Note: Descriptions are shown in the official language in which they were submitted.
Çi2~
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~ 1 --
Brle~ Summar~_ ~ Inven~:ion
~echnical Field
This invention pertains to diesel ~uel
compo~itions for use in dies~l engine~s and to a
method Ior preparing said compos~tions.
Back round or the Invention
The use ot diesel ~uel compositions so
power lignt-du~y ana heavy-duty engines and tnelr
importance throughout ~he wor~d is well known.
However, it is also well known that there is a
definite need to decrease the exhaust emissions from
such aiesel-~owered engines, es~eci~lly in the area
o~ visible smoke particulates an~ oxides or nitrogen
(NOX~. In addition to satisfying obvious
environment~1 concerns and related Environmental
Protection ~gency re~ul~tions~ it is important to
achieve a reduction in smoke/yar~iculate formation
because o~ its relationship to lubricating oil
de~erioration and atten~an~ accelerated englne wear.
Moreover, diesel ruels are sensitive to
wa~er con~amina~ion and u~on such contamin~tlon
exhibit no phase stability for wa~er even at
temperatures o~ well above 0C. Operational
problems ~ttendant with such water contamination are
well known ln the ar~. Tnus ther~ is also a need to
improve the aqueous phase stability or diesel fuels
and ~nereby eliminate or at least minimize ~he
obvious operating yrobl~ms ~hat may be asso ia~ea
with ~he utilization or water contaminated diesel
ruels.
Consequently, the discovery o~ a diesel
fuel composition that would no~ only exhibit
. ~'
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decreased particulate emissions, and would-also
exhibi~ improYed phase stability not only upon
~torage, but towards water a~ well, would obviously
be o~ no small importance to the state o~ the art~
The search for improved diesel fuel
compositions is a constant one as seen, e.g. by the
~ollowing prior art.
The art~cle UDiesel Fuel-Aqueous Ethanol
Microemulsions" by AoW~ 5chwa~ et al appearing in J.
Dispersion Science and Technolog~, 3Sl), yp. 45-60
(1982) which relates to a study of two-phase
mixtures of diesel fuel and aqueous e hanol as well
as a detergen~less system o~ a diesel fuel, aqueous
ethanol an~ butanol.
U.~. Patent Appllcation ~erial No. 256,~06
filed April 21, 1981 entitled "Diesel Fuel-Aqueous
Alcohol Microemulsions" by A.W. Schwab available
from the National ~echnical Information Service,
PB81-248619, which is directed to hybridizing diesel
fuel with high levels of water and a Cl ~o C3
alcohol which are held in a 8 able microemulsion at
low temperatures by means ot a sur~actant.
The article "Microemulsions as Diesel
Fuels" by G. Gillberg et al in Am. Chem. Soc.
~Y~e~ Of the 172 Meeting o~ the American
Chemical Society, San Francisco, Aug. 31 - Sept. 1,
1976 ~pp 221 eo 231) which discloses that
emulsifiers can be used to reduce exhaust emissions
in di*sel fuels.
U.S. Patents 4,162,143; 4,182,614 and
4,244,?al all of which disclose methods ~or reducing
exhaust e~issions of fuel oils using aqueous
emulsified fuel~.
D~13696
Society of Automotive Engineers (SAE)
rechnical Paper Series #790g25 (1979), s~hich
disclo~es the use of water and alcoholic diese} fuel
emulsic:ns to reduce particulate exhau~;'c emissions
S SAE Technical Paper Series ~79095fi (1979)
which discloses a review of alcohol-diesel fuels~.
SAE Technical Paper Series ~810250 (1981)
which discloses a study of the effec~ of water in
diesel fuels.
SAE Technical Paper Series ~810254 ~1981)
which discloses a ~tudy on the use of alcohol in
diesel fuel emulsions.
SAE Technical Paper Series ~700736 (1970)
which discloses a study on the effect~ of emulsified
fuels and water induction on diesel combustion.
It has now been discovered, for the first
time, ~hat phase-stable aqueous d~esel/alcohol fuel
compositions can be prepared having a cloud point of
0C or below without the aid of surfactant
emulsification and that certain of s~ch
surfactant-free, aqueous diesel/alcohol fuel
compositio~s have also exhibited improved
anti pollutant characteristics.
Disrlosure of this Inventlon
2~ Thus it is an object of this invention to
provide novel surfactant-free, phase~stable, aqueous
dieseIfalcohol fuel compositions having improved
anti-pollutant characteristics. Another object of
this invention is So provide a novel method
3~ ~proce~s) for preparing ~aid diesel/alcohol fuel
compositions. Oth~r objects and advantages of this
invention will b~come readily apparen~ from ~he
fQllowing description and appended claim
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More specifically, this invelltion i~
direc~ed to a surfactant-free, phase-~able, agueous
diesel/alcohol fuel composition having a cloud point
o~ 0C vr below, and consisting essen~ially o~ about
0.1 to abou~ 1.0 weight percent wa~er~ about 1 to
a~out 19 weight percent of ~ Cl to C3 aliphatic
al~ohol or ~ixtures thereof, and about 1 to about lB
weight percent of a C4 to C8 aliphatic alcohol
or mixtures thereof, the remainder of said
composi~ion consistiny essentially o~ diesel fuel.
