PROCESS SIMULATION AND OPTIMIZATION FOR PRODUCTION OF FUEL ETHANOL

FROM LIGNOCELLULOSIC BIOMASS

Hee-young Kim, Jin-kuk Ha, Euy-soo Lee

Department of Chemical and Biochemical Engineering, Dongguk University,

Jung-gu, Seoul, 100- 715, Korea
E-mail address : eslee@dgu.edu

Abstract: Fuel ethanol (bioethanol) has economic and environmental benefits as one of the
most important renewable fuels. Lignocellulosic biomass is the most promising feedstock for
producing bioethanol due to its global availability and to the energy gain. Present bioethanol
plant has two-step hydrolysis and high energy required separation: biomass prehydrolysis is
decrystallization for hydrolysis, and hydrolysis step is that gelatin-like converts
monosaccharides like glucose and xylose. After fermentation step, bioethanol is necessary a
separation step using azeotropic distillation. These steps have some disadvantages: before
fermentation step, two-step is required much time and energy. Moreover, azeotropic
distillation is used energy overconsumption. In this work, several process configurations for
fuel ethanol production from lignocellulosic biomass were studied through process
simulation using process simulation program. Simultaneous hydrolysis and fermentation was
one-step process with high concentration H2SO4, which was recycled over 99% using
Simulated Moving Bed (SMB). Instead of azeotropic distillation, pervaporation was used as
dehydration method for production of 99.5% ethanol. In addition, energy balance was
estimated using the results from the simulation and literature data. The flowsheet variants
were analyzed from the energy point of view utilizing as comparison criterion the energy
consumption needed from 1kg biomass. Simultaneous prefermentation process with acid
showed the best results decreasing energy consumption more 20%. In addition, a net ethanol
production of 266g/kg biomass was calculated, 26% increased amount of bioethanol
production. The result showed that there is a possibility of new bioethanol plant using high
concentration acid.

Keywords: Bioetanol, Fuel ethanol, Optimization, Simulation, SMB, Lignocellulosic

biomass

1. INTRODUCTION

Ethanol derived from biomass is one of the most important renewable fuels contributin to possible solutions of
negative environmental impacts. The conversion of biomass into biofuels represents an important option for both the
exploitation of an alternative source of energy and the reduction of polluting gases, mainly carbon dioxide. The most
important biofuel is the fuel ethanol, which can be utilized as an oxygenate of gasoline. Also, ethanol in gasoline
may result in decreased urban air quality, and be associated with substantive risks to water resources and
biodiversity. Fuel ethanol is obtained from sugarcane in some tropical countries like Brazil and India. Beet molasses
are used in some European countries like France. The main feedstock in the US is starch from corn.

The so-called lignocellulosic biomass includes agricultural residues, forestry wastes, municipal solid waste,
agroindustrial wastes, and food processing and other industrial wastes. The importance of lignocellulosic biomass as
ethanol production feedstock is evident. The lignocellulosic complex is the most abundant carbohydrate and it is
present in those profuse materials like sugarcane bagasse, wood chips, sawdust, paper residues and grass. Their use
allows either the production of a valuable biofuel and the utilization of a wide range of residues of domestic,
agricultural and industrial activities. Therefore, the technologies for fuel ethanol production have cost-effective
processes.
 For this reason, the ethanol production costs of from biomass are higher than those ones from corn or sugarcane. It
determined that the production cost of 1L of ethanol obtained from corn was of US$0.88 whereas the production
cost for biomass ethanol was of US$1.50(McAloon et al., 2000). Today, many efforts have been made lowering
these costs as simultaneous saccharification and fermentation (SSF), reaction–reaction processes.

Therefore, the development of cost-effective technologies for fuel ethanol production is a priority for universities
and private firms, and even for different governments. Due to the large amount of existing and not completely
developed technologies for the production of ethanol, the process application engineering tools is required. Process
engineering includes the design of new innovative process configurations aimed at reducing ethanol production
costs. On the other hand, the development of environmentally friendly technologies for bioethanol production can be
carried out utilizing different design approaches.

This work was to investigate different flowsheet combinations for the biotechnological production of fuel ethanol
from lignocellulosic biomass. Through process simulation, it is analyzed them from the energy viewpoint and from
their integration possibilities. For the analysis, the objective function was the energy consumption as the thermal and
electric energy demanded during the production of ethanol from biomass and the amount of MJ required for the
ethanol production to 1kg biomass. In addition, this work is aimed to the preliminary estimation of the energy
balance for the ethanol production process from lignocellulosic biomass based on the results obtained during the
simulation of the best flowsheet configuration.

