University of Pennsylvania ScholarlyCommons Department of Chemical & Biomolecular Senior Design Reports (CBE) Engineering 4-2011 Glycerol to Propylene Glycol Kumar Chatterjee University of Pennsylvania Kelsey Hall University of Pennsylvania Samuel Tell University of Pennsylvania Follow this and additional works at: https://repository.upenn.edu/cbe_sdr Chatterjee, Kumar; Hall, Kelsey; and Tell, Samuel, "Glycerol to Propylene Glycol" (2011). Senior Design Reports (CBE). 26. https://repository.upenn.edu/cbe_sdr/26 This paper is posted at ScholarlyCommons. https://repository.upenn.edu/cbe_sdr/26 For more information, please contact [email protected]. Glycerol to Propylene Glycol Abstract A Cu-ZnO-Al2O3 catalyst has been observed in laboratory scale tests to effectively produce propylene glycol from glycerol using a liquid phase hydrogenolysis reaction, which occurs at 410 F and 580 psia. A trickle-bed reactor will be used to ensure the full contact of liquid and vapor phases with the solid catalyst. This project aims to successfully scale up this reactor model, which has thus far only been tested in bench scale. The design specification stipulates that this process will produce 100 MM lb/year of propylene glycol. Using crude glycerol harvested from biodiesel production, a final product purity of 99.6% was achieved from a feedstock of 80% glycerol, 15% water, 1% methanol, and 4% sodium chloride by weight, plus trace amounts of organic salts. The economic analysis that follows assumes a grassroots plant on the US Gulf Coast. The total capital investment was calculated to be $34.0 million, which includes a working capital of $9.78 million. Under the assumptions that the prices of crude glycerol, hydrogen, and propylene glycol are $0.22, $0.50, and $1.00 per pound respectively, the net present value (NPV) at the end of the 15 year allotted course of the project is $88.4 million and the investors’ rate of return (IRR) is 58.45%. The price of glycerol is projected to remain stable or decrease in the future and the price of propylene glycol is projected to remain stable or increase suggesting that this project could become even more profitable in the future. The apparent profitability of this project is largely caused by the efficient and cost effective method of desalting glycerol through electrodeionization. Unfortunately, the proprietary nature of this new process precludes public access to true costing and specifications for the equipment since firms as Dow largely control the technology. Thus, conservative estimations were made in our economic analysis to account for this uncertainty. This working paper is available at ScholarlyCommons: https://repository.upenn.edu/cbe_sdr/26 Glycerol to Propylene Glycol Glycerol to Propylene Glycol April 12, 2011 Kumar Chatterjee Kelsey Hall Samuel Tell Advisor: Dr. Warren Seider Glycerol to Propylene Glycol Glycerol to Propylene Glycol Professor Warren Seider Professor Leonard Fabiano Department of Chemical and Biomolecular Engineering University of Pennsylvania 220 South 33rd Street Philadelphia, PA 19104 April 12, 2011 Dear Professor Seider and Professor Fabiano, As proposed by Bruce Vrana, we have designed a plant that will produce one hundred million pounds per year of propylene glycol from crude glycerol, which is a byproduct derivative of biodiesel production. This process integrates electrodeionization, an emerging glycerine refinement technology, with a multiphase reaction in a trickle-bed reactor. This report includes the design details for the process, an economic analysis, and recommendations and predictions for the extent of its success. Based on the aforementioned analysis, this process is found to be a viable and profitable alternative to current methods of propylene glycol production. Furthermore, the process is environmentally friendly while also complementing the growth of the biodiesel industry that is predicted to surge over the project’s lifetime. Thank you for your consideration and assistance with this endeavor. Sincerely, Kelsey Hall Kumardipti Chatterjee Samuel Tell Glycerol to Propylene Glycol Glycerol to Propylene Glycol TABLE OF CONTENTS Section 1. Abstract 1 Section 2. Introduction 5 Section 3. Project Charter 9 Section 4. Technology-Readiness Assessment 13 Section 5. Concept Stage 17 Section 6. Preliminary Process Synthesis 25 Section 7. Chemical Database 31 Section 8. Kinetics of Reaction 41 Section 9. Process Flow Diagram and Material Balances 47 Section 10. Bench-Scale Laboratory Work 55 Section 11. Process Description 59 Section 12. Heat Integration: Energy Balance and Utility Requirements 69 Section 13. Equipment List and Unit Descriptions 73 Section 14. Specification Sheets 85 Section 15. Fixed-Capital Investment Summary 105 Section 