U.S. patent number 3,658,654 [Application Number 04/816,695] was granted by the patent office on 1972-04-25 for screw-conveying retorting apparatus with hydrogenation means.
This patent grant is currently assigned to Standard Oil Company. Invention is credited to Louis C. Gutberlet.
United States Patent |
3,658,654 |
Gutberlet |
April 25, 1972 |
SCREW-CONVEYING RETORTING APPARATUS WITH HYDROGENATION MEANS
Abstract
Apparatus for the pyrolysis of solids containing carbonaceous
materials including a cylindrical substantially horizontal
pyrolysis vessel together with solids input and removal means
communicating with the vessel. Solids are conveyed through the
pyrolysis vessel by means of an auger-type conveyor. Heating means
are provided for heating solids between the input and removal
means. Gas input and withdrawal means permit the input and removal
of gas from the pyrolysis vessel, and gas delivery means are
provided for delivering gas to subsequent processing equipment. The
gas is recycled back to the gas input means via gas recycle means.
Stripping gas delivery means are also provided to deliver a
stripping gas to the pyrolysis vessel downstream of the gas
withdrawal means.
Inventors: |
Gutberlet; Louis C. (Crown
Point, MD) |
Assignee: |
Standard Oil Company (Chicago,
IL)
|
Family
ID: |
25221367 |
Appl.
No.: |
04/816,695 |
Filed: |
April 16, 1969 |
Current U.S.
Class: |
202/118; 201/29;
201/37; 201/33; 202/134 |
Current CPC
Class: |
C10B
7/10 (20130101) |
Current International
Class: |
C10B
7/10 (20060101); C10B 7/00 (20060101); C10b
001/06 (); C10b 007/10 (); C10b 047/20 () |
Field of
Search: |
;202/118,119,133,134,135
;201/33,32,29,36-38 ;208/9,10,11 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Yudkoff; Norman
Assistant Examiner: Edwards; David
Claims
I claim:
1. Improved apparatus for the pyrolysis of solids containing
carbonaceous materials comprising: a cylindrical, substantially
horizontal pyrolysis vessel; an auger-type conveyor in said vessel,
said conveyor being adapted to deliver solids in a downstream
direction from an upstream portion to a downstream portion of said
vessel; solids input means for introducing solids containing
carbonaceous materials into said upstream portion of said vessel;
solids removal means for removing solids from said downstream
portion of said vessel; heating means for heating said solids
containing carbonaceous materials between said solids input and
removal means; gas input means communicating with said vessel; gas
withdrawal means communicating with said vessel at a point located
in said downstream direction from said gas input means; stripping
gas input means for introducing a stripping gas into said vessel at
a point located in said downstream direction from said gas
withdrawal means; gas delivery means for delivering gases from said
gas withdrawal means to hydrogenation means; and gas recycle means
for recycling gas from said hydrogenation means to said gas input
means.
2. The apparatus as defined in claim 1 further including gas
preheating means for preheating said gas prior to introduction into
said vessel.
3. The apparatus as defined in claim 2 further including a spent
shale container communicating with said solids removal means, and
wherein said stripping gas input means communicates with said spent
shale container.
4. Improved apparatus for the pyrolysis of oil shale and the like
comprising: a substantially horizontal, cylindrical pyrolysis
vessel; an auger-type conveyor in said vessel, said conveyor being
adapted to deliver solids in a downstream direction from an
upstream portion to a downstream portion of said vessel; a raw
shale container; solids input means providing communication between
said storage container and said upstream portion of said pyrolysis
vessel; a spent shale container; solids removal means providing
communication between said spent shale container and said
downstream portion of said pyrolysis vessel; heating means for
heating said solids containing carbonaceous materials between said
solids input and removal means; gas input means communicating with
said vessel; gas withdrawal means communicating with said vessel at
a point located in said downstream direction from said gas input
means; stripping gas input means communicating with said vessel at
a point located in said downstream direction from said gas
withdrawal means; hydrogenation means; gas delivery means for
delivering gases from said gas withdrawal means to said
hydrogenation means; and gas recycle means for recycling gas from
said hydrogenation means to said gas input means.
5. The apparatus as defined in claim 4 wherein said stripping gas
input means communicates with said pyrolysis vessel at the
downstream end thereof.
6. The apparatus as defined in claim 4 wherein said stripping gas
input means communicates with said pyrolysis vessel through said
spent shale container.
7. The apparatus as defined in claim 4 wherein said stripping gas
input means includes stripping gas preheating means.
8. The apparatus as defined in claim 4 further including gas
preheating means for preheating said gas in said gas recycle means.
Description
The present invention relates to an improved apparatus for the
pyrolysis of solids containing carbonaceous materials.
Oil bearing solids such as oil shale are a significant source of
carbonaceous material used in the manufacture of petroleum
products. It is known that these carbonaceous materials may be
removed from these solids by a simple pyrolysis process, preferably
in the presence of hydrogen to prevent the formation of high
molecular weight materials.
