TECHNICAL FIELD
The present invention relates to the use of a modified alkylphenol-aldehyde resin
in compositions of motor fuels or liquid hydrocarbon-containing fuels.
STATE OF THE ART
It is well known to a person skilled in the art that certain motor fuels or liquid
hydrocarbon-containing fuels stored in the presence of air for long periods of
time are subject to the formation of solid deposits, in particular at low
temperature.
These problems of deposits are connected with the presence of unstable
molecules contained in the motor fuels or liquid hydrocarbon-containing fuels.
These unstable molecules oxidize easily in the presence of oxygen, in
particular in the light, under the effect of ultraviolet (UV) radiation, and/or in the
presence of traces of metals, which catalyse the oxidation reaction and
therefore promote the formation of deposits. The unstable molecules which
are sensitive to oxidation are mainly molecules containing unsaturations, for
example olefins in gasolines, fatty acid methyl or ethyl esters (FAME and
FAEE), esters of animal fats or other sources of triglycerides in biodiesels or
olefins and partially hydrogenated aromatics in the cuts of distillates originating
from catalytic or thermal cracking of products originating from petroleum
refining.
The deposits that accumulate on the filters cause obstruction of the filters. A
great many additives used for reducing the formation of deposits have been
described extensively in the literature. Among the solutions proposed, the use
of conventional antioxidants such as the phenolic or amine antioxidants has
been proposed. By way of illustration, application US2010/0075876 may be
3
mentioned, which proposes a composition comprising at least one cyclic
amine antioxidant, for example diphenylamine and a phenolic antioxidant, 2,6-
di-tert-butyl-4-methylphenol (BHT).
The technical problem that the invention aims to solve is to improve the
oxidation and/or storage stability of compositions of motor fuels or liquid
hydrocarbon-containing fuels.
The present invention aims in particular to stabilize a biodiesel of type B100 in
order to obtain a value of Rancimat induction time (Tind) according to standard EN
15751 greater than or equal to 8 hours. A particular aim of the invention is to
obtain a gain in the induction time value (Tind) greater than or equal to 2.
The alkylphenol-aldehyde resins originating from the condensation of alkylphenol
and aldehyde have long been known as flow improvers for mineral oils: see for
example EP 311 452, which describes products of condensation of at least 80
mol% of dialkylphenols and aldehydes having from 1 to 30 carbon atoms; EP
857 776, which describes the use of alkylphenol-aldehyde resins in which the alkyl
groups of the alkylphenol have from 4 to 12 carbon atoms and the aldehyde from 1
to 4 carbon atoms and not containing more than 10 mol% of alkylphenols having
more than one alkyl group, in combination with ethylene/vinyl ester copolymers or
terpolymers for improving the fluidity of mineral oils; EP1 584 673, which describes
alkylphenol-aldehyde resins with Mn between 1000 and 3000 originating from the
condensation of a C1-C4 aldehyde and a mixture of alkylphenols, predominantly
monoalkylphenol, the alkyl group having from 1 to 20 carbon atoms, intended for
improving the low-temperature flow properties of motor fuel compositions.
Modified alkylphenol-aldehyde resins have also been proposed as additives for
improving the low-temperature flow of mineral oils: EP 1 767 610 describes
alkylphenol resins the condensation reaction of which with the aldehydes is carried
out in the presence of fatty acids having from 2 to 50 carbon atoms, or derivatives
thereof, such as esters.
4
In patent application WO2012/085865 and more recently in application
FR2012/55755, the applicant proposed novel modified alkylphenol-aldehyde
resins, usable for improving the lowtemperature stability of motor fuels and liquid
hydrocarbon-containing fuels.
Continuing this research, the applicant discovered a novel use of these modified
alkylphenol-aldehyde resins in compositions of motor fuels or liquid hydrocarboncontaining
fuels.
In particular, the present invention relates to the use of at least one modified
alkylphenol-aldehyde resin as additive for improving the oxidation and/or storage
stability of a motor fuel or liquid hydrocarbon-containing fuel composition, said
modified alkylphenol-aldehyde resin can be obtained by Mannich reaction of an
alkylphenol-aldehyde condensation resin
 with at least one aldehyde and/or one ketone having from 1 to 8 carbon atoms,
preferably from 1 to 4 carbon atoms;
 and at least one hydrocarbon-containing compound having at least one
alkylmonoamine or alkylpolyamine (alkylamine) group, having between 1 and
30 carbon atoms, preferably between 4 and 30 carbon atoms,
said alkylphenol-aldehyde condensation resin itself can be obtained by
condensation
 of at least one alkylphenol substituted with at least one linear or branched alkyl
group having from 1 to 30 carbon atoms, preferably a monoalkylphenol,
 with at least one aldehyde and/or one ketone having from 1 to 8 carbon atoms,
preferably from 1 to 4 carbon atoms.
According to a particular embodiment, said use makes it possible to improve the
storage stability of the motor fuel or liquid hydrocarbon-containing fuel composition
at a temperature less than 0°C, preferably less than -5°C, more preferably less
than or equal to -10°C.
5
According to another particular embodiment, this use makes it possible to reduce
the quantity of deposits formed during the storage of the motor fuel or liquid
hydrocarbon-containing fuel composition.
According to another preferred particular embodiment, the modified alkylphenolaldehyde
resin can be obtained from at least one alkylphenol substituted in the
para position, preferably starting from p-nonylphenol.
