WO2003102361A1 - Methods of generating gas in and foaming well cement compositions - Google Patents
Methods of generating gas in and foaming well cement compositions Download PDFInfo
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- WO2003102361A1 WO2003102361A1 PCT/GB2003/002211 GB0302211W WO03102361A1 WO 2003102361 A1 WO2003102361 A1 WO 2003102361A1 GB 0302211 W GB0302211 W GB 0302211W WO 03102361 A1 WO03102361 A1 WO 03102361A1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
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- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
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- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
- C09K8/473—Density reducing additives, e.g. for obtaining foamed cement compositions
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0067—Function or property of ingredients for mortars, concrete or artificial stone the ingredients being formed in situ by chemical reactions or conversion of one or more of the compounds of the composition
Definitions
- the present invention relates to methods of generating gas in and foaming well cement compositions during pumping of the compositions.
- Foamed hydraulic cement compositions have heretofore been utilized in oil and gas well cementing applications.
- a hydraulic cement composition is foamed by combining a mixture of foaming and foam stabilizing surfactants with the cement composition on the surface followed by injecting gas, typically nitrogen, into the cement composition containing the surfactants as the cement composition is pumped into the well bore.
- gas typically nitrogen
- This process allows the cement composition to have a gas concentration of from 1% to 99% by volume of the cement composition depending on the downhole pressure and temperature and the amount of gas injected into the cement composition at the surface.
- the equipment required for storing the nitrogen in liquid or gaseous form and injecting it into a cement composition is very elaborate and expensive. In addition, the equipment is frequently unavailable or can not be easily transported to well sites due to their remote locations.
- In-situ gas forming agents have been utilized heretofore in well cement compositions to prevent annular gas migration.
- surfactant coated finely ground aluminum has been included in cement compositions to generate hydrogen gas in the compositions as they are being pumped down well bores and after they are placed in annuluses between the walls of the well bores and casing or other pipe strings therein.
- the presence of the gas in the cement compositions prevents formation fluids from entering the cement compositions as the cement compositions develop gel strength. That is, the development of gel strength reduces the ability of a cement composition column to transmit hydrostatic pressure.
- the fluids enter the well bore and form channels in the cement composition column which remain after the cement composition column sets.
- the presence of the gas which is generated in the cement composition from the finely ground aluminum increases the volume of the cement composition such that the volume increase generated by the gas equals or slightly exceeds the cement composition volume reduction during the development of gel strength due to fluid loss and/or the cement hydration reaction.
- the increase in volume in the compressibility produced in the cement composition by the gas allows the cement composition column to resist the entry of formation fluids into the well bore.
- U.S. Patent No. 4,450,010 issued on May 22, 1984 to Burkhalter et al. discloses a well cementing method and gasified cements useful in carrying out the method. That is, U.S. Patent No. 4,450,010 discloses a method of cementing in subterranean formations using a gasified cement composition which prevents formation fluids from entering the cement composition column formed in the annulus between the well bore and a pipe string therein.
- the cement composition includes a nitrogen gas generating material, an oxidizing agent and a reaction rate control material whereby a quantity of gas is generated in the cement composition to offset the shrinkage in the cement composition column as it develops gel strength and to provide compressibility thereto whereby the entry of formation fluids into the well bore is reduced or prevented.
- the present invention provides improved methods of generating gas in and foaming well cement compositions whereby the cement pump or pumps used do not gas-lock which overcome the deficiencies of the prior art.
- An improved method of the present invention for generating gas in and foaming a cement composition introduced into a subterranean zone penetrated by a well bore is comprised of the following steps.
- a well cement composition is provided comprised of a hydraulic cement, sufficient water to form a pumpable slurry and a water soluble oxidizing agent.
- the cement composition is pumped into the subterranean zone by way of the well bore with one or more cement pumps.
- An aqueous solution or dispersion comprised of water, a gas generating chemical which is activated to produce gas by an oxidizing agent and a water soluble mixture of foaming and foam stabilizing surfactants.
- the aqueous solution or dispersion containing the gas generating chemical and the mixture of surfactants is pumped or otherwise introduced into the cement composition containing the oxidizing agent on the surface downstream of the one or more cement pumps so that the oxidizing agent activates the gas generating chemical whereby gas is produced in the cement composition, and the cement composition is foamed with the gas and stabilized by the mixture of surfactants as the cement composition flows into and through the well bore.
