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WO2013053036A1 - Utilisation d'émulsion d'huile dans l'eau pour la récupération assistée de pétrole - Google Patents

Utilisation d'émulsion d'huile dans l'eau pour la récupération assistée de pétrole Download PDF

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Publication number
WO2013053036A1
WO2013053036A1 PCT/CA2011/001154 CA2011001154W WO2013053036A1 WO 2013053036 A1 WO2013053036 A1 WO 2013053036A1 CA 2011001154 W CA2011001154 W CA 2011001154W WO 2013053036 A1 WO2013053036 A1 WO 2013053036A1
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WO
WIPO (PCT)
Prior art keywords
oil
emulsion
surfactant
phase
formation
Prior art date
Application number
PCT/CA2011/001154
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English (en)
Inventor
Patrick Brunelle
Original Assignee
Diamond Qc Technologies Inc.
Optimal Resources Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Diamond Qc Technologies Inc., Optimal Resources Inc. filed Critical Diamond Qc Technologies Inc.
Priority to PCT/CA2011/001154 priority Critical patent/WO2013053036A1/fr
Publication of WO2013053036A1 publication Critical patent/WO2013053036A1/fr

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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
    • 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

Definitions

  • the present invention relates to an oil in water emulsion to facilitate and optimize enhanced oil recovery and a method for designing an oil in water emulsion.
  • the emulsion may be used as a drive fluid to displace and recover residual oil from a subterranean formation.
  • EOR Enhanced Oil Recovery
  • Typical EOR methods use injection of fluids through an injection well to "push" the oil towards production wells and can be classified as follows:
  • the surfactant also helps reduce the interfacial tension at the oil water interface
  • Alkaline surfactant polymer (ASP) floods wherein the fluid is the same as the polymer caustic flood, except that a surfactant is also added to decrease the interfacial tension of the oil/ water interface;
  • Emulsion flooding is an effective EOR process for heavy oil reservoirs, where heavy oil lacks mobility under reservoir conditions and is not suitable for the application of thermal recovery methods because of environmental and economic issues or technical impediments.
  • the present invention relates specifically to an oil in water emulsion for use in displacing and mobilizing hydrocarbons from a subterranean formation.
  • the invention also relates to a method of using an oil-in-water emulsion flood to displace hydrocarbons from a subterranean formation.
  • McAuliffe et al concluded that the injection of a 0.4% pore volume slug of an oil-in-water emulsion containing 14% oil decreased fingering and increased volumetric sweep efficiency during water flooding that followed the emulsion slug injection.
  • Another study by Ali et al (“Recovery Of Lloydminster and Morichal Crudes By Caustic, Acid And Emulsion Floods," The Journal of Canadian Petroleum (January- March 1979), pp. 53-59) also proposed the use of oil-in-water emulsion slugs as a flooding agent for heavy oil recovery.
  • caustic was used as the emulsifying agent.
  • Caustic reacts with the naturally occurring acids in the - - crude oil to form in-situ surfactants.
  • increasing the pH with caustic is often not practical or desirable when using field produced brine or field produced water in the emulsion, as increasing the pH results in precipitation of various inorganic salts and renders the brine unstable.
  • Microemulsions are oil/water systems where both the oil and water form a continuous phase.
  • Lepper US Patent 4,488,602 discloses a process for emulsion flooding of petroleum reservoirs comprising injecting a microemulsion.
  • microemulsions also known as Winsor III systems
  • Winsor III systems tend to be unstable when there are small changes in the environment such as temperature and salinity.
  • Macroemulsions refer to oil-in water emulsions where the oil is distributed as small oil droplets - - within a water continuous phase or water-in oil emulsions where the water is distributed as small droplets within an oil continuous phase.
  • the present invention satisfies this need.
  • an oil in water emulsion for use in producing hydrocarbons from a subterranean formation, said oil-in-water emulsion comprising an aqueous continuous phase and a hydrocarbon internal phase, said emulsion stabilized by a surfactant, wherein said surfactant has the following properties: (i) has an HLD that is less than 0; (ii) produces an emulsion wherein the interfacial tension between the hydrocarbon phase and the aqueous phase is less than about 5 mN/m, and (iii) does not phase separate at a temperature of from about 10° C to about 20°C above the formation temperature.
