CN111253922B - In-situ synthesized nanoparticle stable foam system and preparation and application thereof - Google Patents

In-situ synthesized nanoparticle stable foam system and preparation and application thereof Download PDF

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CN111253922B
CN111253922B CN201811453002.0A CN201811453002A CN111253922B CN 111253922 B CN111253922 B CN 111253922B CN 201811453002 A CN201811453002 A CN 201811453002A CN 111253922 B CN111253922 B CN 111253922B
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foam system
nanoparticle
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foam
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CN111253922A (en
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邹新源
罗文利
马德胜
周新宇
田茂章
蒋志斌
王正波
冯利娟
许颖
黄丽
何军
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/92—Compositions for stimulating production by acting on the underground formation characterised by their form or by the form of their components, e.g. encapsulated material
    • C09K8/94—Foams
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/10—Nanoparticle-containing well treatment fluids

Abstract

The invention provides an in-situ synthesized nanoparticle stable foam system and preparation and application thereof, wherein the in-situ synthesized nanoparticle stable foam system comprises the following raw materials by taking the total weight of the in-situ synthesized nanoparticle stable foam system as 100 percent: 0.5 to 5 percent of silicate, 0.1 to 1.0 percent of biosurfactant alkyl glycoside and the balance of saline. The foam system provided by the invention is self-generated in-situ nanoparticle stable foam, and the silicate serving as the raw material of the foam system can react with divalent metal ions contained in brine, such as Ca2+、Mg2+、Ba2+And Sr2+The inorganic nano particles are formed by chemical reaction, and the modified nano particles are not required to be added, so that the cost is low and the operation is simple; the formula has better adaptability under the conditions of high temperature and high salt oil reservoir, and the generated nano particles can be adsorbed on a foam Plateau interface, so that the strength and the deformation resistance of a liquid film can be enhanced, and the stability of the foam is obviously improved.

