CN109679008B - Ultrahigh molecular weight anionic polyacrylamide for oil displacement and preparation method and application thereof - Google Patents
Ultrahigh molecular weight anionic polyacrylamide for oil displacement and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an ultra-high molecular weight anionic polyacrylamide for oil displacement and a preparation method and application thereof. The preparation method comprises the following steps: introducing nitrogen into a solution containing acrylamide, sequentially adding an azo initiator, a complexing agent, a chain regulator, an oxidant and a reducing agent into the solution, and polymerizing to obtain a nonionic polyacrylamide colloid; the chain regulator comprises a main component and an auxiliary component, wherein the main component comprises sodium formate, the auxiliary component comprises sodium hypophosphite, and the mass ratio of the main component to the auxiliary component is (10-18): 1; and (3) crushing the nonionic amide colloid, and adding a hydrolytic agent for hydrolysis to obtain the ultrahigh molecular weight anionic polyacrylamide for oil displacement. The viscosity-phase relative molecular mass of the anionic polyacrylamide prepared by the method is more than 3000 ten thousand, the content of water insoluble substances is less than or equal to 0.2 percent, the anionic polyacrylamide is used as an oil displacement agent in tertiary oil recovery in an oil field, the oil displacement efficiency is higher, and the crude oil recovery rate can be improved by 18-29 percent.
Description
Technical Field
The invention relates to the technical field of ultra-high molecular weight polymers, in particular to ultra-high molecular weight anionic polyacrylamide for oil displacement and a preparation method and application thereof.
Background
Polyacrylamide (PAM) is a water-soluble high-molecular polymer, and its molecular structure has amide active groups, which can be easily grafted or cross-linked to obtain various modified substances with branched or network structures. PAM molecules can introduce various ionic groups to obtain specific performance, are widely applied to various fields of chemical industry, metallurgy, geology, coal, petroleum, papermaking, water treatment and the like, have the title of 'all-industry auxiliary agents', and particularly have the largest oil field exploitation dosage. Many oil fields at home and abroad enter a tertiary oil recovery stage along with continuous exploitation. Sufficient crude oil cannot be produced by water injection or gas injection, and the oil production cost is continuously high. The tertiary oil recovery is to inject polymer into the oil well, greatly reduce the oil-water interfacial tension near the oil layer and increase the viscosity and elasticity of the injected water, thereby reducing the oil-water flow rate ratio, expanding the macro and micro sweep coefficients of the oil layer, further displacing the water-driven residual oil, and greatly reducing the saturation of the residual oil, thereby achieving the purpose of improving the crude oil recovery ratio.
The oil displacing polymer is widely applied by anionic polyacrylamide, and has the best oil displacing effect. The oil layer environment is complex, high temperature and high salt, which has high requirements on the polymer performance. The most used polyacrylamide products for oil displacement in the market comprise ultrahigh molecular weight polyacrylamide, temperature-resistant salt-resistant monomer-containing polyacrylamide and the like. The molecular weight of the ultra-high molecular weight polyacrylamide is mainly 2500-3000 ten thousand, and the molecular weight of the ultra-high molecular weight polyacrylamide is rarely 3000-3300 ten thousand, so that molecular chain curling can occur to the polyacrylamide in saline water and high-temperature environment, the viscosity of an aqueous solution is greatly reduced, the oil displacement effect is seriously reduced, the water solubility is poor, and the use effect is influenced; the polyacrylamide containing the temperature-resistant and salt-resistant monomer has higher cost and lower molecular weight after copolymerization, can be only used in a small amount in specific occasions, and cannot be applied to the field of oil displacement in a large scale.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide novel ultra-high molecular weight anionic polyacrylamide for oil displacement, which has low cost, ultra-high molecular weight (more than 3000 ten thousand, and the preferable technical scheme can reach more than 3500 ten thousand) and good solubility, and a preparation method and application thereof, so as to solve one or more problems in the conventional anionic polyacrylamide for oil displacement.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a preparation method of ultra-high molecular weight anionic polyacrylamide for oil displacement comprises the following steps:
(1) introducing nitrogen into a solution containing acrylamide, then sequentially adding an azo initiator, a complexing agent, a chain regulator, an oxidant and a reducing agent into the solution, and polymerizing to obtain a nonionic polyacrylamide colloid; the chain regulator comprises a main component and an auxiliary component, wherein the main component comprises sodium formate, the auxiliary component comprises sodium hypophosphite, and the mass ratio of the main component to the auxiliary component is (10-18): 1;
(2) and (3) crushing the nonionic amide colloid, and adding a hydrolytic agent for hydrolysis to obtain the ultrahigh molecular weight anionic polyacrylamide for oil displacement.
