Note: Descriptions are shown in the official language in which they were submitted.
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BEARING LUBRICANTS FOR PULVERIZING EQUIPMENT
Field of the Invention
[0001] The invention relates to a method of lubricating the bearings
of solid fuel
pulverizers, for example, coal pulverizers. The method involves supplying to
the
bearings a lubricating composition designed to have superior performance
compared
to conventional coal pulverizer bearing lubricants. The invention also
provides a
bearing lubricant for a coal pulverizer as well as its use in coal pulverizing
equipment to improve the service life and/or durability of bearings in coal
pulverizing equipment. The invention also provides an additive composition for
use
in a bearing lubricant for a coal pulverizer, as well as the use of the
additive
composition to improve the service life and/or performance of the bearing
lubricant.
Background of the Invention
[0002] Pulverizers are well known for the reduction of the particle
size of solid
fuel to allow for combustion of the solid fuel in a furnace. A pulverizer
employs
some combination of impact, attrition and crushing to reduce a solid fuel to a
particular particle size. Several types of pulverizer mills can be employed
for the
pulverization of the solid fuel, for example, coal, to a particulate size
appropriate for
firing in a furnace. These can include ball-tube mills, impact mills,
attrition mills,
ball race mills, and ring roll or bowl mills. Most typically, however, bowl
mills with
integral classification equipment are employed for the pulverization of the
solid fuel
to allow for transport, drying and direct firing of the pulverized fuel
entrained in an
air stream. There is an on-going need to improve the mill loading and roll
life of the
bearings of these pulverizers.
[0003] Another factor which deteriorates roll life of the bearings in
addition to
increased mill loading includes solid fuel dust, such as coal dust, for
example, which
flows into and contaminates the bearings as well as the lubricant. Typically,
pulverizers have an interface between the rotatable assembly and stationary
shaft
that is exposed to atmospheric conditions and a differential pressure across
the
assembly allows the coal dust, for example, to flow into the assembly housing
the
bearings. The ingress of coal at this interface, which allows the shaft to
extend there
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through and rotate with respect to the journal assembly, contaminates the
lubricant
and journal bearings thus deteriorating the roll life of the journal bearings.
[0004] Some approaches involve complicated mechanical seals and
expensive
new equipment designed to reduce the amount of dust ingress. However, these
solution do nothing for the current equipment already in use.
[0005] Therefore, there remains a need for a method, and a lubricant,
and an
additive package that increases bearing roll life in these pulverisers, which
facilitates
increased mill loading and prevents damage from contamination of the bearings,
thus allowing more effective use of existing equipment without the need for
costly
refits and modifications.
Summary of the Invention
[0006] The invention provides a method of lubricating the bearings of
a solid
fuel pulverizer. The method involved supplying to the bearings a lubricating
composition designed to have superior performance compared to conventional
solid
fuel pulverizer bearing lubricants. The lubricating composition is designed to
have
improved dust loading capability, in other words, the lubricant is designed to
perform better and/or last longer than conventional lubricants in the harsh
conditions
seen in pulverizers, including conditions related to large amounts of dust in
the
environment, which does get worked into the lubricant. The invention also
provides
a bearing lubricant for a pulverizer as well as its use in pulverizing
equipment to
improve the service life and/or durability of bearings in pulverizing
equipment. The
invention also provides an additive composition for use in a bearing lubricant
for a
pulverizer, as well as the use of the additive composition to improve the
service life
and/or performance of the bearing lubricant. In some embodiments, the solid
fuel
pulverizer described herein is a coal pulverizer.
[0007] The lubricating composition of the invention includes (a) an
oil of
lubricating viscosity, (b) a phosphorus-containing compound, and (c) a
nitrogen-
containing dispersant, where the phosphorus-containing compound and the
nitrogen-
containing dispersant work together to allow for better performance in the
pulverizer
bearing lubricant. In some embodiments, the compositions further include (d) a
sulfur-containing compound.
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[0008] In
some embodiments, the invention deals with mineral base oil
lubricants. In other embodiments, the invention deals with synthetic base oil
lubricants.
[0009] The
invention provides for various phosphorus-containing compound
including an alkyl phosphite, a phosphoric acid ester, an amine salt of a
phosphoric
acid ester, or some combination thereof In some embodiments, the phosphorus-
containing compound comprises an alkyl phosphite.
[0010] The
invention provides for various nitrogen-containing dispersants
including a polyetheramine, a borated succinimide dispersant, a non-borated
succinimide dispersant, a Mannich dispersant comprising the reaction product
of (i)
a dialkylamine, (ii) an aldehyde and (iii) a hydrocarbyl substituted phenol,
as well as
any combination of the various nitrogen-containing dispersants. In
some
embodiments, the nitrogen-containing dispersant comprises a non-borated
succinimide dispersant. The invention further provides for a lubricant
containing an
alkyl phosphite and a non-borated succinimide dispersant.
[0011] In
any of these embodiments, the phosphorus-containing compound may
be present in the lubricant composition from 0.25 or 0.5 up to 2.0 or 1.0
percent by
weight and the nitrogen-containing dispersant is present in the lubricant
composition
from 0.1 or 0.5 up to 2.0 or 1.0 percent by weight, on an oil free basis,
which may
also be described herein is on an actives basis.
Detailed Description of the Invention
[0012]
Various features and embodiments of the invention will be described
below by way of non-limiting illustration.
The Pulverizer and Method of Lubrication
[0013] The
pulverizers suitable for use with the present invention are not overly
limited. Pulverizers may generally be described as devices employable for
purposes
of effecting the grinding of materials. More specifically, the prior art is
replete with
examples of various types of apparatus that have been used to effect the
grinding of
many different kinds of materials. In this regard, in many instances
discernible
differences of a structural nature can be found to exist between individual
pulverizers. The existence of such differences is, in turn, attributable for
the most
part to the diverse functional requirements that are associated with the
individual
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applications in which pulverizers are designed to be employed. For instance,
in the
selection of the particular type of pulverizer that is to be utilized for a
specific
application, one of the principal factors to consider is that of the nature of
the
material that is to be ground in the apparatus. Coal is one such material
wherein
there is a need to grind it in order to render it suitable for use in certain
applications.
Furthermore, fossil fuel fired power generation systems represent one such
application in which it is desired to employ coal, as the source of fuel, and
wherein a
requirement exists to grind, i.e., pulverize, the coal to render it suitable
for use for
this purpose, i.e., for use in a coal-fired power generation system. Thus, in
some
embodiments, the pulverizers used with the invention are coal pulverizers.
[0014] In some embodiments, the pulverizers of the invention may
include a
feeder for feeding solid fuel to the pulverizer, an apparatus for pulverizing
the solid
fuel, a distribution system for distributing the solid fuel after the
pulverization
thereof, a furnace in which the solid fuel is to be burned and the requisite
controls
for effecting the proper operation of the solid fuel-fired power generation
system. Of
particular interest here the apparatus for pulverizing the solid fuel, for
example, coal.
[0015] In some embodiments, the pulverizer of the present invention is
a bowl
mill. A bowl mill may essentially consists of a body portion in which a
grinding
table is mounted for rotation, a plurality of grinding rollers that coact with
the
grinding table to effect the grinding of solid fuel interposed there between,
solid fuel
supply means for feeding to the interior of the bowl mill the solid fuel that
is to be
pulverized, and air supply means for supplying to the interior of the bowl
mill the air
required in the operation of the latter. In accordance with the mode of
operation of
such a bowl mill, the solid fuel, which enters the bowl mill, is pulverized by
virtue
of the coaction of the grinding rollers with the grinding table. After being
pulverized, the solid fuel particles are thrown outwardly by centrifugal force
whereby the particles are fed into a stream of air that is entering the bowl
mill. The
stream of air, which now contains pulverized solid fuel particles, flows
through a
tortuous path that is established in part by the positioning within the bowl
mill of a
suitably supported deflector means. As the stream of air and solid fuel
particles
flows along the aforementioned tortuous path, the sharp turns contained
therein
effects the separation of the coarse solid fuel particles from the air stream.
These
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coarse solid fuel particles are then suitably returned to the grinding table
for further
pulverization while the fine solid fuel particles are carried through the bowl
mill in
the air stream, and exit therefrom along with the air. Each bowl mill will
typically
also have bearings, for example, upper bearings and lower bearings associated
with
the grinding rollers with the grinding table and/or their mounts.
[0016]
Each pulverizer will typically also have a lubrication system for
supplying lubricant to its beatings, including the upper and lower bearings of
a bowl
mill described, but all the various bearing that may be found in the various
types of
pulverizers used in the field.
[0017] The present
invention provides a lubricant composition for the bearings
of a solid fuel pulverizer and also provides a method of lubricating the
bearings of a
coal pulverizer by supplying to said bearings the described lubricant
composition.
The lubricant compositions useful in the invention are described below.
[0018] In
some embodiments, the method of the invention involves supplying
the described lubricant composition to a coal pulverizer. In some embodiments,
the
method of the invention involves supplying the described lubricant composition
to a
bowl mill pulverizer. In some embodiments, the method of the invention
involves
supplying the described lubricant composition to a bowl mill coal pulverizer.
In
some embodiments, the method of the invention involves supplying the described
lubricant composition to the upper bearings of the pulverizer. In some
embodiments, the method of the invention involves supplying the described
lubricant composition to the lower bearings of the pulverizer. In
some
embodiments, the method of the invention involves supplying the described
lubricant composition to the upper and lower bearings of the pulverizer, or
even all
of the bearings in the pulverizer.
The Lubricant Composition
[0019] The
invention includes a bearing lubricating composition made up of (a)
an oil of lubricating viscosity, (b) a phosphorus-containing compound, and (c)
a
nitrogen-containing dispersant, where the phosphorus-containing compound and
the
nitrogen-containing dispersant work together to allow for better performance
in the
pulverizer bearing lubricant. The invention also provides an additive
composition
for use in a bearing lubricant for a pulverizer made up of (a) an optional
diluent
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which may be an oil of lubricating viscosity or solvent, and (b) a phosphorus-
containing compound, and (c) a nitrogen-containing dispersant, where the
phosphorus-containing compound and the nitrogen-containing dispersant work
together to allow for better performance in the pulverizer bearing lubricant.
