CN116877042A - Clean acidification process suitable for improving oil well yield - Google Patents

Clean acidification process suitable for improving oil well yield Download PDF

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CN116877042A
CN116877042A CN202310851291.4A CN202310851291A CN116877042A CN 116877042 A CN116877042 A CN 116877042A CN 202310851291 A CN202310851291 A CN 202310851291A CN 116877042 A CN116877042 A CN 116877042A
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clean
acid
surfactant
oil well
oil
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CN116877042B (en
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孟祥文
徐超
马芮
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DAQING QIXING PETROLEUM SCIENCE AND TECHNOLOGY Ltd
DAQING JINGSHENG WEIYE OILFIELD TECHNOLOGY SERVICE CO LTD
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DAQING QIXING PETROLEUM SCIENCE AND TECHNOLOGY Ltd
DAQING JINGSHENG WEIYE OILFIELD TECHNOLOGY SERVICE CO LTD
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    • EFIXED CONSTRUCTIONS
    • E21EARTH OR ROCK DRILLING; MINING
    • E21BEARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/25Methods for stimulating production
    • E21B43/26Methods for stimulating production by forming crevices or fractures
    • E21B43/27Methods for stimulating production by forming crevices or fractures by use of eroding chemicals, e.g. acids
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/524Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/12Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating

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Abstract

The invention provides a clean acidification process suitable for improving the oil well yield, which comprises the following steps: the clean acidification reagent system consisting of solid organic acid and active heat generating agent is adopted, and through two-step chemical reaction, the first step is to remove the inorganic scale blockage in the near-wellbore zone, recover the stratum permeability, and simultaneously can also react with the argillaceous cementing agent, quartz and feldspar particles to increase the stratum porosity; and then, a large amount of heat and gas are discharged in the second step of reaction, and heat energy is conducted in an oil layer, so that the temperature of the near-wellbore zone of the oil well is increased, the viscosity of high-viscosity organic matters such as colloid, asphaltene and the like is reduced, and the fluidity of the high-viscosity organic matters is increased. The gas released by the reaction and the surfactant generate foam, so that the wetting of the rock surface is changed, the oil-water interfacial tension is reduced, the oil displacement effect is improved, and the effective period of measures is prolonged. The injection mode of the fixed pipe column wellhead is adopted, and the method has the advantages of low cost, simple process, safety and environmental protection.

Description

Clean acidification process suitable for improving oil well yield
Technical Field
The invention relates to the technical field of oilfield blocking removal, in particular to a clean acidification process suitable for improving the oil well yield.
Background
At present, many oil fields in China, such as Daqing oil fields and victory oil fields, enter an extra-high water content development stage, energy needs to be supplemented through water injection, so that the heterogeneity of a reservoir is more serious, the quality of the reservoir is poor, the content of argillaceous clay is high, and the migration damage of particles is serious. These particulate matter filled between rock particles are extremely sensitive and subject to hydrolytic expansion, erosion dispersion, exfoliation migration and blockage, resulting in shrinkage of the pores and reduced permeability. In the production process of an oil well, along with microscopic changes of pressure, oil gas components and the like, paraffin and asphaltene are extremely easy to condense and deposit in a near-wellbore zone, so that a seepage storage space is changed, rock is changed from water to oil, and permeability is reduced. In the process of underground operation, because of the actions of unmatched liquid entering, solid particle invasion, clay hydration, oil-water emulsification and the like, and the changes of environmental conditions, heavy components such as colloid, asphaltene, wax and the like are condensed and accumulated, scale, organic siltation and oil scale interactive plugs are formed at the throat of the near-wellbore zone of the oil well, so that the near-wellbore zone of the oil well is blocked, and the yield of the produced oil well is seriously reduced. Therefore, the water injection oil field needs to be periodically acidized to remove the blockage, the seepage channel can be effectively recovered by the acidizing technology, the matrix skeleton of the reservoir can be eroded, the earthworm pore channel can be formed, the permeability of the reservoir is improved, and the aim of increasing the yield of the oil well is fulfilled. However, in the acidification construction, the acid liquor component relates to dangerous chemicals such as liquid hydrochloric acid, hydrofluoric acid and the like, and the management and control difficulty is high, and the safety and environmental protection risk coefficient is high in the manual preparation, storage and transportation processes; in addition, the residual acid of the acid liquor is not environment-friendly and not degradable, and the residual acid still needs to be returned from the reservoir, so that the construction cost is increased; if the flowback is not timely, the pollution injury of the reservoir layer can be caused again. Part of wells with low productivity often cannot be lifted, and in the subsequent production process, the residual acid can corrode pumps, pipes, oil-water separation devices and the like, and enter a ground production system to influence the production operation, so that the application scale of oil well acidification is limited.
