U.S. patent number 3,919,074 [Application Number 05/499,741] was granted by the patent office on 1975-11-11 for process for the conversion of hydrocarbonaceous black oil.
This patent grant is currently assigned to Universal Oil Products Company. Invention is credited to John G. Gatsis.
United States Patent |
3,919,074 |
Gatsis |
November 11, 1975 |
Process for the conversion of hydrocarbonaceous black oil
Abstract
A process for the conversion of a hydrocarbonaceous black oil,
wherein a heated portion of the charge stock is recycled to the
inlet of the charge heater, is disclosed.
Inventors: |
Gatsis; John G. (Des Plaines,
IL) |
Assignee: |
Universal Oil Products Company
(Des Plaines, IL)
|
Family
ID: |
23986503 |
Appl.
No.: |
05/499,741 |
Filed: |
August 22, 1974 |
Current U.S.
Class: |
208/48R; 208/213;
208/108; 208/251H |
Current CPC
Class: |
C10G
47/00 (20130101) |
Current International
Class: |
C10G
47/00 (20060101); C10G 009/16 (); C10G
013/06 () |
Field of
Search: |
;208/48 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Gantz; Delbert E.
Assistant Examiner: Schmitkons; G. E.
Attorney, Agent or Firm: Hoatson, Jr.; James R. McBride;
Thomas K. Page, II; William H.
Claims
I claim as my invention:
1. A process for the conversion of a hydrocarbonaceous black oil,
which process comprises the steps of:
a. admixing said black oil with hydrogen and heating the resulting
mixture in a heater to a temperature above about 600.degree.F.;
b. recycling at least a portion of the heated mixture to the inlet
of said heater;
c. contacting at least a portion of the heated mixture with a
catalytic composite in a conversion zone maintained at hydrocarbon
conversion conditions; and,
d. recovering a converted hydrocarbon product.
2. The process of claim 1 further characterized in that said heater
is a direct fired heater.
3. The process of claim 1 further characterized in that said black
oil is derived from tar sand, shale or any other inorganic
oil-bearing substance.
4. The process of claim 1 further characterized in that said
hydrocarbon conversion conditions comprise a pressure of from about
500 psig. to about 5,000 psig., a temperature of from about
600.degree.F. to about 900.degree.F., a hydrogen gas circulation
rate from about 1,000 SCFB to about 20,000 SCFB.
Description
DISCLOSURE
The invention described herein is adaptable to a process for the
conversion of petroleum crude oil into boiling hydrocarbon
products. More specifically, the present invention is directed
toward a process for converting atmospheric tower bottoms products,
vacuum tower bottoms products, crude oil residuum, topped crude
oils, crude oils extracted from tar sands, etc., which are
sometimes referred to as "black oils," and which contain a
significant quantity of asphaltic material.
Petroleum crude oils, particularly the heavy oils extracted from
tar sands, topped or reduced crudes, and vaccum residuum, etc.,
contain high molecular weight sulfurous compounds in exceedingly
large quantities. In addition, such crude, or black oils contain
excessive quantities of nitrogenous compounds, high molecular
weight organo-metallic complexes principally comprising nickel and
vanadium, and asphaltic material. Currently, an abundant supply of
such hydrocarbonaceous material exists, most of which has a gravity
less than 20.0.degree. API at 60.degree.F., and a significant
proportion of which has a gravity less than 10.0. This material is
generally further characterized by a boiling range indicating that
10 percent or more, by volume boils above a temperature of about
1,050.degree.F. The conversion of at least a portion of the
material into distillable hydrocarbons--i.e., those boiling below
about 1,050.degree.F.--has hitherto been considered nonfeasible
from an economic standpoint. Yet, the abundant supply thereof
virtually demands such conversion, especially for the purpose of
satisfying the ever-increasing need for greater volumes of the
lower boiling distillables.
The present invention is particularly adaptable to the catalytic
conversion of black oils into distillable hydrocarbons. Specific
examples of the black oils to which the present scheme in uniquely
applicable, include a vacuum tower bottoms product having a gravity
of 7.1.degree. API at 60.degree.F. containing 4.05 percent by
weight of sulfur and 23.7 percent by weight of asphaltics; a
"topped" Middle East Kuwait crude oil, having a gravity of
11.0.degree. API at 60.degree.F., containing 10.1 percent by weight
of asphaltenes and 5.20 percent by weight of sulfur; and a vacuum
residuum having a gravity of 8.8.degree. API at 60.degree.F.,
containing 3.0 percent by weight of sulfur and 3,400 ppm. of
nitrogen and having a 20.0 percent volumetric distillation point of
1,055.degree.F. The principal difficulties, attendant the
conversion of black oils, stem from the presence of the asphaltic
material. This asphaltic material consists primarily of high
molecular weight, non-distillable coke precursors, insoluble in
light hydrocarbons such as pentane or heptane, and which are often
found to be complexed with nitrogen, metals and especially sulfur.
