Preparation method of a phosphorus-free, environmentally friendly and highly efficient scale inhibitor

Abstract

The present invention provides a preparation method of a phosphorus-free, environmentally friendly and highly efficient scale inhibitor, belonging to the field of water treatment. The present invention uses maleic anhydride, aminobenzenesulfonic acid, organic amine, hydroxypropyl acrylate, zinc methacrylate, ethylene boronic anhydride pyridine complex, 5-vinyl-4-methylthiazole, peroxide initiator, and gelatin to prepare the phosphorus-free, environmentally friendly and highly efficient scale inhibitor; the phosphorus-free, environmentally friendly and highly efficient scale inhibitor prepared by the present invention can effectively inhibit the formation of water scales such as calcium carbonate, calcium sulfate, barium sulfate, and silicate, has good dispersibility, greatly alleviates the scaling phenomenon in the industrial use process, and saves the development cost; the scale inhibitor of the present invention does not contain phosphorus, can greatly reduce the phosphorus emission, has good compatibility with phosphorus-based scale inhibitors such as HEDP, ATMP, and EDTMP, and the synthesis process is not too complicated, and the performance is reliable and stable.

Description

Technical Field

[0001] The present invention relates to the field of water treatment, and relates to a preparation method of a phosphorus-free environmental protection and highly efficient scale inhibitor. Background Art

[0002] With the increase in population and the rapid development of industry, the problem of global water resource shortage has become increasingly prominent. To solve this problem, industrial water gradually adopts a circulating water mode. However, the repeated use of cooling water leads to an increasing content of scale-forming ions in the water, causing equipment scaling and corrosion, and affecting the performance of the equipment. Adding corrosion and scale inhibitors is the most convenient and effective method.

[0003] Chinese Patent CN116655914A, a biodegradable bio-based scale inhibitor and its preparation method and application, discloses a biodegradable bio-based scale inhibitor and its preparation method and application. The present invention synthesizes a PASP polymer and modifies it to improve the scale inhibition performance of polyaspartic acid-based scale inhibitors, and simultaneously evaluates the scale inhibition effect of the system on scale substances such as Ca 2+ 、Mg 2+ 、Ba 2+ -type scale substances, filling the gap of multifunctional and universal scale inhibitors in the oilfield field, and providing guidance for screening suitable scale inhibitors in the oil and gas field field.

[0004] Chinese Patent CN116693726A provides a method for preparing a scale inhibitor based on an olefin functional polymer. The method includes: introducing a low-carbon olefin into a reactor, then raising the temperature and pressure, and then adding a functional monomer, an initiator, and a solvent into the reactor to carry out a polymerization reaction; after the polymerization reaction, first carry out gas-solid-liquid separation to recover the low-carbon olefin, and then carry out solid-liquid separation on the remaining material to obtain an olefin functional polymer; carry out an esterification reaction on the olefin functional polymer with an alcohol, and then react the obtained esterified olefin functional polymer with a quaternary ammonium salt, a base, or an acid to obtain a cationic or anionic polymer scale inhibitor. By adopting a heterogeneous polymerization method, the monomer concentration and reaction efficiency are improved, and different types of polymer scale inhibitors are prepared through esterification and cationization / anionization reactions, with good thermal stability and excellent water treatment performance.

[0005] Chinese Patent CN114890557B discloses a slow-release solid scale inhibitor and its application, belonging to the field of tunnel disease prevention. The slow-release solid scale inhibitor of the present invention uses silica aerogel as a carrier, which can adsorb a large amount of effective components of the scale inhibitor, precisely control the release of the effective components of the scale inhibitor, and the long-term slow-release effect can reach 200 days, effectively solving the problems of the traditional scale inhibitor with too fast release and poor scale inhibition effect. The slow-release solid scale inhibitor of the present invention is used in the tunnel drainage system. Due to the seepage process of groundwater in the shotcrete of the initial support of the tunnel, the solution in the drain pipe is in an alkaline state. The drain pipe is easily corroded under the condition of alkaline aqueous solution for a long time. The drain pipe added with the slow-release solid scale inhibitor is basically not affected by the alkaline environment, ensuring the service life of the drain pipe.

