U.S. patent number 3,642,610 [Application Number 04/855,737] was granted by the patent office on 1972-02-15 for two-stage hydrocracking-hydrotreating process to make lube oil.
This patent grant is currently assigned to Atlantic Richfield Company. Invention is credited to Joseph M. Divijak, Jr., Maurice K. Rausch.
United States Patent |
3,642,610 |
Divijak, Jr. , et
al. |
February 15, 1972 |
TWO-STAGE HYDROCRACKING-HYDROTREATING PROCESS TO MAKE LUBE OIL
Abstract
A high-viscosity-index mineral lubricating oil is produced by
treating, for instance, a deasphalted residuum or a raw, heavy
lubricating distillate oil in a two-stage process. The feedstock is
first catalytically hydrocracked, then catalytically hydrogenated
and can be fractionated and dewaxed to produce a finished product.
Catalysts such as nickel-tungstate on boria-alumina and
nickel-molybdate on alumina are employed in the two stages,
respectively. The catalysts are preferably used in sulfided
form.
Inventors: |
Divijak, Jr.; Joseph M.
(Griffith, IN), Rausch; Maurice K. (South Holland, IL) |
Assignee: |
Atlantic Richfield Company (New
York, NY)
|
Family
ID: |
25321960 |
Appl.
No.: |
04/855,737 |
Filed: |
September 5, 1969 |
Current U.S.
Class: |
208/58; 208/87;
208/57; 208/144 |
Current CPC
Class: |
C10G
47/12 (20130101); C10G 2400/10 (20130101) |
Current International
Class: |
C10G
65/12 (20060101); C10G 65/00 (20060101); C10G
47/00 (20060101); C10G 47/12 (20060101); C10g
023/02 (); C10g 013/06 (); C10g 037/00 () |
Field of
Search: |
;208/18,58,59,111,143,144,87 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Gantz; Delbert E.
Assistant Examiner: Schmitkons; G. E.
Claims
It is claimed:
1. A process of preparing a mineral hydrocarbon lubricating oil
having a viscosity index of at least about 90 on a dewaxed basis
which comprises:
a. Contacting a mineral hydrocarbon oil feedstock of lubricating
viscosity at 210.degree. F., at least about 90 weight percent of
which boils above about 600.degree. F. and having a viscosity index
of about 50 to 80, with molecular hydrogen under hydrocracking
conditions including a temperature of about 725 to 875.degree. F.,
in the presence of a catalyst having minor, catalytically effective
amounts of each of nickel, a member selected from the group
consisting of tungsten and molybdenum, and boria on an active
alumina support; and
b. Contacting hydrocarbon oil of lubricating viscosity from step
(a) with molecular hydrogen under hydrogenation conditions
including a temperature of about 550.degree. to 825.degree. F. in
the presence of a solid hydrogenation catalyst at a hydrotreating
severity such that not more than about 5 volume percent of the feed
to step (b) boiling above 600.degree. F. is cracked to material
boiling below about 600.degree. F. to produce oil of lubricating
viscosity having a viscosity index of at least about 90 and at
least about 20 viscosity index number greater than the hydrocarbon
oil feedstock passing to step (a).
2. The process of claim 1 wherein said hydrocracking conditions
include a hydrogen partial pressure of about 1,000 to 5,000
p.s.i.g., a weight hourly space velocity of about 0.3 to 3 WHSV and
a molecular hydrogen to hydrocarbon feed ratio of about 1,000 to
5,000 standard cubic feet per barrel of feed.
3. The process of claim 2 wherein the catalysts are in sulfide
form.
4. The process of claim 3 wherein the hydrocracking catalyst
contains about 2 to 10 weight percent nickel, about 10 to 20
percent of the member selected from the group consisting of
tungsten and molybdenum on an oxide basis, and about 2 to 10
percent boria.
5. The process of claim 4 wherein the selected member of the
catalyst employed in the hydrocracking stage is tungsten.
6. The process of claim 2 wherein said hydrogenation conditions
include a temperature of about 550.degree.to 825.degree. F., a
hydrogen partial pressure of about 1,000 to 5,000 p.s.i.g., a
weight hourly space velocity of about 0.3 to 5 WHSV and a molecular
hydrogen to hydrocarbon feed ratio of about 500 to 3,500 standard
cubic feet per barrel of feed.