In some
embodiments, the compositions further include (d) a sulfur-containing
compound.
[0020] In some embodiments, the lubricant composition contains from
0.01 to
5.0, or from 0.25 to 5.0, or from 0.5 to 5.0, or from 0.5 to 4.0, from 0.75 to
3.0, from
0.9 to 2.0, or from 1 to 2, or even 1 or 2 percent by weight of a phosphorus-
containing compound, on an actives basis (meaning no diluent oil or solvent is
includes, rather the components are considered on a neat basis). In some
embodiments, the lubricant composition contains a phosphorus-containing
compound in an amount sufficient to deliver from 0.01 to 5.0, or from 0.025 to
0.5
or from 0.025 to 0.25, or from 0.05 to 0.1 percent by weight phosphorus to the
overall lubricant composition.
[0021] In some embodiments, the lubricant composition contains from 0.01 or
0.1 or 0.25 to 10 or 5 or 4, or from 0.01 or 0.1 or 0.25 to 5, or from 0.1 to
1.0, or
from 0.4 to 2.0 or 2.5, or from 0.5 to 2.0 percent by weight of a nitrogen-
containing
dispersant on an actives basis.
[0022] In some embodiments, the phosphorus-containing compound and the
nitrogen-containing dispersant are present in the lubricant composition in a
ratio
from 1:10 to 10:1, or from 1:4 to 4:1, or from 1:2 to 4:1, or from 1:1 to 3:1,
or even
about 2:1, where the ratio is a weight ratio considered on an actives free
basis. In
some embodiments, the phosphorus-containing compound and the nitrogen-
containing dispersant are present in the lubricant composition in a ratio from
0.5:1 to
4:1, or from and/or to about 0.5:1, 1:1, 1.2:1, 2:1 or 4:1, where the ratio is
a weight
ratio considered on an oil free basis.
The Oil of Lubricating Viscosity
[0023] One component of the compositions of the invention is an oil of
lubricating viscosity, which can be present in a major amount, for a lubricant
composition, or in a concentrate forming amount, for a concentrate and/or
additive
composition.
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[0024] Suitable oils include natural and synthetic lubricating oils
and mixtures
thereof In a fully formulated lubricant, the oil of lubricating viscosity is
generally
present in a major amount (i.e., an amount greater than 50 percent by weight).
Typically, the oil of lubricating viscosity is present in an amount of 75 to
95 percent
by weight, and often greater than 80 percent by weight of the overall
composition.
The base oil component generally makes up 100 parts by weight (pbw) of the
overall
composition with the pbw ranges for the other components being provided with
this
100 pbw of base oil in mind. In other embodiments, the pbw ranges of the
various
components, including the base oils, are provided such that the total of the
pbw of
all components is 100, and thus the pbw values are equivalent to percent by
weight
values. The pbw ranges provided for the various components described below may
be taken either way, however, in most embodiments they are to be read so as to
be
equivalent to percent by weight values.
[0025] The oil of lubricating viscosity may include natural and
synthetic oils, oil
derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined,
refined
and refined oils or mixtures thereof. Unrefined oils are those obtained
directly from
a natural or synthetic source generally without (or with little) further
purification
treatment. Refined oils are similar to the unrefined oils except they have
been
further treated in one or more purification steps to improve one or more
properties.
Purification techniques are known in the art and include solvent extraction,
secondary distillation, acid or base extraction, filtration, percolation and
the like.
Re-refined oils are also known as reclaimed or reprocessed oils, and are
obtained by
processes similar to those used to obtain refined oils and often are
additionally
processed by techniques directed to removal of spent additives and oil
breakdown
products.
[0026] Natural oils useful as the oil of lubricating viscosity include
animal oils,
vegetable oils (e.g., castor oil, lard oil), mineral lubricating oils such as
liquid
petroleum oils and solvent-treated or acid-treated mineral lubricating oils of
the
paraffinic, naphthenic or mixed paraffinic naphthenic types and oils derived
from
coal or shale or mixtures thereof.
[0027] Synthetic oils of lubricating viscosity include hydrocarbon
oils such as
polymerized and interpolymerised olefins (e.g., polybutylenes, polypropylenes,
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propyleneisobutylene copolymers); poly( 1 -hex enes), poly( 1 -o ctenes),
poly( 1 -
decenes), and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzenes,
tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes); polyphenyls
(e.g., biphenyls, terphenyls, alkylated polyphenyls); alkylated biphenyl
ethers and
alkylated biphenyl sulfides and the derivatives, analogs and homologs thereof
or
mixtures thereof. In some embodiments, the oil of lubricating viscosity used
in the
invention is a synthetic oil that includes polymerized polyisobutylene, and in
some
embodiments, the oil of lubricating viscosity used in the invention is a
synthetic oil
that includes polymerized polyisobutylene and a polyalphaolefin).
[0028] Another synthetic oil of lubricating viscosity include polyol esters
other
than the hydrocarbyl-capped polyoxyalkylene polyol as disclosed herein,
dicarboxylic esters, liquid esters of phosphorus-containing acids (e.g.,
tricresyl
phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic
acid), or
polymeric tetrahydrofurans. Synthetic conventional oil of lubricating
viscosity also
include those produced by Fischer-Tropsch reactions and typically may be
hydroisomerised Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the
oil of lubricating viscosity may be prepared by a Fischer-Tropsch gas-to-
liquid
synthetic procedure as well as other gas-to-liquid oils.
[0029] Oils of lubricating viscosity may further be defined as
specified in the
American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The
five base oil groups are as follows: Group I (sulfur content >0.03 percent by
weight,
and/or <90 percent by weight saturates, viscosity index 80-120); Group II
(sulfur
content <0.03 percent by weight and >90 percent by weight saturates, viscosity
index 80-120); Group III (sulfur content <0.03 percent by weight and >90
percent by
weight saturates, viscosity index >120); Group IV (all polyalphaolefins, or
PAO,
such as PA0-2, PA0-4, PA0-5, PA0-6, PA0-7 or PA0-8); and Group V. The oil
of lubricating viscosity includes API Group I, Group II, Group III, Group IV,
Group
V oil or mixtures thereof In one embodiment, the oil of lubricating viscosity
is an
API Group I, Group II, Group III, Group IV oil or mixtures thereof.
Alternatively,
the oil of lubricating viscosity is often an API Group II, Group III or Group
IV oil or
mixtures thereof.
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[0030] In some embodiments, the lubricating oil component of the
present
invention includes a Group II or Group III base oil, or a combination thereof.
These
are classifications established by the API (American Petroleum Institute).
Group III
oils contain < 0.03 percent sulfur and > 90 percent saturates and have a
viscosity
index of > 120. Group II oils have a viscosity index of 80 to 120 and contain
<0.03
percent sulfur and > 90 percent saturates. The oil can also be derived from
the
hydroisomerization of wax, such as slack wax or a Fischer-Tropsch synthesized
wax. Such "Gas-to-Liquid" oils are typically characterized as Group III.
[0031] The compositions of the present invention may include some
amount of
Group I base oils, and even Group IV and Group V base oils. Polyalphaolefins
are
categorized as Group IV. Group V encompasses "all others". However, in some
embodiments, the lubricating oil component of the invention contains no more
than
20, 10, 5, or even 1 percent by weight Group I base oil. These limits may also
apply
to Group IV or Group V base oils. In other embodiments, the lubricating oil
present
in the compositions of the invention is at least 60, 70, 80, 90, or even 95
percent by
weight Group II and/or Group III base oil. In some embodiments, the
lubricating oil
present in the compositions of the invention is essentially only Group II
and/or
Group III base oil, where small amounts of other types of base oils may be
present
but not in amounts that significantly impact the properties or performance of
the
overall composition.
[0032] In some embodiments, the compositions of the invention include
some
amount of Group I and/or Group II base oils. In other embodiments, the
compositions of the invention are lubricating compositions where the oil of
lubricating viscosity is primarily Group I and/or Group II base oils, or even
essentially Group I and/or Group II base oils, or even exclusively Group I
and/or
Group II base oils.
[0033] In some embodiments, the compositions of the invention include
some
amount of Group I and/or Group II base oils. In other embodiments, the
compositions of the invention are lubricating compositions where the oil of
lubricating viscosity is primarily Group I and/or Group II base oils, or even
essentially Group I and/or Group II base oils, or even exclusively Group I
and/or
Group II base oils.
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[0034] The various described oils of lubricating viscosity may be used
alone or
in combinations. The oil of lubricating viscosity is used in the range of
about 70
percent by weight to about 99 percent by weight, and in another embodiment, in
the
range of about 75 percent by weight to about 98 percent by weight, in another
embodiment in the range of about 88 percent by weight to about 97 percent by
weight of the lubricant.
The Phosphorus-Containing Compound
[0035] The compositions useful in the invention include a phosphorus-
containing compound.
[0036] In some embodiments, the phosphorus-containing compound is a
phosphite. Suitable phosphites include those having at least one hydrocarbyl
group
with 4 or more, or 8 or more, or 12 or more, carbon atoms. Typical ranges for
the
number of carbon atoms on the hydrocarbyl group include 8 to 30, or 10 to 24,
or 12
to 22, or 14 to 20, or 16 to 18. The phosphite may be a mono-hydrocarbyl
substituted phosphite, a di-hydrocarbyl substituted phosphite, or a tri-
hydrocarbyl
substituted phosphite.
[0037] In one embodiment, the phosphite is sulphur-free i.e., the
phosphite is not
a thiophosphite.
[0038] The phosphite having at least one hydrocarbyl group with 4 or
more
carbon atoms may be represented by the formulae:
R3-o\ /H
R4-0P\
0
Or
R5
0
1
P
3
0
R4-0 R
wherein at least one of R3, R4 and R5 may be a hydrocarbyl group containing at
least
4 carbon atoms and the other may be hydrogen or a hydrocarbyl group. In one
embodiment, both R3, R4 and R5 are hydrocarbyl groups. The hydrocarbyl groups
may be alkyl, cycloalkyl, aryl, acyclic or mixtures thereof In the formula
with all
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three groups R3, R4 and R5, the compound may be a tri-hydrocarbyl substituted
phosphite i.e., R3, R4 and R5 are all hydrocarbyl groups.
