U.S. patent number 3,755,138 [Application Number 05/206,888] was granted by the patent office on 1973-08-28 for lube oils by solvent dewaxing and hydrodewaxing with a zsm-5 catalyst.
This patent grant is currently assigned to Mobil Oil Corporation. Invention is credited to Nai Yuen Chen, William E. Garwood.
United States Patent |
3,755,138 |
Chen , et al. |
August 28, 1973 |
**Please see images for:
( Certificate of Correction ) ** |
LUBE OILS BY SOLVENT DEWAXING AND HYDRODEWAXING WITH A ZSM-5
CATALYST
Abstract
A two-step or combination process for preparing low pour point
lube oils is set forth. The process involves subjecting a lube
stock to a mild solvent dewaxing step, so as to obtain high quality
waxes and a lube stock having an intermediate pour point;
recovering the waxes and subjecting said intermediate pour point
lube stock to a hydrowaxing step over a crystalline aluminosilicate
of the ZSM-5 type to obtain a product having a pour point of
0.degree. F and lower.
Inventors: |
Chen; Nai Yuen (Hopewell
Township, Mercer County, NJ), Garwood; William E.
(Haddonfield, NJ) |
Assignee: |
Mobil Oil Corporation (New
York, NY)
|
Family
ID: |
26901762 |
Appl.
No.: |
05/206,888 |
Filed: |
December 10, 1971 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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56652 |
Jul 20, 1970 |
|
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865470 |
Oct 10, 1969 |
3700585 |
Oct 24, 1972 |
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Current U.S.
Class: |
208/33;
208/DIG.2; 208/85; 208/28; 208/111.1; 208/111.35 |
Current CPC
Class: |
B01J
29/405 (20130101); B01J 29/40 (20130101); C01B
33/2876 (20130101); Y10S 208/02 (20130101); C10G
2400/10 (20130101) |
Current International
Class: |
B01J
29/40 (20060101); B01J 29/00 (20060101); C10G
67/04 (20060101); C10G 45/64 (20060101); C10G
67/00 (20060101); C10G 45/58 (20060101); C10g
013/04 () |
Field of
Search: |
;208/DIG 2./
;208/28,33,111,85 |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
3539498 |
November 1970 |
Morris et al. |
|
Primary Examiner: Levine; Herbert
Parent Case Text
CROSS REFERENCE TO RELATED CASES
This application is a continuation of U.S. Pat. Ser. No. 56,652
filed July 20, 1970, now abandoned and which is a
continuation-in-part of U.S. Pat. Ser. No. 865,470 filed Oct. 10,
1969 now U.S. Pat. No. 3,700,585, issued Oct. 24, 1972.
Claims
What is claimed is:
1. A process for preparing low pour point lube oils which comprises
subjecting a petroleum feed stock to solvent dewaxing so as to
obtain a lube oil having an intermediate pour point of 10.degree.
to 50.degree. F and thereafter subjecting said intermediate pour
point product to catalytic hydrodewaxing by contacting the same in
the presence of added hydrogen with a crystalline aluminosilicate
of the ZSM-5 type containing a hydrogenation component and
obtaining a product having a pour point no higher than 0.degree.
F.
2. The process of claim 1 wherein the ZSM-5 type zeolite has X-ray
diffraction patterns corresponding to that set forth in Table
1.
3. The process of claim 1 wherein the ZSM-5 type zeolite is
ZSM-8.
4. The process of claim 1 wherein the ZSM-5 type zeolite has been
base exchanged with hydrogen ions, ammonium ions, and mixtures
thereof.
5. The process of claim 4 wherein the product obtained has a pour
point no higher than -20.degree. F.
Description
DESCRIPTION OF THE INVENTION
This invention relates to a process for dewaxing petroleum oils and
fractions thereof by selectively removing normal paraffinic and
other undesirable hydrocarbons from petroleum oils in which they
are present in admixture with other hydrocarbons, in order to lower
the pour point of such oils. More particularly, the invention
relates to an improved process for selectively removing normal
paraffinic and other undesirable hydrocarbons from petroleum oils
by a two-step process involving solvent dewaxing followed by
contact of such oils with specific types of crystalline
aluminosilicate zeolites identified as those of the ZSM-5 type.
