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    • 专利摘要:
    UNDERGROUND TREATMENT METHODTreatment fluids containing biodegradable chelating agents and methods for using them are described. The methods may comprise providing a treatment fluid comprising an aqueous based fluid and a chelating agent composition and introducing the treatment fluid into at least a portion of an underground formation. Treatment fluids can also be used for the treatment of tubes or pipes such as, for example, well bore tubes or pipes that penetrate an underground formation and above-ground pipelines. Illustrative biodegradable chelating agents include, but are not limited to, glutamic acid diacetic acid, diacetic acid methylglycine, beta-alanine diacetic acid, S, S-ethylene diaminodisuccinic acid, iminodi-succinic acid, hydroxyiminodisuccinic acid, any salt thereof, any derivative thereof of them and any combination of them. Treatment fluids can optionally comprise an acid, which can include hydrofluoric acid or a compound that generates hydrofluoric acid.
    公开号:BR112013026091A2
    申请号:R112013026091-2
    申请日:2012-04-26
    公开日:2020-07-21
    发明作者:Enrique A. Reyes；Thomas D. Welton
    申请人:Halliburton Energy Servicer, Inc.；
    IPC主号:
    专利说明:

    “UNDERGROUND TREATMENT METHOD”
    CROSS REFERENCE TO RELATED APPLICATIONS This application claims priority of 13 / 094,248, which is partly a continuation of United States Patent Application pending 13 / 051,827, filed on March 18, 2011 and currently pending, which is partly a continuation of United States Patent application 11 / 499,447, filed on August 4, 2006 and currently pending, each of which is incorporated herein by reference in its entirety whether or not expressly presented here.
    BACKGROUND The present invention generally relates to treatment fluids that contain chelating agents and, more particularly, to treatment methods using treatment fluids that contain biodegradable chelating agents.
    Treatment fluids can be used in a variety of underground treatment operations. Such treatment operations may include, without limitation, drilling operation, stimulation operations, production operations and sand control treatments. As used herein, the terms "treat," "treatment" and "treating" refer to any operation - underground that uses a fluid in conjunction with obtaining a desired function and / or for a desired purpose. The use of these terms does not imply any particular action by the treatment fluid. Illustrative treatment operations may include, for example, fracture operations, gravel sealing operations, acidification treatments, scale dissolution and removal, consolidation treatments and the like. In alternative embodiments, treatment operations may refer to an operation conducted on a tube, pipe, or similar vessel in conjunction with obtaining a desired function and / or for a desired purpose (for example, removal of scale) .
    In acidification treatments, for example, underground formations comprising acid-soluble components, such as those present in carbonate and sandstone formations, are contacted with a treatment fluid comprising an acid to dissolve the forming matrix. After acidification is completed, the treatment fluid and salts dissolved in it can be recovered by transporting them to the surface (for example, "backflowing" the well), leaving a desired amount of voids or conductive paths (for example, wormhole carbonates) within the formation. Acidification can enhance the permeability of the formation and can increase the rate at which hydrocarbons are subsequently produced from the formation.
    The acidification of a siliceous formation (for example, a sandstone formation or a formation containing clay) must be distinguished from the acidification of a carbonate formation. Carbonate formations can be treated with a variety of acid systems, including mineral acids (eg hydrochloric acid) and organic acids (eg acetic and formic acids), often with similar success, where the acidity of the treatment fluid alone may be sufficient to solubilize the formation cations. The treatment of silica formations with those acids, however, may have little or no effect because they do not react appreciably with the silica and silicates that characterize silica formations. As used herein, the term "siliceous" refers to the characteristic of having silica and / or silicate, including aluminosilicates. Most of the sandstone formations are composed of about 40% to about 98% of sand quartz particles, that is, silica (SiO »), bonded together by various amounts of cementitious material including carbonate (calcite or CaCO; ), aluminosilicates and silicates.
    Decidedly the most common method of treating sandstone and other siliceous formations involves introducing corrosive, very low pH acids that comprise hydrofluoric acid into the well bore and the acid that follows to react with the forming matrix.
    In contrast to other mineral acids, hydrofluoric acid is very reactive with aluminosilicates and silicates (for example, sandstone, clays and feldspars). Hydrochloric acid can be used in addition to hydrofluoric acid in the treatment fluid to maintain a low pH as hydrofluoric acid is spent during a treatment operation, thereby retaining certain species dissolved in a highly acidic solution.
    Hydrofluoric acid acidification is often used to remove damage within the formation.
    Such treatments are generally not considered "stimulating" in the sense of creating or prolonging fractures in the formation as in a typical fracture operation.
    As a result of treatment with hydrofluoric acid, it is desired that the coating value in the formation is zero.
    It is not expected that it will be less than zero.
    Any damage left behind is a positive coating value, which is not desirable.
    Hydrofluoric acid can interact with the formation matrix, basic fluids, or formation fluids to create precipitates, particularly in the presence of metal fons such as AIlº **, Fe **, Group 1 metal ions (for example, Na * and K *) and / or Group 2 metal ions (for example, Mg *, Ca ** and Ba **), thereby leading to another damage and a positive coating value.
    For example, hydrofluoric acid tends to react — very quickly with autogenic clays (eg smectite, kaolinite, illite and chlorite) especially at temperatures above 200º F [93º C] and below pH 1, as a function of mineral surface area .
    Because of this rapid reaction, hydrofluoric acid can only penetrate a short distance in the formation before it becomes spent.
    Simultaneously, - precipitation of various aluminum and silicon complexes can occur as a result of the reaction of the acid with siliceous minerals.
    The damage to the formation can result from this precipitation.
    Under certain temperatures and underground conditions, the dissolution of a sandstone matrix or as siliceous material can occur so quickly that uncontrolled precipitation can become an inevitable problem. Precipitation products can plug the pore spaces and reduce the porosity and permeability of the formation, thus impairing the flow potential.
    Because clays are usually a part of the cementitious materials that hold grains of sand of siliceous formations together, the dissolution of clay also weakens and deconsolidates the formation matrix in the vicinity of the well bore, thus causing damage to the formation. The harmful effects due to both the deconsolidation of the matrix and the precipitation of complexes can clog the formation pore spaces and eliminate or even —reverse effect of the stimulation of an acidification treatment.
    Of particular interest is the formation of calcium fluoride, fluorosilicates, or other insoluble fluorine compounds during treatment with acidifying hydrofluoric acid, which can neutralize the effectiveness of the treatment and cause damage to the formation. This can lead to production delays while damage control operations are conducted. Fluorosilicates may be of particular interest because they are the primary product of dissolving a clay and hydrofluoric acid. In addition, fluorosilicates are difficult to remedy. Calcium fluoride can be a later problem in the process, because the fluoride anion needs to be present in its free phon form and what does not happen until a higher pH is reached. Calcium fluoride can be remedied in some cases. Remediation techniques include a commercially available treatment system from Halliburton Energy Services, Inc. known as the “F-SOL” acid system, which can be used to dissolve calcium fluoride. Another source of the problem is the production of fluoroaluminates as a consequence of the reaction of fluorosilicates with clay minerals. Fluoroaluminates are considered to be soluble as long as the pH is below about 2 and the F / Al ratio is kept below about 2.5. If precipitated, its dissolution requires strong HCl (> 5%).
    Avoiding the formation of calcium fluoride, fluorosilicates, or other insoluble fluorine compounds can be a primary design goal in a treatment operation conducted in an underground formation or elsewhere. Various means have been used with mixed success. Mixtures of organic acids and hydrofluoric acid were used to decrease the rate of solids dissolution kinetics in the formation of sandstone. However, since organic acids have higher pKa values than mineral acids, precipitation can become problematic as the pH of the treatment fluid rises. Pre-flow sequences with acids were used to remove calcium salts from sandstone formations, before the main acidifying sequence was conducted to remove aluminosilicates from the formation. In general, these flows are not completely consumed and typically return, in the retroflow, with a low persistent pH. This can result in corrosion of tubular articles down the hole (including spiral pipes) and surface equipment. Other multi-stage sandstone acidification treatment operations have also been developed, particularly to remove calcium fons. Chelating agents can also be included in the treatment fluids to sequester at least a portion of the formation cations that cause unwanted precipitation. However, there are certain operational problems that are encountered with the use of many common chelating agents. First, many common chelating agents are not biodegradable or have other toxicity problems that make their use in an underground formation problematic. In addition, the salt form of some chelating agents can actually exacerbate precipitation problems in an acidification treatment with hydrofluoric acid instead of decreasing the amount of precipitated solid.
