Recyclable clean fracturing fluid thickener, preparation method and recovery method thereof, and high-temperature resistant clean fracturing fluid

Abstract

Disclosed are a recyclable clean fracturing fluid thickener, a preparation method and a recovery method thereof, and a high-temperature resistant clean fracturing fluid, which relate to the stimulation treatment of oil and gas fields. Diethanolamine and thionyl chloride are used as raw materials and reacted to obtain an intermediate, which is then reacted with an unsaturated fatty acid amidopropyl dimethylamine to produce the recyclable clean fracturing fluid thickener. The clean fracturing fluid can be used in the fracturing stimulation treatment of low and medium permeability reservoirs.

Claims

1. A fracturing fluid thickener of the following structural formula: ##STR00004## wherein R is an unsaturated hydrocarbon chain having 17-21 carbon atoms.

2. The fracturing fluid thickener of claim 1, wherein the fracturing fluid thickener is prepared through steps of: (1) dissolving diethanolamine and thionyl chloride in chloroform to obtain a diethanolamine solution and a thionyl chloride solution, respectively; dropwise adding the thionyl chloride solution to the diethanolamine solution in an ice bath and then heating to perform a reaction; and after the reaction is completed, cooling the reaction mixture to produce an intermediate isolating the intermediate; and (2) mixing the intermediate with an unsaturated C.sub.17-C.sub.21 fatty acid amidopropyl dimethylamine to produce a mixture; dissolving the mixture with ethanol; reacting the reaction mixture under heating; filtering the reaction mixture to obtain a filtrate; and distilling the filtrate under vacuum to produce the fracturing fluid thickener.

3. A method of preparing the fracturing fluid thickener of claim 1, comprising: (1) dissolving diethanolamine and thionyl chloride in chloroform to obtain a diethanolamine solution and a thionyl chloride solution, respectively; dropwise adding the thionyl chloride solution to the diethanolamine solution in an ice bath and then heating to perform a reaction; after the reaction is completed, cooling the reaction mixture to produce an intermediate isolating the intermediate; and (2) mixing the intermediate with an unsaturated C.sub.17-C.sub.21 fatty acid amidopropyl dimethylamine to produce a mixture; dissolving the mixture with ethanol; reacting the reaction mixture under heating; filtering the reaction mixture to obtain a filtrate; and distilling the filtrate under vacuum to produce the fracturing fluid thickener.

4. The method of claim 3, wherein in step (1), a reaction temperature is 30-50 C.; a reaction time is 4.5-5.5 h; and a molar ratio of diethanolamine to thionyl chloride is 1:(2.0-2.4).

5. The method of claim 3, wherein in step (2), a reaction temperature is 70-90 C.; a reaction time is 23.5-24.5 h; and a molar ratio of the intermediate to the unsaturated fatty acid amidopropyl dimethylamine is 1:(2.0-2.2).

6. The method of claim 4, wherein in step (1), the reaction temperature is 35-45 C. and the reaction time is 4.8-5.2 h.

7. The method of claim 6, wherein in step (1), the reaction temperature is 40 C. and the reaction time is 5 h.

8. The method of claim 5, wherein in step (2), the reaction temperature is 75-85 C. and the reaction time is 23.8-24.2 h.

9. The method of claim 8, wherein in step (2), the reaction temperature is 80 C. and the reaction time is 24 h.

10. The method of claim 3, wherein the unsaturated fatty acid amidopropyl dimethylamine is N,N-dimethyloleoamide propylamine or erucamide propyl-N, N-dimethylamine.

11. The method of claim 4, wherein the unsaturated fatty acid amidopropyl dimethylamine is N,N-dimethyloleoamide propylamine or erucamide propyl-N, N-dimethylamine.

12. The method of claim 5, wherein the unsaturated fatty acid amidopropyl dimethylamine is N,N-dimethyloleoamide propylamine or erucamide propyl-N, N-dimethylamine.

13. A method for recovering the fracturing fluid thickener of claim 1, comprising: (1) subjecting a fracturing fluid containing the fracturing fluid thickener of claim 1 to gel breaking to produce a gel-breaking product; (2) adding an acid solution to the gel-breaking product obtained in step (1) for phase separation; and (3) collecting an upper solid phase to recover the fracturing fluid thickener.

14. The method of claim 13, wherein the acid solution comprises hydrogen chloride, sulfuric acid, phosphoric acid or carbonic acid.

15. The method of claim 14, wherein the acid solution comprises hydrogen chloride, and an amount of hydrogen chloride is 2-6% by weight of the gel-breaking product.

