U.S. patent number 3,617,469 [Application Number 04/786,955] was granted by the patent office on 1971-11-02 for hydrotorting of shale to produce shale oil.
This patent grant is currently assigned to Texaco Inc.. Invention is credited to Dale R. Jesse, Warren G. Schlinger, Joseph P. Tassoney.
United States Patent |
3,617,469 |
Schlinger , et al. |
November 2, 1971 |
HYDROTORTING OF SHALE TO PRODUCE SHALE OIL
Abstract
Continuous process for recovering shale oil from a slurry of raw
oil shale in shale oil. Water and hydrogen gas are injected under
pressure into the raw oil shale--shale oil slurry, and the mixture
is immediately introduced into an externally heated noncatalytic
tubular retort maintained at an outlet temperature in the range of
about 850.degree. to 950.degree. F. and at a pressure in the range
of about 300 to 1,000 p.s.i.g., and preferably at 500 p.s.i.g. for
maximum yields of shale oil having a minimum nitrogen content. In
the tubular retort under conditions of turbulent flow, the raw
shale is completely stripped of kerogen in about 1/4 to 3 minutes
(preferably less than a minute), and by simultaneous pyrolysis and
hydrogenation without added catalyst, the kerogen is converted to a
gaseous effluent from which shale oil is separated having a
substantially reduced nitrogen and sulfur content. Yields of such
shale oil from for example Colorado shale are about 116 percent of
the Fischer Assay; however, if desired, still higher yields of
shale oil (about 125 percent of the Fischer Assay) containing a
greater amount of material in the middle distillate boiling range
may be obtained by submitting the prehydrogenated gaseous effluent
from the tubular reaction zone to catalytic hydrogenation, after
first removing essentially all of the spent shale. Water is also
produced by the system in quantities which are in excess of process
requirements.
Inventors: |
Schlinger; Warren G. (Pasadena,
CA), Jesse; Dale R. (Hacienda Heights, CA), Tassoney;
Joseph P. (Whittier, CA) |
Assignee: |
Texaco Inc. (New York,
NY)
|
Family
ID: |
25140046 |
Appl.
No.: |
04/786,955 |
Filed: |
December 26, 1968 |
Current U.S.
Class: |
208/408; 201/27;
208/413; 208/433; 201/20; 201/29; 208/417 |
Current CPC
Class: |
C10G
1/065 (20130101); C10G 1/002 (20130101) |
Current International
Class: |
C10G
1/06 (20060101); C10G 1/00 (20060101); C01b
053/06 () |
Field of
Search: |
;208/8,10,11
;201/20,29,31,32,33,36,37,38 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Davis; Curtis R.
Claims
We claim:
1. A continuous process for hydrotorting raw oil shale to produce
shale oil or improved quality and yield comprising
1. forming in a mixing zone a pumpable slurry of raw oil shale
particles in a heavy shale oil carrier as defined hereinafter;
2. mixing together in a contacting zone below the vaporization
temperature of water the raw oil shale--shale oil slurry of (1), a
stream of recycle water as defined hereinafter in an amount
sufficient to substantially reduce the decomposition of inorganic
carbonates in the raw shale, and a stream of hydrogen rich gas in
an amount sufficient to provide substantially all of the hydrogen
required in the next hydrotorting step;
3. introducing the mixture from the contacting zone of (2) into a
noncatalytic tubular reaction zone located in immediate
juxtapositon to said contacting zone under conditions of turbulent
flow and at a pressure in the range of about 300 to 1,000 p.s.i.g.,
heating said mixture to an outlet temperature in the range of about
850.degree. to 950.degree. F., for a period of about 1/4 to 3
minutes while simultaneously subjecting the raw shale oil particles
in said mixture to the disintegrating action of the highly
turbulent flow therein and to the volumetric expansion and
vaporization of the water and shale oil, thereby simultaneously
effecting pyrolysis and hydrogenation of the raw shale and
hydrogenation of the shale oil produced and forming a gaseous
stream of solid particles of spent shale and ash dispersed in shale
oil vapor, unreacted hydrogen, water vapor, H.sub.2 S, NH.sub.3,
CO.sub.2 and CO;
4. introducing the gaseous effluent stream from (3) into a
gas-solids separating zone, withdrawing substantially all of the
spent shale and ash substantially free from organic matter from
said gas-solids separating zone, and withdrawing the remainder of
the gaseous stream substantially free from spent shale and ash
particles from said separating zone;
5. partially cooling the solids-free gaseous effluent stream from
(4) in a gas cooling zone to a temperature below the dew point of
the tars and heavy shale oil therein but above the dew point of
water and product shale oil, and introducing said liquid and
uncondensed gaseous materials into a gas-liquid separating
zone;
6. withdrawing the stream of uncondensed gaseous materials from the
gas-liquid separating zone of (5) and introducing said stream in
admixture with a stream of hydrogen as defined hereinafter into a
reaction zone containing a hydrogenation catalyst;
7. cooling the gaseous effluent stream from (6) in a gas cooling
