Sie sind auf Seite 1von 40

Pergamon

PI!:S0360-1285(97)00034-8
Prog. Energy Combust. Sci. Vol. 24, pp. 125- 164, 1998
1998 El sevi er Science Ltd
Printed in Great Britain. All rights reserved
0360- 1285/ 98 $19. 00
COMBUS TI ON OF FAT AND VEGETABLE OIL DERI VED FUELS IN
DI ESEL ENGI NES
Michael S. Graboski* and Robert L. McCormick
Colorado Institute f or Fuels and High Altitude Engine Research and Department of Chemical Engineering and
Petroleum Refining, Colorado School of Mines, Golden, CO 80401-1887, U.S.A.
Ab s t r a c t - - I n this article, the status o f fat and oil derived diesel fuels with respect to fuel properties, engi ne
performance, and emi ssi ons is reviewed. The fuels consi dered are primarily the methyl est ers of fatty acids
deri ved from a variety of vegetable oils and animal fats, and referred to as biodiesel. The major obstacle to
widespread use of biodiesel is the high cost relative to petroleum. Economi cs of biodiesel production are
discussed, and it is concl uded that the price of the feedst ock fat or oil is the major fact or det ermi ni ng biodiesel
price. Biodiesel is completely miscible with petroleum diesel fuel, and is generally tested as a blend. The use of
biodiesel in neat or bl ended form has no effect on the energy based engi ne fuel economy. The iubricity o f t hese
fuels is superior to conventional diesel, and this property is imparted to bl ends at levels above 20 vol%. Emi ssi ons
of PM can be reduced dramatically through use o f biodiesel in engi nes that are not high lube oil emitters.
Emi ssi ons of NOx increase significantly for both neat and bl ended fuels in both t wo- and four-stroke engines. The
increase may be lower in newer, lower NOx emitting four-strokes, but additional data are needed to confirm this
conclusion. A discussion of available data on unregulated air t oxi ns is presented, and it is concl uded that
definitive studies have yet to be performed in this area. A detailed discussion of important biodiesel properties and
recommendat i ons for future research is presented. Among the most important recommendat i ons is the need for all
future studies to empl oy biodiesel of wel l -known composi t i on and purity, and to report detailed analyses. The
purity levels necessary for achieving adequate engi ne endurance, compatibility with coatings and elastomers,
col d flow properties, stability, and emi ssi ons performance must be better defined. 1998 Elsevier Science Ltd.
All rights reserved.
CONTENTS
1. Introduction 126
1. 1. History of Veget abl e Oil Based Fuels 126
1. 2. The Transesterification Process 127
1. 3. Economi cs of Biodiesel Manufacture 127
2. Properties of Fatty Aci d Est er Fuels 129
2. I. Chemical Composi t i on and Properties 129
2.2. Combust i on Properties 13 I
2.2.1. Cet ane number 131
2.2.2. Flash point 132
2.3. Distillation Temperatures 134
2.4. Specific Gravity 134
2.5. Heat of Combust i on 134
2.6. Fl ow Properties 135
2.6.1. Low temperature flow properties 135
2.6.2. Viscosity and surface tension 137
2.7. Storage and Stability 137
2.7.1. Iodine number 138
2.7.2. Oxidative stability and gum number 138
2.7.3. Wat er absorption and microbial activity 139
2.8. Biodiesel Industry Fuel Standard 139
3. Engi ne Performance 140
3.1. Fuel Economy 140
3.2. Torque and Acceleration 141
3.3. Engi ne Endurance Issues 142
3.3.1. Durability studies 142
3.3.2. Elastomer compatibility 143
3.3.3. Biodiesel lubricity 143
3.3.4. Summary 146
4. Emi ssi ons 146
4.1. Regulatory Barriers 146
4.2. Regulated Emissions: Engi ne Stand and Chassis Studies 146
4.2.1. Engine dynamomet er studies using two-stroke engi nes 147
4.2.2. Engi ne dynamomet er studies using four-stroke engi nes 152
4.3. Discussion of Increased NO~ Emission for Biodiesel 156
4.4. Smoke Opacity 159
4.5. Unregulated Emission and Air Toxi cs 160
*Corresponding author.
125
126 M. S. Graboski and R. L. McCormick
4.5.1. Soluble organic fraction
4.5.2. Poly-aromatic hydrocarbons
4.5.3. Aldehydes
4.5.4. Summary
5. Conclusions and Summary of Research Needs
6. Acknowledgement
7. References
160
160
161
161
161
162
162
l. INTRODUCTION
Agri cul t ural fats and oils, i n raw or chemi cal l y
modified forms, have the pot ent i al to suppl ant a fraction
of pet rol eum distillates and pet rol eum based petro-
chemi cal s early in the next century. Di esel boi l i ng range
material is of part i cul ar interest because it has been
shown to si gni fi cant l y reduce particulate emi ssi ons
relative to pet rol eum diesel. Bi odi esel is a name appl i ed
to fuels manufact ur ed by the esterification of r enewabl e
oils, fats, and fatty acids. By r enewabl e it is meant that
supplies of these raw mat eri al s can be repl eni shed by the
growth of pl ant s or product i on of livestock. The ul t i mat e
source of the energy cont ent of these fuels is the sun. The
terms met hyl soyat e, soyate, soyester (for met hyl est ers of
soybean oil), t al l owat e (for esters of tallow), a n d many
si mi l ar terms are used to describe these fuels. The
t echnol ogy to produce met hyl est ers from agri cul t ural
fats and oils is well known. The fatty acids may be
deri ved from whol e veget abl e oils such as soybean or
rapeseed (also cal l ed canola), rendered tallows, or waste
mat eri al s such as cooki ng and trap greases.
The maj or obstacle to wi despread use of fats and oi l s
as fuels and chemi cal s is the high cost of the finished
products relative to pet rol eum. The cost of bi odi esel
produced from food-grade oils such as soybean oil is on
the order of $ 2 - 3 per gal l on compared to $0. 50- 0. 60
for pet rol eum diesel on a pretax basis. Soybean oil
carbon is worth approxi mat el y 30 cent s per pound, while
pet rol eum based carbon is val ued at about 7 cent s per
pound. Tal l ow carbon is somewhat cheaper t han that
from soybean oil but is still not compet i t i ve with petro-
diesel. Wast e veget abl e oil carbon may be compet i t i ve
with pet rol eum carbon but may also be l i mi t ed in
vol ume.
Biodiesel is compl et el y mi sci bl e wi t h pet rol eum
diesel fuel (referred to as D- I for Number I and D-2
for Number 2 diesel oils) and is usual l y tested as a bl end.
These bl ends are referred to by the vol ume percent age
bi odi esel in the bl end. For exampl e, B-20 refers to a 20-
vol % biodiesel bl end. B-20 is approxi mat el y 2 wt %
oxygen and the majori t y of studies have been conduct ed
at this bl end level. Test i ng to date has reveal ed several
t echni cal probl ems, al t hough none seem i nsur mount abl e.
For exampl e, bi odi esel tends to i ncrease ni t rogen oxide
emi ssi ons compared to Number 2 diesel in heavy dut y
engi nes. Thi s represents a serious probl em for bi odi esel
use in ozone or PM-10 non- at t ai nment areas. However,
biodiesel or bi odi esel bl ends result i n dramat i cal l y l ower
emi ssi ons of particulate mat t er relative to pet rol eum
deri ved diesel fuel. Thi s is because of the hi gh oxygen
cont ent of these fuels whi ch i ncreases the oxygen present
in fuel rich regi ons of the combust i ng fuel spray,
reduci ng the amount of soot formed. In some cases,
bi odi esel s do not meet wi nt ert i me col d flow property
requi rement s. Probl ems caused by i ncompat i bi l i t y with
el ast omers have also been identified for some specific
bi odi esel formul at i ons. Oxi dat i ve and bi ol ogi cal stability
is also an issue for these bi odegradabl e materials.
Fi nal l y, because of the greater degree of unsat urat i on
compared to pet rol eum diesels, some biodiesels can lead
to format i on of engi ne deposits. In this article, the
current status of fat and oil deri ved diesel fuels with
respect to fuel properties, engi ne performance,
emi ssi ons, and the probl em areas not ed above is
reviewed.
1.1. History of Vegetable Oil Based Fuels
Earl y i n this cent ury, work directed at renewabl e
diesel fuels had been initiated. It was i mmedi at el y
recogni zed that the use of whole veget abl e oils was not
accept abl e i n diesel engi nes. Wal t on I i n 1938 reported
on pi oneer i ng work with veget abl e oils and suggested an
early concept for biodiesel. Three oils were exami ned in
a diesel engi ne whi ch ut i l i zed 0.416 Ib/ bhp-hr of fuel,
si mi l ar to a modern engi ne i n efficiency. Steady-state
testing showed that soybean oil, pal m oil, and cottonseed
oil all gave fuel economi es of 9 0 - 9 1 % compared to
pet rol eum diesel at wide open throttle and various
speeds. Whol e oils were reported to form carbon
deposits and exhi bi t pour poi nt probl ems; pal m oil
corroded copper and brass significantly. Because of the
difficulties experi enced, Wal t on suggested splitting of
the triglycerides and usi ng the resul t i ng fatty acids as
fuel.
The i dea suggested by Wal t on evol ved sl owl y and
consi derabl e effort was devot ed to i nvest i gat i ng vege-
t abl e oils. Mart i nez de Vedi a 2 i n 1944 reported on tests
with 20 and 40% l i nseed oil/diesel blends. Wi t h these
bl ends, l ube oil properties i ncl udi ng acidity, ash,
asphal t ene precipitates, and Conradsen carbon i ncreased
duri ng use, and i ncreased more rapidly t han for diesel
alone. The aut hor found that decant i ng the fuel off of the
precipitate before use coul d mi ni mi ze foul i ng of
i nject ors and cl oggi ng of fuel filters. Car bon deposits
on engi ne combust i on chamber parts were si gni fi cant l y
greater with the bl ends t han with diesel alone. The aut hor
stated that l i nseed oil bl ends woul d be t roubl esome i f
used in commerci al equi pment for ext ended operat i ng
periods. Huguenar d 3 i nvest i gat ed fuel economy and
i ndi cat or card traces for cot t onseed oil/diesel bl ends at
vari ous i nj ect i on t i mi ngs in two laboratory scale IDI
diesel engi nes. Cot t onseed oil and bl ends with diesel
coul d be run with greater t i mi ng advance t han diesel
fuel. After a modest peri od of operation, the first engi ne
Fat and vegetable oil derived fuels 127
fai l ed to make rated load. The engi ne was di ssembl ed
and found to be heavi l y car boni zed and t o have ring
damage. Br uwer and cowor ker s 4 in 1980 report ed that
sunfl ower seed oi l is i nferi or to di esel in t erms o f fuel
economy and power. Furt hermore, as t he i nject ors
coked, unburned fuel began to di l ut e t he crankcase oil
causi ng ring st i cki ng and general engi ne failure. The
i nvest i gat i ons descri bed here are supported by many
ot her studies that poi nt to engi ne endurance issues
associ at ed with the use o f whol e veget abl e oi l s or
veget abl e oi l s bl ended with diesel. 5-9
Br uwer and coworkers, 4 in one of t he first report ed
studies on fatty aci d esters, found that usi ng an est er o f
sunfl ower oil seemed to r esol ve the pr obl ems associ at ed
with t he whol e oil and in fact pr oduced less carbon
deposi t s in a test engi ne than pet r ol eum der i ved diesel.
Smoke opaci t y was also l ower wi t h the est er than with
diesel. Bacon and cowor ker s ~ report that coki ng and
pol ymer i zat i on of veget abl e oi l s can be mi ni mi zed by
transesterification. It was also not ed that hydrogenat i on
to mi ni mi ze st orage stability and coki ng in whol e oi l s
and esters can result in undesi rabl e l ow t emperat ure fluid
properties. For t and Bl umber g 7 per for med engi ne testing
studies of cot t onseed oil, met hyl est er. They obser ved
per for mance compar abl e to di esel wi t h no change in
power out put over a 200-hr endurance test. Engl er and
cowor ker s tt exami ned bl ends of sunfl ower oi l and
sunfl ower oil et hyl est er prepared by conver t i ng 38, 68
and 98% of the initial oil. Unaccept abl e combust i on
chamber deposi t s wer e obser ved for the 38 and 68%
conver si on fuels. For the nearl y pure et hyl est er t hese
deposi t s wer e not significant. These posi t i ve initial
findings wi t h regard to engi ne performance, engi ne
deposits, and emi ssi ons have pr ompt ed consi derabl e
recent research into fat and veget abl e oil est er based
di esel fuels.
1.2. The Transesterification Process
Bi odi esel may be manufact ured in batch or cont i nuous
syst ems by transesterification. ~2 In transesterification,
one est er is conver t ed to another. The react i on is
cat al yzed by react i on with ei t her aci d or base and
i nvol ves react i on with an al cohol , t ypi cal l y met hanol i f a
bi odi esel fuel is the desi red product. A si mpl e mol ecul ar
represent at i on of the react i on is shown in Fig. I. As
t ypi cal l y practiced, a basic cat al yst such as sodi um
hydr oxi de is used to conver t the gl ycerol based triesters
(or triacyl gl yceri des) whi ch make up fats and oi l s to
met hanol based monoest er s (or met hyl est ers) yi el di ng
free gl ycer ol as a byproduct. A st oi chi omet ri c material
bal ance yi el ds the fol l owi ng si mpl i fi ed equat i on:
Fat or Oi l + 3 Met hanol ~ 3 Met hyl est er + Gl ycer ol
O H
II I
R 3 ~ C ' o ' ~ ' H
H
Fat or Oil
+ 3 H3C-OH
Methanol
N a O H
o r
Acid
O
I I
I C CH 3 HO- ~H 2
RI o ' O ~
II
R2.,.C.,o,CH3 + HO- ~H
R3 / C' o ' CH3 HO-CH2
Methyl Esters Glycerol
Fig. 1. Simple representation of the transesterification reaction.
proceeds to a conver si on of 9 0 - 9 7%, in an excess of
met hanol , wi t hi n appr oxi mat el y 1 hr. The r emai ni ng
3 - 1 0 % is gl ycer ol , mono/ di / t ri gl yceri des, and free
fatty acids. Much of t he free fatty aci d is conver t ed to
soap (sodi um salt of t he fatty acid) and water.
Up to 0.5 wt % cat al yst is requi red t o pr omot e the
transesterification. In most processi ng flow sheets the
caustic cat al yst is not r ecover ed and recycl ed. Thus,
fresh caustic must be cont i nuousl y added. Washi ng to
r emove the spent caustic is often accompl i shed with
wat er yi el di ng a si gni fi cant amount of wast ewat er from
the process. Devel opment of a het er ogeneous cat al yst for
this process woul d significantly reduce pr ocessi ng and
envi r onment al costs. The byproduct gl ycer ol is nearl y
i nsol ubl e in bi odi esel and in the feed st ock oil and thus
forms a separate l i qui d phase. The bi odi esel may requi re
distillation to r emove traces of gl yceri des. The gl ycerol
may be purified by vacuum distillation.
Ethanol or ot her al cohol s may be used in the
transesterification process. These are general l y less cost
effect i ve to use, and are not as easi l y react ed with the fat
or oil as is methanol. Bi odi esel can be made fr om wast e
oi l s as wel l . Reed et al. 13 descri be one met hod for
produci ng esters from wast e cooki ng oils cont ai ni ng
si gni fi cant quant i t i es o f free fatty aci ds l i berat ed duri ng
the cooki ng process. The si gni fi cant di ffer ence com-
pared to convent i onal transesterification is that addi-
tional caust i c must be added to neut ral i ze the free fatty
aci ds by conver t i ng them to soap pri or to transesterifica-
tion. These soaps separate from the bi odi esel in final
washing.
1000 kg 107.5 kg 1004.5 kg 103 kg.
1.3. Economics of Biodiesel Manufacture
The mass fl ows shown are for t he case of compl et e con-
versi on of stearic aci d t ri gl yceri de. The process is ver y
simple. At sl i ght l y above r oom t emperat ure this react i on
For a typical bi odi esel plant, the capital cost of the
i nst al l ed faci l i t y i ncl udi ng the cost of project devel op-
ment, cont i ngency, and ot her i t ems may be on the or der
128 M. S. Graboski and R. L. McCormick
Table I. Economics of biodiesel manufacture. Basis: 10 MM gal/year plant
Cost item Annual amount Unit price Annual total
Capital cost 10 years $2 per annual gallon $20 000 000
Labor and burden $20/hr 12 total $499 200
Overhead 50% $249 600
Methanol 1.167 MM gal $0.75/gal $875 250
Caustic 35.8 tons $400/ton $14 320
Power 100 kW $0.07/KWh $56 000
Steam 0.25 MM Btu/hr 5$/MM $10000
Water 1 gal/gal 5$/Mgal $50 000
Local taxes and insurance 2% Capital $400 000
Maintanence 3.5% Capital $700 000
Operating expense ($2 854 370)
Gross income needed $6 262 239
Income tax 35% ($1 491 784)
Depreciation 10 years $2 000 000
Required cash flow 20% DCF $4 770455
Glycerine revenue 738 278 gal $7.50 $5 537 084
Feedstock oil cost 71700 000 Ib $0.25 ($17 925 500)
Biodiesel 10 MM gal $2.15
3. 0
2. 5
2 . 0
1.5
|
. ~ 1. 0
0. 5
0.0
Cl pi t al Colr, t Glycerine Price
S/Annual Gallon
2 . 0 0 5. 00
. . . . . . 2 . 0 0 7 . 5 0
- - 1. 50 7.50 White I
~ - . 1. 50 10. 00
, . -
Wwl~eYellow
Grease / . . . . . ' " 1 . / - . . I
, - I / / " ' /
. .
0 . 0 5
Soybean
Oil
Tallow and
= . . . . I = . . . .
0 . 1 0 0 . 1 5 0. 20
F e e d s t o c k O i l C o s t , $ / I b
Fig. 2. Sensitivity of biodiesel cost per gallon to feed stock cost.
0 . 2 5 0 . 3 0
of $1. 00- 2. 00 per annual gal l on. The manufact ur i ng
costs of bi odi esel are domi nat ed by t he cost of the oil
feed stock. Thi s is readi l y shown by the fol l owi ng
engi neer i ng economi c estimate.
In this cal cul at i on, t he 10 mi l l i on gal l on per year pl ant
is assumed to cost $2 per annual gal l on, a 20% DCF
(di scount ed cash flow) ret urn on i nvest ment is required,
and 100% equi t y fi nanci ng is assumed. The capital
i ncl udes the basi c i nst al l ed pl ant , i nt erest dur i ng
const ruct i on, soft devel opment costs such as permi t t i ng,
feed stock and product sales and purchase contracts,
worki ng capital, and project cont i ngency. A 10-year
project and depreci at i on life is assumed. Wi t h a 35%
combi ned Federal and State i ncome tax rate, the pl ant
annual gross i ncome must be $6.26 mi l l i on to satisfy the
return requi rement . Operat i ng costs are based upon
chemical i ndust ry experi ence (see for exampl e, Ref. 14).
Tot al operat i ng costs are on the order of $2.8 mi l l i on.
Wi t hers and Noordam 15 report a cost of $0.9 mi l l i on for
a canol a to bi odi esel conversi on facility wi t h a capacity
of 2.7 mi l l i on gal l ons per year, i n l i ne with the operat i ng
costs est i mat ed here. Tabl e 1 shows that the largest l i ne
i t em expense is the cost of feed stock oil at $17.9 mi l l i on
when pri ced at a market level of $0.25 per pound for
soybean oil.
The pl ant desi gn is assumed to produce a hi gh qual i t y
glycerol. The gl ycerol byproduct , val ued at $7.50 per
gal l on ($0.75 per pound), produces r evenue whi ch is
approxi mat el y equal to the sum of the requi red ret urn
and operat i ng costs. Thus, the cost of the feed stock oil
must be recovered compl et el y from biodiesel sales. The
sel l i ng price of bi odi esel is thus near the purchase price
of the feed stock oil.
Di fferent capital costs, fi nanci ng assumpt i ons and
Fat and vegetable oil derived fuels 129
oper at i ng s cenar i os wi l l l ead t o s ome wha t di f f er ent
r esul t s but will not al t er t he gener al concl us i on. For
exampl e, it mi ght be ar gued t hat bur de ne d and over -
headed l abor cost s are t oo hi gh. Si nce t he l abor cost is a
smal l par t o f t he over al l pr oduct i on cost , a s s umi ng no
i ncr ease i n l abor needs for cons i der abl y l ar ger scal e
pl ant s has an i ncons equent i al effect on bi odi es el sel l i ng
pri ce.
Fi gur e 2 s hows a s ens i t i vi t y pl ot wi t h cases for l ower
capi t al and va r yi ng gl ycer ol val ues as a f unct i on o f feed
st ock oi l pri ce. Thr ee separ at e f eed st ock cases are s hown
on t he sensi t i vi t y pl ot . Thes e ar e use of s oybean oi l or
ot her veget abl e oil, use of t al l ow a nd c ommodi t y whi t e
gr eas e ( CWG) , and t he use of wast e yel l ow gr ease.
Choi c e whi t e gr eas e is a c ommodi t y t r aded wi t h a
s t andar d speci fi cat i on de ve l ope d by t he soap i ndust r y.
Yel l ow gr eas e is pr i mar i l y r es t aur ant gr eas e a nd off-
speci fi cat i on whi t e grease. The pr i ces for s oybean oil,
t al l ow and CWG are t ypi cal l at e 1995 cas h pr i ces
r epor t ed i n t he Wal l St r eet Jour nal . The yel l ow gr eas e
pr i ce is bas ed upon c onve r s a t i ons wi t h col l ect or s wor k-
i ng for r ender i ng oper at i ons pr oduci ng ani mal feed.
Fi gur e 2 suggest s t hat wast e yel l ow gr eas e is t he f eed
st ock of choi ce. It is t he onl y feed st ock capabl e of
pr oduci ng bi odi es el t hat can c ompe t e wi t h Numbe r 2
di esel . The spot pr i ce of Numbe r 2 oi l has aver aged
about 5 0 c e n t s per gal l on dur i ng 1995. Si nce t he
r ender i ng i ndus t r y c ons ume s t he l i ons ' shar e of t he
wast e yel l ow gr eas e t oday, i t s use f or bi odi es el
manuf act ur e coul d dr i ve up t he yel l ow gr eas e pri ce.
Table 2. Typical elemental composition of soybean oil methyl
esters and conventional Number 2 diesel fuel
Number 2 diesel Methyl soyester ~
wt% C 87 77.2
wt% H 13 11.9
wt% O 0 10.8
wt% S < 0.05 - -
~'Average of data from Refs 19-23.
Ver y l i t t l e i nf or mat i on on t he pr oper t i es and use of wast e
yel l ow gr eas e der i ved bi odi esel is avai l abl e.
The pr e domi na nt est er st udi ed is t he met hyl es t er o f
s oybean oi l , or met hyl s oyat e. Soybe a n oi l is t he ma j or
veget abl e oi l pr oduced i n t he Uni t e d St at es. Eur opean
bi odi es el is ba s e d upon r apes eed oi l me t hyl e s t e r and t hi s
is t he s e c ond mos t wi del y t est ed for m o f bi odi esel .
Si gni f i cant st udi es ha ve al so be e n conduct ed on t al l ow
est er s and l i mi t ed dat a is avai l abl e on a wi de r a nge of
ot her mat er i al s. Thi s pr e domi na nc e o f soy a nd r ape
est er s is r efl ect ed i n t hi s r evi ew.
2. PROPERTIES OF FATTY ACI D ESTER FUELS
Engi ne and vehi cl e st udi es of fat a nd oil der i ved
di esel s ha ve pr oduced hi ghl y var i abl e resul t s. In mos t
cases t hi s can be t r aced t o t he qual i t y and pur i t y of t he
fuel . However , i n ma ny cases exper i ment al er r or or
var i abi l i t y i s l ar ge (or not r epor t ed at al l ) and t he r esul t s
are meani ngf ul onl y i n a ver y qual i t at i ve sense. Thi s
sect i on r evi ews fuel pr oper t i es r el evant t o e ngi ne
pe r f or ma nc e a nd t o unde r s t a ndi ng t he t echnol ogy of
pr oduct i on and use of t hes e fuel s.
2.1. Chemical Composition and Properties
The chemi cal c ompos i t i on of fat a nd oi l es t er s is
de pe nde nt upon t he l engt h a nd degr ee of uns at ur at i on of
t he fat t y aci d al kyl chai ns. Ta bl e 2 pr es ent s el ement al
anal ys i s dat a for met hyl es t er s of s oybean oi l and
c onve nt i ona l di esel fuel . The c a r bon/ hydr oge n r at i o o f
bi odi es el s f r om ot her s our ces wi l l be sl i ght l y di ffer ent ,
de pe ndi ng upon t he degr ee o f uns at ur at i on. The mos t
i mpor t a nt c ompos i t i ona l di f f er ence bet ween D- 2 and
bi odi es el s is oxyge n cont ent . Bi odi es el cont ai ns 1 0 -
12 wt % oxygen, whi c h l ower s e ne r gy densi t y and, a nd as
will be s hown, l ower s t he par t i cul at e emi s s i on. In t he
Uni t e d St at es, on r oad c omme r c i a l Numbe r 2 di esel can
cont ai n up t o 5 0 0 p p m sul fur by ASTM D- 2622.
