CN104371681A - AA/AM/SSS underground cross-linked polymer gel plugging agent and preparation method thereof - Google Patents
AA/AM/SSS underground cross-linked polymer gel plugging agent and preparation method thereof Download PDFInfo
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- CN104371681A CN104371681A CN201410550390.XA CN201410550390A CN104371681A CN 104371681 A CN104371681 A CN 104371681A CN 201410550390 A CN201410550390 A CN 201410550390A CN 104371681 A CN104371681 A CN 104371681A
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- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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Abstract
The invention discloses an AA/AM/SSS underground cross-linked polymer gel plugging agent and a preparation method thereof, belonging to the technical field of oilfield chemistry. The gel plugging agent is a polymer gel system synthesized by taking acrylic acid (AA) and acrylamide (AM) as monomers, sodium styrenesulfonate (SSS) as a functional monomer, and ammonium persulfate and sodium hydrogen sulfite as initiators as well as urotropine (hexamethylenetetramine) as a cross-linking agent; the synthesis condition is that the gel plugging agent comprises the following components in percentage by weight: 8%-12% of the monomers, 0.2%-0.6% of the functional monomer, 0.04%-0.06% of the initiators, 0.6%-1.0% of the cross-linking agent and the balance of water. The gel system is good in heat resistance and salt tolerance, high in plugging rate and good in profile improvement rate. The gel plugging agent can be used for regulating the water injection profile of a water injection well, so that the injected water wave and volume are expanded, and the recovery rate is enhanced.
Description
Technical field
The present invention relates to technical field of oilfield chemistry, particularly underground crosslinked polymer gel plugging agent of a kind of AA/AM/SSS and preparation method thereof.
Background technology
China's land oil more than 80% is by waterflooding.An oil reservoir is often made up of multiple oil reservoir, and due to the difference of each reservoir permeability, injecting water will advance by leaps and bounds along most permeable zone, cause the too early water logging of oil well.Therefore for the oil field of waterflooding, well water is a common problem, understand fully water yield formation in time and produce water direction, take reasonable effective measures and profile control and water plugging measure to be very important (to build, Li monarch. chemical profile control Study on water plugging present situation [J]. grand celebration petroleum geology and exploitation, 2006 (3): 85 ~ 88.).
In water drive and polymer flooding process, because the nonuniformity on stratum is comparatively serious, makes injection water and polymers soln along the uneven propelling of most permeable zone and most permeable zone district, cause middle low permeability layer to involve degree low, oil displacement efficiency is poor, has had a strong impact on the development effectiveness of water drive or polymer flooding.Fundamentally to address this problem, the way of profile control and water plugging just must be adopted to improve intake profile.
In recent years, deep profile controlling chemical agent obtains large development, and polymer gel class is the class profile-controlling and plugging agent that external use is maximum, most widely used at present.But can there is shearing action by the impact of several factors in the process that the polymers soln of polymer gel system injects in underground, make polymer solution viscosity significantly decline, cause the bad stability of system, thus affect the profile control effect of polymer gel.And the stability of polymer gel under high temperature and high salt oil deposit is very poor, it is the difficult problem that profile control technique faces now.
In order to overcome this shortcoming of polymer gel profile control agent, now proposing underground crosslinked mode and carrying out profile control.Monomer is underground crosslinked is that monomer is injected underground together with linking agent and initiator etc., carries out the mode of profile control at underground formation gel.And existing oil field is in the underground condition of high temperature and high salt, the gel of synthesis is needed to have good temperature resistant antisalt performance.Therefore, the molecular structure for polyacrylamide gel improves, from the over-all properties improving polymer gel in all directions.
Summary of the invention
The object of the invention is: for controlling the gelation time of gelling system, improving gel-strength, improving temperature resistant antisalt performance, expand swept volume, underground crosslinked polymer gel plugging agent of a kind of AA/AM/SSS and preparation method thereof is provided.
The technical scheme that the present invention takes for its technical problem of solution is:
One, a kind of feed composition mass percent of underground crosslinked polymer gel plugging agent is:
Monomer, 8 ~ 12%;
Function monomer, 0.2 ~ 0.6%;
Initiator, 0.04 ~ 0.06%;
Linking agent, 0.6 ~ 1.0%;
PH adjusting agent, all the other are water.
