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1. Waste conversion R.Prasanna Technical officer  Leather Process Technology Depatment CSIR-CLRI

2. Extraction of cellulose from renewable resources and its application in leather finishing   A. Tamilselvi , Gladstone Christopher Jayakumar , K. Sri Charan , Bindia Sahu , P.R. Deepa , Swarna V. Kanth , J. Kanagaraj PII: S0959-6526(19)31502-1 DOI: 10.1016/j.jclepro.2019.04.401 Reference: JCLP 16757 To appear in: Journal of Cleaner Production Received Date: 28 January 2019 Accepted Date: 30 April 2019

3. Recycle  

4. Abstract Waste generation from groundnut and sugarcane industries are at high alarming rate due to their disposal constraint.  These wastes are currently used as a raw material for the production of compost, fuel, alcohol, and paper. Cellulose and its derivatives are being used in many industries like paper, and pharmaceutical,   Application of cellulose in the leather industry uses cellulose derivatives as finishing chemicals such as nitrocellulose, ethyl cellulose. In the current study, an attempt has been made to find the application of cellulose from groundnut husk and sugarcane bagasse as an auxiliary chemical in leather finishing.  Cellulose is extracted from wastes by modified acid hydrolysis method to enhance the yield. Extracted cellulose has been characterized and compared with commercial cellulose sample. From the characterization studies, it confirms that extracted cellulose matched with commercial samples.  Extracted cellulose used in leather finishing as an ingredient to upgrade the low-quality leathers, which primarily have grain damages. Cellulose with different concentration of plasticizer has been used in the base coat along with binders and pigments.  Finished leathers have been characterized to understand the physical characteristics. From the various analysis, it ascertains that the cellulose has imparted fullness to the finished leather without impacting the aesthetic property. The study provides a better utilization of sugarcane bagasse and groundnut husk wastes in leather industry leading to effective waste management prototype.

5. What are Plasticizers   Plasticizers are colorless, relatively nonvolatile liquids that can be classified by their chemical structure or function. The most common chemical structures include: Phthalates,Phosphates,Carboxylic acid esters,Epoxidized fatty acid esters,Polymeric polyesters,Modified polymers, Liquid rubbers A plasticizer is a substance that is added to a material to make it softer and more flexible, to increase its  plasticity , to decrease its  viscosity , and/or to decrease  f riction  during its handling in manufacture.

6. Graphical abstract

7. Introduction Groundnut (Arachis hypogaea ) is a member of the legume or bean family. It is widely used as a source for oil, food, lubricants etc. Groundnut is a major source in bridging the vegetable oil deficit in India and hence, is cultivated extensively in the country. India produces around 6 million tons of groundnut annually ( Madhusudhana , 2013) and is the second largest producer in the world. Apart from groundnuts, the byproducts of the groundnut industry which include groundnut husk, kernels, cake, Haulms etc. have several useful applications. Groundnut husk has great potential for commercial use and is used as fuel, filler in cattle feed etc. The chemical composition of groundnut shell is 38.31% cellulose, 21.10% hemicellulose and 27.62% lignin ( Bano and Negi , 2016), making it a viable raw material for cellulose. Similar to groundnut, sugarcane ( Saccharum officinarum ) is also extensively produced in India. India is estimated to produce around 341.2 million tons in 2017/18. Sugarcane is mainly used for the production of sugar. The major byproduct of the sugar industry is sugarcane bagasse, which is used in alcohol production, paper industry, and generation of electricity. Bagasse consists around 35.2% cellulose, 24.5% is hemicellulose, and 22.2% is lignin and ash 20.9% ( Rezende et al., 2011). Cellulose can be extracted from these sources in a cost-effective manner due to the relatively low cost and high availability of raw materials. Cellulose is used in many industries like paper, fuel, leather and pharmaceutical. Cellulose has been applied as a filler in many products like thermoplastics ( Boldizar et al., 1987), adhesives ( Veigel et al., 2011). Currently, cellulose derivatives are being used in the leather finishing like nitrocellulose ( Gumel and Dambatta , 2013), methylcellulose, carboxymethyl cellulose ( Sarkar , 2005) and ethyl cellulose (Koch, 1937). Globally, leather is manufactured in a huge quantity and India is one of the major exporters of leather. The leather exported from India was estimated to be valued around 1.42 billion US$ in April-June quarter, 2017. In this present study, cellulose was extracted from the renewable wastes using acid hydrolysis followed by alkaline hydrolysis and bleaching, and ACCEPTED MANUSCRIPT 4 then the extracted cellulose was applied as a component in the intermediate coat of leather finishing. Leather finishing is the final process in leather manufacture which provides aesthetic property to the leather products. Finishing primarily involves three steps viz , base, intermediate and top coat. Base coat chemically modify the surface property of the crust (post tanned) leathers to fix the finishing chemicals. Finishing formulation for base coat consist of solvents. Intermediate coat majorly consists of binders for filling and enhance the physical properties. It also acts as a carrier for pigments and dyes to be fixed on leather. In addition, depending on the choice of binders and fillers, the finishing properties can be controlled for final application. Fillers in the finishing composition influence the uniform texture and levelling of dyes and pigments on the surface. Top coat is comprising of lacquers based on polyurethane and cellulose derivatives to provide protection to the leather finish. In the present study, the extracted cellulose is used as an ingredient in the intermediate coat in the leather finishing. The prepared formulation has been sprayed on the crust leathers and prepared as a films to understand the physical characteristics