zone to condense out crude shale oil and water containing dissolved
NH.sub.3, H.sub.2 S and CO.sub.2, and introducing said liquid and
uncondensed gaseous materials substantially comprising unreacted
hydrogen containing gas into a gas-liquid separating zone;
8. removing the crude shale oil and water mixture from the
separating zone of (7) and introducing said liquid mixture into a
crude shale oil-water separation zone;
9. removing the water from the crude shale oil-water separation
zone of (8) and introducing said water into a water purifying zone
where NH.sub.3, H.sub.2 S, and CO.sub.2 are separated from pure
water;
10. withdrawing a portion of the pure water from the water
purifying zone of (9) and recycling said water under pressure to
the contacting zone of (2);
11. withdrawing the hydrogen containing gas from the gas-liquid
separating zone of (7), compressing said gas, adding makeup H.sub.2
to a portion of said compressed gas, and recycling said gas to the
contacting zone of (2) as said hydrogen rich gas;
12. introducing the remainder of the compressed gas from (11) into
a gas purifying zone and separating H.sub.2 from other gases
present;
13. withdrawing hydrogen from the gas purifying zone of (12),
heating said hydrogen to a temperature in the range of 700.degree.
to 1,000.degree. F., and introducing said hydrogen into the
catalytic reaction zone of (6) as said stream of hydrogen;
14. removing the crude shale oil from the crude shale oil-water
separating zone of (8) and introducing said crude shale oil into a
fractionation zone where pentane and lighter hydrocarbon fractions
are separated from heavier shale oil fractions;
15. distilling the heavier shale oil fractions from (14) in a
fractionation zone to produce a product shale oil substantially
free from carbon and with reduced nitrogen and sulfur content, and
a heavy shale oil bottoms product; and
16. withdrawing a portion of the heavy shale oil bottoms from the
fractionation zone of (15) for recycle to the mixing zone of (1) as
said heavy shale oil carrier.
2. The process of claim 1, wherein the raw oil shale is present in
the raw oil shale--shale oil slurry of (1) in an amount in the
range of about 30 to 80 weight percent, and said slurry is
introduced into the contacting zone of (2) at a temperature in the
range of about 100.degree. to 500.degree. F.; the hydrogen rich gas
injected into the slurry in (2) comprises 45 or more volume percent
of hydrogen and is supplied to the contacting zone at a temperature
in the range of about 100.degree. to 500.degree. F. and in an
amount in the range of about 5,000 to 20,000 s.c.f. of hydrogen per
ton of raw shale; the recycle water is injected into the slurry in
(2) at a temperature in the range of about 100.degree. to
500.degree. F. and in an amount in the range of about .01 to 0.6
tons of water per ton of raw oil shale; said hydrogen rich gas and
said recycle water are introduced into said contacting zone at a
pressure in the range of from about 25 to 200 p.s.i. greater than
the line pressure and the mixture from the contacting zone of (2)
is introduced into the noncatalytic tubular reaction zone at a
temperature below the vaporization temperature of water and at a
turbulence level,
in the range of about 25 to 100,000 where .epsilon..sub.m is the
average apparent viscosity and .nu. is the kinematic viscosity; and
the reaction zone of (6) comprises a fixed bed of catalyst selected
from the group consisting of cobalt-molybdate, cobalt-nickel or
nickel-molybdate catalyst at a temperature in the range of about
700.degree. to 1,000.degree. F. and a pressure in the range of
about 300 to 1,500 p.s.i.g.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to the recovery of oil from oil shale. More
specifically it relates to an improved process which combines
tubular retorting and hydrogenation of a raw oil shale--shale oil
slurry to produce increased amounts of shale oil of improved
quality and spent shale containing essentially no carbonaceous
residue.
2. Description of the Prior Art
Oil shale consists of compacted sedimentary inorganic rock
particles, generally laminated and partly or entirely encased with
a high-molecular weight organic solid material called kerogen,
which is present in the amount of about 6-22 weight percent.
Kerogen is derived from aquatic organisms or waxy spores and pollen
grains, comprising hydrocarbons and complex organic-nitrogen,
oxygen, and sulfur compounds. Nitrogen in kerogen is largely in the
form of quinoline-pyridine-type compounds, and the sulfur is
largely present in the form of thiophene-type compounds. Crude
shale oil produced from the oil shale by the pyrolysis of the
kerogen differs from crude petroleum by being more unsaturated and
having a higher content of nitrogen compounds. Further, poor color
stability and disagreeable odor of the shale oil products are
related to the presence of these nitrogen compounds. One
approximate empirical formula for raw oil shale is C.sub.158
H.sub.265 O.sub.15 N.sub.4.sup.. 6 S.
