CA1133387A - Selective permeability reduction with polymerizable monomers around steam injection wells - Google Patents
Selective permeability reduction with polymerizable monomers around steam injection wellsInfo
- Publication number
- CA1133387A CA1133387A CA340,033A CA340033A CA1133387A CA 1133387 A CA1133387 A CA 1133387A CA 340033 A CA340033 A CA 340033A CA 1133387 A CA1133387 A CA 1133387A
- Authority
- CA
- Canada
- Prior art keywords
- steam
- monomer
- formation
- vapor
- styrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/13—Methods or devices for cementing, for plugging holes, crevices, or the like
- E21B33/138—Plastering the borehole wall; Injecting into the formation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/592—Compositions used in combination with generated heat, e.g. by steam injection
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/24—Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
Abstract
ABSTRACT OF THE DISCLOSURE
A method is proposed for treating subsurface earth formations in the neighborhood of a steam injection well by selectively altering the effective permeability of the formation through depositing a monomer within the formation where the permeability is to be controlled and the eventual polymerization of that monomer to produce a high-viscosity polymer within the formation to effectively decrease the permeability of that portion of the formation. The monomer is transported to the subsurface formation in vapor form with steam. The mixed vapor first condenses out liquid water only and later condenses out water and immiscible liquid monomer.
The polymerization of the monomer then takes place to produce a high-viscosity polymer within the subsurface formation.
A method is proposed for treating subsurface earth formations in the neighborhood of a steam injection well by selectively altering the effective permeability of the formation through depositing a monomer within the formation where the permeability is to be controlled and the eventual polymerization of that monomer to produce a high-viscosity polymer within the formation to effectively decrease the permeability of that portion of the formation. The monomer is transported to the subsurface formation in vapor form with steam. The mixed vapor first condenses out liquid water only and later condenses out water and immiscible liquid monomer.
The polymerization of the monomer then takes place to produce a high-viscosity polymer within the subsurface formation.
Description
002SELECTIVE PERMEABILITY REDUCTION WIT~
003POLYMERIZABLE MONOMERS ~ROUND S$EAM INJECTION WELLS
006The present invention relates to improving the effi~
007 ciency of a steam drive or steam stimulation in the assisted 008 recovery of hydrocarbons. Steam flooding of subsurface hydro-009 carbon-containing formations has been used to produce the hydro-010 carbons which exist in very heavy or viscous form. The heating 011 is performed with steam to bring the hydrocarbons to a condi-012 tion of mobility where they will flow either by gravity or by 013 formation pressure gradients, either natural or imposed, to a 014 producing well for transport to the earth's surface. The 015 greatest efficiency in such steam flooding operations is accom-016 plished if the formation around the steam injection well is uni-017 formly heated as the steam moves out from the wellbore. Ineffi-018 ciency occurs if one portion of the formation is more permeable Ql9 than other portions so as to sidetrack a large portion of the 020 steam through the more permeable portion, thus causing non-021 uniform heating of the remainder of the formation. A means for 022 selectively affecting the permeability of the subsurface forma-023 tion is therefore desirable.
025 Heretofore, methods have been proposed for treating 026 subsurface earth formations for the purpose of reducing the 027 rate of movement of the fluid materials through selected parts 028 of the formation. Included in the prior art technologies are 029 the in-place formation of gels, either by surface prepared mate-030 rials that are pumped into the well to become operative at a 031 particular time after their first introduction into the well or 032 by the introduction of several components at different times 033 with an introduction procedure that combines one or more of the 034 materials in the formation where the selective permeability 035 reduction may be desired. Most of these prior art systems have 036 been somewhat ineffective because of the inability to control 037 the actual placement of the materials into the position in the 038 formation where the formation treatment is desired.
~RIEF STATEMENT OF INVENTION
In accordance with the present invention, in a steam-flooding production process a material is transported from the earth's surface to the subsurface earth formation with the steam that is being used to steam-flood the formation. The material is intended for effectively controlling the permeability of the subsurface formation at the location where the permeability is to be controlled, The steam carries the material to that location. The ex;stence of a temperature gradient in lateral distance from the steam injection well is empolyed to selectively condense the carrier steam and thus place the carried material.
The placed material is immiscible with the water phase of the condensed steam and is operable to selectively plug or control the permeability of the formation where it is placed.
The invention seeks to provide a method and apparatus for treating subsurface earth formations at subsurface distances from a steam injection well to alter selectively the effective permeability of the formation.
Additionally the present invention seeks to provide a method of positioning a monomer within a subsurface earth forma-tion at a subsurface distance from a steam injection well so as to place the monomer in a position where the effective permea-bility of a formation is to be controlled.
The present invention also seeks to provide for the transportation of a monomer in a continuous vapor phase with steam into subsurface earth formations where the monomer may be selectively condensed from and separated from the condensed steam.
The present invention also seeks to provide for the posi-tioning of a monomer within the subsurface earth formations ata distance from a steam injection well where the monomer may be .,;
~1333~7 polymerized to form a high-viscosity polymer for substantially decreasing the effective permeability of the subsurface earth formation.
Thus this invention provides a method for treating a sub-surface earth formation in the neighborhood of a steam injection well to alter selectively the effective permeability of said formation at said distance comprising the steps of:
(a) producing a vapor mixture consisting of steam and the vapor of a polymerizable monomer, said monomer in liquid state being immiscible with water, the steam being in excess so that at ~he pressures and temperatures of said subsurface earth formation being treated the first condensate will consist of water only; and (b) injecting said mixture into said subsurface earth formation being treated so that within said subsurface earth formation being treated the initial cooling of said vapor causes excess steam to condense out of said vapor, and after further cooling said monomer will begin to condense and deposit a se-parate immiscible phase, whereby said condensed monomer will polymerize to become a high-viscosity polymer, thereby sub-stantially decreasing the effective permeability of said sub-surface earth formation where said polymer has been deposited.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic elevational view, partially in section, illustrating apparatus which may be used to perform the method of the present invention.
Referring no~ to the drawing, FIG.l illustrates a pre-ferred embodiment of apparatus assembled in accordance with the present inven'ion for accomplishing the method herein claimed and described. While it is recognized that the method of the present invention can be accomplished using a variety of ap-paratus, it is preferred that the apparatus used in performing the method of the present invention be assembled in aecordance with that illustrated in FIG. 1. As shown in FIG.l, a pro-ducing formation 20 is penetrated by an injeetion well 22 which may be cased with a easing 24 having perforations 26 at the lo~
eation of the produeing formation. A flow tube 28 is arranged in the well 22 to provide a flow path for steam down the well to the produeing zone 20. In most applieations, it is desir-able to have a packer 30 loeated above and close to the pro-ducing formation 20.
