Controlling iron in aqueous well fracturing fluids

Abstract: Ferric iron contained in a fracturing fluid is prevented from precipitating or otherwise disadvantageously reacting by adding a thioalkyl acid compound to the fracturing fluid. The thioalkyl acid compound reduces ferric ion to ferrous ion which remains in solution at pH levels below about 7.5. The thioalkyl acid compound has the formula: where n is an integer from 1 to 10; Z is R or M; R is hydrogen, -(CH₂) x CH₃,-CH₂COOH or -(CH₂) x C₆H₅ wherein x is 0 or an integer from 1 to 6; M is sodium, potassium, ammonium, calcium, magnesium or H₃N⁺OH; and d is 1 when Z is R, or d is 1 or 2 when Z is M to match the valence of M.

Description: This invention broadly relates to fracturing subterranean well formations to stimulate the production of oil and/or gas therefrom and, more particularly, to controlling iron in aqueous well fracturing fluids to prevent the formation of iron precipitates therein as well as to prevent other undesirable iron reactions. The stimulation of oil and/or gas production from subterranean formations by fracturing the formations is well known to those skilled in the art. Generally, a fracturing procedure is carried out by pumping a fracturing fluid into the formation at a rate and pressure such that the formation is hydraulically fractured. The fractures are extended in the formation by continued introduction of fracturing fluid therein, and the fractures so formed are often propped open by propping agent, e.g. sand, deposited therein. Also, depending upon the type of rock making up the formation, the fracture faces can be etched with acid to form flow channels therein. Once the fractures have been formed, propping agent has been deposited therein and/or flow channels have been formed in the faces of the fractures, the hydraulic pressure exerted on the formation is released which causes the fracturing fluid to reverse flow out of the formation and the fractures to close leaving permeable passages therein through which oil and/or gas flows from the formation to the wellbore. A problem which can be encountered if the fracturing fluid contains dissolved iron is the precipitation of iron compounds such as ferric hydroxide therefrom. Such precipitates can plug or reduce the permeability of the fractured formation whereby the fracturing procedure results in a reduction of oil and/or gas production instead of an increase of such production. Another problem which can be caused by the presence of dissolved iron in a fracturing fluid comprised of a gelled aqueous polymer solution is the undesirable ferric ion cross-linking of the hydrated polymer whereby the viscosity of the fracturing fluid is undesirably increased and/or inconsistent. While iron precipitate control additives have been developed and used heretofore, the presence of such additives in viscosified aqueous fracturing fluids can significantly hasten the destruction of the viscosifying hydrated polymer in the fluids and prevent or impede the successful completion of a fracturing procedure. We have now devised an improved method of controlling iron in an aqueous fracturing fluid whereby ferric ion therein is reduced to ferrous ion which remains in the fracturing fluid without precipitates being produced therefrom. According to the present invention, there is provided a method of controlling iron in an aqueous fracturing fluid having a pH below 7.5, which method comprises adding a ferric ion reducing agent to said fracturing fluid in an amount sufficient to reduce ferric ion contained therein to ferrous ion, said ferric ion reducing agent being a compound of the general formula: wherein n is an integer from 1 to 10; Z is R or M; R is hydrogen, -(CH 2 ) x CH 3 ,-CH 2 COOH or -(CH 2 ) x C 6 H 5 wherein x is 0 or an integer from 1 to 6; M is sodium, potassium, ammonium, calcium, magnesium or H 3 N + OH; and d is 1 when Z is R, or d is 1 or 2 when Z is M to match the valence of M. By the method of the invention, iron contained in an aqueous fracturing fluid having a pH below about 7.5 is controlled by adding a ferric ion reducing agent to the fracturing fluid in an amount sufficient to prevent the precipitation of ferric compounds or the undesirable cross-linking of polymer in the fracturing fluid. Also, the ferric ion reducing agents of this invention generally do not bring about fracturing fluid viscosity loss to as great a degree as prior art iron control agents used heretofore. The term "controlling" and similar terms when used herein in relation to iron contained in a fracturing fluid mean that ferric iron is reduced to ferrous iron and the pH of the fracturing fluid is maintained below about 7.5 whereby ferrous iron precipitates are not formed. Ferric iron can find its way into aqueous fracturing fluids in various ways, the most common of which are by way of the water used in forming the fracturing fluid or by the reaction of the formed fracturing fluid with iron containing compounds in the formation being fractured. When ferric iron (+3 oxidation state) exists in the fracturing fluid, it starts to form ferric hydroxide precipitate when the pH of the fluid increases to about 2.5, and it is completely precipitated when the pH reaches about 3.5. Ferrous iron (+2 oxidation state) on the other