Barite targeting collector and preparation and application thereof

Abstract

The application discloses a targeting barite collector, which comprises a bipyridinium salt and a carboxylic acid. The application also discloses preparation and application thereof. The application provides an oil extraction method by using a low-temperature countercurrent extraction process, a flotation method for extracting barite minerals from oil-removed solid phases, and a method for processing oil-based rock debris resources by using flotation tailings to prepare proppants, and development of high-efficiency extractants and flotation agents. The recovery rate of the barite can reach more than 95%.

Description

Technical Field

[0001] This invention relates to targeted barite collectors, their preparation, and applications. Background Technology

[0002] Oil-based drilling fluids are widely used in the development of unconventional oil and gas resources such as shale gas and tight gas. Composed of mineral oil, water, weighting agents, organic clay, and various oil-soluble chemical treatment agents, they offer advantages such as resistance to high temperatures and salt-calcium erosion, promoting wellbore stability, good lubrication, and minimal damage to oil and gas reservoirs. During drilling operations, oil-based drilling fluids carry drilling cuttings from the formation back to the surface. After processing by the well site solids control system, the lower phase drilling fluid is recycled, while the upper phase remains as oil-based drilling cuttings. The main components of oil-based drilling cuttings are mineral oil, phenols and other organic compounds, and various inorganic ores. If the mineral oil and organic compounds contained within are not properly treated and discharged, they can pollute soil, surface water, and groundwater, directly or indirectly harming plants, animals, human health, and the surrounding ecological environment.

[0003] Oil-based rock cuttings typically contain 25-40% oil, making them economically valuable. Current technologies primarily utilize high-temperature, energy-intensive thermal treatment to extract the oil from these cuttings. However, the oil content in the tailings remains above 2%, and the barite minerals within the tailings are not effectively utilized; therefore, treating them as waste is not environmentally friendly. Summary of the Invention

[0004] This invention was made to further improve the environmentally friendly treatment and comprehensive utilization of oil-based rock cuttings.

[0005] The target oil for extraction as referred to in this invention is the target oil determined based on the type and source of the base oil in the oil-based rock fragments extracted by the countercurrent extractant. For example, the base oil corresponding to diesel-based rock fragments is diesel, and the base oil corresponding to white-based rock fragments is white oil.

[0006] As one aspect of the present invention, a targeted barite collector is disclosed, comprising a bipyridine onium salt and a carboxylic acid, wherein the bipyridine onium salt is:

[0007]

[0008]

[0009] Any one or more mixtures thereof.

[0010] In a specific embodiment, the carboxylic acid is any one or a mixture of oxalic acid, p-hydroxybenzoic acid, trimesic acid, nicotinic acid, and 6-chloronicotinic acid.

[0011] In a specific embodiment, the molar ratio of bipyridinium salt to carboxylic acid is 1:2-2:1.

[0012] As another aspect of the present invention, a method for preparing the above-mentioned targeted barite collector is provided, comprising: dissolving a bipyridinium salt in a solvent to obtain solution 1; dissolving a carboxylic acid in a solvent to obtain solvent 2; and mixing the two solutions by stirring to obtain the barite targeted collector. The solvent is ethanol or N,N-dimethylformyl.

[0013] In another aspect, the invention relates to a method for extracting barite, comprising: using a flotation system comprising the aforementioned targeted barite collector. The flotation system further comprises an inhibitor, a dispersant, and a frother.

[0014] The inhibitor is a compound of sodium phosphate, water glass, and tannic acid in a mass ratio of 1:1-2:1-3, and the dosage is 800-1200 g / t.

[0015] The foaming agent is pine oil, and the dosage is 5-15g / t.

[0016] The dispersant is a compound of sodium pyrophosphate, sodium hexametaphosphate, and water glass in a mass ratio of 1-2:1-3:1, and the dosage is 0.25-1%.

[0017] The flotation temperature is 30-45℃, the flotation time is 40-70 min, and the pulp concentration is 10-20%.

[0018] As another aspect of the present invention, a comprehensive utilization process for oil-based rock cuttings is provided, including the above-mentioned barite extraction method, and further including the preparation of proppant from flotation tailings after barite extraction.

[0019] In a specific embodiment, the preparation of proppant using the flotation tailings refers to: drying the flotation tailings at 105℃ for 3-4 hours; mixing the tailings, bauxite, and potassium feldspar in a mass ratio of 2-3:5-7:1-2; ball milling and sieving to obtain a mixture with a particle size below 45μm; adding polyvinyl alcohol solution (3-5wt%) to the mixture in a mass ratio of 1:7-10; mixing thoroughly; granulating; air-drying; and sieving (15 / 30 mesh, 25 / 40 mesh, 30 / 50 mesh) to obtain raw proppant material; sintering in a resistance furnace at a temperature of 1150-1300℃ and a heating rate of 5-10℃ / min; holding at the reached temperature for 2-3 hours; and then cooling down to obtain proppant products of corresponding mesh sizes (20 / 40 mesh, 30 / 50 mesh, 40 / 70 mesh).

