CN107018666A - Suspension and the method using the suspension recovery hydro carbons for strengthening hydrocarbon recovery - Google Patents

Suspension and the method using the suspension recovery hydro carbons for strengthening hydrocarbon recovery Download PDF

Info

Publication number
CN107018666A
CN107018666A CN201580064674.0A CN201580064674A CN107018666A CN 107018666 A CN107018666 A CN 107018666A CN 201580064674 A CN201580064674 A CN 201580064674A CN 107018666 A CN107018666 A CN 107018666A
Authority
CN
China
Prior art keywords
suspension
amphiphilic nanoparticles
amphiphilic
carbon core
nanoparticles
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.)
Pending
Application number
CN201580064674.0A
Other languages
Chinese (zh)
Inventor
R·苏雷什
O·V·库兹涅佐夫
S·查克拉博蒂
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Baker Hughes Holdings LLC
Original Assignee
Baker Hughes Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US14/519,728 external-priority patent/US9708896B2/en
Application filed by Baker Hughes Inc filed Critical Baker Hughes Inc
Publication of CN107018666A publication Critical patent/CN107018666A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/92—Compositions for stimulating production by acting on the underground formation characterised by their form or by the form of their components, e.g. encapsulated material
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH DRILLING; MINING
    • E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH DRILLING; MINING
    • E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
    • E21B43/20—Displacing by water
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/10—Nanoparticle-containing well treatment fluids

Abstract

The present invention relates to the suspension comprising amphiphilic nanoparticles and at least one carrier fluid.The amphiphilic nanoparticles can be formed by carbonaceous material and at least include hydrophilic parts and hydrophobic parts.The hydrophilic parts are comprising at least one hydrophilic functional group and the hydrophobic parts include at least one hydrophobic functional groups.The method that hydrocarbon materials are removed the invention discloses the method for forming displacement suspension and using the displacement suspension.

