CN103387827B - Nano material association clean fracturing liquid system and the application in oil-gas field thereof - Google Patents
Nano material association clean fracturing liquid system and the application in oil-gas field thereof Download PDFInfo
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Abstract
The invention provides a kind of nano material association clean fracturing liquid system, described system comprises the liquid trivalent alcohol of nano material, clean fracturing fluid and dispersing auxiliary.Nano material association clean fracturing liquid system provided by the invention can be applied to the oil-gas field up to more than 130 DEG C, still can keep certain system viscosity at such a temperature.The temperature tolerance of the nano material association clean fracturing liquid system that the present invention prepares significantly improves, and is conducive to its application in high temperature deep well oil field.And this system makes nanotechnology and petroleum industry combine closely, wide market.
Description
Technical field
The present invention relates to a kind of nano material association clean fracturing liquid system and the application in oil-gas field thereof, the application especially in oil-gas field storey increase design.
Background technology
Hydraulic fracturing technology has played vital role in exploitation of oil-gas field, is the main process technology that low and extra-low permeability reservoir improves per-well production.Without residue clean fracturing fluid to supporting crack and formation damage little, be domestic and international fracturing liquid research development trend and focus.Along with going deep into of deep & ultra-deep well oil-gas exploration and development, the conventional fracturing fluid system shear viscosity that is at high temperature heated reduces too fast, cannot meet the requirement of ultra-deep well fracturing transformation, therefore the raising of fracturing fluid system heat resistance will become the key problem in technology of fracturing technology progress.Nanomaterials and nanotechnology is the cutting edge technology of development in science and technology in recent ten years, because little its surface atom number, surface energy and the surface tension of making of particle size forming nano material sharply increases with the decline of particle diameter, and show many new kink characteristics being different from conventional material, nano material is obtained in a lot of fields and applies widely.In recent years, nano material also causes the attention of oil-field development person gradually, and obtains application in field drilling, development of injection-production, disposing polluted water in oil and oil and gas pipes protection etc.Nano material is incorporated in clean fracturing fluid, forms nano material association clean fracturing liquid system, higher oil-gas field temperature can be tolerated, thus open up the degree of depth of dark oil gas drilling exploitation.These nanoparticles can serve as stablizer and the fluid loss control agents of the completion of petroleum industry and the fluid of frscturing, can maintain fluid high viscosity at high temperature and reduce leak-off, and not causing reservoir injury.
How to develop the problem that resistant to elevated temperatures nano material association clean fracturing liquid system becomes those skilled in the art's care.As Chinese patent application 102093874A relates to a kind of anion type nano compound clean fracturing fluid and preparation method thereof.Its quality product component is as follows: negatively charged ion viscoelastic surfactant: 3 ~ 7 parts, cosurfactant: 0.05 ~ 0.5 part, gegenion salt: 3 ~ 10 parts, nano particle: 0.05 ~ 0.5 part, 100 parts, water.Above component to be stirred by solution blending by proportioning and both can be made into a kind of anion type nano compound clean fracturing fluid.This product has higher visco-elasticity, has good to take grittiness energy, and can meet the on-the-spot fracturing liquid of oil-gas field completely and make seam, take sand requirement, its product can resistance to oil-gas field temperature be 75 ~ 95 DEG C.And document SPE552-558,2008, Nanotechnologyapplicationsinviscoelasticsurfactantstimul ationfuids describes the viscoelastic surfactant fracturing liquid (VES) be combined with nanotechnology, and this New Fracturing Fluid at high temperature still can keep viscosity and not produce injury to reservoir.This nanoparticle is the mineral crystal of a kind of 35nm, and this crystal has unique surfactivity, and it can make VES micella by chemisorption, and (250 ℉ that is 121 DEG C) can not leak-off at relatively high temperatures.
But the raising of the heat resistance of nano material association clean fracturing liquid system need further research and development and improves.
Summary of the invention
The invention provides a kind of nano material association clean fracturing liquid system, described system comprises nano material, clean fracturing fluid and dispersing auxiliary, and wherein, described dispersing auxiliary is liquid trivalent alcohol.
Nano material association clean fracturing liquid system provided by the invention can be applied to the oil-gas field up to more than 130 DEG C, still can keep certain system viscosity at such a temperature, possess good application prospect in oil field.
Nano material of the present invention is MgC
2o
4, Al (OH)
3, γ-Al
2o
3, SiO
2, TiO
2with one or more in ZnO powder.Nano material of the present invention can be purchased; But more preferably described nano material adopts the homemade method in laboratory to obtain, can according to the needs of nano particle diameter and the characteristic being applied to clean fracturing fluid thereof in self-control process, on the preparation method basis of Conventional nano material, suitable adjustment preparation method, makes it be particularly useful for the formation of nano material association clean fracturing liquid system of the present invention.As in the embodiment of the present invention 1 ~ 6 the method preparing nano material that adopts simple, reaction conditions is gentle, and productive rate is high, repeatable strong.
