CN106905934B - Clay stabilizer for preventing water-sensitive damage and preparation method thereof - Google Patents
Clay stabilizer for preventing water-sensitive damage 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 a clay stabilizer for preventing water-sensitive damage and a preparation method thereof. The anti-swelling clay stabilizer has the characteristics of wide raw material source, simple synthesis process and strong oil reservoir adaptability; meanwhile, the mineral resistance and salt tolerance of the mineral water are good, the temperature resistance can reach 300 ℃, and the mineralization resistance can reach 200000 mg/L; has good compatibility with formation water and high expansion-proof rate which reaches 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 a clay stabilizer for preventing water-sensitive damage and a preparation method thereof.
Background
The clay mineral is widely present in an oil layer, and when the oil reservoir contains 5-20% of clay, the oil layer is considered to be the oil layer with high clay content. Such reservoirs, if improperly taken during development, can cause swelling, dispersion and migration of clay minerals, resulting in decreased permeability and formation damage. During swelling, the clay draws water into the crystal structure, causing an increase in the volume of the clay, thereby plugging the formation channels; during migration, clay materials are dispersed by foreign fluids, or carried with production fluids, forming bridging or chokes at the pore throats of the capillaries, which then lead to a decrease in formation permeability. In sandstone formations that do not contain water-swellable clay minerals, formation damage may sometimes occur due to the presence of mobile quartz particles and some other particles of non-swellable clay minerals (illite, etc.).
In the development process of low-permeability oil fields, water injection is an important measure for maintaining reservoir pressure and realizing stable yield and high yield, and the key point for ensuring that a water injection well can inject water and well inject water is that the water injection reservoir is not damaged. For a reservoir with stronger water sensitivity, the clay stabilizer suitable for the characteristics of the stratum is used in a targeted manner, so that the water sensitivity damage of the reservoir can be reduced, and the method has very important significance for the continuous and efficient development of the whole reservoir.
With the development of oil fields, the application of clay stabilizers is more and more extensive, and the development in this respect can be roughly divided into three stages according to different structures and different chemicals used: in the later period of 50 s to 60 s, inorganic salt clay stabilizer is mainly used for preventing swelling; in the 70 s, the inorganic polynuclear polymer and the cationic surfactant clay stabilizer are mainly used for preventing swelling; after the 80 s, the use of cationic organic polymer clay stabilizers to prevent swelling was mainly developed.
The cationic active agent can dissociate surface active cations in water, 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, polyacrylamides, and some biopolymers. The biggest defect is that the water wettability of the reservoir can be changed into oil wettability, and the relative permeability of water can be reduced.
Patent ZL201610041585.0 "clay stabilizer for oil and gas field fracturing and its preparation method" discloses a clay stabilizer for oil and gas field fracturing and its preparation method, the clay stabilizer is prepared by using polyethylene polyamine as initiator, ring-opening addition with ethylene oxide and propylene oxide, and then cationization reaction of amine, which can effectively prevent clay and shale from swelling. However, this invention uses a large amount of chlorine-containing organic compounds, which are highly toxic, and if the produced crude oil contains chlorine, it is likely to cause the deactivation of the cracking catalyst in the later stage.
Penyujie et al 'synthesis and physicochemical property research of ester exchange quaternary amine type cationic soybean oil surfactant' propose a surfactant with low cost and simple process, which belongs to quaternary ammonium salt type, and according to indoor experimental research, the surfactant has excellent anti-swelling effect, temperature resistance and no corrosion. Therefore, the soybean oil modified surfactant can be used as an anti-swelling clay stabilizer for oil fields.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the clay stabilizer with the function of preventing clay from swelling and protecting a reservoir stratum.
The anti-swelling clay stabilizer is prepared by compounding a soybean oil modified surfactant, acetylacetone, calcium 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+1(ii) a R' is CmH2m+1(ii) a M + n is more than or equal to 0 and less than or equal to 15, and m and n are integers.
