Method, apparatus and composition to increase recovery of hydrocarbons by reaction of selective oxidizers and fuels in the subterranean environment

Abstract

A method, apparatus and composition are described for safe energy delivery down hole resulting in increased recovery of subterranean hydrocarbons. The method utilizes the reaction of non-alkane fuels and selective oxidizers which are non-selective toward alkane chemical compounds. The energy released in the subterranean reaction is utilized to heat the wellbore, the formation or the formation hydrocarbons thereby lowering fluid viscosity and permitting greater flow especially for heavy oils. Further, safe delivery of oxidizers can be accomplished without limit on depth as the selective oxidizer may be delivered to point of use down hole as most all formations of interest contain primarily alkane hydrocarbons and will not react with the non-alkane selective oxidizer. In addition some products of reaction may be insoluble in water and can be utilized for fluid loss prevention, flow diversion, abrasive drilling and or as proppants.

1 . A method for recovery of hydrocarbons from a formation, strata, or at least one subterranean reservoir comprising:
 a. Injecting at least one liquid fluid system from the surface of the earth through at least one conduit into at least one wellbore;   b. Said wellbore being in fluid communication with at least one subterranean formation;   c. Said injected fluid system at least partially comprising an oxidizing agent;   d. Said oxidizing agent being comprised substantially of a selective oxidizing agent which is non-selective in reaction toward alkane chemistry;   e. Injecting at least one additional fluid system comprised at least partially of a non-alkane fuel from the surface of the earth through at least one conduit into at least one wellbore;   f. Reaction of said oxidizing agent at least partially with said fuel releasing energy;   g. Recovery back to surface of subterranean hydrocarbons.   
     
     
         2 . The method of  claim 1  wherein the selective oxidizing agent is at least partially comprised of a compound containing at least one of the chemical elements: Vanadium (V), Chromium (Cr), Manganese (Mn), Iron (Fe), Cobalt (Co) and combinations thereof. 
     
     
         3 . The method of  claim 1  wherein the selective oxidizing agent is at least partially comprised of Manganate or Permanganate compounds. 
     
     
         4 . The method of  claim 1  wherein the selective oxidizing agent is at least partially comprised of one of the following chemical compounds: Sodium Dichromate (Na 2 Cr 2 O 7 ), Ammonium Permanganate (NH 4  MnO 4 ), Calcium Permanganate (Ca(MnO 4 ) 2 ), Sodium Permanganate (NaMnO 4 ), Potassium Permanganate (KMnO 4 ) and combinations thereof 
     
     
         5 . The method of  claim 1  wherein the fuel is at least partially comprised of Glycerol (C 3 H 8 O 3 ). 
     
     
         6 . The method of  claim 1  wherein at least one additional fluid system comprises an acid. 
     
     
         7 . The method of  claim 6  wherein at least a portion of the acid is Sulfuric acid (H 2 SO 4 ). 
     
     
         8 . The method of  claim 1  wherein at least one additional fluid system comprises a basic agent. 
     
     
         9 . The method of  claim 8  wherein at least a portion of the basic agent is Sodium Hydroxide (NaOH). 
     
     
         10 . The method of  claim 1  wherein at least one additional fluid system comprises a reductive leaching agent. 
     
     
         11 . The method of  claim 10  wherein at least a portion of the reductive leaching is comprised of one of the following materials: Sucrose (C 12 H 24 O 11 ), molasses, glucose (C 6 H 12 O 6 ), Ferrous Sulfate, Ferrous Chloride, elemental Iron, Hydrogen Peroxide and combinations thereof. 
     
     
         12 . The method of  claim 1  wherein the injected fluid system is heated above surface ambient temperature prior to injection. 
     
     
         13 . The method of  claim 1  wherein the additional fluid system is heated above surface ambient temperature prior to injection. 
     
     
         14 . The method of  claim 1  wherein at least one conduit is a continuous tube having a distal end below the surface and a proximal end in said wellbore. 
     
     
         15 . The method of  claim 14  wherein at least a portion of the said reaction occurs within a distal end reactor attached to said continuous tube. 
     
     
         16 . The method of  claim 1  wherein at least one conduit is a continuous tube having a distal end below the surface and a proximal end above the surface of the earth. 
     
     
         17 . The method of  claim 16  wherein at least a portion of the said reaction occurs within a distal end reactor attached to said continuous tube. 
     
     
         18 . The method of  claim 1  wherein the injection of the additional fluid system is injected simultaneously with the selective oxidizing agent fluid system. 
     
     
         19 . The method of  claim 1  wherein the injection of the additional fluid system is injected alternating with the selective oxidizing agent fluid system. 
     
     
         20 . The method of  claim 1  wherein the reaction of the selective oxidizing agent with the additional fluid system occurs at least partially in the wellbore. 
     
     
         21 . The method of  claim 1  wherein the reaction of the selective oxidizing agent with the additional fluid system occurs at least partially in the formation. 
     
     
         22 . The method of  claim 1  wherein the injection of said fluid systems occurs at a pressure sufficient to hydraulically fracture at least one subterranean stratum. 
     
