Field of the Invention
[0001] The present invention relates to the use of a Fischer-Tropsch derived base oil for
the purpose of reducing the toxicity of used lubricating compositions.
Background of the Invention
[0002] The primary purpose of lubrication is separation of surfaces moving relative to one
another, to minimise friction and wear. The materials most frequently used for this
purpose are oils and greases. The choice of lubricant is mostly determined by the
particular application.
[0003] The lubricating oils in all engines are at risk of contamination from fuel components,
with the consequential reduction in lubricating properties exhibited by the lubricating
oil. In addition, fuel contamination results in an increase in the toxicity of the
lubricant due to accumulation of toxic fuel components in the lubricant. This is especially
the case with spark ignition engines where Platformate (a gasoline blending component)
causes significant light poly-cyclic aromatics accumulation in the lubricant.
[0004] The toxicity increase is a particular issue for the recycling of so-called "used
oil". "Used oil" can be defined as any petroleum-based or synthetic oil that, through
use or handling, has become unsuitable for its original purpose due to the presence
of impurities or loss of original properties. Some examples of types of products that
after use can be labeled as used oil are hydraulic oil, transmission oil, brake fluids,
motor oil, crankcase oil, gear box oil, synthetic oil, and grades #1, 2, 3, and 4
fuel oil.
[0005] Used oil can be used for various purposes including as a fuel in, for example, industrial
furnaces or boilers.
[0006] As mentioned above however, one disadvantage of used lubricants from spark ignition
engines is that they contain toxic materials as a result of having been contaminated
by gasoline fuel components during use. Since it is desirable to recycle these used
lubricants for other purposes, it would be useful to find a way to reduce the toxicity
of the used lubricants from spark ignition engines, such that handling and further
processing becomes safer and more manageable.
[0007] It has now surprisingly been found that by using a particular base oil in the lubricating
composition contained in a spark ignition internal combustion engine, the used lubricating
composition has a reduced toxicity.
Summary of the Invention
[0008] According to the present invention there is provided the use of a Fischer-Tropsch
derived base oil for the purpose of reducing the toxicity of a used lubricating composition
obtained from a spark ignition internal combustion engine fuelled with a gasoline
composition wherein the Fischer-Tropsch derived base oil is incorporated into the
lubricating composition before use in an engine.
Detailed Description of the Invention
[0009] As used herein the term "used lubricating composition" means a petroleum-based or
synthetic-based lubricating composition that, through use, in a gasoline-fuelled spark
ignition internal combustion engine, has become unsuitable for its original purpose
due to the presence of impurities or loss of original properties. The term "through
use" in this context means that the vehicle powered by the gasoline-fuelled spark
ignition internal combustion engine has preferably done at least 3000 miles. It is
recognised by a person skilled in the art that in the case of a bench engine test,
e.g. the API Sequence III G engine test or the ACEA TU-5JP-L4 engine test, the severity
of the bench test is equivalent to the engine having done preferably at least 3000
miles.
[0010] The present invention involves the use of a Fischer-Tropsch derived base oil, wherein
the Fischer-Tropsch derived base oil is incorporated into the lubricating composition
before use in an engine, as defined in the appended claims. Such a use results in
a used lubricating composition having a significantly reduced toxicity.
[0011] As used herein the term "reducing the toxicity of the used lubricating composition"
means that the used lubricating composition obtained from a gasoline-fuelled spark
ignition internal combustion engine and containing a Fischer-Tropsch derived base
oil has a significantly reduced Mutagenicity Index and preferably a significantly
reduced Fold Increase, as measured by the Modified Ames Test Method (according to
ASTM E1687), compared to a used lubricating composition obtained from a gasoline-fuelled
spark ignition internal combustion engine but not containing a Fischer-Tropsch derived
base oil.
[0012] The gasoline composition for use in the present invention comprises gasoline base
fuel. The gasoline may be any gasoline suitable for use in an internal combustion
engine of the spark-ignition (petrol) type known in the art. The gasoline used as
the base fuel in the liquid fuel composition of the present invention may conveniently
also be referred to as 'base gasoline'.
