CA2005853A1 - Method for plugging a high permeability zone with a heat activated gel - Google Patents
Method for plugging a high permeability zone with a heat activated gelInfo
- Publication number
- CA2005853A1 CA2005853A1 CA002005853A CA2005853A CA2005853A1 CA 2005853 A1 CA2005853 A1 CA 2005853A1 CA 002005853 A CA002005853 A CA 002005853A CA 2005853 A CA2005853 A CA 2005853A CA 2005853 A1 CA2005853 A1 CA 2005853A1
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- 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
- E21B43/164—Injecting CO2 or carbonated water
-
- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Mining & Mineral Resources (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Colloid Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
METHOD FOR SELECTIVELY PLUGGING A ZONE HAVING
VARYING PERMEABILITIES WITH A TEMPERATURE ACTIVATED GEL
ABSTRACT
A process for closing pores in a heated steam swept zone of a formation having zones of varying permeabilities where a temperature activated aqueous gellable mixture is utilized following a steam flooding or steam stimulation enhanced oil recovery method.
After being placed into the steam swept zone having varying permeabilities, a temperature above 300°F activates components in the gellable mixture which causes a solid gel to form which closes pores in the steam swept zone. A spacer volume of cold water is pumped into the formation to remove any ungelled mixture. Steam is directed into an unswept zone and hydrocarbonaceous fluids recovered therefrom. Polymers utilized include polyvinyl alcohol and polyacrylamide cross-linked with phenol, and an aldehyde producing compound sufficient to form a phenolic resin in situ.
VARYING PERMEABILITIES WITH A TEMPERATURE ACTIVATED GEL
ABSTRACT
A process for closing pores in a heated steam swept zone of a formation having zones of varying permeabilities where a temperature activated aqueous gellable mixture is utilized following a steam flooding or steam stimulation enhanced oil recovery method.
After being placed into the steam swept zone having varying permeabilities, a temperature above 300°F activates components in the gellable mixture which causes a solid gel to form which closes pores in the steam swept zone. A spacer volume of cold water is pumped into the formation to remove any ungelled mixture. Steam is directed into an unswept zone and hydrocarbonaceous fluids recovered therefrom. Polymers utilized include polyvinyl alcohol and polyacrylamide cross-linked with phenol, and an aldehyde producing compound sufficient to form a phenolic resin in situ.
Description
X0~5853 ~;THOD FOR SELECI IVELY PLUGGING A ZONE HAVING
VARYING P~RMEABILITIES WIIH A TEMPERAllJRE ACIIYAlED GEL
This invention relates to the use of temperature activated gels that can be us~d for profile control after a steam flood so that increased amounts of hydrocarbonaceous fluids can be obtained from a steam underswept zone in a formation.
In the recovery of oil from oil-containing formations, it is usually possible to recover only minor portions of the original oil-in-place by so-called primary recovery methods which utilize only natural forces. To increase the recovery of oil a variety of supplementary rec~very techniques are employed. These techniques include water~looding, miscible flooding, and thermal recovery.
A problem that arises in various flooding processes is that dif~erent strata or zones in the reservoir often possess different permeabilities. Thus, displacing fluids enter high permeability or "thief" zones in preference to zones of lower permeability.
Significant quantities of oil may be left in zones of lower permeability. To circumvent this difficulty the technique of profile control is applied to plug the high permeability zones with polyrneric gels and thus divert the displacing fluid into the underswept low perlneability, oil rich zones. Among the polymers examined for improving waterflood conformance are metal cross-linked polysaccharides, metal cross-linked polyacrylamides, and organic-crosslinked polyacrylamides.
Polymeric ~els are disclosed in several U.S. patents.
Among these is ~.S. Patent No. 4,157,322 which issued to Colegrove on June 5, 1979. Ihis gel is formed rom water, a polysaccharide polymer, an acid generating salt and a melamine resin. ~ polymeric gel is disclosed in U.S. Patent No. 4,658,898 which issued to Paul et al. on April 21, 1987. lhis patent discloses an aqeuous solution of heteropolysaccharide S-130 combined with cations of basic organic compounds which cations contained at least two positively charged centers. U.S. Patent No. 4,716,966, issued to Shu on January 5, 1988, discloses a gel formed by amino resins such as melamine formaldehyde which modify biopolymers in combination with transitional metal ions.
Basic to the problem of diverting displacing fluid with polymeric gels is the necessity of placing the polymer where it is needed, i.e. in the high permeability zone. This is possible when xanthan biopolymers are cross-linked with metal ions such as Cr 3 above ground to give gels. '~ese gels are shear stable and shear thinning. They can be injec~ed into the formation where they then reheal. Due to the gel's rheological properties, they will of necessity go into hig~i permeability zones. However, many other gel systems are formed in-situ. One system disclosed in U.S. Patent 3,557,562 contains acrylamide monomer, methylene-bis-acrylamide as an organic cross-linker, and a free radical initiator. This system undergoes polymerization in the fo~mation to give a polyacrylamide cross-linked with methylene- bis-acrylamide. However, the viscosity of the solution when injected is like that of water. Unless mechanical isolation is used, these solutions are quite capable of penetrating low permeability, oil bearing zones. Another form of in-situ gelation involves the injection of polyacrylamide containing chromium in the form of chromate. A reducing agent such as thiourea or sodium thiosulfate is also injected to reduce the chromate in-situ to Cr~3, a species capable of cross-linking hydrolyzed polyacrylamide. rven though the polyacrylamide solution has a viscosity greateI than water, it is not capable of showing the selectivity that a gel can. Thus, polyacrylamidcs cross-linked with chromium in-situ can also go into low permeability zones. It is not useful to cross-link polyacrylamides above ground and inject them as gels, because polyacrylamide gels undergo shear degradation. There are very few gels that are selective and thermally stable.
In addition to the creation of "thief" zones during a waterflooding recovery technique, steam flooding or steam ~005~3 F-5035 ~ 3 ~
stimulation processes create a unique situation known as gravity override due to the steam's low density. Because of the steam's low density, the sweep path of the steam is therefore biased towards the top of the payzone. Thus, the area invaded by the override steam may or may not be ~ low permeability. Although steam preferentially enters a high permeability or thief zone, the high temperature of the steam will also remove hydrocarbonaceous fluids from portions of low permeability zones. As the distance increases from steam entry into the formation, the temperature will decrease.