Description

For strengthening the suspension of hydrocarbon recovery and using the suspension recovery hydro carbons Method
Prioity claim
This application claims submit on October 21st, 2014 on " SUSPENSIONS FOR ENHANCED OIL RECOVERY, AND METHODS OF RECOVERING HYDROCARBONS USING THE SUSPENSIONS " U.S. The rights and interests of the applying date of patent application serial number 14/519,728, the patent application be submit on January 31st, 2014 on “NANO-SURFACTANTS FOR ENHANCED HYDROCARBON RECOVERY,AND METHODS OF FORMING The continuation application of AND USING SUCH NANO-SURFACTANTS " U.S. Patent Application Serial Number 14/169,432, these Each disclosure is integrally incorporated herein in the way of its reference in document.
Technical field
The embodiment of the disclosure relates generally to form stabilized emulsion and hydrocarbon materials is extracted from subsurface formations Method and system.
Background
Water drive is the conventional method that hydrocarbon materials (such as crude oil, natural gas) are extracted in a kind of enhancing from subsurface formations. In this method, aqueous fluid (such as water, salt solution) is injected so as to will be contained in underground by subsurface formations by injection well Hydrocarbon materials in the clearance space (such as hole, crackle, crack, passage) of layer are driven in the recovery well for being swept to and being offset with injection well. One or more additives can be added in aqueous fluid to aid in the extraction and follow-up processing of hydrocarbon materials.
For example, in certain methods, surfactant, solid particle (such as colloid) or two are added in aqueous fluid Person.Surfactant and/or solid particle can adhere to or be gathered in the interface between hydrocarbon materials and hydrous material so as to shape The stabilized emulsion in the another one of hydrocarbon materials and hydrous material is dispersed in into one of hydrocarbon materials and hydrous material.For example exist Hydrocarbon is mutually dispersed in the emulsion in aqueous phase, and surfactant can reduce the surface tension between hydrocarbon phase and aqueous phase.Pass through surface Interfacial tension between the steady decrease hydrocarbon and water of activating agent, solid particle or both and reduce system capacity, it is to avoid scattered Material (such as hydrocarbon materials or hydrous material) coalescence, and maintain a kind of material to be dispersed in the form of unit (such as drop) In whole another material.Reduction surface tension makes the permeability and mobility of hydrocarbon materials all increase.Therefore, with not using addition The water drive of surfactant and/or solid particle is compared, and hydrocarbon materials can be conveyed more easily in subsurface formations and from ground Extracted in lower stratum.The validity of emulsion is most of by emulsions stable and to be ensured the ability of two-phase mixtures and determines.
However, the application of surfactant is generally by the cost of chemicals and its suction on the rock of hydrocarbon containing formation Echo the limitation of loss.Disadvantageously, there is dissolving salt (for example, being such as generally present in the various salt in subsurface formations) In the case of, the validity of various surfactants may be reduced adversely.In addition, surfactant, which may have, is attached to underground Surface of stratum tendency, it is necessary to more surfactants are added into the aqueous fluid of injection come make up these loss, this It is unfavorable in economics.During follow-up processing, it may be difficult to remove solid particle from stabilized emulsion, so that anti- Only hydrocarbon materials and its hydrous material are agglomerated into different immiscible components, and greatly hinder separating for hydrocarbon materials Collect.In addition, the surfactant usually only function or stably within the scope of specific temperature, and meeting with subsurface formations The high temperature of chance or it is various under the conditions of possible loss function.
Disclosure
Embodiment disclosed herein includes the method that hydrocarbon materials are reclaimed from subsurface formations or from tar sand, Yi Jixiang The stabilized emulsion of pass.For example, according to an embodiment, a kind of method of recovery hydrocarbon materials include will comprising carbon core, at least The amphiphilic nanoparticles of one hydrophilic group and at least one hydrophobic group combine to form suspension with carrier fluid；With making underground At least one of layer and slurry comprising tar sand and water contacts with the suspension amphipathic to be received so as to be formed by described The stabilized emulsion of rice grain；And remove hydro carbons from by the stabilized emulsion of the amphiphilic nanoparticles.
In other embodiments, a kind of method that hydro carbons is removed from subsurface formations is included in comprising CNT, richness Formed at least on one surface of the carbonaceous material of at least one for strangling alkene, carbon Nano diamond, graphene and graphene oxide One hydrophilic group；The carbonaceous material is mixed with carrier fluid to form suspension；The suspension is introduced into subsurface formations And make the hydrocarbon in the subsurface formations contact with the carrier fluid suspension to be formed by the stabilized breast of the carbonaceous material Liquid；And the emulsion is delivered to the surface of the subsurface formations.
In other embodiments, for removing the suspension of hydro carbons from subsurface formations comprising multiple carbon containing amphipathic Nano particle, the amphiphilic nanoparticles include positioned at the carbonaceous material a surface on hydrophobic functional groups and Hydrophilic functional group on another surface of the carbonaceous material.The suspension also includes carrier fluid carrier fluid.
Brief description
Although specification is terminated with claims, claims, which are particularly pointed out and are distinctly claimed, to be considered as Those of embodiment of the present invention, when being read in conjunction with the figure, can pass through some embodiments below with the disclosure Description more easily determine the disclosure embodiment advantage, wherein：
Figure 1A to Fig. 1 C is the rough schematic view of the amphiphilic nanoparticles of the embodiment according to the disclosure；
Fig. 2 is that description is flowed according to a kind of the simplifying for method that hydro carbons is extracted from subsurface formations of the embodiment of the disclosure Cheng Tu；And
Fig. 3 is simple flow of the description according to a kind of method that hydro carbons is reclaimed from tar sand of the embodiment of the disclosure Figure.
Invention embodiment
Figure shown herein does not represent the real views of any specific material, component or system, and is only to use Represented come the idealization for the embodiment for describing the disclosure.
Description provides specific detail, such as material type, composition and processing conditions, so as to provide to the disclosure below Embodiment deep description.However, it will be apparent to those skilled in the art that the embodiment of the disclosure can not use these Detail is put into practice.In fact, the embodiment of the disclosure can be put into practice with reference to the routine techniques industrially used.Hereafter In those necessary process states of embodiment and structure for understanding the disclosure are only described in detail.From subsurface formations or from drip Other behaviors of hydrocarbon materials or material are extracted in blue or green sand (such as oil-sand, Tar sands) to be carried out by conventional technique.
The method that present invention description forms the amphiphilic nanoparticles with difunctional.Term as used in this article " nano particle " means and is less than about 1,000nm particle including averaged particles width or diameter.As used in this article " two Parent's property nano particle " means and including showing the nano particle of two kinds of property of hydrophily and hydrophobicity (such as with Janus nanometers Particle is similar).Amphiphilic nanoparticles can include two-dimensional structure, and the side of the structure shows hydrophobic character and the knot Another opposite side of structure shows hydrophilic characteristics.For example, amphiphilic nanoparticles can include hydrophily and hydrophobic functional groups. In other embodiments, amphiphilic nanoparticles can be formed by hydrophobic core material, and the hydrophobic core material At least side or a part can be by hydrophilic functional groups come functionalization.With the conventional granulates surfactant for stable emulsion Compare, including the surfactant of the amphiphilic nanoparticles can have higher surface area, and in higher temperature With can be stable under salinity.In addition, the functional group on amphiphilic nanoparticles can be formulated into and differently descend ring The various mediums interaction in border.
Amphiphilic nanoparticles can be assembled, adhere to and/or be adsorbed on the mineral matter in subsurface formations, can be adsorbed to On the interface of hydrocarbon materials and hydrous material or it is adsorbed on both.Amphiphilic nanoparticles can be formed comprising multiple units The stabilized emulsion (such as Pickering emulsions) of one of hydrocarbon materials and hydrous material.Term " emulsion " as used in this article Refer to that a kind of immiscible fluid drop is dispersed in the suspension in one other fluid.Emulsion can reduce continuous phase with disperseing Interfacial tension between phase.Hydrocarbon (such as oily) can be increased by reducing the interfacial tension for example disperseed between hydrocarbon phase and continuous aqueous phase Mobility and reclaim from subsurface formations or from the tar sand slurry including hydrocarbon.
Amphiphilic nanoparticles can be formulated into be maintained between polarity phase and nonpolar phase, aqueous favoring and hydrophobic phase it Between and/or the interface between hydrocarbon phase and aqueous phase, be such as maintained at interface, liquid hydrocarbon phase and water between gas phase and aqueous phase Interface or solid phase between phase and the interface between at least one of aqueous phase and hydrocarbon phase.Amphiphilic nanoparticles can make hydrocarbon The emulsion-stabilizing of phase is in aqueous phase or makes the emulsion-stabilizing of aqueous phase in hydrocarbon phase.Emulsion-stabilizing is set to prevent emulsion in emulsion circle Face is coalesced when being formed.The side (such as water-wet side) of amphiphilic nanoparticles, which can be formulated into, is attracted to water Phase, and the opposite side (such as hydrophobic side) of amphiphilic nanoparticles can be formulated into and be attracted to hydrocarbon phase.
The amphiphilic nanoparticles formed by method described herein can have the surface higher than conventional surfactants Product.The functionalized surfaces of amphiphilic nanoparticles can be formulated into interfacial interaction between hydrocarbon phase and aqueous phase or with ground In lower stratum the surface of solids (such as mineral matter) interaction, be consequently formed continuous aqueous phase or hydrocarbon phase with hydrocarbon phase and aqueous phase separately The stable emulsion of the dispersed phase of one.Emulsion intercalation method can be controlled by one or more in the following manner：Control amphiphilic Property solubility of the nano particle in aqueous phase, the pH of control emulsion and/or aqueous phase and the surface for controlling amphiphilic nanoparticles Electric charge.
