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Received January 16, 2018; revised November 07, 2018; accepted November 08, 2018
View online at Wiley Online Library (wileyonlinelibrary.com);
DOI: 10.1002/bbb.1961; Biofuels. Bioprod. Bioref. (2018)
Abstract. This is a review of work on the potential of biorefineries. First, it considers the concept of
a refinery, the differences between biomass and oil, and the advantages of a biorefinery over a refin-
ery. It goes on to describe the bio-based economy and biorefinery concepts, and to discuss its origin
as a promising alternative to dependence on non-renewable feedstocks. It provides an exhaustive
description of the classification of biorefineries, considering aspects such as systems, technological
implementation status, size, feedstocks, platforms, products, and conversion processes. It outlines the
main methodologies for designing biorefineries – conceptual design, optimization, and the ‘early stage’
method. Methodologies for the economic, environmental, and social assessment of a biorefinery are
presented. Finally, challenges linked to the implementation of biorefinery projects at industrial level are
discussed. The authors conclude that the methodologies of conceptual design and optimization must
complement each other to achieve a robust design from a conceptual and mathematical point of view.
© 2018 Society of Chemical Industry and John Wiley & Sons, Ltd.
The refinery concept to the emission of greenhouse gases, the existence of new
reservoirs and technologies (fracking), and competition
A
n oil refinery is defined as an industrial platform that with emerging markets. These factors have led to a search
has, as its main goal, refining oil to obtain fuels for for alternative feedstocks that are widely available, renew-
transport using combustion engine (e.g., gasoline and able, and that are relatively low in cost. Biomass appeared
jet fuel), high-value chemicals, and petrochemical raw materi- to be a promising raw material with these characteristics.
als. Refineries appeared in the 1940s and illustrate the vitality It can be transformed by different conversion methods, in
of the chemical industry. Currently, about 85% by mass of a biorefinery, into products, including food and feed.
refined oil in the refineries corresponds to fuels. The remain- The differences between biomass and oil as raw materials
ing 15% consists of other products.1 All fractions of oil are are:3
used to obtain different products. There are two types of refin-
eries: state and private. All refineries use technologies that are • Crude oil is found in nature just in one form; it is there-
optimized and highly predictable – mature technologies.2 fore a homogeneous raw material. On the other hand,
In recent years, this industry has been affected by fluc- biomass is a heterogeneous raw material that can be
tuations in the oil price, high levels of pollution linked found in a wide variety of forms with different origins.
Correspondence to: Carlos A. Cardona Alzate, Instituto de Biotecnología y Agroindustria, Departamento de Ingeniería Química,
Universidad Nacional de Colombia Sede Manizales, Manizales, Colombia. E-mail: ccardonaal@unal.edu.co
© 2018 Society of Chemical Industry and John Wiley & Sons, Ltd 1
V Aristizábal-Marulanda, CA Cardona Alzate Review: Methods for designing and assesing biorefineries
• Crude oil is found in nature in specific and limited refineries with sustainable alternatives). With design as
places, whereas biomass can be found in almost any the first step, it is possible to demonstrate the potential of
place where there are crops, forests, and living beings. biorefineries.
• Compared to oil, biomass is composed mainly of oxy-
gen, with lower fractions of carbon, hydrogen, and Biobased economy (BBE) concept
sulfur.
• Biomass needs to be depolymerized through complex To understand the origin of the biorefinery concept it is
procedures to access sugars contained in the biomass necessary to consider other terms such as bioeconomy
easily for added value. On the other hand, it is only (BE) and biobased economy (BBE). Generally, BE and
necessary to remove water and impurities from oil for BBE are similar in definition but the first term focuses on
it to be used in fractionation. the global aspect and the second refers to the individual
• Biomass has seasonal changes and so cannot be pro- aspect, the BE term comprises the BBE. Some definitions
duced throughout the entire year. However, it can be given by different institutions are presented below:
cultured in arid soil. According to the European Commission ‘The BE encom-
• Biomass needs to be stabilized before storage to guar- passes the production of renewable biological resources
antee continuous operation of the biorefinery. and their conversion into food, feed, bio-based products
• Biomass has fewer logistical restrictions than oil pro- and bioenergy. It includes agriculture, forestry, fisheries,
duction and use. food and pulp and paper production, as well as parts of
chemical, biotechnological and energy industries.’4
The advantages of a biorefinery compared with an oil The Organization for Economic Co-operation and
refinery are:1,2 Development (OECD) defines the BE as ‘the application of
• Biorefineries have higher capacity and configuration biotechnology to primary production, health and industry,
flexibility. where biotechnology contributes to a significant share of
• A biorefinery chooses the products considering differ- economic output.’5
ent factors such as raw material composition, process- In the First Global Bioeconomy Summit in Berlin in
ing capacity, equipment, and market demand. November 2015, coordinated by the Food and Agriculture
• Operating and product diversity allow production to be Organization of United Nations (FAO), the International
changed over time and protect the biorefinery against Advisory Committee on Bioeconomy defined BE as