The vaporized carbonaceous materials are then conveniently
hydrogenated and/or subjected to other subsequent processing before
being condensed to the liquid state.
Generally, the apparatus of the present invention comprises an
elongated, substantially horizontal pyrolysis vessel having an
auger-type conveyor therein. Solids input means communicate with
the vessel for introducing solids containing carbonaceous
materials, and solids removal means also communicate with the
vessel downstream of the solids input means. As used herein, the
term "downstream" refers to the direction in which the solid
material is moved by the auger in the pyrolysis vessel. The
invention also provides heating means for heating solids containing
carbonaceous materials between the solids input and removal means.
These heating means may be entirely external, and it is not
necessary to burn any portion of the carbonaceous material in order
to provide heat for the pyrolysis. Gas input means and gas
withdrawal means also communicate with the vessel, while stripping
gas input means communicate with the vessel downstream of the gas
withdrawal means. Finally, gas delivery means are provided for
delivering gases from the gas withdrawal means to the subsequent
processing equipment, and gas recycle means are provided for
recycling gas from the subsequent processing equipment back to the
gas input means.
The invention, its organization and method of operation, together
with the preferred embodiments thereof, will be best understood by
reference to the following detailed description, taken together
with the drawing, which is a diagrammatic illustration of an
apparatus embodying the features of the present invention.
Referring to the drawing, the apparatus of the present invention
provides an elongated, substantially horizontal pyrolysis vessel
10, which is preferably cylindrical in shape. The interior of the
pyrolysis vessel 10 contains an auger-type conveyor 12, which is
driven by a motor 14. As will be seen from the subsequent
description, a particular advantage of the present invention is
that many of the parts, such as the motor 14, are outside the
pyrolysis vessel 10, and therefore are not exposed to pyrolysis
temperatures.
A raw shale container 16 communicates with the pyrolysis vessel 10
at an upstream portion thereof through solids input means. The raw
shale container 16 is filled with particulate solids containing
carbonaceous material, in this instance raw oil shale 17. Of
course, other solids containing carbonaceous materials may be
processed in the apparatus of the present invention, as will be
understood by those skilled in the art. The oil shale 17 is
delivered to the pyrolysis vessel 10 through a solids input conduit
18 under the influence of gravity.
Downstream of the input conduit 18, also communicating with the
interior of the pyrolysis vessel 10, is a solids removal conduit
22. The solids removal conduit 22 provides communication between
the pyrolysis vessel 10 and a spent shale container 26, which
collects spent shale 27. It will thus be seen that, when the auger
12 is in operation, particulate solids will be delivered from the
raw shale container 16 through the pyrolysis vessel 10 to the spent
shale container 26. Since the entire system is preferably
maintained under pressure, it will be necessary that the raw shale
container 16 and spent shale container 26 be closed to the
atmosphere. Suitable means, not shown in the drawings, may be
provided for introducing and removing particulate materials from
these containers 16, 26 without the necessity of depressurizing the
system.
Between the solids input conduit 18 and the solids removal conduit
22, there are heating means 28 for heating the solids containing
carbonaceous materials in the pyrolysis vessel 10. The type of
heating means employed is not important, so long as they are
capable of producing pyrolysis temperatures within the pyrolysis
vessel 10. When the apparatus is employed as part of a petroleum
refinery, numerous sources of fuel are available, so that the
heating means may comprise a furnace. On the other hand, electrical
heating coils surrounding the pyrolysis vessel 10 could also be
employed.
The drawing also illustrates gas input and withdrawal means, as
well as stripping gas input means and gas recycle means. Gas is
maintained in the entire system under pressure from a gas source,
preferably a hydrogen source, designated by reference numeral 30.
This gas is delivered to the pyrolysis vessel 10 through a gas
input line 32. In the preferred embodiment a portion of the gas
input line 32 is surrounded by heating means in order to preheat
the gas before it is introduced into the pyrolysis vessel 10. In
the embodiment shown, the gas input line 32 has a coiled portion 34
within the heating means 28. Of course, separate preheating means
on the gas input line 32 may be employed.
Gas is withdrawn from the pyrolysis vessel 10 at a gas withdrawal
line 36, which also serves as gas delivery means for delivering the
gas removed from the pyrolysis vessel 10 to subsequent processing
equipment designated by reference numeral 38. This subsequent
processing equipment 38 may simply be a condenser to separate
vaporized carbonaceous materials from the gas, but preferably
comprises hydrotreating or hydrodesulfurizing equipment wherein the
carbonaceous material is upgraded and separated from the hydrogen
stream. The hydrogen stream is then returned to the gas input line
32 through a recirculation line 40. It will thus be seen that the
gas input line 32, the pyrolysis vessel 10, the gas withdrawal line
36, the subsequent processing equipment 38, and the recirculation
line 40 form a closed loop. To the extent that any hydrogen is
consumed during the pyrolysis and subsequent processing, it is
replaced from the hydrogen source 30.
