12th European Conference and Technology Exhibition on Biomass for Energy, Industry and Climate Protection 17-21 June

2002, Amsterdam, The Netherlands

STABILITY OF BIODIESEL Heinrich PRANKL BLT Federal Institute of Agricultural Engineering Rottenhauser Strasse 1, A 3250 Wieselburg, AUSTRIA E-mail: heinrich.prankl@blt.bmlf.gv.at ABSTRACT: In order to assure customer acceptance standardization and quality assurance is the key factor to the market introduction of biodiesel as a transport and heating fuel. In 1997 the European Commission mandated CEN to develop standards concerning minimum requirements and test methods of biodiesel. Working groups have achieved substantial progress. It was turned out, however, that in one complex key parameter, fuel stability, detailed research is absolutely needed. It is proposed to investigate all relevant topics to overcome this gap of knowledge. Suitable determination methods for the oxidation, thermal and storage stability will be worked out. The influence of storage conditions on the fuel quality properties and the effects of natural and synthetic antioxidants will be investigated. A comprehensive test program including bench and field tests will be carried out in order to find a relationship between the stability and special effects during use.

The project Stability of Biodiesel (BIOSTAB) is supported by the European Commission in the frame of the Quality-of-Life-Program. (Project number: QLK5-2000-00533). The projects duration is March 2001 until August 2003. Keywords: biodiesel, biofuels standardization, oxidation 1 BACKGROUND Biodiesel can reduce the European dependence on oil imports and contribute to the security of energy supply. Liquid biofuels are the only alternative fuels for transportation which can be realised in short term and in considerable amounts. Renewable raw materials from the agriculture for the biodiesel production play an important role in the integrated rural policy. Biodiesel has been produced on an industrial level in the past decade, largely in response to positive signals from the EU institutions. The production of biodiesel in Europe will receive 1 mill. t, produced mainly in Austria, France, Germany and Italy. It absorbs the production of nearly 1 mill. ha of arable land. And it shows tremendous absorbing potential for additional acreage coming into the enlarged European Union from new East European member countries. The European Commission has set itself the ambitious aim to increase the market share of renewable energy to 12% until 2010. The ways and means used for accomplishing this aim, i.e. establishing regulations concerning the creation of favourable conditions for renewable sources of energy, are summarised in the White Paper on Renewable Sources of Energy [1]. The campaign for take-off 1999-2003 determines to support different key sectors, like e.g. 5 million tons of liquid biofuels, by means of specific programmes and actions of the Community. Within the internal market European standards for technical equipment using renewable sources of energy will be developed in CEN. The creation of standards shall help to expand the industry for renewable sources of energy on a EU level [2]. In 1997 the European Commission mandated CEN to develop standards for high-quality biodiesel used as a fuel for diesel engines and as heating fuel as well as the necessary standards concerning the analytical methods applied [3]. The proposed standards support Community objectives of free trade of biodiesel and of high-quality guarantees for the use of biodiesel. In 2001 two drafts June 2002 (prEN14213 FAME as heating fuel and prEN14214 FAME as automotive diesel fuel) were subject of the public inquiry. In the drafting process a lack of knowledge about the stability of biodiesel was established. However the stability was considered as an important issue. It turned out that fuel stability has been overlooked and detailed research is needed in this area. 2 OBJECTIVES The objective of the project is to establish clear criteria and the corresponding analytical methods to determine the stability of biodiesel. The detailed aims are: 1. appropriate methods for the determination of stability under realistic conditions 2. understanding of the influence of storage conditions on the quality of pure and blended biodiesel 3. definition of a minimum level of natural and/or synthetic antioxidants 4. determination of the effects of the fuel stability during utilisation of biodiesel as automotive diesel fuel and as heating fuel. 3 PROJECT PARTNERS Nine partners from industry, research institutes and universities are involved in the project. The consortium is well experienced in biodiesel research. Altogether they represent a significant European dimension: BLT Bundesanstalt fr Landtechnik, Austria (Project co-ordination, contact: Heinrich PRANKL) ITERG - Institut des Corps Gras, Pessac, France (Contact: Dr. Florence LACOSTE) SSOG Stazione Sperimentale Oli e Grassi Technology Department, Milan, Italy (Contact: Dr. Paolo BONDIOLI) BLT Wieselburg