economic recession and seasonal demand cycles. ‘knowledge-based production and utilization of biological
• A biorefinery can affect climate change, energy secu- resources, biological processes and principles to sustainably
rity, and rural development in a positive way if it is provide goods and services across all economic sectors.’6
designed properly.3 The German Bioeconomy Council defined BE as ‘the
sustainable and innovative use of renewable resources to
However, the maturity level of technologies used in provide food, feed and industrial products with enhanced
a biorefinery is a critical issue. Refineries use very well properties. Besides economic growth the BE aims for food
developed and commercialized technology. Logistical con- security, climate protection and conservation of scarce
siderations are important in guaranteeing the availability natural resources.’7
of biomass in a biorefinery. In the case of refineries, the oil The International Energy Agency (IEA) defines BE as
supply is continuous, with few or no constraints. When ‘food and feed industries (agriculture, forestry, horticul-
refineries were developed, no specific methodology for ture, fisheries and aquaculture, plant and animal breeding,
identifying all the possible products, platforms, and tech- the nutrition and beverage industry) + biobased economy’
nologies to use the oil was considered. Over time, trans- and BBE as ‘non-food industries – chemical, material,
formation routes were added to basic refining to exploit medicine, pulp + paper and wood industries + bioenergy
both solid and gas fractions obtained at this stage. For this (including biorefineries).’8 The BE is the BBE plus the pro-
reason, the purpose of this article is to discuss and review duction and use of food and feed.6
the main barriers that biorefinery development encounters Why is the BBE developed? To answer this question factors
today. Efficient strategies are needed to design biorefineries such as population growth, the increase in waste, climate
considering the concept of sustainability to avoid repeat- change, loss of biodiversity, and the depletion of resources
ing the mistakes found in oil refinery design, implementa- need to be considered. These are the starting points that led
tion, and operation (today this sector wants to replace oil to the search for an innovative alternative to oil to generate
2 © 2018 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. (2018); DOI: 10.1002/bbb
Review: Methods for designing and assesing biorefineries V Aristizábal-Marulanda, CA Cardona Alzate
new products and services. The sun and wind can generate The biorefinery concept
energy in electrical form but cannot provide mass and car-
bon compounds or organic molecules. The carbon sources The construction of the BBE solves current difficulties
are essential to obtain tangible products, and in recent years and promotes an environmentally friendly industry. The
oil has been the main feedstock for this. Biomass is a valu- biorefineries are the basis for building a BBE because they
able alternative to oil and its use in industry is known as the provide opportunities in all economic sectors. However,
biobased economy. When a fossil feedstock such as oil is they need continuous innovation. The biorefineries are a
used as a source for generating energy, chemicals, and fuels, medium for achieving sustainable development in indus-
this is known as the fossil-based economy. try through the production of value-added products from
The fossil-based economy needs a transition state to pass biomass and they have the capacity to generate a wide
to the BBE. This state is driven by different considerations, variety of bio-based products and bioenergy to nurture
for example, economic, political, environmental, demo- the BBE. The most important definitions given for a biore-
graphic, agricultural, and food. The challenge is to propose finery and its evolution from stand-alone processes are
an economy based on renewable resources that is techni- described below.
cally, economically, environmentally, and socially feasible. According to the IEA Bioenergy Task 42, a biorefin-
For example, raw materials such as sugar cane and coffee ery is defined as ‘the sustainable processing of biomass
are used as foods, but these crops contain large amounts of into a spectrum of marketable products (chemicals and
biomass that can be valorized to obtain biobased products materials) and energy (fuels, power and heat).’2 Systems
such as biofuels, bioplastics, and biochemicals. This exam- that include a biorefinery can be presented as a facility,
ple shows that the BBE is directly linked to food but does a cluster, a spectrum, or a process. A biorefinery is the
not create any type of competition. integrated processing of biomass to a range of products. It
There is some controversy arising from the increase considers upstream, midstream, and downstream aspects
in food prices as a consequence of the use of crops and in a process. For Task 42 a real biorefinery produces both
agricultural residues for energy and chemical production. energy and non-energy products.
However, two facts should be considered. The first is the According to the National Renewable Energy Laboratory
competition for agricultural products that can be used and the US Department of Energy, a biorefinery is ‘a
to produce biobased and food products. The second is, facility that integrates biomass conversion processes and
the competition for the use of the agricultural sources.9 equipment to produce fuels, power, and value-added
When the biorefinery includes some food and feed prod- chemicals from biomass’ and ‘an overall concept of a
ucts, this controversy can be reformulated. Maltsoglou et promising plant where biomass feedstocks are converted
al. (2014)10 evaluated the effect of bioenergy production and extracted into a spectrum of valuable products.’
