CN106987240B - Anti-swelling clay stabilizer for water injection of low-permeability oil reservoir and preparation method thereof - Google Patents
Anti-swelling clay stabilizer for water injection of low-permeability oil reservoir and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of oil field development, and particularly relates to an anti-swelling clay stabilizer for water injection of a low-permeability oil reservoir and a preparation method thereof, wherein the anti-swelling clay stabilizer is prepared by compounding a soybean oil modified surfactant, tartaric acid, potassium hydroxide and water; wherein the soybean oil-modifying surfactant is a quaternary ammonium salt surfactant having a long carbon chain alkyl group and a quaternary ammonium cation. The anti-swelling clay stabilizer has the characteristics of wide raw material source, simple synthesis process, small using amount and strong oil reservoir adaptability; meanwhile, the composite material has good temperature resistance and salt tolerance, can resist the temperature of 290 ℃, has the mineralization resistance of 220000mg/L, has good compatibility with formation water, and has high expansion prevention rate which is more than 98.0 percent. Therefore, the invention can be widely applied to the technical field of oilfield exploitation.
Description
Technical Field
The invention belongs to the technical field of oilfield exploitation, and particularly relates to an anti-swelling clay stabilizer for water injection of a low-permeability oil reservoir and a preparation method thereof.
Background
Improving the waterflood development effect is one of the key technologies for improving the recovery efficiency of low-permeability oil reservoirs. The clay mineral in the low-permeability water-sensitive reservoir is easy to hydrate and expand, disperse and move, and block the throat. In low permeability reservoirs, the permeability is greatly reduced due to reservoir damage caused by water sensitivity, resulting in difficult injection. Compared with medium and high permeability reservoirs, the water sensitivity of low and ultra-low permeability reservoirs has more prominent influence on the development process. Therefore, care is taken to prevent clay swelling, especially during waterflooding of low, ultra-low permeability water-sensitive reservoirs.
At present, the method commonly adopted for preventing clay swelling is to add a clay stabilizer to the injected water. Because of the different compositions and contents of clay minerals in different types of reservoirs, different types of clay stabilizers must be selectively used for a particular reservoir. Currently, the commonly used methods for evaluating clay stabilizers are: the evaluation method is carried out according to a static evaluation method of the swelling volume change of the clay in water and a dynamic evaluation method through a change value of permeability in the process of a physical simulation experiment. The static evaluation method is widely used because of its simplicity and ease of operation.
According to the water-sensitive mechanism of clay minerals, if some injection agents are added into injected water, the injected water becomes a solution with positive ions, the positive ions and negative ions on the surface of a clay wafer are utilized to combine into an anti-swelling system, a hydrophobic surface is formed on the surface of the clay, and dipoles of silicon oxygen bonds or hydrogen oxygen bonds of the crystal surface of the clay are isolated from attracting water molecules, so that the effect of preventing the clay from hydration and swelling is achieved; secondly, the solution generates the actions of ion repulsion and polymerization condensation in a hydrated clay system, so that the clay mineral is agglomerated under the action of intermolecular force to play a role in preventing the clay from dispersing and transporting, and the assistant capable of eliminating the water sensitivity of the clay mineral is a clay stabilizer.
The cationic surfactant can dissociate in water to form surface active cations, and can adsorb on the surface of clay particles to neutralize the negative charges on the surface of clay, so that it can be used as an anti-swelling agent. However, cationic active agents, when used as clay anti-swelling agents, tend to react with several anionic chemicals to form precipitates, such as petroleum sulfonates or partially hydrolyzed polyacrylamides and some biopolymers used for enhanced oil recovery.
