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Utilization of Fats, Oils and Grease in Biodiesel Production

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Utilization of Fats, Oils and Grease in Biodiesel Production Utilization of Fats, Oils and Grease in Biodiesel Production: From Market Study to Technical Feasibility A thesis submitted to Department of Chemical and Environmental Engineering Division of Graduate Studies University of Cincinnati In partial fulfillment of the requirement for the degree of Master of Science 2017 Junsong Zhang B.E. in Mechanical Engineering, Shandong University, 2014 Committee: Mingming Lu, PhD (Chair) Drew McAvoy, PhD Maobing Tu, PhD Fumin Ren, PhD i Abstract The biodiesel industry has continued to boom in the past few decades and new technologies have been developed to handle low-cost feedstocks. Fats, oils and grease (FOG), a nuisance to the environment, has attracted increasing attention in biodiesel production in recent years. This thesis started with a market feasibility study on FOG management in wastewater treatment plants (WWTPs) to determine the potential market from FOG to biodiesel. Furthermore, a greener alternative titration method for measuring acid numbers in FOG was developed. Lastly, the challenges of reducing sulfur content from FOG to biodiesel are also investigated using three different types of FOG. The purpose of this thesis is to evaluate the utilization of FOG in biodiesel production, from the perspective of market to technical feasibility. We conducted a survey of 29 WWTPs, which indicated that the preferred method of FOG handling depends on geographical location. Landfill is still the major FOG disposal method (76.23% of capacity) followed by anaerobic digestion (12.29%) and incineration (11.48%). Furthermore, FOG processing technology also needs to be custom developed based on each location and each WWTP. A potential market of WWTP-FOG for biodiesel production could be achieved by reducing the current disposal cost significantly and producing environmental- friendly biodiesel. The current titration methods to determine the free fatty acid content in FOG could generate a huge amount of toxic solvent waste such as toluene. In this study, a greener method is proposed for measuring acid numbers (ANs) in comparison with the official AOCS cd 3d-63 method. This greener method can eliminate the use of toluene, and decrease the amount of isopropyl alcohol ii (from 125ml to 50ml), which in turn reduces toxicity and cost. 44 samples of yellow and brown grease with a wide ANs ranging from 0.133 to 170.369 mg KOH/g were titrated to compare to AOCS cd 3d-63. Various statistical tests including repeatability, linear model, f-test, t-test and calibration methods were conducted to evaluate the performance of green methods. Besides, the minimum detection for visual titration is determined as 0.0657 mgKOH/g for the first time. This green method can be recommended for routine titration for biodiesel plants. Sulfur issues may become an obstacle for FOG re-utilization due to high sulfur content (up to 1000 ppm). So it is essential to study sulfur distribution from FOG to biodiesel and ensure that biodiesel produced can meet the ASTM D6751 sulfur standard (15 ppm). In this research, three sources of FOG (SD1, MSD, JTM) were investigated to evaluate the sulfur transfer from FOG to biodiesel. Sulfur content of raw FOG may vary from 300 to 800 ppm. Implementing oil- extraction processes (blending grease with WCO) and biodiesel reactions, sulfur concentration can be reduced significantly, by 66.7% and 96.97%, respectively. By using an appropriate WCO- FOG weight ratio for oil separation (at 3.6 for MSD, 4.5 for SD1), all of the biodiesel products in this study can meet the ASTM D6751 sulfur standards (15ppm). Keywords: FOG, Biodiesel, Market, Acid Number, Titration, Sulfur. Wastewater treatment plants. iii iv [This page is intentionally left blank] v Acknowledgement I would like to thank Dr. Mingming Lu, my committee chair, for offering the major direction and valuable suggestions for this thesis. Also, I deeply appreciate other committee members: Dr. Drew C. McAvoy, and Dr. Maobing Tu and Dr. Fumin Ren, for their effort on my master study. The support from National Science Foundation I-Corps Program (IIP 16 IIP-1660675) is fully appreciated. The committee members in NSF offered not only financial support but also business market strategy for this research. Many thanks to Mr. Art Helmstetter for his advices on the customer discovery project. I would like to thank my other colleges: Qingshi Tu, Yang Liu, Nathan Holliday, Son Dong, Minghao Kong for their help on my master study. Last, I would like to thank my family: Quansheng Zhang, Hongfei Zhao and my fiancé Xiaolin Wang for their forever support on my life study and career. vi Table of Contents Chapter 1. INTRODUCTION ........................................................................................................1 1.1 Background ........................................................................................................1 1.2 Biodiesel Feedback ............................................................................................2 1.3 Fats, Oil and Grease (FOG) ...............................................................................5 1.3.1 FFA Profile in FOG ................................................................................9 1.3.2 FFA Quantification Methods ................................................................10 1.3.3 Sulfur content in FOG ...........................................................................12 1.4 Goal Statement .................................................................................................12 1.4.1 FOG Market Feasibility ........................................................................12 1.4.2 Green Titration Method ........................................................................12 1.4.3 Sulfur Analysis of FOG ........................................................................13 2. MANAGEMENT OF FATS, OILS AND GREASE (FOG) IN WASTEWATER TREATMENT PLANTS (WWTPs) ACROSS THE US ...............................................14 2.1 Objective ..........................................................................................................14 2.2 Current FOG Management – FOG Programs ..................................................16 2.3 Current Disposal/Utilization of FOG ...............................................................17 2.3.1 Landfill ..................................................................................................17 2.3.2 Anaerobic Digestion .............................................................................19 2.3.3 Incineration ...........................................................................................22 2.4 Result Summary ...............................................................................................22 3. A GREEN ALTERNATIVE TITRATION METHOD FOR DETERMINATION OF THE ACID NUMBERS (ANs) OF FATS, OILS, GREASE (FOG) .........................................23 3.1 Objective ..........................................................................................................23 3.2 Acid Number and FFA % ................................................................................23 3.2.1 AOCS Methods .....................................................................................24 3.2.2 ASTM Methods ....................................................................................26 3.3 Literature Review.............................................................................................27 3.4 Methodology ....................................................................................................33 vii 3.4.1 Proposed Green Method .......................................................................33 3.4.2 Detection limit of Visual Titration ........................................................34 3.4.3 Statistic Analysis ...................................................................................36 3.4.4 Method Calibration ...............................................................................38 3.5 Results and Discussion ....................................................................................39 3.5.1 Repeatability .........................................................................................39 3.5.2 Linearity between Green and AOCS Cd 3d-63 Method .......................43 3.5.3 Results of ANOVA f-test and t-test. .....................................................45 3.5.4 Results of Method Calibration ..............................................................46 3.5.5 Density versus Acid Number ................................................................47 3.6 Solvent Recovery in Titration Waste ...............................................................49 3.6.1 Introduction ...........................................................................................49 3.6.2 Results Summary ..................................................................................50 3.7 Conclusion .......................................................................................................53 4. SULFUR ANALYSIS OF FATS, OILs AND GREASE (FOG) ...............................55 4.1 Introduction .....................................................................................................55 4.2 Literature Review and Objectives ....................................................................56 4.3 Sulfur Analysis Standards ................................................................................57 4.4 Materials ..........................................................................................................59
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