As long as the temperature is hot enough hydrocarbonaceous fluids will be removed from the "thief" zone as well as portions of low permeability zones.
When steam has broken through to a production well during a steamflood, a heated portion of the formation will communicate with an injector well. This heated portion may include portions of both high and low permeability steam override zones. For this reason, a gel system which can selectiveiy enter a high permeability "thief"-zone may not enter a low permeability zoné. Thus, a sîze selective gel may not prevent steam from entering into a heated low permeability zone which has been depleted of hydrocarbonaceous fluids.
Therefore, what is needed is a method whereby a gel folms in-situ in a steam overswept zone of a formation only when said zone has been previously heated during a steamflood enhanced oil recovery process regardless of its permeability.
This inven~ion is directed to a method for closing pores in a heated steam overswept zone which composition comprises a temperature activated gellable mixture which ~orms a solid gel. In one embodiment o this invention, the more permeable and the override zones are heated during a steam flcoding enhanced oil recovery (EOR) process. Due to preferential steam flow through said zones, such zones are overswept by steam. Therefore, they are more oil-depleted. Once the steam flow is stopped, the heat activated gellable mixture is injected into the formation. When the gellable X00~353 mixture has travelled the desired distance into the forrnation, injection of said gellable mixture is ceased. Heat emitted fronl the stearn overswept zone activates the gellable mixture upon reaching a temperature of above 300F thereby causing it to form a solid gel and close pores in the steam overswept zone.
Gellable aqueous compositions which can form a solid gel upon reaching a temperature above 300F are comprised of selected water dispersible polyrners, phenolic compounds, and aldehyde producing compounds. Polymers which are utilized herein are selected from a member of the group consisting of polyviJIyl alcohol, polyvinyl alcohol copolyrners, polyacrylamide, polyvinyl amine, sulfonated polyvinyl alcohol, and poly (acrylamide-co-acrylamido-2-methy]propane sulfonate). Phenolic compounds which can be used include phenol, catechol, resorcinol, phloroglucinol, 4,4'-diphenol, 1,3-dihydroxynaphthalene, and related similar compounds. Aldehyde producing compounds which can be utilized herein upon reaching a temperature above 300F include trioxane and paraformaldehyde, tetraoxane.
It is therefore an object of this invention to provide for a temperature activated gellable composition which can be delivered into a heated steam overswept zone having a temperature suf~icient to activate said cornposition and selectively form a solid gel therein.
This invention provides for a temperature activated gellable composition which can be delivered into a forrnation's stearn override zone having a temperature above 300F and thereafter ~orm a solid gel therein.
This invention also provides for a composition which avoids forming a solid gel in a stearn underswept zone of lesser permeability or a low temperature zone of a formation.
This invention further provides for a composition that will minimize gel darnage to a zone of lower penneability while closing pores in a higher permeability zone having a ternperature above 300F.
X00~8S~
F-5035 ~ 5 ~
This in~ention also provides for injecting a temperature activated gellable composition into a producer well, causing a solid gel to form so as to divert sweep fluids into an unswept formation zone.
This invention further provides for a composition which will increase the efficiency of a drive fluid through a formation thereby increasing the yield of hydrocarbonaceous fluids therefrom.
FIG. 1 is a diagrammatic plan v;ew of a formation where steam has passed through a high permeability zone and its override area into a production well.
FIG. 2 is a schematic representation which illustrates temperature distribution into high and low permeability zones of a formation during steam flooding.
FIG. 3 is a diagrammatic plan view where the high permeability and override zones have been closed with a temperature activated gel while steam is passing through a low permeability zone or area.
During the recovery o~ hydrocarbonaceous fluids from a formation wherein a steam flooding process is utilized, as is shown in FIG. 1, steam enters conduit 14 of injection well 10.
Afterwards, steam exits injection well 10 via perforations 22 and enters high permeability zone 20. Steam and hydrocarbons obtained from high permeability zone 20 exit through production well 12 via perforations 26. m ereafter, steam and hydrocarbonaceous fluids exit production well 12 via conduit 16. During this steam flooding process, the formation is heated up by the steam. While being heated, a temperature contour is developed in the steam flooded formation. Thus, the "thief" zones and zones swept by override steam have the highest temperatures in the formation while the underswept parts in the formation have the lowest. This concept is illustrated in FIG. 2. When it becomes uneconomical to continue injecting steam to recover hydrocarbonaceous fluids from high xoosa53 permeability zone 20, high permeability or overswept zone 20 is closed so that hydrocarbonaceous fluids can be removed from low permeability zone 18. Closing of the overswept zone is depicted in Fig. 3. In the practice of this invention, an aqueous gellable temperature acti~ated mixture is injected via conduit 14 into injection well 10 where it enters high permeability or overswept zone 20. When the gellable temperature activated mixture comes into contact with heated high permeability or overswept zone 20, components in the aqueous gellable mixture form a solid gel which blocks pores in high permeability zone 20. Due to the high porosi~y of high permeability or overswept zone 20, the aqueous gellable mixture preferentially enters high permeability zone 20. This aqueous gellable mixture is injected into the high permeability or overswept zone 20 after the steam flooding operation has been ceased.
Once in high permeability zone 20, the aqueous gellable mixture is allowed sufficient time to form a solid gel. Generally the solid gel will form at a temperature greater than 300F in from 1 to 20 days. Although some of the aqueous gellable mixture may enter low permeability or underswept zone 18, it will not form a gel in that portion of low permeability zone 18 where the temperature is too low. Any gellable mixture which cnters low permeability zone 18 where the temperature is too low for gelation can be removed therefrom by pumping a spacer vol~ne of cold water therethrough so as to make the mixture ungellable. An additional beneEit of the ungelled aqueous mixture is that being Viscolls it can act as a mobility control agent so as to facilitate the removal of hydrocarbonaccous fluids from low permeability zone 18.
Alternatively, any ungelled materials can be pumped out or produced back to the surface if the producer well is treated. If the gellable compositions are used in conjunction with a water-alternating-gas tWAG) process, the ungelled material need not be pumped or removed from the formation since it can advantageously act as a mobility control agent. A WAG process is discussed in U.S.
Patent No. 4,640,357.
