Energy 92 (2015) 556e568

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Metrics for sustainability analysis of post-combustion abatement of

CO2 emissions: Microalgae mediated routes and CCS (carbon capture
and storage)

lia de Queiroz Fernandes Araújo a, *, Jose
Ofe
Luiz de Medeiros a, Lídia Yokoyama b,

udia do Rosa
Cla
rio Vaz Morgado c

a
Chemical Engineering Department, School of Chemistry, Federal University of Rio de Janeiro, Rio de Janeiro, RJ, Brazil
b
Inorganic Processes Department, School of Chemistry, Federal University of Rio de Janeiro, Rio de Janeiro, RJ, Brazil
c
Civil Construction Department, Polytechnic School, Federal University of Rio de Janeiro, Rio de Janeiro, RJ, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The capture and utilization of CO2 emissions from power plants is an important aspect of the transition to
Received 8 November 2014 a low-carbon economy. In this context, microalgae are widely recognized for their potential to capture
Received in revised form and biochemically convert CO2, with promising applications as raw material for a variety of products.
19 February 2015
Therefore, the energy penalty conventionally presented by CCS (carbon capture and storage) could be
Accepted 23 March 2015
Available online 18 May 2015
replaced by an alternative that offers added revenues, the biorefinery. The productive arrangement is
approached from a process engineering standpoint and relies on sustainability metrics to assess envi-
ronmental and economic performance. The work presents a sustainability assessment procedure, applied
Keywords:
Microalgae
to tracking sustainability of alternative routes for mitigating CO2 emitted by a NGCC (natural gas com-
Biorefinery bined cycle) power plant, a post-combustion capture concept. The evaluated CO2 destination routes are:
Sustainability metrics a) cultivation of microalgae with flue gas, harvesting of microalgae and downstream processing of
Environmental performance biomass to a chemical commodity (ammonia), evaluating the possibility of recycling part of the inter-
Economic performance mediary syngas stream as renewable fuel to the gas turbine; and b) CO2 capture by chemical absorption,
Post-combustion abatement of CO2 followed by compression and storage steps. The proposed Sustainability Degree indicates biofixation of
CO2 with total conversion of syngas to ammonia as the most sustainable among the evaluated
alternatives.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction This work focus on an alternative route for mitigating CO2

The global economy relies on fossil fuels and the energy demand
is expected to rise, contributing to the increase of CO2 atmospheric
concentration, associated to global warming. The challenge of the
century is hence to expand energy supply in a carbon-constrained
economy. Three alternatives for reducing CO2 emissions associated
to energy generation exist: pre-combustion, post-combustion and
oxy-combustion, with pre- and post-combustion exhibiting the
highest energy penalty [2]. Nevertheless, post-combustion is the
most mature alternative to capture carbon and, for installed plants,
stands as the core technology to allow transition to a long-term
low-carbon economy [20].
* Corresponding author. Tel.: þ55 21 3938 7637.
E-mail addresses: ofelia@eq.ufrj.br (O. de Queiroz Fernandes Araújo), jlm@eq.
ufrj.br (J. Luiz de Medeiros), lidia@eq.ufrj.br (L. Yokoyama), cmorgado@poli.ufrj.br
(C. do Rosa
rio Vaz Morgado).
emissions associated to an NGCC (natural gas combined cycle)
power plant through biofixation of the captured CO2 by microalgae
followed by biomass gasification to yield synthesis gas (syngas).
The alternative has potential for medium term commercial success
due to its flexibility in co-processing with fossil feedstock,
benefiting from the available infrastructure. In the proposed post-
combustion emission reduction approach, the produced syngas
can be used as input to a methanol plant or as auxiliary fuel in the
turbine of the CO2 emitting NGCC plant. CO2 emission-abatement
synergy is sought as a biorefinery integrated to the power plant,
with CO2 acting as feedstock. Furthermore, this work compares
biorefinery arrangements to CCS (Carbon Capture and Storage), the
only alternative recognized at present for disposing of large
amounts of CO2 [6e20] estimates approximately 300 active and
planned CCS-related projects worldwide.
With CCS as a reference process, this study evaluates perfor-
mance of microalgae based biorefinery, with gasification of biomass

http://dx.doi.org/10.1016/j.energy.2015.03.116
0360-5442/© 2015 Elsevier Ltd. All rights reserved.
 O. de Queiroz Fernandes Araújo et al. / Energy 92 (2015) 556e568 557

Nomenclature NM normalized quantitative metrics, matrix of dimension

np  nm
CF criticality factor, np  1 vector MEA monoethanolamine
cfref criticality factor of the Reference Process MCA multi-criteria analysis
CCS carbon capture and storage NGCC natural gas combined cycle
CI carbon intensity CI ¼ kg CO2 =kg product (chemical Nc number of Green Design Criteria
produced) CI ¼ kg CO2 =kW generated (energy Nm number of normalized metrics
generated) NM normalized metrics
E-factor energy factor Np number of process alternatives screened
EI energy intensity NPV net present value
FP footprint FP ¼ ha=kg product Mi,j jth metric of the ith process
GCP green chemistry principles PGC principles of green chemistry
GD Green Design Criteria scores, np  nc matrix PGE principles of green engineering
GDC Green Design Criteria ROI time return of investment (years)
GDCI Green Degree Criticality Index, np  1 vector SDP San Diego Principles
GEP green engineering principles SD Sustainability Degree, np  1 vector
HTS high temperature shift SI severity index, np  1 vector
IGCC integrated gasification combined cycle SM Severity Matrix, np  nm
LCC life-cycle cost LCC ¼ CPþtðCOPþCSMÞþCEOL
tAP SP simplifying principles
LTS low temperature shift WGS water gas shift reaction
WI water intensity

