Note: Descriptions are shown in the official language in which they were submitted.
20~6~3~
PROCESS FOR OLIGOMERIZING OLEFINS USING NOVEL BLENDS OF ACIDIC
MONTMORILLONITE CLAYS AND SULFATE-ACTIVATED GROUP IV OXIDES
(D# 81,065-F)
Background of the Invention
Field of the Invention
The invention relates to the preparation of synthetic
lubricant base stocks, and more particularly to synthetic lubricant
base stocks made by oligomerizing linear olefins.
Description of Related Methods
Synthetic lubricants are prepared from man-made base
stocks having uniform molecular structures and, therefore, well-
defined properties that can be tailored to specific applications.
Mineral oil base stocks, on the other hand, are prepared from crude
oil and consist of complex mixtures of naturally occurring
hydrocarbons. The higher degree of uniformity found in synthetic
lubricants generally results in superior performance properties.
For example, synthetic lubricants are characterized by excellent
thermal stability. As automobile engines are reduced in size to
save weight and fuel, they run at higher temperatures, therefore
requiring a more thermally stable oil. Because lubricants made
from synthetic base stocks have such properties as excellent
oxidative/thermal stability, very low volatility, and good
viscosity indices over a wide range of temperatures, they offer
better lubricatlon, and permit longer drain intervals with less oil
vaporization loss between oil changes, than mineral oil base
stocks.
~6~38
Synthetic base stocks may be prepared by oligomerizing
internal and alpha-olefin monomers to form a mixture of dimers,
trimers, tetramers, and pentamers, with minimal amounts of higher
oligomers. The unsaturated oligomer products are then hydrogenated
to improve their oxidative stability. The resulting synthetic base
stocks have uniform isoparaffinic hydrocarbon structures similar to
high quality paraffinic mineral base stocks, but have the superior
properties mentioned due to their higher degree of uniformity.
Synthetic base stocks are produced in a broad range of
viscosity grades. It is common practice to classify the base
stocks by their viscosities, measured in centistokes (cSt) at
100 C. Those base stocks with viscosities less than or equal to
about 4 cSt are commonly referred to as "low viscosity" base
stocks, whereas base stocks having a viscosity in the range of
around 40 to 100 cSt are commonly referred to as "high viscosity"
base stocks. Base stocks having a viscosity of about 4 to about 8
cSt are referred to as "medium viscosity" base stocks. The low
viscosity base stocks generally are recommended for low temperature
applications. Higher temperature applications, such as motor oils,
automatic transmission fluids, turbine lubricants, and other
industrial lubricants, generally require higher viscosities, such
as those provided by medium viscosity base stocks (i.e. 4 to 8 cSt
grades). High viscosity base stocks are used in gear oils and as
blending stocks.
The viscosity of a base stock is determined by the length
of the oligomer molecules formed during the oligomerization
2~86~3g
reaction. The degree of oligomerization is affected by the
catalyst and reaction conditions employed during the
oligomerization reaction. The length of the carbon chain of the
monomer starting material also has a direct influence on the
properties of the oligomer products. Fluids prepared from short-
chain monomers tend to have low pour points and moderately low
viscosity indices, whereas fluids prepared from long-chain monomers
tend to have moderately low pour points and higher viscosity
indices. Oligomers prepared from long-chain monomers generally are
more suitable than those prepared from shorter-chain monomers for
use as medium viscosity synthetic lubricant base stocks.
One known approach to oligomerizing long-chain olefins to
prepare synthetic lubricant base stocks is to contact the olefins
with boron trifluoride together with a promotor at a reaction
temperature sufficient to effect oligomerization of the olefins.
See, for example, co-assigned U.S. Patent Nos. 4,400,565;
4,420,646; 4,420,647; and 4,434,308. However, boron trifluoride
gas (BF3) is a pulmonary irritant, and breathing the gas or fumes
formed by hydration of the gas with atmospheric moisture poses
hazards preferably avoided. Additionally, the
disposal/neutralization of BF3 raises environmental concerns.
Thus, a method for oligomerizing long-chain olefins using a less
hazardous catalyst would be a substantial improvement in the art.
