FATTY

PRODUCTION ACID METHYL

AND FUEL
ESTERS

PROPERTIES FROM USED

OF FRYING

OIL

M.Mittelbach*,

B.Pokits, A.Silberholz

ABSTRACT In the last years great attention has been paid on the use of straight or modified vegetable oils as fuel in Diesel engines, in developed countries mainly to reduce the enormous amount of subsidies spent for agricultural over-prc&ction, in underdeveloped countries to become less dependent on fossil oil imports. In Europe especially the route of transforming the \.egetable oils into fatty acid methl.1 esters is intensively followed, so there is no need for any mcdilications of the engines. Austria is one of the leading countries in that field, which can be demonstrated by the existence of two industrial plants and se\.eral decentralized plants for the production of rape seed oil methyl esters (RME) \\.ith a total capacity of about 30.000 t per yex. As vegetable oils are economically still not competiti\.e \vith mineml based products, the use of old frying oils as s&rung materials seems \.ery attracti\-e. First investigalions in that field, ;t labordtory scale production and first emission lests in a Diesel engine have already been published (Nye et al., 1983; Mittelbach and Tritthart, 19%). The purpose of the rcscarch reported herein \fxs to collect and analyze representati\,e samples of used fqing oils for their suitability as stxtlng material for the productlon of mcrh>4 cstcrs, to modify and adapt existing tnnsestcrification prtxxsses and to compare the tucl propertics of the obtained methyl esters lr.ith those of RME according to the stclndards established for RME in Austria (ONORhl, 1991). This ij,ork \vas conducted during 1989 and 1991 in cooperation with Vogel & Nwt Industrieanlagcnbuu Gcs.m.b.H., Graz. Austria, and \\a~ supported by the Forschungsftirdcrungsfonds fiir die gcwcrblichc Wirtschaft. KEYWORDS. Vegetable Oils, Used Frying Oil, Fatty Acid Mcth>,l Esters, Dicscl Fuel Used Frwna Oil: Waste or Raw Material? According to the 01 World AMU~ (1988) the per wapiti disappeamncc of fats and oils, \vhich means the avenge production plus imports minus exports, during 1987i88 was 3 1.3 kg in USA and 30.2 kg in Austria The leading country was the Netherlands \r-ith 87.6 kg. About 120.000 t of \,egetable 011sare used in Austria per year, about the half of which is used for frying purposes. According to the Austrian law this material is special nastc, which has to be collcctcd and specially disposed. Today, howe\,er, only a small part of that material is treated according to the law, most of it, especially the fqing oil used for household purposes, is still disposed down the drain. A considerable part of the material, which is collected, is exported mainly for the preparation of animal feed. There are several other possibilities for utilization of used frying oil, the simplest one is burning of the oil. Another possibility is the preparation of soaps by hydrolysis or the purification and reuse as lubricating oil or hydraulic fluid. The production of Diesel fuel out of used frying oils seems to be the most attractive alternative for waste treatment, but certainly will not solve our energy problems, because at the most l-2 5%of our Diesel demand could be covered by this source.

* M.Mittelbach, Associate Professor, Institute of Organic Chemistry, Karl-Franzens Universitit Graz, HeintichstraBe 28, A-8010 Graz, Austria.

