A three-mud treatment agent and preparation method thereof

Abstract

The invention discloses a three-mud treatment agent and a preparation method thereof, which belongs to the technical field of oily sludge treatment, including treatment agent A and treatment agent B, wherein treatment agent B comprises the following raw materials composed of parts by mass: 30-40 parts of polyacrylamide, 8-10 parts of modified attapulgite clay, 5-6 parts of compound, and 40-55 parts of deionized water. The modified attapulgite clay is strongly combined with the protective film at the oil-water and oil-mud interfaces in the oil sludge through electrostatic force, hydrogen bond, and hydrophobic action, destroying the oil-water and oil-mud interface protective films, so that the oil droplets are released and aggregated to form an oil phase, realizing the separation of oil, water, and sludge, and the positive charge carried in the modified attapulgite clay can be adsorbed to the surface of negatively charged sludge particles for sedimentation and precipitation; the carboxyl groups contained in the modified hemicellulose and the hydrophilic groups that can be combined with the sophorolipids form stable mixed micelles, so as to avoid the sophorolipids being easily affected by the environment and failing, resulting in the re-aggregation and precipitation of the oil droplets.

Description

Technical Field

[0001] The invention relates to the technical field of oily sludge treatment, in particular to a three-sludge treatment agent and a preparation method thereof. Background Art

[0002] Oily sludge does not exist inherently in nature. Instead, it is a mixture formed by crude oil running, bubbling, dripping, leaking, and leaking to the ground due to natural sedimentation, various accidents, equipment corrosion and damage, etc. during the process of oil field exploitation, transportation, storage, oil refining and use in the petrochemical industry, and deposited in the soil and mixed with other impurities. It is referred to as oil sludge, and its main components are oil, mud and water. The methods for treating oily sludge include landfill, incineration, centrifuge dehydration, thermal analysis decomposition, traditional thermochemical demulsification and microbial treatment. Among them, traditional thermochemical demulsification and microbial treatment can reduce the pollution impact of oily sludge on the environment, recover the oil and water in the oily sludge, achieve resource reuse, and restore the original use value of the soil.

[0003] The sludge component in oily sludge contains a large number of clay particles. The surface of these clay particles has a porous structure and is easy to adhere to a large amount of crude oil, which makes it difficult to separate the crude oil from the pores, affecting the oil removal rate. The three-mud treatment agent can separate sludge, oil and water, but most of the three-mud treatment agents have the characteristics of small dehydration amount, slow speed, poor demulsification effect, and small scope of application, which affects the treatment efficiency of oil sludge. Summary of the invention

[0004] The purpose of the present invention is to provide a three-mud treatment agent and a preparation method thereof: polybutyl methacrylate is used as a core, and acrylic acid and methacrylate-2-(dimethylamino)ethyl ester copolymer is used as a shell to form core-shell nanoparticles, the positive charge carried on the surface of the core-shell nanoparticles can be combined with the negative charge around the oil droplets in the sludge, and the electrostatic repulsion at the oil-water interface and the oil-mud interface is weakened; a coupling agent is grafted on the surface of the core-shell nanoparticles to consume the remaining carboxyl groups of the core-shell nanoparticles, and avoid the presence of some negatively charged carboxyl groups in the core-shell nanoparticles, which generates repulsion with the negatively charged oil-water and oil-mud interfaces and affects the demulsification effect; stearic acid is grafted on the surface of the core-shell nanoparticles to form modified core-shell nanoparticles, which are strongly bonded to the protective film at the oil-water and oil-mud interfaces in the sludge through electrostatic force, hydrogen bonds, and hydrophobic effects. The modified core-shell nanoparticles are deposited on the surface of attapulgite clay to block the pores of attapulgite clay and prevent the porous structure of attapulgite clay from absorbing oily components and water in the sludge. Succinic anhydride is grafted on the surface of hemicellulose to form amphiphilic hemicellulose with good surface activity and lower interfacial tension, which can be adsorbed on the oil-water interface in the sludge to reduce the oil-water interfacial tension. The modified hemicellulose is mixed with sophorolipids, and the carboxyl groups contained in the modified hemicellulose and the hydrophilic groups that can combine with sophorolipids form stable mixed micelles, which prevent the sophorolipids from being easily affected by the environment and becoming ineffective, resulting in the re-aggregation and precipitation of oil droplets.

