A grey water dispersant based on amps spent liquor and a method of making the same

Abstract

The application discloses a kind of grey water dispersant based on AMPS waste liquid and preparation method thereof, it is related to dispersant preparation field, the application is prepared by mixing AMPS waste liquid and acrylic acid as oil material, hydrogen peroxide is used as water material, it is added dropwise to the bottom material prepared by maleic anhydride and initiator, and the grey water dispersant with good scale inhibition performance can be prepared;The whole process is simple to operate, and the fine pretreatment of AMPS waste liquid is not needed, the processing difficulty of recycling is reduced, and AMPS waste liquid can be completely recycled and utilized.The grey water dispersant prepared based on AMPS waste liquid has excellent scale inhibition performance, and can effectively inhibit scale at less than the dosing amount of conventional dispersant;It reduces the use cost and is convenient for promotion.And it can be compounded with the commonly used dispersant, and the performance will not be affected after compounding, so that it can be directly used under complex scale inhibition requirements, and the application scenario is expanded.

Description

Technical Field

[0001] This invention relates to the field of dispersant preparation, specifically to an ash-water dispersant based on AMPS waste liquid and its preparation method. Background Technology

[0002] 2-Acrylamido-2-methylpropanesulfonic acid (AMPS) has wide applications in the petroleum and water treatment industries. Current production processes primarily involve reacting acrylonitrile, fuming sulfuric acid, and isobutylene under relatively mild conditions. However, due to raw material control issues, existing AMPS synthesis processes generate numerous byproducts such as tert-butylacrylamide, acrylamide, monosulfonated isobutylene, or disulfonated isobutylene. This leads to high AMPS synthesis costs, and the purified waste liquid is difficult to effectively recycle and cannot be directly discharged; it is typically neutralized and precipitated with acid or alkali before discharge. This results in high waste liquid treatment costs. Therefore, how to recycle and reuse AMPS waste liquid to reduce AMPS production costs is a pressing issue that needs to be addressed in this field.

[0003] The prior art CN114933675B discloses a method for recovering and utilizing 2-acrylamido-2-methylpropanesulfonic acid distillation concentrate. However, this method requires multiple processing steps for the concentrate, making the entire process complex.

[0004] Meanwhile, existing dispersants or scale inhibitors require high dosages to achieve better scale inhibition performance, resulting in high scale inhibition costs; and they are difficult to combine with other dispersants, limiting their application scenarios. Summary of the Invention

[0005] To address the aforementioned shortcomings of existing technologies, this invention provides a low-cost, widely applicable ash water dispersant based on AMPS waste liquid and its preparation method.

[0006] To achieve the above-mentioned objectives, the technical solution adopted by this invention is as follows:

[0007] A method for preparing an ash-water dispersant based on AMPS waste liquid is provided, comprising the following steps:

[0008] S1: Prepare oil and water separately; the oil is a mixture of acrylic acid and AMPS waste liquid, and the water is a mixture of deionized water and 27% hydrogen peroxide.

[0009] S2: Add maleic anhydride to deionized water, then add an initiator to obtain the base material. When adding the maleic anhydride solution and the base material, keep the deionized water in a stirring state.

[0010] S3: Add oil and water to the base material, and after the addition is complete, a ash-water dispersant is obtained; during the process of adding oil and water, maintain the temperature at 85-89℃.

[0011] Furthermore, the mass ratio of the oil, water, and base material is 227:500:360; the mass ratio of the acrylic acid to the AMPS waste liquid is 3:2; and the mass ratio of deionized water to 27% hydrogen peroxide in the water material is 5:4.

[0012] Furthermore, the AMPS waste liquid is the waste liquid obtained from AMPS synthesis, including N-tert-butylacrylamide, 2-methylene-1,3-propylene disulfonic acid, 2-methyl-propenylsulfonic acid, acrylonitrile, 2-hydroxy-2-methylpropanesulfonic acid, 1,2-isobutylsulfonate lactone, acetic acid, acrylic acid, acrylamide and sulfuric acid.

[0013] Furthermore, the mass ratio of deionized water to maleic anhydride in the substrate is 150:25-85; and the mass ratio of maleic anhydride to initiator is 75:2.

[0014] Furthermore, the mass ratio of deionized water to maleic anhydride in the substrate is 150:75.