[0020] The present invention also relates to a countercurrent extractant comprising components in the following mass ratio: the mass ratio of the target oil, methyl ethyl ketone, sodium silicate and water is 40-60:10-20:0.2-0.5:20-30, preferably 45-55:15-20:0.2-0.3:20-25.

[0021] The present invention also relates to a method for extracting oil from oil-based rock cuttings, comprising: extracting oil-based rock cuttings using the above-mentioned countercurrent extractant.

[0022] In a specific embodiment, the above method includes the following steps:

[0023] Add oil-based rock cuttings and the above countercurrent extractant at a liquid-to-solid ratio of 3-5:1, and extract at 15-40℃.

[0024] In a specific embodiment, the extraction is a three-stage countercurrent extraction, with a single-stage extraction time of 20-35 min and a stirring speed of 350-500 r / min.

[0025] In a specific embodiment, the method performs liquid-solid separation after the extraction step to obtain a solid phase and a liquid phase, and the liquid phase is then subjected to oil-water separation.

[0026] In a specific embodiment, after oil-water separation, the aqueous phase is recycled for the countercurrent extraction stage, and 80-90% of the oil phase is entered into the countercurrent extraction stage.

[0027] This invention provides a method for the resource utilization of oil-based rock cuttings, which involves oil extraction using a low-temperature countercurrent extraction process, extraction of barite minerals from the deoiled solid phase using flotation, and preparation of proppant from flotation tailings. High-efficiency extractants and flotation agents were also developed. After countercurrent extraction, the oil content of the oil-based rock cutting tailings can be reduced to below 0.3%. Further flotation extraction can achieve a barite recovery rate of over 95%. The proppant prepared from the flotation tailings meets the 35MPa specification requirements of SY / T5108-2014, thus realizing the full resource utilization of oil-based rock cuttings.

[0028] This invention addresses the characteristic of oil-based rock cuttings being rich in valuable components such as white oil or diesel oil (collectively referred to as base oil) and barite minerals. It employs a technical route of "countercurrent extraction to remove base oil – flotation extraction of barite – tailings calcination for proppant production," achieving deep resource utilization of oil-based rock cuttings. The recovered base oil can be used to re-form drilling fluids, the extracted barite can be reused as a weighting agent in drilling fluids, and the remaining flotation tailings can be used as raw materials for preparing fracturing proppant. This achieves the dual goals of harmlessness and resource utilization, solving the environmental problems that have plagued oil and gas field development companies and safeguarding the clean and harmless production of shale gas. Currently, the field of oil-based rock cuttings processing mainly focuses on heavy oil and light solids. Oil recovery often relies on high-temperature, energy-intensive thermal treatment methods, and the oil content of the tailings is higher than 2%. Furthermore, 40-60% of the barite minerals in the tailings are not effectively utilized. To address this issue, a resource-based processing method using low-temperature countercurrent extraction of oil and flotation to extract barite was developed. The tailings after flotation were used to prepare fracturing proppant. Simultaneously, a high-efficiency countercurrent extractant for base oil and a targeted barite collector were developed. This method effectively achieves the goal of extracting oil and minerals from oil-based rock cuttings and using the tailings to prepare proppant, thus realizing a more thorough resource utilization of oil-based rock cuttings. Attached Figure Description

[0029] Figure 1 This is a flowchart of the oil-based rock cuttings resource utilization method provided by the present invention.

[0030] Figure 2 This is a schematic diagram of the operation of the countercurrent extraction unit in the oil-based rock cuttings resource utilization process provided by the present invention. Detailed Implementation

[0031] The embodiments of the present invention are described in detail below: The embodiments of the present invention are implemented under the premise of the technical solution of the present invention, and detailed implementation methods and processes are given. However, the protection scope of the present invention is not limited to the following embodiments. The process parameters in the following embodiments that do not specify specific conditions are generally in accordance with conventional conditions.

[0032] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this invention.

[0033] The corresponding operation steps of the following embodiments can be referred to the appendix. Figure 1 and attached Figure 2 To achieve this.

[0034] The structural formula of the bipyridine onium salt used in the embodiments of the present invention is as follows:

[0035]

[0036]

[0037] Example 1

[0038] Diesel bedrock fragments were crushed to below 75 μm and conveyed to a three-stage countercurrent extraction system. A countercurrent extractant, prepared by mixing diesel oil, methyl ethyl ketone, sodium silicate, and water in a mass ratio of 45:15:0.3:25, was added at a liquid-to-solid ratio of 3:1. The extraction temperature was 25℃, the single-stage extraction time was 25 min, and the stirring speed was 450 r / min. After extraction, solid-liquid separation was performed by centrifugation at a speed of 3000 r·min. -1 The liquid phase undergoes further oil-water separation, with the aqueous phase recycled for countercurrent extraction. Of the resulting oil phase, 90% is used in countercurrent extraction, and 10% is used to prepare drilling fluid. The solid phase obtained by centrifugation has an oil content of 0.25% and is then used for barite extraction via flotation.

