Professional Documents
Culture Documents
United States Patent 1191: Redford
United States Patent 1191: Redford
Redford
[541 IN SlTU GASIFICATION OF SOLID
HYDROCARBON MATERIALS IN A SUBTERRANEAN FORMATION
[75] Inventor: David A. Redford, Fort
3,830,300 8/1974
[ll]
4,026,357
May 31, 1977
[45]
Saskatchewan, Canada
[73] Ass'gneez Texaco Exploration Canada Ltd" Calgary Canada
[22]
[52] [51 ]
[57]
ABSTRACT
Solid hydrocarbon materials present in subsurface earth formation such as, for example, the coke like
residue remaining in a subterranean tar sand deposit
Filed:
[58]
Field of Search ........ .. 166/260, 261, 266, 267, 166/272 _ [56] References C'M UNITED STATES PATENTS 2 584 605 2H9 Me". ct I l 66/266
and a moderating ?u1d such as water, steam or carbon dioxide to control the reaction temperature so as to ensure the generation of carbon monoxide and hydro gen within the, formation. The oxygen and steam or carbon dioxide may be injected as a mixture or simulta neously by separate injection means, or oxygen may be
injected for intervals of time interrupted by brief pe riods of carbon dioxide, steam or water injection. The
effluent is predominantly gaseous carbon monoxide,
2,906,337
3,044,545
9/1959
7/1962
Hennig
Tooke .... ..
166/266
166/260
3,145,772
311741543
8/ 1964
3/1965
Hum
Sharp ---- u
166/26!
l66/26l
3'360'g44 :zxgm
3'442'332
3,605,890 9/l97l
'
166/26
166/267
166/272
l66/26l
5/1969
l0/ 1973
3,4so,os2 ll/l969
3,766,982
Holm ...... ..
___
27-
'
:51 f
: -
[Dill/I570"? FAC/L/f/[J
9 7 __
warn
v
6'
MK 5- axrszw
I
a /'
-'~._. 2
"-5- 3
.-_-1
t-;.
-,
[I] -':;I_l
[:_
_
v:_"..-] 1.31
[a ._ 1-_
1;;
L_J
L_l
U.S. Patent
4,026,357
1
IN SITU GASIFICATION OF SOLID HYDROCARBON MATERIALS IN A
4,026,357
SUBTERRANEAN FORMATION
BACKGROUND OF THE INVENTION 1. Field of the Invention This invention concerns a process for converting solid hydrocarbon materials present in a subterranean
formation into a gaseous material which can be recov
its, the percentage of hydrocarbon materials remaining is too small to justify mining operations, although the
total amount of hydrocarbon present in these forma
tions is considerable because of their volumes there is a
substantial need for a method which will permit recov
converting the solid materials into a gaseous form ple, tar sand deposits as are found in the western part of 20 within the reservoir itself, and recovering the gaseous form materials from the formation where they may be the United States and in the northern part of Alberta, utilized as fuel or feed gas for manufacturing opera Canada contain vast quantities of bituminous petro tions. leum, but essentially no material may be recovered by so called primary means because the viscosity of the SUMMARY OF THE INVENTION bituminous petroleum at reservoir conditions is in the 25 Solid hydrocarbon materials contained in a subsur range of millions of centipoise. Accordingly, some form face, porous, permeable formation may be converted of supplemental recovery process must be applied to to a gaseous form and thereby transported to the sur these tar sand materials, as well as to other subterra face, by contacting the material with a gas which is at nean, viscous petroleum containing formations, in order to recover any appreciable amount of hydrocar 30 least 40 percent oxygen, in combination with a moder ating ?uid such as steam or carbon dioxide to convert bon ?uids therefrom. the carbonaceous material to carbon monoxide and In the case of the tar sand deposits, a particularly
sure differential is applied to the material and the mate rials are present in a permeable formation. For exam
promising supplemental recovery technique has been disclosed in copending application, Ser. No. 481,581
ratio of air and steam to achieve a controlled low tem
oxygen is injected into the formation and sufficient ?led June 21, l974 and in Ser. No. 481,582 ?led June 35 heat is applied to the formation at the point of oxygen injection to initiate an in situ combustion reaction, 21, 1974, which generally involves the use of critical
after which the extraneous heat source is removed and
ating ?uid'is then injected simultaneously or intermit tently with the oxygen, the moderating ?uid being
steam, water or carbon dioxide. The moderating ?uid serves to reduce the oxidation reaction temperature,
mations similar to the tar sand deposits, because the 45 of the reaction is carbon monoxide and hydrogen. The weight ratio of oxygen to steam is thereafter main permeabiliy of the tar sand deposit is too low to permit tained at a value between 0.2 and 3.0. Some thermal application thereto of conventional in situ combustion cracking of the hydrocarbon material will result in the as is practiced in more conventional oil reservoirs.