At least one producing well 32, which also penetrates the producing formation 20, is required in accordance with the present invention. In actual field operations, the method of the present invention will generally utilize a large number of wells with injection wells and the produeing wells positioned in accordance with a preplanned pattern. For example, a 5-spot or 7-spot pattern may be useful in the present invention. In any event, each producing well 32 has suitable producing equip-ment such as a string of producing tubing 34, the lower end of which contains a pump 36. The pump is operated by conventional surfaee equipment 35 which reciprocates a sucker rod 38 to lift -3a-11333~3~
001 ~4~
002 the hydrocar~ons to gathering lines 39 at the s~rface. In 003 accordance with the present invention, steam is injected into 004 the subsurface formations and the hydrocarbons within the forma-005 tion are heated by the injected steam and are caused to flow 006 toward the producing well 32 there to be lifted to the earth's 007 surface for distribution.
008 The improvement proposed by the present invention is 009 the addition of a polymerizable monomer to the injected stream 010 and the positioning of the monomer within the formation in a 011 predetermined location. The invention also contemplates the 012 addition of other additives to the injected steam. Schema-013 tically FIG. 1 illustrates surface elements for accomplishing 014 the proposed improvement.
015 The previously described casing 24 is secured to a 016 well head 40 at the earth's surface. Flow tube 28 passes 017 through the well head. A steam generator 41 is connected 018 through a valve 42 to the flow tube 28. A source of monomer 43 019 is connected through a valve 44 and a pump 45 to the flow tube 020 28 downstream from valve 42. A source of additive 46 is 021 connected through a valve 47 and a pump 48 to the flow tube 28 022 downstream from the valve 42. It should be understood that the 023 steam generator 41 will include the necessary controls to 024 produce steam at a desired temperature, pressure and/or quality 025 and that the sources of both monomer 43 and additive 46 are 026 merely schematic illustrations of sources that may supply 027 vapor, liquid or solid materials as needed. Pumps 45 and 48 028 for the monomer and additive respectively are provided to 029 produce a supply of each material to the flow tube 28 at the 030 pressure of the steam supplied from the steam generator.
032 To understand the details of the method of the 033 present invention it is first necessary to understand a few 034 more details of the problem being solved. Steam injected into 035 an oil-producing formation performs two principal desirable 036 functions. In the first place, it heats the formation rock and 037 the oil and water contained within the formation. The heating 002 of the oil lowers its viscosity so the oil therefore flows more 003 readily toward the nearby producing well (or wells). In the 004 second place, the steam itself performs a pushing function. In 005 the ideal case, the steam (and its condensate) stays behind the 006 oil, pushing the oil toward the producing wells. In actual, 007 non-ideal cases, part of the steam tends to bypass the oil.
008 This non-ideal behavior occurs for at least two different 009 reasons. The first reason is that the steam is less dense than 010 the oil and it therefore tends to flow toward the top of the 011 formation. The steam being in the top of the formation will 012 then push ahead of it only the oil in the upper part of the 013 formation. The second reason is that actual oil-containing 014 formations are heterogeneous in permeability; and the boundary 015 between a pushed fluid and a pushing fluid moves faster in more 016 permeable regions of the formation. This makes the more 017 permeable regions contain higher proportions of the less 018 viscous pushing fluid than do the less permeable regions, and 019 this, in turn, makes the flow relatively still faster in those 020 more permeable regions, so the boundary between the two fluids 021 "fingers" into the more permeable regions, tending to bypass 022 oil in the less permeable regions.
023 For the above reasons a method is needed to decrease 024 the effective permeability of the parts of the formation into 025 which the steam tends to flow most readily, without decreasing 026 the effective permeability of the other parts of the formation 027 that the steam is tending to bypass. More particularly, after 028 a steam injection has been in operation for an initial period, 029 a method is needed that will decrease the effective permeabi-030 lity of parts of the formation into which the steam has already 031 advanced the farthest, without decreasing the permeability of 032 the preceding parts of the formation and the parts that the 033 steam has already tended to bypass. The present invention 034 provides such a method.
035 In the method of the present invention, the permeabi-036 lity-reducing agent is carried with the steam in an inactive 037 state, as far as permeability reduction is concerned, and the ~3~
002 agent does not become active for permeability reduction until 003 the formation temperature has declined to a level such that 004 monomer vapor condenses to a liquid in the parts of the forma-005 tion into which the steam front has advanced. The permeabi-006 lity-reducing agent is a polymerizable monomer carried in the 007 steam as a vapor too dilute to polymerize, but polymerizable 008 after condensation out of the vapor stream as liquid monomer.
009 In the preferred form of the invention, the steam 010 entering the formation contains the monomer vapor and the phase 011 relationships are such that as the steam begins to cool, the 012 first condensate will be pure water, and only after a certain 013 predetermined lower temperature is reached will a two-phase con-014 densate begin to appear, consisting of liquid water, and an 015 essentially immiscible liquid monomer. At that place and time 016 and temperature, the liquid monomer will begin to polymerize to 017 form a solid (or at least a highly viscous body) in the pores 018 of the reservoir rock, thereby reducing the pore volumes 019 between the grains and reducing the permeability of the pore 020 passages.
021 One material that may be used in a method such as 022 described above is styrene, which in liquid state is essen-023 tially immiscible with water, but which will vaporize with 024 steam at any temperature above the temperature at which the sum Q25 of the styrene vapor pressure and the water vapor pressure 026 equals the ambient pressure. When the mixed vapor is 027 condensed, first producing a condensate of pure water, and then 028 producing a two~phase condensate of liquid water and immiscible 029 liquid styrene, the styrene will thermally polymerize to form 030 polystyrene, a thermoplastic that is solid below about 250F, 031 and a very viscous melt at higher temperatures.
032 In a variation of the method sufficient ammonia is 033 added to the boiler feed water or to the steam stream to 034 establish an ammonia concentration in the vapor e~uivalent to 035 about one percent by weight of the proposed styrene concentra-036 tion. Ammonia will tend to inhibit any styrene polymerization 037 in the vapor phase.
