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ANALYZES OF THE USED FRIED OIL UNDER ENVIRONMENTAL PERSPECTIVE AND ITS POSSIBILITIES FOR PRODUCTION OF BIODIESEL Carlo

Alessandro Castellanelli Carolina Iuva de Mello castellanelli@bol.com.br carolinaiuva@hotmail.com Department of Production Engineering, Federal University of Santa Maria (UFSM) Av. Roraima 1000 - 97105-900, Santa Maria - RS - Brazil Abstract. At the moment, questions concerning the environment degradation and the sustainable development are highly argued, but Brazilian companies' efforts for the reduction and elimination of inconsequential effects caused by its products are still presented in incipient numbers. Amongst the products that can generate negative effects to environment and are generated daily and in large amount, it can be cited the used fried oil. The lack of information by the manufacturers makes the consumers directly discard it in sinks, toilets or even in the rivers and soil, contributing with the increase of environmental impacts. This article analyzes the presence of referring information to the correct final destination of the oil in the packings of the main current manufacturers and considers a model of informative stamp aiming the correct disposal and recycling of this used oil to be converted in biodiesel, as well as, shows the ways of production of used fried oil's biodiesel, the reductions of environmental impacts and the costs of this recycling. Keywords: Recycling, Biodiesel, Used Fried Oil.

1. INTRODUCTION Currently, a great increase of strategies adoption for the environment preservation can be observed, as a result of an evolution of the awareness by the citizens and companies in an intrinsic relation between its acts and the pollution of the environment, either in the residences or in the industrial processes. One of the main concerns is about the generation and disposal of solid, liquid or gaseous residues, which arriving at the atmosphere, ground or water, causing environmental

impacts. The edible oils, in special those used in the fry process, appear in this context as a daily generated residue in homes, industries and establishments in Brazil and all the other countries. Due to the lack of information by the population and/or the lack of dissemination of ideas supporting the healthy environment, this residue is poured in waters, in rivers and streams or simply in sanitary sinks and toilets, going to stop in the sewer systems causing damages in the clogging of the pipes and increasing the price of the processes of the Stations of Treatment and causing the pollution of the aquatic environment. In this way, urges the necessity of adoption of strategies, supporting the information to the population, that these attitudes provoke several environmental issues and the correct way of the disposal of this residue. Although already having been treated for many in the past as an ideological question of ecological groups who didn't accept the modern society consumption, the concern about the environment preservation assumes a great importance today for the companies. An important aspect observed in the contemporary environmental question is the commitment of the entrepreneurs and administrators in the search for solutions of the production, distribution and consumption of goods and services issues. To use and to treat the urban solid and liquid residues is a responsibility concerning all the society. Verifying the relative information to the correct destination of the edible oil after-use, the work considers a model of stamp of warning to be incorporated to the label of the edible oil packings, indicating the correct destination of the used oil, creating competitive advantages to the participant companies and environmental profits to the society, contributing for a more harmonic social and economic development between man and nature. This paper analyzes the presence of referring information to the correct final destination of the oil in the Brazilian edible oil packings, as well as shows the ways of production of used fried oil's biodiesel, the reductions of environmental impacts and the costs of this recycling. 2. BIODIESEL AND THE USED FRIED OIL Rudolph Diesel, a German engineer, introduced the diesel engine over a century ago (Nitske and Wilson, 1965). Since then a great deal of research and development has taken place, not only in the design area but also in finding an appropriate fuel. For many years, the ready availability of inexpensive middle-distillate petroleum fuels provided little incentive for experimenting with alternative, renewable fuels for diesel engines. However, since the oil crisis of the 1970s, research interest has expanded in the area of alternative fuels. Many proposals have been made regarding the availability and practicality of an environmentally sound fuel that could be domestically sourced. Methanol, ethanol, compressed natural gas (CNG), liquefied petroleum gas (LPG), liquefied natural gas (LNG), vegetable oils, reformulated gasoline and reformulated diesel fuel have all been considered as alternative fuels. Of these alternative fuels, only ethanol and vegetable oils are non-fossil fuels. Due to the increase in the price of the petroleum and the environmental concerns about pollution coming of exhaust gases from car, biodiesel is becoming a developing area of high concern. There are different ways of production, with different kinds of raw materials: refine, crude or frying oils. Also there are different types of catalyst, basic ones such as sodium or potassium hydroxides, acids such as sulfuric acid, ion exchange resins, lipases and supercritical fluids. It is estimated that in the coming years, the fossil oil price will increase because the oil production cannot meet the projected demand due to oil depletion (Association of Peak Oil and Gas, 2004). This is a result of overconsumption in the developed countries and overpopulation in the developing countries (Korbitz, 1999). A lot of efforts have been carried out to develop an alternative fuel for the current energy and transportation vehicle system, i.e.: fuel cell, electric power, hydrogen or natural gas for internal combustion engines, etc. One of the promising alternatives that are applied in small scale production is biodiesel. The American Society for Testing and Materials (ASTM) defines biodiesel fuel as monoalkyl esters of long chain fatty acids derived from renewable lipid feed stocks, such as vegetable oil or animal fat. "Bio" represents its renewable and biological source in contrast to traditional petroleum based diesel fuel; "diesel" refers to its use in diesel engines. As an alternative fuel, biodiesel can be used in neat form or blended with petroleum based diesel.