and its close relationship with the concept of food secu- Euroview defines a biorefinery in terms of ‘integrated
rity. These authors studied the production of electricity bio-based industries, using a variety of technologies to
in Malawi using the Bioenergy and Food Security (BEFS) produce chemicals, biofuels, food and feed ingredients,
rapid appraisal methodology. The analysis assessed the biomaterials (including fibers) and power from biomass
potential availability of biomass that is additional and / raw materials.’11
or complementary to food, feed, and other uses, and also The authors’ own, more extensive definition is that ‘a
the competition for resources and its negative impact on biorefinery is a complex system, where biomass is inte-
food production. As a result, the authors reported that the grally processed or fractionated to obtain more than one
use of sunflower and soybean oils for electricity genera- product including bioenergy, biofuels, chemicals and high
tion using straight vegetable oil as fuel is the most cost- value-added compounds that only can be extracted from
competitive option in comparison with other technologies bio-based sources. The latter occurs after a comprehensive
such as biomass gasification using corn cobs. The authors study of the raw materials to be used and the creation of
found that rural electricity production was possible in the a sustainable design based on the latest state-of-the-art
Malawi context without affecting the food production and technologies and approaches, which include aspects of the
income from the food industry. Nevertheless, they sug- three pillars of sustainability.’12 This definition addresses
gest that there should be clear energy policies to ensure the need for the comprehensive design and analysis of the
development of the interconnected electricity production biorefinery. Then, it is possible to reach the main goals of
in ways that do not interfere with other well established the biorefineries: maximizing the value of the products
technologies.10 obtained from the biomass, to increase competitiveness
© 2018 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. (2018); DOI: 10.1002/bbb 3
V Aristizábal-Marulanda, CA Cardona Alzate Review: Methods for designing and assesing biorefineries
4 © 2018 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. (2018); DOI: 10.1002/bbb
Review: Methods for designing and assesing biorefineries V Aristizábal-Marulanda, CA Cardona Alzate
• Large production facilities. These are linked to a net- is used in the petrochemical industry, where crude oil is
work of decentralized primary processing plants. fractionated into intermediate products (e.g., naphtha)
• Very large production facilities. These are located near to generate energy and chemicals. The platform products
a port and use different types of biomass. are also known as pillars, bulk chemicals, bio platform
molecules (bPM), or building-block chemicals, and are the
However, it is important to note that there are no objec- basis for obtaining value-added products.3,20,21 The most
tive criteria defining the boundaries between small and important platforms in the formulation of biorefineries are
large scales. described in Table 3.
© 2018 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. (2018); DOI: 10.1002/bbb 5
V Aristizábal-Marulanda, CA Cardona Alzate Review: Methods for designing and assesing biorefineries
6 © 2018 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. (2018); DOI: 10.1002/bbb
Review: Methods for designing and assesing biorefineries V Aristizábal-Marulanda, CA Cardona Alzate
mechanical.2,15,20 Table 4 indicates examples for each con- is coffee cut-stems (CCS) and comes from the agricultural
version process and its description. sector as a lignocellulosic residue obtained in coffee process-
Figure 2 shows an example where the features described ing. This feedstock consists mainly of cellulose, hemicellu-
above are considered to formulate a biorefinery. The feedstock lose, and lignin. The biorefinery has as its goal the production
© 2018 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. (2018); DOI: 10.1002/bbb 7
V Aristizábal-Marulanda, CA Cardona Alzate Review: Methods for designing and assesing biorefineries
of ethanol, furfural, and hydroxymethylfurfural (HMF). The the basis for the production of furfural through a chemi-
ethanol (biofuel) is classified as energy driven, and furfural cal process such as dehydration and mechanical / physical
and HMF are classified as product driven – more exactly, as processes such as extraction and distillation. The C6 sugar
fine chemicals and / or chemical building blocks. The CCS platform is divided in two streams to generate ethanol
biorefinery considers different conversion processes, start- and HMF. In the case of ethanol, biochemical processes
ing with mechanical processes such as milling, chemical such as fermentation and mechanical / physical processes
processes such as acid hydrolysis, and biochemical processes such as distillation are used. In the case of HMF, the same
such as enzymatic hydrolysis, to obtain the platforms for conversion processes are involved that are used in furfural
C5/C6 sugars and C6 sugar. The C5/C6 sugars platform is production.
8 © 2018 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. (2018); DOI: 10.1002/bbb
Review: Methods for designing and assesing biorefineries V Aristizábal-Marulanda, CA Cardona Alzate
Figure 2. Coffee cut-stems: an example of the combination of the features for the
classification of a biorefinery according to Task 42.
© 2018 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. (2018); DOI: 10.1002/bbb 9
V Aristizábal-Marulanda, CA Cardona Alzate Review: Methods for designing and assesing biorefineries
Table 5. Examples of works that consider the conceptual design, optimization or the early-stage method
as methodology to the biorefineries designing.
Description Study case Key aspect Reference
Conceptual design
García et al.22 propose a techno-economic and This methodology is used in order This example uses the methodol- 22
environmental assessment considering different to compare the stand-alone process ogy of Life Cycle Assessment
levels of integration are considered (e.g., mass and biorefinery ways to produce (LCA) in order to carried out the
and energy integration, non-conventional tech- biodiesel, ethanol and butanol as environmental assessment. LCA is
nologies) along with the analysis of the process potential cases for bioenergy produc- not commonly applied to biorefin-
scale to determine the economic profitability tion using fresh fruit bunches as raw eries, since it is long and tedious
and environmental impacts of the proposed material. work.
cases.
