CN105038756B - A kind of displacement of reservoir oil carbon dioxide foam systems of addition hydrophilic nano particle and preparation method thereof - Google Patents
A kind of displacement of reservoir oil carbon dioxide foam systems of addition hydrophilic nano particle and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of displacement of reservoir oil carbon dioxide foam systems of addition hydrophilic nano particle and preparation method thereof.Carbon dioxide foam systems content of component is as follows:0.1 0.3 parts of nonionic surfactant, 12 parts of hydrophilic nano particle, 0.01 0.2 parts of inorganic salts, 0.2 0.8 parts of carbon dioxide, 100 parts of water.Be uniformly dispersed with ultrasonic wave separating apparatus after preparing foaming agent system in proportion, stirred using Waring Blender methods after carbon dioxide is passed through into stirring cup to obtain the final product.It is more preferable compared to the carbon dioxide foaming heat-resistant salt-resistant performance that conventional surfactants produce to the addition of the carbon dioxide foaming of hydrophilic nano, and the foaming agent cost of hydrophobic nanoparticles is low, dispersion stabilization is good than adding, it is easier to promote and apply in Oil Field.
Description
Technical field
The present invention relates to a kind of carbon dioxide foam systems that with the addition of hydrophilic nano particle and preparation method thereof, belong to
Oil-Gas Field Development Engineering technical field.
Background technology
The burning of fossil fuel will produce substantial amounts of carbon dioxide, and the random discharge of carbon dioxide will cause greenhouse
Effect, endangers the weather safety of the mankind.With the increasingly raising that people require for carbon dioxide discharge-reduction, carbon dioxide buries
Deposit with having obtained more and more concerns using technology.
Carbon dioxide can interact with the crude oil in stratum, and playing reduces viscosity of crude, improves crude oil elasticity
The effect of energy, and nitrogen, air and methane gas are compared, carbon dioxide is low with the miscible pressure of crude oil, is led in oil field development
It is a kind of ideal oil displacement agent in domain.Therefore, during carbon dioxide being used crude oil production, it can both play and subtract
The effect of row, and the recovery ratio of crude oil can be improved, there is good social benefit and economic benefit.And since carbon dioxide is on ground
Viscosity is low under the conditions of layer, and big with the mobility ratio of crude oil, many stratum have heterogeneous feature in addition, therefore in oil displacement process
Gas channeling phenomenon easily occurs, causes the sweep efficiency to formation crude oil low, so as to reduce the oil displacement efficiency of carbon dioxide.Foam
The mobility of gas can be reduced, and there is selective shut-off to hypertonic stratum, can preferably solve problem above.Often
The carbon dioxide foaming foaming agent main component of rule is surfactant, and the heatproof of conventional surfactants, salt resistant character compared with
Difference, high temperature and high salinity condition stability inferior in the earth formation are poor, it is impossible to form the higher carbon dioxide foaming of quality.Liu
It is firelight or sunlight, Hua Qingchang oil reservoirs CO2Drive foam system evaluation study, Xi'an Petroleum University, 2012, the paper studies temperature, mineralising
The influences of the factor to the carbon dioxide foaming stability produced by surfactant such as degree.The result shows that surfactant ZY-1
The carbon dioxide foaming of generation half-life period when sodium chloride (NaCl) concentration is 1% is 9.17min, is partly declined when temperature is 60 DEG C
Phase is only 6.67min.
For this problem, there is researcher to propose to improve carbon dioxide foaming on ground by adding hydrophobic nano particle
Stability in layer.Li Zhaomin etc., SiO2Nano particle is with SDS to CO2The synergistic stability effect of foam, Northeast Petroleum University are learned
Report, in June, 2014, the 3rd phase, the document have studied hydrophobic type nano SiO 2 particle with anionic surfactant to two
Aoxidize the stablizing effect of carbon foam.The result shows that in SiO2Mass concentration is the dioxy obtained when 1.5%, SDS concentration is 0.25
Change carbon foam half-life period can reach 37.2min.However, hydrophobic nano particle cost is higher, and since hydrophobicity is strong, in water
In disperse that difficulty is big, and the foaming agent solution dispersion stabilization being prepared into is poor, therefore may will face in Oil Field application
Many construction technology problems.
