CA1247352A - High temperature chemical cement - Google Patents
High temperature chemical cementInfo
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- CA1247352A CA1247352A CA000495602A CA495602A CA1247352A CA 1247352 A CA1247352 A CA 1247352A CA 000495602 A CA000495602 A CA 000495602A CA 495602 A CA495602 A CA 495602A CA 1247352 A CA1247352 A CA 1247352A
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Abstract
HIGH TEMPERATURE CHEMICAL CEMENT
ABSTRACT
A high temperature chemical cement composition comprising temperature resistant particulate matter, a polymerizable resin capable of setting and maintaining its set under formation conditions, a liquid carrier, and a foaming system comprising surfactant and air is disclosed.
In its foamed condition the composition acts and performs as a fluid. Under formation conditions the resin will set and consolidate the composition into a rigid dense mass.
ABSTRACT
A high temperature chemical cement composition comprising temperature resistant particulate matter, a polymerizable resin capable of setting and maintaining its set under formation conditions, a liquid carrier, and a foaming system comprising surfactant and air is disclosed.
In its foamed condition the composition acts and performs as a fluid. Under formation conditions the resin will set and consolidate the composition into a rigid dense mass.
Description
~2~735~ GE TA: O 4 8 IIIGH TEMPERATllRE CHEMICAL CEMENT
This invention relates generally to cements capable of use in oil and qas wells, and more particularly to high temperature cements capable of use in treating high temperature wells and other hiqh temperature subsurface formations.
Cements used in oil and gas wells serve a variety of ; 20 functions. Typically, oil and gas wells are walled with steel tubing called the casingO Cements are employed to secure the cas;ng to the wall of the borehole usually by pumping the cement down the inside and up the outside of the casinq to the desired level. Once the cement sets, the cement and casing provide a seal which protects surrounding fresh water resevoirs and the like from contamination by the formation fluids. Additionally, ~he cemented casing aids in supporting unconsolidated rock formations surrounding the borehole, and helps to prevent blowouts and subsequent waste of the reservoir's resources. Another important application of cement in oil and ~as wells is its use in water-exclusion methods~ In many oil and gas wells, the production of water makes the well uneconomical to operate. This can be overcome by placing a cement seal at the water-oil interface in a borehole to exclude water from the oil production.
Typical cements used in the above applications are cements of the portland and portland-pozzolarl tyPes.
These cements are ~enerally produced by burninq a mixture of finely divided calcareous and argillaceous material and grindinq the resultant residue to produce a fine powder.
The calcium silicates and calcium aluminates produced by the calcining process react chemically with water to form a stone-like mass.
However, these types of cement are often inadequate ~hen used in the high temperature, hi~h pressure, corro-sive environment of many deep wells and subsurface forma-tions such as oil wells, hydrothermal wells, and other ~eothermal formations. Portland and pozzolan type cements tend to deteriorate under these conditions o~ten causinq failure of the cemented well or formation.
Past methods of modifying portland type cements have proved unsatisfactory for many applications. Magnesium or ma~nesium containinq compounds have been added to ~ortland cement to increase temperature resistance. ~nfortunately, unpredictable swelling often occurs making the set of the cement unsatisfactory. In addition, the high viscosity of the ma~nesium containin~ slurry inhibits satisfactory pumping in many instances. Addition of more water to improve pumpability further decreases the settin~, curinq and other physical qualities of the cement. Temperature resistance is claimed to be improved by the use of calcined serpentine, silica and a calcium silicate to form a high temperature cement which is pumped into a well and allowed to hydrothermally cure to form a crystallized diopside and/or serpentine-containing phase. In addition, asbestos fibers have heen added to portland type cements to im~rove temperature resistance, but the requirement o~
a hiqh water to asbestos ratio permits only the use of small amounts of asbestos fibers in order to maintain 7~
ade~uate pumpa~ility. In addition, too hiqh an asbestos fiber content (generally qreater than 2~) in the cement decreases the compressive strength of the cement.
In addition to difficulties with temperature resis-tance, stability and pumpability, settinq time is a major disadvanta~e of portland type cement. The hiqh tempera-ture formations tend to decrease the set time siqnifi-cantly and impair pumpability. Retarder additives such as calcium lignosulfonate and carboxymethyl hydroxyethyl cellulose have been added to portland cement to increase the settin~ time. Unfortunately, the results are qener-ally unpredictahle due to the absence of a homogeneous mixture of the additive throu~hout the cement. Improve-ments have been provided for this condition hy coatinq thecement qrains with crosslinked hydroxyalkyl cellulose in an attempt to provide a uniform concentration of retarder throuqhout the cement.
Althouah improved portland type cemsnts are available, a hiah temperature cement havinq overall qualities of hiqh temperature resistance, stability, pumpability, chemical resistance and controllable settinq time is desired.
The present invention comprises a unique foamed hiah temperature chemical cement havinq the aualities of hiqh st~en~th, chemical resistance, controllable settina time, pumpability and stability.
More particularly, the invention in one as2ect pertains to a high temperature chemical cement composition comprising finely divided particulate cementing matter capable of use under high temperature conditions, a polymeri~able resin capable of coating the particulate '', 3~
L7~
-3a-matter and of setting and maintaining its set under the high temperature conditions, a liquid carrier, and a foaming agent capable of foaming the composition comprising air and surfactant.
