CN101896573A - High temperature aqueous-based zirconium fracturing fluid and use - Google Patents
High temperature aqueous-based zirconium fracturing fluid and use Download PDFInfo
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- CN101896573A CN101896573A CN2008801208902A CN200880120890A CN101896573A CN 101896573 A CN101896573 A CN 101896573A CN 2008801208902 A CN2008801208902 A CN 2008801208902A CN 200880120890 A CN200880120890 A CN 200880120890A CN 101896573 A CN101896573 A CN 101896573A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
- C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
Abstract
A fracturing fluid or crosslinking composition suitable for use at high temperature (275-340 DEG F, 135-171 DEG C) comprising (a) an aqueous liquid, (b) brine, (c) a thermal stabilizer, (d) a non-delaying alkaline buffer sufficient to provide a pH less than 9, (e) an organic acid, (f) hydroxypropyl guar and (g) a zirconium crosslinking agent. The composition is useful as a fracturing fluid in oil field applications, for example, for hydraulically fracturing a subterranean formation or selectively plugging a permeable zone or leak in a subterranean formation.
Description
Invention field
The present invention relates to cross-linked composition and their purposes in field use, such as infiltration area waterfrac treatment and obstruction based on zirconium.
Background of invention
The technology that is called as waterfrac treatment can make from the oil and natural gas of missile silo (stratum) output to be increased production, the viscous fluid composition (fracturing liquid) that wherein comprises suspended prop (for example sandstone, alumina) is via being introduced in oil well or the gasser with certain flow and pressure such as conduits such as pipeline or sleeve pipes, and described pressure can produce, reopen and/or prolong the crack in oil-containing or gas-bearing formation.Propping agent is carried in the crack via fluid composition, and prevents that the stratum is closed behind release of pressure.The fluid viscosity limit fluid composition of described composition is leaked in the stratum.Fluid viscosity also makes propping agent to be suspended in during frac job in the described composition.Usually linking agent such as boric acid ester, titanic acid ester or zirconate are incorporated in the described fluid composition with control viscosity.
Generally speaking, oil well by pressure break after, reduce to gather in output and become no longer before the economy, from this oil well, only can exploit out the recverable oil of less than 1/3rd.The oil production rate that raising is gathered from such stratum usually relates to be attempted with driving liquid displacement residual crude oil, and described driving liquid is for example gas, water, salt solution, steam, polymers soln, foam or micellar solution.It is desirable to, this type of technology (often being called as technology of reservoir sweep) makes the pool with suitable degree of depth be forced to become recovery well; Yet it is usually really not so in the practice.Tryphine is normally heterogeneous, and the perviousness of some of them part is higher than other parts.Therefore, groove frequently occurs, and make to drive liquid and preferentially flow into oil-poor infiltration area (being called as weak zone), rather than flow into and make the profitable that part of area that comprises sufficient oil of oil producing operation.
The oil recovery difficulty that produces owing to weak zone can overcome in the following manner: polymkeric substance with crosslinked with the condition that forms gel under, the aqueous solution of organic polymer and linking agent is injected in the stratum, thereby reduces the stratum driving the perviousness of liquid (gas, water etc.).With some based on the compound crosslink of aluminium, titanium, zirconium and boron, can be used for during these displacement of reservoir oils use based on polysaccharide or based on the fluid of the polyacrylamide of partial hydrolysis.
No matter be used for the pressure break stratum or be used to reduce the perviousness of subterranean formation zone, nowadays crosslinked fluid or gel just are being used in the hotter and darker well under all temps and the pH value condition, and wherein the cross-linked speed with known cross-linked composition may be unacceptable.
The zirconium complex of the trolamine of commercially available acquisition can be all not crosslinked with suitable speed to all organic polymers, for example too fast crosslinked, perhaps under high pH condition and/or about 275 (135 ℃) and higher temperature, they can not keep enough viscosity in cross-linked fluids, cause viscosity significantly to descend because of shearing deterioration, described viscosity degradation also can cause sand fallout.Sand fallout was meant before fluid arrives the breaking zone, improved the situation that the sandy soil (upholder) that cause are deposited on wellbore bottom because of cross-linked fluids lacks viscosity.
United States Patent (USP) 4,801,389 disclose the fracturing liquid of being made up of natural guar gum that can use down at high temperature (250 to 325,121 ℃ to 163 ℃).Use supercarbonate that fluidic pH is controlled at 8 to 10, and described fluid also comprise zirconium crosslink agent such as zirconium lactate, Sulfothiorine, salt solution (KCl).Use supercarbonate to present acceptable viscosity (121 ℃ (250) and 170sec
-1Down, viscosity was 113cp in 1 hour).By contrast, use yellow soda ash to present relatively poor viscosity (23cp) under the same conditions.
United States Patent (USP) 6,737,386 disclose the fracturing liquid that comprises natural guar gum, and it has the temperature of 250 to 340 (121 ℃ to 171 ℃).Described fluid has 9 to 12 pH scope, and comprises zirconium crosslink agent, salt solution, Sulfothiorine, buffer reagent and citric acid.At 340 and 40sec
-1Under the shearing rate, use natural guar gum, the lasting viscosity that provided between 200 to 300cp in 4 hours of described fracturing liquid.