[0013] Gasolines typically comprise mixtures of hydrocarbons boiling in the range from 25
to 230 C (EN-ISO 3405), the optimal ranges and distillation curves typically varying
according to climate and season of the year. The hydrocarbons in a gasoline may be
derived by any means known in the art, conveniently the hydrocarbons may be derived
in any known manner from straight-run gasoline, synthetically-produced aromatic hydrocarbon
mixtures, thermally or catalytically cracked hydrocarbons, hydro-cracked petroleum
fractions, catalytically reformed hydrocarbons or mixtures of these.
[0014] The specific distillation curve, hydrocarbon composition, research octane number
(RON) and motor octane number (MON) of the gasoline are not critical.
[0015] Conveniently, the research octane number (RON) of the gasoline may be at least 80,
for instance in the range of from 80 to 110, preferably the RON of the gasoline will
be at least 90, for instance in the range of from 90 to 110, more preferably the RON
of the gasoline will be at least 91, for instance in the range of from 91 to 105,
even more preferably the RON of the gasoline will be at least 92, for instance in
the range of from 92 to 103, even more preferably the RON of the gasoline will be
at least 93, for instance in the range of from 93 to 102, and most preferably the
RON of the gasoline will be at least 94, for instance in the range of from 94 to 100
(EN 25164); the motor octane number (MON) of the gasoline may conveniently be at least
70, for instance in the range of from 70 to 110, preferably the MON of the gasoline
will be at least 75, for instance in the range of from 75 to 105, more preferably
the MON of the gasoline will be at least 80, for instance in the range of from 80
to 100, most preferably the MON of the gasoline will be at least 82, for instance
in the range of from 82 to 95 (EN 25163).
[0016] Typically, gasolines comprise components selected from one or more of the following
groups; saturated hydrocarbons, olefinic hydrocarbons, aromatic hydrocarbons, and
oxygenated hydrocarbons. Conveniently, the gasoline may comprise a mixture of saturated
hydrocarbons, olefinic hydrocarbons, aromatic hydrocarbons, and, optionally, oxygenated
hydrocarbons.
[0017] Typically, the olefinic hydrocarbon content of the gasoline is in the range of from
0 to 40 percent by volume based on the gasoline (ASTM D1319); preferably, the olefinic
hydrocarbon content of the gasoline is in the range of from 0 to 30 percent by volume
based on the gasoline, more preferably, the olefinic hydrocarbon content of the gasoline
is in the range of from 0 to 20 percent by volume based on the gasoline.
[0018] Typically, the aromatic hydrocarbon content of the gasoline is in the range of from
0 to 70 percent by volume based on the gasoline (ASTM D1319), for instance the aromatic
hydrocarbon content of the gasoline is in the range of from 10 to 60 percent by volume
based on the gasoline; preferably, the aromatic hydrocarbon content of the gasoline
is in the range of from 0 to 50 percent by volume based on the gasoline, for instance
the aromatic hydrocarbon content of the gasoline is in the range of from 10 to 50
percent by volume based on the gasoline.
[0019] The benzene content of the gasoline is at most 10 percent by volume, more preferably
at most 5 percent by volume, especially at most 1 percent by volume based on the gasoline.
[0020] The gasoline preferably has a low or ultra low sulphur content, for instance at most
1000 ppmw (parts per million by weight), preferably no more than 500 ppmw, more preferably
no more than 100, even more preferably no more than 50 and most preferably no more
than even 10 ppmw.
[0021] The gasoline also preferably has a low total lead content, such as at most 0.005
g/l, most preferably being lead free - having no lead compounds added thereto (i.e.
unleaded).