    Likewise, chelating agents can be used in the treatment of pipelines, pipes and similar vessels by removing the metal ion crust from the surface of pipelines or pipes. In such treatment operations, problems with the disposal of significant waste can be encountered, since chelating agents that are commonly used for such purposes are not biodegradable.
    In addition to the foregoing, precipitation of formation cations in matrix acidification operations can also be problematic even when non-silica portions of an underground formation are being treated. Although most formation cations can be dissolved with strong acid treatment fluids, dissolving the formation matrix wears off the acid. As the pH of the treatment fluid rises, certain cations can precipitate and damage the formation. In addition, the use of very strong acids in an underground formation can lead to borehole corrosion problems, as previously mentioned. These problems can also be encountered when treating similar pipelines, pipes and vessels with an acidic fluid. The sequestering of precipitable cations in non-silica formations or in pipelines, pipes, or similar vessels can likewise benefit from a chelating agent in much the same way as described above for silica formations by maintaining the cation in a soluble state in a wide range of HP.
    SUMMARY OF THE INVENTION The present invention generally relates to treatment fluids that contain chelating agents and, more particularly, to treatment methods that use treatment fluids that contain biodegradable chelating agents.
    According to an aspect of the invention there is provided a method which comprises: providing a treatment fluid comprising: an aqueous based fluid; and a chelating agent composition that comprises at least one chelating agent selected from the group consisting of methylglycine diacetic acid, diacetic B-alanine, ethylene diaminodisuccinic acid, S, S-ethylene-diaminodisuccinic acid, iminodisuccinic acid, hydroxyminodi-succinic acid, disuccinic polyamino, N-bis [2- (1,2-dicarboxy-ethoxy) ethylglycine, N-bis [2- (1,2- - dicarboxyethoxy) ethyl-aspartic, N-bis [2- (1,2-dicarboxyetoxy) ethyl Jmethylglycine, N-tris [(1,2-dicarboxyethoxy) -ethyl amine, N-methyliminodiacetic acid, iminodiacetic acid, N- (2-acetamido) iminodiacetic acid, hydroxymethyliminodiacetic acid, 2- (2-carboxyethylamino) succinic acid, 2- (2-carboxymethylamino) succinic, diethylenetriamino-N, N ”-dissuccinic acid, triethylenetetramino-N, N” ”- disuccinic acid, 1,6-hexamethylenediamino-N, N'-disuccinic acid, tetraethylenopentamino-N, N ”” - disuccinic, 2-hydroxy-propylene-1,3-diamino-N, N'-disuccinic acid, 1,2-propylene-diamino-N, N'-disuccinic acid, 1,3-propylenediamino-N, N'- disuccinic acid, cis-cyclohexanediamino-N, N-disuccinic acid, trans-cyclohexane-diamino-N, N'-disuccinic acid, ethylenebis (oxyethylenonitrile) - N, N-disuccinic, glycoeptanoic acid, N-cystic acid, N-diacetic acid, cystic-N-monoacetic acid, alanine-N-monoacetic acid, N- (3-hydroxysuccinyl) aspartic acid, N- [2- (3-hydroxysuccinyl)] - 1-serine, N-aspartic acid, N-diacetic acid, aspartic-N-acid - mono-acetic acid, any salt thereof, any derivative thereof and any combination thereof; and introducing the treatment fluid into at least a portion of an underground formation.
    According to another aspect of the invention there is provided a method which comprises: providing a treatment fluid comprising: an aqueous based fluid; and a chelating agent composition comprising at least one chelating agent selected from the group consisting of diacetic methylglycine acid, any salt thereof, any derivative thereof and any combination thereof; and introducing the treatment fluid into at least a portion of an underground formation.
    According to another aspect of the invention there is provided a method which comprises: providing a treatment fluid comprising: an aqueous based fluid; and a chelating agent composition comprising at least one chelating agent selected from the group consisting of glutamic acid diacetic acid, diacetic acid methylglycine, fB-alanine diacetic acid, ethylenediamine diisuccinic acid, S, S-ethylenediamine diucuccinic acid, iminodisuccinic acid, hydroxyiminic acid polyamino disuccinic acids, N-bis [2- (1,2-dicarboxyethoxy) ethyl] glycine, N-bis [2- (1,2-dicarboxyethoxy) ethyl Jasperic acid, N-bis [2- (1,2 -dicarboxy-ethoxy) ethyl | Jmethylglycine, N-tris [(1,2-dicarboxyethoxy) ethyl Jamina, Nmethyliminodiacetic acid, iminodiacetic acid, N- (2-acetamido) -iminodiacetic acid, hydroxymethyl-iminodiacetic acid, 2- (2 -carboxy-ethylamino) succinic acid, 2- (2-carboxymethylamino) succinic acid, diethylenetriamine-N, N ”-dissuccinic acid, triethylenetetramino-N, N” ”- disuccinic acid, 1,6-hexamethylenediamino-N, N'- disuccinic, tetraethylenepentamino-N, N'-disuccinic acid, 2-hydroxypropylene-1,3-diamino-N, N ' -dissuccinic, 1,2-propylenediamino-N, N'-disuccinic acid, 1,3-propylenediamino-N, N'- disuccinic acid, cis-cyclohexanediamino-N, N '-dissuccinic acid, trans-cyclohexanediaminoN, N' -dissuccinic, ethylenebis (oxyethylenonitrile) - N, N -dissuccinic, glycoeptanoic acid, N-cystic acid, N-diacetic acid, cystic acid-N-monoacetic acid, alanine-N-monoacetic acid, N- (3-hydroxy acid -succinyl) aspartic acid, N- [2- (3-hydroxysuccinyl)] - 1-serine, —aspartic-NN-diacetic acid, aspartic acid-N-acid - monoacetic, any salt thereof, any derivative thereof and any combination thereof; and treating a tube or pipes with the treatment fluid.
    According to another aspect of the invention there is provided a method which comprises: providing a treatment fluid comprising: an aqueous based fluid; and a chelating agent composition comprising at least one chelating agent selected from the group consisting of glutamic acid diacetic acid, any salt thereof, any derivative thereof and any combination thereof; and introducing the treatment fluid into at least a portion of an underground formation. The features and advantages of the present invention will be readily apparent to a person of ordinary skill in the art at a reading of the description of the preferred embodiments which follow.
    BRIEF DESCRIPTION OF THE DRAWINGS The following figure is included to illustrate certain aspects of the present invention and should not be seen as an exclusive embodiment. The subject matter disclosed is capable of modification, alteration and considerable equivalents in form and function, as will occur to those skilled in the art and having the benefit of this disclosure. FIGURE 1 shows an analysis of fractional pore volume effluent.
    DETAILED DESCRIPTION The present invention generally relates to treatment fluids that contain chelating agents and, more particularly, to treatment methods that use treatment fluids that contain biodegradable chelating agents. There are many advantages of the present invention, only a few - few of which are discussed or alluded to here. The compositions and methods of the present invention use biodegradable chelating agents that can be used in conjunction with hydrofluoric acid or other matrix acidification treatments in underground formations that avoid many of the disadvantages associated with other chelating agents, including those discussed above.
    As used herein, the term "biodegradable" refers to a substance that can be decomposed by exposure to environmental conditions that include native or non-native microbes, sunlight, air, heat and the like.
    The use of the term “biodegradable” does not imply a particular degree
    - biodegradability, mechanism or biodegradability, or a specific biodegradation half-life.
    Because of the chelating effect, biodegradable chelating agents are able to help dissolve metal cations, thereby helping to prevent or remedy precipitates that can damage a formation or other surface.
    Additionally,
    - biodegradable chelating agents of the present invention can be used in an ammonium or tetraalkylammonium salt form, which has surprisingly been found to be particularly advantageous for acidification operations with hydrofluoric acid.
    The use of the ammonium or tetralkylammonium salt form can avoid the additional precipitation problems that can sometimes occur when other salt forms (for example, alkali metal salts) are used in the context of this invention.
