CN112940706A - Integrated composite acid and preparation method thereof - Google Patents
Integrated composite acid and preparation method thereof Download PDFInfo
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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
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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
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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
- C09K8/78—Eroding chemicals, e.g. acids combined with additives added for specific purposes for preventing sealing
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Abstract
The invention relates to the technical field of acid fracturing, and particularly discloses an integrated composite acid and a preparation method thereof, wherein the integrated composite acid comprises a polymer fracturing fluid, acidic slick water and gelled acid; the polymer fracturing fluid, the acid slickwater and the gel acid are prepared from the same emulsion gelling agent, and the emulsion gelling agent comprises 30-50 parts of cationic polyacrylamide, 2-4 parts of viscosity regulator, 0.5-1.2 parts of suspending agent, 40-70 parts of solvent and 0.5-1.5 parts of wetting dispersant. Polymer fracturing fluid and acidizing fluid are because of adopting same kind of emulsion gel preparation in this patent for compatibility that can be fine between the two, and adopt the online preparation mode of integration, can carry out the adjustment of acidizing fluid viscosity, acid concentration, acidizing fluid type in real time, also can prepare according to the time limit for a project of fracturing construction simultaneously, solve the acidizing fluid of preparing in advance and use problem rotten in time, and this composite acid system still has advantages such as broken glue is effectual and easy flowback, and is low to the stratum injury.
Description
Technical Field
The invention relates to the technical field of acid fracturing, in particular to an integrated composite acid and a preparation method thereof.
Background
The acid fracturing is one of the main measures for increasing the yield of oil gas, the application ratio of artificial polymers mainly comprising polyacrylamide is higher and higher, the conventional polymer fracturing fluid adopts anionic polyacrylamide, acid liquor (acid slick water and gelled acid) adopts cationic polyacrylamide, and the two components can generate floc and precipitate after being mixed to block pipelines and strata, so that the harm is extremely high, and the two components cannot be mixed in the using process; therefore, the traditional fracturing fluid construction and the acid liquid can not be carried out simultaneously due to incompatibility of systems, and certain fracturing processes can not be implemented.
In addition, the traditional gelled acid and the acidic slickwater are prepared in advance in an acid station, the prepared acid liquid needs to be used in time, the effective service life of the acid liquid is generally not longer than 7 days, but the deterioration of the gelled acid or the acidic slickwater is caused when the construction period is prolonged frequently in fracturing construction, and the subsequent treatment of the deteriorated gelled acid or the acidic slickwater is also a great problem.
Disclosure of Invention
The invention provides an integrated composite acid and a preparation method thereof, and aims to solve the problem that certain fracturing processes cannot be implemented due to the fact that traditional fracturing fluid construction and acid liquor cannot be carried out simultaneously due to incompatibility of systems in the prior art.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the integrated composite acid comprises polymer fracturing fluid, acidic slick water and gelled acid;
the polymer fracturing fluid comprises, by weight, 0.15-0.6 part of an emulsion gelling agent, 0.2-0.5 part of a cross-linking agent, 0.2-0.5 part of a composite synergist and the balance of water;
the acidic slickwater comprises, by weight, 0.1-0.3 part of emulsion gelling agent, 1-2 parts of corrosion inhibitor, 1-2 parts of iron ion stabilizer, 1-2 parts of composite synergist, 5-15 parts of hydrochloric acid and the balance of water;
the gel acid comprises, by weight, 1-3 parts of an emulsion gelling agent, 1-4 parts of a corrosion inhibitor, 1-2 parts of an iron ion stabilizer, 1-2 parts of a composite synergist, 10-20 parts of hydrochloric acid and the balance of water;
the emulsion gelling agent comprises in parts by weight: 30-50 parts of cationic polyacrylamide, 2-4 parts of viscosity regulator, 0.5-1.2 parts of suspending agent, 40-70 parts of solvent and 0.5-1.5 parts of wetting dispersant.
The technical principle and the effect of the technical scheme are as follows:
the integrated composite acid in the scheme adopts an emulsion gelling agent (modified cationic polyacrylamide), is modified on the traditional gelling agent, can be used for preparing polymer fracturing fluid, acidic slickwater and gelled acid, can meet the technical requirements of fracturing in clear water and acid liquor, and avoids the compatibility problem.