  • subterranean formation comprising: - - a) providing a hydrocarbon phase and an aqueous medium for generating an oil-in-water emulsion;
  • a surfactant to stabilize said emulsion comprises the following properties: (i) has an HLD that is less than 0; (ii) produces an oil in water emulsion wherein the interfacial tension between the hydrocarbon phase and the aqueous liquid is less than about 5 mN/m, and (iii) does not phase separate at a temperature of from about 10° C to 20°C above the formation temperature;
  • a method for preparing an oil-in-water emulsion comprising: combining water and a surfactant to form an aqueous solution; combining said aqueous solution with a hydrocarbon and mixing until said oil-in water emulsion is formed, wherein said surfactant comprises the following properties: (i) has an HLD that is less than 0; (ii) produces an emulsion wherein the interfacial tension between the hydrocarbon and the aqueous phase is less than about 5 mN/m; and (iii) does not phase separate at a temperature of from about 10° C to about 20°C above the formation temperature.
  • Emulsion stability is the degree to which an emulsion retains its internal phase as droplets homogeneously distributed when the emulsion is stressed, for instance when an emulsion passes through porous media, or contacting the emulsion with a fluid of different salinity or pH.
  • FIG.l depicts a graph comparing oil recovered and number of pore volumes injected into an exemplary core flood apparatus.
  • FIG. 2 depicts a graph comparing oil recovered and number of pore volumes injected into an exemplary core flood apparatus.
  • the current invention relates to a novel method for enhancing oil recovery using an oil in water emulsion.
  • the present invention also relates to a process for preparing an oil-in-water emulsion, and to the emulsions obtained thereby.
  • the invention may be practiced in various reservoir types, including sand or porous and fractured rock formations to extract naturally occurring hydrocarbons such as crude oil.
  • the oil in the reservoir may be heavy or light typically having viscosities varying from about 1 to about 100,000 centipoise (cP).
  • cP centipoise
  • classes of oil are essentially based on viscosity and density of the material and are broken down as:
  • oil comprises oil of any type or composition, including the classes mentioned above. Factors such as reservoir permeability and porosity will influence the penetration of the emulsion into the reservoir and the recovery of oil.
  • the oil-in-water emulsion of the present invention comprises a hydrocarbon, an aqueous medium and the use of a surfactant to emulsify and stabilise the emulsion.
  • the emulsions relate to an oil-in-water emulsion where the oil is distributed as small oil droplets within a water continuous phase.
  • a polymer may be added to the oil-in-water emulsion, to increase its viscosity in certain applications.
  • the emulsions and methods of making such emulsions according to the present invention can be used as drive fluids to displace residual oils in a formation.
  • the hydrocarbon phase used for making the emulsion should preferably comprise of hydrocarbons previously produced from the same formation where the emulsion will be injected.
  • the emulsions of the present invention are preferably used to recover moderately to extra heavy oils (12° ⁇ API ⁇ 25°). In using the produced oil from the reservoir, compatibility between the injected fluid comprising the emulsion and the reservoir is maintained.
  • the produced oil may contain a variety of other components, such as brine or sand.
  • the hydrocarbon used for the emulsion - - manufacture must also be depleted of brine and sand.
  • produced brine content in the hydrocarbon used for the emulsion can range from between about 0 to 15% by mass.
  • Sand is usually not desirable because of the possibility of damaging the emulsification equipment, the well injection equipment and even the possibility of plugging the reservoir pores with new injected sand. Therefore, it is preferred that the hydrocarbon be treated to remove all sand via filtration or centrifugation methods or other methods known to those of ordinary skill in the art, including but not limited to mechanical separation, the use of heat and the use of chemicals .
  • the aqueous phase used for making the emulsion is preferably produced water from the formation and should have sufficient ion concentration to maintain stability of the emulsion under formation conditions.
