CN111019627B - Drag reducer and preparation method and application thereof - Google Patents
Drag reducer and preparation method and application thereof Download PDFInfo
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- CN111019627B CN111019627B CN201911301620.8A CN201911301620A CN111019627B CN 111019627 B CN111019627 B CN 111019627B CN 201911301620 A CN201911301620 A CN 201911301620A CN 111019627 B CN111019627 B CN 111019627B
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
- C09K8/604—Polymeric surfactants
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
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- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
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- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
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Abstract
The invention provides a drag reducer, a preparation method and application thereof. The raw materials of the drag reducer are polyether polyol, polydimethylsiloxane and polylauryl methacrylate; wherein the mass ratio of the polyether polyol to the polylauryl methacrylate is 1:1-6:1, and the volume ratio of the solution of the polyether polyol containing the polylauryl methacrylate to the polydimethylsiloxane is 2:1-4: 1. The drag reducer can effectively solve the problem of large resistance in the fracturing process of the supercritical carbon dioxide under the condition of not obviously increasing the viscosity of the supercritical carbon dioxide.
Description
Technical Field
The invention relates to a drag reducer, in particular to a drag reducer capable of reducing the resistance of liquid carbon dioxide during fracturing of the liquid carbon dioxide, and belongs to the technical field of oil exploitation.
Background
The carbon dioxide fracturing can obviously increase the complexity and the extension direction of cracks around a shaft, but the carbon dioxide has low viscosity and strong filtration property, the requirement on the discharge capacity of the carbon dioxide fracturing construction is higher, and the liquid carbon dioxide has higher friction resistance compared with the traditional water-based fracturing fluid and is about 1.5 times of the friction resistance of the guanidine gum fracturing fluid, so that the pressure of a well mouth in site construction is overhigh, the problems of difficult construction, less sand carrying, easy air channeling, easy leakage, unsatisfactory yield increasing effect and the like are shown in the site practical application, the construction discharge capacity cannot meet the design requirement, and therefore, the development of a drag reducer suitable for the liquid carbon dioxide fracturing fluid is urgently needed.
Disclosure of Invention
One object of the present invention is to provide a drag reducer that reduces the drag of liquid carbon dioxide when fracturing.
Another object of the present invention is to provide a method for preparing the drag reducer.
It is still another object of the present invention to provide a method for reducing the resistance of liquid carbon dioxide to fracturing.
In order to achieve the above object, the present invention provides a drag reducer, which is prepared from polyether polyol, polydimethylsiloxane and polylauryl methacrylate; wherein the mass ratio of the polyether polyol to the polylauryl methacrylate is 1:1-6:1, and the volume ratio of the solution of the polyether polyol containing the polylauryl methacrylate to the polydimethylsiloxane is 2:1-4: 1.
The polylauryl methacrylate is a solid, and the solution liquid of the polylauryl methacrylate-containing polyether polyol is a mixed solution of polyether polyol and polylauryl methacrylate.
The invention uses the mutual action of polyether polyol, polydimethylsiloxane and polylauryl methacrylate to form the drag reducer, and effectively reduces the resistance of supercritical carbon dioxide under the condition of ensuring that the viscosity of the supercritical carbon dioxide is not increased remarkably.
In one embodiment of the present invention, the polyether polyol has a molecular weight of 1000-. For example, the polyether polyol used may be selected from polyoxypropylene glycol, polytetrahydrofuran glycol, tetrahydrofuran-oxypropylene copolyol and modified polyether polyols.
Wherein, the tetrahydrofuran-propylene oxide copolymerized glycol can be prepared according to the following steps:
tetrahydrofuran and propylene oxide are subjected to ring opening polymerization under the catalysis, and are subjected to neutralization, water washing, dehydration and filtration to obtain the tetrahydrofuran-propylene oxide copolymerized glycol.
In one embodiment of the present invention, the viscosity of polydimethylsiloxane is 5000-.
In one embodiment of the present invention, the molecular weight of polylauryl methacrylate is 1500-.
In one embodiment of the present invention, polylauryl methacrylate is prepared according to the following steps:
respectively dissolving 30-60 mL of lauryl methacrylate and 10-30 mL of divinylbenzene in 80-100 mL of N, N-dimethylformamide to obtain a mixed solution;
dissolving 2g-4g of azobisisobutyronitrile into 20mL-50mL of absolute ethyl alcohol, dripping into the mixed solution under continuous stirring, heating to 70-90 ℃, reacting for 4-6 h, and protecting with nitrogen in the reaction process;
cooling, washing, freezing and drying to obtain blocky polylauryl methacrylate.
