Method for enhanced fracture cleanup using redox treatment

<u>FIELD</u>

This disclosure relates to a composition and method to improve the recovery of hydrocarbons from a fractured formation. More specifically, this disclosure relates to a composition and method to reduce the viscosity of a fracturing fluid.

<u>BACKGROUND</u>

Hydraulic fracturing fluids containing proppants are used extensively to enhance productivity from hydrocarbon reservoir formations, including carbonate and sandstone formations. During hydraulic fracturing operations, a fracturing treatment fluid is pumped under a pressure and rate sufficient for cracking the formation of the reservoir and creating a fracture. Fracturing operations usually consist of three main stages including a pad fluid stage, a proppant fluid stage, and an overflush fluid stage. The pad fluid stage typically consists of pumping a pad fluid into the formation. The pad fluid is a viscous gelled fluid which initiates and propagates the fractures. Auxiliary fractures can propagate from the fractures to create fracture networks. A fracture network can comprise fractures and auxiliary fractures. Auxiliary fractures can connect the fractures.

The proppant fluid stage involves pumping a proppant fluid into the fractures of the formation. The proppant fluid contains proppants mixed with a viscous gelled fluid or a viscoelastic surfactant fluid. The proppants in the proppant fluid are lodged in the fractures and create conductive fractures through which hydrocarbons flow. The final stage, the overflush stage, includes pumping a viscous, gelled fluid into the fractures to ensure the proppant fluid is pushed inside the fractures. While the three stages have different aims, all three make use of highly viscous and/or gelled fluids to achieve those aims.

A downside of the traditional method is that a high volume of gelled or polymeric materials can be left behind in the fractures. The gelled materials can be concentrated around the proppant in the fractures or can be freely in the fractures. The gelled material acts to block the fractures reducing the fracture conductivity. The hydrocarbons which flow from the reservoir formation are unable to move the gelled materials. Traditional methods for cleaning the fractures involve viscosity breakers or other elements to breakdown the fluid. These traditional methods suffer from an inability to completely cleanup the fractures, leaving residual viscous material and reduced conductivity. <patcit id="pcit0001" dnum="US4846227A"><text>US4846227A</text></patcit> describes a continuous process of hydraulic fracturing of a well with <i>in situ</i> nitrogen foam generation.

<u>SUMMARY</u>

This disclosure relates to a composition and method to improve the recovery of hydrocarbons from a fractured formation. More specifically, this disclosure relates to a composition and method to reduce the viscosity of a fracturing fluid, such as, for example, a gelled and/or viscous fracturing fluid.

In one aspect, there is provided a method for improved hydrocarbon recovery from a formation due to cleanup of a residual viscous material, the method comprising the steps of fracturing the formation with a fracturing fluid to generate fractures, the fracturing fluid comprising: a viscous fluid component, the viscous fluid component operable to increase the viscosity of the fracturing fluid and to fracture the formation to create the fractures leaving behind the residual viscous material in the fractures; a proppant component, the proppant component operable to hold open the fractures, wherein the proppant component is carried to the fractures by the viscous fluid component; and a cleanup fluid, the cleanup fluid comprising at least one component (an acid precursor)comprising triacetin; and an exothermic reaction component operable to generate heat after the proppant component has been placed in the fractures, and the exothermic reaction component comprising at least one component selected from the group consisting of: urea, sodium hypochlorite, ammonium chloride, ammonium bromide, ammonium nitrate, ammonium sulfate, ammonium carbonate, ammonium hydroxide, sodium nitrite and potassium nitrite, wherein the heat is operable to reduce a viscosity of the residual viscous material to create a reduced viscosity material, the reduced viscosity material operable to flow from the formation. Fractures can include auxiliary fractures, which propagate from the fractures.

In certain aspects, the exothermic reaction component includes an ammonium containing compound and a nitrite containing compound. In certain aspects of the present disclosure, the ammonium containing compound is NH₄Cl and the nitrite containing compound is NaNO₂. In certain aspects of the disclosure, the at least one component comprised in the cleanup fluid (acid precursor) is triacetin.

