CN113355080A - Multifunctional foam fracturing fluid and preparation method thereof - Google Patents
Multifunctional foam fracturing fluid and preparation method thereof Download PDFInfo
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- CN113355080A CN113355080A CN202110618402.8A CN202110618402A CN113355080A CN 113355080 A CN113355080 A CN 113355080A CN 202110618402 A CN202110618402 A CN 202110618402A CN 113355080 A CN113355080 A CN 113355080A
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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
- C09K8/70—Compositions for forming crevices or fractures characterised by their form or by the form of their components, e.g. foams
- C09K8/703—Foams
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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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/592—Compositions used in combination with generated heat, e.g. by steam injection
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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
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/30—Viscoelastic surfactants [VES]
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Abstract
The invention provides a multifunctional foam fracturing fluid and a preparation method thereof, wherein the multifunctional foam fracturing fluid is an aqueous solution, and a solvent comprises: the self-gassing agent is sodium nitrite; the multifunctional agent is ammonium chloride; the initiator is paraformaldehyde; the foaming agent is one or more of tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and didecyl dimethyl ammonium bromide; the foam stabilizer is one or more of erucamidopropyl betaine, oleamidopropyl betaine, erucamidopropyl hydroxysulfobetaine and hexadecyl hydroxypropyl sulfobetaine. The invention delays the corrosion of the strong acid environment to the tubular column, ensures the supply of hydrogen ions and avoids the continuous consumption of the hydrogen ions under the gas generating condition; the self-gas generation reaction is violent, the generated foam is more and stable, the propping agent can be carried into the deep part of the stratum without causing sand blocking accidents, and a large amount of heat can be released, so that the adsorbed methane is desorbed, and the yield increasing efficiency of the foam fracturing fluid is improved.
Description
Technical Field
The invention belongs to the technical field of foam fracturing fluid, and particularly relates to multifunctional foam fracturing fluid and a preparation method thereof.
Background
The foam fracturing fluid has the advantages of high viscosity, strong sand carrying capacity, low filtration loss, quick flowback and the like, and is applied to hydraulic fracturing exploitation of unconventional natural gas resources such as shale gas, coal bed gas, dense gas and the like at present. However, the foam fracturing fluid has high self friction resistance and low liquid column pressure, and the application of the foam fracturing fluid in deep oil gas hydraulic fracturing is limited. Aiming at the defects, the self-generated foam fracturing fluid is proposed at present, and is generated in the underground and the stratum by virtue of gas generated spontaneously at the bottom of a well, so that the friction between the foam fracturing fluid and a shaft string is avoided, the pumping pressure of ground hydraulic fracturing construction is reduced (the number of required pump trucks is reduced), and the fracturing construction cost is reduced. Meanwhile, the self-generated foam fracturing fluid also avoids the use of gas supply equipment and foam preparation, and reduces the complexity of the hydraulic fracturing construction process.
In the existing self-generating foam fracturing fluid, an acidic initiator is often required to be added to accelerate the gas generation rate. It has been shown that the more acidic the self-generating gas solution system, the faster the gas generated and the more readily foam is formed. However, if the acidity is too strong, the pipe column will be corroded, causing potential safety hazards; if the acidity is too weak, the gas generation speed is low, the foam quality is reduced, a large amount of proppant is difficult to carry at the bottom of the well, and sand blockage is often formed. Meanwhile, in the process of generating the self-generated gas, hydrogen ions are consumed, acidity is weakened, and the later gas generation efficiency is slowed down, namely the efficiency of generating the foam is reduced.
The existing self-generating foam fracturing fluid system comprises self-generating gas, a foaming agent and a foam stabilizer;
the self-generated gas mainly comprises the following components:
(1) CO generation from sodium carbonate or bicarbonate under acidic conditions2；
(2) Ammonium persulfate and sodium nitrite are used for generating N under the acidic condition2；
(3) Ammonium persulfate + urea are used for generating N under acidic condition2；
(4) Under the acidic condition, the ammonium chloride and the sodium nitrite generate N2；
The foaming agent is a surfactant, and the foam stabilizer is gel, guar gum, polymer and the like.
