CA1266558A - Peroxygen breaker systems for well completion fluids - Google Patents

Peroxygen breaker systems for well completion fluids

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Publication number
CA1266558A
CA1266558A CA000512014A CA512014A CA1266558A CA 1266558 A CA1266558 A CA 1266558A CA 000512014 A CA000512014 A CA 000512014A CA 512014 A CA512014 A CA 512014A CA 1266558 A CA1266558 A CA 1266558A
Authority
CA
Canada
Prior art keywords
hydraulic medium
peroxygen compound
weight
free radical
radical scavenger
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
CA000512014A
Other languages
French (fr)
Other versions
CA1266558C (en
Inventor
Robert D. Norris
Richard A. Brown
Gaylen R. Brubaker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FMC Corp
Original Assignee
FMC Corp
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Filing date
Publication date
Application filed by FMC Corp filed Critical FMC Corp
Priority to CA000512014A priority Critical patent/CA1266558A/en
Application granted granted Critical
Publication of CA1266558C publication Critical patent/CA1266558C/en
Publication of CA1266558A publication Critical patent/CA1266558A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S507/00—Earth boring, well treating, and oil field chemistry
    • Y10S507/925—Completion or workover fluid

Abstract

Abstract;

A hydraulic process has been developed and a process to treat subterranean formations whereby the medium can maintain for a period of time a sufficient viscosity to function as a hydraulic medium and optionally to support particulate matter. Subsequently, the viscosity of the medium decreases to facilitate the removal of the medium.

Description

P R _ YGEN BREAKER SYSTEMS FOR WELL COMPL~TION FLUIDS
This invention relates to a composition and to a method useful for hydraulically treating a subterranean formation. The invention is particularly useful for creating and maintaining a fracture in a subterranean formation to stimulate the flow of a fluid therefrom or for placing a permeable or impermeable pack in contact with a formation to facilitate or control fluid flow into or out of the formation. More particularly, the invention relates to hydraulic media containing nitrite to inhibit premature breaking by a peroxygen compound.
Treatment of a subterranean formation with a hydraulic medium to create and maintain a fracture through which a fluid can flow is us~lally practical by injecting a hydraulic medium with a high viscosity.
The purpose of the high viscosity can be either to prevent the premature loss of the hydraulic medium through a thief zone or to suspend solid particles in the liquid. Such solid particles may be deposited in the fracture and serve as propping agents to maintain the integrity of the fracture. Solids suitable as propping agents include sand, gravel, walnut shells and the like.
Solid particles may also be used to form an 1 25 impervious consolidated pack in contact with a \ subterranean formation to seal off a porous formation.
Typical applications include sealing a porous formation to prevent loss of oil or gas from a well, or to block groundwater from flowing through cracks or joints into a sewer or basement.
Subterranean formations may also be treated with a hydraulic medium to place a permeable pack adjacent to an unconsolidated formation to hold the formation in place while withdrawing a fluid from it. A typical application is recovering petroleum from a loose sand formation. Many other applications to control ~' 5~

the flow of a fluid at any natural or artificial subterranean interface will be apparent to those skilled in the art.
Usually, aqueous compositions, including brines, are selected for use as a hydrauli~ medium because of the ready availability and the low cost of water. The hydraulic medium is usu~lly formulated with thickening agents and other additives well-known in the art to be useful under the conditions within the specific subterranean geological formations.
A wide variety of hydratable polymeric materials have been found useful as thickening agents in such hydraulic media.
These include hydratable polysaccharides, polyacrylamides, and polyacrylamide copolymers.
Particularly desirable polysaccharides include galacto~annan gums, derivatives thereof, and cellulose derivatives. Typical polysaccharides include: guar gums, locust bean gum, karagya gum, sodium carboxymethyl guar, hyd}oxyethyl guar, hydroxypropyl guar, sodium hydroxymethyl cellulose, sodium carboxymethyl-hydroxyethyl cellulose, and hydroxyethyl cellulose.
Optionally, cross-linking agents may be added \ 25 which increase the maximum temperature at which the \ hydratable polymers will retain the desired high viscosity. These cross-linking agents are well known in the art and include polyvalent metal ions, such as chromium (III), aluminum (III), titanium (IV) and polyvalent anions, such as borates.
The combination of pH~ the hydratable polymeric material and the cross-linking agent selected can be important factors in obtaining and maintaining the desired viscosity. A p~ of 3 or less will frequently cause breaking or loss of viscosity: a pH of 10 or more the solubility of many of the polymers is insufficient to provide a viscous solution. It is usually desirable that the pH of hydraulic medium is maintained in the tS~

