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WO2014068390A1 - Formulation de tensioactif nanoparticulaire pour le transport d'hydrocarbures - Google Patents

Formulation de tensioactif nanoparticulaire pour le transport d'hydrocarbures Download PDF

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Publication number
WO2014068390A1
WO2014068390A1 PCT/IB2013/002437 IB2013002437W WO2014068390A1 WO 2014068390 A1 WO2014068390 A1 WO 2014068390A1 IB 2013002437 W IB2013002437 W IB 2013002437W WO 2014068390 A1 WO2014068390 A1 WO 2014068390A1
Authority
WO
WIPO (PCT)
Prior art keywords
surfactant
nanoparticulate
water
formulation according
ionic
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.)
Ceased
Application number
PCT/IB2013/002437
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English (en)
Spanish (es)
Inventor
Lilia Rodriguez Rodriguez
Edgar Javier PATIÑO REYES
Rigoberto BARRERO ACOSTA
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.)
Ecopetrol SA
Original Assignee
Ecopetrol SA
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Filing date
Publication date
Application filed by Ecopetrol SA filed Critical Ecopetrol SA
Publication of WO2014068390A1 publication Critical patent/WO2014068390A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C09K8/02—Well-drilling compositions
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • 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
    • C09K8/536—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning characterised by their form or by the form of their components, e.g. encapsulated material
    • 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
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/10—Nanoparticle-containing well treatment fluids