[0005] The technical problem to be solved by the present invention is as follows: the sludge component in the oily sludge contains a large number of clay particles, the surface of these clay particles has a porous structure, and a large amount of crude oil is easily adhered, which makes it difficult to separate the crude oil from the pores, affecting the oil removal rate; the three-sludge treatment agent can separate the sludge, oil and water, but most of the three-sludge treatment agents have the characteristics of small dehydration amount, slow speed, poor demulsification effect, small application range, etc., which affects the treatment efficiency of the oil sludge.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] A three-mud treatment agent comprises a treatment agent A and a treatment agent B; the treatment agent B comprises the following raw materials in parts by weight: 30-40 parts of polyacrylamide, 8-10 parts of modified attapulgite clay, 5-6 parts of a compound, and 40-55 parts of deionized water.

[0008] A method for preparing a three-mud treatment agent specifically comprises the following steps:

[0009] The polyacrylamide, modified attapulgite clay, compound and deionized water are mixed, placed in a stirring kettle, and stirred at 200-300 r / min for 30-40 min to obtain treatment agent B; treatment agent B is mixed with treatment agent A to obtain a three-mud treatment agent.

[0010] Furthermore, the treatment agent A is Bacillus licheniformis, and the mass fraction is 18-22%.

[0011] Furthermore, the mass ratio of treatment agent A to treatment agent B is (8-12):(7-9).

[0012] Furthermore, the modified attapulgite clay is prepared by depositing modified core-shell nanoparticles on the surface of acid-treated attapulgite clay, specifically by the following steps:

[0013] A1. Add attapulgite clay to a 3 mol / L hydrochloric acid aqueous solution, stir at 600 r / min for 20 min at 40°C to obtain a suspension, wash the suspension three times with deionized water, centrifuge at 3900 r / min for 3 min to obtain a precipitate, dry the precipitate in an oven at 80°C for 12 h, and grind to obtain acid-treated attapulgite clay.

[0014] A2. The modified core-shell nanoparticles were added to an ethanol solution and stirred to obtain a dispersion, and the dispersion was evenly coated on the surface of the acid-treated attapulgite clay, and dried in an oven at 85°C to evaporate the organic solvent to obtain modified attapulgite clay.

[0015] Furthermore, in the above-mentioned reaction process A1, the hydrochloric acid treatment of attapulgite clay can effectively remove impurities such as quartz and dolomite in the attapulgite clay, improve the purity of the attapulgite clay, and avoid the influence of the attapulgite clay impurities on the water quality.

[0016] Furthermore, during the above-mentioned A2 reaction process, the modified core-shell nanoparticles are dispersed in ethanol to form a uniform dispersion, which is sprayed onto the surface of the acid-treated attapulgite clay. The porous structure of the attapulgite has good adsorption. After treatment at 85°C, the ethanol solvent evaporates, so that the modified core-shell nanoparticles are deposited on the surface of the attapulgite clay, blocking the pores of the attapulgite clay and preventing the porous structure of the attapulgite clay from adsorbing oily components and water in the sludge.

[0017] Furthermore, in step A1, the ratio of attapulgite clay to aqueous hydrochloric acid solution is (0.7-0.8) g: (10-20) mL.

[0018] Furthermore, in step A2, the ratio of modified core-shell nanoparticles to ethanol solution is (0.5-0.9) g: (35-45) mL.

[0019] Furthermore, the particle size of the core-shell nanoparticles is 60-100 nm.

[0020] Furthermore, the length of attapulgite clay is 1-5 μm and the diameter is 20-70 nm.

[0021] Furthermore, the modified core-shell nanoparticles are made of polybutyl methacrylate as the core and acrylic acid and methacrylate-2-(dimethylamino)ethyl ester copolymer as the shell, and the formed core-shell nanoparticles are reacted with a coupling agent and stearic acid to obtain the obtained nanoparticles.

[0022] Furthermore, the modified core-shell nanoparticles are prepared by the following steps:

[0023] The core-shell nanoparticles and the coupling agent were added to ethanol and deionized water, stirred evenly, and then 95% by mass acetic acid was added to adjust the pH value of the solution to 3.5. The mixture was stirred at 70°C for 0.7h, filtered, washed with deionized water for 3 times, and dried in an oven at 60°C for 15min to obtain amino core-shell nanoparticles.

[0024] Stearic acid and N, N'-dicyclohexylcarbodiimide were added to hexane, stirred evenly, and the amino core-shell nanoparticles were added. The reaction was stirred for 24 hours, filtered, washed twice with n-hexane, washed three times with deionized water, and dried in an oven at 60°C for 10 minutes to obtain modified core-shell nanoparticles.

[0025] Among them, the hydroxyl groups produced by the hydrolysis of the coupling agent can react with the carboxyl groups in the shell of the core-shell nanoparticles, so that the coupling agent is grafted on the surface of the core-shell nanoparticles, consuming the remaining carboxyl groups of the core-shell nanoparticles, avoiding the presence of some negatively charged carboxyl groups in the core-shell nanoparticles, and avoiding the repulsion between the negatively charged oil-water and oil-sludge interfaces, thus affecting the demulsification effect.