~005i853 F-5035 ~ 7 ~
Aqueous gellable temperature activated compositions which can be utili~ed herein are comprised of a polymer, a phenolic compound, and an aldehyde. Polymers utilized herein are water dispersible polymers. The term "polymer" is ernployed generically to include both homopolymers and copolymers. The term "water-dispersible polymers" is used generically to include those polymers which are truly water-soluble and those polymers which are dispersible in water or in other aqueous medium to form stable colloidal suspensions which can be gelled. Also, the term "aqueous dispersion" is utilized generically to include both true solutions and stable colloidal suspensions of colnponents of the composition of this invention which can be gelled as will be described herein.
Water- dispersible polymers which are used herein are selected from a member of the group consisting of polyvinyl alcohol, polyacrylamide, sulfonated polyvinyl alcohol, and poly (acrylamide-co-acrylamido-2-methylpropane sulfonate). Polyvinyl alcohol (PVA) at various degrees of hydrolysis are useful. Other polymers containing OH, NH2, CONH2, and SH aTe a~so useful.
Polyvinyl amine, and copolymers containing the previously mentioned functional groups are useful. Any of these water-dispersible polymers are placed into an aqueous mixture in amount o~ from n.5 to 10.0 wt.%. The aqueous medium can comprise fresh water, brackish water, or sea wateL, and mixtures thereof. Polyacrylamide and poly(2-acrylamido-2- methylpropane sul~onate) are discussed in U.S.
Patent No. 4,440,228 which issued on April 3, 1984 to Swanson.
After placing the selected water-dispersible polymer into the aqueous mediurn, a phenolic compound is added to the mixture.
Phenolic compounds which can be used herein include phenol, naphthol, catechol, resorcinol, phloroglucinol, 4,4'-diphenol, 1,3-dihydroxynaphthalene, and related similar compounds. The arno~mt of phenolic compound utili~ed should be in excess of 0.5 wt.% or higher. The amount of phenolic compound used herein should be sufficient to impart the desired gelation effect within the desired time period.
~0~5853 Once t'he phenolic compound has been added, a water-dispersible aldehyde producing compound is mixed ~nto the aqueous mixture. Representative examples of such aldehydes producing compounds include trioxane, tetraoxane, polyoxymethylene, and other aldehyde precursors. The term "water-dispersible" is employed generically to include aldehyde producing compounds which are truly water-soluble and those aldehydes of limited water solubility but which are dispersible in water or other aqueous media so as to be effective gelling agents. The preferred aldehyde is trioxane.
Any suitable amo,~nt o~ trioxane and phenolic co~pounds can be utilized herein. In all instances, the amount of aldehyde and phenolic compound used should be in an amount sufficient to cause gelation of an aqueous dispersion of a polymer, the aldehyde, and the phenolic compound. As a general guide, the amount o~ aldehyde used in preparing the gel compositions herein will be in the range of from 0.5 to lO.O, preferably l.O to 5.0 wt.% based on the total weight of the composition.
A preferred temperature activated gellable mixture comprises polyvinyl alcohol, phenol, and trioxane. The effect of temperature on said mixture is shown in Table l. When exposed to a formation having a temperature of 300 to 350F or higher, a Eirm gel will form in about l day to 15 days when 0.05 to 0.5 wt.~ of sodium hydroxide is utilized as is shown in Table 2. Polyvinyl alcohol is used in amounts of 0.5 to 5.0 wt.~. Phenol is used in 0.5 to 5.0 wt.% or higher. The phenol to trioxane ratio is 0.5 to 1.5, preferably l.O. l'he polyvinyl alcohol/phenol welght ratio is ~rom 0.2 to 2. OE course, a lower ratio is used when other higher molecular weight polymers are utilized. The total concentration of polymer, phenol, and trio~ane is directly proportional to the gel strength. A rigid gel is ~ormed which is proportional to the total materials content.
Z00~.~53 F-5035 - 9 ~
Temperature Sensitivity of PVA~Phenol/Trioxane * Gelation Temp, F 200 300 350 400 450 Gel Time, days no gel no gel * 2.5% PVA, 4~ phenol, 3% trioxane Effect of N~OH Concentration on Gel * Time 300F 3SOCF ~ 0F 450F
NaOH, %
._ 0.05 No gel lS days8-9 days 4 days 0.1 " lS " 5-7 " 2 "
0.2 " 12 " 2 " 1 day 0.3 " 9 " 1 day 1 "
0.5 " 6 " 1 " 1 "
VARYING P~RMEABILITIES WIIH A TEMPERAllJRE ACIIYAlED GEL
This invention relates to the use of temperature activated gels that can be us~d for profile control after a steam flood so that increased amounts of hydrocarbonaceous fluids can be obtained from a steam underswept zone in a formation.
In the recovery of oil from oil-containing formations, it is usually possible to recover only minor portions of the original oil-in-place by so-called primary recovery methods which utilize only natural forces. To increase the recovery of oil a variety of supplementary rec~very techniques are employed. These techniques include water~looding, miscible flooding, and thermal recovery.
A problem that arises in various flooding processes is that dif~erent strata or zones in the reservoir often possess different permeabilities. Thus, displacing fluids enter high permeability or "thief" zones in preference to zones of lower permeability.
Significant quantities of oil may be left in zones of lower permeability. To circumvent this difficulty the technique of profile control is applied to plug the high permeability zones with polyrneric gels and thus divert the displacing fluid into the underswept low perlneability, oil rich zones. Among the polymers examined for improving waterflood conformance are metal cross-linked polysaccharides, metal cross-linked polyacrylamides, and organic-crosslinked polyacrylamides.
Polymeric ~els are disclosed in several U.S. patents.
Among these is ~.S. Patent No. 4,157,322 which issued to Colegrove on June 5, 1979. Ihis gel is formed rom water, a polysaccharide polymer, an acid generating salt and a melamine resin. ~ polymeric gel is disclosed in U.S. Patent No. 4,658,898 which issued to Paul et al. on April 21, 1987. lhis patent discloses an aqeuous solution of heteropolysaccharide S-130 combined with cations of basic organic compounds which cations contained at least two positively charged centers. U.S. Patent No. 4,716,966, issued to Shu on January 5, 1988, discloses a gel formed by amino resins such as melamine formaldehyde which modify biopolymers in combination with transitional metal ions.
