U.S. patent application number 12/863498 was filed with the patent office on 2010-11-25 for production of additive mixtures.
This patent application is currently assigned to BASF SE. Invention is credited to Andreas Bauder, Andreas Daiss, Matthias Frohberger, Stefan Hirsch, Stephan Hoffmann, Wolfgang Kasel, Frank-Olaf Maehling, Peter Schaeffler, Peter Spang, Irene Troetsch-Schaller, Anja Vinckier, Siegfried Willert.
Application Number | 20100293842 12/863498 |
Document ID | / |
Family ID | 40637251 |
Filed Date | 2010-11-25 |
United States Patent
Application |
20100293842 |
Kind Code |
A1 |
Kasel; Wolfgang ; et
al. |
November 25, 2010 |
PRODUCTION OF ADDITIVE MIXTURES
Abstract
The invention relates to a method for producing additive
mixtures for fuel oils by mixing at least two additive components
in a dynamic mixer or a lamination mixer. The invention further
relates to additive mixtures obtained by said method and fuel oil
compositions containing said additive mixtures.
Inventors: |
Kasel; Wolfgang; (Nussloch,
DE) ; Troetsch-Schaller; Irene; (Bissersheim, DE)
; Spang; Peter; (St. Ingbert, DE) ; Maehling;
Frank-Olaf; (Mannheim, DE) ; Daiss; Andreas;
(Deidesheim, DE) ; Bauder; Andreas; (Mannheim,
DE) ; Vinckier; Anja; (Antwerpen, BE) ;
Hirsch; Stefan; (Neustadt, DE) ; Frohberger;
Matthias; (Heidelberg, DE) ; Willert; Siegfried;
(Ludwigshafen, DE) ; Schaeffler; Peter;
(Ludwigshafen, DE) ; Hoffmann; Stephan;
(Schifferstadt, DE) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND MAIER & NEUSTADT, L.L.P.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
BASF SE
Ludwigshafen
DE
|
Family ID: |
40637251 |
Appl. No.: |
12/863498 |
Filed: |
January 21, 2009 |
PCT Filed: |
January 21, 2009 |
PCT NO: |
PCT/EP2009/050652 |
371 Date: |
July 19, 2010 |
Current U.S.
Class: |
44/393 |
Current CPC
Class: |
C10L 1/143 20130101;
C10L 1/1973 20130101; C10L 10/14 20130101; C10L 1/1616
20130101 |
Class at
Publication: |
44/393 |
International
Class: |
C10L 1/195 20060101
C10L001/195 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 22, 2008 |
EP |
08150496.1 |
Claims
1-16. (canceled)
17. A process for producing additive mixtures for fuel oils, in
which at least two components of the additive mixture are mixed in
a mixer selected from mixing pumps, wherein the at least two
components of the additive mixture comprise (i) at least one cold
flow improver and (ii) at least one solvent.
18. The process according to claim 17, wherein said cold flow
improver is selected from (a) copolymers of ethylene with at least
one further ethylenically unsaturated monomer; (b) comb polymers;
(c) polyoxyalkylenes; (d) polar nitrogen compounds; (e)
sulfocarboxylic acids or sulfonic acids or derivatives thereof; (f)
poly(meth)acrylic esters; (g) alkylphenol-aldehyde resins; and
mixtures thereof.
19. The process according to claim 17, wherein said at least one
cold flow improver comprises (a) at least one copolymer of ethylene
with at least one further ethylenically unsaturated monomer.
20. The process according to claim 18, wherein said at least one
further ethylenically unsaturated monomer is selected from
alkenylcarboxylic esters, (meth)acrylic esters, styrene, styrene
derivatives and olefins other than ethylene.
21. The process according to claim 18, wherein said further
ethylenically unsaturated monomer comprises vinyl acetate.
22. The process according to claim 19, wherein said at least one
cold flow improver also comprises (d) at least one polar nitrogen
compound.
23. The process according to claim 17, wherein said solvent is
selected from aliphatic and aromatic hydrocarbons and mixtures
thereof.
24. The process according to claim 17, wherein said at least two
components of the additive mixture further comprise (iii) at least
one further fuel oil additive which is selected from detergent
additives, ashless dispersants, demulsifiers, dehazers, carrier
oils, cetane number improvers, metal deactivators, corrosion
inhibitors, antioxidants, lubricity improvers, defoamers,
antistats, stabilizers, color markers, fragrances and mixtures
thereof.
25. The process according to claim 17, wherein the mean mixing time
is at most 120 seconds.
26. An additive mixture obtained by a process according to claim
17.
27. A fuel oil composition comprising an additive mixture according
to claim 26.
28. The fuel oil composition according to claim 27, wherein the
fuel oil is a middle distillate.
Description
[0001] The present invention relates to a process for producing
additive mixtures for fuel oils by mixing at least two additive
components in a dynamic mixer or in a lamination mixer. The present
invention further relates to the additive mixtures obtainable via
this process and to fuel oil compositions which comprise such
additive mixtures.
[0002] Mineral oils and crude oils which comprise paraffinic waxes
exhibit a significant deterioration in the flow properties as the
temperature is lowered. The cause of this lies in the
crystallization, which sets in from the temperature of the cloud
point, of relatively long-chain paraffins which form large
platelet-shaped wax crystals. These wax crystals have a spongelike
structure and lead to inclusion of other fuel constituents in the
crystal structure.
[0003] The occurrence of these crystals leads to a deterioration in
the flow properties of the mineral oils and crude oils, as a result
of which disruption can occur in the extraction, transport, storage
and/or use of the oils. For instance, when the oils are transported
through pipelines, in winter in particular, there can be deposits
on the pipe walls and even complete blockage. In the case of
mineral oils, there may be blockage and conglutination of fuel
filters in motor vehicle engines (fuel filters) and boiler, which
prevents reliable metering of the fuels and, under some
circumstances, complete stoppage of the fuel supply occurs. At
temperatures below the pour point (PP), there is finally no longer
any flow of fuel.
[0004] To alleviate these problems, additives which frequently
consist of a combination of nucleators with the actual cold flow
improvers (CFIs) have already been added in low concentrations to
the mineral oils and crude oils for some time. Nucleators are
substances which generate crystal nuclei which promote the
formation of ultra small crystals. Cold flow improvers have similar
crystallization properties to the paraffins present in mineral oil
or crude oil, but prevent their growth. Moreover, wax antisettling
additives (WASAs) which prevent the settling of the ultra small
crystals in the oils are added to the crude oils and mineral oils.
Frequently, mixtures of CFIs and WASAs are also used, which are
also referred to as WAFIs (wax antisettling flow improvers).
[0005] These cold flow improvers are usually added as additive
packages to the mineral oils and crude oils. These additive
packages generally comprise, as well as the cold flow improvers, at
least one solvent and frequently also further additives, for
example detergent additives, dispersants, defoamers and others.
[0006] Since the composition of the crude oils and mineral oils
varies owing to the different origin of the crude oils and the
different operating conditions in the refineries, more or less
tailored additive packages have to be provided for the individual
oils. It is therefore of great economic significance to be able to
provide the additive packages in a rapid, flexible process with
reliably reproducible results. At the same time, the additive
packages should not only have good functional properties, for
example good cold flow-improving properties, but also good handling
properties, for example should be easily incorporable into the
oil.
[0007] In general, additive mixtures are produced batchwise, i.e.
one or more active ingredient components and a solvent are metered
successively into a vessel and then mixed by stirring or pumped
circulation. A disadvantage is the long time required for the
charging, heating and mixing. The achievement of sufficient
homogeneity requires, especially in the case of mixing of active
ingredients and solvents of different viscosity, prolonged stirring
or circulation over several hours to days. The desired or required
mixing temperature is generally established only slowly according
to the amounts of the components to be mixed and their
temperatures, and also the heating output set. Frequently, it
deviates significantly from the mean, for example at the metering
point of the components and at the heating elements, such that the
temperature profile is reproducible only with difficulty during the
mixing operation. Especially in the case of rapid heating at the
heating elements, for example the vessel jacket, significant
overheating can occur, which, in the course of the subsequent
storage of the additive packages, can lead to the sedimentation of
the suspended active ingredients or even to their thermal
decomposition.
[0008] In addition, the flowability or pumpability of dispersions
of these partly crystalline polymers is in many cases dependent on
the mixing conditions. Thus, partially or incompletely molten
formulations of partly crystalline polymers with solvents and
optionally further active ingredients lead to dispersions with a
high intrinsic pour point (PP), whereas completely melted polymers
give rise to dispersions with a significantly lower pour point. The
controlled establishment of a constant pour point of the
formulation produced, which is important for the product handling,
is thus possible in the case of batchwise mixing only with a high
level of additional technical complexity and/or time demands, for
example resulting from heating or cooling of the finished
mixture.