2. The preparation method according to the technical scheme 1, wherein the mass ratio of the main component to the auxiliary component is (12-15): 1.
3. the preparation method according to claim 1, wherein the auxiliary component further comprises dodecyl mercaptan and/or sodium bisulfite.
4. The production method according to any one of claims 1 to 3, wherein the mass of the chain regulator is 0.0015% to 0.0032% of the mass of the solution.
5. According to the preparation method of the technical scheme 1, the mass of the chain regulator is 0.0018-0.0026% of the mass of the solution.
6. According to the preparation method of the technical scheme 1, the solution further comprises a cosolvent, wherein the cosolvent is selected from any one or more of thiourea, urea and acetamide, and accounts for 0.5-2.3% of the mass of the solution; and/or
The mass of the acrylamide accounts for 16-30% of the mass of the solution, and the mass of the acrylamide is preferably 17-23%.
7. According to the preparation method of the technical scheme 6, the mass of the cosolvent accounts for 0.8-1% of the mass of the solution.
8. According to the preparation method of the technical scheme 6, the mass of the acrylamide accounts for 17-23% of the mass of the solution.
9. According to the preparation method of the technical scheme 1, the azo initiator is selected from any one or more of azobisisobutyronitrile, azobisisovaleronitrile, azobisisobutylamidine hydrochloride and 4, 4' -azobis-4-cyanovaleric acid, and the mass of the azo initiator is 0.0015-0.0035% of that of the solution;
the complexing agent is selected from one or more of disodium ethylene diamine tetraacetate, sodium ethylene diamine tetra methylene phosphonate, ethylene diamine tetraacetic acid and substitution alkali, and the mass of the complexing agent is 0.0002-0.0008% of that of the solution;
the oxidant is selected from any one or more of dibenzoyl peroxide, ammonium persulfate, tert-butyl hydroperoxide, potassium persulfate and sodium persulfate, and the mass of the oxidant is 0.00006-0.00018% of that of the solution; and/or
The reducing agent is selected from any one or more of sodium bisulfite, sodium metabisulfite, ferrous ammonium sulfate and ferrous sulfate heptahydrate, and the mass of the reducing agent is 0.00005-0.00015% of the mass of the solution.
10. According to the preparation method of claim 9, the mass of the azo initiator is 0.002% -0.0026% of the mass of the solution.
11. According to the preparation method of claim 9, the mass of the complexing agent is 0.0003% -0.0005% of the mass of the solution.
12. According to the preparation method of claim 9, the mass of the oxidizing agent is 0.00008-0.00015% of the mass of the solution.
13. According to the preparation method of claim 9, the mass of the reducing agent is 0.00006-0.0001% of the mass of the solution.
14. According to the preparation method of the technical scheme 1, the hydrolytic agent is selected from any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, and the mass of the hydrolytic agent is 2.8-5.0% of that of the nonionic polyacrylamide colloid.
15. According to the preparation method of claim 14, the mass of the hydrolytic agent is 3.5-3.9% of the mass of the solution.
16. The preparation method according to claim 1, further comprising the following steps before introducing nitrogen into the solution containing acrylamide: and adjusting the pH of the solution containing the acrylamide to 7.2-7.5 by adopting any one or more of sulfamic acid, adipic acid and acetic acid.
17. According to the preparation method of the technical scheme 1, in the step (1), an azo initiator, a complexing agent, a chain regulator, an oxidant and a reducing agent are sequentially added at 1-3 ℃;
in the step (1), introducing nitrogen for 40-60 min;
in the step (1), the polymerization time is 3-6 h; and/or
In the step (2), the hydrolysis is carried out at 80-90 ℃ for 3-5 h.
18. An ultra-high molecular weight anionic polyacrylamide for oil displacement is prepared by the preparation method of any one of technical schemes 1 to 17, and preferably, the anionic polyacrylamide has the following properties:
the mass of the viscous phase relative molecule is 3900-4100 ten thousand and/or the content of water-insoluble substances is less than or equal to 0.2 percent.