In order to achieve the aim of acid sustained release of the acid blocking remover, CN112480902A discloses an intelligent encapsulated acid and a using method, wherein the intelligent encapsulated acid has a core-shell structure, hydrophobic nano particles (fumed silica, polystyrene, poly (benzyl methacrylate) and fluorine-containing polymer) are used as shells, and liquid acid (hydrochloric acid, formic acid, acetic acid, citric acid, gelled acid, thickened acid and diverting acid) is used as a core material. The encapsulated acid of the patent does not automatically release acid liquid to react with the stratum, and a certain release agent is needed to be added. After the encapsulated acid reaches the formation target location, the encapsulated acid encounters a release agent and the encapsulated acid releases a liquid acid to react with the formation. Thereby achieving the purpose of slowly releasing the acid and improving the effective acidification distance. However, the preparation process of the encapsulated acid is complex, the cost is high, the encapsulated acid is not suitable for industrial production, the flowback residual acid still exists, the reservoir is damaged to a certain extent, and the encapsulated acid is not suitable for an oil field with ultra-high water content. Similarly, CN106479477a, CN104804718A discloses an encapsulated solid acid comprising a capsule core and a capsule wall, the new capsule material being nitric acid powder, the capsule wall being polyacrylamide, polyvinyl chloride, gelatin, chitosan. The capsule slow release acid is prepared by coating acidic substances with shells made of certain materials and is slow released under specific conditions. However, the water quality of the oil field stratum in different areas has great difference and poor applicability. Even in different water injection oil wells of the same oil field, the capsule type acid slow-release blocking removal system has different acid slow-release effects, and has weak applicability.
CN109593518A discloses a solid acid plugging removing system for oilfield acidification plugging removing, which adopts the cooperation of solid acid and ammonium fluoride, and can react after well injection to slowly generate hydrofluoric acid, so as to increase the effective distance of acidification. But still generates residual acid and does not greatly increase the oil yield of the ultra-high water-containing oil well.
Therefore, the clean acidizing blocking remover for the oil well with strong applicability is developed to replace the conventional acidizing fluid, does not need the flowback residual acid, is convenient to apply, has excellent yield increasing effect and has good applicability. At present, the clean acidification technology of the oil well is less studied at home and abroad. The development of the clean acidizing blocking remover for oil well production increase, which is suitable for domestic oil reservoirs, in particular to land sandstone oil reservoirs, has very important scientific research significance and practical industrial value.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a clean acidification process suitable for providing oil well yield, which adopts a clean acidification reagent system consisting of solid organic acid and an active heat generating agent, and achieves the aim of improving the oil well yield through various effects of acidification blocking removal, cleaning wetting of a surfactant, heat, gas and the like generated by chemical reaction. The technical scheme integrates the comprehensive advantages of the solid acid blocking removal technology, the chemical self-heating gas technology and the surfactant throughput technology. The clean acidification reagent system consisting of solid organic acid and active heat generating agent is adopted, and through two-step chemical reaction, the first step is to remove the inorganic scale blockage in the near-wellbore zone, recover the stratum permeability, and simultaneously can also react with the argillaceous cementing agent, quartz and feldspar particles to increase the stratum porosity. The second step of reaction emits a large amount of heat and gas, and heat energy is conducted in an oil layer, so that the temperature of the near-wellbore zone of the oil well is increased, the viscosity of high-viscosity organic matters such as colloid, asphaltene and the like is reduced, and the fluidity of the high-viscosity organic matters is increased; simultaneously, the released gas can enter the pores of the oil layer to break up bridging substances and break up the oil flow resistance caused by capillary force. The gas released by the reaction of the system and the surfactant generate foam, which is favorable for increasing the blocking removal radius, and when the well is opened for production, the gas in the stratum can carry dissolved organic matters out along with the foam in the moving process of the gas to the well shaft, thereby improving the permeability and inducing the oil flow. Meanwhile, the wetting of the surfactant to the rock surface reduces the oil-water interfacial tension, improves the oil displacement effect and prolongs the effective period of measures. The wellhead injection mode is adopted, the operation of a pipe column is not needed, and the method has the characteristics of low cost, simple process, safety, environmental protection and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a clean acidizing process suitable for increasing the production of an oil well comprising the steps of:
(S1) preparing a clean acidification working fluid for improving the oil well yield:
(S101) preparing a clean acidolysis blocking remover, which comprises the following raw materials in percentage by weight: 10-15wt% of solid acid, 1.0-2.0wt% of ammonium bifluoride, 1.5-2.0wt% of surfactant I,1.0-2.0wt% of anti-swelling agent, 0.5-0.8wt% of corrosion inhibitor and the balance of water; the surfactant I is the compound of an anionic surfactant and an alkanolamide surfactant;
(S102) preparing an active heat generating agent, which comprises the following raw materials in percentage by weight: 0.5-1.0wt% of pH regulator, 0.3-0.5wt% of surfactant II,0.3-0.5wt% of anti-swelling agent and the balance of water; the surfactant II is a compound of an anionic surfactant and a polyoxyethylene ether surfactant;
(S2) injecting a clean and acidic working fluid for improving the oil well yield;
(S201) stopping the pumping unit, closing a paraffin removal gate, connecting a pump truck with a ground pipeline, and testing the pressure of clean water;
(S202) reversely injecting a cleaning acid blocking remover from the sleeve gate;
(S203)) back-pouring from the sleeve gate for 10m 3 ~15m 3 Clear water;
(S204) back-injecting the active heat generating agent from the sleeve gate;
(S205) closing a sleeve gate and stewing the well for 3-5 days;
and (S3) starting the pumping unit and normally producing.
