Biodiesel in Europe 1998biodiesel.org/reports/19980722_gen-100.pdf · igure 3 Energy balance for the production of biodiesel versus rapeseed oil 1.1 Chemistry of Transesterification

Biodiesel in Europe 1998Biodiesel Processing Technologies

JConnemann, J.FischerOelmuhle Leer Connemann GmbH & Co., D-26789 Leer(Ostfriesland),Federal Republic of Germany

Paper presented at theINTERNATIONAL LIQUID BIOFUELS CONGRESS,July 19-22, 1998, Curitiba - Parana - Brazil

1. Biodiesel for Transportation

Ladies and Gentlemen.

Brazil is far ahead of the rest of the world in terms of biofuels, so I was very happy about thisinvitation to Curitiba and it’s a real pleasure for me to have this opportunity to disclose myview of the situation of biodiesel and our future to so many interested ladies and gentlemenand stakeholders of biofuels.

I myself was so to speak born into green chemistry, since already in 1750 the Connemannfamily [l] dealt with green soap and glycerine, with oilseeds, vegetable oils and feed cake,with wood and paper, all of these materials of natural origin named renewables today. Weeven made chipboards from bagasse.And today the oil milling part of my enterprise belongs to ADM, the known big producer ofbio-ethanol in the US

1.1 Introduction

A comprehensive review of the history and background of biodiesel in terms of chemistry,technology, quality and operability, taxes and politics is to find behind our homepage underwww.biodiesel.de, item CD paper 97, and still better under the references given in this paperhere, with my best thanks to many important friends, I may mention B.Freedman et a1.[2],W Gambler [3], B.Gutsche [4], W.Korbitz [S], J. Krahl [6], C.L.Peterson [7], C.Plank [B],D Reece [9], A.Schafer [lo], K. Scharmer [ll], L.Schumacher [12], 0 Syassen [13],H.Tschoke [14], G.Vellguth [15], M.Worgetter [16], R.Zilmans [17].

The oil crisis in 1973 triggered numerous studies on natural oils and fats all over the world,which we followed all the time with much interest, but we really entered the field only on the2nd of August 1990, the day the Golf Crisis began.

Today - 8 years later -we in Leer (in the north-western comer of Germany) fee1 responsiblefor approximately 100,000 cars running on biodiesel in mainly Germany, but also Swedenand the Netherlands and some other countries, representing possibly over 90% of today’s carspowered by neat biodiesel in the world, they all run on connediesel from Leer.This means at the same time that we and our distribution partners are most experiencedpeople in all questions of the application of biodiesel in diesel engines of all types.

With this background I want to show you the following:Biodiesel is not a mere question of set-aside-areas in Europe and subsidies or last help forfarmers, it is not a weak substitute for vanishing resources, the only CO2 remedy, etcIt is something else.

And though biodiesel today still depends totally from fiscal politics in Europe and nobodyknows whereto necessary harmonization between the member states in coming years willlead - you have to realize that a possible taxation would only hinder its progress or suppressthe production for some years, because the advantages of biodiesel are so convincing thatcertainly in the next decades it will reach an essential importance as a biomass originatedliquid energy carrier for transport

In this paper 1 will concentrate on processmg technologies, at least on some relevantexamples, and on the feedstock question, which without any doubt represents the main factorof any trial for evaluation and calculation of total costs of biodiesel.But I also want to show some conditions influencing biofuels and their future development.

1.2 Fossil Resources and Environment

The estimated resources oftoday [19] (Fig.1) - while we concentrate on a liquid energycarrier like mineral oil - have a worldwide distribution which implies possible difficulties infuture besides the fact that they are limited, while yearly consumption still rises.

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World Resources: Petroleum and Narural Gas 1998

We just calculated the safe resources with abt. 140 billion tons of fossil oils, the uncertaintiesin behind with additional 50% and came to the following graph (Fig.2). the resulting gapm~q~t he tilld with hinmnqc hinrlimdand Bonn

i

ca from new discoveries

(1994-136mrd.t)

0,o J y--J, I1995 2000 2005 2010 2015 2020 2025 2030 2035 2040 2045 2050

Figure 2. Demand and supply of mineral oil in coming decades

1.3 Renewable Resources

Besides wind and water power thus the use of biomass will have a tremendous future,especially the socalled biofuels

They represent a CO*-cycle in combustion, they mostly have better emissions, they arebiodegradable and contribute to sustainability. They have a considerable environmentallyfriendly potential. One of the important ones is biodiesel.

