Note: Descriptions are shown in the official language in which they were submitted.
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SOLVENT EXTRACTION FOR CORRECTION OF COLOR AND AROMATICS
DISTRIBUTION OF HEAVY NEUTRAL BASE STOCKS
FIELD
[0001] Systems and methods are provided for production of heavy neutral
lubricant oil base
stocks, such as heavy neutral base stocks derived from deasphalted oils
produced by low severity
deasphalting of resid fractions.
BACKGROUND
[0002] Lubricant base stocks are one of the higher value products that can
be generated from
a crude oil or crude oil fraction. The ability to generate lubricant base
stocks of a desired quality
is often constrained by the availability of a suitable feedstock. For example,
most conventional
processes for lubricant base stock production involve starting with a crude
fraction that has not
been previously processed under severe conditions, such as a virgin gas oil
fraction from a crude
with moderate to low levels of initial sulfur content.
[0003] In some situations, a deasphalted oil formed by propane desaphalting
of a vacuum
resid can be used for additional lubricant base stock production. Deasphalted
oils can potentially
be suitable for production of heavier base stocks, such as bright stocks.
However, the severity of
propane deasphalting required in order to make a suitable feed for lubricant
base stock production
typically results in a yield of only about 30 wt% deasphalted oil relative to
the vacuum resid feed.
[0004] U.S. Patent 3,414,506 describes methods for making lubricating oils
by hydrotreating
pentane-alcohol-deasphalted short residue. The methods include performing
deasphalting on a
vacuum resid fraction with a deasphalting solvent comprising a mixture of an
alkane, such as
pentane, and one or more short chain alcohols, such as methanol and isopropyl
alcohol. The
deasphalted oil is then hydrotreated, followed by solvent extraction to
perform sufficient VI uplift
to form lubricating oils.
[0005] U.S. Patent 7,776,206 describes methods for catalytically processing
resids and/or
deasphalted oils to form bright stock. A resid-derived stream, such as a
deasphalted oil, is
hydroprocessed to reduce the sulfur content to less than 1 wt% and reduce the
nitrogen content to
less than 0.5 wt%. The hydroprocessed stream is then fractionated to form a
heavier fraction and
a lighter fraction at a cut point between 1150 F ¨ 1300 F (620 C ¨ 705 C). The
lighter fraction is
then catalytically processed in various manners to form a bright stock.
SUMMARY
[0006] In various aspects, systems and methods are provided for performing
solvent
extraction on heavy neutral base stocks. The aromatic extraction can reduce
aromatics content
while have a reduced or minimized impact on lubricant properties. This can
allow, for example,
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for correction of color and/or haze for heavy neutral base stocks, such as
heavy neutral base stocks
formed from a deasphalted oil.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 schematically shows an example of a configuration for
processing a
deasphalted oil to form a lubricant base stock.
[0008] FIG. 2 schematically shows another example of a configuration for
processing a
deasphalted oil to form a lubricant base stock.
[0009] FIG. 3 schematically shows another example of a configuration for
processing a
deasphalted oil to form a lubricant base stock.
[0010] FIG. 4 shows results from processing a pentane deasphalted oil at
various levels of
hy dropro ces sing severity.
[0011] FIG. 5 shows results from processing deasphalted oil in
configurations with various
combinations of sour hydrocracking and sweet hydrocracking.
[0012] FIG. 6 schematically shows an example of a configuration for
catalytic processing of
deasphalted oil to form lubricant base stocks.
[0013] FIG. 7 schematically shows an example of a configuration for block
catalytic
processing of deasphalted oil to form lubricant base stocks.
[0014] FIG. 8 schematically shows an example of a configuration for block
catalytic
processing of deasphalted oil to form lubricant base stocks.
[0015] FIG. 9 schematically shows an example of a configuration for block
catalytic
processing of deasphalted oil to form lubricant base stocks.
[0016] FIG. 10 shows UV absorption spectra from a heavy neutral base stocks
with and
without aromatic extraction.
DETAILED DESCRIPTION
[0017] 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 expected by a person having ordinary skill
in the art.
Aromatic Extraction of Heavy Neutral Base Stocks
[0018] Some of the difficulties in producing lubricant base stocks, such as
heavy neutral base
stocks, can be related to formation of haze. Without being bound by any
particular theory, it is
believed that a variety of factors can result in haze formation in a lubricant
base stock, either during
processing, immediately after processing, or subsequent to processing (such as
after sitting for a
period of time). One of the factors that can contribute to haze formation is
the presence of
aromatics within a heavy neutral sample. For example, if a heavy neutral base
stock contains an
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excess of heavy aromatic compounds, the heavy aromatic compounds may not stay
completely in
solution after formation of the heavy neutral base stock, which could result
in the base stock having
a hazy appearance over time.
[0019] One example of a lubricant production process that can result in
production of heavy
neutral base stocks with a high content of aromatic compounds is production of
base stocks from
deasphalted oils. In particular, deasphalted oils formed using a solvent
deasphalting process with
a high yield of deasphalted oil (i.e., 50 wt% or greater), can have an
increased likelihood of
containing high contents of aromatics. It has been discovered that heavy
neutral base stock
samples, such as heavy neutral base stocks formed derived (at least in part)
from a deasphalted oil
feed, can be corrected to have a reduced or minimized likelihood of haze
formation by performing
an aromatic (solvent) extraction process on the heavy neutral base stock.
Additionally or
alternately, such an aromatic extraction process can be beneficial for
removing color from a heavy
neutral base stock sample. Without being bound by any particular theory, it is
believed that the
aromatic extraction can remove unstable molecules, such as high molecular
weight polynuclear
aromatics and/or multi-core naphthenic molecules. The aromatic extraction can
be performed after
formation of the heavy neutral base stock, or alternatively the aromatic
extraction can be performed
at an earlier stage in the formation of the heavy neutral base stock.
[0020] The aromatic extraction can be performed using aromatic extraction
solvents that are
commonly used for solvent extraction during solvent processing to form Group I
lubricant base
stocks. Examples of suitable solvents can include, but are not limited to, N-
methyl-pyrrolidone,
furfural, and/or phenol. Any convenient type of solvent contactor can be
suitable. The heavy
neutral base stock can correspond to a base stock with a kinematic viscosity
at 100 C of 6 cSt to
20 cSt, or 6 cSt to 16 cSt, or 6 cSt to 14 cSt, or 6 cSt to 12 cSt, or 8 cSt
to 20 cSt, or 8 cSt to 16
cSt, or 8 cSt to 14 cSt, or 8 cSt to 12 cSt, or 10 cSt to 20 cSt, or 10 cSt to
16 cSt, or 10 cSt to 14
cSt. The viscosity index of the heavy neutral base stock can be at least 80,
or at least 90, or at least
100, or at least 110, or at least 120. Additionally or alternately, the
viscosity index of the heavy
neutral base stock can be 80 to 160, or 80 to 140, or 80 to 120, or 90 to 160,
or 90 to 140, or 90 to
120, or 100 to 160, or 100 to 140, or 120 to 160, or 120 to 140.
[0021] As an example, a Group II heavy neutral (HN) base stock was made
from a
hydroprocessed blend of Cs deasphalted oil and vacuum gas oil. The Cs
deasphalted oil was made
from a pentane deasphalting process with a deasphalted oil yield of 75 wt%.
The "as made" HN
base stock sample had an unusual UV aromatics distribution, and also had more
color than desired,
with the color corresponding to a yellow hue. The HN sample was solvent
extracted with N-
methyl-pyrrolidone at conditions corresponding to a 200 vol% solvent treat
rate, 1 wt% water
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content, and a temperature of 100 C. Table A summarizes the properties of the
HN sample prior
to and after the solvent extraction process.
Table A ¨ Heavy Neutral Properties Before and After Solvent Extraction
Refractive Index 1.4566 1.4553
Total Aromatics ¨ 2 wt% 0.5 ¨ 1 wt%
2+ Ring Aromatics > 0.25 wt% <0.1 wt%
Viscosity Index 95 96
Mutagenicity Index (MI) 0.65 0
Yield, wt% 100 ¨ 79
[0022] As shown in Table A, performing the solvent extraction reduced the
yield and the
aromatics content of the heavy neutral sample, but the properties of the heavy
neutral sample were
otherwise similar before and after the solvent extraction. Additionally, the
solvent extraction
removed the color of the sample, so that post-extraction the heavy neutral
sample was water-white.
It is noted that although 2+ ring aromatics were removed effectively, a
meaningful portion of total
aromatics remain in the HN sample after extraction, which is believed to show
the selective nature
of the extraction process for removing multi-ring structures.
[0023] FIG. 10 provides a UV absorptivity profile for the HN sample prior
to and after the
solvent extraction. FIG. 10 shows a reduction in UV absorptivity at various
wavelengths. More
generally, prior to an aromatics extraction, a heavy neutral sample can have
an absorptivity at 226
nm of at least 0.020, or at least 0.025, or at least 0.030. After extraction,
the heavy neutral sample
can have an absorptivity at 226 nm of less than 0.020, or less than 0.018, or
less than 0.016.
Additionally or alternately, prior to an aromatics extraction, a heavy neutral
sample can have an
absorptivity at 254 nm of at least 0.010, or at least 0.012, or at least
0.014. After extraction, the
heavy neutral sample can have an absorptivity at 254 nm of less than 0.010, or
less than 0.008, or
less than 0.006, or less than 0.004. Additionally or alternately, prior to an
aromatics extraction, a
heavy neutral sample can have an absorptivity at 275 nm of at least 0.010, or
at least 0.012, or at
least 0.014. After extraction, the heavy neutral sample can have an
absorptivity at 275 nm of less
than 0.010, or less than 0.008, or less than 0.006, or less than 0.004.
Additionally or alternately,
prior to an aromatics extraction, a heavy neutral sample can have an
absorptivity at 302 nm of at
least 0.020, or at least 0.025, or at least 0.030. After extraction, the heavy
neutral sample can have
an absorptivity at 302 nm of less than 0.010, or less than 0.008, or less than
0.006, or less than
0.004. Additionally or alternately, prior to an aromatics extraction, a heavy
neutral sample can
have an absorptivity at 310 nm of at least 0.030, or at least 0.035, or at
least 0.040. After extraction,
the heavy neutral sample can have an absorptivity at 310 nm of less than
0.010, or less than 0.008,
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or less than 0.006, or less than 0.004. Additionally or alternately, prior to
an aromatics extraction,
a heavy neutral sample can have an absorptivity at 325 nm of at least 0.010,
or at least 0.012, or at
least 0.014. After extraction, the heavy neutral sample can have an
absorptivity at 310 nm of less
than 0.010, or less than 0.008, or less than 0.006, or less than 0.004.
Overview of Lubricant Base Stock Production from Deasphalted Oil
[0024] In various aspects, methods are provided for producing Group I and
Group II lubricant
base stocks, including Group I and Group II bright stock, from deasphalted
oils generated by low
severity C4+ deasphalting. Low severity deasphalting as used herein refers to
deasphalting under
conditions that result in a high yield of deasphalted oil (and/or a reduced
amount of rejected asphalt
or rock), such as a deasphalted oil yield of at least 50 wt% relative to the
feed to deasphalting, or
at least 55 wt%, or at least 60 wt%, or at least 65 wt%, or at least 70 wt%,
or at least 75 wt%. The
Group I base stocks (including bright stock) can be formed without performing
a solvent extraction
on the deasphalted oil. The Group II base stocks (including bright stock) can
be formed using a
combination of catalytic and solvent processing. In contrast with conventional
bright stock
produced from deasphalted oil formed at low severity conditions, the Group I
and Group II bright
stock described herein can be substantially free from haze after storage for
extended periods of
time. This haze free Group II bright stock can correspond to a bright stock
with an unexpected
composition.
[0025] In various additional aspects, methods are provided for catalytic
processing of C3
deasphalted oils to form Group II bright stock. Forming Group II bright stock
by catalytic
processing can provide a bright stock with unexpected compositional
properties.
[0026] Conventionally, crude oils are often described as being composed of
a variety of
boiling ranges. Lower boiling range compounds in a crude oil correspond to
naphtha or kerosene
fuels. Intermediate boiling range distillate compounds can be used as diesel
fuel or as lubricant
base stocks. If any higher boiling range compounds are present in a crude oil,
such compounds are
considered as residual or "resid" compounds, corresponding to the portion of a
crude oil that is left
over after performing atmospheric and/or vacuum distillation on the crude oil.
[0027] In some conventional processing schemes, a resid fraction can be
deasphalted, with
the deasphalted oil used as part of a feed for forming lubricant base stocks.
In conventional
processing schemes a deasphalted oil used as feed for forming lubricant base
stocks is produced
using propane deasphalting. This propane deasphalting corresponds to a "high
severity"
deasphalting, as indicated by a typical yield of deasphalted oil of about 40
wt% or less, often 30
wt% or less, relative to the initial resid fraction. In a typical lubricant
base stock production
process, the deasphalted oil can then be solvent extracted to reduce the
aromatics content, followed
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by solvent dewaxing to form a base stock. The low yield of deasphalted oil is
based in part on the
inability of conventional methods to produce lubricant base stocks from lower
severity
deasphalting that do not form haze over time.
[0028] In
some aspects, it has been discovered that using a mixture of catalytic
processing,
such as hydrotreatment, and solvent processing, such as solvent dewaxing, can
be used to produce
lubricant base stocks from deasphalted oil while also producing base stocks
that have little or no
tendency to form haze over extended periods of time. The deasphalted oil can
be produced by
deasphalting process that uses a C4 solvent, a C5 solvent, a C6+ solvent, a
mixture of two or more
C4+ solvents, or a mixture of two or more C5+ solvents. The deasphalting
process can further
correspond to a process with a yield of deasphalted oil of at least 50 wt% for
a vacuum resid feed
having a T10 distillation point (or optionally a T5 distillation point) of at
least 510 C, or a yield of
at least 60 wt%, or at least 65 wt%, or at least 70 wt%. It is believed that
the reduced haze formation
is due in part to the reduced or minimized differential between the pour point
and the cloud point
for the base stocks and/or due in part to forming a bright stock with a cloud
point of -5 C or less.
[0029] For
production of Group I base stocks, a deasphalted oil can be hydroprocessed
(hydrotreated and/or hydrocracked) under conditions sufficient to achieve a
desired viscosity index
increase for resulting base stock products. The hydroprocessed effluent can be
fractionated to
separate lower boiling portions from a lubricant base stock boiling range
portion. The lubricant
base stock boiling range portion can then be solvent dewaxed to produce a
dewaxed effluent. The
dewaxed effluent can be separated to form a plurality of base stocks with a
reduced tendency (such
as no tendency) to form haze over time.