[0039] The solid phase obtained by centrifugation was ground to below 50 μm and added to a solution containing an inhibitor (sodium phosphate, water glass, and tannic acid in a mass ratio of 1:1:2, at a dosage of 900 g / t) and a targeted barite collector (a 5 wt% solution of bipyridinium salt (a) dissolved in N,N-dimethylformamide, and a 5 wt% solution of oxalic acid dissolved in ethanol, with the solution added at a molar ratio of bipyridinium salt (a) to oxalic acid of 1:1.5). A flotation system was prepared by mixing solution 1 with solution 2 to obtain a targeted barite collector (500 g / t), a dispersant (sodium pyrophosphate, sodium hexametaphosphate, and water glass in a mass ratio of 1:2:1, 0.35%), and a frother (pine oil, 10 g / t). The flotation temperature was controlled at 35℃, the flotation time at 60 min, and the pulp concentration at 15%. After flotation, the barite recovery rate was 96%, and the density was 4.2 g·cm³. -3 The flotation tailings then enter the proppant preparation stage.

[0040] The flotation tailings were dried at 105℃ for 3 hours. After drying, the tailings, bauxite, and potassium feldspar were mixed in a mass ratio of 2:5:2, ball-milled, and sieved to obtain a mixture with a particle size below 45 μm. Polyvinyl alcohol solution (4 wt%) was added to the mixture in a mass ratio of 1:7, and the mixture was stirred, granulated, and air-dried. The mixture was then sieved (15 / 30 mesh, 25 / 40 mesh, 30 / 50 mesh) to obtain the proppant raw material. This raw material was then sintered in a resistance furnace at 1280℃ with a heating rate of 5℃ / min. After reaching the desired temperature, the furnace was stopped and cooled to obtain proppant clinker of the corresponding mesh sizes (20 / 40 mesh, 30 / 50 mesh, 40 / 70 mesh). The bulk density of the 20 / 40 mesh product was 1.26 g·cm³. -3 The breakage rate at 35 MPa was 9.24%; the bulk density of the 30 / 50 mesh product was 1.30 g·cm³. -3 The breakage rate at 35 MPa was 7.86%; the bulk density of the 40 / 70 mesh product was 1.40 g·cm³. -3 The breakage rate was 6.31% at 35 MPa.

[0041] Example 2

[0042] In this embodiment, the object to be processed is diesel bedrock cuttings. The processing method is the same as in Example 1, except that the extractant is prepared by mixing diesel, methyl ethyl ketone, sodium silicate and water in a mass ratio of 40:10:0.2:20. The extraction temperature is 35℃, the single-stage extraction time is 20 min, the stirring speed is 400 r / min, and the oil content of the tailings after extraction is 0.28%.

[0043] Example 3

[0044] In this embodiment, the object to be processed is diesel bedrock cuttings, and the processing method is the same as in Example 2. The difference between Example 2 and Example 2 is that the extraction temperature is 15℃, the single-stage extraction time is 20min, the stirring speed is 350r / min, and the oil content of the tailings after extraction is 0.5%.

[0045] Example 4

[0046] In this embodiment, the object to be processed is diesel bedrock cuttings. The processing method is the same as in Example 2, except that the extractant is prepared by mixing diesel, methyl ethyl ketone, sodium silicate and water in a mass ratio of 60:20:0.5:30. The extraction temperature is 40℃, the single-stage extraction time is 35 min, the stirring speed is 500 r / min, and the oil content of the tailings after extraction is 0.16%.

[0047] Example 5

[0048] In this embodiment, the object to be processed is diesel bedrock cuttings. The processing method is the same as in Example 2, except that the extractant is prepared by mixing diesel, methyl ethyl ketone, sodium silicate and water in a mass ratio of 60:20:0.5:30. The extraction temperature is 50°C, the single-stage extraction time is 40 min, the stirring speed is 550 r / min, and the oil content of the tailings after extraction is 0.45%.

[0049] Example 6

[0050] In this embodiment, the object to be processed is diesel bedrock cuttings. The processing method is the same as in Example 2, except that the extractant is prepared by mixing diesel, methyl ethyl ketone, sodium silicate and water in a mass ratio of 60:20:0.5:30. The extraction temperature is 10°C, the single-stage extraction time is 15 min, the stirring speed is 300 r / min, and the oil content of the tailings after extraction is 0.85%.

[0051] Example 7

[0052] In this embodiment, the treated material is diesel bedrock cuttings. The treatment method is the same as in Example 1, but differs from Example 1 in the following ways: the inhibitor is a mixture of sodium phosphate, water glass, and tannic acid in a mass ratio of 1:1.5:3, used at a dosage of 800 g / t; the targeted barite collector is a solution 1 obtained by dissolving bipyridinium salt (b) in N,N-dimethylformamide to obtain a 5 wt% solution, and a solution 2 obtained by dissolving p-hydroxybenzoic acid in ethanol to obtain a 5 wt% solution, which is then mixed with solution 2 in a molar ratio of bipyridinium salt (b) to p-hydroxybenzoic acid of 2:1, used at a dosage of 400 g / t; the dispersant is a mixture of sodium pyrophosphate, sodium hexametaphosphate, and water glass in a mass ratio of 1:1:3, used at a dosage of 0.25%; and the foaming agent is pine oil, used at a dosage of 8 g / t. After flotation, the barite recovery rate is 95%, and the density is 4.0 g·cm³. -3 .

