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hMlONAL BlODlESEL BOARD 1
October 15, 1995
TRANSLATING BIODIESEL DOCUMENTS WRITTEN IN THE GERMA5 LANGUAGE
A research activiq desigrled to review past and present biodiesel research
Principal Investigator:
Leon G. Schumacher
Duration of the project:
April 15, 1995 - September 15, 1995
TABLE OF CONTENTS
INTRODUCTION ..__...___........_....._......................__.....___. 1
PURPOSE AND OBJECTIVES . . . . . . . . . . . . . . . . . . _ . . . . . _ . . . , . _ . 1
WORK ACCOMPLISHED .................................................... 2 Travel Itinerary for Dr. Juergen Krahl ...................................... 2 Papers brouoJlt to the United States by Dr. Krahl included: ...................... 3 Abstracts Prepared ..................................................... 8
Biodiesel at the End?, RalfLenge .................................... S Rape for Ener,g Purposes ......................................... 9 TheOilh4illinKiel(NorthGermany)andtheRMEPlant.. ................ 9 Biomass in Comparison to Other Renewable Energ Resources ............ 10 Rapeseed oil fatty acid methyl ester is abbreviated as R&E .............. 10 Exhaust gas emission of an engine runningonRMEatanen,oineteststand .... 11 Polycyclic Aromatic Hydrocarbons in the Exhaust Gases of Diesel Engines _ . _ 12 Alternative Plant Oil Based Fuel for Diesel Etu$es ..................... 13 RME and catalyst provide cleaner diesel engine exhaust emissions .......... 1; RME as fuel for a ta,xi fleet in Freiburg, Germany ....................... 14 Exhaust Gas Emissions of Agricultural Tractors Running on RME .......... 16 Possibilities to reduce the emission of fossil and conventional fuels. ......... 17 Questions, facts and proposals from the view of Fent .................... 1 S Determination of PAHs in Automobile Exhaust Gases by HPLC ........... 1s RME/SME Results of 1000 Hour Durability Testing. .................... 19 RME as a me1 for agricultural tractors ............................... 20 Determination of PAH in the exhaust gases of diesel en-es .............. 2 1 Emission of Tractors Running on Alternative Fuels ...................... 2 1 Vegetable Oils for Fuel and Ener_q Purposes .......................... 2 1 Allowances of Vehicle Producers to Use Biodiesel ...................... 22 Rapid Determination of Selected Polycyclic Aromatic Hydrocarbons ........ 22 Comparison of DF and RIME on Different Diesel En-ties ................. 23 All new VW- Diesel models can be fueled with Biodiesel ................. 23
Recommendations Concerning Documents to Translate ........................ 24 Update NBB about European Biodiesel Activities ............................ 25 Presentations/Updates Given By Dr. J&&l .................................. 27 Sharing of Biodiesel Research/Knowledge Conducted by Dr. Krahl ............... 27 Translation Training for German Speaking Chemistry Student ................... 27 Ovewiew/Summary written by Dr. Krahl ................................... 25
AppendixA .,__,........._........_........,......,......._............... 30
AppendLxB . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..?l
INTRODUCTION
Much biodiesel research has been conducted in Germany and Austria concerning en_@ne durability, engine oil analysis, and exhaust speciation when fueling with 100% neat biodiesel. Gaining insight about some of the findings of this research has provided insi_ght concerning future research needed in the United States.
Interpreting biodiesel research, even for a native-born German speaking citizen, is quite dif3icult. Technical terms used when reporting biodiesel research are not commonly used by the average German speaking person. This project secured the services of a well-know German biodiesel researcher for two weeks. He in return has provided insight concerning biodiesel research wrirten in the German language and the implications concerning the commercialization of biodiesel.
PURPOSE AND OBJECTIVES
The overall purpose for this project was to provide an English translation of biodiesel research that has been reported/documented/written in the German language. Much of this research has been conducted in Germany and Austria. Specifically, the researchers:
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Prepared abstracts in English from German biodiesel documents.
Provided recommendations concerning which biodiesel documents should be completely translated.
Updated the NBB on recent European conferences and activities.
Updated the NBB concerning the researcher’s biodiesel research, particularly his efforts to quantify PAH emissions, aldehydes/ketones, cytotoxicity and mutagenaity of diesel particulate for biodiesel-fueled engines.
Shared theoretical knowledge concerning the appropriate chemical analytical methods that should be used to quantify the physical properties of the biodiesel and biodiesel exhaust gases.
Provided German Biodiesel translation training for an Mu German-born graduate student.
Prepared a concisely written summary of his work associated with this project.
Activities pertaining to each of these objectives are described in the documentation that follows.
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WORK ACCOMPLISHED
Dr. Juergen K.rahl, a researcher trained in biodiesel exhaust gas measurement (including PAH), traveled to Columbia, Missouri on June 2, 1995. The complete list of papers that Dr. Krahl brought to the United States has been typed for review and is reported below. A compiete set of these papers have been placed on file at the University of Missouri. A complete set of these papers were sent to NBB offices during September.
Travel Itinerary for Dr. Juergen Krahl
June 2
June 3
June 4
June 5
June 6
Juue 7
June 8
June 9
June 10
Depart Braunschwei,, m Germany and arrive in St. Louis, Missouri. Met with Leon Schumacher and Alan Weber.
Worked with Leon Schumacher, became familiar with his research and assisted in editing research papers for presentation by Leon Schumacher.
Met with Alan Weber and Leon Schumacher.
Met the faculty in Agricultural Engineerin, u at MU. Began translation activities. Met with Nancy Elser.
Met with NBB staff at Jefferson City, Missouri. Met with representatives from the Missouri Department of Aticultm-e John Hensley and Mark Hitt. Continued translation activities.
Met v4th Dale R Ludwig, Executive Director of Missouri Soybean Merchandising Council: continued with translation activities. Traveled to Ames: IA in preparation for a meeting with NBB Consultant, Jon Van Gerpen.
Met with Jon Van Gerpen, NBB Research Consultant. Visited with Earl Hammand and Lawrence Johnson, Food Scientists at the Institute of Food Technolom and the Department of Mechanical Engineering at Iowa State University. Presented research findings to Jon Van Gerpen, Lawrence Johnson, Steve Marley, Nancy Elser, and Leon Schumacher (and other interested parties). Met in Kansas City, MO: with Steve Howell, Research Director of NBB.
Back at MU Campus, Met with Professor Dabir Viswanath and Annand Chelleppa, MU Chemical engineering researchers. Continued with translation activities.
Saturday
June 11 Met with Nancy Elser & Leon Schumacher, preparing future work in the area of exhaust gas emissions of SME and its blends.
June 12 Continued with translation activities. Presented to MU faculty during the Agricuhural Engineering Noon luncheon. After the presentation, much discussion followed with Donald Van Dyne, MU.
June 13 Concluded translation activities while on campus. Made plans for firture exchanges. Met with Ken Schneeberger, Director of Advancement and Nancy Mays. News Writer- College of Agriculture, Food and Natural Resources. Traveled to St. Louis to visit with Mike Deterding, Vehicle Equipment Specialist of Bi-State Development Agency.
June 14 Met with Mike Deterding, Vehicle Equipment Specialist for Bi-State Development Agency. Depart for Braunschweig, Germany.
Papers brought to the United States and/or made available to NBB bv Dr. Krahl inchded:
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1993. Okologischen Bilanz von Raps01 bzw. Rapsolmethylester als Ersatz von Dieselkrafistoff (Okobilanz Rapsol). Stellungnahmen der e,xtemen Sachverstandigen zur.
1993. Biodiesel vor dem Aus? Top Agror 9/93: 30-33.
Anbau und Verwertung Nachwachsender Rohstoffe. 1995. Eine Chance fix Landwirtschafi und Industrie. Landesbauemverband Sachsen-Anhalt e.V. Industrie-und Handelskammer Magdeburg.
Anbau und Verwertung nachwachsender Rohstoffe. Teilnehrmerhste. Magdeburg, 06./07. Februar.
ASPECTS OF ALTERNATIVE ENERGIES FOR VEHICLE DRIVE. VDI Berichte 1020. Ta,aug Wolfsburg, 24. bis 26. November 1992.
Bailer, J. and K. de Hueber. Determination of Saponifiable Glycerol in “Bio-Diesel”. Landwirtschafiilch-chemische Bundesandstalt.
Batel, V.W., M. Graec G.J. Mejer, RMoller and F. Schoedder. 1980. Pflanzenole fin die Kraftstoff-und Energieversor-mg. GmndLLandtechnik Bd. 30( 1980) Nr. 2.
Batei W. 1952. Eignung von Pflanzenolen und Pflanzenoiderivaten als Kraftstoff fur Dieselmotoren. Grundl.Landtechnik Bd. 32 (1982) Nr. 5.
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9. Boyd, J. 1992. Aspects of Alternative Eneqies for Vehicle Drive. VDI Berichte 1020.
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Bjorseth: A. 1983. Handbook of Polycyclic Aromatic Hydrocarbons. New York:Marcel Dekker, Inc.
Connemann, J. 1994. Biodiesel in Europa 1994. Fat Sci. Technol. 96.Jahrgang December. pg. 536-545.
Crookes, RJ., M.A.A. Nazha and F. Kiannejad. 1991. Biomass Derived Oils as Alternative Fuels for Diesel Engines. International Conference on Environmental Pollution, Proceed&s. Volume One (2 12-2 19).
Drechsler, W., K Kraus and J. Landgebe. Okobilanz von Raps01 bzw. Rapsolmethylester als Ersatz fix Dieselkrafistoff.
Fahrzeugfieigaben fix den Betrieb mit Biodiesel. Bericht.
Graec M. G. Veilurh, 3. Kra and A. Munack. 1994. Fuel loom Sugar Beet and Rape Seed Oil - Mass and Energ Balances for Evaluation. Proceedings of the Sth European Conference on Biomass for Energ, Environment, Agriculture aud Industry.
Gragg, K 1994. Effects of Environmentally Classified Diesel Fuels, RME and Blends of Diesel Fuels an RME on the Exhaust Emissions. Motorcestcenter.
Hartmann, H 1995. Biomasse im Vergleich zu den Ubrigen Verfahren der emeuerbaren Energienutzung. 50.Jahrgang Landtechnik l/95/’
Hartu.ng, V.A. and KH. Lies. 1990. Schnellverftien zur Bestimmung der PAK-Werte. MTZ Motortechnische Zeitschrit? 5 1 ( 1990) pg. 12- 17.
Hartung, V.A and Karl-Heinz Lies. 1990. Schnellverfahren zur Bestimmung der PAK- Werte.
Hartung, A., J. Krafi, KH. Lies and J. Schulze. 1982. Messung polycyclischer aromatischer Kohlenwasserstoffe im Abgas von Dieselmotoren. MT2 Motortechnische Zeitsch&? 43 pg. 263-266.
H&rich, Daimier-Benz AG, Stuttgart. 1992. Rapsolfettsauremethylester als Krafistoff f&r NutzUrzeugdieselmotoren. Proceedings: Rapsmethylester, Vienna S. 47-57, 1992.
Heinrich, V.W. and A. Schafer. 1990. Rapsol-fettsaure- methylester als Kraftstoff fix Nuttiahrzeug-Dieselmotoren. ATZ Automobiltechnische ZeitschrifI 92 pg 168-173.
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Horstmann, B. and W. Stumpf RME/SME Untersuchungsergebnisse. JI Case GmbH- NeusslRhein.
Karst, U., N. Binding, K. Cammann, and U. Witting. 1992. Interferences of nitrogen dioxide in the determination of aldebydes and ketones by sampling on 2,4-dinitro phenylhydrazine-coated solid sorbent. Fresenius J Anal Chem (1993) 345:4S-52.
Kaschani, D.T. and A. Brauns. 1991. Bestimmung von PAHs in Kraftahrezeugabgasen durch HPLC. GIT Spezial-ChromatogTaphie 2/91:66-76.
Krahl, J. G. Velluth M. Graef and A Munack. 1994. Utilization of Rape Seed Oil and Rape Seed Oil Methylester as heIs-Exhaust Gas Emissions and their Effects on Environment and Human Health. Proceedings of the Sth European Conference of Biomass for Energy, Environment, Agriculture and Industry.
Kra J., G. Ve&guth and M. Bahadir. 1992. Bestimmung der Schadstoffemissionen von landwirtschafilichen Schleppem beim Betrieb mit Rapsolmethylest im VergIeich zu DieselkrafrstoflY Landbauforschung Volkem-ode, 42. Jahrgang ( 1992), Heft 4, Seite 247- 254.
Krahl, J. and G. Vellguth. 1994. Ubersicht von Arbeiten zum Einsatz von Raps01 und Rapsolmethylester als Kraftstoffe unter Berucksicht@ng umweltrelevanter Auswirlxngen. Institut fur Biosystemtechnik.
Kroger, J., R Olsaatenverarbeitungs aus Kiel. 1992. Die Olmuhle Kiel und die RME- Fabrik. Raps, 10. Jg(4) 1992. 174-176.
Kroll, M., G. Decker, A. Hartung, A. Post&a and B. Georgi. 1993. Influence ofFuel Composition on NMOG-Emissions and Ozone Forming PotentiaI. SAE Technical Paper Series.
Lange. W.W., A. Schafer, A.Le’Jeune, D. Naber, A.A. Reglitzky and M Gairing. 1993. The Influence of Fuel Properties on E,xhaust Emissions from Advanced Mercedes Benz Diesel Engines. SAE Technical Paper Series.
Levsen, K 19SS. The analysis of diesel particulate. Fresenius Z Anal Chem 33 1:467- 47s.
List of biodiesel abstracts ,oenerated while searching a database
May, H. and U. Hattingen. 1994. Untersuchungen zum verdeichenden Einsatz von Dieselkrofistoff und Rapsolmethylester an verschiedenen Dieselmotoren. Abschlussericht, University Kaiserslautem.
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Mills, G.A and A.G. Howard. 1983. A preliminary investigation of polynuclear aromatic hydrocarbon emissions from a diesel engine operating on vegetable oil-based alternative fuels. Journal of the Institute of Ener-q.
Mittlebach, M. and P. T&hart. 19SS. Diesel Fuel Derived from Vegetable Oils, III. Emissions Tests Using Methyl Esters of Used Frying Oil. JAOCS. Vol. 65, no. 7.
Mittlebach, M., P. T&hart and H. Junek. 1985. Diesel Fuel Derived from Vegetable Oils: II: Emission Tests Using Rape Oil Methyl Ester. Energ in Agriculture 4, 207-215.
Newkirk, M.S., L.R Smith, and P.M. Merritt. 1993. Heavy Duty Diesel Hydrocarbon Speciation: Key Issues and Technological Challenges. SAE Technical Paper Series.
Perkins, L.A., C.L. Peterson and D.L. AuId. 1991. Durability Testing of Transesterilied Winter Rape Oil (Brassica Napus L.) as Fuel in Small Bore, Multi-Cylinder, DI, CI Engines. SAE Technical Paper Series.