According to another preferred particular embodiment, the modified alkylphenolaldehyde
resin can be obtained from at least one aldehyde and/or one ketone
selected from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-
ethylhexanal, benzaldehyde, acetone, and preferably from at least formaldehyde.
According to one variant, the modified alkylphenol-aldehyde resin can be obtained
from at least one alkylamine having at least one primary amine group, and
advantageously at least one compound in which all the amine groups are primary
amines.
According to another variant, the modified alkylphenol-aldehyde resin can be
obtained from p-nonylphenol, formaldehyde and at least one hydrocarboncontaining
compound having at least one alkylmonoamine or alkylpolyamine
group.
According to another preferred particular embodiment, the modified alkylphenolaldehyde
resin can be obtained from at least one fatty-chain alkylamine or from a
mixture of fatty-chain alkylamines, and preferably from alkylamine(s) having a
number of carbon atoms between 12 and 24, preferably between 12 and 22.
According to one variant, the modified alkylphenol-aldehyde resin has a viscosity
at 50°C measured using a dynamic rheometer at a shearing rate of 100 s-1 on a
solution of said resin diluted with 30 % by weight of an aromatic solvent comprised
between 1000 and 10000 mPa.s, preferably between 1500 and 6000 mPa.s and
advantageously between 2500 and 5000 mPa.s.
6
According to certain particular embodiments, the object of the invention also has
one or more features listed below:
 the modified alkylphenol-aldehyde resin is used as an additive in a form
diluted in a solvent, preferably aromatic.
 the modified alkylphenol-aldehyde resin is used in the motor fuel or liquid
hydrocarbon-containing fuel composition in combination with one or more
additional additives.
 the additional additives are selected from dispersants/detergents, carrier
oils, metal deactivators, metallic passivators, antioxidants, dyes, antistatic
additives, corrosion inhibitors, biocides, markers, thermal stabilizers,
emulsifiers, friction reducing agents, surfactants, cetane improvers, anticlouding
agents, additives improving the conductivity, reodorants, lubricity
additives, lubricants and mixtures thereof.
 a quantity of modified alkylphenol-aldehyde resin comprised between 5 and
5000 ppmw, preferably between 10 and 2000 ppm, more preferably
between 50 and 1200 ppm, even more preferably between 50 and 600
ppm, is added to the motor fuel or liquid hydrocarbon-containing fuel
composition.
 the motor fuel or liquid hydrocarbon-containing fuel composition comprises
a motor fuel or liquid hydrocarbon-containing fuel selected from gas oils,
diesel fuels, gasolines, biofuels, jet fuels, domestic fuel oils (DFO) and
heavy fuel oils.
 the motor fuel or liquid hydrocarbon-containing fuel composition comprises
a motor fuel or other fuel selected from the middle distillates with a boiling
point temperature comprised between 100 and 500°C, preferably 140 to
400°C.
 the motor fuel or liquid hydrocarbon-containing fuel composition comprises
vegetable and/or animal oils and/or esters thereof and/or biodiesels of
animal and/or vegetable origin, preferably the esters are fatty acid methyl
esters (FAME) or fatty acid ethyl esters (FAEE), in particular vegetable oil
methyl esters (VOME) or vegetable oil ethyl esters (VOEE).
7
 the motor fuel or liquid hydrocarbon-containing fuel composition is a
biodiesel of type B100, whose value of induction time (Tind) obtained by a
Rancimat test according to standard EN 15751 is greater than or equal to 8
hours, advantageously a gain in value of induction time (Tind) obtained by
the Rancimat test according to standard EN 15751 is greater than or equal
to 2.
DETAILED DESCRIPTION OF THE INVENTION
Other advantages and features will become apparent from the description given
below. The particular embodiments of the invention are given as non-limitative
examples and are represented in the single attached drawing in which:
- Figure 1 shows the quantity of additive Fx added to the solution SFx
CME (ppm) as
a function of the induction time obtained according to a Rancimat test (standard
EN 15751).
Other advantages and features will become apparent from the following
description of particular embodiments of the invention given as non-limitative
examples.
According to a first particular embodiment, a motor fuel or liquid hydrocarboncontaining
fuel composition comprises at least one modified alkylphenol-aldehyde
resin. In particular, a quantity of modified alkylphenol-aldehyde resin preferably
comprised between 1 and 5000 ppmw, preferably between 5 and 2000 ppm, more
preferably between 10 and 1200 ppm, even more preferably between 50 and 600
ppm, is added to the motor fuel or liquid hydrocarbon-containing fuel composition.
For these ranges of product added, the modified alkylphenol-aldehyde resin is
regarded as an additive.
The modified alkylphenol-aldehyde resin is obtained by Mannich reaction of an
alkylphenol-aldehyde condensation resin:
o with at least one aldehyde and/or one ketone having from 1 to 8 carbon atoms,
preferably from 1 to 4 carbon atoms;
o and at least one hydrocarbon-containing compound having at least one
alkylmonoamine or alkylpolyamine group having between 1 and 30 carbon atoms,
8
preferably between 4 and 30 carbon atoms, called hereinafter "alkylamine" for
simplicity and clarity.
The alkylphenol-aldehyde condensation resin is itself obtained by condensation:
o of at least one alkylphenol substituted with at least one linear or branched alkyl
group having from 1 to 30 carbon atoms, preferably a monoalkylphenol,
o with at least one aldehyde and/or one ketone having from 1 to 8 carbon atoms,
preferably from 1 to 4 carbon atoms.
