White Paper

PRO/II Simulation of Bioethanol Production

Authors: Joseph McMullen, Larry Balcom

What’s Inside:
1. Abstract
2. Introduction
3. Overview of Solution
4. Implementation of Details
4.1. Hydrolysis Processes
4.2. Fermentation Processes
4.3. Glucose Fermentation
4.4. Xylose Fermentation
4.5. Separation Processes
5. Conclusions
6. Simulation Benefits
7. References
PRO/II Simulation of Bioethanol Production

1. Abstract
The production of biofuels has emerged as a worldwide market that is becoming increasingly important, drawing public & scientific
attention due in large part to the increased price of oil and the need for increased energy security. The use of biofuels is important to
reduce the reliance on non-renewable energy resources like oil and coal. Biofuels are important to serve future world energy needs
which necessitates that simulation software vendors work closely with the biofuel producers to make sure that the software can help
the biofuel plants perform at peak operating conditions. The production of biofuels can benefit from the recent advances in process
simulation software that allow for the efficient and optimal process design, regulatory compliance, and operational analysis of the
biofuels process. Computer simulation is an essential tool in the design and economic analysis of new bioethanol technologies. This
paper will discuss the use of simulation software in the simulation of a bioethanol process based on the United States Department
of Energy (DOE) Bioethanol Pilot Plant design (National Renewable Energy Laboratory. The DOE Bioethanol Pilot Plant, a tool for
commercialization. DOE/GO-102000-1114, September 2000).

2. Introduction
The production of biofuels has emerged as a worldwide market that is becoming increasingly important, drawing public and scientific
attention due in large part to the increased price of oil and the need for increased energy security. The use of biofuels is important to
reduce the reliance on non-renewable energy resources like oil and coal. Biofuels are important to serve future world energy needs
which necessitates that simulation software vendors work closely with the biofuel producers to make sure that the software can help
the biofuel plants perform at peak operating conditions. The production of biofuels can benefit from the recent advances in process
simulation software that allow for the efficient and optimal process design, regulatory compliance, and operational analysis of the
biofuels process.

Of the many tools that are available to facilitate biofuels production, simulation software is one of the most effective. Simulation
software gives engineers the ability to work with a process in the virtual world without the expense and time delays of testing it in
the real world. Simulation software tools help make the process as efficient as possible during the design phase and minimize its
environmental impact during operation. Recent enhancements to steady-state simulation software like SimSci-Esscor’s™ PRO/II®
enable the addition of custom unit operation calculations via a Microsoft Excel® spreadsheet. Since the development of the initial
proprietary correlations of the process is usually done in Excel, the use of the Excel unit operation allows the user to capitalize on the
initial correlations and reuse the work they have already done in Excel. This can model any proprietary or specialized process that
cannot be modeled using traditional unit operations.

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PRO/II Simulation of Bioethanol Production

Global production of biofuels is increasing to meet the increasing worldwide demand. The increased production is illustrated in
Figure 1. Production increased roughly 270% between 2004 and 2008 from 560 thousand barrels per day to over 1.5 million barrels
per day (U.S. Energy Information Administration. International Energy Statistics, Total Biofuels Production). The increase in biofuel
consumption is illustrated in Figure 2. Consumption increased 278% between 2004 and 2008 from 488 thousand barrels per day to
about 1.4 million barrels per day (U.S. Energy Information Administration. International Energy Statistics, Total Biofuels Consumption).

Figure 1. World Biofuels Production

Figure 2. World Biofuels Consumption by Year

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PRO/II Simulation of Bioethanol Production

Bioethanol is the most common biofuel, accounting for in excess of 90% of total biofuel usage. Ethanol is typically used as a gasoline
additive to oxygenate the fuel, increasing the octane rating, while also lowering the vehicle emissions. Ethanol can be produced
from various biomass sources, such as: corn fiber, sugar cane bagasse, grain straws, wood and paper wastes. The main technologies
for these processes include: thermo-chemical pretreatment, enzymatic hydrolysis, and fermentation via a variety of natural and
recombinant microbes, and distillation. Bioethanol is widely used as a fuel additive in both the United States and Brazil. The United
States uses fuel blends that are 5-10% ethanol, while fuel in Brazil must contain at least 22% ethanol. Ethanol is also a potential
fuel replacement for contemporary gasoline that could reduce the emission of greenhouse gases. New flex-fuel vehicles capable of
running on ethanol-gas mixtures of up to 85% ethanol are becoming more prevalent with over 6 million running worldwide.

