HANDBOOK OF ENVIRONMENTAL ENGINEERING™ VOLUME 11 Environmental BioengineeringEdited by Lawrence K. Wang, pno, Pe, DEE Lenox Institute of Water Technology, Lenox, Massachusetts, USA Krotta Engineering Corporation, Lenox, Massachusetts, USA Zorex Corporation, Newtonville, New York, USA Joo-Hwa Tay, Php, PE Nanyang Technological University, Singapore Stephen Tiong-Lee Tay, pho Nanyang Technological University, Singapore Yung-Tse Hung, pho, PE, DEE Department of Civil and Environmental Engineering Cleveland State University, Cleveland, Ohio, USA 3 Humana Press ISRN: 978-1-5R800-403-7 eISBN: 978.1-60327.031-1 DOE: 10.1001978-1.60327-031-1 Springer Now York Dordroeht side rong London Livy of Congress Contal Namo: 2010028632 © Spritger Science+Business Mea LLC 2010 All ighis reserved, This work may nn be tansleted or copied in whole or in part without the writen permission ofthe publisher (aman Pres, of Springer Scincetlsinest Melia, LLC. 233 Sorin eo. New York. NY 1013, USA). escent for bef excerpts in cancetion with Teuews or scholarly analysis. Use in conaection with any form of information storage and retieval elecroni adaption, computer wftware orby siilar or dstinilr methodology now krown e hereafter developed isforbidsen Te usein this publication of wade rames. trademarks service marks, and sila terms, even if dey are not identified 2s suc, {sol te liten sam expression of opinin as to wholner op nol hey ane stect lo progr right. Dod on acid free paper Humans Pres spt of Springer Sciences Business Media (wwu.springerm)19 Animal Glue Production from Skin Wastes Azni Idris, Katayon Saed, and Yung-Tse Hung, Contents INTRODUCTION PRETREATMENT AND CONDITIONING EXTRACTION CHEMICAL MODIFICATION APPLICATION CASE STUDY: PRODUCTION OF GLUE REFERENCES [Abstract Anal pd is te most important protein adhesive obtained fiom Sil hides, Skins, and bones trough hydrolysis of ihe collagen. Animal glue proton has Ing been ‘crave business in varcus par ofthe World. This chapter discusses pretreatment and Sonuttoning echnigiesinctaing ale aka and enayne proteolysis Which ae ised dling anita gluc production, The extaction methods cluding deoasraion and thermal treater re ako discussed, The ble improvernea ef pot Lie ant mostre resistance banal glu ung chems! maton erga resent The appeaton 9° mie bubble technique for glue peoduction from cow also introduced. 1, INTRODUCTION Animal wastes primarily consist of solid manure and liquid effluent generated from farms and feedlot, Large quantities of animal wastes containing high Jevels of organic pollutants are also produced by slaughterhouses and poultry processing centers. Waste streams from meat processing such as blood, hides or skin, bones and, offals are potential contiibutors both in crms of solid waste, also called animal biomass, and liquid effluent. The application of animal, as useful proxuets is widely practiced worldwide as part of the pollution preven and waste minimization strategy adopted in many countries. In some parts of the world, glue . iS Hane of Erovormentd Enger, Vlume Ts Exironmentl Bogineing Salted by: 1. K.Nanget ae DOL HDI007/o0 | wee ONT Ti, opongerselece 1 nee Med, LLC 2010 685 686 Avldris et al. production from animal bones and hides has been a lucrative business. Proper handling and disposal of animal waste are important in protecting human health (1). This chapter focuses on the utizaion of animal skin or hides forthe production of glue. Usually the hides are processed into various predets fer the Teather indus, bt hoader perspective of converting the into aqueous gel or gelatin also deserves examination,1.1, Animal Skin Generation Rates Knowledge of the quantities of animal skin or hides generated and collected for further processing is of fundamental importance to the management of animal wastes and byproducts. ‘The quality and available quantities of skin or hides also determine the method to be used for economic reasons. The world’s production of animal skin or hides is estimated to be 108 million metric tons per annum in 2003. Literature review reveals the annual production of animal skin or hides from sheep, goat, cattle, and buffalo, Cattle hides account for more than 68% of the total animal skin production (1). In global terms, Asia leads the world by producing more than 2.47 million tons of animal skins in 2003. In contrast, Europe and the United States produced about 1.30 million tons and 1.04 million tons of cattle hides, respectively, in 2003 (2) 1.2, Hide Removal from Cattle and Sheep In animal skin orhide processing, slaughterers normally remove hides from eattle and sheep to reduce the potential contamination of carcasses by hair, dirt, and manure. Usually, hides are removed from cattle and sheep mechanically after the removal of the head, tail, and hooves. ‘The provess of hide removal begins with some initial separation from the carcass manually, using either conventional orait-driven knives, to enable attachment of mechanical pullers. The pullers then remove the hide by cither pulling up from the neck to the tail or pulling in the reverse direction, which is less common. Typically, pulling of the hide is carried out manually with good results, but it requires experienced slaughterhouse personnel to do it efficiently @). The hide must be preserved 1o prevent degradation duc to rapid microbial attack. On-site hide processing can consist of salting for preservation before shipment to leather tanning ‘operations, oF it ean involve washing, defleshing, and salting before shipment. However, on- site hide processing options may also include curing before shipment for off-site tanning or complete processing followed by the marketing of tanned hides (4). 