Alternatively, this invention may be
described as a ~ethod ~or ~reparing a
surfactant-~reer phase-stable, aqueous
diesel/alcohol Xuel com~osition suitable ~or use in
diesel engines, which com~rises mixing a diesel fuel
with water, a Cl to C3 aliphatic alcohol or
mixtures thereor and a C~ to C8 aliphatic
alcohol or mixtures th~reof, wherein said
composition has a cloud point o~ 0C or below, and
2Q consists es~en~ially of ~bout 0~1 to about 1~0
weight percent water~ about 1 to about 19 wçight
percent of said Cl to C3 aliphatic alcohol or
mixtures thereor, and about 1 to about 18 weight
percent of said C4 to C8~aliphatic 21cohol or
mixtures thereo~, the rem~inder o~ said composition
consisting essentially of said die~el fuel.
Detailed Description
The primary component of the diesel/alcohol
fuel composition of thi~ inventions is of cours~ a
bas~ diesel Euel whi~h is present in a major
amountO The base diesel fuel component employable
in the present invention can be any conventionally
known diesel fuel oil~ including hydrocarbon fu~l
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oil mixtures having a diesel boiling range o~ about
175C to abou~ 400C. Such diesel fuel oils and~or
method~ for their ~reparation are well known in the
art.
The Cl to C3 ali~hatic alcohol
employable in the present invention includes
methanol, e~banol, n~propanol and isopropanol, the
most pre~er~red lower alcohol being isopropanol. O~
course mixtures or said Cl to C3 aliphatic
alcohols can also be employed if desired.
The C4 to C8 aliphatic alcohol
employable in the present invention includes
butanols, pentanols, hexanols, heptanols and
octanols, as well as mixtures o~ such alcohols, if
desired~ The more preferred higher alcohols are the
primary alcohols of said C4 to C8 alcohols,
especially n-bu~anol; isobutanol, n-~entanol,
2-methyl-1-butanol, 3-methyl-1-butanol,
2-ethylhexanol, and mixtures thereof.
It is ~o be understood that the
surfactant-free, phase-stable, aqueous
diesel/alcohol fuel compositions o~ ~his invention
are single-phase, clear, transpar*nt, homogeneous
mixtures which are chara~erized by their
thermodynamic stability over a wide range of
temperatures as seen by the fact-tha~ they possess a
cloud point o a~ lea~t 0C or below. As employed
herein the term ~cloud point~ represents tha~
temperature at which the fuel composition changes
from a clear and transparent ~luid to one which is
cloudy. ~oreover as not~d above, the diesel/alcohol
fuel compositions of this invention are
~surfactant~re~N, i.eO, no surfactant is necessary
for the aqueous diesel/alcohol ~uel composition of
D-136g6
28
this invention to achieve a cloud poin~ ot at least
0C or below. Accordinyly, the aqueous
di~sel/alcohol ~uel composltions o~ this invention
are not to be confused wit~ emulsions, or even
microemulsions, o~ diesel ~uels which depend upon
the presence of a sur~ac~ant to obtain their aqueous
clou~ point stabili~y.
The components o~ the dies~l~alcohol ruel
compositions of this invention may be employed
sinyularly or as mixtures and mixea ln any order
using any mixing or blendiny apparatus and technique
desired. Indeed the ruel compositions o~ this
invention are characterized by their spontaneous
formation u~on the proper choice and amounts ot
components employed. Moreover, while the selection
of the various ~uel oomposition component Amounts
required to achieve the results desired will be
dependent upon one's e~perlence in the utilization
of the subject lnvention, only a minimum measure ot
e~eri~entation should be necessary in oraer ~a
asoertain those com~onent amounts which will be
su~rioien~ to produce t~e ~esired results ~or any
given situation.
For inst~nce, in general the amount of C~
25 to C3 aliphatic alcohol or mintures thereo~
present in ~he ~uel compositions or this invention
may generically range Lrom about l to about l9
weight percent based o~ the ~o~al weigh~ o~ the f uel
composition. Likewise the generic range oI t~e
30 remaining components o~ the $uel com~ositions o~
this invention, based on the total weight of the
partlcular ~uel oomposi~ion desire~, include fro~
about 0.1 to about }.0 weiyht percen~ oi water, ~he
more pre~erred upper limit o~ water being about 0.7
D-1369G
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weight percent, a~d ~rom about 1 to about 18 weight
per~ent o~ a C~ to C~ aliphatic alcohol or
mixtures thereof, tne xemainder of the fue}
composition consisting essentially of ~he base
diesel fuel employed.
~ ore specifically, pre~erred phase-stable
fuel compositions having a cloud point of at least
0C or below and containing up t.o about 0.7 weight
percent water may be obtained when the composition
contains ~rom about 1 to 19 weight percent o~
isopropanol and about 1 to 18 weight percent o~ a
butanol or a pen~anol; and when the compo~ition
contains ~rom about 10 to about 18 weight percent of
isopropanol and about 2 to about 7 weight percen~ of
2-ethylhexanolO
In fuel compositions that contain a 50:50
weight percent mixture of methanol and ethanol as
the lower aliphatic alcohol, preferred phase-stabls
compositions having a cloud point o~ at least 0C or
below and containing up to about-0.4 weight percent
water may be obtained when the composition contains
~rom about 1 to about 5 weight percen~ of said
methanol/ethanol ~ixture and about 10 to about 18
weight percent o~ a buta~ol; when the composition
contains about 1 to abou~ 7 weight percent of said
methanol/ethanol mixture and about 7 to about 18
weight percen~ o~ a pentanol; and when ehe
compo~ition contains from about 1 to about 7 weigh~
percent o said methanol/ethanol mixture and about
10 to about 18 weight percent of 2-ethylhexanol.
