Abstract:
A method and product is disclosed which provides emulsion stability and filtration control to invert emulsion drilling fluids. The product comprises a blend of a carboxylic acid terminated polyamide and/or a wetting agent with a reaction product or mixture produced by the Diels-Alder reaction of dienophiles, preferably carboxylic acids, polycarboxylic acids, acid anhydrides, or combinations or mixes thereof, with a mixture of fatty acids and resin acids. The product of the invention is extremely effective, decreasing by about two-thirds the amount of emulsifier generally required to formulate an effective drilling fluid. The product of the invention also greatly reduces and in many cases eliminates the need for conventional fluid loss additives, and additionally provides electrical stability. Moreover, the product of the invention has a pour point as low as about 20 degrees Fahrenheit with minimal solvents, thereby eliminating the need to ship large amounts of inert material for use, and may be transported in a highly active state.

Description:
RELATED APPLICATION 
     This application is a continuation-in-part of U.S. patent application Ser. No. 09/999,799, filed Oct. 31, 2001 now U.S. Pat. No. 6,620,770. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to methods for drilling boreholes in subterranean formations, particularly hydrocarbon bearing formations, and to drilling fluids for use in such drilling operations. More particularly, the present invention relates to oil or synthetic based drilling fluids, fluids comprising invert emulsions, and more particularly drilling fluid additives that facilitate or enhance emulsification, electrical stability or filtration properties of the drilling fluid. 
     2. Description of Relevant Art 
     A drilling fluid or mud is a specially designed fluid that is circulated through a wellbore as the wellbore is being drilled to facilitate the drilling operation. The various functions of a drilling fluid include removing drill cuttings from the wellbore, cooling and lubricating the drill bit, aiding in support of the drill pipe and drill bit, and providing a hydrostatic head to maintain the integrity of the wellbore walls and prevent well blowouts. Specific drilling fluid systems are selected to optimize a drilling operation in accordance with the characteristics of a particular geological formation. 
     Oil or synthetic-based muds, or invert emulsions, are normally used to drill swelling or sloughing shales, salt, gypsum, anhydrite or other evaporite formations, hydrogen sulfide-containing formations, and hot (greater than about 300 degrees Fahrenheit) holes, but may be used in other holes penetrating a subterranean formation as well. These non-aqueous based drilling fluids typically contain oil or a synthetic oil or other synthetic material or synthetic fluid (“synthetic”) as the continuous phase and may also contain water which is dispersed in the continuous phase by emulsification so that there is no distinct layer of water in the fluid. The term “oil mud” or “oil or synthetic-based mud” typically means an invert oil or synthetic mud emulsion or invert emulsion. An all oil mud simply comprises 100% oil by volume as the liquid phase; that is, there is no aqueous internal phase. An invert emulsion drilling fluid may commonly comprise between about 50:50 to 95:5 by volume oil phase to water phase. 
     Most commonly, invert emulsions used in drilling typically comprise: a base oil or synthetic fluid for the external phase; a saline, aqueous solution for the internal phase (typically a solution comprising about 30% calcium chloride); and other agents or additives for suspension, fluid loss, density, oil-wetting, emulsification, filtration, and rheology control. With space at some well sites limited, such as on offshore platforms, and with increasing costs of transport of materials to a wellsite, there is industry-wide interest in, and on-going need for, more efficient and concentrated drilling fluid additives and for drilling fluids which can be formulated and maintained with minimal or fewer additives than common with prior art drilling fluids. 
     SUMMARY OF THE INVENTION 
     An improved and more efficient material or product and method is disclosed for providing emulsion stability and filtration control to invert emulsions and other oil or synthetic based drilling fluids for use in drilling boreholes in subterranean formations, particularly hydrocarbon bearing formations. 
     The product of the invention has the advantage of a pour point at temperatures as low as about 20 degrees Fahrenheit with minimal solvent. Thus, the product of the invention may be transported in a highly (about 90% to about 100%) active state, which reduces the need to inventory products containing different solvents for compatibility with the drilling fluid. This advantage further eliminates the need for shipping large amounts of inert material. Moreover, the product of the invention has the further advantage of providing high levels of filtration control to a drilling fluid made with conventional emulsifiers, especially at temperatures up to about 250° F. Still further, the product of this invention, when added to drilling fluids, reduces or eliminates the need for conventional fluid loss additives. 
     The product of this invention comprises two primary components or parts. One part is a carboxylic acid-terminated polyamide and/or a wetting agent and the other part is itself a mixture produced by the Diels-Alder reaction of dienophiles, preferably carboxylic acids, polycarboxylic acids, acid anhydrides, or combinations or mixes thereof, with a mixture of fatty acids and resin acids. These two components or parts are blended or mixed and further reacted with cations to form soaps. This blending or mixing and this saponification reaction may be achieved in the manufacturing process or it may be effected “in situ” by the presence of or addition of cations to the drilling fluid. As used herein, the term “in situ” shall be understood to mean in the drilling fluid. Typically, such blending and the saponification reaction will occur in the drilling fluid when the drilling fluid is being prepared for use as a drilling fluid or when the drilling fluid is in use as a drilling fluid in drilling a borehole in a subterranean formation. Drilling fluids commonly comprise cations. Sources of such cations include, without limitation, lime, quicklime, and calcium chloride, among others. Further, drilling fluids may incorporate cations contacted in or available from the subterranean formation itself. 
     The method of the invention employs the product of the invention for improved drilling fluids and improved drilling of boreholes in subterranean formations. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a graph comparing the electrical stability of a synthetic based drilling fluid containing the product of the invention with the same synthetic based drilling fluid containing conventional emulsifiers instead of the product of the invention, using data from Tables 1 and 2. 
         FIG. 2  is a graph comparing HTHP filtration of a synthetic based drilling fluid containing the product of the invention with the same synthetic based drilling fluid containing conventional emulsifiers instead of the product of the invention, using data from Tables 3 and 4. 
     
    
    
     DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
     The product of the invention comprises a blend, mixture, or a combination (hereinafter “blend”) of: (1) a carboxylic acid-terminated polyamide and/or a wetting agent (“Component ‘A’”); and (2) a mixture or reaction product (“Component ‘B’”) produced by the Diels-Alder reaction of dienophiles, preferably carboxylic acids, polycarboxylic acids, and anhydrides, or combinations or mixes thereof, with a mixture of fatty acids and resin acids. Component B has a ratio of fatty acids to resin acids preferably ranging from about 4:1 to about 1:1 and a most preferred ratio of about 2:1 and is preferably comprised of fatty acids and resin acids derived from the distillation of crude tall oil. 
     When a carboxylic acid terminated amide is used as Component A, it is preferably concentrated (i.e., about 90% active), and typically made from the condensation reaction between fatty acids and polyamines. The fatty acids and polyamines are reacted in such proportion as to create a “partial amide” intermediate product having a mole ratio of the reactive acid sites to amine sites ranges from about 0.5:1 to about 0.75:1 and most preferably about 0.6:1. This partial amide intermediate product is diluted with a minimum amount of solvent, as needed for further processing, and the remaining amine sites are further reacted with an acid anhydride or polycarboxylic acid to produce the carboxylic acid-terminated polyamide. A most preferred carboxylic acid-terminated fatty polyamide for use in the invention is EZ-MUL® NT CONCENTRATE, the active constituent of EZ-MUL® NT available from Halliburton Energy Services, Inc. in Houston, Tex., although other carboxylic acid terminated fatty polyamides are believed to be useable. 
     Any wetting agent that provides a wetting function in a drilling fluid and preferably that is environmentally acceptable for use in a drilling fluid may be substituted for, or added to, the carboxylic acid terminated amide as Component A in the blend comprising the product of the invention. Examples of such wetting agents include, without limitation, quaternary ammonium salt, lecithin, and sodium dodecylbenzene sulfonate. 
     In comprising the product of the invention, the preferred ratio of Component A to Component B is about 1:5 to about 1:1. Ratios of Component A to Component B of about 1:2 to about 1:3 are most preferred. The exact ratio of these two components or parts may vary greatly depending on the exact desired characteristics of the product. Preferably, however, the quantity of Component B will exceed the quantity of Component A. 
     The blend comprising the product of the invention is preferably made by blending, mixing, or combining these two components—the polyamide and/or wetting agent, and the Diels-Alder modified fatty acid/resin acid mixture or reaction product—together. After blending, the polyamide and/or wetting agent, and the fatty acid/resin acid components, are reacted with cations to form soaps. The polyamide (if present) may undergo some saponification along with or as well as the fatty acid/resin acids. Such blending and saponification may be achieved as part of the manufacturing process of the product of the invention or may be effected in situ the drilling fluid by the presence or addition of cations to the drilling fluid. Calcium cations are preferred and may be obtained, for example, by reacting the modified fatty acid/resin acid component with lime, quicklime, or calcium chloride. The blending in the drilling fluid may occur when the drilling fluid is prepared, when the drilling fluid is at the well surface, or after the drilling fluid has been pumped into the wellbore. When blending in the wellbore, the components may be added to the drilling fluid separately or together. 
     Tall oil is a commonly known product made from acid treatment of alkaline liquors obtained from the manufacture of wood pulp, and tall oil and its derivatives have previously been used in oil-well drilling muds. However, the modified fatty acid/resin acid component of the blend of the product of the invention alone is not effective for achieving the advantages of the invention. EZ-MUL® is known to have utility as an emulsifier for oil based drilling fluids. However, carboxylic acid-terminated fatty polyamides alone cannot achieve all of the advantages of the invention. In the combination disclosed, however, the blend (or mixture) comprising the product of the invention provides a marked advance in the art. 
     Similarly, wetting agents are known to have utility in oil-based drilling fluids. However, wetting agents alone cannot achieve all of the advantages of the product of the invention. In the combination disclosed, however, the blend comprising the product of the invention provides superior performance. 
     The product of the invention is a powerfully efficient additive for oil or synthetic based drilling fluids, affording or effecting enhanced emulsification, and improved electrical stability and fluid loss control, with significantly less volume of additive than previously known or available with prior art drilling fluid additives. The product effects or helps facilitate emulsification typically in amounts of about one-third the quantity commonly needed for emulsification of oil or synthetic based fluids with prior art emulsifiers. That is, amounts of about three pounds to about five pounds of the product of the invention per barrel of drilling fluid can be effective for emulsification. Even lower quantities can improve the electrical stability and filtration control of drilling fluids, even if already emulsified with other emulsifiers. 
     The product of the invention does not rely on a carrier. The material comprising the product is highly active and is believed to be useful with all or substantially all synthetic and oil-based systems known to be effective for drilling fluids. The product of the invention may also add viscosity to the drilling fluid and thus is preferably added to the base drilling fluid before any weighting agents such as barite, for example, are added. 
     The product of this invention is stable even at temperatures up to (and including) about 250 degrees Fahrenheit without filtration additives and up to about 300 degrees to about 350 degrees Fahrenheit with filtration additives. Combining a wetting agent with a carboxylic acid-terminated polyamide as Component A may improve the Theological stability of the product of the invention at temperatures up to about 300° F. Using both a wetting agent and a carboxylic acid terminated amide as Component A, along with Component B, to comprise the product of the invention in an emulsifier package may also improve the oil-wetting nature of the drilling fluid in some base oils or synthetics and/or at certain reservoir conditions. For example, in a hostile or difficult offshore environment, a particular drilling fluid comprising the product of the invention might show enhanced performance upon addition of a wetting agent to the product of the invention, or more particularly or preferably to Component A, while the same drilling fluid in a different environment might show no improvement upon such addition of wetting agent. 
     The product of the invention has a high acid value. Consequently, improved results may be seen when a neutralizer or neutralizing agent is added to the drilling fluid. For example, a preferred maximum of about eight pounds of lime (or similar saponifying agent) might favorably be added per barrel of drilling fluid when about three pounds per barrel of the product of the invention are used in the drilling fluid. A preferred minimum amount of lime is about one-half pound per pound of the product of the invention. Additional lime (or similar saponifying agent) may be helpful or needed with larger quantities of product of the invention for optimum results, although satisfactory results might also be obtained with less. 
     Care is recommended when using the product of this invention to avoid over-treating. Excess emulsifiers (i.e., more than needed to effect emulsification) in drilling fluids can contribute to high fluid viscosity at cold temperatures (i.e., temperatures less than about 45 degrees Fahrenheit). For deepwater operations (i.e., use of drilling fluids at depths of water greater than about 500 feet and at temperatures less than about 45 degrees Fahrenheit), a wetting agent may preferably be used as Component A or added when Component A is a carboxylic acid-terminated amide to help maintain low riser viscosities as drill solids are incorporated in or become carried by the drilling fluid. 
     The method of the invention comprises adding the product of the invention to an oil or synthetic based drilling fluid or employing a drilling fluid comprising the product of the invention in drilling a borehole in a subterranean formation. In another embodiment, the method of the invention comprises adding the product of the invention to an oil or synthetic based drilling fluid to facilitate emulsification of the drilling fluid or the formation of invert emulsions. 
     Experiments were conducted that demonstrate or exemplify the invention. Several formulations of synthetic or oil-based drilling fluids were prepared, typical of those used in the field, and all of which comprised invert emulsions. Specifically, samples of drilling fluids were prepared comprising a synthetic or diesel oil base, to which additives were added, including the product of the invention or a known emulsifier for comparison, as indicated in Tables 1–13 below. The different samples were subjected to different conditions, such as high temperatures or hot rolling, or further additives or contaminants, for example, simulated drill solids or salt water, for comparison of performance and properties. The results of tests tabulated in Tables 1–4 are graphed in  FIGS. 1 and 2 . 
     As used in the tables, the following compounds or products have the meanings indicated below:
     SF BASE™ is a synthetic oil base for drilling fluids typically used in drilling mud systems such as PETROFREE®SF, available from Halliburton Energy Services, Inc. in Houston Tex.;   LE BASE™ is a synthetic oil base for drilling fluids typically used in drilling mud systems such as PETROFREE® LE;   GELTONE® II, is an organoclay for improving viscosity characteristics;   SUSPENTONE® is an organoclay for improving the ability of a drilling fluid to suspend drill cuttings;   INVERMUL® is an emulsifier;   EZ MUL® is an emulsifier with a carboxylic acid terminated polyamide;   LE SUPERMUL® is an emulsifier with a carboxylic acid terminated polyamide;   LE MUL® is an emulsifier;   DRILTREAT™ is a wetting agent;   DEEP-TREAT™ is a wetting agent;   BAROID® is barite, a weighting agent;   DURATONE® HT is a filtration control agent;   BDF-257™ is Component B;   BDF-258™ is the product of the invention having Component B and a carboxylic acid terminated polyamide as Component A;   BD QUAT 2HT™ is dimethyl dihydrogenated tallow quaternary amine and chloride salt; and   Rev Dust is material used to simulate drill solids.
 
All trademarks are the property of Halliburton Energy Services, Inc. and the products are available from Halliburton Energy Services, Inc. in Houston, Tex.
   

     
       
         
               
             
               
               
             
               
               
             
               
             
               
               
               
               
             
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
               
                   
               
               
                 PETROFREE ® SF 
               
               
                 14 lb/gal; 75/25 OWR with 250,000 ppm WPS 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Sample Mark 
                 A (7.33 lb/bbl Active emulsifier content) 
               
               
                   
               
             
          
           
               
                 SF BASE, bbl 
                 0.516 
               
               
                 Freshwater, bbl 
                 0.181 
               
               
                 GELTONE ® II, lb 
                 3 
               
               
                 SUSPENTONE ™, lb 
                 1 
               
               
                 LE ™ MUL, lb 
                 4 
               
               
                 LE ™ SUPERMUL, 
                 6 
               
               
                 lb 
               
               
                 Lime, lb 
                 5 
               
               
                 DURATONE ® HT, 
                 7 
               
               
                 lb 
               
               
                 BAROID ®, lb 
                 330 
               
               
                 Calcium chloride, lb 
                 21.9 
               
               
                 DEEP-TREAT ™, lb 
                 3 
               
               
                   
               
             
          
           
               
                 Mixed 15 minutes at 7000 rpm on a Silverson L4RT before testing; 
               
               
                 mixed 10 minutes after rolling 
               
             
          
           
               
                 Rev Dust, lb 
                 — 
                 45 
                 — 
               
               
                 15% NaCl Brine 
                   
                 — 
                 33 
               
               
                 Added, % vol 
               
             
          
           
               
                 Hot rolled @250° F., 
                 — 
                 16 
                 16 
                 16 
               
               
                 hr 
               
               
                   
               
             
          
           
               
                 Temperature, ° F. 
                 120 
                 40 
                 120 
                 40 
                 120 
                 40 
                 120 
               
               
                   
               
               
                 Plastic viscosity, cP 
                 23 
                 80 
                 24 
                 112 
                 37 
                 108 
                 38 
               