2. ANIMAL GLUE Glue production from animal bones and hides has long been a lucrative business in various parts of the world. Animal glue historically refers to “hide or bone glue” adhesives, which need to be heated and melted before usage. Animal glue is the most important protein adhesive obtained from cattle and other animal hides and bones by hydrolysis of the collagen. Hide glue igher in molecular weight than boue glue and therefore stronger (5). ‘The popularity of this product is due to its unique combination of properties, which cannot be achieved by other synthetic resins, such as the ability to deposit a viscous, tacky film from a hot aqueous solution that forms a fiem gel while cooling. Other properties include ease ofAnimal Glue Production from Skin Wastes 689 contain both amine and carboxylic groups, which are reactive and ionizable, These electrically charged sites affect the interactions among protein molecules and between protein mol and water. These polar and ionizable groups are believed to be largely responsible for the formation of gelatin and the characteristic rheological properties of animal glue. Cross-linkage between protein molecules is possible through hydrogen, ionie, and covalent bonds. ‘Animal glue is amphoteric because the amine and carboxyl groups contained in the polypeptide protein chain are reactive and ionizable. In a strong acid solution, protein is Positively charged and acts as a cation. In a strong alkaline solution, it is negatively charged and acis as an anion, The intermediate point, where the net charge on protein is zero, is known as the isoelectric point (IEP) and is designated in pH units. The TEP varies, depending ‘on whether the pretreatment of collagen is acidic or alkaline. During processing, acidic or alkaline treatments are used to hydrolyze the amide groups in collagen to a greater or lesser extent, liberating the acid functions, Acid-processed glue (little amide group modification) has an IEP near 9.0, and alkaline-processed glue (low residual amide groups) has an IEP close (048 6). Another important characteristic in gelatin production is the gelation of animal glue upon cooling. Gelation involves both intra- and intermolecular reorientation upon cooling of the solution. Itis caused by the formation of random primary and secondary bonds. Intermolecular network formation is primarily the result of a cross-linking mechanism between molecular chains by a hydrogen bond, 2.4, Manufacturing The ultimate objective of glue production is the conversion of material containing collag of different degrees of insolubi glue with good physical-chemical properties such as gel strength, viscosity, low ash content, and clarity. The fundamental production process is based on three stages (8): lity into a maximum quantity of soluble and highly puri ied 1, Preparation of raw material, -e., the elimination of non-collageneous components from the stock ‘material with or without the reduction of cross-linkage hetween collagen components 2. Conversion of purified collagen into glue or gelatin 3. Refinement and recovery of glue or gelatin in dried form Preparation of animal glue is essentially a treatment of a collagen source with heat and water in order to hydrolyze it toa soluble product as rapilly and as efficiently as possible. The resulting solution is filtered, centrifuged to remove fat, concentrated to a suitable concentration in an evaporator, chilled to gel the concentrate, extruded or cut into particles, dried, ground, and analyzed. The quality and cleanliness of the raw materials, their cleaning and preprocessing, and the speed of extraction, concentration, and drying determine the quality of the product hhe quantity of glue obtained is affected by the quantity of hides or bones used initially, the nature of the raw material, the extraction temperature, the time of extraction, the amount of water used and the number of extractions carried out (8). All the raw materials are washed with large volumes of cold water t remove alll con- taminants such as blood, manure, salt, and dirt. ‘The duration of washing will depend on the cleanliness of the raw material at the start, The wash is complete when the water runs clearAnimal Glue Production from Skin Wastes 691 out at two different temperatures of 5 and 10°C for soaking periods of 5, 10, 15, 20, 25, and 30 days with vigorous stirring every 70-72 h, Yield improvement was obtained, with a yield of 34 per 100 g of sample at soaking conditions of 5°C for 30 days, while at 10°C the yield was about 29 g per 100 g for the same period. 