EP2723487A1 - Nanotracers for labeling the injection water in oil fields - Google Patents
Nanotracers for labeling the injection water in oil fieldsInfo
- Publication number
- EP2723487A1 EP2723487A1 EP12728613.6A EP12728613A EP2723487A1 EP 2723487 A1 EP2723487 A1 EP 2723487A1 EP 12728613 A EP12728613 A EP 12728613A EP 2723487 A1 EP2723487 A1 EP 2723487A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nanoparticles
- deposit
- matrix
- colloidal solution
- radicals
- 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.)
- Withdrawn
Links
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0039—Post treatment
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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
- C09K8/588—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0043—Preparation of sols containing elemental metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/18—In situ polymerisation with all reactants being present in the same phase
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- 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
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- 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
- E21B47/00—Survey of boreholes or wells
- E21B47/10—Locating fluid leaks, intrusions or movements
- E21B47/11—Locating fluid leaks, intrusions or movements using tracers; using radioactivity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Definitions
- the field of this invention is that of the exploration and exploitation of oil deposits.
- this invention relates to the development of nanoparticles, useful as tracers, for tracking the movement of fluids injected into a petroleum deposit.
- the injected fluids diffuse through a solid geological medium which constitutes the oil reservoir, thus making it possible to study the latter by following the path of the injected fluids.
- the objective is in particular to control the flows between the injection well (s) and the production well (s) and / or to evaluate the volumes of oil in reserve and water in the deposit and, in the end, optimize oil exploration and development.
- tracers easily detectable in the liquid. These tracers make it possible to follow the injection water.
- the measurement of the amount of tracer at the production wells makes it possible to know the volume and the distribution of the injection fluid in the formation.
- the tracer / oil interaction can be used to determine the proportion of liquids in the reservoir that is the oil field. This is one of the most important parameters that can be determined by the use of such tracing fluids, since this parameter makes it possible, on the one hand, to adjust the water injection program, and on the other hand, to evaluate the quantity of oil remaining to be produced.
- the study method allowing the analysis, the control and the optimized recovery of oil, requires that the tracer concentration in the fluid produces an output. is measured continuously or not, so as to be able to plot tracer concentration curves as a function of time or as a function of the volume of fluid produced.
- the specifications of the tracers that can be used in these injection waters for the optimization of oil recovery include the following specifications:
- the tracer concentration in the output fluids is determined and compared with that of the fluids injected into the injection well (s);
- Canadian patent application CA 2,674,127-Al relates to a method of using a natural carbon 13 isotope for the identification of early breakthrough of injection water in oil wells.
- the tracer molecules known and used have a specific chemical / radioactive signature. These known tracers can be detected with great sensitivity but nevertheless have three major disadvantages:
- the French patent application FR2867180-A1 describes hybrid nanoparticles comprising, on the one hand, a core consisting of a rare earth oxide, possibly doped with a rare earth or an actinide or a mixture of grounds. rare or a mixture of rare earths and actinide and, secondly, a coating around this core, said coating consisting mainly of polysiloxane functionalized with at least one biological ligand grafted by covalent bonding.
- the core may be Tb + doped Gd 2 O 3 base or uranium and the polysiloxane coating may be obtained by reacting an aminopropyltriethoxysilane, a tetraethylsilicate and triethylamine.
- the French patent application FR2922106-A1 relates to the same technical field and aims to use these nanoparticles as sensitizing radio agents to increase the effectiveness of radiotherapy.
- These nanoparticles have a size of between 10 and 50 nanometers.
- the present invention aims to satisfy at least one of the following objectives:
- nanoparticles for use in the study of a petroleum deposit, said nanoparticles being characterized in that they comprise:
- a core consisting of a noble metal or an alloy of noble metals, a matrix comprising (i) polysiloxanes and (ii) an organometallic fluorophore covalently bonded to the polysiloxanes, said matrix being functionalized on its surface to form Silane bonds Si-R, said radicals -R being constituted for at least 50%, preferably at least 75%, of neutral or charged hydrophilic compounds, preferably from polyethers or polyols, or mixtures thereof.
- the invention relates secondly to a method for preparing a colloidal solution of nanoparticles that can be used for the study of a petroleum deposit, said method comprising the following steps:
- a noble metal core coated with a polysiloxane matrix prefunctionalized with hydrophilic silanes is synthesized in an inverse microemulsion, ii. an aqueous colloidal solution of nanoparticles is extracted by decantation after destabilization of the microemulsion, for example in a water / alcohol mixture,
- the nanoparticles are heated to at least 50 ° C, for example about 80 ° C.
- the invention relates to an injection liquid for the study of a petroleum deposit, comprising nanoparticles as defined above, or a colloidal solution of nanoparticles that can be obtained by the process as defined above.
- the invention also relates to the use of these nanoparticles as tracers in injection waters of a petroleum deposit, which are intended for the study of said deposit by diffusion through it, with a view in particular to controlling the flow between an injection well and a production well and / or to evaluate the volumes of oil in reserve in the deposit.
- nanoparticles according to the invention are intended for use as tracers in the study of a petroleum deposit, said nanoparticles being characterized in that they comprise:
- a core consisting essentially of a noble metal or an alloy of noble metals
- a matrix comprising (i) polysiloxanes and (ii) an organometallic fluorophore covalently bound to the polysiloxanes, said matrix being functionalized on its surface to form silane bonds Si-R, said radicals -R constituting for at least 50%, preferably at least 75% of neutral or charged hydrophilic compounds, preferably from polyethers or polyols, or mixtures thereof.
- the nanoparticles according to the invention are detectable, that is to say that one can identify their presence or not in the medium beyond a certain concentration and that one can even quantify their concentration when they are present in the environment.
- These nanoparticles are capable of forming a stable colloidal suspension in a saline medium, which sediments little. For example, this suspension shows no precipitation or agglomeration with time, eg after 6 months at room temperature.
- the core consists essentially of a noble metal, for example gold, silver or platinum, and / or an alloy of noble metals.
- the core consists essentially of gold particles.
- the nanoparticles obtained according to the invention are denser and of a more regular structure than those made with other materials for the choice of the heart.
- the gold has in certain cases an antenna effect which then advantageously makes it possible to amplify the fluorescent signal emitted by the organometallic fluorophore of the matrix during the detection.
- Gold along with other noble metals such as Ag, Pd, Pt, Ir, or Rh, is also detectable by the ICP (or plasma torch spectrometry) detection method and can be used as an internal reference for detection of nanoparticles and their possible degradation.
- gold has the advantage of being also detectable by plasmon absorption allowing the detection and quantification of nanoparticles at very low concentrations, for example, at the level of the single particle, in particular after a dispersion of a volume. given on a support.
- a particle can be detected in at least 10, preferably 100 ⁇ L ⁇ .
- the gold particles forming the core of the nanoparticles have a size of at least 3 nm, preferably between 5 nm and 15 nm.
- the matrix forms a core coating layer of noble metals of the nanoparticle. It makes it possible to encapsulate the detectable molecules for the detection and / or quantification of the nanoparticles.
- the matrix of the nanoparticles according to the invention comprises polysiloxanes and at least one organometallic fluorophore covalently bonded to the polysiloxanes.
- it consists essentially of polysiloxanes, functionalized on the outer surface of the nanoparticles and encapsulating organometallic fluorophores.
- the matrix and core assembly form nanoparticles with an average diameter of preferably between 20 nm and 100 nm, for example between 20 nm and 50 nm.
- the nanoparticles according to the invention have a polydispersity index of less than 0.5, preferably less than 0.3, or less than 0.2, for example less than 0.1.
- the size distribution of the nanoparticles is for example measured using a commercial particle size analyzer, such as a Malvern Zeta sizer Nano-S granulometer based on the PCS (Photon Correlation Spectroscopy). This distribution is characterized by a mean diameter and a polydispersity index.
- a commercial particle size analyzer such as a Malvern Zeta sizer Nano-S granulometer based on the PCS (Photon Correlation Spectroscopy). This distribution is characterized by a mean diameter and a polydispersity index.
- mean diameter means the harmonic mean of the diameters of the particles.
- polydispersity index refers to the width of the size distribution derived from the cumulant analysis. Both of these features are described in ISO 13321: 1996.
- the matrix may comprise, if appropriate, other materials chosen from the group consisting of silicas, aluminas, zirconiums, aluminates, aluminophosphates, metal oxides, or metals (example: Fe, Cu, Ni , Co ...) passivated at the surface by a layer of the oxidized metal or other oxide and their mixtures and alloys.
- An essential function of the matrix is to maintain the organometallic fluorophores in the nanoparticles and in particular to protect them from attacks from the external environment.
- Organometallic fluorophores produce one or more detectable signals by nanoparticle.
- the organometallic fluorophores used in the nanoparticles according to the invention are preferably chosen so as to produce a fluorescent signal which is stable over time and which is not very influenced by the physico-chemical conditions of the environment traversed (for example temperatures, pH, compositions ionic, solvents, redox conditions ).
- the organometallic fluorophores contained in the matrix of the nanoparticles are chosen from vanadates or oxides of rare earths, or their mixtures. In a specific embodiment, they are chosen from lanthanides, their alloys and their mixtures, linked to complexing molecules.
- the organometallic fluorophores are detectable by time-resolved fluorescence. Lanthanides linked to complexing molecules are then particularly preferred.
- the metals of the lanthanide series include atomic number elements from 57 (lanthanum) to 71 (lutetium).
- the lanthanides in the group consisting of: Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm and Yb and their mixtures and / or alloys, linked to complexing molecules, will be chosen.
- complexing molecules or "chelating agent” is meant any molecule capable of forming with a metal agent, a complex comprising at least two coordination bonds.
- a complexing agent having a coordination of at least 6, for example at least 8, and a dissociation constant of the complex, pKd, greater than 10 and preferably greater than 15, with a lanthanide, will be chosen. .
- dissociation constant pKd is understood to mean the measurement of the equilibrium between the ions in the complexed state by the ligands and those free dissociated in the solvent. Precisely, it is less the logarithm in the base of the dissociation product (-log (Kd)), defined as the equilibrium constant of the reaction which translates the transition from the complexed state to the ionic state.
- Such complexing agents are preferably polydentate chelating molecules selected from families of polyamine-type polycarboxylic acid molecules and having a number of potential high coordination sites, preferably greater than 6, such as certain macrocycles.
- DOTA or 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid of the following formula, will be chosen: or one of its derivatives.
- the matrix may also contain, besides the complexing agent, a cyclic agent, for example grafted to the polysiloxanes.
- cyclic agent an organic molecule, comprising at least one aromatic ring or heterocycle, preferably selected from benzene, pyridine or their derivatives, and capable of amplifying the fluorescent signal emitted by the organometallic fluorophore, for example a complexing agent linked to the lanthanide.
- cyclic agents interesting if they are characterized by a high absorbance, are used in particular to amplify the fluorescent signal emitted by the organometallic fluorophores (antenna effect by transfer of the excitation of the agent towards the fluorophore).
- the cyclic agent may be grafted covalently either directly to the polysiloxanes of the matrix or to the organometallic fluorophore.
- the organometallic fluorophores consisting of a lanthanide with a complexing agent are grafted to the polysiloxanes covalently via an amide function.
- the matrix of the nanoparticles according to the invention is functionalized on its surface.
- the functionalization of the matrix comprises the formation of silane bonds Si-, said radicals -R being constituted by at least 50%, preferably at least 75% of neutral or charged hydrophilic compounds, preferably from polyethers or polyols, or their mixtures.
- the functionalization of the nanoparticles is carried out so that the zeta potential of the nanoparticles measured at a pH of 6.5 is less than +10 mV.
- zeta potential refers to the electrokinetic potential in colloidal systems. This is the electrical potential of the double surface layer or the potential difference between the solvent and the liquid layer attached to the particle.
- the zeta potential can be measured with the same apparatus as that used to measure the size distribution as described in the article "Zeta potential of colloids in Water", ASTM Standard D 4187-82, American Society for Testing and Materials, 1985.
- the functionalization aims in particular to obtain good colloidal stability in a saline medium, for example a critical salt concentration of at least 50 g / l, or even at least 100 g / l. Its function is also to modulate the water-rock interactions of the nanoparticle (to minimize its adsorption on the rock for example), or even to modulate (for example minimize) the water-oil interactions.
- the nanoparticles according to the invention exhibit minimal adsorption with this type of test.
- the covalently grafted radicals R based on Si-R silane bonds can comprise:
- hydrophilic groups preferably hydrophilic organic compounds, with molar masses of less than 5000 g / mol and more preferably less than 450 g / mol, preferably chosen from organic groups comprising at least one of the following functions: alcohol, carboxylic acid, amine, amide, ester, ether-oxide, sulfonate, phosphonate and phosphinate, and a combination of these functions,
- neutral hydrophilic groups preferably chosen from sulphonate derivatives, alcohols, for example sugars or polyols, more preferably a polyalkylene glycol or a polyol, more preferably still a polyethylene glycol, diethylenetriamine pentaacetic acid (DTP A), DTP A dithiolated (DTDTPA), a gluconamide or a succinic acid, and mixtures of these neutral hydrophilic groups,
- the -R radicals of silanes Si-R at the surface consist of at least 50%, preferably at least 75%, of neutral hydrophilic radicals, for example chosen from polyols, for example gluconamide, or polyethers, for example polyethylene glycol, or mixtures thereof.
- the radicals -R of the silane bonds are present on the surface at the rate of at least one -R radical for 10 nm of surface, for example at least one -R radical for 1 nm 2, and preferably at least between 1 and Radicals -R per nm 2.
- Surface functionalization is by condensation of silanes at the surface of the matrix.
- Polysilanes such as diethylene-di (trimethoxy) silane
- the invention also relates to a process for preparing a colloidal suspension of nanoparticles that can be used as a tracer for the study of a petroleum deposit.
- the method according to the invention comprises the following steps:
- a noble metal core coated with a polysiloxane matrix prefunctionalized with hydrophilic silanes is synthesized in an inverse microemulsion
- an aqueous colloidal solution of nanoparticles is extracted by decantation after destabilization of the microemulsion, for example in a water / alcohol mixture, for example water / isopropanol, the nanoparticles are heated to at least 50 ° C., for example, approximately
- the core and the matrix are synthesized in inverse microemulsion. If necessary, the nanoparticles can be pre-coated at this stage with a hydrophilic silane.
- microemulsion is then destabilized, for example with a water / alcohol mixture such as water / isopropanol, so as to extract the nanoparticles in the form of a stable aqueous colloidal solution (ie which does not precipitate).
- a water / alcohol mixture such as water / isopropanol
- the nanoparticles are never in the dry phase.
- the dry solid phase-free method would make it possible to obtain nanoparticles of more homogeneous size, and therefore with a lower polydispersity index.
- Another particularly advantageous stage of the process according to the invention is the heating step, at least 50 ° C, for example at least 60 ° C, at least 70 ° C, for example at 80 ° C, for a sufficient time to allow densification of the coating layer, for example at least 30 minutes, preferably at least 1 hour.
- the heating step would make it possible to increase the stability of the particles, in particular over time by limiting the agglomeration phenomena. This would also make it possible to densify the coating and to reduce the number of free surface silanol groups and more generally in the coating layer.
- the adhesion and the stability of the coating layer are thus improved and would also provide additional protection for the fluorophores contained in the matrix.
- the method according to the invention thus makes it possible to obtain colloidal solutions with nanoparticles with advantageous and distinct properties of the prior art, in particular of smaller average diameter, for example, less than 50 nm and a low polydispersity index, for example less than 0.3, or even less than 0.1, and with a very low reactivity with the external environment (stealth tracer), as can be demonstrated by means of the permeation test described as an example .
- the invention also relates to a colloidal solution of nanoparticles, obtainable according to the method of the invention described above.
- the nanoparticles are prepared according to the above method and have the advantageous structural characteristics as defined above.
- the nanoparticles obtained by the above process comprise a noble metal core, for example gold, and a matrix comprising polysiloxanes including an organometallic fluorophore, for example a complexing agent linked to a lanthanide.
- the nanoparticles according to the invention are particularly useful as tracers in injection waters of a petroleum deposit, which are intended for the study of said deposit by diffusion through it, in particular to control the flow between a injection wells and a production well and / or to evaluate the volumes of oil in reserve in the deposit.
- the diffused liquid Prior to the analysis of the diffused liquid, it is concentrated, preferably by filtration or dialysis, and, more preferably still, by tangential filtration and preferably by use of membrane cutoff thresholds of less than 300 kDa (kilo Dalton ).
- the nanoparticles Preferably, it is desired to detect at least two types of signals emitted by the nanoparticles:
- a first signal that can be emitted by the organometallic fluorophores and measured by fluorescence is a first signal that can be emitted by the organometallic fluorophores and measured by fluorescence.
- a second signal capable of being emitted by the noble metal such as gold, silver, platinum and their mixtures and / or alloys, and measured by chemical analysis and / or by ICP;
- said noble metal constituting the heart of the nanoparticle.
- fluorescence detection is preferred in time resolved (for detecting organometallic fluorophores) and / or by ICP (for detection of the noble metal in the heart nanoparticles).
- the time resolved fluorescence detection method is for example described in the article "ultrasensitive bioanalytical assays using resolved time fluorescence detection", Phnrmac. Thu. Flight. 66, pp. 207-335, 21995.