[0009] EP-A-1405896 describes a continuous process for producing
additive mixtures for mineral oils and mineral oil distillates, in
which a cold flow improver is mixed with a further cold flow
improver or a solvent in a static mixer at a defined temperature.
Static mixers are mixing systems in which the energy required for
the mixing operation is introduced by the mixing components. They
frequently comprise fixed internals and bring about mixing of the
components through exploitation of their flow energy.
[0010] The additive mixtures obtained with this mixing process no
longer have many of the disadvantages of the additive mixtures
which are obtained with the older batchwise mixing processes; the
mixing process is also significantly faster. However, some handling
properties of the additive mixtures obtained by the process of
EP-A-1405896, for example the lower mixing temperature and the
filterability, are still unsatisfactory. Moreover, it is virtually
impossible with static mixers to completely and homogeneously mix
components with very different viscosities or else components which
are present in the mixture in very different proportions.
[0011] It was therefore an object of the present invention to
provide additive mixtures for fuel oils which, as well as good
functional properties (i.e. properties for which these additives
are actually added to the fuel oils, for example cold
flow-improving properties), have improved handling properties
compared to the prior art additive mixtures, for example a
relatively low minimum mixing temperature (LMT) and/or a better
filterability of the fuel oil additized with them. Moreover, they
should also have an improved storage stability. In addition, it
should also be possible to compose the additive mixtures
homogeneously from components which have a very different viscosity
and/or are to be present in very different proportions in the
mixture.
[0012] The minimum mixing temperature is an important economic
factor for the blending of the fuel oils with the additives, since
the lower the minimum mixing temperature of an additive is, the
less the fuel oil has to be heated in order to be able to mix the
additive in homogeneously. The minimum mixing temperature is thus
important especially for those refineries which mix the additives
unheated into fuel oils or mix additives into unheated fuel oils.
When the minimum mixing temperature of the additive is high, there
may be filter problems after unheated mixing.
[0013] The filterability of additized fuel oils is a measure of the
solubility and miscibility of the additive used into the fuel oil.
In the context of the present invention, the filterability is
determined by means of the SEDAB method described below. A good
filterability is obtained when the additive added is readily
miscible into or soluble in the fuel oil.
[0014] A prolonged storage stability is likewise an important
economic factor, since it allows the production of the products
from stock, such that it is possible to cope more easily, for
example, with peaks in demand, or to allow production runs (for
individual additive compositions) to run for longer and hence in a
more economically viable manner, without the product quality
falling unacceptably in the course of prolonged storage.
[0015] The object is achieved by a process for producing additive
mixtures for fuel oils, in which at least two components of the
additive mixture are mixed in a mixer selected from dynamic mixers
and lamination mixers.
[0016] The statements made below regarding suitable and preferred
embodiments of the process according to the invention, of the
inventive additive mixture and of the inventive fuel oil
composition, especially of the components to be mixed, of the fuel
oils and of the mixers and of the mixing conditions, apply both
taken alone and in any conceivable combination with one
another.
[0017] In dynamic mixers, the energy input required for the mixing
operation is effected by the mixer itself. These mixers comprise
moving mixing units or a moving vessel. The most common are
so-called rotor-stator systems with a fixed housing (stator) and a
rotating machine part (rotor). In the intermediate spaces between
rotor and stator, the rotating motion of the rotor forms a shear
flow which is frequently but not necessarily turbulent. In this
shear flow, the components are mixed by virtue of new phase
interfaces constantly being created between them.
[0018] In principle, however, all types of dynamic mixers are
suitable for the process according to the invention.
[0019] The dynamic mixers are preferably selected from rotor mills,
toothed ring dispersing machines, inline dispersing machines,
colloid mills, corundum disc mills, scraped heat exchangers, mixing
pumps and ultrasound homogenizers. The dynamic mixers are more
preferably selected from rotor-stator systems, for example from
rotor mills, toothed ring dispersing machines, colloid mills,
corundum disc mills and mixing pumps. In particular, the dynamic
mixers are selected from toothed ring dispersing machines and
mixing pumps.
[0020] A further means of generating particularly good mixtures is
the use of lamination mixers. Lamination mixers are a specific type
of nondynamic mixers, in which the fluid streams to be mixed are
fanned out into a multitude of thin lamellae or films, and these
lamellae are subsequently merged with one another in an alternating
manner, such that diffusion and secondary flows result in very
rapid mixing. The fanning out of the incoming streams of the pure
mixture component can be effected, for example, by means of flow
dividers which divide the incoming streams into lamellar layers or
films of adjustable thickness. By virtue of an appropriate
three-dimensional arrangement, alternating layering of the lamellar
pure substance streams is brought about at the exit from the flow
divider, and, according to the design, may have a two-dimensional
structure in mutually adjacent planes or as concentric ring
streams. As a result of diffusion, a substance concentration
balance then takes place between the layers, and hence mixing of
the components.
[0021] The selection of suitable mixers depends upon factors
including the combination of the particular mixing components and
their use amount, and can be determined by the person skilled in
the art in the individual case, for example by means of simple
preliminary tests.
[0022] Preference is given to using a dynamic mixer. With regard to
suitable and preferred dynamic mixers, reference is made to the
remarks above.
[0023] In the process according to the invention, the components
can also be mixed in several mixers which are arranged in any
sequence, arrangement or combination, at least one of the mixers
being a dynamic mixer or a lamination mixer. The remaining mixers
may be any mixer types, for example one or more further dynamic
mixers and/or lamination mixers and/or static mixers. The mixers
may be arranged in series arrangement or in a combined series and
parallel arrangement.
[0024] In the process according to the invention, the components
are preferably mixed, however, in a single mixer.
[0025] The components are preferably mixed at elevated temperature,
preferably at least 30.degree. C., for example at from 30 to
180.degree. C. or from 30 to 150.degree. C. or from 30 to
100.degree. C., more preferably at least 50.degree. C., for example
at from 50 to 180.degree. C. or at from 50 to 150.degree. C. or at
from 50 to 100.degree. C., and especially at least 70.degree. C.,
for example at from 70 to 180.degree. C. or at from 70 to
150.degree. C. or at from 70 to 100.degree. C. The different
components may have different entrance temperatures at the
mixer.
[0026] The desired mixing temperature can be established either
before or during the mixing operation. The temperature is generally
established before the mixing operation by bringing the components
to be mixed to the desired temperature shortly before they are fed
into the mixer, or by maintaining them at the desired temperature
in a reservoir vessel. When the temperature can fall during the
supply, the components are sensibly first brought to a higher
temperature which falls to the desired mixing temperature during
the supply. The temperature is established during the mixing
operation generally by means of heating elements which are
installed on or in the mixer, for example through a jacket or a
tube bundle. The mixing temperature is preferably adjusted to the
desired temperature or a somewhat higher temperature before the
mixing operation by heating the components to be mixed.
[0027] The components can be supplied into the mixer by all
customary methods, for example by direct addition of all components
in pure form or by addition of suitable premixtures. When
premixtures are used, they can be formed in a separate step or, as
mentioned above, be produced in a mixer connected upstream of the
actual (dynamic or lamination) mixer.
[0028] In the process according to the invention, the establishment
of a homogenous mixture with the desired product properties
generally takes at most 200 seconds, preferably at most 120
seconds, more preferably at most 60 seconds and in particular at
most 45 seconds, especially at most 30 seconds. These time data are
the mean mixing time, i.e. the mean duration of residence of the
components in the mixing zone.
[0029] The process according to the invention can be configured as
a batchwise, semibatchwise or continuous process. However, it is
preferably a continuous process.
[0030] In the continuous process, the mass throughput is preferably
from 0.001 to 200 t/h, more preferably from 0.01 to 100 t/h and
especially from 1 to 100 t/h.
[0031] In the continuous process variant, a dynamic mixer or a
lamination mixer is generally supplied continuously with the
components to be mixed via suitable supply lines, and the
components can be supplied to the mixer, as already stated, either
by direct addition of all components in pure form or by addition of
suitable premixtures. The pure components are preferably brought to
the desired mixing temperature or to a temperature somewhat above
the desired mixing temperature by suitable measures before the
entry into the mixer. Since the mixing duration/residence time is
generally very short, it is generally unnecessary in steady-state
continuous operation to heat the mixer. On completion of mixing,
the mixture is then discharged continuously from the mixer.