Several sources for producing biodiesel have been studied such as rape seed, coal seed, palm oil, sunflower oil, waste cooking oil, soybean oil, etc. Due to the high cost of the fresh vegetable oil, waste cooking oil gives interesting properties because it can be converted to biodiesel and it is available with relatively cheap price (Nisworo, 2005; Zhang et al., 2003). The most common way to produce biodiesel is by transesterification, which refers to a catalyzed chemical reaction involving vegetable oil and an alcohol to yield fatty acid alkyl esters (biodiesel) and glycerol (by-product) as can be seen in Figure 1.

Figure 1 - Transesterification reaction of triglyceride and methanol to fatty acid methyl esters (biodiesel) and glycerol. Source: Kasteren and Nisworo (1996). Transesterification reactions can be alkali-catalyzed, acid-catalyzed or enzyme catalyzed (Bunyakiat et al., 2006). An excess of methanol is used to shift the reaction to the right side in order to achieve high yield of methyl esters/biodiesel. Most biodiesel industries use the alkali catalyzed process. One limitation to the alkali catalyzed process is its sensitivity to both water and free fatty acids. Free fatty acids can react with the alkali catalyst to produce soaps and water. Therefore Freedman et al. (1984) stated that refined vegetable oils with free fatty acids content of less than 0.5% (acid value less than 1) should be used to maximize methyl esters formation. The presence of water may cause ester saponification and can consume the catalyst and reduce the catalyst efficiency. The presence of water has a greater negative effect than that of the free fatty acids. Ma et al. (1998) stated that the water content should be kept below 0.06%. Most industries use pre-treatment step to reduce the free fatty acid and water content of the feed stream. Usually free fatty acid is reduced via an esterification reaction with methanol in the presence of sulfuric acid. The pre-treatment step not only causes the production process to be less efficient (Kusdiana and Saka, 2004) but also increase the capital cost. These facts hinder the efficient use of waste cooking oil, animal fats and crude oils as source for biodiesel since they generally contain water and free fatty acids. Kasteren (2006) says that there is an alternative for biodiesel production, namely the supercritical methanol method. The great advantages of supercritical methanol are: -no catalyst required; -not sensitive to both water and free fatty acid; -free fatty acids in the oil are esterified simultaneously. A comparison of the properties of the supercritical and conventional method can be seen in Table 1. The absence of pre-treatment step, soap removal, and catalyst removal can significantly reduce the capital cost of a biodiesel plant, but the expected high operating cost due to high temperature and pressure can be a drawback for supercritical method. That is why it is interesting to see whether the supercritical methanol method is economically feasible to be applied in a biodiesel plant. Table 1 - Properties of supercritical and conventional transesterification

Source: Kasteren and Nisworo (1996). Concerning the costs, the program of master degree in Engineering of the Federal University of Rio De Janeiro - COPPE/UFRJ indicates US$0,25 as average cost of production for liter of biodiesel, made by used fried oil, the low cost is due to the fact that the used fried oil generally is gotten for free in restaurants, snack bars and other establishments. 3. USED FRIED OIL UNDER THE ENVIRONMENTAL PERSPECTIVE The increasing production of waste frying oils (WFOs) from household and industrial sources is a growing problem in Brazil and all around the world. This residue is regularly poured down the drain, resulting in problems for wastewater treatment plants and energy loss, or is integrated into the food chain through animal feeding, thus becoming a potential cause of human health problems (Costa Neto et al., 2000). There are several end-uses for this waste, such as the production of soaps or of energy by anaerobic digestion, thermal cracking (Zaher, 2003), and more recently the production of biodiesel, a fuel that can be used as a mineral diesel substitute for engines. Due to the high contents of carbohydrates, proteins and lipids (fats or oils) in oilseeds, one of the main applications is to be processed to edible oils (vegetable) for human consumption (diet). Nowadays, most of the used cooking oil is poured into the sewer system of the cities. This practice contributes to the pollution of rivers, lakes, seas and underground water, which is very harmful for environment and human health (Hamasaki et al., 2001; Wilsee, 1998). But there are at least another two reasons to avoid these oil spills. On one hand, oils and grease may cause the clogging of the pipes because they stick to the inner walls and reduce the effective diameter of the sewer pipes. If this layer becomes thicker, it may cause sewage spills. On the other hand, if oil reaches the wastewater treatment plants, it disrupts normal operations and increases both maintenance costs and the rates to be paid for the purification of the water (Payri et al., 2004). A simple alternative, is to place the used fried oils in a plastic bottle (for example, a big soda bottle), to close and place them in the garbage. The garbage is separated, and the bottles will be opened and leaked in an appropriated place instead of being poured in the sewers, in this way, unnecessary expenses with treatment in the sewer stations are prevented. Only a small amount of the used cooking oil is properly collected and recycled, specially in rural areas (Groschen, 2002). A few years ago, this waste was mainly used to make animal food. However, as there is some evidence that highly oxidized fats (during frying, oils are exposed to high temperatures in the presence of atmospheric oxygen) may have carcinogenic properties (Azpilicueta and Remirez, 1991; Chang and Peterson, 1978), animal food from used cooking oil is being prohibited by governments. In this situation, biodiesel manufacturing may be an alternative option for reusing waste cooking oil. Biodiesels from both used and unused vegetable oils are supposed to have very similar properties and potential in reducing pollutant emission from the engine because both are