[0026] Furthermore, N,N'-dicyclohexylcarbodiimide is used as a dehydrating agent, and the carboxyl group of stearic acid can react with the amino group of the amino core-shell nanoparticles, so that stearic acid is grafted onto the surface of the core-shell nanoparticles.

[0027] Furthermore, the dosage ratio of the core-shell nanoparticles, coupling agent, ethanol, and deionized water is (0.3-0.7) g: (0.1-0.2) g: (15-25) mL: (10-20) mL.

[0028] Furthermore, the amount ratio of stearic acid, N,N'-dicyclohexylcarbodiimide, hexane, and amino core-shell nanoparticles is (1.2-1.4) g: (0.1-0.3) g: (15-25) mL: (0.3-0.7) g.

[0029] Furthermore, the coupling agent is selected from 3-aminopropyltriethoxysilane.

[0030] Furthermore, the particle size of the core-shell nanoparticles is 60-100 nm.

[0031] Furthermore, the core-shell nanoparticles are prepared by the following steps:

[0032] Butyl methacrylate and azobisisobutyronitrile are added to 1,2-dioxane, stirred evenly, heated to 70°C and stirred for reaction for 1 hour, cooled to room temperature, acrylic acid and 2-(dimethylamino)ethyl methacrylate are added, stirred evenly, and the reaction is continued at 70°C for 1 hour, cooled to room temperature, placed in hexane to precipitate the product, the precipitated product is filtered, washed, and dried in an oven at 40°C for 10 minutes to obtain core-shell nanoparticles.

[0033] Among them, polybutyl methacrylate is used as the core and acrylic acid and 2-(dimethylamino)ethyl methacrylate copolymer is used as the shell to prepare core-shell nanoparticles. The positive charge carried on the surface of the core-shell nanoparticles can combine with the negative charge around the oil droplets in the sludge, weakening the electrostatic repulsion at the oil-water interface and the oil-sludge interface. The core-shell nanoparticles can replace the asphaltene at the oil-water interface and the oil-sludge interface in the sludge, thereby destroying the protective film at the oil-water and oil-sludge interfaces in the sludge.

[0034] Furthermore, the usage ratio of butyl methacrylate, azobisisobutyronitrile, 1,2-dioxane, acrylic acid, and 2-(dimethylamino)ethyl methacrylate is (1-1.6) g:(0.06-0.1) g:(15-25) mL:(0.2-0.4) g:(2.8-3) g.

[0035] Furthermore, the composite is prepared by surface-modifying hemicellulose with succinic anhydride and then mixing with sophorolipids, and is specifically prepared by the following steps:

[0036] B1. Urea and choline chloride were weighed in a molar ratio of 2:1, mixed and heated to 80°C to form a transparent liquid, hemicellulose and succinic anhydride were added to the transparent liquid, stirred evenly, placed in a microwave reactor at 60°C to react for 10 minutes, anhydrous ethanol was added to form a precipitate, and the precipitate was obtained by centrifugation. The precipitate was washed three times with deionized water, and the crude product was dialyzed in deionized water using a dialysis membrane with a molecular weight cutoff of 1000Da, and finally freeze-dried at -10°C for 1 hour to obtain modified hemicellulose.

[0037] B2. Add modified hemicellulose and sophorolipids to 55 mL of deionized water, stir evenly, place in a 60°C water bath, stir for 30 min, heat to 80°C and continue stirring until the water evaporates to obtain a composite.

[0038] Furthermore, in step B1, in a composite solvent of urea and choline chloride, microwave irradiation is used as a heating method, and the anhydride groups of succinic anhydride can undergo an esterification reaction with the hydroxyl groups in hemicellulose, so that succinic anhydride is grafted on the surface of hemicellulose, thereby achieving amphiphilic modification of hemicellulose. The formed amphiphilic hemicellulose has better surface activity and lower interfacial tension.

[0039] Furthermore, in step B2, the carboxyl groups contained in the modified hemicellulose can combine with the hydrophilic groups of the sophorolipids to form stable mixed micelles, thereby preventing the sophorolipids from being easily affected by the environment and becoming ineffective, resulting in the reaggregation and precipitation of the oil droplets.

[0040] Furthermore, in step B1, the ratio of hemicellulose, succinic anhydride and transparent liquid is (1-3) g: (5-6) g: (80-120) mL.

[0041] Furthermore, in step B2, the ratio of modified hemicellulose, sophorolipid and deionized water is (1-3) g: (1.5-1.9) g: (50-60) mL.

