Note: Descriptions are shown in the official language in which they were submitted.
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LUBRICANT COMPOSITIONS HAVING
IMPROVED LOW TEMPERATURE PERFORMANCE
FIELD
[0001] This disclosure relates to lubricant compositions formulated with
unique Group III base
stocks and blends of such base stocks.
BACKGROUND
[0002] Base oil is the major constituent in finished lubricants and
contributes significantly to
the properties of the lubricant. Engine oils are finished crankcase lubricants
intended for use in
automobile engines and diesel engines and contain two general components,
namely, a base stock
.. or base oil (one base stock or a blend of base stocks) and additives. In
general, a few lubricating
base oils are used to manufacture a variety of engine oils by varying the
mixtures of individual
lubricating base oils and individual additives.
[0003] According to the American Petroleum Institute (API)
classifications, base stocks are
categorized in five groups based on their saturated hydrocarbon content,
sulfur level, and viscosity
index (Table 1). Lube base stocks are typically produced in large scale from
non-renewable
petroleum sources. Group I, II, and III base stocks are all derived from crude
oil via extensive
processing, such as solvent extraction, solvent or catalytic dewaxing, and
hydroisomerization.
Group III base stocks can also be produced from synthetic hydrocarbon liquids
obtained from
natural gas, coal or other fossil resources, Group IV base stocks are
polyalphaolefins (PA0s), and
are produced by oligomerization of alpha olefins, such as 1-decene. Group V
base stocks include
all base stocks that do not belong to Groups I-IV, such as naphthenics,
polyalkylene glycols (PAG),
and esters.
TABLE 1
API
classification Group I Group II Group III Group IV Group
V
% Saturates <90 90 90
Polyalpha- All others
% S >0.03 0.03 0.03 Olefins not
Viscosity 80-120 80-120 120 (PA0s) belonging to
Index (VI) group I-IV
[0004] Base oils are generally produced from the higher boiling
fractions recovered from a
vacuum distillation operation. They may be prepared from either petroleum-
derived or from
syncrude-derived feed stocks or from synthesis of lower molecular weight
molecules. Additives
are chemicals which are added to base oil to improve certain properties in the
finished lubricant so
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that it meets the minimum performance standards for the grade of the finished
lubricant. For
example, additives added to the engine oils may be used to improve oxidation
stability of the
lubricant, increase its viscosity, raise the viscosity index, and control
deposits. Additives are
expensive and may cause miscibility problems the finished lubricant. For these
reasons, it is
generally desirable to optimize the additive content of the engine oils to the
minimum amount
necessary to meet the appropriate requirements.
[0005] Formulations are undergoing changes driven by a need for
increased quality. For
example governing organizations (e.g., the American Petroleum Institute) help
to define the
specifications for engine oils. Increasingly, the specifications for engine
oils are calling for
products with excellent low temperature properties and high oxidation
stability. Currently, only a
small fraction of the base oils blended into engine oils are able to meet the
most stringent of the
demanding engine oil specifications. Currently, formulators are using a range
of base stocks
including Group I, II, III, IV, and V base stocks to formulate their products.
[0006] Industrial oils are also being pressed for improved quality in
oxidation stability,
cleanliness, interfacial properties and deposit control.
[0007] Despite advances in lubricating base oils and lubricant oil
formulation technology, there
exists a need for improving oxidation performance (for example, for engine
oils and industrial oils
that have a longer life) and low temperature performance of formulated oils.
In particular, there
exists a need for improving oxidation performance and low temperature
performance of formulated
oils without the addition of more additives to the lubricant oil formulation.
SUMMARY
[0008] This disclosure relates to formulated lubricant compositions
containing unique Group
III base stocks and blends.
[0009] This disclosure relates in part to lubricating compositions
prepared with Group III base
stocks having a kinematic viscosity at 100 C greater than 2 cSt, such as from
2 cSt to above 14
cSt, for example from 2 cSt to 12 cSt and from 4 cSt to 7 cSt. These base
stocks are also referred
to as lubricating oil base stocks or products in the present disclosure. In an
embodiment, the present
disclosure provides a lubricating composition comprising a Group III base
stock having:
at least 90 wt.% saturated hydrocarbons; kinematic viscosity at 100 C (KV100)
of 4.0 cSt to 12.0
cSt; a viscosity index of from 120 to 133; a ratio of multi-ring naphthenes to
single ring naphthenes
(2R+NRRN) of less than 0.43; and an effective amount of one or more lubricant
additives.
[0010] In another embodiment, the present disclosure provides a
passenger car motor oil
composition comprising a Group III base stock having: at least 90 wt.%
saturated hydrocarbons;
kinematic viscosity at 100 C of from 4.0 cSt up to 5.0 cSt; a viscosity index
of from 120 to less
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than 140; a ratio of multi-ring naphthenes to single ring naphthenes (2R+NRRN)
of less than 0.45;
and an effective amount of one or more lubricant additives.
[0011] In another embodiment, the present disclosure provides a heavy
duty diesel engine
lubricating oil composition comprising a Group III base stock having: at least
90 wt.% saturated
hydrocarbons; kinematic viscosity at 100 C of from 5.5 cSt up to 7.0 cSt; a
viscosity index of from
120 to less than 144; a ratio of multi-ring naphthenes to single ring
naphthenes (2R+NRRN) of
less than 0.56; and an effective amount of one or more lubricant additives.
[0012] In another embodiment, the present disclosure provides a
lubricating composition
comprising a Group III base stock having: at least 90 wt.% saturated
hydrocarbons;
kinematic viscosity at 100 C of 4.0 cSt to 5.0 cSt; a viscosity index of 120
to 140; a ratio of multi-
ring naphthenes to single ring naphthenes (2R+NRRN) of less than 0.52; a ratio
of branched
carbons to straight chain carbons (BC/SC) less than or equal to 0.23; and an
effective amount of
one or more lubricant additives.
[0013] In another embodiment, the present disclosure provides a
lubricating composition
comprising a Group III base stock having: at least 90 wt.% saturated
hydrocarbons; kinematic
viscosity at 100 C of 5.0 cSt to 12.0 cSt; a viscosity index of 120 to 140; a
ratio of multi-ring
naphthenes to single ring naphthenes (2R+NRRN) of less than 0.59; a ratio of
branched carbons
to straight chain carbons (BC/SC) less than or equal to 0.26; and an effective
amount of one or
more lubricant additives.
[0014] In another embodiment, the present disclosure provides a lubricating
composition
prepared with a base stock having a ratio of multi-ring naphthenes to single
ring naphthenes
(2R+NRRN) of less than 0.59 and a ratio of branched chain carbons to terminal
carbons less than
2.6.
[0015] In another embodiment, the present disclosure provides a
lubricating composition
comprising a Group III base stock having: at least 90 wt.% saturated
hydrocarbons; kinematic
viscosity at 100 C (KV100) of 5.0 cSt to 12.0 cSt; a viscosity index of from
120 to 144; a ratio
of multi-ring naphthenes to single ring naphthenes (2R+NRRN) of less than
0.56; and an effective
amount of one or more lubricant additives.
[0016] The Group III base stocks useful in preparing the lubricant
compositions of the present
disclosure can be obtained utilizing a process for producing a diesel fuel and
a Group III base stock.
Generally, a feed stock (e.g., a heavy vacuum gas oil feed stock having a
solvent dewaxed oil feed
viscosity index of from about 45 to about 150) or a mixed feed stock having a
solvent dewaxed oil
feed viscosity index of from about 45 to about 150 is processed through a
first stage which is
primarily a hydrotreating unit which boosts viscosity index (VI) and removes
sulfur and nitrogen.
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This is followed by a stripping section where light ends and diesel are
removed. The heavier lube
fraction then enters a second stage where hydrocracking, dewaxing, and
hydrofinishing are
perfrormed. This combination of feed stock and process approaches produces a
base stock with
unique compositional characteristics. These unique compositional
characteristics are observed in
both the low, medium and high viscosity base stocks produced.
[0017] Other objects and advantages of the present disclosure will
become apparent from the
detailed description that follows.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Fig. 1 is a multi-stage reaction system according to an
embodiment of the disclosure.
[0019] Fig. 2 shows an example of a processing configuration suitable for
producing Group III
base stocks of the present disclosure.
[0020] Fig. 3 is a graph illustrating the relationship between the ratio
of molecules with multi-
ring naphthenes to molecules with single ring naphthenes (2R+NRRN) and the
viscosity index of
light neutral Group III base stocks of the present disclosure as compared to
other Group III base
stocks.
[0021] Fig. 4 is a graph illustrating the relationship between the ratio
of molecules with multi-
ring naphthenes to molecules with single ring naphthenes (2R+NRRN) and the
viscosity index of
medium neutral Group III base stocks of the present disclosure as compared to
other Group III
base stocks.
[0022] Fig. 5 is a graph illustrating the relationship between the ratio of
molecules with multi-
ring naphthenes to molecules with single ring naphthenes (2R+NRRN) and the
degree of branching
(branched carbons/straight chain carbons) of light neutral Group III base
stocks of the present
disclosure as compared to other Group III base stocks.
[0023] Fig. 6 is a graph illustrating the relationship between the ratio
of molecules with multi-
ring naphthenes to molecules with single ring naphthenes (2R+NRRN) and the
nature of the
branching (branched carbon/terminal carbons) of light neutral Group III base
stocks of the present
disclosure as compared to other Group III base stocks.
[0024] Fig. 7 is a graph illustrating the relationship between the ratio
of molecules with multi-
ring naphthenes to molecules with single ring naphthenes (2R+NRRN) and the
degree of branching
(branched carbons/straight chain carbons) of medium and high neutral Group III
base stocks of the
present disclosure as compared to other Group III base stocks.
[0025] Fig. 8 is a graph illustrating the relationship between the ratio
of molecules with multi-
ring naphthenes to molecules with single ring naphthenes (2R+NRRN) and the
nature of the
branching (branched carbon/terminal carbons) of medium and heavy neutral Group
III base stocks
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of the present disclosure as compared to other Group III base stocks.
[0026] Fig. 9 is a graph illustrating the relationship between the pour
point and mini-rotary
viscosity (MRV) behavior of formulated light neutral Group III base stocks
prepared according to
the present disclosure as compared to other Group III base stocks.
[0027] Fig. 10 is a graph illustrating the relationship between the ratio
of molecules with multi-
ring naphthenes to molecules with single ring naphthenes (2R+NRRN) and the
mini-rotary
viscosity (MRV) behavior of formulated light neutral Group III base stocks
prepared according to
the present disclosure as compared to other Group III base stocks.
[0028] Fig. 11 is a graph illustrating the relationship between the pour
point and mini-rotary
ix) viscosity (MRV) behavior of formulated medium neutral Group III base
stocks prepared according
to the present disclosure as compared to other Group III base stocks.
[0029] Fig. 12 is a graph illustrating the relationship between the
ratio of molecules with multi-
ring naphthenes to molecules with single ring naphthenes (2R+NRRN) and the
mini-rotary
viscosity (MRV) behavior of formulated medium neutral Group III base stocks
prepared according
to the present disclosure as compared to other Group III base stocks.
DETAILED DESCRIPTION
[0030] All numerical values within the detailed description and the
claims herein are modified
by "about" or "approximately" the indicated value, and take into account
experimental error and
variations that would be known to a person of ordinary skill in the art.
[0031] As used herein, the term "major component" means a component (e.g.,
base stock)
present in a lubricating oil of this disclosure in an amount greater than
about 50 weight percent
(wt. %).
[0032] As used herein, the term "minor component" means a component
(e.g., one or more
lubricating oil additives) present in a lubricating oil of this disclosure in
an amount less than 50
weight percent.
[0033] As used herein, the term "single ring naphthenes" means a
saturated hydrocarbon group
having the general formula Calm arranged in the form of a single closed ring,
where n is the
number of carbon atoms. It is also denoted herein as 1RN.
[0034] As used herein, the term "multi-ring naphthenes" means a
saturated hydrocarbon group
having the general formula GI-12(n+1-r) arranged in the form of multiple
closed rings, where n is the
number of carbon atoms and r is the number of rings (here, r > 1). It is also
denoted herein as
2+RN.
[0035] As used herein, "kinematic viscosity at 100 C" will be used
interchangeably with
"KV100" and "kinematic viscosity at 40 C" will be used interchangeably with
"KV40." The two
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terms should be considered equivalent.
[0036] As used herein, the term "straight-chain carbons" means the sum
of the alpha, beta,
gamma, delta, and epsilon peaks as measured by '3C nuclear magnetic resonance
(NMR)
spectroscopy.
[0037] As used herein, the term "branched carbons" means the sum of the
pendant methyl,
pendant ethyl, and pendant propyl groups as measured by '3C NMR.
[0038] As used herein, the term "terminal carbons" means the sum of the
terminal methyl,
terminal ethyl, and terminal propyl groups as measured by '3C NMR.
Lubricating Oil Base Stocks
[0039] In accordance with this disclosure, lubricating compositions, such
as engine lubricating
oil compositions, are provided having certain species of paraffin molecules.
