CROSS-REFERENCES TO RELATED APPLICATIONS

[0001] This Application claims the benefit under 35 U.S.C. § 119(e) of U.S. Provisional Patent Application No. 61/778,178 filed March 12, 2013 which is incorporated herein by reference in its entirety as if fully set forth herein.

FIELD OF THE INVENTION [0002] The present disclosure relates to compositions and methods that are effective in hydraulic fracturing and in the energy industry's drilling process using non-corrosive, yet highly effective forms of acids.

BACKGROUND OF THE INVENTION

[0003] Hydraulic fracturing, commonly referred to as "fracking", or "hydrofracking" is a proven technology whereby natural gas and oil producers can safely recover natural gas and oil from deep shale formations. Fracking is the process of initiating and subsequently propagating a fracture of the rock layer by employing the pressure of a fluid as the source of energy. Special fluids are injected underground at high pressures which fracture the rock formations, and free the oil or gas in the rock. Because of the use of hydraulic fracturing in combined with horizontal drilling, vast amounts of deep shale natural gas and oil can now safely be produced.

[0004] Hydraulic fracturing is a process where millions of gallons of water, sand and chemicals are pumped underground to break apart the rock and release the gas. The fracturing is done when a well is drilled into reservoir rock formations consisting of shale rock or coal beds. As the pressure is increased in the rock formations the extraction rates and recovery of oil and natural gas and coal seam gas can proceed. The fracture width is typically maintained after the injection by introducing a "proppant" into the injected fluid. Proppant is a material, such as grains of sand, ceramic, or other particulates that prevent the fractures from closing when the injection is stopped. [0005] While the main industrial use of hydraulic fracturing is in stimulating production from oil and gas wells hydraulic fracturing can also be used to:

1. Stimulate groundwater wells

2. Precondition rock for caving. 3. Enhance waste remediation processes (usually hydrocarbon waste or spills) or spills.

4. Dispose of waste by injection into suitable deep rock formations

5. Measure the stress in the earth.

[0006] The fluid injected into the rock typically contains at least two items: a. a slurry of water, b. proppants

[0007] There are several types of proppant materials used which include silica sand, resin- coated sand, man-made ceramics and chemical additives include an acid, normally hydrochloric acid. Gels, foams, and compressed inert gases, including nitrogen, carbon dioxide and maybe air may also be injected into the wells. [0008] Chemical additives are tailored to the specific geological situation, protect the well, and improve its operation, though the injected fluid is approximately 99 percent water and 1 percent proppants. Initially an acid is used to increase permeability. It can, however, be toxic due to the chemical additives in the proppants. Recovered fluid is sometimes processed so that part of it can be reused in the operations or released into the environment. [0009] When hydraulic fracturing takes place, the best option is to fracture formations using sand and water without any additives, or sand and water with non-toxic additives.

[00010] Another common option is to use diesel in hydraulic fracturing fluids. This should be avoided, since diesel contains the carcinogen benzene, which contains benzene, ethyl benzene, toluene, xylene, naphthalene and other chemicals; polycyclic aromatic

hydrocarbons; methanol; formaldehyde; ethylene glycol; glycol ethers; hydrochloric acid; and sodium hydroxide. [00011] Hydraulic fracturing proppant materials must be effective in create the fractures in the shale to allow the trapped natural gas to escape and to make its way to the well point to be pumped to the surface, and to be effective they must achieve several factors:

1. It must be a strong enough acid to create the cracks /fractures in the rock formation. 2. It must be exposed to the rock beds long enough to be effective.

3. The correct concentration must be used to effectively release the natural gas or oil.

4. The product must remain active in the environment in which it is used.

5. It must not be corrosive to equipment

6. It must be compatible with gelling and foaming agents 7. It must be able to withstand extensive pressure when underground and still be effective.

[00012] The petroleum industry defines a stuck pipe as a condition whereby the drill string cannot move, along its axis, be it a rotated or reciprocated drill system that is employed in the wellbore. Differential sticking typically occurs when high-contact forces caused by low reservoir pressures, high wellbore pressures, or both, are exerted over a sufficiently large area of the drill string. Differential sticking is, for most drilling organizations, the greatest drilling problem worldwide in terms of time and financial cost.

