Note: Descriptions are shown in the official language in which they were submitted.
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CONDUCTIVITY IMPROVING ADDITIVE FOR
FUEL OIL COMPOSITIONS
This invention relates to fuel oils which exhibit improved conductivity
properties, to novel additive systems for providing such properties and to the
use of
such additives for improving the conductivity of fuel oils.
U.S. Patent 6,391,070, issued May 21,2002 to Schield discloses a composition
having increased electrical conductivity, which includes a) a liquid
hydrocarbon; b) an
anti-static amount of at least one hydrocarbon soluble copolymer of an
alkylvinyl
monomer and a cationic vinyl monomer, wherein the copolymer has an alkylvinyl
monomer unit to cationic vinyl monomer unit ratio of from about 1:1 to about
10:1,
the copolymer having an average molecular weight of from about 800 to about
1,000,000; and c) an anti-static amount of at least one hydrocarbon soluble
polysulfone copolymer of at least one olefin and sulfur dioxide. These
polymers are
described by Schield in U. S. Patent 5,672,183 as containing a cationic
quaternary
ammonium monomer.
U.S. Patent 5,792,730 discloses the use of dispersants prepared from heavy
polyamines as additives for lubricants and fuels.
The present invention is based upon the discovery that the use in combination
of an oil soluble succinimide dispersant comprising a functionalized
hydrocarbon
reacted with an alkylene polyamine or with a heavy alkylene polyamine with
certain
commercial conductivity improvers results in a synergistic effect upon the
conductivity properties of a fuel oil having little or no inherent
conductivity.
The invention is particularly useful for the formulation of turbine combustion
fuel oils which are generally those hydrocarbon fuels having boiling ranges
within the
limits of about 150° to 600°F (65 to 315°C) and are
designated by such terms as JP-4,
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JP-5, JP-7, JP-8, Jet A, Jet A-1. JP-4 and JP-5 are fuels defined by U.S.
military
specification MIL-T-5624-N and JP-8 is defined by U.S. Military Specification
MIL-
T83133-D. Jet A, Jet A-1 and Jet B are defined by ASTM specification D1655.
In accordance with the present invention there has been discovered an
improved fuel oil composition comprising a fuel oil having an inherent
conductivity
of less than 15 pS/m containing an effective conductivity improving amount of
a two
component additive system; wherein the two component additive system comprises
the combination of:
(a) an oil soluble succinimide dispersant additive prepared from a
functionalized hydrocarbon or polymer reacted (e.g, derivatized) with
an alkylene polyamine which may be represented by the formula
HRN (alkylene-NR)nH wherein n has an average value between 1 and
about 11, and in one embodiment about 2 to about 7, the "alkylene"
group has from 1 to about 10 carbon atoms, and in one embodiment
about 2 to about 6 carbon atoms, and each R is independently
hydrogen, an aliphatic or hydroxy-substituted aliphatic group of up to
about 30 carbon atoms. Some examples of alkylene polyamines
include methylene polyamines, ethylene polyamines, butylene
polyamines, propylene polyamines, pentylene polyamines, etc.
Specific examples of such polyamines include ethylene diamine,
diethylene triamine, triethylene tetramine, propylene diamine,
trimethylene diamine, tripropylene tetramine, tetraethylene pentamine,
hexaethylene heptamine, pentaethylene hexamine, or a mixture of two
or more thereof. Ethylene polyamines such as tetraethylene pentamine
and pentaethylene hexamine are preferred. Suitable alkylene
polyamines also include those termed "heavy polyamines" as defined
hereinbelow; and,
(b) a conductivity improver comprising (i) an olefin polysulfone and (ii) a
polymeric polyamine reaction product of epichlorohydrin and an
aliphatic primary monoamine or an N-aliphatic hydrocarbyl alkylene
diamine, or the sulfonic acid salt of the polymeric polyamine reaction
CA 02498124 2005-02-23
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product. The weight ratio of the olefin polysulfone to the polymeric
polyamine will be in the range of 40:1 to 1:40,
or the combination of:
(c) an oil soluble succinimide dispersant additive prepared from a
functionalized hydrocarbon or polymer reacted (e.g. derivatized) with a
"heavy polyamine". "Heavy polyamine" as referred to herein includes
higher oligomers or mixtures of higher oligomers of polyalkylene, e.g.
