International Seminar on Chemical Engineering Soehadi Reksowardojo 2011

The Influence of Storing Time to Biodiesel Degradation Rate

Agus Raksodewanto, Bina Restituta Barus, Oni Fariza Balai Rekayasa Desain dan Sistem Teknologi BPPT Telp. (021) 7563213/7563217 Fax. (021) 7563273 Email : araksodewanto64@gmail.com

Abstract. The most complaint from biodiesel consumers lately is about oxidation stability of biodiesel itself. Due to their chemical composition, fatty acid methyl esters are more sensitive to oxidative degradation than fossil diesel. Biodiesel produce from vegetable oils and other feedstocks can be more prone to oxidation than a typical petroleum diesel unless it is modified or treated with additives. Exposure to air, heat, light, water and some metals are contributing factors that will cause it to degrade. Besides that, the fatty acid composition of feedstock, and such as impurities that catalyze the formation of radical compound in oil such as free fatty acid remains, acid catalyst remain from esterification process, metal element, peroxide and hydroperoxide compounds, short-chain of organic acid, etc. Consequently of the presence of those compounds is degradation of biodiesel quality, signed by the increasing of Total Acid Number and viscosity. The samples of biodiesel were made from palm oil and jatropha oil feedstocks with total acid number and viscosity fulfilled the standard of SNI 04-7182-2006. Both of testing biodiesel were stored in stainless steel and carbon steel tanks during six months. The results showed that jatropha biodiesel just survived for four months, while palm biodiesel can be survived for six months. Keywords: biodiesel, oxidation stability, quality degradation

Introduction

Biodiesel, a fuel derived from vegetable oil or animal fats [1,2], is well-positioned to replace some petrodiesel. Compatibility with the existing fuel infrastructure, renewability, domestic origin, biodegradability, inherent lubricity in the neat form, and competitiveness with petrodiesel in terms of many fuel properties are significant attributes of biodiesel. Technical issues remaining when using biodiesel include low-temperatures properties and reduction of NOx exhaust emissions although the interaction with new emissions control technologies still needs to be fully evaluated, along oxidative stability [3]. Transesterifying oil or fat with alcohol (methanol/ethanol), leads to produce methyl ester (biodiesel) as main product and glycerine as by-product. Biodiesel has the same fatty acid profile as the parent oil or fat. Due to the fact that many vegetable oils posses a significant amount of fatty acids with double bonds, oxidative stability is being concerned, espesially when storing biodiesel over an extended period of time. The storage problem is exacerbated by storage conditions which may include exposure to air, light, moisture, higher of ambient temperature, and storage materials. Oxidative stability is not recognized as a parameter in the Indonesia National Standard (SNI 04-7182-2006) that refers to the American Society for Testing and Materials (ASTM D 6751) provisional fuel standard guideline for biodiesel, PS 121 [4] because cummulative effects of autoxidation on engine performance and emissions are difficult to quantify. Autoxidation is known to affect kinematic viscosity (), acid value (AV), and peroxide value (PV) [5-8]. Two of these parameters, and AV, are among the specifications listed within

ISBN 978-979-98300-1-2

Raksodewanto et al. / Int. Sem. Chem. Eng. Soehadi Reksowardojo 2011

PS 121, and extensive oxidation may increase either of these parameters beyond their maximal limits. Although PV itself is not listed as a parameter in the biodiesel fuel spesification, formation of hydroperoxides caused by oxidative degradation during storage is known to influence cetane number [9-10]. In addition to effects on , AV, and PV, extensive degradation may produce insoluble high-MW polymers that clog fuel lines and filters or lead to injector coking, incomplete combustion, and engine deposit. Table 1 Biodiesel specification negatively impacted by autoxidation Parameter Test Method Units ASTM D 6751 EN 14214 ** Oxidative EN 14112 h 3.0 min 6.0 min stability, 110oC Acid Value ASTM D 664 mg KOH/g 0.8 max 0.5 max EN 14104 Kinematic ASTM D 445 cSt 2.3-6.0 3.5-5.0 Viscosity, 40oC EN ISO 310
** Oxidative stability (EN 14214) is accelerated measurement by Rancimat

