Abstract:
This invention relates to a composition and use application of aqueous fluidized polymer suspensions of hydroxyethyl cellulose (HEC) suspended in sodium thiosulfate for use in oil field applications such completion fluids, drilling fluids, fracturing fluids and oil well cement slurries as rheology/viscosity modifier and fluid loss reducer for use where the affect on the marine environment is to be minimized.

Description:
[0001]    This application claims the benefit of Provisional Application 60/906,149 filed on Mar. 9, 2007 which is incorporated by reference. 
     
    
     FIELD OF INVENTION 
       [0002]    The present invention relates to a composition and to the use of sodium thiosulfate based fluidized polymer suspensions of hydroxyethyl cellulose in oil field applications such completion fluids, drilling fluids and oil well cement slurries as rheology/viscosity modifier and fluid loss reducer. 
       BACKGROUND OF THE INVENTION 
       [0003]    Hydroxyethyl cellulose (HEC) is widely used in oilfield water-based fluids. High-viscosity types are generally used, in completion fluids, for rheology and fluid loss control properties. Low viscosity types are typically used, in oil-well cement slurries and drill-in-fluids, for filtration control properties. However, high viscosity types may find functionality, along with low viscosity ones, in oil-well cement slurries as free water control additives. 
         [0004]    For easy handling in oil and gas well rigs and convenient storage on offshore operations, liquid additives are most preferred. However, because of potential environmental hazards when discharged offshore, usage of liquid additives is strictly regulated. A variety of environmentally acceptable solvent based polymer suspensions have been used for the past few years. These suspensions are based on either mineral oil or glycols. However, these types of suspensions still face some use restrictions as none of them meet the entire regulatory requirements regarding the aquatic toxicity, biodegradability and bio-accumulation. 
         [0005]    The search for oil and gas well products which are entirely composed of PLONOR (Pose Little or No Risk to the environment) components is ongoing. All existing products which do not meet the requirements for PLONOR components are placed on a phase-out list, and need to be replaced as soon as “green” additives are available. 
         [0006]    U.S. Pat. No. 5,268,466 to Burdick, incorporated herein by reference in its entirety, discloses that stable suspension of water soluble polysaccharides selected from the group of HEC, (hydroxyethyl cellulose: HPC (hydroxypropyl cellulose, MC (methyl-cellulose), EHEC (ethyl hydroxyethyl cellulose, and the like, and Guar/Guar derivatives can be prepared in a solution of 12 to 40 wt. % dibasic potassium phosphate. The suspension includes 15-30 wt. % of said polysaccharide. The suspension further includes a stabilizing amount of xanthan gum. The industrial application of these stable suspensions was recited as for use in construction and coating materials such as joint compounds and latex paints. 
         [0007]    U.S. Pat. No. 5,407,475 discloses a suspension composition of HEC in sodium or ammonium thiosulfate brines. The composition is claimed for use in drilling fluids (completion) and provides improved thermal stability for HEC. The suspension composition contains at least 30% w/w sodium or ammonium thiosulfate. The patent does not disclose the use of such a composition in oil-well cementing slurries. 
         [0008]    In US Patent Publication 2007/0135312 A1, incorporated herein by reference in its entirety, a PLONOR rated fluidized suspension of HEC was disclosed. This patent application specifically teaches the use of di-potassium phosphate based aqueous suspension of HEC in oil-well servicing fluids. 
         [0009]    To provide a wider compatibility with other cement slurry additives as well as enhance the thermal stability of HEC, there is a clear need to develop a wide range of suspensions that would still be rated PLONOR to meet specific application requirements. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0010]      FIG. 1  is a graph depicting the rheological profiles of suspensions of the present invention and comparative precursor materials at room temperature as well as at elevated temperature in NaCl saturated brine. 
       