[0030] For
production of Group II base stocks, in some aspects a deasphalted oil can be
hydroprocessed (hydrotreated and/or hydrocracked), so that ¨700 F+ (370 C+)
conversion is 10
wt% to 40 wt%. The hydroprocessed effluent can be fractionated to separate
lower boiling portions
from a lubricant base stock boiling range portion. The lubricant boiling range
portion can then be
hydrocracked, dewaxed, and hydrofinished to produce a catalytically dewaxed
effluent. Optionally
but preferably, the lubricant boiling range portion can be underdewaxed, so
that the wax content
of the catalytically dewaxed heavier portion or potential bright stock portion
of the effluent is at
least 6 wt%, or at least 8 wt%, or at least 10 wt%. This underdewaxing can
also be suitable for
forming light or medium or heavy neutral lubricant base stocks that do not
require further solvent
upgrading to form haze free base stocks. In this discussion, the heavier
portion / potential bright
stock portion can roughly correspond to a 538 C+ portion of the dewaxed
effluent. The
catalytically dewaxed heavier portion of the effluent can then be solvent
dewaxed to form a solvent
dewaxed effluent. The solvent dewaxed effluent can be separated to form a
plurality of base stocks
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with a reduced tendency (such as no tendency) to form haze over time,
including at least a portion
of a Group II bright stock product.
[0031] For production of Group II base stocks, in other aspects a
deasphalted oil can be
hydroprocessed (hydrotreated and/or hydrocracked), so that 370 C+ conversion
is at least 40 wt%,
or at least 50 wt%. The hydroprocessed effluent can be fractionated to
separate lower boiling
portions from a lubricant base stock boiling range portion. The lubricant base
stock boiling range
portion can then be hydrocracked, dewaxed, and hydrofinished to produce a
catalytically dewaxed
effluent. The catalytically dewaxed effluent can then be solvent extracted to
form a raffinate. The
raffinate can be separated to form a plurality of base stocks with a reduced
tendency (such as no
tendency) to form haze over time, including at least a portion of a Group II
bright stock product.
[0032] In other aspects, it has been discovered that catalytic processing
can be used to
produce Group II bright stock with unexpected compositional properties from
C3, C4, C5, and/or
C5+ deasphalted oil. The deasphalted oil can be hydrotreated to reduce the
content of heteroatoms
(such as sulfur and nitrogen), followed by catalytic dewaxing under sweet
conditions. Optionally,
hydrocracking can be included as part of the sour hydrotreatment stage and/or
as part of the sweet
dewaxing stage.
[0033] Optionally, the systems and methods described herein can be used in
"block"operation to allow for additional improvements in yield and/or product
quality. During
"block" operation, a deaspahlted oil and/or the hydroprocessed effluent from
the sour processing
stage can be split into a plurality of fractions. The fractions can
correspond, for example, to feed
fractions suitable for forming a light neutral fraction, a heavy neutral
fraction, and a bright stock
fraction, or the plurality of fractions can correspond to any other convenient
split into separate
fractions. The plurality of separate fractions can then be processed
separately in the process train
(or in the sweet portion of the process train) for forming lubricant base
stocks. For example, the
light neutral portion of the feed can be processed for a period of time,
followed by processing of
the heavy neutral portion, followed by processing of a bright stock portion.
During the time period
when one type of fraction is being processed, storage tanks can be used to
hold the remaining
fractions.
[0034] Block operation can allow the processing conditions in the process
train to be tailored
to each type of lubricant fraction. For example, the amount of sweet
processing stage conversion
of the heavy neutral fraction can be lower than the amount of sweet processing
stage conversion
for the light neutral fraction. This can reflect the fact that heavy neutral
lubricant base stocks may
not need as high a viscosity index as light neutral base stocks.
[0035] Another option for modifying the production of base stocks can be to
recycle a portion
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of at least one lubricant base stock product for further processing in the
process train. This can
correspond to recycling a portion of a base stock product for further
processing in the sour stage
and/or recycling a portion of a base stock product for further processing in
the corresponding sweet
stage. Optionally, a base stock product can be recycled for further processing
in a different phase
of block operation, such as recycling light neutral base stock product formed
during block
processing of the heavy neutral fraction for further processing during block
processing of the light
neutral fraction. The amount of base stock product recycled can correspond to
any convenient
amount of a base stock product effluent from the fractionator, such as 1 wt%
to 50 wt% of a base
stock product effluent, or 1 wt% to 20 wt%.
[0036] Recycling a portion of a base stock product effluent can optionally
be used while
operating a lube processing system at higher than typical levels of fuels
conversion. When using
a conventional feed for lubricant production, conversion of feed relative to
370 C can be limited
to 65 wt% or less. Conversion of more than 65 wt% of a feed relative to 370 C
is typically not
favored due to loss of viscosity index with additional conversion. At elevated
levels of conversion,
the loss of VI with additional conversion is believed to be due to cracking
and/or conversion of
isoparaffins within a feed. For feeds derived from deasphalted oil, however,
the amount of
isoparaffins within a feed is lower than a conventional feed. As a result,
additional conversion can
be performed without loss of VI. In some aspects, converting at least 70 wt%
of a feed, or at least
75 wt%, or at least 80 wt% can allow for production of lubricant base stocks
with substantially
improved cold flow properties while still maintaining the viscosity index of
the products at a
similar value to the viscosity index at a conventional conversion of 60 wt%.
[0037] In various aspects, a variety of combinations of catalytic and/or
solvent processing
can be used to form lubricant base stocks, including Group II bright stock,
from deasphalted oils.
These combinations include, but are not limited to:
[0038] a) Hydroprocessing of a deasphalted oil under sour conditions (i.e.,
sulfur content of
at least 500 wppm); separation of the hydroprocessed effluent to form at least
a lubricant boiling
range fraction; and solvent dewaxing of the lubricant boiling range fraction.
In some aspects, the
hydroprocessing of the deasphalted oil can correspond to hydrotreatment,
hydrocracking, or a
combination thereof
[0039] b) Hydroprocessing of a deasphalted oil under sour conditions (i.e.,
sulfur content of
at least 500 wppm); separation of the hydroprocessed effluent to form at least
a lubricant boiling
range fraction; and catalytic dewaxing of the lubricant boiling range fraction
under sweet
conditions (i.e., 500 wppm or less sulfur). The catalytic dewaxing can
optionally correspond to
catalytic dewaxing using a dewaxing catalyst with a pore size greater than 8.4
Angstroms.
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Optionally, the sweet processing conditions can further include hydrocracking,
noble metal
hydrotreatment, and/or hydrofinishing. The optional hydrocracking, noble metal
hydrotreatment,
and/or hydrofinishing can occur prior to and/or after or after catalytic
dewaxing. For example, the
order of catalytic processing under sweet processing conditions can be noble
metal hydrotreating
followed by hydrocracking followed by catalytic dewaxing.
[0040] c) The process of b) above, followed by performing an additional
separation on at
least a portion of the catalytically dewaxed effluent. The additional
separation can correspond to
solvent dewaxing, solvent extraction (such as solvent extraction with furfural
or n-
methylpyrollidone), a physical separation such as ultracentrifugation, or a
combination thereof
[0041] d) The process of a) above, followed by catalytic dewaxing (sweet
conditions) of at
least a portion of the solvent dewaxed product. Optionally, the sweet
processing conditions can
further include hydrotreating (such as noble metal hydrotreating),
hydrocracking and/or
hydrofinishing. The additional sweet hydroprocessing can be performed prior to
and/or after the
catalytic dewaxing.
[0042] Group I base stocks or base oils are defined as base stocks with
less than 90 wt%
saturated molecules and/or at least 0.03 wt% sulfur content. Group I base
stocks also have a
viscosity index (VI) of at least 80 but less than 120. Group II base stocks or
base oils contain at
least 90 wt% saturated molecules and less than 0.03 wt% sulfur. Group II base
stocks also have a
viscosity index of at least 80 but less than 120. Group III base stocks or
base oils contain at least
90 wt% saturated molecules and less than 0.03 wt% sulfur, with a viscosity
index of at least 120.
[0043] In some aspects, a Group III base stock as described herein may
correspond to a
Group III+ base stock. Although a generally accepted definition is not
available, a Group III+ base
stock can generally correspond to a base stock that satisfies the requirements
for a Group III base
stock while also having at least one property that is enhanced relative to a
Group III specification.
The enhanced property can correspond to, for example, having a viscosity index
that is
substantially greater than the required specification of 120, such as a Group
III base stock having
a VI of at least 130, or at least 135, or at least 140. Similarly, in some
aspects, a Group II base
stock as described herein may correspond to a Group II+ base stock. Although a
generally accepted
definition is not available, a Group II+ base stock can generally correspond
to a base stock that
satisfies the requirements for a Group II base stock while also having at
least one property that is
enhanced relative to a Group II specification. The enhanced property can
correspond to, for
example, having a viscosity index that is substantially greater than the
required specification of 80,
such as a Group II base stock having a VI of at least 103, or at least 108, or
at least 113.
[0044] In the discussion below, a stage can correspond to a single reactor
or a plurality of
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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. Note
that a "bed" of
catalyst in the discussion below 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.
[0045] In this discussion, conditions may be provided for various types of
hydroprocessing
of feeds or effluents. Examples of hydroprocessing can include, but are not
limited to, one or more
of hydrotreating, hydrocracking, catalytic dewaxing, and hydrofinishing /
aromatic saturation.
Such hydroprocessing conditions can be controlled to have desired values for
the conditions (e.g.,
temperature, pressure, LHSV, treat gas rate) by using at least one controller,
such as a plurality of
controllers, to control one or more of the hydroprocessing conditions. In some
aspects, for a given
type of hydroprocessing, at least one controller can be associated with each
type of
hydroprocessing condition. In some aspects, one or more of the hydroprocessing
conditions can
be controlled by an associated controller. Examples of structures that can be
controlled by a
controller can include, but are not limited to, valves that control a flow
rate, a pressure, or a
combination thereof; heat exchangers and/or heaters that control a
temperature; and one or more
flow meters and one or more associated valves that control relative flow rates
of at least two flows.
Such controllers can optionally include a controller feedback loop including
at least a processor, a
detector for detecting a value of a control variable (e.g., temperature,
pressure, flow rate, and a
processor output for controlling the value of a manipulated variable (e.g.,
changing the position of
a valve, increasing or decreasing the duty cycle and/or temperature for a
heater). Optionally, at
least one hydroprocessing condition for a given type of hydroprocessing may
not have an
associated controller.
[0046] In this discussion, unless otherwise specified a lubricant boiling
range fraction
corresponds to a fraction having an initial boiling point or alternatively a
T5 boiling point of at
least about 370 C (-700 F). A distillate fuel boiling range fraction, such as
a diesel product
fraction, corresponds to a fraction having a boiling range from about 193 C
(375 F) to about 370 C
(-700 F). Thus, distillate fuel boiling range fractions (such as distillate
fuel product fractions) can
have initial boiling points (or alternatively T5 boiling points) of at least
about 193 C and final
boiling points (or alternatively T95 boiling points) of about 370 C or less. A
naphtha boiling range
fraction corresponds to a fraction having a boiling range from about 36 C (122
F) to about 193 C
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(375 F) to about 370 C (-700 F). Thus, naphtha fuel product fractions can have
initial boiling
points (or alternatively T5 boiling points) of at least about 36 C and final
boiling points (or
alternatively T95 boiling points) of about 193 C or less. It is noted that 36
C roughly corresponds
to a boiling point for the various isomers of a C5 alkane. A fuels boiling
range fraction can
correspond to a distillate fuel boiling range fraction, a naphtha boiling
range fraction, or a fraction
that includes both distillate fuel boiling range and naphtha boiling range
components. Light ends
are defined as products with boiling points below about 36 C, which include
various Cl ¨ C4
compounds. When determining a boiling point or a boiling range for a feed or
product fraction, an
appropriate ASTM test method can be used, such as the procedures described in
ASTM D2887,
D2892, and/or D86. Preferably, ASTM D2887 should be used unless a sample is
not appropriate
for characterization based on ASTM D2887. For example, for samples that will
not completely
elute from a chromatographic column, ASTM D7169 can be used.
Feedstocks
[0047] In various aspects, at least a portion of a feedstock for processing
as described herein
can correspond to a vacuum resid fraction or another type 950 F+ (510 C+) or
1000 F+ (538 C+)
fraction. Another example of a method for forming a 950 F+ (510 C+) or 1000 F+
(538 C+)
fraction is to perform a high temperature flash separation. The 950 F+ (510
C+) or 1000 F+
(538 C+) fraction formed from the high temperature flash can be processed in a
manner similar to
a vacuum resid.
[0048] A vacuum resid fraction or a 950 F+ (510 C+) fraction formed by
another process
(such as a flash fractionation bottoms or a bitumen fraction) can be
deasphalted at low severity to
form a deasphalted oil. Optionally, the feedstock can also include a portion
of a conventional feed
for lubricant base stock production, such as a vacuum gas oil.
[0049] A vacuum resid (or other 510 C+) fraction can correspond to a
fraction with a T5
distillation point (ASTM D2892, or ASTM D7169 if the fraction will not
completely elute from a
chromatographic system) of at least about 900 F (482 C), or at least 950 F
(510 C), or at least
1000 F (538 C). Alternatively, a vacuum resid fraction can be characterized
based on a T10
distillation point (ASTM D2892 / D7169) of at least about 900 F (482 C), or at
least 950 F
(510 C), or at least 1000 F (538 C).
[0050] Resid (or other 510 C+) fractions can be high in metals. For
example, a resid fraction
can be high in total nickel, vanadium and iron contents. In an aspect, a resid
fraction can contain
at least 0.00005 grams of NiN/Fe (50 wppm) or at least 0.0002 grams of NiN/Fe
(200 wppm) per
gram of resid, on a total elemental basis of nickel, vanadium and iron. In
other aspects, the heavy
oil can contain at least 500 wppm of nickel, vanadium, and iron, such as up to
1000 wppm or more.
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[0051] Contaminants such as nitrogen and sulfur are typically found in
resid (or other
510 C+) fractions, often in organically-bound form. Nitrogen content can range
from about 50
wppm to about 10,000 wppm elemental nitrogen or more, based on total weight of
the resid
fraction. Sulfur content can range from 500 wppm to 100,000 wppm elemental
sulfur or more,
based on total weight of the resid fraction, or from 1000 wppm to 50,000 wppm,
or from 1000
wppm to 30,000 wppm.