Bondioli and co-workers stored several drum-quantity samples of biodiesel at ambient conditions for 1 year. One sample was shaken once per week to promote intimate contact with air. Over this period the quiescent samples exhibited little or no change in properties, including only minor reductions in EN 14112 induction time. This contrasts strongly with the results of studies conducted at higher temperatures (for example, 43oC, as in ASTM D 4625), which have shown large changes in acid value and other parameters for some biodiesel samples [11,12]. The agitated sample exhibited significant increases in peroxide and acid values, however, and a large reduction in induction time because of the increased exposure to dissolved oxygen. Mittelbach and Gangl also stored biodiesel produced from rapeseed oil and used frying oil under different conditions for up to 200 days [13]. Degradation caused by oxidation began immediately, as shown by the formation of peroxides and reduction in induction time. The objectives of this research were to determine the stability of biodiesel and blends of biodiesel with straight run petrodiesel over an extended storage period, to evaluate the storage life of biodiesel and and biodiesel/petrodiesel blends without addition of antioxidant and to determine the effect of typical metals present in diesel fuel storage systems on the long-term stability of these fuels and fuel blends.

Experimental Procedures

Materials. Biodiesel Palm and Biodiesel Jatropha were produced in Balai Rekayasa Disain dan Sistem Teknologi (BRDST)-BPPT plant facility. Then, analyzed to know the initial value of each product based on SNI 04-7182-2006. As storage tank, the mechanical team designed and manufactured several tanks from two kind of materials stainless steel and carbon steel. Those tanks were conditioned similar to the Pertamina storage. Espesially to Biodiesel Palm, is blended to petrodiesel (B5, B10, B20, and B-50). Table 2
No. 1 Parameter Acid Value

Properties of Biodiesel Jatropha and Palm

Standard Testing Method ASTM D974 Biodiesel Jatropha 0,2473 Biodiesel Palm 0,2589

max. 0,8 mg KOH/gr

ISBN 978-979-98300-1-2

The Influence of Storing Time to Biodiesel Degradation Rate

2 3 4 5 6 7 8 9 10 11

Free Glycerol Total Glycerol Density Soap Content Ester Content Iodine Value Helphen Test Water and Sediment Content Cloud Point Kinematic Viscosity, 400C

max. 0,02% (w/w) max. 0,24% (w/w) 850-890 kg/m3 Min 96,5% (w/w) max. 115 gI2/100gr Negative max. 0,05% max. 180C 2,3 6,0 cSt

FBI- A01- 03 FBI-A01-03 ASTM D1298 FBI-A03-03 FBI-A03-03 FBI-A04-03 AOCS Cb 1-25 ASTM D2709-96 ASTM D2500 ASTM D445

0,0091 0,2014 862 181,61 99,36 38,79 Negative < 0,05 3 2.88

0,014 0,1914 873 99,58 58,98 Negative < 0,05 15 4,02

Methods. Storing biodiesel were conducted in tanks that placed inside and outside building without limitation of storing time. Biodiesel was stored in tanks without limitation of storing time. This method is adopted from ASTM D 4625, Standard Test Method for Distillate Fuel Storage Stability at 43oC, for a specified period time [14], but in this method, biodiesel sample is stored in bottle, completed with venting as a pathway to contact with the air. 100 ml sample was taken once per day, week, and month from each tanks to analyze the changing of biodiesel fuel properties ( and AV) until the propeties out of specification. Along the storing process, the ambient temperature and humidity were measured by hygrometer. Before taken for analyzing, the biodiesel were mixing to make homogenity of all parts. Kinematic viscosities were determined at 40oC according to ASTM (American Society for Testing and Materials) standard D 445. And acid values were determined with ASTM D 664.

Result and Discussion

The issue of oxidative stability affects biodiesel primarily during extended storage. The influence of parameter such as presence of air, heat, traces of metal, peroxides as well as nature of the storage container was investigated in the studies cited here. Generally, factors such as presence of air, elevated temperatures of presence of metals facilitate oxidation. Studies performed that the biodiesel feedstock influenced the resistancy of biodiesel during storage period. It proved that compound structure of fatty esters, especially unsaturation was even greater.

3.1

Oxidation mechanisms, autoxidation and photoxidation

The rates of oxidation of unsaturated fatty acids or esters can vary considerably. The understanding of oxidation is complicated by the fact that fatty acid occur in complex mixtures, with minor component in this mixtures catalyzing or inhibiting oxidation. This observation affects biodiesel because usually significant amounts of esters of oleic, linoleic and linolenic acids as well as minor components which may affect oxidation are present.