[0053] Example 8

[0054] In this embodiment, the treated material is diesel bedrock cuttings. The treatment method is the same as in Example 1, but differs from Example 1 in the following ways: the inhibitor is a mixture of sodium phosphate, water glass, and tannic acid in a mass ratio of 1:1:1, with a dosage of 1200 g / t; the targeted barite collector is a solution 1 obtained by dissolving bipyridinium salt (c) in solvent N,N-dimethylformamide to obtain a 5 wt% solution, and a solution 2 obtained by dissolving trimellitic acid in solvent ethanol to obtain a 5 wt% solution, which is then mixed with solution 2 in a molar ratio of 1:2, with a dosage of 600 g / t; the dispersant is a mixture of sodium pyrophosphate, sodium hexametaphosphate, and water glass in a mass ratio of 1:1:1, with a dosage of 0.25%; and the foaming agent is pine oil, with a dosage of 5 g / t. After flotation, the barite recovery rate is 90%, and the density is 4.1 g·cm³. -3 .

[0055] Example 9

[0056] In this embodiment, the treated material is diesel bedrock cuttings. The treatment method is the same as in Example 1, but differs from Example 1 in the following ways: the inhibitor is a mixture of sodium phosphate, water glass, and tannic acid in a mass ratio of 1:2:3, used at a dosage of 1200 g / t; the targeted barite collector is a solution 1 obtained by dissolving bipyridinium salt (d) in N,N-dimethylformamide to obtain a 5 wt% solution, and a solution 2 obtained by dissolving nicotinic acid in ethanol to obtain a 5 wt% solution, which is then mixed with solution 2 in a molar ratio of bipyridinium salt (b) to p-hydroxybenzoic acid of 2:1, used at a dosage of 600 g / t; the dispersant is a mixture of sodium pyrophosphate, sodium hexametaphosphate, and water glass in a mass ratio of 2:3:1, used at a dosage of 1%; and the foaming agent is pine oil, used at a dosage of 15 g / t. After flotation, the barite recovery rate is 95%, and the density is 4.3 g·cm³. -3 .

[0057] Example 10

[0058] In this embodiment, the treated material is diesel bedrock cuttings. The treatment method is the same as in Example 1, but differs from Example 1 in the following ways: the inhibitor is a mixture of sodium phosphate, water glass, and tannic acid in a mass ratio of 1:1.5:3, used at a dosage of 800 g / t; the targeted barite collector is a solution 1 obtained by dissolving bipyridinium salt (e) in N,N-dimethylformamide to obtain a 5 wt% solution, and a solution 2 obtained by dissolving 6-chloronicotinic acid in ethanol to obtain a 5 wt% solution, which is then mixed with solution 2 in a molar ratio of 2:1, used at a dosage of 400 g / t; the dispersant is a mixture of sodium pyrophosphate, sodium hexametaphosphate, and water glass in a mass ratio of 1:3:1, used at a dosage of 0.25%; and the foaming agent is pine oil, used at a dosage of 10 g / t. After flotation, the barite recovery rate is 93%, and the density is 4.4 g·cm³. -3 .

[0059] Example 11

[0060] In this embodiment, the treated material is diesel bedrock cuttings. The treatment method is the same as in Example 1, but differs from Example 1 in the following ways: the inhibitor is a mixture of sodium phosphate, water glass, and tannic acid in a mass ratio of 1:1.5:3, used at a dosage of 800 g / t; the targeted barite collector is a solution 1 obtained by dissolving bipyridinium salt (f) in N,N-dimethylformamide to obtain a 5 wt% solution, and a solution 2 obtained by dissolving 6-chloronicotinic acid in ethanol to obtain a 5 wt% solution, which is then mixed with solution 2 in a molar ratio of 2:1, used at a dosage of 400 g / t; the dispersant is a mixture of sodium pyrophosphate, sodium hexametaphosphate, and water glass in a mass ratio of 1:3:1, used at a dosage of 0.25%; and the foaming agent is pine oil, used at a dosage of 5 g / t. After flotation, the barite recovery rate is 96%, and the density is 4.4 g·cm³. -3 .

[0061] Example 12

[0062] In this embodiment, the object of treatment is diesel bedrock cuttings, and the treatment method is the same as in Example 1, except that: the inhibitor is a mixture of sodium phosphate, water glass, and tannic acid in a mass ratio of 1:1.5:3, and the dosage is 900 g / t; the targeted barite collector is a 5 wt% solution obtained by dissolving bipyridinium salt (a) and bipyridinium salt (f) in the solvent N,N-dimethylformamide, and 6-chloronicotinic acid is dissolved in the solvent ethanol. Solution 2, containing 5 wt%, was obtained by mixing solution 1 and solution 2 in a molar ratio of 1:1:1 with bipyridinium salt (a), bipyridinium salt (f), and 6-chloronicotinic acid, at a dosage of 400 g / t. The dispersant was a mixture of sodium pyrophosphate, sodium hexametaphosphate, and water glass in a mass ratio of 1:3:1, at a dosage of 0.25%. The frother was pine oil, at a dosage of 5 g / t. After flotation, the recovery rate of barite was 98%, and the density was 4.4 g·cm³. -3 .

