Note: Descriptions are shown in the official language in which they were submitted.
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Marine Engine Lubrication
FIELD OF THE INVENTION
The invention relates to a method of operating a two-stroke, cross-head, slow
speed,
compression-ignited (diesel) marine engine that is fuelled with a low sulphur
fuel such as
liquid natural gas and, in particular, to cylinder lubrication of the engine
during operation.
BACKGROUND OF THE INVENTION
In a marine diesel cross-head engine, the cylinder liner and the crankcase are
lubricated
separately using a cylinder oil and a system oil respectively. The cylinder
oil, often
referred to as a marine diesel lubricant (or MDCL), lubricates the inner walls
of the engine
cylinder and the piston ring pack, and controls corrosive and mechanical wear.
Such engines are usually fuelled by heavy fuel oil or marine distillate fuel.
These fuels
have a high sulphur and heavy metal content, as well as being of high
viscosity and being
difficult to handle. For example, a heavy fuel oil may have sulphur levels
ranging from
=
50ppm to more than 4.0% by mass. For engines operating with these fuels, the
MDCL has
to be designed to provide base to neutralise the acids produced as a result of
combustion of
the sulphur-containing fuel. Typical MDCL's may have a total base number of 70
¨100mg KOH/g (ASTM D 2896-98).
More recently, efforts are being made to reduce fuel sulphur levels in marine
fuels in order
to reduce the adverse environmental impact of large marine engines.
This invention is concerned with using low sulphur fuels such as liquid
natural gas (LNG)
as the fuel. Since LNG predominantly consists of methane, with the balance
made up of
other hydrocarbons, the MDCL does not require excess base to neutralise acids.
It is,
however, still required to provide wear protection and cleanliness to the
cylinder liner and
piston area of the engine. Low sulphur fuels generally have a sulphur level of
0.5% or less.
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WO 2011/051261-A ('261) generally describes lubricants having a TBN of at
least 10mg
KOH/g for improving deposit formation in marine diesel engines. '261
exemplifies
formulations of marine cylinder oils for use in marine diesel engines.
However, all
examples are conducted at TBN's in excess of 20 and the specification makes no
mention
of LNG-fuelled engines. '261 states that its best examples are Examples 5 and
6, where
the lubricant comprises a low BN Ca sulphonate and a high BN Ca phenate.
A problem in the art is to provide MDCL's for use in a LNG- and similarly
fuelled marine
cross-head engine where the MDCL has a low base content, but yet is still
capable of
providing wear protection and cleanliness properties.
SUMMARY OF THE INVENTION
The above problem is met according to the invention by providing an MDCL of
TBN less
than 20 and having a defined detergent system constitution in combination with
a defined
phenolic compound.
Thus, the present invention provides a method of operating a two-stroke, cross-
head slow-
speed compression-ignited engine comprising
(i) fuelling the engine with a diesel fuel, as a pilot fuel, and with a low
sulphur
fuel such as liquefied natural gas, as a main fuel; and
(ii) lubricating the cylinder(s) of the engine with a cylinder lubricant
having a
base number (BN) of 20 or less, comprising a detergent additive system
comprising one or more metal detergents having a surfactant group selected
from phenate, salicylate and sulphonate, or one or more complex metal
detergents containing two or more different surfactant soap groups selected
from phenate, salicylate and sulphonate and comprising 1-4 mass % based
on the lubricant mass of one or more phenolic compounds comprising
distilled cashew nut shell liquid or hydrogenated distilled cashew nut liquid.
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A two-stroke, cross-head slow-speed compression-ignited engine usually has a
speed of
below 200 rpm, such as, for example, 10-200 rpm or 60-200 rpm.
In this specification, the following words and expressions, if and when used,
have
the meanings ascribed below:
"active ingredients" or "(a.i.)" refers to additive material that is not
diluent or
solvent;
"basicity index (or BI)" in the molar ratio of total base to total soap in an
overbased detergent;
"comprising" or any cognate word specifies the presence of stated features,
steps,
or integers or components, but does not preclude the presence or addition of
one or
more other features, steps, integers, components or groups thereof; the
expressions
"consists of' or "consists essentially or' or cognates may be embraced within
"comprises" or cognates, wherein "consists essentially of" permits inclusion
of
substances not materially affecting the characteristics of the composition to
which
it applies;
"major amount" means 50 mass % or more of a composition;
"minor amount" means less than 50 mass % of a composition;
"TBN" means total base number as measured by ASTM D2896.
