US20070173416A1 - Well treatment compositions for use in acidizing a well - Google Patents

Well treatment compositions for use in acidizing a well Download PDF

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Publication number
US20070173416A1
US20070173416A1 US11/336,474 US33647406A US2007173416A1 US 20070173416 A1 US20070173416 A1 US 20070173416A1 US 33647406 A US33647406 A US 33647406A US 2007173416 A1 US2007173416 A1 US 2007173416A1
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Prior art keywords
well
ester
treatment composition
well treatment
polyester
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US11/336,474
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English (en)
Inventor
Alan Moorehead
William Shumway
Bradley Todd
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Halliburton Energy Services Inc
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Halliburton Energy Services Inc
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Application filed by Halliburton Energy Services Inc filed Critical Halliburton Energy Services Inc
Priority to US11/336,475 priority Critical patent/US7431088B2/en
Priority to US11/336,474 priority patent/US20070173416A1/en
Assigned to HALLIBURTON ENERGY SERVICES, INC. reassignment HALLIBURTON ENERGY SERVICES, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TODD, BRADLEY L., MOOREHEAD, ALAN W., SHUMWAY, WILLIAM W.
Priority to MX2008009332A priority patent/MX2008009332A/es
Priority to CA2637734A priority patent/CA2637734C/en
Priority to MYPI20082658A priority patent/MY145435A/en
Priority to DK07704940.1T priority patent/DK1979433T3/en
Priority to PCT/GB2007/000160 priority patent/WO2007083128A1/en
Priority to BRPI0707170-1A priority patent/BRPI0707170B1/pt
Priority to EA200870184A priority patent/EA014342B1/ru
Priority to AU2007206784A priority patent/AU2007206784B2/en
Priority to CA2705597A priority patent/CA2705597C/en
Priority to EP07704940.1A priority patent/EP1979433B1/en
Priority to ARP070100263A priority patent/AR059140A1/es
Publication of US20070173416A1 publication Critical patent/US20070173416A1/en
Priority to NO20083043A priority patent/NO20083043L/no
Priority to EC2008008637A priority patent/ECSP088637A/es
Priority to EG2008071215A priority patent/EG26613A/en
Abandoned legal-status Critical Current

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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
    • C09K8/72—Eroding chemicals, e.g. acids
    • 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
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning

Definitions

  • the present invention generally relates to hydrocarbon production, and more particularly to well treatment compositions comprising one or more esters or polyesters of hydroxy acid or of glycerol for obtaining controlled acidization in a well.
  • Natural resources such as gas, oil, and water residing in a subterranean formation can be recovered by drilling wells into the formation.
  • Well drilling involves drilling a wellbore down to the formation while circulating a drilling fluid through the wellbore.
  • Various types of drilling fluids also known as drilling muds, have been used in well drilling such as mineral oil-based fluids and synthetic oil-based fluids.
  • Such drilling fluids typically form a thin, slick filter cake on the formation face that provides for successful drilling of the well bore and that helps prevent loss of fluid to the subterranean formation.
  • drilling fluids that produce filter cakes of cellulose and starch derivatives and sized calcium carbonate are often employed.
  • the first stage which is known as the primary production stage, allows the oil to flow into a production well (or wells) under natural forces.
  • the natural forces may be sufficient to drive the oil to the surface where it is recovered.
  • pumps may be required to displace the oil from the wellbore to the surface.
  • the primary production stage usually yields only about 5% to 15% of the oil in the reservoir.
  • a secondary recovery operation thus is typically performed to recover additional amounts of the oil from the reservoir.
  • a common secondary recovery operation known as secondary flooding involves injecting a fluid such as water into a so-called injection well (or wells) to drive oil in the formation to the production well (or wells).
  • Secondary flooding usually recovers up to an additional 50% of the original oil in the reservoir.
  • Tertiary recovery operations such as tertiary flooding may also be used to drive the remaining oil from the formation to the production well.
  • the presence of the filter cake on the face of the subterranean formation may adversely affect the flow of fluid though the injection and production wells.
  • the filter cake may occlude the pore structure of the formation.
  • the pump pressures e.g., fracturing pressures
  • required to inject past the filter cake may be higher than desirable for achieving good sweep efficiency of the oil.
  • a procedure known as acidization has been used for filter cake removal for over a century.
  • the cellulose of which the filter cake is primarily composed may be decomposed by applying acid to the filter cake.
  • the first acidization procedure involved directly injecting strong mineral acids such as hydrochloric acid (HCl) into the well.
  • HCl hydrochloric acid
  • the high reactivity of such strong acids commonly result in the rapid consumption of the acid before it can reach the desired treatment region where the filter cake was located.
  • such acids are highly corrosive and thus attack the metal parts of the well structure, causing irreversible damage to the well.
  • one such treatment solution includes hydrochloric acid emulsified in crude oil such that the aqueous phase, i.e. the solution of acid in water, is surrounded by a continuous oil phase emulsifier that prevents the acid from adversely affecting the metal parts of the well structure.
  • aqueous phase i.e. the solution of acid in water
  • a continuous oil phase emulsifier that prevents the acid from adversely affecting the metal parts of the well structure.
  • a variation on this treatment solution uses a higher concentration of emulsifier to prolong the stability of the emulsion. See U.S. Pat. No. 2,050,932 to de Groote.
  • Another treatment method involves removing any water in contact with the metal parts of the well before introducing HCl gas absorbed in a mineral oil that is practically immiscible with or insoluble in water to insulate the metal of the well from being attacked by the acid. See U.S. Pat. No. 2,206,187 to Herbsman.
  • Yet another method utilizes both an aqueous fluid and a non-aqueous fluid capable of forming or releasing an acid upon dilution with water.
  • the well may be filled with oil to protect the metal from the acid, followed by pumping the aqueous fluid down to the formation. The non-aqueous fluid containing the acid-forming substance may then be introduced to the well. See U.S. Pat. No. 2,059,459 to Hund.
  • a treatment solution that uses an ester, such as that derived from glycerol, as an emulsifying agent for an aqueous acid in oil is described in U.S. Pat. No. 2,681,889 to Menaul et al. The ester undergoes hydrolysis to break the emulsion and release the acid.
  • a similar solution uses an acid anhydride such as acetic anhydride in a hydrocarbon carrier fluid to release acid upon reaction with water. See U.S. Pat. No. 2,863,832 to Pernine.
  • a treatment solution comprising an anhydrous organic acid, such as formic acid, acetic acid, or propionic acid, in an anhydrous hydrocarbon has also been described in U.S. Pat. No. 2,910,436 to Alhambra et al. Unfortunately, such acids are as likely to be prematurely exhausted as mineral acids before reaching the desired treatment region. All of the above-mentioned patents are incorporated by reference herein.
  • One modern acidization method involves the generation of acids in the wellbore via the action of enzymes and suitable acid precursors.
  • this method is limited by the heat tolerance of the particular enzyme being used and the breakdown temperature of the acid precursor. Treatment at high temperatures results in fast acid exhaustion and enzyme deactivation which results in poor filter cake removal.
  • the enzymes and acid precursors thus need to be stored and handled at the well site carefully to avoid being exposed to relatively high temperatures due to heat and sunlight.
  • Another method relies on the triggered release of acid via the lowering of the pH of an aqueous solution comprising an ortho ester to below about 7. Unfortunately, at elevated temperatures this release may occur in a relatively short period of time.
  • esters such as diethyleneglycol diformate
  • an aqueous solution to generate acid such as formic acid.
  • esters such as diethyleneglycol diformate
  • the esters currently being used for this purpose hydrolyze at relatively slow rates at temperatures less than 60° C.
  • those esters hydrolyze too quickly to allow the aqueous solution to be adequately dispersed across the entire filter cake before the acid is consumed.