    In addition, the biodegradable chelating agents and methods of the present invention can be used in preventive embodiments to prevent the formation of precipitates in the presence of hydrofluoric acid, such as
    - discussed above, as well as remediation methods to remove damage to a well bore or underground formation.
    These characteristics beneficially allow treatment fluids containing glutamic acid diacetic acid (“GLDA”) or other biodegradable chelating agents such as, for example, diacetic acid methylglycine
    (MGDA ”), (B-alanine diacetic acid (“ B-ADA ”) ethylenediaminodisuccinic acid, S, S-ethylenediaminodisuccinic acid (“ EDDS ”), iminodisuccinic acid (“ TDS ”), hydroxyiminodi-succinic acid (“ HIDS ”) , polyamine disuccinic acids, N-bis [2- (1,2-dicarboxyethoxy) ethyl] glycine (“BCA6”), N-bis [2- (1,2-dicarboxy-ethoxy) ethyl Jaspártico (“BCAS”) , N-
    bis [2- (1,2-dicarboxyetoxy) ethyl J] methyl-glycine (“MCBAS5”), N-tris [(1,2-dicarboxyethoxy) ethylJamine (“TCAG6”), N-methyliminodiacetic acid (“MIDA”) , —iminodiacetic acid (IDA ”), N- (2-acetamido) iminodiacetic acid (“ ADA ”), hydroxymethyliminodiacetic acid, 2- (2-carboxyethylamino) succinic acid ((CEAA”), 2- (2- carboxymethylamino) succinic (“CMAA”), diethylenetriamine-N, N ”-dissuccinic acid, triethylenetetramino-N, N” ”- disuccinic acid, 1,6-hexamethylenediamine-N, N'-disuccinic acid, tetraethylene-pentamine-N-pentamine , N ”” - disuccinic, 2-hydroxypropylene-1,3-diamino-N, N'-disuccinic acid, 1,2-propylenediamino-N, N'-disuccinic acid, 1,3-propylene diamine-N, N ' -dissuccinic, cyclichexanediamino-N, N -dissuccinic acid, trans-cyclohexanediamino-N, N'-disuccinic acid ethylenebis (oxyethylenonitrile) -N, N'-disuccinic acid, glycoeptanoic acid, cystic acid, N-dia-acid cysteine-N-monoacetic acid, alanine-N- monoacetic acid, N- (3-hydroxysuccinyl) asp arctic, N- [2- (3-hydroxysuccinyl) -l-serine, N-aspartic acid, N-diacetic acid, aspartic acid-N-acid = monoacetic, including any salt, derivative, or combination of these chelating agents, to carry out single stage treatment operations which include, for example, acidification treatments (for example, matrix acidification) and sealing sealing treatments, particularly in underground formations that have carbonates present especially those with> 10% carbonates.
    The beneficial effects can be particularly pronounced in treatment operations conducted using hydrofluoric acid or a compound that generates hydrofluoric acid.
    Likewise, beneficial effects can be observed when treating a tube, pipes, or similar vessel even when the pH is not particularly low.
    The treatment fluids of the present invention generally comprise an aqueous based fluid and at least one biodegradable chelating agent.
    Suitable biodegradable chelating agents can comprise GLDA, any GLDA salt, or any GLDA derivative.
    Suitable biodegradable chelating agents may also comprise MGDA, eDDS, IDS, HIDS, any salt thereof, any derivative thereof, or any combination thereof, which include combinations with GLDA, can be used in the treatment fluids.
    Likewise, any of the biodegradable chelating agents listed above can also be used in conjunction with the present invention.
    Particular advantages of some of these chelating agents are considered in more detail below.
    Optionally, salts, other additives —depH, corrosion inhibitors, surface active agents, anti-sludge agents, mutual solvents, scale inhibitors, viscosifiers, gases, fluid bypass / loss agents and the like can be included in fluids of treatment of the present invention.
    The present treatment fluids can be used in underground formations to prevent or remedy the precipitation of formation damage caused by the dissolution of formation cations, particularly in the presence of hydrofluoric acid.
    Likewise, the present treatment fluids can be used in the treatment of tubes, pipes and similar vessels.
    In general, the base fluid of the present invention can - comprise any aqueous or non-aqueous fluid.
    Preferably, the base fluid may comprise fresh water, brackish water (for example, water containing one or more salts dissolved in it), brine (for example, saturated brackish water), sea water, glycol, any combination thereof, or any derived from them.
    The base fluid can comprise a liquid chelating agent or fouling control agent by itself.
    In general, the base fluid can be from any source, as long as it does not contain components that would adversely affect the stability and / or performance of the treatment fluids of the present invention.
    The chelating agent compositions of the present invention generally comprise a biodegradable chelating agent, any salt thereof, or any derivative thereof. Examples of suitable derivatives of biodegradable chelating agents include alkylated esters and derivatives, for example. In general, any derivative can be used, provided that the derivative still maintains an affinity for bonding metal cations. Examples of suitable salts of biodegradable chelating agents include sodium salts, rubidium salts, lithium salts, potassium salts, cesium salts and ammonium salts, which include tetraalkylammonium salts. Mixed salt forms can also be used, if desired.
    GLDA is manufactured from a raw material that is easily biodegradable, renewable and consumable by humans, monosodium glutamate. In addition, GLDA is easily soluble in high concentrations over a wide pH range. In this regard, GLDA is considered to be superior to many other chelating agents. GLDA chelate metal ions such as, but not limited to, calcium, iron, aluminum and magnesium over a wide pH range and are highly soluble in aqueous treatment fluids.
    At present, GLDA is commercially available in its sodium salt form. Other forms of salt may be available non-commercially, or in smaller quantities, or they may be manufactured using —a phon exchange technique discussed below. The preferred form for use in conjunction with the embodiments described herein in which hydrofluoric acid or a compound that generates hydrofluoric acid is used is not the form of the monovalent metal salt (i.e., an alkali metal salt), but instead instead an ammonium salt or tetraalkylammonium from GLDA. A suitable commercial source of GLDA is a 47% by weight aqueous solution from Akzo-Nobel Corp. available under the brand “DISSOLVINE.” MGDA is also commercially available in its sodium salt form. A suitable commercial source of MGDA is a 40% by weight aqueous solution of the sodium salt form, sold by BASF under the brand name
    "TRILON M." Where a sodium salt of GLDA, MGDA, or any other biodegradable chelating agent is available, it may be desirable to exchange sodium cations for other cations such as, for example, potassium, ammonium or tetraalkylammonium cations. An ammonium or tetraalkylammonium salt is the preferred salt in the context of the present invention for treatment operations conducted on siliceous formations that include, for example, clays and sandstones in which hydrofluoric acid or a compound that generates hydrofluoric acid is used. In the case of carbonates, the potassium salt - may be preferred. The exchange of sodium cations for other cations can prevent the precipitation of compounds such as, for example, NaHSiF6ç. Cation exchange is considered to occur under conditions known to a person of ordinary skill in the art. Methods for exchanging sodium cations for potassium, ammonium, or tetraalkylammonium cations are considered to include, without limitation, phon exchange chromatography and selective precipitation techniques. Other means of exchanging sodium cations can be considered by a person having common skill in the technique. As discussed further below, it is considered that the exchange of at least a portion of the sodium cations can produce better solubility properties and beneficially improve other operational characteristics of a treatment fluid containing GLDA or another biodegradable chelating agent of the present invention.
    Lower concentrations of the free acid of the chelating agent can be produced under acidic conditions by diluting the acid in an appropriate volume of water. The amount to include will depend on the specific minerals and amount present in the underground formation and the purpose of use and the desired pH of the biodegradable chelating agent composition. Exemplary tracks are discussed below. The pH window for clays can be about | up to about 6. The pH window for clays can be from about 1.6 to about 4.5. The pH window for clays can be from about 1.5 to about 1.8. The pH window for clays can be from about 1.6 to about 3. The treatment fluid can have a pH ranging between about 1.5 and about 5, or the treatment fluid can have a pH that varies between about 1.5 and about 3. Particularly below these ranges, chelating agents - biodegradable can be ineffective for coordinating formation cations, as discussed below. When removing carbonate or carbonate crust, the pH of the treatment fluid can be from about 5 to about
    10. A preferred pH range for carbonate formations can be 6 to about 9. The pH will be dependent on what purpose the chelating agent will serve for the hole below. A person having common skill in the technique with the benefit of this disclosure will be able to select the appropriate pH for a given application.
