Note: Descriptions are shown in the official language in which they were submitted.
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TITLE
Method for Preparing a Sulfurized Alkaline Earth Metal Dodecylphenate
BACKGROUND OF THE INVENTION
[0001] The disclosed technology relates to a process for preparing a
sulfurized
alkaline earth metal dodecylphenate exhibiting improved ease of filterability.
[0002] Phenol-based detergents are known. Among these are phenates
based on
phenolic monomers, linked with sulfur bridges or alkylene bridges such as
methylene
linkages derived from formaldehyde. The phenolic monomers themselves are
typically
substituted with an aliphatic hydrocarbyl group to provide a measure of oil
solubility.
[0003] One commonly employed step in the commercial manufacture of
metal
phenates, including overbased metal phenates, is filtration. The filtration
typically
occurs after the overbasing process, and slow filtration can have a negative
impact on
production and economics, in terms of filtration time or alternatively in
amount of filter
aid usage required to maintain an acceptable flow rate. Moreover, recipe
modifications
designed to reduce the amount of monomeric phenolic species may tend to lead
to
worse filtration performance. This is of increasing significance because
certain al-
kylphenols and products prepared from them have come under increased scrutiny
due to
their association as potential endocrine disruptive materials. In particular,
alkylphenol
detergents which are based on oligomers of C12 alkyl phenols may contain
residual
monomeric C12 alkyl phenol species. There has been interest, therefore, in
developing
alkyl-substituted phenate detergents, for uses in lubricants, fuels, and as
industrial
additives, which contain a reduced amount of dodecylphenol component.
[0004] An early reference to basic sulfurized polyvalent metal phenates
is U.S.
Patent 2,680,096, Walker et al., June 1, 1954; see also U.S. Patent 3,372,116,
Mein-
hardt, March 6, 1968. Additionally, U.S. Patent 3,036,971, Otto, May 29, 1962,
dis-
closes lubricating oils containing carbonated basic sulfurized calcium
phenates. Its
preparation includes the use of a glycol containing less than 6 carbon atoms.
[0005] U.S. Patent 3,464,970, Sakai et al., September 2, 1969,
similarly discloses an
overbased sulfurized calcium phenate by heating a mixture of phenolic
compounds,
dihydric alcohol, elementary sulfur and calcium compounds. Somewhat later,
U.S.
Patent 5,024,773, Liston, June 18, 1991, discloses a method of preparing group
II metal
overbased sulfurized alkylphenols involving use of a sulfurization catalyst.
The product
is said to have lower crude sediment, higher Total Base Number, and lower
viscosity.
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[0006] EP 601721, Ethyl Petroleum, June 15, 1994, discloses a process
for preparing
overbased phenates.
[0007] PCT publication WO 2013/119623, Lubrizol, August 15, 2013,
discloses a
sulfurized alkaline earth metal (e.g., calcium) dodecylphenate prepared by
reacting
dodecylphenol with calcium hydroxide or calcium oxide in an amount of about
0.3 to
about 0.7 moles per mole of dodecylphenol charged and an alkylene glycol in an
amount of about 0.13 to about 0.6 moles per mole of dodecylphenol charged; and
reacting the product of the first step with sulfur in an amount of about 1.6
to about 3
moles per mole of dodecylphenol charged The product thus prepared has reduced
levels of monomeric dodecylphenol.
[0008] The disclosed technology provides a method for preparing phenate
detergent
with improved filterability efficiency. In certain embodiments, the disclosed
technology
may also provide a product which contains a reduced amount of monomeric
dodecyl-
phenol within an oligomeric dodecylphenol composition.
SUMMARY OF THE INVENTION
[0009] The disclosed technology provides a process for preparing a
sulfurized alkaline
earth metal alkylphenate, optionally overbased, comprising:
(a) reacting (i) an alkylphenol, wherein the alkyl group contains 6 to 24
carbon atoms,
with (ii) an alkaline earth metal hydroxide or an alkaline earth metal oxide
in an amount
of 0.4 to 10 moles per mole of alkylphenol charged to the reaction; and (iii)
a sulfur
source in an amount to provide 0.8 to 3 moles sulfur (as S) per mole of
alkylphenol
charged to the reaction; in the presence of (iv) an alkylene glycol or
dialkylene glycol, or
ether thereof, in an amount of 0.2 to 2 moles per mole of alkylphenol charged
to the
reaction; and including in the reaction mixture (v) an oil of lubricating
viscosity; and
optionally further reacting the product thereof with (vi) carbon dioxide;
thereby forming a
sulfurized alkaline earth metal alkylphenate composition in oil;
(b) heating said alkylphenate composition to 120 to 280 C or 200 to 250 C;
(c) supplying steam to said alkylphenate composition;
(d) removing said steam under reduced pressure; and
(e) filtering the resulting composition to provide, as the filtrate, a
sulfurized alkaline earth
metal alkylphenate in oil.
[0010] The disclosed technology further provides the product prepared
by the forego-
ing process; a lubricant composition comprising an oil of lubricating
viscosity and the
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foregoing product; and a method for lubricating an internal combustion engine,
compris-
ing supplying thereto the foregoing lubricant composition.
DETAILED DESCRIPTION OF THE INVENTION
[0011] Various preferred features and embodiments will be described
below by way
of non-limiting illustration.
[0012] One of the materials used in the presently disclosed technology
is a sulfur-
bridged phenolic compound. Such materials in general, their methods of
preparation,
and use in lubricants are well known from, for instance, the above-referenced
U.S.
Patent 2,680,096, Walker et al. They may be prepared starting from phenol or,
alterna-
tively, a short chain alkyl phenol such as cresol (o-, m-, or p-methylphenol),
or mixtures
thereof, any of which are readily available as starting materials. The
alkylation of
phenol and its homologues is well known, typically by catalyzed reaction of an
olefin,
often an a-olefin, with phenol (or with cresol or another homologue, as the
case may
be). Alkylation of phenol is described in greater detail in the Kirk-Othmer
Encyclope-
dia of Chemical Technology, third edition (1978) vol. 2, pages 82-86, John
Wiley and
Sons, New York.
[0013] Linking of alkyl-substituted (or more generally, hydrocarbyl-
substituted)
phenols to form oligomeric species is also well known. They may be linked
together to
make sulfur bridged species, which may include bridges of single sulfur atoms
( ¨S¨) or
multiple sulfur atoms (e.g., ¨S.¨ where n may be 2 to 8, typically 2 or 3).