  • the filter cake removal thus may be localized to a proportionately small area when using such methods, further resulting in the premature loss of the acid-generating fluid through pores that have been unclogged by this localized removal. It is therefore desirable to develop an acidization method in which the acid-releasing reaction occurs at a relatively slow rate over a wide temperature range, particularly at relatively high temperatures.
  • An improved acidization solution may comprise an aqueous medium and one or more esters or polyesters of a hydroxy acid or of a glycerol.
  • the solution comprises an ester or polyester of a glycerol
  • the solution is substantially absent of a hydrocarbon such as an oil.
  • the hydrolysis of such esters or polyesters occurs at a slower reaction rate than that of other known acidization esters, such as diethyleneglycol diformate, at temperatures higher than 60° C. or even higher than 100° C.
  • the improved acidization solution may be distributed substantially throughout a region in a well where acidization is required before hydrolysis is completed, despite being exposed to relatively high temperatures.
  • the hydrolysis may result in the slow release of an acid that is capable of consuming undesirable substances in the well, e.g., a filter cake, without being concerned that this consumption might be localized.
  • the strength of this acid may be greater than that of the acid formed by diethyleneglycol diformate, i.e., formic acid. Accordingly, the use of esters or polyesters of hydroxy acid or of glycerol for downhole acidization procedures provides for the removal of all or most of the filter cake present in the well.
  • FIG. 1 depicts an ester hydrolysis apparatus used in the examples provided below.
  • FIG. 2 illustrates the hydrolysis of various esters described herein and of some control esters in pure water at 100° C.
  • FIG. 3 illustrates the hydrolysis of various acetins in neutral water at 100° C.
  • FIG. 4 illustrates the hydrolysis of butyl formate and butyl lactate in neutral water at 100° C.
  • FIG. 5 illustrates the hydrolysis of ethyl lactate in neutral water and in various brines at 100° C.
  • FIG. 6 illustrates the hydrolysis of methyl-, ethyl-, propyl-, and butyl- lactate esters in neutral water at 100° C.
  • Well treatment compositions may include water combined with (a) one or more esters or polyesters of a hydroxy acid, e.g., lactic acid, and/or (b) one or more esters or polyesters of a glycerol in the absence of a hydrocarbon such as an oil.
  • esters or polyesters exhibit a relatively high solubility in the water and are capable of undergoing hydrolysis to produce an acid when exposed to a temperature in a range of from about 60° C. to about 150° C.
  • lactate esters or polyesters release lactic acid when hydrolyzed.
  • the relative amounts of the esters or polyesters and the water in the well treatment compositions may be effective to produce an effective amount of acid to remove most or all of a contaminant in the well such as a filter cake.
  • the amount of the esters or polyesters present in the aqueous treatment composition is in the range of from about 10% to about 23% by weight or volume of the composition.
  • Suitable hydroxy acid esters or polyesters for use in the well treatment compositions include lactic acid derivatives, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, trilactin (a trimester of lactic acid and glycerol), and combinations thereof.
  • Ethyl lactate is considered a particularly good lactate ester due to its ability to hydrolyze over the wide temperature range of from about 60° C. to about 150° C., with its half-life being particularly useful at temperatures ranging from about 80° C. to about 140° C.
  • ethyl lactate is relatively inexpensive and is available worldwide, whereas other esters typically have limited availability. For example, diethyleneglycol diformate has an availability limited to Europe and possibly Africa.
  • esters or polyesters of glycerol for use in the well treatment compositions include tripropionin (a triester of propionic acid and glycerol), trilactin, and esters of acetic acid and glycerol such as monoacetrin, diacetin, and triacetin.
  • esters or polyesters of hydroxy acid and/or glycerol also may be employed to adjust the half-life of the hydrolysis reaction.
  • the water contained in the well treatment compositions may be pure (i.e., neutral) water or salt water.
  • the water may comprise one or more brines capable of forming well treatment compositions having pH values in the range of from about 6 to about 8.
  • brines include sodium bromide (NaBr) brine, calcium chloride (CaCl 2 ) brine, sodium formate (NaCOOH) brine, potassium formate (KCOOH) brine, calcium bromide (CaBr 2 ) brine, potassium chloride (KCl) brine, sodium chloride (NaCl) brine, zinc chloride (ZnCl) brine, zinc bromide (ZnBr) brine, and combinations thereof.
  • the choice of brine is usually determined primarily by the weight of fluid desired.
  • the well treatment compositions may include one or more other types of esters for adjusting the half-life of the hydrolysis reaction.
  • diethyleneglycol diformate may be employed in a treatment composition along with an ester or polyester of a hydroxy acid or of a glycerol to reduce the half-life thereof.
  • the diethyleneglycol diformate therefore could be used to shorten the completion time of the well. It forms formic acid as a result of hydrolysis and is commercially available from Halliburton Energy Services, Inc. under the trade name of BDF-325 diethyleneglycol diformate.
  • esters with which the esters or polyesters described herein may be combined include diethyleneglycolmonoformate, monoethyleneglycoldiformate, monoethyleneglycolmonoformate, and combinations thereof.
  • esters could be added in conjunction with the lactate esters or polyesters described herein to give faster rates of reaction as necessary.
  • the foregoing well treatment compositions may be prepared by mixing the one or more esters or polyesters and any other components with water on-site near the well before the acidization operation is to be performed.
  • the components of the treatment compositions could be mixed off-site and transported on-site for storage until its use; however, the extra space required to accommodate the water, both during transport and during storage, makes this option less desirable.
  • mixing beforehand would require the components to be kept well below 60° C. to avoid hydrolysis of the ester or polyester prior to its addition to the wellbore.
  • Methods of acidizing a well may be performed by pumping a well treatment composition described herein down the well.
  • the temperatures in the well may be sufficient to cause the hydrolysis reaction between the one or more ester or polyester and the water to occur.
  • the temperatures may be in the range of from about 60° C. to about 150° C.
