Controlled release proppant

Abstract

Materials are delivered into oil well reservoirs. Highly sensitive, mechanical, biological and chemical agents can be delivered to subterranean formations with rigid, impermeable capsules. A variety of treatments may be delivered to a subterranean formation.

1 . A method of delivering materials to a subterranean reservoir comprising:
 a) encapsulating a material in a protective capsule;   b) injecting the encapsulated material into a subterranean formation;   c) injecting an activator to open encapsulated material; and   d) activating the encapsulated material,   
       wherein said protective capsule forms an impermeable shell and said encapsulated material is protected during delivery to the subterranean formation. 
     
     
         2 . The method of  claim 1 , wherein said encapsulated material is selected from the group consisting of micro-machines, biological materials, explosives, foams, adhesives, chemo-active materials and combinations thereof. 
     
     
         3 . The method of  claim 1 , wherein said protective capsule comprises hard wax, polypropylene, polyethylene, nylon, vinyl, Teflon, glass, plastic, thermoplastic, rubber, varnish, paint, cellulose, lignin, starch, one or more polymers, one or more conductive polymers, metal, electrically active materials, or and combinations thereof. 
     
     
         4 . The method of  claim 1 , wherein said protective capsule is applied as a spray mist, drop coating, electrostatic coating, thin film, extrusion, in one or more applications. 
     
     
         5 . The method of  claim 1 , wherein said encapsulated material is a component of a binary explosive comprising:
 a) a fuel selected from the group consisting of aluminum, aluminum and sulfur, aluminum and iron oxide, aluminum and magnesium, aluminum and charcoal, cellulose, charcoal, charcoal and sugar, charcoal and sulfur, coal, coal and lignin, coal and starch, coal and sugar, glycerine, iron, iron and aluminum, lignin, magnesium, magnesium and sulfur, phosphorus sesquisulfide, polyvinylchloride (PVC), starch, sugar, sugar and aluminum, sugar and charcoal, sugar and magnesium, sulfur, sulfur and aluminum, sulfur and magnesium, sulfur and starch, zinc, zirconium hydride, combustible powder, fuel oil, nitromethane, nitroethane, and mixtures thereof and   b) an oxidizer selected from the group consisting of oxides, peroxides, nitrates, perchlorates, permanganates, chromates, dichromates, bromates, iodates, magnesium oxide (MgO 2 ), ammonium perchlorate, barium nitrate, barium oxide, barium peroxide, barium sulphate, copper oxide, cupric oxide, potassium bichromate, potassium chlorate, potassium nitrate, potassium perchlorate, potassium permanganate, red iron oxide, sodium nitrate, strontium nitrate, Zirconium phosphate-intercalated magnesium peroxide, calcium oxy-hydroxide [CaO(OH) 2 ], calcium peroxide [Ca(OH) 2 ], calcium carbonate (CaCO 3 ), lithium perchlorate, potassium with lithium chlorate, sodium chlorate with iron powder, barium peroxide with sodium chlorate, calcium peroxide, oxygen impregnated molecular sieves, oxygen impregnated zeolites, and combinations thereof.   
     
     
         6 . The method of  claim 1 , wherein said encapsulated material is a component of an adhesive comprising:
 a) an adhesive resin selected from the group consisting of polyester, vinylester, urethane, polyurethane, rubber, acrylic, cyanoacrylate, epichlorohydrin, and combinations thereof; and   b) a hardener selected from the group consisting of polyamines, bisphenol-A, triethylenetetramine (TETA), diethylenetetramine (DETA), and combinations thereof.   
     
     
         7 . The method of  claim 1 , wherein said encapsulated material is a biological agent selected from the group consisting of an  archae , bacteria, yeast,  Ascomycota , unicellular organisms,  Escherichia, E. coli, Clostridia, C. acetobutylicum, Candida albicans, Saccharomyces cerevisiae, S. Pombe, C. difficile, C. perfringens, A. baumannii , extremophile, iron-reducing bacteria, denitrifying bacteria, sulfate-reducing bacteria,  Desulfovibrio, Desulfobacteriaceae, acetobutylicum, methanobacteria, methanobaccilus, methanococcus, methanosarcina , one or more enzymes, peroxidase, cellulase, nutrients, powdered nutrients, cellulose, microcrystalline cellulose, sugars, glucose, bacteria containing an expression vector, bacteria containing a selection vector, bacteria containing an alkane resistance gene, bacteria containing an alkane degrading gene and combinations thereof. 
     
     
         8 . The method of  claim 1 , wherein said encapsulated material is a micro electro mechanical system comprising one or more components selected from the group consisting of a radio-frequency transmitter; gravitometer; magnetometer; piezoelectric device; accelerometer; Peltier heating element; pH meter; thermometer; thermocouple; pressure sensor; inertial sensor; detonator; battery; a microchip with an antennae; a microchip with a battery and antennae; a microchip with a receiver and transmitter; a microchip with a receiver, transmitter and a battery; and combinations thereof. 
     