--3~

neutral range between 5 and 7.5, which tends to reduce corrosion which would occur at a lower pH and to reduce the cost of buffers or other additivesi but, by proper choice of material, the effective pH range can be from 1 to 12, preferably from 3 to 12.
At the completion of the hydraulic treatment, the viscosity of the hydraulic liquid is generally reduced to facilitate its removal from the vicinity of the treated formation. ~ substantial reduction of 10 viscosity of the hydraulic liquid is generally termed "breaking".
The viscosity of hydraulic media formulated with such hydratab]e polymeric materials will reduce or break in time as the result of either biological action 15 or high temperatures. The breaking can be accelerated by the use of chemical additives called "breakers", such as enzymes, acids, and oxidizing agents.
Peroxygen compounds are well known breakers because the peroxygen compounds readily Eorm effective free 20 radicals under the usual conditions of use and because no objectionable residue remains to cause disposal problems.
U.S. Patent No. 4,144,179 to Chatterji discloses that the minimum practical temperature for peroxygen 25 breakers can be decreased from 50C to about 20C by adding a soluble metal salt wherein the oxidation number of the metal ion is less that the highest possible oxidation number for the metal ion. The metal salts are accelerators which increase the rate of free 30 radical formation by peroxygens and thereby decrease the temperature necessary to generate sufficient free radicals to depolymerize the polymer in a relatively short time. The patent discloses as accelerators cuprous, ferrous, stannolus, cobaltous, chromous, 35 nickelous, titanous, manganous, and arsenous salts of the halides, sulfates, and nitrates.