to syngas, in three arrangements. In a first alternative, the produced
syngas is entirely directed to a methanol plant. Two other alter-
natives, respectively 25% and 50% of the produced syngas is recy-
cled to the NGCC as co-fuel to the turbine, with the remaining
production directed to a methanol plant. Furthermore, although
CO2 utilization adds value to the captured greenhouse gas, such
destination occurs at the expense of energy and other inputs (e.g.,
water and chemicals) to drive process equipment therefore
requiring methodologies to analyse environmental and economic
performance of alternative strategies.
A large and growing number of environmental, social and eco-
nomic indicators are available, covering the three dimensions of
sustainability [7]. From a business management standing
point [27], list factors favouring the adoption of a sustainable
approach, segregated in three sets: managerial, operational and
economic. In addition to the economic factors that classically guide
process design, three factors listed by Sze
kely and Knirsch in the
operational segment are very sensitive to design decisions, namely
environmental footprint, material inputs and energy efficiency.
Evidently, the design of environmental performance indicators
faces the challenge of converting large volume of information into a
useful decision-making tool for sustainable process design. [30]
classifies metrics as those that indicate the state of a system, in-
dicators, and those that measure the behaviour of a system, per-
formance indicators. Several ad hoc criteria are proposed in the
literature to guide design of sustainable systems (e.g. [1,4,5,17]),
and may be used to score sustainability in a qualitative approach.
Although the use of indicators that quantify specific performance
aspects are also widespread (e.g. [7,14,16,26,28]), unifying ap-
proaches are rare, and the designer has often to cope with multi-
criteria approaches.
A main contribution of this work is hence of proposing a
methodology for sustainability analysis applicable to post-
combustion CO2 abatement in NGCC plants, illustrated by the
three microalgae based biorefinery alternatives and CCS. Specif-
ically, this work focus on performance indicators and criteria as a
way of comparing the proposed alternative processes. The contri-
bution herein presented is a methodology that combines ad hoc
criteria to a set of quantitative indicators e a green degree indicator.
1.1. CO2 biofixation and gasification of biomass as feedstock to
syngas
Microalgae presents rapid growth and produces numerous high
added-value bioproducts [24,25]. As advantages of CO2 biofixation
by microalgae compared to energy crops, microalgae grow in var-
iable climates on non-arable land with non-potable water, thus not
competing with food crop production, and they are able to use
direct flue gases as their carbon source [12]. Microalgal biomass is
rich in lipids and, hence, it is a high energy density feedstock for
fuels and chemicals [6,10].
Soh et al. [32] stated that fuel products e e.g., biocrude, biogas,
biohydrogen, bioethanol, and biodiesel e derived from microalgal
biomass depend on the process and target fuel selected. For
instance, biocrude oil and biogas can be produced through ther-
mochemical conversion processes.
Many alternative routes for processing biomass are possible,
biochemical and thermochemical. However, as noted by Tercero
et al. [35]; the economic benefits of microalgae cultivation pro-
cesses has not been clarified, especially for large-scale production,
which is the case of the abatement of CO2 emissions from thermal
power plants. In this context, applying mature technologies as
biomass gasification has potential competitive advantages against
alternative routes, especially due to the many chemical synthesis
commercially operating with syngas as raw material [6]. Fig. 1
presents a selection of pathways involving the gasification of pro-
duced biomass starting with CO2 captured from flue gas at an NGCC
power plant (dashed squares indicate the set of transformations
herein employed).
1.2. Carbon capture and storage
CCS is not considered an economic application; instead, it con-
stitutes only a destination for the excess carbon, i.e., all CO2 that has
to be discarded because it has no economic use [6]. Urech et al. [36]
recognize that CCS introduces capital and operating (energy) pen-
alties such that it will only become competitive if future policies
limiting greenhouse gas emissions or a tax on CO2 are established.
558 O. de Queiroz Fernandes Araújo et al. / Energy 92 (2015) 556e568
Fig. 1. Selected pathway for microalgae biorefineries. Dashed squares indicate the adopted set of transformations employed to illustrate sustainability analysis. M100 and M85 stand
for uses of methanol as transportation fuel: 100% or mixed to gasoline with 85% of methanol.
Nevertheless, chemical absorption is the only mature technol-
ogy for large-scale post-combustion capture of CO2, with the main
energy penalty occurring in the step of solvent regeneration. For
instance, heat consumption of MEA strippers ranges from 167 kJ to
200 kJ/mol of stripped CO2 [6], driving investigations into more
efficient alternatives of solvent regeneration. Finally, it is consid-
ered a critical component in the portfolio of carbon mitigation
solutions [20]. Therefore, any alternative to post-combustion CO2
mitigation has CCS as a benchmark process.
2. Methodology
The methodology applied in this work consists in proposing a
procedure for assessing process sustainability used in order to
screening process alternatives for mitigation of CO2 emissions from
an NGCC power plant, which includes three main steps: (i) CO2
capture, (ii) CO2 biofixation by microalgae, (iii) microalgae gasifi-
cation to yield syngas, and (iv) syngas conversion to methanol.
Syngas is mostly composed of H2, CO, N2, CO2 and CH4, and has
applications in the production of chemicals and fuels, as well as
electricity generation. The H2 to CO ratio can be altered by down-
stream processing, mainly WGS (water gas shift) reaction, which
produces CO2 while enriching the gas in H2, requiring CO2 capture.
Syngas production and CO2 capture are mature technologies, and
energy generation with syngas (enriched in hydrogen) bears
resemblance to the IGCC (Integrated Gasification Combined Cycle)
power generation [21], where coal is gasified and water gas shifted
to produce power with reduced carbon emissions.
For the pathway proposed in Fig. 1, saline microalga Isochrysis
galbana is employed. It is worth noting that the carbon content of
the biomass is approximately 50% [24]. Hence, nearly 2 t of CO2 can
be converted into 1 t of biomass, potentially amenable to 0.2 t of
lipids. However, its contribution to reducing CO2 emissions is only
possible with the production of fuels and commodities, mainly in
biorefinery arrangements. It is worth noting that, in the proposed
arrangement, CO2 is not chemically sequestered in a product
molecule. Nevertheless, the gas mixture (syngas) is produced in
this route from a renewable source (microalga biomass) obtained in
the CO2 biofixation step, replacing natural gas (fossil fuel), its
conventional feedstock, potentially “greening” its production.
According to IFA [15], virtually all nitrogenated fertilizers are
derived from ammonia, and the production of ammonia is
responsible for 87% of global industrial energy consumption, thus
motivating the proposed arrangement. Mass and energy balances
obtained by Soares et al. [31] support calculation of sustainability
metrics used in a mixed procedure employing green engineering
principles and the Sustainability Matrix proposed herein as
decision-making support.
Process configurations presented by Soares et al. [31] are used as
illustrative examples of the proposed multi-criteria sustainability
analysis based on a framework that combines heuristic rules and
quantitative metrics into a Severity Matrix.
Fig. 2a presents a route of microalga mediated CO2 utilization,
which originated three process configurations for analysis: 0% of
syngas recycle, 25% of syngas recycle and 50% of syngas recycle. The
fourth analysed alternative e the Reference Process e consists of a
classic CCS process, presented in Fig. 2b.
Next, process flowsheets developed and simulated by Soares
et al. [31] with the commercial software ASPEN HYSYS (AspenTech
Inc) are reviewed and condensed to produce a process database to
feed the proposed sustainability analysis procedure.
3. Process alternatives: description, design premises and
simulation results
The proposed productive arrangement is illustrated in Fig. 2a,
where a NGCC (natural gas combined cycle) power plant is the
source of CO2. The flue gas is captured and fed into a photo-
bioreactor where CO2 is biofixed by microalgae Isochrysis galbana.
The resulting biomass is harvested and gasified to produce syngas,
which is then converted to ammonia. In the arrangement, syngas
can be directed to the combustor and co-fired with natural gas, a
carbon recycle to combustion (a “reverse combustion path”). Simi-
larly, part of the ammonia produced can be used as a nutrient in the
photobioreactor. Fig. 3 illustrates the integrated process flowsheet
for NGCC with carbon capture and utilization, simulated in ASPEN
HYSYS process simulator (ASPENTECH Inc). Analogously, NGCC
with carbon capture and storage is illustrated in Fig. 4. Design
premises are listed in Table 1.
Biomass gasification is used as source of H2, followed by water
gas shift (CO þ H2O 4 CO2 þ H2) of residual CO. H2 is further
converted to ammonia (NH3). Gasification was simulated as a Gibbs
Reactor, operating at 700  C, neglecting tar formation. Although
increasing temperature has a large impact in tar formation reduc-
tion, this work considers that tar-free syngas can be obtained in a
properly designed biomass gasification process (Ciao et al., 2006)
and use of bed additives introduced to improve fluidization quality
and to reduce tars in the downstream process [29].
The WGSR (water gas shift reaction) reaction is thermody-
namically favoured at low temperatures and kinetically favoured at
high temperatures [18]. The reaction temperature on the design of
the WGSR, varies according with the type of catalyst used e HTC
(high temperature catalysts, FeOeCrO based) or LTC (low
 O. de Queiroz Fernandes Araújo et al. / Energy 92 (2015) 556e568 559

Fig. 2. Process alternatives: (a) microalga biorefinery (CO2 capture and utilization); (b) CCS e the Reference Process.