PFLANZENOLE ALS KRAFTSTOFFE FUR FAHRZEUGMOTOREN UND BLOCKHEIZ-KRAFTWERK_ VDI Berichte 1126. Ta-mg Wurzburg, 4. und 5. Juli 1994.
Plank, C., E. Lorbeer. 1992. Quality Control of Vegetable Oil Methyl Esters used as Diesel Fuel Substitutes: Quantitative Determination of Mono-, Di-, and Triglycerides by Capillary GC. Dr. Alfred Huethig Publishers.
Plank, C. 1992. Quanititative Determination of Free Glycerol, Mono-, Di-, and Triglycerides in Vegetable Oil Methyl Esters by Capillary Gas Chromatography. Journal of High Resolution Chromatography 15 ( 1992) 609.
Plank, C. and E. Lorbeer. 1994. On-Line LC-GC for the Analysis of Free and Esterified Sterols in Vegetable Oil Methyl Esters Used as Diesel Fuel Substitutes. International Symposium on Hyphenated Techniques in Chromatography.
Proceeding 1st European Forum on motor biomels. May 9-l 1, 1994. Biomels in Europe Developments, Applications, and Perspectives 1994-2004.
Rantanen, L. and S. Mikkonen, L. Nylund, P. Kociba, M. Lappi and N. Nylund. 1993. Effect of Fuel ou the Regulated, Unre-tiated and Mutagenic Emissions of DI Diesel En-ties. SAE Technical Paper Series.
Rapsolmethylester als Krdstoff im Feldversuch mit Taxen in Freiburg. 1993. Symposium Nr. 17048/68.325, Technische Akademie Esslingen.
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47. Reghtzky, A.A., H. Schneider, and H. Kmmtn. 1993. Chancen zur Emissionsminderung dtnch konventionelle t.md alternative KrafistofTe. Shell Technischer Dienst.
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Reglitzky, A.A., H. Schnieder and H. Kmmm 1992. Chancen zur Emissionsminderung durch konventionelle und alternative Krafistoffe. Deutsche Shell Aktiengesellschafi.
Riva G. 1994. Experimental results in difberent vegetable oils utilization for diesel en-ties. International Commissions of A-qicultural En~tieering. XII World Congress on Agricultural Engineering. (567-573).
Schafer, A. 1985. Alternative Dieselmotorenkrafistoffe aufder Basis von Pflanzenolen. Raps-Sonderausgabe Mai. pg. 145-145.
Scharmer: K, G. Golbs and I Muschalek. 1993. Pflanzenolkraftstoffe und ihre Umweltauswirh-gen-Argumente und Zahlen zur Umweltbilanz. Union zur Fordemng von Oel-und Proteinpflanzen e.V. (UFOP).
S&at-me:, K, H. Giusing and L. Krings. 1993. Standardanforderungen an Rapsolmethylester als Motorenkraftstoff. Entwurf- zu Teil I: Stand der Technik.
Scharmer, K, H. Glusing and L. Ktings. 1993. Standardanforderungen an Rapsolmethylester als Motorenkrafistoff. GET-Gesellschaft fur Entwicklungstechnolo~q mbH. IndustriestraBe, W-5 173 Aldenhoven.
Scharmer, K. 1992. Raps01 als Energie-Lieferant. Raps:lO.Jg.(2) 1992:95-99.
Schoedder. V.F. and G. Vellguth. 1957. Umwehvertraghchkeit altemativer Krafistoffe. 42.Jahrs. Landtechnik 10, October 1957.
Seiden+nz, J. and G. Benz. 1992. Erfahmngen Beim Betrieb Von Linienbussen Der Verkehrsbetriebe Zuerich Mit Rapsmethylester.
Syassen, V. 1992. Chancen und Problematik nachwachsender Krafistoffe Tei12. MT2 Motortechnische Zeitschrift 53,( 1992) 560-567.
Syassen, V.O. 1992. Chancen und Problematik nachwachsender Krafistoffe Teil 1. MTZ Motortechnische Zeitschrift 53:( 1992)5 10-5 17.
Syassen, O., Xaver Fend & Co., Marktoberdorf Biodiesel-Fragen, Fakten tmd Vorschlage aus der Sicht von Fend.
Symposium 1992. Rapsmethylester. Krafistoff und RohstoK GeseUschafi Osterreichischer Chemiker.
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Vellguth, V.G. 1985. Methylester von Rapsol als Krafistoff fur Schlepper im Praxiseinsatz. GnmdI. Landteclmik Bd.35( 1985) Nr. 5.
Vellguth, V.G. 1987. Emissionen bei Verwendung altemariver Kraftstoffe in Schlepper- Dieselmototen. Grtmcll. Landtechnik Bd. 37( 1987) Nr. 6.
Ziejewsb M., H. J. Goettler, L.W. Cook and J. Flicker. 199 1. Polycyclic Aramatic Hydrocarbons Emissions from Plant Oil Based Alternative Fuels. SAE Technical Paper Series.
Ziejewsk M., K Kaufinan, G. Pratt, J. Walter, P. Aakre. T. German, P. Wailer and .J. Derry. 1993. “Flower Power” Tractor Fuel Testing Program 1981-1957. SAE Technical Paper Series.
Ziejewski, M. and H.J. Goettler. 1992. Comparative Anaiysis of the Exhaust Emissions for Vegetable Oil Based Alternative Fuels. SAE Technical Paper Series.
Abstracts Prepared
Dr. Krahl brought several biodiesel documents (or abstracts of such documents) and has prepared abstracts (and/or notes) for these documents. These, for the most part, were typed for review by NBB and were attached to earlier updates.
Abstract.1
Grrrnan: Biodiesel vor dem Aus?, RalfLenge English: Biodiesel at the End?, Raif Lenge
An overview of transesterification plants in Austria is presented. Aschach and Bruck, with its capacities of 10,000 and 15,OOOt per year, are the most important ones. A number of smaller plants are divided all over the country. Built in 1993, Aschach stopped the transesterification of rapeseed oil because the technique used was old and inefficient. Since this time, the plant only produces non-transesterified oil.
Austria intends to sell biodiesel to Italy. There, it could be used as fuel for heating purposes because in Italy, mineral oil is highly taxed. But the Italian government stopped the importation of RME because they feared losing tax revenue.
The benefits of small plant transesteri&ation are explained. Small plants have had no problems selling RME. But the ,oreat disadvantage is that the production costs are much higher per ton than in larger plants (13 dollars per ton RME).
The &cerol derived from large plants can be used for pharmaceutical purposes. The glycerol of
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smaller plants with its impuriries can reduce the emissions of manure ifit is tilled under. Austria intends to transesterify yellow grease to transform a waste product to a high value fuel.
Key words.. transesteriJication, tax, glycerol, RMIE
Abstract.2 RAPS, IO. Jg. (2) 1992
German: Rapsiil als Energie-lieferant, Klaus Scharmer English: Rape for Energy Purposes
The average relative chanses of fuel consumption, CO, HC, NOx and particulates are presented. The enLtie conG,auration is taken into account. These results of relative changes are a part of a more general compilation from Krahl et. al., 1994. The author mentioned that the PAH, aldehydes, and different HC emissions were taken from the publication of Wurst et. al., 1990. They are not discussed very critically. The volumetric fuel consumption increases to 107 - 110% DF.
Other envirolnmental aspects are pointed out: - rapeseed has a good influence on the microbioIocz of the soil. - rapeseed covers the soil over a long period and reduces soil erosion. - rapeseed is a good addition to crop rotations. - RME is biodegradable. - RME has a positive ener_q balance. Values for the CO, emissions and the ener.gy input of the production of DF are given.
Keywords: HC, CO, NOx, PAN, Aidehydes, file1 conszltnptio~~, energy balance, DF production
Abstract.3 FLAPS, 10. Jg. (4) 1992
German: Die &miihle Kiel und die ME-Fabrik, Justus KrQer, Raiffeisen &aaten verarbeitungs Gm bH, Kiei English: The Oil Mill in Kiei (North Germany) and tit e RME Plant
The oil mill in Kiel is introduced. Its capacity is about 100,OOOt of rape each year. Technical aspects are introduced. The double pressings procedure does not require additional extraction procedures aftenvards. Phosphorous is reduced to a level of about 40 ppm- The exhaust gases are led through a so-called ‘“oiobed” (organic material with bacteria). A scheme of the plant
explains the procedure but is not too detailed.
Besides the technical aspects, one paragraph deals with the high quality of the cake or meal
produced. It has better benefits to animals than the whole seed.
A third aspect of the paper introduces the project in Euro-Biodiesel. Euro-Biodiesel has several
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participants that have commercial interest to create a model for RME and its related products like glycerol. But Euro-Biodiesel deals with technical, economic and quality control as well. (MU is in contact with the president of Euro-Biodiesel M. Karl Groenen. He was in Missouri in October 1994, 27-3 1.)
Keywords: Oil mill, transesterification plant, phosphorus, Euro-Biodiesel, gijxerol, feed.
Abstract. 4 50. Jailrgang LAND TECHMK l/95
German: Biomasse im Vergleich ;I( den iibrigen Verfahren der erneuerbaren Energienutzung English: Biomass in Comparison to Other Renewable Energy Resources
The greatest benefit associated with the use of biomass are with energy and CO2 balances. Concerning economics, the thermal use of solid biomass has the most potential. But it can hardly be compared to the use of solar thermal ener,T (ener,T from the sun). In the text, a table reveals the ener,T potentials of different forms of ener_q carriers.
The use of biomass as a fuel could reduce the CO2 emissions in Germany by 6.6 percent. With the exception of solar-thermal ener,qv, this potential is high compared to others. This potential is available at a relatively low price and has an environmental advantage as well. It is pointed out that a variety of biomass use is necessary. But the most important assumption is the rising costs for fossil energy. The article summarized is the abstract of a complete report.
Keywords: CO:, energy balance, biomass, rape seed oil
Abstract. 5 AT2 Automobiltechtische Zeitschrift 92 (1990)
German:Rapsiiifettstircre-metizvl ester als Kraftstofffiir Nutzfahrzeug-Dieselmotoren, Von Walter Heinrich und Anfsgar Schtifer English: Rape seed oil fatty acid methyl ester is abbreviated as ROME (This is the way Mercedes Benz did it before in 1995. Nowadays, they accept the abbreviation, RME, as well.
The properties of typical DF, certified DF, Rape seed oil and RME are presented. (Additionally, the authors give a hint to the use of alcohol-based fuels in Diesel engines.)
The results of a one-cylinder test engine and a slightly turbo charged 4-cylinder (63 kW/2400 rpm/OM 3 14 (= 3 14A) en-&e are introduced.
Test Engine: to compensate for the lower energy content of RME and therefore the induced higher fuel consumption, the injection angle could be changed about 3”. But the text and the pictures presented deal with standard injection angles. The regulated exhaust gas compounds of RME versus DF are presented:
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- Soot (BOSH): reduced to about 50% by RME - CO: slightly increased. The authors point out that nevertheless, CO is not a problem of diesel engines. - HC: si_@icantly reduced - NOx: increases up to 20% at high BMEP. In general, 1109/o NOx is expected.
It must be noted that the optimization of the fuel consumption by varying the injection angle leads to higher NOx emissions.
4 cylinder engine: The engine was not modified. The results are similar to those of the test engine.
- The lubrication oil dilution was investigated. Of interest were the Rh4E concentration, the change of viscosirv, the TBN and the pH-value. - The FUUE concentration increases over a period of 250h from 0% to 7%. - TM decreases over a period of 250h from 8.7 to 6.5 (mg KOH per gram) - pH-value starts at 6.8 then it increases slightly and after lOOh, it reads the value 6.8 agak. - Viscosity decreases fi-om 95 to 88 within the first 100h. Tinen it increases again. This may be an effect and due to the dilution and polymerization of the engine oil due to the RMIE in the emgine oil.
Keywords: RfWE/RoME, DF, soot, HC, CO, NOx, injection angle, hbricatiorl oil analysis
Abstract. 6 Heft 22, January 1990
German - FORSCHUNGSEERICHTE der Bundesanstait fiir Landtechnik, WZeselburg: Emissionen beim Einsat: von Rapsdlmeih-ylester an einem Prtifstandsmotor, Freiderich Wurst, Rolf Boos, Theodor Frey, Kurt Scheidl, Manfred W&getter English: EAaaltst gas emission of an engine running on RME at an engine test stand.
The investigations deal with a tractor Stehr WD 4 1 US7 (60 KW/220 rpm; 3456 cm3). The tractor had been running nearly 1000 hours on pure RME before the examination started.
The 5-mode cycle test was chosen as the test procedure. An undiluted part from the mainstream exhaust gas was sampled. NOx and HC samples were led through a heated filter and a heated tube (180” C). For the regulated compounds, conventional gas analysis was conducted. AIdehyde determination was done Gth GC and HPLC; aromatics and PAH were quantified with GC. Some special HC were measured using the GC-technique. The analysis of the non-re-dated compounds is described properly. All results are presented in absolute and specific (related to ener&T) values.
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The use of RME has the following effects versus DF @etroleum diesel f%el): In all:
-HC are reduced s&ificantly - Formaldehyde is essentially the same - Acetaldehyde is decreased - Acrolein increases heavily - Ethane increases heavily - Aromatics are reduced in general, but benzene increases - DF and RME are found in the same range as unburned fuels in the exhaust gases while running idle. Much uncombusted R.ME remains in the exhaust gas while the en_gine is idling. - RME reduces the PAH emissions significantly.
The conclusion is that the PAH reduction for RME should be considered. But it is also pointed out that the reduction of carcinogenic PAH is connected with the increase of carcinogenic benzene. Therefore, no definite answer is presented concerning the carcinogenic potential of EuvlE.
The authors point out that the en-ties examined had sot been modified.
Keywords: RWE, DF, HC, CO, CO,, NOx, PAH, AIdehyde, AIhmes, Benzene, Aromatics
Abstract. 7 MTZ Motortechnische Zeitschrift 43 (1982) 6
German: ~fessun,opol~~cyclisc/zer aromatischer Kohlen-wasserstoffe im Abgas von Dieselmotoren, Alfred Hartung, Joachim Kraft, Karl-Heinz Lies und Jiirgen Schulze English: Determination of Poiycyclic Aromatic Hydrocarbons in the Exhaust Gases of Diesel Engin es
Presently, determination of polycyclic aromatic hydrocarbons (PAH) in the exhaust gas of internal-combustion enLties is performed by a method that makes use of condensation and filtration of the total exhaust gas in a cooled sampling system In this study, sampling was done by extracting proportional flows from the diluted exhaust. The particles deposited on filters are sublimated, the sublimate is purified and pre-separated by silica gel.
Glass capillary gas Chromatography and thin-layer fluorometry are used as analytical methods. The corresponding PAH mass emissions measured in the diluted and the undiluted exhaust show good corrslation.
Reconmendarion. The authors had to condense the whole exhaust gas because they measured during a transient test. Lf a non-transient test was used, it would be sufIicient to condense an adequate part of the exhaust gas. Presently, VW does not work with the analytical method that is introduced.