The present inventors
have surprisingly discovered lubricant compositions prepared with base stocks
having a low ratio
of 2R+NRRN and/or fewer branched chain carbons, such as those produced, for
example, by the
method described herein, demonstrate improved low temperature viscosity
properties. Lower
levels of 2R+N molecules and branched carbon species are desirable in
lubricant compositions
because high levels of 2R+N molecules and branched carbon species can hinder
the low
temperature performance, such as low temperature viscosity, of formulated
oils. In particular, the
lubricating compositions of the present disclosure have improved oxidative
performance,
particularly at low temperatures, as compared to conventional lubricants. For
example the
oxidative performance of the formulated base stocks of the present disclosure,
using CEC-L-85 or
ASTM D6186, demonstrate an improvement over lubricants prepared with currently
commercial
conventional base stocks of 10-100 times, for example 20-50 times such as 30-
40 times.
[0040] According to various embodiments of the disclosure, the base
stocks utilized in the
lubricating compositions of the present disclosure are API Group III base
stocks. Group III base
stocks of the present disclosure can be produced by an advanced hydrocracking
process using a
feed stock, for example, a vacuum gas oil feed stock having a solvent dewaxed
oil feed viscosity
index of at least 45, such as at least 55, for example at least 60 up to 150,
or 60 to 90, or a heavy
vacuum gas oil and heavy atmospheric gas oil mixed feed stock having a solvent
dewaxed oil feed
viscosity index of at least 45, such as at least 55, for example, at least 60
to about 150, or 60 to 90.
Group III at least 45, such as at least 55, for example at least 60 to 150, or
60 to 90. Group III base
stocks of the present disclosure can have a kinematic viscosity at 100 C
greater than 2 cSt, such as
from 2 cSt to 14 cSt, for example from 2 cSt to 12 cSt and from 4 cSt to 12
cSt. Group III base
stocks of the present disclosure can have a ratio of multi-ring naphthenes to
single ring naphthenes
(2R+NRRN) less than about 0.59 and a ratio of branched chain carbons to
straight-chain carbons
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of less than or equal to 0.23. Group III base stocks of the present disclosure
can also have a ratio
of branched chain carbons to terminal carbons less than 2.6.
[0041] The API Group III base stocks used in the lubricant compositions
of the present
disclosure can have a ratio of multi-ring naphthenes to single ring naphthenes
of less than 0.59,
such as less than 0.52, such as less than 0.46, such as less than 0.45 or less
than 0.43 for base stocks
having a kinematic viscosity at 100 C of 4-12 cSt. The base stocks can have a
ratio of (branched
chain carbons to terminal carbons (BC/TC)) wherein BC/TC <2.3. The light
neutral base stocks
can have a viscosity index from 102 to 133 and less than or equal to 142*(1 ¨
0.0025
exp(8*(2R+NRRN))). The medium and heavy neutral base stocks can have a
viscosity index 120
to 133 less than or equal to 150.07*(1-
0.0106*exp(4.5*(2R+NRRN))).Additionally, the levels of
naphthenes can be lower in the base stocks of the present disclosure as
compared to commercially
known base stocks across the range of viscosities. The naphthene content can
be 30 wt.% to 70
wt.%.
[0042] The Group III base stocks of the present disclosure can have less
than 0.03 wt.% sulfur,
a pour point of -10 C to -30 C, a Noack volatility of 0.5 wt.% to 20 wt.%, a
CCS (cold crank
simulator) value at -35 C of 100 cP up to 70,000cP,and naphthene content of 30
wt.% to 70 wt.%.
The light neutral Group III base stocks, i.e., those with a KV100 of 2 cSt to
5 cSt, can have a
Noack volatility of from 8 wt.% to 20 wt. %, a CCS value at -35 C of 100 cP to
6,000 cP, a pour
point of -10 C to -30 C and naphthene content of 30 wt. % to 60 wt. %. The
medium neutral
Group III base stocks of the present disclosure, i.e., those with KV100 of 5
cSt to 7 cSt, can have
a Noack volatility of 2 wt. % to 10 wt.%, a CCS value at -35 C of 3,500 cP to
20,000 cP, a pour
point of -10 C to -30 C and naphthene content of 30 wt.% to 60 wt.%. The heavy
neutral Group
III base stocks of the present disclosure, i.e. those with KV100 of 7 cSt to
12 cSt, can have a Noack
volatility of 0.5 wt. % to 4 wt.%, a CCS value at -35 C of 10,000 cP to 70,000
cP, a pour point of
-10 C to -30 C and naphthene content of 30 wt.% to 70 wt.%. According to
various embodiments
of the present invention, the Group III base stocks comprise 30 wt.% to 70%
paraffins, or 31 wt.%
to 69 wt.% paraffins or 32 wt.% to 68 wt.% paraffins. According to various
embodiments of the
present invention, a light neutral Group III base stock can contain 40 wt.% to
70 wt.%, or 45 wt.%
to 70 wt.%, or 45 wt% to 65 wt.% of paraffins. According to various
embodiments of the present
invention, a medium neutral Group III base stock can contain 35 wt.% to 65
wt.%, or 40 wt.% to
65 wt.%, or 40 wt% to 60 wt.% of paraffins. According to various embodiments
of the present
invention, a heavy neutral Group III base stock can contain 30 wt.% to 60
wt.%, or 30 wt.% to 55
wt.%, or 30 wt% to 50 wt.%, or 30 wt.% to 45 wt.%, or 30 wt.% to 40 wt.% of
paraffins.
Process
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100431 The process described below can be used to produce the
compositionally advantaged
Group III base stocks of this disclosure. Generally, a feed stock, for
example, a heavy vacuum gas
oil feed stock having a solvent dewaxed oil feed viscosity index of from at
least 45, preferably at
least 55, and more preferably at least 60 up to about 150, or a mixed feed
stock having a solvent
dewaxed oil feed viscosity index of from at least 45, preferably at least 55,
and more preferably at
least 60 up to about 150 is processed through a first stage which is primarily
a hydrotreating unit
which boosts viscosity index (VI) and removes sulfur and nitrogen. This is
followed by a stripping
section where light ends and diesel are removed. The heavier lube fraction
then enters a second
stage where hydrocracking, dewaxing, and hydrofinishing are performed. This
combination of feed
stock and process approaches produces a base stock with unique compositional
characteristics.
These unique compositional characteristics are observed in both the low,
medium and high
viscosity base stocks produced.
[0044] The process configurations of the present disclosure produce high
quality Group III
base stocks that have unique compositional characteristics with respect to
conventional Group III
base stocks. The compositional advantage may be derived from the muti-ring
naphthenes to single
ring naphthenes ratio of the composition.
[0045] The processes of the present disclosure can produce base stocks
having a kinematic
viscosity at 100 C (KV100) of greater than or equal to 2 cSt, or greater than
or equal to 4 cSt, such
as from 4 cSt to 7 cSt, or greater than or equal to 6 cSt, or greater than or
equal to 8 cSt, or greater
than or equal to 10 cSt, or greater than or equal to 12 cSt, or greater than
or equal to 14 cSt. The
base stocks produced using the processes of the present disclosure can yield
base stocks having a
VI of at least 120 up to about 145, such as 120 to 140 or 120 to 133.
[0046] As used herein, a stage can correspond to a single reactor or a
plurality of reactors.
Optionally, multiple parallel reactors can be used to perform one or more of
the processes, or
multiple parallel reactors can be used for all processes in a stage. Each
stage and/or reactor can
include one or more catalyst beds containing hydroprocessing catalyst or
dewaxing catalyst. It is
noted that a "bed" of catalyst can refer to a partial physical catalyst bed.
For example, a catalyst
bed within a reactor could be filled partially with a hydrocracking catalyst
and partially with a
dewaxing catalyst. For convenience in description, even though the two
catalysts may be stacked
together in a single catalyst bed, the hydrocracking catalyst and dewaxing
catalyst can each be
referred to conceptually as separate catalyst beds.
Configuration Example
[0047] Figure 1 shows an example of a processing configuration suitable
for manufacturing
the base stocks in this disclosure. Figure 2 shows an example of a general
processing configuration
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suitable for processing a feedstock to produce base stocks of the present
disclosure. Note that R1
corresponds to 110 in Figure 2; furthermore, R2, R3, R4, and R5 correspond to
120, 130, 140, and
150 from Figure 2, respectively. Details on the processing configuration can
be found in US
Application 2015/715,555. In Figure 2, a feedstock 105 can be introduced into
a first reactor 110.
A reactor such as first reactor 110 can include a feed inlet and an effluent
outlet. First reactor 110
can correspond to a hydrotreating reactor, a hydrocracking reactor, or a
combination thereof
Optionally, a plurality of reactors can be used to allow for selection of
different conditions. For
example, if both a first reactor 110 and optional second reactor 120 are
included in the reaction
system, first reactor 110 can correspond to a hydrotreatment reactor while
second reactor 120 can
correspond to a hydrocracking reactor. Yet other options for arranging
reactor(s) and/or catalysts
within the reactor(s) to perform initial hydrotreating and/or hydrocracking of
a feedstock can also
be used. Optionally, if a configuration includes multiple reactors in the
initial stage, a gas-liquid
separation can be performed between reactors to allow for removal of light
ends and contaminant
gases. In aspects where the initial stage includes a hydrocracking reactor,
the hydrocracking reactor
in the initial stage can be referred to as an additional hydrocracking
reactor.
[0048] The hydroprocessed effluent 125 from the final reactor (such as
reactor 120) of the
initial stage can then be passed into a fractionator 130, or another type of
separation stage.
Fractionator 130 (or other separation stage) can separate the hydroprocessed
effluent to form one
or more fuel boiling range fractions 137, a light ends fraction 132, and a
lubricant boiling range
fraction 135. The lubricant boiling range fraction 135 can often correspond to
a bottoms fraction
from the fractionator 130. The lubricant boiling range fraction 135 can
undergo further
hydrocracking in second stage hydrocracking reactor 140. The effluent 145 from
second stage
hydrocracking reactor 140 can then be passed into a dewaxing / hydrofinishing
reactor 150 to
further improve the properties of the eventually produced lubricant boiling
range products. In the
configuration shown in Figure 2, the effluent 155 from second stage dewaxing /
hydrofinishing
reactor 150 can be fractionated 160 to separate out light ends 152 and/or fuel
boiling range
fraction(s) 157 from one or more desired lubricant boiling range fractions
155.
[0049] The configuration in Figure 2 can allow the second stage
hydrocracking reactor 140
and the dewaxing / hydrofinishing reactor 150 to be operated under sweet
processing conditions,
corresponding to the equivalent of a feed (to the second stage) sulfur content
of 100 wppm or less.
Under such "sweet" processing conditions, the configuration in Figure 2, in
combination with use
of a high surface area, low acidity catalyst, can allow for production of a
hydrocracked effluent
having a reduced or minimized content of aromatics.
[0050] In the configuration shown in Figure 2, the final reactor (such
as reactor 120) in the
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initial stage can be referred to as being in direct fluid communication with
an inlet to the
fractionator 130 (or an inlet to another type of separation stage). The other
reactors in the initial
stage can be referred to as being in indirect fluid communication with the
inlet to the separation
stage, based on the indirect fluid communication provided by the final reactor
in the initial stage.
The reactors in the initial stage can generally be referred to as being in
fluid communication with
the separation stage, based on either direct fluid communication or indirect
fluid communication.
In some optional aspects, one or more recycle loops can be included as part of
a reaction system
configuration. Recycle loops can allow for quenching of effluents between
reactors / stages as well
as quenching within a reactor / stage.
[0051] In an embodiment, a feedstock is introduced into a reactor under
hydrotreating
conditions. The hydrotreated effluent is then passed to a fractionator where
the effluent is separated
into fuel boiling range fractions and lubricant boiling range fractions. The
lubricant boiling range
fractions are then passed to a second stage where hydrocracking, dewaxing and
hydrofinishing
steps are perfomed. The effluent from the second stage is then passed to a
fractionator where the
Group III base stocks of the present disclosure are recovered.
Feedstocks
[0052] A wide range of petroleum and chemical feedstocks can be
hydroprocessed in
accordance with the invention. Suitable feedstocks include whole and reduced
petroleum crudes
such as Arab Light, extra Light, Midland Sweet, Delaware Basin, West Texas
Intermediate, Eagle
Ford, Murban and Mars crudes, atmospheric oils, cycle oils, gas oils,
including vacuum gas oils
and coker gas oils, light to heavy distillates including raw virgin
distillates, hydrocrackates,
hydrotreated oils, petroleum-derived waxes (including slack waxes), Fischer-
Tropsch waxes,
raffinates, deasphalted oils, and mixtures of these materials.
[0053] One way of defining a feedstock is based on the boiling range of
the feed. One option
for defining a boiling range is to use an initial boiling point for a feed
and/or a final boiling point
for a feed. Another option is to characterize a feed based on the amount of
the feed that boils at
one or more temperatures. For example, a "T5" boiling point / distillation
point for a feed is defined
as the temperature at which 5 wt% of the feed will boil off Similarly, a "T95"
boiling point /
distillation point is a temperature at which 95 wt% of the feed will boil.
Boiling points, including
fractional weight boiling points, can be determined using an appropriate ASTM
test method, such
as the procedures described in ASTM D2887, D2892, D6352, D7129, and/or D86.
[0054] Typical feeds include, for example, feeds with an initial boiling
point of at least 600 F
(-316 C); similarly, the T5 and/or T10 boiling point of the feed can be at
least 600 F (-316 C).
Additionally or alternately, the final boiling point of the feed can be 1100 F
(-593 C) or less;
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similarly, the T95 boiling point and/or T90 boiling point of the feed can also
be 1100 F (-593 C)
or less. As one non-limiting example, a typical feed can have a T5 boiling
point of at least 600 F
(-316 C) and a T95 boiling point of 1100 F (-593 C) or less. Optionally, if
the hydroprocessing
is also used to form fuels, the feed may include a lower boiling range
portion. For example, such a
.. feed can have an initial boiling point of at least 350 F (-177 C) and a
final boiling point of 1100 F
(-593 C) or less.