With reference to Figure 1A, amphiphilic nanoparticles 100 are shown.Amphiphilic nanoparticles 100 can include base portion.Amphiphilic Property nano particle 100 can include hydrophilic parts 102 and hydrophobic parts 104.The surface of base portion can be entered by functional group Row improvement is so as to the physics and chemical property needed for being assigned to the surface of amphiphilic nanoparticles 100.For example, hydrophilic parts 102 can include at least one hydrophilic functional group on base portion surface, and hydrophobic parts 104 can include At least one hydrophobic group on base portion surface.In other embodiments, hydrophobic parts 104 can be by base portion Formed, and hydrophilic parts 102 can include at least one hydrophilic functional group on hydrophobic base part surface.
Base portion can include that chemical modification can be carried out with functional group to form hydrophilic parts 102 and hydrophobicity Any material of part 104.In some embodiments, base portion includes silica matrix.In other embodiments, Base portion includes metal or metal oxide.For example, base portion can include metal, such as iron, titanium, germanium, tin, lead, zirconium, Ruthenium, nickel, cobalt, its oxide and combinations thereof.Again in other embodiments, base portion can include carbon section bar material, such as carbon Nanotube (such as single-walled carbon nanotube (SWCNT), multi-walled carbon nanotube (MWCNT) and combinations thereof), carbon Nano diamond, stone At least one of ink, graphene, graphene oxide, fullerene, green onion shape structure (such as " Buckie green onion ").Therefore, base portion Silica, metal, such as iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, cobalt, CNT, carbon Nano diamond, stone can be included One of black alkene, graphene oxide, fullerene, Buckie green onion and combinations thereof.
Amphiphilic nanoparticles 100 can be formed by multiple hydrophylic precursors and multiple hydrophobicity precursors.As made herein Term " hydrophylic precursor " include with carbon, silicon, iron, titanium, germanium, tin, lead, zirconium, ruthenium, at least one atom of nickel and cobalt and The material of at least one hydrophilic functional group.Term " hydrophobicity precursor " as used in this article include with carbon, silicon, iron, titanium, Germanium, tin, lead, zirconium, ruthenium, at least one atom and the material of at least one hydrophobic functional groups of nickel and cobalt.In some embodiment party In case, multiple hydrophylic precursors can react to form nano particle, the nano particle include carbon, silica, The matrix of at least one of metal and metal oxide, the stromal surface is connected with one or more hydrophilic functional groups.Parent The hydrophilic functional group of aqueous fractions 102 can be formed by the hydrophilic functional group of hydrophylic precursor.
The surface of base portion can carry out chemical modification to form amphiphilic nanoparticles 100, described amphipathic to receive Rice grain 100 also includes hydrophobic parts 104 in addition to hydrophilic parts 102.Hydrophobic parts 104 can be by being connected to matrix The hydrophobic group of part surface is formed.Hydrophobic group can include non-polar group, such as alkyl chain.When base portion by carbon (for example, CNT, carbon Nano diamond, graphite, graphene, graphene oxide, fullerene, Buckie green onion etc.) formed when, hydrophobicity portion Divide 104 can be made up of base portion, and hydrophily portion can be formed at least some surfaces of hydrophobic base part Divide 102.Hydrophilic parts 102 are dissolved in aqueous phase, and hydrophobic parts 104 are dissolved in organic phase.
Amphiphilic nanoparticles 100 are formed as variously-shaped.Can be by making amphiphilic nanoparticles 100 be led in structure Grow to control the shape of amphiphilic nanoparticles 100 in the presence of to agent.The non-limiting examples of structure directing agent include poly- Compound, such as polypyrrole (for example, polyvinylpyrrolidone (PVP)), oxidation polypyrrole, diphenyl ester and cetyl trimethyl Ammonium bromide (CTAB).With continued reference to Figure 1A, amphiphilic nanoparticles 100 can include having solid hydrophilic parts 102 and sky The tubulose matrix of central, tubular hydrophobic parts 104.The amphiphilic nanoparticles 100 formed by SWCNT and MWCNT can be such as figure Tubulose shown in 1A.With reference to Figure 1B, being generally in the shape of for amphiphilic nanoparticles 100 is spherical, is hydrophily portion on side Divide on 102 and opposite side is hydrophobic parts 104.Amphipathic received by what carbon Nano diamond, fullerene and Buckie green onion were formed Rice grain 100 can present spherical shown in Figure 1B.With reference to Fig. 1 C, amphiphilic nanoparticles 100 can have chip shape.Thin slice Side can be hydrophilic parts 102, and the opposite side of thin slice can be hydrophilic parts 104.When amphiphilic nano When grain 100 is formed by the matrix including graphene or graphene oxide, amphiphilic nanoparticles 100 can have as is shown in fig. 1C Chip shape.
In some embodiments, before hydrophobic parts 104 are formed, the hydrophilic of amphiphilic nanoparticles 100 is formed Property part 102.In some embodiments, hydrophilic parts 102 are formed by hydrolyzing hydrophylic precursor.Hydrophylic precursor can With including with general formula RnSiX(4-n)Organosilan, wherein X is hydrolyzable groups, such as alkoxy, acyloxy, amine or halogenation Thing group, and RnIncluding hydrophilic functional group.Term " hydrolyzable groups " as used in this article means and including can be with By hydrolysis (cracking chemical bond by being reacted with water) at least in part depolymerization to reduce the group of molecular weight unit.Can water Solution group can react with hydrous material (such as water).
Hydrophylic precursor can also include one or more hydrophilic functional groups, such as hydroxyl in addition to hydrolyzable groups (–OH-), carboxyl (- COOH-), carbonyl (- C=O), amino (- NH3 +、-NH2,-NHR ,-NRR', wherein R and R' include alkyl, it is all Such as alkyl, alkenyl, alkynyl, aryl, its can each include one or more hydrogen atoms by one or more halogen ions, hydroxyl, Amido or sulfur-containing group substitution), mercapto (- SH), phosphate radical (- PO4 3-) or other hydrophilies or polar functional group.
In some embodiments, the carbonaceous material for forming base portion can include the function of one or more exposures Group, such as hydroxyl, carboxyl, carbonyl, amino, mercapto, phosphate radical, azo group or another hydrophily or polar functional group.Lift For example, CNT can include one on the outside of CNT or at least side of inner side (for example, inwall or outer wall) Individual or multiple hydrophilic functional groups.In other embodiments, graphite flake, graphene platelet or graphene oxide thin slice be extremely Few side can be functionalized by the hydrophilic functional group of at least one type.
For non-limiting examples, carbonaceous material can be by being carried out by concentrated nitric acid, sulfuric acid and combinations thereof oxidation Functionalization.Oxidation can be on the exposed surface of carbonaceous material, such as on the side wall of CNT or in graphene platelet Carboxyl is formed on exposed surface.Exposed carboxyl can form the reactive site for further functionalization carbonaceous material.One In a little embodiments, exposed carboxyl can be exposed to amine (one-level amine (RNH2), secondary amine (RR'NH) or tertiary amine (RR'R " N), wherein R, R' and R " includes alkyl, such as alkyl, alkenyl, alkynyl, aryl, and it is former that it can each include one or more hydrogen Son is replaced by one or more halogen ions, hydroxyl, amido or sulfur-containing group), alkanolamine (including hydroxyl and NH2, NHR and At least one of NRR' compound, wherein R and R' are included above for the identical group described in amine) so as to form amine-functionalized Nanotube.The hydrophilic group being connected with hydrophobicity containing carbon matrix can be formed by being connected to the amido containing carbon matrix.
In other embodiments, the hydroxyl of the exposure of carbon containing core can be with other hydrophylic precursors including terminal hydroxyl React in the condensation reaction so that hydrophilic parts 102 are connected to carbonaceous material.Only for example, the end of carbonaceous material Terminal hydroxy group can be with such as hydroxylamine (for example, HO-NRR', wherein R and R' are including alkyl as described above and including at least One hydrogen is replaced by least one in halogen ion, hydroxyl, amido and sulfur-containing compound) material occur in the condensation reaction instead Should.
Hydrophylic precursor can include TMOS, positive esters of silicon acis, amino silane, silanol, epoxy silane, metal oxidation Thing, hydroxide, metal hydroxides or its combination.Term " TMOS " as used in this article mean and also including comprising There is the material for the silicon atom (for example ,-Si-OR, wherein R are hydrocarbon materials or hydrogen) being bonded with least one oxygen atom.As herein The term " positive esters of silicon acis " used means and including including the silicon atom with four oxygen atom bonds (for example, Si (OR)4, Wherein R is hydrocarbon materials or hydrogen) material.
Hydrophylic precursor can include positive esters of silicon acis, such as positive quanmethyl silicate, tetraethyl orthosilicate (TEOS), positive silicic acid Orthocarbonate, trimethylmethoxysilane, triethyl-ethoxy-silicane alkane or tripropyl npropoxysilane.Trimethylmethoxysilane, The hydrolysis of triethyl-ethoxy-silicane alkane or tripropyl npropoxysilane can form silanol, such as respectively trimethyl silanol, three second Base silanol or tripropyl silanol.In other embodiments, hydrophylic precursor includes Ethoxysilane, such as trimethoxy silicon Alkane, triethoxysilane or tributyl (ethyoxyl) silane.
In other embodiments, hydrophylic precursor includes metal hydroxides and metal salt.For example, hydrophylic precursor can With including metal hydroxides, such as iron hydroxide, titanium hydroxide (such as TiO (OH)2、Ti(OH)4), hydroxide germanium, hydroxide Tin, lead hydroxide, zirconium hydroxide, hydroxide ruthenium, nickel hydroxide and cobalt hydroxide.In some embodiments, hydrophylic precursor Include the salt of metal salt, such as at least one of iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel and cobalt.In some embodiments, wrap Including the hydrophylic precursor of metal hydroxides can react with the hydroxyl of exposure in nano particle stromal surface.
In other embodiments, hydrophylic precursor includes metal oxide.For example, hydrophylic precursor can include oxidation Iron (Fe2O3、Fe3O4), titanium dioxide, germanium oxide (GeO, GeO2), tin oxide (SnO, SnO2), lead oxide (PbO, PbO2、 Pb3O4), zirconium oxide, ruthenium-oxide (RuO2、RuO4), nickel oxide (NiO, Ni2O3) and cobalt oxide (CoO, Co2O3、Co3O4).At it In its embodiment, hydrophylic precursor can include metal alkoxide.For example, hydrophylic precursor can include ethanol iron, isopropanol Titanium, titanium ethanolate, ethanol germanium, ethanol tin, ethanol lead, ethanol zirconium and methanol nickel (II).
In other embodiments, hydrophylic precursor can include the amino silane of at least one amino.It is described At least one amino can be in addition at least two TMOS bases.The non-limiting examples of suitable amino silane include (3- aminopropyls)-diethoxy-methyl-monosilane (APDEMS), (3- aminopropyls)-trimethoxy silane (APTMS), (3- ammonia Base propyl group)-methyldiethoxysilane, (3- aminopropyls)-triethoxysilane (APTES), 3- aminopropyl triethoxies Silane, double (3- triethoxysilylpropyltetrasulfides) amine and double (3- trimethoxy-silylpropyls) amine.Amino TMOS Hydrolysis can form the hydroxy-end capped hydrophilic parts 102 including amino.In some embodiments, amino silane can be with Such as ethylene carbonate reaction includes the hydrophilic parts 102 of exposed hydroxyl so as to be formed.
