Abstract:
The invention provides compositions and methods for sealing subterranean spaces such as natural or induced fractures, vugs or annular spaces. The composition is composed of a base fluid consisting of a soluble alkali silicate, a gas generating additive, solids and a setting agent. The gas generating additive may be coated or uncoated. The gas generating additive may also be in the form of a slurry. In the case of coated additives, the coating may act as a retarder or an accelerator to the expansion and setting agent of the soluble alkali silica. Similarly, the choice of carrier fluid in a slurry may retard or accelerate the expansion and setting of the alkali silicate-based plug.

Description:
[0001]    This application claims priority to U.S. Provisional Patent Application No. 62/253,834 filed in the United States Patent and Trademark Office on Nov. 11, 2015, which is incorporated herein by reference. 
     
    
     BACKGROUND OF INVENTION 
       [0002]    The focus of this invention is on the petroleum industry. People familiar with the art will realize the features of a self-pressurizing soluble alkali silicate-based system can be readily adapted and found useful in industries such as mining and construction. Further the expansion properties may also be used for prevention and correction of subsidence such as in buildings or roadways. 
         [0003]    It has been known since the 1920&#39;s that soluble alkali silicates such as sodium silicate are an effective means for providing conformance control in a reservoir. The term conformance is a broad term and includes control of excess water production with the goal of improving petroleum recovery and reducing costs. Recently, there has been greater interest in the use of soluble, alkali silicates such as sodium silicate. This resurgence is being driven by the performance properties of soluble alkali silicates as well as the environmentally friendly and low cost nature of sodium silicate. 
         [0004]    The chemistry of sodium silicate for conformance has been well documented in the literature. The paper by P. H. Krumrine and S. D. Boyce, Profile Modification and Water Control with Silica Gel-Based Systems, SPE 13578 presented at the 1985 SPE International Symposium on Oilfield and Geothermal Chemistry, Phoenix, Ariz., Apr. 9-11, 1985 is a leading article on the subject. This paper presents the chemistry, properties, benefits, limitations, and methods associated with sodium silicate conformance and provides an extensive list of potential setting agents. This paper is incorporated herein by reference. Also documented have been the use of fillers and bridging materials within a soluble metal silicate. Generally accepted features of soluble alkali silicate systems include;
       initial low viscosity (1-2 centipoise) which promotes penetration   small molecular weight which promotes penetration   excellent thermal stability   excellent chemical stability   high strength on setting   flexible set times (instant to several days)   environmentally friendly   moderate to low cost       
 
         [0013]    Commonly cited constraints of soluble alkali silicate-based technology include;
       gels can show syneresis (i.e. prone to shrinking)   the gel is rigid and prone to fracture       
 
         [0016]    The issue of shrinking/contraction is not exclusive to sodium silicate and is known to occur in polymer as well as cement systems. The lack of a tight seal can result in poor zonal isolation leading to gas migration, gas entrapment, and/or excessive water production among other issues. In the case of cement, several methods have been proposed to offset shrinkage. One such technique is the use of gas generating additives. When a suitable metal is added to the cement slurry, the high pH environment results in the production of hydrogen gas. This technology is described in U.S. Pat. Nos. 3,197,323; 3,579,366 and 3,709,707 for use in structural concrete compositions to offset contraction as well as the tendency to settle. The use of gas generating additives for oilwell cement was described by Carter et al: Expanding Cements for Primary Cementing, Journal of Petroleum Technology, May 1966. This article describes the use of zinc, magnesium, iron and aluminum powders to prepare expansive cements. The metal powders react in a cement slurry to produce minute bubbles of hydrogen. U.S. Pat. No. 4,304,298 describes an improved oil well cement slurry for the generation and entrainment of gas. U.S. Pat. No. 8,689,871 describes the difficulty of high reactivity of metals when exposed to a cement slurry and the coatings that may advantageously delay the gas generation reaction. 
         [0017]    Unlike cement which sets via a hydration reaction, soluble silicates set via a gelation/polymerization reaction caused by a loss of alkalinity. Soluble silicates can also be set via a precipitation reaction with metal cations. Soluble silicates may also be made to set via a dehydration reaction where the loss of water causes the soluble silicate to thicken and eventually revert back to a glass. The setting mechanisms of soluble silicate function to prevent fluid loss. Alkali silicates may also donate their charge which can react with solid material in the plug and also function as a setting mechanism. 
       SUMMARY OF THE INVENTION 
       [0018]    The invention provides compositions and methods for sealing subterranean spaces such as natural or induced fractures, vugs or annular spaces. The composition is composed of a base fluid consisting of a soluble alkali silicate, a gas generating additive, solids and a setting agent. The gas generating additive may be coated or uncoated. In the case of coated additives, the coating may act as a retarder or an accelerator to the expansion and setting agent of the soluble alkali silicate. 
     
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
       [0019]    The present compositions represent a cross section of potential formulations. It should be evident there are wide range of additional material that may be added or substituted to the composition without changing the nature of the invention. The technology is demonstrated herein using hydrogen as the generated gas. It is apparent that other types of gas such as nitrogen or oxygen may also be generated in a soluble alkali silicate environment and it is to be distinctly understood that the principles of the present invention apply equally to such systems. 
         [0020]    Metals that may generate hydrogen in soluble alkali silicate include but are not limited to: aluminum, iron, magnesium, lithium, sodium, potassium, rubidium, cesium, calcium, barium, strontium, radium, and zinc powders. Gas generation can also be achieved by the use of sparingly soluble metal salts. The metals can be of a different shape and size ranging from fine powders to flake or the metals may be used in a slurry form to prepare a self-pressurizing alkali silicate system. The invention also allows for the use of other types of gas generating additives such as those that release nitrogen. When added to the high alkalinity environment of a soluble, alkali silicate, the metal powder reacts to produce hydrogen gas. The resulting gas causes the soluble silicate to expand and self-pressurize in a confined space. Expansion time can be controlled by several factors to allow for desired reaction times under downhole applications. Similar to expandable cements, it is optimal to have the generation take place between the time of placement in the subterranean open space and the early setting stages of the soluble alkali silicate. The gas generation rate can be controlled by several factors, such as:
       type of metal powder   reactive surface area of the metal powder   type of coating   metal from a sparingly soluble salt   in the case of slurried material, the choice of carrier fluid   grade of soluble alkali silicate   setting agents   temperature       
 
