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13

Automated Targeting for the Synthesis


ofanIntegrated Biorefinery

Douglas H. S. Tay and Denny K. S. Ng

CONTENTS
13.1 Introduction......................................................................................................................... 397
13.2 Problem Statement.............................................................................................................. 399
13.3 Automated Targeting.........................................................................................................400
13.4 Case Study 1........................................................................................................................ 403
13.4.1 Scenario 1: Maximum Production of a Single Product (Biofuel) from
aGivenBiomass...................................................................................................... 405
13.4.2 Scenario 2: Maximum Revenue for an Integrated Biorefinery with
MultipleProducts................................................................................................... 406
13.4.3 Scenario 3: Maximum Revenue for an Integrated Biorefinery with
MultipleFeedstocks and Products.......................................................................408
13.5 Case Study 2........................................................................................................................ 409
13.6 Conclusions.......................................................................................................................... 412
Acknowledgments....................................................................................................................... 414
References...................................................................................................................................... 414

13.1Introduction
According to the Annual Energy Outlook 2010 (EIA, 2010), total world consumption of energy is
projected to increase from 495 quadrillion British thermal units (Btu) in 2007 to 580 quadrillion
Btu in 2015 and eventually to 739 quadrillion Btu in 2035. Throughout the projected period,
fossil fuels (i.e., coal, oil, and natural gas) are expected to continue to supply a large share of
energy use worldwide (EIA, 2010). Therefore, the gradual depletion and rising costs of fossil
fuel supplies will soon become a major global problem. As a result, increased attention is being
paid to issues of energy security, resource diversification, and efficiency enhancement.
In addition, the increase of public awareness of environmental sustainability issues has
also motivated a shift from fossil fuels to renewable energy sources. Biofuels are among
the most promising forms of renewable energy because they can be produced from a wide
variety of feedstocks (mainly biomass), which has good potential to reduce greenhouse-
gas emissions. Technologies that convert biomass to value-added products (biodiesel, bio-
ethanol, charcoal, fuel pellets, etc.) through thermal, biological, and physical conversions
are now well established. However, a biorefinery that uses biomass as a feedstock to pro-
duce multiple products, in an analogous way to a petroleum refinery, is a newly proposed
concept (Fernando etal., 2006). In recent years, various concepts of the biorefinery have
been proposed. For example, Kamm etal. (1998) defined a biorefinery as a complex system of

397
398 Integrated Biorefineries

sustainable, environment- and resource-friendly technologies for the comprehensive utilization and
the exploitation of biological raw materials in the form of green and residue biomass from a targeted
sustainable regional land utilisation. Meanwhile, Bridgwater (2003) defined a biorefinery as a
processing facility that is multifunctional, simultaneously producing biofuels, electricity and a
considerable number of chemicals from biomass input via thermal conversion processes. However,
it should be noted that biological conversion processes (e.g., fermentation, hydrolysis) also
play an important role in a biorefinery (Ritter, 2006). Therefore, the latest research and
development efforts on the biorefinery are focusing on integrating the wide spectrum of
biomass conversion technologies (gasification, pyrolysis, fermentation, hydrolysis, cata-
lytic conversion, etc.) to produce a broad range of products. To enhance the overall process
and economic performance, the concept of an integrated biorefinery which integrates
multiple platforms into a whole has been proposed (Fernando etal., 2006).
These concepts can be summarized by saying that the function of a biorefinery is to provide
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a sustainable supply of biofuels and to produce both bulk and fine biochemical products
(methanol, syngas, glycerol, ether, etc.) with minimum waste generation. To date, various
single-product biomass-to-energy technologies such as heat and power generation (Qin etal.,
2006; Mohan and El-Halwagi, 2007), biodiesel production (Elms and El-Halwagi, 2009, 2010;
Myint and El-Halwagi, 2009; Pokoo-Aikins et al., 2009, 2010), and bioalcohol production
(Enguidanis etal., 2002; Gnansounou and Dauriat, 2010) have been analyzed and optimized.
Because a large-scale biorefinery is a capital-intensive project, multilevel analyses of pro-
cess integration should be considered. The integrated biorefinery offers a flexible pathway
that can handle various types of feedstock, is potentially energy self-sufficient, reduces
overall production cost, and increases process efficiency. As other biomass conversion tech-
nologies (gasification, digestion, FischerTropsch synthesis, etc.) become more established,
even more alternative processing pathways can be considered for an integrated biorefinery.
Therefore, it is necessary to screen all potential pathways systematically and to determine
the optimum pathway that produces the desired products. Bao etal. (2011) addressed this
problem by using superstructure optimization to select the optimum pathways for the pro-
duction of desired bioproducts. However, this work is limited to analyzing production rate
(yield) and has yet to be extended to include economics and environmental performance.
Recently, Ng etal. (2009a) proposed a hierarchical approach for the synthesis and analysis
of an integrated biorefinery. In addition, Kokossis and Yang (2009) identified the challenges
of synthesizing and designing sustainable biorefineries. They also proposed an overall sys-
tematic approach to combine multiscale formulations with multistage problem-solving
capabilities for problems involving novel processes. More recently, Kokossis and Yang (2010)
discussed the potential of using various systems engineering tools in the design of complex
biorefineries. Tan etal. (2009) developed an extended inputoutput model using fuzzy lin-
ear programming to determine the optimal capacities of distinct process units given a pre-
defined product mix and environmental goals such as carbon, land, and water footprints.
In addition to the development of synthesis tools for integrated biorefineries, a flexible
framework for determining the profitability, product portfolio, and process configuration
in an integrated biorefinery was proposed by Sammons etal. (2007, 2008). Sammons (2009)
determined the optimum pathway of an integrated biorefinery with the consideration of
both economic and environmental performance using Pareto optimum analysis. More
recently, Tay etal. (2011a) proposed a fuzzy optimization approach to address the same
design problem. Mansoornejad etal. (2010) have further extended the previous work by
adding market aspects, supply-chain network design, and flexible manufacturing design
to the framework. Tay et al. (2011b) have also presented an insight-based synthesis tool
based on a carbonhydrogenoxygen (CHO) ternary diagram for synthesis of an
Automated Targeting for the Synthesis ofanIntegrated Biorefinery 399