[0006] The most commonly used existing method for treating cooling water is to add a scale inhibitor to the cooling water. However, the existing scale inhibitors have problems such as low scale inhibition efficiency, poor corrosion inhibition effect, and poor antibacterial performance. Therefore, it is necessary to provide a scale inhibitor with high scale inhibition efficiency, good corrosion inhibition effect, and excellent antibacterial performance. Summary of the Invention

[0007] To meet the current demand for phosphorus-free environmental protection scale inhibitors and overcome the deficiencies of the existing technology, this patent proposes a preparation method for a phosphorus-free environmental protection and high-efficiency scale inhibitor, which has a simple preparation method, low cost, and good heat resistance.

[0008] A preparation method for a phosphorus-free environmental protection and high-efficiency scale inhibitor specifically includes the following steps:

[0009] A1: By mass, add 10-20 parts of maleic anhydride, 18-36 parts of aminobenzenesulfonic acid, and 2-5 parts of organic amine to a constant-pressure reaction kettle with a stirring device, heat up to 70-85 °C, and react for 30-70 minutes;

[0010] A2: Add 13-26 parts of hydroxypropyl acrylate, 0.02-0.5 part of zinc methacrylate, 0.02-0.5 part of ethylene boronic anhydride pyridine complex, 0.02-0.5 part of 5-vinyl-4-methylthiazole, and 300-400 parts of toluene to the constant-pressure reaction kettle. While stirring, open the funnel and drop in 0.7-2.5 parts of a peroxide initiator and 1.3-3.5 parts of gelatin, and continue to stir and react at a constant temperature of 70-90 °C for a certain period of time. Distill off the toluene to obtain a phosphorus-free environmental protection and high-efficiency scale inhibitor.

[0011] As a preference of the above technical solution, the aminobenzenesulfonic acid monomer in step 1 is one or at least two combinations of 3-amino-4-hydroxybenzenesulfonic acid, aminobenzenesulfonic acid, p-4-aminobenzenesulfonic acid, m-bis-diaminobenzenesulfonic acid, and 2,4-aminobenzenesulfonic acid sodium.

[0012] Preferably, as the above technical solution, the organic amine in step 1 is one or a combination of at least two of ethanolamine, ethylenediamine, butanediamine, hexanediamine, diethylenetriamine, tetraethylenetetraamine, and tetraethylenepentamine.

[0013] Preferably, as the above technical solution, the peroxide initiator in step 2 is one or a combination of at least two of di-tert-butyl peroxide, butyl hydroperoxide, benzoyl peroxide, 2-butanone peroxide, and diisopropyl peroxydicarbonate.

[0014] Preferably, as the above technical solution, the reaction time in step 2 is 4 - 8h.

[0015] The present invention may involve the following reaction mechanism:

[0016] (1) The amino group in aminobenzenesulfonic acid can undergo an addition reaction with maleic anhydride to obtain maleic acid-based benzenesulfonic acid.

[0017] (2) The maleic acid-based benzenesulfonic acid undergoes a polymerization reaction with hydroxypropyl acrylate, zinc methacrylate, vinylboric anhydride pyridine complex, and 5-vinyl-4-methylthiazole to obtain a scale inhibitor.

[0018] Technical effects:

[0019] The technical solution of the present invention can effectively inhibit the formation of scale such as calcium carbonate, calcium sulfate, barium sulfate, and silicate, has good dispersibility, greatly alleviates the scaling phenomenon during industrial use, and saves development costs. The scale inhibitor of the present invention does not contain phosphorus, can greatly reduce the phosphorus emission, has good compatibility with phosphorus-based scale inhibitors such as HEDP, ATMP, and EDTMP, and the synthesis process is not too complicated, and the performance is reliable and stable.

[0020] The vinylboric anhydride pyridine complex: has high reaction activity and prevents these ions from combining with negatively charged substances (such as carbonate ions) in water to form scale. Thiazole may create a weakly acidic environment in the aqueous solution, and this environment can promote the dissolution of scale. By forming complexes with hardness ions, the probability of their combination with negatively charged substances is reduced, thereby reducing the formation of scale. Zinc ions can also replace calcium and magnesium ions in the crystal lattice, making the already formed scale loose and easy to remove. Specific embodiments

[0021] The following details the specific embodiments of the present invention. It should be understood that the preferred embodiments described herein are only for illustrating and explaining the present invention and are not used to limit the present invention.