Typically
there may be 1, 2, or 3, or often 1, S atom per linkage. Sulfurized phenols
may be
prepared by reaction with a sulfur source, that is, an active sulfur species
such as sulfur
monochloride or sulfur dichloride as described on pages 79-80 of the Kirk-
Othmer
reference or with elemental sulfur, as described, for instance, in US
2,680,096. Sulfuri-
zation (with sulfur) may be conducted in the presence of a basic metal
compound such
as calcium hydroxide or calcium oxide, thus preparing a metal salt, as
described in
greater detail, below.
[0014] The process of the disclosed technology begins with an
alkylphenol which
comprises an alkylphenol wherein the alkyl group contains 6 to 24 carbon
atoms, and in
certain embodiments, 8 to 18 or 9 to 15 or 10 to 14 carbon atoms, or 12 carbon
atoms.
Such a material may include a dodecylphenol (e.g., tetrapropenylphenol, "TPP")
such
as, in one embodiment, paradodecylphenol, ("PDDP"). Other substituted phenols
may
be present in TPP as well as PDDP, but in certain embodiments the PDDP may
comprise
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at least 50 weight percent of the monomeric phenolic component and may be 50
to 100
weight percent, or 60 to 99% or 70 to 98% or 80 to 97% or 90-96% or 95 to 98%.
Typically, a commercial grade of TPP may be used, such that phenolic
components
other than PDDP will be those materials that are present along with PDDP in
the com-
mercial grade material. Thus, a certain amount of other isomers may be
present, pre-
dominantly ortho-dodecylphenol or meta-dodecylphenol, but there may also be an
amount of unsubstituted phenol and an amount of unreacted dodecene, as well as
a
certain amount (typically a minor amount) of dialkylated material. Moreover,
since
dodecylphenols are typically prepared by the reaction of a propylene tetramer
with a
phenol, certain amounts of material having C9 or C15 alkyl groups, or a
mixture of alkyl
groups having 9 (or fewer) to 15 (or more) carbon atoms, may also be present.
Some of
these may result from reaction with propylene trimer or pentamer.
Characteristically,
the amount of such other materials may be 5 or 15 to 50 percent or 20 to 40,
or 25 to 35,
or 35 to 40 percent by weight, in commercial PDDP. The amounts of PDDP
referred to
herein generally refer to the total amount of the commercial grade, which
would include
such isomers, byproducts, and other materials. However, when the amount of
"residual
TPP" is reported, those amounts normally include mixtures of closely related
monomer-
ic materials such as ortho- and para- isomers from C9 to C15 alkylphenols,
typically
excluding dialkylated materials.
[0015] The TPP or other alkylphenol may be, in one embodiment, initially
reacted
with a basic alkaline earth metal material, typically an oxide or a hydroxide,
where the
alkaline earth metal may typically be calcium or magnesium, or in some
embodiments,
calcium. Suitable basic materials include calcium (or magnesium) hydroxide or
calcium
(or magnesium) oxide, typically calcium hydroxide. The reaction may be carried
out in
the presence of an alkylene glycol and sulfur. The amount of the alkaline
earth metal
hydroxide or oxide may typically be an amount to provide 0.4 to 10 moles of
the metal
oxide or hydroxide per mole of the alkylphenol (such as TPP) that is charged
to the
reaction. Alternative amounts may be 0.5 to 8 moles or 0.8 to 6 or 1 to 5 or
1.3 to 3 or 1.5
to 2 or 1.7 to 1.9 moles per moles of alkylphenol. Since alkaline earth metals
are divalent,
the broadest above-mentioned amounts would correspond to 0.8 to 20 equivalents
per
mole of the alkylphenol. For amounts less than 1 equivalent per equivalent,
the alkylphe-
nol will not be completely salted or neutralized; for amounts of about 1
equivalent/-
equivalent, a substantially neutral salt may be obtained. For amounts in
excess of 1
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equivalent/ equivalent, an overbased salt may be obtained, as described in
greater detail
below. In another embodiment, the alkylphenol may be initially reacted with a
sulfur
source to form a sulfur-bridged material, and thereafter reacted with the
selected amount
of alkaline earth metal oxide or hydroxide to effect neutralization.
[0016] An alkylene glycol (that is, diol) is typically present, especially
during the
neutralization reaction. The alkylene glycol may be ethylene glycol or it may,
alternative-
ly, be a heavier glycol such as 1,2- or 1,3-propylene glycol or a butylene
glycol. As it is
often considered to be desirable able to remove the alkylene diol after the
reaction is
complete, use of a diol having 6 or fewer or 5, 4, or 3 or fewer carbon atoms,
or a normal
boiling point of less than 230 or 220 or 210 C may be desirable. Ethylene
glycol may
typically be used. Alternatively, a dialkylene glycol may be used, that is, a
material of the
general structure HO-R-O-R-OH, where R represents an alkylene group (the two R
groups
may be the same or different). Alternatively, one or both of the -OH groups of
the al-
kylene- or dialkylene-glycol may be replaced by an ether group, that is, an
alkoxy group
which may contain 1 to 4 or 1 to 2 carbon atoms, such as methoxy, -OCH3.
[0017] The amount of the alkylene glycol or dialkylene glycol, or ether
thereof that
is present in the reaction mixture may be 0.2 to 2 moles per mole of
alkylphenol charged
to the reaction. Alternative amounts may be 0.4 to 1.5, or 1.0 to 1.5, or 0.5
to 1.2, or 0.6
to 1, or 0.5 to 0.8, or 0.65 to 0.8 moles per mole.
[0018] Another component of the reaction mixture will be a sulfur source
which may
be elemental sulfur, which will typically form sulfur-bridges or linkages
between the
aromatic groups of two or more alkylphenol molecules, thereby forming species
that
may be considered dimeric or oligomeric species. The amount of the sulfur
source
charged to the reaction mixture will typically be an amount to provide 0.8 to
3 moles of
sulfur (calculated assuming monomeric S units, molecular weight 32) per mole
of
alkylphenol charged to the reaction. Other amounts may be 1 to 2.5 or 1 to 2
or 1.2 to
1.8 or 1.3 to 1.5 moles per mole.