Need under high temperature (〉=275,135 ℃), to work and when using hydroxypropylguar gum, under these temperature, can provide the fracturing liquid of enough viscosity.HPG is the solvatable polysaccharide of commercially available acquisition.Compare with natural guar gum, during HPG was more soluble in water, this can farthest reduce the damage to the stratum.HPG also has hydration rate faster, and this can farthest reduce the formation of agglomerate when being dissolved in the water.Yet,, obtain unacceptable low viscosity when under certain condition when at high temperature using zirconium crosslink agent to make HPG crosslinked.
Summary of the invention
The invention provides the fracturing liquid or the cross-linked composition that are suitable at high temperature using, it is liquid, aqueous that described fracturing liquid or cross-linked composition comprise (a), (b) salt solution, (c) thermo-stabilizer, (d) be enough to provide non-retardance ealkaline buffer less than 9 pH, (e) organic acid, (f) hydroxypropylguar gum and (g) zirconium crosslink agent.PH is preferably 7.5 to 8.9, and more preferably 8.0 to 8.9.Described buffer reagent is preferably yellow soda ash or salt of wormwood.Described buffer reagent is yellow soda ash more preferably.Described fracturing liquid is particularly suited at high temperature using, promptly under about 275 (135 ℃) or higher temperature, for example under 275 to 340 (135 to 171 ℃) temperature.
The present invention also provides the method that fracturing liquid of the present invention is used for field use, for example is used for the waterfrac treatment stratum.Fracturing liquid of the present invention also can be used for stopping up the infiltration area in the stratum or splits leakage.
Detailed Description Of The Invention
Herein trade mark and trade(brand)name are represented with upper case.
The invention provides the fracturing liquid that comprises HPG that in hot hole, uses with enough viscosity.In addition, make enough viscosity keep the time that is enough to handle subterranean formation zone.More particularly, the invention provides fracturing liquid or cross-linked composition, it is liquid, aqueous that it comprises (a), (b) salt solution, (c) thermo-stabilizer (d) is enough to provide non-retardance ealkaline buffer less than 9 pH, (e) organic acid, (f) hydroxypropylguar gum and (g) zirconium crosslink agent.Every kind of components contents was enough to after the contact component 90 minutes, and the viscosity of at least 100 centipoises (cp) is provided at least under the temperature of 275 (135 ℃).
Liquid, aqueous (a) is selected from water and aqueous alcohol usually.Described liquid, aqueous water, aqueous methanol or the aqueous ethanol of being preferably.
Salt solution (b) is meant one or more components, is preferably used as the salt of clay stabilizer.Salt solution comprises for example hydrochloric acid and chloride salt such as tetramethyl ammonium chloride (TMAC), sodium-chlor or Repone K.Can use salt brine solution, and it for example comprises the clay stabilizer by described of the fracturing fluid gross weight 0.5 weight % to 5.0 weight %.Described salt solution is preferably tetramethyl ammonium chloride or Repone K.
Thermo-stabilizer (c) comprises for example methyl alcohol, alkali metal thiosulfate and ammonium thiosulfate.Described thermo-stabilizer is preferably alkali metal thiosulfate, more preferably Sulfothiorine.The concentration of thermo-stabilizer in described fracturing liquid is that described of the fracturing fluid gross weight is counted 0.1 weight % to 0.5 weight %, the thermo-stabilizer of preferred 0.2 weight % to 0.4 weight %.
Described fracturing liquid comprises the pH buffer reagent (d) of significant quantity, and so that pH is controlled at pH less than 9, described pH buffer reagent is non-retardance ealkaline buffer.The buffer reagent of delayed cross-linking speed not after so-called " non-retardance ealkaline buffer " is meant in joining described composition.Preferred reducing agents is yellow soda ash or salt of wormwood, more preferably yellow soda ash.Preferably pH is 7.5 to 8.9, more preferably 8.0 to 8.9.Described fracturing liquid comprises by described of the fracturing fluid gross weight 0.05 weight % to 0.2 weight %, preferred 0.05 weight % to 0.15 weight %.
Described fracturing liquid comprises organic acid (e).Organic acid is appointed as carboxylic acid.Preferred organic acid is formic acid, acetate, lactic acid and fumaric acid.Described acid is preferably fumaric acid.Described fracturing liquid comprises by described of the fracturing fluid gross weight 0.01 weight % to 0.15 weight %, preferred 0.02 weight % to 0.1 weight %, and the organic acid of 0.04 weight % to 0.08 weight % most preferably.
Described fracturing liquid comprises crosslinkable organic polymer (f), and it is hydroxypropylguar gum (HPG).Described fracturing liquid comprises by described of the fracturing fluid gross weight 0.2 weight % to 1.0 weight %, the HPG of preferred 0.4 weight % to 0.7 weight %.
Described fracturing liquid comprises zirconium crosslink agent (g).Described zirconium crosslink agent is to make the polyreaction compound can form the zirconium-containing compound of three-dimensional network.The example of zirconium crosslink agent comprises zirconium-alkanolamine title complex, zirconium-alkanolamine-polyvalent alcohol title complex and zirconium-lactic acid salt, comprises sodium salt, ammonium salt and alkanol amine salt.