  • the half-life of the one or more lactate esters or polyesters may be effective to allow the treatment composition to be pumped substantially throughout a region in the well where the acidization is required before the hydrolysis is completed.
  • the one or more lactate esters or polyesters have half-lives in a range of from about 6 hours to about 16 hours, alternatively from about 8 hours to about 13 hours, or alternatively from about 10 hours to about 11 hours, when hydrolyzed with neutral water at 100° C.
  • Particular examples of the half-lives of various esters of lactic acid and of glycerol are presented in Table 1 below.
  • “half-life” refers to the time it takes for half of the original amount of the ester or polyester to react. TABLE 1 Half-Life in Neutral Pseudo First Order Water at 100° C. Rate Constant Ester (seconds) (sec.
  • the half-lives of such esters at relatively high temperatures are longer than that of other known acidization esters, e.g., diethyleneglycol diformate, which produces formic acid.
  • the half-life of ethyl lactate may be about 10-11 hours, whereas the half-life of diethyleneglycol diformate may be about only 18-20 minutes in neutral water at 100° C.
  • the reaction of such esters with water proceeds at a slower rate, allowing the treatment composition to be diverted throughout the entire targeted treatment region in the well before the hydrolysis reaction is completed.
  • the production of acid via the hydrolysis reaction occurs during the opportune time at which the acid is in contact with undesirable substances in the well.
  • the choice of which ester or polyester to use in the treatment composition may be based on the application temperature and desired half-life of the ester or polyester.
  • the well treatment composition may be used during a well completion operation such as the removal of filter cake from the inner wall of the well.
  • the relatively slow reaction rate of the one or more esters or polyesters may permit the treatment composition to be dispersed across the entire filter cake before the hydrolysis ends.
  • the acid generated by the hydrolysis may decompose calcium carbonate present in the filter cake, which is a major component in the filter cake.
  • the removal of the filter cake ensures that oil, gas, and/or water residing in a subterranean reservoir penetrated by the well can flow into and through the well during production. Otherwise, the filter cake might block migration pathways such as pores in the earth between the reservoir and the interior of the well, thereby preventing the oil, gas, and/or water from permeating through to the well.
  • the following general procedure was used in each of the examples.
  • the closed system reactor shown in FIG. 1 was used to measure the amount of CO 2 gas that evolved in each reaction.
  • Water or brine was added to a boiling flask 10 , which was heated to 100° C.
  • the CaCO 3 was insoluble in the water and thus was observed at the bottom of flask 10 .
  • a weighed amount of ester was added to flask 10 .
  • the amount of ester employed was always in ratio to the water or to the make-up water used to formulate the brine except where commercially available brines were used.
  • a reflux condenser 12 was affixed to flask 10 .
  • the half-lives of the esters of lactic acid and of glycerol were longer than that of the BDF-325 diethyleneglycol diformate.
  • the butyl formate to CaCO 3 molar ratio was doubled for comparison purposes.
  • the curve for the 1:1 molar ratio reaction was surprisingly similar to that for the 2:1 molar ratio reaction.
  • Doubling the molar ratio of the butyl formate should have lead to an increase in the relative reaction rate; however, this did not happen. It is believed that this behavior was due to the relative insolubility of the butyl formate since the rate of hydrolysis was determined by the concentration of the butyl formate in solution and not by the amount added.
  • Solutions containing 10 volume % monoacetin, diacetin, and triacetin in deionized water were prepared and combined with a molar ratio of CaCO 3 . Hydrolysis reactions were then carried out using the resulting solutions at 100° C. The hydrolysis reactions were monitored, and the half-lives of the esters were compared. The volume of oil displaced by the CO 2 gas is plotted as a function of time in FIG. 3 . The hydrolysis rates of the triacetin and the diacetin were very similar. However, the monoacetin consumed 4-5 times more slowly relative to the other two acetins, and the monoacetin displayed a half-life within the targeted range.
  • butyl lactate is slightly soluble in water while butyl formate exhibits poor solubility in water. Doubling the concentration of butyl lactate doubled its reaction rate. The poor solubility of butyl formate governed its slow reaction rate, making it unsuitable for use in the acidization of a well. This behavior indicates that an ester needs to be soluble in the aqueous phase before any appreciable reaction can take place.
  • methods of acidizing in a well comprise placing an ester or polyester of a hydroxyl acid and water in the well, thereby allowing the ester or polyester to undergo hydrolysis.
  • methods of acidizing in a well comprise placing an aqueous solution comprising an ester or polyester of glycerol in a well, thereby allowing the ester or polyester to undergo hydrolysis, wherein the aqueous solution is substantially absent of a hydrocarbon.
  • well treatment compositions for performing acidization in a well comprise an ester or polyester of a hydroxy acid and water.
  • well treatment compositions for performing acidization in a well comprise an ester or polyester of a glycerol and water.
  • the acidization procedure described herein also may be employed to repair damage to the subterranean formation surrounding the well.
  • This damage may be in the form of hydrocarbon wax deposits and/or inorganic salt deposits, such as calcium carbonate deposits, in the pores of a lime sand, lime stone, calcareous, or magnesium formation.
  • inorganic salt deposits may occur as a result of subterranean water becoming saturated with alkaline earth carbonates under pressure, followed by the precipitation of the carbonates when the pressure is released after the drill-in of the well.
  • the lactic acid produced by the hydrolysis of the lactate ester or polyester may attack and dissolve the wax and salt deposits, thus increasing the porosity of the formation.
  • the one or more lactate ester or polyester and water may be added to different types of carrier fluids commonly used in the well.
  • suitable carrier fluids include but are not limited to a gravel packing fluid, a drilling fluid, a completion fluid, a displacement fluid, and a work-over fluid, all of which are known in the art.

