Patent Publication Number: US-6982000-B2

Title: Cement compositions including silane treated amorphous silica

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
     This application is a divisional of U.S. patent application Ser. No. 10/853,878 filed May 26, 2004. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to cementing generally, and more particularly, to cement compositions which set into resilient high strength masses. 
     2. Description of the Prior Art 
     Hydraulic cement compositions are commonly utilized in forming structures above and below ground. In forming such structures, a hydraulic cement composition is pumped into a form or other location to be cemented and allowed to set therein. Generally, the set cement compositions must have high shear bond strength to avoid bond failure. 
     In the construction and repair of wells such as oil and gas wells, hydraulic cement compositions are pumped into locations therein to be cemented and allowed to set. In primary well cementing, a hydraulic cement composition is pumped into the annular space between the walls of the well bore and the exterior surfaces of a pipe string disposed therein. The cement composition is permitted to set in the annular space thereby forming an annular sheath of hardened substantially impermeable cement therein. The cement sheath physically supports and positions the pipe string in the well bore and bonds the exterior surfaces of the pipe string to the walls of the well bore whereby the undesirable migration of fluids between zones or formations penetrated by the well bore is prevented. 
     The cement sheath in the annulus between a pipe string and the walls of a well bore often fails due to pipe movements which cause shear stresses to be exerted on the set cement. Such stress conditions are commonly the result of relatively high fluid pressures and/or temperatures inside the cemented pipe string during testing, perforating, fluid injection or fluid production. The high internal pipe pressure and/or temperature can result in the expansion of the pipe string, both radially and longitudinally, which places stresses on the cement sheath causing the cement bond between the exterior surfaces of the pipe or the well bore walls, or both, to fail which allows leakage of formation fluids, etc. 
     Thus, there are needs for improved cement compositions and methods whereby after setting, the cement compositions form solid masses which have high bond strengths sufficient to withstand stresses without failure. 
     SUMMARY OF THE INVENTION 
     The present invention provides cement compositions and methods which meet the needs described above and overcome the deficiencies of the prior art. A cement composition of this invention comprises a hydraulic cement, silica hydrophobicized with a mixture of organosilicon compounds and water. 
     Another cement composition of this invention comprises a hydraulic cement, silica hydrophobicized with a mixture of organosilicon compounds present in an amount in the range of from about 10% to about 20% by weight of the hydraulic cement and sufficient water to form a slurry. 
     A method of cementing of this invention comprises the steps of placing a cement composition comprising hydraulic cement, silica hydrophobicized with a mixture of organosilicon compounds and sufficient water to form a slurry in a location to be cemented, and allowing the cement composition to harden therein. 
     Another method of cementing of this invention comprises the steps of placing a cement composition between a pipe string and the walls of a well bore which hardens into a high shear bond strength mass comprising a hydraulic cement, silica hydrophobicized with a mixture of organosilicon compounds present in an amount in the range of from about 10% to about 20% by weight of the hydraulic cement and sufficient water to form a slurry, and allowing the cement composition to harden therein. 
     The objects, features and advantages of the present invention will be readily apparent to those skilled in the art upon a reading of the description of preferred embodiments which follows. 
    