Kuliev et al. attempted to prepare synthetic lubricants
by oligomerizing long-chain (Cg-Cl4) olefins using non-hazardous and
non-polluting acidic clays comprising sulfuric and hydrochloric
acid-activated bentonites from the Azerbaidzhan SSR. See Kuliev,
Abasova, Gasanova, Kotlyarevskaya, and Valiev, "Preparation of
High-Viscosity Synthetic Lubricants Using an Aluminosilicate
Catalyst," Institute of Petrochemical Processes of the ~cademy of
Sciences of the Azerbaidzhan SSR, Azer. Neft. Khoz., 1983, No. 4,
pages 40-43. However, Kuliev et al. concluded that "it was not
possible to prepare viscous or high-viscosity oils by olefin
polymerization over an aluminosilicate catalyst" and that "hydrogen
redistribution reactions predominate with formation of aromatic
hydrocarbon, coke, and paraffinic hydrocarbon." Gregory et al., on
the other hand, used Wyoming bentonite to oligomerize shorter-chain
olefins. (See U.S. Patent No. ~,531,014.) However, like Xuliev et
al., they also were unable to obtain a product high in dimer,
trimer and tetramer, and low in disproportionation products.
Applicants discovered that it is possible to prepare
synthetic :Lubricant base stocks in good yield by oligomerizing
long-chain olefins using certain acidic montmorillonite clay
catalysts. Applicants found that a high conversion of long-chain
olefins to dimer, trimer, and tetramer may be obtained with
formation of very little concomitant hydrogen redistribution by-
product by using an acidic calcium montmorillonite clay having a
moisture content ranging up to about 20 wt.%, a residual acidity in
the range of about 3 to about 30 mg KOH/g (when titrated to a
phenolphthalein end point), and a surface area of about 300 M2/g or
greater. In addition to being excellent catalysts, these clays are
non-hazardous and non-polluting.
20g6Q38
With respect to the present invention, Applicants have
discovered, surprisingly, that an even higher conversion of olefins
to oligomer may be obtained by contacting the olefin with a
catalyst prepared by blending a minor amount of a sulfate-activated
group IV oxide with the clay prior to its use as an oligomerization
catalyst. Moreover, the process of the present invention results
in a higher percentage of trimer and higher oligomers, i.e., a
lower dimer to trimer ratio, another desirable feature.
Summary of the Invention
The invention relates to a process for the preparation of
oligomers, comprising contacting at a temperature in the range of
50 C to 300 C (1) linear olefins containing from 10 to 24 carbon
atoms with (2) a catalyst consisting essentially of a physical
blend of a sulfate-activated Group IV oxide and an acidic
montmorillonite clay having a moisture content ranging up to about
20 wt.%, a residual acidity in the range of about 3 to about 30 mg
KOH/g, and a surface area of about 300 m2/g or greater, wherein the
catalyst contains said Group IV oxide and said acidic
montmorillonite clay in a weight ratio of Group IV oxide to clay of
about 1:1000 to about 1:4. The invention further relates to a
process for the preparation of oligomers, comprising oligomerizing
linear olefins containing from 10 to 24 carbon atoms in the
presence of a catalyst consisting essentially of a physical blend
of sulfate-activated zirconium oxide and an acidic montmorillonite
clay having a moisture content ranging up to about 20 wt.%, a
residual acidity in the range of about 3 to about 30 mg KOH/g, and
`"` 2~6~
a surface area of about 300 m2/g or greater, wherein the catalyst
contains said zirconium oxide and said acidic montmorillonite clay
in a weight ratio of zirconium oxide to clay of about 1:1000 to
about 1:5. The invention also relates to a process for the
preparation of oligomers, comprising oligomerizing linear olefins
containing from 10 to 24 carbon atoms in the presence of a catalyst
consisting essentially of a physical blend of a silicon dioxide-
supported sulfate-activated zirconium oxide and an acidic
montmorillonite clay having a moisture content ranging up to about
20 wt.%, a residual acidity in the range of about 3 to about 30 mg
KOH/g, and a surface area of about 300 m2/g or greater, wherein the
catalyst contains said silicon dioxide-supported zirconium oxide
and said acidic montmorillonite clay in a weight ratio of silicon
dioxide-supported zirconium oxide to clay of about 1:1000 to about
1:4, and wherein the olefins are oligomerized at a temperature in
the range of about 120 C to about 250 C.
