CN111187607B - Temperature response type hydrogel temporary plugging diversion fracturing fluid and preparation method and application thereof - Google Patents
Temperature response type hydrogel temporary plugging diversion fracturing fluid and preparation method and application thereof Download PDFInfo
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- CN111187607B CN111187607B CN201910637568.7A CN201910637568A CN111187607B CN 111187607 B CN111187607 B CN 111187607B CN 201910637568 A CN201910637568 A CN 201910637568A CN 111187607 B CN111187607 B CN 111187607B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/514—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/90—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
- C09K8/905—Biopolymers
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- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/13—Methods or devices for cementing, for plugging holes, crevices, or the like
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- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
Abstract
The invention relates to the technical field of hydraulic fracturing, and provides a temperature response type hydrogel temporary plugging diversion fracturing fluid and a preparation method and application thereof, aiming at solving the problems that the existing fracturing fluid is poor in temperature resistance, gel breaking and leakage are easy to occur in the fracturing process, and polymer residues are damaged on a stratum, wherein the temperature response type hydrogel temporary plugging diversion fracturing fluid consists of the following components in percentage by mass: 0.2-1.2% of chitosan, 4-10% of chitosan oligosaccharide, 1.1-3% of glutaraldehyde and the balance of hydrochloric acid aqueous solution. The invention can realize temperature control and glue forming without adding other temporary plugging agents; gel is formed by the combined action of reversible covalent bonds and intermolecular hydrogen bonds, and has certain shearing resistance; the temperature response type hydrogel fracturing fluid is easy to flow back after gel breaking, cannot cause residual damage to a reservoir, and is suitable for fracturing transformation of oil and gas fields.
Description
Technical Field
The invention relates to the technical field of hydraulic fracturing, in particular to a temperature response type hydrogel temporary plugging diversion fracturing fluid and a preparation method and application thereof.
Background
In the process of oil and gas field development, the stimulation of the stratum is often needed, and fracturing is an important means for reservoir transformation. Common guar gum, modified guar gum and synthetic polymer fracturing fluid are prepared into high molecular solution on the ground and then injected into stratum, the tackifying of the fracturing fluid is realized by utilizing the characteristic of high molecular weight, and high molecular residues are damaged after the construction and the gel breaking.
The Chinese patent literature discloses 'a fracturing fluid containing butane and a preparation method thereof', the application publication number of which is CN103468236A, the invention takes butane as base fluid, dialkyl phosphate synthesized by low-carbon alcohol as a thickening agent, and sodium metaaluminate as a cross-linking agent, but the method adopts a two-step gelling method, the process is complex, the gelling speed is slow, the temperature resistance is poor, and the construction requirements cannot be met.
Chinese patent literature discloses 'a cellulose blending modified polyvinyl alcohol fracturing fluid and a preparation method thereof', the application publication number of which is CN104974739A, the invention discloses a cellulose blending modified polyvinyl alcohol fracturing fluid which comprises 1-15 parts of polyvinyl alcohol, 1-15 parts of cellulose, 1-10 parts of organic titanium cross-linking agent and 300 parts of water 200-containing organic titanium, but the invention can not solve the problems of poor tackifying property, poor temperature resistance and poor shearing resistance of the conventional polyvinyl alcohol and the like. Therefore, in order to improve the fracturing effect and prevent the gel breaking and leakage of the fracturing fluid in the fracturing process, the search of a novel high-temperature-resistant fracturing fluid is an urgent technical problem to be solved in the field.
Disclosure of Invention
The invention provides a temperature response type hydrogel temporary plugging diversion fracturing fluid which is suitable for fracturing operation, easy to flowback and free of damage to a stratum, and aims to solve the problems that the existing fracturing fluid is poor in temperature resistance, easy to break and leak in a fracturing process and easy to damage polymer residues on the stratum.
The invention also provides a preparation method of the temperature response type hydrogel temporary plugging steering fracturing fluid, which has simple steps and can realize the purpose of temporary plugging steering in the cracks formed by hydraulic fracturing without adding other temporary plugging materials.
The invention also provides application of the temperature response type hydrogel temporary plugging diversion fracturing fluid in hydraulic fracturing construction.
In order to achieve the purpose, the invention adopts the following technical scheme:
the temperature response type hydrogel temporary plugging and steering fracturing fluid consists of the following components in percentage by mass: 0.2-1.2% of chitosan, 4-10% of chitosan oligosaccharide, 1.1-3% of glutaraldehyde and the balance of hydrochloric acid aqueous solution.