19. The application of the ultra-high molecular weight anionic polyacrylamide for oil displacement as an oil displacement agent in tertiary oil recovery in an oil field in the technical scheme 18.
Advantageous effects
The technical scheme of the invention has the following advantages:
the method has the advantages of stable preparation process, short reaction time, low cost and high production efficiency, and is suitable for industrial production; the novel ultra-high molecular weight anionic polyacrylamide prepared by the invention has the advantages of low monomer content, good water solubility and ultra-high molecular weight, and the molecular weight of the novel ultra-high molecular weight anionic polyacrylamide exceeds the molecular weight of the conventional ultra-high molecular weight anionic polyacrylamide product for oil displacement in the market, namely 700-1000 ten thousand.
Compared with other types of ultra-high molecular weight anionic polyacrylamide for oil displacement, the novel ultra-high molecular weight anionic polyacrylamide provided by the invention is used as an oil displacement agent in tertiary oil recovery of an oil field, so that the oil displacement efficiency and the crude oil recovery ratio can be effectively improved by 18-29%.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a preparation method of ultra-high molecular weight anionic polyacrylamide for oil displacement, which comprises the following steps:
(1) introducing nitrogen into a solution containing acrylamide, then sequentially adding an azo initiator, a complexing agent, a chain regulator, an oxidant and a reducing agent into the solution, and polymerizing to obtain a nonionic polyacrylamide colloid; the chain regulator comprises a main component and an auxiliary component, wherein the main component comprises sodium formate, the auxiliary component comprises sodium hypophosphite, and the mass ratio of the main component to the auxiliary component is (10-18): 1, more preferably (12-15): 1;
(2) and (3) crushing the nonionic amide colloid, and adding a hydrolytic agent for hydrolysis to obtain the ultrahigh molecular weight anionic polyacrylamide for oil displacement.
In the preparation method provided by the invention, the main component and the auxiliary component in the chain regulator are mixed according to a specific proportion for use, the sodium formate can greatly improve the molecular weight of polyacrylamide, and the molecular weight is obviously higher than that of polyacrylamide synthesized by other chain regulators, but the dissolution process of the polyacrylamide prepared by only adopting the sodium formate as the chain regulator is slower, and the water solubility is poorer. After the sodium hypophosphite is added, the prepared polyacrylamide has short dissolving time (less than 1 h). Therefore, the invention adopts sodium formate as a main regulator and sodium hypophosphite as an auxiliary chain regulator, and the molecular weight of the obtained polyacrylamide is slightly lower than that of the polyacrylamide obtained by only using sodium formate, but the water solubility is obviously better, and the solubility of the polyacrylamide is slightly lower than that of the polyacrylamide obtained by only using sodium hypophosphite, but the molecular weight is obviously higher.
In some embodiments, the adjunct ingredient further comprises dodecyl mercaptan and/or sodium bisulfite.
In some embodiments, the mass of the chain regulator is 0.0015% to 0.0032% of the mass of the solution, for example, can be 0.0015%, 0.0020%, 0.0025%, 0.0030%, 0.0032%, preferably 0.0018% to 0.0026%.
In some embodiments, the solution further comprises a cosolvent selected from any one or more of thiourea, urea and acetamide, the cosolvent accounts for 0.5-2.3% of the mass of the solution, for example, 0.5%, 1.0%, 1.5%, 2.0%, 2.3%, and preferably 0.8-1%.
In some embodiments, the mass of the acrylamide is 16 to 30% of the mass of the solution, for example, 16%, 17%, 18%, 19%, 20%, 25%, 30%, preferably 17 to 23%.
In some embodiments, the azo initiator is selected from any one or more of azobisisobutyronitrile, azobisisovaleronitrile, azobisisobutylamidine hydrochloride, and 4, 4' -azobis 4-cyanovaleric acid in an amount of 0.0015% to 0.0035% by weight of the solution, for example, 0.0015%, 0.0020%, 0.0025%, 0.0030%, 0.0035%, and preferably 0.002% to 0.0026%.
In some embodiments, the complexing agent is selected from any one or more of disodium ethylenediaminetetraacetate, sodium ethylenediaminetetramethylenediphosphonate, ethylenediaminetetraacetic acid, and a surrogate base, and the mass is 0.0002% to 0.0008% of the mass of the solution, for example, 0.0002%, 0.0003%, 0.0004%, 0.0005%, 0.0006%, 0.0007%, 0.0008%, and preferably 0.0003% to 0.0005%.