[00013] Stuck pipes can be categorized by their physical characteristics into 7 categories. Each category and the solution is unique to the operator. These are further broken down as Open-hole and Cased-hole drilling.

[00014] The stuck pipe categories in OPEN HOLE drilling are:

1. Keyseats: An open-hole equivalent of mechanical sticking inside the casing where the drill string is physically captured by the earth and concretion occurs stopping all movement. 2. Differential Sticking: This is the most common type of sticking and is purely frictional resistance. 3. Hole Col pse: This may be related to the geologic formation such as a swelling shale that can bury a drill string as by avalanche, or it may be caused by inadequate hole cleaning as in the buildup of a cuttings bed. Both case, the pipe can become stuck or reduced or blocked circulation. 4. Horizontal Drilling: Depending on the radius of curvature used to reach horizontal, it is many times impossible to use conventional tools and procedures to free a stuck pipe.

[00015] The stuck pipe in CASE HOLE drillings are:

1. Mud, Scale, or Sand Stuck Tubing and Liners: Mud and sand will physically grab the drill string and as the accumulation of materials heats up, the chemistry of concretion increases until the drill string is captured and cannot move any longer. The over manipulation of this type of sticking will cause tubing separation, leading to shut down.

2. Mechanically Stuck Members: This is a wedging action or mechanical interference of the free passage of a tubular or possibly an upset section such as a tubing joint connection. 3. Seal Assemblies: Seal assemblies become stuck in a receptacle usually due to conditions of heat and pressure over time. In effect, it is similar to a vulcanization process that causes the seal to adhere to the wall of the receptacle.

[00016] Each drilling fluid has positive and negative features. The positives for water- based muds are: 1. They do not release free oil;

2. They are usually without toxic contaminants such as cadmium and mercury;

3. They are typically discharged at the well site and are widely used in shallow wells and in shallower portions of deeper wells.

[00017] On the negative side, in deep or extended-reach wells, the performance of water-based muds WBMs is poor, which is the main reason for deep well intervals and complex drilling situations, oil-based muds (OBMs) and synthetic-based muds (SBMs) are preferred. [00018] There are several methods currently used to address stuck pipes:

1. highly reactive, corrosive and dangerous acids,

2. sonics and mechanical pipe manipulation,

3. greases and lubricants, exotic synthetic compounds, 4. extensive training and educational courses for well head crews.

[00019] The current unsticking methods require from one to three days to unstick a pipe, resulting in a complete shutdown of the rig and a loss of several million dollars per well in lost wages, time, and cost to remediate the problem. Some of the methods are as follows:

1. The first is the traditional method which involves mechanical manipulation of the drill string by an experienced crew. The danger of physical or mechanical manipulation of the drill string and casing is that the pipe will actually separate as it is being forcibly twisted and bounced up and down.

2. A second novel approach is to utilize sonic engines attached to the drill string to induce axial forces, while pumping highly acidic and hazardous chemicals into the casing and well bore, attempting to fluidize the portion of the trapped in the pipe.

3. The third approach is to pump specialized highly acidic solutions down the bore to free the pipe and its cuttings and hopefully reestablish circulation through dissolving the mud cake which holds the pipe in its stuck position. The chemicals currently used are hazardous, expensive, and cause environmental concern when finally surfacing. 4. The fourth method of servicing the stuck pipe is operator training, usually conducted by contract services for each drilling crew over a period of 3-5 days at an off-site training facility. This is preventative in nature and cures the operator failures in about 80% of the cases.

SUMMARY OF THE INVENTION

[00020] The present disclosure relates to compositions and methods that are effective in hydraulic fracturing and the energy industry's drilling process using non-corrosive, yet highly effective forms of acids. The disclosed compositions comprise a system comprising an organic acid, a pH buffer, a surfactant, a thickening agent; all in an aqueous composition.