[0032] After the mixing operation, it is favorable to cool the
mixture formed before discharge from the mixing system. Any
customary cooling apparatus is suitable, especially that for
indirect cooling, such as heat exchangers. This achieves the effect
that the mixture remains stable at ambient temperature.
[0033] In a preferred embodiment of the invention, the process
according to the invention serves to produce CFI additive packages.
Accordingly, the at least two components of the additive mixture
comprise
(i) at least one cold flow improver and (ii) at least one
solvent.
[0034] Component (i) and component (ii) are used in a weight ratio
of preferably from 1:99 to 99:1, more preferably from 10:90 to
90:10 and especially from 20:80 to 80:20.
[0035] The cold flow improvers may be all customary prior art cold
flow improvers. However, the cold flow improver is preferably
selected from [0036] (a) copolymers of ethylene with at least one
further ethylenically unsaturated monomer; [0037] (b) comb
polymers; [0038] (c) polyoxyalkylenes; [0039] (d) polar nitrogen
compounds; [0040] (e) sulfocarboxylic acids or sulfonic acids or
derivatives thereof; [0041] (f) poly(meth)acrylic esters; [0042]
(g) alkylphenol-aldehyde resins; and mixtures thereof.
[0043] In the copolymers of ethylene with at least one further
ethylenically unsaturated monomer (a), the monomer is preferably
selected from alkenylcarboxylic esters, (meth)acrylic esters,
styrene, styrene derivatives and olefins.
[0044] Suitable olefins are, for example, those having from 3 to 10
carbon atoms and having from 1 to 3, preferably having 1 or 2,
especially having one carbon-carbon double bond(s). In the latter
case, the carbon-carbon double bond may be arranged either
terminally (.alpha.-olefin) or internally. However, preference is
given to .alpha.-olefins, particular preference to .alpha.-olefins
having from 3 to 6 carbon atoms, such as propene, 1-butene,
1-pentene and 1-hexene.
[0045] Suitable styrene derivatives are
C.sub.1-C.sub.4-alkyl-substituted styrenes such as
.alpha.-methylstyrene, 2-, 3- or 4-methylstyrene, 2-, 3- or
4-ethylstyrene, 2-, 3- or 4-propyl-styrene, 4-isopropylstyrene, 2-,
3- or 4-n-butylstyrene, 4-isobutylstyrene, 4-tert-butylstyrene,
2,4- or 2,6-dimethylstyrene and 2,4- or 2,6-diethylstyrene. Among
these, preference is given to .alpha.-methylstyrene, 2-, 3- or
4-methylstyrene and 2,4- or 2,6-dimethylstyrene and especially 2-,
3- or 4-methylstyrene and 2,4- or 2,6-dimethyl-styrene.
[0046] Suitable (meth)acrylic esters are, for example, esters of
(meth)acrylic acid with C.sub.1-C.sub.20-alkanols, especially with
methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol,
isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol,
2-ethylhexanol, nonanol, decanol, 2-propylheptanol, undecanol,
lauryl alcohol, tridecanol, myristyl alcohol, pentadecanol,
palmityl alcohol, heptadecanol, stearyl alcohol, nonadecanol and
eicosanol.
[0047] Suitable alkenyl carboxylates are, for example, the vinyl
and propenyl esters of carboxylic acids having from 2 to 20 carbon
atoms, whose hydrocarbon radical may be linear or branched. Among
these, preference is given to the vinyl esters. Among the
carboxylic acids with a branched hydrocarbon radical, preference is
given to those whose branch is in the .alpha. position to the
carboxyl group, the .alpha. carbon atom more preferably being
tertiary, i.e. the carboxylic acid being a so-called neocarboxylic
acid. However, the hydrocarbon radical of the carboxylic acid is
more preferably linear.
[0048] Examples of suitable alkenyl carboxylates are vinyl acetate,
vinyl propionate, vinyl butyrate, vinyl neopentanoate, vinyl
hexanoate, vinyl neononanoate, vinyl neodecanoate and the
corresponding propenyl esters, preference being given to the vinyl
esters. A particularly preferred alkenyl carboxylate is vinyl
acetate.
[0049] More preferably, the ethylenically unsaturated monomer is
selected from alkenyl carboxylates. Even more preferably, the
ethylenically unsaturated monomer comprises vinyl acetate.
[0050] Also suitable are copolymers which comprise two or more
different alkenyl carboxylates in copolymerized form, which differ
in the alkenyl function and/or in the carboxylic acid group. One of
the alkenyl carboxylates is preferably vinyl acetate. Likewise
suitable are copolymers which, as well as the alkenyl
carboxylate(s), comprise at least one olefin and/or at least one
(meth)acrylic ester and/or styrene and/or at least one styrene
derivative in copolymerized form. Among these, preference is given
to terpolymers, i.e. copolymers which, as well as an alkenyl
carboxylate, which is preferably vinyl acetate, comprise an olefin
or a (meth)acrylic ester or styrene or a styrene derivative in
copolymerized form. With regard to suitable and preferred olefins,
alkenyl carboxylates, (meth)acrylic esters and styrene derivatives,
reference is made to the above remarks.
[0051] The at least one ethylenically unsaturated monomer is
copolymerized in the copolymer in a total amount of preferably from
1 to 30 mol %, more preferably of from 1 to 25 mol % and especially
of from 5 to 20 mol %, based on the overall copolymer.
[0052] The copolymer (a) preferably has a number-average molecular
weight Mn of from 500 to 20 000, more preferably from 750 to 15
000.
[0053] Comb polymers (b) are, for example, those described in
"Comb-Like Polymers. Structure and Properties", N. A. Plate and V.
P. Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pages 117 to 253
(1974). Among those described there, suitable comb polymers are,
for example, those of the formula II
##STR00001##
in which
D is R.sup.17, COOR.sup.17, OCOR.sup.17, R.sup.18, OCOR.sup.17 or
OR.sup.17,
E is H, CH.sub.3, D or R.sup.18,
G is H or D,
[0054] J is H, R.sup.18, R.sup.18COOR.sup.17, aryl or
heterocyclyl,
K is H, COOR.sup.18, OCOR.sup.18, OR.sup.18 or COOH,
[0055] L is H, R.sup.18, COOR.sup.18, OCOR.sup.18, COOH or aryl,
where R.sup.17 is a hydrocarbon radical having at least 10 carbon
atoms, preferably having from 10 to 30 carbon atoms, R.sup.18 is a
hydrocarbon radical having at least one carbon atom, preferably
having from 1 to 30 carbon atoms, m is a molar fraction in the
range from 1.0 to 0.4 and n is a molar fraction in the range from 0
to 0.6.
[0056] Preferred comb polymers are obtainable, for example, by
copolymerization of maleic anhydride or fumaric acid with another
ethylenically unsaturated monomer, for example with an
.alpha.-olefin or an unsaturated ester, such as vinyl acetate, and
subsequent esterification of the anhydride or acid function with an
alcohol having at least 10 carbon atoms. Further preferred comb
polymers are copolymers of .alpha.-olefins and esterified
comonomers, for example esterified copolymers of styrene and maleic
anhydride or esterified copolymers of styrene and fumaric acid.
Also suitable are mixtures of comb polymers. Comb polymers may also
be polyfumarates or polymaleates. Homo- and copolymers of vinyl
ethers are also suitable comb polymers.
[0057] Suitable polyoxyalkylenes (c) are, for example,
polyoxyalkylene esters, ethers, ester/ethers and mixtures thereof.
The polyoxyalkylene compounds preferably comprise at least one,
more preferably at least two, linear alkyl group(s) having from 10
to 30 carbon atoms and a polyoxyalkylene group having a molecular
weight of up to 5000. The alkyl group of the polyoxyalkylene
radical preferably comprises from 1 to 4 carbon atoms. Such
polyoxyalkylene compounds are described, for example, in EP-A-0 061
895 and in U.S. Pat. No. 4,491,455, which are hereby fully
incorporated by reference. Preferred polyoxyalkylene esters, ethers
and ester/ethers have the general formula III
R.sup.19[O--(CH.sub.2).sub.y].sub.xO--R.sup.20 (III)
in which R.sup.19 and R.sup.20 are each independently R.sup.21,
R.sup.21--CO--, R.sup.21--O--CO(CH.sub.2).sub.z-- or
R.sup.21--O--CO(CH.sub.2).sub.z--CO--, where R.sup.21 is linear
C.sub.1-C.sub.30-alkyl, y is from 1 to 4, x is from 2 to 200, and z
is from 1 to 4.