[0063] Example 13

[0064] In this embodiment, the object of treatment is diesel bedrock cuttings, and the treatment method is the same as in Example 1, except that: the inhibitor is a mixture of sodium phosphate, water glass, and tannic acid in a mass ratio of 1:1.5:3, and the dosage is 900 g / t; the targeted barite collector is a 5 wt% solution 1 obtained by dissolving bipyridinium salt (c) and bipyridinium salt (f) in the solvent N,N-dimethylformamide, and 6-chloronicotinic acid is dissolved in the solvent ethanol. Solution 2, containing 5 wt%, was obtained by mixing solution 1 and solution 2 in a molar ratio of 1:1:1 with bipyridinium salt (c), bipyridinium salt (f), and 6-chloronicotinic acid, at a dosage of 400 g / t. The dispersant was a mixture of sodium pyrophosphate, sodium hexametaphosphate, and water glass in a mass ratio of 1:3:1, at a dosage of 0.25%. The frother was pine oil, at a dosage of 10 g / t. After flotation, the barite recovery rate was 95%, and the density was 4.2 g·cm³. -3 .

[0065] Example 14

[0066] In this embodiment, the object of processing is diesel bedrock cuttings. The processing method is the same as in Example 1, except that the tailings remaining after flotation are dried at 105°C for 4 hours. After drying, the tailings, bauxite, and potassium feldspar are mixed in a mass ratio of 2:5:1, ball-milled, and sieved to obtain a mixture with a particle size of less than 45 μm. Polyvinyl alcohol solution (3 wt%) is added to the mixture at a mass ratio of 1:7 to the mixture, and the mixture is thoroughly mixed, granulated, and air-dried. After sieving (15 / 30 mesh, 25 / 40 mesh, 30 / 50 mesh), the raw proppant is obtained and sent to a resistance furnace for sintering at 1150°C at a heating rate of 5°C / min. After reaching the temperature, the furnace is stopped and cooled to obtain proppant clinker of the corresponding mesh sizes (20 / 40 mesh, 30 / 50 mesh, 40 / 70 mesh). The bulk density of the 20 / 40 mesh product is 1.30 g·cm³. -3 The breakage rate was 10.2% at 35 MPa, and the bulk density of the 30 / 50 mesh product was 1.28 g·cm³. -3 The breakage rate was 8.25% at 35 MPa, and the bulk density of the 40 / 70 mesh product was 1.42 g·cm³. -3 The breakage rate was 7.24% at 35 MPa.

[0067] Example 15

[0068] In this embodiment, the object of processing is diesel bedrock cuttings. The processing method is the same as in Example 1, except that the tailings remaining after flotation are dried at 105°C for 4 hours. After drying, the tailings, bauxite, and potassium feldspar are mixed in a mass ratio of 1.5:7:2, ball-milled, and sieved to obtain a mixture with a particle size of less than 45 μm. Polyvinyl alcohol solution (4 wt%) is added to the mixture in a mass ratio of 1:8 to the mixture, thoroughly mixed, granulated, and naturally air-dried. After sieving (15 / 30 mesh, 25 / 40 mesh, 30 / 50 mesh), the raw proppant is obtained and sent to a resistance furnace for sintering at a temperature of 1300°C and a heating rate of 8°C / min. After reaching the temperature, the furnace is stopped and cooled to obtain proppant clinker of the corresponding mesh sizes (20 / 40 mesh, 30 / 50 mesh, 40 / 70 mesh). The bulk density of the 20 / 40 mesh product is 1.34 g·cm³. -3 The breakage rate at 35 MPa was 6.30%; the bulk density of the 30 / 50 mesh product was 1.38 g·cm³. -3 The breakage rate at 35 MPa was 6.92%; the bulk density of the 40 / 70 mesh product was 1.32 g·cm³. -3 The breakage rate was 6.54% at 35 MPa.

[0069] Example 16

[0070] In this embodiment, the object of processing is diesel bedrock cuttings. The processing method is the same as in Example 1, except that the tailings remaining after flotation are dried at 105°C for 4 hours. After drying, the tailings, bauxite, and potassium feldspar are mixed in a mass ratio of 3:7:2, ball-milled, and sieved to obtain a mixture with a particle size of less than 45 μm. Polyvinyl alcohol solution (5 wt%) is added to the mixture at a mass ratio of 1:10 to the mixture, thoroughly mixed, granulated, and naturally air-dried. After sieving (15 / 30 mesh, 25 / 40 mesh, 30 / 50 mesh), the raw proppant is obtained and sent to a resistance furnace for sintering at a temperature of 1200°C and a heating rate of 10°C / min. After reaching the temperature, the furnace is stopped and cooled to obtain proppant clinker of the corresponding mesh sizes (20 / 40 mesh, 30 / 50 mesh, 40 / 70 mesh). The bulk density of the 20 / 40 mesh product is 1.29 g·cm³. -3 The breakage rate at 35 MPa was 7.25%; the bulk density of the 30 / 50 mesh product was 1.33 g·cm³. -3 The breakage rate at 35 MPa was 7.08%; the bulk density of the 40 / 70 mesh product was 1.23 g·cm³. -3 The breakage rate was 7.36% at 35 MPa.

