CN115873572A - Deep penetration cleaning retarding acid deblocking agent and acidification deblocking method - Google Patents
Deep penetration cleaning retarding acid deblocking agent and acidification deblocking method Download PDFInfo
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- CN115873572A CN115873572A CN202211584097.6A CN202211584097A CN115873572A CN 115873572 A CN115873572 A CN 115873572A CN 202211584097 A CN202211584097 A CN 202211584097A CN 115873572 A CN115873572 A CN 115873572A
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- 239000002253 acid Substances 0.000 title claims abstract description 146
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- 230000035515 penetration Effects 0.000 title claims abstract description 28
- 238000004140 cleaning Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000000979 retarding effect Effects 0.000 title claims abstract description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 96
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 86
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 54
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- -1 iron ion Chemical class 0.000 claims abstract description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052742 iron Inorganic materials 0.000 claims abstract description 29
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- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000013543 active substance Substances 0.000 claims abstract description 16
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- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 17
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- 239000002994 raw material Substances 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
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- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 6
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 6
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 5
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- 239000003340 retarding agent Substances 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 239000004711 α-olefin Substances 0.000 claims 1
- 230000000903 blocking effect Effects 0.000 abstract description 44
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
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- 235000019738 Limestone Nutrition 0.000 description 1
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Abstract
The application relates to the technical field of acidification blockage removal, and particularly discloses a deep penetration cleaning retarding acid blockage removal agent and an acidification blockage removal method. The deep penetration cleaning and retarding acid plugging agent comprises a preposed acid and a main acid, wherein the preposed acid comprises hydrochloric acid, acetic acid, an iron ion stabilizer, purified terephthalic acid, a clay stabilizer and water; the main acid comprises hydrochloric acid, acetic acid, ammonium fluoride, a retarder, an iron ion stabilizer, hydroxyethylidene diphosphonic acid, an active agent and water; wherein the retarder comprises citric acid. The blocking remover has the advantages of continuously generating new acid, and having good blocking removing effect and good blocking removing persistence when the blocking removing capability is strong.
Description
Technical Field
The application relates to the field of acidification blockage removal technologies, in particular to a deep penetration cleaning retarding acid blockage removal agent and an acidification blockage removal method.
Background
The acidification blockage removing process technology is an effective measure for removing the pollution of an oil-gas reservoir near a well zone and recovering the production performance of an oil-gas well, and utilizes the chemical corrosion action of acid liquor to dissolve stratum blockage and enlarge or extend stratum fracture holes, so that the permeability of the stratum is recovered and improved, the resistance of oil flowing into the well or the resistance of water injection is reduced, and the purposes of increasing the yield of the oil well and increasing the injection of the water well are achieved.
In the related art, the acidification and blockage removal technologies generally include a hydrochloric acid acidification technology, an earth acid acidification technology, a foam acid acidification technology, a micelle acid acidification technology and an emulsion acid acidification technology; the hydrochloric acid acidification technology and the earth acid acidification technology are widely used, the hydrochloric acid acidification technology usually adopts 15-28% of hydrochloric acid to add additives, and calcium plugs and carbonate calcium cemented rocks are directly dissolved by acid liquor; but the reaction speed with limestone is too high, so that the treatment range is reduced; the earth acid acidification technology is generally prepared by adding hydrofluoric acid and water into hydrochloric acid, but the reaction is violent and rapid, so the cleaning continuity is short, and the blockage removing effect on a deep penetration pipeline is poor.
Disclosure of Invention
In order to obtain a unblocking agent with good unblocking effect and good unblocking persistence, the application provides a deep penetration cleaning slow acid unblocking agent and an acidification unblocking method.
First aspect, the clean retardant acid hydrolysis stifled agent that penetrates deeply that this application provided adopts following technical scheme:
the deep penetration cleaning slow acid deblocking agent comprises preposed acid and main acid, wherein the preposed acid comprises hydrochloric acid, acetic acid, an iron ion stabilizer, purified terephthalic acid, a clay stabilizer and water; the main acid comprises hydrochloric acid, acetic acid, ammonium fluoride, a retarder, an iron ion stabilizer, hydroxyethylidene diphosphonic acid, an active agent and water; wherein the retarder comprises citric acid.
By adopting the technical scheme, the blocking remover is divided into the preposed acid and the main acid, so that on one hand, the preposed acid can firstly remove the blocking object at the front end of the position to be blocked; on the other hand, the hydrochloric acid in the pre-acid which is not completely reacted can participate in the reaction of the main acid.
