CN114316924B - Waterproof locking agent based on anion-cation pair effect and application thereof - Google Patents
Waterproof locking agent based on anion-cation pair effect and application thereof Download PDFInfo
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Abstract
The invention provides a waterproof locking agent based on anion-cation pair effect, which consists of an anion-cation pair surfactant composition, a zwitterionic surfactant, short-chain alcohol, a defoaming agent and water, wherein the anion-cation pair surfactant composition is formed by compounding an anion surfactant and a cation fluorocarbon surfactant. By utilizing the effect of the anion-cation pair between the anionic surfactant and the cationic fluorocarbon surfactant, the system has the characteristic of lower surface/interfacial tension performance, and the interfacial tension reaches 10 ‑3 The surface tension of mN/m reaches 18mN/m at the minimum, the waterproof locking agent can also improve the wettability of the surface of a stratum towards the double hydrophobic direction of hydrophobic and oleophobic, can effectively increase filtrate flowback, improve gas/oil phase permeability and obviously reduce water locking damage of a reservoir. The waterproof locking agent has low foaming rate of less than 10%, and can meet the use requirements of oil field drilling, well completion, well repair, water injection, recovery ratio improvement and other operations.
Description
Technical Field
The invention relates to the technical field of oil and gas well drilling and oil and gas field development, in particular to a waterproof locking agent for oil field drilling, well completion, well repair, water injection, recovery ratio improvement and other operation processes.
Background
In the operation processes of drilling, well completion, oil testing, well repairing, acidification, fracturing and the like of a low-permeability oilfield, partial fluid (mainly water) in the working fluid enters a pore canal wetted by reservoir water to generate a water locking effect under the action of positive pressure difference due to the fact that the pressure of a water-based working fluid column is larger than the pore pressure of a stratum, so that seepage resistance of oil and gas converging towards a well shaft is increased. In addition, the water self-priming effect of the reservoir rock sucks the water phase in the shaft working fluid into the oil gas seepage channel of the reservoir rock, so that the distribution of oil gas and water around the well hole is changed, the relative permeability of the oil gas is reduced, and the yield of the gas well can be reduced to be lower than 1/3 of the original yield. If oil reservoir protection is implemented on such reservoirs, the oil well yield can be increased by 10% -300%.
The main factors affecting the water lock damage are capillary force and liquid phase retention, and the smaller the capillary radius is, the longer the liquid discharge time is, and the more serious the water lock damage is. The capillary resistance is equal to the difference between the non-wetting phase pressure and the wetting phase pressure on two sides of the capillary meniscus, and the capillary pressure calculation formula p=2σcos θ/r shows that the capillary force is in direct proportion to the surface tension, so that the liquid discharge time can be effectively shortened and the capillary force can be reduced by reducing the surface tension on the premise that the capillary radius and the displacement pressure difference are kept unchanged, and the water lock damage can be effectively prevented and reduced. The waterproof locking agent is added into the working solution to reduce the surface tension of the retention liquid phase, thereby achieving the purpose of preventing and removing the damage of the waterproof lock.
The water-proof locking agent mainly used at present is alcohols such as methanol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and the like, and carbon-based surfactants such as ABSN, ABS, OP-10, tween, and the like. However, these conventional waterproof locking agents have the following disadvantages: (1) Alcohol is easy to be absorbed in stratum, so that the permeability of reservoir is reduced, and the water lock cannot be removed for a long time after alcohol treatment; (2) The waterproof locking agent of the carbon surfactant has the common problems of high surface tension, difficulty in enabling a reservoir to reach air humidity, high foaming rate and incapability of meeting the field use requirement.
Disclosure of Invention
Aiming at the conditions that the prior waterproof locking agent is high in surface tension, difficult to enable a reservoir to reach air humidity and high in foaming rate and cannot meet the field use requirement, the invention provides the waterproof locking agent based on anion-cation pairing effect, which has the advantages of low surface/interface tension, low foaming rate, capability of effectively improving the wettability of the reservoir and the like, can effectively increase filtrate flowback, improve air/oil phase permeability and reduce the water lock damage of the reservoir, and in addition, the waterproof locking agent contains a phosphate defoaming agent with stronger defoaming performance, so that the foaming rate is low and is less than 10 percent, and the field use requirement of working fluid can be met.
