CN116064021B - Nano microemulsion type seepage and absorption oil discharge agent and preparation method and application thereof - Google Patents
Nano microemulsion type seepage and absorption oil discharge agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a nano microemulsion type oil seepage and drainage agent, a preparation method and application thereof. The seepage and oil discharge agent is nano microemulsion or diluent of nano microemulsion, the nano microemulsion consists of 50-60% of oil phase components and 40-50% of water phase components, the oil phase components comprise oil phase substances, oxyethylene nonionic surfactants and alcohol ether, and the water phase components comprise Gemini surfactants, cationic quaternary ammonium salt surfactants, alcohol and water; the external phase of the nano microemulsion is a water phase, and the internal phase is an oil phase; the Gemini surfactant is a polyoxyethylene-containing Gilmidz quaternary ammonium salt, a hyperbranched Gilmidz quaternary ammonium salt and an asymmetric Gilmidz quaternary ammonium salt. The droplet diameter of the oil-penetration drain is 5-20nm, and interfacial tension between the oil-water phase is as low as 9.9X10 ‑4 And the water-soluble polymer has high-efficiency imbibition capacity below mN/m.
Description
Technical Field
The invention belongs to the technical field of chemical oil extraction and crude oil recovery, and particularly relates to a nano microemulsion type seepage and absorption oil discharge agent, and a preparation method and application thereof.
Background
In recent years, the proportion of the medium-high permeability oil-gas resources in the newly-increased exploration reserves is smaller and smaller, and the proportion of the low permeability oil-gas resources is continuously increased. Statistics prove that the low permeability reserves account for 73.7% in the newly-increased oil and gas reserves by 2017. Meanwhile, with the increasing of the existing reserve exploitation degree, the importance degree of the oil-gas resources of the low-permeability reservoirs which are difficult to develop in the past in petroleum and natural gas development is increasing. It is expected that by 2035 years the dense oil production will be more than 45% of the total world crude oil production, and therefore achieving efficient development of low permeability reservoirs is becoming increasingly important. Low permeability reservoirs typically have the "three low two high" characteristics of low original formation pressure, low porosity, low permeability, high capillary pressure, high effective stress, and typically require reservoir modification to provide effective capacity. Meanwhile, the low-permeability oil reservoir has the advantages of universal microcrack development, matrix-fracture dual-flow characteristic of the reservoir, short anhydrous oil recovery period, quick water rise after water breakthrough, large amount of crude oil in the matrix after water breakthrough, low recovery ratio and the like in water injection development, so that the effective development of the low-permeability oil reservoir is always a great problem.
Imbibition oil extraction is an important mode in low-permeability oil reservoir development, plays a very important role in the oil reservoir development, and particularly in the unswept area of fracturing fracture in low-permeability oil reservoirs, the reservoir is compact, the starting pressure is high, an effective displacement system is difficult to establish, and oil production mainly depends on oil-water imbibition exchange between reservoir matrix and natural fracture. Therefore, research on imbibition oil extraction technology has important guiding significance for improving recovery ratio of low-permeability oil reservoirs.
In 2018, li Aifen et al have studied the relationship between the imbibition effect and the interfacial tension of the fracturing fluid by establishing a mathematical model of spontaneous imbibition volume and imbibition time, and have verified that the interfacial tension has a large influence on the imbibition effect by indoor experiments. For the imbibition of the fracturing fluid, the interface tension is not as low as possible, but rather an optimal value exists, and the imbibition effect is optimal.
2021, wang Fei et al put forward a set of pressure drop model of the dead well taking multiple factors into consideration aiming at the production mode of dead well production after fracturing, and found that the dead well pressure drop is in a closed state all the time due to the influence of fluid channeling and fluid loss of the crack in the early stage; the middle stage is a imbibition stage, and the filtration and reservoir imbibition of the fracturing fluid are gradually balanced; the late pressure wave reaches the control boundary, and the filtration and imbibition speed of the fracturing fluid gradually decreases until zero. Dan Jun et al study the tight gas reservoir after fracturing through indoor experiments, namely optimize the fracturing production system, and combine the indoor experimental means such as electron microscope scanning to develop the imbibition indoor experiment, the experimental result shows that imbibition speed and imbibition final recovery ratio are positively correlated with the core hydrophilicity. The lower the concentration of the fracturing fluid used in the fracturing operation, the better the matrix imbibition effect.
At present, the research on imbibition oil extraction is mostly related to the research on the aspects of experimental methods, imbibition mechanisms and the like, and the research on imbibition oil drainage agent which is safe, environment-friendly and has high-efficiency imbibition capacity is lacking.
Disclosure of Invention
The invention aims to provide a seepage-absorption oil drain agent with high-efficiency seepage-absorption capacity.
In order to achieve the above purpose, the present invention provides the following three technical solutions.
The invention provides a nano microemulsion type seepage-absorption oil drainage agent, wherein the nano microemulsion type seepage-absorption oil drainage agent is nano microemulsion or diluent of the nano microemulsion, and the nano microemulsion consists of 50% -60% of oil phase components and 40% -50% of water phase components by taking the mass of the nano microemulsion as 100%, wherein the oil phase components comprise oil phase substances, oxyethylene nonionic surfactants and alcohol ethers, and the water phase components comprise Gemini surfactants, cationic quaternary ammonium salt surfactants, alcohol and water;
the outer phase of the nano microemulsion drop is a water phase, and the inner phase is an oil phase; the distribution of the shell-core structure enables the microemulsion to have lower adsorption rate and adsorption loss in a reservoir, and can improve the acting distance and the sweep range of spontaneous imbibition;
the Gemini surfactant is one or a combination of more than two of cationic Gemini surfactant and derivatives thereof, and the Gemini surfactant is a polyoxyethylene-group-containing Gemini quaternary ammonium salt, a hyperbranched Gemini quaternary ammonium salt and an asymmetric Gemini quaternary ammonium salt.
The nanometer microemulsion type oil seepage and extraction agent has droplet diameter of 5-20nm, and interfacial tension with oil-water phase as low as 9.9X10 -4 And (3) the washing oil rate and the seepage recovery ratio of the nano micro-emulsion type seepage and oil discharge agent with the concentration below mN/m of 0.2wt.% are both more than 50wt.%.
