U.S. patent number 3,922,215 [Application Number 05/365,973] was granted by the patent office on 1975-11-25 for process for production of hydrocarbon liquids and gases from oil shale.
This patent grant is currently assigned to American Gas Association. Invention is credited to Harlan L. Feldkirchner, Henry R. Linden, Paul B. Tarman.
United States Patent |
3,922,215 |
Linden , et al. |
November 25, 1975 |
Process for production of hydrocarbon liquids and gases from oil
shale
Abstract
A process for the production of hydrocarbon liquids and gases
from oil shale comprising the steps of gradually preheating oil
shale in a preheat and prehydrogenation zone to a temperature of
about 700.degree. to about 950.degree.F. in the presence of
hydrogen-rich gas without substantial production of liquid and gas
in the preheat and prehydrogenation zone, then destructively
distilling the preheated and prehydrogenated oil shale in a
hydroretort zone at a temperature of about 850.degree. to about
1,250.degree.F. in the presence of hydrogen-rich gas to form
aliphatic and alicyclic hydrocarbon liquids and low molecular
weight paraffinic hydrocarbon gases from the preheated and
prehydrogenated organic hydrocarbon portion of the oil shale. The
hydrogen-rich gas may be passed countercurrent in thermal exchange
relation to the spent shale to recover heat from the spent shale
heating the hydrogen-rich gas for passage countercurrent and in
thermal exchange relation to fresh oil shale in the preheat and
prehydrogenation zone. The improvement of this process lies in the
exceptionally high conversion of the organic component of oil shale
to products of high value including high yields of readily
distillable liquids comprising a high proportion of aliphatic and
alicyclic hydrocarbon liquids and to low molecular weight
paraffinic hydrocarbon gases. The process can be controlled, if
desired, to maximize production of aliphatic and alicyclic
hydrocarbon liquids. The liquids produced by this invention may be
utilized for a wide variety of purposes including gasification for
the production of synthetic pipeline-quality gas from oil
shale.
Inventors: |
Linden; Henry R. (Chicago,
IL), Tarman; Paul B. (Elmhurst, IL), Feldkirchner; Harlan
L. (Elk Grove Village, IL) |
Assignee: |
American Gas Association
(Arlington, VA)
|
Family
ID: |
23441166 |
Appl.
No.: |
05/365,973 |
Filed: |
June 1, 1973 |
Current U.S.
Class: |
208/408; 208/412;
48/197R |
Current CPC
Class: |
C10B
53/06 (20130101); C10G 1/06 (20130101) |
Current International
Class: |
C10B
53/06 (20060101); C10G 1/00 (20060101); C10G
1/06 (20060101); C10B 53/00 (20060101); C10B
053/06 () |
Field of
Search: |
;208/11 ;48/197R |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Davis; C.
Attorney, Agent or Firm: Speckman; Thomas W.
Claims
We claim:
1. A process for the production of aliphatic and alicyclic
hydrocarbon liquids from oil shale wherein above about 77 percent
of the organic carbon in said oil shale is converted to said
liquids and gases comprising the steps:
introducing fresh oil shale into a preheat and prehydrogenation
zone;
gradually preheating, at a rate of less than about 100.degree.F.
per minute, oil shale in the preheat and prehydrogenation zone to a
temperature of about 700.degree. to about 950.degree.F. in the
presence of hydrogen-rich gas with less than about 20 weight
percent of the organic component of oil shale converted to liquid
and gas in said preheat and prehydrogenation zone, said
hydrogen-rich gas and shale passing countercurrently in said
zone;
destructively distilling the preheated and prehydrogenated oil
shale in a hydroretort zone at a temperature of about 850.degree.
to about 1250.degree.F. in the presence of at least a
stoichiometric amount of hydrogen-rich gas to form aliphatic and
alicyclic hydrocarbon liquids and low molecular weight paraffinic
hydrocarbon gases from the preheated and prehydrogenated organic
portion of said oil shale; and
said hydrogen-rich gas being supplied to said preheat and
prehydrogenation zone in larger volumes than the hydrogen-rich gas
supplied to said hydroretort zone.
2. The process of claim 1 wherein spent shale is passed from said
hydroretort zone to a heat recovery zone wherein hydrogen-rich gas
recycled from said preheat and prehydrogenation zone passes
countercurrent and in thermal exchange relation to said spent shale
cooling the spent shale and heating the hydrogen-rich gas for
introduction to said preheat and prehydrogenation zone.
3. The process of claim 2 wherein hydrogen-rich gas make-up is
added to said hydrogen-rich gas recycle prior to introduction to
said heat recovery zone.