[0052] Still another method for characterizing a resid (or other 510 C+)
fraction is based on
the Conradson carbon residue (CCR) of the feedstock. The Conradson carbon
residue of a resid
fraction can be at least about 5 wt%, such as at least about 10 wt% or at
least about 20 wt%.
Additionally or alternately, the Conradson carbon residue of a resid fraction
can be about 50 wt%
or less, such as about 40 wt% or less or about 30 wt% or less.
[0053] In some aspects, a vacuum gas oil fraction can be co-processed with
a deasphalted
oil. The vacuum gas oil can be combined with the deasphalted oil in various
amounts ranging from
20 parts (by weight) deasphalted oil to 1 part vacuum gas oil (i.e., 20: 1) to
1 part deasphalted oil
to 1 part vacuum gas oil. In some aspects, the ratio of deasphalted oil to
vacuum gas oil can be at
least 1 : 1 by weight, or at least 1.5 : 1, or at least 2 : 1. Typical
(vacuum) gas oil fractions can
include, for example, fractions with a T5 distillation point to T95
distillation point of 650 F
(343 C) ¨ 1050 F (566 C) or 650 F (343 C) ¨ 1000 F (538 C) or 650 F (343 C) ¨
950 F
(510 C), or 650 F (343 C) ¨ 900 F (482 C) or ¨700 F (370 C) ¨ 1050 F (566 C)
or ¨700 F
(370 C) ¨ 1000 F (538 C) or ¨700 F (370 C) ¨ 950 F (510 C) or ¨700 F (370 C) ¨
900 F
(482 C), or 750 F (399 C) ¨ 1050 F (566 C), or 750 F (399 C) ¨ 1000 F (538 C),
or 750 F
(399 C) ¨ 950 F (510 C), or 750 F (399 C) ¨ 900 F (482 C). For example a
suitable vacuum gas
oil fraction can have a T5 distillation point of at least 343 C and a T95
distillation point of 566 C
or less; or a T10 distillation point of at least 343 C and a T90 distillation
point of 566 C or less; or
a T5 distillation point of at least 370 C and a T95 distillation point of 566
C or less; or a T5
distillation point of at least 343 C and a T95 distillation point of 538 C or
less.
Solvent Deasphalting
[0054] Solvent deasphalting is a solvent extraction process. In some
aspects, suitable
solvents for methods as described herein include alkanes or other hydrocarbons
(such as alkenes)
containing 4 to 7 carbons per molecule. Examples of suitable solvents include
n-butane, isobutane,
n-pentane, C4+ alkanes, C5+ alkanes, C4+ hydrocarbons, and C5+ hydrocarbons.
In other aspects,
suitable solvents can include C3 hydrocarbons, such as propane. In such other
aspects, examples
of suitable solvents include propane, n-butane, isobutane, n-pentane, C3+
alkanes, C4+ alkanes, C5+
alkanes, C3+ hydrocarbons, C4+ hydrocarbons, and C5+ hydrocarbons.
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[0055] In this discussion, a solvent comprising Cn (hydrocarbons) is
defined as a solvent
composed of at least 80 wt% of alkanes (hydrocarbons) having n carbon atoms,
or at least 85 wt%,
or at least 90 wt%, or at least 95 wt%, or at least 98 wt%. Similarly, a
solvent comprising Cn+
(hydrocarbons) is defined as a solvent composed of at least 80 wt% of alkanes
(hydrocarbons)
having n or more carbon atoms, or at least 85 wt%, or at least 90 wt%, or at
least 95 wt%, or at
least 98 wt%.
[0056] In this discussion, a solvent comprising Cn alkanes (hydrocarbons)
is defined to
include the situation where the solvent corresponds to a single alkane
(hydrocarbon) containing n
carbon atoms (for example, n = 3, 4, 5, 6, 7) as well as the situations where
the solvent is composed
of a mixture of alkanes (hydrocarbons) containing n carbon atoms. Similarly, a
solvent comprising
Cn+ alkanes (hydrocarbons) is defined to include the situation where the
solvent corresponds to a
single alkane (hydrocarbon) containing n or more carbon atoms (for example, n
= 3, 4, 5, 6, 7) as
well as the situations where the solvent corresponds to a mixture of alkanes
(hydrocarbons)
containing n or more carbon atoms. Thus, a solvent comprising C4+ alkanes can
correspond to a
solvent including n-butane; a solvent include n-butane and isobutane; a
solvent corresponding to a
mixture of one or more butane isomers and one or more pentane isomers; or any
other convenient
combination of alkanes containing 4 or more carbon atoms. Similarly, a solvent
comprising Cs+
alkanes (hydrocarbons) is defined to include a solvent corresponding to a
single alkane
(hydrocarbon) or a solvent corresponding to a mixture of alkanes
(hydrocarbons) that contain 5 or
more carbon atoms. Alternatively, other types of solvents may also be
suitable, such as
supercritical fluids. In various aspects, the solvent for solvent deasphalting
can consist essentially
of hydrocarbons, so that at least 98 wt% or at least 99 wt% of the solvent
corresponds to compounds
containing only carbon and hydrogen. In aspects where the deasphalting solvent
corresponds to a
C4+ deasphalting solvent, the C4+ deasphalting solvent can include less than
15 wt% propane and/or
other C3 hydrocarbons, or less than 10 wt%, or less than 5 wt%, or the C4+
deasphalting solvent
can be substantially free of propane and/or other C3 hydrocarbons (less than 1
wt%). In aspects
where the deasphalting solvent corresponds to a C5+ deasphalting solvent, the
C5+ deasphalting
solvent can include less than 15 wt% propane, butane and/or other C3 - C4
hydrocarbons, or less
than 10 wt%, or less than 5 wt%, or the C5+ deasphalting solvent can be
substantially free of
propane, butane, and/or other C3 ¨ C4 hydrocarbons (less than 1 wt%). In
aspects where the
deasphalting solvent corresponds to a C3+ deasphalting solvent, the C3+
deasphalting solvent can
include less than 10 wt% ethane and/or other C2 hydrocarbons, or less than 5
wt%, or the C3+
deasphalting solvent can be substantially free of ethane and/or other C2
hydrocarbons (less than 1
wt%).
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[0057] Deasphalting of heavy hydrocarbons, such as vacuum resids, is known
in the art and
practiced commercially. A deasphalting process typically corresponds to
contacting a heavy
hydrocarbon with an alkane solvent (propane, butane, pentane, hexane, heptane
etc and their
isomers), either in pure form or as mixtures, to produce two types of product
streams. One type of
product stream can be a deasphalted oil extracted by the alkane, which is
further separated to
produce deasphalted oil stream. A second type of product stream can be a
residual portion of the
feed not soluble in the solvent, often referred to as rock or asphaltene
fraction. The deasphalted oil
fraction can be further processed into make fuels or lubricants. The rock
fraction can be further
used as blend component to produce asphalt, fuel oil, and/or other products.
The rock fraction can
also be used as feed to gasification processes such as partial oxidation,
fluid bed combustion or
coking processes. The rock can be delivered to these processes as a liquid
(with or without
additional components) or solid (either as pellets or lumps).
[0058] During solvent deasphalting, a resid boiling range feed (optionally
also including a
portion of a vacuum gas oil feed) can be mixed with a solvent. Portions of the
feed that are soluble
in the solvent are then extracted, leaving behind a residue with little or no
solubility in the solvent.
The portion of the deasphalted feedstock that is extracted with the solvent is
often referred to as
deasphalted oil. Typical solvent deasphalting conditions include mixing a
feedstock fraction with
a solvent in a weight ratio of from about 1 : 2 to about 1 : 10, such as about
1 : 8 or less. Typical
solvent deasphalting temperatures range from 40 C to 200 C, or 40 C to 150 C,
depending on the
nature of the feed and the solvent. The pressure during solvent deasphalting
can be from about 50
psig (345 kPag) to about 500 psig (3447 kPag).
[0059] It is noted that the above solvent deasphalting conditions represent
a general range,
and the conditions will vary depending on the feed. For example, under typical
deasphalting
conditions, increasing the temperature can tend to reduce the yield while
increasing the quality of
the resulting deasphalted oil. Under typical deasphalting conditions,
increasing the molecular
weight of the solvent can tend to increase the yield while reducing the
quality of the resulting
deasphalted oil, as additional compounds within a resid fraction may be
soluble in a solvent
composed of higher molecular weight hydrocarbons. Under typical deasphalting
conditions,
increasing the amount of solvent can tend to increase the yield of the
resulting deasphalted oil. As
understood by those of skill in the art, the conditions for a particular feed
can be selected based on
the resulting yield of deasphalted oil from solvent deasphalting. In aspects
where a C3 deasphalting
solvent is used, the yield from solvent deasphalting can be 40 wt% or less. In
some aspects, C4
deasphalting can be performed with a yield of deasphalted oil of 50 wt% or
less, or 40 wt% or less.
In various aspects, the yield of deasphalted oil from solvent deasphalting
with a C4+ solvent can be
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at least 50 wt% relative to the weight of the feed to deasphalting, or at
least 55 wt%, or at least 60
wt% or at least 65 wt%, or at least 70 wt%. In aspects where the feed to
deasphalting includes a
vacuum gas oil portion, the yield from solvent deasphalting can be
characterized based on a yield
by weight of a 950 F+ (510 C) portion of the deasphalted oil relative to the
weight of a 510 C+
portion of the feed. In such aspects where a C4+ solvent is used, the yield of
510 C+ deasphalted
oil from solvent deasphalting can be at least 40 wt% relative to the weight of
the 510 C+ portion
of the feed to deasphalting, or at least 50 wt%, or at least 55 wt%, or at
least 60 wt% or at least 65
wt%, or at least 70 wt%. In such aspects where a C4- solvent is used, the
yield of 510 C+
deasphalted oil from solvent deasphalting can be 50 wt% or less relative to
the weight of the
510 C+ portion of the feed to deasphalting, or 40 wt% or less, or 35 wt% or
less.
Hy drotreating and Hy drocracking
[0060] After deasphalting, the deasphalted oil (and any additional
fractions combined with
the deasphalted oil) can undergo further processing to form lubricant base
stocks. This can include
hydrotreatment and/or hydrocracking to remove heteroatoms to desired levels,
reduce Conradson
Carbon content, and/or provide viscosity index (VI) uplift. Depending on the
aspect, a deasphalted
oil can be hydroprocessed by hydrotreating, hydrocracking, or hydrotreating
and hydrocracking.
Optionally, one or more catalyst beds and/or stages of demetallization
catalyst can be included
prior to the initial bed of hydrotreating and/or hydrocracking catalyst.
Optionally, the
hydroprocessing can further include exposing the deasphalted oil to a base
metal aromatic
saturation catalyst. It is noted that a base metal aromatic saturation
catalyst can sometimes be
similar to a lower activity hydrotreating catalyst.
[0061] The deasphalted oil can be hydrotreated and/or hydrocracked with
little or no solvent
extraction being performed prior to and/or after the deasphalting. As a
result, the deasphalted oil
feed for hydrotreatment and/or hydrocracking can have a substantial aromatics
content. In various
aspects, the aromatics content of the deasphalted oil feed can be at least 50
wt%, or at least 55
wt%, or at least 60 wt%, or at least 65 wt%, or at least 70 wt%, or at least
75 wt%, such as up to
90 wt% or more. Additionally or alternately, the saturates content of the
deasphalted oil feed can
be 50 wt% or less, or 45 wt% or less, or 40 wt% or less, or 35 wt% or less, or
30 wt% or less, or
25 wt% or less, such as down to 10 wt% or less. In this discussion and the
claims below, the
aromatics content and/or the saturates content of a fraction can be determined
based on ASTM
D7419.
[0062] The reaction conditions during demetallization and/or hydrotreatment
and/or
hydrocracking of the deasphalted oil (and optional vacuum gas oil co-feed) can
be selected to
generate a desired level of conversion of a feed. Any convenient type of
reactor, such as fixed bed
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(for example trickle bed) reactors can be used. Conversion of the feed can be
defined in terms of
conversion of molecules that boil above a temperature threshold to molecules
below that threshold.
The conversion temperature can be any convenient temperature, such as ¨700 F
(370 C) or 1050 F
(566 C). The amount of conversion can correspond to the total conversion of
molecules within
the combined hydrotreatment and hydrocracking stages for the deasphalted oil.
Suitable amounts
of conversion of molecules boiling above 1050 F (566 C) to molecules boiling
below 566 C
include 30 wt% to 90 wt% conversion relative to 566 C, or 30 wt% to 80 wt%, or
30 wt% to 70
wt%, or 40 wt% to 90 wt%, or 40 wt% to 80 wt%, or 40 wt% to 70 wt%, or 50 wt%
to 90 wt%,
or 50 wt% to 80 wt%, or 50 wt% to 70 wt%. In particular, the amount of
conversion relative to
566 C can be 30 wt% to 90 wt%, or 30 wt% to 70 wt%, or 50 wt% to 90 wt%.
Additionally or
alternately, suitable amounts of conversion of molecules boiling above ¨700 F
(370 C) to
molecules boiling below 370 C include 10 wt% to 70 wt% conversion relative to
370 C, or 10
wt% to 60 wt%, or 10 wt% to 50 wt%, or 20 wt% to 70 wt%, or 20 wt% to 60 wt%,
or 20 wt% to
50 wt%, or 30 wt% to 70 wt%, or 30 wt% to 60 wt%, or 30 wt% to 50 wt%. In
particular, the
amount of conversion relative to 370 C can be 10 wt% to 70 wt%, or 20 wt% to
50 wt%, or 30
wt% to 60 wt%.
[0063] The hydroprocessed deasphalted oil can also be characterized based
on the product
quality. After hydroprocessing (hydrotreating and/or hydrocracking), the
hydroprocessed
deasphalted oil can have a sulfur content of 200 wppm or less, or 100 wppm or
less, or 50 wppm
or less (such as down to ¨0 wppm). Additionally or alternately, the
hydroprocessed deasphalted
oil can have a nitrogen content of 200 wppm or less, or 100 wppm or less, or
50 wppm or less
(such as down to ¨0 wppm). Additionally or alternately, the hydroprocessed
deasphalted oil can
have a Conradson Carbon residue content of 1.5 wt% or less, or 1.0 wt% or
less, or 0.7 wt% or
less, or 0.1 wt% or less, or 0.02 wt% or less (such as down to ¨0 wt%).
Conradson Carbon residue
content can be determined according to ASTM D4530.