    In embodiments in which a tube, pipe, or similar vessel is treated with the treatment fluids, higher pH values may be more advantageous due to the possibility of corrosion that occurs at lower pH values. The pH for treating a pipe, pipe, or similar vessel can vary between about 5 and about 10. Preferably, the pH can vary between about 5 and about 8 or between about 6 and about 8. Alternatively, the pH can be greater than about 8.
    - It should be mentioned that at these higher pH values, chelating agents will be significantly deprotonated and operable to chelate metal ions. For some applications such as, for example, the dissolution of barium scabs, particularly in a tube, pipe, or similar vessel, high pH values such as about 8 or above or about 10 or above can - be beneficial in that aspect.
    In addition to the intended function that the chelating agent will serve as a hole below, the acid dissociation constants of the chelating agent can dictate the pH range in which the treatment fluid can be most effectively used. GLDA, for example, has a pK value of about 2.6 for its more acidic carboxylic acid functionality. Below a pH value of around 2.6, dissolution of the formation cations will be promoted primarily by the acidity of a treatment fluid containing GLDA, rather than by chelation, since the chelating agent will be in a fully protonated state. . MGDA, in contrast, has a pK value, in the range of about 1.5 to 1.6 for its most acidic carboxylic acid group and will not become fully protonated until the pH is lowered to below about 1 , 5 to 1.6. In this respect, MGDA is particularly beneficial for use in acidic treatment fluids, as it extends the acidity range by almost a full pH unit above which the chelating agent is an active chelator. The lower pH of the treatment fluid beneficially allows a more vigorous acidification operation to occur. For comparison purposes, the dissociation constant for EDDS acid (2,4) is comparable to that for GLDA.
    Of the biodegradable chelating agents described herein, GLDA and MGDA are currently available from commercial sources in bulky quantities with a reliable supply chain. From a supply point of view, these biodegradable chelating agents are therefore preferred. For the reasons mentioned above, - these chelating agents are operable in a different range of pH values and they are complementary to each other in this regard. In addition to their pH complementarity, the biodegradable chelating agents described here may have the ability to form selective chelate with different metal fons, both as an inherent stability of the —chelate and a rate of kinetic / thermodynamic formation as a function of pH. In this regard, other biodegradable chelating agents that are less readily available from commercial sources such as, for example eDDS, B-ADA, IDS and / or HIDS can be used alone or combined with GLDA or MGDA in order to "focus" the chelation properties of a treatment fluid.
    Other combinations of biodegradable chelating agents can also be considered.
    Table 1 shows an illustrative list of stability constants for various metal complexes of GLDA, MGDA eDDS, IDS, HIDS, B-ADA and ethylene diaminetetraacetic acid (EDTA). Table 1 Chelating agent Cation OE to AS of EDTA Fell) 10.65 MGDA Fedll) 81 MGDA Fell) 16.5 MGDA Ca (Il) 6.97 ne MODA ooo MED SB anna GILDA Call) 5.9 EDDS Feclll) 22, 0 EDDS Ca (Il) 4.58 nn DDS o MEMDO nn 602 ooo DS Feclll) 15.2 IDS Ca (Il) 6.97 err PDS ooo MAD.
    TABS ooo B-ADA Feclll) 133-16 B-ADA Fedll) 8,9 B-ADA Ca (Il) 5 nn BADA o MEMO SE nano HDS Fed) 6,98 HIDS Fell) 14,36 HIDS Ca (Il) 512 As shown in Table 1 eDDS, for example, can be included in a treatment fluid containing MGDA when a high affinity for Fe (III) binding is desired and / or a more affinity — low for Ca (lI binding) ) is required.
    The combination of MGDA and EDDS has been described for illustrative purposes only and in the knowledge of the stability constant of a given chelating agent for a given metal cation, a person of ordinary skill in the art will be able to predict an appropriate treatment fluid containing any combination biodegradable chelating agents for a given application.
    In addition to the stability constant, a person of ordinary skill in the art will recognize that the ability of a given chelating agent to react with a given cation will be a function of the pH of the treatment fluid. For example, maximum Fe (III) chelation occurs at a pH of about 3 with MGDA and decreases at lower pH values. In contrast, the maximum chelation of Ca (II) and Mg (II) occurs at a higher pH with this chelating agent. Therefore, by adjusting the pH of the treatment fluid, its properties for binding a cation of interest can be changed. In the illustrative example described, a treatment fluid having a pH of about 3 or below can be used to selectively remove Fe (IlD) cations, while leaving Ca (IID) and Mg (II) uncomplexed, thus not wasting the agent chelating in cations whose chelation is unwanted.
    The composition of the chelating agent can comprise about 1% to about 50% by weight of the treatment fluid. Preferably, the composition of the chelating agent can comprise about 3% to about 40% by weight of the treatment fluid. The ratio of the composition of the chelating agent to water in a treatment fluid can be from about 1% to about 50% by weight based on a known or existing concentration. Preferably, the ratio of the chelating agent to water composition in a treatment fluid can be from about 1% to about 20% by weight based on a known or existing concentration. This ratio - can be from about 3% to about 6%. The treatment fluid can further comprise an acid. The acid can be a mineral acid such as, for example, hydrochloric acid. The acid can comprise hydrofluoric acid or a compound that generates hydrofluoric acid. When present, hydrofluoric acid in a treatment fluid - of the present invention can be produced from a suitable compound that generates hydrofluoric acid. Examples of suitable compounds that generate hydrofluoric acid include, but are not limited to, fluoroboric acid, fluorosulfuric acid, hexafluorophosphoric acid, hexafluoroantimonic acid, difluoro-phosphoric acid, hexafluorosilicic acid, potassium difluoride hydrogen, sodium fluoride fluoride boron acetic acid, phosphoric acid boron trifluoride complex, boron trifluoride dihydrate, polyvinylammonium fluoride, polyvinylpyridinium fluoride, pyridinium fluoride, imidazolium fluoride, ammonium fluoride, ammonium fluoride, fluoride salts, tetrafluoride salts hexafluorophosphate salts, bifluoride salts and any combination thereof. When used, a compound that generates hydrofluoric acid can be present in the treatment fluids in an amount ranging from about 0.1% to about 20% by weight of the treatment fluid. An amount of the compound that generates hydrofluoric acid can vary from about 0.5% to about 10% or from about 0.5% to about 8% by weight of the treatment fluid. The treatment fluids of the present invention can also include a viscoelastic surfactant. In general, any suitable surfactant that is capable of imparting viscoelastic properties to an aqueous fluid can be used in accordance with the disclosures of the present invention. These surfactants can be cationic, anionic, non-ionic, zuiterionic or amphoteric in nature and comprise any number of different compounds, which include methyl ester sulfonates (such as those - described in the jointly owned United States patents.
    7,159,659, 7,299,874 and 7,303,019 and United States Patent Application No. 11 / 058,611, filed February 15, 2005 and now available as United States Patent Application Publication 20060183646 each of which is here incorporated by reference), betaines, modified betaines, sulfosuccinates, taurates, amine oxides, ethoxylated fatty amines, quaternary ammonium compounds, any derivative thereof and any combination thereof. When present in the treatment fluids of the present invention, the surfactant is generally present in an amount sufficient to provide a desired viscosity (for example,
    enough viscosity to divert the flow, reduce fluid loss, suspended particles and the like) through the formation of viscosifying micelles. The surfactant in general can comprise from about 0.5% to about 10%, by volume, of the treatment fluid. The surfactant can comprise from about 1% to about 5% by volume of the treatment fluid.
