CN110295033A - A kind of hydrophobic associated polymer and the self-assembly system of surfactant and its preparation method and application - Google Patents
A kind of hydrophobic associated polymer and the self-assembly system of surfactant and its preparation method and application Download PDFInfo
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- CN110295033A CN110295033A CN201810249618.XA CN201810249618A CN110295033A CN 110295033 A CN110295033 A CN 110295033A CN 201810249618 A CN201810249618 A CN 201810249618A CN 110295033 A CN110295033 A CN 110295033A
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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
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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
- C09K8/588—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 polymers
Abstract
The invention belongs to oil field development technical fields, a kind of hydrophobic associated polymer and self-assembly system of surfactant and its preparation method and application are specifically provided, the self-assembly system includes hydrophobic associated polymer, surfactant, Yan Heshui, wherein the mass concentration ratio of hydrophobic associated polymer and surfactant is 3~12: 1, and the surfactant is nonionic Gemini surface active agent.Self-assembly system of the invention can significantly improve hydrophobic associated polymer in critical association concentration solution viscosity below, facilitate the raising of hydrophobic associated polymer oil displacement efficiency.
Description
Technical field
The invention belongs to oil field development technical fields, and in particular to a kind of hydrophobic associated polymer and surfactant from
Assembly system and preparation method thereof and the self-assembly tie up to the application in polymer displacement of reservoir oil tech.
Background technique
The oil field majority of China's exploitation has entered High water cut, high recovery percent of reserves development phase, and chemical flooding is to further increase
The dominant technology of oil recovery rate.The viscosity of oil displacement system is a core parameter of chemical flooding technology, and the mechanism of action is to pass through
The viscosity for improving displacing fluid, increases its filtrational resistance in the porous media of stratum, plays the role of fluidity control, and expansion involves body
Product, to improve recovery ratio.Increasing displacement fluid viscosity is realized by adding partially hydrolyzed polyacrylamide (PHPA) into water, is gathered
The viscosity of acrylamide solution increases with the increase of polymer molecular weight, and existing molecular weight is up to 30,000,000 superelevation point now
Sub- weight polymers product, although the tackifying ability of this super high molecular weight polymer is fine, its shear degradation is serious, and scene makes
With less.What the oil field displacement of reservoir oil used is mostly the polymer that molecular weight is 25,000,000.In addition, Partially Hydrolyzed Polyacrylamide Solution
Viscosity increases with salinity, temperature is increased and significantly reduced, and is not suitable for high temperature, high salinity reservoir.
In recent ten years, have developed the better hydrophobic associated polymer of Efficient Adhesive Promotion both at home and abroad, such as application No. is
The patent document of CN201610548890.9, CN201511018952.7, CN201511018165.2 are disclosed with hydrophilic chain
The copolymer of section and hydrophobic segment has the side chain containing hydrophobic grouping on polymer molecule backbone, by intermolecular hydrophobic group
Association, formed spacial framework, increase substantially solution viscosity.There are a critical associations for hydrophobic associated polymer
Concentration, when polymer concentration is less than critical association concentration, the hydrophobic grouping on polymer molecule side chain based on Intramolecular association,
Intramolecular association reduces polymer molecular size, is helpless to viscosify, and the polymer solution viscosity of this concentration range is lower；It is poly-
When closing object concentration greater than critical association concentration, the hydrophobic grouping on polymer molecule side chain is intermolecular based on Interpolymer Association
Association increases polymer molecular size, and solution viscosity significantly increases.The critical association concentration of hydrophobic associated polymer is generally big
In 1500mg/L.Although the polymer concentration that oil field is actually implanted into is greater than critical association concentration, viscosity is very high, with polymer
Solution is in underground percolation, and the gradually Adsorption And Retention in blowhole, along with the dilution of underground water, polymer concentration will soon
Critical association concentration is reduced to hereinafter, there was only several hundred milligrams of polymer to the general every liter of Produced Liquid of well is produced.Hydrophobic association polymerization
Object plays the polymer solution for being less than critical association concentration of the displacement of reservoir oil in the most of the time of underground percolation.Therefore, it improves
Hydrophobic associated polymer has weight in critical association concentration solution viscosity below, to the oil displacement efficiency for improving hydrophobic associated polymer
Want meaning.
Summary of the invention
For above situation, the object of the present invention is to provide the self assemblies of a kind of hydrophobic associated polymer and surfactant
System, by the way that specific surfactant is added into hydrophobic association polymer solution, by the hydrophobic of hydrophobic associated polymer
Interaction between group and surfactant hydrophobic group forms molecular self-assembly, and it is poly- to be remarkably improved hydrophobic association
Object is closed in critical association concentration solution viscosity below.
