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Critical Reviews in Environmental Science and Technology


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Recovery and Utilization of ChromiumTanned Proteinous Wastes of Leather Making: A Review


V. John Sundar , J. Raghavarao , C. Muralidharan & A. B. Mandal
b a a b a

Leather Process Technology Department, Central Leather Research Institute, Council of Scientific & Industrial Research, Chennai, India
b

Chemical Laboratory, Central Leather Research Institute, Council of Scientific & Industrial Research, Chennai, India Available online: 04 Jul 2011

To cite this article: V. John Sundar, J. Raghavarao, C. Muralidharan & A. B. Mandal (2011): Recovery and Utilization of Chromium-Tanned Proteinous Wastes of Leather Making: A Review, Critical Reviews in Environmental Science and Technology, 41:22, 2048-2075 To link to this article: http://dx.doi.org/10.1080/10643389.2010.497434

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Critical Reviews in Environmental Science and Technology, 41:20482075, 2011 Copyright Taylor & Francis Group, LLC ISSN: 1064-3389 print / 1547-6537 online DOI: 10.1080/10643389.2010.497434

Recovery and Utilization of Chromium-Tanned Proteinous Wastes of Leather Making: A Review


V. JOHN SUNDAR,1 J. RAGHAVARAO,2 C. MURALIDHARAN,1 and A. B. MANDAL2
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Leather Process Technology Department, Central Leather Research Institute, Council of Scientic & Industrial Research, Chennai, India 2 Chemical Laboratory, Central Leather Research Institute, Council of Scientic & Industrial Research, Chennai, India
1

Hides and skins, by-products of the meat industry, are converted into a value-added product, leather, by tanners. Tanning essentially is the process of converting raw hides and skins into an imputrescible substance. The tanning process has number of steps and generates signicant quantities of by-products and wastes. These solid and liquid wastes pose major a environmental problem if not managed effectively. Large-scale production systems are adopted for leather processing in clusters and, therefore, the industry receives focus of environmentalists and society. Consequently tremendous pressure is exerted by various pollution regulatory bodies. The hides and skins are treated with chemicals, which cross-link the collagen bers to form a stable, durable material. The chemicals used may be derived from traditional vegetable products or inorganic metal salts. During leather processing a number of size-reduction, leveling, and purication operations are carried out, which results in generation of untanned and tanned proteinous waste materials. The authors review various recovery processes and utilization methodologies of chrome-tanned proteinous solid wastes emanating from leather processing operations. KEY WORDS: bufng dust, chrome tanning, collagen, leather processing, skins and hides

Address correspondence to V. John Sundar, Central Leather Research Institute, Adyar, Chennai 600020, India. E-mail: johnsundar70@yahoo.co.uk 2048

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I. INTRODUCTION
The leather industry, which basically processes waste from the foodprocessing (meat-processing) industry, could easily be considered to be an environmentally friendly one if it were not for the large amounts of liquid as well as solid waste it generates. Leather products have been useful materials since the dawn of human history. In the tanning industry, raw skin is transformed into leather by means of a series of chemical and mechanical operations. Leather processing technology has evolved naturally from a traditional practice to an industrial activity. The leather industry contributes substantially to the pollution of the environment. Environmental challenges from leather processing arise from both the nature and the quantum of wastes discharged (Gaidau et al., 2009; Popescu et al., 2008; Ramasami et al., 1998; Veeger, 1993). The leather-making process generates substantial quantities of solid, liquid, and gaseous wastes (Figure 1). Processing of one metric ton of rawhide produces 200 kg of tanned leather, 200250 kg of tanned waste leather, 190350 kg of nontanned waste, and 50,000 kg of wastewater (Figure 2). Many cleaner processing approaches aimed at the reduction of liquid and solid wastes proved to be economically and environmentally benecial (Munz et al., 1997; Muralidharan et al., 2001; Sundar et al., 2008; Sundar et al., 2004; Sundar et al., 2002; Sundar et al., 2006; Taotao et al., 2009; Xuechuan et al., 2009). There are numerous options available to contain liquid and gaseous wastes. They include in-process and end-of-pipe treatment solutions. Attempts have also been made to combat the liquid discharge from the tanning processes to near zero levels. Solid wastes from the tanning industry are unavoidable at present. This is because leather processing is primarily associated with purication of a multicomponent, skin, to obtain a single protein, collagen. The intrinsic nature of the leather processing steps and the nature of chemicals employed are also responsible for the generation of certain quantum of solid wastes. Most of these wastes are disposed of through landll or incineration processes, although effective reutilization is greatly desirable, as the methods of disposal involve economic and environmental losses. Chromium has been the dominant tanning agent for the better part of the century, and now accounts for approximately 85% of all leather produced in the world. Other primary and combination tanning agents include vegetable tannin extracts; other metals such as aluminum, zirconium, and titanium; aldehydes; organic syntans; and sh oil. An extensive worldwide research effort has been devoted to alternative tannages, but no satisfactory replacement for chromium has been or appears likely to be found (Jiao et al., 2009; Rutland, 1991; Sundar et al., 2001). Tanning with chromium was invented in 1858 (Sarkar, 2005). Tanning is the main process that protects leather against environmental effects such

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Process Raw hides Unprocessed Trimmings Soaking Fleshing Unhairing + liming Bating Pickling

Waste

Trimmings, Fleshings BOD, COD, SS, Salts, Organic N H2S, NH3 Shavings, Trimmings BOD, COD, SS, Salts, Chrome

Pretanning

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Tanning

Chrome tanning Sammying Sorting Splitting Shaving

Wet finishing

Neutralisation Retanning Dyeing Fatliquoring Sammying Setting Drying Conditioning Staking Buffing Trimming Finishing

Trimmings

BOD, COD, Chrome, Dyes, Fat

Finishing

Solid residue Liquid residues Solvents, Formaldehyde

Leather

Solid wastes; ---- Liquid wastes; . Gaseous emissions

FIGURE 1. Description of the tanning process and outputs.

as microbial degradation, heat, sweat, and moisture. Basic chromium sulfate is the most widely used tanning material for converting putrescible collagen bers into a nonputrescible leather matrix (Gauglhofer, 1986; Groenestijn et al., 2002). One of the reasons for chromium being indispensable is that no other single tanning material can give the desired characteristics to the leather. Hides that have been tanned with chromium salts have improved mechanical resistance, extraordinary dyeing suitability, and better hydrothermal resistance in comparison with hides treated with a vegetable tanning agent or other tanning agents. Chromium is bound to collagen by more than one mechanism. However, all of the bound chromium contributes to an equilibrium that determines the thermal stability of the resulting leather.

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FIGURE 2. Environmental impact of leather processing (Chakraborty, 2003).

Chromium salts also have a higher rate of penetration into the interbrillar spaces of the skins. This results in substantial reduction in process time and better quality of the nished product. Sulfates and chlorides are the most studied chromium salts. Basic chromium chloride solutions contain a significant proportion of polynuclear complexes. This results in poor diffusion of chromium salts through the pelt, leading to supercial tanning. Chromium sulfates contain sulfate radicals, which can readily penetrate the complex ion and mask chromium. With basic chromium sulfates, products can be obtained easily and rapidly with a high molecular weight, giving colloidal solutions of a high tanning ability. This is the reason why chromium sulfate is used in preference to chloride in the tanning process (Chagne et al., 1996). Most tannery and other leather product wastes contain signicant amounts of chromium, which is present exclusively as Cr (III) salts. Production of chrome-tanned leather is done exclusively with Cr (III), usually in the form of basic trivalent chromic sulfate [Cr (OH)(H2 O)5 ]SO4 . This process depends on the unique ability of Cr (III) to form stable, kinetically inert coordination complexes, which can bind and cross-link hide protein bers (collagen). Figure 3 shows the molecular structure of chrome-tanned leather and shavings. Hexavalent chromium compounds are not tanning substances, as they do not have the ability to form such coordination complexes. In addition, typical tanning formulas contain masking agents (organic acid radicals such as formate or acetate), which help control the tanning reaction and

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FIGURE 3. Molecular structure of chrome-tanned leather and shavings (Gammoun et al., 2007).

further ensure the chromium is exclusively trivalent. Given the high organic content of these waste materials, it is highly unlikely that soluble Cr (VI) compounds could even persist as such in environment (Brown and Taylor, 2003; Kolomaznik et al., 2008). The products resulting from the tanning are grain leather, usable splits (a product obtained on horizontal sectioning of leather), and a certain amount of unusable splits (i.e., chrome-containing solid waste). At the end of chrome tanning about 75% of chrome offer (Cr2 O3 ) remains in the collagen structure. Other chemicals and auxiliaries such as tensides, calcium, acids, and bases (in the form of soluble reaction salts) remain in wet blue leather in small amounts (Buljan et al., 1999).