integrated biorefinery. Based on this work, the optimum gasification parameters and the
interaction of gasification with other technologies to prepare the feedstocks and deliver
the required final product can be determined before the detailed design.
To achieve maximum efficiency in an integrated biorefinery, multilevel integration
through process integration approaches is needed. Therefore, process integration tech-
niques are an essential approach to develop an efficient integrated biorefinery with opti-
mum product allocations and portfolios. By means of in-plant material and energy
recovery, generation of waste (carbon dioxide, wastewater, etc.) can be minimized. Besides,
the overall energy consumption of an integrated biorefinery will be lower than that of a
process that operates independently (Ng, 2010). Most recently, Ng (2010) extended the
pinch-based automated targeting approach that was originally developed for synthesis of
resource conservation networks (Ng etal., 2009b,c,d, 2010) to determine the maximum bio-
fuel production and revenue targets for an integrated biorefinery.
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Although some research has been conducted on the synthesis of the integrated biorefin-
ery, the latter is still considered to be in its early development stage. Therefore, research
focusing on the development of systematic tools to aid in the synthesis, design, and opti-
mization of a sustainable integrated biorefinery is needed. In this chapter, the recently
proposed automated targeting approach (Ng, 2010) is first reviewed and then further
extended to synthesize an integrated biorefinery with maximum revenue targets based on
multiple process parameters. In addition, based on the resulting targets, the detailed allo-
cation of raw material (biomass) and intermediate products (alcohol, syngas, etc.) to differ-
ent processes to produce the final products can be determined. With the proposed
approach, the biofuel production and revenue targets for a given feedstock can be deter-
mined before detailed process flowsheet synthesis of the integrated biorefinery.

13.2 Problem Statement


As described in Ng (2010), the carbon contents of raw materials and products are assumed
to be the most important properties for the synthesis of an integrated biorefinery. This is
because carbon is the key element in organic matter (i.e., biomass), and therefore tracking
carbon content from raw material (biomass) to final products is very important. By recov-
ering the carbon content in raw material that may be lost from conversion processes in the
form of gases (e.g., carbon dioxide, carbon monoxide) and solid wastes (e.g., fermentation
residues, charcoal), the overall mass efficiency of a biorefinery can be increased (Ng, 2010).
On the other hand, another process parameter (syngas composition) is also considered to
be a critical process constraint in the design of an integrated biorefinery. For different
types of biomass, different compositions of syngas are produced by gasification. Besides,
most of the conversion technologies, such as methanol synthesis, dimethyl ether synthesis,
and FischerTropsch synthesis, require a specific syngas composition (i.e., H2/CO ratio).
Therefore, this parameter is taken as quality measurement for the synthesis of a gasifica-
tion-based integrated biorefinery, in which syngas is produced as an intermediate.
The problem of synthesizing an integrated biorefinery may be formally stated as follows.
Given a set of biomass/syngas sources SRi, which can be converted into intermediates p,
INTERp or products p, PDp. Each source has a given flow rate FSRi and is characterized by
its carbon fraction (Ci) or H2/CO ratio (Ri). A set of sinks SKj, which are process units that
can convert sources i into intermediates p and products p, is specified. Each sink is
400 Integrated Biorefineries

Source Sink Intermediate

i=1 j=1 p=1 j

i=2 j=2 p=2 j

i=3 j=3 p=3 j


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i=
NSource j = NProcess p = NInter j=N

FIGURE 13.1
Graphic representation of an integrated biorefinery. (Adapted from Ng, D.K.S., 2010. Chem. Eng. J. 162(1), 6774.)

c haracterized by predefined minimum specifications and quality requirement, C min j or


Rmin
j . In addition, the process conversion factors of sources i to intermediates p (Xijp) and
intermediates p to products p (Xpjp) via SKj are also specified.
To reduce the complexity of an integrated biorefinery, only single-stage or two-stage
processes that convert a given source i to any product p will be considered. The problem
structure can be summarized as shown in Figure 13.1. The objective of the methodology is
to determine the maximum production or revenue of a single product (biofuel), or alterna-
tively, the maximum revenue from a mix of multiple products, from given available bio-
mass/syngas feed sources. Furthermore, alternative network designs for an integrated
biorefinery that meets these targets are also determined.

13.3 Automated Targeting


The automated targeting technique was originally developed for mass exchange network
(MEN) synthesis (El-Halwagi and Manousiothakis, 1990) . It was then extended to synthesis
of resource conservation networks (RCN) for cases with reuse, recycle, or both (Ng et al.,
2009b), interception (Ng etal., 2009c, 2009d), and waste treatment (Ng etal., 2010), based on the
cascade analysis technique (Manan etal., 2004; Foo etal., 2006). Automated targeting was also
used to find targets for minimizing the amount of CO2-neutral or low-carbon energy sources
for segregated energy planning problems (Lee etal., 2009). Note that in previous studies on
MEN and RCN syntheses (El-Halwagi and Manousiothakis, 1990; Ng et al., 2009b, 2009c,
2009d, 2010), contaminant concentration and stream flow rate were used as the quality and
quantity measures respectively of process streams. Based on the extracted data, MENs and
RCNs with maximum recovery or minimum annualized operating cost can be synthesized.
For carbon-constrained energy planning, carbon intensity and energy load are used as quality
Automated Targeting for the Synthesis ofanIntegrated Biorefinery 401