[0055] In some aspects, the aromatics content of the feed, as determined
by UV-Vis absorption
or equivalent methods such as ASTM D7419 or ASTM D2007 or equivalent methods,
can be at
least 20 wt%, or at least 25 wt%, or at least 30 wt%, or at least 40 wt%, or
at least 50 wt%, or at
least 60 wt%, such as up 15 to 75 wt% or up to 90 wt%. In particular, the
aromatics content can be
25 wt% to 75 wt%, or 25 wt% to 90 wt%, or 35 wt% to 75 wt%, or 35 wt% to 90
wt%. In other
aspects, the feed can have a lower aromatics content, such as an aromatics
content of 35 wt% or
less, or 25 wt% or less, such as down to 0 wt%. In particular, the aromatics
content can be 0 wt%
to 35 wt%, or 0 wt% to 25 wt%, or 5.0 wt% to 35 wt%, or 5.0 wt% to 25 wt%.
[0056] Particular feed stock components useful in processes of the present
disclosure include
vacuum gas oil feed stocks (e.g., medium vacuum gas oil feeds (MVGO)) having a
solvent
dewaxed oil feed viscosity index of from at least 45, at least 50, at least
55, or at least 60 to 150,
such as from 65 to 125, at least 65 to 110, from 65 to 100 or 65 to 90.
[0057] Other particular feed stock components useful in processes of the
present disclosure
include feed stocks having a mixed vacuum gas oil feed (e.g., medium vacuum
gas oil feed
(MVGO)) and a heavy atmospheric gas oil feed, in which the mixed feed stock
has a solvent
dewaxed oil feed viscosity index of from at least 45, at least 55, at least 60
to 150, such as from 65
to 145, from 65 to 125, from 65 to 100 or 65 to 90.
[0058] In aspects where the hydroprocessing includes a hydrotreatment
process and/or a sour
.. hydrocracking process, the feed can have a sulfur content of 500 wppm to
20000 wppm or more,
or 500 wppm to 10000 wppm, or 500 wppm to 5000 wppm. Additionally or
alternately, the
nitrogen content of such a feed can be 20 wppm to 4000 wppm, or 50 wppm to
2000 wppm. In
some aspects, the feed can correspond to a "sweet" feed, so that the sulfur
content of the feed is 25
wppm to 500 wppm and/or the nitrogen content is 1 wppm to 100 wppm.
.. First Hydroprocessing Stage ¨ Hydrotreating and/or Hydrocracking
[0059] In various aspects, a first hydroprocessing stage can be used to
improve one or more
qualities of a feedstock for lubricant base oil production. Examples of
improvements of a feedstock
can include, but are not limited to, reducing the heteroatom content of a
feed, performing
conversion on a feed to provide viscosity index uplift, and/or performing
aromatic saturation on a
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feed.
[0060] With regard to heteroatom removal, the conditions in the initial
hydroprocessing stage
(hydrotreating and/or hydrocracking) can be sufficient to reduce the sulfur
content of the
hydroprocessed effluent to 250 wppm or less, or 200 wppm or less, or 150 wppm
or less, or 100
wppm or less, or 50 wppm or less, or 25 wppm or less, or 10 wppm or less. In
particular, the sulfur
content of the hydroprocessed effluent can be 1 wppm to 250 wppm, or 1 wppm to
50 wppm, or 1
wppm to 10 wppm. Additionally or alternately, the conditions in the initial
hydroprocessing stage
can be sufficient to reduce the nitrogen content to 100 wppm or less, or 50
wppm or less, or 25
wppm or less, or 10 wppm or less. In particular, the nitrogen content can be 1
wppm to 100 wppm,
or 1 wppm to 25 wppm, or 1 wppm to 10 wppm.
[0061] In aspects that include hydrotreating as part of the initial
hydroprocessing stage, the
hydrotreating catalyst can comprise any suitable hydrotreating catalyst, e.g.,
a catalyst comprising
at least one Group 8 ¨ 10 non-noble metal (for example selected from Ni, Co,
and a combination
thereof) and at least one Group 6 metal (for example selected from Mo, W, and
a combination
thereof), optionally including a suitable support and/or filler material
(e.g., comprising alumina,
silica, titania, zirconia, or a combination thereof). The hydrotreating
catalyst according to aspects
of this invention can be a bulk catalyst or a supported catalyst. Techniques
for producing supported
catalysts are well known in the art. Techniques for producing bulk metal
catalyst particles are
known and have been previously described, for example in U.S. Patent No.
6,162,350, which is
hereby incorporated by reference. Bulk metal catalyst particles can be made
via methods where all
of the metal catalyst precursors are in solution, or via methods where at
least one of the precursors
is in at least partly in solid form, optionally but preferably while at least
another one of the
precursors is provided only in a solution form. Providing a metal precursor at
least partly in solid
form can be achieved, for example, by providing a solution of the metal
precursor that also includes
solid and/or precipitated metal in the solution, such as in the form of
suspended particles. By way
of illustration, some examples of suitable hydrotreating catalysts are
described in one or more of
U.S. Patent Nos. 6,156,695, 6,162,350, 6,299,760, 6,582,590, 6,712,955,
6,783,663, 6,863,803,
6,929,738, 7,229,548, 7,288,182, 7,410,924, 7,544,632, and 8,294,255, U.S.
Patent Application
Publication Nos. 2005/0277545, 2006/0060502, 2007/0084754, and 2008/0132407,
and
International Publication Nos. WO 04/007646, WO 2007/084437, WO 2007/084438,
WO
2007/084439, and WO 2007/084471, inter al/a. Preferred metal catalysts include
cobalt/molybdenum (1-10% Co as oxide, 10-40% Mo as oxide), nickel/molybdenum
(1-10% Ni as
oxide, 10-40% Co as oxide), or nickel/tungsten (1-10% Ni as oxide, 10-40% W as
oxide) on
alumina.
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[0062] In various aspects, hydrotreating conditions can include
temperatures of 200 C to
450 C, or 315 C to 425 C; pressures of 250 psig (-1.8 MPag) to 5000 psig (-
34.6 MPag) or 500
psig (-3.4 MPag) to 3000 psig (-20.8 MPag), or 800 psig (-5.5 MPag) to 2500
psig (-17.2 MPag);
Liquid Hourly Space Velocities (LHSV) of 0.2-10 hr'; and hydrogen treat rates
of 200 scf/B (35.6
m3/m3) to 10,000 scf/B (1781 m3/m3), or 500 (89 m3/m3) to 10,000 scf/B (1781
m3/m3).
[0063] Hydrotreating catalysts are typically those containing Group 6
metals, and non-noble
Group 8 ¨ 10 metals, i.e., iron, cobalt and nickel and mixtures thereof. These
metals or mixtures
of metals are typically present as oxides or sulfides on refractory metal
oxide supports. Suitable
metal oxide supports include low acidic oxides such as silica, alumina or
titania, preferably
alumina. In some aspects, preferred aluminas can correspond to porous aluminas
such as gamma
or eta having average pore sizes from 50 to 200 A, or 75 to 150 A; a surface
area from 100 to 300
m2/g, or 150 to 250 m2/g; and/or a pore volume of from 0.25 to 1.0 cm3/g, or
0.35 to 0.8 cm3/g.
The supports are preferably not promoted with a halogen such as fluorine as
this generally increases
the acidity of the support.
[0064] The external surface area and the micropore surface area refer to
one way of
characterizing the total surface area of a catalyst. These surface areas are
calculated based on
analysis of nitrogen porosimetry data using the BET method for surface area
measurement. See,
for example, Johnson, M. F. L., Jour. Catal., 52, 425 (1978). The micropore
surface area refers to
surface area due to the unidimensional pores of the zeolite in the catalyst.
Only the zeolite in a
catalyst will contribute to this portion of the surface area. The external
surface area can be due to
either zeolite or binder within a catalyst.
[0065] Alternatively, the hydrotreating catalyst can be a bulk metal
catalyst, or a combination
of stacked beds of supported and bulk metal catalyst. By bulk metal, it is
meant that the catalysts
are unsupported wherein the bulk catalyst particles comprise 30-100 wt. % of
at least one Group 8
- 10 non-noble metal and at least one Group 6 metal, based on the total weight
of the bulk catalyst
particles, calculated as metal oxides and wherein the bulk catalyst particles
have a surface area of
at least 10 m2/g. It is furthermore preferred that the bulk metal
hydrotreating catalysts used herein
comprise 50 to 100 wt %, and even more preferably 70 to 100 wt %, of at least
one Group 8¨ 10
non-noble metal and at least one Group 6 metal, based on the total weight of
the particles,
calculated as metal oxides. The amount of Group 6 and Group 8 ¨ 10 non-noble
metals can be
determined via TEM-EDX.
[0066] Bulk catalyst compositions comprising one Group 8 ¨ 10 non-noble
metal and two
Group 6 metals are preferred. It has been found that in this case, the bulk
catalyst particles are
sintering-resistant. Thus the active surface area of the bulk catalyst
particles is maintained during
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use. The molar ratio of Group 6 to Group 8 ¨ 10 non-noble metals ranges
generally from 10:1-
1:10 and preferably from 3:1-1:3, In the case of a core-shell structured
particle, these ratios of
course apply to the metals contained in the shell. If more than one Group 6
metal is contained in
the bulk catalyst particles, the ratio of the different Group 6 metals is
generally not critical. The
same holds when more than one Group 8 ¨ 10 non-noble metal is applied. In the
case where
molybdenum and tungsten are present as Group 6 metals, the molybenum:tungsten
ratio preferably
lies in the range of 9:1-1:9. Preferably the Group 8¨ 10 non-noble metal
comprises nickel and/or
cobalt. It is further preferred that the Group 6 metal comprises a combination
of molybdenum and
tungsten. Preferably, combinations of
nickel/molybdenum/tungsten and
1() cobalt/molybdenum/tungsten and nickel/cobalt/molybdenum/tungsten are
used. These types of
precipitates appear to be sinter-resistant. Thus, the active surface area of
the precipitate is
maintained during use. The metals are preferably present as oxidic compounds
of the
corresponding metals, or if the catalyst composition has been sulfided,
sulfidic compounds of the
corresponding metals.
[0067] In some optional aspects, the bulk metal hydrotreating catalysts
used herein have a
surface area of at least 50 m2/g and more preferably of at least 100 m2/g. In
such aspects, it is also
desired that the pore size distribution of the bulk metal hydrotreating
catalysts be approximately
the same as the one of conventional hydrotreating catalysts. Bulk metal
hydrotreating catalysts can
have a pore volume of 0.05-5 ml/g, or of 0.1-4 ml/g, or of 0.1-3 ml/g, or of
0.1-2 tag determined
by nitrogen adsorption. Preferably, pores smaller than 1 nm are not present.
The bulk metal
hydrotreating catalysts can have a median diameter of at least 50 nm, or at
least 100 nm. The bulk
metal hydrotreating catalysts can have a median diameter of not more than 5000
[tm, or not more
than 3000 [tm. In an embodiment, the median particle diameter lies in the
range of 0.1-50 [tm and
most preferably in the range of 0.5-50 [tm.
[0068] Examples of suitable hydrotreating catalysts include, but are not
limited to, Albemarle
KF 848, KF 860, KF 868, KF 870, KF 880, KF 861, KF 905, KF 907, and Nebula;
Criterion LH-
21, LH-22, and DN-3552; Haldor-Topsoe TK-560 BRIM, TK-562 HyBRIM, TK-565
HyBRIM,
TK-569 HyBRIM, TK-907, TK-911, and TK-951; Axens HR 504, HR 508, HR 526, and
HR 544.
Hydrotreating may be carried out by one catalyst or combinations of the
previously listed catalysts.
Second-Stage Processing ¨ Hydrocracking or Conversion Conditions
[0069]
In various aspects, instead of using a conventional hydrocracking catalyst
in a second
(sweet) reaction stage for conversion of a feed, a reaction system can include
a high surface area,
low acidity conversion catalyst as described herein. In aspects where a
lubricant boiling range feed
has a sufficiently low content of heteroatoms, such as a feed that corresponds
to a "sweet" feed,
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the feed can be exposed to a high surface area, low acidity conversion
catalyst as described herein
without prior hydroprocessing to remove heteroatoms.
[0070] In various aspects, the conditions selected for conversion for
lubricant base stock
production can depend on the desired level of conversion, the level of
contaminants in the input
feed to the conversion stage, and potentially other factors. For example,
hydrocracking and/or
conversion conditions in a single stage, or in the first stage and/or the
second stage of a multi-stage
system, can be selected to achieve a desired level of conversion in the
reaction system.
Hydrocracking and/or conversion conditions can be referred to as sour
conditions or sweet
conditions, depending on the level of sulfur and/or nitrogen present within a
feed and/or present in
.. the gas phase of the reaction environment. For example, a feed with 100
wppm or less of sulfur
and 50 wppm or less of nitrogen, preferably less than 25 wppm sulfur and/or
less than 10 wppm of
nitrogen, represent a feed for hydrocracking and/or conversion under sweet
conditions. Feeds with
sulfur contents of 250 wppm or more can be processed under sour conditions.
Feeds with
intermediate levels of sulfur can be processed either under sweet conditions
or sour conditions.
