Chapter 10. Optimal Synthesis of Sustainable Biorefineries

10
Optimal Synthesis of Sustainable Biorefineries
Mariano Martn and Ignacio E. Grossmann
CONTENTS
10.1 Introduction......................................................................................................................... 325
10.2 History of Biofuel Production Processes......................................................................... 327
10.3 Synthesis of Biofuel Production Processes: Energy and Water Optimization........... 327
10.3.1 Corn-Based Biofuels............................................................................................... 327
10.3.2 Lignocellulose-Based Biofuels.............................................................................. 330
10.3.2.1 Gasification............................................................................................... 330
10.3.2.2 Hydrolysis................................................................................................. 331
10.3.2.3 FischerTropsch-Diesel........................................................................... 333
10.3.2.4 Other Bioproducts.................................................................................... 335
10.3.3 Oil-Based Biofuels................................................................................................... 335
10.3.3.1 First-Generation Biodiesel...................................................................... 336
10.3.3.2 Cooking-Oil-Based Diesel...................................................................... 336
10.3.3.3 Production Process of Biodiesel from Oil............................................. 337
10.3.4 Algae-Based Biofuels.............................................................................................. 338
10.4 Concluding Remarks.......................................................................................................... 339
Acknowledgments.......................................................................................................................340
References...................................................................................................................................... 341
10.1Introduction
The design of a biorefinery poses a substantial number of challenges that require the use
of advanced process synthesis and optimization methods to ensure that these systems are
economically viable, energy-efficient, and have minimum environmental impact.
Process synthesis involves choosing the topology of a process to convert a set of inputs
into a desired set of outputs (Rudd etal., 1973). The objective is to find designs with mini-
mum cost or maximum profit, even though objectives such as maximizing efficiency or
minimizing the usage of a resource (e.g., energy or fresh water) can also be considered.
Major approaches to optimize process flowsheets to meet the desired objectives include
the use of heuristics, the development of physical insights (commonly based on thermody-
namics), and the optimization of superstructures of alternatives. Major contributions to
the first two approaches have been hierarchical decomposition (Douglas, 1988) and pinch
analysis (Linnhoff, 1993), which have proved to be very successful in industrial applica-
tions. A more recent trend has been to combine some of these concepts with the mathemat-
ical-programming approach (Grossmann etal., 1999), which consists of three major steps.
The first is the development of a representation of various alternatives from which the
325
326 Integrated Biorefineries
optimum solution is selected. The second is the formulation of a mathematical program,

generally involving both discrete and continuous variables, to select the configuration and
the operating levels respectively. The third is the solution of the optimization model (com-
monly a mixed-integer nonlinear programming (MINLP) model or a generalized disjunc-
tive programming (GDP) model) to obtain the optimal solution. Although superstructures
can be developed in a systematic way for subsystems, for example, for heat-exchanger net-
works (see, e.g., Yee and Grossmann, 1990), their development for general process flow-
sheets is more complex (Yeomans and Grossmann, 1999). As for the problem formulation,
it is important to note that synthesis models can be formulated at three main levels of
detail: (a) high-level aggregated models concentrate on major features like energy
flows(e.g., the LP transshipment model for HEN [Heat exchanger Network] by Papoulias
and Grossmann (1983), or the NLP heat- and mass-exchanger model by Papalexandri and
Pistikopoulos (1996)); (b) short-cut models that involve cost optimization (investment
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andoperating costs), but in which the performance of the units is predicted using rela-
tively simple nonlinear models (e.g., the MINLP heat-exchanger networks proposed by Yee
and Grossmann (1990), or the MINLP process flowsheets developed by Kocis and
Grossmann (1987)); (c) rigorous models that rely on detailed superstructures and involve
rigorous and complex models for predicting unit performance (e.g., the MINLP synthesis
of distillation sequences by Smith and Pantelides (1995) or the GDP models proposed by
Grossmann etal. (2005)).
It should be noted that at the level of process synthesis, two problems that have major
significance for sustainability are optimization of energy recovery and water manage-
ment. In these cases, the simultaneous optimization and heat integration of a process can
be modeled using the constraints proposed by Duran and Grossmann (1986). However,
this method is restricted to nonisothermal streams. Grossmann etal. (1998) have extended
this model to handle isothermal streams that undergo changes of phase using a disjunc-
tive programming approach. On the problem of synthesizing water process networks, sig-
nificant work has been reported in the literature (for reviews, see Bagajewicz, 2000;
Jezowski, 2008; Bagajewicz and Faria, 2009), using both pinch (Wang and Smith, 1994) and
mathematical programming approaches (e.g., Karuppiah and Grossmann, 2006). The latter
have emerged as the preferred choice for water networks because the pinch approach is
restricted to problems with a single contaminant. These models, aside from optimizing
cost, have as a major goal to minimize the consumption of fresh water. Ahmetovic and
Grossmann (2010) have recently developed a model that accommodates multiple freshwa-
ter sources, recycle within units, and sources or sinks of water in a process, while enabling
the user to control the complexity of the network by limiting the number of piping connec-
tions with 01 variables.
Finally, it should also be pointed out that systematic methods for separation systems
have also played a very important role in the design of sustainable chemical processes. At
this time, very few papers have reported the use of process synthesis techniques with
explicit incorporation of sustainability issues (e.g., Stefanis etal., 1995; Steffens etal., 1999;
Halasz etal., 2005; Carvahlo etal., 2006; Guillen-Gosalbez etal., 2008). Some of these have
applied optimization methods to the molecular design of solvents and the synthesis of the
associated separation processes (Pistikopoulos and Stefanis, 1998; Hostrup etal., 1999).
The design of the biorefinery must face a number of challenges: bioprocess versus chemi-
cal process, selection among alternative technologies, energy and water consumption, and
waste production (Jimenez-Gonzlez and Woodley, 2010), which determine the technical
and economic feasibility of each design. Systematic process synthesis is a powerful tool for
selecting the optimal design among a large number of alternatives. This approach has been
Optimal Synthesis of Sustainable Biorefineries 327
used recently for the design of biorefineries, as will be described later in the chapter, for
example by Agrawal etal. (2007); Karuppiah etal. (2008); and Martn and Grossmann (2010a,
2011a), as well for integrating the various processes for optimal operation of the biorefinery,
for example by Sammons et al. (2006, 2008); Kokossis and Yang (2010); Ng (2010); and
Mansoornejad etal. (2010).
10.2 History of Biofuel Production Processes