When the nano microemulsion type oil seepage and drainage agent provided by the invention is used for oil drainage, a special Gemini surfactant firstly wets the rock to enable a stripped oil film to shrink into oil drops, and then the interfacial tension is reduced due to the adsorption of the special Gemini surfactant on an oil/water interface, so that the oil drops are favorably solubilized and emulsified into water to be cleaned; the special Gemini surfactant and the polyoxyethylene nonionic surfactant act synergistically, so that electrostatic attraction between the surfactants is increased, micelle formation is facilitated, cmc value is reduced, activity is enhanced, interfacial tension between the nano microemulsion and oil-water two phases is further reduced, wettability of a reservoir is changed, and oil washing capability is further enhanced; the oil-water fluidity ratio can be changed by using the polymer and the traditional surfactant at extremely low concentration, the swept volume and space are enlarged, and the oil washing efficiency is improved; the cationic quaternary ammonium salt surfactant, alcohol and alcohol ether help to reduce interfacial tension between the nano-microemulsion and oil-water two phases, improve wettability of a reservoir, stabilize oil-water interfaces and stabilize clay; under the synergistic effect of a special Gemini surfactant, a polyoxyethylene nonionic surfactant, a cationic quaternary ammonium salt surfactant, alcohol and alcohol ether, low-permeability oil reservoir dialysis oil drainage is realized.
According to a preferred embodiment of the first aspect, wherein the nanoemulsion consists of 57.5% oil phase and 42.5% water phase, based on 100% mass of the nanoemulsion.
According to a preferred embodiment of the first aspect, wherein the nano-microemulsion has a mass of 100%, the nano-microemulsion has a content of Gemini surfactant of 10wt.% to 15wt.%, a content of cationic quaternary ammonium salt type surfactant of 12wt.% to 20wt.%, an alcohol content of 5wt.% to 8wt.%, a water content of 4wt.% to 10wt.%, an oil phase material of 18wt.% to 25wt.%, an oxyethylene type nonionic surfactant of 18wt.% to 25wt.%, an alcohol ether content of 13wt.% to 20wt.%,
further, the nano microemulsion comprises, by mass, 100%, 12wt.% of Gemini surfactant, 18wt.% of cationic quaternary ammonium salt surfactant, 6.5wt.% of alcohol, 6.0wt.% of water, 19.5wt.% of oil phase substance, 18.5wt.% of oxyethylene nonionic surfactant and 19.5wt.% of alcohol ether.
According to a preferred embodiment of the first aspect, wherein the Gemini surfactant is a hyperbranched Gemini lathering surfactant 31766; the hyperbranched gemini foamless surfactant 31766 is a novel surfactant formed by modifying a nonionic surfactant, has double performances of nonionic and cationic, has higher Zeta potential, has strong adsorption and stripping effects on crude oil, has good dispersion performance, and can strip and disperse an oil film adsorbed on the surface of rock into a smaller oil film.
According to a preferred embodiment of the first aspect, wherein the cationic quaternary ammonium salt type surfactant comprises one or a combination of two or more of benzalkonium chloride (i.e., benzalkonium chloride), benzalkonium bromide (i.e., benzalkonium bromide), domiphen bromide (i.e., dodecyldimethylbenzyloxyethyl ammonium bromide).
According to a preferred embodiment of the first aspect, wherein the alcohol is a small molecule alcohol having a carbon number of not more than 5; further, the alcohol includes one or a combination of two or more of methanol, propanol, ethylene glycol, ethanol, propanol, isopropanol, ethylene glycol, butanol and pentanol.
According to a preferred embodiment of the first aspect, wherein the water is one of distilled water, deionized water and tap water.
According to a preferred embodiment of the first aspect, wherein the oil phase material comprises one or a combination of two or more of oilfield crude oil, crude oil diluted with light oil, linear saturated aliphatic hydrocarbons; further, the oil phase material is n-hexane.
According to a preferred embodiment of the first aspect, wherein the oxyethylene nonionic surfactant is a fatty alcohol polyoxyethylene ether, such as AEO20.
According to a preferred embodiment of the first aspect, wherein the alcohol ether comprises one or a combination of two or more of a lower alcohol ether of ethylene glycol and a lower alcohol ether of propylene glycol, wherein lower refers to 5 carbons or less.
According to a preferred embodiment of the first aspect, wherein the effective concentration of the nanoemulsion is between 0.05wt.% and 0.7 wt.%, based on 100% of the total mass of the dilution of the nanoemulsion.
In a second aspect, the present invention provides a method for preparing the nano-microemulsion type oil seepage and drainage agent provided in the first aspect, wherein the method comprises the following steps:
uniformly mixing an oil phase substance, an oxyethylene nonionic surfactant and alcohol ether to obtain an oil phase component;
uniformly mixing a Gemini surfactant, a cationic quaternary ammonium salt surfactant, alcohol and water to obtain a water phase component;
and uniformly mixing the oil phase component and the water phase component to form a homogeneous nano microemulsion, thereby preparing the nano microemulsion type oil seepage and drainage agent.
According to a preferred embodiment of the second aspect, wherein the method comprises: the prepared nano-microemulsion is diluted to obtain the nano-microemulsion type oil seepage and drainage agent with the effective concentration of the nano-microemulsion of 0.05wt.% to 0.7wt wt.% (based on 100 percent of the total mass of the nano-microemulsion type oil seepage and drainage agent).
In a third aspect, the present invention provides the use of a nanoemulsion type oil-seepage and drainage agent provided in the first aspect for enhanced oil recovery in low permeability, ultra-low permeability tight reservoirs.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
1. the nano microemulsion type oil seepage and extraction agent provided by the invention has the advantages of small particle size, small droplet size of about 5-20nm, narrow particle size distribution, difficult agglomeration, good stability, capability of penetrating into micro pores of a low-permeability reservoir layer, entering into nano-scale fine throats and micro throats, communication channels, improvement of the flowability of crude oil and excellent oil seepage and extraction effect.
2. The nano microemulsion type oil seepage and drainage agent provided by the invention has the advantages that the smaller the contact angle is, the stronger the wetting inversion capability is, the stronger the capability of peeling crude oil on the surface of rock is, the oil seepage and drainage effect can be effectively improved, and the crude oil recovery ratio is improved.