hand, remains in solution to a pH up to about 7.5. The fracturing fluid compositions of this invention are basically comprised of an aqueous solution, e.g. a gelled aqueous polymer solution or a cross-linked gelled aqueous polymer solution, and the ferric ion reducing agent. The compositions may also include one or more buffering agents to help maintain the pH of the fracturing fluid below about 7.5, preferably in the pH range of from about 1 to about 5. In addition, the compositions can include one or more other agents often added to well treatment fluids including additives for removing oxygen therefrom. Also, when the formation being fractured contains reactive sulfides, the fracturing fluid can include one or more agents for preventing the precipitation of ferrous sulfide. A preferred ferric iron reducing agent is a compound of the above formula wherein n is 1, d is 1 and Z is R. The most preferred ferric iron reducing agent is thioglycolic acid. Other reducing agent which may be used include, for example, α-methylthioglycolic acid, methylthioglycolate, α,α-dimethylthioglycolic acid, α-phenylthioglycolic acid, methyl-α-methylthioglycolate, benzylthioglycolate, α-benzylthioglycolic acid, ammonium thioglycolate, hydroxylammonium thioglycolate, calcium dithioglycolate, β-thiopropionic acid, methyl-β-thiopropionate, sodium-β-thiopropionate and thiomalic acid. The amount of ferric ion reducing agent effective to reduce substantially all of the ferric ion contained in, or to be contained in, a fracturing fluid composition of this invention depends on the temperature of the reduction reaction environment. A satisfactory rate of reduction is provided by an amount of ferric ion reducing agent which will produce the required reduction in about 1 hour. Generally, the ferric ion reducing agent is combined with a fracturing fluid in a minimum amount of about 0.01% by volume of the fracturing fluid to a maximum amount of about 8% by volume of the fracturing fluid. A variety of aqueous solutions can be utilized for forming the fracturing fluid compositions of this invention. Generally, the aqueous solution is comprised of water having one or more viscosity increasing hydratable polymers dissolved therein. Examples of commonly utilized such polymers are polysaccarides including galactomannan polymers, glucomannan polymers and their derivatives. Typical of such polymers are guar gum and guar derivatives and modified cellulose such as hydroxyethylcellulose, carboxymethylcellulose, xanthan gum and other cellulose derivatives. Synthetic polymers can also be utilized examples of which include polyacrylamides, poly-2-amino-2-methyl propane sulfonic acid and others. The polymer is generally present in the aqueous solution in an amount in the range of from about 0.1% to about 2% by weight of solution to thereby produce a gelled aqueous polymer fluid having an apparent viscosity in the range of from about 2 cp to about 200 cp as determined using a Fann Model 50 viscometer. The particular concentration of the polymer depends upon the conditions of the well to be fractured and other factors well known to those skilled in the art. As mentioned above, aqueous polymer solutions can be cross-linked to increase their viscosity by adding a cross-linking compound thereto. Typical such cross-linking compounds are organic chelates of titanium, zirconium, aluminum or other multivalent metals. The selection of an appropriate cross-linking compound depends upon the particular polymer used, and the amount of cross-linking compound depends upon the well conditions and other factors. Generally, a cross-linking compound is added to an aqueous polymer solution in an amount in the range of from about 0.0005% to about 1.2% by weight of the solution to produce a cross-linked gelled aqueous polymer fluid having a viscosity in the range of from about 40 cp to about 6000 cp(.04 to 6 Pa s) as determined using a Fann Model 50 viscometer. As mentioned above, the gelled aqueous polymer fracturing fluid and/or gelled aqueous cross-linked polymer fracturing fluid must have a pH below about 7.5 to prevent the precipitation of ferrous compounds therefrom. The pH of the fracturing fluid composition can be adjusted if necessary using acids, buffering agents and mixtures of acids and bases. Preferably, the pH of the fracturing fluid is adjusted to a level in the range of from about 1 to about 5 and a buffering agent selected from the group consisting of carbon dioxide, organic acids, e.g., acetic or formic acid, acid salts, e.g., ammonium bisulfite and inorganic acids, e.g., hydrochloric acid or sulfuric acid is added to the fracturing fluid to maintain the pH within that range. The most preferred buffering agent is formic acid. Other components and additives that can be combined with the compositions of the present invention include acids, sulfide reactants or scavengers such as aldehydes or ketones, surfactants, corrosion inhibitors, fluid loss additives, biocides, non-emulsifying agents and mutual solvents. 