The patent to Chatterji reco~ni~es that it is necessa~y to delay ~he t iln~ wl~ich the breakin~
takes place~ but the only mearls su~ested is by add-ing the accelerator as a slowly-soluble salt of the metal. As a re~sult, a sufficient concentration of metal ion will not buiId up in the composition to cause breaking under ideal conditions un-til after the treatment of the subterranean forlnation is completed.
This method of control is undesirable because unplan-ned factors can affect the rate of solution of thesolid metal salts, such as the pH and temperature within the formation, as well as the presence of unexpected anions, such as silicates or carbonates.
in addition, the metal ions may be physically removed frorr) the solution by natural zeolites, or alterna-tively, additional ions rnay be leached from local mineral deposits in the forma~ion.
U. S. Patent No. 4,202,795 to Burnam et al. also discloses the desirability of delaying the effect of the breakers. The Burnam et al. patent teaches -the use of a coated pellet containing the accelerator, the coating cornprising a solid, hydratable polymeric material similar to the polymers used to increase the viscosity of the hydraulic rnedium. The method of the Burnam et al. patent has the disadvantage of merely delaying the release of the accelerator; it also has the disadvantage of requiring the blending of pellets into the viscous composition. Furthermore, the pellets may be subject to attrition which may cause a premature release of the accelerator. In addition, after the pellets have been rnanufac-tured there are no rneans to adjust the timing of the release of the accelerator in response to unexpected conditions observed in the forrnation, particularly at the higher ternperatures encountered at increased depths~
Canadian Patent No. 1,217,930 teaches that free radieal ~cavengers such as hydroxylated aromatic compounds and unsaturated alchols are effective in delaying the effect of such breakers in hydraulic treating fluids. While effective in retarding breaking, the costs are appreciable beca~lse the scavengers must be used at high concentrations.
The present invention over~omes these disadvantages of the prior art by providiny an aqueous hydraulic mediurn containing nitrite ion or a source of nitrite ion to control ~nd inhibit the breaking of a hydraulic medium containing a peroxygen compound as a breaking agent.
The present invention is an aqueous composition which is suitable as a hydraulic medium for treating a subterranean formationO This aqueous composition comprises (1) a hydratable polymeric material, ~2) a peroxygen compound capable of subsequently generating free radicals in an amount sufficient to reduce the viscosity of the aqueous composition, and (3) a nitrite ion source. Optionally, the composition may also contain an organic hydroxyl compound effective as a free radical scavenger.
The efficacy of nitrite ion to inhibit the breaking of a hydraulic medium by a peroxygen compound \ 25 is unexpected. It is well known that nitrite ions can reduce peroxygen compounds. It would be expected that nitrite ions would function as part of a redox system and accelerate, rather that inhibit, breaking of a hydraulic medium by a peroxygen compound. In addition, the inhibitors taught by the prior art are compounds capable of forming low energy free radicals, and the nitrite ion is not known to exist as a free radical.
Nitrite ions may be incorporated into the hydrau-lic medium from any convenient source such a5 nitrous acid, a nitrogen oxide which will yield nitrous acid on hydrolysis, or a nitrite salt. Sodium nitrite is particularly clesiral)l ~ use of its re~ldy availa-bi I i ty and lo~v co~ t . I-~"- (:orlveni ence the qllallt i ty o~
nitri te ion i~l~ orpor~lL~d iuto ;l lor~nulatiorl is expressed as ~hc equiv Ll~ llt clu~ t i ty of sodiurn 5 nitrite. Generllly, irom I-oll~ ().I to lO parts by weigh-t of sodiulll ni~riLe per p.,l t by weight of the pe roxy ge n coinf)o und i s l f t e ;- l i v~ to i nh i b i t pre! na t u r e breaking, an(i frol-n O.'j to S p~lrts by weight of sodiu,n nitrite per par-t l>y wc~igllt of the pcroxygen cornpound 0 i5 preferred.