and quantity measures for energy systems to determine the optimum allocation of energy
source(s) to the energy sector(s). Most recently, automated targeting was further extended to
locate maximum production and revenue targets for an integrated biorefinery (Ng, 2010). As
mentioned earlier, tracking carbon content and process parameters (H2/CO ratio) are impor-
tant in synthesizing an integrated biorefinery. Hence, carbon content or H2/CO ratio and
material flow rate are used as the dominant quality and quantity parameters respectively.
Previous analogies for MEN and RCN synthesis as well as energy planning are not directly
applicable to the synthesis of the integrated biorefinery. Therefore, the automated targeting
approach has been further extended in this work for the synthesis of an integrated biorefin-
ery. In addition, the model can also be used to synthesize an integrated biorefinery directly.
Based on previous work (El-Halwagi and Manousiothakis, 1990; Ng etal., 2009b, 2009c,
2009d, 2010; Ng, 2010), the technique involves arranging sources and sinks in descending
order of quality, with the highest quality (lowest impurity concentration, lowest emission
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factor, or most desirable composition) located at the top of the cascade. In this work, the
sources, sinks, intermediates, and products are arranged based on two potential quality
measurements, carbon fraction level (Ck) or H2/CO ratio level (Rk), in descending order
from the highest level k=1 to the lowest level k=n in a biorefinery cascade diagram (BCD), as
shown in Figure 13.2. Synthesis of a generic integrated biorefinery with multiple conver-
sion technologies can also use carbon fraction level (Ck) as a quality measurement. However,
for a more specific design such as a gasification-based integrated biorefinery, H2/CO ratio
level (Rk) provides a more accurate representation. The highest value of carbon fraction or
H2/CO ratio is added as the first level if this value does not exist among the process sinks
and sources. In addition, a final fictitious level of zero (Cn=0; Rn=0) is added at the bottom
of the cascade to enable the calculation of residue load (). Next, material flow rate cascad-
ing is performed across all levels. At each level k, the difference between the total available
material sinks (jFSKj) and sources (iFSRi) is determined. Next, the net material flow cas-
caded from the earlier level k1 (k1) is combined with the flow balance at level k to gener-
ate the net material flow rate at the k-th level (k), as given in Equation 13.1:

k = k 1 + ( i FSRi j FSKj )k kK (13.1)



To ensure that no additional biomass or syngas flow is generated from the final level n
(because that level is to be used only for the calculation of residual process load), a new
constraint (as shown in Equation 13.2) is needed:

k = 0 (13.2)

Process load cascading is performed next. Within each interval, the process load is deter-
mined by the product of the net material flow from level k and the difference between it
and the two adjacent levels. As in the material-flow cascade, the residual of the process
load at each level k (k) is cascaded down to the next level. Hence, the process loads balance
in the BCD, whether it is arranged based on carbon content (Figure 13.2a) or H2/CO ratio
(Figure 13.2b). Within each interval, the process load is determined by the product of the
net material flow from level k and the difference between it and the two adjacent levels. As
in the material-flow cascade, the residual of the process load at each level k (k) is cascaded
down to the next level. Hence, carbon-load balance and hydrogen-load balance at the k-th
level can be determined by Equations 13.3 and 13.4, respectively:

k = k 1 + k (Ck Ck + 1 ) k K (13.3)

402 Integrated Biorefineries

(a) Material cascade Process load cascade


0

C1 FSRi, 1 k=1 FSKj, 1 1 = 0

1 = 0 + (i FSRi j FSKj)1 k=1


C2 FSRi, 2 k=2 FSKj, 2 2 = 1 + 1 (C2 C3)
2 = 1 + (i FSRi j FSKj)2 k=2
C3 FSRi, 3 k=3 FSKj, 3 3 = 2 + 3 (C3 C4)
3 = 2 + (i FSRi j FSKj)3 k=3
C4 FSRi, 4 k=4 FSKj, 4 4 = 3 + 4 (C4 C5)

4 = 3 + (i FSRi j FSKj)4 k=4


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5 = 4 + 5 (C5 C6)

Cn1 FSRi, n1 k = n1 FSKj, n1 n1 = n2 + n1 (Cn1 Cn)

n1 = n2 + (i FSRi j FSKj)n1 k = n1
Cn n = n1 + n (Cn Cn+1)

(b) Material cascade Process load cascade


0

R1 FSRi, 1 k=1 FSKj, 1 1= 0

1 = 0 + (i FSRi j FSKj)1 k=1


R2 FSRi, 2 k=2 FSKj, 2 2 = 1 + 2 (R2 R3)

2 = 1 + (i FSRi j FSKj)2 k=2


R3 FSRi, 3 k=3 FSKj, 3 3 = 2 + 3 (R3 R4)
3 = 2 + (i FSRi j FSKj)3 k=3
R4 FSRi, 4 k=4 FSKj, 4 4 = 3 + 4 (R4 R5)

4 = 3 + (i FSRi j FSKj)4 k=4


5 = 4 + 4 (R5 R6)

n1 = n2 + n1 (Rn1 Rn)
Rn1 FSRi, n1 k = n1 FSKj, n1
n1 = n2 + (i FSRi j FSKj)n1 k = n1
Rn n = n1 + n (Rn Rn+1)

FIGURE 13.2
Generic BCD for (a) carbon content and (b) H2/CO ratio.

k = k 1 + k (Rk Rk + 1 ) k K (13.4)

where k1 is the residue load that is cascaded from level k1.