4. The process of claim 2 wherein hydrogen-rich gas make-up is
added to said heat recovery zone.
5. The process of claim 2 wherein said heated hydrogen-rich gas is
further heated during passage from said heat recovery zone to said
preheat and prehydrogenation zone.
6. The process of claim 2 wherein the hydrogen-rich gas recycle is
passed through a liquid separator after leaving the preheat and
prehydrogenation zone and prior to the addition of hydrogen-rich
gas make-up.
7. The process of claim 2 wherein the hydrogen-rich gas stream
leaving said preheat and prehydrogenation zone is split with one
portion, containing sufficient gas to provide at least the chemical
hydrogen requirements in the hydroretort zone, is passed to said
hydroretort zone and the other portion is recycled to said heat
recovery zone.
8. The process of claim 7 wherein said one portion of hydrogen-gas
stream is further heated during passage to said hydroretort
zone.
9. The process of claim 1 wherein the oil shale is preheated to
about 750.degree. to about 850.degree.F. in said preheat and
prehydrogenation zone.
10. The process of claim 1 wherein said preheated and
prehydrogenated oil shale is passed through said hydroretort zone
in cocurrent thermal exchange relation with said hydrogen-rich
gas.
11. The process of claim 1 wherein the preheated and
prehydrogenated oil shale is heated to about 950.degree. to about
1150.degree.F. in said hydroretort zone.
12. The process of claim 11 wherein the preheated and
prehydrogenated shale in the retort zone is heated by an internal
heating means.
13. The process of claim 1 wherein the preheat and prehydrogenation
zone and the hydroretort zone is at a total gas pressure of about
40 to about 1500 psiz.
14. The process of claim 13 wherein the hydrogen partial pressure
is greater than about 100 psia.
15. The process of claim 1 wherein hydrogen-rich gas is separated
from the aliphatic and alicyclic hydrocarbon liquids formed in said
hydroretort zone and recycled to said hydroretort zone.
16. The process of claim 11 wherein more than about 80 percent of
the organic portion of oil shale is converted to liquid.
17. The process of claim 1 wherein above about 85 percent of the
organic carbon in said oil shale is converted to said liquids and
gases.
18. The process of claim 1 wherein said aliphatic and alicyclic
liquids are gasified in a hydrogasifier and wherein the
hydrogen-rich gas provided to said hydroretort zone is heated by
thermal exchange with the output stream of said hydrogasifier.
Description
This invention relates to an improved process for the production of
aliphatic and alicyclic hydrocarbon liquids and low molecular
weight paraffinic gases from oil shales. Aliphatic hydrocarbons
include open, straight or branched chain molecules which may be
saturated or unsaturated. Alicyclic hydrocarbons are cyclic
molecules substantially free from aromatic double bonds. Low
molecular weight paraffinic hydrocarbon gases include molecules of
4 and less carbon atoms, namely methane, ethane, propane, butane
and isobutane. The aliphatic and alicyclic hydrocarbon liquids
produced by the process of this invention are especially suited for
various further processing. One important use of such liquids is
preparing a high methane content pipeline-quality gas suitable as a
substitute for or as a supplement to natural gas. Other important
uses of such hydrocarbon liquids include production of naphtha,
gasoline, kerosine, jet fuel, diesel oil and light fuel oils, and
other low boiling distillate oils.
Oil shales are sedimentary rocks which are thought to have been
formed from finely divided mineral matter and organic debris from
aquatic organisms and some plant matter which were deposited on the
bottoms of shallow lakes and seas and later solidified. The
resulting oil shales are fine-grained impermeable rocks in which it
is almost impossible to separate the organic component and the
inorganic mineral matter without changing the structure of the
organic component. The largest inorganic constituent of oil shales
are carbonates. Oil shales vary in the amount and in the
constitution of the organic component which is called kerogen.
Typical oil shales contain about 10 to 30 weight percent kerogen.
Kerogen is a high molecular weight hydrocarbon having a molecular
weight of over 3000 and a carbon to hydrogen weight ratio (C/H)
typically of about 7/1 to 8/1.
Due to the high demands upon natural gas supplies and their limited
reserves, synthetic pipeline gas will be needed to supplement such
natural gas in the United States and other countries of the world.
The interest in an economical process for producing synthetic
pipeline gas from oil shales is high. There are abundant reserves
of commercial grades of oil shales in the United States,
particularly in the northwestern areas of Colorado and adjoining
areas of Utah and Wyoming.