3. The nano microemulsion type oil seepage and drainage agent provided by the invention can reduce the interfacial tension between the nano microemulsion and oil-water two phases to 9.9x10 through the synergistic effect of the special Gemini surfactant, the polyoxyethylene nonionic surfactant, the cationic quaternary ammonium salt surfactant, the alcohol and the alcohol ether -4 And (3) the washing oil rate and the seepage recovery ratio of the nano micro-emulsion type seepage and oil discharge agent with the concentration of less than 0.2wt.% are more than 50 wt.%.
4. The nano microemulsion type oil seepage and drainage agent provided by the invention belongs to medium phase microemulsion, and the interfacial tension between the nano microemulsion type oil seepage and drainage agent and oil-water phases can be reduced to 9.9 multiplied by 10 -4 The smaller the interfacial tension is below mN/m, the stronger the deformation capability of crude oil is, the crude oil is easy to pass through the fine throat and the micro throat, the fluidity of the crude oil is improved, and the oil seepage and extraction effect is excellent.
5. The nano microemulsion type seepage and oil discharge agent provided by the invention has small adsorption quantity to the solid phase surface, and can reach all areas of liquid wave; compared with the conventional nano microemulsion, the adsorption of rock can be effectively reduced, the low interfacial tension is maintained, the imbibition action distance is longer, and the imbibition oil discharge effect is good.
6. Compared with the Shah method (namely, an emulsifying system of oil, surfactant and isopropanol is prepared firstly, and then water is added to obtain microemulsion), the preparation method of the nano microemulsion type oil seepage and extraction agent provided by the invention can obviously reduce the interfacial tension of oil and water.
7. The preparation method of the nano microemulsion type oil seepage and drainage agent provided by the invention has the advantages of simple preparation process, environment-friendly preparation process and no environmental pollution.
8. The nano microemulsion type oil seepage and drainage agent provided by the invention has the advantages of easily available raw materials and wide sources, so that the production cost and the use cost of the product are very low.
In conclusion, the technical scheme of the invention has wide application prospect.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for.
In the present invention, unless otherwise indicated, parts are wt.%, temperatures are expressed in degrees celsius or at ambient temperature, and pressures are at or near atmospheric pressure. There are numerous variations and combinations of reaction conditions (e.g., component concentrations, solvents needed, solvent mixtures, temperatures, pressures, and other reaction ranges) and conditions that can be used to optimize the purity and yield of the product obtained by the process. Only reasonable routine experimentation will be required to optimize such process conditions.
The instruments, reagents, materials, etc. used in the following examples are conventional instruments, reagents, materials, etc. existing in the prior art, and are commercially available in a normal manner unless otherwise specified. The experimental methods, detection methods, and the like in the following examples are conventional experimental methods, detection methods, and the like, which are known in the art, unless otherwise specified.
Example 1
The embodiment provides a nano microemulsion type oil seepage and drainage agent, which is nano microemulsion, wherein the nano microemulsion consists of 57.5% of oil phase components and 42.5% of water phase components by taking the mass of the nano microemulsion as 100%, the oil phase components comprise oil phase substances, oxyethylene nonionic surfactants and alcohol ethers, and the water phase components comprise Gemini surfactants, cationic quaternary ammonium salt surfactants, alcohols and water;
the external phase of the nano microemulsion is a water phase, and the internal phase is an oil phase;
the nano microemulsion type oil seepage and absorption agent is prepared by the following steps:
(1) Preparation of oil phase component
Adding 18wt.% of fatty alcohol polyoxyethylene ether AEO20 and 14.5wt.% of ethylene glycol butyl ether into 25wt.% of n-hexane, and uniformly stirring to form an oil phase component;
(2) Preparation of aqueous phase component
Adding 14.5wt.% of benzalkonium chloride (namely benzalkonium chloride), 10wt.% of hyperbranched gemini foamless surfactant 31766 and 8wt.% of ethylene glycol into 10wt.% of clear water, and uniformly stirring and dissolving to form an aqueous phase component;
(3) Preparation of nanoemulsion
And mixing 57.5wt.% of the oil phase component and 42.5wt.% of the water phase component, and stirring until the mixture is uniform to form a homogeneous nano microemulsion, namely the nano microemulsion type oil seepage and drainage agent.
The nano microemulsion type oil seepage and absorption agent has the effective concentration of 100 percent, the appearance is transparent and stable for a long time.
Example 2
The embodiment provides a nano microemulsion type oil seepage and drainage agent, which is nano microemulsion, wherein the nano microemulsion consists of 57.5% of oil phase components and 42.5% of water phase components by taking the mass of the nano microemulsion as 100%, the oil phase components comprise oil phase substances, oxyethylene nonionic surfactants and alcohol ethers, and the water phase components comprise Gemini surfactants, cationic quaternary ammonium salt surfactants, alcohols and water;
the external phase of the nano microemulsion is a water phase, and the internal phase is an oil phase;
the nano microemulsion type oil seepage and absorption agent is prepared by the following steps:
(1) Preparation of oil phase component
Adding 18wt.% of fatty alcohol polyoxyethylene ether AEO20 and 14.5wt.% of ethylene glycol methyl ether into 25wt.% of n-hexane, and uniformly stirring to form an oil phase component;
(2) Preparation of aqueous phase component
Adding 14.5wt.% of benzalkonium bromide, 10wt.% of hyperbranched gemini foamless surfactant 31766 and 8wt.% of ethylene glycol into 10wt.% of clear water, and uniformly stirring and dissolving to form a water phase component;
(3) Preparation of nanoemulsion
And mixing 57.5wt.% of the oil phase component and 42.5wt.% of the water phase component, and stirring until the mixture is uniform to form a homogeneous nano microemulsion, namely the nano microemulsion type oil seepage and drainage agent.
The nano microemulsion type oil seepage and absorption agent has the effective concentration of 100 percent, the appearance is transparent and stable for a long time.
