CN113549443B - Biological gel fracturing fluid thickening agent and preparation method thereof - Google Patents
Biological gel fracturing fluid thickening agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a biogel fracturing fluid thickening agent and a preparation method thereof, and belongs to the technical field of fracturing fluid thickening agents. A thickening agent for biogel fracturing fluid is prepared by mixing emulsion AB and adding reverse demulsifier; a first water phase which comprises 30-50 parts of acrylamide, 1-5 parts of modified beta-cyclodextrin, 80-100 parts of water, 0.008-0.015 part of water-soluble oxidant and 0-0.01 part of azo initiator; the second water phase comprises 30-50 parts of acrylamide, 1-5 parts of functional monomer, 80-100 parts of water, 0.008-0.015 part of water-soluble oxidant and 0-0.01 part of azo initiator. The invention also discloses a preparation method of the biological gel fracturing fluid thickening agent, which is prepared by mixing the emulsion A, the emulsion B and the reverse demulsifier. The biological glue fracturing fluid thickening agent provided by the invention has good thickening effect and excellent temperature resistance and salt resistance.
Description
Technical Field
The invention relates to the technical field of fracturing fluid thickeners, in particular to a biogel fracturing fluid thickener and a preparation method thereof.
Background
Along with the exploration and development of low-permeability and unconventional reservoirs, the reservoir transformation has the characteristics of large displacement, high pump pressure and large scale, which means that a large amount of fracturing flowback waste liquid is generated. The existing fracturing fluid system mostly adopts acrylamide polymers, which are not easy to be biodegraded, so that the treatment difficulty of the flowback fluid is higher. And by introducing the biological monomer, the biological monomer is beneficial to utilizing the metabolism of the formation microorganisms to realize biodegradation, and the residue of polymers in the flowback fluid is reduced, so that a fracturing fluid system is more green and environment-friendly.
Patent CN108048067a discloses a preparation method of biogel for fracturing, which takes abietic acid polyoxyethylene succinic acid monoester sodium sulfonate biosurfactant prepared from natural rosin as a raw material, and the biosurfactant and acrylamide are subjected to emulsion polymerization to prepare the biogel. However, the modified biogums obtained by graft modification all have their own disadvantages, and on one hand, the used modifying agents are strong in hydrophilicity and short in carbon chain, and cannot play a good hydrophobic association role, so that the tackifying effect is poor and the salt resistance is poor, and therefore the requirements of fracturing construction are difficult to meet.
Disclosure of Invention
The applicant considers that if non-covalent bond effects such as association, inclusion and the like can be combined at the same time, a biological monomer is further introduced for modification in a reverse phase emulsion polymerization mode, and therefore a new breakthrough can be made for improving the viscosifying effect and the salt resistance of the fracturing fluid thickening agent.
The invention aims to overcome the technical defects, provides a biological glue fracturing fluid thickening agent and a preparation method thereof, and solves the technical problems of poor thickening effect and poor salt resistance of the fracturing fluid thickening agent in the prior art.
In order to achieve the technical purpose, the technical scheme of the invention provides a biological glue fracturing fluid thickening agent and a preparation method thereof.
A biological glue fracturing fluid thickening agent is prepared by mixing emulsion A and emulsion B and adding an inverse demulsifier;
the emulsion A is prepared by the polymerization reaction of a first water phase and an oil phase; the emulsion B is prepared by the polymerization reaction of a second water phase and an oil phase;
the first water phase comprises, by weight, 30-50 parts of acrylamide, 1-5 parts of modified beta-cyclodextrin, 80-100 parts of water, 0.008-0.015 part of water-soluble oxidant and 0-0.01 part of azo initiator;
the second aqueous phase comprises, by weight, 30-50 parts of acrylamide, 1-5 parts of a functional monomer, 80-100 parts of water, 0.008-0.015 part of a water-soluble oxidant and 0-0.01 part of an azo initiator, wherein the functional monomer is C 8-18 One or more of alkyl hydrophobically modified monomers;
the oil phase comprises 80-100 parts of oil and 1-3 parts of emulsifier according to parts by weight.
Further, the mass ratio of the emulsion A to the emulsion B is (0.8-1.2): 1.