[0064] In various aspects, a feed can initially be exposed to a
demetallization catalyst prior
to exposing the feed to a hydrotreating catalyst. Deasphalted oils can have
metals concentrations
(Ni + V + Fe) on the order of 10 ¨ 100 wppm. Exposing a conventional
hydrotreating catalyst to
a feed having a metals content of 10 wppm or more can lead to catalyst
deactivation at a faster rate
than may desirable in a commercial setting. Exposing a metal containing feed
to a demetallization
catalyst prior to the hydrotreating catalyst can allow at least a portion of
the metals to be removed
by the demetallization catalyst, which can reduce or minimize the deactivation
of the hydrotreating
catalyst and/or other subsequent catalysts in the process flow. Commercially
available
demetallization catalysts can be suitable, such as large pore amorphous oxide
catalysts that may
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optionally include Group VI and/or Group VIII non-noble metals to provide some
hydrogenation
activity.
[0065] In
various aspects, the deasphalted oil can be exposed to a hydrotreating
catalyst
under effective hydrotreating conditions. The
catalysts used can include conventional
hydroprocessing catalysts, such as those comprising at least one Group VIII
non-noble metal
(Columns 8 ¨ 10 of IUPAC periodic table), preferably Fe, Co, and/or Ni, such
as Co and/or Ni;
and at least one Group VI metal (Column 6 of IUPAC periodic table), preferably
Mo and/or W.
Such hydroprocessing catalysts optionally include transition metal sulfides
that are impregnated or
dispersed on a refractory support or carrier such as alumina and/or silica.
The support or carrier
itself typically has no significant/measurable catalytic activity.
Substantially carrier- or support-
free catalysts, commonly referred to as bulk catalysts, generally have higher
volumetric activities
than their supported counterparts.
[0066] The
catalysts can either be in bulk form or in supported form. In addition to
alumina
and/or silica, other suitable support/carrier materials can include, but are
not limited to, zeolites,
titania, silica-titania, and titania-alumina. Suitable aluminas are 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 a pore volume of from 0.25 to 1.0 cm3/g, or 0.35
to 0.8 cm3/g. More
generally, any convenient size, shape, and/or pore size distribution for a
catalyst suitable for
hydrotreatment of a distillate (including lubricant base stock) boiling range
feed in a conventional
manner may be used. Preferably, the support or carrier material is an
amorphous support, such as
a refractory oxide. Preferably, the support or carrier material can be free or
substantially free of
the presence of molecular sieve, where substantially free of molecular sieve
is defined as having a
content of molecular sieve of less than about 0.01 wt%.
[0067] The
at least one Group VIII non-noble metal, in oxide form, can typically be
present
in an amount ranging from about 2 wt% to about 40 wt%, preferably from about 4
wt% to about
15 wt%. The at least one Group VI metal, in oxide form, can typically be
present in an amount
ranging from about 2 wt% to about 70 wt%, preferably for supported catalysts
from about 6 wt%
to about 40 wt% or from about 10 wt% to about 30 wt%. These weight percents
are based on the
total weight of the catalyst. Suitable 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, silica,
silica-alumina, or
titania.
[0068] The
hydrotreatment is carried out in the presence of hydrogen. A hydrogen stream
is, therefore, fed or injected into a vessel or reaction zone or
hydroprocessing zone in which the
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hydroprocessing catalyst is located. Hydrogen, which is contained in a
hydrogen "treat gas," is
provided to the reaction zone. Treat gas, as referred to in this invention,
can be either pure
hydrogen or a hydrogen-containing gas, which is a gas stream containing
hydrogen in an amount
that is sufficient for the intended reaction(s), optionally including one or
more other gasses (e.g.,
nitrogen and light hydrocarbons such as methane). The treat gas stream
introduced into a reaction
stage will preferably contain at least about 50 vol. % and more preferably at
least about 75 vol. %
hydrogen. Optionally, the hydrogen treat gas can be substantially free (less
than 1 vol%) of
impurities such as H2S and NH3 and/or such impurities can be substantially
removed from a treat
gas prior to use.
[0069] Hydrogen can be supplied at a rate of from about 100 SCF/B (standard
cubic feet of
hydrogen per barrel of feed) (17 Nm3/m3) to about 10000 SCF/B (1700 Nm3/m3).
Preferably, the
hydrogen is provided in a range of from about 200 SCF/B (34 Nm3/m3) to about
2500 SCF/B (420
Nm3/m3). Hydrogen can be supplied co-currently with the input feed to the
hydrotreatment reactor
and/or reaction zone or separately via a separate gas conduit to the
hydrotreatment zone.
[0070] 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 300 psig
(2.1 MPag) to 3000
psig (20.8 MPag); liquid hourly space velocities (LHSV) of 0.1 hr' to 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).
[0071] In various aspects, the deasphalted oil can be exposed to a
hydrocracking catalyst
under effective hydrocracking conditions. Hydrocracking catalysts typically
contain sulfided base
metals on acidic supports, such as amorphous silica alumina, cracking zeolites
such as USY, or
acidified alumina. Often these acidic supports are mixed or bound with other
metal oxides such as
alumina, titania or silica. Examples of suitable acidic supports include
acidic molecular sieves,
such as zeolites or silicoaluminophophates. One example of suitable zeolite is
USY, such as a
USY zeolite with cell size of 24.30 Angstroms or less. Additionally or
alternately, the catalyst can
be a low acidity molecular sieve, such as a USY zeolite with a Si to Al ratio
of at least about 20,
and preferably at least about 40 or 50. ZSM-48, such as ZSM-48 with a SiO2 to
A1203 ratio of
about 110 or less, such as about 90 or less, is another example of a
potentially suitable
hydrocracking catalyst. Still another option is to use a combination of USY
and ZSM-48. Still
other options include using one or more of zeolite Beta, ZSM-5, ZSM-35, or ZSM-
23, either alone
or in combination with a USY catalyst. Non-limiting examples of metals for
hydrocracking catalysts
include metals or combinations of metals that include at least one Group VIII
metal, such as nickel,
nickel-cobalt-molybdenum, cobalt-molybdenum, nickel-tungsten, nickel-
molybdenum, and/or
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nickel-molybdenum-tungsten. Additionally or alternately, hydrocracking
catalysts with noble metals
can also be used. Non-limiting examples of noble metal catalysts include those
based on platinum
and/or palladium. Support materials which may be used for both the noble and
non-noble metal
catalysts can comprise a refractory oxide material such as alumina, silica,
alumina-silica, kieselguhr,
diatomaceous earth, magnesia, zirconia, or combinations thereof, with alumina,
silica, alumina-silica
being the most common (and preferred, in one embodiment).
[0072] When only one hydrogenation metal is present on a hydrocracking
catalyst, the
amount of that hydrogenation metal can be at least about 0.1 wt% based on the
total weight of the
catalyst, for example at least about 0.5 wt% or at least about 0.6 wt%.
Additionally or alternately
when only one hydrogenation metal is present, the amount of that hydrogenation
metal can be
about 5.0 wt% or less based on the total weight of the catalyst, for example
about 3.5 wt% or less,
about 2.5 wt% or less, about 1.5 wt% or less, about 1.0 wt% or less, about 0.9
wt% or less, about
0.75 wt% or less, or about 0.6 wt% or less. Further additionally or
alternately when more than one
hydrogenation metal is present, the collective amount of hydrogenation metals
can be at least about
0.1 wt% based on the total weight of the catalyst, for example at least about
0.25 wt%, at least
about 0.5 wt%, at least about 0.6 wt%, at least about 0.75 wt%, or at least
about 1 wt%. Still further
additionally or alternately when more than one hydrogenation metal is present,
the collective
amount of hydrogenation metals can be about 35 wt% or less based on the total
weight of the
catalyst, for example about 30 wt% or less, about 25 wt% or less, about 20 wt%
or less, about 15
wt% or less, about 10 wt% or less, or about 5 wt% or less. In embodiments
wherein the supported
metal comprises a noble metal, the amount of noble metal(s) is typically less
than about 2 wt %,
for example less than about 1 wt%, about 0.9 wt % or less, about 0.75 wt % or
less, or about 0.6
wt % or less. It is noted that hydrocracking under sour conditions is
typically performed using a
base metal (or metals) as the hydrogenation metal.
[0073] In various aspects, the conditions selected for hydrocracking for
lubricant base stock
production can depend on the desired level of conversion, the level of
contaminants in the input
feed to the hydrocracking stage, and potentially other factors. For example,
hydrocracking
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
conditions can be referred to as sour conditions or sweet conditions,
depending on the level of
sulfur and/or nitrogen present within a feed. 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 under sweet conditions. In
various aspects,
hydrocracking can be performed on a thermally cracked resid, such as a
deasphalted oil derived
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from a thermally cracked resid. In some aspects, such as aspects where an
optional hydrotreating
step is used prior to hydrocracking, the thermally cracked resid may
correspond to a sweet feed.
In other aspects, the thermally cracked resid may represent a feed for
hydrocracking under sour
conditions.
[0074] A hydrocracking process under sour conditions can be carried out at
temperatures of
about 550 F (288 C) to about 840 F (449 C), hydrogen partial pressures of from
about 1500 psig
to about 5000 psig (10.3 MPag to 34.6 MPag), liquid hourly space velocities of
from 0.0511-1 to 10
h-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 1500 psig to
about 3000 psig
(10.3 MPag-20.9 MPag), 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 11-1 to
about 50 h-1, or
from about 0.511-1 to about 20 h-1, preferably from about 1.011-1 to about
4.011-1.
[0075] In some aspects, a portion of the hydrocracking catalyst can be
contained in a second
reactor stage. In such aspects, a first reaction stage of the hydroprocessing
reaction system can
include one or more hydrotreating and/or hydrocracking catalysts. The
conditions in the first
reaction stage can be suitable for reducing the sulfur and/or nitrogen content
of the feedstock. 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 contaminant. 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.
[0076] 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
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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).
[0077] 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 H2S. These different products
can be separated
from each other in any convenient manner. Similarly, one or more distillate
fuel fractions can be
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 range is subjected to further hydroprocessing in a second
hydroprocessing stage.
[0078] A
hydrocracking 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 hydrocracking stage can have less severe
conditions than a
hydrocracking process in a sour stage. Suitable hydrocracking conditions for a
non-sour stage can
include, but are not limited to, conditions similar to a first or sour stage.
Suitable hydrocracking
conditions can include temperatures of about 500 F (260 C) to about 840 F (449
C), hydrogen
partial pressures of from about 1500 psig to about 5000 psig (10.3 MPag to
34.6 MPag), liquid
hourly space velocities of from 0.05 to
1011-1, 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 1500 psig to about 3000 psig (10.3 MPag-20.9 MPag),
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 h-1 to about 50 h-1, or from about 0.5 h-1 to about 20
h-1-, preferably from
about 1.011-1 to about 4.011-1.
[0079] In
still another aspect, the same conditions can be used for hydrotreating and
hydrocracking beds or stages, such as using hydrotreating conditions for both
or using
hydrocracking conditions for both. In yet another embodiment, the pressure for
the hydrotreating
and hydrocracking beds or stages can be the same.
[0080] In
yet another aspect, a hydroprocessing reaction system may include more than
one
hydrocracking stage. If multiple hydrocracking 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 1500 psig (10.3 MPag). In such an aspect, other
hydrocracking processes
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can be performed under conditions that may include lower hydrogen partial
pressures. Suitable
hydrocracking conditions for an additional hydrocracking stage can include,
but are not limited to,
temperatures of about 500 F (260 C) to about 840 F (449 C), hydrogen partial
pressures of from
about 250 psig to about 5000 psig (1.8 MPag to 34.6 MPag), liquid hourly space
velocities of from
0.05 to 10
h-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 for an additional
hydrocracking 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 psig to about 3000 psig (3.5 MPag-20.9 MPag), 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 to
about 50 11-1, or from about 0.5 11-1 to about 20 11-1, and preferably
from about 1.0 h-1 to about 4.0 h-1.
Hydroprocessed Effluent ¨ Solvent Dewaxing to form Group I Bright stock
[0081] The
hydroprocessed deasphalted oil (optionally including hydroprocessed vacuum
gas oil) can be separated to form one or more fuel boiling range fractions
(such as naphtha or
distillate fuel boiling range fractions) and at least one lubricant base stock
boiling range fraction.
The lubricant base stock boiling range fraction(s) can then be solvent dewaxed
to produce a
lubricant base stock product with a reduced (or eliminated) tendency to form
haze. Lubricant base
stocks (including bright stock) formed by hydroprocessing a deasphalted oil
and then solvent
dewaxing the hydroprocessed effluent can tend to be Group I base stocks due to
having an
aromatics content of at least 10 wt%.
[0082]
Solvent dewaxing typically involves mixing a feed with chilled dewaxing
solvent to
form an oil-solvent solution. Precipitated wax is thereafter separated by, for
example, filtration.
The temperature and solvent are selected so that the oil is dissolved by the
chilled solvent while
the wax is precipitated.
[0083] An
example of a suitable solvent dewaxing process involves the use of a cooling
tower where solvent is prechilled and added incrementally at several points
along the height of the
cooling tower. The oil-solvent mixture is agitated during the chilling step to
permit substantially
instantaneous mixing of the prechilled solvent with the oil. The prechilled
solvent is added
incrementally along the length of the cooling tower so as to maintain an
average chilling rate at or
below 10 F per minute, usually between about 1 to about 5 F per minute. The
final temperature of
the oil-solvent/precipitated wax mixture in the cooling tower will usually be
between 0 and 50 F
(-17.8 to 10 C). The mixture may then be sent to a scraped surface chiller to
separate precipitated
wax from the mixture.
[0084]
Representative dewaxing solvents are aliphatic ketones having 3-6 carbon atoms
such
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as methyl ethyl ketone and methyl isobutyl ketone, low molecular weight
hydrocarbons such as
propane and butane, and mixtures thereof The solvents may be mixed with other
solvents such as
benzene, toluene or xylene.
[0085] In general, the amount of solvent added will be sufficient to
provide a liquid/solid
weight ratio between the range of 5/1 and 20/1 at the dewaxing temperature and
a solvent/oil
volume ratio between 1.5/1 to 5/1. The solvent dewaxed oil can be dewaxed to a
pour point of -
6 C or less, or -10 C or less, or -15 C or less, depending on the nature of
the target lubricant base
stock product. Additionally or alternately, the solvent dewaxed oil can be
dewaxed to a cloud point
of -2 C or less, or -5 C or less, or -10 C or less, depending on the nature of
the target lubricant
base stock product. The resulting solvent dewaxed oil can be suitable for use
in forming one or
more types of Group I base stocks. Preferably, a bright stock formed from the
solvent dewaxed oil
can have a cloud point below -5 C. The resulting solvent dewaxed oil can have
a viscosity index
of at least 90, or at least 95, or at least 100. Preferably, at least 10 wt%
of the resulting solvent
dewaxed oil (or at least 20 wt%, or at least 30 wt%) can correspond to a Group
I bright stock having
a kinematic viscosity at 100 C of at least 15 cSt, or at least 20 cSt, or at
least 25 cSt, such as up to
50 cSt or more.