In fuel compositions that contai~ methanol
a the lower ~lipha~ic alcohol, pre~erred
phase-stable fuel composition~ having a cloud point
of at least 0C or below and containing up to abou~
D-13696
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0.~5 weight percent water may be obtained wherein
the composition contains about 1 to about 5 weight
pe cent methanol and about 10 to about 18 weight
percent of a butanol; when the composition contains
about 1 to about 8 weight percent of methanol and
about 7 to abou 18 weight percent o~ a pentanol;
and when the ~omposition contains about 1 ~o a~out 8
weight percent of methanol and about 12 ~o 18 weight
percent of 2-ethylhexanol.
1~ In ~uel compositions that contain ethanol
as the lower aliphatic alcohol, preferred
phase-stable ~uel compositions having a cloud point
o~` at least 0C or below and containing up to about
0.5 weight per~ent water may be obtained wherein the
composition contains about 1 to about 7 weight
percent ethanol and about 1~ to about 18 weight
percent of a butanol; when the composition con~ains
about 1 to about 9 weigh~ percent o~ ethanol and
abou~ 8 to abo~t 18 weight percent of a pentanol;
and when the composition contains about 5 to about
10 weight percent of ethanol and about 7 to about 12
weight percent of 2-ethylhexanolO
The subject inventi~n is indeed unique and
beneficial in that it ~r7vides surfactant-free,
25 highly phase-stable, aqueous diesel/alcohol fuel
composi~ions sui~able ~or routine utilization in
diesel engines o conveneional design. Moreover, it
is a common occurrence ~or certain unadultera~ed
diesel fuels ~o appear slightly hazy on pouring, and
30 upon standing for a few days to form a darker
sediment-lik~ layer on ~he bottom of the fuel wbich
could cause operational probIems such as plugging ot
fuel filters and injector nozzles. However, an
added benefi~ of the diesel~alcohol fuel
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~22'~;2~
g ~
compositions of this invention is ~neir clear and
transpara~t characteristics and the ~ac~ that they
have not been round to form such sedi.ment eYen upon
long periods or storage.
Fur~her, in addition to the excellent
thermodynamis~ally stable charactelistis:s (cloud
point o~ at least ODC or below) o~ the
diesel/alcalhol ruel compositions o~ this invention,
isopropanol con~aininy diesel/alcohol co~osi~io~s
o this invention have been found to subs~antially
reduce ~he amount of visi~le smoke and particulates
as well as oxid~s of nitrogen (NOx) in the exhaust
emissions of the ~uel compositions as com~ared to
t~at o~ the unadulterated base diesel ruel
em~loyed. Such excellent anti-pollutant
characteristics should also translate into better
engi~e wear characteristics as well. Moreover,
wnile the diesel/alcohol fuel compositions oi this
invention do possess a lower cetane number (ignition
quality~ than the base diesel ruel pPr se, such a
drawback should be able tO be overcome by the
additional use or small amounts o~ any suitable
conventional cetane improver such as an alkyl
ni~rate, and the like, i~ desired. Thus it is tO be
understood that, i~ desired, ~he fuel compositlons
or this invention may contain minor amounts i.e.
less than l weiyh~ perc~nt o~ any conventional
cetane improver, as well as such amounts o~ any
sui~able conventional corrosion inhibi~Or~ me~al
deactivator or antioxidant.
The ~ollowing examples are illustrative o~
the present invention and are not to be regarded as
limitative~ It is to be unders~ood tnat all ol the
parts, percentages and proportions rererred to
D-13696
~2Z'~ 8
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herein a~d in the appended claims are by weight
unless otherwise noted.
EXAMP~E 1
A series of fuel compositi~n.s were prepared
wherein various amoun~s o~ a diesel ~uel, ~ Gul~)
which had an unadulterated cloud point o~ ~15C,
were mixed With various amounts of isopropanol,
water and a 50:50 weigh~ percent mixture o~
n-butanol and isobutanol an~ the cloud point o~ each
composition determined as outlinea below
~ixture o~
Diesel Isopro- n-butanol &
Fuel panol Wa~er isobutanol Cloud
Com~sition ~ ~wt ~) (wt ~) ~wt ~) Point C
b) 81.84 8.50 0.579.09 -15
c) 85.66 5.43 0.~28.20 6
d) 84.79 5.38 0~719.13 -5
e) 83~94 5.32 0.7010.04 -12
f) ~3.60 5.30 0~7010.~0 -15
O~ the a~ove compositions, composition "~ n
was mos~ pre~erred bec~use o~ its low cloud point
: and hiyh water conten~. Compositions corresponding
to "dn, en, and ~r~ were subse~uently ~re~ared
using a diesel ~uel [XH-CAT (Caterpillar lGlH
Reference ~uel ~rom Howell, ~y~rocarbons Inc.~l that
had an unadulterated cloud point oS -3C and the
aqueous cloud point~ o~ the three compositions so
prepared were ~ound to be 5C, -2C and -5C,
respectively. In addition a ruel composition
containing abou~ 84.78 grams ~90.~ wt. 4~ oi said #2
Gulf di~sel fuel which had an unadulterated cloud
~ poin~ o~ ~15C, about 8.45 grams (9.0 wt. ~)
i~opro~anol and 0.56 grams (0.6 wt. %) water was
cloudy at room temperature indicating tAat the
contained wat~ was not in stable form.