- a well cement composition is provided comprised of a hydraulic cement, sufficient water to form a pumpable slurry and a gas generating chemical which is activated to produce gas by an oxidizing agent.
- the cement composition is pumped into the subterranean zone by way of the well bore with one or more cement pumps.
- An aqueous solution or dispersion is provided comprised of water, a gas generating chemical which is activated to produce gas when introduced into a well cement composition but is not activated to produce gas by an oxidizing agent, a water soluble mixture of foaming and foam stabilizing surfactants and an oxidizing agent.
- the aqueous solution or dispersion containing the gas generating chemical activated by a cement composition, the mixture of foaming and foam stabilizing surfactants and the oxidizing agent are pumped or otherwise introduced into the cement composition containing the gas generating chemical which is activated by an oxidizing agent downstream of the one or more cement pumps so that the well cement composition and the aqueous solution or dispersion are combined, gas is produced in the cement composition and the combined cement composition is foamed with the gas and stabilized by the mixture of surfactants as the cement flows through the well bore.
- a well cement composition is provided comprised of a hydraulic cement, sufficient water to form a pumpable slurry and a gas generating chemical which is activated to produce gas by an oxidizing agent.
- the cement composition is pumped into the subterranean zone by way of the well bore with one or more cement pumps.
- An aqueous solution or dispersion is provided comprised of water, a gas generating chemical which is activated to produce gas when introduced into a well cement composition but is not activated to produce gas by an oxidizing agent and an oxidizing agent.
- the aqueous solution or dispersion containing the gas generating chemical activated by a cement composition and the oxidizing agent are pumped or otherwise introduced into the cement composition containing the gas generating chemical which is activated by an oxidizing agent downstream of the one or more cement pumps so that the well cement composition and the aqueous solution or dispersion are combined and gas is produced in the cement composition.
- An aqueous solution of a mixture of foaming and foam stabilizing surfactants is provided.
- the aqueous solution of the mixture of surfactants is pumped or otherwise introduced into the combined cement composition so that the final composition formed is foamed and stabilized by the mixture of surfactants as the cement composition flows through the well bore.
- gas is generated in the cement composition after the cement composition passes through the cement pumps whereby the cement pumps are not gas-locked.
- the present invention provides improved methods of generating gas in and foaming well cement compositions while the cement compositions are being pumped.
- the methods prevent gas from being generated in a cement composition until after the cement composition has been pumped by one or more cement pumps thereby preventing gas-locking of the pumps.
- a well cement composition is provided comprised of a hydraulic cement, sufficient water to form a pumpable slurry and a water soluble oxidizing agent.
- the cement composition is pumped into a subterranean zone by way of the well bore penetrating the subterranean zone with one or more cement pumps.
- An aqueous solution or dispersion comprised of water, a gas generating chemical which is activated to produce gas by an oxidizing agent and a water soluble mixture of foaming and foam stabilizing surfactants is provided.
- the aqueous solution or dispersion containing the gas generating chemical and the mixture of surfactants is pumped or otherwise introduced into the cement composition containing the oxidizing agent on the surface at a point downstream of the one or more cement pumps.
- the oxidizing agent activates the gas generating chemical whereby gas is produced in the cement composition and the cement composition is foamed and stabilized by the mixture of surfactants as the cement composition flows into and through the well bore.
- a variety of hydraulic cements can be utilized in the cement compositions including those comprised of calcium, aluminum, silicon, oxygen and/or sulfur which set and harden by reaction with water.
- Such hydraulic cements include Portland cements, pozzolana cements, gypsum cements, aluminous cements and silica cements.
- Portland cements or their equivalents are generally preferred for use in accordance with the present invention.
- Portland cements of the types defined and described in the API Specification For Materials And Testing For Well Cements, API Specification 10, 5 th Edition, dated July 1, 1990 of the American Petroleum Institute are particularly suitable.
- Preferred API Portland cements include classes A, B, C, G and H with API classes G and H being the most preferred.
- the water utilized in the cement compositions can be fresh water or salt water.
- Salt water is used herein to mean unsaturated aqueous salt solutions and saturated aqueous salt solutions including brine and seawater.
- the water is generally present in the cement compositions in an amount sufficient to form a slurry, i.e., an amount in the range of from about 30% to about 100% by weight of hydraulic cement in the compositions, more preferably in an amount in the range of from about 35% to about 60%.