Definitions

  • the present invention relates to nanoparticulate surfactant formulations that make it easier to transport heavy hydrocarbons.
  • Hydrocarbons generate more than 50% of the energy consumed worldwide and its reliable supply is vital for the functioning of all countries.
  • Heavy hydrocarbon reserves are constituted as the new source of production due to the reduction of medium and light hydrocarbons.
  • Heavy, extra heavy, fuel oil and barrel bottom products are characterized by having high viscosity, since being chemically constituted by long carbon chains generates high resistance to flow with low or zero mobility.
  • These high viscosity hydrocarbons at a temperature of 25 ° C and atmospheric pressure can be found in a liquid, semi-solid and solid state, requiring high energy consumption for their movement with significant operating costs and a complex infrastructure that limits their transportation through pipelines and subsequent commercialization. .
  • Another method for transporting these hydrocarbons with mobility problems consists in using dispersions and emulsions of hydrocarbon in water, where the hydrocarbon is distributed in small particles within an aqueous continuous phase and is stabilized by the action of a surfactant product (also called surfactant).
  • An emulsion is a dispersion of a liquid in another, not miscible, stabilized by a surfactant (also called emulsifier or emulsifier), whereby the emulsion constitutes a particular case of the dispersions.
  • Ionic surfactants in turn can be anionic, cationic or amphoteric.
  • US patent application US2009127505 A1 refers to the preparation of rare earth metal oxide nanoparticles from inverse aqueous micelles, where the particles have a large surface area with respect to volume and where it is incorporated a surfactant uniformly in each of them, so that when applied to the inner surface of a pipe or sprayed on a stream of fluid in a pipe, the particles reduce the roughness of the inner surface of that pipe.
  • the application mixing this application causes a significant reduction in pressure drops, friction and a better recovery and performance of fluid flowing through the pipe.
  • the international publication WO 2008101947 describes a procedure to reduce the viscosity of a hydrocarbon mixture having a viscosity greater than 10 Pa s (10000 cP) at 20 0 C.
  • the process comprises the steps of: a) putting contact the hydrocarbon mixture with inorganic catalyst particles in the presence of water and a surfactant; b) catalytically reduce the average molecular weight of the hydrocarbon mixture.
  • the process is particularly suitable in order to improve the behavior of heavy fossil fuel sources for processing in conventional refinery equipment. .
  • US patent application 5910467 describes a stabilized solid emulsion and a method of manufacturing it, which is useful in the recovery of hydrocarbons from underground formation. More specifically, the emulsion comprises oil and water and is stabilized using undissolved solid particles, which are preferably at least partially oleophilic. Additionally, carbon dioxide or other gas is added to the emulsion to adjust the viscosity of the emulsion to the desired level.
  • the stabilized solids emulsion can be used as a drive fluid to displace hydrocarbons from the formation or to produce a barrier in order to divert the flow of fluids in the formation.
  • Such solid particles well they may be particles of the formation (ie, native of the formation) or particles not characteristic of the formation (ie, obtained outside the formation).
  • Solid particles not characteristic of the formation may be of natural or synthetic origin. Some preferred solids include clays, quartz, feldspar, plaster, coal dust, asphaltenes and polymers. This document indicates that the fine particles allow to stabilize the emulsion, since the films surrounding the drops of the internal phase of the emulsion are kept in a stable state under formation conditions for a sufficient time to use the emulsion as intended. (for example, increase the rate and / or amount of hydrocarbon production from a formation). Additionally, solid particles are resistant to chemical reactions that tend to deactivate surfactants, thereby causing destabilization or breakage of the emulsion. Consequently, the revealed emulsions are stable over a wide range of salinity of the formation water. This document also indicates that solid particles that interact with water and oil stabilize the foam film.
  • US patent application 7121339 discloses an oil-in-water emulsion stabilized with solids and a method for preparing the dry oil-in-water stabilized extract.
  • the oil-in-water emulsion is formed by combining oil, water, solid particles and a pH enhancing agent, mixing until the emulsion is formed.
  • the low viscosity of the oil-in-water emulsion can be used to increase oil production from underground deposits.
  • the low viscosity of the oil-in-water emulsion can also be used to improve the transport of oil through a pipe. This document indicates that the emulsion disclosed there does not require surfactants, making it less expensive than the solutions that do contain them. Additionally, he points out that it is an emulsion that is easy to demulsify.
  • hydrocarbon dispersions in water manage to significantly reduce the viscosity of the heavy hydrocarbon depending on the oil concentration present.
  • a heavy hydrocarbon with a viscosity value of 5 passes per second (Pa-s) (5000 centi Poise (cP)) measured at 30 ° C and 30 s ' dispersions with a hydrocarbon content heavy in water of 70% by volume have a viscosity of less than 0.5 Pa s (500 cP) (30 ° C, 30 s "1 ).
  • a surfactant is required that improves contact between the phases of the dispersion to achieve a hydrocarbon dispersion in water of lower viscosity or increase the hydrocarbon content to a viscosity suitable for pipeline transport minimizing the consumption of additive at values below 5000 ppm to reduce the production and separation costs of hydrocarbon dispersions in water.
  • nanoparticulate surfactant formulation using hydrophilic nanoparticles, ionic, non-ionic surfactants or mixtures thereof and water.
  • This nanoparticulate surfactant formulation improves the flow properties of hydrocarbon dispersions in water as well as their stability.
  • a surfactant formulation comprising a nanoparticle surfactant of metallic and / or non-metallic origin with a concentration between 15% and 100% of the mass content of the formulation.
  • concentration of the liquid surfactant of ionic, non-ionic origin or mixture thereof is in the range of 0 to 85% of the mass content of the surfactant formulation. According to the viscosity of the surfactant obtained, water between 0% and 70% by mass is added to improve the fluidity of the obtained surfactant.
  • Still another objective of the present invention is to provide a surfactant formulation comprising a surfactant in nanoparticles with a concentration between 250 and 2000 ppm in the hydrocarbon dispersion in water and wherein the concentration of the liquid surfactant of ionic, non-ionic origin or mixture thereof is in the range of 0 to 2500 ppm in the hydrocarbon dispersion in water.