polyethylene, amines containing, e.g., essentially no
tetraethylenepentamine, at most small amounts of
pentaethylenehexamine, but primarily oligomers with 6 to 12,
preferably 7 to 12, nitrogens per molecule and more branching than
conventional polyamine or polyamine mixtures; and,
(d) a conductivity improver comprising a hydrocarbon soluble copolymer
of an alkylvinyl monomer and a cationic vinyl monomer, wherein the
copolymer has an alkylvinyl monomer unit to cationic vinyl monomer
unit ratio of from about 1:1 to about 10:1, the copolymer having an
average molecular weight of from about 800 to about 1,000,000.
The heavy polyamine as the term is used herein contains six or more, up to
about 12, nitrogens per molecule, but preferably comprises polyalkylene
polyamine
oligomers containing 7 or more nitrogens per molecule and with 2 or more
primary
amines per molecule. The heavy polyamine comprises more than 28 wt.% (e.g. >
32
wt.%) total nitrogen and an equivalent weight of primary amine groups of 120-
160
grams per equivalent. Commercial dispersants are based on the reaction of
carboxylic
acid moieties with a polyamine such as tetraethylenepentamine (TEPA) with five
nitrogens per molecule. Commercial TEPA is a distillation cut and contains
oligomers with three and four nitrogens as well. Other commercial polyamines
known generically as PAM, contain a mixture of ethylene amines where TEPA and
pentaethylene hexamine (PEHA) are the major part of the polyamine, usually
less
than about 80%. Typical PAM is commercially available from suppliers such as
the
Dow Chemical Company under the trade name E-100 or from the Union Carbide
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Company as HPA-X. This mixture typically consists of less than 1.0 wt.% low
molecular weight amine, 10-15 wt.% TEPA, 40-50 wt.% PEHA and the balance
hexaethyleneheptamine (HEHA) and higher oligomers. Typically PAM has 8.7-8.9
milliequivalents of primary amine per gram (an equivalent weight of 115 to 112
grams per equivalent of primary amine) and a total nitrogen content of about
33-34
wt. %.
Alkylene polyamines in general, including heavy polyamines, exhibit synergy
with the olefin polysulfonic/polymeric polyamine conductivity improver while
only
the heavy polyamines exhibit synergy with the copolymeric conductivity
improver.
The oil soluble dispersant additive used in the present invention is prepared
by
a derivatization (imidization), using an alkylene polyamine, of functionalized
hydrocarbons or polymers wherein the polymer backbones have a number average
molecular weight (Mn) of greater than 300. Preferably 800 to 7500, most
preferably
900 to 3000. The preferred number average molecular weight depends on the
properties of the particular backbone. For example, for ethylene alpha olefin
copolymers the preferred molecular weight is 1500 to 5000 (e.g. 2000 - 4000).
For
polybutenes the preferred molecular weight is 900 to 3000. A typical example
of
functionalized polymer is polyisobutenyl succinic anhydride (PIBSA) which is a
reaction product of polyisobutene and malefic anhydride. This reaction can
occur via
halogen-assisted functionalization (e.g. chlorination), the thermal "ene"
reaction, or
free radical addition using a catalyst (e.g. a peroxide). These reaction are
well known
in the art. In the present invention the functionalized backbones are
subsequently
derivatized with an alkylene polyamine. In the case of PIBSA, the reaction
with the
polyamine yields a polyisobutenyl succinimide.
The weight average molecular weight of the polysulfone will be in the range
of 10,000 to 1,500,000 with the preferred range being 50,000 to 900,000 and
the most
preferred molecular weight range being in the range of about 100,000 to
500,000.
The olefins useful for the preparation of the polysulfones may have about 6 to
20
carbon atoms, preferably about 6 to 18 carbon atoms, with 1-decene polysulfone
being particularly preferred. The preparation of these materials is known in
the art as
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described for example in U.S. Patent 3,917,466. The polymeric polyamine
component is prepared by heating an anune with epichlorohydrin in the molar
proportions of 1:1 to 1:1.5 in the range of 50°C to 100°C.
