Note: Descriptions are shown in the official language in which they were submitted.
3.~J~
This invention relates to an improved process for
the production of high quality mineral lubricating oils~ More
particularly, this invention re~ates to the production of
such olls employing hydrogen processing of low quality
feedstoc~s.
Many of the present day refininy 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.
U.S. Patent 3,642,610 teaches an improved method of ~ -
producing lubricating oils having increased VI's at increased ;
yields. However, still further improvement in the yields of
these valuable lubricating oils is desirable.
Therefore, one object of the present invention is to
provide an improved method for producing lubricating oils
having increased viscosity indexes.
Another object of the present invention is to ~-
provide an improved method for producing high quality lubricating
oils in increased yields. Other objects and advantages of the ~;
present invention will become apparent hereinafter. -
An improved process for preparing a mineral hydrocarbon
oil having an inereased viscosity index on a dewaxed basis has
now been diseovered. This improved process eomprises
contaeting a mineral hydrocarbon oil feedstoe~, preferably a
residual oil, of lubricating viscosity, at least about 90~ by
- ~
weight of which boils above about 600F~ and having a viseosity
index of about 50 to 85, with molecular hydrogen at hydrocarbon
--1-- , : :
'; ~ .' ' ~ ''
' ,~.
hydrocracking conditions in the presenc~ of a catalyst which
comprises a major amoun-t of ~ ca-talytically-active support
derived by the calcination of a material comprising about
30% to about 70% by weight of sllica and about 30% to about
70% by weight of alumina, based on the total silica and alumina : -
in the support, the silica and alumina being supplied by a mixture
comprising about 40% to about 90% by weight of amorphous .
silica-alumina and about 10% to about 60% by weight of alumina
de.rived from hydrous alumina selected from the group consisting ~ ~
10 of boehmite and mixtures of boehmite and amorphous hydrous .~ . -
alumina, and a minor, catalytically effective amount of each
of at least one metal selected from the group consisting of ~ :~
Group VIb metals, preferably, tungsten, molybdenum and mixtures - .
thereof, and at least one metal selected from the group
consisting of the Group VIII metals, preferably the Group VIII
iron group metals and ~ore preferably nickel; and (2) contacting ~. :
hydrocarbon oil of lubricating viscosity from step (1) with . ; .:
~ molecular hydrogen under hydrocarbon hydrogenation conditions . ;.
in the presence of a solid hydrogenation catalyst at a - .
20 hydrotreating severity such that not more than about 5 volume ;~
percent of the feed to step t2) boiling above about 600F. is
cracked to material boiling below about 600F. to produce oil
of lubricating viscosity having a viscosity index of at least
about 90 and at least about 20 viscosity index numbers greater
than the hydrocarbon oil feedstock contacted in step (1). -
The mineral lubricating oils treated by the process of
the present invention are of lubricating viscosity, e.g., at `~
210F., and are principally stocks having at least about 90% by . ~.
weight boiling above about 600F. Preferably, such oils are
residual mineral oils at least about 90% b~ weight of which boils
: --2~
:~V~
above about l,000F~ sy "residual" is m~ant that ~uch oil is
no~ a distillate, e . g., has not been ta~en overhead in a
distillation column. The feeds are usually oils of at least about
50 VI, e.g., about 50 VI to about ~5 VI, or even about 70 VI
to about 85 ~I, and can be derived, for example, from paraffinic
or mixed base petroleum 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, numbers over that of the feed mineral oil 7 . ' ~'
Both the initial hydrocarbon feedstock and the product of lubrica-
-ting viscosity from the hydrogenation step may boil over a
considerable temperature range, e.g~, over a range of at least
about 100F. and often at least about 200F. The hydrocarbon
feedstock preferably has a specific dispersion (A5TM Designation
D~1218~ in the range of about 105 to about 165 while the specific
dispersion of the product of lubricating viscosity is preferably
in the range of about 100 to about 110. The method of the
present invention is particularly suitable for treating feedstocks
having a specific dispersion in the range o about 135 to about
165, such stocks being the highly contaminated stocks, e.g.,
containing larger amounts of aromatics. Thus, the present
method can utilize an economically cheaper feedstock to produce
high quality lubricating oils in high yields.
