Proceedings Waste 2008: Waste and Resource Management a Shared Responsibility
Stratford-upon-Avon, Warwickshire, England, 16-17 September 2008
2008 Golder Associates (UK) Ltd, managing organisation for Waste 2008 INTEGRATED MANAGEMENT OF POTATO STARCH WASTES C. ISRAILIDES*, A.G. VLYSSIDES o , D. ARAPOGLOU*, TH. VARZAKAS oo , R. MARCHANT ooo AND A.A. VLYSIDES o *Institute of Technology of Agricultural Products, Greece o National Technical University of Athens, Department of Chemical Engineering, Greece oo Technological Educational Institution of Kalamata, School of Agriculture, Greece ooo University of Ulster, School of Biomedical Sciences SUMMARY : The problem of Potato Starch Waste (PSW) management is of great concern to the potato industries in Europe and an integrated and environmental friendly solution is yet to be found and is under investigation. However due to different conditions and production scales in the various industries a single solution for PSW management might not be possible in all cases. Among PSW, Potato Peel Wastes (PPW) are the major waste of the potato industry. This paper discusses the current practice, on PSW utilisation, based on a bilateral UK/Greece exchange programme, and proposes various solutions for its economic and ecological utilisation. 1. INTRODUCTION The potato peel is a zero value waste of the potato processing plants. While consumption of potatoes has decreased, processed products such as French fries, chips, and puree have experienced growing popularity (ZMP, 2000). Losses caused by potato peeling range from 15 to 40%, their amount depending on the procedure applied, i.e. steam, abrasion or lye peeling. (Scieber et al., 2001). The plants peel the potatoes as part of the production of french fries, instant potatoes and similar products. The waste produced is 90kg per tn of influent potatoes and is divided between 50kg of potato skins, 30kg starch and 10kg inert, substances. Another problem for the potato crisp industry is that it uses large amounts of water and therefore produces great quantities of liquid waste. For one tonne of influent potato, 4.78 tn of water is required. This derives from the initial potato washing of 0.57 tn, 0.73 tn for the peeling, 0.28 tn for the water transport, 1.66 tn for the cut and crisp washing and 1.54 tn for the machines and floor washing. Presently, in most industries any starch separation and recovery method is not efficient since solid wastes leave the industry together with the wastewaters. The downstream processing in the potato crisp industry is given in the following general flowchart of figure 1. Figure 1: Procedures in the potato crisps manufacturing and production of liquid wastes. The various steps include: Pre-washing of potatoes with water to remove the soil from the skin. Mechanical peeling of potatoes, in a vessel with rotating bottom. Manual or mechanical sorting of potatoes to include those which are free from diseases and / or removal of parts which are not apt for further treatment. Cutting of the potatoes (mechanical) in thin slices. Washing the sliced potatoes before frying, with clean water. Drying by straining the potato slices. Frying the potatoes in vegetable oil at 190 o C. The oil is recycled with a pump and reaches the required temperature through a heat exchanger. After some hours of circulation the vegetable oil passes through a special filtering vessel where the suspended solids are filtered out. Photoelectric selection of the suitable crisps. Salting of the crisps and addition of various other additives. Weighing and packaging in polypropylene bags. Packaging of bags in larger boxes and loading to tracks for distribution to warehouses, and super markets. The liquid wastes from the potato industry are not the only ones produced from the potato washing. There are also the ones from floor washing and the machinery. The latter are recalcitrant, of high polluting power due to the presence of various oils. The qualitative and quantitative characteristics of the various wastes produced in a potato crisps industry are listed in Table 