Nano-inhibitors

Patent metadata

Field	Value
Publication number	US-2017349810-A1
Application number	US-201415536523-A
Country	US
Kind code	A1
Filing date	Dec 15, 2014
Priority date	Dec 15, 2014
Publication date	Dec 7, 2017
Grant date	—

Abstract

Novel hybrid nanoparticles, useful for inhibiting or slowing down the formation of sulfur deposits or minerals in a well during the extraction of gas or oil. Specifically, the nanoparticles each include (i) a polyorganosiloxane (POS) matrix; and, optionally as a coating over a lanthanide oxide core, (iii) at least one polymeric scale inhibitor during the extraction of gas or oil. The invention also relates to the method for obtaining the nanoinhibitors and the application of same.

First claim

1 . Nanoparticles wherein they each include
(i) a polyorganosiloxane (POS) matrix; (ii) at least one polymeric deposit inhibitor during the extraction of gas or oil.

2 . Nanoparticles according to claim 1 , wherein the mass of the deposit inhibitors represents more than 80% of the total mass of each nanoparticle.

3 . Nanoparticles according to claim 1 , wherein they include a polymeric deposit inhibitor of a molar mass of at least 10 kDa.

4 . Nanoparticles according to claim 1 , wherein the polyorganosiloxane matrix comprises at least 10% (mol/mol) of free amine groups per silica atom.

5 . Nanoparticles according to claim 1 , wherein they include a polymeric deposit inhibitor with a negative charge chosen from polymers or copolymers containing at least one of the following functions:
carboxylic polyacids, sulphonic acid polymers, phosphates or phosphonates, polyphosphinocarboxylic acids, amide functions.

6 . Nanoparticles according to claim 1 , wherein they include a polymeric deposit inhibitor chosen from copolymers of styrene sulphonic acid and (poly)carboxylic acid and copolymers of styrene sulphonic and (poly) amido-amine.

7 . Nanoparticles according to claim 1 , wherein they include furthermore phosphonates.

8 . Nanoparticles according to claim 1 , wherein they have a mean diameter less than 1 μm.

9 . Nanoparticles according to claim 1 , wherein the polyorganosiloxane matrix is functionalised by —R groups.

10 . Nanoparticles according to claim 1 wherein they do not include a lanthanide oxide core.

11 . Nanoparticles according to claim 1 wherein the deposit inhibitors are connected to the polyorganosiloxane matrix by non-covalent electrostatic connections.

12 . Method for obtaining nanoparticles according to claim 1 comprises the following steps:
a. optionally synthesising a core with a lanthanide oxide base,
b. coating the cores of the step (a) with polyorganosiloxane (POS) or preparing a nanoparticle polyorganosiloxane, consisting primarily in implementing a sol/gel technique of hydrolysis-condensation of silicic and alkoxysilane species, in the presence of a base or an acid;
c. overcoating the nanoparticles obtained in step (b) consisting primarily in bringing these coated cores or polyorganosiloxane nanoparticles of the step (b) in contact with a solution of polymeric deposit inhibitors in the presence of a non-aqueous solvent,
d. optionally purification of the nanoparticles;
e. optionally dissolving the cores of lanthanides oxides of the nanoparticles of the step (b) or overcoated nanoparticles of the step (c) consisting primarily in putting them in the presence of a pH modifying agent and/or of a chelator able to complex all or a portion of the lanthanide cations, in such a way that the diameter of the nanoparticles without the overcoating is reduced to a value between 1 and 20 nm;
the steps (c), (d), and (e) are able to be carried out in a different order or at the same time.

13 . Suspension of nanoparticles according to claim 1 and/or obtained by the method for obtaining nanoparticles comprising the following steps:
a. optionally synthesising a core with a lanthanide oxide base,
b. coating the cores of the step (a) with polyorganosiloxane (POS) or preparing a nanoparticle polyorganosiloxane, consisting primarily in implementing a sol/gel technique of hydrolysis-condensation of silicic and alkoxysilane species, in the presence of a base or an acid;
c. overcoating the nanoparticles obtained in step (b) consisting primarily in bringing these coated cores or polyorganosiloxane nanoparticles of the step (b) in contact with a solution of polymeric deposit inhibitors in the presence of a non-aqueous solvent,
d. optionally purification of the nanoparticles;
e. optionally dissolving the cores of lanthanides oxides of the nanoparticles of the step (b) or overcoated nanoparticles of the step (c) consisting primarily in putting them in the presence of a pH modifying agent and/or of a chelator able to complex all or a portion of the lanthanide cations, in such a way that the diameter of the nanoparticles without the overcoating is reduced to a value between 1 and 20 nm;
the steps (c), (d), and (e) are able to be carried out in a different order or at the same time.