Fig. 3. NGCC power plant with carbon capture integrated to biorefinery for synthesis of ammonia.

temperature catalysts, copper based). Lima et al. [18] state that, for
HTC, increasing reaction temperature increases CO conversion,
with best performance in the range from 400  C to 500  C. In the
LTC case, reaction only occurs for temperatures starting at ~200  C,
where conversion rises beyond 90%, decreasing for further increase
in temperature. Industrially, to increase overall conversion, a HTS
(high temperature shift) followed by a (LTS) low temperature shift
reactor is used [22]. Hence, in the proposed process, gas from
gasification is fed to the CO converter (HTS, High Temperature Shift).
The effluent gas stream, containing 2%e4% molar CO (the equilib-
rium concentration) at 400e440  C, is cooled to 205  C and fed to
the low temperature CO converter (LTS, Low Temperature Shift) for
further reducing CO content. Gas leaving LTS has ~18% of CO2, which
is removed by chemical absorption with MEA. MEA is regenerated
in an integrated stripper, which also processes MEA from absorp-
tion of CO2 from NGCC flue gas. Stripped CO2 is fed to

Fig. 4. NGCC power plant with carbon capture and sequestration.

560 O. de Queiroz Fernandes Araújo et al. / Energy 92 (2015) 556e568

Table 1 average monthly bill of US$7926.97/MMCF, i.e., ~0.28$/m3. It was

Process premises. assumed 8322 h of operation per year, 10 years of operation and 2
Combustion years of construction time (40% of the investment in the first year
Natural gas feed (NGCC power plant) 108 t/h and 60% in the second year). Filtration costs were taken as 30% of
Molar composition of natural gas 93.4% CH4 biomass production costs. Energy cost for biomass production was
2.23% N2
3.6% C2H6
used as 0.88 kWh/kg of dry biomass [31].
0.61% C3H8 The simulation in ASPEN HYSYS of biomass production and
Temperature of natural gas feed 205  C harvesting are presented in Appendix A e Biomass Growth and
Air pressure 33 bar Harvesting.
Combustor model (ASPEN HYSYS) Conversion reactor
Table 2 shows a summary of mass and energy balances for NGCC
Residence time 2s
Combustion temperature 1500  C and CO2 utilization, and NGCC with capture and storage (CCS).
CO2 capture In Table 2, it is worth noting that the NGCC section of the four
MEA concentration 30% (w/w) evaluated processes receive identical natural gas feed rate (108 t/h).
Pressure in CO2 absorber and stripper 2 bar Results for the three alternatives of CO2 utilization mediated by
Temperature of rich MEA stream 40  C
Temperature of lean MEA stream 120  C
microalgae (syngas recycle of 0%, 25% and 50%) show that syngas
Photobioreactor and gasifier recycle resulted in an energy generation increase of 45.6% and
Biochemical composition of Isochrysis 45.3% proteins, 37.6%
galbana lipids, 17.1% carbohydrates
Concentration of biomass at 4% (w/w)
Table 2
photobioreactor inlet
Process performances.
Nitrogen source NH4NO3
Phosphor source NaH2PO4.H2O NGCC with carbon capture and utilization
Pressure 1 bar NGCC
Gasifier inlet temperature of biomass 30  C Recycle of syngas to combustor (%) 0% 25% 50%
Gasifier outlet temperature 700  C Natural gas consumption (t/h) 108 108 108
Gasifier model (ASPEN HYSYS) Gibbs reactor Syngas to combustor (t/h) 0 375 542
Shift reactor pressure 40 bar Energy generated (NGCC) (MW) 941 1370 1650
Ammonia synthesis Residual water from fuel compression (t/h) 0 62.2 90.1
Temperature of HTS 350  C Condensed combustion water from flue gas (t/h) 160 372 467
Temperature of LTS 205  C Power consumption in air compression (MW) 401 687 816
HTS, LTS and methanator model Equilibrium reactor Power consumption in fuel compression (MW) 35.7 146 199
(ASPEN HYSYS) Power consumption in steam loop pump (MW) 25.9 23.4 39.7
Inlet reactor pressure 160 bar Total power consumption (compressors 463 856 1060
Reactor model PFR and pump) (MW)
Temperature of produced ammonia 20  C Net power (generated minus consumed) (MW) 478 514 590
CO2 compression to storage Microalgae cultivation, harvesting and gasification
Pressure to injection 350 bar CO2 to photosynthesis (t/h) 4100 1400 990
Distance to injection point Negligible Dry biomass (t/h) 2000 680 490
NH4NO3 (t/h) 821 280 198
NaH2PO4.H2O (t/h) 129 439 31
Water consumed by photosynthesis (t/h) 1530 524 371
Salt water makeup (t/h) 4630 3620 3460
photobioreactor. CO2 poor gas contains CO (~0.3%) which must be O2 produced (t/h) 3630 1240 877
removed (to protect ammonia synthesis catalyst) by methanation Syngas produced (t/h) 4450 1500 1080
(CO þ 4H2 4 CH4 þ 2H2). The treated gas stream goes to a Haber- Gasifier heat duty (MW) 6910 2340 1690
Bosch process, where hydrogen reacts with nitrogen Footprint of photobioreactor (ha) 3020 3000 3000
(assuming 60 L/m2)
(N2 þ 3H2 4 2NH3) at high pressure (8e20 MPa) and temperature
Capture of CO2 produced in WGS and NGCC
(350e480  C). The conversion per pass is 25e35%. Unreacted H2 MEA recirculation pump (MW) 48.7 21.0 21.0
and N2 are recycled to reactor. The molar ratio H2/N2 is ~3. The two- Residual water from top of regenerator (t/h) 0 4.49 5.89
bed ammonia reactor is simulated as two adiabatic plug flow re- Reboiler heat duty (MW) 4550 1290 1230
actors in series. The kinetic model for ammonia synthesis is the CO2 captured (t/h) 4080 1380 991
WGS
same as used by Soares et al. [31]. Methanator heat load (MW) 133 29.6 2.3
The entire process comprehends the following simulated steps: Heat load of WGS reactors (MW) 113 29.6 14.0
(a) Compression of natural gas and atmospheric air; (b) NGCC Power consumption in WGS compressors (MW) 1960 500 243
combustion; (c) Condensation of water from flue gas; (d) CO2 Residual water from gasification (t/h) 38.8 235 170
Residual water from WGS compression (t/h) 885 364 118
capture with MEA; (e) Feed of CO2 to photobioreactor; (f) Biomass
Residual water from WGS (t/h) 99.6 446 115
production in photobioreactor; (g) Biomass gasification; (h) Cooling Residual water from NH3 feed compression (t/h) 113 25.5 3.34
and compression of syngas; (i) Conversion of CO for H2 production Power consumption in NH3 feed compressors (MW) 553 141 70.4
by Water-gas-shift reaction; (j) Elimination of residual CO and CO2 NH3 production
by methanation; and (k) Ammonia synthesis. Produced NH3 (t/h) 2350 607 304
Compressor power in refrigeration cycle (MW) 1930 496 245
Equipment sizing and economic analysis were performed NGCC with carbon capture & storage
considering natural gas cost as US$ 0.079/m3, urea price as US$ 550/ Natural gas consumption (t/h) 108
t and water at US$ 0.28/t. Natural gas cost was taken as the average Energy generated (NGCC) (MW) 941
of Henry Hub Spot Price in the period from March to May of 2012 Condensed combustion water from flue gas (t/h) 160
Power consumption in air compression (MW) 401
(2.25 US$/1000 ft3) [11]. For the same time period, FERTECON [13]
Power consumption in fuel compression (MW) 35.7
presents bulk urea prices from $500/t (NOLA granulated) to $600/t Power consumption in steam loop pump (MW) 25.9
(Yuzhny prilled), supporting the average value of US$ 550/t herein Power for compression of captured CO2 (MW) 32.5
adopted. Last, industrial water tariff is based on monthly water bills Heat load to reboiler of the regenerator (MW) 4550
by system size and customer class [8] considering industrial water Power consumption with MEA recirculating 48.7
pump (MW)
for consumer class Group A (systems producing >75MGD), with
 O. de Queiroz Fernandes Araújo et al. / Energy 92 (2015) 556e568
75.5% respectively for 25% and 50% recycle relatively to the base
case (0% recycle). The corresponding compression power was
enhanced by 84.9% and 128.9%, representing respective net energy
increase (energy generation increase minus compression power
increase) of 7.5% and 23.4%. The energy generation increase is
paralleled by the increase in water recovered in compressing the
natural gas and cooling the flue gas - 171% and 248%, respectively
for syngas recycle of 25% and 50%. The surplus in energy generation
metrici ¼ ½impacti =unit mass of product=½$product=unit mass of product
with co-firing natural gas and syngas (for the 25% and 50% recycle
configurations) reduces the net CO2 generation due to the H2
content in the mixed feeds (the CO2 to photosynthesis line in
Table 2). Additionally, as a consequence of the reduced emission of
CO2, results reported in Table 2 show: (a) decreased energy con-
sumption associated to CO2 capture, i.e., MEA recirculation power
and reboiler duty in MEA regeneration column are reduced; (b)
decreased biomass generation e and consequent decrease in syn-
gas production, and (c) depression of NH3 production, impacting
negatively process revenue. Clearly, recycling syngas to the power
plant affects the overall performance in multiple directions and
evidence the utility of a unified index to support decision on which
alternative process is the most sustainable configuration.
4. Green engineering principles and metrics
Ad hoc principles and quantitative metrics to evaluate process
sustainability are reviewed to construct a framework for sustain-
ability analysis.
4.1. Ad hoc principles for green design
Patel et al. [23] state that the goal of green process engineering is
the design, commercialization, and use of processes and products,
which are feasible and economical while minimizing generation of
pollution at the source and risk to human health and the
environment.
Anastas et al. [4] outlined twelve PGE (principles of green en-
gineering), which move to production environment as the twelve
PGC (principles of green chemistry), proposed by Anastas et al. [3].
Abraham and Nguyen [1] present the results from the San Destin
Conference, defining green engineering principles. More recently,