[0022] When the gasoline comprises oxygenated hydrocarbons, at least a portion of non-oxygenated
hydrocarbons will be substituted for oxygenated hydrocarbons. The oxygen content of
the gasoline may be up to 35 percent by weight (EN 1601) (e.g. ethanol per se) based
on the gasoline. For example, the oxygen content of the gasoline may be up to 25 percent
by weight, preferably up to 10 percent by weight. Conveniently, the oxygenate concentration
will have a minimum concentration selected from any one of 0, 0.2, 0.4, 0.6, 0.8,
1.0, and 1.2 percent by weight, and a maximum concentration selected from any one
of 5, 4.5, 4.0, 3.5, 3.0, and 2.7 percent by weight.
[0023] Examples of oxygenated hydrocarbons that may be incorporated into the gasoline include
alcohols, ethers, esters, ketones, aldehydes, carboxylic acids and their derivatives,
and oxygen containing heterocyclic compounds. Preferably, the oxygenated hydrocarbons
that may be incorporated into the gasoline are selected from alcohols (such as methanol,
ethanol, propanol, 2-propanol, butanol, tert-butanol, iso-butanol and 2-butanol),
ethers (preferably ethers containing 5 or more carbon atoms per molecule, e.g., methyl
tert-butyl ether) and esters (preferably esters containing 5 or more carbon atoms
per molecule); a particularly preferred oxygenated hydrocarbon is ethanol.
[0024] When oxygenated hydrocarbons are present in the gasoline, the amount of oxygenated
hydrocarbons in the gasoline may vary over a wide range. For example, gasolines comprising
a major proportion of oxygenated hydrocarbons are currently commercially available
in countries such as Brazil and U.S.A, e.g. ethanol per se and E85, as well as gasolines
comprising a minor proportion of oxygenated hydrocarbons, e.g. E10 and E5. Therefore,
the gasoline may contain up to 100 percent by volume oxygenated hydrocarbons. Preferably,
the amount of oxygenated hydrocarbons present in the gasoline is selected from one
of the following amounts: up to 85 percent by volume; up to 65 percent by volume;
up to 30 percent by volume; up to 20 percent by volume; up to 15 percent by volume;
and, up to 10 percent by volume, depending upon the desired final formulation of the
gasoline. Conveniently, the gasoline may contain at least 0.5, 1.0 or 2.0 percent
by volume oxygenated hydrocarbons.
[0025] Examples of suitable gasolines include gasolines which have an olefinic hydrocarbon
content of from 0 to 20 percent by volume (ASTM D1319), an oxygen content of from
0 to 5 percent by weight (EN 1601), an aromatic hydrocarbon content of from 0 to 50
percent by volume (ASTM D1319) and a benzene content of at most 1 percent by volume.
[0026] Whilst not critical to the present invention, the base gasoline or the gasoline composition
of the present invention may conveniently additionally include one or more fuel additive(s).
The concentration and nature of the fuel additive(s) that may be included in the base
gasoline or the gasoline composition of the present invention is not critical. Non-limiting
examples of suitable types of fuel additives that can be included in the base gasoline
or the gasoline composition of the present invention include anti-oxidants, corrosion
inhibitors, detergents, dehazers, antiknock additives, metal deactivators, valve-seat
recession protectant compounds, dyes, friction modifiers, carrier fluids, diluents
and markers. Examples of suitable such additives are described generally in
US Patent No. 5,855,629.
[0027] Conveniently, the fuel additives can be blended with one or more diluents or carrier
fluids, to form an additive concentrate, the additive concentrate can then be admixed
with the base gasoline or the gasoline composition of the present invention.
[0028] The (active matter) concentration of any additives present in the base gasoline or
the gasoline composition of the present invention is preferably up to 1 percent by
weight, more preferably in the range from 5 to 1000 ppmw, advantageously in the range
of from 75 to 300 ppmw, such as from 95 to 150 ppmw.
[0029] There is no particular limitation on the type of lubricating composition which can
be used in the present invention, provided it is suitable for use in a spark ignition
internal combustion engine and provided it contains a Fischer-Tropsch derived base
oil.