3.3, Enzymic Proteolysis ‘Typically, the soaking process in alkaline or acidic suspension for an extended period. involves large quantities of materials. Any process that might reduce the conditioning time of hide is worthy of investigation. One such process is that of enzymic proteolysis. The hide is weated in buffer solution at pH 12.5-10.0 at temperature 24-28°C for 2 days, followed by washing and acid treatment in a tumble. The acidification step denatures the enzyme and prevents further proteolysis of extracted gelatin (13). 4. EXTRACTION The extraction process consists of transferring the pretreated washed material into an extraction vessel containing hot water (60-65°C), heating with agitation for a suitable time, and draining the liquor from the bottom. More water is added and the step is repeated at a slightly higher temperature for shorter periods. Several extractions are made in this fashion until the liquor that is removed contains only 1% solids. At this point, the economics of the extraction prevents further processing. Residue (grout) in the extraction vessel is removed and may be dumped, but it is usually dry-rendered to recover fat. As the extraction proceeds, the volume of material shrinks and, thus less water is required. In order to alleviate poor extraction, hot water and agitation are used! prevent packing in the extraction vessel, which ‘causes poor extraction, Rapid operations are essential for the formation of glue material. Glue liquor usually hydrolyzes readily at a concentration of 29%. Deterioration of quality in dilute glue at the formation stage is also common dus to favorable conditions for bacte and fungi t form a natural breeding medium. In practice, the liquor is then filtered as rapidly as possible to remove any suspended fines and transfesred to evaporators. These usually are multiple-effect vacuum machines that can concentrate Fiquors to 20% solids if the quality of glue is not too high. Further concentration of liquor can be accomplished with wiped-film-type evaporators or plate evaporators for maximum concentration, The concentrated liquors or heavy liquors (as they are sometimes called) are readly for a variety of drying processes. The liquor may be chilled for gelling by passing over a chill roll and then through a slicer that forms long strips for the drying oven. The liquor may also be chilled by pumping itto a refrigerated rotator that chills and extrudes it under pressure onto a belt where the noodles are carried 0 a dryer. Cole and McGill (13) reported that the extraciability of the hide may be greatly decreased as animal age increases. The parallel increase in insoluble residue with animal age is to be ‘expected, but the same relationship of gelatin yield to animal age would not necessarily follow, because the yield depends upon the variable salt, hair, and fat contents, If one assumes that calves average 6 months, young animals 20 months and aged animals 60 months, then for the conditions given, the first extraction exiractability decreases by some 0.5% for each monthAnimal Glue Production from Skin Wastes 693 46°C, for a period of 3.5h or less at a water to collagen-containing material ratio of about 1,5-2.5:1 to remove the increased amount of gelatin at relatively low tempera ture. Several more extractions were possible with the extraction temperature maintained below 52°C, and the time of contact of hot water with the collagen-containing material being maintained at 3h or less. Finally, they found that water added in the low-temperature extractions permitted a more efficient extraction and improved the recovery of gelatin in a relatively shorter period. Fadilah et al. (12) used the conventional extraction method in the production of animal glue at different starting temperatures. Samples of collagen-containing material were fed to a glass besker containing 60°C distilled water for Lh. The fat emulsion skimmed up on the water surface was easily separated. The samples were extracted in three stages at increasing temperatures of 60, 70, and 80°C for 8h each, The extracted glue was then filtered, and the clear glue liquid obtained was dried in a temperature controlled water bath at 60°C for 10-14h Lakoche et al. (19) reported an improved process for the manufacture of gelatin from collagen-containing material by utilizing a caustic solution. Collagen-containing material was demineralized to produce Ossein, which was homogenized or ground. The Ossein was added to a water solution of sodium hydroxide or potassium hydroxide at a concentration of at least 44 by weight and a swelling restraining salt (sodium sulfate) at