U.S. patent number 3,870,621 [Application Number 05/383,755] was granted by the patent office on 1975-03-11 for residuum processing.
This patent grant is currently assigned to Exxon Research and Engineering Company. Invention is credited to George T. Arnold, Jack M. Hochman, Robert E. Pennington.
United States Patent |
3,870,621 |
Arnold , et al. |
March 11, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
RESIDUUM PROCESSING
Abstract
A residual petroleum fraction or similar hydrocarbon oil boiling
in excess of about 700.degree. F. is contacted in liquid phase with
a finely divided, noncaking coal in a contacting zone at a
temperature in the range between about 700.degree. F. and about
900.degree. F., cracked products derived from the oil and
hydrocarbons from the coal are recovered overhead from the
contacting zone and fractionated to produce a heavy recycle stream
and lighter products, and a solid char is recovered as a bottoms
product from the contacting zone. The contacting of the oil with
coal in a fluidized bed at relatively low oil-to-coal ratios
results in the production of a low sulfur solid fuel having a Btu
content in the range of from about 12,000 to about 18,000
Btu/lb.
Inventors: |
Arnold; George T. (Baytown,
TX), Hochman; Jack M. (Cobham, EN), Pennington;
Robert E. (Baytown, TX) |
Assignee: |
Exxon Research and Engineering
Company (Linden, NJ)
|
Family
ID: |
23514581 |
Appl.
No.: |
05/383,755 |
Filed: |
July 30, 1973 |
Current U.S.
Class: |
208/415; 208/106;
208/211; 208/417; 201/23; 208/126; 208/129; 208/213; 208/434 |
Current CPC
Class: |
C10G
1/02 (20130101); C10G 11/02 (20130101); C10G
1/00 (20130101) |
Current International
Class: |
C10G
11/00 (20060101); C10G 1/00 (20060101); C10G
11/02 (20060101); C10G 1/02 (20060101); C10g
001/00 () |
Field of
Search: |
;208/8,46,106,129,211,213,11 ;252/445 ;201/23 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: O'Keefe; Veronica
Attorney, Agent or Firm: Reed; J. E.
Claims
We claim:
1. A process for the production of low boiling liquid hydrocarbons
from coal and a high boiling hydrocarbon oil composed primarily of
constituents boiling in excess of about 700.degree. F. which
comprises contacting said oil in a contacting zone with a finely
divided sub-bituminous or lower rank coal at a temperature in the
range between about 700.degree. F. and about 900.degree. F., a
pressure in the range between about 10 and about 100 pounds per
square inch gauge, and a space velocity between about 0.1 and about
3.0 pounds of oil per hour per pound of coal; withdrawing liquid
products overhead from said contacting zone; fractionating said
liquid products to obtain a high boiling liquid fraction boiling in
excess of about 700.degree. F. and a lighter fraction; recycling
said high boiling fraction to said contacting zone; and withdrawing
char from said contacting zone.
2. A process as defined by claim 1 wherein said high boiling
hydrocarbon oil is a residual petroleum fraction having an initial
boiling point in excess of about 700.degree. F.
3. A process as defined by claim 1 wherein said oil is contacted
with said coal in a fixed bed.
4. A process as defined by claim 1 wherein said oil is contacted
with said coal in a moving bed with an oil-to-coal ratio less than
about 10 to 1.
5. A process as defined by claim 1 wherein said oil contains
constituents boiling above 700.degree. F. in a concentration
greater than about 90 weight percent and has an API gravity of
about 25.degree. or lower, a carbon content of about 80 percent or
higher, and a Conradson carbon value of about 1 percent or
more.
6. A process as defined by claim 1 wherein said coal has an oxygen
content of about 15 percent or higher and a hydrogen content of
about 2 percent or lower.
7. A process as defined by claim 1 wherein said oil is a shale
oil.
8. A process as defined by claim 1 wherein said oil is a creosote
oil.
9. A process as defined by claim 1 wherein said oil is a bottoms
fraction from a catalytic cracking unit.
10. A process as defined by claim 1 wherein said oil is contacted
with said coal at a temperature between about 750.degree. F. and
about 850.degree. F. and at a space velocity between about 0.5 and
about 1.5 pounds of oil per pound of coal.
Description
BACKGROUND OF THE INVENTION 1. Field of the Invention
This invention relates to the upgrading of residual petroleum
fractions and similar heavy oils and is particularly concerned with
a process for converting a residual fraction or similar oil into
lighter products by contacting the oil with coal at elevated
temperature and pressure.