The energy balance (Fig.3) is very positive, 1:4 or 1:7 act. chosen relations, approx. 90% lessCO2 development than mineral diesel emits.

r

I RC2S”K mmass takes 15%. aha mmeral diesel needs 15% !+ referred to bmdiesel alone 2S”A are needed !CO2 develqment: Mineral diesel 11556 versus biodiesel 25%, diff. = - 90% !!!

igure 3 Energy balance for the production of biodiesel versus rapeseed oil

1.1 Chemistry of Transesterification

The models of the molecules (Fig.4) show what is intended to do by the transestertticatronprocess, after the exchange of glycerol against methanol (under certain conditions) theresulting methyl esters of fatty acids show a striking similarity to “cetane”, better known as“cetane number” as a measure of the willingness to ignite of a certain fuel, when it getscompressed Every molecule of oils and fats of plants or animals all over the world has thesame configuration, just little differences in length of the chain of carbon atoms or in numberof the double bondings, which result in different melting points, oxidation stability, etc.

Figure 4. Triacylglyceride (let?), methylester and cetane

The chemistry of the exchange (several parallel acting reaction equilibria and phase balances)is verbally described (FigS), (X-analysis [3,7] gives a thorough control of the progess of

1.5 Results of Transesterification of Vegetable Oils

The main aim of the transesterification is to get a lower viscosity (from abt.70 for plant oils to4,5 mm2isec at 40 “C for their methyl esters) and thus one gets a diesel f&l with thefollowing properties (e g. rapeseed oil methyl ester)

cetane number 58no sulphur, no aromatesbest emissions withoxidation catalystsbiodegradable, non-toxichigh oxygene content (11%)exorbitant lubricitywinter operability -22 “C

whrch doubtless can be called a “super diesel”.

Rapeseed oil is well suited for esters in European relations, but also sunflowerseed andsoyabean oil, possibly corrected by mixtures with palm oil and tallow/lard or even used oilscan be discussed

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1.6 Suitability as a fuel for diesel engines

Besides these splendid properties there is the strict challenge for a high and stable productionquality-

high degree of transesterification (> 99.8%)low acid number (KO.5 better <O 2%)

and most important.low content of free glycerine (CO 02 better <O 002%)no polymers, very clean

2. Biodiesel Processing Technologies

2.1 Transesterification of Biogenic Oils and Fats

Since more than 50 years the patent literature delivered many proposals, a rather new andvery comprehensive overview is given by B.Glrtsche [4], mentioning proposals made by Alfn-Luvul, Builestra, Connemann, DeSmet, Feld & Hahn, Henkel, Kirchfeld, Lurgi, IFP, V-N,Westfalin, L lJT and others.Some of these ideas were realized in existing and operating plants in Europe, we will pick outsix examples to compare operating costs and resulting quality, we present three simpleprocess schemes to characterize the differences.

2.1.1 Batchwise Operating Technologies

Most plants in the world within the capacity range of 500-10,000 tonsiyr are built as two-stepbatchwise operating units, each step consisting of a reactor vessel and a settlingtank CFig.7). socalled mixer/settler systems.

Figure 6 Batch process for the production of biodiesel

They are not too expensive, they can reach sufficient product qualities, but they havedifficulties in consistency and safety. But assisted by modem process control they are betterto adapt to changing raw materials and small quantities.

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2.1.2 Henkel Technology for Transesterification

This process probably was designed for general purposes, for different oil qualities as it usesa distillation step

The reaction part is described [4] by Fig.& it contams two tube reactors followed by settlingvessels, the operating pressure is 4-5 bar, the temperature 70-80 “C.

Figure 7: Henkel transesterification technology (reaction part) [4]

The glycerine is held back by coalescence separators, the ester is purified by distillation.Today two plants are operating with together 170,000 tons/yr.The resulting ester quality is good, very light color, high purity, low percentage of glycerides;also the glycerine (92%) quality is good.Disadvantages are. High investment, High energy consumption, content of free glycerine(>0,02%) is too high for biodiesel use, less depression of CFPP and lower oxidation stabilitybecause of the distillation step, and finally a 4-S% residue is lost.