Further, the anionic surfactant is selected from at least one of long-chain alkyl sulfonates such as sodium dodecyl benzene sulfonate, sodium tetradecyl sulfonate, sodium hexadecyl sulfonate; the alkanolamide surfactant is at least one selected from coconut monoethanolamide, coconut diethanolamide and lauric diethanolamide; the polyoxyethylene ether surfactant is at least one selected from fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ether, fatty amine polyoxyethylene ether and ricinoleic acid polyoxyethylene ether.
Further, the surfactant I is an anionic surfactant and an alkanolamide surfactant according to the mass ratio of 3-5:1, compounding; the surfactant II is an anionic surfactant and a polyoxyethylene ether surfactant according to the mass ratio of 1-2: 1-2.
According to the invention, the nonionic surfactant and the anionic surfactant are selected to be compounded, so that a better oil washing effect is achieved. Meanwhile, the inventor also finds that the nonionic surfactant in the clean acid blocking remover is selected from alkanolamide surfactants, and the nonionic surfactant in the active heat generating agent is selected from polyoxyethylene ether surfactants, so that the purposes of improving the oil well yield and stabilizing the production can be more effectively achieved.
In the clean acidification blocking removal process, a clean acidification reagent system consisting of solid organic acid and an active heat generating agent is adopted, the problem of residual acid flowback is thoroughly solved through two-step chemical reaction, the damage to a reservoir is eliminated, the effect of organic matters (asphalt, polymers, colloid and the like) causing oil well blocking is eliminated, the wetting of the surface of rock can be prevented, the wettability of the reservoir is maintained, and the effect of clay lattice expansion is inhibited.
The solid acid is a mixture of urea nitrate and sulfamic acid according to the mass ratio of 2-3:1; the anti-swelling agent is at least one selected from ammonium chloride, sodium chloride and potassium chloride, and is preferably ammonium chloride; the pH regulator is carbonate and/or bicarbonate, and is specifically at least one selected from sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate and ammonium bicarbonate.
The corrosion inhibitor is an imidazoline corrosion inhibitor, preferably the corrosion inhibitor is a modified imidazoline quaternary ammonium salt, and the modified imidazoline quaternary ammonium salt is prepared by a preparation method comprising the following steps:
(T1) carrying out dehydration reaction on anacardic acid, excessive diethylenetriamine and a water carrying agent under protective atmosphere, heating to carry out cyclization reaction, and rotationally evaporating excessive water and diethylenetriamine after the reaction is finished to obtain viscous liquid which is modified imidazoline;
and (T2) heating the modified imidazoline to 100-110 ℃ under protective atmosphere, slowly adding 1, 4-bis (2-chloroethyl) benzene, and preserving the temperature for 1-2h to obtain the product modified imidazoline quaternary ammonium salt.
Further, the molar ratio of cardanic acid, diethylenetriamine and 1, 4-bis (2-chloroethyl) benzene was 1:1.1-1.5:0.4-0.45, in the step (T1), the water carrying agent is selected from at least one of toluene and dimethylbenzene, and the protective atmosphere is nitrogen and/or argon; further, the dehydration reaction temperature is 140-170 ℃ and the reaction time is 2-3h; heating to 180-210 ℃ for cyclization reaction, wherein the cyclization reaction is not carried out for 3-5h; in the step (T2),
the protective atmosphere is nitrogen and/or argon.