12
But it has to be pointed out that the particle collection should not be done with class fiber hlters because PAH oxidization could occur. Teflon-coated glass fiber titers should be used instead.
Keywords: PAH, sampling procedures, analysis
Abstract. 8 RAPS-SONDERAUSGABE Mai 1985
German: Alternative Dieselmotorenkraftstoffe auf der Basis von wanzeniilen, Dr. Ansgar Scit rifer, Weinstadt English: Alternative PIan t Oil Based Fuel for Diesel Engines
The article deals wi[h the adaption of the plant oil to the eqtie (transestetication). The procedure used (transesterification) is well known. Therefore, it is not reported in this abstract.
A picture of an injector nozzle of an engine that had been running 30 hours on a blend (85% DF/ / soybean oil) is presented. A lot of residue can be seen.
Two tables with the properties of the rapeseed o;l wical DF, certified DF, and RME are --en. Advanta,oes of RhE are:
- comparable emtie wear in comparison with DF - no residues in the combustion chamber - at rated power, the energy loss is lower than expected in comparison with DF - fuel consumption is comparable to DF - soot is reduced - HC, CO, NOx emissions are comparable to DF(usually lower)
Problems that can be solved: - lubrication oil dilution, (one should shorten the oil change interval by %) - piston rings might induce problems at lon,o duration time
In all: The article reveals Mercedes Benz’s positive perspective for RME in the year 1988
Keywords: soybean, RUE, DF, HC, CO, NOx, soot, properties, duration, consumption
Abstrnct. 9 Raps, 13. Jg. (1) p. 26-27, 1995
German: Rapsdiesel und Katalvsator machen den Dieselmotor erst richtig sauber, H. Maierlt ofer English: RME and catalyst provide cleaner diesel engine exhaust emissions than DF.
The Verwemmgs_gesellschafi Nachwachsende Rohstoffe (VNR) (Society to use renewable materials) is a strong promotor for RME in Germany. They initiated the construction of a
13
100,000 ton/year transesterification plant near Wuerzburg, Bavaria.
A 4-cylinder DF engine, 4.1 L.: 77 kW/2600 rpm was tested. (13-mode cycle) fuels: LSD&ME (DIN- Norm 5 1606)
Power effectiveness was reduced about 2-j?/, versus LSD when RME was used. The effectiveness of combustion of RME increases slightly. Emissions (RME was measured with and without catalyst in percent of LSD: LSD=lOO%)
HC decreases to 60% (without catalyst) HC decreases to 109/o (with catalyst) CO decreases to 909/o (without, catalyst) CO decreases to 2% (with catalyst) Particulate matter decreases to 70% (without catalyst) Particulate matter decreases to 30% (with catalyst) NOx increases to 110% (without catalyst) NOx increases to lOS% (with catalyst) Aldehydes increase to 120% of LSD (without catalyst) Aldehydes decrease to 15% of LSD (with catalyst) Benzene increases to 11096 ofLSD (without catalyst) Benzene decreases to 20% of LSD (with catalyst) Other Aromatics decrease to 20% of LSD (without catalyst) Other Aromatics decrease to 7% of LSD (with catalyst)
The author says that PAH of LSD and RME (without catalyst) are on the same level. But the figure expresses that RME increases PAH slightly. Using a catalyst on RME exhaust gases, the PAH emissions are heavily reduced.
The author’s conclusion is that RME is an excellent fuel. Using a catalyst, it becomes even better. Soot (not figured but expressed in the text) is reduced to 30% of LSD.
Keywords: RWE, DF, LSD, catalyst, soot, HC, CO, NOx , particulate, aldehydes, aromatics, PAH
ilhstract. IO PKW-Entwicklung, Motor/Triebstrang, Dieselmotoren, 1993
Symposium Nr. 17045 / 65.325, Technische Akadentie Esslirgen Kraftstgfe aus Pflanrerzdl ftir Dieselmotoren
German: “Rapsijlmethylester als Kraftstoff im Feldversuch mit Taxen in Freiburg” Englisll: ME as fuei for a tarijleet in Freiburg, Germany
The author belongs to IkIercedes Benz and -&es a report about a taxi fleet test in Freiburg.
All tests with the 26 taxis were done without modifying any engines. A loss of 4-8% torque and
14
power was observed. In all, about 1.800.00 km were driven with RME. All taxis had a catalyst and a modem exhaust gas clearing technique. Without this technique, they would show the following results:
The averaged FTP-75 HC emission value of RME (DF = 100%) is in the range of 16 to 166%. CO has a range of 93 to 127%. For NOx, 94 to 103% are reported. The particulate matter changes to SO to 116% of the DF value. If a catalyst is used: the total amount of emissions is reduced heavily. Their relative changes (DF = 100%) are: HC 110 - 125%, CO = 95 - 115%, NOx 96 - 103%, Particulate matter 52 - 75%.
During the fleet test (March 1992 to May 1993) EU!4E was not widely accepted by the people of Freiburg because of the typical smell of the exhaust gas emission. A catalyst reduces the smell but even when the motor is cold or running idle, the smell is detectable.
Using RME, the particulate matter has a higher content of absorbed organic compounds than the particulate matter of DF. Therefore, a catalyst reduces the particulate matter more significantly in the relative value because it removes most of the absorbed fraction.
In all, Mercedes Benz fornzulates: Generally, a catalyst, in addition to an exhaust gas recirculation system reduces relevant compounds si_gnificantly. With regard to RME, a catalyst reduces HC, CO and absorbed material of the particulate matter. Mercedes Benz is of the opinion that RME should only be used in connection with highly developed exhaust recirculation/catalyst techniques.
The following paragraphs of the article abstract deal with the practical exoetiences thev have observed durina their tests: - All vehicles of the taxi fleet were brand new and had modem exhaust gas cleaning techniques. - The volumetric fuel consumption increased to about 110%. - ln July 1992, a lot of vehicles had problems with the injection nozzles (carboned-up or plugged). The investigations revealed residues of glycerol in the range of ten percent. - It is assumed that a non-controlled charge of RME with a high glycerol count caused this trouble. This problem never occurred again.
After a duration time of 80,000 to 100,000 km, problems at the injector pumps and at the fuel tubes occurred. So fluorinated materials were used to replace these components; their price is 4 to 5 times higher than the normal price for conventional materials. (It could be noted as well that RME in its winter quality is more aggressive to plastics than “summer RlVlE”).
Moreover, laboratory investigations showed that RME attacks the plastic coating of steel tanks as well. It is pointed out that tests in real life will give more detailed information in the future.
-Some cars produced more noise while fneling on DF (this occur-red while the engine was idling)
15
Durabilitv The durability behavior and the level of emissions of RME are comparable to DF. only the particulate matter emissions of Rh4E increased with time. So the level of DF was reached (at 40,000 km) and increased. This behavior is completely untypical for a DF engine. Normally, a decrease of particulate matter is observed with time. The problem with the particulate matter is not explainable and therefore is not preventable.
Residues on the &&ion nozzles and in the combustion chamber were noted. The source of these carbon residues cannot be determined. When the parts mentioned were cleaned, the particulate emissions were reduced to a normal level again.
At the time of the report, ir. was not certain what caused the high levels of particulate matter. Perhaps it is a general problem or a problem due to the inferior quality of the RME used. In all cases, quality control of RME is needed.
Moreover, Mercedes Benz fears that the discussion about the particulate matter and the smell has a negative effect concerning the acceptance the diesel en-tie industry!! So Mercedes Benz questions the feasibiliry 0fRME as a fuei for diesel enLees while operating in cities. They mention that the studies of “German EPA” (Umweltbundesamt. Berlin) must be reviewed carefUlly when make a decision to fuel with RME.
Furthermore, they point out that the RME equipment for passenger cars is not economical. (Trucks with their steel tubes are easier to convert for RME fheling.)
Keywords: RME, DF, HC, CO, NOx, particulate, durability, catalyst
Ahstrnct. 11 Landbauforschung Wkenrode, 42. ,Jahrgang (1992)247-25-I
German: Bestimmung der Schadstoffemissionen van landwirtschaftlen Schieppern beim Betrieb mit Rapsiilmethylester im Vergoleich zu Dieselkraftstoff, Jiirgen Krahl, Gerhard Vellgu tll un d Mifit Bah adir English: Determination of the Exhaust Gas Emissions of A,@uLtural Tractors Running on RME in Comparison to Diesel Fuel
The exhaust gas emissions of a small diesel engine running on diesel fuel and rape seed oil methyl ester (RME) are compared in regard to emissions of hydrocarbons (HC), carbon monoxide (CO), nitrogen oxides (NOx), aldehydes, ketones and polycyclic aromatic hydrocarbons (PAH). These investigations are based on the steady state “5 Point Test Procedure” that simulates the typical load of agricultural tractors.
HC, CO and NOx are evaluated with commercial measuring instruments. In order to determine the aldehyde and ketone emission factors, the DNPH-procedure is used. The carbonyl compounds are collected by bubbling the exhaust gas through an acidic acetonitrile solution of
16
DNPH reagent. The analysis is done by HPLC and W-detection. For analyzing PAH, a rapid determination method was developed. A part of the hot exhaust gas stream is led through a cooler and a filter. It is cooled down to about 40” C forming condensate. Together with the cooler rinsing phase, the condensed water is concentrated by evaporation and then mixed with toluene. This solution is used for the extraction of PAH from the soot particles. The clean-up of the extract is performed by solid phase e,xtraction on silica gel and thin-layer chromatosaphy. The PAH are determined by HPLC and fluorescence-detection.
Results show that there are lower emissions of HC, CO and NOx with rape seed oil methyl ester than with diesel fuel. The comparison of aldehydes and ketones reveals an increase by 30% ifthe alternative fuel is used. Formaldehyde and acrolein are the main contributors to this. In contrast to the carbonyl compounds, the PAH-level decreases by 90% if RME is substituted for diesel fuel.
It must be pointed out that no motications of adjustments and no adaptation of the en&tie were made when the tiels were evaluated.
An extended description of the sampling procedures and the analytical procedures is given in the dissertation of .I. Krahl.
Keywords: RIME, On/i, PAH, AIdehydes, HC, NOx, CO, soot, rapid deteminatio~~
Abstract. 12
German: Chancen zur Emissionsminderung durch konventionelle und aiternative fiaftstoffe,
A. A. Reglitzky, H. Schnieder, H. Krumm English: Possibilities to reduce the emission offossil and conventional fueis.
Pages 14 and 15 deal with RhG. The authors are of the opinion that the production of RME needs S5?‘0 of its ener,T for process ener,T and technical means. So the input/output ratio is about 1: 1.17. Their conclusion is the use of the whole rape plant for ener_q purposes. But the use of RME, the cake and the glycerol could improve the ratio up to 1: 1.78. Such a calculation has only a theoretical character - so the combustion of the whole plant is to be considered as the most efficient.
With regard to the German Umweltbundesamt (Environmental agency), the authors mention that the use of rape seed oil or RME would not have benefits to the environment.
Furthermore, the maximum reduction of 2.9 tons CO? per year (in Germany) using rape seed oil
based tieIs would reduce costs by 6.2 billion DM. Another way to use rape seed oil is the hydrotreating or the hydrocracking procedure. In this procedure, the pure oil is mixed with residuals of the refining process and then converted to neat DF. Some molecules similar to DF are produced. By this conversion, the price is lower (0.13 DM) than the transester5cation (0.20- 0.30 DM), and a fuel is created that can be taxed. Up to now, no ener,T balance - especially for
17
the hydrogen production - is introduced.
Keywords: rape seed oil, RME, glycerol, energy balance, hydrotreating; hydrocracking
Abstract. 13 Proceedings: Rapsolmethylester, Vienna S. 47-57,1992
German: B:‘odiese! - Frye,?, F&2:: und r/orsch!tige ms der Scht VG:: Fezd, 0. Syassen, Xaver Fend & Co., Marktoberdorf Englisit: Biodiesei - Questions, facts and proposals from the view of Fent (tractor manufacturer in Germany)
Facts: Rape is a plant with a lot of properties for agriculture and the environment. Its energy balance is about 1:2.7. The yield ofrapeseed oil in Europe is in a range of 1000-1300 l/ha. It is assumed that this yield can be doubled - as wheat is the predominate crop grown during recent years.
Diesel engines have a high degree of efficiency and can be driven with RME without great problems. Black carbon is reduced about 50%. Durability tests reveal good results for RME. In some cases: replacement of injection nozzles was necessary. The lubrication oil dilution was observable, but it did not lead to a shorter oil change interval.
Keywords: Rh4E, DF, smoke, injection nozzles, lubrication oil, dilution
Abstract. I4 GIT Spezial - Chromatographie 2/91
German: Bestimmung von PAHs in Kraftfakeugabgasen durclt HPLC - Teil2, D. T. Kascitani, A. Brauns English: Determination of PAHs in Automobile Exitaust Gases by HPLC - Part 2
A chromatographic procedure using solid phase extraction (SPE) for the preparation of samples and high pressure liquid chromatography (HPLC) with fluorescence detection for the separation and determination of 25 polycyclic aromatic hydrocarbons (PAH) in the exhaust gas Corn gasoline and diesel engines of passenger cars is described. SPE was used for economic reasons and a fluorescence detector was used for its sensitivity. The fluorescence extraction and emission wavelengths were changed during the chromatographic analysis to optimize the selectivity for individual PAHs.
The collected PAILS were extracted, the extracts combined, and if applicable, the PAHs were further purified using SPE over water-deactivated florisil and biobeads. The purified and concentrated solutions are separated on a reversed-phase C 18 column and detected with a fluorescence detector. The quantification is done by means of an external or internal standard. The limit of detection of the individual PAH in the HPLC step is 10 to 210 pg. The detection limit of the procedure is 0.2 to 3.1 @sample. Standards deviations of repeatability of 17 selected
18
PAHs in the HPLC step are between 1.8 to 7.8% by n = 6. Standard deviations of repeatability related to the entire procedure (sampling and analytic) are between 5.8 to 24.8% by n = 5.
Results obtained by use of these SPE-HPLC methods are compared with results obtained by gas chromatopaphy, showing some correlation. The research suggests that branched PAHs may disturb the quantification of PAH with 2 to 4 rin,os. In particular, aldehyde and py-renes chanse to chrysen and triphenylen.
Keywords: PAH, HPLC, solid phase extraction, rapid determinatiorl
Ahstrnct. 15 JI Case GmbH - NeusdRhein 1994
German: RME/SME Untersucitungsergebnisse fkglisit: RME/SiVlE Results of IO00 hour durability tests
The report deals with the comparison of RME and SME with special regard to me1 properties, power, fuel consumption, exhaust gas emissions, durability, and conclusions of these aspects. The report has a lot of tables that demonstrate very clearly the outcome of the testing. In contrast to the text: the pictures are _&en in English.
The slides show si_gnificant differences between RME and DF but a comparison of DF, RME, and SME is not always presented.
A large difference is noted between RME and SME: RME has an iodine number of 115, whereas SME has a iodine number of 140. (The German norm and the Austrian norm allow a maximum limit of 115.) This difference is caused by the different composition of soybeans and rapeseed. Soy has more unsaturated fatty acids. Therefore, there is the danser of polymerization of SME if it reaches the lubrication oil.