[0042] Furthermore, the succinic anhydride is selected from any one of butyl succinic anhydride, octenyl succinic anhydride, dodecenyl succinic anhydride and octadecenyl succinic anhydride.

[0043] Furthermore, hemicellulose contains 87-87.2% xylose, 8-8.1% arabinose, 0.4-0.5% galacturonic acid, 2.6-2.7% glucose, 0.7-0.8% galactose, and 1-1.1% glucuronic acid.

[0044] Furthermore, compared with the prior art, the present invention has the following beneficial effects:

[0045] (1) In the technical scheme of the present invention, polybutyl methacrylate is used as the core and acrylic acid and 2-(dimethylamino)ethyl methacrylate copolymer is used as the shell to form core-shell nanoparticles. The positive charge carried on the surface of the core-shell nanoparticles can combine with the negative charge around the oil droplets in the sludge to weaken the electrostatic repulsion between the oil-water interface and the oil-sludge interface. The core-shell nanoparticles can replace the asphaltene on the oil-water interface and the oil-sludge interface in the sludge, thereby destroying the protective film at the oil-water interface and the oil-sludge interface in the sludge, resulting in demulsification, dehydration and deoiling, and finally forming a three-phase stratification of oil, water and mud.

[0046] (2) In the technical scheme of the present invention, the coupling agent is grafted onto the surface of the core-shell nanoparticles to consume the remaining carboxyl groups of the core-shell nanoparticles, thereby avoiding the presence of some negatively charged carboxyl groups in the core-shell nanoparticles, which would generate repulsion with the negatively charged oil-water and oil-sludge interfaces and affect the demulsification effect; stearic acid is grafted onto the surface of the core-shell nanoparticles to form modified core-shell nanoparticles. On the one hand, the positive charge carried in the modified core-shell nanoparticles can generate electrostatic attraction with the negatively charged oil droplets in the oil sludge, and the long-chain alkane structure of stearic acid extends into the oil phase. On the other hand, the positively charged amino groups can generate hydrogen bonds with the asphaltene surfactant molecules in the oil sludge, and then strongly combine with the protective film at the oil-water and oil-sludge interfaces in the oil sludge through electrostatic force, hydrogen bonds, and hydrophobic effects, thereby destroying the oil-water and oil-sludge interface protective films, so that the oil droplets are released and aggregated to form an oil phase, thereby achieving the separation of oil, water, and sludge.

[0047] (3) In the technical scheme of the present invention, attapulgite clay is used as an inorganic demulsifier, which can effectively destroy the protective film at the interface between oil and water and oil sludge; the modified core-shell nanoparticles are deposited on the surface of attapulgite clay to obtain a demulsification aid, which can block the pores of attapulgite clay and prevent the porous structure of attapulgite clay from adsorbing oily components and water in the oil sludge; the formed modified attapulgite clay first destroys the protective film at the interface between oil and water and oil sludge in the oil sludge, so that the sludge is released, and further, the positive charge carried in the modified attapulgite clay can It is adsorbed onto the surface of negatively charged sludge particles, and the attapulgite clay is compatible with the clay in the sludge, so that the sludge and demulsifier aggregate to form particles and settle out, avoiding the demulsifier from remaining in the water and oil, thereby improving the treatment efficiency of the sludge. In addition, the demulsifier adsorbed on the sludge surface contains long hydrophobic chains that can be adsorbed into the pore walls of the porous clay particles in the sludge to form a hydrophobic layer, which produces a nano-slip effect on the water flow, increases the entry of water flow, realizes the displacement of oil by water, and then releases the crude oil in the sludge.

[0048] (4) In the technical scheme of the present invention, succinic anhydride is grafted on the surface of hemicellulose to form amphiphilic hemicellulose with good surface activity and lower interfacial tension. It can be adsorbed at the oil-water interface in the oil sludge, thereby reducing the oil-water interfacial tension. The oil component in the oily sludge tends to disperse or solubilize in the water phase, thereby detaching from the solid surface. It has a synergistic effect with the modified attapulgite clay in destroying the protective film at the oil-water interface, thereby improving the treatment efficiency of the oily sludge. In addition, the amphiphilic molecules are adsorbed on the solid surface of the oily sludge through hydrophobic action, thereby changing its wettability, promoting the desorption of hydrocarbon components, and reducing the oil content of the sludge from the oily sludge.