7. The process of claim 6 wherein the catalyst employed in the
hydrogenation stage contains minor, catalytically-effective amounts
of a member selected from the group consisting of nickel and
cobalt, and molybdenum on alumina.
8. The process of claim 7 wherein the catalyst is in sulfide
form.
9. The process of claim 8 wherein the hydrocracking catalyst
contains about 2 to 10 weight percent nickel, about 10 to 20
percent of the member selected from the group consisting of
tungsten and molybdenum on an oxide basis, and about 2 to 10
percent boria.
10. A process of preparing a mineral hydrocarbon lubricating oil
having a viscosity index of at least about 90 on a dewaxed basis
which comprises:
a. Contacting a mineral hydrocarbon oil feedstock of lubricating
viscosity at 210.degree. F., at least 90 weight percent of which
boils above about 1,000.degree. F. and having a viscosity index of
about 50 to 80, with molecular hydrogen under hydrocracking
conditions including a temperature of about 750.degree. to
850.degree. F., a hydrogen partial pressure of about 1,500 to 3,000
p.s.i.g., a weight hourly space velocity of about 0.5 to 2 WHSV and
a molecular hydrogen to hydrocarbon feed ratio of about 1,500 to
3,000 standard cubic feet per barrel of feed, in the presence of a
catalyst containing about 2 to 10 weight percent nickel, about 10
to 20 percent tungsten on an oxide basis and about 2 to 10 percent
boria on an active alumina support, the metals of the catalyst
being present in the sulfide form; and
b. Contacting hydrocarbon oil of lubricating viscosity from step
(a) with molecular hydrogen under hydrogenation conditions,
including a temperature of about 600.degree. to 800.degree. F., a
hydrogen partial pressure of about 1,500 to 3,000 p.s.i.g., a
weight hourly space velocity of about 0.5 to 3 WHSV and a molecular
hydrogen to hydrocarbon feed ratio of about 1,500 to 2,500 standard
cubic feet per barrel of feed in the presence of a solid
hydrogenation catalyst containing minor, catalytically effective
amounts of a member selected from the group consisting of nickel
and cobalt, and molybdenum on alumina, the metals of the catalyst
being present in the sulfide form, to produce oil of lubricating
viscosity having a viscosity index of at least about 90 and at
least about 30 viscosity index numbers greater than the hydrocarbon
oil feedstock passing to step (a).
11. The process of claim 1 wherein the product from step (b) is
fractionated to separate oil of lubricating viscosity and the
lubricating oil fraction is dewaxed.
12. The process of claim 10 wherein the product from step (b) is
fractionated to separate oil of lubricating viscosity and the
lubricating oil fraction is dewaxed.
Description
The present invention relates to a process for the production of
high quality mineral lubricating oils from feedstocks that are not
normally used in present commercial processes to make such
products. In addition to mineral lube oil distillates and
deasphalted residuums of relatively high quality, stocks containing
high percentages of sulfur, nitrogen and carbon residue, such as
sour oils and more highly contaminated deasphalted oils, may be
employed as feeds. Moreover, a wide range of products is possible.
Lubricating oils with viscosity indexes up to about 150 or more
(ASTM Designation: D-2270) with partial or even complete aromatic
saturation are possible. The present process is also more
economical than present methods for the production of high
viscosity index oils involving solvent treatment, dewaxing and
finishing. The invention produces such oils by hydrocracking the
mineral oil feed while in contact with a catalyst containing
nickel, and tungsten or molybdenum along with boria on an alumina
support, followed by hydrogenation of resulting hydrocracked
materials of lubricating viscosity over a hydrogenation catalyst
whereby a high viscosity index oil is produced.
Many of the present day refining techniques employed to produce
high quality mineral lubricating oils having high viscosity indexes
possess certain undesirable features. For example, the production
of finished oils having a viscosity index of 95 by known methods of
fractionation and solvent extraction of vacuum distillates or
deasphalted residuums followed by dewaxing and finishing with acid,
clay or hydrogen, normally results in yields of about 50 to 65
volume percent. The present invention, however, can produce 95 VI
oils in yields of about 60 to 80 volume percent on a dewaxed basis
and yields of about 40 volume percent or more on a dewaxed basis of
oils having viscosity indexes of about 120 and higher.