In its foamed condition, the composition is liquid in form or liquescent in that it can act and perform as a liquid, thus providing pumpability. At the subsurface formation temperature, the resin will set and consolidate the composition into a rigid dense mass.
Accordingly, the invention also comprehends a method of cementing a subsurface zone comprising intro-ducing the composition into a subsurface zone and maintaining the composition in the subsurface area until the resin has set. A polymer profile control treatment would further include introducing a polymer suitable for profile control into the fracture containing the cement matrix.
_4_ ~ ~73~
Advantaqeously, the permeability of the set composi-tion can be adjusted so as to provide a maximum barrier to the flow of oil, gas, steam, water and the like, or to provide a more permeable partial barrier. Partial bar-riers are desirable in forminq a matrix for later polymertreatment of naturally fractured reservoirs having extremely high local permeability which qenerally prohibit traditional polymer profile control treatments. The permeability of the set composition can be adjusted by varyinq the amount of air and surfactant incorporated into the comPosition.
In addition, the setting time of the composition can be predetermined by varyinq the pH of the composition.
Once se~, the composition is stable to at least tempera-tures of about 400F. Further, the composition once set is chemically resistant to hydrocarbons, acids, bases and most other non-oxidizing chemicals.
The subject invention is a novel hi~h temperature chemical cement. The composition of the chemical cement comprises appropriate temperature resistant finely divided particles combined with a polymerizable resin capable of settin~ under formation conditions and maintaining its set, a liquid carrier, and a foaming system comprisinq surfactant and air. The foaming system provides a pum~able mixture of uniform concentration~ Under formation conditions the resin sets, consolidatinq the composition into a riqid dense mass havinq high strenqth~
temperature and chemical resistance and stability.
~"
, ,,,. ~.
. ~" " , _5~ 7~
The Particulate Matter Component The particulate matter component of the compositions of this invention may be any suitable finely divided particulate cementinq matter, such as powders, dusts, or flours such as silica flour, capable of use under hiqh temperature formation condtions which have the capability of forming a hi~hly imper~eable mass in conjunction with a set resin. In addition, the particulate matter i5 chosen for its strength, economy, and compatibility with other components of the composition and the formation fluids~
_he Thermosettin~ Resin Various resins may be used in the present invention.
This includes true thermosetting resins, often referred to as one-step resins because no curing agent is required, and two-step thermosettinq resins which utilize a catalyst for curing. An example of a true thermosetting resin would be a phenolic, or phenol-formaldehyde, resin of the resole type. An example of a two-step resin would be a phenolic resin of the novolac type. Other thermosetting resins of the aminoplast type may also be used, including urea-formaldehyde and melamine-formaldehyde resins.
~lthough these resins may be used as one-step resins, addition of acid catalysts will speed the curinq time.
Furan resins, including resins produced from the reaction of furfuryl alcohol with urea, formaldehyde or phenols, may also be used~ These resins are generally cured by addition of mineral or organic acid catalysts, althou~h occasionally alkaline catalysts are used for curing. In addition, it is contemplated that epoxy type resins may also be used.
In a preferred embodiment of the present invention, an oil-soluble resin is desirable, for example a urea-~ 2~7;~i2 ~ormaldehyde resin. This allows addition of substantial amounts of water without affecting the polymerization of the resin.
Of primary importance in choosing a resin is the ability to control the settinq time. A sufficient amount of time must be allowed for preparation of the composi-tion, storaqe, and introduction of the mixture into the subsurface formation before setting. In this respect, an oliqomer type resin is preferred to a ~onomer type resin because of the increased settin~ time for the oligomer.
If the thermosetting resin is of the two-step vari-ety, a catalyst is qenerally required. Acid catalysts are usually employed, althouqh base catalysis is qenerally employed in limestone formations. Generally as the pH of the composition is decreased by addition of the acid catalyst, a corresponding decrease in resin setting time results. Ir, a preferred embodiment of the invention, a buf~ered acid catalyst is u~sed to raise the pH of the composition, thereby increasing the setting time of the resin while leaving the total acid quantity nearly the same.
If desired, the resin may be pre-coated on the parti-culate matter before combining it with the other compo-nents of the composition. Methods for making resin coated particles are well known in the art, as typi~ied by Nesbit et al., U.S. Patent No. 2,986,538. Pre-coating is deemed especially desirable in those instances where the resin-forminq material is soluble in water and the liquid car-rier is water.
~7~ ~73~
The Liquid Carrier .
Any suitable liquid may be used in practicinq the present invention. In general, the liquid is chosen on the basis of its economy, fluidity, and chemical compati-bility with the rock formation and the reservoir fluids.
Water, brine and like liquids are generally preferred because they are economical.
The Foaming System The components required to produce a foamed fluid in accor~ance with the present invention will normally in-clude a surfactant and air foaming agent. The foaming agent helps maintain the liquidity of the overall composi-tion. The surfactant may be cationic, anionic or non-ionic, but it must be capable of qeneratinq a foam with a liquid carrier and air at ambient temperatures. Examples of surfactants which may be used are soaps, synthetic detergents, and proteins. Desirable surfactants can be selected from the many alkyl aromatic sulfonic acids. A
principal purpose of the surfactant is to control bubble life in the foam. Buhble strenqth can be increased by addinq minute amounts of polyvalent cations which further stabilizes the foam.