Furthermore in this specification, if and when used:
"calcium content" is as measured by ASTM 4951;
"phosphorus content" is as measured by ASTM D5185;
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"sulphated ash content" is as measured by ASTM D874;
"sulphur content" is as measured by ASTM D2622;
"KV100" means kinematic viscosity at 100 C as measured by ASTM D445.
Also, it will be understood that various components used, essential as well as
optimal and
customary, may react under conditions of formulation, storage or use and that
the
invention also provides the product obtainable or obtained as a result of any
such reaction.
Further, it is understood that any upper and lower quantity, range and ratio
limits set forth
herein may be independently combined.
DETAILED DESCRIPTION OF THE INVENTION
The features of the invention will now be disclosed in more detail below.
Cylinder Lubricant ("MDCL")
As stated the MDCL has a BN of 20 or less. Preferably the BN is 15 or less
such as in the
range from 5 to 15 or 10 to 15.
The MDCL may comprise 10 ¨ 35, preferably 13 ¨ 30, most preferably 16 ¨ 24,
mass% of
a concentrate or additive package, the remainder being oil of lubricating
viscosity. It
preferably includes at least 50, more preferably at least 60, even more
preferably at least
70, mass % of oil of lubricating viscosity based on the total mass of MDCL.
The additive package includes the detergent system defined under the SUMMARY
OF
=
THE INVENTION heading above. It may also include one or more dispersants, one
or
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more anti-wear agents such as zinc compounds and boron compounds, and one or
more
pour point depressants.
Oil Of Lubricating Viscosity
This may be any oil suitable for lubricating the cylinder(s) of a marine
diesel cross-head
engine.
It may range in viscosity from light distillate mineral oils to heavy
lubricating oils.
Generally, the viscosity of the oil ranges from 2 to 40 mm2/sec, as measured
at 100 C.
Natural oils include animal oils and vegetable oils (e.g., castor oil, lard
oil); liquid
petroleum oils and hydrorefined, solvent-treated or acid-treated mineral oils
of the
paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of
lubricating viscosity
derived from coal or shale also serve as useful base oils.
Synthetic lubricating oils include hydrocarbon oils and halo-substituted
hydrocarbon oils
such as polymerized and interpolymerized olefins (e.g., polybutylenes,
polypropylenes,
propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes),
poly(1-
octenes), poly(1-decenes)); alkybenzenes (e.g., dodecylbenzenes,
tetradecylbenzenes,
dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenyls (e.g., biphenyls,
terphenyls,
alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl
sulphides
and derivative, analogues and homologues thereof.
Alkylene oxide polymers and interpolymers and derivatives thereof where the
terminal
hydroxyl groups have been modified, for example by esterification,
etherification,
constitute another class of known synthetic lubricating oils. These are
exemplified by
polyoxyalkylene polymers prepared by polymerization of ethylene oxide or
propylene
oxide, and the alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-
polyiso-
propylene glycol ether having a molecular weight of 1000 or diphenyl ether of
poly-
ethylene glycol having a molecular weight of 1000 to 1500); and mono- and
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polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-
C8 fatty acid
esters and C13 oxo acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating oils comprises the esters of
dicarboxylic
acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl
succinic acids,
maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic
acid, linoleic acid
dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety
of alcohols
(e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol,
ethylene glycol,
diethylene glycol monoether, propylene glycol). Specific examples of such
esters includes
dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl
sebacate,
diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate,
dieicosyl
sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex
ester formed by
reacting one mole of sebacic acid with two moles of tetraethylene glycol and
two moles of
2-ethylhexanoic acid.
Esters useful as synthetic oils also include those made from C5 to C12
monocarboxylic
acids and polyols and polyol esters such as neopentyl glycol,
trimethylolpropane,
pentaerythritol, dipentaerythritol and tripentaerythritol.
Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or
polyaryloxysilicone
oils and silicate oils comprise another useful class of synthetic lubricants;
such oils include
tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate,
tetra-(4-methyl-2-
ethylhexyl)silicate, tetra-(p-tert-butyl-phenyl)
silicate, hexa-(4-methyl-2-
ethylhexyl)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes.
Other
synthetic lubricating oils include liquid esters of phosphorus-containing
acids (e.g.,
tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic
acid) and
polymeric tetrahydrofurans.
Unrefined, refined and re-refined oils can be used in lubricants of the
present invention.
