Western University Scholarship@Western Electronic Thesis and Dissertation Repository 9-4-2015 12:00 AM Catalytic Conversion of Glycerol to Value-Added Chemical Products Malaya Ranjan Nanda Supervisor Dr. Charles Xu The University of Western Ontario Graduate Program in Chemical and Biochemical Engineering A thesis submitted in partial fulfillment of the equirr ements for the degree in Doctor of Philosophy © Malaya Ranjan Nanda 2015 Follow this and additional works at: https://ir.lib.uwo.ca/etd Part of the Catalysis and Reaction Engineering Commons, Polymer Science Commons, and the Thermodynamics Commons Recommended Citation Nanda, Malaya Ranjan, "Catalytic Conversion of Glycerol to Value-Added Chemical Products" (2015). Electronic Thesis and Dissertation Repository. 3215. https://ir.lib.uwo.ca/etd/3215 This Dissertation/Thesis is brought to you for free and open access by Scholarship@Western. It has been accepted for inclusion in Electronic Thesis and Dissertation Repository by an authorized administrator of Scholarship@Western. For more information, please contact [email protected]. CATALYTIC CONVERSION OF GLYCEROL TO VALUE-ADDED CHEMICAL PRODUCTS (Thesis format: Integrated Article) by Malaya Ranjan Nanda Graduate Program in Chemical and Biochemical Engineering A thesis submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy The School of Graduate and Postdoctoral Studies The University of Western Ontario London, Ontario, Canada © Malaya Ranjan Nanda 2015 Abstract Rapid expansion of the biodiesel industry has generated a huge amount of crude glycerol. This thesis aimed to explore utilization of glycerol for the production of solketal as an oxygenated fuel additive and 1, 2-propanediol as a polymer component via catalytic conversion. The thesis work may be divided into two major parts. In the first part, the thermodynamics and kinetics of the glycerol ketalization for the synthesis of solketal were investigated in a batch reactor. From this information, a continuous-flow process was designed, developed and optimized using pure glycerol. Crude glycerol (13 wt% purity) was successfully upgraded into a purified crude glycerol product (> 96 wt% purity) and was used as feedstock in a modified reactor for the synthesis of solketal whose economic feasibility was demonstrated. In the second part, B2O3 promoted Cu/Al2O3 catalysts were used for selective hydrogenolysis of glycerol to 1, 2-propanediol in a flow reactor. Surface properties, acidity, crystallinity, and reducibility of the catalysts were measured using N2 adsorption, NH3-temperature programmed desorption (TPD), X-ray diffraction (XRD), and H2-temperature programmed reduction (TPR), respectively. The fuels/chemicals products obtained were analyzed by GC-MS/FID and Fourier- transformation infrared spectroscopy (FTIR). The ketalization reaction equilibrium constants were determined experimentally in the temperature range of 293-323 K. The activation energy of the overall reaction was determined to be 55.6 ± 3.1 kJ mol-1. Langmuir-Hinshelwood equation was used to model the rate law. The activity of all catalysts tested in the flow reactor follows the order: Amberlyst wet H-beta zeolite Amberlyst dry > Zirconium sulfate > Montmorillonite > Polymax. At optimum conditions (25 °C, 500 psi, acetone-to-glycerol molar ratio of 4 and 2 h-1 WHSV), the maximum solketal yield from pure glycerol was 94±2% over Amberlyst wet. Ketalization of purified crude glycerol over Amberlyst wet, led to 93± 3% glycerol conversion with 92 ±2% solketal yield at the optimum conditions. In the glycerol hydrogenolysis process with 10 wt% aqueous solution of glycerol as the feed, 5Cu-B/Al2O3 ii catalyst demonstrated a very high activity, yielding 98 ±1% glycerol conversion and - 98±1% 1,2-propanediol selectivity at the optimum conditions (250 °C, 6 MPa H2, and 0.1h 1 WHSV). Keywords Glycerol, Crude glycerol, Purified crude glycerol, Catalyst, Amberlyst-36 wet, Solketal, 1,2-propanediol, Ketalization, Hydrogenolysis, Optimization, Thermodynamics, Kinetics, Flow reactor, Acidification, Regeneration, Copper catalyst, Deactivation. iii Co-Authorship Statement Chapter 2: General literature review This chapter will be submitted as a review paper titled “Crude glycerol: A liability or an evolving opportunity” to Biofuels, Bioproducts and Biorefining for consideration of publication. Authors: Nanda, M., Tymchyshyn, M., Yuan, Z., Qin, W., Xu, C. Writing and literature data analysis were conducted by Malaya Nanda assisted by Matthew Tymchyshyn under the supervision of Dr. Zhongshun Yuan and Prof. Wensheng Qin. It was reviewed and revised by Prof. Charles (Chuanbao) Xu. Chapter 3: Innovative and potential technologies towards the sustainable production of solketal as a fuel addivitve: A review. This chapter will be submitted as a review paper to Rewnewable and Sustainable Energy Review for consideration of publication. Authors: Nanda, M., Zhang, Y., Yuan, Z., Qin, W., Ghaziaskar, H., Xu, C. Writing and literature data analysis were conducted by Malaya Nanda assisted by Dr. Yongsheng Zhang, and Dr. Zhongshun Yuan under the supervision of and Prof. Wensheng Qin and Prof.Hassan Ghaziaskar. It was reviewed and revised by Prof. Charles (Chuanbao) Xu. Chapter 4: Recent advancements in catalytic conversion of glycerol into propylene glycol: A review This chapter will be submitted as a review paper to Industrial Crops and Products for consideration of publication. Authors: Nanda, M., Yuan, Z., Qin, W., Xu, C. iv Writing and literature data analysis were conducted by Malaya Nanda assisted by Dr. Zhongshun Yuan under the supervision of and Prof. Wensheng Qin. It was reviewed and revised by Prof. Charles (Chuanbao) Xu. Chapter 5: Thermodynamic and kinetic studies of a catalytic process to convert glycerol into solketal as an oxygenated fuel additive This chapter is a published article: Nanda, M., Yuan, Z., Ghaziaskar, H.S., Qin, W., Poirier, M., Xu, C., Thermodynamics and kinetic studies of a catalytic process to convert glycerol into solketal as an oxygenated fuel additive, Fuel, 2014, 117, 470-477 The experimental work was conducted by Malaya Nanda under the supervision of Prof. Charles (Chuanbao) Xu and guidance of Dr. Zhongshun Yuan. Writing and data analysis were conducted by Malaya Nanda assisted by Wensheng Qin and Marc-Andre Poierer. It was reviewed and revised by Prof. Charles (Chuanbao) Xu, Dr. Zongshun Yuan and Prof. Hassan Ghaziaskar. Chapter 6: A new continuous-flow process for catalytic conversion of glycerol to oxygenated fuel additive: catalyst screening This chapter is a published article: Nanda, M., Yuan, Z., Qin, W., Ghaziaskar , H.S., Poirier, M., Xu, C., A new continuous-flow process for catalytic conversion of glycerol to oxygenated fuel additive: catalyst screening, Applied Energy, 2014,123, 75-81 The experimental work was conducted by Malaya Nanda under the supervision of Prof. Charles (Chuanbao) Xu and guidance of Dr. Zhongshun Yuan. Writing and data analysis were conducted by Malaya Nanda assisted by Wensheng Qin and Marc-Andre Poierer. It was reviewed and revised by Prof. Charles (Chuanbao) Xu, Dr. Zongshun Yuan and Prof. Hassan Ghaziaskar. v Chapter 7: A Catalytic conversion of glycerol to oxygenated fuel additive in a continuous flow reactor: process optimization This chapter is a published article: Nanda, M., Yuan, Z., Qin, W., Ghaziaskar , H.S., Poirier, M., Xu C., Catalytic conversion of glycerol to oxygenated fuel additive in a continuous flow reactor: process optimization, Fuel, 2014,128, 113-119 The experimental work was conducted by Malaya Nanda under the supervision of Prof. Charles (Chuanbao) Xu and guidance of Dr. Zhongshun Yuan. Writing and data analysis were conducted by Malaya Nanda assisted by Wensheng Qin and Marc-Andre Poierer. It was reviewed and revised by Prof. Charles (Chuanbao) Xu, Dr. Zongshun Yuan and Prof. Hassan Ghaziaskar. Chapter 8: Purification of Crude Glycerol Using Acidification: Effects of Acid Types and Product Characterization This chapter is a published article: Nanda, M., Yuan, Z., Qin, W., Poirier, M., Xu, C. Purification of Crude Glycerol Using Acidification: Effects of Acid Types and Product Characterization: Austin J Chem Eng, 2014, 1, 1-7. The experimental work was conducted by Malaya Nanda under the supervision of Prof. Charles (Chuanbao) Xu and guidance of Dr. Zhongshun Yuan. Writing and data analysis were conducted by Malaya Nanda assisted by Wensheng Qin and Marc-Andre Poierer. It was reviewed and revised by Prof. Charles (Chuanbao) Xu, and Dr. Zongshun Yuan Chapter 9: Catalytic conversion of purified crude glycerol ina continuous-flow process for the synthesis of oxygenated fuel additive Authors: Nanda, M., Yuan, Z., Qin, W., Poirier, M., Xu, C. This article has been submitted to Biomass and Bioenergy for consideration of publication. The experimental work was conducted by Malaya Nanda, assisted by Dr. Zongshun Yuan under the supervision of Prof. Wensheng Qin. Writing and data analysis were conducted vi by Malaya Nanda assisted by Marc-Andre Poierer. It was reviewed and revised by Prof. Charles (Chuanbao) Xu, and Dr. Zongshun Yuan Chapter 10: B2O3 promoted Cu/Al2O3 catalysts for selective hydrogenolysis of glycerol and crude glycerol to produce 1,2-propanediol This chapter will be submitted as a research article to Green Chemistry for consideration of publication. Authors: Nanda, M., Yuan, Z., Qin, W., Xu, C. The experimental work was conducted by Malaya Nanda and Dr. Zongshun Yuan under the supervision of Prof.