[0022] Refer to GB / T16632-2008 "Determination of Scale Inhibition Performance of Water Treatment Agents - Calcium Carbonate Deposition Method" to measure the scale inhibition rate of calcium carbonate, and at the same time refer to the standard QSY126-2014 "Technical Specification for Corrosion and Scale Inhibitors for Oilfield Water Treatment"

[0023] Example 1:

[0024] A preparation method of a phosphorus-free, environmentally friendly and highly efficient scale inhibitor specifically includes the following steps:

[0025] A1: Add 10 g of maleic anhydride, 18 g of aminobenzenesulfonic acid, and 2 g of organic amine to a constant-pressure reaction kettle equipped with a stirring device, heat up to 70 °C, and react for 30 minutes;

[0026] A2: Add 13 g of hydroxypropyl acrylate, 0.02 g of zinc methacrylate, 0.02 g of ethylene boronic anhydride pyridine complex, 0.02 g of 5-vinyl-4-methylthiazole, and 300 g of toluene to the constant-pressure reaction kettle. While stirring, open the funnel and drop in 0.7 g of a peroxide initiator and 1.3 g of gelatin. Continue to stir and react at a constant temperature of 70 °C for a certain period of time, and distill off the toluene to obtain a phosphorus-free, environmentally friendly and highly efficient scale inhibitor.

[0027] The aminobenzenesulfonic acid monomer in step 1 is 3-amino-4-hydroxybenzenesulfonic acid.

[0028] The organic amine in step 1 is ethanolamine.

[0029] The peroxide initiator in step 2 is di-tert-butyl peroxide.

[0030] The reaction time in step 2 is 4 h.

[0031] Example 2:

[0032] A preparation method of a phosphorus-free, environmentally friendly and highly efficient scale inhibitor specifically includes the following steps:

[0033] A1: Add 14 g of maleic anhydride, 24 g of aminobenzenesulfonic acid, and 3 g of organic amine to a constant-pressure reaction kettle equipped with a stirring device, heat up to 75 °C, and react for 40 minutes;

[0034] A2: Add 18 g of hydroxypropyl acrylate, 0.2 g of zinc methacrylate, 0.2 g of ethylene boronic anhydride pyridine complex, 0.2 g of 5-vinyl-4-methylthiazole, and 340 g of toluene to the constant-pressure reaction kettle. While stirring, open the funnel and drop in 1.5 g of a peroxide initiator and 2 g of gelatin. Continue to stir and react at a constant temperature of 75 °C for a certain period of time, and distill off the toluene to obtain a phosphorus-free, environmentally friendly and highly efficient scale inhibitor.

[0035] The aminobenzenesulfonic acid monomer in step 1 is aminobenzenesulfonic acid.

[0036] The organic amine in step 1 is ethylenediamine.

[0037] The peroxide initiator in step 2 is butyl hydroperoxide.

[0038] The reaction time in Step 2 is 5 h.

[0039] Example 3:

[0040] A preparation method of a phosphorus-free, environmentally friendly and highly efficient scale inhibitor specifically includes the following steps:

[0041] A1: Add 18 g of maleic anhydride, 33 g of aminobenzenesulfonic acid, and 4 g of organic amine to a constant-pressure reaction kettle equipped with a stirring device, heat up to 80 °C, and react for 60 minutes;

[0042] A2: Add 24 g of hydroxypropyl acrylate, 0.4 g of zinc methacrylate, 0.4 g of ethylene boronic anhydride pyridine complex, 0.4 g of 5-vinyl-4-methylthiazole, and 380 g of toluene to the constant-pressure reaction kettle. While stirring, open the funnel and drop in 2 g of peroxide initiator and 3 g of gelatin. Continue to stir and react at a constant temperature of 85 °C for a certain period of time, and distill off the toluene to obtain a phosphorus-free, environmentally friendly and highly efficient scale inhibitor.

[0043] The aminobenzenesulfonic acid monomer in Step 1 is p-aminobenzenesulfonic acid.

[0044] The organic amine in Step 1 is butanediamine.

[0045] The peroxide initiator in Step 2 is benzoyl peroxide.

[0046] The reaction time in Step 2 is 7 h.