The aim of the invention is achieved by the following technical scheme.
The invention provides a waterproof locking agent based on anion-cation pair effect, which consists of an anion-cation pair surfactant composition, a zwitterionic surfactant, short-chain alcohol, a defoaming agent and water, wherein the mass percent of the anion-cation pair surfactant composition is 10-30%, the mass percent of the zwitterionic surfactant is 10-20%, the mass percent of the short-chain alcohol is 10-15%, the mass percent of the defoaming agent is 5-15%, and the balance is water.
The anion-cation pair surfactant composition is formed by compounding an anion surfactant and a cation fluorocarbon surfactant, wherein the mass ratio of the anion surfactant to the cation fluorocarbon surfactant is 1:10-10:1, and the system has the characteristic of lower surface/interfacial tension performance by utilizing the effect of the anion-cation pair between the anion surfactant and the cation fluorocarbon surfactant.
The anionic surfactant in the anionic surfactant composition is sulfonate anionic surfactant or carboxylate anionic surfactant selected from, but not limited to, petroleum sulfonate, alkylbenzenesulfonate, alkyl sulfonate, fatty alcohol ether carboxylate and alkylbenzene polyether carboxylate.
The cation in the cationic-to-surfactant composition is perfluoroalkyl quaternary ammonium salt or perfluoroalkyl amide quaternary ammonium salt,
the structure of the perfluoroalkyl quaternary ammonium salt is as follows:
C n F 2n+1 CH 2 CH 2 N + (CH 3 ) 2 C 2 H 5 X — n=6-8；
the structure of the perfluoroalkyl amide quaternary ammonium salt is as follows:
C n F 2n+1 CONH(CH 2 ) 3 N + (CH 3 ) 2 X — n=6-8。
the cationic fluorocarbon surfactant not only utilizes the interaction of cationic groups and anionic groups of the anionic surfactant to generate anion-cation pairs, so that the system has the characteristic of lower surface/interfacial tension performance, but also has the characteristic of improving the wettability of stratum, and after the system is injected into a stratum pore canal, the cationic fluorocarbon surfactant is positively charged and can be adsorbed on the surface of the pore canal, and the fluorocarbon chain has the hydrophobic and oleophobic biphobic characteristics, so that the flow resistance of oil-water two phases in the pore canal can be effectively reduced, the reverse drainage is promoted, the permeability is improved, and the water locking damage of a reservoir layer is reduced.
The amphoteric ion surfactant is betaine amphoteric ion surfactant, and the structural general formula is as follows:
RN + (CH 3 ) 2 (CH 2 ) n X -
wherein R is an alkyl chain, n is 0-6, and X is carboxylate or sulfonate.
The introduction of the zwitterionic surfactant can obviously enhance the stability of the system, the anionic surfactant and the cationic surfactant have stronger interaction between anion and cation pairs, when the proportion of the anionic surfactant and the cationic surfactant is close, the anionic surfactant and the cationic surfactant can generate precipitation, the amphoteric surfactant has both cationic groups and anionic groups in the structure, and the amphoteric surfactant can be effectively buffered between the anion and cation pairs when being introduced into the system, so that the precipitation of the anionic surfactant and the cationic surfactant is avoided, and the stability of the system is improved.
The short chain alcohol is one or more of the combination of lower alcohols with carbon chain number of 1-4, preferably but not limited to methanol, ethanol, isopropanol and n-butanol.
The defoamer is one or a combination of more selected from the group consisting of, but not limited to, tricresyl phosphate, triphenyl phosphate, trioctyl phosphate, tri-n-butyl phosphate, triisobutyl phosphate, butyldiphenyl phosphate, cresyl diphenyl phosphate and diphenyl monooctyl phosphate.
The waterproof locking agent system provided by the invention has more surfactants, a large amount of foam can be generated in the use process, the foam generation can affect the site construction and safety, and the foaming performance of the waterproof locking agent can be inhibited by introducing the phosphate defoamer, so that the foaming performance is lower than 10%, and the site construction is ensured to be carried out safely and stably.
