CN109913196B - Acidic clean fracturing fluid and preparation method thereof - Google Patents
Acidic clean fracturing fluid and preparation method thereof Download PDFInfo
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- CN109913196B CN109913196B CN201910246586.2A CN201910246586A CN109913196B CN 109913196 B CN109913196 B CN 109913196B CN 201910246586 A CN201910246586 A CN 201910246586A CN 109913196 B CN109913196 B CN 109913196B
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Abstract
The invention discloses an acidic clean fracturing fluid and a preparation method thereof, belonging to the technical field of oil extraction engineering in the petroleum industry. The invention takes two organic acids, N-dimethylamino compounds and halohydrin as raw materials to synthesize the gemini surfactant; then mixing and stirring the gemini surfactant, hydrochloric acid and water according to a certain proportion to obtain the acidic clean fracturing fluid. Compared with the traditional acid fracturing fluid, the acid clean fracturing fluid has the advantages of small using amount of gemini surfactant (0.5-1%), strong acidizing capability on stratum (HCl concentration is 20%), good temperature resistance and shearing resistance, good sand carrying performance, easy gel breaking and no residue after gel breaking.
Description
Technical Field
The invention relates to an acidic clean fracturing fluid and a preparation method thereof, belonging to the technical field of oil extraction engineering in the petroleum industry.
Background
The acidic clean fracturing fluid is a fracturing fluid which can be gelled under acidic conditions and can effectively carry sand and convey a proppant, and generally comprises a surfactant, an acid solution (one or more mixed solutions) and a small amount of an auxiliary agent. The acid-cleaning fracturing fluid realizes synchronous acid etching and sand carrying, can form longer and multi-branch acid etching-supporting composite fractures in a reservoir section, and improves the yield-increasing effect of the oil-gas well. Meanwhile, the defects that the traditional alkaline fracturing fluid reacts with a rock stratum to generate insoluble precipitates, scales on the surface of construction equipment and the like are eliminated.
Some reports on the research of the acid clean fracturing fluid exist at present, for example, the literature (oil and gas institute, 2010, 32 vol., 6 th, 135-138) discloses an acid clean fracturing fluid and a preparation method thereof, wherein the acid clean fracturing fluid consists of 1.5% of viscoelastic amphoteric surfactant (CHJ-22), 0.4% of a small amount of cationic surfactant (ZJ-1), 10% of hydrochloric acid (or composite acid), 1% of inorganic salt, 0.5% of acid liquor corrosion inhibitor and water. The document (drilling and production process, 2016, volume 39, phase 3, 103-105) reports an acidic clean fracturing fluid and a preparation method thereof, wherein the acidic clean fracturing fluid consists of 2% of a hyperbranched polymer active agent CP-1, 0.5% of an amphoteric gemini surfactant GW-1, 8% of hydrochloric acid, 0.4% of an iron ion stabilizer GY-1 and water. Although the acid fracturing fluid can be applied to the development of carbonate reservoirs, the acid fracturing fluid has the following defects: a plurality of additives are needed when the acid clean fracturing fluid is prepared, the working amount of the prepared fluid is large, the time is long, and the cost is high; the acid liquor concentration in the existing acidic clean fracturing fluid is low (the HCl concentration is generally 8% -10%), and the acidizing capability on the stratum is limited. Therefore, the formula and preparation method of the acidic clean fracturing fluid need to be improved urgently, and the concentration of the acid liquor needs to be further increased to enhance the acidification effect and meet the requirements of site construction fracturing.
Disclosure of Invention
The invention aims to provide an acidic clean fracturing fluid which has strong acidizing capability on stratum, good temperature resistance and shearing resistance, good sand carrying performance and convenient use; another object is to provide a process for the preparation thereof.
