Corrosion-inhibiting scale control dispersant for grey water and method for preparing same

Abstract

The application discloses a kind of corrosion-inhibiting type grey water scale inhibition dispersant and preparation method thereof, belong to grey water dispersant technical field, for solving the scale inhibition performance of grey water scale inhibition dispersant in prior art is unstable, scale inhibition efficiency is not lasting Problem, in addition, the grey water scale inhibition dispersant for industrial use needs to increase certain anticorrosive corrosion inhibition performance is also a technical problem to be solved urgently;The application comprises the following steps: styrene, acrylamide, acrylic acid as raw material, polymer wall material is prepared, polyaspartic acid, modified corrosion inhibitor, vanillin modified chitosan reaction, obtain core material, core material and wall material are prepared by composite coacervation method, obtain corrosion-inhibiting type grey water scale inhibition dispersant, the corrosion-inhibiting type grey water scale inhibition dispersant prepared in the application has the advantages that scale inhibition effect is stable, lasting, and has corrosion inhibition.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ash water dispersant, in particular to an ash water scale inhibition dispersant with corrosion inhibition and a preparation method thereof. BACKGROUND

[0002] In various equipment in power plants, scale is formed at places such as backwater pumps, pipe valves and jet nozzles, which will cause the machines and equipment at various places to not operate normally, and scale inhibition dispersants need to be added to treat the ash water to prevent scale, the high-pH ash water from the ash slurry pool to the ash slurry concentration system, and the air in the vibrating screen, concentration pool and atmosphere contact explosion, which can absorb carbon dioxide in the air to increase the concentration of carbonate in the ash water.

[0003] The scale inhibitor is used to make the heavy metals in fly ash chemically inert or physically coated by technical means to reduce their migration to the environment, and the scale inhibitor is added to the supersaturated solution to be adsorbed on the pipe wall to form an adsorption layer, and the particles are deposited on the contact surface to inhibit and dry the growth of scale, thereby achieving the purpose of scale inhibition.

[0004] However, in various power plant equipment, steel materials are mainly used, which are easy to be corroded during use, and how to alleviate the corrosion phenomenon of mechanical equipment is also a technical problem to be solved. At present, there are many prevention and control measures to reduce metal corrosion loss, such as using various organic / inorganic coating technologies, adding corrosion inhibitors, and performing electrochemical protection. However, the corrosion inhibitor still has some deficiencies in use, such as the toxicity of chromium salt, mercury salt and zinc salt, and the eutrophication of various phosphorus compounds in water bodies. If the ash water scale inhibition dispersant prepared from a polymer material is modified to increase certain corrosion inhibition performance, the scale inhibition of various mechanical equipment can be achieved while the corrosion resistance is increased. In addition, how to prolong the scale inhibition effect of the scale inhibition dispersant and improve the stability of the scale inhibition efficiency is also a technical problem to be solved.

[0005] Patent application CN103708632A discloses a gasification ash water scale inhibition dispersant, which comprises a terpolymer, acrylic acid-hydroxypropyl acrylate, a hydrolyzed maleic anhydride copolymer, a phosphate and the like. The terpolymer is an acrylic acid / 2-methyl-2-acrylamide-propane sulfonic acid copolymer. The prepared gasification ash water scale inhibition dispersant has the advantages of environmental friendliness and good dispersion and scale inhibition effect. However, the above scale inhibition dispersant does not have corrosion inhibition effect and cannot further improve the corrosion resistance of various mechanical equipment.

[0006] The patent application CN10767885A discloses a phosphorus-free corrosion and scale inhibitor, which comprises itaconic acid-acrylic acid-acrylate copolymer, 2-acrylamide-2-methylpropane sulfonic acid-diethyl acrylamide polymer, polyepoxysuccinic acid and hydrolyzed polymaleic anhydride, the phosphorus-free corrosion and scale inhibitor adopts active groups to chelate high-valence metal ions, and has certain corrosion and scale inhibition performance; however, the above-mentioned grey water scale inhibition dispersants all adopt high molecular polymers, the stability of the high molecular scale inhibitor is extremely susceptible to external environment, and the slow-release effect is not stable and continuous.

[0007] In view of the technical defects, a solution is provided. SUMMARY

[0008] The present application aims to provide a corrosion type grey water scale inhibition dispersant and a preparation method thereof, and solve the problems of poor stability and non-durable scale inhibition efficiency of the grey water scale inhibition dispersant in the prior art, and how to improve the corrosion performance of the grey water scale inhibition dispersant is also a technical problem to be solved.

[0009] The object of the present application can be achieved by the following technical solution: a preparation method of a corrosion type grey water scale inhibition dispersant, comprising the following steps:

[0010] S1, uniformly mix styrene, acrylamide, acrylic acid and deionized water to obtain a mixture; add a dispersant and an initiator into the mixture, and react at room temperature for 10-12 hours to obtain a product; and the product is subjected to post-process treatment to obtain a polymer wall material;

[0011] Styrene, acrylamide and acrylic acid are used as monomers, and the polymer wall material is obtained through polyaddition reaction under the action of the dispersant and the initiator; after the acrylamide and the acrylic acid are dissolved in water, opposite charges are generated to cause electrostatic effect, the solubility is reduced and phase separation occurs, and the corrosion type grey water scale inhibition dispersant wall material is formed by condensation.