    When including a surfactant, the treatment fluids of the present invention can also comprise one or more co-surfactants to, among other things, facilitate the formation and / or stabilization of a foam, facilitate the formation of micelles (e.g. viscosifying micelles) , increase salt tolerability and / or stabilize the treatment fluid. The co-surfactant can comprise any surfactant suitable for use in underground environments that do not adversely affect the treatment fluid. Examples of co-surfactants suitable for use in the present invention include, but are not limited to, linear Cio - Cia alkyl benzene sulfonates, branched Cio - Cia alkyl benzene sulfonates, tallow alkyl sulfonates, coconut glyceryl ether sulfonates, condensation products tallow sulfates Cio - Cig alcohols mixed with about 1 to about 14 moles of ethylene oxide and mixtures of higher fatty acids - containing from about 10 to about 18 carbon atoms. The co-surfactant can be present in an amount in the range of about 0.05% to about 5% by volume of the treatment fluid. Preferably, the co-surfactant can be present in an amount in the range of about 0.25% to about 0.5% by volume of the treatment fluid. The type and amount of co-surfactant suitable for a particular application of the present invention may depend on a variety of factors, such as the type of surfactant present in the treatment fluid, the composition of the treatment fluid, the temperature of the treatment fluid and your peers. A person of ordinary skill in the art, with the benefit of this disclosure, will recognize when to include a co-surfactant in a particular application of the present invention, as well as the appropriate type and amount of co-surfactant to include. The treatment fluids of the present invention can optionally comprise one or more salts to modify the rheological properties (e.g., viscosity) of the treatment fluids. These salts can be organic or inorganic. Examples of suitable organic salts (or acid forms free of organic salts) which include, but are not limited to, aromatic sulfonates and carboxylates (e.g., p-toluenesulfonate and naphthalenesulfonate), hydroxynaphthalene carboxylates, —salicylates, phthalates, acid chlorobenzoic acid, phthalic acid, 5-hydroxy-1-naphthoic acid, 6-hydroxy-1-naphthoic acid, 7-hydroxy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 5-hydroxy-2-naphthoic acid, T-hydroxy-2-naphthoic acid, 1,3-dihydroxy-2-naphthoic acid, 3,4-dichlorobenzoate, trimethylammonium hydrochloride and tetramethylammonium chloride. Examples of suitable inorganic salts include water-soluble potassium, sodium and ammonium salts (for example, potassium chloride and ammonium chloride). Any combination of the salts listed above can also be included in the treatment fluids of the present invention. Where included, the one or more salts may be present in an amount ranging from about 0.1% to about 75% by weight of the treatment fluid. Preferably, the one or more salts can be present in an amount ranging from about 0.1% to about 10% by weight of the treatment fluid. A person of ordinary skill in the art, with the benefit of this disclosure, will recognize when to include a salt in an application - particular of the present invention, as well as the appropriate type and amount of salt to include.
    The treatment fluids of the present invention can also include one or more well-known additives, such as gel stabilizers, fluid loss control additives, particulates, acids, corrosion inhibitors, catalysts, clay stabilizers, biocides, friction reducers , additional surfactants, solubilizers, pH adjusting agents, bridging agents, dispersants, flocculants, foaming agents, gases, defoamers, HS decontaminants, CO decontaminants; oxygen decontaminants, fouling inhibitors, lubricants, viscosifiers, weight and the like. A person of ordinary skill in the art, with the benefit of this disclosure, will be able to determine the appropriate type and amount of such additives for a particular application. For example, it may be desired to foam a treatment fluid of the present invention using a gas, such as air, nitrogen, or carbon dioxide.
    The methods described herein may comprise providing a treatment fluid comprising an aqueous based fluid, hydrofluoric acid or a compound that generates hydrofluoric acid and a chelating agent composition comprising glutamic acid, diacetic acid, any salt thereof, or any derivative thereof and introduce the treatment fluid into at least a portion of an underground formation. The treatment fluid can remove potentially harmful precipitates from the formation, for example. Any other biodegradable chelating agent described here as well - can be used in combination with or in place of GLDA.
    Treatment fluids comprising an aqueous based fluid and a chelating agent composition comprising diacetic acid glutamic acid, any salt thereof, or any derivative thereof are described herein.
    The methods described herein may comprise providing a treatment fluid comprising an aqueous based fluid and a chelating agent composition comprising glutamic acid, diacetic acid, any salt thereof, or any derivative thereof and introducing the treatment fluid into the hair. least a portion of an underground formation. Any other biodegradable chelating agent described herein can also be used in combination with or in place of GLDA.
    The methods described herein can comprise providing a treatment fluid comprising an aqueous based fluid and a chelating agent composition comprising at least one chelating agent selected from methylglycine diacetic acid, diacetic B-alanine acid, ethylene diaminodisuccinic acid, S, S acid -ethylenediamino-disuccinic, iminodisuccinic acid, hydroxyiminodissuccinic acid, polyamine disuccinic acids, N-bis [2- (1,2-dicarboxyethoxy) ethylglycine, N- —bis [2- (1,2-dicarboxyetoxy) ethyl Jaspártic, N- bis [2- (1,2-dicarboxy-ethoxy) ethyl Jmethylglycine, - N-tris - [(1,2-dicarboxyethoxy) ethylJamine, N-methyliminodiacetic acid, iminodiacetic acid, imino-diacetic N- (2-acetamido) acid , hydroxymethyliminodiacetic acid, 2- (2-carboxyethylamino) succinic acid, 2- (2-carboxymethylamino) succinic acid, diethylenetriamine-N, N ”-dissuccinic acid, triethylenetetramino-N, N” ”- disuccinic acid, 1, 6-hexamethylenediamino-N, N'-disuccinic, tetraethylenopentamino-N, N ”” - d issuccinic, 2-hydroxypropylene-1,3-diamino-N, N'-disuccinic acid, 1,2-propylenediamino-N, N'-disuccinic acid, 1,3-propylene diamine-N, N'-disuccinic acid, cis acid -cyclohexanediamino- —NQN -dissuccinic, trans-cyclohexanediamino-N, N '-dissuccinic acid, ethylenebis (oxyethylenonitrile) -N, N'-disuccinic, glycoeptanoic acid, cystic acid-N, N-diacetic acid, c-acid -monoacetic acid, alanine-N- acid - “monoacetic acid, N- (3-hydroxysuccinyl) aspartic acid, N- [2- (3-hydroxysuccinyl)] - II serine, aspartic acid-NN-diacetic acid, acid - aspartic -N-monoacetic acid, any salt thereof, any derivative thereof and any combination thereof; and introducing the treatment fluid into at least a portion of an underground formation. The treatment fluid can further comprise an acid. The treatment fluid can further comprise hydrofluoric acid or a compound that generates hydrofluoric acid.
    The methods described herein may comprise providing a treatment fluid comprising an aqueous based fluid and a chelating agent composition comprising at least one chelating agent selected from diacetic acid methylglycine, any salt thereof, any derivative thereof and any combination the same; and introducing the treatment fluid into at least a portion of an underground formation. The treatment fluid can further comprise hydrofluoric acid or a compound that generates hydrofluoric acid. The chelating agent composition - can be substantially free of alkali metal fons and comprise an ammonium or tetraalkylammonium salt of the biodegradable chelating agent. Other biodegradable chelating agents described herein can be used in combination with diacetic acid methylglycine.
    The methods described herein may comprise providing a treatment fluid comprising an aqueous based fluid and a chelating agent composition comprising at least one chelating agent selected from glutamic acid diacetic acid, diacetic acid methylglycine, B-alanine diacetic acid, ethylene diamine acid disuccinic, —S, S-ethylenediaminodisuccinic acid, iminodi-succinic acid, hydroxyiminodissuccinic acid, polyamine disuccinic acids, N-bis [2- (1,2-dicarboxyethoxy) ethylJglycine, N-bis [2- (1,2- dicarboxyetoxy) ethyl Jaspártico, N-bis [2- (1,2-dicarboxyetoxy) ethyl Jmethyl-glycine, N-tris [(1,2-dicarboxyethoxy) ethylJamine, N-methylimino-diacetic acid, iminodiacetic acid, N- ( 2-acetamido) iminodiacetic, acid - hydroxymethyliminodiacetic acid, 2- (2-carboxyethylamino) succinic acid, 2- (2-carboxymethylamino) succinic acid, diethylenetriamine-N, N ”-dissuccinic acid, triethylenetetramino-N, N” - disuccinic acid , 1,6-hexamethylenediamino-N, N'-disuccinic acid, acid tetraethylenopentamino-N, N ”- disuccinic, 2-hydroxypropylene-1,3-diamino-N, N'-disuccinic acid,
    1,2-propylenediamino-N, N'-disuccinic acid, 1,3-propylenediamino-N, N'-disuccinic acid, cis-cyclohexanediamino-N, N-disuccinic acid, trans-cyclohexanediamino N, N-disuccinic acid, ethylenebisobinic acid (oxyethylenonitrile) - N, N-disuccinic, glycoeptanoic acid, cystic acid-N, N-diacetic acid, cystic acid -N-monoacetic acid, alanine-N-monoacetic acid, N- (B-hydroxysuccinyl) aspartic acid, = N - [2- (3-hydroxysucciny1)] - l1-serine, aspartic acid-N, N-acid - diacetic, aspartic acid-N-acid - monoacetic, any salt thereof, any derivative thereof and any combination thereof; and treating a tube or pipes with the treatment fluid. Treating a tube or pipes with the treatment fluid may comprise removing metallic fon crust from the tube or pipes. The tube may comprise a well hole that penetrates at least a portion of an underground formation. The treatment fluid can have a pH ranging from about 6 to about 8. The treatment fluid can have a pH of at least about 8.