2. Description of the Prior Art
Conventional low cost processes for the conversion of residual
petroleum fractions and similar heavy hydrocarbon oils into lower
boiling naphthas and gas oils, such as delayed coking and thermal
cracking, generally require a high level of heat input and often
result in the production of relatively large quantities of low
value coke and gas. These disadvantages can be overcome in most
cases by resorting to more complex processes such as fluid coking
or fluidized catalytic cracking, but these normally entail much
higher initial investments and in some cases may therefore not be
economically feasible.
A number of methods for converting residual fractions and other
oils into lighter products have been suggested in the prior art,
including methods involving the concurrent processing of coal and
oil. Early proposals along these lines included the thermal
cracking of crude oil containing colloidally dispersed coal,
gilsonite or similar material in a still to permit the recovery of
liquid and gaseous hydrocarbons from the oil and solid material,
the mixing of powdered coal with hot oil to form a heavy plastic
mixture which is then baked or carbonized to produce a solid fuel
and oil vapors suitable for cracking and further processing, the
passing of cracked oil vapors through a bed of hot coal particles
to dissolve and distill the more volatile constituents from the
coal and produce coke, the coking of coal in the presence of a low
boiling fuel oil or similar petroleum fraction, and the replacement
of water in the pores of brown coal or a similar material with oil
which is subsequently cracked within the pores of the solid
particles. More recently, processes for the treatment of coal and
related materials with relatively low boiling, highly aromatic oils
to extract liquid constituents from the coal have been developed.
None of these methods, however, has provided a highly effective,
low-cost process for the upgrading of residual petroleum fractions
and similar high boiling oils into more valuable lower boiling
products.
SUMMARY OF THE INVENTION
This invention provides an improved process for the conversion of
high boiling residual petroleum fractions and similar oils into
lower boiling hydrocarbons which alleviates many of the
difficulties encountered heretofore and has pronounced advantages
over methods proposed in the past. In accordance with the
invention, it has now been found that residual petroleum fractions
and other hydrocarbon oils composed primarily of constituents
boiling in excess of about 700.degree. F. can be converted into
lower boiling hydrocarbons by contacting the oil in liquid phase
with a noncaking coal at a temperature in the range between about
700.degree. F. and about 900.degree. F., recovering an oil
containing cracked products overhead from the contacting zone,
fractionating this oil to produce a heavy recycle fraction and
lighter products, and recovering solid char as a bottoms product
from the contacting zone. The process may be carried out in either
a fixed or moving bed vessel at a space velocity between about 0.1
and about 3.0 pounds of oil per hour per pound of coal. In general,
the use of relatively high oil-to-coal ratios and low temperatures
tends to promote the production of high yields of liquid products
in the gas oil boiling range; whereas lower oil-to-coal ratios and
higher temperatures result in formation of more light ends and char
product. Contacting of the oil and coal in a moving bed at
oil-to-coal ratios less than about 10:1 permits the recovery of a
relatively low sulfur char which normally has a Btu content between
about 12,000 and about 18,000 Btu/lb. and is useful as a high
quality solid fuel.
Laboratory work has shown that the simultaneous treatment of
noncaking coal and high boiling oils in accordance with the
invention has a synergistic effect on product yields. The coal
apparently acts as a catalyst to promote cracking of the oil and
thus provides higher distillate product yields than might otherwise
be obtained; while at the same time the heavy oil apparently tends
to solubilize the coal and permit the recovery of coal-derived
liquids. Significantly more naphtha and gas-oil are produced than
are normally obtained in delayed coking and similar operations.
These high yields, coupled with the relatively low heat input level
required and the relatively simple, inexpensive equipment employed
in carrying out the process, permit the conversion of residual
petroleum fractions and similar oils at a cost considerably lower
than that of conventional fluid coking, delayed coking and related
operations and thus make the process of the invention widely
applicable.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 in the drawing is a schematic diagram illustrating the
conversion of a residual petroleum fraction or similar oil into
lighter products by contacting the oil with a sub-bituminous coal
in a fixed bed; and
FIG. 2 depicts a process which is similar to that of FIG. 1 but is
carried out in a fluidized bed.