Hydrocracking of the feedstock, which often includes
some ring opening as well as desulfurization and denitrogenation,
is carried out in step (1) by contacting the feedstock with a
catalyst comprising a major amount of a catalytically active
support derived by the calcination of a material comprising
about 30% to about 70~ by weight of silica and about 30% to
about 70% by weight of alumina, based on the total silica and
alumina in the support, the silica and alumina being supplied
~v~
by a mixture comprlsin~ about ~0~ to about 90% by weight
amorphous silica-alumina and about 10~ to about 60~ by weight
of a group consisting of boehmite and mixtures of boehmite and
amorphous hydrous alurnina, and minor catalytically eff~ctive
amounts of at least one Group VIb metal and at least one
Group VIII metal. These metals may be present in the ~orm 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). The Group VIb metals preferably ~-
are present in the step (1) catalyst in an amount of about 5% to
about 40%, more preferably about 10% to about 30% by weight of - -
the total catalyst, calculated as the metal oxide. The Group
VIII iron-group metal is usually present in an amount of about 2%
to about 15%, preferably about 2~ to about 10~ by weight of
the total catalyst, calculated as the weight of the free metal.
The Group VIII platinum group metal can be, for example, about ~ ;
0.1% to about 3~, preferably about 0.1% to about 1%, by weight ~
of the total catalyst calculated as the elemental metal. ~;
The catalyst composition used in step (1), e.g., the
hydrocracking stage, of the present invention can be formed by / ;~;
various means well known in the art, e.g., extrusion, tabletting,
spheridizing, and the like, into, for example, extrudates
having a diameter of about l/64 inch to about 1/2 inch, prefer- -`
ably about 1/64 inch to about 1/4 inch, and a length of about
1/64 inch to about 1/2 inch, preferably about 1/16 inch to about
1/2 inch, preferably about l/16 inch to about 1/4 inch; and
spheres having a diameter of about 1/64 inch to about 1/2 inch,
preferably about 1/16 inch to about 1/4 inch. These
catalyst particles often have a packed apparent density of
about 0.3 gram/cc. to about 1 ~ram/cc.
~4~
The support of the catal~st used in step (1) contains
a total of about 30% -to about 70~ by weight of silica and about 70%
to about 30~ by weiyht of alumina, preferably about 35% to ~-
about 65~ by weight o~ silica and about 65~ to about 35% by
weight of alumina. This support is a composite formed by the
combination of about 40% to about 90~, preferably about 40% to
about 85%, by weight of amorphous silica-alumina and about 10
to about 60%, preferably about 15% to about 60% by weight of
alumina derived from hydrous alumina selected from the group
consisting of boehmite and mixtures of boehmite and amorphous
hydrous alumina. The amorphous silica-alumina component of the
catalyst may be available in the form of relatively finely divided
particles, e.g., of a particle size of up to about 65 microns,
and contain about 40% to about 92~ by weight of silica and
about 8~ to about 60% by weight of alumina. Commercially
available silica-alumina hydrocarbon cracking catalyst particles
can be used in making the catalyst used in step (1) of this ;
~ invention and, in one instance, can contain 87~ wéight percent
silica and 13~ weight percent alumina.
While these commercially available powders are relatively
finely divided, the average particle diameter may be too large
for most effective utilization in forming the catalyst support, i~
for example, the spherical supports useful in the present ~ ~`
invention.
Reduction of the size of these particles can be
accomplished by milling. The milling can be, for example, wet-
ball milling, dry impact milling, colloidal milling, etc.
For more efficient utilization, in the present invention at ;~
least about 80 weight percent, preferably at least about 90
weight percent, of the silica-alumina particles should have an
~ . :
,, . ,. , . ,. ........ . ... , , .. ~ .. .. , .,........ : :
~3~
average par-ticle diameter of ~bout ~ micron.~ or l~ss. In a
more preferred embodime~t, at least abou-t 50 weight pereerlt of
the silica alumina particles have a diam~er of less than about 30
microns in order that the final ca-talyst particles used in step
(1) of the present invention are devoid of or reduced in surface
cracks and resulting weakness.
The silica-alumina component of the eatalyst used
in step (1) of the present invention may also be prepared by
eonventional methods similar to those methods known to the art
10 for the produetion of synthetic silica-alumina eraeking catalyst. ~ -~
Sueh preparations may involve forming a silica hydrogel by the
preeipitation of an alkali metal silicate solution with an aeid
-sueh as sulfurie aeid. Alumina is then preeipitated by adding
an alum solution to the siliea hydrogel slurry and raising the -~
pH into the alkaline range by the addition of sodium aluminate
solution or by the addition of a base sueh as ammonium hydroxide.