Bi odi esel is essent i al l y sul fur free. Sul fur is c onve r t e d
Table 3. Structural formula, melting, and boiling points for fatty acids and methyl esters in the diesel boiling range
Fatty acids Methyl esters
Acid No. of Structure Melting Boiling Melting Boiling
chain carbons point point point point
(C) (C) (C) (C)
Caprylic 8 CH3(CH2)rCOOH 16.5 239 - 4 0 193
Capric 10 CH3(CH2)aCOOH 31.3 269 - 1 8 224
Lauric 12 CH 3(CH 2) 10COOH 43.6 304 5.2 262
Myristic 14 CH ffCH2) 12COOH 58.0 332 19 295
Palmitic 16 CH3(CH2) ~4COOH 62.9 349 30 338
Palmitoleic 16 CH 3(CH 2) 5CH=CH(CH 2) 7COOH 33 - - 0 - -
Stearic 18 CH3(CH2) ~rCOOH 69.9 371 39.1 352
Oleic 18 CH 3(CH 2) 7CH=CH(CH 2) 7COOH 16.3 - - - 19. 9 349
Linoleic 18 CH 3(CH 2)4CH=CHCH2CH=CH(CH 2) 7COOH - 5 - - - 3 5 366
Linolenic 18 CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)TCOOH - I I - - - - - -
Arachidic 20 CH3(CH2) laCOOH 75.2 - - 50 - -
Eicosenoic 20 CH 3(CH 2) 7CH=CH(CH 2)9COOH 23 - - - 1 5 - -
Behenic 22 CH 3(CH2)20COOH 80 - - 54 - -
Erucic 22 CH3(CH 2) 7CIq=CH(CH2) I ICOOH 34 - - - - - -
130 M. S. Graboski and R. L. McCormick
Table 4. Weight percent of fatty acids in various fat and oils feedstocks
Carbon Saturated acids Mono unsaturated acids
number
8 10 12 14 16 18 > 18 < 16 16 18 > 18
Di Tri
Beef tallow - - - - 0.2 2 - 3 25- 30 21- 26 0. 4-1 0.5 2 - 3 39- 42 0.3 2
Butter I - 2 2 - 3 1- 4 8- 13 25- 32 8- 13 0. 4- 2 1- 2 2 - 5 22- 29 0. 2-1. 5 3
Coconut 5 - 9 4 - 1 0 44-51 13-18 7- 1 0 1- 4 - - - - - - 5 - 8 I - 3
Cod liver - - - - - - 2 - 6 7- 14 0- 1 0 - 2 10-20 25-31 35- 52
Corn - - - - - - 0 - 2 8- 10 1- 4 1- 2 30- 50 0 - 2 34- 56
Cottonseed - - - - - - 0 - 3 17-23 1- 3 23-41 2- 3 34- 55
Lard - - - - - - I 25- 30 12-16 0.2 2 - 5 41-51 2- 3 4 - 2 2
Linseed - - - - - - 0.2 5 - 9 0- 1 - - - - - - 9- 29 8- 29
Palm - - - - - - 1- 6 32- 47 1- 6 - - - - - - 40- 52 2 - I 1
Palm kernal 2 - 4 3 - 7 45- 52 14-19 6 - 9 1- 3 1- 2 0- 1 10-18 1- 2
Peanut - - - - - - 0.5 6-11 3 - 6 5- 10 I - 2 39- 66 17-38
Rapeseed . . . . 2- 5 1- 2 0.9 0.2 I 0- 15 50- 60 i 0 - 2 0
Safflower . . . . 5.2 2.2 76.3 16.2
Soybean - - - - - - 0.3 7-11 3 - 6 5 - I 0 0- 1 22- 34 50- 60
Sunflower 6.0 4.2 1.4 18.7 69.3
Tung . . . . . . . . . 4- 13 8- 15
45- 67
5- 10
2- 10
0.3
bulk
t o s ul f ur oxi de i n t he t ai l pi pe a nd a f r act i on o f t he s ul f ur
oxi de i s c onve r t e d t o sul fur i c aci d, whi ch i s c ount e d as
par t i cul at e, a r egul at ed pol l ut ant . Sul f ur oxi des ar e al so
r egar ded as ai r pol l ut ant s a l t hough t hey ar e not r egul at ed
as s uch f r om di esel engi nes . Pet r ol eum der i ved di esel
al so cont ai ns f r om 20 t o 40 vol % ar omat i c compounds .
Ar oma t i c s are known t o i ncr eas e e mi s s i ons o f par t i cul at e
a nd NOx. Bi odi es el i s es s ent i al l y non- ar omat i c.
Pet r ol eum di esel cont ai ns es s ent i al l y no ol efi ni c bonds .
Bi odi es el s c a n cont ai n a si gni f i cant n umbe r ~f t hes e
r eact i ve, uns at ur at ed si t es.
Al l nat ur al l y occur r i ng fat s a nd oi l s ar e es t er s of t he
t r i - al cohol , gl ycer ol . The s e ar e kn o wn as gl ycer i des,
t r i gl ycer i des, or t r i acyl gl ycer i des. Wi t h f ew except i ons ,
t he car boxyl i c aci ds (fat t y aci ds) f r om whi c h t he fat s and
oi l s ar e der i ved ar e al l s t r ai ght - chai n c o mp o un d s r a ngi ng 16
i n si ze f r om t hr ee t o 18 car bons . Ta bl e 3 s hows t he 17
18
chemi cal s t r uct ur e o f t he fat t y aci d c ha i ns f ound i n t he 19
mos t c o mmo n bi odi es el s our ce mat er i al s. Except f or C3 20
a nd C5 c ompounds , onl y aci ds wi t h an e ve n n umbe r o f 21
c a r bons occur nat ur al l y. Ac i ds ma y be s at ur at ed ( cont ai n 23
24
onl y s i ngl e bonds ) or uns at ur at ed ( cont ai n one or mor e 25
doubl e bonds). A s at ur at ed f at i s one t hat c a nnot 31
c he mi c a l l y add hydr ogen. An uns at ur at ed f at can be 31
hydr ogenat ed; f or each de gr e e o f uns at ur at i on, t hat i s Average
each doubl e bond, one hydr ogen mol ecul e c a n be added
26
per fat t y aci d. Ta bl e 3 al so s hows t he me l t i ng a nd boi l i ng 27
poi nt s o f t he var i ous fat t y aci ds. Th e s at ur at ed aci ds 28
e xhi bi t hi ghe r f r eezi ng poi nt s t ha n t he uns at ur at ed aci ds. 29
St ear i c aci d, f or exampl e, i s sol i d t o 70C, whi l e ol ei c 30
32
aci d mel t s at ! 6C. The onl y di f f er ence is t he pr es ence of
Average
a s i ngl e doubl e bo n d i n t he st r uct ur e of ol ei c aci d. For
f r eezi ng poi nt , chemi cal s t r uct ur e i s ver y i mpor t ant . The 23
boi l i ng poi nt s o f t he aci ds, on t he ot her hand, ar e 23
de pe nde nt on t he l engt h of t he c a r bon chai n but near l y 25
32
i nde pe nde nt of t he degr ee o f uns at ur at i on of t he fat t y 33
aci d. The s e obs er vat i ons r egar di ng t he ef f ect o f chemi cal 33
st r uct ur e on me l t i ng a nd boi l i ng poi nt s al so appl y t o 34
es t er s of t he fat t y aci ds, al t hough t he boi l i ng and me l t i ng 34
35
poi nt s ar e si gni fi cant l y l ower , as not ed i n Ta bl e 3.
Ta bl e 4 s umma r i ze s t ypi cal fat t y aci d c ompos i t i on
dat a f or var i ous t r i gl ycer i des. For mos t fat s and oi l s of
i nt er est t he maj or i t y o f t he fat t y aci ds ha ve 16 and 18
c a r bon l engt h chai ns. Ani ma l t al l ow i s c ompos e d of
about 60% sat ur at ed, pai mi t i c and st ear i c aci ds. The
r e ma i nde r i s si ngl y uns at ur at ed ol ei c aci d. Soybean
oi l , c or n oi l , pe a nut oi l et c. cont ai n pr e domi na nt l y
uns at ur at ed aci ds, t he maj or i t y c ont a i ni ng ol ei c a nd
l i nol ei c aci ds ( doubl y unsat ur at ed). Rapes eed oi l f r om
Table 5. Cetane number of various biodiesels
Reference Fuel Cetane
number
Number 2 diesel 40 (mi n)- 52
Soybean oil methylester 51.4
Soybean oil methylester 45.8
Soybean oil methylester 48.0
Soybean oil methylester 56.4
Soybean oil methylester 53.1
Soybean oil methylester 54.7
Soybean oil methylester 46.2
Soybean oil methylester 56.9
Soybean oil methylester 50.3
Soybean oil methylester 5 I. I
Soybean oil methylester 45.7
Soybean oil methylester 50.9
Rapeseed oil methylester 54.4
Rapeseed oil methylester 48.0
Rapeseed oil methylester 51.6
Rapeseed oil methylester 51.5
Rapeseed oil methylester 50.0
Rapeseed oil methylester 61.8
Rapeseed oil methylester 52.9
Soybean oil ethylester 48.2
Soybean oil butylester 51.7
Tallow methylester 58.8
Rapeseed oil ethylester 64.9
Sunflower oil methylester 49.0
Cottonseed oil methylester 51.2
Palm oil methylester 50.0
Palm stearin methylester 52.0
Frying oil ethylester 61.0
Fat and vegetable oil derived fuels 131
i
6 4
6 2 ~ S oy / N o. 2 R ef . 2 4 r Z = 0.8 9
- - O - - Tallow/N o. 2 R ef . 2 4 r = = 0.9 8 . ~
6 0 ~ S oy / N o. 2 R ef . 1 8 ? = 0 . 9 2
S oy l N o. 2 R ef . 1 9 r Z = 0.9 0
5 8
5 6 vv~
v
5 4 0
5 2
5 0
4 8
4 4 4 6 ~ ~ _ ~ . ~ 4 ~ ~ e
4 2 , . . , . . . . , . . . . , . . . . . . . . . , . . . . i . . . . i
0 2 0 4 0 6 0 8 0
W e i g h t P e r c e n t B i o d i e s e l
Fig. 3. Cetane number for blends of soy and
. . . . i . . . .
1 0 0 120
tallow methylesters with Number 2 diesel.
s ome s our ces cont ai ns a hi gh per cent age o f t he
monouns a t ur a t e d, C22 er uci c aci d.
2.2. Combustion Properties
2.2.1. Cetane number
The cet ane n umbe r of t he fuel , speci fi ed by AS TM
D- 613, is a meas ur e o f i t s i gni t i on del ay wi t h hi ghe r
cet ane numbe r s i ndi cat i ng shor t er t i me bet ween t he
i ni t i at i on of fuel i nj ect i on and i gni t i on, a des i r abl e
pr oper t y in di esel e ngi ne fuel . The cet ane i ndex is
defi ned by ASTM D-976. The cet ane i ndex is a
cal cul at ed pr oper t y t hat cor r el at es wel l wi t h cet ane
numbe r for nat ur al pet r ol eum st ocks. Cet ane i ndex is
al so a meas ur e of fuel ar omat i ci t y and is t her ef or e not
Table 6. Cetane number for pure fatty acid esters
Reference Fuel Cetane
number
36 Caprylic acid methylester 18.0
37 Caprylic acid methylester 33.6
36 Capric acid methylester 47.9
37 Capric acid methylester 47.2
37 Capric acid ethylester 51.2
36 Lauric acid metbylester 60.8
37 Lauric acid metbylester 61.4
36 Myristic acid methylester 73.5
37 Myristic acid methylester 66.2
37 Myristic acid ethylester 66.9
36 Palmitic acid methylester 74.3
37 Palmitic acid methylester 74.5
36 Stearic acid methylester 75.6
37 Stearic acid methylester 86.9
38 Stearic acid etbylester 76.8
38 Oleic acid methylester 55.0
38 Oleic acid ethylester 53.9
38 Linoleic acid methylester 42.2
38 Linoleic acid ethylester 37.1
38 Linolenic acid methylester 22.7
38 Linolenic acid ethylester 26.7
r el evant t o bi odi esel , whi ch cont ai ns no ar omat i c
compounds .
The cet ane n umbe r of bi odi es el s depends on t he par ent
oil sour ce but in gener al is at t he hi gh end of t he r ange
t ypi cal o f Numbe r 2 di esel , as not ed i n Ta bl e 5. Repor t ed
cet ane numbe r s r ange f r om 45. 8 t o 56. 9 for soy and fr om
48 t o 61. 8 for r apes eed met hyl es t er s . Thi s br oad r ange of
val ues is pr obabl y caus ed by di f f er ences i n t he fr act i onal
c onve r s i on of t r i gl ycer i des t o es t er s and by t he pr es ence
of r esi dual met hanol and gl ycer ol i n t he fuel . Exami -
nat i on of fl ash poi nt and di st i l l at i on dat a pr es ent ed bel ow
conf i r ms t hi s concl us i on for t he r ef er ences gi vi ng cet ane
numbe r s bel ow about 50. The aver age of t he avai l abl e
dat a pr es ent ed in Tabl e 5 is 50. 9 for soy and 52. 9 for
r apes eed est ers. For t he ot her est er s l i st ed, onl y one dat a
poi nt is avai l abl e but t hey ha ve cet ane numbe r s i n t he
4 8 - 6 0 range. Hi ghl y sat ur at ed est er s such as t hose
pr epar ed fr om t al l ow and us ed fr yi ng oil ha ve t he hi ghes t
cet ane number s . The ef f ect of bl e ndi ng bi odi esel on
cet ane n umbe r is near l i near f or mi xt ur es of est er s wi t h
ei t her Numbe r 1 or Numbe r 2 fuel s, t9'25 Thi s is s hown in
Fig. 3 wher e t he hi gh cor r el at i on coeffi ci ent s suppor t a
l i near r el at i ons hi p bet ween cet ane numbe r s of t he neat
fuel s and bl ends, in spi t e of t he appar ent cur vat ur e of t he
t r end for s oybean oil met hyl est er s. The dat a in Fig. 3, as
wel l as a gr eat deal of addi t i onal publ i s he d dat a (see
Ref. 20, for exampl e) , i mpl i es t hat t he neat cet ane
numbe r of est er fuel s can be used as t he bl e ndi ng cet ane
number . Fur t her mor e, t hi s s t at ement is t rue ove r t he
ent i r e compos i t i on r ange of mi xt ur es of est er s and di esel .
Cet ane n umbe r dat a for pur e est er s are compi l ed in
Tabl e 6. Cet ane n umbe r i ncr eases wi t h chai n l engt h,
decr eas es wi t h n umbe r of doubl e bonds , and decr eas es as
doubl e bonds a nd car bonyl gr oups move t owar d t he
c e nt e r of t he chai n. For pur e est er s of st ear i c aci d, cet ane
n umbe r was appr oxi mat el y 75, but for est er s of l i nol eni c
acid wi t h t hree doubl e bonds, cet ane numbe r had dropped
t o t he mi d- t went i es. Cet ane n umbe r i ncr eas ed fr om 47. 9
132 M. S. Graboski and R. L. McCormick
Table 7. Flash points for various biodiesels
Reference Fuel Flash point
(C)
Number 2 diesel 60-72
16 Soybean oil methylester > 110
17 Soybean oil methylester 179
20 Soybean oil methylester 143
21 Soybean oil methylester 174
23 Soybean oil methylester 141
24 Soybean oil methylester > 66
25 Soybean oil methylester 117
31 Soybean oil methylester > 110
43 Soybean oil methylester 127
Average Soybean oil methylester ! 31
26 Rapeseed oil methylester 84
28 Rapeseed oil methylester 152
30 Rapeseed oil methylester 188
31 Rapeseed oil methylester 250
32 Rapeseed oil methylester 175
Average Rapeseed oil methylester 170
25 Tallow methylester 138
43 Tallow methylester 96
44 Tallow methylester 23 a
Average Tallow methylester I 17
23 Soybean oil ethylester i 60
23 Soybean oil butylester 158
32 Rapeseed oil ethylester 185
33 Sunflower oil methylester 183
33 Cottonseed oil methylester 110
34 Palm oil methylester 174
34 Palm stearin methylester 165
35 Frying oil ethyl ester 124
aNot included in average.
t o 75.6 for sat urat ed C l0 t hr ough C ~s est ers. At and above
C t2, t he cet ane number s wer e above 60. Preparat i on o f
est er s wi t h l onger chai n al cohol s, such as et hanol or
but anol , had little effect on oct ane number. Emi ssi on
t est i ng has s hown t hat above 5 5 - 6 0 , i ncr eased cet ane
has little or no i mpact on furt her emi s s i ons reduct i ons. 39
Incr easi ng cet ane number has been s hown to r educe
ni t r ogen oxi de (NO~) emi ssi ons. 4 Cet ane number can be
enhanced usi ng i gni t i on i mpr over s whi ch suggest s a
st rat egy f or el i mi nat i ng t he i ncr eased NO, emi ssi on
usually obs er ved wi t h bi odi esel s and bl ends. Cl ark et
al. 23 s howed t hat neat bi odi esel does not r espond t o
t r eat ment wi t h et hyl hexyl ni t r at e whi ch is wi del y used as
a cet ane i mpr over f or l ow quality di esel fuels. Sharp 41'42
s howed t he same for a 20% bl end o f bi odi esel in di esel
fuel (B-20). However , Sharp found t hat B-20 di d r es pond
t o a di ffer ent cet ane i mpr over , di -t -but yi per oxi de, and
NOx was decr eased.
2.2.2. Fl ash poi nt
Fl ash poi nt ( ASTM D-93) is a measur e o f the
t emper at ur e t o whi ch a fuel must be heat ed such t hat
t he mi xt ur e o f vapor and air above t he fuel can be
ignited. All Number 2 di esel fuel s have rel at i vel y hi gh
flash poi nt s (54(2 mi ni mum, 71(2 typical). The flash
poi nt o f neat bi odi esei s is even hi gher, t ypi cal l y gr eat er
t han 90C, as not ed in Tabl e 7. Low flash poi nt s
measur ed in s ome st udi es (i.e., Ref. 44) may be caused
by residual met hanol in t he est er. Thi s may al so be t he
cause o f t he large r ange o f flash poi nt s r epor t ed for a
gi ven est er i n Tabl e 7. Because puri t y is uncert ai n, it is
Table 8. Distillation data for various biodiesels
Reference Fuel IBP (C) T10 (C) T50 (C) T90 (C) EP (C)
Number 2 diesel 185 210 260 315 345
17 Soybean oil methylester 320 331 337 343 351
20 Soybean oil methylester 302 328 334 351 356
23 Soybean oil methylester - - - - 336 342 - -
24 Soybean oil methylester - - 321 (7%) - - - - - -
25 Soybean oil methylester 310 330 336 324 338
43 Soybean oil methylester 265 329 335 337
Average Soybean oil methylester 299 328 336 340 346
27 Rapeseed oil methylester 332 352 351 355 409
28 Rapeseed oil methylester 316 333 336 346 350
29 Rapeseed oil methylester 330 - - - - - - 340
30 Rapeseed oil methylester - - 335 - - 342 - -
Average Rapeseed oil methylester 326 340 344 348 366
25 Tallow methylester 304 326 331 337 337
43 Tallow methylester 21 g 323 332 353 354
44 Tallow methylester 104 (?) - - 327 338 - -
47 Tallow methylester 211 - - 323 - - 327
Average Tallow methylester 209 324 328 342 339
23 Soybean oil ethylester - - - - 336 344 - -
23 Soybean oil butylester - - - - 352 364 - -
34 Palm oil methylester 324 330 334 343 363
34 Palm stearin methylester 320 331 335 343 349
44 Tallow ethylester 99 - - 335 349 - -
44 Tallow butylester I 13 - - 346 353 - -
Fat and veget abl e oil deri ved fuel s 133
38 o
E
36 O
3 4 0
3 2 0
3 0 0
2 8 0
2 6 0
2 4 0
2 2 0
2 0 0
1 8 0
1 6 0
seed Ester
Meth y l Tallow Ester
I B P T I O TSO TgO EP
Fig. 4. Distillation cur ves for Numbe r 2 diesel and vari ous esters; dat a are aver ages from Tabl e 8.
Tabl e 9. Specific gravi t y of vari ous bi odi esel s
Reference Fuel Specific
gravi t y
Numbe r 2 diesel 0.85
16 Soybean oil met hyl est er 0. 8855
18 Soybean oil met hyl est er 0.8831
19 Soybean oil met hyl est er 0. 8844
20 Soybean oil met hyl est er 0. 8855
22 Soybean oil met hyl est er 0. 8810
23 Soybean oil met hyl est er 0. 8840
24 Soybean oil met hyl est er 0. 8880
43 Soybean oil met hyl est er 0. 8870
48 Soybean oil met hyl est er 0. 889
Aver age Soybean oil met hyl est er 0. 8853
26 Rapeseed oil met hyl est er 0. 8738
27 Rapeseed oil met hyl est er 0.885
28 Rapeseed oil met hyl est er 0. 882
29 Rapeseed oil met hyl est er 0.883
30 Rapeseed oil met byl est er 0. 8825
31 Rapeseed oil met hyl est er 0. 8855
32 Rapeseed oil met hyl est er 0. 8802
Aver age Rapeseed oil met hyl est er 0. 8820
25 Tal l ow met hyl est er 0. 8755
43 Tal l ow met hyl est er 0. 8772
44 Tal l ow met hyl est er 0. 8750
47 Tal l ow met hyl est er 0. 8745
Aver age Tal l ow met hyl est er 0. 8756
23 Soybean oil et hyl est er 0. 8810
32 Rapeseed oil et hyl est er 0. 876
34 Sunfl ower oil met hyl est er 0. 8800
33 Cot t onseed oil met hyl est er 0. 8800
34 Pal m oil met hyl est er 0. 8700
34 Pal m stearin met hyl est er 0. 8713
35 Fryi ng oil et hyl est er 0. 8716
44 Tal l ow et hyl est er 0. 8710
44 Tal l ow but yl est er 0. 8680
Tabl e 10. Heat of combust i on dat a for var i ous biodiesel sampl es
Reference Fuel HHV LHV
(Btu/Ib) (Btu/lb)
Numbe r 2 diesel 19300 18640
16 Soybean oil met hyl est er 17176 16000
17 Soybean oil met hyl est er 17650 - -
18 Soybean oil met hyl est er 17996 - -
20 Soybean oil met hyl est er 17156 - -
21 Soybean oil met hyl est er - - 15965
22 Soybean oil met hyl est er - - 15700
23 Soybean oil met hyl est er 17127 - -
24 Soybean oil met hyl est er 17087 - -
25 Soybean oil met hyl est er 17650 - -
43 Soybean oil met hyl est er 17248 - -
47 Soybean oil met hyl est er 17106 16034
Aver age Soybean oil met hyl est er 17355 15925
26 Rapeseed oil met hyl est er 17506 - -
28 Rapeseed oil met hyl est er - - 16224
29 Rapeseed oil met hyl est er - - 15985
30 Rapeseed oil met hyl est er - - 15940
31 Rapeseed oil met hyl est er 17136 - -
32 Rapeseed oil met hyl est er 17446 - -
Aver age Rapeseed oil met hyl est er 17363 16050
25 Tal l ow met hyl est er 17382 - -
43 Tal l ow met hyl est er 17186 - -
44 Tal l ow met hyl est er 17380 - -
Aver age Tal l ow met hyl est er 17283 - -
23 Soybean oil et hyl est er 17208 - -
32 Rapeseed oil et hyl est er 17433 - -
33 Sunfl ower oil met hyl est er - - 16580
33 Cot t onseed oil met hyl est er - - 16735
34 Pal m oil met hyl est er 17271 - -
34 Pal m stearin met hyl est er 17138 - -
35 Fryi ng oil et hyl est er 17428 16004
44 Tal l ow et hyl est er 17940 - -
44 Tal l ow but yl est er 17733 - -
134 M. S. Graboski and R. L. McCormick
di ffi cul t t o c ompa r e fl ash poi nt s o f es t er s f r om var i ous
sources. A mat er i al wi t h a bout 90(2 or gr eat er fl ash poi nt
is c ons i de r e d as non- ha za r dous f r om a st or age and
fi r e- hazar d poi nt of vi ew unde r U. S. De pa r t me nt of
Tr ans por t at i on r egul at i ons. Ne a t bi odi es el i s t hus muc h
safer t ha n di esel i n t hi s r egar d. In bl ends, t he di esel fl ash
poi nt wi l l pr evai l up t o t he 50% bl e nd l evel a nd t he n t he
fl ash poi nt wi l l be gi n t o ri se. 2 The Engi ne Manufact ur er s
Associ at i on ( EMA) 45 has expr essed c onc e m t hat because
of t he oxi dat i ve i nst abi l i t y of soy and t al l ow ester, flash
poi nt (as well as ot her propert i es di scussed bel ow) may
change dur i ng storage. Thi s possi bi l i t y does not appear t o
have be e n i nvest i gat ed i n quant i t at i ve studies.
2.3. Distillation Temperatures
As mi xt ur es of a f ew r el at i vel y s i mi l ar c ompounds , f at
and oi l es t er fuel s ha ve a nar r ow boi l i ng r a nge r el at i ve t o
Numbe r 2 di esel a nd e xhi bi t aver age boi l i ng poi nt s
r a ngi ng be t we e n ~- 325 a nd 350C. As not e d i n Ta bl e 8
and Fig. 4, t hi s t emper at ur e r a nge i s near t he hi gh e nd of
t he r a nge r epor t ed f or di esel . In B- 20 bl ends, fuel s
me e t i ng t he ASTM T- 90 di st i l l at i on speci fi cat i on (as
me a s ur e d by ASTM D- 86) c a n be pr oduced. However ,
EMA 4~ a nd ot her s ha ve r epor t ed t hat i nt ake val ve
depos i t f or ma t i on i s a pr obl e m wi t h soy ba s e d B- 20 at
l i ght l oad a nd t hi s may be r el at ed t o t he l ar ge per cent age
o f ol efi ni c, hi gh boi l i ng mol ecul es i n soyest er s. Not e t hat
sever al o f t he fuel s ampl es r epor t ed i n Ta bl e 8 ha ve
suspi ci ousl y l ow i ni t i al boi l i ng poi nt s, s ugges t i ng t he
pr es ence o f met hanol or gl ycer ol whi ch was not r e move d
af t er es t er synt hesi s. The s e fuel s mi ght al so be expect ed
t o ha ve l ow oct ane numbe r s and fl ash poi nt s, as was
not ed by Si ms 44 i n hi s st udy o f t al l ow met hyl est er s.
