CN103937478B - Preparation method of nanofluid for improving oil recovery - Google Patents

Preparation method of nanofluid for improving oil recovery Download PDF

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CN103937478B
CN103937478B CN201410152028.7A CN201410152028A CN103937478B CN 103937478 B CN103937478 B CN 103937478B CN 201410152028 A CN201410152028 A CN 201410152028A CN 103937478 B CN103937478 B CN 103937478B
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nano
fluid
water
surfactant
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CN103937478A (en
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赵法军
刘永建
张继红
魏建光
闻守斌
胡绍彬
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Northeast Petroleum University
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/10Nanoparticle-containing well treatment fluids

Abstract

The invention discloses a preparation method of a nanofluid for improving oil recovery. The preparation method comprises the following steps: taking 2.0-4.0g of nanopowder, adding 60-80mL of deionized water to the nanopowder and carrying out ultrasonic dispersion at a room temperature for 30-60 minutes; dissolving 2.0g of a silane coupling agent in absolute ethyl alcohol; mixing the nano-base solution with the ethanol solution of the silane coupling agent in a three-neck boiling flask, heating while stirring to the range of 70 to 75 DEG C, reacting for 4-6 hours, filtering, washing by using an anhydrous solvent a plurality of times, and drying in a vacuum drying box at 60-70 DEG C for 12 hours to obtain modified nanoparticles; putting 0.1-0.5g of nanoparticles in the three-neck boiling flask, adding 200-300mL of water, heating to the range of 60-75 DEG C by use of a water bath, mixing a surfactant with PEG (Poly Ethylene Glycol), adding 100mL of mixed solution of the surfactant and the PEG, mechanically stirring for 6-8 hours, washing the stirred dispersion 2-3 times, adjusting the pH value to the range of 8-9, and adding deionized water to 1L, thereby obtaining the water-based nanofluid.

Description

A kind of preparation method of the nano-fluid for improving oil recovery factor
Technical field
The present invention relates to petrochemical industry, more particularly to a kind of nano-fluid is used for improving oil recovery factor method.
Background technology
In the world in many oil reservoirs, about 2/3rds oil can not be exploited by conventional production process.Therefore, in maturated oil Tanaka, improves recovery efficiency technique(EOR)There are very big potentiality.It is relatively economical that water drive improves recovery ratio method, but is leading Will be in initial stage of production, improving water drive in recovery ratio method is relatively reasonable selection.After water drive produces time water drive, can select to add Plus some chemical agents, to increase the efficiency of water drive process as alkali, surfactant and polymer.These chemical substances are added to In injection water, the wetability of rock surface is changed into more hydrophilic state.The injection of polymer can increase the viscosity of injection water, improves non- Homogeneous and the sweep efficiency of viscosity oil reservoir.Surfactant mainly has for reducing interfacial tension, so that because of capillary force bundle Tie up the oil flowing acting in matrix pores.
In oil reservoir, the main difficulty using polymer is chemical degradation and the thermal degradation of polymer.Additionally, typical polymerization Thing molecular weight is difficult to be injected in low-permeability oil deposit for 1000 ~ 25,000,000 polymer.In addition, high temperature and high salt make surfactant Oil displacement process is challenging, can cause damage to surfactant oil displacement efficiency and form blocking, and the addition of alkali leads to mining site to try Occur in testing that oil recovery well shaft fouling is serious, Produced Liquid difficult treatment the problems such as.Additionally, traditional surfactant is to hydrolysis More sensitive.Therefore, it is necessary to exploitation heatproof, salt tolerant can have the new material of economic benefit in reservoir.
Nanometer technology can act on more efficient, less expensive, more environmentally friendly raising oil recovery(EOR)Method.Conventional The diameter of reservoir pore is typically all in micron order;Therefore, nano particle can flow wherein.Additionally, the one of nano particle Key property is skin effect, reduces with particle diameter, the surface area of particulate drastically becomes big, when the particle diameter of nanoparticle reaches 10nm When, specific surface area is 90m2/ g, when particle diameter is 5nm, specific surface area is 180 m2/ g, when particle diameter drops to 2nm, specific surface area is violent Increase to 450 m2/g.Very big specific surface area causes surface atom number to increase sharply, and accounts for quite big positioned at the atom of particle surface Ratio, key state severe mismatch, cause the surface energy that Atomic coordinate is not enough and high, many activated centres occur, surface step and Roughness increases, and chemical non-equilibrium, chemical valence, this chemical property leading to nanometer system and the change of non-integer coordination in surface Learn equilibrium system and very big difference occurs.
