CN118165179A - Biological glue fracturing fluid thickener and preparation method thereof - Google Patents
Biological glue fracturing fluid thickener and preparation method thereof Download PDFInfo
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- CN118165179A CN118165179A CN202211588520.XA CN202211588520A CN118165179A CN 118165179 A CN118165179 A CN 118165179A CN 202211588520 A CN202211588520 A CN 202211588520A CN 118165179 A CN118165179 A CN 118165179A
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- 239000012530 fluid Substances 0.000 title claims abstract description 56
- 239000002562 thickening agent Substances 0.000 title claims abstract description 38
- 239000003364 biologic glue Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000012071 phase Substances 0.000 claims abstract description 39
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 17
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 12
- OJHPPRLQCLHOGY-UHFFFAOYSA-M hexadecyl-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CCOC(=O)C(C)=C OJHPPRLQCLHOGY-UHFFFAOYSA-M 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008346 aqueous phase Substances 0.000 claims abstract description 3
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 14
- 230000000035 biogenic effect Effects 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 230000006378 damage Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 230000008961 swelling Effects 0.000 abstract description 7
- 238000010008 shearing Methods 0.000 abstract description 6
- 238000010276 construction Methods 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 7
- 238000004321 preservation Methods 0.000 description 5
- 239000004576 sand Substances 0.000 description 4
- 230000002579 anti-swelling effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001938 Vegetable gum Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000012688 inverse emulsion polymerization Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
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- Colloid Chemistry (AREA)
Abstract
The invention discloses a biological glue fracturing fluid thickener, which is prepared by polymerizing aqueous phase mixed solution and oil phase mixed solution; wherein the water phase mixed solution is formed by mixing 20-25 parts of acrylamide, 5-10 parts of dimethyl p-benzyl allyl ammonium chloride, 5-10 parts of methacryloyloxyethyl dimethyl hexadecyl ammonium chloride and 70 parts of water by weight; the oil phase mixed solution is formed by mixing 5-8 parts by weight of emulsifying agent and 30-40 parts by weight of white oil; the preparation method comprises the steps of uniformly mixing an oil phase mixed solution and a water phase mixed solution, and reacting for 2-4 hours at 35-55 ℃ under the catalysis of azo diiso Ding Mi hydrochloride; the biological glue fracturing fluid thickener can realize hydrophobic association in water, has the characteristics of good swelling and tackifying effects, discharge assistance, swelling prevention, low residue, little harm, good temperature resistance and shearing resistance and the like, and meets the construction requirements.
Description
Technical Field
The invention relates to the technical field of oil and gas field development, in particular to a biological glue fracturing fluid thickener and a preparation method thereof.
Background
Hydraulic fracturing is an important technical measure for increasing the yield of oil and gas wells, and the fracturing fluid is working fluid in hydraulic fracturing construction and has important effects on increasing the diversion capacity of reservoirs and improving the productivity of the oil and gas wells. The conventional vegetable gum fracturing fluid has good performances of sand carrying, shearing resistance and the like, but has the defects of multiple additive types, long swelling time, need of advanced preparation, high residue content, large damage to stratum and the like; and the bio-gel fracturing fluid is more and more concerned because of the clean and low-damage performance.
The published patent CN108048067A discloses a preparation method of biological glue, which is obtained by adopting inverse emulsion polymerization grafting modification, but the tackifying effect is poor due to the fact that the hydrophilicity is too strong and the carbon chain is shorter; therefore, a novel bio-gel fracturing fluid needs to be developed, and the requirements of good swelling and tackifying effects, cleanliness, low damage and the like are met.
Disclosure of Invention
The invention aims to provide a biological gum fracturing fluid thickener which solves the problems of poor tackifying effect and the like of the existing biological gum fracturing fluid thickener.
The invention further aims to provide a reverse emulsion copolymerization preparation method for preparing the biological gum fracturing fluid thickener.
For this purpose, the technical scheme of the invention is as follows:
A biological glue fracturing fluid thickener is prepared by polymerizing aqueous phase mixed solution and oil phase mixed solution; wherein the water phase mixed solution is formed by mixing 20-25 parts of acrylamide, 5-10 parts of dimethyl p-benzyl allyl ammonium chloride, 5-10 parts of methacryloyloxyethyl dimethyl hexadecyl ammonium chloride and 70 parts of water by weight; the oil phase mixed solution is formed by mixing 5-8 parts by weight of emulsifying agent and 30-40 parts by weight of white oil.