II. TECHNOLOGICAL SOLUTION FOR THE LEATHER WASTE A. Chrome Shavings, Splits, and Trimmings
Because tanned hides are too thick for most purposes, they are split using a machine similar to a horizontal band saw. After splitting, the thickness of the hide must be uniform throughout. This is achieved with a shaving machine used in the process line. The helical-shaped cutting blades level the overall thickness to meet exact specications and open the ber structure to improve the response to subsequent chemical processing. Such chromium-containing shaving and trimming wastes of wet blue leather amount to more than 10% based on the dry weight of hide and skin. Chrome shavings constitute 75% of the solid wastes containing chromium in the leather-making process. It has been estimated that about 0.8 million tons of chrome shavings could be generated per year globally. This waste is partly used in the manufacture of leather board, but most are disposed of as landll. However, such direct

Recovery of Chromium-Tanned Wastes of Leather Making TABLE 1. Characteristics of chrome shavings (Swarnalatha et al., 2009) Parameter Moisture content Ash content Bulk density Fat Dermal COD TOC Chromium (III) Chromium (VI) Carbon Hydrogen Nitrogen Sulfur Oxygen Values 11.15 2% 45.4 3.8% 0.16 0.02 g cm3 4.69 0.26% 74.9 3.6% 840 58 mg g1 315 41 mg g1 10.68 1.98 mg g1 BDL (< 1 g g1) 37.230 3% 6.193 0.7% 6.443 0.72% 1.422 0.24% 24.285 3.1%

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discharge is not accepted in many countries because of the chromium content (Lipsett, 1982; Mukherjee et al., 2005). When the chrome shaving was contacted with water, the chromium in it released into water in the concentration above the maximum allowable concentration limit given as 5 mg/L by the U.S. Environmental Protection Agency. It was determined that the amount of chromium dissolved increased with the increasing contact time and decreased liquid/solid ratio. A thermal stabilization process was applied to the chrome shaving due to its high organic compounds content. Effective stabilization of chromium in the chrome shavings was achieved by heating of chrome shavings at 350 C under the CO2 atmosphere. This was found to be environmentally stable and can be directly discharged (Erdem and Ozverdi, 2008; Sempere et al., 1997). The characteristics of chrome shavings are listed in Table 1. The chromium recovery from this waste is necessary for environmental protection and economic reasons. The costs connected with the gradual introduction of clean technologies into the leather industry could to a certain extent be compensated for by the processing of leather waste (not only from tanneries but also from other leather processing industries) into raw materials, which could be used in other industries (Langmaier et al., 1999).

B. Treatment of Wastes
The most problem-causing type of solid waste is chrome-tanned leather waste, consisting mainly of shavings and trimmings, especially dyed or nished and bufng dust. It is most often taken to industrial waste dumps. From such waste, acid rains release chromic compounds, which inltrate groundwater. Their transition includes oxidation processes, which turn Cr+3 into Cr+6 compounds, which are carcinogenic in nature. This type of waste

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is therefore potentially risky and very expensive for storing in identied places. Studies have been carried out to investigate safe disposal, recovery of chromium and protein, and their reuse in various elds of industry. The processing of tanned waste can hardly in itself represent a nancially lucrative industry, but in connection with the growing pressure on using cleanwaste-freetechnologies, their processing into secondary raw materials is one of the preconditions for the survival of the leather industry.

1. INCINERATION
Shavings discharged as wastes from tanneries may cause environmental pollution by chromium regardless of whether they are incinerated or dumped into the ground. Chrome shavings have a signicant amount of proteins (78.675.2%) and chromium oxide (4.44.3%). Attempts were made to decompose organic components in shavings by wet air oxidation and separate only chromium from the oxidized liquor. The separation of Cr (III) from collagen can be achieved by a combination of the protein (collagen) stabilization (protective cross-linking) and a subsequent labilization of the Cr (III) species bound to the protein. During the separation collagen retains the tertiary triple helical and higher (bril) structures. The process of chromium removal takes place in a restricted aqueous environment, and it can be characterized as semihomogeneous or semiheterogeneous. Investigations were performed on the incinerating conditions of chrome leather scraps to reduce the toxic gas compounds and on the effect of removing them using the scrubber. The amount of the various components of gas was within acceptable levels and the recovered ash could be used as a material in the process of preparing bichromate (Imai and Okamura, 1991). The respective ashes contain meaningful amounts of chromium and some in hexavalent form, and are used as a source of chromium for various applications, including pigment for ceramic glazes. Chromium recovered in the form of soluble chromate by oxidation has been reused in tanning by reduction with Na2 SO3 . This method was effective in chrome recovery, is environmentally friendly, and has economical benets (Carneiro et al., 2003; Erdem, 2006; Ferreira et al., 1999; Okamura and Shirai, 1976; Poulopoulou et al., 1998; Tahiri et al., 2007). Swarnalatha et al. (2009) demonstrated that the organic fractions of chrome shavings could be incinerated without oxidizing trivalent chromium into hexavalent chromium through starved air combustion and for better recovery of energy.
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2. ALKALINE HYDROLYSIS
Tanned solid wastes have a highly organized structure in the form of bers, which are held closely to each other. A technological alternative for the detanning of chrome wastes is through alkaline hydrolysis. The alkaline digestion of chromium wastes to recover protein products uses three alkaline

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agents; calcium hydroxide, sodium hydroxide, and sodium carbonate were found to be effective. Alkaline agent concentration and reaction time were main parameters and the comparisons of various alkali and enzymatic hydrolysis showed that calcium oxide had advantage over MgO, NaOH, and enzymes plus MgO pretreatment. Analyses of amino acid compositions indicate the residue protein in chrome cake was difcult to hydrolyze completely under alkaline conditions due to hydrophobic interaction, covalent bridges, or cross-linking induced by chromium/carboxyl groups complexation. A three-step hydrolysis process was helpful in extracting valuable products at different stages. The collagen hydrolysate obtained and chrome cake had potential applications in the tanning industry (Basak and Vibhavari, 2003; Cantera et al., 1997; Martinelango and Shelly, 2004; Mu et al., 2003; Saha et al., 2003; Tahiri et al., 2006; Zhao et al., 2009). Detanning also can be done using strong oxidizing agents such as hydrogen peroxide or chlorine under slightly alkaline conditions to produce protein hydrolysates. But the less expensive way of detanning is treatment with acid. This technology is developed for production-scale hydrolysis for commercial applications, as the endproduct had many potential uses (Amir et al., 2008; Heidemann, 1991; Kosmac et al., 1995; Stockman, 1996). Cot et al. (1999a, 199b) found that the presence of peroxochromates generated in situ during the oxidation, in alkaline conditions, can produce a partial hydrolysis to the bers of collagen, accelerating the process of isolation of gelatin. But alkaline digestion with sodium hydroxide allowed the recovery of proteins in the aqueous phase and the metallic salts in the solid phase. After lyophilization of the liquid, solid proteins with a high nitrogen percentage and very low chrome content were recovered. The feasibility of using organic chelates as decontamination agents to isolate chromium from the organic matrix of leather waste was found to be efcient in alkaline media and potassium tartrate was found to be the important extracting agent. The oxidative dechroming using hydrogen peroxide augmented with ultrasound, the chrome removal rate can be over 99%, which would greatly favor wider utilization of the collagen products obtained (Malek et al., 2009; Sun et al., 2003; Tahiri et al., 2004).

3. ENZYMATIC DEGRADATION METHODS


Enzymic processing of chrome shavings and trimmings is a viable treatment and provides a 5060% yield of hydrolysate, which shows low ash content and a low content of chromic compounds. Commercially available proteolytic enzymes used at moderate temperatures and for short periods of time to give a chromium product and a protein product that has potential use as a fertilizer is a simple treatment that provides a practical and economical solution. Proteolytic enzymes, active at moderate temperatures, are effective in solubilizing the protein and, as the reaction takes place at an alkaline pH,

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the chromium remains insoluble. The chemical composition of the isolated products is dependent on the type of treatment and on the composition of the original chromium-containing leather waste product. The process can be made cost-effective by reduction in enzyme concentration and isolation of a gelable protein. In two-step process the chrome shavings are treated with alkali to isolate gelatin and in a second step, the enzyme is used to recover the remaining protein so that the chrome cake can be treated and recycled. Protein products with varying properties can be obtained using alkaline protease with reproducibility (Taylor et al., 1998; Taylor et al., 1992; Taylor et al., 1994; Taylor et al., 1991; Taylor et al., 1990). The effects of various alkaline salts on polypeptide size and the stability of triple helical conformations were evaluated to reduce the amount of enzyme used in the recovery process and increase the value of the protein product recovered. Pepsin behaved as a mild enzyme with a controllable effect on leather wastes, trypsin gave a better yield, and isolated gelatin was of high quality and cost-effective. Gelatin products can be deionized and the recovered chrome cake was puried in a chemical process. This was used in the chrome tanning without decrease in the quality of the leather (Brown et al., 1996; Brown et al., 1994; Cabeza et al., 1999a; Cabeza et al., 1998a; Cabeza et al., 1999b; Cabeza et al., 1998b; Cabeza et al., 1997; Cabeza et al., 1999d; Taylor et al., 2000). To further the potential utilization of chrome cake, aerobic biological degradation in an aqueous environment was developed (Dvorackova et al., 2007; Hrncirik et al., 2005; Kupec et al., 2002). Sivaparvathy et al. (1986) explored the possibility of biodegradation of chrome shavings using microbial enzymes (P. aeruginosa) to minimize the time required for the hydrolysis. Using bovine pancreatic homogenate, a source of alkaline protease, for hydrolyzing the pretreated chrome shavings was also found to be feasible. When enzyme Paecilomyces lilacinus was used, the efcient removal of chrome and protein hydrolysate from shavings was observed (Chakraborty, 2004; Sastry et al., 1999). The combination of enzymatic and acid hydrolysis resulted in tailormade, predened molecular weight products tting the intended use. Low molecular weight products are used as the plant biostimulator (Kasparkova et al., 2009). The use of organic bases (Amines) increased the quality of protein hydrolysates and chrome sludge. Protein hydrolysate recovered and channeled as an organic nitrogenous fertilizer to increase the yield of the crop. Recovered chromic salts can be used to tan hides, as chromic pigments for glass making, and in the manufacture of heat-resistant bricks (Kolomaznik et al., 1999).

