Composite material as well as preparation method and application thereof

Abstract

The invention provides a composite material as well as a preparation method and application thereof. The method comprises the following steps: mixing a mixed multi-component monomer with a solvent to obtain a mixed multi-component monomer solution; mixing the mixed multi-element monomer solution, the silicate layered intermediate and a catalytic activity initiator, and copolymerizing to obtain a composite material; wherein the mixed multi-component monomer comprises the following components in parts by molar weight: 0.7-70 parts of a first monomer, 0.2-20 parts of a second monomer and 0.1-10 parts of a third monomer; the molar ratio of the mixed multi-component monomer to the silicate layered intermediate to the catalytic activity initiator is 1: (0.1-10): (0.01-0.5); the first monomer comprises one or a combination of more than two of acrylamide, acrylic acid and propanesulfonic acid group substituted acrylamide; the second monomer comprises sodium p-styrenesulfonate and / or sodium alkyl phenyl sulfonate; the third monomer comprises acryloyl morpholine and / or N-vinyl pyrrolidone.

Description

Technical Field

[0001] The present invention relates to the technical field of oil and gas extraction, and in particular to a composite material and a preparation method and application thereof. Background Art

[0002] Oil and gas exploration and development are developing towards deep wells. Deep oil and gas wells are a general term for deep wells, ultra-deep wells, extra-deep wells and 10,000-meter deep wells.

[0003] Deep oil and gas wells have a series of problems, such as high temperature and high pressure at the bottom of the well, large formation pressure gradient, irregular distribution of formation pores and cracks, multi-scale cracks prone to leakage, large permeability changes, well wall expansion and instability due to fluid absorption, and block falling.

[0004] Existing oil and gas deep well projects include drilling, completion, cementing, fracturing, oil production and well washing projects.

[0005] Modern drilling is crucial for deep oil and gas well engineering. As well depth increases, the pressure differential and temperature within the wellbore gradually increase. To ensure drilling efficiency and protect deep oil and gas formations, multifunctional treatment agents are needed to control drilling fluid properties and meet the diverse needs of deep well engineering. For example, existing technologies use a variety of organic molecules, inorganic materials, and their composites to control drilling fluid rheology (such as viscosity and fluid loss) within an optimal range. However, high fluid loss can easily lead to wellbore collapse and difficulty in drilling. During deep oil and gas well drilling, the properties of pores and fractures (referred to as pores and fractures) in rock formations at different depths vary significantly. Under the induction of penetration by drilling fluids using existing treatment agents, these pores and fractures can easily connect to large channels or caves deep within the formation, causing significant drilling fluid losses, rheological failure, inability to flow, and strong drill string adhesion. This can lead to drilling stagnation or interruption, and even accidents such as drill string sticking and pipe string breakage. Existing ultra-high molecular weight polymer treatment agents, which enter the pores and fissures of deep oil and gas reservoirs through viscoelastic deformation, generate molecular chains that sweep oil molecules from the rock pore walls, improving oil recovery efficiency. However, these agents tend to remain, contaminating the oil and gas formations and reducing production capacity. To increase recovery, secondary or multiple drilling or fracturing procedures are necessary. Existing complex treatment agent compositions stably disperse on the deep well walls, forming a thin, tough, and dense filter cake, preventing drilling fluid or filtrate from entering the formation and reducing the probability of well accidents.

[0006] The complex reservoir structure of deep wells and the large temperature gradients at the bottom of the well place stringent requirements on the temperature resistance of oil and gas engineering fluids, especially drilling fluids. Existing polymer treatment agents are prone to degradation and failure in the high-temperature environment of deep wells. This can lead to poor rheological and filtration properties of drilling fluids, or even failure, which can easily cause downhole accidents.

[0007] The fluid loss reduction and temperature resistance of existing water-based drilling fluid treatment agents have become factors affecting drilling costs, speed, and quality. High-temperature resistant fluid loss reducers are recognized as critical for deep-well oil and gas projects, especially drilling operations. Existing natural polymer, synthetic resin, or polymer-based fluid loss reducer systems have poor temperature resistance and are prone to degradation and failure at high temperatures.