- the method of detection by ICP is for example described in "application of laser ICP-MS in environmental analysis", Fresenieus Journal of Analytical Chemistry, 355: 900-903 (1996).
- the fluorescence detection in time resolved that is to say, triggered with delay after excitation (ie a few microseconds) makes it possible to eliminate a large part of the luminescence intrinsic to the solid medium studied and to measure only that relative to the nanoparticle fescue.
- the invention relates to an injection liquid in a petroleum field, characterized in that it comprises a tracer based on nanoparticles according to the invention as defined above.
- this liquid comprises water and the nanoparticles as defined above.
- the injection waters may comprise, in addition to the nanoparticles, the following elements: surfactants, hydrophilic small polymers, polyalcohols (for example diethylene glycol), salts and other molecules conventionally used in petroleum injection.
- Figure 1 shows the emission spectrum in time resolved (delay 0.1 ms, acquisition time 5 ms) of the nanoparticles containing Eu DTPA and fluorescein under excitation at 395 nm and the excitation spectrum in time resolved (delay 0.1 ms, acquisition time 5 ms) of these same nanoparticles with a fixed emission at 615 nm
- Figure 2 shows the time-resolved excitation spectrum (delay 0.1 ms, acquisition time 5 ms) of the nanoparticles containing Eu DOTA and fluorescein with a fixed emission at 615 nm and the emission spectrum in time resolved (delay 0.1 ms, acquisition time 5 ms) of the particles containing Eu DOTA and fluorescein under excitation at 395 nm
- Figure 3a shows the time-resolved excitation spectrum (delay 0.1 ms, acquisition time 5 ms) of the particles containing nanoparticles containing Tb and pyridine derivatives with a fixed emission at 545 nm
- FIG. 3b shows the emission spectrum in time resolved (delay 0.1 ms, acquisition time 5 ms) of the particles containing nanoparticles containing Tb and pyridine derivatives under excitation at 246 nm
- Figure 4 shows comparative permeation curves between a reference tracer (gray) and the nanoparticles (black) according to the preparation method 4. As abscissa, the volume elapsed. On the ordinate, absorption or fluorescence, normalized to the initial values. After 180 mL, a solution of degassed seawater without tracer is injected. Examples
- Preparation Method 1 Preparation of a colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating fluorescein-derived organic fluorophores and europium (DTPA) complexes.
- DTPABA diethylenetriaminepentaaceticbisanhydride acid
- APTES 0.065 mL of triethylamine
- DMSO dimethylsulfoxide
- EuCl3,6H 2 0 200 mg of EuCl3,6H 2 0 is added.
- the complexation is sufficient; the following steps are then carried out: in a 2.5 mL bottle, 20 mg of FITC (fluorescein isothiocyanate) are introduced with 0.5 mL of APTES ((3-aminopropyl) triethoxysilane) with vigorous stirring. Homogenized for 30 minutes at room temperature.
- FITC fluorescein isothiocyanate
- the polymerization reaction of the silica is completed by the addition of 0.800 ml of NH 4 OH after 10 minutes.
- the microemulsion is stirred for 24 h at room temperature.
- silane-gluconamide N- (3-Triethoxysilylpropyl) gluconamide
- the colloidal solution recovered is then placed in a 300 kDa VIVASPIN ⁇ tangential filtration system and then centrifuged at 4000 rpm until a purification rate greater than 500 is obtained.
- Preparation Process 2 Preparation of a colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating fluorescein-derived organic fluorophores and europium (DOTA) complexes.
- DOTA europium
- the synthesis is similar to that described in Preparation Procedure 1 except that the 200 mg of diethylenetriaminepentaaceticbisanhydride acid is replaced by 256 mg of 1,4,7,10-tetraazacyclodecane-1,4,5,10- glutaric tetraacetic anhydride) (DOTAGA). The rest of the synthesis is identical.
- Preparation Process 3 Preparation of a colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating aromatic ring-containing organic molecules derived from pyridine (antenna) and terbium complexes.
- the polymerization reaction of the silica is completed by the addition of 0.800 ml of NH 4 OH after 10 minutes.
- the microemulsion is stirred for 24 h at room temperature.
- Preparation Process 4 Preparation of a colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating fluorescein-derived aromatic ring-containing organic molecules and particles containing europium complexes.
- FITC fluorescein isothiocyanate
- APTES (3-aminopropyl) triethoxysilane
- APTES APTES
- TEOS tetraethylorthosilicate
- Preparation process 5a Colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating organic molecules containing an aromatic pyridine ring and particles containing europium complexes.
- silane-gluconamide is replaced by an addition of 450 mg of silane (N- (triethoxysilylpropyl) -O-polyethyleneoxideurethane) corresponding to a theoretical amount of 2 silanes per nm of area.
- Preparation process 5b Colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating organic molecules containing an aromatic pyridine ring and particles containing europium complexes.
- the synthesis is similar to that described in preparation method 1 unlike the functionalization performed in the microemulsion.
- the second addition of 190 of silane-gluconamide is replaced by an addition of 340 of silane ([Hydroxy (polyethylenoxy) propyl] triethoxysilane) at 50% in ethanol, corresponding to a theoretical amount of 2 silanes per nm 2 of surface area.
- Preparation process 5c Colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating organic molecules containing an aromatic pyridine ring and particles containing europium complexes.
- the synthesis is similar to that described in preparation method 1 unlike the functionalization performed in the microemulsion.
- the second addition of 190 ⁇ of Silane-gluconamide is replaced by an addition of 185 ⁇ of Silane (N- (trimethoxysilylpropyl) ethylenediaminetriacetic acid) to 45% in water, corresponding to a theoretical amount of 2 silanes per nm of area.
- Preparation process 5d Colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating organic molecules containing an aromatic pyridine ring and particles containing europium complexes.
- the synthesis is similar to that described in preparation method 1 unlike the functionalization performed in the microemulsion.
- the second addition of 190 of silane-gluconamide is replaced by an addition of 60 of silane (3-thiocyanatopropyltriethoxysilane), which corresponds to a theoretical amount of 2 silanes per nm 2 of surface area.
- Preparation process 5e Colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating organic molecules containing an aromatic pyridine ring and particles containing europium complexes.
- the synthesis is similar to that described in preparation method 1 unlike the functionalization performed in the microemulsion.
- the second addition of 190 of silane-gluconamide is replaced by a 60 ⁇ addition of Silane (3-isocyanatopropyltriethoxysilane), which corresponds to a theoretical amount of 2 silanes per nm 2 of surface area.
- the solution obtained according to the preparation method 4 is post-functionalized with a silane (- (2-aminoethyl) -3-aminopropyltriethoxysilane).
- a silane - (2-aminoethyl) -3-aminopropyltriethoxysilane.
- 10 of the diluted silane solution (corresponding to a theoretical amount of 0.1 silane molecule per nm surface of particle) is added to 10 ml of the solution obtained according to the preparation method 4, the resulting solution is stirred at 40 ° C for 48 h.
- the solution obtained according to the preparation method 4 is post-functionalized with a silane (3- (triethoxysilyl) propylsuccinic anhydride).
- a silane (3- (triethoxysilyl) propylsuccinic anhydride).
- 20 ⁇ L of silane is diluted in 10 mL of DEC.
- diluted silane solution (corresponding to a theoretical amount of 0.1 molecule of silane per nm 2 of particle surface) is added to 10 ml of the solution obtained according to the preparation method 4, the resulting solution is stirred at 40 ° C. ° C for 48 hours.
- the solution obtained according to Example 4 is post-functionalized with a silane (O- (propargyloxy) -N- (triethoxysilylpropyl) urethane).
- a silane O- (propargyloxy) -N- (triethoxysilylpropyl) urethane
- 24 of silane is diluted in 10 mL of DEG.
- 10 diluted silane solution (corresponding to a theoretical amount of 0.1 silane molecule per nm of particle area) is added to 10 mL of the solution obtained in Example 4, the solution obtained is stirred at 40 ° C for 48 h.
- Preparation Process 7 Colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating aromatic ring-containing organic molecules derived from pyridine and europium (DTPA) complexes.
- APTES APTES
- TEOS tetraethylorthosilicate
- microemulsion is destabilized in a separatory funnel by adding a mixture of 250 ml of distilled water and 250 ml of isopropanol. The solution is left to settle for 15 minutes and the lower phase containing the particles is recovered.
- the colloidal solution recovered is then placed in a 300 kDa VIVASPIN® filtration system and then centrifuged at 4000 rpm until a purification rate greater than 500 is obtained.
- the solution obtained is then post-functionalized with 3.72 ⁇ l of silane (N- (triethoxysilylpropyl) -O-polyethyleneoxideurethane) (corresponding to a theoretical amount of 0.1 molecule of silane per nm 2 of particle surface) at 40 ° C. with stirring for 48 h.
- silane N- (triethoxysilylpropyl) -O-polyethyleneoxideurethane
- Example 1 50 nm 0.091
- Figures 1, 2 and 3 show the excitation and emission spectra with a delay of 0.1 ms for Examples 1 to 3 respectively. These data show that the nanoparticles have a good time resolved fluorescence property.
- nanoparticles were prepared according to the preparation methods 6a to 6c.
- the following table summarizes the average diameter, polydispersity and zeta potential of the nanoparticles before and after the heating step, the heating step of heating the nanoparticle solution after post-functionalization at 80 ° C for 1 hour and then to cool to room temperature.
- the material used consists of the core, two plugs of the same diameter specially machined to allow the screwing of fittings, transparent PVC tube, a PTFE pattern, Araldite glue and a commercial silicone seal tube.
- the epoxy resin is composed of 70% of a resin base (Epon 828 - Miller -Stephenson Chemical Company, Inc.) and 30% hardener (Versamid 125 - Miller-Stephenson Chemical Company, Inc.)
- a resin base Epon 828 - Miller -Stephenson Chemical Company, Inc.
- 30% hardener Versamid 125 - Miller-Stephenson Chemical Company, Inc.
- a synthetic sea water solution is composed of mineral water (containing 35 ppm of dissolved S1O 2) having dissolved therein the following salts:
- the assembly consists of a double syringe pump for setting a flow rate of between 1 and 1000 mL per hour, typically between 20 and 100 mL / h. This directs a fluid to a cartridge containing the porous rock. The fluid percolates through it, the differential pressure on both sides of the rock is followed by a sensor. The fluid is finally directed to a fraction collector.
- the fluid used is a diluted suspension of particles and Kl.
- the injected fluid is degassed seawater without tracers.
- the flow rate imposed by the pump is 60 mL / h.
- the fractions collected at the rock outlet are of a volume of 5 mL.
- Figure 4 shows a permeation curve of nanoparticles prepared according to Preparation Method 4 (including a heating step at 80 ° C for 1 hour) in comparison with control K1 (ideal tracer).
- the permeation results show that the nanoparticles according to the invention can easily be used as tracers in injection waters. Indeed, a very good correlation is observed between the fluorescent nanoparticulate tracers and the ideal tracer (Kl). In particular, a passage rate of nanoparticles greater than 99% is obtained with a mean deviation from the ideal tracer of less than 10%. To the knowledge of the inventors, such results have not been obtained with nanoparticles, having fluorophores detectable by fluorescence resolved in time, developed with the methods of the prior art.
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Abstract
The field of the present invention relates is that of the exploration for and exploitation of oil deposits. Specifically, the invention relates to the development of nanoparticles that can be used as tracers for tracking the movement of fluids injected into an oil deposit. The injected fluids are diffused through a solid geological medium that constitutes the oil deposit, making it possible to study the latter by tracking the path of the injected fluids. The aim is in particular to monitor the flows between the injection well(s) and the production well(s), and/or to evaluate the amount of reserve oil and water in the deposit, and finally to optimize oil exploration and exploitation.
Description
NANOTRACEURS POUR LE MARQUAGE D'EAUX D'INJECTION DE NANOTRACTERS FOR MARKING INJECTION WATER
CHAMPS PETROLIERS PETROLEUM FIELDS
Le domaine de cette invention est celui de l'exploration et de l'exploitation de gisements pétroliers. The field of this invention is that of the exploration and exploitation of oil deposits.
Plus précisément, cette invention concerne la mise au point de nanoparticules, utilisables comme traceurs, pour suivre le mouvement de fluides injectés dans un gisement pétrolier. More specifically, this invention relates to the development of nanoparticles, useful as tracers, for tracking the movement of fluids injected into a petroleum deposit.
Les fluides injectés diffusent à travers un milieu solide géologique qui constitue le gisement pétrolier, permettant ainsi d'étudier ce dernier en suivant le parcours des fluides injectés. L'objectif est notamment de contrôler les flux entre le(s) puits d'injection et le(s) puits de production et/ou d'évaluer les volumes de pétrole en réserve et d'eau dans le gisement et, in fine, d'optimiser l'exploration et l'exploitation pétrolière. The injected fluids diffuse through a solid geological medium which constitutes the oil reservoir, thus making it possible to study the latter by following the path of the injected fluids. The objective is in particular to control the flows between the injection well (s) and the production well (s) and / or to evaluate the volumes of oil in reserve and water in the deposit and, in the end, optimize oil exploration and development.
ARRIERE-PLAN TECHNOLOGIQUE BACKGROUND
Il est bien connu dans l'exploitation pétrolière d'un gisement, que le plus souvent, on n'extrait pas plus de la moitié, voire moins, du pétrole présent à l'origine dans le gisement. La récupération par les moyens primaires, c'est-à-dire l'utilisation de l'énergie d'extraction résultant de gaz ou de liquides présents dans le sous-sol sous l'effet d'une certaine pression dans le gisement permet seulement d'extraire de faibles pourcentages du pétrole total présent dans le gisement. Pour compléter cette récupération primaire, on procède à une récupération secondaire : elle consiste à mettre en œuvre ce que l'on dénomme une production par « water drive » ou « water flooding », c'est-à dire en injectant de l'eau dans un puits (puits d'injection) à un endroit du gisement, de manière à pousser le pétrole du gisement hors du sous-sol, par au moins un autre puits appelé « puits de production ». It is well known in the oil exploitation of a deposit, that more often, one does not extract more than half, or even less, of oil originally present in the deposit. Recovery by primary means, that is to say the use of the extraction energy resulting from gases or liquids present in the subsoil under the effect of a certain pressure in the deposit only allows to extract small percentages of the total oil present in the deposit. To complete this primary recovery, there is a secondary recovery: it consists in implementing what is called a production by "water drive" or "water flooding", that is to say by injecting water in a well (injection well) at one location in the deposit, so as to push the oil from the deposit out of the subsoil, through at least one other well called a "production well".
Pour connaître le comportement de l'eau d'injection, il est connu d'y ajouter des traceurs aisément détectables dans le liquide. Ces traceurs permettent de suivre l'eau d'injection. La mesure de la quantité de traceur au niveau des puits de production permet de connaître le volume et la répartition du fluide d'injection dans la formation. En outre, l'interaction traceur/huile peut permettre de déterminer la proportion des liquides du réservoir que constitue le gisement pétrolier. C'est l'un des paramètres les plus importants qui peut être déterminé par l'utilisation de tels fluides de traçage,
puisque ce paramètre permet, d'une part, d'ajuster le programme d'injection d'eau, et d'autre part, d'évaluer la quantité de pétrole restant à produire. Dès lors que le fluide contenant le traceur a été détecté au(x) puits de production, le procédé d'étude permettant l'analyse, le contrôle et la récupération optimisée de pétrole, nécessite que la concentration en traceur dans le fluide produit en sortie soit mesurée continuellement ou non, de manière à pouvoir tracer des courbes de concentration en traceurs en fonction du temps ou en fonction du volume de fluide produit. To know the behavior of the injection water, it is known to add tracers easily detectable in the liquid. These tracers make it possible to follow the injection water. The measurement of the amount of tracer at the production wells makes it possible to know the volume and the distribution of the injection fluid in the formation. In addition, the tracer / oil interaction can be used to determine the proportion of liquids in the reservoir that is the oil field. This is one of the most important parameters that can be determined by the use of such tracing fluids, since this parameter makes it possible, on the one hand, to adjust the water injection program, and on the other hand, to evaluate the quantity of oil remaining to be produced. Since the fluid containing the tracer has been detected at the production well (s), the study method allowing the analysis, the control and the optimized recovery of oil, requires that the tracer concentration in the fluid produces an output. is measured continuously or not, so as to be able to plot tracer concentration curves as a function of time or as a function of the volume of fluid produced.
Les traceurs dans les eaux d'injection pour gisements pétroliers permettent également de détecter des aberrations dans les débits provoqués par des différentiels de pression dans le gisement, qui sont provoqués par des facteurs autres que l'injection d'eau et qui dégradent les performances. Tracers in oilfield injection waters also detect aberrations in flow rates caused by pressure differentials in the deposit, which are caused by factors other than water injection and degrade performance.