In some embodiments, the oxidizing agent is selected from any one or more of dibenzoyl peroxide, ammonium persulfate, tert-butyl hydroperoxide, potassium persulfate, and sodium persulfate, and the mass is 0.00006% to 0.00018% of the mass of the solution, for example, 0.00006%, 0.00007%, 0.00008%, 0.00009%, 0.00010%, 0.00011%, 0.00012%, 0.00015%, 0.00016%, 0.00018%, and preferably 0.00008% to 0.00015%.
In some embodiments, the reducing agent is selected from any one or more of sodium bisulfite, sodium metabisulfite, ferrous ammonium sulfate, ferrous sulfate heptahydrate, in a mass of 0.00005% to 0.00015% of the mass of the solution, for example, 0.00005%, 0.00006%, 0.00007%, 0.00008%, 0.00009%, 0.00010%, 0.00011%, 0.00012%, 0.00015%, preferably 0.00006% to 0.0001%.
In some embodiments, the hydrolysis agent is selected from any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate, and the mass is 2.8% to 5.0% of the mass of the nonionic polyacrylamide colloid, for example, may be 2.8%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, and preferably 3.5% to 3.9%.
In some embodiments, the method further comprises the following steps before introducing nitrogen into the solution containing acrylamide: and adjusting the pH of the solution containing the acrylamide to 7.2-7.5 by adopting any one or more of sulfamic acid, adipic acid and acetic acid.
In some embodiments, in the step (1), an azo initiator, a complexing agent, a chain regulator, an oxidant and a reducing agent are sequentially added at 1-3 ℃;
in the step (1), introducing nitrogen for 40-60 min;
in the step (1), the polymerization time is 3-6 h; and/or
In the step (2), the hydrolysis is carried out at 80-90 ℃ for 3-5 h.
The invention also provides the ultra-high molecular weight anionic polyacrylamide for oil displacement, the anionic polyacrylamide is prepared by the preparation method provided by the invention, and in a preferred technical scheme, the anionic polyacrylamide has the following properties:
the mass of the viscous phase relative molecule is 3900-4100 ten thousand and/or the content of water-insoluble substances is less than or equal to 0.2 percent.
The invention provides an application of the ultra-high molecular weight anionic polyacrylamide for oil displacement as an oil displacement agent in tertiary oil recovery of an oil field.
The following are examples of the present invention.
Example 1
(1) Fully stirring and uniformly mixing acrylamide and urea (urea is taken as a cosolvent) by using deionized water to obtain a mixed solution with the weight percentage concentration of total monomer acrylamide of 20%, wherein the mass percentage concentration of the urea in the mixed solution is 0.8%, adjusting the pH of the mixed solution to 7.2 by using sulfamic acid, and then reducing the temperature of the mixed solution to 1 ℃ by using refrigeration equipment.
(2) When the temperature of the mixed solution is reduced to 1 ℃, transferring the mixed solution into an adiabatic reaction kettle, inserting a digital thermometer, introducing high-purity nitrogen for 40min to remove oxygen in the mixed solution, then sequentially adding azodiisobutyl amidine hydrochloride accounting for 0.002% of the mixed solution by mass, disodium ethylenediamine tetraacetate accounting for 0.0003% of the mixed solution by mass, sodium formate accounting for 0.0018% of the mixed solution by mass, sodium hypophosphite accounting for 0.00015% of the mixed solution by mass, tert-butyl hydroperoxide accounting for 0.00008% of the mixed solution by mass and ferrous sulfate heptahydrate accounting for 0.00006% of the mixed solution by mass into the mixed solution, stopping nitrogen filling when the viscosity of the mixed solution is increased and nitrogen bubbling, sealing the adiabatic reaction kettle, observing and recording the temperature change, and continuously reacting for 3h to obtain the colloidal nonionic polyacrylamide colloid.
(3) And crushing the obtained colloidal nonionic polyacrylamide colloid into small blocks with the size of 3-5 mm, adding sodium hydroxide accounting for 3.5% of the mass of the colloid to be hydrolyzed, fully mixing, putting into a constant-temperature drying oven, and keeping the temperature at 80 ℃ for 3 hours to obtain the novel ultra-high molecular weight anionic polyacrylamide colloid.
(4) The novel ultra-high molecular weight anionic polyacrylamide gel for oil displacement is prepared into dry powder by the steps of granulation, drying and crushing in sequence.