- the gas generating chemicals useful in accordance with this invention primarily generate nitrogen along with small amounts of ammonia depending on the chemical structure of the gas generating chemical and the oxidizing agent.
- the gas generating chemicals are generally solid materials that liberate gas or gases on their own when they are heated to a temperature in the range of from about 200°F to about 500°F without requiring an activating oxidizing agent.
- water soluble oxidizing agents that can be used in the well cement compositions of this invention include, but are not limited to, ammonium persulfate, sodium persulfate, potassium persulfate, sodium chlorite, sodium perborate, sodium peroxy carbonate, calcium hypochlorite, sodium hypochlorite, sodium hypobromite, sodium bromite, sodium bromate and sodium chlorate. Of these, sodium chlorite is preferred.
- the oxidizing agent is generally included in the well cement composition in an amount in the range of from about 2%> to about 20% by weight of hydraulic cement in the composition.
- the aqueous solution or dispersion combined with the well cement composition downstream of the well cement pump or pumps is comprised of water, a gas generating chemical which is activated by the oxidizing agent in the well cement composition to produce gas and a water soluble mixture of foaming and foam stabilizing surfactants.
- the water in the aqueous solution or dispersion can be fresh water or salt water as described above.
- the gas generating chemicals which can be used in the aqueous solution or dispersion include, but are not limited to, hydrazine and its salts with acids, azodicarbonamide, azobis(isobutyronitrile), p-toluene sulfonyl hydrazide, p-toluene sulfonyl semicarbazide, carbohydrazide, p-p'-oxybis(benzenesulfonylhydrazide) and mixtures thereof. Of these, carbohydrazide is preferred.
- the gas generating chemical or chemicals are generally present in the aqueous solution or dispersion in an amount in the range of from about 0% to about 50% by weight of water in the aqueous solution or dispersion, more preferably in an amount of from about 0% to about 40%.
- the water soluble mixture of foaming and foam stabilizing surfactants in the aqueous solution or dispersion functions to facilitate foaming of the cement composition and to stabilize the foam after it is formed.
- An example of such a mixture of foaming and foam stabilizing surfactants which is preferred for use in accordance with this invention is comprised of an ethoxylated alcohol ether sulfate surfactant, an alkyl or alkene amidopropylbetaine surfactant and an alkyl or alkene amidopropyldimethylamine oxide surfactant.
- a preferred such mixture is comprised of 63.3 parts by weight of the ethoxylated alcohol ether sulfate surfactant, 31.7 parts by weight of the alkyl or alkene amidopropylbetaine surfactant and 5 parts by weight of the alkyl or alkene amidopropyldimethylamine oxide surfactant.
- the mixture of surfactants is described in detail in U.S. Patent No. 6,063,738 issued on May 16, 2000 to Chatterji et al. which is incorporated herein by reference thereto.
- the mixture of surfactants is generally included in the aqueous solution or dispersion in an amount in the range of from about 2% to about 15% by weight of water therein, more preferably in an amount of about 4% to about 10%.
- the well cement composition and the aqueous solution or dispersion are pumped at rates such that the weight ratio of the oxidizing agent in the well cement composition to the gas generating chemical in the aqueous solution or dispersion is in the range of from about 15:1 to about 1:1.
- the aqueous solution or dispersion described above can also include hydraulic cement. That is, the aqueous solution or dispersion can be a second cement composition which is pumped into the first cement composition downstream of the cement pumps.
- a hydraulic cement is included in the aqueous solution or dispersion it is a hydraulic cement of the various types described above, preferably Portland cement.
- the hydraulic cement is included in the aqueous solution or dispersion in an amount in the range of from about 150% to about 300% by weight of water in the aqueous solution or dispersion.
- a well cement composition comprised of a hydraulic cement, sufficient water to form a pumpable slurry and a gas generating chemical which is activated to produce gas by an oxidizing agent is provided.
- the cement composition is pumped into the subterranean zone by way of the well bore with one or more cement pumps.
- An aqueous solution or dispersion comprised of water, a gas generating chemical which is activated to produce gas when introduced into a well cement composition but is not activated to produce gas by an oxidizing agent, a water soluble mixture of foaming and foam stabilizing surfactants and an oxidizing agent is also provided.