2.4. Specific Gravity
Numbe r 2 di esel exhi bi t s a speci fi c gr avi t y o f 0. 85
( ASTM D- 287). Bi odi es el speci fi c gr avi t y is r epor t ed t o
var y be t we e n 0. 86 a nd 0. 90 (see Ta bl e 9) and i s t ypi cal l y
0. 88. The r e f or e vol umet r i c met er i ng o f bi odi es el (as i n
t he uni t i nj ect or s us ed i n mode r n di esel engi nes ) r esul t s
i n t he del i ver y of a sl i ght l y gr eat er mas s of fuel . As
di s cus s ed i n t he f ol l owi ng sect i on, bi odi es ei s ha ve a
l ower e ne r gy c ont e nt on bot h a vol umet r i c a nd a mas s
basi s. Ther ef or e, al t hough a uni t i nj ect or mi ght de l i ve r a
l ar ger ma s s o f fuel , t he act ual e ne r gy del i ver ed is l ess
t han f or Numbe r 2 di esel .
2.5. Heat ofCombusfion
It i s gener al l y accept ed t hat fuel c ons umpt i on i s
pr opor t i onal t o t he vol umet r i c ener gy densi t y o f t he fuel
Table 11. Low temperature flow properties of biodiesels
Reference Fuel Cloud point (C) Pour point (C) CFPP (C)
50 Number 2 diesel - 15 to 5 - 3 5 to - 15 - 10 to - 2 0
16 Soybean oil methylester - 2 - - - -
17 Soybean oil methylester - 1 - 7 - 4
20 Soybean oil methylester - 3 - 7 - 4
21 Soybean oil methylester 0 - - - -
22 Soybean oil methylester - 2 - 4 - -
23 Soybean oil methylester 2 - 1 - -
24 Soybean oil methylester - I - - - -
25 Soybean oil methylester - - - 1 - -
43 Soybean oil methylester 3 19 - -
50 Soybean oil methylester 3 - 4 1
Average Soybean oil methylester - 0 . 5 - 3 . 8 - 4 . 4
26 Rapeseed oil methylester - 1 - 9 - -
27 Rapeseed oil methylester - 4 - - - -
29 Rapeseed oil methylester - 4 - 12 - 13
30 Rapeseed oil methylester - 1 1 - - 20
31 Rapeseed oil methylester - - - 7 - -
32 Rapeseed oil methylester 0 - 1 5 - -
Average Rapeseed oil methylester - 4 . 0 - 10.8 3.6
25 Tallow methylester - - 13 - -
43 Tallow methylester 12 9
44 Tallow methylester - - 6 - -
50 Tallow methylester 16 I 0 I 1
Average Tallow methylester 13.9 9 I I
23 Soybean oil ethylester - I - 4 - -
32 Rapeseed oil ethylester - 2 - 15 - -
34 Sunflower oil methylester - - - 7 - -
33 Cottonseed oil methylester - - 3 - -
34 Palm oil methylester - - 16
34 Palm stearin methylester - - 1 7
35 Frying oil ethylester 9 8
44 Tallow ethylester - - 6
44 Tallow butylester - - 6 - -
Fat and vegetable oil derived fuels 135
based upon the l ower or net heat i ng val ue (LHV).
Tabl e 10 reports heat i ng val ues for diesel and vari ous
esters. Number 2 diesel cont ai ns t ypi cal l y 131 295 Bt u/
gal (18 642 Btu/Ib) whi l e bi odi esel s cont ai n approxi-
mat el y 10% less (1 Bt u/ Ib = 2.236 MJ/kg). The ratio is
0. 892 for soy diesel. Thus vol umet ri c fuel economy will
be lower on bi odi esel and biodiesel bl ends. As will be
shown bel ow, fuel energy cont ent based fuel economy is
unaffected. Fr eedman and Bagby 36 and Kl opfenst ei n and
Wal ker 46 report heats of combust i on for pure fatty acid
methylesters.
2.6. Flow Properties
2.6.1. Low temperature flow properties
The key flow properties for wi nt er fuel specification
are cl oud and pour point. Cl oud point, ASTM D-2500, is
the temperature at whi ch wax format i on mi ght begi n to
pl ug the fuel filter. It is measured as the temperature of
first format i on of wax as the fuel is cooled. Pour poi nt
(ASTM D-97) is a measure of the fuel gel l i ng point. Thi s
temperature is a measure of the temperature at which the
fuel is no l onger pumpabl e. The pour poi nt is al ways
lower than the cl oud point. The cl oud poi nt is not
general l y affected by additives cal l ed flow improvers.
However, flow i mpr over additives can decrease the size,
or i nhi bi t the formation, of the wax crystallites formed
upon cool i ng the fuel and thus lower the temperature at
which wax pl uggi ng becomes a problem. Pour poi nt
additives can lower the temperature of fuel gel l i ng
significantly. The col d filter pl uggi ng point, CFPP
(Int ernat i onal Pet rol eum Standard IP 309 or ASTM D
4539) temperature is det ermi ned by dynami c testing and
2 0
10
o
"6 - 1 0
I 1.
" 0
o - 2 0
- 3 0
- 4 0
10
oO - 1 0
O
n
, . . - 2 0
0
o .
- 3 0
- 4 0
- - e - - S oy /N o. 1 Diesel
- - O - - S oy /N o. 2 Diesel
Tallow/N o. 1 Diesel
- - V - - Tallow/N o. 2 Diesel
i i l l !
0 I 0 2 0 30 4 0
V o l u me P e r c e n t B i o d i e s e l
S oy /N o. 1 Diesel
- - O - - S oy /N o. 2 Diesel
Tallow/N o. I Diesel
Tallow/N o. 2 Diesel
50
! ~ i i i
0 10 2 0 30 4 0 50
V o l u me P e r c e n t B i o d i e s e l
Fig. 5. Effect of blending soy and tallow methylesters on fuel cold flow properties; data from Ref. 50.
J~EC$ 24:2 ~C
136 M. S. Graboski and R. L. McCormick
measur es sever i t y of wax preci pi t at i on. Thi s test
measures t he t emperat ure at whi ch fuel filters are
expect ed to pl ug due to waxy precipitates. IP 309 is
si mpl er t o conduct than ASTM D 4539. However ,
ASTM D 4539 has been found to cor r el at e bet t er wi t h
Nort h Amer i can vehi cl e per for mance 49 because o f mi nor
di ffer ences in fuel syst em design.
In wi nt er t i me, Number 2 di esel fuel s are oft en di l ut ed
wi t h Number 1 or ker osene t o meet wi nt er t i me fl ow
speci fi cat i ons t hr oughout Nort h Amer i ca and fuel cl oud
and pour poi nt s are var i ed by refi ners to meet l ocal
cl i mat i c condi t i ons. Increasi ngl y, D- 2 fuel s are bei ng
treated wi t h addi t i ves t o mi ni mi ze the probl em. Mi dwes t
Bi ofuel s 5j report dat a for di esel fuel s wi t hout fl ow
i mpr over addi t i ves. The D- I fuel st udi ed exhi bi t ed cl oud
and pour poi nt s of bel ow - 40C. The D- 2 fuel exhi bi t ed
cl oud and pour poi nt s o f - 14 and - 21C. Wi nt er t i me
col d fl ow propert i es o f fuel s are hi ghl y vari abl e bet ween
suppliers and there is a wi de di ffer ence report ed for fuel s
in round robi n testing studies.
A compi l at i on o f bi odi esel cl oud, pour, and col d filter
pl uggi ng poi nt s is report ed in Tabl e 11. Al l bi odi esel
fuel s exhi bi t poor col d fl ow propert i es wi t h cl oud and
pour poi nt s 2 0 - 2 5 C hi gher than t hose of Number 2
diesel. These val ues are rel at i vel y hi gh when compar ed
to wi nt er ambi ent t emperat ures. Fr eezi ng poi nt s of
or gani c mol ecul es are ver y sensi t i ve to chemi cal
structure. The structural propert i es o f bi odi esel that
affect fr eezi ng poi nt are degr ee of unsaturation, chai n
length, and degr ee of branchi ng. Hi ghl y saturated t al l ow
esters are poor er in this respect than soy and rape esters.
Met hyl soy and rape esters exhi bi t aver age cl oud poi nt s
of about 0 and - 5 C and pour poi nt s o f about - 4 and
- 1 0 C, respect i vel y. Met hyl t al l owat e exhi bi t s an
aver age cl oud poi nt of 14C and a pour poi nt of 10C.
The effect o f chai n length, degr ee o f saturation, and
branchi ng has not been consi der ed in bi odi esel manu-
facturing. It has been suggest ed that i sopropyl est ers wi l l
have bet t er col d fl ow propert i es than met hyl , et hyl ,
or butylesters, 5~ al t hough no data t o support this
proposi t i on wer e presented. Reduci ng chai n l engt h and/
or i ncreasi ng chai n branchi ng woul d i mpr ove t he col d
fl ow propert i es of t he fuel. Chai n l engt h and degr ee o f
branchi ng mi ght be al t ered t hrough both plant breedi ng
or genet i c engi neer i ng approaches, as wel l as t hrough
chemi cal processi ng of t he bi odi esel to cl eave certain
doubl e bonds or to for m branched i somers. Ver y little
practical research has been done in the chemi cal
processi ng area. The col d fl ow propert i es of bi odi esel
fuel s are cl earl y an area in need of consi der abl e research.
50
Mi dwest Bi ofuel s also report ed data on soy est er and
t al l ow est er bl ended with Number i and Number 2 di esel
fuels. The di esel fuel s used for bl endi ng had cl oud and
pour points at t he l ow end of t he r ange t ypi cal o f di esel s.
Bl ends of soyat e and t al l owat e wi t h D- I and D-2 fuel s
showed that cl oud and pour poi nt s i ncreased as t he
amount of est er bl ended increased. The effect wi t h D- I
was si gni fi cant l y l arger than wi t h D- 2 as shown in Fig. 5
where t he i ncrease in t emperat ure is much st eeper for
Number I than Number 2 oi l s. In both cases, t he t al l ow
est ers wer e i nfer i or t o t he soy esters, consi st ent wi t h t hei r
chemi cal structure.
Col d fl ow or flow i mpr over addi t i ves can be used to
i mpr ove t he col d fl ow propert i es of di esel fuels. These
addi t i ves do not pr event wax format i on (that is, do not
change t he cl oud point) but keep t he smal l wax crystals
fr om gr owi ng and combi ni ng. They thus affect pour
poi nt and col d filter pl uggi ng point. Fl ow i mpr over
addi t i ves wi l l be r equi r ed for commer ci al bi odi esel fuel s
and blends, especi al l y for wi nt er use. The Mi dwest
Bi ofuel s 5 study o f t he effect o f pour poi nt depressants
showed that gel l i ng coul d be el i mi nat ed wi t h appropriate
commer ci al addi t i ves. The pour poi nt of neat soy
di esel was r educed to - 4 0 C wi t h a commer ci al
addi t i ve al t hough 1000 ppm o f addi t i ve was required.
However , t he results of this study di d not cl earl y show a
reduct i on in CFPP even wi t h hi gh addi t i ve concen-
trations. Devel opment of new flow i mpr over addi t i ves
speci fi cal l y for fat t y aci d esters may be a fruitful area.
Harri ngt on 52 showed that t he smal l pal mi t i c and
stearic aci d cont ent s o f sunfl ower and l i nseed oi l s great l y
i ncrease t he cl oud poi nt compar ed to ol ei c aci d esters
alone. Modi fi cat i on or purification o f t hese materials
mi ght t herefore have a di sproport i onal effect on col d
fl ow propert i es. A mor e recent study 53 exami ned
so- cal l ed wi nt eri zat i on wher e the oi l for est er is
refri gerat ed to i nduce cryst al l i zat i on o f t he hi gh fr eezi ng
Table 12. Viscosity of biodiesels
Reference Fuel Viscosity
(cs @40C)
Number 2 diesel 2.6
16 Soybean oil methylester 3.97
18 Soybean oil methylester 3.77
20 Soybean oil methylester 4.3
21 Soybean oil methylester 3.9
23 Soybean oil methylester 4.08
24 Soybean oil methylester 4.23
25 Soybean oil methylester 4.06
31 Soybean oil methylester 4.32
43 Soybean oil methylester 4.06
48 Soybean oil methylester 4.1
Average Soybean oil methylester 4.08
26 Rapeseed oil methylester 6.1
27 Rapeseed oil methylester 4.48
28 Rapeseed oil methylester 4.57
29 Rapeseed oil methylester 4.5
30 Rapeseed oil methylester 4.5
32 Rapeseed oil methylester 5.65
Average Rapeseed oil methylester 4.83
25 Tallow methylester 4.47
43 Tallow methylester 4.11
44 Tallow methylester 5.83
Average Tallow methylester 4.80
23 Soybean oil ethylester 4.41
32 Rapeseed oil ethylester 6.17
34 Palm oil methylester 4.5
34 Palm stearin methylester 4.6
35 Frying oil ethylester 5.78
44 Tallow ethylester 5.93
44 Tallow butylester 6.17
Fat and vegetable oil defivedfuels 137
7
3
- - t - - S oy M~ / I ma o r ~ I O C , R ef . 21
--0-- Soy Molhylutor ~20eC, R~ 32
R ~ M ~ l h y l u t a r ~
i i i i i i
0 20 4 0 6 0 8 0 100
W e i g h t P e r c e n t B i o d i e s e l
Fig. 6. Effect of blending soybean and rapeseed esters on diesel fuel viscosity.
poi nt component s. The l ower fr eezi ng l i qui d phase is
then decanted Yi el ds of soyest er, havi ng a cl oud poi nt o f
- 2 0 C, wer e onl y 30% by wei ght usi ng this method I f
commer i cal col d fl ow i mpr over addi t i ves wer e bl ended
pri or t o wi nt eri zat i on, yi el d i ncr eased to 80% for a cl oud
poi nt of - 11C.
Van Ger pen 54 has present ed dat a on t he i mpact of
cont ami nant s and i mpuri t i es on t he col d fl ow propert i es
of met hyl soyest er. Unsaponi fi abl e mat t er (sterols,
t ocopherol s, and ot her hydrocarbons) is present in
crude soybean oil at about 1.5 wt %. Thi s leads to
l evel s o f less than ! % in met hyl est ers. Unsaponi fi abl e
mat t er had no effect on col d fl ow propert i es up t o the
2% l evel . The i mpact of unconver t ed mono- and
di gl yceri des, havi ng saturated fatty aci d chains, on
col d fl ow propert i es was al so exami ned. These mat eri al s
had little effect on pour poi nt up t o t he ! wt % l evel but
exhi bi t ed a si gni fi cant effect on cl oud point, even at
0.05 wt %. Unsat urat ed monogl ycer i des had no i mpact
on col d fl ow properties.
figure suggest bl end vi scosi t y is l ower than woul d be
predi ct ed fr om a l i near combi nat i on model , probabl y
because di ssol ut i on of bi odi esel in D-2 mi ni mi zes
i nt r amol ecul ar i nt eract i ons responsi bl e for this property.
Based on t he cur ves in Fig. 6, t he vi scosi t y of blends
cont ai ni ng up to 30 wt % o f soy or rape met hyl est ers wi!l
most l i kel y meet standards for Number 2 diesel.
Surface t ensi on is anot her fuel propert y that affect s
spray at omi zat i on, dropl et size, and ot her i mport ant
propert i es of the di esel spray Onl y ver y l i mi t ed data on
t he surface t ensi on o f neat bi odi esel s and bl ends is
avai l abl e. A typical val ue for Number 2 di esel is
22.5 dyne/ cm at 100C. St ot l er 24 reports a val ue of
34.9 dyne/ cm at 60C for neat soy met hyl est er and
Reece and Pet erson 26 report 25.4 dyne/ cm at 100C for
rapeseed oi l methylester.
2.7. Storage and Stability
St abi l i t y encompasses thermal stability under both
hot and col d condi t i ons, resi st ance to oxi dat i on,
2.6.2. Viscosity and surface tension
The ASTM D-445 speci fi cat i on o f maxi mum 4.1 cSt
vi scosi t y at 40C is barel y met by soybean oil
met hyl est ers, as shown in Tabl e 12. Vi scosi t y val ues
for esters o f rapeseed oil and t al l ow exceed this val ue
17
si gni fi cant l y. In any case, t he vi scosi t y o f neat bi odi esel s 20
is hi gher than for typical Number 2 diesel. Hi gh vi scosi t y 23
l eads to poor er at omi zat i on o f t he fuel spray and less 24
accurat e operat i on of the fuel injectors Addi t i onal l y, t he Average
vi scosi t y o f bi odi esel and bi odi esel bl ends i ncreases
23
mor e rapi dl y as t emperat ure is decr eased than that of 32
Number 2 diesel. 45 Monogl ycer i de i mpuri t i es have al so 32
been shown to si gni fi cant l y i ncrease t he vi scosi t y of 34
met hyl soyesters. 54 The effect o f bi odi esel cont ent on the 34
35
vi scosi t y o f bl ends is shown in Fig. 6. The cur ves in this
Table 13. Stability in terms of iodine number for biodiesels
Reference Fuel lodine
number
Number 2 diesel 8.6
Soybean oil methylester
Soybean oil methylester 133.9
Soybean oil methylester ! 35. I
Soybean oil methylester 130.5
Soybean oil methylester 133.2
Soybean oil ethylester 123
Rapeseed oil methylester 97.4
Rapeseed oil ethylester 99.7
Sunflower oil methylester 125.5
Cottonseed oil methylester 105.7
Frying oil methylester 63.5
138 M. S. Graboski and R. L. McCormick
pol ymer i zat i on, a nd mi cr obi al act i vi t y dur i ng st or age,
and abs or pt i on of wat er. The ma i n s our ce o f i ns t abi l i t y i n
bi odi es el fuel s is uns at ur at i on i n t he fat t y aci d chai n. I f
t wo or mor e doubl e bonds ar e pr esent , t hey ha ve a
mut ual l y act i vat i ng effect . The me t a l s a nd el as t omer s i n
cont act wi t h bi odi es el dur i ng st or age c a n al so i mpact
st abi l i t y. Oxi da t i on l eads t o t he f or ma t i on of hydr o-
per oxi des, whi c h can at t ack el as t omer s or pol ymer i ze t o
f or m i ns ol ubl e gums.
2.7.1. I odine number
I odi ne n umbe r ( DI N 53241/ I P 84/ 81) is a me a s ur e of
t he degr ee o f uns at ur at i on o f t he fuel . Uns a t ur a t i on can
l ead t o depos i t f or ma t i on a nd st or age st abi l i t y pr obl e ms
wi t h fuel s, as not ed above. Soy and r apes eed me t hyl e s t e r
ha ve i odi ne val ues of appr oxi mat el y 133 a nd 97, as not ed
i n Ta bl e 13. Dat a do not a ppe a r t o be avai l abl e f or t al l ow
est er s but a l ower val ue i s expect ed ba s e d on t he gr eat er
degr ee of s at ur at i on of t hi s mat er i al . Me r c e de s Be nz
exper i ence 55 suggest s t hat fuel wi t h i odi ne n umbe r
gr eat er t han 115 is not accept abl e becaus e o f exces s i ve
c a r bon deposi t s. Ma ny bi odi es el s ha ve i odi ne n umbe r
gr eat er t han t hi s val ue, speci fi cal l y met hyl es t er s of
s oybe a n oil (see Ta bl e 13). Ryan et al. 56 addr es s ed
s oybean, sunfl ower , and c ot t ons e e d oi l use i n e ngi ne s
and s ugges t t hat t he ma xi mum i odi ne n umbe r s houl d be
l i mi t ed t o 135. Ma ny bi odi es el fuel s ar e pr oduced f r om
f eed st ocks t hat ar e nat ur al l y hi ghl y unsat ur at ed.
Re mova l o f t he uns at ur at i on by, f or exampl e,
hydr oge na t i on l eads t o a wor s e ni ng of col d fl ow
pr oper t i es. Res ear ch mus t be di r ect ed at addi t i ves t hat
can act t o st abi l i ze t he uns at ur at ed bonds i n bi odi esel
fuel s t o obt a i n an accept abl e st abi l i t y.
2. 7. 2. Oxidative stabil ity and gum number
Oxi dat i ve st abi l i t y i s me a s ur e d by ASTM D2274.
EMA 45 r epor t ed t hat c ompa r e d t o Numbe r 2 di esel ,
met hyl es t er s of t al l ow and soy wer e f ar mor e pr one t o
oxi dat i on i n t hi s test. Numbe r 2 di esel c ons ume d 5% of
t he avai l abl e oxygen, t al l ow met hyl es t er s c ons ume d
60%, and s oybean oi l met hyl es t er s c ons ume d 90%. Van
Ge r pe n 54 has not e d t hat cer t ai n mi nor c ompone nt s of
bi odi es el , s uch as t ocopher ol , are nat ur al ant i oxi dant s
and t ha t t hes e are r e mo v e d i f t he bi odi es el i s pur i fi ed by
di st i l l at i on. In c ompa r a t i ve oxi dat i on t est s, t he per oxi de
va l ue (a meas ur e o f t he a mount of hydr oper oxi des
pr es ent ) i ncr eas ed r oughl y four t i mes f as t er f or a di st i l l ed
soy me t hyl e s t e r t ha n f or undi st i l l ed. Int er est i ngl y,
f or ma t i on of hydr oper oxi des r esul t ed i n a si gni fi cant
i ncr eas e i n cet ane n umbe r ove r t he cour s e of t hes e
r el at i vel y s hor t - t er m t est s (up t o 24 days). Cl ear l y an
unde r s t a ndi ng o f t he ma xi mum accept abl e hydr o-
per oxi de l evel i n bi odi es el is needed. Thi s i nf or mat i on
mus t i ncl ude t he i mpa c t of hydr oper oxi des on el as t omer s
Table 14. Proposed fuel property standard for biodiese145
Property Units Test method Diesel Soybean oil Rapeseed oil
(USA) (ASTM D975) methylester methylester
(NBB standard) (DIN V 51606)
Density at 15C g/cc ASTM D 1298 - - 0. 86-0. 90 0.875-0.900
Viscosity at 40C mm2/s (cSt) ASTM D445 1.3-4.1 1.9-6.0 3. 5-5. 0
Flash point C ASTM D93 52 min 100 min 100 min
Cold filter plugging
Summer C ASTM D4359 * By customer 0 max.
Winter C - 2 0 max.
Pour point
Summer C ASTM D97 * By customer - -
Winter C
Sulfur content wt% ASTM D2622 0.05 max. 0.01 max. 0.01 max.
Distillation
5% Evaporation C ASTM D 1160 None To be determined
95% Evaporation C 282-338 None To be determined
Carbon residue wt% ASTM D189 0.35 max. 0.5 max. 0.3 max.
Coradson
Centane number ASTM D613-86 40 min 40 rain 49 min
Ash content wt% ASTM D482 0.01 max. 0.02 max. 0.01 max.
Water content ASTM D1796 0.05 vol% max. Visual 300 mg/kg max.
Particulate matter g/m 3 DIN 51419 - - Visual 20 max
Copper corrosion ASTM D130-88 3 max. 3 max. I max.
(3 hr at 50C)
Oxidation stability g/m 3 ASTM D2274 To be determined - -
Acid value mg KOH/g ASTM D664 To be determined 0.5 max.
Methanol content wt% To be determined None 0.3 max.
Monoglycerides wt% To be determined None 0.8 max.
Diglycerides wt% To be determined None 0.1 max.
Triglycerides wt% To be determined None 0.1 max.
Bound glycerin wt% To be determined - - - -
Free glycerin wt% To be determined To be determined 0.02 max.
Total glycerin wt% To be determined To be determined 0.25 max.
Iodine number DIN 5324 IflP 84/81 - - None 115 max.
Phosphorous content mg/kg DGF C-VI4 To be determined 10 max.
Fat and vegetable oil derived fuels 139
Table 15. Fuel economy for biodiesel (soybean oil methylesters)
and biodiesel/Number 2 diesel blends over the EPA transient
test, 1991 DDC Series 60 engine 19
Biodiesel CO2 Fuel
(%) (Bt uPahp-hr) (Btu/bhp-hr)
0 7176 7326
20 7040 7192
35 7080 7130
65 7006 7133
100 7038 7038
Avg/std dev 7068/66 7 t 64/106
and metals, fuel combust i on properties, mi crobi al
act i vi t y, and gum format i on.