Zirconium-alkanolamine title complex can make by the reaction of tetraalkyl zirconate and alkanolamine.Zirconium-alkanolamine-polyvalent alcohol title complex can make by the reaction of tetraalkyl zirconate and alkanolamine and suitable polyvalent alcohol.The tetraalkyl zirconate is usually by general formula Zr (OR)
4Expression, wherein each R is independently selected from alkyl, cycloalkyl, alkaryl, each group comprise 1 to about 30 carbon atoms, preferred 2 to about 18 carbon atoms and the alkyl of 2 to 12 carbon atoms most preferably, and each R can be identical or different.In the reaction of tetraalkyl zirconate and alkanolamine, alkanolamine replaces four OR groups in the tetraalkyl zirconate.Zirconium-alkanolamine title complex and zirconium-alkanolamine-polyvalent alcohol title complex can from for example E.I.du Pont de Nemours and Company (Wilmington, DE) commercially available.
The zirconium lactic acid salt can make by the reaction of basic zirconium chloride and lactic acid.After the reaction, available bases such as ammonia, alkali metal hydroxide, alkanolamine neutralize, or react with quaternary ammonium hydroxide.Preferred zirconium-lactic acid salt is zirconium-lactic acid three ammoniums or its sodium salt analogue zirconium-lactic acid trisodium.Zirconium-lactic acid salt can from for example E.I.duPont de Nemours and Company (Wilmington, DE) commercially available.
Described zirconium crosslink agent is preferably selected from alkanolamine title complex, zirconium-alkanolamine-polyvalent alcohol title complex, zirconium-lactic acid three ammoniums and zirconium-lactic acid trisodium.
In zirconium crosslink agent generally is dissolved in organic solvent, water-containing solvent or blended moisture/organic solvent, obtain zirconium solution.Typical solvent comprises water and alcohol, such as ethanol, n-propyl alcohol and Virahol.
Described fracturing liquid comprises by described of the fracturing fluid gross weight between 10 to 50ppm (μ g/g), preferred 30 to 40ppm zirconium (with the form of Zr).
Described fracturing liquid comprises optional components, can comprise those additives that are usually used in field use.Therefore, described fracturing liquid also can comprise one or more propping agents, flow improver, sterilant, organic solvent, chemical breaker, tensio-active agent, stratum control agent or the like.Propping agent comprises sandstone, alumina, granulated glass sphere, nylon pellet, aluminum shot and analogous material.Flow improver comprises polyacrylamide.The available organic solvent comprises monohydroxy-alcohol, dibasic alcohol, polyvalent alcohol and such as the hydrocarbon of diesel oil.Chemical breaker destroys the polymkeric substance (gel) that is crosslinked with controllable manner, and comprises enzyme, alkali metal persulphate and ammonium persulphate.
According to independent component, desired crosslinking time, temperature and by other conditions that exist in the stratum of pressure break or the blocked infiltration area, add these optional components with the significant quantity that is enough to obtain desired cross-linking properties.
Described fracturing liquid makes by following method, and described method comprises usually under agitation, makes crosslinkable polymer (HPG) and liquid, aqueous reaction form base gel.Base gel is contacted with zirconium crosslink agent to obtain fracturing liquid.Other component that comprises optional components can be joined among described base gel, zirconium crosslink agent or the two.
Do not need specific addition sequence though prepare fracturing liquid of the present invention, at first mix with salt solution with liquid, aqueous that to obtain salt brine solution be easily.Can in salt brine solution, continue simultaneously or mutually and add thermo-stabilizer, acid and hydroxypropylguar gum." simultaneously " adding is meant that two or more components add or add the interval simultaneously less than 60 seconds, for example are no more than 30 seconds at interval.Usually liquid, aqueous, salt solution, thermo-stabilizer, acid and hydroxypropylguar gum are mixed to be incorporated in making it leave standstill for some time before adding buffer reagent, the described time is usually less than 60 minutes, and preferred 10 to 40 minutes, such as 30 minutes.Buffer reagent (preferred yellow soda ash or salt of wormwood) joined in the described mixture and before adding zirconium crosslink agent make described mixture leave standstill for some time, the described time is usually less than 60 minutes, and preferred 10 to 40 minutes, such as 30 minutes.Described zirconium crosslink agent generally is the component that joins at last in the described fracturing liquid.
The invention provides the method on waterfrac treatment stratum, described method comprises to be enough in the stratum to produce, to reopen and/or to prolong one or more fissured flow and pressure is introduced fracturing liquid to the stratum, it is liquid, aqueous that described fracturing liquid comprises (a), (b) salt solution, (c) thermo-stabilizer (d) is enough to provide non-retardance ealkaline buffer less than 9 pH, (e) organic acid, (f) hydroxypropylguar gum (HPG) and (g) zirconium crosslink agent.Of the fracturing fluid preferred embodiment is described in above.
In an embodiment of the method on waterfrac treatment stratum,, and be incorporated in the stratum with single logistics form with liquid, aqueous, salt solution, thermo-stabilizer, buffer reagent, acid, hydroxypropylguar gum and zirconium crosslink agent premix.In this embodiment, zirconium crosslink agent contacted before being incorporated into them in the stratum with HPG, made linking agent and HPG polymer reaction form cross linked gel.Preferably zirconium crosslink agent is introduced with the zirconium solution form.Then to be enough in the stratum to produce, to reopen and/or to prolong fissured flow and pressure is incorporated into cross linked gel in the stratum.In this method, by HPG is prepared base gel with liquid, aqueous the mixing.Cross linked gel by with base gel and zirconium crosslink agent solution (zirconium solution) are mixed must.In this embodiment, annexing ingredient (salt solution, thermo-stabilizer, buffer reagent and acid) and any optional components can be joined in base gel, zirconium solution or the two.For example, HPG is mixed to form base gel with liquid, aqueous, salt solution, thermo-stabilizer, buffer reagent and acid.This base gel is mixed with zirconium solution to obtain cross linked gel, be introduced in the stratum then.