[0058] Preferred polyoxyalkylene compounds of the formula III in
which both R.sup.19 and R.sup.20 are R.sup.21 are polyethylene
glycols and polypropylene glycols having a number-average molecular
weight of from 100 to 5000. Preferred polyoxyalkylenes of the
formula III in which one of the R.sup.19 radicals is R.sup.21 and
the other is R.sup.21--CO-- are polyoxyalkylene esters of fatty
acids having from 10 to 30 carbon atoms, such as stearic acid or
behenic acid. Preferred polyoxyalkylene compounds in which both
R.sup.19 and R.sup.20 are an R.sup.21--CO-- radical are diesters of
fatty acids having from 10 to 30 carbon atoms, preferably of
stearic acid or behenic acid.
[0059] The polar nitrogen compounds (d), which are advantageously
oil-soluble, may be either ionic or nonionic and preferably have at
least one, more preferably at least 2, substituent(s) of the
formula >NR.sup.22 in which R.sup.22 is a
C.sub.8-C.sub.40-hydrocarbon radical. The nitrogen substituents may
also be quaternized, i.e. be in cationic form. One example of such
nitrogen compounds is that of ammonium salts and/or amides or
imides which are obtainable by the reaction of at least one amine
substituted with at least one hydrocarbon radical with a carboxylic
acid having from 1 to 4 carboxyl groups or with a suitable
derivative thereof. The amines preferably comprise at least one
linear C.sub.8-C.sub.40-alkyl radical. Suitable primary amines are,
for example, octylamine, nonylamine, decylamine, undecylamine,
dodecylamine, tetradecylamine and the higher linear homologs.
Suitable secondary amines are, for example, dioctadecylamine and
methylbehenylamine. Also suitable are amine mixtures, in particular
amine mixtures obtainable on the industrial scale, such as fatty
amines or hydrogenated tallamines, as described, for example, in
Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 2000
electronic release, "Amines, aliphatic" chapter. Acids suitable for
the reaction are, for example, cyclohexane-1,2-dicarboxylic acid,
cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic
acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic
acid, terephthalic acid and succinic acids substituted with
long-chain hydrocarbon radicals.
[0060] A further example of polar nitrogen compounds is that of
ring systems which bear at least two substituents of the formula
-A-NR.sup.23R.sup.24 in which A is a linear or branched aliphatic
hydrocarbon group which is optionally interrupted by one or more
groups selected from O, S, NR.sup.35 and CO, and R.sup.23 and
R.sup.24 are each a C.sub.9-C.sub.40-hydrocarbon radical which is
optionally interrupted by one or more groups selected from O, S,
NR.sup.35 and CO, and/or substituted by one or more substituents
selected from OH, SH and NR.sup.35R.sup.36 where R.sup.35 is
C.sub.1-C.sub.40-alkyl which is optionally interrupted by one or
more moieties selected from CO, NR.sup.35, O and S, and/or
substituted by one or more radicals selected from
NR.sup.37R.sup.38, OR.sup.37, SR.sup.37, COR.sup.37, COOR.sup.37,
CONR.sup.37R.sup.38, aryl or heterocyclyl, where R.sup.37 and
R.sup.38 are each independently selected from H or
C.sub.1-C.sub.4-alkyl; and R.sup.36 is H or R.sup.35.
[0061] A is preferably a methylene or polymethylene group having
from 2 to 20 methylene units. Examples of suitable R.sup.23 and
R.sup.24 radicals are 2-hydroxyethyl, 3-hydroxypropyl,
4-hydroxybutyl, 2-ketopropyl, ethoxyethyl and propoxypropyl. The
cyclic system may be homocyclic, heterocyclic, fused polycyclic or
nonfused polycyclic systems. The ring system is preferably carbo-
or heteroaromatic, in particular carboaromatic. Examples of such
polycyclic ring systems are fused benzoid structures such as
naphthalene, anthracene, phenanthrene and pyrene, fused nonbenzoid
structures such as azulene, indene, hydrindene and fluorene,
nonfused polycycles such as diphenyl, heterocycles such as
quinoline, indole, dihydroindole, benzofuran, coumarin,
isocoumarin, benzo-thiophene, carbazole, diphenylene oxide and
diphenylene sulfide, nonaromatic or partly saturated ring systems
such as decalin, and three-dimensional structures such as
.alpha.-pinene, camphene, bornylene, norbornane, norbornene,
bicyclooctane and bicyclooctene.
[0062] A further example of suitable polar nitrogen compounds is
that of condensates of long-chain primary or secondary amines with
carboxyl group-comprising polymers.
[0063] The polar nitrogen compounds mentioned here are described in
WO 00/44857 and also in the references cited therein, which are
hereby fully incorporated by reference.
[0064] Suitable polar nitrogen compounds are also described, for
example, in DE-A-198 48 621, DE-A-196 22 052 or EP-B 398 101, which
are hereby incorporated by reference.
[0065] Preferred polar nitrogen compounds are ammonium salts and/or
amides or imides which are obtainable by the reaction of at least
one amine substituted by at least one hydrocarbon radical with a
carboxylic acid having from 1 to 4 carboxyl groups or with a
suitable derivative thereof. Among these, preference is given to
ammonium salts and/or amides or imides of succinic acid substituted
by a long-chain hydrocarbon radical, especially by a polyisobutyl
radical.
[0066] Suitable sulfocarboxylic acids/sulfonic acids or their
derivatives (e) are, for example, those of the general formula
IV
##STR00002##
in which Y is SO.sub.3.sup.-(NR.sup.25.sub.3R.sup.26).sup.+,
SO.sub.3.sup.-(NHR.sup.25.sub.2R.sup.26).sup.+,
SO.sub.3.sup.-(NH.sub.2R.sup.25.sub.2R.sup.26),
SO.sub.3.sup.-(NH.sub.3R.sup.26) or SO.sub.2NR.sup.25R.sup.26, X is
Y, CONR.sup.25R.sup.27,
CO.sub.2.sup.-(NR.sup.25.sub.3R.sup.27).sup.+,
CO.sub.2.sup.-(NHR.sup.252R.sup.27).sup.+, R.sup.28--COOR.sup.27,
NR.sup.25COR.sup.27, R.sup.28OR.sup.27, R.sup.28OCOR.sup.27,
R.sup.28R.sup.27, N(COR.sup.25)R.sup.27 or
Z.sup.-(NR.sup.25.sub.3R.sup.27).sup.+, where R.sup.25 is a
hydrocarbon radical, R.sup.26 and R.sup.27 are each alkyl,
alkoxyalkyl or polyalkoxyalkyl having at least 10 carbon atoms in
the main chain, R.sup.28 is C.sub.2-C.sub.5-alkylene, Z.sup.- is
one anion equivalent and A and B are each alkyl, alkenyl or two
substituted hydrocarbon radicals or, together with the carbon atoms
to which they are bonded, form an aromatic or cycloaliphatic ring
system.
[0067] Such sulfocarboxylic acids and sulfonic acids and their
derivatives are described in EP-A-0 261 957, which is hereby fully
incorporated by reference.
[0068] Suitable poly(meth)acrylic esters (f) are either homo- or
copolymers of acrylic and methacrylic esters. Preference is given
to copolymers of at least two different (meth)acrylic esters which
differ in the esterified alcohol. The copolymer optionally
comprises a further, different copolymerized olefinically
unsaturated monomer. The weight-average molecular weight of the
polymer is preferably from 50 000 to 500 000. A particularly
preferred polymer is a copolymer of methacrylic acid and
methacrylic esters of saturated C.sub.14- and C.sub.15-alcohols, in
which the acid groups have been neutralized with hydrogenated
tallamine. Suitable poly(meth)acrylic esters are described, for
example, in WO 00/44857, which is fully incorporated herein by way
of reference.
[0069] Suitable alkylphenol-aldehyde resins (g) are described, for
example, in Rompp Chemie Lexikon, 9th edition, Thieme Verlag,
1988-1992, page 3352. They are oil-soluble polycondensation
products of aliphatic aldehydes having generally from 1 to 4 carbon
atoms, such as formaldehyde, acetaldehyde, propionaldehyde and
butyraldehyde, especially formaldehyde, with phenols which bear 1
or 2 alkyl groups, preferably 1 alkyl group, having from 1 to 50,
preferably from 1 to 20 and especially from 4 to 12 carbon atoms in
the ortho or para position. The molecular weight of these
polycondensates is generally in the range from 400 to 10 000,
preferably from 400 to 5000.
[0070] The at least one cold flow improver preferably comprises at
least one copolymer of ethylene with at least one further
ethylenically unsaturated monomer (a). With regard to preferred
copolymers, reference is made to the above remarks.
[0071] Also suitable are mixtures of copolymers (a) with at least
one of the cold flow improvers (b) to (g).