Also described is a cleanup fluid for reducing a viscosity of a residual viscous material in fractures is provided. The cleanup fluid includes at least one component (an acid precursor) comprising triacetin, the at least one component operable to trigger an exothermic reaction component, the exothermic reaction component operable to generate heat, wherein the heat is operable to reduce a viscosity of the residual viscous material to create a reduced viscosity material, the reduced viscosity material operable to flow from the fractures.

In certain aspects, the exothermic reaction component includes an ammonium containing compound and a nitrite containing compound. In certain aspects of the present disclosure, the ammonium containing compound is NH₄Cl and the nitrite containing compound is NaNO₂. In certain aspects of the present disclosure, the acid precursor is triacetin.

In another aspect there is provided a method to cleanup fractures in hydraulic fracturing operations, the method comprising the steps of: fracturing a formation in a hydraulic fracturing operation to generate fractures, wherein the step of fracturing the formation comprises the step of fracturing the formation with a fracturing fluid to generate fractures, the fracturing fluid comprising: a viscous fluid component, the viscous fluid component operable to increase the viscosity of the fracturing fluid and to fracture the formation to create the fractures leaving behind residual viscous material in the fractures, the viscous fluid component having a viscosity; a proppant component, the proppant component operable to hold open the fractures, wherein the proppant component is carried to the fractures by the viscous fluid component; and following hydraulic fracturing, injecting a cleanup fluid into the fractures to reduce a viscosity of the residual viscous material by generation of heat and pressure produced from an exothermic reaction, the clean up fluid operable to reduce the viscosity of the residual viscous material, wherein the cleanup fluid comprises: at least one component (an acid precursor) comprising triacetin; and an exothermic reaction component operable to generate heat, and the exothermic reaction component comprising at least one component selected from the group consisting of: urea, sodium hypochlorite, ammonium chloride, ammonium bromide, ammonium nitrate, ammonium sulfate, ammonium carbonate, ammonium hydroxide, sodium nitrite, and potassium nitrite, wherein the heat is operable to reduce the viscosity of the residual viscous material to create a reduced viscosity material, the reduced viscosity material operable to flow from the fractures. In certain aspects of the present disclosure, the exothermic reaction component includes an ammonium containing compound and a nitrite containing compound. In certain aspects, the ammonium containing compound is NH₄Cl and the nitrite containing compound is NaNO₂. In certain aspects, the acid precursor is triacetin.

<u>BRIEF DESCRIPTION OF THE DRAWINGS</u>

These and other features, aspects, and advantages of the present disclosure will become better understood with regard to the following descriptions, claims, and accompanying drawings. It is to be noted, however, that the drawings illustrate only several embodiments of the disclosure and are therefore not to be considered limiting of the disclosure's scope as it can admit to other equally effective embodiments. <ul id="ul0001" list-style="none"><li><figref idref="f0001">FIG. 1</figref> is a graphic representation of the effect of the cleanup fluid on the viscosity of the residual viscous material.</li><li><figref idref="f0002">FIG. 2</figref> is a graphic representation of the heat and pressure generated by the exothermic reaction component.</li><li><figref idref="f0003">FIGS. 3a and 3b</figref> are pictorial representations of the residual viscous material before the reaction of an exothermic reaction component of the cleanup fluid.</li><li><figref idref="f0004">FIG. 4</figref> is a graphic representation of the effect of the reaction of the exothermic reaction component on the viscosity of a fracturing fluid.</li></ul>

<u>DETAILED DESCRIPTION</u>

While the disclosure will be described with several embodiments, it is understood that one of ordinary skill in the relevant art will appreciate that many examples, variations and alterations to the apparatus and methods described herein are within the scope of the disclosure. Accordingly, the embodiments described herein are set forth without any loss of generality, and without imposing limitations, on the claims.

In one aspect, a method for improved hydrocarbon recovery from a formation due to cleanup of a residual viscous material is provided. The hydraulic fracturing operation fractures the formation using fracturing fluid to create fractures. Formations include sandstone and carbonate, for example.