Anaivsis of Used Frying Oil Samples by Al-Kahtani (1991), who and evaluated the quality of the discarded oils. For our research we also collected and analyzed representative samples of used frying oils from households as well as from restaurants and other big consumers. The main analysis parameters were the chemical and physical alteration of the oils, the contamination with water and other food ingredients, the fatty acid composition and the content of free fatty acids. Here we want to describe only the results from 12 representative samples, out of which 8 (samples l-8) were from big consumers like restaurants and hospital kitchens, and 4 samples were from households (sample 912), resulting from various collections during several weeks. The average storage time after usage and before analysis was between 1 week and 1 year. The samples l-8 had solid or semifluid consistence, typical for hardened frying oils, whereas the household oils mainly were liquid vegetable oils. The average heating time for normal frying ptnposes is about 1 to 30 hours at temperatures behveen 130 - 180C. For comparison one sample waskept under laboratory conditions for 100 hours at 200C (sample 13). To determine the chemical deterioration of the oils after heating, the samples were analyzed by column chromatography according to literature (Waltking and Wessels, 1981; Perkins and Pinter, 1988). With this method the part of polar compounds, resulting from radical or nonradical oxidation processes, was determined. The results, which in detail will be published elsewhere, shoned, that the main part of the triglycerides remained unchanged under normal conditions and only 3 to 10 s of the triglycerides were oxidized. By heating the oil, how,ev.er, to 203C for 100 hours, about 60 % of the triglycerides were chemically altered. The main parameters for a simple transesterification process are not only the chemical changes of the fatty acid chains. but the content of lvatcr and free fatty acids, which can require costly purification steps. As you can see in Fig. 1 the content of water in the 12 samples was bctuecn 0.05 and 0.16 ?L, only 1 sample had a content of 1.96 q, lvhich may result from non proper storage conditions. Sample 13, lvhich was heated o\.er a long period, had a water content of 0.95 c7c, w,hich may result from thermal decomposition.
A good survey of analysis methods for used frying oils was published investigated the frying practices and frying conditions at 62 restaurants

10

11

12

13

Sample Number
Figure 1. Water Content of Used Frying Oil Samples

The content of free fatty acids lay between 0.26 and 2.12 %, typica! values for unused and unrefined vegetable oils (Fig. 2). Only heating over a long period led to a significantly higher content of free fatty acids, which can reach values up to 10 % (sample 13). These data show, that normally there are no great differences in the chemical and physical properties between unused and used vegetable oils, so there is no necessity for costly separation and purification steps. In mat cases simple heating and filtering of the solid impurities is sufficient for further transesterification. Only for oils with a high content of water and free fatty acids drying and neutralization steps are necessary.

10

11

12

Sample Number Figure 2. Content of Free Fatty Acids of Used Fping Oil Samples Preparation of Fatty Acid Methyl Esters Prior to tnnsesterification all samples were purified from solid particles by filtering at 40C. For transesterification a low temperature process under alkaline catalysis was used, which has been well tested in existing plants in Austtia (Mittelbach et al., 1988; VNI, 1992). The temperature should be higher than the melting point of the sample but should not exceed 50C. The transesterification was performed in 3 steps to guarantee a high conversion rate and a low content of remaining glycerides. In a three-necked round bottom flask equipped \i*ith a mechanical stirrer, thermometer and dving tube 1000 g of the oil sample was heated to 40C and treated lvith an aliquotc of 15.0 g of potassium hydroxide in 150 ml of methanol. After 20 min of stirring the mixture, which slowly became clear and less viscous, was allo\~~cdto stand for Pi\-c hours. The dark glycerol layer, ivhich contained most of the polar impurilies, was separated. Subsequently Ihe two other steps RXXCpcrformcd analogously Icading to the raw methyl ester phase. After separation of the last glycerol layer the methanol \\a~ remo\cd under reduced pressure at 60C. The resulting ester, u-hich contained considerable amounts of potassium soaps, was purified by passing the ester through a column filled with strongly acid, macroreticular ion exchange resin under ivaterfree conditions. This purification step rcmo\.cci most 01 the soaps as well as other impurities and led to \.cry pure fatty acid methyl esters. This procedure is well suitable for small scale production plants. The yield of esters \\as between 800 g and 900 g. For reconditioning and purification of the resin simple washing l<.ith methanol or regenention ivith diluted aqueous hydrochloric acid can be performed. Fuel Properties of Fattv Acid Methvl Esters The methyl esters obtained by the procedure described above were examined according to the Austrian standards valid for rape seed oil methyl ester used as Diesel fuel (ONORM, 1992). As it can be seen in Tab. 1, all values could be met by the used vegetable oil esters except the cold filter plugging point, which in most cases was over -8C. The solidification temperature strictly correlated with the content of saturated fatty acids, which are main constituents of hardened frying oils (Table 2). The values lay between -12C for a content of saturated fatty acids of 9.6 % (sample 3) and +8C for a content of 47.5 % (sample 10). This fact can cause problems in winter operation, so the use of additives or blends should be taken into consideration. Especial1.ywhen using old frying oil as starting material for the production of methyl esters without further distillation of the products, the content of inorganic compounds like salt and other impurities could be crucial for the use as fuel. The determination of the ash content is therefore of great importance, but no sample had a sulfate ash residue over 0.02 %, which means, that the transesterification process itself is a purification step, because most of the impurities are separated with the glycerol phase. So there is no need for distillation of the product provided, that the process leads to a high conversion and a low content of remaining glycerides.