[0086] In some aspects, the reduced or eliminated tendency to form haze for
the lubricant
base stocks formed from the solvent dewaxed oil can be demonstrated by a
reduced or minimized
difference between the cloud point temperature and pour point temperature for
the lubricant base
stocks. In various aspects, the difference between the cloud point and pour
point for the resulting
solvent dewaxed oil and/or for one or more lubricant base stocks, including
one or more bright
stocks, formed from the solvent dewaxed oil, can be 22 C or less, or 20 C or
less, or 15 C or less,
or 10 C or less, or 8 C or less, or 5 C or less. Additionally or alternately,
a reduced or minimized
tendency for a bright stock to form haze over time can correspond to a bright
stock having a cloud
point of -10 C or less, or -8 C or less, or -5 C or less, or -2 C or less.
Additional Hydroprocessing ¨ Catalytic Dewaxing, Hydrofinishing, and Optional
Hydrocracking
[0087] In some alternative aspects, at least a lubricant boiling range
portion of the
hydroprocessed deasphalted oil can be exposed to further hydroprocessing
(including catalytic
dewaxing) to form either Group I and/or Group II base stocks, including Group
I and/or Group II
bright stock. In some aspects, a first lubricant boiling range portion of the
hydroprocessed
deasphalted oil can be solvent dewaxed as described above while a second
lubricant boiling range
portion can be exposed to further hydroprocessing. In other aspects, only
solvent dewaxing or only
further hydroprocessing can be used to treat a lubricant boiling range portion
of the hydroprocessed
deasphalted oil.
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[0088]
Optionally, the further hydroprocessing of the lubricant boiling range portion
of the
hydroprocessed deasphalted oil can also include exposure to hydrocracking
conditions before
and/or after the exposure to the catalytic dewaxing conditions. At this point
in the process, the
hydrocracking can be considered "sweet" hydrocracking, as the hydroprocessed
deasphalted oil
can have a sulfur content of 200 wppm or less.
[0089]
Suitable hydrocracking conditions can include exposing the feed to a
hydrocracking
catalyst as previously described above. Optionally, it can be preferable to
use a USY zeolite with
a silica to alumina ratio of at least 30 and a unit cell size of less than
24.32 Angstroms as the zeolite
for the hydrocracking catalyst, in order to improve the VI uplift from
hydrocracking and/or to
improve the ratio of distillate fuel yield to naphtha fuel yield in the fuels
boiling range product.
[0090]
Suitable hydrocracking conditions can also include temperatures of about 500 F
(260 C) to about 840 F (449 C), hydrogen partial pressures of from about 1500
psig to about 5000
psig (10.3 MPag to 34.6 MPag), liquid hourly space velocities of from 0.05 11-
1 to 10 11-1, 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 1500 psig to about
3000 psig (10.3 MPag-
20.9 MPag), 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 to
about 50 h-1-, or from about 0.5
11-1 to about 20 h-1, and preferably from about 1.011-1 to about 4.011-1.
[0091] For
catalytic dewaxing, suitable dewaxing catalysts can include molecular sieves
such
as crystalline aluminosilicates (zeolites). In an embodiment, the molecular
sieve can comprise,
consist essentially of, or be ZSM-22, ZSM-23, ZSM-48. Optionally but
preferably, molecular
sieves that are selective for dewaxing by isomerization as opposed to cracking
can be used, such
as ZSM-48, ZSM-23, or a combination thereof Additionally or alternately, the
molecular sieve
can comprise, consist essentially of, or be a 10-member ring 1-D molecular
sieve, such as EU-2,
EU-11, ZBM-30, ZSM-48, or ZSM-23. ZSM-48 is most preferred. Note that a
zeolite having the
ZSM-23 structure with a silica to alumina ratio of from about 20:1 to about
40:1 can sometimes be
referred to as SSZ-32. Optionally but preferably, the dewaxing catalyst can
include a binder for
the molecular sieve, such as alumina, -Mania, silica, silica-alumina,
zirconia, or a combination
thereof, for example alumina and/or titania or silica and/or zirconia and/or -
Mania.
[0092]
Preferably, the dewaxing catalysts used in processes according to the
invention are
catalysts with a low ratio of silica to alumina. For example, for ZSM-48, the
ratio of silica to
alumina in the zeolite can be about 100:1 or less, such as about 90:1 or less,
or about 75:1 or less,
or about 70:1 or less. Additionally or alternately, the ratio of silica to
alumina in the ZSM-48 can
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beat least about 50:1, such as at least about 60:1, or at least about 65:1.
[0093] In various embodiments, the catalysts according to the invention
further include a
metal hydrogenation component. The metal hydrogenation component is typically
a Group VI
and/or a Group VIII metal. Preferably, the metal hydrogenation component can
be a combination
of a non-noble Group VIII metal with a Group VI metal. Suitable combinations
can include Ni,
Co, or Fe with Mo or W, preferably Ni with Mo or W.
[0094] The metal hydrogenation component may be added to the 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
exchange, where a metal precursor is added to a mixture of zeolite (or zeolite
and binder) prior to
extrusion.
[0095] The amount of metal in the catalyst can be at least 0.1 wt% based on
catalyst, or at
least 0.5 wt%, or at least 1.0 wt%, or at least 2.5 wt%, or at least 5.0 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 embodiments where the
metal is a
combination of a non-noble Group VIII metal with a Group VI 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%.
[0096] The dewaxing catalysts useful in processes according to the
invention 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.
Additionally or alternately,
the binder can have a surface area of at least about 25 m2/g. The amount of
zeolite in a catalyst
formulated using a binder can be from about 30 wt% zeolite to 90 wt% zeolite
relative to the
combined weight of binder and zeolite. Preferably, the amount of zeolite is at
least about 50 wt%
of the combined weight of zeolite and binder, such as at least about 60 wt% or
from about 65 wt%
to about 80 wt%.
[0097] Without being bound by any particular theory, it is believed that
use of a low surface
area binder reduces the amount of binder surface area available for the
hydrogenation metals
supported on the catalyst. This leads to an increase in the amount of
hydrogenation metals that are
supported within the pores of the molecular sieve in the catalyst.
[0098] A zeolite 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
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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. The amount of framework
alumina in the catalyst
may range from 0.1 to 3.33 wt%, or 0.1 to 2.7 wt%, or 0.2 to 2 wt%, or 0.3 to
1 wt%.
[0099]
Effective conditions for catalytic dewaxing of a feedstock in the presence of
a
dewaxing catalyst can include a temperature of from 280 C to 450 C, preferably
343 C to 435 C,
a hydrogen partial pressure of from 3.5 MPag to 34.6 MPag (500 psig to 5000
psig), preferably 4.8
MPag to 20.8 MPag, and a hydrogen circulation rate of from 178 m3/m3 (1000
SCF/B) to 1781
m3/m3 (10,000 scf/B), preferably 213 m3/m3 (1200 SCF/B) to 1068 m3/m3 (6000
SCF/B). The
LHSV can be from about 0.2 1-11 to about 10 11-1, such as from about 0.5 1-11
to about 5 ft' and/or
from about 1 h-1 to about 4 h-1.
[00100]
Before and/or after catalytic dewaxing, the hydroprocessed deasphalted oil
(i.e., at least
a lubricant boiling range portion thereof) can optionally be exposed to an
aromatic saturation
catalyst, which can alternatively be referred to as a hydrofinishing catalyst.
Exposure to the
aromatic saturation catalyst can occur either before or after fractionation.
If aromatic saturation
occurs after fractionation, the aromatic saturation can be performed on one or
more portions of the
fractionated product. Alternatively, the entire effluent from the last
hydrocracking or dewaxing
process can be hydrofinished and/or undergo aromatic saturation.
[00101] Hydrofinishing and/or aromatic saturation catalysts can include
catalysts containing
Group VI metals, Group VIII 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 VIII 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 about 30 wt. % or greater based on catalyst. For supported
hydrotreating catalysts, 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 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
about 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.
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[00102] Hydrofinishing conditions can include temperatures from about 125 C to
about 425 C,
preferably about 180 C to about 280 C, a hydrogen partial pressure from about
500 psig (3.4 MPa)
to about 3000 psig (20.7 MPa), preferably about 1500 psig (10.3 MPa) to about
2500 psig (17.2
MPa), and liquid hourly space velocity from about 0.1 hr-1 to about 5 hr-1
LHSV, preferably about
0.5 hr-1 to about 1.5 hr-1. Additionally, a hydrogen treat gas rate of from
35.6 m3/m3 to 1781 m3/m3
(200 SCF/B to 10,000 SCF/B) can be used.
Solvent Processing of Catalytically Dewaxed Effluent or Input Flow to
Catalytic Dewaxing
[00103] For deasphalted oils derived from propane deasphalting, the further
hydroprocessing
(including catalytic dewaxing) can be sufficient to form lubricant base stocks
with low haze
formation and unexpected compositional properties. For deasphalted oils
derived from C4+
deasphalting, after the further hydroprocessing (including catalytic
dewaxing), the resulting
catalytically dewaxed effluent can be solvent processed to form one or more
lubricant base stock
products with a reduced or eliminated tendency to form haze. The type of
solvent processing can
be dependent on the nature of the initial hydroprocessing (hydrotreatment
and/or hydrocracking)
and the nature of the further hydroprocessing (including dewaxing).
[00104] In aspects where the initial hydroprocessing is less severe,
corresponding to 10 wt%
to 40 wt% conversion relative to ¨700 F (370 C), the subsequent solvent
processing can
correspond to solvent dewaxing. The solvent dewaxing can be performed in a
manner similar to
the solvent dewaxing described above. However, this solvent dewaxing can be
used to produce a
Group II lubricant base stock. In some aspects, when the initial
hydroprocessing corresponds to
wt% to 40 wt% conversion relative to 370 C, the catalytic dewaxing during
further
hydroprocessing can also be performed at lower severity, so that at least 6
wt% wax remains in the
catalytically dewaxed effluent, or at least 8 wt%, or at least 10 wt%, or at
least 12 wt%, or at least
wt%, such as up to 20 wt%. The solvent dewaxing can then be used to reduce the
wax content
in the catalytically dewaxed effluent by 2 wt% to 10 wt%. This can produce a
solvent dewaxed oil
product having a wax content of 0.1 wt% to 12 wt%, or 0.1 wt% to 10 wt%, or
0.1 wt% to 8 wt%,
or 0.1 wt% to 6 wt%, or 1 wt% to 12 wt%, or 1 wt% to 10 wt%, or 1 wt% to 8
wt%, or 4 wt% to
12 wt%, or 4 wt% to 10 wt%, or 4 wt% to 8 wt%, or 6 wt% to 12 wt%, or 6 wt% to
10 wt%. In
particular, the solvent dewaxed oil can have a wax content of 0.1 wt% to 12
wt%, or 0.1 wt% to 6
wt%, or 1 wt% to 10 wt%, or 4 wt% to 12 wt%.
[00105] In other aspects, the subsequent solvent processing can correspond
to solvent
extraction. Solvent extraction can be used to reduce the aromatics content
and/or the amount of
polar molecules. The solvent extraction process selectively dissolves aromatic
components to form
an aromatics-rich extract phase while leaving the more paraffinic components
in an aromatics-poor
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raffinate phase. Naphthenes are distributed between the extract and raffinate
phases. Typical
solvents for solvent extraction include phenol, furfural and N-methyl
pyrrolidone. By controlling
the solvent to oil ratio, extraction temperature and method of contacting
distillate to be extracted
with solvent, one can control the degree of separation between the extract and
raffinate phases.
Any convenient type of liquid-liquid extractor can be used, such as a counter-
current liquid-liquid
extractor. Depending on the initial concentration of aromatics in the
deasphalted oil, the raffinate
phase can have an aromatics content of 5 wt% to 25 wt%. For typical feeds, the
aromatics contents
can be at least 10 wt%.
[00106] Optionally, the raffinate from the solvent extraction can be under-
extracted. In such
aspects, the extraction is carried out under conditions such that the
raffinate yield is maximized
while still removing most of the lowest quality molecules from the feed.
Raffinate yield may be
maximized by controlling extraction conditions, for example, by lowering the
solvent to oil treat
ratio and/or decreasing the extraction temperature. In various aspects, the
raffinate yield from
solvent extraction can be at least 40 wt%, or at least 50 wt%, or at least 60
wt%, or at least 70 wt%.
[00107] The solvent processed oil (solvent dewaxed or solvent extracted)
can have a pour
point of -6 C or les, or -10 C or less, or -15 C or less, or -20 C or less,
depending on the nature of
the target lubricant base stock product. Additionally or alternately, the
solvent processed oil
(solvent dewaxed or solvent extracted) can have a cloud point of -2 C or less,
or -5 C or less, or -
C or less, depending on the nature of the target lubricant base stock product.
Pour points and
cloud points can be determined according to ASTM D97 and ASTM D2500,
respectively. The
resulting solvent processed oil can be suitable for use in forming one or more
types of Group II
base stocks. The resulting solvent dewaxed oil can have a viscosity index of
at least 80, or at least
90, or at least 95, or at least 100, or at least 110, or at least 120.
Viscosity index can be determined
according to ASTM D2270. Preferably, at least 10 wt% of the resulting solvent
processed oil (or
at least 20 wt%, or at least 30 wt%) can correspond to a Group II base stock
having a kinematic
viscosity at 100 C of 6 cSt to 20 cSt, or 6 cSt to 16 cSt, or 6 cSt to 14 cSt,
or 6 cSt to 12 cSt, or 8
cSt to 20 cSt, or 8 cSt to 16 cSt, or 8 cSt to 14 cSt, or 8 cSt to 12 cSt, or
10 cSt to 20 cSt, or 10 cSt
to 16 cSt, or 10 cSt to 14 cSt Kinematic viscosity can be determined according
to ASTM D445.
Additionally or alternately, the resulting base stock can have a turbidity of
at least 1.5 (in
combination with a cloud point of less than 0 C), or can have a turbidity of
at least 2.0, and/or can
have a turbidity of 4.0 or less, or 3.5 or less, or 3.0 or less. In
particular, the turbidity can be 1.5 to
4.0, or 1.5 to 3.0, or 2.0 to 4.0, or 2.0 to 3.5.
