Note: Descriptions are shown in the official language in which they were submitted.
- 2 - 201382a
This invention relates to fuel oil compositions and
more especially to fuel oil compositions containing
cracked components which are stabilized against sediment
formation and colour development during storage. Cracked
components are frequently included to give higher yields
of diesel fuel and heating oil.
However, when diesel and heating oils containing
cracked components are stored at ambient or elevated
temperatures in air they become discoloured and precipi-
tate sludge or sediment.
It is clear that thc problem of discoloration and
sediment formation is exacerbated by the presence of
cracked components in the fuel. This is demonstrated by
the results in Table 1 which show the amount of sediment
formed and the colour change when various fuel blends are
tested in the AMS 77.061 accelerated stability test.
Published research (see, for example, Offenhauer et. al,
Industrial and Engineering Chemistry, 1957, Volume 49,
page 1265, and the Proceedings of the 2nd International
Conference on the Long Term Stability of Liquid Fuels,
San Antonio, Texas, published October 1986) suggests
that discoloration and sediment result from the
oxidation of sulphur and nitrogen compounds present in
the fuel. The analysis of cracked components ~s consis-
tent with this. The resultR in Ta~le 2 show that crac~ed
components contain significantly larger quantities of
nitrogen and sulphur than straight distillates. Also,
~ 3 - 2013~25
the addition of nitrogen and sulp~ur compounds to a
stable straight distillate causes an increase in both
sediment and colour in t~e AMS 77.061 test (~able 3)
with the worst result being obtained when both nitrogen
and sulphur compounds are present in the fuel.
It has now been found that sediment and colour
formation may be substantially reduced in diesel fuels or
heating fuels, especially those containing cracked
components, by the addition of certain quaternary
ammonium compounds. According to this invention fuel
compositions comprise a base fuel, which may contain
cracked components, and a quaternary ammonium salt in
which the cation is derivable from, and advantageously
derived from, the reaction of a tertiary amine with an
olefin oxide in the presence of excess water to yield a
solutîon of a ~uaternary ammonium hydroxide, and the
anion is derived from an organic acid, subject to the
proviso that when the acid is an alkane monocarboxylic
acid the alkane is a straight chain alkane.
The ~uaternary ammonium salts may be made in two
stages: ~n the first stage a tertiary amine is reacted
with an olefin oxide in the presence of excess water to
yield a ~olution of a quaternary a~monium hydroxide, e.g.
R'3N + R''2c\-/Rl~2 + H20 (R~3N-cR~2-cl~n2)+oH
o OH
in which each R', w~ich may be the same or different, is
an organic group; and each Rn, which ~ay be the same or
2013825
different, is hydrogen or an organic group.
In the second stage the quaternary ammonium
hydroxide is neutralized with an orqanic acid to form a
quaternary ammonium salt, i.e.
(R'3N-CRn2-1 "2)~0H- + HA (R'3N-CRn2-1Rn2)+A- + H20
OH OH
As exam~les of suitable tertiary amines there may be
mentioned:
(i) amines of the formula R1R2R3N where Rl, R2
and R3 which may be the same or different are each
substituted or unsubstituted alkyl, cycloalkyl, alkenyl,
cycloalkenyl, or aryl. Each group R1, R2 and R3 prefer-
ably has 1 to 20 carbon atoms. Examples of this type of
amine are trimethylamine; ethyldimethylamine; n-propyl-
dimethylamine; triethanolamine, N,N-d~methylbenzylamine;
N,N-dimethylcyclohexylamine; N,N-dimethylaniline; N,N-
dimethyl-~4-methylcyclohexylamine) and N,N-dimethyl-p-
toluidine.
(ii) diamines of the formula R4R5N~CH2~nNR6R7
where n is an integer of one or more, and R4, R5, R6 and
R7, which may be the same or different, are ~s defined
a~ove for R1. Thus, one may use N,N,N',N'-tetramethyl
ethylenediamine.
