CN110157403B - Low-permeability oil reservoir oil displacement agent - Google Patents
Low-permeability oil reservoir oil displacement agent Download PDFInfo
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- CN110157403B CN110157403B CN201910379995.XA CN201910379995A CN110157403B CN 110157403 B CN110157403 B CN 110157403B CN 201910379995 A CN201910379995 A CN 201910379995A CN 110157403 B CN110157403 B CN 110157403B
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- 238000006073 displacement reaction Methods 0.000 title claims abstract description 42
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 38
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 13
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000013329 compounding Methods 0.000 claims abstract description 9
- 230000035699 permeability Effects 0.000 claims description 19
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- 239000003607 modifier Substances 0.000 claims description 10
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical group CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 239000003921 oil Substances 0.000 description 70
- 238000011084 recovery Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000004094 surface-active agent Substances 0.000 description 10
- 239000000839 emulsion Substances 0.000 description 9
- 239000010779 crude oil Substances 0.000 description 8
- 238000004945 emulsification Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 230000001804 emulsifying effect Effects 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000008398 formation water Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 1
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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
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Geochemistry & Mineralogy (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Colloid Chemistry (AREA)
Abstract
The invention provides a low-permeability oil reservoir oil displacement agent. The oil displacement agent for the low-permeability reservoir is prepared by compounding modified polyvinyl alcohol and a trimethyl ammonium bromide cationic surfactant of C12-C18; the compounding mass ratio of the modified polyvinyl alcohol to the C12-C18 trimethyl ammonium bromide cationic surfactant is 1:9-9: 1. The oil displacement agent for the low-permeability reservoir has a good oil displacement effect.
Description
Technical Field
The invention relates to an oil displacement composition, in particular to an oil displacement composition suitable for a low-permeability oil reservoir, and belongs to the technical field of oil reservoir exploitation.
Background
Since the 21 st century, the demand for petroleum has risen dramatically in countries around the world with the rapid growth of national economy. Complex oil reservoirs represented by low-permeability and ultra-low-permeability oil reservoirs become important components for the replacement of petroleum resource yield in China, and are important resource bases for increasing storage and increasing production in the petroleum industry in China in a considerable period of time in the future.
Low permeability reservoirs currently face a number of problems, and low permeability oil fields have a great difference in development effect compared to medium and high permeability reservoirs. Most of the low-permeability oil reservoirs in China adopt a water injection development mode. However, due to low porosity and low permeability, the phenomena of 'no injection and no production' of high water injection pressure generally exist in the development process, and finally the recovery ratio of the oil field is low. In addition, in northwest areas of part of oil fields in China, water resources are deficient, and implementation of water injection development is not facilitated.
The surfactant has a series of performances of low interfacial tension, crude oil emulsification, wettability change and the like, can effectively reduce pressure and increase injection, starts residual oil in a hypotonic matrix, and has huge application prospect in the development process of ultra-hypotonic low-permeability oil reservoirs. Statistically, 80% of crude oil in the world is produced in the form of emulsion, and recent indoor research and field practice show that in a hypotonic oil reservoir, the contribution rate of the emulsification of a surfactant to the recovery rate is larger than the contribution rate of the interfacial activity to the recovery rate.
The surfactants with better emulsification effect applied on site at present are OP series and petroleum sulfonate series. However, they have the disadvantages of environmental pollution and poor temperature resistance.
Therefore, aiming at the conditions of large conventional surfactant displacement amount, poor temperature resistance and poor emulsion stability of the low-permeability reservoir, a self-emulsifying displacement system which has excellent emulsifying property under low viscosity, can spontaneously form stable emulsion in the low-permeability reservoir and further improves the recovery ratio of the low-permeability reservoir is needed to be provided.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a surfactant oil displacement agent with good oil displacement effect.
In order to realize the technical purpose, the invention provides a low-permeability reservoir (the permeability is less than 50mD) oil-displacing agent, which is prepared by compounding modified polyvinyl alcohol and a C12-C18 trimethyl ammonium bromide cationic surfactant; wherein the compounding mass ratio of the modified polyvinyl alcohol to the C12-C18 trimethyl ammonium bromide cationic surfactant is 1:9-9: 1.
In the low-permeability oil reservoir oil displacement agent, the adopted modified polyvinyl alcohol is subjected to hydrophobic modification on polyvinyl alcohol without hydrophobic property, so that a high-molecular surfactant with both hydrophilic groups and hydrophobic groups is constructed. The modified high molecular surfactant has less consumption and high molecular weight and excellent oil drop dispersing performance. Is more economical and friendly.
The high molecular surfactant adopted by the low-permeability oil reservoir oil displacement agent is modified polyvinyl alcohol, and the obtained compound has self-emulsifying oil displacement performance through the synergistic effect of the modified polyvinyl alcohol and the trimethyl ammonium bromide cationic surfactant of C12-C18, and can be spontaneously emulsified without external force.