[0072] In particular, the at least one cold flow improver (i) is a
copolymer of ethylene with at least one further ethylenically
unsaturated monomer (a), more preferably a copolymer of ethylene
with at least one alkenyl carboxylate or a copolymer of ethylene
with an alkenyl carboxylate and a (meth)acrylic ester or a
copolymer of ethylene with an alkenyl carboxylate and styrene, and
especially an ethylene/vinyl acetate copolymer.
[0073] In an alternatively preferred embodiment, the at least one
cold flow improver (i) is a mixture of at least one copolymer of
ethylene with at least one further ethylenically unsaturated
monomer (a) with at least one polar nitrogen compound (d). With
regard to suitable and preferred cold flow improvers (a) and (d),
reference is made to the above remarks.
[0074] The at least one solvent (ii) is a solvent for the at least
one cold flow improver (i) and is preferably selected from
aliphatic and aromatic hydrocarbons and mixtures thereof. What are
used are generally solvents/solvent mixtures as are customary for
fuel additive packages. Examples thereof are gasoline fractions,
kerosene, decane, pentadecane, toluene, xylene, ethylbenzene, or
else commercial solvent mixtures such as Solvent Naphtha,
Shellsol.RTM. AB, Solvesso.RTM. 150, Solvesso.RTM. 200,
Exxsol.RTM., ISOPAR.RTM. and Shellsol.RTM. D types. It is
optionally also additionally possible to use more polar solvents,
for example higher alcohols having from 4 to 14 carbon atoms, such
as n-butanol, 2-ethylhexanol, decanol, isodecanol or isotridecanol,
or higher ethers such as di-n-butyl ether, or esters, which then
act as solubilizers.
[0075] In a preferred embodiment of the invention, the at least two
components to be mixed, as well as components (i) and (ii), also
comprise [0076] (iii) at least one further fuel oil additive which
is selected from detergent additives, ashless dispersants,
demulsifiers, dehazers, carrier oils, cetane number improvers,
metal deactivators, corrosion inhibitors, antioxidants, lubricity
improvers, defoamers, antistats, stabilizers, color markers,
fragrances and mixtures thereof.
[0077] The detergent additives are preferably amphiphilic
substances which have at least one hydrophobic hydrocarbon radical
having a number-average molecular weight (M.sub.a) of from 85 to 20
000 and at least one polar moiety which is selected from: [0078]
(A) mono- or polyamino groups having up to 6 nitrogen atoms, at
least one nitrogen atom having basic properties; [0079] (B) nitro
groups, optionally in combination with hydroxyl groups; [0080] (C)
hydroxyl groups in combination with mono- or polyamino groups, at
least one nitrogen atom having basic properties; [0081] (D)
carboxyl groups or their alkali metal or alkaline earth metal
salts; [0082] (E) sulfonic acid groups or their alkali metal or
alkaline earth metal salts; [0083] (F) polyoxy-C2-C4-alkylene
moieties which are terminated by hydroxyl groups, mono- or
polyamino groups, at least one nitrogen atom having basic
properties, or by carbamate groups; [0084] (G) carboxylic ester
groups; [0085] (H) moieties which derive from succinic anhydride
and have hydroxyl and/or amino and/or amido and/or imido groups;
and/or [0086] (I) moieties obtained by Mannich reaction of
substituted phenols with aldehydes and mono- or polyamines.
[0087] The hydrophobic hydrocarbon radical in the above detergent
additives, which ensures the adequate solubility in the fuel oil,
has a number-average molecular weight (M.sub.n) of from 85 to 20
000, especially from 113 to 10 000, in particular from 300 to 5000.
Typical hydrophobic hydrocarbon radicals, especially in conjunction
with the polar moieties (A), (C), (H) and (I), include relatively
long-chain alkyl or alkenyl groups, especially the polypropenyl,
polybutenyl and polyisobutenyl radical, each having M.sub.n=from
300 to 5000, especially from 500 to 2500, in particular from 700 to
2300.
[0088] Examples of the above groups of detergent additives include
the following:
[0089] Additives comprising mono- or polyamino groups (A) are
preferably polyalkenemono- or polyalkenepolyamines based on
polypropene or conventional (i.e. having predominantly internal
double bonds) polybutene or polyisobutene having Mn=from 300 to
5000. When polybutene or polyisobutene having predominantly
internal double bonds (usually in the beta- and gamma-position) are
used as starting materials in the production of the additives, a
possible production route is by chlorination and subsequent
amination or by oxidation of the double bond with air or ozone to
give the carbonyl or carboxyl compound and subsequent amination
under reductive (hydrogenating) conditions. The amines used here
for the amination may be, for example, ammonia, monoamines or
polyamines, such as dimethylaminopropylamine, ethylenediamine,
diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
Corresponding additives based on polypropene are described in
particular in WO-A-94/24231.
[0090] Further preferred additives comprising monoamino groups (A)
are the hydrogenation products of the reaction products of
polyisobutenes having an average degree of polymerization P of from
5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and
oxygen, as described in particular in WO-A-97/03946.
[0091] Further preferred additives comprising monoamino groups (A)
are the compounds obtainable from polyisobutene epoxides by
reaction with amines and subsequent dehydration and reduction of
the amino alcohols, as described in particular in DE-A-196 20
262.
[0092] Additives comprising nitro groups (B), optionally in
combination with hydroxyl groups, are preferably reaction products
of polyisobutenes having an average degree of polymerization P=from
5 to 100 or from 10 to 100 with nitrogen oxides or mixtures of
nitrogen oxides and oxygen, as described in particular in
WO-A-96/03367 and WO-A-96/03479. These reaction products are
generally mixtures of pure nitropolyisobutenes (e.g.
.alpha.,.beta.-dinitropolyisobutene) and mixed
hydroxynitropolyisobutenes (e.g.
.alpha.-nitro-.beta.-hydroxypolyisobutene).
[0093] Additives comprising hydroxyl groups in combination with
mono- or polyamino groups (C) are in particular reaction products
of polyisobutene epoxides obtainable from polyisobutene having
preferably predominantly terminal double bonds and Mn=from 300 to
5000, with ammonia or mono- or polyamines, as described in
particular in EP-A-476 485.
[0094] Additives comprising carboxyl groups or their alkali metal
or alkaline earth metal salts (D) are preferably copolymers of
C.sub.2-C.sub.40-olefins with maleic anhydride which have a total
molar mass of from 500 to 20 000 and some or all of whose carboxyl
groups have been converted to the alkali metal or alkaline earth
metal salts and any remainder of the carboxyl groups has been
reacted with alcohols or amines. Such additives are disclosed in
particular by EP-A-307 815. Such additives serve mainly to prevent
valve seat wear and can, as described in WO-A-87/01126,
advantageously be used in combination with customary fuel
detergents such as poly(iso)buteneamines or polyetheramines.
[0095] Additives comprising sulfonic acid groups or their alkali
metal or alkaline earth metal salts (E) are preferably alkali metal
or alkaline earth metal salts of an alkyl sulfosuccinate, as
described in particular in EP-A-639 632. Such additives serve
mainly to prevent valve seat wear and can be used advantageously in
combination with customary fuel detergents such as
poly(iso)buteneamines or polyetheramines.
[0096] Additives comprising polyoxy-C.sub.2-C.sub.4-alkylene
moieties (F) are preferably polyethers or polyetheramines which are
obtainable by reaction of C.sub.2-C.sub.60-alkanols,
C.sub.6-C.sub.30-alkane-diols, mono- or
di-C.sub.2-C.sub.30-alkylamines,
C.sub.1-C.sub.30-alkylcyclohexanols or
C.sub.1-C.sub.30-alkylphenols with from 1 to 30 mol of ethylene
oxide and/or propylene oxide and/or butylene oxide per hydroxyl
group or amino group and, in the case of the polyether amines, by
subsequent reductive amination with ammonia, monoamines or
polyamines. Such products are described in particular in EP-A-310
875, EP-A-356 725, EP-A-700 985 and U.S. Pat. No. 4,877,416. In the
case of polyethers, such products also have carrier oil properties.
Typical examples of these are tridecanol butoxylates, isotridecanol
butoxylates, isononylphenol butoxylates and polyisobutenol
butoxylates and propoxylates and also the corresponding reaction
products with ammonia.
[0097] Additives comprising carboxylic ester groups (G) are
preferably esters of mono-, di- or tricarboxylic acids with
long-chain alkanols or polyols, in particular those having a
minimum viscosity of 2 mm.sup.2/s at 100.degree. C., as described
in particular in DE-A-38 38 918. The mono-, di- or tricarboxylic
acids used may be aliphatic or aromatic acids, and particularly
suitable ester alcohols or ester polyols are long-chain
representatives having, for example, from 6 to 24 carbon atoms.