(iii) fully al~ylated alkylene polyamines of the
form~la:
2 Q 1 3 8 ~ ~
-- 5 --
RaR9N tC2N4~ C2N4NRllR12
R10 m
where m is an integer of one or more and R8, R9, Rl~,
Rll, and R12, which may be the same or different, are as
defined for Rl above.
(iv) pyrldine and substituted pyridines e.g., a,
B and gamma- picolines, quinoline and substituted
quinolines and similar heterocyclic tertiary amines.
(v) N-substituted piperidines of the formula:
/CH2 CH2~
CH ~ / NR13
CH2 CH2
where R13 is as defined for R1 above.
(vi) N-substituted pyrrolidines of the formula:
/CH2 - CH2
R14 N\
CH 2 CH 2
where R14 is as defined for R1 above.
(vii) N-substituted morpholines of the formula:
/--~
R15 ~ N O
where R15 is as defined for ~1 a~ove.
(viii) amines of the formula:
- 6 - ~01~82~
~ (CH2)n
N (CH2)n ~ N
(CH2)n~
where n is an integer of two or more e.g. triethylene
diamine.
(xi) hexamethylenetetramine ~CH2)6N4 (hexamine).
The olefin oxides are preferably of the formula:
R16R17C ~ ~CR18Rl9,
where R16 R17, R18, and Rl9 which may be the same or
different, are each hydrogen, or substituted or unsub-
~tituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, or
aryl. Specific examples are ethylene oxide, propylene
oxide, but-l-ene oxide, but-2-ene oxide, oct-1-ene oxide
and styrene oxide.
The organic acid which may be used in the second
stage of the reaction and hence forms the anion in the
quaternary ammonium salt may be, for example, a car-
boxylic acid, carboxylic acid anhydride, phenol, 8ul-
phurized phenol, or sulphonic acid, subject to the
proviso that in the aspect of the in~ention which is a
fuel oil composition, unlimited as to type, then when the
aci~ is an alkane monocar~oxylic acid the al~ane is a
straight chain alkane and, preferably, the acid is an
al~ane l-carb~xylic acid.
The carboxylic acid may be, for example:
i) An acid of the formula:
'
2~13-~2~
R-COOH
where R is hydrogen, or a substituted or unsubstituted ~
alkyl, cycloalkyl, al~enyl, cycloalkenyl, or aryl group.
Examples of such acids include formic acid, acetic acid,
propionic acid, butyric acid, valeric acid, palmitic
acid, stearic acid, cyclohexanecarboxylic acid, Z-
methylcyclohexane carboxylic acid, 4-methylcyclohexane
carboxylic acid, oleic acid, linoleic acid, linolenic
acid, cyclohex-2-eneoic acid, benzoic acid,
2-methylbenzoic acid, 3-methylbenzoic acid, 4-methyl-
benzoic acid, salicylic acid, 2-hydroxy-4-methylbenzoic
acid, 2-hydroxy-4-ethylsalicylic acid, p-hydroxybenzoic
acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid,
o-aminobenzoic acid, p-aminobenzoic acid,
o-methoxybenzoic acid and p-methoxybenzoic acid.
ii) A dicarboxylic acid of the formula
HOOC-(CH2)n-COOH
where n is zero or an integer, including e.g. oxalic
acid, malonic acid, succinic acid, glutaric acid, adipic
acid, pimelic acid and suberic acid. Also included are
acids of the formula
R
HOOC-~cH2)x-c~-(cH2)y-c~
where x is zero or an integer, y is zero or an integer
and x and y may be e~ual or different and ~ is defined
as in (i). ~xamples of such acids include the alkyl or
alkenyl succinic acids, 2-me~hyl~utanedioic acid,
- 8 - 2013825
2-ethylpentanedioic acid, 2-n-dodecylbutanedioic acid,
2-n-dodecenylbutanedioic acid, 2-phenylbutanedioic acid,
and 2-~p-methylphenyl)butanedioic acid. Also included
are polysubstituted alkyl dicarboxylic acids wherein
other R groups as described above may be substituted on
the alkyl chain. These other groups may be substituted
on the same carbon atom or different atoms. Such
examples include 2,2-dimethylbutanedioic acid;
2,3-dimethylbutanedioic acid; 2,3,4-trimethylpentanedioic
acid; 2,2,3-trimethylpentanedioic acid; and 2-ethyl-3-
~ethylbutanedioic acid.