The key points of the current self-generating foam system generation are the selection of the self-generating gas system and the screening of the foaming agent and the foam stabilizer. Aiming at the three important components, the problems of the self-generating foam system at present are as follows:
(1) for the self-generated gas system, the above four systems all need to generate gas under acidic condition, and the generation speed of the gas depends on the strength of the acidity. Strong acidity, fast gas generation, high quality of generated foam, easy carrying of proppant into stratum by formed foam fracturing fluid, and strong acidity, which can corrode the tubular column and cause potential safety hazard. If the acidity is weak, the corrosion to the pipe column can be weakened, but the gas generation is slow, the foam is not easy to generate, the proppant cannot be carried, and sand blockage can be easily caused near the well casing. Meanwhile, in the process of generating the self-generated gas, hydrogen ions are consumed, acidity is weakened, and the later gas generation efficiency is slowed down, namely the efficiency of generating the foam is reduced.
(2) Aiming at the selection of the existing foam stabilizer, a macromolecular polymer is mostly adopted as the foam stabilizer, which can cause a great amount of irreversible damage to low-pore and low-permeability unconventional gas reservoirs such as shale gas, coal bed gas and the like, can block pores seriously, and greatly reduces the flow conductivity of hydraulic cracks.
Disclosure of Invention
This patent provides an initiating agent of slow release hydrogen ion, has not only avoided the corruption of acidity to the tubular column, can guarantee the strong acidity in the foam system of self-generating moreover to produce the foam fast, carry the proppant and get into the stratum, improve hydraulic fracturing's efficiency, avoid forming sand blocking accident. In addition, the multifunctional foam fracturing fluid system related to the patent can be applied to hydraulic fracturing of unconventional natural gas resources such as coal bed gas, shale gas and the like, not only because the foam fracturing fluid has the advantages of high viscosity, strong sand carrying capacity, low filtration loss and rapid flowback, but also because the foam fracturing fluid can release a large amount of heat when self-generated foam is rapidly generated under high acidity, the desorption of adsorbed gas in the coal bed gas and the shale gas is facilitated, and the multifunctional foam fracturing fluid system has multiple functions.
The specific technical scheme is as follows:
the multifunctional foam fracturing fluid is an aqueous solution, and the solvent comprises a self-gassing agent, a multifunctional agent, an initiator, a foaming agent and a foam stabilizer;
the self-gassing agent is sodium nitrite, and the concentration range is as follows: 2-10 wt%;
the multifunctional agent is ammonium chloride, and the concentration ranges are as follows: 2-12 wt%;
the initiator is paraformaldehyde, the polymerization degree n ranges from 10 to 100, and the concentration ranges are as follows: 0.03 wt% -1 wt%;
the foaming agent is one or more of tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and didecyl dimethyl ammonium bromide, and the concentration ranges are as follows: 0.05 wt% -0.5 wt%;
the foam stabilizer is one or more of erucamidopropyl betaine, oleamidopropyl betaine, erucamidopropyl hydroxysulfobetaine and hexadecyl hydroxypropyl sulfobetaine, and the concentration ranges are as follows: 0.5 wt% -3 wt%.
Mixing a multifunctional agent and an initiator to obtain an acidic solution; the multifunctional agent and the self-gas generating agent can obtain self-gas generation, and the multifunctional agent can be used as a clay stabilizer in the fracturing fluid.
The specific configuration method comprises the following steps:
step 1: mixing a multifunctional agent aqueous solution and an initiator aqueous solution at normal temperature, and spontaneously preparing to generate an acidic solution;
step 2: adding a multifunctional agent and a self-gassing agent into the mixed solution in the step 1;
and step 3: and adding a foaming agent, a foam stabilizer and a multifunctional agent into the mixed solution in the step 2.