In other embodiments, hydrophylic precursor can include epoxy silane.The non-limiting examples bag of epoxy silane Include 3- glycidyloxypropyls trimethoxy silane, 3- glycidyloxypropyls methyldiethoxysilane and 3- contractings Water glyceryl epoxide propyl-triethoxysilicane.Epoxy silane can be hydrolyzed to form exposure in hydrophilic parts 102 Hydroxyl.
The synthesis of the hydrophilic parts 102 of amphiphilic nanoparticles 100 can be carried out in polar solvent.Hydrophilic parts 102 dissolve in solvent.Solvent can include alcohol, such as methanol, ethanol, propyl alcohol, butanol, amylalcohol, other alcohol, acetone or its group Close.Hydrophylic precursor is dissolved in solvent.
Other reagents can be added into reaction solution.For example, can into reaction solution mixed structure directed agents, such as gather Vinylpyrrolidone (PVP).The pH of reaction solution can be changed by adding various acid or alkali.For example, can be by molten Sodium acid carbonate, sodium hydroxide or other alkali are added in liquid increases the pH of solution.Can by added into solution such as hydrochloric acid, Acetic acid or other sour acid reduce the pH of solution.
The synthesis of hydrophilic parts 102 can be carried out at room temperature.In some embodiments, reaction solution can be carried out Heating is so as to increase the reaction rate for the hydrophilic parts 102 to form amphiphilic nanoparticles 100.In other embodiments, Reaction rate can be increased by microwave radiation.Reaction can continue to carry out about one minute between a few hours.In some realities Apply in scheme, can form the generated time of hydrophilic parts 102 to increase the size of hydrophilic parts 102 by increase. In embodiment by hydrolyzing to form hydrophilic parts 102, reaction can leave one or more in hydrophilic parts 102 Exposed hydroxyl.Hydrophilic parts 102 can include one or more extra functional groups, such as extra hydroxyl, carboxyl, carbonyl Base, amino, mercapto and phosphate radical.
Hydrophylic precursor can hydrolyze to form the hydrophylic precursor of multiple hydroxyls with exposure.Hydrophylic precursor Exposure hydroxyl can be reacted with each other in the condensation reaction, and formation includes host material and the hydrophily on host surface The hydrophilic parts 102 of functional group.Exposed functional group can be the identical functional group of functional group with hydrophylic precursor.It is hydrophilic Property part 102 surface can have universal architecture as follows, wherein RnIncluding hydrophilic group, and M be carbon, silicon, iron, titanium, At least one of germanium, tin, lead, zirconium, ruthenium, nickel and cobalt.Wherein M be carbon or metal (for example, iron, titanium, germanium, tin, lead, zirconium, ruthenium, Nickel and cobalt) embodiment in, adjacent metallic atom can be bonded and the oxygen atom without insertion directly with one another, and carbon section bar Material can include hydrophily substitution (for example, adjacent carbon atom can directly with one another be bonded or can be by hydrophilic functional group Connection).
Hydrophobicity precursor can be added into the reaction solution including hydrophilic parts 102.Can be into reactant mixture Add hydrophobicity precursor solvable organic solvent wherein.In some embodiments, organic solvent is non-polar solven.It is hydrophobic The hydrophobic functional groups of property precursor are solvable in organic phase, and the hydrophilic functional group on host surface can in aqueous phase It is molten.
Can be by the hydroxyl and one or more hydrophobicity precursors reactions of at least some exposures for making hydrophilic parts 102 To form amphiphilic nanoparticles 100.Hydrophobicity precursor can include the hydroxyl of one or more exposures.In some embodiments In, hydrophobicity precursor is hydrolyzed and exposed hydroxyl is produced on hydrophobicity precursor.
In some embodiments, hydrophobic parts 104 are grown from one end of hydrophilic parts 102.Not by any theory Constraint, it is believed that due to hydrophilic parts 102 in non-polar solven it is insoluble, only some hydrophilic parts 102 contact wherein It is dissolved with the non-polar solven of hydrophobicity precursor.Contact hydrophobicity precursor (for example hydrophilic parts 102 non-polar solven and Interface between polar solvent) the hydroxyls of a part of hydrophilic parts 102 can be with hydrophobicity precursors reaction so as to being formed The hydrophobic parts 104 of amphiphilic nanoparticles 100.The exposed surface of hydrophobic parts 104 can have as shown below logical With structure, wherein RmIncluding hydrophobic functional groups, and Μ be carbon, silicon, iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel and cobalt at least One.In Μ in the embodiment of metal (such as iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel and cobalt), adjacent metallic atom can The oxygen atom without insertion to be bonded directly with one another.
Amphiphilic nanoparticles 100 can include the Hydrophobic non-polar of one or more exposures from hydrophobicity precursor Organic group and from hydrophylic precursor one or more functional groups (for example, hydroxyl, carboxyl, carbonyl, amino, mercapto, Phosphate radical, metal, metal oxide).
Hydrophobicity precursor can include the TMOS comprising apolar organic components.Hydrophobicity precursor can be included at least One central atom (such as carbon, silicon, iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel and cobalt), one be bonded with the central atom Or multiple alkyl and one or more alkoxies with central atom bond.In other embodiments, before hydrophobicity Body includes the hydrocarbon being bonded with isocyanate functional group (- N=C=O), such as isocyanic acid octadecane ester.In some embodiments, Alkyl is alkyl, such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, dodecyl and/or octadecyl, alkane virtue Base, the benzyl such as connected by aryl moiety (such as 4- aminomethyl phenyls, 4- hydroxymethyl phenyls or 4- (2- ethoxys) phenyl, And/or benzyl (alkyl) position is such as connected in phenyl methyl and 4- hydroxyphenylmethyls and/or such as in phenethyl and 4- hydroxyls The aralkyl of 2 is connected in base phenethyl)；Lactone group, imidazole radicals and pyridine radicals.In some embodiments, alkoxy is Methoxyl group, ethyoxyl, propoxyl group or butoxy.Hydrophobicity precursor can include alkoxy silane, such as trialkoxy silane, bag Include trimethoxy silane, isobutyl triethoxy silane, trimethoxysilane, vinyltrimethoxy silane, 16 Alkyl trimethoxysilane (HDTMOS), MTMS, ethyl trimethoxy silane, octyl group trimethoxy silane, Octyltri-ethoxysilane or other TMOSs.
Hydrophobicity precursor can include being configured on the surface of amphiphilic nanoparticles 100 form hydrophobicity official The compound that can be rolled into a ball.In some embodiments, the matrix that the hydroxyl of alcohol or hydrophobicity precursor can be with amphiphilic nanoparticles On exposure hydroxyl react in the condensation reaction so as to forming hydrophobic parts 104.For non-limiting examples, hydrophobicity Precursor can form hydrophobic parts 104 with the exposure hydroxyl reaction on carbonaceous material.In other embodiments, it is hydrophobic Property precursor hydroxyl can in the condensation reaction be reacted with the exposure hydroxyl of hydrophilic parts 102 so as to forming hydrophobic parts 104.Only for example, hydrophobicity precursor can include the alcohol with general formula R R'R "-OH, and wherein R, R' and R " can include hydrogen Or organic group, alkyl, alkenyl, alkynyl, aryl etc..The alcohol can include one or more hydroxyls (such as glycol, three Alcohol etc.).Hydrophobic parts 104 can be only formed on the side of amphiphilic nanoparticles 100 (for example, opposite side is as hydrophilic Property part 102).
Dredging for hydrophobic parts 104 can be controlled by changing the number of functional groups and functional group size of hydrophobicity precursor It is aqueous.In some embodiments, hydrophobic parts 104 are increased by the carbon content for the functional group for increasing hydrophobicity precursor Hydrophobicity.For example, ethyl trimethoxy silane can be more hydrophobic than MTMS.Similarly, cetyl front three TMOS can be more hydrophobic than ethyl trimethoxy silane.Can also be by relative to the hydrophily function in reactant mixture The concentration of the concentration increase hydrophobic functional groups of group reduces shape by the reaction time relative to formation hydrophobic parts 104 Reaction time into hydrophilic parts 102 is so as to increase the hydrophobicity of amphiphilic nanoparticles 100.Again in other embodiments In, when matrix includes carbonaceous material, the hydrophobic parts 104 of amphiphilic nanoparticles 100 can be core, and hydrophily portion It can be any hydrophilic functional group being connected with carbonaceous material to divide 102.
Amphiphilic nanoparticles 100 can be removed from reaction solution by centrifugation, ultrafiltration or its combination.In some implementations In scheme, by making solution flow through film filter so as to reclaim amphiphilic nanoparticles 100.Filter can have about Between 10nm and about 1,000nm, between such as about 10nm and about 100nm, between about 100nm and about 200nm, about 200nm with about Aperture in the range of between 400nm or between about 400nm and about 1,000nm.In some embodiments, solution flows through hole Filter of the footpath between about 200nm and about 400nm.Gained solid residue can be dried and collected.Solid residue may Including the amphiphilic nanoparticles 100 with hydrophilic parts 102 and hydrophobic parts 104.Hydrophobic parts 104 can be with parent Aqueous fractions 102 are relative so that a part for amphiphilic nanoparticles 100 is attracted and is dissolved in hydrocarbon phase, and amphipathic receive Another part of rice grain 100 is then attracted and is dissolved in aqueous phase.
Amphiphilic nanoparticles 100 can have the Size Distribution in the range of between about 10nm and about 1,000nm.One In a little embodiments, Size Distribution can correspond to the size of filter, and solution is by the filter so as to from reaction solution Middle separating nano-particles.Amphiphilic nanoparticles 100 can be monodispersed, wherein each amphiphilic nanoparticles 100 have Substantially the same size, shape and material composition, or can be polydispersion, wherein amphiphilic nanoparticles 100 include A range of size, shape and/or material composition.In some embodiments, each amphiphilic nanoparticles 100 have with Each other amphiphilic nanoparticles 100 substantially the same size and identical shape.
Compared to typical surfactant, amphiphilic nanoparticles 100 can stable emulsion at higher temperatures.Example Such as, typical surfactant degraded or may otherwise lose function at a temperature of more than about 250 DEG C.However, this Amphiphilic nanoparticles 100 described in text are probably stable at a high temperature of may being met with subsurface formations.For example, amphiphilic Property nano particle 100 be probably stable at a temperature of at most about 500 DEG C.In some embodiments, amphiphilic nano Grain 100 is exposed between about 250 DEG C and about 500 DEG C, between such as about 300 DEG C and about 400 DEG C, or about 400 DEG C and about 500 DEG C it Between temperature and can keep stable.