Description of the Preferred Embodiments
The olefin monomer feed stocks used in the present
invention may be selected from compounds comprising (1) alpha-
olefins having the formula R"CH=CH2, where R" is an alkyl radicalof 8 to 22 carbon atoms, and (2) internal olefins having the
formula RCH=CHR', where R and R' are the same or different alkyl
radicals of 1 to 21 carbon atoms, provided that the total number of
carbon atoms in any one olefin molecule shall be within the range
of 10 to 24, inclusive. A preferred range for the total number of
carbon atoms in any one olefin molecule is 12 to 18, inclusiv~,
20~g~3~
with an especially preferred range being 14 to 16, inclusive.
Mixtures of internal and alpha-olefins may be used, as well as
mixtures of olefins having different numbers of carbon atoms,
provided that the total number of carbon atoms in any one olefin
molecule shall be within the range of 10 to 24, inclusive. The
alpha and internal-olefins to be oligomerized in this invention may
be obtained by processes well-known to those sXilled in the art and
are commercially available.
The oligomerization reaction may be represented by the
following general equation:
catalyst
nCmH2m ----~~~~~~~~ CmnH2mn
where n represents moles of monomer and m represents the number of
carbon atoms in the monomer. Thus, the oligomerization of l-decene
may be represented as follows:
catalyst
nClOH20 ~~~~~~~~~--> C10 H
where n represents moles of l-decene. The r~action occurs
sequentially. Initially, olefin monomer reacts with olefin monomer
to form dimers. Some of the dimers that are formed then react with
additional olefin monomers to form trimers, and so on. This
results in an oligomer product distribution that varies with
reaction time. As the reaction time increases, the olefin monomer
conversion increases, and the selectivities for the heavier
oligomers increase. Generally, each resulting oligomer contains
one double bond.
~0~38
The catalyst used in the present inventive process is a
physical blend of an acidic montmorillonite clay and a sulfate-
activated Group IV oxide. Preferably, the catalyst contains the
sulfate-activated Group IV oxide and the acidic montmorillonite
clay in a weight ratio of Group IV oxide to clay of about 1:1000 to
about 1:4 or, more preferably, of about 1:1000 to about 1:5. It is
more preferred that the catalyst contains the sulfate-activated
Group IV oxide in a weight ratio of Group IV oxide to clay of about
1:50 to about 1:9 or, more preferably, about 1:50 to abou~ 1:10.
It is especially preferred that the catalyst contains the sulfate-
activated Group IV oxide and the acidic montmorillonite clay in a
weight ratio of Group IV oxide to clay of about 1:50 to about 1:25
or, still more preferably, about 1:50 to about 1:40. The catalysts
of the present inventive process contain essentially no chromium,
and are non-halogenated, non-polymeric, and non-organometallic.
~ Optionally, the sulfate-activated Group IV oxide
component may be supported on a high surface area Group III or IV
oxide, such as high surface area silicon dioxide. The supported
sulfate-activated Group IV oxide is then blended with the acidic
montmorillonite clay. Applicants have discovered, surprisingly,
that excellent yields of oligomers are obtained when the sulfate-
activated Group IV oxide component is supported on silicon dioxide.
The high surface area of the silicon dioxide support unexpectedly
permits one skilled in the art to obtain substantially the same
benefits of blending unsupported sulfate-activated Group IV oxides
with acidic clays, but requires less of the expensive sulfate-
2~86Q~Y
activated Group IV oxide. When the sulfate-activated Group IV
oxide is supported on silicon dioxide, it is preferred that the
catalyst contains the silicon dioxide-supported Group IV oxide and
the acidic montmorillonite clay in a weight ratio of silicon
dioxide-supported Group IV oxide to clay of about 1:1000 to about
1:4. It is more preferred that the catalyst contains the silicon
dioxide-supported Group IV oxide and the acidic montmorillonite
clay in a weight ratio of silicon dioxide-supported Group IV oxide
to clay of about 1:50 to about 1:9. It is more preferred that the
catalyst contains the silicon dioxide-supported Group IV oxide and
the acidic montmorillonite clay in a weight ratio of silicon
dioxide-supported Group IV oxide to clay of about 1:50 to about
1:20.
The montmorillonite clays used in the present inventive
process are certain silica-alumina clays. Silica-alumina clays,
also called aluminosilicates, are useful cation-exchangeable
iayered clays. Silica-alumina clays primarily are composed of
silicon, aluminum, and oxygen, with minor amounts of magnesium and
iron in some cases. Variations in the ratios of these
constituents, and in their crystal lattice configurations, result
in some fifty separate clays, each with its own characteristic
properties.