[0008] Currently, existing technologies focus on synthetic polymer fluid loss additives. Through molecular structure design, monomers with optimal thermal resistance, hydration, and adsorption properties are selected to create a thermally stable backbone and hydrolysis-resistant side chains. Based on this foundation, existing technologies are also researching the integration of inorganic materials into polymer matrices to create high-temperature-resistant, multifunctional treatment agents. Furthermore, new composite drilling fluids with controllable rheology, fluid loss reduction, and plugging properties are being developed. Adding small amounts of these existing materials to drilling fluids can improve mud cake quality, reduce fluid loss, minimize formation damage, and generate higher cost-effectiveness and benefits.

[0009] Currently, in the field of deep well oil and gas engineering, there is still a need for a high-temperature treatment agent that has good comprehensive high-temperature resistance, filtration loss reduction, sealing and lubrication capabilities. Summary of the Invention

[0010] To address the above-mentioned deficiencies in the prior art, the present invention provides a composite material, a preparation method thereof, and its application. The composite material exhibits excellent high-temperature resistance, fluid loss reduction, plugging, and lubrication capabilities, and is suitable for use in deep, ultra-deep, and unconventional reservoir oil and gas projects.

[0011] In order to achieve the above object, according to a first aspect of the present invention, a method for preparing a composite material is provided, which comprises:

[0012] mixing the mixed multi-monomer with a solvent to obtain a mixed multi-monomer solution;

[0013] Mixing the mixed multi-monomer solution, the silicate layered intermediate, and the catalytically active initiator to obtain a reaction system;

[0014] A protective gas is introduced into the reaction system to initiate a copolymerization reaction at a pH of 7 to 9 to obtain a gel product;

[0015] post-processing the gel product to obtain the composite material;

[0016] Wherein, the mixed multi-monomer comprises, by molar amount, 0.7 to 70 parts of the first monomer, 0.2 to 20 parts of the second monomer, and 0.1 to 10 parts of the third monomer;

[0017] The molar ratio of the mixed multi-monomer, the silicate layered intermediate, and the catalytically active initiator is 1:(0.1-10):(0.01-0.5);

[0018] The first monomer includes one or a combination of two or more of acrylamide, acrylic acid, and propane sulfonic acid substituted acrylamide;

[0019] The second monomer includes sodium p-styrene sulfonate and / or sodium alkylphenyl sulfonate;

[0020] The third monomer includes acryloylmorpholine and / or N-vinylpyrrolidone.

[0021] The composite material obtained in the present invention can be written as PASA-xy-MMT, wherein PASA is a polymer matrix; y-MMT is a silicate layered intermediate, including MMT, O-MMT, I-MMT, etc.; and x is the mass percentage (%) of the silicate layered intermediate in the composite material.

[0022] In some embodiments of the present invention, the mass concentration of the mixed multi-monomers in the mixed multi-monomer solution is 25-35%.

[0023] In some embodiments of the present invention, the silicate layered intermediate is modified.

[0024] In some embodiments of the present invention, the layered silicate intermediate is an intercalation intermediate of a refined layered silicate of one or any two of the associated minerals selected from the group consisting of sepiolite, montmorillonite, kaolinite, and laponite. In some embodiments of the present invention, the refined layered silicate is obtained through an industrial purification process, and the intercalation intermediate of the refined layered silicate is obtained through an intercalation reaction process, and both are in the form of powdered particles.

[0025] In the present invention, the intercalation reaction process or intercalation modification method of the silicate layered intermediate can be carried out with reference to the disclosed prior art (see Ke Yangchuan, Polymer Nanocomposites, Science Press, 2009).

[0026] Preferably, in some specific embodiments of the present invention, the preparation of the silicate layered intermediate comprises:

[0027] (1) Using industrially refined general-purpose commercial montmorillonite (MMT) gel raw material, a 4.0% water-suspended clay slurry was prepared and allowed to stand at 25°C for 24 hours. Then, 300 mL of the clay slurry was placed in a reactor and stirred uniformly in a water bath at a constant temperature of 65°C for 30 minutes.

