Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1947 Study of Methods for Processing Tall Oil. Frank Abel Anderson Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Part of the Chemical Engineering Commons Recommended Citation Anderson, Frank Abel, "Study of Methods for Processing Tall Oil." (1947). LSU Historical Dissertations and Theses. 7897. https://digitalcommons.lsu.edu/gradschool_disstheses/7897 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. MANUSCRIPT THESES Unpublished theses submitted for the master’s and doctor’s degrees and deposited in the Louisiana State University Library are available Tor inspection. Use of any thesis is limited by the rights of the author. Bibliographical references may be noted, but passages may not be copied unless the author has given permission. Credit must be given in subsequent v>?ritten or published work. A library which borrows this thesis for use by its clientele is expected to make sure that the borrower is aware of the above restrictions # LOUISIANA STATE UNIVERSITY LIBRARY 119-a STUDY OF METHODS FOE PROCESSING TALL OIL A Dissertation Submitted to the Graduate Faculty or the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemical Engineering by Frank Abel Anderson S*, University of Southern California, 1936 M.S*, University of Maine, 1940 June, 1947 UMI Number: DP69275 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. UMI Dissertation Publishing UMI DP69275 Published by ProQuest LLC (2015). Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code uest ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 R f 7 f O 10 Acknowledgement The writer is indebted to and gratefully wishes to acknowledge the aid which he received from the following individuals during the various phases of his investigation* To Dr* Paul M* Horton, Head of the Chemical Engineering Depart­ ment, for directing the project and for his continued guidance, helpful suggestions and advice* To Mr* Wilbur F* Gillespie, Technical Director of the Gaylord Container Corporation, and other officials of the company, for sponsoring the fellowship which made the investigation possible* To Mrs. Grace K. Cameron, Chemistry librarian, for her unstinting aid during the literature search* 3 4 * g ;j 9 I. I it TABLE GF CONTENTS CHAPTER PAGE X* ISTRCDUCTION - A SURVEY OF THE ORIGIN, PRODUCTION, PROPERTIES AND USES OF TALL OIL 1 The Constituents of Coniferous Woods 3 Production of Tall Oil 5 The Effect of Wood Variables on the Properties of Tall Oil 7 Tall Oil Yields 9 Tall Oil Analyses lO Processing of Tall Oil 13 Trade Demands on Tall Oil 16 II. SURVEY OF TALL OIL AND RELATED LITERATURE 21 Section X — Treatment of Processed and Unprocessed Ski raisings (Soap) 21 1. Washing 22 2. Solvent Extraction 22 3 . Acid Gas, Acid Salt and Acid Treatment 22 h f Fractional Precipitation and Other Miscellaneous Methods 2h Section II — Treatment and Separation of the Components of Tall Oil 25 1. Distillation 2$ 2. Esterification 23 3. Solvent Treatment and Extraction 31 h* Miscellaneous Methods of Treatment 35 Section III — Treatment of Unsaponifiable Matter 3 9 ill CHAPTER PAGE III* THE INVESTXGATION OF THE USE OF SKB4MINGS (SOAP) AS T ^ STARTING MATERIAL IN THE SEPARATION OF THE COM­ PONENTS OF TALL OIL 1*2 Introduction h2 Summary 1*2 Experimental Procedures and Results 1*3 X* Preliminary Experiments 1*1* 2* Properties of Varsol Soap—Solution Emulsions 1*5 3-* Initial Experiments on the Acidification of Soap Solutions 1*6 h+ The Salting—Out of Soap from Soap Solutions 1*9 5* Extraction of Soap Solutions h9 6* Extraction of Soap Solutions with Solvents Other than Varsol 67 IV* EXPERIMENTS ON THE PRODUCTION AND THE CRYSTALLIZATION OF TALL OIL 70 Int reduction 70 Summary 71 Experimental Procedures and Results 7l* Section I — Determination of the Optimum Conditions for Producing a Refined, Crystallizable Tall Oil 71* 1* Determination of the Optimum Conditions for Producing a Tall Oil—Varsol Solution Directly from Soap 75 2 • Determination of the Optimum Conditions for Acid Treating, Washing and Clay Treating Tall oil—Varsol Solution® 83 Section II — The Crystallization of Tall Oil 100 IT CHAFFEE FACE V. EXPERIMENTS INVOLVING THE ESTER IF ICATION OF TALE OIL 113 Introduction 113 Suam&ry 113 Experimental Procedure® and Result® 115 1. Effect of