[0049] (5) In the technical scheme of the present invention, sophorolipids are used as microbial surface treatment, which has the characteristics of easy degradation, non-toxicity or low toxicity, and can be degraded to separate organic matter in sludge. It is used in combination with modified attapulgite clay to accelerate the separation efficiency of oil, water and sludge. The modified hemicellulose is mixed with sophorolipids. The carboxyl groups contained in the modified hemicellulose can combine with the hydrophilic groups of sophorolipids to form stable mixed micelles, which prevents the sophorolipids from being easily affected by the environment and failing, resulting in the re-aggregation and precipitation of oil droplets. In addition, the composite system usually has a lower surface tension and a smaller critical micelle concentration than a single component, which helps to more effectively reduce the tension of the oil-water interface during the sludge treatment process and promote the dispersion and emulsification of oil droplets. DETAILED DESCRIPTION

[0050] The technical solutions in the embodiments of the present invention are described clearly and completely. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0051] The raw materials used in the embodiments of the present invention are as follows: butyl methacrylate (Jinan Quanxing New Materials Co., Ltd., content 99%); azobisisobutyronitrile (Shandong Haoshun Chemical Co., Ltd., content 99.5%); 1,2-dioxane (analytical grade); 2-(dimethylamino)ethyl methacrylate (Hubei Kewode Chemical Co., Ltd.); γ-aminopropyltriethoxysilane (content 98%, Shanghai Aladdin Biochemical Technology Co., Ltd.); stearic acid (Jinan Century Tongda Chemical Co., Ltd.); N, N'-dicyclohexylcarbodiimide (Shanghai Aladdin Biochemical Technology Co., Ltd.); succinic anhydride (Shanghai Aladdin Biochemical Technology Co., Ltd.); sophorolipids (Hubei Yamade Biomedicine Co., Ltd., content 98%).

[0052] The length of attapulgite is 1-5μm and the diameter is 20-70nm, Nanjing Bermuda Biotechnology Co., Ltd.

[0053] The surface of attapulgite clay is treated with acid, and the preparation method is specifically prepared by the following steps:

[0054] 0.75 g of attapulgite clay was added to 15 mL of 3 mol / L hydrochloric acid aqueous solution, and stirred at 600 r / min for 20 min at 40 ° C to obtain a suspension. The suspension was washed three times with deionized water and centrifuged at 3900 r / min for 3 min to obtain a precipitate. The precipitate was dried in an oven at 80 ° C for 12 h and ground to obtain acid-treated attapulgite clay.

[0055] The core-shell nanoparticles are specifically prepared by the following steps:

[0056] 1.3 g of butyl methacrylate and 0.08 g of azobisisobutyronitrile were added to 20 mL of 1,2-dioxane, stirred evenly, heated to 70°C and stirred for reaction for 1 hour, cooled to room temperature, 0.3 g of acrylic acid and 2.9 g of 2-(dimethylamino)ethyl methacrylate were added, stirred evenly, and the reaction was continued at 70°C for 1 hour. The mixture was cooled to room temperature and placed in hexane to precipitate the product. The precipitated product was filtered, washed, and dried in an oven at 40°C for 10 minutes to obtain core-shell nanoparticles.

[0057] Example 1 The modified attapulgite clay is prepared by the following steps:

[0058] A1. Add 0.5 g of core-shell nanoparticles and 0.12 g of γ-aminopropyltriethoxysilane to 20 mL of ethanol and 15 mL of deionized water, stir evenly, then add 95% acetic acid to adjust the pH value of the solution to 3.5, stir at 70°C for 0.7 h, filter, wash with deionized water three times, and dry in an oven at 60°C for 15 min to obtain amino core-shell nanoparticles.

[0059] A2. Add 1.3 g of stearic acid and 0.2 g of N, N'-dicyclohexylcarbodiimide to 20 mL of hexane, stir evenly, add 0.5 g of amino core-shell nanoparticles, stir and react for 24 h, filter, wash twice with n-hexane, wash three times with deionized water, and dry in an oven at 60 ° C for 10 min to obtain modified core-shell nanoparticles.

[0060] A3. Add 0.7 g of modified core-shell nanoparticles to 40 mL of ethanol solution and stir evenly to obtain a dispersion. The dispersion is evenly coated on the surface of the acid-treated attapulgite clay and placed in an oven at 85°C to dry the organic solvent to evaporate and obtain modified attapulgite clay.

[0061] Comparative Example 1 The difference between this comparative example and Example 1 is that the modified core-shell nanoparticles are replaced by core-shell nanoparticles, and the remaining steps and raw materials are synchronized with Example 1.

[0062] 0.7 g of core-shell nanoparticles were added to 40 mL of ethanol solution and stirred evenly to obtain a dispersion. The dispersion was evenly coated on the surface of the acid-treated attapulgite clay and dried in an oven at 85° C. to evaporate the organic solvent, thereby obtaining modified attapulgite clay.

[0063] Comparative Example 2 The difference between this comparative example and Example 1 is that no modified core-shell nanoparticles are added, and the remaining steps and raw materials are synchronized with Example 1.