[0019] The reaction of the above-described components may be conducted
in a
solvent or other medium such as an oil of lubricating viscosity, also referred
to as a base
oil. If a volatile medium is used, it may be subsequently removed from the
reaction
mixture by evaporation or other means, e.g., steam-stripping. If a base oil is
used as the
medium, it may be retained in the reaction medium since, in some embodiments,
the
overbased product will be used in the presence of diluent oil. The base oil
may be
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selected from any of the base oils in Groups I-V of the American Petroleum
Institute
(API) Base Oil Interchangeability Guidelines, namely
Base Oil Category Sulfur (%) Saturates(%) Viscosity Index
Group I >0.03 and/or <90 80 to 120
Group II <0.03 and >90 80 to 120
Group III <0.03 and >90 >120
Group IV All polyalphaolefins (PA0s)
Group V All others not included in Groups I, II, III or IV
Groups I, II and III are mineral oil base stocks. The oil of lubricating
viscosity can
include natural or synthetic oils and mixtures thereof. Mixture of mineral oil
and
synthetic oils, e.g., polyalphaolefin oils and/or polyester oils, may be used.
[0020] Natural oils include animal oils and vegetable oils (e.g.
vegetable acid esters)
as well as 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. In one embodiment, the oil of lubricating viscosity will be
a mineral
oil. Hydro treated or hydrocracked oils are also useful oils of lubricating
viscosity. Oils
of lubricating viscosity derived from coal or shale are also useful.
[0021] Synthetic oils include hydrocarbon oils and halosubstituted
hydrocarbon oils
such as polymerized and interpolymerized olefins and mixtures thereof,
alkylbenzenes,
polyphenyl, alkylated diphenyl ethers, and alkylated diphenyl sulfides and
their deriva-
tives, analogs and homologues thereof Alkylene oxide polymers and
interpolymers and
derivatives thereof, and those where terminal hydroxyl groups have been
modified by,
e.g., esterification or etherification, are other classes of synthetic
lubricating oils. Other
suitable synthetic lubricating oils comprise esters of dicarboxylic acids and
those made
from C5 to C12 monocarboxylic acids and polyols or polyol ethers. Other
synthetic
lubricating oils include liquid esters of phosphorus-containing acids,
polymeric tetrahy-
drofurans, silicon-based oils such as poly-alkyl-, polyaryl-, polyalkoxy-, or
polyaryloxy-
siloxane oils, and silicate oils. Other synthetic oils include those produced
by Fischer-
Tropsch reactions, typically hydroisomerized Fischer-Tropsch hydrocarbons or
waxes.
In one embodiment oils may be prepared by a Fischer-Tropsch gas-to-liquid
synthetic
procedure as well as other gas-to-liquid oils.
[0022] Unrefined, refined, and rerefined oils, either natural or
synthetic (as well as
mixtures thereof) of the types disclosed hereinabove can be used. Unrefined
oils are
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those obtained directly from a natural or synthetic source without 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.
Rerefined
oils are obtained by processes similar to those used to obtain refined oils
applied to
refined oils which have been already used in service. Rerefined oils often are
addition-
ally processed to remove spent additives and oil breakdown products.
[0023]
The amount of oil of lubricating viscosity present during the reaction of the
alkylphenol with the sulfur source and the alkaline earth compound may be an
amount
suitable to provide a mixture that can be readily processed, that is, stirred
and otherwise
handled. To the extent that the final product will be used as a lubricant
additive, the oil
may serve as the conventional diluent oil in which the product is commercially
supplied.
Additional oil may be added subsequently if desired, in order to adjust the
concentration,
viscosity, or other parameters of the final product. The amount of oil
included in the
above-described reaction mixture may be 10 to 100 parts by weight per 100
parts by
weight of alkylphenol charged to the reaction. Alternative amounts may be 15
to 50, or
to 50, or 20 to 60, or 21 to 40, or 22 to 30, or 23 to 28 parts by weight per
100 parts by
weight of the alkylphenol charged to the reaction mixture. Such amounts may be
present
at the time of initial mixture of the alkylphenol with other reactants, or the
initial amount
of oil may be less and then increased to any of the above values during
subsequent pro-
20 cessing. In one embodiment, the oil of lubricating viscosity is present
in any of the
above-identified amounts at the time of the removal of the steam in step (d),
described
below. In certain embodiments the oil of lubricating viscosity will be present
during the
step of neutralizing the sulfur-bridged phenol but need not be present during
the sulfuriza-
tion step, if the sulfurization is conducted in a step prior to
neutralization.
[0024] In the case where the amount of alkaline earth metal hydroxide or
oxide is
present in an amount in excess of the stoichiometric amount needed to
neutralize the
alkylphenol moieties, the resulting salt is said to be overbased. Overbased
materials in
general, otherwise referred to as overbased or superbased salts, are generally
homogene-
ous Newtonian systems characterized by a metal content in excess of that which
would
be present for neutralization according to the stoichiometry of the metal and
the partic-
ular acidic organic compound reacted with the metal. Overbased materials are
prepared
by reacting an acidic material (typically an inorganic acid or lower
carboxylic acid,
typically carbon dioxide) with a mixture comprising an acidic organic compound
(in this
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instance, the sulfurized phenol or phenate), a reaction medium of at least one
inert,
organic solvent (e.g., mineral oil, naphtha, toluene, xylene) for said acidic
organic
material, a stoichiometric excess of a metal base, and a promoter such as a
phenol or
alcohol. The amount of excess metal is commonly expressed in terms of metal
ratio.
The term "metal ratio" is the ratio of the total equivalents of the metal to
the equivalents
of the acidic organic compound. A neutral metal salt has a metal ratio of one.
A salt
having 4.5 times as much metal as present in a normal salt will have metal
excess of 3.5
equivalents, or a ratio of 4.5.
[0025] In order to facility preparation of an overbased detergent, the
basic composi-
tion may be optionally further reacted with carbon dioxide. Such treatment
will convert
excess basicity arising from the stoichiometric excess of alkaline earth
hydroxide or
oxide to the carbonate. The amount of carbon dioxide may be an amount added
until an
excess is observed that is not absorbed by the reaction mixture. Such an
amount will
depend on the amount of basic alkaline earth material that is present, and any
other basic
materials, but in some embodiments may amount to 0.5 to 2 or 1 to 1.5 or 1.1
to 1.3 or
0.9 to 1.1 moles per mole alkylphenol charged. In some embodiments, the amount
of
carbon dioxide supplied may be 10 to 50 parts by weight per 100 parts by
weight of
alkylphenol charged to the system, alternatively 12 to 25 or 15 to 20 parts
per 100 parts.