These conventional methods for produeing silica-alumina also
: :.
inelude eo-preeipitation techniques wherein the aeid-aeting alum
solution is added to the silicate solution to precipitate ;~-
both silica and alumina simultaneously perhaps with a pH
adjustment for further preeipitation. Also, a eonstant pH
~,~ . .. .
teehni~ue whereby the solutions of each oxide component are
added eontinuously to a mixing vessel may be employed. In any
event, the alumina is preeipitated in the presence of silica
to form what may be referred to as coherent aggregates of silica-
alumina. Although the silica-alumina component of the present
step (1) catalyst supports may have a wide range of surface areas,-
for example, about 50 m.2/gm. to about 500 m.2/gm. or more,
it is preferred that the silica-alumina have a surfaee area ~ -
30 of at least about 300 m.2/gm. The surface areas referred to ~ ;
-6- -
' :; '
. ' .
. .... , , ., .. , - . - .-- , - - -
:: . . ~ . . . ; :. :, ., :. ,,, ~ . - ,
herein are as d~te.rmin~d by ~he B~:T nitrogen adsorption procedure
(JACS, vol. 60, pp. 309 et g~., 1398).
The added alumlna content of the step (1) catalyst
support of the present i~vention is obtained by combining alumina
as hydrous alumina with the silica-alumina which may ~e, at the
time of hydrous alumina addition, in any stage of manufacture,
from the original crude hydrogel as precipitated and separated
from the aqueous s~pernatant liquid to the completely finished
silica-alumina product in either dried or calcined form.
The present step (1) catalyst supports may be
prepared by precipitation of hydrous alumina in the presence of -
the silica-alumina at a pH of about 5 to about 9, or the alumina ;
hydrogel may be prepared separated. In either case, the
preparation is such as to produce a support having added ~ ~ -
alumina in the form derived from hydrous alumina selected from
the group consisting of boehmite and mixtures of boehmite and ~ -
amorphous hydrous alumina. Preferably, the boehmite alumina has -~
a crystallite size of up to about 50 A. as determined by X-ray
diffraction on samples dried to 110C. The boehmite crystallite
O
size L, in angstrom units (A), is an estimate obtained from the
width of one of the diffraction peaks, using the Scherrer equation
in the form
0.9~ _
B cos 1/2
Here B is the width of the line at half maximum measured in-
radians, ~is the wave length of the X-rays used in angstrom
units (1.54), and 3is the spectrometer angle at which the
peak occurs (38). When mixtures of boehmite and amorphous
hydrous alumina are used, the boehmite preferably comprises about
45% to about 85% by weight of the mixture and the amorphous
hydrous alumina comprises about 15% to about 55% by weight
of the mixture.
.,, .' ' ~
3~
The hy~rous alumina precursor of the added alumina
of the present step tl) ca-talyst supports can be prepared by
various methods. Separate preparation of the hydrous alumina may
be, for example, by precipitation of alumina at alkaline pH
by mixing alum with sodium aluminate in aqueous solution or
with a base such as soda ash, ammonia, etc. The solution from
which the hydrous alumina is precipitated may contain a concen-
tration of about 5% to about 20% by weight of the aluminum
salt. Ammonia, or more preferably ammonia water, or other
10 aqueous base, can be added to the solution until the desired -~
amount of alumina hydrate gel is precipitated. Preferably,
at the en~ of precipitation, the slurry is so thick that it
just barely can be stirred. After formation of the alumina
hydrogel is complete~ it may be filtered or decanted prior
to its combination with the silica-alumina. The alumina hydrogel
filter cake may be water washed to remove part or most of its
ion content, e.g., sulfate and sodium ion present in the gel, but `
preferably this step is omitted~ Thereafter, the alumina hydrogel
is ready for mixin~ with the silica-alumina material, for
20 example, silica-alumina hydrogel, and the combined hydrogel ~ ;
slurry is stirred continuously until a uniform mixture is ;
obtained, usually about 30 to about 60 minutes stirring time
is sufficient. The aqueous hydrous alumina-silica-alumina
slurry may then be washed and concentrated as by settling and
the aqueous material filtered off after which the ca~lyst
precursor is thoroughly washed to remove interferxing ions,
especially, sodium and sulfate ions. The final step (1)
catalyst support prefera~ly contains less than about 0.5% by ;;
weight sulfate.