Suitable aliphatic primary
amines will have about 8 to 24 carbon atoms, preferably about 8 to 12 carbon
atoms,
with the aliphatic group being preferably an alkyl group. If the amine used is
an N-
aliphatic hydrocarbyl alkylene diamine, the aliphatic hydrocarbyl group will
have 8 to
24 carbon atoms and will preferably be alkyl and the alkylene group will have
2 to 6
carbon atoms. The preferred N-aliphatic hydrocarbyl alkylene diamine is N-
aliphatic
hydrocarbyl 1,3-propylenediamine which are commercially available. A preferred
commercially available polymeric polyamine is believed to be the polymeric
reaction
product of N-tallow-1,3-propylenediamine with epichlorohydrin sold as "Polyflo
130"
sold by Universal Oil Co. The polymeric polyamine reaction product will have a
degree of polymerization of about 2 to 20. The description of these materials
is also
disclosed in U.S. Patent 3,917,466.
Preferably, the polymeric polyamine reaction product component will be used
in the form of a sulfonic acid salt. Useful are oil soluble sulfonic acids
such as alkane
sulfonic acid or an aryl sulfonic acid. Particularly suitable is dodecyl
benzene
sulfonic acid or dinonyl naphthalene sulphonic acid.
The hydrocarbon soluble copolymer of an alkylvinyl monomer and a cationic
vinyl monomer is described in and may be made by the procedures of U.S. Patent
No.
5,672,183, the entirety of which is incorporated by reference herein. In a
preferred
embodiment, the copolymer has an alkylvinyl monomer unit to cationic vinyl
monomer unit ratio of from 1:1 to about 10:1, the copolymer having an average
molecular weight of from about 800 to about 1,000,000. In another embodiment,
the
cationic vinyl monomer is a cationic quaternary ammonium vinyl monomer, and in
a
preferred embodiment is a cationic quaternary ammonium acrylate monomer or a
cationic quaternary ammonium methacrylate monomer. In another embodiment, the
cationic vinyl monomer corresponds to the formula:
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X-
R3 R~
H2C= C-R-R4_Z+_Rs
R5
wherein Z is selected from the group consisting of nitrogen, phosphorus and
sulfur, X
is a non-halogen atom, R is selected from the group consisting of -C(=O)O-,
-C(=O)NH-, straight chain and branched alkylene groups, divalent aromatic
groups
and divalent alicyclic groups, R3 is selected from the group consisting of
hydrogen
and methyl, R4 is a straight chain or branched alkylene of up to about twenty
carbon
atoms (C~-Cue), and R5, R6 and R' are independently each a straight chain or
branched
alkyl of up to about twenty carbon atoms, provided however that if Z is sulfur
R' is
absent. Optionally, a copolymer of an alkyl vinyl monomer and a nitrile-
containing
monomer may be used in conjunction with the copolymer of alkylvinyl monomer
and
cationic vinyl monomer.
The oil-soluble succinimide dispersants are used in the compositions of the
present invention (on an active ingredient basis, i.e., without regard to
Garner oil or
solvent) in amounts ranging from 5 - 400 ppm, preferably about 10 - 160 ppm
(by
weight), such as about 10 - 60 ppm.
The polysulfonic-polyamine mixture conductivity improver or the alkylvinyl
monomer-cationic vinyl monomer copolymer conductivity improver may each be
used in amounts from 0.10-5 ppm, preferably about 0.25-1 ppm.
The compositions of this invention may also contain a phenolic antioxidant
and the amount of phenolic antioxidant compound incorporated may vary over a
range of about 1 - 100 ppm, preferably about 10 - 50 ppm, such as about 25 ppm
by
weight.
The preferred antioxidant phenolic compounds are the hindered phenolics
which are those which contain a sterically hindered hydroxyl group. These
include
those derivatives of dihydroxy aryl compounds in which the hydroxyl groups are
in
CA 02498124 2005-02-23
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the o- or p- position to each other. Typical phenolic antioxidants include the
hindered
phenols substituted with alkyl groups of a total of 6 or more carbon atoms and
the
alkylene-coupled derivatives of these hindered phenols. Examples of phenolic
materials of this type are 2,6-di-t-butyl-4-methyl phenol (BHT, butylated
hydroxy
toluene); 2-t-butyl-4-heptyl phenol; 2-t-butyl-4-octyl phenol; 2-t-butyl-4-
octyl phenol;
2-t-butyl-4-dodecyl phenol; 2,6-di-t-butyl-4-heptyl phenol; 2,6-di-t-butyl-4-
dodecyl
phenol; 2-methyl-6-di-t-butyl-4-heptyl phenol; and 2-methyl-6-di-t-butyl-4-
dodecyl
phenol. Examples of ortho coupled phenols include 2,2'-bis(6-t-butyl-4-heptyl
phenol); 2,2'-bis(6-t-butyl-4-octyl phenol); and 2,2'-bis(6-t-butyl-4-dodecyl
phenol).