[0039] Alkyl groups may be linear or branched, typically linear, and
saturated or
unsaturated, typically saturated. Examples of alkyl groups for R3, R4 and R5
include
octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,
pentadecyl,
hexadecyl, heptadecyl, octadecyl, octadecenyl, nonadecyl, eicosyl or mixtures
thereof
[0040] In some embodiments, the phosphorus-containing compound is an
amine
salt of a phosphate hydrocarbon ester (i.e., an amine salt of a hydrocarbon
ester of
phosphoric acid). The amine salt of a phosphate hydrocarbon ester may be
derived
from an amine salt of a phosphate. The amine salt of the phosphate hydrocarbon
ester may be represented by the formula:
0 R5
R3-0Il R6
+1 /
P-0- N
R4¨/ 1 \ R7
R8
Wherein: R3 and R4 may be independently hydrogen or hydrocarbon typically
containing 4 to 40, or 6 to 30, or 6 to 18, or 8 to 18 carbon atoms, with the
proviso
that at least one is a hydrocarbon group; and R5, R6, R7 and R8 may be
independently
hydrogen or a hydrocarbyl group, with the proviso that at least one is a
hydrocarbyl
group. The hydrocarbon groups of R3 and/or R4 may be linear, branched, or
cyclic.
[0041] Examples of a hydrocarbon group for R3 and/or R4 include
straight-chain
or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl,
heptyl,
octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl,
heptadecyl and octadecyl. Additional examples include 2-ethylhexl, 4-methy1-2-
pentyl, and isopropyl.
[0042] Examples of a cyclic hydrocarbon group for R3 and/or R4 include
cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, dimethylcyclopentyl,
methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, diethyl-
cyclopentyl, methylcyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl,
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diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl, methylethyl-
cycloheptyl, and diethylcycloheptyl.
[0043] In
one embodiment, the phosphate may be an amine salt of a mixture of
monoalkyl and dialkyl phosphoric acid esters. The monoalkyl and dialkyl groups
may be linear or branched.
[0044] The
amine salt of a phosphate hydrocarbon ester may be derived from an
amine such as a primary amine, a secondary amine, a tertiary amine, or
mixtures
thereof. The amine may be aliphatic, or cyclic, aromatic or non-aromatic,
typically
aliphatic. In one embodiment, the amine includes an aliphatic amine such as a
tertiary-aliphatic primary amine.
[0045]
Examples of suitable primary amines include ethylamine, propylamine,
butylamine, 2-ethylhexylamine, bis-(2-ethylhexyl)amine, octylamine, and
dodecyl-
amine, as well as such fatty amines as n-octylamine, n-decylamine, n-
dodecylamine,
n-tetradecylamine, n-hexadecylamine, n-octadecylamine and oleylamine. Other
useful fatty amines include commercially available fatty amines such as
"Armeen "
amines (products available from Akzo Chemicals, Chicago, Illinois), such as
Armeen C, Armeen 0, Armeen OL, Armeen T, Armeen HT, Armeen S and Armeen
SD, wherein the letter designation relates to the fatty group, such as coco,
oleyl,
tallow, or stearyl groups.
[0046] Examples of
suitable secondary amines include dimethylamine,
diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine,
diheptylamine, methyl ethylamine, ethylbutylamine, N-
methyl-l-amino-
cyclohexane, Armeen 2C and ethylamylamine. The secondary amines may be
cyclic amines such as piperidine, piperazine and morpholine.
[0047] Examples of
tertiary amines include tri-n-butylamine, tri-n-octylamine,
tri-decylamine, tri-laurylamine, tri-hexadecylamine, and dimethyloleylamine
(Armeen DMOD).
[0048] In
one embodiment, the amines are in the form of a mixture. Examples
of suitable mixtures of amines include (i) a tertiary alkyl primary amine with
11 to
14 carbon atoms, (ii) a tertiary alkyl primary amine with 14 to 18 carbon
atoms, or
(iii) a tertiary alkyl primary amine with18 to 22 carbon atoms. Other examples
of
tertiary alkyl primary amines include tert-butylamine, tert-hexylamine, tert-
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octylamine (such as 1,1-dimethylhexylamine), tert-decylamine (such as 1,1-
dimethyloctylamine), tertdodecylamine, tert-tetradecylamine, tert-
hexadecylamine,
tert-octadecylamine, tert-tetracosanylamine, and tert-octacosanylamine.
[0049] In one embodiment, a useful mixture of amines is "Primene0 81R"
or
"Primene0 JMT." Primene0 81R and Primene0 JMT (both produced and sold by
Rohm & Haas) are mixtures of C11 to C14 tertiary alkyl primary amines and C18
to
C22 tertiary alkyl primary amines respectively.
[0050] The amine salt of a phosphate hydrocarbon ester may be prepared
as is
described in US Patent 6,468,946. Column 10, lines 15 to 63 describes
phosphoric
acid esters formed by reaction of phosphorus compounds, followed by reaction
with
an amine to form an amine salt of a phosphate hydrocarbon ester. Column 10,
line
64, to column 12, line 23, describes preparative examples of reactions between
phosphorus pentoxide with an alcohol (having 4 to 13 carbon atoms), followed
by a
reaction with an amine (typically Primene081-R) to form an amine salt of a
phosphate hydrocarbon ester.
[0051] Suitable phosphorus-containing compounds also include
hydrocarbyl
amine salts of dialkyldithiophosphoric acid. Examples of hydrocarbyl amine
salts
of dialkyldithiophosphoric acid are represented by the formula:
R2-4
P
R28,-0
RP
wherein R26 and R27 are independently branched or linear alkyl groups. R26 and
R27
contain about 3 to about 30, preferably about 4 to about 25, more preferably
about
5 to about 20, and most preferably about 6 to about 19 carbon atoms. R23, R24
and
R25 are as described above.
[0052] In some embodiments, the hydrocarbyl amine salts of
dialkyldithiophosphoric acid include but are not limited to the reaction
product(s) of
diheptyl or dioctyl or dinonyl dithiophosphoric acids with ethylenediamine,
morpho line or Primene 81R or mixtures thereof
[0053] The phosphorus-containing compound may be present at 0.01
percent by
weight to 5 percent by weight, or 0.1 percent by weight to 3 percent by
weight, or
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0.2 percent by weight to 1.5 percent by weight, or 0.25 percent by weight to 1
percent by weight, or 0.5 percent by weight to 1 percent by weight of the
described
composition.
The Nitrogen-Containing Dispersant
[0054] The compositions useful in the invention include a nitrogen-
containing
dispersant, which in some embodiments is a hydrocarbyl substituted nitrogen
containing additive. Suitable hydrocarbyl substituted nitrogen containing
additives
for use in the present invention includes additives sometimes referred to as
ashless
dispersants. Dispersants in general are well known in the field of lubricants
and fuel
(though often these additives are referred to as fuel detergents when used in
fuel
applications). Suitable materials include primarily what is known as ashless
dis-
persants and polymeric dispersants. Ashless dispersants are so-called because,
as
supplied, they do not contain metal and thus do not normally contribute to
sulfated
ash when added to a lubricant. However, they may, of course, interact with
ambient
metals once they are added to a lubricant which includes metal-containing
species.
Ashless dispersants are characterized by a polar group attached to a
relatively high
molecular weight hydrocarbon chain. Examples of such materials include
succinimide dispersants, Mannich dispersants, and borated derivatives thereof.
[0055] Mannich dispersants, sometimes referred to as a Mannich base
dispersant
or Mannich detergents, are the reaction product of a hydrocarbyl-substituted
phenol,
an aldehyde, and an amine or ammonia. The hydrocarbyl substituent of the
hydrocarbyl-substituted phenol can have 10 to 400, 30 to 180, 10 or 40 to 110
carbon atoms. This hydrocarbyl substituent can be derived from an olefin or a
polyolefin, such as 1-decene, which are commercially available.
[0056] The polyolefins, which can form the hydrocarbyl substituent can be
prepared, for instance, by polymerizing olefin monomers by well-known
polymerization methods and are also commercially available. The olefin
monomers
include monoolefins, including monoolefins having 2 to 10 carbon atoms such as
ethylene, propylene, 1-butene, isobutylene, and 1-decene. An especially useful
monoolefin source is a C4 refinery stream having a 35 to 75 weight percent
butene
content and a 30 to 60 weight percent isobutene content. Useful olefin
monomers
also include diolefins such as isoprene and 1,3-butadiene. Olefin monomers can
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also include mixtures of two or more monoolefins, of two or more diolefins, or
of
one or more monoolefins and one or more diolefins. Useful polyolefins include
polyisobutylenes having a number average molecular weight of 140 to 5000, in
another instance of 400 to 2500, and in a further instance of 140 or 500 to
1500.
The polyisobutylene can have a vinylidene double bond content of 5 to 69%, in
a
second instance of 50 to 69%, and in a third instance of 50 to 95%. The
polyolefin
can be a homopolymer prepared from a single olefin monomer or a copolymer
prepared from a mixture of two or more olefin monomers. Also possible as the
hydrocarbyl substituent source are mixtures of two or more homopolymers, two
or
more copolymers, or one or more homopolymers and one or more copolymers. The
foregoing description of suitable hydrocarbyl groups or polyolefin groups is
also
applicable to the hydrocarbyl substituent of the succinimide dispersant,
described in
detail below.
[0057] The hydrocarbyl-substituted phenol which is used to prepare the
Mannich dispersant can be prepared by alkylating phenol with an olefin or
polyolefin described above, such as a polyisobutylene or polypropylene, using
well-
known alkylation methods.
[0058] The aldehyde used to form the Mannich dispersant can have 1 to
10
carbon atoms, and is generally formaldehyde or a reactive equivalent thereof
such as
formalin or paraformaldehyde.