The modified imidazoline quaternary ammonium salt prepared by the method is gemini quaternary ammonium salt with imidazoline quaternary ammonium salt at two ends, which is obtained by the reaction of cashew acid modified imidazoline and 1, 4-di (2-chloroethyl) benzene. The corrosion inhibitor has certain surface activity and can effectively play a role in corrosion inhibition. The inventors have unexpectedly found that only the cashew acid modified imidazolinium quaternary ammonium salt can maximize oil well production and effectively perform corrosion inhibition. When the anacardic acid is replaced by rosin and oleic acid, the oil well yield and corrosion resistance cannot be improved at the same time, which is possibly determined by the special chemical structure of anacardic acid.
The preparation of the anacardic acid is self-made or commercially available, and is well known in the art, specifically, anacardic acid is prepared by dissolving anacardic shell liquid in methanol aqueous solution, adding calcium hydroxide, reacting for 4-8 hours at 40-50 ℃ to generate a large amount of anacardic acid calcium precipitate, washing, vacuum drying, dispersing in water, adding acid for acidification, extraction, washing, reduced pressure distillation and drying, and finally anacardic acid is obtained.
Further, in the step (S101), the clean water pressure test process is well known in the art, and in one embodiment of the present invention, clean water is injected to 25-30MPa, the pressure is stabilized for 10-15min, and the pressure drop is not more than 0.7MPa, which is qualified.
Further, in the step (S2), the amount of the clean and acidified working fluid is determined according to the plugging degree of the reservoir of the oil well and in combination with the effective thickness, the porosity and the treatment radius, and the calculation method is as follows:
V=πr 2 hΦδ; wherein the V-working solution extrusion quantity is expressed in unit m 3 The method comprises the steps of carrying out a first treatment on the surface of the r-treatment radius, unit m; h, the effective thickness of the oil layer is m; phi-reservoir porosity in units; delta-filling coefficient, the value of the clean acid blocking remover is 1-1.5, preferably 1-1.2, and the value of the active heat generating agent is 2-3, preferably 2.2-2.5.
The invention starts from analyzing the mechanism, the blocking degree and the characteristics of the reduction cause of the oil well productivity, comprehensively considers that the use safety coefficient of the liquid strong acid is low, and the residual acid can corrode pumps, pipes, oil-water separation devices and the like, and enters a ground production system to influence the production and transportationThe problems of the solid acid blocking removal and the like are solved, and the cleaning acidification blocking removal working solution is adopted and consists of a cleaning acidification working solution and an active heat generating agent, so that the comprehensive advantages of a solid acid blocking removal technology, a chemical self-generation hot gas technology and a surfactant throughput technology are integrated. To ensure an effective radius of treatment for acidification, the solid organic acid is selected to slowly release H + And the ammonium bifluoride continuously generates hydrofluoric acid, and the hydrofluoric acid content is not high and is kept at a certain level in the construction process, so that the method is suitable for deep acidification. In addition, the hydrolyzed HF chemically reacts with clay minerals, reducing the cation exchange capacity of the clay. Therefore, the solid organic acid system has the functions of retarding and stabilizing clay particles, and meets the technical requirements of oil well acid liquid. Meanwhile, the cleaning acidification blocking removal working solution is easy to prepare, store and transport; considering the problems of high formation crude oil saturation, serious organic deposition injury, strong corrosion of underground equipment with residual acid acidity, influence on ground production and the like, the active heat generating agent system mainly comprises (hydrogen) carbonate and surfactant, and chemically reacts with acid in the formation to release a large amount of heat and CO 2 The heat energy generated by the chemical reaction of the gas can raise the flow capacity of the crude oil and release CO 2 The gas and the surfactant generate foam, which is beneficial to increasing the blocking removal radius, and when the well is opened for production, the gas in the stratum can carry dissolved organic matters out along with the foam in the moving process of the gas to the well shaft, thereby improving the permeability and inducing the oil flow. Meanwhile, the wettability of the rock is changed through the surfactant, the tension of an oil-water interface is reduced, the oil displacement effect is improved, and the effective period of measures is prolonged. The wellhead injection mode is adopted, the operation of a pipe column is not needed, and the method has the characteristics of low cost, simple process, safety, environmental protection and the like.