Single hydrophilic nano particle dispersion can not play the role of stable foam, but since its surface can be by part
SURFACTANT ADSORPTION and produce synergistic effect, therefore with part surface activating agent suitably proportioning under, hydrophilic nano
Grain can also play the role of improving carbon dioxide foaming heatproof, salt resistant character.Further, since hydrophilic nano particle cost is remote
Less than hydrophobic nano particle, and it is easy to disperse in water, therefore, practical value is higher in Oil Field, has preferable
Application prospect.
The content of the invention
For deficiency of the prior art, the present invention provides a kind of carbon dioxide foaming body for adding hydrophilic nano particle
System and preparation method thereof.
Term explanation:
Hydrophilic nano SiO 2 particle:Silica nanoparticle surface is modified using silanol, modified
So that nano grain surface carries the silanol of different densities, so as to show different degrees of hydrophobic performance, silanol
Density is bigger, and particle hydrophilicity is stronger, which is conventional commercial products.
Technical scheme is as follows:
A kind of carbon dioxide foam systems for adding hydrophilic nano particle, including material quality part composition are as follows:
0.1-0.3 parts of nonionic surfactant, 1-2 parts of hydrophilic nano particle, 0.01-0.2 parts of inorganic salts, titanium dioxide
0.2-0.8 parts of carbon, 100 parts of water.
, according to the invention it is preferred to, the nonionic surfactant is lauryl alcohol polyethylene glycol oxide polyethenoxy ether
(C12E9P3)。
, according to the invention it is preferred to, the hydrophilic nano particle is hydrophilic nano SiO 2 particle;Further
Preferably, the hydrophilic nano grain diameter is 15-50nm, density of surface silanol groups 1-2/nm2, the contact with water
Angle is 38-60 °.
, according to the invention it is preferred to, the inorganic salts are sodium chloride.
, according to the invention it is preferred to, the carbon dioxide foam systems of described addition hydrophilic nano particle, including raw material
Mass parts composition is as follows:
0.1-0.3 parts of lauryl alcohol polyethylene glycol oxide polyethenoxy ether, 1-2 parts of hydrophilic nano SiO 2 particle, sodium chloride
0.01-0.2 parts, 0.2-0.8 parts of carbon dioxide, 100 parts of water.
, according to the invention it is preferred to, the carbon dioxide foam systems of described addition hydrophilic nano particle, including raw material
Mass parts composition is as follows:
0.1 part of lauryl alcohol polyethylene glycol oxide polyethenoxy ether, 1.5 parts of hydrophilic nano SiO 2 particle, sodium chloride 0.2
Part, 0.2-0.8 parts of carbon dioxide, 100 parts of water.
According to the present invention, the preparation method of the carbon dioxide foam systems of above-mentioned addition hydrophilic nano particle, including step
It is rapid as follows:
(1) hydrophilic nano particle is added to the water and stirred evenly according to proportioning, then sequentially add nonionic table
Face activating agent and inorganic salts, ultrasonic disperse 3-5min;
(2) carbon dioxide 2-5min is continually fed into the system obtained to step (1), then with 7000-9000r/min's
Rotating speed stirs 3-5min min, to obtain the final product.
Hydrophilic nano SiO 2 particle of the present invention, can market buy, can be also prepared by the prior art.