Compared to typical surfactant, amphiphilic nanoparticles 100 can be maintained under higher salinity concentration Effect ground stable emulsion.Due to there is functional group on amphiphilic nanoparticles 100, therefore amphiphilic nanoparticles 100 can be by salt The salt of the aqueous solution repels, rather than functionalized particle may tend to coalesce or be gelled with salt.
Amphiphilic nanoparticles 100 can be stablized in the range of wide pH.For example, amphiphilic nanoparticles 100 can be by It is configured under the pH between about 3.0 and about 12.0 stable.In some embodiments, by by anionic functional group (such as Hydroxyl, carboxylate radical, carboxyl, sulfate radical, phosphate radical or other anionic groups) amphiphilic nanoparticles 100 are formed, it is amphipathic to receive Rice grain 100 is formulated under the pH for being up to about 12.0 stable.In other embodiments, by including cation group (such as amido) end, amphiphilic nanoparticles 100 are formulated under as little as about 3.0 pH stable.
Amphiphilic nanoparticles 100 can in any application for needing stable emulsion stable emulsion.For example, amphipathic Nano particle 100 can be used for water drive to apply or floation tank application.Amphiphilic nanoparticles 100 can be by itself come stable breast Liquid, or amphiphilic nanoparticles 100 can be used together with one or more surfactants.
With reference to Fig. 2, a kind of side that the hydrocarbon materials included in subsurface formations are reclaimed according to the embodiment of the disclosure is shown The simplified flowchart of method.Methods described can include suspension forming process 200, and it, which includes being formed, includes multiple amphiphilic nanos The displacement suspension of particle；Displacement process 202, it includes the displacement suspension being introduced into subsurface formations so that hydrocarbon materials Depart from and formed the stabilized emulsion of hydrocarbon materials and hydrous material from the surface of subsurface formations；Extraction process 204, it include from Subsurface formations flowing (such as driving, drive are swept, forced) stabilized emulsion；And emulsion destabilizer process 206, it includes making Emulsion destabilizer (such as breaking, precipitation) is into different immiscible phases.
Suspension forming process 200 can include forming the suspension comprising amphiphilic nanoparticles and at least one carrier fluid Liquid.At least one carrier fluid can be for example comprising water or saline solution.Term " suspension " as used in this article mean and And including including the material for essentially homogeneously disperseing amphiphilic nanoparticles at least one carrier fluid and carrier fluid.Suspension can To be the displacement suspension that is used in the water drive of subsurface formations such as in enhancing oil recovery process.The amphiphilic of displacement suspension Property nano particle can be compatible with other components (such as material, composition) of displacement suspension.Term as used in this article " compatible " means that material does not damage the function of amphiphilic nanoparticles or do not cause amphiphilic nanoparticles loss to be lived as surface Property agent and the function of emulsion stabilizer.
Displacement suspension, which can be formulated into, to be included in amphipathic in the range of between about 50,000ppm of about 50ppm and receives Rice grain concentration.For example, in some embodiments, displacement suspension can have between about 50ppm and about 500ppm, about Between 500ppm and about 1,000ppm, between about 1,000ppm and about 5,000ppm or higher than amphipathic in the range of 5,000ppm Concentrations of nanoparticles.In some embodiments, displacement suspension can have in about 50ppm to scope between about 5,000ppm Interior concentration.In some embodiments, suspension includes amphiphilic nanoparticles and another portion of the part with carbon core Divide the amphiphilic nanoparticles with another base portion.For example, suspension, which can include Part I, includes carbon containing thing The amphiphilic nanoparticles and Part III that amphiphilic nanoparticles, the Part II of matter include silica core include metal The amphiphilic nanoparticles of core.Compared to displacement suspension, emulsion can have identical, higher or lower amphiphilic nano Grain concentration.
With continued reference to Fig. 2, displacement process 202 can include introducing ground by the displacement suspension comprising amphiphilic nanoparticles So that hydrocarbon materials depart from and formed the stabilized emulsion of hydrocarbon materials and hydrous material from the surface of subsurface formations in lower stratum. Displacement suspension can be provided into subsurface formations by conventional method.For example, the pressurized stream of displacement suspension can use infusion Enter and extend in the injection well of the hope depth in subsurface formations, and (such as infiltration, diffusion) subsurface formations can be penetrated into Clearance space.The permeate the ground degree of clearance space on stratum of displacement suspension depends, at least partially, on displacement suspension The property of the hydrocarbon materials included in property (such as density, viscosity, material composition) and the clearance space of subsurface formations (is for example divided Sub- amount, density, viscosity etc.).
The pH of displacement suspension can be changed to control solubility of the amphiphilic nanoparticles in displacement suspension.Example Such as, when amphiphilic nanoparticles include Cationic functional groups (such as amino), the pH of reduction displacement suspension can increase by two Solubility of parent's property nano particle in aqueous displacement suspension.When amphiphilic nanoparticles include anionic functional group (for example Hydroxyl, carboxyl, carbonyl, phosphate radical, mercapto etc.) when, the pH of increase displacement suspension can increase amphiphilic nanoparticles and exist Solubility in displacement suspension.The surface charge of amphiphilic nanoparticles can be changed by changing the pH of displacement suspension.For example, The anionic amphiphilic in displacement suspension can be increased by increasing the pH for the displacement suspension for including anionic amphiphilic nano particle The net charge of property nano particle.Cation can be increased by reducing the pH for the displacement suspension for including cationic amphiphilic nano particle The net charge of amphiphilic nanoparticles.
Introduced by displacement suspension after subsurface formations, thus it is possible to vary the pH of displacement suspension is so as to reduce amphipathic receive Solubility of the rice grain in the aqueous phase of displacement suspension.For example, when amphiphilic nanoparticles include Cationic functional groups, can To reduce the pH of displacement suspension so as to cause amphiphilic nanoparticles to the Interface Moving between aqueous phase and hydrocarbon phase.In some realities Apply in scheme, pH can be decreased below to about 7.0, such as less than 5.0, less than 4.0 or less than 3.0.When amphiphilic nano When grain includes anionic functional group, the pH of displacement suspension can be increased to cause amphiphilic nanoparticles to aqueous phase and hydrocarbon phase Between Interface Moving.In some embodiments, pH can be increased above to 7.0, such as higher than 8.0, higher than 9.0, height In 10.0 and up to 12.0.
Amphiphilic nanoparticles are by structuring and prepare so as to promote the stabilisation breast to form hydrocarbon materials and hydrous material Liquid.For example, amphiphilic nanoparticles can be assembled by structuring and preparation and (such as coalesce) in hydrocarbon materials and aqueous material The interface of material, it is attached to the interface and/or is adsorbed to the interface so as to forming Pickering emulsions, the breast Unit (such as drop) of the liquid comprising one of hydrocarbon materials and hydrous material is dispersed in the another one of hydrocarbon materials and hydrous material. Amphiphilic nanoparticles can prevent scattered material (such as hydrocarbon materials or hydrous material) from coalescing, and therefore can make to disperse Material to be maintained in the form of unit in whole another material.
Extraction process 204 can include making stabilized emulsion (for example drive, drive is swept, force flowing from subsurface formations flow direction Deng) surface.Amphiphilic nanoparticles prevent scattered material from coalescing and allowing to substantially remove dealkylation from subsurface formations Class.
Once hydro carbons is removed from subsurface formations, it is possible to make at least a portion emulsion in emulsion destabilizer process 206 Go stable so as to form the different immiscible phases including aqueous phase and hydrocarbon phase.It can change and (for example change, change) stable The emulsion of change or one or more properties (such as temperature, PH, material composition, pressure) of aqueous phase so that make breast at least in part Liquid goes stabilization.For example, the pH of aqueous phase can be changed to increase solubility of the amphiphilic nanoparticles in aqueous phase, so that newborn Liquid goes stable and forms different immiscible phases.
In some embodiments, thus it is possible to vary the pH of emulsion or aqueous phase is so as to cause amphiphilic nanoparticles to move to aqueous phase In and make emulsion destabilizer.When amphiphilic nanoparticles include anionic functional group, the pH of aqueous phase can be increased to increase Plus solubility of the amphiphilic nanoparticles in aqueous phase.Can be by adding alkali, such as hydroxide (such as hydrogen-oxygen in aqueous phase Change sodium) or bicarbonate (such as sodium acid carbonate), so as to increase the pH of aqueous phase.When amphiphilic nanoparticles include functionalized cationic During group, the pH of aqueous phase can be reduced to increase solubility of the amphiphilic nanoparticles in aqueous phase.Can be by aqueous phase Hydrochloric acid, phosphoric acid and acetic acid or another acid is added to reduce the pH of the aqueous solution.
Demulsifying agent can be added in emulsion so that emulsion destabilizer and formed include the difference of aqueous phase and hydrocarbon phase Immiscible phase.In some embodiments, by adjusting the pH of at least one of aqueous phase and emulsion and by breast Demulsifying agent is added in liquid so that emulsion destabilizer.
With reference to Fig. 3, other embodiments according to the disclosure are shown, illustrate a kind of recovery hydrocarbon materials from tar sand The simplified flowchart of method.Methods described can include suspension forming process 300, and it, which includes being formed, includes multiple amphipathic receive The suspension of rice grain；Mixed process 302, it includes mixing suspension into steady so as to be formed with the slurry comprising tar sand and water Surely the emulsion changed；Course of conveying 304, it includes Hydraulic transportation slurry；Extraction process 306, it is included from stabilized emulsion Extract hydro carbons；And emulsion destabilizer process 308, it includes making emulsion destabilizer (such as breaking, precipitation) into different Immiscible phase.
Suspension forming process 300 can include forming the suspension comprising amphiphilic nanoparticles and at least one carrier fluid Liquid.Carrier fluid can be for example comprising water, saline solution or caustic soda (NaOH) solution.Suspension can be formulated into including with above The similar amphiphilic nanoparticles concentration of displacement suspension described in reference diagram 2.
