CN111303857B - Microemulsion single-step acid for oil well and preparation method and application thereof - Google Patents
Microemulsion single-step acid for oil well and preparation method and application thereof Download PDFInfo
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- CN111303857B CN111303857B CN202010155291.7A CN202010155291A CN111303857B CN 111303857 B CN111303857 B CN 111303857B CN 202010155291 A CN202010155291 A CN 202010155291A CN 111303857 B CN111303857 B CN 111303857B
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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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
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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
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
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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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/725—Compositions containing polymers
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- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B37/00—Methods or apparatus for cleaning boreholes or wells
- E21B37/06—Methods or apparatus for cleaning boreholes or wells using chemical means for preventing, limiting or eliminating the deposition of paraffins or like substances
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- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
Abstract
The invention provides a microemulsion single-step acid for an oil well as a preparation method and application thereof. The microemulsion single-step acid for the oil well comprises the following raw materials: 2 to 3 percent of wax crystal improver, 18 to 24 percent of organic scale blocking remover, 15.0 to 20.0 percent of amine oxide surfactant, 30.0 to 40.0 percent of hydrochloric acid, 7.0 to 12.0 percent of hydrofluoric acid, 12 to 16 percent of polycarboxylic acid chelating agent and the balance of water. The microemulsion single-step acid can effectively dissolve inorganic scale and organic scale in a near-wellbore area without flowback, the acid solution can effectively generate chelation with calcium ions, barium ions, iron ions and the like when reacting with the inorganic scale in a stratum, secondary precipitation generated in an acidification process is effectively inhibited, the action distance of the acid solution is increased, blockage formed by wax and asphaltene in the stratum is effectively dissolved, lattice distortion of the wax and the asphaltene is generated, flowback is not needed in the acidification process, construction is facilitated, and environmental pollution is avoided.
Description
Technical Field
The invention relates to the field of chemical agents for oilfield exploitation, in particular to a preparation method and application of a microemulsion single-step acid for an oil well.
Background
The acidification technology can improve the permeability of the near wellbore zone by dissolving and corroding rocks and plugs in the near wellbore zone so as to increase the productivity of an oil well and the water injection capacity of a water injection well, the acidification technology becomes a main measure for low-permeability stratum reconstruction, and the traditional acid system is mainly used for removing inorganic plugs and dissolved rocks in the near wellbore zone, cannot remove organic plugs and suspended oil in the near wellbore zone, and cannot remove the influence of emulsified oil on the water phase permeability. The existing micro-emulsion acid has the following problems:
(1) the plugging removal effect on organic matters such as formation wax, asphaltene and the like is poor, the used oil phase is mainly diesel oil, and the wax dissolution rate is only 0.005 g/min; (2) a certain amount of secondary precipitation is generated in the operation process, so that the effective period of the acidification operation is shortened; (3) the environmental pollution is increased by the need of flowback after the operation, and the operation period is longer.
Disclosure of Invention
Aiming at the defects of the existing acid liquor, the invention provides a microemulsion single-step acidification system which can be directly used for sandstone reservoirs. The microemulsion single-step acid liquid for the oil well has high wax dissolving rate and good secondary precipitation inhibition effect, does not need to flow back after the operation is finished, effectively reduces the condensation point of crude oil while removing the blockage of inorganic scale and organic scale in the near-wellbore area of the oil well, greatly prolongs the action distance of the acid liquid, and finally achieves the purposes of deep acidification blockage removal of the oil well and improvement of the productivity of the oil well.
The technical scheme adopted by the invention is as follows: the invention provides a microemulsion single-step acid for an oil well, the total mass of the microemulsion single-step acid for the oil well is 100%, and the microemulsion single-step acid for the oil well comprises the following raw materials: 2 to 3 percent of wax crystal improver, 18 to 24 percent of organic scale blocking remover, 15.0 to 20.0 percent of amine oxide surfactant, 30.0 to 40.0 percent of hydrochloric acid, 7.0 to 12.0 percent of hydrofluoric acid, 12 to 16 percent of polycarboxylic acid chelating agent and the balance of water. The sum of the mass percentages of the raw materials of the microemulsion single-step acid for the oil well is 100%.
The oil well microemulsion single-step acid comprises 2-3% of wax crystal modifier, wherein the selected wax crystal modifier is hot melt grade ethylene-vinyl acetate copolymer EVA260 which is purchased from DuPont in the United states. The hot-melt-grade ethylene-vinyl acetate copolymer with the vinyl acetate content of 28 percent and the melt index of 25 percent can distort the crystal lattice of the wax component after the acid solution is unblocked, so that the wax crystal after the unblocking does not absorb along with the reduction of the temperature, and the effects of wax prevention and pour point depression are achieved.
