CN103937478A - Preparation method of nanofluid for improving oil recovery - Google Patents

Preparation method of nanofluid for improving oil recovery Download PDF

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CN103937478A
CN103937478A CN201410152028.7A CN201410152028A CN103937478A CN 103937478 A CN103937478 A CN 103937478A CN 201410152028 A CN201410152028 A CN 201410152028A CN 103937478 A CN103937478 A CN 103937478A
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nano
fluid
water
preparation
silane coupling
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CN103937478B (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
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2208/10Nanoparticle-containing well treatment fluids

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  • Oil, Petroleum & Natural Gas (AREA)
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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 for improving the preparation method of nano-fluid of oil recovery factor
?
Technical field
The present invention relates to petrochemical industry, particularly relate to a kind of nano-fluid for improving oil recovery factor method.
Background technology
In many oil reservoirs, about 2/3rds oil can not be exploited by conventional production method in the world.Therefore,, in mature oilfield, improve recovery efficiency technique (EOR) and have very large potentiality.It is relatively economical that water drive improves recovery ratio method, but mainly early production period, improving water drive in recovery ratio method is comparatively reasonably to select.Water drive is produced after time water drive, can select to add some chemical agents, as alkali, tensio-active agent and polymkeric substance increase the efficiency of water drive process.These chemical substances are joined in injected water, and the wettability of rock surface becomes more hydrophily.The injection of polymkeric substance can increase the viscosity of injected water, improves the sweep efficiency of heterogeneous body and viscosity oil reservoir.Tensio-active agent mainly contains for reducing interfacial tension, thereby makes to act on the oil flow in matrix pores because of capillary force constraint.
The main difficulty that uses polymkeric substance in oil reservoir is chemical degradation and the thermal destruction of polymkeric substance.In addition, typical polymers molecular weight is that 1000 ~ 2,500 ten thousand polymkeric substance are difficult to be injected in low-permeability oil deposit.In addition, high temperature and high salt make surfactant flooding process challenging, cause damage and form obstruction to surfactant oil displacement efficiency, and alkali add problems such as causing occurring in field test the fouling of producing well pit shaft is serious, Produced Liquid difficult treatment.In addition, traditional tensio-active agent is also comparatively responsive to hydrolysis.Therefore, be necessary that exploitation energy heatproof, salt tolerant in reservoir have the novel material of economic benefit.
Nanotechnology can act on more efficient, more cheap, raising oil recovery (EOR) method of more environmental protection.The diameter of conventional reservoir pore is generally all at micron order; Therefore, nano particle can flow therein.In addition, a key property of nano particle is surface effects, and along with particle diameter reduces, the surface-area of particulate sharply becomes greatly, and in the time that the particle diameter of nanoparticle reaches 10nm, specific surface area is 90m 2/ g, when particle diameter is 5nm, specific surface area is 180 m 2/ g, when particle diameter drops to 2nm, specific surface area is surged to 450 m 2/ g.Very large specific surface area causes surface atom number to increase sharply, the atom that is positioned at particle surface accounts for sizable ratio, the serious mismatch of key state, cause the surface energy that Atomic coordinate is not enough and high, there are many active centre, surface step and roughness increase, and the chemical valence of chemical non-equilibrium, non-integer coordination appears in surface, and this causes the chemical property of nanometer system and Chemical Equilibria Systems to occur very big difference.
Nano particle due to surface-area and volume ratio larger, thereby increased surperficial energy.The adsorption of the active substance on solid surface can change the wettability of surface energy and system.Thereby greatly reduce oil water interfacial tension, make to inject fluid at hole displacement process, make crude oil be easy to peel off into little oil droplet, and driven liquid displacement out.In addition, nano-fluid particle has temporary transient ponding to the little duct of reservoir, thereby expand swept volume, make the mother oil displacement that do not fed through in hole out, reach the object that improves recovery ratio, step-down augmented injection, therefore, carry out the research work of nano-fluid raising oil recovery factor field produces is had to direct production meaning, particularly some low permeability oil fields are had more to practical significance.