Example 3
The embodiment provides a nano microemulsion type oil seepage and drainage agent, which is nano microemulsion, wherein the nano microemulsion consists of 57.5% of oil phase components and 42.5% of water phase components by taking the mass of the nano microemulsion as 100%, the oil phase components comprise oil phase substances, oxyethylene nonionic surfactants and alcohol ethers, and the water phase components comprise Gemini surfactants, cationic quaternary ammonium salt surfactants, alcohols and water;
the external phase of the nano microemulsion is a water phase, and the internal phase is an oil phase;
the nano microemulsion type oil seepage and absorption agent is prepared by the following steps:
(1) Preparation of oil phase component
18wt.% of fatty alcohol polyoxyethylene ether AEO20 and 14.5wt.% of propylene glycol butyl ether are added into 25wt.% of normal hexane, and the mixture is stirred uniformly to form an oil phase component;
(2) Preparation of aqueous phase component
Adding 14.5wt.% of domiphen bromide (namely dodecyl dimethyl phenethyl ammonium bromide, 10wt.% of hyperbranched gemini foamless surfactant 31766 and 8wt.% of ethylene glycol into 10wt.% of clear water, and uniformly stirring and dissolving to form a water phase component;
(3) Preparation of nanoemulsion
And mixing 57.5wt.% of the oil phase component and 42.5wt.% of the water phase component, and stirring until the mixture is uniform to form a homogeneous nano microemulsion, namely the nano microemulsion type oil seepage and drainage agent.
The nano microemulsion type oil seepage and absorption agent has the effective concentration of 100 percent, the appearance is transparent and stable for a long time.
Example 4
The embodiment provides a nano microemulsion type oil seepage and drainage agent, which is nano microemulsion, wherein the nano microemulsion consists of 57.5% of oil phase components and 42.5% of water phase components by taking the mass of the nano microemulsion as 100%, the oil phase components comprise oil phase substances, oxyethylene nonionic surfactants and alcohol ethers, and the water phase components comprise Gemini surfactants, cationic quaternary ammonium salt surfactants, alcohols and water;
the external phase of the nano microemulsion is a water phase, and the internal phase is an oil phase;
The nano microemulsion type oil seepage and absorption agent is prepared by the following steps:
(1) Preparation of oil phase component
Adding 22.5wt.% of fatty alcohol polyoxyethylene ether AEO20 and 15.5wt.% of propylene glycol methyl ether into 19.5wt.% of n-hexane, and uniformly stirring to form an oil phase component;
(2) Preparation of aqueous phase component
Adding 18wt.% of benzalkonium chloride (namely benzalkonium chloride), 12wt.% of hyperbranched gemini foamless surfactant 31766 and 6.5wt.% of ethylene glycol into 6wt.% of clear water, and uniformly stirring and dissolving to form a water phase component;
(3) Preparation of nanoemulsion
And mixing 57.5wt.% of the oil phase component and 42.5wt.% of the water phase component, and stirring until the mixture is uniform to form a homogeneous nano microemulsion, namely the nano microemulsion type oil seepage and drainage agent.
The nano microemulsion type oil seepage and absorption agent has the effective concentration of 100 percent, the appearance is transparent and stable for a long time.
Example 5
The embodiment provides a nano microemulsion type oil seepage and drainage agent, which is nano microemulsion, wherein the nano microemulsion consists of 57.5% of oil phase components and 42.5% of water phase components by taking the mass of the nano microemulsion as 100%, the oil phase components comprise oil phase substances, oxyethylene nonionic surfactants and alcohol ethers, and the water phase components comprise Gemini surfactants, cationic quaternary ammonium salt surfactants, alcohols and water;
The external phase of the nano microemulsion is a water phase, and the internal phase is an oil phase;
the nano microemulsion type oil seepage and absorption agent is prepared by the following steps:
(1) Preparation of oil phase component
Adding 20wt.% of fatty alcohol polyoxyethylene ether AEO20 and 18wt.% of propylene glycol butyl ether into 19.5wt.% of n-hexane, and uniformly stirring to form an oil phase component;
(2) Preparation of aqueous phase component
15wt.% of domiphen bromide (namely dodecyl dimethyl phenethyl ammonium bromide, 10wt.% of hyperbranched gemini foamless surfactant 31766 and 8wt.% of ethylene glycol are added into 9.5wt.% of clear water, and the mixture is stirred and dissolved uniformly to form a water phase component;
(3) Preparation of nanoemulsion
And mixing 57.5wt.% of the oil phase component and 42.5wt.% of the water phase component, and stirring until the mixture is uniform to form a homogeneous nano microemulsion, namely the nano microemulsion type oil seepage and drainage agent.
The nano microemulsion type oil seepage and absorption agent has the effective concentration of 100 percent, the appearance is transparent and stable for a long time.
Example 6
The embodiment provides a nano microemulsion type oil seepage and drainage agent, which is nano microemulsion, wherein the nano microemulsion consists of 57.5% of oil phase components and 42.5% of water phase components by taking the mass of the nano microemulsion as 100%, the oil phase components comprise oil phase substances, oxyethylene nonionic surfactants and alcohol ethers, and the water phase components comprise Gemini surfactants, cationic quaternary ammonium salt surfactants, alcohols and water;
The external phase of the nano microemulsion is a water phase, and the internal phase is an oil phase;
the nano microemulsion type oil seepage and absorption agent is prepared by the following steps:
(1) Preparation of oil phase component
25wt.% of fatty alcohol polyoxyethylene ether AEO20 and 17.5wt.% of propylene glycol butyl ether are added into 15wt.% of normal hexane, and the mixture is stirred uniformly to form an oil phase component;
(2) Preparation of aqueous phase component
Adding 20wt.% of benzalkonium chloride (namely benzalkonium chloride), 13.5wt.% of hyperbranched gemini foamless surfactant 31766 and 5wt.% of ethylene glycol into 4.0wt.% of clear water, and uniformly stirring and dissolving to form a water phase component;
(3) Preparation of nanoemulsion
And mixing 57.5wt.% of the oil phase component and 42.5wt.% of the water phase component, and stirring until the mixture is uniform to form a homogeneous nano microemulsion, namely the nano microemulsion type oil seepage and drainage agent.
The nano microemulsion type oil seepage and absorption agent has the effective concentration of 100 percent, the appearance is transparent and stable for a long time.