Mixed process 302 can include mixing suspension with the slurry comprising tar sand and water forming stabilized Emulsion.Slurry can include hot water, caustic soda and tar sand.Course of conveying 304 can include slurry waterpower being delivered to can be with The position of stabilized emulsion is processed to remove hydro carbons (such as from tar sand) therefrom.In some embodiments, mix Conjunction process 302 can simultaneously be carried out with course of conveying 304.In some embodiments, can be in mixed process and course of conveying The pH of regulation slurry is so as to reduce solubility and increase of the amphiphilic nanoparticles in the hydrophilic parts of slurry during 304 Solubility of the amphiphilic nanoparticles in stabilized emulsion.
Amphiphilic nanoparticles are by structuring and prepare so as to promote to form hydrocarbon materials and the stabilized emulsion of aqueous phase.Example Such as, amphiphilic nanoparticles can be gathered in interface, the attachment of hydrocarbon materials and hydrous material by structuring and preparation To the interface and/or the interface is adsorbed to so as to form Pickering emulsions, the emulsion is comprising hydrocarbon materials and contains The unit (such as drop) of one of water material is dispersed in the another one of hydrocarbon materials and hydrous material.
Extraction process 306 can include extracting hydro carbons from stabilized emulsion.In some embodiments, extraction process 306 are included in floatation process hydro carbons are extracted from the stabilized emulsion of slurry.
It can make at least one in emulsion destabilizer process 308 after removing hydro carbons from aqueous phase in floatation process Stabilized emulsion destabilizer is divided to form the different immiscible phases including aqueous phase and hydrocarbon phase.It can change (for example Change, change) stabilized emulsion or aqueous phase one or more properties (such as temperature, pH, material composition, pressure) so as to Make emulsion destabilizer at least in part.For example, the pH of aqueous phase can be changed to increase amphiphilic nanoparticles in aqueous phase Solubility, thus makes emulsion destabilizer and forms different immiscible phases.Can change the pH of stabilized emulsion from And cause amphiphilic nanoparticles to be shifted in aqueous phase and make emulsion destabilizer, as the emulsion destabilizer mistake above with reference to Fig. 2 Described by journey 206.In other embodiments, demulsifying agent can be added in emulsion so that emulsion destabilizer and being formed Different immiscible phases including aqueous phase and hydrocarbon phase.
After emulsion destabilizer is made, hydrocarbon materials can be made to be separated and recovered from hydrous material.Afterwards, can be from aqueous phase Reclaim amphiphilic nanoparticles.In some embodiments, the pH of the aqueous solution can be adjusted to reduce amphiphilic nanoparticles Solubility in aqueous phase and amphiphilic nanoparticles are made to be precipitated from the aqueous solution.For example, when amphiphilic nanoparticles are included During the functional group of such as amine functional group, the pH of reduction hydrous material can reduce the dissolving of amphiphilic nanoparticles in aqueous Degree, thus causes amphiphilic nanoparticles to be precipitated out from the aqueous solution.It is hydroxyl, carboxylic in the functional group of amphiphilic nanoparticles In base, carbonyl, mercapto, the embodiment of phosphate radical or other anionic groups, the pH of the increase aqueous solution may cause to amphiphilic Property nano particle is precipitated out from the aqueous solution.In other embodiments, amphiphilic is reclaimed by filter filtering solution Property nano particle.Filter can have the aperture in the range of between about 10nm and about 5,000nm, and this depends on amphipathic receive The size of rice grain.In some embodiments, more than one filtration step can be carried out.For example, the first filtration step can be with Filter out the sand and other solid particles that there is larger diameter than amphiphilic nanoparticles.Afterwards, it can be separated from the aqueous solution Amphiphilic nanoparticles.
Other non-limiting example embodiments of the disclosure are set forth below.
Embodiment 1：A kind of method for reclaiming hydrocarbon materials, methods described includes：Will be comprising carbon core, positioned at the carbon core one The multiple of hydrophilic functional group on individual surface and the hydrophobic functional groups on another surface of carbon core amphipathic receive Rice grain combines to form suspension with carrier fluid；Make at least one of subsurface formations and the slurry comprising tar sand and water with The suspension contacts to be formed by the stable emulsion of the amphiphilic nanoparticles；And from by the amphiphilic nanoparticles Hydro carbons is removed in the stable emulsion.
Embodiment 2：The method of embodiment 1, wherein will be hydrophilic comprising carbon core, on described one surface of carbon core Property functional group and the hydrophobic functional groups on another surface of carbon core multiple amphiphilic nanoparticles and carrier fluid group Close includes combining comprising CNT, carbon Nano diamond, graphite, graphene, graphene oxide, fullerene to form suspension And the amphiphilic nanoparticles of at least one of Buckie green onion.
Embodiment 3：The method of embodiment 2, in fact wherein by comprising carbon core, on described one surface of carbon core Multiple amphiphilic nanoparticles of hydrophilic functional group and the hydrophobic functional groups on another surface of carbon core are with carrying Liquid combination includes combining the amphiphilic nanoparticles comprising amido functional group with the carrier fluid to form suspension.
Embodiment 4：The method of any one of embodiment 1 to 3, be additionally included in the carbon core with it is described at least one At least one described hydrophilic group is formed on the relative surface of hydrophilic group.
Embodiment 5：The method of embodiment 4, wherein forming at least one described hydrophilic group includes making the carbon core At least one hydrophylic precursor hydrolysis on the surface.
Embodiment 6：The method of any one of embodiment 1 to 5, is additionally included on the outer wall of CNT and forms described At least one hydrophilic group.
Embodiment 7：The method of any one of embodiment 1 to 6, is additionally included on the side of graphene platelet and forms institute State at least one hydrophilic group.
Embodiment 8：The method of any one of embodiment 1 to 7, is additionally included in from steady by the amphiphilic nanoparticles Removed in the fixed emulsion after hydro carbons, increase solubility of the amphiphilic nanoparticles in aqueous phase.
Embodiment 9：The method of embodiment 8, wherein increasing solubility of the amphiphilic nanoparticles in aqueous phase PH including changing the aqueous phase.
Embodiment 10：The method of any one of embodiment 1 to 9, in addition to by the amphiphilic comprising silica matrix Property nano particle is mixed into the carrier fluid.
Embodiment 11：The method of any one of embodiment 1 to 10, wherein will be comprising carbon core, positioned at the carbon core one The multiple of hydrophilic functional group on individual surface and the hydrophobic functional groups on another surface of carbon core amphipathic receive Rice grain is combined with carrier fluid to be included forming the suspension to include described the two of about 50ppm to about 500ppm to form suspension Parent's property nano particle.
Embodiment 12：The method of any one of embodiment 1 to 11, being additionally included in makes subsurface formations and comprising pitch After at least one of slurry of sand and water is contacted with the suspension, change the pH of the suspension.
Embodiment 13：The method of any one of embodiment 1 to 12, is additionally included in from by the amphiphilic nanoparticles After removing hydro carbons in the stable emulsion, reduce solubility of the amphiphilic nanoparticles in aqueous phase and from described At least one of amphiphilic nanoparticles are reclaimed in emulsion.
Embodiment 14：The method of any one of embodiment 1 to 13, is additionally included in removing by the amphiphilic nano Make the emulsion destabilizer after the stabilized hydro carbons of grain.
Embodiment 15：A kind of method that dealkylation is removed from subsurface formations, methods described includes：Comprising CNT, Fullerene, carbon Nano diamond, formed on a surface of the carbonaceous material of at least one of graphene and graphene oxide to A few hydrophilic group；The carbonaceous material is mixed with carrier fluid to form suspension；The suspension is introduced into subsurface formations In and the hydro carbons in the subsurface formations is contacted with the suspension so as to being formed by the stabilized breast of the carbonaceous material Liquid；And the emulsion is delivered to the surface of the subsurface formations.
Embodiment 16：The method of embodiment 15, is additionally included on another surface of the carbonaceous material and is formed at least One hydrophobic functional groups.
Embodiment 17：The method of embodiment 16, wherein forming at least one on another surface of the carbonaceous material Individual hydrophobic functional groups, which are included on the surface relative with least one described hydrophilic group, forms at least one hydrophobicity official Can group.
Embodiment 18：The method of any one of embodiment 15 to 17, wherein the shape on a surface of carbonaceous material It is included in at least one hydrophilic group on the carbonaceous material and forms at least one amido.
Embodiment 19：The method of any one of embodiment 15 to 18, in addition to on the carbonaceous material at least At least one described hydrophilic group of hydroxyl hydrolysis of the exposure of one hydrophilic group on the carbonaceous material so that form hydrophobic group.
Embodiment 20：The method of any one of embodiment 15 to 19, wherein the shape on a surface of carbonaceous material It is included in at least one hydrophilic group on the outer wall of CNT and forms at least one described hydrophilic group.
Embodiment 21：The method of any one of embodiment 15 to 19, wherein the shape on a surface of carbonaceous material It is included in at least one hydrophilic group on the side of graphene platelet and forms at least one described hydrophilic group.
Embodiment 22：The method of any one of embodiment 15 to 21, in addition to by two comprising silica matrix Parent's property nano particle is mixed into the carrier fluid.
Embodiment 23：A kind of suspension for being used to remove hydro carbons from subsurface formations, the suspension is included：It is multiple to contain Carbon amphiphilic nanoparticles, the amphiphilic nanoparticles are included：Hydrophobicity on a surface of the carbonaceous material Functional group；And the hydrophilic functional group on another surface of the carbonaceous material；And carrier fluid.
Embodiment 24：The suspension of embodiment 23, wherein described on another surface of the carbonaceous material Hydrophilic functional group is located on the surface relative with the hydrophobic functional groups of the carbonaceous material.
Although the disclosure easily carries out various modifications and alternative form, it has been exemplarily illustrated in the accompanying drawings simultaneously And specific embodiment is described in detail herein.However, the disclosure is not limited to disclosed particular form.On the contrary, this public affairs Open covering fall through all modifications form in the range of the disclosure that appended claims and its legal equivalents form are limited, Equivalents and alternative form.