The invention provides a multifunctional foam fracturing fluid, which has the following specific principle:
(1) firstly, when the multifunctional agent and the initiator are mixed together, the two agents can generate nucleophilic reaction in organic chemistry so as to slowly release hydrogen ions, and the concentration of the multifunctional agent and the initiator can be adjusted according to the required acidity, so that a strong acidic solution environment is obtained.
(2) Under the condition of slowly releasing hydrogen ions, the solution is strongly acidic, and excessive multifunctional agent and the self-gas generating agent undergo oxidation-reduction reaction to generate a large amount of N2And simultaneously, a large amount of heat is released, which is beneficial to desorption of methane adsorption gases such as coal bed gas, shale gas and the like.
(3) In a large number of N2At the same time, a large amount of foam is generated due to the foaming agent contained in the system.
(4) Because the system contains the foam stabilizer for increasing the viscosity of the system, the stability of the foam can be greatly improved, and the foam can be continuously pumped into the deep part of the stratum.
(5) The generated foam carries the proppant into the stratum quickly, and sand blocking accidents caused by accumulation in the near-wellbore area are avoided.
The invention has the technical effects that:
(1) the strong acid environment in the system is generated by the nucleophilic reaction of the multifunctional agent and the initiator, and hydrogen ions generated by the multifunctional agent and the initiator can be slowly released, so that the corrosion of the strong acid environment to a pipe column is delayed, the supply of the hydrogen ions is ensured, and the condition that the hydrogen ions are continuously consumed under the gas generation condition and the acidity is reduced (once the acidity is reduced, the gas generation speed is reduced) is avoided.
(2) Under the condition of strong acidity, the self-generated gas has violent reaction, can release a large amount of gas in a short time, and generates a large amount of stable foam in the presence of a foaming agent and a foam stabilizer, so that the proppant can be carried into the deep part of a stratum without causing sand blocking accidents.
(3) The reaction of self-generated gas is redox reaction, and can release a large amount of heat while generating gas, so that the adsorbed methane can be further desorbed under the hydraulic fracturing of unconventional natural gas resources such as coal bed gas and shale gas, and the yield increasing efficiency of the foam fracturing fluid is improved.
(4) The foam stabilizer in the system is a micromolecular viscoelastic surfactant, replaces polymers in conventional foam fracturing fluid, avoids a great deal of damage to stratum, and is a necessary choice for a low-damage fracturing fluid system especially for low-pore and low-permeability coal bed gas and shale gas.
(5) The self-generated foam fracturing fluid system can simplify the fracturing construction process and reduce the cost.
Drawings
FIG. 1 shows the acid concentration changes of the multifunctional agent and the initiator at different ratios in example 1 at normal temperature;
figure 2 is the self-generated foam generated from the multifunctional foam-based fracturing fluid system of example 4.
Detailed Description
The specific technical scheme of the invention is described by combining the embodiment.
Example 1:
the multifunctional agent of 0.3 wt% and the initiator of 0.3 wt% are mixed according to the volume ratio of different proportions to obtain the acid concentration curve at normal temperature, and as can be seen from the figure, the multifunctional agent and the initiator can rapidly generate acid within five minutes after mixing at normal temperature, and when the volume ratio is 1:1, the obtained acid solution has the highest concentration, namely the proportion can reduce the pH value of the system environment to the lowest, which is beneficial to the subsequent gas generation of the multifunctional agent and the self-gas generating agent under the strong acid condition.
Example 2:
mixing 0.1mol of multifunctional agent and 0.1mol of self-gassing agent in a volume ratio of 1:1 into 200ml of solution, taking half of the volume of the solution, adjusting the pH value to 2, adjusting the pH value of the other half of the volume of the solution to 3.5, putting the two solutions in a water bath kettle at 60 ℃, and measuring the gas production rate and the gas production speed of the two solutions in different time periods, wherein the specific data are shown in the following table 1. As is clear from the table, the stronger the acidity of the self-generating gas system, the greater the gas generation amount, and the higher the gas generation speed, the more favorable the subsequent generation of self-generating foam.