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US11/336,474 2006-01-20 2006-01-20 Well treatment compositions for use in acidizing a well Abandoned US20070173416A1 (en)

Priority Applications (16)

Application Number Priority Date Filing Date Title
US11/336,475 US7431088B2 (en) 2006-01-20 2006-01-20 Methods of controlled acidization in a wellbore
US11/336,474 US20070173416A1 (en) 2006-01-20 2006-01-20 Well treatment compositions for use in acidizing a well
EP07704940.1A EP1979433B1 (en) 2006-01-20 2007-01-19 Methods for acidization in a wellbore
EA200870184A EA014342B1 (ru) 2006-01-20 2007-01-19 Способы и композиции для кислотной обработки в стволе скважины
AU2007206784A AU2007206784B2 (en) 2006-01-20 2007-01-19 Methods and compositions for acidization in a wellbore
MYPI20082658A MY145435A (en) 2006-01-20 2007-01-19 Methods and compositions for acidization in a wellbore
DK07704940.1T DK1979433T3 (en) 2006-01-20 2007-01-19 A process for the acidification in a wellbore
PCT/GB2007/000160 WO2007083128A1 (en) 2006-01-20 2007-01-19 Methods and compositions for acidization in a wellbore
BRPI0707170-1A BRPI0707170B1 (pt) 2006-01-20 2007-01-19 Método de acidificação em um poço
MX2008009332A MX2008009332A (es) 2006-01-20 2007-01-19 Metodos y composicones para acidificacion en un pozo.
CA2637734A CA2637734C (en) 2006-01-20 2007-01-19 Methods and compositions for acidization in a wellbore
CA2705597A CA2705597C (en) 2006-01-20 2007-01-19 Methods and compositions for acidization in a wellbore using an ester or polyester of a glycerol
ARP070100263A AR059140A1 (es) 2006-01-20 2007-01-22 Metodos de acidificacion controlada en un pozo
NO20083043A NO20083043L (no) 2006-01-20 2008-07-09 Fremgangsmater og sammensettinger for syrebehandling i et borehull
EC2008008637A ECSP088637A (es) 2006-01-20 2008-07-18 Métodos y composiciones para acidificación en un pozo
EG2008071215A EG26613A (en) 2006-01-20 2008-07-20 Methods and formulations for conversion to acid in a wellbore