         [0029]    The generation of gas can be further controlled by selection of the soluble alkali silicate. Soluble silicates are produced with varying degrees of alkalinity as measured by the ratio of SiO 2  to Me 2 O where Me is the alkali metal and is most commonly sodium or potassium. Generally, the low-ratio, more alkali silicates generate gas at a quicker rate. Conditions such as downhole temperature are typically difficult to control; reaction rate can be adjusted by selection of the appropriate ratio soluble alkali silicate. PQ Corporation produces a wide range of soluble, alkali silicate having a weight ratio of SiO 2  to Me 2 O of generally 1.0 to 8.5. Table 1 provides a cross section of some of the different grades of sodium and potassium silicate as well as specialty soluble alkali silicates. The option exists to fine tune reaction times via the addition of alkali or acid to the soluble alkali silicate system. 
         [0000]    
       
         
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
               
                   
               
               
                 PQ Corporation 
                   
                 %  
                 %  
                 %  
                   
               
               
                 Product Name 
                 SiO 2 /Me 2 O 
                 SiO 2   
                 Me 2 O 
                 Solids 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Sodium/Potassium Silicates 
               
             
          
           
               
                 KASIL ® 1 
                 2.5 
                 20.8 
                 8.3 
                 29.1 
                 Liquid 
               
               
                 KASIL ® 6 
                 2.1 
                 26.5 
                 12.65 
                 39.15 
                 Liquid 
               
               
                 EcoDrill ® K45 
                 3.0 
                 18.0 
                 6.0 
                 24.0 
                 Liquid 
               
               
                 KASOLV ® 16 
                 1.6 
                 52.8 
                 32.5 
                 85.3 
                 Hydrous 
               
               
                   
                   
                   
                   
                   
                 powder 
               
               
                 KASIL ® SS 
                 2.5 
                 71.0 
                 28.4 
                 99.4 
                 Ground Glass 
               
               
                 BW ™ 50 
                 1.60 
                 26.2 
                 16.75 
                 42.55 
                 Liquid 
               
               
                 BJ ™ 120 
                 1.80 
                 23.7 
                 13.15 
                 36.85  
                 Liquid 
               
               
                 D ™ 
                 2.00 
                 29.4 
                 14.7 
                 44.1 
                 Liquid 
               
               
                 RU ™ 
                 2.40 
                 33.0 
                 13.9 
                 47.1 
                 Liquid 
               
               
                 M ® 
                 2.58 
                 32.1 
                 12.4 
                 44.5 
                 Liquid 
               
               
                 K ® 
                 2.88 
                 31.7 
                 11.0 
                 42.7 
                 Liquid 
               
               
                 N ® 
                 3.22 
                 28.7 
                 8.9 
                 37.6 
                 Liquid 
               
               
                 EcoDrill ® S45 
                 4.50 
                 21.0 
                 4.7 
                 26.0  
                 Liquid 
               
               
                 SS ® 20 
                 3.22 
                 75.0 
                 23.3 
                 99.2  
                 Ground glass 
               
               
                 G ® 
                 3.22 
                 61.8 
                 19.2 
                   
                 Hydrous 
               
               
                   
                   
                   
                   
                   
                 powder 
               
               
                 GD ® 
                 2.00 
                 54.0 
                 27.0 
                   
                 Hydrous 
               
               
                   
                   
                   
                   
                   
                 Powder 
               
               
                 Metso Beads ® 
                 1.00 
                 47.0 
                 51.0 
                   
                 Granule 
               
               
                 2048 
                   
                   
                   
                   
                   
               
             
          
           
               
                 Other Silicates 
               
             
          
           
               
                 Lithisil ® 25 
                 8.2 
                 20.5 
                 2.5 
                 23.0 
                 Liquid lithium 
               
               
                   
                   
                   
                   
                   
                 silicate 
               
               
                 EcoDrill ® 
                 1.7 
                 27.9 
                 16.2 
                 45.7 
                 Aqueous 
               
               
                 AAAS 
                   
                   
                   
                   
                 alkali alumino 
               
               
                   
                   
                   
                   
                   
                 silicate 
               
               
                 Quram 
                   
                   
                   
                   
                 Quaternary 
               
               
                   
                   
                   
                   
                   
                 ammonium 
               
               
                   
                   
                   
                   
                   
                 silicate 
               
               
                   
               
             
          
         
       
     