    
    
     SUMMARY OF THE INVENTION 
       [0011]    A suspension composition comprising a fluid polymer suspension comprising hydroxyethyl cellulose (HEC) suspended in an aqueous solution of sodium thiosulfate, further comprising a stabilizer wherein the stabilizer is a xanthan gum or a PLONOR rated preservative such as Sodium Benzoate. The composition is useful when combined with oil field servicing fluid selected from the group consisting of drilling fluids, completion/workover fluids, stimulation fluids, such as fracturing fluids, oil well cementing fluids, gravel packing fluids and enhanced oil recovery fluids. 
       DETAILED DESCRIPTION OF THE INVENTION 
       [0012]    An objective of this invention is to provide an improved suspension of HEC in a concentrated aqueous sodium thiosulfate salt solution that has improved compatibility with other additives used in oilfield servicing fluids. 
         [0013]    Sodium thiosulfate has the advantage to be listed on the PLONOR approved list of products for use in the North Sea. 
         [0014]    To develop an improved long-term stability of sodium thiosulfate suspensions, modifications of the compositions have been implemented. One improvement to the sodium thiosulfate suspensions is to include a suspending agent as well as a preservative selected from the PLONOR list of approved chemicals. Suspensions containing this suspending agent have been observed to be physically stable for over 3 months. 
         [0015]    It has been discovered that suspensions of HEC in concentrated aqueous sodium thiosulfate brine, stabilized with a small amount of xanthan gum and optionally containing a preservative such as sodium benzoate provide stable compositions that are entirely composed of components listed as PLONOR substances. 
         [0016]    The suspension composition comprises water, HEC in an amount of about 5 to about 80 wt %, sodium thiosulfate in an amount of about 10 to about 30 wt. %, xanthan gum present in an amount of about 0.01 to about 0.50 wt %. Optionally in addition, a preservative of sodium benzoate may be present in an amount of about 0.1 to about 1.0 wt %. 
         [0017]    To prepare the suspension composition the components are added in any order, and mixed at room temperature. 
         [0018]    The following examples illustrate the typical performance of this type of suspensions of the present invention in completion fluids and low temperature oil-well cement slurry compositions 
       EXAMPLE 1 
       [0019]    The suspension composition of this invention used in Example 1 consists of the following components: water; sodium thiosulfate, at about 24% by weight; HEC, at about 20% by weight; a minor amount of xanthan gum, at about 0.15% to about 0.20% by weight; and optionally a minor amount of a preservative such as sodium benzoate at an effective amount, typically at about 0.50% by weight. The resulting suspensions had excellent flow properties (Brookfield viscosity 1600-2100 cPs). After 3 months storage at room temperature, no signs of phase separation were observed. 
         [0020]    Additionally, the suspensions showed excellent freeze/thaw stability. The freezing point for the suspensions was measured below −15° C. See Table 1 for detailed suspension compositions, all parts and percentages being by weight, unless otherwise indicated. 
         [0000]    
       
         
               
             
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Detailed Suspensions Composition 
               
             
          
           
               
                 Ingredients 
                 Suspension 1 
                 Suspension 2 
                 Suspension 3 
               
               
                   
               
               
                 DI water 
                 55.33% 
                 55.89% 
                 55.33% 
               
               
                 Xanthan gum (Rhodopol ® 
                  0.17% 
                  0.20% 
                  0.17% 
               
               
                 23 xanthan gum, 
               
               
                 available from Rhodia USA) 
               
               
                 Na. Benzoate 
                  0.50% 
                 — 
                  0.50% 
               
               
                 Na. Thiosulfate 
                 24.00% 
                 23.95% 
                 24.00% 
               
               
                 HEC (Natrosol ® 250 
                 20.00% 
                 19.96% 
                 — 
               
               
                 JR HEC, available from 
               
               
                 Hercules Incorporated) 
               
               
                 HEC (Natrosol ® 
                 — 
                 — 
                 20.00% 
               
               
                 Hivis HEC, available from 
               
               
                 Hercules Incorporated) 
               
               
                   
               
             
          
         
       
     