To be suitable as use for pipeline gas, the heating value must be
about 900 to 1100 BTU/SCF which results from high methane content,
normally 80 percent by volume or greater. Such specifications
require that for pipeline-quality gas the carbon to hydrogen weight
ratio be low, approaching as low as 3/1.
To produce a high yield of valuable hydrocarbons from oil shales,
it is desirable to limit the coking and aromatization of the oil
shales' organic component and to maximize the production of
low-boiling aliphatic and alicyclic hydrocarbon liquids from the
oil shales. In further processing such hydrocarbons, in turn, give
the highest yields of valuable liquid products or fuel gases and
cause the least formation of high-boiling aromatic oils and carbon
or coke during gasification. It is also desired in the production
of desired quality hydrocarbons from oil shales, to limit
decomposition of mineral carbonates present in the oil shale and
resultant carbon dioxide formation which increases process heat
requirements, consumption of hydrogen, and greatly increases the
difficulty of further processing.
Previous processes for the production of hydrocarbon fuels from oil
shale have the disadvantages of lower thermal efficiency and/or
lower conversion of the organic component oil shale to suitable gas
or readily gasifiable liquids.
It is an object of this invention to optimize the production of
aliphatic and alicyclic hydrocarbon liquids and paraffinic
hydrocarbon gases from oil shale suitable for further
processing.
It is another object of this invention to provide a process for the
production of aliphatic and alicyclic hydrocarbon liquids and low
molecular weight paraffinic hydrocarbon gases from oil shale
wherein the oil shale is preheated and prehydrogenated by
countercurrent flow of hydrogen-rich gas and may be hydroretorted
by countercurrent or cocurrent flow of hydrogen-rich gas.
It is still another object of this invention to provide a process
for high yield production of pipeline-quality gas from oil shale by
a process characterized by its high thermal efficiency.
Further objects of this invention will appear to one skilled in the
art as this description proceeds and by reference to the
figures.
Preferred embodiments of this invention are illustrated in the
drawings wherein:
FIG. 1 is a block flow diagram illustrating the production of
hydrocarbon liquids from oil shale using one embodiment of the
process of this invention; and
FIG. 2 is a block diagram showing the production of
pipeline-quality gas from oil shale by one embodiment of this
invention.
The process of this invention is applicable to a wide variety of
oil shales. For high efficiency it is desired that the Fischer
Assay, which indicates the oil yield obtained by conventional
retorting of the oil shale, be 25 gallons per ton or more. However,
the process of this invention is also applicable to oil shales
having lower Fischer Assays, down to about 10 gallons per ton.
The size of the shale particles used in the process of this
invention is not important, but particles generally of the size
1/16 inch to 1 inch diameter are utilized. Use of very fine
particle shales may give difficulty in clogging during processing
and large particle shales have a lower surface area and may result
in longer processing times.
The fresh oil shale is fed into a preheat and prehydrogenation zone
and gradually preheated to a temperature of about 700.degree. about
950.degree.F. in the presence of hydrogen-rich gas. It is preferred
that the temperature to which the oil shale is heated in the
preheat and prehydrogenation zone is about 750.degree. to about
850.degree.F. At 700.degree.F. the rate of adequate
prehydrogenation is slow, but may be achieved by a residence time
of several hours. At the higher temperatures of about 950.degree.F.
prehdyrogenation occurs in a few minutes. The criteria of adequate
prehydrogenation is the ultimate increased recovery of organic
matter from the shale which is expressed most conveniently in terms
of organic carbon recovery. By the process of this invention, as
much as about 95 percent of the organic carbon can be removed from
oil shale in the form of valuable liquid and gaseous hydrocarbons.
Longer residence times at the higher temperatures lead to undesired
production of oil and gas by hydroretorting in the preheat and
prehydrogenation zone. It is desired to limit oil production in the
preheat and prehydrogenation zone to avoid plugging of the shale in
this zone. It is desired not to produce substantial quantities of
hydrocarbons in the preheat and prehydrogenation zone, preferably
less than about 15 to 20 weight percent of the organic component of
the shale is converted to normally liquid or gaseous hydrocarbons.
It is especially preferred to convert less than about 10 weight
percent of the organic component of the shale to liquid or gas in
this zone.
The terminology "hydrogen-rich gas" throughout this description and
claims, means gases with sufficient hydrogen partial pressure to
effect high organic carbon recovery from the organic material in
the oil shales. Such hydrogen- rich gases may be obtained by a
number of processes well known in the chemical process industry.