         [0030]    Gas generation rate can be further controlled in a soluble alkali system by having the metal particles coated or encapsulated with organic or inorganic layers. The coating may be selected to degrade with temperature, water or the presence of alkali. Delay in the generation of gas may range from several minutes to hours. A coating may be selected that will also act as a setting agent for soluble alkali silicate. 
         [0031]    Metal particles can be suspended in a slurry. The use of a slurry mitigates handling issues associated with powder metals. The carrier fluid can also function as a setting agent for the alkali silicate. Examples of suitable carrier fluids that can suspend and carry metal while acting to set sodium silicate include but are not limited to acid generating liquids such as propylene carbonate, triacetin, ethyl acetate, among others. The carrier fluid can also serve to retard the expansion reaction via the use of organic carrier fluids, such as mineral oil, polyalphaolefins, polyethylene glycol, polypropylene glycol, among others. 
         [0032]    Soluble alkali silicate can be made to set by gelation reaction or a precipitation reaction. The gelation reaction involves the polymerization of silicate molecules brought on by the loss of alkalinity. The previous referenced paper by Krumrine contains an extensive list of acids, aldehydes, polyhydric alcohols, esters, amides, salts and natural materials that may be used of induce the gelation reaction. Gelation times can be controlled from seconds to days depending on choice and concentration of setting agent. 
         [0033]    The precipitation reaction involves the reaction of the multivalent metal with the Si—O −  group. This results in the formation of a metal silicate. The metal additives used to generate gas can also act as a setting agent. As the metal reacts in a silicate solution to form the corresponding metal hydroxide it become reactive towards the alkali soluble silicate. This imparts further strength to the setting alkali silicate. 
         [0034]    The soluble alkali silicate solution can be run with or without solid material. The addition of solid material serves a multi-functional role: cost reduction, set time control, strength enhancement, improved temperature resistance, density control and viscosity control as well as aid in setting and insolubilizing the alkali silicate, to name a few. Examples of some potential filler material include barite, calcium carbonate, clay, walnut hulls, silica, zeolite, hollow glass spheres, fibrous material, fly ash, and the like. The performance of the self-compressing alkali silicate can be further adjusted via the addition of other additives such as viscosifiers, fluid loss additives, surfactants, and the like. 
         [0035]    Coated and uncoated aluminum powder as well as zinc powder &amp; flake were provided by BYK. Tables 2a and 2b provides a description of the products. Also provided by BYK were aluminum and zinc in a slurry form. Table 2c provides a description of the carrier fluid and metal. To aid in suspension and dispersion, slurried products also contained trace amounts of wetting, dispersing, and suspending additives. 
         [0000]    
       
         
               
             
               
               
               
             
           
               
                 TABLE 2a 
               
             
             
               
                   
               
               
                 Aluminum Powder 
               
             
          
           
               
                 Sample 
                 Coating 
                 Particle size 
               
               
                   
               
               
                 PCA 
                 Organic coated aluminum powder 
                 5-100 microns 
               
               
                 PCR 
                 Inorganic coated aluminum powder 
                 5-100 microns 
               
               
                 SDF 2-681 
                 Dedusted aluminum powder 
                 5-100 microns 
               
               
                 LSC-895 
                 Phosphoric acid ester 
                 5-100 microns 
               
               
                 LSC-894 
                 Fatty acid, tall-oil compounds 
                 5-100 microns 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
             
           
               
                 TABLE 2b 
               
             
             
               
                   
               
               
                 Zinc Powder 
               
             
          
           
               
                 Sample  
                 Shape  
                 Coating  
                 Particle size 
               
               
                   
               
               
                 Zinc flake  
                 Flake  
                 uncoated  
                 5-100 microns 
               
               
                 LSC-912  
                 Granular  
                 90-100% zinc, 2.5-10% 
                   
               
               
                   
                   
                 phosphoric acid ester, 2.5-5% 
                   
               
               
                   
                   
                 ethyl alcohol 
                   
               
               
                 LSC-913  
                 Granular  
                 90-100% zinc, 1-2.5% mineral 
                   
               
               
                   
                   
                 spirits low aromatic, 0.1-1% 
                   
               
               
                   
                   
                 fatty acid, tall oil compds, 1- 
                   
               
               
                   
                   
                 2.5% other components 
                   
               
               
                 LSC-914  
                 Flake  
                 90-100% zinc, 2.5-10% 
                   
               
               
                   
                   
                 phosphoric acid ester, 2.5-5% 
                   
               
               
                   
                   
                 ethyl alcohol 
                   
               
               
                 LSC-915  
                 Flake  
                 90-100% zinc, 1-2.5% mineral 
                   
               
               
                   
                   
                 spirits low aromatic, 0.1-1% 
                   
               
               
                   
                   
                 fatty acid, tall oil compds, 1- 
                   
               
               
                   
                   
                 2.5% other components 
                   
               
               
                 GTT  
                 Flake  
                 Steric acid 
                   
               
               
                 AT  
                 Flake  
                 Steric acid 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
             
           
               
                 TABLE 2c 
               
             
             
               
                   
               
               
                 Zinc &amp; Aluminum as a Slurry 
               
             
          
           
               
                 Sample 
                 Metal 
                 Carrier fluid 
               
               
                   
               
               
                 RXG-7575-PG 
                 Zinc flake 
                 Polyethylene glycol 
               
               
                 RXG-7575-PC 
                 Zinc flake 
                 Propylene carbonate 
               
               
                   
               
             
          
         
       
     
       Example 1 
       [0036]    Example 1 shows the dimensional stability, compressive strength, resistance to contraction and seal integrity using expanded sodium silicate vs. non expanded sodium silicate. The self-compressing silicates contain zinc flake while the control were formulated free of zinc. Samples were prepared to the indicated weight percent. PVC piping (1 inch diameter and 2 inch height) sealed on the bottom were filled with 15 g of the indicated composition. Samples were placed in a heated compression chamber for 2 hrs. at 50° C. under 50 psi pressure and then cured for an additional 24 hrs. and 7 days. An Ingstrom Model 3345 was used to measure the compressive strength as well as the pressure to push the plug out of the PVC piping. The extruded plug was weighed and measured to determine the change in density. 
         [0000]    
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Extrusion Pressure of self-compressing silicate vs. control 
               
             
          
           
               
                   
                   
                   
                 24 hrs @ 50° C. 
                 7 days @ 50° C. 
               