`
-8-
'`. : '
~ t~3~
The hydrous alumina precursor may be prepared in the
presenc~ of the silica-alumina component of ~he present
step (1) catalyst supports. In this procedure, -the hydrated gel
is preferably formed by reactlng an aqueous solution of an
aluminum salt of a strong inorganic acid, usually aluminum
sulfate, with a base preferably ammonia water, at a pH which
may vary within the range of about 5 to about 9, preferably
substantially all of the alumina is precipitated at a pH of
about 7 to about 7.5. Precipitation of alumina from an aqueous
solution of an alkali aluminate by addition of an acid may also
be employed. Also, the hydrous alumina may be precipitated by
hydrolysis from alcohol solutions of aluminum alkoxides although
the use of inorganic salts is preferred.
One particularly preferred method for preparing this
precursor hydrous alumina is by the conventional acid hydrolysis
of finely divided aluminum. In this manner, the dispersion or
slurry of hydrous alumina prepared by this method can obtain
amorphous alumina as well as boehmite.
In the acid hydrolysis process, aluminum, preferably
20 in a state of extremely fine subdivision and high surface area, ~ ;
is contacted with water, preferably at a temperature near the
boiling point of water, in the presence of a non-oxidizing acid.
The reaction produces a fine particle hydrous alumina slurry in
water, the hydrous alumina comprising either boehmite or both of
the valuable boehmite and amorphous forms.
In this hydrolysis process step, the aluminum employed
can be finer than most materials referred to as "powder" and the
metal can have a surface area of about 75 thousand to about 1
million square millimeters per gram. preferably about 150,000 ~;~
to about 600,000 mm.2/gm~ The aluminum may often be in the
_g_
- - ~ . -
general particle siæe rancJe o~ about 2 to abou~ 100 microns.
Preferably at ~east about 50 percent of the particles are about
10 to about 40 microns. The aluminum is usually one where at
least about 90 percent can pass a 325 mesh sieve (U.S. Standard
Sieve Series).
An aluminum suitable for this hydrolysis may have
a purity greater than about 99% by weight or even greater than
99.9% by weight and may be obtained by atomizing molten
aluminum in air. -~
Water soluble, organic carboxylic acids generally are
preferred for the reaction, in particular, the soluble saturated
lower fatty acids, say of 1 to 2 carbon atoms, e.g., formic acid,
-acetic acid, tri-chloroacetic acid, etc. The monobasic acids
are advantageous and formic acid is the most preferred.
The total reaction mixture usually contains a ratio of
about one mole acid to about 2 to about 30 gram atoms of aluminum ;~
metal to at least about 18, e.g., about 18 to 2,250 moles, of
water. Preferably about 100 to about 750 moles of water and
about 5 to about 15 gram atoms of aluminum are often used per
mole of acid.
It may often be preferred to add the aluminum metal and/or
the formic acid incrementally to the water during the course of
the reaction. Such incremental additions of formic acid and
aluminum metal should preferably be at such rates that the approxi-
mate 1:5 to 15:100 to 750 acid-aluminum-water ratio described `
above and the about 3 to about 4 pH are maintained essentially
throughout the reaction. Such manipulations accelerate tha rate
of reaction and provide for improved concentration of A12O3 in
the product slurry. For ease of handling, the fine aluminum
30 powder may often be transported to the reaction zone as a -~
slurry in water.
-10
.1 ~.'.', ~,
~ ;~
''.
L~3B''
Reaction conditions ~or producing the alumina yenerally
include a temperature of at least about 60C., although the reaction
may be slow below the preferred range of about 90C. to about
110C The reaction can readily take place at a higher temper-
ature, e.g., up to about 500 pounds steam pressure, that is, ~ -
about 250C., but pressurized equipment is required at this
temperature to keep the necessary liquid phase. At the preferred
temperature or below, one atmosphere pressure is satisfactory
and water may be refluxed during the reaction. Often the reaction -~-
produces a relatively highly concentrated alumina slurry which
can be sent directly to an alumina coagulation procedure.
Sometimes, however, it may be desirable to further concentrate
'the slurry and in such cases, additional acid may be used after the
reaction to peptize the alumina particles. Subsequent evaporation
can then be employed to obtain a pourable thick slurry containing
up to about 60 weight percent or more hydrous alumina.
Once the aqueous hydrous alumina-silica-alumina slurry
is obtained, particles of the present step (1) catalyst support
may be formed, washed, dried and calcined using methods well
known in the art. It may be necessary to adjust the free water
concentration of the above-noted slurry depending on how the
catalyst support particles are to be formed. Tabletting, for
example, generally requires a dryer mix than does extruding,
which usually calls for a free water content of about 20% to
about 40% by weight. Therefore, the slurry may be partially dried.