PARAMEI-ER &Jnit]

STANDARDS FOR ONORMC 1190

USED FRYING OIL MErHYLExIERS Typical Values

I I

Visaxitv at 20C imm%l Flash Point [Cl

I
I

6.f s -8 I 0.02 248 51 0.3 (5s0.20)* 0.03 (55 0.02)* I 0.25

I

Cold Filter Plugging PointlW I CCR [% m/rr _ Sulfate Ash [% m/m] I Cetane Number Neutralization Number [mg KOH/g] Methanol [% m/m] Free Glycerine [% m/m] Total Glycerine 1% m/m]

-5 0.008 49 0.65 0.10 0.018 0.22 I

* Planned for 1993 Table 1. Fuel Propcrtics of Used Fving Oil Methyl E3tcrs The dctcrmination of the Conradson Carbon Rcsiduc (CCR). \r,hich was done according to DIN 51 551 b!- burning 10 g of the ester under o\):gcn dcflicicncy simulating very simplified the burning condlllons in an cnginc, gi\cs a good prcdrction of the quality of an cstcr fuel. VCQ! pure rncthJ.1 cstcrs ha1.ca CCR of about 0.01 %, \\,hich means that they ha\,c long conknts of gl~ccridcs, swp$ and other inorganic impurities. As it can bc SW-I in Tab.2 the \.alucs for the CCR shw\.cd vc~) gwxJ correlation ivith Ihc transcstcrification dcprcc, \\fhich \vas dctcrmincd according to Tmthnigg and Mittclbach (1990). The %alucs rcachcd from 0.01 % for \fcll kanscstcrificd products up 10 0.08 % for UrnpIt 5, \vhich had an contcnl of mclhylcstcrs of only 90 LTC.

Table 2. CCR-Residues and Solidification Temperatures of Methyl Esters

1.

Al-hlmn~, ti.A. lY91. h-vey Chem.Soc. 68: 857-862.

01 quality 01 used iqlng

011s

Irom resIauranLs. J.Hmer. 011

3 -.

Mittelbach, M. and P.Tritthart 1988. Diesel fuel derived from vegetable oils, III. Emission tests using methyl esters of used frying oil. J.Amer.OiI Chem.Soc. 65: 1185-l l&7. Mittelbach, M., F.Andreae and H.Junek 1988. Verfahren und Vonichtung zur Herstellung eines aIs Kmft- bzw. Brennstoff geeigneten Fettskreestergemisches. AT 388.743. Nye, M.J., T.W.Williamson, SDeshpande, J.H.Schrader, W.H.Snively, T.P.Yurkewich and C.L.French 1983. Conversion of used frying oil to Diesel fuel by transesterification: Preliminary tests. J.Amer.Oil Chem.Soc. 60: 1598. Oil World Annual 1988. J.Amer.Oil Chem.Soc. 65: 1030 (1989). ONORM C 1190 1991. Rapsiilmethjlester, Anforderungen (1.2.1991). Perkins, E.G. and S.Pinter 1988. Studies on the concentration of oxidized components of abused fats and the application of HPLC to their separation. J.Amer.Oil Chem.Soc. 6.5: 783. Trathnigg, B. and M.Mittclbach 1990. Anal!% of triglyccridc mcthanol>xis mi\;turcs using wcratic HPLC \\*ith density dctcction. J.Liqu.Chromatogr. 13: 95. Vogel & Noot Industricanla_genbau Gcs.m.b.H. 1992. Process for pnxiucing Fatty acid esters of lo\\*cr alcohols. WO 92X0268. Walking, A.E. and H.Wesscls 1981. Chromatographic separation of polar and nonpolar comooncnts of fning Fats.J.Asstx.Off.Anul.Chcm. 61: 1329.

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