In second embodiment of the method on waterfrac treatment stratum, zirconium crosslink agent did not contact before being incorporated into them in the stratum with HPG.This method comprises that (a) is by preparing base gel with HPG with liquid, aqueous the mixing; (b) base gel is incorporated in the stratum, (c) when being incorporated into base gel in the stratum or afterwards, zirconium crosslink agent is incorporated in the stratum; (d) make base gel and linking agent in the stratum, form cross linked gel.Preferably zirconium crosslink agent is introduced with the zirconium solution form.Annexing ingredient (salt solution, thermo-stabilizer, buffer reagent and acid) and any optional components can be joined in base gel, zirconium solution or the two.For example, HPG is mixed to form base gel with liquid, aqueous, salt solution, thermo-stabilizer, buffer reagent and acid.This base gel and zirconium crosslink agent are mixed in the stratum to form cross linked gel.
Alternatively, when zirconium crosslink agent did not contact before being incorporated into them in the stratum with HPG, use the pit shaft earth penetrating.Zirconium crosslink agent preferably contacts to form cross linked gel with base gel in pit shaft with the form of zirconium solution.By pit shaft cross linked gel is incorporated in the stratum.Zirconium solution makes by zirconium crosslink agent is dissolved in solvent such as water or the alcohol.This waterfrac treatment comprises that by the method on the stratum that pit shaft penetrates (a) makes base gel by making hydroxypropylguar gum with liquid, aqueous the contact; (b) base gel is incorporated in the pit shaft; (c) when being incorporated into base gel in the pit shaft or afterwards, zirconium crosslink agent solution is incorporated in the pit shaft; (d) base gel and zirconium crosslink agent are reacted to form cross linked gel in pit shaft; (e) to be enough in the stratum to produce, to reopen and/or to prolong fissured flow and pressure is incorporated into cross linked gel in the stratum from pit shaft.Before being incorporated into base gel and zirconium crosslink agent in the pit shaft, annexing ingredient (salt solution, thermo-stabilizer, buffer reagent and acid) and any optional components can be mixed with base gel, zirconium crosslink agent or the two independently.For example, HPG is mixed to form base gel with liquid, aqueous, salt solution, thermo-stabilizer, buffer reagent and acid.This base gel is mixed with zirconium crosslink agent to obtain cross linked gel, be introduced in the stratum then.
After producing one or more crack, described method comprises that also the fracturing liquid that will comprise zirconium crosslink agent, crosslinkable organic polymer and propping agent is incorporated in one or more crack.Do not comprise under the situation of propping agent being used to produce one or more fissured cross-linked composition, preferably implement the second time of zirconium and introduce.Crosslinkable organic polymer in adding for the second time can be hydroxypropylguar gum or any other suitable crosslinkable organic polymer.
The present invention also provides selectivity to stop up infiltration area and the method for splitting leakage in the stratum, described method comprises to infiltration area and ground slabbing leaks site introducing fracturing liquid, it is liquid, aqueous that described fracturing liquid comprises (a), (b) salt solution, (c) thermo-stabilizer (d) is enough to provide non-retardance ealkaline buffer less than 9 pH, (e) organic acid, (f) hydroxypropylguar gum and (g) zirconium crosslink agent.Before fracturing liquid being incorporated into infiltration area or slabbing leakage site, aforesaid optional components can be joined in the fracturing liquid.
Infiltration area or split in the embodiment of method of leakage in stopping up the stratum with liquid, aqueous, salt solution, thermo-stabilizer, buffer reagent, acid, hydroxypropylguar gum and zirconium crosslink agent premix, and is incorporated in the stratum with single logistics form.In this embodiment, zirconium crosslink agent contacted before being incorporated into them in the stratum with HPG, made the reaction of HPG polymkeric substance and zirconium crosslink agent form cross linked gel.Preferably zirconium crosslink agent is introduced with the zirconium solution form.Then cross linked gel is incorporated in the stratum.In this method, by HPG is prepared base gel with liquid, aqueous the mixing.Cross linked gel can be by mixed with base gel and zirconium crosslink agent (being preferably the zirconium solution form).In this embodiment, annexing ingredient (salt solution, thermo-stabilizer, buffer reagent and acid) and any optional components can be joined in base gel, zirconium crosslink agent or the two.For example, HPG is mixed to form base gel with liquid, aqueous, salt solution, thermo-stabilizer, buffer reagent and acid.This base gel is mixed with zirconium crosslink agent to obtain cross linked gel, be introduced in the stratum then.
Infiltration area or split in second embodiment of method of leakage in stopping up the stratum, zirconium crosslink agent did not contact before being incorporated into them in the stratum with HPG, and took place crosslinked in the stratum.Preferably zirconium crosslink agent is introduced with the zirconium solution form.This method comprises that (a) is by preparing base gel with HPG with liquid, aqueous the mixing; (b) base gel is incorporated into the infiltration area or the ground slabbing is leaked the site, (c) when base gel being incorporated into infiltration area or ground slabbing to leak the site or afterwards, zirconium crosslink agent is incorporated into the infiltration area or the ground slabbing is leaked in the site; (d) make base gel and linking agent reaction forming cross linked gel with the described zone of leak stopping and/or split leakage.In this embodiment, annexing ingredient (salt solution, thermo-stabilizer, buffer reagent and acid) and any optional components can be joined in base gel, zirconium crosslink agent or the two.For example, HPG is mixed to form base gel with liquid, aqueous, salt solution, thermo-stabilizer, buffer reagent and acid.This base gel and zirconium crosslink agent are mixed in the stratum to form cross linked gel.
