US20070213232A1 - Viscoelastic Surfactant Gels With Reduced Salt Concentration - Google Patents

Viscoelastic Surfactant Gels With Reduced Salt Concentration Download PDF

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US20070213232A1
US20070213232A1 US10/574,592 US57459204A US2007213232A1 US 20070213232 A1 US20070213232 A1 US 20070213232A1 US 57459204 A US57459204 A US 57459204A US 2007213232 A1 US2007213232 A1 US 2007213232A1
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fluid
wellbore fluid
gel
ves
surfactant
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Robert Hartshorne
Trevor Lloyd Hughes
Gary Tustin
Jian Zhou
Timothy Jones
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Schlumberger Technology Corp
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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
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
    • 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
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
    • 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
    • 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
    • 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
    • C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/25—Methods for stimulating production
    • E21B43/26—Methods for stimulating production by forming crevices or fractures
    • 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
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/30—Viscoelastic surfactants [VES]

Definitions

  • the present invention relates to the use of organic compounds for raising the viscosities and/or reducing the salt requirements of viscoelastic surfactant (VES) gels, and particularly organic compounds having one or more alcohol or amine groups and compositions derived therefrom.
  • VES viscoelastic surfactant
  • hydrocarbons such as oil and gas
  • wellbore treatment fluids such as drilling fluids, completion fluids, work over fluids, packer fluids, fracturing fluids, diverting fluids, acidising fluids, conformance or permeability control fluids and the like.
  • Typical viscoelastic surfactants are N-erucyl-N,N-bis(2-hydroxyethyl)-N-methyl ammonium chloride (known as EHAC) and potassium oleate, solutions of which form gels that are responsive to oil when mixed with aqueous brine.
  • EHAC N-erucyl-N,N-bis(2-hydroxyethyl)-N-methyl ammonium chloride
  • potassium oleate potassium oleate
  • the salt concentration required to form the VES gels is typically between 3 and 12 weight percent.
  • FIG. 1 shows the measured rheological profiles of two VES gels based on EHAC and potassium oleate. The salt concentrations required for these systems are between 3 to 4 wt % and 6 to 8 wt %, respectively.
  • VES gels A general feature of VES gels is that the viscosity of the gel decreases with increasing temperature. In many cases the viscosity of the gel will show a decrease above a critical temperature. This effect can be clearly seen in FIG. 1 where the viscosities of the gels decrease suddenly above about 60° C. In many hydrocarbon well applications, the downhole temperature can be above this critical temperature. When this happens, the performance of a treatment fluid based on the VES gel can be impaired.
  • Patist et al. have observed that long-chain alcohols have an effect upon the NMR relaxation time of spherical micelles (Patist, A., Axelberd, T., and Shah, D. O., “Effect of long chain alcohols on micellar relaxation time and foaming properties of sodium dodecyl sulfate”, J. Coll. Int. Sci., 208 , 259 (1998)). They postulate that the sodium dodecyl sulfate micelles pack more tightly when the alcohol is present.
  • the present invention is at least partly based on the discovery that the temperature at which the viscosity of a VES gel decreases can be increased by the addition of an alcohol or amine. It was also discovered that such an addition can cause an increase in the viscosity of the VES gel.
  • a first aspect of the present invention provides a wellbore fluid and its use including an organic compound having one or more polar groups to raise the critical temperature of a VES gel useful in a wellbore treatment fluid.
  • organic compound can be used to extend the range of downhole operating temperatures under which VES gels can be usefully employed.
  • a second aspect of the present invention provides the use of an organic compound having one or more alcohol or amine groups to reduce the concentration of inorganic salt that raises the viscosity of a VES gel above a level useful in a wellbore treatment fluid.
  • the present invention provides the use of an organic compound having one or more alcohol or amine groups to reduce or substantially eliminate the amount of that salt.
  • the salt concentration of the well bore fluid in wt % preferably ranges between 0 and 6, more preferably between 0 and 4 and even more preferable between 0 and 3, or even under 3 using for example fresh water instead of brine.