It is well known in the art to form various lubricating oils,
commonly referred to as lubes, from hydrocarbon fractions derived
from petroleum crudes. A heretofore practiced common procedure
known in the art is to extract these hydrocarbon fractions with
various solvents so as to give a raffinate of a desired high
viscosity index, such material being resistant to changes in
viscosity with changes in temperature and thus being useful under
varying operating conditions. Moreover, it is particularly desired
that the lube oil have a low pour point so that it can be
effectively used at low temperature conditions, since excessive
thickening at low temperatures is often unacceptable. It is also
known in the art to carry out dewaxing operations by contacting
hydrocarbon fractions with crystalline aluminosilicate zeolites
having pore sizes of about 5 Angstrom units so as to selectively
remove normal paraffins.
The present invention is concerned with an improved process for
dewaxing normal paraffin-containing oils which is more economical
than conventional solvent dewaxing procedures or catalytic dewaxing
procedures involving 5 Angstrom unit zeolites and which, with
certain feedstocks, produces a higher product yield with equivalent
or higher pour point reduction.
Briefly, the present process employs the use of a conventional
solvent dewaxing step but only to slightly reduce the pour point of
the treated stock and obtain a product having an intermediate pour
point. Quite obviously, the product of intermediate pour point is
unsuitable for use as a low temperature lubricant at this stage. In
accordance with the invention, this intermediate product is then
subjected to hydrodewaxing with a crystalline aluminosilicate of
the ZSM-5 type to yield a product having excellent low temperature
properties.
It is to be immediately noted that the sequence of steps of the
instant combination process is critical. In order to achieve the
maximum economic advantage the solvent dewaxing must come first
followed by the catalytic hydrodewaxing step. This is so because
the highest quality wax which is obtained from a given feed is that
obtained in the initial stages of the solvent dewaxing. If the feed
stock were first subject to catalytic hydrodewaxing, the highest
quality wax would be destroyed.
Additionally, it has been found that catalytic hydrodewaxing with a
ZSM-5 type catalyst is more effectively carried out with
intermediate pour point product than with a conventional lube
stock. Thus, the unique processing scheme of this invention
provides a maximization of desirable products from a given feed
stock.
The feedstocks adapted for treatment in accordance with the present
invention may be generally defined as hydrocarbon oils boiling
above about 650.degree. F and particularly between about
650.degree. and about 1,100.degree. F.
As has heretofore been stated, the first step of the novel process
of this invention involves subjecting a feed stock of the type
above-described to a mild solvent dewaxing.
By mild solvent dewaxing is meant that the lube stock feed material
is treated until it has a pour point of 10.degree. to 50.degree. F
and preferably from 20.degree.-30.degree. F.
The solvent dewaxing step is carried out in a conventional manner
according to well known techniques. Suitable solvent mixtures
include methyl ethyl ketone-toluene, methyl ethyl ketone-methyl
isobutyl ketone etc.
The products from the solvent dewaxing step are high quality waxes
which are recovered and an intermediate pour point stock which is
then subjected to hydrodewaxing over a catalyst comprising a
crystalline zeolite of the ZSM-5 type.
While not wishing to be bound by any theory of operation,
nevertheless, it appears that the crystalline zeolitic materials
employed in the instant invention cannot simply be characterized by
the recitation of a pore size or a range of pore sizes. It would
appear that the uniform pore openings of this new type of zeolite
are not circular in nature, as is usually the case in the
heretofore employed zeolites, but rather, are elliptical in nature.