In the present invention, the volume fraction of described trivalent alcohol in described clean fracturing liquid system is preferably 5 ~ 50%, and more preferably 10 ~ 20%; The dispersing auxiliary trivalent alcohol of consumption like this makes nano material to be dissolved in completely in described clean fracturing fluid, and it is excessive and damage effect and the cost of idleness of clean fracturing liquid system to be unlikely to consumption.
In the present invention, through experimental results demonstrate, the massfraction of described nano material in described clean fracturing liquid system is preferably 0.01 ~ 20%, and more preferably 0.1 ~ 1%.
Clean fracturing fluid of the present invention such as containing viscoelastic surfactant concentration be the aqueous solution of 0.1 ~ 4wt%.
The present invention also provides the application of a kind of nano material association clean fracturing liquid system described above in oil-gas field storey increase design.Wherein, described application of temperature is 120 ~ 180 DEG C, and more preferably described application of temperature is 125 ~ 175 DEG C.
The preparation method of nano material association clean fracturing liquid system of the present invention is such as: 0.1g nano material be scattered in 5ml dispersing auxiliary, joined in 40ml clean fracturing fluid and form clean fracturing liquid system.
The temperature tolerance of the nano material association clean fracturing liquid system that the present invention prepares significantly improves, and is conducive to its application in high temperature deep well oil field.This system makes nanotechnology and petroleum industry combine closely, wide market.
Accompanying drawing explanation
Fig. 1 is nanometer MgC in embodiment 1
2o
4the XRD spectra of powder;
Fig. 2 is nanometer Al (OH) in embodiment 2
3the XRD spectra of powder;
Fig. 3 is nanometer γ-Al in embodiment 3
2o
3the XRD spectra of powder;
Fig. 4 is Nano-meter SiO_2 in embodiment 4
2the XRD spectra of powder;
Fig. 5 is nano-TiO in embodiment 5
2the XRD spectra of powder;
Fig. 6 is the XRD spectra of nano ZnO powder in embodiment 6;
Fig. 7 does not use the clean fracturing fluid of nano material at 130 DEG C and 170s in comparative example 1
-1viscosity under shearing rate;
Fig. 8 uses Nano-meter SiO_2 in embodiment 7
2clean fracturing fluid at 130 DEG C and 170s
-1viscosity under shearing rate;
Fig. 9 uses nano-TiO in embodiment 8
2clean fracturing fluid at 130 DEG C and 170s
-1viscosity under shearing rate;
Figure 10 uses Nano-meter SiO_2 in embodiment 9
2clean fracturing fluid at 150 DEG C and 170s
-1viscosity under shearing rate;
Figure 11 uses nano-TiO in embodiment 10
2clean fracturing fluid at 170 DEG C and 170s
-1viscosity under shearing rate.
Embodiment
Below by embodiment, the present invention is described further, and protection scope of the present invention is not as restriction.
Embodiment 1
Nanometer MgC
2o
4preparation method: be the magnesium chloride hexahydrate of 50:1:50 by mol ratio, oxalic acid tetraacethyl disodium (C
10h
14n
2o
8na
22H
2o) and sodium oxalate be dissolved in wiring solution-forming in distilled water, wherein the concentration of magnesium chloride is 0.5mol/L, stir 1h, ageing 20h, 80 DEG C of oven dry, 500 DEG C of roasting 3h, obtain nanometer MgC
2o
4powder, its particle diameter is 11.8nm, carries out the spectrogram of XRD sign as shown in Figure 1 to it.
Embodiment 2
Nanometer Al (OH)
3preparation method: respectively prepare massfraction be 27% and 12% aluminum nitrate and ammonium bicarbonate soln.Join in aluminum nitrate solution by a certain amount of CTAB, the amount of substance of aluminum nitrate and CTAB, than being 1:0.006, stirring and obtains settled solution.Then ammonium bicarbonate soln is slowly added drop-wise in the aluminum nitrate solution of vigorous stirring, after dropwising, continues to stir 1h, ageing 48h, wet gel is dry at 80 DEG C, obtain nanometer Al (OH)
3powder, its particle diameter is 37.8nm, carries out the spectrogram of XRD sign as shown in Figure 2 to it.
Embodiment 3
Nanometer γ-Al
2o
3preparation method: by the nanometer Al (OH) prepared in embodiment 2
3powder obtains nanometer γ-Al at 500 DEG C of roasting 3h
2o
3powder, its particle diameter is 18.7nm, carries out the spectrogram of XRD sign as shown in Figure 3 to it.