Comparative example 1
The comparative example provides a nano microemulsion type oil seepage and drainage agent which is nano microemulsion, wherein the nano microemulsion consists of 50% of oil phase components and 50% of water phase components by taking the mass of the nano microemulsion as 100%, the oil phase components comprise oil phase substances, oxyethylene nonionic surfactants and alcohol ethers, and the water phase components comprise cationic quaternary ammonium salt surfactants, alcohols and water;
The external phase of the nano microemulsion is a water phase, and the internal phase is an oil phase;
the nano microemulsion type oil seepage and absorption agent is prepared by the following steps:
(1) Preparation of oil phase component
Adding 18wt.% of fatty alcohol polyoxyethylene ether AEO20 and 12wt.% of propylene glycol butyl ether into 20wt.% of n-hexane, and uniformly stirring to form an oil phase component;
(2) Preparation of aqueous phase component
Adding 20wt.% of benzalkonium chloride (namely benzalkonium chloride) and 8wt.% of ethylene glycol into 22wt.% of clear water, and uniformly stirring and dissolving to form a water phase component;
(3) Preparation of nanoemulsion
And mixing the 50wt.% of the oil phase component and the 50wt.% of the water phase component, and stirring until the mixture is uniform to form a homogeneous nano-microemulsion, namely the nano-microemulsion type oil seepage and drainage agent.
The nano microemulsion type oil seepage and absorption agent has the effective concentration of 100 percent, the appearance is transparent and stable for a long time.
Comparative example 2
The comparative example provides a nano microemulsion type oil seepage and drainage agent which is nano microemulsion, wherein the nano microemulsion consists of 57.5% of oil phase components and 42.5% of water phase components by taking the mass of the nano microemulsion as 100%, the oil phase components comprise oil phase substances, oxyethylene nonionic surfactants and alcohol ethers, and the water phase components comprise cationic quaternary ammonium salt surfactants, alcohols and water;
The external phase of the nano microemulsion is a water phase, and the internal phase is an oil phase;
the nano microemulsion type oil seepage and absorption agent is prepared by the following steps:
(1) Preparation of oil phase component
18wt.% of fatty alcohol polyoxyethylene ether AEO20 and 14.5wt.% of propylene glycol butyl ether are added into 25wt.% of normal hexane, and the mixture is stirred uniformly to form an oil phase component;
(2) Preparation of aqueous phase component
Adding 12wt.% of benzalkonium chloride (namely benzalkonium chloride) and 8wt.% of ethylene glycol into 22.5wt.% of clear water, and uniformly stirring and dissolving to form a water phase component;
(3) Preparation of nanoemulsion
And mixing 57.5wt.% of the oil phase component and 42.5wt.% of the water phase component, and stirring until the mixture is uniform to form a homogeneous nano microemulsion, namely the nano microemulsion type oil seepage and drainage agent.
The nano microemulsion type oil seepage and absorption agent has the effective concentration of 100 percent, the appearance is transparent and stable for a long time.
Comparative example 3
The comparative example provides a nano microemulsion type oil seepage and drainage agent which is nano microemulsion, wherein the nano microemulsion consists of 57.5% of oil phase components and 42.5% of water phase components by taking the mass of the nano microemulsion as 100%, the oil phase components comprise oil phase substances, oxyethylene nonionic surfactants and alcohol ethers, and the water phase components comprise cationic quaternary ammonium salt surfactants, alcohols and water;
The external phase of the nano microemulsion is a water phase, and the internal phase is an oil phase;
the nano microemulsion type oil seepage and absorption agent is prepared by the following steps:
(1) Preparation of oil phase component
25wt.% of fatty alcohol polyoxyethylene ether AEO20 and 19.5wt.% of propylene glycol butyl ether are added into 13wt.% of normal hexane, and the mixture is stirred uniformly to form an oil phase component;
(2) Preparation of aqueous phase component
Adding 15wt.% of benzalkonium chloride and 5wt.% of ethylene glycol into 22.5wt.% of clear water, and uniformly stirring and dissolving to form a water phase component;
(3) Preparation of nanoemulsion
And mixing 57.5wt.% of the oil phase component and 42.5wt.% of the water phase component, and stirring until the mixture is uniform to form a homogeneous nano microemulsion, namely the nano microemulsion type oil seepage and drainage agent.
The nano microemulsion type oil seepage and absorption agent has the effective concentration of 100 percent, the appearance is transparent and stable for a long time.
Comparative example 4
The comparative example provides a nano microemulsion type oil seepage and drainage agent which is nano microemulsion, wherein the nano microemulsion consists of 57.5% of oil phase components and 42.5% of water phase components by taking the mass of the nano microemulsion as 100%, and the oil phase components comprise oil phase substances, oxyethylene type nonionic surfactants and alcohol ethers, and the water phase components comprise Gemini surfactants, alcohol and water;
The external phase of the nano microemulsion is a water phase, and the internal phase is an oil phase;
the nano microemulsion type oil seepage and absorption agent is prepared by the following steps:
(1) Preparation of oil phase component
18wt.% of fatty alcohol polyoxyethylene ether AEO20 and 14.5wt.% of propylene glycol butyl ether are added into 25wt.% of normal hexane, and the mixture is stirred uniformly to form an oil phase component;
(2) Preparation of aqueous phase component
Adding 15wt.% of hyperbranched gemini foamless surfactant 31766 and 8wt.% of ethylene glycol into 19.5wt.% of clear water, and uniformly stirring and dissolving to form a water phase component;
(3) Preparation of nanoemulsion
And mixing 57.5wt.% of the oil phase component and 42.5wt.% of the water phase component, and stirring until the mixture is uniform to form a homogeneous nano microemulsion, namely the nano microemulsion type oil seepage and drainage agent.
The nano microemulsion type oil seepage and absorption agent has the effective concentration of 100 percent, the appearance is transparent and stable for a long time.
Comparative example 5
The comparative example provides a nano microemulsion type oil seepage and drainage agent which is nano microemulsion, wherein the nano microemulsion consists of 57.5% of oil phase components and 42.5% of water phase components by taking the mass of the nano microemulsion as 100%, the oil phase components comprise oil phase substances and alcohol ether, and the water phase components comprise Gemini surfactant, cationic quaternary ammonium salt surfactant, alcohol and water;
The external phase of the nano microemulsion is a water phase, and the internal phase is an oil phase;
the nano microemulsion type oil seepage and absorption agent is prepared by the following steps:
(1) Preparation of oil phase component
Adding 23.5wt.% of propylene glycol butyl ether into 34wt.% of n-hexane, and uniformly stirring to form an oil phase component;
(2) Preparation of aqueous phase component
Adding 14.5wt.% of domiphen bromide (namely dodecyl dimethyl phenethyl ammonium bromide), 10wt.% of hyperbranched gemini foamless surfactant 31766 and 8wt.% of ethylene glycol into 10wt.% of clear water, and uniformly stirring and dissolving to form a water phase component;
(3) Preparation of nanoemulsion
And mixing 57.5wt.% of the oil phase component and 42.5wt.% of the water phase component, and stirring until the mixture is uniform to form a homogeneous nano microemulsion, namely the nano microemulsion type oil seepage and drainage agent.