Thus, the pore openings of the instant zeolitic materials have both
a major and a minor axis, and it is for this reason that the
unusual and novel molecular sieving effects are achieved. This
elliptical shape can be referred to as a "keyhole." From their
dynamic molecular sieving properties it would appear that the major
and minor axes of the elliptical pore in this family of zeolites
have effective sizes of about 7.0 .+-. 0.7A and 5.0 .+-. 0.5A,
respectively.
The family of ZSM-5 type compositions has the characteristic X-ray
diffraction pattern set forth in Table 1, hereinbelow. ZSM-5
compositions can also be identified, in terms of mole ratios of
oxides, as follows:
0.9 .+-. 0.2 (M.sub.2 O/n) : W.sub.2 O.sub.3 : 5-100 YO.sub.2 : 2
H.sub.2 O
wherein M is a cation, n is the valence of said cation, W is
selected from the group consisting of aluminum and gallium, Y is
selected from the group consisting of silicon and germanium, and Z
is from 0 to 40. In a preferred synthesized form, the zeolite has a
formula, in terms of mole ratios of oxides, as follows:
0.9 .+-. 0.2 (M.sub.2 O/n) : Al.sub.2 O.sub.3 : 5-100 SiO.sub.2 : z
H.sub.2 O
and M is selected from the group consisting of a mixture of alkali
metal cations, especially sodium, and tetraalkylammonium cations,
the alkyl groups of which preferably contain 2-5 carbon atoms.
In a preferred embodiment of ZSM-5, W is aluminum, Y is silicon and
the silica/alumina mole ratio is at least 10 and ranges up to about
60.
Members of the family of ZSM-5 zeolites possess a definite
distinguishing crystalline structure whose X-ray diffraction
pattern shows the following significant lines:
TABLE I
Interplanar Spacing d(A) Relative Intensity 11.1 .+-. 0.2 S 10.0
.+-. 0.2 S 7.4 .+-. 0.15 W 7.1 .+-. 0.15 W 6.3 .+-. 0.1 W 6.04 .+-.
0.1 W 5.97 .+-. 0.1 W 5.56 .+-. 0.1 W 5.01 .+-. 0.1 W 4.60 .+-.
0.08 W 4.25 .+-. 0.08 W 3.85 .+-. 0.07 VS 3.71 .+-. 0.05 S 3.64
.+-. 0.05 M 3.04 .+-. 0.03 W 2.99 .+-. 0.02 W 2.94 .+-. 0.02 W
these values as well as all other X-ray data were determined by
standard techniques. The radiation was the K-alpha doublet of
copper, and a scintillation counter spectrometer with a strip chart
pen recorder was used. The peak heights, I, and the positions as a
function of two times theta, where theta is the Bragg angle, were
read from the spectrometer chart. From these, the relative
intensities, 100 I/I, where I is the intensity of positions as a
function of two times theta, where theta is the Bragg angle, were
read from the spectrometer chart. From these, the relative
intensities, 100 I/I, where I is the intensity of the strongest
line or peak, and d (obs.), the interplanar spacing in A,
corresponding to the recorded lines, were calculated. In Table I
the relative intensities are given in terms of the symbols S =
strong, M = medium, MS = medium strong, MW = medium weak and VS =
very strong. It should be understood that this X-ray diffraction
pattern is characteristic of all the species of ZSM-5 compositions.
Ion exchange of the sodium ion with cations reveals substantially
the same pattern with some minor shifts in interplanar spacing and
variation in relative intensity. Other minor variations can occur
depending on the silicon to aluminum ratio of the particular
sample, as well as if it has been subjected to thermal treatment.
Various cation exchanged forms of ZSM-5 have been prepared. X-ray
powder diffraction patterns of several of these forms are set forth
below. The ZSM-5 forms set forth below are all
aluminosilicates.