[0071] Example 17

[0072] White oil bedrock fragments were crushed to below 75 μm and fed into a three-stage countercurrent extraction system. A countercurrent extractant, prepared from white oil, methyl ethyl ketone, sodium silicate, and water in a mass ratio of 45:15:0.3:25, was added at a liquid-to-solid ratio of 3:1. The extraction temperature was 25℃, the single-stage extraction time was 25 min, and the stirring speed was 450 r / min. After extraction, solid-liquid separation was performed by centrifugation at a speed of 3000 r·min. -1 The resulting aqueous phase is recycled for countercurrent extraction. 90% of the resulting oil phase is recycled for countercurrent extraction, and 10% is used to prepare drilling fluid. The solid phase obtained by centrifugation has an oil content of 0.27% and is sent to the flotation stage for barite extraction.

[0073] The solid phase obtained by centrifugation was ground to below 50 μm and added to a solution containing an inhibitor (sodium phosphate, water glass, and tannic acid in a mass ratio of 1:1:2, at a dosage of 900 g / t) and a targeted barite collector (a 5 wt% solution of bipyridinium salt (a) dissolved in N,N-dimethylformamide, and a 5 wt% solution of 6-chloronicotinic acid dissolved in ethanol, at a molar ratio of 1:1.5). A flotation system was prepared by mixing solution 1 and solution 2 to obtain a targeted barite collector (500 g / t), a dispersant (sodium pyrophosphate, sodium hexametaphosphate, and water glass in a mass ratio of 1:2:1, 0.35%), and a frother (pine oil, 10 g / t). The flotation temperature was controlled at 35℃, the flotation time at 60 min, and the pulp concentration at 15%. After flotation, the barite recovery rate was 95%, and the density was 4.0 g·cm³. -3 The flotation tailings then enter the proppant preparation stage.

[0074] The flotation tailings were dried at 105℃ for 3 hours. After drying, the tailings, bauxite, and potassium feldspar were mixed in a mass ratio of 2:5:2, ball-milled, and sieved to obtain a mixture with a particle size below 45 μm. Polyvinyl alcohol solution (4 wt%) was added to the mixture in a mass ratio of 1:7, and the mixture was stirred, granulated, and air-dried. The mixture was then sieved (15 / 30 mesh, 25 / 40 mesh, 30 / 50 mesh) to obtain the proppant raw material. This raw material was then sintered in a resistance furnace at 1280℃ with a heating rate of 5℃ / min. After reaching the desired temperature, the furnace was stopped and cooled to obtain proppant clinker of the corresponding mesh sizes (20 / 40 mesh, 30 / 50 mesh, 40 / 70 mesh). The bulk density of the 20 / 40 mesh product was 1.26 g·cm³. -3 The breakage rate at 35 MPa was 9.24%; the bulk density of the 30 / 50 mesh product was 1.30 g·cm³. -3 The breakage rate at 35 MPa was 7.86%; the bulk density of the 40 / 70 mesh product was 1.40 g·cm³. -3The breakage rate was 6.31% at 35 MPa.

[0075] Example 18

[0076] In this embodiment, the object to be processed is white oil-based rock fragments, and the processing method is the same as in Example 17. The difference between Example 17 and Example 17 is that the extractant is prepared by compounding white oil, methyl ethyl ketone, sodium silicate and water in a mass ratio of 40:10:0.2:20, the extraction temperature is 35℃, the single-stage extraction time is 20 min, the stirring speed is 400 r / min, and the oil content of the tailings after extraction is 0.25%.

[0077] Example 19

[0078] In this embodiment, the object to be processed is white oil-based rock fragments, and the processing method is the same as in Example 18. The difference between Example 18 and Example 18 is that the extractant is prepared by compounding white oil, methyl ethyl ketone, sodium silicate and water in a mass ratio of 60:20:0.5:30, the extraction temperature is 40℃, the single-stage extraction time is 35min, the stirring speed is 500r / min, and the oil content of the tailings after extraction is 0.20%.

[0079] Example 20

[0080] In this embodiment, the object to be processed is white oil-based rock fragments, and the processing method is the same as in Example 18. The difference between Example 18 and Example 18 is that the extractant is prepared by compounding white oil, methyl ethyl ketone, sodium silicate and water in a mass ratio of 45:15:0.3:25. The extraction temperature is 10℃, the single-stage extraction time is 25 min, the stirring speed is 500 r / min, and the oil content of the tailings after extraction is 0.35%.