1. Table 1: Quantitative and qualitative characteristics of liquid waste produced in a potato crisp industry. (TSS: Total Suspended Solids, VSS: Volatile Suspended Solids, COD: Chemical Oxygen Demand, BOD 5 : Biological Oxygen Demand) Procedure Flow TSS VSS COD BOD 5 m 3 /tn kg/tn kg/tn mg/l mg/l 1 Prewash potato 0.57 12.2 1.0 736 27 2 Peeling 0.73 50.4 43.8 8004 3165 3 Sorting by size 0.28 8.3 7.4 8188 3312 4 Slicing 0.5 12.4 11.4 8464 3539 5 Water crisp transfer 0.35 18 17.3 8832 3854 6 Final wash 0.8 9.1 8.7 8832 3854 7 Floor washing 1.54 1.01 0.3 2300 261 Total 4.77 111.4 89.9 5552 2067 The main drawbacks of current PSW management according to the flow chart of figure 1, are the following: 1. The excessive use of clean water, resulting in the production of large quantities of liquid wastes. 2. The demand for the operation of large biological treatment, due to high hydraulic loads. 3. The inadequate utilization of solid wastes, due to sorting difficulties according to their commercial value (eg. Separation of starch from soil and peelings). 4. Insufficient operation of biological treatment units due to the presence of recalcitrant wastes like the used frying oils and wastes with high COD/BOD 5 ratio such as the ones from floor wash and potato pre-wash. Another major stumbling block for the efficient operation of biological treatment units is that starch comes in a coagulated form of colloidal starch. This results in the blocking of pipes and poor operation of the system and requires a pre-treatment step to make the wastes more appropriate for biological treatment. An integrated system of PSW management should include: 1. Minimization of water use by recycling. 2. Separation of starch and PSW and its utilization for the production of high added value products, including bioethanol for energy. 3. The improvement of the efficiency of biological treatment unit, in order to become lighter to operate due to acceptance of less hydraulic and polluting loads. Oxidation of the liquid wastes as a pretreatment stage before biological treatment, using a physicochemical method such as the Fenton method. (Vlyssides et al., 2003, 2008). This will also make its operation simpler with a simultaneous reduction of the required, main and functional costs. This paper reports on an integrated management of potato industry wastes and proposes various solutions for an ecological and feasible utilisation of the PSW and PPW. 2. MATERIALS AND METHODS Samples of PPW were brought to biotechnology laboratory of the national agricultural research foundation (www.nagref.gr) in Greece and were dried. The moisture was determined by oven drying at 105 o c to a constant weight. Total sugars were estimated by the colorimetric method of Dubois et al. (1956) and reducing sugars by the DNS method (Miller, 1959). Protein was estimated by the Kjeldahl method by multiplying residual nitrogen (N) by 6.25. Fat was determined by the Soxhlet method (AOAC, 1995). Heavy metal analysis was performed by atomic absorption according to the standard methods for the examination of water and wastewater, (APHA, 1989). Fermentations for ethanol production were carried out in 250ml Erlen Mayer Flasks with fermentation traps (Fig. 2). Figure 2: Laboratory set up for PPW ethanol fermentation with a trap. In each flask the following reagents were added: 1. PPW 40.2 g (moisture 85% - starch 52.09% per dry weight). 2. NH 4 NO 3 0.5% (w/v) 3. Peptone 0.1% (w/v) 4. HCl 0.5M 120 ml The mixture was sterilised at 121 0 C for 15 min. During sterilization the carbohydrates of PPW were hydrolysed to fermentable sugars. The pH was corrected to 4.15 with Na OH (1 M). Forty eight hours old culture of Saccharomyces cereviciae grown in synthetic fungal medium was used to inoculate the PPW broth at 6.2% (v/v). Fermentation was carried out for five days. The results presented are the averages of three runs. For the determination of total carbohydrates, there was an initial hydrolysis of the sample with HCl 0.5 M for 30 min at 90 o C. Starch was measured quantitatively with the Behringer Mannheim/R-Biopharm, Kit. Cat. No 10207748035. 