    Preferably, an acidic treatment fluid of the present invention comprising an aqueous-based fluid, hydrofluoric acid or a compound that generates hydrofluoric acid and a biodegradable chelating agent composition comprising diacetic acid glutamic acid, any salt - of diacetic acid glutamic acid , or any derivative of diacetic acid glutamic acid can be used in the prevention methods to prevent the formation of precipitates such as, for example, those produced in conjunction with a treatment with hydrofluoric acid in a sandstone formation. These embodiments are more suitable for formations that - comprise clays or include cations that can be problematic in terms of precipitate formation. Alternatively, other biodegradable chelating agents such as, for example MGDA, B-ADA eDDS, IDS, RIDS, any salt thereof, any derivative thereof, any combination thereof, or any other biodegradable chelating agents described herein may be used instead of or in combination with GLDA, any GLDA salt, or any GLDA derivative. Optionally, the hydrofluoric acid or compound that generates hydrofluoric acid can be omitted from the treatment fluid, particularly if the underground formation that is treated is not a sandstone or similar silica formation.
    The treatment fluids of the present invention can be used as a pre-treatment for a fracture treatment especially in underground formations that contain different layers of sedimentary rock. In such embodiments, a treatment fluid of the present invention comprising an aqueous-based fluid, hydrofluoric acid or a compound that generates hydrofluoric acid and a chelating agent composition of the present invention comprising glutamic acid diacetic acid, any salt of the glutamic acid diacetic acid, or any derivative of glutamic acid diacetic acid is placed in an underground formation through a well bore before a fracture treatment. The subsequent fracture treatment can be a traditional fracture treatment or an additional acidification treatment aimed at sealing treated particulate introduced during the fracture operation. In such embodiments, the use of the treatment fluid of the present invention can be considered a preventive mechanism for preventing the formation of potentially problematic precipitates. As before, other biodegradable chelating agents such as, for example MGDA, B-ADA eDDS, IDS, HIDS, any salt thereof, any derivative thereof, —combination thereof, or any other biodegradable chelating agent described herein can be used in the instead of or in combination with GLDA, any GLDA salt, or any GLDA derivative and the hydrofluoric acid or compound that generates hydrofluoric acid can optionally be omitted.
    A treatment fluid of the present invention comprising an aqueous-based fluid, hydrofluoric acid or a compound that generates hydrofluoric acid and a chelating agent composition of the present invention comprising glutamic acid diacetic acid, any salt of diacetic acid glutamic acid, or any derivative of glutamic acid — acidodiacetic can be used to clean the borehole area before taking the well to final production. Using such a treatment fluid it is possible to remove damage, blockages, fragments and natural clays from the formation, for example. In at least some embodiments, this method can be considered a remediation method of the present invention. As before, - other biodegradable chelating agents such as, for example MGDA, p-ADA eDDS, IDS, HIDS, any salt thereof, any derivative thereof, any combination thereof, or any other biodegradable chelating agents described herein can be used in place or in combination with GLDA, any GLDA salt, or any GLDA derivative and the hydrofluoric acid or compound that generates hydrofluoric acid can optionally be omitted.
    The treatment fluids of the present invention can be useful in formations that comprise siliceous materials, for example, naturally occurring sandstone, support material, etc. A siliceous material can be naturally present in the formation, for example, sandstone, or deliberately introduced, for example, a quartz shoring. Due to the geochemical processes operating in the formation, such as high temperature, high pressure and abrupt changes to the geochemical balance after the introduction of treatment fluids of different ionic concentration, the siliceous material can undergo rapid changes that lead to reduced hydraulic permeability or conductivity. When the treatment is carried out in the sandstone matrix, it is believed that the effect is to remove aluminosilicates from the conductive pathways. In a particulate seal or supported fracture, the effects are combined because, under certain scenarios, geochemical fouling can occur. Another reason is due to the migration of fines, which is the displacement of particles from the rock matrix into the seal and its subsequent deposition. In addition, the presence of aluminum in a sandstone and in these ceramic struts made with alumina exacerbates the - problem due to its intrinsic reactivity in the low pH medium or under abrupt changes to the chemical potential of a fluid that leads to the dissolution of the material. This means that the varying amounts of silicon and / or aluminum that are put into solution, can migrate and re-precipitate or crystallize and form new minerals that obstruct the flow of fluids.
    Where clays or other siliceous minerals are not present in the formation, the treatment fluid may not include hydrofluoric acid or a compound that generates hydrofluoric acid. Glutamic acid diacetic acid, any salt of diacetic acid glutamic acid, any derivative of diacetic acid glutamic acid or any of the alternative biodegradable chelating agents described herein, or any of its salts or derivatives described here may be sufficient to carry out the preventive action desired. In some embodiments where clays are present in the formation, it may be desirable to remedy the damage of precipitate present in the well bore or in the formation which can be blocking pore bottlenecks within the formation. Such methods can be appropriate at any time where production declined due to the presence of particulates or fines that obstructed the pore bottlenecks in the area near the well hole.
    An additional acid can be included in the treatment fluid. The additional acid can be a mineral acid such as, for example, hydrochloric acid, which can be included in the hydrofluoric acid treatment fluid or a compound that generates hydrofluoric acid. The additional acid can be an organic acid such as, for example, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, or methanesulfonic acid. In each case, the additional acid can serve to maintain the fluid's pH at a desired low level, particularly a level at which the chelating agent is active for chelation to occur.
    It may be desirable to include a salt or a salt substitute in the treatment fluid. The beneficial effects of a salt or salt substitute are surprising, since it is conventionally believed that the addition of a salt to a treatment fluid can exacerbate precipitation problems. A preferred example of a suitable salt is ammonium chloride or as an ammonium salt. This is believed to be a specific problem for treatment fluids that contain hydrofluoric acid or a compound that generates hydrofluoric acid, since alkali metal salts such as sodium and potassium salts can promote the formation of precipitates in the presence of of fluoride fons. In contrast, the addition of an ammonium salt will not exacerbate the precipitation problem.
    The treatment fluids of the present invention can be used to treat a strut seal, particularly where the hydraulic conductivity of the strut seal has been impacted.
    To facilitate a better understanding of the present invention, the following examples of preferred embodiments are given. In no way should the following examples be read as limiting, or - as defining, the scope of the invention.
    EXAMPLES Experiment 1 A solution of DISSOLVINEG & (GLNA40S) available from AkzoNobel was used in the preparation of the treatment fluid. A solution - containing 3.5% by weight of GLNA4OS was prepared by dissolving 363.5 g of the concentrated form in a base fluid. The base fluid consisted of 2% NaCl containing 20 g / L of tannic acid. After mixing all the components thoroughly, the pH of the final volume of solution (4 L) was adjusted to pH 1.6 with 35% HCl. The solution was filtered through a 0.40 micron membrane.
    It was stable for the duration of the test period (days). A 2 ”x 12” (5 x 30 cm) long Hassler glove was used to conduct an acid core flood test at 320º F [160º C]. The glove was sealed with a mixture —homogenized quartz (Oklahoma sand t1) (94% by weight), K - feldspar (2% by weight) and aluminosilicate chlorite (4% by weight). The pore volume (PV) of the sealed column corresponded to 110 ml.
