CN112552449A - Preparation method and application of pH-sensitive water-swelling resin - Google Patents
Preparation method and application of pH-sensitive water-swelling resin Download PDFInfo
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- CN112552449A CN112552449A CN202011400826.9A CN202011400826A CN112552449A CN 112552449 A CN112552449 A CN 112552449A CN 202011400826 A CN202011400826 A CN 202011400826A CN 112552449 A CN112552449 A CN 112552449A
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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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- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
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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
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/426—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for plugging
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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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
Abstract
The invention belongs to the field of preparation of absorption expansion resin, and particularly relates to a preparation method and application of pH-sensitive water absorption expansion resin. The preparation method of the pH-sensitive water-swelling resin comprises the following steps: carrying out copolymerization reaction on acrylamide, acrylic acid, methacryloyloxyethyl trimethyl ammonium salt and a crosslinking agent N, N-methylene bisacrylamide in a solvent under the condition that the pH value is 5-7; the mol ratio of acrylamide to methacryloyloxyethyl trimethyl ammonium salt is (1-2) to (1-2), the mass of acrylic acid accounts for 18-22% of the mass of acrylamide, and the mass of the cross-linking agent accounts for 1-6% of the total mass of acrylamide, acrylic acid and methacryloyloxyethyl trimethyl ammonium salt monomers. According to the preparation method of the pH-sensitive water-swellable resin, the comonomer and the cross-linking agent are selected, so that the resin has pH sensitivity and strong water retention capacity and can endure complex formation pressure environment.
Description
Technical Field
The invention belongs to the field of preparation of absorption expansion resin, and particularly relates to a preparation method and application of pH-sensitive water absorption expansion resin.
Background
With the deep development of oil and gas exploitation, the severe geological conditions and the disordered pressure layer of the complex stratum can damage the sealed annular cement sheath, so that a large number of microcracks are generated on the rigid cement sheath, the microcracks gradually extend and communicate with each other along with the time, and finally the integrity and the packing property of the cement sheath are damaged.
After the well cementation cement sheath is damaged, the conventional remedial measures mainly comprise: and (5) supplementary cement injection, cement squeezing injection or secondary well cementation. However, the remedial measures also face the difficulties that the squeeze position is difficult to determine, the waiting time is difficult to adjust, the well must be shut down and the production is stopped, and the like, so that the cost is extremely high, the success rate is very limited, and the remedial measures have great significance on completing the repair work of the well cementation cement sheath under the premise of ensuring the success rate and not influencing the exploitation progress and strictly controlling the cost.
Based on the technical scheme, the research on the new technology for solving the micro-annular space of the cement sheath of the oil-gas well, namely the research on the self-repairing cement, becomes a research hotspot of the novel well cementing fluid in recent years. The self-repairing technology of oil well cement aims to enable a cement system to have a self-repairing function so as to provide long-term interlayer packing. The most advantages are as follows: the long-term durability of the cement sheath is improved without interrupting the normal production of the oil and gas well.
One of the ideas of the self-repairing cement is to add pH sensitive water-absorbing expansion resin into cement slurry, so that the resin only absorbs a small amount of water in the cement slurry, and all performances of the well cementation cement slurry are ensured to basically meet the requirements. When the hardened set cement generates micro cracks inside, the resin is exposed on the surface of the micro cracks, the formation water is neutral or weakly acidic, and the resin exposed by the micro cracks absorbs water and expands after meeting formation water flow to plug the micro cracks, so that the self-repairing of the set cement micro cracks is realized. The material developed by the principle can effectively prevent the formation fluid from channeling and ensure the long-term operation of the well cementation cement sheath.
At present, pH-sensitive hydrogel related to Chinese patent application with publication number CN101074286A and super absorbent resin related to publication number CN102311517A have higher water absorption expansion effect in alkalescent environment, are not consistent with cement slurry and stratum water environment, and cannot be applied to oil well cement to block micro cracks.
Disclosure of Invention
The invention aims to provide a preparation method of pH-sensitive water-swelling resin, which has the advantages of large water absorption swelling under neutral or weakly acidic conditions, less water absorption under alkaline conditions, strong water retention capacity and capability of tolerating complex stratum pressure environments.