nez-Gonza
Jime
lez and Constable [17] reviewed sustainability
principles and proposed a simplified set of three green principles.
Table 3 presents these principles stressing out correspondences
among them subsidizing the proposition of a set of heuristic
decision-making criteria. Note that Table 3 interprets several pro-
posed ad hoc green principles and criteria [1,3,4,17] as equivalent
principles, resulting in a set of GDC (Green Design Criteria).
4.2. Sustainability metrics
Tabone et al. [34] pointed out the inexistence of a universally
recognizable standard for assessing sustainability. Hence, princi-
ples such as the PGE and PGC mostly guide process design. How-
ever, in order to propose a process structure, priorities must be set
for the productive complex, and quantification precedes prioriti-
zation, demanding metrics. Sustainability indices to support
561
decision-making processes should be simple, rely on available data
and exhibit resilience to data uncertainties.
Schwarz et al. [26] proposed five categories of metrics: material
intensity, energy intensity, water consumption, toxic emissions,
and pollutant emissions. The authors opted to express the eco-
nomic performance implicitly, as denominators of the metrics, Eq.
(1), and recognize that “social denominators” still need to be
developed.
(1)
As pointed out by Schwarz et al. [26], the lower the metric, the
more effective the impact of the process. In such approach, an
outstanding economic or social performance (denominators)
would render even significant environmental impacts (numera-
tors) numerically negligible.
An alternative is to group metrics: (a) environmental impacts, (b)
economic performance, and (c) social performance. With this
approach, Monteiro et al. [19] employed Pareto optimization of a
biorefinery of microalgal biomass aiming at maximizing sustain-
ability, as a dual objective problem: minimizing environmental
impact while maximizing economic performance. Social metrics
were neglected both due to lack of recognized indicators and to the
georeferencing nature of such quantification. Monteiro et al. [19]
proposed a superstructure for a biorefinery and concluded that
increasing the weight of environmental objectives against economic
performance makes unattractive some sectors of the biorefinery.
Tabone et al. [34] employed a decision matrix comparatively to a
classic LCA. The authors empirically compared adherence to green
design principles in plastics to the environmental impacts of the
production of each plastic, reporting a qualified positive correlation
between adherence to green design principles and a reduction of
the environmental impacts of production. They further concluded
that atom economy is an indicative predictor of low life-cycle
environmental impacts, although low atom economy does not
necessarily represent poor environmental performance.
As auxiliary tool to the proposed decision-making principles, a
quantitative set of sustainability metrics should supplement heu-
ristic design criteria (GDC, Green Design Criteria).
4.2.1. A reduced set of sustainability metrics
A reduced set of simple metrics applicable to decision support is
presented in Table 4. Metrics are defined in a way that the smallest
the value, the greenest the alternative. It is relevant that the set
should include quantities with minimum computational effort.
Such orientation is the driving principle in proposing the reduced
set of Table 4.
5. Proposed multi-criteria sustainability analysis: Severity
Matrix, Criticality Factor and Sustainability Degree
MCA (multi-criteria analysis), or multi-objective decision-mak-
ing, is any structured approach for determining preferences among
alternative objectives. The analysis considers that quantitative and
qualitative indicators (through scoring, ranking and weighting)
may influence policies. Therefore, social, environmental, technical
and economic criteria are simultaneously considered.
The present work proposes a combination of green principles
(Table 3) e qualitative and dependent on expert judgement - and
simple metrics (Table 4) based on MCA, consisting in:
Table 3
Criteria and principles of green design.
GDC (green design criteria)
GDC#1: preventing rather than treating GCP#1: prevention
waste is the best environmental
protection strategy.
GDC#2: incorporating all materials GCP#2: atom economy
used in the process into the final
product, designing tailored to needs
with maximum efficiency.
GDC#3: using and generating
substances that possess little or no
toxicity to human health and the
environment, while preserving
efficacy of use.
GDC#4: recognizing environmental and
economic impacts of energy
requirements and minimizing it.
GDC#5: using renewable rather than
depleting materials.
GDC#6: avoiding unnecessary
derivatization and minimizing
complexity in products.
GDC#7: avoiding by-products using
catalytic reagents as selective as
possible.
GDC#8: product should not persist in
the environment after usefulness.
Targeted durability, not immortality,
should be a design goal.
GDC#9: real-time, in-process
monitoring and control to minimize
pollution and release of hazardous
substances.
GDC#10: embody a holistic, systems
approach to risk reduction.
GDC#11: complexity must be viewed as
an investment when making design
choices on recycle, reuse, or
beneficial disposition.
GDC#12: material diversity in
multicomponent products should be
minimized to promote disassembly
and value retention.
GDC#13: design for performance in a
commercial “afterlife”. Design for
disassembly.
GDC#14: holistically design with
innovative solutions, while meeting
geographic and cultural specificities.
562
The twelve green chemistry The twelve green engineering The nine San Destin principles [1] The three simplifying principles [17]
principles [3] principles [4]
GEP#2: prevention instead of SDP#2: conserve and improve natural ecosystems while protecting SP#2: eliminate and minimize hazards
treatment. human health and well-being; SDP#6: strive to prevent waste. and pollution.
GEP#4: maximize efficiency; GEP#8: SDP#2: conserve and improve natural ecosystems while protecting SP#1: Maximize resource efficiency.
meet need, minimize excess; GEP#10: human health and well-being; SDP#6: Strive to prevent waste.
integrate material and energy flows;
GEP#5: Output-pulled versus input-
pushed.
GCP#3: less hazardous GEP#1: inherent rather than SDP#4: ensure that all material and energy inputs and outputs are as SP#2: eliminate and minimize hazards
chemical syntheses; circumstantial. inherently safe and benign as possible. and pollution.
GCP#4: designing safer
chemicals; GCP#5: safer
solvents and auxiliaries
GCP#6: design for energy GEP#4: maximize efficiency; GEP#8: SP#1: maximize resource efficiency.
efficiency meet need, minimize excess; GEP#10:
O. de Queiroz Fernandes Araújo et al. / Energy 92 (2015) 556e568
integrate material and energy flows.
GCP#7: use of renewable GEP#12: renewable rather than SDP#2: conserve and improve natural ecosystems while protecting SP#3 design systems holistically and
feedstocks depleting. human health and well-being; SDP#5: minimize depletion of natural using life cycle thinking.
resources.
GCP#8: reduce derivatives. GEP#3: design for separation. SDP#1: ensure that all material and energy inputs and outputs are as SP#1: maximize resource efficiency.
inherently safe and benign as possible.
GCP#9: catalysis. GEP#3: design for separation. SDP#3: use life cycle thinking in all engineering activities. SP#1: maximize resource efficiency.
GCP#10: design for GEP#7: durability rather than SDP#2: conserve and improve natural ecosystems while protecting SP#3 design systems holistically and
degradation. immortality. human health and well-being; SDP#4: ensure that all material and using life cycle thinking.
energy inputs and outputs are as inherently safe and benign as possible.
GCP#11: real-time analysis SP#2: eliminate and minimize hazards
for pollution prevention. and pollution.
GCP#12: inherently safer GEP#1: inherent rather than SDP#1: engineer processes and products holistically, use systems SP#2: eliminate and minimize hazards
chemistry for accident circumstantial. analysis, and integrate environmental impact assessment tools. and pollution; SP#3 design systems
prevention. holistically and using life cycle thinking.
GEP#6: conserve complexity. SDP#1: engineer processes and products holistically, use systems SP#2: eliminate and minimize hazards
analysis, and integrate environmental impact assessment tools. and pollution.
GEP#9: minimize material diversity. SDP#3: use life cycle thinking in all engineering activities. SP#3 design systems holistically and
using life cycle thinking.
GEP#11: design for commercial SDP#2: conserve and improve natural ecosystems while protecting SP#3 design systems holistically and
“afterlife”. human health and well-being; SDP#4: ensure that all material and using life cycle thinking.
energy inputs and outputs are as inherently safe and benign as possible.
SDP#1: engineer processes and products holistically, use systems SP#3 design systems holistically and
analysis, and integrate environmental impact assessment tools. SDP#7: using life cycle thinking.
develop and apply engineering solutions, while being cognizant of local
geography, aspirations and cultures; SDP#8: create engineering
solutions beyond current or dominant technologies; improve, innovate
and invent (technologies) to achieve sustainability; SP#9: actively
engage communities and stakeholders in development of engineering
solutions.
 O. de Queiroz Fernandes Araújo et al. / Energy 92 (2015) 556e568 563