centage recovery as compared to other supplemental 50 hydrocarbons which may be either gaseous or a liquid, but a substantial portion of the solid hydrocarbon ma recovery processes for use in tar sand deposits, a car terial will be converted to carbon monoxide and hydro bon residue does remain on the sand grains in the for
mation after termination of a controlled oxidation reac
tion. .
gen. Carbon monoxide and hydrogen are produced from a spaced apart production well and subjected on
the surface to additional treatment as necessary, de
BRIEF DESCRIPTION OF THE DRAWING materials to steam and oxygen under controlled condi 60 The attached drawing depicts a subterranean hydro carbon containing formation being subjected to the tions in a suitably fabricated reactor. For example, the
It is known by persons skilled in the art, and amply described in the literature, that many viscous liquid hydrocarbon materials, and under certain conditions granulated solid hydrocarbon materials, may be con verted to a synthesis gas by subjecting the hydrocarbon
following U.S. Patents deal with various aspects of gasi?cation of liquid or solid carbonaceous materials in
surface reactors under conditions of high temperature DESCRIPTION OF THE PREFERRED and pressure. U.S. Pat. No.i2,864,677, Eastman, et al.; 65 EMBODIMENTS U.S. Pat. No. 2,976,134, Paull; U.S. Pat. No. Brie?y, this invention concerns a method for con 2,992,907, Atwell; U.S. Pat. No. 3,097,081, Eastman, verting solid hydrocarbon materials contained in sub et al.; U.S. Pat. No. 3,556,751, Slater, et al.; and U.S.
4,026,357
supplemental recovery techniques, to a predominantly gaseous form by means of which the carbon materials
may be transported to the surface and used as a fuel or
is opened and steam is mixed with the heated oxygen from heater 8 and the hot mixture is introduced into the formation. Initially the ratio of oxygen to steam is 3 or more (3 pounds of oxygen per pound of steam), and this ratio is decreased or tapered gradually with time
until a value about 1 is achieved after a period of ap
feed stocks for manufacturing operations. One particu larly attractive embodiment of this invention involves treating a subterranean tar sand deposit which has previously been exploited by a controlled oxidation reaction of the type wherein air and steam are injected into the formation for the purpose of propagating a low temperature, controlled oxidation reaction through the formation, whereby a substantial portion of the bitumi nous petroleum material present in the tar sand deposit may be recovered. Although the process results in an
proximately 10 days. This ensures that the oxidation reaction will continue so as to provide the necessary heat for the partial oxidation reaction to occur.
Oxygen and steam react in the formation with the carbon residue to generate carbon monoxide and hy
percent hydrocarbons, of which 1.6 percent is soluble in hot toluene and the remaining 1.6 percent, predomi
hydrogen sul?de will be produced and the amount of hydrogen generated will be reduced. The above de scribed partial' oxidation reaction is exothermic, and
- nantly carbon residue, is not soluble in hot toluene. The 20 produces suf?cient heat to ensure that the reaction is
self sustaining. The reaction continues at the autoge nous temperature resulting from the exothermic partial high, as contrasted to the original very low permeability oxidation reaction. that existed in the tar sand deposit prior to the con Although the desired or optimum temperatures for trolled oxidation recovery program. The hydrocarbon material remaining in the formation is principally in the 25 conducting the above described reaction in a surface reactor is around l500 to 2500 F., the reaction occurs form of a thin ?lm distributed somewhat evenly spontaneously in the formation without the need for throughout the formation, all of the sand grains being controlling the temperature because of the dramati fairly uniformly coated. Although the weight percent of cally longer dwell time that the reactants have in the hydrocarbon residue is only 'about 3.2 percent, it subterranean formation as compared to a reactor on should be realized that this still amounts to approxi the surface. The typical dwell times fora partial oxida mately 5 pounds of hydrocarbon material per cubic tion reactor on the surface may range from 1 to 3 sec foot of formation. The commercial signi?cance of this onds, whereas the reactants are present together in the is considerable when compared to the volume of tar formation for much longer periods of time in applica sand material that might be encountered in an ordinary section of a reservoir. For example, in a 5,000 acre 35 tion of the present process. Because of the heat generated by the above de segment in which there is a tar sand deposit 100 feet thick, there is 105 billion pounds of hydrocarbon mate scribed reaction, the temperatures present within the rial remaining in the formation after completion of the formation are adequate to accomplish some in situ
The process of my inventionv may be best understood by referring to the attached drawing, in which tar sand
larly that portion of the residue described above which is soluble in hot toluene. The cracking reaction pre cedes according to the following equation:
deposit 1 is penetrated by injection well 2 and produc tion well 3, both wells being completed throughout the