               
                 Yield point, lb/100 ft 2   
                 15 
                 18 
                 8 
                 19 
                 8 
                 26 
                 11 
               
               
                 10 Sec gel, lb/100 ft 2   
                 8 
                 7 
                 6 
                 10 
                 7 
                 9 
                 6 
               
               
                 10 Min gel, lb/100 ft 2   
                 9 
                 11 
                 8 
                 18 
                 10 
                 12 
                 10 
               
             
          
           
               
                 Electrical stability, v 
                 690 
                 235 
                 488 
                 77 
               
               
                 HTHP filtrate 
                 2.4 
                 2.4 
                 10.4 
                 7.6 
               
               
                 @250° F., ml 
                   
                   
                   
                 (0.5 water) 
               
             
          
           
               
                 Fann 35 dial readings 
               
             
          
           
               
                 600 rpm 
                 61 
                 178 
                 56 
                 243 
                 82 
                 242 
                 87 
               
               
                 300 rpm 
                 38 
                 98 
                 32 
                 131 
                 45 
                 134 
                 49 
               
               
                 200 rpm 
                 29 
                 69 
                 24 
                 91 
                 33 
                 94 
                 36 
               
               
                 100 rpm 
                 20 
                 38 
                 15 
                 51 
                 20 
                 53 
                 23 
               
               
                  6 rpm 
                 7 
                 7 
                 5 
                 10 
                 5 
                 10 
                 7 
               
               
                  3 rpm 
                 6 
                 6 
                 4 
                 9 
                 4 
                 8 
                 6 
               
               
                   
               
               
                 Note: 
               
               
                 Contaminated samples were made up with mud already hot rolled 16 hr. @250° F. 
               
             
          
         
       
     
     
       
         
               
             
               
               
             
               
               
             
               
             
               
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
               
                   
               
               
                 PETROFREE ® SF 
               
               
                 14 lb/gal; 75/25 OWR with 250,000 ppm WPS 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Sample Mark 
                 H3 
               
               
                   
               
             
          
           
               
                 SF BASE, bbl 
                 0.516 
               
               
                 Freshwater, bbl 
                 0.181 
               
               
                 GELTONE ® II, lb 
                 3 
               
               
                 SUSPENTONE ™, lb 
                 1 
               
               
                 BDF-258, lb 
                 3 
               
               
                 Lime, lb 
                 8 
               
               
                 DURATONE ® HT, lb 
                 7 
               
               
                 BAROID ®, lb 
                 330 
               
               
                 Calcium chloride, lb 
                 21.9 
               
               
                 DEEP-TREAT ™, lb 
                 3 
               
               
                   
               
             
          
           
               
                 Mixed 15 minutes at 7000 rpm on a Silverson L4RT before testing; mixed 10 minutes after rolling 
               
             
          
           
               
                 Rev Dust, lb 
                 — 
                 45 
                 — 
               
               
                 15% NaCl Brine Added, % vol 
                   
                 — 
                 33 
               
             
          
           
               
                 Hot rolled @250° F., hr 
                 — 
                 — 
                 16 
                 16 
                 16 
               
               
                   
               
             
          
           
               
                 Temperature, ° F. 
                 120 
                 40 
                 120 
                 40 
                 120 
                  40 
                 120 
                 40 
                 120 
               
               
                   
               
               
                 Plastic viscosity, cP 
                 29 
                 78 
                 27 
                 72 
                 26 
                 N/A 
                 49 
                 113 
                 43 
               
               
                 Yield point, lb/100 ft 2   
                 16 
                 33 
                 14 
                 24 
                 12 
                 N/A 
                 24 
                 43 
                 20 
               
               
                 10 Sec gel, lb/100 ft 2   
                 8 
                 15 
                 7 
                 13 
                 7 
                  27 
                 16 
                 19 
                 13 
               
               
                 10 Min gel, lb/100 ft 2   
                 10 
                 17 
                 9 
                 15 
                 9 
                  57 
                 36 
                 20 
                 13 
               
             
          
           
               
                 Electrical stability, v 
                 638 
                 669 
                 630 
                 884 
                 393 
               
               
                 HTHP filtrate @250° F., ml 
                   
                 2.0 
                 1.6 
                 5.2 
                 2.4 
               
             
          
           
               
                 Fann 35 dial readings 
               
             
          
           
               
                 600 rpm 
                 74 
                 189 
                 68 
                 168 
                 64 
                 O/S 
                 122 
                 269 
                 106 
               
               
                 300 rpm 
                 45 
                 111 
                 41 
                 96 
                 38 
                 186 
                 73 
                 156 
                 63 
               
               
                 200 rpm 
                 35 
                 82 
                 32 
                 72 
                 30 
                 139 
                 56 
                 116 
                 48 
               
               
                 100 rpm 
                 24 
                 53 
                 22 
                 45 
                 20 
                  88 
                 38 
                 72 
                 32 
               
               
                  6 rpm 
                 9 
                 17 
                 8 
                 14 
                 8 
                  29 
                 15 
                 21 
                 12 
               
               
                  3 rpm 
                 8 
                 15 
                 7 
                 12 
                 7 
                  26 
                 14 
                 19 
                 11 
               
               
                   
               
               
                 Note: 
               
               
                 O/S indicates an off-scale reading or &gt;300. Contaminated samples were made up with mud already rolled 16 hr @250° F. 
               
             
          
         
       
     
     
       
         
               
             
               
               
             
               
               
             
               
             
               
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
               
                   
               
               
                 PETROFREE ® LE 
               
               
                 14 lb/gal; 75/25 OWR with 250,000 ppm WPS 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Sample Mark 
                 C 
               
               
                   
               
             
          
           
               
                 LE BASE, bbl 
                 0.5094 
               
               
                 Freshwater, bbl 
                 0.1793 
               
               
                 GELTONE ® II, lb 
                 3.5 
               
               
                 SUSPENTONE ™, lb 
                 2 
               
               
                 LE ™ MUL, lb 
                 7 
               
               
                 LE ™ SUPERMUL, lb 
                 4 
               
               
                 Lime, lb 
                 7 
               
               
                 DURATONE ® HT, lb 
                 6 
               
               
                 Calcium chloride, lb 
                 21.8 
               
               
                 BAROID ®, lb 
                 332.3 
               
               
                 DEEP-TREAT ™, lb 
                 3.5 
               
               
                   
               
             
          
           
               
                 Mixed 15 minutes at 7000 rpm on a Silverson L4RT before testing; mixed 10 minutes after rolling 
               
             
          
           
               
                 Rev Dust, lb 
                 — 
                 45 
                 — 
               
               
                 15% NaCl Brine Added, % vol 
                   
                 — 
                 33 
               
             
          
           
               
                 Hot rolled @250° F., hr 
                 — 
                 — 
                 16 
                 16 
                 16 
               
               
                   
               
             
          
           
               
                 Temperature, ° F. 
                 120 
                 40 
                 120 
                 40 
                 120 
                 40 
                 120 
                 40 
                 120 
               
               
                   
               
               
                 Plastic viscosity, cP 
                 23 
                 94 
                 22 
                 77 
                 23 
                 82 
                 32 
                 87 
                 35 
               
               
                 Yield point, lb/100 ft 2   
                 12 
                 51 
                 9 
                 18 
                 6 
                 12 
                 5 
                 14 
                 4 
               
               
                 10 Sec gel, lb/100 ft 2   
                 6 
                 17 
                 6 
                 9 
                 5 
                 8 
                 5 
                 7 
                 5 
               
               
                 10 Min gel, lb/100 ft 2   
                 9 
                 21 
                 8 
                 15 
                 7 
                 15 
                 8 
                 10 
                 6 
               
             
          
           
               
                 Electrical stability, v 
                 737 
                 676 
                 474 
                 545 
                 230 
               
               
                 HTHP filtrate @250° F., ml 
                   
                 4.4 
                 2.0 
                 10.0 
                 12.0 - 1.1 
               
               
                   
                   
                   
                   
                   
                 emul. 
               
