U.S. patent number 3,617,474 [Application Number 05/045,081] was granted by the patent office on 1971-11-02 for low sulfur fuel oil from coal.
This patent grant is currently assigned to Hydrocarbon Research, Inc.. Invention is credited to Michael Calderon, Clarence A. Johnson, Harold H. Stotler.
United States Patent |
3,617,474 |
Stotler , et al. |
November 2, 1971 |
LOW SULFUR FUEL OIL FROM COAL
Abstract
The economic production of a low sulfur residual fuel oil by the
hydroconversion of coal is accomplished in an "ebullated" bed
system in the absence of downstream processing and the use of a
minimum of hydrogen to produce a fuel of high B.t.u. value and low
sulfur content.
Inventors: |
Stotler; Harold H. (Westfield,
NJ), Calderon; Michael (Flushing, NY), Johnson; Clarence
A. (Princeton, NJ) |
Assignee: |
Hydrocarbon Research, Inc. (New
York, NY)
|
Family
ID: |
21935899 |
Appl.
No.: |
05/045,081 |
Filed: |
June 10, 1970 |
Current U.S.
Class: |
208/409; 208/422;
208/432; 208/419; 208/429 |
Current CPC
Class: |
C10G
1/083 (20130101) |
Current International
Class: |
C10G
1/08 (20060101); C10G 1/00 (20060101); C01g
001/06 () |
Field of
Search: |
;208/10 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Gantz; Delbert E.
Assistant Examiner: O'Keefe; Veronica
Claims
We claim:
1. The process of producing a low sulfur fuel oil comprising less
than about 1 weight percent of sulfur by the hydrogenation of a
coal comprising greater than one weight percent of sulfur which
comprises:
a. passing an oil-coal slurry upwardly through a reaction zone
operating under a hydrogen partial pressure between about 800 and
about 2,500 p.s.i., and under a temperature between about
800.degree. and about 900.degree. F.;
b. consuming hydrogen, in the reaction zone, at a rate of at least
2 standard cubic feet (s.c.f.) and not to exceed 10 s.c.f. per
pound of coal;
c. maintaining a space velocity between about 75 and about 200 lbs.
of coal per hour per cubic foot of the reaction zone;
d. removing a coal effluent which comprises gases, liquids, ash and
unconverted coal solids;
e. separating a solids containing fraction from said effluent;
and
f. recovering a hydrocarbon fraction boiling above about
400.degree. F. plus, the volume of which is at least 2.5 barrels
per ton of coal fed to the reaction zone.
2. The process of claim 1 in which the reaction zone contains an
ebullated bed of particulated solids wherein said particulated
solids comprise cobalt molybdate on alumina.
3. The process of claim 1 in which the reaction zone contains an
ebullated bed of particulated solids wherein said particulated
solids comprise activated alumina.
4. The process of producing a low sulfur fuel oil comprising less
than about 1 percent of sulfur by the hydrogenation of a coal
comprising greater than one weight percent of sulfur which
comprises:
a. passing an oil-coal slurry upwardly through a reaction zone
operating under a hydrogen partial pressure between about 800 and
about 2,500 p.s.i. and under a temperature between about 800 and
about 900.degree. F.;
b. consuming hydrogen, in the reaction zone, at a rate of at least
2 standard cubic feet (s.c.f.) and not to exceed 10 s.c.f. per
pound of coal;
c. maintaining a space velocity between about 75 and about 200 lbs.
of coal per hour per cubic foot of the reaction zone;
d. removing a coal effluent which comprises gases, liquids, ash,
and unconverted coal solids;
e. separating a solids containing fraction from said effluent;
and
f. recovering a hydrocarbon fraction boiling above about
900.degree. F. plus, the volume of which is at least 1 barrel per
ton of coal fed to the reaction zone.
5. The process of claim 4 in which the reaction zone contains an
ebullated bed of particulated solids wherein said particulated
solids comprise cobalt molybdate on alumina.
6. The process of claim 4 in which the reaction zone contains an
ebullated bed of particulated solids wherein said particulated
solids comprise activated alumina.
7. The process of claim 4 wherein the hydrocarbon fraction boiling
above about 900.degree. F. plus is allowed to solidify and ground
for use as a particulate solid fuel.
8. The process of claim 1 wherein the hydrogen partial pressure is
about 1,890 p.s.i. and the temperature is about 850.degree. F.