D-13696
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11 --
Example 2
A series of fuel compositions were prepared
~y mixing various amounts of a diesel fuelr ~#2
Gulf) which had an unadulterated cloud poant of
-15C, with various a~ounts of isopropanol, wat r,
and a mixture of primary amyl alcohols [analysis:
about 98.7 wt. ~ total primary amyl alcohol; about
66.14 wt. % n-pentanol and about 32~ 56 wt. ~
2-me~hyl-1-butanol arld 3-methyl-1-butanolJ. The
c:ompositions so prepared along with their cloud
points were as follows.
~. Mixture of
Die~el Isopro- Primary ~myl
15Fuel panol ~ater Alcohols Cloud
Composition (wt.9~) (wt.%) ~t ~) ~wt.%~ Point C
~) 86.918.66 0.58 3.85 4
b) 84.928.B2 0.59 5.66 ~9
c) 82.598.59 01~6 8.26 -13
20d) 85. 338 . 86 0 . 60 5. 21 -6
e) 78.7510.75 Q.66 9O84 -12
f) 84.138~74 ~.59 6.5~
. 9) 85.738.90 0.60 4.76 -3
Above compositions "b", "f" and ''9~ were
subsequently prepared using another diesel fuel
[I~-CAT (Caterpillar lGlH Reference Fuel ~rom ~owell
Hydrocarbons Inc.)] having an unadultera~ed cloud
point of -3C. The cloud point~ of these three
compositions so prepared were -3C, -7C and -1C,
respectively.
A series of ~uel compositions were prepared
by mixing various amounts of a diesel fuel, (#2
Gulf) which had an unadulterated cloud point of
-15C, with various amounts of isopropanol, water
and i~o-butanol. The compositions so prepared along
with their cloud points were ~5 followsc
D-13696
~2~6~
~ 12 o
Diesel IsoprQ-
Fuel panol Water Isobutanol Cloud
Compos tion (wt.%L (wt.~) ~wt.~) (w~ L~ Point C
a) 86.91 8.66 0,583~85 5
b~ 85.73 8.gl 0.504~,76
c3 84.92 8.83 0.5B5.66 -4
d) 84.13 8.74 0.596.54 -7
e) 82.59 8.~9 0~568026 -}4
f~ 81.84 8.5~ ~.579O0~ -15
9) ~1~74 7.36 0.681~.22 -12
Three compositions corresponding to
: composition n~ above were prepared wherein the
isobutanol was ~eplaced with n-bu~anol, n-pentanol
and 2-ethylhexanol, respectively, and their
respective cloud points were ~ound to be -13C,
-14C and -7C.
Example 4
A series o~ ~uel compositions were prepared
consisting o~ about 81~7.8 wt. ~ o~ a diesel ~uel,
(~2 Gulf) having an unadultered cloud point of
-15C, and about S.56 w~, ~ of anhydrous (200 proor)
: ethanol, about 0.57 wt. ~ water and about 9.09 wt.
; of a higher alcohol. The cloud points or` said
composition~ were as ~ollows.
25 ~ Cloud Point (C~
n-butanol ~ 14
iso-butanol 17
n-pentanol -2
Mixture of pri~ary amy~ alcohols*
30 2-ethylhexanol -2
*(Analysis: about 98.7 wt. ~ tota} amyl alcohol;
abou~ 66-14 wt. ~ n-peAtanol and about 32.56 wt.
~methyl~ butanol and 3-me~hyl-1-butanol).
Two fuel oompo~itions were prepared by
mixing a diesel fuelr ~2 Gulf) which had an
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~2Z~6~
- 13 -
unadulterated cloud point o~ C, with me~hanol,water and a mix~ure of primary amyl alcohols
(analysis: about 98.7 wt. ~ total amyl alcohvls;
about 66.14 wt. ~ n~pPntanol and about 32~56 wt.
2-methyl-1-butanol and 3-methyl-1-bu~a~ol). The
compositions so prepared alo~g with their cloud
points were as. ~ollows:
~ixture o~
Diesel Meth- Primary amyl
Fuel ano~ Water Alcohols Cloud
Composition (wt.~) ~wt~) (wt.%) (wt.~) Point C
a) 84.04 4.17 0.2~ 11.50 ~9
b~ 75.59 7.92 0.53 15.97
Another fuel composition consisting of
15 74.3B wt. ~ diesel ~uel, (#2 Gul~) which had an
unadulterated cloud point of -15C, 7.75 wt. 4
~eehanol, 0.52 wt. ~ water and 17.36 wt. ~
iso~utanol, had a cloud point of only 20~C.