038 A possible operating procedure involves metering ~333~
002 styrene into the steam stream between the generator and the 003 well head at about one part styrene to four parts water by 004 weight. The styrene will flash evaporate to form a 005 styrene-steam vapor. Upon cooling this vapor will first 006 condense out pure liquid water and later a two phase liquid 007 mixture of water and immiscible styrene. If ammonia has been 008 added to the stream, part of it will remain in the uncondensed 009 vapor and part of it will be dissolved in the liquid water 010 phase. The styrene droplets will coalesce and undergo thermal 011 polymerization to form polystyrene.
012 Monomers useful in this invention include monomers 013 that are vaporizable into the steam stream at the injection 014 temperature and pressure, that are condensable within the 015 petroleum-containing formation at the temperature and pressure 016 prevailing in the formation location where permeability 017 alteration is desired, and that are thermally polymerizable in 018 the condensed state at the temperature prevailing in the 019 formation location where permeability alteration is desired.
020 Preferred monomers are essentially immiscible with water in the 021 condensed state at temperatures and pressures of interest.
022 Monomers useful in this invention can be further 023 categorized by considering the phenomena involved. The 024 vaporization and condensation equilibria for immiscible liquids 025 are discussed by Barnett F. Dodge, "Chemical Engineering 026 Thermodynamics", McGraw-Hill Book Company, Inc., New York, 027 1944, pp 533-535. The equilibrium vapor pressure over a 028 mixture of immiscible liquids, such as styrene and water, is 029 the sum of the vapor pressures of the individual components.
030 The system boiling point temperature is independent of the 031 liquid composition and is the temperature at which the sum of 032 the vapor pressures of the pure components equals the total 033 pressure. This phenomenon is important in that monomers with 034 boiling point temperatures considerably higher than the boiling 035 point temperature of water can be useful in this invention.
036 From the discussions above, limits may be set that 037 will better define monomers useful in the invention. The :1133387 002 monomer and water should be chemically nonreactive with each 003 other in the liquid and vapor states, and should be essentially 004 immiscible in the liguid state over the temperature range of 005 interest (say 60-600F). Any water-immiscible monomer with a 006 vapor pressure can be vaporized into a steam stream. For 007 practicality, a monomer that has a three-phase equilibrium 008 point (for the meaning of this point see Dodge, loc. cit.) 009 vapor monomer content of at least 10 wt. percent would be 010 preferred so that the condensed monomer phase will be of 011 sufficient local volume to effectively reduce the permeability.
012 For a monomer with a molecular weight of 80, the corresponding 013 three-phase equilibrium point composition data are shown in 014 Table 1.
018 Vapor Pressure, 019 Monomer, Wt.% Monomer, Mole% % of Total Pressure _ _ 02050 22.5 22.5 02120 5.6 5.6 02210 2.5 2.5 023 Thus a monomer useful in the invention would have as 024 an upper limit a vapor pressure on the order of 2.5% or 025 preferably 5.6~ of the total system pressure (the system 026 temperature and pressure are established by the saturated steam 027 injection stream). At a saturated steam pressure of 1 028 atmosphere (212F) the monomer vapor pressure would then be on 029 the order of 19 mm or preferably 43 mm Hg or greater. Thus 030 some monomers with 1 atmosphere boiling temperatures as high as 031 400F would be useful in the invention.
032 A lower boiling point limit for monomers useful in 033 the invention is established by considering the formation 034 temperature in which the monomer must condense. Thus the lower 035 boiling point limit for a monomer useful in the invention would 036 be several degrees F above the original reservoir temperature 037 at the pressure existing within the condensation region.
~133~7 002 The remaining requirement for monomers useful in the 003 invention is that the monomers must be thermally polymerizable 004 at the temperatures of interest. The rates of polymerization 005 are not too important. An immediate or "flash" polymerization 006 would be undesirable because the condensed monomer would not 007 have time to coalesce into a bulk phase. However, no common 008 monomers that meet the other monomer requirements will "flash"
009 polymerize under thermal initiation. Polymerizations extending 010 over days or weeks may not be detrimental in that low molecular 011 weight polymers may be as effective as higher molecular weight 012 polymers in permeability reduction.
013 Type of monomers that may be useful in this invention 014 are: vinyl compounds such as styrene and ring-substituted 015 styrene, 2-vinyl pyridine, 2-methyl-5-vinyl pyridine; vinyl 016 esters such as vinyl butyrate, vinyl-2-ethylhexanoate; vinyl 017 ethers such as vinyl butylether, vinyl 2-ethylhexyl ether;
018 acrylates such as acrylonitrile, acrylic and methacrylic acid 019 esters; dienes such as isoprene, chloroprene, 2-ethyl-1,3-buta-020 diene; acetylenes such as phenyl acetylene and phenoxy 021 acetylene. Combinations of monomers may also be used 022 effectively.
023 A preferred monomer in the invention is styrene, 024 preferred for its chemical and physical properties, its ready 025 availability, and low cost. Selected properties of styrene are 026 listed in Table 2. Table 3 lists data on the styrene-water 027 system.
003STYRENE (VINYLBENZENE) 004PHYSICAL AND CHEMICAL PROPE~TIES
006 Formula C6H5CH:CH2 007 Molecular Weight 104.144 008 Boiling Point, 1 atm. 145.2C 293.4F
009 Freezing Point in Air, 1 atm. -30.6C -23.1F
010 Critical Temperature 641K
011 Critical Pressure 575 psia 012Vapor Pressure log PmmHg = 6.95711-1445.58/(tC+203.43) 013At 200C 51.64 psia 014Liquid Density, g./ml. dt = 0.9238 - 0.0008766 t(C) 01525C 0.9019 016200C 0.7485 017Viscosity, cp at 25C 0.730 018 Heat Capacity, Liquid, 25-200C, Cal/g/C 0.525 Average 019 Heat of Vaporization, 200C, Cal/g. approx. 80 020Heat of Polymerization, Cal/g, 25C160.2 021 Volume Shrinkage on Polymerization17 025Vapor Pressure 026 100mm200mm 400mm 760mm 50 psia500 psia 027 Water, tF 125152 181 212 281 467 028 Styrene, tF 180 214 252 293 389 030 Polymer Pro~erties 031 Thermal polymerization of styrene monomer at 392F
032 should lead to polystyrene with a weight average molecular 033 weight near 25,000. In the absence of oxygen, this polymer 034 should be relatively stable at temperatures below 500F. Melt 035 viscosity may be on the order of 5000 centipoises.
036 To indicate the behavior that may be expected in the 037 field using styrene with steam, several laboratory experiments 038 were performed.
~.~3338~
002 Styrene and water were codistilled through a short 003 path distillation apparatus, with minimum reflux, at 004 temperatures near 200F. Distillations were done with and 005 without added ammonia in the system. No evidence of polymeri-006 zation was noted in the distillation flask or still head.