    The column was treated with the following fluid sequence: 4 PV, 2% NaCl (pH 6), 2 PV, 3.5% GLNA4OS (pH 1.6) with Tannic acid, 3 PV, 5% Acetate ammonium (pH 4.5) and 3 PV, 2% NaCl (pH 6). The results of the core flooding indicated that during exposure to 2 PV of DISSOLVINEG (GLNAA40S), indicated in Figure 1 by the arrow that crosses samples 4 to 12, the amount of Alº *, as detected by the ICP-OES, gradually increases until the injection of the chelating agent was stopped.
    Once the sand / chlorite seal was no longer exposed to the chelating fluid, the release of aluminum in the solution ceased.
    The flow rate was 2 ml / min for the entire first 1.5 PV and then increased to 5 ml / min for the last 0.5 PV.
    The effluent was collected at 0.5 and 1 PV intervals analyzed for AIº * and Si ** by ICP, no quantitative precipitate was observed in the effluent which was stable for days at room temperature after collection.
    The respective effluent samples collected for the ICP analysis - were not acidified with any additional acid, instead they were analyzed at their respective pH at the time of collection.
    The amount of silicon remained almost constant.
    Experiment 2 The description that follows corresponds to the visual observations and titrations conducted. All tests, which include core flooding (described above in Experiment 1), used a fluid consisting of DISSOLVINEGO GLDA (GL-NAA40S) and tannic acid.
    The solubility of Alº ** at concentrations of 200 to 3000 ppm was independently tested at room temperature. 100 ml of a stock solution (1.45 M pH 1.45) was placed in a stirred beaker and the pH was gradually raised with a strong base (1 M NaOH or 2 M NHAOH in order to minimize volume changes due to dilution). Precipitation of aluminum hydroxide which resulted shortly after reaching pH 2.5 and almost completely precipitated quantitatively at pH 3 in the absence of any chelating agent. When GLDA was used in concentrations of 3.5% by weight or 12% by weight, precipitation was effectively suppressed as the pH increased from the starting pH from 1.45 to 4. After reaching pH 4, a relatively smaller amount of flocculated particles were evident, but no precipitate formed for days. The GLDA solution used in this case contained tannic acid but this had no effect on the chelation of AIº **. Instead, the effective complexation of Alº ** in the presence of another reagent (GLDA) has been shown to be effective in the same pH range.
    Experiment 3 A glass bottle containing 5 g of mineral (clay or quartz) was mixed with 15 or 20 ml of treatment fluid. The treatment fluid was composed of 15% by weight GLDA and 3% by weight NHAHF, with sufficient HCl to adjust the pH to the value indicated in Table 2 - below. The reaction mixtures were heated in a cylinder heated to 95 ºC for 0.5, 1, 2, 3, 4 hours and automatically stirred (at 200 rpm). The reaction fluid was collected using a syringe and filtered through a 0.45 micron membrane filter before the analysis of ICP-AES, the pH of the solution was not adjusted by any means. The analysis and, list for each mineral is provided in Table 2.
    It is worth noting that the point of these experiments was not to optimize the fluid composition, but instead to show the effectiveness of GLDA even in the presence of a compound that generates hydrofluoric acid such as ammonium bifluoride. Although there are pentafluoro-silicates and sodium hexafluorosilicates , the known harmful precipitates that result from the HSiFs- reaction (primary reaction) as identified by XRD in the powder of the solid mixture after drying completely in an oven at 100 ºC for 2 to 4 h, the amount of silicon dissolved in these fluids remained substantial . The illite reaction with the fluid showed that the clay was attacked by the fluid since the spent fluid contained all the elements present in the virgin structure. The chlorite reaction was shown to be more effective as demonstrated by the higher concentration of Al and Si, as well as all others having fons. Kaolinite on the other hand showed decreased dissolution, as expected, for this clay mineral under the conditions of the experiment. Bentonite also showed decreased reactivity, this may be due to the actual precipitation for the dissolved silica or pentafluorosilicates. The sand does not react significantly. Table 2 Al Si Sample mg / L mg / L PH Vol. [Ppm] [pm] mr) Illite 1 816 304 1.3 20 2 768 309 1.3 20 3 2.041 364 1.3 20 4 531 258 1.3 20 5 522 281 1.3 20 Chlorite 6 1789 754 13 20 7 1.654 752 1.3 20 8 1.702 748 1.3 20 9 1.400 933 1.3 20 10 1.375 898 13 20 Kaolinite 11 750 220 13 20 12 1.167 220 1 , 3 20 13 684 197 1.3 20 14 684 201 1.3 20
    Bentonite 15 138 273 3 15
    16 275 198 3 15
    17 177 257 3 15
    18 132 277 3 15
    Sand 23 x 405 1.3 20
    24 x 103 1.3 20
    25 x 112 1.3 20
    26 x 50 1.3 20 Therefore, the present invention is well adapted to achieve the mentioned purposes and advantages as well as those that are inherent here.
    The particular embodiments disclosed above are illustrative only, since the present invention can be modified and practiced in different but equivalent ways evident to those skilled in the art having the benefit of the disclosures here.
    In addition, no limitation is intended for the construction or design details shown here, other than as described in the claims below.
    It is therefore evident that the particular illustrative embodiments disclosed above can be altered, combined, or modified and all such variations are considered to be within the scope of the present invention.
    Although the compositions and methods are described in terms of "understanding," "containing," or "including" various components or steps, the compositions and methods can also "consist essentially of or" consist "of the various components and steps.
    All numbers and ranges disclosed above may vary by some amount.
    Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range that falls within the range is specifically disclosed.
    In particular, each range of values (of the form, “from about a to about b, 'or equivalent,“ approximately from a to b,' or equivalently, “approximately from ab”) disclosed herein should be understood to present each number and range covered within the broadest range of values.
    Also, the terms in the claims have their simple, common meaning unless otherwise explicitly and clearly defined by the patent holder.
    In addition, the indefinite articles "one" or "one," as used in the claims, are defined herein to mean one or more than one of the element they introduce.
    If there is any conflict in the use of a word or term in this specification and one or more patents or other documents that may be incorporated herein by reference, definitions that are compatible with the specification should be adopted.
    权利要求:
    Claims (19)
    [1]
    1. Underground treatment method, characterized by the fact that it comprises: providing a treatment fluid comprising: an aqueous-based fluid; and a chelating agent composition comprising at least one chelating agent selected from the group consisting of methylglycine diacetic acid, B-alanine diacetic acid ethylene diaminedisuccinic acid, S, S-ethylene diaminedisuccinic acid, —minodisuccinic acid, hydroxyiminodisuccinic acid, polyamino acids -bis [2- (1,2-dicarboxyethoxy) ethylglycine, N-bis [2- (1,2-dicarboxyetoxy) ethylJaspártico, N-bis [2- (1,2-dicarboxy-ethoxy) ethyl J] methylglycine , - N-tris [(1,2-dicarboxyethoxy) ethyl amine, N-methyliminodiacetic acid, iminodiacetic acid, —N- (2-acetamido) - iminodiacetic acid, hydroxymethyliminodiacetic acid, 2- (2-carboxyethylamino) succinic acid , 2- (2-carboxymethylamino) succinic acid, diethylenetriamine-N, N ”-dissuccinic acid, triethylenetetramino-N, N” ”- disuccinic acid, 1,6-hexamethylenediamino-N, N'-disuccinic acid, tetraethylenopentamino-N , N ”” - disuccinic, 2-hydroxypropylene-1,3-diamino-N, N'-disuccinic acid, 1,2-propylene iamino-N, N '-dissuccinic, 1,3-propylenediamino-N, N'-disuccinic acid, cis-cyclohexanediamino-N, N-disuccinic acid, trans-cyclohexanediamino-N, N'-disuccinic acid, ethylenebis (oxyethylenonitrile) ) -N, N'-disuccinic, glycoeptanoic acid, cystic acid-N, N-diacetic acid, cystic acid-N-monoacetic acid, alanine-N-acid - “monoacetic acid, N- (3-hydroxysuccinyl) aspartic acid, N - [2- (3-hydroxysuccinyl) -L-serine, aspartic acid-N, N -diacetic acid, aspartic acid-N-monoacetic acid, any salt thereof, any derivative thereof and any combination thereof; and introducing the treatment fluid into at least a portion of an underground formation.
    [2]
    2. Method according to claim 1, characterized by the fact that it additionally comprises: treating a shoring seal in the formation portion - underground.