The cost for the transesterification is assumed to be about 0.40 DM per liter.
HC emissions are reduced using RME or SME versus DF. In addition, a blend of 30% SMEI70% DF was tested. It increased the HC emissions to a value between that of DF and SME.
In general, there were no differences concerning the HC, CO, NOx and PM emissions of RME and SME when they were compared to DF. The opacity does not correlate to the PM because there is more HC absorbed at the surface of the soot particles resulting from RMWSME than at the surface of the DF soot particles.
For both alternative fuels, constant operation at rated power was better than chargtig loads. Both fuels have a sli@t tendency to form a deposit at the top of the injection nozzle (as is formed when fueling with DF).
19
Both fuels lead to a slight dilution of the lubrication oil. These effects are stronger using SME than when using RME. When using RME, a slick was formed in the lubrication oil. This is due to the hii_& level of unsaturated fatty acids of SME. Some results of lubrication oil analysis are given, but they are not discussed in the te,xt.
III all the results are: - No wear of the em&e using RME - Higher wear of the engine using Sh4E (The emissions are not discussed in the conclusion)
Keywords: SUE, RALE, DF, emission, wear, lubrication oil dilutron
Grundhgen der Landtechnik 35 (5) P. 137 - 141 (1985)
German: Methylester von Raps61 als Kraftstoffftir Schlepper in Praxisseinsatz, G. Vellguth English: RME as a fuel for agricultural tractors.
The use of methyl esters of rapeseed, soybean and sunflower oils reduces the impact of carbon base residues in the engine [see also literature no. 5-S].
The transesteritication process: 100 kg rapeseed oil + 11 kg methanol + 100 kg RME + 11 kg glycerol 100 kg rapeseed oil + 16 kg ethanol + 105 kg RME + 16 kg glycerol
The test tractor of the FAL is introduced. Lent farmers 306 LSA 4-cylinder MAN-engine type D226.4; 52 kW/2200 rpm A drop in torque (10%) was noted when operated on RME.
Lubrication oil dilution occurred. It was not possible to reduce this condition by changing the injection angle to -4” as with the test en-tie (see Vellguth, 1952). It is known that even with DF, lubrication oil dilution occurs when the en-gin-e does not become warm Therefore, the initial temperature of the thermostat was changed from 75°C to 87°C (see fig. 5a - 5g).
The oil analysis results suggest that the elevated coolant temperature was beneficial for the engine (see fig. 511). The dilution after 200h (87°C) was comparable to that of IOOh (75”).
In subsequent intervals (jk), the RME content was lower (5/7%). Changing the thermostat can be considered a solution for this problem. But fi g. 5 (Lm) shows that increasing the coolant temperature is not always the solution, as engine operation/load may allow the engine to operate below the optimum coolant temperature.
To compensate for the loss of torque, the injection nozzle volume was increased.
Keywords: RWE, lubrication oil dilution, torque loss, injection angle
20
Abstract. 17 Motortechnische Zeitschrifu 43 (6), p. 262-266 (1982)
German: Messungpofycyclischer aromatischer Kohlenwasserstofe im Abgas von Dieseimotoren, Hart& A., J. fiaft, R H. Lies & F. Schulze English: Determination of PAH in the exhaust gases of diesel engines
The szmqhg procedures used are of wortance. The authors had to condense the entire exhaust gas volume because they measured durin_e a transient test. Lfnon-transient tests were used, it would be sufficient to condense a sample of the exhaust gas.
Presently, VW does not work with the analytical method that is introduced. Collection of particulate matter should not be done with glass fiber filters because of possible PAH oxidation. Teflon-coated glass fiber fdters should be used.
Keywords: PAH, sampling procedures, analysis
Abstract. 18 Grundlage der Landtechnik 37(6)? p. 207-213 (1987)
German: Emissionen bei Verwendung Alterniativer Kraftstofe in Schlepper Dieselmotoren, Vellgu th, G. English: Emission of Tractors Running on Alternative Fuels This paper introduces the 5-mode cycle for aecultural tractors. Table 1 shows the location of these points on the engine torque map. Table 5 shows the time coefficients of this mode in correlation to different powers of tractors.
The gas analyzers for the regulated compounds are introduced in detail (chapter 3.3).
Table 6 and Figure 2 suggest a flaw in the findings of the research. These must be taken into account when results are discussed.
Regulated emissions of DF, RIME, and blend are shown in Figure 5.
Keywords: J-mode cycle, bled, gas, analyzers, variety of n~easuring errors
Abstract. 19 Gtundlagen der Landtechnik 30(2) p. 40-51 (1980)
German: Pflan~eniile fiir die Kraftstoff und Energieversorguing, Bartef eL al. E~l,o(i~h: Vegetable Oils for Fuel and Energy Pqvoses
The paper deals with ener,T balances. However, there are currently newer and more sophisticated calculations. Some information that may be of interest include:
21
Table 1 shows the compositions of different oils (e .g. soy/rape) (a translation is in the text). Table 2 shows necessary amounts of fertilizer. Table 5 shows loss of ener,z in each puritication step of the fuel production. Table 6 shows the phosphorous and free acid content of soybean and rapeseed. Table 7 shows physical and chemical properties of 7 oils compared to DF.
Keywords: physical, chemical properties
Abstract.20 Raps 13 (l), p. 28 1995
German: Fahrzeugfreigabe fiir den Betrieb mit Biodiesel, Bockey, D. English: The Approval of Biodiesei by Veiticle Producers
Benefits of RME are introduced. Of importance is the high cetane number and oxygen content of 1 lo/. Engineers expect a large potential of development with special regard to the properties of RME. Until now, the engines have been optimized only to DF.
A table gives an overview of which manufacturers allow the use of RME in their vehicles.
Keywords: RA.4EV engine development, allowance
Abstract.21 Motortechnische Zeitschnft 51(l) p. 12-17, 1990
German: Schneilverfahren ziir Bestimmung der PAK- Werte, Hartung A. English: Rapid Determination of Selected Polycyclic Aromatic Hydrocarbons in Motor Vehicle Exit aust
Due to incomplete combustion, numerous polycyclic aromatic hydrocarbons (PM) and PAH- derivatives are present in motor vehicle exhaust, Figs. 1 and 3. Extensive sample preparation and analytical work would be necessary to analyze these compound groups thorou~rjily. Concerning en-gin-e development and assembly line testing, though, determination of a selected number of these compounds is sufficient: Fig. 4 and 7. In regard to this purpose, a rapid determination method was developed, making use of coupling high-performance detection. UV- and fluorescence analytical results agree well with gas-chromatographic values, Fig. 8, for various engine concepts (diesel and gasoline with/without catalyst). Gas-chromatographic methods, however, require extensive sample preparation.
This procedure works well ifnew entities are examined. PAHs derived from diesel engines with high smoke numbers cannot be determined accurately. Presently, VW uses solid phase extraction procedures based on silica gel and sephaclex techniques - but this procedure works only on new en_gines.
22
Keywords: PAH, rapid determination Absiract. 22 Abschlufibericht, UniversitHt Kaiserslautern, 1994
German: Untersuchungen zum vergleichenden Einsatz von Dieselkraftstoff und Raps6imethyiester an verschiedenen Dieselmotoren English: Comparison of DF and RME on Different Diesel Engines
This study deals with the comparison of DF and RME. The influence of an oxidation catalyst with special regard to PAH and aldehydes is presented.
Passenger cars: -Volkswagen Ventre l.jL, turbocharged, catalyst -Audi 80 TDI, turbocharged, catalyst. Both are examined according to ECE/lXJDC-test and to FTP-75. -HC, NOx, PM, PAH, and aldehydes were compared. -The results show that RME has positive effects on HC, PM, and PAH (30%). Heavy-dutv ensrines tested: -Deutz-MWM, 3-cylinder tractor -Mercedes Benz OM 40 lL, 6-cylinder bus engines -The regulated compounds were determined according to 13-mode cycle. The non- re-dated compounds were determined according to IS0 8178 D2.
This test was modified for generating data with intermittent load. The data cannot be used to make comparisons to either tractors or buses because it consists onIy of rated speed modes. The results show significant reductions of PAH, PM, and HC.
There is indication of the relative standard deviations of the results, although values of aldehydes and PAH are presented to the hundredth part.
Keywords: PAH, oxidation catalyst, 13 mode testing, IS0 8178,emissions
Abstract. 23 All new VW- Diesel models can be fueled with Biodiesel Wolfsburg, Sept. 12, 1995
Starting in 1996, all VW models that have economical diesel engines can be alternatively fueled with mineral oil diesel, biodiesel or a desired mixture of the two. The biofkels rapeseed oil methly ester(RME) or “plant methyl ester” (PME) is a renewable resource that is being grown on uncultivated (or fallow lying) fields.
The emission of carbon dioxide, hydrocarbons and carbon monoxide as welI as particulate matter is reduced with the use of RME or PME, without reducing the engine performance. In this way, biodiesel not only preserves natural resources but also represents active environmental protection.
23
All Golf and Jetta (in German: Vento) models after 1992 that have an IDI-diesel engine can be adapted for use with biodiesei.
Volkswagen is the first automobile manufacturer to provide a program for the use of these renewable firels.
Keywords: ME9 PME, emissions, Volkwagen
Recommendations Concerning Documents to Translate
A recommendation concerning whether or not an article/document should be completely translated has been made on a case by case basis. A list of documents that Dr. Krahl felt should be completely translated follows.
1.
? -.
3.
4.
5.
6.
7.
S.
9.
‘Bestimmung der Schadstoffemission von 1andwirtschafUichen Schleppem beim Betrieb mir Rapsolmethylester im Vergleich zu Dieselkraftstoe” Krahl, J.; translate all 99 pages- (exhaust emissions from a_ticultural vehicles)
“Zytotoxizitat und Mutagenitat von Diesem bei Verwendung von Rapsohnethylester als KraftstofX” Stalder et al., translate 4 pages (q-toxicity and mutagenicity of RME particulate matter)
‘XME-Einsatz in Traktoren,” Krahl et al., translate 3 pages (use of RME in tractors)
“okobilanz von Raps61 bzw. Rapsijlmethylester als Ersatz fiir Dieselkraftstoff,” Drechsler et al., S ummarize 1 l-page article (ecological balance of RME and rapeseed oil as a substitute for diesel fuel)
‘??flanzenole als Kraftstoffe fir Fahrzeumotoren und Blockheizkraflwerke,” VDI Berichte, translate the table of contents, 2 pages (vegetable oils as fi.rels for diesel engines)
“Anbau and Verwertung nachwachsender Rohstoffe,” translate series of short abstracts (Cultivation and use of renewable resources)
“Abschlussbericht: ErWrungen beim Betrieb von Linienbussen der Verkehrsbetriebe Ziirich mit Rap smethylester,” 50 pages, translate figures only (experiences fueling city buses in Zurich with RME)
“Chancen und Problematik nachwachsender Kraftstoffe,” Parts 1 und 2, 15 pages, summarize (Opportunities and problems encountered with renewable resources)
“Biodiesel in Europa 1994,” Connernan, J.; 12 pages, summarize (proceeding for a biodiesel conference)
24
10.
11.
12.
1;.
‘Neuere Untersuchungen iiber die Umweltvertriglichkeit und die Dauerstandfestigkeit von Vorkammer- turd direckteinspritzenden Dieselmotoren bei Betrieb mit Rapsijl und Rapsolmethyletier,” May et al., 20 pages, translate short summary (durability results for direct injected engines while fueled with rapeseed oil and RME)
‘Tinsatz von Krafisroffen aus nachwachsenden Rohstoffen in VW/Audi Dieselmotor,” Weidemann et al., 21 pages, summarize (use of renewable &els in an Audi diesel en-gin-e)
‘Pilot project ‘Biodiesel’,” Woergetter and Schrottmaier, 14 pages, short summary
“Emissionen von Pflanzenol-Kraftstoffen und ihre Umweltwirkungen,” Selected articles, translate total of approx. 22 pages (emissions from vegetable oil fireIs and their effect on the environment)
Update NBB about European Biodiesel Activities
Several E-Mail have taken place between been the principal investigator and Dr. Krahl before and after his return to Germany. Hi~&lights that were most interesting included:
1.
2.
?.
a
4.
6.
The Elsbett engine company went bankrupt and is now part of Heizomat. Elsbett produced an engine that used raw vegetable oil rather than methyl esters.
Mercedes Benz has published new findings concerning biodiesel fueling. Juergen is securing copies for NBB.
The biodiesei plant in Bruck Austria has closed. They were unable to break even with their production costs.
Volkswagen has developed a kit that sells for 560 DM or approximately $400.00 that permits warrantee biodiesel fueling. Mercedes Benz has developed a similar kit.
Juergen is presently conducting emissions tests with using a modem VW en-tie (during the first week in July).
He reports that a researcher by the name of Fiedler (1995) has been able to reduce NOx by 30 to 40 percent under specific conditions. He is sending a copy of the paper for NBB. (Injection pressure was increased by lo%, timing retarded by 10%)
25
Several FAX and E-Mail have been undertaken by the principal investigator and Dr. Krahl since the start of the project began. Dr. Krahl noted by E-mail that several documents would be sent to MU for review. MU received 12 additional documents in the mailing that followed.
1. List of biodiesel production facilities in German, France, Italy, England, & Belgium. 2. Press release Corn Mercedes Benz concerning the sale of their ‘biodiesel engine”. 3. Overview of the Tntemationales Wiener Motorensymposium (5/5/95). 4. New Biodiesel plant opened in Germany. 5. Biodiesel plant closed in Bruck, Austria. 6. List ofbiodiesel plants in Europe (11 countries, 26 different plants). 7. Using RME in two-stage high pressure injection systems. 8. Using glycerin as a feed. 9. UniMOG and use of rapeseed oils for hydraulic purposes.
10. MAN will allow the use of RME, but not sunflower oil. 11. Mercedes Benz service information for fueling with RME. 12. Fueling the Golf(Volkswagen) Ecomatic with Biodiesel.
Mercedes identilied a complete list of the parts that must be changed to make the [email protected] and engine fuel system ready for biodiesel fueling. The list of parts that must be exchanged include:
1. Injection pump 2. Diesel fuel filter 3. Seal for the diesel fuel filter 4. Rubber caps must be replaced on cylinder 1 and cylinder 2 5. Fuel line to the fuel tank 6. Fuel line to transfer pump 7. Fuel line to heat exchanger S. Fuel line from heat exchanger 9. Heat exchanger
10. Fuel thermostat 11. Fuel tank 12. Fill tube for fuel tank 13. Seal for fuel tank 14. Strap around fuel tank and padding for strap 15. Tank me1 filter 16. Fuel vent tube for fuel tank 17. Fuel line to fuel filter 1% Return fuel line to he1 tank 19. Seal at bottom of the tank 20. Fuel level indicator 2 1. Biodiesel name plate (BD = OK) on vehicle 22. Biodiesel label under the hood of the vehicle
26
Presentations/Oj,dutes Given By Dr. KrahI
Dr. Krahl’s work concerning Pm emissions analysis has direct implications concerning fUtu.re research and marketing planned by the NBB. It has even greater implications concerning regulated emissions levels set by the EPA For example, Dr. Krahl found that he could increase the mass of the PM by nearly twelve before the cancer-causing potential of the RME PM equaled that ofpetroleum diesel fiiel. E-le also was able to prove that RME particulate matter is much larger than petroleum diesel meL These &lings clearly suggest that the standards, which were developed for petroleum diesel fuel that were based on the cancer causing potential and the size of the PM, are not appropriate for RME. Lfone keeps this in perspective, realizing the fact that PM and NO, are inversely related, the diesel engine can be tuned to much lower levels of NO, than what is possible when fueling with petroleum diesel fuel.