Bioethanol is an alcohol produced by fermenting sugars typically from plant materials like sugar cane or corn. However, recent
advances in cellulosic biomass are enabling the production of bioethanol from trees or grass. The difficult part is designing the
bioethanol production process for optimal production and optimal economics. This is an instance where simulation software can be
used to alleviate the problem. Simulation software aids not only in the design of environmentally friendly and safe processes, but
also helps reduce capital and operating costs. Process simulation software can also provide the functionality and flexibility required
to model high fidelity biofuel processes with integrated correlations and reaction models. Process simulation software can be used to
design improved heat recovery processes, reconcile process data, and verify operating conditions. Use of simulation software for the
design of biofuels processes is good not only for the environment, but also for the bottom line.

Computer simulation is an essential tool in the design and economic analysis of new bioethanol technologies. This paper will discuss
the use of simulation software in the simulation of a bioethanol process based on the United States Department of Energy Bioethanol
Pilot Plant design (National Renewable Energy Laboratory. The DOE Bioethanol Pilot Plant, a tool for commercialization. DOE/GO-
102000-1114, September 2000). This simulation includes material recycles and thermal integration, as well as techniques to customize
unit operations and integrate user created models of the hydrolysis and fermentation processes. This paper will outline examples of
how process simulation software can be used for efficient design and operation of a biofuels production plant.

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PRO/II Simulation of Bioethanol Production

3. Overview of Solution
Steady-state simulation software is used in the conceptual and basic design phases of the plant life cycle, which is the ideal time
to commit to green engineering because it can have the greatest impact on the long-term environmental impact of the process.
Steady state simulation is essential to understanding the process, as well as the environmental and business ramifications of different
configurations. Simulation software provides the tools and flexibility to model the bioethanol process with high fidelity, and integrate
proprietary correlations and reaction models. The simulation in Figure 3 includes these processing steps:

• Dilute acid hydrolysis of long chain carbohydrates to sugars

• Fermentation of sugars to alcohols
• Separate unit operations are used to provide several examples of integrating custom reactions & kinetics
• Recovery of alcohols via vacuum distillation

The Excel unit operation provides the customization platform for the hydrolysis process and xylose fermentation. The conversion
reactor and a calculator unit operation provide the customization for glucose fermentation. The Excel unit operation utilizes existing or
new spreadsheet models and integrates them into the simulation calculation sequence as a native unit operation. This allows simple
integration of R&D correlations and mathematical models directly into the simulation without the cumbersome process of generating
and compiling user added subroutines. Simply copy the provided interface sheet into your Excel file, and then browse to the
workbook from within PRO/II. Link the feed stream and product stream cells to your Excel model using cell formulas, and the interface
is complete and ready to be used in the software.

Figure 3. Pro/II model of Bioethanol Production

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PRO/II Simulation of Bioethanol Production

4. Implementation Details
4.1. Hydrolysis Processes
The Excel unit operation conversion reactor template, Figure 4 (see next page), is used to model the hydrolysis reactions. There are
several technologies for hydrolysis, but all convert the long chain carbohydrates (cellulose and hemicellulose) to sugars and soluble
oligomers for microbial digestion. This simulation simplifies the hydrolysis reactions down to the 2 main sugars produced: xylose (from
hemicellulose), and glucose (from cellulose). The dilute acid process is modeled by the addition of dilute sulfuric acid to the biomass
feed, and heating of the reaction mass to 437 °F (225 °C) to drive the reaction, and release the sugars.