ISBN 978-979-98300-1-2

Raksodewanto et al. / Int. Sem. Chem. Eng. Soehadi Reksowardojo 2011

Table 3

Fatty Acid Composition of Biodiesel Palm and Jatropha

No. 1 2 3 4 5 6 7 8 9 10

Compound Lauric Acid Myristic Acid Palmitic Acid Palmitoleic Acid Stearic Acid Oleic Acid Linoleic Acid Linolenic Acid Aradic Acid Erucate Acid C12:0 C14:0 C16:0 C16:1 C18:0 C18:1 C18:2 C18:3 C20:0 C22:1

CPO (Patzaris) 0 0.4 0.6 1.7 41.1 47 0 0.6 3.7 5.6 38.2 43.5 6.6 11.9 0 0.5 0 0.8 -

CJO (Gubitz) 0 0.1 14.1 15.3 0 1.3 3.7 9.8 34.3 45.8 29.0 44.2 0 0.3 0 0.3 -

Oxidation of fatty materials promoted by factors such as elevated temperature, presence of light or extraneous materials such as metals or initiators. The nature of the radicals also influences the product observed and double bond geometry can also play a role. Antioxidants function by delaying oxidation but not preventing it. Oxidation mechanism in oil and fat is as follow:

Initiation RH + I

R*

IH

Propagation R* + O2 ROO* ROO* + RH ROOH Termination R* + R* R-R ROO* + ROO*

R*

stable product

Photo-oxidation is more rapid than autoxidation by several orders of magnitude. For oleat, photo-oxidation is about 30,000 times more rapid and for linoleat and linolenate this value 1500 and 900 [15]. Literature values for relative autoxidation rates of oleate, linoleat, and linolenate are 1, 27, and 77, respectively [15] and 1, 41, and 98 respectively [16] with that of 20:4 being 195. The relative oxidation rate of triaglycerols is lower, that trilinolein being 50. Thus the relative rates of photo-oxidation between oleate, linoleate, and linolenate are considerably smaller compared to autoxidation. The autoxidation process usually exhibits an induction time during which overall reaction is slow, followed by a more rapid stage. The purpose of antioxidants is to either prolong the onset of the initiation reaction or to enhance the termination, reducing the length of propagation. However, the rates of oxidation in natural mixtures such as vegetable oils can differ from those in studies on pure compounds due to the presence of pro- and antioxidants.

ISBN 978-979-98300-1-2

The Influence of Storing Time to Biodiesel Degradation Rate

3.2

Oxidation of Biodiesel

The oxidation reactions mentioned above utimately affect the fuel quality of biodiesel, primarily during extended storage. Beside oxidation caused by exposure to air (oxygen), biodiesel is also potentially subject to hydrolitic degradation due to the presence of water. This is largely a housekeeping issue although the presence of, for example, mono- and diglycerides (intermediates in the transesterification reaction) or glycerol which can emulsify water can play a major role [17]. \ As mentioned above, double bonds may also be prone to polymerization-type reactions so that molecular weight products, leading to an increase in viscosity, can occur. This may lead to formation of insoluble species which can clog fuel lines and pumps. One study [18] reports that polymers formed during storage under controlled conditions are soluble in biodiesel due to its polar nature and are insoluble only when mixing the biodiesel with petrodiesel. The formation of higher molecular weight species, which posses higher viscosity, is a reason why the viscosity specification in biodiesel standards can be used to assess the fuel quality status of stored biodiesel. Long term storage tests on biodiesel have been conducted. Viscosity and acid value increased in biodiesel stored for six months.

3.2.1

Effect of Storing Period to Kinematic Viscosity at 40oC

Viscosity increases with chain length (number of carbon atoms) and with increasing degree of sturation. Free fatty acids have greater viscosity than the corresponding methyl or ethyl esters. Bouble bond configuration influences viscosity (cis double bond configuration giving a lower viscosity than trans) while double bond position affects viscosity less. Since oxidation processes lead to the formation of free fatty acids, double bond isomerization, usually cis to trans, saturation and products of higher molecular weight, viscosity increases with increasing oxidation. Biodiesel from Palm and Blended Biodiesel Palm-Petrodiesel stored for 180 days, while Biodiesel from Jatropha stored for 120 days at temperature 25-31oC and humidity 57-98% did not exceed the range of viscosity (2,3-6,0 cSt). On the other hand, following the test results, increasing of viscosity just represented the indication that oxidation occur during the storing period.