Table 4
Reduced set of sustainability metrics.
a
Aspect measured Metrics

Category Definition

Environmental E-factor for chemicals production, given  E-factor ¼ MI1

MI ¼ mass of input per unit mass of product
E-factor for energy production, given  E-factor ¼ EE1
EE ¼ (kW input as natural gas þ kW input as syngas)/kW generated
EI (energy intensity)  Unit of electric energy per unit mass of product (EEI)
 Unit of thermal energy per unit mass of product (TEI)
CI (carbon intensity)  CI ¼ kg CO2 =kg product (chemical produced)
 CI ¼ kg CO2 =kW generated (energy generated)
WI (water intensity)  WI ¼ kg water=kg product
CPþtðCOPþCSMÞþCEOL
Economic LCC intensityb  LCC ¼ tAP

NPV (net present value)c  NPV ¼ I0 þ Pn CFi

i¼1
ð1þrÞi

Time of return of investment  ROI

a
Indicators were selected based on simplicity of calculation, frequency of use and availability of primary data, and adapted from Refs. [7,30,16,26,28,14].
b
LCC ¼ Life cycle cost; CP ¼ Cost of purchase (CAPEX); COP ¼ Cost of Operation; CSM ¼ Cost of service and maintenance (OPEX ¼ COP þ CBM); CEOL ¼ Cost of end-of-life
management, t ¼ operation life-time (assumed as 20 years), AP ¼ annual production (ton).
c
IO e Investment, r ¼ discount rate, CFi ¼ cash flow in the ith future time period.

 Scoring design alternatives based on GDC (Green Design the number of green design criteria). A GDCI (Green Degree Criticality
Criteria); Index) can be proposed according to Eq. (3).
 Scoring quantitative metrics,
 Computing the multi-criteria SM (Severity Matrix),
GDCI ¼ GD$PWV (3)
 Computing the Criticality Factor, and
 Computing the Sustainability Degree
where

2 3
5.1. Scoring design alternatives according to the GDC (Green Design gd1;1 gd1;2 / gd1;nc 2 3
6 gd1;2 wp1
6 gd1;2 / gd2;nc 7
7
Criteria) GD ¼ 4 PWV ¼ 4 « 5
/ / / / 5
wpnc ncx1
GDC, first column in Table 3, are scored according to three levels: gdnp;1 gdnp;1 / gdnp;nc npxnc

 1 ¼ High compliance to a given GDC, np and nc are, respectively, the number of screened processes and
 3 ¼ Medium compliance to a given GDC, and the number of green design criteria (herein proposed as 14 criteria,
 9 ¼ Low compliance to a given GDC. according to the first column in Table 3).
GDCI can be interpreted as indexes of how critical a process is to
the environment, given the adopted policy. Therefore, GDCI can be
5.2. Scoring quantitative metrics taken as an intensity measure of potential impacts. Hence, combi-
nation of quantitative metrics (matrix NM) and such measure of
Computed quantitative metrics (chosen, for instance, among criticality yields the proposed SM (Severity Matrix).
metrics listed in Table 4) are represented as matrix M (np rows and To calculate the SM, a matrix of green degree criticality factors is
nm columns), and normalized as shown in Eq. (2) to produce matrix constructed as shown in Eq. (4).
NM (normalized metrics):


NMi;j ¼ Mi;j M  (2) MGDCI ¼ GDCInp1 $½ 1 1 /1 1 1nm
j 2 3
gdci1 gdci1 / gdci1
where NMi,j is the ith normalized metric (i ¼ 1, …, nm) for the jth 6 gdci2 gdci2 / gdci2 7
¼46 7 (4)
process (j ¼ 1, …, np) and hMj i is the average value of the ith metric / / / / 5
calculated among the values exhibited by the np processes. Scores gdcinp gdcinp / gdcinp npnm
are attributed as:
The Hadamard product of matrices MGDCI and NM yield the SM
(Severity Matrix) presented in Eq. (5).
 1 (Good performance), if NMi,j < 1;
 3 (Regular performance), if 1  NMi,j < 3;
 9 (Poor performance), if NMi,j  3. SMnpnm ¼ MGDCInpnm $NMnpnm (5)

where
5.3. Computing de multi-criteria SM (Severity Matrix)
2 3
NM1;1 NM1;2 / NM1;nm
Given GD as the matrix with scores of the GDC for the np 6 NM2;1 NM2;2 / NM2;nm 7
6
NM ¼ 4 7
screened processes, and a PWV (Policy Weight Vector) to weight / / / / 5
decision-making priorities (e.g., recognizing environmental and NMnp;1 NMnp;2 / NMnp;nm npnm
economic impacts of energy requirements and minimizing them e
GDC#4). For equally weighted policies, PWVi is equal to 1/nc (nc is
564 O. de Queiroz Fernandes Araújo et al. / Energy 92 (2015) 556e568