[0071] In aspects that include hydrocracking as part of an initial
hydroprocessing stage under
sour conditions, the initial stage hydrocracking catalyst can comprise any
suitable or standard
hydrocracking catalyst, for example, a zeolitic base selected from zeolite
Beta, zeolite X, zeolite
Y, faujasite, ultrastable Y (USY), dealuminized Y (Deal Y), Mordenite, ZSM-3,
ZSM-4, ZSM-18,
ZSM-20, ZSM-48, and combinations thereof, which zeolitic base can
advantageously be loaded
20 with one or more active metals (e.g., either (i) a Group 8 ¨ 10 noble metal
such as platinum
and/or palladium or (ii) a Group 8 ¨ 10 non-noble metal such nickel, cobalt,
iron, and combinations
thereof, and a Group 6 metal such as molybdenum and/or tungsten). In this
discussion, zeolitic
materials are defined to include materials having a recognized zeolite
framework structure, such
as framework structures recognized by the International Zeolite Association.
Such zeolitic
materials can correspond to silicoaluminates, silicoaluminophosphates,
aluminophosphates, and/or
other combinations of atoms that can be used to form a zeolitic framework
structure. In addition to
zeolitic materials, other types of crystalline acidic support materials may
also be suitable.
Optionally, a zeolitic material and/or other crystalline acidic material may
be mixed or bound with
other metal oxides such as alumina, titania, and/or silica. Details on
suitable hydrocracking
catalysts can be found in U52015/715,555.
[0072] In some optional aspects, a high surface area, low acidity
conversion catalyst as
described herein can optionally be used as part of the catalyst in an initial
stage.
[0073] A hydrocracking process in a first stage (or otherwise under sour
conditions) can be
carried out at temperatures of 200 C to 450 C, hydrogen partial pressures of
from 250 psig to 5000
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psig (-1.8 MPag to ¨34.6 MPag), liquid hourly space velocities of from 0.2 hr-
'to 10 hr-1, and
hydrogen treat gas rates of from 35.6 m3/m3 to 1781 m3/m3 (-200 SCF/B to
¨10,000 SCF/B),
Typically, in most cases, the conditions can include temperatures in the range
of 300 C to 450 C,
hydrogen partial pressures of from 500 psig to 2000 psig (-3.5 MPag to ¨13.9
MPag), liquid hourly
space velocities of from 0.3 hrito 5 hrland hydrogen treat gas rates of from
213 m3/m3 to 1068
m3/m3 (-1200 SCF/B to ¨6000 SCF/B).
[0074] In a multi-stage reaction system, a first reaction stage of the
hydroprocessing reaction
system can include one or more hydrotreating and/or hydrocracking catalysts. A
separator can then
be used in between the first and second stages of the reaction system to
remove gas phase sulfur
and nitrogen contaminants. One option for the separator is to simply perform a
gas-liquid
separation to remove contaminants. Another option is to use a separator such
as a flash separator
that can perform a separation at a higher temperature. Such a high temperature
separator can be
used, for example, to separate the feed into a portion boiling below a
temperature cut point, such
as about 350 F (177 C) or about 400 F (204 C), and a portion boiling above the
temperature cut
point. In this type of separation, the naphtha boiling range portion of the
effluent from the first
reaction stage can also be removed, thus reducing the volume of effluent that
is processed in the
second or other subsequent stages. Of course, any low boiling contaminants in
the effluent from
the first stage would also be separated into the portion boiling below the
temperature cut point. If
sufficient contaminant removal is performed in the first stage, the second
stage can be operated as
a "sweet" or low contaminant stage.
[0075] Still another option can be to use a separator between the first
and second stages of the
hydroprocessing reaction system that can also perform at least a partial
fractionation of the effluent
from the first stage. In this type of aspect, the effluent from the first
hydroprocessing stage can be
separated into at least a portion boiling below the distillate (such as
diesel) fuel range, a portion
boiling in the distillate fuel range, and a portion boiling above the
distillate fuel range. The distillate
fuel range can be defined based on a conventional diesel boiling range, such
as having a lower end
cut point temperature of at least about 350 F (177 C) or at least about 400 F
(204 C) to having an
upper end cut point temperature of about 700 F (371 C) or less or 650 F (343
C) or less.
Optionally, the distillate fuel range can be extended to include additional
kerosene, such as by
selecting a lower end cut point temperature of at least about 300 F (149 C).
[0076] In aspects where the inter-stage separator is also used to
produce a distillate fuel
fraction, the portion boiling below the distillate fuel fraction includes,
naphtha boiling range
molecules, light ends, and contaminants such as H25. These different products
can be separated
from each other in any convenient manner. Similarly, one or more distillate
fuel fractions can be
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formed, if desired, from the distillate boiling range fraction. The portion
boiling above the distillate
fuel range represents the potential lubricant base stocks. In such aspects,
the portion boiling above
the distillate fuel boiling range is subjected to further hydroprocessing in a
second hydroprocessing
stage. The portion boiling above the distillate fuel boiling range can
correspond to a lubricant
boiling range fraction, such as a fraction having a T5 or T10 boiling point of
at least about 343 C.
Optionally, the lighter lube fractions can be distilled and operated in the
catalyst dewaxing sections
in a blocked operation where the conditions are adjusted to maximize the yield
and properties of
each lube cut.
[0077] A conversion process under sweet conditions can be performed
under conditions similar
to those used for a sour hydrocracking process, or the conditions can be
different. In an
embodiment, the conditions in a sweet conversion stage can have less severe
conditions than a
hydrocracking process in a sour stage. Suitable conversion conditions for a
non-sour stage can
include, but are not limited to, conditions similar to a first or sour stage.
Suitable conversion
conditions can include temperatures of about 550 F (288 C) to about 840 F (449
C), hydrogen
partial pressures of from about 1000 psia to about 5000 psia (-6.9 MPa-a to
34.6 MPa-a), liquid
hourly space velocities of from 0.05 hrito 10111-1, and hydrogen treat gas
rates of from 35.6 m3/m3
to 1781 m3/m3 (200 SCF/B to 10,000 SCF/B). In other embodiments, the
conditions can include
temperatures in the range of about 600 F (343 C) to about 815 F (435 C),
hydrogen partial
pressures of from about 1000 psia to about 3000 psia (-6.9 MPa-a to 20.9 MPa-
a), and hydrogen
treat gas rates of from about 213 m3/m3 to about 1068 m3/m3 (1200 SCF/B to
6000 SCF/B). The
LHSV can be from about 0.25 hrito about 50 hi-1, or from about 0.5 hrito about
20 hi-1, and
preferably from about 1.0 hr-'to about 4.0 hr-1.
[0078] In still another aspect, the same conditions can be used for
hydrotreating,
hydrocracking, and/or conversion beds or stages, such as using hydrotreating
conditions for all
beds or stages, using hydrocracking conditions for all beds or stages, and/or
using conversion
conditions for all beds or stages. In yet another embodiment, the pressure for
the hydrotreating,
hydrocracking, and/or conversion beds or stages can be the same.
[0079] In yet another aspect, a hydroprocessing reaction system may
include more than one
hydrocracking and/or conversion stage. If multiple hydrocracking and/or
conversion stages are
present, at least one hydrocracking stage can have effective hydrocracking
conditions as described
above, including a hydrogen partial pressure of at least about 1000 psia (-6.9
MPa-a). In such an
aspect, other (subsequent) conversion processes can be performed under
conditions that may
include lower hydrogen partial pressures. Suitable conversion conditions for
an additional
conversion stage can include, but are not limited to, temperatures of about
550 F (288 C) to about
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840 F (449 C), hydrogen partial pressures of from about 250 psia to about 5000
psia (1.8 MPa-a
to 34.6 MPa-a), liquid hourly space velocities of from 0.05 hflto 10 hfl, and
hydrogen treat gas
rates of from 35.6 m3/m3 to 1781 m3/m3 (200 SCF/5 B to 10,000 SCF/B). In other
embodiments,
the conditions for an additional conversion stage can include temperatures in
the range of about
600 F (343 C) to about 815 F (435 C), hydrogen partial pressures of from about
500 psia to about
3000 psia (3.5 MPa-a to 20.9 MPa-a), and hydrogen treat gas rates of from
about 213 m3/m3 to
about 1068 m3/m3 (1200 SCF/B to 6000 SCF/B). The LHSV can be from about 0.25
hflto about
50 hr', or from about 0.5 hr' to about 20 hr', and preferably from about 1.0
hrito about 4.0 hr'.
Additional Second Stage Processing ¨ Dewaxing and Hydrofinishing / Aromatic
Saturation
[0080] In various aspects, catalytic dewaxing can be included as part of a
second and/or sweet
and/or subsequent processing stage, such as a processing stage that also
includes conversion in the
presence of a high surface area, low acidity catalyst. Preferably, the
dewaxing catalysts are zeolites
(and/or zeolitic crystals) that perform dewaxing primarily by isomerizing a
hydrocarbon feedstock.
More preferably, the catalysts are zeolites with a unidimensional pore
structure. Suitable catalysts
include 10-member ring pore zeolites, such as EU-1, ZSM-35 (or ferrierite),
ZSM-11, ZSM-57,
NU-87, SAPO-11, and ZSM-22. Preferred materials are EU-2, EU-11, ZBM-30, ZSM-
48, or Z SM-
23. ZSM-48 is most preferred. Note that a zeolite having the ZSM-23 structure
with a silica to
alumina ratio of from 20:1 to 40:1 can sometimes be referred to as SSZ-32.
Other zeolitic crystals
that are isostructural with the above materials include Theta-1, NU-10, EU-13,
KZ-1, and NU-23.
U.S. Patent Nos. 7,625,478, 7,482,300, 5,075,269 and 4,585,747 further
disclose dewaxing
catalysts useful in the process of the present disclosure, all of which are
incorporated herein by
reference.
[0081] In various embodiments, the dewaxing catalysts can further
include a metal
hydrogenation component. The metal hydrogenation component is typically a
Group 6 and/or a
Group 8 ¨ 10 metal. Preferably, the metal hydrogenation component is a Group 8
¨ 10 noble metal.
Preferably, the metal hydrogenation component is Pt, Pd, or a mixture thereof.
In an alternative
preferred embodiment, the metal hydrogenation component can be a combination
of a non-noble
Group 8 ¨ 10 metal with a Group 6 metal. Suitable combinations can include Ni,
Co, or Fe with
Mo or W, preferably Ni with Mo or W.
[0082] The metal hydrogenation component may be added to the dewaxing
catalyst in any
convenient manner. One technique for adding the metal hydrogenation component
is by incipient
wetness. For example, after combining a zeolite and a binder, the combined
zeolite and binder can
be extruded into catalyst particles. These catalyst particles can then be
exposed to a solution
containing a suitable metal precursor. Alternatively, metal can be added to
the catalyst by ion
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exchange, where a metal precursor is added to a mixture of zeolite (or zeolite
and binder) prior to
extrusion.
[0083] The amount of metal in the dewaxing catalyst can be at least 0.1
wt % based on catalyst,
or at least 0.15 wt %, or at least 0.2 wt %, or at least 0.25 wt %, or at
least 0.3 wt %, or at least 0.5
wt % based on catalyst. The amount of metal in the catalyst can be 20 wt % or
less based on
catalyst, or 10 wt % or less, or 5 wt % or less, or 2.5 wt % or less, or 1 wt
% or less. For aspects
where the metal is Pt, Pd, another Group 8 - 10 noble metal, or a combination
thereof, the amount
of metal can be from 0.1 to 5 wt %, preferably from 0.1 to 2 wt %, or 0.25 to
1.8 wt %, or 0.4 to
1.5 wt %. For aspects where the metal is a combination of a non-noble Group 8
¨ 10 metal with a
1() Group 6 metal, the combined amount of metal can be from 0.5 wt % to 20
wt %, or 1 wt % to 15
wt %, or 2.5 wt % to 10 wt %.
[0084] Preferably, a dewaxing catalyst can be a catalyst with a low
ratio of silica, to alumina.
For example, for ZSM-48, the ratio of silica to alumina in the zeolite can be
less than 200:1, or less
than 110:1, or less than 100:1, or less than 90:1, or less than 80:1. In
particular, the ratio of silica
to alumina can be from 30:1 to 200:1, or 60:1 to 110:1, or 70:1 to 100:1.
[0085] A dewaxing catalyst can also include a binder. In some
embodiments, the dewaxing
catalysts used in process according to the invention are formulated using a
low surface area binder,
a low surface area binder represents a binder with a surface area of 100 m2/g
or less, or 80 m2/g
or less, or 70 m2/g or less, such as down to 40 m2/g or still lower.
[0086] Alternatively, the binder and the zeolite particle size can be
selected to provide a
catalyst with a desired ratio of micropore surface area to total surface area.
In dewaxing catalysts
used according to the invention, the micropore surface area corresponds to
surface area from the
unidimensional pores of zeolites in the dewaxing catalyst. The total surface
corresponds to the
micropore surface area plus the external surface area. Any binder used in the
catalyst will not
contribute to the micropore surface area and will not significantly increase
the total surface area of
the catalyst. The external surface area represents the balance of the surface
area of the total catalyst
minus the micropore surface area. Both the binder and zeolite can contribute
to the value of the
external surface area. Preferably, the ratio of micropore surface area to
total surface area for a
dewaxing catalyst will be equal to or greater than 25%.