[0059] The amine used to form the Mannich dispersant can be a
monoamine or a
polyamine, including those materials described below for the succinimide
dispersants, including alkanolamines having one or more hydroxyl groups.
Useful
amines include ethanolamine, diethanolamine, methylamine, dimethylamine,
ethylenediamine, dimethylaminopropylamine, diethylenetriamine and 2-(2-amino-
ethylamino)ethanol. The Mannich dispersant can be prepared by reacting a
hydrocarbyl-substituted phenol, an aldehyde, and an amine as described in U.S.
Patent No. 5,697,988. In one embodiment, the Mannich reaction product is
prepared
from an alkylphenol derived from a polyisobutylene, formaldehyde, and an amine
that is a primary monoamine, a secondary monoamine, or an alkylenediamine, in
particular, ethylenediamine or dimethylamine. In one embodiment, the
alkylphenol
may be prepared from a high-vinylidene polyisobutene, having, e.g., greater
than 50,
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greater than 70 or greater than 75 percent terminal vinylidene groups (i.e.,
such
percentage of polyisobutylene molecules having vinylidene end groups.) The
foregoing description of the amine is also applicable to the description of
the amine
used in preparing the succinimide dispersant, described below.
[0060] In one embodiment, the Mannich dispersant comprises the reaction
product of a hydrocarbyl-substituted phenol, formaldehyde or a reactive
equivalent
of formaldehyde, and a primary or secondary amine. In one embodiment, the
Mannich dispersant comprises the reaction product of a polyisobutene-
substituted
phenol, formaldehyde or a reactive equivalent of formaldehyde, and
dimethylamine.
[0061] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl
group" is used in its ordinary sense, which is well-known to those skilled in
the art.
Specifically, it refers to a group having a carbon atom directly attached to
the
remainder of the molecule and having predominantly hydrocarbon character.
Examples of hydrocarbyl groups include hydrocarbon substituents, including
aliphatic, alicyclic, and aromatic substituents; substituted hydrocarbon
substituents,
that is, substituents containing non-hydrocarbon groups which, in the context
of this
invention, do not alter the predominantly hydrocarbon nature of the
substituent; and
hetero substituents, that is, substituents which similarly have a
predominantly
hydrocarbon character but contain other than carbon in a ring or chain. A more
detailed definition of the term "hydrocarbyl substituent" or "hydrocarbyl
group" is
found in paragraphs [0137] to [0141] of published application US 2010/0197536.
[0062] Another suitable hydrocarbyl substituted nitrogen containing
additive is
a succinimide dispersant, which may also be referred to as a succinimide fuel
detergent. In one embodiment, the succinimide dispersant is a condensation
product of hydrocarbyl-substituted succinic anhydride or a reactive equivalent
thereof (e.g., an anhydride, ester, or acid halide), with an amine such as a
polyethylene polyamine. Succinimide dispersants may generally be viewed as
comprising a variety of chemical structures including typically
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0 0
R'l i\IR1
N¨[R2-NFlix-R2-
where each R1 is independently an alkyl group, frequently a polyisobutylene
group
with a molecular weight (M.) of 500-5000 based on the polyisobutylene
precursor,
and R2 are alkylene groups, commonly ethylene (C2H4) groups. Such molecules
are
commonly derived from reaction of an alkenyl acylating agent with a polyamine,
and a wide variety of linkages between the two moieties is possible beside the
simple imide structure shown above, including a variety of amides and
quaternary
ammonium salts. In the above structure, the amine portion is shown as an
alkylene
polyamine, although other aliphatic and aromatic mono- and polyamines may also
be used, including those described above and below. Also, a variety of modes
of
linkage of the R1 groups onto the imide structure are possible, including
various
cyclic linkages. The ratio of the carbonyl groups of the acylating agent to
the
nitrogen atoms of the amine may be 1:0.5 to 1:3, and in other instances 1:1 to
1:2.75
or 1:1.5 to 1:2.5. Succinimide dispersants are more fully described in U.S.
Patents
4,234,435 and 3,172,892 and in EP 0355895.
[0063] Succinimide dispersants may also be described as being prepared
from
hydrocarbyl-substituted succinic acylating agent which are, in turn, prepared
by the
so-called "chlorine" route or by the so-called "thermal" or "direct
alkylation" route.
These routes are described in detail in published application US 2005-0202981,
paragraphs 0014 through 0017. A direct alkylation or low-chlorine route is
also
described in U.S. Patent 6,077,909; refer to column 6 line 13 through col. 7
line 62
and column 9 lines 10 through col. 10 line 11. Illustrative thermal or direct
alkylation processes involve heating a polyolefin, typically at 180 to 250 C,
with
maleic anhydride under an inert atmosphere. Either reactant may be in excess.
If
the maleic anhydride is present in excess, the excess may be removed after
reaction
by distillation. These reactions may employ, as the polyolefin, high
vinylidene
polyisobutylene, that is, having greater than 50, 70, or 75% terminal
vinylidene
groups, in some embodiments alpha vinylidene end groups. In certain
embodiments,
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the succinimide dispersant may be prepared by the direct alkylation route. In
other
embodiments, it may comprise a mixture of direct alkylation and chlorine-route
dispersants.
[0064] Any of these additives may be post-treated with any of a
variety of
agents to impart desirable properties thereto. Such post-treatment includes
reaction
with urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes,
ketones,
carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles,
epoxides,
boron compounds such as boric acid, phosphorus compounds, or mixtures thereof.
References detailing such treatment are listed in U.S. Patent 4,654,403.
[0065] Additional suitable hydrocarbyl substituted nitrogen containing
additives
include acylated amines, hydrocarbyl substituted amines, or mixtures thereof.
[0066] Suitable acylated amines include reaction products of one or
more
carboxylic acylating agent and one or more amine. The carboxylic acylating
agents
include C8_30 fatty acids, C14-20 isoaliphatic acids, Ci8-44 dimer acids,
addition
dicarboxylic acids, trimer acids, addition tricarboxylic acids, and
hydrocarbyl
substituted carboxylic acylating agents, including those described above.
Dimer
acids are described in U.S. Pat. Nos. 2,482,760, 2,482,761, 2,731,481,
2,793,219,
2,964,545, 2,978,468, 3,157,681, and 3,256,304. Suitable amines may be any of
those described above, in some embodiments a polyamine, such as an
alkylenepolyamine or a condensed polyamine. Acylated amines, their
intermediates
and methods for preparing the same are described in U.S. Pat. Nos. 3,219,666;
4,234,435; 4,952,328; 4,938,881; 4,957,649; 4,904,401; and 5,053,152.
[0067] The hydrocarbyl substituted nitrogen containing additive may
also be a
hydrocarbyl-substituted amine. These hydrocarbyl-substituted amines are well
known to those skilled in the art. These amines are disclosed in U.S. Pat.
Nos.
3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,755,433; and 3,822,289.
Typically,
hydrocarbyl substituted amines are prepared by reacting olefins and olefin
polymers,
including the above polyalkenes and halogenated derivatives thereof, with
amines
(mono- or polyamines). The amines may be any of the amines described herein,
and
in some embodiments is an alkylenepolyamine.
[0068] Examples of hydrocarbyl substituted amines include ethylene
polyamines
such as diethylenetriamine; poly(propylene)amine; N,N-dimethyl-N-
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poly(ethylene/propylene)amine, (50:50 mole ratio of monomers); polybutene
amine;
N,N-di(hydroxyethyl)-N-polybutene amine; N-(2-hydroxypropy1)-N-polybutene
amine; N-polybutene-aniline; N-polybutenemorpholine; N-
poly(butene)ethylenediamine; N-poly(propylene)trimethylenediamine; N-
poly(butene)diethylenetriamine; N',N'-poly(butene)tetraethylenepentamine; N,N-
dimethyl-N'-poly(propylene)-1,3-propylenediamine and the like.
[0069] In
some embodiments, the hydrocarbyl substituted nitrogen containing
additives described above are borated. Any of the additives described herein
may be
borated, generally prepared by the reaction of the additive with a boron-
containing
compound, for example, boric acid.
[0070] In
one embodiment, the boron compound is a borated dispersant.
Typically, the borated dispersant contains from about 0.1% to about 5%, or
from
about 0.5% to about 4%, or from 0.7% to about 3% by weight boron. In one
embodiment, the borated dispersant is a borated acylated amine, such as a
borated
succinimide dispersant. Borated dispersants are described in U.S. Pat. Nos.
3,000,916; 3,087,936; 3,254,025; 3,282,955; 3,313,727; 3,491,025; 3,533,945;
3,666,662 and 4,925,983. In one embodiment, the boron compound is an alkali or
mixed alkali metal and alkaline earth metal borate. These metal borates are
generally
hydrated particulate metal borates which are known in the art. Alkali metal
borates
include mixed alkali and alkaline metal borates. These metal borates are
available
commercially. Representative patents disclosing suitable alkali and alkali
metal and
alkaline earth metal borates and their methods of manufacture include U.S.
Pat. Nos.
3,997,454; 3,819,521; 3,853,772; 3,907,601; 3,997,454; and 4,089,790.
[0071]
Hydrocarbyl substituted nitrogen containing additives described above
can also be post-treated by reaction with any of a variety of agents besides
borating
agents. Among these are urea, thiourea, dimercaptothiadiazoles, carbon
disulfide,
aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic
anhydrides,
nitriles, epoxides, and phosphorus compounds. References detailing such
treatment
are listed in U.S. Patent 4,654,403.
[0072] The amines
used in the preparation of the hydrocarbyl substituted
nitrogen containing additives described above may be polyamines. Suitable
polyamines include aliphatic, cycloaliphatic, heterocyclic and aromatic
polyamines.
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Examples of the polyamines include alkylene polyamines, hydroxy containing
polyamines, aryl polyamines, and heterocyclic polyamines.