Hydrochloric acid and acetic acid in the main body acid firstly react with substances at the blockage removal position to remove blockage; the citric acid and the hydrochloric acid can continuously generate acetic acid; the residual hydrochloric acid can further react with ammonium fluoride to generate hydrofluoric acid which reacts with substances at the blockage removal position to continue blockage removal; in thatIn the acidification process, new acid is continuously generated, and the acidification process is multistage. The retarder and the hydroxyethylidene diphosphonic acid can play a role in slowing down the reaction speed, reduce the surface tension of the main acid and ensure that the blockage removal has high blockage removal capacity and good blockage removal continuity. The purpose of adding the iron ion stabilizer is that when the preposed acid and the main acid are unblocked, some iron ions are dissolved, the preposed acid and the main acid are gradually consumed to become residual acid, and when the pH value is increased to 2-3, a large amount of Fe is generated 3+ Form precipitate, and the iron ion stabilizer can prevent Fe from complexing, reducing and dispersing 3+ Reprecipitation of (1).
The blockage removing agent has the advantages of smooth whole blockage removing process, good blockage removing effect and long blockage removing duration.
Optionally, the pre-acid comprises the following raw materials in parts by weight: 9-11 parts of hydrochloric acid, 1-2 parts of acetic acid, 0.2-0.6 part of iron ion stabilizer, 0.5-0.9 part of purified terephthalic acid, 0.05-0.3 part of clay stabilizer and 20-50 parts of water.
By adopting the technical scheme, the hydrochloric acid is used as a main component and is matched with other components, so that the effect of corrosion and blockage removal of the preposed acid on substances at the blockage removal position is better; the addition of the purified terephthalic acid ensures that various components in the pre-acid are better dissolved with each other; the effect is easier to cooperate.
Optionally, the main acid comprises the following raw materials in parts by weight: 10-12 parts of hydrochloric acid, 1-3 parts of acetic acid, 2-5 parts of ammonium fluoride, 1-2 parts of a retarder, 0.3-0.7 part of an iron ion stabilizer, 0.6-1 part of hydroxyethylidene diphosphonic acid, 0.1-0.4 part of an active agent and 20-50 parts of water; the citric acid accounts for 30-50% of the weight of the retarder; the weight parts of the raw materials are based on the weight part of the main acid.
By adopting the technical scheme, the hydrochloric acid is used as a main component and is matched with the ammonium fluoride, so that the hydrochloric acid can react with the ammonium fluoride to generate hydrofluoric acid while being used as a main blockage removal component, and the citric acid in the retarder can react with water to generate acetic acid; the new acid is continuously generated, and the acid forming process is multistage, so the reaction speed is slow, the reaction duration is long, and the effect of deep penetration plugging removal can be achieved. The main acid contains an active agent, can permeate and dissolve heavy hydrocarbon, dissolves oil dirt covered on the surface of rock or inorganic dirt, and can dissolve part of oil dirt into micelles of the active agent, so that organic blockage is removed, and subsequent acid liquor can continuously remove inorganic blockage.
Optionally, the retarder comprises a polymer prepared by polymerizing 2-acrylamido-2-methylpropanesulfonic acid, acrylamide and sodium alpha-alkenyl sulfonate, and citric acid; wherein the molar ratio of the 2-acrylamide-2-methylpropanesulfonic acid to the acrylamide to the alpha-sodium alkenyl sulfonate is 1: (5-10): (0.05-0.2).
By adopting the technical scheme, the acrylamide has good water solubility, and the molecular main chain of the acrylamide can ensure that the retarder molecules have good solubility in acid liquor; the alpha-sodium alkenyl sulfonate has high stability and is used as an emulsifier, so that the retarder has better fluidity and better salt resistance; 2-acrylamide-2-methyl propanesulfonic acid has good salt resistance due to the special chemical structure and molecular structure, so that the retarder molecules still have good retarding performance in mineralized water; therefore, the polymer prepared by polymerizing the alpha-sodium alkenyl sulfonate, the acrylamide and the 2-acrylamido-2-methylpropanesulfonic acid has good stability; in the continuous reaction and heat release process of the main acid, the polymer absorbs heat and continuously generates a chain growth effect, so that the viscosity is higher, the retarding effect is better, and the blockage relieving duration can be further prolonged. The citric acid can participate in the multistage reaction of the main acid, and the effect of slowing down is achieved.