The waterproof locking agent provided by the invention can be applied to the operation processes of oilfield drilling, well completion, well repair, water injection, recovery ratio improvement and the like.
The invention utilizes the effect of anion-cation pair between anionic surfactant and cationic fluorocarbon surfactant, the system has the characteristic of lower surface/interfacial tension performance, and the interfacial tension reaches 10 -3 The surface tension of mN/m reaches 18mN/m at the minimum, the waterproof locking agent can also improve the wettability of the surface of a stratum towards the double hydrophobic direction of hydrophobic and oleophobic, can effectively increase filtrate flowback, improve gas/oil phase permeability and obviously reduce water locking damage of a reservoir. The waterproof locking agent has low foaming rate of less than 10%, and can meet the use requirements of oil field drilling, well completion, well repair, water injection, recovery ratio improvement and other operations.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
The embodiment provides a waterproof locking agent based on anion-cation pairing, wherein the mass percentage of anions and cations to the surfactant composition is 10%, and the mass percentage of the zwitterionic surfactant C is as follows 8 H 17 N + (CH 3 ) 2 COO - The mass percentage of the water-soluble polymer is 20%, the mass percentage of the n-butanol is 10%, the mass percentage of the tri-n-butyl phosphate is 15%, and the balance is water. The anionic and cationic surfactant composition is sodium dodecyl benzene sulfonate and perfluoroalkyl quaternary ammonium salt C 6 F 13 CH 2 CH 2 N + (CH 3 ) 2 C 2 H 5 Cl — Of both substancesThe ratio of the amounts is 1:2.
Example 2
The embodiment provides a waterproof locking agent based on anion-cation pairing, wherein the mass percentage of anions and cations to the surfactant composition is 30%, and the mass percentage of the zwitterionic surfactant C is as follows 8 H 17 N + (CH 3 ) 2 (CH 2 ) 2 SO 3 The mass percentage of the water-soluble polymer is 10%, the mass percentage of the isopropanol is 15%, the mass percentage of the triisobutyl phosphate is 5%, and the balance is water. The anion-cation pair surfactant composition is fatty alcohol polyoxyethylene ether sodium carboxylate and perfluoroalkyl amide quaternary ammonium salt C 6 F 13 CONH (CH 2 ) 3 N + (CH 3 ) 2 Cl — The mass ratio of the two substances is 4:1.
Example 3
The embodiment provides a waterproof locking agent based on anion-cation pairing, wherein the mass percentage of anions and cations to the surfactant composition is 20%, and the mass percentage of the zwitterionic surfactant C is as follows 6 H 13 N + (CH 3 ) 2 (CH 2 ) 2 SO 3 15% by mass of ethanol, 15% by mass of trioctyl phosphate, 10% by mass of water and the balance. Anionic and cationic surfactant composition sodium nonylphenol polyoxyethylene ether carboxylate and perfluoroalkyl amide quaternary ammonium salt C 8 F 17 CONH (CH 2 ) 3 N + (CH 3 ) 2 Cl — The mass ratio of the two substances is 10:1.
Example 4
The embodiment provides a waterproof locking agent based on anion-cation pairing, wherein the mass percentage of anions and cations to the surfactant composition is 20%, and the mass percentage of the zwitterionic surfactant C is as follows 6 H 13 N + (CH 3 ) 2 (CH 2 ) 2 SO 3 15% by mass of methanol, 10% by mass of butyldiphenyl phosphate and the balance of water. Surface active of anion and cation pairThe agent composition is petroleum sulfonate and perfluoroalkyl quaternary ammonium salt C 8 F 17 CH 2 CH 2 N + (CH 3 ) 2 C 2 H 5 Cl — The mass ratio of the two substances is 1:10.