Typically this phase uses multiple staged reactors to optimize the production of sugars and minimize by-products. Additional heat
exchangers and reactors can be added to match process requirements. The “strong acid” process can be modeled in this same way,
as can the much less energy intensive enzymatic hydrolysis process.

The Excel unit operation conversion reactor template is used to model the hydrolysis reactions. Reactions are defined by entering
the molar quantities involved under each reaction column. Negative quantities are reactants, and positive quantities are products.
The base component name is identified in the “Base Component” row (row 10, see Figure 4). The conversion percent is entered in
the “Conversion Mole %” row (row 11, see Figure 4) for each reaction. “Conversion Mole %” is the amount of the base component
that will be reacted. The conversion amount can be a fixed number, a cell formula, or be transferred from PRO/II. In addition it may
be calculated within Excel via a mathematical model, or a Visual Basic program. Any of the tools available to you within Excel can be
employed to create the data you need in the most efficient manner possible.

Figure 4. Excel Unit Operation depicting a digester unit

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PRO/II Simulation of Bioethanol Production

4.2. Fermentation Processes

The xylose and glucose streams are split for demonstration purposes. In many processes, co-fermentation is done to consume both
sugars in the same process vessel. Different microbes can be used to digest each type of sugar, 5-carbon and 6-carbon. Also recombinant
bacterium engineered to be able to convert both types of sugars to ethanol and other useful products are being developed and im-
proved. In either case, it is a reasonable modeling simplification to separate the sugars, and handle the conversion processes in separate
unit operations, each having its own kinetics model. From a process standpoint, these reactions would be happening in the same vessel.

4.3. Glucose Fermentation

Glucose fermentation is carried out in a standard conversion reactor unit operation. This simplified reaction set is defined in the
PRO/II reactions data entry window shown in Figure 5. This is intended to be an illustrative example; a full reaction set for most
microbes would be far more complex.

Figure 5. Data entry window in Pro/II for reaction definitions

The reaction set is referenced in the conversion reactor configuration as shown in Figure 6. This allows multiple unit operations on the
same flowsheet to use the same reaction set. This not only reduces data entry tasks, but also ensures a consistent set of reactions are
used throughout the flowsheet to prevent data entry errors.

Figure 6. Data entry window in Pro/II for the conversion reactor

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PRO/II Simulation of Bioethanol Production

The Extent of Reactions data entry window allows the reactions to be reordered, and have their conversion rate defined by an
included quadratic equation, or by an external value via the “Define” feature. This configuration, shown in Figure 7, uses both
methods to illustrate the possible techniques.

Figure 7. Extent of reaction data entry window in Pro/II

The Define feature, figure 8, allows simple equations to specify the conversion rate for reactions in the conversion reactor unit
operation. The methanol reaction in the conversion reactor is defined as the “R2” value in the “RX_CONV” calculator unit operation.
The define data entry window shows the name of the variable as it is defined in the calculator unit operation for clarity.

Figure 8. Reaction definition window in Pro/II linking the reaction to calculated results

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PRO/II Simulation of Bioethanol Production

The calculator unit operation, Figure 9, allows a custom equation to be associated with the reaction conversion rate. In this example,
the conversion rate is varied based on the reactor inlet temperature. The biological activity function is approximated by a linear
equation spanning the temperature range of 50 °F to 180 °F, with peak activity at 115 °F. This activity function is calculated with this
small FORTRAN program.

Figure 9. Calculator unit in Pro/II definition

4.4. Xylose Fermentation

Xylose fermentation is modeled using customized kinetics in the Excel unit operation conversion reactor template. Its reactions are
defined in the Excel reactor model in the same way as the hydrolysis process.

However, the conversion rates for the four reactions are calculated based on inputs from the Excel unit operation, and a kinetics model
in the Excel workbook, as shown in Figure 10. The base reaction rates are specified in the parameters section of the PRO/II Excel unit
operation. The ratios between the different reactions are set, and passed to Excel.