TABLE 1 Effect of pH on biogas and gas production Rate at 60 deg.C
Example 3:
mixing 0.1mol of multifunctional agent and 0.1mol of self-gassing agent in a volume ratio of 1:1 into 200ml of solution, taking half of the volume of the solution, adjusting the pH value to 2, adjusting the pH value of the other half of the volume of the solution to 4.8, putting the two solutions in a water bath kettle at 30 ℃, and measuring the gas production rate and the gas production speed of the two solutions in different time periods, wherein the specific data are shown in the following table 2. As can be seen from the table, the stronger the acidity of the self-generating gas system, the greater the amount of gas generation, and the higher the gas generation speed, the more favorable the subsequent generation of the self-generating foam system.
TABLE 2 influence of pH on biogas production and gas production rate at 30 deg.C
Example 4:
a multifunctional foam fracturing fluid system comprises a self-gas generating agent, a multifunctional agent, an initiator, a foaming agent and a foam stabilizer, and the preparation method comprises the following steps:
step 1: preparing 50ml of 0.6 wt% aqueous solution of an initiator;
step 2: preparing 50ml of 0.6 wt% multifunctional initiator aqueous solution, mixing the multifunctional initiator aqueous solution with the initiator aqueous solution obtained in the step 1, and uniformly stirring to obtain 100ml of solution;
and step 3: on the basis of the mixed solution obtained in the step 2, 5.34 wt% of multifunctional agent and 6.9 wt% of self-gassing agent are added;
and 4, step 4: on the basis of the mixed solution obtained in step 3, 0.1 wt% of a foaming agent such as tetradecyltrimethylammonium bromide, 1 wt% of a foam stabilizer such as erucamidopropylbetaine, and 2 wt% of a multifunctional agent are further added.
The mixed system was placed in a water bath at 60 ℃ and the formation of foam was observed. The results show that: the system rapidly foams at 60 ℃ and the resulting foam volume can fill the entire cylinder in a 1L cylinder, 3 hours later the height of the foam begins to decrease and the final foam has a volume half-life of 8 hours.
Claims (3)
1. The multifunctional foam fracturing fluid is characterized by being an aqueous solution, and the solvent comprises a self-gassing agent, a multifunctional agent, an initiator, a foaming agent and a foam stabilizer;
the self-gassing agent is sodium nitrite;
the multifunctional agent is ammonium chloride;
the initiator is paraformaldehyde, and the polymerization degree n ranges from 10 to 100;
the foaming agent is one or more of tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and didecyl dimethyl ammonium bromide;
the foam stabilizer is one or more of erucamidopropyl betaine, oleamidopropyl betaine, erucamidopropyl hydroxysulfobetaine and hexadecyl hydroxypropyl sulfobetaine.
2. The multifunctional foam fracturing fluid of claim 1, wherein the concentration of the self-gassing agent is 2 wt% to 10 wt%; the concentration of the multifunctional agent is 2-12 wt%; the concentration of the initiator is 0.03 to 1 weight percent; the concentration of the foaming agent is 0.05 wt% -0.5 wt%; the concentration of the foam stabilizer is 0.5-3 wt%.
3. The preparation method of the multifunctional foam fracturing fluid as claimed in claim 1 or 2, which is characterized by comprising the following steps:
step 1: mixing a multifunctional agent aqueous solution and an initiator aqueous solution at normal temperature, and spontaneously preparing to generate an acidic solution;
step 2: adding a multifunctional agent and a self-gassing agent into the mixed solution in the step 1;
and step 3: and adding a foaming agent, a foam stabilizer and a multifunctional agent into the mixed solution in the step 2.
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