U.S. patent number 3,730,876 [Application Number 05/099,644] was granted by the patent office on 1973-05-01 for production of naphthenic oils.
This patent grant is currently assigned to Texaco Inc.. Invention is credited to Avilino Sequeira, Jr..
United States Patent |
3,730,876 |
Sequeira, Jr. |
May 1, 1973 |
PRODUCTION OF NAPHTHENIC OILS
Abstract
Naphthenic oils are prepared by hydrocracking a petroleum
residuum and catalytically dewaxing the lubricating oil so
produced. The dewaxed oil is then subjected to solvent extraction
or mild hydrogenation.
Inventors: |
Sequeira, Jr.; Avilino
(Nederland, TX) |
Assignee: |
Texaco Inc. (New York,
NY)
|
Family
ID: |
22275978 |
Appl.
No.: |
05/099,644 |
Filed: |
December 18, 1970 |
Current U.S.
Class: |
208/59; 208/18;
208/95; 208/111.3; 208/111.35; 208/DIG.2; 208/58; 208/96 |
Current CPC
Class: |
C10G
45/64 (20130101); Y10S 208/02 (20130101); C10G
2400/10 (20130101) |
Current International
Class: |
C10G
67/04 (20060101); C10G 45/64 (20060101); C10G
65/00 (20060101); C10G 67/00 (20060101); C10G
65/12 (20060101); C10G 45/58 (20060101); C10g
013/02 (); C10g 037/04 (); C10g 037/10 (); C01b
033/28 () |
Field of
Search: |
;208/59,111 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Gantz; Delbert E.
Assistant Examiner: Schmitkons; G. E.
Claims
I claim:
1. A process for the production of naphthenic oils which comprises
contacting an asphaltene-and residue-containing petroleum fraction
having an initial boiling point of at least about 800.degree.F.
with a catalyst comprising a Group VI metal and a Group VIII metal
or their compounds or mixtures thereof on an amorphous support
having cracking activity and having a surface area of at least 250
m.sup.2 /g, a pore volume of at least 0.6 cc/g and an average pore
diameter of 50-95A., under hydrocracking conditions to convert at
least a portion of the charge to a fraction boiling in the
lubricating oil range, subjecting the lube oil fraction so produced
to catalytic dewaxing by contacting same with a catalyst comprising
a Group VI metal and a Group VIII metal or their compounds or
mixtures thereof supported on a mordenite having a silica-alumina
ratio of at least 20:1 in the presence of hydrogen under dewaxing
conditions and recovering a naphthenic oil from the dewaxed
product.
2. The process of claim 1 in which the charge is a vacuum
residuum.
3. The process of claim 1 in which the dewaxing catalyst has a
silica:alumina ratio of at least 40.
4. The process of claim 1 in which the surface area is between 280
and 400 m.sup.2 /g, the pore volume is between 0.6 and 1.0 cc/g and
the average pore diameter is between 70 and 90A.
5. The process of claim 1 in which the catalytically dewaxed oil is
mildly hydrogenated.
6. The process of claim 1 in which the catalytically dewaxed oil is
subjected to a solvent extraction treatment.
7. The process of claim 6 in which the solvent is furfural.
8. The process of claim 6 in which the solvent is N-methyl
pyrollidone.
9. The process of claim 5 in which the entire effluent of the
dewaxing zone is introduced into the mild hydrogenation zone.
10. The process of claim 1 in which the charge is introduced into a
fixed bed of hydrocracking catalyst at an intermediate point
thereof and at least 3,000 SCF hydrogen per barrel of charge is
introduced at the lower end of said bed to flow countercurrently to
downwardly flowing heavier components of said charge and
concurrently with upwardly flowing lighter components of said
charge and the products of the hydrocracking reaction and removing
from the hydrocracking zone an overhead product containing a lube
oil fraction.
11. The process of claim 10 in which the entire overhead is
introduced into the dewaxing zone.
12. The process of claim 11 in which the entire dewaxing zone
effluent is introduced into a mild hydrogenation zone.
Description
This invention relates to the hydroconversion of petroleum
fractions. More particularly, it is concerned with the conversion
of low value stocks such as residuum into valuable oils.
Previously it was customary to use naphthenic oils as bases for
specialty oils such as turbine oils, torque fluids, transformer
oils and the like. However, recently the supply of crudes from
which naphthenic oils are obtained has diminished to such an extent
that there is a distinct shortage of naphthenic oils. It is
therefore an object of this invention to produce naphthenic oils.