16. The method of claim 15, wherein the amount of hydrogen chloride is 6% by weight of the gel-breaking product.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a molecular structure and 1H-NMR spectrum of a thickener prepared in Example 6 of the disclosure.

(2) FIG. 2 shows the comparison between the aqueous solutions of a crude thickener product and a pure thickener product in the creep recovery and proppant-suspending performance according to Experimental Example 1 of the disclosure.

(3) FIG. 3 shows the test results of the rheological property of the fracturing fluid prepared in Experimental Example 2 of the disclosure.

(4) FIG. 4 shows the phase separation of the fracturing fluid system after gel breaking according to Experimental Example 2.

(5) FIG. 5 is a scanning electron micrograph of the fracturing fluid prepared from the thickener recovered in Experimental Example 2 according to Experimental Example 3 of the disclosure.

(6) FIG. 6 shows the test results of the rheological property of the fracturing fluid prepared from the thickener recovered in Experimental Example 2 according to Experimental Example 3 of the disclosure.

(7) FIG. 7 shows the test results of the rheological property of the fracturing fluid prepared in Experimental Example 4 of the disclosure.

(8) FIG. 8 illustrates the phase separation of the fracturing fluid system after gel breaking according to Experimental Example 4 of the disclosure.

(9) FIG. 9 is a scanning electron micrograph of the fracturing fluid prepared from the thickener recovered in Experimental Example 4 according to Experimental Example 5 of the disclosure.

(10) FIG. 10 shows the test results of the rheological property of the fracturing fluid prepared in Experimental Example 5 of the disclosure.

DETAILED DESCRIPTION OF EMBODIMENTS

(11) The principles and features of the disclosure will be described below with reference to the accompanying drawings and embodiments. These embodiments are merely illustrative of the disclosure, and are not intended to limit the disclosure. Unless otherwise specified, the process in the following embodiments is carried out under conventional conditions or the conditions recommended by the manufacturer. Unless otherwise specified, the reagents or instruments used below are all commercially available.

(12) The unsaturated fatty acid used in the following embodiments is exemplified by oleic acid. In some embodiments, the unsaturated fatty acid may be palmitic acid or erucic acid.

Example 1

(13) Provided herein was a method of preparing a recyclable clean fracturing fluid thickener, which was specifically described as follows.

(14) Diethanolamine was added to a round-bottomed flask, to which chloroform was added to dissolve the diethanolamine to produce a diethanolamine solution. Thionyl chloride was dissolved in a certain amount of chloroform and dropwise added to the diethanolamine solution in an ice-water bath. After the dropwise adding was completed, the reaction mixture was heated in an oil bath to 30 C. and refluxed for 5.5 h, where a molar ratio of diethanolamine to thionyl chloride was 1:2. After the reaction was completed, the reaction mixture was cooled to 20 C. to produce a white hydrochloride intermediate A. Then the intermediate A and N, N-dimethyloleoaminde propylamine were added to a flask, dissolved with an appropriate amount of ethanol, heated to 70 C. and reacted for 24.5 h, where a molar ratio of the intermediate A to N, N-dimethyloleoaminde propylamine was 1:2. The reaction mixture was filtered, and the filtrate was distilled under vacuum to produce a yellow gelatinous thickener.

Example 2

(15) Provided herein was a method of preparing a recyclable clean fracturing fluid thickener, which was specifically described as follows.

(16) Diethanolamine was added to a round-bottomed flask, to which chloroform was added to dissolve the diethanolamine to produce a diethanolamine solution. Thionyl chloride was dissolved in a certain amount of chloroform and dropwise added to the diethanolamine solution in an ice-water bath. After the dropwise adding was completed, the reaction mixture was heated in an oil bath to 50 C. and refluxed for 4.5 h, where a molar ratio of diethanolamine to thionyl chloride was 1:2.2. After the reaction was completed, the reaction mixture was cooled to 20 C. to produce a white hydrochloride intermediate A. Then the intermediate A and N, N-dimethyl oleoaminde propylamine were added to a flask, dissolved with an appropriate amount of ethanol, heated to 90 C. and reacted for 23.5 h, where a molar ratio of the intermediate A to N, N-dimethyloleoaminde propylamine was 1:2.1. The reaction mixture was filtered, and the filtrate was distilled under vacuum to produce a yellow gelatinous thickener.

Example 3

(17) Provided herein was a method of preparing a recyclable clean fracturing fluid thickener, which was specifically described as follows.