The history of biofuels has been linked to the automobile industry since its very beginning
back in the nineteenth century. By the time the diesel engine was patented in 1893, R. Diesel
stated, The use of vegetable oils for engine fuels may seem insignificant today. But such
oils may become in course of time as important as petroleum and the coal tar products of
the present time (Agarwal, 1997). The first car produced on an assembly line, the Ford
Model T (19081927), can be regarded as the first flexible-fuel vehicle because it had an
adjustable carburetor so that the car could be run on gasoline, ethanol, or a blend. However,
the ready availability of crude-based fuels displaced the use of biofuels for decades, and the
use of renewable resources was focused more on pulp and paper production from wood,
saccharification of wood, nitration of cellulose for guncotton and viscose silk, production of
soluble cellulose for fibers, fat curing, and the production of furfural for nylon.
Nowadays, the increasing shortage of energy resources, the increasing demand for and
dependency on fossil fuels, and the growing concerns about the environment have led
humans to consider alternative and renewable energy sources. Presently, the entire world is
in a race to develop alternative energy resources which must be cheap, renewable, and non-
polluting, or at least with neutral emissions. In the transportation sector, which is the
most challenging one because of its need for high-density energy sources, only biomass
provides an alternative that can be implemented in the short term (Cole, 2007). Therefore,
bioethanol and biodiesel have become the most promising alternatives. Todays biorefinery
technologies are based: (1) on the utilization of the whole plant or complex biomass, and (2)
on integration of traditional and modern processes for utilization of biological raw materi-
als. Figure 10.1 provides an overview of various processing alternatives using biomass and
waste as raw material. The next section presents a number of process alternatives for the
production of first- and second-generation biofuels based on systematic process synthesis.
10.3Synthesis of Biofuel Production Processes: Energy and Water

Optimization
10.3.1 Corn-Based Biofuels
Karuppiah etal. (2008) considered energy optimization of the dry-grind process for the
corn-based bioethanol plant, which accounts for 95% of the ethanol produced in the United
States. In such plants, fuel ethanol is produced using corn kernels as the feedstock. Fuel-
grade ethanol must be very close to 100% pure before it can be blended with gasoline for use
in automobiles. However, conventional distillation columns produce an azeotropic mixture
Hydrolysis
and
fermentation
Grain
Ethanol
Pretreatment
Lignin
Electricity
Gasification
CO2
Lignocellulosic Biomass
Water gas shift Hydrogen
Pretreatment Drying zone
Pyrolysis Syngas Methanol

zone CO2
Air Combustion zone Catalysis
The throat
Reduction zone Ethanol
Gas The grate

Ash removal
Fermentation Hydrogen
FischerTropsch FT-diesel
Pyrolysis
Gasoline
Petrochemicals
Char
CO2 Bio-oil
Microalgae
Digestion
Biogas
Liquid
Glycerol
Oil extraction
Waste oil
Transesterification Biodiesel
FIGURE 10.1
Raw materials, technologies, and biofuels. (Martn, M. and Grossmann, I.E. 2010d. Industrial & Engineering
Chemistry Research. With permission.)
of ethanol and water (95% ethanol5% water), which has to be purified further for making
fuel ethanol. The main challenge impeding commercial production of fuel ethanol is that
the process is very energy-intensive and requires large amounts of steam and electricity for
use in the rectifiers to obtain an azeotropic mixture of ethanol and water, as well as the use
of expensive molecular sieves to obtain 100% pure ethanol. Karuppiah etal. (2008) devel-
oped a simplified model to predict the performance of a bioethanol flowsheet that includes
grinding, scarification, fermentation, centrifugation, and drying operations (Figure 10.2). A
superstructure was also postulated in which some of the major alternatives included sepa-
ration by molecular sieves, corn grits, or both, and different ways to accomplish drying of
grain solids, the cattle-feed by-product. The objective was to optimize the flowsheet by
determining the connections in the network and the flow in each stream in the network,
such that the energy requirements of the overall plant would be minimized while the yields
were maximized. Optimization without heat integration (MINLP model) led to a decrease in
manufacturing cost from $1.50/gal (base case) to $1.36/gal. In the next step, heat integration
was added to the optimization, which further reduced the cost to $1.28/gal. However, it
Washing water Superheated steam Enzyme Enzyme
Src2 Src4 Src5 Src6
HX1 HX2
Feedstock
Src1 Wash1 Grind1 Mix2 Premix1 Jet1 Col1 Liq1 Sac1
HX3
To recycle
Vent gas
CO2, O2 Storage tank Yeast, Urea, Water
Snk1 Fer1 Str1 Mix3 Src7
VOC removal
Snk9 Spl7 95%

Ethanol
Cond2
Str2 Storage tank Mix4 Rec1 Spl4
Dry DDGS HX10 Solids 10.8%

Ethanol
Snk8 Dry1 MecP1 Spl1 72% Snk2
Ethanol
Proteins Flot Adsorbent:

100%
1 corn grits
Ethanol
BC1 HX6 Src9 97.7%
Ethanol
HX4 Ethanol
Spl3 Spl2 Mix5 Ads1 Spl5 Mix7 Snk5
Cond1 HX5
Spl6 Snk3
HX11 Absorbent
HX8 Dry air