[0081] Example 21

[0082] In this embodiment, the object of treatment is white oil-based rock fragments. The treatment method is the same as in Example 17, except that: the inhibitor is a mixture of sodium phosphate, water glass, and tannic acid in a mass ratio of 1:1.5:3, with a dosage of 800 g / t; the targeted barite collector is a solution 1 obtained by dissolving bipyridinium salt (f) in solvent N,N-dimethylformamide to obtain a 5 wt% solution, and a solution 2 obtained by dissolving oxalic acid in solvent ethanol to obtain a 5 wt% solution, which is then mixed with solution 2 in a molar ratio of bipyridinium salt (f) and oxalic acid of 2:1, with a dosage of 400 g / t; the dispersant is a mixture of sodium pyrophosphate, sodium hexametaphosphate, and water glass in a mass ratio of 1:1:3, with a dosage of 0.25%; and the frother is pine oil, with a dosage of 8 g / t. After flotation, the barite recovery rate is 96%, and the density is 4.2 g·cm³. -3 .

[0083] Example 22

[0084] In this embodiment, the object of treatment is white oil-based rock fragments. The treatment method is the same as in Example 17, except that the targeted barite collector is prepared by dissolving bipyridinium salt (a) and bipyridinium salt (f) in N,N-dimethylformamide to obtain a 5wt% solution 1, and dissolving 6-chloronicotinic acid in ethanol to obtain a 5wt% solution 2. Solution 1 and solution 2 are then mixed at a molar ratio of 0.5:1:1, with a dosage of 500 g / t. The dispersant is prepared by compounding sodium pyrophosphate, sodium hexametaphosphate, and water glass at a mass ratio of 1.5:1:2, with a dosage of 0.75%. The foaming agent is pine oil, with a dosage of 12 g / t. After flotation, the barite recovery rate is 98%, and the density is 4.4 g·cm³. -3 .

[0085] Example 23

[0086] In this embodiment, the object of treatment is white oil-based rock fragments. The treatment method is the same as in Example 17, except that the targeted barite collector is prepared by dissolving bipyridinium salt (a) and bipyridinium salt (f) in N,N-dimethylformamide to obtain a 5wt% solution 1, and dissolving trimellitic acid in ethanol to obtain a 5wt% solution 2. Solution 1 and solution 2 are then mixed at a molar ratio of 1:1:2, with a dosage of 600 g / t. The dispersant is prepared by compounding sodium pyrophosphate, sodium hexametaphosphate, and water glass in a mass ratio of 1.5:1:2, with a dosage of 0.75%. The foaming agent is pine oil, with a dosage of 15 g / t. After flotation, the barite recovery rate is 97%, and the density is 4.3 g·cm³. -3 .

[0087] Example 24

[0088] In this embodiment, the object of treatment is white oil-based rock fragments. The treatment method is the same as in Example 17, except that the targeted barite collector is prepared by dissolving bipyridinium salt (a) and bipyridinium salt (c) in N,N-dimethylformamide to obtain a 5wt% solution 1, and dissolving trimellitic acid in ethanol to obtain a 5wt% solution 2. Solution 1 and solution 2 are then mixed at a molar ratio of 1:1:2, with a dosage of 600 g / t. The dispersant is prepared by compounding sodium pyrophosphate, sodium hexametaphosphate, and water glass in a mass ratio of 1.5:1:2, with a dosage of 0.75%. The frother is pine oil, with a dosage of 15 g / t. After flotation, the barite recovery rate is 93%, and the density is 4.0 g·cm³. -3 .

[0089] Example 25

[0090] In this embodiment, the object of treatment is white oil-based rock fragments. The treatment method is the same as in Example 17, except that the targeted barite collector is prepared by dissolving bipyridinium salt (a) and bipyridinium salt (e) in N,N-dimethylformamide to obtain a 5wt% solution 1, and dissolving trimellitic acid in ethanol to obtain a 5wt% solution 2. Solution 1 and solution 2 are then mixed at a molar ratio of 1:1:2, with a dosage of 600 g / t. The dispersant is prepared by compounding sodium pyrophosphate, sodium hexametaphosphate, and water glass in a mass ratio of 1.5:1:2, with a dosage of 0.75%. The foaming agent is pine oil, with a dosage of 5 g / t. After flotation, the barite recovery rate is 92%, and the density is 4.1 g·cm³. -3 .

[0091] Example 26

[0092] In this embodiment, the object being processed is white oil-based rock fragments. The processing method is the same as in Example 17, except that the targeted barite collector is prepared by dissolving bipyridinium salt (b) and bipyridinium salt (f) in N,N-dimethylformamide to obtain a 5wt% solution 1, and dissolving p-hydroxybenzoic acid in ethanol to obtain a 5wt% solution 2. Solution 1 and solution 2 are then mixed at a molar ratio of 1:1:2, with a dosage of 600 g / t. The dispersant is prepared by compounding sodium pyrophosphate, sodium hexametaphosphate, and water glass in a mass ratio of 1:1:1, with a dosage of 1%. The frother is pine oil, with a dosage of 10 g / t. After flotation, the barite recovery rate is 90%, and the density is 4.2 g·cm³. -3 .