             
          
           
               
                 Fann 35 dial readings 
               
             
          
           
               
                 600 rpm 
                 58 
                 239 
                 53 
                 172 
                 52 
                 176 
                 69 
                 188 
                 74 
               
               
                 300 rpm 
                 35 
                 145 
                 31 
                 95 
                 29 
                 94 
                 37 
                 101 
                 39 
               
               
                 200 rpm 
                 26 
                 108 
                 24 
                 67 
                 22 
                 66 
                 28 
                 70 
                 29 
               
               
                 100 rpm 
                 17 
                 66 
                 16 
                 38 
                 13 
                 37 
                 17 
                 38 
                 17 
               
               
                  6 rpm 
                 6 
                 19 
                 5 
                 9 
                 4 
                 8 
                 4 
                 7 
                 5 
               
               
                  3 rpm 
                 5 
                 17 
                 4 
                 8 
                 3 
                 7 
                 3 
                 6 
                 4 
               
               
                   
               
               
                 Note: 
               
               
                 O/S indicates an off-scale reading, or &gt;300. Contaminated samples were made up with mud already hot rolled 16 hr @250° F. 
               
             
          
         
       
     
     
       
         
               
             
               
               
             
               
               
             
               
             
               
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 4 
               
               
                   
               
               
                 PETROFREE ® LE 
               
               
                 14 lb/gal; 75/25 OWR with 250,000 ppm WPS 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Sample Mark 
                 B2 
               
               
                   
               
             
          
           
               
                 LE BASE, bbl 
                 0.5163 
               
               
                 Freshwater, bbl 
                 0.1796 
               
               
                 GELTONE ® II, lb 
                 3 
               
               
                 SUSPENTONE ™, lb 
                 2 
               
               
                 BDF-258, lb 
                 3 
               
               
                 Lime, lb 
                 7 
               
               
                 DURATONE ® HT, lb 
                 6 
               
               
                 Calcium chloride, lb 
                 21.8 
               
               
                 BAROID ®, lb 
                 333.2 
               
               
                 DEEP-TREAT ™, lb 
                 3.3 
               
               
                   
               
             
          
           
               
                 Mixed 15 minutes at 7000 rpm on a Silverson L4RT before testing; mixed 10 minutes after rolling 
               
             
          
           
               
                 Rev Dust, lb 
                 — 
                 45 
                 — 
               
               
                 15% NaCl Brine Added, % vol 
                   
                 — 
                 33 
               
             
          
           
               
                 Hot rolled @250° F., hr 
                 — 
                 — 
                 16 
                 16 
                 16 
               
               
                   
               
             
          
           
               
                 Temperature, ° F. 
                 120 
                 40 
                 120 
                 40 
                 120 
                 40 
                 120 
                 40 
                 120 
               
               
                   
               
               
                 Plastic viscosity, cP 
                 26 
                 72 
                 23 
                 64 
                 23 
                 98 
                 34 
                 96 
                 36 
               
               
                 Yield point, lb/100 ft 2   
                 12 
                 29 
                 9 
                 16 
                 7 
                 26 
                 6 
                 32 
                 11 
               
               
                 10 Sec gel, lb/100 ft 2   
                 7 
                 14 
                 6 
                 12 
                 6 
                 13 
                 6 
                 16 
                 10 
               
               
                 10 Min gel, lb/100 ft 2   
                 9 
                 18 
                 8 
                 16 
                 9 
                 28 
                 8 
                 21 
                 9 
               
             
          
           
               
                 Electrical stability, v 
                 554 
                 615 
                 568 
                 574 
                 269 
               
               
                 HTHP filtrate @250° F., ml 
                   
                 2.2 
                 2.2 
                 3.0 
                 1.8 
               
             
          
           
               
                 Fann 35 dial readings 
               
             
          
           
               
                 600 rpm 
                 64 
                 173 
                 55 
                 144 
                 53 
                 222 
                 74 
                 224 
                 83 
               
               
                 300 rpm 
                 38 
                 101 
                 32 
                 80 
                 30 
                 124 
                 40 
                 128 
                 47 
               
               
                 200 rpm 
                 29 
                 75 
                 25 
                 58 
                 23 
                 89 
                 29 
                 94 
                 36 
               
               
                 100 rpm 
                 20 
                 47 
                 17 
                 35 
                 15 
                 52 
                 18 
                 58 
                 23 
               
               
                  6 rpm 
                 7 
                 15 
                 6 
                 10 
                 6 
                 13 
                 4 
                 16 
                 8 
               
               
                  3 rpm 
                 6 
                 14 
                 5 
                 9 
                 5 
                 11 
                 3 
                 14 
                 7 
               
               
                   
               
               
                 Note: 
               
               
                 O/S indicates an off-scale reading, or &gt;300. Contaminated samples were made up with mud already hot rolled 16 hr @250° F. 
               
             
          
         
       
     
     
       
         
               
             
               
               
             
               
               
             
               
             
               
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 5 
               
               
                   
               
               
                 PETROFREE ® SF 
               
               
                 14 lb/gal; 75/25 OWR with 250,000 ppm WPS 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Sample Mark 
                 H2 
               
               
                   
               
             
          
           
               
                 SF BASE, bbl 
                 0.516 
               
               
                 Freshwater, bbl 
                 0.181 
               
               
                 GELTONE ® II, lb 
                 3 
               
               
                 SUSPENTONE ™, lb 
                 1 
               
               
                 BDF-258, lb 
                 3 
               
               
                 Lime, lb 
                 8 
               
               
                 DURATONE ® HT, lb 
                 7 
               
               
                 BAROID ®, lb 
                 330 
               
               
                 Calcium chloride, lb 
                 21.9 
               
               
                 DEEP-TREAT ™, lb 
                 3 
               
               
                 DRILTREAT ®, lb 
                 1 
               
               
                   
               
             
          
           
               
                 Mixed 15 minutes at 7000 rpm on a Silverson L4RT before testing; mixed 10 minutes after rolling 
               
             
          
           
               
                 Rev Dust, lb 
                 — 
                 45 
                 — 
               
               
                 15% NaCl Brine Added, % vol 
                   
                 — 
                 33 
               
             
          
           
               
                 Hot rolled @250° F., hr 
                 — 
                 — 
                 16 
                 16 
                 16 
               
               
                   
               
             
          
           
               
                 Temperature, ° F. 
                 120 
                 40 
                 120 
                 40 
                 120 
                 40 
                 120 
                 40 
                 120 
               
               
                   
               
               
                 Plastic viscosity, cP 
                 28 
                 82 
                 25 
                 86 
                 25 
                 N/A 
                 46 
                 116 
                 41 
               
               
                 Yield point, lb/100 ft 2   
                 14 
                 36 
                 16 
                 29 
                 14 
                 N/A 
                 22 
                 45 
                 22 
               
               
                 10 Sec gel, lb/100 ft 2   
                 7 
                 17 
                 7 
                 14 
                 8 
                 28 
                 18 
                 19 
                 12 
               
               
                 10 Min gel, lb/100 ft 2   
                 10 
                 20 
                 9 
                 18 
                 10 
                 60 
                 31 
                 21 
                 12 
               
             
          
           
               
                 Electrical stability, v 
                 603 
                 694 
                 684 
                 846 
                 409 
               
               
                 HTHP filtrate @250° F., ml 
                   
                 1.2 
                 1.6 
                 4.0 
                 1.6 
               
             
          
           
               
                 Fann 35 dial readings 
               
             
          
           
               
                 600 rpm 
                 70 
                 200 
                 66 
                 201 
                 64 
                 O/S 
                 114 
                 277 
                 104 
               
               
                 300 rpm 
                 42 
                 118 
                 41 
                 115 
                 39 
                 201 
                 68 
                 161 
                 63 
               
               
                 200 rpm 
                 33 
                 89 
                 32 
                 84 
                 30 
                 149 
                 52 
                 119 
                 48 
               
               
                 100 rpm 
                 22 
                 57 
                 22 
                 51 
                 21 
                 93 
                 34 
                 74 
                 33 
               
               
                  6 rpm 
                 8 
                 19 
                 8 
                 15 
                 8 
                 28 
                 13 
                 22 
                 13 
               
               
                  3 rpm 
                 7 
                 17 
                 7 
                 14 
                 7 
                 24 
                 12 
                 19 
                 12 
               
               
                   
               
               
                 Note: 
               
               
                 O/S indicates an off-scale reading, or &gt;300. Contaminated samples were made up with mud already rolled 16 hr @250° F. 
               