- the aqueous solution or dispersion containing the gas generating chemical activated by a cement composition, the mixture of surfactants and the oxidizing agent is pumped or otherwise introduced into the cement composition downstream of the one or more cement pumps.
- the gas generating chemical in the cement composition is activated by the oxidizing agent in the aqueous solution or dispersion to produce gas and the gas generating chemical in the aqueous solution or dispersion is activated by the cement composition to produced gas.
- the cement composition is foamed with the gas and stabilized by the mixture of surfactants in the aqueous solution, or dispersion, all as the resulting cement composition flows through the well bore and into the subterranean zone.
- the hydraulic cement utilized in the well cement composition can be any of the various hydraulic cements described above and is preferably Portland cement.
- the water utilized in the cement composition and the aqueous solution or dispersion is selected from the group consisting of fresh water or salt water. The water is generally present in the cement composition in an amount in the range of from about 30% to about 70% by weight of the hydraulic cement therein.
- the gas generating chemical in the well cement composition which is activated to produce gas by an oxidizing agent includes, but is not limited to, toluene sulfonyl hydrazide, carbohydrazide, toluene sulfonyl semicarbazide, hydrazine and its salts with acids, and mixtures thereof. Of these, carbohydrazide is preferred.
- the gas generating chemical which is activated by an oxidizing agent is present in the well cement composition in an amount in the range of from about 2% to about 15% by weight of hydraulic cement in the composition.
- the water in the aqueous solution or dispersion can be fresh water or salt water as described above.
- the gas generating chemical in the aqueous solution or dispersion which is activated when introduced into a well cement composition is selected from the group consisting of azodicarbonamide, azobis(isobutyronitrile) and azodicarboxylic acid and its salts of alkali and alkaline earth metals and mixtures thereof. Of these, azodicarbonamide is preferred.
- the gas generating chemical which is activated when introduced into a well cement composition is present in the aqueous solution or dispersion in an amount in the range of from about 0% to about 50% by weight of water in the aqueous solution or dispersion.
- the water soluble mixture of foaming and foam stabilizing surfactants is comprised of a mixture of an ethoxylated alcohol ether sulfate surfactant, an alkyl or alkene amidopropylbetaine surfactant and an alkyl or alkene amidopropyldimethylamine oxide as described above.
- the mixture of surfactants is present in the aqueous solution or dispersion in an amount in the range of from about 2% to about 15% by weight of water in the aqueous solution.
- the well cement composition and the aqueous solution or dispersion are pumped at rates such that the weight ratio of the gas generating chemical in the well cement composition to the oxidizing agent in the aqueous solution or dispersion is in the range of from about 1 :1 to about 1:15.
- the gas generating chemical in the well cement composition is activated to produce gas by the oxidizing agent in the aqueous solution or dispersion and the gas generating chemical in the aqueous solution or dispersion is activated to produce gas by the well cement composition.
- the combined cement composition is foamed with the produced gas as it travels through the well bore into the subterranean zone and the foam is facilitated and stabilized by the mixture of surfactants.
- a well cement composition is provided comprised of a hydraulic cement, sufficient water to form a pumpable slurry and a gas generating chemical which is activated to produce gas by an oxidizing agent.
- the cement composition is pumped into the subterranean zone by way of the well bore with one or more cement pumps.
- An aqueous solution or dispersion is provided comprised of water, a gas generating chemical which is activated to produce gas when introduced into a well cement composition but is not activated to produce gas by an oxidizing agent and an oxidizing agent.
- the aqueous solution or dispersion containing the gas generating chemical activated by a cement composition and the oxidizing agent are pumped or otherwise introduced into the cement composition containing the gas generating chemical which is activated by an oxidizing agent downstream of the one or more cement pumps so that the well cement composition and the aqueous solution or dispersion are combined and gas is produced in the cement composition.
- An aqueous solution of a mixture of foaming and foam stabilizing surfactants is also provided.
- the aqueous solution of the mixture of surfactants is pumped or otherwise introduced into the combined cement composition so that the final composition formed is foamed and stabilized by the mixture of surfactants as the cement composition flows through the well bore.
- the hydraulic cement, the water and the gas generating chemical utilized in the above described method are the same and present in the same amounts as those set forth above for the preceding method.
- the water, the gas generating chemical which is activated to produce gas when introduced into a well cement composition but is not activated to produce gas by an oxidizing agent are also as described above and are present in the amounts given above.
