Fuel 116 (2014) 1418

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Fuel
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Effect of metal contents on oxidation stability of biodiesel/diesel blends

Siddharth Jain a,, M.P. Sharma b
a b

NUS Environmental Research Institute, National University of Singapore, 5A Engineering Drive 1, #02-01, Singapore 117411, Singapore Biofuel Research Laboratory, Alternate Hydro Energy Centre, Indian Institute of Technology Roorkee, Roorkee, Uttarakhand 247667, India

h i g h l i g h t s
 Stability of metal contaminated biodiesel blend has been checked.  Effectiveness of different antioxidants has also been checked.  Biodiesel blends with diesel have shown the better oxidation stability.  Effect of metals on the oxidation stability of biodiesel has found catalytic.

a r t i c l e

i n f o

a b s t r a c t
Present paper deals with the evaluation of oxidation stability of metal contaminated biodiesel/diesel blend. Effectiveness of different antioxidants with respect to different biodiesel/diesel blends has also been checked. It is found that pyrogallol (PY) is the most effective antioxidant. As the % of diesel is increased in the blend, the oxidation stability of biodiesel/ diesel blend also increased. From the experiments it is found that B100 required large amount of antioxidant for maintaining the specication followed by B30, B20, B10 and B7 samples with metal contents. Therefore it is possible to attain requisite oxidation stability of metal contaminated biodiesel by blending 70% petro-diesel in Jatropha curcas biodiesel (JCB). This optimum combination is expected to reduce the cost of biodiesel substantially and require lower quantity of antioxidant. 2013 Elsevier Ltd. All rights reserved.

Article history: Received 5 September 2011 Received in revised form 24 July 2013 Accepted 25 July 2013 Available online 14 August 2013 Keywords: Biodiesel Jatropha Oxidation stability Antioxidants Metal contaminants

1. Introduction Biodiesel is a fuel consisting of the alkyl monoesters of vegetable oils or animal fats. Biodiesel fueled engines produces less carbon monoxide, unburnt hydro carbons and particulate matters than diesel fueled engines. One drawback of biodiesel is that it is susceptible to oxidation which can induce polymerization of the ester and can form insoluble gums and sediments which are known to cause fuel lter plugging. Biodiesel, derived from vegetable oil and animal fats, is being used as engine fuel in USA and Europe to reduce air pollution and to reduce dependence on limited fossil fuel, localized to some specic regions. Because of the surplus availability of edible oils like soybean oil, sunower oil and rapeseed oil, these countries are using edible oils as feedstocks for biodiesel production. On the other hand, the possibility of biodiesel production from edible oil resources in India is very less as the indigenous edible oil production is much less than the actual demand which is met by its import [1]. India accounts for 9.3% of worlds total oil seed production and is the
Corresponding author. Tel.: +65 81594224/+91 9456382050; fax: +91 1332 273517. E-mail address: arthjain2001@gmail.com (S. Jain).
0016-2361/$ - see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.fuel.2013.07.104

fourth largest edible oil producer in the world and still about 46% of total edible oil is imported to meet the domestic requirements and as such the question of diverting edible oil resources for biodiesel production in India does not arise. The only possibility seems to be the non-edible oil resources like Jatropha, pongamia, Mahua and sal, which can be commercially grown on waste lands and the oil resources can be used for biodiesel production. Jatropha curcas has been identied as one of the important source for biodiesel production in India. Almost all the biodiesels have signicant amounts of esters of oleic, linoleic or linolenic acids and the trend of increasing stability is linolenic < linoleic < oleic [2]. These esters undergo autooxidation with different rates depending upon the numbers and positions of the double bonds and result in the formation of a series of by-products like acids, esters, aldehydes, ketones, lactones, etc. A number of reports have been found in the literature on the storage and oxidative stability of biodiesel synthesized from edible oils but only very few reports are available on the effect of blending of biodiesel with diesel on the oxidation stability of that blend. However, to the knowledge of the author of this work, no work has been reported on the effect of metal contaminants on non edible biodiesel/diesel blend oxidation stability.