2. PROCESS CONFIGURATION

The lignocellulosic biomass is made up from very complex carbohydrate polymers: cellulose, hemicellulose and
lignin. For conversion to ethanol, a complex pretreatment process to transform the polymers into fermentable sugars
is required. Obtained sugars are converted into ethanol by yeasts or bacteria and dilute aqueous solutions of ethanol.
Overall fuel ethanol production from lignocellulosic biomass includes five main steps: biomass pretreatment,
cellulose hydrolysis, fermentation, separation and effluent treatment (see Fig. 1). The sequential configuration
employed to obtain cellulosic ethanol implies that the solid fraction of pretreated lignocellulosic material undergoes
hydrolysis (saccharification); this fraction contains the cellulose in an accessible to acids or enzymes form. Once
hydrolysis is completed, the cellulose hydrolyzate is fermented and converted into ethanol by yeasts. This process is
called separate hydrolysis and fermentation (SHF). SHF is one of the configurations that has been tested more
extensively. Pentose fermentation is accomplished in an independent unit.

The need of separate fermentations is due to the fact that hexoses fermentation is dependent on fentoses
fermentation. Moreover, the former microorganisms are more sensitive to the inhibitors and to the produced ethanol.
For this reason, the hemicellulose hydrolyzate resulting from pretreatment should be detoxified. If the fermentation
of the hemicelluloses and cellulose hydrolyzates is carried out in a separate way, less liquid volumes of hydrolyzate
have to be detoxified.

All these steps have been investigated with intensity on last years, and many improved technologies have been
proposed. In particular, some schemas involving reaction–reaction integration processes are being studied. Among
these processes, SSF has been proposed for fuel alcohol production. This process implies the realization of cellulose
hydrolysis and hexose fermentation in the same vessel. The main advantage of this configuration is to avoid the
inhibition of cellulases by glucose. In this way, the glucose produced by enzymatic hydrolysis is immediately
consumed by the yeast that converts it into ethanol. If microorganisms capable of assimilating pentoses and hexoses
are used, the socalled SSCF process can be implemented for the production of bioethanol from biomass. In this case,
both fractions of the hemicellulose hydrolyzate are unified and utilized for the conversion of their soluble sugars
into ethanol.

The information was used for selecting different improvement options in each step. Thus, two types of
pretreatment and hydrolysis schemas (with deviation of the liquid fraction of hemicellulose hydrolyzate or without
it), three types of fermentation processes (separate hexose and pentose fermentation, SSF or SSCF), two types of
separation technologies (azeotropic distillation or pervaporation) and three types of effluent treatment schemas
(without recycling of water or with two alternatives for recycling water), were selected for the subsequent
simulation. The selection procedure are more improvements of the process and the viability of their implementation.
Fig. 1. Generic block diagram of fuel ethanol production from lignocellulosic biomass. Possibilities for reaction–
reaction integration are shown inside the shaded boxes: CF, co-fermentation; SSF, simultaneous saccharification
and fermentation; SSCF, simultaneous saccharification and co-fermentation. Main stream components: C,
cellulose; H, hemicellulose; L, lignin; Cel, cellulases; G, glucose; P, pentoses; I, inhibitors; EtOH, ethanol.

Table 1 Main process data for the base case

Feature Value Feture Value
Feedstock Hardwood chips Separation 1
composition(w/w) Cellulose 45.5%, No. of columns 20
Hemicellulose 28.5%, Pressure of columns 1.79 atm
Lignin 15.3%, moisture
10%
Feed flowrate 1kg
Pretreatment Separation 2
Agent Dilute acetic acid No. of columns 15
Temperature 190 ℃ Pressure of columns 1.58 atm
Pressure 12.2 atm
Hemicellulose conversion 75% Convent. distillation
Fermentation No. of columns 20
Pentose bioagent Candida shehatae Pressure of columns 2.1 atm
Hexose bioagent S. cerevisiae Feed columns 13 tray
Temperature 30℃
Fig. 2. Simplified flowsheet(base case) using NRTL model for liquid phase, Hayden-O’Connell equation for gas
phase: 1, pretreatment, 2, pentose fermentation, 3, hexose fermentation, 4, mixer, 5, separation 1, 6, separation 2, 7,
convention distillation.

After this selection, a base case configuration of the flowsheet for ethanol production from biomass was defined in
Table 1.For the simulation of this base case, process data from above-cited sources were used. The corresponding
flowsheet of base case is shown in Fig. 2. The goal of given process is the production of anhydrous ethanol to be
used as an oxygenate of the gasoline.

For configuration process, the variant are treatment process (with prehydrolysis and hydrolysis step) , processing
material like acid, and separation technology that are summarized in Table 2 and Fig. 3. In addition to this process, it
is proposed the use of condensed water and acid prom using simulated moving bed (SMB).