[0087] A zeolite (or other zeolitic material) can be combined with binder
in any convenient
manner. For example, a bound catalyst can be produced by starting with powders
of both the zeolite
and binder, combining and mulling the powders with added water to form a
mixture, and then
extruding the mixture to produce a bound catalyst of a desired size. Extrusion
aids can also be used
to modify the extrusion flow properties of the zeolite and binder mixture.
Optionally, a binder can
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be composed of two or more metal oxides can also be used.
[0088] Process conditions in a catalytic dewaxing zone can include a
temperature of from 200
to 450 C, preferably 270 to 400 C, a hydrogen partial pressure of from 1.8 to
34.6 MPag (-250 to
¨5000 psi), preferably 4.8 to 20.8 MPag, a liquid hourly 5 space velocity of
from 0.2 to 10 hr-1,
preferably 0.5 to 3.0 hr-1, and a hydrogen circulation rate of from 35.6 to
1781 m3/m3 (-200 to
¨10,000 SCF/B), preferably 178 to 890.6 m3/m3 (-1000 to ¨5000 scf/B).
Additionally or
alternately, the conditions can include temperatures in the range of 600 F (-
343 C) to 815 F
(-435 C), hydrogen partial pressures of from 500 psig to 3000 psig (-3.5 MPag
to ¨20.9 MPag),
and hydrogen treat gas rates of from 213 m3/m3 to 1068 m3/m3 (-1200 SCF/B to
¨6000 SCF/B).
[0089] In various aspects, a hydrofinishing and/or aromatic saturation
process can also be
provided. The hydrofinishing and/or aromatic saturation can occur prior to
dewaxing and/or after
dewaxing. The hydrofinishing and/or aromatic saturation can occur either
before or after
fractionation. If hydrofinishing and/or aromatic saturation occurs after
fractionation, the
hydrofinishing can be performed on one or more portions of the fractionated
product, such as being
performed on one or more lubricant base stock portions. Alternatively, the
entire effluent from the
last conversion or dewaxing process can be hydrofinished and/or undergo
aromatic saturation.
[0090] In some situations, a hydrofinishing process and an aromatic
saturation process can
refer to a single process performed using the same catalyst. Alternatively,
one type of catalyst or
catalyst system can be provided to perform aromatic saturation, while a second
catalyst or catalyst
system can be used for hydrofinishing. Typically a hydrofinishing and/or
aromatic saturation
process will be performed in a separate reactor from dewaxing or hydrocracking
processes for
practical reasons, such as facilitating use of a lower temperature for the
hydrofinishing or aromatic
saturation process. However, an additional hydrofinishing reactor following a
hydrocracking or
dewaxing process but prior to fractionation could still be considered part of
a second stage of a
reaction system conceptually.
[0091] Hydrofinishing and/or aromatic saturation catalysts can include
catalysts containing
Group 6 metals, Group 8 ¨ 10 metals, and mixtures thereof. In an embodiment,
preferred metals
include at least one metal sulfide having a strong hydrogenation function. In
another embodiment,
the hydrofinishing catalyst can include a Group 8 ¨ 10 noble metal, such as
Pt, Pd, or a combination
thereof. The mixture of metals may also be present as bulk metal catalysts
wherein the amount of
metal is 30 wt. % or greater based on catalyst. Suitable metal oxide supports
include low acidic
oxides such as silica, alumina, silica-aluminas or titania, preferably
alumina. The preferred
hydrofinishing catalysts for aromatic saturation will comprise at least one
metal having relatively
strong hydrogenation function on a porous support. Typical support materials
include amorphous
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or crystalline oxide materials such as alumina, silica, and silica-alumina.
The support materials
may also be modified, such as by halogenation, or in particular fluorination.
The metal content of
the catalyst is often as high as 20 weight percent for non-noble metals. In an
embodiment, a
preferred hydrofinishing catalyst can include a crystalline material belonging
to the M41S class or
family of catalysts. The M41S family of catalysts are mesoporous materials
having high silica
content. Examples include MCM-41, MCM-48 and MCM-50. A preferred member of
this class is
MCM-41. If separate catalysts are used for aromatic saturation and
hydrofinishing, an aromatic
saturation catalyst can be selected based on activity and/or selectivity for
aromatic saturation, while
a hydrofinishing catalyst can be selected based on activity for improving
product specifications,
1() such as product color and polynuclear aromatic reduction. U.S. Patent
Nos. 7,686,949, 7,682,502
and 8,425,762 further disclose catalysts useful in the process of the present
disclosure, all of which
are incorporated herein by reference. U.S. Patent Nos. 7,686,949, 7,682,502
and 8,425,762 further
disclose catalysts useful in the process of the present disclosure, all of
which are incorporated
herein by reference.
[0092] Hydrofinishing conditions can include temperatures from 125 C to 425
C, preferably
180 C to 280 C, total pressures from 500 psig (-3.4 MPag) to 3000 psig (-20.7
MPag), preferably
1500 psig (-10.3 MPag) to 2500 psig (-17.2 MPag), and liquid hourly space
velocity (LHSV) from
0.1 hr-1 to 5 hr-1, preferably 0.5 hr-1 to 1.5 hr-1.
[0093] A second fractionation or separation can be performed at one or
more locations after a
second or subsequent stage. In some aspects, a fractionation can be performed
after hydrocracking
in the second stage in the presence of the USY catalyst under sweet
conditions. At least a lubricant
boiling range portion of the second stage hydrocracking effluent can then be
sent to a dewaxing
and/or hydrofinishing reactor for further processing. In some aspects,
hydrocracking and dewaxing
can be performed prior to a second fractionation. In some aspects,
hydrocracking, dewaxing, and
aromatic saturation can be performed prior to a second fractionation.
Optionally, aromatic
saturation and/or hydrofinishing can be performed before a second
fractionation, after a second
fractionation, or both before and after.
[0094] If a lubricant base stock product is desired, the lubricant base
stock product can be
further fractionated to form a plurality of products. For example, lubricant
base stock products can
be made corresponding to a 2 cSt cut, a 4 cSt cut, a 6 cSt cut, and/or a cut
having a viscosity higher
than 6 cSt. For example, a lubricant base oil product fraction having a
viscosity of at least 2 cSt
can be a fraction suitable for use in low pour point application such as
transformer oils, low
temperature hydraulic oils, or automatic transmission fluid. A lubricant base
oil product fraction
having a viscosity of at least 4 cSt can be a fraction having a controlled
volatility and low pour
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point, such that the fraction is suitable for engine oils made according to
SAE J300 in OW- or 5W-
or 10W-grades. This fractionation can be performed at the time the diesel (or
other fuel) product
from the second stage is separated from the lubricant base stock product, or
the fractionation can
occur at a later time. Any hydrofinishing and/or aromatic saturation can occur
either before or after
fractionation. After fractionation, a lubricant base oil product fraction can
be combined with
appropriate additives for use as an engine oil or in another lubrication
service. Illustrative process
flow schemes useful in this disclosure are disclosed in U.S. Patent No.
8,992,764, 8,394,255, U.S.
Patent Application Publication No. 2013/0264246, and U.S. Patent Application
Publication No.
2015/715,555 the disclosures of which are incorporated herein by reference in
their entirety.
ix) Lubricating Oil Additives
[0095] A base oil constitutes the major component of the engine or other
mechanical
component oil lubricant composition of the present disclosure and typically is
present in an amount
from about 50 to about 99 weight percent, preferably from about 70 to about 95
weight percent,
and more preferably from about 85 to about 95 weight percent, based on the
total weight of the
composition. As described herein, additives constitute the minor component of
the engine or other
mechanical component oil lubricant composition of the present disclosure and
typically are present
in an amount ranging from about less than 50 weight percent, preferably less
than about 30 weight
percent, and more preferably less than about 15 weight percent, based on the
total weight of the
composition.
[0096] Mixtures of base oils may be used if desired, for example, a base
stock component and
a co-base stock component. The co-base stock component is present in the
lubricating oils of this
disclosure in an amount from about 1 to about 99 weight percent, preferably
from about 5 to about
95 weight percent, and more preferably from about 10 to about 90 weight
percent, based on the
total weight of the composition. In a preferred aspect of the present
disclosure, the low-viscosity
and the high-viscosity base stocks are used in the form of a base stock blend
that comprises from
5 to 95 wt. % of the low-viscosity base stock and from 5 to 95 wt. % of the
high-viscosity base
stock. Preferred ranges include from 10 to 90 wt. % of the low-viscosity base
stock and from 10 to
90 wt. % of the high-viscosity base stock. The base stock blend can be present
in the engine or
other mechanical component oil lubricant composition from 15 to 85 wt. % of
the low-viscosity
base stock and from 15 to 85 wt. % of the high-viscosity base stock,
preferably from 20 to 80 wt.
% of the low-viscosity base stock and from 20 to 80 wt. % of the high-
viscosity base stock, and
more preferably from 25 to 75 wt. % of the low-viscosity base stock and from
25 to 75 wt. % of
the high-viscosity base stock, based on the total weight of the oil lubricant
composition.
[0097] In one aspect of the present disclosure, a low-viscosity, medium
viscosity and/or high
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viscosity base stock is present in the engine or other mechanical component
oil lubricant
composition in an amount of from about 50 to about 99 weight percent,
preferably from about 70
to about 95 weight percent, and more preferably from about 85 to about 95
weight percent, based
on the total weight of the composition.
[0098] The formulated lubricating oil useful in the present disclosure may
contain one or more
of the other commonly used lubricating oil performance additives including but
not limited to
antiwear additives, detergents, dispersants, viscosity modifiers, corrosion
inhibitors, rust
inhibitors, metal deactivators, extreme pressure additives, anti-seizure
agents, wax modifiers, other
viscosity modifiers, fluid-loss additives, seal compatibility agents,
lubricity agents, anti-staining
agents, chromophoric agents, defoamants, demulsifiers, emulsifiers,
densifiers, wetting agents,
gelling agents, tackiness agents, colorants, and others. For a review of many
commonly used
additives, see "Lubricant Additives, Chemistry and Applications", Ed. L. R.
Rudnick, Marcel
Dekker, Inc. 270 Madison Ave. New York, N.J. 10016, 2003, and Klamann in
Lubricants and
Related Products, Verlag Chemie, Deerfield Beach, FL; ISBN 0-89573-177-0.
Reference is also
made to "Lubricant Additives" by M. W. Ranney, published by Noyes Data
Corporation of
Parkridge, NJ (1973); see also U.S. Patent No. 7,704,930, the disclosure of
which is incorporated
herein in its entirety. These additives are commonly delivered with varying
amounts of diluent oil
that may range from 5 weight percent up to greater than 90 weight percent.
[0099] The additives useful in this disclosure do not have to be soluble
in the lubricating oils.
Insoluble additives such as zinc stearate in oil can be dispersed in the
lubricating oils of this
disclosure.
[00100] When lubricating oil compositions contain one or more additives, the
additive(s) are
blended into the composition in an amount sufficient for it to perform its
intended function. As
stated above, additives are typically present in lubricating oil compositions
as a minor component,
typically in an amount of less than 50 weight percent, preferably less than
about 30 weight percent,
and more preferably less than about 15 weight percent, based on the total
weight of the
composition. Additives are most often added to lubricating oil compositions in
an amount of at
least 0.1 weight percent, preferably at least 1 weight percent, more
preferably at least 5 weight
percent. Typical amounts of such additives useful in the present disclosure
are shown in Table 1
below.
[00101] It is noted that many of the additives are shipped from the additive
manufacturer as a
concentrate, containing one or more additives together, with a certain amount
of base oil diluents.
Accordingly, the weight amounts in the Table 1 below, as well as other amounts
mentioned herein,
are directed to the amount of active ingredient (that is the non-diluent
portion of the ingredient).
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The weight percent (wt. %) indicated below is based on the total weight of the
lubricating oil
composition.
Table 2
Typical Amounts of Other Lubricating Oil Components
Approximate Approximate
Compound wt. % (Useful) wt. % (Preferred)
Dispersant 0.1-20 0.1-8
Detergent 0.1-20 0.1-8
Friction Modifier 0.01-5 0.01-1.5
Antioxidant 0.1-5 0.1-1.5
Pour Point Depressant (PPD) 0.0-5 0.01-1.5
Anti-foam Agent 0.001-3 0.001-0.15
Viscosity Modifier (solid 0.1-2 0.1-1
polymer basis)
Antiwear 0.2-3 0.5-1
Inhibitor and Antirust 0.01-5 0.01-1.5
[00102] The foregoing additives are all commercially available materials.
These additives may
be added independently but are usually precombined in packages which can be
obtained from
suppliers of lubricant oil additives. Additive packages with a variety of
ingredients, proportions
and characteristics are available and selection of the appropriate package
will take the requisite use
of the ultimate composition into account.
[00103] Lubricant compositions including the base stocks of the instant
disclosure have
improved oxidative stability relative to conventional lubricant compositions
including Group III
base stocks. The low temperature and oxidation performance of lubricating oil
base stocks in
formulated lubricants are determined from MRV (mini-rotary viscometer) for low
temperature
performance measured by ASTM D4684, or for oxidation performance measured by
oxidation
stability time measured by pressure differential scanning calorimetry (CEC-L-
85, which is the
equivalent of ASTM D6186). The lubricating oils of this disclosure are
particularly advantageous
as passenger vehicle engine oil (PVEO) products.
[00104] The lubricating oil base stocks of this disclosure provide
several advantages over
typical conventional lubricating oil base stocks including, but not limited
to, improved oxidation
performance such as oxidation induction time measured by pressure differential
scanning
calorimetry (CEC-L-85, which is the equivalent of ASTM D6186) in engine oils.