composed of methyl esters of fatty acids. Further, analyses of used cooking oil showed that the differences between used and unused oils are not very great and in most cases a simple pretreatment (removal by filtration of solid particles, esterification process to reduce the content of free fatty acids) is enough for subsequent transesterification (Chang and Peterson, 1978). 4. ENVIRONMENTAL RESPONSIBILITY AS AN ENTERPRISE STRATEGY There is an increasing worldwide concern for environmental protection and for conservation of non-renewable natural resources. Day by day fossil fuel resources deplete due to rapidly increasing population and industrialization all around the world. For this reason, the possibility of developing alternative energy sources to replace traditional fossil fuels has been receiving a large interest in the last few decades. After the two great wars, the environmental variable enters in scene and many companies start to incorporate environmental concerns as business-oriented strategies. Donaire (1995) shows that one of the important components of this overturn in the ways of thinking and acting was the growth of the ecological conscience in the society, in the government and the proper companies, who had started to incorporate this orientation in its strategies. Ferraz et al. (1995), demonstrate that, due the productive and technological qualification in Brazil, the environmental issue offers the chance to be one of the renewable bases of the Brazilian companies' competitiveness. However, the adoption of a pro-active position with regard to the environment becomes necessary by the entrepreneurs, and this can construct, in medium and long terms, competitive advantages of difficult overcoming for the competitors. The industry is the greatest responsible for the dispersion of toxic substancies in the environment and therefore it, becomes urgent and necessary to promote changes in the form to treat the environmental problems. To attenuate and control the pollutants became insufficient, being necessary to direct the efforts to reduce and mainly to prevent the harmful substance discarding in the environment. (Giannetti & Almeida, 2006, p. 19). 5. BRAZILIAN LAW CONCERNING THE USED FRIED OIL In August of 2005 was published in Official Daily of the Brazilian Federal Senate, the project of law n 296, authorship of Senator Valmir Amaral, "concern the obligatoriness to consist in the label of the edible oil packings, a warning about the correct destination of the product after it use" (BRAZIL, 2005). This project decrees that the label of the edible oil packings will have to contain an explainable note, in legible and visible forms, about the convenience to place the product after it use, in closed plastic bottles, as well as to place them in the garbage, as a way to prevent the contamination of the hydro resources. In case that the project being accepted, the labeling made in disagreement with the stipulated one in the previous paragraph, will constitute punishable infraction with administrative sanctions, amongst foreseen in the Law n 8,078, of 11 of September of 1990 - Consumer Code of Defense. In accordance with the Daily one of the Federal Senate, the edible oil manufacturers and importers are considered infractors. Currently, the project is in transaction in the Federal Senate. This project of law is considered as an alert to the companies preparing themselves for the future, where there is a great probability of the companies to assume the responsibilities for its products during all the phases of its cycle of life, also the discarding. The principle is to integrate the environment function to the strategical planning of the company" (Maimon, 1994, P. 122). 6. METHODOLOGY In this paper, the necessity appears by the adoption of methodological criteria to reach the pre-established objectives, through the inquiry techniques, appealing itself, simultaneously, the documentary and not documentary information. The research method is the set of systematic and rational activities that, with bigger security, allows reaching the considered objectives, indicating the way to be followed (LAKATOS and MARCONI, 1995). The nature of the research is applied, Silva (2005) and objective to generate knowledge for practical application and directed to the

