Patent Abstract:
The invention relates to methods and apparatuses for the subterranean injection of reactive substances like propellants into wellbores and subterranean reservoirs. These methods and apparatuses controls the temperature of a reactive substance for safe handling at surface and controls the decomposition rate of the substances in the subterranean environment. In addition, these methods and apparatuses provide a means for safe dilution of reactive fluids in the event of a leak or spillage of the reactive substance.

Full Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
       [0001]    This application claims priority to U.S. Provisional Patent Application No. 61/045,062, filed on Apr. 15, 2008, which is incorporated by reference herein in its entirety. 
     
    
     TECHNICAL FIELD 
       [0002]    The present invention is directed to methods and apparatus to inject high energy density substances into subterranean environments where they react. More specifically, this invention is directed to methods and apparatus to inject high energy density fluids like reactive mono-propellants and other hypergolic fluids into subterranean environments through wellbores into the earth. 
       BACKGROUND OF THE INVENTION 
       [0003]    When a fluid, such as oil and natural gas, is being produced from a subterranean reservoir through a wellbore the reservoir&#39;s ability to produce such fluids is often enhanced by processes that inject fluids and solids from the surface through a wellbore into subterranean reservoirs. There is one field of work that uses these fluids and is known to those familiar with the art of oil and gas production as stimulation fluids or hydraulic fracturing fluid, and the process involving these fluids is often referred to as hydraulic fracturing job or stimulation job. It is commonly believed that fracturing the subterranean rock in the reservoir will enhance hydrocarbon production from the well. This is accomplished by pumping the fluids at very high pressures that are greater than the fracture pressure of the subterranean reservoir, thus cracking the rock. 
         [0004]    In early days explosives like nitroglycerin were dropped in wells to break up, crack, or otherwise stimulate the subterranean rock to produce fluids. These explosives had the limitation of only cracking the rock near the wellbore. Therefore, the idea of extending the fractures and cracks in the rocks far afield from the wellbore was developed using the injection of high pressure hydraulic fracturing fluids. The fluids injected as stimulation or fracture fluids are often mixed at surface with a variety of chemicals and solids prior to injection. Many fluid types are used including freshwater, saltwater, nitrogen, carbon dioxide, hydrogen peroxide, monopropellants, hydrogen fluoride, acids, bases, surfactants, alcohols, diesel, propane, liquid natural gas, with many combinations of these fluids and many more fluids. Some of these fluids are blended with solids like sand, bauxite, ceramic proppants, propellants, proppants, and/or catalysts and the fluid and solids are pumped as a slurry into the wellbore and reservoir rocks. 
         [0005]    There are further chemicals and fluids mixed at the surface and injected with stimulation processes like acid stimulation jobs or steam injection stimulations to improve the reservoir&#39;s ability to produce back the injected stimulation fluids to surface and enhance the reservoir production of hydrocarbon fluids. This is because the stimulation fluids remaining in the rock matrix of the subterranean reservoir or the chemicals transported by the fluids reduce the reservoirs ability to produce commercial hydrocarbon fluids. Additionally, those familiar with the art of stimulation or fracture technology in the oil and gas industry often mix at surface viscosifier agents and/or cross-linkers to the stimulation fluid, enhancing the fluid&#39;s ability to transport solids into the reservoirs. What is needed is a method and apparatus to add large amounts of heat generated inside the well during well stimulation as opposed to generating heat at surface and transporting the heat down the well. 
         [0006]    Further, current industry practice of adding to stimulation fluids chemicals such as hydroxypropyl guars, polyacryl imides, and cellulose gelling agents reduces the hydraulic friction between the fluids being pumped and the well conduits that transport the fluids from surface to the subterranean reservoir. These are often referred to as friction reducer chemicals. As the oil and gas industry continues to find more gas and oil in lower permeability rocks, and in ever lower pressured “resource plays,” like shale gas and coal bed methane, shale oil, and tar sands, it becomes ever more important to find substances to pump into the reservoir rock to enhance the hydrocarbon production by reducing the detrimental effects of the chemicals added for friction reduction. 
         [0007]    Moreover, there is a problem with these methods when the fluids, particularly water, are produced back from the wells because they must be treated to re-use in subsequent wells or safely and environmentally disposed. There are many detrimental issues with this produced back fluid. For example, while flowing back from the subterranean environment, injected fluids containing friction reduction chemicals, gelling agents, scale inhibitors surfactants, crosslinkers, and hydrogen sulfide gas often contain bacteria that feed on the gels and poly acrylimdes and thus are not suitable for surface disposal or re-injection into subsequent wells during a subsequent stimulation, enhanced oil recovery method, or hydraulic fracture treatment. In the case of hydrogen sulfide gas production while flowing fluids from the wells, the ability to neutralize and treat this gas in the wellbore system would be a great improvement over the current art of flowing to facilities where the hydrogen sulfide (H 2 S) gas is stripped out with various ammine solutions. Moreover, the lack of water resources in areas of large hydrocarbon recovery restricts the use of water as a treatment fluid. 
