Simulation of the BioEthnaol Process

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1 Ian David Lockhart Bogle and Michael Fairweather (Editors), Proceedings of the 22nd European Symposium on Computer Aided Process Engineering, June 2012, London Elsevier B.V. All rights reserved. Simulation of the BioEthnaol Process Joseph Mc Mullen a Larry Balcom b Roy Calder c a Invensys Operations Management, 223 Wilmington West, Chadds Ford, United States of America b Invensys Operations Management, 223 Wilmington West, Chadds Ford, United States of America c Invensys Operations Management, Manor Royal, Crawley RH106SJ United Kingdom Abstract Global production of biofuels is increasing in response to worldwide demand. Simulation software aids not only in the design of environmentally friendly and safe processes, but also helps reduce capital and operating costs. Simulation software provides the functionality and flexibility required to model high fidelity biofuel processes with integrated correlations and reaction models. Process simulation software can be used to improve heat recovery processes, reconcile data, and verify operating conditions. Simulation software contributes to efficient and safe process design. Use of simulation software for the design of biofuels processes is good not only for the environment, but also for the bottom line. Several technology demonstration plants have been built and operated to verify technical feasibility and economic viability of the technology in the current energy market. Ethanol is an important additive to oxygenate gasoline, and increase the octane rating in light of the recent ban on the MTBE additive. Ethanol can be produced from various bio-mass sources, such as: corn fiber, sugar cane bagasse, grain straws, wood and paper wastes. The main technologies for these processes include: thermo-chemical pretreatment, ensymatic hydrolysis, and fermentation via a variety of natural and recombinant microbes, and distillation. Nation Renewable Energy Laboratory (NREL) provides funding and technology transfer packages to assist the private sector in creating the needed biomass to ethanol capability. 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 (1). This simulation includes material recycles and thermal integration, as well as techniques to customise unit operations and integrate user created models of the hydrolysis and fermentation processes. Keywords: BioEthanol, Simulation, Reactions Excel. 1. 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.

2 2 Joseph McMullen et al 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 minimise 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 capitalise on the initial correlations and reuse the work they have already done in Excel. This can model any proprietary or specialised process that cannot be modeled using traditional unit operations. 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 commercialisation. DOE/GO , September 2000). This simulation includes material recycles and thermal integration, as well as techniques to customise unit operations and integrate user created models of the hydrolysis and fermentation processes. 2. Overview of the 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

3 Simulation of the BioEthanol Process 3 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 1 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 Figure 1 - PRO/II Model of BioEthanol Production The Excel unit operation provides the customisation platform for the hydrolysis process and xylose fermentation. The conversion reactor and a calculator unit operation provide the customisation for glucose fermentation. 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. 3. Implementation Details 3.1. Hydrolysis Processes The Excel unit operation conversion reactor template, Figure 2, 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 225 C to drive the reaction, and release the sugars.

4 4 Joseph McMullen et al Figure 2 - EXCEL Unit Operation depicting a digester unit Typically this phase uses multiple staged reactors to optimise the production of sugars and minimise 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 ensymatic 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. The conversion percent is entered in the Conversion Mole % row 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 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 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.

5 Simulation of the BioEthanol Process 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. 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. 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 Xylose Fermentation Xylose fermentation is modeled using customised 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 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. Conclusions Simulation software gives users the ability to analyse their design to optimise 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 analysing the process in the design phase is that the overall operating and capital costs can be minimised with new processes and existing processes can be optimised with various configurations. Optimising the plant profit by decreasing capital costs and lowering operating costs is an important aspect in not only making the process as environmentally friendly as possible, but is an integral step in ensuring that the process is economically feasible in the long run.

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