Nano particle is larger due to surface area and volume ratio ratio, thus increased the energy on surface.On a solid surface The suction-operated of active material can change the wetability of surface energy and system.Thus greatly reducing oil water interfacial tension, So that injection fluid, in hole displacement process, makes crude oil be easy to peel off into little oil droplet, and driven liquid displacement is out.Additionally, To reservoir, little duct has temporary occlusion to act on to nano-fluid particle, thus expanding swept volume, makes not fed through in hole Mother oil displacement out, reached raising recovery ratio, the purpose of increasing injection, therefore, carry out nano-fluid improve oil recovering Rate research work produces to oil field has direct production meaning, particularly some low permeability oil fields is more of practical significance.
There is scholar to develop a kind of metal (W, Ni, and Mo) nano-colloid particle-catalytic agent being dispersed in water to be dripped Blue or green exploitation.Nanocatalyst and the asphalt viscosity no under nano particle effect is had to carry out comparing result and show, nanocatalyst pair The viscosity reducing pitch is effective.Ponnapati et al. is found that water-soluble silica-zirconia ethylene type nanometer is gathered Compound.Although these nano-complexes do not produce high viscosity in the concentration determining, author thinks the polymer of higher molecular weight Higher grafting density can improve viscosity.
Ju et al. carries out the adsorption test of lipophobia and hydrophilic polysilicon nanometer particle to verify the wet of sandstone surface Lubricant nature changes.Observe hydrophily nano silicon particles and can improve oil recovering compared with pure water in size range 10-500 nm Rate about 9%, it is effective that polysilicon nanometer particle improves recovery efficiency technique to water drive.
Hendraningrat et al. research uses hydrophilic silicon oxides nano-particle, to the shadow improving oil recovery factor Sound, the size including nano-particle and concentration, initial wetability and the isoparametric impact of temperature.Result shows, by carrying High-temperature, reduces nanoparticle size and reduction nano-fluid injection rate can improve oil recovery factor.Additionally, also achieving rock Stone, from middle wetting state, obtains highest oil recovery factor and oil displacement efficiency.And find oil recovery factor and nanometer stream Bulk concentration is not directly proportional, that is, enhancing of recovering the oil when nano-fluid concentration increases, but when concentration is less than a critical value, adopts Yield can reduce.
Karimi et al. passes through the experimental study shadow of the wettability modification to carbonate reservoir for the zirconia nanopowder fluid Ring.Test result indicate that, nano-fluid can wet to become strong water wet from oily by force by the wetability of rock.
Giraldo et al. studying alumina nano-fluid is changing the wetability of Sandstone Cores and the wetability of induction oleophylic Validity.Research shows, the wetability that nano-fluid can change Sandstone Cores makes rock wet to be changed into water wet from oil.
Content of the invention
For the deficiencies in the prior art, the present invention adopts the following technical scheme that:
A kind of preparation method of the nano-fluid for improving oil recovery factor, comprises the steps:
1)Preparation nanometer base fluid:Take the nano-powder of 2.0-4.0g, add deionized water 60-80 mL, room temperature ultrasonic disperse 30-60min;
2)Separately take silane coupler 2.0g dissolving absolute ethyl alcohol 30-60mL;
3)Modified Nano particle:Nanometer base fluid is put in there-necked flask with silane coupler ethanol solution and mixes, while stirring Mix side and be heated to 70-75 DEG C, after reaction 4-6h, filtration anhydrous solvent washs for several times, is placed on 60-70 DEG C of vacuum drying chamber In 12h is dried after, obtain modification nano-particle;
4)Water-based nano-fluid:0.1-0.5g nano-particle is taken to put into there-necked flask, add water 200-300mL, warming-in-water To 60-75 DEG C, surfactant is mixed with PEG, and add its mixed solution 100mL, mechanical agitation 6-8h, after stirring Dispersion liquid carries out washing 2-3 time, then pH value is adjusted to 8-9, and adds deionized water to 1L, obtains water-based nano-fluid.
Described nano-powder is:Nano-TiO2, zinc oxide, nanometer Fe3O4, Nano-meter SiO_22At least one in powder.
