Alternative fuel properties of tall oil fatty acidmethyl esterdiesel fuel blends

Abstract In this experimental work, tall oil methyl esterdiesel fuel blends as alternative fuels for diesel engines were studied. Tall oil methylester was produced by reacting tall oil fatty acids with methyl alcohol under optimum conditions. The blends of tall oil methyl esterdieselfuel were tested in a direct injection diesel engine at full load condition. The e V ects of the new fuel blends on the engine performance andexhaust emission were tested. It was observed that the engine torque and power output with tall oil methyl esterdiesel fuel blendsincreased up to 6.1% and 5.9%, respectively. It was also seen that CO emissions decreased to 38.9% and NO x emissions increased up to30% with the new fuel blends. The smoke opacity did not vary signi W cantly

1. Introduction Investigations of alternative renewable energy resourcescontinue, with many studies focused on biodiesel fuels. Oneof the alternative renewable energy sources for dieselengines is vegetable oil. Use of vegetable oil as an alterna-tive fuel for diesel engines is not a new concept; as early as1900, a diesel-cycle engine was demonstrated running withgroundnut oil at the Paris Exposition (Alt n, 1998).In the last decade, several vegetable oils, such as sunX ower oil, corn oil, olive oil, soybean oil, cotton seed oil andpeanut oil, have usually been used for producing biodieselfuel. Investigations have shown that pure vegetable oils arenot a suitable direct replacement for diesel fuel, due tohigher viscosity and higher molecular weight (Doradoetal., 2003; Dunn, 2002 ). These properties cause pooratomisation, low volatility, incomplete combustion andengine deposits (Klass, 1998; Rakopoulos, 1992). There-fore, several methods are used to reduce the viscosity of vegetable oil, including dilution, pyrolysis, micro-emulsionand transesteri W cation (Ma and Hanna, 1999; Solantaustae t a l . , 1 9 9 3 ). Nowadays, transesteri W cation is the currentmethod which is used e Y ciently. The transesteri W cationprocess involves the reaction of alcohol with the oil torelease three ester chains from the glycerine backbone of each triglyceride. The reaction requires heat and a strongbase catalyst to achieve complete conversion of the vegeta-ble oil into the separated esters and glycerine (Ayd n andKeskin, 2000; Knothe etal., 2002 ). The esters are called bio-diesel and can be used in neat form, or mixed with petro-leum diesel fuel in any unmodi W ed diesel engines (Canakciand Van Gerpen, 2003). The transformation of sun X oweroil by transesteri W cation to produce biodiesel has beenstudied and the results showed that the biodiesel was anexcellent substitute for fossil fuels under optimum condi-tions in length) and contains aromatic hydrocarbons (benzene,toluene, xylenes, etc.), sulphur and crude oil residue con-taminants (Klass, 1998). However, the chemical composi-tion of biodiesel is di V erent from that of petroleum baseddiesel fuel. Biodiesel hydrocarbon chains are generally 16 20 carbons in length and contain oxygen at one end. Biodie-sel contains about 10% oxygen by weight. Biodiesel doesnot contain any sulphur, aromatic hydrocarbons, metals orcrude oil residues (Arkoudeas etal., 2003; Kalligeros etal., 2003). These properties improve combustion e Y

ciency andemission pro W le. Biodiesel fuel blends reduce particulatematerial (PM), hydrocarbon (HC), carbon monoxide (CO)and sulfuroxide (SO x ) emissions (Tyson, 2004). However,NO x emissions are slightly increased depending on biodie-sel concentration in the fuel (Van Gerpen, 2005; etinkayae t a l . , 2 0 0 5 ).Consumption of diesel fuel is 15,000,000ton/year in Tur-key. Biodiesel fuel norms are published to apply in 2005.Therefore, statistical data on production rates are not yetknown in Turkey, where many biodiesel production plantsare already in operation. World biodiesel production wasover 3,000,000ton/year in 2004 and has increased day afterday. Many countries importing crude petrol encourage theproduction of biodiesel by reducing taxes and by giving lowinterest credits. The 2003/30/EC directive forces fuel pro-ducers to use 2% biodiesel in diesel fuel mixtures and thisratio is planned to increase up to 5.75% by the end of 2010.In this work, free fatty acids were obtained from crudetall oil by fractional distillation for production of tall oilmethyl ester as a novel process. Crude tall oil is a by-prod-uct in the manufacture of paper pulp by pulping processes.Crude tall oil contains 4050% resinic acids, 3040% fattyacids and 10% neutral or unsaponi W able material (Nogue-ira, 1996). Elemental analysis shows that tall oil contains11.0% oxygen, 79.1% carbon and 9.9% hydrogen (Sharmaand Bakhshi, 1991). The chemical composition varies withthe age, pine species, geographical location of the conifer-ous trees and pulping process (Drew and Propst, 1981).Crude tall oil in Turkey is obtained at 25,000ton/yearand is cheaper than other vegetable oils. Tall oil is widely

used in industrial applications, e.g. nylon, adhesives, iron steel etc., and also as an additive to improve cetane numberin diesel fuel (Feng etal., 1993; Jacoby etal., 2003 ).In this experimental study, tall oil methyl ester was pro-duced by reacting tall oil fatty acids with methyl alcoholand properties of test fuels were determined. Blends of talloil methyl ester with diesel fuel were tested in a direct injec-tion diesel engine at full load condition. 2. Methods Crude tall oil was taken from the SEKA Ta o ucu (inTurkey) paper plant and distilled in a batch distillationapparatus. Temperatures were recorded at intervals of 5min starting from 15C. After distilling o V water at tem-peratures between 98C and 104C, free fa tty acids used for producing biodiesel were obtained between 235C and3 3 3 C . The esteri W cation reaction was carried out in a 2000mlreaction vessel equipped with re X ux condenser, stirrer andthermometer. Sulphuric acid was used as catalyst. 1000g of tall oil fatty acids, 200g of methyl alcohol and 50g of sulphuric acid were mixed. The mixture was heated to 65 80C and held at this temperature with stirring for 2h. Thetemperature and ratio of alcohol/oil were investigated asparameters to determine optimal conditions for biodieselsynthesis. After this, the mixture was washed with an aque-ous sodium bicarbonate solution to remove suspendedimpurities, unreacted methanol and catalyst. Sodium bicar-bonate solution is alkaline and therefore reduces the acidityof crude methyl ester. Crude methyl ester was distilled toobtain pure methyl ester. A X ow diagram of the tall oilmethyl ester production process is shown inF i g . 1 .For this experimental study, a single cylinder, directinjection diesel engine was used. The engine characteristicsare shown inTable 1. Blends of tall oil methyl ester and die-sel fuel were tested at full load condition. Engine speed waschanged

from 1800 to 3200rpm with an interval of 200rpm.Before each test, the engine was warmed up with diesel fuelfor about 15min until the engine temperature stabilised. A