Alternatively, when zirconium crosslink agent did not contact before they being incorporated into the infiltration area in the stratum or splitting in the leakage with HPG, available pit shaft penetrated described zone or stratum.Zirconium crosslink agent preferably contacts to form cross linked gel with base gel in pit shaft with the form of zirconium solution.By pit shaft cross linked gel is incorporated in the stratum.Zirconium solution can make by zirconium crosslink agent is dissolved in solvent such as water or the alcohol.This method (wherein penetrate described zone or split leakage with pit shaft) of stopping up infiltration area in the stratum or splitting leakage comprises that (a) is by preparing base gel with hydroxypropylguar gum and liquid, aqueous the mixing; (b) base gel is incorporated in the pit shaft; (c) when being incorporated into base gel in the pit shaft or afterwards, zirconium crosslink agent solution is incorporated in the pit shaft; (d) base gel and zirconium crosslink agent are reacted in pit shaft and form cross linked gel; (e) cross linked gel is incorporated in zone or the stratum by pit shaft.Before being incorporated into base gel and zirconium crosslink agent in the pit shaft, annexing ingredient (salt solution, thermo-stabilizer, buffer reagent and acid) and any optional components can be mixed with base gel, zirconium crosslink agent or the two independently.For example, HPG is mixed to form base gel with liquid, aqueous, salt solution, thermo-stabilizer, buffer reagent and acid.This base gel is mixed to form cross linked gel in pit shaft with zirconium crosslink agent, be introduced in the stratum then.
The relative quantity of HPG and zirconium crosslink agent title complex can change.Can use less and effective amount, the amount of the two will change according to condition, described condition for stratigraphic type for example, implement the degree of depth that described method (for example fluid fracturing, the infiltration area is stopped up or split and leaks obstruction) locates, temperature, pH value etc.In general, every kind of the least possible component of usage quantity obtains required viscosity, such as form behind the cross linked gel 90 minutes viscosity of 100cp at least, to obtain required result, be the pressure break stratum, or stop up the infiltration area or split the required degree of leaking to promoting from the stratum abundant refiltered oil or gas.
Surprisingly, in the method on waterfrac treatment stratum, or stop up in the stratum infiltration area or split in the method for leakage in selectivity, join in the of the fracturing fluid base gel and use ealkaline buffer that pH is kept less than 9 acid, can make HPG under about 275 (135 ℃) or higher temperature, can be used as the crosslinkable organic polymer.
Embodiment
Zirconium crosslink agent zirconium-lactylate salt (TYZOR 217 organic zirconium hydrochlorates), alkanolamine zirconate (TYZOR 212 organic zirconium hydrochlorates) and trolamine zirconate (TYZOR TEAZ organic zirconium hydrochlorate) all can from E.I.du Pont de Nemours and Company (Wilmington, DE) commercially available.Zirconium-lactic acid ammonium salt can make with the ammonium hydroxide neutralization then by basic zirconium chloride and lactic acid reaction.
Carboxymethyl hydroxypropyl guar (CMHPG), hydroxypropylguar gum (HPG) and natural guar gum can be from Rhodia, and Inc. (NJ) is commercially available.(Milwaukee WI) buys from AldrichChemical Company to be used for all other chemical reagent of this paper.
Comparative Example A An 1 and A2
Mix in broken machine wide-necked bottle and the KCl salt solution (20g) by distilled water (1L) being joined watt woods, make base gel.With solution stirring, and with hydroxypropylguar gum (HPG 4.2g) joins in the vortex of stirred solution.With described solution stirring 30 minutes.Sodium bicarbonate buffer agent (1.45g) and Sodium Thiosulfate Pentahydrate (1.2g) join in the solution.With described solution stirring 30 minutes.The gained gel was left standstill at least one hour, add zirconium crosslink agent afterwards to make fracturing liquid.
Comparative Examples B
Mix in broken machine wide-necked bottle and the Sodium Thiosulfate Pentahydrate (3.6g) by distilled water (1L) being joined watt woods, make base gel.With solution stirring, and with hydroxypropylguar gum (HPG 6.6g) joins in the vortex of stirred solution.With described solution stirring 30 minutes.Add sodium carbonate buffer with pH regulator to 9.5.Add sodium hydroxide then with pH regulator to 10.With described solution stirring 5 minutes, and add aqueous citric acid solution (25%, 0.75g).With described solution stirring 5 minutes.The gained gel was left standstill 30 minutes at least, add zirconium crosslink agent afterwards to make fracturing liquid.
Comparing embodiment C1 and D1
(TMAC 2g) in the aqueous solution, makes base gel by distilled water (1L) being joined mixed broken machine wide-necked bottle of watt woods and 50% tetramethyl ammonium chloride salt.With solution stirring, and with Carboxymethyl hydroxypropyl guar (CMHPG 6g) is sprinkled in the vortex of stirred solution.With the pH regulator to 6 of sodium Diacetate (buffer reagent), and stirred 30 minutes gained solution.Use 10% sodium hydroxide solution with pH regulator to 10 then.Stop to stir, described gel was left standstill 30 minutes at least, add zirconium crosslink agent afterwards to make fracturing liquid.