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IFC Graz - Institute of Chemistry, Karl-FranzensUniversitt Graz, Austria (Contact: Prof. Dr. Martin MITTELBACH) GUT Graz University of Technology, Austria (Contact: Jrgen BLASSNEGGER) OMV AG, Vienna, Austria (Contact: Dr. Thomas BREHMER) TEAGASC, Oak Park Research Centre, Carlow, Ireland (Contact: Dr. Andreas FRHLICH) NOVAOL, Paris, France (Contact: Bertrand DUFRENOY) OLC - lmhle Leer Connemann, Germany (Contact: Dr. Jrgen FISCHER)

reactions. However, the natural content of antioxidants in biodiesel varies significantly depending on the feedstock as well as process technology. For instance, distilled biodiesel, which from the chemical standpoint has the highest purity and therefore has been used as reference fuel, contains no antioxidants, which were separated during distillation. Because of that facts natural or synthetic antioxidants have to be found to improve the oxidation stability. Also the influence of natural and synthetic antioxidants on other quality parameters must be studied. 4.4 Utilisation of biodiesel Biodiesel is used both as automotive diesel fuel and as heating fuel. Tests are carried out on vehicles and veh icle systems, as well as on heating systems. The results of the tests will help to find a relationship between laboratory test methods and effects during the utilisation. Due to the variety of applications the test program is very comprehensive. Thus, the task is divided in 2 subwork packages: 4.4.1 Utilisation of biodiesel as automotive diesel (J. Blassnegger, GUT, Austria) The test program comprises: bench tests with different injection systems and test fuels with a varying stability long term tests with two diesel engines a fleet test using biodiesel with a low stability a fleet test with blends of fossil diesel and biodiesel with a low stability. 4.4.2 Utilisation of biodiesel as heating fuel (T. Brehmer, OMV, Austria) The test program comprises: bench tests with heating systems (emission, functionality, long term) field tests with heating systems.

Seven of the nine partners (BLT, ITERG, SSOG, Uni Graz, OMV, Novaol and OLC) are member in one or more working groups of CEN. 4 PROJECT WORKPLAN The project is divided into 4 thematic work packages. For each work package (WP) a leader is responsible to co-ordinate the tasks between the several partners. The participation in several tasks ensures an active interchange of information and interim results. 4.1 Work package 1: Determination methods (F. Lacoste, Iterg, France) Although a variety of several determination methods are known from the food industry, the knowledge about the effects of fuel stability on technical applications is very limited. Concerning fuel stability it is distinguished between: - oxidation stability: influence of oxygen and ambient air - thermal stability: influence of temperature - storage stability: influence of time and storage conditions Oxidation stability: the Rancimat test has been chosen as test method for thermal oxidation stability. (figure 1). The relationship between the induction period provided by this test and other quality parameters will be clarified. Thermal stability and storage stability: Due to a lack of knowledge no test method has been chosen for these two items so far. It is the task to select a method for each item (already existing or new) considering criteria such as reflection of real conditions, correlation with quality parameters of biodiesel, precision and costs. 4.2 Work package 2: Storage tests (P. Bondioli, SSOG, Italy) In this work package different storage environments will be simulated. Previous research demonstrated that storage conditions (i.e. temperature, light, atmosphere, presence of pro-oxidant metals, etc.) have a strong impact on storage behaviour. Also the nature of feedstock may dramatically influence the final result. 4.3 Work package 3: Antioxidants (M. Mittelbach, Uni Graz, Austria) The natural content of antioxidants like tocopherol and carotenoids in vegetable oils prevent oxidation June 2002

Figure 1: Rancimat for determination of oxidation stability 5 RESULTS SO FAR 5.1 Work package 1: Determination methods Data was collected about conditions of biodiesel storage and use in automotive which helped to define the conditions for the determination methods. The method for oxidation stability (Rancimat test which was already fixed by CEN) could be correlated with different quality BLT Wieselburg