007 Collected distillate separated into two liquid phases. Nuclear 008 magnetic resonance (NMR~ spectra of the collected styrene layer 009 gave no indication of compounds other than styrene monomer (NMR
010 detects as little as 0.5 weight percent polystyrene in styrene 011 solution). After several days at room temperature, the 012 uninhibited styrene distillate had polymerized to a syrupy 013 stage.
014 A 4.5 inch, 40 x 60 mesh sand pack in a Hassler cell 015 was heated to 275F, and steam at 220F was injected for some 016 time to establish rate. Styrene (30 ml) was then metered into 017 the steam stream to produce a 10% by volume vapor. The pack 018 effluent, still vaporized, was condensed. Almost all of the 019 injected styrene was recovered as distillate. NMR indicated no 020 polystyrene in the distillate. No indication of polystyrene 021 was found in the sand pack.
022 Styrene and water, with and without ammonia added, 023 were heated at 392F in Hoke bombs under autogeneous pressure.
024 After heating two hours, the bombs were cooled to room tempera-025 ture and opened. In all cases the styrene layer had 026 polymerized to hard, glassy polystyrene.
027 A 60-inch, 40 x 60 mesh sand pack in a Hassler cell 028 was used for the following experiment. About one pore volume 029 (liquid basis) of steam was injected into the cold sand pack to 030 warm it up and establish injection rates. All effluent 031 collected was cool, liquid water. A 10% styrene - 90% steam 032 stream was injected until 20 ml styrene was in the sand pack.
033 No styrene was noted in the effluent. Injection was then 034 stopped, the ends of the sand pack were plugged, and the 035 ~assler cell was heated at 230F for 10 hours. The cooled sand 036 pack was not consolidated, but sand grains were stuck together.
037 Polystyrene was identified by NMR.
002 At room temperature, water was injected through 4.5 003 inch, 40 x 60 mesh sand packs to establish initial permeabi-004 lity. Liquid styrene and water were coinjected at equal 005 volumetric rates, with and without ammonia added, until styrene 006 was obvious in the effluent fluid. The sand packs were then 007 plugged at both ends and heated for 16 hours at 300F. After 008 cooling, solid polystyrene was cleaned from the end plugs and 009 water permeability was measured. In both cases, permeability 010 reduction was about 75%. The sand packs were found to be con-011 solidated with polystyrene; the consolidated sands were quite 012 friable.
013 These experiments show that styrene monomer poly-014 merizes in the presence of water and ammonia (1) in the bulk 015 liquid state at 392F, (2) after condensation in a sand pack at 016 230F, (3) as bulk liquid in a sand pack at 300F. They also 017 show that a styrene-water vapor stream can pass through a short 018 sand pack at 2759F with no apparent styrene polymerization.
019 While a certain preferred embodiment of the invention 020 has been specifically disclosed it is understood that the 021 invention is not limited thereto as many variations will be 022 readily apparent to those skilled in the art and the invention 023 is to be given its broadest possible interpretation within the 024 terms of the following claims.
003POLYMERIZABLE MONOMERS ~ROUND S$EAM INJECTION WELLS
006The present invention relates to improving the effi~
007 ciency of a steam drive or steam stimulation in the assisted 008 recovery of hydrocarbons. Steam flooding of subsurface hydro-009 carbon-containing formations has been used to produce the hydro-010 carbons which exist in very heavy or viscous form. The heating 011 is performed with steam to bring the hydrocarbons to a condi-012 tion of mobility where they will flow either by gravity or by 013 formation pressure gradients, either natural or imposed, to a 014 producing well for transport to the earth's surface. The 015 greatest efficiency in such steam flooding operations is accom-016 plished if the formation around the steam injection well is uni-017 formly heated as the steam moves out from the wellbore. Ineffi-018 ciency occurs if one portion of the formation is more permeable Ql9 than other portions so as to sidetrack a large portion of the 020 steam through the more permeable portion, thus causing non-021 uniform heating of the remainder of the formation. A means for 022 selectively affecting the permeability of the subsurface forma-023 tion is therefore desirable.
025 Heretofore, methods have been proposed for treating 026 subsurface earth formations for the purpose of reducing the 027 rate of movement of the fluid materials through selected parts 028 of the formation. Included in the prior art technologies are 029 the in-place formation of gels, either by surface prepared mate-030 rials that are pumped into the well to become operative at a 031 particular time after their first introduction into the well or 032 by the introduction of several components at different times 033 with an introduction procedure that combines one or more of the 034 materials in the formation where the selective permeability 035 reduction may be desired. Most of these prior art systems have 036 been somewhat ineffective because of the inability to control 037 the actual placement of the materials into the position in the 038 formation where the formation treatment is desired.
~RIEF STATEMENT OF INVENTION
In accordance with the present invention, in a steam-flooding production process a material is transported from the earth's surface to the subsurface earth formation with the steam that is being used to steam-flood the formation. The material is intended for effectively controlling the permeability of the subsurface formation at the location where the permeability is to be controlled, The steam carries the material to that location. The ex;stence of a temperature gradient in lateral distance from the steam injection well is empolyed to selectively condense the carrier steam and thus place the carried material.
The placed material is immiscible with the water phase of the condensed steam and is operable to selectively plug or control the permeability of the formation where it is placed.
The invention seeks to provide a method and apparatus for treating subsurface earth formations at subsurface distances from a steam injection well to alter selectively the effective permeability of the formation.
Additionally the present invention seeks to provide a method of positioning a monomer within a subsurface earth forma-tion at a subsurface distance from a steam injection well so as to place the monomer in a position where the effective permea-bility of a formation is to be controlled.
The present invention also seeks to provide for the transportation of a monomer in a continuous vapor phase with steam into subsurface earth formations where the monomer may be selectively condensed from and separated from the condensed steam.
The present invention also seeks to provide for the posi-tioning of a monomer within the subsurface earth formations ata distance from a steam injection well where the monomer may be .,;
~1333~7 polymerized to form a high-viscosity polymer for substantially decreasing the effective permeability of the subsurface earth formation.