    [3]
    3. Method according to claim 1, characterized by the fact that it additionally comprises: performing a stimulation operation in the underground formation portion.
    [4]
    4. Method according to claim 1, characterized by the fact that it additionally comprises: remedying the precipitation damage present on a surface in the portion of the underground formation.
    [5]
    Method according to claim 1, characterized by the fact that it additionally comprises: treating a tube that comprises a well hole that penetrates the underground formation.
    [6]
    6. Method according to claim 1, characterized in that the introduction of the treatment fluid occurs at a pressure that is less than a fracture pressure of the underground formation.
    [7]
    7. Method according to claim 1, characterized in that the introduction of the treatment fluid occurs at a pressure that is equal to or greater than a fracture pressure of the underground formation.
    [8]
    8. Underground treatment method, characterized by the fact that it comprises: providing a treatment fluid comprising: an aqueous-based fluid; and a chelating agent composition comprising at least one chelating agent selected from the group consisting of diacetic acid methylglycine, any salt thereof, any derivative thereof and any combination thereof; and introducing the treatment fluid into at least a portion of an underground formation.
    [9]
    Method according to any one of claims 1 to 8, characterized in that the treatment fluid has a pH ranging from about 1.5 to about 5.
    [10]
    Method according to any one of claims 1 to 9, characterized in that the treatment fluid has a pH ranging between about 1.5 and about 3.
    [11]
    Method according to claim 8, characterized in that the chelating agent composition additionally comprises at least one chelating agent selected from the group consisting of B-alanine - diacetic acid - ethylenediaminodisuccinic acid, S, S-ethylenediaminodisuccinic acid , iminodisuccinic acid, hydroxy-iminodisuccinic acid, polyamino-disuccinic acids, N-bis [2- (1,2-dicarboxyethoxy) ethyl] glycine, N-bis [2- (1,2-dicarboxyetoxy) ethyl] -aspartic , N-bis [2- (1,2-dicarboxyethoxy) ethyl Jmethylglycine, N-tris [(1,2-dicarboxyethoxy) ethylJamine, N-methyliminodiacetic acid, iminodiacetic acid, N- (2-acetamido) iminodiacetic acid, hydroxy-methyliminodiacetic, 2- (2-carboxyethylamino) succinic acid, 2- (2-carboxymethylamino) succinic acid, diethylenetriamine-N, N ”-dissuccinic acid, triethylenetetramino-N, N” ”- disuccinic acid, 1,6- hexamethylenediamino-N, N'-disuccinic, tetraethylenopentamino-N, N ”” - disucceínico, 2-hydroxyproic acid pilene-1,3-diamino-N, N'-disuccinic, 1,2-propylenediamino-N, N'-disuccinic acid, 1,3-propylenediamino-N, N'-disuccinic acid, cis-cyclohexanediamino-N acid, N'-disuccinic, trans-cyclohexanediamino-N, N'-disuccinic acid - ethylenebis (oxyethylenonitrile) - N, N-disuccinic, glycoheptanoic acid, cystic-N, N-diacetic acid, N-diacetic acid-N- monoacetic acid, alanine-N-monoacetic acid,
    N- (3-hydroxysuccinyl) aspartic, N- [2- (3-hydroxysuccinyl)] - L-serine, N-aspartic acid, N-diacetic acid, aspartic acid-N-monoacetic acid, glutamic acid diacetic acid, any salt thereof, any derivative thereof and any combination thereof.
    [12]
    12. Underground treatment method, characterized by the fact that it comprises: providing a treatment fluid comprising: an aqueous based fluid; and a chelating agent composition that comprises at least one chelating agent selected from the group consisting of diacetic acid glutamic acid, diacetic methylglycine acid, ethylenediaminethisuccinic B-alanine diacetic acid, S, S-ethylenediamine diisuccinic acid, iminodisuccinic acid, hydroxy-imino acid polyamine disuccinic acids, N-bis [2- (1,2-dicarboxyethoxy) ethyl | glycine, N-bis [2- (1,2-dicarboxyethoxy) ethyl] -aspartic acid, N-bis [2- (1, 2- dicarboxyethoxy) ethylJmethylglycine, N-tris - [(1,2-dicarboxiethoxy) ethylJamine, N-methyliminodiacetic acid, iminodiacetic acid, N- (2-acetamido) iminodiacetic acid, hydroxy-methyliminodiacetic acid, 2- (2-carboxyethylamino acid) ) succinic, 2- (2-carboxymethylamino) succinic acid, diethylenetriamine-N, N ”-dissuccinic acid, triethylenetetramino-N, N” ”- disuccinic acid, 1,6-hexamethylenediamino-N, N'-disuccinic acid, tetraethylenepentinent -N, N ”” - disuccinic, 2-hydroxypropylene-1,3-diamino-N, N'-disuccinic acid, 1,2-propylenediamino-N, N'-disuccinic acid, 1,3-propylenediamino-N, N'-disuccinic acid, cis-cyclohexanediamino-N, QN-disuccinic acid, trans-cyclohexanediamino-N, N'- disuccinic acid ethylenebis (oxyethylenonitrile) -N, N'-disuccinic, glycoheptanoic acid, N-cystic acid, N-diacetic acid, cystic acid-N-monoacetic acid, alanine-N-acid - “monoacetic, N- (3 -hydroxisuccinyl) aspartic, N- [2- (3-hydroxysuccinyl] -L-serine, N-aspartic acid, N-diacetic acid, aspartic acid-N-monoacetic acid, any salt thereof, any derivative thereof and any combination thereof; and treating a tube or pipes with the treatment fluid.
    [13]
    13. Method according to claim 12, characterized by the fact that treating a tube or pipes with the treatment fluid comprises removing metal scale encrustation from them.
    [14]
    Method according to claim 12 or claim 13, characterized in that the tube comprises a well hole that penetrates at least a portion of an underground formation.
    [15]
    Method according to any one of claims 12 to 14, characterized in that the treatment fluid has a pH ranging from about 6 to about 8.
    [16]
    16. Method according to any one of claims 12 to 14, characterized by the fact that the treatment fluid has a hair pH - less than 8.
    [17]
    Method according to any one of claims 1 to 16, characterized in that the treatment fluid additionally comprises hydrofluoric acid or a compound that generates hydrofluoric acid.
    [18]
    18. Method according to claim 17, characterized in that the compound that generates hydrofluoric acid is selected from the group consisting of fluoroboric acid, fluorosulfuric acid, hexafluorophosphoric acid, hexafluoroantimonic acid, difluorophosphoric acid, hexafluorosilicic acid, potassium difluoride hydrogen , hydrogen sodium fluoride, boron trifluoride and acetic acid complex, boron trifluoride and phosphoric acid complex, boron trifluoride dihydrate, polyvinylammonium fluoride, polyvinylpyridinium fluoride, pyridinium fluoride, amidazolium fluoride, fluoride, fluoride ammonium, tetrafluoroborate salts, hexafluoroantimonate salts, hexafluorophosphate salts, bifluoride salts and any combination thereof.
    [19]
    19. Method according to any one of claims 1 to
    18, characterized by the fact that the chelating agent composition is substantially free of alkali metals and comprises an ammonium or tetraalkylammonium salt of at least one chelating agent.
    1/1 "Concentration of effluent 1600 NETWORK REST oIEmEAAAO .. 2. Us 1400 ço: 1200 | e 'o 1000 ee 7 800 2 | o: 600 + ... 400 + - 200 nan a Ss B o HERSUEADSÕOS" AL 0 , .0 + o 5 10 15 20 Sample of fractional pore volume Figure 1 |
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    同族专利:
    公开号 | 公开日
    CA2831490A1|2012-11-01|
    CA2831490C|2016-01-26|
    US9120964B2|2015-09-01|
    AR086041A1|2013-11-13|
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    法律状态:
    2020-07-28| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-11-24| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|
    2021-11-03| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    优先权:
    申请号 | 申请日 | 专利标题
    US13/094,248|US9120964B2|2006-08-04|2011-04-26|Treatment fluids containing biodegradable chelating agents and methods for use thereof|
    US13/094248|2011-04-26|
    PCT/GB2012/000385|WO2012146895A1|2011-04-26|2012-04-26|Treatment fluids containing biodegradable chelating agents and methods for use thereof|
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