Sulfur containing phenols can also be used. The sulfur can be present as
either
aromatic or aliphatic sulfur within the phenolic antioxidant molecule. BHT is
especially preferred, as are 2,6- and 2,4-di-t-butylphenol and 2,4,5- and
2,4,6-
triisopropylphenol, especially for use in jet fuels.
The compositions will preferably contain about 0.1 - 50 ppm of a metal
deactivator, preferably 1 - 10 ppm by weight. Examples of suitable metal
deactivators
include:
(a) Benzotriazoles and derivatives thereof, for example, 4- or 5-
alkylbenzotriazoles (e.g. tolutriazole) and derivatives thereof; 4,5,6,7-
tetrahydrobenzotriazole and 5,5'-methylenebisbenzotriazole; Mannich
bases of benzotriazole or tolutriazole, e.g. I-[bis(2-
ethylhexyl)aminomethyl]tolutriazole and 1-[bis(2-ethylhexyl)amino-
methyl]benzotriazole; and alkoxyalkylbenzotriazoles such as 1-
(nonyloxymethyl)-benzotriazole, I-(1-butoxyethyl)benzotriazole and
1-( I-cyclohexyloxybutyl)-tolutriazole;
(b) 1,2,4-triazoles and derivatives thereof, for example, 3-alkyl(or aryl)-
1,2,4-triazoles, and Mannich bases of 1,2,4-triazoles, such as 1-[bis(2-
ethylhexyl)aminomethyl-1,2,4-triazole; alkoxyalkyl-1,2,4-triazoles
such as 1-(1-butoxytheyl)-1,2,4-trizole; and acylated 3-amino-1,2,4-
triazoles;
(c) Imidazole derivatives, for example, 4,4'-methylenebis(2-undecyl-5-
methylimidazole) and bis((N-methyl)imidazol-2-yl]carbinol octyl
ether;
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(d) Sulfur-containing heterocyclic compounds, for example 2-
mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole and
derivatives thereof; and 3,5-bis[di(2-ethyl-hexyl)aminomethyl]-1,3,4-
thiadiazolin-2-one; and
(e) Amino compounds and imino compounds, such as N,N'-disalicylidene
propylene diamine, which is preferred, salicylaminoguanadine and
salts thereof.
The fuel oil compositions of this invention may also contain one or more other
additives commonly employed in fuels and present in such amounts so as to
provide
their normal attendant functions. Examples are cold flow improvers such as
ethylene-
unsaturated ester copolymers, comb polymers containing hydrocarbyl groups
pendant
from a polymer backbone, polar nitrogen compounds, compounds having a cyclic
ring
system having at least two substituents of the formula -A-NRlSRis where A is
linear
or branched hydrocarbylene and R'S and R16 are C9-C~ hydrocarbyl, hydrocarbon
polymers such as ethylene alpha-olefin copolymers, polyoxyethylene esters,
ethers
and ester/ether mixtures such as behenic diesters of polyethylene glycol.
Other
additives include lubricity additives such as fatty acids, dimers of fatty
acids, esters of
fatty acids or dimers of fatty acids, corrosion inhibitors, anti-icing
additives such as
ethylene glycol monornethyl ether or diethylene glycol monomethyl ether,
biocides,
thermal stability additives, anti-rust agents, anti-foam agents, demulsifiers,
detergents,
dispersants, cetane improvers, stabilisers, antioxidants, static dissipator
additives and
the like.