  • the hydrocarbon dispersion in water obtained by using the surfactant formulation of the present invention has a lower viscosity than that obtained with a dispersion prepared with a liquid surfactant of ionic, non-ionic origin or mixture thereof under equal conditions of preparation, hydrocarbon content and total surfactant content.
  • Figure 1 shows a block diagram of obtaining the nanoparticulate surfactant formulation in accordance with the present invention.
  • Figure 2 illustrates a block diagram of obtaining hydrocarbon dispersions in water with the nanoparticulate surfactant formulation in accordance with the present invention.
  • Figure 3 corresponds to a rheological curve of hydrocarbon dispersions in water with a conventional ionic surfactant formulation derived from petroleum sulphonates.
  • Figure 4 corresponds to a rheological curve of hydrocarbon dispersions in water with a nanoparticulate surfactant formulation in accordance with the present invention and with a conventional ionic surfactant formulation derived from petroleum sulphonates.
  • the nanoparticulate surfactant formulation object of the present invention comprises a nanoparticulate surfactant (1) and a liquid surfactant of ionic, non-ionic origin or mixture thereof (2) which are added to a stream of water (3) in a homogenization unit (100) to obtain the nanoparticulate surfactant mixture (4).
  • the pH of the nanoparticulate surfactant mixture (4) is adjusted in the homogenization unit (200) by the addition of an aqueous acidic or basic solution (5) to obtain a nanoparticulate surfactant formulation (6) with the pH of specification.
  • the nanoparticulate surfactant (1) has a hydrophilic nature and has a metallic and / or non-metallic origin with an average particle size between 20 and 90 nm, a surface area between 150 and 250 m 2 / g and a concentration of acid sites between 0, 5 and 3.5 equivalent / kg.
  • the mass content of the nanoparticulate surfactant (1) in the surfactant formulation is between 15% and 100%.
  • the nanoparticulate surfactant (1) is obtained from various natural sources and comprises silica, metallic nanoparticles or mixtures thereof, which have been modified to provide the desired properties.
  • Modified silica-derived nanoparticles and nanoparticulate surfactant component (1) characterized in that the percentage of unreacted silanol (Si-OH) groups is in a range between 50 and 100%.
  • the nanoparticles of metallic origin component of the nanoparticulate surfactant (1) that include metal compounds such as calcium oxide, magnesium oxide, copper oxides, aluminum oxide, iron oxides among others.
  • the liquid surfactant (2) can be an ionic, cationic, anionic, amphoteric, non-ionic surfactant or a mixture thereof.
  • the liquid surfactant (2) is selected according to the pH and hardness conditions of the water used to form the hydrocarbon dispersion in water thus:
  • Anionic liquid ionic surfactant for waters with hardness greater than 180 mg / L (expressed as mg CaC0 3 / L), pH between 6 and 14, selected from the group of: petroleum alkyl sulphonates, sodium and potassium alkyl benzene sulphonates , sodium and potassium alkyl aryl benzene sulfonate, alpha olefin sulphonates, hydroxy alkane sulphonates, hydroxy alkane sulfate sulfate, alpha olefin sulfonate and alkyl aryl sulfonates of petroleum.
  • Ionic liquid cationic liquid surfactant for water with hardness greater than 120 mg / l and less than or equal to 180 mg / L (expressed as mg CaC0 3 / L), pH between 2 and 4, selected from the group of: quaternary ammonium salts, alkyl linear amine and alkyl ammonium, dodecyl amine or lauryl amine, alkyl dimethyl benzyl ammonium, quaternary salts.
  • the liquid surfactant (2) is present in the formulation of the invention in a mass proportion is between 0 and 85% of the formulation.
  • the surfactant formulation (6) has a pH between 4.0 and 8.5 and is adjusted by an acidic or basic aqueous current (5) as required.
  • the homogenization units (100, 200) correspond to a tank arrangement with mechanical agitation and / or a static mixer or a series of them to achieve adequate homogenization of the materials that make up the formulation of the nanoparticulate surfactant (6) according to the present invention.
  • the nanoparticulate surfactant (6) is used to obtain hydrocarbon dispersions in water for which it is added to a stream of water (7) in order to homogenize it in a static mixer or a series of them (300) and obtain a diluted stream of water and nanoparticulate surfactant (8).
  • the hydrocarbon (9) is in fluid form by heating, dilution or mixing and is pumped to a dispersion unit (400) where it is pre-mixed with the diluted stream of water and nano-particulate surfactant (8).
  • This premix stream (10) passes to the homogenization unit (500) where the hydrocarbon dispersion in water (1) is formed.
  • the hydrocarbon dispersion in water (11) can be stored in tanks or pumped directly to a transport pipeline as required.
  • the homogenization unit (500) corresponds to a mixer or a series of them, which can be sonic, magnetic, mechanical or static as required.
  • the hydrocarbon dispersion in water (11) has a concentration of the nanoparticle surfactant (1) between 250 and 2000 ppm and in turn the concentration of the liquid surfactant (2) of ionic, non-ionic origin or mixture of they are in the range of 0 to 2500 ppm.
  • nanoparticulate surfactant formulation according to the present invention In order to demonstrate a better efficiency of the nanoparticulate surfactant formulation according to the present invention with respect to the formulations conventionally employed and containing only Ionic, non-ionic surfactants or mixtures thereof to obtain dispersions of hydrocarbons in water, the two formulations are evaluated under the same conditions of preparation, hydrocarbon content and surfactant dosage. In the following examples all the dynamic viscosities presented are measured at 30 ° C and 30 S "1
  • a typical liquid surfactant formulation with a 25% mass content of petroleum sulphonate ionic surfactant was prepared.
  • a surfactant formulation with a content of 6% nanoparticles and 19% ionic liquid surfactant was prepared.
  • a hydrophilic silica nanoparticulate surfactant with a particle size of 55 nm was used.
  • Example 3 The conventional ionic surfactant formulation prepared in Example 1, water and a heavy hydrocarbon with a viscosity of 4.53 Pa s (4530 cP) was used to prepare hydrocarbon dispersions in water ( Figure 3) with a concentration of 1300 ppm of surfactant additive.
  • Table 1 presents the viscosity results of the different dispersions of hydrocarbons in water using the ionic surfactant derived from petroleum sulphonates.
  • nanoparticulate surfactant formulation it is possible to obtain hydrocarbon dispersions in water with lower viscosity and stability suitable for transport and storage.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Nanotechnology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