  • the water contains at least 5000 ppm of dissolved solids.
  • Produced water typically contains brine, dissolved solids, salts and minerals of sufficiently high content to require treatment prior to disposal in every day oil recovery operations. This invention allows for the disposal of the produced water back into the same reservoir, therefore eliminating the problems associated with the disposal of brine containing high salt concentration.
  • Another advantage of the present invention is that fresh water is not required for EOR. Emulsions described in the prior art requiring fresh water can be difficult to achieve as low salinity conditions are difficult to maintain since ionic species can dissolve from the rock causing breakdown of the emulsion. However, if fresh water is used as the aqueous phase according - - to the present invention, compatibility of the water is adjusted with that of the formation, for instance the ion concentration of the water, so that the emulsion stability is not affected.
  • One method of adjusting ion concentration is adding salts, to the aqueous solution as needed for stabilising the emulsion under formation conditions.
  • the methods and compositions of this invention incorporate a surfactant to stabilise the oil-in-water emulsion.
  • the surfactant is added to the hydrocarbon and water solution during the preparation of the emulsion.
  • the chemical nature of the surfactant compound may be anionic, cationic, non-ionic, and/or amphoteric.
  • the surfactant that is used is a non-ionic surfactant.
  • Emulsion stability is the degree to which an emulsion retains its internal phase as droplets homogeneously distributed when the emulsion is stressed, for instance when an emulsion passes through porous media, or contacting the emulsion with a fluid of different salinity or pH.
  • the surfactant is selected according to the oil and brine chemistries of the reservoir.
  • the surfactant should have the following properties: (a) has an HLD value that is effective in producing an oil-in water emulsion; (b) does not phase separate at a temperature of from about 10°C to about 20° above the reservoir temperature; and (c) produce an interfacial tension that is less than about 5 mN/m at the oil water interface. Preferably, less than 1 mg of surfactant should adsorb onto lgram of formation rock.
  • a suitable surfactant is also based on the oil and brine chemistries of the hydrocarbon and aqueous phase, for example, by using well-known theories such as the HLD Theory of Jean-Louis Salager. - -
  • the HLD number (or Hydrophilic Lipophilic Deviation) of a surfactant is a well known quantity and needs no extended explanation herein. The reader is referred to J.L. Salager et al., "Principles of Emulsion Formulation Engineering," in Dinesh O. Shah and K . L Mittal, eds., Adsorption and Aggregation of Surfactants in Solution (CRC Press, 2002) 501-523. Using the HLD Theory and equations, the effects of the salts present in the aqueous phase (e.g. Na+, Ca2+, Mg2+, etc) can be predicted.
  • the salts present in the aqueous phase e.g. Na+, Ca2+, Mg2+, etc
  • HLD means the equations described by J.L. Salager and for the reader's reference, the equations for non-ionic and ionic surfactants are reproduced below.
  • the HLD equations for all other types of surfactants have not been reproduced below but are accessible by referring to Salager' s HLD Theory as described above.
  • HLD a - EON - AACN - bS + aC A + c (T- T ref )
  • EON is the average number of ethylene oxide groups per non-ionic surfactant molecule
  • ACN is the alkane carbon number
  • S is the salinity as wt% NaCl
  • CA is the alcohol concentration
  • T is the Temperature
  • a is a parameter that is characteristic of the surfactant lipophilic group type and branching. It increases linearly with the number of carbon atoms in the alkyl tail.
  • the k, a, b, and c are numerical coefficients.
  • HLD ⁇ + ln(S) - &ACN + c(T- T ref ) + a A
  • ⁇ is a parameter that is characteristic of the surfactant
  • S is the salinity as wt% NaCl
  • ACN is the alkane carbon number
  • T is the
  • a surfactant with an HLD of less than zero is selected for use in the present invention.
  • Interfacial tension is a measure of the ability of a liquid-liquid interface to deform. Different surfactants affect the interfacial tension differently. Typical surfactants used in surfactant based emulsion floods according to the prior art, will decrease the interfacial tension from >10mN/m to ⁇ 0.01mN/m. The surfactants used with the present invention reduce the interfacial tension from >10mN/m to less than about 5mN/n, however the interfacial tension is preferably maintained above >0.01 mN/m. The reduction in interfacial tension provides stability to the emulsion, however the interfacial tension cannot be lowered too much or the emulsion will become unstable. The objective is to maintain the emulsion stable through the flood.