Generally, the asphaltic material is found to be colloidally
dispersed within the crude oil, and, when subjected to elevated
temperatures, has the tendency to flocculate and polymerize whereby
the conversion thereof to more valuable oil-soluble products
becomes extremely difficult.
Not only does the flocculation and polymerization of the asphaltic
material decrease the yield of valuable hydrocarbon products but
when these coke precursors form coke during heating and prior to
entering the catalytic reaction zone, the internal surfaces of the
heaters which contact the oil become coated with coke. Such coking
or fouling of the heater's heat transfer surface causes less
favorable heat transfer rates and in order to compensate for this
lower heat transfer rate, the heater temperatures must be increased
which only further aggravates the coking problem.
I have discovered that this problem can be alleviated by providing
a recycle of previously heated black oil to the inlet of the heater
to ensure adequate turbulence and ample mixing of the black oil
being heated. This recycle will lessen the temperature gradient
across the heat transfer area of the heater, and provide a more
uniform oil temperature in the entire cross-section of the flowing
black oil. Furthermore, this recycle will promote better heat
transfer, thereby lowering the temperature of the heat transfer
surface which, in turn, lessens the propensity of the black oil
along with the asphaltenes contained therein to form coke and heavy
polymers.
A principal object of the present invention is to retard and
inhibit the formation of undesirable coke and polymers on the heat
transfer surfaces of the primary heater in a process for the
conversion of hydrocarbonaceous black oil.
Another object is to promote better initial heat transfer rates in
such a heater which will permit a lower temperature for the heat
transfer surfaces which, in turn, will minimize coke-producing high
temperatures.
Yet another object is to extend the length of time between
maintenance of the heat exchange surfaces for the removal of
accumulated coke and polymers.
In one embodiment, therefore, the present invention relates to a
process for the conversion of a hydrocarbonaceous black oil, which
process comprises the steps of: (a) admixing said black oil with
hydrogen and heating the resulting mixture in a heater to a
temperature above about 600.degree.F.; (b) recycling at least a
portion of the heated mixture to the inlet of said heater; (c)
contacting at least a portion of the heated mixture with a
catalytic composite in a conversion zone maintained at hydrocarbon
conversion conditions; and, (d) recovering a converted hydrocarbon
product.
A black oil is intended to connote a hydrocarbonaceous mixture of
which at least about 10 percent boils above a temperature of about
1,050.degree.F., and which has a gravity, .degree.API at
60.degree.F., of about 20 or less. As will be readily noted by
those skilled in the art of petroleum refining techniques, the
conversion conditions hereinafter enumerated are well known and
commercially employed. The conversion conditions include
temperatures above about 600.degree.F., with an upper limit of
about 800.degree.F., measured at the inlet to the catalytic
reaction zone. Since the bulk of the reactions are exothermic, the
reaction zone effluent will be at a higher temperature. In order to
preserve catalyst stability, it is preferred to control the inlet
temperature such that the effluent temperature does not exceed
about 900.degree.F. Hydrogen is admixed with the black oil charge
stock by compressive means in an amount generally less than about
20,000 SCFB, at the selected pressure and preferably in an amount
of from about 1,000 to about 10,000 SCFB. The operating pressure
will be greater than 500 psig. and generally in the range of about
1,500 psig. to about 5,000 psig. It is not essential to my
invention to employ a particular type of reaction zone. Upflow,
downflow or radial flow reaction zones may suitably be employed
within the reaction zone in a fixed bed, moving bed, ebullating bed
or a slurry system. Likewise, the type, form or composition of the
catalyst is not essential to my invention and any suitable black
oil hydrocarbon conversion catalyst may be selected. The catalyst
disposed within a fixed bed or moving bed reaction zone can be
characterized as comprising a metallic component having
hydrogenation activity, which component is composited with a
refractory inorganic oxide carrier material of either synthetic or
natural origin. The precise composition and method of manufacturing
the carrier material is not considered essential to the present
process, although a siliceous carrier, such as 88 percent alumina
and 12 percent silica, or 63 percent alumina and 37 percent silica,
or an all alumina carrier, are generally preferred. Suitable
metallic components having hydrogenation activity are those
selected from the group consisting of the metals of Group VI-B and
VIII of the Periodic Table, as indicated in the Periodic Chart of
the Elements, Fisher Scientific Company (1953). Thus the catalytic
composite may comprise one or more metallic components from the
group of molybdenum, tungsten, chromium, iron, cobalt, nickel,
platinum, palladium, iridium, osmium, rhodium, ruthenium and
mixtures thereof. The concentration of the catalytically active
metallic component, or components, is primarily dependent upon the
particular metal as well as the characteristics of the charge
stock. For example, the metallic components of Group VI-B are
preferably present in an amount within the range of about 1.0
percent to about 20.0 percent by weight, the iron-group metals in
an amount within the range of about 0.2 percent to about 10.0
percent by weight, whereas the platinum-group metals are preferably
present in an amount within the range of about 0.1 percent to about
5.0 percent by weight, all of which are calculated as if the
components existed within the finished catalytic composite as the
elemental metal.