DESCRIPTION OF EXEMPLARY EMBODIMENTS

[00021] In this specification and in the claims that follow, reference will be made to a number of terms that shall be defined to have the following meanings:

[00022] Throughout this specification, unless the context requires otherwise, the word

"comprise," or variations such as "comprises" or "comprising," will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps. [00023] The term "effective amount" as used herein means "an amount of a composition as disclosed herein, effective at dosages and for periods of time necessary to achieve the desired result." An effective amount may vary according to factors known in the art, such as the state, age, species, and size of the area being treated. Although particular dosage regimes may be described in examples herein, a person skilled in the art would appreciated that the dosage regime may be altered to provide optimum therapeutic response.

[00024] It must be noted that, as used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a carrier" includes mixtures of two or more such carriers, and the like. [00025] "Coal beds" is used herein refers to a layers, beds or veins of a black or brownish sedimentary rock which is combustible. Its hardness can be increased by pressure and temperature.

[00026] "Optional" or "optionally" means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.

[00027] Ranges may be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations by use of the antecedent "about," it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint and independently of the other endpoint.

[00028] A weight percent of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included.

[00029] By "contacting" is meant an instance of applying a composition to a domesticated animal. Contacting can include applying a composition directly by hand or brush, by dipping the domesticated animal or a part or portion thereof in a container comprising a disclosed composition, by spraying and by applying the disclosed composition to the domesticated animal's surroundings such as on straw or a milking machine such that the disclosed composition contacts the domesticated animal.

[00030] By "sufficient amount" and "sufficient time" means an amount and time needed to achieve the desired result or results, e.g., control and/or prevention of infection of a domesticated animal.

[00031] "Admixture" or "blend" as generally used herein means a physical combination of two or more different components

[00032] "Controlled release" as used herein means the use of a material to regulate the release of another substance. [00033] "Thickening agent" is used herein to refer to products that forms a gel or to increase the viscosity of the final mixture.

[00034] "WBM" is used herein to refer to Water Based Muds.

[00035] "OBM" is used herein to refer to Oil Based Muds

[00036] 'Tracking" as used herein refers to the process of initiating and subsequently propagating a fracture of the rock layer by employing the pressure of a fluid as the source of energy.

[00037] "SBM" is used herein to refer to Synthetic Based Muds [00038] "Shale" is used herein to refer to is a fine-grained, sedimentary rock composed of mud that is a mix of flakes of tiny fragments of other minerals such as quartz.

[00039] "Non-corrosive acid System" is used herein to refer to an acid system that is safe and non-corrosive to human tissue.

[00040] "Stuck pipe" is used herein to refer to any drilling pipe or string of pipes that is plugged or where the flow is restricted or stopped.

[00041] "String of pipes" is used herein to refer to any drilling pipes that are continuous or where two or more than two length of drilling pipes are attached.

[00042] "Mud cake" is used herein to define the material in a stuck pipe that causes the restricted flow or blockage.

[00043] "Drilling process" is used herein to refer to the actual process or system that is utilized in oil or gas patches to access to remove the oil or gas from the ground or on the sea- floor.

[00044] "Proppant" is used herein to refer to any granular material that, in an aqueous mixture, can be used to fracture the rock formation.

[00045] The present disclosure addresses solutions to several unmet needs as defined below:

1. Providing compositions effective in creating the cracks in the underlying rock formations.

2. Providing compositions effective to be used in a gel form to aid in the extracting of the gas and oil.

3. Providing compositions effective that will not decompose under extreme pressure and temperature.

4. Providing compositions effective to work in all types of proppants.

5. Providing compositions effective in releasing the drill string in both open hole and closed hole drilling operations. 6. Providing compositions effective that can unstick a pipe in a matter of hours and when used as a spotting fluid in the annulus of a bore hole that permits drill cuttings.

7. Providing compositions that are still effective yet concentrated enough to require less product and therefore require less storage space.

8. Providing compositions that significantly reduce the down time needed to free a stuck pipe.

9. Providing compositions that are non-corrosive yet able to be reactive with the shale rock formations.

10. Providing compositions that are non-corrosive, yet act as a strong acids in the underground rock formations and in the drilling process.