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4. PYROLYSIS
Pyrolysis may be one of the alternative routes for the treatment of solid wastes from tannery wastes. Three different types of tannery wastes (chromium- and

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vegetable-tanned shavings, and bufng dust) can be pyrolyzed, resulting in gas, oil, ammonium carbonate, and carboneous residues. The gas can be used as fuel and the oil can either be used as fuel or as raw material for chemicals. The carbonaceous residue can be burned as fuel or safely disposed of. In addition, this residue is also suitable for production of activated carbon (Yilmaz et al., 2007). The elimination of the organic matter resulted in chromium-rich material, which could be suitably used as a ceramic pigment (Abreu and Toffoli, 2009; Lollar, 1981). The addition of coal ash from uid bed combustion technologies, at a suitable temperature and pH, results in effective removal of Cr (III) compounds present in the wastes. The method is very simple, cheap, and effective, and could be used for different compositions (Bulewicz et al., 1997).

III. USES OF RECOVERED MATERIAL A. Animal Feed/Chicken Feed/Fertilizer


The possibility of transforming recovered materials from chrome wastes into useful proteins seemed to present an interesting challenge, being of economic value as well. High-value-added, industrially reusable bioproduct whose application elds could include veterinary medicine, medicine, and pharmacology were isolated (Cot et al., 1986). Good-quality food-grade gelatin can be produced by hydrolysis if the hide has been tanned with conventional chrome tanning salts. Hydrolyzed protein, because of its high nitrogen content, has potential applications as animal feed additive, which provides food supplement amino acids (Bataille et al., 1983; Brown et al., 1996; Hauck, 1974; Smith and Donovan, 1982). Hydrolysates resemble gelatine or glues, which are used in industry, mainly due to their easy gel-sol transition. This sol-gel ability is signicant when used as a secondary raw material (Langmaier et al., 1999; Langmaier et al., 2001). It is possible to produce an almost chromium-free leather meal (less than 0.1 ppm Cr), which is high in protein with a high digestibility. Its amino acid pattern is of a better quality than feather meal and is equal to meat meal and soybean meal with regard to cost competitiveness. Recovered protein also used as food supplement for Tilspia oreochromis niloticus (Boushy et al., 1991; Chakraborty and Sarkar, 1999; Katsifas et al., 2004; Langmaier et al., 2002; Montoneri et al., 1994; Nogami et al., 2000; Reis and Beleza, 1991).

B. In Leather Processing
A new method was evolved for utilizing leather waste in preparing newer types of surfactants from protein hydrolysates. These low-cost surfactants are used in soaking and fatliquoring of leather processing (Narasimhan et al., 1980). Collagen hydrolysates have proven to be useful contributors

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to increase the chromium oxide content of the leathers at the end of the chrome-tanning process. Collagen hydrolysate in posttanning showed attractive properties by its cosmetic, lubricating, and restoring effects by developing a synergetic action with acrylic-retanning agents, by forming polyelectrolyte complexes by enhancing the leather grain properties and providing softness and improved tensile strength. Collagen hydrolysates are also used as dye exhaust aids (Afsar et al., 2009; Aslan et al., 2006; Cantera et al., 1997; Cantera et al., 1999; Cantera et al., 2002; Cantera 2003; Munoz et al., 2002). The gelatin has potential to be chemically modied to produce valueadded leather nishing agents. Glutaraldehyde-modied low-quality gelatin and collagen hydrolysate was used in lling of veiny areas in chrome tanned calfskin leather. Modied gelatin products are also used in leather processing, more specically in preparation of coatings and llers for leather (Cao et al., 2005; Chen et al., 2001; Crispim and Mota, 2003; Mu et al., 2003; Taylor et al., 2005). The dechromed collagenic residues can be transformed into a raw material for the leather and paper industries as a substitute for casein and as a pretanning/retanning agent (Cot et al., 2003). The high protein content of chrome shavings has been utilized for reduction of chromium (VI) in the preparation of chrome tanning agent and developed products exhibit more masking due to the formation of intermediate organic oligopeptides (Rao et al., 2002, 2004).

C. Adhesives/Cosmetics/Films
High-purity and demineralized protein hydrolysates have potential uses in cosmetics (e.g., moisturizing creams, lotions, hair sprays) and biomedical products (e.g., burn dressings, implant coverings; Cakl et al., 1998). Historically, hydrolysis products from collagen, such as technical gelatin and animal glue, were used as eco-friendly adhesives, paints, encapsulating agents, occulating agents, and reproong agents. The gelatin was used in the application of microencapsulation to microencapsulate drugs, essential oils, perfumes, and other materials. Depending on the application of the gelatin, different modiers can be used to get the desired functional properties. Films were prepared from commercial gelatins by enzymatic treatment and glycerol as a plasticizer to be used in the preparation of coatings, edible lms and sausage casings, and also in the packaging material. The addition of polyvinyl alcohol further improved the tensile strength and mechanical properties of lms and were biodegradable (Cabeza et al., 1998a, b, c, and d; Cabeza et al., 1999a; Cabeza et al., 1999b; Cabeza et al., 1999c; Taylor et al., 1998; Taylor et al., 1997a; Taylor et al., 1995; Taylor et al., 1997b; Taylor et al., 2001; Taylor et al., 2002; Taylor et al., 2003). Modied protein hydrolysates have potential to be used as good biodegradable lms (e.g., for agriculture applications; Krncirik et al., 2009).

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D. Biological Uses
Shanthi and Shelly (2003) established the usefulness of the collagen hydrolysate from chrome shavings as a support matrix for immobilization of organophosphorus hydrolyse enzyme. The collagen hydrolysate represents a good mixture and a good source of amino acids as a carbon and nitrogen source (Aslan et al., 2007). The manufacture of chromium-enriched brewers yeast from chromium-containing leather waste is feasible because of its chromium (III) content, which is an essential trace element and cofactor for insulin has important biological functions in metabolism (Liu and Yang, 2006).
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E. As Carbon
As collagen ber is an abundant natural biomass, the preparation of porous carbon ber from collagen ber as precursor is facile, cost-efcient, and sustainable. The collagen ber, with hierarchical super molecular structures, can be used to prepare well-dened porous carbon ber, which has large surface area, high mesopore ratio, and controllable pore size, which has great potential in selective adsorption and as chemical sensors and catalyst. In another method, the wet-blue leather waste after controlled pyrolysis was transformed into chromium-containing activated carbons with microporous and mesoporous structure (Deng et al., 2008; Oliveira et al., 2008a).

F. In Waste Treatment
Tannery solid wastes are formed mainly by proteins and have a highly organized structure in the form of bers ( = 100 nm). The waste has the potential to be used as a low-cost adsorbent for the removal of surfactants from wastewater (Na et al., 2006; Oliveira et al., 2007). The use of chromium shavings also brings potential adsorbents for vegetable tannins from mixed efuents. The tannin-bearing chrome shavings were reused in BCS preparation as reductant. The removal of dyes was also studied and the dye-adsorbed solid wastes were used for the preparation of pigments. The chrome wastes have a possibility to remove the dyes from textile efuents (Saravanabhavan et al., 2004, 2007; Sreeram et al., 2004; Tahiri et al., 2002). Another ability of wet-blue shavings to remove motor oils, oily wastes, and hydrocarbons from contaminated water was studied and found that they are capable of absorbing many times their weight in oil or hydrocarbons. Low density, high buoyancy of bers, porosity, and nontoxicity are the main advantages of tanned solid wastes, and these wastes can be easily treated by incineration. The detanned hide powder also was utilized for the manufacture of an ecological agent suitable for removing environmentally hazardous

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organic substances. (Gammoun et al., 2007a;Gammoun et al., 2007b; Przepiorkowska et al., 2003). The chrome wastes showed good potential for the removal of chromate and arsenate from aqueous media. Fe (III)- and Al (III)loaded adsorbents can be prepared by using skin-split waste of tannery as supporting matrix and can be transformed into low-cost and environmental protection material (Huang et al., 2009; Oliveira et al., 2008b).

G. In the Pigment Industry


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The recovered chromium from solid wastes showed the possibility of producing commercial pigments for paints (Berry et al., 2001, 2002; Tahiri et al., 2001a; Tahiri et al., 2001b). The possibility of thermoresistant pigments for the ceramic industry was explored and the improvement of environment quality and decrease in pigments cost was noticed (Lazau et al., 2007).

H. In Energy
The tannery wastes disposed contain more than half of the energy value of coal, and if recovered and converted into useful energy could satisfy all of a tannerys own heat energy requirements for leather processing. So, an attempt was made to combine drying and gasication to eliminate tannery solid wastes while providing combustible gas as a renewable energy source that the tannery can directly reuse (Bowden, 2003).

I. In Ceramic/Asphalt Mixtures
The addition of chrome shavings, which is used in the production of Portland cement, produced better distribution and pore volume results. Incinerated chrome-tanned shavings were characterized and used to develop a refractory product with the addition of ashes. The technological properties of the obtained product were also evaluated and found to be benecial (Basegio et al., 2006; Basegio et al., 2009; Trezza and Scian, 2007). Krummenauer and Andrade (2009) investigated the usability of leather sawdust in asphalt microsurface layer mixtures and found it to be technically and economically feasible. Biocomposite layers of silica obtained from coatings of silica sols mixed with proteins in water/dioxane revealed that such coatings are highly biocompatible, with excellent mechanical properties (Brasack et al., 2000).

J. In Chromate Manufacturing
The possibility of substituting chromic ore (the typically used natural raw material) with chromic waste in the sodium chromate production process

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has been proven (Kowalski and Walawska, 2001; Vieira and Marcilio, 2004; Walawska and Kowalski, 2000, 2001).