.
The foaminq system can be adapted to give a set cement with minimal permeability, such as desired for plugging a well or sealing a porous formation, or to give a set cement havin~ more than minimal permeability, such as desired for providing a matrix for polymer profile control treatments. Generally, the fractures of naturally fractured resevoirs have extremely high local perme-ability, and as a result typical polymer profile control has limited success. By regulating the foaming system to ProVide a more permeable cement, an effective cement matrix can be provided in the fracture so that a Polymer will hold.
Generally, the foaming system can be adapted to provide a cement with more than minimal Permeability by (1) incorporating more air into the composition, ~2) in-creasinq the concentration of surfactant in the composi~
tion, or both. Cements of minimal permeability are pro-vided by incorporatinq as little air as possible into the composition and decreasing surfactant compositon.
EXAMPLES
The following examples describe the invention in more detail. Such examples are for the purpose of illustrating the invention and do not limit the scope of the invention.
Example 1 A chemical cement for use under conditions where minimal permeability is desired was constructed from the components listed in Table 1.
~2 ?~7 3 ~
g Equivalent Laboratory Material Field Units W4iqht Comments -Silica Flour 208 lb.500 g 400 mesh Resin I 1.70 qal. 40 a Urea/for?Taldehyde type *
Resin II 1.76 qal. 40 q ?~uacorr 1300: Butyl Acetate (80:20 by wt.) Catalyst 2.10 gal.50 g 39.2% Phosphoric Acid 15 Component t85%), 4.4~ Fluos il ic i c Acid (40%), 20.0~ Toluene Sulfonic Acid, 36.4 Water 20Surfactant- 3.80 qal. l00 g 35.3% Phosphoric Acid, Catalyst 3.9~ Fluosilicic Acid, Co~ponent 18~ Toluene Sulfonic Acid, 10% Dodecyl Benezene Sulfonic Acid, 32.8% Water Water/A~monium 10.00 qal. 200 ?~ Enough Amm~nium Hydroxide Hydroxide to bring the mixture's pH
^ to 6 The Quacorr 1300 referred to in Table 1 is a partially polymerized furfuryl alcohol resin supplied by the Quaker Oats Ch?emical Company (the butylacetate serves as a solvent for the resin) 35 as ~?ell as a water scaven~er for the polymerization reaction.) Example 2 The components of Example 1 were mixed in a Kitchen Aide mixer at the lowest speed settinq so as to incorpo-rate as little air as possible. The silica flour was mixed with resins I and II until coated. The catalyst and surfactant comPOnents and the water/ammonium hydroxide solution were then added. (These may be premixed before adding). Mixing was continued until the silica flour * Trademarks ~ ~.
? ,, '.
? ~1~,, ,,,.1 -10~ 73~
mixture was liquidized. Further mixina will not damage the results.
Example 3 A six inch pipe nipple was packed with solvent stripped formation material and equipped with fittin~s.
An initial permeability to water was measured and found to be 3.49 darcies. A liquidi~ed silica flour mixture pre-pared according to Example 2 was injectsd into the pipeni~ple under 5 psi and allowed to set. The core was then uncapped and visually inspected. The silica flour was well dispersed in the core as evidenced by the uniform consolidation of the core material at both injection and production ends of the core. The core was recapped ~ith clean end caps and the permeability was remeasured. The core was found to be plu~ed. The core was thsn placed in an oven at 392bF for 96 hours to see if the heat would deqrade the polymerized resinO After the 96 hours, the permeability was remeasured and the core was found to still be plua~ed. Visual examination revealed no damaqe as well.
Example 4 A chemical cement for use under conditions where more than minimal permeability is desired was constructed from the components listed in Table 2.
Equivalent Laboratory Materi0 Field Units Weiaht G~,ents Silica Flour 208 lb. 500 a 400 mesh Resin I 1.70 aal. 40 9 Urea/formaldehyde t~pe Resin II 1~76 gal. 40 q Quacorr 1300: Butyl Acetate (80:20 by wt.) Catalyst None Ccmponent Surfactant- 5.7 qal. 150 g Increased amount of the Catalyst surfactant component as Component ~escribed in Table l.
Ihis c ~ onent contains 0.5% Aluminum cation based on the D~decyl Benzene Sulfonic Acid wei~ht.
~ater/A~moniu~ lO.0 qal. 200 9 Enouqh Ammonium to Hydroxide brin~ the pH to 6.
Example 5 The components of Example 4 were mixed as in Example
This invention relates generally to cements capable of use in oil and qas wells, and more particularly to high temperature cements capable of use in treating high temperature wells and other hiqh temperature subsurface formations.
Cements used in oil and gas wells serve a variety of ; 20 functions. Typically, oil and gas wells are walled with steel tubing called the casingO Cements are employed to secure the cas;ng to the wall of the borehole usually by pumping the cement down the inside and up the outside of the casinq to the desired level. Once the cement sets, the cement and casing provide a seal which protects surrounding fresh water resevoirs and the like from contamination by the formation fluids. Additionally, ~he cemented casing aids in supporting unconsolidated rock formations surrounding the borehole, and helps to prevent blowouts and subsequent waste of the reservoir's resources. Another important application of cement in oil and ~as wells is its use in water-exclusion methods~ In many oil and gas wells, the production of water makes the well uneconomical to operate. This can be overcome by placing a cement seal at the water-oil interface in a borehole to exclude water from the oil production.