Le cahier des charges des traceurs utilisables dans ces eaux d'injection pour l'optimisation de la récupération de pétrole comprend les spécifications suivantes : The specifications of the tracers that can be used in these injection waters for the optimization of oil recovery include the following specifications:
- économique ; - economic ;
- compatible avec les fluides naturellement présents dans le gisement, et avec la roche pétrolifère en elle-même ainsi qu'avec les fluides injectés dans le gisement, à savoir les liquides (eaux) d'injection; - compatible with the fluids naturally present in the deposit, and with the oil rock itself as well as with the fluids injected into the deposit, namely the liquids (water) injection;
- détection qualitative et quantitative aisée du traceur quels que soient les matériaux présents dans le fluide en sortie du puits de production. Par exemple, une solution aqueuse de chlorure de sodium ne peut être utilisée comme traceur, en raison du fait que la plupart des champs pétrolifères contiennent de l'eau de mer et donc du chlorure de sodium en quantité substantielle, de sorte que la détection de chlorure de NaCl utilisé comme traceur serait particulièrement difficile ; - Easy qualitative and quantitative tracer detection regardless of the materials present in the fluid output of the production well. For example, an aqueous solution of sodium chloride can not be used as a tracer, because most of the oilfields contain seawater and therefore sodium chloride in a substantial amount, so that the detection of NaCl chloride used as a tracer would be particularly difficult;
- traceur furtif, c'est-à-dire non aisément absorbable dans le milieu solide traversé ou éliminable du fluide de traçage, puisque dans la technique analytique utilisée, on détermine la concentration en traceur dans les fluides produits en sortie et on la compare avec celle des fluides injectés dans le(s) puits d'injection ; stealth tracer, that is to say not easily absorbable in the solid medium passed through or removed from the tracer fluid, since in the analytical technique used, the tracer concentration in the output fluids is determined and compared with that of the fluids injected into the injection well (s);
- résistance du traceur à la contamination bactérienne, aux hautes températures et hautes pressions existant dans les gisements pétroliers ; - tracer resistance to bacterial contamination, high temperatures and high pressures existing in oil fields;
- offrir la possibilité au traceur d'interagir ou non avec l'environnement du gisement, à savoir les milieux géologiques pétrolifères ou non ; - offer the tracer the possibility of interacting with or not interacting with the deposit's environment, namely oil-bearing geological environments or not;
- accès à un grand nombre de traceurs et codages différents pour des détections simultanées possibles (plusieurs puits d'injections) ou des essais de traçages successifs dans le temps.
Concernant l'état de la technique propre à de tels traceurs pour des eaux d'injection (fluide de traçage) permettant de sonder des gisements pétroliers par diffusion entre un puits d'injection et un puits de production, on peut citer les brevets US 4,231,426- Bl et 4,299,709-Bl qui divulguent des fluides traceurs aqueux comprenant de 0,01 à 10 % en poids d'un sel de nitrate associé à un agent bactéricide choisi parmi les composés aromatiques (benzène, toluène, xylène). access to a large number of different tracers and codings for possible simultaneous detections (several injection wells) or successive tracing tests over time. Regarding the state of the art specific to such tracers for injection water (tracer fluid) for probing oil deposits by diffusion between an injection well and a production well, mention may be made of US Patents 4,231,426 - B1 and 4,299,709-B1 which disclose aqueous tracer fluids comprising from 0.01 to 10% by weight of a nitrate salt associated with a bactericidal agent selected from aromatic compounds (benzene, toluene, xylene).
La demande de brevet canadien CA 2 674 127-Al est relative à un procédé consistant à utiliser un isotope naturel du carbone 13 pour l'identification de percée précoce des eaux d'injection dans des puits de pétrole. Canadian patent application CA 2,674,127-Al relates to a method of using a natural carbon 13 isotope for the identification of early breakthrough of injection water in oil wells.
Par ailleurs, il existe une dizaine de familles de molécules adaptées et validées actuellement comme traceur pour eaux d'injection dans des gisements pétroliers. Ces familles de molécules sont par exemple les acides benzoïques fluorés ou les acides naphtalènes sulfoniques. In addition, there are about ten families of molecules adapted and currently validated as a tracer for injection water in oilfields. These families of molecules are, for example, fluorinated benzoic acids or naphthalenesulphonic acids.
Les molécules traceurs connues et utilisées ont une signature chimique/radioactive spécifique. Ces traceurs connus peuvent se détecter avec une grande sensibilité mais présentent néanmoins trois inconvénients majeurs : The tracer molecules known and used have a specific chemical / radioactive signature. These known tracers can be detected with great sensitivity but nevertheless have three major disadvantages:
- leur quantification réclame un processus assez complexe et cher, et ne peut se faire que dans un centre spécialisé, souvent éloigné des sites de production ; - their quantification requires a rather complex and expensive process, and can only be done in a specialized center, often far from the production sites;
- ces molécules peu nombreuses ne permettent pas d'effectuer un multi- marquage ou des marquages répétés ; these few molecules do not make it possible to carry out multi-marking or repeated markings;
- certains de ces marqueurs connus sont voués à disparaître en raison de leur impact négatif sur l'environnement. - some of these known markers are doomed to disappear because of their negative impact on the environment.
En outre, le site de "Institute for Energy Technology" (IFE) a mis en ligne une présentation power point intitulée SIP 2007 - 2009 « New functional tracers based on nanotechnology and radiotracer generators Department for Réservoir and Exploration Technology » (dernière modification en date du 7 Mars 2011). En particulier, ce document suggère l'utilisation de nanoparticules modifiées en surface, à titre de traceur pour le contrôle des flux dans des gisements pétroliers et des puits de pétrole et dans des études de procédés. Cette présentation décrit des nanoparticules traceurs fonctionnalisées comprenant un cœur à base Gd203 et un revêtement de surface à base de siloxane fonctionnalisé avec des molécules additionnelles. Il est
également suggéré que le cœur en terre rare et/ou les molécules additionnelles peuvent émettre des signaux lumineux par fluorescence ou des signaux radioactifs. In addition, the Institute for Energy Technology (IFE) website has put online a power point presentation entitled SIP 2007 - 2009 "New functional tracers based on nanotechnology and radiotracer generators Department for Reservoir and Exploration Technology" (last modification of March 7, 2011). In particular, this paper suggests the use of surface-modified nanoparticles as a tracer for flow control in oilfields and oil wells and in process studies. This disclosure describes functionalized tracer nanoparticles comprising a Gd 2 0 3 core and a siloxane-based surface coating functionalized with additional molecules. It is also suggested that the rare earth core and / or additional molecules may emit fluorescent light signals or radioactive signals.
Dans un tout autre domaine, la demande de brevet français FR2867180-A1 décrit des nanoparticules hybrides comprenant, d'une part, un cœur constitué d'un oxyde de terre rare, éventuellement dopé avec une terre rare ou un actinide ou un mélange de terres rares ou bien un mélange de terres rares et d'actinide et, d'autre part, un enrobage autour de ce cœur, ledit enrobage étant constitué majoritairement de polysiloxane fonctionnalisé par au moins un ligand biologique greffé par liaison covalente. Le cœur peut être à base Gd203 dopé par du Tb + ou par de l'uranium et l'enrobage de polysiloxane peut être obtenu en faisant réagir un aminopropyltriéthoxysilane, un tétraéthylsilicate et de la triéthylamine. Ces nanoparticules sont utilisées en tant que sondes pour la détection, le suivi, et la quantification de systèmes biologiques. In a completely different field, the French patent application FR2867180-A1 describes hybrid nanoparticles comprising, on the one hand, a core consisting of a rare earth oxide, possibly doped with a rare earth or an actinide or a mixture of grounds. rare or a mixture of rare earths and actinide and, secondly, a coating around this core, said coating consisting mainly of polysiloxane functionalized with at least one biological ligand grafted by covalent bonding. The core may be Tb + doped Gd 2 O 3 base or uranium and the polysiloxane coating may be obtained by reacting an aminopropyltriethoxysilane, a tetraethylsilicate and triethylamine. These nanoparticles are used as probes for the detection, monitoring, and quantification of biological systems.
La demande de brevet français FR2922106-A1 relève du même domaine technique et vise l'utilisation de ces nanoparticules comme agents radio sensibilisants pour augmenter l'efficacité de radiothérapie. Ces nanoparticules ont une taille comprise entre 10 et 50 nanomètres. The French patent application FR2922106-A1 relates to the same technical field and aims to use these nanoparticles as sensitizing radio agents to increase the effectiveness of radiotherapy. These nanoparticles have a size of between 10 and 50 nanometers.
PROBLEME TECHNIQUE ET OBJECTIFS A ATTEINDRE TECHNICAL PROBLEM AND OBJECTIVES TO BE REACHED
Dans ce contexte, la présente invention vise à satisfaire au moins l'un des objectifs suivants : In this context, the present invention aims to satisfy at least one of the following objectives:
- proposer un nouveau procédé d'étude d'un milieu solide, par exemple un gisement pétrolier, par diffusion d'un liquide au travers dudit milieu solide, qui soit simple à mettre en œuvre et économique ; proposing a new process for studying a solid medium, for example a petroleum deposit, by diffusion of a liquid through said solid medium, which is simple to implement and economical;
- remédier aux inconvénients des traceurs pour eaux d'injection de gisements pétroliers selon l'art antérieur ; to overcome the drawbacks of tracers for injection water from petroleum deposits according to the prior art;
- fournir un traceur qui suit parfaitement les eaux d'injection dans leur diffusion (percolation), au travers des milieux solides que constituent les gisements pétroliers, sans présenter d'interaction avec le sous-sol géologique traversé (ni attraction, ni répulsion) ; - to provide a tracer which perfectly follows the injection waters in their diffusion (percolation), through the solid media that constitute the oil deposits, without presenting any interaction with the geological subsoil crossed (neither attraction nor repulsion);
- fournir un traceur pour eaux d'injection de gisements pétroliers dont les interactions (attraction - répulsion) vis-à-vis du milieu géologique au travers duquel il percole, sont contrôlables à dessein ; - provide a tracer for injection water from oil deposits whose interactions (attraction - repulsion) vis-à-vis the geological medium through which it percolates, are controllable by design;
- fournir un nouveau traceur furtif pour eaux d'injection de gisements pétroliers ;
- fournir un nouveau traceur pour eaux d'injection de gisements pétroliers possédant une sensibilité et/ou facilité de détection substantiellement améliorée par rapport aux traceurs connus jusqu'à ce jour ; - provide a new stealth tracer for oilfield injection water; - provide a new tracer for oilfield injection waters with sensitivity and / or ease of detection substantially improved over tracers known to date;
- fournir un nouveau traceur pour eaux d'injection de gisements pétroliers possédant plusieurs signaux aisément détectables pour réaliser une multi détection et multiplier les analyses au cours du temps ou de l'espace ; - provide a new tracer for oilfield injection waters with several easily detectable signals to perform multi detection and multiply analyzes over time or space;
- fournir un nouveau traceur pour eaux d'injection de gisements pétroliers et co-compatible ; - provide a new tracer for oilfield injection water and co-compatible;
- fournir un nouveau traceur pour eaux d'injection de gisements pétroliers stable sur le plan physique, chimique et biologique dans les milieux solides géologiques que constituent les gisements pétroliers ; - provide a new tracer for oilfield injection waters that is physically, chemically and biologically stable in the geological solid environments of oil reservoirs;
- fournir un nouveau liquide, en particulier de nouvelles eaux d'injection, pour gisements pétroliers utilisables notamment dans un procédé d'étude d'un milieu solide par exemple un gisement pétrolier par diffusion dudit liquide au travers dudit milieu solide ; providing a new liquid, in particular new injection water, for petroleum deposits that can be used in particular in a process for studying a solid medium, for example a petroleum deposit, by diffusion of said liquid through said solid medium;
- fournir un nouveau procédé de synthèse de tels traceurs qui soit simple et économique à mettre en œuvre. - Provide a new method of synthesis of such tracers that is simple and economical to implement.
BREVE DESCRIPTION DE L'INVENTION BRIEF DESCRIPTION OF THE INVENTION
Ces objectifs, parmi d'autres, sont atteints par l'invention qui concerne en premier lieu des nanoparticules pour leur utilisation dans l'étude d'un gisement pétrolier, lesdites nanoparticules étant caractérisées en ce qu'elles comprennent : These objectives, among others, are achieved by the invention, which primarily concerns nanoparticles for use in the study of a petroleum deposit, said nanoparticles being characterized in that they comprise:
- un cœur constitué d'un métal noble ou d'un alliage de métaux nobles, une matrice comprenant (i) des polysiloxanes et (ii) un fluorophore organométallique lié de manière covalente aux polysiloxanes, ladite matrice étant fonctionnalisée à sa surface pour former des liaisons silanes Si-R, lesdits radicaux -R étant constitués pour au moins 50%, de préférence au moins 75%, de composés hydrophiles neutres ou chargés, de préférence parmi des polyéthers ou des polyols, ou leurs mélanges. a core consisting of a noble metal or an alloy of noble metals, a matrix comprising (i) polysiloxanes and (ii) an organometallic fluorophore covalently bonded to the polysiloxanes, said matrix being functionalized on its surface to form Silane bonds Si-R, said radicals -R being constituted for at least 50%, preferably at least 75%, of neutral or charged hydrophilic compounds, preferably from polyethers or polyols, or mixtures thereof.
L'invention concerne en second lieu un procédé de préparation d'une solution colloïdale de nanoparticules utilisable pour l'étude d'un gisement pétrolier, ledit procédé comprenant les étapes suivantes : The invention relates secondly to a method for preparing a colloidal solution of nanoparticles that can be used for the study of a petroleum deposit, said method comprising the following steps:
i. on synthétise un cœur de métal noble enrobé d'une matrice de polysiloxane préfonctionnalisée avec des silanes hydrophiles, au sein d'une microémulsion inverse,
ii. on extrait une solution colloïdale aqueuse de nanoparticules par décantation après déstabilisation de la microémulsion, par exemple dans un mélange eau/alcool, i. a noble metal core coated with a polysiloxane matrix prefunctionalized with hydrophilic silanes is synthesized in an inverse microemulsion, ii. an aqueous colloidal solution of nanoparticles is extracted by decantation after destabilization of the microemulsion, for example in a water / alcohol mixture,
iii. on chauffe les nanoparticules à au moins 50°C, par exemple, environ 80°C. iii. the nanoparticles are heated to at least 50 ° C, for example about 80 ° C.
En troisième lieu, l'invention concerne un liquide d'injection pour l'étude d'un gisement pétrolier, comprenant des nanoparticules telles que définies ci-dessus, ou une solution colloïdale de nanoparticules susceptible d'être obtenue par le procédé tel que défini ci-dessus. Third, the invention relates to an injection liquid for the study of a petroleum deposit, comprising nanoparticles as defined above, or a colloidal solution of nanoparticles that can be obtained by the process as defined above.
L'invention porte également sur l'utilisation de ces nanoparticules comme traceurs dans des eaux d'injection d'un gisement pétrolier, lesquels sont destinés à l'étude dudit gisement par diffusion au travers de celui-ci, en vue notamment de contrôler les flux entre un puits d'injection et un puits de production et/ou d'évaluer les volumes de pétrole en réserve dans le gisement. The invention also relates to the use of these nanoparticles as tracers in injection waters of a petroleum deposit, which are intended for the study of said deposit by diffusion through it, with a view in particular to controlling the flow between an injection well and a production well and / or to evaluate the volumes of oil in reserve in the deposit.
DESCRIPTION DETAILLEE DE L'INVENTION DETAILED DESCRIPTION OF THE INVENTION
Les nanoparticules Nanoparticles
Les nanoparticules selon l'invention sont destinées à leur utilisation comme traceurs dans l'étude d'un gisement pétrolier, lesdites nanoparticules étant caractérisées en ce qu'elles comprennent : The nanoparticles according to the invention are intended for use as tracers in the study of a petroleum deposit, said nanoparticles being characterized in that they comprise:
- un cœur constitué essentiellement d'un métal noble ou d'un alliage de métaux nobles, a core consisting essentially of a noble metal or an alloy of noble metals,
une matrice comprenant (i) des polysiloxanes et (ii) un fluorophore organométallique lié de manière covalente aux polysiloxanes, ladite matrice étant fonctionnalisée à sa surface pour former des liaisons silanes Si-R, lesdits radicaux -R étant constitués pour au moins 50%, de préférence au moins 75%, de composés hydrophiles neutres ou chargés, de préférence parmi des polyéthers ou des polyols, ou leurs mélanges. a matrix comprising (i) polysiloxanes and (ii) an organometallic fluorophore covalently bound to the polysiloxanes, said matrix being functionalized on its surface to form silane bonds Si-R, said radicals -R constituting for at least 50%, preferably at least 75% of neutral or charged hydrophilic compounds, preferably from polyethers or polyols, or mixtures thereof.
Les nanoparticules selon l'invention sont détectables, c'est-à-dire que l'on peut identifier leur présence ou non dans le milieu au-delà d'une certaine concentration et que l'on peut même quantifier leur concentration dès lors qu'elles sont présentes dans le milieu.
Ces nanoparticules sont aptes à former une suspension colloïdale stable en milieu salin, qui sédimente peu. Par exemple, cette suspension ne présente pas de précipitation ou d'agglomération avec le temps, e.g. après 6 mois à température ambiante. The nanoparticles according to the invention are detectable, that is to say that one can identify their presence or not in the medium beyond a certain concentration and that one can even quantify their concentration when they are present in the environment. These nanoparticles are capable of forming a stable colloidal suspension in a saline medium, which sediments little. For example, this suspension shows no precipitation or agglomeration with time, eg after 6 months at room temperature.