The temperature at which the drying is performed is not critical
but it is generally preferred to operate at temperatures up to
about 400F. It may be - because of the type of equipment employed,
or for watever reason - that it is preferable to dry the slurry
completely, or relatively so, and then add back sufficient water
to obtain a formable, e.g., extrudable, coag~able (for spheridizing)
etc., mix. In many instances, for example, when the final catalyst
--11-- ,
r~
is to be in the form of extruda-t~s, tablets, pills and the like,
the slurry may be dried, for example, by spray-dryiny, to form
microspherical particles which can be impregnated with the Group
VIb and/or Group VIII metal using methods well known in the
art. This impregnated material may be Eormed, dried and calcined
using conventional methods to produce the final step (1) catalyst
of the present invention. Also, the catalytically-acti~re metals
may be added after the support is formed, washed, dried and
calcined and when the catalyst is to be in the form of spheres
10 produced by the oil drop method, this procedure is preferred. ~ ~ -
The formed particles are calcined at temperatures
suf~icient to effect the release of water of hydration from
the particles and to provide a ca~lytically active alumina.
Generally suitable are temperatures of about 600F. to about
1350F., preferably about 800F. to about 1150F. The calcination
can be effected in an oxidizing, reducing or inert atmosphere, the
more economical use of a dry air calcining atmosphere being `
preferred. It is usually advantageous to calcine in a flowing
stream of the gaseous atmosphere~ Pressure can be atmospheric,
super-atmospheric or sub-atmospheric. Preferably, the final step
(1) catalyst has a surface area of at least about 140 m.2/gm.
When the above-noted commercially available silica-
alumina particles are to be used in combination with hydrous
alumina derived from acid hydrolysis of aluminum to form generally
spherical catalyst supports, it is preferred that the silica-alumina
particles be added in more or less dry conditions, e.g., either
dried-milled or dried, wet-milled, to the acid hydrolysis product
to prevent further dilution of the slurry. The mixture of silica~
alumina and alumina is fed to a spheridizing column to form the
generally spherical support. The spheres can be, for example,
up to about 1~8 inch in diameter, often about 1/64 inch in
diameter. ~
-- -12- ;
The spheres may be prepared by -the oil-drop method,
for example, as disclosed in U.S. Patent 3,558,508. In the
oil-drop method, drops of a coagulable aqueous slurry o~ the
mixture of silica-alumina and hydrous alumina are fed with a
column of a water-immiscible liquid, e.g., mineral oil, which
can be maintained at close to ambient temperature, e.g., up to
about 120F. The column can also contain a coagulating agent ~
which is preferably gaseous ammonia passing upwardly through the ~ -
column. As the drops descend in the column essentially firm ~`
spheroidal particles are formed. The resulting particles can
be collected in the lower portion of the column separated from
the water-immiscible or other li~uid and, if desired, aged in -~
ammonia water, washed, dried and calcined. If the solid precursor
is calcined, the resulting product is a hard, porous spheroidal
alumina gel. Calcination is at a temperature which gives a catalyti-
cally active alumina, for example, about 800F. to about 1350F.
The gelation of the spheroidal particles can be brought
about in part by the presence of a coagulating agent in the
water-immiscible liquid. Although ammonia is preferred, other
coagulating agents can be used. Among the useful materials are
the weak bases which are water-soluble and have a strong buffering
action at a-p~ from about 4 to about 10, preferably about 5 to
about 9, e.g., hexamethylene tetramine. Various nitrogen-
containing bases can be used~ e.g., urea, tetramethyl ammonium
hydroxide, etc. some of which may release ammonia in the water-
immiscible liquid. ~he coagulating agent can be mixed with the `;
alumina before the latter is formed into drops providing the `
alumina is not unduly gelled which may particularly be a problem
if too much gelling agent is added or if the mixed material
30 is allowed to sit for too long a time before being released from ~ ~ ;
the drop-forming mechanism. It is preferred, however, that the
-13~
' ~ :
coagulating agent be mixed ~lith the water-immiscible liquid
into which the drops are passed.
A frequently used water-immiscible medium is white
mineral oil having a specific gravity of at least about 0.850.
The medium utilized is dependent upon the leng-th of the oil
column and the specific gravity of the slurry which is in turn
dependent upon the total solids concentration in the slurry.
If the specific gravity of the oil medium is too low, the
spheroidal particles will fall through the column at a high rate -
~
which may cause incomplete gelation, thus making the handlingand processing difficult. If the specific gravity is too high,
this may retard completely the descent of the spheroids.