[0064] 0.75 g of attapulgite clay was added to 15 mL of 3 mol / L hydrochloric acid aqueous solution, and stirred at 600 r / min for 20 min at 40°C to obtain a suspension. The suspension was washed three times with deionized water and centrifuged at 3900 r / min for 3 min to obtain a precipitate. The precipitate was dried in an oven at 80°C for 12 h and ground to obtain modified attapulgite clay.

[0065] Embodiment 2 The composite material is specifically prepared by the following steps:

[0066] B1. Urea and choline chloride were weighed in a molar ratio of 2:1, mixed and heated to 80°C to form a transparent liquid, 2 g of hemicellulose and 5.56 g of succinic anhydride were added to 100 mL of the transparent liquid, and the mixture was stirred evenly. The mixture was placed in a microwave reactor at 60°C to react for 10 min, and then anhydrous ethanol was added to form a precipitate. The precipitate was obtained by centrifugation, and the precipitate was washed three times with deionized water. The crude product was dialyzed in deionized water using a dialysis membrane with a molecular weight cutoff of 1000 Da, and finally freeze-dried at -10°C for 1 h to obtain modified hemicellulose.

[0067] B2. Add 2 g of modified hemicellulose and 1.7 g of sophorolipid to 55 mL of deionized water, stir evenly, place in a 60°C water bath, stir for 30 min, heat to 80°C and continue stirring until the water evaporates to obtain a composite.

[0068] Comparative Example 3 The difference between this comparative example and Example 2 is that the modified hemicellulose is replaced by hemicellulose, and the remaining steps and raw materials are synchronized with Example 2.

[0069] 2 g of cellulose and 1.7 g of sophorolipid were added to 55 mL of deionized water, stirred evenly, placed in a 60° C. water bath, stirred for 30 min, heated to 80° C. and continued to stir until the water evaporated to obtain a composite.

[0070] Comparative Example 4 The difference between this comparative example and Example 2 is that no sophorolipid is added, and the remaining steps and raw materials are the same as Example 2.

[0071] Urea and choline chloride were weighed in a molar ratio of 2:1, mixed and heated to 80°C to form a transparent liquid, 2 g of hemicellulose and 5.56 g of succinic anhydride were added to 100 mL of the transparent liquid, stirred evenly, placed in a microwave reactor at 60°C to react for 10 min, and then anhydrous ethanol was added to form a precipitate. The precipitate was obtained by centrifugation, washed three times with deionized water, and the crude product was dialyzed in deionized water using a dialysis membrane with a molecular weight cutoff of 1000 Da, and finally freeze-dried at -10°C for 1 h to obtain modified hemicellulose.

[0072] Example 3 A three-mud treatment agent includes treatment agent A and treatment agent B; treatment agent B includes the following raw materials in parts by mass: 30 parts of polyacrylamide, 8 parts of modified attapulgite clay, 5 parts of a compound, and 40 parts of deionized water.

[0073] A method for preparing a three-mud treatment agent specifically comprises the following steps:

[0074] Polyacrylamide, modified attapulgite clay, a compound and deionized water were mixed, placed in a stirring kettle, and stirred at 200 r / min for 30 minutes to obtain a treatment agent B; the treatment agent B was mixed with the treatment agent A to obtain a three-mud treatment agent.

[0075] Wherein, the treatment agent A is Bacillus licheniformis, and the mass fraction is 20%.

[0076] The mass ratio of treatment agent A to treatment agent B is 8:7.

[0077] Example 4 A three-mud treatment agent includes treatment agent A and treatment agent B; treatment agent B includes the following raw materials in parts by mass: 35 parts of polyacrylamide, 9 parts of modified attapulgite clay, 5.5 parts of a compound, and 45 parts of deionized water.

[0078] A method for preparing a three-mud treatment agent specifically comprises the following steps:

[0079] Polyacrylamide, modified attapulgite clay, a compound and deionized water were mixed, placed in a stirring kettle, and stirred at 250 r / min for 35 minutes to obtain a treatment agent B; the treatment agent B was mixed with the treatment agent A to obtain a three-mud treatment agent.

[0080] Wherein, the treatment agent A is Bacillus licheniformis, and the mass fraction is 20%.

[0081] The mass ratio of treatment agent A to treatment agent B is 10:8.

[0082] Example 5 A three-mud treatment agent includes treatment agent A and treatment agent B; treatment agent B includes the following raw materials in parts by mass: 40 parts of polyacrylamide, 10 parts of modified attapulgite clay, 6 parts of a compound, and 55 parts of deionized water.