         [0008]    Before the current invention, methods to enhance production of hydrocarbons from wells used by those familiar with the art of treating stimulation fluids mixed friction reducers, gelling agents, cross linkers, and/or surfactants into water at surface prior to injecting the fluid and chemicals down a well casing or tubing. These chemicals are typically batch mixed into the stimulation fluids to be injected at the surface into large holding tanks, known as frac tanks, or the chemicals are added “on the fly” at surface to the stimulation or fracture fluid by injecting them into the discharge of a large centrifugal pump at the surface. The mixed fluid is then pumped through high pressure pumps and injected into the well and the reservoir at very high pressures and normally high injection rates thereby exceeding the fracture pressure of the reservoir rock. Hence the stimulation or rock fracturing is largely done with hydraulic forces. 
         [0009]    This process, often referred to as “hydraulic fracturing,” is thought to crack or break the subterranean rock in the reservoir giving the reservoir more conductivity for the production of reservoir fluids like oil and gas. The objective is to put as much energy out away from the wellbore into the formation rock well beyond the wellbore to crack rock far field from the wellbore thereby improving the fluid conduction path from the far afield rock to the wellbore. Using current methods the hydraulic energy is highest at the wellbore where the stimulation or fracture chemicals enter into the well, and the energy available to crack and stimulate becomes progressively less as the stimulation and fracture fluids travel out beyond the wellbore. The typical method of treating heavy oil, tar sands, and depleted light oil reservoirs is to heat fresh water into steam and inject the steam into the wellbore once again concentrating most of the energy injected into the reservoir rock to near the wellbore. This stimulation or enhanced oil recovery method requires large amounts of fresh water, and the process loses considerable amounts of the heat energy in the transportation of the steam from surface to the subterranean environment. 
         [0010]    A still further method of fracturing or stimulating subterranean rock reservoirs or stimulating subterranean reservoirs has been the dropping of explosives into the wells or injecting liquid and solid propellants, like nitroglycerin, dynamite and high grades of hydrogen peroxide, directly into reservoir rock. Hydrogen peroxide is known to decompose into hot water and oxygen in many reservoir rocks where the rocks act as a catalyst for the decomposition and no oxygen is required. The problem with this method is the very rapid and uncontrolled decomposition rate of hydrogen peroxide near the wellbore and the unpredictability of the reactivity of the reservoir rock as a catalyst. 
         [0011]    It is desirable to use fluids with large chemical energy storage that do not require an oxygen environment to combust or decompose so that more chemical energy is available in the subterranean environment and may be placed far underground and far afield from the wellbore out into the reservoir to stimulate the subterranean reservoir with energy other than solely hydraulic energy, like heat and the expanding products of the fluids combustion and decomposition in the presence of catalyst, ignitors, and geothermal temperatures. 
         [0012]    When a fluid, such as oil and natural gas, is being produced from a subterranean reservoir the reservoir energy depletes with time. It has been found that by the injection of certain fluids from the surface such as, nitrogen, water, steam, carbon dioxide, flue gas, air, and combinations of these fluids into a depleted or mature hydrocarbon reservoir the production of hydrocarbons from the depleted reservoir can be enhanced. There is one field of work that uses these fluids and is known to those familiar with the art of oil and gas production as Enhanced Oil Recovery, EOR. It is also known that the injection of heat can greatly enhance the injected fluid&#39;s ability to recover hydrocarbons from the depleted or mature reservoirs. This is particularly the case in “steam floods” and “steam assisted gravity drainage methods”, known as SAGD to those in the field of EOR, which uses injected steam from the surface but suffer from the heat loss as the steam is injected from surface and heat is lost along the length of the well and the surface pipe infrastructure in a field thereby delivering less heat energy to the subterranean reservoir. What is needed is a method to generate heat in-situ. 
         [0013]    It has been found that by the injection of certain fluids like air, natural gas, oxygen, and combinations of these fluids into a depleted or mature hydrocarbon reservoir the production of hydrocarbons from the depleted reservoir can be enhanced by igniting the oil, natural gas, coal, tar sand, shale oil, shale gas, or kerogen located in-situ in the reservoir. The field of work that uses these burning fluids is known to those familiar with the art of oil and gas production as Fire Flooding or In-Situ retorting. It is known that the placement of heat in-situ can greatly enhance the fuel in-situ to ignite. This is particularly the case in tar sands and shale oil reservoirs. What is needed is a method to generate heat in-situ in the reservoir as far from the wellbore as possible with ignitable fluids or with fluids that will assist in the ignition of the in-situ reservoir fluids. 