Table I shows the effect of the hydrogen partial pressure and the
heatup rate upon organic carbon recovery from prehydrogenated oil
shales which had an original organic carbon content of 21.1 weight
percent. The maximum temperature to which the shale was heated was
1150.degree.F.
TABLE I ______________________________________ Percent Organic
Carbon Recovery Hydrogen Total Pressure (psia) at Indicated Partial
at Indicated Heating Rate Pressure Hydrogen Content (.degree.F/min)
(psia) 25% 50% 90% 10 30 50 ______________________________________
0 Inert gas (500psig Helium) 77 77 77 35 140 70 39 87 87 87 115 460
230 128 89 87 87 215 860 430 239 92 88 87 515 2060 1030 572 94 92
88 ______________________________________
Table I shows that hydrogen-rich gases of 35 psia hydrogen partial
pressure are suitable for use in this invention. It is preferred to
use hydrogen-rich gas having a partial pressure of hydrogen greater
than about 100 psia. The upper operating pressures are limited only
by equipment and economic considerations. One benefit of the higher
hydrogen partial pressure is that it allows higher rates hence,
less residence time and smaller reactors. Total operating pressures
throughout the system are usually substantially the same. Normally
the process of this invention may be carried out at total pressures
of about 40 to about 1500 psia, preferably about 500 to 1000
psia.
It is preferred that the oil shale not be thermally shocked by
abrupt temperature changes, but that it be gradually heated at a
rate in the order of less than about 100.degree.F. per minute. It
is preferred that the heating rate be less than about 50.degree.F.
per minute.
The oil shale and hydrogen-rich gas may be heated by external
heating means or internal heating means in the preheat and
prehydrogenation zone by a wide variety of methods which are
readily apparent to one skilled in the art. Such variety of heating
means allow both cocurrent and countercurrent operation of the
preheat and prehydrogenation zone with respect to the shale and
hydrogen-rich gas. One method which is preferred is the
introduction of oil shale at ambient temperatures at one end of the
preheat and prehydrogenation zone and the introduction of the
hydrogen-rich gas at the other end of the preheat and
prehydrogenation zone at a temperature in quantities sufficient to
heat the oil shale to about 700.degree. to about 950.degree.F. by
countercurrent flow of the hydrogen-rich gas in thermal exchange
relation to the oil shales. To maximize the production of aliphatic
and alicyclic hydrocarbon liquids from the oil shales, it can be
seen from Table I that the preferred partial pressure of hydrogen
at its introduction to the preheat and prehydrogenation zone should
be about 100 psia, or greater.
The preheated and prehydrogenated oil shale is destructively
distilled in a hydroretort zone at a temperature of about
850.degree. to about 1250.degree.F. in the presence of
hydrogen-rich gas to form aliphatic and alicyclic hydrocarbon
liquids and low molecular weight paraffinic hydrocarbon gases from
the preheated and prehydrogenated organic portion of the oil
shales. It is necessary to reach a temperature of about
850.degree.F. in order ot obtain the desired hydroretorting in a
reasonable period of time. It is desired, in order to obtain the
maximum yield of aliphatic and alicyclic hydrocarbon liquids and
low molecular weight paraffinic hydrocarbon gases, to maintain the
temperature in the hydroretort zone at lower than about
1250.degree.F. The maintenance of the temperature in the
hydroretort zone at lower than about 1250.degree.F. limits the
inorganic carbonate decomposition to acceptable levels and also
limits the destructive hydrogenation of organic matter to gaseous
paraffinic hydrocarbons called hydrogasification, in the
hydroretort zone. Formation of carbon dioxide by inorganic
carbonate decomposition in the hydroretort zone is undesirable due
to its direct dilution of the hydrogen-rich gas, its consumption of
hydrogen in conversion to carbon monoxide and steam, and its use of
heat for decomposition. Therefore, if pipeline-quality gas is
desired, additional purification is required to remove the carbon
dioxide and carbon monoxide so formed.
Table II shows the effect of temperature in the hydro- retort zone
upon the decomposition of mineral carbonate under conditions
wherein the oil shale was heated at a rate of 33.degree.F. per
minute and the original mineral carbonate content of the oil shale
was 12.54 weight percent.