[0028] (2) According to the CEC value range (0.70-1.0 mmol / g) of the MMT gel raw material, a corresponding CEC=1.0 mmol / g amount of cetyltrimethyl ammonium bromide (CTAB) powder is weighed, dissolved in a proper amount of deionized water to form a CTAB solution, and then slowly dripped into the above reactor while continuously passing N2 protective gas.

[0029] (3) The water bath is controlled to slowly warm up to 70°C, and after the clay slurry is reacted with CTAB under N2 protection for 10 h to form a suspension, the upper and lower layers are separated by a separatory funnel, and the lower suspension is retained, followed by separation of the intercalated clay layered intermediate (O-MMT) using a Buchner funnel, and then the layered intermediate sample is washed and purified with anhydrous ethanol and water three times each until there is no Br - .

[0030] (4) The purified sample obtained in (3) is placed in a 70°C oven for constant temperature drying, and then the dried sample is crushed by a pulverizer and passed through a 200-mesh sieve to obtain the product. The preparation method described above is only an example, and other silicate layered intermediates can also be prepared by those skilled in the art according to the disclosed technology in the art.

[0031] In some embodiments of the present application, the protective gas comprises nitrogen.

[0032] In some embodiments of the present application, the temperature of the copolymerization reaction is 30-60°C, and the time is 4-10 h.

[0033] In some embodiments of the present application, the water content of the composite material is less than 5%;

[0034] Preferably, the gel product is subjected to a dehydration treatment, and more preferably, the dehydration treatment comprises:

[0035] The gel product is dried at 50-70°C.

[0036] In some embodiments of the present application, the solvent comprises water.

[0037] In some embodiments of the present application, the catalytically active initiator comprises one or more than two combinations of ammonium persulfate, sodium bisulfite, and dibenzoyl peroxide.

[0038] According to another aspect of the present application, a composite material obtained by the above preparation method is provided.

[0039] In some embodiments of the present application, the thermal decomposition temperature of the composite material subjected to existing thermogravimetric analysis is higher than 300°C.

[0040] According to another aspect of the present application, there is provided an oil and gas engineering high-temperature resistant treatment agent comprising the composite material and the industrial clay.

[0041] In some embodiments of the present application, the oil and gas engineering high-temperature resistant treatment agent comprises 0.5-2 parts of the composite material and 4 parts of the industrial clay by mass fraction, and is configured as a suspension, wherein the solid content is 0.5-5 wt%, and the suspension satisfies one or a combination of more than two of the following conditions:

[0042] The performance is stable at 180-220℃ high-temperature aging for 24 hours, and the filtration loss is less than 20 ml;

[0043] The plugging pressure-bearing capacity of the oil and gas reservoir engineering can reach 7-15 MPa;

[0044] The thermal gravimetric analysis performance is stable at a temperature of 370℃.

[0045] According to another aspect of the present application, there is also provided an application of the oil and gas engineering high-temperature resistant treatment agent in deep, ultra-deep, and unconventional reservoir oil and gas engineering.

[0046] The composite material provided by the present application can be used as a key component of an excellent oil and gas engineering high-temperature resistant treatment agent, and has a good market application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0047] Figure 1 TGA thermogravimetric analysis curves of PASA721 obtained in Example 5 and PASA-1.0-OMMT obtained in Example 9 are shown. DETAILED DESCRIPTION

[0048] In order to have a clearer understanding of the technical features, objectives and beneficial effects of the present application, the technical solutions of the present application are described in detail as follows, but it should not be understood as a limitation on the implementable scope of the present application.

[0049] In the present application, a single diffraction peak is tested by a conventional X-ray diffraction (XRD) method, and the interlayer spacing of the layered intermediate or the oil and gas engineering high-temperature resistant treatment agent is calculated according to the diffraction angle and the Bragg equation:

[0050] The X-ray test layer crystal face diffraction peak position satisfies the Bragg equation condition formula,

[0051] 2d sinθ = nλ (1)

[0052] In formula (1), d is the interlayer spacing of the layered crystal face, θ is the included angle between the reflected line of the incident line of the X-ray and the reflected crystal face, λ is the X-ray wavelength, and n is the reflection order.

