The 2nd AUN/SEED-Net Regional Conference on New&Renewable Energy Faculty of Enigneering, Burapha University, Thailand January 21-22, 2010

Effectiveness of Combined Additives on Long-term Storage Stability and Fuel Properties of Palm-Biodiesel
M. Husnawan1, 2*, M.H. Jayed1, H.H. Masjuki1, M.A. Kalam1, T.M.I. Mahlia1, M. Ropandi3, M.Y. Cheah1
Department of Mechanical Engineering, University of Malaya 50603 Kuala Lumpur Malaysia 2 Department of Mechanical Engineering, Syiah Kuala University Jl. S. Abd. Rauf, No.7 Darussalam Banda Aceh, Indonesia 3 Malaysian Palm Oil Board, Energy and Environment Unit, 43000 Kajang, Selangor, Malaysia
*
1

Corresponding Author: jayedhussan@gmail.com

Abstract
The use of biodiesel is expanding rapidly around the world, making it imperative to fully understand the impacts of biodiesel on diesel engine as they have slightly different properties compared with conventional diesel. This has leads to the establishment of biodiesel standards in many countries that focused on several key fuel properties where producers must conformed with. As with other natural substances, if left untreated, biodiesel is susceptible to oxidative degradation that may be caused by long period of storage. The degradation of biodiesel leads to the formation of lower molecular weight acids, peroxides and gums that, in turn, could cause unwanted changes in both the properties and performance of the biodiesel. These deposits and gums can cause damage to the engine and also to the fuel injection systems. This paper aimed to investigate the changes on several key properties of palm-biodiesel after a storage period of 1, 2 and 6 months. The fuel samples were divided into two groups - samples with combined additives and samples without any additives. The fuel was stored in transparent High Density Poly Ethylene (HDPE) box without sunlight exposure at room temperature. Fuel properties were measured after the stipulated storage period and the results from the two groups were compared against the established standards. The results had shown that fuel samples with added additives were better protected against rapid deterioration due to oxidation than those that were without, particularly during extended storage duration.

Keywords: Biodiesel, Palm Oil, Oxidation Stability, Storage Time

1. Introduction In search of a greener alternative fuel to petro diesel, biodiesel have been a primary and obvious choice. Biodiesel is derived from different type of vegetable oils and it had been tested by the inventor of diesel in engine, Dr. Rudolph Diesel in 1900 at the Paris Exposition [1]. As an alternative to petro diesel in transportation, biodiesel can easily be a crucial solution for the current environmental problems as it does not require any engine modifications and it reduces greenhouse gas (GHG) emission

substantially. The use of biodiesel also improves the lubricity of the fuel. All of the above factors have make biodiesel usage more adaptable and attractive to the current energy scenario which is to ensure energy security, environmental sustainability, and to boost rural development by shifting of power dependency from petro to agro-industry, simultaneously [2]. In the last two decades, biodiesel with different blending percentage has been in use in many countries. However, due to the reason of biodiesel being derived from edible oil, it has

The 2nd AUN/SEED-Net Regional Conference on New&Renewable Energy Faculty of Engineering, Burapha University, Thailand January 21-22, 2010

come into conflict with the food security issues [3]. On the other hand, mass production and the use of biodiesel require good storage stability; where biodiesel is severely lacking from petro-diesel. Good storage stability of biodiesel is a must for customer acceptance, standardization and quality assurance of biodiesel in the market. Transesterification or alcoholysis is the usual conversion process used to convert triglycerides of vegetable oil into fatty acid methyl esters (FAME) by displacing alcohol from an ester by another alcohol [4]. For each triglyceride three monohydric alcohols reacts to produce (m) ethyl ester and glycerin. Biodiesel which is a transesterified methyl ester is chemically prone to oxidation in the presence of air or oxygen. The oxidation of ester to alcohol will produce acid that will leads to the reduction in ash point and the increase of total acid number [5]. Insoluble gums, acids, and aldehydes that formed from oxidative degradation may in turn cause engine problems such as lter clogging, injector coking and corrosion of metal parts. Generally, long storage period will leads to the increase of oxidized biodiesel due to its unstable nature and the usage of such fuel will subsequently cause damage to engine parts, mainly the fuel supply system. This is why oxidation stability is an important criterion for biodiesel [6]. Usually, the rates of oxidation is very much depended on factors such as the presence of air, elevated temperatures, the presence of metals that facilitate oxidation and also the chemical structure of the biodiesel where unsaturated methyl esters with more double bond is more incline to oxidation. Different oxidation mechanisms like auto-oxidation, photooxidation and primary oxidation are described in many literatures [7-10]. To date one of the most common approaches to increase oxidation stability is the use of antioxidants. Antioxidants delay the onset of