[0093] Example 27

[0094] In this embodiment, the object being processed is white oil-based rock fragments. The processing method is the same as in Example 17, except that the flotation tailings are dried at 105°C for 4 hours. After drying, the tailings, bauxite, and potassium feldspar are mixed in a mass ratio of 3:5:1, ball-milled, and sieved to obtain a mixture with a particle size below 45 μm. Polyvinyl alcohol solution (4 wt%) is added to the mixture in a mass ratio of 1:8, mixed thoroughly, granulated, and naturally air-dried. After sieving (15 / 30 mesh, 25 / 40 mesh, 30 / 50 mesh), the raw proppant is obtained and sent to a resistance furnace for sintering at 1200°C at a heating rate of 10°C / min. After reaching the temperature, the furnace is stopped and cooled to obtain proppant clinker of the corresponding mesh sizes (20 / 40 mesh, 30 / 50 mesh, 40 / 70 mesh). The bulk density of the 20 / 40 mesh product is 1.33 g·cm³. -3The breakage rate was 9.8% at 35 MPa; the bulk density of the 30 / 50 mesh product was 1.25 g·cm³. -3 The breakage rate at 35 MPa was 8.74%; the bulk density of the 40 / 70 mesh product was 1.36 g·cm³. -3 The breakage rate was 9.12% at 35 MPa.

[0095] Example 28

[0096] In this embodiment, the object being processed is white oil-based rock fragments. The processing method is the same as in Example 17, except that the flotation tailings are dried at 105°C for 4 hours. After drying, the tailings, bauxite, and potassium feldspar are mixed in a mass ratio of 1.5:7:2, ball-milled, and sieved to obtain a mixture with a particle size of less than 45 μm. Polyvinyl alcohol solution (4 wt%) is added to the mixture in a mass ratio of 1:8, mixed thoroughly, granulated, and naturally air-dried. After sieving (15 / 30 mesh, 25 / 40 mesh, 30 / 50 mesh), the raw proppant is obtained and sent to a resistance furnace for sintering at a temperature of 1300°C and a heating rate of 8°C / min. After reaching the temperature, the furnace is stopped and cooled to obtain proppant clinker of the corresponding mesh sizes (20 / 40 mesh, 30 / 50 mesh, 40 / 70 mesh). The bulk density of the 20 / 40 mesh product is 1.38 g·cm³. -3 The breakage rate at 35 MPa was 7.22%; the bulk density of the 30 / 50 mesh product was 1.35 g·cm³. -3 The breakage rate at 35 MPa was 7.06%; the bulk density of the 40 / 70 mesh product was 1.41 g·cm³. -3 The breakage rate was 7.98% at 35 MPa.

[0097] As can be seen from Examples 1-28 above, the developed high-efficiency oil-based rock cuttings degreasing agent can effectively reduce the oil content of oil-based rock cuttings to below 1% under normal temperature conditions of 15-40℃. Example 6 further demonstrates that even at a low temperature of 10℃, the oil content after treatment with the invented degreasing agent can still be below 1%. Comparing Examples 2, 4, and 5, it can be seen that temperature has a certain influence on the degreasing effect of the degreasing agent, and its degreasing effect is better in the temperature range of 35-40℃. Further comparing Examples 1, 2, and 4, and Examples 19 and 20, it can be seen that the degreasing effect increases with the increase of the proportion of diesel or white oil and methyl ethyl ketone in the degreasing agent, but the subsequent centrifugation difficulty increases with the decrease of the water content. To balance the degreasing and centrifugation effects, the optimal application range of the degreasing agent is a compound of diesel or white oil, methyl ethyl ketone, sodium silicate, and water in a mass ratio of 45-55:15-20:0.2-0.3:20-25.

[0098] As can be seen from Examples 1-28 above, the developed targeted barite collectors can all achieve a barite recovery rate of ≥90% and a density of ≥4.0 g·cm³. -3 This meets the requirements for well site reuse. Comparison of Examples 1, 7, 8, 9, 10, and 11 shows that the targeted collector prepared using bipyridinium salt (a) and bipyridinium salt (f) is more effective than the targeted collector prepared using bipyridinium salt (b), bipyridinium salt (c), bipyridinium salt (d), and bipyridinium salt (a). Examples 12 and 13 show that the targeted collector obtained by combining two or more bipyridinium salts is more effective than the targeted collector prepared using a single bipyridinium salt.

Claims

1. A targeted barite collector, characterized in that, The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following:

2. A method of preparing the targeting barite collector of claim 1, characterized by, The mixture of any one or more of the following: The mixture of any one or more of the following:

3. The method of claim 2, wherein, The mixture of any one or more of the following:

4. A method of barite extraction, characterized in that, The mixture of any one or more of the following: The mixture of any one or more of the following:

5. The method of extracting barite as claimed in claim 4 wherein, The mixture of any one or more of the following:

6. The method of extracting barite of claim 5, wherein, The mixture of any one or more of the following:

7. The method of extracting barite of claim 5, wherein, The mixture of any one or more of the following:

8. The method of extracting barite of claim 5, wherein, The mixture of any one or more of the following:

9. The method of claim 5, wherein the barite is extracted by the process of, The mixture of any one or more of the following:

10. A process for comprehensive utilization of oil-based drill cuttings, characterized in that, The mixture of any one or more of the following:

11. The integrated utilization process of oil-based cuttings of claim 10, characterized in that, The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more of the following: The mixture of any one or more

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