TABLE 2
X-Ray Diffraction
ZSM-5 Powder in Cation Exchanged Forms
d Spacings Observed
As Made HCl NaCl CaCl.sub.2 ReCl.sub.3 AgNO.sub.3 11.15 11.16 11.19
11.19 11.19 11.19 10.01 10.03 10.05 10.01 10.06 10.01 9.74 9.78
9.80 9.74 9.79 9.77 9.01 9.02 8.99 8.06 7.44 7.46 7.46 7.46 7.40
4.46 7.08 7.07 7.09 7.11 7.09 6.70 6.72 6.73 6.70 6.73 6.73 6.36
6.38 6.38 6.37 6.39 6.37 5.99 6.00 6.01 5.99 6.02 6.01 5.70 5.71
5.73 5.70 5.72 5.72 5.56 5.58 5.58 5.57 5.59 5.58 5.37 5.38 5.37
5.38 5.37 5.13 5.11 5.14 5.12 5.14 4.99 5.01 5.01 5.01 5.01 5.01
4.74 4.61 4.62 4.62 4.61 4.63 4.62 4.46 4.46 4.46 4.36 4.37 4.37
4.36 4.37 4.37 4.26 4.27 4.27 4.26 4.27 4.27 4.08 4.09 4.09 4.09
4.09 4.00 4.01 4.01 4.00 4.01 4.01 3.84 3.85 3.85 3.85 3.86 3.86
3.82 3.82 3.82 3.82 3.83 3.82 3.75 3.75 3.75 3.76 3.76 3.75 3.72
3.72 3.72 3.72 3.72 3.72 3.64 3.65 3.65 3.65 3.65 3.65 3.60 3.60
3.60 3.61 3.60 3.48 3.49 3.49 3.48 3.49 3.49 3.44 3.45 3.45 3.44
3.45 3.45 3.34 3.35 3.36 3.35 3.35 3.35 3.31 3.31 3.32 3.31 3.32
3.32 3.25 3.25 3.26 3.25 3.25 3.26 3.17 3.17 3.18 3.13 3.14 3.14
3.14 3.15 3.14 3.05 3.05 3.05 3.04 3.06 3.05 2.98 2.98 2.99 2.98
2.99 2.99 2.97 2.95 2.95 2.94 2.95 2.95 2.86 2.87 2.87 2.87 2.87
2.87 2.80 2.78 2.78 2.78 2.73 2.74 2.74 2.73 2.74 2.74 2.67 2.68
2.66 2.65 2.60 2.61 2.61 2.61 2.61 2.61 2.59 2.59 2.57 2.57 2.56
2.57 2.50 2.52 2.52 2.52 2.52 2.49 2.49 2.49 2.49 2.49 2.49 2.45
2.41 2.42 2.42 2.42 2.42 2.39 2.40 2.40 2.39 2.40 2.40 2.38 2.35
2.38 2.33 2.33 2.32 2.33 2.30 2.24 2.23 2.23 2.20 2.21 2.20 2.20
2.18 2.18 2.17 2.17 2.13 2.13 2.11 2.11 2.11 2.10 2.10 2.08 2.08
2.08 2.08 2.07 2.07 2.04 2.01 2.01 2.01 2.01 2.01 2.01 1.99 2.00
1.99 1.99 1.99 1.99 1.97 1.96 1.95 1.95 1.95 1.95 1.95 1.94 1.92
1.92 1.92 1.92 1.92 1.91 1.91 1.88 1.87 1.87 1.87 1.87 1.87 1.87
1.86 1.84 1.84 1.84 1.84 1.83 1.83 1.83 1.83 1.83 1.82 1.81 1.82
1.77 1.77 1.79 1.78 1.77 1.76 1.76 1.76 1.76 1.76 1.76 1.75 1.75
1.74 1.74 1.73 1.71 1.72 1.72 1.71 1.70 1.67 1.67 1.67 1.67 1.67
1.66 1.66 1.66 1.66 1.66 1.65 1.65 1.64 1.64 1.63 1.63 1.63 1.63
1.62 1.61 1.61 1.61 1.61 1.58 1.57 1.57 1.57 1.57 1.56 1.56
1.56
zeolite ZSM-5 can be suitably prepared by preparing a solution
containing tetrapropyl ammonium hydroxide, sodium oxide, an oxide
of aluminum or gallium, an oxide of silica or germanium, and water
and having a composition, in terms of mole ratios of oxides,
falling within the following ranges:
TABLE 3
Particularly Broad Preferred Preferred OH.sup.-/SiO 0.07-1.0
0.1-0.8 0.2-0.75 R.sub.4 N+/(R.sub.4 N .sup.++Na.sup.+) 0.2-0.95
0.3-0.9 0.4-0.9 H.sub.2 O/OH.sup.- 10-300 10-300 10-300 YO.sub.2
/W.sub.2 O.sub.3 5-100 10-60 10-40
wherein R is propyl, W is aluminum or gallium and Y is silicon or
germanium maintaining the mixture until crystals of the zeolite are
formed. Thereafter, the crystals are separated from the liquid and
recovered. Typical reaction conditions consist of heating the
foregoing reaction mixture to a temperature of from about
150.degree. C to 175.degree. C for a period of time of from about 6
hours to 60 days. A more preferred temperature range is from about
160.degree. to 175.degree. C with the amount of time at a
temperature in such range being from about 12 hours to 8 days.