This is a de&rite marketing advantage for biodiesel. The fact remains, however, that Dr. Krahl’s work is based on 100% RME. Research should follow that allows similar comparisons to be made with soybean derived biodiesel as well as biodiesel blends. A complete reproduction of the transparencies used by Dr. Krahl can be found in Appendix A.
Sharing of Biodiesel Research/Knowledge Conducted by Dr. Krah I
Ms. Elser completely translated a paper written by Dr. Krahl that can be found in Appendix B. This paper outlines the analytical methods that he recommends when quantifying the chemical properties of biodiesel. Specifically, the analytical methods used to determine the PAH or polycyclic aromatic hydrocarbons that are produced when fueling with biodiesel are discussed.
Translation Training for German Speaking Chemistry Student
Nancy Elser, a graduate student who earned her MS degree in analytical chemistry while living in Germany, has met and visited with Dr. Krahl concerning the translation of technical German documents. Ms. Elser has translated a document that explains the durability research that was conducted by CASE-M in Germany. CASE-M fueled 3.9L, 5.9L and 8.3L engines for 1000 hours. She has also completely translated a paper written by Dr. Krahl that focuses on PAH emissions associated with biodiesel fieling. Ms. Elser has expressed an interest in performing additional translations for NBB after the close of this project.
Suggestions concerning the revision of the paper recently translated by Ms. Elser were provided by Dr. Krahl. Dr. JKrahl forwarded these to the University of Missouri via E-Mail.
27
Overview/Summary written by Dr. Krahl
From my point of view, the fist contact in June 1995 was an important step to begin a new cooperation between researchers from the USA and Germany, who both @r. K&l& Dr. Schumacher] conduct practical research on biodiesel.
Both FAL, MU (and N3B) have conducted research that enables a more precise estimation of the potential use of biodieseL
In detail, it was demonstrated that the sharing of certain knowledge led to an increase of know- how, especially in the area of biodiesel exhaust emissions and their environmental effects. The NBB profits more f?om this additional knowledge because commercially, biodiesel has less economic potential in the USA than in Germany. This is due to differences found in fossil fuel prices in both countries.
Presently, we European biodiesel researchers] are be-Pinning to formulate an argument that the reduction in the carcinogen&$ of the particulate matter must be taken into account when commercializing biodiesel. Additionally, the positive effects of non- regulated compounds can be an important ar_ment to offset the s&_&t NOx increase found in biodiesel exhaust.
For fi&ure work I propose:
1).
2).
3).
The cooperation should continue. NBB should enable Dr. Leon Schumacher and an European researcher of his choice to conduct research that quantifies the environmental effects of biodiesel. In particular, the non-regulated compounds such as PAH and aldehydes, in addition to mutagenic and cytotoxic effects must be investigated. Further, Dr. Schumacher should organize a meeting with competent scientists of the Environmental Protection Agency (EPA) and/or the California Air Resources Board (CARB) to inform them about NOx and carcinogenic effects (benefits) of RME (please note that these effects/benefits have yet to be researched and documented for SME).
NBB should initiate research that quantifies the aldehyde and PAH emission associated with biodiesel tieling. I suggest that Dr. Schumacher coordinate these efforts. Nancy Elser, Mu Chemistry student and German translator, is qualified to conduct much of this research. I am willing to provide Dr. Schumacher and Ms. Elser special training during the fall, 1996, in Braunschweig, Germany to facilitate this research. Training Ms. Elser and Dr. Schumacher would reduce the cost to conduct this research in comparison with the costs of developing new PAH-analysis procedures that I found are needed when analyzing biodiesel exhaust. NBB would need to buy/rent a HPLC to take advantage of this training session upon their return to the USA.
NBB should provide the resources necessary so that I can determine the carcinogenicity of SME versus DF. I believe that Professor Dr. Stalder (FAL researcher) who is an expert
2s
On this area is willing to assist with these investigations.
4). IfNBB intends to learn more about European biodiesel research, they should continue their review of literature and German translation activities. Money spent in this manner is as beneficial as conducting their own research. It also places the NBB in a stronger position to promote and commercialize biodieseL
IfNBB would like to work with me in the future, NBB should seriously review my proposals and/or suggestions and discuss them with Dr. Schumacher and myself These cooperative research and translation activities should continue between NBB and myself In my opinion, this would most easily be accomplished if Dr. Leon Schumacher worked out a new contract of cooperation that would enable work to be conducted at FAL (in Germany), or if desired, at a research laboratory located in the USA.
In summary, I agree to future endeavors with the NBB. Both sides WB and FAL] should try to find an efficient and proactive way for mutual cooperation.
SUMMARY
The benefits of Dr.Krahl’s travels to the United States to help translate biodiesel documents were twofold. As an expert in his field, Dr. Krahl offered an accurate translation, and went further by “filling in information” concerning the research that was not be evident from the writings. The exchange of theories and findings that have taken place between Dr. Krahl and biodiesel researchers in the United States has been mutually beneficial to all parties involved.
29
Appendix A
Jiirgen Krahl
Institute of Biosystems Engineering Federal Agricultural Research Centre
Braunschweig - Wkenrode, Germany
Location of the FAL in Europe
Federal Agricultural Research Centre Organizatimal Structure
Bodies
Research Institutes
pg-l-a
Central Institutions
; . . . . .
. :
1. Structural Research
Data Processing Center Central Library
Experimental Station Information Services
Phe use of rape seed oil
I . Introduction
2 . Motivation
3 . Measurement
4. Results and effects
Arguments to use renewable resources for energy purposes
0 protection of fossile resources
0 alleviation of the farmers’ problems
0 environmental aspects
Institute of Biosystems Engineering -.-i::;
Material circle for rtipe as renewable energy source
Injection nozzle of a DI-engine running
50 hours on rape seed oil
irxtitute of Biosystems EnGineerinS: &;:
Possible use of rape seed oil as fuel
@ Adaption of the engines to the oil
- Elsbett-engine
- chamber-‘and DI-engines (KHD, MWM, TMW...)
0 adaption of the oil to the engine
- transesterification
hvdrotreatina
institute of Biosystems Engineering ;.;,.;
zi E .- 0 d)
I I
0 1
0 - N
-
Characteristics of Diesel fuel, rape seed oil and RIME
Diesel rape seed RME
fuel oil, refines
heating value MJ/kg 40.6-44.4 37.6 37.2
density (20 “C) kg/l 0.8-I-0.85 0.91 0.88
vol. heating value MJ/I 35.2 34.4 32.7
kin. viscosity mm*/s 1.2-10 98 6.3-8.1
(20 “C)
Cetane number CN > 45 51 54
lnsriture of Bicsvsren?s Engineering __:..
Energy balance of rape seed oil methylester (RME)
sun sun energy energy 156 GJ/ha 156 GJ/ha
technical technical means means 17.7 GJ/ha 17.7 GJ/ha
P E L E
-
rape straw 78.2
GJ/ha
rape seed 77.8
G J/ha
- F “0
-
phosphatides etc. 1.5 GJ/ha
glycerine 28.2 GJ/ha
ra e seed oi raw P 49.6 GJ/ha
,2.2 GJ/ha
process ’ energy 4.6 GJ/ha
’ factory (0.3 GJ/ha) ’ transesterification
(On4 GJ’ha) methanol degumming (0.5 GJ/ha) 2.7 GJ/ha
energy IossL 23.1 GJ/ha
lnstltute of Blosystems Englneerlng
sossible substitution of Diesel fuel in Germany via rape seed oil ba- sed fuels
quota of plough-land
sstern Germany lossible production - traditional use - for use as fuel - substitutes DF Iota of DF consumption ---_-~ ------
w Germany lossible production : - traditional use - for use as fuel - substitutes DF ota of DF consumption
10%
( w 800
(1 t> ( 690
(W 110
(k9 96 0.5 % -..-_--_,--
(kt) 1320
( w 870
(kt) 450
( w ‘7 390 1.6 %
15%
200
690 510
444
1
2.7 %
1980 2640 870 870
1110 1770 970 1540
4.1 % 6.4 %
Institute of Biosystems Engineering Federal Agricultural Research Cenlre
20 %
1600
690 910
790 4.8 % --
se of rape seed oil
I . Introduction
3 .
4 .
Measurement
Results and effects
Schematical description of a Diesel soot particle
Institute of Biosvstems Enaineerina :
EPA standard 610
Naphthaline Acenaphthylene Acenaphthene Fluorene
Anthracene Pyrene Benz(a)anthracene
libenz(a,h)anthracene Fluoranthene Benzo(b)fluoranthene
- I
w
Chrysene
Benzo(k)fluoranthem
mzo(a)pyrene Institute of Biosystems Engineering
Benzo(ghi)perylene Indeno(l,2,3-cd)pyrene Federal Agricultural Research Centre
Braunschweig -- Wkenrode, Germany
Ozone forming potentials in g OJg component
@ Alkanes (61) 01
Methane 0.01 Ethane 03 Trimethylpentane I:6 Methylcyclopentane 2.8
o Alkenes/Alkines (47)
Ethene Propene Butadiene Propine
o Aromatics (33)
Benzene Toluene Xylene Trimethylbenzene
8 Aldehydes (9)
. I
06
Formaldehyde 7.2 Acetaldehyde 5.5 Acrolein 6.8
06
7.3 9.4 9.4 4.1
05 .-
0.4 2.7 7
IO
Institute of Biosvstems Enaineerinn
se of rape see ase uels
1 .
2 .
Introduction
Motivation
4 I Results and effects
Engine test stand and measuring device
-
impingers
I-- --
up
-
1 HPLC &, 4 clean-up ‘* cooler
n-l I FLD
lnstltute of Blosystems Englneerlng - W- condensate beueral Agricultural Research Centre . : y, Braunschweig - Vdkenrode, Qermany
Technical description .of the engines us.ed
/-- Rape Seed Oil/DieselFuel
1. MB-trac 1000 6 cylinders, 70 kW, Elsbett modified
6 cylinders, 70 kW, Elsbett modified
3. Deutz D 6206 alias Deutz (I) 4 cylinders, 42 kW, swirl 1 chamber
4. Deutz D 6206 alias Deutz (II) 4 cylinders, 42 kW, swirl/ 1 chamber I
i-1- RME/Diesel Fuel
5Farymann K54 1 cylinder, 3.5 kW, directin- jection
6. FendtFarmer306 LSAalias 4 cylinders, 52 kW, directin- Fendt (I) jection .c
7. FendtFarmer306 LSAalias 4 cylinders, 52 kW, direct in- 1 Fendt (II) jection I
-.
I’ 1 ; , ,
Institute of Biosystems Engineering ,.d’& J Feoeral Agricultural Research Centre
j (F-31: i Sraunschweig - Vdlkenrode. Germany ~+&g?
.
8
Performance characteristics of tractor engines-
work procedures and time coefficients
engine torque*
%
engine* load
%
load mode
engine time coefficient
%
work procedures
primary tillage and full load p.t.6.
standard p.t.o. on road and off road transport runs
cultivation operations without p.t.o. low range work procedures, partly with creep speed road transport runs, manoevring
idle running
speed* %
A 84 95 88 31
18 e 41 48 85
21 6 40 53 19
20 D 15 100 15
E 0 0 ‘12 40
average average total 100
z1 (A-E) average 41 47
* related to rated values for rated power
- . . :
Aldehydes/ketones sampling probe
-
1
Jr-
-4
-- c
pll0
part stream
exhaust gas stream
Institute of Biosystems Engineering Federal Agricultural Research Centre Eraunschweia - Vblkenrode. Germanv
Fundamental reaction of the aldehyde/ketone determination
NO \
2
R n \
/ C = 0 + H2ii - NH- - NO 2
RI
R n \
/ C iii - iH
R, :
NO \
2
RI = H or Rn ‘,
- NO2 + H20
Institute of Biosystems Engineering Federal Agricultural Research Centre Braunschweig - Vblkenrode, Germany
HPLC-chramatogram of a aldehydelketone sample
10
, . a 5.60’ - ’ io.bo’ ’ ’ i5.b n
. I , I 20.00
time (min)
Signal of the syn- and
anti-2,4-dinitrophenylhydrazine of
acetaldehyde
time (min) _a
‘r7stitlJte oi Siosvstems Erloinpnrinn
lsomeric forms of syn- and anti- 2,4=dinitrophenylhydrazines
RI = H (aldehydes) RI c R2 (ketones) NO 2 NO 2
/N \ lN \ H N H N
/I /I / c\ /C\
R2 RI RI: R2
SY” anti
Particulate and PAW sampling probe
’ I I i 1 I
exhaust gas stream ; i
4 ///f//f//f//////Y/////////////.~////// bm 400 I-- 400 -_ .--_- -4 -
Institute of Biosystems Engineering Federal Agricultural Research Centre Braunschwelo - Vtjlkenrode Germnnv
\ \ ‘\ \ ‘\ \ I
-. *. =\ \ -. -. : ‘\ \ -. I /
-. *. ‘\ \ *. -. .* ‘\ -. -. _. i ’ I \ =-.. ‘\ \
c.3 =-... ‘\ \ CD **-..-\ \
0 .- =..:q I
+ ‘. ’ 2
‘.:\I . -Q
a, P ca - 2 F ‘0 .- E .-
F .- - a. E a cd 0 .- zi c .- 0 z .-
I
I I i / ./’
i / i *,.’ _. /
Effects of non - isokinatic sampling
ti I I
d
procedures
I I I
t
I I \
\
wP < Wm WP ’ w, Biirkholz, 1991
wp probe velocity
w, main stream velocity
mstitute of BiosystecS Znqineerina
HPLC-chromatogram of a PAH sample before thin layer purification
5.00 10.00 15.00 20.00 25.00 30.00 time (min)
Scheme of a loaded TLC plate. i with different wave-lent ‘c
I I I I -~
I I .
sample
iluminated ths
EPA standard
HPLC-chromatogram of a PAH sample after thin layer purification
1
2
I, I I I 1,
1 1 r ,‘I’ 11
’ “‘I””
\ I
15.00 20.00 25.00 30.00 35.00 40.00
time (min) _,
1 . Introduction
2 . Motivation
3 . Measurement
Institute of bsystems Engineering :Y~!‘;
Comparison of chrysene signals at different excitation/emission
280/430 nm
wave- length
290/430 nm 290/450 nm
Federal Agricultural Research Centre
Wave-length program of the fluorescence detector wave- length program:
Fluoranthene Pyrene
excitation mm1
237 237
emission [ 1 nm 440 440
IO
Benz(a)anthracene Chrysene
290 290
450 450
13
Benzo(b)fluoranthene 297 4.60 13
Benzo(k)fluoranthene 290 425 Benzo(a)pyrene 290 425
13
Di benz(a, h)anthracene Benzo(ghi)perylene
Indeno(l,2,3-cd)pyrene
290 290
14
3- Quaterphenyle
410 410
504
335
13 27
247 ‘3
220 11 32
gain time [min] 0
17.3
22.0
24.05
29.9
Braunschwelg - Wlkenrode, Germany
1 .ooo
mgh
800
200
0
Emissions of aldehydes and ketones; Fendt tractor (1) 2478.12 2676.03 1243.04
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .._......