In many proposed procedures, crude shale oil is obtained by
pyrolysis of the solid insoluble organic part of the raw shale
(kerogen). Thus, raw shale is subjected to destructive distillation
in a retort at a temperature of about 850.degree. to 950.degree. F.
The chemical decomposition of the kerogen which takes place by the
action of heat alone yields crude shale oil vapors, together with
water, gas, and spent shale containing carbonaceous residue and
mineral matter. The application of hydrogenation to the tubular
retorting of oil shale for upgrading shale oil has been previously
proposed, for example U.S. Pat. No. 3,177,072 issued to DuBois
Eastman and Warren G. Schlinger. However, the liquid yields in
prior art processes are generally less than the Fischer Assay, the
nitrogen content in the crude shale oil is still high, consumption
of pure hydrogen is high and relatively high-reaction pressures and
temperature (1,000 to 20,000 p.s.i.g. and up to 1,500 F. are
required.
The Fischer Assay Test is a laboratory evaluation test for
estimating the maximum oil recoverable in a conventional air retort
system at atmospheric pressure. It does not measure the total
hydrocarbon content of oil shale, and spent shale from this assay
typically contains 5 percent organic and free carbon. In the
Fischer Assay, a 100 gram sample of crushed (-8 mesh) oil shale is
heated in an aluminum retort at atmospheric pressure to a
temperature of 932.degree. F. (500.degree. C.) in 40 minutes; and,
it is then maintained at this temperature for an additional 20
minutes. The overhead vapors from the retort comprising essentially
shale oil and water are cooled, condensed, and collected in a
graduated centrifuge tube. Water is separated from the oil by
centrifuging, the quantities of oil and water produced are
measured, and the results for each are reported in units of gallons
per ton of raw shale. For further details of the Fischer Assay
refer to "Method of Assaying Oil Shale by a Modified Fischer
Retort" by K. E. Stanfield and I. C. Frost, R. I. 4477, June 1949,
U.S. Department of the Interior.
Contemporary retorting methods may be classified in general by the
manner which heat is applied: (1) indirect heating through the wall
of the retorting vessel; (2)direct heating by hot gases from
combustion within the retorting vessel: (3) heat transfer from an
externally heated carrier fluid; and (4) heat transfer from
recycled hot solids.
Disadvantage of some proposed retorting schemes include low heat
transfer rates and correspondingly low shale throughput, limited
vessel size, poor thermal control and low thermal efficiency,
difficult material-handling problems, high operating and equipment
costs, low yields in comparison with the Fischer Assay, and poor
quality of the shale oil. Furthermore, hydrogen consumption is
generally excessive, pressures are high (above 1,000 p.s.i.g.),
relatively long retort periods are necessary (6 to 20 hours), spent
shale retains some carbonaceous residue, and in comparison with
crude petroleum, the shale oil recovered is a very low grade.
Most commercial processes for converting raw shale into such liquid
fuels as jet and diesel fuels include the operations of (1)
retorting raw shale to produce crude shale oil (2) delayed coking,
(3) hydrogenation, and (4) fractionation. Established procedures
for shale oil refining generally involve a combination of cracking,
distillation, and chemical refining treatment which must of
necessity be very carefully controlled in order to prevent
excessive loses of valuable reactive unsaturated hydrocarbons.
In contrast with the prior art, by our hydrotorting process, a
hydrogenated shale oil is produced at a comparatively moderate
pressure. Furthermore, sulfur and nitrogen levels of the shale oil
may be reduced to those usually found in crude petroleum, there is
minimum degradation in the distillate boiling range, and yields are
greater. Such shale oil would then be amenable to further
processing by conventional crude refinery technique with high
yields for a minimum of treating. Further, the spent shale is
comparatively free from any organic or carbonaceous residue from
the kerogen. By our process, retorting and hydrogenation may be
combined in one operation, obviating the delayed coking step
commonly used by other processes during refining, and thereby
saving costs.