The digestion of the gel particles is carried out until crystals
form. The solid product is separated from the reaction medium, as
by cooling the whole to room temperature, filtering, and water
washing.
The foregoing product is dried, e.g., at 230.degree. F, for from
about 8 to 24 hours. Of course, milder conditions may be employed
if desired, e.g., room temperature under vacuum.
ZSM-5 is preferably formed as an aluminosilicate. The composition
can be prepared utilizing materials which supply the appropriate
oxide. Such compositions include for an alumino-silicate, sodium
aluminate, alumina, sodium silicate, silica hydrosol, silica gel,
silicic acid, sodium hydroxide and tetrapropylammonium hydroxide.
It will be understood that each oxide component utilized in the
reaction mixture for preparing a member of the ZSM-5 family can be
supplied by one or more initial reactants and they can be mixed
together in any order. For example, sodium oxide can be supplied by
an aqueous solution of sodium hydroxide, or by an aqueous solution
of sodium silicate; tetrapropylammonium cation can be supplied by
the bromide salt. The reaction mixture can be prepared either
batchwise or continuously. Crystal size and crystallization time of
the ZSM-5 composition will vary with the nature of the reaction
mixture employed. ZSM-5 is disclosed and claimed in copending U.S.
Pat. application Ser. No. 865,472, filed Oct. 10, 1969.
Another operable zeolite falling within the above class is zeolite
ZSM-8 which is described and claimed in U.S. Pat. Ser. No. 865,418,
filed Oct. 10, 1969 now abandoned.
ZSM-8 can also be identified, in terms of mole ratios of oxides, as
follows:
0.9 .+-. 0.2 (M.sub.2 O/n) : Al.sub.2 O.sub.3 : 5-100 SiO.sub.2 : z
H.sub.2 O
wherein M is at least one cation, n is the valence thereof and z is
from 0 to 40. In a preferred synthesized form, the zeolite has a
formula, in terms of mole ratios of oxides, as follows:
0.9 .+-. 0.2 (M.sub.2 O/n) : Al.sub.2 O.sub.3 : 10-60 SiO.sub.2 : z
H.sub.2 O
and M is selected from the group consisting of a mixture of alkali
metal cations, especially sodium, and tetraethylammonium
cations.
ZSM-8 has an exceptionally high degree of thermal stability thereby
rendering it particularly effective for use in processes involving
elevated temperatures. In this connection, ZSM-8 appears to be one
of the most stable zeolites known to date.
ZSM-8 possesses a definite distinguishing crystalline structure
having the following X-ray diffraction pattern.