The specific chemical structure of the biological glue fracturing fluid thickener is as follows:
preferably, the emulsifier is a mixture of span-60 and op-10.
More preferably, the weight ratio of span-60 to op-10 is (0.6-0.8): 1.
The preparation method of the biological glue fracturing fluid thickener comprises the following preparation steps:
S1, uniformly mixing and stirring acrylamide, dimethyl p-benzyl allyl ammonium chloride, methacryloyloxyethyl dimethyl hexadecyl ammonium chloride and water to obtain a water phase mixed solution;
S2, uniformly mixing the emulsifier and the white oil to obtain an oil phase mixed solution;
S3, uniformly mixing the oil phase mixed solution and the water phase mixed solution, introducing nitrogen to remove oxygen under the stirring condition, and heating to 35-55 ℃; and dropwise adding azo-diiso Ding Mi-line hydrochloride accounting for 0.008-0.012 wt.% of the total weight of the acrylamide, the dimethyl p-benzyl allyl ammonium chloride and the methacryloxyethyl dimethyl hexadecyl ammonium chloride into the reaction mixed solution, and continuing the heat-preserving reaction for 2-4 h to obtain the biological glue fracturing fluid thickener.
Compared with the prior art, the biological glue fracturing fluid thickener can realize hydrophobic association tackifying in water, has the characteristics of good swelling tackifying effect, discharge assistance, swelling prevention, low residue, little harm, good temperature resistance and shearing resistance and the like, meets construction requirements, and has good market application and popularization prospects.
Drawings
FIG. 1 (a) is an SEM image of a bio-gel fracturing fluid thickener prepared in example 4 of the present invention prior to association with water;
FIG. 1 (b) is an SEM image of the biogenic fracturing fluid thickener prepared in example 4 of the present invention after being associated with water;
FIG. 2 is a graph showing the viscosity change with time after the biogenic fracturing fluid thickeners of examples 1 to 5 of the present invention are mixed with water.
Detailed Description
The invention will now be further described with reference to the accompanying drawings and specific examples, which are in no way limiting.
Example 1
A biological glue fracturing fluid thickener is prepared by the following preparation method:
S1, uniformly mixing and stirring 20 parts by weight of acrylamide, 5 parts by weight of dimethyl p-benzyl allyl ammonium chloride, 5 parts by weight of methacryloyloxyethyl dimethyl hexadecyl ammonium chloride and 70 parts by weight of water to obtain a water phase mixed solution;
S2, uniformly mixing 5 parts by weight of emulsifying agent and 30 parts by weight of white oil to obtain an oil phase mixed solution; wherein the emulsifier is a mixture of span-60 and op-10, and the weight ratio of the span-60 to the op-10 is 0.8:1;
And S3, uniformly mixing the oil phase mixed solution and the water phase mixed solution, introducing nitrogen to remove oxygen under the stirring condition, heating to 35 ℃, dropwise adding 0.0024 part by weight of azodiiso Ding Mi hydrochloride, and continuing to perform heat preservation reaction for 4 hours to obtain the biological glue fracturing fluid thickener.
Example 2
A biological glue fracturing fluid thickener is prepared by the following preparation method:
S1, mixing and stirring 23 parts by weight of acrylamide, 10 parts by weight of dimethyl p-benzyl allyl ammonium chloride, 8 parts by weight of methacryloyloxyethyl dimethyl hexadecyl ammonium chloride and 70 parts by weight of water uniformly to obtain a water phase mixed solution;
S2, uniformly mixing 8 parts by weight of an emulsifier and 35 parts by weight of white oil to obtain an oil phase mixed solution; wherein the emulsifier is a mixture of span-60 and op-10, and the weight ratio of the span-60 to the op-10 is 0.6:1;
And S3, uniformly mixing the oil phase mixed solution and the water phase mixed solution, introducing nitrogen to remove oxygen under the stirring condition, heating to 45 ℃, dropwise adding 0.0041 part by weight of azodiiso Ding Mi hydrochloride, and continuing to perform heat preservation reaction for 3 hours to obtain the biological glue fracturing fluid thickener.