The modified alkylphenol-aldehyde resin according to the invention is,
advantageously, obtained starting from at least one para-substituted alkylphenol.
Nonylphenol will preferably be used.
The preferred average number of phenol nuclei per molecule of nonylphenolaldehyde
resin is preferably greater than 6 and less than or equal to 25, and more
preferably comprised between 8 and 17, and even more preferably between 9 and
16, phenol nuclei per molecule. The number of phenol nuclei can be determined
by nuclear magnetic resonance (NMR) or gel permeation chromatography (GPC).
According to a variant, the modified alkylphenol-aldehyde resin can be obtained
starting from at least one aldehyde and/or one ketone selected from formaldehyde,
acetaldehyde, propionaldehyde, butyraldehyde, 2-ethylhexanal, benzaldehyde,
acetone, preferably at least formaldehyde.
According to a particular embodiment, the modified alkylphenol-aldehyde resin is
obtained from at least one alkylamine having at least one primary and/or
secondary amine group. In particular, the alkylamine is selected from the primary
or secondary amines substituted with, respectively, one or two alkyl groups,
preferably with 12 and 24 carbon atoms, more preferably with 12 and 22 carbon
atoms.
According to a preferred variant, the modified alkylphenol-aldehyde resin is
obtained from at least one alkylamine having at least one primary amine group. In
9
particular, the modified alkylphenol-aldehyde resin can advantageously be
obtained starting from at least one alkylamine having at least one primary amine
group and at least one compound in which all the amine groups are primary
amines. The alkylamine is preferably a fatty-chain alkylamine having between 12
and 24 carbon atoms, preferably between 12 and 22 carbon atoms.
According to another preferred variant, the modified alkylphenol-aldehyde resin is
obtained starting from at least one alkylamine having at least one primary amine
group and comprising a fatty chain having between 12 and 24 carbon atoms,
preferably between 12 and 20 carbon atoms.
The commercial alkylamines are not generally pure compounds, but mixtures.
Among the alkylamines marketed that are suitable, the fatty-chain alkylamines
marketed under the names: Noram®, Trinoram®, Duomeen®, Dinoram®,
Trinoram®, Triameen®, Armeen®, Polyram®, Lilamin® and Cemulcat® may be
mentioned in particular.
As a preferred example, Trinoram S may be mentioned, which is a tallow
dipropylenetriamine, also known under the name N-
(tallowalkyl)dipropylenetriamine.
According to a particular embodiment, the modified alkylphenol-aldehyde resin is
used as an additive in a form diluted in a solvent or a dispersant. As an example,
the solvent or dispersant is selected from the aliphatic and/or aromatic
hydrocarbons or mixtures of hydrocarbons, for example the fractions of gasoline,
kerosene, decane, pentadecane, toluene, xylene, ethylbenzene, mixtures of
commercial solvents such as Solvarex 10, Solvarex 10 LN, Solvent Naphtha,
Shellsol AB, Shellsol D, Solvesso 150, Solvesso 150 ND, Solvesso 200, Exxsol,
ISOPAR. The solvent or dispersant is preferably aromatic. The solvent or
dispersant used can also contain a polar dissolution adjuvant, such as 2-
ethylhexanol, decanol, isodecanol and/or isotridecanol.
10
The concentration by weight of the modified alkylphenol-aldehyde resin diluted in
the solvent or dispersant can advantageously vary from 1 to 99.5%, preferably
from 5 to 95%, more preferably from 10 to 90% and even more preferably from 30
to 90%.
The viscosity of the modified alkylphenol-aldehyde condensation resin, diluted with
30 % by weight of aromatic solvent measured at 50°C using a dynamic rheometer
with a shearing rate of 100 s-1 is preferably comprised between 1000 and 10000
mPa.s, preferably between 1500 and 6000 mPa.s, and advantageously between
2500 and 5000 mPa.s.
The modified alkylphenol-aldehyde resin can also be used in a motor fuel or liquid
hydrocarbon-containing fuel composition in combination with one or more
additional additives.
Besides the modified alkylphenol-aldehyde resin described above, the motor fuel
or liquid hydrocarbon-containing fuel composition can contain additional additives
selected from dispersants/detergents, carrier oils, metal deactivators, metallic
passivators, antioxidants, dyes, antistatic additives, corrosion inhibitors, biocides,
markers, thermal stabilizers, emulsifiers, friction reducing agents, surfactants,
cetane number improvers, anti-clouding agents, additives improving the
conductivity, reodorants, lubricity additives, lubricants and mixtures thereof.