Conversely, the residual process load must have a positive value, which implies that a
feasible load cascade has been achieved (Manan et al., 2004; Foo et al., 2006; Ng et al.,
2009b,c,d, 2010; Ng, 2010). Therefore, the maximum allowable process load of the sink at
Automated Targeting for the Synthesis ofanIntegrated Biorefinery 403

each level is achieved. Therefore, Equation 13.5 is included as a constraint in the formula-
tion of the model:

k 0 k K (13.5)

It is interesting to note that, when the residual process load is determined as zero in the
model solution at level k (k=0), a pinch point occurs. In physical terms, the zero process load
means that, at the optimal solution, the minimum requirements of all sinks above the pinch
point are completely fulfilled by the sources (Manan etal., 2004; Foo etal., 2006; Ng etal.,
2009b,c,d, 2010; Ng, 2010). The identification of the pinch point provides valuable insights to
decision makers. Its primary value is to identify the system bottleneck. Thus, the golden
rule of pinch analysis can be applied to this problem to meet all the specified process require-
ments in the integrated biorefinery. In this case, fresh resources (i.e., biomass) must be sup-
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plied only to those process sinks below the pinch point. Allocation of this resource to process
sink(s) above the pinch point will lead to a nonoptimal solution (Ng, 2010).
Note also that the above formulation is a linear programming (LP) model that can be
solved easily to yield a global optimal solution if such a solution exists. In this research, the
LP models were solved using LINGO v.10.0. However, in practice, the automated targeting
model can be implemented using any LP solver, such as those found in common spread-
sheet environments. In addition, in some cases, a nonlinear system may result from addi-
tional case-specific process constraints or objectives. Such variants can be optimized using
appropriate optimization software.
To determine the maximum production of desired products (FPD), the BCD (Figure 13.2)
is used, with the optimization objective formulated as

Maximize FPD (13.6)

Alternatively, the maximum revenue solution can be obtained for cases with multiple
products, in which case the optimization objective is set as

Maximize REV (13.7)

where REV is the total revenue generated from selling the product. REV can be calculated
as follows:

REV = p (MPp FPDp TC p FPDp ) (13.8)


where MPp, FPDp, and TCp are the market price, flow rate, and total annualized fixed and
variable costs of product p, respectively. In the following section, two hypothetical case
studies are solved to illustrate the proposed automated targeting model for synthesis of
the integrated biorefinery.

13.4 Case Study 1


Case study 1 is adapted from Ng (2010) to illustrate the proposed automated targeting
approach for synthesis of an integrated biorefinery with carbon content as the dominant
404 Integrated Biorefineries

TABLE 13.1
Conversion Table of Biomass to Intermediate and Final Products
Intermediate Conversion, Xijp or
Process Sink j Raw Material p/Product p Xpjp(kgProduct/kg Raw Material)
Digestion Biomass Methane (CH4) 0.147
Biomass residual 0.79
Fermentation Biomass Ethanol 0.27
Biomass residual 0.61
Gasification Biomass Syngas (CO) 0.18
Pyrolysis Biomass Bio-oil 0.54
Dehydration Ethanol Biofuel 0.65
Synthetic fuel Methane Biofuel 0.286
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Synthetic fuel Bio-oil Biofuel 0.1425


FischerTropsch Syngas Biofuel 0.9
Source: Adapted from Ng, D.K.S., 2010. Chem. Eng. J. 162(1), 6774.

quality parameter. Tables 13.1 and 13.2 show the conversion and other data for sinks and
sources for the hypothetical case. In this case study, three scenarios are to be analyzed. In the
first scenario, the optimization objective is to determine the maximum production of a single
product (biofuel) from a given amount of biomass. In the second scenario, a maximum rev-
enue target for a case with multiple products is presented. In the last scenario, the model is
further used to synthesize an integrated biorefinery with multiple feedstocks and products.
In this case study, municipal solid waste (MSW) is selected as the raw material for the inte-
grated biorefinery to produce biofuel. The MSW consists of 70%wt polysaccharides (C6H10O5),
27%wt lignin (CH1.12O0.377), and 3%wt ash (Vinzant etal., 1990). Based on the above informa-
tion, the carbon fraction of the biomass can be calculated as 0.477. Four processes can be used
to convert raw material (biomass) to intermediates such as methane, ethanol, syngas, and bio-
oil by digestion, fermentation, gasification, and pyrolysis, respectively (see Table 13.1). Note
that all intermediates can also be further converted to biofuels by the four potential pro-
cesses, as shown in Table 13.1. Theoretical or empirical conversions of raw material to inter-
mediates or products for these processes are also included in Table 13.1.
Note that further recovery of biomass residues from digestion and fermentation pro-
cesses enables the enhancement of the production of biofuel because these residues have
high carbon content and high energy potential. Therefore, both biomass residues are taken
as sources, SR2 and SR3 (see Table 13.2). Based on theoretical or experimental data reported

TABLE 13.2
Data for Case Study 1
Minimum
Carbon Requirement of
Available Source Fraction Carbon Fraction
Source (kg) (Ci) Sink (C min
j )
SR1 MSW 5000 0.477 SK1 Digestion 0.477
SR2 Digested residual 79% inlet biomass 0.474 SK2 Fermentation 0.477
biomass to digestion
SR3 Fermented 61% inlet biomass 0.170 SK3 Pyrolysis 0.250
residual biomass to fermentation
SK4 Gasification 0.250
Automated Targeting for the Synthesis ofanIntegrated Biorefinery 405

in the literature, the carbon fraction of biomass residues can be estimated (Ng, 2010). As
shown in Table 13.2, the carbon fractions of digested and fermented biomass residues were
found to be 0.474 and 0.170, respectively.
The four processes (digestion, fermentation, pyrolysis, and gasification) that accept simi-
lar raw materials (biomass, biomass residues, or a mixture of both) to produce various inter-
mediates are considered to be sinks (see Table 13.2). Each sink has a specific minimum value
of the carbon fraction (C min
j ) which is required to produce intermediates or products. Note
that the processes that further convert intermediates to final products are not considered as
process sinks in Table 13.2 because such processes are not constrained by the carbon frac-
tions of the intermediates. In addition, these processes require different raw materials or
intermediates to produce a final product (biofuel). Examples of these processes include
FischerTropsch, dehydration, and synthetic fuel processes that require syngas (carbon
monoxide and hydrogen), alcohol, and methane/bio-oil, respectively, to produce biofuel.
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To locate the maximum production target, Equations 13.9 and 13.10 are included in the
automated targeting formulation (Equations 13.1 through 13.5):