Typical representatives of the esters are adipates, phthalates,
isophthalates, terephthalates and trimellitates of isooctanol, of
isononanol, of isodecanol and of isotridecanol. Such products also
have carrier oil properties.
[0098] Additives comprising moieties derived from succinic
anhydride and having hydroxyl and/or amino and/or amido and/or
imido groups (H) are preferably corresponding derivatives of alkyl-
or alkenyl-substituted succinic anhydride and especially the
corresponding derivatives of polyisobutenylsuccinic anhydride which
are obtainable by reacting conventional or highly reactive
polyisobutene having M.sub.n=from 300 to 5000 with maleic anhydride
by a thermal route or via the chlorinated polyisobutene. Particular
interest attaches to derivatives with aliphatic polyamines such as
ethylene-diamine, diethylenetriamine, triethylenetetramine or
tetraethylenepentamine. The moieties having hydroxyl and/or amino
and/or amido and/or imido groups are, for example, carboxylic acid
groups, acid amides of monoamines, acid amides of di- or polyamines
which, in addition to the amide function, also have free amine
groups, succinic acid derivatives having an acid and an amide
function, carboximides with monoamines, carboximides with di- or
polyamines which, in addition to the imide function, also have free
amine groups, or diimides which are formed by the reaction of di-
or polyamines with two succinic acid derivatives. Such fuel
additives are described in particular in U.S. Pat. No.
4,849,572.
[0099] Additives comprising moieties (I) obtained by Mannich
reaction of substituted phenols with aldehydes and mono- or
polyamines are preferably reaction products of
polyisobutene-substituted phenols with formaldehyde and mono- or
polyamines such as ethylenediamine, diethylenetriamine,
triethylenetetramine, tetraethylenepentamine or
dimethylaminopropylamine. The polyisobutenyl-substituted phenols
may stem from conventional or highly reactive polyisobutene having
M.sub.n=from 300 to 5000. Such "polyisobutene-Mannich bases" are
described in particular in EP-A-831 141.
[0100] For a more precise definition of the fuel additives detailed
individually, reference is explicitly made here to the disclosures
of the abovementioned prior art documents. Particular preference is
given to detergent additives from group (H). These are preferably
the reaction products of alkyl- or alkenyl-substituted succinic
anhydrides, especially of polyisobutenylsuccinic anhydrides, with
amines. It will be appreciated that these reaction products are
obtainable not only when substituted succinic anhydride is used,
but also when substituted succinic acid or suitable acid
derivatives, such as succinyl halides or succinic esters, are
used.
[0101] Particularly preferred detergent additives are
polyisobutenyl-substituted succinimides, especially the imides with
aliphatic polyamines. Particularly preferred polyamines are
diethylenetriamine, tetraethylenepentamine and
pentaethylenehexamine, particular preference being given to
tetraethylenepentamine. The polyisobutenyl radical has a
number-average molecular weight M.sub.n of preferably from 500 to
5000, more preferably from 500 to 2000 and in particular of about
1000.
[0102] It is self-evident that the detergent additives can be used
alone or in combination with at least one of the aforementioned
detergent additives.
[0103] Suitable mineral carrier oils are the fractions obtained in
crude oil processing, such as brightstock or base oils having
viscosities, for example, from the SN 500-2000 class; but also
aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols.
Likewise useful is a fraction which is obtained in the refining of
mineral oil and is known as "hydrocrack oil" (vacuum distillate cut
having a boiling range of from about 360 to 500.degree. C.,
obtainable from natural mineral oil which has been catalytically
hydrogenated under high pressure and isomerized and also
deparaffinized). Likewise suitable are mixtures of abovementioned
mineral carrier oils.
[0104] Examples of synthetic carrier oils are selected from:
polyolefins (poly-alpha-olefins or poly(internal olefin)s),
(poly)esters, (poly)alkoxylates, polyethers, aliphatic polyether
amines, alkylphenol-started polyethers, alkylphenol-started
polyether amines and carboxylic esters of long-chain alkanols.
[0105] Examples of suitable polyolefins are olefin polymers having
M.sub.n=from 400 to 1800, in particular based on polybutene or
polyisobutene (hydrogenated or unhydrogenated).
[0106] Examples of suitable polyethers or polyetheramines are
preferably compounds comprising polyoxy-C.sub.2-C.sub.4-alkylene
moieties which are obtainable by reacting
C.sub.2-C.sub.60-alkanols, C.sub.6-C.sub.30-alkanediols, mono- or
di-C.sub.2-C.sub.30-alkylamines,
C.sub.1-C.sub.30-alkylcyclo-hexanols or
C.sub.1-C.sub.30-alkylphenols with from 1 to 30 mol of ethylene
oxide and/or propylene oxide and/or butylene oxide per hydroxyl
group or amino group, and, in the case of the polyether amines, by
subsequent reductive amination with ammonia, monoamines or
polyamines. Such products are described in particular in EP-A-310
875, EP-A-356 725, EP-A-700 985 and U.S. Pat. No. 4,877,416. For
example, the polyether amines used may be
poly-C.sub.2-C.sub.6-alkylene oxide amines or functional
derivatives thereof. Typical examples thereof are tridecanol
butoxylates or isotridecanol butoxylates, isononylphenol
butoxylates and also polyisobutenol butoxylates and propoxylates,
and also the corresponding reaction products with ammonia.
[0107] Examples of carboxylic esters of long-chain alkanols are in
particular esters of mono-, di- or tricarboxylic acids with
long-chain alkanols or polyols, as described in particular in
DE-A-38 38 918. The mono-, di- or tricarboxylic acids used may be
aliphatic or aromatic acids; suitable ester alcohols or polyols are
in particular long-chain representatives having, for example, from
6 to 24 carbon atoms. Typical representatives of the esters are
adipates, phthalates, isophthalates, terephthalates and
trimellitates of isooctanol, isononanol, isodecanol and
isotridecanol, for example di(n- or isotridecyl) phthalate.
[0108] Further suitable carrier oil systems are described, for
example, in DE-A-38 26 608, DE-A-41 42 241, DE-A-43 09 074, EP-A-0
452 328 and EP-A-0 548 617, which are explicitly incorporated
herein by way of reference.
[0109] Examples of particularly suitable synthetic carrier oils are
alcohol-started polyethers having from about 5 to 35, for example
from about 5 to 30, C.sub.3-C.sub.6-alkylene oxide units, for
example selected from propylene oxide, n-butylene oxide and
isobutylene oxide units, or mixtures thereof. Nonlimiting examples
of suitable starter alcohols are long-chain alkanols or phenols
substituted by long-chain alkyl in which the long-chain alkyl
radical is in particular a straight-chain or branched
C.sub.6-C.sub.18-alkyl radical. Preferred examples include
tridecanol and nonylphenol.
[0110] Further suitable synthetic carrier oils are alkoxylated
alkylphenols, as described in DE-A-10 102 913.6.
[0111] Preferred carrier oils are synthetic carrier oils,
particular preference being given to polyethers.
[0112] Suitable corrosion inhibitors are, for example, succinic
esters, in particular with polyols, fatty acid derivatives, for
example oleic esters, oligomerized fatty acids, substituted
ethanolamines and products which are sold under the trade name RC
4801 (Rhein Chemie Mannheim, Germany) or HiTEC 536 (Ethyl
Corporation).
[0113] Suitable demulsifiers are, for example, the alkali metal or
alkaline earth metal salts of alkyl-substituted phenol- and
naphthalenesulfonates and the alkali metal or alkaline earth metal
salts of fatty acids, and also neutral compounds such as alcohol
alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates, e.g.
tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty
acids, alkylphenols, condensation products of ethylene oxide (EO)
and propylene oxide (PO), for example including in the form of
EO/PO block copolymers, polyethyleneimines or else
polysiloxanes.
[0114] Suitable dehazers are, for example, alkoxylated
phenol-formaldehyde condensates, for example the products
obtainable under the tradenames NALCO 7D07 (Nalco) and TOLAD 2683
(Petrolite).
[0115] Suitable antifoams are, for example, polyether-modified
polysiloxanes, for example the products obtainable under the
tradenames TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and
RHODOSIL (Rhone Poulenc).
[0116] Suitable cetane number improvers are, for example, aliphatic
nitrates such as 2-ethyl-hexyl nitrate and cyclohexyl nitrate, and
peroxides such as di-tert-butyl peroxide.
[0117] Suitable antioxidants are, for example, substituted phenols
such as 2,6-di-tert-butylphenol and
2,6-di-tert-butyl-3-methylphenol, and phenylenediamines such as
N,N'-di-sec-butyl-p-phenylenediamine.