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Sarin et al. [3] have used palm and Jatropha biodiesel blends to minimize the dosage of antioxidants and found an increase in the induction period of Jatropha biodiesel after it was blended with palm biodiesel. Sarin et al. [4] investigated the Synergistic effect of metal deactivator and antioxidant on oxidation stability of metal contaminated Jatropha biodiesel. Research was conducted to increase the oxidation stability of metal contaminated Jatropha biodiesel by doping metal deactivator with antioxidant, with varying concentrations in order to meet the aforementioned standard required for oxidation stability. It was found that usage of antioxidant can be reduced by 30% to 50%, therefore the cost, even if very small amount of metal deactivator is doped in Jatropha biodiesel to meet EN-14112 specication. Sarin et al. [5] analyzed the effect of blending of biodiesels synthesized from non-edible and edible oils on oxidation stability. Dependence of the OS on esters of fatty acid composition was also examined. Good correlation between the OS and PAME (palmitic acid methyl ester) was obtained. Das et al. [6] have carried out long-term storage stability analysis of biodiesel produced from Karanja oil and reported that the oxidative stability of Karanja oil ME (KOME) decreased with increase in storage time of the biodiesel. Knothe and Dunn [7] indicated that presence of Cu, even in 70 ppm in rapeseed oil greatly increases the oxidizability of the fuel. Copper has also been found to reduce the Oxidation Stability Index (OSI) of methyl oleate more than either Fe or Ni. Karavalakis et al. [8] have evaluated the oxidation stability of biodiesel/diesel blend. They used animal fats and used frying oil for biodiesel. They examined the factors inuencing the stability of several biodiesel blends with low and ultra low sulphur automotive diesel fuels. Sarin et al. [9] have evaluated the oxidation stability of metal contaminated biodiesel and found that inuence of metal was detrimental to oxidation stability and catalytic. From the above literature, it can be concluded that oxidation cannot be entirely prevented but can be signicantly slowed down by the use of antioxidants which are chemicals that inhibit the oxidation process. Two types of antioxidants are generally known: chain breakers and hydroperoxide decomposers [10]. Literature related to hydroperoxide decomposers is very scarce. The two most common types of chain breaking antioxidants are phenolic and amine-types. Almost all the work related to stability of fatty oil and ester applications is limited to the phenolic type of antioxidant. The mechanism of all chain breaking antioxidants is shown below in Fig. 1. As can be seen, the antioxidant contains a highly labile hydrogen that is more easily abstracted by a peroxy radical than fatty oil or ester hydrogen. The resulting antioxidant free radical is either stable or further reacts to form a stable molecule which is further resistant to chain oxidation process. Thus the chain breaking antioxidants interrupt the oxidation chain reaction in order to enhance stability. The effectiveness of antioxidant is generally measured by stressing a fatty oil or ester molecule both with and without the antioxidant. As per National Mission on Biodiesel in India, Jatropha biodiesel has undertaken for the present study in order to improve the stability of biodiesel and make it acceptable to oil marketing companies in India. The present paper aims to study the effect of metal