González et al.23 evaluated fruit-based biorefin- The proposed methodology is This case uses an Amazonian 23
eries subjected to conditions of the Amazonas applied to Makambo (Theobroma exotic fruit for the generation of
region, by using techno-economic and environ- bicolor) biorefinery that considers added-value products.
mental criteria (details of the biorefinery con- the obtaining of pasteurized pulp,
figuration and to establish some understanding butter, residual cake (paste used as
about the economic aspects without address- a substitute for cacao), extract rich
ing marketing aspects). in phenolic compounds, biogas and
biofertilizer.
Moncada et al.24 used the conceptual design This methodology is applied to a sug- This example considers different 24
methodology applied to a simulation procedure arcane biorefinery for the Colombian conversion pathways as function
in order to evaluate biorefinery schemes for all case and two more scenarios for the of feedstock distribution and tech-
the scenarios, using Aspen Plus software, that sugar, fuel ethanol, PHB, anthocya- nologies for products.
include productivity analysis, energy calcula- nins and electricity production.
tions and economic evaluation for each process
configuration.
Optimization
Bao et al.25 propose a shortcut method to This methodology is applied to dif- The methodology provides an 25
screen potential transformation routes and ferent case studies where integrated effective and quick solution to
synthesize integrated biorefineries, considering biorefineries are considered. The select a transformation route.
different objective functions (e.g., maximum integrated term refers to systems
earnings, productivity, etc.). that consider multiple transformation
routes and platforms.
Ponce-Ortega et al.26 indicate a general The proposed methodology is This methodology has the con- 26
approach for the optimal arrangement of applied to a study case that com- straint that does not allow the
processing routes in a biorefinery including prises several processing routes for selection of various conversion
sequential steps for the superstructure build- bioalcohols production using ligno- routes simultaneously attractive
ing and disjunctive programming models. The cellulosic biomass. from economic and environmental
approach grants the selection of optimal biore- The optimization problem is formu- point of view.
finery configuration considering a specific factor lated as a mixed integer nonlinear
(e.g., economic, environmental, social, etc.). program (MINLP) and is solved using
BARON solver.
Pham and El-Halwagi27 present a systematic The proposed approach is applied to This approach is similar to the 27
approach that involves two stages, synthesis a study case where various pathways methodology indicated by Ponce-
and optimization, in order to generate the best to produce alcohol from lignocellu- Ortega et al.26
biorefinery configuration considering available losic biomass are considered.
feedstocks and desired products.
This methodology involves various products This methodology is applied to Kelloway and Daoutidis28 report a 28
and processing routes with a multiobjective biorefineries that use numerous feed- similar approach that mentioned
optimization considering economic (e.g., net stocks and products. The optimiza- Bao et al.25
present value) and environmental (e.g., carbon tion problem is formulated as a mixed
efficiency) aspects. integer nonlinear program (MINLP)
and is solved using BARON solver.
10 © 2018 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. (2018); DOI: 10.1002/bbb
Review: Methods for designing and assesing biorefineries V Aristizábal-Marulanda, CA Cardona Alzate
Table 5. (Continued)
Description Study case Key aspect Reference
29 30 29,30
Bertran et al., Rosengart develop a method- This approach is applied to case Despite of this methodology pre-
ology for synthesis and design of transforma- studies as, biorefinery, carbon cap- sents excellent characteristics, it
tion routes based on 3-stage approach. In first ture utilization and adipic acid pro- does not consider the energy inte-
stage, the optimal transformation routes are duction. The optimization problem is gration topic.
determined through the superstructure optimi- formulated as a Mixed-Integer Linear
zation. In second stage, design problems are Programming (MILP) systems that are
solved and improvement objectives are stab- solved using CPLEX solver.
lished using integrated tools. Finally, in the third
stage, new option are created using the deter-
mined route and stablished objectives.
Early-stage method
Patel et al.31 proposed a methodology that is The methodology is applied to eight The methodology is applied to 31
based on a multi-criteria approach that consid- new bio-based process alternatives processes in stages of laboratory
ers five indicators in an only value. The indicators of the CatchBio research consortium and expected future.
involves aspects as, economic, environmental and in the Netherlands.
risks based on techno-economic and life cycle
assessments and green chemistry principles.
Moncada et al.32 indicated a method that com- The methodology is applied to three The methodology includes cata- 32
bines indicators describing economic, environ- study cases, catalytic conversion of lytic and biochemical conversion
mental, and operational aspects. The indicators bio-based syngas, biochemical conver- processes in biorefinery systems.
are combined in an only score and compared sion of carbohydrates and biochemical
with petrochemical processes. and catalytic conversion of glycerol.
results. Finally, the US-EPA Waste Reduction (WAR) the technologies and their critical points. An extension
algorithm and / or GREENSCOPE or LCA studies allow of the well known onion diagram is used to design the
the environmental impact to be determined. Two types of process schemes and processing routes that compose a
integration can be developed: (i) mass (using commercial biorefinery.