The invention has the following technical advantages:
1. the clean acidolysis blocking remover consists of solid organic acid and anionic and nonionic surfactant. The solid acid solves the problems of high control difficulty, high safety and environmental protection risk coefficient and slow release of H in the process of storing, preparing and transporting by adopting the liquid strong acid component in the acidizing fluid at present + Continuously generates hydrofluoric acid, has the advantages of retarding and stabilizing adhesionThe soil particles can meet the technical requirements of oil well acid liquor, and the corrosion rate of the natural rock debris is more than 12.0% after 16 hours; rate of fracture<3.0%。
2. The gemini modified imidazoline quaternary ammonium salt prepared by the method has the functions of a corrosion inhibitor and a surfactant. The inventor unexpectedly discovers that gemini quaternary ammonium salt synthesized by using cashew acid modified imidazoline can effectively improve the oil well yield while maintaining corrosion inhibition performance. It is generally believed that cationic surfactants (such as quaternary ammonium salts) and anionic surfactants (such as sulfonates) are not miscible. Because two surfactants of different electrical properties will combine due to charge interactions, precipitation may occur. However, the applicant finds that the cashew acid modified imidazoline quaternary ammonium salt and the surfactant I are compounded together in a certain proportion, so that the cashew acid modified imidazoline quaternary ammonium salt has stronger surface activity. This is probably because the complex formed, due to the association of the two different charges, forms micelles more easily in solution, resulting in higher surface activity and wetting. While other organic acids such as oleic acid, abietic acid, cinnamic acid, etc., are not as effective as the cashew acid modified imidazolinium quaternary ammonium salts to increase oil well production. The possible reason is that the imidazoline quaternary ammonium salt prepared by modifying the organic acid cannot be well matched with the anionic surface activity.
Detailed Description
The invention will be further illustrated with reference to specific examples:
the anacardic acid reference document "study on synthesis and curing reaction characteristics of anacardic acid epoxy resin", chen Jian, volume 40, and 4, used in the examples of the present invention. Specifically, 100 parts by mass of cashew shell liquid (cashew acid content 82.6 wt.%) was dissolved in 750 parts by mass of 95% aqueous methanol solution, and 50 parts by mass of Ca (OH) was slowly added with stirring at 200rpm 2 After the addition is completed in 1h, reacting for 4h at 45-55 ℃, generating a large amount of precipitate after the reaction is completed, filtering to obtain a crude product of the calcium cashew, washing with methanol, vacuum drying to obtain the calcium cashew, dispersing in 500 parts by mass of water, slowly dropwise adding 150 parts by mass of 8M HCl, stirring for 1h, extracting with ethyl acetate, washing with distilled water, and organic solventThe phase was concentrated by distillation under reduced pressure, dried over anhydrous sodium sulfate, and 62.6 parts by mass of anacardic acid was finally obtained. The molecular weight was about 340g/mol as measured by GPC.
Preparation example 1
(T1) 1 mole part of anacardic acid and 1.4 mole parts of diethylenetriamine, and toluene, carrying out dehydration reaction for 3 hours at 150 ℃ under the nitrogen atmosphere, then heating to 200 ℃ for cyclization reaction, carrying out reaction for 2 hours, and evaporating excessive water and diethylenetriamine by rotary evaporation after the reaction is finished to obtain viscous liquid which is modified imidazoline;
and (T2) heating the modified imidazoline to 110 ℃ in a nitrogen atmosphere, slowly adding 0.4 molar part of 1, 4-bis (2-chloroethyl) benzene in 1h, and reacting for 2h under heat preservation to obtain the product modified imidazoline quaternary ammonium salt.
Comparative preparation example 1
Other conditions and operations were the same as in preparation example 1 except that anacardic acid was replaced with an equimolar amount of rosin.
Comparative preparation example 2
Other conditions and operations were the same as in preparation example 1 except that cardanic acid was replaced with an equimolar amount of oleic acid.
Comparative preparation example 3
Other conditions and operations were the same as in preparation example 1 except that anacardic acid was replaced with an equimolar amount of lauric acid.
PREPARATION EXAMPLE 2-1
(1) 10 parts by mass of solid acid (a mixture of urea nitrate and sulfamic acid according to a mass ratio of 2:1), 1 part by mass of ammonium bifluoride, 1.5 parts by mass of surfactant I (compounding of sodium dodecyl benzene sulfonate and coco diethanol amide according to a mass ratio of 3:1), 1.0 parts by mass of ammonium chloride, 0.5 parts by mass of modified imidazoline quaternary ammonium salt corrosion inhibitor prepared in preparation example 1 and 86 parts by mass of water are weighed to prepare a clean acidification blocking remover 1.
(2) 0.5 part by mass of sodium carbonate as a pH regulator, 0.3 part by mass of surfactant II (the mixture of sodium dodecyl benzene sulfonate and fatty alcohol-polyoxyethylene ether according to the mass ratio of 1:1), 0.3 part by mass of ammonium chloride and 98.9 parts by mass of water are weighed to prepare an active heat generating agent 1.