[0047] Example 4:

[0048] A preparation method of a phosphorus-free, environmentally friendly and highly efficient scale inhibitor specifically includes the following steps:

[0049] A1: Add 20 g of maleic anhydride, 36 g of aminobenzenesulfonic acid, and 5 g of organic amine to a constant-pressure reaction kettle equipped with a stirring device, heat up to 85 °C, and react for 70 minutes;

[0050] A2: Add 26 g of hydroxypropyl acrylate, 0.5 g of zinc methacrylate, 0.5 g of ethylene boronic anhydride pyridine complex, 0.5 g of 5-vinyl-4-methylthiazole, and 400 g of toluene to the constant-pressure reaction kettle. While stirring, open the funnel and drop in 2.5 g of peroxide initiator and 3.5 g of gelatin. Continue to stir and react at a constant temperature of 90 °C for a certain period of time, and distill off the toluene to obtain a phosphorus-free, environmentally friendly and highly efficient scale inhibitor.

[0051] The aminobenzenesulfonic acid monomer in Step 1 is 2,4-aminobenzenesulfonic acid sodium salt.

[0052] The organic amine in Step 1 is tetraethylenepentamine.

[0053] In step 2, the peroxide initiator is diisopropyl peroxydicarbonate.

[0054] In step 2, the reaction time is 8 h.

[0055] Comparative Example 1:

[0056] In the preparation process of the phosphorus-free environmentally friendly and highly efficient scale inhibitor in this example, except for not adding the ethylene boronic anhydride pyridine complex, the others are the same as in Example 1.

[0057] The results are as follows:

[0058] Table 1 Scale inhibitor effects of specific implementation schemes

[0059]

[0060] As can be seen from the above specific implementation manners, the phosphorus-free environmentally friendly and highly efficient scale inhibitor prepared by the present invention can effectively inhibit the formation of scale such as calcium salts, magnesium salts, silicate salts, and iron salts; and the sediment structure is fluffy and easy to fall off, making the already formed scale become loose and easy to remove.

[0061] The above is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed by the present invention should be covered by the protection scope of the present invention.

Claims

1. A preparation method of a phosphorus-free, environmentally friendly and highly efficient scale inhibitor, specifically comprising the following steps: A1: By mass, add 10 - 20 parts of maleic anhydride, 18 - 36 parts of aminobenzenesulfonic acid monomers, and 2 - 5 parts of organic amine to a constant-pressure reaction kettle with a stirring device, heat up to 70 - 85 °C, and react for 30 - 70 minutes; A2: Add 13 - 26 parts of hydroxypropyl acrylate, 0.02 - 0.5 part of zinc methacrylate, 0.02 - 0.5 part of ethylene boron anhydride pyridine complex, 0.02 - 0.5 part of 5-vinyl-4-methylthiazole, and 300 - 400 parts of toluene to the constant-pressure reaction kettle. While stirring, open the funnel and drop in 0.7 - 2.5 parts of a peroxide initiator and 1.3 - 3.5 parts of gelatin. Continue to stir and react at a constant temperature of 70 - 90 °C for a certain time, and distill off the toluene to obtain the phosphorus-free, environmentally friendly and highly efficient scale inhibitor; The aminobenzenesulfonic acid monomer in step 1 is one or a combination of at least two of 3-amino-4-hydroxybenzenesulfonic acid, aminobenzenesulfonic acid, p-4-aminobenzenesulfonic acid, m-bis-diaminobenzenesulfonic acid, and 2,4-aminobenzenesulfonic acid sodium.

2. The preparation method of a phosphorus-free environmental protection and high-efficiency scale inhibitor according to claim 1, characterized in that: The organic amine in step 1 is one or a combination of at least two of ethanolamine, ethylenediamine, butanediamine, hexanediamine, diethylenetriamine, tetraethylenetetraamine, and tetraethylenepentamine.

3. The preparation method of a phosphorus-free environmental protection and high-efficiency scale inhibitor according to claim 1, characterized in that: The peroxide initiator in step 2 is one or a combination of at least two of di-tert-butyl peroxide, butyl hydroperoxide, benzoyl peroxide, 2-butanone peroxide, and diisopropyl peroxydicarbonate.

4. The preparation method of a phosphorus-free environmentally friendly and highly efficient scale inhibitor according to claim 1, characterized in that: The reaction time in step 2 is 4 - 8 h.

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