The second purpose of the invention is to provide the application of the resin obtained by the preparation method in oil well cement slurry.
In order to realize the purpose, the technical scheme of the preparation method of the pH-sensitive water-swelling resin is as follows:
a preparation method of pH-sensitive water-swelling resin comprises the following steps: carrying out copolymerization reaction on acrylamide, acrylic acid, methacryloyloxyethyl trimethyl ammonium salt and a crosslinking agent N, N-methylene bisacrylamide in a solvent under the condition that the pH value is 5-7; the mol ratio of the acrylamide to the methacryloyloxyethyl trimethyl ammonium salt is (1-2) to (1-2), the mass of the acrylic acid accounts for 18-22% of the mass of the acrylamide, and the mass of the cross-linking agent accounts for 1-6% of the total mass of the acrylamide, the acrylic acid and the methacryloyloxyethyl trimethyl ammonium salt.
According to the preparation method of the pH-sensitive water-swellable resin, the comonomer and the cross-linking agent are selected, so that the resin has pH sensitivity and strong water retention capacity and can endure complex formation pressure environment. In an acid environment, the amino group of an acrylamide unit in the resin is combined with hydrogen ions, and a methacryloyloxyethyl trimethyl ammonium salt unit is ionized, so that copolymer molecules carry positive charges and repel each other, molecular chains stretch, and the water absorption capacity of the resin is increased; in a neutral environment, the unit of methacryloyloxyethyl trimethyl ammonium salt is mainly ionized, the charged positive electricity quantity is smaller than that in an acid environment, and the water absorption capacity of the resin is correspondingly reduced; in an alkaline environment, the ionization of the methacryloyloxyethyl trimethyl ammonium salt unit is inhibited, the copolymer molecule is basically uncharged, and therefore the water absorption capacity of the resin is greatly reduced.
Preferably, the copolymerization reaction uses potassium persulfate as an initiator, and the mass of the added potassium persulfate is 0.5-1% of the total mass of the acrylamide and the methacryloyloxyethyl trimethyl ammonium salt. Further preferably, the temperature of the copolymerization reaction is 80 ℃, and the reaction time is 4-6 h. The method is characterized by easy polymerization, simple operation, low cost and higher synthesis efficiency, and can improve the safety performance of production and reduce the production cost.
Preferably, the methacryloyloxyethyl trimethyl ammonium salt is methacryloyloxyethyl trimethyl ammonium chloride in view of both raw material cost and polymerization effect reaction.
Preferably, the solvent is water, and the total mass of the acrylamide and the methacryloyloxyethyl trimethyl ammonium salt accounts for 20-40% of the water; adjusting the pH value of the system to 5-7 by using acetic acid. The aqueous solution polymerization method is adopted, so that the cost is low and the environmental protection property is good. The acetic acid is added for pH adjustment, the price is low, the toxicity is avoided, and the pH value adjusting agent is easier to obtain compared with other pH value adjusting aids such as hydrochloric acid and the like.
And (3) placing the copolymerization product in water for repeated swelling and impurity removal, and replacing the water at intervals. The process is an impurity removal process, and can remove incompletely reacted raw materials in copolymerization reaction by utilizing the water absorption of resin. The interval time is not particularly limited, and the water can be replaced once within 6-12 h. Further, drying and crushing the copolymerization product after impurity removal. The drying temperature can be set to about 100 ℃.
The technical scheme of the application of the pH sensitive water-absorbing swelling resin is as follows:
the water-swelling resin obtained by the preparation method of the pH-sensitive water-swelling resin is applied to oil well cement slurry.
The pH sensitive water-absorbing expansion resin is directly added into the well cementing cement slurry to form a self-repairing cement slurry system, and the pH sensitive water-absorbing expansion resin has extremely low water absorption in a cement slurry environment (alkaline environment), so that the influence on the rheological property of the oil well cement slurry and the compressive strength of cured cement stones is small, and the smooth implementation of well cementing operation can be ensured.