9. The process of claim 4 wherein the hydrogen partial pressure is
about 1,890 p.s.i. and the temperature is about 850.degree. F.
Description
BACKGROUND
The increase in government concern regarding air pollution,
especially with regard to sulfur emission into the atmosphere, has
resulted in legislative action which could eliminate the use of
some of our conventional coals in the utilities market. This is
particularly true for coals such as Pittsburgh No. 8 which contains
about 4 percent sulfur, as well as Illinois No. 6. A process which
can economically convert coal to a fuel which will meet anticipated
air pollution regulations is of prime economic interest.
While it is known that such coals can be processed to produce
gasoline boiling range materials, together with some gas and some
heavier boiling products, it has been found that the high
consumption of hydrogen and catalyst, and relatively low coal
throughput per volume of reactor, is not economical unless gasoline
is the principal product made.
Hydrogenation of coal depends on many factors including the
characteristics of the coal as to oxygen, ash, and volatile
content. Other factors include those controllable reaction
conditions of temperature, pressure, throughput, and catalyst.
Equally as a controlling factor is the quality of the end
product.
Normally, the hydrogenation of coal has proceeded to the ultimate
production of gasoline or similar high quality fuels. In such case,
the use of hydrogen, a relatively expensive commodity has directed
the research into conditions of high conversion, usually requiring
two or more reaction stages and separation equipment.
SUMMARY OF THE INVENTION
This invention is primarily adapted to make an inexpensive, low
cost, fuel substitute of low gravity which may be used either as
ground-up solids or as a liquid if maintained at a temperature
above the melting point. The low sulfur characteristic is
especially beneficial for reduction of pollution.
DRAWING
The drawing is a schematic view of a reactor and auxiliary
equipment for a coal hydrogenation process.
DESCRIPTION OF PREFERRED EMBODIMENT
Coal at 10, appropriately ground at 12 (and not necessarily dried),
is mixed at 14 with recycle slurry oil 16 to form a coal-oil
slurry. This slurry is passed by line 18 through heater 20 into the
lower part of reactor 22. Hydrogen is added at 24. Liquid oil and
hydrogen pass upwardly through a bed of catalyst or activated
alumina at sufficient velocity to maintain an ebullated bed of
catalyst or inert solids such as disclosed in the Schuman U.S. Pat.
No. 3,281,393.
A gaseous phase is removed overhead at 26 and a liquid stream is
removed at 28. The liquid stream is in part recycled through pump
30 to maintain the desired liquid velocity and a net liquid stream
is removed at 32.
Preferably the coal is initially ground to all pass 20 mesh and not
more than about 10 percent passing 325 mesh (Tyler). The slurry at
18 is a pumpable slurry with at least equal parts of oil and coal
but, if for operating reasons, it is desirable to recycle an
additional amount of slurry oil, slurries of one part coal and up
to 10 parts oil may be used.
A temperature of 800.degree.-900.degree. F. preferably about
850.degree. F. and a hydrogen partial pressure of 800-2500 p.s.i.
and preferably about 1,890 p.s.i. is maintained in the reactor.
The vapors 26 leaving the upper part of the reactor are cooled at
34. Condensed light ends are separated in drum 36 and removed at
42. Vapors leaving drum 36 at 40 are cooled in exchanger 64 and
scrubbed with an absorber oil in column 63 to remove light
hydrocarbon gases at 65 and hydrogen leaving at 38 is recycled. The
recycle hydrogen stream 38 plus makeup hydrogen at 44 also passes
through heat exchanger 34, through heater 67 and becomes the
hydrogen feed line 24.
The liquid leaving the reactor at 32 is separated in one or more
fractionation columns 50 into a light ends stream 52, a middle
distillate at 53, a heavy gas oil at 54 and a heavy ends at 56.
The heavy ends at 56 contain a substantial amount of solids which
are sent to a filter 58. The filter cake is recovered at 60. The
filter cake comprises a char and ash product and may contain up to
20 percent of oil which can be recovered thermally. A centrifuge
could also be used.
The filtrate leaving filter 58 provides the slurry oil recycle
stream 16 and the fuel oil product, 62.