  • the selected surfactant should not phase separate at a temperature of from about 10° C to about 20° C above the formation temperature. This is another property which allows the emulsion according to the present invention to be stable, as surfactants tend to become less soluble with increasing temperature.
  • the "formation temperature” is defined as the temperature of fluids resident in a formation rather than the operating temperature of the formation, which can vary depending on operating conditions such as heated fluids being injected into a reservoir.
  • Surfactant adsorption is an important feature governing the economic viability of an EOR flooding process. Typically surfactant adsorption on formation rock leads to gradual breakdown of an emulsion. - -
  • the most desirable surfactant is one that does not adsorb at all; however, such surfactants may not be effective as oil-recovery agents. Therefore, it is preferable that the surfactant is chosen from a family of surfactants such that less than 1 mg of surfactant adsorbs onto 1 gram of substrate.
  • non-ionic surfactant is used.
  • non-ionic surfactants that could be considered for the oil-in- water emulsion of the present invention include and are not limited to:
  • a polymer may optionally be added to the aqueous medium prior to emulsification.
  • a polymer may be used to increase the viscosity of the emulsion and therefore, also increase the mobility ratio between the oil in the formation and the injection fluid being used to flood the reservoir.
  • a suitable polymer may be selected from the visco-elastic polymer family most commonly used for standard polymer floods and alkaline surfactant polymer (ASP) floods.
  • the emulsions of this invention are prepared by mixing an aqueous phase with the oil phase in any manner.
  • the oil-in-water emulsion is typically manufactured using standard emulsification equipment, such as colloidal mills or static mixers.
  • the emulsions of the invention are prepared using colloidal mills because of their ease of use and their adaptability to different process conditions.
  • - - different emulsification equipment and shearing devices could also be used, as would be known to one of ordinary skill in the art.
  • the oil in water emulsion is formed by adding the hydrocarbon to the aqueous medium, in small aliquots or continuously and placing the mixture in a colloidal mill for a time sufficient to disperse the oil as small droplets in the continuous aqueous phase.
  • the hydrocarbon content may vary from 0.1% to 80%, however it is preferred to have an emulsion comprising about 5-30% volume percent hydrocarbon.
  • the desired particle size of the internal phase droplets will depend on the pore size in the formation.
  • the objective is that individual emulsion droplets pass through the pores unimpeded.
  • Preferred droplet size is one third of the pore size in the formation, so that the emulsion droplets are not impeded in flow when they pass through such formation.
  • Average pore size in a formation can be derived by performing permeability measurements, as known to a person skilled in the art.
  • droplets can be sheared to achieve a desired size when making the emulsion.
  • the polymer can be added to the water prior to emulsification or added directly to the oil-in water emulsion.
  • the oil in water emulsion can be used in several different tertiary oil recovery methods.
  • the emulsion of the present invention can be used as a drive fluid for displacing oil from a subterranean formation.
  • the oil in water emulsion is prepared at the surface and a slug is then injected into the reservoir at an injection well.
  • the oil-in-water emulsion then displaces the oil in the formation towards a production well.
  • the emulsion flooding was tested in a core flood apparatus (2" diameter, 12" long).
  • the core was filled with Ottawa sand, given a permeability of approximately 7D, which is typical of Alberta heavy oil fields.
  • the core was saturated with 12 API dead oil from an Alberta heavy oil field.
  • Primary and secondary recovery was simulated with injection of produced reservoir brine (80,000ppm) for an equivalent of 4 pore volumes (4 X ⁇ 120mL). The injection rate was fixed at 9 mL/hr.
  • NP-330 is a non-ionic surfactant and a commercial product from Akzo Nobel. Use of such a surfactant needs to be screened for local consumption and possible environmental constraints.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Colloid Chemistry (AREA)