SUMMARY
We have discovered a continuous process for preparing maximum
yields of shale oil of reduced nitrogen and sulfur content from raw
shale under relatively reduced pressure. More particularly, the
invention relates to the discovery that raw shale can be readily
converted to shale oil and relatively kerogen-free, dry-powdered
shale by injecting a slurry of raw oil shale in shale oil with
hydrogen (about 5,000 to 20,000 s.c.f of hydrogen per tone of raw
shale) and water (about 0.01 to 0.6 tons of water per ton of raw
shale) under pressure, and immediately introducing the mixture into
an externally fired tubular retort under conditions of turbulent
flow. Within a period of from about one-fourth to 3 minutes at an
outlet temperature of about 850.degree. to 950.degree. F. and at a
pressure in the range of about 300 to 1,000 p.s.i.g. and preferably
at a critical pressure of about 475 to 525 p.s.i.g., hydrogenation
takes place with no addition of a supplementary catalyst. Shale oil
is produced having a substantially reduced nitrogen and sulfur
content and with increased yields of about 116 volume percent of
the Fischer Assay. Furthermore, if desired, still greater yields of
shale oil may be obtained (in some instances as much as 135 percent
of the Fischer Assay) by submitting solids-free prehydrogenated
gaseous effluent from the tubular reaction zone to further
hydrogenation in a separate catalytic hydrogenation zone.
The principal object of this invention is to recover from raw oil
shale increased yields of hydrogenated shale oil of improved
product quality.
Another object of this invention is to simultaneously retort raw
oil shale and hydrogenate the kerogen and shale oil to produce
increased yields of a shale oil with a substantially reduced
nitrogen and sulfur content.
A still further object of this invention is to provide a continuous
process for producing shale oil, water, and spent shale containing
essentially no carbonaceous matter from raw oil shale by means of a
continuous process having a high-thermal efficiency, high-oil
yield, and a high-retorting rate.
DESCRIPTION OF THE INVENTION
The present invention involves an improved process for recovering
high-quality shale oil from raw oil shale at substantially improved
yields. Crushed raw oil shale is mixed with heavy shale oil derived
by the process of out invention, as hereinafter described, to
produce a pumpable raw oil shale--shale oil slurry comprising from
about 30 to 80 weight percent of raw oil shale. The particle size
of the crushed raw oil shale preferably is less than 1/4-inch
diameter (more preferably one-eighth inch or less) and the slurry
is pumpable at reasonable pressure levels, i.e. 100 p.s.i.g.
The raw oil shale--shale oil slurry is pumped to an externally
heated, elongated, noncatalytic tubular retorting zone of
relatively great length in comparison with its cross-sectional area
(for example about 1 to 8 inches inside diameter and larger, and
about 500-4,000 feet long). A similar tubular retort is described
in U.S. Pat. No. 3,117,072 issued to DuBois Eastman and Warren G.
Schlinger. However, immediately prior to being introduced into said
tubular retorting zone, the raw oil shale--shale oil slurry is
introduced into a contacting zone where it is mixed with a stream
of hydrogen gas and a stream of liquid water under pressure. The
volume and velocities of the slurry, hydrogen, and water in the
tubular reaction zone are controlled to ensure highly turbulent
flow conditions, which combined with heat and pressure therein
promotes the disintegration of the shale and the dispersal of the
shale particles in the slurry-hydrogen mixtures. By the improvement
of our invention, turbulence in the tubular reactor is increased
and the desired turbulence level in the range of about 25 to
100,000, and preferably at least 1,000 is easier to attain than
ever before. Thus, the velocity of the slurry may be decreased for
a given sized tubular reactor without affecting the high-reaction
rate. As used herein, turbulence level is defined by the ratio
where .epsilon..sub.m is the average apparent viscosity and .nu. is
the kinematic viscosity, and is more fully described in U.S. Pat.
No. 2,989,461 issued to DuBois Eastman et al.
For example, in a gas-liquid contacting zone from about 5,000 to
20,000 s.c.f. of hydrogen per ton of raw shale at a temperature of
about 100.degree. to 500.degree. F. are injected into the slurry,
maintained at a temperature in the range of about 100.degree. to
500.degree. F. Water is also injected into the slurry in the amount
of about 0.01 to 0.6 tons of water per ton of crushed raw shale and
preferably about 0.1 to 0.4 tons of water per ton of crushed raw
oil shale. Both the hydrogen-rich gas (comprising 45 or more volume
percent H.sub.2 dry basis) and the recycle water is supplied to the
contacting zone at a pressure of about 25 to 200 p.s.i. greater
than the system line pressure.