         [0014]    Additionally, enhanced oil recovery projects, in-situ retorting of shale oil, fire floods, and fracture and stimulation treatments are often performed in parts of the world that have high ambient surface temperatures, where the use of explosive and reactive fluids like hydrogen peroxide becomes more dangerous as these fluids become more reactive as their temperature increases at surface. Likewise, enhanced oil recovery projects, in-situ retorting, fire floods, fracture, and stimulation treatments are often performed in parts of the world that have low surface temperatures, such that the reactive fluids like hydrogen peroxide might freeze, rendering them unpumpable. Currently, when using water as the work fluid this cold condition is easily resolved by heating the working fluid, e.g. water, with heat exchangers for stimulation or EOR projects. The methods to maintain the temperatures on the surface of highly reactive mono-propellants for example is not currently available. What is needed are methods and apparatus to allow for the temperature control of high energy density fluids to allow them to be injected safely at well sites into wells. 
         [0015]    For example currently, a hot oiler truck comes to the well that is to be stimulated with water fracture based fluids and, by burning propane on the truck&#39;s heat exchangers and passing the working fluid to be pumped into the well, the truck heats up the working fluid on the truck such that heated fluid passes through heat exchangers on the truck and at the same time passes the working fluid, usually water, to be used for the stimulation treatment over the truck&#39;s heat exchanger and then re-circulates the fracture treatment water back to a heated holding tank. In this way the fracture treatment water is heated in cold weather such that it can be pumped and does not get solid on the surface. However, this heating method of pumping the fluids into a heat exchanger on a truck that is burning propane is exceedingly dangerous when the fluids to be pumped are mono-propellants like hydrogen peroxide or hydrazine. 
         [0016]    A still further need to transmit large amount of energy beyond the wellbore in an interval is known to those familiar with the art of enhanced oil recovery, EOR, and in-situ retorting of hydrocarbons. This need to get energy out into the subterranean reservoirs beyond the wellbore can also be extended to the new and evolving field of enhanced gas recovery, EGR, and fluid sequestering like CO2. In both EOR and EGR, there is a need to get energy down wellbores and out into the reservoir. Indeed, the method of horizontal wells for steam flooding was developed to allow the steam energy to contact larger portions of the subterranean reservoir. 
         [0017]    A still further method of enhanced oil recovery, or indeed subterranean in-situ retorting of oil is to place large heaters in the earth to heat hydrocarbons and kerogens such that they can be produced from the subterranean intervals. Subterranean heaters, however, cannot heat large areas of the subterranean reservoir far afield from the wellbore because the heater is located in wellbore and the earth is a great heat sink. To improve the heating of the subterranean reservoir, one must drill either a large number of heater wells and add exceeding large amounts of heat in these wells from surface or drill very expensive and long horizontal wells in which heaters are placed. In all cases the desire is to get energy, and in the case of enhanced oil and gas recovery, heat energy large distances from the wellbore. In the case of oil shale, the immense amount of heat needed to remove the oil from the shale is not cost effective, hence a method is needed to ignite and to feed oxygen to the oil shale, using the in-situ generated heat from the combustion of some of the oil shale or kerogen to heat the oil shale reservoir. However, getting oxygen to the oil shale is not easy due to the shale&#39;s low inherent permeability which makes the injection of oxygen into the rock away from the wellbore very difficult. What is needed is a fluid that can heat the rock, ignite in the rock, and deliver oxygen to the rock while assisting in the burning of in-situ fluids. 
         [0018]    What is needed is a method to transmit large amounts of energy beyond the wellbore in a subterranean interval being stimulated to enhance oil or gas production. A further need is to accomplish this far field from the injection wellbore for enhancement effect in the subterranean reservoir with substances that will not reduce the permeability of the reservoir or otherwise inhibit the reservoir to produce fluids back to the wellbore and to the surface. A further need is to reduce the environmental damage done on the surface of the earth and sea by the flow back to surface of stimulation and fracture fluids containing chemicals and bacteria. A still further need is to have available methods and apparatuses to safely handle and control the rate of reaction of reactive fluids and solids such as propellants, catalyst, and fuels pumped into subterranean environments like reservoir rocks at outdoor well sites that may have cold and hot surface environments. Many wells are located in locations on the earth where the surface temperatures are below the sublimation temperatures of many reactive mono-propellant fluids like hydrogen peroxide or hydrazine. What is needed is a method to keep these reactive high energy density substances, like liquid propellants, from freezing at well sites with cold surface temperatures. 
       BRIEF SUMMARY OF THE INVENTION 
       [0019]    The present invention is directed to new methods and apparatuses to treat subterranean reservoirs through wellbores with reactive high energy density substances. This invention teaches methods and apparatuses that allow substances such as mono-propellants, oxidizers, catalysts, and fuels to be injected into subterranean environments to release large amounts of energy into the subterranean environment by controlling their temperature, thus allowing these fluids to be injected safely. 
         [0020]    In one aspect of the present invention, surface vessels, conduits, and/or pumps are designed to perform a process that maintains the highly reactive substances and their transport fluids in a low reactive state by controlling their temperature while at surface. 
