Verfahren zur Modifikation von FAME Überblick über neuere Entwicklungen Processes to modify FAME Survey on recent developments Axel Munack 1 Jürgen Krahl 2 Michael Meier 3 1 Johann Heinrich von Thünen Institute 2 Coburg University of Applied Sciences 3 University of Potsdam
Modifications of FAME
Modifications of FAME
Boiling Curves for Different Diesel Fuels Temperature [ C] 4 35 3 25 2 15 1 DF EN 59 Mk I V-Power RME Palm oil methyl ester Coconut oil methyl ester Coco/Palm Palm/Soy Coco/Palm/Soy/Rape 2 4 6 8 1 Percentage of vaporized compounds [%]
Ageing of RME Ageing experiments B B1 B2, aged through 2 years
Spectroscopic Monitoring of Aging in the Sunlight Extinction at 5 nm 1.8 1.6 1.4 1.2 1..8.6 B8 B6 B4 B2 B1 B.4.2 1 2 3 4 5 6 7 8 9 Week
Artificial Ageing by Thermo-xidation or UV Irradiation Thermo-oxidation T = 11 C Aeration xidation by UV irradiation Aeration = 256 nm
Ageing through xidation by UV Irradiation Extinction 2,5 2 1,5 1 RME fresh RME 1 h UV RME 2 h UV RME 3 h UV RME 4,25 h UV + air RME 5,5 h UV + air RME 7,7 h UV + air,5 35 4 45 5 55 6 65 Wavelength [nm]
Thermo-xidation of RME Exposed to 14 C in Air Trends of Antioxidants and Acid Number 25 4 Carotinoides [mg/l] 2 15 1 5 Carotinoides NaH.2M 35 3 25 2 15 1 NaH. 2M [ml] 5 : 2: 4: 6: 8: 1: 12: Time [h]
Sedimentation ccurs when xidized RME is Mixed with GTL
Indissoluble ligomers in Blends of GtL and xidized RME Indissoluble oligomers [mg/1ml] 16 14 12 1 8 6 4 2 1 2 3 4 5 6 7 8 9 1 xidized RME in GtL [%]
Sediment Formation in DF-Biodiesel Blends.4.3 Deposition [g].2.1 2 4 6 8 1 Biodiesel in ULSD [%] Source: Fang and McCormick, 26 SAE Paper 26-1-33
Mutagenicity of Particulate Extracts in the AMES Test; MAN D8, ETC Test
Elementary Analyses ligomers Biodiesel* 65.6 9.6.1 24.8 76.99 12.27 1.6 [% wt ] Carbon Hydrogen Nitrogen xygen Sulphur [% wt ] *Source: Matthias, C., Melin, T., Beyer, H., Heinzel, A. (28). Entwicklung eines Biodieselreformers mit Metallmembran für den APU- Einsatz in Nutzfahrzeugen in Kombination mit einer PEM-Brennstoffzelle. AiF-Schlussbericht
Possible Mechanism: ligomerization 9 1 12 11 13 15 14 16 16 11 11 13 15 16 13 15 or - linkages 2 2 14 Source: Fang and McCormick, 26 SAE Paper 26-1-33
Possible ligomers CCH3 CCH3 CCH3 CCH3 CCH3 Trimer R31 Dimer R26 CCH3 CCH3 CCH3 C CCH3 CCH3 C Aldol Dimer R'25 (R' < R) Aldol ligomer R'2R9 Source: Fang and McCormick, 26 SAE Paper 26-1-33
Further Results from the Literature Precipitate gels were detected by Peyton, McGinnis and Bureman (NALC), too. These occurred in soy oil methyl ester and mixed FAME in the case of B5 and B2 not in case of B1. No sedimentation was found for palm oil methyl ester in every blend (B5 B1). For soy oil methyl ester and mixed FAME the precipitate forming compounds were also found in B1; however, in the neat fuels they stayed dissolved and did not precipitate. The compounds were identified as azelaic acid monomethyl ester (formed by oxidative degradation of methyl oleate) and hexanoic acid (formed by the oxidative degradation of methyl linoleate). Source: Peyton, K., McGinnis, T., Bureman, P.: Preventing Sediment Formation In Stored Biodiesel Fuel Blends. Biodiesel Magazine, December 28
Modifications of FAME
Dissolution of the Sediments
Dissolution of Sediments in B1GTL via Addition of Fresh RME (UV/VIS) Extinction at 85 nm [-] 1.4 RME-GtL Shell Blend 1.2 1..8.6.4.2 5 1 15 Addition of fresh RME [Vol %] 2
Dissolution of Sediments in B1GTL via Addition of Fresh RME (UV/VIS) 4 B1 B1 + 4% RME B1 + 7% RME B1 + 11% RME 3 B1 + 14% RME Extinction [-] B1 + 17% RME B1 + 19% RME 2 1 35 4 45 5 55 6 Wavelength [nm] 65 7 75 8 85
Dissolution of Sediments via Addition of Alcohols Extinction at 85 nm [-].3.25.2.15.1.5.5 1 1.5 2 2.5 Addition of iso-butanol [Vol %] 3 3.5
Dissolving the Sediments
spec. N x e missions [g/kwh] Dissolution of Sediments via Addition of Ethanol Effects on the Emission of NX; M96, ESC Test 6 5 Regulated value: 5 g/kwh 4 3 2 1 DF B2 B2agd B2E2 B2agdE2RMEagd RME
More Results from the Literature Peyton, McGinnis und Bureman propose to add antioxidants in order to prevent sediment formation. Source: Peyton, K., McGinnis, T., Bureman, P.: Preventing Sediment Formation In Stored Biodiesel Fuel Blends. Biodiesel Magazine, December 28
Modifications of FAME
Biodiesel: Demands of engine manufacturers, fuel producers, consumers, and the society, which may lead to changes in oil composition, processing, and utilization Results of the Biodiesel Workshop, Wuhan, 27 Plant oil composition - Boiling (start) temperature must be brought down chain lengths 12 16 - Melting point (resp.: CFPP) should be low enough non-saturated fatty acids - No polymerization 1 or 2, not 3 double bonds C12:1 C16:2 Processing Further demands - Low phosphorus content - Biotechnical methods for transesterification? Environment and health - Alternative pathways for utilization of glycerol? - Low summer smog formation potential - Low mutagenic potency - Low cytotoxic effects
Schematic of the Cross-Metathesis of leic Acid Methyl Ester for the Formation of New Biodiesel Blends excess Metathesis catalyst Sdp. ~ 215 C excess Metathesis catalyst Sdp. ~ 23 C excess Metathesis catalyst Sdp. ~ 25 C
Schematic of the Cross-Metathesis of Methyl Linoleate for the Formation of Biodiesel Compounds with Very Low Boiling Point excess Metathesis catalyst
Influence of Metathesis Products and Additives on the Boiling Behaviour of Diesel Fuels 6 Metathesis-RME (SimDist) DF (Distillation) RME (SimDist) Metathesis-RME-Blend (SimDist) RME + 1 % Additive (SimDist) RME + 2 % Additive (SimDist) Boiling point [ C] 5 4 3 2 1 1 2 3 4 5 % [m/m] 6 7 8 9 1
Thank you very much for your kind attention! Acknowledgement: The authors thank the Verband der Deutschen Biokraftstoffindustrie e.v. (VDB) and the Union zur Förderung von el- und Proteinpflanzen e.v. (UFP) for their support of the underlying research projects.