11. Providing compositions that will not decompose under extreme pressure and temperature

Treatment Compositions

[00046] Compositions that are a non-corrosive, strong acidic mixture for use in the underground rock formations of hydraulic fracking and the energy industry's drilling process, consisting of: a) from about 0.01% to about 10.0 % by weight of a non-corrosive acid system, comprising: i. an organic acid at least 0.01% to 25.0% by weight; and ii. at least about 10.0% by weight of an pH buffer agent; and b) from about 0.01% to 5.0% by weight of a surfactant; and c) from about 0.10% to about 10.0% by weight of a thickening agent; and d) the balance being an aqueous based carrier.

[00047] Additional advantages will be set forth in part in the description that follows and in part will be obvious from the description or may be learned by practice of the aspects described below. The advantages described below will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive. Noncorrosive Acid System

[00048] The disclosed compositions comprise a noncorrosive acid system which comprises an organic acid and a pH buffer.

Or2anic Acid

[00049] Organic acids which are safe under the FDA GRAS guidelines for food production yet still effective in decomposition of carbonates found in the soils and in rock formations. The basic principle action of organic acids on carbonates is to cause the disassociation or the carbonate to produce the oxide and carbon dioxide.

[00050] The first group of suitable organic acids is Lactic, Acetic, Formic, Fumaric,

Citric, Oxalic, Adipic and Uric. [00051] The second group of suitable organic acids is the carboxylic acids, whose acidity is associated with their carboxyl group -COOH. Sulfonic acids, containing the group -SO ₂ OH, are relatively stronger acids. The relative stability of the conjugate base of the acid determines its acidity. In some biological systems more complex organic acids such as L- lactic, citric, and D-glucuronic acids are formed. These use the hydroxyl or carboxyl group. [00052] The third group of suitable organic acids is Humic, Sebacic, Stearic, Gallic,

Palmitic, Caffeic, Glyoxylic, Fulvic, Carnosic, Anthranilic, Ellagic, Lipoic, Chlorogenic, Rosmarinic, Phosphoric, Methacrylic, Oleanic, Nitrohumic, Florocinnamic, Hexaflorosilicic, Hydrofluoric, Hydroxycitric and Silicofluoric.

[00053] The fourth group of suitable organic acids is fruit acids. The acids in fruits are chiefly acetic, malic, citric, tartaric, oxalic, and in some instances boric. Malic acid is present in apples, pears, currants, blackberries, raspberries, quince, pineapple, cherries, and rhubarb. Citric acid is found in lemons, oranges, grapefruit, lemons, limes, quince, gooseberry, strawberry, raspberry, currant, and cranberry. Tartaric acid occurs in grapes. Boric acid is found in many fresh fruits and vegetables. Mandelic acid is present in almonds. [00054] The fifth group of suitable organic acids is beta hydroxy acids which is a type of phenolic acid. Salicylic acid is a colorless crystalline organic acid whose main active ingredient obtained from this source is a monohydroxiybenzoic acid. pH Buffer [00055] A non-corrosive acid composition, having a maximum proton count of 1.5

X10 ^A 25, an embodied conductivity range of from 250 mV to 1500mV and a 0.1% solution of the composition having a pH of under 2.0.

Surfactant

[00056] A surfactant component includes ingredients that modify the water in the system making it suitable from use with several types of water such as hard water, soft water, sulfite contaminated water, rain water, pond water, well water or calcium rich water. The method for improving the stickiness properties of the composition encompasses adding an effective amount of a polymer comprising:

1. about 60 to about 99%, based on total polymer weight, of a quaternary diallyl dialkyl ammonium monomer, wherein alkyl groups are independently selected from alkyl groups of

1 to 18 carbon atoms, preferably C i_ ₄ alkyl, and wherein said quaternary diallyl dialkyl ammonium monomer's counterion is selected from the group consisting of conjugate bases of acids having an ionization constant greater than 10 ¹³ , more preferably selected from the group consisting of fluoride, chloride, bromide, hydroxide, nitrate, acetate, hydrogen sulfate, and primary phosphates; and