Thus this invention provides a method for treating a sub-surface earth formation in the neighborhood of a steam injection well to alter selectively the effective permeability of said formation at said distance comprising the steps of:
(a) producing a vapor mixture consisting of steam and the vapor of a polymerizable monomer, said monomer in liquid state being immiscible with water, the steam being in excess so that at ~he pressures and temperatures of said subsurface earth formation being treated the first condensate will consist of water only; and (b) injecting said mixture into said subsurface earth formation being treated so that within said subsurface earth formation being treated the initial cooling of said vapor causes excess steam to condense out of said vapor, and after further cooling said monomer will begin to condense and deposit a se-parate immiscible phase, whereby said condensed monomer will polymerize to become a high-viscosity polymer, thereby sub-stantially decreasing the effective permeability of said sub-surface earth formation where said polymer has been deposited.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic elevational view, partially in section, illustrating apparatus which may be used to perform the method of the present invention.
Referring no~ to the drawing, FIG.l illustrates a pre-ferred embodiment of apparatus assembled in accordance with the present inven'ion for accomplishing the method herein claimed and described. While it is recognized that the method of the present invention can be accomplished using a variety of ap-paratus, it is preferred that the apparatus used in performing the method of the present invention be assembled in aecordance with that illustrated in FIG. 1. As shown in FIG.l, a pro-ducing formation 20 is penetrated by an injeetion well 22 which may be cased with a easing 24 having perforations 26 at the lo~
eation of the produeing formation. A flow tube 28 is arranged in the well 22 to provide a flow path for steam down the well to the produeing zone 20. In most applieations, it is desir-able to have a packer 30 loeated above and close to the pro-ducing formation 20.
At least one producing well 32, which also penetrates the producing formation 20, is required in accordance with the present invention. In actual field operations, the method of the present invention will generally utilize a large number of wells with injection wells and the produeing wells positioned in accordance with a preplanned pattern. For example, a 5-spot or 7-spot pattern may be useful in the present invention. In any event, each producing well 32 has suitable producing equip-ment such as a string of producing tubing 34, the lower end of which contains a pump 36. The pump is operated by conventional surfaee equipment 35 which reciprocates a sucker rod 38 to lift -3a-11333~3~
001 ~4~
002 the hydrocar~ons to gathering lines 39 at the s~rface. In 003 accordance with the present invention, steam is injected into 004 the subsurface formations and the hydrocarbons within the forma-005 tion are heated by the injected steam and are caused to flow 006 toward the producing well 32 there to be lifted to the earth's 007 surface for distribution.
008 The improvement proposed by the present invention is 009 the addition of a polymerizable monomer to the injected stream 010 and the positioning of the monomer within the formation in a 011 predetermined location. The invention also contemplates the 012 addition of other additives to the injected steam. Schema-013 tically FIG. 1 illustrates surface elements for accomplishing 014 the proposed improvement.
015 The previously described casing 24 is secured to a 016 well head 40 at the earth's surface. Flow tube 28 passes 017 through the well head. A steam generator 41 is connected 018 through a valve 42 to the flow tube 28. A source of monomer 43 019 is connected through a valve 44 and a pump 45 to the flow tube 020 28 downstream from valve 42. A source of additive 46 is 021 connected through a valve 47 and a pump 48 to the flow tube 28 022 downstream from the valve 42. It should be understood that the 023 steam generator 41 will include the necessary controls to 024 produce steam at a desired temperature, pressure and/or quality 025 and that the sources of both monomer 43 and additive 46 are 026 merely schematic illustrations of sources that may supply 027 vapor, liquid or solid materials as needed. Pumps 45 and 48 028 for the monomer and additive respectively are provided to 029 produce a supply of each material to the flow tube 28 at the 030 pressure of the steam supplied from the steam generator.
032 To understand the details of the method of the 033 present invention it is first necessary to understand a few 034 more details of the problem being solved. Steam injected into 035 an oil-producing formation performs two principal desirable 036 functions. In the first place, it heats the formation rock and 037 the oil and water contained within the formation. The heating 002 of the oil lowers its viscosity so the oil therefore flows more 003 readily toward the nearby producing well (or wells). In the 004 second place, the steam itself performs a pushing function. In 005 the ideal case, the steam (and its condensate) stays behind the 006 oil, pushing the oil toward the producing wells. In actual, 007 non-ideal cases, part of the steam tends to bypass the oil.
008 This non-ideal behavior occurs for at least two different 009 reasons. The first reason is that the steam is less dense than 010 the oil and it therefore tends to flow toward the top of the 011 formation. The steam being in the top of the formation will 012 then push ahead of it only the oil in the upper part of the 013 formation. The second reason is that actual oil-containing 014 formations are heterogeneous in permeability; and the boundary 015 between a pushed fluid and a pushing fluid moves faster in more 016 permeable regions of the formation. This makes the more 017 permeable regions contain higher proportions of the less 018 viscous pushing fluid than do the less permeable regions, and 019 this, in turn, makes the flow relatively still faster in those 020 more permeable regions, so the boundary between the two fluids 021 "fingers" into the more permeable regions, tending to bypass 022 oil in the less permeable regions.
023 For the above reasons a method is needed to decrease 024 the effective permeability of the parts of the formation into 025 which the steam tends to flow most readily, without decreasing 026 the effective permeability of the other parts of the formation 027 that the steam is tending to bypass. More particularly, after 028 a steam injection has been in operation for an initial period, 029 a method is needed that will decrease the effective permeabi-030 lity of parts of the formation into which the steam has already 031 advanced the farthest, without decreasing the permeability of 032 the preceding parts of the formation and the parts that the 033 steam has already tended to bypass. The present invention 034 provides such a method.
035 In the method of the present invention, the permeabi-036 lity-reducing agent is carried with the steam in an inactive 037 state, as far as permeability reduction is concerned, and the ~3~
002 agent does not become active for permeability reduction until 003 the formation temperature has declined to a level such that 004 monomer vapor condenses to a liquid in the parts of the forma-005 tion into which the steam front has advanced. The permeabi-006 lity-reducing agent is a polymerizable monomer carried in the 007 steam as a vapor too dilute to polymerize, but polymerizable 008 after condensation out of the vapor stream as liquid monomer.
009 In the preferred form of the invention, the steam 010 entering the formation contains the monomer vapor and the phase 011 relationships are such that as the steam begins to cool, the 012 first condensate will be pure water, and only after a certain 013 predetermined lower temperature is reached will a two-phase con-014 densate begin to appear, consisting of liquid water, and an 015 essentially immiscible liquid monomer. At that place and time 016 and temperature, the liquid monomer will begin to polymerize to 017 form a solid (or at least a highly viscous body) in the pores 018 of the reservoir rock, thereby reducing the pore volumes 019 between the grains and reducing the permeability of the pore 020 passages.