    
     DESCRIPTION OF PREFERRED EMBODIMENTS 
     The present invention provides improved cement compositions and methods of cementing whereby the hardened cement compositions are solid masses having high bond strengths. 
     A cement composition of this invention comprises a hydraulic cement, silica hydrophobicized with a mixture of organosilicon compounds and water. 
     Another cement composition of this invention comprises a hydraulic cement, silica hydrophobicized with a mixture of organosilicon compounds present in an amount in the range of from about 10% to about 20% by weight of hydraulic cement and sufficient water to form a slurry. 
     A variety of hydraulic cements can be utilized in accordance with the present invention including those comprising 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, high aluminum content cements, silica cements and high alkalinity cements. Portland cements are generally preferred for use in accordance with the present invention. Portland cements of the types defined and described in  API Specification For Materials And Testing For Well Cements , API Specification 10B, 22 nd  Edition, dated Dec. 1, 1997 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 more preferred and class G being the most preferred. 
     The water utilized in the cement compositions of this invention can be fresh water or salt water including brines and seawater. 
     It has been discovered that the addition of precipitated amorphous silica hydrophobicized with a mixture of organosilicon compounds to the cement compositions of this invention significantly improves the shear bond strengths of the hardened cement compositions. The silica hydrophobicized with a mixture of organosilicon compounds that is useful in accordance with the present invention is described in detail in U.S. Pat. No. 6,613,139 issued to Revis on Sep. 2, 2003, which is incorporated herein by reference thereto. More specifically, amorphous silica is contacted with a mixture of organosilicon compounds. One such mixture that can be utilized is a mixture of diorganodihalosilane and monoorganotrihalosilane present in a weight ratio of 1:0.1 to 1:2, respectively. The mixture can further comprise mercaptopropyltriethoxysilane. Other mixtures that can be utilized include a mixture of dialkyldichlorosilane and a monoalkyltrichlorosilane including, but not limited to, a mixture of dimethyldichlorosilane and methyltrichlorosilane and a mixture of dimethyldichlorosilane and n-propyltrichlorosilane, phenyltricholorosilane or cyanopropyltrichlorosilane. Another mixture of organosilicon compounds that can be utilized is a mixture of a diorganodihalosilane, a monoorganotrihalosilane and an alkoxysilane such as mercaptopropyltriethoxysilane. 
     The cement compositions of this invention can also be foamed cement compositions. That is, the compositions can include a foaming surfactant and a gas whereby upon being mixed, a foamed cement composition is formed. Examples of foaming surfactants that can be used include, but are not limited to, a mixture of the ammonium salt of alcohol ether sulfate (HOWCO SUDS™) and cocoylamidopropyl betaine (HC-2™) commercially available from Halliburton Energy Services, Inc.; a 2:1 mixture of the sodium salt of alpha-olefin sulfonate (AQF-2™) and cocylamidopropyl betaine (HC-2™) commercially available from Halliburton Energy Services, Inc.; and a mixture of an ethoxylated alcohol ether sulfate, an alkyl or alkyene amidopropyl betaine and an alkyl or alkene amidopropyldimethylamine oxide commercially available from Halliburton Energy Services, Inc. under the trade name ZONESEALANT 2000™. Of these, ZONESEALANT 2000™ additive is preferred. 
     The gas is generally air or nitrogen with nitrogen being preferred. The foaming surfactant is present in the cement composition in an amount in the range of from about 1% to about 5% by weight of water. The gas is present in an amount sufficient to form a foam, generally in an amount in the range of from about 20% to about 80% by weight of water in the cement composition. 
     A cement composition of this invention comprises: a hydraulic cement; silica hydrophobicized with a mixture of organosilane compounds; and water. 
     Another resilient, high shear bond strength cement composition of the present invention comprises: a hydraulic cement, silica hydrophobicized with organosilane compounds present in an amount in the range of from about 10% to about 20% by weight of the hydraulic cement and sufficient water to form a slurry. 
     A method of cementing of this invention comprises: placing a cement composition comprising hydraulic cement, silica hydrophobicized with a mixture of organosilicon compounds and sufficient water to form a slurry in a location to be cemented; and allowing the cement composition to harden therein. 
     Another method of cementing of this invention comprises: placing a cement composition between a pipe string and the walls of a well bore which hardens into a high shear bond strength mass comprising a hydraulic cement, silica hydrophobicized with a mixture of organosilicon compounds present in an amount in the range of from about 10% to about 20% by weight of the hydraulic cement and sufficient water to form a slurry; and allowing the cement composition to harden therein. 
     In order to further illustrate the compositions and methods of the present invention, the following examples are given. 
     EXAMPLE 
     A reaction flask was charged with 2000 grams of amorphous silica slurry and 165 grams of concentrated sulfuric acid. The slurry was heated to a temperature of 70° C. and a mixture containing 9.1 grams of methyltrichlorosilane and 16.38 grams of dimethyldichlorosilane was added to the reaction flask over a period of about 2 to 7 minutes. The treated slurry was then stirred and cooled to room temperature over a 60 minute period. 600 milliliters of a solution containing 25% by weight of sodium hydroxide was added to the stirred slurry in order to adjust the pH to a range of from 3.4 to 3.7. The slurry was then transferred to a Buchner funnel and vacuum filtered to remove the aqueous phase. The filter cake was then washed with water until the filtrate read less than 100 micro ohms. After allowing it to air dry, the treated silica was reslurried in deionized water to provide a slurry containing 20% to 40% by weight of the treated silica. The slurry was mixed until the solids were broken up and then pumped to a spray drier at a rate of about 20 milliliters per minute with an inlet temperature of 260° C. and an outlet temperature between 120° C. to 140° C. The dried silica was collected. 
     An elemental analysis of the resulting hydrophoicized silica showed that it had a carbon content of 5.13%; a hydrogen content of 0.96%; a nitrogen content of 0.05%; and a surfactant of 0.53%. An elemental analysis of the untreated amorphous silica showed that it had a carbon content of 1.33%; a hydrogen content of 0.23%; a nitrogen content of 0.02%; and a sulfur content of 0.53%. 
     Non-foamed and foamed cement slurries containing 10, 15 and 20% of hydrophobicized and untreated silica were prepared. After setting, the shear bond strengths of the various cements were determined. The results of these tests are shown in the Table below. 
     
