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TANNING EMU SKINS: an ASSESSMENT of the PROCESSES, the LEATHER PROPERTIES, and the POTENTIAL for CHROMIUM REDUCTION by VENKATESW

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TANNING EMU SKINS: an ASSESSMENT of the PROCESSES, the LEATHER PROPERTIES, and the POTENTIAL for CHROMIUM REDUCTION by VENKATESW TANNING EMU SKINS: AN ASSESSMENT OF THE PROCESSES, THE LEATHER PROPERTIES, AND THE POTENTIAL FOR CHROMIUM REDUCTION by VENKATESWARA REDDY KOTLA, B.Tech. A THESIS IN CIVIL ENGINEERING Submitted to the Graduate Faculty of Texas Tech University in Partial Fulfillment of the Requirements for the Degree of MASTER OF SCIENCE CIVIL ENGINEERING Approved Accepted Dean of the Grad\idte/}^})oo] May, 1996 73 ^ ' "^ ' t. ACKNOWLEDGMENTS fJO . ^ I would like to thank Dr. R. W. Tock for his valuable guidance, scholarly suggestions, and constant encouragement throughout this research work. I am grateful to the other members of my committee. Dr. R. H. Ramsey and Dr. T. R. Mollhagen, for tiiefr valuable suggestions and advice throughout my degree program. I take this opportunity to thank the Leather Research Instimte (LRI) which sponsored this research and the State of Texas for funding this project. I am thankful to Dr. Eberspacher of LRI for giving me complete access to the LRI Ubrary. Special thanks are due to my wife for helping me many times during the course of this research work and for aU she has endured. And lastly, my sincere thanks to my family for their constant support and encouragement. Without their blessings and good wishes, I would not be at this stage today. u TABLE OF CONTENTS ACKNOWLEDGMENTS ii ABSTRACT v LIST OF TABLES vi LIST OF FIGURES vii CHAPTER I. INTRODUCTION 1 Overview of the Leather Industry 1 Types of Leather Produced 1 Types of Animals Slaughtered 5 Emus 5 Objectives of the Research 6 II. BACKGROUND INFORMATION 8 Structure and Composition of Hides 8 Tanning Processes 11 Chemistry of Chrome Tanning 20 Industrial Wastewater 24 Industrial Waste Treatment 26 Tannery Effluent Characteristics 27 Tannery Waste Treatment 31 iii 11 L EXPERIMENTAL APPROACH 41 Hide Preservation 41 Hide Preparation 41 Tanning Process 42 Mechanical Testing 46 Wastewater Analysis 46 Chemical Precipitation 47 IV. RESULTS AND DISCUSSION 48 General Appearance of Tanned Emu Leather 48 Thickness Variations 48 Area and Weight 48 Tensile Properties 50 Waste Characteristics 48 Waste Treatment 53 V. CONCLUSIONS AND RECOMMENDATIONS 64 Suggestions for Further Studies 65 REFERENCES 68 IV ABSTRACT The tanning of ratite skins has not been actively practiced in the United States. There is scant Hterature available on the tanning and properties of ratite skins. In this context, the Leather Research Instimte at Texas Tech University has undertaken an experimental program to tan emu skins and then investigate the potential for this leather to be used as a commercial product. The traditional chrome tanning process was used in the tanning of emu skins. An Instron Universal Testing Machine (Model 1122) was used to estimate the strength of the tanned leather. The leather was characterized by the thinness and the presence of pores from where the feathers were removed. The strength of the leather was almost 50% of the strength of bovine leather. It was also decided to investigate the recoverabiUty of chromium from the spent tan liquor. The available literature on treating the tannery effluent was reviewed and it was decided to use the widely accepted method of chemical precipitation of chromium by pH adjustment. Lime was used as the precipitating agent. This resulted in a 99.9 percent removal of chromium at a pH of 8.5 while the removal of other parameters like COD and solids was not encouraging. A methodology was devised from the results to recover and reuse the chromium from the spent tan liquor but no tests using this methodology have been conducted. LIST OF TABLES 1.1 End Uses of Leather from Different Hides and Skins 3 2.1 Tanning Substances and Their Characteristics 18 2.2 Leather Tanning and Finishing Industry Subcategory 28 2.3 Effluent Characteristics for Various Tanneries 32 2.4 Pollutant Loads for Beamhouse and Tanyard/Retan/Wet Finish Operations 36 2.5 Chromium Removal from Chrome Liquor by Adsorption 40 4.1 Tensile Properties of Emu Leather 51 4.2 Characteristics of Spent Chrome Tan Liquor 52 4.3 Comparison of Raw and Treated Chrome Tan Waste 58 4.4 Effluent Discharge Limitations for Chromium 62 VI LIST OF HGURES 1.1 Geographical Distribution of U.S. Tanneries 2 2.1 Approximate Composition of a Hide 9 2.2 Structure of an Animal Skin 10 2.3 Hair Removal Processes 14 2.4 Effect of Sah on Acid Swelling 16 2.5 Stages in the Cross-Linkage of a Chrome Tannage 23 3.1 Leather Tannery Process-Chrome Tanning 43 3.2 Leather Tannery Process-Organic Tanning 45 4.1 General Shape and Thickness (in.) of a Chrome Tanned Emu Skin 49 4.2 COD Removal by pH Adjustment 54 4.3 Suspended