Although the effect achieved by the choice of polymer in clay stabilizer applications is significant, care should be taken that it has a large relative molecular mass, which would severely affect the water injection well permeability in the anti-swelling treatment once the water injection well reservoir is in a low permeability state. Using the BY-14 stabilizer application as an example, if the anti-swelling treatment process is completed before well re-injection, it may be found difficult to inject into the formation if the pressure is maintained at 30 MPa. Therefore, the evaluation of the adaptability of the clay stabilizer to the stratum is required to be well performed in the process of screening the clay stabilizer. For example, in the case of a low permeability reservoir, after air permeability measurement, BF-901 and J-1 stabilizers are injected separately, and both are maintained at a mass concentration of 20g/L, solution permeability measurement may be performed, and the permeability after distilled water transfer may be measured. Thus, it was found that the use of a stabilizer is likely to plug the core at higher molecular weights, whereas the stability of the core during the anti-swelling treatment can be ensured relative to a stabilizer having a lower molecular weight. Therefore, in the actual screening of the clay stabilizer, in order to avoid the damage of the low-permeability reservoir during the anti-swelling treatment, the relative molecular mass of the clay stabilizer is ensured to be low.
Patent ZL201310118314.7 discloses a method for preparing a low molecular weight clay stabilizer, which is prepared by polymerizing ammonium salt containing carbon and 2-acrylamide-2-methylpropanesulfonic acid in an aqueous solution, wherein the number average molecular weight of the polymer is less than 5 ten thousand. Sulfonic acid groups are introduced into the polymer stabilizer, so that the water solubility and the temperature resistance of the polymer are improved. It can form multi-point adsorption with several clay particles in water, and after adsorption, a layer of adsorption protecting film is formed on the surface of clay particles to prevent the clay particles from swelling and moving. But the stabilizer is difficult to use in low permeability oil fields.
Pengyijie et al 'synthesis and physicochemical property research of ester exchange quaternary amine type cationic soybean oil surfactant' proposes a surfactant with low cost and simple process, the surfactant belongs to a quaternary ammonium salt type, according to indoor experimental research, the surfactant has excellent anti-swelling effect, temperature resistance and no corrosion, and meanwhile, the surfactant belongs to a small molecular cationic surfactant and is suitable for low permeability oil reservoirs. Therefore, the soybean oil modified surfactant can be used as an anti-swelling clay stabilizer for low-permeability oil fields.
Disclosure of Invention
The invention provides a clay stabilizer with the function of protecting a reservoir stratum aiming at the defects of the prior art, and the clay stabilizer can be used for a low-permeability oil reservoir and has the advantages of good temperature resistance and salt resistance, low price and simple process.
The invention discloses a water-injection anti-swelling clay stabilizer for a low-permeability oil reservoir, which is prepared by compounding a soybean oil modified surfactant, tartaric acid, potassium hydroxide and water, wherein the soybean oil modified surfactant is a quaternary ammonium salt surfactant with long-carbon-chain alkyl and quaternary ammonium cations, and the molecular general formula of the surfactant is as follows:
wherein: r' is CnH2n+1N is more than or equal to 0 and less than or equal to 15; r' is CmH2m+1，0≤m≤15。
The anti-swelling clay stabilizer for water injection of the low-permeability oil reservoir comprises the following components:
preferably, the anti-swelling clay stabilizer for low-permeability reservoir water injection comprises the following components:
the invention also aims to provide a preparation method of the anti-swelling clay stabilizer for water injection of the low-permeability oil reservoir, which comprises the following specific steps:
(1) putting the water in the proportion into a beaker, and heating in a constant-temperature water bath kettle at the temperature of 40-65 ℃; under the condition that the stirring speed is 300-350 rpm, adding the tartaric acid in the proportion, and after the tartaric acid is completely added, continuously stirring for 10-20 min to obtain a mixed solution;
(2) adjusting the temperature of the mixed solution to 25-30 ℃, slowly adding the potassium hydroxide according to the proportion at the stirring speed of 200-300 rpm, and continuously stirring for 30-50 min after completely adding the potassium hydroxide; then heating to 60-75 ℃, and keeping the temperature for 10-15 min to obtain a transparent solution;
(3) and (3) adjusting the temperature of the transparent solution to 45-50 ℃, stirring at the speed of 350-500 rpm, adding the soybean oil modified surfactant in the proportion, stirring at a constant temperature for 10-30 min, and naturally cooling to room temperature to obtain a final product, namely the anti-swelling clay stabilizer.