- the aqueous solution of a mixture of foaming and foam stabilizing surfactants includes the mixture of surfactants described above present in the solution in an amount in the range of from about 25% to about 50% by weight of the water in the solution.
- the well cement composition, the aqueous solution or dispersion and the aqueous solution of foaming and foam stabilizing surfactants are pumped at rates such that the weight ratio of the gas generating chemical in the well cement composition to the oxidizing agent in the aqueous solution or dispersion to the mixture of surfactants in the aqueous solution thereof is in the range of from about 1 :1:0.1 to about 1:15:0.6.
- the cement compositions of this invention can include a variety of additives for improving or changing the properties of the cement compositions.
- additives include, but are not limited to, set retarding agents, fluid loss control agents, dispersing agents, set accelerating agents and formation conditioning agents.
- a preferred method of this invention for generating gas in and foaming a cement composition introduced into a subterranean zone penetrated by a well bore comprises the steps of: (a) providing a well cement composition comprised of a hydraulic cement, sufficient water to form a pumpable slurry and a water soluble oxidizing agent; (b) pumping the cement composition into the subterranean zone by way of the well bore with one or more cement pumps; (c) providing an aqueous solution or dispersion comprised of water, a gas generating chemical which is activated to produce gas by an oxidizing agent and a water soluble mixture of foaming and foam stabilizing surfactants; and (d) pumping the aqueous solution or dispersion containing the gas generating chemical and the mixture of surfactants or otherwise introducing it into the cement composition containing the oxidizing agent downstream of the one or more cement pumps so that the well cement composition and said aqueous solution or dispersion are combined, the oxidizing agent activates the gas generating chemical whereby gas is
- Another method of this invention for generating gas in and foaming a cement composition introduced into a subterranean zone penetrated by a well bore comprises the steps of: (a) providing a well cement composition comprised of a hydraulic cement, sufficient water to form a pumpable slurry and an oxidizing agent selected from the group consisting of ammonium persulfate, sodium persulfate, potassium persulfate, sodium chloride, sodium chlorate, hydrogen peroxide, sodium perborate, sodium peroxy carbonate, calcium hypochlorite, sodium hypochlorite, sodium hypobromite, sodium bromite, sodium bromate, sodium chlorate and mixtures thereof; (b) pumping the well cement composition into the subterranean zone by way of the well bore with one or more cement pumps;
- Still another method of generating gas in and foaming a cement composition introduced into a subterranean zone penetrated by a well bore comprises the steps of: (a) providing a well cement composition comprised of a hydraulic cement, sufficient water to form a pumpable slurry and a gas generating chemical which is activated to produce gas by an oxidizing agent; (b) pumping the well cement composition into the subterranean zone by way of the well bore with one or more cement pumps; (c) providing an aqueous solution or dispersion comprised of water, a gas generating chemical which is activated to produce gas when introduced into a well cement composition but is not activated to produce gas by an oxidizing agent, a water soluble mixture of foaming and foam stabilizing surfactants and an oxidizing agent; and (d) pumping the aqueous solution or dispersion containing the gas generating chemical activated by a cement composition, the mixture of foaming and foam stabilizing surfactants and the oxidizing agent or otherwise introducing it into the cement composition containing
- Yet another method of generating gas in and foaming a cement composition introduced into a subterranean zone penetrated by a well bore comprises the steps of: (a) providing a well cement composition comprised of a hydraulic cement, sufficient water to form a pumpable slurry and a gas generating chemical which is activated to produce gas by an oxidizing agent; (b) pumping the well cement composition into the subterranean zone by way of the well bore with one or more cement pumps; (c) providing an aqueous solution or dispersion comprised of water, a gas generating chemical which is activated to produce gas when introduced into a well cement composition but is not activated to produce gas by an oxidizing agent and an oxidizing agent; (d) pumping the aqueous solution or dispersion containing the gas generating chemical activated by a cement composition and the oxidizing agent or otherwise introducing it into the cement composition containing the gas generating chemical which is activated by an oxidizing agent downstream of the one or more cement pumps so that the well cement composition and the
- a dry blend of 3,000 pounds of Class A cement with 150 pounds of toluenesulfonyl hydrazide was mixed with water to prepare a slurry of density of 16.3 pounds per gallon.