There is scholar to develop a kind of metal (W, Ni, and Mo) nanometer colloid particle-catalytic agent being scattered in water and carry out pitch exploitation.Have nanocatalyst and carry out comparing result without the asphalt viscosity under nano particle effect to show, nanocatalyst is effective to the viscosity that reduces pitch.The people such as Ponnapati have found water-soluble silicon-dioxide-ethylene oxide type nanometer polymer.Although these nano-complexes do not produce high viscosity in definite concentration, author thinks that the polymkeric substance of higher molecular weight and higher grafting density can improve viscosity.
The people such as Ju carry out the adsorption test of lipophobia and hydrophilic polysilicon nanometer particle and verify that the wettability of sandstone surface changes.Observe wetting ability nano silicon particles and can improve oil recovery factor approximately 9% at size range 10-500 nm compared with pure water, it is effective that polysilicon nanometer particle improves recovery efficiency technique to water drive.
The people such as Hendraningrat study and use wetting ability Nano particles of silicon dioxide, on improving the impact of oil recovery factor, comprise the size of nanoparticle and concentration, initial wettability and the isoparametric impact of temperature.Result shows, by improving temperature, reduces nanoparticle size and reduces nano-fluid input rate and can improve oil recovery factor.In addition, also realize rock from middle wetting regime, obtained the highest oil recovery factor and oil displacement efficiency.And find that oil recovery factor and nano-fluid concentration are not directly proportional, when namely nano-fluid concentration increases, recover the oil and strengthen, but when concentration is during lower than a threshold value, recovery ratio can reduce.
The people such as Karimi have studied the impact of the wettability modification of zirconium white nano-fluid on carbonate reservoir by experiment.Experimental result shows, nano-fluid can by the wettability of rock, from strong oil, wet to become strong water wet.
People's studying alumina nano-fluids such as Giraldo are changing the wettability of Sandstone Cores and the validity of the wettability of induction oleophylic.Research shows, the wettability that nano-fluid can change Sandstone Cores makes rock, and from oil, wet to become water wet.
Summary of the invention
For the deficiencies in the prior art, the present invention adopts following technical scheme:
For improving the preparation method of nano-fluid for oil recovery factor, comprise the steps:
1) prepare nanometer base fluid: get the nano-powder of 2.0-4.0g, add deionized water 60-80 mL, the ultrasonic dispersion of room temperature 30-60min;
2) separately get silane coupling agent 2.0g and dissolve dehydrated alcohol 30-60mL;
3) modified Nano particle: nanometer base fluid is put into there-necked flask with silane coupling agent ethanolic soln and mix, be heated to while stirring 70-75 DEG C, after reaction 4-6h, filter with anhydrous solvent washing several, be placed in 60-70 DEG C of vacuum drying oven and be dried after 12h, obtain the nanoparticle of modification;
4) water-based nano-fluid: get 0.1-0.5g nanoparticle and put into there-necked flask, 200-300mL adds water, warming-in-water is to 60-75 DEG C, tensio-active agent is mixed with PEG, and add its mixing solutions 100mL, mechanical stirring 6-8h, dispersion liquid after stirring is washed 2-3 time, again pH value is adjusted to 8-9, and adds deionized water to 1L, obtain water-based nano-fluid.
Described nano-powder is: nano-TiO 2, zinc oxide, nanometer Fe 3o 4, nanometer SiO 2at least one in powder.
Described silane coupling agent is selected: Silane coupling reagent KH-570, silane coupling agent KH-56 or hexadecyl Trimethoxy silane.
Concrete, the described nano-TiO of preparing 2adopt Silane coupling reagent KH-570 (γ-methacryloxypropyl trimethoxy silane); Prepare nano zine oxide nano-fluid and adopt silane coupling agent KH-560 (γ-glycidyl ether propoxy-Trimethoxy silane); Preparation nanometer Fe 3o 4adopt silane coupling agent KH-560 (γ-glycidyl ether propoxy-Trimethoxy silane); Preparation nanometer SiO 2fluid adopts hexadecyl Trimethoxy silane.
Described anhydrous solvent is: dehydrated alcohol or anhydrous n-hexane.
Described tensio-active agent is: Sodium dodecylbenzene sulfonate, oleic acid are received or sodium alkylarysulfonate.