       
         
           
               
             
               
                 TABLE 
               
             
            
               
                   
               
               
                 Slurry: Class G Cement + Amorphous Silica + Water 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Treat 
                   
                   
                   
                   
               
               
                 Amorphous 
                 Amphorous 
                 Slurry 
                 Foamed 
                   
                   
               
               
                 Silica 
                 Silica 1   
                 Weight 
                 Weight 
                 Water 
                 Shear Bond 2   
               
               
                 % 
                 % 
                 #/gal 
                 #/gal 
                 Gal/sk 
                 Psi 
               
               
                   
               
               
                 10 
                   
                 15.00 
                   
                 6.53 
                 223.5 
               
               
                   
                 10 
                 15.00 
                   
                 6.53 
                 252.5 
               
               
                 10 
                   
                 15.00 
                 13.00 
                 6.53 
                 234.0 
               
               
                   
                 10 
                 15.00 
                 13.00 
                 6.53 
                 292.0 
               
               
                 15 
                   
                 15.00 
                   
                 6.73 
                 164.0 
               
               
                   
                 15 
                 15.00 
                   
                 6.73 
                 208.0 
               
               
                 15 
                   
                 15.00 
                 13.00 
                 6.73 
                 214.0 
               
               
                   
                 15 
                 15.00 
                 13.00 
                 6.73 
                 287.0 
               
               
                 20 
                   
                 15.00 
                   
                 6.93 
                 213.0 
               
               
                   
                 20 
                 15.00 
                   
                 6.93 
                 257.0 
               
               
                 20 
                   
                 15.00 
                 13.00 
                 6.93 
                 273.0 
               
               
                   
                 20 
                 15.00 
                 13.00 
                 6.93 
                 410.0 
               
               
                   
               
               
                   1 Treated with 9.1 grams of Methyltrichloro Silane and 16.38 grams of Dimethyldichloro Silane 
               
               
                   2 The slurries were cured at 140° F. for 72 hours for shear bond measurements following API procedure. 
               
            
           
         
       
     
     From the Table, it can be seen that the cement compositions containing treated amorphous silica had significantly higher shear bonds than the cement compositions containing non-treated amorphous silica. 
     Thus, the present invention is well adapted to carry out the objects and advantages mentioned as well as those which are inherent therein. While numerous changes may be made by those skilled in the art, such changes are encompassed within the spirit of this invention as defined by the appended claims.