Optionally, an exothermic agent is also included.
By adopting the technical scheme, the exothermic agent is added, on one hand, the higher the temperature of the retarder is, the higher the viscosity is, so that the temperature of the deblocking agent is increased by adding the exothermic agent, the viscosity of the retarder is increased, the fluidity is smaller, the deblocking duration time is prolonged, and the deblocking effect at the same position is improved; on the other hand, after the self temperature of the blocking remover reaches 60 ℃, the blocking remover does not form secondary precipitation, the blocking remover is blocked in a superficial layer of the earth surface, the temperature is lower, and the temperature of the blocking remover can be increased by the exothermic agent.
Optionally, the exothermic agent is concentrated nitric acid.
Through adopting above-mentioned technical scheme, concentrated nitric acid not only can regard as the unblock composition of unblock agent, and concentrated nitric acid meets the water and releases heat for the temperature of whole unblock agent rises, and the viscosity of retardant increases, and mobility is less, increases the duration of unblocking and the unblock effect of same position.
In a second aspect, the acidification deblocking method of the deep penetration cleaning retarding acid deblocking agent provided by the application adopts the following technical scheme:
the acidification blockage removing method of the deep penetration cleaning retarding acidolysis blockage remover comprises the following steps:
step 3, uniformly mixing hydrochloric acid, acetic acid, ammonium fluoride, a retarder, an iron ion stabilizer, hydroxyethylidene diphosphonic acid, an active agent and water to obtain main acid; and continuously pouring the main acid into the position needing to be unblocked for reaction.
By adopting the technical scheme, the reaction in the step 1 leads the front end and the periphery of the blockage removing part to be firstly removed; the purpose of step 2 is to remove the precipitate from the reaction of step 1; step 3, carrying out inner deep blockage removal; and (3) the step 1 and the step 2 are carried out, so that the deep blockage removing effect of the step 3 is good.
Optionally, 1-2L of the front acid in the step 1 is used each time; the volume ratio of the addition amount of the main acid in the step 3 to the volume of the position to be deblocked is 1: (0.5-2).
By adopting the technical scheme, when the blockage removing object is completely blocked, the blockage removing reaction is carried out on the blockage removing object by using the same volume of the main acid, so that the blocked part can be completely removed; the preposed acid rarely participates in deep blockage removal reaction and only removes blockage from the initial end and the periphery of a blockage removal object, so that the adding amount of the preposed acid is 1-2L each time.
Optionally, the acidification deblocking method of the deep penetration cleaning retarded acid deblocking agent includes the following steps:
step 3, uniformly mixing hydrochloric acid, acetic acid, ammonium fluoride, a retarder, an iron ion stabilizer, hydroxyethylidene diphosphonic acid, an active agent and water to obtain main acid; continuously pouring the main acid into the position needing to be unblocked for reaction;
and 4, immediately pouring the exothermic agent after pouring the main acid.
Through adopting above-mentioned technical scheme, increase step 4's aim at, because exothermic agent meets water and just releases heat, consequently, pour into main part acid, add exothermic agent immediately, exothermic agent will release heat in the inside of deblocking department, and because deblocking department is generally seal structure such as pipeline, a large amount of heats can be preserved, increase the viscosity of retardant in the reaction process, increase the mobility of whole deblocking agent, the extension deblocking time.
Optionally, the volume ratio of the exothermic agent to the host acid is (0.05-0.1): 1.
by adopting the technical scheme, the exothermic agent accounts for about 10 percent of the main acid, so that the temperature which can be increased by the exothermic agent is 10-20 ℃; when the underground shallow layer is unblocked, a heat releasing agent is not added, the temperature is 30-40 ℃, the heat releasing agent is added, so that the overall temperature reaches over 50 ℃, the reaction can be completed after the blockage is unblocked at high temperature, and almost no solid residue exists.