La présente invention concerne des formulations de tensioactifs nanoparticulaires qui permettent de transporter avec une plus grande facilité des hydrocarbures lourds. La formulation comprend un agent tensioactif nanoparticulaire sélectionné dans le groupe constitué de nanoparticules hydrophiles de silice, métalliques ou de mélanges de ces dernières et d'un agent tensioactif liquide ionique, non ionique ou d'un mélange de ceux-ci.
PCT/IB2013/002437 2012-11-01 2013-11-01 Formulation de tensioactif nanoparticulaire pour le transport d'hydrocarbures Ceased WO2014068390A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CO12197752A CO6940084A1 (es) 2012-11-01 2012-11-01 Formulación de sufractante nanoparticulado para el transporte de hidrocarburos
CO12-197752 2012-11-01

Publications (1)

Publication Number Publication Date
WO2014068390A1 true WO2014068390A1 (fr) 2014-05-08

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PCT/IB2013/002437 Ceased WO2014068390A1 (fr) 2012-11-01 2013-11-01 Formulation de tensioactif nanoparticulaire pour le transport d'hydrocarbures

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CO (1) CO6940084A1 (fr)
WO (1) WO2014068390A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10053616B2 (en) 2015-04-09 2018-08-21 Saudi Arabian Oil Company Encapsulated nanocompositions for increasing hydrocarbon recovery
US10125307B2 (en) 2016-01-13 2018-11-13 Saudi Arabian Oil Company Stabilization of petroleum surfactants for enhancing oil recovery
US11760944B2 (en) 2019-07-19 2023-09-19 Instituto Mexicano Del Petroleo Hydroprocessing of heavy crudes by catalysts in homogenous phase

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030220204A1 (en) * 2002-05-24 2003-11-27 3M Innovative Properties Company Use of surface-modified nanoparticles for oil recovery
WO2008036812A2 (fr) * 2006-09-20 2008-03-27 Baker Hughes Incorporated Nanoparticules servant a stabiliser des fluides tensioactifs viscoelastiques
WO2010045545A1 (fr) * 2008-10-17 2010-04-22 Frac Tech Services, Ltd. Procédé pour des opérations d’intervention dans des formations d’hydrocarbure souterraines

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030220204A1 (en) * 2002-05-24 2003-11-27 3M Innovative Properties Company Use of surface-modified nanoparticles for oil recovery
WO2008036812A2 (fr) * 2006-09-20 2008-03-27 Baker Hughes Incorporated Nanoparticules servant a stabiliser des fluides tensioactifs viscoelastiques
WO2010045545A1 (fr) * 2008-10-17 2010-04-22 Frac Tech Services, Ltd. Procédé pour des opérations d’intervention dans des formations d’hydrocarbure souterraines

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
S. KUMAR ET AL.: "Size-dependent interaction of silica nanoparticles with different surfactants in aqueous solution", LANGMUIR, vol. 28, 2012, pages 9288 - 9297 *
S. KUMAR ET AL.: "Tuning of nanoparticle-surfactant interactions in aqueous system", JOURNAL OF PHYSICS: CONDENSED MATTER, vol. 23, 2011, pages 035101 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10053616B2 (en) 2015-04-09 2018-08-21 Saudi Arabian Oil Company Encapsulated nanocompositions for increasing hydrocarbon recovery
US10550311B2 (en) 2015-04-09 2020-02-04 Saudi Arabian Oil Company Encapsulated nanocompositions for increasing hydrocarbon recovery
US10125307B2 (en) 2016-01-13 2018-11-13 Saudi Arabian Oil Company Stabilization of petroleum surfactants for enhancing oil recovery
US10538693B2 (en) 2016-01-13 2020-01-21 Saudi Arabian Oil Company Stabilization of petroleum surfactants for enhancing oil recovery
US11760944B2 (en) 2019-07-19 2023-09-19 Instituto Mexicano Del Petroleo Hydroprocessing of heavy crudes by catalysts in homogenous phase
US11866652B2 (en) 2019-07-19 2024-01-09 Instituto Mexicano Del Petroleo Hydroprocessing of heavy crudes by catalysts in homogeneous phase

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CO6940084A1 (es) 2014-05-09

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