Basic to the problem of diverting displacing fluid with polymeric gels is the necessity of placing the polymer where it is needed, i.e. in the high permeability zone. This is possible when xanthan biopolymers are cross-linked with metal ions such as Cr 3 above ground to give gels. '~ese gels are shear stable and shear thinning. They can be injec~ed into the formation where they then reheal. Due to the gel's rheological properties, they will of necessity go into hig~i permeability zones. However, many other gel systems are formed in-situ. One system disclosed in U.S. Patent 3,557,562 contains acrylamide monomer, methylene-bis-acrylamide as an organic cross-linker, and a free radical initiator. This system undergoes polymerization in the fo~mation to give a polyacrylamide cross-linked with methylene- bis-acrylamide. However, the viscosity of the solution when injected is like that of water. Unless mechanical isolation is used, these solutions are quite capable of penetrating low permeability, oil bearing zones. Another form of in-situ gelation involves the injection of polyacrylamide containing chromium in the form of chromate. A reducing agent such as thiourea or sodium thiosulfate is also injected to reduce the chromate in-situ to Cr~3, a species capable of cross-linking hydrolyzed polyacrylamide. rven though the polyacrylamide solution has a viscosity greateI than water, it is not capable of showing the selectivity that a gel can. Thus, polyacrylamidcs cross-linked with chromium in-situ can also go into low permeability zones. It is not useful to cross-link polyacrylamides above ground and inject them as gels, because polyacrylamide gels undergo shear degradation. There are very few gels that are selective and thermally stable.
In addition to the creation of "thief" zones during a waterflooding recovery technique, steam flooding or steam ~005~3 F-5035 ~ 3 ~
stimulation processes create a unique situation known as gravity override due to the steam's low density. Because of the steam's low density, the sweep path of the steam is therefore biased towards the top of the payzone. Thus, the area invaded by the override steam may or may not be ~ low permeability. Although steam preferentially enters a high permeability or thief zone, the high temperature of the steam will also remove hydrocarbonaceous fluids from portions of low permeability zones. As the distance increases from steam entry into the formation, the temperature will decrease.
As long as the temperature is hot enough hydrocarbonaceous fluids will be removed from the "thief" zone as well as portions of low permeability zones.
When steam has broken through to a production well during a steamflood, a heated portion of the formation will communicate with an injector well. This heated portion may include portions of both high and low permeability steam override zones. For this reason, a gel system which can selectiveiy enter a high permeability "thief"-zone may not enter a low permeability zoné. Thus, a sîze selective gel may not prevent steam from entering into a heated low permeability zone which has been depleted of hydrocarbonaceous fluids.
Therefore, what is needed is a method whereby a gel folms in-situ in a steam overswept zone of a formation only when said zone has been previously heated during a steamflood enhanced oil recovery process regardless of its permeability.
This inven~ion is directed to a method for closing pores in a heated steam overswept zone which composition comprises a temperature activated gellable mixture which ~orms a solid gel. In one embodiment o this invention, the more permeable and the override zones are heated during a steam flcoding enhanced oil recovery (EOR) process. Due to preferential steam flow through said zones, such zones are overswept by steam. Therefore, they are more oil-depleted. Once the steam flow is stopped, the heat activated gellable mixture is injected into the formation. When the gellable X00~353 mixture has travelled the desired distance into the forrnation, injection of said gellable mixture is ceased. Heat emitted fronl the stearn overswept zone activates the gellable mixture upon reaching a temperature of above 300F thereby causing it to form a solid gel and close pores in the steam overswept zone.
Gellable aqueous compositions which can form a solid gel upon reaching a temperature above 300F are comprised of selected water dispersible polyrners, phenolic compounds, and aldehyde producing compounds. Polymers which are utilized herein are selected from a member of the group consisting of polyviJIyl alcohol, polyvinyl alcohol copolyrners, polyacrylamide, polyvinyl amine, sulfonated polyvinyl alcohol, and poly (acrylamide-co-acrylamido-2-methy]propane sulfonate). Phenolic compounds which can be used include phenol, catechol, resorcinol, phloroglucinol, 4,4'-diphenol, 1,3-dihydroxynaphthalene, and related similar compounds. Aldehyde producing compounds which can be utilized herein upon reaching a temperature above 300F include trioxane and paraformaldehyde, tetraoxane.
It is therefore an object of this invention to provide for a temperature activated gellable composition which can be delivered into a heated steam overswept zone having a temperature suf~icient to activate said cornposition and selectively form a solid gel therein.
This invention provides for a temperature activated gellable composition which can be delivered into a forrnation's stearn override zone having a temperature above 300F and thereafter ~orm a solid gel therein.
This invention also provides for a composition which avoids forming a solid gel in a stearn underswept zone of lesser permeability or a low temperature zone of a formation.
This invention further provides for a composition that will minimize gel darnage to a zone of lower penneability while closing pores in a higher permeability zone having a ternperature above 300F.
X00~8S~
F-5035 ~ 5 ~
This in~ention also provides for injecting a temperature activated gellable composition into a producer well, causing a solid gel to form so as to divert sweep fluids into an unswept formation zone.
This invention further provides for a composition which will increase the efficiency of a drive fluid through a formation thereby increasing the yield of hydrocarbonaceous fluids therefrom.
FIG. 1 is a diagrammatic plan v;ew of a formation where steam has passed through a high permeability zone and its override area into a production well.
FIG. 2 is a schematic representation which illustrates temperature distribution into high and low permeability zones of a formation during steam flooding.
FIG. 3 is a diagrammatic plan view where the high permeability and override zones have been closed with a temperature activated gel while steam is passing through a low permeability zone or area.
During the recovery o~ hydrocarbonaceous fluids from a formation wherein a steam flooding process is utilized, as is shown in FIG. 1, steam enters conduit 14 of injection well 10.
Afterwards, steam exits injection well 10 via perforations 22 and enters high permeability zone 20. Steam and hydrocarbons obtained from high permeability zone 20 exit through production well 12 via perforations 26. m ereafter, steam and hydrocarbonaceous fluids exit production well 12 via conduit 16. During this steam flooding process, the formation is heated up by the steam. While being heated, a temperature contour is developed in the steam flooded formation. Thus, the "thief" zones and zones swept by override steam have the highest temperatures in the formation while the underswept parts in the formation have the lowest. This concept is illustrated in FIG. 2. When it becomes uneconomical to continue injecting steam to recover hydrocarbonaceous fluids from high xoosa53 permeability zone 20, high permeability or overswept zone 20 is closed so that hydrocarbonaceous fluids can be removed from low permeability zone 18. Closing of the overswept zone is depicted in Fig. 3. In the practice of this invention, an aqueous gellable temperature acti~ated mixture is injected via conduit 14 into injection well 10 where it enters high permeability or overswept zone 20. When the gellable temperature activated mixture comes into contact with heated high permeability or overswept zone 20, components in the aqueous gellable mixture form a solid gel which blocks pores in high permeability zone 20. Due to the high porosi~y of high permeability or overswept zone 20, the aqueous gellable mixture preferentially enters high permeability zone 20. This aqueous gellable mixture is injected into the high permeability or overswept zone 20 after the steam flooding operation has been ceased.