Concrete, the described nano-TiO of preparing 2adopt surfactant Sodium dodecylbenzene sulfonate; Preparing nano zine oxide nano-fluid employing surfactant is that oleic acid is received; Preparation nanometer Fe 3o 4it is that oleic acid is received that nano-fluid adopts surfactant; Preparation nanometer SiO 2it is sodium alkylarysulfonate that nano-fluid adopts surfactant.
For improving the using method of nano-fluid for oil recovery factor, by the nano-fluid of preparation, be 8.2-9.5cm in length, diameter is 2.5cm, rate of permeation is 1.42-1.51 μ m 2synthetic core on carry out indoor physical simulation oil displacement experiment;
Rock core is put in clamper, vacuumizes 6 hours, saturation simulation local water, measures rock core saturation ratio and rate of permeation; Oil expelling water, measures initial oil saturation; Constant temperature 12h at 45 DEG C of thermostatic drying chamber set temperatures, first carry out water displacing oil to moisture 92-93%, recording water drive oil displacement efficiency is 41.5-42.8%, the nano-fluid of metaideophone 0.3pV again, then follow-up water drive outlet water ratio is 98-100%, and the oil displacement efficiency that records nano-fluid has improved 13.5-16.8% than water drive water drive oil displacement efficiency.
Technical scheme of the present invention exists under high temperature and high salt condition oil displacement efficiency poor for the oil-displacing agent containing tensio-active agent, polymkeric substance in prior art, the deficiency of corrosion and incrustation injury etc. that the high and alkali of working concentration brings stratum and oil well, can obtain good dispersity, stable nano-fluid by technical scheme provided by the invention, the method technique is simple, mild condition, raw material availability is high, cost is low, be easy to industrialization.
Brief description of the drawings
Fig. 1 detects through high-resolution electron microscopy (HRTEM), the TEM figure of the water-base nano TiO2 fluid of the town particle size of catalyst surface between 20-50nm.
Embodiment
Below by specific embodiment, the present invention is described in detail.
embodiment 1
Get the nano-TiO of 2.0g 2powder, adds deionized water 60 mL, and the ultrasonic dispersion of room temperature 30min separately gets Silane coupling reagent KH-570 (γ-methacryloxypropyl trimethoxy silane) 2.0g and dissolves dehydrated alcohol 40mL, by nano-TiO 2base fluid mixes with silane coupling agent KH-560 ethanolic soln, puts into there-necked flask, is heated to while stirring 70 DEG C of temperature, for filtering absolute ethanol washing for several times, be placed on dry in 60 DEG C of vacuum drying ovens after, obtain the TiO of modification 2nanoparticle.
Get 0.5g TiO 2nanoparticle is put into there-necked flask, 300mL adds water, warming-in-water to 70 DEG C, add 2g Sodium dodecylbenzene sulfonate and 2g PEG-4000 mixing solutions 100mL, mechanical stirring 8h, washs the dispersion liquid after stirring three times, then pH value is adjusted to 8, and add deionized water to 1L, obtain TiO 2water-based nano-fluid.
Fig. 1 is water-base nano TiO 2the TEM figure of fluid, as seen from Figure 1, nano-TiO 2particle still can keep single particle not reunite at intensive state like this, illustrates that the nanoparticle of preparation can reach the object of not reuniting.
embodiment 2
Get the nanometer Zinc oxide powder of 2.0g, add deionized water 80 mL, the ultrasonic dispersion of room temperature 60min, separately get silane coupling agent KH-560 (γ-glycidyl ether propoxy-Trimethoxy silane) 2.0g and dissolve dehydrated alcohol 30mL, nano zine oxide base fluid is mixed with silane coupling agent KH-560 ethanolic soln, put into there-necked flask, stir on limit, limit is heated to 70 DEG C of temperature, after reaction 4h, filter with absolute ethanol washing several, be placed in 60 DEG C of vacuum drying ovens dry after, obtain the zinc oxide nano-particle of modification.