             
          
           
               
                 1:1  
                   
                   
                   
                 Extrusion 
                 Comp. 
                   
                 Comp. 
               
               
                 silicate:filler 
                 Zinc 
                   
                 Density, 
                 Pressure 
                 Strength 
                 Density,  
                 strength 
               
             
          
           
               
                 N sil. 
                 CaCO 3   
                 flake 
                 Lactose 
                 g/cm 3   
                 psi 
                 psi 
                 g/cm 3   
                 psi 
               
               
                   
               
             
          
           
               
                 30 
                 g 
                 30 
                 g 
                 1.5 
                 g 
                 1.5 
                 g 
                 0.63 
                 7.5 
                 111 
                 0.57 
                 542 
               
               
                 30 
                 g 
                 30 
                 g 
                 1.5 
                 g 
                 3.0 
                 g 
                 0.58 
                 10.3 
                 135 
                 0.50 
                 605 
               
               
                 30 
                 g 
                 30 
                 g 
                 3.0 
                 g 
                 1.5 
                 g 
                 0.73 
                 6.4 
                 204 
                 0.60 
                 683 
               
               
                 30 
                 g 
                 30 
                 g 
                 3.0 
                 g 
                 3.0 
                 g 
                 0.55 
                 11 
                 81 
                 0.52 
                 547 
               
               
                 30 
                 g 
                 30 
                 g 
                 0 
                 g 
                 3.0 
                 g 
                 1.87 
                 3.4 
                 1130 
                 1.85 
                 1582 
               
               
                   
               
             
          
         
       
     
         [0037]    The expanded samples required a higher degree of force to push out of the mold vs the control. Compressive strength of the expanded samples were lower than the control but this is a reflection of the reduced density. The expanded samples showed signs of deformation under compressive strength testing vs. the more brittle control. 
       Example 2 
       [0038]    Example 2 shows the expansion rate and degree of expansion can be controlled by the alkalinity of the soluble silicate. Samples were placed in clear plastic cup and the level of expansion measured as a function of time. Change in density was used to measure the degree of expansion. Expansion time was measured by visual observation above a start line 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 4 
               
             
             
               
                   
               
               
                 expansion rate vs. alkalinity of soluble silicate 
               
             
          
           
               
                   
                   
                   
                   
                   
                   
                 Final 
               
               
                 Soluble  
                   
                   
                   
                 Initial  
                 4 hr 
                 Density 
               
               
                 Alkali  
                 Calcium  
                 Zinc  
                   
                 Density  
                 Density  
                 (~72 hrs  
               
               
                 Silicate  
                 Carbonate  
                 Flake  
                 Lactose  
                 21° C.  
                 21° C.  
                 @ 65° C.) 
               
               
                   
               
               
                 25 g  
                 25 g  
                 1.25 g  
                 1.25 g  
                 1.8 
                 1.09 
                 0.69 
               
               
                 2.5 ratio 
                   
                   
                   
                   
                   
                   
               
               
                 Star ® 
                   
                   
                   
                   
                   
                   
               
               
                 grade 
                   
                   
                   
                   
                   
                   
               
               
                 sodium 
                   
                   
                   
                   
                   
                   
               
               
                 silicate 
                   
                   
                   
                   
                   
                   
               
               
                 25 g  
                 25 g 
                 1.25 g  
                 1.25 g 
                 1.8  
                 1.71 
                 1.55 
               
               
                 8.9 ratio 
                   
                   
                   
                   
                   
                   
               
               
                 Lithisil 
                   
                   
                   
                   
                   
                   
               
               
                 25 
                   
                   
                   
                   
                   
                   
               
               
                 lithium 
                   
                   
                   
                   
                   
                   
               
               
                 silicate 
               
               
                   
               
             
          
         
       
     
         [0039]    Star® sodium silicate is a mid-ratio alkali silicate or moderately alkaline sodium silicate. Lithisil 8.9 represents the very high ratio alkali silicate or low alkaline lithium silicate. The lower alkalinity lithium silicate took much longer to expand and therefore lose density under equivalent conditions. 
       Example 2b 
       [0040]    As another example of expansion rate as a as a function of alkalinity or ratio of SiO 2 :Me 2 O is also demonstrated using a range of different ratio sodium silicates. The high ratio, low alkaline S45 showed no expansion under ambient conditions and required a higher temperature environment to generate expansive gas vs. the low ratio BW®. Prepared slurry material were filled to the 15 ml mark of a 50 ml cylinder. The cylinder was sealed and expansion was measured as a function of increased volume in relation to time and temperature. Size restraints limited expansion to a maximum of 3×&#39;s starting volume. 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 4b 
               
             
             
               
                   
               
               
                 Expansion rate vs. ratio of sodium silicate at 50° C. 
               
             
          
           
               
                   
                 Silicate 
                   
                   
                   
                   
                   
                   
                   
               
               
                   
                 ratio 
                   
                 Zinc 
                 Initial 
                 1 hr 
                 2 hr 
                 4 hr 
                 4 hr 
               
               
                 Alkali silicate 
                 SiO 2 :Na 2 O 
                 CaCO 3   
                 flake 
                 density 
                 50° C. 
                 50° C. 
                 50° C. 
                 20° C. 
               