[0015] Furthermore, in step S3, the dripping rate of the oil is 65-75 g / s; the dripping rate of the water is 35-45 g / s.

[0016] Furthermore, after the oil and water are added in step S3, the mixture needs to be aged at 89–95°C for 2 hours.

[0017] The present invention also provides a ash water dispersant prepared by the above preparation method, which is used for scale inhibition, and the dosage of the ash water dispersant is 10-40 mg / L.

[0018] Furthermore, the ash water dispersant can also be compounded with hydroxyethylidene diphosphonic acid (HEDP) for scale inhibition, and the mass ratio of ash water dispersant to HEDP is 9:1.

[0019] Furthermore, the ash water dispersant can also be compounded with terpolymers or polymaleic anhydride for use as a reverse osmosis antiscalant, with a mass ratio of ash water dispersant to terpolymers or polymaleic anhydride of 1:1; the ash water dispersant can also be compounded with zinc sulfate heptahydrate for use as a phosphorus-free antiscalant, with a mass ratio of ash water dispersant to zinc sulfate heptahydrate of 3:2.

[0020] The beneficial effects of this invention are as follows:

[0021] This invention prepares an oil by mixing AMPS waste liquid with acrylic acid and adding hydrogen peroxide as a water component, both of which are dripped into a substrate prepared from maleic anhydride and an initiator. This process produces a grey water dispersant with excellent scale inhibition properties. The entire process is simple to operate, requires no fine pretreatment of AMPS waste liquid, reduces the difficulty of recycling, and enables the complete recycling of AMPS waste liquid.

[0022] This invention provides an ash water dispersant prepared from AMPS waste liquid that exhibits excellent scale inhibition performance. It effectively inhibits scale growth even at lower dosages than conventional dispersants, reducing usage costs and facilitating widespread adoption. Furthermore, it can be compounded with commonly used dispersants without affecting performance, allowing for direct application in complex scale inhibition scenarios and expanding its application scope. Detailed Implementation

[0023] The specific embodiments of the present invention are described below to enable those skilled in the art to understand the present invention. However, it should be understood that the present invention is not limited to the scope of the specific embodiments. For those skilled in the art, various changes are obvious as long as they are within the spirit and scope of the present invention as defined and determined by the appended claims. All inventions utilizing the concept of the present invention are protected.

[0024] Example 1

[0025] This embodiment provides a method for preparing an ash-water dispersant based on AMPS waste liquid, comprising the following steps:

[0026] S1: To prepare the oil, add 200 kg of AMPS waste liquid to 300 kg of acrylic acid and stir to mix well. The AMPS waste liquid comes from Shandong Juye County Zhonghai Chemical Co., Ltd. It includes 35.58% N-tert-butylacrylamide, 12.61% 2-methylene-1,3-propylene disulfonic acid, 7.80% 2-methyl-allylsulfonic acid, 7.45% acrylonitrile, 3.97% 2-hydroxy-2-methylpropanesulfonic acid, 3.48% 1,2-isobutylsulfonate lactone, 3.22% acetic acid, 1.99% acrylic acid, and 1.96% acrylamide; the remainder is sulfuric acid.

[0027] To prepare the water mixture, add 200 kg of deionized water and 160 kg of 27% hydrogen peroxide to the water mixture feeding tank, and stir until well mixed.

[0028] S2: Add 150 kg of deionized water to the stirrer, keep the stirrer running, add 75 kg of maleic anhydride to the deionized water, and after the maleic anhydride dissolves, add 2 kg of initiator, mix well to obtain the base material; in specific implementation, the initiator is an organic peroxide or an azo compound, such as methyl ethyl ketone peroxide (MEKP) or benzoyl peroxide (BPO); in this embodiment, methyl ethyl ketone peroxide (MEKP) is used;

[0029] S3: Heat the prepared base material in the reactor to 70°C, then begin dripping oil and water. Control the dripping rate within 30 minutes of the start of the reaction, maintaining the dripping temperature between 85 and 89°C. Specifically, in the initial stage of the reaction, the temperature of the reaction system will rise rapidly, potentially exceeding 90°C. Immediately close the steam valve to release the fumes, introduce cooling water, and stop the dripping. During the dripping process, maintain the dripping temperature at 85–89°C and control the dripping rate. The dripping time is 2.0 hours for oil and 2.5 hours for water.