TABLe II ______________________________________ Percent Mineral
Carbonate Temperature .degree.F Decomposition
______________________________________ 1000 0 1100 7.1 1200 13.3
______________________________________
Hydrogasification in the hydroretort zone is not necessarily
detrimental if the desired product is only fuel gas. At higher
temperatures than about 1250.degree.F., increasing proportions of
paraffinic hydrocarbon gases are formed which are the most valuable
constituents of fuel gases and are the only acceptable major
constituents of pipeline-quality gas. However, at temperatures
above about 1250.degree.F. the yield of liquid hydrocarbons begins
to decrease substantially and the liquids which are produced become
increasingly aromatic in composition. The data showing product
distribution and organic carbon recovery are illustrated in Table
III for a typical heat-up rate and hydrogen partial pressure in
laboratory work simulating the combined results of the preheating,
prehydrogenation and hydroretorting steps. Eventually, as
temperatures are increased further, the total organic carbon
recovery drops to unacceptable levels because of coke and carbon
formation of the organic component of the oil shale.
TABLE III
__________________________________________________________________________
Liquid Product Properties I.B.P.-400.degree.F. Distillate Fraction
(percent) Maximum Average Hydrogen I.B.P.-400.degree.F* Aliphatic
and Temperature Partial Pressure Percent Organic Carbon Recovery
Distillate Alicyclic .degree.F. (psia) Total As Gases As Liquids
(percent) Saturated Aromatic
__________________________________________________________________________
1203 247 90.8 10.7 80.1 31 28 65 7 1298 252 95.0 50.7 44.3 36 5 39
56 1414 236 92.8 63.3 29.5 40 5 35 60
__________________________________________________________________________
NOTE: *I.B.P.-400.degree.F. shows the fraction boiling between the
initia boiling point and 400.degree.F.
As can be seen from Tables II and III, the maximum hydroretorting
temperature to obtain a combination of low mineral carbonate
decomposition, high total organic carbon recovery and a high
proportion of low boiling aliphatic and alicyclic hydrocarbons in
the hydrocarbon liquid products, is about 1250.degree.F. The
preferred temperature range is about 950.degree. to about
1150.degree.F. These temperatures vary somewhat over the specified
ranges of hydrogen partial pressure and heat-up rate or retention
time.
One further consideration which favors hydroretorting at
temperatures not exceeding about 1250.degree.F., is that the
increase in hydrogasification reached at the higher temperatures
may cause temperature control problems since hydrogasification is
exothermic.
The hydrogen-rich gas supplied to the hydroretort zone should
contain sufficient hydrogen to meet the chemical requirements
sufficient to convert the organic portion of the oil shale to
aliphatic and alicyclic hydrocarbon liquids and paraffinic
hydrocarbon gases. It may also be desirable to add a controlled
excess of hydrogen to the hydroretort zone. For example, sufficient
excess hydrogen may be added to the hydroretort zone to ultimately
convert all of the hydrocarbons recovered, and the carbon monoxide
remaining after final purification, to methane. The use of such an
excess of hydrogen in the hydroretort zone is also a means for
providing a portion of the heat necessary to achieve the desired
temperatures in the hydroretort zone. However, other heating means
may be used and such excess hydrogen may be added at a later stage.
More than such excess of hydrogen, if not separated prior to
subsequent gasification, will only dilute the gaseous products and
may require further separation if pipeline-quality gas is desired.
Less than such excess may lead to undesired carbon deposition if
the aliphatic and alicyclic hydrocarbon liquids are subsequently
hydrogasified in another processing step. Lesser than the amounts
of hydrogen required chemically for conversion of the
prehydrogenated component of oil shale to aliphatic and alicyclic
hydrocarbon liquids and low molecular weight paraffinic hydrocarbon
gases results in lower organic carbon recovery.
The hydrogen-rich gas may be passed cocurrent or countercurrent to
the oil shale in the hydroretort zone. It is preferred to pass the
hydrogen-rich gas in cocurrent thermal exchange relation with the
preheated and prehydrogenated shale in the hydroretort zone to
avoid condensation of hydroretorted liquids. The retention time in
the hydro-retort zone is sufficient, dependent upon the particular
temperature, pressure and hydrogen concentration in the
hydrogen-rich gas, to produce by hydroretorting a quantity of
aliphatic and alicyclic hydrocarbon liquids and low molecular
weight gases from the preheated and prehydrogenated organic
components of the oil shale equivalent to a total organic carbon
recovery of above 85 percent, and preferably above 90 percent. If
the desired end product is pipeline-quality gas, the amount of low
molecular weight gases produced in the hydroretort zone is not
important. However, when the aliphatic and alicyclic hydrocarbon
liquids are going to be further processed to a liquid product, it
may be desirable to limit gas formation in this zone by operation
in the lower ranges of temperature.
The hydroretort zone may be heated by any suitable method as will
be obvious to one skilled in the art. One method is to supply
hydrogen-rich gas of sufficiently high temperature to raise the
temperature of the shale to the desired temperature by direct
thermal exchange. The hydroretort zone may be optionally internally
heated by any suitable means such as fuel oil/oxygen burner.