PREPARATION EXAMPLE 2-2
(1) 15 parts by mass of solid acid (a mixture of urea nitrate and sulfamic acid according to a mass ratio of 3:1), 1.5 parts by mass of ammonium bifluoride, 2 parts by mass of surfactant I (the mixture of sodium hexadecyl sulfonate and coconut monoethanolamide according to a mass ratio of 5:1) and 2.0 parts by mass of ammonium chloride are weighed, and 0.8 part by mass of the modified imidazoline quaternary ammonium salt corrosion inhibitor prepared in preparation example 1 and 78.7 parts by mass of water are prepared to prepare a clean acid blocking remover 2.
(2) 1 part by mass of sodium carbonate as a pH regulator, 0.5 part by mass of surfactant II (the mixture of sodium hexadecyl sulfonate and polyoxyethylene ricinoleate according to the mass ratio of 1:2), 0.5 part by mass of ammonium chloride and 98.0 parts by mass of water are weighed to prepare an active heat generating agent 2.
PREPARATION EXAMPLES 2-3
The preparation of the clean acid blocking remover 3 is carried out under the same conditions as in preparation example 2-1, except that the surfactant I is the compound of sodium dodecyl benzene sulfonate and coco diethanolamide according to the mass ratio of 1:1.
PREPARATION EXAMPLES 2 to 4
The clean acid blocking remover 4 was prepared under the same conditions as in preparation example 2-1 except that the amount of the surfactant I used was 2 parts by mass.
PREPARATION EXAMPLES 2 to 5
Clean acidolysis blocking remover 5 was prepared under the same conditions as in preparation example 2-1 except that the solid acid was urea nitrate in an amount of 10 parts by mass.
Preparation examples 2 to 6
Clean acidolysis blocking remover 6 was prepared under the same conditions as in preparation example 2-1 except that the solid acid was 10 parts by mass of sulfamic acid.
Preparation examples 2 to 7
Clean acidolysis blocking remover 7 was prepared under the same conditions as in preparation example 2-1 except that 0.5 parts by mass of modified imidazoline quaternary ammonium salt corrosion inhibitor was prepared by comparative preparation example 1.
Preparation examples 2 to 8
Clean acidolysis blocking remover 8 was prepared under the same conditions as in preparation example 2-1 except that 0.5 parts by mass of modified imidazoline quaternary ammonium salt corrosion inhibitor was prepared by comparative preparation example 2.
Preparation examples 2 to 9
Clean acidolysis blocking remover 9 was prepared under the same conditions as in preparation example 2-1 except that 0.5 parts by mass of modified imidazoline quaternary ammonium salt corrosion inhibitor was prepared by comparative preparation example 3.
Effect example
1. Cleaning acid complex and Properties
Secondary precipitation, such as iron, calcium, magnesium and other compounds are easy to form after acid liquor reacts with clay minerals, secondary precipitation generated after acidification can cause formation damage, and the secondary precipitation is also a key for determining whether acidification construction is successful or not. The pH of the residual acid is the main factor affecting secondary precipitation, fe (OH) 3 Precipitation occurs at a pH of 2-4. At Fe 3+ Under the condition that the concentration of the standard solution is 0.5g/L, the experimental result shows that the performance of the clean acidification blocking remover for complexing iron ions is superior to that of the conventional acidification solution, and the requirement of complexing index can be met. The complex of the cleaning acid and the performance evaluation experimental data are shown in table 1. Reference standard: SY/T6571-2012.
TABLE 1 Complex property evaluation of cleaning acids
2. Clean acid natural rock core blocking removal performance
And evaluating the modification degree of the clean acid on the rock core through a rock core blocking removal simulation experiment. Experimental results show that the permeability of the clean acid before and after displacement is improved by more than about 2.2 times, and the end faces of the rock core before and after displacement are intact. The test data of the core blocking removal performance evaluation of the clean acid are shown in Table 2.
Table 2 core plug removal performance evaluation of clean acid
K 1 Is the standard brine displacement core permeability;K 2 the core permeability is displaced by using standard saline after acid liquor displacement.
Permeability increase = (K) 2 One K 1 )/K 1 ×100%。
Application example the present invention is used for in-situ effect testing for improving oil well production:
examples 1 to 6 the clean acidolysis blocking remover and the active heat generator prepared in preparation examples 2-1 to 2-6 were used; comparative examples 1 to 3 clean-up acidolysis blocking remover and active heat generator formulated in preparation examples 2 to 7 to 2 to 9.
Daqing oilfield clean acidification process field test for improving oil well yield: firstly, preparing a cleaning and acidifying working solution for improving the oil well yield, wherein the working solution comprises a cleaning and acidifying blocking remover and an active heat generating agent; stopping the pumping unit, closing the paraffin removal gate, connecting the pump truck with a ground pipeline, testing the pressure of 25MPa with clear water, and stabilizing the pressure for 10min; reverse injection of cleaning acid blocking remover from sleeve gate and reverse injection of clear water for 10m 3 Reversely injecting an active heat generating agent; closing a sleeve gate and stewing the well for 3-5 days; and starting the pumping unit and normally producing.