2 3 attributed according to the judgement of the authors and could be

gdci1 NM1;1 gdci1 NM1;2 / gdci1 NM1;nm refined by collecting a larger ensemble of opinions from specialists.
6 gdci2 NM2;1 gdci2 NM2;2 / gdci2 NM2;nm 7
SM ¼ 6
4
7
5
It can be observed that CO2 capture and utilization alternatives
/ / / / (biorefinery) differ in GDC#5, GDC#6 and GDC#12. GDC#5 con-
gdcinp NMnp;1 gdcinp NMnp;2 / gdcinp NMnp;nm npnm siders the case of 0% syngas recycle as the worst alternative
(score ¼ 3) as the recycle would contribute to reducing natural gas
consumption.
However, as recycling syngas requires additional pieces of
5.4. Computing the CF (Criticality Factor) and the SD (Sustainability equipment, and introducing H2 into the combustor is a derivati-
Degree) zation, scores attributed to GDC#6 and GDC#12 consider the
absence of recycle as a more sustainable alternative. It is also worth
The Severity Matrix presents multiple environmental perfor- noting that CO2 capture and storage is rated as unsustainable
mances as severities (intensified by the GDC). To support decision- (score ¼ 9) in all GDC except GDC#6 (absence of chemical reaction
making process, single performance indexes are proposed: the CF or addition of chemical species), GDC#7 (absence of chemical re-
(Criticality Factor) and the SD (Sustainability Degree). Given matrix action) and GDC#12 (reduced number of equipment pieces mini-
NM (matrix of normalized metrics) and the GDCI (Green Degree mizes material diversity). The overall GDC scores indicates CO2
Criticality Index), CF and SD are calculated according to Eqs. (6)e(8). capture and utilization without syngas recycle as the best process
alternative.
0 2 3 1
1 The sustainability metrics for the evaluated process alternatives,
B 617 C based on mass and energy balances shown in Table 2, are computed
CF ¼ GDCInp1 $B 6 7
@NMnpnm $4 « 5
C
A from calculation results of indexes presented in Table 4 (environ-
1 nm1 mental and economic) and are presented in Appendix B. The
2 P
nm 3 normalization procedures described in Section 6 were applied to
6 gdci1 j¼1 NM1;j 7 the obtained values to yield the computed performance metrics
6 7 shown in Table 5. The quantitative performance metrics, as
6 P
nm 7
6 7
6 gdci2 NM2;j 7 occurred with the heuristic GDCs, are not uniformly pointing to-
¼6 7 (6)
6 j¼1 7 wards one specific process alternative. For instance, economic
6 « 7
6 7 performance indicates the refinery with 0% syngas recycle as the
4 P
nm 5
gdcinp NMnp;j best alternative while E-factor, EEI (electric energy intensity), CI
j¼1 np1 and WI (Water Intensity) indicate CCS as the preferred choice.
Clearly, a decision-making support tool is needed to perform the
100 multi-criteria decision.
SI ¼ CF (7) The GDC (Green Degree Criteria) indexes displayed in Fig. 5 are
cfref
used along with the computed sustainability metrics (environ-
where cfref is the criticality factor for the Reference Process, a process mental and economic) to construct the multi-criteria sustainability
elected among the np screened processes, and SI is a Severity Index analysis presented in Section 5.
vector. The higher an element in the SI vector the more inferior its
sustainability is. A SD (Sustainability Degree) vector is therefore
constructed based on SI as indicated in Eq. (8): 6.1. Sustainability analysis
2 3
1=si1 Based on scores for GDC (Fig. 5) and sustainability metrics
6 1=si2 7 shown in Table 5, matrices GD (GDC scores) and NM (normalized
SD ¼ 100$6
4 « 5
7 (8)

quantitative metrics) are constructed, resulting in the following SM,
1 sinp np1 SI, CF and SD:

where si1 … sinp are the elements of the SI vector.

2 3
2:0000 3:1429 1:4286 3:7143 2:0000 1:4286 1:4286 1:4286
6 4:7143 3:4571 1:5714 2:2000 2:2000 4:7143 1:5714 1:5714 7
6
SM ¼ 4 7
4:0857 2:8286 1:5714 2:2000 6:6000 14:1429 14:1429 14:1429 5
6:0000 6:0000 54:0000 6:0000 6:0000 54:0000 54:0000 54:0000

6. Results and discussion 2 3 2 3 2 3

16:5714 6:9048 14:4828
6 22:0000 7 6 9:1667 7 6 10:9091 7
The procedure is illustrated with processes shown in Figs. 2e4. CF ¼ 6 7
4 59:7143 5 SI ¼ 6 7
4 24:8810 5 SD ¼ 6
4 4:0191 5
7
The alternative named CO2 Capture and Utilization (Biorefinery) is
240:000 100:000 1:0000
further evaluated under three scenarios of syngas recycled to an
NGCC combustor: (I) 0%, (II) 25% and (III) 50%. CO2 Capture and The index of Sustainability Degree proposed in the present work
Storage is the Reference Process. indicates CO2 capture and utilization without syngas recycle as the
A Map of Compliance with GDC (Green Design Criteria) is dis- most sustainable alternative evaluated. To visualize the contribu-
played in Fig. 5 (entries to matrix of metrics M), with scores tion of each metric to the overall severity of the screened processes,
 O. de Queiroz Fernandes Araújo et al. / Energy 92 (2015) 556e568 565

Fig. 5. Map of Compliance with GDC (Green Design Criteria). Green Degree Criteria presented in Table 3, column 1.

Table 5 intensity). Clearly, the multiplicity of metrics (and corresponding

Computed performance metrics. severities) renders the analysis cumbersome. The introduction of
E-factor EEI TEI CI WI NPV ROI LCCI the Sustainability Degree simplifies the decision of the most sus-
0% syngas recycle 1.4 2.2 1 2.6 1.4 1 1 1
tainable process.
25% syngas recycle 3 2.2 1 1.4 1.4 3 1 1 From a purely environmental vision, CCS would be the recom-
50% syngas recycle 2.6 1.8 1 1.4 4.2 9 9 9 mended process. Such observations brings focus to the relevance of
CCS 1 1 9 1 1 9 9 9 the PWV (Policy Weighting Vector), which can completely change
the result of the sustainability analysis. The procedure is, in this
sense, flexible to accommodate regional scenarios within the sus-
Severity Contribution matrix is defined in Eq. (9). The calculated SC tainability evaluation task.
and SD are pictured in Fig. 6, for the four screened processes: 1- A final observation concerns water intensity of microalgae
biorefinery without syngas recycle, 2 - biorefinery with 25% syngas production. Subhrada and Edwards [33] consider that a technology
recycle, 3 - biorefinery with 50% syngas recycle and 4 - CCS. bottleneck to biofuels production from such feedstock may be the
2 3 large amounts of freshwater. However, in the proposed biorefinery
arrangement, downstream processes produce residual water
6 7
6 7 streams that mitigate water footprint of the microalgal cultivation
6 sm1;1 7
6 Pnm Psm 1;2
/ Psm 1;nm
7 and harvesting steps.
6 1 sm1;j nm
sm1;j
nm
sm1;j 7
6 1 1 7
6 sm2;1 7
6 Pnm Psm 2;2
/ Psm 2;nm 7
6 nm nm 7 7. Conclusions
SC ¼ 100:6 1 sm2;j 1
sm2;j 1
sm 2;j 7 (9)
6 / / / / 7
6 7
6 7
6 Psmnp;1 Psm /
smnp;nm 7
Pnm
The proposed framework for sustainability analysis condenses
6 nm sm 7
np;2
nm
6 1 np;j smnp;j sm np;j 7 results from ad hoc evaluation into a score-based value, the GDCs,
6 1 1
7
4 5 which are used to intensify or attenuate scores of quantitative
metrics, yielding a Criticality Factor and a Sustainability Degree used
npnm
for ranking process alternatives. As defined, the largest the Sus-
For process #1, the most significant contributions to severity are tainability Degree, the more sustainable a process alternative is.
CI (carbon intensity) and EEI (electric energy intensity). In process Based on the procedure, CO2 capture and utilization (biorefinery)
#2, E-factor and NPV (net present value) are the dominant severity with no recycle of syngas to combustor is the greenest process
contribution. Process #3 has the economic factors (NPV, ROI and life flowsheet for utilization of CO2 in a one-product microalgae bio-
cycle cost) dominating severity while process #4 has its sustain- refining configuration, among the four alternatives evaluated
ability reduced by the economic factors and TEI (thermal energy herein.