In order to realize the purpose of the invention, the technical scheme of the invention is as follows:
the acid clean fracturing fluid is prepared by the following method:
1) uniformly mixing two organic acids and an N, N-dimethylamino compound, adding a solid super-strong base catalyst, heating to 90-140 ℃, and reacting to obtain an intermediate;
2) uniformly mixing the intermediate obtained in the step (1) and halogenated alcohol in a mixed solvent, heating to 60-80 ℃, and reacting to obtain a gemini surfactant;
3) the acid clean fracturing fluid is obtained by mixing and stirring according to the following mixture ratio, and the components are calculated by mass percent: 0.5-1% of gemini surfactant obtained in the step (2), 20% of hydrochloric acid and the balance of water;
the organic acid 1 is selected from: r1COOH, wherein R1Is phenyl, cyclohexyl, CnH2n+1，n＝14-22；
The organic acid 2 is selected from: r2COOH, wherein R2Is C9H18＝C12H23,C7H14＝C8H15,CH3(CH2)5CHOHCH2CH＝C8H15,C5H10＝C8H15,CH3(CH2)7CH＝CH(CH2)7；
The structural formula of the N, N-dimethylamino compound is as follows:
R2N(CH3)2
the solid super strong base catalyst is KF/Al2O3、K/MgO、Na/MgO、K/γ-Al2O3、KNO3/Al2O3、KNO3/ZrO2、Na/NaOH/γ-Al2O3、KCO3/γ-Al2O3Or KCO3/ZrO2；
The halogenated alcohol is selected from 1, 3-dichloro-2-propanol and 1, 3-dibromo-2-propanol;
the mixed solvent in the step (2) is ethanol or isopropanol and water;
the feeding mol ratio of the organic acid to the N, N-dimethylamino compound is 1: 0.2-0.6;
the feeding molar ratio of the organic acid to the solid super base catalyst is 10-60: 1;
the feeding molar ratio of the organic acid to the halogenated alcohol is 0.2-1.2: 1;
the adding mass of the mixed solvent in the step (2) is 10-20% of the total mass of the reactants.
The invention has the advantages that: (1) the prepared acid clean fracturing fluid is high in acid liquid concentration (HCl concentration is 20%), and strong in formation acidizing capability. (2) The prepared acid clean fracturing fluid has good temperature resistance, still maintains good performance at 140 ℃, and can meet the use requirements of high-temperature oil and gas fields. (3) The traditional acid clean fracturing fluid usually uses a plurality of additives, and the gemini surfactant content is high, so that the field fluid preparation workload is large, the time is long, and the cost is high; the gemini surfactant content of the acid clean fracturing fluid is low (0.5-1%), the fluid preparation process is simple, the use is convenient, and the cost is low. (4) The water quality of the prepared liquid has no special requirements, and formation water can be directly used for rapid preparation when the preparation liquid is used on site. (5) The sand carrying performance is good; (6) the gel breaking agent can break gel when meeting stratum oil water, no gel breaking agent is required to be added, the viscosity of the gel breaking liquid is low, no residue is generated, no filter cake is generated, and no damage is caused to a bottom layer.
Drawings
Figure 1 is a graph of apparent viscosity versus shear time for an acidic clean fracturing fluid of the present invention.
Figure 2 is the apparent viscosity of the acidic clean fracturing fluid of the present invention as a function of temperature.
Detailed Description
The following embodiments will more fully describe the present invention.
Example 1
The molar ratio of stearic acid to erucic acid to 2-amino-N, N-dimethylacetamide to KF/gamma-Al2O31:2:1:0.3 stearic acid erucic acid l, 3-dichloro-2-propanol 1:2:3, mixed solvent VEthanol:VWater (W)＝1:1。
Adding stearic acid, erucic acid, 2-amino-N, N-dimethylacetamide and KF/gamma-Al into a reaction kettle which is provided with an electric stirrer, a condenser pipe, a thermometer and an oil bath under heating conditions according to the molar ratio2O3Stirring and heating to 90 ℃, keeping the temperature for reaction for 8 hours, and cooling to room temperature to obtain an intermediate. And uniformly mixing the intermediate and the l, 3-dichloro-2-propanol in a mixed solvent, stirring and heating to 70 ℃, keeping the temperature for reaction for 6 hours, and cooling to room temperature to obtain reddish brown liquid, namely the gemini surfactant.