             
          
         
       
     
     
       
         
               
             
               
               
             
               
               
             
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 6 
               
               
                   
               
               
                 PETROFREE ® SF 
               
               
                 14 lb/gal; 75/25 OWR with 250,000 ppm WPS 
               
               
                 NO DURATONE ® HT 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Sample Mark 
                 O 
               
               
                   
               
             
          
           
               
                 SF BASE, lb 
                 0.516 
               
               
                 Freshwater, bbl 
                 0.181 
               
               
                 GELTONE ® II, lb 
                 4 
               
               
                 SUSPENTONE ™, lb 
                 1 
               
               
                 BDF-258, lb 
                 3 
               
               
                 Lime, lb 
                 9 
               
               
                 Calcium chloride, lb 
                 21.9 
               
               
                 BAROID ®, lb 
                 330 
               
               
                 DRILTREAT ®, lb 
                 1 
               
               
                 DEEP-TREAT ™, lb 
                 3 
               
               
                   
               
             
          
           
               
                 Mixed 15 minutes at 7000 rpm on a Silverson L4RT before testing; mixed 10 minutes after rolling 
               
             
          
           
               
                 Hot rolled @250° F., hr 
                 — 
                 — 
                 16 
                 16 
                 16 
               
               
                 Rev Dust, lb 
                 — 
                 — 
                 — 
                 45 
                 — 
               
               
                 15% NaCl brine, % vol 
                   
                   
                 — 
                 — 
                 33 
               
               
                   
               
             
          
           
               
                 Temperature, ° F. 
                 120 
                 40 
                 120 
                 40 
                 120 
                  40 
                 120 
                  40 
                 120 
               
               
                   
               
               
                 Plastic viscosity, cP 
                 28 
                 88 
                 33 
                 85 
                 29 
                 N/A 
                 50 
                 N/A 
                 69 
               
               
                 Yield point, lb/100 ft 2   
                 5 
                 19 
                 8 
                 20 
                 8 
                 N/A 
                 5 
                 N/A 
                 45 
               
               
                 10 Sec gel, lb/100 ft 2   
                 5 
                 10 
                 7 
                 9 
                 5 
                  5 
                 3 
                  48 
                 25 
               
               
                 10 Min gel, lb/100 ft 2   
                 8 
                 14 
                 9 
                 13 
                 7 
                  14 
                 10 
                 &gt;60 
                 62 
               
             
          
           
               
                 Electrical stability @120° F., v 
                 471 
                 519 
                 496/230 
                 218 
                 285 
               
               
                 HTHP filtrate @250° F., ml 
                   
                 0.2 
                 1.6 
                 4.0 
                 3.4–0.4 
               
               
                   
                   
                   
                   
                   
                 H 2 O 
               
             
          
           
               
                 Fann 35 dial readings 
               
             
          
           
               
                 600 rpm 
                 61 
                 195 
                 74 
                 190 
                 66 
                 O/S 
                 105 
                 O/S 
                 183 
               
               
                 300 rpm 
                 33 
                 107 
                 41 
                 105 
                 37 
                 173 
                 55 
                 O/S 
                 114 
               
               
                 200 rpm 
                 25 
                 75 
                 31 
                 75 
                 27 
                 123 
                 39 
                 256 
                 87 
               
               
                 100 rpm 
                 16 
                 43 
                 20 
                 44 
                 17 
                  68 
                 21 
                 163 
                 57 
               
               
                  6 rpm 
                 5 
                 10 
                 7 
                 10 
                 5 
                  7 
                 3 
                  45 
                 26 
               
               
                  3 rpm 
                 4 
                 8 
                 6 
                 8 
                 4 
                  5 
                 2 
                  40 
                 24 
               
               
                   
               
               
                 Note: 
               
               
                 O/S indicates an off-scale reading, or &gt;300. Contaminated samples were made up with mud already rolled 16 hr @250° F. 
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 7 
               
               
                   
               
               
                 INVERMUL ® 
               
               
                 14 lb/gal; 250,000 WPS 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Sample Mark 
                 1 
                 2 
                 3 
                 4 
                 5 
               
               
                   
               
               
                 Diesel, bbl 
                 0.5395 
                 0.5234 
                 0.5679 
                 0.5743 
                 0.5608 
               
               
                 Fresh water, bbl 
                 0.1814 
                 0.1815 
                 0.1449 
                 0.1453 
                 0.1454 
               
               
                 Oil-to-Water Ratio 
                 75/25 
                 75/25 
                 80/20 
                 80/20 
                 80/20 
               
               
                 GELTONE ® II, lb 
                 2 
                 2 
                 2 
                 2 
                 2 
               
               
                 SUSPENTONE ™, lb 
                 1 
                 1 
                 — 
                 — 
                 — 
               
               
                 BDF-258, lb 
                 3.5 
                 — 
                 6 
                 3 
                 — 
               
               
                 INVERMUL ® NT, lb 
                 — 
                 3 
                 — 
                 — 
                 3 
               
               
                 Lime, lb 
                 8 
                 8 
                 12 
                 8 
                 8 
               
               
                 DURATONE ® HT, lb 
                 6 
                 6 
                 6 
                 6 
                 6 
               
               
                 EZ MUL ® NT, lb 
                 — 
                 6 
                 — 
                 — 
                 6 
               
               
                 Calcium chloride, lb 
                 22.0 
                 22.1 
                 17.6 
                 17.7 
                 17.7 
               
               
                 BAROID ®, lb 
                 302 
                 301 
                 307 
                 310 
                 309 
               
               
                 Rev Dust, lb 
                 20 
                 20 
                 20 
                 20 
                 20 
               
               
                 DRILTREAT ®, lb 
                 — 
                 — 
                 — 
                 1.5 
                 — 
               
             
          
           
               
                 Hot rolled @300 ° F., hr 
                 — 
                 — 
                 — 
                 16 
                 — 
                 16 
                 — 
                 16 
                   
               
               
                 Plastic viscosity @150° F., cP 
                 25 
                 26 
                 21 
                 23 
                 22 
                 19 
                 20 
                 22 
               
               
                 Yield point, lb/100 ft 2   
                 31 
                 53 
                 17 
                 11 
                 13 
                 9 
                 30 
                 8 
               
               
                 10 Sec gel, lb/100 ft 2   
                 26 
                 32 
                 12 
                 14 
                 8 
                 8 
                 16 
                 8 
               
               
                 10 Min gel, lb/100 ft 2   
                 34 
                 34 
                 23 
                 29 
                 15 
                 16 
                 16 
                 9 
               
               
                 Electrical stability, v 
                 593 
                 1140 
                 923 
                 1302 
                 697 
                 783 
                 1404 
                 766 
               
               
                 HTHP filtrate @300° F., ml 
                 11.6* 
                 3.8 
                 6.2 
                 16.4 
                 5.6 
                 10.0 
                 5.4 
                 7.6 
               
             
          
           
               
                 Fann 35 dial readings 
               
             
          
           
               
                 600 rpm 
                 81 
                 105 
                 59 
                 57 
                 57 
                 47 
                 70 
                 52 
                   
               
               
                 300 rpm 
                 56 
                 79 
                 38 
                 34 
                 35 
                 28 
                 50 
                 30 
               
               
                 200 rpm 
                 46 
                 69 
                 30 
                 26 
                 28 
                 21 
                 42 
                 23 
               
               
                 100 rpm 
                 36 
                 56 
                 22 
                 17 
                 19 
                 14 
                 32 
                 16 
               
               
                  6 rpm 
                 21 
                 33 
                 10 
                 8 
                 8 
                 7 
                 17 
                 7 
               
               
                  3 rpm 
                 20 
                 32 
                 9 
                 7 
                 7 
                 6 
                 16 
                 6 
               
               
                   
               
               
                 *Trace of water/emulsion was seen in the filtrate. 
               