The mineral lubricating oils treated by the process of the present
invention are of lubricating viscosity at 210.degree. F. and are
principally stocks having at least about 90 weight percent boiling
above about 600.degree. F.; preferably the feed is a residuum at
least about 90 weight percent of which boils above about
1,000.degree. F. The feeds are usually oils of at least about 50
VI, e.g., about 50 to 80, or even about 70 to 80 VI, and can be
derived from paraffinic or mixed base crude oils. The total or full
range oil of lubricating viscosity obtained by the method of the
present invention has a viscosity index in the range of at least
about 90, say up to about 150 or more, with the increase in the
viscosity index of the product being at least about 20, preferably
at least about 30, over that of the feed. Both the initial
hydrocarbon feedstock and the product of lubricating viscosity from
the hydrogenation reaction boil over a considerable temperature
range, e.g., over a range of at least about 100.degree. F., often
at least about 200.degree. F. The hydrocarbon feedstock preferably
has a specific dispersion (ASTM Designation: D-1218) in the range
of about 105-165 while the specific dispersion of the product of
lubricating viscosity is preferably in the range of about 100-110.
The method of the present invention is particularly suitable for
treating feedstocks having a specific dispersion in the range of
about 135-165, such stocks being the highly contaminated stocks,
containing larger amounts of aromatics and frequently having been
subjected only to fractionation and deasphalting. Thus the present
method can utilize these economically cheaper feedstocks to produce
high quality lubricating oils in high yields.
Hydrocracking of the feedstock which includes ring opening and
usually desulfurization and denitrogenation, is carried out in
contact with a catalyst containing nickel and one or both of
molybdenum or tungsten supported, along with boria, on a
catalytically active alumina base. The metals of the catalyst may
be present in the form of free metals or in combined form such as
the oxides and sulfides, the sulfides being the preferred form.
Examples of such mixtures or compounds are nickel molybdate or
tungstate (or thiomolybdate or thiotungstate). These catalytic
ingredients, along with boria, are employed while disposed on a
catalytically-active alumina. The catalyst is composed of minor,
catalytically effective amounts of nickel, tungsten and/or
molybdenum and boria on the alumina base. Nickel may often comprise
about 1-40 weight percent of the catalyst, preferably about 2-10
percent, with the total amount of tungsten and molybdenum being
about 5-30 weight percent, preferably about 10-20 percent, of the
catalyst on a metal oxide basis. Preferably the boria is present in
an amount of about 2 to 10 weight percent, based on the total
weight of the catalyst while the alumina is the major component of
the catalyst, e.g., the essential balance of the composition.
The catalyst composition used in the hydrocracking stage of the
present invention can be prepared by adding the nickel, tungsten,
molybdenum and boria components to the alumina by the various
methods known to the art, for example by impregnation or
precipitation and coprecipitation using suitable compounds of the
metals and boron. For example, alumina particles containing boria
or a material which upon heating yields boria, can be mixed with
aqueous ammonia solutions containing nickel and tungsten, and/or
molybdenum, or other aqueous solutions of water-soluble compounds
of nickel and tungsten and/or molybdenum, so that the metal
components are absorbed on the base. Alternatively, the promoting
materials can be precipitated on the boria-containing alumina base
through suitable reaction of an aqueous slurry of the support
containing water-insoluble salts of the promoting metals. The
boria-containing particles can be formed into macrosize either
before or after being mixed with the nickel and tungsten and/or
molybdenum components. The catalyst can be dried and calcined,
e.g., at temperatures of about 800 to 1,200.degree. F. or somewhat
more. Prior to use the catalyst is preferably sulfided at elevated
temperature.