FINTERp = Xijp FSKj (13.9)


FPDp = X pjp FINTERp (13.10)


Based on the above equations, the flow rates of the intermediates p (FINTERp) and the final
product p (FPDp) can be determined. Because the biomass residues are considered as SR2
and SR3, the flow rates of these sources can only be determined once the model is opti-
mized. Therefore, the FSRi of biomass residues are included as variables in the automated
targeting algorithm.

13.4.1Scenario 1: Maximum Production of a Single Product (Biofuel) from a


GivenBiomass
The optimization objective (Equation 13.6) is then solved, subject to the constraints in
Equations 13.1 through 13.3, 13.5, 13.9, and 13.10, yielding the solution illustrated in the
BCD shown in Figure 13.3. Note that for a given 5000kg of biomass (SR1), 4115.3kg of bio-
mass is fed to the fermentation process (SK2), and the balance of the biomass (884.7kg) is
gasified via SK4. Based on the given conversions given in Table 13.1, 1111.1kg, and 2510.3kg
of ethanol and biomass residue (SR3) respectively are generated when 4115.3kg of biomass
is fermented in SK2. As shown in Figure 13.3, 884.7kg of SR1 (3) and 2510.3kg of SR3 (4)
are used to produce syngas via gasification (SK4). Based on Table 13.1, the conversion rate
of syngas from biomass (Xijp) is 0.18; hence, 611.1kg of syngas is generated from 3395.0kg
(=2510.3+884.7kg) of biomass mixture. Because the biomass is processed via fermenta-
tion and gasification, two intermediate products (ethanol and syngas) are generated. The
objective of this scenario it to find the maximum conversion of biomass to biofuel, and
therefore both these intermediates are further processed via dehydration and Fischer
Tropsch processes, respectively. Based on the optimization model and the conversion data
in Table 13.1, 1272.2kg of biofuel is produced, where 722.2 and 550kg are derived from
ethanol and syngas, respectively. In line with this detailed allocation of fresh resource
(biomass) and intermediates (residual biomass, ethanol, and syngas), a preliminary design
of an integrated biorefinery for Scenario 1 is shown in Figure 13.4. Note that the unrecov-
ered solid and gas wastes are not shown for simplicity.
406 Integrated Biorefineries

Material cascade Carbon load cascade


0 = 0
0 = 0
C1 = 1.00 0 k=1 0

1 = 0 k=1
FSR1 FSK2 1 = 0
C2 = 0.477 k=2
5000 4115.3
2 = 884.7 k=2
2 = 2.654
C3 = 0.474 0 k=3 0
3 = 884.7 k=3
FSK4 3 = 200.9
C4 = 0.25 0 k=4
3395.0
4 = 2510.3 k=4
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FSR3 0 4 = 0
C5 = 0.17 k=5
2510.3
5 = 0 k=5

C6 = 0 5 = 0

FIGURE 13.3
BCD for Scenario 1: Maximum production of biofuel.

Ethanol Biofuel
Biomass (SR1) 4115.3 kg 1111.1 kg 722.2 kg
Fermentation (SK2) Dehydration
5000 kg
Biofuel
Biomass residual (SR3) 1272.2 kg
2510.3 kg
Syngas
884.7 kg 611.1 kg
Gasification (SK4) FischerTropsch
Biofuel
550 kg

FIGURE 13.4
Preliminary integrated biorefinery design for Scenario 1.

13.4.2Scenario 2: Maximum Revenue for an Integrated Biorefinery


withMultipleProducts
A second scenario with multiple products will now be examined. The optimization objec-
tive is to maximize revenue for a given fixed raw material cost by selecting the optimum
product portfolio. Table 13.3 shows typical market prices for various intermediates and
final products based on historical data.
Because some intermediates p have a market value (MPp), these intermediates can also
be taken as final products. To determine the flow rates of these multiple products, a p
rocess
mass balance (Equation 13.11) is included in the model:
I I
FPDp = FPD p FINTERp (13.11)

I
where FPD p is the flow rate of product p that can be produced from the first biomass pro-
I
cessing step, and FINTER p denotes the flow rate of product p that requires further processing
(which is also considered as an intermediate p).
Automated Targeting for the Synthesis ofanIntegrated Biorefinery 407

TABLE 13.3
Revenues from Intermediates and Final Products
Intermediates/Final Products Market Price, MPp ($/kg)
Biofuel 0.93
Methane (CH4) 1.02
Ethanol 0.78
Bio-oil 0.008
Source: Adapted from Ng, D.K.S., 2010. Chem. Eng. J. 162(1),
6774.