software) and (ii) energy (using pinch analysis or energy • Sequencing. The sequencing concept establishes a logical
analysis). Experimental data such as feedstock charac- order step by step to associate transformation routes with
terization, reaction kinetics, yields, and operation condi- products. The implementation of this concept considers
tions, reported in the literature, are fed into the simula- factors such as (i) platforms, (ii) technological develop-
tion tools. A comparison between the results for different ments, and (iii) constraints on the quality of products.
scenarios can be made to choose those presenting the best The determination of the most promising sequences
performance. Conceptual design applied to biorefiner- requires systematic tools to identify routes, distributions,
ies comes from the synthesis of the chemical processes platforms, and products with the best characteristics.
approach.22,23,33–35 However, the approach is extended to Optimization is used in decision making.
complex systems (i.e., biorefineries with multi-product • Integration. This concept defines the possibilities of
portfolios) because new elements are included. Three integration between feedstocks, processing routes, and
concepts constitute the conceptual design: (i) hierarchy, products. Integration emphasizes the maximum use of
(ii) sequencing, and (iii) integration.12,33,36 These concepts resources in the biorefinery. In the case of feedstocks,
are interlinked and their combination leads to a process the remaining streams of a process can be exploited in
synthesis approach to obtain biorefinery models. A brief other process to reduce waste streams. For processing
description of these concepts is presented below: routes there are two types of integration – (i) mass and
(ii) energy – which are directly linked to economic and
• Hierarchy. The hierarchy concept considers the hierar- environmental aspects.
chical decomposition of the main elements in a biore-
finery such as feedstocks, products, and technologies.
The first analysis is focused on feedstocks and prod-
Optimization
ucts, where the feedstock composition and possible Optimization can help bioprocessing in the assessment
decomposition in platforms to generate a set of prod- of the profitability of transformation routes and prod-
ucts is considered. The second analysis is focused on uct portfolios. Stakeholder value is maximized through
© 2018 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. (2018); DOI: 10.1002/bbb 11
V Aristizábal-Marulanda, CA Cardona Alzate Review: Methods for designing and assesing biorefineries
the global optimization of the supply chain (SC). Many and/or CHEMCAD, among others, (iii) validation of
authors have applied optimization methodology to the performance of models, (iv) integration of processes
design of all types of biorefineries, for example Martin using tools as pinch analysis, thermal management,
and Grossmann, 37 Sammons Jr et al., 38 Sammons Jr et and resource conservation strategies to optimize
al., 39 Zondervan et al.,40 Santibañez-Aguilar et al.,41 the simulation models, (v) optimization of simula-
Giarola et al.,42 Bao et al., 25 Ponce-Ortega et al., 26 Pham tion models considering the minimum use of utili-
and El-Halwagi, 27 You et al.,43 El-Halwagi et al.,44Wang et ties, maximum use of resources, and reduction in
al.,45 Tong et al.,46 Kelloway and Daoutidis, 28 Gong et al.,47 environmental impact, and vi) obtaining economic
Santibañez-Aguilar et al.,48 Geraili et al.,49 Rizwan et al.,50 data through cost estimation software and references,
Belletante et al.,51 Hernández-Calderon et al.,52 Bertran et supplier data, etc., and environmental data using the
al., 29 Rosengart.30 This methodology allows the assessment US-EPA Waste Reduction (WAR) algorithm, SimaPro,
of different optimization objectives such as maximizing GREENSCOPE, databases, etc. In the validation step
yield and profit, minimizing costs, minimizing waste or (i.e., substep iii), when a process needs the use of a
fixed costs, and environmental impact. solvent, techniques for molecular design should be
The main steps of the optimization methodology of employed to select the best option from the environ-
superstructures are given below.38,39 The majority of mental and safety points of view.
authors follow this order or make small changes. The six substeps mentioned before are the basis for
generating a compact model library and performance
1. To define the scope and complexity of the problem. A pro- database and a superstructure of transformation routes
cess systems engineering (PSE) approach is needed to (a tree with all optimized models). This approach pro-
solve the complexity of the product allocation problem in motes constant upgrading of models or inclusion of
the processing facilities. The complexity of the problem new models, without changing the methodology.
does not allow it to be solved by heuristics or rules of 3. To optimize the biorefinery. The optimization frame-
thumb. The PSE approach uses techniques such as process work considers a combination between the models
integration and mathematical optimization to ensure library and economic performance with a numerical
a target approach combining simulation and experi- solver – a mixture of the following factors: (i) Objec-
mental work. The PSE can ensure high economic and tives of process design, (ii) processing super-structures,
social benefit, reducing the use of feedstocks and energy. (iii) constraints, (iv) a performance framework data-
Optimization methodology involves the superstructure base (economic potential), and (v) numerical solver
concept, where all possible transformation routes to routines such as MILP (mixer integer linear program),
obtain a product set are considered, maximizing the net and MINLP (mixed integer non-linear program).
present value and minimizing environmental impact. The optimization framework aims to identify the
Mathematical optimization based on the framework solutions capable of maximizing the economic perfor-
is carried out to fulfill the objectives mentioned before. mance and when the solution is positive, it passes to
This allows the inclusion of techno-economic aspects, the assessment of the environmental performance. If a
information from experimental studies, modeling, and solution fulfills the environmental constraints, an opti-
simulation. The framework addresses issues such as mal process scheme has been identified. If the envi-
product prices, product amount, the best configura- ronmental solution is negative, constraints are relaxed
tion, and optimal conditions. until acceptable environmental results are achieved.