Once in high permeability zone 20, the aqueous gellable mixture is allowed sufficient time to form a solid gel. Generally the solid gel will form at a temperature greater than 300F in from 1 to 20 days. Although some of the aqueous gellable mixture may enter low permeability or underswept zone 18, it will not form a gel in that portion of low permeability zone 18 where the temperature is too low. Any gellable mixture which cnters low permeability zone 18 where the temperature is too low for gelation can be removed therefrom by pumping a spacer vol~ne of cold water therethrough so as to make the mixture ungellable. An additional beneEit of the ungelled aqueous mixture is that being Viscolls it can act as a mobility control agent so as to facilitate the removal of hydrocarbonaccous fluids from low permeability zone 18.
Alternatively, any ungelled materials can be pumped out or produced back to the surface if the producer well is treated. If the gellable compositions are used in conjunction with a water-alternating-gas tWAG) process, the ungelled material need not be pumped or removed from the formation since it can advantageously act as a mobility control agent. A WAG process is discussed in U.S.
Patent No. 4,640,357.
~005i853 F-5035 ~ 7 ~
Aqueous gellable temperature activated compositions which can be utili~ed herein are comprised of a polymer, a phenolic compound, and an aldehyde. Polymers utilized herein are water dispersible polymers. The term "polymer" is ernployed generically to include both homopolymers and copolymers. The term "water-dispersible polymers" is used generically to include those polymers which are truly water-soluble and those polymers which are dispersible in water or in other aqueous medium to form stable colloidal suspensions which can be gelled. Also, the term "aqueous dispersion" is utilized generically to include both true solutions and stable colloidal suspensions of colnponents of the composition of this invention which can be gelled as will be described herein.
Water- dispersible polymers which are used herein are selected from a member of the group consisting of polyvinyl alcohol, polyacrylamide, sulfonated polyvinyl alcohol, and poly (acrylamide-co-acrylamido-2-methylpropane sulfonate). Polyvinyl alcohol (PVA) at various degrees of hydrolysis are useful. Other polymers containing OH, NH2, CONH2, and SH aTe a~so useful.
Polyvinyl amine, and copolymers containing the previously mentioned functional groups are useful. Any of these water-dispersible polymers are placed into an aqueous mixture in amount o~ from n.5 to 10.0 wt.%. The aqueous medium can comprise fresh water, brackish water, or sea wateL, and mixtures thereof. Polyacrylamide and poly(2-acrylamido-2- methylpropane sul~onate) are discussed in U.S.
Patent No. 4,440,228 which issued on April 3, 1984 to Swanson.
After placing the selected water-dispersible polymer into the aqueous mediurn, a phenolic compound is added to the mixture.
Phenolic compounds which can be used herein include phenol, naphthol, catechol, resorcinol, phloroglucinol, 4,4'-diphenol, 1,3-dihydroxynaphthalene, and related similar compounds. The arno~mt of phenolic compound utili~ed should be in excess of 0.5 wt.% or higher. The amount of phenolic compound used herein should be sufficient to impart the desired gelation effect within the desired time period.
~0~5853 Once t'he phenolic compound has been added, a water-dispersible aldehyde producing compound is mixed ~nto the aqueous mixture. Representative examples of such aldehydes producing compounds include trioxane, tetraoxane, polyoxymethylene, and other aldehyde precursors. The term "water-dispersible" is employed generically to include aldehyde producing compounds which are truly water-soluble and those aldehydes of limited water solubility but which are dispersible in water or other aqueous media so as to be effective gelling agents. The preferred aldehyde is trioxane.
Any suitable amo,~nt o~ trioxane and phenolic co~pounds can be utilized herein. In all instances, the amount of aldehyde and phenolic compound used should be in an amount sufficient to cause gelation of an aqueous dispersion of a polymer, the aldehyde, and the phenolic compound. As a general guide, the amount o~ aldehyde used in preparing the gel compositions herein will be in the range of from 0.5 to lO.O, preferably l.O to 5.0 wt.% based on the total weight of the composition.
A preferred temperature activated gellable mixture comprises polyvinyl alcohol, phenol, and trioxane. The effect of temperature on said mixture is shown in Table l. When exposed to a formation having a temperature of 300 to 350F or higher, a Eirm gel will form in about l day to 15 days when 0.05 to 0.5 wt.~ of sodium hydroxide is utilized as is shown in Table 2. Polyvinyl alcohol is used in amounts of 0.5 to 5.0 wt.~. Phenol is used in 0.5 to 5.0 wt.% or higher. The phenol to trioxane ratio is 0.5 to 1.5, preferably l.O. l'he polyvinyl alcohol/phenol welght ratio is ~rom 0.2 to 2. OE course, a lower ratio is used when other higher molecular weight polymers are utilized. The total concentration of polymer, phenol, and trio~ane is directly proportional to the gel strength. A rigid gel is ~ormed which is proportional to the total materials content.
Z00~.~53 F-5035 - 9 ~
Temperature Sensitivity of PVA~Phenol/Trioxane * Gelation Temp, F 200 300 350 400 450 Gel Time, days no gel no gel * 2.5% PVA, 4~ phenol, 3% trioxane Effect of N~OH Concentration on Gel * Time 300F 3SOCF ~ 0F 450F
NaOH, %
._ 0.05 No gel lS days8-9 days 4 days 0.1 " lS " 5-7 " 2 "
0.2 " 12 " 2 " 1 day 0.3 " 9 " 1 day 1 "
0.5 " 6 " 1 " 1 "
2.5% PVA, 4% phenol, 3~ trioxane Prior to injecting thc aqueous temperature activated gellable mixture, the fonnation is heated as mentioned above during the steam flooding enhanced oil recovery process. A formation temperature of 300F or greater is preferred. The mcthod of this invention can also be used when the area in or substar.tially near either the injection well or the production well has becn heated to the desired temperature. This method is particularly beneficial when it is desired to close the heated area around a production well which has suffered a premature steam breakthrough. In this 2s situation, steam injection is ceased and the temperature activated gellable mixture is injected into the production well for a time sufficient to enter the areas which comprise the premature breakthrough zone. Afterwards the gellable mixtu~e in that zone is allowed to form a solid gel. Once the solid gel is formed, an enhanced oil recovery method in which a drive fluid is utilized can be injected either through the injection well or the production well to recover hydrocarbonaceous fluids from a less permeable zone of the fonnation.