The first aspect of the present invention provides the self-assembly system of a kind of hydrophobic associated polymer and surfactant, should be certainly
Assembly system includes hydrophobic associated polymer, surfactant, Yan Heshui, wherein hydrophobic associated polymer and surfactant
Mass concentration ratio is 3~12: 1, and the surfactant is nonionic Gemini surface active agent.
The second aspect of the present invention provides the preparation method of above-mentioned self-assembly system, which includes:
1) salting liquid is prepared according to total salinity；
2) hydrophobic association polymer solution and surfactant solution are prepared by solvent of salting liquid made from step 1)；
3) salting liquid, hydrophobic association polymer solution and surfactant solution are taken respectively according to mass concentration, is being stirred
Under the conditions of, the salting liquid of acquirement and surfactant solution are sequentially added in hydrophobic association polymer solution, obtain it is described from
Assembly system.
The third aspect of the present invention provides above-mentioned self-assembly system and the self-assembly as made from above-mentioned preparation method
Tie up to the application in polymer displacement of reservoir oil tech.
The present invention forms self-assembly system by the way that specific surfactant is added into hydrophobic association polymer solution, can
To significantly improve hydrophobic associated polymer in critical association concentration solution viscosity below, help to further increase hydrophobic association
The oil displacement efficiency of polymer.The quality solubility of hydrophobic associated polymer can be 300~1700mg/L in the self-assembly system, be applicable in
Concentration range it is wide, and preparation method is simple.
Other features and advantages of the present invention will then part of the detailed description can be specified.
Specific embodiment
To keep the present invention easier to understand, below in conjunction with embodiment, the present invention will be described in detail, these embodiment party
Formula only serves illustrative, is not intended to restrict the invention.
The first aspect of the present invention provides the self-assembly system of a kind of hydrophobic associated polymer and surfactant, should be certainly
Assembly system includes hydrophobic associated polymer, surfactant, Yan Heshui, wherein hydrophobic associated polymer and surfactant
Mass concentration ratio is 3~12: 1, and the surfactant is nonionic Gemini surface active agent.
In the present invention, the hydrophobic associated polymer can be selected from acrylamide/2- acrylamide alkyl sulfonic acid copolymer,
18 resin copolymer of acrylamide/acrylic acid, acrylamide/N- decyl/2- acrylamide-2-methylpro panesulfonic acid
Copolymer, acrylamide/n-vinyl pyrrolidone/2- methylacryoyloxyethyl-dimethyl-dodecylamine base ammonium bromide copolymerization
Object, acrylamide/N- alkyl phenyl acrylamide copolymer, acrylamide/acrylic acid/N, N- dihexyl acrylamide copolymer
With in acrylamide/hexadecyldimethyl benzyl ammonium allyl ammonium chloride/2- acrylamide-2-methylpro panesulfonic acid copolymer at least
It is a kind of.
Under preferable case, the hydrophobic associated polymer is APP5.The hydrophobic associated polymer is polymerize by Sichuan light Asia
The polymeric articles of object Co., Ltd production, APP5 are its trade mark.
Preferably, the surfactant is DWS, which is raw by Dalian Davis's chemical agent Co., Ltd
It produces, DWS is its trade mark.
In the present invention, the salt can be selected from NaCl, KCl, CaCl2、MgCl2·6H2O、Na2SO4、Na2CO3And NaHCO3In
At least one, preferably NaCl.
According to the present invention, the total salinity of the self-assembly system can be 3000~40000mg/L, preferably 3000~
6000mg/L。
In the present invention, the mass concentration of the hydrophobic associated polymer can be 300~1700mg/L, preferably 300~
1200mg/L, further preferably 300~1000mg/L.
The second aspect of the present invention provides the preparation method of above-mentioned self-assembly system, which includes:
1) salting liquid is prepared according to total salinity；
2) hydrophobic association polymer solution and surfactant solution are prepared by solvent of salting liquid made from step 1)；
3) salting liquid, hydrophobic association polymer solution and surfactant solution are taken respectively according to mass concentration, is being stirred
Under the conditions of, the salting liquid of acquirement and surfactant solution are sequentially added in hydrophobic association polymer solution, obtain it is described from
Assembly system.
The concentration of the hydrophobic association polymer solution and surfactant solution prepared in step 2) is respectively higher than self assembly
Concentration both in system.For example, 5000mg/L can be formulated as the concentration of hydrophobic association polymer solution, surfactant is matched
It is made as the solution of 1wt%.
The third aspect of the present invention provides above-mentioned self-assembly system and the self-assembly as made from above-mentioned preparation method
Tie up to the application in polymer displacement of reservoir oil tech.
Self-assembly system of the invention can significantly improve hydrophobic associated polymer in critical association concentration solution below
Viscosity facilitates the raising of hydrophobic associated polymer oil displacement efficiency.
The present invention is described in detail by the following examples.