[0030] Fischer-Tropsch derived base oils are known in the art. By the term "Fischer-Tropsch
derived" is meant that a base oil is, or is derived from, a synthesis product of a
Fischer-Tropsch process. A Fischer-Tropsch derived base oil may also be referred to
as a GTL (Gas-To-Liquids) base oil. Suitable Fischer-Tropsch derived base oils that
may be conveniently used as the base oil in the lubricating composition are those
as for example disclosed in
EP 0 776 959,
EP 0 668 342,
WO97/21788,
WO 00/15736,
WO 00/14188,
WO 00/14187,
WO 00/14183,
WO 00/14179,
WO 00/08115,
WO 99/41332,
EP 1 029 029,
WO 01/18156 and
WO 01/57166.
[0031] A preferred base oil for use in the lubricating composition herein is a Fischer-Tropsch
derived base oil, for example GTL 5 (having a kinematic viscosity at 100°C of approximately
5 mm
2/s) and GTL 8 (having a kinematic viscosity at 100°C of approximately 8 mm
2/s), both of which may be prepared according to the method described in
WO02/070631.
[0032] The Fischer-Tropsch derived base oil is preferably present in the lubricating composition
in an amount in the range of from 60% to 95%, more preferably in the range of from
70% to 95% and even more preferably in the range of from 80% to 90%, by weight of
the lubricating composition.
[0033] The lubricating composition may comprise other types of base oils in addition to
the Fischer-Tropsch derived base oil, as well as lubricant performance additives.
WO2007/128740 discloses suitable lubricating base oils and additives which may be incorporated
into the lubricating composition herein.
[0034] Typically the lubricating composition has a relatively low phosphorus content such
as below 0.12 wt.% (according to ASTM D 5185). Preferably, the lubricating composition
has a phosphorus content of less than 0.08 wt.%. Preferably, the composition has a
phosphorus content of above 0.06 wt.%.
[0035] Also, it is preferred that the lubricating composition has a sulphur content of less
than 0.6 wt.% (according to ASTM D 5185).
[0036] Further it is preferred that the lubricating composition has a chlorine content of
less than 200 ppm (according to ASTM D 808).
[0037] According to an especially preferred embodiment, the lubricating composition has
an ash content of below 2.0 wt.% (according to ASTM D 874).
[0038] According to an especially preferred embodiment of the present invention, the lubricating
composition comprises a zinc dialkyl dithiophosphate (ZDDP) compound. Typically, if
present, the ZDDP compound is present in an amount of 0.01-1.5 wt.%, preferably 0.4-1.0
wt.%. The ZDDP compound may have been made from primary, secondary, tertiary alcohols
or mixtures thereof, preferably containing less than 12 carbon atoms. Preferably,
the ZDDP compound has been made from secondary alcohols containing 3 to 8 carbon atoms.
[0039] There are no particular limitations regarding the additional base oils which can
be used in the lubricating composition, and various conventional mineral oils, synthetic
oils as well as naturally derived esters such as vegetable oils may be conveniently
used.
[0040] Any additional base oil used may conveniently comprise mixtures of one or more mineral
oils and/or one or more synthetic oils; thus, the term "base oil" may refer to a mixture
containing more than one base oil. Mineral oils include liquid petroleum oils and
solvent-treated or acid-treated mineral lubricating oil of the paraffinic, naphthenic,
or mixed paraffinic/naphthenic type which may be further refined by hydrofinishing
processes and/or dewaxing.
[0041] Suitable base oils for use in the lubricating oil composition are Group I-III mineral
base oils, Group IV poly-alpha olefins (PAOs), and mixtures thereof.
[0042] By "Group I", "Group II", "Group III" and "Group IV" base oils are meant lubricating
oil base oils according to the definitions of American Petroleum Institute (API) for
categories I-IV. These API categories are defined in API Publication 1509, 16th Edition,
Appendix E, April 2007.
[0043] Synthetic oils include hydrocarbon oils such as olefin oligomers (including polyalphaolefin
base oils; PAOs), dibasic acid esters, polyol esters, polyalkylene glycols (PAGs),
alkyl naphthalenes and dewaxed waxy isomerates. Synthetic hydrocarbon base oils sold
by the Shell Group under the designation "Shell XHVI" (trade mark) may be conveniently
used.