[0053] Crystals are selected to meet the Bragg equation test, the extinction behavior of the system is eliminated, and the X-ray diffraction curve and characteristic crystal diffraction peaks are obtained. The interlayer spacing is calculated according to the Bragg equation and the existing data accumulation and database of the maximum interlayer spacing of layered materials. Combined with the X-ray diffraction peak position, critical interlayer spacing and intercolloidal force, the critical interlayer force is calculated to obtain the layered intermediate.

[0054] In the present invention, a conventional thermogravimetric analyzer (TGA) is used to test the heating temperature-mass loss curve of the dry powder sample. The heating rate is set to 10°C / min, and the temperature is raised from room temperature to 800°C. An integral curve and a differential curve are obtained. The maximum thermal decomposition temperature integral peak is identified from the curve where the weight loss is greater than 5%, and compared with the differential peak to obtain the corresponding temperature at different weight loss locations.

[0055] In the present invention, a conventional rheometer and a high-temperature and high-pressure rheometer are used to test the rheological parameters and the fluid loss parameters at room temperature and pressure and at high temperature and high pressure of the sample according to API standards.

[0056] In the present invention, the preparation methods are conventional methods unless otherwise specified; the raw materials used are available from public industrial and commercial sources unless otherwise specified. The composition ratios described are calculated by mass ratio, except for molar ratios specified otherwise.

[0057] Example 1

[0058] Preparation of silicate layered intermediates

[0059] (1) Using industrially refined general-purpose commercial montmorillonite (MMT) gel raw material, a 4.0% water-suspended clay slurry was prepared and cured at 25°C for 24 hours. Then, 300 mL of the clay slurry was placed in a reactor and stirred uniformly in a water bath at a constant temperature of 65°C for 30 minutes.

[0060] (2) According to the CEC value range of the MMT gel raw material (0.70-1.0 mmol / g), cetyltrimethylammonium bromide (CTAB) powder with a corresponding CEC of 1.0 mmol / g was weighed and dissolved in an appropriate amount of deionized water and stirred evenly to form a CTAB solution, which was then slowly dripped into the above-mentioned reactor while continuously introducing N2 protective gas.

[0061] (3) The water bath was slowly heated to 70 °C, and the clay slurry and CTAB were reacted under N2 protection for 10 h to form a suspension. The upper and lower layers were separated by a separatory funnel, and the lower suspension was retained. The intercalated clay layered intermediate (O-MMT) was then separated by a Buchner funnel. The layered intermediate sample was then washed and purified three times with anhydrous ethanol and water respectively until there was no Br in the washing liquid. - .

[0062] (4) The purified sample obtained in (3) was placed in an oven at 70°C for constant temperature drying, and then the dried sample was crushed by a grinder and passed through a 200-mesh sieve to obtain the product.

[0063] Example 2

[0064] The only difference from Example 1 is that montmorillonite (MMT) is replaced by Huaian clay (G1, China Petroleum Engineering Technology Research Institute Co., Ltd.); the obtained silicate layered intermediate sample is marked as I-MMT1.

[0065] Example 3

[0066] The only difference from Example 1 is that montmorillonite (MMT) is replaced by Halliburton clay (HB1, Halliburton Company); the resulting silicate layered intermediate sample is labeled I-MMT2.

[0067] Example 4

[0068] The only difference from Example 1 is that montmorillonite (MMT) is replaced by Great Wall soil; the obtained silicate layered intermediate sample is marked as I-MMT3.

[0069] Example 5

[0070] Preparation of polymer materials

[0071] In beaker 1, acrylamide (AM), sodium p-styrenesulfonate (SSS), and acryloylmorpholine (ACMO) monomers were prepared at a molar ratio of 7:2:1 to form a 30 wt% mixed monomer solution, which was placed in a water bath reactor.

[0072] Prepare 35% NaOH solution, add it to the mixed multi-monomer solution, stir and mix evenly, and adjust the pH to 8. During this period, keep N2 in the solution at room temperature for 30 minutes;

[0073] Then, an initiator accounting for 0.3 wt% of the mass of the mixed multi-monomers was added dropwise to the reactor solution. The initiator was ammonium persulfate ((NH4)2S2O8) and sodium sulfite (NaHSO3) in a mass ratio of 1:1. After stirring with N2 gas for 30 minutes, the water bath reactor was sealed and placed in a temperature-controlled water bath at 60°C for 6 hours to produce a gel product.