As demonstrated, the novelty of this invention is that the cross-linking reaction is activated at elevated temperatures greater than 300P. The cross-linking reaction is not activated at temperatures under 300F. At high temperatures, trioxane, a cyclic dimer of fo~naldehyde decomposes to yield formaldehyde which in turn reacts with phenol to form phenolic resin, the gelant, in situ.
Phenolic resin then gels the polymer.
Where it is desired to obtain increased sweep efficiency, gels of this invention can be used to plug a previously sweep portion of a formation which has been heated to a temperature in excess of 300F. Said gels call be directed to areas of increased porosity. Once a solid gel has formed, hydrocarbonaceous fluids can be removed from an area of lesser permeability or an underswept zone by utilization in any of the below methods.
One method where gels of this invention can be utilized is prior to a waterflooding process for the recovery of oil Erom a subterranean formation. After plugging the more penneable zones of a heat~l formation with the novel gels of this invention, a waterflooding process can be commenced. U.S. Patent No. 4,479,894, issued to Chen et al., describes one such waterflooding process.
Steamflood processes which can be utilized when employing the gels described herein are detailed in l).S. Patent Nos. 4,489,783 and 3,918,521 issued to Shu and Snavely, respe(-tively.
Gels described herein can also be used in conjunction with a cyclic carbon dioxide steam stimulation process to recover heavy oil from a lower permeability zone to obtain greater sweep efficiency. Cyclic carbon dioxide steam stimulation can be commenced after plugging the more permeable zones of the reservoir Z005~3S3 with the novel temperature activated gels of this invention. A
suitable process is described in U.S. Patent No. 4,565,249 which issued to Pebdani et al. This process relates to a carbon dioxide-steam push-pull or "huff and puff" stimulation method for the recovery of viscous oil from a subterranean viscous oil-containing formation wherein a specific ratio of carbon dioxide to steam is used to obtain maximum oil recovery. Increased sweep efficiency can be obtained when the subject gels are used in combination with a carbon dioxide process by lowering the minimum miscibility pressure ('~MP") with carbon dioxide and recovering oil. Prior to comm~rlcement of the carbon dioxide process, a more permeable or overswept zone is heated and subsequently plugged with these novel gels. Carbon dioxide MMP in an oil recovery process is described in ~.S. Patent No. 4,513,821 issued to Shu.
Although the present invention has been described with preferred embodiments, it is to be understood that modifications and variations may be resorted to wlthout departing from the spirit and scope of this invention, as those skilled in the art will readily understand. Such modi~ications and variations are considered to be within the purview and scope of the appended claims.
As demonstrated, the novelty of this invention is that the cross-linking reaction is activated at elevated temperatures greater than 300P. The cross-linking reaction is not activated at temperatures under 300F. At high temperatures, trioxane, a cyclic dimer of fo~naldehyde decomposes to yield formaldehyde which in turn reacts with phenol to form phenolic resin, the gelant, in situ.
Phenolic resin then gels the polymer.
Where it is desired to obtain increased sweep efficiency, gels of this invention can be used to plug a previously sweep portion of a formation which has been heated to a temperature in excess of 300F. Said gels call be directed to areas of increased porosity. Once a solid gel has formed, hydrocarbonaceous fluids can be removed from an area of lesser permeability or an underswept zone by utilization in any of the below methods.
One method where gels of this invention can be utilized is prior to a waterflooding process for the recovery of oil Erom a subterranean formation. After plugging the more penneable zones of a heat~l formation with the novel gels of this invention, a waterflooding process can be commenced. U.S. Patent No. 4,479,894, issued to Chen et al., describes one such waterflooding process.
Steamflood processes which can be utilized when employing the gels described herein are detailed in l).S. Patent Nos. 4,489,783 and 3,918,521 issued to Shu and Snavely, respe(-tively.
Gels described herein can also be used in conjunction with a cyclic carbon dioxide steam stimulation process to recover heavy oil from a lower permeability zone to obtain greater sweep efficiency. Cyclic carbon dioxide steam stimulation can be commenced after plugging the more permeable zones of the reservoir Z005~3S3 with the novel temperature activated gels of this invention. A
suitable process is described in U.S. Patent No. 4,565,249 which issued to Pebdani et al. This process relates to a carbon dioxide-steam push-pull or "huff and puff" stimulation method for the recovery of viscous oil from a subterranean viscous oil-containing formation wherein a specific ratio of carbon dioxide to steam is used to obtain maximum oil recovery. Increased sweep efficiency can be obtained when the subject gels are used in combination with a carbon dioxide process by lowering the minimum miscibility pressure ('~MP") with carbon dioxide and recovering oil. Prior to comm~rlcement of the carbon dioxide process, a more permeable or overswept zone is heated and subsequently plugged with these novel gels. Carbon dioxide MMP in an oil recovery process is described in ~.S. Patent No. 4,513,821 issued to Shu.
Although the present invention has been described with preferred embodiments, it is to be understood that modifications and variations may be resorted to wlthout departing from the spirit and scope of this invention, as those skilled in the art will readily understand. Such modi~ications and variations are considered to be within the purview and scope of the appended claims.
Claims (20)
1. A method for closing pores in a heated zone of a formation having zones of varying permeability comprising:
a) heating by a steam enhanced oil recovery process a zone of said formation to a temperature sufficient to cause a temperature activated gellable mixture to form a solid gel;
b) terminating steam injection into the formation; and c) injecting into said formation the temperature activated gellable mixture which mixture enters said heated zone, where it is heated to a temperature sufficient to cause a solid gel to form and close pores in said heated zone regardless of the permeability of said zone.
a) heating by a steam enhanced oil recovery process a zone of said formation to a temperature sufficient to cause a temperature activated gellable mixture to form a solid gel;
b) terminating steam injection into the formation; and c) injecting into said formation the temperature activated gellable mixture which mixture enters said heated zone, where it is heated to a temperature sufficient to cause a solid gel to form and close pores in said heated zone regardless of the permeability of said zone.