  • the above salt concentration may include organic salts.
  • the organic compound used in this way allows the inorganic salt requirements of VES gels to be reduced. Indeed, under certain circumstances, the useful viscosity level can be achieved in the absence of inorganic salt.
  • first and second aspects can be combined and an organic compound having one or more alcohol or amine groups can be used to both raise the temperature at which the viscosity of a VES gel falls below a level useful in a wellbore treatment fluid, and to reduce the concentration of inorganic salt required to raise the viscosity of a VES gel above that level.
  • a further aspect of the present invention provides a method of treating a subterranean formation of a hydrocarbon well comprising injecting a treatment fluid into the well, the fluid comprising a surfactant for forming a VES gel, an organic compound having one or more alcohol or amine groups, and optionally an inorganic salt; whereby the organic compound raises the temperature at which the viscosity of the VES gel falls below a level useful for treating a subterranean formation of a hydrocarbon well, and/or reduces the concentration of inorganic salt required to raise the viscosity of the VES gel above that level.
  • the wellbore treatment fluid may be e.g. a fracturing fluid, a selective acidising fluid or diverting fluid, or a water shut-off fluid.
  • Fracturing fluids are used to create opening or cracks in the formation and carry components such as proppants to prevent the openings from closing.
  • Diverting fluids are fluids that inhibit access of subsequently injected fluids, such as acidising fluids, into formation layers with low oil saturation.
  • the viscosity level useful for most well bore applications is generally between 50 and 100 cP at a shear rate of 100 s ⁇ 1 .
  • Fluids in accordance with the present invention may exhibit viscosities of 50 cP or 60 cP at temperatures above 50 degrees Celsius, or above 60 degrees Celsius and even above 70 degrees Celsius without increasing the salt level above 6 wt %.
  • the useful viscosity level should be attained at a broad range of reservoir temperatures. Typically reservoir temperatures can range from around 30° C. to around 200° C. Using the present invention, the critical temperature before significant loss of viscosity occurs, can be raised to above 100, 130 and even 150 degrees Celsius without turning to high salt concentrations.
  • the low shear viscosity level useful for effective transport of proppant particles is suitably >1000 cP at less than or equal to 1 s ⁇ 1 .
  • the viscosity level of a diverting gel useful for VES diversion systems is suitably >20 cP at 100 s ⁇ 1 .
  • the viscosity level useful for water control treatments is typically ⁇ 100 cP at encountered shear rates.
  • the organic compound may be suitably miscible with the VES gel formulation and it is typically non-ionic.
  • the organic compound may be composed of a linear or branched saturated or partially unsaturated carbon chain comprising one or more polar groups, wherein the polar groups are typically —OH, —SH or —NH 2 . As the observed effect becomes more pronounced at high molecular weight, the organic compound may be preferably selected from a range comprising between 7 and 22 carbon atoms or more preferably comprising between 7 and 16 carbon atoms.
  • the organic compound may contain at least one other group selected from an ether, ketone, amide, ester, phosphate ester or phosphonate ester group.
  • the organic compound may be a mono-alcohol, a diol, an ethoxylated alcohol, ethyoxylated amine, alkanolamide or fatty acid ethoxylate, for example propan-2-ol, butanol, octan-1-ol, oleyl alcohol, versatyl alcohol, butanediol, butyl amine, oleyl amine or a dimeric oleyl amine.
  • the VES gel may be formed from a surfactant which is anionic, cationic or zwitterionic, and is, for example, a carboxylate or modified carboxylate, a compound of formula R—X—Y-Z (as hereinafter defined), a quaternary ammonium compound, an alkyl betaine/sulphobetaine or an alkyl amido betaine/sulphobetaine.
  • a surfactant which is anionic, cationic or zwitterionic, and is, for example, a carboxylate or modified carboxylate, a compound of formula R—X—Y-Z (as hereinafter defined), a quaternary ammonium compound, an alkyl betaine/sulphobetaine or an alkyl amido betaine/sulphobetaine.