Comparative example 6
The comparative example provides a nano microemulsion type oil seepage and drainage agent which is nano microemulsion, wherein the nano microemulsion consists of 57.5% of oil phase components and 42.5% of water phase components by taking the mass of the nano microemulsion as 100%, the oil phase components comprise oil phase substances and oxyethylene nonionic surfactants, and the water phase components comprise Gemini surfactants, cationic quaternary ammonium salt surfactants, alcohols and water;
The external phase of the nano microemulsion is a water phase, and the internal phase is an oil phase;
the nano microemulsion type oil seepage and absorption agent is prepared by the following steps:
(1) Preparation of oil phase component
Adding 25wt.% of fatty alcohol polyoxyethylene ether AEO20 into 32.5wt.% of normal hexane, and uniformly stirring to form an oil phase component;
(2) Preparation of aqueous phase component
Adding 14.5wt.% of domiphen bromide (namely dodecyl dimethyl phenethyl ammonium bromide), 10wt.% of hyperbranched gemini foamless surfactant 31766 and 8wt.% of ethylene glycol into 10wt.% of clear water, and uniformly stirring and dissolving to form a water phase component;
(3) Preparation of nanoemulsion
And mixing 57.5wt.% of the oil phase component and 42.5wt.% of the water phase component, and stirring until the mixture is uniform to form a homogeneous nano microemulsion, namely the nano microemulsion type oil seepage and drainage agent.
Comparative example 7
The embodiment provides a nano microemulsion type oil seepage and drainage agent, which is nano microemulsion, wherein the nano microemulsion consists of 57.5% of oil phase components and 42.5% of water phase components by taking the mass of the nano microemulsion as 100%, the oil phase components comprise oil phase substances, oxyethylene nonionic surfactants and alcohol ethers, and the water phase components comprise Gemini surfactants, cationic quaternary ammonium salt surfactants, alcohols and water;
The external phase of the nano microemulsion is a water phase, and the internal phase is an oil phase;
the nano microemulsion type oil seepage and absorption agent is prepared by the following steps:
(1) Preparation of oil phase component
18wt.% of fatty alcohol polyoxyethylene ether AEO20 and 14.5wt.% of propylene glycol butyl ether are added into 25wt.% of normal hexane, and the mixture is stirred uniformly to form an oil phase component;
(2) Preparation of aqueous phase component
Adding 14.5wt.% of domiphen bromide (namely dodecyl dimethyl phenoxyethyl ammonium bromide), 10wt.% of GEMINI surfactant (octadecylamine) and 8wt.% of glycol into 10wt.% of clear water, and uniformly stirring and dissolving to form an aqueous phase component;
(3) Preparation of nanoemulsion
And mixing 57.5wt.% of the oil phase component and 42.5wt.% of the water phase component, and stirring until the mixture is uniform to form a homogeneous nano microemulsion, namely the nano microemulsion type oil seepage and drainage agent.
Experimental example 1
The experimental examples were used to verify the performance of the nano-microemulsion type oil-penetration and drainage agent provided by each example and each comparative example, and the temperature stability, salt stability (100000 ppm), average particle size, interfacial tension, wettability and adsorption rate of the nano-microemulsion type oil-penetration and drainage agent provided by each example and each comparative example were respectively verified according to the following methods.
(1) Temperature stability, salt stability (100000 ppm) test: the nano microemulsion type seepage and oil discharge agent provided by each example and comparative example is diluted by clear water until the effective concentration of the nano microemulsion is 0.3%, and then is put into a sample pool, and the TSI value of the nano microemulsion type seepage and oil discharge agent with the effective concentration of the nano microemulsion is 0.3% is measured.
(2) Particle size measurement: the nano-microemulsion type seepage and oil discharge agent provided by each example and comparative example is diluted by clean water until the effective concentration of the nano-microemulsion is 0.07%, and then is put into a sample cell, and the particle size of the nano-microemulsion type seepage and oil discharge agent with the effective concentration of the nano-microemulsion is 0.3% is measured by using a Zeta particle size analyzer.
(3) And (3) testing the oil-water interfacial tension: the nano microemulsion type seepage and oil discharge agent provided by each example and comparative example is diluted by clear water until the effective concentration of the nano microemulsion is 0.07%, then is injected into a glass capillary together with crude oil, and then is put into a sample cell of an interfacial tension meter, the rotation speed is kept at 6000 r/min for 1 min, and the interfacial tension value between the nano microemulsion type seepage and oil-water two phases, in which the effective concentration of the nano microemulsion is 0.3%, is measured by adopting a TX-500 rotary drop interfacial tension meter.
(4) Solid-liquid contact angle measurement: diluting the nano microemulsion type seepage drainage agent provided by each example and comparative example with clear water until the effective concentration of the nano microemulsion is 0.3%, aging a quartz plate in silicone oil for seven days, soaking the aged quartz plate in the nano microemulsion type seepage drainage agent with the effective concentration of the nano microemulsion of 0.3%, standing for 3 days for modification, and measuring the contact angle of the quartz plate after modification; specifically, deionized water is dripped onto a quartz plate by using a static dripping method, a gas-water-solid three-phase contact angle is measured according to a three-point method, and an average value is obtained by measuring three times.
(5) Imbibition enhanced recovery experiment
The nano microemulsion type oil seepage and drainage agent provided by each example and comparative example is diluted by clear water until the effective concentration of the nano microemulsion is 0.3%. The self-made rock core is dried and placed in a drying vessel to be cooled to room temperature, the mass of the rock core is weighed and recorded as m1, the rock core is placed in a middle container for displacement to be vacuumized, the pressure is increased to 15 MPa after the vacuum pumping is finished, the middle container full of kerosene is connected, saturated kerosene is operated by utilizing pressure difference, the kerosene fully enters into rock pores, the rock core is placed in an oven to be aged for 1 week at 60 ℃, the surface kerosene of the rock core is wiped clean after the rock core is taken out, and the mass m2 of the rock core after saturated aging is recorded. Wiping the surface of the saturated and aged core, filling the core into a seepage bottle, adding a nano microemulsion type seepage oil discharge agent with the effective concentration of nano microemulsion of 0.3 percent until the core is over to reach the scale mark of the capillary of the seepage bottle, sealing and standing, and recording the change of the oil discharge amount V along with the time.