The microemulsion single-step acid comprises 18-24% of organic scale blocking remover, the selected organic scale blocking remover is dimethylbenzene, the effective content of the xylene is 99%, the wax and the asphaltene in the stratum can be quickly dissolved, and the corrosion of acid liquor to a pipe column can be reduced.
The raw material composition of the microemulsion single-step acid contains 10.0-20.0% of amine oxide surfactant, the selected amine oxide surfactant is dodecyl dimethyl amine oxide, the effective content of the amine oxide surfactant is 40%, the release speed of hydrogen ions can be reduced, and the action distance of the acid solution can be effectively increased.
The raw material composition of the microemulsion single-step acid contains 30.0-40.0% of hydrochloric acid, the effective content of the hydrochloric acid is 31%, and the blockage formed by calcium carbonate salt or hydroxide of the stratum can be effectively eliminated.
The raw material composition of the microemulsion single-step acid contains 7.0-12.0% of hydrofluoric acid, the effective content of the hydrofluoric acid is 40%, and the permeability of the sandstone formation is improved.
The single-step acid microemulsion comprises 12-16% of polycarboxylic acid chelating agent, the selected polycarboxylic acid chelating agent is acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer AA/AMPS, the effective content of the polycarboxylic acid chelating agent is 50%, calcium ions, iron ions and the like generated in the acidification process can be effectively formed into chelate, secondary precipitation of the substances can be effectively inhibited, the release rate of hydrogen ions in acid liquor can be effectively slowed down, and the action distance of hydrofluoric acid can be increased.
The invention also provides a preparation method of the microemulsion single-step acid for the oil well, which comprises the following steps:
under the condition of room temperature, sequentially adding a wax crystal improver and an organic scale blocking remover into a reaction kettle, heating to 40 ℃, stirring for 30 minutes, then controlling the rotating speed of the reaction kettle to be 600r/min, cooling to room temperature, then adding an amine oxide surfactant, hydrofluoric acid, a polycarboxylic acid chelating agent and the balance of water, and stirring for 30 minutes to obtain the microemulsion single-step acid for the oil well.
The microemulsion single-step acid for the oil well is applied to dissolving inorganic scale and organic scale formed in a sandstone stratum in an operation process, and effectively solves the problems of pressure rise and insufficient injection of the oil well. The microemulsion single-step acid for the oil well can be directly used for sandstone reservoir acidification construction.
The invention has the following beneficial effects:
1. the microemulsion single-step acid for the oil well can be directly used for a reservoir acidification construction process, can remove inorganic scale and organic scale plugs in a near-wellbore region, erodes a stratum to improve the permeability of the reservoir, forms a chelate with calcium, iron and the like, and effectively inhibits the substances from forming secondary precipitation; the method can prevent water sensitivity and quick sensitivity of a reservoir, the wax dissolution rate can reach 0.02g/min, the wax prevention rate is above 40%, the corrosion rate is above 20% at 60 ℃, the secondary precipitation inhibition rate can reach about 90%, and the damage to the secondary precipitation is avoided.
2. The microemulsion single-step acid for the oil well can be directly used for a reservoir acidification construction process, can quickly remove a near-wellbore area, can dissolve carbonate plugs caused by incompatibility of injected water and formation water, and effectively dissolve plugs formed by waxiness and asphaltene in the formation, so that the waxiness and the asphaltene generate lattice distortion, and are not required to be discharged back in an acidification process, thereby avoiding environmental pollution. When production is recovered, the condensation point of the crude oil can be effectively reduced, and the wax precipitation of the crude oil is prevented.
3. The microemulsion single-step acid for the oil well is microemulsion polyhydroic acid, can remove inorganic blockages and corrosion rocks in a near-wellbore zone, and can also remove the influence of organic blockages, suspended oil in the near-wellbore zone and emulsified oil on the water phase permeability. The microemulsion single-step acid has lower interfacial tension and secondary inhibition performance, can effectively generate chelation with calcium ions, barium ions, iron ions and the like when reacting with inorganic scale in a stratum, effectively inhibits the substances from forming secondary precipitation, improves the action distance of acid liquor, prevents reservoir water sensitivity and speed sensitivity, avoids the damage to the stratum caused by the expansion and migration of clay minerals in water, effectively recovers the stratum permeability and improves the oil well productivity.
4. The microemulsion single-step acid is an acid oil-in-acid microemulsion which is formed by dispersing an organic scale blocking remover, a surfactant and a chelating acid solution system in an acid medium through oil phases separated by amphiphilic compound monomolecular layers in a nano-scale oil drop mode and is a thermodynamic stabilizer. The traditional acid system is mainly used for removing solid plugs, inorganic scales and corrosion rocks in a near-wellbore area, the influence of organic plugs such as near-wellbore suspended oil and emulsified oil on the water phase permeability cannot be removed, and meanwhile, a certain amount of secondary sediment is generated in the acidification process to cause secondary damage to a stratum.