  • the surfactant is derived from oleic acid, linoleic acid or mixtures thereof, erucic acid, tallow acid, dimeric/trimeric/oligomeric carboxylic acids; or is E1018, oleyl ester succinate, oleyl amide succinate, oleyl sarcosinate or N-erucyl-N,N-bis(2-hydroxyethyl)-N-methyl ammonium chloride.
  • the molar ratio, the ration between the concentration measured in mol/l, of the organic compound to the surfactant on which the VES gel is based is 0.5 or less. More preferably, the molar ratio is in the range of 0.05 to 3, and even more preferably in the range of 0.05 to 2.
  • FIG. 1 Rheological profile as a function of temperature of 4 wt % N-erucyl-N,N-bis(2-hydroxyethyl)-N-methyl- ammoniumchloride (EHAC) and 4 wt % potassium oleate gels with respectively 3 and 8 wt % KCl.
  • EHAC N-erucyl-N,N-bis(2-hydroxyethyl)-N-methyl- ammoniumchloride
  • FIG. 2 Rheological profile as a function of temperature of two 4 wt % dimeric surfactant gels with respectively 4 and 8 wt % KCl.
  • FIG. 3 Rheological profile as a function of temperature of two 4 wt % dimeric surfactant gels, both with 4 wt % KCl and one with 0.3 molar ratio of oleyl alcohol.
  • FIG. 4 Rheological profile as a function of temperature of two 4 wt % monomeric amide surfactant gels with and without 0.1 molar ratio of oleyl alcohol.
  • FIG. 5 Rheological profile as a function of temperature of three 4 wt % oleyl sarcosinate gels, one without alcohol, and the other two with respectively 0.3 molar ratio of 1-octanol and 0.15 molar ratio of oleyl alcohol.
  • FIG. 6 Rheological profile as a function of temperature two 4 wt % oleyl sarcosinate gels with and without 0.1 molar ratio of oleyl amine.
  • FIG. 7 Rheological profile as a function of temperature of four 4 wt % oleic acid dimer (E1018, supplied by Cognis Oleochemicals) gels, three with 6 wt % and one with 8 wt % KCl. Two of the gels with 6 wt % KCl also contain 0.15 molar ratio of respectively oleyl alcohol and 1-octanol.
  • E1018 4 wt % oleic acid dimer
  • FIG. 8 Liow shear viscosity of viscoelastic gels based on 3.375 wt % EHAC with and without 1.125 wt % iso-propanol (IPA) as a function of salt (KCl) concentration and temperature.
  • IPA iso-propanol
  • FIG. 9 Variation of KCl concentration required to produce an optimum viscosity, against temperature for two VES gels based on 3.375 wt % EHAC with and without the addition of 1.125 wt % IPA.
  • FIG. 10 Viscosity at 80° C. as a function of shear rate (0.1-100 s ⁇ 1 ) of a 4 wt % oleyl ester succinate/1.5 wt % KCl gel with and without 0.1 molar ratio oleyl alcohol.
  • FIG. 11 Rheological profile as a function of temperature of three gels based on Edenor UKDTM (supplied by Cognis Oleochemicals), one gel containing 2.5 wt % EdenorTM and 3 wt % KCl, another gel containing 2 wt % EdenorTM and 3 wt % KCl and 0.5 wt % oleyl diethanolamide, and the last gel containing 2 wt % EdenorTM and 10 wt % KCl.
  • Edenor UKDTM supplied by Cognis Oleochemicals
  • the temperature dependence of the viscosity may be controlled to some extent by varying the concentration of salt in the VES gel.
  • FIG. 2 shows the effect of varying the salt concentration on the rheological properties of a VES gel. It can be seen that raising the salt concentration in the gel increases the critical temperature of the VES gel. However, as illustrated by FIG. 8 (discussed more fully below in relation to Example 7), the viscosity tends to drop off beyond a certain salt concentration.
  • the viscosity level of a wellbore treatment fluid and in particular of such a fluid useful for treating a subterranean formation of a hydrocarbon well will depend on the type of treatment.