When the well cementation cement sheath has microcracks due to stratum pressure environment, the pH sensitive water absorption swelling resin can absorb a large amount of weakly acidic or neutral underground water to absorb water to swell, and due to good water retention, the resin can effectively fill the microcracks generated in the set cement to block the microcracks, so that the oil well set cement microcracks can be automatically blocked when encountering water.
Detailed Description
The following examples are provided to further illustrate the practice of the invention.
First, specific examples of the method for preparing the pH-sensitive water-swellable resin of the invention
Example 1
The preparation method of the pH-sensitive water-swellable resin comprises the following steps:
measuring 40g of deionized water, adding the deionized water into a three-mouth beaker, opening a magnetic stirrer, introducing nitrogen, then sequentially adding 8.34g of acrylamide, 1.67g of acrylic acid, 4.16g of methacryloyloxyethyl trimethyl ammonium chloride, 0.14g N and N-methylene bisacrylamide, stirring for 10min, then slowly adding 1mol/L of acetic acid solution for neutralization to enable the whole system to be neutral or weakly acidic, adding 0.13g of potassium persulfate, stopping introducing the nitrogen, continuously stirring for 20min, placing the mixture into a constant-temperature water bath kettle at 80 ℃ for continuous reaction, and controlling the reaction time to be 6 h. And taking out the product, repeatedly soaking the product for 24 hours by using pure water to remove impurities, and replacing the deionized water every 8 hours. And finally, drying in a 99 ℃ oven and crushing.
Example 2
The preparation method of the pH-sensitive water-swellable resin comprises the following steps:
40g of deionized water is weighed and added into a three-mouth beaker, a magnetic stirrer is opened, nitrogen is introduced, then 6.25g of acrylamide, 1.25g of acrylic acid, 6.25g of methacryloyloxyethyl trimethyl ammonium chloride, 0.14g N and N-methylene bisacrylamide are added in sequence, and stirring is carried out for 10 min. Then slowly adding 1mol/L acetic acid solution for neutralization to make the whole system neutral or weakly acidic, adding 0.13g of potassium persulfate, stopping introducing nitrogen, continuously stirring for 20min, placing in a water bath kettle with constant temperature of 80 ℃ for continuous reaction, and controlling the reaction time to be 6 h. And taking out the product, repeatedly soaking the product for 24 hours by using pure water to remove impurities, and replacing the deionized water every 8 hours. And finally, drying in a 99 ℃ oven and crushing.
Example 3
The preparation method of the pH-sensitive water-swellable resin comprises the following steps:
40g of deionized water is weighed and added into a three-mouth beaker, a magnetic stirrer is opened, nitrogen is introduced, and then 4.16g of acrylamide, 0.83g of acrylic acid, 8.34g of methacryloyloxyethyl trimethyl ammonium chloride, 0.13g N and N-methylene bisacrylamide are sequentially added and stirred for 10 min. Then slowly adding 1mol/L acetic acid solution for neutralization, adding 0.13g of potassium persulfate into the whole system in a neutral or weakly acidic state, stopping introducing nitrogen, continuously stirring for 20min, placing into a water bath kettle with a constant temperature of 80 ℃ for continuous reaction, and controlling the reaction time to be 6 h. And taking out the product, repeatedly soaking the product for 24 hours by using pure water to remove impurities, and replacing the deionized water every 8 hours. Finally, the mixture is put into a 99 ℃ oven for drying and crushing.
Example 4
The preparation method of the pH-sensitive water-swellable resin comprises the following steps:
40g of deionized water is weighed and added into a three-mouth beaker, a magnetic stirrer is opened, nitrogen is introduced, then 8.34g of acrylamide, 1.67g of acrylic acid, 4.16g of methacryloyloxyethyl trimethyl ammonium chloride, 0.42g N and N-methylene bisacrylamide are added in sequence, and stirring is carried out for 10 min. Then slowly adding 1mol/L acetic acid solution for neutralization, adding 0.13g of potassium persulfate into the whole system in a neutral or weakly acidic state, stopping introducing nitrogen, continuously stirring for 20min, placing into a water bath kettle with a constant temperature of 80 ℃ for continuous reaction, and controlling the reaction time to be 6 h. And taking out the product, repeatedly soaking the product for 24 hours by using pure water to remove impurities, and replacing the deionized water every 8 hours. And finally, drying in a 99 ℃ oven and crushing.