Oxi dat i on product s for med in bi odi esel wi l l affect fuel
st orage l i fe and cont ri but e to deposi t format i on in tanks,
fuel syst ems and filters. Gum number is a measur e of
deposi t format i on. Fuel s with hi gh i odi ne numbers may
possess hi gh gum numbers. Cl ark et al. 23 det er mi ned
gum numbers for met hyl - and et hyl est ers o f soybean oi l
and found 16400 and 19 200, r espect i vel y. A compar -
abl e val ue for Number 2 di esel is 6 - 7. Bessee and Fey 57
exami ned the compat i bi l i t y o f pure soy met hyl est ers, as
wel l as bl ends wi t h D-2 and JP-8, wi t h six met al s
commonl y found in fuel systems. The test cont i nued for
6 mont hs wi t h peri odi c visual i nspect i on and measure-
ment o f Tot al Aci d Number (TAN), a measur e of t he
ext ent of fuel oxi dat i on as wel l as cor r osi ve t endency. At
the end of t he 6- mont h test, TAN had not i ncr eased for
the base fuel s cont ai ni ng no bi odi esel . Al l bi odi esel fuel s
exhi bi t ed ei t her a dramat i c i ncrease in TAN or t he
format i on o f gum deposits. Gum deposi t s wer e most
si gni fi cant for met al s cont ai ni ng copper whi l e aci d
numbers wer e hi ghest for sampl es in cont act wi t h steel
and al umi num. Cl ear l y soy based bi odi esel fuel s exhi bi t
poor stability r el at i ve to convent i onal diesel. Thi s is also
true for rapeseed based bi odi esel , as demonst rat ed duri ng
a 2- year st orage stability study wher e per oxi de and aci d
val ues i ncreased by mor e than one or der o f magni t ude. 32
Thi s is a part i cul arl y i mport ant area for future research i f
t hese fuel s are to become commer ci al l y accept abl e.
2.7.3. Water absorption and microbial activity
Wat er present in fuel can cause t he format i on of rust
and, in t he pr esence o f aci ds and hydr oper oxi des for med
by fuel oxi dat i on, l ead to corrosi on. Wat er is also a
necessary i ngredi ent for mi crobi al growt h, whi ch can
occur at t he i nt erface bet ween the fuel and any free wat er
phase. ASTM standard D-975 al l ows up to 500 ppm
wat er in D-2. As the sol ubi l i t y o f wat er in D-2 is onl y
about 60 ppm (at 25C), 58 any wat er above this l evel wi l l
be present as a separat e phase ei t her at t he bot t om o f the
tank or suspended as an emul si on. Wat er sol ubi l i t y data
are avai l abl e for met hyl soyest er and for a 20% bl end
with D-2. 54 The sol ubi l i t y of wat er in pure met hyl
soyest er was found to be ~- 1500ppm whi l e onl y
40 ppm (a val ue t hought to be statistically the same as
t he 60 ppm report ed in Ref. 58) di ssol ved in t he B-20.
Pure esters subj ect ed to convent i onal fuel handl i ng
pract i ces will most l i kel y be saturated with water. Thus,
upon bl endi ng of this wat er-sat urat ed material wi t h D-2,
a separat e wat er phase wi l l for m pr ovi di ng a site for
mi crobi al growt h.
Bi odi esel s pr oduced fr om soybean and rapeseed are
readily bi odegradabl e and furt hermore, the presence of
bi odi esel (i.e., in B-20) enhances the bi odegradabi l i t y of
pet r ol eum der i ved di esel in t he presence o f water. 32
However , there appear t o be no data fr om cont r ol l ed tests
avai l abl e on t he i mpact o f mi cr obi al act i vi t y on bi odi esel
fuel s duri ng storage or on t he use o f addi t i ves to pr event
mi cr obi al growt h. Gr owt h, of al gae in fuel st orage tanks
was not ed in a bi odi esel transit bus demonst rat i on
program. ~ 06
2.8. Biodiesel Industry Fuel Standard
Dat a on fuel propert i es di scussed above, and the data
on engi ne per for mance and emi ssi ons whi ch fol l ows,
exhi bi t a hi gh degr ee of vari abi l i t y for a gi ven bi odi esel
source. One possi bl e cause o f this is the fact that no
at t empt was made to insure that the bi odi esel fuels all
met t he same qual i t y standard. The Nat i onal Bi odi esel
Boar d (NBB) has been devel opi ng a fuel standard for soy
di esel , whi ch is shown in Tabl e 14 al ong with a DIN
(German) standard for rapeseed oil methylester. The
EMA has stated that devel opment o f such a standard is
necessary i f any manufact urer is to ext end warrant y
cover age to bi odi esel fuel ed engi nes. The EMA 45 ci t es a
number of areas of concer n bei ng addressed by NBB' s
fuel speci fi cat i on i ncl udi ng vi scosi t y, flow properties,
oxi dat i ve stability, corrosi on, free met hanol and
est eri fi cat i on byproduct s, and bi ol ogi cal growt h.
Sever al of t he standards are currently undefi ned such
as oxi dat i ve stability and aci d value. Resul t s present ed in
pr evi ous sect i ons i ndi cat e that standards for these
propert i es are cri t i cal for commer ci al devel opment of
Table 16. Fuel economy data for a series of engines operating with catalysts and timing changes (btu/bhp-hr)
Fuel Set-up DDEC MUI DDEC MUI MECH-L- 10 MUI-6V-
6V-92-TA 6V-71N 6V-92TA 6V-92 1987 92TA 1987
1991 1977 1 9 8 8 -1981/1989
Reference 59 60 41 61 24 24
DF-2 Stock 8593 8374 8426 8735 7252 8911
B-20 Stock 8529 8439 8258 8759 7192 8837
B-20 Timing 8599 8375 8475 8874 7066 8873
B-20 Timing + cat 8580 8835 8421 8835 7138 8819
Timing deg 3 4 1 2 ?
140 M.S. Graboski and R. L. McCormick
biodiesel fuels and research must be directed at their
definition. Efforts by researchers to insure that the
biodiesels they use meet the standards in Table 14 should
lead to results that are more consistent than those
reported in the past.
3. ENGI NE PERFORMANCE
3.1. Fuel Economy
In most reported studies, fuel consumption is calcu-
lated from the carbon dioxide emissions and an analysis
of the fuel carbon content. A more accurate approach is to
combine CO2 emission measurements with a gravimetric
measurement of fuel consumption. The uncertainty in
fuel economy values from CO2 emissions alone is
necessarily larger since the researchers do not close the
fuel/emissions carbon balance. The carbon balance
approach was taken by Graboski et al . 19 for soy
methylesters and blends with Number 2 diesel tested in
a four-stroke engine using the EPA heavy duty transient
test. Table 15 presents fuel economy data in Btu/bhp-hr
(1 Btu/bhp-hr = 0.0141 MJ/kW-hr) from this study. In
these tests, carbon input to and carbon output from the
engine differed by less than 2%. The standard deviation
in fuel economy by each method is ~ 1.5%. The data
clearly show that within experimental error, the energy
efficiency is independent of fuel composition.
Table 16 presents fuel economy data for a series of
engines operating on biodiesel and evaluated with and
without catalysts and timing changes. Timing changes
are investigated for biodiesels to eliminate the increased
NOx emissions observed for these fuels, as described in
Section 4 of this review. In general, these data show that
adding biodiesel to D-2 has no effect on energy fuel
economy. Within the accuracy of the data, employing a
catalyst and retarding timing for NOx control also does
not significantly impact fuel economy.
In addition to transient testing, energy fuel economy
data are available for steady-state and multi-mode
steady-state testing. For example, Clark et al. 23 studied
diesel, methylsoyate and ethyl soyate in a John Deere
4239TF direct injected turbocharged diesel engine
attached to an eddy current dynamometer. Fuel
economy, torque and horsepower at wide-open throttle
were all directly related to volumetric heating value of
the fuels.
Much of this data is summarized in Fig. 7 which
presents energy economy data for biodiesel and biodiesel
blends compared to Number 2 diesel for steady-state and
transient testing and covering a broad range of engine
models and vintages. Biodiesel blends vary from 10% to
neat, and include methyl, ethyl- and butylesters of
soybean oil and tallow. As the figure shows, the energy
fuel economy is independent of the fuel mixture fed to
the engine. Thus, the crude oil replacement benefits of
biodiesel depend on the total quantity used but not the
blend concentration.
Several road tests support the conclusions from engine
testing. Battelle 63 reported on a soy methylester B-20 bus
study carried out at Bi-State Development Agency in St
1 1 0 0 0
r . -
&
r - -
- - z
E
0
e -
8
uJ
" I
L I..
._ m
r n
1 0 0 0 0
9 0 0 0
8 0 0 0
7 0 0 0
6 0 0 0
5 0 0 0
5 0 0 0
Slope=1.004
r 2= 0. 9 79
I I I I I
6 0 0 0 7 0 0 0 8 0 0 0 9 0 0 0 1 0 0 0 0 1 1 0 0 0
N O. 2 Di e s e l Ec o n o my , B t u / b h p - h
Fig. 7. Fuel economy for neat biodiesel and blends. Data include a wide range of engines with soy and tallow based methylesters,
from Refs 16, 18, 22, 24, 4 I, 42, 44 and 59-62.
Fat and vegetable oil derived fuels 141
Loui s wher e fi ve buses each wer e run on B- 20 and fi ve
on cont rol Number 2 diesel. Appr oxi mat el y
200000 mi l es wer e accumul at ed wi t h each fleet. The
di esel buses wer e run 7 days per week whi l e t he
bi odi esel buses wer e operat ed 5 d a ys per week.
The measur ed fuel economy was 3. 76 mpg for B- 20
and 4.01 mpg for cont rol di esel , a 6% reduction. A 1 - 3 %
loss was expect ed based upon t he l ower heat i ng val ue o f
bi odi esel and no expl anat i on was pr ovi ded for the
di screpancy. The fuel s wer e not i nt erchanged for a gi ven
bus; t he fl eet si ze was so smal l that hardware di ffer ences
may have a si gni fi cant effect on mi l eage. Dat a on
passenger l oadi ng, dr i ver assi gnment and rout es wer e not
provi ded. Wi t hi n t he l i mi t at i ons o f t he desi gn o f this
study, ener gy cont ent based fuel economy was
unaffect ed by bl endi ng bi odi esel wi t h diesel.
ATE Management and Ser vi ce Company 64 report ed
on a st udy conduct ed by Ci nci nnat i Met ro. Si x buses
wer e t est ed wi t h soy met hyl est er B- 30 fuel . Four wer e
equi pped wi t h 1987 MUI and t wo wi t h 1989 El ect r oni c
DDC 6V- 92 t wo- st r oke power plants. Pri or t o t he test all
engi nes wer e t uned up and r ecei ved new injectors. Each
bus was power basel i ned on a chassis dynamomet er wi t h
D-2. The buses wer e not assi gned to fi xed rout es and
exper i enced a vari et y o f dr i vi ng situations. Fuel mi l eage
data wer e gi ven for each bus and mi l eage was on aver age
5% l ower wi t h B-30. The expect ed loss in mi l eage based
upon fuel heat i ng val ue was 3. 2%. The agr eement is thus
excel l ent wi t hi n t he accuracy o f this t ype o f study.
Dani el 65 report ed on t he Li nk Transi t Bi odi esel
Demonst r at i on Pr oj ect in t he state o f Washi ngt on. Thi s
study was a 1-month 104 000- mi l e demonst rat i on o f 20%
soybean oil met hyl est er bi odi esel . The base di esel was
not defined. They saw no si gni fi cant change in fuel
economy for 1991 and 1993 6V- 92TA DDEC II engi nes
in Or i on 1 Coaches. The expect ed change woul d have
been a 2. 2% loss in mi l eage.
Yost 66 report ed on a 6- mont h fi el d test by Spokane
Transit on D- I wi t h 30 and 20% soy met hyl est er.
Ei ght een coaches wer e used (6 each wi t h 6V- 71, 6V- 92,
6 L-71 engi nes of 1974- 92 vi nt age). The fuel mi l eage
was 1/2 mpg bet t er than wi t h D-1. The l ower heat i ng
val ue o f D- I is appr oxi mat el y t he same as for met hyl
soyester. However , it is not known how fuel economy
di ffer ences wer e act ual l y comput ed and whet her t here
was any cont rol o f propert i es on t he D- i empl oyed.
Howes and Ri deout 67"68 i nvest i gat ed emi ssi ons and
fuel economy for t wo urban buses usi ng t hree bus chassis
cycl es for di esel , soy met hyl est er B-20, as wel l as B-20
with t i mi ng changes and catalyst. Tabl e 17 shows the
fuel economy in mpg based on CO2 emi ssi ons. No data
on fuel composi t i on wer e r epor t ed and it was not stated
whet her t he B- 20 was pr oduced by mi xi ng with the
di esel reference fuel used. Tabl e 17 shows that t here was
no si gni fi cant effect o f bi odi esel addi t i on on mi l eage,
both with and wi t hout a 1.5 t i mi ng change. The
confi dence l i mi t s on the data encompass t he expect ed
2. 2% loss in mi l eage based upon fuel ener gy cont ent .
Addi t i on o f a cat al yst caused a 6. 2 and 8. 3% loss in
mi l eage for t he 6V- 92 and 8V-71 engi nes, r espect i vel y.
Table 17. Chassis dynamometer based fuel economy data
(mile/gal) 67'6s
Cycle Biodiesel 1988 DDC 1981 DDC
6V-92TA 8V-71
(%) (mpg) (mpg)
CBD Stock 0 3.69 3.59
CBD Stock 20 3.68 3.63
CBD Timing 20 3.54 3.59
CBD Cat 20 3.35 3.18
CBD Timing + cat 20 3.26 3.30
Arterial Stock 0 4.67 3.92
Arterial Stock 20 4.72 3.91
Arterial Timing 20 4.89 3.93
Arterial Cat 20 4.64 3.40
Arterial Timing + cat 20 4.56 3.84
Composite Stock 0 3.70 3.66
Composite Stock 20 3.63 3.52
Composite Timing 20 3.50 3.63
Composite Cat 20 3.34 3.21
Composite Timing + cat 20 3.33 3.43
Table 18. Effect of biodiesel content on engine peak torque. A
1991 Detroit diesel series 60 engine 19
% Biodiesel/test no. Peak torque, ft-lb
(1200 rpm)
0/1056 1283
0/1071 1279
0/1085 1278
0/1111 1286
20/1064 1275
35/1105 1270
65/1117 1256
100/1091 1210
Thi s is probabl y because of the effect of back pressure on
vehi cl e per for mance regardl ess of t he fuel , al t hough
back pressure measur ement s were not reported.
Based upon t he data descri bed above, neat bi odi esel
and bi odi esel bl ends exhi bi t a fuel economy proport i onal
to t hei r l ower heat i ng value. No i mpr ovement or
degradat i on in ener gy effi ci ency is expect ed.
3.2. Torque and Acceleration
The t orque devel oped is rel at ed to t he ener gy densi t y
o f t he fuel. St udi es have document ed reduct i ons in
t or que for bi odi esel bl ends and neat bi odi esel . Graboski
et al. 19 found that the peak t orque decreased with
bi odi esel bl end cont ent , usi ng a common Number 2
di esel base stock, as shown in Tabl e 18. Four separat e
det ermi nat i ons o f pet rodi esel peak t orque bracket t he
bi odi esel bl end runs and are shown to demonst rat e that
t he t or que does not change wi t h t i me (chr onol ogi cal l y
shown by run number). The r el at i ve t or que bet ween neat
bi odi esel and 100% Number 2 is 94. 6% whi ch is in good
agr eement wi t h that expect ed fr om t he ener gy densi t y
rat i o o f t he fuels. Peak t orque is not si gni fi cant l y affect ed
18
up t o 35% bi odi esel . Ort ech International present ed
t orque data for a DDC 6V- 92 TA engi ne and report ed no
si gni fi cant loss in t or que at up to 40% bi odi esel in
142 M. S. Graboski and R. L. McCormick
bl ends, in agreement with the Series 60 observat i ons
gi ven above. A more recent Ortech study 69 ut i l i zed a
Cummi ns NI 4 engi ne and observed peak torque to
decl i ne by the same percent age as fuel energy densi t y for
bi odi esel bl ends.
The U.S. Ar my conduct ed accel erat i on and pull bar
tests at the U.S. Ar my Provi ng Gr ounds, Yuma Ar i zona
on five di fferent mi l i t ary vehicles. 7 The Ar my has
recently used JP-8 as a battlefield fuel in place of
Number 2 diesel. Bi odi esel has a hi gher energy densi t y
t han JP-8 and can also reduce smoke. A 20% bi odi esel
bl end with JP-8 provi ded 6.8 and 5. 6% faster accelera-
t i on times for a cargo carrier and a tactical truck
compared to JP-8 alone. Three other vehi cl es showed no
di fference bet ween the bl end and the JP-8. Accel erat i on
t i mes worsened for all five vehi cl es by 11- 14. 5% when
the JP-8/biodiesel bl end was compared to D-2. The
drawbar pull test measures del i vered torque. Except for
one vehicle, all showed equal or i ncreased drawpul l
val ue operat i ng on JP-8/biodiesel compared to neat JP-8
and 6.2 to 19.2 lower drawpul l val ue t han D-2.
The test results show that accel erat i on and torque are
in general related to t he energy densi t y of the fuel used.
Tor que generat i on at i nt ermedi at e throttle posi t i ons will
be lower but the requi rement for t orque can be met by
i ncreasi ng the throttle posi t i on slightly. Thus, the onl y
power related dri vabi l i t y probl ems that mi ght be
experi enced with bi odi esel are slightly lower accelera-
t i on at wi de-open throttle and slightly reduced horse-
power at wide open throttle. Int ermedi at e crui se
condi t i ons are not affected.
3.3. Engine Endurance Issues
At this time, most engi ne manufact urers have not
ext ended warranty coverage to bi odi esel . 55'71-74 There-
fore, an i mport ant barrier to bi odi esel use is suffi ci ent
endur ance t est i ng to al l ow manufact urers to warrant y
engi nes operat i ng on these fuels. A test st and durabi l i t y
study is t ypi cal l y requi red because in on-road demon-
stration testing vehicles do not operate l ong enough on
the fuel. EMA 45 has summar i zed many of the key
endur ance issues and the i mport ant fuel properties whi ch
might affect endurance. Unreact ed mono-, di-, and
triglycerides, free fatty acids, met hanol and gl ycerol
need to be removed. Tri gl yceri des are unconver t ed
veget abl e oil or fat and form i nject or deposits, as not ed in
early studies usi ng raw oils on fuels. Monogl yceri des,
glycerol, and fatty acids ' dr y' corrode beari ng metals.
Because of the high boi l i ng poi nt of bi odi esel , l ube oil
di l ut i on and val ve/ port deposits are an issue. Val ve
deposits occur at light load when low vol at i l i t y fuel is
deposi t ed on val ve surfaces and undergoes coke-formi ng
reactions. High boi l i ng fuel that becomes mi xed with the
l ube oil will not evaporat e as the engi ne oil heats up.
Lube oil di l ut i on by bi odi esel s leads to di fferent i n-use
l ube oil properties (such as l ube oil acidity) t han
pet rol eum diesel and needs to be careful l y exami ned.
Sol vent properties relative to engi ne el ast omers are also
i mport ant as unsat urat ed methylesters, or oxi dat i on
products such as hydroperoxi des and carboxyl i c acids,
can act as plasticizers. Wat er absorpt i on i nt o the
bi odi esel mi ght l ead to corrosi on of fuel syst em parts.
Many of these probl ems can be addressed through proper
puri fi cat i on of the raw met hyl est er fuel to el i mi nat e
gl yceri ne and unconver t ed mono- and diglycerides.
3.3.1. Durability studies
To address these issues a number of l ong term
durabi l i t y tests have been performed. Several of these
studies were funded by NBB and t wo of the most
si gni fi cant are revi ewed here. Nat i onal Bi odi esel Board
(NBB) 75 funded a 1000-hr durabi l i t y test usi ng a DDC
6V- 92TA, el ect roni c cont rol l ed engi ne and a 20%
met hyl soyester bl end. Approxi mat el y 10000 gal l ons
of the B-20 bl end were consumed dur i ng the test. The
condi t i oni ng cycl e i ncl uded idle, wi de-open throttle, and
i nt ermedi at e power condi t i ons. At about 700 hr, the
fol l owi ng condi t i ons were observed: low fuel ret urn
pressure, l ow horsepower, l ow fuel consumpt i on, and
high crankcase bl owby. It was observed that fuel
r et umi ng to the day t ank was bl ack and si gni fi cant
deposits o n ai r box covers, pi st on component s, and
i nject ors was observed. The fuel l i nes, fuel filters, and
fuel transfer pump were replaced duri ng a bri ef shut-
down at 700 hr. Aft er a l onger shut down at 750 hr, it was
found that engi ne parameters had ret urned to normal .
Duri ng the final 250 hr, performance deteriorated in a
pattern si mi l ar to the first 750 hr. Aft er engi ne tear down,
subst ant i al deposits were found on many engi ne
component s. The source of these deposits appeared to
be the l ube oil. Cavi t at i on erosi on of the i nject or needl e
val ves had caused i nject ors to deteriorate to the poi nt that
al most no fuel at omi zat i on was occurri ng. Det eri orat i ng
fuel pump seals were proposed to have i nt roduced
mi croscopi c ai r bubbl es i nt o the fuel causi ng the
cavi t at i on erosion. El evat ed soot and wear met al s were
observed i n t he l ubri cant . Broken fire and compressi on
rings were also found on several cyl i nders. Soft eni ng of
fuel syst em seals was observed.
A second NBB- funded durabi l i t y study was performed
usi ng a 1987 Cummi ns NI 4 engi ne and B-20 (soy
methylester). 76 The test was i nt ended to be of 1000-hr
durat i on but was t ermi nat ed at 650 hr due to failure of
the engi ne PT pump, a part of the fuel system. Fai l ure
was caused by bui l d up in the pump of a residue
composed of fatty aci d esters, free fatty acids, and aci d
salts. Thi s same resi due had pl ugged a fuel filter and the
PT pump earlier in the durabi l i t y test. Fuel injectors were
in good condi t i on at the end of the test. Oi l anal ysi s
reveal ed no si gni fi cant degradation. It was proposed that
the operat i onal pr obl ems experi enced duri ng this test
were caused by i nst abi l i t y toward oxi dat i on of t he B-20
fuel. Not abl y, both the neat soy diesel and No. 2 diesel
used to make the B-20 used in this study were found to be
stable.
The Uni versi t y of Idaho 32 has conduct ed 200-hr
durabi l i t y tests with 4-stroke, direct injected, nat ural l y
aspirated engi nes. The fuels used were D-2, neat
Fat and vegetable oil derived fuels 143
rapeseed met hyl - and et hyl est ers, neat hydr ogenat ed
soybean oi l et hyl est er (fryi ng oi l et hyl est er), as wel l as 80
and 20% bl ends o f the hydr ogenat ed soy est er with D-2.
No si gni fi cant pr obl ems wer e encount er ed in t hese
r el at i vel y short tests. At the concl usi on o f t he tests,
lube oil iron cont ent was si gni fi cant l y hi gher for t he
r apeseed oi l based fuel s compar ed to D-2 suggest i ng
abnormal wear. Thi s was not the case for t he hydro-
genat ed soybean oil fuels. The unsaturation o f the
rapeseed est er fatty aci d chai ns probabl y lead to
oxi dat i on and aci d for mat i on causi ng corrosion.
Goya174 report ed a study usi ng t he I SO 8178-4 of f
road test with rapeseed methylester. A Deer e 4239T
engi ne was run for 1450 hr. Power loss was 6 - 8 %. Af t er
1000 hr of rated operat i on, carbon bui l d-up in ports and
piston ri ngs was observed. Af t er 300 hr of l i ght load
testing, l acquer and varni sh deposi t s wer e obser ved on
combust i on chamber parts. Some gaskets wer e
distressed, suggest i ng i ncompat i bi l i t y wi t h met hyl est ers.
Addi t i onal studies pr ovi de some confi rmat i on of the
pr obl ems not ed above. Lucas 7 report ed si mi l ar fuel
filter and pump pr obl ems to t hose descri bed above in his
study of soy met hyl est er B-20 for mul at ed with JP-8 (jet
fuel). Fl eet studies wi t h rapeseed oi l met hyl est ers 29'3
have found that fuel tank coat i ngs can be di ssol ved by
t hese fuels. The i mpact of t hese cont ami nant s on the
engi ne fuel syst em was not assessed.
Low dut y cycl e engi nes may be especi al l y subject to
l ube oi l di l ut i on. Bl ackburn 77 report ed 50% oi l vi scosi t y
loss in 50 hr usi ng et hyl soyate. Macchi 7s report ed a
hi gher di l ut i on for rapeseed met hyl est er. Schloeg179
report ed serious di l ut i on with vi scosi t y droppi ng 50%
and total base number droppi ng 30% in 200 hr. The l ow
duty cycl e engi nes used showed val ve and port deposits.
3.3.2. El a st omer compat i bi l i t y
Many of the pr obl ems encount er ed duri ng the
durabi l i t y studies descri bed above can be t raced to
i ncompat i bi l i t y o f bi odi esel wi t h cert ai n el ast omers. The
sol vent propert i es of bi odi esel can di ssol ve el ast omer s as
wel l as fuel tank deposi t s and l ead t o fuel filter and
i nj ect or pl uggi ng. 7j-74 Most of t he el ast omer s used wi t h
convent i onal di esel swel l by absorpt i on o f aromat i c
compounds. Thi s swel l i ng is normal and is account ed for
in fuel syst em design. Bi odi esel fuel s may l each
aromat i cs from the el ast omer as wel l as addi t i ves
desi gned to pr event hardeni ng and cracki ng.
Met hyl est er s have been shown to swel l t ri l obut yl -
di l ene and nitrile rubber, common aut omot i ve seal and
gasket materials. 55 Fl uor i ne cont ai ni ng el ast omers di d
not exhi bi t si gni fi cant swel l i ng. Hawki ns et al . sj
report ed accept abl e per for mance with Vi t on A. Bessee
and Fey 57 exami ned the effect of exposur e to met hyl
soyest er and D-2 blends on the t ensi l e strength,
el ongat i on, hardness, and swel l i ng of several common
el ast omers. Ni t ri l e rubber, Nyl on 6/6, and hi gh-densi t y
pol ypr opyl ene all exhi bi t ed changes in physi cal
properties. Tefl on , Vi t on 401-C, and Vi t on GFLT
were unaffect ed. Ther e is general agr eement that
fluorinated el ast omers must be used for bi odi esel
servi ce. 29"55'73 Most engi ne manufact urers appear to be
usi ng this t ype of el ast omer in t hei r newer model
engi nes.