[0073] Alkylene polyamines are represented by the formula:
(H)(R5)N-(Alkylene-N).-(R5)(R5)
wherein n has an average value from 1, or about 2 to about 10, or to about 7,
or to
about 5, and the "Alkylene" group has from 1, or about 2 to about 10, or to
about 6,
or to about 4 carbon atoms. Each R5 is independently hydrogen, or an aliphatic
or
hydroxy-substituted aliphatic group of up to about 30 carbon atoms.
[0074] Such alkylenepolyamines include methylenepolyamines,
ethylenepolyamines, butylenepolyamines,
propylenepolyamines,
pentylenepolyamines, etc. The higher homologs and related heterocyclic amines
such as piperazines and N-aminoalkyl-substituted piperazines are also
included.
Specific examples of such polyamines are ethylenediamine, diethylenetriamine
(DETA), triethylenetetramine (TETA), tris-(2-aminoethyl)amine,
propylenediamine,
trimethylenediamine, tripropylenetetramine, tetraethylenepentamine, hexa-
ethyleneheptamine, pentaethylenehexamine, etc.
[0075] Higher homologs obtained by condensing two or more of the
above-noted alkylene amines are similarly useful as are mixtures of two or
more of
the aforedescribed polyamines.
[0076] Ethylenepolyamines, such as those mentioned above, are useful.
Such
polyamines are described in detail under the heading Ethylene Amines in Kirk
Othmer's "Encyclopedia of Chemical Technology", 2d Edition, Vol. 7, pages 22-
37,
Interscience Publishers, New York (1965). Such polyamines are most
conveniently
prepared by the reaction of ethylene dichloride with ammonia or by reaction of
an
ethylene imine with a ring opening reagent such as water, ammonia, etc. These
reactions result in the production of a complex mixture of
polyalkylenepolyamines
including cyclic condensation products such as the aforedescribed piperazines.
Ethylenepolyamine mixtures are also useful.
[0077] Other useful types of polyamine mixtures are those resulting
from
stripping of the above-described polyamine mixtures to leave as residue what
is
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often termed "polyamine bottoms". In general, alkylenepolyamine bottoms can be
characterized as having less than two, usually less than 1% (by weight)
material
boiling below about 200 C. A typical sample of such ethylene polyamine bottoms
obtained from the Dow Chemical Company of Freeport, Texas designated "E-100"
has a specific gravity at 15.6 C of 1.0168, a percent nitrogen by weight of
33.15 and
a viscosity at 40 C of 121 centistokes. Gas chromatography analysis of such a
sample contains about 0.93% "Light Ends" (most probably DETA), 0.72% TETA,
21.74% tetraethylene pentamine and 76.61% pentaethylenehexamine and higher (by
weight). These alkylenepolyamine bottoms include cyclic condensation products
such as piperazine and higher analogs of diethylenetriamine,
triethylenetetramine
and the like. These alkylenepolyamine bottoms can be reacted solely with the
acylating agent or they can be used with other amines, polyamines, or mixtures
thereof.
[0078]
Another useful polyamine is a condensation reaction between at least one
hydroxy compound with at least one polyamine reactant containing at least one
primary or secondary amino group. The hydroxy compounds are in some
embodiment's polyhydric alcohols and amines. The polyhydric alcohols are
described above. In some embodiments, the hydroxy compounds are polyhydric
amines. Polyhydric amines include any of the above-described monoamines
reacted
with an alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide,
etc.)
having two to about 20, or to about four carbon atoms. Examples of polyhydric
amines include tri-(hydroxypropyl)amine, tris-(hydroxymethyl)amino methane, 2-
amino-2-methy1-1,3 -prop anediol,
N,N,N',N'-tetrakis(2-hydroxypropyl)ethylene
diamine, and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine, and in some
embodiments tris(hydroxymethyl)aminomethane (THAM).
[0079] In
another embodiment, the polyamines are hydroxy-containing
polyamines. Hydroxy-containing polyamine analogs of hydroxymonoamines,
particularly alkoxylated alkylenepolyamines (e.g.,
N,N(diethanol)ethylenediamine)
may also be used. Such polyamines may be made by reacting the above-described
alkylenepolyamines with one or more of the above-described alkylene oxides.
Similar alkylene oxide-alkanolamine reaction products may also be used such as
the
products made by reacting the aforedescribed primary, secondary or tertiary
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alkanolamines with ethylene, propylene or higher epoxides in a 1:1 to 1:2
molar
ratio. Reactant ratios and temperatures for carrying out such reactions are
known to
those skilled in the art.
[0080]
Specific examples of alkoxylated alkylene polyamines include
N-(2-hydroxyethyl)ethylenediamine, N,N-bis(2-
hydroxyethyl)ethylenediamine,
1 -(2-hydroxyethyl)pip erazine, mono (hydroxypropyl)sub stituted
tetraethylene-
pentamine, N-(3-hydroxybutyl)tetraethylene diamine, etc. Higher homologs
obtained by condensation of the above-illustrated hydroxy-containing
polyamines
through amino groups or through hydroxy groups are likewise useful.
Condensation
through amino groups results in a higher amine accompanied by removal of
ammonia while condensation through the hydroxy groups results in products
containing ether linkages accompanied by removal of water. Mixtures of two or
more of any of the aforesaid polyamines are also useful.
[0081] In
another embodiment, the amine is a heterocyclic polyamine. The
heterocyclic polyamines include aziridines, azetidines, azolidines, pyridines,
pyrroles, indoles, piperidines, imidazoles, piperazines, isoindoles, purines,
morpho-
lines, thiomorpholines, N-aminoalkylmorpholines, N-aminoalkylthiomorpholines,
N- amino alkylpiperazines, N,N'-di amino alkylpip erazines , azepines,
azocines,
azonines, azecines and tetra-, di- and perhydro derivatives of each of the
above and
mixtures of two or more of these heterocyclic amines. In some embodiments, the
heterocyclic amines are the saturated 5- and 6-membered heterocyclic amines
containing only nitrogen, oxygen and/or sulfur in the hetero ring, especially
the
piperidines, piperazines, thiomorpholines, morpholines, pyrrolidines, and the
like.
Piperidine, aminoalkyl-substituted piperidines, piperazine, aminoalkyl-
substituted
piperazines, morpholine, aminoalkyl-substituted morpholines, pyrrolidine, and
aminoalkyl-substituted pyrrolidines. Usually the aminoalkyl substituents are
substituted on a nitrogen atom forming part of the hetero ring. Specific
examples of
such heterocyclic amines include N-aminopropylmorpholine, N-amino-
ethylpip erazine, and N,N'- diamino ethylpip erazine.
Hydroxy heterocyclic
polyamines are also useful. Examples include N-(2-
hydroxyethyl)cyclohexylamine,
3-hydroxycyclopentylamine, para-hydroxyaniline, N-hydroxyethylpiperazine, and
the like.
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[0082] The amines used in the preparation of the hydrocarbyl
substituted
nitrogen containing additives described above may also be amines having at
least 4
aromatic groups, at least one -NH2 functional group, and at least 2 secondary
or
tertiary amino groups.
[0083] Suitable amines having at least 3 aromatic groups, at least one -NH2
functional group, and at least 2 secondary or tertiary amino groups may be
represented by the formula:
H H
N...........,,./. N --------...,
I I 1
t
H 2 N H X U ______ 1 NH2
1
R2
w
wherein independently each variable may be defined as follows: R1 may be
hydrogen or a C1_5 alkyl group (typically hydrogen); R2 may be hydrogen or a
C1_5
alkyl group (typically hydrogen); U may be an aliphatic, alicyclic or aromatic
group,
with the proviso that when U is aliphatic, the aliphatic group may be linear
or
branched alkylene group containing 1 to 5, or 1 to 2 carbon atoms; and w may
be 1
to 10, or 1 to 4, or 1 to 2 (typically 1).
[0084] Suitable amines having at least 3 aromatic groups, at least one -NH2
functional group, and at least 2 secondary or tertiary amino groups may be
represented by the formula:
_
H
N 0
1
101 NH2
_______________________________________________________________________ H
H 2N
U
R1
R2
w
_
wherein independently each variable may be defined as follows: R1 may be
hydrogen or a C1_5 alkyl group (typically hydrogen); R2 may be hydrogen or a
C1_5
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alkyl group (typically hydrogen); U may be an aliphatic, alicyclic or aromatic
group,
with the proviso that when U is aliphatic, the aliphatic group may be linear
or
branched alkylene group containing 1 to 5, or 1 to 2 carbon atoms; and w may
be 1
to 10, or 1 to 4, or 1 to 2 (typically 1).
[0085] Alternatively, the amines may also be represented by the formula:
_
H
N
NH1
I. U 0 NH2
1 1 1
H2N";:zi 0 U 7NH2 N\i
H
R
-
w
wherein each variable U, R1, and R2 are the same as described above and w is 0
to 9
or 0 to 3 or 0 to 1 (typically 0).
[0086] Examples of suitable amines having at least 3 aromatic groups
may be
represented by any of the following formulae:
H H
10 N 10 0 N 0
H2N C 2 NH2
H
Or
NH2
HN WI
401
H H
N N
H2
H2N 0 $ NH2
[0087] In one embodiment, the amine having at least 3 aromatic groups
may
include mixtures of compounds represented by the formulae disclosed above. A
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person skilled in the art will appreciate that these compounds may also react
with the
aldehyde described below to form acridine derivatives. In addition to such
compounds, a person skilled in the art will also appreciate that other
acridine
structures may be possible where the aldehyde reacts with other benzyl groups
bridged with the >NH group. Any or all of the N-bridged aromatic rings are
capable
of such further condensation and perhaps aromatization.
[0088]
Examples of suitable amines having at least 3 aromatic groups may be
bis[p-(p-aminoanilino)phenyl]-methane, 2-(7-amino-acridin-2-ylmethyl)-N-4-
{444-
(4-amino-phenylamino)-b enzyl] -phenyl} -benzene-1,4-diamine, N4- {4- [4-(4-
amino -
phenylamino)-b enzyl] -phenyl} -2-[4-(4-amino -phenylamino)-cyclohex a-1,5-
dienylmethyl] -b enzene-1 ,4-diamine, N44-
(7-amino-acridin-2-ylmethyl)-phenyl] -
benzene-1,4-diamine, or mixtures thereof.