In a specific embodiment of the invention, the compounding mass ratio of the modified polyvinyl alcohol to the trimethyl ammonium bromide cationic surfactant with the carbon number of C12-C18 is 1:9, 3:7, 5:5, 7:3 or 9: 1.
In one embodiment of the present invention, the C12-C18 trimethylammonium bromide cationic surfactant used is cetyl trimethylammonium bromide.
Namely, the oil displacement agent for the low permeability reservoir is compounded by modified polyvinyl alcohol and hexadecyl trimethyl ammonium bromide; wherein the compounding mass ratio of the modified polyvinyl alcohol to the hexadecyl trimethyl ammonium bromide can be 1:9-9: 1.
In one embodiment of the present invention, the molecular weight of the modified polyvinyl alcohol used is 2000-3000. The modified polyvinyl alcohol with the molecular weight has better oil drop dispersing performance and emulsifying performance. For example, the modified polyvinyl alcohol used may have a molecular weight of 2200.
In one embodiment of the present invention, the modified polyvinyl alcohol has both hydrophobic and hydrophilic groups.
In one embodiment of the present invention, the modified polyvinyl alcohol is obtained by hydrophobically modifying polyvinyl alcohol with a modifier.
For example, the modifier used may be bromohexadecane or 2, 3-epoxypropyltrimethylammonium chloride.
Preferably, the modifier used is bromohexadecane. Namely, the modified polyvinyl alcohol is obtained by modifying polyvinyl alcohol with bromohexadecane. The structural formula of the modified polyvinyl alcohol is shown as the following formula:
wherein x is an integer not less than 1, y is an integer not less than 1, m is an integer not less than 1, n is an integer not less than 1, and x + y + m + n is not less than 40 and not more than 70.
In one embodiment of the invention, the amount of modifier is 12.5% to 17.5% by mass of the polyvinyl alcohol. For example, the modifiers are used in amounts of 13%, 14%, 15%, 16% and 17% by mass of the polyvinyl alcohol.
In one embodiment of the present invention, the modified polyvinyl alcohol is prepared by the following steps:
mixing the modifier with polyvinyl alcohol at 55-75 ℃, and reacting for 40-50 h (preferably 48h) to obtain the modified polyvinyl alcohol.
In the low-permeability oil reservoir oil displacement agent, a trimethyl ammonium bromide cationic surfactant of C12-C18 is compounded with modified polyvinyl alcohol. CTAB is a common chemical reagent in oilfield field and laboratory research, and has enough research support for application in the field of petroleum. In addition, the CTAB has a structure with 16 carbon chains similar to the hydrophobic part of the modified polyvinyl alcohol, so that the CTAB has a certain synergistic effect and is beneficial to the occurrence of spontaneous emulsification.
When the low-permeability oil reservoir oil displacement agent is specifically used for emulsifying a low-permeability oil reservoir, the implementation can be carried out according to the conventional oil displacement agent implementation mode in the field. Wherein the addition amount of the oil displacement agent for the low-permeability reservoir is 3000 mg/L.
The low-permeability oil reservoir oil displacement agent can be prepared by the following steps:
and adding modified polyvinyl alcohol and a trimethyl ammonium bromide cationic surfactant of C12-C18 into the simulated formation water, mixing and stirring for 30min, and standing to obtain the low-permeability oil reservoir oil displacement agent.
The oil displacement agent for the low-permeability oil reservoir has wide raw material source and low price, and can spontaneously form an emulsified oil displacement system with the low-permeability oil reservoir.
The oil displacement agent for the low-permeability reservoir has a good physical simulation oil displacement effect, can further improve the crude oil recovery rate after conventional water displacement of the low-permeability core, and can improve the recovery rate by about 60%.
The oil displacement agent for the low-permeability oil reservoir is a self-emulsifying oil displacement system, can be spontaneously emulsified without external force, and provides a basis for screening a method for improving the recovery ratio of a suitable oil field.
Drawings
FIG. 1 is a curve of interfacial tension of the oil displacement agent of the low permeability reservoir in example 1 as a function of the formulation ratio.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides a self-emulsifying oil displacement agent for a low-permeability oil reservoir, which is prepared by the following steps:
preparing a self-emulsifying oil displacement system by using simulated formation water, wherein the total concentration is 3000mg/L, the concentration of modified PVA-1570 (with the molecular weight of 2200) (obtained by modifying polyvinyl alcohol with bromohexadecane) is 2100mg/L, the concentration of CTAB (cetyl trimethyl ammonium bromide) is 900mg/L, stirring for 30min, and standing to obtain the self-emulsifying polymer composite oil displacement agent.