a concentration of at least 3% by weight for 10-120 h (0 form a reacted slurry, The slurry was heated at a temperature of at least 45°C for 30 min to produce a gelatin-containing solution that was then clarified by raising the pH of the solution to greater than 9.8, Sulfate salt was added to the gelatin solution to reduce the pH ranging between 7 and 8, Phosphoric acid was aelded to the solution to reduce the pH ranging between 5 and 6, Following extraction and clarification, the gelatin solution was filtered, oxidized or de-ionized to achieve the desired level of micro-constituents, prior to concentration and drying 5. CHEMICAL MODIFICATION Animal glue can be produced using a chemical modification process. The modification of the chemical constituent of animal glie involves reactions either with the polypeptide backbone of the molecule or more commonly with the side-chain groups along the polypeptile backbone, which are the amino group and the carboxy! group, ‘Gupta et al. (20) developed a process to convert animal glue into a hot set adhesive in which both the pot life and the moisture resistance of animal glue were improved. They indicated that animal glue can be applied to plywood along with paddy husk gel as an extender with a small percentage of potassium dichromate and paraformaldchyde to give a composition, witich when passed at about 100°C (25°C) met the requirement for tea chest plywood. They also suggested that the hot set composition of gluing, based on animal glue, had an advantage over the urea-formaldehyde based composition of reducing the cost of gluing to about 25% Stocts (21) invented a new thermal insulating foam from clear animal glue. This foam replaced highly flammable polyurethane foams, and flame-retardant types, which had a ten- dency to produce significant quantities of toxic smoke during a fire. The new foam produced was also better than cellulose insulation materials, including either flame retardants which696 A. Idris et al. Furthermore, Mohammed Issam studied the bacterial resistance of the cured adhesives against bacteria and fingus. Bacterial attack was observed in the animal glue sample after 3 days. For the cross-linked animal glue with MF, the bacterial growth was observed after I week. No bacterial growth was observed on the cross-linked animal glue blended with MP, and MUP, cross-linked animal glue blended with MUP after a 2-week experimental period (26) Mohammed Issam documented that the blending of animal glue with melamine-based. s had greatly improved the pot hfe of blended adhesives compared to the pot life of MUF resin used alone, For instance, the pot life obtained for the animal glue blended with MUF was 45 min, and for MUF alone, it was was 15 min, showing 66.6% improvement. The pot life obtained from blended animal glue and MP. and MUP was 30 min, showing 50% improvement over MUF (26). Additional glue factory waste management information ean be found from the literature (27). REFERENCES 1. Mustafa MY, Anjam AA (2009) A tetal quality management approach to handle veterinary hospital ‘waste management, J Animal Plant Sei 19(3)-163-164 2. ip faosttFao.0F8/ 2007) 3. USEPA (20(2) Development Document for the Proposed Effluent Limitations Guidelines and Standards for the Meat and Poultry Products Industry Point Souree Category (40 CTR 432) 4, hupil/wwwcboneglue.nevbonegluve-bunliskolnazicateks (2007) 5. Pearson CL (1964) Animal glues and adhesives. In: Pizzi P, Mital KL. (eds) A handbook of adhesives technology, Marcel Dekker, New York, pp 479-494 6. Enyieghalam ME (1985) Hydeolytic exirction of glue from femoral tone. Int T Aches Adhes 5(3):217-218 7. htep:swww.bjom netprod.htm (2007) 8. Ware AG, Courts A (1977) The science and technology of gelatin, Academic, Lordon, England 9. Poppe J, Ridoux C, Grouber B, Schoentjes M (1988) Gelatin product having highly improved properties of Wettabilty and Dispersibility andl a method of making the same. USA Patent, March 4,722, 897 10. Reich G (1952) Relationship between collagen and gelatin. In: Ward AG. science and technology of gelatin. Academic, London, England 11, Babloyan 00 (1968) Relationship between collagen and gelatin In: Ward AG, Courts A (eds) The science and technology of gelatin. Academic, London, England 12. Padiluh BM, Ab. Kadir MO, Said AZ, Abd Ruhman N (1994) The effect of size und ereatmeat ‘method on the conversion of dred cattle hide into glue. Int Symp Bioproducts Processing, Januaty. pp 270-273 13. Cole CGB, MoGill AEF (1988) Technical note: effect of animal age and conditioning method on the conversion of bovine hide into gelatine. In J Tood Sei Technol 23:525-529 14, Cole CGB, Robeats 1J (1956) Gelatine fluorescence and its relationship to animal age and gelatine color. S Afr Food Sei Nutr 8(4):130-143 15. Flory PI, Weaver ES (1960) Relationship between collagen and gelatin. In: Ward AG, Courts A (cds) The science and technology of gelatin, Academie, London, England Courts A (eds) The