Le cœur des nanoparticules permet de structurer la nanoparticule. Selon la présente invention, le cœur est constitué essentiellement d'un métal noble, par exemple l'or, l'argent ou le platine, et/ou un alliage de métaux nobles. Dans un mode de réalisation préféré, le cœur est essentiellement constitué de particules d'or. The heart of the nanoparticles makes it possible to structure the nanoparticle. According to the present invention, the core consists essentially of a noble metal, for example gold, silver or platinum, and / or an alloy of noble metals. In a preferred embodiment, the core consists essentially of gold particles.
En effet, il a été constaté, de manière surprenante, que les nanoparticules obtenues selon l'invention sont plus denses et de structure plus régulière que celles réalisées avec d'autres matériaux pour le choix du cœur. En outre, l'or présente dans certains cas un effet d'antenne qui permet alors avantageusement d'amplifier le signal fluorescent émis par le fluorophore organométallique de la matrice lors de la détection. Indeed, it has been found, surprisingly, that the nanoparticles obtained according to the invention are denser and of a more regular structure than those made with other materials for the choice of the heart. In addition, the gold has in certain cases an antenna effect which then advantageously makes it possible to amplify the fluorescent signal emitted by the organometallic fluorophore of the matrix during the detection.
L'or, avec d'autres métaux nobles comme l'Ag, Pd, Pt, Ir, ou Rh, est également détectable par la méthode de détection ICP (ou spectrométrie par torche à plasma) et peut être utilisé comme référence interne pour la détection des nanoparticules et de leur éventuelle dégradation. Gold, along with other noble metals such as Ag, Pd, Pt, Ir, or Rh, is also detectable by the ICP (or plasma torch spectrometry) detection method and can be used as an internal reference for detection of nanoparticles and their possible degradation.
Enfin, l'or présente l'avantage d'être aussi détectable par absorption plasmon permettant la détection et la quantification des nanoparticules à des concentrations très faibles, par exemple, au niveau de la particule unique, en particulier après une dispersion d'un volume donnée sur un support. On peut détecter une particule dans 10 au moins, préférentiellement 100 μL·. Finally, gold has the advantage of being also detectable by plasmon absorption allowing the detection and quantification of nanoparticles at very low concentrations, for example, at the level of the single particle, in particular after a dispersion of a volume. given on a support. A particle can be detected in at least 10, preferably 100 μL ·.
Les particules d'or formant le cœur des nanoparticules ont une taille d'au moins 3 nm, de préférence comprise entre 5 nm et 15 nm. The gold particles forming the core of the nanoparticles have a size of at least 3 nm, preferably between 5 nm and 15 nm.
La matrice forme une couche enrobant le cœur de métaux nobles de la nanoparticule. Elle permet d'encapsuler les molécules détectables pour la détection et/ou la quantification des nanoparticules. The matrix forms a core coating layer of noble metals of the nanoparticle. It makes it possible to encapsulate the detectable molecules for the detection and / or quantification of the nanoparticles.
La matrice des nanoparticules selon l'invention comprend des polysiloxanes et au moins un fluorophore organométallique lié de manière covalente aux polysiloxanes. Dans un mode de réalisation spécifique, elle est constituée essentiellement de
polysiloxanes, fonctionnalisés sur la surface extérieure des nanoparticules et encapsulant des fluorophores organométalliques. The matrix of the nanoparticles according to the invention comprises polysiloxanes and at least one organometallic fluorophore covalently bonded to the polysiloxanes. In a specific embodiment, it consists essentially of polysiloxanes, functionalized on the outer surface of the nanoparticles and encapsulating organometallic fluorophores.
L'ensemble matrice et cœur forment des nanoparticules d'un diamètre moyen de préférence compris entre 20 nm et 100 nm, par exemple, compris entre 20 nm et 50 nm. Dans un mode de réalisation avantageux, les nanoparticules selon l'invention ont un indice de polydispersité inférieur à 0,5, de préférence inférieur à 0,3, ou inférieur à 0,2, par exemple inférieur à 0,1. The matrix and core assembly form nanoparticles with an average diameter of preferably between 20 nm and 100 nm, for example between 20 nm and 50 nm. In an advantageous embodiment, the nanoparticles according to the invention have a polydispersity index of less than 0.5, preferably less than 0.3, or less than 0.2, for example less than 0.1.
La distribution de taille des nanoparticules est par exemple mesurée à l'aide d'un granulomètre commercial, tel qu'un granulomètre Malvern Zêta sizer Nano-S basé sur la PCS (Photon Corrélation Spectroscopy). Cette distribution est caractérisée par un diamètre moyen et un indice de polydispersité. The size distribution of the nanoparticles is for example measured using a commercial particle size analyzer, such as a Malvern Zeta sizer Nano-S granulometer based on the PCS (Photon Correlation Spectroscopy). This distribution is characterized by a mean diameter and a polydispersity index.
Au sens de l'invention, par « diamètre moyen » on entend la moyenne harmonique des diamètres des particules. L'indice de polydispersité fait référence à la largeur de la distribution en taille dérivant de l'analyse des cumulants. Ces deux caractéristiques sont décrites dans la norme ISO 13321 : 1996. For the purposes of the invention, "mean diameter" means the harmonic mean of the diameters of the particles. The polydispersity index refers to the width of the size distribution derived from the cumulant analysis. Both of these features are described in ISO 13321: 1996.
La matrice peut comprendre le cas échéant, d'autres matériaux, choisis dans le groupe constitué par les silices, les alumines, les zircones, les aluminates, les aluminophosphates, les oxydes métalliques, ou encore les métaux (exemple : Fe, Cu, Ni, Co...) passivés en surface par une couche du métal oxydé ou d'un autre oxyde et leurs mélanges et alliages. The matrix may comprise, if appropriate, other materials chosen from the group consisting of silicas, aluminas, zirconiums, aluminates, aluminophosphates, metal oxides, or metals (example: Fe, Cu, Ni , Co ...) passivated at the surface by a layer of the oxidized metal or other oxide and their mixtures and alloys.
Une fonction essentielle de la matrice est de maintenir les fluorophores organométalliques dans les nanoparticules et en particulier des les protéger des agressions de l'environnement extérieur. An essential function of the matrix is to maintain the organometallic fluorophores in the nanoparticles and in particular to protect them from attacks from the external environment.
Les fluorophores organométalliques permettent de produire un ou plusieurs signaux détectables par nanoparticule. Les fluorophores organométalliques utilisés dans les nanoparticules selon l'invention sont de préférence choisis de manière à produire un signal fluorescent stable dans le temps et qui soit peu influencé par les conditions physico-chimiques de l'environnement traversé (par exemple températures, pH, compositions ioniques, solvants, conditions redox ...). Organometallic fluorophores produce one or more detectable signals by nanoparticle. The organometallic fluorophores used in the nanoparticles according to the invention are preferably chosen so as to produce a fluorescent signal which is stable over time and which is not very influenced by the physico-chemical conditions of the environment traversed (for example temperatures, pH, compositions ionic, solvents, redox conditions ...).
De préférence, les fluorophores organométalliques contenus dans la matrice des nanoparticules sont choisis parmi les vanadates ou les oxydes de terres rares, ou leurs
mélanges. Dans un mode de réalisation spécifique, ils sont choisis parmi les lanthanides, leurs alliages et leurs mélanges, liés à des molécules complexantes. Preferably, the organometallic fluorophores contained in the matrix of the nanoparticles are chosen from vanadates or oxides of rare earths, or their mixtures. In a specific embodiment, they are chosen from lanthanides, their alloys and their mixtures, linked to complexing molecules.
Dans un mode de réalisation préféré, les fluorophores organométalliques sont détectables par fluorescence résolue dans le temps. Les lanthanides liés à des molécules complexantes sont alors particulièrement préférés. In a preferred embodiment, the organometallic fluorophores are detectable by time-resolved fluorescence. Lanthanides linked to complexing molecules are then particularly preferred.
Les métaux de la série des lanthanides comprennent les éléments de numéros atomiques de 57 (lanthane) à 71 (lutécium). Par exemple, on choisira les lanthanides dans le groupe constitué par : Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm et Yb et leurs mélanges et/ou alliages, liés à des molécules complexantes. The metals of the lanthanide series include atomic number elements from 57 (lanthanum) to 71 (lutetium). For example, the lanthanides in the group consisting of: Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm and Yb and their mixtures and / or alloys, linked to complexing molecules, will be chosen.
Par « molécules complexantes » ou « agent chélatant », on entend toute molécule capable de former avec un agent métallique, un complexe comprenant au moins deux liaisons de coordination. By "complexing molecules" or "chelating agent" is meant any molecule capable of forming with a metal agent, a complex comprising at least two coordination bonds.
Dans un mode de réalisation préféré, on choisira un agent complexant ayant une coordinance d'au moins 6, par exemple au moins 8, et une constante de dissociation du complexe, pKd, supérieure à 10 et de préférence supérieur à 15, avec un lanthanide. In a preferred embodiment, a complexing agent having a coordination of at least 6, for example at least 8, and a dissociation constant of the complex, pKd, greater than 10 and preferably greater than 15, with a lanthanide, will be chosen. .
Au sens de l'invention, par constante de dissociation pKd, on entend la mesure de l'équilibre entre les ions à l'état complexé par les ligands et ceux libres dissociés dans le solvant. Précisément, c'est moins le logarithme en base 10 du produit de dissociation (-log(Kd)), défini comme la constante d'équilibre de la réaction qui traduit le passage de l'état complexé à l'état ionique. For the purposes of the invention, dissociation constant pKd is understood to mean the measurement of the equilibrium between the ions in the complexed state by the ligands and those free dissociated in the solvent. Precisely, it is less the logarithm in the base of the dissociation product (-log (Kd)), defined as the equilibrium constant of the reaction which translates the transition from the complexed state to the ionic state.
De tels agents complexants sont de préférence des molécules chélatantes polydentates choisies parmi les familles de molécules de type polyamines, polyacides carboxyliques et possédant un nombre de sites potentiels de coordination élevé de préférence supérieur à 6, comme certains macrocycles. Such complexing agents are preferably polydentate chelating molecules selected from families of polyamine-type polycarboxylic acid molecules and having a number of potential high coordination sites, preferably greater than 6, such as certain macrocycles.
Dans un mode de réalisation plus préféré, on choisira le DOTA, ou acide 1,4,7,10- tétraazacyclododécane-l,4,7,10-tétraacétique, de formule suivante :
ou l'un de ses dérivés. In a more preferred embodiment, DOTA or 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid, of the following formula, will be chosen: or one of its derivatives.
La matrice peut également contenir, outre l'agent complexant, un agent cyclique, par exemple greffé aux polysiloxanes. The matrix may also contain, besides the complexing agent, a cyclic agent, for example grafted to the polysiloxanes.
Par « agent cyclique », on entend une molécule organique, comportant au moins un cycle ou hétérocycle aromatique, de préférence choisi parmi le benzène, la pyridine ou leurs dérivés, et susceptibles d'amplifier le signal fluorescent émis par le fluorophore organométallique, par exemple un agent complexant lié au lanthanide. Ces agents cycliques, intéressants s'ils sont caractérisés par une forte absorbance, sont utilisés en particulier pour amplifier le signal fluorescent émis par les fluorophores organométalliques (effet d'antenne par transfert de l'excitation de l'agent vers le fluorophore). By "cyclic agent" is meant an organic molecule, comprising at least one aromatic ring or heterocycle, preferably selected from benzene, pyridine or their derivatives, and capable of amplifying the fluorescent signal emitted by the organometallic fluorophore, for example a complexing agent linked to the lanthanide. These cyclic agents, interesting if they are characterized by a high absorbance, are used in particular to amplify the fluorescent signal emitted by the organometallic fluorophores (antenna effect by transfer of the excitation of the agent towards the fluorophore).
L'agent cyclique peut être greffé de manière covalente soit directement aux polysiloxanes de la matrice, soit au fluorophore organométallique. The cyclic agent may be grafted covalently either directly to the polysiloxanes of the matrix or to the organometallic fluorophore.
Dans un mode de réalisation spécifique, les fluorophores organométalliques constitués d'un lanthanide avec un agent complexant sont greffés aux polysiloxanes de manière covalente via une fonction amide. In a specific embodiment, the organometallic fluorophores consisting of a lanthanide with a complexing agent are grafted to the polysiloxanes covalently via an amide function.
La matrice des nanoparticules selon l'invention est fonctionnalisée à sa surface. La fonctionnalisation de la matrice comprend la formation de liaisons silanes Si- , lesdits radicaux -R étant constitués pour au moins 50%, de préférence au moins 75% de composés hydrophiles neutres ou chargés, de préférence parmi des polyéthers ou des polyols, ou leurs mélanges. The matrix of the nanoparticles according to the invention is functionalized on its surface. The functionalization of the matrix comprises the formation of silane bonds Si-, said radicals -R being constituted by at least 50%, preferably at least 75% of neutral or charged hydrophilic compounds, preferably from polyethers or polyols, or their mixtures.
Dans un mode de réalisation préféré, la fonctionnalisation des nanoparticules est réalisée de sorte à ce que le potentiel zêta des nanoparticules mesuré à un pH à 6,5 soit inférieur à +10 mV.
Au sens de l'invention, le terme « potentiel zêta » fait référence au potentiel électrocinétique dans les systèmes colloïdaux. C'est le potentiel électrique de la double couche de surface ou encore la différence de potentiel entre le solvant et la couche de liquide attachée à la particule. Le potentiel zêta peut être mesuré avec le même appareil que celui utilisé pour mesurer la distribution de taille comme décrit dans l'article « zêta potential of colloïds in Water », ASTM Standard D 4187-82, American Society for Testing and Materials, 1985. In a preferred embodiment, the functionalization of the nanoparticles is carried out so that the zeta potential of the nanoparticles measured at a pH of 6.5 is less than +10 mV. For the purposes of the invention, the term "zeta potential" refers to the electrokinetic potential in colloidal systems. This is the electrical potential of the double surface layer or the potential difference between the solvent and the liquid layer attached to the particle. The zeta potential can be measured with the same apparatus as that used to measure the size distribution as described in the article "Zeta potential of colloids in Water", ASTM Standard D 4187-82, American Society for Testing and Materials, 1985.
La fonctionnalisation a pour objectif, en particulier, d'obtenir une bonne stabilité colloïdale en milieu salin, par exemple une concentration de sel critique d'au moins 50 g/L, voire d'au moins 100 g/L. Elle a également pour fonction de moduler les interactions eau-roche de la nanoparticule (minimiser son adsorption sur la roche par exemple), voire de moduler (par exemple minimiser) les interactions eau-huile. The functionalization aims in particular to obtain good colloidal stability in a saline medium, for example a critical salt concentration of at least 50 g / l, or even at least 100 g / l. Its function is also to modulate the water-rock interactions of the nanoparticle (to minimize its adsorption on the rock for example), or even to modulate (for example minimize) the water-oil interactions.
De telles interactions peuvent être mesurées lors d'une expérience de perméation sur carotte telle que décrite dans les exemples ci-dessous. Selon un mode de réalisation préféré, les nanoparticules selon l'invention présentent une adsorption minimale avec ce type de test. Such interactions can be measured in a carrot permeation experiment as described in the examples below. According to a preferred embodiment, the nanoparticles according to the invention exhibit minimal adsorption with this type of test.
Les radicaux -R greffés par covalence à base de liaisons silanes Si-R peuvent comprendre: The covalently grafted radicals R based on Si-R silane bonds can comprise:
i. des groupements hydrophiles chargés, de préférence des composés organiques hydrophiles, de masses molaires inférieures à 5 000 g/mol et, mieux encore inférieures à 450 g/mol, de préférence choisis parmi les groupements organiques comportant au moins l'une des fonctions suivantes: alcool, acide carboxylique, aminé, amide, ester, éther-oxyde, sulfonate, phosphonate et phosphinate, et une combinaison de ces fonctions, i. charged hydrophilic groups, preferably hydrophilic organic compounds, with molar masses of less than 5000 g / mol and more preferably less than 450 g / mol, preferably chosen from organic groups comprising at least one of the following functions: alcohol, carboxylic acid, amine, amide, ester, ether-oxide, sulfonate, phosphonate and phosphinate, and a combination of these functions,
ii. des groupements hydrophiles neutres, de préférence choisis parmi les dérivés sulfonates, les alcools, par exemple les sucres ou les polyols, de façon plus préférée, un polyalkylèneglycol ou un polyol, plus préférentiellement encore un polyéthylèneglycol, acide Diéthylène- TriaminePentaAcétique (DTP A), DTP A dithiolé (DTDTPA), un gluconamide ou un acide succinique, et les mélanges de ces groupements hydrophiles neutres, ii. neutral hydrophilic groups, preferably chosen from sulphonate derivatives, alcohols, for example sugars or polyols, more preferably a polyalkylene glycol or a polyol, more preferably still a polyethylene glycol, diethylenetriamine pentaacetic acid (DTP A), DTP A dithiolated (DTDTPA), a gluconamide or a succinic acid, and mixtures of these neutral hydrophilic groups,
iii. le cas échéant des groupements hydrophobes, par exemple choisis parmi des molécules contenant des chaînes alkyles ou fluorées.