K. In Plastics/Rubber/Resin
Successful commercial applications for the hydrolysate include its use in the manufacture of biodegradable polymers for agriculture sowing tapes. Potential applications include its use in the production of antiskid agents in PVC and rubber compounds, agents for increasing adhesion to textile backing in conveyor belt manufacture, heat stabilizers in PVC paste, and additives to concrete and plaster (Kolomaznik et al., 1999; Pearson, 1982). There has been an increasing interest in the development of biodegradable polymers owing to the growing problem of waste disposal of plastics. Protein hydrolysate is easily and uniformly blended with metallocene-based linear low-density polyethylene (mLLDPE) and the obtained polymer lm retains mechanical strength properties and biodegradability behavior. The hydrolysate is also used to modify biodegradable plastics. The lm based on polyvinyl alcohol (PVA) is modied with protein hydrolysate to be used in agricultural applications (Kresalkova et al., 2002; Saha et al., 2003; Shin et al., 2007). The utilization of collagen as a ller for isoprene and butadieneacrylonitritle rubber mixes was found to have good resistance to aging and also provides increased recaptivities to microbiological decomposition. The leather powder mixed with zinc oxide is the best form of its addition to rubber mixes. The mechanical properties of collagen-added carboxylated butadiene-acrylonitrile rubber indicates an increase in tensile strength and elongation at break (Przepiorkowska et al., 2006; Przepiorkowska et al., 2007; Przepiorkowska et al., 2004; Przepiorkowska et al., 2005). The chrome wastes used as ller in a polymer matrix and PVCleather ber composites were prepared due to their leather-like appearance. The leather-like sheets are exible and exhibit sufcient water absorption to be suitable for several applications in the footwear and clothing industry (Santana et al., 1998). Further, the short leather bers were modied by emulsion polymerization of methyl methacrylate (MMA) in order to increase the compatibility of leather bers with several commodity polymers used in shoe industries. The treatment signicantly improved the thermal stability of bers and reduced water adsorption capacity, as a coating of PMMA is produced over the leather surface (Babanas et al., 2001; Santana et al., 2002). By reacting hydrolysates with glutaraldehyde, inexpensive UF adhesives was developed with reduced formaldehyde emissions (Langmaier et al., 2003; Langmaier et al., 2004a; Langmaier et al., 2004b). The application of collagen hydrolysates in the cross-linking of epoxide resins resulted in solvent-free biodegradable epoxide lms. Cross-linking of hydrolysate with epichlorhydrin is an advantage for applications such

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as degradable packing materials. Collagen hydrolysate was plasticized with glycerol and low-molecular-weight polyethylene glycols, and the resultant hydrophilic plasticizers efciency and their action mechanisms are useful for the production of soft capsules on collagen hydrolysate (Langmaier et al., 2006; Langmaier et al., 2008; Langmaier et al., 2007).

L. In Leather Boards
Chrome-shaving wastes were used to make leather boards for industrial purposes. Chrome tanned grain shavings, trimmings, and splits, in combination with cotton and kraft pulp, were used to manufacture good-quality leather boards, which are strong, exible, and have a high elongation at break (Crispim and Mota, 2003; Gish, 1999; Okamura and Shirai, 1972).

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IV. BUFFING DUST


During the leather manufacturing process, the inner-collagen layer of the nished leather is buffed to get a smooth and ne feel. This process generates a ne powder of collagen brils in large quantities in leather industries, which is called bufng dust. Bufng dust is a proteinous solid waste impregnated with chromium, synthetic fat, oil, tanning agents, and dye chemicals, which is generated during manufacture of leather. About 26 kg of bufng dust is liberated as a solid waste per ton of skin or hide processed. Bufng dust is a microne solid particulate and carries about 2.7% chromium on dry weight basis. It is carcinogenic in nature and it causes clinical problems such as respiratory tract ailments, as well as allergic dermatitis, ulcers, perforated nasal septum, kidney malfunctions, and lung cancer in humans. The characteristics of bufng dust are listed in Table 2. The present practice of disposing of bufng dust consists of (a) incineration and (b) land codisposal. Incineration causes serious air pollution problems because of the release of toxic Sox and Nox gases, and it has been observed that at 800 C about 40% of Cr (III) is converted into Cr (VI). The land codisposal method poses a threat to groundwater resources because the dust carries organic compounds that can be leached by solvents and water at pH 59. The leachates from bufng dust interact with soil particles
TABLE 2. Characteristics of bufng dust (Sekaran et al., 1998) Parameter Carbon TKN Chromium Ash Value 461 93 28 88.49 mg/g mg/g mg/g mg/g

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to a level affecting physicochemical characteristics of soil. So there are many studies undertaken for possible use of bufng dusts. An investigation was done by subjecting chrome bufng dust to starved incineration and the bottom ash was effectively solidied and stabilized using Portland cement and ne aggregate. The study indicated that the organic fractions of chrome bufng dusts can be destructed without oxidizing trivalent chromium into hexavalent chromium through starved air incineration. The solidied block can be used as low-cost hollow cement blocks for its compressive strength and metal xation capacity (Swarnalatha et al., 2008). Conversion of bufng dust into activated carbon is a rational idea of combating solid waste pollution and is able to remove more dye, compared with commercially activated carbon. Activated carbons with high adsorption capacity have good market potential for use as the tertiary treatment of wastewater because they can decrease the cost of operation and upgrade the quality of the treated efuents. Bufng dusts have proven to be a much better adsorbent than chrome shavings for cationic dyes. Bufng dusts of crust leather wastes are capable of absorbing oil many times their weight (Gammoun et al., 2007b; Sekaran et al., 1998; Tahiri et al., 2003). The thermoplastic polymer, acrylonitrile-butadiene-styrene (ABS), was used as the matrix and leather bufng powder material as the ller to prepare a particulate-reinforced composite and the process indicated reduced cost, resource utilization, and environmental benets (Ramaraj, 2006). Buffing dust also was used as an active ller of XNBR and NBR vulcanizates and found higher cross-linking density, better strength properties, and higher hardness, as well as lower elasticity and shock absorption (Chronska and
TABLE 3. Critical appraisal of waste management methodologies Type of waste Chrome shavings Method of treatment Incineration Benets/Limitations Generation of toxic gases High ash content Need for starved air combustion to prevent Cr (VI) formation Possibility of complete hydrolysis with chemicals such as sodium hydroxide The resultant chrome cake also can be reused in tanning sector. Products with low ash content Shorter duration Variety of products can be obtained through controlled hydrolysis for multiple end uses High energy requirement Not cost competitive

Chrome shavings

Alkaline hydrolysis

Chrome shavings and trimmings

Enzymatic degradation

Chromium/vegetable tanned shavings and bufng dust

Pyrolysis

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TABLE 4. Application of various recovered products Waste Chrome waste Product Proteins Gelatin Protein hydrolysates Collagen ber/ hydrolysates Protein ber Chromium Chromium waste Application Veterinary, medicine, pharmacology Animal/chicken meal Cosmetics/adhesives/lms/biodegradable polymers/rubber, leather processing Carbon/nitrogen source Removal of oil wastes Pigments/chromate production Energy Cement/ceramic/asphalt mixtures Leather boards Powder Ash Sheet Polymer ller, absorbent of dyes/oil Portland cement, activated carbon Wallets, key cases

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Incinerated chrome shavings Chromium splits/ shavings/trimmings Bufng dust

Przepiorkowska, 2008). A leather-like sheet has been developed using a combination of natural and synthetic polymers for its use in manufacture of leather-like products such as wallets and key cases (Vedaraman et al., 2002).

V. CONCLUSION
The leather industry has outgrown the principal meat industry in terms of global turnover. Most solid waste generated from tannery industries is presently unutilized and wasted. Leather wastes can be recovered and processed at industrial scales to generate value-added products, which can emerge as an important commercial activity on its own while eliminating environmental concerns of the leather process industry. A critical appraisal of various waste management methodologies and application of recovered products is provided in Tables 3 and 4. The growing environmental concerns pose a new challenge to leather chemists, calling for renewed research and development to facilitate sustenance of the traditional industry. Generation of industrial bioproducts and development of biomedical applications for some of them would ensure higher protability for leather making or lead to the development of new economic models exclusively for waste processing.

REFERENCES
Abreu, M.A., and Toffoli, S.M. (2009). Characterization of a chromium-rich tannery waste and its potential use in ceramics. Ceramics International, 35, 22252234.