[0030] After the dropwise reaction is complete, maintain the aging temperature at 89–95°C for 2 hours. The condensate generated during the dropwise addition and aging process should be collected and returned to the reactor via an oil tank.

[0031] A pale yellow to brownish-yellow liquid was prepared, with a pH (1% aqueous solution) of 2.0–4.0 and a density ≥1.15 g / cm³. 3 Solid content reference value: 48%–52%; viscosity: ≤500 mPa·S.

[0032] Example 2

[0033] The ash water dispersant prepared in Example 1 was compounded with ATMP, PBTCA and HEDP. Monomer compounding and multi-component compounding were set up. All compounding agents were diluted with an equal mass of water. The compounding parameters are shown in Table 1 below.

[0034] Table 1

[0035] serial number dispersant ATMP PBTCA HEDP water 1 45 2.5 2.5 0 50 2 45 5 0 0 50 3 45 0 5 0 50 4 45 0 0 5 50 5 45 2.5 2.5 0 50 6 50 0 0 0 50

[0036] ATMP, PBTCA, and HEDP were all purchased from Shandong Taihe Technology Co., Ltd. The prepared compound solutions were placed in a refrigerator at 3°C ​​for observation. After preparation, all compound solutions were clear. On the second day, compound solution No. 1 became cloudy, while the other compound solutions showed no significant change. On the fourth day, compound solution No. 3 became cloudy, but less so than compound solution No. 1. On the sixth day, compound solution No. 5 became cloudy, but less so than compound solution No. 1. On the twelfth day, compound solution No. 2 became cloudy. At this point, compound solution No. 1 had a significant amount of precipitate, while solutions No. 2, 3, and 5 were all cloudy. After filtering out the precipitate from compound solution No. 1, it was left to stand for another 12 days without significant change. In conclusion, ash water dispersant can be compounded with HEDP without any precipitation.

[0037] The ash water dispersant prepared in Example 1 was compounded with a terpolymer, polymaleic anhydride and zinc sulfate heptahydrate. The monomer compounding was set up, and all compounding agents were diluted with water. In specific implementation, the terpolymer was a commercially available conventional copolymer. In this example, the terpolymer was an acrylic acid-AMPS-hydroxypropyl acrylate terpolymer. The compounding parameters are shown in Table 2 below.

[0038] Table 2

[0039] serial number dispersant terpolymer Polymaleic anhydride Zinc sulfate heptahydrate water 7 30 30 0 0 40 8 30 0 30 0 40 9 30 0 0 20 50

[0040] No obvious phenomena were observed when the compound agents No. 7 to No. 9 were placed in a refrigerator at 3°C ​​for 12 days. The ash water dispersant of the present invention has good compatibility with polymaleic anhydride and terpolymer, and can be used as a reverse osmosis antiscalant. It has good compatibility with zinc sulfate heptahydrate and can be used in phosphorus-free formulations.

[0041] Example 3

[0042] The performance of the scale inhibitor was evaluated according to the national standard GB / T16632-2008 "Performance Determination of Scale Inhibitors in Water Treatment Agents". The target solution was a mixed solution of calcium carbonate and calcium hydroxide. Two batches of AMPS waste liquid were obtained from Shandong Juye Zhonghai Chemical Co., Ltd., with an interval of one month between the two batches. The dispersant prepared using the method in Example 1 was named the first dispersant, and the dispersant prepared from the second batch of AMPS waste liquid was named the second dispersant. Scale inhibition tests were also conducted using PBTCA purchased from Shandong Taihe Technology Co., Ltd. The test results are shown in Table 3 below.

[0043] Table 3

[0044]

[0045] Table 3 shows that when the target solutions are 600 mg / L calcium carbonate and 600 mg / L calcium hydroxide, the dosage of the ash water dispersant prepared according to this invention is 20 mg / L, which effectively inhibits scale, and the scale inhibition effect is close to that of PBTCA. When the target solutions are 800 mg / L calcium carbonate and 300 mg / L calcium hydroxide, and the dosage of the ash water dispersant prepared according to this invention is 20 mg / L, a 100% scale inhibition rate can be achieved. When the dosage is set to 10 mg / L, the scale inhibition performance of the ash water dispersant prepared according to this invention is slightly lower than that of PBTCA.