Group II Base Stock Products
[00108] For deasphalted oils derived from propane, butane, pentane, hexane
and higher or
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mixtures thereof, the further hydroprocessing (including catalytic dewaxing)
and potentially
solvent processing can be sufficient to form lubricant base stocks with low
haze formation (or no
haze formation) and novel compositional properties. Traditional products
manufactured today
with kinematic viscosity of about 32 cSt at 100 C contain aromatics that are >
10% and/or sulfur
that is > 0.03% of the base oil.
[00109] In various aspects, base stocks produced according to methods
described herein can
have a kinematic viscosity of at least 14 cSt, or at least 20 cSt, or at least
25 cSt, or at least 30 cSt,
or at least 32 cSt at 100 C and can contain less than 10 wt% aromatics /
greater than 90 wt%
saturates and less than 0.03% sulfur. Optionally, the saturates content can be
still higher, such as
greater than 95 wt%, or greater than 97 wt%. In addition, detailed
characterization of the
branchiness (branching) of the molecules by C-NMR reveals a high degree of
branch points as
described further below in the examples. This can be quantified by examining
the absolute number
of methyl branches, or ethyl branches, or propyl branches individually or as
combinations thereof
This can also be quantified by looking at the ratio of branch points (methyl,
ethyl, or propyl)
compared to the number of internal carbons, labeled as epsilon carbons by C-
NMR. This
quantification of branching can be used to determine whether a base stock will
be stable against
haze formation over time. For 13C-NMR results reported herein, samples were
prepared to be 25-
30 wt% in CDC13 with 7% Chromium (III) -acetylacetonate added as a relaxation
agent. 13C NMR
experiments were performed on a JEOL ECS NMR spectrometer for which the proton
resonance
frequency is 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, 64 K data
points and 2400 scans. All spectra were referenced to TMS at Oppm. Spectra
were processed with
0.2-1 Hz of line broadening and baseline correction was applied prior to
manual integration. The
entire spectrum was integrated to determine the mole % of the different
integrated areas as follows:
170-190 PPM (aromatic C); 30-29.5 PPM (epsilon carbons); 15-14.5 PPM (terminal
and pendant
propyl groups) 14.5 - 14 PPM ¨ Methyl at the end of a long chain (alpha); 12-
10 PPM (pendant
and terminal ethyl groups). Total methyl content was obtained from proton NMR.
The methyl
signal at 0-1.1 PPM was integrated. The entire spectrum was integrated to
determine the mole%
of methyls. Average carbon numbers obtained from gas chromatography were used
to convert
mole% methyls to total methyls.
[00110] Also unexpected in the composition is the discovery using Fourier
Transform Ion
Cyclotron Resonance- Mass Spectrometry (FTICR-MS) and/or Field Desorption Mass
Spectrometry (FDMS) that the prevalence of smaller naphthenic ring structures
below 6 or below
7 or below 8 naphthene rings can be similar but the residual numbers of larger
naphthenic rings
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structures with 7 or more rings or 8+ rings or 9+ rings or 10+ rings is
diminished in base stocks
that are stable against haze formation.
[00111] For FTICR-MS results reported herein, the results were generated
according to the
method described in U.S. Patent 9,418,828. The method described in U.S. Patent
9,418,828
generally involves using laser desorption with Ag ion complexation (LDI-Ag) to
ionize petroleum
saturates molecules (including 538 C+ molecules) without fragmentation of the
molecular ion
structure. Ultra-high resolution Fourier Transform Ion Cyclotron Resonance
Mass Spectrometry is
applied to determine exact elemental formula of the saturates-Ag cations and
corresponding
abundances. The saturates fraction composition can be arranged by homologous
series and
molecular weights. The portion of U.S. Patent 9,418,828 related to determining
the content of
saturate ring structures in a sample is incorporated herein by reference.
[00112] For FDMS results reported herein, Field desorption (FD) is a soft
ionization method
in which a high-potential electric field is applied to an emitter (a filament
from which tiny
"whiskers" have formed) that has been coated with a diluted sample resulting
in the ionization of
gaseous molecules of the analyte. Mass spectra produced by FD are dominated by
molecular
radical cations M+. or in some cases protonated molecular ions [M+H1+. Because
FDMS cannot
distinguish between molecules with 'n' naphthene rings and molecules with
'n+7' rings, the FDMS
data was "corrected" by using the FTICR-MS data from the most similar sample.
The FDMS
correction was performed by applying the resolved ratio of "n" to "n+7" rings
from the FTICR-
MS to the unresolved FDMS data for that particular class of molecules. Hence,
the FDMS data is
shown as "corrected" in the figures.
[00113] Base oils of the compositions described above have further been
found to provide the
advantage of being haze free upon initial production and remaining haze free
for extended periods
of time. This is an advantage over the prior art of high saturates heavy base
stocks that was
unexpected.
[00114] Additionally, it has been found that these base stocks can be
blended with additives
to form formulated lubricants, such as but not limited to marine oils, engine
oils, greases, paper
machine oils, and gear oils. These additives may include, but are not
restricted to, detergents,
dispersants, antioxidants, viscosity modifiers, and pour point depressants.
More generally, a
formulated lubricating including a base stock produced from a deasphalted oil
may additionally
contain one or more of the other commonly used lubricating oil performance
additives including
but not limited to antiwear agents, dispersants, other detergents, corrosion
inhibitors, rust
inhibitors, metal deactivators, extreme pressure additives, anti-seizure
agents, wax modifiers,
viscosity index improvers, viscosity modifiers, fluid-loss additives, seal
compatibility agents,
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friction modifiers, 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 Klamann in
Lubricants and
Related Products, Verlag Chemie, Deerfield Beach, FL; ISBN 0-89573-177-0.
These additives are
commonly delivered with varying amounts of diluent oil, that may range from 5
weight percent to
50 weight percent.
[00115] When so blended, the performance as measured by standard low
temperature tests
such as the Mini-Rotary Viscometer (MRV) and Brookfield test has been shown to
be superior to
formulations blended with traditional base oils.
[00116] It has also been found that the oxidation performance, when blended
into industrial
oils using common additives such as, but not restricted to, defoamants, pour
point depressants,
antioxidants, rust inhibitors, has exemplified superior oxidation performance
in standard oxidation
tests such as the US Steel Oxidation test compared to traditional base stocks.
[00117] Other performance parameters such as interfacial properties,
deposit control, storage
stability, and toxicity have also been examined and are similar to or better
than traditional base
oils.
[00118] In addition to being blended with additives, the base stocks
described herein can also
be blended with other base stocks to make a base oil. These other base stocks
include solvent
processed base stocks, hydroprocessed base stocks, synthetic base stocks, base
stocks derived from
Fisher-Tropsch processes, PAO, and naphthenic base stocks. Additionally or
alternately, the other
base stocks can include Group I base stocks, Group II base stocks, Group III
base stocks, Group
IV base stocks, and/or Group V base stocks. Additionally or alternately, still
other types of base
stocks for blending can include hydrocarbyl aromatics, alkylated aromatics,
esters (including
synthetic and/or renewable esters), and or other non-conventional or
unconventional base stocks.
These base oil blends of the inventive base stock and other base stocks can
also be combined with
additives, such as those mentioned above, to make formulated lubricants.
Configuration Examples
[00119] FIG. 1 schematically shows a first configuration for processing of a
deasphalted oil feed
110. Optionally, deasphalted oil feed 110 can include a vacuum gas oil boiling
range portion. In
FIG. 1, a deasphalted oil feed 110 is exposed to hydrotreating and/or
hydrocracking catalyst in a
first hydroprocessing stage 120. The hydroprocessed effluent from first
hydroprocessing stage 120
can be separated into one or more fuels fractions 127 and a 370 C+ fraction
125. The 370 C+
fraction 125 can be solvent dewaxed 130 to form one or more lubricant base
stock products, such
as one or more light neutral or heavy neutral base stock products 132 and a
bright stock product
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134.
[00120] FIG. 2 schematically shows a second configuration for processing a
deasphalted oil
feed 110. In FIG. 2, solvent dewaxing stage 130 is optional. The effluent
from first
hydroprocessing stage 120 can be separated to form at least one or more fuels
fractions 127, a first
370 C+ portion 245, and a second optional 370 C+ portion 225 that can be used
as the input for
optional solvent dewaxing stage 130. The first 370 C+ portion 245 can be used
as an input for a
second hydroprocessing stage 250. The second hydroprocessing stage can
correspond to a sweet
hydroprocessing stage for performing catalytic dewaxing, aromatic saturation,
and optionally
further performing hydrocracking. In FIG. 2, at least a portion 253 of the
catalytically dewaxed
output 255 from second hydroprocessing stage 250 can be solvent dewaxed 260 to
form at least a
solvent processed lubricant boiling range product 265 that has a T10 boiling
point of at least 510 C
and that corresponds to a Group II bright stock.
[00121] FIG. 3 schematically shows another configuration for producing a Group
II bright
stock. In FIG. 3, at least a portion 353 of the catalytically dewaxed output
355 from the second
hydroprocessing stage 250 is solvent extracted 370 to form at least a
processed lubricant boiling
range product 375 that has a T10 boiling point of at least 510 C and that
corresponds to a Group
II bright stock.
[00122] FIG. 6 schematically shows yet another configuration for producing a
Group II bright
stock. In FIG. 6, a vacuum resid feed 675 and a deasphalting solvent 676 is
passed into a
deasphalting unit 680. In some aspects, deasphalting unit 680 can perform
propane deasphalting,
but in other aspects a C4+ solvent can be used. Deasphalting unit 680 can
produce a rock or asphalt
fraction 682 and a deasphalted oil 610. Optionally, deasphalted oil 610 can be
combined with
another vacuum gas oil boiling range feed 671 prior to being introduced into
first (sour)
hydroprocessing stage 620. A lower boiling portion 627 of the effluent from
hydroprocessing stage
620 can be separated out for further use and/or processing as one or more
naphtha fractions and/or
distillate fractions. A higher boiling portion 625 of the hydroprocessing
effluent can be a) passed
into a second (sweet) hydroprocessing stage 650 and/or b) withdrawn 626 from
the processing
system for use as a fuel, such as a fuel oil or fuel oil blendstock. Second
hydroprocessing stage 650
can produce an effluent that can be separated to form one or more fuels
fractions 657 and one or
more lubricant base stock fractions 655, such as one or more bright stock
fractions.
[00123] FIGS. 11 to 13 show examples of using blocked operation and/or partial
product recycle
during lubricant production based on a feed including deasphalted resid. In
FIGS. 11 to 13, after
initial sour stage processing, the hydroprocessed effluent is fractionated to
form light neutral, heavy
neutral, and brightstock portions. FIG. 11 shows an example of the process
flow during processing
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to form light neutral base stock. FIG. 12 shows an example of the process flow
during processing
to form heavy neutral base stock. FIG. 13 shows an example of the process flow
during processing
to form brightstock.
[00124] In FIG. 11, a feed 705 is introduced into a deasphalter 710. The
deasphalter 710
generates a deasphalted oil 715 and deasphalter rock or residue 718. The
deasphalted oil 715 is
then processed in a sour processing stage 720. Optionally, a portion 771 of
recycled light neutral
base product 762 can be combined with deasphalted oil 715. Sour processing
stage 720 can include
one or more of a deasphalting catalyst, a hydrotreating catalyst, a
hydrocracking catalyst, and/or
an aromatic saturation catalyst. The conditions in sour processing stage 720
can be selected to at
least reduce the sulfur content of the hydroprocessed effluent 725 to 20 wppm
or less. This can
correspond to 15 wt% to 40 wt% conversion of the feed relative to 370 C.
Optionally, the amount
of conversion in the sour processing stage 720 can be any convenient higher
amount so long as the
combined conversion in sour processing stage 720 and sweet processing stage
750 is 90 wt% or
less.
[00125] The hydroprocessed effluent 725 can then be passed into fractionation
stage 730 for
separation into a plurality of fractions. In the example shown in FIG. 11, the
hydroprocessed
effluent is separated into a light neutral portion 732, a heavy neutral
portion 734, and a brightstock
portion 736. To allow for blocked operation, the light neutral portion 732 can
be sent to
corresponding light neutral storage 742, the heavy neutral portion 734 can be
sent to corresponding
heavy neutral storage 744, and the brightstock portion 736 can be sent to
corresponding brightstock
storage 746. A lower boiling range fraction 731 corresponding to fuels and/or
light ends can also
be generated by fractionation stage 730. Optionally, fractionation stage can
generate a plurality of
lower boiling range fractions 731.
[00126] FIG. 11 shows an example of the processing system during a light
neutral processing
block. In FIG. 11, the feed 752 to sweet processing stage 750 corresponds to a
feed derived from
light neutral storage 742. The sweet processing stage 750 can include at least
dewaxing catalyst,
and optionally can further include one or more of hydrocracking catalyst and
aromatics saturation
catalyst. The dewaxed effluent 755 from sweet processing stage 750 can then be
passed into a
fractionator 760 to form light neutral base stock product 762. A lower boiling
fraction 761
corresponding to fuels and/or light ends can also be separated out by
fractionator 760. Optionally,
a portion of light neutral base stock 762 can be recycled. The recycled
portion of light neutral base
stock 762 can be used as a recycled feed portion 771 and/or as a recycled
portion 772 that is added
to light neutral storage 742. Recycling a portion 771 for use as part of the
feed can be beneficial
for increasing the lifetime of the catalysts in sour processing stage 720.
Recycling a portion 772
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to light neutral storage 742 can be beneficial for increasing conversion
and/or VI.
[00127] FIG. 12 shows the same processing configuration during processing of a
heavy neutral
block. In FIG. 12, the feed 754 to sweet processing stage 750 is derived from
heavy neutral storage
744. The dewaxed effluent 755 from sweet processing stage 750 can be
fractionated 760 to form
lower boiling portion 761, heavy neutral base stock product 764, and light
neutral base stock
product 762. Because block operation to form a heavy neutral base stock
results in production of
both a light neutral product 762 and a heavy neutral product 764, various
optional recycle streams
can also be used. In the example shown in FIG. 12, optional recycle portions
771 and 772 can be
used for recycle of the light neutral product 762. Additionally, optional
recycle portions 781 and
784 can be used for recycle of the heavy neutral product 764. Recycle portions
781 and 784 can
provide similar benefits to those for recycle portions 771 and/or 772.
[00128] FIG. 13 shows the same processing configuration during processing of a
bright stock
block. In FIG. 13, the feed 756 to sweet processing stage 750 is derived from
bright stock storage
746. The dewaxed effluent 755 from sweet processing stage 750 can be
fractionated 760 to form
lower boiling portion 761, bottoms product 766, heavy neutral base stock
product 764, and light
neutral base stock product 762. Bottoms product 766 can then be extracted 790
to form a bright
stock product 768. The aromatic extract 793 produced in extractor 790 can be
recycled for use,
for example, as part of the feed to deasphalter 710.
