REMOVAL OF RESIN AND FATTY ACIDS FROM PULP MILL WASTEWATER STREAMS A Dissertation Presented to The Academic Faculty By Stephen P. Makris In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Chemical and Biomolecular Engineering School Georgia Institute of Technology September, 2003 Removal of Resin and Fatty Acids from Pulp Mill Wastewater Streams Approved by: Dr. Sujit Banerjee, Advisor Dr. Yulin Deng Dr. Howard L. Empie Dr. Lucian A. Lucia Dr. Spyros G. Pavlostathis Approved January 5, 2004 ACKNOWLEDGEMENTS Pursuing a Ph.D. degree is both a journey and a commitment requiring the support of many people. I have been extremely fortunate to be surrounded by many talented and caring mentors, colleagues, friends and family. I would like to recognize the assistance of some of these people here. First, I would like to acknowledge the support of the member companies of the Institute of Paper Science and Technology for partially funding this research and my education. My thanks are also extended to Georgia-Pacific Corporation for additional funding and assistance from Keith Bentley, Robert Sackellares, Myra Carpenter, Carl Rush, and Tobin Finley. I would also like to thank Greg Hollod and Dell Majure at Riverwood International for their support of this research. I gratefully thank my advisor, Sujit Banerjee, for the guidance, inspiration and the moments of levity that helped to keep me on course and focused on the completion of this dissertation. I would also like to thank my dissertation committee, Yulin Deng, Howard L. “Jeff” Empie, Lucian A. Lucia, and Spyros G. Pavlostathis, for their time reviewing this manuscript and their thoughtful advice. I give special thanks to my friends and family for their unwavering support; I truly could not have completed this journey without them. My greatest thanks go to my wife, best friend, and light of my life. Libby, this dissertation is dedicated to you. iii TABLE OF CONTENTS Acknowledgement ............................................................................................................ iii Table of contents............................................................................................................... iv List of Tables ................................................................................................................... vii List of Figures................................................................................................................... ix List of Symbols and Abbreviations................................................................................... xi Summary.......................................................................................................................... xii 1. Background..................................................................................................................... 1 1.1. Toxicity Definitions and Testing ................................................................ 2 1.2. Toxicity of Effluent Components ............................................................... 7 Bleach Plant Byproducts................................................................................. 7 Natural Components ....................................................................................... 9 1.3. Effluent treatment systems........................................................................ 13 1.4. Sources of Toxic Components.................................................................. 16 1.5. Partitioning of Resin Acids....................................................................... 18 1.6. Section Summary...................................................................................... 24 2. Dissertation Questions and Research Objectives.......................................................... 27 2.1. Research Objectives.................................................................................. 28 2.2. Thesis Approach ....................................................................................... 30 3. RFA and Toxicity Removal Across the ETS................................................................ 32 3.1. Section Overview...................................................................................... 32 3.2. Experimental Approach ............................................................................ 33 3.3. Experimental............................................................................................. 35 3.4 Results and Discussion ............................................................................. 44 iv 3.5. Section Summary...................................................................................... 69 4. DHA Acute and Chronic Toxicity in Treatment System Effluents.............................. 71 4.1. Section Overview..................................................................................... 71 4.2. Experimental Approach ........................................................................... 73 4.3. Experimental............................................................................................ 74 Microtox® bioassays .................................................................................... 74 Ceriodaphnia dubia bioassays..................................................................... 76 4.4. Results and Discussion ............................................................................ 78 Microtox® dose-response experiments ........................................................ 78 C. dubia dose-response experiments............................................................ 81 4.5. Section Summary..................................................................................... 85 5. Mapping Pulp Mill Sewers for Resin and Fatty Acids ................................................ 86 5.1. Section Overview..................................................................................... 86 5.2. Experimental Approach ........................................................................... 87 5.3. Experimental............................................................................................ 93 5.4. Results and Discussion ............................................................................ 95 5.5. Section Summary.....................................................................................100 6. Resin and Fatty Acids Removal from Pulp Mill Sewers using Flotation....................102 6.1. Section Overview.....................................................................................102 6.2. Experimental Approach ...........................................................................103 6.3. Experimental............................................................................................109 v 6.4. Results and Discussion ..........................................................................113 6.5. Section Summary...................................................................................124 7. Conclusions and Recommendations ..........................................................................125 Appendix A.1.................................................................................................................134 Appendix A.2.................................................................................................................140 References......................................................................................................................146 vi LIST OF TABLES Table 1.1. Fatty acids most commonly found in wastewater streams. ............................. 11 Table 1.2: LC50 (Rainbow trout) of key extractives. ....................................................... 13 Table 3.1. Mill A effluent treatment system characteristics. ............................................ 36 Table 3.2. Summary of sample collection dates and testing matrix. ................................ 43 Table 3.3. Operational ranges for Mill A ETS influent. .................................................. 45 Table 3.4. Operational ranges for Mill A ETS final effluent........................................... 45 Table 3.5. Overall ETS operating efficiencies and flow rates at Mill A. ........................ 46 Table 3.6. Statistical significance of COD levels across ETS (α = 0.05)......................... 48 Table 3.7. Acute and chronic toxicity for December 6-10, 1999. .................................... 49 Table 3.8. Acute and chronic toxicity for March 6-9, 2000. ............................................ 49 Table 3.9 Average RFA and TSS concentration during effluent treatment...................... 52 Table 3.10 Average RFA and TSS removal contributions to overall removal rate.......... 54 Table 3.11. Physicochemical properties for model resin and fatty acids,......................... 59 Table 3.12. Comparison of DHA and RFA levels (ppm) across Mills A and B. ............. 68 Table 4.1. Volumetric concentrations used in Microtox® dose-response experiments. ... 75 Table 4.2. Test conditions for DHA chronic toxicity dose-response experiments. .......... 77 Table 4.3. Results of the Microtox® dose-response experiments. .................................... 79 Table 4.4. Sample pH range over duration of chronic dose-response experiments.......... 82 Table 5.1 – Separation processes and operating principles. ............................................. 88 Table 5.2 – Physicochemical properties of DHA. ...........................................................