     
         23 . The method of  claim 1  wherein the injection of said fluid systems occurs at a pressure below hydraulic fracture pressure of at least one subterranean statum. 
     
     
         24 . The method of  claim 1  wherein at least a portion of the products of reaction of the said selective oxidizing agent and the said fuel are utilized as a proppant material. 
     
     
         25 . The method of  claim 24  wherein the product of reaction is Manganese (IV) Dioxide (MnO 2 ). 
     
     
         26 . The method of  claim 24  wherein the product of reaction is Chromium (III) Oxide (Cr 2 O 3 ). 
     
     
         27 . The method of  claim 1  wherein the fuel is at least partially comprised of one of the following: Bitumen, Asphaltene, Resin, Aromatic Hydrocarbons, Kerogen, Alkenes, Alkynes, Alcohols and combinations thereof. 
     
     
         28 . The method of  claim 1  wherein recovery back to surface of subterranean hydrocarbons is through said wellbore. 
     
     
         29 . The method of  claim 1  wherein recovery back to surface of subterranean hydrocarbons is through wellbores other than those wherein said oxidizing agent was injected. 
     
     
         30 . The method of  claim 1  wherein the reaction of said oxidizing agent and fuel is fuel rich. 
     
     
         31 . The method of  claim 1  wherein the reaction of said oxidizing agent and fuel is oxidizer rich. 
     
     
         32 . The method of  claim 1  wherein the additional fluid system is at least partially composed of one of the following: friction reducer, proppant, gelling agent and combinations thereof. 
     
     
         33 . The method of  claim 1  wherein the injected fluid system is at least partially composed of one of the following: friction reducer, proppant, gelling agent and combinations thereof. 
     
     
         34 . The method of  claim 1  wherein the subterranean hydrocarbons recovered back to surface may be visually inspected for color to determine efficiency of said energy release. 
     
     
         35 . The method of  claim 1  wherein at least a portion of the products of reaction of the said selective oxidizing agent and the said fuel are utilized for drilling, abrasive drilling, perforating or cutting. 
     
     
         36 . The method of  claim 1  wherein at least a portion of the products of reaction of the said selective oxidizing agent and the said fuel are utilized for flow diversion or fluid loss prevention. 
     
     
         37 . An injection system operable for use with one or more selective oxidizing agents and operable for use in recovering one or more hydrocarbons from a formation, strata, and/or at least one subterranean reservoir, comprising:
 a. a first fluid container operable to contain at least a first fluid;   b. a second fluid container operable to contain at least a second fluid;   c. a plurality of pumps operable to pump one or more fluids;   d. a wellbore extending at least partially below ground;   e. a well casing contained at least partially inside said wellbore, said well casing: operable to be in communication with said first fluid container and/or with said second fluid container; and comprising one or more perforations in said well casing permitting a fluid inside said well casing to flow out of said well casing;   f. one or more conduits operable for delivering a fluid into said well casing, including one or more conduits operable for delivering a fluid into said well casing or to a selected location down or near bottom of said wellbore;   g. one or more conduits operable for recovery of one or more hydrocarbons;   h. said injection system comprising further limitations, wherein said injection system comprises:
 i. a selective oxidizing agent comprising oxygen, wherein said selective oxidizing agent is operable for preferential attack by oxygen on a plurality of chemical components in a material wherein said plurality of chemical components are not of alkane chemistry, and/or said oxidizing agent is operable to be non-selective toward alkane chemistry; 
 ii. a non-alkane fuel which is a fluid; 
 iii. wherein said first fluid at least partially comprises a said selective oxidizing agent, wherein a said first fluid is injected into said well casing utilizing one or more pumps of said plurality of pumps; 
 iv. wherein said second fluid at least partially comprises a said non-alkane fuel, wherein utilizing one or more pumps of said plurality of pumps a said second fluid is injected into said well casing down to at or near bottom of said wellbore; 
 v. wherein said injection system is operable to cause said first fluid and said second fluid and/or a mixture thereof to flow through one or more of said perforations of said well casing; 
 vi. wherein at a time after said first fluid and said second fluid are injected into said well casing, said first fluid and said second fluid and/or a mixture thereof are operable to cause an oxidation reaction outside and/or substantially outside said well casing resulting in an energy release and creation of reaction products. 
   
     
     
         38 . The injection system as claimed in  claim 37 , said injection system with further limitations comprising:
 a. a first set of one or more conduits operable for delivering a fluid into said well casing;   b. a second set of one or more conduits operable for delivering a fluid into said well casing to a selected location down said wellbore;   c. wherein said first fluid is injected via said first set of one or more conduits and said second fluid is injected via said second set of one or more conduits; or wherein said second fluid is injected via said first set of one or more conduits and said first fluid is injected via said second set of one or more conduits; and,   d. wherein said injection system is operable to permit said first fluid and said second fluid to come into contact at a selected location down said wellbore, and/or after flowing out of one or more perforations in said well casing into said subterranean reservoir.