Addition of hydrogen to the slurry and the hydrogenation of the
pyrolysis products of the kerogen improves the yield of the produce
shale oil and provides the product with a greater amount of the
desirable middle distillate material, while the formation of heavy
polymers, unsaturated hydrocarbons and carbonaceous residues which
characterize known processes are suppressed. Injecting water into
the slurry before the tubular retort was found to have several new,
unexpected and unobvious results. The velocity through the tubular
retort, the turbulent flow, and the heat transfer coefficient of
the mixture in the retort are all increased. Thus, rapid heat
transfer is brought about which allows conversion of the kerogen to
crude shale oil in the retort coils at residence times of about 1/4
to 3 minutes. Furthermore, vaporization of the water in the coils
tends to disintegrate the shale particles and facilitates
atomization of the shale oil. Also, coking of the slurry may be
minimized or eliminated at a substantially reduced hydrogen
consumption. Other unobvious advantages for injecting the water
under pressure into the shale-oil slurry just prior to introducing
the slurry into the tubular reactor include: (1) greater
concentrations of raw shale may be incorporated in pumpable
oil-shale slurries, (2) less water is required in our process than
when water is added to the shale in the slurry-mixing tank; (3)
clogging of the retort tubing is prevented; (4) better control of
the amount of water added; and, finally, (5) it was unexpectedly
found that water addition reduces the endothermic decomposition of
inorganic carbonates in the shale to form CO.sub.2, thereby
preventing the undesirable reaction between CO.sub.2 and hydrogen
to form H.sub.2 O and CO. Thus by water injection, there is a
savings of energy in the form of heat used for carbonate
decomposition as well as a reduction of hydrogen consumption in the
tubular retort.
The mixture of raw oil shale--shale oil slurry, water, and hydrogen
is introduced into the tubular retort and is heated to a
temperature in the range of about 700.degree. to 1,100.degree. F.
and preferably 850.degree. to 950.degree. F. while at a pressure in
the range of from 300 to 1,000 p.s.i.g., and preferably at a
pressure range of about 475 to 525 p.s.i.g.
The residence time in the tubular retort must be long enough to
permit disintegration of the raw shale, pyrolysis of all of the
kerogen, and hydrogenation of the shale oil. However, excess time
in the tubular retort may cause coking and result in degraded shale
oil. Thus, the residence time in the tubular retort is maintained
at about 1/4 to 3 minutes (preferably less than 1 minute) while at
the previously mentioned conditions of temperature, pressure,
turbulence and feed.
It was unexpected found that maximum yields of shale oil of
improved quality and containing a greater amount of C.sub.6
material are obtained by operating the tubular retort within a
critical pressure range of about 475 to 525 p.s.i.g. Oil yields of
about 36.3 gallons of 24.0 API gravity oil per ton of raw shale may
be expected in comparison with a Fischer Assay of about 31.2
gallons per ton. This represents an increase of about 16 percent
which represents an improvement over the yield from contemporary
processes. Also, examination of the hydrotort shale oil produced at
this pressure shows it to be of superior quality; that is compared
with a Fischer Assay of the same shale, the sulfur and nitrogen
content of our shale oil are each about 25 to 35 percent lower.
Further, the nitrogen content of the hydrotort oil reaches a
minimum at the critical pressure of about 500 p.s.i.g. However, the
sulfur content of the shale oil decreases as the pressure increases
above 500 p.s.i.g.
The gaseous effluent stream leaving the tubular retort, comprises
vapors of shale oil and water, unreacted hydrogen, NH.sub.3, CO,
CH.sub.4, H.sub.2 S, and CO.sub.2, along with entrained spent shale
particles (about 200 to 350 mesh) and is introduced into a suitable
gas-solids separating zone to effect separation of the spent shale
particles from the remaining gaseous stream. The gas-solids
separator may include, for example, a downwardly converging bottom
chamber containing baffling elements. The spent shale recovered is
substantially free from carbonaceous material and is a suitable
feedstock for further processing, such as making cement.
The hot gaseous effluent leaving overhead from the gas-solids
separating zone comprises shale oil vapor, unreacted hydrogen,
water vapor, hydrogen sulfide, ammonia, methane and carbon oxides.
This gaseous stream may be cooled to liquefy and thereby facilitate
the recovery of product shale oil, at a yield of 116 percent of
Fischer Assay, and water. Or alternately, the hot gases may be
subjected to gaseous hydrogenation over a hydrogenation catalyst to
raise the yield of the recovered product shale oil to 125 percent
of Fischer Assay, or more. For example, the hot effluent vapors
from the gas-solids separator, at a pressure in the range of about
300 to 1,500 p.s.i.g. and preferably the same pressure as in the
tubular retort less normal pressure drop in the lines of about 100
p.s.i.g., and at a temperature in the range of about 700.degree. to
1000.degree. F. and preferably the same temperature as in the
retort less line losses, are directed over one or more beds of
catalyst which are effective for promoting the hydrogenation of
hydrocarbons, such as a fixed bed of cobalt-molybdate,
cobalt-nickel or nickel-molybdate hydrogenation catalyst. Effective
catalysts in general include compounds of the Group VI metals and
of the first transition series of Group VIII of the Periodic table
of the Elements. Suitable known solid hydrogenation catalysts
include oxides or sulfides of molybdenum, cobalt, tungsten,
chromium, iron, vanadium, or nickel on a suitable carrier material
such as silica, alumina, bauxite, magnesia, zirconia, aluminum
silicate or clay. For example, the catalyst may comprise from about
1 to 10 weight percent of cobalt oxide and about 5 to 20 percent of
molybdenum oxide on an alumina support.