WWT1
Mix6 MS1 MS2 Src8
HX7 Humid air

Snk7 Snk6
HX9 Snk4
Treated Removed
water components
FIGURE 10.2
Corn-based ethanol production process. (Karuppiah, R. et al. 2008. AIChE Journal 54(6): 14991525. With
permission.)
became clear that the scope of heat integration is limited by the relatively low temperature
in the fermentor. To improve the potential for heat integration, the authors considered mul-
tiple-effect distillation in the beer column and in the azeotropic column as alternatives
for optimization (Figure 10.2). This finally led to a 65% savings in steam and cooling-water
consumption with a cost reduction to $1.24/gal. Figure 10.5, which appears later in the chap-
ter, shows the energy consumption and cooling needs of the process. This example illus-
trates the potential for cost reduction in biofuel plants with an optimization approach.
However, sustainability involves more than just low energy consumption. Corn-based
ethanol has been criticized, not only for its energy balance, but also because of its high
demand for water. The first data available in the literature for water consumption in etha-
nol plants revealed values ranging from 3 to 15galwater/galethanol (Aden 2007). Over the last
decades, there has been some improvement to reach the current industrial mean value for
the newest plants of 3.4galwater/galethanol (MATP, 2008). Based on this, the suggested best-
practice possible water consumption for a corn-based process is 2.85galwater/galethanol (Aden
2007, Pfromm 2008). They also developed an optimum water network for the cases for
which Karuppiah etal. (2008) optimized the energy consumption. It is worth pointing out
that energy optimization plays a very important role in reducing water consumption
because cooling needs are greatly reduced, as are the losses in the cooling tower. In this
way, by coupling energy optimization and the design of optimal water networks where
waste water is treated and recycled, and by using air cooling to replace water partially as
a cooling agent, the water consumption of a corn-based ethanol plant can be reduced to
only 1.17galwater/galethanol, as shown in Figure 10.6 later in the chapter. This value is less
than others recently published in the literature and also confirms the technical feasibility
of the claims made by the Delta T company, which has reported consumptions of 1.5gal/
gal (Delta, 2009). Furthermore, the energy-optimization and water-network design also
play an important role in the move toward zero water discharge, achieving discharge val-
ues of 0.27galwater/galethanol (Martn etal., 2010b). However, better and cheaper wastewater
technologies are needed to reach the goal of zero discharge.
10.3.2 Lignocellulose-Based Biofuels

Corn ethanol has the disadvantage that it competes with the food chain. Therefore,
second-generation bioethanol is based on lignocellulosic materials which offer yields