In summary, the present application has the following beneficial effects:
1. in the application, hydrochloric acid and acetic acid in main acid firstly react with substances at a blockage removal part to remove blockage; the citric acid and the hydrochloric acid can continuously generate acetic acid; the residual hydrochloric acid can further react with ammonium fluoride to generate hydrofluoric acid which reacts with substances at the blockage removal position, and in the acidification process, new acid is continuously generated, and the acid formation process is multistage, so that the blockage removal capability is strong, and the blockage removal continuity is good;
2. in the retarder, acrylamide is good in water solubility; the alpha-sodium alkenyl sulfonate has high stability, is used as an emulsifier, has better fluidity and better salt resistance; 2-acrylamide-2-methyl propanesulfonic acid has good salt resistance, so that the retarder molecules still have good retarding performance in mineralized water; therefore, the polymer prepared by polymerizing the alpha-sodium alkenyl sulfonate, the acrylamide and the 2-acrylamido-2-methylpropanesulfonic acid has good stability and good retarding performance;
3. in the acidification blockage removing method, the step 4 is added, the main acid is poured in, the heat releasing agent is added immediately, the heat releasing agent releases heat in the blockage removing position, and the blockage removing position is generally a sealing structure such as a pipeline, a large amount of heat can be stored, the viscosity of the retarder is increased in the reaction process, the fluidity of the whole blockage removing agent is increased, and the blockage removing time is prolonged.
Drawings
Fig. 1 is intended to show the erosion rate of the deblocking agent of example 3 and comparative examples 3, 4, 5, 6 to the core as a function of time;
fig. 2 is intended to show the fracture rate of the deblocking agent of example 3 and comparative example 5 for the core;
FIG. 3 is intended to show the state of lateral penetration of the deblocking agent of example 3 with the deblocking agent of comparative example 5;
FIG. 4 is a diagram for showing the state of the blocking remover before, during and after blocking removal.
Detailed Description
The present application will be described in further detail with reference to examples and comparative examples.
The following examples and comparative examples are provided as raw material sources: the raw materials of the examples and the comparative examples are all commercially available, and CX-30B low-foaming surfactant is used as the active agent; the clay stabilizer is polyacrylamide clay stabilizer; the hydrochloric acid concentration was 37% and the acetic acid concentration was 10%.
Preparation example of retarder
Preparation example 1
Preparation of polymer: weighing 10mol of acrylamide, 1mol of 2-acrylamido-2-methylpropanesulfonic acid and 0.05mol of alpha-sodium alkenylsulfonate into a beaker, adding 25mL of water, stirring for dissolving, preparing a sodium hydroxide solution, adjusting the pH value of the solution, and adjusting the pH value to 8 to obtain a mixed solution; after the reaction is finished, adding the mixed solution into a three-neck flask, setting the temperature of a constant-temperature water bath kettle to be 60 ℃, weighing 0.3g of potassium persulfate serving as an initiator, adding the potassium persulfate into the three-neck flask, opening a stirrer for stirring, introducing nitrogen into the mixed solution for 30min, stopping introducing the nitrogen after the solution is sticky, and continuously reacting for 20min to obtain a polymer;
preparing a retarder: and (3) mixing citric acid and the polymer uniformly, and stirring to obtain the retarder, wherein the weight ratio of the citric acid to the polymer is 1.
Preparation example 2
The difference from preparation example 1 is that the following raw materials for polymer preparation were added in different amounts; specifically 5mol of acrylamide, 1mol of 2-acrylamido-2-methylpropanesulfonic acid and 0.2mol of alpha-sodium alkenylsulfonate.
Preparation example 3
The difference from preparation example 1 was that the following raw materials for the polymer preparation were added in different amounts; specifically 7mol of acrylamide, 1mol of 2-acrylamide-2-methylpropanesulfonic acid and 0.1mol of alpha-sodium alkenyl sulfonate;
preparation example 4
The difference from preparation example 1 is that the retarder is prepared differently; the weight ratio of citric acid to polymer was 3.
Preparation example 5
The difference from preparation example 1 is that the retarder is prepared differently; the weight ratio of citric acid to polymer was 4.
Comparative preparation example 1
The difference from preparation example 1 is that the retarder is prepared differently; citric acid is not added into the retarder.
Examples of deep penetration cleaning of retarded acid deblocking agent
Example 1
The acidification deblocking method of the deep penetration cleaning retarding acid deblocking agent comprises the following steps:
step 3, uniformly mixing 100kg of hydrochloric acid, 30kg of acetic acid, 20kg of ammonium fluoride, 20kg of the retarder prepared in preparation example 1, 3kg of iron ion stabilizer 2066A, 10kg of hydroxyethylidene diphosphonic acid, 1kg of active agent and 500kg of water to obtain main acid; the volume of the main body acid is configured to be the same as that of the blockage removal rock core; and continuously pouring the main acid into the position to be unblocked, and reacting until the residual acid is completely flowed out and the blocking object is removed visually.