[00105] The lubricant compositions can be employed in the present disclosure
in a variety of
lubricant-related end uses, such as a lubricant oil or grease for a device or
apparatus requiring
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lubrication of moving and/or interacting mechanical parts, components, or
surfaces. Useful
apparatuses include engines and machines. The lube base stocks of the present
disclosure are
suitable for use in the formulation of automotive crank case lubricants,
automotive gear oils,
transmission oils, many industrial lubricants including circulation lubricant,
industrial gear
lubricants, grease, compressor oil, pump oils, refrigeration lubricants,
hydraulic lubricants and
metal working fluids. Furthermore, the lube base stocks of this disclosure may
be derived from
renewable sources; such base stocks may qualify as sustainable product and can
meet
"sustainability" standards set by industry groups or government regulations.
[00106] The following non-limiting examples are provided to illustrate
the disclosure.
1() EXAMPLES
[00107] For Examples 1 and 2, Feeds A and B were processed according to the
process
described in the present disclosure and depicted in Figure 1. In particular,
the feeds having the
properties described in Table 3 were processed to produce the Group III base
stocks of the present
disclosure. After Stage 1 hydroprocessing, the intermediate feeds having the
properties described
in Table 4 were subjected to Stage 2 hydroprocessing to produce the Group III
base stocks of the
present disclosure. Feed A represented a raffinate feed with ¨67 VI, and Feed
B represented a high-
quality VG0 feed with ¨92 VI.
[00108] Five different catalysts were used for processing in Examples 1 and 2,
with details
provided below. For both examples, stage 1 hydrotreating used catalysts A and
B and stage 2
hydroprocessing used catalysts C, D, and E.
[00109] Catalyst A: Commercially available hydrotreating catalyst that
consists of NiMo
supported on A1203.
[00110] Catalyst B: Commercially available hydrotreating catalyst that
consists of a bulk
NiMoW oxide.
[00111] Catalyst C: 0.6 wt% Pt on USY, bounded with Versal-300 alumina. The
USY had a
ratio of silica to alumina (5i02 : A1203) of roughly 75 : 1. USY is a zeolite
with 12-member ring
pore channels.
[00112] Catalyst D: Commercially available dewaxing catalyst that consists of
Pt supported on
ZSM-48.
[00113] Catalyst E: Commercially available hydrofinishing catalyst that
consists of Pt/Pd
supported on MCM-4 1.
Example 1:
[00114] Feed A properties are shown in Table 3. The feed was hydrotreated at
two conversion
levels, namely 17% and 33%, and then blended (44.6/55.4) to give the product
with properties
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shown in Table 3. For the dry wax amount, the amount of dry wax was corrected
to the expected
value at a pour point of -18 C based on a correction of -0.33 wt% / C of pour
point. For the
viscosity index, the viscosity index was corrected to the expected value at a
pour point of -18 C
based on a correction of 0.33 VI / C of pour point.
Table 3
Feed A Feed B
Solvent Dewaxed Oil VI
67 92
@ -18 C Pour
KV100 (cSt) 5.302 5.063
GC Distillation
Initial Boiling Pt ( C) 209 196
10% Off ( C) 328 343
50% Off ( C) 417 417
90% Off ( C) 495 509
Final Boiling Pt ( C) 570 560
N (ppm) 666 297
S (mass%) 1.28 0.47
% Dry Wax 16.8 23.0
Total Aromatics (mmol/kg) 922 562
3+ Ring Aromatics
312 185
(mmol/kg)
Table 4
Feed to Stage Feed to Stage Feed to Stage
2(A) 2(A) 2(B)
Low Stage 1 High Stage 1
Conversion Conversion
Waxy VI 118 129 144
Solvent Dewaxed Oil VI @
98 111 124
-18 C Pour
KV100 (cSt) 5.1182 4.3955 4.4009
GC Distillation
Initial Boiling Pt ( C) 335 335 331
10% Off ( C) 367 364 369
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50% Off ( C) 420 415 418
90% Off ( C) 496 492 500
Final Boiling Pt ( C) 579 568 547
N (ppm) 1 <1 <1
S (ppm) 7 <5 <5
% Dry Wax 18.7 21.6 33.9
[00115] Feed A, having a solvent dewaxed oil feed viscosity index of about 67
was processed
through the first stage which is primarily a hydrotreating unit which boosts
viscosity index (VI)
and removes sulfur and nitrogen. Both catalysts A and B were loaded in the
same reactor, with the
feed contacting catalyst A first. The hydrotreated feed was followed by a
stripping section where
light ends and diesel were removed. During Stage 1 hydrotreating, Feed A was
split and underwent
conversion at two different levels (labeled "low" and "high" conversion). The
properties of the
intermediate feeds (Al and A2) are shown in Table 4. The heavier lube
fractions from Al and A2
then entered the second stage where hydrocracking, dewaxing, and
hydrofinishing were performed.
Various processing conditions for each of these steps (described below) were
used to produce five
Group III base stocks, Al -A6, the properties of which are shown in Tables 6
(4-5 cSt), 7 (5-7 cSt),
and 8 (8-11 cSt). This combination of feed and process has been found to
produce a Group III base
stock with unique compositional characteristics. These unique compositional
characteristics were
observed in both the lower and higher viscosity base stocks produced as shown
in Figures 3 and 4.
[00116] Processing conditions for each of the steps described above ¨
hydrotreating,
hydrocracking, catalytic dewaxing, and hydrofinishing ¨ were tuned based on
the desired
conversion and VI of the final base stock products. The conditions used to
manufacture the Group
III base stocks that are the subject of this disclosure can be found in Table
5. The extent of 700 F+
conversion in the first hydrotreating stage ranged from 20 to 40%, and
processing conditions in the
first stage included a temperature from 635 F to 725 F; hydrogen partial
pressure from 500 psig to
3000 psig; liquid hourly space velocity from 0.5 hr-1 to 1.5 hr-1; and a
hydrogen circulation rate
from 3500 scf/bbl to 6000 scf/bbl.
[00117] The second stage, which consisted of hydrocracking, catalytic
dewaxing, and
hydrofinishing, was carried out in a single reactor with a hydrogen partial
pressure of 300 psig to
5000 psig; a hydrogen circulation rate from 1000 scf/bbl to 6000
scf/bblCatalysts C, D, and E were
loaded into the same reactor in the second stage and the feed contacted them
in the order C, D, E.
Process parameters were tuned to achieve a desired 700 F+ conversion of 15-
70%.
[00118] Processing conditions in the hydrocracking step included a temperature
from 250 F to
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700 F; a liquid hourly space velocity from 0.5 hr-1 to 1.5 hr-1. Processing
conditions in the catalytic
dewaxing step included a temperature from 250 F to 660 F; and liquid hourly
space velocity from
1.0 hr-1 to 3.0 hr-1. Processing conditions in the hydrotreating step included
a temperature from
250 F to 480 F; and liquid hourly space velocity from 0.5 hr-1- to 1.5 111-1.
Example 2:
[00119] The properties of Feed B are also shown in Table 3. Feed B was
processed through the
first stage hydrotreating unit, which boosts viscosity index (VI) and removes
sulfur and nitrogen.
The hydrotreated feed was followed by a stripping section where light ends and
diesel were
removed. Both catalysts A and B were loaded in the same reactor, with the feed
contacting catalyst
A first. During Stage 1 hydrotreating, Feed B was subjected to one conversion
level and displayed
the properties shown in Table 4. The heavier lube fraction from this
intermediate then entered the
second stage where hydrocracking, dewaxing, and hydrofinishing were performed.
Various
processing conditions for each of these steps, shown in Table 4, were used to
produce six Group
III base stocks, B1-B6, which are shown in Tables 6-8. This combination of
feed and process has
been found to produce a base stock with unique compositional characteristics.
[00120] Processing conditions for each of the steps described above ¨
hydrotreating,
hydrocracking, catalytic dewaxing, and hydrofinishing ¨ were tuned based on
the desired
conversion and VI of the final base stock products. The conditions used to
manufacture the Group
III base stocks that are the subject of this disclosure can be found in Table
5. The extent of 700 F+
conversion in the first hydrotreating stage ranged from 20 to 40%, and
processing conditions in the
first stage included a temperature from 635 F to 725 F; hydrogen partial
pressure from 500 psig to
3000 psig; liquid hourly space velocity from 0.5 hr-1- to 1.5 111-1,
preferably from 0.5 hr-1- to 1.0 hr
-
1, most preferably from 0.7 hr-1 to 0.9 hr-; and a hydrogen circulation rate
from 3500 scf/bbl to
6000 scf/bbl.
[00121] The second stage, which consisted of hydrocracking, catalytic
dewaxing, and
hydrofinishing, was carried out in a single reactor with a hydrogen partial
pressure of 300 psig to
5000 psig; a hydrogen circulation rate from 1000 scf/bbl to 6000
scf/bblCatalysts C, D, and E were
loaded into the same reactor in the second stage and the feed contacted them
in the order C, D, E.
Process parameters were tuned to achieve a desired 700 F+ conversion of 15-
70%, preferably 15-
55%.
[00122] Processing conditions in the hydrocracking step included a temperature
from 250 F to
700 F; and a liquid hourly space velocity from 0.5 hr-1 to 1.5 hr-1.
[00123] Processing conditions in the catalytic dewaxing step included a
temperature from
250 F to 660 F; and liquid hourly space velocity from 1.0 hr-1 to 3.0 hr-1.
Processing conditions in
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the hydrotreating step included a temperature from 250 F to 480 F; and liquid
hourly space
velocity from 0.5 hr-1 to 1.5 hfl.
Table 5
Stage 1
Feed Cats A & B Cats A Cats A & Feed
&B B
Description Stage 1 700F+
Stage 2
Feed VI Con. (wt. T ( F)
LHSV Feed VI
%) (hr-1)
LIGHT NEUTRALS
Al 66.6 20.9 684 0.8 97.9
A2 66.6 38.9 717 0.8
110.7
A3 66.6 38.9 717 0.8
110.7
B1 91.6 30.3 725 0.8
123.5
B2 91.6 30.3 725 0.8
123.5
MEDIUM NEUTRALS
A4 66.6 20.9 684 0.8 97.9
AS 66.6 38.9 717 0.8
110.7
B3 91.6 30.3 725 0.8
123.5
B4 91.6 30.3 725 0.8
123.5
HEAVY NEUTRALS
A6 66.6 38.9 717 0.8
110.7
B5 91.6 30.3 725 0.8
123.5
B6 91.6 30.3 725 0.8
123.5
Table 5: Continued
Stage 2
Cat C Cat C Cat D Cat D Cat E Cat E
Description
700F+
Con. T LHSV T ( F) LHSV T ( F) LHSV
(wt. %) ( F) (hr-1) (hr-1) (hr-1)
LIGHT
NEUTRAL
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Al 66.9 645 1.3 620 2.0 480 1.2
A2 58.1 624 1.3 626 2.0 480 1.2
A3 52.1 624 1.3 615 2.0 480 1.2
B1 49.7 610 1.3 609 2.0 480 1.2
B2 17.6 250 1.3 620 2.0 480 1.2
MEDIUM
NEUTRAL
S
A4 66.9 645 1.3 620 2.0 480 1.2
AS 58.1 624 1.3 626 2.0 480 1.2
B3 49.7 610 1.3 609 2.0 480 1.2
B4 17.6 250 1.3 620 2.0 480 1.2
HEAVY
NEUTRAL
A6 58.1 624 1.3 626 2.0 480 1.2
B5 49.7 610 1.3 609 2.0 480 1.2
B6 17.6 250 1.3 620 2.0 480 1.2
Table 5: Continued
Description Yield Yield Yield Yield
LN MN HN Yield (%) Total Lube
Yield (%) Yield (%) Yield (%)
LIGHT
NEUTRAL
Al 7.3 4.3 2.7 14.3
A2 6.5 4.6 2.0 13.1
A3 10.5 2.8 2.6 15.9
B1 14.6 3.0 3.7 21.2
B2 20.6 7.4 7.7 35.7
MEDIUM
NEUTRAL
A4 7.3 4.3 2.7 14.3
AS 6.5 4.6 2.0 13.1
B3 14.6 3.0 3.7 21.2
B4 20.6 7.4 7.7 35.7
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HEAVY
NEUTRAL
A6 6.5 4.6 2.0 13.1
B5 14.6 3.0 3.7 21.2
B6 20.6 7.4 7.7 21.2
Example 3 (Comparative):
[00124] A high quality vacuum gas oil feedstock was processed according to the
conventional
base stock hydroprocessing scheme shown by Figure 1. This conventional
hydroprocessing scheme
used widely commercially available catalysts, and is meant to be
representative of conventionally
hydroprocessed Group III base stocks. Base stocks produced by this method are
noted in the tables
and figures as K1 and K2. Additionally, the properties of several commercially
available base
stocks can be found in the tables and figures below and are labeled as
Commercial Comparative
examples. The Commercial Comparative base stocks are all widely commercially
available and
.. are representative of the range of Group III products offered on the market
today. Taken together,
these commercial base stocks and base stocks K1 and K2 are used to illustrate
the uniqueness of
the inventive base stocks that are the subject of this disclosure.
Measurement Procedures
[00125] The lubricating oil base stock compositions were determined using a
combination of
advanced analytical techniques including gas chromatography mass spectrometry
(GCMS),
supercritical fluid chromatography (SFC), and carbon-13 nuclear magnetic
resonance CC NMR).