Among the other additional additives, the following may be mentioned in particular:
a) procetane additives, in particular selected from (but not limited to) the alkyl
nitrates, preferably 2-ethylhexyl nitrate, the aroyl peroxides, preferably benzyl
peroxide, and the alkyl peroxides, preferably ditert-butyl peroxide;
b) antifoaming additives, in particular selected from (but not limited to) the
polysiloxanes, the oxyalkylated polysiloxanes, and the amides of fatty acids
originating from vegetable or animal oils; examples of such additives are given
in EP0861182, EP0663000, EP0736590;
c) detergent and/or anti-corrosion additives, in particular selected from (but not
limited to) the group consisting of the amines, succinimides,
alkenylsuccinimides, polyalkylamines, polyalkyl polyamines and
11
polyetheramines; examples of such additives are given in EP0938535,
US2012/0010112 and WO2012/004300;
d) lubricity additives or anti-wear agents, in particular selected from (but not limited
to) the group consisting of the fatty acids and the ester or amide derivatives
thereof, in particular glycerol monooleate, and the derivatives of mono- and
polycyclic carboxylic acids; examples of such additives are given in the
following documents: EP0680506, EP0860494, WO1998/04656, EP0915944,
FR2772783, FR2772784;
e) cloud point additives, in particular selected from (but not limited to) the group
consisting of the long-chain olefin/(meth)acrylic ester/maleimide terpolymers,
and the polymers of esters of fumaric/maleic acids. Examples of such additives
are given in EP0071513, EP0100248, FR2528051, FR2528051, FR2528423,
EP112195, EP0172758, EP0271385, EP0291367;
f) anti-sedimentation additives and/or paraffin dispersants in particular selected
from (but not limited to) the group consisting of the (meth)acrylic acid/alkyl
(meth)acrylate copolymers amidated with a polyamine, the polyamine
alkenylsuccinimides, the derivatives of phthalamic acid and of double-chain fatty
amine; alkylphenol/aldehyde resins different from the alkylphenol/aldehyde
resins according to the invention; examples of such additives are given in
EP0261959, EP0593331, EP0674689, EP0327423, EP0512889, EP0832172,
US2005/0223631, US5998530, WO1993/014178;
g) polyfunctional additives for low temperature operability in particular selected
from the group consisting of the polymers based on olefin and alkenyl nitrate as
described in EP0573490;
h) additives for improving low-temperature performance and filterability (CFI), such
as the ethylene/vinyl acetate (EVA) copolymers and/or ethylene/vinyl propionate
(EVP) copolymers, the ethylene/vinyl acetate/vinyl versatate (E/VA/VEOVA)
terpolymers; the amidated maleic anhydride/alkyl(meth)acrylate copolymers can
be obtained by reaction of a maleic anhydride/alkyl(meth)acrylate copolymer
and an alkylamine or polyalkylamine having a hydrocarbon-containing chain
from 4 to 30 carbon atoms, preferably from 12 to 24 carbon atoms; the
amidated alpha-olefin/maleic anhydride copolymers can be obtained by reaction
of a copolymer of alpha-olefin/maleic anhydride and an alkylamine or
polyalkylamine, where the alpha-olefin can be selected from the C12-C40,
12
preferably C16-C20 alpha-olefin and the alkylamine or polyalkylamine having,
advantageously, a hydrocarbon-containing chain from 4 to 30 carbon atoms,
preferably from 12 to 24 carbon atoms. As examples of terpolymers, those
described in EP01692196, WO2009/106743 and WO2009/106744 may be
mentioned.
i) other antioxidants of the hindered phenol type or alkylated amine antioxidants of
the paraphenylene diamine type;
j) metal passivators, such as triazoles, alkylated benzotriazoles and alkylated
tolutriazoles;
k) metal sequestering agents such as disalicylidene propanediamine (DMD)
l) acidity neutralizers such as the cyclic alkylamines
In particular, the motor fuel and liquid hydrocarbon-containing fuel composition can
contain, in addition to the modified alkylphenol-aldehyde resin, a filterability
additive or a combination of a first and a second filterability additive as described
in patent application FR2012/055755 filed on 19/06/2012 by the applicant, cited as
an example and incorporated by way of reference in the present application.
The motor fuel and liquid hydrocarbon-containing fuel composition can
advantageously contain a filterability additive selected from:
o terpolymers of C4 to C22, preferably C18 to C22, alkyl (meth)acrylate, of C20 to
C24 alpha-olefin and of N-substituted maleimide with a hydrocarbon-containing
chain having between 4 and 30, preferably between 14 and 20, more preferably
between 16 and 18 carbon atoms, it being understood that the closed Nsubstituted
maleimide structure may also, depending on the conditions of use or
storage, open so that it has an open amide/ammonium salt or diamide structure,
o C1 to C40 alkyl (meth)acrylate homopolymers, preferably C1 to C40, more
preferably C8 to C24, alkyl polyacrylates,
o ammonium salts of mono- or polycarboxylic acid comprising at least one
hydrocarbon-containing chain, linear or branched, saturated or unsaturated and
having between 4 and 30 carbon atoms.
The combination of a first and a second filterability additive can correspond to at
least one first filterability additive selected from the C1 to C40 alkyl (meth)acrylate
13
homopolymers, preferably the C8 to C24 alkyl polyacrylates and at least one
second filterability additive selected from:
o terpolymers of C4 to C22 alkyl (meth)acrylate, of C20 to C24 alpha-olefin
and of N-substituted maleimide with a hydrocarbon-containing chain
having between 4 and 30 carbon atoms,
o ammonium salts of mono- or polycarboxylic acid comprising at least
one hydrocarbon-containing chain, linear or branched, saturated or
unsaturated and having between 4 and 30 carbon atoms.
Each additive can be incorporated separately in the motor fuel and liquid
hydrocarbon-containing fuel composition, optionally diluted with one or more
solvent or dispersant agents described above. According to one variant,
compositions of additives can, for example, be prepared before incorporation in
the motor fuel and liquid hydrocarbon-containing fuel composition by dissolving or
dispersing each constituent, separately or in a mixture, with one or more solvent or
dispersant agents described above.
The additional filterability additive can be present in the motor fuel or liquid
hydrocarbon-containing fuel composition in a quantity ranging from 0.5 to 1000
ppm, preferably from 1 to 500 ppm, more preferably from 1 to 400 ppm.
