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Removal of 2, 4-Dinitrophenol by Ferrate

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Removal of 2, 4-Dinitrophenol by Ferrate University of Central Florida STARS Electronic Theses and Dissertations, 2004-2019 2008 Removal Of 2, 4-dinitrophenol By Ferrate Gianna Cooley University of Central Florida Part of the Environmental Engineering Commons Find similar works at: https://stars.library.ucf.edu/etd University of Central Florida Libraries http://library.ucf.edu This Masters Thesis (Open Access) is brought to you for free and open access by STARS. It has been accepted for inclusion in Electronic Theses and Dissertations, 2004-2019 by an authorized administrator of STARS. For more information, please contact [email protected]. STARS Citation Cooley, Gianna, "Removal Of 2, 4-dinitrophenol By Ferrate" (2008). Electronic Theses and Dissertations, 2004-2019. 3619. https://stars.library.ucf.edu/etd/3619 REMOVAL OF 2, 4-DINITROPHENOL BY FERRATE by GIANNA GRIFFITH COOLEY B.S. Loyola Univeristy New Orleans, 2002 A thesis submitted in partial fulfillment of the requirements for the degree of Master of Environmental Engineering in the Department of Civil and Environmental Engineering in the College of Engineering and Computer Science at the University of Central Florida Orlando, Florida Fall Term 2008 Major Professor: Debra R. Reinhart © 2008 Gianna Griffith Cooley ii ABSTRACT VI 2- Ferrate (molecular formula, Fe O4 ) has been studied increasingly since the 1970s as a disinfectant and coagulant for domestic wastewater and also as an oxidant for industrial wastewaters (Murmann and Roginson, 1974, Gilbert et al., 1978, Kazama, 1994, Jiang et al., 2002, and Sharmaet al., 2005). This research was performed to explore whether ferrate could possibly be used as chemical treatment for industrial wastewaters from plastic, chemical, dye, soap, and wood stain producing plants that contain 2, 4-Dinitrophenol (DNP). DNP is listed on the United States Environmental Protection Agency (EPA) Drinking Water Contaminant Candidate List (CCL). This list includes compounds which are not currently regulated at the national level, but there is a growing concern for the harm they may cause to the environment. Therefore, the EPA prioritizes these compounds and conducts extensive research to determine if these compounds should be regulated (USEPA, 2005). The effects of Ferrate on DNP were evaluated during these experiments. The effect of various dosages of Ferrate and different pH values was monitored over 17 minutes using UV 254 to determine the extent of oxidation of 300 mg L-1 DNP. Removal of DNP at all pHs and dosages was noted, however, a pH of 4 and a molar ratio of 14: 1 (Ferrate to DNP) removed the highest percentage of DNP at 87.3. The by-products of the 3.5 and 14: 1 molar ratio of Ferrate to DNP reactions at a pH of 4 and their toxicity were determined by measuring biochemical oxygen demand 5 day (BOD5), dissolved organic carbon (DOC), chlorine residual and chemical oxygen demand (COD), and gas chromatography/mass spectrometry (GC/MS) analysis. The BOD5 indicated toxicity, either from the residual chlorine or the organisms used for seeding not being acclimated to DNP and by-products. DOC of the 3.5 : 1 molar ratio was higher than calculated iii values indicating more ring breakage than was originally measured by UV 254. DOC of the 14: 1 molar ratio experiment was lower than calculated values, which indicated human error in measuring the DNP concentration. The chlorine residual was high for both experiments, 112 and 594 mg L-1, for the 3.5 and 14: 1 molar ratios, respectively. COD was unable to be measured due to chloride interference. The GC/MS data showed several chlorine-substituted benzene rings as well as carbon tetrachloride for the 3.5:1 molar ratio DNP experiments. The 14:1 GC/MS data indicated much more ring breakage with carbon tetrachloride, a substituted butane chain, many unknown straight chain chlorinated compounds and dichloro-pentane isomers as by-products. iv Dedicated to my husband, Stuart. Thank you for supporting me throughout these two years. I could not have done it without you. v ACKNOWLEDGMENTS I would like to thank my advisor, Debra R. Reinhart for her advice throughout this project. I would also like to thank Dr. Andrew Randall for answering many questions that I had and teaching me in his classes, and Dr. Diego Diaz for expanding my knowledge of electrochemistry and serving on my committee. Thank you to Dr.Stephen Medlin for his analytical advice, and Brian Picard and Ted Schrein from Southern Analytical for their field expertise. I appreciate Luke Daly, Craig Alig, and Chris Huban of Ferrate Treatment Technologies for the financial support to perform this research. I especially want to express my sincere appreciation to my parents, Sam and Joyce Griffith, for their love and support throughout my life, and encouraging me to strive for success in my career choice. vi TABLE OF CONTENTS LIST OF FIGURES ....................................................................................................................... ix LIST OF TABLES .......................................................................................................................... x CHAPTER 1: INTRODUCTION .................................................................................................. 