Example 6
20 A series o~ fuel compositions were prepared
by mixing various amounts o~ a diesel ~uel, (#2
Phillips P troleum) which had an unadulterated ~loud
poin~ o~ C; with various amounts o~ isopropanol,
water and iso-butanol. The compositions 50 prepared
along with their cloud points were as ~ollows.
Diesel Isopro-
Fuel panol Water Isobutanol Cloud
(wt.%l (w~0~) (wt~) (wt.~?_ Point C
a~ 81.43 ~~~7 0.713.90 -18
30 b) 84~413.97 0.710.92 -14
c) 80.~415.89 0.72098 -3
~) 8304~7.94 ~.77.94 -8
e) 95.193.27 0.121.42 -17
f) 34.803.24 0.181.78 ~3
~5 9) g~243022 0.182.36 -8
h) 93.673c21 0.182.94 ~16
i) g3.333.77 ~.~02.70 -16
jJ 95.223.72 0.1~0.94 -9
k) 9S.192.79 0.121~90 -12
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2~62~3
- 14 -
1)94.91 20 78 0~122.19 -17
95.17 1.~6 ~.12~.85 -16
n~95.15 0.93 . 0.123.80 -16
ol94.20 3.72 0. 18lo ~0 ~5
~
A series of fuel compositions were prepared
by ~ixiny various amounts o~ a diesel ~uel, (~2
Phillips Petroleum) which had an unadulterated clou~
point of -18C, wi~h various amoun~s o~ isopropanol,
water, and a mixture of primary amyl alcohols
(analysis: about 98.7 wt. æ total primary amyl
alcohol; about 6~.14 wt. ~ n-pentanol and about
32.56 wt. ~ 2-methyl-1-butanol and
3-methyl-1-butanol). The compositions so prepared
along with their cloud points were as follows:
~ixture of
Diesel Isopro-- P~imary Amyl
Fuel panol Water Alcohols Cloud
Composition (wt.%~ (wt.~) Iwt~ 4) Point C
20 a)82.00 5.30 0.7012.00 -17
b)82.C014.30 0~703.00 -6
85.50 6.8~ 0.7~7.~0 -1~
d~86.0011.30 0.702.00 ~18
~ .00 8.30 0.705O00 `+5
25 f)94~55 4~30 OolS1~01) ~10
g)94~07 4~29 O~lS1~49 ~3
)93~ 624~ 2~i 0~ 15lo 97 -13
i)95~19 2~7~ 0~121~90 -17
A ~eries o~ ~ue} compositions were prepared
: by mixing various amounts sf a diesel ruel, (~2
Phillips Petroleum) which had an unadulterated cloud
point of -18C, with various amounts of i~opropanol,
water and 2-ethylAexanol. The compositions so
prepared along with their cloud points were as
follows.
D-13696
- 15 -
Diesel Isopro- 2-Ethyl-
Fuel panol Wa~er hexanol Cloud
omposition ~ wt.~ L Polnt C
a) 82.00 11.30C.70 6.00 -17
ij) 8100(~ 17.3!~0~70 loC~0 ~;2
c ) 83~00 13~3~70 3~00 -6
~1) 8~ o ~010 ~ 3~ 0~ 70 S~ 01~
Another fuel composi~ion consisting of
B6.25 wt. ~ diesel fuel, (~2 Gulf) having an
unadulterated cloud point of -15C~ 8.60 wt.
isopropanol, 0.57 w~O ~ water and 4.58 wt. ~
2-ethylhexanol had a cloud point o only 15~C.
~,
A series of ~uel compositions were ~repared
wherein various amounts of diesel fuel, (#2 Phillips
Petroleum) which had an unadulterated cloud point of
-18C, wexe mixed with various amounts o~ a 50:50
weigh~ percent mix~ure o~ methanol and ethanol,
water and isobutanol and the cloud point o~ each
composition de~ermined as outlined below
Diesel Iso- Cloud
: Compo- Puel ~e~hanol Ethanol Water butanol Point
sition ~ wt.~) (wt ~L (wt ~) (wit ~)- C
b) 87.64 0O80 0~80 0~4010~36 -4
c) ~7.64 1.50 1.50 0.408.96 +15
~ .
Example 10
.. .
A ~eries of fueL com~ositions were prepared
by mixing various amounts of a diesel ~uel, (~2
Phillips Petroleum) w~ich had an unadulterated cloud
point of -18C, with various amounts of a 50:50 wt.