The motor fuel or liquid hydrocarbon-containing fuel composition advantageously
comprises a motor fuel or liquid hydrocarbon-containing fuel selected from gas
oils, diesel fuels, gasolines, biofuels, jet fuels, domestic fuel oils (DFO) and heavy
fuel oils.
According to a particular embodiment, the motor fuel or liquid hydrocarboncontaining
fuel composition comprises a motor fuel or other fuel selected from the
middle distillates with a boiling point temperature comprised between 100 and
500°C, preferably 140 to 400°C, more preferably between 120 to 500°C, even
more preferably from 140 to 400°C.
These middle distillates can, for example, be selected from distillates obtained by
direct distillation of crude hydrocarbons, vacuum distillates, hydrotreated
14
distillates, distillates originating from catalytic cracking and/or hydrocracking of
vacuum distillates, distillates resulting from methods of conversion of the ARDS
type (by desulphurization of atmospheric residue) and/or from visbreaking,
distillates originating from the upgrading of Fischer-Tropsch cuts, distillates
resulting from BTL (biomass to liquid) conversion of vegetable and/or animal
biomass, and/or mixtures thereof.
The motor fuels and liquid hydrocarbon-containing fuels can also contain distillates
originating from refining operations that are more complex than those originating
from the direct distillation of hydrocarbons. The distillates can, for example,
originate from cracking, hydrocracking and/or catalytic cracking processes and
visbreaking processes.
The motor fuels and liquid hydrocarbon-containing fuels can also contain new
sources of distillates, among which the following may be mentioned in particular:
- the heaviest cuts originating from cracking and visbreaking processes with high
concentration of heavy paraffins, comprising more than 18 carbon atoms,
- the synthetic distillates originating from gas conversion such as those originating
from the Fischer-Tropsch process,
- the synthetic distillates resulting from the treatment of biomass of vegetable
and/or animal origin, such as in particular NexBTL.
- and vegetable and/or animal oils and/or esters thereof, preferably the fatty acid
methyl esters (FAME) or fatty acid ethyl esters (FAEE), in particular vegetable oil
methyl esters (VOME) or vegetable oil ethyl esters (VOEE).
- hydrotreated and/or hydrocracked and/or hydrodeoxygenated (HDO) vegetable
and/or animal oils
- or biodiesels of animal and/or vegetable origin.
The motor fuel or liquid hydrocarbon-containing fuel composition can comprise
only new sources of distillates or can consist of a mixture with conventional
petroleum middle distillates as fuel base of the diesel type and/or base of domestic
fuel oil. These new sources of distillates generally comprise long paraffin chains
greater than or equal to 10 carbon atoms, and preferably from C14 to C30.
15
In general, the sulphur content of the motor fuel and liquid hydrocarbon-containing
fuel compositions is less than 5000 ppm, preferably less than 500 ppm, and more
preferably less than 50 ppm, or even less than 10 ppm and advantageously is
sulphur-free, in particular for fuels of the gas oil type.
EXAMPLES
Synthesis of a modified alkylphenol-aldehyde resin according to the invention,
designated C0
In a first step, an alkylphenol-aldehyde resin is prepared by condensation of paranonylphenol
and formaldehyde (for example according to the procedure described
in EP 857 776) with viscosities at 50°C (measured at 50°C using a dynamic
rheometer with a shearing rate of 10 s-1 on the resin diluted with 30 % by weight of
aromatic solvent (Solvesso 150)) comprised between 1800 and 4800 mPa.s.
In a second step, the alkylphenol-aldehyde resin originating from the first step is
modified by Mannich reaction by adding 2 molar equivalents of formaldehyde and
2 molar equivalents of tallow dipropylenetriamine, known under the name N-
(tallowalkyl)dipropylenetriamine and marketed for example under the name
Trinoram S, relative to the alkylphenol-aldehyde resin.
The characteristics of the resin obtained are presented in the following Table 1:
Table 1
Resin No. alkylamine
used
Dry matter Viscosity at
50°C
(mPa.s)*
Average number of
phenol nuclei per
molecule of resin**
(1g-30 min-200°C)
C0 Trinoram S 70.10% 4855 14.1
* measured on a resin diluted with 70 % by weight of Solvesso 150, shearing rate 10s-1 using a
Haake RheoWin rheometer
** measured by nuclear magnetic resonance (NMR)
Test of oxidation and storage stability
. Initial components
. S: aromatic solvent marketed under the name "Solvarex 10"
. C1: modified alkylphenol-aldehyde resin C0 diluted with 50 % by weight of
aromatic solvent (Solvesso 150)
16
. C2: 2,6-di-tert-butyl-4-methylphenol (BHT) (CAS number 128-37-0); purity 99 %
by weight
. C3: 2,6-di-tert-butyl-4-sec-butylphenol (CAS number 17540-75-9); purity 95 % by
weight
. C4: 2,6-di-tert-butyl-4-nonylphenol (CAS number 4306-88-1); purity 90 % by
weight
. C5: 2-tert-butyl phenol (CAS number 88-18-6) at 90 % by weight
. C6: N,N-disalicylidene-1,2-diaminopropane (DMD; CAS number 94-91-7) diluted
with 50 % by weight of aromatic solvent (Solvarex 10)
Compositions C2, C3, C4 and C5 are sterically hindered phenols known to be
antioxidant compounds. BHT (C2) is a conventional antioxidant additive commonly
used for fatty acid methyl esters (FAME), in particular for vegetable oil methyl
esters (VOME).