The dicarboxylic acids also include acid~ of the
formula:
HOOC-(cr~2r-2)cOOH
where r is an integer of 2 or more. Examples include
maleic acid, fumaric acid, pent-2-enedioic acid, hex-2-
enedioic acid; hex-3-enedioic acid, 5-methylhex-2-
enedioic acid; 2,3-di-methylpent-2-enedioic acid:
2-methylbut-2-enedioic ac~d; 2-dodecylbut-2-enedioic
acid: and 2-polyisobutylbut-2-enedioic acid.
The dicarboxylic acids also include aromatic
dicarboxylic acids e.g. phthalic acid, isophthalic acid,
terephthalic acid and substituted phthalic acids of the
formula:
HOOC
~ COOH
(R)n
9 ~0138~5
where R is defined as in (i) and n - 1, 2, 3 or 4 and
when n > 1 then the R groups may be the same or
different. Examples of such acids include 3-methyl-
benzene-1,2-dicarboxylic acid; 4-phenylbenzene-1,3-
dicarboxylic acid; 2-tl-propenyl)benzene-1,4-dicar-
boxylic acid, and 3,4-dimethylbenzene-1,2-dicarboxylic
acid.
The carboxylic acid anhydrides include the
anhydrides that may be derived from the carboxylic acids
described above. Also included are the anhydrides that
may be derived from a mixture of any of the carboxylic
acids described above. Specific exa~ples include acetic
anhydride, propionic anhydride, benzoic anhydride, maleic
anhydride, succinic anhydride, dodecylsuccinic anhydride,
dodecenylsuccinic anhydride, an optionally substituted
polyisobutylenesuccinic anhydride, advantageously one
having a molecular weight of between 500 and 2000
daltons, phthalic anhydride and 4-methylphthalic
~nhydride.
The phenols from which the anion of the quaternary
ammonium compound may be derived are of many different
types. Examples of suitable phenols include:
(i) Phenols of the formula:
~20)"
~ OH
where n = 1, 2, 3, 4 or 5, where R20 is define~ below and
- lO - 2013~2~
when n > 1 then the substituents may be the sa~e or
different. R20 may be hydrogen, or a substituted or
unsubstituted, alkyl, cycloalkyl, alkenyl, cycloalkenyl
or aryl group. The hydrocarbon group(s) may be bonded to
the benzene ring by a keto or thio-keto group.
Alternat~vely the hydrocarbon group(s) may be bonded
through an oxygen, sulphur or nitrogen atom. Examples of
such phenols include o-cresol; m-cresol; p-cresol;
2,3-dimethylphenol; 2,4-dimethylphenol; 2,3,4-trimethyl-
phenol; 3-ethyl-2,4-dimethylphenol; 2,3,4,5-tetramethyl-
phenol; 4-ethyl-2,3,5,6-tetramethylphenol; 2-ethylphenol;
3-ethylphenol; 4-ethylphenyl: 2-n-propylphenol;
2-isopropylphenol; 4-isopropylphenol; 4-n-butylphenol;
4-isobutylphenol; 4-secbutylphenol; 4-t-butylphenol;
4-nonylphenol; 2-dodecylphenol; 4-dodecylphenol;
4-octadecylphenol; 2-cyclohexylphenol; 4-cyclohexyl-
phenol; 2-allylphenol; 4-allylphenol; 2-hydroxydiphenyl;
4-hydroxydiphenol; 4-methyl-4'-hydroxydiphenyi;
o-methoxyphenol: p-methoxyphenol; p-phenoxyphenol;
2-hydroxydiphenylsulphide; 4-hydroxydiphenylsulphide;
4-hydroxyphenylmethylsulphide; and
4-hydroxyphenyldimethylamine. Also included ~re alkyl
phenols where the alkyl group is obtained by polymeri-
zation of a low moleculsr weight olefin e.g. polypropyl-
phenol or polyisobutylphenol.