             
          
         
       
     
     
       
         
               
             
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 8 
               
               
                   
               
               
                 INVERMUL ® 
               
               
                 14 lb/gal; 80/20 OWR with 250,000 WPS 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Sample Mark 
                 10 
                 11 
               
               
                   
               
               
                 Diesel, bbl 
                 0.577 
                 0.577 
               
               
                 Fresh water, bbl 
                 0.145 
                 0.145 
               
               
                 GELTONE ® II, lb 
                 6 
                 6 
               
               
                 BDF-258, lb 
                 3 
                 3 
               
               
                 Lime, lb 
                 8 
                 8 
               
               
                 Calcium chloride, lb 
                 17.6 
                 17.6 
               
               
                 DEEP-TREAT ™, lb 
                 1.5 
                 1 
               
               
                 BAROID ®, lb 
                 312 
                 312 
               
               
                 Rev Dust, lb 
                 20 
                 20 
               
               
                 DRILTREAT ®, lb 
                 — 
                 1 
               
             
          
           
               
                 Hot rolled @ 150° F., hr 
                 16 
                 — 
                 16 
                 — 
               
               
                 Hot rolled @ 250° F., hr 
                 — 
                 16 
                 — 
                 16 
               
               
                 Plastic viscosity @ 150° F., cP 
                 23 
                 24 
                 23 
                 24 
               
               
                 Yield point, lb/100 ft 2   
                 28 
                 10 
                 25 
                 12 
               
               
                 10 Sec gel, lb/100 ft 2   
                 17 
                 10 
                 18 
                 11 
               
               
                 10 Min gel, lb/100 ft 2   
                 22 
                 16 
                 20 
                 20 
               
               
                 Electrical stability, v 
                 686 
                 783 
                 561 
                 723 
               
               
                 HTHP filtrate @ 250° F., ml 
                 5.6 
                 6.8 
                 6.6 
                 9.4 
               
               
                 HTHP filt.cake thickness, 1/32″ 
                 4 
                 3 
                 5 
                 5 
               
               
                 Fann 35 dial readings 
               
               
                 600 rpm 
                 74 
                 58 
                 71 
                 60 
               
               
                 300 rpm 
                 51 
                 34 
                 48 
                 36 
               
               
                 200 rpm 
                 42 
                 26 
                 39 
                 28 
               
               
                 100 rpm 
                 32 
                 17 
                 30 
                 19 
               
               
                  6 rpm 
                 17 
                 7 
                 17 
                 8 
               
               
                  3 rpm 
                 16 
                 6 
                 17 
                 8 
               
               
                   
               
               
                 Note: 
               
               
                 0.4 lb/bbl DEEP-TREAT ™ was sufficient to wet in the barite and Rev Dust in mud 11. Additional product was added after the Rev Dust to total 1 lb/bbl. 
               
             
          
         
       
     
     
       
         
               
             
               
               
             
               
               
             
               
             
               
               
               
               
               
               
             
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 9 
               
               
                   
               
               
                 PETROFREE ® SF 
               
               
                 14 lb/gal; 75/25 OWR with 250,000 ppm WPS 
               
               
                 NO DURATONE ® HT 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Sample Mark 
                 I 
               
               
                   
               
             
          
           
               
                 SF BASE, bbl 
                 0.516 
               
               
                 Freshwater, bbl 
                 0.181 
               
               
                 GELTONE ® II, lb 
                 4 
               
               
                 SUSPENTONE ™, lb 
                 1 
               
               
                 BDF-258, lb 
                 3.5 
               
               
                 Lime, lb 
                 9 
               
               
                 DURATONE ® HT, lb 
                 — 
               
               
                 Calcium chloride, lb 
                 21.9 
               
               
                 DEEP-TREAT ™, lb 
                 3 
               
               
                 BAROID ®, lb 
                 330 
               
               
                   
               
             
          
           
               
                 Mixed 15 minutes at 7000 rpm on a Silverson L4RT before testing; mixed 10 minutes after rolling 
               
             
          
           
               
                 Hot rolled @250° F., hr 
                 — 
                 — 
                 16 
                 16 
                 16 
               
             
          
           
               
                 Rev Dust, lb 
                 — 
                 45 
                 — 
               
               
                 15% NaCl Brine Added, % vol 
                   
                 — 
                 33 
               
               
                   
               
             
          
           
               
                 Temperature, ° F. 
                 120 
                 40 
                 120 
                 40 
                 120 
                  40 
                 120 
                  58 
                 120 
               
               
                   
               
               
                 Plastic viscosity, cP 
                 29 
                 85 
                 32 
                 76 
                 31 
                 N/A 
                 54 
                 N/A 
                 71 
               
               
                 Yield point, lb/100 ft 2   
                 9 
                 17 
                 9 
                 15 
                 6 
                 N/A 
                 7 
                 N/A 
                 53 
               
               
                 10 Sec gel, lb/100 ft 2   
                 7 
                 10 
                 8 
                 9 
                 7 
                  6 
                 4 
                  55 
                 34 
               
               
                 10 Min gel, lb/100 ft 2   
                 8 
                 15 
                 11 
                 10 
                 7 
                  13 
                 8 
                 — 
                 65 
               
             
          
           
               
                 Electrical stability, v 
                 482 
                 529 
                 241 
                 234 
                 293 
               
               
                 HTHP filtrate @250° F., ml 
                   
                 1.6 
                 2.8* 
                 6.0 
                 5.0–1.0 H 2 O 
               
             
          
           
               
                 Fann 35 dial readings 
               
             
          
           
               
                 600 rpm 
                 67 
                 187 
                 73 
                 167 
                 68 
                 O/S 
                 115 
                 O/S 
                 195 
               
               
                 300 rpm 
                 38 
                 102 
                 41 
                 91 
                 37 
                 186 
                 61 
                 278 
                 124 
               
               
                 200 rpm 
                 29 
                 73 
                 31 
                 65 
                 28 
                 130 
                 43 
                 220 
                 97 
               
               
                 100 rpm 
                 19 
                 42 
                 20 
                 38 
                 18 
                  71 
                 23 
                 151 
                 67 
               
               
                  6 rpm 
                 6 
                 10 
                 7 
                 9 
                 6 
                  8 
                 3 
                  53 
                 29 
               
               
                  3 rpm 
                 5 
                 8 
                 6 
                 7 
                 5 
                  5 
                 2 
                  50 
                 28 
               
               
                   
               
               
                 Note: 
               
               
                 O/S indicates an off-scale reading, or &gt;300. Contaminated samples were made up with mud already rolled 16 hr @250° F. 
               
               
                 *Some small water droplets were observed in the filtrate 
               
             
          
         
       
     
     
       
         
               
             
               
               
             
               
               
             
               
             
               
               
               
               
               
               
             
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 10 
               
               
                   
               
               
                 PETROFREE ® SF 
               
               
                 14 lb/gal; 75/25 OWR with 250,000 ppm WPS 
               
               
                 NO DURATONE ® HT 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Sample Mark 
                 N 
               
               
                   
               
             
          
           
               
                 SF BASE, lb 
                 0.516 
               
               
                 Freshwater, bbl 
                 0.181 
               
               
                 GELTONE ® II, lb 
                 4 
               
               
                 SUSPENTONE ™, lb 
                 1 
               
               
                 BDF-258, lb 
                 3.5 
               
               
                 Lime, lb 
                 9 
               
               
                 Calcium chloride, lb 
                 21.9 
               
               
                 DEEP-TREAT ™, lb 
                 4 
               
               
                 BAROID ®, lb 
                 330 
               
               
                   
               
             
          
           
               
                 Mixed 15 minutes at 7000 rpm on a Silverson L4RT before testing; mixed 10 minutes after rolling 
               
             
          
           
               
                 Hot rolled @250° F., hr 
                 — 
                 — 
                 16 
                 16 
                 16 
               
             
          
           
               
                 Rev Dust, lb 
                 — 
                 45 
                 — 
               
               
                 15% NaCl brine, % vol 
                   
                 — 
                 33 
               
               
                 DEEP-TREAT ™, lb 
                 — 
                 2 
                 2 
               
               
                   
               
             
          
           
               
                 Temperature, ° F. 
                 120 
                 40 
                 120 
                 40 
                 120 
                 40 
                 120 
                  40 
                 120 
               
               
                   
               
               
                 Plastic viscosity, cP 
                 35 
                 103 
                 38 
                 80 
                 31 
                 124 
                 44 
                 N/A 
                 53 
               
               
                 Yield point, lb/100 ft 2   
                 11 
                 18 
                 11 
                 16 
                 6 
                 22 
                 5 
                 N/A 
                 10 
               
               
                 10 Sec gel, lb/100 ft 2   
                 8 
                 10 
                 7 
                 8 
                 6 
                 5 
                 5 
                  8 
                 6 
               
               
                 10 Min gel, lb/100 ft 2   
                 14 
                 16 
                 11 
                 9 
                 7 
                 8 
                 7 
                  10 
                 7 
               
             
          
           
               
                 Electrical stability @120° F., v 
                 503 
                 527 
                 209 
                 275 
                 156 
               
               
                 HTHP filtrate @250° F., ml 
                   
                 0.6 
                 1.2 
                 1.6 
                 1.0–trace emul 
               
             
          
           
               
                 Fann 35 dial readings 
               
             
          
           
               
                 600 rpm 
                 81 
                 224 
                 87 
                 176 
                 68 
                 270 
                 93 
                 O/S 
                 116 
               
               
                 300 rpm 
                 46 
                 121 
                 49 
                 96 
                 37 
                 146 
                 49 
                 189 
                 63 
               
               
                 200 rpm 
                 35 
                 85 
                 37 
                 68 
                 29 
                 101 
                 35 
                 134 
                 44 
               
               
                 100 rpm 
                 22 
                 49 
                 24 
                 39 
                 18 
                 55 
                 20 
                  74 
                 25 
               
               
                  6 rpm 
                 7 
                 10 
                 7 
                 8 
                 6 
                 6 
                 4 
                  10 
                 5 
               
               
                  3 rpm 
                 6 
                 8 
                 6 
                 7 
                 5 
                 4 
                 3 
                  7 
                 4 
               
               
                   
               
               
                 Note: 
               
               
                 O/S indicates an off-scale reading, or &gt;300. Contaminated samples were made up with mud already rolled 16 hr @250° F. 
               