The reaction with the carbon dioxide may take place over 1 to 10 hours, or 2
to 8 or 3 to
6 or 3.5 to 5 hours.
[0026] Overbased detergents are often characterized by Total Base
Number (TBN, as
measured by ASTM D-2896). TBN is the amount of strong acid needed to
neutralize all
of the overbased material's basicity, expressed as potassium hydroxide
equivalents (mg
KOH per gram of sample). Since overbased detergents are commonly provided in a
form which contains a certain amount of diluent oil, for example, 40-50% oil,
the actual
TBN value for such a detergent will depend on the amount of such diluent oil
present,
irrespective of the "inherent" basicity of the overbased material. For the
purposes of the
present invention, the TBN of an overbased detergent is to be recalculated to
an oil-free
basis, except as noted. Detergents which are useful in the present technology
typically
have a TBN (oil-free basis) of 100 to 800, and in one embodiment 150 to 750,
and in
another, 400 to 700. In certain embodiments, the amount of alkaline earth
metal hydrox-
ide or oxide will be the amount suitable to provide a product with a TBN of
200 to 600
on an oil-free basis; such materials are typically considered "overbased."
Products that
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are substantially "neutral," that is, not overbased or not significantly
overbased, may
nevertheless exhibit a TBN of 100-350. The overall TBN of the composition,
including
oil, will be derived from the TBN contribution of the individual components.
In the
case of a final lubricant formulation, the various components contributing TBN
may
include dispersants, the detergents, and other basic materials.
[0027] Metal compounds useful in making basic metal salts are generally
any Group
1 or Group 2 metal compounds (CAS version of the Periodic Table of the
Elements).
The Group 1 metals of the metal compound include Group la alkali metals such
as
sodium, potassium, and lithium, as well as Group lb metals such as copper. The
Group
2 metals of the metal base include the Group 2a alkaline earth metals such as
magnesi-
um, calcium, and barium, as well as the Group 2b metals such as zinc or
cadmium. In
one embodiment the Group 2 metals are magnesium, calcium, barium, or zinc, and
in
another embodiments magnesium or calcium or, in particular, calcium. In
certain
embodiments the metal is calcium or sodium or a mixture of calcium and sodium.
Generally the metal compounds are delivered as metal salts. The anionic
portion of the
salt can be hydroxide, oxide, carbonate, borate, or nitrate.
[0028] Such overbased materials are well known to those skilled in the
art. Patents
describing techniques for making basic salts of sulfonic acids, carboxylic
acids, (hydro-
carbyl-substituted) phenols, phosphonic acids, and mixtures of any two or more
of these
include U.S. Patents 2,501,731; 2,616,905; 2,616,911; 2,616,925; 2,777,874;
3,256,186;
3,384,585; 3,365,396; 3,320,162; 3,318,809; 3,488,284; and 3,629,109.
[0029] The order of addition of the components for the above-described
reaction,
and the conditions of reaction, can be varied as will be apparent to the
person skilled in
the art. For instance, the alkylphenol, the alkaline earth metal compound,
sulfur source,
and alkylene glycol or dialkylene glycol, and oil, may be added to a reaction
vessel
simultaneously or in varying orders of addition. In one embodiment, the
alkylphenol
may be first mixed (in oil) with an approximately stoichiometric amount of the
alkaline
earth metal compound and thereafter sulfur may be charged to the mixture,
along with
the glycol material. The sulfur may be supplied in one or in multiple charges.
Like-
wise, the alkaline earth metal compound may be provided in one or in multiple
charges.
Particularly if the product is to be overbased, addition of the alkaline earth
metal com-
pound and treatment with carbon dioxide may be done in multiple stages. In
another
embodiment, the alkylphenol may be first reacted with the sulfur source, in
the presence
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of the alkylene glycol (or dialkylene glyocol, or ether thereof) in the
absence (or in the
presence) of oil, and thereafter the resulting sulfur-bridged component may be
reacted
with the alkaline earth metal compound, typically in the presence of oil.
[0030] During the reaction sequence, the mixture is typically
maintained at elevated
temperature, such as 80 to 150 C, or 100 to 149 C, or 95 to 130 C, or 100
to 125
C. Temperatures and reaction times may vary depending on the order of addition
of
reagents; if different reagents are added in different stages or times, the
temperature and
reaction time of each stage may be adjusted as will be apparent to the skilled
person. In
one embodiment the temperature of the reaction mixture is increased during a
first stage,
in that the alkylphenol may be initially heated to 90 to 110 C, e.g., about
100 C, and
after the other components are added, the mixture may be further heated to 120
to 130
C, e.g., about 124 or 125 C. Alternatively, reaction with the sulfur may be
conducted
at an elevated temperature, such as 160 to 230 C, or 170 to 230 C, or 180 to
230 C, or
190 to 225, or 200 to 220, or 210 to 220 C. At any stage during the reaction,
volatile
materials may be removed by distillation or they may be retained in the
reaction mix-
ture. The reaction mixture may be maintained at an elevated temperature for a
period of
time sufficient to permit reaction to occur to the desired extent, which will,
of course,
depend to some extent on the temperature selected. Typical overall times of
reaction
may be 1/2 to 20 hours, or 1 to10, or 2 to 9, or 3 to 8, or 4 to 7, or 5 to 6
hours.
[0031] Following reaction and, if desired, treatment with carbon dioxide,
the reac-
tion mixture will be subjected to treatment with steam. In this steam-
treatment process,
the alkylphenate composition thus prepared will be heated to 120 to 280 C or
alterna-
tively 200 to 250 C, or 210 to 230, or 216 to 240 C, and steam will be
supplied thereto.
The steam may be provided at superatmospheric pressure and at a temperature of
120 C
to 250 C, or alternatively 190-240 C, but in any event should be supplied as
steam and
not as liquid water. Supplying the steam at superatmospheric pressure means
that the
steam may be provided from a source of steam at superatmospheric pressure; the
actual
contact between the steam and the reaction mixture is not necessarily
conducted at
superatmospheric pressure.