DF RME Federal Agricultural Research Centre
Weighted, relative standard deviation of aldehydes- and ketones-quantifications;
Fendt tractor (I)
Formaldehyde Acetaldehyde Acetone Acrolein Propionaldehyde Crotonaldehyde Butanone Iso butyraldehyde Benzaldehyde ’ Hexanaldehyde
7 weighted, relative standard
deviations of single aldehydes and ketones
in %
DF RME
2 2 4 6 7
13 7
12 16 24
2 3 3 3 4
.- 15 6
IO IO
6
I
I
I I
MO14 SSEXU pa$ywa
Weighted, relative standard deviations of the PAH -qutintificati’ons;
Fendt tractor (I)
weighted, relative standard deviations of’single PAH
in %
DF RME
Fluoranthene 6 II Pyrene 6 12 Benz(a)anthracene 7 14
Chrysene IO 8 Benzo(b)fluoranthene 9 II Benzo(k)fluoranthene 9 II Benzo(a)pyrene 16 .- 7
Dibenz(a,h)anthracene .I1 18
Benzo(ghi)perylene 7 11 Indeno(l,2,3-cd)pyrene 8 8
institute of Biosystems Enqineerir,s :.I: -.
Relative emissions of the engines fueled with rape seed oil
350 I- 0 / 0
300 I--
250
200
150
100
50
0,
1 MB-trac EEI Unimog Dkutz (I) q Deutz (II) lnstltute of Blosystems Englneerlng Federal Agricultural Research Centre Braunschwela - Vdlkenrode. Germanv
Relative emissions of the engines fueled with RME
35c %
3oc
E 25C
7 200
2 ; 150
100
50
0
I-
)--
I--
l--
I--
l--
Iii Farymann Iii! Fendt (I) Fendt (II) lnstltute of Blosystems Englneering
Federal Agricukural Research Cenire
m > El
W > cc
300 wvh
250
200
1
Weighted, specific emissions of aldehydes
150 -
100 -
50 -
O- Fendt I Fendt II MB-trac Unimog Deutz I Deutz II
Diesel fuel RME 0 rape seed oil lnstltute of EHosystems Englneerlng Federal Agricultural Research Cenlre
1200 pg/kWh
1000
800
600
400
Weighted, specific emissions of PAH
3257
Fandt I Fendt II MB-trac Unimog Deutz I Deutz II
RME q rape seed oil . Federal Aencultural Research Centre
Mutations of Salmonella Typhimurium TA 100 induced by the extracts of particulates derived from DF and RME
volume PI
200.00 1272
100.00 1024 50.00 : 615’ 25.00 252 12.50 313
6.25 277 .,
number of mutations
rated power
DF RME
450
376 276 208 183
I DF RME
591 490 395
. 278 216 188
:
119 149 150 140 103 126
Institute of Biosystems Engineering Federal Agricultural Research Centre Braunschweig - Vblkenrode. Germany
+ u-4 a4 4d4 ‘3 -4izbd uid rvUi&i U3CU)ry
photographs of particulate filters of a Fendt tractor
Reduction of particulate mass
T = 2O”C, ret. humidity 50 %, P - IO5 Pa
091 I L L I 1 1 extraction
0 20 40 .,60 80 100 120 i vacuum
., time[d] PwlPa
Fendt tractor (II), 16.04. -30.08.1993 5-mode-cycle
lnstltute of Blosystems Englneerlng Federal Agricultural Research Centre Braunschweig - Vdlkenrode, Germany
Cytotoxicity of parti& DF and
& ca E 2 - 8
90 0 /
8;
70
60
50
40
30
20
IO
0
ates derived from 3ME
undeluted extract
Diesel fuel RME water
Institute of Biosystems Engineering 2;:~
Conclusions
Rape seed oil as fuel compared to DF
GJ special engines are required
a emissions change depending on engine conception
@ black carbon and PAH are significantly reduced
.- 0 aldehydes increase heavily.
Institute of Biosvstems Enaineerina :
Conclusions RME as fuel compared to DF
8 useable in every Diesel engine
e MC-emissions are reduced, CO and NO, are comparable
0 aldehydes are slightly inweased
Q black carbon and PAH are significantly reduced
0 cancerogenic potential of the particulate is significantly reduced
Institute Of bsystems Engineering $T
Acknowledgement
The investigations demonstrated were supported by:
Herr Dipblng. G. Vellguth
Herr Prof. Dr.-Ing. A. Munack -.’
Herr Prof. Dr. Dr. M. Mmdir
Herr Prof. Dr. K. Stalder
Frau B. Ringe
Herr H. Seidel ,’
‘,:
‘nstitute of Ziosystems Enoineorina : .-
Scanning Electron Microscopy photography of particulate filters of
MB-trac a
igineering ..:- w.,.. >’ ‘-.+. > 3Efl!X
Appendix I3
31
Review: Utilization of Rapeseed Oil, Rapeseed Oil Methyl Ester or Diesel Fuel: Exhaust Gas Emissions and Estimation of Environmental Effects*
Jiirgen Krahlt), Axe1 Munackl), MiXit Bahadir2), Leon Schumacher3) and Nancy Elser3)
‘) Institute of Biosvstems Engineering, Federal Agricultural , Research Centre, Braunschweig, Germany
?) Institute of Ecological Chemistry, Technical University, Braunschweig, Germany
j) Institute of Agricultural Engineering, University of Missoury, Columbia, U.S.A.
* dedicated to Herrn Dipl.-In g. Gerhard Vellguth on the occasion of his retirement
1. Introduction
The use of rapeseed oil fuels in diesel engines has been intensively investigated since the beginning of the on-going energy crisis. In the beginnin g, the emphasis was pIaced on the technical possibili- ties associated with the use of rapeseed oil as a fuel. However, research has shown that pure rapeseed oil can only be used in specially designed engines. Research that followed indicated that rapeseed oil methyl ester (RME) was a suitable replacement for petroleum diesel fuel (DF) (Vellguth, 1982). Af- ter this discovery, research has focused on the engine exhaust emissions that result when fueling with both unmodified rapeseed oil and RME.
Initially, research concentrated on the federally regulated hydrocarbons (HC), carbon monoxide (CO) and nitrogen oxides (NO,) exhaust gas emissions (Vellguth, 1987). These components, and occasionally particulate matter (PM), have been investigated in a large number of studies and reports involving engine exhaust emissions testing. In addition, a series of current publications compare the environmentally important but non-regulatedpolycyclic aromatic hydrocarbons (PAH), aldehydes, ketones and in some cases, the aromatic compounds. According to the United States Clean Air Act (Gorse et al. 199 l), butadiene, benzene, formaldehyde, acetaldehyde and polycyclic organic mate- rial are the principal toxic airborne exhaust gas components found in engine exhaust gas emissions. Butadiene, however, has not been reported when examining the exhaust gases of engines fueled with rapeseed oil and RME. Likewise, the influence of rapeseed oil fuels on the formation of photochemi- cal smog, whose main component is ozone, is unknown.The undisputed advantages of rapeseed oil fuels, however, lie in their sulfur free emissions and the reduced atmospheric CO2 emissions.
An estimation of the environmental effects caused by emissions from engines fueled with rapeseed oil and rapeseed oil methyl ester fuels can be made by a relative comparison with DF. An evaluation of the potential health effects, as presented recently for gasoline and diesel-powered engines in an environmental assessment of the “Sachverstandigenrates fur Umweltfragen” (1994) (German Au- thority Council for Environmental Issues), must be replicated for RME and rapeseed oil fuels.
The goal of this review is to summarize the published emissions measurements from different au- thors, to compare these results and, where possible, identify trends that may exist. In order to classify and evaluate the conclusions, it is necessary to begin with a description of the experimental condi- tions applied, or in other words, the engine testing procedures (section 2). The currenr state of knowl- edge concerning the environmental effects of the components of exhaust gas are discussed. in order
to assess the environmental relevance of the test results. Section 4 contains a summary of the mea- sured values, that are discussed under conclusions in section 5 regarding their environmental impor- tance, whereby also some standing problems, whose research needs exist, are examined.
3 -. Engine testing procedures
The engine test procedures must be selected carefully. Engines emit harmful substances depending upon load and engine speed. A comparative evaluation of the engine exhaust emissions is only pos- sible when specific engine testing procedures are employed. For automobiles, test cycles that con- tain city and highway portions should be used. The test cycles that are used most frequently include the American Federal Test Procedure (FTP), which simulates typical city and highway usage in Los Angeles (Code of Federal Regulations) and the European ECE-15 Test (ECE = Economic Commis- sion for Europe). The ECE test procedure now includes a section that measures emissions at higher speeds to adjust to the traffk conditions that exist in Europe and is denoted MVEG-A Test (Motor Vehicles Emissions Group).
The results of exhaust gas emissions from these test procedures are not directly comparable, as the driving cycles load the engines differently. For this reason, the limiting values of legally regulated emissions are always based upon the test applied (Schaefer, 199 1). Table 1 provides a comparison of the results of the FTP-75 and the ECE-15 tests. A vehicle was fueled with rapeseed oil and dieset fuel and in each case was subjected to both driving cycles. The emission values of the rapeseed oil combustion are based on the respective value of DF (100%) (Menrad et al., 1989). The significant differences of the single values emphasize the influence of the engine test procedure on the results. For this reason it is necessary to indicate the test cycle used when specifying the emissions results and their comparison with limiting values.
HC
co
NO,
particulate matter
co2
FTP-75 ECE-15
230 162
185 214
97 94
2$7 320
107 112
benzo(a)pyren 141 169 pyrene 260 302
fluoranthene 212 308 2 PAH 189 271
formaldehyde 286 289
acetaldehyde 402 293
acrolein 825 575
1 aldehyde 382 336
Table 1: Exhaust gas emission (%) of a vehicle fueled with rapeseed oil compared to the emissions of a vehicle fueled with diesel fuel, using the FJYP-75 and WE-15 tests.
Worldwide many different test procedures are likewise available for trucks. In the EU (EU = Euro- pean Union), truck emissions are analyzed using the 13-mode steady-state test cycle ECE R49. This test describes the engine load with city use and takes into consideration the European driving style and construction of the vehicles (Fraenkle and Stein, 1988). Diagram 1 illustrates the selected oper- ating points used during the engine emissions test procedure and the weighting factors for each part of the test. The idle mode, which is weighted 8 l/3 % each time, is repeated three times during the test procedure.
100 8
% 80 2
u 60 2 2
40
engine speed
thirteen mode test (ECE R 49 13-mode test)
%
%
% I /7 18%
engine speed
eight mode test (IS0 8178 Cl ; off-road vehicles)
engine speed
five mode test
Diagram 1: The load points of the 13- , 8- and S-mode tests
Truck and car test cycles are not suitable to judge the engine exhaust from agricultural tractors. The simulated city and highway tests are not appropriate for agricultural vehicles, because the engines are loaded differently. The steady-state 5-mode test developed by Vellguth (1987) has been adjusted for emissions testing of agricultural engines. This emissions test procedure is based on research con- ducted by Welschof (198 1), whereby 5 modes accurately predict the typical exhaust emissions pro- file of agricultural vehicles.
The International Standards Organization (ISO) is currently discussing an g-mode test to certify agricultural engines. This test is based on the 13-mode test. As is evident in diagram 1, only two engine speeds in addition to idling are considered. Today it is not proven if the cycle recommended in the IS0 plan 8 178-Cl can be relied upon not only for certification but also to estimate the exhaust emissions actually produced by agricultural use.
In conclusion, in view of the comparability of the emissions values determined among the various test procedures, a direct comparison of the absolute values is not admissible. For this reason, the following results will be represented based on the engine test procedure used.
3. Environmental effects of the main exhaust gas components
The effects of components of exhaust gas have been a subject of research for some time. Here the evnected effects will he nresented mlv in shortened form. Soecialized information can be obtained
from the extensive literature covering the subject. Information can be found in the studies of the “Landerausschuss fiir Immissionsschutz” (Studies of the German States for Immissions Protection) (1992), Lenz et al. (1993) and Krahl et al. (1994), and “Sachverstandigenrat ftir Umweltfragen” (German Authority Council for Environmental Issues) (1994).
3.1. Gaseous regulated components HC, CO, and NO,
The hydrocarbon emissions produced by motor traffic are either toxicologically of little relevance (alkanes, alkenes, as well as methane, ethane, or ethene) or can be carcinogenic (benzene, polycyclic aromatic hydrocarbons). The latter are handled separately in the following sections. Some hydrocar- bons are also of importance in atmospheric chemistry (see section 3.3).
The carbon monoxide emissions arising from engine combustion, aside from suffocation in closed rooms or garages, are insignificant in light of the other environmental problems caused by motor traffic (Henschler, 1994).
Oxides of nitrogen contribute to the formation of acid rain. When combined with volatile hydrocar- bons or aldehydes in the presence of sunlight, the concentration of ozone at low altitudes increases (see section 3.3). NO exhaust emissions are at a low enough concentration that they are not perceived as a health risk. In contrast, NO;! is a lung irritant that attacks the membranes of human lung alveoli, even in small doses (Henschler, 1994).
3.2. Aromatic compounds, PAH and diesel soot
Benzene, toluene, xylene and ethyl benzene are the main aromatic compounds that have been inves- tigated in connection with engines fueled with rapeseed oil fuels. In accordance with the US Clean Air Act, benzene is an especially environmentally relevant and toxic airborne component (see sec- tion 1). In Germany, benzene is identified as a carcinogenic hazardous material (Gefahrstoffverord- nung, Gruppe 11) and as an unequivocal carcinogenic material (MAK III Al; maximum work area concentration, group III Al). The alkyl aromatic compounds are considerably less environmentally relevant with regard to their direct effect on humans.
In addition to the biological effect of aromatic compounds, the indirect influence of these com- pounds on tropospheric ozone formation must be taken into account when discussing engine exhaust emissions (see section 3.3). In this light, the importance of benzene and its alkyl derivatives is re- versed, as the ozone formation potential of 1 g benzene is approximately 25 times less than that of 1 g 1,3,5-trimethyl benzene (Carter, 1991). At this time, however, there is little data evaluating the role of aromatic compounds produced by diesel exhaust emissions on ozone formation at low altitudes.