         [0021]    In a further aspect of the present invention highly reactive high energy density substances are frozen into solid form and mixed into cold fluids to allow the solid substances to be delivered to a well site, pumped and transported as a slurry into the well and out into the reservoir with the transport fluids that keep the substances cold. The invention further teaches methods to blend the substances with fuels, oxidizers, mono-propellants, and catalysts at low temperatures to keep the blend in a low reaction state. 
         [0022]    In another aspect of the present invention highly reactive high energy density fluids are heated, and monitored to maintain them in a liquid state on surface at a well site where cold surface environment temperatures are below the propellants freezing point, to allow the propellant to be pumped as a liquid into the well. 
         [0023]    In a still further aspect of the present invention a method is presented to form solid reactive materials from liquid reactive materials using cold solids to seed the formation of the reactive fluids. 
         [0024]    In a still further aspect of the present invention a method is presented to ignite highly reactive high energy density fluids in a down hole reaction chamber connected to a coiled tubing thereby directing said fluids to be pumped from an appropriately temperature controlled surface storage vessel, through surface lines, through a coiled tubing string disposed in a well through a wellhead sealing pack off elastomeric device with a reaction chamber on the coiled tubing distal end that atomizes high energy density fluid and ignites the fluid allowing the coiled tubing to articulate in the well bore the position of the reaction chamber while pumping the fluid from surface thereby releasing heat and or decomposition products from the reaction chamber into the subterranean environment. 
         [0025]    In a still further aspect of the present invention a method is presented to provide energy to a subterranean environment by directing a reactive high energy density fluid from a surface storage vessel (that is optionally temperature controlled), through surface lines, through a conduit such as a coiled tubing string disposed in a wellbore, and into the wellbore where the fluid decomposes or reacts. In some embodiments, upon exiting the conduit, the fluid enters a down hole reaction chamber connected to the conduit. In the reaction chamber, the high energy density fluid is ignited, and may atomized to assist in ignition. The reaction chamber can have a one-way valve that allows the fluid and/or reaction/decomposition products to exit the chamber and enter the formation, but prevents flow in the reverse direction. 
         [0026]    The method can include reciprocating the reaction chamber (such as by reciprocating the conduit) to release heat or reaction/decomposition products along a length of the wellbore. At or near the wellhead, the conduit can be directed through an appropriate pack off elastomeric device to provide a seal. 
         [0027]    In another aspect, a method is provided for the in situ treatment of hydrogen sulfide, comprising pumping a reactant that reacts with hydrogen sulfide to produce desirable products such as elemental sulfur into a wellbore via a stainless steel (as opposed to carbon steel) conduit and reacting the reactant with the hydrogen sulfide to produce desirable products. In some embodiments, the reactant comprises hydrogen peroxide and the product comprises elemental sulfur. 
         [0028]    The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter which form the subject of the claims of the invention. It should be appreciated by those skilled in the art of hydrocarbon production enhancement from wells that the conception and specific embodiment disclosed may be readily utilized as a basis for modifying or designing other structures and methods for carrying out well hydrocarbon production enhancement. For example the well production enhancement for enhanced oil recovery, in-situ processing of shale oil, coal, coal bed methane, shale gas, and tar sands, as well as other well enhancement fields, can use the methods and apparatuses of this invention. It should also be realized by those skilled in the art that such equivalent constructions do not depart from the spirit and scope of the invention as set forth in the appended claims. The novel features which are believed to be characteristic of the invention, both as to its organization and method of operation, together with further objects and advantages will be better understood from the following description when considered in connection with the accompanying figures. It is to be expressly understood, however, that each of the figures is provided for the purpose of illustration and description only and is not intended as a definition of the limits of the present invention. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS  
         [0029]    For a more complete understanding of the present invention, reference is now made to the following descriptions taken in conjunction with the accompanying drawing, in which: 
           [0030]      FIG. 1  is a schematic showing the well site and equipment of the present invention; 
           [0031]      FIG. 2  is a schematic of the well site and equipment of the present invention; 
           [0032]      FIG. 3  is a schematic of an apparatus used to ignite monopropellants in a subterranean environment in a reaction chamber attached to a stainless steel coiled tubing while reciprocating the reaction chamber; and, 
           [0033]      FIG. 4  is a schematic of hydrogen sulfide gas sweetened in-situ. 
       
    
    
     DETAILED DESCRIPTION OF THE INVENTION  
       [0034]    As used herein, “a” or “an” means one or more. Unless otherwise indicated, the singular contains the plural and the plural contains the singular. 
         [0035]    In many aspects and embodiments, the present invention uses reactive high energy density substances that can deliver a relatively high amount of energy per unit weight. Examples of such substances include 10% hydrogen peroxide, 100% hydrogen peroxide, hydrazine mixtures, and other substances. 