DESCRIPTION OF THE SPECIFIC EMBODIMENTS
The high-boiling oil employed as a feed material in the process
depicted in FIG. 1 of the drawing may be a distillate or residual
petroleum fraction, a shale oil, or a similar hydrocarbon oil
composed primarily of constituents boiling in excess of about
700.degree. F. Suitable oils include atmospheric and vacuum
residuums obtained by the distillation of crude oils, bottoms
fractions from catalytic cracking units and other refinery
operations, asphalts, raw creosote oils, high-boiling crude oils,
heavy shale oils, high-boiling oils derived from tar sands, and the
like. Such oils will normally contain constituents boiling above
700.degree. F. in concentrations of about 90 weight percent or
higher and will have API gravities of about 25.degree. or lower,
carbon contents of about 80 percent of higher, and Conradson carbon
values of about 1 percent or more. The use of high-boiling residual
petroleum fractions having initial boiling points above about
700.degree. F. is generally preferred for purposes of the
invention.
In the particular embodiment of the invention shown in FIG. 1, a
high boiling residual petroleum fraction or similar heavy oil is
introduced into the system from a pipe still or similar unit at a
temperature of about 700.degree. F. and passed through line 10 into
the lower end of fractionating tower 11. Here the oil is heated and
the lighter fractions are flashed off. Lighter constituents boiling
below about 450.degree. F. are taken off overhead from the
fractionator through line 12, cooled in condenser 13, and passed to
flash drum 14. Noncondensable gases are taken off overhead through
line 15 and distillate in the naphtha boiling range is withdrawn
through line 16. The gas and naphtha streams may be passed to
downstream processing units for further treatment and subsequent
utilization. The heavier condensate separated from the overhead
stream is recycled to the upper end of the fractionating tower as
reflux through line 17. A heavier gas oil fraction boiling in the
range between about 450.degree. and about 700.degree. F. is
withdrawn from the fractionating tower through line 18 and passed
to downstream units for further processing.
The bottoms products from fractionator 11 are withdrawn through
line 19 and passed to furnace 20 where the heavy oil is heated to
the required conversion temperature between about 700.degree. F.
and about 900.degree. F., preferably to a temperature between
750.degree. F. and 850.degree. F. The heated oil withdrawn from the
furnace through line 21 is then passed into one of two or more
parallel fixed bed reaction vessels 22 and 23. These vessels are
fitted with inlet lines 24 and 25 containing valves 26 and 27 so
that the heated oil can be directed into either vessel. One of the
vessels is normally used for contacting the heated oil with coal
while the other is being cleaned and readied for reuse. The
reaction vessels are provided with overhead outlet lines 28 and 29
containing valves 30 and 31. These valves and those in the inlet
lines can be operated manually or fitted with electrical or
hydraulic controls and programmed to operate in a predetermined
sequence. As indicated earlier, more than two reaction vessels may
be employed if desired.
The fixed beds in reaction vessels 22 and 23 are charged with a
sub-bituminous or lower rank noncaking coal which has previously
been crushed and screened into the desired particle size. In
general, suitable coals include sub-bituminous coals, brown coals,
lignites, and similar materials having oxygen contents of about 15
percent or higher and hydrogen contents of about 2 percent of
lower. The coal size employed will depend upon the particular
method used to support the coal within the reaction vessels. It is
generally preferred to employ relatively coarse particles between
about 1/4 inch and 1 inch in size in order to reduce the pressure
drop through the bed and minimize plugging but other particles may
also be used, particularly if the bed is supported on suitable
grids or other devices designed to control distribution of the
upflowing oil and promote effective contact between the coal and
oil. As pointed out above, one of the reaction vessels is employed
for contacting oil with coal while the other vessel is being
cleaned and recharged with fresh coal. While oil is being
introduced into vessel 22 through line 24 containing valve 26, for
example, valve 27 in line 25 is closed. The heated oil from furnace
20, at a temperature between about 700.degree. F. and about
900.degree. F. and a pressure within the range between about 10
pounds per square inch gauge and about 100 pounds per square inch
gauge, is passed upwardly through the bed of sub-bituminous coal,
lignite, brown coal or the like in vessel 22 at a space velocity
within the range between about 0.1 to about 3.0 pounds of oil per
hour pound of coal. In general, space velocities between about 0.5
and about 1.5 pounds of oil per hour per pound of coal are
preferred. The upflowing oil is catalytically cracked in the
pressure of the coal to form lower boiling products. Some
extraction of liquids from the coal by the oil apparently also
takes place. The cracked products are withdrawn overhead from
vessel 22 through line 28 containing valve 30 and passed through
line 32 through the lower end of fractionation tower 11. Valve 31
in line 29 is closed to prevent the flow of products into vessel 23
during this period. The cracked products fed to the fractionation
tower supply heat to the heavy oil introduced through line 10 and
are ultimately recovered from the fractionating tower through lines
12 and 18. Any high-boiling constituents present in the stream
introduced through line 32 are mixed with the heavy oil feed and
recycled through line 19 to the contacting zone.