'Such components and additives are well known to those skilled in the art, and their use depends on the conditions of the subterranean formation to be fractured and other factors. In order to further illustrate the methods and compositions of the present invention, the following examples are given. Example 1 A quantity of an aqueous treatment fluid recovered from the Antrim Shale formation containing ferric hydroxide precipitate (90 ppm ferric ion) was obtained having a pH of 6.26. The aqueous suspension of ferric hydroxide was divided into samples and various iron control additives including a ferric ion reducing agent of this invention were added to the samples in quantities equivalent to 20 pounds (9.06kg)of additive per 1000 U.S. gallons (3.79m 3 ) of aqueous suspension. The ferric ion reducing agent of the present invention used was thioglycolic acid and the other additives were prior art iron control additives, namely, citric acid, hydroxylamine and the ferric ion reducing composition described in United States Patent No. 4,683,954 issued on August 4, 1987, i.e., a mixture of hydroxylamine hydrochloride, gluconodeltalactone and a catalytic amount of cuprous ion. The samples containing the additives were heated from ambient to 125°F (51°C) over a time period of about 1 hour. None of the prior art additives reacted with the aqueous ferric hydroxide suspension which retained its original opaque orange color. The sample to which the thioglycolic acid was added reacted whereby the ferric ion in the precipitate was reduced to ferrous ion and dissolved. As the reaction took place, the suspension was converted from opaque orange to a clear colorous solution. Example 2 An aqueous fracturing fluid containing a guar gum viscosifying polymer in an amount of about 0.36% by weight of the aqueous polymer solution was prepared having a viscosity of 19.5 cp(.0195 Pa s) as determined by a Fann Model 50 viscometer. The polymer solution was divided into two test samples, to one of which was added thioglycolic acid in an amount of 0.05% by weight of the resulting solution. The ferric ion reducing composition described in U.S. Patent No. 4,683,954 issued on August 4, 1987, i.e., a mixture of hydroxylamine hydrochloride, gluconodeltalactone and a catalytic amount of cuprous ion was added to the other polymer solution sample in an amount of about 0.12% by weight of the resulting solution. The viscosities of the test samples containing the additives were continuously monitored over time after the addition of the additives utilizing a Fann Model 50 viscometer at 300 rpm. The results of the tests are set forth and compared in the Table below. Additive Effect on Fracturing Fluid Viscosity Additive Additive Quantity, % by wt. Initial Viscosity, cp (Pa s) 4 min. 5 min. 7 min. 9 min. 15 min. 20 min. 25 min. 30 min. Additive of this Invention 0.36 19.5 (.0195) 19.5 (.0195) 19.0 (.019) 19.0 (.019) 19.0 (.019) 18.5 (.0185) 18.5 (.0185) 18.0 (.018) 18.0 (.018) Prior Art Additive 0.36 19.5 (.0195) 19.0 (.019) 18.5 (.0185) 18.0 (.018) 17.5 (.0175) 15.5 (.0155) 14.0 (.014) 12.0 (.012) 11.0 (.011) From Table I it can be seen that the ferric ion reducing additive of the present invention causes viscosity reduction to a substantially lesser degree than does the prior art additive tested.

Claims: A method of controlling iron in an aqueous fracturing fluid having a pH below 7.5, which method comprises adding a ferric ion reducing agent to said fracturing fluid in an amount sufficient to reduce ferric ion contained therein to ferrous ion, said ferric ion reducing agent being a compound of the general formula: wherein n is an integer from 1 to 10; Z is R or M; R is hydrogen, -(CH 2 ) x CH 3 ,-CH 2 COOH or -(CH 2 ) x C 6 H 5 wherein x is 0 or an integer from 1 to 6; M is sodium, potassium, ammonium, calcium, magnesium or H 3 N + OH; and d is 1 when Z is R, or d is 1 or 2 when Z is M to match the valence of M. A method according to claim 1, wherein the reducing agent is added to the aqueous fracturing fluid in an amount of from 0.01% to 8% by volume of said fracturing fluid. A method according to claim 1 or 2, wherein n is 1, d is 1 and Z is R. A method according to claim 1,2 or 3, wherein the reducing agent is thioglycolic acid. A method according to claim 1, 2, 3 or 4, wherein the aqueous fracturing fluid is a gelled aqueous polymer solution, a cross-linked gelled aqueous polymer solution, or an emulsion or foam containing a gelled aqueous polymer solution or cross-linked gelled aqueous polymer solution. A method according to claim 5, wherein the fracturing fluid is a gelled aqueous polymer solution containing polymer in an amount of from 0.1% to 2% by weight of said solution. A method according to any of claims 1 to 6, which further comprises adding a buffering agent to the fracturing fluid to maintain the pH of said fracturing fluid in the range from 1 to 5. A method according to claim 7, wherein the buffering agent is carbon dioxide, an organic acid, an acid salt or an inorganic acid. A method according to claim 8, wherein the buffering agent is formic acid. A method of fracturing a subterranean well formation wherein there is used a fracturing fluid made by the method of any of claims 1 to 9.

Inventors: BREZINSKI MICHAEL, GARDNER TOMMY R, HARMS WELDON M, KING KAREN L, LANE JR JAMES L, BREZINSKI, MICHAEL, GARDNER, TOMMY R., HARMS, WELDON M., KING, KAREN L., LANE, JR., JAMES L.
Applicants: HALLIBURTON ENERGY SERV INC, HALLIBURTON ENERGY SERVICES, INC.
Application year: 1993
Main classification: E21B43
IPC codes: C09K8, E21B43