3. PROCESS SIMULATION PROCUDERE

The different flowsheet configurations were simulated using PRO/II(Simulation Science Inc.,USA). This software
enables getting information about the behaviour of distillation processes and the definition of their most important
specifications through short-cut methods. The simulations utilized the NRTL model for the calculations of activities
of the liquid phase and the Hayden–O’Connell equation of state for the gas phase. The rigorous calculation of the
operation conditions in the distillation columns was developed using the RadFrac module based on the inside-out
equilibrium method that utilizes MESH equations.
The amount of feedstock was the same for each cases and composition of woodchips too. The objective function
was the energy consumption defined as the thermal and electric energy demanded during the production of ethanol
from biomass.
Bioagent like yeast was calculated through biochemical reactions recognizing reactor in process simulation. In
configuration process, SSF was selected for fermentation.
 Table 2 Main process data for configuration case

Feature Value Feture Value

Feedstock Hardwood chips Separation 1(SMB)
composition(w/w) Cellulose 45.5%, Type One-ST-Valve-Per-Column
Hemicellulose 28.5%, (1ST1C)
Lignin 15.3%, moisture Valve developed by Valco Inc
10% (Houston, TX)
Feed flowrate 1kg No. of zones 4
Pretreatment Regenerator NaOH
Agent Strong sulphuric acid Temperature 65℃
Temperature 90 ℃ Acid concentration
Pressure 1 atm No. of columns 3
Acid ratio 1.25 Convent. distillation
Conversion 95% No. of columns 20
Fermentation Pressure of columns 2.1 atm
bioagent S. cerevisiae Feed columns 13 tray
Temperature 30℃ Pervaporation
Reaction time 24 hr Membrane 300
selectivity

Fig. 3. Simplified flowsheet for configuration case for ethanol production from lignocellulosic biomass
 Table 3 Comparison of some pretreatment and fermentation alternatives

Energy costs(percentage for

Flowsheet variant Ethanol yield(g/kg biomass) Unit energy costs
the base case)
Base case 197 49.91 100
Configuration case 266 43.04 86.24

Table 4 Ethanol yield for configuration case involving recycling of water and acid with the base case

Sugar concentration in Sugar concentration

Ethanol yield(g/kg
Flowsheet variant recycling water in recycling acid
biomass)
Glucose Xylose e Glucose Xylose
Base case - - - - 197
Configuration case 5.63 6.82 <0.001 <0.001 266

4. PROCESS RESULTS

The ethanol production process from lignocellulosic biomass requires steam, electricity and a cooling water supply.
Thermal energy in the form of steam is the main type of energy used in this process. Table 3 shows the ethanol yield
and unit thermal energy costs for the base case and other modification. The conversion of glucose into ethanol by
yeasts is performed simultaneously with the cellulose hydrolysis in order to increase fractional conversion of
cellulose by cellulases. In this case, the glucose is immediately consumed by the yeasts. This process is carried out
at 30℃ in a cascade of continuous reactors. It was showed that energy savings could be reached if the
lignocellulosic biomass is not split into two streams for carrying out two separate fermentation processes. Thus, the
thermal energy and the energy consumed for agitation and maintenance of the continuous regime in one train of
bioreactors. In Table 4, the fraction of the liquid stream from centrifuge that will be recycled to the process was
shown for the production of production ethyl alcohol (>99.5% w/w).
For the simulation of the water recovery step, the acid concentration distillation system was used to result recycling
90% (w/w) water. The SMB is added as separator for recycling acid more than 99% (w/w) .
In the separation step, configuration process used conventional distillation and pervaporation system for the
filtration for removal water in ethanol solution. The distilled head was direct to membrane to concentrate, more over
99.5% ethanol was product. The bottom fluid of membrane was recycled to the distillation resulting reduction of
expending of ethanol. In consequence, as the table 3, separation costs were reduced in 14% significantly.
Finally, amount of ethanol production in configuration case was increased about 35% using high concentration acid
process. It was result that was important to access the suitable process for the production of fuel ethanol.

5. CONCLUSION

For fuel ethanol production, the proposed procedures demonstrate to be a powerful tool when several options in
each process step must be assessed. Additionally, the contribution of each proposed modification can be evaluated in
terms of energy. The analysis of the bioethanol process shows that heat integration of distillation and rectification
gives the largest reduction of heat demand. But a considerable amount of heat is also necessary in the SMB and
saccharification section to convert much reactants.
The energy balance of the production process of biomass ethanol is outstanding compared with base case and
configuration. However, for biomass process, the performed analysis showed that limitations in the distillation step
and fermentation step, then technologies is necessary to set up pilot and industrial scale.
Further work will investigate the possibility to SMB optimization through changing valve sequence and location,
length of zones, and reaction time needing less energy.
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