Example 2
The acidification deblocking method of the deep penetration cleaning retarding acid deblocking agent comprises the following steps:
step 3, uniformly mixing 120kg of hydrochloric acid, 10kg of acetic acid, 50kg of ammonium fluoride, 10kg of the retarder prepared in preparation example 2, 7kg of iron ion stabilizer 2066A, 6kg of hydroxyethylidene diphosphonic acid, 4kg of active agent and 200kg of water to obtain main acid; configuring the volume of the main body acid to be the same as that of the blockage removal rock core; and continuously pouring the main acid into the position to be unblocked, and reacting until the residual acid is completely flowed out and the blocking object is removed visually.
Example 3
The acidification blockage removing method of the deep penetration cleaning retarding acidolysis blockage remover comprises the following steps:
step 3, uniformly mixing 110kg of hydrochloric acid, 20kg of acetic acid, 40kg of ammonium fluoride, 15kg of the retarder prepared in preparation example 3, 5kg of iron ion stabilizer 2066A, 8kg of hydroxyethylidene diphosphonic acid, 2kg of active agent and 350kg of water to obtain main acid; the volume of the main body acid is configured to be the same as that of the blockage removal rock core; and continuously pouring the main acid into the position to be unblocked, and reacting until the residual acid is completely flowed out and the blocking object is removed visually.
Example 4
The difference from example 3 is that the retarder obtained in preparation example 4 was used in step 3.
Example 5
The difference from example 3 is that the retarder obtained in preparation example 5 was used in step 3.
Example 6
The acidification deblocking method of the deep penetration cleaning retarding acid deblocking agent comprises the following steps:
step 3, uniformly mixing 110kg of hydrochloric acid, 20kg of acetic acid, 40kg of ammonium fluoride, 15kg of the retarder prepared in preparation example 3, 5kg of iron ion stabilizer, 8kg of hydroxyethylidene diphosphonic acid, 2kg of active agent and 350kg of water to obtain main acid; the volume of the main body acid is configured to be the same as that of the blockage removal rock core; continuously pouring the main acid into the position needing to be unblocked for reaction;
Comparative example 1
Except for using the retarder prepared in comparative preparation example 1 in step 3.
Comparative example 2
The difference from example 3 is that no retarder was added to the host acid.
Comparative example 3
The formula of the blocking remover purchased in the market is as follows: the 12% HC1+5% of the content of HAc +3% of HBF4+1% of HF, the rest of the proportion being water.
Comparative example 4
The formula of the blocking remover purchased in the market is as follows: 12% of HCl +3% of HBF4+1% of HF, the rest being water.
Comparative example 5
The formula of the blocking remover purchased in the market is as follows: 12% HCl +3% HF, the rest being water.
Comparative example 6
The blocking remover purchased on the market has the following formula: 12% of H3PO4+3% of HF, the balance being water.
Performance test
The blocking remover prepared in the examples 1 to 6 and the comparative examples 1 to 6 is used for performance test, and the corrosion rate variation of the rock core is detected for 8h to 10 h; the calculation method comprises the following steps: (core mass before experiment-core mass after experiment)/core mass before experiment x 100%, the test results are shown in table 1;
the change of the corrosion rate of the blocking remover of the example 3 and the comparative examples 3, 4, 5 and 6 on the rock core along with time is detected, and the test result is shown in the attached figure 1 of the specification;
detecting the breaking rate of the blocking remover of example 3 and comparative example 5 on the rock core; the calculation method comprises the following steps: (original weight of the core-weight of rock debris sieved by a standard sieve of 0.56 mm)/original weight of the core multiplied by 100%, and the test result is shown in the attached figure 2 of the specification;
the self-precipitation amount of the main acid in the blocking remover prepared in the embodiments 1, 2 and 3 at different time and different temperature is detected, and the detection results are shown in the following table 2;
TABLE 1
TABLE 2
By combining examples 1 and 2 and example 3, it can be seen that the corrosion rates of 8h to 10h in table 1 are all 3.3-3.5%, and the corrosion rate of the core is relatively high, which proves that the raw material dosage ratios of examples 1 and 2 and example 3 are reasonable within the protection scope of the claims of the application; the effect of the durable corrosion of the rock core is better. As can be seen from table 2, although the raw material ratio has an effect on the self-precipitation of the blocking remover, the effect is small; the temperature has great influence on the self-precipitation of the blocking remover, the higher the temperature is, the less the self-precipitation of the blocking remover is, and the blocking remover does not generate self-precipitation when the temperature reaches 60 ℃; it was demonstrated that the secondary precipitation can be eliminated by increasing the reaction temperature.