Further, the mass ratio of the reverse demulsifier to the beta-cyclodextrin is (0.5-2): 1-5.
Further, the modified beta-cyclodextrin is one or two of the following structural formulas:
Further, the water-soluble oxidizing agent is one or more of potassium persulfate, ammonium persulfate, sodium persulfate, tert-butyl hydroperoxide, sodium bromate and potassium bromate; and/or the azo initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride and azobisisobutyrimidazole hydrochloride; and/or the oil is one or more of white oil, kerosene, liquid paraffin, dearomatized solvent naphtha and isoparaffin solvent naphtha.
Further, the emulsifier is a cellulose surfactant.
In addition, the invention also provides a preparation method of the biological glue fracturing fluid thickening agent, which comprises the following steps:
preparation of emulsion A: mixing a first water phase and an oil phase to prepare a first mixed solution, emulsifying and shearing the first mixed solution, introducing inert gas into the first mixed solution to remove oxygen, adding a first water-soluble reducing agent, and carrying out polymerization reaction at 40-50 ℃ to prepare emulsion A;
preparation of emulsion B: mixing a second water phase and an oil phase to prepare a second mixed solution, emulsifying and shearing the second mixed solution, introducing inert gas into the second mixed solution to remove oxygen, adding a second water-soluble reducing agent, and carrying out polymerization reaction at 40-50 ℃ to prepare emulsion B;
and mixing the emulsion A and the emulsion B, and adding a reverse demulsifier to obtain the biological gel fracturing fluid thickening agent.
Further, in the preparation of the emulsion A or the emulsion B, the emulsifying and shearing time is 1-15min.
Further, the polymerization reaction is carried out for 4 to 8 hours in preparing the emulsion A or the emulsion B.
Furthermore, the mass ratio of the first water-soluble reducing agent to the modified beta-cyclodextrin is (0.008-0.015) to (1-5); the mass ratio of the second water-soluble reducing agent to the functional monomer is (0.008-0.015) to (1-5).
Compared with the prior art, the invention has the beneficial effects that: the modified beta-cyclodextrin molecule in the emulsion A is in a truncated cone-shaped cavity structure, the inner cavity is hydrophobic, the outer side is hydrophilic, the functional monomer in the emulsion B has a long hydrophobic chain, and the long hydrophobic chain can enter the inner cavity of the cyclodextrin when the emulsion A and the emulsion B are mixed, so that the inclusion effect similar to the 'lock-key' is formed. Compared with the traditional hydrophobic association polymer, the driving force of the hydrophobic association polymer is derived from cyclodextrin inclusion, and the hydrophobic association polymer is a structural fluid based on pure intermolecular inclusion, so that a fracturing fluid thickening agent with better tackifying effect and better temperature resistance and salt resistance is obtained, the viscosity of a base solution prepared by adding 1.75g of the fracturing fluid thickening agent into 500mL of water at 70 ℃ is up to more than 80 mPas, the viscosity of a base solution prepared by adding 1.75g of the fracturing fluid thickening agent into 500mL of saline water at 70 ℃ is up to more than 70 mPas, and the viscosity of the base solution prepared by adding 7.5g of the fracturing fluid thickening agent into 500mL of water at 70 ℃ can be increased to 287 s.
Drawings
FIG. 1 is a graph of the rheology of a base fluid 1 of the present invention;
FIG. 2 is a graph of the rheology of base fluid 2 of the present invention;
FIG. 3 is a graph of the rheology of the base fluid 6 of the present invention;
figure 4 is a graph of the rheology of the base fluid 7 of the present invention.