Also included are phenols of the formula:
201382~
OH OH OH OH
~ CN2 ~ ~nd/or ~ ~
R2om ln R2om R21n
and/or
HO ~ CH2 ~ ~ OH
R20m R21n
where R2~ and R21 which may be the same or different are
as defined above for R20 and m and n are integers and for
each m or n greater than 1 each R20 or R21 may be the
same or different. Examples of such phenols include
2,2'-dihydroxy-5,5'-dimethyldiphenylmethane; 5,5'-
dihydroxy-2,2'-dimethyldiphenylmethane; 4,4'-dihydroxy-
2,2'-dimethyl-dimethyldiphenylmethane : 2,2'-dihydroxy-
5,5'-dinonyldiphenylmethane; 2,2'-dihydroxy-5,5'-
didodecylphenylmethane 2,2',4,4'-tetra-t-~utyl-3,3'-
dihydroxy-5,5'-didodecylphenylmethane; and 2,2',4,4'-
tetra-t-butyl-3,3'-dihydroxydiphenylmethane.
Also included are sulphurized phenols of the
formula:
20~ 38'~
- 12 -
OH OH OH OH
and/or
m R2ln R2om R2ln
and/or ~ Sx ~ OH
R20 R21
m n
where R20 and ~21 which may be the same or different are
as defined a~ove, and m and n are integers, for each m
and n greater than 1 each R20 and R21 may be the same or
different, and x is 1,2,3 or 4. Examples of such phenols
include:
2,2'-dihydroxy-5,5'-dimethyldiphenylsulphide:
5,S'-dihydroxy-2,2'-di-t-butyldiphenyldisulphide;
4,4'-dihydroxy-3,3'-di-t-butyldiphenylsUlphide;
2,2'-dihydroxy-5,5'-dinonyldiphenyldisulphide;
2,2'-dihydroxy-5,5'-didodecyldiphenyldisulphide;
2,2'-dihydroxy-5,5'-didodecyldiphenyltrisulphide; and
2,2'-dihydroxy-5,5'-didodecyldiphenyltetrasulphide.
The sulphonic acids from which the anion of the
quaternary ammonium salt can ~e derived include alkyl and
aryl sulphonic scid6 which have a total of 1 to 200
car~on ato~s per molecule although the preferred range is
2013~2~
1~-80 atoms per molecule. Included in this description
are aryl sulphonic acids of the formula: ~
R22p ~
~ S03H
where p = 1, 2, 3, 4, 5 and when p > 1 the substituents
may be the same or different, and R22 may represent R20
as defined above.
The hydrocarbon group(s) may ~e bonded to the
benzene ring through a carbonyl group or a thio-keto
group. Alternatively the hydrocar~on group(s) may be
bonded to the benzene ring throuqh a sulphur, oxygen or
nitrogen atom. Thus examples of sulphonic acids that may
be used include: benzene sulphonic acid; o-toluene-
sulphonic acid, m-toluenesulphonic acid; p-toluene-
sulphonic acid; 2,3-dimethylbenzenesulphonic acid;
2,4-dimethylbenzenesulphonic acid;
2,3,4-trimethyl~enzenesulphonic acid;
4-ethyl-2,3-dimethylbenzenesulphonic acid:
4-ethylbenzenesulphonic acid;
4-n-propylbenzenesulphonic acid;
4-n-butylbenzenesulphonic acid;
4-isobutylbenzenesulphonic acid;
4-sec-butylbenzenesulphonic acid;
4-t-butylbenzenesulphonic acid:
4-nonylbenzenesulphonic acid;
2-dodecylbenzenesulphonic acid; 4-dodecylbenzenesulphonic
- 14 - 2013~25
acid; 4-cyclohexylbenzenesulphonic acid;
2-cyclohexylbenzenesulphonic acid;
2-allylbenzenesulphonic acid;
2-phenylbenzenesulphonic acid:
4(4'-methylphenyl)benzenesulphonic acid:
4-methylmercaptoben2enesulphonic acid: 2-methoxybenzene
sulphonic acid; 4-phenoxybenzenesulphonic acid;
4-methylaminobenzenesulphonic acid;
2-dimethylaminobenzenesulphonic acid: and
2-phenylaminobenzenesulphonic acid. Also included are
sulphonic acids of the type listed above where R22 is
derived from the polymerization of a low molecular weight
olefin e.g. polypropylbenzenesulphonic acid and
polyisobutylenebenzenesulphonic acid.