One class of silica-alumina clays comprises smectite
clays. Smectite clays have unusual intercalation properties that
afford them a hi~h surface area. Smectites comprise layered sheets
of octahedral sites between sheets of tetrahedral sites, where the
2~8~03~
distance between the layers can be adjusted by swelling, using an
appropriate solvent. Three~layered sheet-type smectites include
montmorillonites. The montmorillonite structure may be represented
by the following formula:
n+
MX/n~ yH20 (A14_xMgx) (Sig) O20(OH)4
where M represents the interlamellar (balancing) cations, normally
sodium or lithium; and x, y and n are integers.
Montmorillonite clays may be acid-activated by such
mineral acids as sulfuric acid, hydrochloric acid, and the like.
Mineral acids activate montmorillonites by attacking and
solubilizing structural cations in the octahedral layers. This
opens up the clay structure and increases surface area. These
acid-treated clays act as strong Bronsted acids. Suitable acid-
treated clays include, for example, acidic calcium montmorillonite
clays having a moisture content ranging up to about 20 wt.%, a
residual acidity in the range of about 3 to about 30 mg KOH/g (when
titrated to a phenolphthalein end point), and a surface area of
about 300 m2/g or greater. Illustrative examples of commercially
available acid-treated clays include Engelhard Corporation's
Grade F24, having a moisture content of 12 wt.%, a residual acidity
of 16 mg KOH/g, and a surface area of 350 m2/g; Grade F124, having
a moisture content of 4 wt.%, a residual acidity of 14 mg KOH/g,
and a surface area of 350 m2/g; Grade F13, having a moisture
content of 12 wt.%, a residual acidity of ~5 mg KOH/g, and a
surface area of 300 m2/g; Grade F113, having a moisture content of
2~038
wt.%, a residual acidity of lS mg KOH/g, and a surface area of
300 m2/g; and Grade F224, having virtually no moisture, and having
a residual acidity of 5 mg KOH/g, and a surface area of 350 m2/g.
Preferably, the acidic montmorillonite clay is activated
by heat treatment before being blended with the sulfate-activated
Group IV oxide component. Applicants have found, surprisingly,
that heat treatment of the clay component prior to being blended
with the sulfate-activated Group IV oxide component causes the
catalyst to be more active and produce higher olefin conversions.
Additionally, clays heat treated in this manner are more stable,
remaining active during the oligomerization reaction for a longer
period of time. The clays may be heat treated at temperatures in
the range of about 50 to 400 C, with or without the use of a
vacuum. A more preferred temperature range is 50 to 300 C.
Optionally, an inert gas may be used during heat treatment as well.
Preferably, the clay should be heat treated under conditions and
for a length of time that will reduce the water content of the clay
to approximately 1 wt.~ or less.
In one embodiment, the sulfate-activated Group IV oxide
component of the blended catalyst may be prepared by treating a
Group IV oxide with a sulfate-containing compound. Preferably, the
sulfate-containing compound is selected from the group consisting
of ammonium sulfate, ammonium hydrogen sulfate, sulfuric acid,
sulfur trioxide, sulfur dioxide, and hydrogen sulfide. Especially
preferred su~fating agents are ammonium sulfate and sulfuric acid.
Said agents may be employed neat, or as an aqueous, ketonic,
2~ 038
alcoholic, or ether solution, but preferably as an aqueous
solution. Said sulfating agents also may be employed as mixtures
of the sulfating agents listed above. Excess sulfating agent may
be removed by known procedures, such as filtration.
Preferably, the sulfated Group IV oxide is then calcined
prior to being blended with the acidic clay component of the
oligomerization catalyst. Calcination in air or in an inert gas
environment, such as nitrogen, may be conducted at a temperature of
at least 100 C, but below the temperature at which thermal
destruction leads to deactivation. The optimal temperature range
can be determined by routine experimentation for a particular
catalyst. Typically, the sulfated catalyst is calcined for about
1 to 24 hours, preferably around lS hours, at a temperature of from
about 500 to 800 C, preferably around 650 C, in a stream of
nitrogen. Temperatures above 900 C should be avoided.
Suitable Group IV oxides used in conjunction with said
sulfur-containing compounds include, for example, the oxides of
silicon, titanium, zirconium, hafnium, germanium, tin, and lead, as
well as combinations thereof. Particularly preferred are oxides of
titanium and zirconium, such as the anatase or rutile forms of
titania and zirconia. Zirconia is especially preferred.