The hydrocracking step is carried out under conditions designed to
selectively crack the feed so that opening of aromatic and
naphthenic rings is favored, rather than the splitting of chains
into lower molecular weight compounds. Such conditions include a
temperature of about 725.degree.to 875.degree. F., preferably about
750.degree.to 850.degree. F. The other reaction conditions often
include a hydrogen partial pressure of about 1,000 to 5,000
p.s.i.g., preferably about 1,500 to 3,000 p.s.i.g. In the
production of 95 VI oils by the method of this invention, cracking
may take place to the extent that from about 5 to 10 percent by
volume of the product of the hydrocracking stage is material
boiling below about 600.degree. F. In the production of 120 VI
oils, about 30 to 40 percent by volume of the product of the
hydrocracking stage may be comprised of such materials. The amount
of free hydrogen employed during hydrocracking can be generally
about 1,000 to 5,000 standard cubic feet per barrel of hydrocarbon
feed, preferably about 1,500 to 3,000 standard cubic feet per
barrel. The weight hourly space velocity (WHSV), weight units of
feed introduced into the reaction zone per weight unit of catalyst
per hour, will often be in the range of about 0.3 to 3, preferably
about 0.5 to 2. The reactor effluent from the first or
hydrocracking stage can be flashed to prevent hydrogen sulfide and
ammonia from going to the hydrogenation stage, but this is not
necessary, especially if nonprecious metal hydrogenation catalysts
are used in the hydrogenation stage. Also, if desired any light
hydrocarbons can be removed from the feed to the hydrogenation
stage.
Lubricating oil from the hydrocracking stage is subjected to a
hydrogenation operation which involves contacting lubricating oil,
preferably the essentially full range lube oil, from the
hydrocracking stage in the presence of hydrogen with a solid
hydrogenation catalyst at a temperature of about 550.degree.to
825.degree. F., preferably about 600.degree. to 800.degree. F. It
is preferred that the temperature employed in the second stage be
at least about 50.degree. F. less than the temperature of the first
stage for optimum decolorization and saturation. The other reaction
conditions often include pressures of about 1,000 to 5,000
p.s.i.g., preferably about 1,500 to 3,000 p.s.i.g.; space
velocities (WHSV) of about 0.3 to 5, preferably about 0.5 to 3; and
molecular hydrogen to feed ratios of about 500 to 3,500 standard
cubic feet of hydrogen per barrel of hydrocarbon feed, preferably
about 1,500 to 2,500 standard cubic feet of hydrogen per barrel of
hydrocarbon feed.
The solid catalyst employed in the hydrogenation operation is
preferably a sulfur-resistant, nonprecious metal hydrogenation
catalyst, such as those conventionally employed in the
hydrogenation of heavy petroleum oils. Examples of suitable
catalytic ingredients are tin, vanadium, members of Group VIB in
the periodic table, i.e., chromium, molybdenum and tungsten and
metals of the iron group, i.e., iron, cobalt and nickel. These
metals are present in minor, catalytically effective amounts, for
instances, about 2 to 30 weight percent of the catalyst, and may be
present in the elemental form or in combined form such as the
oxides or sulfides, the sulfide form being preferred. Mixtures of
these materials or compounds of two or more of the oxides or
sulfides can be employed, for example, mixtures or compounds of the
iron group metal oxides or sulfides with the oxides or sulfides of
Group VIB constitute very satisfactory catalysts. Examples of such
mixtures or compounds are nickel molybdate, tungstate or chromate
(or thiomolybdate, thio-tungstate or thiochromate) or mixtures of
nickel or cobalt oxides with molybdenum, tungsten or chromium
oxides. As the art is aware and as the specific examples below
illustrate, these catalytic ingredients are generally employed
while disposed upon a suitable carrier of the solid oxide
refractory type, e.g., a predominantly calcined or activated
alumina. To avoid undue cracking the catalyst base and other
components have little, if any, hydrocarbon cracking activity.
Usually not more than about 5 volume percent, preferably not more
than about 2 volume percent, of the feed is cracked in the second
or hydrogenation stage to produce materials boiling below about
600.degree. F. Commonly employed catalysts have about 1 to 10
weight percent of an iron group metal and about 5 to 25 percent of
a Group VIB metal (calculated as the oxide). Advantageously, the
catalyst is nickel molybdate or cobalt molybdate, supported on
alumina. Such preferred catalysts can be prepared by the method
described in U.S. Pat. No. 2,938,002.
Other suitable hydrogenation catalysts which can be employed in the
method of this invention include the platinum group metal types.