The effect of fatty acid structure (e.g., degr ee of
saturation) on el ast omer compat i bi l i t y does not appear to
have been exami ned. Perhaps most i mport ant l y, t he
i mpact of bi odi esel purity does not appear to have been
addressed in quant i t at i ve studies. Hi ghl y unst abl e free
fatty aci ds as wel l as unreact ed mono-, di-, and
t ri gl yceri des, gl ycer ol , and met hanol may have a great
i mpact on el ast omers. These aspects o f compat i bi l i t y
with el ast omers are a t opi c for future research.
3.3.3. Bi odi esel l ubri ci l y
Fuel lubricity is i mport ant because in many fuel -
pumps the movi ng parts are act ual l y l ubri cat ed by t he
di esel fuel itself. Lubri ci t y is measured by the Ball On
Cyl i nder Lubri ci t y Eval uat or or BOCLE test, and the
Hi gh Fr equency Reci pr ocat i ng Ri g or HFRR test.
Resul t s are shown in Tabl e 19. The BOCLE test is
accurat e to _+ 200 g and fuel s wi t h good lubricity gi ve
BOCLE results in the 4500- 5000 g range. For t he HFRR
Table 19. Results of biodiesel lubricity tests for soybean oil methylester and ethyl- and methylesters of rapeseed oil
Fuel BOCLE result HFRR
(g) Scar (mm) friction
Conventional low sulfur diesel 8 4200 0.492 0.24
Conventional low sulfur diesel 9~ 4250 0.405 - -
Methyl soyester s 6100 - - - -
Methyl rapeseed ester 9~ 7000 0.140 - -
Ethyl rapeseed ester 9~ > 7000 0.085 - -
B-2 (Soy methylester) 8 4400
B-5 (Soy methylester) s 4500
B- 10 (Soy methylester) 8 5200
B-20 (Soy methylester) s 5200 0.193 0.13
B-30 (Soy methylester) 8 - - 0.206 0.13
B-20 (Rape methylester) 91 4600 0.190 - -
B-50 (Rape methylester) 9t 5550 0.180 - -
B-20 (Rape ethylester) 91 4700 0.165 - -
B-50 (Rape ethylester) 9] 5700 0.165 - -
144 M, S. Graboski and R. L. McCor mi ck
o o
II
2
II
E
"? ,
d
I ~ I ~ = ~
I I I I
~ o ~ I ~ I I ~
O0 0 0 0
~ ~
~ 0 0 0 0 0 0
I I ~ I I I
~ ~ t ~ t ~ t ~ t o ~ l
o ~ ~ ~ ~ o o o ~
i
Fa t a n d v e g e t a b l e oi l d e r i v e d f u e l s 145
N 2 d 2 ~ ~ 2 d ~ N d N ~ 4 d ~ d d ~ N
~ m ~ . . . . m ~ ~. ~. --. ~. ~. ~ ~. ~ ~ ~. ~. ~. ~ ~. ~. ~.
/ I I t I I I I " ~ I I I I
d ~ ~ d d e d d d d d d d d
I I
~ = ~ = ~ ~ =~. ~ = = . . ~ ~ N ~ . -~ =. ~ ~ ~ ~ - - ~ =~. .
~ H ~ - ~ N ~ ~ ~ ~ ~ ~ ~ . . . . . . . . ~ . . . ~ ~ ~
. . . . . . . . . . . . . . ~ = ~ ~ ~ ~
- - ~ ~ , , + ~ + + ~ ~ , t . + ~ ' ~
E-
r..)
, i . -
146 M.S. Graboski and R. L. McCormick
test, scar values over 0.400 mm are considered failing.
These results show that biodiesel, or at least soybean and
rapeseed oil methylesters, have superior iubricity when
compared to conventional low sulfur diesels. Blending
biodiesel at concentrations of 20 vol% or higher results
in an improvement in lubricity over that of the D-2.
3.3.4. Summary
These durability results suggest that the use of
biodiesel blends can result in a loss of oxidative stability
of the lube oil and degradation of fuel system elastomers
and coatings, which may have ultimately damaged fuel
pumps and injectors. Oxidative stability of the biodiesel
itself can impact elastomer compatibility although no
studies of this effect appear to have been done.
Hydroperoxides formed upon oxidation, as well as
impurities such as unconverted mono- and diglycerides
and glycerine can lead to engine deposit formation.
Biodiesels have superior lubricity to conventional diesel
so this will not be an engine endurance issue.
4. EMI S S I ONS
4.1. Regulatory Barriers
In the United States, diesel engines are currently
regulated for smoke opacity, total nitrogen oxides (NOx),
total particulate matter less than 10/xm (PM-10 or PM),
carbon monoxide (CO), and total hydrocarbon (THC)
according to test procedures defined by EPA in the Code
of Federal Regulations. s2 Since the magnitude of diesel
emissions are fuel composition dependent, emission
certification testing is conducted with 'certification
diesel fuel' which represents the U.S. annual average
diesel. Depending on the type of diesel engine and its
use, EPA has defined a useful life. For many on road
engines, the defined useful life is 290000 miles. Diesel
engines must meet emission standards throughout
their useful life without deterioration. This is demon-
strated to EPA through deterioration testing. There are
other emissions from diesel engines such as aldehydes
and poly-aromatic hydrocarbons (PAH) which are
currently unregulated but which may be regulated in
the future in an attempt to control ambient levels of air
toxins.
EPA is presently considering a regulatory action to
define 'substantially similar' diesel fuels. Substantially
similar fuels must demonstrate similar emissions, engine
performance and durability. Petroleum distillates contain
no chemically bound oxygen and EPA' s current defi-
nition of diesel fuel limits oxygen content to less than
1 wt%. 83 Current in-use diesel fuels Ray contain very
small amounts of oxygen (i.e., 0.1%) present in additives
such as cetane enhancers. A blend of conventional diesel
with oxygenates, or the neat oxygenates, may not be
considered substantially similar to conventional diesel
fuel. These fuels would then be subject to the require-
ments of Section 21 l(b) of the Clean Air Act, which
requires health effect testing. Non-substantially similar
fuels might also obtain a fuel formulation use waiver
based upon extensive emissions and durability testing
which demonstrates equivalency.
Under the Clean Air Act Amendments of 1990, 84
diesel fuel and fuel additives must undergo health effects
testing to determine the potential impact of emissions on
the public. EPA has defined a three-step program which
involves a literature study of the mutagenicity and
detailed speciation of diesel exhaust emissions, a live
animal exposure test protocol, and an optional extended
exposure study based upon the findings of the first two
steps. To control costs, EPA has allowed the refining
industry to form a consortium to test diesel fuel. Exhaust
toxic materials from biodiesel blends are likely to be
different than diesel (as discussed below in the section on
Emissions of Unregulated Air Toxins) and thus require
separate testing not funded through the consortium.
Since the type of oxygenate could significantly impact
the type and quantity of irritants and mutagenic
compounds in the exhaust, very extensive testing may
be required for biodiesel fuels. Engine family, blend
level, and the type of oxygenate (soy ester, tallow ester,
etc.) are variables which could result in very costly
testing matrices producing a significant barrier to
widespread use of biodiesel blends.
4.2. Regulated Emissions: Engine Stand and
Chassis Studies
Biodiesel and biodiesel blends can alter all regulated
emissions from diesel engines relative to petroleum
derived diesel. Quantitative values of regulated
emissions are dependent on the engine technology
employed and the type of emission test used.
An important property of oxygenates in diesel fuel in
general is their ability to reduce total particulate
emissions from an engine. For regulatory purposes, the
level of PM emission in g/bhp-hr (0.7457 g/bhp-hr =
1 g/kW-hr) is determined by an engine dynamometer test
known as the EPA heavy duty transient test. 82 Particulate
emissions are defined by EPA as condensed or solid
material collected on an appropriate filter at a temper-
ature of 52C or lower. Particulate matter thus includes
soot carbon, fuel and lube oil derivatives, and sulfuric
acid aerosols. Particulate matter is often fractionated in
terms of sulfate, soluble organic fraction (SOF) or
volatile organic fraction (VOF), and carbon. 85 Extraction
of particulate samples (SOF method) using an et hanol -
toluene solvent yields similar results to volatilization
under vacuum at high temperatures (VOF method). In
the following discussion, SOF is used to refer to the
fraction measured by either the SOF or VOF methods.
Soot is produced by pyrolysis reactions in the flame
front in the combustion chamber. Fuel based SOF
emissions are principally generated during the engine
start. Lubricating oil is emitted from the engine by the
action of scavenging air and exhaust gases, which
vaporize and shear oil droplets from cylinder surfaces.
Biodiesel, and diesel fuel oxygenates in general, can
Fat and vegetable oil derived fuels 147
i mpact soot and fuel based SOF but not l ubri cat i ng oi l
based SOF as it is not i nvol ved in t he combust i on
process.
Regul at ed emi ssi ons (NOx as NO2, CO, THC, PM) as
wel l as t he SOF fract i on of total PM, r epor t ed on a gr am
per brake hor sepower hour basis, are l ogi cal l y separat ed
into data for ol der t wo-st roke engi nes and for moder n
four-st roke engi nes. Di esel engi nes are si gni fi cant
cont ri but ors of NOx and PM t o ambi ent ai r pol l ut ant
i nvent ori es. The quant i t y of CO and THC der i ved fr om
di esel engi nes is gener al l y smal l in compar i son to
emi ssi ons fr om l i ght duty vehi cl es. For this reason,
bi odi esel fuel s are bei ng consi der ed for use on t he basis
of t hei r i mpact on PM and NOx, and t he fol l owi ng r evi ew
is pr i mar i l y di rect ed t oward t hese emi ssi ons. It is
i mport ant to note, however , that di esel oxygenat es such
as bi odi esel pr oduce l arge reduct i ons in emi ssi ons of CO
and THC whi ch mi ght be i mport ant in some air sheds.
4.2.1. Engine dynamometer studies using two-stroke
engines
The t wo mai n t ypes o f di esel engi nes are cl assi fi ed as
t wo- st r oke and four-st roke. Two- st r oke engi nes produce
power for ever y pi st on stroke, rather than for ever y t wo
as in t he case o f four-st roke engi nes. Bef or e t he stringent
emi ssi on cont rol s on di esel engi nes began to be i mposed
in the 1990s, t wo-st roke di esel engi nes wer e favor ed for
t hei r l ow wei ght t o power ratio. However , l ubri cat i ng oil
losses to the exhaust are much hi gher for t wo-st roke
engi nes resul t i ng in excessi ve part i cul at e emi ssi ons.
Al so, a substantial port i on of t he air suppl i ed t o the
engi ne by the t urbocharger is not used to cont rol
emi ssi ons in t he combust i on process but instead is used
to i mpr ove t he vol umet r i c effi ci ency t hrough cyl i nder
scavengi ng duri ng val ve overl ap. That is, s ome of t he air
is bl own through the cyl i nder wi t h both i nt ake and
exhaust val ves open to purge t he cyl i nder of exhaust
gases. Oi l dropl et s may be bl own out duri ng this
scavengi ng port i on o f the t wo-st roke cycl e. Thi s results
in a l ower exhaust t emperat ure (345C maxi mum
compar ed to about 540C for four st roke engi nes on
the EPA heavy- dut y transient test) whi ch affect s the
per for mance of t he t urbocharger and exhaust catalysts.
Soy-diesel emissions. Thi s col l ect i on of i nvest i gat i ons
was pri mari l y di rect ed by t he Nat i onal Bi odi esel Boar d
(NBB) for the EPA Urban Bus Rebui l d/ Ret rofi t
Program. Two- st r oke Det roi t Di esel engi nes represent
a substantial portion o f t he power plants used in ol der bus
fleets in the uni t ed states. For the general market pl ace,
EPA is in the process of regul at i ng fuel s through a
substantially si mi l ar rule that requi res that new fuels and
addi t i ves not i ncrease any regul at ed emi ssi on in t he
di esel fleet. In cert ai n capt ured fleet operations, EPA
al l ows combi ned hardware and fuel changes whi ch
pr ovi de certain emi ssi ons benefits. In the case of urban
buses, ol der engi nes are subject to rebui l d rules that
requi re a defined reduct i on o f part i cul at e emi ssi ons (at
least 20%). Ot her emi ssi ons must be mai nt ai ned at or
bel ow t he emi ssi on standards for the engi ne model in
quest i on when compar ed t o emi ssi ons fr om D-2
cert i fi cat i on fuel when the engi ne is in the OEM
(ori gi nal equi pment manufact urer) confi gurat i on.
Because bi odi esel fuel s are known to i ncrease emi ssi ons
of NO~, t hese i nvest i gat i ons cent er ed on strategies for
obt ai ni ng a PM reduct i on wi t h no net NOx increase. The
" ~ 3 0
U)
.e_
GI
4 )
2 0
t l
r n
.oq
. ~ 1 0
D.
3
x -10
0
Z
.N
= ) - 2 0
o )
=..
t~
t -
O - 3 0
o
Q. -40
P M
0 N O x
o J
o 7
. . . . i , , , , I . . . . I . . . . I . . . . I . . . .
0 2 4 6 8 1 0 1 2
Wei ght Percent Ox y ge n in Bi odi es el Bl end
Fig. 8. Change in PM and NO, emissions as a function of oxygen content for soybean oil methylesters in a stock, two-stroke engine
(DDC 6V-92TA-etectronic); data selected from Table 20.
148 M. S. Graboski and R. L. McCormick
Table 21. The effect of the addition of 20% soybean oil methylester biodiesel to diesel on PM emissions from two-stroke engines
Reference Engine SOP % for base diesel Change in PM (%) Change in NO.~ (%)
16 6V-71 N-77 MUI 88 - 2. 4 2.4
17 6V-92TA-91 DDECI1 40 - 11. 2 5.4
24 6V-92TA-87 MUI NA - 5. 1 3. I
31 1987 6V-92TA MUI 52 +5. I 6.1
41 1988 6V-92TA DDECII 58 0 4.8
59 1991 6V-92TA DDECII 25 - 22. 5 2.5
60 1977 6V-71N-MUI 75 + 14.5 1.4
61 1981/89 6V-92TA-MUI 54 - 3.0 4.4
87 1989 6V-92TA DDECII a NA - 15.4 2.3
~Measurements for B- 10 blend.
20
0
O4
10
c 0
@
c
0 -10
ID
C
~ -20
o.
- 3 0
2 0
i
3O
i i i i i
4 0 5 0 6 0 7 0 8 0
P er cent S O F in Total P M f or N o. 2 Diesel
i
90 100
NBB st rat egy was to i nvest i gat e how NO~ and PM are
affect ed by t i mi ng, tuning, rebui l di ng, and SOF oxi da-
tion catalysts t o det er mi ne how much PM r educt i on was
achi evabl e wi t h no net NOx change.
Tabl e 20 present s a summar y o f emi ssi ons fr om t hese
ol der engi nes i nvest i gat ed usi ng t he EPA heavy- dut y
engi ne dynamomet er transient test prot ocol . Mos t o f
t hese wer e i n-use engi nes that had a si gni fi cant number
of operat i ng hours l ogged befor e bi odi esel t est i ng. Al l
tests wi t h bi odi esel , desi gnat ed as B- XX wher e XX is t he
vol ume per cent age o f bi odi esel in t he bl end, ut i l i zed t he
r efer ence di esel denot ed as D- I or D-2 as t he bl end
stock. The percent age changes in NO~ and PM col umns
i ndi cat e t he change in t hese emi ssi ons r el at i ve t o st ock
engi ne set -up wi t h t he base di esel fuel.
For stock, t wo- st r oke engi nes wi t hout t i mi ng changes
or exhaust catalyst, t he f ol l owi ng general emi ssi ons
trends resul t r el at i ve t o t he base di esel fuel when soyest er
bi odi esel is bl ended wi t h Number 1 or 2 di esel fuel :
NOx i ncreases;
PM, CO and THC decrease;
t he soot (sol i d carbon fract i on of PM) mass emi ssi on
decreases.
Fi gur e 8 is represent at i ve o f how NOx and PM
emi ssi ons var y wi t h t he oxygen cont ent of bl ends of base
di esel and soybean oi l met hyl est er fuel s for t wo-st roke
engi nes. Thi s pl ot i ncl udes onl y dat a for el ect r oni cal l y
cont r ol l ed Det r oi t Di esel 1991 DDEC II 6V- 92TA
engi nes. Tabl e 21 present s dat a for PM and NOx changes
and SOF l evel s for pri nci pal l y B- 20 bl ends in a
col l ect i on of mechani cal and el ect r oni c t wo-st roke
engi nes. Wi t h 20% bi odi esel (2% oxygen), t he NO,.
i ncrease var i ed fr om 1.4 to 6. 1%, PM changed by
- 2 2 . 5 % to +14. 5%, and SOF (on t he base di esel fuel)
ranged fr om 25 to 75%. Low SOF percent ages are
obt ai ned fr om newer model engi nes and engi nes with
l ow mi l es or hours o f operation. Si nce t he SOF port i on of
PM fr om ol der engi nes is 5 0 - 75 % o f t he total PM, the
full val ue o f t he oxygenat e for PM reduct i on is not
real i zed and PM emi ssi ons may act ual l y appear to
increase. Thi s is cl ear l y shown in Fi g. 9 where t he
per cent age reduct i on in total PM emi ssi ons is shown as a
funct i on o f t he base di esel SOF mass emi ssi on for t wo-
and four-st roke engi nes. As SOF emi ssi ons decrease, t he
i mpact o f bi odi esel on part i cul at e becomes not i ceabl e.
The data suggest that t he PM i ncrease or decr ease is
Fig. 9. Percentage PM reduction using B-20 for two-stroke engines as a function of SOF level when burning Number 2 diesel. Data
for both mechanical and electronic engines in Table 20.
Fat and vegetable oil derived fuels 149
m
2 0
o
o - 10
" ~ - 20
J~
,.-, - 3 0
e , .
a . - 4 0
P M
o N Ox
v
l
.
|

u . . . . i . . . . u . . . . i . . . . i . . . .
2 4 6 8 10 12
W e i g h t P e r c e n t O x y g e n in B i o d i e s e l B l e n d
Fig. 10. Change in PM and NOt emissions as a function of oxygen content in several stock, two-stroke engines; data for soy, tallow,
and rape methylesters from Table 20.
i ndependent of engi ne vi nt age or t ype of fuel i nj ect i on
system. The i mpact on PM emi ssi ons does depend on
engi ne wear as it impacts oil consumpt i on. Wor n engi nes
slip oil past the rings to the ai r intake ports. Duri ng
scavengi ng when the i nt ake port and exhaust val ve are
open, ai r transports oil from the i nt ake ports to the
exhaust resul t i ng in oil based PM. For high SOF
engi nes ( > 50% of PM as oil), little PM benefi t is
obt ai ned wi t h biodiesel. There is little reason to
bel i eve that PM act ual l y i ncreases at very high SOF
emi ssi ons. The apparent i ncrease at high SOF
emi ssi on levels is probabl y due to the lack of
repeatability i nherent i n emi ssi ons measur ement s from
engi nes that are si gni fi cant oil users.
Tabl es 20 and 21 suggest that the NOx i ncrease is
i ndependent of engi ne vintage, i nject or technology, and
wear to a good approxi mat i on. Fi gure t 0 is si mi l ar to
Fig. 8 except that it cont ai ns all data from Tabl e 20,
i ncl udi ng data on rapeseed and t al l ow esters and all
engi nes listed. The PM reduct i on correlates poorl y with
fuel oxygen cont ent and aside from the t wo data poi nt s at
10% oxygen (neat bi odi esel ) there may be no correlation.
For this dat a set biodiesel may have had no effect on PM
on average. However, the NOx i ncrease correlates
reasonabl y well and is thus i ndependent of engi ne and
SOF level. A di scussi on of possi bl e causes of the
i ncreased NOx emi ssi ons is provi ded in a later section of
this review.
A series of studies showed that by ret ardi ng the
i nj ect i on t i mi ng of ol der engi nes from 1 - 4 ,
the emi ssi ons of NOx for B-20 can be decreased to a
level equal to or bel ow the D-2 base emi ssi ons with no
t i mi ng change. Ret ardi ng the t i mi ng also i ncreases the
particulate emi ssi on since changes that reduce NO~
cause a decrease in cyl i nder peak temperature resul t i ng
in an i ncrease of PM and a correspondi ng i ncrease in fuel
consumpt i on. For the various two-stroke engi nes
studied, the NOx decreased by 1.9% to 7. 3% per
degree of t i mi ng change with a 4 maxi mum change
investigated. Si mul t aneousl y, PM i ncreased by 0. 5% to
8.5% relative to B-20 with no t i mi ng change. Changes of
several degrees can negat i vel y i mpact dri vabi l i t y.
Rebui l di ng and r et uni ng also i mpact ed NOx. Import ant l y
for a gi ven engi ne, the percent age changes in NOx and
PM were i ndependent of the fuel. Thus, at any gi ven
engi ne set -up (timing, rebuild, t uni ng), NO~ was al ways
greater for B-20 fuels while PM was al ways lower.
In order to obt ai n NOx neut ral i t y while mai nt ai ni ng
the desired PM reduct i on, NBB proposed to combi ne a
t i mi ng change with an oxi dat i on catalyst. It was found
that for two-stroke engi nes with a catalyst and t i mi ng
change, there was little advant age compared to the stock
engi ne with catalyst and D-2. The reason for this resul t is
that oxi dat i on catalysts can convert the SOF port i on of
the PM onl y. Oxi dat i on catalysts are flow through
monol i t hs. Engi ne emi ssi ons of l i qui d oil droplets and
soot are general l y less t han one mi cron in size and are not
readily capt ured by i mpact i on due to changes in flow
direction. Thus, these mat eri al s pass through the catalyst
monol i t h. Onl y combust i bl e species that are abl e to
diffuse rapidly to the catalyst surface can be oxidized.
Lube oil and fuel species are vapor when the engi ne is
under sufficient load to produce a sufficiently high
exhaust temperature. Thus, the efficiency of oxi dat i on
catalysts to convert PM is general l y much less t han
100% and is dependent on the severity of the dri ve cycle.
Non-soy biodiesel studies. The Adept Gr oup 31
i nvest i gat ed a 1983 6V92TA MUI engi ne rebui l t to
150 M. S. Graboski and R. L. McCormick
Table 22. Chassis dynamometer based emissions results for B-20 fuel, older two-stroke engine, NY bus composite cycle 66'68
NO~ PM SOF Aldehydes
(g/mile) (g/mile) (%) (g/mile)
1981DDC 8V-71
D-2 35.2 0.91 51.8 0.40
B-20 30.7 1.48 72.2 0.42
B-20 + catalyst 32.2 0.89 48.3 0.25
B-20 + timing change 26.3 1.55 67. I 0.48
B-20 + catalyst + timing change 34.3 1.12 49.4 0.30
1988 DDC 6V-92TA
D-2 27.3 1.30 65.6 0.31
B-20 27.1 1.46 68.0 0.31
B-20 + catalyst 23.7 1.02 5 !.0 0.28
B-20 + timing change 26.9 1.79 52.0 0.39
B-20 + catalyst + timing change - - 1.21 36.5 0.34
1987 EPA D- bus l ow emi ssi on standards usi ng bl ends of
soy and rape (canol a) met hyl est ers wi t h CARB and U. S.
l ow sul fur di esel fuel s (EPA di esel ). Transi ent test
emi ssi ons wer e report ed for CARB and EPA di esel and
are listed in Tabl e 20. The aver age SOF emi ssi on fr om
t he engi ne was 51% o f total PM for t he t wo di esel
basel i ne fuels. NOx i ncreased for both rapeseed and soy
esters in proport i on to t he oxygen cont ent of t he fuel , and
this data is i ncl uded in Fig. 10.
Emi ssi on measur ement s report ed are not repl i cat ed
except for t he CARB basel i ne dat a that show si gni fi cant
variation. At 20% r apeseed met hyl est er NOx i ncreased
by 4. 5 and 3. 8% r espect i vel y for EPA and CARB di esel
blends, whi l e NOx i ncr eased 5. 7% for t he soy met hy-
l e s t e r - CARB bl end. PM was reduced by 10.2 and 4. 8%
r espect i vel y usi ng 20% bl ends o f rape met hyl est er wi t h
EPA and CARB di esel base stocks. PM i ncr eased 5. 1%
for a 20% bl end o f soy met hyl est er wi t h CARB di esel .
However , t he CARB di esel basel i ne PM decr eased by
4. 8% for t he soyest er series compar ed t o t he rape-est er
series. I f this is taken as a measur e o f exper i ment al
uncertainty, then it can be concl uded that t he effect of
rape and soy met hyl est ers in 20% bl ends for NOx and
PM emi ssi ons is t he same.
Tabl e 20 also present s dat a col l ect ed usi ng a 6V- 92TA
DDECI I engi ne compar i ng soy and t al l ow met hyl est er /
D-2 blends. 59 The NOx emi ssi on for 20% soy and t al l ow
bl ends wer e 4.51 and 4.71 g/ bhp- hr r espect i vel y whi l e
the PM emi ssi ons wer e 0. 214 and 0. 219 g/ bhp-hr. Wi t hi n
t he preci si on of t he data for this engi ne, there is no
si gni fi cant di ffer ence bet ween NOx and PM emi ssi ons
for soy and t al l ow based fuels.