Referring to FIG. 1, the fresh oil shale is supplied to preheat and
prehydrogenation zone 10 wherein hot hydrogen-rich gas passes
countercurrent and in thermal exchange relation to the oil shale at
a temperature sufficient to gradually preheat the oil shale to a
temperature of about 700.degree. to about 950.degree.F. The
preheated and prehydrogenated oil shale is then passed to
hydroretort zone 11 wherein it is passed cocurrently and in thermal
exchange relation with hydrogen-rich gas of sufficient temperature
to heat the oil shale to a temperature of about 850.degree. to
about 1250.degree.F. In hydroretort zone 11, the organic component
of the oil shale is destructively distilled to form aliphatic and
alicyclic hydrocarbon liquids and low molecular weight paraffinic
hydrocarbon gases. The aliphatic and alicyclic hydrocarbon liquids,
remaining hydrogen-rich gas and any newly formed gaseous
hydrocarbons are removed from the hydroretort zone. The aliphatic
and alicyclic hydrocarbon liquids may be subjected to further
treatment to form other desired products, such as pipeline-quality
gas. The spent shale is removed from hydroretort zone 11 and passed
through heat recovery zone 12 in countercurrent and thermal
exchange relation to hydrogen-rich gas which cools the spent shale
to less than about 300.degree.F., preferably to about 150.degree.F.
The hydrogen-rich gas is heated in heat recovery zone 12 for
recycle to preheat and prehydrogenation zone 10.
One advantage of the process of this invention is the high thermal
efficiency wherein the hydrogen-rich gas may remove a large portion
of the thermal energy of the spent shale for reutilization in
preheating of the fresh oil shale. FIG. 1 shows a preferred
embodiment of this invention wherein hydrogen-rich gas from preheat
and prehydrogenation zone 10 passes through separator 13 for
removal of liquids, namely water and hydrocarbon liquids which may
be formed in preheat and prehydrogenation zone 10. The organic
hydrocarbon liquids from separator 13 may be fed into the
hydrocarbon liquid output from hydroretort zone 11.
The hydrogen-rich gas leaving separator 13 follows a split stream,
one portion recycling to heat recovery zone 12 and another portion
supplying hydroretort zone 11. Valve 17 adjusts the split in the
hydrogen-rich gas flow dependent upon the chemical hydrogen
requirement in hydroretort zone 11. The hydrogen-rich gas passing
from separator 13 to hydroretort zone 11 may be heated by any
suitable heating means shown as 15, prior to introduction to
hydroretort zone 11. Alternatively, the hydrogen-rich gas may be
supplied directly to the hydroretort zone 11 without preheating and
hydroretort zone 11 may be heated by any suitable means shown in
FIG. 1 as heat input means 16. Heat input means 16 may be
combustion of fuel with oxygen.
The other portion of the stream of hydrogen-rich gas from separator
13 is recycled to heat recovery zone 12. The amount of
hydrogen-rich gas makeup is determined by the amount of hydrogen
consumed in the prehydrogenation and hydroretort zones and
discharged from hydroretort zone 11. The hydrogen-rich gas is
heated in heat recovery zone 12 and upon passing from heat recovery
zone 12 may be further heated by any suitable heater means 14 prior
to introduction to preheat and prehydrogenation zone 10 to obtain
the desired temperature for entry to preheat and prehydrogenation
zone 10. It is seen from FIG. 1 that a larger volume of
hydrogen-rich gas passes through preheat and prehydrogenation zone
10 then passes through hydroretort zone 11.
The advantages of the process of this invention appear to be
achieved by the controlled gradual preheating and prehydrogenation
in zone 10 followed by higher temperature hydroretorting of the
preheated and prehydrogenated oil shale in zone 11. While prior
processes of retorting oil shale without gradual preheating and
prehydrogenation of the organic component have resulted in less
than 80 percent recovery of the organic carbon from the shale, we
have found that with our two-zone hydroretorting process, it is
possible to recover as much as about 95 percent of the organic
carbon from the oil shale.
One important use for the aliphatic and alicyclic hydrocarbon
liquids obtained from the hydroretort zone by the process of this
invention, is for further processing to produce pipeline-quality
gas. Pipeline-quality gas may be obtained from such readily
gasifiable liquids by any suitable method of producing a
methane-rich gas. The aliphatic and alicyclic hydrocarbon liquids
may be further treated to produce pipeline-quality gas by many
known processes including hydrogasification by gas recycle
hydrogenation or fluidized bed hydrogenation, naphtha reforming,
catalytic-rich gas, methane-rich gas or Lurgi Gasynthan
processes.