Detailed Description
The specific embodiment provides a biological glue fracturing fluid thickening agent, which is prepared by mixing emulsion A and emulsion B and adding a reverse demulsifier;
the emulsion A is prepared by the polymerization reaction of a first water phase and an oil phase; the emulsion B is prepared by the polymerization reaction of a second water phase and an oil phase;
the first water phase comprises, by weight, 30-50 parts of acrylamide, 1-5 parts of modified beta-cyclodextrin, 80-100 parts of water, 0.008-0.015 part of water-soluble oxidant and 0-0.01 part of azo initiator;
the second aqueous phase comprises, by weight, 30-50 parts of acrylamide, 1-5 parts of a functional monomer, 80-100 parts of water, 0.008-0.015 part of a water-soluble oxidant and 0-0.01 part of an azo initiator, wherein the functional monomer is C 8-18 One or more of alkyl hydrophobically modified monomers, preferablyIs C 14-18 The alkyl hydrophobic modified monomer has the following molecular structure:
wherein x =6-16, preferably x =12-16;
the oil phase comprises 80-100 parts of oil and 1-3 parts of emulsifier according to parts by weight;
the mass ratio of the emulsion A to the emulsion B is (0.8-1.2) to 1; the mass ratio of the reverse demulsifier to the beta-cyclodextrin is (0.5-2) to (1-5).
Further, the modified beta-cyclodextrin is one or two of the following structural formulas:
The reaction mechanism of the modified beta-cyclodextrin and the functional monomer is shown as follows:
the specific embodiment also comprises a preparation method of the biological glue emulsion thickening agent, which comprises the following steps:
preparation of a first aqueous phase: uniformly mixing acrylamide, modified beta-cyclodextrin, water, a water-soluble oxidant and an azo initiator according to the mixture ratio of the components to prepare a first water phase;
preparation of a second aqueous phase: uniformly mixing acrylamide, a functional monomer, water, a water-soluble oxidant and an azo initiator according to the mixture ratio of the components to prepare a second water phase;
preparing an oil phase: mixing the oil and the emulsifier to obtain an oil phase;
preparation of emulsion A: mixing a first water phase and an oil phase to prepare a first mixed solution, emulsifying and shearing the first mixed solution for 1-15min, introducing inert gas into the first mixed solution to remove oxygen, and adding a first water-soluble reducing agent to perform polymerization reaction at 40-50 ℃ for 4-8h to prepare emulsion A; the mass ratio of the first water-soluble reducing agent to the modified beta-cyclodextrin is (0.008-0.015) to (1-5);
preparation of emulsion B: mixing a second water phase and an oil phase to prepare a second mixed solution, emulsifying and shearing the second mixed solution for 1-15min, introducing inert gas into the second mixed solution to remove oxygen, and adding a second water-soluble reducing agent to perform a polymerization reaction at 40-50 ℃ for 4-8h to prepare an emulsion B; the mass ratio of the second water-soluble reducing agent to the functional monomer is (0.008-0.015) to (1-5);
and mixing the emulsion A and the emulsion B, and adding a reverse demulsifier to obtain the thickening agent of the biogel fracturing fluid.
Further, the water-soluble reducing agent is one or more of sodium bisulfite, tetramethylethylenediamine, sodium metabisulfite and molar salt; the reverse emulsifier is at least one of OP-10, alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether and cocamidopropyl betaine; the alcohol polyoxyethylene ether is one or more of isomeric dodecyl polyoxyethylene ether, isomeric undecyl polyoxyethylene ether and isomeric tridecyl polyoxyethylene ether, and the nonylphenol polyoxyethylene ether is one or more of TX-4, TX-6, TX-7 and TX-10
The first aqueous phase and the second aqueous phase are mixed with the formulation amounts of the oil phase according to the present embodiment.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The embodiment provides a thickening agent for a biogel fracturing fluid, which is prepared by mixing emulsion A and emulsion B and adding an inverse demulsifier;
the emulsion A is prepared by the polymerization reaction of a first water phase and an oil phase; the emulsion B is prepared by the polymerization reaction of a second water phase and an oil phase;
the first water phase comprises, by weight, 40 parts of acrylamide, 3 parts of modified beta-cyclodextrin, 85 parts of deionized water, 0.01 part of water-soluble oxidant potassium persulfate and 0.005 part of azo initiator azodiisobutylimidazoline hydrochloride, and the pH is adjusted to be =7;
the second water phase comprises, by weight, 40 parts of acrylamide, 2 parts of a functional monomer, namely a hexadecyl hydrophobic modified monomer, 85 parts of deionized water, 0.01 part of a water-soluble oxidizing agent potassium persulfate and 0.005 part of azo initiator azodiisobutylimidazoline hydrochloride, and the pH is adjusted to be =7;
the oil phase comprises 85 parts of white oil and 1.5 parts of emulsifier cellulose surfactant according to parts by weight;
the mass ratio of the emulsion A to the emulsion B is 1:1; the mass ratio of the reverse demulsifier OP-10 to the beta-cyclodextrin is 1:3.
