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Winterization of Biodiesel by Micro Process Engineering

Winterization of Biodiesel by Micro Process Engineering



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Published by: natyquimica on Jul 17, 2009
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Winterization of biodiesel by micro process engineering
S. Kerschbaum, G. Rinke
, K. Schubert
Karlsruhe Research Center, Institute for Micro Process Engineering, Postfach 3640, 76021 Karlsruhe, Germany
Received 26 July 2007; received in revised form 18 January 2008; accepted 23 January 2008Available online 21 February 2008
A new method for winterization of biodiesel based on waste cooking oil is demonstrated, using micro heat exchangers with channeldiameters of 200
m. Biodiesel is pumped from a vessel through a micro heat exchanger in such a way, that pure seed crystals of satu-rated fatty acid methyl esters are produced at the outlet of the micro channels and injected back into the biodiesel vessel. Thus microprocess engineering allows the reduction of the sum of saturated fatty acid methyl esters within biodiesel based on waste cooking oilfrom 21.3% to 9.6%. This corresponds to a reduction in CFPP value of 11 K, which means that this biodiesel can be used at temperaturesdown to 264 K.
2008 Elsevier Ltd. All rights reserved.
Biodiesel; Winterization; Micro heat exchanger
1. Introduction
Rapeseed oil can be used as fuel for combustion engines,but its viscosity is much higher than usual diesel fuel andrequires modifications of the engines. To avoid such mod-ifications of the engines rapeseed oil is converted into bio-diesel by transesterification. Biodiesel fuels have a lot of environmental advantages[1–3], e.g. they are biodegrad-able, non-toxic and show low emission during combustion.However, there are some disadvantages. The costs of pro-ducing biodiesel are larger than of normal diesel fuel andbiodiesel is often only competitive because it is tax-favoured. These costs can be reduced if waste cooking oilis used as raw material instead of rapeseed oil[4–6].Atechnicalaspectisthatpartsofautomotiveenginesmaybe chemically attacked by biodiesel components. Biodieselhas a limited storage stability, which depends on chemicalcompositionofbiodiesel[7].Furthermore,inwintercrystal-lization of high melting saturated fatty acid methyl estersmay lead to plugging of filters and tubes. A fuel suited forlow ambient temperatures must have a low cold filter plug-ging point (CFPP). There is a correlation between saturatedfatty acid methyl esters, the higher the concentration of sat-urated compounds the higher CFPP value[8].One possibility to overcome this disadvantage arising atlow temperatures is the so-called winterization. This tech-nique can be applied to pure oils[9]or biodiesel[10,11]. In case of biodiesel the concentration of saturated fattyacid methyl esters has to be reduced. One possibility is toozonize vegetable oil[11], which cannot prevent the forma-tion of crystals, but will lead to smaller crystals. The sim-plest method is to cool down biodiesel with subsequentremoval of crystals by filtration[10]. In this paper, biodie-sel based on waste cooking oil was used and the treatmentresulted in a reduction of the CFPP value of 4 K. However,the method did not work reliable and sometimes failed. Toenhance the yield, it may be advantageous to use a solvent,e.g. hexane[12]. After this treatment hexane has to beremoved. This is associated with additional process engi-neering and costs. Another possibility to produce biodieselwith low cloud points is the chemical reaction of soy oilusing solid acid catalysts at high temperatures[13], wherethe cloud point (first crystals arise) of biodiesel based onsoy oil, was reduced for 6 K. Unfortunately the viscosity
0016-2361/$ - see front matter
2008 Elsevier Ltd. All rights reserved.doi:10.1016/j.fuel.2008.01.023
Corresponding author. Tel.: +49 7247 823556; fax: +49 7247 823186.
E-mail address:
 Available online at www.sciencedirect.com
Fuel 87 (2008) 2590–2597
increased. A simple method is the blending of biodieselwith mineral diesel to get a lower CFPP value[14].Recently, attempts were made to use additives, e.g. Visco-plex 10-305
[15]. In this case biodiesel based on a mix-ture of 80% rapeseed oil and 16% pork lard methyl estershowed a reduction of CFPP value of 7 K. Although thecrystals produced with these additives are small enoughto fulfil the CFPP standard, they are not always smallenough to pass modern fuel filters. For this and other rea-sons Viscoplex 10-305 is no more available commercially.
Aim of this work is the winterization of biodiesel basedon waste cooking oil, which is less expensive than biodieselbased on rapeseed oil. Until now, no method and no addi-tives are known to solve this problem in an economic way.Our new method does not use additives or blends andemploys a pure physical method. The method is based onwinterization with micro system technology using microheat exchangers[16]developed by the Karlsruhe ResearchCenter.
2. Experimental procedures
 2.1. Samples