The acid clean fracturing fluid Y1 is obtained by mixing and stirring according to the following mixture ratio, and the components are calculated by mass percent: the invention relates to a gemini surfactant, which comprises 0.8 percent of gemini surfactant, 20 percent of hydrochloric acid and the balance of water.
Example 2
The molar ratio of the massage is as follows: palmitic acid 4-amino-N, N-dimethylaniline K/gamma-Al2O31:1:1:0.1 palmitic acid erucic acid l, 3-dibromo-2-propanol 1:1:2, and V as mixed solventIsopropanol (I-propanol):VWater (W)＝1:1.5。
Is provided with an electric stirrer, a condenser tube and a thermometerAnd adding palmitic acid, erucic acid, 4-amino-N, N-dimethylaniline and K/gamma-Al into the reaction kettle in the molar ratio under the condition of oil bath heating2O3And stirring, heating to 110 ℃, keeping the temperature for reaction for 10 hours, and cooling to room temperature to obtain an intermediate. And uniformly mixing the intermediate and the l, 3-dibromo-2-propanol in a mixed solvent, stirring and heating to 80 ℃, keeping the temperature for reacting for 8 hours, and cooling to room temperature to obtain reddish brown liquid, namely the gemini surfactant.
The acid clean fracturing fluid Y2 is obtained by mixing and stirring according to the following mixture ratio, and the components are calculated by mass percent: the invention relates to a gemini surfactant, which comprises 0.5 percent of gemini surfactant, 20 percent of hydrochloric acid and the balance of water.
Example 3
The molar ratio of the massage is as follows: benzoic acid oleic acid 4-methyl-N, N-dimethyl phenylacetamide KCO3/γ-Al2O31:2:1:0.3 benzoic acid, oleic acid, l, 3-dibromo-2-propanol, 1:2:4 and V as mixed solventEthanol:VWater (W)＝1.5:1。
Adding benzoic acid, oleic acid, 4-methyl-N, N-dimethyl phenylacetamide and KCO into a reaction kettle which is provided with an electric stirrer, a condenser pipe, a thermometer and an oil bath under heating conditions according to the molar ratio3/γ-Al2O3Stirring and heating to 100 ℃, keeping the temperature for reaction for 12 hours, and cooling to room temperature to obtain an intermediate. And uniformly mixing the intermediate and the l, 3-dibromo-2-propanol in a mixed solvent, stirring and heating to 60 ℃, keeping the temperature for reaction for 12 hours, and cooling to room temperature to obtain reddish brown liquid, namely the gemini surfactant.
The acid clean fracturing fluid Y3 is obtained by mixing and stirring according to the following mixture ratio, and the components are calculated by mass percent: the invention relates to a gemini surfactant, which comprises 1 percent of gemini surfactant, 20 percent of hydrochloric acid and the balance of water.
Application example 1
The performance of the clean fracturing fluid Y1 was evaluated.
The clean fracturing liquid belongs to a viscoelastic surfactant fracturing system, and the technical standard adopts SY/T6376-2008 'fracturing liquid general technical conditions' table 4 (viscoelastic surfactant fracturing liquid general technical index), SY/5107-2005 'water-based fracturing liquid performance evaluation method'.
1. Rheological Properties
The shear stability of the acid clean fracturing fluid was evaluated using an RV-20 rheometer. FIG. 1 shows the temperature of 50, 80 and 120 ℃ for 170s-1Viscosity change of fracturing fluid 2h of shear. As can be seen from fig. 1, the acid clean fracturing fluid has better shear resistance and less change of viscosity with time under the conditions of 50 and 80 ℃ and 120 ℃. The test on the shearing resistance of the acid clean fracturing fluid under 3 temperature conditions shows that the change of the apparent viscosity of the acid clean fracturing fluid along with time is small and the reduction is smooth under a certain shearing rate, so that the fracturing fluid has good shearing resistance and can meet the requirements.