         [0021]    The viscosity of the Suspension 1 was 2,100 cPs, the viscosity of Suspension 2 was 1,660 cPs and the viscosity of Suspension 3 was 2,240 cPs as measured after preparation using a Brookfield viscometer. 
       EXAMPLE 2 
     Application in Completion Fluids 
       [0022]    The thickening efficiency of a suspension of the present invention (Natrosol® HIVIS HEC suspension, available from Hercules Incorporated (Suspension 3)) was evaluated against HEC, not in suspension form, but rather as a dry powder (Natrosol® HIVIS HEC, available from Hercules Incorporated). The HEC in dry powder form was compared to the HEC suspension by dissolving 2 lb/bbl (0.57 wt. %) equivalent dry HEC in NaCl saturated brine. The NaCl saturated brine was first prepared by dissolving 360 g NaCl in 1000 ml Deionized water. Then, 2.0 g dry HEC or 10.0 g as-is Suspension 3 was added into 420 g NaCl saturated water while mixing on Hamilton beach mixer (˜11,500 rpm). To speed up the hydration of the polymer, 1-ml 10% NaOH solution was added into the polymer solution to raise the pH. To reduce/eliminate excess foaming, a few drops of defoamer were added. The solution was mixed for an elapsed time of 60 minutes. Two separate solutions have been prepared, homogenized and then split into two portions for aging. One portion was static aged for overnight at room temperature (˜25° C.), and the other portion was hot-rolled for overnight at 121° C. Fann rheology measurements were then performed after the aging period. 
         [0023]    Data in Table 2 indicates that Suspension 3 (Example 2) performs slightly better than its dry precursor (Comparative Example 1) when used at a same active dosage in NaCl saturated water. Suspension 3 (Example 2) provides a higher overall rheology than the dry precursor (Comparative Example 1). 
         [0024]    Also, it is important to note that the Suspension 3 (Example 2) provides much better thermal stability than its dry precursor (Comparative Example 1). The brine solution thickened with the Suspension 3 (Example 2) retains 87.2%/78.7% of its apparent viscosity/Yield value versus 67.8%/41.8% for Comparative Example 1, when submitted to hot-rolling for overnight at 121° C. 
         [0000]    
       
         
               
             
               
               
               
             
               
               
               
             
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
             
               
             
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Comparative Thermal Stability in NaCl Saturated Brine 
               
             
          
           
               
                   
                 Comp. Example 1 
                 Example 2 
               
               
                   
                 Natrosol ® HIVIS HEC 
                 Suspension 3 
               
               
                   
                   
               
             
          
           
               
                 Form 
                 Powder 
                 Liquid 
               
               
                 Activity 
                 100% 
                 20% 
               
               
                 Dosage 
                 2 ppb 
                 10 ppb as-is 
               
             
          
           
               
                 Aging Conditions 
               
             
          
           
               
                 Aging time 
                 Overnight 
                 Overnight 
                 Overnight 
                 Overnight 
               
               
                 Aging temperature 
                 25° C. 
                 121° C. 
                 25° C. 
                 121° C. 
               
               
                 Conditions 
                 Static 
                 Hot-Rolled 
                 Static 
                 Hot-Rolled 
               
               
                 pH 
                 10.18 
                 8.14 
                 10.39 
                 9.95 
               
             
          
           
               
                 Fann Dial readings 
               
             
          
           
               
                 600 rpm 
                 96.6 
                 65.5 
                 101.2 
                 88.2 
               
               
                 300 rpm 
                 72.1 
                 42.7 
                 76 
                 64.1 
               
               
                 200 rpm 
                 59.6 
                 32.2 
                 63.3 
                 52.3 
               
               
                 100 rpm 
                 41.9 
                 19.1 
                 45.3 
                 35.7 
               
               
                  60 rpm 
                 31.8 
                 12.6 
                 34.4 
                 26.5 
               
               
                  30 rpm 
                 20.9 
                 7.1 
                 23.2 
                 16.9 
               
               
                  6 rpm 
                 6.3 
                 1.6 
                 7.6 
                 5.1 
               
               
                  3 rpm 
                 3.8 
                 1 
                 4.6 
                 2.9 
               