[0083] A method for preparing a three-mud treatment agent specifically comprises the following steps:

[0084] Polyacrylamide, modified attapulgite clay, a compound and deionized water are mixed, placed in a stirring kettle, and stirred at 300 r / min for 40 minutes to obtain a treatment agent B; the treatment agent B is mixed with the treatment agent A to obtain a three-mud treatment agent.

[0085] Wherein, the treatment agent A is Bacillus licheniformis, and the mass fraction is 20%.

[0086] The mass ratio of treatment agent A to treatment agent B is 12:9.

[0087] Comparative Example 5 The difference between this comparative example and Example 4 is that the modified attapulgite clay is replaced by the material prepared in Comparative Example 1, and the remaining steps and raw materials are synchronized with Example 4.

[0088] Comparative Example 6 The difference between this comparative example and Example 4 is that the modified attapulgite clay is replaced by the nanomaterial prepared in Comparative Example 2, and the remaining steps and raw materials are synchronized with Example 4.

[0089] Comparative Example 7 The difference between this comparative example and Example 4 is that the compound is replaced by the substance prepared in Comparative Example 3, and the remaining steps and raw materials are synchronized with Example 4.

[0090] Comparative Example 8 The difference between this comparative example and Example 4 is that the compound is replaced by the substance prepared in Comparative Example 4, and the remaining steps and raw materials are synchronized with Example 4.

[0091] The performance of the three mud treatment agents prepared in Examples 3-5 and Comparative Examples 5-8 was tested;

[0092] The oily sludge selected in the experiment had a water content of 81.6% m / m, an oil content of 8.4% m / m, and a total weight of 200 g.

[0093] Mix the oily sludge with the three-mud treatment agent, oscillate on an oscillator for 5 minutes, and after reaction and homogenization, place it in a 40°C constant temperature water bath, and continue to react until bubble-like oil flowers float on the surface of the sedimentation and dehydration. At the same time, gradually increase the temperature to 76°C (if it contains more wax or colloid asphalt, the heating temperature needs to be increased to above 90°C), and fully react for 40 minutes; pump it into a three-phase centrifuge to separate the three phases of oil, sewage and mud to obtain oil phase, water phase and solid phase.

[0094] The water content (%) in the oil phase was determined by the distillation method according to the national standard GB / T8929-2006.

[0095] The ultraviolet fluorescence method is used to detect the oil content (mg / L) in water. The ultraviolet fluorescence method: the separated water phase is subjected to ultraviolet fluorescence detection. The ultraviolet light emitted by the light source is irradiated on the flowing separated water phase. The oil component in the separated water phase absorbs the ultraviolet light and transitions to a high-energy state. The high-energy state is unstable and then transitions back to a low-energy state to emit fluorescence, and the value is recorded.

[0096] The calcination differential weight method is used to detect the oil content and water content in the mud after separation: 5g of separated sludge is placed in an automatic ash moisture meter, kept at 100℃ for 4h, then heated to 600℃ and kept for 6h. The water content (%) and solid content (%) in the mud after separation can be calculated based on the weight change; Oil content in the mud after separation = 1-water content-solid content.

[0097] After separation, the water content in the oil-water is 1.88%, the oil content in the water is less than 434 mg / L, and the oil content in the mud is 2.81%, which meets the national emission standards;

[0098] The results are shown in Table 1 below:

[0099] Table 1

[0100]

[0101]

[0102] It can be seen from the data in Table 1 that in Comparative Example 5, the modified core-shell nanoparticles are replaced with modified attapulgite clay prepared by core-shell nanoparticles, and added to the three-phase separation agent, and the oil, water, and sludge three-phase separation efficiency is low. This may be because stearic acid is grafted on the surface of the core-shell nanoparticles through a coupling agent, and is strongly combined with the protective film at the oil-water and sludge interfaces in the sludge through electrostatic force, hydrogen bond, and hydrophobic effect, thereby achieving the separation of oil, water, and sludge; in Comparative Example 6, the modified attapulgite clay prepared by not adding modified core-shell nanoparticles is When added to the three-mud treatment agent, the oil, water and sludge three-phase separation efficiency is low. This may be because the modified core-shell nanoparticles are deposited on the surface of the attapulgite clay, which can block the pores of the attapulgite clay, and the attapulgite clay deposited with modified core-shell nanoparticles can be adsorbed to the surface of the negatively charged sludge particles, and the attapulgite clay is compatible with the clay in the sludge, so that the sludge and demulsifier aggregate to form particles and settle out, avoiding the demulsifier from remaining in the water and oil, thereby improving the treatment efficiency of the sludge.