Get 0.5g Zinc oxide nanoparticle and put into there-necked flask, add deionized water 200mL, warming-in-water to 70 DEG C, adding 1g oleic acid receives and 1g PEG-4000 mixing solutions 100mL, mechanical stirring 8 h, wash the dispersion liquid after stirring three times, then pH value are adjusted to 8, and add deionized water to 1L, obtain the water base nano-fluid of zinc oxide.
embodiment 3
Get nanometer Fe 3o 4powder 4g, adds deionized water 80 mL, and the ultrasonic dispersion of room temperature 40min separately gets silane coupling agent KH-560 (γ-glycidyl ether propoxy-Trimethoxy silane) 2g and dissolves dehydrated alcohol 30mL, by nanometer Fe 3o 4base fluid mixes with silane coupling agent KH-560 ethanolic soln to be put into there-necked flask and stirs, and after 70 DEG C of water-bath 8h, vacuum filtration obtains solid, puts into constant temperature blast drying oven dry 12 hours, obtains the Fe of modification 3o 4particle.
Get 0.1g nanometer Fe 3o 4particle is put into there-necked flask, 300mL adds water, warming-in-water to 60 DEG C, adding 1g oleic acid receives and 1g PEG-4000 (macrogol) mixing solutions 100mL, mechanical stirring 6h, washs the dispersion liquid after stirring three times, then pH value is adjusted to 8, and add deionized water to 100mL, obtain Fe 3o 4water-based nano-fluid.
embodiment 4
Get the nanometer SiO of 2.0g 2powder, adds deionized water 60 mL, and the ultrasonic dispersion of room temperature 30min separately gets silane coupling agent (hexadecyl Trimethoxy silane) 2.0g and dissolves dehydrated alcohol 60mL, by nanometer SiO 2base fluid mixes with silane coupling agent (hexadecyl Trimethoxy silane) ethanolic soln, put into there-necked flask, be heated to while stirring 75 DEG C of temperature, filter with anhydrous n-hexane washing several, be placed in 70 DEG C of vacuum drying ovens dry after, obtain the SiO of modification 2nanoparticle.
Get 0.5g SiO 2nanoparticle is put into there-necked flask, the 300mL that adds water, warming-in-water to 75 DEG C, add 2g sodium alkylarysulfonate and 2g PEG-4000 mixing solutions 100mL, mechanical stirring 8h, washs the dispersion liquid after stirring 2 times, again pH value is adjusted to 9, and adds deionized water to 1L, obtain SiO 2water-based nano-fluid.
embodiment 5
By the nano-fluid of increased substantially recovery ratio synthetic in embodiment 1, be 8.2cm in length, diameter is 2.5cm, rate of permeation is 1.42 μ m 2synthetic core on carry out indoor physical simulation oil displacement experiment.First water drive, to moisture 93%, record water drive and can improve oil recovery factor 42.6%, then the nano-fluid of metaideophone 0.3pV (volume of voids), and water drive, to moisture 98%, record on water drive basis and can improve oil recovery factor 16.8% again.
embodiment 6
By the nano-fluid of increased substantially recovery ratio synthetic in embodiment 2, be 8.6cm in length, diameter is 2.5cm, rate of permeation is 1.48 μ m 2synthetic core on carry out indoor physical simulation oil displacement experiment.First water drive, to moisture 92%, record water drive and can improve oil recovery factor 41.5%, then the nano-fluid of metaideophone 0.3pV (volume of voids), and water drive, to moisture 100%, record on water drive basis and can improve oil recovery factor 14.9% again.
embodiment 7
By the nano-fluid of increased substantially recovery ratio synthetic in embodiment 3, be 8.7cm in length, diameter is 2.5cm, rate of permeation is 1.51 μ m 2synthetic core on carry out indoor physical simulation oil displacement experiment.First water drive, to moisture 93%, record water drive and can improve oil recovery factor 41.5%, then the nano-fluid of metaideophone 0.3pV (volume of voids), and water drive, to moisture 98%, record on water drive basis and can improve oil recovery factor 14.3% again.
embodiment 8
By the nano-fluid of increased substantially recovery ratio synthetic in embodiment 4, be 9.5cm in length, diameter is 2.5cm, rate of permeation is 1.5 μ m 2synthetic core on carry out indoor physical simulation oil displacement experiment.First water drive, to moisture 92%, record water drive and can improve oil recovery factor 42.8 %, then the nano-fluid of metaideophone 0.3pV (volume of voids), and water drive, to moisture 98%, record on water drive basis and can improve oil recovery factor 13.5% again.