               
                   
               
             
          
           
               
                 Ecodrill ® S45-50 g 
                 4.5 
                 50  
                 g 
                 2.5  
                 g 
                 1.67 
                 1.67 
                 1.67 
                 1.25 
                 1.67 
               
               
                 N ® silicate-50 g 
                 3.2 
                 50  
                 g 
                 2.5  
                 g 
                 1.8 
                 — 
                 0.9 
                 0.64 
                 1.54 
               
               
                 BW ® silicate-50 g 
                 1.6 
                 50  
                 g 
                 2.5  
                 g 
                 1.8 
                 0.6 
                 0.6 
                 0.6 
                 0.6 
               
               
                   
               
             
          
         
       
     
       Example 3 
       [0041]    Example 3 illustrates the expansion rate being a function of using coated vs. non-coated metal. Time to max expansion time was measured using different fillers in a low ratio aqueous alkali aluminosilicate Filler material included, barite, calcium carbonate, and flyash. 
         [0000]    
       
         
               
             
               
               
               
               
             
           
               
                 TABLE 5 
               
             
             
               
                   
               
               
                 Time to &gt;75% max expansion 
               
             
          
           
               
                   
                   
                 Aluminum 
                   
               
               
                   
                 Silicate &amp; filler/ 
                 powder 
                 Time to expand at room temp 
               
               
                   
                   
               
               
                   
                 1:1 of 
                  1.5% PCR 
                 ~30 min 
               
               
                   
                 AAAS:Barite + 
                  1.5% PCA 
                  ~5 min 
               
               
                   
                 5% ZnCO 3   
                  1.5% SDF 
                 Immediate 
               
               
                   
                 1:1 of 
                  1.5% PCR 
                 ~30 min 
               
               
                   
                 AAAS:CaCO 3  + 
                  1.5% PCA 
                  ~5 min 
               
               
                   
                 5% ZnCO 3   
                  1.5% SDF 
                 Immediate 
               
               
                   
                 1:1 of AAAS:Fly 
                  1.5% PCR 
                 ~10 min 
               
               
                   
                 ash 
                  1.5% PCA 
                  ~5 min 
               
               
                   
                   
                  1.5% SDF 
                 Immediate 
               
               
                   
                   
                 0.75% PCR 
                 ~10 min 
               
               
                   
                   
                 0.75% PCA 
                  ~5 min 
               
               
                   
                   
                 0.75% SDF 
                 Immediate 
               
               
                   
                   
               
             
          
         
       
     
         [0042]    The inorganic coated aluminum (PCR) showed distinctly slower expansion times vs. the uncoated control. By being able to slow down the expansion rate via a coating on the metal, the option exists for formulating the self-compressing alkali silicate to be pumped and placed to a greater depth prior to the start of expansion. 
       Example 4 
       [0043]    Example 4 illustrates that expansion and setting can take place without the addition of filler or extender material. The only solids present being the zinc. Lactose is dissolved into N® grade sodium silicate and then the zinc powder is mixed into the slightly viscous solution. Materials are then 1 inch diameter form with a sealed bottom. The prepared samples are then put into a pressure vessel at 100 psi pressure and 50° C. for 4 hrs. As well as expansion, the example shows that zinc can react with zinc to impart increased strength and water resistance 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 6 
               
             
             
               
                   
               
               
                 Expansion and compressive strength without the use of fillers 
               
             
          
           
               
                 N 
                 Zinc 
                   
                   
                   
                   
                 Initial 
                 Final 
                 Compressive 
               
               
                 Sodium 
                 flake 
                   
                 Lactose 
                   
                   
                 density 
                 Density, 
                 Strength 
               
               
                 Silicate 
                 AT % 
                 g 
                 % 
                 g 
                 temp 
                 g/cm 3   
                 g/cm 3   
                 psi 
               
               
                   
               
             
          
           
               
                 30 g 
                 2.5%  
                 0.75 
                 g 
                 2.50% 
                 0.75 
                 g 
                 50° C. 
                 1.46 
                 0.81 
                 39 
               
               
                   
                 2.5%  
                 0.75 
                 g 
                 5.00% 
                 1.5 
                 g 
                   
                   
                 0.74 
                 26 
               
               
                   
                 5.0% 
                 1.5 
                 g 
                 2.50% 
                 0.75 
                 g 
                   
                   
                 0.66 
                 26 
               
               
                   
                 5.0% 
                 1.5 
                 g 
                 5.00% 
                 1.5 
                 g 
                   
                   
                 0.76 
                 28 
               
               
                   
                 0.0% 
                 0 
                 g 
                 2.50% 
                 0.75 
                 g 
                   
                   
                 1.4 
                 12 
               
               
                   
                 0.0% 
                 0 
                 g 
                 5.00% 
                 1.5 
                 g 
                   
                   
                 1.4 
                 11 
               
               
                   
               
             
          
         
       
     
         [0044]    For placement into fine fractures, channels or micro-annuli it is desirable to be solids free or close to solids free to allow for greater depth of penetration and mitigate the chance that suspended material will bridge at fracture openings. 
       Example 5 
       [0045]    Example 5 shows that expansion can also take place using metal salts. The use of metal salts can also generate hydrogen and allow for slower expansion at higher temperatures. Zinc carbonate (ZnCO 3 ) was as selected as a sparingly soluble salt of zinc. Expansion shows the degree of expansion under at atmospheric conditions. Aqueous alkali alumino silicate was used as the base sodium silicate. Barite was used as an inert filler and triacetin was used as a setting agent for the silicate. Test specimens were prepared by filling up the 50 ml of plastic cylinder, the cylinder was first curing overnight at 75° C., the firm set specimen was then taken out from plastic cylinder and continue curing for overnight at 150° C./300° F. and 250° C./482° F. The original volume of test specimen has expanded to ˜1.5× volume after curing overnight at the high temperature of 150° C. and 250° C. with very good thermal strength. 
         [0000]    
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 7 
               
             
             
               
                   
               
               
                 Expansion at high temperatures using a sparingly soluble metal salt 
               
             
          
           
               
                   
                   
                   
                   
                 Compressive  
               
               
                   
                   
                 Setting agents 
                 Volume expansion 
                 strength, psi 
               
             
          
           
               
                 AAAS 
                 Barite  
                 Triacetin 
                 ZnCO 3   
                 75° C. 
                 150° C. 
                 250° C. 
                 75° C. 
                 150° C. 
                 250° C. 
               