[0074] The gel sample was washed three times with anhydrous ethanol and water respectively, and the gel product was placed in a constant temperature oven at 70°C for drying. The dried sample was crushed into powder using a grinder to obtain a polymer material, which was recorded as PASA721. Its TGA curve is shown in FIG. Figure 1 shown.

[0075] Example 6

[0076] The difference from Example 5 is that the mixed multi-monomers are prepared according to the molar ratio of AM:SSS:ACMO=7:1:2, and the obtained polymer material is recorded as PASA712.

[0077] Example 7

[0078] The difference from Example 5 is that the mixed monomers are prepared according to the molar ratio of AM:SSS:ACMO=6:3:1, and the obtained polymer material is recorded as PASA631.

[0079] Example 8

[0080] Preparation of composite materials

[0081] (1) Using a graduated cylinder, measure an appropriate amount of deionized water into beaker 1, weigh the O-MMT prepared in Example 1 so that the mass ratio of O-MMT in the composite material is 5 wt%, and stir evenly;

[0082] (2) In beaker 2, acrylamide (AM), sodium p-styrenesulfonate (SSS), and acryloylmorpholine (ACMO) monomers were prepared at a molar ratio of AM:SSS:ACMO = 7:2:1 to form a 30 wt% mixed monomer solution, which was placed in a water bath reactor;

[0083] (3) Prepare 35% NaOH solution in beaker 2 and add it to the water bath reactor to adjust the solution to pH = 8;

[0084] (4) Then, 0.3 wt% of the initiator accounting for the total monomer amount was added dropwise to the reactor solution. The initiator was ammonium persulfate ((NH4)2S2O8) and sodium sulfite (NaHSO3) in a mass ratio of 1:2. After stirring for 30 min through N2 gas, the water bath reactor was sealed and placed in a water bath controlled at 60°C for 6 h to prepare a gel sample.

[0085] (5) The gel sample was washed three times with anhydrous ethanol and water, respectively, and then dried in a constant temperature oven at 70°C. The dried sample was crushed into powder using a grinder to obtain PASA-0.5-OMMT.

[0086] Example 9

[0087] The difference from Example 8 is that the mass percentage of O-MMT is 1.0 wt%. It is recorded as PASA-1.0-OMMT. Its TGA curve is as follows Figure 1 As shown by Figure 1 It can be seen that the composite material of the present invention has excellent thermal stability.

[0088] Example 10

[0089] The difference from Example 8 is that the mass percentage of O-MMT is 1.5 wt %, which is recorded as PASA-1.5-OMMT.

[0090] Example 11

[0091] The difference from Example 8 is that the mass percentage of O-MMT is 2.0 wt %. This is recorded as PASA-2.0-OMMT.

[0092] Example 12

[0093] The PASA-2.0-OMMT obtained in Example 11 was mixed with fresh water base slurry at a mass concentration of 1.0% to prepare a high-temperature resistant drilling fluid for oil and gas engineering.

[0094] Example 13

[0095] 1 part by mass of PASA-1.0-OMMT (Example 9) and 4 parts by mass of industrial clay were mixed to form a suspension having an analyzed solid content of 1.5 wt % to prepare a high-temperature resistant drilling fluid for oil and gas engineering.

[0096] Comparative Example 1

[0097] Unmodified MMT is an industrial or commercial montmorillonite product made from layered silicate minerals.

[0098] Comparative Example 2

[0099] G1, clay mineral powder from Huaian, Hebei.

[0100] Comparative Example 3

[0101] HB1, clay mineral powder from Halliburton.

[0102] The X-ray diffraction curve of the layered intermediate sample was measured, and the interlayer spacing and physical properties of the layered intermediate were calculated. The results are shown in Table 1.

[0103] Table 1

[0104]

[0105] Thermogravimetric analysis (TGA) and rheological parameters of the samples were performed. The results are shown in Table 2.