[0032] The steam which has been added is subsequently removed, and with it
a
portion of the volatile byproducts or unreacted components from the reaction
mixture.
The steam will be both added and removed in a continuous or semi-continuous
manner
commonly referred to as steam stripping, which is a well-known industrial
process. If
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desired, the steam may be re-used in multiple passes through the reaction
mixture, or it
may be used once after a single pass. The steam (and other volatile
components) may
be removed under reduced pressure of 1.3 to 53 kPa (10 to 400 mmHg), or
alternatively
2.7-13 or 4.0-6.6 kPa (20-100 mmHg or 30-50 mmHg). The total amount of steam
employed in the stripping process may be 1 to 40 parts by weight steam per 100
parts by
weight of alkylphenol charged to the reaction, or alternatively 3 to 36, or 10
to 30, parts
by weight. Greater than 36 or 40 parts by weight of steam may also be used,
although
the relative benefit obtained by using higher amounts may be less.
[0033] After the steam stripping, the reaction mixture will contain a
commercial
grade of overbased, sulfur-bridged alkylphenate in oil. The mixture will
typically be
filtered to remove any insoluble materials. This filtration may be conducted
at 130-
200 C or 149-185 C and may make use of a filter aid such as diatomaceous earth
in a
method which is well known to those skilled in the art. In brief, the filter
aid may be
mixed with the batch to be filtered and the mixture passed through any of
several types
of pressure leaf filters, such as those using screens or cloth, to form a cake
of filter aid.
The cake of filter aid performs the actual removal of solids. The filtration
may optional-
ly be assisted by vacuum. Since, a small amount of liquid and dissolved solids
are
necessarily retained within the filter cake, it is desirable that the smallest
possible
amount of filter aid be used in order to provide the highest yield of product.
[0034] The preparation of the optionally overbased, sulfur-bridged
alkylphenate by
means of the disclosed technology provides a material with significantly
improved
filterability and ease of filtration. In an industrial environment, improved
filterability is
reflected in a reduced amount of filter aid required to permit effective
filtration. If too
little filter aid is used, the filter will become plugged, resulting in
reduced flow of
filtrate and inefficiency in production of product. If excessive filter aid is
used or
required, the filtrate may flow unimpeded but an unacceptably large amount of
liquid
will be retained in the filter pad, with a loss of yield. It is therefore
desired to have an
amount of filter aid sufficient to absorb all the solid materials, but still
having porosity
or channels to permit flow of the filtrate liquids therethrough.
[0035] Filtration efficiency may thus be expressed in terms of filter aid
usage con-
sumption (FAUC). FAUC, which is expressed in units of weight percent of the
final
batch yield, may be determined by a manual batch test or series of batch
tests, in which
filter aid is added in increasing amounts until the amount is just sufficient
to obtain good
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flow of filtrate. "Good flow" is defined as a filtration time of no longer
than 60 seconds
or, alternatively, 90 seconds, for a mixture of 100 mL sample mixed with 100
mL
diluent oil, containing the specified amount of filter aid, through a screen
filter assisted
by vacuum to provide a sensibly dry filter cake. In certain embodiments, the
present
technology can be employed with a FAUC of less than 3 percent, such as 0.5 to
2.5
percent or 0.8 to 2 percent or 1 to 1.5 percent.
[0036] It is unexpected that treatment of the optionally overbased
alkylphenate with
a steam-stripping step should lead to improved filterability. It has been
recognized that
the presence of water in the overbasing process can cause the CaCO3 component
formed
thereby to convert to the vaterite form, which leads to problems with
solubility and
filtration. It appears that contact with high temperature steam has a contrary
impact on
filterability.
[0037] The sulfurized calcium alkylphenate prepared by the disclosed
technology
may also have a reduced level of free monomeric alkylphenate or alkylphenol
than
materials prepared by conventional means without the steam-stripping step.
When the
alkylphenol starting material is a tetrapropenyl phenol (TPP) such as, in one
instance,
paradodecyl phenol (PDDP), the resulting product may thereby be reduced in
amount of
residual, monomeric or unreacted, PDDP or its salt.
[0038] The amount of monomeric TPP within the product may be
determined, if
desired, by reverse phase ultra-high performance liquid chromatography by
comparison
with calibration standards prepared containing known amounts of TPP, using a
UV detector
at 225 nm. The solvent for the sample may be a mixture of 15% acetic acid in
methyl-t-
butyl ether. Suitable conditions may involve injection of a 2 ilL sample of
filtered material
onto a 100x2.1 mm Waters UPLCO column with 1.7 gm particle size packing. The
column
temperature may be 40 C and a flow rate of eluent may be 0.35 4/min, with a
gradient of
eluent composition from 75% methanol/25% water to 100% methanol. The TPP
monomer
amount is determined by integration of the appropriate peaks.
[0039] The materials of the disclosed technology are typically employed
in an oil to
form a composition that may be used as a lubricant. The oil is typically
referred to as
an oil of lubricating viscosity, and various types thereof have been described
above.
The amount of the oil of lubricating viscosity present in a lubricant is
typically the
balance remaining after subtracting from 100 weight % the sum of the amount of
the
compound of the disclosed technology and the other performance additives.
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[0040] The bridged phenolic compound may be used as one component of a
lubri-
cant formulation. Its amount, when so used, may vary depending on the end-use
appli-
cation. When used in a passenger car lubricant it may be present as low as 0.1
weight
percent, and when used in a marine diesel cylinder lubricant it may be present
in
amounts as high as 25 percent by weight of the lubricant. Therefore, suitable
ranges
may include 0.1 to 25%, or 0.5 to 20%, or 1 to 18% or 3 to 13 % or 5 to 10%.,
or 0.7 to
5 weight percent or 1 to 3 weight percent, all on an oil-free basis Similar
overall
amounts may also be used if the bridged phenolic compound is not overbased.
[0041] In lubricants containing the material of the disclosed
technology, either a
single detergent (that of the disclosed technology) or multiple detergents may
be pre-
sent. If there are multiple detergents, the additional detergents may be
additional
phenate detergents, or they may be detergents of other types. An example of
another
type of detergent is a sulfonate detergent, prepared from a sulfonic acid.