Selon un mode de réalisation de l'invention, les radicaux -R des silanes Si-R en surface sont constitués pour au moins 50%, de préférence au moins 75%, de radicaux hydrophiles neutres, par exemple choisis parmi les polyols, par exemple le gluconamide, ou les polyéthers, par exemple le polyéthylèneglycol, ou leurs mélanges. iii. where appropriate, hydrophobic groups, for example chosen from molecules containing alkyl or fluorinated chains. According to one embodiment of the invention, the -R radicals of silanes Si-R at the surface consist of at least 50%, preferably at least 75%, of neutral hydrophilic radicals, for example chosen from polyols, for example gluconamide, or polyethers, for example polyethylene glycol, or mixtures thereof.
Avantageusement, les radicaux -R des liaisons silanes sont présents en surface à raison d'au moins un radical -R pour 10 nm de surface, par exemple au moins un radical -R pour 1 nm 2 , et de préférence au moins entre 1 et 10 radicaux -R par nm 2. Advantageously, the radicals -R of the silane bonds are present on the surface at the rate of at least one -R radical for 10 nm of surface, for example at least one -R radical for 1 nm 2, and preferably at least between 1 and Radicals -R per nm 2.
La fonctionnalisation de surface se fait par condensation des silanes à la surface de la matrice. On peut également ajouter des polysilanes (tels que le diéthylène- di(triméthoxy)silane) lors de la condensation pour passiver la surface de l'enrobage et lui assurer une meilleure tenue. Surface functionalization is by condensation of silanes at the surface of the matrix. Polysilanes (such as diethylene-di (trimethoxy) silane) can also be added during the condensation to passivate the surface of the coating and provide it with a better hold.
Procédé de préparation d'une suspension colloïdale de nanoparticules Process for preparing a colloidal suspension of nanoparticles
L'invention porte également sur un procédé de préparation d'une suspension colloïdale de nanoparticules utilisable comme traceur pour l'étude d'un gisement pétrolier. The invention also relates to a process for preparing a colloidal suspension of nanoparticles that can be used as a tracer for the study of a petroleum deposit.
Le procédé selon l'invention comprend les étapes suivantes : The method according to the invention comprises the following steps:
on synthétise un cœur de métal noble enrobé d'une matrice de polysiloxane préfonctionnalisée avec des silanes hydrophiles, au sein d'une microémulsion inverse, a noble metal core coated with a polysiloxane matrix prefunctionalized with hydrophilic silanes is synthesized in an inverse microemulsion,
on extrait une solution colloïdale aqueuse de nanoparticules par décantation après déstabilisation de la microémulsion, par exemple dans un mélange eau/alcool, par exemple eau/isopropanol, on chauffe les nanoparticules à au moins 50°C, par exemple, environ an aqueous colloidal solution of nanoparticles is extracted by decantation after destabilization of the microemulsion, for example in a water / alcohol mixture, for example water / isopropanol, the nanoparticles are heated to at least 50 ° C., for example, approximately
80°C. 80 ° C.
Plus précisément, selon le procédé de l'invention, le cœur et la matrice sont synthétisés en microémulsion inverse. On peut, le cas échéant, pré-enrober les nanoparticules à ce stade avec un silane hydrophile. More precisely, according to the process of the invention, the core and the matrix are synthesized in inverse microemulsion. If necessary, the nanoparticles can be pre-coated at this stage with a hydrophilic silane.
La microémulsion est ensuite déstabilisée, par exemple avec un mélange eau/alcool tel qu'eau/isopropanol, de sorte à extraire les nanoparticules sous la forme d'une solution aqueuse colloïdale stable (i.e. qui ne précipite pas). En outre, on peut laver la
solution extraite par décantation par exemple par fïltration tangentielle. Ainsi, dans un mode de réalisation avantageux du procédé selon l'invention, les nanoparticules ne sont jamais en phase sèche. The microemulsion is then destabilized, for example with a water / alcohol mixture such as water / isopropanol, so as to extract the nanoparticles in the form of a stable aqueous colloidal solution (ie which does not precipitate). In addition, we can wash the solution extracted by decantation, for example by tangential filtration. Thus, in an advantageous embodiment of the process according to the invention, the nanoparticles are never in the dry phase.
Le procédé sans phase solide sèche permettrait d'obtenir des nanoparticules de taille plus homogène, et donc avec un indice de polydispersité plus faible. The dry solid phase-free method would make it possible to obtain nanoparticles of more homogeneous size, and therefore with a lower polydispersity index.
Une autre étape particulièrement avantageuse du procédé selon l'invention est l'étape de chauffage, à au moins 50°C, par exemple au moins 60°C, au moins 70°C, par exemple à 80°C, pendant un temps suffisant pour permettre de densifïer la couche d'enrobage, par exemple au moins 30 minutes, de préférence au moins 1 h. L'étape de chauffage permettrait d'augmenter la stabilité des particules, en particulier dans le temps en limitant les phénomènes d'agglomération. Cela permettrait aussi de densifïer l'enrobage et de diminuer le nombre de groupement silanols libres de surface et plus généralement dans la couche d'enrobage. L'accrochage et la stabilité de la couche d'enrobage sont ainsi améliorés et permettraient également une protection supplémentaire des fluorophores contenus dans la matrice. Another particularly advantageous stage of the process according to the invention is the heating step, at least 50 ° C, for example at least 60 ° C, at least 70 ° C, for example at 80 ° C, for a sufficient time to allow densification of the coating layer, for example at least 30 minutes, preferably at least 1 hour. The heating step would make it possible to increase the stability of the particles, in particular over time by limiting the agglomeration phenomena. This would also make it possible to densify the coating and to reduce the number of free surface silanol groups and more generally in the coating layer. The adhesion and the stability of the coating layer are thus improved and would also provide additional protection for the fluorophores contained in the matrix.
Le procédé selon l'invention permet donc d'obtenir des solutions colloïdales avec des nanoparticules aux propriétés avantageuses et distinctes de l'art antérieur, en particulier de plus faible diamètre moyen, par exemple, inférieure à 50 nm et un faible indice de polydispersité, par exemple inférieure à 0,3, voire inférieure à 0,1, et avec une très faible réactivité avec l'environnement extérieur (traceur furtif), tels que cela peut être mis en évidence à l'aide du test de perméation décrit en exemple. The method according to the invention thus makes it possible to obtain colloidal solutions with nanoparticles with advantageous and distinct properties of the prior art, in particular of smaller average diameter, for example, less than 50 nm and a low polydispersity index, for example less than 0.3, or even less than 0.1, and with a very low reactivity with the external environment (stealth tracer), as can be demonstrated by means of the permeation test described as an example .
Aussi, l'invention porte également sur une solution colloïdale de nanoparticules, susceptible d'être obtenue selon le procédé de l'invention décrit ci-dessus. Also, the invention also relates to a colloidal solution of nanoparticles, obtainable according to the method of the invention described above.
De manière encore plus préférée, les nanoparticules sont préparées selon le procédé ci-dessus et présentent les caractéristiques structurales avantageuses telles que définies plus haut. En particulier, les nanoparticules obtenues par le procédé ci- dessus, comprennent un cœur de métal noble, par exemple d'or, et une matrice comprenant des polysiloxanes incluant une fluorophore organométallique, par exemple un agent complexant lié à un lanthanide. Even more preferably, the nanoparticles are prepared according to the above method and have the advantageous structural characteristics as defined above. In particular, the nanoparticles obtained by the above process comprise a noble metal core, for example gold, and a matrix comprising polysiloxanes including an organometallic fluorophore, for example a complexing agent linked to a lanthanide.
Méthodologie
Les nanoparticules selon l'invention sont particulièrement utiles comme traceurs dans des eaux d'injection d'un gisement pétrolier, lesquels sont destinés à l'étude dudit gisement par diffusion au travers de celui-ci, en vue notamment de contrôler les flux entre un puits d'injection et un puits de production et/ou d'évaluer les volumes de pétrole en réserve dans le gisement. Methodology The nanoparticles according to the invention are particularly useful as tracers in injection waters of a petroleum deposit, which are intended for the study of said deposit by diffusion through it, in particular to control the flow between a injection wells and a production well and / or to evaluate the volumes of oil in reserve in the deposit.
Préalablement à l'analyse du liquide ayant diffusé, on concentre celui-ci, de préférence par filtration ou dialyse, et, plus préférentiellement encore, par fïltration tangentielle et de préférence par utilisation de membrane de seuils de coupures inférieurs à 300 kDa (kilo Dalton). Prior to the analysis of the diffused liquid, it is concentrated, preferably by filtration or dialysis, and, more preferably still, by tangential filtration and preferably by use of membrane cutoff thresholds of less than 300 kDa (kilo Dalton ).
De préférence, on cherche à détecter au moins deux types de signaux émis par les nanoparticules : Preferably, it is desired to detect at least two types of signals emitted by the nanoparticles:
• un premier signal susceptible d'être émis par les fluorophores organométalliques et mesuré par fluorescence. A first signal that can be emitted by the organometallic fluorophores and measured by fluorescence.
• et un second signal susceptible d'être émis par le métal noble (comme l'or, l'argent, le platine et leurs mélanges et/ou alliages), et mesuré par analyse chimique et/ou par ICP; And a second signal capable of being emitted by the noble metal (such as gold, silver, platinum and their mixtures and / or alloys), and measured by chemical analysis and / or by ICP;
ledit métal noble constituant le cœur de la nanoparticule. said noble metal constituting the heart of the nanoparticle.
Dans un mode de réalisation préféré, pour mesurer la quantité de nanoparticules dans le liquide ayant diffusé, on privilégie une détection par fluorescence en temps résolu (pour détecter les fluorophores organométalliques) et/ou par ICP (pour la détection du métal noble dans le cœur des nanoparticules). In a preferred embodiment, to measure the amount of nanoparticles in the diffused liquid, fluorescence detection is preferred in time resolved (for detecting organometallic fluorophores) and / or by ICP (for detection of the noble metal in the heart nanoparticles).
La méthode de détection par fluorescence en temps résolu est par exemple décrite dans l'article « ultrasensitive bioanalytical assays using time resolved fluorescence détection », Phnrmac. Thu. Vol. 66, pp. 207-335, 21995. La méthode de détection par ICP est par exemple décrite dans « application of laser ICP-MS in environmental analysis », Fresenieus Journal of Analytical Chemistry, 355 : 900-903 (1996). The time resolved fluorescence detection method is for example described in the article "ultrasensitive bioanalytical assays using resolved time fluorescence detection", Phnrmac. Thu. Flight. 66, pp. 207-335, 21995. The method of detection by ICP is for example described in "application of laser ICP-MS in environmental analysis", Fresenieus Journal of Analytical Chemistry, 355: 900-903 (1996).
La détection par fluorescence en temps résolu, c'est-à-dire enclenchée avec retard après excitation (i.e. quelques microsecondes) permet d'éliminer une grande partie de la luminescence intrinsèque au milieu solide étudié et de ne mesurer que celle relative à la nanoparticule traçante. The fluorescence detection in time resolved, that is to say, triggered with delay after excitation (ie a few microseconds) makes it possible to eliminate a large part of the luminescence intrinsic to the solid medium studied and to measure only that relative to the nanoparticle fescue.
LÎQMide d injeçtion _(m Means of Injection _ (m
pétrolier
Selon un autre de ses objets, l'invention concerne un liquide d'injection dans un gisement pétrolier, caractérisé en ce qu'il comprend un traceur à base de nanoparticules selon l'invention comme définie plus haut. tanker According to another of its objects, the invention relates to an injection liquid in a petroleum field, characterized in that it comprises a tracer based on nanoparticles according to the invention as defined above.
Avantageusement, ce liquide comprend de l'eau et les nanoparticules telles que définies ci-dessus. Advantageously, this liquid comprises water and the nanoparticles as defined above.
Les eaux d'injection peuvent comprendre, outre les nanoparticules, les éléments suivants : des tensioactifs, des petits polymères hydrophiles, des polyalcools (par exemple du diethylèneglycol), des sels et autres molécules classiquement utilisées en injection pétrolière. The injection waters may comprise, in addition to the nanoparticles, the following elements: surfactants, hydrophilic small polymers, polyalcohols (for example diethylene glycol), salts and other molecules conventionally used in petroleum injection.
Description des figures Description of figures
Figure 1 : La figure 1 montre le spectre d'émission en temps résolu (délai 0,1 ms, temps d'acquisition 5 ms) des nanoparticules contenant Eu DTPA et fluorescéine sous excitation à 395 nm et le spectre d'excitation en temps résolu (délai 0,1 ms, temps d'acquisition 5 ms) de ces mêmes nanoparticules avec une émission fixe à 615 nm Figure 1: Figure 1 shows the emission spectrum in time resolved (delay 0.1 ms, acquisition time 5 ms) of the nanoparticles containing Eu DTPA and fluorescein under excitation at 395 nm and the excitation spectrum in time resolved (delay 0.1 ms, acquisition time 5 ms) of these same nanoparticles with a fixed emission at 615 nm
Figure 2: La figure 2 montre le spectre d'excitation en temps résolu (délai 0,1 ms, temps d'acquisition 5 ms) des nanoparticules contenant Eu DOTA et fluorescéine avec une émission fixe à 615 nm et le spectre d'émission en temps résolu (délai 0,1 ms, temps d'acquisition 5 ms) des particules contenant Eu DOTA et fluorescéine sous excitation à 395 nm Figure 2: Figure 2 shows the time-resolved excitation spectrum (delay 0.1 ms, acquisition time 5 ms) of the nanoparticles containing Eu DOTA and fluorescein with a fixed emission at 615 nm and the emission spectrum in time resolved (delay 0.1 ms, acquisition time 5 ms) of the particles containing Eu DOTA and fluorescein under excitation at 395 nm
Figure 3 : La figure 3a montre le spectre d'excitation en temps résolu (délai 0,1 ms, temps d'acquisition 5 ms) des particules contenant les nanoparticules contenant Tb et dérivés de pyridine avec une émission fixe à 545 nm Figure 3: Figure 3a shows the time-resolved excitation spectrum (delay 0.1 ms, acquisition time 5 ms) of the particles containing nanoparticles containing Tb and pyridine derivatives with a fixed emission at 545 nm
La figure 3b montre le spectre d'émission en temps résolu (délai 0,1 ms, temps d'acquisition 5 ms) des particules contenant les nanoparticules contenant Tb et dérivés de pyridine sous excitation à 246 nm FIG. 3b shows the emission spectrum in time resolved (delay 0.1 ms, acquisition time 5 ms) of the particles containing nanoparticles containing Tb and pyridine derivatives under excitation at 246 nm
Figure 4 : La figure 4 montre des courbes de perméation comparatives entre un traceur de référence (gris) et les nanoparticules (noir) selon le procédé de préparation 4. En abscisses, le volume écoulé. En ordonnées, l'absorption ou la fluorescence, normalisée aux valeurs initiales.
Après 180 mL, une solution d'eau de mer dégazée sans traceurs est injectée. Exemples Figure 4: Figure 4 shows comparative permeation curves between a reference tracer (gray) and the nanoparticles (black) according to the preparation method 4. As abscissa, the volume elapsed. On the ordinate, absorption or fluorescence, normalized to the initial values. After 180 mL, a solution of degassed seawater without tracer is injected. Examples
Procédé de Préparation 1. Préparation d'une solution colloïdale de nanoparticules avec un cœur d'or et une matrice de silice encapsulant des fluorophores organiques dérivés de fluorescéine et des complexes (DTPA) d'europium. Preparation Method 1. Preparation of a colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating fluorescein-derived organic fluorophores and europium (DTPA) complexes.
Dans une bouteille de 10 mL, 200 mg d'acide diéthylènetriaminepentaacetiquebisanhydride (DTPABA), 0,130 mL d'APTES et 0,065 mL de triéthylamine sont introduits avec 4 mL de DMSO (diméthylsulfoxyde) sous agitation vigoureuse. Après 24 heures, 200 mg d'EuCl3,6H20 est ajouté. Après 48 heures la complexation est suffisante ; on réalise alors les étapes suivantes : dans une bouteille de 2,5 mL, 20 mg de FITC (fluorescéine isothiocyanate) sont introduites avec 0,5 mL d'APTES ((3-aminopropyl)triéthoxysilane) sous agitation vigoureuse. On homogénéise pendant 30 minutes à température ambiante. In a 10 mL bottle, 200 mg of diethylenetriaminepentaaceticbisanhydride acid (DTPABA), 0.130 mL of APTES and 0.065 mL of triethylamine are introduced with 4 mL of DMSO (dimethylsulfoxide) with vigorous stirring. After 24 hours, 200 mg of EuCl3,6H 2 0 is added. After 48 hours the complexation is sufficient; the following steps are then carried out: in a 2.5 mL bottle, 20 mg of FITC (fluorescein isothiocyanate) are introduced with 0.5 mL of APTES ((3-aminopropyl) triethoxysilane) with vigorous stirring. Homogenized for 30 minutes at room temperature.