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Afsar, A., Gulumser, G., Aslan, A., and Ocak, B. (2009). A study on usability of collagen hydrolysate along with oxazolidine in leather processing. Paper presented at the International Leather Engineering Symposium, Turkey, April 29May 1. Amir, S., Benlboukht, F., Cancian, N., Winterton, P., and Hadi, M. (2008). Physicochemical analysis of tannery solid waste and structural characterization of its isolated humic acids after composting. J. Hazard. Mater., 160, 448455. Aslan, A., Gulumser, G., and Ocak, B. (2006). Increased chromium tanning efciency with collagen hydrolysates. J. Soc. Leather Technol. Chem., 90, 201204. Aslan, A., Karavana, H.A., Gulumser, G., Yasa, I., and Cadirci, B.H. (2007). Utilization of collagen hydrolysate in keratinase production from Bacillus subtilis ATCC 6633. J. Am. Leather Chemical. Assoc., 102, 129134. Babanas, K., Tarantili, P.A., and Andreopoulos, A.G. (2001). Plasticized poly (vinyl chloride) lled with waste leather particles. J. Elast. Plast., 33, 7285. Basak, N., and Vibhavari, S. (2003). Isolation of protein products from chrome shavings by acidic treatment: A study. J. Indian Leather Technol. Assoc., 53, 935940. Basegio, T., Haas, C., Pokorny, A., Bernardes, A.M., and Bergmann, C.P. (2006). Production of materials with alumina and ashes from incineration of chromium tanned leather shavings: Environmental and technical aspects. J. Hazard. Mater., B137, 11561164. Basegio, T., Leao, A.P.B., Bernardes, A.M., and Bergmann, C.P. (2009). Vitrication: An alternative to minimize environmental impact caused by leather industry wastes. J. Hazard. Mater., 165, 604611. Bataille, P., Gagnon, F., and Smith, W.E. (1983). Upgrading leather and felt scrap into proteins. J. Am. Leather Chemical. Assoc., 78, 328337. Berry, F.J., Costantini, N., and Smart, L.E. (2001). Recovery and reuse of chromium from leather shavings: Formation of chromium-containing ceramic pigments. J. Am. Leather Chemical. Assoc., 96, 4653. Berry, F.J., Costantini, N., and Smart, L.E. (2002). Synthesis of chromium pigments from chromium recovered from leather waste. Waste Manage., 22, 761772. Bulewicz, E.M., Kozak, A., and Kowalski, Z. (1997). Treatment of chrome tannery wastes using coal ashes from uidized bed combustion of coal. Ind. Eng. Chem. Res., 36, 43814384. Boushy, A.R.E., Poel, A.F.B.V., Koene, J.I.A., and Dieleman, S.H. (1991). Tanning waste by-product from cattle hides, its suitability as a feedstuff. Bioresource Technology, 35, 321323. Bowden, W. (2003). Gasication: Achieving zero waste. J. Am. Leather Chemical. Assoc., 98, 1926. Brasack, I., Bottcher, H., and Hempel, U. (2000). Biocompatibility of modied silicaprotein composite layers. J. Sol-Gel Sci. Techn., 19, 479482. Brown, E.M., and Taylor, M.M. (2003). Essential chromium? J. Am. Leather Chemical. Assoc., 98, 408414. Brown, E.M., Taylor, M.M., and Marmer, W.N. (1996). Production and potential uses of co-products from solid tannery waste. J. Am. Leather Chemical. Assoc., 91, 270276. Brown, E.M., Thompson, C.J., and Taylor, M.M. (1994). Molecular size and conformation of protein recovered from chrome shavings. J. Am. Leather Chem. Assoc., 89, 215220.

Downloaded by [Central Leather Research Institute] at 01:01 01 December 2011

2066

V. J. Sundar et al.

Buljan, J., Reich, G., and Ludvik, J. (1999). Mass balance in leather processing. World Leather, 12, 3446. Cabeza, L.F., Clauson, S.M., Taylor, M.M., Brown, E.M., Marmer, W.N., and Merck, K.B. (1999a). The effect of surfactants on the isolation of protein products from chromium-containing solid tannery waste. Inuence on the process and on the chemical, physical and functional properties of the resultant gelatin. J. Am. Leather Chem. Assoc., 94, 190198. Cabeza, L.F., McAloon, A.J., Yee, W.C., Taylor, M.M., Brown, E.M., and Marmer, W.N. (1998a). Process simulation and cost estimation of treatment of chromiumcontaining leather waste. J. Am. Leather Chem. Assoc., 93, 299315. Cabeza, L.F., Taylor, M.M., Brown, E.M., and Marmer, W.N. (1999b). Potential applications for Gelatin isolated from chromium-containing solid tannery waste: Microencapsulation. J. Am. Leather Chem. Assoc., 94, 182189. Cabeza, L.F., Taylor, M.M., Brown, E.M., and Marmer, W.N. (1997). Inuence of pepsin and trypsin on chemical and physical properties of isolated gelatin from chrome shavings. J. Am. Leather Chem. Assoc., 92, 200207. Cabeza, L.F., Taylor, M.M., Brown, E.M., and Marmer, W.N. (1998b). Chemical and physical properties of protein products isolated from chromium-containing leather waste using two consecutive enzymes. J. Soc. Leather Technol. Chem., 82, 173179. Cabeza, L.F., Taylor, M.M., Brown, E.M., and Marmer, W.N. (1999c). Isolation of protein products from chromium-containing leather waste using two consecutive enzymes and purication of nal chromium product: Pilot plant studies. J. Soc. Leather Technol. Chem., 83, 1419. Cabeza, L.F., Taylor, M.M., Brown, E.M., Marmer, W.N., Carrio, R., Grau, E., Celma, P.J., Cot, J., and Manich, M. (1999d). Treatment of sheep skin chrome shavings. Isolation of high value protein products and reuse of chromium in the tanning process. J. Am. Leather Chemical. Assoc., 94, 268287. Cabeza, L.F., Taylor, M.M., DiMaio, G.L., Brown, E.M., Marmer, W.N., Carrio, R., Celma, P.J., and Cot, J. (1998c). Processing of leather waste: Pilot scale studies on chrome shavings. Isolation of potentially valuable protein products and chromium. Waste Manage., 18, 211218. Cabeza, L.F., Taylor, M.M., DiMaio, G.L., Brown, E.M., Marmer, W.N., Carrio, R., Celma, P.J., and Cot, J. (1998d). Processing of leather waste: Pilot scale studies on chrome shavings. Part II. Purication of chrome cake and tanning trials. J. Am. Leather Chemical. Assoc., 93, 8398. Cabeza, L.F., Taylor, M.M., DiMaio, G.L., Brown, E.L., Marmer, W.N., Carrio, R., Celma, P.J., and Cot, J. (1999e). Cost effective processing of leather waste: Pilot scale studies on chrome shavings from cattle hides and sheepskins isolation of potentially valuable protein products and utilization of recovered chromium. Proc. of XXV IULTCS Congress held in Chennai, Waste Management Technologies., 465472. Cakl, J., Sir, J., Medvedikova, L., and Blaha, A. (1998). Demineralization of protein hydrolysates from enzymatic hydrolysis of leather shavings using membrane dialteration. Separation Sci., and Technol., 33, 12711281. Cantera, C.S. (2003). Adding value to chrome shavings: Hydrolysates as retanning materials. World Leather, 16, 2729.

Downloaded by [Central Leather Research Institute] at 01:01 01 December 2011

Recovery of Chromium-Tanned Wastes of Leather Making

2067

Cantera, C.S., De Giuste, M., and Soa, A. (1997). Hydrolysis of chrome shavings: Application of collagen hydrolysate and acrylicprotein in post tanning operations. J. Soc. Leather Technol. Chem., 81, 183191. Cantera, C.S., Goya, L., and Mingo, R. (1999). Collagen hydrolysate: Soluble skin applied in post tanning processes Part 1: Characterisation. J. Soc. Leather Technol. Chem., 84, 2937. Cantera, C.S., Martegani, J., Esterelles, G., and Vergara, J. (2002). Collagen hydrolysate: Soluble skin applied in post tanning processes Part 2: Interaction with acrylic retanning agents. J. Soc. Leather Technol. Chem., 86, 195202. Cao, J., Lu, Y., Chang, G., and Tang, K. (2005). Glutaraldehyde modication of collagen hydrolysate obtained from chrome shavings. J. Am. Leather Chemical. Assoc., 100, 265272. Carneiro, S., Almeida, M.F., and Ferreira, M.J. (2003). Factors inuencing chromium recovery from chromium sulphate tanned leather scrap ashes. J. Soc. Leather Technol. Chem., 87, 110. Chagne, C., Silvestre F., and Gaset, A. (1996). Review of chrome tanning. Part 1. Leather, 198, 1726. Chakraborty, R. (2003). Ecofriendly solid waste management in the leather industry. Environmental biotechnology newsletter, University of Kalyani, India, 3, 2. Chakraborty, R. (2004). Optimization of hydrolysis of chrome shavings by enzyme from P. Lilacinus. J. Am. Leather Chemical. Assoc., 99, 103109. Chakraborty, R., and Sarkar, S.K. (1999). Eco-friendly biofertilizer from solid waste. Proc. XXV IULTCS Congress held in Chennai, Waste Management Technologies, 481483. Chen, W., Cooke, P.H., DiMaio, G., Taylor, M.M., and Brown, E.M. (2001). Modied collagen hydrolysate, potential for use as a ller for leather. J. Am. Leather Chemical. Assoc., 96, 262267. Chronska K., and Przepiorkowska, A. (2008). Bufng dust as a ller of carboxylated butadiene-acrylonitrile rubber and butadiene-acrylonitrile rubber. J. Hazard. Mater., 151, 348355. Cot, J., Aramon, C., Baucells, M., Lacort, G., and Roura, M. (1986). Waste processing in the tannery: Production of gelatin, Reconstituted collagen and glue from chrome-tanned leather splits and trimmings subjected to a modied detanning process. J. Soc. Leather Technol. Chem., 70, 6976. Cot, J., Manich, A.M., Marsal, A., Fort, M., Celma, P.J., Carrio, R., Choque, R., and Cabeza, L.F. (1999). Processing of collagenic residues isolation of gelatin by the action of peroxochromates. J. Am. Leather Chemical. Assoc., 94, 115128. Cot, J., Manich, A.M., Marsal, A., Fort, M., Celma, P.J., Carrio, R., Choque, R., and Cabeza, L.F. (1999). Processing of collagenic residues isolation of gelatin by the action of peroxochromates. Proc. XXV IULTCS Congress held in Chennai, Process Innovations, 135145. Cot, J., Marsal, A., Manich, A., Celma, P., Choque, R., Cabeza, L., Labastida, L., Lopez, J., and Salmeron, J. (2003). Minimization of industrial wastes: Adding value to collagenic materials Proctor Memorial Lecture. J. Soc. Leather Technol. Chem., 87, 9197. Crispim, A., and Mota, M. (2003). Leather shavings treatment: An enzymatic approach. J. Soc. Leather Technol. Chem., 87, 203207.