Solving the model using the objective function in Equation 13.7 and subject to all
c onstraints (Equations 13.1 through 13.3, 13.5, and 13.8 through 13.11) yields the results
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shown in Figure 13.5. Note that digestion (SK1), fermentation (SK2), and gasification (SK4)
processes are involved in this scenario. As shown in Figure 13.5, for a given 5000kg of
biomass, 1080.8 and 3919.2kg of biomass are digested into methane and fermented to etha-
nol, respectively. In this scenario, two types of residual biomass (SR2 and SR3) are gener-
ated from digestion and fermentation processes. Based on Table 13.1, the flow rates of SR2
and SR3 are determined as 853.8kg (=0.791080.8kg) and 2390.7kg (=0.613919.2kg),
respectively (see Figure 13.5).
In addition, the maximum revenue target is found to be $1476 when 5000kg of biomass
is processed. Based on the optimized model, 1058.2kg of ethanol and 158.9kg of methane
from fermentation and digestion processes, respectively, are considered to be final prod-
ucts. Meanwhile, 3244.5kg (=853.8+2390.7kg) of biomass residues from both processes
are gasified to 584kg of syngas and then further converted to 525.6kg of biofuel via a
FischerTropsch process. The preliminary design of the integrated biorefinery for Scenario 2
is shown in Figure 13.6. As in to the previous scenario, the unrecovered waste streams are
neglected and excluded from Figure 13.6 for simplicity. Note that the preliminary i ntegrated

Material cascade Process load cascade


0 = 0
0 = 0
C1 = 1.00 0 k=1 0

1 = 0 k=1
FSR1 FSK1 F 1 = 0
C2 = 0.477 k=2 + SK2
5000 1080.0 3919.2
2 = 0 k=2
FSR2 2 = 0
C3 = 0.474 853.8 k=3 0
3 = 853.8 k=3
FSK4 3 = 191.3
C4 = 0.25 0 k=4
3244.5
4 = 2390.7 k=4
FSR3 0 4 = 0
C5 = 0.17 k=5
2390.7
5 = 0 k=5

C6 = 0 5 = 0

FIGURE 13.5
BCD for Scenario 2: Maximum revenue for cases with multiple products.
408 Integrated Biorefineries

Methane Biomass residual


158.9 kg (SR2)
Biomass (SR1) 1058.2 kg Digestion 853.9 kg
5000 kg (SK1)
Syngas Biofuel
Gasification 584 kg 525.6 kg
FischerTropsch
(SK4)

3919.2 kg Fermentation Biomass residual


(SK2) (SR3)
Ethanol 2390.7 kg
1058.2 kg

FIGURE 13.6
Preliminary integrated biorefinery design for Scenario 2.
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biorefinery design of Scenario 2 is different from Scenario 1. In Figure 13.6, an additional


digestion process is used to generate methane, which is considered as a product. Therefore,
based on a different optimization objective, an alternative preliminary integrated design
for the integrated biorefinery is obtained.

13.4.3Scenario 3: Maximum Revenue for an Integrated Biorefinery with Multiple


Feedstocks and Products
In this scenario, the proposed model is used to analyze an integrated biorefinery with
multiple feedstocks and products. In this scenario, two types of available biomass (wood
waste (SR1) and MSW (SR2)) are considered (see Table 13.4).
Based on the ultimate analysis, the carbon fractions of SR1 and SR2 are calculated as
0.490 and 0.477, respectively. Note that the process sink requirements and the residual bio-
mass values shown in Table 13.4 are similar to those in previous scenarios. In addition,
conversion and revenue data similar to those presented in Tables 13.1 and 13.3 are also
used in this scenario. Because multiple feedstocks are available in this scenario, to ensure
that the total consumption of the process sink is not greater than the available fresh
resources (SR1 and SR2), Equation 13.12 is included in the model:

j FSKj FSR 1 + FSR 2 (13.12)


TABLE 13.4
Data for Scenario 3
Minimum
Carbon Requirement
Available Source Fraction of Carbon
Source (kg) (Ci) Sink Fraction (C min
j )
SR1 Wood waste 5000 0.490 SK1 Digestion 0.477
SR2 MSW 5000 0.477 SK2 Fermentation 0.477
SR3 Digested residual 79% inlet biomass 0.474 SK3 Pyrolysis 0.250
biomass to digestion
SR4 Fermented residual 61% inlet biomass 0.170 SK4 Gasification 0.250
biomass to fermentation
Source: Adapted from Ng, D.K.S., 2010. Chem. Eng. J. 162(1), 6774.
Automated Targeting for the Synthesis ofanIntegrated Biorefinery 409

Material cascade Process load cascade


0 = 0
0 = 0
C1 = 1.00 0 k=1 0

1 = 0 k=1
FSR1 1 = 0
C2 = 0.490 k=2 0
5000
2 = 5000 k=2
FSR2 FSK1 F 2 = 65
C3 = 0.477 k=3 + SK2
5000 1873.7 8126.3
3 = 0 k=3
FSR3 0 3 = 65
C4 = 0.474 k=4
1480.2
4 = 1480.2 k=4
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FSK4 4 = 396.6
C5 = 0.25 0 k=5 6437.3
5 = 4957.1 k=5
FSR4 k=6 5 = 0
C6 = 0.17 0
4957.1
6 = 0 k=6
C7 = 0 6 = 0

FIGURE 13.7
BCD for Scenario 3Maximum revenue for cases with multiple feedstocks and products. (Adapted from Ng,
D.K.S., 2010. Chem. Eng. J. 162(1), 6774.)