~ mixtu~e of methanol and ethanol, water and a
mixture of primary amyl alcohol~ (analysis: about
98.7 wt. ~ total amyl alcohol; about 66.1~ wt. ~
n-pentanol and about 32~56 wt~ ~ 2-methyl-1-butanol
~-136~6
~4621~
- 16 -
and 3-methyl-1-butanol). The cDmposi~ions so
prepared along with thelr cloud points were as
gollows:
Mix~ure o~
Primary
Di~sel amyl Cloud
Compo- Fuel Methanol Ethanol Water Alcohols Point
sition (w~wt ~) (wt.~) (wt.4) (wt.~)
a) 80.68 2 49 2.49 0.4013.94 -18
b~ 87.14 1~25 1.25 0.409.9S ~18
c) 85.66 1.99 1.99 0.409.96 -12
d~ 82.16 3.74 3.74 0.409.96 ~8
Exam~le 11
A series o~ ~uel compositions were pre~ared
wherein various amounts of a diesel fuel, (#2
Phillips Petroleum) which had an unadulterated cloud
point of -18C, were mixed with various amounts of a
: 50:50 weight p~rcent mixture o~ methanol and
ethanol, water and 2-ethylhexanol and the cloud
point of each composition determined as outlined
below
Diesel 2-Ethyl Cloud
Compo- Fuel Methanol Ethanol Water ~exanol Point
sition ~ (wt.~ ~w~ wt.~L ~wt.~)C
a) 80.27 2.7g2.79 0.4013075 -17
b3 82.66 3.49~.49 0.40g.96 ~8
c~ ~1.68 ~.991.99 0.4013.94 ~7
d) 81.67 2.492.49 0.4012.95 -~
e) 80.B7 30393.39 0.4011.95 -16
Example 12
A series o~ ~uel compositions were prepared
by mixing various amounts oE a di2s~1 fuel, (~2
Phillips Petroleum) which had an unadulterated cloud
point of ~18C, with various amounts o methanol,
water and isobutanol. The compositions ~o ~repared
along with their cloud points were as follows.
D~13696
~2;~gL621~
- 17
Diesel
Fuel ~ethanol Wa~er ~sobutanol Cloud
omposition ~ (wt.~ ~wt.4) (s~t.~) Point ~C
a) 86.78 2000 0.2510.~7 -16
b) 81.79 3.93 0.25:L3.97 -10
c~ 84.79 2.99 ~.25~L1~97 ~8
d~ B5.78 ~99 0.2~ 8.98 +27
Example 13
series of uel composi~ions were prepar~d
by mixing various amounts o a diesel ~u~ 2
Phillips Petroleum) which had an unadulterated cloud
point of -18C, with various amoun~s of methanol,
water and 2-ethy~hexanol. The compositions so
~repare~ along with their cloud points were as
follows.
Diesel 2~Ethyl-
Fuel ~ethanol Water hexanol Cloud
~omposition (wt ~) Iw~ wt %? (wt ~) Point C
20 b) 8L.79 3.99 0.2513.97 -17
c) 83~79 3.99 0.2511.97 -8
: d) 84.79 3.99 0.2510.97 +1
e) 81080 6.98 0.2510.97 +6
xam~le 14
A series of fuel compositions were prepared
by mixing various amounts of a diesel ~uel, (~2
Phillips Petroleum) whic~ had an unadulterated cloud
point of -18C, with various amounts of me~hanol,
wa~er and a mixture of primary amyl alcohols
(analysis: about 98. 7 ~t. ~ total prim~ry amyl
alcohol; about 66.14 wt.~ n-pentanol and about 32.56
wt.% 2-methyl-1-butanol and 3-methyl-1-butanol~.
The compositions ~o prepared along with their cloud
p~ints were a~ follows.
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~ixture
Diesel of Primary Cloud
Fuel Methanol Water ~myl Alco- Poin~
Composition ~wt~ L_ (wt.~) ho~ C
a) 8g.771, ao o. 2~ 8.9~ -lS
b) 810196.68 0O25 11.83 ~18
c) 86.003.~5 0.25 10.0~ -12
~3 90.~02,25 0.25 7.50 -10
e~ 89.~899 0.25 6.98 ~5
~) 88.782.99 0.25 7.98 -10
~) 81.007.7~ 0.25 11.00 -~7
h~ 81.835.99 0.20 11.9~ -12
i) 81.~65.98 0.30 11.96 -~
j) R5.833.99 0.20 9.98 ol3
k) 8S.743.99 0.30 9.97 ~4
Example.15
A series of ~uel compositions were prepared
by mixing various amounts or a diesel ~uel, (~2
Phillips Petroleum) which had an unadulterated cloud
point of ~18C, with various amounts of ethanol,
water and i~obutanol. Tha compositions so prepared
along with their c~oud points were as follows.
Diesel Isobu-
Fuel Et~anol Water tanol Cloud
~ L~ (wt.%)_ Point C
a) 80.591.0~ 0.5017.91 -18
b) 87.551.~0 0.5010.95 -}0
c) 85.562.99 ~.5010.9~ ~
d) 83.583.g8 0.5011.94 -11
e) 85.573.98 0.509.9S +2
~) 79-605 D 9 7 0-5013.93 13
A series of fuel compositions were p~epared
by ~ixing various amounts of a diesel fuel, ~2
Phillips Petroleum) which had an unadulte~ated cloud
point o~ -18~C, with various amounts of ethanol,
- water and a mixture of primary amyl alcohols
(analysis: abou~ 98.7 wt.~ total primary amyl
alcohol; about 66.14 wt.~ n-pentanol a~d about 32.56
D~13696
.
~2~62~
19 --
~t.~ 2-~ethyl-l-butanol and 3-methyl-l-hutanol).