Fig. 6. Severity Contributions (from SC matrix) and Sustainability Degrees (from SD vector) for the screened processes: biorefinery without syngas recycle, biorefinery with 25%
syngas recycle, biorefinery with 50% syngas recycle and CCS.
566 O. de Queiroz Fernandes Araújo et al. / Energy 92 (2015) 556e568
GDCs are able to rule out the CCS option but can barely
discriminate among the syngas recycle options in the biorefinery
process. The quantitative metrics embodied in the proposed
framework point out the overall sustainability performance. Addi-
tionally, it was suggested that regional policies might alter the
analysis through the Policy Weighting Vector, attributing flexibility
to the proposed procedure.
Furthermore, the Severity Contribution matrix introduced in
Section 7 allows the designer to identify which metrics most in-
fluence the Severity Index and, hence, the sustainability analysis. It
is clear that economic metrics are dominant in condemning per-
formance of NGCC with CCS (67.5% of the index). Analogously, in the
biorefinery alternatives, the economic metrics are determinant of
the poor performance of the design with 50% recycle of syngas.
Economic performance is favoured by alternatives that boost
ammonia production. Recycling syngas penalises performance as it
decreases this feedstock supply to ammonia production even
though energy generation (a less valued revenue when compared
to ammonia value) is enhanced. Clearly, a social metric or weight-
ing GDC#14 - Holistically design with innovative solutions, while
meeting geographic and cultural specificities is necessary to enhance
the proposed decision support tool. Moreover, when economic
performance is good, the environmental metrics are dominated by
the energy related values (EEI and TEI) followed by the carbon in-
tensity score.
Acknowledgements
The authors acknowledge financial support from CNPq: Grants
404778/2013-5, 405851/2013-8 and PRH41/ANP. Thanks are due to
A. C. F. Soares, G. F. A. Rocha and M. J. Velozo for ASPEN HYSYS
simulation.
Appendix A. Biomass simulation in ASPEN HYSYS
The compositional information of the biomass (as percent-
ages of lipids, proteins and carbohydrates) is fed into the
Fig. A1. Definition of biomass stream in process simulator.
simulation environment as process streams “lipids”, “protein”,
and “carbohydrate”. Streams “protein” and “carbohydrate” are
pure component streams, the former being a pseudo-
component with molecular formula C10H16N2O8 and the later
sucrose. The “lipids” stream is composed of a set of carboxylic
acids. The work adopts analytical results from the Laboratory
H2CIN of the Federal University of Rio de Janeiro for the species
Isochrysis galbana: 45.33% of proteins, 37.59% of lipids (with lipid
mass fraction profile of 0.45 in oleic acid, 0.15 of stearic acid, 0.3
of linoleic acid and 0.1 of palmitic acid) and 17.07% of carbohy-
drate. In Fig. A1, each metabolic pool is segregated in the
respective feed streams and specification blocks (“P/C” and “L/
C”) are responsible to meet experimental mass ratio results
(from Laboratory H2CIN) of protein to lipid (1.783) and protein
to carbohydrate (2.248). An “Adjust” block (ADJ-2 in Fig. A1)
modifies flow rate of the “carbohydrate” feed stream to meet dry
biomass weight specified according to the molar flow of CO2 fed
to the photobioreactor. The set amount of biomass exiting the
mixer of metabolic pools (MIX-100-2) is calculated in a
spreadsheet (SPRDSHT-3) considering the carbon content of
Isochrysis galbana as 54.51% (in weight) (experimental infor-
mation) and that the autotrophic growth captures 100% of the
fed CO2. From the stoichiometric consumption of water due to
photosynthesis, calculated based on the amount of CO2
consumed, a water makeup stream is added, in MIX-101, to the
amount of water necessary to produce a biomass suspension of
4 g/L (calculations are done in SPREADSHT-1). Block “SET-1” is
responsible for adjusting the amount of nutrient fed to the
photobioreactor. The final biomass suspension, to feed the har-
vesting and gasification sections of the biorefinery is completed
with MIX-100.
The stream “Biomass Suspension” has a biomass concentration
specified as 4% (biomass dry weight percentage). A Component
Splitter and a Spreadsheet Block calculate mass and energy bal-
ance to remove water of the stream to a final stream with 60%
water content, which is fed to a gasifier (Humid Gasification,
Fig. A2).
 O. de Queiroz Fernandes Araújo et al. / Energy 92 (2015) 556e568 567

Fig. A2. Humid gasification: humid biomass and syngas product.

Appendix B. Results of process alternative performances
Mass and energy balances obtained with process simulation for
the three alternative processes were used to compute performance
indexes listed in Table 4. Results are shown in Table B1. For each
index, procedure of normalization described in Section 6
was applied, yielding results displayed in Table B2. The
consolidated indexes for the biorefineries were taken as the
average value of the indexes of each sector of the alternative,
accordingly to Table B2.

Table B1
Performance indexes for the evaluated process alternatives.

Performance CO2 capture and utilization (biorefinery) CO2

indexes capture
0% recycle of syngas 25% recycle of syngas 50% recycle of syngas
and
NGCC Integrated Microalga WGS Ammonia NGCC Integrated Microalga WGS Ammonia NGCC Integrated Microalga WGS Ammonia storage
CO2 growth, CO2 capture growth, CO2 growth,
capture harvesting & harvesting & capture harvesting &
gasification gasification gasification

E-factor 0.53 0.00 0.48 1.55 0.10 16.50 0.10 0.49 2.11 0.09 13.9 0.14 0.47 0.47 0.09 0.05
EEI 0.46 0.01 0.00 0.97 0.82 0.62 0.015 0.00 0.97 0.82 0.61 0.02 0.00 0.00 0.81 0.12
TEI (kW/kg) 0.00 1.12 1.56 0.10 0.00 0.00 0.94 1.56 0.09 0.00 0.00 1.24 1.55 1.55 0.00 16.80
CI (kg/kg) 4.33 0.01 0.00 0.00 0.00 0.60 0.10 0.00 0.00 0.00 1.01 0.04 0.00 0.00 0.00 0.02
WI (kg/kg) 0.17 0.02 1.04 0.44 0.00 0.34 0.06 2.41 1.61 0.00 0.32 0.09 3.19 3.19 0.00 0.25
NPV 11.3 5.13 9.86 7.46
(Billions
US$)
ROI (years) 8.3 8.7 e e
LCCI 437 700 1690 1120
(US$/t)

Table B2
Normalized performance indexes for the biorefineries

CO2 capture and 0% syngas recycle NGCC 1 3 1 9 1

utilization (biorefinery) CO2 capture 1 1 1 1 1
Microalga growth and gasification 1 1 1 1 3
WGS 3 3 1 1 1
Ammonia synthesis 1 3 1 1 1
Average 1.4 2.2 1 2.6 1.4
25% syngas recycle NGCC 9 3 1 3 1
CO2 capture 1 1 1 1 1
Microalga growth and gasification 1 1 1 1 3
WGS 3 3 1 1 1
Ammonia synthesis 1 3 1 1 1
Average 3 2.2 1 1.4 1.4
50% syngas recycle NGCC 9 3 1 3 1
CO2 capture 1 1 1 1 1
Microalga growth and gasification 1 1 1 1 9
WGS 1 1 1 1 9
Ammonia synthesis 1 3 0 1 1
Average 2.6 1.8 0.8 1.4 4.2
568 O. de Queiroz Fernandes Araújo et al. / Energy 92 (2015) 556e568