Figure 10. Depiction of a link from Pro/II to excel calculations of reactions

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PRO/II Simulation of Bioethanol Production

Then, the actual conversion values are calculated based on the fermenter inlet temperature in Figure 11. The rate of conversion is
represented by a normal distribution around the optimal temperature of 115 °F. Any appropriate correlation can be used that best fits
your actual process or lab data.

Figure 11. Graphical fermentation rate used for the reaction

Once the correlation is entered in Excel, the overall conversion rate can be calculated. In Figure 12.

Fermentation Rate Calculation

Inlet Temp: 119.7 (deg F)
Curve X: 0.35923 (Sigma)
Curve Y: 0.3740 (Probability)
Actual Fermentation Rate: 2.083% (% Conversion / hr)

Total Fermentation Capacity: 200,000 (lb-mol)

Inlet Flowrate: 69.8 (lb-mol/min)
Residence Time: 48 (hr)
Residence Time: 1.99 (days)
Overall Fermentation %: 99.5%  
Figure 12. Tabular fermentation rate used for the reaction

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PRO/II Simulation of Bioethanol Production

Each individual conversion rate is calculated from the overall conversion rate based on the inlet temperature and the base rates for
each reaction that was passed to Excel from the PRO/II Excel unit operation shown in Figure 13.

Figure 13. Excel Spreadsheet integration custom kinetic data into Pro/II via the Excel unit operation

Using this methodology, sophisticated kinetics and custom correlations can be easily integrated into PRO/II to embed your process
knowledge into the simulation.

4.5. Separation Processes

Standard unit operations model the downstream separations processes to refine the alcohols produced into saleable fuel grade
material. A low pressure flash tank is used to produce an improved water stream for recycle to the process inlet, followed by a
distillation column to provide the bulk of the material separations. Energy integration operations are modeled quite easily with the
simple heat exchanger unit operation by connecting process streams to both the hot and cold sides. Calculated duties can also be
linked between heat exchangers where it is impractical to show the process streams connected to the same heat exchanger.

5. Conclusions
Simulation software also gives users the ability to analyze their design to optimize the process by using case studies to evaluate
the use of heat integration, various operating conditions, various operating configurations, or different raw material compositions.
Integration with Excel automates these case studies so that they can be run sequentially and so that the data can be evaluated easily
in a side-by-side comparison. The value of analyzing the process in the design phase is that the overall operating and capital costs can
be minimized with new processes and existing processes can be optimized with various configurations. Optimizing the plant profit by
decreasing capital costs and lowering operating costs is an important aspect in only making the process as environmentally friendly as
possible, and is an integral step in ensuring that the process is economically feasible in the long run.

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PRO/II Simulation of Bioethanol Production

6. Simulation Benefits
The example in this paper provides a starting point for anyone interested in exploring the design and operation of a bioethanol facility.
While the process in the paper is a fairly good representation of the bioethanol production process, the purpose of the example is to
demonstrate proper simulation techniques that can applied to biofuel processes. This model was not tuned to any particular/ actual
biofuels application. As a process design is developed, additional details can be added to the simulation model to provide a more
accurate depiction of an actual biofuels application or to add information for equipment sizing, project costing, or full economic
analysis of the bioethanol process. The techniques provided in this example give the user all the base capability needed to complete
this work in an efficient and effective manner.

Simulation software is an invaluable tool in understanding your process. Regardless the brand of simulation software used, it has
proven to be an important tool in the oil and gas industries.

7. References
National Renewable Energy Laboratory. The DOE Bioethanol Pilot Plant, a tool for commercialization. DOE/GO-102000-1114,
September 2000.

U.S. Energy Information Administration. International Energy Statistics, Total Biofuels Consumption, http://tonto.eia.doe.gov/cfapps/
ipdbproject/IEDIndex3.cfm?tid=79&pid=79&aid=2.

U.S. Energy Information Administration. International Energy Statistics, Total Biofuels Production, http://tonto.eia.doe.gov/cfapps/
ipdbproject/IEDIndex3.cfm?tid=79&pid=79&aid=1.

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