- the slurry was held in the mixing equipment for 5 minutes.
- 5 gallons of the foaming and foam stabilizing surfactant mixture was injected with minimal agitation.
- 138 pounds of potassium persulfate was dissolved in 36 gallons of water.
- 30 pounds of azodicarbonamide was added with stirring to obtain an aqueous dispersion.
- the two fluids were combined by pumping both fluids into a pressurized flow loop.
- the two fluids flowed through a 1" choke to assure mixing of the fluids.
- the fluid loop had a constant pressure of 500 psi through the pumping process.
- the fluid loop included a 10 ft. inline sample chamber having valves at opposite ends. All fluid flow was maintained through the sample chamber.
- the valves were closed trapping the foamed cement in the 10 ft. x 2 in. (diameter) pipe.
- the sample pressure was 500 psi as with the flow loop pressure.
- the sample chamber was then removed and the cement slurry was allowed to set. Considerable amount of heat was generated during the gas generation process.
- a metal pipe made of 17-4 stainless steel and pressure rated for 30,000 psi, with an outer diameter of 3.5" and an inner diameter of 2.44" and provided with Acme threads at the top and at about 2" from the bottom end was drilled to provide four entry points at equal distances from each other.
- One hole was fitted with a thermocouple, the second and third holes were fitted to serve as ports for pumping or withdrawing fluids, and the fourth hole was provided with a plug.
- the bottom end of the chamber was fitted with a sealed stirring mechanism connected to a paddle on the inside and an electric motor on the outside.
- the height of the paddle was such that the injected fluids entered at about the middle of the paddle.
- the chamber was provided with a tightly fitting piston provided with an O-ring and a rod.
- the top of the chamber was fitted with a lid assembly with a hole in the center through which the rod attached to the piston could move up and down.
- the lid assembly was provided with an inlet for connection to a water supply line that had an inline SpragueTM pump.
- a fluid pump manufactured by Ruska Instrument Corporation, Houston, Texas was used to pump fluid into the chamber.
- the equipment was calibrated to read volume increase by measuring the length of the rod extending through the top lid assembly.
- a cement slurry was prepared by mixing 350 grams Class A cement and 27 grams of sodium chlorite (79% active content) with 146 grams water. About 250 cubic centimeters of this slurry were introduced into the chamber through one of the injection ports. The apparatus was pre-assembled such that the space below the piston becomes liquid-full with 250 cubic centimeters of an aqueous fluid. A 26.3 milliliter portion of an aqueous solution containing carbohydrazide (18.75% by weight) and foaming and foam stabilizing surfactants (5% by weight) was injected by means of the fluid injection pump. The density of the slurry with all the components added was 15.6 pounds per gallon.
- a pressure of 1,000 psi was exerted on top of the piston with pressurized water using the SpragueTM pump.
- the slurry was stirred at 2,000 rpm for 5 minutes. Any pressure increase due to gas generation was released such that a constant pressure of 1,000 psi on top of the cement slurry was maintained.
- the temperature increased to about 170°F due to chemical reactions in the slurry.
- the extension of the rod attached to piston was measured and the expansion of the slurry volume due to gas generation was measured from the calibration curve.
- the slurry was collected in a collection chamber under a pressure of 950 psi and was allowed to set at that pressure at room temperature.
- the measured density of the set cement was 13.8 pounds per gallon.
- the % nitrogen gas present in set cement collected and cured at 1,000 psi was calculated to be about 11% by volume.
- the preassembled chamber was charged with 288 cubic centimeters of a cement slurry prepared by mixing 800 grams of Class A cement, 8 grams sulfonated acetone formaldehyde condensate, and 52 grams carbohydrazide. After half of the slurry was added to the chamber, 2.3 grams of the foaming and foam stabilizing surfactant solution was injected and then the remaining slurry was added. The addition hole was closed with a plug, and 141 grams of sodium chlorite solution (37% active) was injected through a port in the chamber. The chamber was pressurized 750 psi and stirred at about 2,500 rpm for 5 minutes.
- the reaction was completed within this period as indicated by the rod extension. Based on the volume increase the amount of gas generated was calculated to be 47% by volume at 750 psi.
- the foamed slurry was collected into a collection vessel pressurized to 740 psi and collection vessel was kept overnight in a water bath maintained at 160°F.
- the set cement had a density of 10.5 pounds per gallon indicating the presence of gas phase at 33% by volume.