(18) Diethanolamine was added to a round-bottomed flask, to which chloroform was added to dissolve the diethanolamine to produce a diethanolamine solution. Thionyl chloride was dissolved in a certain amount of chloroform and dropwise added to the diethanolamine solution in an ice-water bath. After the dropwise adding was completed, the reaction mixture was heated in an oil bath to 35 C. and refluxed for 5.2 h, where a molar ratio of diethanolamine to thionyl chloride was 1:2.4. After the reaction was completed, the reaction mixture was cooled to 20 C. to produce a white hydrochloride intermediate A. Then the intermediate A and N, N-dimethyloleoaminde propylamine were added to a flask, dissolved with an appropriate amount of ethanol, heated to 75 C. and reacted for 24.2 h, where a molar ratio of the intermediate A to N, N-dimethyloleoaminde propylamine was 1:2.2. The reaction mixture was filtered, and the filtrate was distilled under vacuum to produce a yellow gelatinous thickener.

Example 4

(19) Provided herein was a method of preparing a recyclable clean fracturing fluid thickener, which was specifically described as follows.

(20) Diethanolamine was added to a round-bottomed flask, to which chloroform was added to dissolve the diethanolamine to produce a diethanolamine solution. Thionyl chloride was dissolved in a certain amount of chloroform and dropwise added to the diethanolamine solution in an ice-water bath. After the dropwise adding was completed, the reaction mixture was heated in an oil bath to 45 C. and refluxed for 4.8 h, where a molar ratio of diethanolamine to thionyl chloride was 1:2.4. After the reaction was completed, the reaction mixture was cooled to 20 C. to produce a white hydrochloride intermediate A. Then the intermediate A and N, N-dimethyloleoaminde propylamine were added to a flask, dissolved with an appropriate amount of ethanol, heated to 85 C. and reacted for 23.8 h, where a molar ratio of the intermediate A to N, N-dimethyloleoaminde propylamine was 1:2.2. The reaction mixture was filtered, and the filtrate was distilled under vacuum to produce a yellow gelatinous thickener.

Example 5

(21) Provided herein was a method of preparing a recyclable clean fracturing fluid thickener, which was specifically described as follows.

(22) Diethanolamine was added to a round-bottomed flask, to which chloroform was added to dissolve the diethanolamine to produce a diethanolamine solution. Thionyl chloride was dissolved in a certain amount of chloroform and dropwise added to the diethanolamine solution in an ice-water bath. After the dropwise adding was completed, the reaction mixture was heated in an oil bath to 40 C. and refluxed for 5 h, where a molar ratio of diethanolamine to thionyl chloride was 1:2.4. After the reaction was completed, the reaction mixture was cooled to 20 C. to produce a white hydrochloride intermediate A. Then the intermediate A and N, N-dimethyloleoaminde propylamine were added to a flask, dissolved with an appropriate amount of ethanol, heated to 80 C. and reacted for 24 h, where a molar ratio of the intermediate A to N, N-dimethyloleoaminde propylamine was 1:2.2. The reaction mixture was filtered, and the filtrate was distilled under vacuum to produce a yellow gelatinous thickener

Example 6

(23) Diethanolamine was added to a round-bottomed flask, to which chloroform was added to dissolve the diethanolamine to produce a diethanolamine solution. Thionyl chloride was dissolved in a certain amount of chloroform and dropwise added to the diethanolamine solution in an ice-water bath. After the dropwise adding was completed, the reaction mixture was heated in an oil bath to 40 C. and refluxed for 5 h, where a molar ratio of diethanolamine to thionyl chloride was 1:2.05. After the reaction was completed, the reaction mixture was cooled to 20 C. to produce a white hydrochloride intermediate A. Then the intermediate A and N, N-dimethyloleoaminde propylamine were added to a flask, dissolved with an appropriate amount of ethanol, heated to 80 C. and reacted for 24 h, where a molar ratio of the intermediate A to N, N-dimethyloleoaminde propylamine was 1:2.05. The reaction mixture was filtered, and the filtrate was distilled under vacuum to produce a yellow gelatinous thickener

(24) In order to further improve the purity of the thickener, ethyl acetate was used herein to crystallize the crude product for purification, and the crystallized product had a purity of 99% or more. The molecular structure and 1H-NMR of the obtained thickener were shown in FIG. 1.

Experimental Example 1

(25) The crude thickener product obtained in Example 5 and its purified product (the purification was performed according to the above process) were tested for the creep recovery and proppant-suspending property, and the results were shown in FIG. 2 and Table. 1. The results demonstrated that the aqueous solution prepared from the crude product had better proppant-suspending property, indicating that the synthesized product did not need to be purified, and the conversion rate of the raw material was 100%.