               
                   
               
               
                 50 g 
                 50 g 
                 3.9 g 
                 2.1 g 
                 1.0 × V 
                 ~1.5 × V 
                 ~1.5 × V 
                 &gt;1500 
                 1370 
                 1484 
               
               
                   
               
             
          
         
       
     
         [0046]    At lower temperatures there is a strong set but no expansion, the increase to higher temperature allows for sufficient elemental zinc to generate hydrogen. This reaction allows for the use of the system at higher temperatures without premature reaction. 
       Example 6 
       [0047]    On-site formulation of expandable silicate-based plugs allows for increased flexibility in formulating to specific subterranean conditions. For defined and routine conditions it is operationally simpler to have a “add water and stir” product. A further advantage to dry blending material is mitigation of handling issues associated with powder metals. Table 8a shows an all-in-one product formulated by dry blending granular sodium metasilicate, class F fly ash and inorganic coated aluminum powder (PCR-214). This blend was mixed with tap water to an approximate weight ratio of 2.5:1, dry blended material to water. A closed 50 ml plastic cylinder was filled to ⅓ of volume and sealed. The contained mixture was aged overnight (˜16 hrs.) at 20° C., 50° C. and 85° C. 
         [0048]    Table 8b demonstrates a dry blended product made using a spray dried 2.0 ratio sodium silicate powder. The lower alkalinity of the 2.0 ratio showed less expansion under similar test conditions. 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 8a 
               
             
             
               
                   
               
               
                 Dry blended high alkali mixture 
               
             
          
           
               
                 Metso 
                   
                 Aluminum 
                   
                   
                   
                 Strength after  
               
               
                 beads 
                 Flyash 
                 PCR- 
                   
                 Expansion 
                 Density 
                 7 days, psi 
               
             
          
           
               
                 2048 
                 F 
                 214 
                 Water 
                 at 20° C. 
                 g/cm 3   
                 20° C. 
                 50° C. 
                 85° C. 
               
               
                   
               
             
          
           
               
                 10  
                 g 
                 90  
                 g 
                 0.0  
                 g 
                 40  
                 g 
                 No 
                 1.67 
                 1264 
                 1500 
                 1390 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 expansion 
                   
                   
                   
                   
               
               
                 7.5  
                 g 
                 91.5  
                 g 
                 1.0  
                 g 
                 40  
                 g 
                 2.0 × 
                 0.83 
                 100 
                 136 
                 215 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 volume 
                   
                   
                   
                   
               
               
                 10.0  
                 g 
                 89.5  
                 g 
                 0.5  
                 g 
                 40  
                 g 
                 2.7 × 
                 0.62 
                 109 
                 182 
                 162 
               
             
          
           
               
                   
                   
                   
                   
                 volume 
                   
                   
                   
                   
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 8b 
               
             
             
               
                   
               
               
                 Dry blended lower alkalinity 
               
             
          
           
               
                   
                   
                   
                   
                   
                   
                 Strength,  
               
               
                   
                   
                 Alumi-  
                   
                   
                   
                 psi 
               
               
                   
                   
                 num 
                   
                   
                   
                 20 hrs  
               
               
                 Sodium 
                 Flyash 
                 PCR- 
                   
                 Expansion 
                 Density 
                 @ 
               
               
                 silicate 
                 F 
                 214 
                 Water 
                 at 20° C. 
                 g/cm 3   
                 20° C. 
               
               
                   
               
               
                 GD, 
                 89 g 
                 1.0 g 
                 50 g 
                 1.2 × volume 
                 1.4 
                 21 
               
               
                 10 g 
               
               
                   
               
             
          
         
       
     
       Example 7 
       [0049]    For certain subterranean applications such as lost circulation, it is often necessary to formulate to a low density to avoid exceeding the fracture gradient. This example shows a low density and higher temperature expandable alkali silicate system. In this set of experiments a higher ratio, 3.2 ratio sodium silicate was used with urea as a setting agent. Hollow glass spheres (i.e. Potters Q-Cel) were used as light weight additive to adjust the density of other fillers. The filler of 1:1 of Q-Cel:CaCO 3  blend gave an approximate starting density of ˜1.1 g/cm 3 . 
         [0050]    Table 9a compares zinc in a slurry form used a slurry material consisting of 48% zinc flake and 52% polyethylene glycol. The zinc slurry in polyethylene glycol allowed for a longer expansion and set while the propylene carbonate allowed for quick set with less expansion. 
         [0000]    
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 9a 
               
             
             
               
                   
               
               
                 Light weight SPS prepared with different forms of zinc 
               
             
          
           
               
                 Silicate and setting  
                   
                   
                   
                   
               
               
                 aid solution 
                   
                   
                   
                 Den- 
               
             
          
           
               
                 N 
                   
                   
                 Filler blend 
                   
                 Set  
                 sity 
               
             
          
           
               
                 silicate 
                 Urea 
                 Water 
                 Q-Cel 
                 CaCO 3   
                 Zinc 
                 Time 
                 g/cm 3   
               
               
                   
               
             
          
           
               
                 Control- 
                 10  
                 g 
                 10  
                 g 
                 40  
                 g 
                 40  
                 g 
                 — 
                 — 
                 1.1 
               
             
          
           
               
                 100  
                 g 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 100  
                 g 
                 10  
                 g 
                 10  
                 g 
                 30  
                 g 
                 30  
                 g 
                 2.5 g  
                 ~4   
                 0.55 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 as Zn 
                 hrs 
                   
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 slurry 
                 at  
                   
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 RXG- 
                 90° C. 
                   