TABLE 4
dA.degree. I/I.sub.o I/I.sub.o dA.degree. 11.1 46 4 2.97 10.0 42 3
2.94 9.7 10 2 2.86 9.0 6 1 2.78 7.42 10 4 2.73 7.06 7 1 2.68 6.69 5
3 2.61 6.35 12 1 2.57 6.04 6 1 2.55 5.97 12 1 2.51 5.69 9 6 2.49
5.56 13 1 2.45 5.36 3 2 2.47 5.12 4 3 2.39 5.01 7 1 2.35 4.60 7 1
2.32 4.45 3 1 2.28 4.35 7 1 2.23 4.25 18 1 2.20 4.07 20 1 2.17 4.00
10 1 2.12 3.85 100 1 2.11 3.82 57 1 2.08 3.75 25 1 2.06 3.71 30 6
2.01 3.64 26 6 1.99 3.59 2 2 1.95 3.47 6 2 1.91 3.43 9 3 1.87 3.39
5 1 1.84 3.34 18 2 1.82 3.31 8 3.24 4 3.13 3 3.04 10 2.99 6
zeolite ZSM-8 can be suitably prepared by reacting a solution
containing either tetraethylammonium hydroxide or
tetraethylammonium bromide together with sodium oxide, aluminum
oxide, and an oxide of silica and water.
The relative operable proportions of the various ingredients have
not been fully determined and it is to be immediately understood
that not any and all proportions of reactants will operate to
produce the desired zeolite. In fact, completely different zeolites
can be prepared utilizing the same starting materials depending
upon their relative concentration and reaction conditions as is set
forth in U.S. Pat. No. 3,308,069. In general, however, it has been
found that when tetraethylammonium hydroxide is employed, ZSM-8 can
be prepared from said hydroxide, sodium oxide, aluminum oxide,
silica and water by reacting said materials in such proportions
that the forming solution has a composition in terms of mole ratios
of oxides falling within the following range
SiO.sub.2 /Al.sub.2 O.sub.3 -- from about 10 to about 200
Na.sub.2 O/tetraethylammonium hydroxide -- from about 0.05 to
0.20
Tetraethylammonium hydroxide/SiO.sub.2 -- from about 0.08 to
1.0
H.sub.2 o/tetraethylammonium hydroxide -- from about 80 to about
200
Thereafter, the crystals are separated from the liquid and
recovered. Typical reaction conditions consist of heating the
foregoing reaction mixture to a temperature of from about
100.degree. to 175.degree. C for a period of time of from about 6
hours to 60 days. A more preferred temperature range is from about
150.degree. to 175.degree. C with the amount of time at a
temperature in such range being from about 12 hours to 8 days.
The digestion of the gel particles is carried out until crystals
form. The solid product is separated from the reaction medium, as
by cooling the whole to room temperature, filtering, and water
washing.
The foregoing product is dried, e.g., at 230.degree. F for from
about 8 to 24 hours. Of course, milder conditions may be employed
if desired, e.g., room temperature under vacuum.
ZSM-8 is prepared utilizing materials which supply the appropriate
oxide. Such compositions include sodium aluminate, alumina, sodium
silicate, silica hydrosol, silica gel, silicic acid, sodium
hydroxide and tetraethylammonium hydroxide. It will be understood
that each oxide component utilized in the reaction mixture can be
supplied by one or more initial reactants and they can be mixed
together in any order. For example, sodium oxide can be supplied by
an aqueous solution of sodium hydroxide, or by an aqueous solution
of sodium silicate, tetraethylammonium cation can be supplied by
the bromide salt. The reaction mixture can be prepared either
batchwise or continuously.
The zeolites used in the instant invention can have the original
cations associated therewith replaced by a wide variety of other
cations according to techniques well known in the art. Typical
replacing cations would include acidic cations such as hydrogen,
ammonium and metal cations including mixtures of the same. Of the
replacing metallic cations, particular preference is given to
cations of metals such as rare earth metals, manganese, calcium, as
well as metals of Group II of the Periodic Table, e.g. zinc, and
Group VIII of the Periodic Table, e.g., nickel.
Typical ion exchange techniques would be to contact the particular
zeolite with a salt of the desired replacing cation or cations.