1 1.1 Experiment Objectives ......................................................................................................... 2 CHAPTER 2: LITERATURE REVIEW ....................................................................................... 3 2.1 Ferrate Production ................................................................................................................ 3 2.2 Ferrate Reactions ................................................................................................................. 5 2.2 2,4 Dinitrophenol (DNP) Review ........................................................................................ 9 CHAPTER THREE: METHODS ................................................................................................ 14 3.1 Introduction ........................................................................................................................ 14 3.2 pH Optimization ................................................................................................................ 14 3.3 Evaluation of the Kinetic Rate of Reaction of Ferrate with 2, 4 DNP .............................. 18 3.4 Dose Optimization ............................................................................................................. 19 3.5 Reaction Products .............................................................................................................. 19 CHAPTER FOUR: RESULTS AND DISCUSSION .................................................................. 22 4.1 Introduction ........................................................................................................................ 22 4.2 UV Spectra ......................................................................................................................... 22 4.3 Optimizing pH ................................................................................................................... 24 4.4 Kinetic Experiments .......................................................................................................... 26 4.5 Dosage Optimization with pH 4 ........................................................................................ 27 4.6 Reaction Products .............................................................................................................. 29 CHAPTER 5: CONCLUSIONS AND RECOMMENDATIONS ............................................... 33 vii APPENDIX A: RESULTS SUMMARY TABLES ..................................................................... 35 APPENDIX B: RAW DATA....................................................................................................... 39 APPENDIX C: ENCO LABORATORY REPORT .................................................................... 67 REFERENCES ........................................................................................................................... 100 viii LIST OF FIGURES Figure 1. Standard Curve for the HACH 4000, 0-2.5 mg L-1. ...................................................... 15 Figure 2. HACH Standard Curve for concentrations 0.2-2.5 mg L-1. ........................................... 16 Figure 3. HACH 5000 Standard Curve for 3-6 mg L-1. ............................................................... 16 Figure 4. HACH 5000 Standard Curve for 4.5-10 mg L-1. .......................................................... 17 Figure 5. Wavelength scan of 6 mg L-1 DNP (no Ferrate). .......................................................... 23 Figure 6. Wavelength scan of 3.5: 1 Molar Ratio of Ferrate:DNP. ............................................. 23 Figure 7. Wavelength scan of 14:1 Molar Ratio Ferrate: DNP. .................................................. 24 Figure 8. Comparison of the test pH on DNP Removal at similar dosages. ................................ 25 Figure 9. pH 4 reaction data at various molar ratios of Ferrate : DNP (average of duplicates). 26 Figure 10. pH 6 reaction data at approximately 4.2 molar ratio of Ferrate to DNP. ................... 26 Figure 11. pH 8 reaction data for approximately 5.5 molar ratio of Ferrate to DNP. ................. 27 Figure 12. Effects of molar ratio on DNP removal at various pH values. ................................... 28 ix LIST OF TABLES Table 1. Summary of Reaction Product Tests (average
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