[0044] Poly-alpha olefin base oils (PAOs) and their manufacture are well known in the art.
Preferred poly-alpha olefin base oils that may be used in the lubricating compositions
may be derived from linear C
2 to C
32, preferably C
6 to C
16, alpha olefins. Particularly preferred feedstocks for said poly-alpha olefins are
1-octene, 1-decene, 1-dodecene and 1-tetradecene.
[0045] The total amount of base oil (including the Fischer-Tropsch derived base oil) incorporated
in the lubricating composition is preferably present in an amount in the range of
from 60 to 99 wt.%, more preferably in an amount in the range of from 65 to 98 wt.%,
even more preferably in an amount in the range of from 70 to 95 wt.%, and especially
in an amount in the range of from 80% to 90 wt.%, with respect to the total weight
of the lubricating composition.
[0046] Preferably, the finished lubricating composition has a kinematic viscosity in the
range of from 2 to 80 mm
2/s at 100 °C, more preferably in the range of from 3 to 70 mm
2/s, most preferably in the range of from 4 to 30 mm
2/s.
[0047] The lubricating composition may further comprise additional additives such as anti-wear
additives, anti-oxidants, dispersants, detergents, friction modifiers, viscosity index
improvers, pour point depressants, corrosion inhibitors, defoaming agents and seal
fix or seal compatibility agents.
[0049] Preferably the detergent, if present, is selected from phenate- and sulphonate-type
detergents; accordingly.
[0050] The lubricating compositions may be conveniently prepared by admixing the additives
that are usually present in lubricating compositions, for example as hereinbefore
described, with the base oil.
[0051] The used lubricating composition obtained from a spark-ignition internal combustion
engine and comprising a Fischer-Tropsch derived base oil has a reduced toxicity, i.e.
it has a significant reduced Mutagenicity Index and also preferably a significantly
reduced Fold Increase as measured by the Modified Ames Test (according to ASTM E 1687),
compared with a used lubricating composition obtained from a spark ignition internal
combustion engine not containing a Fischer-Tropsch derived base oil, e.g. compared
with a used lubricating composition based on a mineral oil base oil.
[0052] In one embodiment, at the end of the API Sequence III G test the used lubricating
composition has a Mutagenicity Index of less than 0.2 as measured by the Modified
Ames Test Method.
[0053] In another embodiment, at the end of the ACEA TU-5JP-L4 test the used lubricating
composition has a
[0054] Mutagenicity Index of less than 1.5 as measured by the Modified Ames Test Method.
[0055] In a further embodiment the difference in Mutagenicity Index as measured by the Modified
Ames Test Method between said used lubricating composition containing a Fischer-Tropsch
derived base oil and a used lubricating composition not containing a Fischer-Tropsch
derived base oil is 0.1 or greater.
[0056] The used lubricating composition is suitable for a variety of uses, such as a fuel
in, for example, industrial furnaces or boilers.
[0057] The present invention will now be described by reference to the following Examples
which are not intended to limit the scope of the invention in any way.
Examples
[0058] To determine the effect of a Fischer-Tropsch derived base oil on the mutagenicity
of used lubricants from gasoline-fuelled spark ignition engines, compared to a mineral
oil based used lubricant, industry standard engine tests were carried out.
[0059] The first standard engine test was the API Sequence III G test, a test for ILSAC
GF-4 and GF-5 and API SM and SN performance level categories. Two different lubricants
were used in these tests (Lubricants 1 and 2). The formulations of these two lubricants
are set out in Table 1 below. The gasoline fuel used in the test was the industry
standard fuel required for the Sequence III G engine test.