[00126] Viscosity index (VI) was determined according to ASTM method D2270. VI
is related
to kinematic viscosities measured at 40 C and 100 C using ASTM Method D445.
Note that these
will be abbreviated as KV100 and KV40. Pour point was measured by ASTM D5950.
[00127] Noack volatility was estimated using the results from gas
chromatograph distillation
(GCD) and previously established correlations between key boiling points and
measured Noack
using ASTM D5800. This correlation has been found to predict the measured
result within the
reproducibility of ASTM D5800. Similarly, the cold cranking simulator (CCS) at
-35 C was
estimated using the Walther equation. Inputs into the equation were the
experimentally measured
.. kinematic viscosities at at 40 C and 100 C (ASTM D445), as well as density
at 15.6 C (ASTM
D4052). On average, these estimated CCS at -35 C results match the measured
results of other
base stocks within reproducibility of ASTM D5293. All results for Noack and
CCS shown in
Tables 6-8 were estimated using the above methods, so they can be compared
against each other.
[00128] The unique compositional character of the lube base stocks of the
present disclosure
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may be determined by the amount and distribution of naphthenes, branched
carbons, straight-chain
carbons and terminal carbons as determined by GCMS, as shown in Figures 5-8.
Preferably, the
GCMS results are corrected by SFC; however, it was found that the 2R+NRRN
ratios are identical
regardless of whether or not the GCMS results were corrected by SFC.
[00129] SFC was conducted on a commercial supercritical fluid chromatograph
system. The
system was equipped with the following components: a high pressure pump for
delivery of the
supercritical carbon dioxide mobile phase; temperature controlled column oven;
auto-sampler with
high pressure liquid injection valve for delivery of sample material into
mobile phase; flame
ionization detector; mobile phase splitter (low dead volume tee); back
pressure regulator to keep
the CO2 in a supercritical phase; and a computer and data system for control
of components and
recording of data signal.
[00130] For analysis, ¨ 75 mg of sample was diluted in 2 mL of toluene and
loaded into standard
septum cap autosampler vials. The sample was introduced via a high pressure
sampling valve. SFC
separation was performed using multiple commercial silica packed columns (5
p.m with either 60
or 30 A pores) connected in series (250 mm in length and either 2 mm or 4 mm
inner diameter).
Column temperature was typically held at 35 or 40 C. For analysis, the column
head pressure was
typically 250 bar. Liquid CO2 flow rates were typically 0.3 mL/minute for 2 mm
inner diameter
(i.d.) columns or 2.0 mL/minute for 4 mm i.d. columns. The samples run were
mostly all saturate
compounds that eluted before the solvent (here, toluene). The SFC FID signal
was integrated into
paraffin and naphthenic regions. A chromatograph was used to analyze lube base
stocks for splits
of total paraffins and total naphthenes. The paraffin/naphthene ratio was
calibrated using a variety
of standard materials.
[00131] SFC was conducted on a commercial supercritical fluid chromatograph
system. The
system was equipped with the following components: a high pressure pump for
delivery of the
supercritical carbon dioxide mobile phase; temperature controlled column oven;
auto-sampler with
high pressure liquid injection valve for delivery of sample material into
mobile phase; flame
ionization detector; mobile phase splitter (low dead volume tee); back
pressure regulator to keep
the CO2 in a supercritical phase; and a computer and data system for control
of components and
recording of data signal. For analysis, ¨ 75 mg of sample was diluted in 2 mL
of toluene and loaded
into standard septum cap autosampler vials. The sample was introduced via a
high pressure
sampling valve. SFC separation was performed using multiple commercial silica
packed columns
(5 p.m with either 60 or 30 A pores) connected in series (250 mm in length and
either 2 mm or 4
mm inner diameter). Column temperature was typically held at 35 or 40 C. For
analysis, the
column head pressure was typically 250 bar. Liquid CO2 flow rates were
typically 0.3 mL/minute
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for 2 mm inner diameter (i.d.) columns or 2.0 mL/minute for 4 mm i.d. columns.
The samples run
were mostly all saturate compounds that eluted before the solvent (here,
toluene). The SFC FID
signal was integrated into paraffin and naphthenic regions. A chromatograph
was used to analyze
lube base stocks for splits of total paraffins and total naphthenes. The
paraffin/naphthene ratio was
.. calibrated using a variety of standard materials.
[00132] For GCMS used herein, approximately 50 milligram of a base stock
sample was added
to a standard 2 milliliter auto-sampler vial and diluted with methylene
chloride solvent to fill the
vial. Vials were sealed with septum caps. Samples were run using an Agilent
5975C GCMS (Gas
Chromatography Mass Spectrometer) equipped with an auto-sampler. A non-polar
GC column was
used to simulate distillation or carbon number elution characteristics off the
GC. The GC column
used was a Restek Rxi -1ms. The column dimensions were 30 meters in length x
0.32 mm internal
diameter with a 0.25 micron film thickness for the stationary phase coating.
The GC column was
connected to the split / split-less injection port (held at 360 C and operated
in split-less mode) of
the GC. Helium in constant pressure mode (¨ 7 PSI) was used for GC carrier
phase. The outlet of
.. the GC column was run into mass spectrometer via a transfer line held at a
350 C. The temperature
program for the GC column is a follows: 2 minute hold at 100 C, program at 5 C
per minute, 30
minute hold at 350 C. The mass spectrometer was operated using an electron
impact ionization
source (held at 250 C) and operated using standard conditions (70 eV
ionization). Instrumental
control and mass spectral data acquisition were obtained using the Agilent
Chemstation software.
Mass calibration and instrument tuning performance validated using vendor
supplied standard
based on instrument auto tune feature.
[00133] GCMS retention times for samples were determined relative to a normal
paraffin
retention based on analysis of standard sample containing known normal
paraffins. Then the mass
spectrum was averaged.
[00134] Samples were prepared for 13C NMR by dissolving 25-30 wt% sample in
CDC13 with
7% Cr(III)-acetylacetonate added as a relaxation agent. NMR experiments were
performed on a
JEOL ECS NMR spectrometer for which the proton resonance frequency was 400
MHz.
Quantitative 13C NMR experiments were performed at 27 C using an inverse gated
decoupling
experiment with a 45 flip angle, 6.6 seconds between pulses, 64k data points
and 2400 scans. All
spectra were referenced to trimethylsiloxane (TMS) at 0 ppm. Spectra were
processed with 0.2-1
Hz of line broadening and a baseline correction was applied prior to manual
integration. The entire
spectrum was integrated to determine the mole % of the different integrated
areas as follows: 32.19-
31.90 ppm gamma carbons; 30.05-29.65 ppm epsilon carbons; 29.65-29.17 ppm
delta carbons;
22.96-22.76 ppm beta carbons; 22.76-22.50 ppm pendant and terminal methyl
groups; 19.87-18.89
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ppm pendant methyl groups; 14.73-14.53 ppm pendant propyl groups; 14.53-14.35
ppm terminal
propyl groups; 14.35-13.80 ppm alpha carbons; 11.67-11.22 ppm terminal ethyl
groups; and 11.19-
10.57 ppm pendant ethyl groups.
[00135] For the analysis herein, straight-chain carbons are defined as the sum
of the alpha, beta,
gamma, delta, and epsilon peaks. Branched carbons are defined as the sum of
pendant methyl,
pendant ethyl, and pendant propyl groups. Terminal carbons are defined as the
sum of the terminal
methyl, terminal ethyl, and terminal propyl groups.
[00136] Examples of Group III low viscosity lubricating oil base stocks of
this disclosure and
having a KV100 in the range of 4-5 cSt are shown in Table 6. For reference,
the low viscosity
1() lubricating oil base stocks of this disclosure are compared with
typical Group III low viscosity base
stocks having the same viscosity range. The Group III base stocks with unique
compositions
produced by the advanced hydrocracking process exhibit a range of base stock
KV100 from 4 cSt
to 12 cSt. The differences in composition include a difference in the ratio of
multi-ring naphthenes
to single ring naphthenes (2R+NRRN), the ratio of branched chain carbons to
straight chain
carbons (BC/SC) and the ratio of branched chain carbons to terminal carbons
(BC/TC), as shown
in Tables 6-8, as well as Figures 3-8.
Table 6
Properties of Light Neutral Base Stocks
Sample Feedstock KV100,
cSt KV40, cSt VI
Pour Pt., C
LIGHT
NEUTRALS
Commercial
Comparative Ex. Slack Wax 4.073 17.23
140 -19
A
Commercial
Waxy VG0 4.208 18.57 135 -18
Comparative Ex. B
Commercial
VG0 4.263 19.49 127
-16
Comparative Ex. C
Commercial
Comparative Ex. VG0 4.220 19.47 122
-15
Raffinate/VG
Al 4.240 19.79 120 -24
Blend
Raffinate/VG
A2 4.210 19.00 128 -20
Blend
Raffinate/VG
A3 4.173 18.48 132 -8
Blend
B1 VG0 4.144 18.07 132
-18
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B2 VG0 4.290 19.89 124 -
19
K1 Comparative VG0 4.173 19.25 121 -
26
K2 Comparative VG0 4.934 23.68 137 -
17
Commercial
Extracted VG0 4.624 23.45 114 -
19
Comparative Ex. E
Commercial
Extracted VG0 4.624 23.45 114 -
19
Comparative Ex. F
Table 6: Continued
Est. CCS
Sample at -35 C, Est. Noack'
1RN, wt% 2R+N, wt% 2R+N / 1RN
wt%
cP
LIGHT
NEUTRALS
Commercial
Comparative Ex. 1610 13.1 19.87 6.31
0.32
A
Commercial
Comparative Ex. 2020 12.4 23.29 9.61
0.41
B
Commercial
Comparative Ex. 2640 13.7 36.87 19.83
0.54
C
Commercial
Comparative Ex. 2880 16.0 41.04 21.56
0.53
D
Al 3040 14.3 34.29 15.82
0.46
A2 2420 13.0 26.88 10.92
0.41
A3 2140 12.6 24.08 9.62
0.40
B1 2050 14.1 29.46 9.35
0.32
B2 2910 14.5 37.41 16.60
0.44
K1 Comparative 2830 18.1 35.17 18.75
0.53
K2 Comparative 3580 13.5 38.44 15.82
0.41
Commercial
Comparative Ex. 5290 14.1 43.24 25.56
0.59
E
Commercial
Comparative Ex. 5290 14.1 44.82 25.08
0.56
F
Table 6: Continued
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Branched Straight Terminal
MRV at -
Sample BC/SC BC/TC
C C C
40 C,cSt
LIGHT
NEUTRALS
Commercial
Comparative 6.9 28.4 0.24 3.27 2.10
7900
Ex. A
Commercial
Comparative 6.4 30.1 0.21 3.00 2.13
13800
Ex. B
Commercial
Comparative 5.9 29.9 0.20 2.97 2.00
15200
Ex. C
Commercial
Comparative 5.6 29.5 0.19 2.83 1.98
22500
Ex. D
Al 5.8 29.4 0.20 2.92 2.00
12200
A2 5.7 30.3 0.19 2.85 2.00
21400
A3 5.7 33.3 0.17 2.83 2.01
400,000+
B1 5.9 30.8 0.19 2.88 2.03
14900
B2 5.3 26.8 0.20 2.70 1.95
K1 Comparative 6.2 25.6 0.24 3.43 1.81
Commercial
Comparative 5.0 24.9 0.20 2.82 1.79
22500
Ex. E
Commercial
Comparative 5.0 24.9 0.20 2.82 1.79
Ex. F
Table 7
Properties of Medium Neutral Base Stocks
Sample Feedstock KV100, cSt KV40, cSt VI Pour
Pt., C
MEDIUM
NEUTRALS
Commercial
Slack Wax 6.547 34.99 144 -27
Comparative Ex. G
Commercial
VG0 6.427 36.17 131 -12
Comparative Ex. H
Commercial
VG0 6.181 34.27 130 -24
Comparative Ex. I
Raffinate/VG
A4 5.760 31.67 125 -20
Blend
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Raffinate/VG
A5 5.714 32.23 133 -16
Blend
B3 VG0 6.464 34.42 141 -12
B4 VG0 6.379 35.47 132 -15
Commercial
Extracted VG0 6.563 42.42 106 -17
Comparative Ex. J
Table 7: Continued
Est. CCS
Est. Noack, 2R+N, 2R+N / 1RN
Sample at -35 C, 1RN, wt%
wt% wt%
cP
MEDIUM
NEUTRALS
Commercial
Comparative 6910 7.1 36.80 15.90 0.43
Ex. G
Commercial
Comparative 9630 5.5 40.74 24.06 0.59
Ex. H
Commercial
Comparative 8970 5.2 39.39 22.82 0.58
Ex. I
A4 8600 6.4 38.24 22.56 0.59
AS 6650 5.3 29.44 12.36 0.42
B3 7250 2.7 32.52 9.32 0.29
B4 9120 3.6 41.00 17.01 0.41
Commercial
Comparative 24890 8.0 46.73 35.38 0.76
Ex. J
Table 7: Continued
MRV at -
Sample Branched Terminal 30 C, cP
Straight C BC/SC BC/TC
C C
MEDIUM
NEUTRALS
Commercial
15900
Comparative 5.0 28.1 0.18 2.37 2.11
Ex. G
Commercial
12900
Comparative 6.0 26.1 0.23 2.78 2.17
Ex. H
Commercial
20400
Comparative 4.6 22.5 0.20 2.59 1.76
Ex. I
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A4 5.6 29.4 0.19 2.83 1.96
13100
17800
A5 5.7 29.6 0.19 2.80 2.03
B3 5.6 31.5 0.18 2.54 2.22
22200
B4 5.9 27.3 0.22 5.78 2.12
23400
Commercial
11400
Comparative 6.1 27.9 0.22 2.61 2.33
Ex. F
Table 8
Properties of Heavy Neutral Base Stocks
Sample Feedstock KV100, cSt KV40, cSt VI Pour Pt., C
HEAVY
NEUTRALS
Raffinate/VG
A6 10.570 77.23 122 -22
Blend
B5 VG0 8.767 53.35 140 -13
B6 VG0 9.244 59.70 135 -18
Table 8: Continued
Sample Est. CCS Est. Noack, wt% 1RN, wt% 2R+N,
2R+N /
at -35 C, wt% 1RN
cP
HEAVY
NEUTRA
LS
A6 47430 0.9 43.56 20.55
0.57
B5 16260 1.0 56.88 11.52
0.36
B6 22220 0.9 45.73 15.58
0.40
Table 8: Continued
Sample MRV at
Branched Straight BC/SC BC/TC Terminal
30 C, cP
C C C
HEAVY
NEUTRALS
A6 0.154 2.20
B5 0.173 2.29
B6 0.189 2.37
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[00137] Figures 5 and 6 and Tables 6-8, demonstrate the unique area of
compositional space
demarcated by light neutral (LN) base stocks of the present disclosure. Figure
5 depicts the
naphthene ratio (measured by GCMS) versus degree of branching (measured by
NMR), and
demonstrates that the base stocks of the present disclosure occupy a unique
region of the plot. This
region, marked by dashed lines, occurs at values of < 0.52 for naphthene ratio
and < 0.21 for degree
of branching.