2.1.3 CD PROCESS for Transesterification

We in Leer instead designed our process precisely for biodiesel and on the basis of refined orwell degummed crude rapeseed oilThus a new low-cost processing technology was developed, the socalled CD PROCESS, CDderives from “continuous deglycerolization”, using well-known machinery of modernchemical industryThe CD PROCESS represented in 1991 the first conti-operating low-pressuretransesterification process in Europe, realized by reaction columns and centrihgal separators,aided by a closed cycle for alcoholysis (pref. methanol/ethanol) and a second closed loop ofwater for the extraction of glycerol and the washing purification of the ester.

The first plant produced 1 ton/day in already embarassing quality, a technical pilot plant for20 tons/day followed in 1993, producing 8,000 tonsiyr. and reproduced the last details neededto build a big plant

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In the same year the CD PROCESS was selected by DGXVII of the EU commission withinthe program THERMIE 93 and we got a 20% help to invest totally DM 20 million for the

1. European Industrial Demonstration Plantfor the Production of Biodiesel

m Leer/Germany, combined with the existing oil mill crushing rapeseed and sunflowerseed

This plant for 80,000 tonsiyr was fully onstream without any difficulties after only 12months, because agricultural coops and marketing groups as UFOP (German Farmers’Federation) and our own staff created a fast growing market for biodiesel in Germany.

New in this CD PROCESS is the efficient combination (Fig.8) and completely new is the factthat in the CD PROCESS we work with a countercurrent stream of a water-based extractionmedium into the reaction process itself which normally is to be kept under anhydrousconditions

6D PROCESS~~liansestcrtiicafion of Blogenlc Olsand FAs (Pst. DE 42 09 779, US 5.354878:

I-

_, 8 CD PROCESS for transesterification of triacylglycerols

Thereby we additionally extract the already exchanged and freed but still dispersed glycerineand reach a better degree of transesterifrcation, a significant lower content of free and bondedglycerine, for far bigger quantities in shorter times with astonishing consistency.Typical data reached by the CD PROCESS are shown (Fig.9).

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B io d ie s e I S ta n d a rd sP ro p e rtie 5 S p e c i f i c t o E s t e r s

Target data A.Ct”aII dataD i e s e l f u e l connediesel

L- .~~ E D I N 51606 m a d e i n LIsity 15’C [ g l m I 1 0,975-0,890 1-L--:_. Or I.” /-

I C F P PD e s c r i p t i o n :

%ppm

%“C

-0,20 ,I0 10

ss t h a n0 10

1, 0 1 w i n t e r : -226B i o d i e s e l f r o m F A M Econnediese‘I M E 991-201-10. -01

‘ s a m e f l a s h p o i n t D i e s e l f u e l E D I N 5160Q - FAM.Ei f a d d i t i v a t e d V e g e t a b l e o i l m e t h y l e s t e r

Figure 9: Biodiesel standards, properties and production data act. E DIN 5 1606

In the meantime we were granted several patents [4] with priority of March 26, 1992, also forBrazil and Argentine, and the CD PROCESS or CD PROCESS PLANTS are offered byseveral licensees like FELD & HAHN GmbH (KHD), WESTFALIA SEPARATOR AG(GEA), Franz Kirchfeld KG (FERROSTAAL) and others.

Today our plant is operating with 80,000 tons/yr, another one was planned with 100,000tonsiyr but postponed because of unfavorable feedstock prices since autumn 1997.

The advantage of the CD PROCESS: Compact plant, rather low- investment, operating atambient pressure and a temperature of 65-7O”C, capacities from 8,000 to 150,000 tonsiyr andmore, low energy consumption, excellent product quality, very high consistency and safetystandards

Disadvantage Not yet suItable for acid raw marerials (> 2% fatty acid), but it will be adaptedwithin some time. Color. yellowish, depending on raw material, if bleached, near distilledproduct

2.2 Esterification of Biogenic Acid Oils and Fatty Acids

The elder technology - huge and costly high pressure plants with heterogeneous catalysts,operating at 50-100 bar and 200.240°C - still exists, but was not used for biodieselproduction because of high specific costs.Under the sharply changed market conditions of today (with significantly higher prices forvegetable oils) one has to look again for other options of feedstock, thus existing processeshave to be adapted.Socalled used oils have to be treated with caution, they may contain oxidation andpolymerization products which have to be separated thoroughly.