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Application Number Priority Date Filing Date Title
US11/336,475 US7431088B2 (en) 2006-01-20 2006-01-20 Methods of controlled acidization in a wellbore
US11/336,474 US20070173416A1 (en) 2006-01-20 2006-01-20 Well treatment compositions for use in acidizing a well

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US11/336,474 Abandoned US20070173416A1 (en) 2006-01-20 2006-01-20 Well treatment compositions for use in acidizing a well

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EP (1) EP1979433B1 (ru)
AR (1) AR059140A1 (ru)
AU (1) AU2007206784B2 (ru)
BR (1) BRPI0707170B1 (ru)
CA (2) CA2705597C (ru)
DK (1) DK1979433T3 (ru)
EA (1) EA014342B1 (ru)
EC (1) ECSP088637A (ru)
EG (1) EG26613A (ru)
MX (1) MX2008009332A (ru)
MY (1) MY145435A (ru)
NO (1) NO20083043L (ru)
WO (1) WO2007083128A1 (ru)

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WO2008038033A1 (en) * 2006-09-29 2008-04-03 Halliburton Energy Services, Inc. Methods and compositions relating to the control of the rates of acid-generating compounds in acidizing operations
US7833943B2 (en) 2008-09-26 2010-11-16 Halliburton Energy Services Inc. Microemulsifiers and methods of making and using same
US7906464B2 (en) 2008-05-13 2011-03-15 Halliburton Energy Services, Inc. Compositions and methods for the removal of oil-based filtercakes
US7998910B2 (en) 2009-02-24 2011-08-16 Halliburton Energy Services, Inc. Treatment fluids comprising relative permeability modifiers and methods of use
WO2014065972A1 (en) 2012-10-22 2014-05-01 Halliburton Energy Services, Inc. Wellbore servicing compositions and methods of making and using same
WO2014065975A1 (en) 2012-10-26 2014-05-01 Halliburton Energy Services, Inc. Wellbore servicing materials and methods of making and using same
WO2014092888A1 (en) 2012-12-10 2014-06-19 Halliburton Energy Services, Inc. Wellbore servicing compositions and methods of making and using same
US9115304B2 (en) 2012-04-09 2015-08-25 Halliburton Energy Services, Inc. Wellbore servicing fluid system and methods of use
WO2016010548A1 (en) * 2014-07-18 2016-01-21 Halliburton Energy Services, Inc. Methods for increasing the surface area of fractures or to increase the depth of penetration fractures in low permeability oil and gas reservoirs containing shale to increase productivity
US9410076B2 (en) 2012-10-25 2016-08-09 Halliburton Energy Services, Inc. Wellbore servicing methods and compositions comprising degradable polymers
US9702238B2 (en) 2012-10-25 2017-07-11 Halliburton Energy Services, Inc. Wellbore servicing methods and compositions comprising degradable polymers
US9951266B2 (en) 2012-10-26 2018-04-24 Halliburton Energy Services, Inc. Expanded wellbore servicing materials and methods of making and using same
US20180282609A1 (en) * 2017-03-30 2018-10-04 The University Of North Carolina At Chapel Hill Titanium Chloride Encapsulation for Acid Generation

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GB2412389A (en) * 2004-03-27 2005-09-28 Cleansorb Ltd Process for treating underground formations
GB0724191D0 (en) * 2007-12-11 2008-01-23 Cleansorb Ltd Process fpr treatment of underground formations
US10023788B2 (en) 2014-06-06 2018-07-17 Halliburton Energy Services, Inc. Acidizing fluids and methods for use in subterranean formations
WO2015200444A1 (en) 2014-06-24 2015-12-30 Saudi Arabian Oil Company Encapsulation of an acid precursor for oil field applications
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US7431088B2 (en) 2008-10-07
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