Description

In-situ synthesized nanoparticle stable foam system and preparation and application thereof
Technical Field
The invention relates to an in-situ synthesized nanoparticle stable foam system and preparation and application thereof, belonging to the technical field of oil and gas field development and oil extraction engineering.
Background
The foam flooding has the advantages of improving the heterogeneity of an oil reservoir, expanding the displacement wave and volume, improving the oil displacement efficiency and the like due to the selective plugging, and the stability of the foam plays a crucial role in the oil displacement effect of the foam.
Especially under severe formation conditions of high temperature, high salt and the like, divalent salt ions such as Ca2+、Mg2+、Ba2+And Sr2+And the influence on the foam stability is larger than that of monovalent salt ions, most of the surfactant directly generates precipitates under the condition of high divalent salt, so that the loss of the surfactant is serious, the foaming performance of the foam formula is obviously reduced, and the foam system is difficult to stably exist in a stratum.
The nano particles can move in the porous medium, the rock adsorption retention is small, and the nano particles are adsorbed on a gas-liquid interface to generate a synergistic effect, so that the effect of stabilizing foam is achieved. For example, chinese patent CN108300447A provides a nanoparticle foam system for improving oil displacement efficiency, which is a synergistic effect of five components, namely a foaming agent, a shielding agent, a reinforcing agent, a stabilizer and nanoparticles, to stabilize foam, but the system is complicated to operate when applied in a mine site and can only be applied under the condition of low-salinity oil deposit; chinese patent CN102746841A provides a compound foam system added with nano particles for oil and gas fields, which consists of an anionic surfactant, modified silica nano particles and a counter ion salt, but the modified silica nano particles are expensive, so that the cost of the foam system is obviously increased, and the field application is limited.
Therefore, providing a novel in-situ synthesized nanoparticle-stabilized foam system has become a technical problem to be solved in the art.
Disclosure of Invention
To address the above-described shortcomings and drawbacks, it is an object of the present invention to provide an in situ, authigenic, nanoparticle-stabilized foam system.
It is another object of the present invention to provide a method for preparing the in situ authigenic nanoparticle-stabilized foam system.
It is still another object of the present invention to provide the use of the in situ self-generated nanoparticle stabilized foam system in a reservoir oil recovery gas drive or foam drive. One of the problems solved by the in-situ synthesized nanoparticle stable foam system provided by the invention is that most of the existing foam systems have poor adaptability under the condition of high-salt oil reservoirs, and particularly have poor adaptability in strata with high contents of calcium, magnesium, barium, strontium ions and the like; secondly, the problems that the cost of the nano particles is high and the nano particles are difficult to use on site in most foam systems adopting the nano particles for stabilization can be solved.
In order to achieve the above objects, in one aspect, the present invention provides an in-situ synthesized nanoparticle-stabilized foam system, wherein the in-situ synthesized nanoparticle-stabilized foam system comprises the following raw materials, based on 100% of the total weight of the in-situ synthesized nanoparticle-stabilized foam system: 0.5 to 5 percent of silicate, 0.1 to 1.0 percent of biosurfactant alkyl glycoside (APG) and the balance of saline.
According to a specific embodiment of the present invention, in the in-situ synthesized nanoparticle stable foam system, the raw material composition comprises, based on 100% of the total weight of the in-situ synthesized nanoparticle stable foam system: 0.5 to 3.0 percent of silicate, 0.25 to 0.8 percent of biosurfactant alkyl glycoside and the balance of saline.
According to a specific embodiment of the present invention, in the in-situ synthesized nanoparticle stable foam system, the raw material composition comprises, based on 100% of the total weight of the in-situ synthesized nanoparticle stable foam system: 0.5 to 2.5 percent of silicate, 0.25 to 0.8 percent of biosurfactant alkyl glycoside and the balance of saline.
According to a specific embodiment of the present invention, in the in-situ synthesized nanoparticle stable foam system, the raw material composition comprises, based on 100% of the total weight of the in-situ synthesized nanoparticle stable foam system: 0.5 to 2.5 percent of silicate, 0.4 percent of biosurfactant alkyl glycoside and the balance of saline.
According to a specific embodiment of the present invention, the in situ authigenic nanoparticle-stabilized foam system includes inorganic nanoparticles having a diameter of 10-120 nm.
According to a specific embodiment of the present invention, in the in situ authigenic nanoparticle-stabilized foam system, the silicate comprises sodium silicate and/or potassium silicate.
According to a specific embodiment of the invention, in the in situ synthesized nanoparticle stable foam system, the alkyl chain carbon number of the biosurfactant alkyl glycoside is 6-14.