Downloaded by [Central Leather Research Institute] at 01:01 01 December 2011

2068

V. J. Sundar et al.

Deng, D., Liao, X., and Shi, B. (2008). Synthesis of porous carbon bers from collagen ber. Chem. Sus. Chem., 1, 298301. Dvorackova, M., Julinova, M., Mikulcakova, H., and Kupec, J. (2007). Testing aerobic degradation of the protein portion of lter cake after ltration of chrome tanned waste. J. Am. Leather Chemical. Assoc., 102, 7784. Erdem, M. (2006). Chromium recovery from chrome shaving generated in tanning process. J. Hazard. Mater., B129, 143146. Erdem, M., and Ozverdi, A. (2008). Leaching behavior of chromium in chrome shaving generated in tanning process and its stabilization. J. Hazard. Mater., 156, 5155. Fathima, N.N., Aravindhan, R., Rao, J.R., and Nair, B.U. (2005). Solid waste removes toxic liquid waste: Adsorption of chromium (VI) by iron complexed protein waste. Environ. Sci. Technol., 39, 28042810. Fengxia, C., Hanbo, Z., Yahong, Z., Weihua, L., and Xianyong, J. (2005). Preparation of chrome liquor using chrome shavings as reducing agent. J. Am. Leather Chemical. Assoc., 100, 217224. Gaidau, C., Niculescu, M., Stepan, E., Taloi, D., and Filipescu, L. (2009). Additives and advanced biomaterials obtained from leather industry by-products. Rev. De Chim., 60, 501507. Gammoun, A., Tahiri, S., Albizane, A., Azzi, M., and Guardia, M.D.L. (2007b). Decontamination of water polluted with oil through the use of tanned solid wastes. J. Environ. Eng. Sci., 6, 553559. Gammoun, A., Tahiri, S., Albizane, A., Azzi, M., Moros, J., Garrigues S., and Guardia, M.D.L. (2007a). Separation of motor oils, oily wastes and hydrocarbons from contaminated water by sorption on chrome shavings. J. Hazard Mater., 145, 148153. Gauglhofer, J. (1986). Environmental aspects of tanning with chromium. J. Soc. Leather Technol. Chem., 70, 1113. Gish, A.J. (1999). Leather board, a practical use of tannery offal. J. Am. Leather Chemical. Assoc., 94, 4347. Groenestijn, J.W.V., Langerwerf, J.S.A., and Lucas, M. (2002). Reducing environmental emissions in tanneries. J. Environ. Sci. Health., A37, 737743. Hauck, R.A. (1974). Some notes on utilization of eshings and blue shavings. J. Am. Leather Chemical. Assoc., 69, 195203. Heidemann, E. (1991). Disposal and recycling of chrome-tanned materials. J. Am. Leather Chemical. Assoc., 86, 331333. Hrncirik, J., Dvorackova, M., Hruska, F., Kupec, J., and Kolomaznik, K. (2005). Kinetics of alkaline hydrolysis of the insoluble protein fraction following enzymatic hydrolysis of chrome-tanned shavings. J. Am. Leather Chemical. Assoc., 100, 17. Huang, X., Liao, X., and Shi, B. (2009). Adsorption removal of phosphate in industrial wastewater by using metal-loaded skin split waste. J. Hazard. Mater., 166, 12611265. Imai, T., and Okamura, H. (1991). Studies on incineration of chrome leather waste. J. Am. Leather Chemical. Assoc., 86, 281294. Jiao, L., Liao, X., and Shi, B. (2009). Adsorptive removal of As(V) from aqueous solution by Zr(IV) loaded skin shavings. J. Am. Leather Chemical. Assoc., 104, 308315.

Downloaded by [Central Leather Research Institute] at 01:01 01 December 2011

Recovery of Chromium-Tanned Wastes of Leather Making

2069

Kasparkova, V., Kolomaznik, K., Burketova, L., Sasek, V., and Simek, L. (2009). Characterization of low-molecular weight collagen hydrolysates prepared by combination of enzymatic and acid hydrolysis. J. Am. Leather Chemical. Assoc., 104, 4651. Katsifas, E.A., Giannoutsou, E., Lambraki, M., Barla, M., and Karagouni, A.D. (2004). Chromium recycling of tannery waste through microbial fermentation. J. Ind. Microbial Biotechnol., 31, 5762. Kolomaznik, K., Adamek, M., Andel, I., and Uhlirova, M. (2008). Leather waste: Potential threat to human health, and a new technology of its treatment. J. Hazard Mater., 160, 514520. Kolomaznik, K., Mladek, M., Langmaier, F., Janacova, D., and Taylor, M.M. (1999). Expereince in industrial practice of enzymatic dechromation of chrome shavings. J. Am. Leather Chemical. Assoc., 94, 5563. Kosmac, V.S.E., Gantar, A., and Anzur,I. (1995). Modication of collagen hydrolysates. Resour. Conserv., and Recycle., 13, 97104. Kowalski, Z., and Walawska, B. (2001). Utilization of tannery wastes for the production of sodium chromate (VI). Ind. Eng. Chem. Res., 40, 826832. Kresalkova, M., Hnanickova, L., Kupec, J., Kolomaznik, K., and Alexy, P. (2002). Application of protein hydrolysate from chrome shavings for polyvinyl alcoholbased biodegradable material. J. Am. Leather Chemical. Assoc., 97, 143149. Krncirik, J.H., Pseja, J., Kupec, J., Noskova, R., and Olsak, J. (2009). Anaerobic biological degradation of protein hydrolysate cross-linked with higher-molecular weight diepoxides. J. Am. Leather Chemical. Assoc., 104, 3645. Krummenauer, K., and Andrade, J.J.D.O. (2009). Incorporation of chromium tanned leather residue to asphalt micro-surface layer. Constr. Build. Mater., 23, 574 581. Kupec, J., Dvorackova, M., Rudlova, S., Ruicka, J., and Kolomaznik, K. (2002). Deproteination of chrome waste by washing and enzymatic hydrolysis. J. Am. Leather Chemical. Assoc., 97, 349354. Langmaier, F., Kolomaznik, K., and Mladek, M. (2003). Modifying products of enzymatic breakdown of chrome-tanned leather wastes with glutaraldehyde. J. Soc. Leather Technol. Chem., 87, 5561. Langmaier, F., Kolomaznik, K., Sukop, S., and Mladek, M. (1999). Products of enzymatic decomposition of chrome-tanned leather waste. J. Soc. Leather Technol. Chem., 83, 187195. Langmaier, F., Mladek, M., Kolomaznik, K., Sivarova, J., and Sukop, S. (2002). Calorimetry of the reactions of hydrolysates of chromed shavings with aldehydes. J. Therm. Anal. Cal., 67, 659666. Langmaier, F., Mokrejs, P., Karnas, R., Mladek, M., and Kolomaznik, K. (2006). Modication of chrome-tanned leather waste hydrolysate with epichlorhydrin. J. Soc. Leather Technol. Chem., 90, 2934. Langmaier, F., Mokrejs, P., Kolomaznik, K., and Mladek, M. (2008). Plasticizing collagen hydrolysate with glycerol and low-molecular weight poly (ethylene glycols). Thermochim. Acta., 469, 5258. Langmaier, F., Mokrejs, P., Kolomaznik, K., Mladek, M., and Karnas, R. (2007). Cross-linking epoxide resins with hydrolysates of chrome-tanned leather waste. J. Therm. Anal. Cal., 88, 857862.

Downloaded by [Central Leather Research Institute] at 01:01 01 December 2011

2070

V. J. Sundar et al.

Langmaier, F., Sivarova, J., Kolomaznik, K., and Mladek, M. (2004a). Curing of ureaformaldehyde adhesives with collagen type hydrolysates under acid condition. J. Therm. Anal. Cal., 76, 10151023. Langmaier, F., Sivarova, J., Mladek, M., and Kolomaznik, K. (2004b). Curing adhesives of urea: Formaldehyde type with collagen hydrolysates of chrome-tanned leather waste. J. Therm. Anal. Cal., 75, 205219. Langmaier, F., Stibora, M., Mladek, M., and Kolomaznik, K. (2001). Gel-sol transitions of chrome tanned leather waste hydrolysate. J. Soc. Leather Technol. Chem., 85, 100105. Lazau, R.I., Pacurariu, C., Becherescu, D., and Ianos, R. (2007). Ceramic pigments with chromium content from leather wastes. J. Europe Ceramic Soc., 27, 18991903. Lipsett, V.A. (1982). Offal blue: Sources and current deposition of chrome offals. J. Am. Leather Chemical. Assoc., 77, 291301. Liu, Y., and Yang, Z. (2006). Uses for chrome leather waste: Chromium-enriched brewers yeast. J. Soc. Leather Technol. Chem., 90, 1418. Lollar, R.M. (1981). Potential uses of tanned collagen. J. Am. Leather Chemical. Assoc., 76, 192193. Malek, A., Hachemi, M., and Didier, V. (2009). New approach of depollution of solid chromium leather waste by the use of organic chelates: Economical and environmental impacts. J. Hazard Mater., 170, 156162. Martinelango, K., and Shelly, D.C. (2004). Multidimensional analysis of magnesium oxide hydrolysis of wet-blue shavings. J. Am. Leather Chemical. Assoc., 99, 258268. Montoneri, E., Rizzi, G., Rizzi, A., Mordenti, A., Bauli, A., Riolfatti, M., and Pellegrini, L. (1994). Hydrolysis of tannery wastes to protein meal for animal feedstuffs: A process and product evaluation. J. Chem. Tech. Biotechnol., 59, 91 99. Mu, C., Lin, W., Zhang, M., and Zhu, Q. (2003). Towards zero discharge of chromiumcontaining leather waste through improved alkali hydrolysis. Waste Manage., 23, 835843. Mukherjee, G., Chakraborty, S., Biswas, G.K., and Basu, S.K. (2005). Chromium tanned leather and its environmental impact. J. Indian Leather Technol. Assoc., 55, 239246. Munoz, J.M., Maldonado, M.V., and Rangel, A.S. (2002). Development of a tanning process based on using hydrolyzated material collected from leather scrap. J. Am. Leather Chemical. Assoc., 97, 8387. Munz, K.H., Sundar, V.J., Muralidharan, C., and Parthasarathy, K. (1997). Chrome tannage without pickling. Das Leder, 48, 128132. Muralidharan, C., Sundar, V.J., Rao, V.S.S., and Ramasami. T. (2001). Two-stage tanning: A new approach for chrome management. J. Am. Leather Chemical. Assoc., 96, 6166. Na, Z.M., Pin, L.X., and Bi, S. (2006). Adsorption of surfactants on chromium leather waste. J. Soc. Leather Technol. Chem., 90, 16. Narasimhan, K., Sehgal, P.K., and Joseph, K.T. (1980). Condensation of aromatic sulfonic acid with hydrolysates from leather wastes. J. Am. Leather Chemical. Assoc., 75, 211215.