Combining examples 3 and 4 and 5, it can be seen that example 3 in table 1 is different from examples 4 and 5 only in that the ratio of the polymer in the retarder to the citric acid is 1,7.
By combining examples 3 and 6, it can be seen that example 6 in table 1 is different from example 3 in that step 4 is added in example 6, and a step of adding concentrated nitric acid is added, and the corrosion rate of the blocking remover prepared in example 6 on the core from 8h to 10h is greater than that of the blocking remover prepared in example 3 on the core from 8h to 10 h; proved by the fact that the increase of the concentrated nitric acid is beneficial to promoting the duration of the dissolution and corrosion of the rock core by the blocking remover. And the table 2 is combined, so that the higher the temperature is, the smaller the self-precipitation quality of the blocking remover is, secondary precipitation cannot be formed, the damage to the core framework is small, and the retarding performance is good.
By combining example 3 and comparative examples 1 and 2, it can be seen that the corrosion rate change of 8h to 10h in example 3 is greater than that of comparative examples 1 and 2 compared to example 3 when citric acid is not added to the retarder of comparative example 1 in table 1 and the retarder is not added directly to comparative example 2; the addition of the retarder component and the retarder is proved to be very important for the blockage removing effect of the blockage removing agent.
By combining example 3 and comparative examples 3, 4, 5 and 6, it can be seen that comparative examples 3, 4, 5 and 6 are all commercial deblocking agents composed of different acids without adding retarders, and the change of the corrosion rate of 8h to 10h in comparative examples 3, 4, 5 and 6 is much smaller than that of example 3; the formula of the blocking remover is proved to have better continuous blocking removal effect on the rock core compared with other commercially available blocking removers.
In the corrosion curve, the plugging removal agents of comparative examples 3, 4, 5 and 6 have high corrosion rate and corrosion rate at the initial stage of the core, but the retarding effect is not obvious, and after 8 hours, the corrosion rate is almost not changed, so that deep acidizing plugging removal cannot be realized. With reference to the accompanying drawing 1 (b) of the specification, on the premise that the corrosion rate of the blocking remover in embodiment 3 of the present application is high, 37.1% of the corrosion rate can be achieved within 12 hours, and the corrosion rate changes relatively smoothly, so that the requirement of retarded and durable acidification can be met.
With reference to the attached figure 2 of the specification, it can be seen that the crushing rate of the blocking remover of the comparative example 5 is far less than that of the blocking remover of the example 3 of the application; proved that the blocking remover has good corrosion effect on the rock core.
In conjunction with the accompanying fig. 3 of the specification, it can be seen that the deblocking agent of example 3 has a greater lateral penetration capacity than the deblocking agent of comparative example 5.
In the description, fig. 4 is combined, and it can be seen that the top three figures are in a macroscopic state, and the bottom six figures are in a microscopic state; the blocking remover before blocking removal is in a liquid state; the blocking remover obviously becomes viscous when blocking is removed; the blocking remover after blocking removal is residual acid and is in a liquid state.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The deep penetration cleaning slow acid deblocking agent is characterized by comprising a preposed acid and a main acid, wherein the preposed acid comprises hydrochloric acid, acetic acid, an iron ion stabilizer, purified terephthalic acid, a clay stabilizer and water; the main acid comprises hydrochloric acid, acetic acid, ammonium fluoride, a retarder, an iron ion stabilizer, hydroxyethylidene diphosphonic acid, an active agent and water; wherein the retarder comprises citric acid.
2. The deep penetration cleaning retarding acid plugging agent as claimed in claim 1, wherein the pre-acid comprises the following raw materials in parts by weight: 9-11 parts of hydrochloric acid, 1-2 parts of acetic acid, 0.2-0.6 part of iron ion stabilizer, 0.5-0.9 part of purified terephthalic acid, 0.05-0.3 part of clay stabilizer and 20-50 parts of water.