[0089] In
one embodiment, the amine having at least 3 aromatic groups may be
bis[p-(p-aminoanilino)phenyl]-methane, 2-(7-amino-acridin-2-ylmethyl)-N-4- {4-
[4-
(4-amino-phenylamino)-benzyl]-phenyl} -benzene-1,4-diamine or mixtures
thereof.
[0090] The
amine having at least 3 aromatic groups may be prepared by a
process comprising reacting an aldehyde with an amine (typically 4-
aminodiphenylamine). The resultant amine may be described as an alkylene
coupled amine having at least 3 aromatic groups, at least one -NH2 functional
group,
and at least 2 secondary or tertiary amino groups.
[0091] In
some embodiments, the hydrocarbyl substituted nitrogen containing
additives are succinimide dispersants. In some embodiments, the hydrocarbyl
substituted nitrogen containing additives are non-borated succinimide
dispersants.
In some embodiments, the succinimide dispersants are derived from an alkyl
aryl
amine, polyethylene polyamines, or some combination thereof. In some
embodiments, the succinimide dispersants are derived from a hydrocarbyl-
substituted succinic anhydride or acid (a reactive equivalent thereof e.g., an
ester,
acid halide, etc.) where the hydrocarbyl-substituted succinic anhydride
contains a
polyisobutylene group with a molecular weight from 500 to 3000, or from 1600
to 3000, or from 1000 to 2000.
[0092]
Suitable hydrocarbyl substituted nitrogen containing additives also
include quaternary ammonium salts, also referred to as quaternary ammonium
salt
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detergents and/or dispersants. Examples of suitable quaternary ammonium salts
include (i) imide quaternary ammonium salts, (ii) Mannich quaternary ammonium
salts, (iii) polyalkene substituted amine quaternary ammonium salts, (iv)
amide
quaternary ammonium salts, (v) ester quaternary ammonium salts, (vi) polyester
quaternary ammonium salts, or (vii) any combination thereof
[0093] These various types of quaternary ammonium salts may be
prepared in
any number of ways but generally are prepared by reacting a non-quaternized
nitrogen-containing compound with a quaternizing agent. Each of the different
types of quaternary ammonium salts described uses a different non-quaternized
nitrogen-containing compound in its preparation, but generally the non-
quaternized
nitrogen-containing compound contains a tertiary nitrogen capable of being
quaternized (or a primary or secondary nitrogen atom that can be alkylated to
a
tertiary nitrogen that can then be quaternized) and a hydrocarbyl substituent
group.
The non-quaternized compounds are typically detergents and/or dispersants
themselves, put once converted to quaternary ammonium salts, can provide
improved performance.
[0094] The hydrocarbyl substituent groups of the quaternary ammonium
salt
detergents and/or dispersants, and/or of the non-quaternized nitrogen-
containing
compounds from which they are prepared, are not overly limited and may be any
of
the hydrocarbyl substituent groups derived herein.
[0095] Each of the quaternary ammonium salts described above is
prepared
using a quaternizing agent. Suitable quaternizing agents are not overly
limited so
long as they are able to convert the tertiary nitrogen of the non-quaternized
precursor to a quaternized nitrogen. Suitable quaternizing agents include
dialkyl
sulfates, benzyl halides, hydrocarbyl substituted carbonates, hydrocarbyl
epoxides,
esters of certain polycarboxylic acids, or mixtures thereof. Any of the these
agents,
including the hydrocarbyl epoxides and hydrocarbyl substituted carbonates, may
be
used in combination with an acid, for example acetic acid. Suitable acids
include
carboxylic acids, such as acetic acid, propionic acid, 2-ethylhexanoic acid,
and the
like. In some embodiments, including, for example, the amide quaternary
ammonium salts, the quaternizing agents, including the hydrocarbyl epoxides
and
hydrocarbyl substituted carbonates, are used without the addition of such an
acid. In
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some embodiments, particularly when no acid is used, some amount of water is
present during the reaction.
[0096] In some embodiments, the quaternizing agent can be a
hydrocarbyl
epoxides, as represented by the following formula:
R15 0 R17
R' R'8
wherein R15, R165 R17
and R18 can be independently H or a C1_50 hydrocarbyl group.
Examples of suitable hydrocarbyl epoxides include: styrene oxide, ethylene
oxide,
propylene oxide, butylene oxide, stilbene oxide, C2_50 epoxides, or
combinations
thereof
[0097] With regards to the amide quaternary ammonium salt described above,
the presence of the amide group and its impact on the rest of the structure
allows the
salt to be "self-salting" and thus not requiring of a separate anion assuming
the
structure also includes at least one other acid group. For example, when
hydrocarbyl substituted succinic anhydrides, and similar materials are used to
prepare the non-quaternized nitrogen-containing compounds, the resulting
quaternary ammonium salt can have an amide group and an acid group, where the
acid group becomes the counter anion for the quaternized nitrogen or the
resulting
amide quaternary ammonium salt. These materials may be described as betaines.
The preparation of these quaternary ammonium salts is typically marked by the
use
of an alkylene oxide quaternizing agent, or a similar agent, without the
addition of a
separate acid.
[0098] In another embodiment, the quaternizing agent can be an ester
of a
carboxylic acid or an ester of a polycarboxylic acid. In some embodiments, the
quaternizing agent includes dimethyl oxalate, methyl 2-nitrobenzoate and
methyl
salicylate.
[0099] In some embodiments, the quaternary ammonium salt is a
quaternized
polymer formed by polymerizing the condensation product of a hydrocarbyl-
substituted acylating agent and a compound having an oxygen or nitrogen atom
capable of condensing the acylating agent wherein the condensation product has
at
least one tertiary amino group, or even polymerizing the hydrocarbyl-
substituted
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acylating agent which is then reacted with a compound having an oxygen or
nitrogen atom. One or more of the tertiary amino groups on the polymer may
then
be quaternized using the methods described herein resulting in a quaternized
polymer.
[0100] Any of the quaternary ammonium salts described above may be derived
in the presence of a protic solvent. In some embodiments, the process used to
prepare these additives is substantially free of to free of methanol. In one
embodiment, the protic solvent includes compounds that contain 1 or more
hydroxyl
functional groups, and may include water. In some embodiments, the protic
solvent
is water.
[0101] Additional details on quaternary ammonium salts, examples
thereof and
methods of making the same can be found in US Patent 7,951,211 and 7,906,470,
US published applications US 2008/0113890, US 2012/0010112, and US
2011/0315107, and international publications WO 2010/132259, WO 2010/097624,
and W02011/095819.
[0102] The nitrogen containing dispersant may be a polyetheramine. In
some
embodiments, the polyetheramine can include compounds having two or more
consecutive ether groups and at least one primary, secondary or tertiary amine
group
where the amine nitrogen has some basicity. The polyetheramines of this
invention
can include poly(oxyalkylene) amines having a sufficient number of repeating
oxyalkylene units to render the poly(oxyalkylene)amine soluble in a normally
liquid
fuel, such as, in hydrocarbons boiling in a gasoline or diesel fuel range and
blends of
hydrocarbon fuel with non-hydrocarbon fuel. Generally, poly(oxyalkylene)amines
having at least 5 oxyalkylene units are suitable for use in the present
invention.
[0103] Poly(oxyalkylene)amines can include: hydrocarbylpoly(oxyalkylene)-
amines, hydrocarbylpoly(oxyalkylene)polyamines, hydropoly(oxyalkylene)-
amines,
hydropoly(oxyalkylene)polyamines, and derivatives of polyhydric alcohols
having
at least two poly(oxyalkylene)amine and/or poly(oxyalkylene) polyamine chains
on
the molecule of the derivative.
[0104] In one embodiment, the poly(oxyalkylene)amine for use in the
invention
is represented by the formula:
R60(A20)m R7NR8R9
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wherein R6 is a hydrocarbyl group of 1 to 50 carbon atoms, or 8 to 30 carbon
atoms;
A2 is an alkylene group having 2 to 18 carbon atoms and in some embodiments 2
to
6 carbon atoms; m is a number from 1 to 50; R7 is an alkylene group having 2
to 18
carbon atoms or in some embodiments 2 to 6 carbon atoms; and R8 and R9 are
independently hydrogen, a hydrocarbyl group Or
-[R'N(R")]nR'" wherein R' is an alkylene group having 2 to 6 carbon atoms, R"
and R'"
are independently hydrogen or a hydrocarbyl group, and n is a number from 1 to
7.
[0105] In
another embodiment, the poly(oxyalkylene)amine of the present
invention can be represented by the formula:
R100 [CH2CH(CH2CH3)0]zCH2CH2CH2NH2
wherein R1 is an aliphatic group or alkyl-substituted phenyl group of 8 to 30
carbon
atoms; and Z is a number from 12 to 30. In yet another embodiment, the poly-
(oxyalkylene)amine of the present invention can be represented by the formula
above wherein R1 is CH3CH(CH3)[CH2CH(CH3)]2CH(CH3)CH2CH2- and Z is a
number from 16 to 28. Poly(oxyalkylene)amines of the present invention can
have a
molecular weight in the range from 300 to 5,000.
[0106] The
polyetheramines of the present invention can be prepared by using
the polyethers described above as intermediates and converting them to
polyetheramines. The polyether intermediates can be converted to
polyetheramines
by several methods. The polyether
intermediate can be converted to a
polyetheramine by a reductive amination with ammonia, a primary amine or a
polyamine as described in U.S. Patent Nos. 5,112,364 and 5,752,991. In one
embodiment, the polyether intermediate can be converted to a polyetheramine
via an
addition reaction of the polyether to acrylonitrile to form a nitrile which is
then
hydrogenated to form the polyetheramine. U.S. Patent No. 5,264,006 provides
reaction conditions for the cyanoethylation of the polyether with
acrylonitrile and
the subsequent hydrogenation to form the polyetheramine. In yet another
embodiment, the polyether intermediate or poly(oxyalkylene) alcohol is
converted to
the corresponding poly(oxyalkylene) chloride via a suitable chlorinating agent
followed by displacement of chlorine with ammonia, a primary or secondary
amine,
or a polyamine as described in U.S. Patent No. 4,247,301.
