CN113755149A - Self-generated acid crosslinking fracturing fluid and application thereof - Google Patents
Self-generated acid crosslinking fracturing fluid and application thereof Download PDFInfo
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- 239000012530 fluid Substances 0.000 title claims abstract description 50
- 238000004132 cross linking Methods 0.000 title claims abstract description 23
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000011435 rock Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002562 thickening agent Substances 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 18
- 239000012190 activator Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 14
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 14
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 12
- 229920002866 paraformaldehyde Polymers 0.000 claims description 12
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- 229940116333 ethyl lactate Drugs 0.000 claims description 7
- 239000004310 lactic acid Substances 0.000 claims description 7
- 235000014655 lactic acid Nutrition 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 150000003754 zirconium Chemical class 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
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- 238000000034 method Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 6
- 239000012085 test solution Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- -1 hydrogen ions Chemical class 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
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- 238000010008 shearing Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
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- 229920001744 Polyaldehyde Polymers 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
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- 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
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
- C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
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- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
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- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
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- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
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Abstract
The invention relates to a self-generated acid crosslinking fracturing fluid and application thereof. The fracturing fluid comprises a thickening agent, a cross-linking agent, an acid generator, an activator and water, wherein the thickening agent accounts for 0.6-1% of the total mass of the self-acid-generating cross-linking fracturing fluid, the cross-linking agent accounts for 0.6-1%, the acid generator accounts for 40-45%, the activator accounts for 8-10%, and the water accounts for 45-50%. It can be used in carbonate acid fracturing, especially in high-temperature carbonate rock at 130-150 deg.C.
Description
Technical Field
The invention relates to a self-generated acid crosslinking fracturing fluid, in particular to an application of the self-generated acid crosslinking fracturing fluid in carbonate rock acid fracturing.
Background
Acid fracturing is one of the main production and injection increasing measures used in low-permeability oil and gas fields at home and abroad. The carbonate rock oil and gas reservoir newly found at home and abroad has the characteristics of deep burial, high temperature and the like, so that the acid rock reaction speed is high and the acid corrosion effective distance is short in the acid fracturing process, and the acid fracturing modification effect is severely restricted.
At present, one of the main means for solving the problems is to increase the viscosity of the acid liquor, namely, the increase of the viscosity is utilized to reduce the convection effect of the acid liquor in the artificial fracture and reduce the mass transfer rate of hydrogen ions in the acid liquor, thereby reducing the reaction rate of acid rock. The viscosity of the acid liquor is increased to meet the requirement of reducing the reaction rate of acid rocks to a certain extent, but in the face of the development of deep carbonate rocks with the temperature of more than 140 ℃ such as Tahe and Tarim, the effective action distance of the high-viscosity acid liquor only reaches 70-100m, and the acid liquor penetration distance or the transformation range cannot be further increased.
Patent application No. 201611191123.3 provides a fracturing fluid capable of self-generating acid, a preparation method and application thereof, which is composed of organic ester, thickening agent and degradable fluid loss additive. The fracturing fluid not only meets the filtration loss reduction performance of the water-based fracturing fluid and carries out fracturing and crack formation, but also can slowly generate acid under the high-temperature condition of the stratum to acid-corrode the stratum, thereby realizing effective acid corrosion of the front section of the crack. But the method has the defects that the acid liquid is a non-crosslinking self-generating acid system and cannot meet the viscosity retention characteristic of the deep well reservoir under long-time shearing. Patent application No. 201510342102.6 provides a composite acid fracturing process for high temperature deep well carbonate reservoirs with a self-generated acid composition of 50% polyaldehydes + 50% ammonium salts. But has the disadvantage that the viscosity of the produced acid is low and cannot enter deep strata.
In summary, when the existing authigenic acid system is applied to a deep carbonate reservoir, the viscosity-shear resistance is poor, and the viscosity-temperature performance and the slow-generation acidity performance of authigenic acid cannot be considered at the same time, so that the authigenic acid cannot enter the deep reservoir. Therefore, in order to meet the technical requirements of deep acid fracturing of carbonate rocks, particularly for the development of the carbonate rocks with deeper burial depth and higher temperature, the invention needs to invent the self-generated acid crosslinking fracturing fluid so as to improve the acid fracturing effect of the deep carbonate rocks such as Tahe, Tarim and the like.
Disclosure of Invention
The invention provides an acid-generating crosslinking fracturing fluid which comprises a thickening agent, a crosslinking agent, an acid generator, an activator and water, wherein the thickening agent accounts for 0.6-1% of the total mass of the acid-generating crosslinking fracturing fluid, the crosslinking agent accounts for 0.6-1%, the acid generator accounts for 40-45%, the activator accounts for 8-10%, and the water accounts for 45-50%.