The fracturing fluid includes a viscous fluid component and a proppant component. The viscous fluid component has a viscosity. The viscous fluid component is operable to increase the viscosity of the fracturing fluid. Viscous fluid components include viscosified water-based fluids, non-viscosified water-based fluids, gel-based fluids, gel oil-based fluids, acid-based fluids, and foam fluids. Gel-based fluids include cellulose derivatives and guar-based fluids. Cellulose derivatives include carboxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxypropyl cellulose, and methyl hydroxyl ethyl cellulose.

Guar-based fluids include hydroxypropyl guar, carboxymethyl guar, guar cross-linked boron ions from an aqueous borax/boric acid solution, and guar cross-linked with organometallic compounds. Organometallic compounds include zirconium, chromium, antimony, and titanium salts. Gel oil-based fluids include aluminum phosphate-ester oil gels. In at least one embodiment of the present disclosure, the viscous fluid component is an aqueous guar solution, having a concentration of guar gum between about 0.1% and about 15%, between about 0.1% and about 10%, between about 1% and about 10%, between about 2% and about 8%, and between about 4% and about 6%.

The proppant component includes a proppant. The proppant is operable to hold open fractures created by the viscous fluid component. Any proppants capable of holding open fractures to create a conductive fractures are suitable for use in the present disclosure. In some embodiments, the proppant component includes a viscous carrier fluid having a viscosity. Viscous carrier fluids include viscosified water-based fluids, non-viscosified water-based fluids, gel-based fluids, gel oil-based fluids, acid-based fluids, and foam fluids. Gel-based fluids include cellulose derivatives and guar-based fluids. Cellulose derivatives include carboxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxypropyl cellulose, and methyl hydroxyl ethyl cellulose.

Guar-based fluids include hydroxypropyl guar, carboxymethyl guar, guar cross-linked boron ions from an aqueous borax/boric acid solution, and guar cross-linked with organometallic compounds. Organometallic compounds include zirconium, chromium, antimony, and titanium salts. Gel oil-based fluids include aluminum phosphate-ester oil gels. In some embodiments, the hydraulic fracturing operation uses a one stage fracturing fluid, in which the fracturing fluid includes both the viscous fluid component and the proppant component, in which the viscous fluid component carries the proppant component to the fractures.

In at least one embodiment, the hydraulic fracturing operation uses a multi-stage fracturing fluid in which the viscous fluid component is injected into the formation, followed by the proppant component in the viscous carrier fluid. In some embodiments, the injection of the proppant component is followed by injection of additional viscous fluids to ensure the proppants are placed in the fractures. The additional viscous fluids have a viscosity.

In some embodiments, the viscosity of the viscous fluid component, the viscous carrier fluid, and additional viscous fluids are the same. In some embodiments, the viscosity of the viscous fluid component, the viscous carrier fluid, and additional viscous fluids are different. The injection of the fracturing fluid ceases after the proppants are placed in the fractures and the fracturing fluid is allowed to seep from the fractures. In some embodiments, the injection of the hydraulic fracturing fluid including the viscous fluid component and/or the proppant component and/or the overflush component and/or the exothermic reaction component does not generate foam or introduce foam into the hydraulic formation including the hydraulic fractures.

The hydraulic fracturing operation can leave residual viscous material in the fractures of a hydraulic formation. Residual viscous materials can include carboxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxypropyl cellulose, methyl hydroxyl ethyl cellulose, guar gum, hydroxypropyl guar, carboxymethyl guar, guar cross-linked with boron, aluminum phosphate-ester oil gel, and guar cross-linked with organometallic compounds. Organometallic compounds include zirconium, chromium, antimony, and titanium salts. In some embodiments of the present disclosure, the residual viscous material is a gelled material. In some embodiments of the present disclosure, the residual viscous material is a polymeric material. In at least one embodiment of the present disclosure, the residual viscous material is guar gum. The residual viscous material has a viscosity greater than the fracturing fluid. In at least one embodiment of the present disclosure, the residual viscous material is surrounding and/or adjacent to the proppants placed in the fractures.