Example 5
The embodiment provides a waterproof locking agent based on anion-cation pairing, wherein the mass percentage of anions and cations to the surfactant composition is 20%, and the mass percentage of the zwitterionic surfactant C is as follows 6 H 13 N + (CH 3 ) 2 (CH 2 ) 2 SO 3 The mass percentage of the diphenyl monooctyl phosphate is 20%, the mass percentage of the n-butanol is 10%, the mass percentage of the diphenyl monooctyl phosphate is 15%, and the balance is water. The cationic and anionic surfactant composition is dodecyl sulfonate and perfluoroalkyl quaternary ammonium salt C 8 F 17 CH 2 CH 2 N + (CH 3 ) 2 C 2 H 5 Cl — The mass ratio of the two substances is 1:4.
Example 6
The embodiment provides a waterproof locking agent based on anion-cation pairing, wherein the mass percentage of anions and cations to the surfactant composition is 25%, and the mass percentage of the zwitterionic surfactant C is as follows 6 H 13 N + (CH 3 ) 2 (CH 2 ) 2 SO 3 The mass percentage of the water-based paint is 20%, the mass percentage of the ethanol is 10%, the mass percentage of the trioctyl phosphate is 15%, and the balance is water. Anionic and cationic surfactant composition sodium nonylphenol polyoxyethylene ether carboxylate and perfluoroalkyl amide quaternary ammonium salt C 8 F 17 CONH (CH 2 ) 3 N + (CH 3 ) 2 Cl — The mass ratio of the two substances is 1:1.
Example 7
The embodiment provides a waterproof locking agent based on anion-cation pairing, wherein the mass percentage of anions and cations to the surfactant composition is 10%, and the mass percentage of the zwitterionic surfactant C is as follows 8 H 17 N + (CH 3 ) 2 (CH 2 ) 2 SO 3 15% by mass of isopropyl alcohol, 15% by mass of triisobutyl phosphate and the balance of water. The anion-cation pair surfactant composition is fatty alcohol polyoxyethylene ether sodium carboxylate and perfluoroalkyl amide quaternary ammonium salt C 6 F 13 CONH (CH 2 ) 3 N + (CH 3 ) 2 Cl — The mass ratio of the two substances is 6:1.
Example 8
The embodiment provides a waterproof locking agent based on anion-cation pairing, wherein the mass percentage of anions and cations to the surfactant composition is 30%, and the mass percentage of the zwitterionic surfactant C is as follows 8 H 17 N + (CH 3 ) 2 COO - The mass percentage of the water-soluble polymer is 20%, the mass percentage of the n-butanol is 15%, the mass percentage of the tri-n-butyl phosphate is 15%, and the balance is water. The anionic and cationic surfactant composition is sodium dodecyl benzene sulfonate and perfluoroalkyl quaternary ammonium salt C 6 F 13 CH 2 CH 2 N + (CH 3 ) 2 C 2 H 5 Cl — The mass ratio of the two substances is 1:6.
Comparative examples 1 to 4
The fluorocarbon surfactant component of examples 1-4 was removed to obtain samples of comparative examples 1-4.
Comparative examples 5 to 8
The anionic surfactant component of examples 5 to 8 was removed to obtain samples of comparative examples 5 to 8.
Test example 1
This test example the waterproof locking agents based on the effect of the pair of anions and cations prepared in the above examples 1 to 8 and the samples in comparative examples 1 to 8 were subjected to a surface tension test in clear water and 10% NaCl simulated saline.
Surface tension test: the test is carried out by adopting a TX500C rotary drop meter interfacial tension meter, and the test conditions are as follows: the temperature was 25℃and the concentration of the sample agent was 0.1% and 0.5%.
The test results are shown in Table 1. From the results, it can be seen that: the surface tension of the sample of the example is obviously lower than that of the sample of the comparative example in clear water or 10% NaCl simulated saline, the difference between the example and the comparative example is that the interaction of the anions and cations exists in the example, and the anion surfactant or the cation fluorocarbon surfactant exists only singly in the comparative example, no ion pairing is formed, so that the sample based on the anion and cation pairing in the example has better surface tension reducing performance.
Table 1 results of surface tension property test of examples and comparative examples
Test example 2
This test example the waterproof locking agents based on the effect of the pair of anions and cations prepared in examples 1 to 8 and the samples in comparative examples 1 to 8 were subjected to a performance test for reducing the interfacial tension of simulated crude oil in clear water and 10% NaCl simulated brine.