Typical cements used in the above applications are cements of the portland and portland-pozzolarl tyPes.
These cements are ~enerally produced by burninq a mixture of finely divided calcareous and argillaceous material and grindinq the resultant residue to produce a fine powder.
The calcium silicates and calcium aluminates produced by the calcining process react chemically with water to form a stone-like mass.
However, these types of cement are often inadequate ~hen used in the high temperature, hi~h pressure, corro-sive environment of many deep wells and subsurface forma-tions such as oil wells, hydrothermal wells, and other ~eothermal formations. Portland and pozzolan type cements tend to deteriorate under these conditions o~ten causinq failure of the cemented well or formation.
Past methods of modifying portland type cements have proved unsatisfactory for many applications. Magnesium or ma~nesium containinq compounds have been added to ~ortland cement to increase temperature resistance. ~nfortunately, unpredictable swelling often occurs making the set of the cement unsatisfactory. In addition, the high viscosity of the ma~nesium containin~ slurry inhibits satisfactory pumping in many instances. Addition of more water to improve pumpability further decreases the settin~, curinq and other physical qualities of the cement. Temperature resistance is claimed to be improved by the use of calcined serpentine, silica and a calcium silicate to form a high temperature cement which is pumped into a well and allowed to hydrothermally cure to form a crystallized diopside and/or serpentine-containing phase. In addition, asbestos fibers have heen added to portland type cements to im~rove temperature resistance, but the requirement o~
a hiqh water to asbestos ratio permits only the use of small amounts of asbestos fibers in order to maintain 7~
ade~uate pumpa~ility. In addition, too hiqh an asbestos fiber content (generally qreater than 2~) in the cement decreases the compressive strength of the cement.
In addition to difficulties with temperature resis-tance, stability and pumpability, settinq time is a major disadvanta~e of portland type cement. The hiqh tempera-ture formations tend to decrease the set time siqnifi-cantly and impair pumpability. Retarder additives such as calcium lignosulfonate and carboxymethyl hydroxyethyl cellulose have been added to portland cement to increase the settin~ time. Unfortunately, the results are qener-ally unpredictahle due to the absence of a homogeneous mixture of the additive throu~hout the cement. Improve-ments have been provided for this condition hy coatinq thecement qrains with crosslinked hydroxyalkyl cellulose in an attempt to provide a uniform concentration of retarder throuqhout the cement.
Althouah improved portland type cemsnts are available, a hiah temperature cement havinq overall qualities of hiqh temperature resistance, stability, pumpability, chemical resistance and controllable settinq time is desired.
The present invention comprises a unique foamed hiah temperature chemical cement havinq the aualities of hiqh st~en~th, chemical resistance, controllable settina time, pumpability and stability.
More particularly, the invention in one as2ect pertains to a high temperature chemical cement composition comprising finely divided particulate cementing matter capable of use under high temperature conditions, a polymeri~able resin capable of coating the particulate '', 3~
L7~
-3a-matter and of setting and maintaining its set under the high temperature conditions, a liquid carrier, and a foaming agent capable of foaming the composition comprising air and surfactant.
In its foamed condition, the composition is liquid in form or liquescent in that it can act and perform as a liquid, thus providing pumpability. At the subsurface formation temperature, the resin will set and consolidate the composition into a rigid dense mass.
Accordingly, the invention also comprehends a method of cementing a subsurface zone comprising intro-ducing the composition into a subsurface zone and maintaining the composition in the subsurface area until the resin has set. A polymer profile control treatment would further include introducing a polymer suitable for profile control into the fracture containing the cement matrix.
_4_ ~ ~73~
Advantaqeously, the permeability of the set composi-tion can be adjusted so as to provide a maximum barrier to the flow of oil, gas, steam, water and the like, or to provide a more permeable partial barrier. Partial bar-riers are desirable in forminq a matrix for later polymertreatment of naturally fractured reservoirs having extremely high local permeability which qenerally prohibit traditional polymer profile control treatments. The permeability of the set composition can be adjusted by varyinq the amount of air and surfactant incorporated into the comPosition.
In addition, the setting time of the composition can be predetermined by varyinq the pH of the composition.
Once se~, the composition is stable to at least tempera-tures of about 400F. Further, the composition once set is chemically resistant to hydrocarbons, acids, bases and most other non-oxidizing chemicals.
The subject invention is a novel hi~h temperature chemical cement. The composition of the chemical cement comprises appropriate temperature resistant finely divided particles combined with a polymerizable resin capable of settin~ under formation conditions and maintaining its set, a liquid carrier, and a foaming system comprisinq surfactant and air. The foaming system provides a pum~able mixture of uniform concentration~ Under formation conditions the resin sets, consolidatinq the composition into a riqid dense mass havinq high strenqth~
temperature and chemical resistance and stability.
~"
, ,,,. ~.
. ~" " , _5~ 7~
The Particulate Matter Component The particulate matter component of the compositions of this invention may be any suitable finely divided particulate cementinq matter, such as powders, dusts, or flours such as silica flour, capable of use under hiqh temperature formation condtions which have the capability of forming a hi~hly imper~eable mass in conjunction with a set resin. In addition, the particulate matter i5 chosen for its strength, economy, and compatibility with other components of the composition and the formation fluids~
_he Thermosettin~ Resin Various resins may be used in the present invention.