             
          
         
       
     
     
       
         
               
             
               
               
             
               
               
             
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 11 
               
               
                   
               
               
                 PETROFREE ® SF 
               
               
                 14 lb/gal; 75/25 OWR with 250,000 ppm WPS 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Sample Mark 
                 BB 
               
               
                   
               
             
          
           
               
                 SF BASE, lb 
                 0.516 
               
               
                 Freshwater, bbl 
                 0.181 
               
               
                 GELTONE ® II, lb 
                 4 
               
               
                 SUSPENTONE ™, lb 
                 1 
               
               
                 BDF-258, lb 
                 3.5 
               
               
                 Lime, lb 
                 9 
               
               
                 Calcium chloride, lb 
                 21.9 
               
               
                 BD QUAT 2HT, lb 
                 1 
               
               
                 BAROID ®, lb 
                 330 
               
               
                 DEEP-TREAT ™, lb 
                 3 
               
               
                   
               
             
          
           
               
                 Mixed 15 minutes at 7000 rpm on a Silverson L4RT before testing; mixed 10 minutes after rolling 
               
             
          
           
               
                 Hot rolled @250° F., hr 
                 — 
                 — 
                 16 
                 16 
                 16 
               
               
                 Rev Dust, lb 
                 — 
                 — 
                 — 
                 45 
                 — 
               
               
                 15% NaCl brine, % vol 
                   
                   
                 — 
                 — 
                 25 
               
               
                   
               
             
          
           
               
                 Temperature, ° F. 
                 120 
                 40 
                 120 
                 40 
                 120 
                 40 
                 120 
                 40 
                 120 
               
               
                   
               
               
                 Plastic viscosity, cP 
                 29 
                 76 
                 30 
                 75 
                 28 
                 119 
                 40 
                 119 
                 43 
               
               
                 Yield point, lb/100 ft 2   
                 15 
                 32 
                 17 
                 24 
                 10 
                 16 
                 6 
                 35 
                 14 
               
               
                 10 Sec gel, lb/100 ft 2   
                 8 
                 14 
                 8 
                 11 
                 7 
                 7 
                 5 
                 15 
                 8 
               
               
                 10 Min gel, lb/100 ft 2   
                 13 
                 17 
                 9 
                 12 
                 8 
                 11 
                 10 
                 15 
                 9 
               
             
          
           
               
                 Electrical stability @120° F., v 
                 633 
                 *486 average 
                 333 
                 576 
                 223 
               
               
                 HTHP filtrate @250° F., ml 
                   
                 2.2 
                 5.4 
                 4.0 
                 3.0–0.2 emul. 
               
             
          
           
               
                 Fann 35 dial readings 
               
             
          
           
               
                 600 rpm 
                 73 
                 184 
                 77 
                 174 
                 66 
                 254 
                 86 
                 273 
                 100 
               
               
                 300 rpm 
                 44 
                 108 
                 47 
                 99 
                 38 
                 135 
                 46 
                 154 
                 57 
               
               
                 200 rpm 
                 34 
                 81 
                 36 
                 73 
                 30 
                 93 
                 33 
                 111 
                 42 
               
               
                 100 rpm 
                 23 
                 52 
                 24 
                 45 
                 19 
                 50 
                 19 
                 65 
                 26 
               
               
                  6 rpm 
                 8 
                 16 
                 8 
                 13 
                 7 
                 7 
                 4 
                 15 
                 8 
               
               
                  3 rpm 
                 7 
                 14 
                 7 
                 11 
                 6 
                 5 
                 3 
                 13 
                 7 
               
               
                   
               
               
                 Note: 
               
               
                 Contaminated samples were made up with mud already hot rolled 16 hr.@250° F. 
               
               
                 *ES readings ranged from 347 to 656 volts. 
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 12 
               
             
             
               
                   
               
               
                 BDF-257 and BDF-258 Summary 
               
               
                 PETROFREE SF: 14 lb/gal; 75/25 OWR with 250,000 ppm WPS 
               
             
          
           
               
                 Sample Mark 
                 A 
                 B 
                 C 
                 D 
                 E 
               
               
                   
               
             
          
           
               
                 SF BASE, bbl 
                 0.516 
                 0.516 
                 0.516 
                 0.516 
                 0.516 
               
               
                 Freshwater, bbl 
                 0.181 
                 0.181 
                 0.181 
                 0.181 
                 0.181 
               
               
                 GELTONE II, lb 
                 3 
                 3 
                 3 
                 3 
                 3 
               
               
                 SUSPENTONE, lb 
                 1 
                 1 
                 1 
                 1 
                 1 
               
               
                 LE MUL, lb 
                 4 
                 — 
                 — 
                 — 
                 — 
               
               
                 BDF-257, lb 
                 — 
                 3.5 
                 4.9 
                 7 
                 — 
               
               
                 BDF-258, lb 
                 — 
                 — 
                 — 
                 — 
                 3 
               
               
                 LE SUPERMUL, lb 
                 6 
                 4.8 
                 2.9 
                 — 
                 — 
               
               
                 Lime, lb 
                 5 
                 5 
                 5 
                 18 
                 8 
               
               
                 DURATONE HT, lb 
                 7 
                 7 
                 7 
                 7 
                 7 
               
               
                 BAROID ®, lb 
                 330 
                 330 
                 330 
                 330 
                 330 
               
               
                 Calcium chloride, lb 
                 21.9 
                 21.9 
                 21.9 
                 21.9 
                 21.9 
               
             
          
           
               
                 DEEP-TREAT, lb 
                 3 
                 3 
                 3 
                 3 
                 6 
                 3 
               
             
          
           
               
                 Mixed 15 minutes on a Silverson L4RT at 7000 rpm &amp; Hot Rolled for 16 hours at 150° F. Before Testing 
               
             
          
           
               
                 Hot rolled @ 250° F., hrs 
                 — 
                 16 
                 — 
                 16 
                 — 
                 16 
                 — 
                 16 
                 — 
                 16 
               
               
                   
               
             
          
           
               
                 Temperature, ° F. 
                 120 
                 120 
                 40 
                 120 
                 120 
                 40 
                 120 
                 120 
                 40 
                 120 
                 120 
                 40 
                 120 
                 120 
                 40 
               
               
                   
               
               
                 Plastic viscosity, cP 
                 23 
                 24 
                 80 
                 27 
                 27 
                 91 
                 35 
                 33 
                 113 
                 33 
                 42 
                 129 
                 27 
                 26 
                 72 
               
               
                 Yield point, lb/100 ft 2   
                 15 
                 8 
                 18 
                 14 
                 8 
                 31 
                 15 
                 11 
                 42 
                 21 
                 14 
                 42 
                 14 
                 12 
                 24 
               
               
                 10 Sec gel, lb/100 ft 2   
                 8 
                 6 
                 7 
                 8 
                 6 
                 9 
                 9 
                 7 
                 23 
                 14 
                 10 
                 22 
                 7 
                 7 
                 13 
               
               
                 10 Min gel, lb/100 ft 2   
                 9 
                 8 
                 11 
                 10 
                 7 
                 14 
                 13 
                 12 
                 56 
                 21 
                 17 
                 34 
                 9 
                 9 
                 15 
               
               
                 Electrical stability, v 
                 690 
                 235 
                 — 
                 680 
                 284 
                 — 
                 650 
                 262 
                 — 
                 765 
                 320 
                 — 
                 669 
                 630 
                 — 
               
             
          
           
               
                 HTHP filtrate @ 250° F., ml 
                 2.4 
                 2.4 
                 1.6 
                 3.6 
                 1.2 
                 2.0 
                 0.6 
                 0.0 
                 2.0 
                 1.6 
               
             
          
           
               
                 Fann 35 dial readings 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 600 rpm 
                 61 
                 56 
                 178 
                 68 
                 62 
                 213 
                 85 
                 77 
                 268 
                 87 
                 98 
                 300 
                 68 
                 64 
                 168 
               