In a more specific embodiment, the Group IV oxide is
treated with sulfuric acid by adding said acid neat or, if desired,
diluted with distilled water, to the oxide extrudates. The slurry
is then mixed for about 1 to 24 hours, filtered, washed, and
calcined in a stream of air for about 1 to 24 hours. The prepared
20~3~
sulfuric acid-treated oxide should then have a titratable acidity
of at least 0.1 meq/g.
The weight percent of sulfuric acid to Group IV oxide
should be such that the concentration of the sulfur in the
formulated sulfate-activated Group IV oxide is in the range of
about 0.1 wt.% to 30 wt.~, although concentrations outside this
range also may be employed.
A suitable procedure to be used is to immerse zirconia
pellets, for example, in an aqueous or polar organic solvent
solution of the acid, preferably at ambient temperature. Higher
temperatures of about 100 C to about 150 C may be used, if
desired. This treatment should be continued, preferably with
agitation, for about 0.1 to about 5 hours. The conditions should
be sufficient to permit the solution to penetrate the pores of the
zirconia pellet. The amount of acid solution that is used should
be adequate to permit full immersion of the zirconia pellets.
Larger amounts of the solution can be used, if desired, but there
is no particular advantage in doing so. At the end of the
immersion step, the excess solution can be evaporated from the
treated pellets, or the pellets can be removed from the solution
and permitted to dry (e.g., in a drying oven).
The Group IV oxide may be in the form of powders,
pellets, spheres, shapes and extrudates. Pellets may be prepared
by extrusion or by compaction in conventional pelleting apparatus
using a pelleting aid such as graphite. Extrudates which work well
include HSA titania carrier extrudate from Norton Company, with a
208~Q~
surface area of 51 m2/g, and zirconia extrudates from Norton having
a surface area of 77 m2/g.
In a second embodiment, the sulfate-activated Group IV
oxide component may be prepared by a one-step process, comprising
heating a compound such as titanium sulfate hydrate at a
temperature in the range of about 500 C to about 625 C. Sulfate-
activated zirconium dioxide compounds may be prepared in a similar
manner using, for example, zirconium sulfate hydrate.
In a third embodiment, the sulfate-activated Group IV
oxide is supported on a silicon dioxide substrate, and the silicon
dioxide-supported sulfate-activated Group IV oxide is blended with
the acidic clay. The silicon dioxide substrate may be any of the
various - primarily amorphous - forms of sio2. See Kirk-Othmer,
Encyclopedia of Chemical Technoloay, 3d. ed., vol. 20, pp. 748-764
(1981), incorporated herein by reference. Silica gels, which
contain three-dimensional networks of aggregated silica particles
of colloidal dimensions, are preferred. Silica gels are
commercially available in at least the following mesh sizes: 3-8;
6-16; 14-20; 14-42; and 28-200 and greater. A suitable
commercially available silica gel is the grade 12, 28-200 mesh,
silica gel available from Aldrich Chemical Co., Inc.
The silica gel should be added to a solution of about
0.05 to about 25 wt.%, preferably from about 10 to about 20 wt.%
Group IV sulfate in water. The ratio of silica gel to Group IV
sulfate solution should be sufficient to provide a quantity of
Group IV sulfate deposited on the silica gel ranging from about
14
2086~3~
0.05 to about 15 wt.%, preferably from about 0.05 to about 5.0
wt.%. The silica gel should remain in the Group IV sulfate
solution for a period of time and under agitation to the extent
necessary to meet these requirements, and then filtered and dried.
5Optionally, after filtration, the silica gel may be washed with
distilled water before being dried, preferably under mild
conditions. Preferably, the Group IV sulfate is titanium sulfate
or zirconium sulfate. Zirconium sulfate is especially preferred.
The silicon dioxide substrate having the Group IV sulfate
10deposited thereon should be calcined prior to use as a component in
the blended oligomerization catalyst. Calcination in air or in an
inert gas environment, such as nitrogen, may be conducted at a
temperature of at least 100 C, but below the temperature at which
thermal destruction leads to deactivation. Typically, the silicon
15dioxide substrates having the Group IV sulfate deposited thereon
are calcined for about 1 to 24 hours, preferably from about 15 to
about 20 hours, at a temperature of from about 400 to 800 C,
preferably from about 500 to about 800 C, more preferably at about
650 C for 18 hours. Temperatures above 900 C should be avoided.
20Once prepared, the sulfate-activated Group IV oxide
component, whether supported on silicon dioxide or unsupported, is
physically blended with the acidic montmorillonite clay in the
proportions disclosed above. Optionally, the blended components
may then be pelletized for easier handling. Diameters ranging from
25about 0.794 mm (1/32 inch) to about 9.525 mm (3/8 inch) possess
desirable dimensions. The shape and dimensions of the pellets are
2a~
not critical to the present invention; pellets of any suitable
shape and dimensions may be used.