  • the viscosity of a VES-based fracturing fluid should be 50-100 cP at 100 s ⁇ 1, preferably >75 cP at 100 s ⁇ 1.
  • the fracturing fluid should also have a much higher low shear viscosity, typically >100 cP at ⁇ 1 s ⁇ 1.
  • the viscosity of the diverting gel should be greater than about 30 cp at 100 s ⁇ 1 and preferably about 50 cP at 100 s ⁇ 1.
  • the typical fluid viscosity during injection should be ⁇ 100 cP and preferably ⁇ 50 cP throughout the range of shear rates encountered during placement.
  • VES gel-based fluid will display an optimum salt concentration at which the critical temperature shows a maximum.
  • This optimum salt concentration is often above the 6 wt % commonly achievable in oilfield operations and may, in some cases be above 12 wt %.
  • VES gels according to the present invention the addition of an organic compound such as an alcohol or amine to the VES gel has the effect of increasing the critical temperature of the gel.
  • an organic compound such as an alcohol or amine reduces or possibly substantially eliminates the salt requirement of the gel. In many cases this allows gels to be formed with similar viscosities to those achieved with the optimum salt concentration in the absence of the organic compound.
  • critical temperature means the temperature above which the viscosity of the gel ceases to be useful for a wellbore treatment fluid and in particular for the treatment of a subterranean formation of a well.
  • the critical temperature will vary depending on the exact composition of the VES gel, but can be determined for a particular gel using techniques known and available in the art.
  • the organic compound is typically a compound which is miscible with the VES gel formulation and which either resides mainly in the continuous aqueous phase of the fluid or at least partially resides within the worm-like micellar phase of the fluid. If the compound is too hydrophobic, then a low molar ratio of the compound will migrate to the interior of the worm-like micelles causing the worm-like micellar structure to be broken resulting in a reduction in the viscosity of the fluid at ambient temperature.
  • the preferred compounds are more hydrophilic such that a molar ratio of the compound to the surfactant ⁇ 0.5 or preferably ⁇ 0.3 or more preferably ⁇ 0.1 does not cause the worm-like structure of the fluid to break, but rather it enhances the viscosity at elevated temperatures and it also reduces the concentration of inorganic salt which is required to optimize the high temperature tolerance of the gel.
  • the organic compound is preferably non-ionic. Typically it may be composed mainly of a linear or branched saturated or partially unsaturated carbon chain with a sufficient number of polar groups to impart a hydrophilic-lipophilic balance (HLB) high enough to render the compound miscible with the aqueous VES gel formulation and high enough such that low molar ratios of the compound do not break the worm-like micellar structure of the VES gel.
  • Typical polar group(s) of the compound are —OH, —SH, —NH 2 .
  • the compound may also contain other groups such as ether, ketone, amide, ester, phosphate ester or phosphonate ester groups.
  • the compound when it contains —OH groups, it can be a simple mono-alcohol such propan-2-ol, butanol, octan-1-ol or oleyl alcohol, an alpha-branched alcohol such as versatyl alcohol, a diol such as butanediol or a more complex molecule such as an ethoxylated alcohol, ethoxylated amine, alkanolamide or fatty acid ethoxylate. Dimeric or oligomeric forms such as a dimer acid ethoxylate may also be used.
  • the compound is more hydrophilic and completely miscible with the continuous phase, e.g.
  • the compound can be symmetric or asymmetric.
  • the compound is more hydrophobic, e.g. octan-1-ol or oleyl alcohol, then the compound is asymmetric such that it can penetrate the worm-like micelles.
  • the compound does not contains —OH groups, it can be an amine such as butyl amine, oleyl amine or a dimeric oleyl amine.
  • the concentrations of additive required to elevate the critical temperature are similar.
  • the molar ratio of the additive to the surfactant which forms the VES gel may be 0.5 or less, and more preferably the molar ratio is in the range from 0.01 and 0.4.
  • the VES gel may be formed from a surfactant which is anionic, cationic or zwitterionic.