Composition C6 contains DMD, a known metal sequestering/chelating additive.
. Formulations Fx
The percentage by weight of the various components of each formulation F1 to F4
and of each formulation Fc1 to Fc4 evaluated for comparison is detailed in Table 2
below:
Table 2
Fx
(% by weight)
F1 F2 F3 F4 Fc1 Fc2 Fc3 Fc4
C1 100 50 50 50
C2 45 25 40 25
C3 48
C4 50 48
C5 75 60 73
C6 2 2 2
S 55
Tantiox *
(%)
50 70 68.2 70.6 45 92.25 93.6 91.45
* Level of active material corresponding to the percentage by weight of active material of the
antioxidant compounds or compounds involved in the antioxidant effect, namely resin C0, the
hindered phenol compounds and the metal sequestering/chelating agent (DMD).
17
.Example 1: Test of oxidation stability (Rancimat) and storage stability on a
solution of colza oil methyl esters (CME)
The antioxidant properties of different formulations F1 to F4 and Fc1 to Fc4 were
evaluated by a Rancimat test according to standard DIN EN 15751, on a solution
of colza oil methyl esters (CME) (marketed by the company Mosselman under the
name EMC). In the context of a Rancimat test, an induction time (TInd) is
determined, expressed in hours, following the procedure specified by standard NF
EN 15751. Induction time means the time elapsed between the start of
measurement and the moment when formation of oxidation products begins to
increase rapidly. The induction time is representative of the oxidation stability. The
more significant the induction period, the higher the oxidation stability of the CME
solution. The CME solution was chosen because it has a very low value of
induction time (1.5 h) and is therefore particularly discriminating.
The measurements were carried out on the initial solution of CME, designated
S0
CME, and on the solution of CME with addition of 1200 ppm of the different
formulations F1 to F4 and Fc1 to Fc4, designated SFx
CME. The results are presented
in Table 3 below and are represented graphically in Figure 1.
Moreover, the weight of each formulation F1 to F4 and Fc1 to Fc4 (mFx) necessary in
order to reach an induction time of 3.5 hours, i.e. the weight required for increasing
the Rancimat of the solution S0
CME by 2 hours (arrow in Figure 1), was determined
graphically on the basis of the Figure 1 obtained. The weight of active material
required in order to reach an induction time of 3.5 hours was also calculated from
the values "mFx" and from the level of the respective active material "Tantiox", for
each formulation F1 to F4 and Fc1 to Fc4.
Finally, the storage stability of each solution SFx
CME was determined for different
storage temperatures, designated Ts. For this measurement, 50 ml of solution
SFx
CME is put in a 60-ml glass conical flask and stored at the storage temperature
(Ts). The phase that has settled to the bottom of the flask is measured at regular
time intervals, namely every 24 hours. If the deposit is less than 0.4 ml, the
solution is considered to be stable. Starting from a quantity of deposit greater than
0.4 ml, the solution is considered to be unstable.
18
The results obtained are given in Table 3 below:
Table 3
Fx F1 F2 F3 F4 Fc1 Fc2 Fc3 Fc4
TInd
S
0
CME
(h) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
TInd
S
Fx
CME
(h) 11.56 7.06 7.3 8.17 3.39 3.3 4.09 6.06
mFx (ppm) 240 430 420 360 1200 1200 940 540
mFx x
Tantiox
(ppm)
120 301 286 254 540 1007 880 494
Storage stability
Ts (°C)
20°C ++ ++ ++ ++ ++ ++ ++ ++
-5°C ++ ++ ++ ++ - ++ ++ ++
-10°C ++ ++ ++ ++ - ++ ++ ++
"-": unstable after storage for 24 hours
"++": stable for at least 3 weeks of storage
Oxidation stability
Starting from the results obtained (Table 3 and Figure 1), it can be seen that
formulation F1 at 50 % by weight of resin C0 according to the invention is the most
effective formulation as antioxidant additive. The formulations comprising resin C0
according to the invention (F1, F2, F3 and F4) all have improved efficacy on the
oxidation stability compared to the known formulations of antioxidant according to
the prior art (Fc1, Fc2, Fc3 and Fc4).
In particular, F1 is more effective than Fc1 containing BHT, a conventional
antioxidant for FAMEs, with an induction time of 11.56 hours versus 3.39 hours.
Thus, the level of treatment of the CME to reach a gain of 2 hours in the Rancimat
test (TInd (h) = 3.5h) is reduced by a factor of about 5. It changes from 1200 ppm
for Fc1 to 240 ppm for F1 or, only taking into account the quantity of active material,
it changes from 540 ppm for Fc1 to 120 ppm for F1.
By comparing the results for F1 and F2, it can be seen that addition of another
hindered phenol antioxidant compound (C4) replacing part of the composition C1
decreases the antioxidant effect of formulation F2. The hindered phenol antioxidant
19
compound C4 is therefore less effective than composition C1. Nevertheless, F2
maintains an antioxidant effect at a level above the desired objective, namely a
gain in induction time greater than 5 hours at 1200ppm relative to the induction
time of S0
CME.