The integrated composite acid in the scheme can be prepared on line, the viscosity and the acid concentration of the acid solution can be adjusted in real time according to the content of the emulsion gelling agent, and different acid solution types (acid slickwater or gelled acid or mixture of the acid slickwater and the gelled acid) are selected to meet different requirements of the fracturing fluid system.
The integrated composite acid system prepared by the scheme has the characteristics of good gel breaking effect and easiness in flowback, is easy to pump and inject and has low damage to the stratum; in addition, the gelled acid has good temperature resistance and shear resistance, the viscosity can gradually rise under the condition of formation temperature, the hydrochloric acid can be slowly released, the acid rock reaction can be fully carried out, and the purpose of deep acidification is achieved.
Further, the viscosity regulator comprises isophorone diamine and polyvinylpyrrolidone K10, the suspending agent is fumed silica, the solvent is methyl nylon acid, and the wetting dispersant is dioctyl sodium sulfosuccinate.
Further, a method of preparing the emulsion gellant, comprising the steps of:
s1: preparing the components according to the proportion of the emulsion gel;
s2: adding a solvent into a reaction kettle, starting a stirring and emulsifying pump, adding a suspending agent into the reaction kettle according to a ratio, stirring and emulsifying, adding a viscosity regulator, continuing stirring and emulsifying, and then adding cationic polyacrylamide, stirring and emulsifying;
s3: adding wetting dispersant, stirring uniformly, and then passing the whole through a sand mill to obtain the emulsion gel.
Further, the online liquid distribution system for the polymer fracturing liquid, the acidic slick water and the gelled acid comprises a plurality of metering pumps, a liquid supply pry and an outlet pipeline, wherein outlet ends of the metering pumps are respectively connected with a liquid adding port of the liquid supply pry.
Further, the preparation method of the polymer fracturing fluid comprises the steps that different metering pumps respectively pump the emulsion gelling agent, the cross-linking agent and the composite synergist, and the emulsion gelling agent, the cross-linking agent and the composite synergist are uniformly mixed with clear water pumped by the liquid supply pry in the liquid supply pry to form the polymer fracturing fluid.
Further, the preparation method of the acidic slickwater comprises the steps that different metering pumps respectively pump the emulsion gelling agent, the corrosion inhibitor, the iron ion stabilizer and the composite synergist, and the emulsion gelling agent, the corrosion inhibitor, the iron ion stabilizer and the composite synergist are uniformly mixed with hydrochloric acid pumped by the liquid supply pry in the liquid supply pry to form the acidic slickwater.
Further, the preparation method of the gelled acid comprises the steps of respectively pumping the emulsion gelling agent, the corrosion inhibitor, the iron ion stabilizer and the composite synergist by different metering pumps, and uniformly mixing the pumped emulsion gelling agent, the corrosion inhibitor, the iron ion stabilizer and the composite synergist with hydrochloric acid pumped by the liquid supply pry in the liquid supply pry to form the gelled acid.
Drawings
FIG. 1 is a schematic illustration of the appearance of a polymer fracturing fluid formulated in example 1 of the present invention;
FIG. 2 is a schematic of the appearance of acid slickwater formulated in example 1 of the present invention;
FIG. 3 is a schematic representation of the appearance of gelled acid formulated in example 1 of the present invention;
FIG. 4 is a schematic diagram of the appearance of gelled acid prepared by using a common emulsion thickener in the present invention;
FIG. 5 is a schematic illustration of the appearance of sand-laden polymer fracturing fluid formulated in example 1 of the present invention;
FIG. 6 is a temperature and shear resistant graph of a polymer fracturing fluid formulated in example 1 of the present invention;
FIG. 7 is a temperature and shear resistant graph of gelled acid formulated in example 1 of the present invention.
Detailed Description
The following is further detailed by way of specific embodiments:
example 1:
the integrated composite acid comprises a polymer fracturing fluid, acidic slick water and gelled acid, wherein the polymer fracturing fluid comprises 0.15 part of emulsion gelling agent, 0.2 part of cross-linking agent, 0.2 part of composite synergist and the balance of water in parts by mass; the acidic slickwater comprises, by mass, 0.1 part of emulsion gelling agent, 1 part of corrosion inhibitor, 1 part of iron ion stabilizer, 1 part of composite synergist, 5 parts of hydrochloric acid and the balance of water; the gel acid comprises, by mass, 1 part of an emulsion gelling agent, 1 part of a corrosion inhibitor, 1 part of an iron ion stabilizer, 1 part of a composite synergist, 10 parts of hydrochloric acid and the balance of water.