The conventional hydrogel is normal-temperature gel, and a gel system becomes solution after heating. The temperature response type hydrogel system provided by the invention is a three-dimensional structure formed by the combined action of reversible covalent bonds and hydrogen bonds between molecules of the gel factor. The reversible covalent bond is formed only when being heated, the hydrogel system is liquid at normal temperature, gel can be formed in the heating process, and the reversible covalent bond is destroyed to form the liquid after being further heated, so the temperature response type hydrogel system is provided. The performance of the whole gel can be changed by changing the molar ratio of each component or changing any one component, and the system has wide adjustability so that the gel can adapt to different environmental use conditions.
The viscosity of the conventional fracturing fluid is generally reduced along with the increase of temperature, and the construction may be unsuccessful due to the fact that the viscosity of the fracturing fluid is reduced or gel breaking is easy to cause the leakage of the fracturing fluid in the fracturing construction process. The temperature response type hydrogel provided by the invention can realize the multiphase conversion of solution-gel-solution along with the temperature change, the system is low-viscosity liquid at normal temperature, gel is formed at 40-80 ℃, and the temperature is continuously increased to break the gel at 110-130 ℃, so that the gel can be automatically broken into solution along with the rise of the formation temperature after the construction is finished, and the hydrogel is easy to flowback and has no damage. And the temporary plugging diversion fracturing fluid can realize the purpose of temporary plugging diversion in the cracks formed by hydraulic fracturing without adding other temporary plugging materials.
Preferably, the concentration of the hydrochloric acid aqueous solution is 0.35-0.5 wt%, the solubility of the hydrochloric acid aqueous solution is related to the viscoelastic property and the gelling time of the hydrogel, the gelling time is prolonged and the viscoelasticity is poor due to too low concentration, and the gelling is difficult due to too high concentration.
Preferably, the viscosity of the chitosan is 100-200 mPa.s, and the viscosity is too low, so that the gelling viscoelasticity is low, and the anti-shearing effect is poor; excessive viscosity can make initial pumping difficult.
Preferably, the weight average molecular weight of the chitosan oligosaccharide is 1000-6000.
Preferably, the weight average molecular weight of the chitosan is 40 to 2500 ten thousand.
Preferably, the gel forming temperature of the temperature response type hydrogel temporary plugging diversion fracturing fluid is 40-80 ℃, and the gel breaking temperature is 110-130 ℃.
The invention provides a temperature response type hydrogel system suitable for fracturing operation, which is flowable low-viscosity liquid at normal temperature, loses fluidity after the viscosity increases within a certain time after the temperature rises to 40-80 ℃, recovers to flowable low-viscosity liquid within a certain time after the temperature continues to rise to above 110-130 ℃, becomes liquid after the temperature rises along with the temperature of a stratum after construction is completed, is easy to return, has no harm to the stratum, and has wide market prospect.
According to the proportion, sequentially adding chitosan and chitosan oligosaccharide into a hydrochloric acid aqueous solution, uniformly stirring, then adding glutaraldehyde, and uniformly stirring to obtain the temperature response type hydrogel temporary plugging diversion fracturing fluid.
The application of the temperature response type hydrogel temporary plugging diversion fracturing fluid in water conservancy fracturing construction is characterized in that the diversion fracturing fluid is prepared on the ground, the viscosity fluidity of the diversion fracturing fluid is easy to inject into a stratum, the construction is easy, the temperature of the fracturing fluid can be gradually increased in the process of injecting the fracturing fluid into the stratum, the temperature of the fracturing fluid injected at the front end is increased fastest, when the temperature is increased to 40-80 ℃, the viscosity of the fracturing fluid is rapidly increased until the fracturing fluid is in a gel state, the fluidity of the fracturing fluid is slowed down or the fracturing fluid is in a non-flowing state, so that cracks or karst caves can be plugged in the stratum, the leakage of the fracturing fluid is prevented, and the pressure is easily suppressed in the stratum to enable the stratum to be easily pressed open.
Therefore, the invention has the following beneficial effects:
(1) the temperature-responsive hydrogel temporary plugging diversion fracturing fluid can realize temperature control gelling without adding other temporary plugging agents;
(2) the temperature response type hydrogel fracturing fluid is formed into gel by means of the combined action of reversible covalent bonds and intermolecular hydrogen bonds, so that the temperature response type hydrogel fracturing fluid has certain shearing resistance;
(3) the temperature response type hydrogel fracturing fluid is easy to flow back after gel breaking, cannot cause residual damage to a reservoir, and is suitable for fracturing transformation of oil and gas fields.
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
EXAMPLE 1 HCG-1 hydrogel diversion fracturing fluid
Firstly, taking 5ml of 0.35 wt% hydrochloric acid aqueous solution, then respectively adding 0.01g of chitosan with the viscosity of 200mPa.s and 0.225g of chitosan oligosaccharide with the weight-average molecular weight of 1000, uniformly stirring, then adding 0.12g of glutaraldehyde, and uniformly stirring to obtain the temperature response type hydrogel temporary plugging diversion fracturing fluid, which is marked as HCG-1 hydrogel diversion fracturing fluid.