The principle of the present invention:
Hydrophilic nano particle is predominantly located in liquid phase since hydrophilicity is too strong, it is impossible to gas-liquid interface is adsorbed onto, because
And stable foam can not be played the role of.The polar group of lauryl alcohol polyethylene glycol oxide polyethenoxy ether and the silicon of nano grain surface
Hydroxyl can be formed by hydrogen bond action and adsorbed so that and nano particle hydrophobic performance strengthens, and can be adsorbed onto on gas-liquid interface, so that
Stabilization is played to foam.And when laruyl alcohol polyoxyethylene poly-oxygen propylene aether excessive concentration, under the action of Van der Waals force,
Double-deck absorption can be formed between surfactant in particle surface so that particle hydrophilicity strengthens, and loses the effect of foam stabilizing.
Therefore, only under suitable proportioning, the two could play carbon dioxide foaming the stable effect of collaboration.
Compared to nitrogen and air, the solubility of carbon dioxide in water is larger, and diffusion velocity is very fast in the liquid phase, exacerbates
The disproportionation of carbon dioxide foaming, causes carbon dioxide foaming more unstable compared to nitrogen and air foam.And nanometer
Grain can reduce contact of the carbon dioxide with liquid phase when it is adsorbed onto on gas-liquid interface since size is much larger than surfactant
Area, so as to reduce disproportionation, enhances the stability of foam.In addition, the addition of nano particle can increase liquid phase
Viscosity, so as to slow down the drain age velocity of foam.And the addition of appropriate sodium chloride can reduce the surface potential of nano particle, subtract
Small intergranular electrostatic repulsion so that arrangement of the particle on gas-liquid interface is even closer, further increases carbon dioxide
The stability of foam.
The excellent technique effect of the present invention:
1st, by the compounding with nonionic surfactant, make can not the hydrophilic nano particle of independent foam stabilizing obtain foam stabilizing
Performance.Diffusion rate is very fast in the liquid phase for carbon dioxide, therefore the disproportionation of carbon dioxide foaming is formed compared to other gases
Foam become apparent, and since nano particle is larger compared to the size of surfactant, when it is adsorbed in gas-liquid interface
The contact area of carbon dioxide and liquid phase can be reduced, the disproportionation of foam is reduced, greatly improve carbon dioxide foaming
Stability.
2nd, hydrophilic nano particle has the characteristics that solid particle, and heatproof, salt resistant character are stronger, carbon dioxide foaming is existed
High temperature, high salt formation condition under still there is preferable stability, play the advantage of its displacement of reservoir oil.
3rd, hydrophilic nano particle is smaller compared to formation pore throat size, can freely migrate, stratum will not be damaged;
In addition, hydrophilic nano particle is easy to disperse in water, foaming agent system preparation method and site construction technology are simple, and compare
Hydrophobic nanoparticles are of low cost, it is easier to are promoted and applied in oil field.
Embodiment:
It is below the further explanation done in conjunction with specific embodiments to the present invention, but scope of the present invention
It is not limited to the scope involved by embodiment.
Raw materials used in embodiment is convenient source, and device therefor is conventional equipment.
Wherein:Hydrophilic nano SiO 2 particle, gloomy trade Co., Ltd of Guangzhou Holley are on sale.
Embodiment 1:
A kind of carbon dioxide foam systems for adding hydrophilic nano particle, including material quality part composition are as follows:
Lauryl alcohol polyethylene glycol oxide polyethenoxy ether (C12E9P3) 0.15g, hydrophilic nano SiO 2 particle (average grain diameter
16nm, surface silicon alkanol density 1.5/nm2, the contact angle with water is 38.8 °) and 1.5g, sodium chloride (NaCl) 0.2g, carbon dioxide
0.5g, distilled water 100g.
Preparation method is as follows:
(1) hydrophilic nano SiO 2 particle is added in distilled water and stirred evenly, sequentially added laruyl alcohol and gather
Ethylene oxide polyethenoxy ether (C12E9P3) and sodium chloride (NaCl), ultrasonic disperse is carried out to mixed system using ultrasonic wave separating apparatus
3min;
(2) foam is produced using Waring Blender methods:3min dioxies are continually fed into the system obtained to step (1)
Change carbon, 3min is then stirred to system with the rotating speed of 8000r/min, up to carbon dioxide foam systems 315ml.