In embodiment and comparative example below:
In shear rate 7.34s-1The lower viscosity with rheometer (Anton Paar company MCR301) test system.
Hydrophobic association polymer solution and surfactant solution are all made of the NaCl solution that salinity is 5000mg/L and make
It is made for solvent.
Embodiment 1-6 is used to illustrate the self-assembly system and its system of hydrophobic associated polymer and surfactant of the invention
Preparation Method.
Embodiment 1
Self-assembly system composition: hydrophobic associated polymer concentration 1200mg/L, surfactant concentration 300mg/L, polymerization
The mass concentration ratio of object and surfactant is 4: 1, and total drug concentration is 1500mg/L in solution.
24 grams of hydrophobic association polymer solution of concentration 5000mg/L are weighed, 1.0wt% surfactant solution 3 is weighed
Gram, weigh 73 grams of NaCl solution that salinity is 5000mg/L.Electric mixer revolving speed is set as 400 revs/min, in stirring bar
Part lower load weighted NaCl solution, surfactant solution are successively added in polymer solution, and after mixing evenly, test is certainly
Viscosity of the assembly system at 60 DEG C, 70 DEG C, 80 DEG C, the results are shown in Table 1.
Embodiment 2
Self-assembly system composition: hydrophobic associated polymer concentration 1000mg/L, surfactant concentration 250mg/L, polymerization
The mass concentration ratio of object and surfactant is 4: 1, and total drug concentration is 1250mg/L in solution.
20 grams of hydrophobic association polymer solution of concentration 5000mg/L are weighed, 1.0wt% surfactant solution 2.5 is weighed
Gram, weigh 77.5 grams of NaCl solution that salinity is 5000mg/L.Electric mixer revolving speed is set as 400 revs/min, is being stirred
Under the conditions of load weighted NaCl solution, surfactant solution are successively added in polymer solution, after mixing evenly, test
Self-assembly ties up to the viscosity at 60 DEG C, 70 DEG C, 80 DEG C, the results are shown in Table 1.
Embodiment 3
Self-assembly system composition: hydrophobic associated polymer concentration 700mg/L, surfactant concentration 175mg/L, polymer
Mass concentration ratio with surfactant is 4: 1, and total drug concentration is 875mg/L in solution.
14 grams of hydrophobic association polymer solution of concentration 5000mg/L are weighed, 1.0wt% surfactant solution is weighed
1.75 grams, weigh 84.25 grams of NaCl solution that salinity is 5000mg/L.Electric mixer revolving speed is set as 400 revs/min,
Load weighted NaCl solution, surfactant solution are successively added in polymer solution under agitation, stirred evenly
Afterwards, test self-assembly ties up to the viscosity at 60 DEG C, 70 DEG C, 80 DEG C, the results are shown in Table 1.
Embodiment 4
Self-assembly system composition: hydrophobic associated polymer concentration 500mg/L, surfactant concentration 125mg/L, polymer
It is 4: 1 with surfactant qualities concentration ratio, total drug concentration is 625mg/L in solution.
10 grams of hydrophobic association polymer solution of concentration 5000mg/L are weighed, 1.0wt% surfactant solution is weighed
1.25 grams, weigh 88.75 grams of NaCl solution that salinity is 5000mg/L.Electric mixer revolving speed is set as 400 revs/min,
Load weighted NaCl solution, surfactant solution are successively added in polymer solution under agitation, stirred evenly
Afterwards, test self-assembly ties up to the viscosity at 60 DEG C, 70 DEG C, 80 DEG C, the results are shown in Table 1.
Embodiment 5
Self-assembly system composition: hydrophobic associated polymer concentration 1200mg/L, surfactant concentration 100mg/L, polymerization
Object and surfactant qualities concentration ratio are 12: 1, and total drug concentration is 1300mg/L in solution.
24 grams of hydrophobic association polymer solution of concentration 5000mg/L are weighed, 1.0wt% surfactant solution 1.0 is weighed
Gram, weigh 75 grams of NaCl solution that salinity is 5000mg/L.Electric mixer revolving speed is set as 400 revs/min, in stirring bar
Part lower load weighted NaCl solution, surfactant solution are successively added in polymer solution, and after mixing evenly, test is certainly
Viscosity of the assembly system at 60 DEG C, 70 DEG C, 80 DEG C, the results are shown in Table 1.
Embodiment 6
Self-assembly system composition: hydrophobic associated polymer concentration 1200mg/L, surfactant concentration 200mg/L, polymerization
Object and surfactant qualities concentration ratio are 6: 1, and total drug concentration is 1400mg/L in solution.