3. The deep penetration cleaning retarding acid plugging agent as claimed in claim 1, wherein the main acid comprises the following raw materials in parts by weight: 10-12 parts of hydrochloric acid, 1-3 parts of acetic acid, 2-5 parts of ammonium fluoride, 1-2 parts of a retarder, 0.3-0.7 part of an iron ion stabilizer, 0.6-1 part of hydroxyethylidene diphosphonic acid, 0.1-0.4 part of an active agent and 20-50 parts of water; the citric acid accounts for 30-50% of the weight of the retarder; the weight parts of the raw materials are based on the weight parts of the main acid.
4. The deep penetration cleaning retarding acid plugging agent as claimed in claim 1, wherein the retarding agent comprises a polymer prepared by polymerizing 2-acrylamido-2-methylpropanesulfonic acid, acrylamide and sodium α -olefin sulfonate, and citric acid; wherein the molar ratio of the 2-acrylamide-2-methylpropanesulfonic acid to the acrylamide to the alpha-sodium alkenyl sulfonate is 1: (5-10): (0.05-0.2).
5. The deep penetration cleaning retarded acid plugging agent according to claim 1 further comprising an exothermic agent.
6. The deep penetration cleaning retarded acid plugging agent according to claim 5, wherein said exothermic agent is concentrated nitric acid.
7. An acidification deblocking method of deep penetration cleaning retarded acid deblocking agent according to any one of claims 1 to 4, characterized by comprising the steps of:
step 1, uniformly mixing hydrochloric acid, acetic acid, an iron ion stabilizer, purified terephthalic acid, a clay stabilizer and water to obtain a pre-acid; pouring preposed acid into a position needing to be unblocked to react;
step 2, carrying out water washing after the pre-acid reaction is carried out for 20-50 min;
step 3, uniformly mixing hydrochloric acid, acetic acid, ammonium fluoride, a retarder, an iron ion stabilizer, hydroxyethylidene diphosphonic acid, an active agent and water to obtain main acid; and continuously pouring the main acid into the position to be unblocked for reaction.
8. The acidification deblocking method of the deep penetration cleaning retarded acid deblocking agent according to claim 7, characterized in that the pre-acid of step 1 is used 1-2L each time; the volume ratio of the addition amount of the main acid in the step 3 to the volume of the position to be deblocked is 1: (0.5-2).
9. The acidification deblocking method of the deep penetration cleaning retarded acid deblocking agent according to claim 5 or 6, characterized by comprising the following steps:
step 1, uniformly mixing hydrochloric acid, acetic acid, an iron ion stabilizer, purified terephthalic acid, a clay stabilizer and water to obtain a preposed acid; pouring the preposed acid into a position needing to be unblocked for reaction;
step 2, carrying out water washing after the pre-acid reaction is carried out for 20-50 min;
step 3, uniformly mixing hydrochloric acid, acetic acid, ammonium fluoride, a retarder, an iron ion stabilizer, hydroxyethylidene diphosphonic acid, an active agent and water to obtain main acid; continuously pouring the main acid into the position needing to be unblocked for reaction;
and 4, immediately pouring the exothermic agent after pouring the main acid.
10. The method as claimed in claim 9, wherein the volume ratio of exothermic agent to main acid is (0.05-0.1): 1.
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| CN202211584097.6A CN115873572A (en) | 2022-12-10 | 2022-12-10 | Deep penetration cleaning retarding acid deblocking agent and acidification deblocking method |
| CN202311683167.8A CN117777974A (en) | 2022-12-10 | 2023-12-09 | Deep penetration clean retarded acidolysis blocking remover and acidification blocking removing method |
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| CN202311683167.8A Pending CN117777974A (en) | 2022-12-10 | 2023-12-09 | Deep penetration clean retarded acidolysis blocking remover and acidification blocking removing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103740353A (en) * | 2013-12-16 | 2014-04-23 | 中国石油化工股份有限公司 | Composite blocking remover and method for removing blockage of compact sandstone reservoir pressing crack commissioning horizontal well in composite manner |
| CN106811186A (en) * | 2017-01-12 | 2017-06-09 | 大庆市杰森钻采助剂厂 | A kind of acidification blocking remover |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103740353A (en) * | 2013-12-16 | 2014-04-23 | 中国石油化工股份有限公司 | Composite blocking remover and method for removing blockage of compact sandstone reservoir pressing crack commissioning horizontal well in composite manner |
| CN106811186A (en) * | 2017-01-12 | 2017-06-09 | 大庆市杰森钻采助剂厂 | A kind of acidification blocking remover |
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