contaminants on the stability of Jatropha biodiesel/diesel blend. Also the effectiveness of various antioxidants is checked in metal contaminated biodiesel and its blend with diesel. 2. Materials Butylated hydroxytoluene (BHT), tert-butyl hydroquinone (TBHQ), butylated hydroxyanisole (BHA), propyl gallate (PG), and pyrogallol (PY) were the additives employed for their evaluation on diesel/biodiesel blends. All chemicals were of analytical grade and purchased from Sigma Aldrich, India. Different transition metalsiron (Fe), nickel (Ni), manganese (Mn), cobalt (Co), and copper (Cu) have also been purchased from Sigma Aldrich, India. Biodiesel is prepared in the laboratory and the procedure is discussed in the experimental section. 3. Experimental 3.1. Biodiesel preparation Since the FFA contents of Jatropha curcas oil (JCO) were very high (15.4%), a two step acidbase catalyzed transesterication process is used to prepare biodiesel and the method is discussed in our previous publications [11,12]. After completion of the reaction, the reaction mixture was transferred to separating funnel and both the phases were separated. Upper phase was biodiesel and lower phase contained glycerin. Alcohol from both the phases was distilled off under vacuum. The glycerin phase was neutralized with acid and stored as crude glycerin. Upper phase i.e. methyl ester (biodiesel) was washed with the water twice to remove the traces of glycerin, unreacted catalyst and soap formed during the transesterication. Fatty acid composition of biodiesel was analyzed using Gas chromatograph [13] and is given in Table 1 which shows that the JCB is maximum composed of unsaturated fatty acids (75.3%) responsible for poor oxidation and thermal stability of biodiesel. The biodiesel samples prepared above were tested for physicochemical properties as per ASTM D-6751 and Indian IS-15607 specication given in Table 2 which shows that the biodiesel prepared from JCO meet most of the specications except oxidation stability test. As per National Mission on Biodiesel in India, the use of biodiesel should reach a minimum of 20% in 2012, while the revised European standard EN 590 already includes a provision for automotive diesel fuel to be blended with biodiesel up to 7% (v/v). According to European standard there is no specication beyond B7 for oxidation stability. Therefore same oxidation stability specication requirement (20 h) is considered for oxidation stability for all biodiesel blends beyond B7. As Indian standard follow the European standards for stability of biodiesel therefore basis of study is very correct. 3.2. Biodiesel/diesel blends preparation For the purpose of experimentation, biodiesel is mixed with diesel in different proportions (B80, B50, B40, B30, B20, B10 and B7). Also to see the effect of metal contents on biodiesel, different metal contents (Fe, Ni, Mn, Co and Cu) are added in biodiesel in predecided concentrations with and without antioxidants. 3.3. Oxidation stability measurement Oxidation stability of biodiesel from different feedstocks and their blends with automotive diesel was quantied by the induction period (IP). The IP was evaluated according to the Rancimat

Fig. 1. Mechanism of all chain breaking antioxidants [2].

16 Table 1 ASTM and IS specication of biodiesel. S. No. 1 2 3 4 5 6 7 8 9 10 11 Property (unit) Flash point (C) Viscosity at 40 C (cSt) Water and sediment (vol%) Free glycerin (% mass) Total glycerin (% mass) Oxidation stability of FAME (hr) Oxidation stability of FAME blend (hr) Free glycerol Total glycerol Acid value Ester content

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ASTM D6751 D-93 D-445 D-2709 D-6584 D-6584 EN14112 D6584 D6584 D664

ASTM D6751 limits Min. 130 1.96.0 Max. 0.05 Max. 0.02 Max. 0.24 3 0.02 (max) 0.25 (max) 0.5 (max)

IS 15607 IS 1448 IS 1448 D-2709 D-6584 D-6584 EN 14112 EN 590 D6584 D6584 D664 EN14103

IS 15607 limits

Jatropha ME 172 4.38 0.05 0.01 0.03 3.27 0.01 0.12 0.38 98.5

Max. 0.05 Max. 0.02 Max. 0.24 Min. 6 Min. 20 0.02 (max) 0.25 (max) 0.5 (max) 96.5 (max)

Table 2 Fatty acid composition of Jatropha curcas oil. Fatty acid Palmitic acid (P) Stearic acid (S) Oleic acid (O) Linoleic acid (L) Linolenic acid (LL) Molecular formula C16H32O2 C18H38O2 C18H34O2 C18H32O2 C18H30O2 Structure CH3(CH2)14COOH CH3(CH2)16COOH CH3(CH2)7ACH@CHA(CH2)7COOH CH3(CH2)4CH@CHACH2ACH@CHA(CH2)7COOH CH3(CH2)4CH@CHACH2ACH@CHACH2ACH@CHA(CH2)4COOH % Composition 16.8 7.7 39.1 36.0 0.2

method EN 14112 for pure biodiesel and the modied Rancimat method EN 15751 for the biodiesel blends with petro-diesel. In the modied Rancimat method, a number of parameters were changed, mainly because of the higher volatility of hydrocarbon fuels compared to methyl esters, which may lead to higher sample evaporation. All stability measurements were carried out on a Metrohm 873 Biodiesel Rancimat instrument. Samples of 3 g of pure biodiesel and 7.5 g of biodiesel blends were analyzed under a constant air ow of 10 L/h, passing through the fuel and into a vessel containing distilled water. The samples were held at 110 C heating block temperature. The end of the induction period is indicated when the conductivity starts to increase rapidly. This accelerated increase is caused by the dissociation of volatile carboxylic acids produced during the oxidation process and absorbed in the water. When the conductivity of this measuring solution is recorded continuously, an oxidation curve is obtained whose point of inection is known as the IP. This provides the good characteristic value for the oxidation stability.