Table 1
| |
Lubricant 1 (5W-20 GTL) |
Lubricant 2 (5W-20 Motiva) |
| Performance Additive Package |
12 |
12 |
| Viscosity Modifier |
3 |
3.2 |
| Pour Point Depressant |
0.2 |
0.2 |
| Motiva Star 5+1 |
0 |
69.6 |
| Motiva Star 62 |
0 |
15 |
| GTL base oil (4 cSt)3 |
48.8 |
0 |
| GTL base oil (8 cSt)4 |
36 |
0 |
1. A Group II mineral oil base oil commercially available from Motiva Enterprises
LLC, Port Arthur, TX, USA
2. A Group II mineral oil base oil commercially available from Motiva Enterprises
LLC, Port Arthur, TX, USA
3. A Fischer-Tropsch derived base oil having a kinematic viscosity at 100°C at approximately
4 cSt which may be conveniently prepared by the process described in WO 02/070631
4. A Fischer-Tropsch derived base oil having a kinematic viscosity at 100°C of approximately
8 cSt which may be conveniently prepared by the process described in WO 02/070631 |
[0060] The second standard engine test was the ACEA TU-5JP-L4 test, a test for e.g. ACEA
A1-02, ACEA A2-96, ACEA A3-02, ACEA A5-2 and ACEA C4 performance level categories.
Two different lubricants were used in this test (Lubricants 3 and 4). The formulations
of these two lubricants are set out in Table(s) 2 below. The gasoline fuel used in
the trial was the industry standard fuel required for the ACEA TU-5JP-L4 engine test.
Table 2
| |
Lubricant 3 (5W-30 Yubase) %m |
Lubricant 4 (5W-30 GTL) %m |
| Performance Additive Package |
12 |
12 |
| Pour Point Depressant |
0.5 |
0.5 |
| Antifoam agent |
0.1 |
0.1 |
| Viscosity Modifier concentrate |
5.0 |
3.7 |
| GTL base oil (4 cSt)5 |
0 |
22.5 |
| GTL base oil (8 cSt)6 |
0 |
61.2 |
| Yubase 47 |
49.4 |
0 |
| Yubase 68 |
33.0 |
0 |
5. A Fischer-Tropsch derived base oil having a kinematic viscosity at 100°C of approximately
4 cSt which may be conveniently prepared by the process described in WO 02/070631
6. A Fischer-Tropsch derived base oil having a kinematic viscosity at 100°C of approximately
8 cSt which may be conveniently prepared by the process described in WO 02/070631
7. API Group III base oil commercially available from SK Energy, Ulsan, South Korea
8. API Group III base oil commercially available from SK Energy, Ulsan, South Korea |
[0061] Each engine test type used the appropriate standard gasoline fuel and one lubricant
(1, 2 ,3 or 4) as shown in Table 3 below. The Mutagenicity Index (MI) of each of the
lubricants was measured before the vehicle had done any mileage (designated as "start"
of the test in Table 3 below) and was measured again at the end of the industry standard
test, (designated as "end" of the test in Table 3 below) using the Modified Ames Test
Method (according to ASTM E1687). The results are shown in Table 3 below.
Table 3
| Test No. |
Engine Test Type |
Lubricant (1/2/3/4) |
Start/ End of Test |
MI |
| 1 |
API Sequence III G test |
1 (5W-20 GTL) |
Start |
0 |
| 1 |
API Sequence III G test |
1 (5W-20 GTL) |
End |
0.1 |
| 2 |
API Sequence III G test |
2 (5W-20 Motiva Group II) |
Start |
0 |
| 2 |
API Sequence III G test |
2 (5W-20 Motiva Group II) |
End |
0.21 |
| 3 |
ACEA TU-5JP-L4 |
3 (5W-30 Yubase) |
Start |
0 |
| 3 |
ACEA TU-5JP-L4 |
3 (5W-30 Yubase) |
End |
1.6 |
| 4 |
ACEA TU-5JP-L4 |
4 (5W-30 GTL) |
Start |
0 |
| 4 |
ACEA TU-5JP-L4 |
4 (5W-30 GTL) |
End |
1.2 |
Discussion
[0062] As can be seen from the results in Table 3 Lubricants 1 and 4 (containing a GTL base
oil) had a much lower Mutagenicity Index at the end of the relevant test than their
corresponding Lubricants 2 and 3 (not containing a GTL base oil).