Although a wide variety of salts can be employed, particular
preference is given to chlorides, nitrates and sulfates.
Representative ion exchange techniques are disclosed in a wide
variety of patents including U.S. Pat. No. 3,140,249; U.S. Pat No.
3,140,251; and U.S. Pat. No. 3,140,253.
Following contact with the salt solution of the desired replacing
cation, the zeolites are then preferably washed with water and
dried at a temperature ranging from 150.degree. F to about
600.degree. F and thereafter calcined in air or other inert gas at
temperatures ranging from about 500.degree. F to 1,500.degree. F
for periods of time ranging from 1 to 48 hours or more. It has been
further found in accordance with the invention that catalysts of
improved selectivity and having other beneficial properties in some
hydrocarbon conversion processes such as catalytic cracking are
obtained by subjecting the zeolite to treatment with steam at
elevated temperatures ranging from 800.degree. to 1,500.degree. F
and preferably 1,000.degree. F and 1,400.degree. F. The treatment
may be accomplished in atmospheres of 100 percent steam of an
atmosphere consisting of steam and a gas which is substantially
inert to the zeolites.
A similar treatment can be accomplished at lower temperatures and
elevated pressures, e.g., 350.degree.-700.degree. F at 10 to about
200 atmospheres.
The ZSM-5 type zeolites must be used in intimate combination with a
hydrogenating component such as tungsten, vanadium, molybdenum,
rhenium, nickel, cobalt, chromium, manganese, zinc, or a noble
metal such as platinum or palladium since a
hydrogenation/dehydrogenation function is to be performed. Such
component can be exchanged into the composition, impregnated
therein or physically intimately admixed therewith. Such component
can be impregnated in or onto zeolite such as, for example, by, in
the case of platinum, treating the zeolite with a platinum
metal-containing ion. Thus, suitable platinum compounds include
chloroplatinic acid, platinous chloride and various compounds
containing the platinum ammine complex.
The compounds of useful platinum or other metals can be divided
into compounds in which the metal is present in the cation of the
compound and compounds in which it is present in the anion of the
compound. Both types of compounds which contain the metal in the
ionic state can be used. A solution in which platinum metals are in
the form of a cation or cationic complex, e.g., Pt(NH.sub.3).sub. 4
Cl.sub.2 is particularly useful.
Prior to use, the zeolites should be dehydrated at least partially.
This can be done by heating to a temperature in the range of
200.degree. to 600.degree. C in an inert atmosphere, such as air,
nitrogen, etc. and at atmospheric or subatmospheric pressures for
between 1 and 48 hours. Dehydration can also be performed at lower
temperatures merely by using a vacuum, but a longer time is
required to obtain a sufficient amount of dehydration.
Operating conditions include temperatures between 650.degree. F and
1,000.degree. F, a pressure between 100 and 3,000 psig but
preferably between 200 and 1,500 psig. The liquid hourly space
velocity is generally between 0.1 and 100, preferably between 0.5
and 20 and the hydrogen to hydrocarbon mole ratio is generally
between 1 and 80 preferably between 4 and 40.
The following examples will illustrate the best mode now
contemplated for carrying out this invention.
EXAMPLES 1 - 2
Examples 1 and 2 are directed towards conventional solvent dewaxing
and in each case the charge stock was a furfural raffinate having
the following properties:
Gravity, .degree.API 32.1 Pour Point, .degree.F. +105 K.V. at
210.degree.F, cs. 5.45
In both examples, conventional solvent ratios were employed which
were as follows on a volume to volume basis:
Solvent --*MEK/Toluene 60/40 Dilution, Solvent/Oil 3/1 Wash,
Solvent/Oil 1/1 * methylethylketone
In Example 1 the dewaxing was carried out at 0.degree. F whereas in
Example 2 the temperature employed was -20.degree. F.
Typical results of dewaxing at 0.degree. F and -20.degree. F are as
follows:
Example 1 2 Dewaxing Temperature, .degree.F. 0 -20 Yield of Oil,
Wt. % 83 80.5 Gravity, .degree.API 29.5 29.1 Pour Point, .degree.F.