While vessel 22 is thus being used for the contacting of heavy oil
with the coal, vessel 23 is being cleaned and recharged with fresh
coal. Steam, water or other suitable cooling medium can be
introduced into vessel 23 to recover heat from the char produced by
the reactions taking place between the oil and coal and facilitate
removal of the char. Mechanical means for dislodging the char can
also be employed if necessary. The char product is recovered
through line 33 containing valve 34 and may be employed as a fuel,
fed to a gasifier, or used for other purposes. The bed in vessel 23
is then recharged with fresh sub-bituminous coal, lignite, brown
coal or the like. When the conversion rate in the vessel 22 falls
below the desired level, valves 27 and 31 are opened to permit the
circulation of heated oil through vessel 23 and valves 26 and 30
are closed to permit the cleaning and charging of vessel 22. The
two vessels are thus cycled to permit semicontinuous operation.
FIG. 2 in the drawing illustrates an alternate embodiment of the
process in which a moving bed of coal is employed as a catalyst in
lieu of the fixed bed described above. In this embodiment, finely
divided sub-bituminous or lower rank coal is introduced
continuously through line 50 into hopper 51 from storage or a
suitable preparation plant. The coal employed will normally have a
particle size less than about 8 mesh, preferably less than about 20
mesh, on the Tyler Screen Scale. The finely divided coal is
discharged from the hopper through screw conveyor or a similar
device 52 into reaction vessel 53. Here the coal particles form a
downwardly moving bed supported by upflowing oil introduced into
the lower end of the reaction vessel through line 54. Hot char
particles are withdrawn near the lower end of the reaction vessel
through line 55 and are passed to a heat recovery unit not shown in
the drawing before being utilized as fuel or employed for other
purposes. The fluidized bed in vessel 53 is maintained at a
temperature within the range between about 700.degree. and about
900.degree. F. and at a pressure between about 10 and about 100
psig. The space velocity is preferably controlled between about 0.5
and about 1.5 pounds of oil per hour per pound of coal to permit
the recovery of a low sulfur, high Btu solid fuel through line 55.
Higher space velocities which will result in the production of a
lower quality solids product and increased yields of liquid
products may be employed if desired.
The liquid and gaseous products produced by the catalytic cracking
of the feed oil in the presence of the coal, together with
uncoverted heavier hydrocarbons, are taken off overhead from vessel
53 through line 56 and introduced into the lower end of
fractionating tower 57. Here the lighter constituents are taken off
overhead through line 58, cooled in heat exchanger 59, and passed
to flash drum 60. Gaseous constituents are recovered by means of
line 61, intermediate products boiling up to about 450.degree. F.
are recovered as naphtha through line 62, and the heavier
condensate is recycled as reflux through line 63. Liquids in the
gas oil range boiling up to about 700.degree. F. are withdrawn as a
side stream through line 64. The bottom products from the cracked
fluids introduced through line 56 and the heavy constituents from a
heavy oil feed introduced into the system through line 65 from a
pipe still or similar source are withdrawn from the fractionating
tower through line 66, heated to a temperature within the range
between about 700.degree. and about 900.degree. F. in furnace 67
and introduced into the catalytic cracking zone in vessel 53
through line 54. The process of the invention can thus be carried
out in either fixed bed or fluidized bed operations.
The nature and objects of the invention are further illustrated by
the results of laboratory and pilot plant tests carried out in
accordance with the invention.
In the first of a series of such tests, approximately equal parts
by weight of Wyodak coal and a heavy asphaltic residual petroleum
fraction were heated to a temperature of 750.degree. F. in a bench
size reaction vessel operating at essentially atmospheric pressure.
The reactor was vented to the atmosphere through a condenser to
permit the collection of distillation products and through a dry
test meter to permit determination of the quantity of gas produced.