5. The microemulsion single-step acid of the present application also has the following features: (1) the single-step acid of the microemulsion is a thermodynamic stable body, can not break emulsion at high temperature, and increases the acidification distance. (2) The method can avoid the damage to the oil layer framework caused by excessive acidification of the near-well stratum and the sand production of the stratum. (3) The acid rock reaction speed can be reduced, acid is brought into the deep part of the stratum to react with the plug and sandstone particles, and the oil pipe and the casing pipe are prevented from being damaged. (4) For oil-water wells with repeated acidification, the pollution caused by the fact that the residual acid without activity pushes dispersed particles and the generated sediment in the stratum to the deep part of the stratum can be avoided.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides a microemulsion single-step acid for an oil well, and the composition of the raw materials of the microemulsion single-step acid for the oil well comprises: 2 percent of hot-melt ethylene-vinyl acetate copolymer EVA260, 20 percent of dimethylbenzene, 15.0 percent of dodecyl dimethyl amine oxide, 40.0 percent of hydrochloric acid, 10.0 percent of hydrofluoric acid, 12 percent of acrylic acid-2-acrylamide-2-methyl propane sulfonic acid copolymer AA/AMPS and the balance of water, wherein the raw materials are calculated according to mass percentage.
The microemulsion single-step acid for the oil well is prepared by the following steps:
under the condition of room temperature, sequentially adding hot-melt ethylene-vinyl acetate copolymer, namely EVA260 and xylene, into a reaction kettle, heating to 40 ℃, stirring for 30 minutes, then cooling to room temperature, then adding dodecyl dimethyl amine oxide, hydrofluoric acid, acrylic acid-2-acrylamide-2-methyl propane sulfonic acid copolymer AA/AMPS and the balance of water, and stirring for 30 minutes to obtain the microemulsion single-step acid for the oil well.
The oil well microemulsion single-step acid of the embodiment is tested indoors for wax dissolution rate, wax prevention rate, corrosion rate and secondary precipitation inhibition rate, and experimental data are as follows.
(1) Determination of wax dissolution Rate and wax control Rate
The wax dissolving rate and the wax prevention rate are tested according to SY/T6300-2009 technical conditions for clear and wax-proof agents for oil recovery, and the wax dissolving rate is tested by putting 1g of wax balls into 100mL of acid solution in a constant-temperature water bath at 50 ℃.
(2) Determination of erosion Rate
Crushing and drying rock minerals, sieving the crushed rock minerals by a sieve of 80 meshes, accurately weighing 2g of rock powder by using an electronic balance with the sensing quantity of 0.1mg, putting the rock powder into an inert plastic beaker, simultaneously adding 20mL of acid liquor, covering the beaker by using a preservative film, putting the beaker into a constant-temperature water bath (60 ℃), reacting for 2 hours, filtering and separating, drying and weighing filter residues, and calculating the acid liquor corrosion rate.
(3) Secondary precipitation inhibition test
Sequentially adding 10.00g of an acid liquor system, 40.00g of water and 2-3 drops of phenolphthalein into a 250mL plastic beaker; titrating with a sodium hydroxide solution, adding 4.00g of a 10% sodium hydroxide solution when the test liquid turns red from colorless, and then adding 3.00g of a 10% ferric chloride solution, 1g of calcium chloride and 100g of water; after the liquids are uniformly mixed, placing the plastic beaker in a water bath at 60 ℃ for 60min, taking out the beaker, immediately filtering the beaker by using filter paper, and washing the beaker by using distilled water for 2-3 times to ensure that all insoluble substances in the beaker are transferred to a funnel; washing the precipitate on the filter paper with 100mL of distilled water for 3-4 times, transferring the filter paper with the precipitate into an oven, taking out the filter paper with the precipitate after 2 hours at 105 ℃, putting the filter paper with the precipitate into a dryer, standing for 30 minutes, weighing (accurately to 0.0001g), recording the mass of the precipitate generated by different acid liquid systems, and arranging the data to be m respectively(Tu acid)，m(polyhydroic acid)。
(4) Evaluation of Corrosion inhibition Performance
At the temperature of 60 ℃, the corrosion inhibition performance is tested according to a static weight loss method in SY/T5405-1996 performance test method and evaluation index of corrosion inhibitor for acidification, and the test time is 4 h.