When cylindrical pellets of catalyst of the type
described above are used in a fixed bed continuous flow reactor,
the liquid hourly space velocity may be varied within wide limits
(e.g., 0.1 to 10) in order to obtain a desired rate of conversion.
Normally, space velocities of about 0.5 to 2 LHSV will be employed.
The oligomerization reaction may be carried out either
batchwise, in a stirred slurry reactor, or continuously, in a fixed
bed continuous flow reactor. The catalyst concentration should be
sufficient to provide the desired catalytic effect. The
temperatures at which the oligomerization may be performed are
between about 50 and 300O C, with the preferred range being about
120 to 250 C, a more preferred range being about 140 to 180 C,
and an especially preferred range being about 160 to about 180 C.
At temperatures of about 200 C or greater, the amount of
unsaturation remaining in the products of the oligomerization
reaction may decrease, thus reducing the degree of hydrogenation
necessary to remove unsaturation from the base stocks. However, at
temperatures above 200 C, the olefin conversion may decrease. The
dimer to trimer ratio may increase. Applicants have found that the
addition of a hydrocarbon containing a tertiary hydrogen, such as
methylcyclohexane, may further reduce the amount of unsaturation
present in the base stocks. One skilled in the art may choose the
reaction conditions most suited to the results desired for a
16
2~a3g
particular application. The reaction may be run at pressures of
from 0 to 1000 psig.
Following the oligomerization reaction, the unsaturated
oligomers may be hydrogenated to improve their thermal stability
and to guard against oxidative degradation during their use as
lubricants. The hydrogenation reaction for 1-decene oligomers may
be represented as follows:
catalyst
C10nH20n + H2 ~~~~~~----> C10 H
where n represents moles of monomer used to form the oligomer.
Hydrogenation processes known to those skilled in the art may be
used to hydrogenate the oligomers. A number of metal catalysts
are suitable for promoting the hydrogenation reaction, including
nickel, platinum, palladium, copper, and Raney nickel. These
metals may be supported on a variety of porous materials such as
kieselguhr, alumina, or charcoal, or they may be formulated into a
bulk metal catalyst. A particularly preferred catalyst for this
hydrogenation is a nickel-copper-chromia catalyst described in U.S.
Patent No. 3,152,998, incorporated by reference herein. Other U.S.
patents disclosing known hydrogenation procedures include U.S.
Patent Nos. 4,045,508; 4,013,736; 3,997,622; and 3,997,621.
Unreacted monomers may be removed either prior to or
after the hydrogenation step. Optionally, unreacted monomers may
be stripped from the oligomers prior to hydrogenation and recycled
to the catalyst bed for oligomerization. The removal or recycle of
unreacted monomers or, if after hydrogenation, the removal of non-
oligomerized alkanes, should be conducted under mild conditions
17
8~03~
using vacuum distillation procedures known to those skilled in the
art. Distillation at temperatures exceeding 250 C may cause the
oligomers to break down in some fashion and come off as volatiles.
Preferably, therefore, the reboiler or pot temperature should be
kept at or under about 225 C when stripping out the monomers.
Procedures known by those skilled in the art to be alternatives to
vacuum distillation also may be employed to separate unreacted
components from the oligomers.
While it is known to include a distillation step after
the hydrogenation procedure to obtain products of various 100 C
viscosities, it is preferred in the method of the present invention
that no further distillation (beyond monomer flashing) be
conducted. In other words, the monomer-stripped, hydrogenated
bottoms are the desired synthetic lubricant components. Thus, the
method of this invention does not require the costly, customary
distillation step, yet, surprisingly, produces a synthetic
lubricant component that has excellent properties and that performs
in a superior fashion. However, in some contexts, one skilled in
the art may find subsequent distillation useful in the practice of
this invention.
The invention will be further illustrated by the
following examples, which are given by way of illustration and not
as limitations on the scope of this invention. The entire text of
every patent, patent application or other reference mentioned above
is hereby incorporated herein by reference.