Claims (8)

1. for improving the preparation method of nano-fluid for oil recovery factor, it is characterized in that: comprise the steps:
1) prepare nanometer base fluid: get the nano-powder of 2.0-4.0g, add deionized water 60-80 mL, the ultrasonic dispersion of room temperature 30-60min;
2) separately get silane coupling agent 2.0g and dissolve dehydrated alcohol 30-60mL;
3) modified Nano particle: nanometer base fluid is put into there-necked flask with silane coupling agent ethanolic soln and mix, be heated to while stirring 70-75 DEG C, after reaction 4-6h, filter with anhydrous solvent washing several, be placed in 60-70 DEG C of vacuum drying oven and be dried after 12h, obtain the nanoparticle of modification;
4) water-based nano-fluid: get 0.1-0.5g nanoparticle and put into there-necked flask, 200-300mL adds water, warming-in-water is to 60-75 DEG C, tensio-active agent is mixed with PEG, and add its mixing solutions 100mL, mechanical stirring 6-8h, dispersion liquid after stirring is washed 2-3 time, again pH value is adjusted to 8-9, and adds deionized water to 1L, obtain water-based nano-fluid.
2. according to claim 1 a kind of for improving the preparation method of nano-fluid of oil recovery factor, it is characterized in that: described nano-powder is: nano-TiO 2, zinc oxide, nanometer Fe 3o 4, nanometer SiO 2at least one in powder.
3. according to claim 1 a kind of for improving the preparation method of nano-fluid of oil recovery factor, it is characterized in that: described silane coupling agent is selected: Silane coupling reagent KH-570, silane coupling agent KH-56 or hexadecyl Trimethoxy silane.
4. according to claim 2 a kind of for improving the preparation method of nano-fluid of oil recovery factor, it is characterized in that: the described nano-TiO of preparing 2adopt Silane coupling reagent KH-570; Prepare nano zine oxide nano-fluid and adopt silane coupling agent KH-560; Preparation nanometer Fe 3o 4adopt silane coupling agent KH-560; Preparation nanometer SiO 2fluid adopts hexadecyl Trimethoxy silane.
5. according to claim 1 a kind of for improving the preparation method of nano-fluid of oil recovery factor, it is characterized in that: described anhydrous solvent is: dehydrated alcohol or anhydrous n-hexane.
6. according to claim 1 a kind of for improving the preparation method of nano-fluid of oil recovery factor, it is characterized in that: described tensio-active agent is: Sodium dodecylbenzene sulfonate, oleic acid are received or sodium alkylarysulfonate.
7. according to claim 2 a kind of for improving the preparation method of nano-fluid of oil recovery factor, it is characterized in that: the described nano-TiO of preparing 2adopt surfactant Sodium dodecylbenzene sulfonate; Preparing nano zine oxide nano-fluid employing surfactant is that oleic acid is received; Preparation nanometer Fe 3o 4it is that oleic acid is received that nano-fluid adopts surfactant; Preparation nanometer SiO 2it is sodium alkylarysulfonate that nano-fluid adopts surfactant.
8. for improving the using method of nano-fluid for oil recovery factor, it is characterized in that:
By the nano-fluid of preparation, be 8.2-9.5cm in length, diameter is 2.5cm, rate of permeation is 1.42-1.51 μ m 2synthetic core on carry out indoor physical simulation oil displacement experiment;
Rock core is put in clamper, vacuumizes 6 hours, saturation simulation local water, measures rock core saturation ratio and rate of permeation; Oil expelling water, measures initial oil saturation; Constant temperature 12h at 45 DEG C of thermostatic drying chamber set temperatures, first carry out water displacing oil to moisture 92-93%, recording water drive oil displacement efficiency is 41.5-42.8%, the nano-fluid of metaideophone 0.3pV again, then follow-up water drive outlet water ratio is 98-100%, and the oil displacement efficiency that records nano-fluid has improved 13.5-16.8% than water drive water drive oil displacement efficiency.
CN201410152028.7A 2014-04-16 2014-04-16 Preparation method of nanofluid for improving oil recovery Expired - Fee Related CN103937478B (en)

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