16. Environmental Considerations 110 Section 17. Health and Safety Concerns 115 Section 18. Startup Considerations 121 Section 19. Plant Layout 125 Section 20. Operating Costs and Economic Analysis 129 Section 21. Conclusion and Recommendations 153 Section 22. Acknowledgements 157 Section 23. Bibliography 161 Section 24. Appendix 165 Section 25. Problem Statement 185 Section 26. Patent and Aspen Simulation Report 191 Glycerol to Propylene Glycol Abstract Section 1 ABSTRACT 1 Glycerol to Propylene Glycol Abstract Abstract A Cu-ZnO-Al2O3 catalyst has been observed in laboratory scale tests to effectively produce propylene glycol from glycerol using a liquid phase hydrogenolysis reaction, which occurs at 410 F and 580 psia. A trickle-bed reactor will be used to ensure the full contact of liquid and vapor phases with the solid catalyst. This project aims to successfully scale up this reactor model, which has thus far only been tested in bench scale. The design specification stipulates that this process will produce 100 MM lb/year of propylene glycol. Using crude glycerol harvested from biodiesel production, a final product purity of 99.6% was achieved from a feedstock of 80% glycerol, 15% water, 1% methanol, and 4% sodium chloride by weight, plus trace amounts of organic salts. The economic analysis that follows assumes a grassroots plant on the US Gulf Coast. The total capital investment was calculated to be $34.0 million, which includes a working capital of $9.78 million. Under the assumptions that the prices of crude glycerol, hydrogen, and propylene glycol are $0.22, $0.50, and $1.00 per pound respectively, the net present value (NPV) at the end of the 15 year allotted course of the project is $88.4 million and the investors’ rate of return (IRR) is 58.45%. The price of glycerol is projected to remain stable or decrease in the future and the price of propylene glycol is projected to remain stable or increase suggesting that this project could become even more profitable in the future. The apparent profitability of this project is largely caused by the efficient and cost effective method of desalting glycerol through electrodeionization. Unfortunately, the proprietary nature of this new process precludes public access to true costing and specifications for the equipment since firms as Dow largely control the technology. Thus, conservative estimations were made in our economic analysis to account for this uncertainty. 2 Glycerol to Propylene Glycol Abstract 3 Glycerol to Propylene Glycol Abstract 4 Glycerol to Propylene Glycol Introduction Section 2 INTRODUCTION 5 Glycerol to Propylene Glycol Introduction Introduction Propylene glycol (also called 1,2-propanediol) is an incredibly versatile compound that is used in a number of industrial applications that range from transportation and construction to food and pharmaceutical production. Pharmaceutical (USP) grade propylene glycol is at least 99.5% pure by weight and is used in health- sensitive products such as food, personal consumer goods, cosmetics, and pharmaceuticals. Due to its highly sensitive applications, USP grade propylene glycol is regulated carefully by the FDA and producers must comply with strict regulations to ensure the quality and purity of their product. Industrial grade propylene glycol is at least 95% pure and is an important player in the transportation industry as it is used in aircraft de-icer, antifreeze, and brake fluid. It is also used in the construction industry as the primary component in unsaturated polyester resins (UPRs) that are used to make fiberglass reinforced plastics. Propylene glycol’s chemical neutrality and nonreactivity make it very useful as a solvent. It can be used as an emulsifier to stabilize mixtures of two or more immiscible liquids. This often occurs in the preparation of cosmetics, where oil and water must be mixed to produce creams or lotions, and in the preparation and processing of some foods. It is a useful excipient, a pharmacologically inactive substance that acts as a carrier for the active ingredients in medication. It can be used for boiling point elevation or freezing point reduction, which makes it an effective de-icer and antifreeze solution. Historically, propylene glycol has been produced by the hydration of propylene oxide, which occurs at 392 F and 174 psia, or catalytically at 302-356 F, and produces di- 6 Glycerol to Propylene Glycol Introduction and tripropylene glycols and small quantities of higher glycols in side reactions (ICIS, 2011). This process has a large negative environmental impact due to pollution and use of valuable resources, so alternative methods, such as production from glycerol, are under investigation worldwide. This option is especially promising in light of the recent surge in