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[0107] The mixed alkoxylates of the present invention may also include
an
alkoxylated fatty amine, which can include amines represented by the formula:
, (A30),(FI
R11N
N(A40) H
Y
wherein R11 is a hydrocarbyl group having 4 to 30 carbon atoms, A3 and A4 are
vicinal alkylene groups, and the sum of x and y is an integer that is at least
1. The
hydrocarbyl group is a univalent radical of carbon atoms that is predominantly
hydrocarbon in nature, but can have nonhydrocarbonaceous substituent groups
and
can have heteroatoms. The hydrocarbyl group R11 can be an alkyl or alkylene
group
of 4 to 30 carbon atoms, or 10 to 22 carbon atoms. The vicinal alkylene groups
A3
and A4 can be the same or different and include: ethylene(-CH2-), propylene (-
CH2CH2CH2-) and butylene (-CH2CH2CH2CH2-) having the carbon to nitrogen and
carbon to oxygen bonds on adjacent or neighboring carbon atoms. Examples of
alkoxylated fatty amines can include: diethoxylated tallowamine, diethoxylated
oleylamine, diethoxylated stearylamine, and the diethoxylated amine from
soybean
oil fatty acids. Alkoxylated fatty amines are commercially available from Akzo
under the Ethomeen0 series.
[0108] The nitrogen-containing compound may be present at 0.01 percent
by
weight to 5 percent by weight, or 0.1 percent by weight to 3 percent by
weight, or
0.2 percent by weight to 1.5 percent by weight, or 0.25 percent by weight to 1
percent by weight, or 0.5 percent by weight to 1 percent by weight of the
described
composition.
The Sulfur-containing compound
[0109] In some embodiments, the bearing lubricant of invention, or the
methods
using the same, may also include (d) a sulfur-containing compound.
[0110] Suitable sulfur-containing compounds include sulfurized
olefins. Any
the olefins described herein for other components are also suitable olefins
from
which sulfurized olefins may be prepared. In some examples, the sulfur-
containing
compound is a sulfurized olefin derived from isobutylene, butylene, propylene,
ethylene, or some combination thereof In some examples, the sulfur-containing
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compound is a sulfurized olefin derived any of the natural oils or synthetic
oils
described above, or even some combination thereof. For example, the sulfurized
olefin may be derived from vegetable oil.
[0111] When present, the sulfur-containing compound may be present at
0.01
percent by weight to 5 percent by weight, or 0.1 percent by weight to 3
percent by
weight, or 0.2 percent by weight to 1.5 percent by weight, or 0.25 percent by
weight
to 1 percent by weight, or 0.5 percent by weight to 1 percent by weight of the
described composition.
Additional Additives
[0112] Optionally, the lubricating compositions of the invention include
one or
more additional additives, which may be selected from the group including: a
foam
inhibitor, a demulsifier, a pour point depressant, an antioxidant, a
dispersant other
than those described above, a metal deactivator (such as a copper
deactivator), an
antiwear agent other than those described above, extreme pressure agent,
viscosity
modifiers, or mixtures thereof. The optional additives may each be present in
the
range from 50, 75, 100 or even 150 ppm up to 5, 4 , 3, 2 or even 1.5 percent
by
weight, or from 75 ppm to 0.5 percent by weight, from 100 ppm to 0.4 percent
by
weight, or from 150 ppm to 0.3 percent by weight, where the percent by weight
values are with regards to the overall lubricating oil composition. However,
it
is noted that some optional additives, including viscosity modifying polymers,
which may alternatively be considered as part of the base fluid, may be
present
in higher amounts including up to 30, 40, or even 50% by weight when
considered separate from the base fluid. The optional additives may be used
alone or mixtures thereof
[0113] Antifoams, also known as foam inhibitors, are known in the art and
include but are not limited to organic silicones and non-silicon foam
inhibitors.
Examples of organic silicones include dimethyl silicone and polysiloxanes.
Examples of non-silicon foam inhibitors include but are not limited to
polyethers,
polyacrylates and mixtures thereof as well as copolymers of ethyl acrylate, 2-
ethylhexylacrylate, and optionally vinyl acetate. In some embodiments, the
antifoam is a polyacrylate. Antifoams may be present in the composition from
0.001 to 0.012 or 0.004 pbw or even 0.001 to 0.003.
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[0114] Demulsifiers are known in the art and include but are not
limited to
derivatives of propylene oxide, ethylene oxide, polyoxyalkylene alcohols,
alkyl
amines, amino alcohols, diamines or polyamines reacted sequentially with
ethylene
oxide or substituted ethylene oxides or mixtures thereof. Examples of
demulsifiers
include polyethylene glycols, polyethylene oxides, polypropylene oxides,
(ethylene
oxide-propylene oxide) polymers and mixtures thereof. In some embodiments, the
demulsifiers is a polyether. Demulsifiers may be present in the composition
from
0.002 to 0.012 pbw.
[0115] Pour point depressants are known in the art and include but are
not
limited to esters of maleic anhydride-styrene copolymers, polymethacrylates;
polyacrylates; polyacrylamides; condensation products of haloparaffin waxes
and
aromatic compounds; vinyl carboxylate polymers; and terpolymers of dialkyl
fumarates, vinyl esters of fatty acids, ethylene-vinyl acetate copolymers,
alkyl
phenol formaldehyde condensation resins, alkyl vinyl ethers and mixtures
thereof.
[0116] The compositions of the invention may also include a rust inhibitor,
other
than some of the additive described above. Suitable rust inhibitors include
hydrocarbyl amine salts of dialkyldithiophosphoric acid, hydrocarbyl amine
salts of
hydrocarbyl arenesulphonic acid, fatty carboxylic acids or esters thereof, an
ester of
a nitrogen-containing carboxylic acid, an ammonium sulfonate, an imidazoline,
mono-thio phosphate salts or esters, or any combination thereof; or mixtures
thereof
[0117] Examples of hydrocarbyl amine salts of dialkyldithiophosphoric
acid of
the invention include but are not limited to those described above, as well as
the
reaction product(s) of diheptyl or dioctyl or dinonyl dithiophosphoric acids
with
ethylenediamine, morpholine or Primene 81R or mixtures thereof Suitable
hydrocarbyl amine salts of hydrocarbyl arenesulphonic acids used in the rust
inhibitor package of the invention are represented by the formula:
15124
0-;)i ey_601 \ /R25
(V)
// I
1423
wherein Cy is a benzene or naphthalene ring. R28 is a hydrocarbyl group with
about
4 to about 30, preferably about 6 to about 25, more preferably about 8 to
about 20
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carbon atoms. z is independently 1, 2, 3, or 4 and most preferably z is 1 or
2. R23,
R24 and R25 are as described above.
[0118]
Examples of hydrocarbyl amine salts of hydrocarbyl arenesulphonic acid
of the invention include but are not limited to the ethylenediamine salt of
dinonylnaphthalene sulfonic acid.
[0119]
Examples of suitable fatty carboxylic acids or esters thereof include
glycerol monooleate and oleic acid. An example of a suitable ester of a
nitrogen-
containing carboxylic acid includes oleyl sarcosine.
[0120] The
rust inhibitors may be present in the range from 0.02-0.2, from 0.03
to 0.15, from 0.04 to 0.12, or from 0.05 to 0.1 pbw of the lubricating oil
composition. The rust inhibitors of the invention may be used alone or in
mixtures
thereof.
[0121] The
lubricating compositions of the invention may also include a metal
deactivator. Metal deactivators are used to neutralise the catalytic effect of
metal for
promoting oxidation in lubricating oil. Suitable metal deactivators include
but are
not limited to triazoles, tolyltriazoles, a thiadiazole, or combinations
thereof, as well
as derivatives thereof. Examples include derivatives of benzotriazoles other
than
those described above, benzimidazole, 2-alkyldithiobenzimidazoles, 2-
alkyldithiobenzothiazoles, 2-(N,N'-dialkyldithio-carbamoyl)benzothiazoles, 2,5-
bis(alkyl-dithio)-1,3,4-thiadiazoles, 2,5 -bis(N,N
' -dialkyldithio carb amoy1)-1,3,4 -
thiadiazoles, 2-alkyldithio-5-mercapto thiadiazoles or mixtures thereof These
additives may be used from 0.01 to 0.25 percent by weight in the overall
composition.
[0122] In
some embodiments, the metal deactivator is a hydrocarbyl substituted
benzotriazole compound. The
benzotriazole compounds with hydrocarbyl
substitutions include at least one of the following ring positions 1- or 2- or
4- or 5-
or 6- or 7- benzotriazoles. The hydrocarbyl groups contain about 1 to about
30,
preferably about 1 to about 15, more preferably about 1 to about 7 carbon
atoms,
and most preferably the metal deactivator is 5-methylbenzotriazole used alone
or
mixtures thereof.
[0123] The
metal deactivators may be present in the range from 0.001 to 0.1,
from 0.01 to 0.04 or from 0.015 to 0.03 pbw of the lubricating oil
composition.
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Metal deactivators may also be present in the composition from 0.002 or 0.004
to
0.02 pbw. The metal deactivator may be used alone or mixtures thereof.
[0124] Antioxidants may also be present including (i) an alkylated
diphenylamine, and (ii) a substituted hydrocarbyl mono-sulfide. In
some
embodiments, the alkylated diphenylamines of the invention are bis-nonylated
diphenylamine and bis-octylated diphenylamine. In some embodiments, the
substituted hydrocarbyl monosulfides include n-dodecy1-2-hydroxyethyl sulfide,
1-
(tert-dodecylthio)-2-propanol, or combinations thereof In some embodiments,
the
substituted hydrocarbyl monosulfide is 1-(tert-dodecylthio)-2-propanol.
[0125] The
antioxidant package may also include sterically hindered phenols.