The above oil displacing agent of the present example was subjected to a surface tension test. The instrument adopts a TX-500C interfacial tension meter, the oil phase adopts degassed and dehydrated crude oil of a certain oil field, and the water phase is actual formation water of the oil field. The test temperature was 45 ℃ and the oil-water interfacial tension was measured at 5000 rpm. The result shows that when the compounding mass ratio is 7:3, the system has self-emulsifying property and the emulsion stability is good.
As can be seen from figure 1, the compound system of the modified PVA-1570 and the CTAB respectively reaches a low interfacial tension state (less than or equal to 10) when the mass ratio is 9:1 and 7:3-2mN/m)。
The oil-displacing agent of the present example was subjected to performance tests, and the results are shown in table 1.
TABLE 1
As can be seen from Table 1, the viscosity of the self-emulsifying system is very low and is similar to that of water although the self-emulsifying system is a high molecular surfactant compound system. Too high a viscosity can make displacement of the chemical agent in a low permeability reservoir difficult, and formation plugging and the like occur. And the system has low viscosity, and is more favorable for the application of the system in the enhanced recovery of low-permeability oil reservoirs.
A core displacement experiment is carried out by using a self-emulsifying oil displacement system, the core length is 10.0cm, the permeability is 15mD, the saturated water is 18mL, and the post-saturated oil is 10 mL. Water flooding-chemical flooding-water flooding was performed with the recovery ratio as in table 2.
TABLE 2
As can be seen from Table 2, the self-emulsifying oil displacement agent has low interfacial tension and high emulsion stabilization time, and spontaneously emulsifies crude oil to improve the oil-water mixing capability. It can be seen that the self-emulsifying oil displacement agent of the embodiment can obviously improve the recovery ratio. Firstly, carrying out water flooding on the oil-containing low-permeability core, wherein the recovery ratio is 41%, then carrying out self-emulsification flooding (namely tertiary oil recovery) so as to improve the recovery ratio by 12%, and then carrying out secondary water flooding so as to improve the recovery ratio by 3%. The total recovery was 56%.
When the dosage of the oil displacement agent in this embodiment is 3000mg/L, and the NaCl concentration is 10000-20000mg/L, the spontaneous emulsification effect is the best, and the oil sample can spontaneously enter the water phase to form an emulsion when being added. The emulsion has strong stability, and still keeps good emulsification effect after standing for 30 min.
The oil-displacing agent solution of this example was placed in a test tube with a pipette and allowed to stand in an incubator at 45 ℃ for 2 hours. Then taking out the test tube, taking the crude oil (water-oil ratio 9:1) with constant temperature of 45 ℃ by using a pipette, suspending and dripping the crude oil at a position 1cm away from the test tube, and observing the change condition of the solution in the test tube after the crude oil is dripped. The oil drops spontaneously enter the water phase to form an emulsion, which indicates that the emulsifier has spontaneous emulsifying property.
The above examples illustrate that the oil displacing agent for low permeability reservoirs of the present invention has better enhanced oil recovery effect for low permeability reservoirs. In addition, the produced fluid can be obviously seen to exist in an emulsion form in the displacement process, so that the application range of the produced fluid is expanded, and a new idea that the high molecular surfactant can be used for tertiary oil recovery of a low-permeability oil reservoir is provided.
Claims (7)
1. The low-permeability oil reservoir oil displacement agent is characterized by being prepared by compounding modified polyvinyl alcohol and a C12-C18 trimethyl ammonium bromide cationic surfactant; wherein the compounding mass ratio of the modified polyvinyl alcohol to the trimethyl ammonium bromide cationic surfactant of C12-C18 is 1:9-9: 1;
the modified polyvinyl alcohol is prepared by the following steps:
mixing the modifier with polyvinyl alcohol at 55-75 ℃, and reacting for 40-50 h to obtain modified polyvinyl alcohol; the modifier is bromohexadecane.
2. The low permeability reservoir oil-displacing agent of claim 1, wherein the formulation mass ratio of the modified polyvinyl alcohol to the trimethyl ammonium bromide cationic surfactant of C12-C18 is 1:9, 3:7, 5:5, 7:3 or 9: 1.
3. A low permeability reservoir oil displacing agent according to claim 1 or 2, wherein the C12-C18 trimethyl ammonium bromide cationic surfactant is cetyl trimethyl ammonium bromide.
4. The low permeability reservoir oil displacement agent of claim 1, wherein the molecular weight of the modified polyvinyl alcohol is 2000-3000.
5. The low permeability reservoir oil-displacing agent of claim 1, wherein the amount of the modifier is 12.5-17.5% by mass of the polyvinyl alcohol.
6. The low permeability reservoir oil-displacing agent of claim 5, wherein the modifier is used in an amount of 15% by mass of the polyvinyl alcohol.
7. The use of a low permeability reservoir oil displacing agent according to any one of claims 1-6, wherein the low permeability reservoir oil displacing agent is added at 3000mg/L when used to emulsify a low permeability reservoir.
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