According to the prior literature, the synthetic route of the soybean oil modified surfactant is as follows:
wherein: r' is CnH2n+1N is more than or equal to 0 and less than or equal to 15; r' is CmH2m+1，0≤m≤15。
Hair brushThe soybean oil surfactant in the stabilizer belongs to a micromolecular quaternary ammonium salt cationic surfactant, and the soybean oil surfactant is dissociated in water to generate cations with high positive electrovalence, can form multi-point adsorption with clay particles, and can replace K on the surface of a clay crystal layer+、Na+、Ca2+And the like metal cations. After the clay particles are adsorbed, an adsorption protective film of organic cations is formed on the surfaces of the clay particles to protect the clay particles and prevent the hydration, expansion, dispersion and migration of the clay particles. Tartaric acid is used as a chelating agent, can capture and separate specific divalent and trivalent metal ions, has the function of fixing cations, and simultaneously, the formed salt can be used for changing the wettability of the rock so as to change the rock from oil wetting to water wetting; the inorganic salt potassium hydroxide is easy to enter clay cavities, is firmly combined with the clay and plays a role in fixing the clay. Meanwhile, the soybean oil surfactant has moderate molecules, carbon chains are not easy to break, the soybean oil surfactant has good temperature resistance, the molecules can be tightly combined with clay without curling, the salt resistance is excellent, and the use efficiency is effectively improved.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the anti-swelling clay stabilizer has the advantages of wide raw material source, simple synthesis process and low cost;
(2) the anti-swelling clay stabilizer has low consumption, can be used for preventing swelling of water injection clay of a low-permeability oil reservoir and meets the development requirement of an oil field;
(3) the anti-swelling clay stabilizer has good temperature resistance and salt tolerance, can resist the temperature up to 290 ℃, has the mineralization degree up to 220000mg/L, and has good compatibility with formation water;
(4) the anti-swelling clay stabilizer can be strongly adsorbed to the surface of clay, is not easy to decompose, is permanently effective, and has high anti-swelling rate which can reach more than 98 percent.
Detailed Description
The present invention is described in further detail below with reference to specific examples and with reference to the data. It will be understood that these examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
Example 1: anti-swelling clay stabilizer E1And method for preparing the same
(1) Anti-swelling clay stabilizer E1The components and the components are as follows:
according to the prior literature, the synthetic route of the soybean oil modified surfactant is as follows:
wherein: r' is CnH2n+1N is more than or equal to 0 and less than or equal to 15; r' is CmH2m+1，0≤m≤15。
(2) Anti-swelling clay stabilizer E1The preparation method comprises the following steps:
50 parts of water is put into a beaker and heated in a constant-temperature water bath kettle at the temperature of 40 ℃; adding 0.1 part of tartaric acid under the condition that the stirring speed is 300rpm, and continuously stirring for 10min after the tartaric acid is completely added to obtain a mixed solution;
adjusting the temperature of the mixed solution to 25 ℃, slowly adding 0.01 part of potassium hydroxide at the stirring speed of 200rpm, and continuously stirring for 30min after completely adding the potassium hydroxide; then heating to 60 ℃, and keeping the temperature for 10min to obtain a transparent solution;
thirdly, adjusting the temperature of the transparent solution to 45 ℃, stirring at the speed of 350rpm, adding 15 parts of soybean oil modified surfactant, stirring at constant temperature for 10min, and naturally cooling to room temperature to obtain a final product, namely the anti-swelling clay stabilizer E1。
Example 2: anti-swelling clay stabilizer E2And method for preparing the same
(1) Anti-swelling clay stabilizer E2The components and the components are as follows:
according to the prior literature, the synthetic route of the soybean oil modified surfactant is as follows:
wherein: r' is CnH2n+1N is more than or equal to 0 and less than or equal to 15; r' is CmH2m+1，0≤m≤15。