021 One material that may be used in a method such as 022 described above is styrene, which in liquid state is essen-023 tially immiscible with water, but which will vaporize with 024 steam at any temperature above the temperature at which the sum Q25 of the styrene vapor pressure and the water vapor pressure 026 equals the ambient pressure. When the mixed vapor is 027 condensed, first producing a condensate of pure water, and then 028 producing a two~phase condensate of liquid water and immiscible 029 liquid styrene, the styrene will thermally polymerize to form 030 polystyrene, a thermoplastic that is solid below about 250F, 031 and a very viscous melt at higher temperatures.
032 In a variation of the method sufficient ammonia is 033 added to the boiler feed water or to the steam stream to 034 establish an ammonia concentration in the vapor e~uivalent to 035 about one percent by weight of the proposed styrene concentra-036 tion. Ammonia will tend to inhibit any styrene polymerization 037 in the vapor phase.
038 A possible operating procedure involves metering ~333~
002 styrene into the steam stream between the generator and the 003 well head at about one part styrene to four parts water by 004 weight. The styrene will flash evaporate to form a 005 styrene-steam vapor. Upon cooling this vapor will first 006 condense out pure liquid water and later a two phase liquid 007 mixture of water and immiscible styrene. If ammonia has been 008 added to the stream, part of it will remain in the uncondensed 009 vapor and part of it will be dissolved in the liquid water 010 phase. The styrene droplets will coalesce and undergo thermal 011 polymerization to form polystyrene.
012 Monomers useful in this invention include monomers 013 that are vaporizable into the steam stream at the injection 014 temperature and pressure, that are condensable within the 015 petroleum-containing formation at the temperature and pressure 016 prevailing in the formation location where permeability 017 alteration is desired, and that are thermally polymerizable in 018 the condensed state at the temperature prevailing in the 019 formation location where permeability alteration is desired.
020 Preferred monomers are essentially immiscible with water in the 021 condensed state at temperatures and pressures of interest.
022 Monomers useful in this invention can be further 023 categorized by considering the phenomena involved. The 024 vaporization and condensation equilibria for immiscible liquids 025 are discussed by Barnett F. Dodge, "Chemical Engineering 026 Thermodynamics", McGraw-Hill Book Company, Inc., New York, 027 1944, pp 533-535. The equilibrium vapor pressure over a 028 mixture of immiscible liquids, such as styrene and water, is 029 the sum of the vapor pressures of the individual components.
030 The system boiling point temperature is independent of the 031 liquid composition and is the temperature at which the sum of 032 the vapor pressures of the pure components equals the total 033 pressure. This phenomenon is important in that monomers with 034 boiling point temperatures considerably higher than the boiling 035 point temperature of water can be useful in this invention.
036 From the discussions above, limits may be set that 037 will better define monomers useful in the invention. The :1133387 002 monomer and water should be chemically nonreactive with each 003 other in the liquid and vapor states, and should be essentially 004 immiscible in the liguid state over the temperature range of 005 interest (say 60-600F). Any water-immiscible monomer with a 006 vapor pressure can be vaporized into a steam stream. For 007 practicality, a monomer that has a three-phase equilibrium 008 point (for the meaning of this point see Dodge, loc. cit.) 009 vapor monomer content of at least 10 wt. percent would be 010 preferred so that the condensed monomer phase will be of 011 sufficient local volume to effectively reduce the permeability.
012 For a monomer with a molecular weight of 80, the corresponding 013 three-phase equilibrium point composition data are shown in 014 Table 1.
018 Vapor Pressure, 019 Monomer, Wt.% Monomer, Mole% % of Total Pressure _ _ 02050 22.5 22.5 02120 5.6 5.6 02210 2.5 2.5 023 Thus a monomer useful in the invention would have as 024 an upper limit a vapor pressure on the order of 2.5% or 025 preferably 5.6~ of the total system pressure (the system 026 temperature and pressure are established by the saturated steam 027 injection stream). At a saturated steam pressure of 1 028 atmosphere (212F) the monomer vapor pressure would then be on 029 the order of 19 mm or preferably 43 mm Hg or greater. Thus 030 some monomers with 1 atmosphere boiling temperatures as high as 031 400F would be useful in the invention.
032 A lower boiling point limit for monomers useful in 033 the invention is established by considering the formation 034 temperature in which the monomer must condense. Thus the lower 035 boiling point limit for a monomer useful in the invention would 036 be several degrees F above the original reservoir temperature 037 at the pressure existing within the condensation region.
~133~7 002 The remaining requirement for monomers useful in the 003 invention is that the monomers must be thermally polymerizable 004 at the temperatures of interest. The rates of polymerization 005 are not too important. An immediate or "flash" polymerization 006 would be undesirable because the condensed monomer would not 007 have time to coalesce into a bulk phase. However, no common 008 monomers that meet the other monomer requirements will "flash"
009 polymerize under thermal initiation. Polymerizations extending 010 over days or weeks may not be detrimental in that low molecular 011 weight polymers may be as effective as higher molecular weight 012 polymers in permeability reduction.
013 Type of monomers that may be useful in this invention 014 are: vinyl compounds such as styrene and ring-substituted 015 styrene, 2-vinyl pyridine, 2-methyl-5-vinyl pyridine; vinyl 016 esters such as vinyl butyrate, vinyl-2-ethylhexanoate; vinyl 017 ethers such as vinyl butylether, vinyl 2-ethylhexyl ether;
018 acrylates such as acrylonitrile, acrylic and methacrylic acid 019 esters; dienes such as isoprene, chloroprene, 2-ethyl-1,3-buta-020 diene; acetylenes such as phenyl acetylene and phenoxy 021 acetylene. Combinations of monomers may also be used 022 effectively.
023 A preferred monomer in the invention is styrene, 024 preferred for its chemical and physical properties, its ready 025 availability, and low cost. Selected properties of styrene are 026 listed in Table 2. Table 3 lists data on the styrene-water 027 system.