This includes true thermosetting resins, often referred to as one-step resins because no curing agent is required, and two-step thermosettinq resins which utilize a catalyst for curing. An example of a true thermosetting resin would be a phenolic, or phenol-formaldehyde, resin of the resole type. An example of a two-step resin would be a phenolic resin of the novolac type. Other thermosetting resins of the aminoplast type may also be used, including urea-formaldehyde and melamine-formaldehyde resins.
~lthough these resins may be used as one-step resins, addition of acid catalysts will speed the curinq time.
Furan resins, including resins produced from the reaction of furfuryl alcohol with urea, formaldehyde or phenols, may also be used~ These resins are generally cured by addition of mineral or organic acid catalysts, althou~h occasionally alkaline catalysts are used for curing. In addition, it is contemplated that epoxy type resins may also be used.
In a preferred embodiment of the present invention, an oil-soluble resin is desirable, for example a urea-~ 2~7;~i2 ~ormaldehyde resin. This allows addition of substantial amounts of water without affecting the polymerization of the resin.
Of primary importance in choosing a resin is the ability to control the settinq time. A sufficient amount of time must be allowed for preparation of the composi-tion, storaqe, and introduction of the mixture into the subsurface formation before setting. In this respect, an oliqomer type resin is preferred to a ~onomer type resin because of the increased settin~ time for the oligomer.
If the thermosetting resin is of the two-step vari-ety, a catalyst is qenerally required. Acid catalysts are usually employed, althouqh base catalysis is qenerally employed in limestone formations. Generally as the pH of the composition is decreased by addition of the acid catalyst, a corresponding decrease in resin setting time results. Ir, a preferred embodiment of the invention, a buf~ered acid catalyst is u~sed to raise the pH of the composition, thereby increasing the setting time of the resin while leaving the total acid quantity nearly the same.
If desired, the resin may be pre-coated on the parti-culate matter before combining it with the other compo-nents of the composition. Methods for making resin coated particles are well known in the art, as typi~ied by Nesbit et al., U.S. Patent No. 2,986,538. Pre-coating is deemed especially desirable in those instances where the resin-forminq material is soluble in water and the liquid car-rier is water.
~7~ ~73~
The Liquid Carrier .
Any suitable liquid may be used in practicinq the present invention. In general, the liquid is chosen on the basis of its economy, fluidity, and chemical compati-bility with the rock formation and the reservoir fluids.
Water, brine and like liquids are generally preferred because they are economical.
The Foaming System The components required to produce a foamed fluid in accor~ance with the present invention will normally in-clude a surfactant and air foaming agent. The foaming agent helps maintain the liquidity of the overall composi-tion. The surfactant may be cationic, anionic or non-ionic, but it must be capable of qeneratinq a foam with a liquid carrier and air at ambient temperatures. Examples of surfactants which may be used are soaps, synthetic detergents, and proteins. Desirable surfactants can be selected from the many alkyl aromatic sulfonic acids. A
principal purpose of the surfactant is to control bubble life in the foam. Buhble strenqth can be increased by addinq minute amounts of polyvalent cations which further stabilizes the foam.
.
The foaminq system can be adapted to give a set cement with minimal permeability, such as desired for plugging a well or sealing a porous formation, or to give a set cement havin~ more than minimal permeability, such as desired for providing a matrix for polymer profile control treatments. Generally, the fractures of naturally fractured resevoirs have extremely high local perme-ability, and as a result typical polymer profile control has limited success. By regulating the foaming system to ProVide a more permeable cement, an effective cement matrix can be provided in the fracture so that a Polymer will hold.
Generally, the foaming system can be adapted to provide a cement with more than minimal Permeability by (1) incorporating more air into the composition, ~2) in-creasinq the concentration of surfactant in the composi~
tion, or both. Cements of minimal permeability are pro-vided by incorporatinq as little air as possible into the composition and decreasing surfactant compositon.
EXAMPLES
The following examples describe the invention in more detail. Such examples are for the purpose of illustrating the invention and do not limit the scope of the invention.
Example 1 A chemical cement for use under conditions where minimal permeability is desired was constructed from the components listed in Table 1.
~2 ?~7 3 ~
g Equivalent Laboratory Material Field Units W4iqht Comments -Silica Flour 208 lb.500 g 400 mesh Resin I 1.70 qal. 40 a Urea/for?Taldehyde type *
Resin II 1.76 qal. 40 q ?~uacorr 1300: Butyl Acetate (80:20 by wt.) Catalyst 2.10 gal.50 g 39.2% Phosphoric Acid 15 Component t85%), 4.4~ Fluos il ic i c Acid (40%), 20.0~ Toluene Sulfonic Acid, 36.4 Water 20Surfactant- 3.80 qal. l00 g 35.3% Phosphoric Acid, Catalyst 3.9~ Fluosilicic Acid, Co~ponent 18~ Toluene Sulfonic Acid, 10% Dodecyl Benezene Sulfonic Acid, 32.8% Water Water/A~monium 10.00 qal. 200 ?~ Enough Amm~nium Hydroxide Hydroxide to bring the mixture's pH
^ to 6 The Quacorr 1300 referred to in Table 1 is a partially polymerized furfuryl alcohol resin supplied by the Quaker Oats Ch?emical Company (the butylacetate serves as a solvent for the resin) 35 as ~?ell as a water scaven~er for the polymerization reaction.) Example 2 The components of Example 1 were mixed in a Kitchen Aide mixer at the lowest speed settinq so as to incorpo-rate as little air as possible. The silica flour was mixed with resins I and II until coated. The catalyst and surfactant comPOnents and the water/ammonium hydroxide solution were then added. (These may be premixed before adding). Mixing was continued until the silica flour * Trademarks ~ ~.