               
                 300 rpm 
                 38 
                 32 
                 98 
                 41 
                 35 
                 122 
                 50 
                 44 
                 155 
                 54 
                 56 
                 171 
                 41 
                 38 
                 96 
               
               
                 200 rpm 
                 29 
                 24 
                 69 
                 32 
                 26 
                 87 
                 38 
                 33 
                 113 
                 42 
                 44 
                 123 
                 32 
                 30 
                 72 
               
               
                 100 rpm 
                 20 
                 15 
                 38 
                 22 
                 17 
                 50 
                 25 
                 21 
                 68 
                 29 
                 29 
                 74 
                 22 
                 20 
                 45 
               
               
                  6 rpm 
                 7 
                 5 
                 7 
                 8 
                 6 
                 10 
                 9 
                 7 
                 19 
                 13 
                 10 
                 20 
                 8 
                 8 
                 14 
               
               
                  3 rpm 
                 6 
                 4 
                 6 
                 7 
                 5 
                 8 
                 8 
                 6 
                 17 
                 12 
                 9 
                 17 
                 7 
                 7 
                 12 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 13 
               
             
             
               
                   
               
               
                 Summary of Contamination Results 
               
               
                 PETROFREE SF: 14 lb/gal; 75/25 OWR with 250,000 ppm WPS 
               
             
          
           
               
                 Sample Mark 
                 A 
                 B 
                 C 
                 D 
                 E 
               
               
                   
               
             
          
           
               
                 SF BASE, bbl 
                 0.516 
                 0.516 
                 0.516 
                 0.516 
                 0.516 
               
               
                 Freshwater, bbl 
                 0.181 
                 0.181 
                 0.181 
                 0.181 
                 0.181 
               
               
                 GELTONE II, lb 
                 3 
                 3 
                 3 
                 3 
                 3 
               
               
                 SUSPENTONE, lb 
                 1 
                 1 
                 1 
                 1 
                 1 
               
               
                 LE MUL, lb 
                 4 
                 — 
                 — 
                 — 
                 — 
               
               
                 BDF-257, lb 
                 — 
                 3.5 
                 4.9 
                 7 
                 — 
               
               
                 BDF-258, lb 
                 — 
                 — 
                 — 
                 — 
                 3 
               
               
                 LE SUPERMUL, lb 
                 6 
                 4.8 
                 2.9 
                 — 
                 — 
               
               
                 Lime, lb 
                 5 
                 5 
                 5 
                 18 
                 8 
               
               
                 DURATONE HT, lb 
                 7 
                 7 
                 7 
                 7 
                 7 
               
               
                 BAROID ®, lb 
                 330 
                 330 
                 330 
                 330 
                 330 
               
               
                 Calcium chloride, lb 
                 21.9 
                 21.9 
                 21.9 
                 21.9 
                 21.9 
               
               
                 DEEP-TREAT, lb 
                 3 
                 3 
                 3 
                 6 
                 3 
               
             
          
           
               
                 *Base mud (HR @  250° F.), 
                 1.0 
                 0.8 
                 1.0 
                 0.8 
                 1.0 
                 0.8 
                 1.0 
                 0.8 
                 1.0 
                 0.8 
               
               
                 bbl 
               
               
                 Rev Dust, lb 
                 45 
                 — 
                 45 
                 — 
                 45 
                 — 
                 45 
                 — 
                 45 
                 — 
               
               
                 15% wt NaCl brine, bbl 
                 — 
                 0.2 
                 — 
                 0.2 
                 — 
                 0.2 
                 — 
                 0.2 
                 — 
                 0.2 
               
             
          
           
               
                 Hot rolled @  250° F., hr 
                 16 
               
               
                   
               
             
          
           
               
                 Temperature ° F. 
                 120 
                 120 
                 40 
                 120 
                 120 
                 40 
                 120 
                 120 
                 40 
                 120 
                 120 
                 40 
                 120 
                 120 
                 40 
               
               
                   
               
               
                 Plastic viscosity, cP 
                 37 
                 42 
                 108 
                 34 
                 45 
                 N/A 
                 55 
                 58 
                 N/A 
                 N/A 
                 84 
                 N/A 
                 49 
                 43 
                 113 
               
               
                 Yield point, lb/100 ft 2   
                 8 
                 7 
                 26 
                 10 
                 12 
                 N/A 
                 25 
                 37 
                 N/A 
                 N/A 
                 53 
                 N/A 
                 24 
                 20 
                 43 
               
               
                 10 Sec gel, lb/100 ft 2   
                 7 
                 6 
                 9 
                 8 
                 6 
                 13 
                 14 
                 16 
                 46 
                 54 
                 27 
                 49 
                 16 
                 13 
                 19 
               
               
                 10 Min gel, lb/100 ft 2   
                 10 
                 10 
                 12 
                 10 
                 9 
                 18 
                 38 
                 28 
                 — 
                 80 
                 37 
                 85 
                 36 
                 13 
                 20 
               
               
                 Electrical stability, v 
                 488 
                 77 
                 — 
                 553 
                 116 
                 — 
                 575 
                 145 
                 — 
                 1500 
                 150 
                 — 
                 884 
                 393 
                 — 
               
             
          
           
               
                 HTHP filtrate @  250° F., ml 
                 10.4 
                 7.6 
                 0.6 
                 0.6 
                 1.6 
                 1.6 
                 3.8 
                 2.2 
                 5.2 
                 2.4 
               
               
                   
                   
                 (0.5 H 2 O) 
               
             
          
           
               
                 Fann 35 dial readings 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 600 rpm 
                 82 
                 87 
                 242 
                 78 
                 102 
                 O/S 
                 135 
                 153 
                 O/S 
                 O/S 
                 221 
                 O/S 
                 122 
                 106 
                 269 
               
               
                 300 rpm 
                 45 
                 49 
                 134 
                 44 
                 57 
                 216 
                 80 
                 95 
                 284 
                 202 
                 137 
                 299 
                 73 
                 63 
                 156 
               
               
                 200 rpm 
                 33 
                 36 
                 94 
                 32 
                 41 
                 154 
                 59 
                 72 
                 214 
                 160 
                 105 
                 230 
                 56 
                 48 
                 116 
               
               
                 100 rpm 
                 20 
                 23 
                 53 
                 20 
                 25 
                 90 
                 36 
                 47 
                 137 
                 112 
                 70 
                 152 
                 38 
                 32 
                 72 
               
               
                  6 rpm 
                 5 
                 7 
                 10 
                 6 
                 6 
                 16 
                 10 
                 15 
                 41 
                 47 
                 25 
                 50 
                 15 
                 12 
                 21 
               
               
                  3 rpm 
                 4 
                 6 
                 8 
                 5 
                 5 
                 12 
                 8 
                 13 
                 37 
                 43 
                 15 
                 44 
                 14 
                 11 
                 19 
               
               
                   
               
               
                 Note: 
               
               
                 O/S indicates an off-scale reading, or &gt;300. 
               
               
                 *These contaminated samples were made up with fluid that was previously hot rolled for 16 hours at 250° F. 
               
             
          
         
       
     
     These experimental results show that the product of the invention has emulsion-forming capabilities comparable to or exceeding prior art emulsifiers at only about one-third the concentration and that the product of the invention improves the electrical stability of the drilling fluid, even after heat stress. These results also show that the product of the invention imparts very low filtration properties to the drilling fluids. Further, the product of the invention provides significantly better filtration control than conventional emulsifiers, even after solids and brine contamination. As demonstrated by the data in the tables above, inclusion of a wetting agent with a carboxylic acid terminated polyamide to comprise Component A may provide significant performance advantages in some drilling fluids at certain temperatures or under certain well conditions. Substitution of a wetting agent for the polyamide in Component A may also yield certain advantages with some drilling fluids in some environments. Carboxylic acid terminated polyamides without wetting agent to comprise Component A may yield superior performance in other drilling fluids and/or in other environments. 
     Still further, the tests showed that no fluid loss control additives were needed for the same filtration properties as prior art emulsifiers when the product of the invention was used. The tests also indicated that the product of the invention performs well with other emulsifying products, which should allow simpler maintenance treatments in oil or synthetic based fluids when using the product of the invention. 
     In the method of the invention, the product of the invention is added to an oil or synthetic based drilling fluid or a drilling fluid comprising an invert emulsion to improve or facilitate the emulsification of the oil or synthetic base fluid. 
     The foregoing description of the invention is intended to be a description of preferred embodiments. Various changes in the details of the described product and method can be made without departing from the intended scope of this invention as defined by the appended claims.