(26) TABLE-US-00001 TABLE 1 Proppant-suspending property of the thickener products before and after purification Product J-22 J-22 Concentration (Before purification) (After purification) (%) 1 2 3 4 5 1 2 3 4 5 Settling time (s) 15.7 / / / / 1.26 1.58 2.26 4.24 7.57 15.69 / / / / 1.45 1.34 2.57 4.35 7.66 19.99 / / / / 1.32 1.46 2.48 4.42 7.32 18.26 / / / / 1.26 1.55 2.62 4.47 7.44 16.36 / / / / 1.46 1.43 2.54 4.55 7.54 17.1 / / / / 1.51 1.51 2.47 4.38 7.69 17.2 / / / / 1.55 1.46 2.55 4.42 7.78 15.95 / / / / 1.43 1.53 2.61 4.67 7.33 Average settling 17.03 / / / / 1.41 1.48 2.51 4.44 7.54 time (s) Settling speed 1.47 / / / / 17.79 16.86 9.95 5.63 3.32 (cm/s) Notes: Proppant: 20-40 mesh ceramsite (375-750 m); Settling height: 25 cm; Temperature: room temperature; / means the ceramsite does not settle.

Experimental Example 2

(27) The surfactant prepared in Example 5 was tested to have a critical micelle concentration of 1.4710.sup.4 mol/L, and then the surfactant was used as a thickener to prepare a fracturing fluid containing 3.7% by weight of the thickener, 0.25% by weight of KCl and 0.1% by weight of KBr.

(28) The above fracturing fluid was subjected to rheological property tests under the shearing conditions of 160 C. and 170 s.sup.1, and the test results were shown in FIG. 3. As shown in FIG. 3, the fracturing fluid system prepared from the thickener provided herein had a resistance to a temperature of 160 C. Moreover, it also had an excellent proppant-suspending property. The fracturing fluid system was subjected to gel breaking with 30% kerosene, and the resulting gel-breaking product was free of residue. Then the gel-breaking product was added with 2% of hydrochloric acid, and a small number of white floccules were generated. The gel-breaking product was layered by standing for a while (as shown in FIG. 4), where the white floccule was recovered as the thickener with a recovery rate of 42%.

Experimental Example 3

(29) The product recovered in Experimental Example 2 was again prepared into a fracturing fluid, which had an obvious micro-network structure (as shown in FIG. 5). The fracturing fluid was tested again for the rheological property under the conditions of 140 C. and 170 s.sup.1, and the test results were shown in FIG. 6. It can be seen from FIGS. 5-6 that the thickener still had desirable performance when reused.

Experimental Example 4

(30) The surfactant prepared in Example 6 was tested to have a critical micelle concentration of 1.4710.sup.4 mol/L, and then the surfactant was used as a thickener to prepare a fracturing fluid containing 4% by weight of the thickener, 0.5% by weight of KCl and 0.15% by weight of KBr.

(31) The above fracturing fluid was subjected to the rheological property test under the shearing conditions of 160 C. and 170 s.sup.1, and the test results were shown in FIG. 7. As shown in FIG. 7, the fracturing fluid system showed resistance to the temperature of 160 C., and there was no obvious settlement in the 2-hour static proppant-suspending process, indicating that it had good proppant-suspending property. The fracturing fluid system was subjected to gel breaking with 30% kerosene, and the resulting gel-breaking product was free of residue. Then the gel-breaking product was added with 6% of hydrochloric acid, and a small number of white floccules were generated. The gel-breaking product was layered by standing for a while (as shown in FIG. 8), where the white floccule was recovered as the thickener with a recovery rate of 100%. It can be obtained from the comparison with Experimental Example 2 that the addition amount of hydrochloric acid significantly affected the recovery rate, specifically, when the hydrochloric acid content was increased from 2% (in Experimental Example 2) to 6%, the recovery rate was accordingly raised from 42% to 100%, indicating that the 6% hydrochloric acid can give rise to the best recovery effect.

Experimental Example 5

(32) The product recovered in Experimental Example 4 was again prepared into a fracturing fluid, which had an obvious micro-network structure (as shown in FIG. 9). The fracturing fluid was tested again for the rheological property under the conditions of 140 C. and 170 s.sup.1, and the test results were shown in FIG. 10. It can be seen from FIGS. 9-10 that the fracturing fluid prepared from the recovered product still had good temperature resistance and micro-network structure.

(33) Described above are only preferred embodiments of the disclosure, which are not intended to limit the disclosure. Any modification, replacement, and improvement made without departing from the spirit of the disclosure shall fall within the scope of the invention.