[00129] Because block operation to form a bright stock results in production
of a bright stock
product 768 as well as a light neutral product 762 and a heavy neutral product
764, various optional
recycle streams can also be used. In the example shown in FIG. 9, optional
recycle portions 771
and 772 can be used for recycle of the light neutral product 762, while
optional recycle portions
781 and 784 can be used for recycle of the heavy neutral product 764.
Additionally, optional
recycle portions 791 and 796 can be used for recycle of the bottoms product
766. Recycle portions
791 and 796 can provide similar benefits to those for recycle portions 771,
772, 781, and/or 784.
Example 1
[00130] A deasphalted oil and vacuum gas oil mixture shown in Table B was
processed in a
configuration similar to FIG. 3.
Table 1 ¨ Pentane deasphalted oil (65%) and vacuum gas oil (35%) properties
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API Gravity 13.7
Sulfur (wt%) 3.6
Nitrogen (wppm) 2099
Ni (wppm) 5.2
V (wppm) 14.0
CCR (wt%) 8.1
Wax (wt%) 4.2
GCD Distillation (wt%) ( C)
5% 422
10% 465
30% 541
50% 584
70% n/a
90% 652
[00131] The deasphalted oil in Table 1 was processed at 0.2 hr-1 LHSV, a treat
gas rate of
8000scf/b, and a pressure of 2250 psig over a catalyst fill of 50 vol%
demetalization catalyst, 42.5
vol% hydrotreating catalyst, and 7.5% hydrocracking catalyst by volume. The
demetallization
catalyst was a commercially available large pore supported demetallization
catalyst. The
hydrotreating catalyst was a stacked bed of commercially available supported
NiMo hydrotreating
catalyst and commercially available bulk NiMo catalyst. The hydrocracking
catalyst was a
standard distillate selective catalyst used in industry. Such catalysts
typically include NiMo or
NiW on a zeolite / alumina support. Such catalysts typically have less than 40
wt% zeolite of a
zeolite with a unit cell size of less than 34.38 Angstroms. A preferred
zeolite content can be less
than 25 wt% and/or a preferred unit cell size can be less than 24.32
Angstroms. Activity for such
catalysts can be related to the unit cell size of the zeolite, so the activity
of the catalyst can be
adjusted by selecting the amount of zeolite. The feed was exposed to the
demetallization catalyst
at 745 F (396 C) and exposed to the combination of the hydrotreating and
hydrocracking catalyst
at 761 F (405 C) in an isothermal fashion.
[00132] The above processing conditions resulted in conversion relative to 510
C of 73.9 wt%
and conversion relative to 370 C of 50 wt%. The hydroprocessed effluent was
separated to remove
fuels boiling range portions from a 370 C+ portion. The resulting 370 C+
portion was then further
hydroprocessed. The further hydroprocessing included exposing the 370 C+
portion to a 0.6 wt%
Pt on ZSM-48 dewaxing catalyst (70:1 silica to alumina ratio, 65 wt% zeolite
to 35 wt% binder)
followed by a 0.3 wt% Pt / 0.9 wt% Pd on MCM-41 aromatic saturation catalyst
(65% zeolite to
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35 wt% binder). The operating conditions included a hydrogen pressure of 2400
psig, a treat gas
rate of 5000 scf/b, a dewaxing temperature of 658 F (348 C), a dewaxing
catalyst space velocity
of 1.0 hr', an aromatic saturation temperature of 460 F (238 C), and an
aromatic saturation
catalyst space velocity of 1.0 hr-1. The properties of the 560 C+ portion of
the catalytically
dewaxed effluent are shown in Table 2. Properties for a raffinate fraction and
an extract fraction
derived from the catalytically dewaxed effluent are also shown.
Table 2¨ Catalytically dewaxed effluent
Product Fraction 560 C+ Raffinate Extract
CDW effluent (yield 92.2%)
API 30.0 30.2 27.6
VI 104.2 105.2 89
KV A100 C 29.8 30.3 29.9
KV @40 C 401 405 412
Pour Pt ( C) -21 -30
Cloud Pt ( C) 7.8 -24
[00133] Although the catalytically dewaxed effluent product was initially
clear, haze developed
within 2 days. Solvent dewaxing of the catalytically dewaxed effluent product
in Table 2 did not
reduce the cloud point significantly (cloud after solvent dewaxing of 6.5 C)
and removed only
about 1 wt% of wax, due in part to the severity of the prior catalytic
dewaxing. However, extracting
the catalytically dewaxed product shown in Table 9 with N-methyl pyrrolidone
(NMP) at a solvent
/ water ratio of 1 and at a temperature of 100 C resulted in a clear and
bright product with a cloud
point of -24 C that appeared to be stable against haze formation. The
extraction also reduced the
aromatics content of the catalytically dewaxed product from about 2 wt%
aromatics to about 1
wt% aromatics. This included reducing the 3-ring aromatics content of the
catalytically dewaxed
effluent (initially about 0.2 wt%) by about 80%. This result indicates a
potential relationship
between waxy haze formation and the presence of polynuclear aromatics in a
bright stock.
Example 2
[00134] A feed similar to Example 1 was processed in a configuration similar
to FIG. 2, with
various processing conditions were modified. The initial hydroprocessing
severity was reduced
relative to the conditions in Example 1 so that the initial hydroprocessing
conversion was 59 wt%
relative to 510 C and 34.5 wt% relative to 370 C. These lower conversions were
achieved by
operating the demetallization catalyst at 739 F (393 C) and the hydrotreating
/ hydrocracking
catalyst combination at 756 F (402 C).
[00135] The hydroprocessed effluent was separated to separate fuels boiling
range fraction(s)
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from the 370 C+ portion of the hydroprocessed effluent. The 370 C+ portion was
then treated in
a second hydroprocessing stage over a hydrocracking catalyst and a dewaxing
catalyst.
Additionally, a small amount of a hydrotreating catalyst (hydrotreating
catalyst LHSV of 10 hr-1)
was included prior to the hydrocracking catalyst, and the feed was exposed to
the hydrotreating
catalyst under substantially the same conditions as the hydrocracking
catalyst. The reaction
conditions included a hydrogen pressure of 2400 psig and a treat gas rate of
5000 scf/b. In a first
run, the second hydroprocessing conditions were selected to under dewax the
hydroprocessed
effluent. The under-dewaxing conditions corresponded to a hydrocracking
temperature of 675 F
(357 C), a hydrocracking catalyst LHSV of 1.2 hr-1, a dewaxing temperature of
615 F (324 C), a
dewaxing catalyst LHSV of 1.2 hr-1, an aromatic saturation temperature of 460
F (238 C), and an
aromatic saturation catalyst LHSV of 1.2 hr-1. In a second run, the second
hydroprocessing
conditions were selected to more severely dewax the hydroprocessed effluent.
The higher severity
dewaxing conditions corresponded to a hydrocracking temperature of 675 F (357
C), a
hydrocracking catalyst LHSV of 1.2 hr-1, a dewaxing temperature of 645 F (340
C), a dewaxing
catalyst LHSV of 1.2 hr', an aromatic saturation temperature of 460 F (238 C),
and an aromatic
saturation catalyst LHSV of 1.2 hr-1. The 510 C+ portions of the catalytically
dewaxed effluent
are shown in Table 3.
Table 3¨ Catalytically dewaxed effluents
Product Fraction Under-dewaxed Higher severity
VI 106.6 106.4
KV A100 C 37.6 30.5
KV @40 C 551 396
Pour Pt ( C) -24 -24
Cloud Pt ( C) 8.6 4.9
[00136] Both samples in Table 3 were initially bright and clear, but a haze
developed in both
samples within one week. Both samples were solvent dewaxed. This reduced the
wax content of
the under-dewaxed sample to 6.8 wt% and the wax content of the higher severity
dewaxing sample
to 1.1 wt%. The higher severity dewaxing sample still showed a slight haze.
However, the under-
dewaxed sample, after solvent dewaxing, had a cloud point of -21 C and
appeared to be stable
against haze formation.
Example 3 ¨ Viscosity and Viscosity Index relationships
[00137] FIG. 4 shows an example of the relationship between processing
severity, kinematic
viscosity, and viscosity index for lubricant base stocks formed from a
deasphalted oil. The data in
FIG. 4 corresponds to lubricant base stocks formed form a pentane deasphalted
oil at 75 wt% yield
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on resid feed. The deasphalted oil had a solvent dewaxed VI of 75.8 and a
solvent dewaxed
kinematic viscosity at 100 C of 333.65.
[00138] In FIG. 4, kinematic viscosities (right axis) and viscosity indexes
(left axis) are shown
as a function of hydroprocessing severity (510 C+ conversion) for a
deasphalted oil processed in
a configuration similar to FIG. 1, with the catalysts described in Example 1.
As shown in FIG. 4,
increasing the hydroprocessing severity can provide VI uplift so that
deasphalted oil can be
converted (after solvent dewaxing) to lubricant base stocks. However,
increasing severity also
reduces the kinematic viscosity of the 510 C+ portion of the base stock, which
can limit the yield
of bright stock. The 370 C ¨ 510 C portion of the solvent dewaxed product can
be suitable for
forming light neutral and/or heavy neutral base stocks, while the 510 C+
portion can be suitable
for forming bright stocks and/or heavy neutral base stocks.
Example 4 ¨ Variations in Sweet and Sour Hydrocracking
[00139] In addition to providing a method for forming Group II base stocks
from a challenged
feed, the methods described herein can also be used to control the
distribution of base stocks
formed from a feed by varying the amount of conversion performed in sour
conditions versus sweet
conditions. This is illustrated by the results shown in FIG. 5.
[00140] In FIG. 5, the upper two curves show the relationship between the cut
point used for
forming a lubricant base stock of a desired viscosity (bottom axis) and the
viscosity index of the
resulting base stock (left axis). The curve corresponding to the circle data
points represents
processing of a C5 deasphalted oil using a configuration similar to FIG. 2,
with all of the
hydrocracking occurring in the sour stage. The curve corresponding to the
square data points
corresponds to performing roughly half of the hydrocracking conversion in the
sour stage and the
remaining hydrocracking conversion in the sweet stage (along with the
catalytic dewaxing). The
individual data points in each of the upper curves represent the yield of each
of the different base
stocks relative to the amount of feed introduced into the sour processing
stage. It is noted that
summing the data points within each curve shows the same total yield of base
stock, which reflects
the fact that the same total amount of hydrocracking conversion was performed
in both types of
processing runs. Only the location of the hydrocracking conversion (all sour,
or split between sour
and sweet) was varied.
[00141] The lower pair of curves provides additional information about the
same pair of process
runs. As for the upper pair of curves, the circle data points in the lower
pair of curves represent all
hydrocracking in the sour stage and the square data points correspond to a
split of hydrocracking
between sour and sweet stages. The lower pair of curves shows the relationship
between cut point
(bottom axis) and the resulting kinematic viscosity at 100 C (right axis). As
shown by the lower
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pair of curves, the three cut point represent formation of a light neutral
base stock (5 or 6 cSt), a
heavy neutral base stock (10¨ 12 cSt), and a bright stock (about 30 cSt). The
individual data points
for the lower curves also indicate the pour point of the resulting base stock.
[00142] As shown in FIG. 5, altering the conditions under which hydrocracking
is performed
can alter the nature of the resulting lubricant base stocks. Performing all of
the hydrocracking
conversion during the first (sour) hydroprocessing stage can result in higher
viscosity index values
for the heavy neutral base stock and bright stock products, while also
producing an increased yield
of heavy neutral base stock. Performing a portion of the hydrocracking under
sweet conditions
increased the yield of light neutral base stock and bright stock with a
reduction in heavy neutral
base stock yield. Performing a portion of the hydrocracking under sweet
conditions also reduced
the viscosity index values for the heavy neutral base stock and bright stock
products. This
demonstrates that the yield of base stocks and/or the resulting quality of
base stocks can be altered
by varying the amount of conversion performed under sour conditions versus
sweet conditions.
Example 5 ¨ Blocked Operation
[00143] A configuration similar to the configuration shown in FIGS. 7 to 9
was used to process
a resid-type feed that substantially included 510 C+ components. The
configuration for this
example did not include recycle products as part of the feed for the sour
stage or for further sweet
stage processing. The feed was initially deasphalted using n-pentane to
product 75 wt%
deasphalted oil and 25 wt% deasphalter rock or residue. The resulting
deasphalted oil had an API
gravity of 12.3, a sulfur content of 3.46 wt%, and a nitrogen content of ¨2760
wppm. The
deasphalted oil was then hydroprocessed in an initial sour hydroprocessing
stage that included four
catalyst beds. The first two catalyst beds corresponded to commercially
available demetallization
catalysts. The third catalyst bed corresponded to commercially available
hydrotreating catalyst,
including at least a portion of a commercially available bulk metal
hydrotreating catalyst. The
fourth catalyst bed included a commercially available hydrocracking catalyst.
The effluent from
each catalyst bed was cascaded to the next catalyst bed. The average reaction
temperature across
each catalyst bed was 378 C for the first demetallization catalyst bed, 388 C
for the second
demetallization catalyst bed, 389 C for the hydrotreating catalyst bed, and
399 C for the
hydrocracking catalyst bed. The flow rate of the feed relative to the total
volume of catalyst in the
sour hydroprocessing stage was an LHSV of 0.16 hr-1. The hydrogen partial
pressure was 2500
psia (17.2 MPa-a) and the hydrogen treat gas flow rate was 8000 scf/b (-1420
Nm3/m3). Under
these conditions, the hydroprocessing consumed roughly 2300 scf/b (-400
Nm3/m3). The
conditions resulted in roughly 50 wt% conversion relative to 370 C.
[00144] After processing in the initial sour stage, a fractionator was used to
separate the
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hydroprocessed effluent into various fractions. The fractions included light
ends, at least one fuels
fraction, a light neutral fraction, a heavy neutral fraction, and a
brightstock fraction. Table 4 shows
additional details regarding the hydroprocessed effluent from the initial sour
stage.