2. Temperature resistance
Using RV-20 rheometer at a shear rate of 170s-1Under the conditions of (1), the temperature resistance of the acid clean fracturing fluid is evaluated. The apparent viscosity of the acid-cleaned fracturing fluid is shown in figure 2 as a function of increasing temperature. As can be seen from FIG. 2, the viscosity of the acidic clean fracturing fluid is increased along with the temperature, the viscosity of the system is increased rapidly, and the viscosity reaches a peak at the temperature of about 70 ℃; after 70 ℃, the viscosity continuously decreases along with the continuous rise of the temperature; when the temperature is raised to 140 ℃, the viscosity is still above 30mPa & s, which shows that the acid clean fracturing fluid has strong temperature resistance.
3. Sand carrying capability
A static sand suspension experiment is adopted to represent the sand carrying performance of the acid clean fracturing fluid. The acid clean fracturing fluid was heated to 50 ℃, 80 ℃, 120 ℃, 30% quartz sand was added by mass at constant temperature, and the rate of decrease was observed, with the results shown in table 1. As can be seen from table 1, the acid clean fracturing fluid system has better sand-carrying performance.
Table 1 evaluation of sand-carrying properties of acidic clean fracturing fluids of the invention
4. Gel breaking performance
The acid clean fracturing fluid can break gel when meeting formation oil water, a gel breaker is not required to be added, the viscosity of the gel breaker is low, no residue is generated, no filter cake is generated, and no damage is caused to a bottom layer. The indoor test can break the gel of the acid clean fracturing fluid by adding 1:1 kerosene or 4% ethylene glycol monobutyl ether.
Claims (5)
1. The acid clean fracturing fluid is characterized by being prepared by the following method:
1) uniformly mixing two organic acids, namely organic acid 1 and organic acid 2, with the N, N-dimethylamino compound, adding a solid super-strong base catalyst, heating to 90-140 ℃, and reacting to obtain an intermediate;
2) uniformly mixing the intermediate obtained in the step (1) and halogenated alcohol in a mixed solvent, heating to 60-80 ℃, and reacting to obtain a gemini surfactant;
3) the acid clean fracturing fluid is obtained by mixing and stirring according to the following mixture ratio, and the components are calculated by mass percent: 0.5-1% of gemini surfactant obtained in the step (2), 20% of hydrochloric acid and the balance of water;
the organic acid 1 is selected from: r1COOH, wherein R1Is phenyl, cyclohexyl, CnH2n+1，n=14-22；
The organic acid 2 is selected from: r2COOH, wherein R2Is C9H18=C12H23,C7H14=C8H15,
CH3(CH2)5CHOHCH2CH=C8H15, C5H10=C8H15,CH3(CH2)7CH=CH(CH2)7；
The structural formula of the N, N-dimethylamino compound is as follows:
the solid super-gradeSelecting KF/Al as strong base catalyst2O3、K/MgO、Na/MgO、K/γ-Al2O3、
KNO3/Al2O3、KNO3/ZrO2、Na/ NaOH/γ-Al2O3；
The halogenated alcohol is selected from 1, 3-dichloro-2-propanol and 1, 3-dibromo-2-propanol;
the mixed solvent is ethanol or isopropanol and water.
2. The acid-clean fracturing fluid of claim 1, wherein the molar ratio of the organic acid to the N, N-dimethylamino compound is selected from 1: 0.2-0.6.
3. The acidic clean fracturing fluid of claim 1, wherein the molar ratio of the organic acid to the solid superbase catalyst is selected from the range of 10 to 60: 1.
4. The acid-clean fracturing fluid of claim 1, wherein the molar ratio of the organic acid to the halohydrin is selected from 0.2 to 1.2: 1.
5. The acid-clean fracturing fluid of claim 1, wherein the mixed solvent is added in an amount of 10-20% by weight of the total mass of the reactants.
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