? ,, '.
? ~1~,, ,,,.1 -10~ 73~
mixture was liquidized. Further mixina will not damage the results.
Example 3 A six inch pipe nipple was packed with solvent stripped formation material and equipped with fittin~s.
An initial permeability to water was measured and found to be 3.49 darcies. A liquidi~ed silica flour mixture pre-pared according to Example 2 was injectsd into the pipeni~ple under 5 psi and allowed to set. The core was then uncapped and visually inspected. The silica flour was well dispersed in the core as evidenced by the uniform consolidation of the core material at both injection and production ends of the core. The core was recapped ~ith clean end caps and the permeability was remeasured. The core was found to be plu~ed. The core was thsn placed in an oven at 392bF for 96 hours to see if the heat would deqrade the polymerized resinO After the 96 hours, the permeability was remeasured and the core was found to still be plua~ed. Visual examination revealed no damaqe as well.
Example 4 A chemical cement for use under conditions where more than minimal permeability is desired was constructed from the components listed in Table 2.
Equivalent Laboratory Materi0 Field Units Weiaht G~,ents Silica Flour 208 lb. 500 a 400 mesh Resin I 1.70 aal. 40 9 Urea/formaldehyde t~pe Resin II 1~76 gal. 40 q Quacorr 1300: Butyl Acetate (80:20 by wt.) Catalyst None Ccmponent Surfactant- 5.7 qal. 150 g Increased amount of the Catalyst surfactant component as Component ~escribed in Table l.
Ihis c ~ onent contains 0.5% Aluminum cation based on the D~decyl Benzene Sulfonic Acid wei~ht.
~ater/A~moniu~ lO.0 qal. 200 9 Enouqh Ammonium to Hydroxide brin~ the pH to 6.
Example 5 The components of Example 4 were mixed as in Example
2 with the exception that more air was incorporated into the mixture to produce a more hiqhly foamed composition.
As evidenced in Table 2, foaminq was further increased by addinq more surfactant. The soap bubbles of the foam were strengthened by use of an aluminium cation as a foam stabilizer.
Example 6 -A fracture-like environment was created for testing the compositions of Examples 1 and 4 in the followin~
manner. Two Berea cores, 2x2x12 inches were cut in half and two qrooves were placed on each of the newly formed
As evidenced in Table 2, foaminq was further increased by addinq more surfactant. The soap bubbles of the foam were strengthened by use of an aluminium cation as a foam stabilizer.
Example 6 -A fracture-like environment was created for testing the compositions of Examples 1 and 4 in the followin~
manner. Two Berea cores, 2x2x12 inches were cut in half and two qrooves were placed on each of the newly formed
3~
faces. The cores were then fitted back together according to their original orientation with the sides of the cores sealed with epoxyO The grooves served to insure a fracture-like environment within the cores. The cores were then equipped with fittings at each end to facilitate the introduction of fluids and cast in epoxy resin. After the epoxy resin had set, the cores were ready for treatment.
Example 7 An initial permeability to water was run on one of the cores prepared accordin~ to Example 6 and found to be 14.67 darcies. Liquidized silica flour constructed accordinq to Example 2 was ~ravity flowed into the core and allowed sufficient time to set. The permeability was remeasured and found to be 0~ The fittinqs were removed and found to be plugqed. The core was fitted with new fittings and the permeability was found to be 0.822 darcies. This corresponds to a 94.4% reduction in perme-ability.
Example 8 An initial permeability to water was run on the other core prepared in accordance with example 6 and was found to be 21.7 darcies. Liquidized silica flour prepared accordinq to Example 5 was ~ravity flowed into the core.
After the silica flour had set and the fittin~s were replaced, the permeability was remeasured and found to be 1.64 darcies. This corresponds to a 92.4% reduction in permeability. A summary of the results are listed below in Table 3.
3~2 TABLE: 3 FRACTURE RESULTS
5 ~ Initial K _ Final K ~ Reduction 714.67 darcies 0.82 darcies 94.4 821.70 darcies 1.64 darcies 92.4 Because the mixture is non-viscous and the aggregate used, the silica flour, is very fine ~400 mesh), the mix-ture will penetrate high permeability formations easily.
In the practice of the invention, the rate of poly-merization of the resin material qenerally increases alonq with increasing temperature. In addition, polymerization rate is varied by the type of resin used. A monomer-type resin will polymerize faster than an oligomer-type resin, qiven the same monomer chemistry. The Quacorr 1300 referred to in the above examples is water-insoluble.
Since Quacorr 1300 is an oligomer, it polymerizes slowly, and since it is oil-soluble, it permits substantial amounts of water to be added to the mixture thereby increasing liquidity but not suppressing the setting polymerization reaction.