14 . Injection liquid for inhibiting or slowing down the formation of deposits during the exploitation of gas or oil, it comprises nanoparticles according to claim 1 and/or, nanoparticles obtained by the method for obtaining nanoparticles comprising the following steps:
a. optionally synthesising a core with a lanthanide oxide base,
b. coating the cores of the step (a) with polyorganosiloxane (POS) or preparing a nanoparticle polyorganosiloxane, consisting primarily in implementing a sol/gel technique of hydrolysis-condensation of silicic and alkoxysilane species, in the presence of a base or an acid;
c. overcoating the nanoparticles obtained in step (b) consisting primarily in bringing these coated cores or polyorganosiloxane nanoparticles of the step (b) in contact with a solution of polymeric deposit inhibitors in the presence of a non-aqueous solvent,
d. optionally purification of the nanoparticles;
e. optionally dissolving the cores of lanthanides oxides of the nanoparticles of the step (b) or overcoated nanoparticles of the step (c) consisting primarily in putting them in the presence of a pH modifying agent and/or of a chelator able to complex all or a portion of the lanthanide cations, in such a way that the diameter of the nanoparticles without the overcoating is reduced to a value between 1 and 20 nm;
the steps (c), (d), and (e) are able to be carried out in a different order or at the same time;
and/or the suspension of nanoparticles.

15 . Method for obtaining nanoparticles according to claim 1 comprising the following steps:
a. optionally synthesising a core with a lanthanide oxide base,
b. coating the cores of the step (a) with polyorganosiloxane (POS) or preparing a nanoparticle polyorganosiloxane, consisting primarily in implementing a sol/gel technique of hydrolysis-condensation of silicic and alkoxysilane species, in the presence of a base or an acid;
c. overcoating the nanoparticles obtained in step (b) consisting primarily in bringing these coated cores or polyorganosiloxane nanoparticles of the step (b) in contact with a solution of polymeric deposit inhibitors in the presence of a non-aqueous solvent,
d. optionally purification of the nanoparticles;
e. optionally dissolving the cores of lanthanides oxides of the nanoparticles of the step (b) or overcoated nanoparticles of the step (c) consisting primarily in putting them in the presence of a pH modifying agent and/or of a chelator able to complex all or a portion of the lanthanide cations, in such a way that the diameter of the nanoparticles without the overcoating is reduced to a value between 1 and 20 nm;
the steps (c), (d), and (e) are able to be carried out in a different order or at the same time;
and/or a suspension of nanoparticles, in order to inhibit or slow down the formation of sulphur and/or mineral deposits during the extraction of gas of oil.

16 . The method according to claim 15 , in order to inhibit or slow down the formation of sulphur and/or mineral deposits during the extraction in an oil or gas well operating at more than 10 MPa.

17 . The method according to claim 15 , in the form of an injection of the nanoparticles in squeeze.

Assignees

• Total Sa
• Univ Claude Bernard Lyon
• Centre National De La Rech Scientifique-Cnrs-
• Centre National De La Recherche Scient -Cnrs-

Inventors

• Hurtevent Christian
• Baraka-Lokmane Salima
• Ordonez-Varela John-Richard
• Tillement Olivier
• Marais Arthur
• Moussaron Albert

Classifications

• C09K8/528

  inorganic depositions, e.g. sulfates or carbonates · CPC title

• C09K2208/10

  Nanoparticle-containing well treatment fluids · CPC title

• B01J13/14

  Polymerisation; cross-linking · CPC title

• C08L83/08

  containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen · CPC title

• C09K8/035

  Organic additives · CPC title