Under room temperature, the carbon dioxide foam systems analysis liquid half-life period that the present embodiment obtains is 29.93min.
Embodiment 2:
A kind of carbon dioxide foam systems for adding hydrophilic nano particle, including material quality part composition are as follows:
Lauryl alcohol polyethylene glycol oxide polyethenoxy ether (C12E9P3) 0.1g, hydrophilic nano SiO 2 particle (average grain diameter
20nm, surface silicon alkanol density 1/nm2, the contact angle with water is 50.4 °) and 1.5g, sodium chloride (NaCl) 0.2g, carbon dioxide
0.5g, distilled water 100g.
Preparation method is as follows:
(1) hydrophilic nano SiO 2 particle is added in distilled water and stirred evenly, sequentially added laruyl alcohol and gather
Ethylene oxide polyethenoxy ether (C12E9P3) and sodium chloride (NaCl), ultrasonic disperse is carried out to mixed system using ultrasonic wave separating apparatus
3min;
(2) foam is produced using Waring Blender methods:3min dioxies are continually fed into the system obtained to step (1)
Change carbon, 3min is then stirred to system with the rotating speed of 8000r/min, up to carbon dioxide foam systems 379ml.
Under room temperature, the carbon dioxide foam systems analysis liquid half-life period that the present embodiment obtains is 42.64min.
Embodiment 3:
A kind of carbon dioxide foam systems for adding hydrophilic nano particle, including material quality part composition are as follows:
Lauryl alcohol polyethylene glycol oxide polyethenoxy ether (C12E9P3) 0.1g, hydrophilic nano SiO 2 particle (average grain diameter
20nm, surface silicon alkanol density 1/nm2, the contact angle with water is 50.4 °) and 1.5g, sodium chloride (NaCl) 0.2g, carbon dioxide
0.5g, distilled water 100g.
Preparation method is as follows:
(1) hydrophilic nano SiO 2 particle is added in distilled water and stirred evenly, sequentially added laruyl alcohol and gather
Ethylene oxide polyethenoxy ether (C12E9P3) and sodium chloride (NaCl), ultrasonic disperse is carried out to mixed system using ultrasonic wave separating apparatus
3min;
(2) mixed system is placed in 80 DEG C of insulating boxs, constant temperature 3h;
(3) foam is produced using Waring Blender methods:3min dioxies are continually fed into the system obtained to step (2)
Change carbon, 3min is then stirred to system with the rotating speed of 8000r/min, up to carbon dioxide foam systems 328ml;
(4) obtained carbon dioxide foaming is moved quickly to 80 DEG C of insulating boxs, measures its half-life period.
Heat resistance:At 80 DEG C, the carbon dioxide foam systems analysis liquid half-life period that the present embodiment obtains is 38.77min.Phase
It is smaller than the half-life period fall under room temperature in embodiment 2, illustrate carbon dioxide foam systems temperature tolerance made from this method
Can be stronger.
Embodiment 4:
A kind of carbon dioxide foam systems for adding hydrophilic nano particle, including material quality part composition are as follows:
Lauryl alcohol polyethylene glycol oxide polyethenoxy ether (C12E9P3) 0.1g, hydrophilic nano SiO 2 particle (average grain diameter
20nm, surface silicon alkanol density 1/nm2, the contact angle with water is 50.4 °) and 1.5g, sodium chloride (NaCl) 0.2g, carbon dioxide
0.5g, distilled water 100g.
Preparation method is as follows:
(1) hydrophilic nano SiO 2 particle is added in distilled water and stirred evenly, sequentially added laruyl alcohol and gather
Ethylene oxide polyethenoxy ether (C12E9P3) and sodium chloride (NaCl), ultrasonic disperse is carried out to mixed system using ultrasonic wave separating apparatus
3min;
(2) 0.2g calcium chloride (CaCl is sequentially added into mixed system2) and 0.2g magnesium chlorides (MgCl2), stir evenly;
(3) foam is produced using Waring Blender methods:3min dioxies are continually fed into the system obtained to step (1)
Change carbon, 3min is then stirred to system with the rotating speed of 8000r/min, up to carbon dioxide foam systems 336ml.