The cleanup fluid acts, after the proppants have been placed in the fractures, to remove the residual viscous material. In one aspect of the invention, the cleanup fluid is mixed with the fracturing fluid. In at least one embodiment of the present disclosure, where a multi-stage fracturing fluid is used, the cleanup fluid is a component of the fluids used at each stage of the hydraulic fracturing operation. In an alternate embodiment, the cleanup fluid is added only to the fluid of the final stage of the hydraulic fracturing operation, such as, for example, the overflush stage. In another aspect of the invention, the cleanup fluid is pumped to the fractured formation as a separate step following the hydraulic fracturing operation.

The cleanup fluid includes at least one component (an acid precursor) and an exothermic reaction component. The reaction of the exothermic reaction component results in a release of kinetic energy and thermal energy. The reaction of the exothermic reaction component generates heat and increases the pressure. The generated heat increases the temperature of the surrounding fluids, including fracturing fluid remaining in the fractures and residual viscous material. The increase in temperature reduces the viscosity of the fracturing fluid. The increase in temperature reduces the viscosity of the residual viscous material left in the fractures to create a reduced viscosity material. The reduced viscosity material flows from the fractures of the formation to the wellbore. The increase in pressure provides lift energy to push the reduced viscosity materials through the wellbore toward the surface. The removal of the residual viscous material increases the conductivity of the fractures. Increased conductivity of the fractures increases seepage of the fracturing fluid, improves fracturing efficiency, minimizes need for additional fracturing jobs, minimizes time between fracturing and well production, and increases hydrocarbon flow, which translates to increased hydrocarbon recovery.

The at least one component (acid precursor) comprises triacetin (1,2,3-triacetoxypropane). Those skilled in the art will appreciate that other suitable acid that releases hydrogen ions to trigger the reaction of the exothermic reaction component may be used, such as methyl acetate, HCl, and acetic acid. In at least one embodiment, the acid precursor is triacetin. In at least one embodiment, the acid precursor further comprises acetic acid.

The exothermic reaction component includes one or more redox reactants that exothermically react to produce heat and increase pressure, selected from the group consisting of urea, sodium hypochlorite, ammonium containing compounds, and nitrite containing compounds. In at least one embodiment of the present disclosure, the exothermic reaction component includes ammonium containing compounds. Ammonium containing compounds include ammonium chloride, ammonium bromide, ammonium nitrate, ammonium sulfate, ammonium carbonate, and ammonium hydroxide.

In at least one embodiment, the exothermic reaction component includes nitrite containing compounds. Nitrite containing compounds include sodium nitrite and potassium nitrite. In at least one embodiment, the exothermic reaction component includes both ammonium containing compounds and nitrite containing compounds. In at least one embodiment, the ammonium containing compound is ammonium chloride, NH₄Cl. In at least one embodiment, the nitrite containing compound is sodium nitrite, NaNO₂.

In at least one embodiment of the present disclosure, the exothermic reaction component includes two redox reactants: NH₄Cl and NaNO₂, which react according to the following: <chemistry id="chem0001" num="0001"><img file="EP3132000B1_D0001.tif" /></chemistry>

In a reaction of the exothermic reaction components according to the above equation, generated gas and heat contribute to the reduction of the viscosity of the residual viscous material.

The exothermic reaction component is triggered to react. In at least one embodiment of the present disclosure, the exothermic reaction component is triggered within the fractures. In at least one embodiment of the present disclosure, the at least one component (acid precursor) triggers the exothermic reaction component to react by releasing hydrogen ions.

In at least one embodiment, the exothermic reaction component is triggered by heat. The wellbore temperature is reduced during a pre-pad injection or a pre-flush with brine and reaches a temperature below 120°F (48.9°C). The fracturing fluid of the present disclosure is then injected into the well and the wellbore temperature increases. When the wellbore temperatures reaches a temperature greater than or equal to 120°F (48.9°C), the reaction of the redox reactants is triggered. The reaction of the redox reactants may be triggered by temperature. The exothermic reaction component may be triggered by heat when the exothermic reaction component is within the fractures.

