Efficient water clarifier and preparation method thereof

Abstract

The invention discloses an efficient water clarifier and a preparation method thereof. The efficient water clarifier comprises the following raw materials in percentage by mass: 5-25% of organic amine B; 4%-20% of water-borne epoxy resin; 5%-25% of a thio-modified reagent; 10%-25% of a 50% sodium hydroxide solution D; 0%-3% of a 50% sodium hydroxide solution E; 0.2%-3% of micromolecular organic amine F; 0.5%-10% of water-soluble polyether; 0.5%-10% of an organic solvent; and 25%-60% of water. The preparation method comprises the following steps: reacting waterborne epoxy resin with organic amine to obtain an intermediate A; and under an alkaline condition, dropwise adding a thio-modified reagent into the intermediate A to obtain a water clarifier C, adjusting the pH value, and mixing the water clarifier C with water-soluble polyether and small-molecular organic amine to obtain the efficient water clarifier. The water clarifier is stable in product quality, and when the water clarifier is used for treating oil-containing sewage of an oil field, formed oil droplets are large, floating is fast, water is clear, and the water clarification effect is remarkable.

Description

Technical Field

[0001] This invention relates to the field of water purification agents, and in particular to a high-efficiency water purification agent and its preparation method. Background Technology

[0002] After treatment, produced fluid from offshore platforms is either exported as qualified crude oil or discharged as oily wastewater after further treatment to meet standards. Oily wastewater typically undergoes two-stage separation. The first stage of separation is completed in a production separator, and the second stage is completed in devices such as hydrocyclones, flotation tanks, or walnut shell separators. In the production separator, produced fluid undergoes oil-water separation based on density differences, and the water at the separator outlet enters the second stage of separation. To reduce the water treatment load in the second stage, the produced fluid needs to be efficiently separated in the production separator to reduce the oil content in the water outlet. Offshore platforms typically add a water-cleaning agent before the production separator to assist in rapid oil-water separation.

[0003] As offshore oilfields age, water content gradually increases, with some now exceeding 97%. To stabilize and increase production, offshore oilfields continuously open new wells and increase fluid production, leading to increasingly larger water treatment volumes on the platforms and shorter residence times of oily wastewater in production separators. Currently used cleaning agents cannot effectively separate oil and water in a short time. Therefore, there is a need to develop a cleaning agent product for rapid oil-water separation. Summary of the Invention

[0004] In order to solve the above-mentioned technical problems, the present invention provides a highly efficient water purification agent and its preparation method.

[0005] In a first aspect, the present invention provides a highly efficient water cleaning agent, which is achieved by the following technical solution.

[0006] A highly effective water purification agent, comprising the following raw materials in weight percentages: Organic amine B: 5%–25%; Waterborne epoxy resin: 4%–20%; Thio-modifying reagents: 5%–25%; 50% sodium hydroxide solution D: 10%~25%; 50% sodium hydroxide solution E: 0%~3%; Small molecule organic amine F: 0.2%~3%; Water-soluble polyether: 0.5%–10%; Organic solvents: 0.5%–10%; Water: 25%–60%.

[0007] Furthermore, the organic amine B is selected from one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dihexamethylenetriamine, and polyethyleneimine.

[0008] Furthermore, the waterborne epoxy resin is selected from one or more of the following: ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, lipoalkyl diglycidyl ether, glycerol triglycidyl ether, and pentaerythritol tetraglycidyl ether.

[0009] Furthermore, the thiomodifying agent is carbon disulfide.

[0010] Furthermore, the small molecule organic amine F is selected from one or more of diethylenetriamine, triethylenetetraamine, and tetraethylenepentamine.

[0011] Furthermore, the water-soluble polyether is selected from one or more of the following: nonylphenolic resin polyether, phenolic amine resin polyether, triblock modified polyether, higher alcohol polyether, and polyethylene glycol modified phenolic resin polyether.

[0012] Furthermore, the organic solvent may be one or more of methanol, ethanol, and propanol.

[0013] Secondly, the present invention provides a method for preparing a high-efficiency water purification agent, which is achieved by the following technical solution.

[0014] A method for preparing the above-mentioned high-efficiency water purification agent includes the following steps: S1. Synthesis of intermediate A: Add waterborne epoxy resin dropwise to organic amine B or add organic amine B dropwise to waterborne epoxy resin, stir, control the reaction temperature at 20-60℃, and continue the reaction for 1-4 hours after the addition is complete to obtain intermediate A. S2. Synthesis of water-purifying agent C Add water and 50% sodium hydroxide solution D to intermediate A obtained in step S1, and control the temperature at 10-35℃; after the sodium hydroxide solution is added dropwise, start adding the thiomodifying reagent, and control the temperature at 15-60℃; after the thiomodifying reagent is added dropwise, continue the reaction at 15-60℃ for 2-6 hours to obtain water-clearing agent C; add 50% sodium hydroxide solution E to water-clearing agent C to adjust the pH to 10-13; S3. Product compounding Under stirring conditions, organic solvent and small molecule organic amine F are added sequentially to the water-removing agent C obtained in step S2, stirred evenly, and finally water-soluble polyether is added and stirred for 10 to 40 minutes to obtain a high-efficiency water-removing agent.