oxidation by extending the induction period. However, antioxidants can only help in delaying the onset of auto-oxidation but not photooxidation. In order to measure the effectiveness of an antioxidant on auto-oxidation, palm oil methyl ester (POME) samples were kept in dark to avoid photo-oxidation and were tightly sealed to minimize air exposure and. Key fuel properties such as peroxide value, water content, acid value, calorific value, oxidation value, pour point and viscosity were measured for both groups after the specified storage durations of 1, 2 and 6 months. The main objective of this investigation was to evaluate the effectiveness of antioxidant additive on several key fuel characteristics in POME blend.

2. Experimental test and procedure

2.1 Raw Material and Sample Preparation The no. 2 diesel fuel used for blending with POME was normal commercial fuel obtained from PETRONAS while the biodiesel was collected from the Malaysian Palm Oil Board (MPOB). The blended fuel samples were kept at room temperature and stored in transparent High-density polyethylene (HDPE) containers. The containers were made from hard material that would not corrode during the storage period. All the containers were kept in a dark room to avoid photo-oxidation. Additive blended in a combination of: Tertiary Butyl Hydroquinone (TBHQ) and Ethylene Vinyl Acetate (EVA) which are mixed stoichiometrically with POME by percent of weight (%wt). 2.2 Sample Analysis Fuel samples compositions was given below: POME 1(100% pure POME), POME 2 (POME1 blended with 3% additives), POME 3 (POME1 blended with 10% additives), POME 4 (80% no. 2 blended with 20% POME, widely known as B20). All the blending and samples preparation were prepared in the dark room at room temperature to prevent any exposure to sunlight. Samples were taken for analysis of the key properties before and after the specific storage durations.

The 2nd AUN/SEED-Net Regional Conference on New&Renewable Energy Faculty of Engineering, Burapha University, Thailand January 21-22, 2010

Viscosity of 4 different blends was measured at 40C and 100C in a Houlion Viscometer. Data was taken 3 times and averaged thereafter. Pour Point of petroleum blends is the index of the lowest temperature at which the fuel has utility in certain applications. MPP 5Gs machine (manufactured by ISL) was used to measure the pour points of the fuel blends following ASTM D 97 method. Oxidation Value was measured by the Fourier transform infrared (FTIR) spectroscopy machine using the Rancimat method. The automatic adiabatic bomb calorimeter was used to measure the calorific value following the ASTM D240 method while acid value was measured in TAN analyzer following the SAE standard. FTIR spectroscopy was used to measure peroxide values and also the water content.

Increase of viscosity was also observed from biodiesel samples with added additives; however, the rate of increase was relatively slower than that of samples without additives. For biodiesel-diesel blend, the observed viscosity change was not significant. This might be due to the higher percentage of petroleum diesel which made the fuel more stable in the first 2 months; however, the viscosity of the blended samples began to increase after 6 months of storage. The result has also confirmed that the use of this additive can help to maintain the viscosity of palm-biodiesel for up to 6 months of storage period. 3.2 Pour Point The pour point of every sample before and after storage was shown in Fig.2. The result has showed that, with the presence of additive the pour point was successfully lowered. This was due to the contamination of Ethylene Vinyl Acetate (EVA) as an additive for reducing pour point. The result also showed that by increasing the percentage of additive, the pour point could be further lowered; however it was only applicable for sample that was stored for less than 6 months. For samples that were stored for 6 months or more, significant increase of pour point was recorded especially for samples with 10% additive.