Claims (15)

1. a kind of method for reclaiming hydrocarbon materials, methods described includes：
By the hydrophilic functional group comprising carbon core, on a surface of the carbon core and another table positioned at the carbon core Multiple amphiphilic nanoparticles of hydrophobic functional groups on face combine to form suspension with carrier fluid；
Make at least one of subsurface formations and the slurry comprising tar sand and water contact with the suspension to be formed by institute State the stable emulsion of amphiphilic nanoparticles；And
Hydro carbons is removed from by the stable emulsion of the amphiphilic nanoparticles.
2. the method as described in claim 1, wherein by the hydrophily official comprising carbon core, on a surface of the carbon core It can roll into a ball and multiple amphiphilic nanoparticles of hydrophobic functional groups on another surface of the carbon core are combined with carrier fluid With formed suspension include combination comprising CNT, carbon Nano diamond, graphite, graphene, graphene oxide, fullerene with And the amphiphilic nanoparticles of at least one of Buckie green onion.
3. method as claimed in claim 2, wherein by the hydrophily official comprising carbon core, on a surface of the carbon core It can roll into a ball and multiple amphiphilic nanoparticles of hydrophobic functional groups on another surface of the carbon core are combined with carrier fluid Include combining the amphiphilic nanoparticles comprising amido functional group with the carrier fluid to form suspension.
4. the method as described in claim 1, is additionally included in the surface relative with least one described hydrophilic group of the carbon core At least one hydrophilic group described in upper formation.
5. method as claimed in claim 4, wherein forming at least one described hydrophilic group includes making the table of the carbon core At least one hydrophylic precursor hydrolysis on face.
6. the method as described in claim 1, is additionally included on the outer wall of CNT and forms at least one described hydrophilic group.
7. the method as described in claim 1, is additionally included on the side of graphene platelet and forms at least one described hydrophilic group.
8. the method as described in claim 1, is additionally included in and is removed from by the stable emulsion of the amphiphilic nanoparticles Go after hydro carbons, increase solubility of the amphiphilic nanoparticles in aqueous phase.
9. method as claimed in claim 8, wherein increasing solubility of the amphiphilic nanoparticles in aqueous phase includes changing Become the pH of the aqueous phase.
10. method as claimed in any one of claims 1-9 wherein, in addition to by the amphiphilic nano comprising silica matrix Particle is mixed into the carrier fluid.
11. method as claimed in any one of claims 1-9 wherein, wherein by comprising carbon core, positioned at a surface of the carbon core On hydrophilic functional group and the hydrophobic functional groups on another surface of the carbon core multiple amphiphilic nanos Grain is combined with carrier fluid to be included forming the suspension with comprising the described amphipathic of about 50ppm to about 500ppm to form suspension Nano particle.
12. method as claimed in any one of claims 1-9 wherein, being additionally included in makes subsurface formations and comprising tar sand and water At least one of slurry contacted with the suspension after, change the pH of the suspension.
13. method as claimed in any one of claims 1-9 wherein, is additionally included in from by amphiphilic nanoparticles stabilization After removing hydro carbons in the emulsion, reduce solubility in aqueous phase of the amphiphilic nanoparticles and from the emulsion Reclaim at least one of amphiphilic nanoparticles.
14. a kind of suspension for being used to remove hydro carbons from subsurface formations, the suspension is included：
Multiple amphiphilic nanoparticles, the amphiphilic nanoparticles are included：
Carbon core；
Hydrophobic functional groups on a surface of the carbon core；And
Hydrophilic functional group on another surface of the carbon core；And
Carrier fluid.
15. suspension as claimed in claim 14, wherein the hydrophily function on another surface of the carbon core Cumularsharolith is on the surface relative with the hydrophobic functional groups of the core.
CN201580064674.0A 2014-10-21 2015-10-19 Suspension and the method using the suspension recovery hydro carbons for strengthening hydrocarbon recovery Pending CN107018666A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US14/519728 2014-10-21
US14/519,728 US9708896B2 (en) 2014-01-31 2014-10-21 Methods of recovering hydrocarbons using a suspension
PCT/US2015/056185 WO2016064718A1 (en) 2014-10-21 2015-10-19 Suspensions for enhanced hydrocarbon recovery, and methods of recovering hydrocarbons using the suspensions