entire thickness of the tar sand deposit. The tar sand
neously with any production of methane or higher mo oxidation, and their remains deposited on the sand lecular weight gaseous or liquid hydrocarbons. The grains within these deposits a thin ?lm of carbon resi coke produced as a result of the thermal cracking reac due as described above. A steam generator 4 supplied by boiler feed quality water 5 has its output 6 con 50 tion described above may be present either in the form of an additional carbon residue deposited on the sand nected to injection well 2. An air fractionation plant
reaction, or a ?ne powdery carbon black-like material is sometimes produced. The material will not cause any
particular problem in application of this process as described herein, since the permeability of the tar sand deposit after depletion by controlled oxidation is ade
quate to allow a certain amount of deposition of fine
(not shown) is positioned in injection well 2 adjacent the perforations establishing communication with the
tar sand deposit 1. The heater is a 20,000 kilowatt
applied to a virgin tar sand deposit which had not been previously depleted to some extent by the low tempera electric heater capable of heating a portion of the for ture oxidation reaction. mation immediately adjacent to the injection well to a Carbon monoxide and hydrogen are the principal temperature of about 1 100 F. with oxygen ?owing into the well, which results in the ignition of the carbon 65 effluents from production well 3, although some meth ane is produced and some liquid hydrocarbons may be residue on the sand grains in tar sand deposit 1. The produced as wellrln order to ensure that the pressure heater is utilized for only the ?rst 34 hours of opera remaining within the formation is high enough to sus tion, and is thereafter removed from the well. Valve 9
4,026,357
surned.
6 .
From about 0.3 to about 1.2 pounds of oxygen per pound of hydrocarbon to be treated will ultimately be
value of at least several hundred pounds ,per square 5 required, and the ratio of pounds of steam per pound of hydrocarbon material will be from about 0.25 to about inch. This is monitored in the embodiment illustrated in the ?gure by gauge 21 which reads the pressure down
2.2. ' .
necessary because the permeability of a partially de pleted tar sand deposit is so high that essentially no
pressure di?erential would be developed as a conse
and oxygen are injected into the formation, will ordi narily be a critical factor which must be controlled fairly closely. In order to maintain a reasonably con
stant linear volicity of the reaction front as it progresses
quence of the resistance to?ow within the formation. The gaseous effluents pass through line 11 into heat
ually increase the injection rate with time. It is pre is quite high, in the order of 500 or 600 F., and so it 15 ferred that the initial oxygen injection rate be approxi mately 100 standard cubic feet of oxygen per foot of is desirable to recover a substantial portion of this heat formation thickness per hour. This may be increased to for use in the process. Once the temperature of the about 300 after 5 days, and to an ultimate constant gaseous e?luent has risen to a value of above about operating value of about 800 standard cubic feet per 300 F., generation of at least a portion of the steam used in the process may be accomplished by this heat 20 hour per foot of formation thickness after two weeks or more of oxygen injection. The steam injection rate may scavenging means. Steam generation is accomplished be keyed to the oxygen injection rate according to the by passing boiler feed quality water into heat exchanger ratios given above. , . 1 12, the heat being removed from the gaseous effluents The process of my invention may be understood and utilized to generate steam which is transported via line 13 back through superheater 22 to the injection 25 more clearly by reference to the following ?eld exam ple, which is offered only as an additional illustrative well. The cooled effluents are then passed into a me embodiment, and is not intended to be limitative or chanical separator 14 which may be a cyclone type of restrictive thereof. . ' centrifugal separator or an electrostatic precipitator to A tar sand deposit is located under an overburden remove the particulate matter such as ash and, coke thickness of approximately 700 feet, and the thickness from the e?luent stream. The produced gas then passes of the tar sand deposit is 125 feet. The injection well is through line 15 to a carbon dioxide scrubber 16. Car located 200 feet from the production well. A boiler bon dioxide may be scrubbed from the produced gas by capable of producing super heated steam at a tempera absorption in water, methanol, monoethanolamine, or tue of around 800 F. and a pressure of 600 pounds per with a light hydrocarbon. Amine scrubbing is an espe cially effective and preferred method of removing the 35 square inch is installed with the output connected to a mixing chamber for mixing with the oxygen enriched carbon dioxide. Carbon dioxide removal is not essential gas. An air fractionating plant is located near by, which for some purposes, butin this application it is fre separates air into oxygen and nitrogen. Essentially 98 quently a desirable process. The carbon dioxide may be