The embodiment also provides a preparation method of the biological gel fracturing fluid thickening agent, which comprises the following steps:
preparation of emulsion A: adding a first water phase into an oil phase, mixing to prepare a first mixed solution, emulsifying and shearing the first mixed solution for 10min, introducing inert gas into the first mixed solution to remove oxygen, adding a first water-soluble reducing agent sodium bisulfite, and carrying out polymerization reaction at 45 ℃ for 6h to prepare emulsion A; the mass ratio of the first water-soluble reducing agent sodium bisulfite to the modified beta-cyclodextrin is 0.01;
preparation of emulsion B: adding a second water phase into the oil phase, mixing to obtain a second mixed solution, emulsifying and shearing the second mixed solution for 10min, introducing inert gas into the second mixed solution to remove oxygen, adding a second water-soluble reducing agent sodium bisulfite, and carrying out polymerization reaction for 6h at 45 ℃ to obtain emulsion B; the mass ratio of the second water-soluble reducing agent sodium bisulfite to the functional monomer is 0.01;
and mixing the emulsion A and the emulsion B according to a mass ratio of 1:1, and adding a reverse demulsifier to obtain the biogel fracturing fluid thickening agent, wherein the mass ratio of the reverse demulsifier to the beta-cyclodextrin is 1:3.
Wherein, the molecular structure of the functional monomer A is as follows:
Example 2
The embodiment provides a thickening agent for a biogel fracturing fluid, which is prepared by mixing emulsion A and emulsion B and adding an inverse demulsifier;
the emulsion A is prepared by the polymerization reaction of a first water phase and an oil phase; the emulsion B is prepared by the polymerization reaction of a second water phase and an oil phase;
the first water phase comprises, by weight, 30 parts of acrylamide, 1 part of modified beta-cyclodextrin, 80 parts of deionized water, 0.008 part of water-soluble oxidant ammonium persulfate and 0.008 part of azo initiator azobisisoheptonitrile, and the pH is adjusted to be =7;
the second water phase comprises, by weight, 30 parts of acrylamide, 1 part of a hydrophobic monomer octadecyl hydrophobic modified monomer, 80 parts of deionized water, 0.008 part of a water-soluble oxidant sodium persulfate and 0.008 part of azo initiator azobisisobutyronitrile, and the pH is adjusted to be =7;
the oil phase comprises 80 parts of kerosene and 1 part of emulsifier cellulose surfactant by weight;
the mass ratio of the emulsion A to the emulsion B is 0.8; the mass ratio of the reverse demulsifier OP-10 to the beta-cyclodextrin is 0.5.
The embodiment also provides a preparation method of the biological gel fracturing fluid thickening agent, which comprises the following steps:
preparation of emulsion A: adding a first water phase into an oil phase, mixing to prepare a first mixed solution, emulsifying and shearing the first mixed solution for 15min, introducing inert gas into the first mixed solution to remove oxygen, adding a first water-soluble reducing agent tetramethylethylenediamine, and carrying out polymerization reaction for 4h at 40 ℃ to prepare an emulsion A; the mass ratio of the tetramethylethylenediamine used as the first water-soluble reducing agent to the modified beta-cyclodextrin used is 0.008;
preparation of emulsion B: adding a second water phase into the oil phase, mixing to obtain a second mixed solution, emulsifying and shearing the second mixed solution for 15min, introducing inert gas into the second mixed solution to remove oxygen, and adding a second water-soluble reducing agent, namely tetramethylethylenediamine, to perform a polymerization reaction for 4h at 40 ℃ to obtain emulsion B; the mass ratio of the second water-soluble reducing agent tetramethylethylenediamine to the functional monomer is 0.008;
mixing the emulsion A and the emulsion B according to a mass ratio of 0.8 to 1, and adding a reverse demulsifier to obtain the biogel fracturing fluid thickening agent, wherein the mass ratio of the reverse demulsifier to the beta-cyclodextrin is 0.5.