[0118] Suitable metal deactivators are, for example, salicylic acid
derivatives such as N,N'-disalicylidene-1,2-propanediamine.
[0119] Component (iii) is preferably selected from antioxidants,
corrosion inhibitors and antistats.
[0120] When component (iii) is used in the process according to the
invention, the individual additives are used in those amounts
customary for such packages in relation to component (i).
[0121] When component (iii) is used in the process according to the
invention, preference is given to mixing all three components (i),
(ii) and (iii) in the dynamic mixer or in the lamination mixer.
[0122] Alternatively, in the process according to the invention,
preferably only component (i) and component (ii) are mixed in the
dynamic mixer or in the lamination mixer.
[0123] In the case that only components (i) and (ii) are mixed in
the dynamic mixer or lamination mixer used in accordance with the
invention, component (iii) can also be incorporated subsequently
into the additive mixture obtained in accordance with the
invention, for example by customary stirring in or mixing, when the
finished additive package is also to comprise component (iii). This
would be possible, for example, when the mixing in of component
(iii) does not present any particular problems and a homogeneous
package which does not have any handling disadvantages can also be
obtained by conventional mixing processes.
[0124] In the context of the present invention, fuel oils are
understood to mean liquid fuels. Suitable fuel oils are gasoline
fuels and middle distillates. Middle distillates are preferably
selected from diesel fuels, heating oil and turbine fuels.
[0125] The heating oils are, for example, low-sulfur or sulfur-rich
mineral oil raffinates, or hard coal or brown coal distillates,
which typically have a boiling range of from 150 to 400.degree. C.
The heating oils are preferably low-sulfur heating oils, for
example those having a sulfur content of at most 0.1% by weight,
preferably of at most 0.05% by weight, more preferably of at most
0.005% by weight and especially of at most 0.001% by weight.
Examples of heating oil include especially heating oil for domestic
oil-fired boilers or EL heating oil. The quality requirements for
such heating oils are laid down, for example, in DIN 51-603-1 (cf.
also Ullmann's Encyclopedia of Industrial Chemistry, 5th edition,
vol. A12, p. 617 ff., which is hereby explicitly incorporated by
reference).
[0126] The diesel fuels are, for example, mineral oil raffinates
which typically have a boiling range of from 100 to 400.degree. C.
They are usually distillates having a 95% point up to 360.degree.
C. or even higher. They may, however, also be so-called "ultra low
sulfur diesel" or "city diesel", characterized by a 95% point of,
for example, not more than 345.degree. C. and a sulfur content of
not more than 0.005% by weight, or by a 95% point of, for example,
285.degree. C. and a sulfur content of not more than 0.001% by
weight.
[0127] In addition to the diesel fuels obtainable by refining (of
mineral oil), renewable diesel fuels, synthetic diesel fuels and
mixtures of all of these diesel fuel types fall under the term
"diesel fuels".
[0128] Synthetic fuels generally refer to gasoline and diesel fuels
which are obtained from various primary energy sources by the
Fischer-Tropsch process. The primary energy carrier is converted
first to synthesis gas which is then reacted further catalytically
to give the desired fuel type. The type of process determines
whether synthetic diesel fuels or else synthetic gasoline fuels are
obtained. When coal is used as the primary energy source, reference
is made to a CTL fuel (CTL: coal-to-liquid); when natural gas is
used, the end product is called GTL fuel (GTL: gas to liquid). When
biomass is the starting material, the fuel is a BTL fuel (BTL:
biomass-to-liquid).
[0129] Renewable fuels are fuels which are obtained from renewable
raw materials, especially from plants. These include vegetable
oils, biodiesel, bioethanol and also the BTL fuels already
mentioned. Bioethanol is used in gasoline engines in particular and
therefore does not belong to the renewable diesel fuels, but rather
is counted among the renewable gasoline fuels. Biodiesel is
generally understood to mean the lower alkyl esters of vegetable
oils (or else animal fats), i.e. their C.sub.1-C.sub.4-alkyl
esters, in particular their ethyl or methyl esters and especially
their methyl esters. In Europe, the most frequently used biodiesel
is rapeseed oil methyl ester (RME). Biodiesel is obtained by the
transesterification of vegetable oils, which of course consist in
particular of glyceryl esters of long-chain fatty acids, with lower
alcohols (C.sub.1-C.sub.4 alcohols), especially with methanol, but
in some cases also with ethanol.
[0130] Preferred diesel fuels are diesel fuels which are obtained
by refining, synthetic diesel fuels, the GTL, CTL and BTL diesel
fuels, vegetable oils, biodiesel and mixtures of these diesel fuel
types.
[0131] Suitable turbine fuels, which are also referred to as
aviation turbine fuels, jet fuels, aviation fuels or turbo fuels,
are, for example, fuels of the Jet A, Jet A-1, Jet B, JP-4, JP-5,
JP-7, JP-8 and JP-8+100 designation. Jet A and Jet A-1 are
commercially available turbine fuel specifications based on
kerosene. The corresponding standards are ASTM D 1655 and DEF STAN
91-91. Jet A and Jet A-1, according to their particular
specification, have maximum freezing points of -40.degree. C. and
-47.degree. C. respectively. Jet B is a more widely cut fuel based
on naphtha and kerosene fractions. JP-4 is equivalent to Jet B.
JP-4, JP-5, JP-7, JP-8 and JP-8+100 are military turbine fuels, as
used, for example, by the marines and airforce. Some of these names
denote formulations which already comprise additives, such as
corrosion inhibitors, icing inhibitors, static dissipators, etc.
Preferred turbine fuels are Jet A, Jet A-1 and JP 8.
[0132] Conventional gasoline fuels are described, for example, in
Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., 1990,
volume A16, p. 719 ff. Owing to their composition, gasoline fuels
have a lower boiling point range and a lower density compared to
middle distillates.
[0133] The gasoline fuels may either be fuels for gasoline engines
in automobiles or aviation gasoline (leaded gasoline fuel with an
RON of from 100 to 130).
[0134] Preferred fuel oils are middle distillates, preference being
given to diesel fuels and heating oil. The diesel fuels may, as
already stated, be synthetic (GTL, CTL) or renewable diesel fuels
obtainable by refining, or mixtures thereof.
[0135] The invention further provides additive mixtures which are
obtainable by the process according to the invention. Reference is
made to the remarks made above with regard to suitable and
preferred measures of the process according to the invention and of
the mixture components to be used and of their quantitative
ratios.
[0136] Finally, the invention provides a fuel oil composition which
comprises an inventive additive mixture. Reference is made to the
remarks made above with regard to suitable and preferred measures
of the process according to the invention, of the mixture
components to be used and of their quantitative ratios, and also to
suitable and preferred fuel oils.
[0137] The fuel oil composition comprises the inventive additive
mixture generally in customary amounts, for example in an amount of
10 to 2000 ppm by weight, preferably of 20 to 1000 ppm by weight
and especially of 50 to 500 ppm by weight.
[0138] By virtue of the use of dynamic mixers or lamination mixers
in the process according to the invention, additive mixtures
superior to the additive mixtures produced by conventional mixing
processes with regard to their handling properties are obtained.
The functional properties (for example cold flow-improving
properties, such as CP, PP and CFPP of the fuel oils additized with
the additive mixtures, or intrinsic CP and PP) are at the same time
essentially unchanged. "Essentially unchanged" means that the
deviation is at most 10%, preferably at most 5%, more preferably at
most 3% and especially at most 1% (compared to additive mixtures
which are produced by conventional mixing processes). In
particular, the inventive additive mixtures have a reduced lower
mixing temperature (LMT), a greater storage stability and/or a
better filterability according to the SEDAB test described below,
compared to additive mixtures which have been produced by
conventional mixing processes. Preferably, at least one of these
parameters is improved by at least 10% compared to the prior art
additive mixtures. Preferably, all three parameters are improved.
More preferably, all three parameters are improved by at least 10%
compared to the prior art additive mixtures. When only some of
these parameters are improved, the remaining parameters are not
worsened or are only insignificantly worsened compared to
conventionally produced additive components. "Only insignificantly"
means that the particular measurement is worse by at most 5%,
preferably by at most 3%. The process according to the invention
additionally allows components with very different viscosities or
else components which are present in very different proportions in
the mixture to be mixed with one another completely and
homogeneously and hence additive mixtures which are significantly
more homogeneous than mixtures produced by conventional mixing
processes to be obtained. The process according to the invention
especially allows production of additive mixtures from cold flow
improvers in solvents as typically used in additive packages for
fuel oils, which possess outstanding handling properties. Cold flow
improvers are generally high-viscosity waxes which cannot
automatically be incorporated homogeneously into such solvents.