Polycyclic aromatic hydrocarbons (PAH) have become a known hazard for humans and the environ- ment that must be taken seriously because of its carcinogenic and mutagenic properties. The individ- ual PAH compounds have, dependent upon structure, varying tumor-inducing effects. Whereas benzo(e)pyrene has been shown to be non-carcinogenic, its structural isomer benzo(a)pyrene be- longs to one of the most cancer-inducing substances in animal experiments (Huber et al., 1987). Different combination< of P.4H can work svneroisticallv or antngnisticallv. $0 it is imoossihle to
predict the carcinogenic potential of a mixture of PAH according to the known effects of the single components (Heinrich, 1991; Kaschani and Brauns, 1991). When discussing PAH, one must also consider that the PAH itself is not the ultimate carcinogen, but rather a reactive rnetabolite, the PAH- diol-epoxide, possesses the tumor-inducing potential (Grover, 1986).
Even more complex is the association between the induction of lung tumors and diesel engine emis- sions (DEE). Not only the PAH compounds adsorbed to soot particles have a strong cancer-inducing potential, but the assumption can be made that the PAH-free soot also induces carcinomas. Experi- ments with rats have shown that soot which is virtually free of adsorbed organic compounds can induce lung cancerjust as the actual diesel particles do. It is probable that soot, in connection with the deposited substances, is responsible for the formation of tumors (Heinrich, 1991; Pott, 1991; Boeckh, 1992). Independent of the question, whether the PAH, the pure carbon fraction or their added effect is the main inducer of lung cancer, the fact remains that DEE, because of its potential health hazard, was classified in 1987 as a human carcinogen (MAK III A2, by the “Senatskommis- sion der Deutschen Forschungsgemeinschaft zur Priifung gesundheitsschadlicher Arbeitsstoffe” (Senate Commission of the German Research Community for occupational health) when investigat- ing health hazardous materials (Henschler, 1987).
3.3. Environmentally relevant effects of aldehydes and ketones
Aldehydes and ketones are compounds with a pungent, membrane-irritating smell. The most well- known example of this class of compounds is formaldehyde, whose detrimental effect on human health is well documented. Acrolein, a characteristic exhaust gas component of engines fueled by RME (Wurst et al., 1990), is considered a potential carcinogen (Office of Health, 1990). These ef- fects, however, are not alone decisive for the environmental relevance of the carbonyl compounds emitted by engines, which have only a short half-life in the atmosphere (Lofti et al., 1990). More importantly, in the presence of NO2, aldehydes and ketones promote the formation of photo oxidants in air, the so-called “photochemical smog,” which contains up to 90% ozone (Moussiopoulos et al., 1989; Wagner, 1991).
In the following section, the photochemical reactions responsible for ozone formation as described in detail by Moussipoulos et al. (1989) are outlined.
Ozone is formed by the reaction of oxygen molecules in the triplet state:
02 + 0 (JP) -> 03 (1).
Oxygen atoms in the ground state are formed by photolysis of stable molecules:
O3 + hv -> 0 (3P) + 02
NO2 + hv -> 0 (3P) + NO (3).
Although the ozone concentration can also be reduced through deposition or reactions with other --Pln-*-l.?r r!-0 ny;Alt;np nf‘2Tf-T +n r\!f3- ;C rn,ncide-PJ *n b the mnct effrcieqt fnrm nf cle:rndatinn.
NO+03->N02+02 (4).
In the absence of further reactants, an equilibrium between ozone formation and ozone breakdown can be reached (eq. (1) - (3) and eq. (4), respectively). The equilibrium constant for this reaction requires an unrealistic NO, level of loo0 ppb to attain an ozone concentration of 100 ppb. As such, excess ozone must be formed by further reactions.
An excess of ozone is created, during the photolysis of NO;! when newly formed ozone is not used up in the oxidation of NO. One way this can happen is by the photolysis of aldehydes:
RCHO + hv -> R. + HCO. (3
R. + 02 -> ROO. (6) ‘.
HCO. + O2 -> HOO. + CO (7).
Peroxyl and hydroperoxyl radicals are formed. which can now react with NO and oxidize it to NO2 without the presence of ozone. The newly created NO2 initiates ozone formation (eq. (1) and (3)).
NO + ROO. -> NO2 + RO- W
NO + HOO. -> NO:! + HO. (9).
The hydroxyl radicals are also environmentally important, as they can react with aldehydes to create acyl radicals:
HO- + RCHO -> RCO. + H20 (10).
Peroxyacyl radicals can form from these acyl radicals: ,..
RCO. + O2 -> RCOO. (1lL II 0
Peroxyacyl radicals can react with NO2 to form the known phytotoxic and suspected mutagenic per- oxyacylnitrates (PAN) (Kirschmer, 1989; Smith et al., 1989):
RCOO. + NO2 -> RCOON02 (12). II II 0 0
In addition to these reactions, a large number of other mechanisms exist (Sattler and Jaeschke, 199O), that are not reported in this paper. Most of the other hydrocarbon compounds found in exhaust gas also contribute to ozone formation in the atmosphere through complex chain reactions when suffi-
cient NO;! is present (Moussiopolus et al., 1989). It has been estimated, that motor vehicle traffic in West Germany is responsible for nearly 30% of anthropogenic emission of volatile hydrocarbons (Reichow. 1992).
The automobile industry has shown more interest for ozone reduction than for either CO2 reduction or for energy savings (Krumm et al., 1992). To reduce the ozone burden, new limiting values for carbon dioxide emissions have been issued by the California Air Resources Board (CARB, 1994). No longer is the sum of all hydrocarbons totaled, but rather only the methane-free portion (Hockel et al., 1992), as methane contributes only slightly to ozone formation (Schaefer, 199 1). The remaining hydrocarbons, along with a few other compounds in exhaust gas (such as carbonyl compounds, alco- hols and ether), are designated NMOG (non-methane organic gases) and are regulated after 1994 for all automobiles from each manufacturer (Bayer1 et al., 1992; Boyd. 1992). A recommendation for the specific determination of NMOG-emissions can be found in CARB regulations (1992).
The varied ozone-forming potential of approximately 150 gaseous organic compounds in exhaust gas is the reason for the interest in the differentiated hydrocarbon and carbonyl determination (CARB, 1991a; CARB 199 lb). Each of these components is assigned a maximum incremental reac- tivity (MIR) by CARB. A listing of MIR factors can be found in Carter (199 1) and Kriill et al. (1993).
Using the MIR factors and the compounds of the NMOG list, it is now possible to compare different types of gasoline in reference to their ozone-forming potential (Chang and Rudy, 1990; Kriill et al., 1993). These factors and the NMOG list facilitate the determination of the total potential of the con- tribution of individual exhaust gas. In experiments using a diesel engine, it could be shown that form-, acet- and propionaldehyde alone make up more than 40% of the ozone-forming potential of engine exhaust gas.
4. Comparison of emissions from rapeseed oil, RME and diesel fuels
4.1. Gaseous regulated exhaust gas components, particulate matter and soot number
Many publications are available that describe comparative measurements of 100% rapeseed oil and RME. Because the quantification of HC, CO and NOx are usually undertaken with reliable and com- mercially available gas analyzers, the discussion of the analytical procedures and their results that are used to determine relative changes in these components is unnecessary. Likewise, standardized methods with good reproducibility exist for determination of particulate matter and soot number. In constructing the following summary, we have referenced current secondary literature (Scharmer et al., 1993, Irmscher and Jaskulla, 1994) related to the topic. However, the quoted relative changes in emissions must be corrected in same cases after the comparison to fit the original literature.
4.1.1. Comparative measurements of DF and rapeseed oil
Diagrams 2 to 5 show the results of the regulated gaseous components, particulate matter (PM) and soot number. A distinction is made in each diagram according to the test cycle used and engine de- cin7-1 t;v,rlirP-t ;n;ertinn m-m direct iniPctinn K)T\ nr srycinl cnnstruction\.
o Engine with indirect injection (rapeseed oil)
200 ; 0 0
A Eisbett engine (rapeseed oil)
0 n Knickpleuel engine (rapeseed oil)
A
q
A A m
Diesel fuel --
A
HC CO NOx
I PM soot number
Diagram 2: Emission of regulated compounds in engines fueled with rapeseed oil compared to diesel fuel in the FTP-75 test (DF = 100%)
350
A
0
A Diesel fuel
@ Engine with indirect injection (rapeseed oil)
A Elsbett engine (rapeseed oil)
0 1 / I 4 4 J
HC co NOx PM soot number
Diagram 3: Emissions of regulated compounds in an engine fueled with rapeseed oil rnrn~qr~4 rn nerrnlp.lm rfierel flIpI ;n the FCF 1 q-mnde teqt fl3F = ICY%\
350 /
% @ Engine with indirect 300 injection (rapeseed oil) -
0 A Elsbett engine (rapeseed oil)
250 @I -
0
200 1 A 0
150 0
m A
0 / Diesel fuel
/
t
w
8 A
HC
I
co NOx PM soot number
Diagram 4: Emissions of regulated compounds and soot number in engines fueled with rapeseed oil compared to petroleum diesel fuel in the 13-mode test (DF = 100%)
350 /
%
300 -
8
@ Engine with indirect injection (rapeseed oil)
A Elsbett engine (rapeseed oil)
250
i
200
i I
150 -I
100
A
A A A
/ Diesel fuel
A Q
50 -
B
0 . 0
I
HC co NOx PM soot number
Diagram 5: Emissions of regulated compounds and soot number in engines fueled with --,9,-,,>rl -,;I --mTT,,rorl *c nntrnlpllm rl;ncp1 fllO1 ;rT +ho i-mode rect tl3F = IMPA\
Independent of test cycle, uniform tendencies concerning engine exhaust emissions when fueling with rapeseed oil are observed. HC and CO are increased sharply, whereby the NO, values remain basically unchanged. PM increased when using the transient (automobile) test cycle, while the en- gine was fueled by 100% rapeseed oil. However, when the results-are based on the steady state 13-mode test, a 20% decrease in PM was observed. The soot number was also reduced by about the same amount. An even stronger reduction in soot number (70%) was observed with the use of ra- peseed oil.
4.1.2. Comparative measurements of DF and RME
More results of exhaust gas analyses are available for engines fueled by RME than for rapeseed oil. Diagrams 6 to 11 show the relative differences in values for regulated emissions compounds and soot number compared to DE The distinction is made here according to the engine test procedure and engine construction.
160
%
140 - 0
120 0 0
i
Diesel fuel 0
100 8
- m
I 8 80 ’
0 1 0
60 b : 0
40
0, I
HC co NOx PM soot number
Diagram 6: Emissions of regulated compounds in an IDI engine fueled with RME compared to petroleum diesel fuel in the FTP-75 test (DF = 100%)
160
s/o
140
120
100
80
60
x * X Diesel fuel
HC co NOx PM soot number
Diagram 7: Emissions of regulated compounds in a DI engine fueled with FME compared to petroleum diesel fuel in the FTP-75 test (DF = 100%)
160
o/o
140
120
100
80
60
40
20
0
T
I
c
/ Diesel fuel
8 0
i a
8
0
0
8
0
HC co NOX PM soot number
Diagram 8: Emissions of regulated compounds and soot number in a IDI engine fueled with DYTC s--m”lrn4 PI-- nprrnlnl,rr rliecnl CI7,z.l ;n ‘ho 1 q-mr\Ar= ~PCT /n?= = 1 nncI,l
160
9/o
140
60
242X 162 x 210 x
X X
X
X X
X Y
& X
-
,.
M
F
v /\
X
w
/
Diesel fuel
Y X 9-c X x
k F ?I
F 1
HC co N Ox PM soot number
Diagram 9: Emissions of regulated compounds and soot number in a DI engine fueled with RME compared to petroleum diesel fuel in the 13-mode test (DF = 100%)
160 A
76
140 1
120 - X X
X X Diesel fuel
100 - v / X
if
X
80 -
60 1
X
X
0 I ” I I !
HC co NOx PM soot number
Diagram 10: Emissions of regulated compounds and soot number in a DI engine fueled wirh RME compared to petroleum diesel fuel in the 5-mode test (DF = 100%)
160
%
140
120
100
80
60
40
20
0
1
r
/ Diesel fuel
l l
0 0
0
0 MVEG test (RME)
0 ECE-15 test (RME)
HC co NOx PM soot number Diagram 11: Emissions of regulated compounds and soot number in an ID1 engine fueled with
RME compared to petroleum diesel fuel using different test procedures (DF= 100%)
The comparison of steady state and transient test cycles show no significant variations. The use of DI or IDI engines did not reveal any significant advantages for either engine type.
In particular, HC discharge of both engine concepts was reduced by about 20% in the FTP-75 test. For IDI engines running on RME, a HC reduction of approximately 40% in the 13-mode test is ob- served, whereas this value with DI engines was decreased by only about 10%. These observed ten- dencies, however, should be interpreted with caution, as a much larger database is available for DI engines.
CO was reduced on average by 15% for all engine designs with RME use, whereby IDI engines show some advantages. NO, emissions increased by almost 10%. No PM changes were observed for DI engines tested with the 13-mode test with either RME or rapeseed oil. In almost all other cases, a reduction of approximately 20 to 40% occurred when compared to the DI engine when RME was used. IDI engines generally emit smaller particulate matter. The soot number is independent of en- gine design and test cycle. A reduction in soot number of approximately 40% was noted when FWE and rapeseed oil were compared to diesel fuel.
4.2. Non-regulated exhaust gas components PAH, aldehydes, and aromatic compounds
In contrast to the diverse comparative measurements of regulated emissions, the availability of data is limited for the non-regulated compounds. Among the unregulated components of exhaust gas, aldehydes have been more thoroughly investigated than PAH. In isolated cases, indications of ernis- sions of benzene and alkyl benzene derivatives have also been reported. The expenditure necessary to quantify carbonyl compounds is much lower compared to that of PAH, which explains the varying amount of information on aldehvdes and P,4H.
Within the framework of the following section, the analytical precision of PAH, aldehyde and aro- matic compound determinations will not be discussed. Many of the PAH values are based on single measurements without repetition. The relative deviation of the aldehyde measurements with re- peated measurements range from + 2 - 20%, whereas the repeated standard deviation with multiple PAH measurements varied from 5 to 40%. Detailed information concerning the following test re- sults of unregulated emissions are documented by Krahl et al. ( 1994), including sources, description of analytical procedures, number of repeated measurements and, when available, relative standard deviation of repeated measurements.
The following criteria were used to select data for comparison purposes: 1) common engine test cycle, 2) information can be used quantitatively according to the analytical laboratory, 3) the engine tested ran without breakdowns at least during the assessment period. However, the third criterion cannot be equated for actual usage with the suitability of the engine for continuous operation with biofuels. In addition to the selection criteria mentioned above, experiments were also excluded, when the analytical laboratory stated a deviation of + 100%. Diagram 12 illustrates acompilation of the measured values which were considered.