In the components, the cross-linking agent is organic zirconium; the composite synergist is a fluorocarbon surfactant; the corrosion inhibitor is imidazole; the iron ion stabilizer is citric acid.
The emulsion gelling agent comprises in parts by weight: 35 parts of cationic polyacrylamide, 3 parts of a viscosity regulator, 0.5 part of fumed silica, 60 parts of methyl nylon acid and 1.5 parts of dioctyl sodium sulfosuccinate, wherein the viscosity regulator comprises isophorone diamine and polyvinylpyrrolidone K10 in a ratio of 2: 1; the molecular weight of the cationic polyacrylamide is 1700 ten thousand.
The preparation method of the emulsion gelling agent comprises the following steps:
s1: preparing the components according to the proportion of the emulsion gel;
s2: adding a solvent into a reaction kettle, starting a stirring mechanism and an emulsification pump, adding a suspending agent (fumed silica) into the reaction kettle according to a ratio, keeping the production temperature not higher than 50 ℃, stirring and emulsifying for 1 hour, adding a viscosity regulator (isophorone diamine and polyvinylpyrrolidone K10 in a ratio of 2: 1), and continuing stirring and emulsifying for 30 minutes; adding cationic polyacrylamide, stirring and emulsifying for 2 hours;
s3: adding wetting dispersant (dioctyl sodium sulfosuccinate), stirring for 10 min, and grinding to obtain emulsion gel with a temperature not higher than 50 deg.C.
In this embodiment, the integrated on-line liquid preparation system for composite acid comprises 4 sets of metering pumps for pumping raw materials, a liquid supply pry and an outlet pipeline, wherein the 4 sets of metering pumps in the system are respectively a first metering pump for pumping an emulsion gelling agent, a second metering pump for pumping a composite synergist, a third metering pump for pumping an iron ion stabilizer, a fourth metering pump for pumping a corrosion inhibitor, and outlet ends of the 4 sets of metering pumps are respectively connected to a liquid supply pry medicine adding port.
By adopting the online liquid preparation system, the preparation method of the polymer fracturing liquid comprises the following steps: 0.15 part of emulsion gelling agent is pumped by a first metering pump, 0.2 part of cross-linking agent is pumped by a third metering pump, 0.2 part of composite synergist is pumped by a fourth metering pump, 94.4-98.45 parts of clear water is pumped by a liquid supply skid, and the pumped emulsion gelling agent, the corrosion inhibitor, the cross-linking agent and the clear water are uniformly mixed in the liquid supply skid to form the polymer fracturing fluid.
The preparation method of the acid slickwater comprises the following steps: 0.1 part of emulsion gelling agent is pumped by a first metering pump, 1 part of corrosion inhibitor is pumped by a second metering pump, 1 part of iron ion stabilizing stabilizer is pumped by a third metering pump, 1 part of composite synergist is pumped by a fourth metering pump, 5 parts of hydrochloric acid is pumped by a liquid supply skid, and the pumped emulsion gelling agent, the corrosion inhibitor, the iron stabilizer and the composite synergist are uniformly mixed with hydrochloric acid (dilute hydrochloric acid) in the liquid supply skid to form the acidic slickwater.
The preparation method of the gelled acid comprises the following steps: pumping 1 part of emulsion gelling agent by using a first metering pump, pumping 1 part of corrosion inhibitor by using a second metering pump, pumping 1 part of iron ion stabilizer by using a third metering pump, pumping 1 part of composite synergist by using a fourth metering pump, pumping 10 parts of hydrochloric acid by using a liquid supply skid, and uniformly mixing the pumped emulsion gelling agent, the corrosion inhibitor, the iron stabilizer and the composite synergist with the hydrochloric acid in the liquid supply skid to form gelled acid.