Examples 2 to 7 were prepared in substantially the same manner as in example 1 except that the differences were as shown in Table 1.
The viscosity phase of the products obtained in examples 1 to 7 was determined with respect to the molecular mass and the insoluble content, and the test method was as follows:
(1) determination of molecular mass by viscosity phase: the flow-out times of the NaCl solution and the 0.1% (mass concentration: 0.1%) sample solution measured by Ubbelohde viscometer were respectively represented as t0And t1The molecular mass is converted into viscosity-average relative molecular mass according to the following formula:
wherein A represents the solid content of the sample, m represents the mass of the sample,
-average molecular weight, η sp ═ η r-1, η r ═ t1/t0，[η]-intrinsic viscosity.
(2) Determination of insoluble matter content: 2.0g of the sample was weighed to the nearest 0.0002g and slowly added to a stirred beaker of 1998.0g of deionized water, maintaining the vortex depth at about 2cm until dissolution was complete (time about 1 hour). Filtering the solution, naturally washing with tap water until insoluble substances are visible, draining the liquid solution on the stainless steel mesh as far as possible, and weighing the mass of the stainless steel mesh and the insoluble substance colloid.
Wherein w 1-insoluble matter content in mass fraction, m0Total mass of sample (total mass of deionized water and dry powder), m1Mass of stainless steel net, m2The total mass of stainless steel mesh and insolubles.
(3) And (3) determination of crude oil recovery: the crude oil recovery ratio is the percentage of the petroleum reserves which can be extracted from the original geological reserves of the oil reservoir under the modern engineering technical conditions within a certain economic limit, and the calculation formula is as follows:
wherein the A-crude oil recovery is in mass fraction, V0Reservoir original geological storage, V1Crude oil production.
The test results are shown in Table 1.
Example 4 was prepared using only sodium formate as the chain regulator. From the test results, it can be seen that the product obtained in example 4 has a slightly higher viscosity-average relative molecular mass than the product of example 1 at the same amount of the chain regulator as in example 1, but has poor solubility and a high content of insoluble materials (up to 1.61%, 16 times that of example 1), and therefore the oil recovery ratio is inferior to that of example 1.
Example 5 was prepared using only sodium hypophosphite as the chain regulator. From the test results, it can be seen that the product obtained in example 5 has better solubility, but the viscosity relative molecular mass is far inferior to that of the product obtained in example 1, and the viscosity relative molecular mass is less than 3000 ten thousand, and the influence on the crude oil recovery is also large under the condition that the amount of the chain regulator is the same as that of the product obtained in example 1.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (16)
1. A preparation method of ultra-high molecular weight anionic polyacrylamide for oil displacement is characterized by comprising the following steps:
(1) introducing nitrogen into a solution containing acrylamide, then sequentially adding an azo initiator, a complexing agent, a chain regulator, an oxidant and a reducing agent into the solution, and polymerizing to obtain a nonionic polyacrylamide colloid; the chain regulator comprises a main component and an auxiliary component, wherein the main component comprises sodium formate, the auxiliary component comprises sodium hypophosphite, and the mass ratio of the main component to the auxiliary component is (10-18): 1;
(2) and (3) crushing the non-ionic polyacrylamide colloid, and adding a hydrolytic agent for hydrolysis to obtain the ultra-high molecular weight anionic polyacrylamide for oil displacement.
2. The method according to claim 1, wherein the auxiliary component further comprises dodecyl mercaptan and/or sodium bisulfite.
3. The production method according to claim 1, wherein the mass ratio of the main component to the auxiliary component is (12 to 15): 1.
4. the production method according to claim 1 or 2, wherein the mass of the chain regulator is 0.0015% to 0.0032% of the mass of the solution.
5. The method according to claim 4, wherein the mass of the chain regulator is 0.0018 to 0.0026% of the mass of the solution.
6. The preparation method of claim 1, wherein the solution further comprises a cosolvent selected from any one or more of thiourea, urea and acetamide, and the mass of the cosolvent accounts for 0.5-2.3% of the mass of the solution; and/or
The mass of the acrylamide accounts for 16-30% of the mass of the solution.
7. The preparation method according to claim 6, wherein the mass of the cosolvent accounts for 0.8-1% of the mass of the solution;
the mass of the acrylamide accounts for 17-23% of the mass of the solution.