Thus by our improved process, shale oil may be produced by one or
two hydrogenation steps: in one step, water under pressure is
injected into a raw oil shale--shale oil slurry and hydrotorting
takes place immediately in a tubular retort with no supplementary
hydrogenation catalyst added; and secondly if desired, a second
hydrogenation step may be added wherein the effluent from the first
step is hydrogenated in a fixed or fluid bed of hydrogenation
catalyst, after particulate matter, tar, and heavy hydrocarbons are
removed. Direct contact of the gaseous effluent with catalyst in
the second step eliminates the need for condensing and reheating
the hydrocarbons prior to catalytic treatment. The first
hyrogenation step reduces the nitrogen contact of the shale oil to
a level which permits the use of fixed bed catalysts. The more
reactive olefins and hydrocarbons present are also saturated and
the Conradson carbon is reduced to only one-fourth to one-half the
carbon residue normally associated with shale oil. Thus the gaseous
effluent is suitable for direct vapor catalytic processing without
the normal coke-stilling step. At the cost of additional hydrogen,
the second hydrogenation step over a fixed catalyst bed may be
used, if desired, to improve both the quantity and quality of the
shale oil product. Thus, shale oil recovered by our double
hydrogenation process was unexpectedly found to show an increased
characterization factor and .degree.API, improved distillation
characteristics, greater yields (i.e. about 125 percent of the
Fischer Assay), and considerably less sulfur, nitrogen and carbon
residues. The characterization factor, K, is an index of the type
of hydrocarbon recovered and is described by Watson, Nelson, and
Murphy, Ind. Eng. Chem. 25, 880 (1933); 27, 1460 (1935).
By the process of our invention, the higher boiling hydrocarbons
are subjected to viscosity-breaking with substantially immediate
hydrogenation of the molecular fragments and without further
breakdown, thereby materially increasing the production of material
boiling in the 400.degree.-700.degree. F. range without substantial
increase in lower boiling gaseous hydrocarbons and heavy tars and
coke.
A more complete understanding of the invention may be had by
reference to the accompanying schematic drawing which shows the
previously described process in detail. Although the drawing
illustrates a preferred embodiment of the process of this
invention, it is not intended to limit the invention to the
particular apparatus or materials described.
FIRST EMBODIMENT
With reference to the drawing, in the first embodiment of our
invention, particles of raw shale in line 1 and heavy shale oil in
line 2 are introduced into mixing tank 3 where they are mixed by
agitator 4, forming a raw oil shale--shale oil slurry. This slurry
is passed from the bottom of mixing tank 3 through valve 5 and into
the suction end of screw pump 6. At a temperature in the range of
about 100.degree. to 500.degree. F., the slurry is pumped through
line 7 to a conventional gas-liquid contactor 8, which may be in
the form of a venturi mixer. Recycle hydrogen from line 9 and
makeup hydrogen from line 10 are mixed in line 11 and injected into
the accelerated slurry stream at the throat of the venturi 8.
Recycle water in line 12 is similarly injected into the slurry. The
pressure of each of the streams in lines 11 and 12 exceeds the
system line pressure by about 25 to 200 p.s.i.
The intimate mixture of hydrogen gas, water, raw oil shale
particles, and heavy shale oil at a temperature below the
vaporization temperature of water leaving contactor 8 is directed
through line 13 into externally heated tubular retort 14 situated
immediately after contactor 8. Under conditions of high turbulence
in tubular retort 14, the mixture is raised within seconds to a
temperature in the range of about 700.degree. to 1,100.degree. F.
and disintegration and pyrolysis of the raw shale, vaporization of
the shale oil and water, and hydrogenation of the kerogen and shale
oil all take place simultaneously. No supplementary catalyst need
be added to the aforesaid materials in the tubular retort to
promote the reactions therein.
A hot gaseous effluent stream comprising shale oil vapor, unreacted
hydrogen, water vapor, H.sub.2 S, NH.sub.3, CO.sub.2, CO and shale
dust in the form of a fine dry powder of about 200 to 325 mesh,
leaves tubular retort 14 through line 15 and is discharged into
gas-solids separator 16. Spent shale, substantially free from any
hydrocarbonaceous residue, falls to the bottom of chamber 16 and is
removed from the system through line 17. To prevent plugging with
spent shale and heat loss, the gas-solids separation chamber 16,
the overhead transfer lines, line 15 from the tubular reactor, and
exposed flanges and pipe joints are insulated to maintain the
gaseous stream at a temperature of about 850.degree. to 950.degree.
F.