The dosages of the cleaning acidolysis blocking remover and the active heat generating agent are calculated according to the formula: v=pi r 2 hΦδ; wherein the V-working solution extrusion quantity is expressed in unit m 3 The method comprises the steps of carrying out a first treatment on the surface of the r-treatment radius, unit m; h, the effective thickness of the oil layer is m; phi-reservoir porosity in units; delta-filling coefficient, the value of the clean acidification blocking remover is 1, and the value of the active heat generating agent is 2.5.
And (3) analyzing the field test condition and the effect:
the clean and acidic working solution is adopted to select an oil well with geological conditions, water quality and oil yield close to those of a ternary composite flooding block of a Daqing oil field, the fixed pipe column is used for acidizing and unblocking, and the reaction residual liquid is not returned after the working solution is injected into the oil well, so that the ground electric dehydrator works normally. The data of the field test yield increase effect and the change of the produced liquid property for improving the oil well yield cleaning and acidizing process are shown in Table 5. The effective period refers to the period when the injected working fluid is unblocked, the yield is increased, but the daily oil yield gradually decreases with the lapse of time, and the daily oil yield is reduced to the date of the daily oil yield before the measure, namely the effective period.
Table 5 data on yield effect of field test
According to the clean acidification process, no acid is returned by matching the clean acidification working solution and the active heat generating agent, so that the damage to the stratum is reduced. The two-step working solution optimizes the blocking removal process, can effectively improve the yield, has long effective period, and has the characteristics of low cost, simple process, safety, environmental protection and the like.

Claims (10)

1. A clean acidizing process suitable for increasing the production of an oil well comprising the steps of:
(S1) preparing a clean acidification working fluid for improving the oil well yield:
(S101) preparing a clean acidolysis blocking remover, which comprises the following raw materials in percentage by weight: 10-15wt% of solid acid, 1.0-2.0wt% of ammonium bifluoride, 1.5-2.0wt% of surfactant I,1.0-2.0wt% of anti-swelling agent, 0.5-0.8wt% of corrosion inhibitor and the balance of water; the surfactant I is the compound of an anionic surfactant and an alkanolamide surfactant; the corrosion inhibitor is modified imidazoline quaternary ammonium salt;
(S102) preparing an active heat generating agent, which comprises the following raw materials in percentage by weight: 0.5-1.0wt% of pH regulator, 0.3-0.5wt% of surfactant II,0.3-0.5wt% of anti-swelling agent and the balance of water; the surfactant II is a compound of an anionic surfactant and a polyoxyethylene ether surfactant;
(S2) injecting a clean and acidic working fluid for improving the oil well yield;
(S201) stopping the pumping unit, closing a paraffin removal gate, connecting a pump truck with a ground pipeline, and testing the pressure of clean water;
(S202) reversely injecting a cleaning acid blocking remover from the sleeve gate;
(S203)) back-pouring clean water from the cannula gate;
(S204) back-injecting the active heat generating agent from the sleeve gate;
(S205) closing a sleeve gate and stewing the well for 3-5 days;
and (S3) starting the pumping unit and normally producing.
2. The clean acidizing process suitable for use in increasing the production of oil wells according to claim 1, wherein the anionic surfactant is selected from at least one of long chain alkyl sulfonates such as sodium dodecyl benzene sulfonate, sodium tetradecyl sulfonate, sodium hexadecyl sulfonate; the alkanolamide surfactant is at least one selected from coconut monoethanolamide, coconut diethanolamide and lauric diethanolamide; the polyoxyethylene ether surfactant is at least one selected from fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ether, fatty amine polyoxyethylene ether and ricinoleic acid polyoxyethylene ether.
3. The clean acidification process for oil well production according to claim 1, wherein surfactant I is an anionic surfactant and an alkanolamide surfactant according to a mass ratio of 3 to 5:1, compounding; the surfactant II is an anionic surfactant and a polyoxyethylene ether surfactant according to the mass ratio of 1-2: 1-2.
4. The clean acidification process for increasing oil well production according to claim 1, wherein said solid acid is a mixture of urea nitrate and sulfamic acid in a mass ratio comprised between 2 and 3:1; the anti-swelling agent is at least one selected from ammonium chloride, sodium chloride and potassium chloride, and is preferably ammonium chloride; the pH regulator is carbonate and/or bicarbonate, and is specifically at least one selected from sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate and ammonium bicarbonate.