The exothermic reaction component may be triggered by pH. A base is added to the fracturing fluid of the present disclosure to adjust the pH to between 9 and 12. In at least one embodiment, the base is potassium hydroxide. The fracturing fluid with the base is injected into the formation. Following the injection of the fracturing fluid, an acid is injected to adjust the pH to below 6. When the pH is below 6, the reaction of the redox reactants is triggered. In at least one embodiment, the exothermic reaction component is triggered by pH when the exothermic reaction component is within the fractures.

In an aspect of the present invention, the cleanup fluid is introduced to the fractures following the hydraulic fracturing operation. Dual-string coiled tubing may be used to introduce the exothermic reaction component and the acid precursor to the wellbore. In at least one embodiment, the exothermic reaction component includes NH₄Cl and NaNO₂. Described herein, but not forming part of the present invention, are methods wherein the acid precursor is acetic acid, wherein the acetic acid is mixed with NH₄Cl and injected in parallel with the NaNO₂, using different sides of a dual-string coiled tubing, wherein the exothermic reaction component and the acid precursor mix within the fractures.

EXAMPLES

Example 1. An exothermic reaction component of a cleanup fluid consisting of 3M NH₄Cl and 3M NaNO₂ was added to a solution of 1% by volume guar at room temperature, see <figref idref="f0003">FIG. 3</figref>. The exothermic reaction component was triggered by heat. The viscosity of the solution was measured before, during, and after the reaction using a Chandler viscometer. Prior to reaction of the exothermic reaction component, the viscosity of the residual viscous material was 85 cP. <figref idref="f0001">FIG. 1</figref> is a graph of the viscosity following the reaction of the exothermic reaction component. The graph shows that the viscosity of the residual viscous material was reduced to less than 8.5 cP. <figref idref="f0003">FIG. 3b</figref> shows the solution, including the residual viscous material after the reaction of the exothermic reaction component.

Example 2. A solution of an exothermic reaction component was prepared from 3M NH₄Cl and 3M NaNO₂. The solution was placed in an autoclave reactor at room temperature and an initial pressure of 1,000 psi (6894 kPa). The reactor temperature was increased. The reaction was triggered at about 120°F (48.9°C), see <figref idref="f0002">FIG. 2</figref>. Due to the reaction, the temperature in the reactor reached a temperature of 545°F (285°C) and a pressure of 3,378 psi (23290 kPa), see <figref idref="f0002">FIG. 2</figref>.

Example 3. The exothermic reaction component showed compatibility with the viscous fluid component (here an x-linked gel). The fracturing fluid with the viscous fluid component, the exothermic reaction component, and the proppant component was also prepared and showed compatibility. The fracturing fluid, without the proppant component, was activated in the autoclave reactor by heating to the wellbore temperature to trigger the reaction of the exothermic reaction component. The heat generated by the reaction reduced the viscosity of the viscous fluid component to produce a reduced viscosity material, without injecting the viscosity breaker. Using a chandler viscometer, the viscosity of the fracturing fluid, containing the viscous fluid component and the exothermic reaction component, was measured pre-reaction and post-reaction. The viscosity of the fracturing fluid was reduced from 1600 cp to 10 cp, as shown in <figref idref="f0004">FIG. 4</figref>. The results show that the exothermic reaction component and this type of treatment can clean-up the fractures post a fracturing job.

The singular forms "a," "an," and "the" include plural referents, unless the context clearly dictates otherwise.

Optional or optionally means that the subsequently described event or circumstances can or may not occur. The description includes instances where the event or circumstance occurs and instances where it does not occur.

Throughout this application, where patents or publications are referenced, the disclosures of these references are intended to more fully describe the state of the art to which the disclosure pertains, except when these references contradict the statements made herein.

As used herein and in the appended claims, the words "comprise," "has," and "include" and all grammatical variations thereof are each intended to have an open, nonlimiting meaning that does not exclude additional elements or steps.

As used herein, terms such as "first" and "second" are arbitrarily assigned and are merely intended to differentiate between two or more components of an apparatus. It is to be understood that the words "first" and "second" serve no other purpose and are not part of the name or description of the component, nor do they necessarily define a relative location or position of the component. Furthermore, it is to be understood that that the mere use of the term "first" and "second" does not require that there be any "third" component, although that possibility is contemplated under the scope of the present disclosure.