8. The preparation method according to claim 1, wherein the azo initiator is selected from one or more of azobisisobutyronitrile, azobisisovaleronitrile, azobisisobutylamidine hydrochloride and 4, 4' -azobis 4-cyanovaleric acid, and the mass of the azo initiator is 0.0015-0.0035% of that of the solution;
the complexing agent is selected from one or more of disodium ethylene diamine tetraacetate, sodium ethylene diamine tetra methylene phosphonate, ethylene diamine tetraacetic acid and substitution alkali, and the mass of the complexing agent is 0.0002-0.0008% of that of the solution; the oxidant is selected from any one or more of dibenzoyl peroxide, ammonium persulfate, tert-butyl hydroperoxide, potassium persulfate and sodium persulfate, and the mass of the oxidant is 0.00006-0.00018% of that of the solution; and/or
The reducing agent is selected from any one or more of sodium bisulfite, sodium metabisulfite, ferrous ammonium sulfate and ferrous sulfate heptahydrate, and the mass of the reducing agent is 0.00005-0.00015% of the mass of the solution.
9. The preparation method according to claim 8, wherein the mass of the azo initiator is 0.002-0.0026% of the mass of the solution;
the mass of the complexing agent is 0.0003% -0.0005% of the mass of the solution;
the mass of the oxidant is 0.00008-0.00015% of the mass of the solution;
the mass of the reducing agent is 0.00006-0.0001% of the mass of the solution.
10. The preparation method according to claim 1, wherein the hydrolytic agent is selected from any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, and the mass of the hydrolytic agent is 2.8-5.0% of the mass of the nonionic polyacrylamide colloid.
11. The method according to claim 10, wherein the mass of the hydrolysis agent is 3.5 to 3.9% of the mass of the nonionic polyacrylamide gel.
12. The method according to claim 1, wherein the step of introducing nitrogen into the solution containing acrylamide further comprises: and adjusting the pH of the solution containing the acrylamide to 7.2-7.5 by adopting any one or more of sulfamic acid, adipic acid and acetic acid.
13. The preparation method according to claim 1, wherein in the step (1), an azo initiator, a complexing agent, a chain regulator, an oxidizing agent and a reducing agent are sequentially added at 1-3 ℃;
in the step (1), introducing nitrogen for 40-60 min;
in the step (1), the polymerization time is 3-6 h; and/or
In the step (2), the hydrolysis is carried out at 80-90 ℃ for 3-5 h.
14. An ultra-high molecular weight anionic polyacrylamide for oil displacement, which is characterized by being prepared by the preparation method of any one of claims 1 to 13.
15. The ultra-high molecular weight anionic polyacrylamide for flooding according to claim 14, wherein the anionic polyacrylamide has the following properties:
the mass of the viscous phase relative molecule is 3900-4100 ten thousand and/or the content of water-insoluble substances is less than or equal to 0.2 percent.
16. The use of the ultra-high molecular weight anionic polyacrylamide for flooding according to claim 14 or 15 as an oil displacement agent in tertiary oil recovery in oil fields.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6753388B1 (en) * | 2000-06-29 | 2004-06-22 | Nalco Company | Structurally-modified polymer flocculants |
| CN102372807A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Preparation method of heat-resistance and salt-tolerance anionic polyacrylamide for oil displacement |
| CN103242483A (en) * | 2013-05-20 | 2013-08-14 | 安徽天润化学工业股份有限公司 | Preparation method of instant polyacrylamide |
| CN103509146A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method of ultra-high molecular weight anionic polyacrylamide |
| CN105111342A (en) * | 2015-09-18 | 2015-12-02 | 河南省科学院高新技术研究中心 | High-concentration acrylamide water solution polymerization method |
-
2019
- 2019-01-14 CN CN201910032124.0A patent/CN109679008B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6753388B1 (en) * | 2000-06-29 | 2004-06-22 | Nalco Company | Structurally-modified polymer flocculants |
| CN102372807A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Preparation method of heat-resistance and salt-tolerance anionic polyacrylamide for oil displacement |
| CN103509146A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method of ultra-high molecular weight anionic polyacrylamide |
| CN103242483A (en) * | 2013-05-20 | 2013-08-14 | 安徽天润化学工业股份有限公司 | Preparation method of instant polyacrylamide |
| CN105111342A (en) * | 2015-09-18 | 2015-12-02 | 河南省科学院高新技术研究中心 | High-concentration acrylamide water solution polymerization method |
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