In one embodiment, the thickener is prepared from acrylamide and sodium 2-acrylamido-2-methyl-propanesulfonate in a mass ratio (1.5 to 2): 1 through copolymerization.
In one embodiment, the weight average molecular weight of the thickener is from 600 to 800 ten thousand.
In one embodiment, the cross-linking agent is a mixture of lactic acid, methanol, a zirconium salt (e.g., zirconium oxychloride), triethanolamine, and water.
In one embodiment, the lactic acid is present in an amount of 2% to 3%, the methanol is present in an amount of 2% to 3%, the zirconium salt (e.g., zirconium oxychloride) is present in an amount of 2% to 3%, the triethanolamine is present in an amount of 2% to 3%, and the water is present in an amount of 88% to 92%, based on 100% total mass of the crosslinking agent.
In one embodiment, the acid generator is a mixture of ethyl lactate, ethyl acetate, and methanol.
In a specific embodiment, the content of the ethyl lactate is 40% to 45%, the content of the ethyl acetate is 40% to 45%, and the content of the methanol is 10% to 20% based on 100% of the total mass of the acid generator.
In one embodiment, the activator is a mixture of paraformaldehyde and ammonium chloride.
In one embodiment, the relative molecular weight of the paraformaldehyde is from 240 to 900.
In one embodiment, the mass ratio of paraformaldehyde to ammonium chloride is 1: (0.9 to 1). The second invention provides the application of the self-generated acid crosslinking fracturing fluid in carbonate rock acid fracturing.
In a specific embodiment, the carbonate rock is a high temperature carbonate rock at 130 ℃ to 150 ℃, for example, a high temperature carbonate rock at 140 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) the self-generated acid crosslinking fracturing fluid can be suitable for the acid fracturing of a high-temperature deep carbonate reservoir. The self-acid-generating cross-linking fracturing fluid can enter a stratum fracture through a pump of a ground pump truck, the filtration loss is reduced by utilizing the high viscosity characteristic of the self-acid-generating cross-linking fracturing fluid to extend an artificial main fracture channel to the maximum extent, and hydrogen ions are slowly released after entering the deep part of the fracture by utilizing the characteristic of low acid generation rate of self-acid generation, so that an acid-etched fracture channel is formed by etching the wall surface of the fracture. Compared with the prior art, the method has stronger applicability and can be applied to the high-temperature deep-crack type carbonate reservoir transformation process.
(2) The autogenous acid crosslinking fracturing fluid of the invention has better rheological property.
(3) The autogenous acid crosslinking fracturing fluid can keep better viscosity characteristics under high shear rate. Therefore, compared with the prior art, the composite material has the characteristic of higher shear resistance.
(4) The self-acid-generating crosslinking fracturing fluid has stronger temperature resistance, and the temperature resistance is over 140 ℃. Therefore, compared with the prior art, the method is more suitable for the acid fracturing of the carbonate rock buried deeper.
Drawings
FIG. 1 shows the autogenous acid crosslinked fracturing fluid prepared in example 1 at a constant temperature of 140 ℃ and a constant shear rate of 170s-1Viscosity change with shear for 2 h.
FIG. 2 shows the autogenous acid crosslinked fracturing fluid prepared in example 2 at a constant temperature of 140 ℃ and a constant shear rate of 170s-1Viscosity change at 2h shear
FIG. 3 shows the autogenous acid crosslinked fracturing fluid prepared in example 3 at a constant temperature of 140 deg.C and a constant shear rate of 170s-1Viscosity change at 2h shear
FIG. 4 shows the autogenous acid crosslinked fracturing fluid prepared in example 4 at a constant temperature of 140 deg.C and a constant shear rate of 170s-1Viscosity change at 2h shear
FIG. 5 shows the autogenous acid crosslinked fracturing fluid prepared in example 5 at a constant temperature of 140 deg.C and a constant shear rate of 170s-1Viscosity change with shear for 2 h.
Detailed Description
The above-described aspects of the invention are explained in more detail below by means of preferred embodiments, but they are not intended to limit the invention.
The reagents in the examples of the present invention were all commercially available unless otherwise specified.
Example 1
A thickening agent: acrylamide and 2-acrylamido-2-methyl-sodium propane sulfonate are mixed according to a mass ratio of 2: 1, and the weight average molecular weight of the thickening agent is 800 ten thousand.
A crosslinking agent: lactic acid, methanol, zirconium oxychloride, triethanolamine and clear water in a mass ratio of 3: 2: 3: 2: 90 are mixed together.
An acid generator: ethyl lactate, ethyl acetate and methanol in a mass ratio of 2: 2: 1 are mixed.