Table 4¨ Hydroprocessed Effluent (Sour Stage)
Product Wt% (of total Nitrogen content Solvent dewaxed VI
effluent) (wPPIT)
H2S 3.7
NH3 0.3
Ci 0.4
C2 0.4
C3 0.7
C4 0.9
C5 1.3
C6 to 370 C (fuels 45.6
fraction)
Light Neutral 13.9 1 102.8
Heavy Neutral 14.0 1 99.8
Brightstock 22.2 5 - 10 110.5
[00145] The light neutral, heavy neutral, and brightstock fractions from the
initial sour
hydroprocessing stage were then further hydroprocessed in the presence of a
noble metal
hydrocracking catalyst (0.6 wt% Pt on alumina-bound USY) and a noble metal
dewaxing catalyst
(0.6 wt% Pt on alumina bound ZSM-48. The sweet stage conditions for each
fraction were selected
separately to achieve desired VI values.
[00146] For the light neutral feed, the sweet stage conditions were selected
to achieve roughly
30 wt% conversion relative to 370 C. This produced a light neutral lubricant
base stock in a 70.6
wt% yield relative to the light neutral feed. The resulting light neutral base
stock had a VI of 109.9
and a kinematic viscosity at 100 C of 5.8 cSt. For the heavy neutral feed, the
sweet stage
conditions were selected to achieve roughly 6 wt% conversion relative to 370
C. This produced a
heavy neutral lubricant base stock in a 93.7 wt% yield relative to the heavy
neutral feed. The
resulting heavy neutral base stock had a VI of 106.6 and a kinematic viscosity
at 100 C of 11.7
cSt. For the brightstock feed, the sweet stage conditions were selected to
achieve roughly 30 wt%
conversion relative to 370 C. This produced a brightstock base stock in a 54.3
wt% yield relative
to the brightstock feed. The resulting brightstock base stock had a VI of 103
and a kinematic
viscosity at 100 C of 32 cSt. Additionally, a yield of 16.1 wt% of a light
neutral lubricant boiling
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range product was generated with a kinematic viscosity at 100 C of 6 cSt and a
viscosity index of
roughly 100. This additional light neutral lubricant boiling range product was
optionally suitable
for recycle to either the light neutral or heavy neutral processing block.
This could allow, for
example, the light neutral or heavy neutral processing block to be operated at
a reduced temperature
(due to further reduced nitrogen in the combined feed). Such reduced
temperature can be favorable
for further reducing any additional aromatics that might be present in the
recycled product.
Alternatively, the additional light neutral product could be recycled to the
initial sour stage for
further upgrading, although this could lead to additional production of fuels
as opposed to lubricant
products.
Example 6 ¨ Production of Base Stocks (Including Bright Stock) at High
Conversion
[00147] Another series of processing runs were performed using a C5 DAO (75
wt% yield) as a
feed for lubricant production. The configuration was similar to Example 5.
Block processing was
used for the sweet processing stage. The light neutral, heavy neutral, and
brightstock portions were
processed under conditions to produce two levels of conversion relative to 370
C. In a first set of
runs, the combined sour stage and sweet stage conversion was 60 wt%. In a
second set of runs,
the combined sour stage and sweet stage conversion was 82 wt%. It is noted
that at high rates of
conversion during a single pass, any portions of a lubricant product that are
recycled could
potentially undergo conversion amounts of greater than 70 wt%, or greater than
75 wt%, or greater
than 80 wt%, such as up to 90 wt% or more.
[00148] Conventionally, conversion of greater than roughly 70 wt% of a
feedstock during
lubricant product is believed to lead to large reductions in viscosity index
for resulting lubricant
products. Without being bound by any particular theory, this is believed to be
due in part to
conversion of isoparaffins with the feed at elevated levels of conversion. It
has been surpisingly
discovered that feeds derived from high yield deasphalted oils (such as
deasphalting yields of at
least 50 wt%) can be undergo greater than 70 wt% conversion without having
substantial
reductions in VI. This is believed to be related to the unusually high
aromatic content of lubricant
feeds derived from high yield deasphalted oils.
[00149] Table 5 shows results from processing the C5 DAO feed in this example
at conversion
amounts of 60 wt% and 82 wt% (combined conversion across initial sour stage
and second sweet
stage) for production during block operation of a light neutral product, a
heavy neutral product,
and a brightsock product. As shown in Table 5, increasing the combined
conversion results in
products with comparable (or potentially higher) viscosity index values, while
also allowing
generating products with substantially reduced pour point values.
Table 5¨ Product properties at varying conversion
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82 wt% combined conversion 60 wt% combined conversion
(relative to 370 C) (relative to 370 C)
Light Neutral
VI 106 106
Pour Point ( C) -64 -34
KV @ 100 C (cSt) 4.9 4.3
Heavy Neutral
VI 100.9 100.5
Pour Point ( C) -48 -34
KV @ 100 C (cSt) 11.9 12.6
Bright Stock
VI 109 106.3
Pour Point ( C) -32 -20
KV @ 100 C (cSt) 34.6 43.2
Additional Embodiments
[00150] Embodiment 1. A method for making lubricant base stock, comprising:
hydroprocessing a feedstock comprising a 370 C+ fraction under first effective
hydroprocessing
conditions to form a hydroprocessed effluent, the at least a portion of the
deasphalted oil having
an aromatics content of at least about 50 wt%, the hydroprocessed effluent
comprising a sulfur
content of 300 wppm or less, a nitrogen content of 100 wppm or less, or a
combination thereof;
separating the hydroprocessed effluent to form at least a first fraction
comprising a T5 distillation
point of at least 370 C and a kinematic viscosity at 100 C of 6 cSt to 20 cSt
(or 8 cSt to 16 cSt, or
cSt to 14 cSt); hydroprocessing at least a portion of the first fraction under
second effective
hydroprocessing conditions, the second effective hydroprocessing conditions
comprising catalytic
dewaxing conditions, to form a catalytically dewaxed effluent comprising a 370
C+ portion; and
solvent extracting at least a portion of the 370 C+ portion of the
catalytically dewaxed effluent to
form a solvent processed effluent.
[00151] Embodiment 2. A method for making lubricant base stock, comprising:
performing
solvent deasphalting, optionally using a C4+ solvent, under effective solvent
deasphalting
conditions on a feedstock having a T5 boiling point of at least about 370 C
(or at least about 400 C,
or at least about 450 C, or at least about 500 C), the effective solvent
deasphalting conditions
producing a yield of deasphalted oil of at least about 50 wt% of the
feedstock; hydroprocessing at
least a portion of the deasphalted oil under first effective hydroprocessing
conditions to form a
hydroprocessed effluent, the at least a portion of the deasphalted oil having
an aromatics content
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of at least about 50 wt%, the hydroprocessed effluent comprising a sulfur
content of 300 wppm or
less, a nitrogen content of 100 wppm or less, or a combination thereof;
separating the
hydroprocessed effluent to form at least a first fraction comprising a T5
distillation point of at least
370 C and a kinematic viscosity at 100 C of 6 cSt to 20 cSt (or 8 cSt to 16
cSt, or 10 cSt to 14
cSt); hydroprocessing at least a portion of the first fraction under second
effective hydroprocessing
conditions, the second effective hydroprocessing conditions comprising
catalytic dewaxing
conditions, to form a catalytically dewaxed effluent comprising a 370 C+
portion; and solvent
extracting at least a portion of the 370 C+ portion of the catalytically
dewaxed effluent to form a
solvent processed effluent.
[00152] Embodiment 3. A method for making lubricant base stock, comprising:
hydroprocessing a feedstock comprising a 370 C+ fraction under first effective
hydroprocessing
conditions to form a hydroprocessed effluent, the at least a portion of the
deasphalted oil having
an aromatics content of at least about 50 wt%, the hydroprocessed effluent
comprising a sulfur
content of 300 wppm or less, a nitrogen content of 100 wppm or less, or a
combination thereof;
separating the hydroprocessed effluent to form at least a first fraction
having a T5 distillation point
of at least 370 C; hydroprocessing at least a portion of the first fraction
under second effective
hydroprocessing conditions, the second effective hydroprocessing conditions
comprising catalytic
dewaxing conditions, to form a catalytically dewaxed effluent comprising a 370
C+ portion, the
370 C+ portion comprising a second fraction comprising a kinematic viscosity
at 100 C of 6 cSt
to 20 cSt (or 8 cSt to 16 cSt, or 10 cSt to 14 cSt); and solvent extracting at
least a portion of the
second fraction to form a solvent processed effluent.
[00153] Embodiment 4. A method for making lubricant base stock, comprising:
performing
solvent deasphalting, optionally using a C4+ solvent, under effective solvent
deasphalting
conditions on a feedstock having a T5 boiling point of at least about 370 C
(or at least about 400 C,
or at least about 450 C, or at least about 500 C), the effective solvent
deasphalting conditions
producing a yield of deasphalted oil of at least about 50 wt% of the
feedstock; hydroprocessing at
least a portion of the deasphalted oil under first effective hydroprocessing
conditions to form a
hydroprocessed effluent, the at least a portion of the deasphalted oil having
an aromatics content
of at least about 50 wt%, the hydroprocessed effluent comprising a sulfur
content of 300 wppm or
less, a nitrogen content of 100 wppm or less, or a combination thereof;
separating the
hydroprocessed effluent to form at least a first fraction comprising a T5
distillation point of at least
370 C; hydroprocessing at least a portion of the first fraction under second
effective
hydroprocessing conditions, the second effective hydroprocessing conditions
comprising catalytic
dewaxing conditions, to form a catalytically dewaxed effluent comprising a 370
C+ portion, the
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370 C+ portion comprising a second fraction comprising a kinematic viscosity
at 100 C of 6 cSt
to 20 cSt (or 8 cSt to 16 cSt, or 10 cSt to 14 cSt); and solvent extracting at
least a portion of the
second fraction to form a solvent processed effluent.
[00154] Embodiment 5. The method of Embodiment 3 or 4, further comprising
separating at
least a portion of the catalytically dewaxed effluent to form the second
fraction or separating at
least a portion of the 370 C+ portion of the catalytically dewaxed effluent to
form the second
fraction.
[00155] Embodiment 6. The method of any of the above embodiments, wherein the
solvent
processed effluent comprises a VI of at least 80 and a kinematic viscosity at
100 C of 6 cSt to 20
cSt.
[00156] Embodiment 7. The method of any of the above embodiments, wherein the
solvent
processed effluent comprises a pour point of -6 C or less (or -10 C or less,
or -15 C or less, or -
20 C or less), a cloud point of -2 C or less (or -5 C or less or -10 C or
less, or -15 C or less, or -
20 C or less), or a combination thereof
[00157] Embodiment 8. The method of any of the above embodiments, wherein the
solvent
extracting comprises solvent extracting with N-methylpyrrolidone, furfural,
phenol, or a
combination thereof
[00158] Embodiment 9. The method of any of Embodiments 2 or 4 - 8, wherein the
yield of
deasphalted oil is at least 55 wt%, or at least 60 wt%, or at least 65 wt%, or
at least 70 wt%, or at
least 75 wt%, or wherein the deasphalted oil has an aromatics content of at
least 55 wt%, or at least
60 wt%, or at least 65 wt%, or at least 70 wt% based on a weight of the
deasphalted oil, or a
combination thereof
[00159] Embodiment 10. The method of any of Embodiments 2 or 4 - 9, wherein
the C4+ solvent
comprises a C5+ solvent, a mixture of two or more Cs isomers, or a combination
thereof
[00160] Embodiment 11. The method of any of the above embodiments, wherein the
solvent
processed effluent comprises a viscosity index of 80 to 160, or 80 to 140, or
80 to 120, or 90 to
160, or 90 to 140, or 90 to 120, or 100 to 160, or 100 to 140, or 120 to 160,
or 120 to 140.
[00161] Embodiment 12. The method of any of the above embodiments, wherein
prior to the
solvent extracting, the 370 C+ portion of the catalytically dewaxed effluent
or the second fraction
comprises an absorptivity at 226 nm of at least 0.020, or at least 0.025, or
at least 0.030, the 370 C+
portion of the catalytically dewaxed effluent or the second fraction after
extraction comprising an
absorptivity at 226 nm of less than 0.020, or less than 0.018, or less than
0.016.
[00162] Embodiment 13. The method of any of the above embodiments, wherein
prior to the
solvent extracting, the 370 C+ portion of the catalytically dewaxed effluent
or the second fraction
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comprises an absorptivity at 254 nm of at least 0.010, or at least 0.012, or
at least 0.014, the 370 C+
portion of the catalytically dewaxed effluent or the second fraction after
extraction comprising an
absorptivity at 254 nm of less than 0.010, or less than 0.008, or less than
0.006, or less than 0.004.
[00163] Embodiment 14. The method of any of the above embodiments, wherein
prior to the
solvent extracting, the 370 C+ portion of the catalytically dewaxed effluent
or the second fraction
comprises an absorptivity at 275 nm of at least 0.010, or at least 0.012, or
at least 0.014, the 370 C+
portion of the catalytically dewaxed effluent or the second fraction after
extraction comprising an
absorptivity at 275 nm of less than 0.010, or less than 0.008, or less than
0.006, or less than 0.004.
[00164] Embodiment 15. The method of any of the above embodiments, wherein
prior to the
solvent extracting, the 370 C+ portion of the catalytically dewaxed effluent
or the second fraction
comprises an absorptivity at 302 nm of at least 0.020, or at least 0.025, or
at least 0.030, the 370 C+
portion of the catalytically dewaxed effluent or the second fraction after
extraction comprising an
absorptivity at 302 nm of less than 0.010, or less than 0.008, or less than
0.006, or less than 0.004.
[00165] Embodiment 16. The method of any of the above embodiments, wherein
prior to the
solvent extracting, the 370 C+ portion of the catalytically dewaxed effluent
or the second fraction
comprises an absorptivity at 310 nm of at least 0.030, or at least 0.035, or
at least 0.040, the 370 C+
portion of the catalytically dewaxed effluent or the second fraction after
extraction comprising an
absorptivity at 310 nm of less than 0.010, or less than 0.008, or less than
0.006, or less than 0.004.
[00166] Embodiment 17. The method of any of the above embodiments, wherein
prior to the
solvent extracting, the 370 C+ portion of the catalytically dewaxed effluent
or the second fraction
comprises an absorptivity at 325 nm of at least 0.010, or at least 0.012, or
at least 0.014, the 370 C+
portion of the catalytically dewaxed effluent or the second fraction after
extraction comprising an
absorptivity at 310 nm of less than 0.010, or less than 0.008, or less than
0.006, or less than 0.004.
[00167] Embodiment 18. A solvent processed effluent produced according to any
of
Embodiments 1 ¨ 17.
[00168] Embodiment 19. A formulated lubricant formed from the solvent
processed effluent
of Embodiment 18, the formulated optionally comprising an additive.
[00169] 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
invention 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 invention. 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
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the present invention, including all features which would be treated as
equivalents thereof by those
skilled in the art to which the invention pertains.
[00170] The present invention 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.