Suitable
sulfonic acids include sulfonic and thiosulfonic acids, including mono or
polynuclear
aromatic or cycloaliphatic compounds. Certain oil-soluble sulfonates can be
represented
by R2T(503-)a or R3(503-)b, where a and b are each at least one; T is a cyclic
nucleus
such as benzene or toluene; R2 is an aliphatic group such as alkyl, alkenyl,
alkoxy, or
alkoxyalkyl; (R2)-T typically contains a total of at least 15 carbon atoms;
and R3 is an
aliphatic hydrocarbyl group typically containing at least 15 carbon atoms. The
groups
T, R2, and R3 can also contain other inorganic or organic substituents. In one
embodi-
ment the sulfonate detergent may be a predominantly linear
alkylbenzenesulfonate
detergent having a metal ratio of at least 8 as described in paragraphs [0026]
to [0037]
of US Patent Application 2005-065045. In some embodiments the linear alkyl
group
may be attached to the benzene ring anywhere along the linear chain of the
alkyl group,
but often in the 2, 3 or 4 position of the linear chain, and in some instances
predomi-
nantly in the 2 position.
[0042] In one embodiment, an overbased material is an overbased
saligenin deter-
gent. Overbased saligenin detergents are commonly overbased magnesium salts
which
are based on saligenin derivatives. A general example of such a saligenin
derivative
can be represented by the formula
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OM OM
xY
0 ______ X
Rlp _ m
where X is -CHO or -CH2OH, Y is -CH2- or -CH2OCH2-, and the -CHO groups
typically
comprise at least 10 mole percent of the X and Y groups; M is hydrogen,
ammonium, or
a valence of a metal ion (that is, if M is multivalent, one of the valences is
satisfied by
the illustrated structure and other valences are satisfied by other species
such as anions
or by another instance of the same structure), R1 is a hydrocarbyl group of 1
to 60
carbon atoms, m is 0 to typically 10, and each p is independently 0, 1, 2, or
3, provided
that at least one aromatic ring contains an R1 substituent and that the total
number of
carbon atoms in all R1 groups is at least 7. When m is 1 or greater, one of
the X groups
can be hydrogen. In one embodiment, M is a valence of a Mg ion or a mixture of
Mg
and hydrogen. Saligenin detergents are disclosed in greater detail in U.S.
Patent
6,310,009, with special reference to their methods of synthesis (Column 8 and
Example
1) and preferred amounts of the various species of X and Y (Column 6).
[0043] Salixarate detergents are overbased materials that can be
represented by a
compound comprising at least one unit of formula (I) or formula (II) and each
end of the
compound having a terminal group of formula (III) or (IV):
R4 R4
(R2) j
R5
H = R7 R5 HO
R7
00R3 R6
COOR3 R6
(I) (II) (III) (IV)
such groups being linked by divalent bridging groups A, which may be the same
or
different. In formulas (I)-(IV) R3 is hydrogen, a hydrocarbyl group, or a
valence of a
metal ion; R2 is hydroxyl or a hydrocarbyl group, and j is 0, 1, or 2; R6 is
hydrogen, a
hydrocarbyl group, or a hetero-substituted hydrocarbyl group; either R4 is
hydroxyl and
R5 and R7 are independently either hydrogen, a hydrocarbyl group, or hetero-
substituted
hydrocarbyl group, or else R5 and R7 are both hydroxyl and R4 is hydrogen, a
hydro-
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carbyl group, or a hetero-substituted hydrocarbyl group; provided that at
least one of R4,
R5, R6 and R7 is hydrocarbyl containing at least 8 carbon atoms; and wherein
the mole-
cules on average contain at least one of unit (I) or (III) and at least one of
unit (II) or
(IV) and the ratio of the total number of units (I) and (III) to the total
number of units of
(II) and (IV) in the composition is 0.1:1 to 2:1. The divalent bridging group
"A," which
may be the same or different in each occurrence, includes -CH2- and -CH2OCH2-
, either
of which may be derived from formaldehyde or a formaldehyde equivalent (e.g.,
para-
form, formalin).
[0044] Salixarate derivatives and methods of their preparation are
described in
greater detail in U.S. patent number 6,200,936 and PCT Publication WO
01/56968. It is
believed that the salixarate derivatives have a predominantly linear, rather
than macro-
cyclic, structure, although both structures are intended to be encompassed by
the term
"salixarate."
[0045] Glyoxylate detergents are similar overbased materials which are
based on an
anionic group which, in one embodiment, may have the structure
C(0)0-
= H I
(I:6
0
= R
wherein each R is independently an alkyl group containing at least 4 or 8
carbon atoms,
provided that the total number of carbon atoms in all such R groups is at
least 12 or 16
or 24. Alternatively, each R can be an olefin polymer substituent. The acidic
material
upon from which the overbased glyoxylate detergent is prepared is the
condensation
product of a hydroxyaromatic material such as a hydrocarbyl-substituted phenol
with a
carboxylic reactant such as glyoxylic acid or another omega-oxoalkanoic acid.
Over-
based glyoxylic detergents and their methods of preparation are disclosed in
greater
detail in U.S. Patent 6,310,011 and references cited therein.
[0046] This supplemental overbased detergent can also be an overbased
salicylate,
e.g., an alkali metal or alkaline earth metal salt of a substituted salicylic
acid. The
salicylic acids may be hydrocarbyl-substituted wherein each substituent
contains an
average of at least 8 carbon atoms per substituent and 1 to 3 substituents per
molecule.
The substituents can be polyalkene substituents. In one embodiment, the
hydrocarbyl
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substituent group contains 7 to 300 carbon atoms and can be an alkyl group
having a
molecular weight of 150 to 2000. Overbased salicylate detergents and their
methods of
preparation are disclosed in U.S. Patents 4,719,023 and 3,372,116.
[0047] Other overbased detergents can include overbased detergents
having a Man-
nich base structure, as disclosed in U.S. Patent 6,569,818.
[0048] The amount of any supplemental overbased detergent or
detergents, if present
in a lubricant, may be 0.1 to 20, or 0.5 to 18, or 1, 2, or 3 to 13 percent by
weight.
[0049] Lubricants prepared using the materials of the presently-
disclosed technology
will typically contain one or more additional additive of the types that are
known to be
used as lubricant additives. One such additive is a dispersant. Dispersants
are well
known in the field of lubricants and include primarily what is known as
ashless-type
dispersants and polymeric dispersants. Ashless type dispersants are
characterized by a
polar group attached to a relatively high molecular weight hydrocarbon chain.