Examples of suitable hydrocarbyl groups include but are not limited to 2-
ethylhexyl
or n-butyl ester, dodecyl or mixtures thereof Examples of methylene-bridged
sterically hindered phenols include but are not limited to 4,4'-methylene-
bis(6-tert-
butyl o-cresol), 4,4'-methylene-bis(2-tert-amyl-o-cresol), 2,2'-methylene-
bis(4-
methyl-6-tert-butylphenol), 4,4 -methylene-bis(2,6-di-tertbutylphenol) or
mixtures
thereof.
[0126] In
some embodiments, the compositions of the invention are essentially
free of, or even completely free of alkylated phenols, alkaryl amines, or
both, or
contain them at not more than 2.0 percent by weight, 1.0 percent by weight, or
even
0.5 percent by weight where the percent by weight values refer to the total
amount
of alkylated phenols and/or alkaryl amines present in the overall lubricant.
Examples
[0127] The
invention will be further illustrated by the following examples,
which set forth particularly advantageous embodiments. While the examples are
provided to illustrate the invention, they are not intended to limit it.
Example Set/
[0128] A
set of examples of coal pulverizer lubricant compositions is prepared.
The formulations of the examples are summarized in the table below in percent
by
weight, with the phosphorus-containing compound and nitrogen containing
dispersant listed on an actives basis:
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TABLE 1
Ex 1 Ex 2 Ex 3 Ex 4 Ex 5 Ex 6 Ex 7 Ex 8
Ex 95
COMP COMP COMP
COMP
Base
1 99.26 97.80 98.6 95.55 96.87 96.45 97.81 96.66 NA
Medium
Phosphorus-
containing 0 1.47 0 1.87 1.93 0.95 0.97 1.43 NA
compound2
Nitrogen
Containing 0 0 1.21 1.87 0.48 1.89 0.49 1.19 NA
Dispersant3
Additional
0.74 0.73 0.73 0.70 0.72 0.71 0.73 0.72
NA
Additives4
1 ¨ The base medium is a mixture of polyalphaolefin (Group IV) base oil and
polyisobutylene base
oil. The same base medium is used in each example unless otherwise noted, and
on a PBW basis is
present in the same amount in each example. Differences in the percent by
weight listed for each
example is solely due the different amounts of the phosphorus-containing
compound and nitrogen
containing dispersant that are in each example.
2 ¨ The phosphorus-containing compound in the examples is an alkenyl
phosphite.
3 ¨ The nitrogen containing dispersant in the examples is a succinimide
dispersant.
4 ¨ The same additional additive package is used for each example, and on a PB
W basis is present in
the same amount in each example. Differences in the percent by weight listed
for each example is
solely due the different amounts of the phosphorus-containing compound and
nitrogen containing
dispersant that are in each example.
5 ¨ Example 9 is a commercially available lubricant marketed for this
application. The formulation
of the lubricant is not known and so the material is included only as an
example of the conventional
lubricants commercially available for this application.
[0129] Each of the example lubricants is tested in a procedure that
simulates the
harsh conditions seen in the bearings of pulverizers, and specifically coal
pulverizers. Coal dust is added to the example lubricant to simulate the
contamination that occurs in the field and the impact on lubricant performance
is
measured to demonstrate the examples ability to provide acceptable performance
under those conditions. The test uses a high load KRL type tester and a SNR
32008.0 test bearing. The test procedure involves the following steps:
(1) Clean a new test bearing in an ultrasonic bath with toluene for 15
minutes. Rinse with textile spirits and allow the bearing to dry.
(2) Obtain the start of test bearing weight to the tenth of a milligram.
(3) Place bearing in the test head of the KRL type tester.
(4) Add 0.9 percent by weight coal dust to the example lubricant. Mix the
lubricant and coal dust well using a high speed shaker and then fill the
test head with 30 ml of the coal dust contaminated example lubricant.
(5) Install test head into the KRL type tester.
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(6) Run the test conditions outlined in Table 2, which are designed to
simulate the harsh conditions and manner of operation experienced in the
bearings of pulverizers:
TABLE 2
Phase Speed Load Temp Time
(rpm) (kg) (Degrees C)
(hrs)
Break In 150 800 90 1
Break In 300 800 90 1
Break In 430 800 90 2
Break In 150 1600 90 1
Break In 300 1600 90 1
Break In 430 1600 90 2
Break In 150 2400 90 1
Break In 300 2400 90 1
Test 430 2400 90 48
(7) At the end of test remove, save, and label the example lubricant.
(8) Clean the test bearing by rinsing with textile spirits and then clean
the
bearing in ultrasonic bath with toluene for 15 minutes. Rinse again with
textile spirits and allow the bearing to dry.
(9) Obtain the end of test bearing weight to the tenth of a milligram.
(10) Determine weight loss from the start and end of test weights
and analyze
the end of test example lubricant for the amount of wear metals.
[0130] The results from the testing of the example lubricants are
summarized in
the table below:
TABLE 3
Ex 1 Ex 2 Ex 3 Ex 4 Ex 5 Ex 6
Ex 72 Ex 83 Ex 94
COMP COMP COMP
COMP
Total
Weight Loss 8.7 15.6 9.9 8.9 4.9 9.5 8.2 14.1
22.6
(mg)1
Iron in
Lubricant 172 266 229 322 337 293 128 294
770
(11Pni)
1 ¨ For the total weight loss, the lower the value the better the performance
of the lubricant. Total
weight loss is the more important result presented above in regards to
evaluating lubricant
performance.
2 ¨ The results shown for Example 7 are the average of two test results.
3 ¨ The results shown for Example 8 are the average of three test results.
4 ¨ The results shown for Example 9 are the average of four test results.
[0131] The results show that the pulverizer bearing lubricants of the
present
invention, and the methods of using the same, can provide significant
performance
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under the harsh conditions seen by pulverizer bearings. The described
lubricants
and methods are particularly advantageous compared to the current commercially
available options for these applications.
Example Set 2
[0132] A second set of examples of coal pulverizer lubricant compositions
is
prepared without adding any additional additives. The formulations of the
examples
are summarized in the table below in percent by weight, with the phosphorus-
containing compound and nitrogen containing dispersant listed on an actives
basis:
TABLE 4
Ex 105 Ex 115 Ex 12 Ex 13 Ex 14 Ex 15 Ex 16 Ex 17 Ex 18
COMP COMP COMP COMP
Base
1 NA NA 100 99.26 94.44 98.53 99.01 99.50 99.63
Medium
Phosphorus-
containing NA 0.50 0.00 0.50 3.70 0.98 0.99
0.00 0.25
compound2
Nitrogen
Containing NA 0.25 0.00 0.25 1.85 0.49 0.00
0.50 0.12
Dispersant3
Additional
NA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Additives4
1 - The base medium is a mixture of polyalphaolefin (Group IV) and
polyisobutylene base oil. The
same base medium is used in each example unless otherwise noted. See footnote
1 in Table 1 above.
2 - The phosphorus-containing compound in the examples is an alkenyl
phosphite.
3 - The nitrogen containing dispersant in the examples is a succinimide
dispersant.
4 - No additional additives are added to these examples.
5 - Example 10 is a commercially available lubricant marketed for this
application. The formulation
of the lubricant is not known and so the material is included only as an
example of the conventional
lubricants commercially available for this application. Example 11 is the same
commercially
available lubricant but now top treated with the additive combination of the
present invention.
[0133] The examples of Table 4 are evaluated in the same test procedure
described above. The results are summarized in the table below:
TABLE 5
Ex 102 Ex 11 Ex 123 Ex 13 Ex 14 Ex 15 Ex 16 Ex 17
Ex 18
COMP COMP COMP COMP
Total
Weight 22.6 21.5 8.7 8.7 11.4 11.3 4.7 13.3
4.2
Loss (mg)1
Iron in
Lubricant 770 177 172 124 258 156 449 222 123
(111701)
1 - For the total weight loss, the lower the value the better the performance
of the lubricant. Total
weight loss is the more important result presented above in regards to
evaluating lubricant
performance.
2 - The results shown for Example 10 are the average of three test results.
3 - The results shown for Example 11 are the average of four test results.
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CA 02869329 2014-10-01
WO 2013/151911
PCT/US2013/034754
[0134] The results show that the pulverizer bearing lubricants of the
present
invention, and the methods of using the same, can provide significant
performance
under the harsh conditions seen by pulverizer bearings. The described
lubricants
and methods are particularly advantageous compared to the current commercially
available options for these applications.
[0135] In particular, it is noted that the inventive examples
(Examples 13, 14,
15, and 18) all have better weight loss results than the conventional and un-
additized
lubricants (Examples 10 and 12). Example 16 has a good weight loss result but
the
amount of iron in the lubricant at end of test is far too high. Likewise,
Example 17
has a reasonable, but still high, amount of iron, but has high weight loss. In
contrast,
the inventive examples give a good balance of results in both areas.
Furthermore,
the top treated commerical example (Example 12) showed significant improvement
as well, when the present invention was applied to it.
[0136] Each of the documents referred to above is incorporated herein by
reference. Except in the Examples, or where otherwise indicated, all numerical
quantities in this description specifying amounts, reaction conditions,
molecular
weights, number of carbon atoms, etc., are to be understood as modified by the
word
"about." Unless otherwise indicated, all percent and formulation values are on
a
weight basis. Unless otherwise indicated, all molecular weights are number
average
molecular weights. Unless otherwise indicated, each chemical or composition
referred to herein should be interpreted as being a commercial grade material
which
may contain the isomers, by-products, derivatives, and other such materials
which
are normally understood to be present in the commercial grade. However, the
amount of each chemical component is presented exclusive of any solvent or
diluent, which may be customarily present in the commercial material, unless
otherwise indicated. It is to be understood that the upper and lower amount,
range,
and ratio limits set forth herein may be independently combined. Similarly,
the
ranges and amounts for each element of the invention can be used together with
ranges or amounts for any of the other elements. As used herein, the
expression
"consisting essentially of' permits the inclusion of substances that do not
materially
affect the basic and novel characteristics of the composition under
consideration.
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