(6) Compatibility test with acid solution
The nano microemulsion type oil seepage and drainage agent provided by each example and comparative example is diluted by clear water to the effective concentration of 0.3% of nano microemulsion at normal temperature and normal pressure, then is mixed with 20% hydrochloric acid or 12% hydrochloric acid plus 3% hydrofluoric acid according to the mass ratio of 1:1, and is stood for 2 hours, and the state of the mixed solution is observed.
(7) Determination of the extent of pore usage of a nanoemulsion type oil-bleeding drainage agent by NMR
The nano microemulsion type oil seepage and drainage agent provided by each example and comparative example is diluted by clear water until the effective concentration of the nano microemulsion is 0.3%. And (3) placing the core saturated kerosene in a permeation bottle, and performing permeation experiments under the conditions of constant flow rate of 0.1 mL/min and 2 MPa confining pressure of the nano microemulsion type permeation oil discharging agent with the effective concentration of 0.3% of the nano microemulsion. Nuclear magnetic resonance observation is carried out on cores before imbibition (0 h), during imbibition (30 h, 72 h) and after imbibition (100 h), the resonance frequency is 12.8MHz, the oil recovery rate is determined by the area change of a nuclear magnetic spectrum, and the area reduction amplitude corresponds to the amount of the displaced oil.
The TSI value, particle diameter, oil-water interfacial tension, solid-liquid contact angle, anti-swelling rate, permeation recovery ratio and compatibility index with acid of the nano microemulsion type permeation oil drain agent provided in each example and comparative example are shown in Table 1.
TABLE 1
In Table 1, O indicates no incompatibility such as delamination, precipitation, flocculation, etc., and X indicates delamination
Experiments prove that the synergistic effect of Gemini surfactant, cationic quaternary ammonium salt surfactant, oxyethylene nonionic surfactant and the like can reduce the oil-water interfacial tension between the nano microemulsion and the crude oil of the stratum to 9.9 multiplied by 10 -4 mN/m, the ultra-low interfacial tension is achieved, the absorption rate is improved to more than 45%, the anti-swelling rate is improved to more than 90%, and the compatibility with acid is good.
Experimental example 2
The experimental example was used to verify the performance of the nano-microemulsion type oil-penetration and drainage agent provided in example 3, and the temperature stability, salt stability (100000 ppm), average particle size, interfacial tension, wettability and adsorption rate of the nano-microemulsion type oil-penetration and drainage agent provided in example 3 were respectively verified according to the following method.
(1) Temperature stability, salt stability (100000 ppm) test: the nano-microemulsion type oil seepage and drainage agent provided in the example 3 is diluted by clear water until the effective concentration of the nano-microemulsion is 0.07%, 0.2%, 0.4%, 0.6% and 0.7%, and then is put into a sample cell, and the TSI value of the nano-microemulsion type oil seepage and drainage agent under different concentrations is measured.
(2) Particle size measurement: the nano-microemulsion type oil seepage and drainage agent provided in the embodiment 3 is diluted by clear water until the effective concentration of the nano-microemulsion is 0.07%, 0.2%, 0.4%, 0.6% and 0.7%, and then is placed into a sample cell, and the particle size of the nano-microemulsion type oil seepage and drainage agent under different concentrations is measured by using a Zeta particle size analyzer.
(3) And (3) testing the oil-water interfacial tension: the nano microemulsion type oil seepage and drainage agent provided in the embodiment 3 is diluted by clear water until the effective concentration of the nano microemulsion is 0.07%, 0.2%, 0.4%, 0.6% and 0.7%, then the nano microemulsion type oil seepage and drainage agent and crude oil are injected into a glass capillary together, and the glass capillary is placed into a sample cell of an interfacial tension meter, the rotation speed is kept 6000 r/min, the time interval is kept for 1 min, and the interfacial tension value between the nano microemulsion type oil seepage and drainage agent and oil-water phases under different concentration is measured by adopting a TX-500 rotary drop interfacial tension meter.
(4) Solid-liquid contact angle measurement: diluting the nano microemulsion type oil seepage and extraction agent provided in the embodiment 3 with clear water until the effective concentration of the nano microemulsion is 0.07%, 0.2%, 0.4%, 0.6% and 0.7%, aging a quartz plate in silicone oil for seven days, soaking the aged quartz plate in nano microemulsion type oil seepage and extraction agents with different concentrations, standing for 3 days for modification, and measuring the contact angle of the modified quartz plate; specifically, deionized water is dripped onto a quartz plate by using a static dripping method, a gas-water-solid three-phase contact angle is measured according to a three-point method, and an average value is obtained by measuring three times.
(5) Imbibition enhanced recovery experiment
The nano-microemulsion type oil seepage and drainage agent provided in the embodiment 3 is diluted by clear water until the effective concentration of the nano-microemulsion is 0.07%, 0.2%, 0.4%, 0.6% and 0.7%. The self-made rock core is dried and placed in a drying vessel to be cooled to room temperature, the mass of the rock core is weighed and recorded as m1, the rock core is placed in a middle container for displacement to be vacuumized, the pressure is increased to 15 MPa after the vacuum pumping is finished, the middle container full of kerosene is connected, saturated kerosene is operated by utilizing pressure difference, the kerosene fully enters into rock pores, the rock core is placed in an oven to be aged for 1 week at 60 ℃, the surface kerosene of the rock core is wiped clean after the rock core is taken out, and the mass m2 of the rock core after saturated aging is recorded. Wiping the surface of the saturated and aged core, filling the core into a seepage bottle, adding nano microemulsion type seepage oil drainage agent with different concentrations until the core is not used to reach the scale mark of the capillary of the seepage bottle, sealing and standing, and recording the change of the oil output V with time.