Example 2:
the integrated composite acid comprises a polymer fracturing fluid, acidic slick water and gelled acid, wherein the polymer fracturing fluid comprises 0.6 part of emulsion gelling agent, 0.3 part of cross-linking agent, 0.2 part of composite synergist and the balance of water in parts by mass; the acidic slickwater comprises, by mass, 0.15 part of emulsion gelling agent, 1 part of corrosion inhibitor, 1 part of iron ion stabilizer, 1 part of composite synergist, 10 parts of hydrochloric acid and the balance of water; the gel acid comprises, by mass, 2 parts of an emulsion gelling agent, 3 parts of a corrosion inhibitor, 1.5 parts of an iron ion stabilizer, 2 parts of a composite synergist, 20 parts of hydrochloric acid, and the balance of water.
The emulsion gelling agent comprises in parts by weight: 40 parts of cationic polyacrylamide, 2 parts of a viscosity modifier, 1 part of fumed silica, 56 parts of methyl nylon acid ester and 1 part of dioctyl sodium sulfosuccinate, wherein the viscosity modifier comprises isophorone diamine and polyvinylpyrrolidone K10 in a ratio of 2: 1.
The preparation of the emulsion gelling agent, and the preparation of the polymer fracturing fluid, the acidic slick water and the gelled acid were the same as in example 1.
Comparative example 1:
the difference from example 1 is that: the emulsion gellant contained no wetting dispersant (dioctyl sodium sulfosuccinate).
Comparative example 2:
the difference from example 1 is that: the emulsion gellant contained no viscosity modifier (isophorone diamine and polyvinylpyrrolidone K10 in a 2:1 ratio).
And (3) testing:
the polymer fracturing fluids obtained in examples 1 to 2 and comparative examples 1 to 2, the acidic slickwater and the gelled acid were subjected to gel breaking viscosity tests, and the test results are shown in table 1 below.
TABLE 1
From table 1 above, it can be observed that:
the time for the acidic slickwater and the gelled acid prepared by the emulsion gelling agent provided in examples 1-2 to reach the maximum viscosity is significantly lower than that of comparative example 1, because the wetting dispersant is adopted in examples 1-2, and the dissolution speed of the emulsion gelling agent in the acid solution (the acidic slickwater or the gelled acid) is increased.
The maximum viscosity of the acidic slickwater and the gelled acid prepared by the emulsion gelling agent provided by the examples 1-2 is obviously higher than that of the comparative example 2, because the viscosity regulator is adopted in the examples 1-2, the viscosity release rate of the emulsion gelling agent in the acid solution is higher.
Common powder gelling agents (PAM, cationic polyacrylamide) and emulsion thickening agents (anionic emulsion polyacrylamide) are selected to replace the emulsion gelling agents in the example 1, polymer fracturing fluid, acidic slickwater and gelled acid are respectively prepared, and the fluid preparation performance is detected and shown in Table 2.
TABLE 2
As can be seen from Table 2, the emulsion gellant provided in example 1 can be used to prepare a polymer fracturing fluid, an acidic slick water and a gelled acid simultaneously in an on-line preparation manner, and the three prepared fluids are shown in FIGS. 1-3, respectively. The emulsion thickener cannot prepare the polymer fracturing fluid in an online preparation manner, and the phenomenon of incompatibility is generated when preparing the acidic slickwater and the gelled acid, and the prepared gelled acid is shown in figure 2. The powder gelatinizer can only prepare polymer fracturing fluid, acidic slick water and gelled acid at an acid preparation station or before acid fracturing construction.
The properties of the polymer fracturing fluid, the acid slick water and the gelled acid prepared in the example 1 were measured separately and are shown in table 3.
Table 3 properties of 3 liquids formulated in example 1
As can be seen from table 3, the proppant carried by the polymer fracturing fluid prepared in example 1 does not settle, the sand carrying property is shown in fig. 5, and the temperature-resistant and shear-resistant curve of the polymer fracturing fluid is shown in fig. 6; the corrosion inhibition rate of the prepared acidic slickwater at 150 ℃ reaches 38.4 g/(m)2H); the corrosion inhibition rate of the prepared gelled acid reaches 39.8 g/(m)2H) the temperature resistance and shear resistance curves of the formulated gelled acid are shown in figure 7.