Embodiment 4
Nano-meter SiO_2
2preparation method: preparation 25ml concentration is the acetic acid aqueous solution of 0.01mol/l, then add 2.5g polyoxyethylene glycol, fully stir and make it dissolve, and then add 11.25ml methyl silicate, after ice-water bath half an hour, after 40 DEG C of water-baths formation gels, ageing 1 day, adds 0.01mol/l ammoniacal liquor, is placed in reactor, 120 DEG C of hydro-thermal 6h, 80 DEG C of dryings, 550 DEG C of roastings, grinding obtains Nano-meter SiO_2
2powder, its particle diameter is 0.8nm, carries out the spectrogram of XRD sign as shown in Figure 4 to it.
Embodiment 5
Nano-TiO
2preparation method: the anhydrous C butyl (tetra) titanate of 5mL being slowly added drop-wise under vigorous stirring 15mL
2h
5in OH, continue to stir the first solution that 20min obtains homogeneous transparent.In addition, under room temperature, deionized water is added anhydrous C
2h
5make the ethanolic soln that volume ratio is 1:4 in OH, obtain the second solution.Under the condition of vigorous stirring, be added dropwise in the second solution by the first solution, dropwise rear continuation and stir 30min, evaporate to dryness under 80 DEG C of water-baths, be placed in 80 DEG C of baking ovens dry, 400 DEG C of roasting 3h, obtain nano-TiO
2powder, its particle diameter is 10.8nm, carries out the spectrogram of XRD sign as shown in Figure 5 to it.
Embodiment 6
The preparation method of nano-ZnO: prepare sodium carbonate solution that 200ml concentration is 0.5mol/l respectively and 300ml concentration is the solution of zinc sulfate of 0.1mol/l, then, under the condition of vigorous stirring, solution of zinc sulfate is slowly added drop-wise in sodium carbonate solution, after dropwising, continue to stir half an hour, after aging 1 hour, fully wash, 80 DEG C of dryings, 300 DEG C of roasting 3h, obtain nano ZnO powder, its particle diameter is 10.5nm, carries out the spectrogram of XRD sign as shown in Figure 6 to it.
Comparative example 1
After filling it up with the clean fracturing fluid not adding nano material in rheometer sample cup, sample is heated.Rotor is with shearing rate 170s simultaneously
-1rotate, controlling heat-up rate is that 3 DEG C ± 0.2 DEG C/min is to probe temperature 130 DEG C ± 0.3 DEG C, and keep this temperature in whole process of the test, evaluate the rheological under the heatproof resistant to shearing ability of clean fracturing liquid system and high temperature, the viscosity curve of gained as shown in Figure 7.In figure, left ordinate zou and represent viscosity, right ordinate zou and △ represent temperature, abscissa representing time, as we can see from the figure, along with the rising viscosity of temperature is in decline, when temperature reaches 130 DEG C, when nano material, the viscosity of clean fracturing fluid drops to below 30mPas in 60min.
Embodiment 7
By the Nano-meter SiO_2 of preparation in 0.1g embodiment 4
2be scattered in after in 5ml dispersing auxiliary glycerol, join in 40ml clean fracturing fluid (be 0.8% containing viscoelastic surfactant concentration) the clean fracturing liquid system formed containing nano material, in rheometer sample cup, fill it up with this kind containing after the clean fracturing liquid system of nano material, sample is heated.Rotor is with shearing rate 170s simultaneously
-1rotate, controlling heat-up rate is that 3 DEG C ± 0.2 DEG C/min is to probe temperature 130 DEG C ± 0.3 DEG C, and keep this temperature in whole process of the test, evaluate containing the rheological under the heatproof resistant to shearing ability of clean fracturing liquid system of nano material and high temperature, the viscosity curve of gained as shown in Figure 8.In figure, left ordinate zou and represent viscosity, and right ordinate zou and △ represent temperature, abscissa representing time, as we can see from the figure, along with the rising viscosity of temperature is in decline, when temperature reaches 130 DEG C, add SiO
2when nano material, the viscosity of clean fracturing fluid can 130 DEG C remain on 50mPas and more than.Graphical results shows the viscosity of clean fracturing fluid energy stabilized fluid when high temperature that nano material is associated.