Unrefined oils are those obtained directly from a natural or synthetic source
without
further purification treatment. For example, a shale oil obtained directly
from retorting
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operations; petroleum oil obtained directly from distillation; or ester oil
obtained directly
from esterification and used without further treatment, are unrefined oils.
Refined oils are
similar to unrefined oils except that the oil is further treated in one or
more purification
steps to improve one or more properties. Many such purification techniques,
such as
distillation, solvent extraction, acid or base extraction, filtration and
percolation, are
known to those skilled in the art. Re-refined oils are obtained by processes
similar to
those used to provide refined oils but that begin with oil that has already
been used in
service. Such re-refined oils are also known as reclaimed or reprocessed oils
and are often
subjected to additional processing using techniques for removing spent
additives and oil
breakdown products.
The American Petroleum Institute (API) publication "Engine Oil Licensing and
Certification System", Industry Services Department, Fourteenth Edition,
December 1996,
Addendum 1, December 1998 categorizes base stocks into various groups.
The oil of lubricating viscosity in the lubricant used in this invention
comprises 50 mass %
or more of the lubricant. Preferably, it comprises 60, such as 70, 80 or 90,
mass % or
more of the lubricant.
Detergent Additive System
As stated, the detergent additive system comprises (A) one or more metal
detergents each
having a surfactant group selected from phenate, salicylate and sulphonate; or
(B) at least
one complex metal detergent containing two or more different surfactant soap
groups
selected from phenate, salicylate and sulphonate.
The metal may, for example, be an alkaline earth metal, preferably calcium.
In (B), one or more metal detergents having one surfactant group may be
present with the
complex detergent(s). By "complex" (or hybrid) detergent is meant a detergent
prepared
from a mixture of more than one metal surfactant, such as a calcium alkyl
phenate and a
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calcium alkyl salicylate. Such a complex detergent is a hybrid material in
which the
surfactant groups, for example phenate and salicylate, are incorporated during
the
overbasing process. Examples of complex detergents are described in the art
(see, for
example, WO 97/46643, WO 97/46644, WO 97/46645, WO 97/46646 and WO 97/46647).
As an example of (B), there may be mentioned (i) a complex metal
phenate/sulphonate
detergent or a complex metal phenate, salicylate and sulphonate detergent and,
optionally,
(ii) one or more individual phenate, sulphonate or salicylate detergents.
Surfactants for the surfactant system of the metal detergents contain at least
one
hydrocarbyl group, for example, as a substituent on an aromatic ring. The
term "hydrocarbyl" as used herein means that the group concerned is primarily
composed
of hydrogen and carbon atoms and is bonded to the remainder of the molecule
via a carbon
atom, but does not exclude the presence of other atoms or groups in a
proportion
insufficient to detract from the substantially hydrocarbon characteristics of
the group.
Advantageously, hydrocarbyl groups in surfactants for use in accordance with
the
invention are aliphatic groups, preferably alkyl or alkylene groups,
especially alkyl groups,
which may be linear or branched. The total number of carbon atoms in the
surfactants
should be at least sufficient to impact the desired oil-solubility.
Advantageously the alkyl
groups include from 5 to 100, preferably from 9 to 40, carbon atoms. Where
there is more
than one alkyl group, the average number of carbon atoms in all of the alkyl
groups is
preferably at least 9 to ensure adequate oil-solubility.
The detergents may be non-sulphurized or sulphurized, and may be chemically
modified
and/or contain additional substituents. Suitable sulphurizing processes are
well known to
those skilled in the art.
The detergents may be borated, using borating processes well known to those
skilled in the
art.
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The detergents in the detergent system may be low base number (LBN), medium
base
number (MBN) or high base number (HBN), where the meanings of those numbers
are set
out in the table below.
Phenate Salicylate Sulphonate
LBN <100 <50
MBN >100 and <200 >100 and <250 >50 and <400
HBN >200 >250 >400
The complex detergents generally have BN's in the range 300 to 420 mg KOH/g.
Phenolic Compounds
The invention employs distilled or hydrogenated-distilled cashew nut shell
liquid (CNSL).
Distilled CNSL is a mixture of biodegradable meta-hydrocarbl substituted
phenols, where
the hydrocarbyl group is linear and unsaturated, including cardanol.
Catalytic
hydrogenation of distilled CNSL gives rise to a mixture of meta-hydrocarbyl
substituted
phenols, predominantly rich in 3-pentadecylphenol.