(2) Anti-swelling clay stabilizer E2The preparation method comprises the following steps:
putting 80 parts of water into a beaker, and heating in a constant-temperature water bath kettle at 45 ℃; adding 0.5 part of tartaric acid under the condition that the stirring speed is 320rpm, and continuously stirring for 12min after completely adding the tartaric acid to obtain a mixed solution;
regulating the temperature of the mixed solution to 28 ℃, slowly adding 0.08 part of potassium hydroxide at the stirring speed of 250rpm, and continuously stirring for 40min after completely adding the potassium hydroxide; then heating to 65 ℃, and keeping the temperature for 13min to obtain a transparent solution;
thirdly, adjusting the temperature of the transparent solution to 48 ℃, stirring at the speed of 400rpm, adding 15 parts of soybean oil modified surfactant, stirring at constant temperature for 15min, and naturally cooling to room temperature to obtain a final product, namely the anti-swelling clay stabilizer E2。
Example 3: anti-swelling clay stabilizer E3And method for preparing the same
(1) Anti-swelling clay stabilizer E3The components and the components are as follows:
according to the prior literature, the synthetic route of the soybean oil modified surfactant is as follows:
wherein: r' is CnH2n+1N is more than or equal to 0 and less than or equal to 15; r' is CmH2m+1，0≤m≤15。
(2) Anti-swelling clay stabilizer E3The preparation method comprises the following steps:
putting 150 parts of water into a beaker, and heating in a constant-temperature water bath kettle at 55 ℃; under the condition that the stirring speed is 330rpm, adding 1.0 part of tartaric acid, and after completely adding, continuing stirring for 15min to obtain a mixed solution;
adjusting the temperature of the mixed solution to 26 ℃, slowly adding 0.05 part of potassium hydroxide at the stirring speed of 220rpm, and continuously stirring for 45min after completely adding the potassium hydroxide; then heating to 70 ℃, and keeping the temperature for 12min to obtain a transparent solution;
thirdly, adjusting the temperature of the transparent solution to 46 ℃, stirring at the speed of 460rpm, adding 15 parts of soybean oil modified surfactant, stirring at constant temperature for 20min, and naturally cooling to room temperature to obtain a final product, namely the anti-swelling clay stabilizer E3。
Example 4: anti-swelling clay stabilizer E4And method for preparing the same
(1) Anti-swelling clay stabilizer E4The components and the components are as follows:
according to the prior literature, the synthetic route of the soybean oil modified surfactant is as follows:
wherein: r' is CnH2n+1N is more than or equal to 0 and less than or equal to 15; r' is CmH2m+1，0≤m≤15。
(2) Anti-swelling clay stabilizer E4The preparation method comprises the following steps:
putting 200 parts of water into a beaker, and heating in a constant-temperature water bath kettle at 65 ℃; adding 2 parts of tartaric acid under the condition that the stirring speed is 350rpm, and continuously stirring for 20min after the tartaric acid is completely added to obtain a mixed solution;
adjusting the temperature of the mixed solution to 30 ℃, slowly adding 0.1 part of potassium hydroxide at the stirring speed of 300rpm, and continuously stirring for 50min after completely adding the potassium hydroxide; then heating to 75 ℃, and keeping the temperature for 15min to obtain a transparent solution;
thirdly, adjusting the temperature of the transparent solution to 50 ℃, stirring at the speed of 500rpm, adding 15 parts of soybean oil modified surfactant, stirring at constant temperature for 30min, and naturally cooling to room temperature to obtain a final product, namely the anti-swelling clay stabilizer E4。
Example 5
Accurately weighing 5.0g of the above E1～E4The anti-swelling clay stabilizer sample is dissolved in 995.0g of distilled water and stirred for 30min to form a uniform solution for later use.
Example 6
The anti-swelling rate of the product at 290 ℃ and the mineralization degree of 220000mg/L is evaluated according to the performance evaluation method of the clay stabilizer for water injection SY/T5971-94. The clay stabilizer solution used in this experiment was the solution prepared in example 5, and the results are shown in Table 1.