The invention also provides a preparation method of the drag reducer, which comprises the following steps:
mixing polyether polyol and polydimethylsiloxane, and adding polylauryl methacrylate.
The drag reducer can be used for reducing the resistance of liquid carbon dioxide in fracturing, wherein the mass ratio of the drag reducer to the carbon dioxide is 0.3-0.5%: 1.
the drag reducer has the drag reduction rate of over 63.01 percent, does not form solid compounds at the temperature of 80-100 ℃ underground, and can return with fracturing fluid to prevent stratum retention from causing damage; the drag reducer has good solubility with liquid carbon dioxide, and can form a uniform mixed solution within 2 min; after addition of drag reducer, at 170s-1The viscosity of the liquid carbon dioxide under shear conditions was 0.03465cp, less than that of clear water.
The drag reducer disclosed by the invention realizes ordered motion of carbon dioxide by utilizing a carbon chain skeleton of the polylauryl methacrylate, as shown in figure 2, solves the resistance caused by the disorder of carbon dioxide molecules (as shown in figure 1), reduces the friction resistance of the carbon dioxide, increases the viscosity of the carbon dioxide and increases the sand carrying capacity. Polyether and polysiloxane are used as main raw materials, a liquid film is formed on the surface of a fracture wall (as shown in figure 3), so that the friction coefficient mu of carbon dioxide and the fracture in the relative movement process is reduced, and according to the condition that F (friction resistance) is equal to mu (friction coefficient) N (pressure), when the pressure is not changed, the reduction of the friction coefficient effectively reduces the surface friction force and the friction resistance.
The drag reducer is a high molecular weight organic mixture with a specific molecular weight, and can effectively solve the problem of large resistance in the supercritical carbon dioxide fracturing process without remarkably increasing the viscosity of the supercritical carbon dioxide.
Drawings
FIG. 1 is a schematic diagram of carbon dioxide molecules in different fluid states.
FIG. 2 is a schematic view showing the effective combination of organic polymer material and carbon dioxide.
FIG. 3 is a schematic diagram of the movement of supercritical carbon dioxide fluid in the fracture wall before and after film coating.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides a drag reducer for reducing resistance of liquid carbon dioxide in fracturing, which is prepared by the following steps.
Preparing polyether polyol: tetrahydrofuran and propylene oxide are catalyzed to open ring and polymerize, and through neutralization, water washing, dewatering, filtering and other steps, tetrahydrofuran-propylene oxide polyglycol with molecular weight of 2000 is prepared.
Mixing tetrahydrofuran-propylene oxide copolymer glycol and polydimethylsiloxane with the viscosity of 8000 according to the mass ratio of 5:2, mixing them uniformly.
Preparing polylauryl methacrylate, which is prepared according to the following steps:
respectively dissolving 40mL of lauryl methacrylate and 22mL of divinylbenzene in 87mL of N, N-dimethylformamide to obtain a mixed solution;
dissolving 2g-4g of azobisisobutyronitrile into 38mL of absolute ethyl alcohol, dropwise adding into the mixed solution under continuous stirring, heating to 82 ℃ and reacting for 300min, wherein nitrogen is used for protection in the reaction process;
cooling, washing, and freeze drying to obtain blocky polylauryl methacrylate with molecular weight of 2000.
Mixing a solution of polyether polyol containing polylauryl methacrylate (the mass ratio of the polyether polyol to the polylauryl methacrylate is 3:1) with polydimethylsiloxane, wherein the volume ratio of the solution of polyether polyol containing polylauryl methacrylate to the polydimethylsiloxane liquid is 3: 1. To obtain the drag reducer.
Example 2
When the carbon dioxide fracturing is carried out by using water, the pressure difference between the inlet and the outlet of the pipeline is 0.73Mpa, after the drag reducer in the embodiment 1 is added, the pressure difference between the inlet and the outlet is reduced to 0.27Mpa, and the drag reduction rate exceeds 55 percent and reaches 63.1 percent.