Dans un ballon de 500 mL, 36 mL de Triton X-100 (tensioactif), 36 mL de n-hexanol (co-tensioactif), 150 mL de cyclohexane (huile) et 21 mL de solution aqueuse contenant 9 mL de HAuCl403H2O à 16,7 mM, 9 mL de MES (Sodium 2- mercaptoéthanesulfonate) à 32,8 mM et 3 mL de NaBH4 à 412 mM sont introduits sous agitation vigoureuse. Après 5 minutes, 0,400 mL de solution contenant la fluorescéine est ajoutée dans la microémulsion avec 1 mL de la solution contenant le complexe d'europium. Puis 0,200 mL d'APTES et 1,5 mL de TEOS (tetraéthylorthosilicate) sont également ajoutés à la microémulsion. In a 500 ml flask, 36 ml of Triton X-100 (surfactant), 36 ml of n-hexanol (co-surfactant), 150 ml of cyclohexane (oil) and 21 ml of aqueous solution containing 9 ml of HAuCl 4 O 3H From 0 to 16.7 mM, 9 ml of 32.8 mM MES (Sodium 2-mercaptoethanesulfonate) and 3 ml of 412 mM NaBH 4 are introduced with vigorous stirring. After 5 minutes, 0.400 ml of solution containing fluorescein is added to the microemulsion with 1 ml of the solution containing the europium complex. Then 0.200 mL of APTES and 1.5 mL of TEOS (tetraethylorthosilicate) are also added to the microemulsion.
La réaction de polymérisation de la silice est complétée par l'addition de 0,800 mL de NH4OH après 10 minutes. On agite la microémulsion pendant 24 h à température ambiante. The polymerization reaction of the silica is completed by the addition of 0.800 ml of NH 4 OH after 10 minutes. The microemulsion is stirred for 24 h at room temperature.
Ensuite, 190 de Silane-gluconamide (N-(3-Triéthoxysilylpropyl)gluconamide) à 50% dans l'éthanol est ajouté à la microémulsion sous agitation à température ambiante. Then 190% of silane-gluconamide (N- (3-Triethoxysilylpropyl) gluconamide) at 50% in ethanol is added to the microemulsion with stirring at room temperature.
Après 24 h, 190 de Silane-gluconamide sont à nouveau ajoutés à la solution toujours sous agitation à température ambiante.
Après 24 h, la microémulsion est déstabilisée dans une ampoule à décanter par ajout d'un mélange de 250 mL d'eau distillée et 250 mL d'isopropanol. La solution est laissée à décanter 15 minutes et la phase inférieure contenant les particules est récupérée. After 24 hours, 190 of silane-gluconamide are again added to the solution, still stirring at room temperature. After 24 hours, the microemulsion is destabilized in a separatory funnel by adding a mixture of 250 ml of distilled water and 250 ml of isopropanol. The solution is left to settle for 15 minutes and the lower phase containing the particles is recovered.
La solution colloïdale récupérée est ensuite placée dans un système de filtration tangentielle VIVASPIN© à 300 kDa puis centrifugée à 4000 tr/min jusqu'à obtention d'un taux de purification supérieur à 500. The colloidal solution recovered is then placed in a 300 kDa VIVASPIN © tangential filtration system and then centrifuged at 4000 rpm until a purification rate greater than 500 is obtained.
La solution ainsi obtenue est alors filtrée à 0,2 μπι et diluée par 5 dans du DEG (diéthylèneglycol). The solution thus obtained is then filtered at 0.2 μπι and diluted 5 in DEG (diethylene glycol).
Procédé de Préparation 2. Préparation d'une solution colloïdale de nanoparticules avec un cœur d'or et une matrice de silice encapsulant des fluorophores organiques dérivés de fluorescéine et des complexes (DOTA) d'europium. Preparation Process 2. Preparation of a colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating fluorescein-derived organic fluorophores and europium (DOTA) complexes.
La synthèse est similaire à celle décrite dans le procédé de préparation 1 à la différence que les 200 mg d'acide diéthylènetriaminepentaacetiquebisanhydride sont remplacés par 256 mg d'acide l,4,7,10-tétraazacyclodécane-l,4,5,10-tétraacétique glutarique anhydride) (DOTAGA). Le reste de la synthèse est identique. The synthesis is similar to that described in Preparation Procedure 1 except that the 200 mg of diethylenetriaminepentaaceticbisanhydride acid is replaced by 256 mg of 1,4,7,10-tetraazacyclodecane-1,4,5,10- glutaric tetraacetic anhydride) (DOTAGA). The rest of the synthesis is identical.
Procédé de Préparation 3. Préparation d'une solution colloïdale de nanoparticules avec un cœur d'or et une matrice de silice encapsulant des molécules organiques contenant un cycle aromatique dérivées de pyridine (antenne) et des complexes de terbium. Preparation Process 3. Preparation of a colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating aromatic ring-containing organic molecules derived from pyridine (antenna) and terbium complexes.
Dans une bouteille de 2,5 mL, 85 mg de 2-Pyridinethioamide (antenne), 70 mg de NHS (N-hydroxysuccinimide) et 230 mg d'EDCIn a 2.5 mL bottle, 85 mg of 2-pyridinethioamide (antenna), 70 mg of NHS (N-hydroxysuccinimide) and 230 mg of EDC
(éthyl(diméthylaminopropyl)carbodiimide) sont introduites avec 2 mL de DMSO (diméthylsulfoxyde) sous agitation vigoureuse. Après 30 minutes, 140 μί d'APTES sont ajoutés et on attend 5 heures. (Ethyl (dimethylaminopropyl) carbodiimide) are introduced with 2 ml of DMSO (dimethylsulfoxide) with vigorous stirring. After 30 minutes, 140 μί of APTES are added and waiting 5 hours.
Ensuite, dans une bouteille de 2,5 mL, 1 lot de nanoparticules d'oxyde de terbium lyophilisées (diamètre 5 nm) achetés chez la société Nano-H SAS sont re -dispersées dans 2 mL d'eau distillée. Then, in a 2.5 mL bottle, 1 batch of lyophilized terbium oxide nanoparticles (diameter 5 nm) purchased from Nano-H SAS are re-dispersed in 2 mL of distilled water.
Dans un ballon de 500 mL, 36 mL de Triton X-100 (tensioactif), 36 mL de «-hexanol (co-tensioactif), 150 mL de cyclohexane (huile) et 21 mL de solution aqueuse
contenant 9 mL de HAuCl403H2O à 16,7 mM, 9 mL de MES (Sodium 2- mercaptoéthanesulfonate) à 32,8 mM et 3 mL de NaBH4 à 412 mM sont introduits sous agitation vigoureuse. Après 5 minutes, 0,600 mL de solution contenant les antennes est ajoutée dans la microémulsion avec 2 mL de la solution contenant les particules de terbium. Ensuite 0,550 mL d'APTES et 1,5 mL de TEOS (tetraéthylorthosilicate) sont également ajoutés à la microémulsion. In a 500 ml flask, 36 ml of Triton X-100 (surfactant), 36 ml of hexanol (co-surfactant), 150 ml of cyclohexane (oil) and 21 ml of aqueous solution. containing 9 mL of 16.7 mM HAuCl 4 O 3 H 2 O, 9 mL of 32.8 mM MES (Sodium 2-mercaptoethanesulfonate) and 3 mL of 412 mM NaBH 4 are added with vigorous stirring. After 5 minutes, 0.600 mL of solution containing the antennas is added to the microemulsion with 2 mL of the solution containing the terbium particles. Then 0.550 mL of APTES and 1.5 mL of TEOS (tetraethylorthosilicate) are also added to the microemulsion.
La réaction de polymérisation de la silice est complétée par l'addition de 0,800 mL de NH4OH après 10 minutes. On agite la microémulsion pendant 24 h à température ambiante. The polymerization reaction of the silica is completed by the addition of 0.800 ml of NH 4 OH after 10 minutes. The microemulsion is stirred for 24 h at room temperature.
La fonctionnalisation avec le silane-gluconamide et le traitement de la microémulsion sont comme décrit pour le procédé de préparation 1. Functionalization with silane-gluconamide and treatment of the microemulsion are as described for the preparation process 1.
Procédé de Préparation 4. Préparation d'une solution colloïdale de nanoparticules avec un cœur d'or et une matrice de silice encapsulant des molécules organiques contenant un cycle aromatique dérivées de fluorescéine et des particules contenant des complexes d'europium. Preparation Process 4. Preparation of a colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating fluorescein-derived aromatic ring-containing organic molecules and particles containing europium complexes.
Dans une bouteille de 2,5 mL, 20 mg de FITC (fluorescéine isothiocyanate) sont introduites avec 0,5 mL d'APTES ((3-aminopropyl)triéthoxysilane) sous agitation vigoureuse. On homogénéise pendant 30 minutes à température ambiante. In a 2.5 mL bottle, 20 mg of FITC (fluorescein isothiocyanate) are introduced with 0.5 mL of APTES ((3-aminopropyl) triethoxysilane) with vigorous stirring. Homogenized for 30 minutes at room temperature.
Dans une bouteille de 2,5 mL, 1 lot de nanoparticules SRP-europium lyophilisées (diamètre 5 nm - 20 micromoles équivalent europium - Small Rigid Platform polysiloxane-DOTA(Eu)) (société Nano-H SAS, France) est re-dispersées dans 1,5 mL d'eau distillée. In a 2.5 mL bottle, 1 lot of lyophilized SRP-europium nanoparticles (diameter 5 nm - 20 micromoles europium equivalent - Small Rigid Platform polysiloxane-DOTA (Eu)) (Nano-H SAS, France) is re-dispersed in 1.5 mL of distilled water.
Dans un ballon de 500 mL, 36 mL de Triton X-100 (tensioactif), 36 mL de n-hexanol (co-tensioactif), 150 mL de cyclohexane (huile) et 21 mL de solution aqueuse contenant 9 mL de HAuCl4e3H20 à 16,7 mM, 9 mL de MES (Sodium 2- mercaptoéthanesulfonate) à 32,8 mM et 3 mL de NaBH4à 412 mM sont introduits sous agitation vigoureuse. Après 5 minutes, 0,400 mL de solution contenant la fluorescéine est ajoutée dans la microémulsion avec 1,5 mL de la solution contenant les particules d'europium. Dans la foulée 0,200 mL d'APTES et 1,5 mL de TEOS (tetraéthylorthosilicate) sont également ajoutés à la microémulsion.
La réaction de polymérisation de la silice est complétée par l'addition de 0,800 mL de NH40H après 10 minutes. On agite la microémulsion pendant 24 h à température ambiante. In a 500 ml flask, 36 ml of Triton X-100 (surfactant), 36 ml of n-hexanol (co-surfactant), 150 ml of cyclohexane (oil) and 21 ml of aqueous solution containing 9 ml of HAuCl 4 e 3 H 2 O at 16.7 mM, 9 mL of 32.8 mM MES (Sodium 2-mercaptoethanesulfonate) and 3 mL of 412 mM NaBH 4 are introduced with vigorous stirring. After 5 minutes, 0.400 ml of solution containing fluorescein is added to the microemulsion with 1.5 ml of the solution containing the europium particles. In the wake 0.200 mL of APTES and 1.5 mL of TEOS (tetraethylorthosilicate) are also added to the microemulsion. The polymerization reaction of the silica is completed by the addition of 0.800 ml of NH 4 OH after 10 minutes. The microemulsion is stirred for 24 h at room temperature.
La fonctionnalisation avec le silane-gluconamide et le traitement de la microémulsion sont similaires au procédé de préparation 1. Functionalization with silane-gluconamide and treatment of the microemulsion are similar to preparation method 1.
Procédé de préparation 5a. Solution colloïdale de nanoparticules avec un cœur d'or et une matrice de silice encapsulant des molécules organiques contenant un cycle aromatique de pyridine et des particules contenant des complexes d'europium. Preparation process 5a. Colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating organic molecules containing an aromatic pyridine ring and particles containing europium complexes.
La synthèse est similaire à celle décrite dans le procédé de préparation 1 à la différence de la fonctionnalisation effectuée dans la microémulsion. Le deuxième ajout de 190 de Silane-gluconamide est remplacé par un ajout de 450 mg de Silane (N-(Triéthoxysilylpropyl)-O-polyéthylèneoxideuréthane) correspondant à une quantité théorique de 2 silanes par nm de surface. The synthesis is similar to that described in preparation method 1 unlike the functionalization performed in the microemulsion. The second addition of 190 of silane-gluconamide is replaced by an addition of 450 mg of silane (N- (triethoxysilylpropyl) -O-polyethyleneoxideurethane) corresponding to a theoretical amount of 2 silanes per nm of area.
Procédé de préparation 5b. Solution colloïdale de nanoparticules avec un cœur d'or et une matrice de silice encapsulant des molécules organiques contenant un cycle aromatique de pyridine et des particules contenant des complexes d'europium. Preparation process 5b. Colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating organic molecules containing an aromatic pyridine ring and particles containing europium complexes.
La synthèse est similaire à celle décrite dans le procédé de préparation 1 à la différence de la fonctionnalisation effectuée dans la microémulsion. Le deuxième ajout de 190 de Silane-gluconamide est remplacé par un ajout de 340 de Silane ([Hydroxy(polyéthylènoxy)propyl]triéthoxysilane) à 50% dans l'éthanol, correspondant à une quantité théorique de 2 silanes par nm2 de surface. The synthesis is similar to that described in preparation method 1 unlike the functionalization performed in the microemulsion. The second addition of 190 of silane-gluconamide is replaced by an addition of 340 of silane ([Hydroxy (polyethylenoxy) propyl] triethoxysilane) at 50% in ethanol, corresponding to a theoretical amount of 2 silanes per nm 2 of surface area.
Procédé de préparation 5c. Solution colloïdale de nanoparticules avec un cœur d'or et une matrice de silice encapsulant des molécules organiques contenant un cycle aromatique de pyridine et des particules contenant des complexes d'europium. Preparation process 5c. Colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating organic molecules containing an aromatic pyridine ring and particles containing europium complexes.
La synthèse est similaire à celle décrite dans le procédé de préparation 1 à la différence de la fonctionnalisation effectuée dans la microémulsion. Le deuxième ajout de 190 μΐ, de Silane-gluconamide est remplacé par un ajout de 185 μΐ, de Silane (acide N-(triméthoxysilylpropyl)éthylènediaminetriacétique) à 45% dans l'eau, correspondant à une quantité théorique de 2 silanes par nm de surface.
Procédé de préparation 5d. Solution colloïdale de nanoparticules avec un cœur d'or et une matrice de silice encapsulant des molécules organiques contenant un cycle aromatique de pyridine et des particules contenant des complexes d'europium. The synthesis is similar to that described in preparation method 1 unlike the functionalization performed in the microemulsion. The second addition of 190 μΐ of Silane-gluconamide is replaced by an addition of 185 μΐ of Silane (N- (trimethoxysilylpropyl) ethylenediaminetriacetic acid) to 45% in water, corresponding to a theoretical amount of 2 silanes per nm of area. Preparation process 5d. Colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating organic molecules containing an aromatic pyridine ring and particles containing europium complexes.
La synthèse est similaire à celle décrite dans le procédé de préparation 1 à la différence de la fonctionnalisation effectuée dans la microémulsion. Le deuxième ajout de 190 de Silane-gluconamide est remplacé par un ajout de 60 de Silane (3-thiocyanatopropyltriéthoxysilane), ce qui correspond à une quantité théorique de 2 silanes par nm2 de surface. The synthesis is similar to that described in preparation method 1 unlike the functionalization performed in the microemulsion. The second addition of 190 of silane-gluconamide is replaced by an addition of 60 of silane (3-thiocyanatopropyltriethoxysilane), which corresponds to a theoretical amount of 2 silanes per nm 2 of surface area.
Procédé de préparation 5e. Solution colloïdale de nanoparticules avec un cœur d'or et une matrice de silice encapsulant des molécules organiques contenant un cycle aromatique de pyridine et des particules contenant des complexes d'europium. Preparation process 5e. Colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating organic molecules containing an aromatic pyridine ring and particles containing europium complexes.
La synthèse est similaire à celle décrite dans le procédé de préparation 1 à la différence de la fonctionnalisation effectuée dans la microémulsion. Le deuxième ajout de 190 de Silane-gluconamide est remplacé par un ajout de 60 μΐ, de Silane (3-isocyanatopropyltriéthoxysilane), ce qui correspond à une quantité théorique de 2 silanes par nm2 de surface. The synthesis is similar to that described in preparation method 1 unlike the functionalization performed in the microemulsion. The second addition of 190 of silane-gluconamide is replaced by a 60 μΐ addition of Silane (3-isocyanatopropyltriethoxysilane), which corresponds to a theoretical amount of 2 silanes per nm 2 of surface area.
Procédé de préparation 6a : Preparation process 6a:
La solution obtenue selon le procédé de préparation 4 est post fonctionnalisée par un silane ( -(2-aminoéthyl)-3-aminopropyltriéthoxysilane). Dans un flacon de 15 mL, 20 μΐ^ de silane est dilué dans 10 mL de DEC Dans un flacon de 15 mL, 10 de la solution de silane dilué (correspondant à une quantité théorique de 0,1 molécule de silane par nm de surface de particule) est ajouté à 10 mL de la solution obtenue selon le procédé de préparation 4, la solution obtenue est mise sous agitation à 40°C pendant 48 h. The solution obtained according to the preparation method 4 is post-functionalized with a silane (- (2-aminoethyl) -3-aminopropyltriethoxysilane). In a flask of 15 mL, 20 μΐ ^ silane was diluted in 10 mL of December in a flask of 15 mL, 10 of the diluted silane solution (corresponding to a theoretical amount of 0.1 silane molecule per nm surface of particle) is added to 10 ml of the solution obtained according to the preparation method 4, the resulting solution is stirred at 40 ° C for 48 h.
Procédé de préparation 6b. Preparation process 6b.