Two, a kind of preparation method of underground crosslinked polymer gel plugging agent
Monomeric acrylic 1.6 ~ 2.4g, acrylamide 6.4 ~ 9.6g are added to the water, then add 0.2 ~ 0.6g function monomer Sodium styrene sulfonate, be stirred to evenly; Treat that monomer and function monomer add sodium hydroxide or acrylic acid solution and regulate pH to be 6 after all dissolving; By the solution regulated, be placed in 55 DEG C of thermostat water baths, add 0.04 ~ 0.06g redox initiator, then stirring reaction; The above-mentioned solution be stirred is added 0.6 ~ 1.0g linking agent, and after abundant stirring reaction, 40 ~ 60h obtains underground crosslinked Gelling Water shutoff Agent.
The invention has the beneficial effects as follows: the underground crosslinked Gelling Water shutoff Agent that the present invention uses is monomer by vinylformic acid (AA), acrylamide (AM), Sodium styrene sulfonate (SSS), with sodium bisulfite and ammonium persulphate for initiator, urotropine (six methyne four ammoniums) for linking agent formulated, the Gelling Water shutoff Agent gelation time of formation is controlled; Gel-strength is high, is conducive to heavy dose of injection and deep profile controlling; Sealing ratiod and profile improvement rate high; There is certain temperature resistant antisalt performance.This plugging agent can be used for adjusting profile-log of water injection, improves water flooding effect.
Accompanying drawing explanation
Fig. 1 is the synthesis infrared spectrogram of underground crosslinked Gelling Water shutoff Agent;
Embodiment
Below by embodiment, the present invention is further described.
The synthesis of embodiment 1:AA/AM/SSS polymer gel
Monomeric acrylic 1.6 ~ 2.4g, acrylamide 6.4 ~ 9.6g are added to the water, then add 0.2 ~ 0.6g function monomer Sodium styrene sulfonate, be stirred to evenly; Treat that monomer and function monomer add sodium hydroxide or acrylic acid solution and regulate pH to be 6 after all dissolving; By the solution regulated, be placed in 55 DEG C of thermostat water baths, add 0.04 ~ 0.06g redox initiator, then stirring reaction; The above-mentioned solution be stirred is added 0.6 ~ 1.0g linking agent, obtained underground crosslinked Gelling Water shutoff Agent after abundant stirring reaction 40 ~ 60h.And the gelation time recorded at set intervals in wide-necked bottle and gel-strength (survey method with bottle and judge gelling strength).
The sign of embodiment 2:AA/AM/SSS polymer gel
By the polymer gel ethyl alcohol purification of synthesis, oven dry, pulverizing, gained pressed powder adopts KBr pressed disc method to carry out infrared spectrum test analysis on WQF-520 type Fourier transformation infrared spectrometer, the infrared spectrogram of oligomer gel as shown in Figure 1: in amide group, the stretching vibration absorption peak of N-H is positioned at 3593.3cm
-1; In amide group, the scissoring vibration absorption peak of N-H is positioned at 3171.8cm
-1;-CH
2stretching vibration absorption peak is positioned at 2932cm
-1; In alkyl carboxylic acid, the stretching vibration absorption peak of C=O is positioned at 1699cm
-1; The absorption peak of the feature of carboxylic acid ion is positioned at 1561.1cm
-1; In carboxylate radical, the charateristic avsorption band of C-O is positioned at 1319.3cm
-1; In sulfonic acid group, the symmetrical stretching vibration absorption peak of S=O lays respectively at 1181.4cm
-1and 1043.5cm
-1; In sulfonic acid group, the stretching vibration absorption peak of S-O is positioned at 629.7cm
-1, prove to have synthesized target product.
The Evaluation of Thermal Stability of embodiment 3:AA/AM/SSS Gelling Water shutoff Agent
According to preparing underground crosslinked Gelling Water shutoff Agent 3 parts in embodiment 1, treat its complete plastic after 60h and label of weighing.The gel of formation is placed in the aging 30d of baking oven of 60 DEG C, and claims the quality of gel in a wide-necked bottle at set intervals.And calculating its dehydration rate, experimental data is as shown in table 1, illustrates that the polymer gel formed has good thermostability.