Example 3
A biological glue fracturing fluid thickener is prepared by the following preparation method:
s1, uniformly mixing and stirring 25 parts by weight of acrylamide, 8 parts by weight of dimethyl p-benzyl allyl ammonium chloride, 10 parts by weight of methacryloyloxyethyl dimethyl hexadecyl ammonium chloride and 70 parts by weight of water to obtain a water phase mixed solution;
S2, uniformly mixing 6 parts by weight of emulsifying agent and 40 parts by weight of white oil to obtain an oil phase mixed solution; wherein the emulsifier is a mixture of span-60 and op-10, and the weight ratio of the span-60 to the op-10 is 0.6:1;
And S3, uniformly mixing the oil phase mixed solution and the water phase mixed solution, introducing nitrogen to remove oxygen under the stirring condition, heating to 55 ℃, dropwise adding 0.00516 parts by weight of azo diiso Ding Mi hydrochloride, and continuing to perform heat preservation reaction for 4 hours to obtain the biological glue fracturing fluid thickener.
Example 4
A biological glue fracturing fluid thickener is prepared by the following preparation method:
S1, uniformly mixing and stirring 25 parts by weight of acrylamide, 8 parts by weight of dimethyl p-benzyl allyl ammonium chloride, 8 parts by weight of methacryloyloxyethyl dimethyl hexadecyl ammonium chloride and 70 parts by weight of water to obtain a water phase mixed solution;
s2, uniformly mixing 8 parts by weight of emulsifying agent and 30 parts by weight of white oil to obtain an oil phase mixed solution; wherein the emulsifier is a mixture of span-60 and op-10, and the weight ratio of the span-60 to the op-10 is 0.6:1;
And S3, uniformly mixing the oil phase mixed solution and the water phase mixed solution, introducing nitrogen to remove oxygen under the stirring condition, heating to 50 ℃, dropwise adding 0.0041 part by weight of azodiiso Ding Mi hydrochloride, and continuing to perform heat preservation reaction for 3 hours to obtain the biological glue fracturing fluid thickener.
Example 5
A biological glue fracturing fluid thickener is prepared by the following preparation method:
S1, uniformly mixing and stirring 20 parts by weight of acrylamide, 6 parts by weight of dimethyl p-benzyl allyl ammonium chloride, 5 parts by weight of methacryloyloxyethyl dimethyl hexadecyl ammonium chloride and 70 parts by weight of water to obtain a water phase mixed solution;
s2, uniformly mixing 6 parts by weight of an emulsifier and 35 parts by weight of white oil to obtain an oil phase mixed solution; wherein the emulsifier is a mixture of span-60 and op-10, and the weight ratio of the span-60 to the op-10 is 0.6:1;
And S3, uniformly mixing the oil phase mixed solution and the water phase mixed solution, introducing nitrogen to remove oxygen under the stirring condition, heating to 40 ℃, dropwise adding 0.00248 parts by weight of azo diiso Ding Mi hydrochloride, and continuing to perform heat preservation reaction for 3 hours to obtain the biological glue fracturing fluid thickener.
Performance test:
The biogenic fracturing fluid thickeners prepared in examples 1 to 5 were added to water and formulated into 1.0wt.% biogenic fracturing fluid, respectively, and each performance of the biogenic fracturing fluid was tested.
(1) Microstructure test:
The microstructures of the biogenic fracturing fluid thickener prepared in example 4 before and after the biogenic fracturing fluid is prepared are compared; specifically, as shown in fig. 1 (a), SEM electron microscope images of the biogenic fracturing fluid thickener prepared in example 4 before associating with water are shown; an SEM electron micrograph of the biogenic fracturing fluid thickener prepared in example 4 after association with water is shown in fig. 1 (b).
As can be seen from fig. 1 (a), the thickener did not form a network structure before associating with water; as can be seen from fig. 1 (b), the thickener and water strongly associate with each other, so that a viscoelastic fluid with a cross-woven network structure having sand carrying capacity is rapidly formed, and the proppants are carried into the cracks by the viscoelastic sand carrying; therefore, the biological glue fracturing fluid thickener is directly prepared into aqueous solution for use without using a cross-linking agent, and a space reticular structure can be formed only by special acting force among polymer molecules of the space reticular structure, so that excellent sand carrying performance of the liquid is maintained.
(2) Swelling property test:
The viscosity of the biogenic fracturing fluids prepared in examples 1 to 5 was tested over time. FIG. 2 is a graph showing the viscosity of the biogenic fracturing fluids prepared in examples 1 to 5 over time. Accordingly, the viscosity test results are shown in table 1 below.