La solution obtenue selon le procédé de préparation 4 est post fonctionnalisée par un silane (anhydride 3-(triéthoxysilyl)propylsuccinique). Dans un flacon de 15 mL, 20 μΐ, de silane est dilué dans 10 mL de DEC Dans un flacon de 15 mL, \0 μΐ, de la
solution de silane dilué (correspondant à une quantité théorique de 0,1 molécule de silane par nm2 de surface de particule) est ajouté à 10 mL de la solution obtenue selon le procédé de préparation 4, la solution obtenue est mise sous agitation à 40°C pendant 48 h. The solution obtained according to the preparation method 4 is post-functionalized with a silane (3- (triethoxysilyl) propylsuccinic anhydride). In a 15 mL vial, 20 μL of silane is diluted in 10 mL of DEC. In a 15 mL vial, diluted silane solution (corresponding to a theoretical amount of 0.1 molecule of silane per nm 2 of particle surface) is added to 10 ml of the solution obtained according to the preparation method 4, the resulting solution is stirred at 40 ° C. ° C for 48 hours.
Procédé de préparation 6c. Preparation process 6c.
La solution obtenue selon l'exemple 4 est post fonctionnalisée par un silane (O- (propargyloxy)-N-(triéthoxysilylpropyl)uréthane). Dans un flacon de 15 mL, 24 de silane est dilué dans 10 mL de DEG. Dans un flacon de 15 mL, 10 de la solution de silane dilué (correspondant à une quantité théorique de 0,1 molécule de silane par nm de surface de particule) est ajouté à 10 mL de la solution obtenue dans l'exemple 4, la solution obtenue est mise sous agitation à 40°C pendant 48 h. The solution obtained according to Example 4 is post-functionalized with a silane (O- (propargyloxy) -N- (triethoxysilylpropyl) urethane). In a 15 mL vial, 24 of silane is diluted in 10 mL of DEG. In a 15 mL flask, 10 diluted silane solution (corresponding to a theoretical amount of 0.1 silane molecule per nm of particle area) is added to 10 mL of the solution obtained in Example 4, the solution obtained is stirred at 40 ° C for 48 h.
Procédé de préparation 7. Solution colloïdale de nanoparticules avec un cœur d'or et une matrice de silice encapsulant des molécules de organiques contenant un cycle aromatique dérivées de pyridine et des complexes (DTPA) d'europium. Preparation Process 7. Colloidal solution of nanoparticles with a gold core and a silica matrix encapsulating aromatic ring-containing organic molecules derived from pyridine and europium (DTPA) complexes.
Dans une bouteille de 2,5 mL, 140 mg d'antennes (2,2' :6',2"-terpyridine), 70 mg de NHS (N-hydroxysuccinimide) et 230 mg d'EDCIn a 2.5 mL bottle, 140 mg of antennas (2,2 ': 6', 2 "-terpyridine), 70 mg of NHS (N-hydroxysuccinimide) and 230 mg of EDC
(éthyl(diméthylaminopropyl)carbodiimide) sont introduites avec 2 mL de DMSO (diméthylsulfoxyde) sous agitation vigoureuse. Après 30 minutes, 140 μί d'APTES sont ajoutés. (Ethyl (dimethylaminopropyl) carbodiimide) are introduced with 2 ml of DMSO (dimethylsulfoxide) with vigorous stirring. After 30 minutes, 140 μί of APTES are added.
Dans une bouteille de 10 mL, 200 mg d'acide diéthylènetriammepentaacétique (DTPA), 0,130 mL d'APTES et 0,065 mL de triéthylamine sont introduits avec 4 mL de DMSO (diméthylsulfoxyde) sous agitation vigoureuse. Après 24 heures, 200 mg d'EuCi3,6H20 est ajouté. Après 48 heures la complexation est suffisante. Dans un ballon de 500 mL, 36 mL de Triton X-100 (tensioactif), 36 mL de n-hexanol (co- tensioactif), 150 mL de cyclohexane (huile) et 21 mL de solution aqueuse contenant 9 mL de HAuCl4e3H20 à 16,7 mM, 9 mL de MES (Sodium 2- mercaptoéthanesulfonate) à 32,8 mM et 3 mL de NaBH4 à 412 mM sont introduits sous agitation vigoureuse. Après 5 minutes, 0,400 mL de solution contenant la fluorescéine est ajoutée dans la microémulsion avec 1 mL de la solution contenant le complexe d'europium. Ensuite, 0,200 mL d'APTES et 1,5 mL de TEOS (tetraéthylorthosilicate) sont également ajoutés à la microémulsion.
La réaction de polymérisation de la silice est complétée par l'addition de 0,800 mL de NH4OH après 10 minutes. On agite la microémulsion pendant 24 h à température ambiante. In a 10 mL bottle, 200 mg of diethylenetriaminepentaacetic acid (DTPA), 0.130 mL of APTES and 0.065 mL of triethylamine are introduced with 4 mL of DMSO (dimethylsulfoxide) with vigorous stirring. After 24 hours, 200 mg of EuCi3,6H20 is added. After 48 hours the complexation is sufficient. In a 500 mL flask, 36 mL of Triton X-100 (surfactant), 36 mL of n-hexanol (co-surfactant), 150 mL of cyclohexane (oil) and 21 mL of aqueous solution containing 9 mL of HAuCl 4 eH From 16 to 16.7 mM, 9 mL of 32.8 mM MES (Sodium 2-mercaptoethanesulfonate) and 3 mL of 412 mM NaBH 4 were added with vigorous stirring. After 5 minutes, 0.400 ml of solution containing fluorescein is added to the microemulsion with 1 ml of the solution containing the europium complex. Then, 0.200 mL of APTES and 1.5 mL of TEOS (tetraethylorthosilicate) are also added to the microemulsion. The polymerization reaction of the silica is completed by the addition of 0.800 ml of NH 4 OH after 10 minutes. The microemulsion is stirred for 24 h at room temperature.
Ensuite, 190 μί de Silane-gluconamide (N-(3-Triéthoxysilylpropyl)gluconamide) à 50% dans Péthanol est ajouté à la microémulsion sous agitation à température ambiante. Then, 190 μl of 50% Silane-gluconamide (N- (3-Triethoxysilylpropyl) gluconamide) in ethanol is added to the microemulsion with stirring at room temperature.
Après 24 h, 190 de Silane-gluconamide sont à nouveau ajoutés à la solution toujours sous agitation à température ambiante. After 24 hours, 190 of silane-gluconamide are again added to the solution, still stirring at room temperature.
Après 24 h, la microémulsion est déstabilisée dans une ampoule à décanter par ajout d'un mélange de 250 mL d'eau distillée et 250 mL d'isopropanol. La solution est laissée à décanter 15 minutes et la phase inférieure contenant les particules est récupérée. After 24 hours, the microemulsion is destabilized in a separatory funnel by adding a mixture of 250 ml of distilled water and 250 ml of isopropanol. The solution is left to settle for 15 minutes and the lower phase containing the particles is recovered.
La solution colloïdale récupérée est ensuite placée dans un système de fïltration VIVASPIN© à 300 kDa puis centrifugée à 4000 tr/min jusqu'à obtention d'un taux de purification supérieur à 500. The colloidal solution recovered is then placed in a 300 kDa VIVASPIN® filtration system and then centrifuged at 4000 rpm until a purification rate greater than 500 is obtained.
La solution ainsi obtenue est alors filtrée à 0,2 μηι et diluée par 5 dans du DEG (diéthylèneglycol). The solution thus obtained is then filtered at 0.2 μηι and diluted by 5 in DEG (diethylene glycol).
La solution obtenue est alors post- fonctionnalisée avec 3,72 μΐ de silane (N- (triéthoxysilylpropyl)-O-polyéthylèneoxideurethane) (correspondant à une quantité théorique de 0,1 molécule de silane par nm2 de surface de particule) à 40°C sous agitation pendant 48 h. The solution obtained is then post-functionalized with 3.72 μl of silane (N- (triethoxysilylpropyl) -O-polyethyleneoxideurethane) (corresponding to a theoretical amount of 0.1 molecule of silane per nm 2 of particle surface) at 40 ° C. with stirring for 48 h.
Résultats Results
Diamètre moyens et polydispersité des nanoparticules selon les procédés de préparation 1 à 5 (exemples 1 à 5). Mean diameter and polydispersity of the nanoparticles according to the preparation methods 1 to 5 (Examples 1 to 5).
Des solutions colloïdales de nanoparticules ont été préparées selon les procédés de préparations 1 à 5 (exemples 1 à 5 respectivement). Colloidal solutions of nanoparticles were prepared according to the methods of Preparation 1 to 5 (Examples 1 to 5 respectively).
Le tableau suivant donne le diamètre moyen et l'indice de polydispersité des nanoparticules telles qu'obtenues selon les exemples 1 à 5.
Exemples Diamètre moyen PolydispersitéThe following table gives the average diameter and the polydispersity index of the nanoparticles as obtained according to Examples 1 to 5. Examples Average diameter Polydispersity
Exemple 1 50 nm 0,091 Example 1 50 nm 0.091
Exemple 2 62 nm 0,057 Example 2 62 nm 0.057
Exemple 3 37 nm 0,060 Example 3 37 nm 0.060
Exemple 4 41 nm 0,055 Example 4 41 nm 0.055
Exemple 5 a 46 nm 0,050 Example 5 at 46 nm 0.050
Exemple 5b 44 nm 0,109 Example 5b 44 nm 0.109
Exemple 5 c 55 nm 0,083 Example 5 c 55 nm 0.083
Exemple 5d 53 nm 0,081 Example 5d 53 nm 0.081
Exemple 5 e 70 nm 0,109 Example 5 e 70 nm 0.109
Les figures 1, 2 et 3 présentent les spectres d'excitation et d'émission avec un délai de 0,1 ms pour les exemples 1 à 3 respectivement. Ces données montrent que les nanoparticules présentent une bonne propriété de fluorescence en temps résolu. Figures 1, 2 and 3 show the excitation and emission spectra with a delay of 0.1 ms for Examples 1 to 3 respectively. These data show that the nanoparticles have a good time resolved fluorescence property.
Comparaison des propriétés des nanoparticules avant et après étape de chauffage Comparison of nanoparticle properties before and after heating step
Pour les exemples 6a à 6c, on a préparé des nanoparticules selon les procédés de préparation 6a à 6c. For Examples 6a to 6c, nanoparticles were prepared according to the preparation methods 6a to 6c.
Le tableau suivant résume le diamètre moyen, la polydispersité et le potentiel zêta des nanoparticules avant et après l'étape de chauffage, l'étape de chauffage consistant à chauffer la solution de nanoparticules après la post fonctionnalisation à 80°C durant 1 h et puis à la refroidir à température ambiante. The following table summarizes the average diameter, polydispersity and zeta potential of the nanoparticles before and after the heating step, the heating step of heating the nanoparticle solution after post-functionalization at 80 ° C for 1 hour and then to cool to room temperature.
Exemples Valeurs avant chauffage Valeurs après chauffage Examples Values before heating Values after heating
Diamètre moyen Diamètre moyen Average diameter Average diameter
Polydispersité PolydispersitéPolydispersity Polydispersity
Potentiel zêta Potentiel zêtaZeta Potential Zeta Potential
Exemple 1 50 nm 51 nm Example 1 50 nm 51 nm
0,091 0,075 0.091 0.075
n/d n/d n / a n / a
Exemple 3 37 nm 39 nm Example 3 37 nm 39 nm
0,060 0,077 0.060 0.077
n/d n/d
Exemple 4 41 nm 47 nm n / d n / d Example 4 41 nm 47 nm
0,055 0,026 0.055 0.026
n/d n/d n / a n / a
Exemple 6a 35 nm 35 nm Example 6a 35 nm 35 nm
0,053 0,066 0.053 0.066
3,69 mV mesuré à pH 6,2 5,15 mV mesuré à pH 6,5 3.69 mV measured at pH 6.2 5.15 mV measured at pH 6.5
Exemple 6b 35 nm 34 nm Example 6b 35 nm 34 nm
0,034 0,116 0.034 0.116
13,0 mV mesuré à pH 6,2 -22,2 mV mesuré à pH 6,5 13.0 mV measured at pH 6.2 -22.2 mV measured at pH 6.5
Exemple 6c 33 nm 38 nm Example 6c 33 nm 38 nm
0,077 0,035 0.077 0.035
13,7 mV mesuré à pH 6,2 -25,0 mV mesuré à pH 6,5 13.7 mV measured at pH 6.2 -25.0 mV measured at pH 6.5
Test de perméation Permeation test
Nous décrivons ici la fabrication d'une cartouche permettant à un fluide de percoler à travers une carotte cylindrique de roche poreuse dans le sens longitudinal, sans perte de fluide par le côté de celle-ci et la perméation de particules. We describe here the manufacture of a cartridge allowing a fluid to percolate through a cylindrical core of porous rock in the longitudinal direction, without loss of fluid by the side of it and the permeation of particles.
Le matériel utilisé est composé de la carotte, de deux bouchons de même diamètre spécialement usinés pour permettre le vissage de raccords, de tube en PVC transparent, d'un patron en PTFE, de colle Araldite et d'un tube de joint silicone commercial. The material used consists of the core, two plugs of the same diameter specially machined to allow the screwing of fittings, transparent PVC tube, a PTFE pattern, Araldite glue and a commercial silicone seal tube.
Enfoncer un des deux bouchons dans le patron, le fixer avec la silicone, puis laisser sécher pendant 30 minutes. Préparer la colle Araldite dans une coupelle en aluminium puis placer la carotte sur le bouchon et la coller, laisser sécher quelques minutes. Faire de même pour le bouchon du dessus. Découper le tube PVC à la longueur correspondante, mettre de la silicone sur la base du tube puis le retourner sur le patron. Mettre le tout à l'étuve à 50°C pendant ½ heure. Press one of the two plugs into the pattern, secure with silicone, and allow to dry for 30 minutes. Prepare the Araldite glue in an aluminum cup then place the carrot on the cap and stick it, let dry a few minutes. Do the same for the top cap. Cut the PVC tube to the corresponding length, put silicone on the base of the tube and turn it on the pattern. Put all in an oven at 50 ° C for ½ hour.
Déterminer le volume de résine époxy en tenant compte du phénomène d'imbibition dans la roche (volume équivalent à 0,4 cm de diamètre de la colonne. La résine époxy est composée à 70% d'une base de résine (Epon 828 - Miller-Stephenson Chemical Company, Inc) et à 30% d'un durcisseur (Versamid 125 - Miller-Stephenson Chemical Company, Inc). Dans un gobelet plastique à usage unique, mélanger la
résine avec le durcisseur pendant 10 minutes, puis placer le mélange à 50°C pendant 40 à 50 minutes jusqu'à obtention d'un mélange transparent et fluide. Verser lentement le mélange le long du tube PVC, puis laisser à température ambiante pendant deux heures. Placer ensuite l'ensemble à 70°C pendant deux heures. Laisser refroidir à température ambiante. Determine the volume of epoxy resin taking into account the phenomenon of imbibition in the rock (volume equivalent to 0.4 cm of column diameter.) The epoxy resin is composed of 70% of a resin base (Epon 828 - Miller -Stephenson Chemical Company, Inc.) and 30% hardener (Versamid 125 - Miller-Stephenson Chemical Company, Inc.) In a disposable plastic cup, mix the resin with the hardener for 10 minutes, then place the mixture at 50 ° C for 40 to 50 minutes until a transparent and fluid mixture is obtained. Slowly pour the mixture along the PVC tube, then leave at room temperature for two hours. Then place the assembly at 70 ° C for two hours. Allow to cool to room temperature.
Une solution d'eau de mer synthétique est composée d'eau minérale (contenant 35 ppm de S1O2 dissous) dans laquelle sont dissous les sels suivants : A synthetic sea water solution is composed of mineral water (containing 35 ppm of dissolved S1O 2) having dissolved therein the following salts:
Sels Concentration (g/L) Salts Concentration (g / L)
NaCl 24,80 NaCl 24.80
KC1 0,79 KC1 0.79
MgCl2 5,25 MgCl 2 5.25
CaCl2 1,19 CaCl 2 1.19
NaHC03 0,10 NaHC0 3 0.10
Na2S04 4,16 Na 2 S0 4 4.16
A cette solution, est ajouté une quantité connue de d'iodure de potassium - l'ion iodure ayant un comportement de traceur idéal pour les tests de perméation - de manière à se trouver à une concentration de 1 g/L en Kl. L'ensemble est dégazé par agitation vive sous vide pendant 5 à 10 minutes. To this solution is added a known amount of potassium iodide - the iodide ion having an ideal tracer behavior for permeation tests - so as to be at a concentration of 1 g / L in Kl. The mixture is degassed by vigorous stirring under vacuum for 5 to 10 minutes.
Nous disposons de suspensions concentrées dans l'eau ou dans le diéthylène glycol (DEG) nanoparticules, selon les exemples précédents. Nous diluons une quantité connue de ces suspensions dans la solution précédente à un volume de 300 à 500 mL de manière à se trouver à une concentration en particules comprise entre 0,1 et 10 mg/L. La suspension est laissée sous agitation légère pendant 10 minutes, puis filtrée sur une membrane de 0,2 μιη. We have suspensions concentrated in water or diethylene glycol (DEG) nanoparticles, according to the previous examples. We dilute a known amount of these suspensions in the previous solution to a volume of 300 to 500 mL so as to be at a particle concentration of between 0.1 and 10 mg / L. The suspension is stirred gently for 10 minutes and then filtered through a membrane of 0.2 μιη.