The oil well microemulsion single-step acid of the embodiment is tested indoors for wax dissolution rate, wax prevention rate, corrosion rate and secondary precipitation inhibition rate, and the test results are shown in table 1:
TABLE 1 microemulsion single step acid Performance test results for oil wells
| Performance index | Unit of | The result of the detection |
| Rate of wax dissolution | g/min | 0.023 |
| Wax control ratio | ％ | 83.2 |
| Rate of erosion | ％ | 24.3 |
| Corrosion rate (60 ℃, 4h) | g/(m2·h) | 1.15 |
| Secondary precipitation inhibition rate | ％ | 96.3 |
The microemulsion single-step acid for oil well of the present example was compared with a 2-port microemulsion single-step acid-acidified well and a 2-port earth acid-acidified well in an oil field of an highland, and the effects of the implementation are shown in table 2.
TABLE 2 highland barley field construction data
The construction result shows that after the single-step acid treatment of the microemulsion for the oil well, the average daily oil increment is 2.17t, the average effective days are 159 days, the cumulative oil increment is 693.1t, compared with the soil acid acidification, the effective days are prolonged by 42.6%, the cumulative measure oil increment is 439.5%, the yield increase effect is obvious, and the microemulsion for the oil well has good application value.
Example 2
The embodiment provides a microemulsion single-step acid for an oil well, and the composition of the raw materials of the microemulsion single-step acid for the oil well comprises: 3 percent of hot-melt-grade ethylene-vinyl acetate copolymer EVA260, 24 percent of dimethylbenzene, 18.0 percent of dodecyl dimethyl amine oxide, 40.0 percent of hydrochloric acid, 12.0 percent of hydrofluoric acid, 16 percent of acrylic acid-2-acrylamide-2-methyl propane sulfonic acid copolymer AA/AMPS and the balance of water.
The microemulsion single-step acid for the oil well is prepared by the following steps:
under the condition of room temperature, sequentially adding hot-melt ethylene-vinyl acetate copolymer, namely EVA260 and xylene, into a reaction kettle, heating to 40 ℃, stirring for 30 minutes, then cooling to room temperature, then adding dodecyl dimethyl amine oxide, hydrofluoric acid, acrylic acid-2-acrylamide-2-methyl propane sulfonic acid copolymer AA/AMPS and the balance of water, and stirring for 30 minutes to obtain the microemulsion single-step acid for the oil well.
The single-step acid of the microemulsion for oil wells in the embodiment is tested indoors for wax dissolution rate, wax prevention rate, corrosion rate and secondary precipitation inhibition rate, and the test results are shown in the following table 3:
TABLE 3 microemulsion single step acid Performance test results for oil wells
| Performance index | Unit of | The result of the detection |
| Rate of wax dissolution | g/min | 0.028 |
| Wax control ratio | ％ | 87.2 |
| Rate of erosion | ％ | 25.1 |
| Corrosion rate (60 ℃, 4h) | g/(m2·h) | 1.21 |
| Secondary precipitation inhibition rate | ％ | 98.7 |
The microemulsion single-step acid for oil wells of the present embodiment is compared with a 2-port microemulsion single-step acid acidification well and a 2-port earth acid acidification well in the cijiang oil field, and the implementation effect is shown in table 4.
TABLE 4 data of construction site of oil field around river
The construction result shows that after the single-step acid treatment of the microemulsion for the oil well, the average daily oil increment is 0.835t, the average effective days are 163.5 days, the cumulative oil increment is 186.61t, compared with the soil acid acidification, the effective days are prolonged by 32.38%, the cumulative measure oil increment is 216.23%, the yield increase effect is obvious, and the microemulsion for the oil well has good application value.
Claims (3)
1. The microemulsion single-step acid for the oil well is characterized by comprising the following raw materials in percentage by weight: 2 to 3 percent of wax crystal improver, 18 to 24 percent of organic scale blocking remover dimethylbenzene, 15.0 to 20.0 percent of amine oxide surfactant dodecyl dimethyl amine oxide, 30.0 to 40.0 percent of hydrochloric acid, 7.0 to 12.0 percent of hydrofluoric acid, 12 to 16 percent of polycarboxylic acid chelating agent acrylic acid-2-acrylamide-2-methyl propane sulfonic acid copolymer AA/AMPS and the balance of water, wherein the sum of the mass percentages of the raw materials of the microemulsion acid for the oil well is 100 percent; wherein the wax crystal modifier is hot-melt-grade ethylene-vinyl acetate copolymer EVA260, and the hot-melt-grade ethylene-vinyl acetate copolymer has a vinyl acetate content of 28%.
2. The use of the microemulsion single step acid for oil wells according to claim 1, wherein the microemulsion single step acid for oil wells is used for dissolving sandstone formations to form inorganic and organic scales during operation.
3. The use of the microemulsion single-step acid for oil wells according to claim 2, wherein the microemulsion single-step acid for oil wells is directly used for sandstone reservoir acidizing construction.
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