Wherein, the molecular structure of the functional monomer A is as follows:
Example 3
The embodiment provides a thickener for a biogel fracturing fluid, which is prepared by mixing emulsion A and emulsion B and adding a reverse demulsifier;
the emulsion A is prepared by the polymerization reaction of a first water phase and an oil phase; the emulsion B is prepared by the polymerization reaction of a second water phase and an oil phase;
the first water phase comprises, by weight, 50 parts of acrylamide, 5 parts of modified beta-cyclodextrin, 90 parts of deionized water, 0.015 part of water-soluble oxidant sodium bromate, 0.01 part of azo initiator and 0.01 part of dimethyl azodiisobutyrate, and the pH is adjusted to be =7;
the second water phase comprises, by weight, 50 parts of acrylamide, 5 parts of a functional monomer, namely a hexadecyl hydrophobic modified monomer, 90 parts of deionized water, 0.015 part of a water-soluble oxidizing agent, 0.01 part of an azo initiator and 0.01 part of dimethyl azodiisobutyrate, and the pH is adjusted to be =7;
the oil phase comprises 90 parts of liquid paraffin and 3 parts of emulsifier cellulose surfactant by weight;
the mass ratio of the emulsion A to the emulsion B is 1.2; the mass ratio of the reverse demulsifier OP-10 to the beta-cyclodextrin is 1.5.
The embodiment also provides a preparation method of the biological gel fracturing fluid thickening agent, which comprises the following steps:
preparation of emulsion A: adding a first water phase into an oil phase, mixing to prepare a first mixed solution, emulsifying and shearing the first mixed solution for 10min, introducing inert gas into the first mixed solution to remove oxygen, and adding a first water-soluble reducing agent sodium metabisulfite to perform a polymerization reaction at 50 ℃ for 7h to prepare an emulsion A; the mass ratio of the first water-soluble reducing agent sodium pyrosulfite to the modified beta-cyclodextrin is 0.015;
preparation of emulsion B: adding a second water phase into the oil phase, mixing to obtain a second mixed solution, emulsifying and shearing the second mixed solution for 10min, introducing inert gas into the second mixed solution to remove oxygen, adding a second water-soluble reducing agent sodium metabisulfite, and carrying out polymerization reaction for 7h at 50 ℃ to obtain emulsion B; the mass ratio of the second water-soluble reducing agent sodium metabisulfite to the functional monomer is 0.015;
and mixing the emulsion A and the emulsion B, and adding a reverse demulsifier to obtain the biological gel fracturing fluid thickening agent.
Wherein, the molecular structure of the functional monomer A is as follows:
Example 4
The embodiment provides a thickening agent for a biogel fracturing fluid, which is prepared by mixing emulsion A and emulsion B and adding an inverse demulsifier;
the emulsion A is prepared by the polymerization reaction of a first water phase and an oil phase; the emulsion B is prepared by the polymerization reaction of a second water phase and an oil phase;
the first water phase comprises, by weight, 45 parts of acrylamide, 2 parts of modified beta-cyclodextrin, 100 parts of deionized water, 0.012 part of water-soluble oxidant tert-butyl hydroperoxide and 0.006 part of azo initiator azo diisobutyramidine hydrochloride, and the pH is adjusted to be =7;
the second water phase comprises, by weight, 45 parts of acrylamide, 2 parts of a functional monomer hydrophobic monomer octadecyl hydrophobic modified monomer, 100 parts of deionized water, 0.01 part of water-soluble oxidant tert-butyl hydroperoxide and 0.006 part of azo initiator azo diisobutyl amidine hydrochloride, and the pH is adjusted to be =7;
the oil phase comprises 100 parts of white oil and 2 parts of emulsifier cellulose surfactant according to parts by weight;
the mass ratio of the emulsion A to the emulsion B is 0.9; the mass ratio of the reverse demulsifier OP-10 to the beta-cyclodextrin is 1.5.