8. Major sugarcane producing countries  

9. Major Groundnut P roducing C ountries

10. Materials and Methods Materials Sugarcane bagasse and groundnut husk are kindly supplied by local vendors and farmers, respectively. Chemicals used for analysis are of analytical grade. 2.2. Isolation of Cellulose Cellulose was recovered from agricultural wastes following technique reported by Azubuike et al. (2011). Groundnut shells were grinded into very small size and washed with water. Sample was dried in a hot air oven at 65oC for 24 h. To remove the lignin, 10 g of the sample was dispersed in 100 mL of a solution containing 3.5% (v/v) nitric acid and 1 mg of sodium nitrite and maintained at a temperature of 90oC for 2 h. 100 mL solution containing 2% (w/v) sodium sulfite and 2% (w/v) sodium hydroxide was added and maintained at 50oC ACCEPTED MANUSCRIPT 5 for 1 h. A solution containing 17.5% (w/v) of sodium hydroxide was added and maintained for 30 min at 82oC. The sample was dried at 60oC for 16 h. The sample was bleached with 100 mL solution containing 4% sodium hypochlorite and maintained at 40oC for 2 h. This step was repeated until the residue turns to white color. Then the solution was filtered to separate the residue and washed thoroughly after each step. The product was washed until pH becomes 7 and dried to get the constant weight at 70oC for 14 h. 2.3. Application of cellulose in leather finishing In the present, extracted cellulose was used an ingredients of the base coat residue as given in Table 2. The chemicals were added as given in Table 2 and the solution was thoroughly mixed. 1% (w/v) cellulose was added to the chemical constituents. To study the interaction of cellulose with base coat residue, finish films were prepared by drying the chemicals at 50-55°C for 24 h. Whereas for leathers, finishing residue was applied in 5 coatings through spray method on white crust leather from goatskin after each coating leathers were sun dried (shade) for a period of 1 h. Topcoat containing Lacquer was applied through spray dyeing to fix the base coat. Plating Technique was done to provide smoothness and glossy nature to leather samples. 2.4. Characterization methods 2.4.1. Fourier Transform Infrared (FTIR) Analysis FTIR and ATR- FTIR Analysis were done to determine the surface functional groups using JASCO FTIR 4700. Samples were dried and mixed with KBr in a ratio of 1:100(w/w). FTIR spectra of the extracted cellulose was recorded over the range of wavenumber (400-4000 cm-1). The scan was done with a resolution of 4 cm-1 . ATR-FTIR analysis for finish films was done over the range of (600 cm-1-4000 cm-1) with a resolution of 4 cm-1 . 2.4.2. Thermogravimetric analysis (TGA) Thermal gravimetric analysis of raw materials, extracted cellulose and finish films were analyzed to study thermal stability of samples between the ranges of 25-600oC at a heating rate ACCEPTED MANUSCRIPT 6 of 20oC/min. The analysis was done in a nitrogen atmosphere with gas flowrate of 100 (mL/min) to inhibit thermo-oxidative degradation using a TA instruments Q50 series thermogravimetric analyzer. DTG graphs for all the samples were prepared using Origin Pro Software. 2.4.3. Differential Scanning Calorimetry (DSC) DSC analysis was analyzed to study thermal behavior of finish films using TA Instruments DSC Q200. DSC analysis was done over the range of 30-300oC at a heating rate of 10oC/min under Nitrogen atmosphere (50 mL/min). 2.4.4. Physical Strength Analysis Control and experimental finished leathers were maintained at standard conditions approved for leather testing by IS 2419 standard at a temperature of 25oC with a relative humidity of 65%. Leathers were placed inside the climatic chamber for 48 h before cutting test specimens for testing. The physical analysis was done for leather by following their respective standard procedures. Finished leathers were analyzed for tensile strength, tear strength, water vapor permeability and rub fastness as per the SATRA standard norms (SATRA TM 162, 172, 43 and 8).

11. Results and Discussion In the present investigation, renewable resource waste has been utilized to extract cellulose and use it as an ingredient in leather finishing. Cellulose is prepared from renewable resources like groundnut husk (GH) and sugarcane bagasse (SCB). Percentage yield of cellulose extracted from groundnut husk and sugarcane bagasse are 36.7 and 31.8, respectively based on the raw material weight. Nitric acid assists in removal of lignin ( Azubuike et al., 2012) and at high temperatures, nitric acid

12. Conclusion In this study, cellulose has been extracted from renewable resources, ground nut shells and used as an ingredient in leather finishing. Extraction method has been finely tuned to enhance the yield of cellulose. Extracted cellulose had been characterized using various physico -chemical techniques to establish the purity and physical characteristics. From various characterization studies, it is clearly established that the extracted cellulose is similar to commercial samples.