Table 1: the dehydration rate analysis of gel at 60 DEG C
The Evaluation of Salt Tolerance of embodiment 4:AA/AM/SSS polymer gel
Prepare underground crosslinked Gelling Water shutoff Agent with the simulated formation water of different salinity respectively according to embodiment 1, observe and record gelation time and the gelling strength of each sample.Experimental data is as shown in table 2, even if result shows that compared with in the simulated formation water of high salinity, the polymer gel formed still has good intensity.
The gelation time of solution and intensity under the different salinity condition of table 2
The seal-off effect evaluation of embodiment 5:AA/AM/SSS polymer gel
Fill fill out sand tube with the quartz sand of different meshes, when rate of water injection is 1.0ml/min, measure original permeability K
1, then to the non-gelling solution of the fill out sand tube injection 0.3PV of different rate of permeation, seal fill out sand tube and import and export, and fill out sand tube is placed on the solidifying 60h of time in 55 DEG C of baking ovens; Afterwards to measure the rate of permeation K of rock core after shutoff under the waterflood injection rate of 1.0ml/min
2, calculate the sealing ratiod of Gelling Plugging Agent, experimental data is as shown in table 3, and result shows: in single fill out sand tube, the lower sealing ratiod of rate of permeation and breakthrough pressure higher; The polymer gel of preparation is in fill out sand tube after plastic, and following injected water pressure significantly raises.
The sealing ratiod of fill out sand tube under the different rate of permeation of table 3
The profile improvement rate evaluation of embodiment 4:AA/AM/SSS polymer gel
Fill and present the one dimension sand-packed model of low permeability and high permeability respectively with the quartz sand of different meshes, measure rate of permeation and the porosity of two sand-filling tube models with the rate of water injection of 1.0ml/min respectively; By two fill out sand tube parallel connections, measure fractional flow.Inject 0.3PV polymer gel profile control agent with the speed of 1.0ml/min again, at 55 DEG C, wait solidifying 60h, guarantee to form gel.Carry out sequent water flooding after plastic, measure the fractional flow of each fill out sand tube, calculate its profile improvement rate.The profile improvement rate of different rate of permeation fill out sand tube is as shown in table 4.Can be obtained by data in table, in fill out sand tube in parallel, system preferentially enters the high fill out sand tube of rate of permeation, when carrying out sequent water flooding after solution plastic, the fill out sand tube fractional flow that rate of permeation is high obviously reduces, illustrate that the fill out sand tube of polymer gel to different rate of permeation has selectively blocking off ability, preferentially can enter most permeable zone.Further, there is good section in certain differential scope and improve ability.
Profile improvement rate under the different rate of permeation fill out sand tube combination of table 4
Claims (4)
1. underground crosslinked polymer gel plugging agent of AA/AM/SSS and preparation method thereof, it is characterized in that, each component percentages is:
Monomer, 8 ~ 12%;
Function monomer, 0.2 ~ 0.6%;
Initiator, 0.04 ~ 0.06%;
Linking agent, 0.6 ~ 1.0%;
PH adjusting agent, all the other are water.
2. underground crosslinked polymer gel plugging agent as claimed in claim 1, it is characterized in that, described monomeric acrylic (AA) is 1.6 ~ 2.4%, acrylamide (AM) is 6.4 ~ 9.6%, function monomer is Sodium styrene sulfonate (SSS), pH adjusting agent is sodium hydroxide or vinylformic acid, initiator is redox initiator sodium bisulfite-ammonium persulphate, and linking agent is urotropine (hexamethylenetetramine).
3. a underground crosslinked polymer gel plugging agent, is characterized in that, described synthetic method comprises;
Monomeric acrylic 1.6 ~ 2.4g, acrylamide 6.4 ~ 9.6g are added to the water, then add 0.2 ~ 0.6g function monomer Sodium styrene sulfonate, be stirred to evenly;
Treat that monomer and function monomer add sodium hydroxide or acrylic acid solution and regulate pH to be 6 after all dissolving;
By the solution regulated, be placed in 55 DEG C of thermostat water baths, add 0.04 ~ 0.06g redox initiator, then stirring reaction;
The above-mentioned solution be stirred is added 0.6 ~ 1.0g linking agent, obtained underground crosslinked polymer gel plugging agent after abundant stirring reaction 40 ~ 60h.