Bennet hum and Wi ns or 88 exami ned t he oxygenat ed
compound di gl yme (di et hyl ene gl ycol di met hyl et her) in
a 1991 6V- 92TA DDECI I engi ne. Heavy- dut y transient
test results with t he t reat ed fuel showed a 6% PM
reduct i on at 0. 2% oxygen as di gl yme. At 2% oxygen as
di gl yme, a 20% PM reduct i on was obser ved whi l e NOx
r emai ned essent i al l y unchanged. McCor mi ck et al. 87
i nvest i gat ed 1% oxygen bl ends in a 1989 6V- 92TA
DDECI I engi ne usi ng n-oct anol , decanoi c acid, and
met hyl soyester. Al l oxygenat es t est ed pr oduced a
si gni fi cant PM reduct i on in t he range of 12- 17%.
Met hyl soyest er pr oduced a mor e than 2% i ncrease in
NOx emi ssi ons, si gni fi cant at t he 95% confi dence l evel .
The l ower mol ecul ar wei ght oxygenat es (decanoi c aci d
and oct anol ) di d not si gni fi cant l y change NOx. These
studies suggest that t he effect o f oxygenat es in general is
to r educe PM based upon t he quant i t y o f oxygen added to
t he fuel. Furt hermore, t he data suggest that NOx
emi ssi ons may depend upon t he oxygenat e used
al t hough gi ven t he ver y smal l data set this concl usi on
must be regarded as tentative.
Chassis studies with two- stroke engines. Howes and
Ri deout 67"68 of Envi r onment Canada tested t wo in-use
buses for NBB usi ng t hree cycl es, t he CBD, t he Art eri al ,
and t he NY Bus Compos i t e on a smal l roll wat er brake
chassis dynamomet er . Low sulfur di esel and a B-20
bl end (undefi ned t r i gl ycer i de source but most l i kel y
soybean oi l ) wer e i nvest i gat ed. Regul at ed emi ssi ons as
wel l as s of and al dehydes wer e measured. Addi t i onal l y
t he effect o f cat al yst and i nj ect i on t i mi ng was studied.
Tabl e 22 present s a summar y o f results for t he NY
composi t e cycl e. For t he 1981 8V-71 power ed bus, B- 20
apparently rai sed t he part i cul at e emi ssi on by 50%.
Empl oyi ng a cat al yst and al t eri ng engi ne t i mi ng never
reduced emi ssi ons t o t he l ow sul fur di esel case. The
cat al yst di d ef f ect i vel y r educe a port i on o f t he al dehydes
that are responsi bl e for t he odor fr om t he vehi cl e. Wi t h
the 1988 6V- 92TA power ed bus, t i mi ng change and
cat al yst resul t ed in a mi nor (7%) part i cul at e reduction,
no NOx change, and an al dehyde increase. In both cases,
t he SOF emi ssi on fr om t he engi ne was hi gh i ndi cat i ng a
l arge l ubri cat i ng oil emi ssi on. The i ncrease in B- 20 PM
emi ssi ons wi t h ei t her a reduct i on or no change in NOx is
Table 23. Emission comparison of low sulfur D-2 and neat
soyester, CBD cycle, 6V-92 two-stroke (average of several
runs) 89
Emissions Low 1 0 0 % Change
(g/mile) sulfur Methyl (%)
diesel soyester
THC 2.58 1.04 - 59. 8
NOx 44.53 48.68 9.3
CO 56.87 36.23 - 36. 3
PM 5. I 0 2.71 - 46. 8
F a t a n d v e g e t a b l e o i l d e r i v e d f u e l s 151
&
II
<
2
r-
II
#
o
c-

,o
E
E
E
o
b-
~2
I I I
I I I I I t
I
~ . r-:
I I I I
i ~ l l l ~ l l l l ~ o ~ ~ 1 _ _ _ o o
I - ~ ~ ~ ~ ~ -
~ , I , ~ 7 , , ~ , S ?
. . . . . . . . . . - ~ ~. ~. . . . . . . . . - _ ~. ~. ~. ~. ~. ~. ~. ~, - - ~ . . . . . -
~__~~~~ _ ~ ~ ~ ~ ~ ~ ~ ~ o o oo~o ~
~ z ~ ~ ~ ~
~ ~ z z ~ ~
~ +
. r - . _ ,r" . -
E ~ E
o~
E
E
152 M. S. Graboski and R. L. McCormick
not in agr eement wi t h the report ed engi ne studies and
may refl ect t he much great er degr ee of difficulty of
per for mi ng hi gh qual i t y chassis measurement s.
Graboski 88 obt ai ned results for a Denver RTD bus
fuel ed on l ow sul fur di esel and neat soy met hyl est er
bi odi esel . These pr evi ousl y unpubl i shed dat a are
present ed in Tabl e 23. The bus was power ed wi t h a
high mi l eage DDEC- I I 6V- 92 TA power pl ant and was
ready for rebuild. The bus had except i onal l y hi gh
part i cul at e emi ssi ons because o f a t urbocharger mal -
funct i on but was not an oi l user. Thus t he SOF
percent age of the total PM was probabl y l ow, al t hough
it was not measured. For this bus, bi odi esel i ncreased
NOx by 9% and l ower ed PM by 46. 8%. The Adept
Gr oup 3] report ed CBD cycl e data for t he 1983 6V92TA
MUI engi ne descr i bed previ ousl y. For 20% soy met hyl -
est er in CARB diesel, THC, CO and PM decr eased 16.7,
20.2 and 6. 1%, r espect i vel y, whi l e NOx i ncr eased 4. 5%.
Bat t el l e 63 present ed CBD chassis cycl e dat a for buses
fuel ed wi t h cont rol di esel and B- 20 (soy met hyl est er)
whi ch wer e col l ect ed usi ng t he Wes t Vi r gi ni a Uni ver si t y
mobi l e chassis dynamomet er . The emi ssi on results wer e
hi ghl y vari abl e across fleets and changed dramat i cal l y
fr om t he first tests conduct ed at 8000 mi l es t o t he second
set col l ect ed at 40 000 mi l es. NOx i ncreased by 20% for
both fuel s fr om t he first to t he second test that suggest s
that t he bus i nert i a was charact eri zed di fferent l y, t he
cycl e was dr i ven di fferent l y, or emi ssi ons measur ement s
wer e i nconsi st ent bet ween tests. The di esel buses
consumed 4qua r t s of oi l per 1000mi l es whi l e t he
bi odi esel buses used 1.7 quart s suggest i ng that a di rect
compar i son of PM emi ssi on data to est i mat e a bi odi esel
i mpact coul d be confounded by di fferi ng SOF emi ssi ons.
Two di esel engi nes wer e r epai r ed duri ng t he fl eet test
and consequent l y oi l consumpt i on fell. Si nce PM is
domi nat ed by l ube oil emi ssi ons for t hese 1988 buses,
little or no PM benefit mi ght be expect ed for bi odi esel .
For all tests t he bi odi esel fleet emi ssi ons for NOx, CO,
and THC wer e 3. 2% l ower, 11.3% l ower, and 9. 1%
l ower, r espect i vel y, than for t he di esel fleet. The PM
emi ssi on was 9. 2% higher. The percent age changes
mi ght be meani ngl ess because t he buses fuel ed with
di esel and t hose fuel ed wi t h bi odi esel wer e different. The
pr obl em with this data set is that control and candi dat e
fleets are t oo smal l to det er mi ne statistically si gni fi cant
emi ssi ons di ffer ences due to fuel changes. Al t hough
apparent percent age di ffer ences wer e report ed by
Bat t el l e, NOx and PM emi ssi ons for t he t wo fuels
wer e statistically the same at t he 95% confi dence l evel
due t o t he l arge vari at i on in measur ement s across t he t wo
fleets.
Thes e results show that mor e i n-use data are requi red
to quant i fy the benefits of bi odi esel fuels. However , the
general concl usi on that bi odi esel i ncreases NOx and
decreases hydrocarbon and CO hol ds whet her testing is
done in an engi ne dynamomet er or chassis dynamomet er
format . Part i cul at e emi ssi ons wi l l ei t her remai n const ant
for hi gh oi l use engi nes or decr ease for engi nes that do
not emi t a large percent age o f PM as oil (measured as
SOF).
4 . 2 . 2 . Engine dynamometer studies using four-stroke
engines
Four st roke engi nes pr oduce one power stroke for
ever y t wo-pi st on strokes. The additional st roke is for
purgi ng t he cyl i nder of combust i on gases. The most
moder n four-st roke engi nes are t urbocharged and
i nt er cool ed t o i ncrease t he power out put per unit
wei ght and t o cont rol NOx emi ssi ons. In addition, t hese
C B
.o_
G )
/ )
_ o
ne
n
O
Z
.c_
r -
t ~
t -
O
c -
O
o .
2 0
1 0
0 -
- I 0
- 20
- 30
- 4 0
- 50
- 6 o
- 70
0
____._9
A
O N O x DDC Eng ines
P M Cummins Eng ines
L~ N O x Cummins Eng ines
. . . . i . . . . D . . . . i . . . . i . . . . J . . . .
2 4 6 8 10
W e i g h t P e r c e n t O x y g e n i n B i o d i e s e l o r B l e n d
1 2
Fig. I I. Change in PM and NOx emissions for soy methylester as well as rapeseed methyl- and ethylester blends in stock, four-stroke
engines; data from Table 24.
Fat and vegetable oil derived fuels 153
engines have sophisticated electronic controls, which
are capable of varying the fuel injection timing and other
engine parameters to minimize emissions. Four-stroke
engines are more efficiently lubricated and thus the
SOF portion due to fugitive oil emissions is much
lower than for two-stroke engines, being typically 30%
or less.
Available results for four-stroke engines are summar-
ized in Table 24. Data are reported for methylesters of
soybean oil as well as methyl- and ethylesters of
rapeseed oil. Figure 11 shows how biodiesel emissions
change with blend level in four-stroke engines from
two manufactures and model years from 1987 to 1995.
The results include four independent studies using
different DDC Series 60 engines. 19"42'87"9 Data for
Cummins L-10, N-14, and B5.9 engines 24'69'9] are also
included Differences between engines from the two
manufacturers are probably related to the different
approaches taken toward optimization of the NOJPM
trade-off. It is important to note that, when operating on
D-2, engines from both manufacturers meet emissions
standards for the given model year. Figure 11, compared
to Figs 8 and 10 for two-strokes, shows that the NOx
increase in the newer four-stroke engines may be less
than for older two-stroke engines as a function of fuel
oxygen. For example, at 2 wt% oxygen the NOx increase
is roughly 3%, compared to about 5% for two-strokes,
and the PM reduction is roughly 15%, compared to
perhaps 10% for two-strokes. The larger change in PM
emissions might be expected because of the much lower
SOF fraction in four strokes. For the three Cummins
engines, the average NO~ increase was only 0.4% and the
slope of the regression line was less than 0.02. Therefore,
within the uncertainty of these data, NOx emissions did
not increase for the Cummins engines as a group.
Inspection of the data in Table 24, however, indicates
that the two 1987 model year engines did produce a NOr
increase. The 1995 B5.9 engine actually exhibited a
decrease in NOx emissions when operating on soybean or
rapeseed ester fuels. However, the PM reduction
obtainable with the Cummins engines was markedly
less than obtained with the DDC engines. It must be
noted that these conclusions are based on only two
engines for oxygen content above 2%.
Figure 11 suggests that the regulated emissions
change nearly linearly with oxygen content for a given
manufacturer's calibration or engine design approach. If
linearity is assumed, then the air-shed wide emissions
effects of biodiesel in four-stroke engines are inde-
pendent of its concentration in Number 2 fuel and
depend only on engine manufacturer or calibration.
Clearly, a larger body of data on four-stroke engine
emissions is needed. These data must include a wider
range of blending levels, triglyceride sources other than
soy, and a wider range of engine technologies.
For biodiesel content above 20%, the data in Table 24
consistently indicates a small increase in emissions of
SOF, for studies that measured SOF. This suggests that
the combination of biodiesel or a biodiesel blend and a
diesel oxidation catalyst might yield enhanced PM
reduction benefits. Several of the studies reported in
Table 24 examined the effect of oxidation catalysts and
the results are summarized in Fig. 12. Data are available
only for Cummins engines and suggest that a large
enhancement in PM reduction can be obtained by
combining these two approaches. Only one study
tested the oxidation catalyst without biodiesel. Based
on the single data point a definitive conclusion cannot be
drawn, however the data suggest that for four-stroke
engines the use of an oxidation catalyst is far more
_ 2O
10
Jo
~ - 10
Ilg
r -
c
m
I~. -70
0
1 9 6 7 Cummi n s I . - 1 0
0 1 9 6 7 Cummi n s N - 1 4
1 9 e 5 Cummi n s B 5 . 9
- - - - W ~ Cat al y st
VV'~llout Cat al y st
, i . . . . i . . . . t . . . . i . . . . i . . . . i . . . .
0 2 4 6 8 1 0 12
W e i g h t P e r c e n t O x y g e n i n B i o d i e s e l o r B l e n d
Fig. 12. Comparison of change in PM emissions for four-stroke engines, with and without diesel oxidation catalyst, at various
biodiesel levels; data from Refs 24, 69 and 91 for soybean oil methylester, rapeseed oil methyl- and ethylesters.
154 M. S. Graboski and R. L. McCormick
ef f ect i ve for PM reduct i on than bi odi esel at any bl end
l evel . When t he oxi dat i on cat al yst and bi odi esel are
combi ned, PM reduct i ons in excess o f 50% can
apparent l y be obt ai ned at t he hi gher oxygen contents.
One approach to r educi ng bi odi esel NOx emi ssi ons t o
a l evel equal t o that fr om D- 2 has i nvol ved ei t her
i ncreasi ng cet ane number or decr easi ng aromat i cs. The
effect of t hese propert i es on di esel emi ssi ons in general
is r eveal ed in several studies (see Ref. 40, for exampl e).
Gener al l y, bi odi esel bl ends do not respond to et hyl -
hexyl ni t rat e cet ane addi t i ve treatments. 23'41"42 Sharp 42
found that B- 20 di d r espond to di -t -but yl per oxi de in a
DDC Seri es 60 engi ne, as not ed in Tabl e 24. He was abl e
to l ower NO~ by 6. 2% whi l e pr eser vi ng a 9. 1% benefi t
in part i cul at e emi ssi ons fr om bi odi esel . Thi s is an
i mport ant result that needs to be repl i cat ed in ot her
engi nes and wi t h ot her di esel base stocks. Not e,
however , that B- 20 pr oduced no not i ceabl e i ncrease in
NOx for this engi ne. The same addi t i ve had no effect on
NOx in a t wo- st r oke 6V-92. 41
Graboski et al. 19 pr oposed that NO~ neutral bl ends
with bi odi esel coul d be pr oduced by al t eri ng ei t her t he
base fuel aromat i c cont ent or natural cet ane number.
Thi s t hesi s was recent l y t est ed by Dani el s et al. 92 wi t h a
1995 DDC Seri es 50 engi ne. A l ow aromat i c fuel
(23. 9%) was treated wi t h bi odi esel (to make B-20) and a
smal l amount o f cet ane (n- hexadecane) to rai se t he
cet ane number of t he test bl end t o t he same val ue as
Number 2 cert i fi cat i on fuel. The l ower ar omat i c cont ent
of t he fuel compar ed t o cert i fi cat i on fuel was enough t o
offset t he NOx i ncrease pr oduced by t he bi odi esel . At t he
same t i me, t he part i cul at e mat t er was r educed r el at i ve t o
t he cert i fi cat i on fuel by 24%. It coul d be ar gued that t he
part i cul at e benefit was due to t he propert i es of t he base
st ock and not t he bi odi esel si nce r educi ng t he aromat i c
cont ent al so reduces part i cul at e matter. However , t he
part i cul at e emi ssi on for t he bi odi esei / l ow aromat i c bl end
was 14% bel ow that fr om t he l ow ar omat i c base st ock
alone. Thi s suggest s that fuel r efor mul at i on wi t h oxygen
and aromat i c cont rol is a rout e t o pr oduci ng NOx neutral
but PM reduci ng fuels.
Ti mi ng changes have been i nvest i gat ed in Cummi ns
L-1024 and Cummi ns N-1469 engi nes and results are
summar i zed in Tabl e 24. As not ed for t wo- st r oke
engi nes, ret ardi ng i nj ect i on t i mi ng can r educe NOx
wi t h a loss of s ome effect i veness for PM reduct i on and
a loss of fuel economy. For exampl e, in t he Or t ech N- 14
study, 69 changi ng t he t i mi ng act ual l y i ncr eased PM
emi ssi ons on B- 20 to 4. 1% above t he base di esel l evel .
The same t i mi ng wi t h an oxi dat i on cat al yst pr oduced a
23% reduct i on in PM and a si mul t aneous 3. 5% reduct i on
in NOx. Si mi l ar results wer e obser ved in t he L- 10 study.
Addi t i onal data are needed to confi r m and quant i fy t hese
results, however , the r equi r ement that engi nes have a
speci al cal i brat i on for operat i on on bi odi esel is not
wi t hout costs. The engi nes wi l l have to be cert i fi ed for
emi ssi ons compl i ance wi t h t he new t i mi ng and s omehow
rest ri ct ed to operat e onl y on t he speci fi c bi odi esel bl end
used for cert i fi cat i on.
Other diesel oxygenates. Spreen et al . 93-95 st udi ed a
fuel set wi t h cet ane number fr om 45 t o 60, aromat i cs
fr om 10 t o 30%, and 0, 2 and 4% oxygen by wei ght .
Test s wer e conduct ed usi ng a DDC Seri es 60 and a
Navi st ar DTA- 466, each t est ed wi t h bot h 1994 and 1998
calibrations. Oxygen was added as monogl yme (et hyl ene
gl ycol di met hyl et her) and di gl yme (di et hyl ene gl ycol
di met hyl et her). For t he Seri es 60, t he change fr om 1994
to 1998 cal i brat i on i nvol ved compl et el y di fferent ECM
programs. For t he Navi st ar engi ne, t i mi ng was si mpl y
ret arded 3 . Fuel s wi t h monogl yme wer e mor e respon-
si ve to et hyl hexyl ni t rat e cet ane enhancer than di gl yme.
The data wer e regressed and summar i zed as a model .
Because o f the l i mi t ed number of oxygen combi nat i ons,
t he model s are st at i st i cal l y weak for t he effect of fuel
oxygen. For the Seri es 60, at 5 g NOx cal i brat i on, 1%
oxygen i ncreased NOx 0. 8% and part i cul at e was reduced
8%. For the 4 g cal i brat i on, NOx was i ncreased 0. 5% but
t he i ncrease was not statistically significant. PM was
r educed 7%. For t he DTA- 466, onl y di gl yme signifi-
cant l y affect ed NOx at t he 5- g cal i brat i on. Fuel oxygen
had a si gni fi cant effect for PM reduct i on wi t h t he 5- and
4- g cal i brat i ons. It is not cl ear how t hese results
rel at e quant i t at i vel y t o bi odi esel . They are i ncl uded
here because t hey suggest that t he effect o f oxygen on
NOx emi ssi ons mi ght be further di mi ni shed in 1998
cal i brat i on engi nes.
Chassis studies with f our-stroke engines. Pet erson and
Reece 96 i nvest i gat ed 1994 and 1995 Cummi ns B 5. 91
engi nes in t wo Dodge pi ckup t rucks on a chassis
dynamomet er usi ng t he doubl e arterial cycl e and t he
chassis ver si on of t he Heavy- Dut y Transi ent test.
Rapeseed met hyl - and et hyl est er fuel s wer e used in
testing. The arterial cycl e gave l ower emi ssi ons on a
g/ mi l e basis compar ed to t he heavy- dut y chassis cycl e
but t he r el at i ve effect o f fuel oxygen on emi ssi ons was
essent i al l y t he same. NOx decreased by 13% and PM
i ncreased by 43% compar ed to di esel for t he et hyl est er.
NOx for t he met hyl est er was 3. 4% hi gher than for t he
et hyl est er wi t h t he 1994 truck, whi l e PM was 6% higher.
It is not cl ear why t he chassis based emi ssi ons do not
f ol l ow t he trends obser ved by Sharp 91 usi ng t he engi ne
dynamomet er test procedure. The rapeseed et hyl est er
used by bot h Sharp 91 and Pet erson and Reece 96 was
94. 75% est eri fi ed and cont ai ned si gni fi cant amount s of
gl ycer ol and mono- , di- and t ri gl yceri des. Whi l e this
l ow purity l evel mi ght pr ove pr obl emat i c in engi ne
endur ance tests, it is not known how purity influences
emi ssi ons performance.
Other emissions studies. FEV Engi ne Technol ogy 18
i nvest i gat ed i nj ect i on t i mi ng and i nject i on pressure for
Table 25. Thirteen-mode steady-state emissions for the Navistar
HEUI engine; % change relative to base diesel t8
Biodiesel 10 20 30 50 100
(%)
NO~ 3.5 5.3 6.9 15.8 28.2
PM - 33. 9 -24. 1 - 37. 5 - 26. 8 - 33. 9
HC - 2 8 - 3 2 - 5 3 - 50. 7 - 75. 5
CO - 10. 6 - 8. 1 - 18. 8 - 6. 9 - 13. 8
BSFC 1.9 2.2 3.2 8.5 12.4
Fat and vegetable oil derived fuels 155
various soy blends with diesel, in comparison to diesel,
using a 13-mode steady-state test with the Navistar 7.3 1
HEUI engine. It is important to note that NO, emissions
are primarily related to engine load and speed and less
dependent on whether the operation is transient or steady
state but particulate and other emissions are significantly
affected by transient operation. Table 25 presents the
emissions from the stock engine. Data are presented
which provide several strategies for optimizing the fuel
management function with respect to emissions. FEV
found that NOx increased with biodiesel under all
conditions of speed and load. However, the rate of
generation of particulate and its form varied with
conditions. Biodiesel blends reduced particulate at high
speed and all loads. At lower speeds, particulate was
reduced at light and heavy loads but particulate was
increased at intermediate loads. SOF was always higher
for biodiesel.
The FEV steady-state study also found that relatively
low blending levels of 10-30% methyl soyester are more
responsive to parameter changes over the engine map
than high blends (50 and 100%). For the low oxygen
blends, it was possible to lower NOx at fixed PM but not
to simultaneously reduce PM and NO~ using engine
timing and pressure changes. Any change made to
pressure or timing for biodiesel blends worked equally
well for Number 2 diesel. Thus, NO, emissions increased
and PM, CO and THC emissions fell relative to diesel at
any fixed configuration. An exhaust gas recirculation
(EGR) strategy was examined and it was claimed that a
proposed strategy (not necessarily optimal) could reduce
NO, by 10% without PM or fuel economy penalty.
Again, all fuels might gain from this benefit.
Police et al . 28 investigated a direct injected 90 bhp
diesel engine using a 13-mode steady-state test with
Number 2 diesel and 100% rapeseed oil methylester.
Both fuels had the same cetane number (51.5-51.6). The
diesel had a high boiling with a T-90 of 346C. At low
speed (2200 rpm), as torque increased the ratio of NO~
lbr the ester fuel compared to diesel increased from 1.2
to 1.4, while at rated speed (3800 rpm), the NOx ratio
was constant at about 1.2. These data indicate that NOx
emissions increase at all points in the engine map but
even more so under lugging conditions.
Marshall 22 conducted multi-mode steady-state testing
using a Cummins L-10 engine which showed that NO~
increased from 6.4 to 7.4 g/bhp-hr when comparing D-2
and 100% methyl soyester. He examined ethanol, ETBE
(ethyl t-butylether), and alkylate as NOx reduction
additives. Addition of 20% heavy alkylate made a NOx
neutral fuel compared to the base diesel. This agrees
with the results of Daniels et al . 92 who employed
n-hexadecane (similar to alkylate) and reduction of
aromatic content to reduce NOx emissions. These
studies demonstrate how diesel can be reformulated to
include oxygenates but with a lower aromatic content to
simultaneously control emissions of NO~ and PM.
McDonald et al . 97 examined unique mining transient
cycles. Testing was conducted without and with a diesel
oxidation catalyst on D-2 and B-100. The catalyst
produced sulfate under some heavy load test conditions
resulting in increased particulate. In the cycles driven,
soy ester reduced NOx and particulate. NO, fell by 5 to
10%. Particulate matter without catalyst fell 25 to 33%.
With catalyst, the PM fell 50% relative to D-2. Peak
power decreased 9% and fuel consumption increased
13.7% on soybean oil methylester. The fact that NOx and
PM both decreased may be a result of the specific cycles
used or may be related to the calibration of the
Caterpillar engine employed.
Schumacher et al . 88 examined five tractors using the
ISO 8178 CI, 8-mode steady-state test. Peak power
generally fell in proportion to the soy diesel content.
Smoke was reduced with most soy diesel blends. With
neat ester, smoke was reduced 50 to 70% and
simultaneously NOx increased by 3 to 35%. Goyal TM
used the ISO 8178-4 off-road test with neat methyl
soyester. A Deere 4045T engine run on soyester showed
a 4- 6% power loss. Emissions showed a 10% NOt
increase and a 4% PM decrease. By adjusting the fuel
pump for equal engine output power, the NOx emission
fell to a 2% increase but PM increased by 12%. PM was
much higher in SOF for the soyester (28% for diesel
versus 70% with soyester). With a 4 timing retard, NOt
fell more than 20% and soy diesel NOx was nearly equal
to diesel NOx at both power settings. PM was 25% lower
than base diesel.
Rantanen et al . 27 presented the results of a study
which utilized four European heavy duty engines
ranging from 200 to 280 bhp with the ECE R49 multi-
mode steady-state test. Rapeseed oil methylester
emissions were compared to a typical Finnish diesel
fuel which has an analysis essentially the same as U.S.
average Number 2 diesel except for a higher sulfur
content. Neat rape methylester used in three different
engines produced a 4- 10% increase in NO~ and a 2 -
33% reduction in PM. Krahl et al . 99 reviewed European
data on regulated emissions from rape methylester. Most
data are for light duty diesels using various European
multi-mode steady-state engine tests and U.S. light duty
FTP driving cycle. Emissions are highly dependent on
the driving cycle. NOn increased for all cycles and
engines discussed. The typical increase was 20%.