The clay stabilizer comprises the following components:
preferably, the components of the clay stabilizer are as follows:
the invention also discloses a preparation method of the anti-swelling clay stabilizer, which comprises the following specific steps:
(1) adding the water in the proportion into a beaker, placing the beaker in a constant-temperature water bath kettle at the temperature of 60-75 ℃ for heating, adding the acetylacetone in the proportion under the condition that the stirring speed is 200-300 rpm, and continuously stirring for 15-30 min after the acetylacetone is completely added to obtain a mixed solution;
(2) adjusting the temperature of the mixed solution to 25-35 ℃, slowly adding the calcium hydroxide according to the proportion at a stirring speed of 500-600 rpm after the temperature is constant, continuously stirring for 20-30 min after the calcium hydroxide is completely added, then heating to 60-75 ℃, and keeping the temperature for 30-40 min to obtain a transparent solution;
(3) and (3) adjusting the temperature of the transparent solution to 50-60 ℃, adding the soybean oil modified surfactant in the proportion under the condition that the stirring speed is 200-300 rpm, stirring at a constant temperature for 20-30 min, and naturally cooling to room temperature to obtain a final product, namely the clay stabilizer.
The synthetic route of the anti-swelling clay stabilizer is as follows:
wherein R' is CnH2n+1(ii) a R' is CmH2m+1(ii) a M + n is more than or equal to 0 and less than or equal to 15, and m and n are integers.
The soybean oil surfactant belongs to quaternary ammonium salt cationic surfactant, which 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. Acetyl acetone is used as a chelating agent, can capture and separate out specific metal ions and has the function of fixing cations; the inorganic salt calcium hydroxide can enter clay holes to be firmly combined and reacts with clay to be converted into calcium aluminosilicate, so that negative charge repulsion among crystal layers of the clay mineral is eliminated, water molecules are difficult to enter among the crystal layers of the clay mineral, and hydration expansion of the clay is prevented. 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 clay stabilizer has the advantages of wide raw material source, simple synthesis process and low cost;
(2) the clay stabilizer has less consumption and strong oil reservoir adaptability, and can meet the requirement of oil field development;
(3) the clay stabilizer has good temperature resistance and salt tolerance, can resist the temperature of 300 ℃ and the mineralization degree of 200000mg/L, and has good compatibility with formation water;
(4) the clay stabilizer can be strongly adsorbed on the surface of clay, is not easy to decompose, 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: clay stabilizer D1And method for preparing the same
(1) Clay stabilizer D1The 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) Clay stabilizer D1The preparation method comprises the following steps:
adding 20 parts of water into a beaker, placing the beaker in a constant-temperature water bath kettle at 60 ℃ for heating, adding 0.2 part of acetylacetone under the condition of stirring speed of 200rpm, and continuously stirring for 15min after completely adding the acetylacetone to obtain a mixed solution;
adjusting the temperature of the mixed solution to 28 ℃, slowly adding 0.01 part of calcium hydroxide at the stirring speed of 500rpm after the temperature is constant, continuously stirring for 20min after the calcium hydroxide is completely added, then heating to 60 ℃, and keeping the temperature for 30min to obtain a transparent solution;
thirdly, regulating the temperature of the transparent solution to 50 ℃, adding 10 parts of soybean oil modified surfactant under the condition of stirring speed of 200rpm, stirring for 20min at constant temperature, and naturally cooling to room temperature to obtain a final product, namely the clay stabilizer D1。
Example 2: clay stabilizer D2And method for preparing the same
(1) Clay stabilizer D2The 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) Clay stabilizer D2The preparation method comprises the following steps:
adding 45 parts of water into a beaker, placing the beaker in a constant-temperature water bath kettle at 65 ℃ for heating, adding 1.5 parts of acetylacetone under the condition that the stirring speed is 300rpm, and continuously stirring for 20min after completely adding the acetylacetone to obtain a mixed solution;
adjusting the temperature of the mixed solution to 32 ℃, slowly adding 0.05 part of calcium hydroxide at the stirring speed of 530rpm after the temperature is constant, continuously stirring for 25min after the calcium hydroxide is completely added, then heating to 75 ℃, and keeping the temperature for 33min to obtain a transparent solution;
thirdly, the temperature of the transparent solution is adjusted to 52 ℃, and the stirring speed is 280rpmThen, 10 parts of soybean oil modified surfactant is added, the mixture is stirred for 25min at constant temperature, and then the mixture is naturally cooled to room temperature to obtain a final product, namely the clay stabilizer D2。
Example 3: clay stabilizer D3And method for preparing the same
(1) Clay stabilizer D3The 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) Clay stabilizer D3The preparation method comprises the following steps:
adding 80 parts of water into a beaker, placing the beaker in a constant-temperature water bath kettle at 70 ℃ for heating, adding 2.0 parts of acetylacetone under the condition that the stirring speed is 220rpm, and continuously stirring for 25min after completely adding the acetylacetone to obtain a mixed solution;
adjusting the temperature of the mixed solution to 25 ℃, slowly adding 0.02 part of calcium hydroxide at the stirring speed of 550rpm after the temperature is constant, continuously stirring for 20min after the calcium hydroxide is completely added, then heating to 65 ℃, and keeping the temperature for 37min to obtain a transparent solution;
thirdly, regulating the temperature of the transparent solution to 56 ℃, adding 10 parts of soybean oil modified surfactant under the condition of stirring speed of 250rpm, stirring for 22min at constant temperature, and naturally cooling to room temperature to obtain a final product, namely the clay stabilizer D3。
Example 4: clay stabilizer D4And method for preparing the same
(1) Clay stabilizationAgent D4The 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) Clay stabilizer D4The preparation method comprises the following steps:
adding 100 parts of water into a beaker, placing the beaker in a constant-temperature water bath kettle at 75 ℃ for heating, adding 2.5 parts of acetylacetone under the condition that the stirring speed is 260rpm, and continuously stirring for 30min after completely adding the acetylacetone to obtain a mixed solution;
adjusting the temperature of the mixed solution to 35 ℃, slowly adding 0.1 part of calcium hydroxide at the stirring speed of 600rpm after the temperature is constant, continuously stirring for 30min after the calcium hydroxide is completely added, then heating to 70 ℃, and keeping the temperature for 40min to obtain a transparent solution;
thirdly, regulating the temperature of the transparent solution to 60 ℃, adding 10 parts of soybean oil modified surfactant under the condition that the stirring speed is 300rpm, stirring for 30min at constant temperature, and naturally cooling to room temperature to obtain a final product, namely the clay stabilizer D4。
Example 5
Accurately weighing 5.0g of the above D1～D4The 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 300 ℃ and the mineralization degree of 200000mg/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 D1～D4Evaluation results of (2)
| Product(s) | Anti-swelling rate of% |
| D1 | 99.4 |
| D2 | 99.5 |
| D3 | 98.7 |
| D4 | 99.0 |
As can be seen from Table 1, anti-swelling clay stabilizer D1～D4The anti-swelling rates of the clay stabilizers D are all more than 98.0 percent, wherein2The anti-swelling rate is the highest and reaches 99.5 percent. The clay stabilizer developed by the invention has good capability of preventing the bentonite from hydration expansion under the conditions of 300 ℃ and the mineralization degree of 200000 mg/L.
Example 7
And performing a sample linear expansibility experiment according to a shale inhibitor evaluation method for drilling fluid SY/T6335-1997 in the China oil and gas industry standard. 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% |
| D1 | 20.6 |
| D2 | 19.0 |
| D3 | 20.2 |
| D4 | 19.5 |
As can be seen from Table 2, clay stabilizer D1～D4The reduction rate of 16h relative to clear water is lower than 21 percent, wherein, the clay stabilizer D2The lowest reduction rate of 16h relative to clear water reaches 19.0 percent, which shows that the clay stabilizer product prepared by the invention can effectively inhibit the hydration expansion of clay.
Claims (4)
1. The clay stabilizer is characterized by being prepared by compounding a soybean oil modified surfactant, acetylacetone, calcium hydroxide and water, wherein the soybean oil modified surfactant is a quaternary ammonium salt surfactant with long carbon chain alkyl and quaternary ammonium cation, 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 clay stabilizer according to claim 1, wherein the clay stabilizer comprises the following components:
3. the clay stabilizer according to claim 2, wherein the clay stabilizer comprises the following components:
4. the method for preparing a clay stabilizer according to any one of claims 2-3, wherein the method comprises the following steps:
(1) adding water into a beaker, placing the beaker in a constant-temperature water bath kettle at the temperature of 60-75 ℃ for heating, adding acetylacetone under the condition that the stirring speed is 200-300 rpm, and continuously stirring for 15-30 min after completely adding the acetylacetone to obtain a mixed solution;
(2) adjusting the temperature of the mixed solution to 25-35 ℃, slowly adding calcium hydroxide at a stirring speed of 500-600 rpm after the temperature is constant, continuously stirring for 20-30 min after the calcium hydroxide is completely added, then heating to 60-75 ℃, and keeping the temperature for 30-40 min to obtain a transparent solution;
(3) and (3) adjusting the temperature of the transparent solution to 50-60 ℃, adding a soybean oil modified surfactant under the condition that the stirring speed is 200-300 rpm, stirring at a constant temperature for 20-30 min, and naturally cooling to room temperature to obtain a final product, namely the clay stabilizer.
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