         [0036]    In the embodiment of  FIG. 1 , tank  1  holds a reactive fluid  50  and has shroud  3  located around inner tank  2 . Many reactive fluids may be used, including but not limited to hydrogen peroxide, hydrazine, monopropellants, hydrogen fluoride, hypergolic fluids (i.e., combustible without an ignition source), acids, bases, alcohols, diesel, propane, liquid natural gas, and combinations thereof. The reactive fluid  50  is preferably stored, monitored, and temperature controlled inside inner tank  2 . Located inside tank shroud  3  are heat exchanger tubes  4  connected to a heat exchanger  5 , which is preferably outside reactive fluid tank  1 . Heat exchange tubes  4  are also located inside inner tank  2 . The heat exchange permits safe temperature control of a reactive fluid, preferably cooling it to a temperature to retard its reactivity, but keeping it above a temperature such that it can be pumped into the well. This allows a reactive fluid to be introduced to a well in a activity-reduced state so that it can be directed to the outer parts of the reservoir  28  before reacting completely. In some embodiments, temperature control is required to heat the reactive fluid, such as when the ambient temperature would freeze the fluid to a point where it cannot be pumped. 
         [0037]    In one embodiment, heat exchanger fan  6  blows air across heat exchanger tubes  4  in heat exchanger  5 , and is driven by prime mover  7 . Other means of heat exchange are also in the scope of this invention. In one embodiment, the tank shroud  3  is filled with a suitable fluid, and heat exchanger tubes  4  are submersed in the reactive fluid. The reactive fluid is enclosed by shrouds filled with dilution fluids like water that allows for dilution of the reactive fluid in the event of a leak. In one embodiment, the fluid filling tank shroud  3  is water, and for convenience this disclosure may refer to water. Of course, other fluids can be used that provide either heat exchange or safety via dilution, or preferably, both. Heat exchanger  5 , tank  1 , inner tank  2 , shroud  3 , and tubes  4  are not limited to the geometries, orientations, or structure disclosed in the  FIG. 1  and  FIG. 2 , but rather can be any form suitable for the objects of this invention. 
         [0038]    The water in shroud  3  can be circulated from water tank  10  through pump  11  with the water returning from tank shroud  3  to water tank  10 . In one embodiment, tank  1  can be instrumented with temperature monitoring sensors  8 , and in one embodiment the sensors are optical fibers  8 , disposed inside tubes  4  and tubes  9  located inside tank  1 , both in tank shroud  3  and inside inner tank  2 . Optical fibers  8  can be used as temperature sensors themselves and are preferably monitored with an Optical Time Domain Reflectometer machine (“OTDR”)  12  that launches light down the fibers and interprets the backscatter light back to the machine to give continual distributed temperature profiles from the optical fibers  8 . This device is often referred to as an OTDR Distributive Temperature System (“OTDR DTS”). Additionally, the circulation of water from tank  10  through tank  1  in shroud  3  allows for an even heat to be maintained in the reactive fluid inside inner tank  2 . Thus,  FIG. 1  shows the adding or removing of heat from the reactive fluid using a heat transfer fluid in tank  1 . Additionally,  FIG. 1  shows the continuously monitoring of the temperature of shroud  3  and fluid inside inner tank  2 . For example, monitoring the temperature using optical fibers  8  interrogated with OTDR DTS machine  12 . 
         [0039]    The embodiment of  FIG. 1  has a hot oiler truck  13  that can heat the water in tank  10 , but other heating systems can be used. The hot oiler truck puts energy, Q in , into the system. The water can be transferred from the tank  10  through suction line  14  by pump  15 . The water is heated in hot oil truck  13  by burning propane on the truck and passing the water from tank  10  across the hot heat exchangers of truck  13  and then returning the heated water to tank  10 . The heated water from tank  10  can then be transferred to tank  1  through pump  11  and line  16 . The water from tank  1  is returned to tank  10  through line  17  to water tank  10 . Temperature sensors such as optical fibers  18  can monitor the temperature in tank  10  via methods such as an OTDR DTS machine  12 . Thus, the reactive fluid is indirectly heated by hot oil truck  13  using the fluid from tank,  10  which increases the safety of the temperature control process. 
         [0040]    Thus  FIG. 1  demonstrates how heat can be added to or removed from the reactive fluid  50  in tank  1  by using heat exchanger tubes  4  from the water in tank  10 . In some cases, the water in tank  10  is heated from the heat exchanger on truck  13 . The temperature of shroud  3  and the fluid inside inner tank  2  can be monitored continuously using temperature sensors, such as optical fibers interrogated with an OTDR DTS machine  12 . 