Also included are sulphonic acids of the formula:
R23-So3H
where R23 is substituted or unsubstituted alkyl,
cycloalkyl, alkenyl or cycloalkenyl. Examples of such
sulphonic acids that may be used include methylsulphonic
acid: ethylsulphonic acid;
n-propylsulphonic acid; n-butylsulphonic acid;
isobutylsulphonic acid; sec-~utylsulphonic acid;
t-butylsulphonic; nonylsulphonic acid; dodecylsulphonic
acid; polypropylsulphonic acid; polyiso~utylsulphonic
lS 201382~
acid; cyclohexylsulphonic acid; and
4-methylcyclohexylsulphonic acid.
The quaternary ammonium salts may be made in two
stages, the first stage of which comprises the reaction
of a tertiary amine with an olefin oxide.
Generally 1 mole of the tertiary amine i9 treated
with A moles of the olefin oxide (where A is the number
of tertiary nitrogens in the amine molecule) in the
presence of an excess of water over that required by the
stoichiometry of the reaction.
Thus pyridine (1 mole) is treated with an olefin
oxide (1 mole) in water (>1 mole). Triethylenediamine (1
mole) is treated with an olefin oxide (2 moles) in water
(>2 mole). Hexamine (1 mole) is treated with an olefin
oxide (4 moles) in water (>4 moles).
However, the olefin oxide may be used in excess if
required, or desired, the excess olefin oxide then
reacting with the quaternary ammonium hydroxide. One
possible mechanism for this further reaction with olefin
oxide is illustrated by the equations:
N + CH2-c~2 + H20 ~ ~ +-CH2-CH20H OH-
~-C~off + XcH2-cH2 ~ ~ N+(cH2-cH2-o)x+l H
- ~6 - 2a~38~
As indicated above any guantity of water may be
used as long as it represents an excess oYer that
required by the stoichiometry of the reaction.
~ he reaction may be carried out in the following
ways:
(i) The amine i6 stirred with the olefin oxide
in the reactor and the water added to the reaction
mixture. The rate of addition of the water does not
affect the quality of the final product but slow addition
of water may be used to control an exothermic reaction.
(ii) The amine is mixed with the water in the
reactor and the olefin oxide is added to the stirred
reaction mixture. The olefin oxide may be added as:
(a) a gas either pure or diluted with an inert
carrier (e.g., nitrogen)
(b) a liquid
(c) a solution in water
(d) a solution in a water miscible organic
solvent (e.g., methyl or ethyl alcohol).
The rate of addition of the olefin oxide is not
critical for the quality of the final product but 8 slow
addition rate may be used to control an exothermic
reaction.
(iii) The olefin oxide i5 ~ixed with the water in
the reactor and the amine is added to the reaction
mixture. The amine may ~e added as:
(a) a pure gas, liquid or solid
- 1? - 201382~
(b) a solution in water
(c) a solution in a water soluble organic
solvent.
As with the olefin oxide and water addition, slow
addition of the amine may be used to control an
exothermic reaction.