Downloaded by [Central Leather Research Institute] at 01:01 01 December 2011

Recovery of Chromium-Tanned Wastes of Leather Making

2071

Nogami, E.M., Kimura, C.C.M., Malagutti, A.R., Galli, D., Gallo, D., Castilho, T.J., Rodrigues, C., and Nozaki, J. (2000). Recovery of protein from chrome shavings and application as a food supplement for Tilapia Oreochromis Niloticus. J. Am. Leather Chemical. Assoc., 95, 119124. Okamura, H., and Shirai, K. (1972). Basic studies on the manufacture of leatherboard from chrome collagen ber. J. Am. Leather Chemical. Assoc., 67, 148162. Okamura, H., and Shirai, K. (1976). Recovery of chromium from shavings by wet air oxidation. J. Am. Leather Chemical. Assoc., 71, 173179. Oliveira, D.Q.L., Goncalves, M., Oliveira, L.C.A., and Guilherme, L.R.G. (2008a). Removal of As (V) and Cr (VI) from aqueous solutions using solid waste from leather industry. J. Hazard Mater., 151, 280284. Oliveira, L.C.A., Goncalves, M., Oliveira, D.Q.L., Guerreiro, M.C., Guilherme, L.R.G., and Dallago, R.M. (2007). Solid waste from leather industry as adsorbent of organic dyes in aqueousmedium. J. Hazard Mater., 141, 344347. Oliveira, L.C.A., Guerreiro, M.C., Concalves, M., Oliveira, D.Q.L., and Costa, L.C.M. (2008b). Preparation of activated carbon from leather waste: A new material containing small particle of chromium oxide. Materials Letters, 62, 37103712. Pearson, C.L. (1982). Animal glue in industry and the use of chrome-tanned hide collagen in the production of animal glue. J. Am. Leather Chemical. Assoc., 77, 306311. Popescu, C., Budrugeac, P., Wortmann, F.J., Miu, L., Demco, D.E., and Baius, M. (2008). Assessment of collagen-based materials which are supports of cultural and historical objects. Poly. Degrad. Stability., 93, 976982. Poulopoulou, V.G., Katakis, D., and Vrachnou, E. (1998). A method for the removal of chromium from tanned leather wastes. J. Air Waste Manage. Assoc., 48, 846852. Przepiorkowska, A., Chronska, K., Prochon, M., and Zaborski, M. (2006). New possibilities for managing the leather industry wastes. Przemysl Chemiczny., 85, 971975. Przepiorkowska, A., Chronska, K., and Zaborski, M. (2007). Chrome tanned leather shavings as a ller of butadiene-acrylonitrile rubber. J. Hazard Mater., 141, 252257. Przepiorkowska, A., Janowska, G., Slusarski, L., and Wolniak, S. (2003). Leather powder as an agent for removing environmentally hazardous organic compounds. J. Soc. Leather Technol. Chem., 87, 223226. Przepiorkowska, A., Prochon, M., and Zaborski, M. (2004). Use of waste collagen as a ller for rubber compounds. J. Soc. Leather Technol. Chem., 88, 223227. Przepiorkowska, A., Prochon, M., Zaborski, M., Zakowska, Z., and Piotrowska, M. (2005). Biodegradable protein-containing elastomeric vulcanizates. Rubber Chem. Technol., 78, 868878. Ramaraj, B. (2006). Mechanical and thermal properties of ABS and leather waste composites. J. Applied Polymer Science., 101, 30623066. Ramasami, T., Sreeram, K.J., and Gayatri, R. (1998). Emerging leather processing options for waste minimization. UNIDO Report, Regional Workshop on Cleaner Tanning Technologies. Rao, J.R., Thanikaivelan, P., Sreeram, K.J., and Nair, B.U. (2002). Green route for the utilization of chrome shavings (chromium-containing solid waste) in tanning industry. Environ. Sci. Technol., 36, 13721376.

Downloaded by [Central Leather Research Institute] at 01:01 01 December 2011

2072

V. J. Sundar et al.

Rao, J.R., Thanikaivelan, P., Sreeram, K.J., and Nair, B.U. (2004). Tanning studies with basic chromium sulfate prepared using chrome shavings as a reductant: A call for wealth from waste approach to the tanning industry. J. Am. Leather Chemical. Assoc., 99, 170176. Rutland, F.H. (1991). Environmental compatibility of chromium-containing tannery and other leather product wastes at land disposal site. J. Am. Leather Chemical. Assoc., 86, 364375. Reis, M.A.D., and Beleza, V. (1991). Utilization of leather waste: Animal feedstuff from chrome shavings. Part 1: Pilot plant study. J. Soc. Leather Technol. Chem., 75, 1519. Saha, N., Kresalkova, M., Saha, L., and Kolomaznik, K. (2003). The effect of anaerobic digestion on chrome sludge: A by-product of tanned leather waste. J. Am. Leather Chemical. Assoc., 98, 256262. Saha, N., Zatloukal, M., and Saha, P. (2003). Modication of polymers by protein hydrolysate: A way to biodegradable materials. Polym. Adv. Technol., 14, 854860. Santana, T.J.M., Torres, A.C., and Lucero, A.M. (1998). Extrusion and Mechanical characterization of PVC-leather ber composites. Polym. Compos., 19, 431439. Santana, T.J.M., Vega, M.J.A., Lucero, A.M., and Moreno, F.V. (2002). Production of leather like composites using chemically modied short leather bers. I: Chemical modication by emulsion polymerization. Polym. Compos., 23, 4960. Saravanabhavan, S., Sreeram, K.J., Rao, J.R., and Nair, B.U. (2004). The three pot solution for chromium, tannins and solid wastes: Recovery and reuse technique for spent semi-chrome liquor and chrome shavings. J. Soc. Leather Technol. Chem., 88, 202207. Saravanabhavan, S., Sreeram, K.J., Rao, J.R., and Nair, B.U. (2007). The use of toxic solid waste for the adsorption of dyes from waste streams. J. Chem. Technol. Biotechnol., 82, 407413. Sarkar, K.T. (2005). Theory and practice of leather manufacture (Rev. Ed.), Sarkar Publications, Calcutta, India Sastry, T.P., Ranganayaki, M.D., Rose, C., and Rajini, R. (1999). Extraction of gelatin from chrome shavings using pancreatic enzymes. Proc. XXV IULTCS Congress, held in Chennai, Waste Management Technologies, 513519. Sekaran, G., Shanmugasundaram, K.A., and Mariappan, M. (1998). Characterization and utilization of bufng dust generated by the leather industry. J. Hazard Mater., 63, 5368. Sempere, J.F., Martinez, M.L.B., Montesinos, R.F., and Lillo, M.C.S. (1997). Characterization of tannery wastes comparison of three leachability tests. J. Hazard. Mater., 54, 3145. Shanthi, C., and Shelly, D.C. (2003). Immobilization of degradative enzyme onto collagen hydrolysate lms. J. Am. Leather Chemical. Assoc., 98, 612. Shin, E.C., Lee, S.C., Kim, W.J., and Heo, J.S. (2007). Development of regenerated protein bers from a collagen-polyvinyl alcohol complex. J. Am. Leather Chemical. Assoc., 102, 315321. Sivaparvathy, M., Suseela, K., and Nanda, S.C. (1986). Hydrolytic action of Pseudomonas Aerugihosa on chrome shavings. Leather Sci., 33(1), 811. Smith, L.R., and Donovan, R.G. (1982). Preparation of high quality gelatin with low chromium content from chrome-tanned stock. J. Am. Leather Chemical. Assoc., 77, 301306.