Typical
ashless dispersants include nitrogen-containing dispersants such as N-
substituted long
chain alkenyl succinimides, also known as succinimide dispersants. Succinimide
dispersants are more fully described in U.S. Patents 4,234,435 and 3,172,892.
Another
class of ashless dispersant is high molecular weight esters, prepared by
reaction of a
hydrocarbyl acylating agent and a polyhydric aliphatic alcohol such as
glycerol, pentae-
rythritol, or sorbitol. Such materials are described in more detail in U.S.
Patent
3,381,022. Another class of ashless dispersant is Mannich bases. These are
materials
which are formed by the condensation of a higher molecular weight, alkyl
substituted
phenol, an alkylene polyamine, and an aldehyde such as formaldehyde and are
described
in more detail in U.S. Patent 3,634,515. Other dispersants include polymeric
dispersant
additives, which are generally hydrocarbon-based polymers which contain polar
func-
tionality to impart dispersancy characteristics to the polymer. Dispersants
can also be
post-treated by reaction with any of a variety of agents. Among these are
urea, thiourea,
dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic
acids, hydrocar-
bon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, and
phosphorus
compounds. References detailing such treatment are listed in U.S. Patent
4,654,403. The
amount of dispersant in the present composition can typically be 1 to 10
weight percent,
or 1.5 to 9.0 percent, or 2.0 to 8.0 percent, all expressed on an oil-free
basis.
[0050] Another component is an antioxidant. Antioxidants encompass
phenolic
antioxidants, which may comprise a butyl substituted phenol containing 2 or 3
t-butyl
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groups. The para position may also be occupied by a hydrocarbyl group, an
ester-
containing group, or a group bridging two aromatic rings. Antioxidants also
include
aromatic amine, such as nonylated diphenylamines or (optionally alkylated)
phenyl-
naphthylamine. Other antioxidants include sulfurized olefins, titanium
compounds, and
molybdenum compounds. U.S. Pat. No. 4,285,822, for instance, discloses
lubricating
oil compositions containing a molybdenum and sulfur containing composition.
U.S.
Patent Application Publication 2006-0217271 discloses a variety of titanium
com-
pounds, including titanium alkoxides and titanated dispersants, which
materials may
also impart improvements in deposit control and filterability. Other titanium
com-
pounds include titanium carboxylates such as neodecanoate. Typical amounts of
antiox-
idants will, of course, depend on the specific antioxidant and its individual
effective-
ness, but illustrative total amounts can be 0.01 to 5 percent by weight or
0.15 to 4.5
percent or 0.2 to 4 percent. Additionally, more than one antioxidant may be
present, and
certain combinations of these can be synergistic in their combined overall
effect.
[0051] Viscosity improvers (also sometimes referred to as viscosity index
improvers
or viscosity modifiers) may be included in the compositions of this invention.
Viscosity
improvers are usually polymers, including polyisobutenes, polymethacrylic acid
esters,
hydrogenated diene polymers, polyalkylstyrenes, esterified styrene-maleic
anhydride
copolymers, hydrogenated alkenylarene-conjugated diene copolymers and
polyolefins.
Multifunctional viscosity improvers, which also have dispersant and/or
antioxidancy
properties are known and may optionally be used.
[0052] Another additive is an antiwear agent. Examples of anti-wear
agents include
phosphorus-containing antiwear/extreme pressure agents such as metal
thiophosphates,
phosphoric acid esters and salts thereof, phosphorus-containing carboxylic
acids, esters,
ethers, and amides; and phosphites. In certain embodiments a phosphorus
antiwear
agent may be present in an amount to deliver 0.01 to 0.2 or 0.015 to 0.15 or
0.02 to 0.1
or 0.025 to 0.08 percent phosphorus. Often the antiwear agent is a zinc
dialkyldithio-
phosphate (ZDP). For a typical ZDP, which may contain 11 percent P (calculated
on an
oil free basis), suitable amounts may include 0.09 to 0.82 percent. Non-
phosphorus-
containing anti-wear agents include borate esters (including borated
epoxides), dithio-
carbamate compounds, molybdenum-containing compounds, and sulfurized olefins.
[0053] Other materials that may be used as antiwear agents include
tartrate esters,
tartramides, and tartrimides. Examples include oleyl tartrimide (the imide
formed from
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oleylamine and tartaric acid) and alkyl diesters (from, e.g., mixed C12-16
alcohols).
Other related materials that may be useful include esters, amides, and imides
of other
hydroxy-carboxylic acids in general, including hydroxy-polycarboxylic acids,
for
instance, acids such as tartaric acid, citric acid, lactic acid, glycolic
acid, hydroxy-
propionic acid, hydroxyglutaric acid, and mixtures thereof These materials may
also
impart additional functionality to a lubricant beyond antiwear performance.
These
materials are described in greater detail in US Publication 2006-0079413 and
PCT
publication W02010/077630. Such derivatives of (or compounds derived from) a
hydroxy-carboxylic acid, if present, may typically be present in the
lubricating composi-
tion in an amount of 0.1 weight % to 5 weight %, or 0.2 weight % to 3 weight
%, or
greater than 0.2 weight % to 3 weight %.
[0054] Other additives that may optionally be used in lubricating oils
include pour
point depressing agents, extreme pressure agents, color stabilizers and anti-
foam agents.
In one embodiment the lubricant may comprise at least one of a supplemental
overbased
detergent, a dispersant, an antioxidant, a viscosity improver, an anti-wear
agent, a pour
point depressant, or an extreme pressure agent.
[0055] Lubricants containing the materials of the disclosed technology
may be used
for the lubrication of a wide variety of mechanical devices, including
internal combus-
tion engines, both two-stroke cycle and four-stroke cycle, spark-ignited and
compres-
sion-ignited, sump-lubricated or non-sump-lubricated. The engines may be run
on a
variety fuels including gasoline, diesel fuel, alcohols, bio-diesel fuel, and
hydrogen, as
well as mixtures of these (such as gasoline-alcohol mixtures, e.g., E-10, E-
15, E-85).
[0056] The disclosed lubricants are suitable for use as lubricants for
marine diesel
engines, particularly as cylinder lubricants. In one embodiment, the present
technology
provides a method for lubricating an internal combustion engine, comprising
supply-
ing thereto a lubricant comprising the composition as described herein. The
invention
is suitable for 2-stroke or 4-stroke engines, including marine diesel engines,
such as 2-
stroke marine diesel engines.