     
         9 . The method of  claim 1 , wherein two or more encapsulated materials are injected simultaneously. 
     
     
         10 . A method of delivering materials to a subterranean reservoir comprising:
 a) encapsulating a first material in a first protective capsule;   b) encapsulating a second material in a second protective capsule;   c) injecting the first and second encapsulated materials into a subterranean formation; and   d) activating the encapsulated materials;   
       wherein said first and second protective capsules form an impermeable shell and said encapsulated materials are protected during delivery to the subterranean formation. 
     
     
         11 . The method of  claim 10 , wherein said encapsulated material is selected from the group consisting of micro-machines, biological materials, explosives, foams, adhesives, chemo-active materials and combinations thereof. 
     
     
         12 . The method of  claim 10 , wherein said protective capsule comprises hard wax, polypropylene, polyethylene, nylon, vinyl, Teflon, glass, plastic, thermoplastic, rubber, varnish, paint, cellulose, lignin, starch, one or more polymers, one or more conductive polymers, metal, electrically active materials, or and combinations thereof. 
     
     
         13 . The method of  claim 10 , wherein said protective capsule is applied as a spray mist, drop coating, electrostatic coating, thin film, extrusion, in one or more applications. 
     
     
         14 . The method of  claim 10 , wherein said encapsulated material is a component of a binary explosive comprising:
 a) a fuel selected from the group consisting of aluminum, aluminum and sulfur, aluminum and iron oxide, aluminum and magnesium, aluminum and charcoal, cellulose, charcoal, charcoal and sugar, charcoal and sulfur, coal, coal and lignin, coal and starch, coal and sugar, glycerine, iron, iron and aluminum, lignin, magnesium, magnesium and sulfur, phosphorus sesquisulfide, polyvinylchloride (PVC), starch, sugar, sugar and aluminum, sugar and charcoal, sugar and magnesium, sulfur, sulfur and aluminum, sulfur and magnesium, sulfur and starch, zinc, zirconium hydride, combustible powder, fuel oil, nitromethane, nitroethane, and mixtures thereof; and   b) an oxidizer selected from the group consisting of oxides, peroxides, nitrates, perchlorates, permanganates, chromates, dichromates, bromates, iodates, magnesium oxide (MgO 2 ), ammonium perchlorate, barium nitrate, barium oxide, barium peroxide, barium sulphate, copper oxide, cupric oxide, potassium bichromate, potassium chlorate, potassium nitrate, potassium perchlorate, potassium permanganate, red iron oxide, sodium nitrate, strontium nitrate, Zirconium phosphate-intercalated magnesium peroxide, calcium oxy-hydroxide [CaO(OH) 2 ], calcium peroxide [Ca(OH) 2 ], calcium carbonate (CaCO 3 ), lithium perchlorate, potassium with lithium chlorate, sodium chlorate with iron powder, barium peroxide with sodium chlorate, calcium peroxide, oxygen impregnated molecular sieves, oxygen impregnated zeolites, and combinations thereof.   
     
     
         15 . The method of  claim 10 , wherein said encapsulated material is a component of an adhesive comprising:
 a) an adhesive resin selected from the group consisting of polyester, vinylester, urethane, polyurethane, rubber, acrylic, cyanoacrylate, epichlorohydrin, and combinations thereof; and   b) a hardener selected from the group consisting of polyamines, bisphenol-A, triethylenetetramine (TETA), diethylenetetramine (DETA), and combinations thereof.   
     
     
         16 . The method of  claim 10 , wherein said encapsulated material is a biological agent selected from the group consisting of an  archae , bacteria, yeast,  Ascomycota , unicellular organisms,  Escherichia, E. coli, Clostridia, C. acetobutylicum, Candida albicans, Saccharomyces cerevisiae, S. Pombe, C. difficile, C. perfringens, A. baumannii , extremophile, iron-reducing bacteria, denitrifying bacteria, sulfate-reducing bacteria,  Desulfovibrio, Desulfobacteriaceae, acetobutylicum, methanobacteria, methanobaccilus, methanococcus, methanosarcina , one or more enzymes, peroxidase, cellulase, nutrients, powdered nutrients, cellulose, microcrystalline cellulose, sugars, glucose, bacteria containing an expression vector, bacteria containing a selection vector, bacteria containing an alkane resistance gene, bacteria containing an alkane degrading gene and combinations thereof. 
     
     
         17 . The method of  claim 10 , wherein said encapsulated material is a micro electro mechanical system comprising one or more components selected from the group consisting of a radio-frequency transmitter; gravitometer; magnetometer; piezoelectric device; accelerometer; Peltier heating element; pH meter; thermometer; thermocouple; pressure sensor; inertial sensor; detonator; battery; a microchip with an antennae; a microchip with a battery and antennae; a microchip with a receiver and transmitter; a microchip with a receiver, transmitter and a battery; and combinations thereof. 
     