FIG. 2 illustrates a preferred embodiment of this invention in the
production of pipeline-quality gas. Aliphatic and alicyclic
hydrocarbon liquids are produced in generally the same manner as
previously described with further increases in thermal efficiency
of the process being obtained by recovery of some hydrogen-rich gas
recycle from the product of hydroretort zone 11 and by utilization
of heat from a heat exchanger cooling the gas output of a
hydrogasifier to heat hydrogen-rich gas input to hydroretort zone
11.
In the embodiment shown in FIG. 2, the effluent stream of
hydroretort zone 11 is passed through cooler 30 and liquid-gas
separator 31 to separate the hydrocarbon liquids from hydrogen-rich
gas. A portion of the hydrogen-rich gas so separated may then be
recycled to hydroretort zone 11 through control valve 38. Any
hydrogen-rich gas not necessary in hydrogasifier 33 may be recycled
in this manner. The hydrocarbon liquid output from liquid-gas
separator 31 is passed to fractionator 32 which separates high
boiling hydrocarbon liquids from the low boiling hydrocarbon
liquids, thereby obtaining the preferred C/H ratio of about 7/1
prior to hydrogasification. The high boiling liquids may be used as
fuel to supply heat to the process or as feed to produce hydrogen
make-up gas. The low boiling hydrocarbon liquids from fractionator
32 are then fed through a convention hydrogasifier shown as 33
which is usually maintained at a temperature of about 1200.degree.
to about 1500.degree.F. and suitable pressure to effect
gasification. The effluent gas from hydrogasifier 33 is passed
through heat exchanger 34 wherein the hydrogen-rich gas passing to
hydroretort zone 11 may be heated by thermal exchange with the
hydrogasified gas. The cooled by hydrogasified gas is then passed
through a condenser-cooler removing water, benzene, toluene, xylene
followed by purification to remove any remaining quantities of
undesired steam, carbon monoxide carbon dioxide, hydrogen sulfide,
and nitrogen. Following such purification, the hydrogasified
product is methanated in a conventional manner to increase the
amount of methane in the resulting pipeline-quality gas.
The combination of the hydrogasifier process with the process for
production of hydrocarbon liquids and gases from oil shale results
in high overall thermal efficiency.
Suitable apparatus for use in the process of this invention will be
readily apparent to one skilled in the art. It is apparent that the
process of this invention may be operated in a physically separated
preheat and prehydrogenation zone and hydroretort zone or the
preheat and prehydrogenation zone and the hydroretort zone may be
physically contained in one vessel appropriately separated. When
operated on a batch basis, the preheat and prehydrogenation
conditions may first be subjected to a single zone to which same
zone the hydroretort conditions are later applied. It is readily
apparent the process of this invention may be carried out on either
a batch or continuous flow basis. A continuous flow process is
preferred.
While no specific means of distribution of the hydrogen-rich gas
throughout the zones containing oil shale is shown, it is readily
apparent that it is desirable to have a suitable gas distribution
means such as a gas manifold distribution system at the
introduction area of the gas to the particular zone. The desirable
factor is that the hydrogen-rich gas be effectively distributed to
the cross-sectional area of the zone upon its introduction or
shortly thereafter.
Suitable materials for construction of an apparatus suitable for
the process of this invention are well known to persons skilled in
the art and need only be sufficient to contain the pressures
obtained in the process and to effect suitable heat retentions in
the different thermal zones of the process of this invention.
EXAMPLE I
Oil shale having a Fischer Assay of 24 gallons per ton was crushed
into particles of about one-half inch in size. The crushed shale,
at ambient temperature of about 77.degree.F., was introduced into a
vessel having an upper preheat and prehydrogenation zone, a
hydroretort zone in the middle and a heat recovery zone in the
lower portion. These zones are separated by two decks, one between
the bottom of the preheat and prehydrogenation zone and the top of
the hydroretort zone and the other between the bottom of the
hydroretort zone and the top of the heat recovery zone. Solid flow
by gravity through these zones was controlled by a solids flow
controller at the spent shale exit in the bottom of the heat
recovery zone. The entire system operated at a total pressure of
1000 psia and lock hoppers were used to introduce the crushed shale
to the upper end of the preheat and prehydrogenation zone and moved
through this zone countercurrent to hydrogen-rich gas.