Particulate generally decreased and the PM reduction
was cycle dependent, with the FTP giving the smallest
decrease (0-20%), and the 13-mode steady-state test
giving a 0- 60% decrease.
Staat and Gateau 29 reported the results of a 3-year test
program using rape methylester. Chassis and engine
testing using Renault bus engines for 0 and 100% ester
were presented. Using the 13-mode engine test, NO~
emissions increased by 9.5%. Using the AQA chassis
cycle NOx decreased by 6.4%. PM decreased by 37.5%
in the engine test and by 8.3% in the chassis test.
Montagne 3 presented data for naturally aspirated and
turbocharged Renault truck engines fueled with 5 and
20% rape methylester blends using a European chassis
truck driving cycle. NOx increased by up to ~ 5% with
increasing ester level for two naturally aspirated and two
turbocharged engines tested in vehicles. Particulate was
156 M. S. Graboski and R. L. McCormick
1 2 oo-
2 0 ~ B i o d i l l ~ 3 S % ~iolI ieI iil
- . . (
~ ,.,o ,. '~*
\ ~ ./-~10.,~ :~ , ' ~ - - ; L
(_ 2. , . , z x
eO0 800 1000 1200 14~0 ~ 0 0 1800
1200"
800 800 1000 1200 1400 1600 1800
6 5 % B iodiesel 1 0 0 % B iodiesel
1.0 I o ) "~, 1~ 1.0 I
o. , , , ~ , '~ , o ~ ~ ., : 2' , o ~ , 7 ~ . . ~ ~ '(~ ,~.~ ~ ..~Y~,~-:~-'~-~'?/~ ~ ' ~ ~ ~
' :--~.0) ~ 4~0::~ ~ -
~00 800 10~0 1200 1400 1(100 lifO0 ~ 0 800 10~0 1200 1400 1600 1800
q . , * d , ~ Speed, q . .
Fig. 13. Contour plots showing ratio of NOx emission with biodiesel to NOx for Number 2 diesel as a function of speed and torque in
the heavy-duty transient test. DDC series 60 engine; data from Ref. 19.
nearl y unchanged for t hree engi nes but doubl ed for t he
fourt h engi ne wi t h B-20. For that vehi cl e, no PM change
was seen for B-5.
Whi l e t he steady-state emi ssi on studies descr i bed in
this section are not r el evant fr om an emi ssi ons
compl i ance poi nt o f vi ew, t hey confi r m that an
i ncrease in NOx emi ssi ons is t ypi cal l y obser ved usi ng
bi odi esel . However , NOx and PM are hi ghl y dependent
upon t he engi ne or chassis cycl e empl oyed and
under s ome condi t i ons PM i ncreased and NOx went
down. It is not cl ear fr om t hese studies whet her t he NOx
i ncrease occur s at all speeds and l oads or onl y in speci fi c
r egi ons of t he engi ne map. The ver y di fferent test
procedures and bl endi ng Number 2 di esel stocks used
in t hese studies make it di ffi cul t to draw general
concl usi ons.
4.3. Discussion of Increased NOx Emission for
Biodiesel
Dat a fr om t he soydi esel study of Graboski et al . 19
have been r eanal yzed to gai n a great er underst andi ng of
t he i ncrease in NOx emi ssi ons. Modal or real t i me NOt
emi ssi ons data for bi odi esel or bi odi esel blends, as ppm
NOx in the di l ut ed exhaust , have been nor mal i zed by
di vi di ng by t he real t i me NOx emi ssi ons for Number 2
diesel. Thi s NOx rat i o is t hen pl ot t ed as cont ours over t he
engi nes s pe e d- t or que map. Thi s approach was used to
gener at e t he pl ot s in Fi gs 13 and 15.
Fi gur e 13 shows cont our pl ot s for neat soydi esel and
soydi esel at several bl end l evel s. The NOx emi ssi on is
cl earl y dependent upon speed and load. The figure shows
that NOx is el evat ed at l ow speed and hi gh t orque
Fat and vegetable oil derived fuels 157
1200
1000
8 00
: 6oo
4 00
200
0
0.00
0.00
0. 25
0. 9 5
0. 4 5
0. 73
0. 23
0.00
1.29
0. 74
0. 50
0.58
2. 22
2. 14
1.09
0. 24
0. 16
0.17 0,20 0. 6 3 0.00
6 00 8 00 1000 1200 14 00 16 00 18 00
S peed, r pm
Fig. 14. Percentage of total work generated over different regions of the heavy-duty transient cycle; shaded regions represent nearly
75% of work generated.
(roughly 1000 rpm and 600- 1000 ft-lb) for the Series
60 engine. NOx levels are also elevated in the
1200-1600 rpm range and at torque below 400 ft-lb. At
the highest speeds and loads, NO~ emissions are
essentially unchanged with biodiesel. The NO~ increase
becomes more significant as the oxygen content of the
fuel increases. In Fig. 14, the work done in various
regions of the transient cycle is shown as a percentage of
total work. The shaded areas represent ~ 75% of the
work performed and so increased NOx concentration in
the exhaust in these regions will have the biggest impact
on the NOx mass emission. Clearly the most important
region of the DDC Series 60 map for NOx emissions
increase is the 1400-1600 rpm and 200- 600 ft-lb range.
The increase in exhaust NOx concentration observed in
this region most likely accounts for all of the increase in
NO~ mass emissions observed for this engine when
operating on biodiesel fuels.
McCormick et al . 87 reported on the relative NOx
emissions for 2% oxygen as octanol or as methyl
soyester, compared to a base Number 2 diesel for
transient tests conducted with the same DDC Series 60
engine. Figure 15 shows contour plots of the modal (real
time) data collected over the test cycle. The increased
NOx emissions are concentrated in the same regions as in
the previously described study. The type of oxygenate
has an impact on the local NOx emission. Octanol
produces a much smaller relative NOx peak under the
lugging condition and actually lowers NOx at high speed
and load. The form of the oxygenate is clearly important
in determining the NOx emission and further research
into the causes of this could help to improve the emission
characteristics of biodiesel and other oxygenated diesel
fuels.
Fuel density is known to effect emissions of NOx
from diesel engines. For example, Signer et al . loo report
a 3- 4% increase in NOx for a 3.5% increase in fuel
density using the EEC 13-mode test cycle. The NO~
increase occurred because the fuel injectors inject a
constant volume or larger mass for the more dense fuel,
at a given speed and load. Because a larger mass of fuel
is burned, more NO~ is produced. As noted in Table 9,
the density change for neat biodiesel relative to base
diesel fuel is ~ 3.5%. Note, however, that biodiesels and
biodiesel blends have a reduced heating value relative to
the Number 2 diesel. For example, the heating value of
the 2 wt% oxygen soyester blend is more than 2% lower
than for the base diesel but density would be expected to
be well below 1% different. This lower heating value
effect competes with, and should be larger than the effect
of fuel density on the heat and NOx generated per
injection.
158 M. S. Graboski and R. L. McCormick
. Q
e"
Er
1200
1000
NO=(m ye=ler)/NO,(diuel)
80O
6 00
40O
200
0
60O 8 00 1000 1200 14 00 16 00 18 00
Speed, rpm
NO=(octanol)/NO=(diesel)
1200
d= 6 o0
$
6 00 8 00 1000 1200 14 00 16 00 18 00
Speed, rpm
Fig. 15. Contour plots showing ratio of NOx emission with oxygenate to NO~ emission without oxygenate as a function of speed and
torque in the heavy-duty transient test. DDC series 60 engine, 2 wt% fuel oxygen, 17 vol% oxygenate, s7
Parker Il has recent l y di scussed possi bl e causes for
t he i ncr eased NOx duri ng bi odi esel and di esel oxygenat e
combust i on:
1. An i ncrease in t he fl ame t emperat ure in ei t her the
pr emi xed or di ffusi onal burn r egi mes. Whi l e
oxygenat ed fuel s have a l ower adiabatic fl ame t em-
perature, car bonaceous PM or soot part i cl es are
ver y ef f ect i ve heat radiators. Ther efor e, t he net
resul t of t he PM reduct i on caused by suppl yi ng
oxygen to t he fuel pyrol ysi s zone may be t o
i ncrease fl ame t emperat ure because o f this loss o f
radiant heat transfer.
2. Spray propert i es may be al t ered due t o di fferences
in vi scosi t y, surface tension, and fuel boi l i ng poi nt
for t he oxygenat ed fuels. Spray propert i es affect ed
may i ncl ude dropl et size, dropl et moment um and
hence degr ee o f mi xi ng and penet rat i on, evapor a-
tion rate, and radiant heat t ransfer rate. A change in
Fat and vegetable oil derived fuels 159
any of t hese propert i es mi ght l ead t o di ffer ent rel a-
t i ve durat i on o f the pr emi xed versus di ffusi onal
burn r egi mes. Si nce it is possi bl e that di fferent
fuel fract i ons are consumed in pr emi xed and di ffu-
sional burn, and si nce t he t wo burni ng pr ocesses
may have di fferent pol l ut ant for mat i on charact er-
istics, this di ffer ence in i gni t i on del ay coul d be the
cause of the i ncreased NOx emi ssi on. Changes in
spray propert i es may also change charact eri st i cs of
the di ffusi onal burn r egi me that l ead to i ncreased
fl ame t emperat ure and hi gher l evel s of NOr
format i on.
3. Oxygenat es may change i gni t i on del ay in ways not
det ect ed by measur i ng cet ane number. Igni t i on
del ay wi t hi n an engi ne can be a funct i on of both
t he fuel s used and fuel spray propert i es. The i mpor-
t ance of i gni t i on del ay is that l onger del ays pr ovi de
t i me for mor e fuel to become pr emi xed and
t herefore consumed in t he pr emi xed phase rather
than in t he di ffusi onal burn phase wi t h possi bl e
di ffer ences in emi ssi ons as di scussed above.
4. Fuel chemi st r y effect s in t he fl ame r egi on coul d
account for a change in nitric oxi de product i on.
Ther mal , or Zel dovi ch NO is unaffect ed by fuel
chemi st ry, however , pr ompt NO can account for
30% or mor e of t he total nitric oxi de emi ssi on. ~2
Si nce prompt nitric oxi de is sensi t i ve to radical
concent rat i ons at t he fl ame front, an i ncrease in
prompt NO coul d be attributed to fuel chemi st r y
effect s. The var i ous mechani sms o f NOx format i on
have been ext ensi vel y r evi ewed. 13
5. Removal of the car bonaceous PM fr om t he com-
bustion envi r onment may el i mi nat e NO- c a r bo n
reactions. The i mport ance of NO- c a r bo n react i ons
in di esel combust i on is unknown.
Gi ven that not all oxygenat es descri bed in the
literature i ncreased NO~ but all gave a si mi l ar l evel of
PM reduct i on; the data report ed here do not support
hypot hesi s (1) above. The current data are i nsuffi ci ent to
di st i ngui sh bet ween the r emai ni ng hypot heses, however ,
we can di scuss the effect of oxygenat ed bl endi ng on the
fuel physi cal propert i es i mport ant in spray combust i on.
Di esel spray propert i es, speci fi cal l y t he dropl et size
di st ri but i on and Saut er mean di amet er, are i nfl uenced by
fuel surface t ensi on and vi scosi t y. 39 Saut er mean
di amet er has been shown to i ncrease wi t h i ncreasi ng
surface t ensi on and vi scosi t y, t4 As noted, i ncreased
dropl et size can r educe the fract i on of fuel burned in the
pr emi xed combust i on phase and l ead to i ncreased
durat i on o f di ffusi on fl ame combust i on. We have
est i mat ed t he surface t ensi on and vi scosi t y of bi odi esel
and ot her di esel oxygenat e bl ends and found changes in
fuel propert i es that are easi l y large enough to i mpact
spray propert i es whi ch in turn i mpact emi ssi ons. 87
Anot her fact or whi ch may be r el evant to t he i ncreased
NOx emi ssi ons fr om bi odi esel s is the r el at i vel y hi gh
boi l i ng poi nt of t hese oxygenat es. Hi gher boi l i ng poi nt
fuel s may requi re l onger to be heat ed to boi l i ng and to
vapori ze. Thi s effect may reduce the rate o f dropl et
evaporat i on and lead to consumpt i on of a smal l er
fract i on of the fuel in pr emi xed r el at i ve to di ffusi on
burn combust i on. Cl ari fi cat i on of t hese issues awai t s
additional engi ne, combust i on bomb, and model i ng
studies.
4.4. Smoke Opaci~
Smoke emi ssi ons are regul at ed usi ng a procedure
speci fi ed in the Code of Federal Regul at i ons. Jo5 Smoke
is onl y l oosel y rel at ed to total part i cul at e si nce opaci t y is
great er for dark smoke than for whi t e smoke and in fact,
smoke opaci t y may be compl et el y uncorrel at ed with
mass emi ssi ons of PM. In most instances, smoke opaci t y
is used as an i ndi cat or of engi ne mal funct i on in an
i nspect i on and mai nt enance program. Onl y a l i mi t ed
number of studies have exami ned smoke opaci t y usi ng
the CFR procedure and t hese results are summar i zed in
Tabl e 26. Fosseen 6 report data for a t wo-st roke engi ne
that show no benefit in smoke opaci t y for bi odi esel .
Combi nat i on of an oxi dat i on cat al yst and bi odi esel
pr ovi ded a si gni fi cant reduct i on in smoke opaci t y.
Ort ech 69 report ed smoke opaci t y measur ement s for
B-10 and B- 20 soy bl ends in a four-st roke engi ne. The
use of bi odi esel si gni fi cant l y reduced smoke opaci t y.
Bi odi esel had t he great est effect on smoke in the l uggi ng
mode where B-10 reduced smoke by 28. 6% and B- 20
reduced smoke by 50%. Combi ni ng an oxi dat i on cat al yst
with B-20 pr ovi ded onl y a small additional benefit.
A number of studies report smoke opaci t y for engi nes
or vehi cl es at vari ous speeds and l oads usi ng non-
standard procedures. Lucas 7 report ed the results of snap
idle and l ong term smoke reduct i on benefits usi ng
bi odi esel bl ends with JP- 8 compar ed to JP-8 alone. Al l
vehi cl es showed marked smoke reduct i on with the
Table 26. Smoke opacity results (%) for Number 2 diesel and biodiesel blends using the CFR 40 Part 86 Subpart I procedure
Reference Engine Set-up Fuel Mode
Acceleration Lugging Peak
60 DDC 6V-71 N-77 MUI
69 Cummins N-14-87 MUI
Stock D-2 1.2 1.8 1.8
Stock B-20 (Soy) 1.1 1.9 2.0
Stock + cat D-2 1.4 2.1 2.1
Stock + cat B-20 (Soy) 0.9 1.7 1.7
Stock D-2 7.1 1.4 22.5
Stock B-10 (Soy) 6.3 1.0 20.7
Stock B-20 (Soy) 5.4 0.7 18.3
Stock + cat B-20 (Soy) 5.3 0.7 17.3
160 M.S. Graboski and R. L. McCormick
biodiesel blends in snap idle testing. One vehicle tested
had a initial opacity of 57% without biodiesel. After the
introduction of biodiesel blends, the initial opacity was
46% falling to 22% after 10000 miles. Biodiesel might
have exhibited detergent action in the fuel system.
Several studies have noted that the Bosch smoke number
is reduced 10-20%, especially at higher loads, when
operating on B-20.18"2s'4s Fosseen, in an NBB funded
study of biodiesel performance in a bus fleet, also noted a
20% reduction in opacity. ~6 Based on these data it
seems likely that, for newer two-stroke and four-stroke
engines, biodiesel significantly reduces smoke opacity.
4.5. Unregulated Emissions and Air Toxins
At some future time, regulatory agencies may limit the
emission of specific compounds, classes or compounds,
or fractions of the exhaust such as SOF. Thus it is
important to have an understanding of the impact of
biodiesel on these emissions, and to understand if use of
biodiesei leads to an increase in emissions of any specific
classes of toxic compounds. Air toxic emissions from
diesel can be divided into two groups: those in the THC
portion of the gaseous emission and multi-ring PAH
found in the SOF portion of the particulate. Many
volatile compounds are known to have mutagenic or
carcinogenic activity. The most important of these are
light aldehydes (such as formaldehyde and acetaldehyde)
diolefins especially 1,3-butadiene, and light aromatics,
particularly benzene. Only limited data on these
emissions are available from testing in the U.S. on soy,
tallow and waste oil based esters. The European
Community has gathered more extensive data for rape
methylesters, using primarily the European steady-state
test, on a variety of heavy-duty diesel engines. However,
few studies have reported quantitative mass emissions of
air toxins for biodiesel fuels. Thus, at this time it is
difficult to draw general conclusions on unregulated
emissions for biodiesei and this is clearly an area in need
of more extensive research.
4.5.1. Soluble organic f raction
Particulate is conventionally speciated into three
fractions. These are soot or carbon, liquids derived
from fuel and oil (SOF), and sulfuric acid from fuel
sulfur (measured as sulfate). SOF is unregulated except
in California ARB diesel. SOF contains PAH and nitro-
PAH compounds known to be highly mutagenic. As
noted in an earlier section of this review, much of the
SOF from two-stroke engines is engine lubricant and so
it is difficult to assess the impact of biodiesel on the total
SOF emission. Based on steady-state testing, biodiesel
particulate is believed to be much higher in SOF than
Number 2 diesel fuels, although this is not particularly
clear from the transient emissions data reported in Tables
20, and 23. The fact that use of diesel oxidation catalysts,
which are designed to convert SOF, leads to even higher
PM reduction for biodiesei fuels than for Number 2
diesel also indicates that biodiesel increases SOF.
Future research must address the questions of the
effect of biodiesels on mass emissions of SOF and on
the nature of the SOF with respect to reactive, toxic, and
mutagenic properties. Some data related to these
questions are described in the section on PAH emissions
below.
4.5.2. Poly-aromatic hydrocarbons
A large number of qualitative studies seem to indicate
that use of biodiesel decreases PAH. McDonald et al . 97
examined emissions for off-road mining applications
using a Caterpillar 3304 PCNA and the ISO 8178-C! 8
mode off-highway test as noted above. Mutagenicity
with soyester and a diesel catalyst was reduced to one-
half of that of D-2. The reduction is due to a reduction in
emissions of PAH. Krahl et al. 99 reviewed European
data on air toxins from rape methylester fuels. Most data
were based on light duty diesels using various European
multi-mode steady-state engine tests and the U.S. light
duty FFP driving cycle. Emissions are highly dependent
on the driving cycle. PAH emissions with biodiesel in
direct injection engines ranged from 80 to I 10% of those
for D-2 for the FTP, and from near zero to 80% of diesel
PAH emissions for various steady-state tests. Staat and
Gateau 29 reported the results of a 3-year test program
using rape methylester blends. Chassis and engine
testing using Renault bus engines for 0, 30 and 50%
blends suggested that total PAH emissions were
unchanged. Montagne 3 presented data for naturally
aspirated and turbocharged engines Renault truck
engines fueled with 5 and 20% rape methylester blends
using a European chassis truck driving cycle. For
turbocharged engines, rape methylester decreased
PAH by 40-50%. Shafer ~7 reported the results of a
study by Mercedes Benz using palm oil esters. The
Mercedes Benz indirect injection bus engine employed
experienced a total PAH decrease.
In much more quantitative studies, Rantanen et al. 27
presented results for air toxins as well as regulated
emissions from rape methylesters. Brake specific PAH
emissions were reported at several steady-state condi-
tions. Total PAH emissions decreased by approximately
75% for B-30 and by more than 85% for B-100 relative
to Finnish D-2. Mutagenicity tests were conducted based
upon Salmonella strains that are highly sensitive to nitro-
PAH compounds. This showed mutagenic activity was
only about 10% lower for the biodiesel particulate than
for D-2, for the one set of engine data reported. Using
nitro-PAH insensitive strains, the mutagenicity of rape
methylester exhaust fell to about one-third that of diesel.
Thus, for rape methylester, the total PAH emission is
lower but the mutagenic activity of the PAH appeared to
be significantly higher than for diesel. This may be
caused by the presence of nitrated polycyclic hydro-
carbons like l-nitropyrene. Based upon EPA transient
tests in a Cummins B5.9 engine, Sharp 91 reported that
PAH emissions were also reduced with biodiesel. For
neat ethyl- and methylesters of rapeseed oil brake
specific PAH emissions declined by 37 and 54%,
Fat and vegetable oil derived fuels 161
respect i vel y. The PAH reduct i on was in t he range of 2 0 -
30% for B- 50 bl ends and was i nsi gni fi cant for B-20.
Kado t8 report ed on PAH emi ssi ons fr om di esel and
neat met hyl and et hyl rape esters. The GC/ MS
analytical t echni que empl oyed was report ed to exhi bi t
a standard devi at i on of about 10%. Emi ssi ons of
phenanthrene, pyr ene and benzant hr acene wer e 2 0 -
40% less for t he est er than for diesel. Benzopyr ene
i ncreased slightly. Usi ng AMES Sal monel l a testing, the
esters exhi bi t ed l ower act i vi t y exhaust than t he diesel
base fuel.
4.5.3. Al d eh yd es
As for PAH, a great deal of qual i t at i ve i nformat i on is
avai l abl e on t he effect o f bi odi esel on emi ssi ons of
al dehydes. McDonal d et al . 97 exami ned emi ssi ons for
off- r oad mi ni ng appl i cat i ons usi ng a Cat erpi l l ar 3304
PCNA and the ISO 8178-C1 8 mode off- hi ghway test as
not ed above. For mal dehyde was not si gni fi cant l y
i ncreased usi ng a bl end or neat soyester. A di esel
oxi dat i on cat al yst reduced for mal dehyde by 26%. Krahl
et al . 99 found that total al dehydes for di rect i nj ect i on
engi nes gener al l y i ncreased with bi odi esel by 0 - 7 5 %,
i ndependent of test cycl e. Staat and Gat eau z9 report ed
that for 0, 30 and 50% blends, C~ through C5 al dehyde
emi ssi ons i ncrease with est er concent rat i on. Acr ol ei n
i ncreased by 50% wi t h 50% est er blends. The i ncrease in
acrol ei n, a car ci nogeni c air toxin, was attributed to
gl ycer i des in the boi di esel fuel, agai n rei nforci ng the
need fi)r hi gh purity bi odi esel . Mont agne 3 present ed
data for naturally aspirated and t urbocharged engi nes,
Renault truck engi nes fuel ed with 5 and 20% rape
met hyl est er bl ends usi ng a European chassis truck
dri vi ng cycl e. For t urbocharged engi nes, rape met hyl -
est er i ncreased for mal dehyde by about 60%, and
i ncreased acrol ei n by 2 5 - 4 0 %. Shafer ~v report ed the
results of a study by Mer cedes Benz usi ng pal m oil
esters. Compar ed to di esel , all al dehydes except
acrol ei n decreased. The i ncrease in acrol ei n was
attributed to gl ycer ol in the fuel. Above 50% load at
rated speed all regul at ed and unregul at ed emi ssi ons
for the est er were l ower, whi l e at l i ght er l oad and rated
speed, di esel emi ssi ons are lower. In chassis studies
with buses, Howes and Ri deout 67'68 report ed no
i ncrease in for mal dehyde emi ssi ons for B- 20 (soy)
rel at i ve to D-2.
Rant anen et al . 25 present ed results l br air t oxi cs as
well as regul at ed emi ssi ons from rape methylesters.
Exhaust gases wer e anal yzed by FTIR. For mal dehyde
was found above the det ect i on l i mi t in diesel and rape
met hyl est er exhaust at the same levels. Thus, even
though rape met hyl est er coul d yi el d for mal dehyde by
l br mat i on of a met hyl radical from the ester, the authors
suggest that this di d not occur to any si gni fi cant degree.
Based upon EPA transient tests in a Cummi ns 5.9-1
engi ne, Sharp 91 report ed that bi odi esel (REE and RME)
does not in general i ncrease al dehyde emi ssi ons and
oxygenat es may have act ual l y pr oduced a reduct i on in
emi ssi ons o f formal dehyde.
4.5.4. Summa r y
Ther e is consi der abl e data that emi ssi ons of SOF, or at
least the fract i on of the PM that is SOF, i ncreases for
bi odi esel . Ther e also seems to be agr eement that the use
of bi odi esel results in both a decr ease in emi ssi ons of
PAH, and in the mut ageni c act i vi t y of t he di esel exhaust.
The mut ageni c act i vi t y o f the PAH itself, however , may
be hi gher than that fr om convent i onal diesel. Because of
the l i mi t ed number o f truly quant i t at i ve studies (such as
Refs 27, 91 and 108), it is not possi bl e to state the
magni t ude o f the PAH decrease that mi ght be expect ed
for a gi ven engi ne t echnol ogy or bi odi esel source. The
most quant i t at i ve studies find no i ncrease in al dehyde
emi ssi ons for hi gh qual i t y (high purity) bi odi esel .
However , emi ssi ons of acrol ei n may i ncrease i f gl ycer ol
or gl ycer i des are present in the fuel.
Ther e is some evi dence that emi ssi ons of benzene
i ncrease for rape met hyl est er but it is unknown i f this
phenomenon is gener al l y true for all bi odi esel fuel s and
all dri ve cycl es. For exampl e Krahl et al . 99 found
benzene emi ssi ons for di rect i nject i on engi nes fell by
50% for t he FTP but i ncreased by 40% in steady-state
testing. Staat and Gat eau 29 report ed benzene emi ssi ons
i ncreased by about 15% for 50% est er fuel. Shafer ~7
report ed benzene, xyl enes, and t ol uene i ncreased with
pal m esters. It is i mport ant to note that defi ni t i ve studies
in this area have not been performed. Ther efor e, any
concl usi ons drawn regardi ng unregul at ed emi ssi ons and
toxins must be treated as prel i mi nary observat i ons.