solution of specific problems. It involves local truths and interests. In the point of view of its objectives (Gil apud Silva, 2005) the research is exploratory: it aims to provide great familiarity with the problem to become explicit or to construct hypotheses. It involves bibliographical survey and market analysis, stimulates the understanding of the problem. 6.1 Procedures and techniques The first step was the accomplishment of the survey and research about the subject in question, thus this work is characterizes as being a bibliographical research, that in accordance with Lakatos and Marconi, (1995, P. 43), "it s not a repetition of what already was said or written on a certain subject, but propitiates the examination of a subject under a new approach or boarding, creating innovative conclusions". Fachin (2001, p. 126) affirms that "the material consisting of primary or secondary data is understood for bibliographical survey that can be used by the researcher". After the first step, the existing products in the market had been analyzed to verify if it had some company which informs the consumer of the correct destination of the edible oil after it use. The universe of the research consists of eleven distinct edible oil manufacturers (soy, canola, sunflower and maize). The technician procedures had been: bibliographical research and actionresearch that, in accordance with Gil (1991), is that one conceived through a narrow association with an action and the researchers of the situation or the problem are involved in a cooperative or participative way. 7. RESULTS Forty six (46) packings of edible oil of 11 (eleven) different manufacturers had been analyzed and none of them contained any information or warning about the correct disposal of the product (oil). It is evidenced, that amongst the diverse producing and importing companies of edible oils in Brazil, none of them presents this important information, either due to a current law that not obligate this act, lack of knowledge by the companies or still, a lack of an environmental strategical vision. To insert the environmental interests in the capitalist productive process, that is, to internalize in the economic sphere the environmental question, means an attempt of raising the interests of the capital, making the environmental issue, part of the decisive process and the economic activities, in order to present a clear alignment of the strategies of development supported by the capitalist strategy of the profits preservation (Young, 2001). 7.1 Considered model The main objective of the stamp (figure 2) is to inform the consumer that the used oil when poured directly in sinks and toilets cause the bad functioning and the blockage of canalizations and nets of sewer and raise the prices of the treatment of residues, and if launched in the rivers, lakes and ground, provokes innumerable environmental impacts. Following the steps shown in the stamp, it will be preventing future problems in the residences and contributing with the whole environment. This model is basically destined to prevent expenses and environmental impacts of the incorrect destination of used oils, however the hypothesis of this model can contribute with the optimization of a permanent system collection by the cities that desire to generate jobs and profit, from this residue that have being wasted, as the manufacture of cleanness products and mainly the generation of biofuels.

Figure 2 - Model of used oil stamp. 8. CONCLUSIONS In the past decade, energy consumption related to environmental pollution and supply diversification has been the focus of environmental protection and economic development for pursuing sustainable development and creating renewable energy in the world. Because of the limited petroleum reserves and increased environmental concerns, alternate fuels from agricultural resources have become increasingly important in the near future. From the viewpoints of resource recycling and energy utilization, biodiesel fuel from used fried oil for diesel engines can be considered as one of green energies. However, the fact that biodiesel is still expensive that fossil fuel has been a major barrier that prevents its widespread use. To greatly promote the use of biodiesel fuel as an alternative to petroleum-based fuels in Brazil, the following measures are recommended and enhanced: -Grant food enterprises to build an used fried oil-to-biodiesel demonstration plant in Brazil for the purpose of reducing transportation and production costs. -Demonstrate commercial feasibility on utilizing used fried oil as biodiesel. -Regulate the return of waste edible oil to be regenerated due to the dietary health, and illegal dumping into sewer system and trash because it has been listed as one of recyclable items. The production of biodiesel from used frying oils is feasible by basic catalyzed transesterification and the biodiesel produced has the quality required to be a diesel substitute. A total lack of information is perceived too, by the companies, concerning the correct destination of the used edible oil, aiming at: (i) to reduce the environmental impacts; (II) to improve the environmental quality of the products; (III) to establish a more qualified relation with the community where the company is inserted and with the agencies of environmental control; and, (IV) to explore the ecological marketing in result of the adoption of these attitudes. In accordance with the opinion of Maimon (1994), most of the companies are characterized for a reactive position, adopting only the measures demanded by the environmental legislation. At the moment no law exist in the country that demands that the edible oil manufacturer inform the correct destination of the product, however is necessary to incorporate this environmental vision, perceiving that this attitudes, with a minimum cost or without any cost, contribute to the whole environment and propitiates a positive return to the proper company. The model has the purpose to be adopted by the edible oil manufacturers, or to be demanded to the same ones through specific laws edited by the competent agencies. It is important, in one way or another, that be used to mitigate a several ways of pollution, caused by the activities of the modern society.

REFERENCES Association of Peak Oil and Gas (ASPO); http://www.peakoil.net/uhdsg/ Default.htm). updated 2004 (Internet source:

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