Downloaded by [Central Leather Research Institute] at 01:01 01 December 2011

Recovery of Chromium-Tanned Wastes of Leather Making

2073

Sreeram, K.J., Saravanabhavan, S., Rao, J.R., and Nair, B.U. (2004). Use of chromiumcollagen wastes for the removal of tannins from wastewaters. Ind. Eng. Chem. Res., 43, 53105317. Stockman, G. (1996). Practical considerations of the production scale hydrolysis of blue shavings. J. Am. Leather Chemical. Assoc., 91, 190193. Sun, D., Liao, X., and Shi, B. (2003). Oxidative dechroming of leather shavings under ultrasound. J. Soc. Leather Technol. Chem., 87, 103106. Sundar, V.J., Haribabu, V., Muralidharan, C., and Sadulla, S. (2008). Turning to nature for eco benign stabilization of skin protein. J. Leather Sci., 4, 2428. Sundar, V.J., Ramesh, R., Rao, P.S., Saravanan, P., Sridharnath, B., and Muralidharan, C. (2001). Water management in leather industry. J. Sci. Ind. Res., 60, 443450. Sundar, V.J., Rangasamy, T., Sivakumar, V., and Muralidharan, C. (2004). A novel pickle free high exhaust chrome tanning method: An approach for total dissolved solids management. J. Soc. Leather Technol. Chem., 88, 252255. Sundar, V.J., Rao, J.R., and Muralidharan, C. (2002). Cleaner chrome tanning: Emerging options. J. Clean. Prod., 10, 6974. Sundar, V.J., Vedaraman, N., Balakrishnan, P.A., Chakrabarti, S., and Muralidharan, C. (2006). Sulphide free unhairing: Studies on ozone based depilation. J. Am. Leather Chemical. Assoc., 101, 231234. Swarnalatha, S., Ganesh Kumar, A., Tandaiah, S., and Sekaran, G. (2009). Efcient and safe disposal of chrome shavings discharged from leather industry using thermal combustion. J. Chem. Tech. Biotechnol., 84, 751760. Swarnalatha, S., Srinivasulu, T., Srimurali, M., and Sekaran, T. (2008). Safe disposal of toxic chrome bufng dust generated from leather industries. J. Hazard. Mater., 150, 290299. Tahiri, S., Albizane, A., Abargues, M.R., and Guardia, M.D.L. (2006). Recovery of proteinaceous materials from tanned solid wastes: Yields and characterization of isolated products. J. Solid Waste Technol. Manage., 32, 138148. Tahiri, S., Albizane, A., Messaoudi, A., Azzi, M., Bennazha, J., Younssi, S.A., and Bouhria, M. (2007). Thermal behaviour of chrome shavings and of sludges recovered after digestion of tanned solid wastes with calcium hydroxide. Waste Manage., 27, 8995. Tahiri, S., Azzi, M., Albizane, A., Messaoudi, A., Bouhria, M., and Sibari, A. (2001a). Processing of chrome tanned solid waste generated in the leather industry: Recovery of proteins and synthesis of a pigment for paint. J. Am. Leather Chemical. Assoc., 96, 18. Tahiri, S., Azzi, M., Albizane, A., Messaoudi, A., Bouhria, M., Younssi, S.A., Mourid A., and Amrhar, J. (2001b). Study of quality of a pigment prepared by complexation of chromates recovered from treated chrome shavings and tanned splits. J. Am. Leather Chemical. Assoc., 96, 426436. Tahiri, S., Azzi, M., Messaoudi, A., Albizane, A., Bouhria, M., Younssi, S.A., and Mabrour, J. (2002). Removal of methylene blue from aqueous solutions by adsorption on tanned solid wastes. J. Am. Leather Chemical. Assoc., 97, 261266. Tahiri, S., Bouhria, M., Albizane, A., Messaoudi, A., Azzi, M., Younssi, S.A., and Mabrour, J. (2004). Extraction of proteins from chrome shavings with sodium hydroxide and reuse of chromium in the tanning process. J. Am. Leather Chemical. Assoc., 99, 1625.

Downloaded by [Central Leather Research Institute] at 01:01 01 December 2011

2074

V. J. Sundar et al.

Tahiri, S., Messaoudi, A., Albizane, A., Azzi, M., Bouhria, M., Younssi, S.A., Bennazha, J., and Mabrour, J. (2003). Removal of dyes from aqueous solutions by adsorption on chrome tanned solid wastes generated in the leather industry. Water Qual. Res. J. Canada., 38, 393411. Taotao, Q., Xuechuan, W., and Longfang, R. (2009). Recovery of collagen from phosphonium tanned leather shavings and application as formaldehyde scavenger. J. Am. Leather Chemical. Assoc., 104, 316322. Taylor, M.M., Cabeza, L.F., DiMaio, G.L., Brown, E.M., and Marmer, W.N., Carrio, R., Celma, P.J., and Cot, J. (1998). Processing of leather waste: Pilot scale studies on chrome shavings. Part, I. Isolation and characterization of protein products and separation of chrome cake. J. Am. Leather Chemical. Assoc., 93, 6182. Taylor, M.M., Cabeza, L.F., Marmer, W.N., and Brown, E.M. (1997a). Computerassisted method to measure the adhesive properties of hydrolysis products from collagen. J. Am. Leather Chemical. Assoc., 92, 2837. Taylor, M.M., Cabeza, L.F., Marmer, W.N., and Brown, E.M. (2000). Use of tryptec enzyme preparations in treatment of chrome shavings. J. Am. Leather Chemical. Assoc., 95, 243252. Taylor, M.M., Cabeza, L.F., Marmer, W.N., and Brown, E.M. (2001). Enzymatic modication of hydrolysis products from collagen using a microbial transglutaminase. I. Physical properties. J. Am. Leather Chemical. Assoc., 96, 319 332. Taylor, M.M., Cabeza, L.F., Marmer, W.N., Brown, E.M., and Kolomaznik, K. (1998). Functional properties of hydrolysis products from collagen. J. Am. Leather Chemical. Assoc., 93, 4050. Taylor, M.M., Diefendorf, E.J., Brown, E.M., and Marmer, W.N. (1992). Characterization of products isolated by enzyme treatment of chromium containing leather waste. J. Am. Leather Chemical. Assoc., 87, 380389. Taylor, M.M., Diefendorf, E.J., and Marmer, W.N. (1991). Efciency of enzymic solubilization of chrome shavings as inuenced by choice of alkalinity-inducing agents. J. Am. Leather Chemical. Assoc., 86, 199208. Taylor, M.M., Diefendorf, E.J., Marmer, W.N., and Brown, E.M. (1994). Effect of various alkalinity inducing agents on chemical and physical properties of protein products isolated from chromium containing leather waste. J. Am. Leather Chemical. Assoc., 89, 221228. Taylor, M.M., Diefendorf, E.J., Marmer, W.N., and Brown, E.M. (1995). Effect of deionization on physical properties of gelable protein products recovered from solid tannery waste. J. Am. Leather Chemical. Assoc., 90, 365374. Taylor, M.M., Diefendorf, E.S., and Na, G.C. (1990). Enzymic treatment of chrome shavings. J. Am. Leather Chemical. Assoc., 85, 264275. Taylor, M.M., Diefendorf, E.J., Thompson, C.J., Brown, E.M., Marmer, W.N., and Cabeza, L.F. (1997b). Extraction of value added byproducts from the treatment of chromium containing collagenous leather industry waste. J. Soc. Leather Technol. Chem., 81, 513. Taylor, M.M., Liu, C.K., Latona, N., Marmer, W.N., and Brown, E.M. (2002). Enzymatic modication of hydrolysis products from collagen using a microbial transglutaminase. II. Preparation of lms. J. Am. Leather Chemical. Assoc., 97, 225234.

Downloaded by [Central Leather Research Institute] at 01:01 01 December 2011

Recovery of Chromium-Tanned Wastes of Leather Making

2075

Downloaded by [Central Leather Research Institute] at 01:01 01 December 2011

Taylor, M.M., Liu, C.K., Marmer, W.N., and Brown, E.M. (2003). Enzymatic modication of hydrolysis products from collagen using a microbial transglutaminase. III. Preparation of lms with improved mechanical properties. J. Am. Leather Chemical. Assoc., 98, 435444. Taylor, M.M., Marmer, W.N., and Brown, E.M. (2005). Characterization of biopolymers prepared from gelatin and sodium caseinate for potential use in leather processing. J. Am. Leather Chemical. Assoc., 100, 149159. Trezza, M.A., and Scian, A.N. (2007). Waste with chrome in the Portland cement clinker production. J. Hazard Mater., 147, 188196. Vedaraman, N., Rangasamy, T., Muralidharan, C., and Rao, P.G. (2002). A process for preparation of leather like sheet and the sheet prepared thereby. No.752 Del 2002. Veeger, L. (1993). Ecological procedure to solve the tannery waste problems. J. Am. Leather Chemical. Assoc., 88, 326329. Vieira, M.S., and Marcilio, N.R. (2005). Recovery of chromium from chrome containing leather waste from the leather industry: The optimization of the process. Paper presented at Second Mercosur Congress on Chemical Engineering Proceedings, Rio De Janeiro, Brazil, August 1418. Walawska, B., and Kowalski, Z. (2000). Selection of technological variants of sodium chromate (VI) production process with the use of chromic waste. J. Environmental Studies., 9, 103111. Walawska, B., and Kowalski, Z. (2001). Environmental evaluation of the effects of using chromic waste in the production of chromium compounds. J. Cleaner Production., 9, 219226. Xuechuan, W., Longfang, R., and Taotao, Q. (2009). Novel way of transformation of tannery waste to environmentally friendly formaldehyde scavenger. Environmental Progress & Sustainable Energy, 28, 285290. Yilmaz, O., Kantarli, C. I., Yuksel, M., Saglam, M., and Yanik, J. (2007). Conversion of leather wastes to useful products. Resources Conservation and Recycling, 49, 436448. Zhao, S., Zhang, M., Li, G., and Liu, W. (2009). Preparation and characterization of alkali-soluble collagen from pigskin shavings. J. Am. Leather Chemical. Assoc., 104, 344351.

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