4., as underground crosslinked polymer gel plugging agent as described in arbitrary in claims 1 to 3 and preparation method thereof, it is characterized in that, this gelling system heat and salt resistance is good; Sealing ratiod is high; Profile improvement rate is good.This plugging agent can be used for adjusting profile-log of water injection, expands and injects water swept volume, improves water flooding effect.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273133A (en) * | 2015-10-27 | 2016-01-27 | 中国石油大学(北京) | Efficient selective water plugging agent for oil fields and preparation method thereof |
| CN105820804A (en) * | 2016-04-11 | 2016-08-03 | 中国石油天然气股份有限公司 | Hypersalinity-resistant oil reservoir deep liquid flow diversion chemical agent and preparation method and application thereof |
| CN106675540A (en) * | 2016-11-21 | 2017-05-17 | 山东诺尔生物科技有限公司 | Temperature-resistant salt-resistant profile control plugging agent and preparation method thereof |
| CN108441196A (en) * | 2018-02-23 | 2018-08-24 | 中国石油化工股份有限公司江汉油田分公司石油工程技术研究院 | One kind is for low temperature, fracture formation underground synthesized gel rubber profile control agent and its preparation method and application |
| CN108570122A (en) * | 2018-04-09 | 2018-09-25 | 中国石油化工股份有限公司 | Caves oil reservoir is from spread chemical clapboard composition and its method for implanting |
| CN108643881A (en) * | 2018-04-27 | 2018-10-12 | 中国石油大学(华东) | A kind of control bottom water rising chemical clapboard and the preparation method and application thereof |
| CN116554846A (en) * | 2023-01-02 | 2023-08-08 | 西南石油大学 | Gel plugging agent suitable for hypotonic ultra-hypotonic fractured reservoir and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273133A (en) * | 2015-10-27 | 2016-01-27 | 中国石油大学(北京) | Efficient selective water plugging agent for oil fields and preparation method thereof |
| CN105820804A (en) * | 2016-04-11 | 2016-08-03 | 中国石油天然气股份有限公司 | Hypersalinity-resistant oil reservoir deep liquid flow diversion chemical agent and preparation method and application thereof |
| CN105820804B (en) * | 2016-04-11 | 2018-09-04 | 中国石油天然气股份有限公司 | Hypersalinity-resistant oil reservoir deep liquid flow diversion chemical agent and preparation method and application thereof |
| CN106675540A (en) * | 2016-11-21 | 2017-05-17 | 山东诺尔生物科技有限公司 | Temperature-resistant salt-resistant profile control plugging agent and preparation method thereof |
| CN108441196A (en) * | 2018-02-23 | 2018-08-24 | 中国石油化工股份有限公司江汉油田分公司石油工程技术研究院 | One kind is for low temperature, fracture formation underground synthesized gel rubber profile control agent and its preparation method and application |
| CN108570122A (en) * | 2018-04-09 | 2018-09-25 | 中国石油化工股份有限公司 | Caves oil reservoir is from spread chemical clapboard composition and its method for implanting |
| CN108570122B (en) * | 2018-04-09 | 2020-06-16 | 中国石油化工股份有限公司 | Self-spreading chemical partition plate composition for karst cave oil reservoir and injection method thereof |
| CN108643881A (en) * | 2018-04-27 | 2018-10-12 | 中国石油大学(华东) | A kind of control bottom water rising chemical clapboard and the preparation method and application thereof |
| CN108643881B (en) * | 2018-04-27 | 2020-04-14 | 中国石油大学(华东) | Chemical partition plate for controlling bottom water to rise and preparation method and application thereof |
| CN116554846A (en) * | 2023-01-02 | 2023-08-08 | 西南石油大学 | Gel plugging agent suitable for hypotonic ultra-hypotonic fractured reservoir and preparation method thereof |
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