Since this first embodiment of our invention involves the
production of shale oil by hytrotorting in tubular retort 14 only,
that is, with no subsequent hydrogenation in a catalytic reactor
19, valves 20, 21, and 22 are closed and bypass valve 23 is opened.
Hot gaseous effluent from separator 16 comprising shale oil vapor,
water vapor, H.sub.2, and minor amounts of NH.sub.3, H.sub.2 S,
CO.sub.2, CO and CH.sub.4 is then directed to cooler 24 by way of
lines 18, 25, 26 and 27. The water and shale oil that are condensed
out in cooler 24 pass through line 28 and into gas-liquid separator
29. Unreacted hydrogen and the other uncondensed gases are removed
from the top of separator 29 and are passed through line 30 into
compressor 331. Compressed hydrogen-rich gas from lines 32 and 9
are mixed in line 11 with makeup from line 10 in the manner
previously described. If necessary this hydrogen-rich mixture may
be heated to a temperature in the range of 100.degree. to
500.degree. F. before it is introduced into conductor 8 by means of
one of the many heat exchangers in the system.
Shale oil-water mixture is withdrawn from the bottom of gas-liquid
separator 29 and is passed through line 33 into shale oil-water
separator 34, where the lighter shale oil separates out and floats
on a water layer which contains dissolved H.sub.2 S, NH.sub.3 and
CO.sub.2. The water layer is removed at the bottom of separator 34
through line 35 and is introduced into a standard water purifier 36
where H.sub.2 S, NH.sub.3 and CO.sub.2 are removed through line 37
and are directed to a standard NH.sub.3, H.sub.2 S, and CO.sub.2
recovery system. Purified water is removed through line 38 and a
portion may be recycled to contactor 8 by means of pump 39 through
lines 40 and 12, in the manner previously described. Surplus water
is discharged from the system through line 41. Since most oil shale
deposits are located in arid regions, one significant advantage of
our process is that there is not net consumption of water; but in
fact, an excess of water may be produced.
The crude shale oil layer in separator 34 is withdrawn through line
42 and is introduced into stabilizer 43 where by fractionation,
pentane and lighter hydrocarbon fractions are separated and are
passed out the top through line 44. Crude shale oil is withdrawn
from the bottom of stabilizer 43 through line 45 and is introduced
into fractionation column 46. A portion of the heavy shale oil
bottoms from column 46 at a temperature of about 600.degree. to
900.degree. F. is recycled through lines 47, 48 and 2 into mixing
tank 3 for making the raw oil shale--shale oil slurry feed to the
process, in the manner previously described. Generally, no heavy
shale oil recycle pump is necessary since the system pressure will
move the oil to the mix tank. The remainder of the heavy shale oil
is removed from the system through line 49. Product shale oil is
removed from the system through line 50.
SECOND EMBODIMENT
The second embodiment of our invention involves two separate
hydrogenation steps: first, the raw oil shale--shale oil slurry is
hydrogenated in the noncatalytic tubular retort as described
previously in the first embodiment; and second, the prehydrogenated
shale oil vapors from the first step are hydrogenated in a fixed or
fluid bed hydrogenation catalytic reactor 19. Also, a gas
purification system is integrated into the system to supply pure
hydrogen to the catalytic reactor and to 600.degree.the buildup of
gaseous impurities in the recycle hydrogen stream.
Catalytic reactor 19 and gas purifier 60 are introduced into the
previously described first embodiment of our invention by closing
bypass valve 23 and opening valves 20, 21 and 22. The hot gaseous
stream from gas-solids separator 16 is then passed through lines
18, 61, and 62 into cooler 63 where heavy shale oil and tars
condense out and pass with the uncondensed gases into gas-liquid
separator 64 by way of line 65. Separator 64 also serves as a catch
pot for any shale dust that may have passed through gas-solids
separator 16. Heavy shale oil and tar, which are the least valuable
portion of the product shale oil may then be removed from the
system through line 66 at the bottom of separator 64. This also
protects the catalyst in reactor 19 from contamination. However, if
desired all or a portion of the material in line 66 may be
introduced into mixing tank 3 by way of line 2 for slurrying with
the raw shale.
The gaseous stream leaving from the top of gas-liquid separator 64
is passed through lines 67 and 68 and into the catalytic reactor 19
where hydrogenation takes place. This hydrogenation step is
facilitated by a hot stream of pure hydrogen which is introduced
into reactor 19 by way of line 69. The preferred mole ratio of
hydrogen (from line 69) to gaseous feed to the catalytic chamber
(from line 68) is within the range of 0.0 to 0.3. Heat exchanger 70
is provided to help maintain the gas stream at the inlet to
catalytic reactor 19 at the proper temperature to effect maximum
denitrification and desulfurization. If it is desired to operate
the catalytic reactor at a higher pressure than the pressure in
tubular retort 14, then a pump may be inserted in line 68. The
effluent from catalytic reactor 19 is discharged through lines 71,
72, and 27 into cooler 24 where the treated shale oil and water are
condensed out. Except for the gas purification unit, the remainder
of the system involves shale oil-water separator 34, water purifier
36, stabilizer 43, and fractionation column 46. The operation and
function of these units are the same as that which has already been
described in connection with the first embodiment of our invention.