Embodiment 8
By the nano-TiO of preparation in 0.45g embodiment 5
2be scattered in after in 5ml dispersing auxiliary glycerol, join in 40ml clean fracturing fluid (be 0.8% containing viscoelastic surfactant concentration) the clean fracturing liquid system formed containing nano material, in rheometer sample cup, fill it up with this kind containing after the clean fracturing liquid system of nano material, sample is heated.Rotor is with shearing rate 170s simultaneously
-1rotate, controlling heat-up rate is that 3 DEG C ± 0.2 DEG C/min is to probe temperature 130 DEG C ± 0.3 DEG C, and keep this temperature in whole process of the test, evaluate containing the rheological under the heatproof resistant to shearing ability of fracturing fluid system of nano material and high temperature, the viscosity curve of gained as shown in Figure 9.In figure, left ordinate zou and represent viscosity, and right ordinate zou and △ represent temperature, abscissa representing time, as we can see from the figure, along with the rising viscosity of temperature is in decline, when temperature reaches 130 DEG C, add TiO
2when nano material, the viscosity of clean fracturing fluid can 130 DEG C remain on 60mPas and more than.Graphical results shows the viscosity of clean fracturing fluid energy stabilized fluid when high temperature that nano material is associated.
Embodiment 9
By the Nano-meter SiO_2 of preparation in 1.0g embodiment 4
2be scattered in after in 5ml dispersing auxiliary glycerol, join in 40ml clean fracturing fluid (be 0.8% containing viscoelastic surfactant concentration) the clean fracturing liquid system formed containing nano material, in rheometer sample cup, fill it up with this kind containing after the clean fracturing liquid system of nano material, sample is heated.Rotor is with shearing rate 170s simultaneously
-1rotate, controlling heat-up rate is that 3 DEG C ± 0.2 DEG C/min is to probe temperature 150 DEG C ± 0.3 DEG C, and keep this temperature in whole process of the test, evaluate containing the rheological under the heatproof resistant to shearing ability of clean fracturing liquid system of nano material and high temperature, the viscosity curve of gained as shown in Figure 10.In figure, left ordinate zou and represent viscosity, and right ordinate zou and △ represent temperature, abscissa representing time, as we can see from the figure, along with the rising viscosity of temperature is in decline, when temperature reaches 150 DEG C, add SiO
2when nano material, the viscosity of clean fracturing fluid can 150 DEG C remain on 50mPas and more than.Graphical results shows the viscosity of clean fracturing fluid energy stabilized fluid when high temperature that nano material is associated.
Embodiment 10
By the nano-TiO of preparation in 2.25g embodiment 5
2be scattered in after in 5ml dispersing auxiliary glycerol, join in 40ml clean fracturing fluid (be 0.8% containing viscoelastic surfactant concentration) the clean fracturing liquid system formed containing nano material, in rheometer sample cup, fill it up with this kind containing after the clean fracturing liquid system of nano material, sample is heated.Rotor is with shearing rate 170s simultaneously
-1rotate, controlling heat-up rate is that 3 DEG C ± 0.2 DEG C/min is to probe temperature 170 DEG C ± 0.3 DEG C, and keep this temperature in whole process of the test, evaluate containing the rheological under the heatproof resistant to shearing ability of clean fracturing liquid system of nano material and high temperature, the viscosity curve of gained as shown in figure 11.In figure, left ordinate zou and represent viscosity, and right ordinate zou and △ represent temperature, abscissa representing time, as we can see from the figure, along with the rising viscosity of temperature is in decline, when temperature reaches 170 DEG C, add SiO
2when nano material, the viscosity of clean fracturing fluid can 170 DEG C remain on 50mPas and more than.Graphical results shows the viscosity of clean fracturing fluid energy stabilized fluid when high temperature that nano material is associated.
Claims (6)
1. a nano material association clean fracturing liquid system, it is characterized in that, described system is made up of nano material, clean fracturing fluid and dispersing auxiliary, wherein, described dispersing auxiliary is liquid trivalent alcohol, the volume fraction of described trivalent alcohol in described clean fracturing liquid system is 5-50%, and the massfraction of described nano material in described clean fracturing liquid system is 0.01-20%, and described nano material is MgC
2o
4, Al (OH)
3, γ-Al
2o
3, SiO
2, TiO
2with one or more in ZnO powder, described clean fracturing fluid is be the aqueous solution of 0.1-4wt% containing viscoelastic surfactant concentration.
2. system according to claim 1, is characterized in that, the volume fraction of described trivalent alcohol in described clean fracturing liquid system is 10-20%.
3. system according to claim 1 and 2, is characterized in that, the massfraction of described nano material in described clean fracturing liquid system is 0.1-1%.
4. one kind as the application of nano material association clean fracturing liquid system in oil-gas field storey increase design as described in any one in claims 1 to 3.
5. application according to claim 4, is characterized in that, the temperature of described application is 120-180 DEG C.
6. application according to claim 4, is characterized in that, the temperature of described application is 125-175 DEG C.
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