In the compositions describe above, changing the quantity of acid downward to extend setting time could prevent polymerization entirely. Adding 6N ammonium hydroxide to the acid mixture to raise the pH had the effect of leaving the total acid quantity nearly the same while providing hydrogen ions more slowly. The hiqher the pH, the longer the set time for a given temperature. Con-sequently, higher temperature mixtures require a higher pl~
to achieve the same set time as lower temperature mix-tures. Very hiqh temperatures may require reduction of total acidity.
-14- '~
The foregoing description has been directed to a particular embodiment of the invention for the purposes of illustration and explanation. Those skilled in the art will readily appreciate modifications and changes in the procedures and components set forth without departin~ from the scope and spirit of the invention. Applicant's intsnt is that the folowin~ claims be interpreted to embrace all such modifications and variations.
faces. The cores were then fitted back together according to their original orientation with the sides of the cores sealed with epoxyO The grooves served to insure a fracture-like environment within the cores. The cores were then equipped with fittings at each end to facilitate the introduction of fluids and cast in epoxy resin. After the epoxy resin had set, the cores were ready for treatment.
Example 7 An initial permeability to water was run on one of the cores prepared accordin~ to Example 6 and found to be 14.67 darcies. Liquidized silica flour constructed accordinq to Example 2 was ~ravity flowed into the core and allowed sufficient time to set. The permeability was remeasured and found to be 0~ The fittinqs were removed and found to be plugqed. The core was fitted with new fittings and the permeability was found to be 0.822 darcies. This corresponds to a 94.4% reduction in perme-ability.
Example 8 An initial permeability to water was run on the other core prepared in accordance with example 6 and was found to be 21.7 darcies. Liquidized silica flour prepared accordinq to Example 5 was ~ravity flowed into the core.
After the silica flour had set and the fittin~s were replaced, the permeability was remeasured and found to be 1.64 darcies. This corresponds to a 92.4% reduction in permeability. A summary of the results are listed below in Table 3.
3~2 TABLE: 3 FRACTURE RESULTS
5 ~ Initial K _ Final K ~ Reduction 714.67 darcies 0.82 darcies 94.4 821.70 darcies 1.64 darcies 92.4 Because the mixture is non-viscous and the aggregate used, the silica flour, is very fine ~400 mesh), the mix-ture will penetrate high permeability formations easily.
In the practice of the invention, the rate of poly-merization of the resin material qenerally increases alonq with increasing temperature. In addition, polymerization rate is varied by the type of resin used. A monomer-type resin will polymerize faster than an oligomer-type resin, qiven the same monomer chemistry. The Quacorr 1300 referred to in the above examples is water-insoluble.
Since Quacorr 1300 is an oligomer, it polymerizes slowly, and since it is oil-soluble, it permits substantial amounts of water to be added to the mixture thereby increasing liquidity but not suppressing the setting polymerization reaction.
In the compositions describe above, changing the quantity of acid downward to extend setting time could prevent polymerization entirely. Adding 6N ammonium hydroxide to the acid mixture to raise the pH had the effect of leaving the total acid quantity nearly the same while providing hydrogen ions more slowly. The hiqher the pH, the longer the set time for a given temperature. Con-sequently, higher temperature mixtures require a higher pl~
to achieve the same set time as lower temperature mix-tures. Very hiqh temperatures may require reduction of total acidity.
-14- '~
The foregoing description has been directed to a particular embodiment of the invention for the purposes of illustration and explanation. Those skilled in the art will readily appreciate modifications and changes in the procedures and components set forth without departin~ from the scope and spirit of the invention. Applicant's intsnt is that the folowin~ claims be interpreted to embrace all such modifications and variations.
Claims (30)
1. A high temperature chemical cement composition comprising:
(a) finely divided particulate cementing matter capable of use under high temperature conditions;
(b) a polymerizable resin capable of coating said particulate matter and of setting and maintain-ing its set under said high temperature conditions;
(c) a liquid carrier;
(d) a foaming agent capable of foaming said composi-tion comprising air and surfactant.
(a) finely divided particulate cementing matter capable of use under high temperature conditions;
(b) a polymerizable resin capable of coating said particulate matter and of setting and maintain-ing its set under said high temperature conditions;
(c) a liquid carrier;
(d) a foaming agent capable of foaming said composi-tion comprising air and surfactant.
2. The composition of claim 1 in which the particulate matter is silica flour.
3. The composition of claim 1 in which the resin is a thermosetting resin.
4, The composition of claim 1 in which the resin is a two-step catalyzed resin.
5. The composition of claim 1 in which the resin is a partially polymerized furfuryl alcohol.
6. The composition of claim 1 in which the liquid car-rier is water or brine.
7. The composition of claim 1 in which the foaming system further comprises entrained air,
8. The composition of claim 1 in which the surfactant is an alkyl aromatic sulfonic acid.
9. The composition of claim 1 further comprising a foam stabilizer.
10. The composition of claim 1 further comprising a catalyst to catalyze the polymerization of said resin.
11. A method of polymer profile control treatment comprising:
A. introducing into a fracture a composition capable of providing a permeable cement matrix comprising:
(1) particulate cementing matter capable of use in subsurface formation fractures;
(2) a polymerizable resin capable of coating said particulate matter and of setting and maintaining its set under formation conditions;
(3) a liquid carrier; and (4) a foaming agent capable of foaming said composition comprising surfactant and air;
B. maintaining said composition in said fracture until the resin has set; and C. introducing a polymer suitable for profile control into said fracture containing said cement matrix.