2. To integrate modeling and experimental data. A com-
plete and robust library composed by simulation mod-
els of transformation routes and a database of yields
The ‘early stage’ method
is built in this step. Experimental results are used to The ‘early stage’ sustainability assessment method uses a
validate the simulations of processes made with com- multi-objective decision framework for the preliminary
mercial software packages. assessment of chemical processes at the laboratory stage.
The proposal is to assess stand-alone processes (i.e., This method allows chemical processes to be revised tak-
simulation models) that comprise the global biorefin- ing sustainability into account because a multi-criteria
ery considering these substeps: (i) Extraction of data approach is used, with a combination of economic, envi-
and knowledge from literature and experiments, (ii) ronmental, safety and health indicators.53 However, this
simulation of models using Aspen Plus, HYSYS, Pro II approach is modified for bio-based processes and con-
12 © 2018 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. (2018); DOI: 10.1002/bbb
Review: Methods for designing and assesing biorefineries V Aristizábal-Marulanda, CA Cardona Alzate
siders characteristics such as biomass pretreatment, co- applied to a biorefinery is to determine its economic and
product numbers, risks, and comparison with equivalent social profitability. High profitability can generate benefits
petrochemical counterparts.31,54,55 at a social level to improve the quality of life of differ-
This approach applied to the design of biorefineries is an ent communities associated direct or indirectly with the
alternative to methodologies such as (i) optimization of process.
superstructures and (ii) process engineering and concep- Some useful parameters that can be used to calculate
tual design of processes.32,55 The early stage sustainability the economic assessment of a biorefinery are capital cost
assessment method applied to biorefineries has as its goal (or fixed capital investment), operating cost (operating
the assessment biorefinery products systematically to expenses), net present value (NPV), return on investment
identify those with the best potential from a sustainability (ROI), discounted payback period (DPBP), payback period
point of view at an early design stage.32,55 (PBP), internal rate of return (IRR), and gross margin (or
The method enables the sustainability of catalytic and economic margin, profit margin),56–58 which can be esti-
chemical processes to be determined and identifies their mated using computer programs such as economic analyz-
strengths and weaknesses. Three sustainability indicators ers.59 Plant capacity and mass and energy balances are the
are considered: (i) economic constraints (EC), (ii) energy- basis for the estimation of costs. Operating costs include
related impact of raw materials (EIRM), and (iii) process raw material costs, plant location, labor, and utilities (i.e.,
complexity (PC). These indicators are grouped in a single steam, water, fuel, electricity). Raw material costs change
index with help of weighting factors to provide fast com- according to the availability and characteristics of the raw
parison and choosing of process.32,55 This method, applied materials. Utility charges are usually expressed as money
to the design of biorefineries, involves five steps:32 unit / ton, money unit/m3, money unit/MW, money unit/
kWh of utility.35 The money unit can be expressed in USD,
1. Modification of the method. Initially, the method is € or any unit, depending on the location of the biorefinery
applied to chemical processes and stand-alone bio- project or the needs of the evaluator, company, or market.
based processes considering five indicators. Then, the
method is applied to biorefinery design (i.e., a combi-
nation of chemical, thermochemical, mechanical, and Environmental assessment
biochemical processes) considering the three indicators
mentioned before. The environmental assessment is a methodological tool to
2. Definition of the study cases. The definition of the study identify, assess, and enable decisions to be made about the
cases is according to the literature revision and the environmental impacts generated in a process or biore-
selection of chemicals, derivatives and platforms. finery. In the literature there are methods that allow this
3. Data collection. The data collection is based on the impact to be determined. In the case of a biorefinery, three
literature, databases, and analysis of stand-alone pro- main methods are used and are mentioned below.
cesses.
4. Application of the method. In first place, sustainability Physical-chemical analysis
scores are estimated for stand-alone bioprocesses and
The conventional assessment of bio-based processes from
then a comparison with the reference system is made. The
an environmental point of view has been made with
method includes analysis of sensitivity and scenarios.
physical-chemical techniques such as the determina-
5. Analysis of results. The analysis of results considers the
tion of biochemical oxygen demand (BOD) and chemical
classification of derivatives, comparison of platforms,
oxygen demand (COD).60 Biochemical oxygen demand is
and identification of promising derivatives.