,. 300 I
0
Q
0 Engine with indirect injection (rapeseed oil)
A Elsbett engine (rapeseed oil)
150’
1 / Diesel fuel
FTP - 75 test ECE - 15 test 13 -mode test 5 - mode test
Diagram 12: Relative PAH emissions values from engines fueled with rapeseed oil compared to petroleum diesel fuel (DF = 100%)
4.2.1 Comparative measurements of PAH in DF and rapeseed oil
The results from the FTP-75 cycle show large fluctuations. In the ECE-15 test, an increased PAH emission for rapeseed oil operation when compared to DF operation can be uniformly identified. In contrast, the ECE-R49 and 5-mode tests lead with rapeseed oil operation to a reduction of PAH in th,= auh 711ct V?C
In summary, PAH values are strongly decreased in steady-state tests during engine operation with rapeseed oil. PAH are increased in the transient ECE-15 cycle and also in the FTP-‘75 test. In the Smode test, the relative PAH reduction was more pronounced in pre-chambered engines than in the direct injecting Elsbett engine. The original literature, however, indicated that the absolute PAH dis- charge of pre-chambered engines represented a 10 to 20-fold increase when compared to the Elsbett engine
4.2.2. Comparative measurement of P,4H with DF and RUE
In the final result of the experiments shown in diagram 13. it is clear that fueiing with RIME signifi- cantly reduced PAH exhaust emissions of most engines. This decrease was especially noticeable with the 5-mode test that was designed for agricultural engines.
200 % 180
1 160-1
140
0 Engine with indirect injection @ME)
X Engine with direct injection (RME)
n AQA-test, French city cycle (RME)
/ Diesel fuel
1 oo-. X i x
80 X X
60
20 E
- ,
FTP-75 test ECE- 15 test 13-mode test 5-mode test
Diagram 13: Relative PAH emissions values from engines fueled with RME compared to petroleum diesel fuel (DF = 100%)
4.2.3. Comparative measurements of aldehydes with DF and rapeseed oil
Diagram 14 shows a relative comparison of aldehyde and ketone emissions for the varying engine test procedures according to the selection criteria. A drastic rise in aldehyde emissions was noted (200-300% of the DF value) when fueling with rapeseed oil. Formaldehyde and acrolein are largely responsible for this increase. Emissions from pre-chambered engines (IDI) fueled with rapeseed oil tended to increase more strongly than those of Elsbett engines. However, one case showed compara- h/p pm;~sin-s fnr hnth fl!elc \xfithin the lipilq nfdetlinrinn
zoo{ I
0
A 0
0 A
100 A / Diesel fuel. A _-
0 Engine with indirect injection (rapeseed oil)
A Elsbett engine lraoeseed oil1
FTP - 75 test ECE- 15 test 13-mode test 5 -mode test
Diagram 14: Aldehydes emissions from engines fueled with rapeseed oil compared to petroleum diesel fuel (DF = 100%)
4.2.4. Comparative measurements of aldehydes with DF and FUME
The relative values of aldehyde and ketone emissions are represented for the different test cycles in Diagram 15. ME aldehyde emissions increased approximately 40% compared to operation with DE Again formaldehyde and acrolein were responsible for this increase. It is interesting to note that the upper and lower extreme emissions cases were produced by the same engine manufacturer in the FTP-75 test. There is no certain explanation for this discrepancy. The emissions from one vehicle that was fueled with RME was quite high compared to the other engines that were evaluated. When this case was removed, RhE produced a 20% increase in exhaust emissions. The comparison of indirect-injected with direct-injected engines doesn’t reveal any particular tendency.
400 %
350-
300-
0 Engine with indirect injection (RME)
X Engine with direct injection (RME)
250-
200-
150-
100
X 0 Diesel fuel
x /
i I
n # X
m X
50
1
FTP - 75 test ECE-15 test 13-mode test 5-mode test
Diagram 15: Aldehydes emissions from engines fueled with RME compared to petroleum diesel fuel (DF = 100%)
4.2.5. Comparative measurements of aromatic compounds
The emissions of benzene, toluene, xylenes (BTX) as well as ethylbenzene have only been sparingly investigated for engines fueled with rapeseed oil and RME. Diagram 16 shows the available in- formation in relative representation. It is clear that for the comparison of RME with DF in the FTP-75 and in 5-mode tests, a reduction of aromatic compounds emissions are found, similar to the levels noted concerning PAH emissions. In contrast, an increase in the level of aromatic emissions can be seen in the outcome of the 13-mode test when the test engine was fueled with rapeseed oil.
200 %
180-
160-
140
120 A
Q Engine with indirect in’ection (rapeseed oil’
A Efsbett engine (rapeseed oil)
a Engine with indirect injection (RME)
X Engine with direct injection (RME)
/ Diesel fuel
X
40
I
Y 20
FTP-75 test ECE- 15 test 13-mode test 5-mode test
Diagram 16: Aromatic compounds emissions from engines fueled with rapeseed oil or RME compared to petroleum diesel fuel (DF = 100%)
Total emissions of BTX and ethylbenzene correlate strongly with the measured values for benzene, an especially important compound. Diagram 17 shows the relative emission values of benzene. With the exception of the engine in the 5-mode test, similar tendencies were noted for the sum of the aromatic compounds and benzene emissions. Elsbett engines produced slightly higher Jevels in ben- zene emissions when compared to the sum of aromatic compounds emissions. The sharp rise in ben- zene emissions is significant when compared with the lower total emissions of aromatic compounds from the engine in 5-mode test.
A 0 x
/ Diesel fuel
801
60 1
40-
20-
0 Engine with indirect in’ection (rapeseed oil.1
A Ekbett engine (rapeseed oil)
0 Engine with indirect injection @ME)
X Engine with direct injection (RME)
FTP -75 test ECE- 15 test 13 -mode test 5 -mode test
Diagram 17: Benzene emissions from engines fueled with rapeseed oil or RME compared to petroleum diesel fuel (DF = 100%)
4.3. Summary of the known test results
The influence of rapeseed oil and RME on the emission of federally regulated components has been investigated extensively.
Table 2 presents a summary of average values for engines fueled with rapeseed oil and Rh4E compared to engines powered with diesel fuel. Please note that the table does not indicate the num- ber of measurements conducted.
Component
hydrocarbons (HC)
rapeseed oil
210 % IDI
110 % DI
RME
70 % IDI
80 - 90% DI
carbon monoxide (CO) I 1
180 % ID1 70 - 90% IDI
I 1
115 % DI 100 % DI
nitrogen oxides (NOJ
particulate matter (PM)
100 %
320 % trans. IDI
90 % stead. IDI
80 % DI
110 %
100 % DI
60 - 80 %
1 soot number I 55 % I 60 % I
IDI: indirect injection; DI: direct injection; stead.: steady-state test; trans.: transient test
Table 2: Emissions of regulated compounds and soot number in engines fueled with raneseed oil and RME (DF = 100%)
In summarizing the following section concerning non-regulated compounds, the differentiation of the engine design cannot be determined, as too little data were evaluated by the researchers. It must be noted, however, that the PAH values reported in some literature are questionable.
The tendencies stated are not only based on averages of repeated measurements but also on single determinations. Table 3 provides a comparison of measurements for operation with rapeseed oil and RME relative to operation with diesel fuel. The relative values do not indicate the number of under- lying measurements nor do they give the accuracy of the repeated measurements; information con- cerning these factors was documented by Krahl et al. (1994).
Component rapeseed oil RME
PAH 10 - 75 % FTP/13/5 75% trans.
240 % ECE 75% 1.3
15% 5
aldehydes 280 % 120%
400% FTP
aromates 135 % 60%
special: benzene 160 % 70%
135%
FTP: FTP-75 test; ECE: ECE-15 test; 13: 13-mode test; 5: 5-mode test;
trans.: transient test
Table 3: Unregulated emissions from engines fueled with rapeseed oil and FCME compared to petroleum diesel fuel (DF = 100%)
5. Effects of rapeseed oil and RIG
,_. _ . .
5.1. Gaseous regulated components
No significant differences in direct effects can be deduced from changes in the gaseous regulated components. Section 5.3 discusses possible indirect photochemical effects of specific hydrocarbons.
5.2. PAH, particulate matter and soot
Because PAH have a higher carcinogenic potential synergistically with soot particles than each com- ponent alone (Heinrich, 1994), an estimation of the cancer-inducing effect of exhaust gas is only possible when considering these compounds collectively. When discussing soot particles, it is also
relevant, that pure carbon on which no compounds have accumulated can also induce lung cancer. Krahl(l993) summarized in preliminary, previous research, which show that particle size and dis- tribution frequency from the filtrate of undiluted exhaust gas from diesel fuel and RME present dis-
similarities that favor the use of the alternative fuel. Parallel to this result, a considerable reduction in PAH emissions has been noted when fueling with RME. Using Salmonella cultures, Stalder et al. (1993) noted a reduction of mutagenic potential in RME particulate matter during full load and idle when compared to that of diesel fuel. Similar results were found by Eckl(l994).
The data were not uniformly distributed when unmodified for rapeseed oil was used as fuel. PAH and particulate matter concentrations were less homogenious with the use of rapeseed oil. Mutagen- icity tests similarly show strong fluctuations (Stalder et al., 1994).
At this time, research is still needed on the mutagenic and carcinogenic effects of particulate matter for both RME and raw rapeseed oil. The continuing investigation on the influence of biofuels on soot particle size and concentration is also of importance. It should be reiterated, that current knowledge indicates clear advantages for RME regarding soot, particle and PAH emission in conjunction with distribution of particles and mutagenic potential. Only non-uniform results were noted for raw ra- peseed oil.
5.3. Aldehydes
The discharge of aldehydes into the atmosphere is of environmental relevance in two ways (see sec- tion 3.3). In light of the direct effect of aldehydes, Wolfensberger (1994), during a experiment in the city of Zurich, noted that exhaust gas fumes from buses run with RME caused some of the mainte- nance staff and drivers to become ill. However, the typical odor of vegetable oil fuels was practically eliminated by a oxidative catalytic convertor (see also Krausgrill and Schmidt, 1993). Stalder et al. (1993) found in preliminary laboratory experiments that RME-soot elevated cytotoxicity. Addi- tional systematic experiments, however, could lead to more certain results. Aldehydes also have a great influence on tropospheric ozone formation. Because aldehydes from diesel engine combustion eventually contribute to more than 40% of the ozone-forming potential, the increase in aldehyde discharge (which is sometimes extreme, as in the case of operation with raw rapeseed oil) deserves attention, especially when vehicles fueled by RME and rapeseed oil are used in cities. The increase of ethene and ethyne which has been determined during engine operation with RME (Wurst et al., 1990) is also worthy of consideration. Together both components are suspected to contribute to over 30% of the total formation of ozone induced by diesel engines (Hartung, 1993).
Consequently there exists a considerable need for research in the area of aldehydes, alkenes and al- kynes, if biofuels are to be used in overcrowded industrial regions.
5.4. Aromatic compounds
Emissions of aromatic compounds are decreased when fueling with RME. However, they are ele- vated for rapeseed oil. Wurst et al. (1990) reported a distinct increase of benzene emissions during the 5-mode test. This phenomenon cannot be satisfactorily explained. A need exists for research concerning the ozone-forming potential of the alkyl derivatives of benzene found in RME exhaust gas. The benzene emissions and their environmental impact should be systematically investigated at the same time.
5.5. Conclusion
The comprehensive review of all research shows both advantages and disadvantages for rapeseed oil and FUVIE usage. The direct acting disadvantages are less pronounced for FME as for rapeseed oil. A definitive evaluation can partially be found in the Unit-Risk-Assessment of Otto-(gasoline) and Diesel engines, recently published (1994) by the “Sachverstandigenrat fiir Umweltfragen.” This publication, however, needs to expand upon specific characteristics of biofuels including the size distribution of soot particles. In light of the effects of emissions, future research should include a systematic investigation of the cytotoxic, mutagenic and carcinogenic characteristics of these alter- native fuels. Likewise, the ozone-forming potential of vegetable oil fuels, when used in regions other than agricultural areas, should be determined.
summary
Based on the extensive literature about exhaust gas emissions resulting from the combustion of ra- peseed oil and its methyl ester (RME), data were compiled and differentiated according to the under- lying engine test procedure, fuel and engine design. In light of the known effects of individual ex- haust gas components presented in the beginning, an effort was made to estimate the environmental relevance of rapeseed oil and FWIE compared to diesel fuel.
RME seems to present fewer disadvantages of the two fuels compared based on current knowledge. However, in order to make a sound evaluation of the emissions characteristics of these alternative biofuels, additional research is necessary. Unregulated exhaust gas emissions must be determined. Likewise, the mutagenic, carcinogenic and cytotoxic effects resulting from rapeseed oil or RME use have not been sufficiently investigated when compared to the on-going investigation of effects of petroleum diesel. In addition, in order to utilize these alternative fuels in regions with high NOx con- centration, it is necessary to determine the expected ozone formation in low altitudes that result from their emissions and to compare this with that of petroleum diesel fuel.
Appendix C
33
Release for Biodiesel According to research conducted by the FUiG -Hannover and UFOPl Standings from Sept. 1995
Manufacturer TFe Comments Volkswagen Automobiles l Released for all diesel models after 1996
l Conversion kits available for 1.9 L IDI- engines_afIer year ‘92; for Golf and Jetta built after December ‘94.
Mercedes
Opel AG
Automobiles l Released for C 200 D, C 220 D, E 200 D, E220 D models used for taxis
Trucks l Individual release possible for models of the 300 and 400 series after 1988 T
. New vehicles given release directly from factory possible
ullimog 6 Release given
Tractors l New tractors one year warranty
Automobiles
. Used tractors without factory warranty
. Individual reIeases given after application
. Further releases announced during the course of 1995
Ford AG Automobiles l Applicable for 2.5 L injectors
. General release expected for 1995
MANAG
Tractors
Trucks
Iveco Ma-@us Trucks
. Release for all new tractors, 2 year warranty
. RME package available upon customer request
a Release for some engine types between 160 and 400 horsepower
. Individual releases possible after consultation l Conversion packages offered
Isecki
Holder
Fendt
Fiatagri
Case
John Deere
Lindner
Massey-Ferguson
Renault
Same
Steyr
Nissan
Farymann Diesel
Hanomag-Komatsu
Tractors
Tractors
Tractors
Tractors
Tractors
Tractors
Tractors
Tractors
Tractors
Tractors
Tractors
Tractors
Forklift
Engines
Engines
l Release for 3000 and 5000 series
. Release for A 440, 550, 550 S, 560 T, C 550, 560 T, A 650,660 T, C 660 T, C 5000, 5000 T, 6000
l Release given for Deutz engine
l Individual releases after consultation
. Release for all new tractors without restriction on the warranty
. New tractors must be converted, without loss of warranty
l Release for individual model types, warranty given for 2 years or 1,500 hour operation
l 1 year warranty possible for models after ‘85
l after 1989 warranty for 1 year or 800 hours of operation
l Release for all models with W-water cooled or air-cooled Deutz eqines
l After 1980, warranty for 4 yrs. maximum
l Release for all tractors after year ‘88 without conversion
l After year ‘74 release after modification
l Release given
l Release given
l General release
18. . . l