with a super heated steam, and injected into the injec tion wellbore. The injection pressure is maintained at 600 pounds per square inch. The production well is equipped with gauge for monitoring the pressure of the system if the produced gas is to be utilized as a fuel gas, 45 effluent gas being produced, and a throttling valve is installed to maintain the back pressure on the produc or into additional processing equipment depending on tion well at a preselected value, 400 pounds per square the manufacturing use to be made of the gases. inch in this instance. The output of the production well _ in the embodiment illustrated, the option is provided is fed to a heat exchanger so that heat from the pro for passing the carbon monoxide and hydrogen into a methanizer 19, wherein the following reaction occurs: 50 duced effluent gases may be scavenged and utilized to
the formation via injection well 2. The scrubbed pro duced gas exiting from the amine scrubber 16 passes through line 18, which may connect with a gathering
This conversion of hydrogen and carbon monoxide into methane occurs at temperatures above 500 F. ,in the
presence of a nickel catalyst. This is a particularly de sirable reaction to perform if it is desired to utilize the
the heater is removed and the oxidation reaction is self ane is more than three times the BTU content of either carbon monoxide or hydrogen, and so methane is a 60 sustaining. The oxygen injection rate during this igni
more preferred fuel. In some applications it is satisfac tory to convert only a portion of the carbon monoxide in the methane, and enrich the carbon monoxide
hydrogen mixture with methane so as to increase its
BTU content to some predetermined value. It should 65 oxygen to steam is around 3.0 during the ?rst week of
be realized, of course that additional hydrogen must be supplied as by line 20 to the methanation reaction for it
4,026,357
to 2.0. After an additional week of operating under these conditions, the injection rate is increased to
100,000 standard cubic feet per hour and the oxygen to steam weight ratio is_reduced to 1.0 and, maintained at this value during the continuation of the operation.
Gaseous e?'luents are obtained from the production well which are analyzed and found to be 42 percent
content of the oxygen enriched gas is above 90 percent. 3. A method as recited in'claim 1 wherein the moder
ating ?uid is water. ' i >
methane, 2 percent water, and approximately 5 percent liquid hydrocarbons. The balance is essentially all car bon dioxide, and carbon dioxide is-removed from the effluent gas by meansof diethanolamine scrubbing.
The carbon dioxide removed .by this method is comin gled with the injected oxygen and steam. The carbon
ratio of oxygen to steam varies from 0.2 to 3.0. 8. A method as recited in claim 1 wherein the weight 15 monoxide and hydrogen are further treated to remove ratio of oxygen to steam introduced into the formation water and particulate matter, and then the carbon mon is decreased with injection of oxygen and steam into
the formation.
ammonium manufacturing plant for hydrogenating nitrogen from the air separation plant.
Thus, I have disclosed that essentially solid hydrocar
rated from the produced gas on the surface and mixed with oxygen being introduced into the formation. bon materials such as the carbon residue on sand grains 10. A method as recited in claim 1 wherein the for in a tar sand deposit after completion of a controlled mation being treated is a subterranean tar sand forma oxidation petroleum recovery operation can be con 25 tion which has previously been subjected to treatment
verted into a gaseous mixture of carbon monoxide and
hydrogen which can be utilized as fuel or manufactur
ture oxidation reaction to stimulate production of liq_ uid petroleum, resulting inv deposition of a coke like
material on the formation sand grains. '
number of speci?c illustrative embodiments it is not so limited, as many variations thereof will be apparent to persons skilled in the related art. Similarly, while a mechanism and reactions to describe the phenomena 35 occurring upon application of the process of my inven tion to a subterranean solid hydrocarbon containing
a. introducing a mixture of air and steam into the formation at a predetermined ratio for the purpose
reaction which propagates from the injection well toward the production well and recovering petro leum from the production well, which low tempera
ture oxidation results in the formation of a solid, coke-like material on the formation sand grains; b. thereafter introducing a gas which is at least 40%
oxygen into the formation at a temperature of at
l. A method of recovering hydrocarbons from a sub 45 terranean porous, permeable viscous petroleum con
group consisting of water, superheated steam, satu rated steam, carbon dioxide, and'mixtures thereof
_ to comingle with the gas causing conversion of the
b. thereafter introducing a gas which is at least 40% 55 moderating ?uid 13. A method oxygen into the formation at a temperature of at least 600 F and a pressure of at least 200 lbs. per moderating ?uid '14. A method square inch; moderating ?uid c. introducing a moderating ?uid selecting from a
is saturated steam.
as recited in claim 11 wherein the is water.
as recited in claim 11 wherein the
is superheated steam.
1
is oxygen-enriched air.
. * * * * *