IBP3171_10 SIMULATION OF BIOETHANOL PRODUCTION Joseph McMullen1, Larry Balcom 2

Copyright 2010, Brazilian Petroleum, Gas and Biofuels Institute - IBP

This Technical Paper was prepared for presentation at the Rio Oil & Gas Expo and Conference 2010, held between September, 1316, 2010, in Rio de Janeiro. This Technical Paper was selected for presentation by the Technical Committee of the event according to the information contained in the abstract submitted by the author(s). The contents of the Technical Paper, as presented, were not reviewed by IBP. The organizers are not supposed to translate or correct the submitted papers. The material as it is presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institute opinion, nor that of its Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Oil & Gas Expo and Conference 2010 Proceedings.

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 bio-ethanol technologies. This paper will discuss the use of simulation software in the simulation of a bio-ethanol process based on the United States Department of Energy (DOE) Bio-ethanol Pilot Plant design (National Renewable Energy Laboratory. The DOE Bioethanol Pilot Plant, a tool for commercialization. DOE/GO-102000-1114, September 2000).

1. Introduction
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. 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 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. 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).

______________________________ 1 BS Chemical Engineer, Masters Business, Product Manager Invensys Operations Management 2 BS Chemical Engineer, Technical Sales Consultant Invensys Operations Management

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Figure 1. World Biofuels Prod F d duction

Figure 2. World Biof e fuels Consump ption by year Bioethanol is the mo common bi ost iofuel, account ting for in exce of 90% of t ess total biofuel usage. Ethanol is s typically used as a gasoline a t additive to oxygenate the fuel increasing th octane rating while also lo l, he g, owering the veh hicle emissions. Eth e hanol can be produced from v various biomass sources, such as: corn fiber sugar cane ba h r, agasse, grain st traws, wood and pape wastes. The main technolo w er ogies for these p processes inclu thermo-ch ude: hemical pretrea atment, enzyma atic hydrolysis, and fermentation via a variety o natural and r h d of recombinant m microbes, and di istillation. Bioethanol is wide ely used as a fuel a u additive in both the United St h tates and Brazi The United States uses fue blends that a 5-10% ethan il. el are nol, while fuel in Brazil must con w B ntain at least 22 ethanol. Eth 2% hanol is also a potential fuel r replacement fo contemporar or ry gasoline that could reduce th emission of g g he greenhouse gas New flex-f vehicles capable of runn ses. fuel ning on ethanol l-gas mixtures of up to 85% ethano are becomin more prevale with over 6 million running worldwide. m p ol ng ent . 2

Rio Oil & Gas Expo and Conference 2010 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 bio-ethanol technologies. This paper will discuss the use of simulation software in the simulation of a bio-ethanol process based on the United States Department of Energy Bio-ethanol 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.

2. 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 bio-ethanol process with high fidelity, and integrate proprietary correlations and reaction models. This simulation 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.

Biomass to Ethanol Process

XYLO_FEED FEED_RATIOS

Excel
XYLO_FERMENT

VENT FERM_PROD_2

COL_OVERHEAD 1

FERM_OVER 2 GAS_REMOVAL 3 4 5

CELLULOSE HYDRO_FEED ACID CAT_FEED PREHEATER M1 RECYLCE_H2O SUGARS S9 RX_CONV COOLER HYDR_PROD

6 7 8 9 FERM_PROD F1 RECY_2_COL RECYCLE COL_PREHEAT COL_FEED 10 11 12 13 14 SP1 MATBAL_TABLE 15 16 17 18 HX_TABLE 19 20 S1 COL1 21 22 M2 COL_BOTTOMS WASTE COL_TABLE

Excel
HYDROLYSIS

SC1 GLUC_FEED

GLUC_FERMENT

DRY_ALCOHOLS REGEN_H2O

MOL_SIEVES

Figure 3. PRO/II model of bioethanol production

3. Implementation Details
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Rio Oil & Gas Expo and Conference 2010 3.1. Hydrolysis Processes 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 byproducts. 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). The conversion percent is entered in the Conversion Mole % row (row 11) 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 3.2. Fermentation Processes The xylose and glucose streams are split for demonstration purposes. In many process, co-fermentation is done to consume both sugars in the same process vessel. Different microbes can be used to digest each type of sugar, 5carbon 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 improved. 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. 3.3. 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. This is intended to be an illustrative example; a full reaction set for most microbes would be far more complex.

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Figure 5. Data entry window in PRO/II for reaction definitions The reaction set is referenced in the conversion reactor configuration. 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. Date entry window in PRO/II for the conversion reactor 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 uses both methods to illustrate the possible techniques.

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Figure 7. Extent of reaction data entry window in PRO/II The define feature 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 The calculator unit operation 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 deg F to 180 deg F, with peak activity at 115 deg F. This activity function is calculated with this small FORTRAN program.

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Figure 9. Calculator unit in PRO/II definition 3.4. 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. 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 link from PRO/II to Excel calculations of reactions Then, the actual conversion values are calculated based on the fermenter inlet temperature. The rate of conversion is represented by a normal distribution around the optimal temperature of 115 deg F. Any appropriate correlation can be used that best fits your actual process or lab data.

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Figure 11. Graphical fermentation rate used for the reaction Once the correlation is entered in Excel, the overall conversion rate can be calculated. Fermentation Rate Calculation Inlet Temp: Curve X: Curve Y: Actual Fermentation Rate: 119.7 0.35923 0.3740 2.083% (deg F) (Sigma) (Probability) (% Conversion / hr)

Total Fermentation Capacity: Inlet Flowrate: Residence Time: Residence Time: Overall Fermentation %:

200,000 69.8 48 1.99 99.5%

(lb-mol) (lb-mol/min) (hr) (days)

Figure 12. Tabular fermentation rate used for the reaction 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.

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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. 3.5. 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.

4. Data Analysis & 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.

5. 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 9

Rio Oil & Gas Expo and Conference 2010 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.

6. References
National Renewable Energy Laboratory. The DOE Bioethanol Pilot Plant, a tool for commercialization. DOE/GO102000-1114, September 2000 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 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

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