As the drawing illustrates, a stripping gas input line 42 also
communicates with the interior of the pyrolysis vessel 10. Two
embodiments are shown in the drawing. In the first embodiment, the
stripping gas input line 42 communicates with the interior of the
spent shale container 26. Since the solids in the spent shale
container 26 will be hot, the stripping gas will be heated by these
solids so that it will vaporize residual carbonaceous material
carried by the solids subsequent to pyrolysis. However, if
sufficient heating is not provided by the solids in the spent shale
container 26, auxiliary preheating means 44 on the stripping gas
input line 42 may be provided.
As shown by a phantom line 46, the stripping gas input line 42 may
optionally communicate directly with the end of the pyrolysis
vessel 10, bypassing the spent shale container 26. In any event,
the stripping gas should preferably flow in a direction opposite to
the flow between the hydrogen gas input and the withdrawal lines
32, 36, respectively, in order to prevent the collection of gas and
vaporized carbonaceous materials at the end of the pyrolysis vessel
10.
The stripping gas may be any gas that does not react with the
hydrogen or carbonaceous materials in the pyrolysis vessel 10. In
the preferred embodiment, the stripping gas is hydrogen, and is
drawn from the hydrogen source 30.
The following examples are intended to illustrate the present
invention, and should not be construed as limitative, the scope of
the invention being determined by the appended claims.
The runs described in the following examples were performed in an
apparatus constructed in a manner similar to that shown in the
drawing, wherein the optional stripping gas inlet line shown by the
phantom line 46 was employed. The pyrolysis vessel was constructed
of 2-inch diameter stainless steel pipe, and hydrogen entering
through the gas input line 32 was preheated through the last 5 feet
of piping, and entered the pyrolysis vessel immediately downstream
of the raw shale container. The pyrolysis vessel was electrically
heated from the gas input line 32 to the solids removal conduit 22.
Temperatures were measured opposite the gas input line 32, the gas
withdrawal line 36, and midway between these two points. The auger
12 was normally rotated at a speed of 0.5 rpm, producing a shale
residence time in the pyrolysis vessel of 46 minutes. The raw shale
storage container 16 was filled with 14-28 mesh oil shale No. 4,
having the following Fischer assay:
Water yield: 1.38 weight percent Oil yield: 18.70 weight percent
Oil gravity: 25.0.degree. API
the operating pressure was 500 psig.
EXAMPLE I
Seven runs were made at varying temperatures. The temperatures
shown in Table I represent the average wall temperature in the
downstream half of the pyrolysis zone. ##SPC1##
As the above table shows, an acceptable product is produced under
any of the reaction conditions shown. However, at the temperatures
above 900.degree. F. a substantial reduction in the amount of coke
is achieved, although larger amounts of carbon oxides are produced.
The shale oil production in each of the runs was acceptable.
EXAMPLE II
A series of additional runs was made, in which the vapors of the
pyrolysis product were conducted directly to a hydrogenation
reactor where they were hydrogenated over a conventional
cobalt-molybdena-alumina catalyst. The reaction conditions and
results are shown in Table II below.
TABLE II
Run No. 8 9 10 Retorting conditions Maximum temp., .degree.F. (b)
932 940 940 Shale feed rate, 1b/day 36.8 39.1 40.0 Recycle gas
rate, SCF/ton .times. 10.sup.-.sup.3 375 343 336 Stripping gas
rate, SCF/ton .times. 10.sup.-.sup.3 6.8 6.4 5.9 Hydrogenation
conditions Average temp., .degree.F. 710 835 725 H.sub.2 /oil
ratio, SCF/bbl .times. 10.sup.- .sup.3 281 268 272 Space velocity
(Wt/Wt/hr) 0.39 0.52 0.46 Space velocity (Vol/Vol/hr) 0.35 0.46
0.40 Throughput (Vol oil/Vol catalyst) 1.33 3.00 4.42 Total
carbonaceous matter recovered (wt % based on raw shale) 22.7 27.1
23.4 Product Distribution, wt % Carbon Oxides 3.0 1.6 3.2 Dry Gas
10.3 11.4 10.0 Shale Oil 76.5 79.7 79.7 Shale Coke 10.2 7.3 7.1 Oil
inspections Gravity, .degree.API 33.1 37.5 32.2 Sulfur, wt % 0.16
0.015 0.12 Nitrogen, wt % 1.40 0.91 1.49
As shown by Table II, in each instance, a high yield of shale oil
is obtained.
Obviously, many modifications and variations of the invention as
hereinbefore set forth may be made without departing from the
spirit and scope thereof, and it is intended to cover in the
appended claims all such modifications and variations as fall
within the true spirit and scope of the invention.
* * * * *