18
208~3~
EXAMPLES
In the examples detailed in Table I below, the following
procedures were used:
Preparation of Catalysts
Zr2 catalyst component #1: Norton ZrO2 pellets were
placed in a crucible and covered with 10 ~ (NH4)2SO4, and let stand
for an hour, and then heated to 650 C. The crucible was held at
this temperature for 15 hours under nitrogen flow, and then cooled
and placed in a stoppered bottle until use.
Zr2 catalyst component ~2: Johnson Matthey 97 %
Zr(SO4)2-4H2O was placed in a crucible and set in an oven and heated
to 650 C. The crucible was held at this temperature for 15 hours
under nitrogen flow, and then cooled and placed in a stoppered
bottle until use.
Oligomeriz~ation of Olefins
Samples of the ZrU2 catalyst components prepared above
were ground to a fine powder with Engelhard Corporation's Grade F13
acidic montmorillonite clay, in the proportions listed in the table
below. Olefin and blended catalyst were charged to a flask
equipped with an overhead stirrer, thermometer, heating mantle, and
a water-cooled condenser (N2 purge). The mixture was vigorously
stirred and heated to the desired temperature for the desired time.
The mixture was then cooled to ambient temperature and filtered
with suction. The liquid was analyzed by liquid chromatography.
The results obtained are detailed in the following table.
2~o~
Tabld I
l ~ -- ---- - ~--- --- --- --
Ex. OlcGn (by(g) o8 Calrlys~ (8) of Timd/Tcmp. Con. D/T+
No. carbonOldfin Calalyst (~r)/(C) (%) Ralio
numbc r) Compone nts
l C-14 a 100 ZrO, ~2 10 5/160 66.8 3.04 l
I . . __
2 C-14 n 100 Dry Clay-13 10 5/160 83.1 1.81 l
l _
3 C-14 a 100 Dry Clay-13 10 5/160 84.6 1.73 l
I _
4 C-14 a 100 Dry Cl~y-13/ZrO. #7 9.8/0.2 5/160 85.6 1.35 l
I_ I
C-14 a 100 Dry Clay-13/ZrO. ~2 9.2/0.8 5/160 85.2 1.17
_ . _ _
6 C-10 a 100 Dry Clay-13/ZrO~ #2 10 5/160 89.8 1.04
7 C-10 a 100 Dry Clay-13/ZrO2 #2 9.8/0.2 5/160 91.6 0.76
8 C-10 a 100 Dry Clay-13/ZrO2 ~2 9.6/0.4 5/160 91.9 0.77
___ I
9 C-10 a 100 Dry Clay-13/ZrO. #2 9.2/0.5 S/160 93.8 0.74 l
I _ , I
C-14 a 100 Dry Clay-13/ZrO2 ~2 10 4/180 84.5 1.12 l
I _ I
11 C-14 a 100 Dry Clay-13/ZrO. #2 9.8/0.2 4/180 87.6 1.10 l
I .. _ . I
lS 12 C-14 a 100 Dry Cl~y-13/ZrO~ #2 9.6/0.4 4/180 86.9 1.47
13 C-14 a 100 Dry Clry-13/ZrO. #2 9.2/0.8 4/180 86.6 1.17
14 C-10 a 100 Dry Clay-13/ZrO. #2 10 4/180 88.4 1.16
_ _
1S C-10 G 1OO Dry Clay-13/ZrO2 ~2 9 8/0.2 4/180 90.8 0.95
16 C-10 1 100 Dry Clay-13/ZrO, #2 9.6/0.4 4/180 91.4 0.70
2 0 17 C-10 a 100 Dry Clay-13/ZrO. A~2 9.2/0.8 4/180 92.1 0.93
18 C-1314 i 100 Dry Clay-13/ZrO. #2 10 4/-180 79.2 3.22
__
19 C-1314 1 100 Dry Clay-13/ZrO. ~2 9.8/0.2 4/180 85.1 1.56
I
C-1314 1 100 Dry Clay-13/ZrO2 ~2 9.6/0.4 4/180 84.2 1.73
21 C-1314 1 100 Dry Cl~y-13/ZIO, #2 9.2/0.4 4/180 81.7 2.70
¦ 22 C-14 a 100 Dry Clay-13/ZrO1 ~1 9.0/1.0 S/160 88.3 1.15
_ _ _ ___ _ _ __ - -7
a = Alpha Oldfin; I = Inlcrnal Olcfin; Con. = Olcfin Convcrsion:
DiT+ = R~fio ol Dimcr: Tlimdr + Tdlr~mdr + Pdmamdr, ~Ic.