[0103] In Comparative Example 7, the modified hemicellulose is replaced with a compound prepared by hemicellulose, and the compound is added to the three-mud treatment agent. The oil, water and sludge three-phase separation efficiency is low. This may be because succinic anhydride is grafted on the surface of hemicellulose, and the amphiphilic hemicellulose formed has good surface activity and lower interfacial tension, and has a synergistic effect with the modified attapulgite clay in destroying the oil-water interface protective film, thereby improving the treatment efficiency of the sludge; in Comparative Example 8, the compound prepared without adding sophorolipids is added to the three-mud treatment agent, and the oil, water and sludge three-phase separation efficiency is low. This may be because sophorolipids can be degraded to separate organic matter in the sludge, and are used in combination with modified attapulgite clay to accelerate the separation efficiency of oil, water and sludge.

[0104] The data in Table 1 show that the three-mud treatment agents prepared in Examples 3-5 meet the test performance requirements, while the three-mud treatment agents prepared in Comparative Examples 5-8 do not meet the performance requirements, indicating that the three-mud treatment agents prepared in the present invention can effectively achieve the three-phase separation containing sludge, and the water content in the oil phase, the oil content in the water phase, and the oil content in the sludge all meet the emission standards.

[0105] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0106] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A three-mud treatment agent, which can achieve the separation of oil, water and sludge, characterized in that: The invention comprises a treatment agent A and a treatment agent B, wherein the treatment agent A is Bacillus licheniformis, and the treatment agent B comprises the following raw materials in parts by weight: 30-40 parts of polyacrylamide, 8-10 parts of modified attapulgite clay, 5-6 parts of a compound, and 40-55 parts of deionized water; The modified attapulgite clay is prepared by depositing modified core-shell nanoparticles on the surface of acid-treated attapulgite clay; The modified core-shell nanoparticles are made of polybutyl methacrylate as the core and acrylic acid and methacrylate-2-(dimethylamino)ethyl ester copolymer as the shell, and the formed core-shell nanoparticles are then reacted with a coupling agent and stearic acid to obtain the modified core-shell nanoparticles. The compound is prepared by surface-modifying hemicellulose with succinic anhydride and then mixing with sophorolipid.

2. A three-mud treatment agent according to claim 1, characterized in that: The core-shell nanoparticles are specifically prepared by the following steps: Butyl methacrylate and azobisisobutyronitrile are added to 1,2-dioxane, stirred evenly, stirred for reaction, cooled to room temperature, acrylic acid and 2-(dimethylamino)ethyl methacrylate are added, stirred evenly, continued to stir for reaction, cooled to room temperature, placed in hexane to precipitate the product, filtered, washed and dried to obtain core-shell nanoparticles.

3. A three-mud treatment agent according to claim 2, characterized in that: The usage ratio of butyl methacrylate, azobisisobutyronitrile, 1,2-dioxane, acrylic acid, and 2-(dimethylamino)ethyl methacrylate is (1-1.6) g: (0.06-0.1) g: (15-25) mL: (0.2-0.4) g: (2.8-3) g; The particle size of the core-shell nanoparticles is 60-100 nm.

4. A three-mud treatment agent according to claim 1, characterized in that: The coupling agent is selected from 3-aminopropyltriethoxysilane.

5. A three-mud treatment agent according to claim 1, characterized in that: The acid-treated attapulgite clay is specifically prepared by the following steps: The attapulgite clay is added to a 2-4 mol / L hydrochloric acid aqueous solution, and stirred at 550-650 r / min at 35-45° C. to obtain a suspension, and the suspension is washed with deionized water and centrifuged to obtain a precipitate, and the precipitate is dried and ground to obtain acid-treated attapulgite clay.

6. A three-mud treatment agent according to claim 5, characterized in that: The attapulgite clay has a length of 1-5 μm and a diameter of 20-70 nm.

7. A three-mud treatment agent according to claim 6, characterized in that: The succinic anhydride is selected from any one of butyl succinic anhydride, octenyl succinic anhydride, dodecenyl succinic anhydride and octadecenyl succinic anhydride.

8. A three-mud treatment agent according to claim 1, characterized in that: The hemicellulose contains 87-87.2% of xylose, 8-8.1% of arabinose, 0.4-0.5% of galacturonic acid, 2.6-2.7% of glucose, 0.7-0.8% of galactose and 1-1.1% of glucuronic acid.

9. A three-mud treatment agent according to claim 1, characterized in that: The mass fraction of the Bacillus licheniformis is 18-22%.

10. The method for preparing a three-mud treatment agent according to any one of claims 1 to 9, characterized in that: The specific steps include: The polyacrylamide, modified attapulgite clay, compound and deionized water are mixed, placed in a stirring kettle, and stirred at 200-300 r / min for 30-40 min to obtain treatment agent B; treatment agent B is mixed with treatment agent A to obtain a three-mud treatment agent.

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