3. Results and Discussions

3.1 Viscosity Oxidation of methyl ester began with the buildup of peroxides. Viscosity started to increase only after certain amount of peroxides was created. During storage, the viscosity of the methyl esters increased by the formation of more polar, oxygen containing molecules and also by the formation of oxidized polymeric compounds that could lead to the formation of gums and sediments that clog filters. Fig.1 showed that the viscosity increased significantly after 1 month of storage especially for the 100% biodiesel samples.

Fig.1

Viscosity of Palm-Biodiesel before and after storage

Fig.2

Pour point of Palm-Biodiesel before and after storage 3

The 2nd AUN/SEED-Net Regional Conference on New&Renewable Energy Faculty of Engineering, Burapha University, Thailand January 21-22, 2010

3.3 Oxidation Value The result of oxidation value that was measured by FT-IR was shown in Fig.3. Basically, oxidation occurred when oxygen attacks the fluid. The process was accelerated by heat, metal catalyst, acids, water content and solid contaminants. The thermal oxidation value of the tested samples versus the storage duration was presented in Fig.3. Although, the rapid test of oxidation value for biodiesel was measured using the Rancimat method, but the literature related to the use of this method was limited to the use of fresh sample and it may not be appropriate for the aged samples.

of chemical structure as well as the production optimization to fulfill the biodiesel standard and most of the research was based on fresh oil. The effect of storage duration on palm-biodiesel calorific value was presented in Fig.4.

Fig.4

Net calorific value of Palm-Biodiesel before and after storage

Fig.3

Oxidation value of Palm-Biodiesel before and after storage

The result has also showed that the presence of additive in the sample can effectively lowered the oxidation value compared with the nonadditive sample. The oxidation value of biodiesel-diesel blended fuel recorded was also lower than the others. However, for the time being, the oxidation stability of biodiesel-diesel blended fuel was not a crucial issue since the focus of biodiesel standards was on pure biodiesel. Therefore, several strategies including the use of a number of different additives were utilized to help meet the standard. 3.4 Calorific Value Calorific value was one of the important properties use to determine the suitability of a fuel to be use as a combustible fuel. The research of storage effect on combustion properties was limited. Currently, most of the research has been focusing on the modification

The result has shown that with presence of 3% additive, the calorific value of palm-biodiesel was relatively stable compared with other samples. Fig. 4 also showed that only palmbiodiesel with 3% additive and biodiesel-diesel blend have a constant calorific values after 1 month of storage. The decrease of calorific value for POME 2 and POME 4 were found to be insignificant compared with the others. Moreover, by using 3% additive, the calorific value of palm-biodiesel was maintained at the limit of the biodiesel standard (35 MJ/kg) even after 6 month of storage. 3.5 Acid Value Normally, the acid number increase with the increase of peroxides because the esters were first oxidized to form peroxides, which then undergo a complex reaction that formed the more reactive aldehydes before being be further oxidize into acids. Acids could also formed when traces of water causes hydrolysis of the esters into alcohols and acids. The acid value of biodiesel samples would also increase with the increase of storage duration as a result from the hydrolysis of fatty acids methyl esters (FAME) into fatty acids

The 2nd AUN/SEED-Net Regional Conference on New&Renewable Energy Faculty of Engineering, Burapha University, Thailand January 21-22, 2010

(FA). The effect of storage period on acid value of palm-biodiesel was shown in Fig. 5.

moisture in the sample. However, further analysis was needed to support this argument.