the content of biodegradable organic matter in the waste-
This method is closer to the conceptual design method, water of a process and it is measured by the amount of
using practically the same tools to provide the starting data. oxygen required for the oxidation. The oxygen demand
is the result of three types of materials: organic carbonic
materials (useful as a source of feed by aerobic organisms),
Economic assessment oxidable nitrogen (derived of nitrogen organic compounds
such as sources of feed for bacteria), and chemical reduc-
The economic assessment of a biorefinery focuses on the tion compounds (ferrous ions, sulfites, sulfides). The COD
calculation of the parameters that can determine its eco- is the measure of oxygen equivalent to the content of
nomic feasibility. The main goal of economic assessment organic matter of a stream that is susceptible to oxidation
© 2018 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. (2018); DOI: 10.1002/bbb 13
V Aristizábal-Marulanda, CA Cardona Alzate Review: Methods for designing and assesing biorefineries
for a strong chemical oxidant. The oxidation under some and products. The LCA is the methodological approach
conditions of acidity, temperature, and time, transforms used most worldwide to carry out global assessments
the organic matter in carbon dioxide and water. Wilkie et (economic, energy, environmental, and social).69 With
al.,61 Fava et al.,62 and Sanchez et al.63 are some authors the LCA it is possible to calculate the environmental dif-
that have used these methods to determine the organic ficulties associated with complex and multi-disciplinary
burden in the wastewater streams of bio-based processes processes. This method can be applied to sectors as build-
and biorefineries. ing, agriculture, transport, and engineering, among oth-
ers. Uihlein and Schebek,70 Cherubini and Jungmeier,71
Impact categories Cavalett et al.,57 De Meester,72 and Karka et al.73 have
illustrated the relevance of this approach in the assessment
The categorization of environmental impacts is promoted
of biorefineries. In general terms, an LCA consists of four
by the United States Environmental Protection Agency
stages:69
(US-EPA) through the Waste Reduction Algorithm
(WAR) and the Gauging Reaction Effectiveness for the 1. Goal definition. What is the goal? Which processes
Environmental Sustainability of Chemistries with a include the LCA and how?
Multi-Objective Process Evaluator (GREENSCOPE). The 2. Inventory analysis of the LCA. Determination of input
GREENSCOPE tool is useful for quantifying process sus- and output flows and calculation of emissions for dif-
tainability and the generation of the life cycle inventory ferent environmental resources.
(LCI). The analysis consider the mass and energy balances, 3. Impact analysis of the LCA. Classification and assess-
including input-output streams such as raw materials, ment of results and comparison with standards, mod-
reagents, residues, and products, and the energy demand els, or known tools.
by equipment. The WAR is based on the determination of 4. Interpretation of results. Results analysis, considering
the potential environmental impact (PEI), which meas- the goal of the LCA and recommendations according
ures the average unrealized effect or impact that mass and to the results.
energy emissions would have on the environment.64 The
PEI considers impacts such as the human toxicity poten- Ahlgren et al.74 made a review of the main existing
tial by ingestion (HTPI), the human toxicity potential by standards and guidelines for LCA of biorefinery systems
exposure (HTPE), the aquatic toxicity potential (ATP), ter- (e.g., ISO 14040:2006, ISO 14044:2006, International
restrial toxicity potential (TTP), global warming potential Reference Life Cycle Data System (ILCD), ISO 14025:2006,
(GWP), ozone depletion potential (ODP), photo-chemical etc.) and concluded that six key steps should be consid-
oxidation potential (PCOP), and the acidification poten- ered for the analysis. The key steps are mentioned and
tial (AP). The WAR algorithm is mainly a tool to compare explained below.
process configurations,35 Lou et al.,65 Moncada et al.,66
• Goal definition. This step determines the methodologi-
Aristizábal et al.,67 and Moncada et al.68 are some authors
cal options that an LCA should consider. A clear goal
who have used this methodology to determine the PEI in
definition is necessary for the interpretation of the
bio-based processes and biorefineries.
results. Based on two standards, ISO 14040 and ISO
Environmental impact can also be categorized using the
14044, the goal is composed of (i) reasons for the study
Ecoinvent database, with impacts such as abiotic depletion
(formulation of research questions), (ii) accurate defini-
potential (ADP), global warming potential (GWP), ozone
tion of the product, (iii) functional unit definition, (iv)
layer depletion potential (ODP), photochemical oxida-
description of the system boundaries, (v) requirements
tion potential (POCP), human toxicity potential (HTP),
and assumptions, (vi) expected public. The formulation
eco-toxicity potential (ETP), acidification potential (AP),
of the questions is an important part in goal definition,
eutrophication potential (EP), and comparison of eco-
for the biorefineries case, these can be formulated con-
efficiency. Eco-efficiency is defined as ‘emissions per unit
sidering the feedstock use and number of products. The
of output’, which represents the environmental intensity of
time horizons of the LCA should also be specified in
production.65
the goal and scope definition.
• Functional unit. Standards and guidelines define the
Life-cycle assessment (LCA) selection of functional units as a key aspect of the com-
Life-cycle assessment (LCA) is defined as a method to parison of cases and the interpretation of results. Given
assess and determine the environmental impact of systems that the biorefinery considers more than one product,
14 © 2018 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. (2018); DOI: 10.1002/bbb
Review: Methods for designing and assesing biorefineries V Aristizábal-Marulanda, CA Cardona Alzate
© 2018 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. (2018); DOI: 10.1002/bbb 15
V Aristizábal-Marulanda, CA Cardona Alzate Review: Methods for designing and assesing biorefineries
For this reason, an important challenge is the upgrad- • A biorefinery should ensure that production output is
ing and evolution of these biorefineries to industrial maximized and that consumption of inputs (reagents,
infrastructures and their integration into the market. energy) is minimized.