Le montage est composé d'une pompe à double seringues permettant de fixer un débit compris entre 1 et 1000 mL par heure, typiquement entre 20 et 100 mL/h. Celle-ci dirige un fluide vers une cartouche contenant la roche poreuse. Le fluide percole à travers celle-ci, la pression différentielle de part et d'autre de la roche est suivie par un capteur. Le fluide est enfin dirigé vers un collecteur de fractions. The assembly consists of a double syringe pump for setting a flow rate of between 1 and 1000 mL per hour, typically between 20 and 100 mL / h. This directs a fluid to a cartridge containing the porous rock. The fluid percolates through it, the differential pressure on both sides of the rock is followed by a sensor. The fluid is finally directed to a fraction collector.
Dans le cas d'une perméation de particules, le fluide utilisé est une suspension diluée de particules et de Kl. Dans le cas d'un lavage de la roche ou un test de désorption de
particules après perméation, le fluide injecté est de l'eau de mer dégazée sans traceurs. In the case of permeation of particles, the fluid used is a diluted suspension of particles and Kl. In the case of a rock wash or a desorption test of particles after permeation, the injected fluid is degassed seawater without tracers.
Dans ces fractions, nous mesurons d'une part l'absorption UV à λ = 254 nm du fluide. Celle-ci est très faible lorsque le fluide ne contient pas d'iodure, et devient importante en présence de celui-ci. L'absorption UV permet donc de suivre la perméation du traceur idéal. D'autre part, nous mesurons la fluorescence des fractions dans des conditions qui permettent de détecter le(s) fluorophore(s) présent(s) dans les particules. Cette technique permet donc de suivre la perméation des particules. In these fractions, we measure on the one hand the UV absorption at λ = 254 nm of the fluid. This is very low when the fluid does not contain iodide, and becomes important in the presence of it. The UV absorption thus makes it possible to follow the permeation of the ideal tracer. On the other hand, we measure the fluorescence of the fractions under conditions that make it possible to detect the fluorophore (s) present in the particles. This technique makes it possible to follow the permeation of the particles.
La roche a les caractéristiques suivantes : The rock has the following characteristics:
Type : Bentheimer Type: Bentheimer
Nature du matériau : grès, avec argiles (< 5%). Nature of the material: sandstone, with clays (<5%).
Dimensions : 5 cm de diamètre ; 12,5 cm de longueur Dimensions: 5 cm in diameter; 12.5 cm long
Perméabilité : 800 mD environ Permeability: about 800 mD
Porosité : 20% Porosity: 20%
Particules utilisées, préparées selon exemple 4. Particles used, prepared according to Example 4.
Le débit imposé par la pompe est de 60 mL/h. Les fractions collectées en sortie de roche sont d'un volume de 5 mL. The flow rate imposed by the pump is 60 mL / h. The fractions collected at the rock outlet are of a volume of 5 mL.
La figure 4 montre une courbe de perméation de nanoparticules préparées selon le procédé de préparation 4 (comprenant une étape de chauffage à 80°C pendant 1 heure) en comparaison avec le contrôle Kl (traceur idéal). Les résultats de perméation montrent que les nanoparticules selon l'invention peuvent être aisément utilisées comme traceurs dans des eaux d'injection. On observe en effet une très bonne corrélation entre les traceurs nanoparticulaires fluorescents et le traceur idéal pris en référence (Kl). En particulier, un taux de passage de nanoparticules supérieur à 99% est obtenu avec un écart moyen par rapport au traceur idéal inférieur à 10%. A la connaissance des inventeurs, de tels résultats n'avaient pas été obtenus avec des nanoparticules, possédant des fluorophores détectable par fluorescence résolue en temps, élaborées avec les procédés de l'art antérieur.
Figure 4 shows a permeation curve of nanoparticles prepared according to Preparation Method 4 (including a heating step at 80 ° C for 1 hour) in comparison with control K1 (ideal tracer). The permeation results show that the nanoparticles according to the invention can easily be used as tracers in injection waters. Indeed, a very good correlation is observed between the fluorescent nanoparticulate tracers and the ideal tracer (Kl). In particular, a passage rate of nanoparticles greater than 99% is obtained with a mean deviation from the ideal tracer of less than 10%. To the knowledge of the inventors, such results have not been obtained with nanoparticles, having fluorophores detectable by fluorescence resolved in time, developed with the methods of the prior art.
Claims
1. Nanoparticules pour leur utilisation dans l'étude d'un gisement pétrolier, lesdites nanoparticules étant caractérisées en ce qu'elles comprennent : 1. Nanoparticles for use in the study of a petroleum field, said nanoparticles being characterized in that they comprise:
i. un cœur constitué d'un métal noble ou d'un alliage de métaux nobles, ii. une matrice comprenant des polysiloxanes et un fluorophore organométallique lié de manière covalente aux polysiloxanes, ladite matrice étant fonctionnalisée à sa surface pour former des liaisons silanes Si-R, lesdits radicaux -R étant constitués pour au moins 50%, de préférence au moins 75% de radicaux hydrophiles neutres ou chargés, de préférence choisis parmi des polyéthers ou des polyols, ou leurs mélanges. i. a heart made of a noble metal or alloy of noble metals, ii. a matrix comprising polysiloxanes and an organometallic fluorophore covalently bound to the polysiloxanes, said matrix being functionalized on its surface to form silane bonds Si-R, said radicals -R being constituted for at least 50%, preferably at least 75% neutral or charged hydrophilic radicals, preferably selected from polyethers or polyols, or mixtures thereof.
2. Nanoparticules selon la revendication 1, caractérisées en ce qu'elles comprennent un cœur essentiellement constitué de particules d'or. 2. Nanoparticles according to claim 1, characterized in that they comprise a core consisting essentially of gold particles.
3. Nanoparticules selon la revendication 1 ou 2, caractérisées en ce qu'elles ont un diamètre moyen inférieur à 100 nm, par exemple compris entre 20 nm et 100 nm, de préférence entre 20 nm et 50 nm et un indice de polydispersité inférieur à 0,3, de préférence inférieur à 0,1. 3. Nanoparticles according to claim 1 or 2, characterized in that they have a mean diameter of less than 100 nm, for example between 20 nm and 100 nm, preferably between 20 nm and 50 nm and a polydispersity index of less than 0.3, preferably less than 0.1.
4. Nanoparticules selon l'une quelconque des revendications 1 à 3, caractérisées en ce que le fluorophore organométallique est choisi parmi les lanthanides, leurs alliages et leurs mélanges, lesdits lanthanides étant liés à des molécules complexantes. 4. Nanoparticles according to any one of claims 1 to 3, characterized in that the organometallic fluorophore is selected from lanthanides, their alloys and mixtures thereof, said lanthanides being linked to complexing molecules.
5. Nanoparticules selon la revendication 4, caractérisées en ce que ladite molécule complexante a une coordinance d'au moins 6 et une constante de dissociation pKd supérieure à 10, de préférence supérieur à 15, de préférence, le DOTA ou l'un de ses dérivés. Nanoparticles according to claim 4, characterized in that said complexing molecule has a coordination of at least 6 and a dissociation constant pKd greater than 10, preferably greater than 15, preferably DOTA or one of its derivatives.
6. Nanoparticules selon l'une quelconque des revendications précédentes, caractérisées en ce que la matrice des nanoparticules est fonctionnalisée de sorte à ce que le potentiel zêta des nanoparticules, mesuré à un pH de 6,5, est inférieur à +10 mV. 6. Nanoparticles according to any one of the preceding claims, characterized in that the matrix of the nanoparticles is functionalized so that the zeta potential of the nanoparticles, measured at a pH of 6.5, is less than +10 mV.
7. Nanoparticules selon l'une quelconque des revendications précédentes, caractérisées en ce que les radicaux -R des silanes Si-R en surface sont constitués pour au moins 50%, de préférence au moins 75%, de radicaux hydrophiles neutres. 7. Nanoparticles according to any one of the preceding claims, characterized in that the -R radicals of silanes Si-R at the surface consist of at least 50%, preferably at least 75%, of neutral hydrophilic radicals.
8. Nanoparticules selon la revendication 7, caractérisées en ce que les radicaux hydrophiles neutres sont choisis parmi les polyols, par exemple le gluconamide, ou les polyéthers, par exemple le polyéthylèneglycol, ou leurs mélanges. 8. Nanoparticles according to claim 7, characterized in that the neutral hydrophilic radicals are chosen from polyols, for example gluconamide, or polyethers, for example polyethylene glycol, or mixtures thereof.
9. Nanoparticules selon l'une quelconque des revendications précédentes, caractérisées en ce que les radicaux -R des liaisons silanes sont présents en surface à raison d'au moins un radical -R par nm2 de surface et de préférence au moins entre 1 et 10 radicaux -R par nm2. 9. Nanoparticles according to any one of the preceding claims, characterized in that the radicals -R of the silane bonds are present on the surface at the level of at least one -R radical per nm 2 of surface and preferably at least between 1 and Radicals -R per nm 2 .
10. Procédé de préparation d'une solution colloïdale de nanoparticules utilisables comme traceurs pour l'étude d'un gisement pétrolier, ledit procédé comprenant les étapes suivantes : 10. A process for preparing a colloidal solution of nanoparticles that can be used as tracers for the study of a petroleum deposit, said process comprising the following steps:
i. on synthétise un cœur de métal noble enrobé d'une matrice de polysiloxane préfonctionnalisée avec des silanes hydrophiles au sein d'une microémulsion inverse, i. a noble metal core coated with a polysiloxane matrix prefunctionalized with hydrophilic silanes is synthesized in an inverse microemulsion,
ii. on extrait une solution colloïdale aqueuse de nanoparticules par décantation après déstabilisation de la microémulsion, par exemple dans un mélange eau/isopropanol, ii. an aqueous colloidal solution of nanoparticles is extracted by decantation after destabilization of the microemulsion, for example in a water / isopropanol mixture,
iii. on chauffe les nanoparticules à au moins 50°C, par exemple, environ 80°C. iii. the nanoparticles are heated to at least 50 ° C, for example about 80 ° C.
11. Procédé selon la revendication 10, caractérisé en ce que les nanoparticules ne sont jamais en phase sèche solide au cours dudit procédé. 11. The method of claim 10, characterized in that the nanoparticles are never dry solid phase during said process.
12. Procédé selon la revendication 10 ou 11, caractérisé en ce que la solution colloïdale de nanoparticules est lavée après l'étape (ii) d'extraction, par exemple par fïltration tangentielle. 12. The method of claim 10 or 11, characterized in that the colloidal solution of nanoparticles is washed after step (ii) of extraction, for example by tangential filtration.
13. Procédé selon l'une quelconque des revendications 10 à 12, caractérisé en ce que l'on transfert la solution colloïdale aqueuse de nanoparticules dans un solvant non aqueux, par exemple un polyol, de préférence du diéthylène glycol, avant l'étape de chauffage. 13. Process according to any one of Claims 10 to 12, characterized in that the aqueous colloidal solution of nanoparticles is transferred into a non-aqueous solvent, for example a polyol, preferably diethylene glycol, before the heater.
14. Procédé selon l'une quelconque des revendications 10 à 13, caractérisé en ce que l'on procède à une post-fonctionnalisation de la matrice des nanoparticules en présence d'un solvant non aqueux, par exemple un polyol, de préférence du diéthylène glycol, avant ou après l'étape de chauffage. 14. Process according to any one of Claims 10 to 13, characterized in that the nanoparticle matrix is post-functionalized by the presence of a non-aqueous solvent, for example a polyol, preferably diethylene glycol, before or after the heating step.
15. Procédé selon l'une des revendications 10 à 14, caractérisé en ce que l'on filtre la solution colloïdale de nanoparticules obtenue après chauffage et/ou post- fonctionnalisation. 15. Process according to one of Claims 10 to 14, characterized in that the colloidal solution of nanoparticles obtained after heating and / or post-functionalization is filtered.
16. Solution colloïdale de nanoparticules, susceptible d'être obtenue par le procédé selon l'une quelconque des revendications 10 à 15. 16. A colloidal solution of nanoparticles, obtainable by the method according to any one of claims 10 to 15.
17. Solution colloïdale de nanoparticules selon la revendication 16, caractérisée en ce que les nanoparticules ont en outre les caractéristiques des nanoparticules définies selon l'une quelconque des revendications 1 à 9. 17. colloidal nanoparticle solution according to claim 16, characterized in that the nanoparticles further have the characteristics of the nanoparticles defined according to any one of claims 1 to 9.
18. Liquide d'injection pour l'étude d'un gisement pétrolier, comprenant des nanoparticules selon l'une quelconque des revendications 1 à 9, ou une solution colloïdale selon l'une des revendications 16 ou 17. 18. An injection liquid for the study of a petroleum deposit, comprising nanoparticles according to any one of claims 1 to 9, or a colloidal solution according to one of claims 16 or 17.
19. Utilisation des nanoparticules telles que définies dans l'une quelconque des revendications 1 à 9 comme traceurs dans des eaux d'injection d'un gisement pétrolier, lesquels sont destinés à l'étude dudit gisement par diffusion au travers de celui-ci, en vue notamment de contrôler les flux entre un puits d'injection et un puits de production et/ou d'évaluer les volumes de pétrole en réserve dans le gisement. 19. Use of the nanoparticles as defined in any one of claims 1 to 9 as tracers in injection waters of a petroleum deposit, which are intended for the study of said deposit by diffusion therethrough, in particular to control the flows between an injection well and a production well and / or to evaluate the volumes of oil in reserve in the deposit.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP14178564.2A EP2813287A3 (en) | 2011-06-22 | 2012-06-22 | Nano-tracers for marking injection water in oil fields |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1155513A FR2976825B1 (en) | 2011-06-22 | 2011-06-22 | NANOTRACTERS FOR THE MARKING OF PETROLEUM FIELD INJECTION WATER |
| PCT/EP2012/062075 WO2012175665A1 (en) | 2011-06-22 | 2012-06-22 | Nanotracers for labeling the injection water in oil fields |
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| Application Number | Title | Priority Date | Filing Date |
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| EP14178564.2A Division EP2813287A3 (en) | 2011-06-22 | 2012-06-22 | Nano-tracers for marking injection water in oil fields |
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| EP14178564.2A Withdrawn EP2813287A3 (en) | 2011-06-22 | 2012-06-22 | Nano-tracers for marking injection water in oil fields |
| EP12728613.6A Withdrawn EP2723487A1 (en) | 2011-06-22 | 2012-06-22 | Nanotracers for labeling the injection water in oil fields |
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| US (1) | US20140323363A1 (en) |
| EP (2) | EP2813287A3 (en) |
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| US10240419B2 (en) | 2009-12-08 | 2019-03-26 | Baker Hughes, A Ge Company, Llc | Downhole flow inhibition tool and method of unplugging a seat |
| US9707739B2 (en) | 2011-07-22 | 2017-07-18 | Baker Hughes Incorporated | Intermetallic metallic composite, method of manufacture thereof and articles comprising the same |
| US9010416B2 (en) | 2012-01-25 | 2015-04-21 | Baker Hughes Incorporated | Tubular anchoring system and a seat for use in the same |
| WO2014203614A1 (en) | 2013-06-19 | 2014-12-24 | コニカミノルタ株式会社 | Fluorescent nanoparticles for biomolecular staining and manufacturing method for same |
| EP2821445A1 (en) * | 2013-07-05 | 2015-01-07 | Danmarks Tekniske Universitet | Method of tracing engineered nanoparticles |
| US10150713B2 (en) | 2014-02-21 | 2018-12-11 | Terves, Inc. | Fluid activated disintegrating metal system |
| US11167343B2 (en) | 2014-02-21 | 2021-11-09 | Terves, Llc | Galvanically-active in situ formed particles for controlled rate dissolving tools |
| US10689740B2 (en) | 2014-04-18 | 2020-06-23 | Terves, LLCq | Galvanically-active in situ formed particles for controlled rate dissolving tools |
| US10865465B2 (en) | 2017-07-27 | 2020-12-15 | Terves, Llc | Degradable metal matrix composite |
| FR3023180B1 (en) * | 2014-07-03 | 2016-08-12 | Commissariat Energie Atomique | USE OF ALUMINOSILICATES FOR MARKING PURPOSES |
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2011
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- 2011-10-25 FR FR1159676A patent/FR2976826B1/en not_active Expired - Fee Related
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2012
- 2012-06-22 US US14/128,194 patent/US20140323363A1/en not_active Abandoned
- 2012-06-22 WO PCT/EP2012/062075 patent/WO2012175665A1/en active Application Filing
- 2012-06-22 EP EP14178564.2A patent/EP2813287A3/en not_active Withdrawn
- 2012-06-22 EP EP12728613.6A patent/EP2723487A1/en not_active Withdrawn
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| WO2012175665A1 (en) | 2012-12-27 |
| FR2976825B1 (en) | 2014-02-21 |
| FR2976825A1 (en) | 2012-12-28 |
| FR2976826A1 (en) | 2012-12-28 |
| EP2813287A2 (en) | 2014-12-17 |
| US20140323363A1 (en) | 2014-10-30 |
| FR2976826B1 (en) | 2013-07-05 |
| EP2813287A3 (en) | 2015-03-04 |
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