The refractory inorganic oxide carrier material may comprise
alumina, silica, zirconia, magnesia, titania, boria, strontia,
hafnia, and mixtures of the two or more including silica-alumina,
alumina-silica-boron phosphate, silica-zirconia, silica-magnesia,
silica-titania, alumina zirconia, alumina-magnesia,
alumina-titania, magnesia-zirconia, titania-zirconia,
magnesia-titania, silica-alumina-zirconia, silica-alumina-magnesia,
silica-alumina-titania, silica-magnesia-zirconia,
silica-alumina-boria, etc. It is preferred to utilize a carrier
material containing at least a portion of silica, and preferably a
composite of alumina and silica with alumina being in the greater
proportion. The catalysts utilized in a slurry system preferably
contain at least one metal selected from the metals of Group VI-B,
V-B and VIII. Slurry system catalysts usually are colloidally
dispersed in the hydrocarbonaceous charge stock and may be
supported or unsupported.
The following examples are given to illustrate the process of the
present invention and the effectiveness thereof in inhibiting and
retarding the formation of undesirable coke and polymers of the
heat transfer surfaces of the primary heater in a process for the
conversion of hydrocarbonaceous black oil. In presenting these
examples, it is not intended that the invention be limited to the
specific illustrations, nor is it intended that the process be
limited to particular operating conditions, catalytic composite,
processing techniques, charge stocks, etc. It is understood,
therefore, that the present invention is merely illustrated by the
specifics hereinafter set forth.
EXAMPLE I
A topped Middle-East Kuwait crude containing 5.2 percent by weight
sulfur and 10 percent by weight oil-insoluble asphaltenic material
and having a gravity of 11.degree. API at 60 .degree.F. is selected
for desulfurization in a catalytic reaction zone containing a
desulfurization catalyst which contains 2 percent by weight nickel
and 16 percent by weight molybdenum composited with a carrier
material of 88 percent alumina and 12 percent silica. The
desulfurization catalyst is loaded into fixed beds in a downflow
catalytic reaction zone. The topped crude is admixed with
sufficient hydrogen to achieve a hydrogen circulation rate of 6,000
SCFB. The admixture of topped crude and hydrogen is passed over the
heat exchange surfaces of a primary heater and then into the
catalytic reaction zone. A desulfurized hydrocarbonaceous black oil
is recovered from the reaction zone effluent. A target 1 percent
residual sulfur (the equivalent of 80 percent desulfurization) in
the hydrocarbon product is maintained by periodically adjusting the
outlet temperature of the primary heater. With a liquid hourly
space velocity of 0.9 hr..sup.-.sup. 1, the initial catalyst inlet
temperature required to reach the 1 percent target is 725.degree.F.
The hereinabove processing scheme is continuously operated for 90
days and then is shut down. Inspection of the heat exchange
surfaces shows that the carbon and polymer buildup on these
surfaces amounts to 40 grams per square meter.
EXAMPLE II
The processing scheme in Example I is modified to permit a
slipstream of heated black oil to be taken from the effluent of the
primary heater and recycled to the inlet of said primary heater.
The heat exchange surfaces are thoroughly cleaned to remove the
accumulated carbon and polymers. A fresh batch of catalyst which is
identical to that used in Example I is loaded into the catalytic
reaction zone and fresh topped crude is desulfurized at the same
operating conditions utilized in Example I except that 10 percent
of the liquid effluent from the primary heater is recycled to the
inlet of the primary heater. The processing scheme is also
continuously operated for 90 days and is then shut down. Inspection
of the heat exchange surfaces shows that the carbon and polymer
buildup on these surfaces amounts to 30 grams per square meter
which is considerably less than that produced in Example I.
The foregoing specification and illustrative examples clearly
indicate the means by which the present invention is effected, and
the benefits afforded through the utilization thereof.
* * * * *