And (3) placing the prepared HCG-1 hydrogel diverting fracturing fluid into an oil bath pan for heating, fixing the temperature to 80 ℃, observing the phenomenon every 5min, and recording the final gelling time to be 50 min. The hydrogel is fixed in a closed reaction kettle at 120 ℃ and heated, and the time for completely breaking the gel into liquid is found to be 2 hours.
Example 2 HCG-2 hydrogel diverting fracturing fluid
Firstly, 5ml of 0.35 wt% hydrochloric acid aqueous solution is taken, then 0.02g of chitosan with the viscosity of 100mPa.s and 0.2g of chitosan oligosaccharide with the weight-average molecular weight of 6000 are respectively added into the hydrochloric acid aqueous solution and uniformly stirred, and then 0.12g of glutaraldehyde is added and uniformly stirred, so that the temperature response type hydrogel temporary plugging diversion fracturing fluid is prepared and recorded as HCG-2 hydrogel diversion fracturing fluid.
And (3) putting the prepared HCG-2 hydrogel diverting fracturing fluid into an oil bath pan for heating, fixing the temperature to be 60 ℃, observing the phenomenon every 5min, and recording the final gelling time to be 110 min. The hydrogel was fixed in a closed reaction vessel at 110 ℃ and heated, and the time taken for complete gel breaking to become liquid was found to be 3 hours.
Example 3 HCG-3 hydrogel diversion fracturing fluid
Firstly, taking 5ml of 0.5wt% hydrochloric acid aqueous solution, then respectively adding 0.06g of chitosan with the viscosity of 150mPa.s and 0.15g of chitosan oligosaccharide with the weight-average molecular weight of 4000 into the aqueous solution, uniformly stirring the mixture, then adding 0.12g of glutaraldehyde, and uniformly stirring the mixture, namely, preparing the temperature response type hydrogel temporary plugging diversion fracturing fluid which is marked as HCG-3 hydrogel diversion fracturing fluid.
And (3) putting the prepared HCG-3 hydrogel diverting fracturing fluid into an oil bath pan for heating, fixing the temperature to 80 ℃, observing the phenomenon every 5min, and recording the final gelling time to be 30 min. The hydrogel is fixed in a closed reaction kettle at 120 ℃ and heated, and the time for completely breaking the gel into liquid is found to be 2 h.
Example 4 HCG-4 hydrogel diversion fracturing fluid
Firstly, taking 5ml of 0.5wt% hydrochloric acid aqueous solution, then respectively adding 0.06g of chitosan with the viscosity of 120mPa.s and 0.15g of chitosan oligosaccharide with the weight-average molecular weight of 3000 into the aqueous solution, uniformly stirring the mixture, then adding 0.12g of glutaraldehyde, and uniformly stirring the mixture, namely, preparing the temperature response type hydrogel temporary plugging diversion fracturing fluid which is marked as HCG-4 hydrogel diversion fracturing fluid.
And (3) placing the prepared HCG-4 hydrogel diverting fracturing fluid into an oil bath pan for heating, fixing the temperature to be 40 ℃, observing the phenomenon every 5min, and recording the final gelling time to be 3 h. The hydrogel was fixed in a closed reaction vessel at 130 ℃ and heated, and the time taken for complete gel breaking to become liquid was found to be 2 hours.
Example 5 HCG-5 hydrogel diversion fracturing fluid
Firstly, 5ml of 0.4 wt% hydrochloric acid aqueous solution is taken, then 0.06g of chitosan with the viscosity of 150mPa.s and 0.15g of chitosan oligosaccharide with the weight-average molecular weight of 4000 are respectively added into the aqueous solution and stirred uniformly, and then 0.12g of glutaraldehyde is added into the aqueous solution and stirred uniformly, so that the temperature response type hydrogel temporary plugging diversion fracturing fluid is prepared and obtained, and the temperature response type hydrogel temporary plugging diversion fracturing fluid is marked as HCG-3 hydrogel diversion fracturing fluid.
And (3) putting the prepared HCG-5 hydrogel diverting fracturing fluid into an oil bath pan for heating, fixing the temperature to 80 ℃, observing the phenomenon every 5min, and recording the final gelling time to be 30 min. The hydrogel is fixed in a closed reaction kettle at 120 ℃ and heated, and the time for completely breaking the gel into liquid is found to be 2 hours.