1 0

2.3 Cost Comparison Biodiesel Processing Technologies

Careful examination and combination of known or published facts leads to the comparison ofthe operating costs of six different existing and operating plants [Fig. lo], possible subsidieson total investments are not taken in account, prices on normal level, expressed in Deutsche

illarkFig. 10: Comparison of production costs of operating biodiesel plants

The results show that operating costs decrease very much with used capacity, it also showsdifferences between technologies, but one has always to keep in mind that they all do refer tothe minor part of the total cost of biodiesel, the main part (85-95%) always is the raw materialitselfHelp for comparison. lOO,-DM/t = approx. 0,20 $/gal, thus 33,- DiWt means only 7 cts/gal astotal production costs

2.4 Biodiesel Production in Europe 1998

Our yearly revised producers’ list (Fig. 11) gives an estimate for the 1997/98 productionfigures in Europe which is very difficult to make due to high prices or the lack of rapeseed oilor other vegetables oils This fact is politically influenced by the EU commission within theCAP (Common Agricultural Policy) with decision on the share of set-aside-area which can beused for non-food purposes

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Nwzd + dhrs Llvcrm

Figure 11 Biodiesel producers in Europe 1997198

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3. Biodiesel Potential and Outlook

3.1 Taxation of Biofuels in Europe

We in Europe have rather high excise duties for !Lzls for transportation. For biodiesel thereare exemptions in some countries e g. in Germany, France, Italy, Sweden, Austria andCzechia. The EU commission intends to develop a 5% market share for biotiels up to theyear 2005 and recommends time-limited exemptions or reductions of taxes on biofuels to O-10% of normal amounts for the first 10 years, then to increase stepwise.

With Fig.12 another view is given, which in a simplified manner tells:Short-running energy carriers (the fossils) have to be taxed,long-running energy carriers (the renewables)have to be developed as fast as possibleto gain a certain percentage (10 20%) of total supply1 I!

Where are taxes heading for?Time horizon - Sustainability

-10”4” 40 40 60 250 500 10”.000 a n d mvch

Sustainability (years) ionpT ?? qq fowl . ..., q wageuemployment q mineral oil ta⌧ I

m\.nr ~~_. 0 Subsidies - I

Fig 12. Taxation of energy carriers according availability [16]

3.2 Biodiesel and Environment

It is hard to understand that opinions are divided so distinctly, as some people in Europe talkabout agricultural monoculture, about the danger of high NzO emissions, about aldehydes andNOx Others say that with ,,good agricultural practice“ there is no problem with too muchnitrogen, no danger of N20 at all (the rape plant is a deep-rooted most efficient N-user), thatthe aldehyde emissions of diesel motors are far below those of gasoline motors and besidesare eliminated almost totally by catalytic converters and finally that NO, emissions can be

1 3

influenced remarkably by changing the point of injection by only 2-3 degrees and apparentlyby higher prepressures in modern common rail injection systems

And as an enhancement of engine life seems to develop (the first German truck having donemore than 1.250 million km with its first engine has entered the Guinness Book of Records)there are experienced people [I31 who call biodiesel ,,champaign for the engine“.

3.3 Biodiesel Potential

In Germany we consider rapeseed as the most sunable basis for FAME, the maximum area togrow rapeseed is estimated at I 7 million hectares, which means approx. 2 million tons ofbiodiesel or 8% of today’s diesel fuel consumption.

For Europe we think in rapeseed and sunflowerseed and others, also partly in animal fats andused oils. Especially the seeds in France, Spain, the UK and Germany and in all EasternEuropean countries have a considerable area potential, especially in view of the alreadyexisting heavy surplus in wheat and other grains, so a diesel fuel share of IO-15% in Europeseems to be achievable.

In North America the possibilitres are stmilar to Europe, but in Brazil, whole South America.in Africa and Asia we will see palm trees growing with a yearly yield of up to 8-10tons/hectare of palm oil, besides all other oil seeds.

One reports that world’s forests decline with a rate of 0.3% or approx. 13 million hectaresyearly; and on the other side tree plantations’ cover worldwide in the last 15 years has alreadybeen doubled and increased by 80 million hectares (FAO 1997) Thus there is a potential.

4. General Assessment of Biodiesel

Biodiesel is an excellent diesel fuel, it improves the environmental conditions and gives acertain contribute to gain energy sustainability and security in the transportation sector.According the EU commission biotuels already in 2005 should reach a 5% share of the totalfuel consumption, wherein biodiesel on behalf of its potential will take an interestingposition.