               
                 Apparent viscosity 
                 48.3 
                 32.75 
                 50.6 
                 44.1 
               
               
                 cPs 
               
               
                 Plastic Viscosity cPs 
                 24.5 
                 22.8 
                 25.2 
                 24.1 
               
               
                 Yield value lb/ 
                 47.6 
                 19.9 
                 50.8 
                 40 
               
               
                 100 ft 2   
               
             
          
           
               
                 Retained Rheology after Hot rolling 
               
             
          
           
               
                 Apparent viscosity 
                 67.8% 
                 87.2% 
               
               
                 Plastic Viscosity 
                 93.1% 
                 95.6% 
               
               
                 Yield value 
                 41.8% 
                 78.7% 
               
               
                   
               
             
          
         
       
     
         [0025]    It can be seen from Table 2, and in  FIG. 1 , that the Suspension 3 (Example 2) is an effective thickener of completion/workover fluids while providing additional thermal stability over its dry precursor. 
       EXAMPLE 3 
     Application in Oil-Well Cement Slurries 
       [0026]    The following examples illustrate the typical performance of aqueous suspension of HEC (Suspension 2 (Natrosol®) 250 JR HEC, available from Hercules Incorporated)) in low and medium temperature oil-well cement slurry compositions. The effect of temperature on low and medium temperature oil-well cement slurry compositions was evaluated up to 180° F. (82° C.), and salt tolerance up to 18% by weight of water (bwow) NaCl. 
         [0027]    The oil-well cement slurries were formulated using additives and mixing/formulation techniques commonly employed in the industry as recommended by the American Petroleum Institute (API). All concentrations of additives in the slurry compositions (Examples 3-6) are based on weight of cement (bwoc). 
         [0028]    The oil-well cement slurry was prepared by adding the cement dry mixture into the mix-water, eventually, containing the fluid loss additive (FLAC). The dry mixture consists of 600 g Calport G cement, 2.3% synthetic dispersant (1.15 wt. % active), 0.10% Antifoam and 2.0% Suspension 2 (0.40% active FLAC). For experiments at 180° F. (82° C.), 2.0% retarder (38% Ca. Lignosulfonate solution) was added to the slurry. 
         [0029]    The performance testing of the oil-well cement slurries were conducted in terms of rheology and fluid loss control properties. Typically, the “mixing rheology” was measured with Fann type viscometer just after the slurry preparation at room temperature (˜80° F., ˜27° C.), to simulate the mixing and pumping at the surface, while the “API rheology” was measured after conditioning the slurry at test temperature for 20 minutes. The fluid loss control properties were measured at 80° F. (27° C.) and 180° F. (82° C.) after the slurry conditioning. 
         [0030]    Data in Table 3 shows that the Suspensions 2, object of this invention, provides excellent rheology properties combined with good fluid loss control properties, at a reasonably low dosage (0.40% active). 
         [0000]    
       
         
               
             
               
               
               
             
               
               
               
               
               
               
               
               
               
             
               
               
               
             
               
               
               
             
               
               
               
               
               
               
               
               
               
             
               
               
               
             
           
               
                 TABLE 3 
               
               
                   
               
               
                 Rheology and Fluid Loss data of “Suspension 2” in an oil well cement slurry 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Example 3 
                 Example 4 
               
             
          
           
               
                   
                 g 
                 mls 
                 bwoc 
                 gps 
                 g 
                 mls 
                 bwoc 
                 gps 
               
               
                   
               
               
                 Ingredients 
               
               
                 Calport G cement 
                 600 
                 — 
                 — 
                 — 
                 600 
                 — 
                 — 
                 — 
               
               
                 NaCl, bwow (total water) 
                 — 
                 — 
                 — 
                 — 
                 45.55 
                 — 
                   18% 
               
               
                 Advantage A96 antifoam 
                 0.60 
                 0.60 
                 0.10% 
                 0.0113 
                 0.60 
                 0.60 
                 0.10% 
                 0.0113 
               