Comparing embodiment C2 and D2
Mix in the broken machine wide-necked bottle and add 50% tetramethyl ammonium chloride salt (TMAC, the 2g) aqueous solution makes base gel by distilled water (1L) being joined watt woods.With solution stirring, and with hydroxypropylguar gum (HPG 6g) joins in the vortex of stirred solution.With the pH regulator to 6 of sodium Diacetate, and stirred 30 minutes gained solution.Use sodium hydroxide solution (10%) with pH regulator to 10 then.Described gel was left standstill 30 minutes at least, add zirconium crosslink agent afterwards to make fracturing liquid.
Comparing embodiment E
Mix in the broken machine wide-necked bottle by distilled water (1L) being joined watt woods, and add KCl salt solution (20g), make base gel.Stir described solution.Sodium Thiosulfate Pentahydrate (2.4g), fumaric acid (0.55g) and natural guar gum (6.0g) are joined in the described solution, and with described solution stirring 30 minutes.Use then yellow soda ash (buffer reagent) with pH regulator to pH 8.8.Stop to stir, described gel was left standstill 30 minutes at least, add zirconium crosslink agent afterwards to make fracturing liquid.
Embodiment 1 to 5
Mix in the broken machine wide-necked bottle by distilled water (1L) being joined watt woods, and add KCl salt solution (20g), make base gel.Stir described solution.(HPG 6.0g) joins in the described solution (promptly adding at interval less than 60 seconds) simultaneously, and with described solution stirring 30 minutes with Sodium Thiosulfate Pentahydrate (2.4g), fumaric acid (0.55g) and hydroxypropylguar gum.Use then yellow soda ash (buffer reagent) with pH regulator to 7.8 to 8.8.Stop to stir, described gel was left standstill 30 minutes at least, add zirconium crosslink agent afterwards to make fracturing liquid.
Embodiment 6
Mix in the broken machine wide-necked bottle by distilled water (1L) being joined watt woods, and add KCl salt solution (20g), make base gel.Stir described solution.(HPG 6.0g) joins in the described solution, and with described solution stirring 30 minutes with Sodium Thiosulfate Pentahydrate (2.4g), acetate (0.58g) and hydroxypropylguar gum.Use then yellow soda ash (buffer reagent) with pH regulator to pH 8.8.Stop to stir, described gel was left standstill 30 minutes at least, add zirconium crosslink agent afterwards to make fracturing liquid.
Embodiment 7
Mix in the broken machine wide-necked bottle by distilled water (1L) being joined watt woods, and add KCl salt solution (20g), make base gel.Stir described solution.(HPG 6.0g) joins in the described solution, and with described solution stirring 30 minutes with Sodium Thiosulfate Pentahydrate (2.4g), lactic acid (0.76g) and hydroxypropylguar gum.Use then yellow soda ash (buffer reagent) with pH regulator to pH 8.8.Stop to stir, described gel was left standstill 30 minutes at least, add zirconium crosslink agent afterwards to make fracturing liquid.
Embodiment 8
Mix in the broken machine wide-necked bottle by distilled water (1L) being joined watt woods, and add KCl salt solution (20g), make base gel.Stir described solution.(HPG 6.0g) joins in the described solution, and with described solution stirring 30 minutes with Sodium Thiosulfate Pentahydrate (2.4g), formic acid (0.44g) and hydroxypropylguar gum.Use then yellow soda ash (buffer reagent) with pH regulator to pH 8.8.Stop to stir, described gel was left standstill 30 minutes at least, add zirconium crosslink agent afterwards to make fracturing liquid.
The viscosity measurement of zirconate crosslinked base gel
After making base gel, the zirconium crosslink agent (32 to 148ppm) of aequum is joined in every kind of base gel (250mL), then with gained solution stirring 30 seconds.Fracturing liquid (base gel (25mL) that comprises linking agent after promptly stirring) is put in the cup of FANN 50 viscometers, unless fracturing liquid gelling in blender.With 170sec
-1Shearing rate is sheared and under 275 °F to 340 °F (135 ℃ to 171 ℃), is measured viscosity continuously.Under the possible situation, write down the viscosity measurement value after 10 minutes, 30 minutes, 60 minutes and 90 minutes.
Table 1: results of property
Table 2: results of property
The result
Table 1 and 2 provides the results of property of comparing embodiment of the present invention and embodiment.Table 1 and 2 has been listed zirconium crosslink agent type, guar gum type and the concentration among each comparing embodiment of the present invention and the embodiment, used salt solution, organic acid (if you are using), temperature, pH and the viscosity results that records.Guar gum concentration is that unit measures with pptg (pound/1000 gallons), and is weight % unit in the bracket." Zr carrying capacity " is meant that be the zirconium amount that unit adds by described fracturing liquid gross weight with part each 1,000,000 parts (ppm).With designated time intervals, be that unit mensuration viscosity is measured with centipoise (cp).If the crosslinked base gel of zirconium keeps acceptable viscosity (for example greater than 100cp) 90 minutes, then described gel work is good.If viscosity is less than 100cp after 90 minutes, if perhaps viscosity is classified "-" ((before 90 minutes) viscosity is crossed low so that the gel deterioration during the expression measurement) as, then the crosslinked gel of zirconium is considered to " defective ".Alternatively, if fracturing liquid gelling before measuring viscosity (promptly being described as " gelling in blender " in the table), then described fracturing liquid is defective.