[0057] 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
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substituents; substituted hydrocarbon substituents, that is, substituents
containing non-
hydrocarbon groups which, in the context of this invention, do not alter the
predomi-
nantly hydrocarbon nature of the substituent; and hetero substituents, that
is, substitu-
ents 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
substitu-
ent" or "hydrocarbyl group" is found in paragraphs [0137] to [0141] of
published
application US 2010-0197536.
[0058] The amount of each chemical component described is presented
exclusive of
any solvent or diluent oil, which may be customarily present in the commercial
material,
that is, on an active chemical basis, unless otherwise indicated. However,
unless other-
wise indicated, each chemical or composition referred to herein should be
interpreted as
being a commercial grade material which may contain the isomers, by-products,
deriva-
tives, and other such materials which are normally understood to be present in
the
commercial grade.
[0059] It is known that some of the materials described above may interact
in the
final formulation, so that the components of the final formulation may be
different from
those that are initially added. For instance, metal ions (of, e.g., a
detergent) can migrate
to other acidic or anionic sites of other molecules. The products formed
thereby, includ-
ing the products formed upon employing the composition of the present
invention in its
intended use, may not be susceptible of easy description. Nevertheless, all
such modifi-
cations and reaction products are included within the scope of the present
invention; the
present invention encompasses the composition prepared by admixing the
components
described above.
EXAMPLES
[0060] Example 1. A calcium overbased alkylphenol sulfide is manufactured
via a
process as set forth generally in Example 1 of PCT Publication W02013/119623
(Lubri-
zol), August 15, 2013, although typically conducted on a larger, commercial
scale, and
without the specific stripping step as described therein. That is, as it is
generally de-
scribed in W02013/119623: to a 3 L four-necked round-bottom flask, equipped
with a
thermowell and nitrogen inlet, with subsurface sparge tube, a Dean-Stark trap,
Fried-
richs condenser, and a scrubber, is charged 501.0 g para-dodecylphenol (PDDP).
The
PDDP is heated to 100 C and 59.6 g hydrated lime and 22.7 g ethylene glycol
are
added. The temperature is increased to 121 C and 163.9 g sulfur is added. The
mixture
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is heated over the course of 20 minutes to 215 C and maintained at that
temperature for
an additional 6 hours, at which time 123.3 g diluent oil is added and the
reaction is
allowed to cool. During this reaction, 32.9 g distillate is collected from the
reactor.
[0061] The material in the reactor is heated to 135 C, and 204.4 g
hydrated lime,
138.2 g ethylene glycol, 43.3 g alkylbenzenesulfonic acid, and 173.5 g decyl
alcohol are
added. The mixture is heated to 168 C and maintained at that temperature for
10
minutes, until liquid is no longer readily distilling. Flow of carbon dioxide
is begun at
17-25 L/hr (0.6-0.9 ft3/hr) and continued for 4 hours.
[0062] Volatile materials are removed from a commercial-scale product
correspond-
ing to Example 1, above, by the stripping process described either in Example
2 or
Reference Example 3, below:
[0063] Example 2. A batch of carbon dioxide-treated material is
stripped by circu-
lating the batch, originating in a feed tank, though an external heat
exchanger and then
a flash tank, and finally back to the feed tank, for a period of time referred
to as "strip-
back." During the strip-back, the external heat exchanger batch exit
temperature target
it 218-238 C. Heat is also applied directly to the stripper feed tank
throughout the strip-
back phase, until the batch reaches a target temperature of 218-226 C. The
flash tank is
operated at a target pressure of 8-16 kPa (60-120 mm Hg absolute), with a
residence
time of approximately 3 minutes. Flow through the flash tank provides 2 to 3
volumet-
ric turnovers of the batch through the flash tank during the strip-back phase,
over
approximately 6 hours. Thereafter, the liquid outflow from the flash tank is
redirected
to a filter-feed tank, with stripping conditions otherwise maintained.
Throughout the
stripping process, steam is fed to the flash tank via a sub-surface inlet
line, at an approx-
imately uniform rate, targeting delivery of approximately 18 parts by weight
total steam
(based on 100 parts by weight of initial alkylphenol reactant, before sulfur
coupling and
neutralization/overbasing). The batch is filtered by use of 1 weight% filter
aid (FAUC).
[0064] Example 3 (Reference). A batch of carbon dioxide-treated
material is
stripped as described in Example 2, except that no steam is fed to the flash
tank at any
time. The batch is filtered by use of 3.5 weight % filter aid (FAUC).
[0065] Each of the documents referred to above is incorporated herein by
reference,
including any prior applications, whether or not specifically listed above,
from which
priority is claimed. The mention of any document is not an admission that such
docu-
ment qualifies as prior art or constitutes the general knowledge of the
skilled person in
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any jurisdiction. Except in the Examples, or where otherwise explicitly
indicated, all
numerical quantities in this description specifying amounts of materials,
reaction condi-
tions, molecular weights, number of carbon atoms, and the like, are to be
understood as
modified by the word "about." 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.
[0066] As used herein, the transitional term "comprising," which is
synonymous with
"including," "containing," or "characterized by," is inclusive or open-ended
and does not
exclude additional, un-recited elements or method steps. However, in each
recitation of
"comprising" herein, it is intended that the term also encompass, as
alternative embodi-
ments, the phrases "consisting essentially of" and "consisting of," where
"consisting of"
excludes any element or step not specified and "consisting essentially of"
permits the
inclusion of additional un-recited elements or steps that do not materially
affect the
essential or basic and novel characteristics of the composition or method
under consider-
ation. The expression "consisting of" or "consisting essentially of," when
applied to an
element of a claim, is intended to restrict all species of the type
represented by that
element, notwithstanding the presence of "comprising" elsewhere in the claim.
[0067] While certain representative embodiments and details have been
shown for the
purpose of illustrating the subject invention, it will be apparent to those
skilled in this art
that various changes and modifications can be made therein without departing
from the
scope of the subject invention. In this regard, the scope of the invention is
to be limited
only by the following claims. In certain jurisdictions, recitation of one or
more of nar-
rower values for a numerical range or recitation of a narrower selection of
elements from
a broader list means that such recitations represent preferred embodiments.
21