Fig.5 Acid value of Palm-Biodiesel before and after sotrage

Fig.6

Water content of Palm-Biodiesel before and after storage

The standard limit of 0.5 mg KOH/g was exceeded for samples without additive after 2 months of storage; whereas samples with lower percentage of additive was found to have successfully maintained the acid value for up to 6 months of storage. However, samples of palmbiodiesel mixed with 10% additive and biodiesel-diesel blended fuel have also showed an acid value that exceeded the limit after 6 months of storage. This was most probably due to the composition of fatty acids of the vegetable oils used as raw materials and also the storage condition. Yet, further study was needed to determine the extent of this effect, namely the materials of the storage container and also the environmental condition on biodiesel during long term storage. 3.6 Water Content The water content of every sample before and after storage was shown in Fig. 6. The result has indicated that palm-biodiesel with 3% of additive has successfully maintained the water content for up to 6 months of storage. Although, there was an increase of water content in the 3% additive added palm-biodiesel samples compared with other samples but the increase was not significant. This may be due to the fact that additive at this concentration could have prevented the change of temperature inside the storage container by altering the fluid thermal conductivity. The increase of additive was suspected to have the ability to promote

3.7 Peroxide Value At the time being, peroxide value was not mentioned in the biodiesel standards; however, this property influences the cetane number where the increase of peroxide will also increase the cetane number of the biodiesel. Higher cetane number will reduce the ignition delay time that may bring about some negative effect, particularly with the compatibility of the biodiesel with certain plastics and elastomers.

Fig.7 Peroxide value of Palm-Biodiesel before and after storage

The peroxide value for every sample before and after storage was shown in Fig. 7. The result has indicated that biodiesel without additive has recorded an increase of peroxide value after 6 months of storage compared with samples with additive. The results obtained have also

The 2nd AUN/SEED-Net Regional Conference on New&Renewable Energy Faculty of Engineering, Burapha University, Thailand January 21-22, 2010

indicated that samples with 3% additive have successfully suppressed peroxide formation after long term storage. Even though sample with 10% additive has shown otherwise. This may be due to the presence of water traces that may have caused oxidation of the sample. The formation of moisture occurred when the samples were blended with 10% additive, because of several unidentified reaction as well as changing of molecular structure. 4. Conclusion The effect of long term storage and the usage of additive on palm-biodiesel properties have been investigated in this experiment. 1. Generally, the addition of the selected combined additive has worked well in maintaining the biodiesel properties. 2. Biodiesel sample with the addition of 3% combined additive has performed better than its higher percentage (10%) counterpart. 3. Palm-biodiesel was found not suitable for long term storage (more than 1 month) unless they were to be blended with several type of additive such as antioxidant and pour point depressant. 5. Acknowledgement The authors would like to thank University of Malaya, UMRG Grant No. 036/09AET and Mr. Sulaiman Ariffin for his technical assistances. 6. References [1] Nitschke, W.R. and C.M. Wilson, Rudolph diesel, pioneer of the age of power. Norman, OK. The University of Oklahoma Press, 1965. Jayed, M.H., et al., Environmental aspects and challenges of oilseed produced biodiesel in Southeast Asia. Renewable and Sustainable Energy Reviews, 2009. 13(9): pp. 2452-2462. Srinivasan, S., The food v. fuel debate: A nuanced view of incentive structures.

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Renewable Energy, 2009. 34(4): pp. 950-954. Srivastava, A. and R. Prasad, Triglycerides-based diesel fuels. Renewable and Sustainable Energy Reviews, 2000. 4(2): pp. 111-133. Sarin, A., et al., Influence of metal contaminants on oxidation stability of Jatropha biodiesel. Energy, 2009. 34(9): pp. 1271-1275. Dunn, R. and G. Knothe, Oxidative stability of biodiesel in blends with jet fuel by analysis of oil stability index. Journal of the American Oil Chemists' Society, 2003. 80(10): pp. 1047-1048. Knothe, G., Some aspects of biodiesel oxidative stability. Fuel Processing Technology, 2007. 88(7): pp. 669-677. Frankel, E.N., Lipid Oxidation, second edition. The Oily Press, PJ Barnes & Associates, Bridgwater, England, 2005. Gunstone, F.D., J.L. Harwood, and A.J. Dijkstra, Chemical properties of lipids, in: The Lipid Handbook. CRC Press, 2007. Morita, M. and M. Tokita, The real radical generator other than mainproduct hydroperoxide in lipid autoxidation. Lipids, 2006. 41(1): pp. 91-95.

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