Such a decrease in induction time (TInd) may not be found by comparing the results
obtained for Fc1 (TInd = 3.39) and those obtained with the formulations Fc2 (TInd =
3.3) and Fc3 (TInd = 4.09) corresponding to mixtures of hindered phenol
compounds C2+C5. Addition of another hindered phenol antioxidant compound
(C5) has little effect on the efficacy of BHT (C2). In fact, the formulations Fc1, Fc2
and Fc3 have equivalent antioxidant properties (Figure 1).
By adding 2 % by weight of C6 (DMD) to the mixture C2+C5, a significant increase
of about 3 hours in the induction time for formulation Fc4 (TInd = 6.06) may be found
compared to Fc2 (TInd = 3.3). The combination of a metal sequestering/chelating
agent such as DMD with the conventional hindered phenol compound improves
the oxidation stability considerably.
Conversely, the metal sequestering/chelating agent (C6) has hardly any effect on
the oxidation stability when a resin C0 according to the present invention is used,
as shown by the results of F3 (TInd = 7.3) compared to F2 (TInd = 7.06).
Storage stability
The formulation Fc1 containing only BHT is unstable at low temperature starting
from -5°C. The formulations comprising resin C0 according to the invention (F1, F2,
F3 and F4) are all stable in storage not only at ambient temperature but also at low
temperature, at least down to -10°C.
Thus, the use of resin C0 according to the invention in CME makes it possible to
improve the storage stability at a temperature equal to -10°C.
.Example 2: Test of oxidation stability (Rancimat) on an engine gas oil (EGO) of
type B100
A Rancimat test according to standard DIN EN 15751 is carried out on an engine
gas oil of type B100, i.e. containing 100% by volume of vegetable oil methyl esters
20
(VOME) without addition (EGO0) and with addition of 1200 ppm of F1 or Fc1
described above (EGO1). The characteristics of the engine gas oil EGO0 are
presented in Table 4 below and the results of the Rancimat test are given in Table
5.
Table 4
EGO°
CFPP (°C) NF EN 116 -5
Cloud point (°C) NF EN 23015 0
MV15 (kg/m3) NF EN ISO12185 880
Viscosity at 40°C
EN ISO 3104
4
Oxidation stability (at 110°C, h)
EN 14112
6.4
Total aromatics (% by weight)
NF EN 12916
18.2
Polyaromatics (% by weight)
NF EN 12916
2.5
FAME content (% w/w) 96.5
Table 5
Fx F1 Fc1
TInd EGOo (h) 6.4  0.1 6.4 0.1
TInd
EGO1 (h) 8.6  0.1 7.7  0.1
 TInd =
(TInd
EGO1 - TInd
EGOo) (h)
2.2  0.2 1.3  0.2
Use of a resin C0 according to the present invention as an additive in engine gas oil
of type B100 makes it possible to reach an induction time greater than 8 hours
with a gain in the Rancimat test of more than 2 hours.
21
Example 3: Test of oxidation stability on a domestic fuel oil (DFO)
A test of oxidation stability according to standard ISO 12205 is carried out on a
heating fuel for domestic use, also called DFO ("domestic fuel oil") (DFO°), with
the characteristics given in Table 6 below.
Table 6
DFOo Distillation ASTM D86 (°C)
Total paraffins (% by weight) 12.95 0% 158.6
CFPP (°C) - NF EN 116 -5 5% 183.7
Pour point (°C) - NF-T60-105 -12 10% 194
Cloud point (°C) - NF EN 23015 -5 20% 215.4
MV15 (kg/m3) - NF EN ISO12185 829.23 30% 236.1
Sulphur content (mg/kg) 7.80 40% 255.60
Monoaromatics (% by weight) - NF EN 12916 15.7 50% 273.6
Diaromatics (% by weight) - NF EN 12916 2 60% 289.1
Triaromatics (% by weight) - NF EN 12916 0.5 70% 303.7
Total aromatics (% by weight) - NF EN 12916 18.2 80% 319.5
Polyaromatics (% by weight) - NF EN 12916 2.5 90% 337.1
VOME content (vol%) 0 95% 350
100% 358.6
The principle of the test according to standard ISO 12205 consists of exposing the
test sample to a temperature of 95°C for a period of 16 hours. Then the sample is
cooled to ambient temperature and filtered in order to determine the quantity of
deposits generated.
The test was also carried out on a sample of DFO1 corresponding to the pure DFO
(DFOo) with addition of 120 ppm of formulation F1 described above (50% of active
material).
22
The results of the tests of oxidation stability are given in Table 7 below.
Table 7
Oxidation stability
EN 12205 – unit g/m3
DFO° 204.3
DFO1 43.23
% reduction in deposits 78.8%
A substantial decrease in deposits is seen, with a reduction in deposits of nearly
79%. Thus, it is deduced from this that the use of resin C0 according to the
invention makes it possible to reduce the quantity of deposits formed during
storage of DFO significantly (about 80%).
The modified alkylphenol-aldehyde resins according to the invention have
particularly remarkable properties as antioxidant additive for motor fuel or
hydrocarbon-containing fuel compositions, in particular such as gas oils, diesel
fuels, gasolines, biofuels, jet fuels, domestic fuel oils (DFO) and heavy fuel oils.
The modified alkylphenol-aldehyde resins according to the invention are
particularly effective for the motor fuel or liquid hydrocarbon-containing fuel
compositions that comprise vegetable and/or animal oils and/or esters thereof.
The modified alkylphenol-aldehyde resins are particularly suitable for biodiesels of
animal and/or vegetable origin, alone or mixed with other compositions of motor
fuels or other fuels.