5. The clean acidification process for oil well production according to claim 1, wherein said modified imidazoline quaternary ammonium salt is obtained by a preparation process comprising the steps of:
(T1) carrying out dehydration reaction on anacardic acid, excessive diethylenetriamine and a water carrying agent under protective atmosphere, heating to carry out cyclization reaction, and rotationally evaporating excessive water and diethylenetriamine after the reaction is finished to obtain viscous liquid which is modified imidazoline;
and (T2) heating the modified imidazoline to 100-110 ℃ under protective atmosphere, slowly adding 1, 4-bis (2-chloroethyl) benzene, and preserving the temperature for 1-2h to obtain the product modified imidazoline quaternary ammonium salt.
6. The clean acidification process for oil well production according to claim 5, wherein the molar ratio of cardanic acid, diethylenetriamine and 1, 4-di (2-chloroethyl) benzene is 1:1.1-1.5:0.4-0.45, in the step (T1), the water carrying agent is selected from at least one of toluene and dimethylbenzene, and the protective atmosphere is nitrogen and/or argon.
7. The clean acidification process for oil well production according to claim 5, wherein the dehydration reaction temperature is between 140 and 170 ℃ and the reaction time is between 2 and 3 hours; and heating to carry out cyclization reaction, namely heating to 180-210 ℃ and not reacting for 3-5h.
8. The clean acidification process for oil well production according to claim 5, wherein cardanic acid is obtained by a process comprising: dissolving cashew shell liquid in methanol water solution, adding calcium hydroxide, reacting at 40-50deg.C for 4-8 hr to obtain cashew acid calcium precipitate, washing, vacuum drying, dispersing in water, adding acid for acidification, extracting, washing, vacuum distilling, and drying to obtain cashew acid.
9. The clean acidizing process for increasing the production of a well according to claim 1, wherein in step (S2), the amount of said clean acidizing fluid is determined according to the degree of plugging of the reservoir of the well in combination with the effective thickness, the porosity and the treatment radius, calculated as follows:
V=πr 2 hΦδ; wherein the V-working solution extrusion quantity is expressed in unit m 3 The method comprises the steps of carrying out a first treatment on the surface of the r-treatment radius, unit m; h, the effective thickness of the oil layer is m; phi-reservoir porosity in units; delta-filling coefficient, the value of the clean acid blocking remover is 1-1.5, and the value of the active heat generating agent is 2-3.
10. The clean acidizing procedure suitable for increasing the yield of an oil well according to claim 9, wherein δ = 1-1.2 in the clean acidizing plug removal agent dosage; in the active heat generating agent, delta=2.2-2.5.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118165721A (en) * 2024-05-15 2024-06-11 山东海嘉石油化工有限公司 Organic retarded acid and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5692566A (en) * 1996-01-22 1997-12-02 Texaco Inc. Formation treating method
US20050250666A1 (en) * 2004-05-05 2005-11-10 Weatherford/Lamb, Inc. Foamer/sulfur scavenger composition and methods for making and using same
CN102635344A (en) * 2012-04-13 2012-08-15 中国石油天然气股份有限公司 Composite blockage removal method for improving flow conductivity of three-low sandstone reservoir
US20140332212A1 (en) * 2011-11-30 2014-11-13 Verutek Technologies, Inc. Compositions and methods for enhanced hydrocarbon recovery
CN106281273A (en) * 2015-05-15 2017-01-04 中国石油天然气股份有限公司 Acid liquor system for acidifying carbonate reservoir
CN115703962A (en) * 2021-08-16 2023-02-17 中国石油化工股份有限公司 Blocking remover and construction method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5692566A (en) * 1996-01-22 1997-12-02 Texaco Inc. Formation treating method
US20050250666A1 (en) * 2004-05-05 2005-11-10 Weatherford/Lamb, Inc. Foamer/sulfur scavenger composition and methods for making and using same
US20140332212A1 (en) * 2011-11-30 2014-11-13 Verutek Technologies, Inc. Compositions and methods for enhanced hydrocarbon recovery
CN102635344A (en) * 2012-04-13 2012-08-15 中国石油天然气股份有限公司 Composite blockage removal method for improving flow conductivity of three-low sandstone reservoir
CN106281273A (en) * 2015-05-15 2017-01-04 中国石油天然气股份有限公司 Acid liquor system for acidifying carbonate reservoir
CN115703962A (en) * 2021-08-16 2023-02-17 中国石油化工股份有限公司 Blocking remover and construction method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
贾虎;蒲万芬;赵金洲;金发扬;: "裂缝性油藏控水堵水方法研究与应用", 地质科技情报, no. 05 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118165721A (en) * 2024-05-15 2024-06-11 山东海嘉石油化工有限公司 Organic retarded acid and preparation method and application thereof

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