The fuel oil may be a hydrocarbon fuel such as a petroleum-based fuel oil for
example gasoline, kerosene or distillate fuel oil. The fuel oil can comprise
atmospheric distillate or vacuum distillate, or cracked gas oil or a blend in
any
proportion of straight run and thermally and/or catalytically cracked
distillates. The
most common petroleum distillate fuels are kerosene, jet fuels, diesel fuels,
low sulfur
diesel fuels and ultra low sulfur diesel fuels, automotive gas oil, heating
oils, premium
heating oils and heavy fuel oils. The heating oil or diesel fuel may be a
straight
atmospheric distillate, or it may contain minor amounts, e.g, up to 35 wt.%,
of
vacuum gas oil or cracked gas oils or of both.
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Heating oils may be made of a blend of virgin distillate, e.g. gas oil,
naphtha,
etc and cracked distillates, e.g. catalytic cycle shock. A representative
specification
for a diesel fuel includes a minimum flash point of 38°C and a 90%
distillation point
S between 282 and 380°C (see ASTM Designations D-396 and D-975).
The fuel oil may have a sulfur concentration of 0.2% by weight or less based
on the weight of the fuel. Preferably, the sulfur concentration is 0.05% by
weight or
less, such as 0.035% by weight or less or 0.01% by weight or less. The art
describes
methods for reducing the sulfur concentration of hydrocarbon middle distillate
fuels,
such methods including solvent extraction, sulfuric acid treatment, and
hydrodesulfurisation. The additive of the invention is advantageous in the
fuels
having low sulfur contents, providing lubricity improvement and detergency.
Also, the fuel oil may be a biofuel, i.e. come from an animal or vegetable
source, for example a vegetable or animal oil or both or derivatives thereof,
or a
mineral oil as described above in combination with biofuel.
Vegetable oils are mainly triglycerides of monocarboxylic acids, e.g.
containing 10-25 carbon atoms of the structure shown below;
CH20COR
CHOCOR
CH20COR
where R is an aliphatic radical of 10-25 carbon atoms which may be saturated
or
unsaturated.
Generally, such oils contain glycerides of a number of acids, the number and
kind varying with the source vegetable of the oil.
CA 02498124 2005-02-23
Examples of oils are rapeseed oil, tall oil, coriander oil, soyabean oil,
cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, maize oil,
almond oil,
palm kernel oil, coconut oil, mustard seed oil, beef tallow and fish oils.
Rapeseed oil,
which is a mixture of fatty acids esterified with glycerol, is preferred as it
is available
5 in large quantities and can be obtained in a simple way by pressing from
rapeseed.
Examples of derivatives thereof are alkyl esters, such as methyl esters, of
fatty
acids of the vegetable or animal oils. Such esters can be made by
transesterification.
The preferred alkyl esters of fatty acids are the methyl esters of oleic acid,
linoleic
10 acid, linolenic acid and erucic acid.
Commercial mixtures of the stated kind are obtained for example by cleavage
and esterification of natural fats and oils by their transesterification with
lower
aliphatic alcohols. For production of lower alkyl esters of fatty acids, it is
advantageous to start from fats and oils with high iodine number, such as, for
example, sunflower oil, rapeseed oil, coriander oil, castor oil, soyabean oil,
cottonseed
oil, peanut oil or beef tallow. Lower alkyl esters of fatty acids based on a
new variety
of rapeseed oil, the fatty acid component of which is derived to more than 80
wt.%
from unsaturated fatty acids with 18 carbon atoms, are preferred.
The invention is particularly useful for the formulation of turbine combustion
fuel oils (jet fuels) which are generally those hydrocarbon fuels having
boiling ranges
within the limits of about 150° to 600°F (65 to 315°C)
and are designated by such
terms as JP-4, JP-5, JP-7, JP-8, Jet A, Jet A-1. JP-4 and JP-5 are fuels
defined by U.S.
military specification MIL-T-5624-N and JP-8 is defined by U.S. Military
Specification MIL-T83133-D. Jet A, Jet A-1 and Jet B are defined by ASTM
specification D1655.
The invention will now be described by way of example only.
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EXAMPLES
The three fuels described below were tested.