The specific gravity of the feed slurry is often in the range
of about 1.150 to about 1.1700 The length of the oil column
can vary widely depending, for instance, on the speed of coagu~
lation. The column will usually be from about 1 foo-~ to about
30 feet in length, more often about 6 feet to about 20 feet.
The calcined step (1) catalyst support particles,
e.g., spheres, may be impregnated with the catalytic metals,
e.g., Group VIb and Group VIII metals. The catalytic metals
can be present in the final catalyst as the free metals or in
combined form such as the oxides and sulfides. Especially
preferred catalysts contain nickel together with either tungsten
oxide or sulfide or molybdenum oxide or sulfide.
The impregnation can be carried out as is known in the ` -
~art. The metal is preferably in solution as a compound which is - ~;
a precursor of the form, e.g., free metal, metal oxide or metal ~-
sulfide, desired in the step (1) catalyst. For example, to
prepare a catalyst containing nickel and molybdenum oxide (MoO3),
: ,,~ . .
a solution of nickel nitrate and ammonium molybdate in ammonia
and water can be used as the impregnating solution. The
-14- ;~
~3~ f~
lmpregnated support can then be dried, ag, for example, at a
temperature of about 200F, to about 270F. for a time such as
15 to 20 hours, and then calcined in flowing air at a temperature
of about 900F. to about 100F. for about 2 hours to about 4 hours.
Alternatively, ammonium molybdate can be dissolved in a solution
of aqueous ammonia, prepared by admixing 29% ammonia and water
in a ratio of 1.76:1, nickel nitrate is then added in this solution
and forms the nickel amine complex
(Ni(NH3)6++)
10 This solution can then be used as the impregnant with the --
impregnated support being dried and calcined as before.
The impregnation of the support with the catalytic metal solutions
can also be performed sequentially, that is, impregnation with a -
solution of ammonium molybdate in ammonia followed by drying and
calcination of the particles and then impregnation of the
molybdenum-oxide containing support with a solution of nickel
nitrate followed by another drying and calcination. Alternatively, ~;
--the support may be impregnated with the Group VIII metal first. ~ ;
The impregnated support can be reduced in hydrogen, as
by heating the support in a stream of hydrogen at a temperature of
about 400F. to about 1000F., preferably about 500F. to about
800 F. To convert the metal and/or metal oxides in the catalyst
to the sulfides, the support containing the metals in oxide
form as obtained from the calcination may be sulfided by passing
hydrogen sulfide, either pure or diluted with another gas,
such as, for instance, hydrogen, over the catalyst bed at
temperatures usually below about 800F., preferably about 400F.
to about 600F., for a time sufficient to convert a major
portion of the oxides of the metal components to their respective
-15-
~L~3~
sulfides. Alternakely, the step (l) catalyst may be sulfided
during processiny by the sulfur in the hydrocarbon feed. Also,
the metals can be deposited in the sulfide form when slurried
as the sulfide in the manufacture of the step (1) càtalyst.
Step l is carried out under conditions to selectively ;
hydrocrack the mineral hydrocarbon oil feedstock so that opening
of aromatic and naphthenic rings is favored, rather than the
splitting of chains into lower molecular weight compounds. Such `~
conditions preferably include a temperature of about 725F. to ~- ;
lO about 875F., more preferably about 750F~ to about 850~F. The
other reaction conditions preferably include a hydrogen partial
pressure of about 1,000 psigO, to about 5,000 psig., more
preferably about 1,500 psig. to about 3,000 psig. 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 about 10 percent
by volume of the product of step (1) is material boiling below
about 600F. In the production of 120 VI oils, about 30 to about
40 percent by volume of the product of step (1) may be
comprised of such materials. The ratio of free hydrogen to hydro-
20 carbon feed employed in step (l) can be preferably about 1,000 ;~
standard cubic feet per barrel of hydrocarbon feed (s.c.f./b.)
to about 8,000 s.c.f./b., more preferably about 1,500 s.c.f./b.
to about 3,000 s.c.f./b. The weight hourly space velocity (WHSV),
weight of feed introduced into the reaction zone per unit weight
o~ catalyst per hour, is preferably in the range of abbut 0.3 to
about 3, more preferably about 0.5 to about 2. The reactor effluent -
from the step (l), e.g., the hydrocracking stage, can be flashed ~- ~
to prevent hydrogen sulfide and ammonia from going to step (2). ; -
However, such processing is not necessary, especially if non~
precious metal cataIysts are used in step (2) of the present
invention. Also, if desired any light hydrocarbons can be
-16
.~ ,
~(3~.r~ '
removed from the fee~ to step (2).