Fig. 2. Effect of metal contaminants on oxidation stability of biodiesel.

4. Results and discussion 4.1. Effect of metal contaminants on the oxidation stability of biodiesel/diesel blends To check the effect of metal contaminants on the oxidation stability of biodiesel, it is added with different metal contents with pre-decided concentration and the effect of these on oxidation stability is shown in Fig. 2 it is clear from gure that as the concentration of metal increases, oxidation stability decreases but after 2 ppm concentration oxidation stability become constant. This is due to the catalytic effect of metals on oxidation stability [4,9]. Fe is found to have least catalytic effect on oxidation stability followed by Ni, Mn, Co and Cu. As the oxidation stability of biodiesel become constant beyond 2 ppm metal concentration therefore biodiesel/diesel samples were mixed with different metals contents with 2 ppm concentration. Then the oxidation stability is checked using Rancimat test as discussed in experimental section and the results are shown in Fig. 3. It is clear from Fig. 3 that as the amount of diesel increases in the blend, the oxidation stability also increases. Fe is found to

Fig. 3. Effect of metal contaminants on the oxidation stability of biodiesel/diesel blends.

have least catalytic effect on oxidation stability followed by Ni, Mn, Co and Cu. This statement is in agreement with the pure biodiesel case as shown in Fig. 2.

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Fig. 4. Effectiveness of antioxidants on biodiesel/diesel blends.

4.2. Effect of antioxidants on metal contaminated biodiesel/diesel blends To check the effectiveness of antioxidants on biodiesel and biodiesel/diesel blend, these are doped with different antioxidants with 200 ppm concentration and the results are shown in Fig. 4. PY is found as most effective antioxidants followed by PG, TBHQ, BHT and BHA. Based on the results of Fig. 4, the different biodiesel/diesel blends with and without metal contents are doped with PY antioxidants with different concentrations up to 600 ppm and the results and shown in Figs. 5 and 6. Fig. 5 shows the effect of PY on the oxidation stability of biodiesel (B100) and biodiesel/diesel blends (B80, B50 and B40) with and without metal contaminants. Fig. 5 shows that for B100 sample without metal contents, 80 ppm PY is required to maintain the specication (EN14214) however for metal contaminated B100 sample amount of PY is increased to 300, 400, 400, 500 and

600 ppm for Fe, Ni, MN, Co and Cu metals respectively. For B80 sample without metal contents 400 ppm PY is required to maintain the specication (EN590) however as the sample is doped with metals the amount of PY is increased beyond 600 ppm to maintain the same specication. All the B80 metal contaminated samples are failed to maintain the specication with PY antioxidant up to 600 ppm. For B50 and B40 samples without metal contents the PY required is 300 ppm and 200 ppm respectively. Only Fe contaminated blend is maintaining the specication (EN590) with 600 ppm PY however all other metal contaminated B50 and B40 blends are fail to maintain the specication with PY up to 600 ppm. Fig. 6 shows the effect of PY on the oxidation stability of biodiesel/diesel blends (B30, B20, B10 and B7) with and without metal contaminants. For B30 sample without metal contents, 50 ppm PY is required to maintain the specication. However for metal contaminated B30 sample, PY required is 290, 300, 310, 400 and 410 ppm for Fe, Ni, Mn, Co and Cu respectively. For B20 sample without metal content, no antioxidant is required to maintain the specication. However for metal contaminated B20 sample, PY required is 100, 180, 200, 280 and 300 ppm for Fe, Ni, Mn, Co and Cu respectively. Oxidation stability of B10 and B7 samples without metal contents and antioxidants is very high. Also for metal contaminated B10 and B7 blends, amount of antioxidant is very less as compared to blends with high amount of biodiesel. For B10 sample amount of PY required is 50, 90, 100, 200 and 210 for Fe, Ni, Mn, Co and Cu respectively. For B7 sample amount of PY required is 50, 60 and 80 for Mn, Co and Cu respectively however no antioxidant is required for Fe and Ni contaminated B7 sample. Fig. 7 showing the concentration of antioxidant (PY) required for maintaining the specication of 6 h (EN14214) for B100 and 20 h (EN 590) for biodiesel/diesel blends. It is clear from the Fig. 7 that B100 required large amount of antioxidant for maintaining the specication followed by B30, B20, B10 and B7. Thus, it is