[0046] Example 4

[0047] A zinc-stabilizing plating test was conducted using the ash-water dispersant prepared according to this invention. The target solution was 2 L and contained: Ca 2+ 750 mg / L; Alkalinity: 150 mg / L; Mg 2+ 280 mg / L; SO4 2- : 500mg / L; TFe: 0.5mg / L.

[0048] Test temperature: 45±1℃; pH: 8.0~8.5; Test time: 50h; Coating: 2 A3 steel pieces;

[0049] The first dispersant, the second dispersant in Example 3, and polymaleic anhydride and high-efficiency zinc solvent purchased from Shandong Taihe Technology Co., Ltd. were used for the test. At the same time, the first dispersant and zinc sulfate heptahydrate were mixed at a mass ratio of 3:2 as a compound zinc stabilizer. The test results are shown in Table 4 below.

[0050] Table 4

[0051]

[0052] As shown in Table 4, when the ash water dispersant prepared in this invention is used directly as a zinc stabilizer, its average corrosion rate is close to that of polymaleic anhydride and lower than that of the high-efficiency zinc dissolving agent; while the phosphorus-free compound zinc stabilizer prepared by using the first dispersant and zinc sulfate heptahydrate has a slightly increased corrosion rate, but both are far below the national standard.

Claims

1. A method for preparing an ash-water dispersant based on AMPS waste liquid, characterized in that, Includes the following steps: S1: Prepare oil and water separately; the oil is a mixture of acrylic acid and AMPS waste liquid, and the water is a mixture of deionized water and 27% hydrogen peroxide. The AMPS waste liquid comprises 35.58% N-tert-butylacrylamide, 12.61% 2-methylene-1,3-propylene disulfonic acid, 7.80% 2-methyl-allylsulfonic acid, 7.45% acrylonitrile, 3.97% 2-hydroxy-2-methylpropanesulfonic acid, 3.48% 1,2-isobutylsulfonate lactone, 3.22% acetic acid, 1.99% acrylic acid, and 1.96% acrylamide; the remainder is sulfuric acid. S2: Add maleic anhydride to deionized water, then add an initiator to obtain the base material. When adding maleic anhydride and initiator, keep the deionized water in a stirring state. S3: Add oil and water to the base material, and after the addition is complete, a ash-water dispersant is obtained; during the process of adding oil and water, maintain the temperature at 85~89℃; The mass ratio of the oil, water, and base material is 500:360:227; the mass ratio of the acrylic acid to AMPS waste liquid is 3:2; and the mass ratio of deionized water to 27% hydrogen peroxide in the water is 5:

4. The mass ratio of deionized water to maleic anhydride in the substrate is 150:25~85; and the mass ratio of maleic anhydride to initiator is 75:

2.

2. The preparation method according to claim 1, characterized in that, The mass ratio of deionized water to maleic anhydride in the substrate is 150:

75.

3. The preparation method according to any one of claims 1-2, characterized in that, In step S3, the dripping rate of the oil is 65~75 g / s; the dripping rate of the water is 35~45 g / s.

4. The preparation method according to claim 3, characterized in that, After the oil and water are added in step S3, the mixture needs to be aged at 89-95℃ for 2 hours.

5. A water-based ash dispersant prepared by the method described in claim 4, characterized in that, The ash water dispersant is used for scale inhibition, and the dosage of the ash water dispersant is 10~40 mg / L.

6. The ash-water dispersant according to claim 5, characterized in that, The ash water dispersant is compounded with hydroxyethylidene diphosphonic acid (HEDP) to inhibit scale formation, and the mass ratio of ash water dispersant to HEDP is 9:

1.

7. The ash-water dispersant according to claim 5, characterized in that, The ash water dispersant, when compounded with a terpolymer or polymaleic anhydride, is used as a reverse osmosis antiscalant, and the mass ratio of the ash water dispersant to the terpolymer or polymaleic anhydride is 1:

1.

8. The ash-water dispersant according to claim 5, characterized in that, The ash water dispersant, when combined with zinc sulfate heptahydrate, is used for phosphorus-free scale inhibition, and the mass ratio of the ash water dispersant to zinc sulfate heptahydrate is 3:2.

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