Activating agent: the composite material is prepared from paraformaldehyde and ammonium chloride according to a mass ratio of 1: 1 are mixed. Wherein the molecular weight of the paraformaldehyde is 240 to 900.
Clear water, a thickening agent, a cross-linking agent, an acid generating agent and an activating agent are mixed according to the mass percentage of 50.4: 0.8: 0.8: 40: 8, mixing to obtain the self-generated acid crosslinked fracturing fluid No. 1.
Example 2
Clear water, a thickening agent, a cross-linking agent, an acid generating agent and an activating agent are mixed according to the mass percentage of 43: 1.0: 1.0: 45: 10 to obtain the self-generated acid crosslinked fracturing fluid No. 2. The rest is the same as example 1.
Example 3
Clear water, a thickening agent, a cross-linking agent, an acid generating agent and an activating agent are mixed according to the mass percentage of 50: 0.6: 0.6: 40: 8.8 to obtain the self-generated acid crosslinked fracturing fluid No. 3. The rest is the same as example 1.
Example 4
A thickening agent: acrylamide and 2-acrylamido-2-methyl-sodium propane sulfonate are mixed according to a mass ratio of 1.5: 1, and the weight-average molecular weight of the thickening agent is 600 ten thousand.
A crosslinking agent: lactic acid, methanol, zirconium oxychloride, triethanolamine and clear water in a mass ratio of 3: 3: 3: 3: 88, and mixing.
An acid generator: ethyl lactate, ethyl acetate and methanol in a mass ratio of 2: 2: 1 are mixed.
Activating agent: the composite material is prepared from paraformaldehyde and ammonium chloride according to a mass ratio of 1: 0.9, and mixing. Wherein the molecular weight of the paraformaldehyde is 240 to 900.
Clear water, a thickening agent, a cross-linking agent, an acid generating agent and an activating agent are mixed according to the mass percentage of 50: 0.8: 0.8: 40.4: 8, mixing to obtain the autogenous acid crosslinked fracturing fluid No. 4.
Example 5
A thickening agent: acrylamide and 2-acrylamido-2-methyl-sodium propane sulfonate are mixed according to a mass ratio of 2: 1, and the molecular weight of the thickening agent is 700 ten thousand.
A crosslinking agent: lactic acid, methanol, zirconium oxychloride, triethanolamine and clear water in a mass ratio of 2: 2: 2: 2: 92 are mixed together.
An acid generator: ethyl lactate, ethyl acetate and methanol in a mass ratio of 9: 9: 2, mixing the components.
Activating agent: the composite material is prepared from paraformaldehyde and ammonium chloride according to a mass ratio of 1: 1 are mixed. Wherein the molecular weight of the paraformaldehyde is 240 to 900.
Clear water, a thickening agent, a cross-linking agent, an acid generating agent and an activating agent are mixed according to the mass percentage of 50: 0.8: 0.8: 40.4: 8, mixing to obtain the self-generated acid crosslinked fracturing fluid No. 5.
Comparative example 1
Thickening acid: polyacrylamide (having a relative molecular weight of 800 ten thousand) having a degree of hydrolysis of 15%, hydrochloric acid having a mass concentration of 36%, and water were mixed at a ratio of 0.7: 49: 50.3 by mass ratio.
Comparative example 2
Crosslinking acid: firstly, mixing polyacrylamide with the hydrolysis degree of 15% (relative molecular weight is 800 ten thousand), hydrochloric acid with the mass concentration of 36% and water in a proportion of 0.7: 49: 50.3, and preparing the thickening acid; preparing an organic zirconium aqueous solution: the mass ratio of zirconium oxychloride, methanol, triethanolamine and water is 3: 3: 5: 89; the gelled acid was then mixed with an aqueous organozirconium solution at a ratio of 98.5: 1.5, and preparing the crosslinking acid.
Example 6
Rheological Property test
The evaluation method comprises the following steps:
(1) the MARSIII rheometer was set at a constant temperature of 140 ℃ and a constant shear rate of 170s-1；
(2) The autogenous acid crosslinked fracturing fluids of examples 1 to 5 were placed in a shear cylinder of a rheometer and sheared for 2 hours to test the viscosity change of the autogenous acid crosslinked fracturing fluids. The results are shown in FIGS. 1 to 5.
As can be seen from the test data in FIG. 1, the autogenous acid crosslinked fracturing fluid of the invention lasts for 170s at 140 DEG C-1The viscosity is still more than 200 mPa.s after shearing for 2h, which shows that the liquid of the invention has high viscosity, strong anti-shearing capability and good temperature resistance.