Fig. 5. Effect of PY on metal contaminated biodiesel/diesel samples (B100, B80, B50 and B40) oxidation stability.

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Fig. 6. Effect of PY on metal contaminated biodiesel/diesel samples (B30, B20, B10 and B7) oxidation stability.

compared to pure biodiesel to maintain the specication of oxidation stability. B100 required large amount of antioxidant for maintaining the specication followed by B30, B20, B10 and B7. Thus, it is recommended to attain requisite oxidation stability of biodiesel by blending 70% petro-diesel in JCB. This optimum combination is expected to reduce the cost of biodiesel substantially and require lower quantity of antioxidant. References
[1] Jain S, Sharma MP. Prospects of biodiesel from Jatropha in India: a review. Renew Sust Energ Rev 2010;14(2):76371. [2] Jain S, Sharma MP. Stability of biodiesel and its blends: a review. Renew Sust Energ Rev; 14 (2), 2010, p. 66778. [3] Sarin R, Sharma M, Sinharay S, Malhotra RK. Jatrophapalm biodiesel blends: an optimum mix for Asia. Fuel 2007;86(1011):136571. [4] Sarin A, Arora R, Singh NP, Sarin R, Malhotra RK, Sharma M, et al. Synergistic effect of metal deactivator and antioxidant on oxidation stability of metal contaminated Jatropha biodiesel. Energy 2010;35:23337. [5] Sarin A, Arora R, Singh NP, Sarin R, Malhotra RK. Blends of biodiesels synthesized from non-edible and edible oils: inuence on the OS (oxidation stability). Energy 2010;35:344953. [6] Das LM, Bora Dilip Kumar, Pradhan Subhalaxmi, Naik Malaya K, Naik SN. Longterm storage stability of biodiesel produced from Karanja oil. Fuel 2009;88(11):23158. [7] Knothe G, Dunn RO. Dependence of oil stability index of fatty compounds on their structure and concentration and presence of metals. J Am Oil Chem Soc 2003;80:10216. [8] Karavalakis G, Stournas S, Karonis D. Evaluation of oxidation stability of diesel/ biodiesel blends. Fuel 2010;89:24839. [9] Sarin A, Arora R, Singh NP, Sharma M, Malhotra RK. Inuence of metal contaminants on oxidation stability of Jatropha biodiesel. Energy 2009;34:12715. [10] Pospisil J, Klemchuk PP. ed. Oxidation inhibition in organic materials. CRC Press. 1990. p. 1. [11] Jain S, Sharma MP. Kinetics of acid base catalyzed transesterication of Jatropha curcas oil. Bioresour Technol 2010;101(20):77016. [12] Jain S, Sharma MP. Biodiesel production from Jatropha curcas oil. Renew Sust Energ Rev 2010;14(9):31407. [13] Determination of ester and linolenic acid methyl ester contents, English version of DIN EN 14103 (2003).

Fig. 7. PY concentration required to maintain the specication of oxidation stability for different samples with and without metal contents.

possible to attain requisite oxidation stability of biodiesel by blending 70% petro-diesel in Jatropha biodiesel. This optimum combination is expected to reduce the cost of biodiesel substantially and require lower quantity of antioxidant.

5. Conclusion When JCB is blended with petro-diesel, it leads to a composition having improved oxidation stability. In the present paper effect of metal contaminants on the oxidation stability of biodiesel/diesel blend is checked with and without antioxidants. From the experiments it is found that PY is the most effective antioxidant to increase the oxidation stability of different biodiesel/diesel blends. The amount of PY required in biodiesel/diesel blend is lower as