Under room temperature, the carbon dioxide foam systems analysis liquid half-life period that the present embodiment obtains is 39.28min.
Salt resistant character:Due to adding calcium chloride (CaCl common in stratum in the embodiment2) and magnesium chloride (MgCl2),
Salinity has reached 4000mg/L, a degree of destruction is played to foam stability, but compare and partly decline in embodiment 2
Phase fall is still smaller, illustrates that carbon dioxide foam systems salt resistant character is stronger made from this method method.
Comparative example 1:
As described in Example 1, unlike:
Lauryl alcohol polyethylene glycol oxide polyethenoxy ether (C12E9P3) additive amount is 0.6g.
Under room temperature, the carbon dioxide foam systems analysis liquid half-life period that this comparative example obtains is 6.24min.
Decline to a great extent compared to half-life period in embodiment 1, this is because excessive lauryl alcohol polyethylene glycol oxide polyethenoxy ether
(C12E9P3) so that surfactant forms double-deck absorption in particle surface, cause the hydrophilicity of particle to strengthen, return again
Into liquid phase, it can not be adsorbed onto on gas-liquid interface, so that stable foam cannot be played the role of.
Comparative example 2:
As described in Example 1, unlike:
Hydrophilic nano SiO 2 particle 5g.
Under room temperature, the carbon dioxide foam systems analysis liquid half-life period that this comparative example obtains is 1.65min.
Decline to a great extent compared to half-life period in embodiment 1, this is because comparing lauryl alcohol polyethylene glycol oxide polyethenoxy ether
(C12E9P3) concentration, granule density is excessive, lauryl alcohol polyethylene glycol oxide polyethenoxy ether (C12E9P3) in the adsorbance of particle surface
It is very few, unobvious are acted on to the hydrophobization of particle, particle is still located in liquid phase, can not play the role of stable foam.
Claims (3)
1. a kind of carbon dioxide foam systems for adding hydrophilic nano particle, including material quality part composition are as follows:
0.1-0.3 parts of nonionic surfactant, 1-2 parts of hydrophilic nano particle, 0.01-0.2 parts of inorganic salts, carbon dioxide
0.2-0.8 parts, 100 parts of water;
The nonionic surfactant is lauryl alcohol polyethylene glycol oxide polyethenoxy ether(C12E9P3);
The hydrophilic nano particle is hydrophilic nano SiO 2 particle;
The hydrophilic nano grain diameter is 15-50nm, density of surface silanol groups 1-2/nm2, the contact angle with water is
38-60°;
The inorganic salts are sodium chloride.
2. the carbon dioxide foam systems of addition hydrophilic nano particle according to claim 1, it is characterised in that described
Addition hydrophilic nano particle carbon dioxide foam systems, including material quality part composition it is as follows:
0.1 part of lauryl alcohol polyethylene glycol oxide polyethenoxy ether, 1.5 parts of hydrophilic nano SiO 2 particle, 0.2 part of sodium chloride, two
0.5 part of carbonoxide, 100 parts of water.
A kind of 3. preparation side of the carbon dioxide foam systems of claim 1-2 any one of them addition hydrophilic nano particle
Method, including step are as follows:
(1)Hydrophilic nano particle is added to the water and stirred evenly according to proportioning, then sequentially adds non-ionic surface work
Property agent and inorganic salts, ultrasonic disperse 3-5min;
(2)To step(1)Carbon dioxide 2-5min is continually fed into obtained system, then with the rotating speed of 7000-9000r/min
Stir 3-5min, to obtain the final product.
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CN104498016B (en) * | 2014-12-17 | 2017-02-22 | 唐山冀油瑞丰化工有限公司 | Foam agent used in carbon-dioxide flooding and preparation method of foam agent |
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