References [18] Lima DFB, Zanella FA, Lenzi MK, Ndiaye PM. Modeling and simulation of water
gas shift reactor: an industrial case. ISBN: 978-953-51-0411-7, InTech. In:
Vivek Patel, editor. Petrochemicals; 2012. http://dx.doi.org/10.5772/37181.
[1] Abraham MA, Nguyen N. Green engineering: defining the principles e results
Available from:, http://www.intechopen.com/books/petrochemicals/
from the San Destin Conference. Environ Prog 2003;22(4):233e6.

ndez CG, Carlier RN, Martin JR. Energetic analysis modeling-and-simulation-of-water-gas-shift-reactors-an-industrial-case.
[2] Alvaro AJ, Paniagua IL, Ferna
[19] Monteiro JGMS, Silva PA, Araujo OQF, de Medeiros JL. Pareto optimization of
of a syngas-fueled chemical-looping combustion combined cycle with inte-
an industrial ecosystem: sustainability maximization. Braz J Chem Eng
gration of carbon dioxide sequestration. Energy 2014;76:694e703.
2010;27:429e40.
[3] Anastas PT, Warner JC. Green chemistry: theory and practice. New York:
[20] Muradov N. Carbon capture and storage: in the quest for clean fossil energy.
Oxford University Press; 1998.
Liberating energy from carbon: introduction to decarbonization. Lecture
[4] Anastas PT, Zimmerman JB. Design through the twelve principles of green
Notes in Energy 22, [Chapter 7], DOI 10.1007/978-1-4939-0545-4_7. New
engineering. Environ Sci Technol 2003;37(5):94Ae101A.
York: Springer ScienceþBusiness Media; 2014. p. 185e6.
[5] Anastas PT, Eghbali N. Green chemistry: principles and practice. Chem Soc Rev
[21] Holt NA. Integrated gasification combined-cycle plants. In: Encyclopedia of
2010;39:301e12.
physical science and technology. 3rd ed. London: Academic Press; 2001.
[6] Araújo OQF, Medeiros JL, Alves RMB. CO2 utilization: a process systems en-
[22] Newsome D. The water gas shift reaction,. Catal Rev 1980;21(2):275e318.
gineering vision. Alves. In: Esteves Victor, Morgado Claudia RV, editors. CO2
[23] Patel D, Kellici S, Saha B. Green process engineering as the key to future
utilization: a process systems engineering vision, CO2 sequestration and
processes. Processes 2014;2(1):311e32.
valorization; 2014. http://dx.doi.org/10.5772/57560. ISBN: 978-953-51-1225-
[24] Picardo MC, de Medeiros JL, Monteiro JGMS, Chaloub RM, Giordano M,
9, InTech. Available from: http://www.intechopen.com/books/co2-
Araujo OQF. A methodology for screening of microalgae as a decision making
sequestration-and-valorization/co2-utilization-a-process-systems-engineer-
tool for energy and green chemical process applications. Clean Technol En-
ing-vision.
viron Policy 2013;15(2):275e91.
[7] Azapagic A, Perdan S. Indicators of sustainable development for industry: a
[25] Picardo MC, de Medeiros JL, Araujo OQF, Chaloub RM. Effects of CO2 enrich-
general framework. Process Saf Environ 2000;78(4):243e61.
ment and nutrients supply intermittency on batch cultures of Isochrysis gal-
[8] Beecher JA. Consolidated water Rates: issues and practices in single-tariff
bana. Bioresour Technol 2013;143:242e50.
pricing. In: A Joint Publication of the U.S. Environmental Protection Agency
[26] Schwarz J, Beloff B, Beaver E. Use sustainability metrics to guide decision-
and the National Association of Regulatory Utility Commissioners; September
making. Chem Eng Progress; 2002 (July). p. 58e63.
1999. Available from: http://www.epa.gov/ogwdw000/utilities/stptitle.pdf
[27] Sze
kely F, Knirsch M. Responsible leadership and corporate social re-
[accessed 28.01.15].
sponsibility: metrics for sustainable performance. Eur Manage J 2005;23(6):
[9] Cao Y, Wang Y, Riley JT, Pan WT. A novel biomass air gasification process for
628e47.
producing tar-free higher heating value fuel gas. Fuel Process Technol
[28] Singh RK, Murty HR, Gupta SK, Dikshit AK. An overview of sustainability
2006;87:343e53.
assessment methodologies. Ecol Indic 2012;15:281e99.
[10] Chisti Y. Biodiesel from microalgae. Biotechnol Adv 2007;25:294e306.
[29] Shen Y, Yoshikawa K. Recent progresses in catalytic tar elimination during
[11] EIA. U.S. Energy Information Administration. Short-term energy outlook.
biomass gasification or pyrolysisdA review. Renew Sust Energ Rev 2013;21:
2015. Available from: http://www.eia.gov/forecasts/steo/tables/# [accessed
371e92.
28.01.15].

ndez FGA, Gonza
lez-Lo
pez CV, Sevilla JMF, Grima EM. Conversion of CO2 [30] Sikdar S. Sustainable development and sustainability metrics. AIChE J
[12] Ferna
2003;49(8):1928e32.
into biomass by microalgae: how realistic a contribution may it be to signif-
[31] Soares ACF, Rocha GFA, Velozo MJ. An

cnico-econo
alise te ^ mica de polo in-
icant CO2 removal? Appl Microbiol Biotechnol 2012;96:577e86.
dustrial carbono sequestrante integrado a termoele
trica NGCC. Final Project.
[13] FERTECON. Nitrogen report. 2012. Available from: https://fertecon.agra-net.
Chemical Engineering Course, Federal University of Rio de Janeiro; 2012.
com/wp-content/uploads/2012/05/Nitrogen-report.pdf [accessed 28.01.15].
[32] Soh L, Montazeri M, Haznedaroglu BZ, Kelly C, Peccia J, Eckelman MJ, et al.
[14] Fiksel F, Eason T, Frederickson H. A framework for sustainability indicators at
Evaluating microalgal integrated biorefinery schemes: empirical controlled
EPA. In: Eason T, editor. National risk management research laboratory. Office
growth studies and life cycle assessment. Bioresour Technol 2014;151:19e27.
of Research and Development United State Environmental Agency. EPA/600/
[33] Subhadra B, Edwards M. An integrated renewable energy park approach for
R/12/687; October 2012. Available from: http://www.epa.gov/sustainability/
algal biofuel production in United States. Energy Policy 2010;38:4897e902.
docs/framework-for-sustainability-indicators-at-epa.pdf [accessed Feb/
[34] Tabone MD, Cregg JJ, Beckman RJ, Landis AE. Sustainability metrics: life cycle
08.02.15].
assessment and green design in polymers. Environ Sci Technol 2010;44:
[15] IFA, International Fertilizer Industry Association. www.fertilizer.org. [accessed
8264e9.
28.11.11].
[35] Tercero EAR, Domenicali G, Bertucco A. Autotrophic production of biodiesel
[16] Jensen N, Coll N, Gani R. An integrated computer-aided system for generation
from microalgae: an updated process and economic analysis. Energy 2014;76:
and evaluation of sustainable process alternatives. Clean Technol Environ
807e15.
Policy 2003;5:209e25.
[36] Urech J, Tock L, Harkin T, Hoadley A, Mare
chal F. An assessment of different
[17] Jime
nez-Gonz
alez C, Constable DJC. Green chemistry and engineering: a
solvent-based capture technologies within an IGCC-CCS power plant. Energy
practical design approach. Wiley; 2011.
2014;64:268e76.