Interfacial tension test: the test is carried out by adopting a TX500C rotary drop meter interfacial tension meter, and the test conditions are as follows: the temperature is 90 ℃ and the concentration of the sample agent is 0.5%.
The test results are shown in Table 2. From the results, it can be seen that: the interfacial tension of the sample of the example in the simulated brine of clear water and 10% NaCl can reach 10 due to the interaction of the anion-cation pair and the simulated crude oil -3 The comparative examples with no ion pair formation, which gave poor interfacial tension in the simulated crude oil, were only 10 at the lowest -1 mN/m。
Table 2 results of interfacial tension performance test for example and comparative example samples to reduce simulated crude oil
| Reducing the interfacial tension of simulated crude oil in clear water, mN/m | Reducing the interfacial tension of simulated crude oil in 10% NaCl simulated saline, mN/m | |
| Example 1 | 0.00156 | 0.00345 |
| Example 2 | 0.00318 | 0.00421 |
| Example 3 | 0.00624 | 0.00531 |
| Example 4 | 0.00259 | 0.00338 |
| Example 5 | 0.00521 | 0.00421 |
| Example 6 | 0.00663 | 0.00529 |
| Example 7 | 0.00463 | 0.00516 |
| Example 8 | 0.00265 | 0.00368 |
| Comparative example 1 | 0.126 | 1.062 |
| Comparative example 2 | 0.096 | 0.352 |
| Comparative example 3 | 0.351 | 0.982 |
| Comparative example 4 | 1.263 | 2.61 |
| Comparative example 5 | 0.624 | 1.023 |
| Comparative example 6 | 0.379 | 0.835 |
| Comparative example 7 | 0.316 | 0.821 |
| Comparative example 8 | 0.865 | 1.534 |
Test example 3
This test example the waterproof locking agents based on the effect of the pair of anions and cations prepared in examples 1 to 8 and the samples in comparative examples 1 to 8 were subjected to the test for improving the wettability of the core.
Improved core wettability test: the contact angle of the water drop and the oil drop on the original core is measured by adopting a contact angle tester, then the core is soaked in the samples of the examples and the comparative examples for 24 hours, and the contact angle of the water drop and the oil drop on the original core is re-measured after the core is taken out.
The test results are shown in Table 3. From the results, it can be seen that: the core has good hydrophobic and oleophobic properties after being treated by the sample provided by the embodiment of the invention.
Table 3 example and comparative example samples improved core wettability test results
| Water drop contact angle ° | Oil drop contact angle degree | |
| Working fluid | Spreading out | Spreading out |
| Example 1 | 73.2 | 23.3 |
| Example 2 | 78.2 | 24.6 |
| Example 3 | 80.5 | 23.1 |
| Example 4 | 76.2 | 28.5 |
| Example 5 | 74.6 | 25.1 |
| Example 6 | 81.3 | 20.9 |
| Example 7 | 72.4 | 26.1 |
| Example 8 | 75.3 | 21.6 |
| Comparative example 1 | 13.2 | Spreading out |
| Comparative example 2 | 17.1 | Spreading out |
| Comparative example 3 | 20.2 | Spreading out |
| Comparative example 4 | 12.4 | Spreading out |
| Comparative example 5 | 61.8 | 11.3 |
| Comparative example 6 | 59.4 | 13.5 |
| Comparative example 7 | 68.7 | 10.6 |
| Comparative example 8 | 67.1 | 12.3 |
Test example 4
This test example the waterproof locking agent based on the effect of the pair of anions and cations prepared in the above examples 1 to 8 and the samples in comparative examples 1 to 8 were subjected to foaming property test.
Foaming ability test: the high-speed stirrer is adopted, and the specific test conditions are as follows: the rotation speed is 10000rpm, the stirring time is 5min at room temperature, the sample concentration is 0.1%, and the solution quantity is 100mL.