         [0041]    The embodiment in  FIG. 1  shows a reactive fluid being transferred from tank  1  where the reactive fluid  50  is stored and maintained at a temperature sufficiently above its solid temperature to allow transport downhole but sufficiently below a temperature such that its action is reduced. In one embodiment, the chilled reactive fluid travels through injection pump  19  through a shrouded suction conduit  16 A, which has water or other fluid circulated inside its shroud from water tank  10 . Water is delivered to shroud of conduit  16 A, via pump  11  and water line  16 , and the water returns from the shroud through line  17 . 
         [0042]    In one embodiment, pump  19  is enclosed in shroud  20 , which may use fluid from tank  10  in a manner similar to other shrouds described above. Pump  19  is powered by any known means, but preferably by hydraulic power pack  21  and controlled remotely from a frac van  22  with hydraulic controls via hydraulic control line  23 . Hydraulic control pack  21  is powered by prime mover  24  that is preferably monitored and controlled remotely from the frac van  22  by hydraulic control line  25 . The use of hydraulic power increases safety when working with reactive fluids. 
         [0043]    Injection pump  19  pressurizes the reactive fluid and the substances from tank  1  and injects them into (preferably shrouded) high pressure conduit  26  for injection into well  27  and out into subterranean reservoirs  28 . In a manner similar to other shrouds described, shrouded high pressure conduit  26  can have water supplied from tank  10  via pump  11  and line  29 , and water is returned to water tank  10  through line  34 . In one embodiment, wellhead  30  is shrouded with wellhead shroud  20 , which receives a fluid such as water from tank  10  through line  29 A, and the fluid returns to tank  10  through line  31 . 
         [0044]    Thus  FIG. 1  demonstrates how a temperature controlled reactive fluid is transferred from a temperature controlled tank and injected into well  27  and into subterranean reservoirs  28 . The water and other fluids in the shrouded conduits and pumps maintains the high pressure reactive fluid at a desirable temperature and maintains a means to capture and dilute any reactive fluid that may leak out from the inner high pressure conduit. In some embodiments, shrouds will serve to cool the reactive fluid, while in other embodiments they will serve to heat the reactive fluid. Thus, a reactive fluid is maintained at a proper temperature in a surface vessel located at a well site, tank  1 , and the reactive fluid is then injected at the desirable temperature into well  27  to allow the injected reactive fluid and substances to reach the subterranean reservoirs  28  in a low reactive state, thereby allowing the reactive fluid to be injected far afield beyond the wellbore,  40 , before the fluid and the substances react and release chemical energy. The position beyond the wellbore is shown in  FIG. 1  as element  40 . 
         [0045]    In one embodiment, the temperature of the reactive fluid is continually monitored in the well using at least one temperature sensor such as optical fiber  32  using the OTDR DTS machine  12 . Thus,  FIG. 1  shows an exemplary embodiment that illustrates that the down hole temperature of an injected reactive fluid can be controlled from surface by adding or removing heat at surface from the fluid in tank  1  through the heat exchanger  5 . It is clear to those familiar with the art of well treatment that multiple injection pumps  19  can be used to inject reactive fluid from multiple reactive fluid tanks  1  and the temperature controlled by multiple heat exchangers  5  and injected through multiple surface shrouded conduit lines  26  into single well  27  allowing higher injection rates into subterranean reservoirs  28 . 
         [0046]    In another embodiment shown in  FIG. 2 , a reactive fluid can be mixed with other materials in mixer  36 . In one embodiment, temperature controlled tank  1  holds a cold fluid, like liquid nitrogen or liquid CO 2 , which is delivered to blender vessel  36  through pump  35 . Tank  1  can be temperature controlled by any known manner. A reactive material, like solid 90% hydrogen peroxide, is transferred into blender vessel  36  from tank  33  and the materials from tank  1  and tank  33  are then mixed into a pumpable form, such as a slurry, in blender vessel  36  and injected into well  27  through high pressure injection pump  19  and far into the subterranean reservoirs. 
         [0047]    In another embodiment a reactive fluid like hydrogen peroxide can transferred from tank  1  at a controlled temperature, and solids like sand, ceramics, bauxite, proppants, and/or catalyst, can be added from tank  33  through a pump  240  into blender vessel  36 . Other reactive fluids and solids can be used as are known in the art. In embodiments where the temperature of the fluid in vessel  36  is desired to be cold, solids from tank  33  are preferably cool or cold. The solids and reactive fluid are mixed and injected into the well  27  and out into the reservoir  28 . Thus, reactive fluids are delivered into the reservoir  28  at a low temperature, increasing the distance the reactive fluid can be placed beyond the wellbore, releasing energy into the far field of subterranean reservoir  28 . 
         [0048]    In another embodiment a reactive fluid is transferred from tank  1  at a controlled temperature, and very cold solids can be added from tank  33  into blender vessel  36 . The solids preferably have a temperature lower than the freezing point of the reactive fluid from tank  1 , thereby causing the reactive fluid to freeze around and in the solids. The solids thusly coated with reactive fluid are pumped out of blending vessel  36  into well  27  and into the subterranean reservoirs  28 . Thus, reactive fluids are delivered into the reservoir  28  at a low temperature, greatly increasing the distance the reactive fluid can be placed beyond the wellbore, releasing energy into the far field of subterranean reservoir  28 . 