Abstract

L'invention porte sur une émulsion d'huile dans l'eau destinée à être utilisée dans la production d'hydrocarbures à partir d'une formation souterraine, ladite émulsion d'huile dans l'eau comprenant une phase continue aqueuse et une phase interne constituée d'hydrocarbures, ladite émulsion étant stabilisée par un tensioactif, ledit tensioactif ayant les propriétés suivantes : (i) il a une valeur de HLD qui est inférieure à 0 ; (ii) il produit une émulsion dans laquelle la tension interfaciale entre la phase d'hydrocarbures et la phase aqueuse est inférieure à environ 5 mN/m ; et (iii) il ne provoque pas de séparation de phases à une température d'environ 10°C à environ 20°C au-dessus de la température de formation.
PCT/CA2011/001154 2011-10-14 2011-10-14 Utilisation d'émulsion d'huile dans l'eau pour la récupération assistée de pétrole WO2013053036A1 (fr)

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PCT/CA2011/001154 WO2013053036A1 (fr) 2011-10-14 2011-10-14 Utilisation d'émulsion d'huile dans l'eau pour la récupération assistée de pétrole

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016108867A1 (fr) * 2014-12-31 2016-07-07 Halliburton Energy Services, Inc. Ajout dosé automatique de tensioactif pour l'augmentation d'hydrocarbures récupérés
WO2016108879A1 (fr) * 2014-12-31 2016-07-07 Halliburton Energy Services, Inc. Conception de tensioactif optimal pour l'augmentation d'hydrocarbures récupérés
WO2016108874A1 (fr) * 2014-12-31 2016-07-07 Halliburton Energy Services, Inc. Sélection de tensioactifs optimaux pour la mise en œuvre d'une récupération assistée de pétrole par injection de tensioactif
WO2016108870A1 (fr) * 2014-12-31 2016-07-07 Halliburton Energy Services, Inc. Sélection de tensioactifs inhibiteurs d'hydrates optimaux destinés à être utilisés dans des opérations concernant du gaz et du pétrole
WO2022098891A1 (fr) * 2020-11-04 2022-05-12 Saudi Arabian Oil Company Procédés et systèmes pour la génération d'émulsion stable huile-dans-eau ou eau-dans-huile pour une récupération améliorée d'huile

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3630953A (en) * 1968-01-02 1971-12-28 Chevron Res Tailored surfactants for use in forming oil-in-water emulsions of waxy crude oil
GB2182345A (en) * 1985-10-24 1987-05-13 Pfizer Method for improving production of viscous crude oil

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3630953A (en) * 1968-01-02 1971-12-28 Chevron Res Tailored surfactants for use in forming oil-in-water emulsions of waxy crude oil
GB2182345A (en) * 1985-10-24 1987-05-13 Pfizer Method for improving production of viscous crude oil

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016108867A1 (fr) * 2014-12-31 2016-07-07 Halliburton Energy Services, Inc. Ajout dosé automatique de tensioactif pour l'augmentation d'hydrocarbures récupérés
WO2016108879A1 (fr) * 2014-12-31 2016-07-07 Halliburton Energy Services, Inc. Conception de tensioactif optimal pour l'augmentation d'hydrocarbures récupérés
WO2016108874A1 (fr) * 2014-12-31 2016-07-07 Halliburton Energy Services, Inc. Sélection de tensioactifs optimaux pour la mise en œuvre d'une récupération assistée de pétrole par injection de tensioactif
WO2016108870A1 (fr) * 2014-12-31 2016-07-07 Halliburton Energy Services, Inc. Sélection de tensioactifs inhibiteurs d'hydrates optimaux destinés à être utilisés dans des opérations concernant du gaz et du pétrole
US9657565B2 (en) 2014-12-31 2017-05-23 Halliburton Energy Services, Inc. Optimal surfactant design for recovered hydrocarbon enhancement
US9856727B2 (en) 2014-12-31 2018-01-02 Halliburton Energy Services, Inc. Automatic dosing of surfactant for recovered hydrocarbon enhancement
US10053981B2 (en) 2014-12-31 2018-08-21 Halliburton Energy Services, Inc. Selection of optimal hydrate inhibitor surfactants for use in oil and gas operations
US10072204B2 (en) 2014-12-31 2018-09-11 Halliburton Energy Services, Inc. Selection of optimal surfactants for performing surfactant flooding enhanced oil recovery
WO2022098891A1 (fr) * 2020-11-04 2022-05-12 Saudi Arabian Oil Company Procédés et systèmes pour la génération d'émulsion stable huile-dans-eau ou eau-dans-huile pour une récupération améliorée d'huile
US12145112B2 (en) 2020-11-04 2024-11-19 Saudi Arabian Oil Company Methods and systems for the generation of stable oil-in-water or water-in-oil emulsion for enhanced oil recovery

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