2.1 Enzymatic Hydrolysis For enzymatic hydrolysis of PPW the following enzyme preparations from Novozymes A/S, Denmark, were made: Viscozyme L. The activity if Viscozyme L was 120 Fungal Beta-Glucanase Units (FBG)/ml. One FBG is the amount of the enzyme required under the standard condition (30 o C, pH 5.0, reaction time 30 min) to degrade barley -glucan to reducing carbohydrates with a reduction power corresponding to 1mol glucose/min. Ternamyl 120L. Ternamyl 120L is a heat-stable amylase from Bacillus licheniformis.The enzyme activity was 120 KNU/g (kilo novo units of -amylase). The KNU is the amount of enzyme which breaks down 5.26 g of starch per hour according to Novozymes standard method for the determination of -amylase. Liquozyme Supra. Liquozyme Supra is a heat stable -amylase from Bacillus lichneniformis. The enzyme activity was 200 KNU/g. 2.2 Procedure Two g of dry Potato Peel Waste (PPW) was mixed with 100ml of distilled water. The mixture was treated with enzymes in two steps. The first step, liquefaction, was performed with Ternamyl 120 L at 85 o C and pH 6.0 at reaction time 1h, or with Liquozyme Supra at 55 o C, pH 5.5 and reaction time 20h. The second step, saccharification, was performed at 44 o C, pH 4.6 for 2.5h reaction time with a following enzyme combinations: a. Liquozyme Supra 1% (v/w) and 6 FBG Units Viscozyme. b. Ternamyl 120 L, 0.24 KNU and 6 FBG Units Viscozyme. Another combination of Ternamyl 2.4 KNU and Viscozyme 12 FBG was also run. 3. RESULTS AND DISCUSSION The chemical analysis of PPW is given on Table 2. Table 2: Chemical composition of Potato Peel Wastes (PPW). Parameters % dry weight Moisture 85.06 Nitrogen 1.3 Protein (N tot *6.25) 8.0 Total Soluble Sugar 1.0 Total Carbohydrates 58.7 Reducing Sugars 0.61 Fat 2.6 Ash 6.34 3.1 Ethanol Production from PPW Bioethanol produced from potato waste has a large potential market. If federal Government regulations are adopted in light of the Kyoto accord, the mandated blending of bioethanol with traditional gasoline in amounts up to 10% will result in requirements for large quantities of bioethanol. Among the bioenergy crops used for fuel ethanol production, sugarcane is the main feedstock utilized in tropical countries like Brazil and India. In North America and Europe, fuel ethanol is mainly obtained from starchy materials, especially corn. On the other hand, intensive research on the utilization of lignocellulosic biomass as feedstock for energy purposes has been carried out during the last few years. The PPW contain sufficient quantities of starch, cellulose, hemicellulose and fermentable sugars and can serve as an ethanol feedstock. A number of the batches of PPW where fermented to determine fermentability and ethanol production. The final pH at the end of fermentation was 3.89. After initial chemical hydrolysis the total sugars were 19.37 gL -1 , while the reducing sugars were 18.14 gL -1 . The reducing sugars after enzymatic hydrolysis were as such: For combination (a), 14.06 gL -1 , while for (b) was 10.27 gL -1 for the lower enzyme concentration and 14.69 gL -1 for the higher concentration respectively. At the end of fermentation the reducing sugars were 4.34 gL -1 . Therefore the sugars consumed were 15.03 gL -1 . The ethanol produced from fermentation was 6.97 gL -1 . The product yield Y p/ S (g of product / g of sugar consumed) was 0.463 (or 46.3%). This corresponds to 92.6% of the max theoretical yield. The production of ethanol from PPW is a feasible option provided that this will be confirmed by a scaling up technico-economical study. Also the willingness of the company to get involved and devote resources in this direction will play a major role. An alternative possible solution could be for a nearby ethanol producing Company, to use the PPW as a raw material. This has been successfuly practised in the U.S.A. (Idaho) by an ethanol plant from the J.R. Simplot Co. (www.vincentcorp.com). 