According to a specific embodiment of the present invention, in the in situ synthesized nanoparticle stabilized foam system, the polymerization degree of the biosurfactant alkyl glycoside is 1-2.
According to a specific embodiment of the present invention, in the in situ authigenic nanoparticle-stabilized foam system, the brine is a brine containing divalent metal ions;
wherein the total mineralization of the brine is 10000-300000mg/L, and the content of divalent metal ions is more than 1000 mg/L.
According to a specific embodiment of the present invention, in the in situ authigenic nanoparticle-stabilized foam system, the divalent metal ion includes Ca2+、Mg2+、Ba2+And Sr2+One or a combination of several of them.
Wherein, in the specific embodiment of the invention, the total mineralization is 10000-300000mg/L, and the content of the divalent metal ions is more than 1000mg/L, the brine can be prepared by adding NaCl, CaCl and the like at normal temperature2One or more of magnesium chloride, barium chloride and strontium chloride are added into water and stirred to prepare the product.
In another aspect, the present invention further provides a preparation method of the in-situ synthesized nanoparticle stable foam system, wherein the preparation method comprises the following steps:
and sequentially adding a biosurfactant alkyl glycoside and silicate into the saline water, uniformly stirring, and standing to obtain the in-situ authigenic nanoparticle stable foam system.
According to a specific embodiment of the present invention, in the preparation method, the stirring is performed for 45 minutes on a magnetic stirrer.
According to a particular embodiment of the invention, in said preparation process, said resting time is comprised between 5 and 10 minutes.
In another aspect, the invention also provides the application of the in-situ self-generated nanoparticle stable foam system in reservoir oil exploitation gas flooding or foam flooding.
According to the specific embodiment of the invention, in the application, the oil reservoir temperature is 20-150 ℃, the total mineralization degree of water is 10000-300000mg/L, and the content of divalent metal ions is more than 1000 mg/L.
According to a particular embodiment of the invention, in said use, said divalent metal ion comprises Ca2+、Mg2+、Ba2 +And Sr2+One or a combination of several of them.
Compared with the prior art, the invention has the following advantages:
the foam system provided by the invention is in-situ self-generated nanoparticle stable foam, and the silicate serving as the raw material of the foam system can react with divalent metal ions contained in brine, such as Ca2+、Mg2+、Ba2+And Sr2+The inorganic nano particles are formed by chemical reaction, and the modified nano particles are not required to be added, so that the cost is low and the operation is simple; the formula has better adaptability under the conditions of high temperature and high salt oil reservoir, and the generated nano particles can be adsorbed on a foam Plateau interface, so that the strength and the deformation resistance of a liquid film can be enhanced, and the stability of the foam is obviously improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a scanning electron microscope image of in situ synthesized nanoparticles prepared in example 1 of the present invention.
FIG. 2 shows the foam formulations prepared in example 3 of the present invention in different CaCl2Foaming capacity and stability of the foam at concentration.
Detailed Description
In order to clearly understand the technical features, objects and advantages of the present invention, the following detailed description of the technical solutions of the present invention will be made with reference to the following specific examples, which should not be construed as limiting the implementable scope of the present invention.
Example 1
The embodiment provides preparation and characterization of in-situ synthesized nano foam stabilizing particles, which specifically comprises the following steps:
the experimental water adopts the water produced from the middle east Abuza reservoir, the total mineralization degree of the water is 217308.72mg/L, wherein, Ca2+、Mg2+The total content of the divalent ions is 19940 mg/L.
Weighing 1.5g of silicate (sodium silicate) by using an electronic balance, slowly pouring the silicate (sodium silicate) into a beaker filled with 100mL of Abuzat oil reservoir produced water, stirring the solution by using a magnetic stirrer for 30min, and putting the solution into an ultrasonic oscillator for oscillation for 20min to obtain the nano-particles.
By using G3Filtering with glass sand core funnel (average diameter of micropores is 15-40 μm) to obtain milky flocculent emulsion. A certain amount of the suspension (i.e., milky white flocculent emulsion) was taken and characterized by scanning electron microscopy, and the results are shown in FIG. 1. from FIG. 1, the nanoparticles prepared in this example were aggregates with a single particle diameter of 80 nm.
Example 2
The embodiment provides a series of in-situ synthesized nano-stable foam systems which are respectively numbered from 1 to 7, and tests the foaming capacity and stability of the in-situ synthesized nano-stable foam systems, and the method specifically comprises the following steps:
the in-situ synthesized nanoparticle stable foam system comprises the following raw materials by taking the total weight of the in-situ synthesized nanoparticle stable foam system as 100 percent: silicate (sodium silicate), biosurfactant alkyl glycoside (APG), and brine.
In the foam formulas 1 to 7, the weight percentages of silicate, biosurfactant alkyl glycoside (APG) and brine are shown in the following table 1, wherein the foam formula 1 only contains APG and brine;
in the foam formulas 1-7, the brine is the produced water of the middle east Abuzer reservoir, the total mineralization degree of the brine is 217308.72mg/L, and the Ca content is2+、Mg2+The total content of the divalent ions is 19940 mg/L.
The above foam formulations 1-7 can be prepared by a preparation method comprising the following steps:
adding alkyl glycoside biosurfactant and sodium silicate into the saline water in sequence (no sodium silicate is added in the formula 1, namely no inorganic nano-particles are generated in the formula 1, and the formula 1 is used for comparing with the formula 2-7), stirring on a magnetic stirrer for 45 minutes, and standing for 5-10 minutes to obtain the foam formula;
in the embodiment, the biosurfactant alkyl glycoside (APG) is APG0814 which is a mixture with an alkyl chain of 8-14 carbon atoms and has an average polymerization degree of 1.3-1.5;
the diameters of the inorganic nanoparticles contained in the in situ authigenic nanoparticle-stabilized foam systems 2-7 provided in this example are all around 80 nm.
Testing by adopting a Wu Yin stirring method (Waring Blender), respectively pouring 200mL of prepared foaming agent solution (foam formula 1-7) with a certain concentration into a Wu Yin (Waring) stirrer, stirring at the rotating speed of 7000r/min for 1 minute, then pouring the foam into a 1000mL measuring cylinder within 30 seconds, and recording the volume of the foam and the half-time of liquid separation, namely the half-life of the liquid separation;
the experimental water in the evaluation of foam foaming capacity and stability adopts the middle east Abuz oil reservoir produced water, the total mineralization is 217308.72mg/L, wherein, Ca2+、Mg2+The total content of the divalent ions is 19940mg/L, and the experimental temperature is 90 ℃. The foaming capacity and foam stability test results for the various foam formulations are shown in table 1 below.
TABLE 1 foaming Capacity and foam stability test results for various foam formulations
Numbering Foam formulations Foaming volume (mL) Half life of liquid(s)
1 0.4％APG 960 229
2 0.4％APG+0.5％Na2SiO3 930 231
3 0.4％APG+1.0％Na2SiO3 930 237
4 0.4％APG+1.5％Na2SiO3 950 254
5 0.4％APG+2.0％Na2SiO3 940 252
6 0.4％APG+2.5％Na2SiO3 930 238
7 0.4％APG+3.0％Na2SiO3 910 217
As can be seen from table 1, after a certain amount of sodium silicate is added, the stability of the foam system is significantly increased because the sodium silicate can chemically react with the divalent metal ions contained in the brine to form inorganic nanoparticles.
Example 3
The test was performed at 90 ℃ using wu-yin stirring and the foam volume and the half-life of the eluent was recorded for the foam formulation system (formulation 4 in table 1 for the test object) at different salt concentrations by varying the divalent salt concentration.
The experimental water is deionized water; the divalent salt for experiment is CaCl2The fixed mass concentration of the foaming agent APG is 0.4%, and the fixed mass concentration of the sodium silicate is 1.5%. The foam volume and liquid half-life curves for the foam formulation systems at different salt concentrations are shown in figure 2.
As can be seen in FIG. 2, the foam formulation is at a higher CaCl2The nanoparticles produced at a concentration of (a) contribute to the stability of the foam.
Example 4
Drag factor, residual drag factor test
The experimental temperature is 90 ℃, and the experimental water is middle east AbbupleurumThe resistance factor and the residual resistance factor of the foam formula (formula 1 and formula 4 in table 1) were determined by using a beret core with a length of 10cm, a diameter of 2.5cm and a permeability of 30mD in the produced water of the oil reservoir. Water-driving at a speed of 0.3mL/L, and recording the pressure difference delta P between the inlet end and the outlet end of the core holder after the pressure is balanced1(ii) a Injecting foam slug at 0.3mL/L speed, and recording pressure difference delta P between inlet end and outlet end of the core holder after pressure is balanced2(ii) a And finally, performing subsequent water drive at the same speed, and recording the pressure difference delta P between the inlet end and the outlet end of the rock core holder after the pressure is balanced3；△P2/△P1I.e. the drag factor, Δ P3/△P1I.e. the residual drag factor. The experimental results of the drag factors and residual drag factors for formulations 1 and 4 are shown in table 2 below.
TABLE 2 Experimental results for the drag factor and residual drag factor of the foam formulations
Foam formulations Gas (es) Gas to liquid ratio Resistance factor Residual drag factor
0.4％APG Nitrogen gas 3:1 27.83 16.02
0.4％APG+1.5％Na2SiO3 Nitrogen gas 3:1 34.62 22.74
As can be seen from table 2, the stability of the foam formulation can be increased by adding sodium silicate to the foam formulation, resulting in a significant increase in the blocking capacity of the foam.