Described silane coupler is selected:Silane coupling reagent KH-570, silane coupler KH-56 or cetyl trimethoxy Base silane.
Specifically, described prepare nano-TiO2Using Silane coupling reagent KH-570 (γ-methacryloxypropyl three Methoxy silane);Prepare nano zine oxide nano-fluid and adopt silane coupler KH-560 (γ-glycidol ether propoxyl group three Methoxy silane);Preparation nanometer Fe3O4Using silane coupler KH-560 (γ-glycidol ether propoxyl group trimethoxy silicon Alkane);Prepare Nano-meter SiO_22Fluid adopts hexadecyl trimethoxy silane.
Described anhydrous solvent is:Absolute ethyl alcohol or anhydrous n-hexane.
Described surfactant is:Neopelex, oleic acid are received or sodium alklyarylsulfonate.
Specifically, described prepare nano-TiO2Using surfactant neopelex;Prepare nano zine oxide to receive Meter Liu Ti is received for oleic acid using surfactant;Preparation nanometer Fe3O4Nano-fluid is received for oleic acid using surfactant;Prepare Nano-meter SiO_22 It is sodium alklyarylsulfonate that nano-fluid adopts surfactant.
A kind of using method of the nano-fluid for improving oil recovery factor, the nano-fluid of preparation in length is 8.2-9.5cm, a diameter of 2.5cm, permeability is 1.42-1.51 μm2Artificial core on to carry out the indoor physical simulation displacement of reservoir oil real Test;
Rock core is put in clamper, vacuumizes 6 hours, saturation simulation stratum water, measure rock core saturation degree and permeability; Oily expelling water, measures initial oil saturation;Constant temperature 12h under thermostatic drying chamber setting temperature 45 C, carries out water drive oil first to containing Water 92-93%, recording water drive oil displacement efficiency is 41.5-42.8%, then the nano-fluid of metaideophone 0.3pV, then sequent water flooding outlet Moisture content is 98-100%, and the oil displacement efficiency recording nano-fluid improves 13.5-16.8% than water drive water drive oil displacement efficiency.
Technical scheme is directed in prior art has high temperature and high salt containing surfactant, the oil displacement agent of polymer Under the conditions of oil displacement efficiency poor, the deficiency of concentration is high and alkali brings to stratum and oil well corrosion and incrustation injury etc., lead to The technical scheme crossing present invention offer can obtain good dispersion, stable nano-fluid, the method process is simple, condition temperature With, raw material availability height, low cost, be easy to industrialization.
Brief description
Fig. 1 is that the town particle size of catalyst surface is between 20-50nm through high resolution electron microscopy (HRTEM) detection The TEM figure of water-base nano TiO2 fluid.
Specific embodiment
Below by specific embodiment, the present invention is described in detail.
Embodiment 1
Take the nano-TiO of 2.0g2Powder, adds deionized water 60 mL, room temperature ultrasonic disperse 30min, separately takes silane coupled Agent KH-570 (γ-methacryloxypropyl trimethoxy silane) 2.0g dissolves absolute ethyl alcohol 40mL, by nano-TiO2Base Liquid is mixed with silane coupler KH-560 ethanol solution, puts in there-necked flask, is heated to 70 DEG C of temperature while stirring, filters and uses Absolute ethanol washing for several times, is placed on after being dried in 60 DEG C of vacuum drying chambers, obtains the TiO of modification2Nano-particle.
Take 0.5g TiO2Nano-particle puts into there-necked flask, and add water 300mL, warming-in-water to 70 DEG C, adds 2g 12 Sodium alkyl benzene sulfonate and 2g PEG-4000 mixed solution 100mL, mechanical agitation 8h, the dispersion liquid after stirring is carried out washing three Secondary, then by pH value regulation to 8, and add deionized water to 1L, obtain TiO2Water-based nano-fluid.
Fig. 1 is water-base nano TiO2The TEM figure of fluid, as seen from Figure 1, nano-TiO2Particle so intensive state according to Single particle so can be kept not reunite, illustrate that the nano-particle prepared can reach the purpose do not reunited.