In particular, the modified alkylphenol-aldehyde resins according to the invention
improve the oxidation stability and/or storage stability of motor fuel or liquid
hydrocarbon-containing fuel compositions that comprise up to 100 % by weight of
fatty acid methyl esters (FAME) or fatty acid ethyl esters (FAEE), in particular
vegetable oil methyl esters (VOME) or vegetable oil ethyl esters (VOEE).

Claims
1. Use of at least one modified alkylphenol-aldehyde resin as additive for
improving the oxidation and/or storage stability of a motor fuel or liquid
hydrocarbon-containing fuel composition, said modified alkylphenol-aldehyde resin
being obtainable by Mannich reaction of an alkylphenol-aldehyde condensation
resin
 with at least one aldehyde and/or one ketone having from 1 to 8 carbon atoms,
preferably from 1 to 4 carbon atoms;
 and at least one hydrocarbon-containing compound having at least one
alkylmonoamine or alkylpolyamine (alkylamine) group, having between 1 and
30 carbon atoms, preferably between 4 and 30 carbon atoms,
said alkylphenol-aldehyde condensation resin itself being obtainable by
condensation
 of at least one alkylphenol substituted with at least one linear or branched alkyl
group having from 1 to 30 carbon atoms, preferably a monoalkylphenol,
 with at least one aldehyde and/or one ketone having from 1 to 8 carbon atoms,
preferably from 1 to 4 carbon atoms.
2. Use according to claim 1, for improving the storage stability of the motor fuel
or liquid hydrocarbon-containing fuel composition at a temperature less than 0°C,
preferably less than -5°C, more preferably less than or equal to -10°C.
3. Use according to one of claims 1 and 2, for reducing the quantity of deposits
formed during storage of the motor fuel or liquid hydrocarbon-containing fuel
composition.
4. Use according to any one of claims 1 to 3, wherein the modified alkylphenolaldehyde
resin is used as an additive in a form diluted in a solvent, preferably
aromatic.
24
5. Use according to any one of claims 1 to 4, wherein the modified alkylphenolaldehyde
resin is used in the motor fuel or liquid hydrocarbon-containing fuel
composition in combination with one or more additional additives.
6. Use according to claim 5, wherein the additional additives are selected from
dispersants/detergents, carrier oils, metal deactivators, metallic passivators,
antioxidants, dyes, antistatic additives, corrosion inhibitors, biocides, markers,
thermal stabilizers, emulsifiers, friction reducing agents, surfactants, cetane
improvers, anti-clouding agents, additives improving the conductivity, reodorants,
lubricity additives, lubricants and mixtures thereof.
7. Use according to any one of claims 1 to 6, wherein an amount of modified
alkylphenol-aldehyde resin comprised between 5 and 5000 ppmw, preferably
between 10 and 2000 ppm, more preferably between 50 and 1200 ppm, even
more preferably between 50 and 600 ppm, is added to the motor fuel or liquid
hydrocarbon-containing fuel composition.
8. Use according to any one of claims 1 to 7, wherein the motor fuel or liquid
hydrocarbon-containing fuel composition comprises a motor fuel or liquid
hydrocarbon-containing fuel selected from gas oils, diesel fuels, gasolines,
biofuels, jet fuels, domestic fuel oils (DFO) and heavy fuel oils.
9. Use according to any one of claims 1 to 8, wherein the motor fuel or liquid
hydrocarbon-containing fuel composition comprises a motor fuel or other fuel
selected from the middle distillates with a boiling point temperature comprised
between 100 and 500°C, preferably 140 to 400°C.
10. Use according to any one of claims 1 to 9, wherein the motor fuel or liquid
hydrocarbon-containing fuel composition comprises vegetable and/or animal oils
and/or esters thereof and/or biodiesels of animal and/or vegetable origin.
25
11. Use according to claim 10, wherein the esters are fatty acid methyl esters
(FAME) or fatty acid ethyl esters (FAEE), preferably vegetable oil methyl esters
(VOME) or vegetable oil ethyl esters (VOEE).
12. Use according to claim 11, wherein the motor fuel or liquid hydrocarboncontaining
fuel composition is a biodiesel of type B100 and whose value of
induction time (Tind) obtained by a Rancimat test according to standard DIN EN
15751 is greater than or equal to 8 hours.
13. Use according to claim 12, wherein a gain in value of induction time (Tind)
obtained by the Rancimat test according to standard DIN EN 15751 is greater than
or equal to 2.
14. Use according to any one of claims 1 to 13, wherein the modified alkylphenolaldehyde
resin can be obtained from at least one para-substituted alkylphenol,
preferably from p-nonylphenol.
15. Use according to any one of claims 1 to 14, wherein the modified alkylphenolaldehyde
resin can be obtained starting from at least one aldehyde and/or one
ketone selected from formaldehyde, acetaldehyde, propionaldehyde,
butyraldehyde, 2-ethylhexanal, benzaldehyde, acetone, and preferably starting
from at least formaldehyde.
16. Use according to any one of claims 1 to 15, wherein the modified alkylphenolaldehyde
resin is obtained starting from at least one alkylamine having at least one
primary amine group.
17. Use according to any one of claims 1 to 16, wherein the modified alkylphenolaldehyde
resin can be obtained starting from at least one fatty-chain alkylamine or
from a mixture of fatty-chain alkylamines, and preferably alkylamine(s) having a
number of carbon atoms between 12 and 24, preferably between 12 and 22.