Following a similar approach to Scenario 2, the model is solved using the objective func-
tion in Equation 13.7, subject to the constraints in Equations 13.1 through 13.3, 13.5, and 13.8
through 13.12, to yield the results shown in Figure 13.7.
Similarly to Scenario 2, digestion (SK1), fermentation (SK2), and gasification (SK4)
are needed to produce multiple products in an integrated biorefinery to generate the
maximum revenue. In this scenario (Figure 13.7), 1873.7 and 8126.3kg of biomass (the
total of SR1 and SR2) are digested into methane and fermented to ethanol via SK1 and
SK2, respectively. Based on Table 13.1, 1480.2kg (=0.791873.7kg) of SR3 and 4957.0kg
(=0.618126.3kg) of SR4 are generated, with 1873.7 and 8126.3kg of biomass being
digested and fermented, respectively. The maximum revenue target is determined to be
$2962 based on the given wood waste and MSW. In addition, 2194kg of ethanol and 275kg
of methane are produced from fermentation and digestion processes and are considered
as final products. Meanwhile, all residual biomass from SK1 and SK2 (6437.3kg) is gas-
ified to 1168kg of syngas and then further converted to 1042.8kg of biofuel via a Fischer
Tropsch process. The preliminary integrated biorefinery design for this scenario is shown
in Figure 13.8, which is similar to that in Scenario 2, but with different flow rates.

13.5 Case Study 2


Case study 2 illustrates the application of automated targeting to synthesis of a gasifica-
tion-based integrated biorefinery. Table 13.5 shows the process data for a hypothetical case
410 Integrated Biorefineries

Methane Biomass residual


275 kg (SR3)
Wood waste 1873.7 kg Digestion 1480.2 kg
(SR1) (SK1)
5000 kg Syngas Biofuel
+ Gasification 1158.7 kg 1042.8 kg
Energy crop FischerTropsch
(SK4)
(SR2)
5000 kg
8126.3 kg Fermentation Biomass residual
(SK2) (SR4)
Ethanol 4957.0 kg
2194 kg

FIGURE 13.8
Preliminary integrated biorefinery design for Scenario 3. (Adapted from Ng, D.K.S., 2010. Chem. Eng. J. 162(1),
Downloaded by [Cornell University] at 04:45 09 September 2016

6774.)

where syngas is taken as an intermediate. In this case study, various types of biomass are
assumed to be first gasified to syngas. As mentioned previously, different types of biomass
lead to different syngas compositions; therefore, four types of syngas (SR1SR4) produced
from oil palm empty fruit bunches (EFB), switchgrass, bagasse, and corn stover, respec-
tively, are considered (Table 13.5). As shown, the flow rates of syngas (SR1SR4) are assumed
to have a maximum value of 100kg/h. In this case study, four processes which convert
syngas to valuable products (mixed alcohols, methanol, FischerTropsch fuel, and dimethyl
ether fuel) were included, as shown in Table 13.6. Note that the conversion of syngas to
final products is based on CO flow rate; therefore, the corresponding CO molar flow rate of
each source (100 kg/h) is taken as the quantitative measurement instead of the mass flow
rate. The corresponding CO molar flow rate of syngas, which can be predicted by a gasifi-
cation model (Tay etal., 2011c), is given in Table 13.5. Note also that each process requires
a minimum H2/CO ratio (C min j ) to convert syngas to the desired products. To fulfill this
process requirement, fresh syngas (FG) with an H2/CO ratio (R FG) of 3.0, produced from a

TABLE 13.5
Hypothetical Case Study 2
Corresponding Minimum
Available CO Molar Flow Requirement
Source H2/CO Rate of H2/CO
Source (kg/h) (Ri) (kmol/hFSRi) Sink ( Rjmin )
SR1 Syngas (EFB) 100 0.9 2.2567 SK1 Mixed 2.5
alcohols
synthesis
SR2 Syngas 100 0.7 2.2583 SK2 Methanol 2.0
(switchgrass) synthesis
SR3 Syngas 100 0.6 2.2640 SK3 Fischer 2.0
(bagasse) Tropsch
synthesis
SR4 Syngas (corn 100 0.5 2.2600 SK4 Dimethyl 1.0
stover) ether
synthesis
FG Fresh syngas To be 3.0 To be
(SMR) determined determined
Automated Targeting for the Synthesis ofanIntegrated Biorefinery 411

TABLE 13.6
Conversion Table of Syngas to Final Products
Conversion, Xijp or Xpjp
Process Sink j Raw Material Product p (Gallon Product/kmol CO)
Mixed alcohols synthesis Syngas Mixed alcohol fuel 1.9547
Methanol synthesis Syngas Methanol 10.5684
FisherTropsch synthesis Syngas FischerTropsch fuel 3.7371
Dimethyl ether synthesis Syngas Dimethyl ether fuel 8.1620

steam methane reformer (SMR), is readily available. Theoretical and empirical conversions
of syngas to the desired products for all processes are presented in Table 13.6.
The optimization objective of this case study is to determine the maximum revenue of a
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product portfolio from a given amount of syngas sources. In this case study, because the
intermediate (syngas) is taken as a process source, Equations 13.9 and 13.10 can be com-
bined as Equation 13.13:

FPDp = X pjp FSKi (13.13)


Based on the above equation, the flow rates of the final product p (FPDp) can be deter-
mined. As shown in Table 13.5, the available CO flow rates of sources (SR1SR4), FSRi, were
given as 2.2567, 2.2583, 2.2640, and 2.2600kmol/h, respectively. Therefore, Equations 13.14
through 13.17 are included in the model based on their corresponding CO molar flow rates:

FSR12.2567kmol/h (13.14)

FSR22.2583kmol/h (13.15)

FSR32.2640kmol/h (13.16)

FSR42.2600kmol/h (13.17)

In this case study, the optimization objective was to determine the maximum revenue,
and therefore Equation 13.8 was revised to yield Equation 13.18:

REV = p (REVp FPDp CPRODp FPDp ) i (CSRi FSRi ) CFGFFG (13.18)


where CPRODp is the annualized fixed and variable cost of producing product p, CSRi is the
cost of syngas SRi, CFG is the production cost of syngas by steam methane reforming, and
FFG is the flow rate of syngas from steam methane reforming (FG). Economic data for this
case study are presented in Table 13.7.
An additional equation (Equation 13.19) is needed in the optimization model to calculate
its net present value of profit/loss over the course of the plant operating life span, t. In this
case study, t was assumed to be 25 years with a discount rate (r) of 15% (Sammons, 2009):

(REV A)
NPV = (1 + r )t (13.19)
t

where A is the annual plant operating hour (8330h).