Example 7
Corrosion inhibition performance test
And (3) testing the corrosion inhibition of the autogenous acid crosslinking fracturing fluid by adopting a coupon corrosion method.
The evaluation method comprises the following specific steps:
(1) the autogenous acid crosslinked fracturing fluids prepared in examples 1 to 5 were warmed to 90 ℃;
(2) placing a metal hanging sheet made of N80 into the autogenous acid crosslinking fracturing fluid, keeping the temperature at 90 ℃, and statically corroding for 4 hours;
(3) the mass of the metal coupon before and after corrosion was measured, and the corrosion rate, i.e., (mass before reaction-mass after reaction)/surface area before reaction/time, was calculated. The results are shown in Table 1.
TABLE 1
As can be seen from the test data in Table 1, the corrosion rate of the autogenous acid crosslinked fracturing fluid of the invention at 90 ℃ is 1.67 g/(m)2H) satisfies 10 g/(m)2H) the following industry standard requirements.
Example 8
Acid rock reaction rate test
The plug size of the carbonate core used was 25mm x 20mm, and the acid rock reaction rates of the autogenous acid crosslinked fracturing fluids of examples 1 to 5, the gelled acid of comparative example 1, and the crosslinked acid of comparative example 2 were tested on the carbonate core by acid rock reaction experiments.
The evaluation method comprises the following steps:
(1) respectively heating the test solutions to 140 ℃, and then injecting the test solutions into a reaction kettle to contact and react with the carbonate rock core;
(2) stirring the test solution and the carbonate rock core to continuously react for 5min at the constant temperature of 140 ℃;
(3) the concentration change of hydrogen ions in the test solution before and after the test reaction is carried out, and the reaction rate of the acid rock is calculated, wherein the reaction rate is (the mole number of the hydrogen ions in the test solution before the reaction-the mole number of the hydrogen ions in the test solution after the reaction)/the surface area before the reaction/time. The test results are shown in Table 2.
TABLE 2
From the test data in table 2, it can be seen that the autogenous acid crosslinked fracturing fluid of the present invention has the lowest acid rock reaction rate, which is beneficial to increasing the effective action distance of acid corrosion and entering the deep part of the fracture for acid corrosion.
Claims (10)
1. The self-acid-generating crosslinking fracturing fluid comprises a thickening agent, a crosslinking agent, an acid generator, an activator and water, wherein the thickening agent accounts for 0.6-1% of the total mass of the self-acid-generating crosslinking fracturing fluid, the crosslinking agent accounts for 0.6-1%, the acid generator accounts for 40-45%, the activator accounts for 8-10%, and the water accounts for 45-50%.
2. The autogenous acid crosslinked fracturing fluid of claim 1, wherein the thickener consists of acrylamide and sodium 2-acrylamido-2-methyl-propanesulfonate in a mass ratio of (1.5 to 2): 1 through copolymerization.
3. The autogenous acid crosslinked fracturing fluid of claim 2, wherein the weight average molecular weight of the viscosifier is from 600 to 800 ten thousand.
4. The autogenous acid crosslinked fracturing fluid of any one of claims 1 to 3, wherein the crosslinking agent is a mixture of lactic acid, methanol, zirconium salt, triethanolamine, and water.
5. The autogenous acid crosslinked fracturing fluid of claim 4, wherein the lactic acid is present in an amount of 2% to 3%, the methanol is present in an amount of 2% to 3%, the zirconium salt is present in an amount of 2% to 3%, the triethanolamine is present in an amount of 2% to 3%, and the water is present in an amount of 88% to 92%, based on 100% by mass of the total crosslinking agent.
6. The self-acid-generating crosslinked fracturing fluid of any one of claims 1 to 5, wherein the acid generator is a mixture of ethyl lactate, ethyl acetate and methanol.
7. The self-acid-generating crosslinked fracturing fluid of claim 6, wherein the ethyl lactate is 40 to 45%, the ethyl acetate is 40 to 45%, and the methanol is 10 to 20% based on 100% of the total mass of the acid generator.
8. The autogenous acid crosslinked fracturing fluid of any one of claims 1 to 7, wherein the activator is a mixture of paraformaldehyde and ammonium chloride; preferably, the relative molecular weight of the paraformaldehyde is 240 to 900.
9. The self-generating acid crosslinked fracturing fluid of claim 8, wherein the mass ratio of paraformaldehyde to ammonium chloride is 1: (0.9 to 1).
10. Use of an autogenous acid crosslinked fracturing fluid according to any one of claims 1 to 9 in carbonate acid fracturing, preferably the carbonate is high temperature carbonate at 130 ℃ to 150 ℃; preferably, the carbonate rock is a high temperature carbonate rock at 140 ℃.
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