(6) Compatibility test with acid solution
The nano-microemulsion type oil seepage and drainage agent provided in the embodiment 3 is diluted by clear water at normal temperature and normal pressure until the effective concentration of the nano-microemulsion is 0.07%, 0.2%, 0.4%, 0.6% and 0.7%, then mixed with 20% hydrochloric acid or 12% hydrochloric acid and 3% hydrofluoric acid according to the mass ratio of 1:1, and the mixture is stood for 2 hours, and the state of the mixed solution is observed.
(7) Determination of the extent of pore usage of a nanoemulsion type oil-bleeding drainage agent by NMR
The nano-microemulsion type oil seepage and drainage agent provided in the embodiment 3 is diluted by clear water until the effective concentration of the nano-microemulsion is 0.07%, 0.2%, 0.4%, 0.6% and 0.7%. And (3) placing the core saturated kerosene in a seepage bottle, and performing a seepage experiment under the conditions of constant flow rate of 0.1 mL/min and 2 MPa confining pressure of nano-microemulsion type seepage oil drainage agents with different concentrations. Nuclear magnetic resonance observation is carried out on cores before imbibition (0 h), during imbibition (30 h, 72 h) and after imbibition (100 h), the resonance frequency is 12.8 MHz, the oil recovery rate is determined by the area change of a nuclear magnetic spectrum, and the area reduction amplitude corresponds to the amount of the displaced oil.
The TSI value, particle diameter, oil-water interfacial tension, solid-liquid contact angle, anti-swelling rate, permeation recovery ratio and compatibility index with acid of the nano-microemulsion type permeation oil drain agent provided in example 3 under different concentrations are shown in Table 2.
TABLE 2
In Table 2, O means that there is no incompatibility such as delamination, precipitation, flocculation, etc
The microemulsion imbibition oil drain provided in example 3 with an effective concentration of 0.2% can better spontaneously imbibe into the nanoscale pore throat to displace the remaining oil, with a spontaneous imbibition recovery of up to 57.5%.
Experimental example 3
The experimental examples were conducted to obtain the data shown in table 3, by way of example, with clear water, 0.2wt.% OP-10 surfactant, 0.2wt.% nano-microemulsion type permeation oil drain provided in example 2, 0.2wt.% nano-microemulsion type permeation oil drain provided in example 3, and 0.2wt.% nano-microemulsion type permeation oil drain provided in example 4.
TABLE 3 Table 3
The micro-emulsion seepage and oil discharge agent provided in the embodiment 2, the embodiment 3 and the embodiment 4 has larger use degree on small holes, can spontaneously seep into nano-level pore throats to replace residual oil, and improves the spontaneous seepage and oil recovery ratio.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (11)
1. The nano microemulsion type oil seepage and absorption agent is nano microemulsion or diluent of nano microemulsion, and based on 100% of nano microemulsion, the nano microemulsion consists of 50-60% of oil phase components and 40-50% of water phase components, wherein the oil phase components comprise oil phase substances, oxyethylene nonionic surfactants and alcohol ethers, and the water phase components comprise Gemini surfactants, cationic quaternary ammonium salt surfactants, alcohols and water;
the external phase of the nano microemulsion is a water phase, and the internal phase is an oil phase;
the Gemini surfactant is one or a combination of more than two of cationic Gemini surfactant and derivatives thereof, and the Gemini surfactant is a polyoxyethylene-group-containing Gemini quaternary ammonium salt, a hyperbranched Gemini quaternary ammonium salt and an asymmetric Gemini quaternary ammonium salt;
wherein the cationic quaternary ammonium salt type surfactant comprises one or more than two of Jierten, xinterfenamid and domiphen bromide;
wherein the alcohol is small molecular alcohol with carbon number not more than 5;
wherein the oxyethylene nonionic surfactant is fatty alcohol polyoxyethylene ether;
wherein the alcohol ether comprises one or more than two of lower alcohol ether of ethylene glycol and lower alcohol ether of propylene glycol, and the lower carbon is less than 5 carbons.
2. The bleeding oil drainage agent according to claim 1, wherein the content of Gemini surfactant is 10wt.% to 15wt.%, the content of cationic quaternary ammonium salt surfactant is 12wt.% to 20wt.%, the content of alcohol is 5wt.% to 8wt.%, the content of water is 4wt.% to 10wt.%, the content of oil phase substance is 18wt.% to 25wt.%, the content of oxyethylene nonionic surfactant is 18wt.% to 25wt.%, and the content of alcohol ether is 13wt.% to 20wt.%, based on 100 wt.% of the nanoemulsion.
3. The oil penetration drain of claim 1 wherein the alcohol comprises one or a combination of two or more of methanol, propanol, ethylene glycol, ethanol, propanol, isopropanol, ethylene glycol, butanol, and pentanol.
4. The bleed oil formulation of claim 1 wherein the oxyethylene nonionic surfactant is AEO20.
5. The bleeding oil drainage agent of claim 1, wherein the Gemini surfactant is a hyperbranched Gemini foamless surfactant 31766.
6. The oil-bleeding agent according to claim 1, wherein the water is one of distilled water, deionized water, and tap water.
7. The oil bleeding agent according to claim 1, wherein the oil phase substance comprises one or a combination of two or more of oilfield crude oil, crude oil diluted with light oil, and linear saturated aliphatic hydrocarbon.
8. The oil penetration enhancer of any one of claims 1-7 wherein the effective concentration of the nanoemulsion is between 0.05wt.% and 0.7 wt.%, based on 100% of the total mass of the nanoemulsion dilution.
9. A method of preparing a range hood as claimed in any one of claims 1 to 8, wherein the method comprises:
uniformly mixing an oil phase substance, an oxyethylene nonionic surfactant and alcohol ether to obtain an oil phase component;
uniformly mixing a Gemini surfactant, a cationic quaternary ammonium salt surfactant, alcohol and water to obtain a water phase component;
and uniformly mixing the oil phase component and the water phase component to form a homogeneous nano microemulsion, thereby preparing the nano microemulsion type oil seepage and drainage agent.
10. The method of manufacturing according to claim 9, wherein the method comprises: and diluting the prepared nano-microemulsion to obtain the nano-microemulsion type oil seepage and drainage agent with the effective concentration of the nano-microemulsion of 0.05 to 0.7 to wt percent.
11. Use of a bleed oil formulation according to any of claims 1 to 8 for enhanced oil recovery from low permeability, ultra low permeability tight reservoir nano pore throat bleed oil.
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