Such catalysts often have a minor catalytically effective amount,
say about 0.05 to 2 weight percent, preferably about 0.1 to 1
weight percent of one or more platinum group metals carried on a
solid support, especially an active alumina. Suitable platinum
group metals include platinum, rhodium and ruthenium with platinum
being preferred.
The catalysts employed in both the hydrocracking and hydrogenation
stages of the method of this invention are preferably disposed in
the reaction zones as fixed beds. Such fixed bed catalysts are
usually particles of macrosize, e.g., about one sixty-fourth to
one-fourth inch, preferably about one-sixteenth to one-eighth inch,
in diameter, and, about one sixty-fourth to 1 inch or more,
preferably about one-eighth to one-half inch in length. These
catalysts can be made by extrusion, tableting or other suitable
procedures.
The hydrogenation operation provides additional aromatic
saturation, color improvement and stability towards oxidation and
corrosion. Additional color improvement can be provided by
subjecting the effluent from the hydrogenation operation to
treatment with ultraviolet light. The treatment was found to
lighten considerably the color of the darker oils, a surprising
result since such treatment usually produces the opposite effect.
The reactor effluent from the hydrogenation stage may be flashed to
recover hydrogen for possible recycle and fed to a steam stripper
to remove excess light hydrogenated components. The oil can then be
fractionated and the lube fractions dewaxed. This dewaxing step can
be carried out, for example, by pressing or by solvent dewaxing
using methyl ethyl ketone and toluene as the solvent system.
Dewaxing may be carried out prior to the initial hydrocracking step
but it is preferred to conduct dewaxing after hydrogenation has
been completed. No additional finishing is required. Yields of
about 60 to 80 volume percent, based on the raw stock, of 95 VI
oils are not uncommon and finished base oils having viscosity
indexes of 120 and higher are obtained in economical yields, e.g.,
in the range of about 40 volume percent and higher.
The following example is illustrative of the method of this
invention:
Deasphalted petroleum residuum was fed to an isothermal reactor
unit having a nickel-tungstate on boria-aluminia catalyst in the
first or hydrocracking stage and nickel-molybdate on alumina
catalyst in the second or hydrogenation stage. The catalysts were
macrosize and presulfided. The feedstock employed had the following
specifications:
VI (D-2270) (dewaxed basis) 76 Gravity, .degree.API 23.1 Flash,
.degree.F. 555 Viscosity, SUS/210.degree.F. 154.4 Pour, .degree.F.
120+ ASTM color Dark Carbon residue (Con.), wt.% 1.58 10% boiling
point >1,000.degree.F.
table I lists operating conditions and dewaxed oil inspections for
nominal 100 and 130 VI operations.
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TABLE I
Operation 100 VI 130 VI
__________________________________________________________________________
Pressure, p.s.i.g., (1st & 2nd stages) 2,500 2,500 Temperature
(1st stage),.degree.F. 775 815 (2nd stage),.degree.F. 700 700 WHSV
(1st stage) 1.0 1.0 (2nd stage) 1.5 th 1.5 H.sub.2 Rate,
SCF/bbl.(1st & 2nd stages) 2,500 2,500 Second-Stage Product Oil
Inspection (dewaxed basis) Yield, vol. % 61 50 Gravity, .degree.API
28.7 33.2 Flash, .degree.F. 405 375 Viscosity, SUS/100.degree.F.
605.8 180.9 Viscosity, SUS/210.degree.F. 70.17 47.27 VI (D-2270)
100 128 Pour, .degree.F. +5 +10 ASTM Color L2.0 L1.5 Carbon Residue
(Con.) 0.026 0.004 Specific Dispersion 102.4 101.5
__________________________________________________________________________
The catalysts employed in the successive stages analyzed as
follows:
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TABLE II
NiW on NiMo on Boria-Alumina Alumina
__________________________________________________________________________
Nickel, wt.% 5.35 2.30 Tungsten Oxide, wt.% 12.15 -- Molybdenum
Oxide, wt.% -- 15.60 Silicon Dioxide, wt.% 0.29 -- Boria, wt.% 5.06
-- Volatile matter at 1,200.degree. F. 3.98 (at 1,000.degree. F.)
0.86 Apparent Density, g./ml. 0.75 0.765
__________________________________________________________________________
* * * * *