The embodiment also provides a preparation method of the biological glue fracturing fluid thickening agent, which comprises the following steps:
preparation of emulsion A: adding a first water phase into an oil phase, mixing to obtain a first mixed solution, emulsifying and shearing the first mixed solution for 5min, introducing inert gas into the first mixed solution to remove oxygen, adding a first water-soluble reducing agent sodium metabisulfite, and carrying out polymerization reaction for 7h at 50 ℃ to obtain emulsion A; the mass ratio of the first water-soluble reducing agent sodium metabisulfite to the modified beta-cyclodextrin is 0.012;
preparation of emulsion B: adding a second water phase into the oil phase, mixing to obtain a second mixed solution, emulsifying and shearing the second mixed solution for 5min, introducing inert gas into the second mixed solution to remove oxygen, and adding a second water-soluble reducing agent sodium metabisulfite to perform polymerization reaction for 7h at 45 ℃ to obtain emulsion B; the mass ratio of the second water-soluble reducing agent sodium metabisulfite to the functional monomer is 0.012;
and mixing the emulsion A and the emulsion B, and adding a reverse demulsifier to obtain the thickening agent of the biogel fracturing fluid.
Wherein the molecular structure of the functional monomer A is as follows:
Example 5
The embodiment provides a thickener for a biogel fracturing fluid, which is prepared by mixing emulsion A and emulsion B and adding a reverse demulsifier;
the emulsion A is prepared by the polymerization reaction of a first water phase and an oil phase; the emulsion B is prepared by the polymerization reaction of a second water phase and an oil phase;
the first water phase comprises 35 parts of acrylamide, 4 parts of modified beta-cyclodextrin, 95 parts of deionized water, 0.01 part of water-soluble oxidant potassium persulfate and 0.007 part of azo initiator azodiisoheptanonitrile in parts by weight, and the pH is adjusted to be =7;
the second water phase comprises 35 parts of acrylamide, 4 parts of a functional monomer hexadecyl hydrophobic modified monomer, 95 parts of deionized water, 0.01 part of a water-soluble oxidant sodium persulfate and 0.007 part of azo initiator dimethyl azodiisobutyrate in parts by weight, and the pH is adjusted to be =7;
the oil phase comprises 95 parts of white oil and 2.5 parts of emulsifier cellulose surfactant according to parts by weight;
the mass ratio of the emulsion A to the emulsion B is 1.1; the mass ratio of the reverse demulsifier OP-10 to the beta-cyclodextrin is 1:4.
The embodiment also provides a preparation method of the biological gel fracturing fluid thickening agent, which comprises the following steps:
preparation of emulsion A: adding a first water phase into an oil phase, mixing to prepare a first mixed solution, emulsifying and shearing the first mixed solution for 3min, introducing inert gas into the first mixed solution to remove oxygen, adding a first water-soluble reducing agent sodium bisulfite, and carrying out polymerization reaction at 45 ℃ for 5h to prepare emulsion A; the mass ratio of the first water-soluble reducing agent sodium bisulfite to the modified beta-cyclodextrin is 0.01;
preparation of emulsion B: adding a second water phase into the oil phase, mixing to obtain a second mixed solution, emulsifying and shearing the second mixed solution for 3min, introducing inert gas into the second mixed solution to remove oxygen, adding a second water-soluble reducing agent sodium bisulfite, and carrying out polymerization reaction at 45 ℃ for 5h to obtain emulsion B; the mass ratio of the second water-soluble reducing agent sodium bisulfite to the functional monomer is 0.01;
and mixing the emulsion A and the emulsion B, and adding a reverse demulsifier to obtain the biological gel fracturing fluid thickening agent.
Wherein, the molecular structure of the functional monomer A is as follows:
Comparative example 1
The biogel fracturing fluid thickening agent prepared in the comparative example is different from that prepared in the example 1 in that the modified beta-cyclodextrin is not added, and other formulas and processes are the same as those of the example 1.
Comparative example 2
The difference between the thickening agent of the bio-gel fracturing fluid prepared by the comparative example and the thickening agent of the bio-gel fracturing fluid prepared by the example 1 is that no hexadecyl hydrophobic modified monomer is added, and the other formula and the process are the same as those of the example 1.