(Figure 10.9) even higher than those from corn (especially switchgrass), but which have no
footprint on the food supply chain. Two paths can be used to obtain ethanol from lignocel-
lulosic raw materials: gasification or hydrolysis.
10.3.2.1Gasification
To produce ethanol from switchgrass by gasification, syngas is produced and used to obtain
ethanol. Martn and Grossmann (2011a) developed a conceptual design of a production
process for ethanol from switchgrass by optimizing a superstructure of alternatives. The
process consists of four steps: gasification (followed by gas cleanup), concentration adjust-
ment, sour-gas removal, and ethanol synthesis. Two gasification alternatives were evalu-
ated, indirect (Phillips etal., 2007) and direct (Gissy etal., 1992, Dutta and Philips, 2009). The
gas obtained is treated using either steam reforming or partial oxidation to remove hydro-
carbons; subsequently it must be cleaned to remove solids as well as other compounds like
NH3 using either a hot or cold cleaning process. Next, the gas composition is adjusted to a
CO/H2 ratio of one. Three alternatives (bypass, membrane-PSA, and watergas shift) were
evaluated. Then the removal of the sour gases CO2 and H2S is required. Three alternatives,
membrane separation, absorption in ethylamines, and PSA were considered for this task.
Once the syngas has been prepared, two synthetic paths were evaluated: (1) high-alcohols
catalytic process with one of two possible distillation sequences (direct and indirect), and
(2) a syngas fermentation followed by one of four possible dehydration processes: distilla-
tion, water adsorption in corn grits, molecular sieves, and pervaporation. The number of
alternative designs is large, and therefore systematic optimization methods are a powerful
tool for designing the production process. The superstructure is written as an MINLP
which is solved by partial enumeration of the integer variables in terms of gasification tech-
nologies, reforming modes, and synthesis paths, generating eight subproblems. For each of
the subproblems, the cleaning stages and the separation processes are optimized to mini-
mize energy consumption. Subsequently, multiple-effect columns and the design of the
optimal HEN are implemented in each of the subproblems. Finally, an economic evaluation
to account for the contribution of hydrogen as a by-product, raw-material consumption, and
utilities yields the flowsheet with the lowest production cost, as shown in Figure 10.3. Figure
10.5, presented later in the chapter, shows the energy consumption and cooling needs of the
process (Martn and Grossmann, 2011a).
The most profitable process uses high-pressure direct gasification followed by steam
reforming, which increases the production of hydrogen. Composition adjustment is c arried
MEA
T = 29C
P = 29 bar
Bypass
Pretreatment Direct gasification Steam reforming Filter HBC removal
PSA H2
T = 853C P = 21 bar T = 500C T = 25C
P = 21 bar P = 21 bar P = 4.5 bar T = 25C
P = 4.5 bar PSA CO2 removal
T = 25C
P = 4.5 bar
Ethanol Direct distillation seq. Catalytic
T = 300C
P = 68 bar
FIGURE 10.3
Thermochemical ethanol production from biomass. (Martn, M. and Grossmann, I.E. 2011a. AIChE Journal
57(12), 34083428. With permission.)
out by removing the excess of hydrogen from the stream using a hybrid system consisting
of PSA and membranes. Then sour gases are removed in two steps, PSA to remove CO2,
and MEA to get rid of H2S. Finally, the catalytic path is selected, followed by the direct
distillation sequence. The process generates 18MW of energy and requires 68MW of cool-
ing. The production cost of this design turned out to be $0.41/gal due to the contribution of
hydrogen as a by-product. The fermentation path is not economically attractive because of
the low concentration of ethanol in the reactor, which results in high-energy consumption
to dehydrate the waterethanol mixture. It has been estimated that if the concentration of
ethanol were to reach a value of 15% (Martn and Grossmann, 2011a), then this synthesis
path would also become promising. Several studies have focused on increasing the con-
centration of ethanol in the fermentor by removing it from the liquid phase using adsor-
bents (Nielsen and Prather, 2009).
The production process of ethanol from switchgrass by gasification and catalytic synthe-
sis requires a large amount of water in the form of cooling water, due to the high pressures
and temperatures in the entire process, and in the form of steam to perform the gasifica-
tion. Values of 5.99.8galwater/galethanol have been reported in the literature when using
switchgrass as a raw material (Wu etal., 2009), and values of 2galwater/galethanol have been
reported when using hybrid poplar (Philips et al., 2007). Because of these high cooling
needs, some authors have supported the use of air-cooling technologies to replace part of
the cooling water (Philips etal., 2007). By adding this technology to the process energy
optimization presented earlier, it is possible to reduce cooling-water use to achieve a total
freshwater consumption of 1.8galwater/galethanol. This value also accounts for the produc-
tion of a significant amount of hydrogen. In Figure 10.6, shown later in the chapter, the
water consumption for the production of ethanol alone is presented, revealing a value of
only 0.36gal/gal when all the water sources within the process are treated and reused.
(Martn etal., 2010b) There is no water discharge because the large amount of water circu-
lating within the process enables enough dilution of the TDS to reuse the stream.
10.3.2.2Hydrolysis
Another possible route to produce ethanol from lignocellulosic raw material is hydrolysis
of the biomass. To pretreat switchgrass to expose the hemicelluloses and cellulose for fur-
ther treatment, two methods have been found to be competitive for industrial ethanol
production due to their high efficiency in liberating cellulose and hemicelluloses from the
plant matrix: (1) dilute acid (H2SO4) pretreatment (Schell etal., 2003; Aden, 2009; Piccolo
and Bezzo, 2009; Zhang et al., 2009) and (2) ammonia fiber explosion (AFEX) (Sun and
Cheng, 2002; Alizadeh et al., 2005; Murnen et al., 2007). Martn and Grossmann (2010a)
proposed an optimal conceptual design for ethanol production by hydrolysis which
involved solving a superstructure that accommodates both pretreatment alternatives
(AFEX and dilute acid) together with biomass hydrolysis, sugar fermentation, and four
ethanol dehydration technologies (rectification, adsorption using corn grits, molecular
sieves, and pervaporation). According to the MINLP solution, the optimal flowsheet
includes dilute-acid pretreatment, which is cheaper and more environmentally friendly
than the other options because it consumes less energy and requires less cooling water.
Once the physical structure of the switchgrass is broken down to enable contact between
the polymers and the enzymes, hydrolysis of the polymeric sugars takes place. This pro-
cess is carried out in stirred-tank reactors at 50C where the accessible cellulose and hemi-
celluloses are broken down into fermentable sugars (Gregg etal., 1995; Wooley etal., 1999;
Hamelink etal., 2005; Piccolo and Bezzo, 2009; Zhang etal., 2009). The sugars, mainly glu-
cose and xylose, are fermented in water into ethanol. The reactions are different in terms
of yield and velocity. The optimal temperature is 38C, so that both are fermented at the
same time. A number of different products are obtained together with ethanol, such as
different acid products of the metabolic paths of the microorganisms used (Z. mobilis bac-
terium) (Wooley etal., 1999; Zhang etal., 2009; Piccolo and Bezzo, 2009). The purification
stages consist of the removal of solids, lignin, and cells from the liquid slurry coming out
of the fermentor. The lignin is used to obtain energy for the process. Finally, ethanol is
dehydrated by means of a beer column followed by molecular sieves to achieve fuel-grade
quality. Next, heat integration is performed. Figure 10.4 shows the flowsheet as developed
by Martn and Grossmann (2010a), and Figure 10.5 presents the energy consumption and
cooling needs of the process. The production cost is $0.80/gal.
The production of ethanol from hydrolysis of switchgrass is a gentler process than gasifi-
cation in terms of operating pressures and temperatures resulting in cooling requirements
less than half those for the thermochemical process (Figure 10.5). However, the lower tem-
peratures prevent the extensive use of air cooling to replace water as a cooling agent. The
design of the optimal water network (Martn et al., 2011b) reveals a total freshwater con-
sumption of 1.66galwater/galethanol (see Figure 10.6) and a wastewater discharge of 0.52galwater/
galethanol because the lower flowrates in the water network do not allow TDS dilution and the
high cost of removing TDS results in this water being discharged instead of treated.
Solids handling
Pretreatment Dilute acid treatment Hydrolysis Fermentation Solids separation

Liquid
neutralization
Lignin
Gypsum
Fuel ethanol Molecular sieves Beer column
FIGURE 10.4
Hydrolysis-based production process for ethanol from switchgrass. (Martn, M. and Grossmann, I.E. 2010a.
AIChE Journal doi: 10.1002/aic.12735. With permission.)
100,000
Energy (kW) Cooling (kW)
80,000
60,000
40,000
Energy (kW)
20,000
20,000
40,000
60,000
Corn Thermochem Thermo-bio Hydrolisys Thermo NREL NREL
chem(b) hydrolisys thermochem
FIGURE 10.5
Energy consumption and cooling requirements for ethanol production processes. (Martn, M., Ahmetovic, E.,
and Grossmann, I.E. 2011c. Industrial & Engineering Chemistry Research 49(17): 79727982. With permission.)
3
Water consumption Water discharge
2.5
2
gal Water/gal EtOH
1.5
0.5
0
Corn Thermochem Thermo-bio Hydrolisys NREL NREL Gasoline
hydrolisys thermochem
FIGURE 10.6
Water consumption of ethanol production processes. (M. Martn. E. Ahmetovic, IE. Grossmann. Ind. Eng. Chem
Res. 50 (7), pp. 37053721, 2011. With permission.)
10.3.2.3FischerTropsch-Diesel
Not only bioethanol can be produced from lignocellulosic materials, but also diesel or
hydrogen. The history of FT synthesis can be traced back to the beginning of the 20th cen-
tury, when in 1902 Sabatier and Senderens discovered that CO could be hydrogenated over
Co, Fe, and Ni to methane. Later, in 1925, Franz Fischer, founding director of the Kaiser
Wilhelm Institute of Coal Research in Mlheim an der Ruhr, and Hans Tropsch reported
synthesis of hydrocarbon liquids and solid paraffins on CoFe catalyst under mild
c onditions of 250300C. FT technology was extensively developed and commercialized in