The compositions so prepared along with their cloud
points were as follows,
~ixture
Diesel Q~ Primary Cloud
Fuel Ethanol ~ater Amyl Alco- Poin~
Composi~ion (w ~) (wt.%)_ (wt.~) ~ols ~wt.~) C
a~ 80.59 l.00 0.50 17~91 -17
b) 86~56 1.99 O.S0 10.~5 -17
c) 79.59 fl.96 G.50 10.95 -16
d) 81.58 8.~6 0.50 8096 -S
~) 85.~6 4.g8 0.50 8.96 -12
~) 85.57 5.97 0.50 7.96 ~2
A serie~ o~ fuel composltions were prepared
by mixing various amounts of a die~el ~uelr (~2
Phillips Petroleum) which had an unadulterated cloud
poi~t o -18C, with various amounts o~ etha~ol,
water and 2-ethylhexanol. The compositions so
prepared along with their cloud points were as
: follo~s.
Diesel ~-Ethyl-
Fuel ~thanol Water hexanol Cloud
Composition ~wt.~ L~ 5wt.%) ~wt.~) Point C
a) 82.58 Ç097 0.5~ 9095 -17
b~ 83.57 6.97 0.50 8.g6 -4
~) 81.59 g.9~. 0.50 7.96 -2
d) 83.57 8.96 0.50 6.97 +8
Example 18
A fuel composition designated ~D4~ which
consisted o~ abou~ 830~4 wt.~ of a diesel fuel
[IH-CAT ~Caterpillar lGl~ Reference Fuel from Howell
~ydrocarbon Inc.)~ whicb had an unadulterated cloud
point of -3C, about 5.30 wt.~ o~ isopropa~ol, about
35 0070 wt.~ ~a~er and about 10.40 wt.~ of SQ:50 w~.
mixture o~ n~bu~anol and isobutanol, said
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. ~ 20 -
c~mposition ~D4a having a cloud point of -5C~ 9
along with another composition designat~d ~D5u
which c~nsisted o~ about 85.73 wt.~ oE the same
diesel fuel em~loyed in composition D4, about 8. 90
wt.~ of isopropanol, about O.SO wt.~ water ana aDoUt
4 . 76 w~. % of a mixture of primary amyl alcohols
~analysis: about 98.7 wt.~ total amyl alcohol;
abQut 66.14 wt.~ n~pentanol and about~32.56 wt.#
2-methyl-1-butanol and 3-methyl-1-butanol), said
com~osition UD5" having a cloud point of -1C.,
were prepared ~n~ evaluated ver~us the same
unadulterat~d base diesel ~ue~ employed in preparing
each oomposition D4 and DS in terms of exhaust
emission~ and ~uel economy.
The ~er~ormance tests were conducted on a 6
cylinder diesel engine geared to a dynamometer
capable of loading the engine to SOOHP wet gap. The
performance of ~uel composition D4 ~as compared
with the performance o~ the base dies~l fuel at two
en~ine modes . (a) 1200 RP~/557 lbs. load (which
corresponds to an engine operation in a very rich
fuel (excess fuel) Mode) and (b) 1400 RP~/600 lbs.
load (which corresponds to a normal operation or the
engine under considerable load (e.g. climbing a
hlll). The per~orma~ce of ~uel composition D5 was
also compared with the per~ormance of the base
diesel fuel at engine modes (a) 1200 RPM/560 lbs.
load and (b) 1400 RPM~605 lbs. load. In addition
the per~ormance o~ composi~ion D5 was assessed at
an engine mo~e (c) 2090 RPM/475 lbs. load as
sompared to the base diesel ~uel at an engine mode
of 2Q84 RPM/508 lbs. load (which corresponds to an
~ngine operation a~ high speed and high load).
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The tes results are reported below
tU~l economy value~ being an average o~ ~ive
measurements; all smoke measurements being an
average o five mea~urements and all particulate
measurements being an aver3ge o~ ~hree measuremen~s.
Fuel Concumption (lbs./hour~
Operating ~ode Base Diesel Fuel Comp. Fuel Comp.
Fuel D-4 D-5
1200/557 83.20 87.0~ -
10 1200/5S0 ~3.10 - ~4.gl
1400/600 101.98105.14
1400/605 10~.36 - 101.99
2084/508 ~32.51 - -
~090/~75 _ - 127.5
15 Particulates (Grams)
Operating Mode Base Diesel ~uel Comp. Fuel Comp.
Fu~l D-4 _ D-5
1200/557 .0163 .0174
1200/560 .0175 - .~167
20 1400/5~0 .0104 .00~1 -
14~0/605 .0140 .0143
2084/508 .~024 - -
~090/~75 ~ ~ .0~14
Smoke (~ O~acity)
Opera~ing Mode ~ase Diesel Fuel Comp. Fuel Comp.