Publications (1)

Publication Number Publication Date
CN107018666A true CN107018666A (en) 2017-08-04

Family

ID=55761359

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201580064674.0A Pending CN107018666A (en) 2014-10-21 2015-10-19 Suspension and the method using the suspension recovery hydro carbons for strengthening hydrocarbon recovery

Country Status (3)

Country Link
CN (1) CN107018666A (en)
RU (1) RU2672116C1 (en)
WO (1) WO2016064718A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109852359A (en) * 2018-12-29 2019-06-07 浙江海洋大学 A kind of Pickering lotion and preparation method thereof for heavy crude reservoir
CN110740971A (en) * 2017-06-19 2020-01-31 株式会社大赛璐 Surface-modified nanodiamond, dispersion liquid containing surface-modified nanodiamond, and resin dispersion
CN113698921A (en) * 2020-05-22 2021-11-26 中石化石油工程技术服务有限公司 Controllable preparation method of novel amphiphilic particle material

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11708274B2 (en) 2020-04-15 2023-07-25 Saudi Arabian Oil Company Synthesis of polyethylenimine-silica janus nanoparticles
US20210363408A1 (en) * 2020-05-20 2021-11-25 University Of Wyoming Quantum dot nanofluids

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100243248A1 (en) * 2006-12-01 2010-09-30 Golomb Dan S Particle Stabilized Emulsions for Enhanced Hydrocarbon Recovery
US20120015852A1 (en) * 2010-06-28 2012-01-19 Baker Hughes Incorporated Nanofluids and Methods of Use for Drilling and Completion Fluids
US20130200291A1 (en) * 2012-01-27 2013-08-08 Queen's University At Kingston Tertiary Amine-Based Switchable Cationic Surfactants and Methods and Systems of Use Thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8357639B2 (en) * 2007-07-03 2013-01-22 Baker Hughes Incorporated Nanoemulsions
US8222190B2 (en) * 2009-08-19 2012-07-17 Nanotek Instruments, Inc. Nano graphene-modified lubricant
US20130233559A1 (en) * 2012-03-07 2013-09-12 Halliburton Energy Services, Inc. Surfactant Additives for Stimulating Subterranean Formation During Fracturing Operations
WO2014035861A1 (en) * 2012-08-29 2014-03-06 Baker Hughes Incorporated Controllably tuning properties of a fluid using modified nanoparticles
CA2840675A1 (en) * 2013-01-18 2014-07-18 Apex Engineering Inc. Method for destabilizing bitumen-water and oil-water emulsions using lime

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100243248A1 (en) * 2006-12-01 2010-09-30 Golomb Dan S Particle Stabilized Emulsions for Enhanced Hydrocarbon Recovery
US20120015852A1 (en) * 2010-06-28 2012-01-19 Baker Hughes Incorporated Nanofluids and Methods of Use for Drilling and Completion Fluids
US20130200291A1 (en) * 2012-01-27 2013-08-08 Queen's University At Kingston Tertiary Amine-Based Switchable Cationic Surfactants and Methods and Systems of Use Thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110740971A (en) * 2017-06-19 2020-01-31 株式会社大赛璐 Surface-modified nanodiamond, dispersion liquid containing surface-modified nanodiamond, and resin dispersion
CN109852359A (en) * 2018-12-29 2019-06-07 浙江海洋大学 A kind of Pickering lotion and preparation method thereof for heavy crude reservoir
CN113698921A (en) * 2020-05-22 2021-11-26 中石化石油工程技术服务有限公司 Controllable preparation method of novel amphiphilic particle material

Also Published As

Publication number Publication date
RU2672116C1 (en) 2018-11-12
WO2016064718A1 (en) 2016-04-28

Similar Documents

Publication Publication Date Title
CN106103889B (en) For enhancing the nanometer surfactant of hydrocarbon harvesting, and the method for being formed and using the nanometer surfactant
US9708896B2 (en) Methods of recovering hydrocarbons using a suspension
CN107018666A (en) Suspension and the method using the suspension recovery hydro carbons for strengthening hydrocarbon recovery
US20220010198A1 (en) Methods of recovering a hydrocarbon material
US11401454B2 (en) Hydrocarbon formation treatment micellar solutions
US20190048251A1 (en) Suspensions for removing hydrocarbons from subterranean formations and related methods
US20130045897A1 (en) Amphiphilic nanoparticle, composition comprising same and method of controlling oil spill using amphiphilic nanoparticle
Khoramian et al. The development of novel nanofluid for enhanced oil recovery application
US11305251B2 (en) Methods including functionalizing nanoparticles and forming suspensions
US20210395601A1 (en) Silicon Dioxide Janus Nanosheets Relative Permeability Modifier (RPM) for Reducing Subterranean Formation Water Permeability in Carbonate and Sandstone Formations
EP3015429A1 (en) Monolayer from at least one layered double hydroxide (LDH)
US20190316028A1 (en) Working fluids
Ngouangna et al. Surface modification of nanoparticles to improve oil recovery Mechanisms: A critical review of the methods, influencing Parameters, advances and prospects
US20150353836A1 (en) Flocculants and methods for recovering bitumen from oil sands
WO2022020719A1 (en) Enhanced oil recovery with janus nanoparticles
CN114667330A (en) Silica nanoparticles for recovery of crude oil using carbon dioxide and crude oil recovery process
CN105498696A (en) Method for preparing magnetic nanoparticles suitable for emulsified oil wastewater treatment
US10190388B2 (en) Diverter fluid diverter fluid
US20180118587A1 (en) Methods of removing fines and coarse particles from oil sand tailings, and related mixtures
Suresh et al. Click reaction functionalization of hydroxylated nanoparticles by cyclic azasilanes for colloidal stability in oilfield applications
CN116004213B (en) Surfactant/nanoparticle composite oil displacement agent and preparation method and application thereof
Ghosh et al. Oil Recovery from Mining Effluents Using Nanotechnology
CN116063342A (en) Quaternary ammonium salt modified SiO 2 Nanometer material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
AD01 Patent right deemed abandoned
AD01 Patent right deemed abandoned

Effective date of abandoning: 20201113