412 Integrated Biorefineries

TABLE 13.7
Economic Data for a Gasification-Based Integrated Biorefinery
CSRi CPRODp REVp
Source ($/kmol CO) Sink p ($/gallon) ($/gallon)
SR1 Syngas 0.1753 SK1 Mixed alcohols Mixed alcohol 4.0080 1.77
synthesis fuel
SR2 Syngas 1.5655 SK2 Methanol Methanol 4.1500 1.00
synthesis
SR3 Syngas 0.4626 SK3 FischerTropsch FischerTropsch 1.1140 1.54
synthesis fuel
SR4 Syngas 0.8566 SK4 Dimethyl ether Dimethyl ether 0.6508 0.99
synthesis fuel
FG Fresh syngas 6.8000
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(steam
reformer)
Source: Adapted from Sammons, N.E. Jr., 2009. A Framework for Optimal Polygeneration Product Allocation. PhD
Dissertation (Chemical Engineering), Auburn University.

Based on the proposed approach, the optimization model (Equations 13.1 through 13.2, 13.4,
13.13 through 13.19) is solved with the optimization objective (Equation 13.7) to determine the
optimum allocation of syngas for production of value-added products with maximum profit.
The resulting BCD is shown in Figure 13.9. Note that all available biomasses are being gasified
to produce syngas (SR1SR4) at the corresponding CO molar flow rate, as shown in Table 13.6.
Note also that 1.4694 CO kmol/h of syngas from SMR, which is equivalent to 49.96kg/h of
syngas (1.4693MWCO+31.4693MWH2, where MWCO and MWH2 are the molecular
weights of CO and H2, respectively), is supplied to improve the syngas produced from bio-
mass to meet the minimum SK4 requirement (R4min ). As shown in Figure 13.9, all syngas from
SMR and biomass gasification (10.51kmol/h of CO, which corresponds to a total syngas flow
rate of 315.30kg/h) is sent to SK4 for production of dimethyl ether fuel (DME).
Based on the optimized model, the maximum annual profit is targeted as US$ 0.1015
million with production of 85.78gal/h dimethyl ether fuel (=10.51kmol/h8.1620gal
DME/kmol CO). Over the course of 25 years at a discount rate of 15%, the net present value
of the integrated biorefinery profit was determined to be US$ 0.7546 million. Figure 13.10
shows the preliminary integrated biorefinery design for case study 2.
It is worth mentioning that the values presented in Tables 13.1 through 13.7 may vary based
on market price, state of advancement of technologies, and various operating conditions as
well as the types of feedstocks. In addition, price fluctuations and feedstock quality varia-
tions will certainly be encountered in biomass supply chains. Hence, with such variations
and uncertainties, the production and revenue targets as well as the network design may
change. However, the proposed automated targeting can be easily revised and reformulated
to locate the targets and to identify the processes involved in the integrated biorefinery.

13.6Conclusions
In this chapter, an automated targeting approach for finding the maximum biofuel pro-
duction and revenue targets of an integrated biorefinery has been presented. These targets
Automated Targeting for the Synthesis ofanIntegrated Biorefinery 413

Material cascade Process load cascade


0 = 0

R1 = 3 k=1 0 0 = 0
FG = 1.4694
1 = 1.4694 k=1

0 k=2 0 1 = 0.7347
R2 = 2.5
2 = 1.4694 k=2

0 k=3 0 2 = 1.4694
R3 = 2
3 = 1.4694 k=3
FSK4 3 = 2.9388
R4 = 1 0 k=4
10.51
4 = 9.039 k=4
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FSR1 4 = 2.0349
R5 = 0.9 k=5 0
2.2567
5 = 6.7823 k=5
FSR2 0 5 = 0.6784
R6 = 0.7 k=6
2.2583
6 = 4.5240 k=6
FSR3 6 = 0.2260
R7 = 0.6 k=7 0
2.2640
7 = 2.2600 k=7
FSR3
R8 = 0.5 k=8 0 7 = 0
2.2600
8 = 0 k=8
R9 = 0 8 = 0

FIGURE 13.9
BCD for case study 2: Maximum revenue for a gasification-based integrated biorefinery.

can be found before detailed design of the integrated biorefinery. Then the preliminary
integrated biorefinery design that achieves the targets can be determined using the pro-
posed approach. In addition, the proposed approach can also be easily revised and refor-
mulated to accommodate uncertainties in feedstock quality, market conditions, and
process yields. Further work is still needed, however, to develop a unified approach to
designing a robust and flexible integrated biorefinery that can handle different types of
feedstock. In addition, extension of the current model to account for seasonality and the
biomass supply chain remains to be considered.

Syngas from SMR 1.4693 kmol/h


CO (49.96 kg/h) 10.51 kmol/h Dimethyl ether
(H2/CO ratio = 1) synthesis Dimethyl ether fuel
+ (Conversion = 85.78 gallon/h
Syngas from biomass gasification 8.1620 gal DME/
9.04 kmol/h CO (400 kg/h) kmol CO

FIGURE 13.10
Preliminary integrated biorefinery design for case study 2.
414 Integrated Biorefineries

Acknowledgments
Financial support from the University of Nottingham Research Committee through its
New Researcher Fund (NRF 5021/A2RL32) is gratefully acknowledged. The authors would
also like to express their gratitude to Professor Raymond Tan from De La Salle University,
Philippines, for some helpful suggestions to improve the current work.

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