  • Typical anionic viscoelastic surfactants include carboxylates and modified carboxylates where the typical carboxylates can be those derived from oleic acid, linoleic acid, erucic acid, mixtures of oleic and linoleic acid, tallow acid, dimeric/trimeric/oligomeric carboxylic acids and where the modified carboxylates can be ethoxycarboxylates, ester carboxylates or amide carboxylates.
  • Exemplary modified carboxylates include oleyl ester succinate, oleyl amide succinate and oleyl sarcosinate.
  • the viscoelastic surfactant when it is anionic, it may be of general formula R—X—Y-Z (as described in WO/02/064945 and WO/02/064947) and in which R is the hydrophobic tail of the surfactant, Z is the hydrophilic head of the surfactant, said hydrophilic head group being charged, X is a stabilising group and Y is a linear, saturated or unsaturated chain of 1, 2 or 3 carbon atoms or a branched, saturated or unsaturated hydrocarbon chain wherein the main chain is of 1, 2 or 3 carbon atoms, possibly incorporating an aromatic ring.
  • the anionic group Z can be carboxylate, COO ⁇ or sulphonate, SO 3 ⁇ .
  • Typical cationic surfactants include quaternary ammonium compounds such as N-erucyl-N,N-bis(2-hydroxy-ethyl)-N-methyl ammonium chloride.
  • Typical zwitterionic surfactants include the alkyl betaines/sulphobetaines and alkyl amido betaines/sulphobetaines where the alkyl group is typically oleyl or erucyl and dimeric/trimeric/oligomeric forms of these betaines/sulphobetaines.
  • VES surfactants to which the present invention may be applied include conventional commercially available surfactants, such as oleyl ester succinate, oleyl amide succinate, dimeric oleyl amide succinate, oleyl sarcosinate, oleic acid salt, oleic acid salt dimer, EHAC and a mixture of linoleic and oleic acids, as well as e.g. the surfactant compounds (I-VII) shown below which are intended to have extended temperature capabilities.
  • surfactant compounds I-VII
  • VES-based treatment fluids according to the present invention show wide applicability in wellbore applications.
  • the fluids may be used as, for example, fracturing fluids, selective acidising fluids, water shut-off fluids, well clean-out fluids, diversion fluids for acid and scale dissolver treatments.
  • VES-based treatment fluids of the present invention are particularly useful in the treatment of a subterranean formation of a well.
  • VES gel treatment fluids of the present invention may be formulated by simple admixing of the VES surfactant with an appropriate alcohol or amine additive.
  • the treatment fluid may also comprise other elements such as a proppant, if the gel is formulated as a fracturing fluid, such as 20-40 mesh sand, bauxite, glass beads etc.
  • the alcohol or amine additive may be pre-mixed with the surfactant to a given concentration. This facilitates transport of the alcohol or amine additives to oilfield sites.
  • water or aqueous salt solution usually KCl brine
  • KCl brine water or aqueous salt solution
  • the alcohol or amine additive may be mixed on-site with the surfactant and water/brine to form the treatment fluid.
  • VES surfactant systems according to the present invention have been assessed in terms of the rheology (variation of viscosity with temperature or salt concentration) of the respective gel.
  • a controlled stress rheometer (Bohlin model type CVO-50) was used to measure the rheological properties of the solutions.
  • the viscosity was then obtained for each measurement by dividing the measured stress by the calculated shear rate.
  • a surfactant derived from dimeric oleyl amide succinate forms a gel when it is dissolved in aqueous base and salt is added.
  • the optimum salt concentration is around 8 wt % KCl.
  • the temperature at which the viscosity of the gel drops below 50 cp is just over 130° C. This temperature drops dramatically to just over 70° C. if only 4 wt % KCl is added. This effect can be seen in FIG. 2 .
  • the temperature at which the viscosity of the gel drops below 50 cp is raised when a 0.3 molar ratio of oleyl alcohol is added.
  • Monomeric oleyl amide succinate shows similar behaviour to that of its dimeric counter-part in forming VES gels on addition of aqueous base and a salt.
  • the rheological performance of the monomeric version of oleyl amide succinate is shown in FIG. 4 .