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parameters. Promising methods for the determination of the thermal and storage stability were proposed and are being evaluated and improved at present. 5.2 Work package 2: Storage tests A storage test using eleven drums of biodiesel from different sources began in July 2001. Methyl ester made from rapeseed, sunflower, used frying oils and tallow is stored in 200 l drums under different conditions. Samples are taken out periodically and different quality parameters are monitored. The data will be used for developing the method for the determination of storage stability. After completing the first storage year some samples will be used for bench tests at University of Technology in Graz. 5.3 Work package 3: Antioxidants Based on the findings of an extensive literature survey, twenty synthetic antioxidants were selected, all of which are commercially available at an affordable price. The stabilising effect of the selected antioxidants was tested with biodiesel prepared from four different raw materials (RME - rapeseed oil methyl ester, SME sunflower oil methyl ester, UFOME - used frying oil methyl ester and AFME - animal fat methyl ester). Both distilled and undistilled biodiesel samples were tested, and Rancimat induction times were used to indicate oxidation stabilities. Antioxidants with good stabilising effect were tested at different concentrations in order to determine the optimum antioxidant levels. The effect of natural antioxidants on the oxidation stability of biodiesel was also evaluated. The relatively high stability of RME which cannot be attributed to the detected natural antioxidants is being investigated. 5.4 Work package 4: Utilisation of biodiesel 5.4.1 Sub work package 4.1: Biodiesel as automotive diesel fuel Long term tests on an injection test bed are carried out on 3 different injection systems: heavy duty common rail, personal car direct injection and personal car common rail injection system. Biodiesel with low, standard and high stability is used. A fleet test with four cars using only biodiesel with a low stability has already started. The test fuel was aged by air and heated before use. The conditions of the vehicles are monitored continuously by a data logging system. Bench and emission tests have been also carried out at the beginning of the test. A further fleet tests is carried out with three vehicles using mineral diesel fuel containing 5% of used frying oil methyl ester. The influence of fuel stability on the performance of the fuel delivery chain from storage tank to the vehicle fuel system is investigated. Emission testing at a chassis dynamometer were done at the beginning. No problems occurred so far, neither in the fuel system nor in the engine or engine oil performance. 5.4.2 Sub work package 4.2: Utilisation of biodiesel as heating fuel Bench tests: Emission tests and tests of functionality were carried out in the start up mode on several heating systems. 1000h intersectional tests with four fuels (containing 5% and 20% biodiesel) will be done on three different small-scale combustion units with conventional technology. Interval checks, emission control June 2002

measurements and product analysis will be carried out regularly. Field test programme: 8 test facilities were installed in Lower Austria. The heating systems were selected in agreement with the owners of system (one family households) and the burner and boiler manufacturers. Rape seed oil methyl ester and used frying oil methyl ester is used in blends of 5% to mineral oil based distillate heating fuels. Four of the eight systems are operated with fuel stabilised by antioxidants. Fuel analyses is carried out periodically. The operating parameters (temperatures, pressures, operation times) are recorded automatically. 6 DISCUSSION AND CONCLUSIONS Different methods for determining the extent of oxidation, thermal and storage stability of biodiesel can be proposed. The results of long term storage tests will give us a better understanding of the effect of the chemical composition on the stability of biodiesel. Several antioxidants were found to stabilise biodiesel, but they have not been fully evaluated yet. Bench and car fleet tests have started already, but results will not be available before completion of the tests. The experimental results which will be obtained in the present project, will improve greatly our understanding of the stability of biodiesel. With better understanding it will be possible to recommend the inclusion of relevant stability parameters in the biodiesel standard. A more stable product will boost customer confidence in this renewable liquid biofuel and improve its market share. Therefore it will help to achieve the goals set out in the "White Paper for a Community Strategy on Renewable Sources of Energy" and in the "Campaign for Take-Off". 7 REFERENCES [1] Energy for the future: Renewable Sources of Energy. White Paper for a Community Strategy and Action Plan. European Commission, Brussels (1997). [2] Energy for the future: Renewable Sources of Energy. Campaign for Take-Off. DGXVII. [3] M/245 Mandate to CEN for the elaboration and adoption of standards concerning minimum requirement specification including test methods for fatty acid methyl ester (FAME) as fuel for diesel engines and for heating (29 January 1997).

BLT Wieselburg