And (3) viscosity performance testing:
(1) Weighing analytical reagents KCl 2g, naCl 5.5g and MgCl 2 ·6H 2 O 0.96g、CaCl 2 0.55g of the extract is dissolved in a volumetric flask of 1000mL by distilled water, the volume is accurately determined, and the extract is shaken up and then placed for more than 2 hours to obtain one tenth of standard saline;
(2) Weighing 1.75g of the thickening agent for the biogel fracturing fluid prepared in the examples 1-5 and the comparative examples 1-2, weighing 500mL of distilled water in a mixer, starting at a low speed, slowly adding the weighed thickening agent for the biogel fracturing fluid, and stirring at 6000rpm +/-200 rpm for 5min to obtain base fluids 1-7, wherein the base fluids 1-5 correspond to the examples 1-5 respectively, and the base fluids 6-7 correspond to the comparative examples 1-2 respectively;
(3) Weighing 1.75g of the thickening agent of the bio-gel fracturing fluid prepared in the examples 1-5 and the comparative examples 1-2, weighing 500mL of standard saline water in a mixer, starting at a low speed, slowly adding the weighed thickening agent of the bio-gel fracturing fluid, and stirring at 6000rpm +/-200 rpm for 5min to obtain a base fluid 8-14; base liquids 8 to 12 correspond to examples 1 to 5, respectively, and base liquids 6 to 7 correspond to comparative examples 1 to 2, respectively;
(4) 3.5g, 5g and 7.5g of the thickening agent for the bio-gel fracturing fluid prepared in example 1 are weighed and mixed with 500mL of distilled water respectively to prepare base fluids 15 (3.5 g), 16 (5 g) and 17 (7.5 g) according to the step (2);
(5) Taking 50mL of base fluid 1-17, sequentially placing into a rheometer sample cup, evaluating rheological properties, setting the temperature at 70 ℃, and the shear rate at 170s -1 The viscosity of the liquid after 1h of shear was recorded and the results are shown in tables 1-3.
As can be seen from the rheological curves of FIGS. 1-4, the viscosity of each base fluid decreases as the temperature increases from 30 ℃ to 70 ℃. At 70 deg.C for 170s -1 After 1 hour of shear at the rate of (3), the viscosity of the base liquid 1 was finally 83 mPas, the viscosity of the base liquid 2 was 84 mPas, the viscosity of the base liquid 3 was 74 mPas, and the viscosity of the base liquid 4 was 77 mPas. The viscosity of the thickening agent of the biogel fracturing fluid in brine is slightly reduced compared with that in distilled water,but still reaches the index of the industry standard (50 mPas).
TABLE 1 results of viscosity measurements of base fluids 1-7
| Base liquid numbering | Viscosity (mPa. S) |
| 1 | 83 |
| 2 | 84 |
| 3 | 85 |
| 4 | 81 |
| 5 | 80 |
| 6 | 55 |
| 7 | 52 |
As can be seen from table 1, the proposed bio-gel fracturing fluid thickeners of the present invention have better consistency at lower concentrations, up to 80mPa · s, while comparative examples 1 and 2 have significantly lower consistency due to the lack of modified β -cyclodextrin or cetyl hydrophobically modified monomer, indicating that the bio-gel fracturing fluid thickeners of the present invention achieve their consistency improvement in combination with other components.
TABLE 2 results of viscosity measurements of base fluids 8-14
| Base fluid numbering | Viscosity (mPa. S) |
| 8 | 74 |
| 9 | 77 |
| 10 | 76 |
| 11 | 75 |
| 12 | 73 |
| 13 | 21 |
| 14 | 20 |
As can be seen from Table 2, the viscosity of the thickening agent of the bio-gel fracturing fluid provided by the invention in saline water is slightly reduced compared with that in distilled water, but the viscosity is still more than 70mPa & s and still reaches the index of the industrial standard (50 mPa & s), while the viscosity of comparative examples 1 and 2 is as low as 20mPa & s, the influence of saline water environment on the consistency of comparative examples 1 and 2 is large, and the salt resistance of the thickening agent of the bio-gel fracturing fluid provided by the invention can be further improved under the matching of the components.