Germany d uring World War II when that country was denied access to petroleum-rich
regions of the world. Likewise, when South Africa faced a world oil embargo during their
era of apartheid, it used FT technology to sustain its national economy. FT liquids can be
refined to various proportions of renewable (green) gasoline, diesel fuel, and aviation fuel
depending on process conditions. Depending on the types and quantities of FT products
desired, either low- (200240C) or high-temperature (300350C) synthesis at pressures
ranging from 10 to 40bar is used with either cobalt- or iron-based catalysts (Brown and
Wright, 2009).
Martn and Grossmann (2010c) proposed a superstructure which embeds various alter-
native technologies for the optimization of biodiesel production from switchgrass. The
process starts with gasification of the biomass. Two different alternatives are evaluated,
direct and indirect gasification. The gas obtained is reformed and cleaned up, and its com-
position may be adjusted in terms of the CO/H2 ratio for the optimal production of the
diesel fraction using up to three possible technologies (bypass, PSA, and water shift). Next,
the removal of CO2 and H2S is performed by means of two cleanup processes, absorption
in ethylamines and PSA. Then the FT reaction is carried out and the products separated.
Hydrocracking of the heavy products is also considered to increase the yield toward die-
sel. Again, the number of alternative processes and tradeoffs makes it difficult to propose
a flowsheet without the help of a systematic approach. The system optimization is formu-
lated as an MINLP problem where short-cut models, reduced-order models, design equa-
tions, and mass and energy balances are used for the various units involved in the
production process, with special focus on the FT reactor, the hydrocracking unit, and the
CO/H2 adjustment unit. The MINLP is solved for optimal production of the biodiesel frac-
tion while minimizing energy consumption. Energy integration and an economic evalua-
tion are also performed.
The optimal solution requires the use of indirect gasification followed by steam reform-
ing. The CO/H2 ratio is maintained at the value obtained after gas reforming because there
is a reasonable excess of hydrogen, while the temperature is adjusted at the FT reactor and
at the hydrocracker to increase biodiesel production, resulting in a promising production
cost of $0.71/gal. Figure 10.7 shows the optimal flowsheet.
MEA
Switchgrass 30 bar
29C
Pretreatment Indirect gasification Steam reforming Scrub. HBC removal
1.6 bar 1.2 bar 4.5 bar

890C 40C 25C PSA CO2 removal
4.5 bar
Flue gas 25C
Catalytic
FT-diesel Distillation 30 bar
201C
Hydrocracking = 0.90
350C H2/CO = 1.4
FIGURE 10.7
Optimal flowsheet for the production of FT diesel. (Martn, M. and Grossmann, I.E. 2011b. Industrial &
Engineering Chemistry Research 50(23): 1348513499. With permission.)
10.3.2.4 Other Bioproducts

Figure 10.8 shows a summary of the products that can also be obtained from lignocellulosic
biomass. The syngas obtained from biomass is an interesting building block for a number of
chemicals. This chapter does not describe the production of high-value products such as fine
chemicals or polymers, but rather focuses on hydrogen, a valuable fuel for fuel-cell-powered
vehicles or an intermediate needed for the production of petroleum-based chemicals.
Hydrogen can also be produced by generating syngas by gasification and then cleaning
up the gas and shifting the energy value of the CO to H2 using the watergas shift reac-
tion (WGSR). To reduce the production cost, a new reactor design which is capable of
separating the hydrogen produced through a permeable membrane has been proposed
(Doong etal., 2005; Fu and Wu, 2007; Ji etal., 2009; Adrover etal., 2009; Sa etal., 2009).
Martn and Grossmann (2011b) coupled the newly developed reactor design using mem-
brane technology (Ji etal., 2009) with two different gasification technologies, direct and
indirect gasification, and two reforming modes, partial oxidation and steam reforming,
creating a superstructure in the form of an MINLP. The operating conditions in the gasifi-
ers and at the WGSR are optimized for hydrogen production in each of the four alternative
technologies. Next, energy is integrated.
Finally, an economic evaluation is performed to determine the production cost. It turns
out that indirect gasification with steam reforming is the preferred technology, providing
higher production yields (0.13kg/kgdryBiomass) than those reported in the literature for
hydrogen from natural gas and at a lower and promising production cost of $0.68/kg.
10.3.3 Oil-Based Biofuels

Many researchers have concluded that vegetable oils hold promise as alternative fuels for
diesel engines (Scholl and Sorenson, 1993; Wagner etal., 1984). However, using raw vege-
table oils for diesel engines can cause numerous engine-related problems (Korus et al.,
1982). The increased viscosity, low volatility, and poor cold-flow properties of vegetable
oils lead to severe engine deposits, injector coking, and piston-ring sticking (Pestes and
Stanislao, 1984; Perkins et al., 1991). Therefore, research has focused on developing
Fuels and energy
Biomass
Fine chemicals
and
polymers
FIGURE 10.8
Biorefinery. (Martn, M. and Grossmann, I.E. 2010d. Industrial & Engineering Chemistry Research. With permission.)
t ransformation products by means such as pyrolysis, microemulsion, and transesterifica-

tion. The transesterification process has been used most widely. It removes glycerol from
the triglycerides and replaces it with radicals from the alcohol used for the conversion
process (Kusy, 1982). This process decreases the fuels viscosity, but maintains the cetane
number and heating value. The monoesters produced bytransesterifying vegetable oils
with alcohol are known as biodiesel (Canakci and Gerpen, 1999; Fukuda etal., 2001).
10.3.3.1 First-Generation Biodiesel