The low sulfur fuel oil product 62 will have an API gravity of
about -14.degree. with a B.t.u. value in excess of 16,600 BTU's per
pound. Normally this product has a boiling point not less than
400.degree. F. and must be kept hot in order to permit pumpability
or distillates can be removed to give a product boiling at
900.degree. F. and higher.
Alternatively, the fuel oil product can be cooled, solidified and
ground and used as a solid combustible fuel low in ash and sulfur,
especially when free of distillates.
The reactor 22 may be operated under varying conditions depending
upon the maximum sulfur desired in the fuel oil product. The
following table illustrates experimental results from the
operations. Approximately three barrels of fuel oil with a sulfur
content of less than 0.5 weight percent sulfur and 0.56 barrels of
naphtha have been produced per ton of Illinois No. 6 coal.
Treatment of coal from the Pittsburgh No. 8 seam has yielded 3.48
barrels of fuel oil per ton and 0.21 barrels per ton of naphtha. In
this case the fuel oil product contained approximately 1 percent
sulfur.
The versatility of the reactor is indicated in the table below in
which, in one case, 93 pounds of Illinois No. 6 coal per hour per
cubic foot was the coal feed rate utilizing a cobalt molybdate on
alumina catalyst. In such case the hydrogen consumption was
approximately 3.75 s.c.f./lb.
The Pittsburgh No. 8 coal was operated at a throughput rate of 187
pounds of coal per hour per cubic foot with activated alumina and
only 2 s.c.f./lb. of hydrogen was consumed.
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EXAMPLE OF TYPICAL COAL ANALYSES
Illinois No. 6 Pittsburgh No. 8
__________________________________________________________________________
Carbon 70.51 74.29 Hydrogen 5.14 5.49 Nitrogen 1.28 1.49 Sulfur
3.39 4.03 Oxygen 8.08 6.40 Ash 11.60 8.30 Volatile Matter (MAF)*
44.56 46.46 Organic sulfur 1.24 2.10
REACTOR CONDITIONS
Pressure, total--p.s.i.g. 2,250 2,250 Temperature .degree. F. 850
850 Hydrogen Consumption s.c.f./lb. 3.75 2 Catalyst CoMo on Alumina
Alumina Throughput lbs./hr./cu.ft. 93 187
__________________________________________________________________________
*MAF - Moisture and Ash Free
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EXAMPLES OF YIELDS
(Pounds per 100 pounds of dry coal)
Illinois No. 6 Pittsburgh No. 8 CO.sub.2 0.92 1.0 CO 0.31 C.sub.1
1.66 4.81 C.sub.2 0.80 C.sub.3 1.28 C.sub.4 -400 7.71 2.85 400-650
18.19 3.83 650-975 9.19 16.41 Residuum (975.degree. F. plus) 35.31
53.15 Coal Residue 7.34 6.90 Ash 11.60 8.30 H.sub.2 S 1.75 1.80
NH.sub.3 0.72 0.20 H.sub.2 O 5.27 1.80 102.05 101.05 Yield Summary
Fuel Oil 400.degree. F. plus B/T 3.06 3.48 Naphtha B/T 0.56 0.21
Sulfur (product) % by weight 0.46 1.02
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*B/T--Barrels per ton
The relatively low consumption of hydrogen, the high throughput of
the reactor, and the substantial absence of downstream refining
processing makes it possible to produce the low sulfur residual
fuel oil at a cost of about one half that for production of
gasoline.
Although but two examples of coal conversions are given, it is our
experience that operating ranges will be as follows:
Temperature 800-900.degree. F. Pressure, total 1,000-3,000 p.s.i.g.
Feed rate 75-200 lbs./hr./cu.ft. of reactor space
When the fuel oil recovered boils at 400.degree. F. plus it is
preferably maintained as a liquid fuel although it can be used as a
solid fuel. Where the fuel oil recovered is free of distillates, it
is preferable that the remaining fuel oil boil at 900.degree. F.
plus. This 900.degree. F. plus fuel oil is suitable for use as a
liquid fuel although it is preferably allowed to cool and used as a
solid fuel.
Ammonia and hydrogen sulfide produced in the coal hydrogenation
step are recovered and the hydrogen sulfide may be converted to
elemental sulfur by the Claus process providing ammonia and sulfur
as byproducts.
While we have shown and described a preferred form of embodiment of
our invention, we are aware that modifications may be made thereto
within the scope and spirit of our disclosure and the claims
hereinafter attached.
* * * * *