[0139] The invention will now be illustrated in detail with
reference to the nonlimiting examples which follow.
EXAMPLES
1. Production of the Additive Mixtures
[0140] Additive mixtures composed of a cold flow improver and a
solvent have been produced and tested with regard to their
properties. In all tests, a 50% polymer solution was produced,
using an ethylene/vinyl acetate copolymer having a vinyl acetate
content of 30% by weight and a viscosity of 310 mm.sup.2/s (at
120.degree. C.) as the cold flow improver and Solvent Naphtha as
the solvent. The temperature of the polymer supplied and also the
mixing temperature was in each case 90.degree. C. in all examples.
In all cases, the polymer solution formed was cooled via indirect
cooling by means of a spiral heat exchanger (length: 1.8 m;
diameter: 8 mm) in a waterbath before the discharge from the
system.
Example 1
[0141] Mixer: toothed ring dispersing machine from Kinematica,
MT5000 type; speed 20 000 rpm [0142] Throughput: 10 kg/h [0143]
Mean residence time: 19.8 s [0144] Discharge temperature:
48.degree. C.
Example 2
[0144] [0145] Mixer: toothed ring dispersing machine from
Kinematica, MT5000 type; speed 20 000 rpm [0146] Throughput: 10
kg/h [0147] Mean residence time: 19.8 s [0148] Discharge
temperature: 59.degree. C.
Example 3
[0148] [0149] Mixer: toothed ring dispersing machine from
Kinematica, MT5000 type; speed 6000 rpm [0150] Throughput: 10 kg/h
[0151] Mean residence time: 19.8 s [0152] Discharge temperature:
59.degree. C.
Example 4
[0152] [0153] Mixer: mixing pump from K-Engineering, HMR 040 type;
speed 3000 rpm [0154] Throughput: 10 kg/h [0155] Mean residence
time: 3.9 s [0156] Discharge temperature: 55.degree. C.
Example 5
[0156] [0157] Mixer: mixing pump from K-Engineering, HMR 040 type;
speed 3000 rpm [0158] Throughput: 10 kg/h [0159] Mean residence
time: 3.9 s [0160] Discharge temperature: 61.degree. C.
Comparative Example 1
[0160] [0161] Mixer: static mixer from Sulzer, SMX type, diameter 8
mm, length to diameter ratio=10 [0162] Throughput: 9.6 kg/h [0163]
Mean residence time: 1.4 s [0164] Discharge temperature: 52.degree.
C.
Comparative Example 2
[0164] [0165] Mixer: static mixer from Sulzer, SMX type, diameter 8
mm, length to diameter ratio=10 [0166] Throughput: 10 kg/h [0167]
Mean residence time: 1.3 s [0168] Discharge temperature: 49.degree.
C.
2. Determination of the Properties of the Additive Mixtures
[0169] The filterability and the minimum mixing temperature of the
additive mixtures produced above into a fuel oil were determined.
In addition, the CFPP (cold filter plugging point) of fuel oils
additized with the additive mixtures was determined. Additionally,
the CP (cloud point) and the PP (pour point) of the cold flow
improvers were determined. The CP was determined to ASTM D 2500,
the CFPP in the fuel oil to DIN EN 116 and the PP to ASTM D 97. The
storage stability, the minimum mixing temperature (lower mixing
temperature; LMT) and the filterability (SEDAB) were determined as
described below.
[0170] The CFPP was determined at in each case a 400 ppm dosage of
the additive mixtures produced above in a fuel oil with the
following specification: Winter diesel fuel; Austria;
CFPP=-14.degree. C.; CP=-11.degree. C.; density=833.6 kd/m.sup.3;
IBP=167.degree. C.; FBP=361.degree. C.; 90-20=117.degree. C.; 19.2%
paraffins
[0171] The storage stability was determined visually. For this
purpose, it was examined whether, within the period in question, a
phase separation, which can also be manifested in cloudiness, had
occurred.
SEDAB Filtration Test (ARAL In-House Method)
[0172] For this test, a stainless steel vacuum filtration system
(SM 16201 from Sartorius) with a 500 ml filter cup, a 2000 ml
suction bottle and a membrane filter (stock number 11304 50 N from
Sartorius; diameter 50 mm, pore width 0.8 .mu.m; dried at
90.degree. C. for 30 min and stored under dry conditions) is
used.
[0173] To remove water, soil and coke constituents, the fuel oil is
prefiltered through a fluted filter. 500 ml of the prefiltered fuel
oil per test are filled into a 1000 ml mixing cylinder. 500 ppm of
the additive mixture are added and then the mixture is stored at
room temperature for 16 h. Subsequently, the sample is homogenized
by twice tilting the mixing cylinder by 180.degree.. The membrane
filter is placed into the filtration system and, with the tap
closed, the pressure is adjusted to 200 mbar. The attached filter
cup is filled with the homogenized sample (500 ml). The tap is
opened and the filtration time is determined.
[0174] Samples which are completely filterable within 120 s are
considered to be uncritical. Samples which are completely
filterable within 120 s are considered as a "PASS"; the filtration
time is recorded. Samples for which the filtration time is more
than 120 s are considered as a "FAIL".
Determination of the Minimum Mixing Temperature (LMT)
[0175] The minimum mixing temperature is important particularly for
those refineries which mix additives unheated into fuel oils or mix
additives into unheated fuel oils. When the minimum mixing
temperature of the additive is high, there may be filter problems
after the unheated mixing.
[0176] The minimum mixing temperature was determined by a modified
SEDAB filtration test:
[0177] For this test, a stainless steel vacuum filtration system
(SM 16201 from Sartorius) with a 500 ml filter cup, a 2000 ml
suction bottle and a membrane filter (stock number 11304 50 N from
Sartorius; diameter 50 mm, pore width 0.8 .mu.m; dried at
90.degree. C. for 30 min and stored under dry conditions) is
used.
[0178] To remove water, soil and coke constituents, the fuel oil is
prefiltered through a fluted filter. 500 ml of the prefiltered and
unadditized fuel oil per test are filled into a 1000 ml mixing
cylinder and brought to the test temperature. The
temperature-controlled fuel oil is admixed with the undiluted
additive mixture at 40.degree. C. (500 ppm) and immediately
homogenized by gently tilting the mixing cylinder ten times. The
membrane filter is placed into the filtration system by the top
side of the filter and, with the tap closed, the pressure is
adjusted to 200 mbar. The attached filter cup is filled with the
homogenized sample (500 ml). The tap is opened and the filtration
time is determined.
[0179] Samples which are completely filterable within 120 s are
considered as a "PASS"; the filtration time at the given
temperature is recorded. Samples for which the filtration time is
more than 120 s are considered as a "FAIL"; the residual volume
still present in the filter cup after 120 s is determined. For such
samples, the temperature of the fuel oil is increased by 5.degree.
C. and the filtration time is determined again. The temperature
increase by 5.degree. C. in each case is repeated until the sample
is completely filterable within 120 s; the filtration time at the
appropriate temperature is recorded. Conversely, in the case of
samples which are completely filterable within 120 s, the
temperature of the fuel oil is lowered successively by 5.degree. C.
in each case until the sample is no longer completely filterable
within 120 s. The temperature should not go below the minimum
temperature value of 10.degree. C.
[0180] The LMT was determined at a dosage of the additive at
40.degree. C. of 500 ppm in a fuel oil with the following
specification:
Diesel fuel; Germany; CFPP=-13.degree. C.; CP=-12.2.degree. C.,
density=835.5 kg/m.sup.3; IBP=206.degree. C.; FBP=343.degree. C.;
90-20=74.degree. C.; 22.6% n-paraffins.
[0181] The passage time of the unadditized fuel at 10.degree. C.
was 74 s.
[0182] The results are listed in the table below.
TABLE-US-00001 TABLE Example Passage time.sup.1 [s]
Storability.sup.2 LMT [.degree. C.] CFPP [.degree. C.] PP [.degree.
C.] SC.sup.3 [%] 1 78 0 30 -21 15 49 2 87 + 30 -22 15 49 3 83 + 30
-21 15 49 4 55 + 25 -23 12 50 5 57 + 25 -24 12 55 Comp. 1 >120 -
35 -22 15 49 Comp. 2 110 - 35 -23 15 50 .sup.1Filterability
according to SEDAB test .sup.2+ = more than 6 months; 0 = 6 months;
- = less than 6 months .sup.3SC = solids content; determined by
evaporating volatile constituents at elevated temperature and
reduced pressure
* * * * *