2. The method as recited in claim 1 where a spacer volume of cold water is pumped into the formation after step c) which keeps any ungelled mixture from forming a solid gel.
3. The method as recited in claim 1 where a steam flooding or a steam stimulation enhanced oil recovery process is commenced after step c).
4. The method as recited in claim 1 where the gellable mixture comprises water, polyvinyl alcohol, phenol, and trioxane which forms a solid gel at a temperature of about 300°F or greater.
5. The method as recited in claim 1 where the gellable mixture comprises water, polyvinyl alcohol, phenol, and trioxane where the polyvinyl alcohol to phenol ratio is 0.2:2.0, the phenol to trioxane ratio is 0.5:1.5, and a gel forms in from 1 to 15 days with the addition of 0.05 to 0.5 wt.% of sodium hydroxide.
6. The method as recited in claim 1 where after step c) a drive fluid is injected into a low temperature zone of lesser permeability in said formation where the gellable mixture does not form a gel but serves as a mobility control agent to enhance the recovery of hydrocarbonaceous fluids.
7. The method as recited in claim 1 where said gellable mixture comprises a polymer such as polyacrylamide, sulfonated polyvinyl alcohol, poly(acrylamide-co-acrylamido 2-methylpropane sulfonate) cross-linked with a phenolic resin formed in situ.
8. The method as recited in claim 1 where said gellable mixture comprises a polymer such as polyacrylamide, sulfonated polyvinyl alcohol, poly(acrylamide-co-acrylamido-2-methylpropane sulfonate) cross-linked with a phenolic resin which is formed in situ.
9. A method for closing pores in a heated zone of a formation having zones of varying permeability comprising:
a) heating a zone in said formation by a steam flooding enhanced oil recovery process to a temperature greater than about 300°F which temperature is sufficient to activate a gellable mixture and cause it to form a solid gel;
b) terminating steam injecting into the formation;
c) injecting into the formation a temperature activated gellable aqueous mixture which contains sufficient amounts of a polymer selected from a member of the group consisting of polyvinyl alcohol, polyacrylamide, sulfonated polyvinyl alcohol, and poly(acrylamide- co-acrylamido-2-methylpropane sulfonate) cross-linked in situ with a phenolic compound and an aldehyde producing compound in an amount sufficient to form a solid gel which mixture upon reaching a temperature of 300°F forms a solid gel and closes pores in said heated zone regardless of the permeability of said zone; and d) directing a drive fluid into a zone which has not reached a temperature sufficient to cause gelation and removing any ungelled mixture and hydrocarbonaceous fluids therefrom.
a) heating a zone in said formation by a steam flooding enhanced oil recovery process to a temperature greater than about 300°F which temperature is sufficient to activate a gellable mixture and cause it to form a solid gel;
b) terminating steam injecting into the formation;
c) injecting into the formation a temperature activated gellable aqueous mixture which contains sufficient amounts of a polymer selected from a member of the group consisting of polyvinyl alcohol, polyacrylamide, sulfonated polyvinyl alcohol, and poly(acrylamide- co-acrylamido-2-methylpropane sulfonate) cross-linked in situ with a phenolic compound and an aldehyde producing compound in an amount sufficient to form a solid gel which mixture upon reaching a temperature of 300°F forms a solid gel and closes pores in said heated zone regardless of the permeability of said zone; and d) directing a drive fluid into a zone which has not reached a temperature sufficient to cause gelation and removing any ungelled mixture and hydrocarbonaceous fluids therefrom.
10. The method as recited in claim 9 where a spacer volume of cold water is pumped into the formation after step c) which keeps any ungelled mixture from forming a solid gel.
11. The method as recited in claim 9 where a steam flooding or a steam stimulation enhanced oil recovery process is commenced after step c).
12. The method as recited in claim 9 where the polyvinyl alcohol to phenol ratio is 0.2:2.0, the phenol to trioxane ratio is 0.5:1.5, and a gel forms in from 1 to 15 days when sodium hydroxide in 0.05 to 0.5 wt.% is added to the gellable mixture.
13. The method as recited in claim 9 where said drive fluid is derived from a carbon dioxide or water flood enhanced oil recovery process.
14. The method as recited in claim 9 where the gellable mixture does not form a gel but serves as a mobility control agent to enhance the recovery of hydrocarbonaceous fluids from said zone of lesser permeability.
15. The method as recited in claim 9 where said polymer is contained in the mixture in from 0.5 to 5.0 wt.%.
16. The method as recited in claim 9 where said aldehyde is a member selected from the group consisting of aldehydes having from 1 to 10 carbon atoms per molecule, such as trioxane and tetraoxane which aldehyde is contained in said gellable mixture in 0.5 to 5.0 wt. %.
17. The method as recited in claim 9 where the phenolic compound is contained in said gellable mixture in 0.5 to 5.0 wt.%
and is a member selected from the group consisting of phenol, naphthol, catechol, resorcinol, phloroglucinol, pyrogallol, 4,4'diphenol, and 1,3-dihydroxynaphthalene.
and is a member selected from the group consisting of phenol, naphthol, catechol, resorcinol, phloroglucinol, pyrogallol, 4,4'diphenol, and 1,3-dihydroxynaphthalene.
18. A method for closing pores in a zone of a formation having varying permeabilities which has a temperature greater than 300°F comprising:
a) conducting a steam flooding or steam stimulation enhanced oil recovery process in a formation until steam breakthrough occurs;
b) ceasing injection of steam into the formation;
c) injecting a temperature activated gellable mixture into the formation which mixture comprises water, polyvinyl alcohol, phenol and trioxane in an amount sufficient to form a phenolic resin in situ which mixture cross-links with said alcohol at a temperature greater than 300°F thereby forming a solid gel in a zone of said formation having a temperature greater than 300°F regardless of the permeability of said zone;
e) injecting cold water into the formation in an amount sufficient to prevent any ungelled mixture from forming a solid gel;
and f) injecting thereafter steam into the formation which enters a zone of the formation where the temperature was not previously heated above 300°F and removing hydrocarbonaceous fluids therefrom.
a) conducting a steam flooding or steam stimulation enhanced oil recovery process in a formation until steam breakthrough occurs;
b) ceasing injection of steam into the formation;
c) injecting a temperature activated gellable mixture into the formation which mixture comprises water, polyvinyl alcohol, phenol and trioxane in an amount sufficient to form a phenolic resin in situ which mixture cross-links with said alcohol at a temperature greater than 300°F thereby forming a solid gel in a zone of said formation having a temperature greater than 300°F regardless of the permeability of said zone;
e) injecting cold water into the formation in an amount sufficient to prevent any ungelled mixture from forming a solid gel;
and f) injecting thereafter steam into the formation which enters a zone of the formation where the temperature was not previously heated above 300°F and removing hydrocarbonaceous fluids therefrom.