Biodiesel is obtained using vegetable oils such as sunflower, cottonseed oil, rapeseed oil,
soybean oil, palm oil, peanut oil, and canola oil as raw materials (Levelton Engineering Ltd,
2002; Shahid and Jamal, 2008). Their use is distributed across the globe depending on the
production capabilities of different countries. For example, canola is the preferred oil in
Canada, cottonseed oil is abundantly produced in Pakistan, palm oil is very frequently used
in Malaysia; meanwhile, soybeans remain the largest oilseed crop produced. Biodiesel can
be twice as expensive as crude-based diesel (biodiesel from soybeans is estimated to cost
approximately $2.00$2.50/gal), but the capital investment for a biodiesel plant is far lower
(Tao and Aden, 2009). However, the competition of these technologies with the food chain
and the cost of the raw material are directing the focus to the use of alternative sources of oil.
10.3.3.2 Cooking-Oil-Based Diesel

Among oils, waste cooking oil is a promising alternative to vegetable oil for biodiesel pro-
duction because it is much less expensive than pure vegetable oil. So far, waste oils have
been sold commercially as animal feed. However, since 2002, the European Union has
enforced a ban on feeding these mixtures to animals because many harmful compounds
are formed during frying. Obviously, the conditions used for frying (temperatures of
160200C) cause major physical and chemical changes to the oil, which differ from oil to
oil depending on the composition of each. In general, three types of reactions occur during
frying: thermolytic, oxidative, and hydrolytic. As a result, some of the common physical
changes observed in vegetable oil are: (i) increase in viscosity, (ii) increase in specific heat,
(iii) change in surface tension, (iv) change in color, and (v) increase in the tendency of fat to
foam. As a combined result of all these chemical reactions, many undesirable compounds
are formed, increasing the polar fraction and preventing the use of waste cooking oil as an
additive to feed mixtures for domestic animals because it could result in the reintroduc-
tion of harmful compounds back into the food chain through animal meat (Kulkarni and
Dalai, 2006). Hence, waste cooking oil must be disposed of safely or be used in a way that
is not harmful to human beings.
The quantity of waste cooking oil generated per year is huge (Kulkarni and Dalai, 2006).
The disposal of waste cooking oil is a problem because disposal methods may contaminate
the water. Many developed countries have set policies that penalize the disposal of waste oil
through water drainage systems. Therefore, the production of biodiesel from waste cooking
oil becomes a better way to reuse the oil and to dispose of it efficiently and economically
(Felizardo etal., 2006; Phan and Phan, 2008; Banerjee and Chakraborty, 2009). However, the
high demand for diesel fuel and the limited availability of waste cooking oil (Wiltsee, 1998;
Zhang etal., 2003; Pugazhvadivu and Jeyachandran, 2005; Kulkarni and Dalai 2006) indicate
that biodiesel from cooking oil cannot replace diesel fuel, but can contribute to reducing
dependency on crude-based diesel. The properties of biodiesel from waste cooking oils
would be largely dependent on the physiochemical properties of these feedstocks.
10.3.3.3 Production Process of Biodiesel from Oil

The transesterification reaction depends on several parameters such as reaction tempera-
ture and pressure, reaction time, rate of agitation, type of alcohol used, molar ratio of alco-
hol to oil, type and concentration of catalyst used, and concentrations of moisture and free
fatty acids (FFA) in the feed oil. Methanol is the alcohol most commonly used because of its
low price, but ethanol has also been tested. There are four alternatives for performing the
transesterification of the oil toward biodiesel depending on the catalysts used: acid-cata-
lyzed, alkali-catalyzed, enzymatic, and no catalyst under supercritical conditions. The
alkali-catalyzed reaction is limited because of the formation of soaps between the catalyst
and the FFA and the negative effect of the presence of water in the oil which favors saponi-
fication, although the reaction is quick. The acid-catalyzed reaction is not limited by
thepurity of the reactants, but by the reaction time, which is approximately four days. The
enzyme-catalyzed reaction is insensitive to water and FFA, and it is easier to purify theprod-
ucts. However, the catalyst is more expensive, and its conversion rate is still lower than that
of the previous two processes. Finally, it is possible to transesterify oil using supercritical
methanol. Although the yield of methyl ester is high, the molar ratio of methanol to oil is
extremely high (1:42) and the operating conditions are extreme (350C and 45MPa).
(Tomasevic and Siler-Marinkovic, 2003; Kulkarni and Dalai, 2006; Meher etal., 2006; Zheng
etal., 2006; Sharma etal., 2008; Marchetti and Errazu, 2008; Utla and Kocak, 2008).
A number of authors have developed and evaluated production processes based on
those technologies from both technical and economic points of view using a simulation
approach. These studies have revealed that the acid-catalyzed process is preferable because
it is less affected by impurities in the raw material, thus reducing the need for purification
pretreatment stages. Recently, the use of heterogeneous catalyzed processes (enzymatic,
basic, or acid-based) or supercritical-fluid-based processes is gaining support because of
the reduction in the number of separation stages, resulting in a very competitive price
(Zhang etal., 2003a,b; Hass, 2006; Harding etal., 2007; West etal., 2008; Marchetti, 2008;
Apostolakou etal., 2009; Diaz etal., 2009; Glisic, 2009; Santana etal., 2009; Sotof etal., 2010;
van Kasteren and Nisworo, 2007). Recently, Martn and Grossmann (2010d) have opti-
mized the production of biodiesel in terms of technology (homogeneous alkali and acid-
catalyzed, heterogeneous enzymatic, or basic and noncatalyzed under supercritical
conditions) and operating conditions using surface-response models for the reactors. The
model was formulated as a GDP in which each of the flowsheets was simultaneously opti-
mized and heat-integrated. The result is that for cooking oil, the heterogeneous catalyzed
reaction is the best process, yielding a production price of $0.66/gal with an energy con-
sumption of 1.94MJ/gal (half the best estimates) and a water consumption of 0.33gal/gal
of biodiesel, almost one-third of values reported in the literature (Pate etal., 2007).
A by-product of the transesterification of oil is glycerol. Because of the expected
increase in the production of biodiesel, research has focused on the use of glycerol to
produce different value-added chemicals such as hydrogen (Cortright etal., 2002; Deluga
etal., 2004; Davda etal., 2005; Hashaikeh etal., 2006; Dauenhauer etal., 2006; Byrd etal.,
2008; Slinn, 2008; Adhikari, 2009); 1,3-propanediol which can be used in composites,
adhesives, laminates, powders, UV-cured coatings, moldings, novel aliphatic polyesters,
copolyesters, solvents, antifreeze, and for other end uses (Shell Chemicals, 2006); 1,2 pro-
panediol, which is a major commodity chemical with an annual production of over 1
billion pounds in the United States (Dasari etal., 2005); dihydroxyacetone, used in the
cosmetics industries as a tanning agent (Bauer etal., 2005); succinic acid, which can be
used for the manufacture of synthetic resins and biodegradable polymers and as an
intermediate for chemical synthesis (Zeikus, 1980); and polyglycerol esters which are
used as antifogging and antistatic additives, lubricants, and plasticizers (Clacens etal.,
2002), as well as polyesters and polyhydroxyalkonates (Pachauri and He, 2006).
10.3.4 Algae-Based Biofuels