3.2 Animal Feed The nutritive value of potato processing wastes for animal feed has been studied in mixed rations for dairy cattle. (Onwubuemeli et al., 1985). According to the study potato waste did not significantly affect the digestibility of crude protein or dry matter, but at 20% substitution for high moisture corn, the digestibility of acid detergent fiber was decreased, while milk fat concentration was decreased. The direction of PPW for animal feed may be a risky option. Firstly the material as it comes out of the factory has high moisture content (70-80%) which limits its value as an animal feed. Drying might prove very costly and increase significantly haulage costs. Second, the amount of protein (8%) of dry matter is considered low for animal feed even for ruminants. However this level maybe enhanced by appropriate semisolid fermentation, (Han and Callihan, 1974) especially with the use of edible basidiomycete strains (Lentinula edodes, Pleurotus ostreatus) which contain powerful lignocellulolytic enzymes. Table 3, shows the heavy metal profile of PPW. Taking into account the data from Table 3, PPW could be incorporated in ruminant rations at a level up to 5% (w/w) of their normal diet. Also its use in pig diets may also be considered, subject to further feeding trials for the assessment of the final levels in the diet. (Animal Research Institute, NAGREF, Greece, Personal Communication). Table 3: Concentration of heavy metals in PPW. / Parameter Value (mg kg -1 ) 1 Cd 3.66 0.54 2 Total Cr 16.66 1.4 3 Cu 2.66 0.5 4 Pb 74.01 8.3 5 Zn 271 23 6 Ni 253 45 7 Ca 1345 85 8 Na 543 38 9 K 2185 122 10 Fe 1850 210 3.3 Composting Composting PPW, is a simple and easy process which could be done on site. The produced compost has a sale value of 300 /tn. Given an estimated cost of production of 200 /tn, for a factory producing 450 tn PPW/year (figures taken from a potato industry, Chipita Co., in Greece) the net gain from the selling of compost would be 450 tn x 100 / tn = 45.000 /year. 3.4 Small Scale Pyrolysis The aim of Pyrolysis of PPW is the production of energy through heat. It seems a good option but needs feasibility studies. 3.5 Anaerobic Fermentation Anaerobic fermentation for the production of biogas (CH 4 ) could be done together with the liquid (starch waste) stream and utilising all the other wastes from the potato processing. It has the advantage that it is a simple and low cost operation and could be done in the same area in situ. It has been proven that for each tn of starch waste about 250 m 3 of methane is produced and 5 tn of starch waste per day minimum is necessary for a feasible application. 3.6 Production of High Added Value Products Through Fermentation The production of high added value products from potato wastes is possible, yet it requires infrastructure which makes it rather difficult to apply in small units. However starch waste has been shown to be a suitable feedstock for industrial fermentations, comparable to traditional substrates such as molasses and syrups in many cases (Underkofler and Lockwood, 1976). The production of extra-cellular enzymes, amylases, proteases and polygalacturonases from PPW extracts from the bacterium Bacillus subtilis, maybe promising for industrial applications. (Mahmood et al., 1998). Also an industrially important polysaccharide pullulan can be produced by enzymic hydrolysis of potato starch waste (PSW), followed by fermentation by the yeast Aureobasidium pullulans (Barnett et al., 1999). Furthermore the substrate yield and purity of the pullulan produced from PSW was among the highest compared to other agro-industrial wastes used, which is an important factor in terms of the economic viability for pullulan production (Israilides et al., 1999). 3.7 Other Potential Applications Potato peel aqueous extracts (PPE) showed strong antioxidant, free radical scavenging activity, suggesting the possibility that PPW could be employed as an ingredient in health or functional foods (Nandita & Rajini, 2004, Friedman, 1997). This is due to the fact that PPE were shown to be a source of phenolic acids, especially of chlorogenic, gallic, protocatechuic and caffeic acids. 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