[0015] This application has the following beneficial effects: The high-efficiency water cleaning agent of this invention reacts with oily wastewater to form large oil droplets that rise quickly, which can promote rapid oil-water separation, effectively reduce the oil content (OIW) in the water phase of the separator outlet sample, improve the water quality of the platform, and help the offshore platform achieve stable and increased production. Attached Figure Description

[0016] Figure 1 This is a comparison diagram of the water purification effect of the present invention. From left to right, they are Q-101, Q-102, and Q-103, representing the water purification agents in use. Detailed Implementation

[0017] The present patent application will be further described below with reference to the accompanying drawings and embodiments.

[0018] The diethylene glycol diglycidyl ether used in the following embodiments of this application was purchased from Nanjing Renxin Chemical Co., Ltd. The glycerol triglycidyl ether used in the following embodiments of this application was purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd. The triblock modified polyether used in the following embodiments of this application is the P1PEP-1 product described in Example 1 of Chinese Invention Patent No. CN112300379A, entitled "A Crosslinked Polyether Reverse Demulsifier and Its Preparation Method". The high carbon alcohol polyether used in the following embodiments of this application is the component C: octadecyl alcohol polyoxypropylene polyoxyethylene polyoxypropylene ether, which is a solution obtained by dissolving octadecyl alcohol polyoxypropylene polyoxypropylene ether in a mixture of methanol and deionized water at a mass ratio of 8:2, as described in Example 1 of Chinese Invention Patent Publication No. CN116179236A, entitled "A Demulsifier for Crude Oil Emulsion Layer Treatment". Example 1:

[0019] 1) Synthesis of intermediate A1: Add 25g of triethylenetetramine to the reaction vessel, stir, cool with cooling water, slowly add 14g of diethylene glycol diglycidyl ether, control the reaction temperature at 30℃, and continue the reaction for 3 hours after the addition is complete to obtain a pale yellow viscous intermediate A1. 2) Synthesis of DTC water purification agent C1: Add 80g of water to intermediate A and stir well. Slowly add 43.3g of 50% sodium hydroxide solution, using cooling water to maintain the temperature at 30-35℃. After the sodium hydroxide solution is completely added, slowly add 46.2g of carbon disulfide, maintaining the temperature at 30-35℃. After the addition is complete, continue the reaction for 4 hours to obtain a reddish-brown homogeneous liquid DTC water-purifying agent C1. Add 3.6g of 50% sodium hydroxide solution to DTC water-purifying agent C1 to adjust the pH to 12.5. 3) Product compounding: Add 10g of ethanol and 3g of diethylenetriamine to water-cleaning agent C1 in sequence, and stir for 10 minutes; finally add 5g of triblock modified polyether (P1PEP-1), stir for 30 minutes, and remove from the reactor to obtain the target product, high-efficiency water-cleaning agent Q-101. Example 2:

[0020] 1) Synthesis of intermediate A2: Add 25g of triethylenetetramine to the reaction vessel, stir, cool with cooling water, slowly add 40g of glycerol triglycidyl ether, control the reaction temperature at 30℃, and continue the reaction for 4 hours after the addition is complete to obtain a pale yellow viscous intermediate A2. 2) Synthesis of DTC water purification agent C2: Add 80g of water to intermediate A2 and stir until homogeneous. Slowly add 43.3g of 50% sodium hydroxide solution, cooling with condenser to maintain the temperature at 30-35℃. After the sodium hydroxide solution is completely added, slowly add 46.2g of carbon disulfide, maintaining the temperature at 30-35℃. After the addition is complete, continue the reaction for 4 hours to obtain a reddish-brown homogeneous liquid, DTC water-purifying agent C2. Add 2.5g of 50% sodium hydroxide solution to DTC water-purifying agent C2 to adjust the pH to 11.5. 3) Product compounding: Add 10g of methanol and 3g of diethylenetriamine to water-cleaning agent C2 in sequence, and stir for 10 minutes; finally add 3g of triblock modified polyether (P1PEP-1), stir for 30 minutes, and remove from the reactor to obtain the target product, high-efficiency water-cleaning agent Q-102. Example 3:

[0021] 1) Synthesis of intermediate A3: Add 25g of diethylenetriamine to the reaction vessel, stir, cool with cooling water, slowly add 50g of glycerol triglycidyl ether, control the reaction temperature at 30℃, and continue the reaction for 3 hours after the addition is complete to obtain a pale yellow viscous intermediate A3. 2) Synthesis of DTC water purification agent C3: Add 90g of water to intermediate A3 and stir until homogeneous. Slowly add 50.6g of 50% sodium hydroxide solution, cooling with condenser to maintain the temperature at 30-35℃. After the sodium hydroxide solution is completely added, slowly add 54.2g of carbon disulfide, maintaining the temperature at 30-35℃. After the addition is complete, continue the reaction for 3 hours to obtain a reddish-brown homogeneous liquid DTC water-soluble agent C3. Add 3g of 50% sodium hydroxide solution to DTC water-soluble agent C3 to adjust the pH to 11.5. 3) Product compounding: Add 10g of ethanol and 2g of triethylenetetramine to water-cleaning agent C3 in sequence, and stir for 10 minutes; finally add 4.5g of high carbon alcohol polyether, stir for 30 minutes, and remove from the reactor to obtain the target product, high-efficiency water-cleaning agent Q-103.

[0022] Performance testing The water purification performance of products Q-101, Q-102, and Q-103 from Examples 1-3 was compared with that of an in-use water purification agent (the main component of which is small molecule dithiocarbamate). The results are shown in Table 1 and Table 2, respectively. Figure 1 .

[0023] Table 1 Performance Evaluation Record of Water-Clearing Agent & Reverse Demulsifier Sample: Oil-water sample from the oilfield; Test temperature: 85℃; Oil sample collection point: manifold. Volume: 500ml Dilution concentration: 100% Mixing method: Shake 50 times Note: Oil droplet rising speed (fast: A+, A, A-; average: B+, B, B-; slow: C+, C, C-) Oil droplet size (large: A+, A, A-; medium: B+, B, B-; small: C+, C, C-) Water color (Clear: A+, A, A-; Average: B+, B, B-; Poor: C+, C, C-) The results above show that the three samples obtained in Examples 1-3 formed large oil droplets after reacting with oily wastewater, which floated quickly. Furthermore, the water color after reacting with the three samples was better than that of the water purification agent used in the past, which can effectively improve the treatment effect of oily wastewater on the platform.

[0024] The embodiments described herein are preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Therefore, all equivalent changes made in accordance with the structure, shape, and principle of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A highly efficient water cleaning agent, characterized in that: Including the following percentages by weight of raw materials: Organic amine B: 5%–25%; Waterborne epoxy resin: 4%–20%; Thio-modifying reagents: 5%–25%; 50% sodium hydroxide solution D: 10%~25%; 50% sodium hydroxide solution E: 0%~3%; Small molecule organic amine F: 0.2%~3%; Water-soluble polyether: 0.5%–10%; Organic solvents: 0.5%–10%; Water: 25%–60%.

2. The high-efficiency water cleaner according to claim 1, characterized in that: Organic amine B is selected from one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dihexamethylenetriamine, and polyethyleneimine.

3. The high-efficiency water cleaner according to claim 1, characterized in that: The waterborne epoxy resin is selected from one or more of the following: ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dibromonepentyl glycol diglycidyl ether, lipohydrocarbon diglycidyl ether, glycerol triglycidyl ether, and pentaerythritol tetraglycidyl ether.

4. The high-efficiency water cleaner according to claim 1, characterized in that: The thiomodifying agent is carbon disulfide.

5. The high-efficiency water cleaner according to claim 1, characterized in that: The small molecule organic amine F is selected from one or more of diethylenetriamine, triethylenetetraamine, and tetraethylenepentamine.

6. The high-efficiency water cleaner according to claim 1, characterized in that: The water-soluble polyether is selected from one or more of the following: nonylphenolic resin polyether, phenolic amine resin polyether, triblock modified polyether, high carbon alcohol polyether, and polyethylene glycol modified phenolic resin polyether.

7. The high-efficiency water cleaner according to claim 1, characterized in that: The organic solvent may be one or more of methanol, ethanol, and propanol.

8. A method for preparing the high-efficiency water-cleaning agent according to any one of claims 1-7, characterized in that: Includes the following steps: S1. Synthesis of intermediate A: Add waterborne epoxy resin dropwise to organic amine B or add organic amine B dropwise to waterborne epoxy resin, stir, control the reaction temperature at 20-60℃, and continue the reaction for 1-4 hours after the addition is complete to obtain intermediate A. S2. Synthesis of water-purifying agent C Add water and 50% sodium hydroxide solution D to intermediate A obtained in step S1, and control the temperature at 10-35℃; after the sodium hydroxide solution is added dropwise, start adding the thiomodifying reagent, and control the temperature at 15-60℃; after the thiomodifying reagent is added dropwise, continue the reaction at 15-60℃ for 2-6 hours to obtain water-clearing agent C; add 50% sodium hydroxide solution E to water-clearing agent C to adjust the pH to 10-13; S3. Product compounding Under stirring conditions, organic solvent and small molecule organic amine F are added sequentially to the water-removing agent C obtained in step S2, stirred evenly, and finally water-soluble polyether is added and stirred for 10 to 40 minutes to obtain a high-efficiency water-removing agent.

Images