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 7575 PG 
                   
                   
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 (poly- 
                   
                   
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 ethylene 
                   
                   
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 glycol) 
                   
                   
               
               
                 100  
                 g 
                 10  
                 g 
                 10  
                 g 
                 30  
                 g 
                 30  
                 g 
                 2.7 
                 ~10  
                   
               
             
          
           
               
                   
                   
                   
                   
                   
                 RSG- 
                 minute 
                   
               
               
                   
                   
                   
                   
                   
                 7575 
                 set at  
                   
               
               
                   
                   
                   
                   
                   
                 PC 
                 25° C. 
                   
               
               
                   
                   
                   
                   
                   
                 Propyl- 
                   
                   
               
               
                   
                   
                   
                   
                   
                 ene 
                   
                   
               
               
                   
                   
                   
                   
                   
                 car- 
                   
                   
               
               
                   
                   
                   
                   
                   
                 bonate 
               
               
                   
               
             
          
         
       
     
       Example 8 
       [0051]    The presence of oil-based drilling fluids can adversely affect the performance of plugging/blocking material such as Portland cement. Example 8 shows the self-pressurizing silicate plug tolerant towards oil-based drilling fluid. The oil-based drilling fluid being a typical 85:15 water in oil emulsion-based fluid obtained from the field. The zinc flake was made into a slurry using triacetin as the carrier fluid and silicate setting agent. The mixture is shown to be tolerant to the presences of a high level of contamination by oil-based drilling fluids. Walnut hull was used as a filler material. 
         [0052]    A 50 ml plastic cylinder with lid is used, fills 35 g of mixture up to 25 ml (density 1.4 g/cm3), close the lid and the sample was cured overnight at 20° C., 50° C. and 75° C. 
         [0053]    All mixtures remained pumpable up to 1 hour and start expanding at room temperature. The presence of oil based drilling fluid decreased the amount of expansion but had minimal effect on compressive strength. 
         [0000]    
       
         
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 10 
               
             
             
               
                   
               
               
                   
                   
                 Zinc 
                   
                   
                   
                   
               
               
                   
                   
                 flake 
                   
                 Oil 
                 Density after 
                 Strength after 
               
               
                   
                   
                 LSC- 
                   
                 based 
                 20 hrs, g/cm 3   
                 20 hrs, psi 
               
             
          
           
               
                 AAAS 
                 Walnut 
                 915 
                 Triacetin 
                 mud 
                 20° C. 
                 50° C. 
                 75° C. 
                 20° C. 
                 50° C. 
                 75° C. 
               
               
                   
               
             
          
           
               
                   
                   
                   
                   
                   
                   
                   
                   
                 Initial 
                   
                   
                   
                   
                   
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 density 1.4 
                   
                   
                   
                   
                   
               
             
          
           
               
                 100 
                 g 
                 25 
                 g 
                 2.5 
                 g 
                 7.5 
                 g 
                 0 
                 g 
                 0.59 
                 0.57 
                 0.60 
                 23 
                 40 
                 35 
               
               
                 100 
                 g 
                 25 
                 g 
                 2.5 
                 g 
                 7.5 
                 g 
                 10 
                 g 
                 0.89 
                 0.77 
                 0.83 
                 36 
                 36 
                 36 
               
               
                 100 
                 g 
                 25 
                 g 
                 2.5 
                 g 
                 7.5 
                 g 
                 20 
                 g 
                 0.92 
                 0.81 
                 0.81 
                 27 
                 42 
                 54 
               
               
                   
               
             
          
         
       
     
       Example 9 
       [0054]    Degree of expansion can be control by adjusting shape (particle vs. flake) and type of coating. The larger surface area of flake providing for greater expansion vs. powder. Example also shows the type of coating impacting degree of expansion and final strength of set material. 
         [0000]    
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 11a 
               
             
             
               
                   
               
               
                 Effect of metal shape and coating on expansion and setting 
               
             
          
           
               
                   
                   
                   
                   
                 After 20 hrs  
                 After 20 hrs 
               
               
                   
                   
                   
                   
                 @ 50° C. 
                 @ 75° C. 
               
             
          
           
               
                 Silicate 
                   
                 Expansion 
                 Setting 
                   
                 Comp. 
                   
                 Comp. 
               
               
                 Ecodrill ® 
                 Filler 
                 Agent 
                 Agent 
                   
                 Strength 
                   
                 Strength 
               
               
                 AAAS 
                 CaCO 3   
                 zinc 
                 lactose 
                 density 
                 psi 
                 density 
                 psi 
               
               
                   
               
             
          
           
               
                 50 
                 g 
                 50 
                 g 
                 no zinc 
                 8.1 
                 g 
                 1.82 
                 810 
                 1.82 
                 1180 
               
               
                 50 
                 g 
                 50 
                 g 
                 LSC-912 
                 8.1 
                 g 
                 1.44 
                 234 
                 1.45 
                 405 
               
               
                 50 
                 g 
                 50 
                 g 
                 LSC-913 
                 8.1 
                 g 
                 1.36 
                 422 
                 1.20 
                 787 
               
               
                 50 
                 g 
                 50 
                 g 
                 LSC-914 
                 8.1 
                 g 
                 1.30 
                 280 
                 1.25 
                 311 
               
               
                 50 
                 g 
                 50 
                 g 
                 LSC-915 
                 8.1 
                 g 
                 1.20 
                 514 
                 0.99 
                 788 
               
               
                 50 
                 g 
                 50 
                 g 
                 GTT 
                 8.1 
                 g 
                 1.05 
                 622 
                 0.81 
                 857 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 11b 
               
             
             
               
                   
               
               
                 Effect of metal shape and coating on expansion and setting 
               
             
          
           
               
                   
                   
                   
                   
                 After 20 hrs  
                 After 20 hrs  
               
               
                   
                   
                   
                   
                 @ 50° C. 
                 @ 75° C. 
               