         [0049]    For example, the fluid in blender vessel  36  is kept cool by adding cold fluids, such as, cryogenic fluids, liquid nitrogen, methanol, or water, from tank  38  through pump  39  to the shroud of vessel  36 . Heat can be removed from mixing vessel  36  in heat exchanger  5 . Likewise, if the surface environmental temperatures are lower than the reactive fluids freezing point, blender  36  can be heated via a shroud or other heat exchanging system, which receives fluid such as hot water from tank  38 . Hot oiler truck  13  can heat the water in tank  38  using the propane burners and a heat exchanger on hot oiler truck  13 . If desired, the slurry leaving blender vessel  36  can be further temperature controlled before well injection by adding or removing heat via a heat exchange fluid in tank  37 , which can be controlled in any known manner, preferably with hot oiler truck  13  when heat, Q IN , is required. 
         [0050]    Once the injected fluid and solid warms up in the subterranean reservoir  28  and releases energy, Q out , e.g., by igniting, the in-situ energized fluid in the reservoir can be flowed back to the well surface through a line to a surface tank. This high temperature reaction in the reservoir and the reaction products will combine and further enhance the in-situ hydrocarbons&#39; ability to flow from the well. 
         [0051]      FIG. 3  shows a schematic of an apparatus used to ignite monopropellants in a subterranean environment in a reaction chamber attached to a stainless steel coiled tubing while reciprocating the reaction chamber. In FIG., the reaction chamber,  310  has an igniter,  302 , located in reaction chamber  310  and is connected to an electrical power transmission cable,  309 . The electrical power transmission cable is interwoven in the continuous coiled tubing and the cable is connected to a battery and/or capacitor,  301 . The battery and/or capacitor is positioned near the reaction chamber  310 . The coiled tubing,  307 , is lowered from a reeling device  311  or drum, through an elastomeric seal,  308 . The elastomeric seal is located at the surface and separates the surface environment from the subterranean well environment containing the reaction chamber. The reactor chamber  310  is positioned in the well,  312 , inside a well casing  306 . In one aspect of the present invention, the igniter  302  inside the reaction chamber  310  is powered using electrical power from a surface source  313  and/or a subterranean source  301 . Monopropellant fluid  315  is then pumped from a vessel  314  on surface with at least one pump  316  and the monopropellant fluid is transmitted through a swivel joint  317  and through the coiled tubing  309  on reel  311 . The fluid is then ejected from atomizers  303  located inside the reaction chamber  310 . Within the reaction chamber,  310 , the atomized fluid is ignited using the igniter  302 . The igniter is initiated using transmitted electrical power from the surface source  313 , and/or the down hole source  301  to the igniter. Once the monopropellant  315  is ignited in the reaction chamber, the combustion products  316  are transmitted out of the reaction chamber  310  into the well casing  306  along with the heat produced by the combustion reaction within the chamber. The elastomeric seal  308  allows for the reciprocation of the coiled tubing  309  from surface. The coiled tubing is reciprocated from the surface to the reaction chamber  310  inside the well  312  while simultaneously pumping the monopropellant  315  into the coiled tubing  307 . The coiled tubing is directed through the coiled tubing injector head  321 , the elastomeric seal  308  and into the well casing  306 . Also, the coiled tubing transports the electrical power to the igniter in the reaction chamber  310 . Another function of the coiled tubing is to dispose the combustion products  316  and to direct the heat into the surrounding subterranean reservoir  304 . While simultaneously flowing well fluids  318  from a subterranean reservoir  304  through perforations  305 , directing combustion products  316  to surface and igniting monopropellant fluids  315  in the reaction chamber  310 , the surface injector head  321  reciprocates the coiled tubing  309  in the well. 
         [0052]    In  FIG. 3 , a Optical Time Domain Reflectometry machine,  319 , directs light down an optical fiber  320  which is disposed in the coiled tubing  309 . Directing light from the source  319  into the optical fiber  320  and monitoring the back scatter light reflected back to the optical machine, a computer  319  uses algorithms to analyze the reflected light and to determine the temperature profile of the well. Since an optical fiber is used, the entire length of the optical fiber  320  is capable of being used as a sensor. 