Unexpectedly, a col~v~ntional organic free radical scaverlger selected froln the ~roup consistirlg of un-saturated alcohols~ phenols, allylic mor)omers and rnixtures thereof, and ii nitr i-te ion in colnbination 15 are mole eftective in inhibiting prernature breaking than either component alone. This synergism suggests that the inhibiting effect of a nitrite ion is not relàted to free radical form.l-tion for then the ef ~ect would be at best additive. The nitrite ion may be 20 added to the hydraulic rncdiuln alone, or with a frec radic~l scavenger eitl)~r to del~y the time at which the hydraulic rnedium wi ll break, that is, lose vis-cosity, or to perrr-it the hydraulic medium -to rnaintain -the desired viscosity at higher ternperatures.
The usage of the ~ree radical scavengers wi I I
va r y acco rd i ng to t he e f f i cacy o f t he cornpound s and the desired conditiorl of use. Generllly, frorn 0.01 to 5 parts of a free radicdl scaveilger is added yer hundred parts of the hydraul ic me(lium; preferably 30 0.05 to 2.5 parts of the scaverlger is added per hundred parts of aqueous solution. -~his is equi-valen~ -to 0.1 to lO parts by weight of -the free radical scavenger per part by weight of peroxygen compound in the hydralJlic mediuln and pr. ferably .5 to 35 5 parts by weight ot the free r~ldical scavenger are used per pdrt by weight of the p~-roxygell cornpound.
~ne skilled in the art will normally ~elect the ingredients c~ th~ hycl~ 1]ic ~ `diu,n 011 dn overall cost-perforl-n~ ce blsis ~)r Ul .lviil~b ility basis.
Any convenient hydr.~tdl)le polyi"~lic Indterial rnay be used; such as ti-le hydrat~ble polysaccharides, polysaccilaride derivativ~s, polyl~ryla~rlides, and polyacrylalnide copoly~n~ conv~rlLionalIy used. Fr(jl-r I to lO0 kilogrdms of a hydr~t(d polyir)eric material per cubic rneter (I to lO0 g/lit~l-) oE the hydraulic mecliuln is generdlly satisflcL~ry ~o provide a usdble viscosity~
Similarly, any converlierlt peroxy~en may be selected dS -the breaker. IJsually it is desirable to u~se a relatively inexpensive peroiygen compound which will readily generate free radicals at the telnpera-tures found in the forrnation. It is generallypreferable to use a peroxyg-n colnl>ound selected from tl-e group consisting of hydrogell peroxide, t-butylhydroperoxide, the arrr-nonium and alkali metal salts of InonopersulEuric acid, arld ammonium ancl alkali rnetal salts of dipersulfuric acid. The per-oxygen compound may be present in thè hydraulic mediuln in an alnount equdl to froln I to 20 parts by weight of the hydratable polyineric inaterial present therein.
The following exarnples are presented to illustrate the practicirlg of the invention.
~'Xa''!L'I~s The experilnental proceclures used in Examples I to 21 were variations of the following example - as indicated in the tables.
A viscous solution or ~el was forrnecd by dis-solving 3.8 g of a hydratable polyloeric matèrial, such as hydroxypropyl guar, in 380 rnl water. After cornplete dissolution, a peroxygen breaker, usually 0.2 g arrrnonium persulfate, was added followed by any other additives as specified~ such as activators or ~ree r-ddical ~cav~ngers as ir,hihitors. The pH of the ~ 3 solution was ~djusted to pi~ 5 U iing 1O~ sul~uric acid or bllffered witll sodiu.l~ arbonate. rhe solutlon was allowed to st~lnd at r,')C. rht viscosity was determirled periodicclly u in, ~n `~L aaroid r~ehomete at 600 rp,n.
Exarr-lples 3 and 4 d~!noustr~te th~.~ the nitrite ion which was providecl IS sodiulrll,itrite is more eEfect-ive on a weight basii th~ known free rddical scavengers, such ~15, .~1 Iyl alcol-~ol (Exainples 5 and ~), phenol (Exarnples 7 ~ncl 8) ~nd 2-butene-1,4-diol (Example 15). Ihe synergistic eifects with free radical scavengers can be seen, for exalnple, when cornparing Examples 4 and 5 with Exal-nple 15.