Comparative Example A An 1 and A2 are the base gels crosslinked with zirconium-lactic acid salt, and it also is called as fracturing liquid, can adopt United States Patent (USP) 4,801, and the condition of describing in 389 makes.Described fracturing liquid has initial high viscosity, but after 10 minutes, viscosity is lower than desirable value, and becomes defective less than 20 minutes fracturing liquids.Fracturing liquid among Comparative Example A An 1 and the A2 is defective down at 275 °F (135 ℃) and 340 °F (171 ℃) respectively.
According to United States Patent (USP) 6,737,386 preparations but be to use HPG rather than natural guar gum be used for Comparative Examples B with the crosslinked base gel of zirconium-lactic acid salt.Therefore the gelling immediately of described fracturing liquid does not have viscosity and measures.Surprisingly, when natural gel is derived guar gum HPG when substituting, United States Patent (USP) 4,801, the condition that is fit to natural gel in 389 or 6,737,386 is invalid.
Use natural guar gum to substitute HPG, that uses that condition of the present invention makes is used for comparing embodiment E with the crosslinked base gel of zirconium-lactic acid salt.Surprisingly, described cross-linked composition gelling immediately.
Comparing embodiment C1 and C2 be use CMHPG and HPG to make respectively and with the alkanolamine zirconate crosslinked to make of the fracturing fluid base gel.At high temperature, the CMHPG-fluid can be worked during 90 minutes well, but the HPG-fluid showed low viscosity in the time of 10 minutes, and defective down at 250 °F.Therefore, when HPG rather than CMHPG are used in hope, if or can't obtain CMHPG the time, the condition that is fit to CMHPG always can not be successfully used to HPG.
Comparing embodiment D1 and D2 be use CMHPG and HPG to make respectively and with the trolamine zirconate crosslinked to make of the fracturing fluid base gel.At high temperature, the CMHPG-fluid can be worked during 60 minutes well, but the HPG-fluid is defective down at 275 °F (135 ℃) after 10 minutes.Equally, these comparing embodiments show that HPG and CMHPG are not interchangeable in fracturing liquid.
Fracturing liquid in the embodiment of the invention 1 to 8 can use HPG and zirconium-lactylate salt, zirconium-lactic acid ammonium salt and alkanolamine zirconate, is making under the temperature of 275 to 340 (135 ℃ to 171 ℃).Embodiment 1 to 8 is showing desired viscosity (viscosity is greater than 100cp after 90 minutes) during 90 minutes, and does not show the premature deterioration that is caused by shearing that is shown in the comparing embodiment of using HPG.Use HPG in fracturing liquid of the present invention, viscosity and viscosity retentivity in time is suitable each other under test high temperature, and suitable with the comparing embodiment of employing CMHPG in the fracturing liquid that uses the trolamine zirconate.
Therefore show, comprise zirconium crosslink agent, salt solution (KCl), stablizer, non-retardance ealkaline buffer (yellow soda ash), acid and the fracturing liquid of the present invention that has less than the temperature in 9 pH and 275 to 340 (135 ℃ to 171 ℃) scopes can be used as hydrofrac fluid.These fracturing liquids can be used in the pressure break or blocking field of high temperature deep well, and wherein HPG is used main guar gum.
Claims (14)
1. it is liquid, aqueous to comprise (a), (b) salt solution, and (c) thermo-stabilizer (d) is enough to provide non-retardance ealkaline buffer less than 9 pH, (e) organic acid, (f) hydroxypropylguar gum and (g) fracturing liquid of zirconium crosslink agent.
2. the fracturing liquid of claim 1, wherein said pH is 7.5 to 8.9.
3. the fracturing liquid of claim 1, wherein said liquid, aqueous water and the aqueous alcohol of being selected from.
4. the fracturing liquid of claim 1, wherein said buffer reagent is yellow soda ash or salt of wormwood.
5. the fracturing liquid of claim 4, wherein said salt solution is tetramethyl ammonium chloride or Repone K; Described thermo-stabilizer is methyl alcohol, alkali metal thiosulfate or ammonium thiosulfate; Described acid is formic acid, acetate, lactic acid or fumaric acid.
6. the fracturing liquid of claim 5, wherein said liquid, aqueous be water, described thermo-stabilizer is a Sulfothiorine, described buffer reagent is a yellow soda ash, and described acid is fumaric acid.
7. the method on waterfrac treatment stratum, described method comprises that to introduce (a) to described stratum liquid, aqueous to be enough in the stratum to produce, reopen and/or to prolong fissured flow and pressure, (b) salt solution, (c) thermo-stabilizer, (d) be enough to provide non-retardance ealkaline buffer, (e) organic acid, (f) hydroxypropylguar gum less than 9 pH, (g) zirconium crosslink agent, the temperature on wherein said stratum is in the scope of 275 to 340 (135 ℃ to 171 ℃).
8. the method for claim 7 wherein is incorporated in the described stratum with described liquid, aqueous, salt solution, thermo-stabilizer, buffer reagent, acid, hydroxypropylguar gum and described zirconium crosslink agent premix and with single logistics form.
9. the method for claim 7 wherein penetrates described stratum with pit shaft; And described method comprises that (a) makes base gel by making hydroxypropylguar gum with liquid, aqueous the contact; (b) base gel is incorporated in the pit shaft; (c) when being incorporated into base gel in the pit shaft or afterwards, zirconium crosslink agent solution is incorporated in the pit shaft; (d) base gel and zirconium crosslink agent are reacted to form cross linked gel in pit shaft; (e) to be enough in the stratum to produce, to reopen and/or to prolong fissured flow and pressure is incorporated into cross linked gel the described stratum from pit shaft.