ISBN 978-979-98300-1-2

Raksodewanto et al. / Int. Sem. Chem. Eng. Soehadi Reksowardojo 2011

Figure 1

Increasing of Kinematic Viscosity on Biodiesel Palm

Figure 2

Increasing of Kinematic Viscosity on Biodiesel Jatropha

ISBN 978-979-98300-1-2

The Influence of Storing Time to Biodiesel Degradation Rate

3.2.2

Effect of Storing Period to Acid Value

Acid Number is a good indicator of the level of Free Fatty Acids (FFA) in Biodiesel. High teste values for Acid Number can be correlated to manufacturing a FAME fuel from unrefined feedstock (i.e. high in Free Fatty Acids) and/or poor process control in the conversion of the feedstock oils or fats to a FAME fuel (i.e. methanol carryover). High acid levels in Biodiesel can cause fuel system deposits and is another indicator that the fuel will act as a solvent resulting in the deterioration of rubber components of a fuel system. Furthermore, moisture be present in transport or storage tanks, the methyl esters in the Biodiesel will degrade quicker resulting in further increases in Acid Number. Moisture causes the methyl esters in Biodiesel to undergo hydrolysis forming Free Fatty Acids. Moisture is very common in diesel storage tanks and should be minimized or eliminated when storing Biodiesel. Users of Biodiesel should monitor the Acid Number when the fuel is received and during storage to see if the Biodiesel is susceptible to degradation or if degradation is occurring. Normally moisture would not present a problem with diesel fuel or diesel equipment, however, moisture is detrimental when combined with any Biodiesel product and would ultimately affect both equipment performance and equipment maintenance. Another concern with moisture presence in diesel fuel storage is the possibility of the formation of bacteria. If algae appear in Biodiesel storage tanks, it is recommended that periodic testing be done to ensure microorganisms are not present in diesel fuel storage tanks. The testing have found that when moisture is present in Biodiesel degradation fuel by hydrolysis to Free Fatty Acids is more of a problem to the user than bacteria growth and pushed the degradation of biodiesel signed by the increasing of acid value.

Figure 3

Increasing of Acid Value on Biodiesel Palm

ISBN 978-979-98300-1-2

Raksodewanto et al. / Int. Sem. Chem. Eng. Soehadi Reksowardojo 2011

Figure 4

Increasing of Acid Value on Biodiesel Palm

Refers to SNI 04-7182-2006, the maximum value of acid value is 0,8 mg KOH/g sample. The testing shown that biodiesel palm without antioxidant were starting to decrease after six months (180 days) stored period both of inside and outside, whereas biodiesel jatropha started to exceed the maximum limit after four months (120 days) stored period. The different stored environment (light, air, moisture) had influenced the characteristic of biodiesel itself. Biodiesel that placed outside were prone to decompose faster than inside the building. It was indicated that the air, light, and heat play big role in degradation process of biodiesel.

3.2.3

Oxidation Stability by Rancimat

OSI (hour) was measured following EN 14112 at 110oC utilizing a Metrohm 743 instrument. Measurement of oxidative stability can be accomplished with accelerated method whereby various experimental parameters are influenced to yield results in a reasonable period of time. Such parameters may include elevated temperature, presssure, and/or flowrate of air (oxygen) through the sample, among others.

ISBN 978-979-98300-1-2

The Influence of Storing Time to Biodiesel Degradation Rate

Figure 5

Rancimat Result of Storage Testing on Biodiesel Palm and Jatropha

The degradation of biodiesel palm and jatropha were measured according to stored period bytwo method manually ( and AV) and accelerated method (Rancimat). Both of method had described the degradation of biodiesel during the stored period. The additional of antioxidants could be delayed but not completely prevented.