A. introducing into a fracture a composition capable of providing a permeable cement matrix comprising:
(1) particulate cementing matter capable of use in subsurface formation fractures;
(2) a polymerizable resin capable of coating said particulate matter and of setting and maintaining its set under formation conditions;
(3) a liquid carrier; and (4) a foaming agent capable of foaming said composition comprising surfactant and air;
B. maintaining said composition in said fracture until the resin has set; and C. introducing a polymer suitable for profile control into said fracture containing said cement matrix.
12. The method of claim 11 in which the particulate matter is silica flour.
13. The method of claim 11 in which the resin is a thermosetting resin.
14. The method of claim 11 in which the resin is a two-step catalyzed resin.
15. The method of claim 11 in which the resin is a partially polymerized furfuryl alcohol.
16. The method of claim 11 in which the liquid carrier is water or brine.
17. The method of claim 11 in which the air is entrained into the composition.
18. The method of claim 11 in which the surfactant is an alkyl aromatic sulfonic acid.
19. The method of claim 11 which includes adding a foam stabilizer to the composition.
20. The method of claim 11 which includes adding a catalyst to the composition to catalyze the polymerization of said resin.
21. A method of cementing a subsurface zone comprising:
A. introducing into a subsurface zone a composition comprising:
(1) particulate cementing matter capable of use under, subsurface conditions;
(2) a polymerizable resin capable of coating said particulate matter and of setting and maintaining its set under subsurface conditions;
(3) a liquid carrier; and (4) a foaming agent capable of foaming said composition comprising surfactant and air;
and B. maintaining said composition in said subsurface area until said resin has set.
A. introducing into a subsurface zone a composition comprising:
(1) particulate cementing matter capable of use under, subsurface conditions;
(2) a polymerizable resin capable of coating said particulate matter and of setting and maintaining its set under subsurface conditions;
(3) a liquid carrier; and (4) a foaming agent capable of foaming said composition comprising surfactant and air;
and B. maintaining said composition in said subsurface area until said resin has set.
22. The method of claim 21 in which the particulate matter is silica flour.
23. The method of claim 21 in which the resin is a thermosetting resin.
24. The method of claim 21 in which the resin is a two-step catalyzed resin.
25. The method of claim 21 in which the resin is a partially polymerized furfuryl alcohol.
26. The method of claim 21 in which the liquid carrier is water or brine.
27. The method of claim 21 in which the air is entrained into the composition.
28. The method of claim 21 in which the surfactant is an alkyl aromatic sulfonic acid.
29. The method of claim 21 which includes adding a foam stabilizer to the composition.
30. The method of claim 21 which includes adding a catalyst to the composition to catalyze the polymerization of said resin.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US67289584A | 1984-11-19 | 1984-11-19 | |
| US672,895 | 1984-11-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1247352A true CA1247352A (en) | 1988-12-28 |
Family
ID=24700472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000495602A Expired CA1247352A (en) | 1984-11-19 | 1985-11-18 | High temperature chemical cement |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1247352A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994012445A1 (en) * | 1992-11-20 | 1994-06-09 | Sinvent A/S | Alternative cementing materials for completion of deep, hot oil-wells |
| EP0881353A1 (en) * | 1997-05-28 | 1998-12-02 | Institut Francais Du Petrole | Process and material for well cementing |
| US6802375B2 (en) | 2000-05-22 | 2004-10-12 | Shell Oil Company | Method for plugging a well with a resin |
| US7059415B2 (en) | 2001-07-18 | 2006-06-13 | Shell Oil Company | Wellbore system with annular seal member |
| CN117189049A (en) * | 2023-09-28 | 2023-12-08 | 大庆油田有限责任公司 | Nano profile control and flooding method suitable for low-permeability fractured reservoir |
-
1985
- 1985-11-18 CA CA000495602A patent/CA1247352A/en not_active Expired
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994012445A1 (en) * | 1992-11-20 | 1994-06-09 | Sinvent A/S | Alternative cementing materials for completion of deep, hot oil-wells |
| EP0881353A1 (en) * | 1997-05-28 | 1998-12-02 | Institut Francais Du Petrole | Process and material for well cementing |
| FR2763991A1 (en) * | 1997-05-28 | 1998-12-04 | Inst Francais Du Petrole | METHOD AND MATERIAL FOR CEMENTING WELLS |
| US6065539A (en) * | 1997-05-28 | 2000-05-23 | Institute Francois Du Petrole | Well cementing method and material containing fine particles |
| US6802375B2 (en) | 2000-05-22 | 2004-10-12 | Shell Oil Company | Method for plugging a well with a resin |
| US7059415B2 (en) | 2001-07-18 | 2006-06-13 | Shell Oil Company | Wellbore system with annular seal member |
| CN117189049A (en) * | 2023-09-28 | 2023-12-08 | 大庆油田有限责任公司 | Nano profile control and flooding method suitable for low-permeability fractured reservoir |
| CN117189049B (en) * | 2023-09-28 | 2024-04-23 | 大庆油田有限责任公司 | Nano profile control and flooding method suitable for low-permeability fractured reservoir |
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