TABLE 1 anti-swelling clay stabilizer E1～E4Evaluation results of (2)
As can be seen from Table 1, anti-swelling clay stabilizer E1～E4The anti-swelling rates of the clay stabilizers E are all more than 98.0 percent, wherein2The anti-swelling rate is the highest and reaches 99.6 percent. The clay stabilizer developed by the invention has good capability of preventing the bentonite from hydration expansion under the conditions of 290 ℃ and the mineralization degree of 220000 mg/L.
Example 7
And performing a sample linear expansibility experiment according to a Chinese petroleum and natural gas industry standard 'evaluation method of shale inhibitors for drilling fluids' SY/T6335-1997. The instrument used was an NP-01 shale expansion tester. 8.00g of secondary bentonite (the diameter is 0.01-0.05 mm) dried for 4h at 105 ℃ is weighed and pressed into tablets on a press (the pressure is 10MPa, and the time is 5 min). The tablets were placed in a shale expansion instrument, the prepared stabilizer solution (solution prepared in example 6) of a certain concentration was added, and the expansion rate of the shale tablets after the test solution immersion was measured. The smaller the expansion rate of the shale tablets is, the stronger the capability of the product for inhibiting the hydration expansion of the clay is; otherwise, the worse. The results of the experiment are shown in table 2.
TABLE 2 test results of linear expansion ratio test
| Product(s) | 16h reduction rate relative to clear water% |
| E1 | 20.5 |
| E2 | 19.7 |
| E3 | 20.0 |
| E4 | 21.2 |
As can be seen from Table 2, clay stabilizer E1～E4The reduction rate of 16h relative to clear water is lower than 22 percent, wherein, the clay stabilizer E2The lowest reduction rate of 16h relative to clear water reaches 19.7 percent, which shows that the clay stabilizer product prepared by the invention can effectively inhibit the hydration expansion of clay.
Claims (4)
1. The anti-swelling clay stabilizer for water injection of the low-permeability oil reservoir is characterized by being prepared by compounding a soybean oil modified surfactant, tartaric acid, potassium hydroxide and water, wherein the soybean oil modified surfactant is a quaternary ammonium salt surfactant with long-carbon chain alkyl and quaternary ammonium cations, and the molecular general formula of the surfactant is as follows:
wherein: r' is CnH2n+1N is more than or equal to 0 and less than or equal to 15; r' is CmH2m+1，0≤m≤15。
2. The water-flooding anti-swelling clay stabilizer for low-permeability reservoirs according to claim 1, wherein the anti-swelling clay stabilizer comprises the following components:
3. the water-flooding anti-swelling clay stabilizer for low-permeability reservoirs according to claim 2, characterized in that the anti-swelling clay stabilizer comprises the following components:
4. the preparation method of the clay stabilizer for low permeability reservoir water injection and expansion prevention according to any one of claims 2 to 3, which is characterized by comprising the following steps:
(1) putting water into a beaker, and heating in a constant-temperature water bath kettle at 40-65 ℃; adding tartaric acid under the condition that the stirring speed is 300-350 rpm, and after the tartaric acid is completely added, continuously stirring for 10-20 min to obtain a mixed solution;
(2) adjusting the temperature of the mixed solution to 25-30 ℃, slowly adding potassium hydroxide at the stirring speed of 200-300 rpm, and continuously stirring for 30-50 min after completely adding the potassium hydroxide; then heating to 60-75 ℃, and keeping the temperature for 10-15 min to obtain a transparent solution;
(3) and (3) adjusting the temperature of the transparent solution to 45-50 ℃, stirring at the speed of 350-500 rpm, adding a soybean oil modified surfactant, stirring at a constant temperature for 10-30 min, and naturally cooling to room temperature to obtain a final product, namely the anti-swelling clay stabilizer.
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| 季铵硫酸化蓖麻油的制备;李云飞;《河南职工医学院学报》;20080615(第03期);219-221 * |
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