Embodiment 2
Take the nanometer Zinc oxide powder of 2.0g, add deionized water 80 mL, room temperature ultrasonic disperse 60min, separately take silane even Connection agent KH-560 (γ-glycidol ether propoxyl group trimethoxy silane) 2.0g dissolving absolute ethyl alcohol 30mL, by nano zine oxide Base fluid is mixed with silane coupler KH-560 ethanol solution, puts in there-necked flask, while stirring, while be heated to 70 DEG C of temperature, instead After answering 4h, filtration absolute ethanol washing for several times, is placed on after being dried in 60 DEG C of vacuum drying chambers, obtains the zinc oxide of modification Nano-particle.
0.5g Zinc oxide nanoparticle is taken to put into there-necked flask, plus deionized water 200mL, warming-in-water to 70 DEG C, add 1g oleic acid is received and 1g PEG-4000 mixed solution 100mL, mechanical agitation 8 h, and the dispersion liquid after stirring is carried out washing three Secondary, then by pH value regulation to 8, and add deionized water to 1L, obtain zinc oxide water-based nano-fluid.
Embodiment 3
Take nanometer Fe3O4Powder 4g, adds deionized water 80 mL, room temperature ultrasonic disperse 40min, separately takes silane coupler KH-560 (γ-glycidol ether propoxyl group trimethoxy silane) 2g dissolves absolute ethyl alcohol 30mL, by nanometer Fe3O4Base fluid and silicon Stirring in there-necked flask is put in the mixing of alkane coupling agent KH-560 ethanol solution, and after 70 DEG C of water-bath 8h, vacuum filtration obtains Solid, puts in constant temperature blast drying oven and is dried 12 hours, obtains the Fe of modification3O4Particle.
Take 0.1g nanometer Fe3O4Particle puts into there-necked flask, and add water 300mL, warming-in-water to 60 DEG C, adds 1g oleic acid and receives With 1g PEG-4000 (macrogol) mixed solution 100mL, mechanical agitation 6h, the dispersion liquid after stirring is carried out washing three Secondary, then pH value is adjusted to 8, and add deionized water to 100mL, obtain Fe3O4Water-based nano-fluid.
Embodiment 4
Take the Nano-meter SiO_2 of 2.0g2Powder, adds deionized water 60 mL, room temperature ultrasonic disperse 30min, separately takes silane coupled Agent (hexadecyl trimethoxy silane) 2.0g dissolves absolute ethyl alcohol 60mL, by Nano-meter SiO_22Base fluid and silane coupler (ten Six alkyl trimethoxysilanes) ethanol solution mixing, put in there-necked flask, be heated to 75 DEG C of temperature while stirring, filter and use Anhydrous n-hexane washs for several times, is placed on after being dried in 70 DEG C of vacuum drying chambers, obtains the SiO of modification2Nano-particle.
Take 0.5g SiO2Nano-particle puts into there-necked flask, and add water 300mL, warming-in-water to 75 DEG C, adds 2g alkyl virtue Base sodium sulfonate and 2g PEG-4000 mixed solution 100mL, mechanical agitation 8h, the dispersion liquid after stirring is carried out washing 2 times, then By pH value regulation to 9, and add deionized water to 1L, obtain SiO2Water-based nano-fluid.
Embodiment 5
By the nano-fluid of the increased substantially recovery ratio of synthesis in embodiment 1, it is 8.2cm in length, a diameter of 2.5cm, permeability is 1.42 μm2Artificial core on carry out indoor physical simulation oil displacement experiment.First water drive, to aqueous 93%, is surveyed Obtain water drive and can improve oil recovery factor 42.6%, then the nano-fluid of metaideophone 0.3pV (pore volume), water drive to aqueous 98%, survey Obtain and can improve oil recovery factor 16.8% on the basis of water drive again.
Embodiment 6
By the nano-fluid of the increased substantially recovery ratio of synthesis in embodiment 2, it is 8.6cm in length, a diameter of 2.5cm, permeability is 1.48 μm2Artificial core on carry out indoor physical simulation oil displacement experiment.First water drive, to aqueous 92%, is surveyed Obtain water drive and can improve oil recovery factor 41.5%, then the nano-fluid of metaideophone 0.3pV (pore volume), water drive to aqueous 100%, Record and can improve oil recovery factor 14.9% on the basis of water drive again.