003STYRENE (VINYLBENZENE) 004PHYSICAL AND CHEMICAL PROPE~TIES
006 Formula C6H5CH:CH2 007 Molecular Weight 104.144 008 Boiling Point, 1 atm. 145.2C 293.4F
009 Freezing Point in Air, 1 atm. -30.6C -23.1F
010 Critical Temperature 641K
011 Critical Pressure 575 psia 012Vapor Pressure log PmmHg = 6.95711-1445.58/(tC+203.43) 013At 200C 51.64 psia 014Liquid Density, g./ml. dt = 0.9238 - 0.0008766 t(C) 01525C 0.9019 016200C 0.7485 017Viscosity, cp at 25C 0.730 018 Heat Capacity, Liquid, 25-200C, Cal/g/C 0.525 Average 019 Heat of Vaporization, 200C, Cal/g. approx. 80 020Heat of Polymerization, Cal/g, 25C160.2 021 Volume Shrinkage on Polymerization17 025Vapor Pressure 026 100mm200mm 400mm 760mm 50 psia500 psia 027 Water, tF 125152 181 212 281 467 028 Styrene, tF 180 214 252 293 389 030 Polymer Pro~erties 031 Thermal polymerization of styrene monomer at 392F
032 should lead to polystyrene with a weight average molecular 033 weight near 25,000. In the absence of oxygen, this polymer 034 should be relatively stable at temperatures below 500F. Melt 035 viscosity may be on the order of 5000 centipoises.
036 To indicate the behavior that may be expected in the 037 field using styrene with steam, several laboratory experiments 038 were performed.
~.~3338~
002 Styrene and water were codistilled through a short 003 path distillation apparatus, with minimum reflux, at 004 temperatures near 200F. Distillations were done with and 005 without added ammonia in the system. No evidence of polymeri-006 zation was noted in the distillation flask or still head.
007 Collected distillate separated into two liquid phases. Nuclear 008 magnetic resonance (NMR~ spectra of the collected styrene layer 009 gave no indication of compounds other than styrene monomer (NMR
010 detects as little as 0.5 weight percent polystyrene in styrene 011 solution). After several days at room temperature, the 012 uninhibited styrene distillate had polymerized to a syrupy 013 stage.
014 A 4.5 inch, 40 x 60 mesh sand pack in a Hassler cell 015 was heated to 275F, and steam at 220F was injected for some 016 time to establish rate. Styrene (30 ml) was then metered into 017 the steam stream to produce a 10% by volume vapor. The pack 018 effluent, still vaporized, was condensed. Almost all of the 019 injected styrene was recovered as distillate. NMR indicated no 020 polystyrene in the distillate. No indication of polystyrene 021 was found in the sand pack.
022 Styrene and water, with and without ammonia added, 023 were heated at 392F in Hoke bombs under autogeneous pressure.
024 After heating two hours, the bombs were cooled to room tempera-025 ture and opened. In all cases the styrene layer had 026 polymerized to hard, glassy polystyrene.
027 A 60-inch, 40 x 60 mesh sand pack in a Hassler cell 028 was used for the following experiment. About one pore volume 029 (liquid basis) of steam was injected into the cold sand pack to 030 warm it up and establish injection rates. All effluent 031 collected was cool, liquid water. A 10% styrene - 90% steam 032 stream was injected until 20 ml styrene was in the sand pack.
033 No styrene was noted in the effluent. Injection was then 034 stopped, the ends of the sand pack were plugged, and the 035 ~assler cell was heated at 230F for 10 hours. The cooled sand 036 pack was not consolidated, but sand grains were stuck together.
037 Polystyrene was identified by NMR.
002 At room temperature, water was injected through 4.5 003 inch, 40 x 60 mesh sand packs to establish initial permeabi-004 lity. Liquid styrene and water were coinjected at equal 005 volumetric rates, with and without ammonia added, until styrene 006 was obvious in the effluent fluid. The sand packs were then 007 plugged at both ends and heated for 16 hours at 300F. After 008 cooling, solid polystyrene was cleaned from the end plugs and 009 water permeability was measured. In both cases, permeability 010 reduction was about 75%. The sand packs were found to be con-011 solidated with polystyrene; the consolidated sands were quite 012 friable.
013 These experiments show that styrene monomer poly-014 merizes in the presence of water and ammonia (1) in the bulk 015 liquid state at 392F, (2) after condensation in a sand pack at 016 230F, (3) as bulk liquid in a sand pack at 300F. They also 017 show that a styrene-water vapor stream can pass through a short 018 sand pack at 2759F with no apparent styrene polymerization.
019 While a certain preferred embodiment of the invention 020 has been specifically disclosed it is understood that the 021 invention is not limited thereto as many variations will be 022 readily apparent to those skilled in the art and the invention 023 is to be given its broadest possible interpretation within the 024 terms of the following claims.
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method for treating a subsurface earth formation in the neighborhood of a steam injection well to alter selectively the effective permeability of said formation at said distance, comprising the steps of:
(a) producing a vapor mixture consisting of steam and the vapor of a polymerizable monomer, said monomer in liquid state being immiscible with water, the steam being in excess so that at the pressures and temperatures of said subsurface earth formation being treated the first condensate will consist of water only; and (b) injecting said mixture into said subsurface earth formation being treated so that within said subsurface earth formation being treated the initial cooling of said vapor causes excess steam to condense out of said vapor, and after further cooling said monomer will begin to condense and deposit a separate immiscible phase, whereby said condensed monomer will polymerize to become a high-viscosity polymer, thereby substantially decreasing the effective permeability of said subsurface earth formation where said polymer has been deposited.
(a) producing a vapor mixture consisting of steam and the vapor of a polymerizable monomer, said monomer in liquid state being immiscible with water, the steam being in excess so that at the pressures and temperatures of said subsurface earth formation being treated the first condensate will consist of water only; and (b) injecting said mixture into said subsurface earth formation being treated so that within said subsurface earth formation being treated the initial cooling of said vapor causes excess steam to condense out of said vapor, and after further cooling said monomer will begin to condense and deposit a separate immiscible phase, whereby said condensed monomer will polymerize to become a high-viscosity polymer, thereby substantially decreasing the effective permeability of said subsurface earth formation where said polymer has been deposited.
2. The method of Claim 1 wherein said monomer is added to said steam as a liquid form and is vaporized into said steam to form a vapor mixture whose first condensation product as it cools will consist of liquid water only.
3. The method of Claim 1 wherein said monomer is added to said steam in vapor form.
4. The method of Claim 1 with the addition of ammonia to said mixture.
5. The method of Claim 4 wherein said ammonia is added to establish an ammonia concentration in the mixture equivalent to about 1% by weight of the monomer concentration.
6. The method of Claim 1 wherein the monomer is styrene and the mixture of steam and monomer is at a weight ratio of about 1 to 4 of monomer to steam.