Another object is to produce valuable naphthenic oils from
petroleum fractions of low value such as petroleum residue. These
and other objects will be obvious to those skilled in the art from
the following disclosure.
According to our invention there is provided a process for the
production of naphthenic oils which comprises contacting a
residue-containing petroleum fraction having an initial boiling
point of at least about 800.degree.F. with a catalyst comprising a
Group VI metal and a Group VIII metal or their compounds or
mixtures thereof on a support having cracking activity under
hydrocracking conditions to convert at least a portion of the
charge to a fraction boiling in the lubricating oil range,
subjecting the lube oil fraction so produced to catalytic dewaxing
by contacting same with a catalyst comprising a Group VI metal and
a Group VIII metal or their compounds or mixtures thereof supported
on a mordenite having a silica-alumina ratio of at least 20:1 in
the presence of hydrogen under dewaxing conditions and recovering a
naphthenic oil from the dewaxed product.
The charge stocks used in the process of this invention are heavy
residue-containing petroleum fractions having an initial boiling
point of at least about 800.degree.F. They may be derived from any
suitable crude source such as West Texas-New Mexico Sour, tar sand
oil, shale oil and the like. Ordinarily they are obtained by
distilling the crude to remove all of the materials boiling below
about 800.degree.F. Preferred starting materials are residua having
an IBP of at least 900.degree.F. obtained by vacuum distillation of
the crude oil.
The charge stock is first subjected to hydrocracking by contact in
the presence of hydrogen with a hydrocracking catalyst.
The hydrocracking catalyst comprises a Group VI metal or compound
thereof in association with a Group VIII metal or compound thereof.
Preferred metals are nickel, iron, cobalt, molybdenum and tungsten.
Preferred compounds are the oxides and sulfides. The Group VIII
metal may be present in an amount based on the entire catalyst
composite of about 1-10 percent by weight preferably 2-8 weight
percent. The Group VI metal may be present in an amount between
about 5 and 40 percent preferably between 6 and 25 percent by
weight. The catalyst support is composed of an amorphous inorganic
oxide such as alumina, silica, magnesia, zirconia or the like.
Since the charge stock contains asphaltenes, the catalyst should
have a surface area of at least 250 m.sup.2 /g preferably at least
300 m.sup.2 /g, a pore volume of at least 0.6 cc/g and an average
pore diameter of less than 100A., preferably between 50A. and 95A.
The pore diameter is calculated from the formula 4V/S where V is
the pore volume and S is the surface area and is expressed in
Angstrom units. As a practical matter, where the catalyst must
withstand the rigorous conditions of commercial operation in large
units, the surface area should not exceed 800 m.sup.2 /g and the
pore volume should not exceed about 1.0 cc/g. Good results have
been obtained using catalysts having a surface area of 280-400
m.sup.2 /g, a pore volume of 0.6-0.8 cc/g and an average pore
diameter of 70-90A.
The catalyst may be shaped as pellets or spheres and may be used in
the form of a fixed, moving or fluidized bed. In a preferred
embodiment the catalyst is pellet-shaped and is used in the form of
a fixed bed. The charge stock may be passed upwardly or downwardly
through the reactor concurrently with the hydrogen or may be passed
downwardly countercurrent to an up-flowing stream of hydrogen. In a
specific embodiment, the charge stock is introduced into a fixed
bed of catalyst at an intermediate point thereof and hydrogen at
the rate of at least 3,000 SCF per barrel of charge sufficient to
maintain liquid above the point of introduction is introduced at or
near the base of the catalyst bed to flow countercurrent to the
downward-flowing heavier components of the charge and cocurrent to
the upward flowing lighter components of the charge and the
products of the hydrocracking reaction. The heavier materials
withdrawn from the bottom of the hydrocracking zone may be recycled
to the charge and the overhead removed from the upper end of the
hydrocracking zone may be sent in all or in part to the catalytic
dewaxing zone. In this embodiment the separation of the unconverted
residuum charge takes place in the hydrocracking zone. In the other
methods where the product is removed in its entirety from one
outlet of the hydrocracking zone, then the entire effluent
including hydrogen, hydrocracked product and unconverted charge may
be sent to the catalytic dewaxing zone or the effluent may be
separated into various components and the lube oil fraction sent to
the catalytic dewaxing zone with separated hydrogen or with fresh
hydrogen.