In the examples detailed in Table II below, the following
procedures were used:
Pre~aration of Catalyst
Aldrich silica gel (Grade 12, 28-200 mesh) in a crucible,
was treated with 500 g of 20 % ZrSO4 in D.M. water. The crucible
was placed in an oven, heated to 650 C, and held at this
-\ 2~g~Q~
temperature for lB hours under a flow of nitrogen. The white solid
was cooled under nitrogen and stored in a stoppered bottle until
used. Atomic absorption analysis showed 4.8 % zirconium.
Oliqomerization of Olefins
Samples of the ZrO2lSiO2 catalyst components prepared
above were ground to a fine powder with Engelhard Corporation's
Grade F13 acidic montmorillonite clay, in the proportions listed in
the table below. Olefin and blended catalyst were charged to a
flask equipped with an overhead stirrer, thermometer, heating
mantle, and a water-cooled condenser (N2 purge). The mixture was
vigorously stirred and heated to the desired temperature for the
desired time. The mixture was then cooled to ambient temperature
and filtered with suction. The liquid was analyzed by liquid
chromatography. The results obtained are detailed in the table
below.
2~6038
TABLE 11
_ _ - __ _ _
E.~. Olcfiln (by (g) of C~lys~ (~) of Time/Tdmp. Con. DIT+
No. cnrbon Olefiln C~talyst (Hr)/(~C) (%) R~lio
numbcr) Componenls
C-14 a 100 Dry Cl;ly-13 9.5 5/160 86.8 1.26
l ZrO21SiO2 0.5
¦~ C-14 a 100 Dry Chly-13 2 0 5/160 86.2 H46
¦~ C-14 a 100 Dry Cllly-13i0 5/160 83.1 1.81
¦~ C-14 100 Dry Clay-13 10 5/160 84.6 R73
¦~ C-14 a 100 ZrO lSiO2 - 5/160 54 3 4 95
¦~ C- 14 a 100 ZrO~lSIO, 0 ~ 5/ i 60 84.7 1.57
¦ 7 C-14 a 100 Dry Clr~y 13 9.5 5/160 85.9 1.44
ZrO2/SiO2 0 .5
¦ 8 C-li a 100 Dry Clrly-139.0 5/160 85.3 1.38
l ZrO ISiO, 1.0
¦~ C-14 a 100 D''Y'/C5jo i3 8 5 5/160 84.0 1.53
r C-IS a 100 ZrO.lSiO, 2 0 51160 83.8 1.45
¦~ C-14 a 100 Dry Cl~y-13 9 5 4/180 89.1 1.16
¦~ C-14 a 100 Dry Clry-1391 O 4/180 85.2 2.05
¦~ C-1314 1 100 Dry Cl~y-13 5/160 46.3 4.02
14 ¦ C-1314 1 100 Dry Clrly-139.5 5/160 42.0 6.W
ZrO,lSiO. 0 .5
¦ C-1314 1 100 Dry Cby-13 9.0 51160 45.8 4.16
ZrO,lSiO, 1.0 .
16 ¦ C-i314 1 100 ZrO lSIO. 2 0 51160 34 ~ 3.89
- 17 ¦ C-1314 1 100 Dry Cl~y 13 10 41180 73.4 3.95
18 C-1314 1 100 DzrrOJcs~lo;l3 0 5 4il80 79.8 3.0
19 C-131-11 100 Dry Cl~y-13 1 0 41180 83.7 R77
C-131-11 100 ZDrrO./CSll~O i3 2 0 41180 8NI 2.76
~ C-14 a 100 ZDrrO.ClSI10;l3 0 2 51160 83.3 1.47
2 5 ~ C-14 100 Dry Cl~ly 13 9.6 51160 83.6 1.55
ZrO.lSiO. 0.4
¦~ G 1-1 a 100 Dry Clsy 13 9? 51160 85.3 1.30
ZrO.lSiO. 0.8
C-14 ~ 1 7 D~y Cl-7-13 9 0 51160 ~7~7 I IS
a = Alph~ Olclin: I = Inlernsl Olcr~n; Con. = Ohrtn Convcrsion;
DiT+ = R~io ot Dimcr: Tnmor + Tolr~mer + Pcmrlmcr, elc.