At least a portion of the lubricating oll ~rom step (1)
is subjected to step (2), which involves contacting lubricating
oil, preferably the essentially full range lube oil from
step (l) in the presence of hydrogen with a solid catalyst,
preferably at a temperature of about 550F. to about 825F.,
more preferably about 600F. to about 800F. It is preferred
that the temperature employed in step (2) be at least about 50F.
less than the temperature of step (l) for optimum decolorization
and saturation. The other conditions in step (2) preferably
include pressures of about l~000 psig. to about 5,000 psig., more -~
preferably about 1,500 psig. to about 3,000 psig., WHSV of about 0.3 ~ -
to about 5~ more preferably about 0. 5 to about 3~ and molecular ;~ -
hydrogen to feed ratios of about 500 s.c.f./b. to about 3~500
s.c.f./b., more preferably about 1~500 s.c.f./b. to about 3r000
s.c.f.~b.
The solid catalyst employed in step ~2), eOg., the
--hydrogenation operation, is prefexably a sulfur-resistant, non-
precious 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 Group VIII iron group, i.e., iron ~;~
cobalt and nickel. ~hese metals are present in minor, catalyti- ; `
cally e~fective amounts, for instance, about 2 to about 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 metals
constitute very satisfactory catalysts. Examples of such mixtures
-17-
or compounds are nick~1 molybdate, tuncJstate 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 7 Usually, not ;
10 more than about 5 volume percent, preferably not more than about -
2 volume percent, of the hydrocarbon feed to step (2) is cracked
in this step to produce materials boiling below about 600F.
Commonly employed catalysts have about l to about 10 weight
percent of at least one iron group metal (calculated as elemental
metal) and about 5 to about 25 weight percent of at least one
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. Patent No. 2,938,002.
Other suitable hydrogenation catalysts which can be -
employed in the method of this invention include the Group VIII
platinum group metal types. Such catalysts often have a minor
catalyticaIly effective amount, say about 0.05 to about 2 weight~ `
percent, preferably about 0.1 to about 1 weight percent of one or
more platinum group metals carried on a solid support, especially
an active alumina. Preferred platinum group metals include
platinum, palladium, rhodium and ruthenium with platinum being ~ ;
,,~ .,.
more preferredO
The catalysts employed in both the step (l) and (2)
30 hydrogenation stages of the method of this invention are preferably ~;
disposed in one or more reaction æones as fixed beds.
-18-
.
8~
Step (2) of the present metho~ often provides additional
aromatic saturation, color improvement and stability towards
oxidation and corroslon. Additional color improvement can be
provlded by subjecting at least a portion of the effluent from
step (2) to treatment with ultraviolet light. The treatment was
~ound to lighten considerably the color of the darker oils.
The reactor effluent from step (2) 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 e~hyl ketone and toluene as the solvent ;~
system. Dewaxing may be carried out prior ~o step (1), but it is
pre~erred to conduct dewaxing after step (~) has been completed.
No additional finishing is required.
Increased yields of high quality lubricating oils are ;~
obtained by practicing the present invention. For example, yields
of about 60 to about 80 volume percent, based on the raw stock, of .
95 VI oils are not uncommon and finished base oils having viscosity
20 indexes of 120 and higher are obtained in economical yields, ~`
e.g., in the range of about 40 volume percent and higher. ``~
E~AMPLES
The following examples illustrate certain of the
benefits of the method of this invention. `~
A series of five (5) step (1) catalysts were prepared
and employed at the hydrocracking conditions described herein.
Each of these step (1) catalysts was prepared using ;
conventional techniques well known in the art. A list of the proper~
ties of these catalysts follows.
. . - .:
- 1 9
:,. " ~ ~:: '
3'j
CATALYST ~(4) (5) B(7) C(5) D(6) E(7)
__
Compo.sition
Nickel (1), Wt.~ 5.1 3.7 3.5 6.8 6.4
Molybdenum(2), Wt.~ - 15.4 16.0
Tungsten(2), Wt~% 11.3 ~ - 13.5 20.3
Boria, Wt.~ 8.0
Silica-Alumina, Wt.% - 42.7 50.7 48 37.3
Gamma Alumina(3), Wt.% - 38.2 29.8 31.7 36.0
Physical Properties
10Surface Area, m.2/gm. 148 169 251 223 137 -
Total Pore Volume cc./gm~ .42 0.83 0.39 0.39 0.71
(l)Calculated as elemental metalO
(2)Calculated as the metal oxide.