               
                 Synthetic dispersant (50%) 
                 16.54 
                 13.78 
                 2.30% 
                 0.2186 
                 16.54 
                 13.78 
                 2.30% 
                 0.2186 
               
               
                 Ca. Ligosulfonate solution (38%) 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Suspension 2 
                 15.84 
                 12.00 
                 2.00% 
                 0.171  
                 15.84 
                 12.00 
                 2.00% 
                 0.171  
               
               
                 Deionized water 
                 233.31 
                 233.31 
                 38.89% 
                 4.388  
                 233.31 
                 233.31 
                 38.89%  
                 4.388  
               
               
                 (42.17% total mix water) 
               
             
          
           
               
                 Mixing Rheology @80° F. 
                   
                   
               
               
                 P.V. (1.5 × Fx(300 DR − 100 DR), cPs 
                 189 
                 168 
               
               
                 Yv (Fx300 DR − PV), lb/100 ft2 
                 5 
                 5 
               
               
                 API Rheology 
                 80° F. 
                 80° F. 
               
               
                 P.V. (1.5 × Fx(300 DR − 100 DR), cPs 
                 247.5 
                 264 
               
               
                 Yv (Fx300 DR − PV), lb/100 ft2 
                 13.5 
                 20 
               
               
                   
                 80° F. 
                 80° F. 
               
               
                 30′ API Fluid Loss, cc 
                 22.8 
                 74.8 
               
               
                   
               
             
          
           
               
                   
                 Example 5 
                 Example 6 
               
             
          
           
               
                   
                 g 
                 mls 
                 bwoc 
                 gps 
                 g 
                 mls 
                 bwoc 
                 gps 
               
               
                   
               
               
                 Ingredients 
               
               
                 Calport G cement 
                 600 
                 — 
                 — 
                 — 
                 600 
                 — 
                 — 
                 — 
               
               
                 NaCl, bwow (total water) 
                 — 
                 — 
                 — 
                 — 
                 45.55 
                 — 
                   18% 
                 — 
               
               
                 Advantage A96 antifoam 
                 0.60 
                 0.60 
                 0.10% 
                 0.0113 
                 0.60 
                 0.60 
                 0.10% 
                 0.0113 
               
               
                 Synthetic dispersant (50%) 
                 16.54 
                 13.78 
                 2.30% 
                 0.2186 
                 16.54 
                 13.78 
                 2.30% 
                 0.2186 
               
               
                 Ca. Ligosulfonate solution (38%) 
                 14.39 
                 12.00 
                 2.00% 
                 0.188 
                 14.39 
                 12.00 
                 2.00% 
                 0.188 
               
               
                 Suspension 2 
                 15.84 
                 12.00 
                 2.00% 
                 0.171 
                 15.84 
                 12.00 
                 2.00% 
                 0.171 
               
               
                 Deionized water 
                 224.38 
                 224.38 
                 37.40% 
                 4.22 
                 224.38 
                 224.38 
                 37.40%  
                 4.22 
               
               
                 (42.17% total mix water) 
               
             
          
           
               
                 Mixing Rheology @80° F. 
                   
                   
               
               
                 P.V. (1.5 × Fx(300 DR − 100 DR), cPs 
                 201 
                 223.5 
               
               
                 Yv (Fx300 DR − PV), lb/100 ft2 
                 5 
                 5 
               
               
                 API Rheology 
                 180° F. 
                 180° F. 
               
               
                 P.V. (1.5 × Fx(300 DR − 100 DR), cPs 
                 105 
                 162 
               
               
                 Yv (Fx300 DR − PV), lb/100 ft2 
                 −1 
                 84 
               
               
                   
                 180° F. 
                 180° F. 
               
               
                 30′ API Fluid Loss, cc 
                 59.6 
                 152.4 
               
               
                   
               
             
          
         
       
     
         [0031]    It can be seen from Table 3, that the FLAC suspension, subject of his invention, is an effective fluid loss control additive of oil-well cement slurries.