Solids Removal by pH Adjustment 55 4.4 Total Solids Removal by pH Adjustment 56 4.5 Chromium Removal by pH Adjustment 57 4.6 Qualitative Element Identification: Supernatant 60 4.7 Qualitative Element Identification: Sludge 61 vu CHAPTER I INTRODUCTION Overview of the Leather Industry The American tanning industry originated during colonial times, and hence became concentrated in New England and the middle AUantic States. However, during the 19th and 20th Centuries, the sources of animal hides shifted westward resulting in the origin of some tanneries west of the Mississippi River as shown in Figure 1.1 (U. S. EPA 1980). Even so, nearly 85% of all tanneries are still located in the Eastern United States. The tanning of hides and skins into leather was an ancient practice followed by primitive man to cover himself. Animal skin consists of outer (epidermal) and inner (dermal) layers. The inner layer constitutes the leather-making portion of the skins namely collagen. The process of tanning involves two activities (Churchill 1983): 1. removal of layers which cannot be converted into leather, and 2. the treatment of other layers (that can be converted into leather), so that they do not putrefy but remain flexible and strong. Today, even though leather is being used for a variety of purposes, it has become a non-essential commodity. In essence, the leather tanning industry is a by-product industry skice it handles the hides and skins of slaughtered animals, bfrds, ratites, and reptiles used in the meat industry. Types of Leather Produced The type of leather produced depends on the requirements of the ultimate user as well as the type of raw material utilized. Table 1.1 gives some of the different types of end uses for leather produced from different types of hides and skins. In general, most of the leather produced can be classified into the following types: o 00 < Ui CO of/y •c H CO D o a o -a u o Si G 'B G c/l (d 7o3 :s x: D> C4 G 00 -H O O (0 • 4J ^.^ -^ c « CoJ r gu CO in •p Id '-i o 4J CO • • •• r~n u: M - < a: i^ I Table 1.1 End Uses of Leather from Different Hides and Skins* Skin Origin End Use of Leather Cow and Steer Shoe and boot uppers, soles, insoles, linings; patent leather; garments; work gloves; waist belts; luggage and cases; upholstery; transmission beltkig; sporting goods; packings. Calf Shoe uppers; slippers; handbags and bfllfolds; hat sweatbands; book bindings. Sheep and Lamb Grain and suede garments; shoe linings; slippers; dress and work gloves; hat sweatbands; book bindings; novelties. Goat and Kid Shoe uppers, finings; dress gloves; garments; handbags. Pig Shoe suede uppers; dress and work gloves; billfolds; fancy leather goods. Deer Dress gloves; moccasins; garments. Horse Shoe uppers; straps; sporting goods. Reptile Shoe uppers; handbags; fancy leather goods. Source: Leather Facts (1977). Heavy Leather - Sole Leather This type of leather is usually used in shoe manufacture. As the name indicates, this leather is thick and so the hides used are from heavy-skinned animals like steers and cows. Vegetable tanning processes are usually employed to convert the heavy skins into sole leather. Not much can be varied with respect to the color and texture in this type of leather. Side Leather This type of leather is used in the manufacture of shoe uppers, work gloves, heavy garments, etc. Different varieties of leather can be made with changes in color and texture. The tanner* s artistry in fashions can be put to fuU use in the manner in which he manipulates the color, texture, and the finish of the leather. The chrome tanning method is usually employed to convert the skins into side leather. Garment Suede Leather This type of leather is made primarily from the skins of lamb and sheep produced in New Zealand. The tanner* s expertise in using the proper dyes to develop the desired colors is important for a successfiil operation of a garment suede tannery. These tanneries are usually smaller but more simple than the side upper tanneries. The properties usually demanded for this fashion leather are large areas (6 sq. ft) of uniform color and thickness, soft handle, and good drape (Shaiphouse 1989). Glove Leathers and Fancy Leathers Glove leathers are predominantiy made from sheep and lamb skkis and to some extent from deer, pig, goat, and kid skins. Glove leathers are used for riding, driving, and sports wear. Other types of glove leathers include the work gloves which are made primarily from horse, cattie, calf, sheep, and pig skins. Fancy leathers are those made from hides and skins of any kind that are commercially acceptable because of gram and the distinctive finish. The tanneries that produce glove and fancy leathers are usually small in comparison to those of shoe upper leatiier or sole leather tanneries. Types of Animals Slaughtered Different types of animals are slaughtered to produce different typ.es of leather products.
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