The reactor was held at the 700.degree. F. reaction temperature for
a period of one hour. At the end of that time, the heat was turned
off and oil was drained from the bottom of the reaction vessel. The
quantities of gas and light ends, distillate, char, and drain oil
were measured. A blank run was then made using only the asphaltic
oil so that any thermal cracking or distillation of front ends of
the oil could be detected. A Fischer Assay of the coal with a
terminal temperature of 750.degree. F. was also carried out to
determine the yield due to pyrolysis of the coal in the absence of
the asphaltic oil. The results obtained in these tests are set
forth in Table I below:
TABLE I
__________________________________________________________________________
Reaction of Asphaltic Oil With Sub-Bituminous Coal
__________________________________________________________________________
Wt., Est'd. from Est'd Net from Coal, Dry Water Free* Product Gms.
Asph. Blank, gms. Gms. % Fischer Assay, %
__________________________________________________________________________
Gas & Lt. Ends 90 50 40 7.4 5.0 Distillate 309 216 93 17.3 8.3
Char 504 -- 504 93.7 86.7 Drain Oil 478 577 (99) (18.4) --
__________________________________________________________________________
*Fischer Assay with terminal temperature of 750.degree. F.
It will be noted from the above table that the yields of gas and
light ends and of distillate obtained by heating the heavy oil in
the presence of the sub-bituminous coal were substantially higher
than those obtained by heating the oil alone and that the yield of
drain oil was considerably less than that obtained when the oil
alone was heated. This indicates that the coal apparently had a
catalytic effect on the cracking of the heavy oil and resulted in
the conversion of a substantial part of the drain oil into gas,
light ends and distillate. The Fischer Assay results can be
considered a minimum yield available from pyrolysis of the coal in
the absence of oil. The estimated net yields from the coal,
obtained by subtracting the asphalt blank yields from the actual
yields obtained, were significantly higher than the Fischer Assay
values. Although some of this difference may have been due to a
solvent effect of the asphalt oil upon the coal, the test results
indicate that the coal acted as a catalyst to promote cracking and
upgrading of the heavy oil.
Tests similar to those described above were carried out with a
heavy West Texas vacuum residuum and Wyodak coal at a temperature
of 800.degree. F. Again equal parts of the coal and heavy oil by
weight were used. A blank test of the residuum without any coal and
a Fischer Assay of the coal were run. The results of this second
series of tests are set forth in Table II below:
TABLE II
__________________________________________________________________________
Upgrading of West Texas Vacuum Residuum With Wyadak Coal
__________________________________________________________________________
Wt., Est'd from Est'd Net from Coal, Dry Water Free* Product Gms.
Resid. Blank, Gms. Gms. % Fischer Assay, %
__________________________________________________________________________
Gas & Lt. Ends 215 64 151 26.7 7.3 Distillate 633 340 293 51.9
10.2 Char 568 -- 568 100.5 82.5 Drain Oil 9 456 (477) (79.1) --
__________________________________________________________________________
*Fischer Assay at 800.degree. F. terminal temperature.
The results obtained with the heavy West Texas vacuum residuum were
even more striking than those obtained with the heavy asphaltic
oil. It will be noted that the yields of gas and light ends and of
distillate were again much higher than those obtained from the run
in which no coal was present. At the end of the 1-hour reaction
period, only 9 grams of the oil remained in the system. This is
about the holdup of oil in the pipe nipple connecting the drain
valve to the bottom of the reaction vessel. On comparing the
estimated net yields from coal with the minimum pyrolysis yields by
the Fischer Assay tests, it can be seen that sharply enhanced
residuum conversion must have contributed strongly to the yields of
gas, light ends and distillate. It is thus evident that the
sub-bituminous coal has a pronounced catalytic effect on the
cracking of the heavy oil and that this effect can be employed to
permit the upgrading of the residuum into more valuable lighter
products.
Following the tests described above, additional tests in which a
heavy West Texas residual petroleum fraction was contacted with a
fixed bed of Wyodak coal were carried out. In these tests, wet coal
was charged to a fixed bed reactor provided with an oil inlet at
its lower end and a product outlet at the upper end. Nitrogen was
passed through the reactor as it was brought up to temperature to
sweep out moisture and any coal pyrolysis liquids formed. After the
desired temperature had been reached, the heavy residual oil was
passed over the coal and the products formed were accumulated. Runs
were carried out at temperatures of 750.degree. F.., 800.degree. F.