• Appropriate implementation of industrial biorefineries • The characteristics and composition of biomass
requires mature technologies, starting with R&D tasks, should be well known to obtain optimal conver-
followed by pilot-plant tasks, demonstrations, and sion, optimal availability of biomass, and economic
deployment strategies. benefit.
16 © 2018 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. (2018); DOI: 10.1002/bbb
Review: Methods for designing and assesing biorefineries V Aristizábal-Marulanda, CA Cardona Alzate
• Lignin is the main residue of biomass processing (20– Conclusions and future research
30%) and it is normally used for energy generation. A work
challenge for biorefineries is to transform this material
in value-added products using advanced technologies. It is clear that existing design methodologies appear to fail
This can contribute to the success of biorefineries. in their purpose of providing sustainable biorefineries.
• The transformation of lignocellulosic biomass to simple For example, the conceptual design strategy needs to be
sugars needs the use of enzymes. The challenge is to optimized to consider possible alternatives, and the opti-
develop efficient and cheap enzymes to extract sugars mization strategy requires conceptual design to establish
efficiently. that the optimization bounds are in real, practical ranges
• Another challenge is the development of biochemical needed in industry. The biorefinery definition is also not
and chemical catalysts with a high yield of the desired very clear; nor is it clear how to identify and guarantee
product. that a biorefinery is efficient.
• Feedstock processing associated with densification and Biorefinery design is important for achieving sustain-
conservation techniques, and the distribution network ability at the technical, economic, environmental, and
of products, are presented as logistical challenges. In social levels. A biorefinery should involve a large number
the latter case, existing infrastructure can be used for of alternatives to obtain the best processing line. If many
the transport of biofuels. alternatives are not considered, the biorefinery’s process-
• The integration of bioproducts in current value chains, ing line is not guaranteed as the best.
and funding difficulties, are commercial challenges in Both at the academic and the industrial level, there
the industrialization of biorefineries. are still deficiencies in the understanding of biorefinery
• The biorefineries face challenges related to land-use design. Many authors are making great efforts in order
change and its impact on the emission of pollutants not to make the same mistakes when refineries are imple-
and food security. When agricultural lands are used to mented. When biorefineries first appeared, oil separation
obtain energy crops, the food supply and biodiversity was used only to obtain a few important products; 80%
can be affected. was regarded as trash and there was no further technical
• Many countries do not have established state poli- analysis of its processing. The evolution of the industry has
cies regarding the use of biorefineries to reduce oil led to the addition of process lines and reduction of waste.
dependence. These systems therefore face challenges The main barriers to the development of future biorefin-
associated with financing and economic support for eries include: (i) The need to produce robust and efficient
technological development and for engineering solu- design methodologies for most integrated biorefineries
tions to overcome obstacles to operating success and (for greater sustainability); (ii) the need for technical,
industrial progress. Two examples of R&D programs, economic, environmental, and social viability, and (iii)
in the USA and the EU, illustrate the benefits of state ignorance of relevant theoretical concepts for building
initiatives. The US Department of Agriculture (USDA) biorefineries in a suitable way. Other barriers not dis-
National Institute of Food and Agriculture (NIFA) cussed in this work are: (i) logistical strategies to address
and US Department of Energy’s (DOE) Bioenergy the reasons why biomass supply chains can fail in any new
Technologies Office promote funding for research and large-scale project; (ii) government policies, which are
into improving biorefinery technology through the very important for further research and implementation of
Integrated Biorefinery Optimization program.86 The these systems. Startup financial support from government
Biobased Industries Consortium (BIC) and the EU will be needed.
operate a public-private partnership (PPP) to provide The authors intend to construct a methodological
funding programs to bio-based projects for rural approach for designing and assessing biorefineries, incor-
development European reindustrialization. The PPP porating aspects of the well known conceptual design
presents three main areas for action: (i) Feedstocks, and optimization methodologies. The authors consider
promoting a tenable biomass supply and constituting that these methodologies could complement each other
innovative value chains; (ii) biorefineries, optimizing to generate promising alternatives. The authors also pro-
transformation routes using R&D, and upscaling demo pose a study of the logistics and supply chain applied to
and large-scale biorefineries; (iii) policies, products and biorefineries and a review about government financial and
markets, optimizing policy structures and establishing investment policies and the integration of this topic with
markets for bio-based products.87 the so-called ‘bioeconomies’.
© 2018 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. (2018); DOI: 10.1002/bbb 17
V Aristizábal-Marulanda, CA Cardona Alzate Review: Methods for designing and assesing biorefineries
Acknowledgements 18. Obydenkova SV, Kouris PD, Hensen EJM, Heeres HJ and Boot
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20 © 2018 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. (2018); DOI: 10.1002/bbb