All experiments were done with samples based on wastecooking oil methyl ester (WME). They were taken directlyafter production from a biodiesel plant
and consumedwithin one month.
 2.2. Analytics
For analyzing the chemical composition of biodieselduring the winterization process we used a gas chromato-graph (Agilent 6850 Series II, Injector Agilent 7683) witha DB-Wax column (length: 30 m) and a FID at 573 K.Helium was used as carrier gas with a throughput of 64 ml min
. Furthermore H
with 30 ml min
and airwith 400 ml min
were employed. The temperature pro-gram started at 403 K. This temperature was hold for1 min and then heated up with a rate of 5 K min
to atemperature of 513 K. This temperature was hold for10 min for the rest of the chromatogram. The calibrationof this column was done with three standard samples Rot-ichrom ME11, ME19 and FO7
containing all fatty acidmethyl esters, we needed. The temperature program wasoptimized to get well separated peaks. The integrated peaksof all measured compounds were linear as a function of concentration. The reproducibility and accuracy of thesemeasurements amount ±0.1%.Fig. 1shows a typical chro-matogram of our biodiesel sample. The relevant com-pounds are shown inTable 1together with the retentiontimes.
 2.3. Preliminary investigations
The simplest idea for winterization is to cool down bio-diesel slowly in order to precipitate high melting saturatedfatty acid methyl esters. This was done first with a double-
Fig. 1. Gas chromatogram of biodiesel based on waste cooking oil, seeTable 1for more details.
RohMax Additives GmbH, Kirschenallee, 64293 Darmstadt,Germany.
Biowerk Sohland GmbH, Saxony, Germany.
Carl-Roth GmbH, Karlsruhe, Germany.
S. Kerschbaum et al./Fuel 87 (2008) 2590–259
walled glass vessel, filled with biodiesel in its middle part. Acooled ethylene–glycol mixture was flowing through thedouble-walled space. In spite of the fact that crystals wereproduced, no change in chemical composition wasobserved. Another experiment was done with a vessel, sur-rounded by a cooling coil and thermal insulation. At theinner wall of this vessel crystals were generated andremoved by a rotating scraper. In this experiment nochange in chemical composition of the liquid phase wasobserved, neither. The compositions were measured bythe described gas chromatographic method. Because theconcentrations of the liquid phase did not change, the crys-tals have to be clusters of saturated fatty acid methyl esterscontaining liquid unsaturated fatty acid methyl estersinside. As fractionized crystallization methods failed, welooked for possibilities to produce pure crystals of satu-rated fatty acid methyl esters. Micro process engineeringwas found to solve the problem. This method is describedin detail in the following.For a proper design of micro heat exchangers for cool-ing of biodiesel the cold flow behaviour of biodiesel mustbe known. The most important property is viscosity, asthe pressure drop in heat exchangers depends on viscosity.So far most measurements have been done at room temper-ature or above[17,18]. Little information is available fortemperatures below room temperature. Therefore, we mea-sured the viscosity of biodiesel based on waste cooking oilat temperatures down to 258 K[19].
 2.4. Experimental setup
Fig. 2gives a schematic view of the experimental setup.A thermally insulated 5 l beaker was filled with a biodieselsample, which may be stirred with a magnetically coupledstirrer. The biodiesel is delivered by a gear pump (pump2) to a cross flow micro heat exchanger[16], which is showninFig. 3. The micro heat exchanger consists of 75 foils perpassage, each foil having 100 rectangular channels 40 mmlong with 200
m width and 100
m depth. Having passedthe micro heat exchanger the biodiesel returns back to thebeaker. To be sure that no crystals of saturated fatty acidmethyl esters enter the micro heat exchanger, the tubebetween the beaker containing biodiesel with crystals andthe micro heat exchanger was surrounded with a heatingtube. Within this heating tube hot water of 323 K was cir-cled, coming from thermostat 3. For cooling the biodieselwithin the micro heat exchanger thermostat 1 (Haake Pho¨-nix C25P), filled with a 1:1 mixture by volume of water andethylene glycol, was used. This cooling liquid is pumped(pump 1) through the second passage of the micro heatexchanger and then back to thermostat 1. Thermostat 2is filled with the same refrigerant and is cooling the beaker
Table 1Retention times of gas chromatographic peaks for each compoundCompound Retention time (min)Myristic acid methyl ester 8.44Palmitic acid methyl ester 11.78Stearic acid methyl ester 15.14Oleic acid methyl ester 15.50Linoleic acid methyl ester 16.22
-Linolenic acid methyl ester 17.19Arachidic acid methyl ester 18.2611-Eicosenic acid methyl ester 18.56Behenic acid methyl ester 21.28Eruric acid methyl ester 21.60Fig. 2. Schematic view of the experimental setup.Fig. 3. Cross flow micro heat exchanger with inner structures.2592
S. Kerschbaum et al./Fuel 87 (2008) 2590–2597 

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