and 850.degree. F. and space velocities of from 0.3 to 1.2 pounds
of oil per pound of coal per hour. The reactor was operated at a
pressure of 25 pounds per square inch gauge. The results of these
tests are shown in Table III below:
TABLE III
__________________________________________________________________________
Continuous Flow of West Texas Resid Over a Packed Bed of Wyodak
Coal Average of 12-Hour Runs
__________________________________________________________________________
Pressure, psig 25 25 25 25 25 Temperature, .degree.F. 750 750 800
800 850 Approximate Space Velocity.sup.a 0.3 1.0 0.3 1.2 1.0
Product Distribution Based on Oil Charged, Wt. % Oil Recovered
100.4 98.6 52.0 77.3 -- Gas + Light Ends 0.6 0.2 19.1 12.6 -- Net
Char Made.sup.b 1.3 3.1 27.2 9.5 -- Total 102.3 101.9 98.3 99.4
--.sup.c
__________________________________________________________________________
.sup.a Wt. resid feed/wt. wet coal charged/hour. .sup.b Net of
total char made and Fischer Assay char on coal charged. .sup.c Run
terminated under noncontrolled conditions because of reactor
plug.
The data in the above table show that relatively little gas, light
ends and char were formed at 750.degree. F. As the temperature was
increased, the cracking became more severe and hence the oil yield
was reduced and more gas, light ends were formed. It should be
noted that the split between oil recovered and gas and light ends
in the above table was not precise because of inadequate light
liquid recovery equipment when operating the unit at essentially
atmospheric pressure and that the run carried out at 850.degree. F.
was terminated early because of rapid coke buildup and
plugging.
Following the runs described above, the oil recovered from the run
carried out at 800.degree. F. and a space velocity of 1.2 was
fractionated and the ultimate product distribution in a full scale
unit where the bottoms product would be recycled was estimated on
the basis on the oncethrough product distribution. The selectivity,
based on the 950.degree. F.+ constituents in the feedstock, was
also determined for the estimated ultimate product distribution.
The yields that would be obtained from this feedstock in a
950.degree. F. fluid coking reaction were predicted on the basis of
the feed characteristics and established fluid coking correlations.
The results of these are shown in Table IV below:
TABLE IV
__________________________________________________________________________
Product Distribution and Selectivity
__________________________________________________________________________
For 800.degree. F., 1.2 Space Velocity Product Dis- Selectivity
950.degree. F. Fluid tribution Based on Oil Estimated of
950.degree. F. + Coking Charged, Wt. % Once-Through Ultimate
Conversion Prediction
__________________________________________________________________________
Gas + Light Ends 12.6 18.0 22.7 8.5 C.sub.4 /430.degree. F. 8.5
12.1 15.2 14.8 430/950.degree. F. 45.7 56.1 44.1 60.7 950.degree.
F.+ 23.7 0 -- 0 Char 9.5 13.8 18.0 16.0 100.0 100.0 100.0 100.0
__________________________________________________________________________
The results set forth above show that the Wyodak coal has a
surprisingly pronounced effect on the cracking of the heavy
residual petroleum fraction and that the ultimate results are
comparable to those obtained at 950.degree. F. in a fluid coking
unit. Since fluid coking requires a heavy investment in complex
equipment and is expensive to operate because of the higher
temperature level and the complexity of the equipment, the
economics of the process of the invention appear favorable.
In still further tests of the process, runs were carried out with
heavy shale oils, fluid catalytic cracking bottoms, and creosote
oils. These tests were carried out at temperature of 800 and
850.degree. F. in a fixed bed reactor containing Wyodak
sub-bituminous coal at substantially atmospheric pressure. The
results of these later tests are shown in Tables V, Vi and VII
below:
TABLE V
__________________________________________________________________________
Catalytic Cracking of Shale Oil Over Wyodak Coal
__________________________________________________________________________
Distillations Feed 800.degree. F. Product 850.degree. F. Product
__________________________________________________________________________
Wt.% at 430.degree. F. 0.0 8.52 7.51 950.degree. F. 72.0 96.0 89.0
Recoveries, Wt. % 800.degree. F. Run 850.degree. F. Run Measured
Normalized Measured Normalized
__________________________________________________________________________
Oil 94.7 93.48 92.3 90.49 Gas 0.1 0.10 3.0 2.94 Char 6.5 6.42 6.7
6.57 101.3 100.00 102.0 100.00 Yields, Wt. % 800.degree. F. Run
850.degree. F. Run Gross Net Ult. Gross Net Ult.