The results of the shear resistance tests on the temperature-responsive hydrogel fracturing fluids prepared in examples 1-5 are shown in Table 1:
TABLE 1 shear resistance test results for steering fracturing fluids
The data in Table 1 show that the fracturing fluid has low normal-temperature viscosity and is easy to pump and inject during construction; after high-temperature complete gel breaking, the viscosity is increased compared with the normal temperature, but the overall viscosity is still very low and is easy to flow back, and the flow conductivity is increased after flow back; under high shear frequency, the gel system still has considerable apparent viscosity retention rate, which indicates that the internal network structure of the gel is stable, and the diverting fracturing fluid system has better shear resistance.
Comparative example 1 (viscosity of chitosan is too low)
The difference between the comparative example 1 and the example 1 is that the viscosity of the chitosan is 80mPa.s, the rest processes are completely the same, and the HCG-6 hydrogel diversion fracturing fluid is prepared.
And (3) putting the prepared HCG-6 hydrogel diverting fracturing fluid into an oil bath pan for heating, fixing the temperature to be 60 ℃, observing the phenomenon every 5min, and recording the final gelling time to be 65 min. The hydrogel is fixed in a closed reaction kettle at 110 ℃ and heated, and the time for completely breaking the gel into liquid is found to be 2 hours.
Comparative example 2 (viscosity of chitosan is too high)
The difference between the comparative example 2 and the example 1 is that the viscosity of the chitosan is 240mPa.s, the rest processes are completely the same, and the HCG-7 hydrogel diverting fracturing fluid is prepared.
And (3) putting the prepared HCG-7 hydrogel diverting fracturing fluid into an oil bath pan for heating, fixing the temperature to 80 ℃, observing the phenomenon every 5min, and recording the final gelling time to be 25 min. The hydrogel was fixed in a closed reaction vessel at 120 ℃ and heated, and the time taken for complete gel breaking to become liquid was found to be 2.5 hours.
Comparative example 3 (concentration of aqueous hydrochloric acid solution is too high)
The difference between the comparative example 3 and the example 1 is that the concentration of the hydrochloric acid aqueous solution is 0.8 wt%, the rest processes are completely the same, and the HCG-8 hydrogel diverting fracturing fluid is prepared.
And (3) placing the prepared HCG-8 hydrogel diverting fracturing fluid into an oil bath pan for heating, fixing the temperature to 80 ℃, observing the phenomenon every 5min, and observing for 3h to prevent the hydrogel from being formed.
Comparative example 4 (concentration of aqueous hydrochloric acid solution was too low)
The difference between the comparative example 4 and the example 1 is that the concentration of the hydrochloric acid aqueous solution is 0.3 wt%, the rest processes are completely the same, and the HCG-7 hydrogel diverting fracturing fluid is prepared.
And (3) putting the prepared HCG-7 hydrogel diverting fracturing fluid into an oil bath pan for heating, fixing the temperature to 80 ℃, observing the phenomenon every 5min, and recording the final gelling time to be 90 min. The hydrogel is fixed in a closed reaction kettle at 120 ℃ and heated, and the time for completely breaking the gel into liquid is 100 min.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the scope of the present invention as set forth in the claims.
Claims (4)
1. The temperature response type hydrogel temporary plugging and steering fracturing fluid is characterized by comprising the following components in percentage by mass: 0.2-1.2% of chitosan, 4-10% of chitosan oligosaccharide, 1.1-3% of glutaraldehyde and the balance of hydrochloric acid aqueous solution;
the concentration of the hydrochloric acid aqueous solution is 0.35-0.5 wt%;
the viscosity of the chitosan is 100-200 mPa.s;
the weight average molecular weight of the chitosan oligosaccharide is 1000-6000;
the weight average molecular weight of the chitosan is 40-2500 ten thousand.
2. The temperature-responsive hydrogel temporary plugging and diverting fracturing fluid as claimed in claim 1, wherein the gel forming temperature of the temperature-responsive hydrogel temporary plugging and diverting fracturing fluid is 40-80 ℃ and the gel breaking temperature is 110-130 ℃.
3. The preparation method of the temperature response type hydrogel temporary plugging diversion fracturing fluid as claimed in any one of claims 1 to 2, wherein chitosan and chitosan oligosaccharide are sequentially added into the hydrochloric acid aqueous solution according to the proportion, the mixture is uniformly stirred, and then glutaraldehyde is added and the mixture is uniformly stirred, so that the temperature response type hydrogel temporary plugging diversion fracturing fluid is obtained.
4. Use of a temperature responsive hydrogel temporary plugging diversion fracturing fluid of any one of claims 1-2 in hydraulic fracturing construction.
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| CN113847005B (en) * | 2020-06-28 | 2024-03-08 | 中国石油化工股份有限公司 | Method for carrying out repeated fracturing by using temperature-sensitive foam fracturing fluid and application |
| CN116410716A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气集团有限公司 | Supermolecule gel temporary plugging agent and preparation method thereof |
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