Microalgae are also a biomass source with great potential. Microalgal oils are now believed
to be a promising feedstock for biodiesel production because the oil they generate has a
fatty-acid composition similar to that of vegetable oils (Zhang etal., 2009; Mata etal., 2010).
To produce a sufficient amount of oil, microalgae must be carefully selected so that they
are capable of producing large quantities of lipids while being tolerant to fluctuations in
operating conditions. Algae convert sunlight, saline water, nutrients, and CO2 into pro-
teins, carbohydrates, and lipids, with a growth rate that doubles their biomass up to five
times a day. Later, growth is stopped by nutrient limitations, and then only lipids are pro-
duced. Algae can grow not only on normal carbon sources, such as glucose, fructose, and
other sugars, but also on wastes from the agriculture and food industries, and using saline
water or wastewater, thus lowering the cost of microalgal oil while providing a good water
treatment to remove NH +2 , NO 3 , and PO 3
4 (Mata etal., 2010). Next, the algae are harvested
to eliminate the water that accompanies them, which can be recycled, using flotation, set-
tling (helped by flocculation), centrifugation, or filtration. Finally, the oil is extracted and
either transesterified (using the same processes as for any other oil), or catalytically con-
verted into gasoline (Johnson and Sprage, 1987).
The main problem with producing biodiesel from algae is that to make it commercially
viable, the algae need a concentrated and plentiful CO2 source, which is not available in
sufficient quantities, and furthermore it is necessary to reduce the high harvesting costs
(Pokoo-Aikins etal., 2009). The current microalgae oil price is $0.25/lb (http://www.soley.
cn/oil-trade.html), but it could be as low as $0.07/lb (Pokoo-Aikins etal., 2009). However,
certain processes for the production of ethanol, hydrogen, or FT diesel by gasification gen-
erate significant amounts of CO2 that could be used in this process. Furthermore, new
technologies are under development to reduce the harvesting costs of microalgae
(Univenture, 2009). The potential yield of biofuel from microalgae is one or two orders of
magnitude higher than for any other crop and five times greater than the best yield for
ethanol, as can be seen Figure 10.9 (Oak Ridge NL, 2005; Fulton, 2006; Christi, 2007; UNFAO,
2008). The use of microalgae as feedstock for the production of biodiesel has been spon-
sored by the U.S. Department of Energy. It is reported that microalgae can be produced
using salt water (eliminating the problem of water usage), and that with 13 million acres,
approximately 25% of the cropland currently used in the United States, it would be pos-
sible to meet U.S. diesel needs. Furthermore, the production of diesel from algae could be
achieved at a lower cost than the current price of diesel (Pimentel and Patzek, 2005). In a
study by Martn and Grossmann (2010d), it was demonstrated that oil from algae can be
produced at $0.06/lb as long as new technology released by Univenture Inc. (2009) is
implemented. Next, a GDP similar to the one proposed for the production of biodiesel
from cooking oil has been solved to determine the best production process among the five
alternatives mentioned earlier, homogeneous acid- or alkali-catalyzed, heterogeneous
enzymatic, basic, or noncatalyzed under supercritical conditions, simultaneously optimiz-
ing and with heat integration for each process. For this type of oil, the best process is the
alkali-catalyzed process, with a production cost of $0.42/gal, requiring 1.94MJ/gal of
energy and 0.60gal/gal of water. The second-best process is fairly close, only $0.02/gal
more expensive, and is the heterogeneous basic catalyzed process.
Ethanol Biodiesel 5020