             
          
           
               
                   
                   
                 Expansion 
                 Setting 
                   
                 Comp. 
                   
                 Comp. 
               
               
                 Silicate 
                 Filler 
                 Agent 
                 Agent 
                   
                 Strength 
                   
                 Strength 
               
               
                 N ® 
                 CaCO 3   
                 Zinc 
                 lactose 
                 density 
                 psi 
                 density 
                 psi 
               
               
                   
               
             
          
           
               
                 50 
                 g 
                 50 
                 g 
                 no zinc 
                 4.5 
                 g 
                 1.82 
                 290 
                 1.82 
                 1470 
               
               
                 50 
                 g 
                 50 
                 g 
                 LSC-912 
                 4.5 
                 g 
                 1.29 
                 534 
                 1.28 
                 1026 
               
               
                 50 
                 g 
                 50 
                 g 
                 LSC-913 
                 4.5 
                 g 
                 1.02 
                 507 
                 0.97 
                 508 
               
               
                 50 
                 g 
                 50 
                 g 
                 LSC-914 
                 4.5 
                 g 
                 0.97 
                 229 
                 0.95 
                 265 
               
               
                 50 
                 g 
                 50 
                 g 
                 LSC-915 
                 4.5 
                 g 
                 0.71 
                 300 
                 0.66 
                 395 
               
               
                 50 
                 g 
                 50 
                 g 
                 GTT 
                 4.5 
                 g 
                 0.68 
                 451 
                 0.61 
                 389 
               
               
                   
               
             
          
         
       
     
       Example 10 
       [0055]    For subterranean applications can use a two component placement technique to achieve quicker more dramatic set times. A two component system will involve either sequentially pumping and placing one component and then pumping in the second component. Alternatively, material can be pumped simultaneously pumped down to separate pipes or channels and then combined and mixed at the desired location. Demonstrated for a lost circulation application is a potassium silicate based drilling fluid (10% by weight of Ecodrill 317) weighted to a specific gravity of 1.4 using barite with xanthan gum and polyanionic cellulose as viscosity and fluid loss additives. Upon mixing the material set in minutes but did allow for some expansion into a firm but compressible material. The indicated weight of the zinc slurry was added to a clear 50 ml plastic cylinder. The indicated weight of drilling fluid was then added and lightly mixed. The contained was sealed and placed in an oven at 50° C. 
         [0000]    
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 12 
               
             
             
               
                   
               
               
                 downhole mixing of reactive components 
               
             
          
           
               
                 Drilling Fluid containing 
                   
                   
                 30 minute  
               
               
                 10% potassium silicate 
                 Zinc Slurry 
                 Initial density 
                 at 50° C. 
               
               
                   
               
             
          
           
               
                 12.5 g 
                 RXG-PC - 2.5 g 
                 1.37 
                 .96 
               
               
                 12.5 g 
                 RXG-PG - 12.5 g 
                 1.37 
                 1.02 
               
               
                   
               
             
          
         
       
     
       Example 11 
       [0056]    A higher level of gas generation can be obtained in a controlled manner by increasing the metal content in the self-compressing silicate system. Table 13 shows a pumpable solution prepared using different combinations of filler material and a 10% loading of zinc on liquid sodium silicate. A 50 ml cylinder was filled to 10 ml and sealed. Samples were aged at the indicated temperature. 
         [0000]    
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 13 
               
             
             
               
                   
               
               
                 Expansion rate with higher metal loading 
               
             
          
           
               
                   
                 Filler 
                   
                   
                   
               
             
          
           
               
                   
                   
                 Hollow 
                   
                   
                   
                 Density 
               
               
                 Sodium 
                   
                 Glass 
                 Zeolite 
                 Zinc 
                 Starting  
                 after 16 hrs 
               
             
          
           
               
                 Silicate 
                 CaCO 3   
                 Spheres 
                 A 
                 Flake 
                 Density 
                 20° C. 
                 50° C. 
                 85° C. 
               
               
                   
               
             
          
           
               
                 S45 40 g 
                 10 
                 g 
                 10 
                 g 
                 — 
                 4.0  
                 g 
                 1.0 
                 — 
                 0.77 
                 0.33 
               
             
          
           
               
                 S45 50 g 
                 — 
                 5 
                 g 
                 20 
                 g 
                 4.0  
                 g 
                 1.1 
                 — 
                 0.77 
                 0.44 
               
             
          
           
               
                 N silicate 
                 10 
                 g 
                 10 
                 g 
                 — 
                 4.0  
                 g 
                 1.2 
                 0.48 
                 0.32 
                 0.24 
               
             
          
           
               
                 40 g 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
             
          
           
               
                 N silicate 
                 — 
                 5 
                 g 
                 20 
                 g 
                 5.0  
                 g 
                 1.3 
                 0.43 
                 0.34 
                 0.26 
               
             
          
           
               
                 50 g 
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                   
               
             
          
         
       
     
         [0057]    Although the present invention has been described with respect to its application in subterranean environments, it is to be distinctly understood that the present invention can also be used for certain ground applications. 
         [0058]    Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.