The embodiment is used for drilling and production of petroleum and natural gas, the mass ratio of the added drag reducer to the carbon dioxide is 0.3-0.5% in the fracturing process, and the drag reducer can be added into a pipeline before the carbon dioxide is introduced. The drag reducer is used in supercritical CO2The drag reduction rate can reach 63% at most in the fracturing process, the fracturing fluid can be degraded when meeting water/hydrocarbon substances or can be quickly discharged after being pressed, the damage caused by the retention of the stratum is prevented, and meanwhile, the drag reduction agent and liquid CO are mixed2Has good solubility, can form uniform mixed solution within 2min, and can be added with drag reducer within 170s-1Liquid CO under shear conditions2The viscosity is less than that of clear water, namely the viscosity is less than 1 cp. The supercritical CO can be well utilized after the drag reducer is added2And (5) fracturing.
Comparative example 1
This comparative example provides a drag reducing agent that is similar to that of example 1 except that the polyether polyol has a molecular weight of 800, the polydimethylsiloxane has a viscosity of 4000cp at 25 ℃, and the lauryl polymethacrylate has a molecular weight of 1000, giving a drag reduction rate of up to 32%; the viscosity of the solution was 2.378cp after dissolution in liquid carbon dioxide.
Comparative example 2
This comparative example provides a drag reducing agent that is similar to that used in example 1, except that the polyether polyol has a molecular weight of 3000, the polydimethylsiloxane viscosity is 10000, and the polylauryl methacrylate has a molecular weight of 3000. The drag reduction was 56% but the viscosity was 7.232cp after dissolution in liquid carbon dioxide.
Comparative example 3
The present comparative example provides a drag reducing agent made from a polyether polyol having a molecular weight of 2000, a polydimethylsiloxane having a viscosity of 8000, and a polylauryl methacrylate having a molecular weight of 2000; wherein the mass ratio of the polyether polyol to the polylauryl methacrylate is 7:1, and a mixed solution is formed. The volume ratio of the solution of polyether polyol containing polylauryl methacrylate to polydimethylsiloxane was 5: 2. The drag reduction ratio was 57.6%, and the viscosity was 0.674 cp.
Comparative example 4
The present comparative example provides a drag reducing agent made from a polyether polyol having a molecular weight of 2000, a polydimethylsiloxane having a viscosity of 8000, and a polylauryl methacrylate having a molecular weight of 2000; wherein the mass ratio of the polyether polyol to the polylauryl methacrylate is 5:1, a mixed solution is formed, and the volume ratio of the solution containing the polylauryl methacrylate to the polydimethylsiloxane is 5: 1. The drag reduction ratio was 53.3%, and the viscosity was 0.187 cp.
Claims (7)
1. The raw materials of the drag reducer are polyether polyol, polydimethylsiloxane and polylauryl methacrylate; wherein the mass ratio of the polyether polyol to the polylauryl methacrylate is 1:1-6:1, and the volume ratio of the solution of the polyether polyol containing the polylauryl methacrylate to the polydimethylsiloxane is 2:1-4: 1;
wherein the molecular weight of the polyether polyol is 1000-2000;
the viscosity of the polydimethylsiloxane is 5000-10000cp at 25 ℃;
the molecular weight of the polylauryl methacrylate is 1500-3000.
2. The drag reducer of claim 1, wherein the polyether polyol is selected from the group consisting of polyoxypropylene diol, polytetrahydrofuran diol, tetrahydrofuran-oxypropylene co-diols, and modified polyether polyols.
3. The drag reducer of claim 1, wherein the polylauryl methacrylate is prepared by:
respectively dissolving 30-60 mL of lauryl methacrylate and 10-30 mL of divinylbenzene in 80-100 mL of N, N-dimethylformamide to obtain a mixed solution;
dissolving 2g-4g of azobisisobutyronitrile into 20mL-50mL of absolute ethyl alcohol, dripping into the mixed solution while stirring, heating to 70-90 ℃ for reaction, and protecting with nitrogen in the reaction process;
cooling, washing, freezing and drying to obtain blocky polylauryl methacrylate.
4. The drag reducer of claim 3, wherein the elevated temperature reaction is for 4h to 6 h.
5. A process for the preparation of a drag reducing agent according to any of claims 1 to 3, which process comprises the step of blending polylol polyol with polydimethylsiloxane, followed by the step of compounding with polylauryl methacrylate.
6. Use of a drag reducer as claimed in any one of claims 1 to 3 for reducing drag in fracturing of liquid carbon dioxide.
7. Use according to claim 6, wherein the mass ratio of drag reducer to liquid carbon dioxide is between 0.3% and 0.5%: 1.
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| CN113136196A (en) * | 2020-11-20 | 2021-07-20 | 中国石油天然气股份有限公司 | Fracturing fluid composition, preparation method of fracturing fluid, fracturing fluid and fracturing method |
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