5000
4000
Gallons per acre
3000
2000
1150
1000 585 483 506
401 213 140
59 110 170
0
ha
l)
a)
ss
)
S)
S)
e
or
ed
sia
na
ga
zi
di
ra
(U
(U
op
st
se
ra
hi
al
ay
(In
hg
Ca
tr
ro
n
(B
pe
n
(C
al
itc
r
ea
Ja
ic
ne
(M
Co
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ne
n
yb
Sw
M
r
ca
ca
Co
lm
So
ar
ar
pa
g
g
Su
Su
il
O
FIGURE 10.9
Yield of ethanol and diesel from different raw materials. (Martn, M. and Grossmann, I.E. 2010d. Industrial &
Engineering Chemistry Research. With permission.)
The potential of microalgae is not limited to the oil they can generate, but they can also be
used to obtain ethanol by fermenting the starch and cellulose contained in them, hydrogen
by gasification or biological conversion, liquid fuels by pyrolysis or thermal liquefaction,
methane by digestion, or other high-value products (Li etal., 2008; Rsch, 2009; Brennan
and Owende, 2010). It is also possible to use the oil for biodiesel production while the resi-
dues are used to obtain ethanol by fermentation (Bush and Hall, 2006; Chen etal., 2009).
10.4 Concluding Remarks

Strong competition in the energy market requires alternative fuels based on biomass (e.g.,
bioethanol, biodiesel) to be produced in an efficient and sustainable way. Mathematical
optimization techniques together with conceptual design have been traditionally used in
the petrochemical industry to improve the performance and operation of processes.
Therefore, as has been shown in this chapter, process systems engineering tools can be
effectively used for the optimal design of biofuel processes. Sustainable designs must be
optimized in terms of energy and freshwater consumption as the two most important
indices for efficient performance. Mathematical programming techniques, process synthe-
sis concepts, and newly developed technologies have been used to develop optimal pro-
cesses for the production of bioethanol, biodiesel, and hydrogen. These designs must of
course be validated with more detailed simulations and pilot-plant data.
As for future work, one logical step is to use the information obtained from the models
reported in this chapter in the design and operation of biorefineries such as that illus-
trated in Figure 10.10, which are capable of producing a wide variety of products from
fuels to chemicals or even energy (Bridgwater, 2003; Kamm and Kamm, 2007; Rsch etal.,
2009). This line of work has begun to be addressed by several authors (Sammons etal.,
2006, 2008; Dimian, 2007; Kokossis and Yang, 2010; Ng, 2010; Mansoornejad etal., 2010).
Biomass
Cereals/ Sugar Grass/

Wood corn cane Seeds Alfalfa Microalgae
Lignin Carbohydrates Fats Proteins
Amino acids
Enzymes
Cellulose Starch Saccharose Oil
Energy Xylose Glucose Biodiesel

Acetic acid
Syngas Lactic acid

Ethanol
FT-Diesel Acrylic acid

Ethene
Gasoline H2 Polymers
Methanol
Formaldehyde
MTBE DME
FIGURE 10.10
Network of raw materials and processes for a biorefinery.
However, there is scope for including concepts from enterprise-wise optimization

(Grossmann, 2005; Varma et al., 2007) such as deterministic multiperiod mixed-integer
linear design models in which biorefineries are treated as process networks (Sahinidis
and Grossmann, 1989; Norton and Grossmann, 1994; Wassick, 2009). Furthermore, to
address uncertainties in the supplies of and demands for raw materials and products,
stochastic programming models for process network planning can also be developed
(Pistikopoulos, 1995; Liu and Sahinidis, 1995; Ierapetritou etal., 1996; Cheng etal., 2003;
Barbaro and Bagajewicz, 2004; Jung etal., 2008). Finally, these process network models
can be coupled with inventory models to determine optimal safe inventory levels (Zipkin,
2000; You and Grossmann, 2008). This, however, requires the solution of nonconvex
MINLP problems (You and Grossmann, 2010).
Acknowledgments
The authors gratefully acknowledge NSF Grant CBET0966524 and the Center for
Advanced Process Decision-making at Carnegie-Mellon University. Dr. M. Martin grate-
fully acknowledges the financial support from the Ministry of Education and Science of
Spain and the Fulbright Commission which provided an MICINNFulbright postdoctoral

fellowship.
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10

Optimal Synthesis of Sustainable Biorefineries

Mariano Martn and Ignacio E. Grossmann

optimum solution is selected. The second is the formulation of a mathematical program,

10.2 History of Biofuel Production Processes

10.3Synthesis of Biofuel Production Processes: Energy and Water

Pretreatment Drying zone

Pyrolysis Syngas Methanol

Gas The grate

Washing water Superheated steam Enzyme Enzyme

Src2 Src4 Src5 Src6

Snk9 Spl7 95%

Dry DDGS HX10 Solids 10.8%

Proteins Flot Adsorbent:

Spl3 Spl2 Mix5 Ads1 Spl5 Mix7 Snk5

HX8 Dry air

HX7 Humid air

10.3.2 Lignocellulose-Based Biofuels

second-generation bioethanol is based on lignocellulosic materials which offer yields

Ethanol Direct distillation seq. Catalytic

Pretreatment Dilute acid treatment Hydrolysis Fermentation Solids separation

Fuel ethanol Molecular sieves Beer column

c onditions of 250300C. FT technology was extensively developed and commercialized in

1.6 bar 1.2 bar 4.5 bar

10.3.2.4 Other Bioproducts

10.3.3 Oil-Based Biofuels

Fuels and energy

t ransformation products by means such as pyrolysis, microemulsion, and transesterifica-

10.3.3.1 First-Generation Biodiesel

10.3.3.2 Cooking-Oil-Based Diesel

10.3.3.3 Production Process of Biodiesel from Oil

10.3.4 Algae-Based Biofuels

Ethanol Biodiesel 5020

10.4 Concluding Remarks

Cereals/ Sugar Grass/

Lignin Carbohydrates Fats Proteins

Energy Xylose Glucose Biodiesel

Syngas Lactic acid

FT-Diesel Acrylic acid

However, there is scope for including concepts from enterprise-wise optimization

Spain and the Fulbright Commission which provided an MICINNFulbright postdoctoral

Papoulias, S. and Grossmann, I. 1983. A structural optimization approach in process synthesis. 2.

Food Sciences, South China University of Technology. http://www.paper.edu.cn/en/paper.

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10.3Synthesis of Biofuel Production Processes: Energy and Water