[00138] A similar case is made using Figure 6, which depicts the naphthene
ratio (measured by
GCMS) vs. nature of branching (measured by NMR). The phrase "nature of
branching" indicates
the ratio of branched carbons to terminal carbons, where higher ratios
indicate more internal
branching. Lower ratios here indicate more branching near the ends of the
molecules (terminal C).
As was the case in Figure 5, the base stocks of the present disclosure in
Figure 6 occupy a unique
region of the plot denoted by dashed lines.
[00139] As was the case for LN base stocks, Figures 7 and 8, as well as Tables
6-8, demonstrate
the unique area of compositional space demarcated by the MN base stocks.
Figure 7 demonstrates
the naphthene ratio (measured by GCMS) versus degree of branching (measured by
NMR), and
demonstrates that the inventive base stocks occupy a unique region of the
plot. This region, marked
by dashed lines, occurs at values of < 0.59 for naphthene ratio and < 0.216
for degree of branching.
[00140] Figure 8 illustrates the naphthene ratio (measured by GCMS) vs. nature
of branching
(measured by NMR). The phrase "nature of branching" indicates the ratio of
branched carbons to
terminal carbons, where higher ratios indicate more internal branching. Lower
ratios indicate more
branching near the ends of the molecules (terminal carbons). The region marked
with dashed lines
occur at values of <0.59 naphthene ratio and <0.23 for degree of branching.
Unlike Figure 7, the
base stocks of the present disclosure now occupy a region of the plot denoted
by a line (rather than
a box).
.. Example 4
[00141] For testing low temperature of Group III MN base stocks, a 10W-40
heavy-duty engine
oil (HDEO) formulation was used as the "parent" formulation. The formulation
chosen uses an
additive package formulated for ACEA E6, a 9 SSI styrene-isoprene VM, and a
Group III light
neutral co-base stock. The formulation strategy entailed keeping all non-base-
stock components
constant between blends; only the Group III base stock was varied. The
formulation is provided
in Table 9, and low-temperature results are provided in Table 5. Once blended,
the HDEOs were
tested for low-temperature performance using a mini-rotary viscometer (MRV) at
-30 C, according
to ASTM D4684. Table 9 illustrates a formulation used to test Group III MN
base stocks in
HDE0s. Low-temperature performance data (MRV) are shown in Table 5.
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Table 9
Component Treat (wt.%)
Name
Group III MN 40.0
Base Stock
Yubase 4 26.6
ACEA E6 21.4
Additive Package
Styrene-i soprene 12.0
Viscosity
Modifier
Total weight 100
percent
[00142] Regarding the MRV of medium neutral (MN) base stocks vs. the nature of
branching,
i.e. the branched C / terminal C ratio measured by NMR, lubricants prepared
with Group III base
stocks of the present disclosure show nearly orthogonal behavior to the
conventionally
hydroprocessed base stocks. A similar trend is seen in the MRV behavior of
light neutral (MN)
base stocks blended into OW-20 PCMOs.
Example 5
[00143] For testing in a fully formulated passenger car motor oil
(PCMO), a "parent" OW-
20 formulation was chosen that uses a market-general GF-5 additive package, 50
SSI high ethylene
.. olefin copolymer (RE OCP) VM, and a polymethacrylate (PMA) PPD. The
formulation is provided
below in Table 10. The formulation strategy entailed keeping all non-base-
stock components
constant between blends; only the Group III base stock was varied. Once
blended, the PCMOs
were tested for low temperature performance in the MRV at -40 C (ASTM D4684).
Table 10
Component Treat (wt.%)
Name
Group III MN 83.1
Base
Yubase 4 9.8
ACEA E6 6.8
Styrene-isoprene 0.3
Total weight 100
percent
[00144] Figure 9 demonstrates that the MRV behavior of lubrication
compositions prepared
with light neutral (LN) base stocks blended into OW-20 PCMOs is roughly
uncorrelated to pour
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point. One notable exception is the sample with a relatively high pour point (-
8 C), which showed
an MRV result that was essentially solid (>400,000 mPa.$) at the tested
temperature. This point
was omitted from Figure 9 for clarity.
[00145] Figure 10 shows the MRV behavior of lubrication compositions prepared
with light
neutral (LN) base stocks blended into OW-20 PCMOs as a function of the
naphthene ratio. Unlike
the plots of MRV viscosity vs. pour point, the naphthene ratio demonstrates
clear differences for
lubrication compositions prepared with base stocks of the present disclosure
vs. lubrication
compositions prepared with conventionally hydroprocessed base stocks. The
equations for the lines
in Figure 10 are:
Line for inventive compositions: VI = 89582 - 167956*(2R+NRRN)
Cony. HDP line: VI = -8840 + 49814*(2R+NRRN)
[00146] Figure 11 shows that the MRV behavior of lubrication compositions
prepared with
medium neutral (MN) base stocks blended into 10W-40 HDEOs is roughly
uncorrelated to pour
point. This is a similar conclusion to that reached for the LN base stocks.
Similarly, Figure 12
shows the MRV behavior of lubrication compositions prepared with medium
neutral (MN) base
stocks blended into 10W-40 HDEOs as a function of the naphthene ratio. Unlike
the plots of MRV
viscosity vs. pour point, the naphthene ratio demonstrates clear differences
for lubrication
compositions prepared with base stocks of the present disclosure vs.
conventionally
hydroprocessed base stocks. It is worth noting that the same trend ¨
lubrication compositions
prepared with base stocks of the present disclosure show a negative
correlation between MRV
viscosity and naphthene ratios, whereas lubrication compositions prepared with
conventionally
hydroprocessed base stocks show a positive correlation ¨ was observed in both
viscosity grades of
base stocks. This can be seen by the similar appearances of Figures 10 and 12.
The equations for
the lines in Figure 12 are:
Inventive compositions line: VI = 39054 - 44125*(2R+NRRN)
Cony. line: VI = -1480 + 28197*(2R+NRRN)
[00147] PCT and EP Clauses
[00148] 1. A lubricating composition comprising: a Group III base stock,
the Group III base
stock comprising at least 90 wt.% saturated hydrocarbons and having a
kinematic viscosity at
100 C (KV100) of 4.0 cSt to 12.0 cSt, a viscosity index of from 120 to 133,
and a ratio of multi-
ring naphthenes to single ring naphthenes (2R+NRRN) of less than 0.43; and an
effective amount
of one or more lubricant additives.
[00149] 2. The composition of clause 1, wherein the base stock has a KV100 of
from 4.0 cSt to
5.0 cSt.
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[00150] 3. The composition of clause 1, wherein the base stock has a KV100 is
from 5.0 cSt to
7.0 cSt.
[00151] 4. The composition of clause 2, wherein the viscosity index is
120 to 133 and is less
than or equal to 142*(1 ¨ 0.0025 exp(8*(2R+NRRN))).
[00152] 5. The composition of clause 3, wherein the viscosity index is 120
to 133 and is less
than or equal to 150.07*(1-0.0106*exp(4.5*(2R+NRRN))).
[00153] 6. A passenger car motor oil composition comprising: a Group III base
stock
comprising: at least 90 wt.% saturated hydrocarbons; kinematic viscosity at
100 C of from 4.0 cSt
up to 5.0 cSt; a viscosity index of from 120 to less than 140; and a ratio of
multi-ring naphthenes
to single ring naphthenes (2R+NRRN) of less than 0.45; and an effective amount
of one or more
lubricant additives.
[00154] 7. The composition of clause 6, wherein the viscosity index is
120 to 140 and is less
than or equal to 142*(1 ¨ 0.0025 exp(8*(2R+NRRN))).
[00155] 8. A heavy duty diesel engine lubricating oil composition comprising:
a Group III base
stock comprising: at least 90 wt.% saturated hydrocarbons; kinematic viscosity
at 100 C of from
5.5 cSt up to 7.0 cSt; a viscosity index of from 120 to less than 144; and a
ratio of multi-ring
naphthenes to single ring naphthenes (2R+NRRN) of less than 0.56; and an
effective amount of
one or more lubricant additives.
[00156] 9. The composition of clause 8, wherein the viscosity index is
120 to 144 and is less
than or equal to 142*(1 ¨ 0.0025 exp(8*(2R+NRRN))).
[00157] 10. A lubricating composition comprising: a Group III base stock
comprising: at least
90 wt.% saturated hydrocarbons; kinematic viscosity at 100 C of 4.0 cSt to 5.0
cSt; a viscosity
index of 120 to 140; a ratio of multi-ring naphthenes to single ring
naphthenes (2R+NRRN) of less
than 0.52; and a ratio of branched carbons to straight chain carbons (BC/SC)
less than or equal to
0.21; and an effective amount of one or more lubricant additives.
[00158] 11. The lubricating composition of clause 10, wherein the base
stock has a ratio of
branched chain carbons to terminal carbons (BC/TC) less than or equal to 2.1.
[00159] 12. A lubricating composition comprising: a Group III base stock
comprising: at least
90 wt.% saturated hydrocarbons; kinematic viscosity at 100 C of 5.0 cSt to
12.0 cSt; a viscosity
index of 120 to 140; a ratio of multi-ring naphthenes to single ring
naphthenes (2R+NRRN) of less
than 0.59; and a ratio of branched carbons to straight chain carbons (BC/SC)
less than or equal to
0.26; and an effective amount of one or more lubricant additives.
[00160] 13. The lubricating composition of clause 12, wherein the base
stock has a ratio of
multi-ring naphthenes to single ring naphthenes (2R+NRRN) of less than 0.59
and BC/TC < 2.3.
CA 03084989 2020-06-05
WO 2019/126009
PCT/US2018/065949
- 43 -
[00161] 14. A lubricating composition comprising: a Group III base stock
comprising: at least
90 wt.% saturated hydrocarbons; kinematic viscosity at 100 C (KV100) of 4.0
cSt to 5.0 cSt; a
viscosity index of from 120 to 140; and a ratio of multi-ring naphthenes to
single ring naphthenes
(2R+NRRN) of less than 0.45; and an effective amount of one or more lubricant
additives.
[00162] 15. The composition of clause 14, wherein the base stock KV100 of
4.0 to 4.7.
[00163] 16. A lubricating composition comprising: a Group III base stock
comprising: at least
90 wt.% saturated hydrocarbons; kinematic viscosity at 100 C (KV100) of 5.0
cSt to 12.0 cSt; a
viscosity index of from 120 to 144; a ratio of multi-ring naphthenes to single
ring naphthenes
(2R+NRRN) of less than 0.56; and an effective amount of one or more lubricant
additives.
[00164] 17. The composition of clause 16, wherein the base stock KV100 of
5.5 to 7Ø
[00165] All patents and patent applications, test procedures (such as ASTM
methods, UL
methods, and the like), and other documents cited herein are fully
incorporated by reference to the
extent such disclosure is not inconsistent with this disclosure and for all
jurisdictions in which such
incorporation is permitted.
[00166] When numerical lower limits and numerical upper limits are listed
herein, ranges from
any lower limit to any upper limit are contemplated. While the illustrative
embodiments of the
disclosure have been described with particularity, it will be understood that
various other
modifications will be apparent to and can be readily made by those skilled in
the art without
departing from the spirit and scope of the disclosure. Accordingly, it is not
intended that the scope
of the claims appended hereto be limited to the examples and descriptions set
forth herein but rather
that the claims be construed as encompassing all the features of patentable
novelty which reside in
the present disclosure, including all features which would be treated as
equivalents thereof by those
skilled in the art to which the disclosure pertains.
[00167] The present disclosure has been described above with reference to
numerous
embodiments and specific examples. Many variations will suggest themselves to
those skilled in
this art in light of the above detailed description. All such obvious
variations are within the full
intended scope of the appended claims.