     
         18 . The method of  claim 10 , wherein two or more encapsulated materials are injected simultaneously. 
     
     
         19 . A method of delivering materials to a subterranean reservoir comprising:
 a) encapsulating a first material in a first protective capsule;   b) coating the first capsule with a second material;   c) encapsulating the entire pellet in a second protective capsule;   d) injecting the encapsulated materials into a subterranean formation; and   e) activating the encapsulated materials,   
       wherein said first and second protective capsules form an impermeable shell and said encapsulated materials are protected during delivery to the subterranean formation. 
     
     
         20 . The method of  claim 19 , wherein said encapsulated material is selected from the group consisting of micro-machines, biological materials, explosives, foams, adhesives, chemo-active materials and combinations thereof. 
     
     
         21 . The method of  claim 19 , wherein said protective capsule comprises hard wax, polypropylene, polyethylene, nylon, vinyl, Teflon, glass, plastic, thermoplastic, rubber, varnish, paint, cellulose, lignin, starch, one or more polymers, one or more conductive polymers, metal, electrically active materials, or and combinations thereof. 
     
     
         22 . The method of  claim 19 , wherein said protective capsule is applied as a spray mist, drop coating, electrostatic coating, thin film, extrusion, in one or more applications. 
     
     
         23 . The method of  claim 19 , wherein said encapsulated material is a component of a binary explosive comprising:
 a) a fuel selected from the group consisting of aluminum, aluminum and sulfur, aluminum and iron oxide, aluminum and magnesium, aluminum and charcoal, cellulose, charcoal, charcoal and sugar, charcoal and sulfur, coal, coal and lignin, coal and starch, coal and sugar, glycerine, iron, iron and aluminum, lignin, magnesium, magnesium and sulfur, phosphorus sesquisulfide, polyvinylchloride (PVC), starch, sugar, sugar and aluminum, sugar and charcoal, sugar and magnesium, sulfur, sulfur and aluminum, sulfur and magnesium, sulfur and starch, zinc, zirconium hydride, combustible powder, fuel oil, nitromethane, nitroethane, and mixtures thereof and   b) an oxidizer selected from the group consisting of oxides, peroxides, nitrates, perchlorates, permanganates, chromates, dichromates, bromates, iodates, magnesium oxide (MgO 2 ), ammonium perchlorate, barium nitrate, barium oxide, barium peroxide, barium sulphate, copper oxide, cupric oxide, potassium bichromate, potassium chlorate, potassium nitrate, potassium perchlorate, potassium permanganate, red iron oxide, sodium nitrate, strontium nitrate, Zirconium phosphate-intercalated magnesium peroxide, calcium oxy-hydroxide [CaO(OH) 2 ], calcium peroxide [Ca(OH) 2 ], calcium carbonate (CaCO 3 ), lithium perchlorate, potassium with lithium chlorate, sodium chlorate with iron powder, barium peroxide with sodium chlorate, calcium peroxide, oxygen impregnated molecular sieves, oxygen impregnated zeolites, and combinations thereof.   
     
     
         24 . The method of  claim 19 , wherein said encapsulated material is a component of an adhesive comprising:
 a) an adhesive resin selected from the group consisting of polyester, vinylester, urethane, polyurethane, rubber, acrylic, cyanoacrylate, epichlorohydrin, and combinations thereof and   b) a hardener selected from the group consisting of polyamines, bisphenol-A, triethylenetetramine (TETA), diethylenetetramine (DETA), and combinations thereof.   
     
     
         25 . The method of  claim 19 , wherein said encapsulated material is a biological agent selected from the group consisting of an  archae , bacteria, yeast,  Ascomycota , unicellular organisms,  Escherichia, E. coli, Clostridia, C. acetobutylicum, Candida albicans, Saccharomyces cerevisiae, S. Pombe, C. difficile, C. perfringens, A. baumannii , extremophile, iron-reducing bacteria, denitrifying bacteria, sulfate-reducing bacteria,  Desulfovibrio, Desulfobacteriaceae, acetobutylicum, methanobacteria, methanobaccilus, methanococcus, methanosarcina , one or more enzymes, peroxidase, cellulase, nutrients, powdered nutrients, cellulose, microcrystalline cellulose, sugars, glucose, bacteria containing an expression vector, bacteria containing a selection vector, bacteria containing an alkane resistance gene, bacteria containing an alkane degrading gene and combinations thereof. 
     
     
         26 . The method of  claim 19 , wherein said encapsulated material is a micro electro mechanical system comprising one or more components selected from the group consisting of a radio-frequency transmitter; gravitometer; magnetometer; piezoelectric device; accelerometer; Peltier heating element; pH meter; thermometer; thermocouple; pressure sensor; inertial sensor; detonator; battery; a microchip with an antennae; a microchip with a battery and antennae; a microchip with a receiver and transmitter; a microchip with a receiver, transmitter and a battery; and combinations thereof. 
     
     
         27 . The method of  claim 19 , wherein two or more encapsulated materials are injected simultaneously.