Fuel _ D-4 D-5
1~00/557 1~.74 11.9
1200/560 12~7~ 8
1400~600 ~.30 5.0~ -
30 1400/505 9.38 - 7.52
2084/508 2.18
2090/475 - - 1.64
T~e above da~a shows that operation of ~he
engine wi~h ~uel composi~ions D4 and D5 of this
Dol3696
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-- 2
invention resulted in a s~grlif icant reduction in
both smoke opacity and particulate content of the
exhaust over that shown when employing the ba~e
diesel fuel if the engine is not strained l:o a
5 maximum. As aeen the average decrea~;e in smoke
opacity for DA a~ modes 12û0/55 7 and 1400/600 was
6 . 3% and 45% and for D5 at ~des 1200/560 and
1400/605 was 7.1~6 and 20.2%7 Likewise the average
decrease in particulate content for D4 at mode
1400/600 was 41.3~ ~mode 1200/557 showing an average
increase of 6.7~ and for D5 at mode 1200/560 was
4.6% 5mode 1400/~05 showing an average increase of
~.1%). It should be noted that smoke and
particulate formation is a complex phenomena, so
these measurements will not necessarily always
coin~ide. ~owever, it is possible to have both
reduced opacity in smoke emission, ~nd at the same
time, a decrease in parti~ulate emission~ Moreov~r
due to the inherent difficulties with particulate
2~ analysi~ one should consider trends in the data and
~ot absolute Yalues. While operation with D4 at
modes 1200/557 and 1400/600 showed an average loss
in fuel economy of 4.6% and 3.0% respectively, and
operation of D5 at modes 1200/560 and 1400/605
showed an average loss in fuel economy of 2.2~ and
1.6~ respectively. ~owever, with D4 the varia~ion
in ~uel consumption is good compared to what
industry accepts as a variatlon. Moreover the
engine ran ~uite well with the D4 and ~5 fuels.
3~ Mor*over, while a one to one comparison
between the data of ~ at mode 2090/475 and th~
base diesel fuel a~ mode 20~4/50~ cannot be made
~ince the data can not be normalized because the
fuel consumption o~ D5 was less than the ba~e fuel
~-~3~9~ .
~z2~2~
- ~3 -
and D5 was not pullinq the same engine load as the
base fuel and thus had a different power
performan~e, which makes it difficult to say just
how large the effect is, nonetheless it is clear
~ that D~ exhibit~d a signifi~ant positive effect on
: smoke and particulate emission and also on the fuel
consumption as seen by its unnormaliz~d average
i~crease sf 3.8~ in ~uel economy and unnormalized
average d~creases o~ 27.3~ in smoke opacity and 42
in particulate cOntent of the exhaust.
The physical properties as listed in
ASTM-D975, except f~r cetane number7 water and
sediment~ of fuel compositions D4 and D5 as well
as of the base diesel fuel (I~-CAT~ employed in
Example 18 are listed belowO
D-4 D-5 ~ CAT
Flash Point, F 45 56 170
Cloud Point, ~F 18 18 20
Carbon Residue, ~ 0.21 0.21 0.06
Ash, wt. % 0.01 ~0.005 0.003
Viscosity at 40C, cSt2.97374 2.957543.31@100~C
Sulfur, wt. % 0.3717 0~3608 0.399
25 Copper Strip Corrosion l-A l-A l-A
Distillation, F
.
Initial :3Oilins~ Point~ F 174 176 334
10~ 33vaporated 215 20~ 466
2096 Evaporated 352 352 488
30 50% Evaporat~d 506 506 52 7
90~6 Evaporated 589 590 611
End Point, nF 636 610 664
ecGvered 98 9 7O 599. 0
% Residue 1.5 1.5 1~0
35 % Loss 0 5 1~ 0
The above e~aluation shows that fuel
compositions D~ and D5 of this invention meet
all the standard pecifications for No. 2 diesel
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- 2~ -
fuels (ASTM-D-975) except for the ~lash point.
Another e~aluation of the flash points of D-4, D-5
and the I~-C~T showed 80F, 69F and 169F,
respectively.
~xample 20
A fuel composition designated ~D6"
consis~ing of about 83~ ~0 wt. % of a diesel fuel,
(#2 Phillips P~troleum~ which had a cloud point of
-18C, about 5.30 wt. % of isopropanol, abou~ 0.70
10 wt. ~ water and about 10~40 wt. % of a 50:50 wt. ~
mixture of n-butanol and isobutanol said composition
having a cloud point of -18C, along with a fuel
composition designated ~D7" which was th~ same as
composition "D~n, but al50 contained about 0015
wt~ o a commercial cetane improver ~an alkyl
nitrate) were prepared and evaluat~d versus the same
unadulterated base diesel fuel employed in preparing
each composition D6 and D7 in terms of exhaust
emissions and fuel economy. The performance tests
were conducted on a chassis-mounted 5.7 liter
Oldsmobile and followed standard cold-start Feaeral
Test Procedures (CFR, Title 40, Part 86, SubPart
B). The results of ~aid tests based on an average
o~ duplica~e runs for each fuel were as follows:
~~_ EMISSIONS tq/mile)
Fuel fi8~eer Particula~es Nx ~r~ons M~n~xl~e MPG
Base
Diesel 48 0.389 1.34 0.327 1.21 21~3
30 D6 4~ 0.311 1.27 0.390 1.46 21~2
D7 46 0.322 1.27 0.386 1.40 21.4
The above results how that operation of
the e~gine witb fuel compositions D~ and D7 of
this invention resulted in a ~ignificant reductiQn
in both particulates and oxides o~ nitrogen in the
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- 25 - -
~xhau~t ~ver that shown when employing ~he base
diesel fuel while fuel economy remained essentially
the ~ame.
Various modifications and varia~ions of
S this invention will be obvious to a worker skilled
in the art and it is ~o be understood that such
modifications and variations are to be included
wienin the pur~iew o~ this application and the
spirit and scope of the appended claims.
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