The test results are shown in Table 4. The foaming rates of the samples of the examples and the comparative examples are lower than 10%, which indicates that the phosphate defoamer adopted in the invention has better defoaming effect, the foaming performance of the samples is effectively inhibited, the foaming rates are less than 10%, and the foaming agents meet the field operation requirements of oil fields.
Table 4 results of foaming property test of examples and comparative examples
| Foaming Properties | |
| Example 1 | 8.6% |
| Example 2 | 7.9% |
| Example 3 | 5.6% |
| Example 4 | 6.7% |
| Example 5 | 9.1% |
| Example 6 | 6.8% |
| Example 7 | 2.2% |
| Example 8 | 3.3% |
| Comparative example 1 | 8.6% |
| Comparative example 2 | 5.8% |
| Comparative example 3 | 6.8% |
| Comparative example 4 | 9.5% |
| Comparative example 5 | 8.5% |
| Comparative example 6 | 5.5% |
| Comparative example 7 | 7.6% |
| Comparative example 8 | 6.4% |
Test example 5
This test example core permeability recovery performance test was performed on the waterproof lock based on the effect of the pair of anions and cations prepared in examples 1 to 8 and the samples in comparative examples 1 to 8.
Core injury performance evaluation: and comparing and testing the core permeability recovery value of the working fluid by adopting a core flow test and adding the waterproof lock composition.
The test results are shown in Table 5. From the results, it can be seen that: the sample provided by the embodiment of the invention has better performance of recovering the core permeability.
Table 5 results of core permeability recovery performance test for examples and comparative samples
Claims (5)
1. A waterproof locking agent based on the effect of anion-cation pairing is characterized in that: the waterproof locking agent based on the anion-cation pair effect consists of an anion-cation pair surfactant composition, a zwitterionic surfactant, short-chain alcohol, a defoaming agent and water, wherein the anion-cation pair surfactant composition is formed by compounding an anion surfactant and a cation fluorocarbon surfactant; 10-30% of anion-cation pair surfactant composition, 10-20% of zwitterionic surfactant, 10-15% of short-chain alcohol, 5-15% of defoamer and the balance of water; the cationic fluorocarbon surfactant is perfluoroalkyl quaternary ammonium salt or perfluoroalkyl amide quaternary ammonium salt,
the structure of the perfluoroalkyl quaternary ammonium salt is as follows:
C n F 2n+1 CH 2 CH 2 N + (CH 3 ) 2 C 2 H 5 X — n=6 or 8, x is Cl;
the structure of the perfluoroalkyl amide quaternary ammonium salt is as follows:
C n F 2n+1 CONH(CH 2 ) 3 N + (CH 3 ) 2 X — n=6 or 8, x is Cl;
the ratio of the anions to the cations in the surfactant composition to the anionic surfactant and the cationic fluorocarbon surfactant is 1:10-10:1;
the anionic surfactant is selected from petroleum sulfonate, alkylbenzenesulfonate, alkyl sulfonate, fatty alcohol ether carboxylate and alkylbenzene polyether carboxylate;
the amphoteric ion surfactant is betaine amphoteric ion surfactant selected from C 8 H 17 N + (CH 3 ) 2 COO - 、C 8 H 17 N + (CH 3 ) 2 (CH 2 ) 2 SO 3 — Or C 6 H 13 N + (CH 3 ) 2 (CH 2 ) 2 SO 3 — 。
2. The cation-pairing-based waterproof locking agent according to claim 1, wherein: the short-chain alcohol is one or a combination of a plurality of low-carbon alcohols with carbon chain number of 1-4.
3. The cation-pairing-based waterproof locking agent according to claim 2, wherein: the short-chain alcohol is methanol, ethanol, isopropanol or n-butanol.
4. The cation-pairing-based waterproof locking agent according to claim 1, wherein: the defoamer is one or a combination of more selected from tricresyl phosphate, triphenyl phosphate, trioctyl phosphate, tri-n-butyl phosphate, triisobutyl phosphate, butyl diphenyl phosphate, cresyl diphenyl phosphate and diphenyl monooctyl phosphate.
5. The anion-cation pair based waterproof locking agent according to claim 1 is used in oilfield drilling, well completion, well repair, water injection and enhanced oil recovery processes.
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