The foregoing is merely an example of the present invention and common general knowledge of the known specific materials and characteristics thereof has not been described herein in any greater extent. It should be noted that, for those skilled in the art, without departing from the scope of the invention, several variations and modifications can be made, which should also be regarded as the protection scope of the invention, and these will not affect the effect of the implementation of the invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (7)
1. The integrated composite acid is characterized in that: comprises polymer fracturing fluid, acid slick water and gelled acid;
the polymer fracturing fluid comprises, by weight, 0.15-0.6 part of an emulsion gelling agent, 0.2-0.5 part of a cross-linking agent, 0.2-0.5 part of a composite synergist and the balance of water;
the acidic slickwater comprises, by weight, 0.1-0.3 part of emulsion gelling agent, 1-2 parts of corrosion inhibitor, 1-2 parts of iron ion stabilizer, 1-2 parts of composite synergist, 5-15 parts of hydrochloric acid and the balance of water;
the gel acid comprises, by weight, 1-3 parts of an emulsion gelling agent, 1-4 parts of a corrosion inhibitor, 1-2 parts of an iron ion stabilizer, 1-2 parts of a composite synergist, 10-20 parts of hydrochloric acid and the balance of water;
the emulsion gelling agent comprises in parts by weight: 30-50 parts of cationic polyacrylamide, 2-4 parts of viscosity regulator, 0.5-1.2 parts of suspending agent, 40-70 parts of solvent and 0.5-1.5 parts of wetting dispersant.
2. The integrated composite acid of claim 1, wherein: the viscosity regulator comprises isophorone diamine and polyvinylpyrrolidone K10, the suspending agent is fumed silica, the solvent is nylon acid methyl ester, and the wetting dispersant is dioctyl sodium sulfosuccinate.
3. The integrated composite acid of claim 2, wherein: the preparation method of the emulsion gelling agent comprises the following steps:
s1: preparing the components according to the proportion of the emulsion gel;
s2: adding a solvent into a reaction kettle, starting a stirring and emulsifying pump, adding a suspending agent into the reaction kettle according to a ratio, stirring and emulsifying, adding a viscosity regulator, continuing stirring and emulsifying, and then adding cationic polyacrylamide, stirring and emulsifying;
s3: adding wetting dispersant, stirring uniformly, and then passing the whole through a sand mill to obtain the emulsion gel.
4. The integrated composite acid of claim 1, wherein: the polymer fracturing fluid, the acid slick water and the gelled acid are used in an online liquid distribution system, the online liquid distribution system comprises a plurality of metering pumps, a liquid supply pry and an outlet pipeline, and outlet ends of the metering pumps are respectively connected with a liquid adding port of the liquid supply pry.
5. The method for preparing the integrated composite acid according to claim 4, wherein: the preparation method of the polymer fracturing fluid comprises the steps of respectively pumping the emulsion gelling agent, the cross-linking agent and the composite synergist by using different metering pumps, and uniformly mixing the emulsion gelling agent, the cross-linking agent and the composite synergist with clear water pumped by the liquid supply pry in the liquid supply pry to form the polymer fracturing fluid.
6. The method for preparing the integrated composite acid according to claim 4, wherein: the preparation method of the acidic slickwater comprises the steps of respectively pumping the emulsion gelling agent, the corrosion inhibitor, the iron ion stabilizer and the composite synergist by different metering pumps, and uniformly mixing the emulsion gelling agent, the corrosion inhibitor, the iron ion stabilizer and the composite synergist with hydrochloric acid pumped by the liquid supply skid in the liquid supply skid to form the acidic slickwater.
7. The method for preparing the integrated composite acid according to claim 4, wherein: the preparation method of the gelled acid comprises the steps of respectively pumping the emulsion gelling agent, the corrosion inhibitor, the iron ion stabilizer and the composite synergist by using different metering pumps, and uniformly mixing the pumped emulsion gelling agent, the corrosion inhibitor, the iron ion stabilizer and the composite synergist with hydrochloric acid pumped by the liquid supply pry in the liquid supply pry to form the gelled acid.
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Cited By (2)
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| CN114984804A (en) * | 2022-07-15 | 2022-09-02 | 兰州凯宏中原石油科技有限公司 | Oil field oil-water well composite acid mixing and blending method |
| CN115873585A (en) * | 2022-11-30 | 2023-03-31 | 中石化石油工程技术服务有限公司 | Integrated acid liquid system for hot dry rock fracturing and application thereof |
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