  • the optimum salt concentration for this VES system is 10 wt % and again, a dramatic loss of performance is observed when the salt concentration is reduced to 4 wt %.
  • Addition of a 0.1 molar ratio of oleyl alcohol increases the temperature at which the system has gel properties, therefore increasing the application range of the material.
  • Example 1 is also applicable to other amide systems, such as oleyl sarcosinate (commercially available from Dow chemicals and known as Hamposyl O).
  • oleyl sarcosinate commercially available from Dow chemicals and known as Hamposyl O.
  • a 4 wt % solution of the amide requires 10 wt % KCl to remain as a gel up to around 100° C.
  • the viscosity of the same material with only 6 wt % KCl loses its gel properties at just under 80° C.
  • the addition of a 0.15 molar ratio of oleyl alcohol to the gel containing 6 wt % KCl restores the temperature at which the viscosity falls below 50 cp to around 95° C.
  • the rheological profile is shown in FIG. 5 .
  • VES gels derived from the salts of oleic acid dimers have also been examined.
  • the KCl concentration required to achieve optimum performance for these systems is around 8 wt %.
  • VES gels based on one of these oleic acid dimers, E1018 (supplied by Cognis) is of interest due to its reasonable tolerance to the presence of divalent cations such as calcium.
  • the gel formed from this blend of oligomeric acids (E1018) has an upper operating temperature of around 90° C. This temperature drops to below 80° C. when the KCl concentration is reduced to the 6 wt % which is manageable in the field.
  • the temperature at which the viscosity of a gel formed form E1018 with 6 wt % KCl falls below 50 cp can be raised to around 90° C. by the addition of a 0.15 molar ratio of an alcohol such as 1-octanol or oleyl alcohol. This effect is shown in the rheological profile of FIG. 7 .
  • N-erucyl-N,N-bis(2-hydroxyethyl)-N-methylammonium chloride forms VES gels in the presence of chloride salt solutions (see FIG. 1 ). However, the concentration of salt required to form the strongest gel is reduced when iso-propanol is added to the system.
  • VES gels were formulated with 3.375 wt % EHAC and varying overall concentrations of KCl. The viscosity of these gels was tested at each of 40, 60, 80, and 100° C. The results of these tests are shown in FIG. 8 as the solid lines of the rheological profiles. It can be seen from FIG. 8 that this gel system shows a definite optimum salt concentration which results in the highest viscosity at each temperature tested. For the gels containing only EHAC and KCl, the optimum salt concentration lies between 4 and 6 wt % depending upon the temperature of the gel.
  • a second range of VES gels was then formulated again with 3.375 wt % EHAC and varying overall concentrations of KCl but now with an additional 1.125 wt % iso-propyl alcohol (IPA).
  • the viscosity of these gels was tested at each of 40, 60, 80, and 100° C. The results of these tests are shown in FIG. 8 as the dashed lines of the rheological profiles. It can be seen that in each case, the addition of IPA results in the optimum salt concentration at which the highest viscosity is achieved being shifted to lower values. In addition, the maximum viscosity achieved at each of the temperatures tested is higher in the gels containing IPA than in those with only EHAC and KCl.
  • FIG. 9 The effect of adding 1.125 wt % IPA to the 3.375 wt % EHAC solution is shown in FIG. 9 . From this figure it can be seen that the addition of 1.125 wt % IPA to the EHAC based VES gel results in the lowering of the optimum KCl concentration by between 2 and 2.5 wt %.
  • VES gels Two VES gels were formulated, the first using 4 wt % oleyl ester succinate surfactant and 1.5 wt % KCl and the second the same but including 0.1 molar ratio or oleyl alcohol.
  • the viscosity at 80° C. of the gels is shown in FIG. 10 as a function of shear rate (0.1-100 s ⁇ 1). It can be seen that the viscosity of the VES gel containing oleyl alcohol is higher than that without the added alcohol with increasing shear rates.