Embodiment 7
By the nano-fluid of the increased substantially recovery ratio of synthesis in embodiment 3, it is 8.7cm in length, a diameter of 2.5cm, permeability is 1.51 μm2Artificial core on carry out indoor physical simulation oil displacement experiment.First water drive, to aqueous 93%, is surveyed Obtain water drive and can improve oil recovery factor 41.5%, then the nano-fluid of metaideophone 0.3pV (pore volume), water drive to aqueous 98%, survey Obtain and can improve oil recovery factor 14.3% on the basis of water drive again.
Embodiment 8
By the nano-fluid of the increased substantially recovery ratio of synthesis in embodiment 4, it is 9.5cm in length, a diameter of 2.5cm, permeability is 1.5 μm2Artificial core on carry out indoor physical simulation oil displacement experiment.First water drive, to aqueous 92%, is surveyed Obtain water drive and can improve oil recovery factor 42.8 %, then the nano-fluid of metaideophone 0.3pV (pore volume), water drive to aqueous 98%, Record and can improve oil recovery factor 13.5% on the basis of water drive again.

Claims (3)

1. a kind of preparation method of the nano-fluid for improving oil recovery factor it is characterised in that:Comprise the steps:
1)Preparation nanometer base fluid:Take the nano-powder of 2.0-4.0g, add deionized water 60-80 mL, room temperature ultrasonic disperse 30- 60min;
2)Separately take silane coupler 2.0g dissolving absolute ethyl alcohol 30-60mL;
3)Modified Nano particle:Nanometer base fluid is put in there-necked flask with silane coupler ethanol solution and mixes, while stirring It is heated to 70-75 DEG C, after reaction 4-6h, filtration anhydrous solvent washs for several times, be placed in 60-70 DEG C of vacuum drying chamber dry After dry 12h, obtain the nano-particle of modification;
4)Water-based nano-fluid:Take step(3)Modified nano-particle 0.1-0.5g puts into there-necked flask, and add water 200-300mL, Warming-in-water to 60-75 DEG C, surfactant is mixed with PEG, and adds its mixed solution 100mL, mechanical agitation 6-8h, will Dispersion liquid after stirring carries out washing 2-3 time, then pH value is adjusted to 8-9, and adds deionized water to 1L, obtains water base receiving Meter Liu Ti;Described nano-powder is:Nano-TiO2, zinc oxide, nanometer Fe3O4, Nano-meter SiO_22At least one in powder;Institute The silane coupler stated is selected:Silane coupling reagent KH-570, silane coupler KH-56 or hexadecyl trimethoxy silane;Institute That states prepares nano-TiO2Using Silane coupling reagent KH-570;Prepare nano zine oxide nano-fluid and adopt silane coupler KH- 560 ;Preparation nanometer Fe3O4Using silane coupler KH-560;Prepare Nano-meter SiO_22Fluid adopts hexadecyl trimethoxy silicon Alkane;Described anhydrous solvent is:Absolute ethyl alcohol or anhydrous n-hexane;Described surfactant is:Neopelex, Enuatrol or sodium alklyarylsulfonate.
2. the preparation method of a kind of nano-fluid for improving oil recovery factor according to claim 1, its feature exists In:Described prepares nano-TiO2Using surfactant sodium dodecyl base benzene sulfonic acid sodium salt;Prepare nano zine oxide nano-fluid to adopt It is enuatrol with surfactant;Preparation nanometer Fe3O4It is enuatrol that nano-fluid adopts surfactant;Prepare Nano-meter SiO_22 It is sodium alklyarylsulfonate that nano-fluid adopts surfactant.
3. a kind of using method of the nano-fluid for improving oil recovery factor it is characterised in that:
By the nano-fluid of the claims 1 preparation method acquisition, its using method is:It is 8.2-9.5cm in length, directly Footpath is 2.5cm, and permeability is 1.42-1.51 μm2Artificial core on carry out indoor physical simulation oil displacement experiment;
Rock core is put in clamper, vacuumizes 6 hours, saturation simulation stratum water, measure rock core saturation degree and permeability;Oil drives Water, measures initial oil saturation;Constant temperature 12h under thermostatic drying chamber setting temperature 45 C, carries out water drive oil extremely aqueous 92- first 93%, recording water drive oil displacement efficiency is 41.5-42.8%, then the nano-fluid of metaideophone 0.3pV, then sequent water flooding outlet moisture content For 98-100%, the oil displacement efficiency recording nano-fluid improves 13.5-16.8% than water drive water drive oil displacement efficiency.
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