The hydrogen need not necessarily be pure hydrogen. Hydrogen having
a purity of at least 65 percent preferably 70-95 percent may be
used. Suitable sources of hydrogen are catalytic reformer
by-product hydrogen, hydrogen obtained by partial oxidation of
hydrocarbonaceous material followed by shift conversion and
CO.sub.2 removal and electrolytic hydrogen.
Reaction conditions in the hydrocracking zone include a temperature
of 650.degree.-950.degree.F., a pressure of 500-5000 psig, a space
velocity of 0.1-10 volumes of charge per volume of catalyst per
hour and a hydrogen rate of 1000-10,000 SCFB. Preferred conditions
are a temperature between 750.degree. and 900.degree.F., a pressure
between 1,000 and 3,000 psig, a space velocity between 0.3 and 1.5
v/v/hr and a hydrogen rate between 3,000 and 10,000 SCFB.
Conditions are chosen so that there is a substantial conversion,
e.g., at least 30 percent to materials boiling below the initial
boiling point of the charge. For example, if the temperature is at
the lower end of the above range, then the space velocity should
also be low but a low temperature should not be combined with a
high space velocity. As mentioned above, the entire effluent from
the hydrocracking zone or a selected portion thereof may be sent to
the catalytic dewaxing zone.
The oil is then subjected to catalytic dewaxing. In this stage the
oil is contacted with a catalyst in the presence of hydrogen at
elevated temperatures and pressures. The temperature will range
from 450.degree.-850.degree.F., preferably 550.degree.-750.degree.
F. Pressures of from atmospheric to 5,000 p.s.i.g. and higher may
be used although a preferred range is from 300 to 2,000 p.s.i.g. A
suitable liquid hourly space velocity is from 0.5 to 3.0 volumes of
oil per hour per volume of catalyst although space velocities of
from 0.1-10 may be used. Advantageously, hydrogen in an amount
ranging up to 20,000 s.c.f.b. (standard cubic feet per barrel) of
charge may be present, preferred rates being 500-10,000
s.c.f.b.
The catalyst used in the dewaxing stage of the process comprises a
hydrogenating component supported on a low sodium mordenite.
Synthetic mordenite is usually prepared as the alkali metal alumino
silicate which for the purpose of the present invention is an
inactive form. To convert the synthetic mordenite to a form active
for the hydrocracking of the waxy components of the oil, it is
converted to the hydrogen form by removal of the alkali metal ion,
usually sodium. The removal of the sodium ion is accomplished by
contacting the synthetic mordenite with ammonia or a compound
thereof usually in the form of a water solution to incorporate the
ammonium ion in the mordenite. Subsequent calcination converts the
mordenite to the active or acid form. The mordenite may also be
converted to the low sodium or acid form by contact with a dilute
acid such as 3N or 6N HCl. However, in addition to converting the
mordenite to the acid form, the mordenite is additionally treated
with acid to leach out a portion of the alumina thereby to increase
the silica-alumina ratio to at least 20:1 and preferably to at
least 40:1.
Of the various natural and synthetic zeolites now available in the
industry only the low sodium or acid form of mordenite is
satisfactory for the purposes of the present invention. Other
crystalline zeolites such as zeolite A, faujasite, zeolite X and
zeolite Y are unsatisfactory whether or not they have a low alkali
metal content. This is attributed to the combination of pore size
and unusual catalytic activity of the mordenite. Whereas zeolite A
and faujasite have pore openings of 5 A. and zeolites X and Y have
uniform pore openings of 10-13 A., the catalyst support used in our
process has sorption channels which are parallel to the C-axis of
the crystal and are elliptical in cross-section. The dimensions of
the sorption channels of sodium mordenite based on crystallographic
studies have been reported as a minor diameter of 5.8-5.9 A., a
major diameter of 7.0-7.1 A. and an average diameter of 6.6 A. The
hydrogen form of the mordenite appears to have somewhat larger pore
openings with a minor diameter of not less than 5.8 A. and a major
diameter less than 8 A. The effective working pore diameter of the
hyrogen mordenite prepared by acid treating synthetic mordenite
appears to be in the range of 8 A. to 10A. as indicated by the
absorption of aromatic hydrocarbons.