TABLE 3 results of viscosity measurements of base fluid 1 and base fluids 15-17
| Base liquid numbering | Viscosity (mPa. S) |
| 1 | 83 |
| 15 | 156 |
| 16 | 218 |
| 17 | 287 |
As can be seen from Table 3, the viscosity of the bio-gel fracturing fluid thickening agent can be obviously increased by gradually increasing the concentration of the bio-gel fracturing fluid thickening agent, and when the concentration of the bio-gel fracturing fluid thickening agent is 7.5g/500mL, the viscosity of the bio-gel fracturing fluid thickening agent is as high as 287mPa & s.
In addition, the invention adopts the biological material as the comonomer, and can be easily biodegraded, thereby effectively solving the problem of difficult treatment of the subsequent fracturing flow-back fluid. Therefore, the biological glue fracturing fluid thickening agent is more green and environment-friendly.
According to the invention, through proper molecular chain structural design, a biological material is adopted as a reaction raw material, cellulose and the like are adopted as emulsifying agents, modified beta-cyclodextrin is adopted as a comonomer, and non-covalent bond effects such as association, inclusion, complexation and the like are combined to form the novel biological gel fracturing fluid thickening agent, so that various performances such as salt resistance, high-efficiency thickening, salt thickening, structural sand suspension and the like are realized, and the requirements of environmental protection can be met.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (8)
1. The biological glue fracturing fluid densifier is characterized in that the densifier is obtained by mixing emulsion A and emulsion B and adding a reverse demulsifier;
the emulsion A is prepared by the polymerization reaction of a first water phase and an oil phase; the emulsion B is prepared by the polymerization reaction of a second water phase and an oil phase;
the first water phase comprises, by weight, 30-50 parts of acrylamide, 1-5 parts of modified beta-cyclodextrin, 80-100 parts of water, 0.008-0.015 part of water-soluble oxidant and 0-0.01 part of azo initiator;
the second water phase comprises, by weight, 30-50 parts of acrylamide, 1-5 parts of a functional monomer, 80-100 parts of water, 0.008-0.015 part of a water-soluble oxidant and 0-0.01 part of an azo initiator, wherein the functional monomer is C 8-18 One or two of alkyl hydrophobic modification monomers;
the oil phase comprises 80-100 parts of oil and 1-3 parts of emulsifier by weight, and the modified beta-cyclodextrin is one or two of the following structural formulas:
2. The biological gel fracturing fluid thickening agent according to claim 1, wherein the mass ratio of the emulsion A to the emulsion B is (0.8-1.2): 1.
3. The biogel fracturing fluid thickener according to claim 1, wherein the mass ratio of the reverse demulsifier to the modified beta-cyclodextrin is (0.5-2) to (1-5).
4. The biogel fracturing fluid viscosifier according to claim 1, wherein the water soluble oxidant is one or more of potassium persulfate, ammonium persulfate, sodium persulfate, tert-butyl hydroperoxide, sodium bromate and potassium bromate; and/or the azo initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride and azobisisobutyrimidazoline hydrochloride; and/or the oil is one or more of kerosene, liquid paraffin, dearomatized solvent oil and isoparaffin solvent oil.
5. The biogel fracturing fluid viscosifier of claim 1, wherein the emulsifier is a cellulosic surfactant.
6. A method for preparing the thickening agent for biogel fracturing fluid as set forth in any one of claims 1 to 5, which comprises the steps of:
preparation of emulsion A: mixing a first water phase and an oil phase to prepare a first mixed solution, emulsifying and shearing the first mixed solution, introducing inert gas into the first mixed solution to remove oxygen, adding a first water-soluble reducing agent, and performing polymerization reaction at 40-50 ℃ to prepare emulsion A;
preparation of emulsion B: mixing a second water phase and an oil phase to prepare a second mixed solution, emulsifying and shearing the second mixed solution, introducing inert gas into the second mixed solution to remove oxygen, adding a second water-soluble reducing agent, and carrying out polymerization reaction at 40-50 ℃ to prepare emulsion B;
and mixing the emulsion A and the emulsion B, and adding a reverse demulsifier to obtain the thickening agent of the biogel fracturing fluid.
7. The method of claim 6, wherein the emulsifying and shearing time is 1-15min during the preparation of the emulsion A or the emulsion B.
8. The method of claim 6, wherein the polymerization is carried out for 4-8 hours in the preparation of the emulsion A or the emulsion B.
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