19. The method as recited in claim 18 where steam is injected into the formation via an injection well and hydrocarbonaceous fluids are produced therefrom by a production well.
20. The method as recited in claim 18 where the polyvinyl alcohol to phenol ratio is 0.2:2.0, the phenol to trioxane ratio is 0.5:1.5, and a gel forms in from 1 to 15 days with the addition of 0.05 to 0.5 wt.% of sodium hydroxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US292,795 | 1989-01-03 | ||
| US07/292,795 US4940091A (en) | 1989-01-03 | 1989-01-03 | Method for selectively plugging a zone having varying permeabilities with a temperature activated gel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2005853A1 true CA2005853A1 (en) | 1990-07-03 |
Family
ID=23126234
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002005853A Abandoned CA2005853A1 (en) | 1989-01-03 | 1989-12-18 | Method for plugging a high permeability zone with a heat activated gel |
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| Country | Link |
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| US (2) | US4940091A (en) |
| CA (1) | CA2005853A1 (en) |
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| US4940091A (en) * | 1989-01-03 | 1990-07-10 | Mobil Oil Corporation | Method for selectively plugging a zone having varying permeabilities with a temperature activated gel |
| US5115084A (en) * | 1989-07-19 | 1992-05-19 | Biocarbons Corporation | Method for controlling oil reservoir permeability using biomass oil |
| US5215147A (en) * | 1991-12-19 | 1993-06-01 | Mobil Oil Corporation | Method for selectively closing an intermediate zone of a near wellbore area |
| CA2091489C (en) * | 1992-04-13 | 2001-05-08 | Ahmad Moradi-Araghi | Gelation of water soluble polymers |
| US5404951A (en) * | 1993-07-07 | 1995-04-11 | Atlantic Richfield Company | Well treatment with artificial matrix and gel composition |
| US5492176A (en) * | 1994-12-01 | 1996-02-20 | Mobil Oil Corporation | Method for treating formations to plug flow |
| WO2004042187A1 (en) * | 2002-11-06 | 2004-05-21 | Shell Internationale Research Maatschappij B.V. | Inhibiting breakthrough of driving fluid via a permeable geological layer into an oil production well |
| US8076271B2 (en) * | 2004-06-09 | 2011-12-13 | Halliburton Energy Services, Inc. | Aqueous tackifier and methods of controlling particulates |
| US7128148B2 (en) * | 2004-04-16 | 2006-10-31 | Halliburton Energy Services, Inc. | Well treatment fluid and methods for blocking permeability of a subterranean zone |
| US7809538B2 (en) | 2006-01-13 | 2010-10-05 | Halliburton Energy Services, Inc. | Real time monitoring and control of thermal recovery operations for heavy oil reservoirs |
| GB2439076B (en) * | 2006-06-15 | 2008-07-23 | Aberdeen Petroleum Engineering | Controlled location of the precipitation of scale in reservoirs |
| US7832482B2 (en) | 2006-10-10 | 2010-11-16 | Halliburton Energy Services, Inc. | Producing resources using steam injection |
| US7770643B2 (en) | 2006-10-10 | 2010-08-10 | Halliburton Energy Services, Inc. | Hydrocarbon recovery using fluids |
| FR2918102B1 (en) * | 2007-06-29 | 2012-10-05 | Inst Francais Du Petrole | METHOD FOR RECOVERING OIL OR BITUMEN BY INJECTING A RECOVERY FLUID AND A DIVERSION AGENT |
| CA2772487A1 (en) * | 2011-03-31 | 2012-09-30 | Resource Innovations Inc. | Method for managing channeling in geothermal recovery of hydrocarbon reservoirs |
| US8662173B2 (en) | 2011-04-11 | 2014-03-04 | Saudi Arabian Oil Company | Plugging thief zones and fractures by in-situ and in-depth crystallization for improving water sweep efficiency of sandstone and carbonate reservoirs |
| US9702235B2 (en) * | 2011-08-17 | 2017-07-11 | Wintershall Holding GmbH | Method of improving mineral oil production by heating the formation and forming gel |
| CN103275687B (en) * | 2013-05-24 | 2015-07-08 | 中国石油天然气股份有限公司 | Thickened oil cold production agent and preparation method and application thereof |
| CA2972203C (en) | 2017-06-29 | 2018-07-17 | Exxonmobil Upstream Research Company | Chasing solvent for enhanced recovery processes |
| CA2974712C (en) | 2017-07-27 | 2018-09-25 | Imperial Oil Resources Limited | Enhanced methods for recovering viscous hydrocarbons from a subterranean formation as a follow-up to thermal recovery processes |
| CA2978157C (en) | 2017-08-31 | 2018-10-16 | Exxonmobil Upstream Research Company | Thermal recovery methods for recovering viscous hydrocarbons from a subterranean formation |
| CA2983541C (en) | 2017-10-24 | 2019-01-22 | Exxonmobil Upstream Research Company | Systems and methods for dynamic liquid level monitoring and control |
| CN109868126B (en) * | 2017-12-01 | 2021-09-28 | 中国石油天然气股份有限公司 | Water plugging agent and preparation method and application thereof |
| CN113773822B (en) * | 2020-06-10 | 2023-01-10 | 中国石油天然气股份有限公司 | Steam flooding profile control agent and preparation method and application thereof |
| CN115403720B (en) * | 2021-05-26 | 2023-11-28 | 中国石油天然气股份有限公司 | Phenolic resin cross-linking agent and preparation method thereof |
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-
1989
- 1989-01-03 US US07/292,795 patent/US4940091A/en not_active Expired - Fee Related
- 1989-12-18 CA CA002005853A patent/CA2005853A1/en not_active Abandoned
-
1990
- 1990-05-02 US US07/517,890 patent/US5022466A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US4940091A (en) | 1990-07-10 |
| US5022466A (en) | 1991-06-11 |
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