Esterification on Crystallisation 115 2* Extraction of Rosin Acids from Partially Esterified Tall Oil 120 VI. MISCELLANEOUS EXPERIMENTS 131 Introduction 1 31 S s m a r y 131 Experimental Procedure® and Results 133 1. Salting—out and the Selective Precipitation of Soap Solutions 133 2. Effect of Treating Skimming a with Hot Caustic Solutions I3 6 3« Effect of Washing Soap with Sulfate Turpentine and Cooling a Tall Oil—Turpentine Solution to O^C. 13 8 it. Effect of Using a Large Excess of H2S0|, to Treat a Tall OiL-Varsol Solution 139 5* Aramoniation of a Tall Oil-Varsol Solution 1^3 6 . Effect of Treating a Tall Oil—Varsol Solution with an Excess of Super—filtrol (Cold Treatment) 1^3 7-m Effect of Treating a Tall Oil—Varsol Solution with «AAW Fullers Earth (Cold Treatment) 1&3 8 . Effect of Treating a Tall Oil-Varaol Solution with Super—filtrol (Hot Treatment) ibfa 9 m Effect of Cooling a Tall Oil-Varsol Solution U 4I4 10* Effect of Adding Water to a Tall 011-Absolute Alcohol Solution H 4JU 11. Partial Saponification of Tall Oil 11*6 v CHAPTER PAGE 12, Extraction of a Tall Oil-Varsol Solution with a Concentrated Solution of Sodium Salicylate 1U6 13, Reaction of Tall Oil with Haleic Anhydride IU7 Hi* Esterification of Tall Oil with Zeo-Karb H as a Catalyst Hi? VII* VACUUM DISTILLATION AND TOPPING OF TALL OIL lh9 Introduction 12*9 Summary 1U9 Experimental Procedures and Results 151 1, Distillation of a Mixture of a Bogalnsa Crude Tall Oil and Borax 151 2, Vacuum Distillation of a Crude Tall Oil 152 3* Vacuum Distillation of a Bogalusa Refined Tall Oil 153 it. Vacuum Topping of a Bogalusa Refined Tall Oil 157 5. Vacuum Topping of a Bogalusa Crude Tall Oil 157 6, Vacuum Topping of a Laboratory Prepared Crude Tall Oil 163 7* Production and Refining of Tall Oil 161*. 8, Vacuum Fractional Distillation of Crude Tall Oil 168 BIBLIOGRAPHY 177 AUTOBIOGRAPHY 192 vi LIST <F TABLES TABLE FACE 1. Summary of Kurthfs Bate on the Ether Extractive® from Fine Wood 8 lit Tall Oil Yields from Various Mills 9 XXI. Seasonal Variations of Tall Oil Yields 10 XV. Representative Analyses of Various Tall Oils 11 V. Specifications of a Tall Oil to be Used to Replace a Heavy Mineral Oil 11 YX? Average Composition of the Fatty Acid Portion of Six American Tall Oils 12 VXX. Prices of Tall Oil 16 VIII. Summary of the Results of the Extraction of a Partially Acidified 1055 Soap Solution with Varsol (Test 1?) 52 XX. Analyses of Varsol Extracts from Test 1? 55 X. Analyses of a Tall Oil Before and After L 8 Hours of Crystallization (Test 69) 85 XI. The Effect of Acid Treating on the Rosin Acids Content of a Refined Tall Oil (Test 7h) 88 XXI. Color of Products after Various Treatments (Test ?L) 69 XIII. Effect of Treating Tall Oil-Varsol Solutions with Equal Amounts of i^SO^ Applied in Varying Concentra­ tions 90 XIV. Effect of Varying Clay Treatments on the Properties of Tall Oil-Varsol Solutions and Refined Tall Oil 91* XV. Analyses of 11 Ester Oil” andHosin Oil" Fractions from Test 103 121* XVI. Bata and Results for Tests 103 $ 105 and 106 128 XVII. Results of the Vacuum Distillation of a Bogalusa Crude Tall Oil - Test 111* 151* vii TABLE RfcDE XVIII. Results of the Vacuum Distillation of a Bogalusa Refined Tall Gil - Test 116-B 155 XU* Accumulative Data far Test 116-B 158 XX* Accumulative Data for Test 116-B (On Basis of Fatty Acids) 259 XXI* Vacates Topping of a Refined Tall Oil — Test 118 160 XXXX* Vacuum Topping of a Bogalusa Crude Tall Oil - Test 119 162 2X1II. Vacuum Topping and Treating of a laboratory Prepared Crude Tall Oil - Test 120 165 XXXV* Weight Material Balance for Test 121—A 166 XXV* Analyses of the Treated Distillation Products — Test 121 169 XXVI* Analyses of Treated Products from Test 122 171 XXVXI* Analyses of Products from Test 125 17U XXVIII. Results of Test 125 1 ^ 6 viii LIST GF FISGEES FIGURE PAGE !♦ Effect of the Addition of 10$ HgSGjL on the pH of a 10$ Soap Solution (Test 10} U7 2* pH of a Partially Acidified Soap Solution vs* Volume of 10$ (2.2H) %S0^ Added (Test 1?) 51 3* Soap Extraction Column 60 li* Rate of Crystallization of Tall Oil 112 ix LIST OF ILLUSTRATIONS Structures of Some Tall Oil Components X. Abstract Tall oil, the by-product mixture of rosin acids, fatty acids and unsaponifiable matter obtained by splitting the crude soap recovered from the black