Supported on the hydrogen form of the mordenite is a hydrogenating
component which comprises a Group VIII metal or compound thereof,
for example the oxide or sulfide, which may be associated with a
Group VI metal or compound thereof. Noble metals such as platinum,
palladium and rhodium have been found especially useful and may be
used in amounts of 0.1-5 percent based on the total catalyst weight
with a range of 0.5-2.5 being preferred. Other suitable
hydrogenating components comprise nickel, cobalt and iron,
particularly when used in conjunction with a Group VI metal such as
molybdenum or tungsten. Suitable combinations include cobalt
molybdenum, nickel molybdenum and nickel tungsten. The latter type
of hydrogenating component may be present in an amount ranging from
5-40 percent by weight, preferably 10-25 percent. The hydrogenating
component may be incorporated into the support by ion exchange or
by impregnation, each of these methods being well known in the
art.
In the catalytic dewaxing stage of the process, the waxy components
are cracked to lighter components having a boiling point
considerably lower than the desired lube oil fraction and therefore
are easily separated therefrom. The principal byproducts of our
catalytic dewaxing process are light hydrocarbons such as ethane,
propane, butane and the corresponding olefins.
The following example is submitted for illustrative purposes
only.
EXAMPLE
In this example the charge is a mixture containing 90 percent West
Texas-New Mexico Sour and 10 percent Lafitte Paradis Vacuum Residua
having the following characteristics:
Gravity, .degree.API 11.7 Kinematic Viscosity, cs at 170.degree.F.
6030 at 210.degree.F. 1117 Conradson Carbon Residue, wt. %. 19.7
n-Pentane Insolubles, wt. % 10.2 Pour Point, 20 F. 120.+ Sulfur,
wt. % 2.88 Total nitrogen, ppm 4615 Metals, ppm Nickel 46 Vanadium
52 Iron 79 Initial boiling point, .degree.F. (approximate) 1000
The hydrocracking catalyst is in the form of a fixed bed of
pelleted cobalt molybdate on alumina catalyst having the following
characteristics:
Surface area, m.sup.2 /g 290 Pore volume, cc/g 0.63 *Average pore
diameter, A 86.9 Cobalt, wt. % 2.0 Molybdenum, wt. % 9.0 Silica,
wt. % 3.9 Alumina, wt. % 78.9 *d=4 Vg/Sg where d= average pore
diameter Vg = pore volume per unit mass and Sg = surface area per
unit mass.
Hydrocracking is effected under the following conditions with the
yields listed below:
Average Operating Conditions Space velocity, v/v/hr 0.4 Pressure,
psig 2000 Hydrogen rate, SCFB 7710 Temperature, .degree.F. 815
Hydrogen purity, vol. % 88 Hydrogen consumption, SCFB 1575
1000.degree.F.+ conversion, vol. % of feed 61.8
Product yield Volume % Weight % Ammonia 0.31 Hydrogen Sulfide 2.65
Dry Gas (C.sub.1 -C.sub.3) 2.20 Butanes 1.7 1.0 Pentanes 1.5 0.9
Naphtha (C.sub.6 -410.degree.F.) 11.3 8.9 Light Gas Oil
(410.degree.F.-600.degree.F.) 15.4 13.3 Lube Fraction
(600.degree.F.-1000.degree.F.) 37.9 35.2 Residuum (1000.degree.F.+)
38.2 38.1
the 600.degree.-1000.degree.F. lube oil cut is separated into four
fractions, (1) a heavy gas oil, (2) a spindle oil, (3) a light lube
fraction and (4) a heavy lube fraction. They have the following
properties:
Fraction 1 2 3 4 Gravity, .degree.A:I 29.9 23.9 21.1 Viscosity,
SUS, 100.degree.F. 52.4 67.5 165.0 830 210.degree.F. 33.5 35.6 43.2
72.1 Pourpoint, .degree.F. +5 +45 +85 +115 Carbon Residue, wt. %
0.20 0.06 0.05 0.74 Sulfur, Wt. % 0.06 0.06 0.10 0.18 Viscosity
Index 78 71 74 69
The four fractions are then catalytically dewaxed by being passed
with hydrogen through a fixed bed of particulate dewaxing catalyst
composed of 2 weight percent palladium on on acid-leached mordenite
having a silica:alumina mole ratio of 53:1. Operating conditions
and results are as follows:
Operating Conditions 1 2 3 4 Temperature, .degree.F. 650 650 650
650 Pressure, psig 300 300 300 850 Hydrogen rate, SCFB 2000 2000
2000 2000 Space Velocity, v/v/hr 1.0 1.0 0.5 0.5 Yield, vol. % 60
88 75 55 Product Gravity, .degree.API 29.9 29.7 26.1 23.5
Viscosity, SUS, 100.degree.F. 305 345 380 500 210.degree.F. 53.5
77.3 177 1200 Viscosity Index 64 70 75 50 Pourpoint, .degree.F. -70
+10 +5 +15
to improve the properties of the dewaxed oil such as color and
viscosity index the oil may be subjected to a mild hydrogenation or
hydrorefining or may be subjected to solvent extraction.