Fuel Details:
Base FuelBase FuelBase Fuel
2 3 4
Test UnitsResult Result Result
Densit @ 15C K 814 829 835
Distillation
1BP C 168 174.6 216.6
10% 184.2 228.9 240.7
50% 210.2 274.0 277.0
90% 235.2 322.7 327.6
FBP 255 349.2 358.1
RESmUE vol% 1.1 2.0 2.0
LOSS vol% 1 0 0
FIA Anal sis vol%
Aromatics 15.2 28.2
Total Sulfur IP 336/95 %m/m 0.0006 <0.001 0.0036
Flash Point (Abel) 1P 54
170/99
Freezin oint IP 16/98 -54
Viscosit at -20C 1P71 5.48
!Existent um <1
CP -20
CFPP -9 -19
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Code Description of Additive
Dispersant A a succinimide made from a polyisobutenyl (Mn 950) succinic
anhydride reacted with a heavy polyamine having a 10-12%
pentaethylene hexamine content, 32% nitrogen and 7.7 meq/g of
primary nitrogen, the succinimide having 3.85% nitrogen.
Dispersant B a succinimide made from a polyisobutenyl (Mn 1000) succinic
anhydride and the same heavy polyamine used to make
Dispersant A, the succinimide having 4.74% nitrogen.
Dispersant C a succinimide made from a polyisobutenyl (Mn 950) succinic
anhydride reacted with a commercial PAM mixture of ethylene
polyamines, the succinimide having 2.0% nitrogen.
Dispersant D a succinimide made from a polyisobutenyl (Mn 1000) succinic
anhydride reacted with tetraethylene pentamine the succinimide
having 1.35% nitrogen
Dispersant E a succinimide made from a polyisobutenyl (Mn 2250) succinic
anhydride reacted with pentaethylene hexamine the succinimide
having 0.7% nitrogen
Stadis 450 66% toluene, 13.3% 1-decene polysulfone, 13.3% polyamine (a
reaction product of N-tallow-1,3-propylenediamine and
epichlorohydrin) and 7.4% dodecylbenzene sulfonic acid.
T3514 a commercial hydrocarbon soluble copolymer of an alkylvinyl
monomer and a cationic vinyl monomer sold as "T3514" by
Baker Petrolite as a conductivity improver.
Fuel Conductivi~ Tests
The fuels described above were tested for conductivity using an EMCEE 1152
conductivity meter. The results are given in Table 1 below. Tests were carried
out on
the fuel without any additives, fuels 2, 3 and 4 containing each of Dispersant
A and B
(which were dispersants made with heavy polyamines), Stadis 450 and T3514, the
latter two being commercial conductivity additives. Fuels containing a
combination
of this invention exhibit a synergistic cooperative effect in low conductivity
fuels not
, CA 02498124 2005-02-23
13
predictable from the values obtained when the additives are tested
individually. "BF"
refers to Base Fuel. Dispersants C, D and E (made with conventional ethylene
polyamines, i.e., not the heavy type) were tested only in fuel 2 and showed
synergy
with the ''Stadis 450" commercial conductivity improver. Dispersants made from
the
heavy polyamines show synergy with both types of commercial conductivity
improvers.
Additive ppm ConductivityConductivityConductivity
(pS/m) (pS/m) (pS/m)
BF 3 BF 4 BF 2
Base Fuel 0 18 1.7 3
Stadis 450 0.25 39.7 38.7 55
T3514 0.25 46.7 9.7 58
Dispersant A 33 65 34.7 523
Dispersant A + Stadis 33 + 96.7 131.3 707
450 0.25
Predicted Dispersant 104.7 73.4 578
A + Stadis 450
Dispersant A + T3514 33 + 93.7 78 617
0.25
Predicted Dispersant 111.7 44.4 581
A + T3514
Dispersant B 40 150 106.3 825
Dispersant B + Stadis 40 + 189.7 202.3 954
450 0.25
Predicted Dispersant 189.7 145 880
B + Stadis 450
Dispersant B + T3514 40 + 195.3 153.3 923
0.25
Predicted Dispersant 196.7 116 883
B + T3514
Dispersant C 25 188
Dispersant C + Stadis 25 + 317
450 0.25
Predicted Dispersant 243
C + Stadis 450
Dispersant D 19 100
Dispersant D + Stadis 19 + 240
450 0.25
Predicted Dispersant 155
D + Stadis 450
Dispersant E 29 35
Dispersant E + Stadis 29 + 147
450 0.25
Predicted Dispersant 90
E + Stadis 450