__________________________________________________________________________
Gas (Incl. C.sub.5 + in Gas) 0.10 0.12 2.94 4.56 C.sub.5
-430.degree. F (Not Incl. C.sub.5 + in Gas) 7.96 9.19 6.80 10.55
430-950.degree. F. 81.78 9.78 83.28 73.74 1.74 74.70 950.degree.
F.+ Liquid 3.74 -24.26 0.00 9.95 -18.05 0.00 Char 6.42 7.41 6.57
10.19 100.00 100.00 100.00 100.00
__________________________________________________________________________
TABLE VI
__________________________________________________________________________
Catalytic Cracking of Fluid Catalytic Cracking Bottoms Over Wyodak
__________________________________________________________________________
Coal Distillations Feed 800.degree. F. Product 850.degree. F.
Product
__________________________________________________________________________
Wt.% at 430.degree.F. 0.0 0.0 0.0 950.degree.F. 80.5 88.0 99.2
Recoveries, Wt. % 800.degree. F. Run 850.degree. F. Run Measured
Normalized Measured Normalized
__________________________________________________________________________
Oil 98.8 97.05 80.0 86.68 Gas 0.6 0.59 1.0 1.08 Char 2.4 2.36 11.3
12.24 101.8 100.00 92.3 100.00 Yields, Wt. % 800.degree. F. Run
850.degree. F. Run Gross Net Ult. Gross Net Ult.
__________________________________________________________________________
Gas (Incl. C.sub.5 + in Gas) 0.59 1.47 1.08 1.12 C.sub.5
-430.degree.F. (Not Incl. C.sub.5 + in Gas) 0.00 0.00 0.00 0.00
430-950.degree. F. 85.40 4.90 92.67 85.99 5.49 86.19 950.degree.
F.+ Liquid 11.65 -7.85 0.00 0.69 -18.81 0.00 Char 2.36 5.86 12.24
12.69 100.00 100.00 100.00 100.00
__________________________________________________________________________
TABLE VII
__________________________________________________________________________
Catalytic Cracking of Creosote Oil Over Wyodak Coal
__________________________________________________________________________
Distillations Feed 800.degree. F. Product 850.degree. F. Product*
__________________________________________________________________________
Wt.% at 430.degree. F. 8.0 5.94 9.8 950.degree. F. 93.7 96.3 100.0
Recoveries, Wt. % 800.degree. F. Run (107C) 850.degree. F. Run
(130C) Measured Normalized Measured Normalized
__________________________________________________________________________
Oil 97.6 94.76 94.5 95.36 Gas 0.4 0.39 0.1 0.10 Char 5.0 4.85 4.5
4.54 103.0 100.00 99.1 100.00 Yields, Wt. % 800.degree. F. Run
850.degree. F. Run* Gross Net Ult. Gross Net Ult.
__________________________________________________________________________
Gas (Incl. C.sub.5 + in Gas) 0.39 0.88 0.10 0.10 C.sub.5
-430.degree. F. (Not Incl. C.sub.5 + in Gas) 5.63 -2.37 2.65 9.35
1.35 9.35 430-950.degree. F. 85.62 -0.08 85.52 86.01 0.31 86.01
950.degree. F.+ Liquid 3.51 -2.79 0.00 0.00 -6.30 0.00 Char 4.85
10.95 4.54 4.54 100.00 100.00 100.00 100.00
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* Distillation had poor material balance.
Again the data show that the sub-bituminous coal behaved as a
catalyst to promote cracking of the heavy oils into lower boiling,
more valuable products. The data obtained with shale oil are
particularly significant because such oils contain high
concentrations of nitrogen compounds and other materials which
rapidly poison conventional catalytic cracking catalysts and are
therefore difficult and expensive to upgrade.
In view of the foregoing it should be apparent that the process of
the invention has pronounced advantages over conventional residuum
conversion processes. These advantages include a heat load which is
significantly lower than that required in conventional residuum
conversion processes, the use of equipment which is much simpler
and less expensive than that required for fluidized coking and the
like, yields which are significantly better in terms of naphtha and
gas oil than those obtained in typical delayed coking operations,
and the ability to produce a high quality, low sulfur, solid fuel
by carrying out the process in a moving bed at relatively low
residuum-to-coal ratios. As a result of these and other advantages,
the process permits the conversion of residual fractions at a cost
considerably below that of fluid coking while achieving product
yields which are comparable to fluid coking and significantly
better than those obtained by delayed coking.
* * * * *