Example 5
The preparation method of the pH-sensitive water-swellable resin comprises the following steps:
40g of deionized water is weighed and added into a three-mouth beaker, a magnetic stirrer is opened, nitrogen is introduced, then 8.34g of acrylamide, 1.67g of acrylic acid, 4.16g of methacryloyloxyethyl trimethyl ammonium chloride, 0.85g N and N-methylene bisacrylamide are added in sequence, and stirring is carried out for 10 min. Then slowly adding 1mol/L acetic acid solution for neutralization, adding 0.13g of potassium persulfate into the whole system in a neutral or weakly acidic state, stopping introducing nitrogen, continuously stirring for 20min, placing into a water bath kettle with a constant temperature of 80 ℃ for continuous reaction, and controlling the reaction time to be 6 h. And taking out the product, repeatedly soaking the product for 24 hours by using pure water to remove impurities, and replacing the deionized water every 8 hours. And finally, drying in a 99 ℃ oven and crushing.
In other embodiments of the method for preparing the pH sensitive water swellable resin of the present invention, the methacryloyloxyethyl trimethylammonium salt may be other series of materials such as methacryloyloxyethyl trimethylammonium sulfate, and the amount of the initiator added may be 0.8%, 0.9%, 1% or more of the total mass of the polymerized monomers (acrylamide and acrylic acid and methacryloyloxyethyl trimethylammonium salt); the acetic acid can be added in an amount to achieve a neutralization degree of 70%, 80%, etc., and can be neutral or weakly acidic. The corresponding copolymerization reaction temperature can be 75 ℃, 85 ℃ and the time can be 4h, 5h and 6h, and the corresponding water-absorbing expansion resin can be obtained.
Second, specific examples of applications of the pH-sensitive water-swellable resin of the present invention
Example 6
An example of the application of the pH-sensitive water-swellable resin of this example comprises the steps of:
5.68G of the pH sensitive water-swelling resin in example 3 is weighed and added into 1130.68G of cement dry powder, the addition amount of the pH sensitive water-swelling resin is 0.5 mass percent of the cement dry powder, then other solid cement additives are sequentially added, and the cement is G-grade oil well cement and is uniformly mixed in the dry powder stage. The uniformly mixed dry cement powder was then added to 500g of water at a water-cement ratio of 0.44 and stirred with a standard stirrer. Then pouring the cement paste into a mold, curing in water bath at 50 ℃ after initial setting, wherein the curing time is 7 days. The cement sample was taken out and the compressive and flexural strength was measured for 7 days.
Example 7
An example of the application of the pH-sensitive water-swellable resin of this example comprises the steps of:
11.36G of the pH sensitive water-swellable resin in example 3 was weighed and added to 1125G of cement dry powder in an amount of 1% by mass of the cement dry powder, and then other solid cement additives were sequentially added thereto, and the cement was mixed uniformly at the dry powder stage using G-grade oil well cement. The uniformly mixed dry cement powder was then added to 500g of water at a water-cement ratio of 0.44 and stirred with a standard stirrer. Then pouring the cement paste into a mold, curing in water bath at 50 ℃ after initial setting, wherein the curing time is 7 days. The cement sample was taken out and the compressive and flexural strength was measured for 7 days.
Third, Experimental example
In the experiment example, a pH sensitivity experiment is carried out, 0.5g of the pH sensitivity water-swelling resin in the example is weighed and placed into a 400-mesh sample net, then the sample net is placed into solutions with different pH values and cement slurry filtrate, samples are taken out every 3h and 24h, the samples are drained for 5min and weighed, and the water absorption rate of the water-swelling resin is calculated, and the results are shown in Table 1.