24 grams of hydrophobic association polymer solution of concentration 5000mg/L are weighed, 1.0wt% surfactant solution 2.0 is weighed
Gram, weigh 74 grams of NaCl solution that salinity is 5000mg/L.Electric mixer revolving speed is set as 400 revs/min, in stirring bar
Part lower load weighted NaCl solution, surfactant solution are successively added in polymer solution, and after mixing evenly, test is certainly
Viscosity of the assembly system at 60 DEG C, 70 DEG C, 80 DEG C, the results are shown in Table 1.
Comparative example 1~6
Measurement concentration is 1500mg/L, 1250mg/L, 875mg/L, 625mg/L, 1300mg/L and 1400mg/L respectively
The viscosity of hydrophobic association polymer solution, the results are shown in Table 1.
Table 1
By the data of embodiment and comparative example it is found that self-assembly system of the invention is remarkably improved hydrophobic associated polymer
In critical association concentration solution viscosity below, and highly viscous system is conducive to improve oil recovery factor.
The embodiment of the present invention is described above, above description is exemplary, and non-exclusive, and also not
It is limited to disclosed embodiment.Without departing from the scope and spirit of illustrated embodiment, for the art
Many modifications and changes are obvious for those of ordinary skill.
Claims (10)
1. the self-assembly system of a kind of hydrophobic associated polymer and surfactant, which is characterized in that the self-assembly system includes
Hydrophobic associated polymer, surfactant, Yan Heshui, wherein the mass concentration ratio of hydrophobic associated polymer and surfactant be
3~12: 1, the surfactant is nonionic Gemini surface active agent.
2. self-assembly system according to claim 1, wherein the hydrophobic associated polymer is selected from acrylamide/2- third
Acrylamide alkyl sulfonic acids copolymer, 18 resin copolymer of acrylamide/acrylic acid, acrylamide/N- decyl/2-
Acrylamide-2-methylpro panesulfonic acid copolymer, acrylamide/n-vinyl pyrrolidone/2- methylacryoyloxyethyl-two
Methyl-dodecanoic base ammonium bromide copolymer, acrylamide/N- alkyl phenyl acrylamide copolymer, acrylamide/acrylic acid/
N, N- dihexyl acrylamide copolymer and acrylamide/hexadecyldimethyl benzyl ammonium allyl ammonium chloride/2- acrylamido -2-
At least one of methyl propane sulfonic acid copolymer.
3. self-assembly system according to claim 1, wherein the hydrophobic associated polymer is APP5.
4. self-assembly system according to claim 1, wherein the surfactant is DWS.
5. self-assembly system according to claim 1, wherein the salt is selected from NaCl, KCl, CaCl2、MgCl2·6H2O、
Na2SO4、Na2CO3And NaHCO3At least one of.
6. self-assembly system according to claim 1, wherein the total salinity of the self-assembly system be 3000~
40000mg/L。
7. self-assembly system according to claim 1, wherein the mass concentration of the hydrophobic associated polymer be 300~
1700mg/L。
8. self-assembly system according to claim 7, wherein the mass concentration of the hydrophobic associated polymer be 300~
1200mg/L。
9. the preparation method of self-assembly system described in any one of claim 1-8, which is characterized in that the preparation method packet
It includes:
1) salting liquid is prepared according to total salinity；
2) hydrophobic association polymer solution and surfactant solution are prepared by solvent of salting liquid made from step 1)；
3) salting liquid, hydrophobic association polymer solution and surfactant solution are taken respectively according to mass concentration, in stirring condition
Under, the salting liquid of acquirement and surfactant solution are sequentially added in hydrophobic association polymer solution, the self assembly is obtained
System.
10. made from self-assembly system described in any one of claim 1-8 and the preparation method as described in claim 9 certainly
Application of the assembly system in polymer displacement of reservoir oil tech.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112858580A (en) * | 2020-12-28 | 2021-05-28 | 中国石油大学(北京) | Method for determining critical association concentration of polymer based on hydrodynamic size |
| CN114605981A (en) * | 2022-04-15 | 2022-06-10 | 西南石油大学 | Hydrophobic association polymer quick solvent based on surfactant and dissolving method |
-
2018
- 2018-03-23 CN CN201810249618.XA patent/CN110295033A/en active Pending
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112858580A (en) * | 2020-12-28 | 2021-05-28 | 中国石油大学(北京) | Method for determining critical association concentration of polymer based on hydrodynamic size |
| CN112858580B (en) * | 2020-12-28 | 2022-01-18 | 中国石油大学(北京) | Method for determining critical association concentration of polymer based on hydrodynamic size |
| CN114605981A (en) * | 2022-04-15 | 2022-06-10 | 西南石油大学 | Hydrophobic association polymer quick solvent based on surfactant and dissolving method |
| CN114605981B (en) * | 2022-04-15 | 2022-08-30 | 西南石油大学 | Hydrophobic association polymer quick solvent based on surfactant and dissolving method |
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