To facilitate the reaction, the mixed reactants may
be heated together at a given temperature while the third
reactant is added at a rate sufficient to maintain a
steady reaction. Alternatively the reactants may be
heated in a pressure vessel but, when heating the
reactants to promote the reaction, a temperature greater
than 1004C should be avoided to prevent decomposition of
the quaternary ammonium hydroxide.
The second stage of the reaction comprises
neutralization of the quaternary ammonium hydroxide
formed in the first stage with the organic acid.
Generally, sufficient acid is mixed with the
solution obtained from the first stage to neutralize the
quaternary ammonium hydroxide. However, an excess of
acid may be used if required, as for example when only
one carboxylic acid group of a polybasic acid is to be
neutralized. The neutralization reaction may ~e carried
out:
(i) In the absence of any solvent.
~ii) In the presence of an alcoho}, e.g.,
methanol, ethanol, isopropanol, ethyl
201382~
- 18 -
Cellosolve (a trademark), or ethylene
glycol.
(iii) In the presence of any other polar orqanic
solvent, e.g., acetone, methyl ethyl ketone,
chloroform, carbon tetrachloride, or sym-
tetrachloroethane.
(iv) In the presence of a hydrocarbon solvent,
e.g., hexane, heptane, white spirit,
; benzene, toluene or xylene.
(v) In the presence of a mixture of any of the
above solvents.
The neutralization reaction may be carried out at
ambient temperature but generally an elevated temperature
is used. When the reaction is completed the water and
any solvents used may be removed by heating under vacuum.
The product is generally diluted with mineral oil, diesel
fuel, kerosene, or an inert hydrocarbon olvent to
prevent the product being too viscous.
The fuel composition advantageously comprises a
minor proportion by weight of the quaternary ammonium
compound, preferably less than 1% ~y weight, more prefer-
ab~y from 0.000001 to 0.1%, especially 2 to 200 ppm.
The cracked component in the f~el oil which leads
to t~e undesira~le colour formation and sedime~t is
generally obtained by cracking of heavy oil and may be
fuel oil in which the main constituent is a fraction
~ otained from a residual oil.
2013825
Typical methods available for the thermal cracking
are visbreaking and delayed coking. Alternatively the
fuels may be obtained by catalytic cracking, the prin-
cipal methods being moving-bed cracking and fluidized-
bed cracking. After cracking, the distillate oil is
extracted by normal or vacuum distillation, the boiling
point of the distillate oil obtained usually being 60-
500-C, and is a fraction called light-cycle oil,
preferably corresponding to the boiling point range of
light oil of 150-400 C. Compositions composed entirely
of this fuel or fuels which are mixtures of the cracked
fraction and normal distillates may be used in the
present invention.
The proportion by weight of direct-distillation
fraction and cracked fraction in a fuel oil composition
which is a mixture can vary considerably, but is usually
1:0.03 - 1:2 and preferably 1:0.05 - 1:1. Typically the
content of cracked fraction is usually 5-97%, and
preferably 10-50%, based on the weight of the composi-
tion.
The present invention accordingly also provides a
fuel oil composition comprising a distillate fraction and
a cracked fraction and a quaternary ammonium compound the
cation of which is the reaction product of a tertiary
amine, an olefin oxide, and water, the anion being
derived from an organic acid. The invention also
provides the use of such a compound in inhibiting
sediment and colour formation in a fuel oil composition,
~ 01 ~ S
- 20 -
especially one containing a component obtain2d by the
cracking of heavy oil.
The fuel sil compositions of the present invention
may contain othsr additives such as antioxidants,
anticorrosion agents, fluidity improvers, agents
absorbing ultraviolet radiation, detergents, dispersants
and cetane improvers in small amounts (for example,
usually less than 2~ based on the weight of the
composition).