  • FIG. 11 shows the rheological profile of two Edenor-based VES gels with respectively 3 and 10 wt % KCl added and a further gel which contains 0.5 wt % oleic diethanolamide and 3 wt % KCl. It can be seen in FIG. 11 that the viscosity of the VES gel with 10 wt % added KCl drops below the 50 cp threshold at just over 80° C.
  • the gel contains only 3 wt % KCl, this temperature is lowered dramatically to about 35° C. However, when 0.5 wt % oleic diethanolamide is added to the gel with 3 wt % KCl, this temperature recovers to almost the same level as the gel with 10 wt % KCl.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Detergent Compositions (AREA)
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GB0323916A GB2406864A (en) 2003-10-11 2003-10-11 Viscoelastic fluid with increased thermal stability and reduced salt concentration
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PCT/GB2004/004280 WO2005040554A1 (en) 2003-10-11 2004-10-11 Viscoelastic surfactant gels with reduced salft concentration

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US20090209438A1 (en) * 2008-02-04 2009-08-20 Sanjel Corporation Low residue fluid fracturing system and method of use
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US7670995B2 (en) * 2000-08-07 2010-03-02 Schlumberger Technology Corporation Viscoelastic wellbore treatment fluid
US20100152068A1 (en) * 2007-02-23 2010-06-17 Schlumberger Technology Corporation Wellbore treatment fluid
US20100256025A1 (en) * 2009-04-07 2010-10-07 Halliburton Energy Services, Inc, Viscoelastic surfactants and methods of making and using same
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WO2015071607A1 (fr) 2013-11-14 2015-05-21 Arkema France Composition fluide pour la stimulation dans le domaine de la production de pétrole et de gaz
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WO2015126418A1 (en) 2014-02-21 2015-08-27 Halliburton Energy Services Inc. Amido- functionalized gemini surfactant for fluid control in subterranean formations
CN110819332B (zh) * 2019-11-19 2022-03-15 西安石油大学 一种基于小分子凝胶对油水识别的智能驱油剂及其制备方法

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US7858563B2 (en) 2000-08-07 2010-12-28 Schlumberger Technology Corporation Wellbore treatment with hydrocarbon-responsive fluid containing oligomeric viscoelastic surfactant
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US20080161207A1 (en) * 2006-12-29 2008-07-03 Halliburton Energy Services, Inc. Subterranean treatment fluids comprising viscoelastic surfactant gels
US8815785B2 (en) 2006-12-29 2014-08-26 Halliburton Energy Services, Inc. Utilization of surfactant as conformance materials
US20090143256A1 (en) * 2006-12-29 2009-06-04 Halliburton Energy Services, Inc. Utilization of surfactant as conformance materials
US8252730B2 (en) 2007-02-23 2012-08-28 Schlumberger Technology Corporation Wellbore treatment fluid
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US20090209438A1 (en) * 2008-02-04 2009-08-20 Sanjel Corporation Low residue fluid fracturing system and method of use
US8193127B2 (en) 2008-02-04 2012-06-05 Sanjel Corporation Low residue fluid fracturing system and method of use
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US8728990B2 (en) 2009-12-04 2014-05-20 Elementis Specialties, Inc. Phosphate ester oil gellant
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WO2015071607A1 (fr) 2013-11-14 2015-05-21 Arkema France Composition fluide pour la stimulation dans le domaine de la production de pétrole et de gaz
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US20150203741A1 (en) * 2014-01-17 2015-07-23 Elevance Renewable Sciences, Inc. Natural Oil-Derived Wellbore Compositions and Methods of Use
US10017682B2 (en) * 2014-01-17 2018-07-10 Elevance Renewable Sciences, Inc. Natural oil-derived wellbore compositions and methods of use

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GB0606698D0 (en) 2006-05-10
EA014308B1 (ru) 2010-10-29
GB0323916D0 (en) 2003-11-12
CA2547919A1 (en) 2005-05-06
GB2422167B (en) 2007-11-07
WO2005040554A1 (en) 2005-05-06
CA2547919C (en) 2013-08-27
GB2406864A (en) 2005-04-13
EA200600753A1 (ru) 2006-10-27

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