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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MXPA04011873A MXPA04011873A (en) | 2002-05-31 | 2003-05-22 | Methods of generating gas in and foaming well cement compositions. |
AU2003227966A AU2003227966B2 (en) | 2002-05-31 | 2003-05-22 | Methods of generating gas in and foaming well cement compositions |
CA002486570A CA2486570A1 (en) | 2002-05-31 | 2003-05-22 | Methods of generating gas in and foaming well cement compositions |
EP03725434A EP1511913A1 (en) | 2002-05-31 | 2003-05-22 | Methods of generating gas in and foaming well cement compositions |
BR0311421-0A BR0311421A (en) | 2002-05-31 | 2003-05-22 | Method for generating gas and producing foam in a cement composition introduced into an underground zone penetrated by a wellbore |
NO20045634A NO20045634L (en) | 2002-05-31 | 2004-12-23 | Process for generating gas and foaming a cement mixture |
Applications Claiming Priority (2)
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US10/159,001 US6858566B1 (en) | 2002-05-31 | 2002-05-31 | Methods of generating gas in and foaming well cement compositions |
US10/159,001 | 2002-05-31 |
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PCT/GB2003/002211 WO2003102361A1 (en) | 2002-05-31 | 2003-05-22 | Methods of generating gas in and foaming well cement compositions |
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EP (1) | EP1511913A1 (en) |
BR (1) | BR0311421A (en) |
CA (1) | CA2486570A1 (en) |
MX (1) | MXPA04011873A (en) |
NO (1) | NO20045634L (en) |
WO (1) | WO2003102361A1 (en) |
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CN101423756B (en) * | 2008-10-14 | 2010-12-22 | 中国石油集团川庆钻探工程有限公司工程技术研究院 | Gas well water blocking damage treating agent |
CN101423755B (en) * | 2008-10-14 | 2010-12-22 | 中国石油集团川庆钻探工程有限公司工程技术研究院 | Formula of gas well water blocking damage treating agent |
US8689871B2 (en) | 2010-11-08 | 2014-04-08 | Schlumberger Technology Corporation | Compositions and methods for well completions |
US9738822B2 (en) | 2013-10-02 | 2017-08-22 | Schlumberger Technology Corporation | Compositions and methods for cementing wells |
WO2019147635A1 (en) * | 2018-01-24 | 2019-08-01 | Saudi Arabian Oil Company | Settable, form-filling loss circulation control compositions comprising in situ foamed calcium aluminate cement systems and methods of using them |
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US10450495B2 (en) | 2018-01-24 | 2019-10-22 | Saudi Arabian Oil Company | Settable, form-filling loss circulation control compositions comprising in situ foamed calcium aluminate cement systems and methods of using them |
US10526524B2 (en) | 2018-01-24 | 2020-01-07 | Saudi Arabian Oil Company | Settable, form-filling loss circulation control compositions comprising in situ foamed non-hydraulic sorel cement systems and method of use |
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US10544350B2 (en) | 2018-01-24 | 2020-01-28 | Saudi Arabian Oil Company | Settable, form-filling loss circulation control compositions comprising in situ foamed non-hydraulic sorel cement systems and method of use |
WO2020172511A1 (en) * | 2019-02-21 | 2020-08-27 | Saudi Arabian Oil Company | Gas generating compositions |
US10858565B2 (en) | 2019-02-21 | 2020-12-08 | Saudi Arabian Oil Company | Gas generating compositions |
WO2020172512A3 (en) * | 2019-02-21 | 2020-12-10 | Saudi Arabian Oil Company | Storable gas generating compositions |
US10934468B2 (en) | 2019-02-21 | 2021-03-02 | Saudi Arabian Oil Company | Storable gas generating compositions |
US11203708B2 (en) | 2019-02-21 | 2021-12-21 | Saudi Arabian Oil Company | Gas generating compositions |
Also Published As
Publication number | Publication date |
---|---|
AU2003227966A1 (en) | 2003-12-19 |
CA2486570A1 (en) | 2003-12-11 |
BR0311421A (en) | 2005-03-15 |
MXPA04011873A (en) | 2005-03-31 |
EP1511913A1 (en) | 2005-03-09 |
NO20045634L (en) | 2005-02-23 |
US6858566B1 (en) | 2005-02-22 |
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