To prevent the buildup of gaseous impurities in the system, a
portion of the uncondensed gases from gas-liquid separator 29
comprising unreacted hydrogen and traces of H.sub.2 S, CO.sub.2, CO
and CH.sub.4 is purified, and the hydrogen is returned to the
system. For example, a portion of compressed recycle gas in line 32
is passed through lines 73 and 74 into a standard gas purifier 60
where H.sub.2 S, CO.sub.2, CO, and CH.sub.4 are separated from pure
H.sub.2 and leave respectively by way of lines 75, 76, 77 and 78
for recovery. A standard gas purifier utilizing refrigeration and
chemical absorption may be employed to effect separation of the
gases, e.g. U.S. Pat. No. 3,001,373 issued to DuBois Eastman and
Warren G. Schlinger. Hydrogen leaves gas purifier 60 by way of line
79 and is passed into heater 80 where it is raised to a temperature
in the range of about 800.degree. to 900.degree. F. before it is
introduced through line 69 into catalytic reactor 19, in the manner
previously described. If desired, high purity makeup hydrogen from
an external source may be introduced into the system by mixing with
the H.sub.2 in line 79. The preferred mole ratio of gases recycled
in line 73 to gases passed through line 11 is in the range of about
0.1 to 1.0.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following examples are offered as a better understanding of the
present invention but the invention is not to be construed as
limited thereto.
EXAMPLE I
Colorado oil shale having a Fischer Assay of 31.2 gallons of shale
oil per ton of raw oil shale and 2.9 gallons of H.sub.2 0 per ton
of raw oil shale is crushed to -8 mesh and mixed with heavy shale
oil to form a slurry comprising 75.6 weight percent of raw shale.
Immediately after water and hydrogen are injected into the slurry
under pressure, the mixture is hydrogenated in a 1 inch SCH. 40
pipe .times. 530 feet long noncatalytic tubular retort.
Operating conditions and results of runs in accordance with the
first embodiment of the process of our invention as previously
described are summarized in table I, column 1. In column 2 there is
shown a summary of the conditions and results of double
hydrogenation, first in the noncatalytic tubular retort and second
over a Co-Mo hydrogenation catalyst, as described in the aforesaid
second embodiment of our invention. It appears, from a comparison
of columns 1 and 2, that the second embodiment is the preferred
procedure because it provides high yields of product shale oil
having a higher .degree.API and characterization factor, improved
distillation characteristics and considerably less sulfur,
nitrogen, and carbon residue. Further, in comparison with the
Fischer Assay, the data for both embodiments show a substantial
increase in product-oil yields; an improvement in API gravity, pour
point and yield of distillate; and a reduction in the nitrogen and
the sulfur content in the shale oil product. ##SPC1##
EXAMPLE II
This example demonstrates the critical relationship between shale
oil yields and pressure for the continuous noncatalytic tubular
hydrotort described previously in the first embodiment of our
invention.
Shale oil is produced from Colorado shale in a noncatalytic tubular
retort at a pressure of 500 p.s.i.g. in accordance with the
operating conditions and test results summarized in table I, column
1, representing the first embodiment of our invention. The process
is repeated at essentially the same operating conditions but at
other pressures in the range of from about 300 to 1,000 p.s.i.g.
Test results are summarized in table II.
In particular it may be shown from the data in table II that shale
oil yields increase with pressure to a maximum of 500 p.s.i.g. Then
yields decrease with increasing pressure to about 900 p.s.i.g.
where they seem to level out. Hydrotort shale oil yields range from
103 to 116 percent of the Fischer Assay (F.A.) and the water yields
range from 159 to 283 percent of the F.A. Lower yields would be
expected at temperatures higher than 950.degree. F. due to cracking
of the oil to gas. At temperatures lower than 850.degree. F.
incomplete cracking of kerogen would be anticipated, producing
lower liquid yields. It is also shown from the data in table II
that maximum denitification occurs at a critical pressure of about
500-600 p.s.i.g. However, desulfurization and water yield vary
directly with retort pressure. ##SPC2##
The process of the invention has been described generally and by
examples with reference to raw shale--shale oil slurry feedstocks
of particular compositions for purposes of clarity and illustration
only. It will be apparent to those skilled in the art from the
foregoing that various modifications of the process and materials
disclosed herein can be made without departure from the spirit of
invention.
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