Operation Of Engine
The marine two stroke engine is operated by igniting a minor charge of liquid
hydrocarbon
fuel such as diesel, marine distillate fuel (MDO), marine gas oil (MGO), heavy
fuel oil
(HFO). A major charge of a low sulphur content fuel (e.g. having less than 0.1
mass % of
atoms of sulphur) is then applied. The low sulphur content fuel may, for
example be a
gaseous fuel such as liquefied natural gas (LNG) or compressed natural gas
(CNG), or a
liquid fuel such as fuel derived from bio matter, e.g. palm oil.
EXAMPLES
The following examples illustrate the invention.
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A set of MDCL's was formulated, each having a BN of 10 and containing a Zn/B
part
package (formulated to deliver approx. 100ppm B, 0.2% Zn and approximately
470ppm
N). The members of the set comprised a base oil and detergent system of the
following
calcium detergents, identified by the indicated codes:
Codes
LBN Sul: Ca Sulfonate of BI 0.4
HBN Sul: Ca Sulfonate of BI 22
MBN Phe: Ca Phenate of BI 1.8
HBN Phe: Ca Phenate of BI 2.9
HBN Sal: Ca Salicylate of BI 7.8
HBN Complex (3): Ca Sulfonate/ Phenate/ Salicylate of BI 10
HBN Complex (2): Ca Sulfonate/ Phenate of BI 18
LBN, MBN and HBN represents low, medium and high BN respectively;
A characteristic structural feature of the alkylphenol materials used in the
invention is
meta hydrocarbyl-substitution of the aromatic ring where the substituent is
attached to the
ring at its first (Cl) carbon atom. This structural feature is not available
by chemical alkyl
phenol synthesis such as the Friedel-Crafts reaction of phenol with olefins.
The latter
typically gives mixtures of ortho and para alkyl phenols (but only around 1 %
of meta
alkyl phenols), and where attachment of the alkyl group to the aromatic ring
is at the
second (C2) or higher carbon atom.
Cardanol, the product obtained by distilling technical CNSL, typically
contains 3-
pentadecylphenol (3 %); 3-(8-pentadecenyl) phenol (34-36 %); 3-(8, 11-
pentadecadienyl)
phenol (21-22 %); and 3-(8, 11, 14-pentadecatrienyl) phenol (40-41 %), plus a
small
amount of 5-(pentadecyl) resorcinol (c. 10 %), also referred to as cardol.
Technical CNSL
contains mainly cardanol plus some polymerized material. Cardanol may
therefore be
expressed as containing significant amounts of meta-linear hydrocarbyl
substituted phenol,
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where the hydrocarbyl group has the formula CI5H25.31 and is attached to the
aromatic ring
at its first carbon atom (C1).
Thus, both cardanol and technical CNSL contain significant quantities of
material having
long linear unsaturated side chains and only small quantities of material with
long linear
saturated side chains. The present invention preferably employs material where
a major
proportion, preferably all of the phenol, contains material with long linear
saturated side
chains. Such latter material is obtainable by hydrogenating cardanol; a
preferred example .
is 3-(pentadecyl) phenol, where the pentadecyl group is linear and is attached
to the
aromatic ring at its first carbon atom. It may constitute 50 or more, 60 or
more, 70 or
more, 80 or more, or 90 or more, mass % of additive compound (A). It may
contain small
quantities of 3-(pentadecyl) resorcinol together with hydrogenated distilled
cashew nut
shell liquid (CNSL), ex Sigma Aldrich.
Further MDCL's, for use in comparison or reference tests, were made comprising
the
detergent, without hydrogenated distilled CNSL, and hydrogenated distilled
CNSL,
without detergent.
Testing
Samples of each the MDCL's were tested in the Panel Coker High Temperature
Detergency Test ("PC"), the High Frequency Reciprocating Rig (HT HFRR) Test
and the
Komatsu Hot Test (for High Temperature Resistance, 330 C, 16 hours) (KHTT).
The test procedures are described as follows.
=
Panel Coker
The Panel Coker Test involves splashing the MDCL onto a heated test panel to
see if it
degrades and leaves any deposits that might affect engine performance. The
test uses a
panel coker tester (model PK-S) supplied by Yoshida Kagaku Kikai Co, Osaka,
Japan.