7. The method of treating a subsurface earth formation to selectively control the effective permeability therein, comprising the steps of:
(a) producing steam and injecting said steam into said subsurface earth formation at a temperature and pressure that will cause said steam to be a vapor at the subsurface formation whose effective permeability is to be controlled;
(b) vaporizing a polymerizable monomer into said produced steam so as to form a mixture of steam and monomer and injecting said mixture into said subsurface earth formation;
(c) terminating the addition of monomer to said steam while continuing to inject steam to drive said mixture into said subsurface earth formation so as to cause said mixture to be placed within said subsurface earth formation in said formation whose effective permeability is to be controlled;
so that said injected mixture will condense within said subsurface earth formation to produce a liquid water phase and a liquid monomer phase within said subsurface earth formation whose effective permeability is to be controlled and so that said monomer will polymerize within said formation to form a high-viscosity polymer within said formation to reduce the effective permeability thereof.
(a) producing steam and injecting said steam into said subsurface earth formation at a temperature and pressure that will cause said steam to be a vapor at the subsurface formation whose effective permeability is to be controlled;
(b) vaporizing a polymerizable monomer into said produced steam so as to form a mixture of steam and monomer and injecting said mixture into said subsurface earth formation;
(c) terminating the addition of monomer to said steam while continuing to inject steam to drive said mixture into said subsurface earth formation so as to cause said mixture to be placed within said subsurface earth formation in said formation whose effective permeability is to be controlled;
so that said injected mixture will condense within said subsurface earth formation to produce a liquid water phase and a liquid monomer phase within said subsurface earth formation whose effective permeability is to be controlled and so that said monomer will polymerize within said formation to form a high-viscosity polymer within said formation to reduce the effective permeability thereof.
8. The method of Claim 7 wherein said monomer has a boiling point at atmospheric pressure within the range of about 60°F to 400°F.
9. In the recovery of subsurface petroleum by steam injection, into a petroleum-containing formation, the method of increasing the sweep efficiency of the steam injection, comprising:
adding to the injected steam a monomer, said monomer being:
(a) vaporizable into the steam at the injection pre-ssure and temperature;
(b) condensable at the prevailing temperatures and pressures within the petroleum-containing formation; and (c) thermally polymerizable in the condensed state at the prevailing temperatures and pressures within the petroleum-containing formation.
adding to the injected steam a monomer, said monomer being:
(a) vaporizable into the steam at the injection pre-ssure and temperature;
(b) condensable at the prevailing temperatures and pressures within the petroleum-containing formation; and (c) thermally polymerizable in the condensed state at the prevailing temperatures and pressures within the petroleum-containing formation.
10. The method of Claim 9 in which said monomer in its liquid phase is immiscible with water.
11. In the recovery of subsurface petroleum by steam in-jection, the method of increasing the sweep efficiency of the steam injection comprising:
adding styrene monomer vapor to the steam to be injected, and injecting said steam containing styrene into said subsurface.
adding styrene monomer vapor to the steam to be injected, and injecting said steam containing styrene into said subsurface.
12. The method of Claim 11 in which the concentration of styrene monomer vapor in the injected steam is kept below that concentration at which liquid styrene could exist in equili-brium with the composite vapor of water and styrene.
13. The method of Claim 11 in which ammonia is added to the styrene-containing steam to inhibit the vapor-phase polymerization of styrene during passage of the styrene-containing steam down the wellbore and out into its intended formation location.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US27,537 | 1979-04-05 | ||
| US06/027,537 US4250963A (en) | 1979-04-05 | 1979-04-05 | Selective permeability reduction with polymerizable monomers around steam injection wells |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1133387A true CA1133387A (en) | 1982-10-12 |
Family
ID=21838292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA340,033A Expired CA1133387A (en) | 1979-04-05 | 1979-11-16 | Selective permeability reduction with polymerizable monomers around steam injection wells |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US4250963A (en) |
| CA (1) | CA1133387A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3405201A1 (en) * | 1984-02-14 | 1985-08-22 | Lentia GmbH Chem. u. pharm. Erzeugnisse - Industriebedarf, 8000 München | METHOD FOR IMPROVING THE DETOILING OF UNDERGROUND OIL RESOURCES |
| US4799548A (en) * | 1987-01-23 | 1989-01-24 | Phillips Petroleum Company | Gelable compositions and use thereof in steam treatment of wells |
| US4845134A (en) * | 1987-01-23 | 1989-07-04 | Phillips Petroleum Company | Gelable compositions and use thereof in steam treatment of wells |
| US4817721A (en) * | 1987-12-14 | 1989-04-04 | Conoco Inc. | Reducing the permeability of a rock formation |
| US4903770A (en) * | 1988-09-01 | 1990-02-27 | Texaco Inc. | Sand consolidation methods |
| DE4004240C1 (en) * | 1990-02-12 | 1990-11-29 | Forschungszentrum Juelich Gmbh, 5170 Juelich, De | |
| US5199490A (en) * | 1991-11-18 | 1993-04-06 | Texaco Inc. | Formation treating |
| CN105308261A (en) | 2013-06-18 | 2016-02-03 | 国际壳牌研究有限公司 | Oil recovery system and method |
| CN105339585A (en) | 2013-06-27 | 2016-02-17 | 国际壳牌研究有限公司 | Remediation of asphaltene-induced plugging of wellbores and production lines |
| WO2015095479A1 (en) * | 2013-12-20 | 2015-06-25 | Shell Oil Company | Oil recovery process, system, and composition |
| MX2016012834A (en) * | 2014-04-01 | 2017-04-27 | Future Energy Llc | Thermal energy delivery and oil production arrangements and methods thereof. |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2272673A (en) * | 1936-03-24 | 1942-02-10 | Gulf Research Development Co | Gas repressuring of oil fields |
| US2274297A (en) * | 1938-12-16 | 1942-02-24 | Dow Chemical Co | Method of treating earth and rock formations |
| US2799341A (en) * | 1955-03-04 | 1957-07-16 | Union Oil Co | Selective plugging in oil wells |
| US3180414A (en) * | 1961-03-27 | 1965-04-27 | Phillips Petroleum Co | Production of hydrocarbons by fracturing and fluid drive |
| US3373812A (en) * | 1965-07-09 | 1968-03-19 | Gulf Research Development Co | Method of permeably consolidating incompetent sands with a heat-curable resin |
| US3369603A (en) * | 1965-09-02 | 1968-02-20 | Phillips Petroleum Co | Plugging of a formation adjacent an oil stratum |
-
1979
- 1979-04-05 US US06/027,537 patent/US4250963A/en not_active Expired - Lifetime
- 1979-11-16 CA CA340,033A patent/CA1133387A/en not_active Expired
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| US4250963A (en) | 1981-02-17 |
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