Summary and Conclusion

Biodiesel oxidation is a very complex process that is affected by a variesty of factors, including the composition of the fuel itself and conditions of storage. The different unsaturated components of biodiesel can generate different degradation products. Periodic monitoring of biodiesel during storage may be necessary to ensure effects of autoxidation do not compromise fuel quality. Both of and AV showed the greatest potential in terms of timely and relative ease of measurement. Either of these parameters should provide insight to determine whether storage conditions are need to be upgrade. Either parameter should also provide quantitative information on status of the fuel before its oxidation induction period has expired. According this testing result, biodiesel palm could be survive until six months without any addition of antioxidant, while biodiesel jatropha will survive for only four months without antioxidant.

References

[1] G. Knothe, J. Krahl, J. Van Gerpen (Eds), The Biodiesel Handbook, AOCS Press, Champaign, IL, 2005. [2] M. Mittelbach, C. Remschmidt, Biodiesel The Comprehensive Handbook, M. Mittelbach Karl-Franzens University Graz, Austria, 2004. [3] American Oil Chemist Society Official Method Cd 12b-92, Oil Stability Index (OSI), AOCS, Champaign, IL, 2005. [4] ASTM PS121, Provinsial Specification for Biodiesel Fuel (B100) Blend Stock for Distillate Fuel, in Annual Book of ASTM Standards, American Society for Testing and Materials,. West Conshohocken, PA, 2000. [5] Thompson, J.C., C.L. Peterson, D.L. Reece, and S.M. Beck, Two-Year Storage Study with Methyl and Ethyl Esters of Rapeseed, Trans. ASAE 41:931-939 (1998). [6] Bondioli, P., A. Gasparoli, A. Lanzani, E. Fedeli, S. Veronese, and M. Sala, Storage Stability of Biodiesel, J. Am. Oil Chem. Soc. 72:699-702 (1995).

ISBN 978-979-98300-1-2

Raksodewanto et al. / Int. Sem. Chem. Eng. Soehadi Reksowardojo 2011

[7] Du Plessis, L.M, J.B.M. de Villiers, and W.H. Van der Walt, Stability Studies on Methyl and Ethyl Fatty Acid Esters of Sunflower Seed Oil, Ibid. 62:748-752 (1985). [8] Du Plessis, L.M, and J.B.M. de Villiers, Stability Studies on Methyl and Ethyl Esters of Sunflower Seed Oil, in Vegetable Oil as Diesel Fuel Seminar III, edited by M.O. Bagby and E.H. Pryde, USDA Northern Regional Research Center, Peoria, 1983, pp. 57-62. [9] Van Gerpen, J.H., Cetane Number Testing of Biodiesel, in Proceedings, Third Liquid Fuel Conference: Liquid Fuel and Industrial Products from Renewable Resources, edited by J.S. Cundiff and E.E. Gavett, American Society of Agricultural Engineers, St. Joseph, MI 1996, pp 197-206. [10] Clothier, P.Q.E., B.D. Aguda, A. Moise, and H. Pitchard, How do Diesel Fuel Ignition Improvers Work? Chem. Soc. Rev. 22:101-108 (1993). [11] Westbrook, S. R. An Evaluation and Comparison of Test Methods to Measure the Oxidation Stability of Neat Biodiesel, NREL/SR-540-38983; National Renewable Energy Laboratory: Golden, Colorado,USA, 2005. [12] Bondioli, P.; Gasparoli, A.; Della Bella, L.; Tagliabue, S. Eur. J.Lipid Sci. Technol. 2002, 104, 777784. [13] Mittelbach, M.; Gangl, S. J. Am. Oil Chem. Soc. 2001, 78, 573577. [14] P. Bondioli, A. Gasparoli, L. Della Bella, S. Tagliabue, G. Toso, Biodiesel stability under commerical storage conditions over one year, Eur. J. Lipid Sci. Tech, 105 (2003), pp. 735-741. [15] F.D. Gunstone, Oxidation through reaction with oxygen, in The Chemistry of Fats and Oils by Gunstone, F.D., Blackwell Publishing, CRC Press, Oxford, UK, 2004, pp. 150-168. [16] E.N. Frankel, Lipid Oxidation, second edition, The Oily Press, PJ Barnes & Associates, Bridgwater, England, 2005. [17] J.M. Weiksner Sr., P.E., S. Crump, and Thomas L. White, Understanding Biodiesel Fuel Quality and Performance, available electronically at http://www.osti.gov/bridge.

ISBN 978-979-98300-1-2