Hydrogen-rich gas containing 93.9 mol percent hydrogen was
introduced at a rate of 4.3 mols/hr. at a temperature of
950.degree. F. to the bottom of the preheat and prehydrogenation
zone through a gas distributor. The shale was introduced at the
rate of 100 pounds per hour for a residence time of about 15
minutes flowing countercurrent to the hydrogen-rich gas. The shale
left the preheat and prehydrogenation zone at a temperature of
850.degree.F. and entered directly to the top of the hydroretort
zone. About 0.6 pounds per hour of hydrocarbon oils having a
carbon/hydrogen ratio of 6.95/1 and about 0.34 pounds per hour of
water were formed in the preheat and prehydrogenation zone. The oil
and water were removed from the hydrogen-rich gas leaving the top
of the preheat and prehydrogenation zone and the oil was fed
directly to a gas phase hydrogasifier.
The shale was further heated in the hydroretort zone to
1100.degree.F. by a combination of cocurrent flow with
hydrogen-rich gas introduced to the top of the hydroretort zone at
1350.degree.F. and by direct firing of fuel and oxygen within the
zone. 0.12 pound per hour of the aromatic liquids produced in the
gas phase hydrogasifier were used as fuel for this purpose. 0.5
mols/hr. of gas containing hydrogen were supplied to more than
satisfy the chemical requirements for complete hydroretorting. This
gas was removed from the top of the preheat and prehydrogenation
zone and after liquids removed, was heated to 1350.degree.F. and
introduced to the top of the hydroretort zone. The residence time
of the shale in the hydroretort zone was about 5 minutes. The
output of the hydroretort zone showed that 90.8 percent of the
organic carbon in the shale had been converted, 82.7 percent to
hydrocarbon liquids having a C/H ratio of 7.4/1 and 8.1 percent to
low molecular weight paraffinic hydrocarbon gases.
The spent shale was removed from the bottom of the hydroretort zone
to the top of the heat recovery zone wherein it was cooled to
150.degree.F. by countercurrent flow with hydrogen-rich gas
recycled from the preheat and prehydrogenation zone. 3.8 mols per
hour of gas containing 93.8 mol percent hydrogen were recycled from
the preheat and prehydrogenation zone at 100.degree.F., heated to
792.degree.F. in the heat recovery zone and further heated to
950.degree.F. by a furnace in the recycle line bypassing the
hydroretort zone and fed to the bottom of the preheat and
prehydrogenation zone. 0.51 mols/hr. of 94.4 percent hydrogen-rich
make-up gas was added to the hydrogen-rich gas fed to the bottom of
the heat recovery zone. 10.3 pounds per hour of hydrocarbon liquids
from the hydroretort zone and 1.2 pounds per hour of water were
separated from the product gases by cooling. The hydrocarbon
liquids were then fractionated and the low boiling hydrocarbon
fraction produced at the rate of 4.2 pounds per hour and having a
C/H ratio of 7.0/1 were fed, together with the product gases from
the separator, to a recycle type gas phase hydrogasifier operated
at 1400.degree.F. Hydrocarbons having a C/H ratio of 7.0/1 or less
limit the carbon deposition in the hydrogasifier. The high boiling
hydrocarbon fraction produced at the rate of 6.0 pounds per hour
and having a C/H ratio of 7.7/1 were fed to a partial oxidation
plant for producing hydrogen-rich gas make-up for use in the
process. The product of the hydrogasifier at 1400.degree.F. was
passed in thermal exchange relation with the hydrogen-rich gas
removed from the top of the preheat and prehydrogenation zone prior
to its introduction to the top of the hydroretort zone, heating
such hydrogen-rich gas from 100.degree.F. to 1350.degree.F. and
cooling the product of the hydrogasifier to 720.degree.F. After
passing through this heat exchanger, the gaseous product was
further cooled and 0.034 pounds per hour of water and 0.73 pounds
per hour of aromatic liquids were removed. Then 0.012 mols per hour
of carbon dioxide and 0.010 mols per hour of hydrogen sulfide were
removed and the gas methanated resulting in dried pipeline-quality
gas having a gross heating value of 951 BTU/SCF and containing less
than 0.1 percent carbon monoxide. 1.58 SCF of pipeline-quality gas
containing 92.8 mol percent methane was produced per pound of dry
shale.
While in the foregoing specification this invention has been
described in relation to certain preferred embodiments thereof, and
many details have been set forth for purpose of illustration, it
will be apparent to those skilled in the art that the invention is
susceptible to additional embodiments and that certain of the
details described herein can be varied considerably without
departing from the basic principles of the invention.
* * * * *