         [0053]    Now directing your attention to the  FIG. 4  which illustrates hydrogen sulfide gas sweetened in-situ. In  FIG. 4 , a stainless steel continuous tube,  401 , is disposed inside a production tubing  402 . The production tubing is also disposed in a well casing  403 . The well casing has a packer  404  located on the production tubing. This packer seals the well casing  403  above the packer  404  from fluids in the casing below the packer  404 . Hydrogen peroxide fluid  405  is disposed in a temperature controlled vessel  406 , and pumped into the stainless steel coiled tubing  401 . As the hydrogen peroxide is pumped into the stainless steel coiled tubing, hydrogen peroxide is forced out an injection valve  407 . This injection valve is located at the distal end of the coiled tubing  401  which provides a means for mixing the hydrogen peroxide  405  with hydrogen sulfide fluids  408  being produced in the subterranean reservoir. The mixing of the hydrogen peroxide with the hydrogen sulfide allows the subterranean hydrogen sulfide fluid being produced from the reservoir to react with the hydrogen peroxide fluid  405  being injected into the well  312 . As stated above, the hydrogen peroxide is injected through the coiled tubing  401 . This subterranean fluid mixing serves to remove hydrogen sulfide gas from the flowing well fluid  408 . Because the fluid is flowing, the reaction products resulting from the reaction of hydrogen peroxide  405  and the well fluids with hydrogen sulfide gas  408  flows to the surface and these products are directed out of the well into a flow line  409  at surface. 
         [0054]    In another embodiment, at least one hypergolic component is pumped down a wellbore. In yet another embodiment, at least two hypergolic components are separately pumped down a wellbore released such that they will mix in the wellbore. For example, a first reactive substance such as hydrogen peroxide is pumped from the surface into the wellbore and reservoir using one conduit, and a second substance that will spontaneously ignite with the first substance, such as ammonia, is pumped from the surface into the wellbore and reservoir using a separate conduit. The two substances will mix in the wellbore and subterranean formation forming a hypergolic fluid. The substances may, in some embodiments, be temperature, pressure controlled, and/or shrouded as described in any one of the above embodiments. 
         [0055]    In any of the embodiments, the containers and conduits can be made from any material known in the art, such as stainless steel. The containers and/or conduits can, if desired, be passivated, coated with films, chemical films, or metal oxides, and/or otherwise treated to enhance the overall process. If a surface is passivated, it is desirable to test the surface for passivation at various times. In some embodiments, pressure monitoring and/or testing is desired for certain containers and/or conduits. 
         [0056]    In another embodiment, a method provides energy to a subterranean environment by directing a reactive high energy density fluid from a surface source (such as a temperature controlled vessel), through surface lines, through a conduit (such as a coiled tubing) disposed in a wellbore, and into the wellbore where the fluid decomposes, ignites, or reacts to form products that comprise elemental oxygen. The energy of this reaction heats the surrounding formation. In addition, the elemental oxygen product reacts with in situ hydrocarbons to propagate additional reactions into the formation, which can generate heat, decompose heavy hydrocarbons and kerogen into lighter hydrocarbons, and increase the productivity of the well. 
         [0057]    In an another aspect of the present invention, acoustical and/or seismic energy is transmitted from the surface to the reaction chamber. This energy is used to ignite an explosive in the reaction chamber. In an alternate and/or specific example, acoustical energy is used to heat at least one element in the reaction chamber. 
         [0058]    In some embodiments, upon exiting the conduit, the fluid enters a down hole reaction chamber connected to the conduit. In the reaction chamber, the high energy density fluid is ignited, and atomized to aid the ignition. The reaction chamber can have a one-way valve that allows the fluid and/or reaction/decomposition products to exit the chamber and enter the formation, but prevents flow in the reverse direction. In some cases, the method includes reciprocating the reaction chamber (such as by moving the conduit) to release heat or reaction/decomposition products along a length of the wellbore. At or near the wellhead, the conduit is directed through an appropriate pack off elastomeric device to provide a seal. 
         [0059]    In another embodiment, a method is provided for the in situ treatment of hydrogen sulfide. Hydrogen sulfide is a dangerous chemical with many undesirable qualities. Hydrogen peroxide reacts with hydrogen sulfide to produce elemental sulfur and other products. Moreover, hydrogen peroxide reacts with or interacts with many materials found in oxides of metals and subterranean minerals, with a very reactive catalyst being iron oxide. Hence the injection or transport of hydrogen peroxide into wells with iron or carbon steel tubulars, frac lines, or well heads is highly dangerous, and becomes exceedingly dangerous as the percentage of active hydrogen peroxide is increased. 
         [0060]    In some embodiments, the current method uses a stainless steel (as opposed to carbon steel) conduit to carry substances, such as hydrogen peroxide, that react with hydrogen sulfide to produce desirable products, such as elemental sulfur. The reactant is delivered into a wellbore via a stainless steel conduit, where it reacts with the hydrogen sulfide to produce desirable products. Thus, as fluids are produced back, they contain less (or no) harmful hydrogen sulfide, which increases safety and saves time and money because the need to treat the hydrogen sulfide is reduced or eliminated. In any or all of the embodiments, the conduit is a continuous conduit, meaning that it is not made up from repeated threaded joints. 
         [0061]    Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the disclosure of the present invention, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized according to the present invention. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

Technology Classification (CPC): 4