Claims (13)

1. An in-situ synthesized nanoparticle-stabilized foam system, which is characterized by comprising the following raw materials in percentage by weight based on 100 percent of the total weight of the in-situ synthesized nanoparticle-stabilized foam system: 0.5 to 2.5 percent of silicate, 0.1 to 1.0 percent of biosurfactant alkyl glycoside and the balance of saline;
wherein the silicate is sodium silicate and/or potassium silicate;
the content of divalent metal ions in the brine is more than 1000mg/L, and the divalent metal ions are Ca2+、Mg2+、Ba2+And Sr2+One or a combination of several of them.
2. The in situ self-generated nanoparticle stabilized foam system according to claim 1, wherein the raw material composition comprises, based on 100% of the total weight of the in situ self-generated nanoparticle stabilized foam system: 0.5 to 2.5 percent of silicate, 0.25 to 0.8 percent of biosurfactant alkyl glycoside and the balance of saline.
3. The in situ self-generated nanoparticle stabilized foam system according to claim 2, wherein the raw material composition comprises, based on 100% of the total weight of the in situ self-generated nanoparticle stabilized foam system: 0.5 to 2.5 percent of silicate, 0.4 percent of biosurfactant alkyl glycoside and the balance of saline.
4. The in situ self-generating nanoparticle stabilized foam system according to any one of claims 1-3, wherein the inorganic nanoparticles contained in the in situ self-generating nanoparticle stabilized foam system have a diameter of 10-120 nm.
5. The in situ authigenic nanoparticle stabilizing foam system as recited in any one of claims 1-3, wherein the biosurfactant alkyl glycoside has an alkyl chain carbon number of from 6 to 14.
6. The in situ authigenic nanoparticle-stabilized foam system according to any one of claims 1-3, wherein the biosurfactant alkyl glycoside has a degree of polymerization of 1-2.
7. The in situ authigenic nanoparticle-stabilized foam system as recited in any one of claims 1-3, wherein the total salinity of the brine is 10000-300000 mg/L.
8. The method of preparing an in situ authigenic nanoparticle-stabilized foam system as described in any one of claims 1-7, wherein the method comprises the steps of:
and sequentially adding a biosurfactant alkyl glycoside and silicate into the saline water, uniformly stirring, and standing to obtain the in-situ authigenic nanoparticle stable foam system.
9. The method of claim 8, wherein the stirring is on a magnetic stirrer for 45 minutes.
10. The method of claim 8 or 9, wherein the standing time is 5 to 10 minutes.
11. Use of the in situ authigenic nanoparticle stabilized foam system of any one of claims 1-7 in a reservoir oil recovery gas drive or foam drive.
12. According to claim11, characterized in that the reservoir temperature is 20-150 deg.foC, the total mineralization degree of the water is 10000-300000mg/L, and the content of the divalent metal ions is more than 1000 mg/L.
13. Use according to claim 12, wherein the divalent metal ion comprises Ca2+、Mg2+、Ba2+And Sr2+One or a combination of several of them.
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Publication number Priority date Publication date Assignee Title
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US3805893A (en) * 1972-08-28 1974-04-23 Union Oil Co Mobility-controlled caustic flood
US4848465A (en) * 1987-11-20 1989-07-18 Mobil Oil Corp. Use of alkali metal silicate foam with a chemical blowing agent
US5086840A (en) * 1989-01-27 1992-02-11 Dowell Schlumberger Incorporated Delayed rigid foam systems and applications in particular for plugging selective treatments in the oil industry
CN104845602A (en) * 2015-04-02 2015-08-19 中国石油大学(华东) Environmentally friendly over-stable polyphase foam system and preparation method thereof

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