Ladies and gentlemen, thank you for your attention for our esteemed biodiesel

Curitiba - Paranti - Brazil, July 21, 1998

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References

[1] Wilhelm Connemann, 200 Jahre Firmengeschichte, Verlag Rautenberg, Leer, 1950

[2] B Freedman, E.H.Pryde and T L.Mounts, J. AmOil Chem. Sot. 61, 1638 (1984)

[3] W Gombler, K Olthoff, Analytik von Biodiesel, AbschluDberichtProj. F A.-Nr 1991.051, Fachhochschule Ostfriesland, Emden, 1994

[4] B.Gutsche, Technologie der Methylesterherstellung-Anwendung fiir dieBiodieselproduktionFen/Lipid 99, Nr. 12, 418 (1997)

[5] W Korbitz, Biodiesel. A Summary ofEnvironmental Benefits,Austrian Biofuels Institute ABI, Vienna, 1998

[6] J Krahl, J Bunger, A Munack, K Prieger, Energie- und Umweltbilanz von Biodiesel,FVV-Workshop Biodiesel, Frankfurt/Main, 1997

[7] C.L.Peterson, Biodiesel fuel productioniproperties, Proceedings of the 3’d Liquid FuelConference of ASAE, Nashville, USA ( 1996)

[8] C.Plank, E.Lorbeer, Quality Control of Vegetable Oil Methyl Esters used as Diesel FuelSubstitutes: Quantitative Determination of Mono-, Di-, and Triglycerides byCapillary GC, J.High Resol Chromatogr. 15, 609 (1992).

[9] D Reece, Commercialisation of Biodiesel: Environmental and HealthBenefits,University of Idaho, May 1996

[ lO]A.Schafer, D Naber, M. Gairing, Biodiesel als alternativer Kraftstoff fir Mercedes-Benz-Dieselmotoren, Mineralolanwendungstechnik 3, Beratungsgesellschaf furMineralolanwendungstechnik mbH, Hamburg, 1998

] 1 I] K Scharmer, G Golbs, Biodiesel- Energie und Umweltbilanz Rapsolmethylester,GET, Julich 1997

[12] L. Schumacher, Biodiesel Research in the United States,Fachtagung “Biodiesel”, FAL Braunschweig, 1998

I1 31 0 Syassen, Chancen und Problematik nachwachsender Kraftstoffe,Motortechnische Zeitschrifi 53 (1992) H&e 11 und 12, Sonderdruck Franckh-KosmosVerlag, Stuttgart, 1993

1141 H Tschoke, “1st eine spezielle Motorenentwicklung t?ir Biodiesel notwendig?“,Fachtagung “Biodiesel”, FAL Braunschweig, 1998

[ 151 G.Vellguth, Energetische Nutzung von Rapsol und Rapsolmethylester.Dokumentation Nachwachsende Rohstoffe (1991), ‘Biofuels’,European Commission, DG XII, Eur. 15647 EN (1994)

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[16]M W&getter, Eigenschaften van Biodiesel,Fachtagung “Biodiesel”, FAL Braunschweig, 1998

[17]R. Zilmans (Editor), Biodiesel for Vehicles, TUV Bayern Holding AG, 1996

[ 181 J Connemann, Biodiesel in Europa 1994, Fat Sci.Technol. 96, 536 (1994)

[19] ANEP 98, European Petroleum Year Book 31. URBAN-VERLAG:Hamburg/Wien, 1998

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List of Figures

Fig. 1

Fig.2

Fig 3

Fig.4

Fig.5

Fig.6

Fig. 7

Fig.8

Fig.9

Fig. 10

Fig. 11

Fig 12

World resources of petroleum and natural gas 1998 [19]

Demand and supply of mineral oil in coming decades [ 181

Energy balance for the production of biodiesel versus rapeseed oil [18]

Molecule models of transesteritication: triacylglyceride methyl ester andcetane [18]

Reaction and solubility balances [18]

Batch process for the production of biodiesel [4]

Henkel transesteritication technology (reaction part) [4]

CD PROCESS for transesterification of triacylglycerols(Patents EU 0 562 504, US 5,354,878,)

Biodiesel standards, properties and production data act. E DIN 51606

Comparison of production costs of operating biodiesel plants

Biodiesel producers in Europe 1997198

Taxation of energy carriers according availability [18]