10. the method for claim 9, wherein said zirconium crosslink agent is the form of zirconium solution, described zirconium solution makes by described zirconium crosslink agent is dissolved in water or the alcohol, and wherein described hydroxypropylguar gum is mixed with the formation base gel with described liquid, aqueous, salt solution, thermo-stabilizer, buffer reagent and acid.
11. infiltration area or split the method for leakage in the obstruction stratum, described method comprises to described zone or describedly splits in the leakage that to introduce (a) liquid, aqueous, (b) salt solution, (c) thermo-stabilizer, (d) be enough to provide non-retardance ealkaline buffer, (e) organic acid, (f) hydroxypropylguar gum less than 9 pH, (g) zirconium crosslink agent, the temperature on wherein said zone or stratum is in the scope of 275 to 340 (135 ℃ to 171 ℃).
12. the method for claim 11 wherein is incorporated in the described stratum with described liquid, aqueous, salt solution, thermo-stabilizer, buffer reagent, acid, hydroxypropylguar gum and zirconium crosslink agent premix and with single logistics form.
13. the method for claim 11, wherein said zirconium crosslink agent did not contact before being incorporated into them in the stratum with hydroxypropylguar gum, and wherein penetrate described zone or stratum with pit shaft, described method comprises that (a) passes through hydroxypropylguar gum and the liquid, aqueous mixed base gel that gets; (b) base gel is incorporated in the pit shaft; (c) when being incorporated into base gel in the pit shaft or afterwards, zirconium crosslink agent solution is incorporated in the pit shaft; (e) base gel and zirconium crosslink agent are reacted to form cross linked gel in pit shaft; (f) cross linked gel is incorporated into described zone or the stratum from pit shaft.
14. the method for claim 13, wherein said zirconium crosslink agent is the form of zirconium solution, described zirconium solution makes by described zirconium crosslink agent is dissolved in water or the alcohol, and wherein described hydroxypropylguar gum is mixed with the formation base gel with described liquid, aqueous, salt solution, thermo-stabilizer, buffer reagent and acid.
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| US160307P | 2007-11-02 | 2007-11-02 | |
| US61/001603 | 2007-11-02 | ||
| PCT/US2008/082024 WO2009059160A1 (en) | 2007-11-02 | 2008-10-31 | High temperature aqueous-based zirconium fracturing fluid and use |
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| CN101896573A true CN101896573A (en) | 2010-11-24 |
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| CN2008801208902A Pending CN101896573A (en) | 2007-11-02 | 2008-10-31 | High temperature aqueous-based zirconium fracturing fluid and use |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20090114390A1 (en) |
| EP (1) | EP2209868A1 (en) |
| CN (1) | CN101896573A (en) |
| CA (1) | CA2704542A1 (en) |
| MX (1) | MX2010004912A (en) |
| RU (1) | RU2010122306A (en) |
| WO (1) | WO2009059160A1 (en) |
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| CN102504798A (en) * | 2011-10-17 | 2012-06-20 | 中国石油化工股份有限公司西北油田分公司工程技术研究院 | Ground crosslinked acid liquid for acid fracturing and preparation method thereof |
| CN103666436A (en) * | 2012-09-18 | 2014-03-26 | 中国石油天然气股份有限公司 | Acidic modified seaweed gel fracturing fluid |
| CN105916959A (en) * | 2013-12-02 | 2016-08-31 | 埃奥格资源公司 | Fracturing process using liquid ammonia |
| CN109852365A (en) * | 2018-12-17 | 2019-06-07 | 中国石油天然气股份有限公司 | Prepare method, the guanidine gum fracturing fluid by this method preparation and its application of guanidine gum fracturing fluid |
| CN111117593A (en) * | 2018-11-01 | 2020-05-08 | 中国石油化工股份有限公司 | Crosslinking agent and preparation method thereof |
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| US11268016B2 (en) | 2014-12-11 | 2022-03-08 | Saudi Arabian Oil Company | High temperature treatment fluids with nano-crosslinkers |
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| CN102504798A (en) * | 2011-10-17 | 2012-06-20 | 中国石油化工股份有限公司西北油田分公司工程技术研究院 | Ground crosslinked acid liquid for acid fracturing and preparation method thereof |
| CN102504798B (en) * | 2011-10-17 | 2013-05-22 | 中国石油化工股份有限公司西北油田分公司工程技术研究院 | Ground crosslinked acid liquid for acid fracturing and preparation method thereof |
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| CN105916959A (en) * | 2013-12-02 | 2016-08-31 | 埃奥格资源公司 | Fracturing process using liquid ammonia |
| CN111117593A (en) * | 2018-11-01 | 2020-05-08 | 中国石油化工股份有限公司 | Crosslinking agent and preparation method thereof |
| CN109852365A (en) * | 2018-12-17 | 2019-06-07 | 中国石油天然气股份有限公司 | Prepare method, the guanidine gum fracturing fluid by this method preparation and its application of guanidine gum fracturing fluid |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2209868A1 (en) | 2010-07-28 |
| MX2010004912A (en) | 2010-05-14 |
| WO2009059160A1 (en) | 2009-05-07 |
| RU2010122306A (en) | 2011-12-10 |
| CA2704542A1 (en) | 2009-05-07 |
| US20090114390A1 (en) | 2009-05-07 |
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