2. About 1 to about 40%, based on total polymer weight, of an anionic monomer selected from the group consisting of acrylic acid and methacrylic acid; wherein the average molecular weight of said polymer ranges from about 50,000 to about 10,000,000, as determined by gel permeation chromatography. [00057] The polymer base can also be a combination of one or more bases, for example, glycerol in combination with ethoxylated partial glyceride fatty acid esters. These include branched chain esters, ethoxylated partial glyceride fatty acid esters, protein derivatives, lanolin and lanolin derivatives, and fatty alcohol ethoxylates, emollient oils, fatty acids, fatty alcohols and their esters. Other examples of suitable bases include glycerine, sortibal aloe, poylglycols, polyethylene glycol, polyoxyethylene and polyethylene oxide.

Thickenin2 A2ent

[00058] The disclosed compositions further comprise from about 0.1% to about 10% by weight of a thickening agent. Suitable thickening agents include hydroxynethyl cellulose, hydroxyethyl cellulose, methylcellulose, hydroxypropyl cellulose, methyl cellulose, carboxy methylcellulose, emulsifying waxes, alkyl triammonium methosulfate, and ceteraryl octanoate. Although the disclosed compositions are aqueous based, certain ingredients may require the presence of a more lipophilic solvent for proper stabilization. Preferred additional solvents are polyhydric alcohol solvents, or "polyol" solvents, such as the polyalkylene glycols having alkylene moieties containing about 2-3 carbon atoms, preferably the polyethylene glycols. Molecular weight ranges of from about 200-4000 are preferred for the polyalkylene glycols e.g., propylene glycol.

[00059] Other examples of thickeners are polysaccharides and linear sulfated polysaccharides of natural origin, which increase the viscosity increase in solution, even at small concentrations. These can be classified as uncharged or ionic polymers natural gums obtained from seaweeds. These are Agar, Alginic acid Sodium alginate, Carrageenan (kappa, Iota or lambda), Gum arabic, Gum ghatti, Gum tragacanth, Karaya gum, Guar gum, Locust bean gum, Beta-glucan, Chicle gum, Dammar gum, Glucomannan, Mastic gum, Psyllium seed husks, Spruce gum, Tara gum Gellan gum and Xanthan gum.

[00060] Another example of a suitable thickener poylsaccharides is starch which can be unmodified or modified using acid, enzymes, alkaline, bleached, oxidized, acetylated, hydroxpropylated, octenylsuccinic anhydride, carboxyethylated, phosphate, hydroxypropyl, and acetylated oxidated) , cationic, cold water, pregelatinized and instant starch. Carriers

[00061] The balance of the disclosed compositions comprises a carrier. The carrier can be any suitable material that can dissolve the active ingredients and co-ingredients. Water is a convenient carrier for liquid embodiments of the disclosed composition Formulations

The following are non-limiting examples of the disclosed compositions:

Table 1

Table 2

Methods of Use

[00062] The disclosed compositions can be used for various applications with the application methods and dosage regimens dictated by the needs and demand.

1) Liquid applications usually consist of a composition that is enough to make contact with the underground rock formations to create the sinus or fractures in the layers of shale and coal beds where these trapped reservoirs of natural gas or oil occur. The sinus created, will allow the trapped mixture to travel to the well point to be extracted. The acidic composition must be adequate enough so when under high pressure and increased temperature it remains stable and also makes contact with any pregnant rocks will free its contents.

2) Gel applications can be utilized as a replacement for the liquid composition.

The main advantage of the gel is its thickness which will allow the embodied composition a longer contact period with the rocks and fill the voids created by the escaped gas and oil. This also must be stable at elevated temperature and under high pressure.

3) The disclosed compositions and methods are effective in preventing and/or releasing stuck pipes that are a physical limitation in the drilling process associated with hydraulic fracturing.

Test Results

[00063] The results in Table 3 show that the inventive compositions are able to remove

WBM and OBM from any active borehole operation. Table 3

[00064] While particular embodiments of the present disclosure have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the disclosure. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this disclosure.