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APS NaNO2 ~31~ i Vl~(cosity Rei-naining After Exalnple & ~__ g 2 h_ 4 hr 6 hr. 2? hr.

13 0 0 0 ~ L~ 82 ~2 14 0.2 0 0 5 3 3 3 0.2 0 6 37 8 5 4 16 0.2 1 6 ~3 28 17 5 17 0.2 2 6 71 41 23 7 18 0.2 4 6 60 35 18 4 19 0.2 0 12 51 13 7 5 0.2 2 12 Xl 59 35 13 21 0.2 4 12 71 55 38 14 Key 3.8 g of hydratable polyrneric material in 380 ml water plus addi-tives as indicated APS = ATmonium Persulfate NaNK?2 = Sodium Nitrite BD = 2-butane-1,4-dio

Claims (14)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A process for treating a subterranean formation characterized by introducing into said subterranean formation an aqueous hydraulic medium having a pH between 1 and 12 comprising a) from 1 to 100 kilograms per cubic meter of a hydratable polymeric material selected from the group consisting of polysaccharides, polysaccharide derivatives, polyacrylamides, polyaccharlamide copolymers and mixtures thereof, b) a peroxygen compound capable of generating free radicals, in an amount equal, to 1 to 20 parts by weight per 100 parts by weight of said polymeric material, thereby breaking or reducing the viscosity of the hydraulic medium to facilitate the removal of said medium from the vicinity of the treated formation, and c) nitrite ions for convenience expressed as the equivalent quantity of sodium nitrite, said nitrite ions in an amount of from 0.1 to 10 parts by weight per part by weight of the peroxygen compound in the hydraulic medium, said nitrite ions being incorporated into the hydraulic medium as a nitrogen compound capable of yielding a nitrite ion in the hydraulic fluid on hydrolysis or on solution thereby inhibiting the breaking of the hydraulic medium.
2. The process of claim 1 wherein said pH is between 3 and 12.
3. The process of claim 1 wherein said pH is between 3 and 10 .
4. The process of claim 1 wherein said pH is between 5 and 7.5.
5. The process of claim 1, 2 or 3 characterized in that said hydraulic medium also comprises from 0.1 to 10 parts of an organic free radical scavenger per part by weight of said peroxygen compound in said hydraulic medium.
6. The process of claim 1, 2 or 3 characterized in that said peroxygen compound is selected from hydrogen peroxide, t-butylhydroperoxide, ammonium and alkali metal salts of monopersulfuric acid, and ammonium and alkali metal salts of dipersulfuric acid.
7. The process of claim 1, 2 or 3 characterized in that said hydraulic medium also comprises from 0.1 to 10 parts of an organic free radical scavenger per part by weight of said peroxygen compound in said hydraulic medium, and said free radical scavenger is selected from unsaturated alcohols, phenols and allylic monomers.
8. The process of claim 1, 2 or 3 characterized in that said hydraulic medium also comprises from 0.1 to 10 parts of an organic free radical scavenger per part by weight of said peroxygen compound in said hydraulic medium and said peroxygen compound is selected from hydrogen peroxide, t-butylhydro-peroxide, ammonium and alkali metal salts of monopersulfuric acid, and ammonium and alkali metal salts of dipersulfuric acid.
9. The process of claim 1, 2 or 3 characterized in that said hydraulic medium also comprises from 0.1 to 10 parts of an organic free radical scavenger per part by weight of said peroxygen compound in said hydraulic medium, said peroxygen compound is selected from hydrogen peroxide, t-butylhydroperoxide, ammonium and alkali metal salts of monopersulfuric acid, and ammonium and alkali metal salts of dipersulfuric acid, and said free radical scavenger is selected from unsaturated alcohols, phenols and alkylic monomers.
10. The process of claim l, 2 or 3 characterized in that said hydraulic medium also comprises 0.5 to 5 parts of an organic free radical scavenger per part by weight of the peroxygen compound in the hydraulic medium.
11. The process of claim 1., 2 or 3 characterized in that said hydraulic medium also comprises 0.5 to 5 parts of an organic free radical scavenger per part by weight of the peroxygen compound in the hydraulic medium and said peroxygen compound is selected from hydrogen peroxide, t-butylhydroperoxide. ammonium and alkali metal salts of monopersulfuric acid, and ammonium and alkali metal salts of dipersulfuric acid.
12. The process of claim 1, 2 or 3 characterized in that said hydraulic medium also comprises 0.5 to 5 parts of an organic free radical scavenger per part by weight of the peroxygen compound in the hydraulic medium, and said free radical scavenger is selected from unsaturated alcohols, phenols and allylic monomers.
13. The process of claim 1, 2 or 3 characterized in that said hydraulic medium also comprises 0.5 to 5 parts of an organic free radical scavenger per part by weight of the peroxygen compound in the hydraulic medium, said peroxygen compound is selected from hydrogen peroxide, t-butylhydroperoxide, ammonium and alkali metal salts of monopersulfuric acid, and ammonium and alkali metal salts of dipersulfuric acid and said free radical scavenger is selected from unsaturated alcohols, phenols and allylic monomers.
14. The process of claim 1, 2 or 3 wherein said hydraulic medium contains in suspension solid particles suitable for use as propping agents to maintain a fracture in the formation or to form a pack in contact with the formation.
CA000512014A 1985-08-07 1986-06-20 Peroxygen breaker systems for well completion fluids Expired - Lifetime CA1266558A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CA000512014A CA1266558A (en) 1985-08-07 1986-06-20 Peroxygen breaker systems for well completion fluids

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US763,169 1985-08-07
US06/763,169 US4610795A (en) 1985-08-07 1985-08-07 Peroxygen breaker systems for well completion fluids
CA000512014A CA1266558A (en) 1985-08-07 1986-06-20 Peroxygen breaker systems for well completion fluids

Publications (2)

Publication Number Publication Date
CA1266558C CA1266558C (en) 1990-03-13
CA1266558A true CA1266558A (en) 1990-03-13

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CA000512014A Expired - Lifetime CA1266558A (en) 1985-08-07 1986-06-20 Peroxygen breaker systems for well completion fluids

Country Status (7)

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US (1) US4610795A (en)
EP (1) EP0213095B1 (en)
JP (1) JPS6233995A (en)
AT (1) ATE54719T1 (en)
CA (1) CA1266558A (en)
DE (1) DE3672716D1 (en)
MX (1) MX164215B (en)

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DE3672716D1 (en) 1990-08-23
ATE54719T1 (en) 1990-08-15
US4610795A (en) 1986-09-09
EP0213095B1 (en) 1990-07-18
EP0213095A3 (en) 1987-08-26
JPS6233995A (en) 1987-02-13
JPH0444677B2 (en) 1992-07-22
EP0213095A2 (en) 1987-03-04
CA1266558C (en) 1990-03-13
MX164215B (en) 1992-07-27

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