The calculation formula is as follows: water absorption rate SR ═ Wt/W0×100％
W0-water swellingDry weight of expanded resin
WtWater-swellable resin after water absorption
In table 1, the pH 6 solution was prepared from hydrochloric acid and water, the pH 13 solution was prepared from sodium hydroxide and water, and the slurry filtrate was filtered from the slurry. The water absorption data of the cement slurry filtrate in 24 hours is that the cement slurry filtrate is firstly placed in the original cement slurry filtrate for 3 hours and then placed in deionized water for 21 hours; the cement slurry is generally solidified basically after the third hour, at the moment, the water-absorbing resin can not absorb water from the cement slurry any more, and the application effect in the well cementation cement ring is simulated by adopting the experimental method. The data in the table are calculated water absorption rates.
TABLE 1 test results of water absorption multiplying power of different water-swellable resins
The experimental results in table 1 show that the pH-sensitive water-swellable resin of the examples has pH sensitivity, has a large water absorption capacity in a weakly acidic (nearly neutral) environment, has a small water absorption capacity in a cement slurry filtrate, and is very suitable for application in a self-repairing cement slurry system.
Claims (8)
1. A preparation method of pH-sensitive water-swelling resin is characterized by comprising the following steps: carrying out copolymerization reaction on acrylamide, acrylic acid, methacryloyloxyethyl trimethyl ammonium salt and a crosslinking agent N, N-methylene bisacrylamide in a solvent under the condition that the pH value is 5-7; the mol ratio of the acrylamide to the methacryloyloxyethyl trimethyl ammonium salt is (1-2) to (1-2), the mass of the acrylic acid accounts for 18-22% of the mass of the acrylamide, and the mass of the cross-linking agent accounts for 1-6% of the total mass of the acrylamide, the acrylic acid and the methacryloyloxyethyl trimethyl ammonium salt.
2. The process for producing a pH-sensitive water-swellable resin according to claim 1, wherein potassium persulfate is used as an initiator in the copolymerization reaction, and the amount of potassium persulfate added is 0.5 to 1% by mass based on the total mass of acrylamide, acrylic acid and methacryloyloxyethyltrimethylammonium salt.
3. The method for preparing a pH-sensitive water-swellable resin of claim 2, wherein the copolymerization reaction is carried out at a temperature of 80 ℃ for a reaction time of 4 to 6 hours.
4. The method for preparing a pH-sensitive water swellable resin of claim 1, wherein the methacryloyloxyethyl trimethyl ammonium salt is methacryloyloxyethyl trimethyl ammonium chloride.
5. The method for preparing a pH-sensitive water-swellable resin according to any of claims 1-4, wherein the solvent is water, and the total mass of acrylamide, acrylic acid, methacryloyloxyethyl trimethyl ammonium salt is 20-40% of water; adjusting the pH value of the system to 5-7 by using acetic acid.
6. The method for preparing a pH-sensitive water-swellable resin as claimed in claim 1, wherein the copolymerization product is subjected to repeated swelling and impurity removal by replacing water at intervals.
7. The method for preparing a pH-sensitive water-swellable resin of claim 6, wherein the copolymer product after impurity removal is dried and pulverized.
8. Use of the water-swellable resin for oil-well cement obtained by the method for preparing a pH-sensitive water-swellable resin according to claim 1.
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| CN113502151A (en) * | 2021-07-14 | 2021-10-15 | 王建平 | Manufacturing method of water-absorbing plugging cement slurry |
| WO2023279712A1 (en) * | 2021-07-07 | 2023-01-12 | 中国石油天然气集团有限公司 | Ph-responsive nano-gel plugging material, and preparation method therefor and use thereof |
| CN116239724A (en) * | 2023-02-13 | 2023-06-09 | 中国石油化工股份有限公司 | Alkali-resistant pH-sensitive water-absorbing swelling material, and preparation method and application thereof |
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| WO2023279712A1 (en) * | 2021-07-07 | 2023-01-12 | 中国石油天然气集团有限公司 | Ph-responsive nano-gel plugging material, and preparation method therefor and use thereof |
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| CN116239724A (en) * | 2023-02-13 | 2023-06-09 | 中国石油化工股份有限公司 | Alkali-resistant pH-sensitive water-absorbing swelling material, and preparation method and application thereof |
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