+20 0 K.V. at 100.degree.F, cs. 43.0 45.0 K.V. at 210.degree.F, cs.
6.11 6.23 Viscosity Index 95 92 Yield of Wax, Wt. % 17 19.5 Melting
Point, .degree.F. +132 +127 Oil Content 1.9 3.85
The small incremental wax from dewaxing to 0.degree. F pour
(Example 2) over +20.degree. F pour (Example 1) hurts the quality
of the wax, i.e., melting point goes down and oil content goes up.
For highest quality wax it is therefore desirable to first dewax to
about +20.degree. F, and then further process to reduce the pour to
0.degree. F. When this is done by solvent dewaxing, the material
removed is commonly combined with "foot's oil" and sent to
catalytic cracking.
EXAMPLE 3
This example illustrates further pour point reduction by
conventional solvent dewaxing. This example is carried out at
-35.degree. F which represents the lower limit at which solvent
dewaxing is practical. The solvents were those used in Example 1
and the charge stock is the solvent dewaxed oil of Example 1 having
a pour point of +20.degree. F.
The results are as follows:
Dewaxing Temp., .degree.F -35 Oil, Wt. % (of +20.degree.F chg.)
76.4 Gravity, .degree.API 28.8 Pour Point, .degree.F -15 K.V. at
100.degree.F, cs 49.16 K.V. at 210.degree.F, cs 6.63 V.I. 94 "Wax",
wt.% 23.6
EXAMPLE 4
The +105.degree. F pour point raffinate used as feed material in
Example 1 was subjected to catalytic hydrodewaxing with a ZSM-5
type catalyst which contained zinc and which had been base
exchanged with ammonium ions (This catalyst was prepared by the
same general procedure used to prepare the catalyst in Example 9 of
parent U.S. Pat. application Ser. No. 865,470, filed Oct. 10,
1969). This hydrodewaxing took place without first carrying out
solvent dewaxing. The operation conditions were 750 psig,
750.degree. F, 1 LHSV, and 8,000 SCF H.sub.2 /bbl. The results
obtained were as follows:
Oil, Wt. % 54 Gravity, .degree.API 29.9 Pour Point, .degree.F. +25
K.V. at 100.degree.F, cs 36.28 K.V. at 210.degree.F, cs 5.64 V.I.
103 Cracked Products, Wt. % 46
Note that although the pour point was indeed lowered, the yield of
oil was only 54 percent as compared to 83 percent for solvent
dewaxing, i.e., see Example 1.
EXAMPLES 5-7
These examples will illustrate operations in accordance with this
invention.
In each of these examples a charge stock was first subjected to
solvent dewaxing in the same manner as Example 1. The oil resulting
from the treatment of Example 1, i.e., the +20 pour point fraction,
was then subjected to hydrodewaxing with a Zn/HZSM-5 catalyst (This
catalyst was prepared according to the same procedure as that used
in Example 9 of U.S. Pat. Ser. No. 865,470).
The results and operating conditions are set forth below:
Example 5 6 7 Yield of Oil, Wt. % 86 84 74 Gravity, .degree.API
27.8 28.5 27.7 Pour Point, .degree.F -20 -40 <-80 K.V. at
100.degree.F, cs 47.95 53.38 46.93 K.V. at 210.degree.F, cs 6.42
6.72 6.08 Viscosity Index 89 83 76 Cracked Products, Wt. % 14 16 26
Reaction Conditions Pressure, psig 500 750 750 Temperature,
.degree.F 750 750 750 H.sub.2, SCF/bbl (H.sub.2 /HC mol ratio)
11,000 2,000 2,000 (30) (5.4) (5.4) LHSV 8 4 1
as can be seen from the above results, the process of this
invention allows for greater yields of lower pour point material as
well as taking advantage of producing and recovering high quality
waxes from the conventional solvent extraction step.
* * * * *