Table 1:
as can be seen from fig. 2 and table 1, the bio-gel fracturing fluids prepared in examples 1 to 5 gradually increased in viscosity with time, and all of them were completely swelled for about 100 seconds, and the thickening effect was remarkable.
(3) Temperature and shear resistance
With reference to the standard SY/T5107 water-based fracturing fluid liquid evaluation method, the viscosity of the biological gum fracturing fluids prepared in examples 1 to 5 after shearing for 120min at 170s -1 and 120 ℃ is tested to verify the temperature and shear resistance. The specific test results are shown in table 2 below.
Table 2:
As shown by the test results in Table 2, the viscosity of the bio-gel fracturing fluids prepared in examples 1 to 5 is maintained above 60mPa.s after the temperature-resistant shearing test, and meets the standard requirements, so that the bio-gel fracturing fluid has good temperature-resistant shearing-resistant performance.
(3) Surface interfacial tension, anti-swelling Property
With reference to the standard SY/T5107 water-based fracturing fluid evaluation method, the biological gum fracturing fluids prepared in examples 1 to 5 were tested for surface tension, interfacial tension, anti-swelling properties, residue, core damage rate and the like. The specific test results are shown in table 3 below.
Table 3:
As can be seen from Table 3, the bio-gel fracturing fluids prepared in examples 1 to 5 can achieve complete gel breaking within 120min, and the viscosity after gel breaking is 3.3 to 3.6mPa.s; the surface tension is in the range of 22.3N/m-22.8 mN/m, the interfacial tension is in the range of 0.95N/m-1.08 mN/m, and the method has lower surface tension and interfacial tension, and is beneficial to flowback after fracturing; the anti-swelling rate is kept above 85%, and the swelling and migration of clay can be prevented; in addition, the damage rate of the core of the fracturing fluid gel breaking liquid is kept below 10%, the content of residues is kept below 5mg/L, and the real low damage can be truly realized.
Claims (4)
1. The biological glue fracturing fluid thickener is characterized by being prepared by polymerizing aqueous phase mixed solution and oil phase mixed solution; wherein the water phase mixed solution is formed by mixing 20-25 parts of acrylamide, 5-10 parts of dimethyl p-benzyl allyl ammonium chloride, 5-10 parts of methacryloyloxyethyl dimethyl hexadecyl ammonium chloride and 70 parts of water by weight; the oil phase mixed solution is formed by mixing 5-8 parts by weight of emulsifying agent and 30-40 parts by weight of white oil.
2. The biogenic fracturing fluid thickener according to claim 1, wherein the emulsifier is a mixture of span-60 and op-10.
3. The biogenic fracturing fluid thickener according to claim 2, wherein the weight ratio of span-60 to op-10 is (0.6 to 0.8): 1.
4. A method for preparing the biogenic fracturing fluid thickener according to any of claims 1 to 3, comprising the following steps:
S1, uniformly mixing and stirring acrylamide, dimethyl p-benzyl allyl ammonium chloride, methacryloyloxyethyl dimethyl hexadecyl ammonium chloride and water to obtain a water phase mixed solution;
S2, uniformly mixing the emulsifier and the white oil to obtain an oil phase mixed solution;
S3, uniformly mixing the oil phase mixed solution and the water phase mixed solution, introducing nitrogen to remove oxygen under the stirring condition, and heating to 35-55 ℃; and dropwise adding azo-diiso Ding Mi-line hydrochloride accounting for 0.008-0.012 wt.% of the total weight of the acrylamide, the dimethyl p-benzyl allyl ammonium chloride and the methacryloxyethyl dimethyl hexadecyl ammonium chloride into the reaction mixed solution, and continuing the heat-preserving reaction for 2-4 h to obtain the biological glue fracturing fluid thickener.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211588520.XA CN118165179A (en) | 2022-12-09 | 2022-12-09 | Biological glue fracturing fluid thickener and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211588520.XA CN118165179A (en) | 2022-12-09 | 2022-12-09 | Biological glue fracturing fluid thickener and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118165179A true CN118165179A (en) | 2024-06-11 |
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|---|---|---|---|
| CN202211588520.XA Pending CN118165179A (en) | 2022-12-09 | 2022-12-09 | Biological glue fracturing fluid thickener and preparation method thereof |
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| Country | Link |
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| CN (1) | CN118165179A (en) |
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- 2022-12-09 CN CN202211588520.XA patent/CN118165179A/en active Pending
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