For the hydrorefining, the catalytically dewaxed oil is introduced
into the hydrorefining stage and brought into contact with the
hydrogenating catalyst at elevated temperatures and pressures in
the presence of hydrogen. Suitable catalysts comprise the oxides
and/or sulfides of metals such as cobalt, molybdenum, nickel,
tungsten, chromium, iron, manganese, vanadium and mixtures thereof.
The catalytic materials may be used alone or may be deposited on or
mixed with a support such as alumina, magnesia, silica, zinc oxide,
natural and synthetic zeolites or the like. Particularly suitable
catalysts are nickel tungsten sulfide, molybdenum oxide on alumina,
a mixture of cobalt oxide and molybdenum oxide generally referred
to as cobalt molybdate on alumina, molybdenum oxide and nickel
oxide on alumina, molybdenum oxide, nickel oxide and cobalt oxide
on alumina, nickel sulfide on alumina, molybdenum sulfide, cobalt
sulfide and nickel sulfide on alumina.
In the hydrorefining zone, pressures and temperatures may range
broadly between 500-5,000 p.s.i.g. and 500.degree.-900.degree.F.,
preferred ranges being 800-3,000 p.s.i.g. and
600.degree.-800.degree.F., respectively. Space velocities of
0.25-3.0 may be used although a rate between 0.5 and 1.5 is
preferred. The hydrogen rate may range between 200 and 10,000
s.c.f.b. although suitable results are obtained at hydrogen rates
between 2,000 and 6,000 s.c.f.b. The hydrorefining treatment
conditions are selected so that it results in a hydrogenated
product having substantially the same boiling range as the charge
to the hydrorefining zone and is termed non-destructive
hydrogenation as distinguished from destructive hydrogenation in
which a substantial portion of the product boils at a temperature
below that of the charge.
In the solvent refining operation the oil undergoing treatment is
subjected to liquid-liquid contact with a selective solvent which
preferentially dissolves the more aromatic constituents from the
oil undergoing treatment. It is a characteristic of the selective
solvent employed that it is partially miscible with the oil
undergoing treatment so that during the solvent refining operation
there are formed two phases, a raffinate phase containing
substantially only a solvent refined oil having a reduced amount or
proportion of aromatic hydrocarbons as compared to the oil charged
to the solvent refining operation, and an extract phase or mix
comprising selective solvent and dissolved therein extract or
extracted oil having a relatively increased proportion or amount of
more aromatic hydrocarbons as compared with the charge oil. The
aforesaid solvent refining operation may be carried out stagewise
(combinations or mixer-settler) or continuously in a suitable
contacting apparatus, e.g., packed or plate tower, rotating disc
contactor, either concurrently or countercurrently. Selective
solvents which are suitably employed include furfural, phenols,
liquid sulfur dioxide, nitrobenzene, .beta.
,.beta.'-dichloroethylether, dimethyl-formamide, diethylene glycol,
N-methyl pyrrolidine and the like.
If stability to ultraviolet light is not important then the
catalytically-dewaxed oil may be finished by the hydrorefining
treatment. However, if it is desired to produce an oil which is
stable to ultraviolet light, then the catalytically dewaxed oil
should be finished with a solvent extraction treatment preferably
using furfural or N-methyl pyrrolidone as the solvent.
When mild hydrogenation is used as the finishing step, the entire
effluent from the catalytic dewaxing zone may be sent to the
hydrorefining zone unless it is desired to recover the low boiling
olefins such as ethylene and propylene present in which case these
products are removed from the catalytic dewaxing zone effluent
prior to the hydrorefining.
* * * * *