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The test starts by heating the MDCL to a temperature of 100 C through an oil
bath. A test
panel made of aluminium alloy, which has been cleaned using acetone and
heptane and
weighed, is placed above the MDCL and heated to 320 C using an electric
heating
element. When both temperatures have stabilised, a splasher splashes the MDCL
onto the
heated test panel in a discontinuous mode: the splasher splashes the MDCL for
15 seconds
and then stops for 45 seconds. The discontinuous splashing takes place over 1
hour, after
which the test is stopped, everything is allowed to cool down, and then the
aluminium test
panel is weighed and rated visually. The difference in weight of the aluminium
test panel
before and after the test, expressed in mg, is the weight of deposits. This
test is used for
simulating the ability of MDCL to prevent deposit formation on pistons. The
panel is also
rated by an electronic optical rater using a Video-Cotateur from ADDS, for
discolouration
caused by MDCL deposits. The higher the merit rating, the cleaner the panel.
HT HFRR
The HFRR or High Frequency Reciprocating Rig Test is a computer-controlled
reciprocating oscillatory friction and wear test system for the wear testing
of lubricants
under boundary lubrication conditions. An electromagnetic vibrator oscillates
a steel ball
over a small amplitude while pressing it with a load of lON against a
stationary steel disc.
The lower, fixed disc is heated electrically and is fixed below the MDCL. The
temperature is ramped from 80 C to 380 C in 15 minutes. The friction
coefficient is
measured vs. temperature. The friction coefficient decreases with increase in
temperature
due to the viscosity decrease of the MDCL, until a temperature at which oil
film
breakdown begins. At this point, the friction coefficient begins to increase
again. The
temperature at which the friction coefficient is a minimum is measured; the
higher this
temperature, the better the MDCL is at protecting the cylinder liner against
scuffing wear.
KHTT
The Hot Tube Test evaluates the high temperature stability of a lubricant. Oil
droplets are
pushed up by air inside a heated narrow glass capillary tube and the thin film
oxidative
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stability of the MDCL is measured by the degree of lacquer formation on the
glass tube,
the resulting colour of the tube being rated on a scale of 0-10. A rating of 0
refers to
heavy deposit formation and a rating of 10 means a clean glass tube at the end
of the test.
The method is described in SAE paper 840262. The level of lacquer formation in
the tube
reflects the high temperature stability of the MDCL and its tendency during
service to
form deposits in high temperature areas of the engine.
Results
The results of the tests are set out in the table below.
=
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Detergent System HT HFRR
=
Ex CNSL KHTT
PC
Type %Ca B1 (%) Min Fn T of Min Fn % Fn
incr
Ref- 2.00 721.20 0.056 309.4 112.5 .. 0.0162
A HBN Sal 0.32 7.8 107.60 0.072 234.6
34.2 0.00267
1 " 2.00 7.10 0.005 337.9 86.5
0.0216
B LBN Sul 0.09 0.4 21.50
0.103 347.6 111.9 -0.0059
HBN Sul 0.31 22
2 " " 2.00 4.10 0.056 311.1 50.0
0.0254 .
C HBN Sul 3.4 22 244.70 0.127 299.2
73.4 0.0203
3 " 2.00 2.90 0.048 339.9 47.5
0.1411
- D HBN Phe 0.33 2.9 541.35 0.127 228.3
63.1 0.0501
4 2.00 361.50 0.113 251.5
47.8 0.0328
E Phe/Sal Complex 0.34 18 - 1.10
0.103 354.5 100.9 0.0642
" - - 2.00 4.95 0.063 352.7 87.5 0.0257
F Phe/Sul/Sal Complex 0.34 10 - 30.00 0.100 283.3
239.0 0.0286
6 2.00 2.15 0.048 351.3 25.3
0.0223
G MBN Phe 0.33 1.8 - 350.15 0.132
348.0 109.0 0.02
7 2.00 15.00 0.115 317.9
150.4 0.0106
-
8 " 4.00 7.20 0.092 349.4 96.8
0.0085
"
9 " " " 6.00 9.30 0.104 246.6 39.5
0.0162
The KHTT results are expressed as mass of deposits forming, a lower value
indicating a
better performance.
The HT HFRR results are expressed as: .
minimum coefficient of friction ("Min Fn"), a lower value indicating a better
performance;
temperature in C of minimum friction ("T of Min Fn"), a higher value
indicating a
better performance; and
.
% friction increment ("% Fn incr), a lower value indicating a better
performance.
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The PC results are expressed as mass of deposits formed in g, a lower value
indicating a
better performance.
In the table, examples of the invention are denoted by numbers; the other
examples are
reference or comparison examples.
The data show that the combination of detergent and CNSL generally gives rise
to better
MDCL performance than the use of either detergent or CNSL alone.