[0106] Table 2

[0107]

[0108]

[0109] As can be seen from the data in Table 2, the overall rheological properties of the solution of the present invention at high temperatures are relatively higher, and the high-temperature filtration loss is improved.

[0110] The apparent viscosity, filtration loss and HTHP filtration loss of the high-temperature-resistant drilling slurry prepared from the high-temperature-resistant treatment agent for oil and gas engineering in Example 12 were tested by the API standard and the existing flow rate viscometer, the aging temperature was 140℃, 160℃, 180℃, 200℃ and 220℃ respectively, and the aging time was 16h. The pure PASA polymer fluid loss additive with a mass concentration of 1wt% was also tested under the same conditions, and was recorded as Comparative Test Examples 1-5. The results are shown in Table 3. In this test, the structural units and the proportion of each structural unit in PASA were exactly the same as the polymer matrix used in Example 12.

[0111] Table 3

[0112]

[0113] As can be seen from the data in Table 3, the overall rheological property of the solution of the present application is relatively higher, and the high-temperature filtration property is improved.

[0114] The apparent viscosity, filtration loss and HTHP filtration loss of the slurry of the high-temperature-resistant treatment agent for oil and gas engineering in Example 13, CMC (carboxymethyl cellulose), SMP (sulfomethyl phenolic resin) and LSY-1 (aluminate) were tested by the API standard and the existing flow rate viscometer, and the test results are shown in Table 4.

[0115] Table 4

[0116]

[0117]

[0118] As can be seen from the data in Table 4, the overall rheological property of the solution obtained by the present application is relatively higher, and the high-temperature filtration property is improved.

Claims

1. A method for preparing a composite material, characterized in that: include: mixing the mixed multi-monomer with a solvent to obtain a mixed multi-monomer solution; Mixing the mixed multi-monomer solution, the silicate layered intermediate, and the catalytically active initiator to obtain a reaction system; A protective gas is introduced into the reaction system to initiate a copolymerization reaction at a pH of 7 to 9 to obtain a gel product; post-processing the gel product to obtain the composite material; Wherein, the mixed multi-monomer comprises, by molar amount, 0.7 to 70 parts of the first monomer, 0.2 to 20 parts of the second monomer, and 0.1 to 10 parts of the third monomer; The molar ratio of the mixed multi-monomer, the silicate layered intermediate, and the catalytically active initiator is 1:(0.1-10):(0.01-0.5); The first monomer includes one or a combination of two or more of acrylamide, acrylic acid, and propane sulfonic acid substituted acrylamide; The second monomer includes sodium p-styrene sulfonate and / or sodium alkylphenyl sulfonate; The third monomer includes acryloylmorpholine and / or N-vinylpyrrolidone.

2. The method for preparing a composite material according to claim 1, wherein: In the mixed multi-monomer solution, the mass concentration of the mixed multi-monomer is 25-35%.

3. The method for preparing a composite material according to claim 1, wherein: The silicate layered intermediate is an intercalation intermediate of refined layered silicates of one of the layered silicates, sepiolite, montmorillonite, kaolinite, and laponite, or any two of these layered silicates that are associated with each other.

4. The method for preparing a composite material according to claim 1, wherein: The copolymerization reaction temperature is 30-60° C. and the reaction time is 4-10 hours.

5. The method for preparing a composite material according to claim 1, wherein: The water content of the composite material is less than 5%; Preferably, the gel product is subjected to a dehydration treatment, more preferably, the dehydration treatment comprises: The gel product is dried at 50-70°C.

6. The method for preparing a composite material according to claim 1, wherein: The catalytically active initiator includes one or a combination of two or more of ammonium persulfate, sodium bisulfite, and dibenzoyl peroxide.

7. A composite material obtained by the method for preparing a composite material according to any one of claims 1 to 6.

8. The composite material according to claim 7, characterized in that The thermal decomposition temperature of the composite material measured by thermogravimetric analysis is higher than 300°C.

9. A high temperature resistant treatment agent for oil and gas engineering, characterized in that: The composite material comprises the composite material according to claim 7 or 8 and industrial clay.

10. Use of the oil and gas engineering high temperature resistant treatment agent according to claim 9 in deep, ultra-deep and unconventional reservoir oil and gas engineering.

Images