(3)Derived from hydrous alumina predominating-in
a mixture of boehmite and amorphous hydrous
alumina. Also, the silica~alumina contained
25 wt.% alumina.
(4)Catalyst A is similar to that described in
U.S. Patent 3,642,610; the remainder of such
catalyst being a conventional alumina support.
(5)In the form of 1/16 inch diameter extrudates.
(6)In the form of 1/8 inch diameter tabletts.
(7)In the form of 5/64 inch diameter beads.
The test procedure using each of these catalysts
was as follows. A propane deasphalted residual oil was used
as the hydrocarbon feedstock. This residual oil had the
following properties~
'`' `'~'':
:,:
-20- ;
.. ~ ::
''- ` ~' ~ .
'' ~ .
,
Viqcosity Index (dewaxed
baSis) (D 227D) 79
Graviky, ~PI 23.2
Viscosity, SUS/210~. 33.9 -
Wt.% Hydrogen 12.73
Wt.% Sul~ur 0.54 ;
Wt~ Nitrogen 0. l~s `
Boiling Point (ASTM-D1160)F.
5% ~85
40% 1051
This resldual oil was contacted in an isothermal
laboratory reaction zone with each of the step (1) catalysts -~
described previously in the presence of hydrogen at the
s~ ~,~:-, : . ::
following conditlons~
PRESSURE, psig. 2500
H2 Rate, s.c.f./b. 2500
WHSV 1~0
Temperature as indicated
Bach;of the catalysts was presulfided, using conventional
20 techniques. `~
The resulting hydrocarbon effluents~from these
~contactings were analyzed for viscosity index~and weight ~
yield, on a dewaxed basis. ~Results obtained from this test
procedure~are summarized below.
., ~
:: i:, ~.
~ ~ : ' ;^.-.'., ,, ~ .
. :: ::
38~ 35
STEP (1) C}~TALYST A B C D (9) E (9)
.
100 V,I. Oil Produced
Step (1) Temperature,F. 779776 778 783 780
Yield, Wt.% Based on
Residual Oil Feedstock ~8 70 69 65 66
Relative Activity of
Step (1) Catalyst (8) 1.01.1 1.0 0.9 l.O
125 V.I. Oil Prcduced
Step (1) Temperature,F. 827802 811 835 825
10 Yield, wt.% Based On
Residual Oil Feedstock 46.5 54 49 37 43
Relative Activity of
Step (1) Catalyst (8) 1.02.0 1.6 0.8 1.1 - -~
(8~Relative activity is a measure of the hydro~
cracking catalytic activity related to viscosity
index improvement of each of the step (1)
catalysts based on such catalytic activity
;. .
of catalyst A.
(9)Because of differences in various experimental
factors, e.g., catalyst particle size and shape,
the laboratory results obtained using catalysts B,
D and E cannot be directly compared to the results ~ ~
obtained with catalyst A. ~ ~ -
~ . ..
High V.I~ lubricating oils in good yields are obtained from ;
,
the effluents of each of these further contactings.
These results clearly demonstrate that the present
process provides high yields of lubricating oils with
increased viscosity indexes. In addition, the above data show
that the present invention, which involves the use of a step
-22~
.; '~--::': : .
. ~,, .
,~:.'" ' '
(1) catalyst containiny both silica-alumina and alumina,
provides improved results, e.g., increased yields o~ high
quality lubricating oil, relative to results obtained using
a prior art boria-containing catalyst. An zdditional advan-
tage of the present step (1) catalyst i8 that of regenerability.
That is, the hydrocracking activity of the present silica-
alumina and alumina-containing catalyst can be at least par-
tially restored by contacting the deactivated catalyst, e.g.,
catalyst from processing having carbonaceous material deposited
10 thereon, with an oxyyen-containing gas at conditions to combust ~ -
at least a portion of the carbonaceous deposit material.
Attempts to regenerate boria-alumina catalysts in this manner
tend to result in reductions in catalyst boron content and,
therefore, permanent catalyst deactivation.
The above data and observations make clear the substan-
tial improvement achieved by the present invention. High ~ `;
quality lubricating oils are obtained in improved yields.
Moreover, the present step (1) catalyst possess substantial
processing advantage over prior art catalysts. ;
While this invention has been described with respect
to various specific examples and embodiments, it is to be
understood that the invention is not limited thereto and that
it can be variously practiced within the scope of the
following claims.
. '
-23- ~-
' ''
':~' ~.' :~
- ' '" '"':' -, .