Details and examples of the synthesis of the
quaternary ammonium compounds have been given in British
Specification No. 1,445,993, the disclosure of which is
incorporated by reference herein. The products were
tested in a fuel that was a blend of a stable distillate
(Fuel A), containing 50 ppm nitrogen and 0.24% sulphur,
and an unhydrofined catalytically cracked gas oil (Puel
B) with 6g5 ppm nitrogen and 1.11% sulphur. ~he present
invention i5 illustrated by the following exa~ples.
Table 1 shows the effect on sediment and colour in
the AMS 77.061 test of blending different amounts of the
straight distillate fuel with the unhydrofined catalyti-
cally cracked gas oil.
Table 2 shows the nitrogen and sulphur contents of
various fuels.
Table 3 shows the effect on colour and sediment of
doping the sta~le fuel (A~ with compounds containing
nitrogen and sulphur.
2013825
- 21 -
Table 4 shows the effect on sediment and colour in
the AMS 77.061 test of addinq 100 ppm of quaternary
ammonium compounds to a fuel containing 20% of cracked
components. Comparison of the results for the fuels
treated with quaternary ammonium compounds with the
results for the untreated fuel show that the compounds of
this invention control sediment and colour.
Table 5 shows the long term storage c~aracteristics
of fuel to which has been added 100 ppm of quaternary
ammonium compound. It can be seen that the sediment and
colour of the treated fuel are much better in the lonq
term than that of the untreated fuel.
20~38~
- 22 -
Table 1
The Eff~ct of Fuel Com~osition on Se~i~ent and
ColouF in the ANS 77.061 Accçlerated Stability Test
Fuel A Fuel B Sediment Colour (a)
wt.~ wt.~ mg/100 ml
100 0 0.14 + o.og #0.5,<0.5,<0.5
0.61 + 0.13 ~1.0, 1.0, 1.0
1.12 + 0.10 ~1.0,~1.0,#1.0,~1.0
4~ 60 1.80 + 0.04 ~2.0, ~2.0
2.10 + 0.10 ~2.0, ~2.0
0 100 2.90 6.0
(a) Colour change (ASTM D1500 test)
Table 2
~he Nit~ogen and Sul~hur Contents of Various Fuels
Type of Fuel Nitrogen (ppm) Sulphur (%)
Unhydrofined CCGO 695 1.11
n ~ 650 1 . 70
Straight distillate 50 0.24
~ n 70 0.25
.. .. 97 0.23
n n 128 0.24
_ 179 1 . 44
201382~
- 23 -
Ta~le 3
Effect of doping with dimethyl pyrrole ~DMP~ and
a s~l~honic acid (SA~ on the stability of a
strai~ht distillate fuel in the AMS 77.061 test
DMP SA Sediment Colour
ppm(a) pp~(b) (mg/100 ml) Before After C
. . .
Nil Nil 0.06,0.10 <0.5 <1.0 0.5
Nil 50 0.02,0.00 <0.5 <1.5 1.0
<0.5 <1.5 1.0
Nil 0.76,0.59 <0.5 <1.0 0.5
<0.5 <1.0 0.5
1.06,1.01 <1.5 <3.0 1.5
<1.5 c3.0 1.5
_
(a) 2,5-dimethylpyrrole
(~) A commercially available alkyl-aryl sulphonic acid
having a standard acid number of approximately 80 mg
KOH/g of acid.
---, -
o 2013g2
~ ~ -~
v. a ~ o o o o o r
r o ~ o o o o o o ~u~
r~
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_ _ .
o ~ ~ ~ ~ ~ ~
~ o ô o o o ~ ~
~ e N O O O O O 'a~
~ ~ CD O O ~` O ~1
~ ~/ O O O O O
I ~ . ~ _ _ _ _ _ _~ COo
I ~ ~ a
H ~ ~ ~ P~ U:~ P~ 1~
~ ~ ~ ~ ~ z a ~q ~
~ ~ C ~ ~ ~ V ~ -
E~H H H H H ~ ~ O
~ a :~o o o o o
o ~ z ~ ~ ~ oo~a ~
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