5. CONCLUSIONS AND SUMMARY OF RESEARCH NEEDS
Research and devel opment effort s usi ng pri mari l y
met hyl est ers o f vari ous fats and oils have shown that
t hese bi odi esel s can be suitable fuel s for diesel engi nes.
The use of bi odi esel in neat or bl ended for m has no effect
on the Btu based engi ne fuel economy. The lubricity of
t hese fuel s is superi or to convent i onal diesel and this
propert y is i mpart ed to blends at l evel s above 20 vol %.
Emi ssi ons of PM can be reduced dramat i cal l y through
the use of bi odi esel in engi nes that are not high lube oil
emitters. Emi ssi ons of NOx i ncrease si gni fi cant l y for
both neat and bl ended fuel s in both t wo- and four-st roke
engi nes, The i ncrease may be l ower in newer, l ower NOr
emi t t i ng four-strokes, but additional data are need to
confi rm this concl usi on. Effort s at el i mi nat i ng this NO,
increase based on combi nat i ons of i nject i on t i mi ng
changes and SOF oxi dat i on catalysts are successful but
work equal l y wel l for pet rol eum der i ved diesel.
Bi odi esel s manufact ured fr om soybean or rapeseed oils
cannot be pri ced l ow enough for market forces al one to
guarant ee their use. Pri ce is al most t ot al l y gover ned by
feed stock cost i ndi cat i ng that l ower cost waste oils may
be mor e economi cal l y attractive. Ot her approaches, such
as plant breedi ng or modi fi cat i on to i mpr ove oil yi el d or
chemi cal modi fi cat i on o f the oil to produce high val ue
coproduct s may also have promi se.
The data r evi ewed in this art i cl e suggest a number of
162 M. S. Graboski and R. L. McCormick
i mport ant areas for fut ure research. Among t he most
i mport ant r ecommendat i ons is the need for all future
studies to empl oy bi odi esel o f wel l known composi t i on
and purity and to report det ai l ed analyses. Ot her areas for
additional research i ncl ude:
1. Exami nat i on o f l ower cost feed st ock mat eri al s for
manufact ure o f esters, i ncl udi ng studies o f t he
t ransest eri fi cat i on process appl i ed to t hese feeds,
purification and propert i es o f t he est er product ,
and per for mance in engi nes and vehi cl es.
2. Devel opment o f a hi ghl y act i ve het er ogeneous
cat al yst for t he t ransest eri fi cat i on react i on, capabl e
o f achi evi ng ver y hi gh gl ycer i de conver si on, is
needed. Whi l e this devel opment wi l l have onl y a
mi nor i mpact on bi odi esel product i on cost , it wi l l
great l y si mpl i fy t he product i on process. Thi s pro-
cess si mpl i fi cat i on wi l l al l ow i mpr oved cont rol of
product qual i t y.
3. Processi ng schemes for produci ng additional
product s fr om fats and oi l s, as wel l as bi odi esel
wi t h i mpr oved propert i es (hi gher stability and
l ower boi l i ng poi nt , for exampl e) shoul d be i nvest i -
gated. By pr oduci ng a suite o f val uabl e product s,
t he bi odi esel sales pri ce mi ght be l ower ed
significantly.
4. The effect of bi odi esel purity on propert i es,
stability, and per for mance in engi nes and vehi cl es
needs furt her i nvest i gat i on. The puri t y l evel s
necessary for achi evi ng adequat e engi ne
endurance, compat i bi l i t y wi t h coat i ngs and el ast o-
mers, col d fl ow propert i es, stability, and emi ssi ons
per for mance must be defined.
5. A det ai l ed underst andi ng o f what const i t ut es an
accept abl e l evel o f oxi dat i ve and bi ol ogi cal
stability is needed, al ong wi t h knowl edge o f
accept abl e l evel s o f oxi dat i ve degradat i on pro-
ducts.
6. A det ai l ed underst andi ng of t he effect o f bi odi esel
chemi cal structure on col d fl ow propert i es and
stability is needed. Addi t i onal l y, fl ow i mpr over
addi t i ves and stabilizers speci fi c for bi odi esel s
and bi odi esel bl ends need t o be devel oped.
7. Fundament al model i ng, combust i on bomb, and
shock tube studies o f bi odi esel combust i on, i ncl ud-
i ng the causes o f i ncreased emi ssi ons of NOx, are
needed. These shoul d i ncl ude t he i mpact of bi o-
di esel on fuel spray propert i es. Basi c research in
engi nes t o mor e ful l y understand t he NOf f PM
t r adeoff as a funct i on of speed and t or que may
al l ow opt i mi zat i on o f engi ne cal i brat i on for bi odi e-
sel. Thes e studies wi l l appl y not j ust t o bi odi esel
but to di esel oxygenat es in general .
8. Subst ant i al l y mor e i n-use and engi ne- t est i ng data
in four-st roke engi nes usi ng all sources of bi odi esel
are required. Det ai l ed quant i t at i ve measur ement s
o f r egul at ed emi ssi ons and unregul at ed t oxi c
emi ssi ons are needed.
9. The effect o f cet ane i mpr over s and bl endi ng di esel
r efor mul at i on on bi odi esel emi ssi ons per for mance
shoul d be i nvest i gat ed in much mor e detail.
10. Defi ni t i ve studies o f t he effect o f bi odi esel fr om
var i ous sources, and di esel oxygenat es in general ,
on emi ssi ons o f t oxi c, mut ageni c, and carci no-
ge ni c compounds need to be performed.
Acknowledgement--The authors wish to thank the U.S.
Department of Agriculture, Office of Energy and New Uses
for supporting the preparation of this review.
REFERENCES
I. Walton, J., Gas & Oil Power, p. 167, July 1938.
2. Martinez de Vedia, R., Diesel Power and Diesel
Transportation, p. 1298, December 1944.
3. Huguenard, C. M., Dual fuel diesel engines using cotton-
seed oil with variable injection timing. M.S. thesis, Ohio
State University, 1951.
4. Bruwer, J. J., van D Boshoff, B., Hugo, F., du Pleiss L. M.,
Fuls, J., Hawkins, C., van der Walt, A. and Englebrecht,
A., Sunflower seed oil as an extender for diesel fuel in
agricultural tractors. Presented at the 1980 Symposium of
the South African Institute of Agricultural Engineers, 11
June 1980.
5. Varde, K. S., Vegetable oil fuels. In Proceedings of the
International Conference on Plant and Vegetable Oils as
Fuels, American Society of Agricultural Engineers,
Publication 4-82, p. 303, 1982.
6. Baranescu, R. A. and Lusco, J. J., Vegetable oil fuels. In
Proceedings of the International Conference on Plant and
Vegetable Oils as Fuels, American Society of Agricultural
Engineers, Publication 4-82, p. 312, 1982.
7. Fort, E. F. and Blumberg, P. N., Vegetable oil fuels. In
Proceedings of the International Conference on Plant and
Vegetable Oils as Fuels, American Society of Agricultural
Engineers, Publication 4-82, p. 374, 1982.
8. Johanson, O. and Mordstrom, O., Vegetable oil fuels. In
Proceedings of the International Conference on Plant and
Vegetable Oils as Fuels, American Society of Agricultural
Engineers, Publication 4-82, p. 337, 1982.
9. Peterson, C. L. and Feldman, M., EMA test cycles:
influence of fatty acid composition on engine deposits, in
The potential of vegetable oil as an alternate source of
liquid fuel for agriculture in the Pacific Northwest--V.
Final report of College of Agriculture and Engineering,
University of Idaho, pp. 132-137, 1987.
10. Bacon, D. M., Brear, F., Moncrieff, I. D. and Walker, K.
L., The use of vegetable oils in straight and modified form
as diesel engine fuels. In Beyond the Energy Crisis,
Volume 3, Third International Conference on Energy Use
Management, ed. R. Fazzolare and C. B. Smith. Pergamon
Press, New York, 1981, p. 1525.
I 1. Engler, C. R., Johnson, L. A., Jegasothy, H., Reddy, M.B.
and Yarbrough, C.M., Proceedings: Vegetable Oil as a
Diesel Fuel Seminar 111, Peoria, IL, p. 71, 1983.
12. Freedman, B., Pryde, E. H. and Mounts, T. L., J. Am. Oil
Chem. Soc., 1984, 61, 1638.
13. Reed, T. B., Graboski, M. S. and Gaur, S., Biomass and
Bioenergy, 1992, 3, 111.
14. Peters, M. S. and Timmerhans, K. D., Plant Design and
Economics f or Chemical Engineers. McGraw-Hill, New
York, 1980.
15. Withers, R. V. and Noordam, M., Proceedings of the 3rd
Liquid Fuels Conference, 15-17 September, Nashville,
TN, 366pp., 1996.
16. Fosseen Manufacturing and Development, Emission
testing on biodiesel and biodiesel blends. Final Report
No. NSDB4FI5 to National Soy Diesel Development
Board, Jefferson, MO, July 1994.
17. Manicom, B., Green, C. and Goetz, W., Methyl soyate
evaluation of various diesel blends in a DDC 6V-92TA
Fat and vegetable oil derived fuels 163
engine, Ortech International. Final Report No. 93-E14-21
to Fosseen Manufacturing and Development, 12 April
1993.
18. FEV Engi ne Technology, Inc., Emi ssi ons and perfor-
mance characteristics of the Navistar T444E DI engi ne
fueled with bl ends of biodiesel and low sulfur diesel.
Phase 1 Final Report to National Biodiesel Board, 6
December 1994.
19. Graboski, M. S., Ross, J. D. and McCormick, R. L., Soc.
Aut omot i ve Eng. Technical Paper No. 961166, 1996.
20. Schumacher, L., Chellappa, A. , Wetherell, W. and
Russell, M. D., The physical and chemical characteriza-
tion of biodiesel low sulfur diesel fuel blends. Final Report
to National Biodiesel Board, Jefferson, MO, 30 December
1995.
21. McDonald, J., Purcell, D., McClure, B. and Kittelson, D.,
Soc. Automotive Eng. Technical Paper No. 950400, 1995.
22. Marshall, W., Improved control of NOX emi ssi ons with
biodiesel fuels. Final Report, DOE Contract DE-AC22-
94PC91008, March 1994.
23. Clark, S. J., Wagner, L., Schrock, M. D. and Piennaar, P.
G., J. Am. Oil Chem. Soc., 1984, 61 (10), 1632.
24. Stotler, R. and Human, D., Transient emi ssi on evaluation
of biodiesel fuel blend in a 1987 Cummi ns L-10 and DDC
6V-92-TA. ETS Report No. ETS-95-128 to National
Biodiesel Board, 30 November 1995.
25. Mi dwest Biofuels Inc., Biodiesel Cetane Number Engi ne
Testing Compari son to Calculated Cet ane Index Number.
Mi dwest Biofuels Inc., Overland Park, Kansas, 1993.
26. Reece, D. and Peterson, C. L., Progress report Idaho on-
road test with vegetable oil as a diesel fuel. In
Proceedings: First Biomass Conference of the Americas,
National Renewabl e Laboratory, 30 Augus t - 2 September,
p. 891, 1993.
27. Rantanen, L., Mikkonen, S., Nylund, L., Kociba, P.,
Lappi, M. and Nylund, N.-O., Soc. Aut omot i ve Eng.
Technical Paper No. 932686, 1993.
28. Police, G., Prati, M. V., Auriemma, M. and Alfuso, S.,
Regulated emi ssi ons of DI diesel engines fuelled with
methyl est er of rape seed oil. In Fuels f or Automotive and
Industrial Diesel Engines. Institution of Mechanical
Engineers, London, p. 139, 1993.
29. Staat, F. and Gateau, P., Soc. Automotive Eng. Technical
Paper No. 950053, 1995.
30. Montagne, X., Soc. Automotive Eng. Technical Paper No.
962065, 1996.
31. Adept Group, Emi ssi ons and engi ne performance of soya
and canola methyl esters with ARB#2 diesel fuels, Report
to Saskatchewan Canola Devel opment Commi ssi on,
Saskatoon, Saskatchewan, July 1995.
32. Peterson, C. L., Reece, D. L., Thompson, J. L., Zhang, X.,
Hammond, B. L. and Beck, S., Devel opment of rapeseed
biodiesel for use in hi gh-speed diesel engines. Report to
U.S.D.O.E., Contract No. 93BIO9233, University of
Idaho, No. 302, Sept ember 1996.
33, Geyer, S. M.. Jacobus, M. J. and Lestz, S.S., TransASAE,
1984, 27, 375.
34, Masjuki, H., Zaki, A. M. and Sapuan, S. M. Methyl ester
of palm oil as an alternative diesel fuel. In Fuels f or
Automotive and hzdustrial Diesel Engines. Institution of
Mechanical Engineers, London, p. 129, 1993.
35. Peterson, C., Reece, D., Hammond, B., Thompson, J. and
Beck, S., Maki ng and testing a biodiesel fuel made from
ethanol and waste french fry oil. Idaho Department of
Water Resources Report, July 1995.
36. Freedman, B. and Bagby, M. 0. , J. Am. Oil Chem. Sot.,
1990, 67 (9), 565.
37. Klopfenstein, W. E., Proceedings: Vegetable Oil as a
Diesel Fuel Seminar 111, Peoria, IL, p. 104, 1983.
38. Knothe, G., Bagby, M. O. and Ryan, T. W,, Soc.
Automotive Eng. Technical Paper No. 971681, 1997.
39. Heywood, J. B., Internal Combustion Engine Fundamen-
tals. McGraw-Hill, New York, 1988.
40. Ullman, T,, Mason, R. and Montalvo, D., Study of cet ane
number and aromatic content effect s on regulated
emi ssi ons from a heavy-duty engine. Sout hwest Research
Institute Report No. 08-2940, CRC Contract VE-1,
Sept ember 1990.
41. Sharp, C. A., Transient emi ssi ons testing of biodiesel in a
6V-92TA DDEC engine. Southwest Research Institute
Report 6602 and 6673 to National Biodiesel Board,
Oct ober 1994.
42. Sharp, C. A. , Transient emi ssi ons testing of biodiesel and
ot her additives in a DDC Series 60 engine. Southwest
Research Institute Report for National Biodiesel Board,
December 1994.
43. Ali, Y., Hanna, M. and Cuppett, S., J. Am. Oil Chem. Soc.,
1995, 72 (12), J7654- 1.
44. Sims, R., TransASAE, 1985, 29, 716.
45. Engine Manufacturers Association, Biodiesel Fuels and
Their Use in Diesel Engine Applications. Engine
Manufacturers Association, Chicago, IL, August 1995.
46. Klopfenstein, W. E. and Walker, H. S., J. Am. Oil Chem.
Soc., 1983, 60 (8), 81.
47. Ali, Y. and Hanna, M., Bioresource Technology, 1994, 47,
131.
48. Scholl, K. W. and Sorenson, S. C., Soc. Aut omot i ve Eng,
Technical. Paper No. 930934, 1993.
49. Chandler, J. E., Horneck, F. G. and Brown, G. I., Soc.
Automotive Eng. Technical Paper No. 922186, 1992.
50. Mi dwest Biofuels Inc., Biodiesel pour poi nt and col d flow
study. Report to National Soydiesel Devel opment Board,
30 Sept ember 1993.
51. Schmidt, K. and Van Gerpen, J., Soc. Automotive Eng.
Technical Paper No. 961086, 1996.
52. Harrington, K., Biomass, 1986, 9, 1.
53. Dunn, R. O., Shockley, M. W. and Bagby, M. O., Soc.
Automotive Eng. Technical Paper No. 971682, 1997.
54. Van Gerpen, J., Hammond, E. G., Yu, L. and Monyem, A.,
Soc. Automotive Eng. Technical Paper No. 971685, 1997.
55. Shafer, A., Biodiesel r es ear ch- - Mer cedes Benz-engi ne
warranty policy. Presented at Commercialization of
Biodiesel: Establishment of Engine Warranties,
University of Idaho National Cent er for Advanced
Transportation Technology, pp. 125-141, 1994.
56. Ryan III, T., Dodge, L. G. and Callahan. T. J., J. Am. Oil
Chem, Soc., 1984, 61, 1610.
57. Bessee, G. B. and Fey, J. P., Soc. Aut omot i ve Eng.
Technical Paper No. 971690, 1997.
58. Garrett, T. K., Automotive Fuels and Fuel Systems.
Volume 2: Diesel. Society of Automotive Engineers,
Warrendale, PA, 1994.
59. Ortech International, Evaluation of methylsoyate/diesel
blend in a DDC 6V-92TA engine: optimization of NOX
emissions. Report 93-E14-36, 20 July 1993; Evaluation of
tallow/diesel blend in a DDC 6V-92TA engine. Report 93-
E14-37, 21 July 1993.
60. Fosseen manufacturing and development, optimize 20%
methylsoyate and diesel blend- 1977 DDC 6V-71N coach.
Report to National Biodiesel Board, Contract 219-2, 10
January 1995.
61. Fosseen manufacturing and development, DDC 6V-92 TA
MUI coach upgrade emi ssi on optimization on 20%/80%
soy/diesel blend. Report 260-2 and 241-1, 30 Sept ember
1994.
62. Ali, Y., Eskridge, K. M. and Hanna, M. A., Bioresource
Technology, 1995, 53, 243.
63. Batelle Institute, Interim alternative fuel transit bus
assessment results, Columbus, OH. Report to National
Renewable Energy Laboratory, August 1995.
64. ATE Management and Service Company, Inc., Cincinnati
metro soydiesel project -100000 mile field test. Final
Report, Cincinnati, OH, January 1994.
65. Daniel. T., Link Transit Biodiesel Demonstration Project.
Presented at Commercialization of Biodiesel: Establish-
ment of Engine Warranties, University of Idaho National
164 M. S. Graboski and R. L. McCormick
Center for Advanced Transportation Technology, pp. 71 -
77, 1994.
66. Yost, D., Biodiesel Research--Spokane Transit Project.
Presented at Commercialization of Biodiesel: Establish-
ment of Engine Warranties, University of Idaho National
Center for Advanced Transportation Technology, p. 69, 1994.
67. Howes, P. and Rideout, G., Evaluation of biodiesel in an
urban transit bus powered with a 1988 DDEC II6V92 TA
engine. MSED Report No. 95-26743-1, Environment
Canada, 1995.
68. Howes, P. and Rideout, G., Evaluation of biodiesel in an
urban transit bus powered with a 1981 DDC 8V-71 engine
MSED Report No. 95-26743-2, Environment Canada,
1995.
69. Ortech Corporation, Operation of Cummins NI 4 diesel on
biodiesel: Performance, emissions and durability. Final
Report for Phase I to National Biodiesel Board, Report
No. 95 El I-B004524, Mississauga, Ontario, 19 January
1995.
70. Lucas, W. Summary Test Report for the Bio-Diesel Fuel
Evaluation for the U.S. Army Tactical Wheeled Vehicles,
U.S. Army Yuma Proving Ground, Yuma, AZ, April 1995.
71. Baranescu, R., Biodiesel r esear ch- - engi ne warranty
policy. Presented at Commercialization of Biodiesel:
Establishment of Engine Warranties, University of Idaho
National Center for Advanced Transportation Technology,
pp. 102-106, 1994.
72. Koontz, K., Biodiesel r esear ch- - engi ne warranty policy-
cummins. Presented at Commercialization of Biodiesel:
Establishment of Engine Warranties, University of Idaho
National Center for Advanced Transportation Technology,
pp. 107-124, 1994.
73. Walker, L., Biodiesel research--Det roi t diesel-engine
warranty policy. Presented at Commercialization of
Biodiesel: Establishment of Engine Warranties,
University of Idaho National Center for Advanced
Transportation Technology, p. 69, 1994.
74. Goyal, M., Biodiesel research--Deere power-diesel
engine durability issues using biodiesel. Presented at
Commercialization of Biodiesel: Establishment of Engine
Warranties, University of Idaho National Center for
Advanced Transportation Technology, 1994.
75. Fosseen Manufacturing and Development, 1000 Hour
durability testing DDC 6V-92TA DDEC II engine. Final
Report to National Biodiesel Board Contract No. 214-1,
27 January 1995.
76. Ortech Corporation, Operation of Cummins NI 4 diesel on
biodiesel: Performance, emissions and durability. Final
Report for Phase 2 to National Biodiesel Board, Report
No. 95 El I-B004524, Mississauga, Ontario, 20 December
1995.
77. Blackburn, J., Pinchen, R., Nobre, J., Crichton, B. and
Cruse H., Soc. Automotive Eng. Technical Paper No.
831355, 1983.
78. Macchi, S., Overview on Biodiesel Utilization f or S + L +
H Tractor Engines. AVE AVL Conference, "Engi ne and
Envi ronment ", Graz, Austria, 1991.
79. Schloegl, H. and Weisbauer, H., Motor und Umwelt.
Sommerakademie, Graz, Austria, 1989.
80. Howell, S., Lubricity of biodiesel fuel: Update No. 3.
Report to National Biodiesel Board, MARC-IV, Kansas
City, MO, 21 July 1994.
81. Hawkins, D., Fuls, J. and Hugo, F., Soc. Automotive Eng.
Technical Paper No. 831356, 1983.
82. United States Code of Federal Regulation, Vol. 40, Part
86, Subpart N.
83. Kortum, D., New fuels and fuel additives, Section 21 l(b)
Programs. Presented at Commercialization of Biodiesel:
Environmental and Health Benefits, Mammoth Hot
Springs, Yellowstone National Park, p.30, 21- 22 May
1996.
84. Clean Air Act Amendments of 1990, Section 21 I.
85. Coordinating Research Council, Chemical methods for the
measurement of unregulated diesel emissions--carbonyls,
aldehydes, particulate characterization, sulfates, PAl-I/
NO2PAH. CRC Report No. 551, 1987.
86. Winsor, R. E., in Fuels f or Automotive and Industrial
Diesel Engines. Institute of Mechanical Engineers:
Seminar 1993-2, London, 1993.
87. McCormick, R. L., Ross, J. D. and Graboski, M.,
Environmental Science and Technology, 1997, 31, 1144.
88. Bennethum, J. and Winsor, R., Soc. Automotive Eng.
Technical Paper No. 912325, 1991.
89. Graboski, M. S., Chassis testing of Denver RTD bus
#4882 fueled on neat soydiesel. Unpublished results,
1993.
90. Liotta, Jr, F. and Montalvo, D., Soc. Automotive Eng.
Technical Paper No. 932734, 1993.
91. Sharp, C. A., Emissions and lubricity evaluation of
rapeseed derived biodiesel fuels. Final Report from
SWRI to Montana Department of Environmental Quality,
November 1996.
92. Daniels, T. L., McCormick, R. L. and Graboski, M. S.
Unpublished results, 1996.
93. Ullman, T. L., Spreen, K. E. and Mason, R. L., Soc.
Automotive Eng. Technical Paper No. 941020, 1994.
94. Spreen, K. E., Ullman, T. L. and Mason, R. L., Soc.
Automotive Eng. Technical Paper No. 950250, 1995.
95. Spreen, K. E., Ullman, T. L. and Mason, R. L., Effects of
fuel oxygenates, cetane number, and aromatic content on
emissions from 1994 and 1998 prototype heavy duty diesel
engines. Southwest Research Institute, Final Report, CRC
Contract VE-10, May 1995.
96. Peterson, C. L. and Reece, D. L., Soc. Automotive Eng.
Technical Paper No. 961114, 1996.
97. McDonald, J., Purcell, D. L. and McClure, B. T.,
Methylester oxygenated fuels for diesel mining applica-
tions. In Proceedings of the 7th US Mine Ventilation
Symposium, p. ! 16, 1994.
98. Schumacher, L. G., Borgelt, S. C. and Hires, W. G.,
Fueling diesel engines with blends of methylester soybean
oil and diesel fuel. Agricultural Engineering Department,
University of Missouri, Columbia, MO, 1994.
99. Krahl, J., Munack, A., Bahadir, M., Schumacher, L. and
Elser, N., Soc. Automotive Eng. Technical Paper No.
962096, 1996.
1130. Signer, M., Heinze, P., Mercogliano, R. and Stein, H. J.,
Soc. Automotive Eng. Technical Paper No. 961074, 1996.
101. Parker, T. E., Private communication, 1996.
102. Sato, J., Konishi, K., Okada, H. and Nioka, T., 21st
Symposium on Combustion, p. 695, 1986.
103. Miller, J. A. and Bowman, C. T., Prog. Energy Combust.
Sci., 1989, 15, 287.
104. Hiroyasu, H., in Diagnostics and Modeling of Combustion
in Reciprocating Engines, COMODIA, Proceedings of
Symposium, Tokyo, 4 - 6 September 1985, pp. 53-75.
105. United States Code of Federal Regulation, Vol. 40, Part
86, Subpart I.
106. Fosseen manufacturing and development, five seasons
transportation Linn County lifts methyl soyate demonstra-
tion. Report to Iowa Soybean Promotion Board, Des
Moines, IA, 19 December 1995.
107. Shafer, A., Environmental and health concerns at
Mercedes Benz. Presented at Commercialization of
Biodiesel: Environmental and Health Benefits, Mammoth
Hot Springs, Yellowstone National Park University of
Idaho and DOE, 21- 22 May 1996.
108. Kado, N., Toxic compound studies with ethyl and methyl
esters. Presented at Commercialization of Biodiesel:
Environmental and Health Benefits, Mammoth Hot
Springs, Yellowstone National Park University of Idaho
and DOE, 21- 22 May 1996.