[0012] S2, dissolve the composite scale inhibition dispersant in ethanol to prepare a 10wt% core material solution; dissolve the polymer wall material in deionized water to prepare a 10wt% wall material solution; heat 100mL of the core material solution to 40-45℃, and then add 100mL of the wall material solution dropwise into the core material solution to obtain a mixed solution; and the mixed solution is subjected to post-process treatment to obtain the corrosion type grey water scale inhibition dispersant.

[0013] The polymer wall material is dissolved in deionized water to prepare a wall material solution, the composite scale inhibitor is dissolved in ethanol to prepare a core material solution, the core material solution is adjusted to a pH value by glacial acetic acid, then the wall material solution is added drop by drop to carry out a composite coacervation reaction to obtain a composite coacervation product, the mixed solution is cooled to a low temperature state to terminate the composite coacervation reaction, the wall material is allowed to analyze out, then the pH value of the composite coacervation product is adjusted, formaldehyde is used as a curing crosslinking agent to carry out curing to prepare the corrosion-inhibiting type grey water scale and dispersant.

[0014] Further, the preparation method of the composite scale and dispersant comprises the following steps:

[0015] A1, chitosan, vanillin and anhydrous ethanol are mixed, refluxed and reacted at 70-80°C for 2-3h, then filtered under reduced pressure to obtain a solid; the solid is dried at 70-80°C under vacuum to a constant weight to obtain vanillin modified chitosan;

[0016] Chitosan contains free amino groups, which can react with the aldehyde group in vanillin to generate a methanimine characteristic group, thereby obtaining vanillin modified chitosan.

[0017] The reaction formula of chitosan and vanillin to obtain vanillin modified chitosan is as follows:

[0018]

[0019] A2, polyaspartic acid, modified corrosion inhibitor, vanillin modified chitosan and 40-50wt% ethanol solution are mixed, refluxed and reacted at 70-80°C for 10-12h, then distilled at 100-110°C until all the liquid is volatilized, and the obtained solid is the composite scale and dispersant.

[0020] The imino and amino functional groups contained in the polyaspartic acid and modified corrosion inhibitor solid can react with the hydroxyl group in the vanillin modified chitosan to prepare the composite scale and dispersant.

[0021] The reaction formula of polyaspartic acid, modified corrosion inhibitor solid and vanillin modified chitosan is as follows:

[0022]

[0023] Further, in step A1, the amount ratio of chitosan, vanillin and anhydrous ethanol is 20-40g: 15-25g: 100mL; in step A2, the amount ratio of polyaspartic acid, modified corrosion inhibitor, vanillin modified chitosan and ethanol solution is 30-50g: 30-40g: 30-40g: 200mL.

[0024] Further, in step A2, the preparation method of the modified corrosion inhibitor comprises the following steps:

[0025] B1, triazole, acetone, potassium carbonate and ethyl chloroacetate are mixed, and refluxed at 80-90 DEG C for 10-12h in a closed system to obtain a mixture; the mixture is filtered, and the filtrate is distilled under reduced pressure at -0.1 MPa to -0.09 MPa to obtain white solid intermediate A;

[0026] Triazole and ethyl chloroacetate are subjected to N-alkylation to prepare intermediate A, and the reaction formula is as follows:

[0027]

[0028] B2, intermediate A, hydrazine hydrate and ethanol are mixed and refluxed at 70-80 DEG C for 10-12h to obtain a reaction liquid; the reaction liquid is distilled at 75-80 DEG C until the volume of the precipitated solid is constant, and the solid is collected; the solid is dried under vacuum at 70-80 DEG C until the weight is constant to obtain a modified corrosion inhibitor.

[0029] Intermediate A and hydrazine hydrate are reacted to prepare a modified corrosion inhibitor, and the reaction formula is as follows:

[0030]

[0031] Further, in step B1, the amount ratio of triazole, acetone, potassium carbonate and ethyl chloroacetate is 7-14g:150mL:5-10g:15-20mL; in step B2, the amount ratio of intermediate A, hydrazine hydrate and ethanol is 25-35g:5-10mL:100mL.

[0032] Further, in step S1, the amount ratio of styrene, acrylamide, acrylic acid and deionized water is 5-10mL:20-30g:20-30mL:100mL; the dispersant is sodium dodecyl sulfonate, and the amount is 0.15-0.3g; the initiator is potassium persulfate, and the amount is 0.3-0.5g.

[0033] Further, in step S1, the post-process treatment is specifically transferring the product into a dialysis bag, and dialyzing for 3d to obtain a polymer wall material.

[0034] Further, in step S2, the post-process treatment is specifically adding 5wt%-10wt% of glacial acetic acid into the mixed solution, adjusting the pH value of the mixed solution to 3.5-4, stirring for 10-15min to obtain a composite coacervation product; the composite coacervation product is naturally cooled to room temperature, and then cooled to 10-15 DEG C by using an ice water bath, and then 10wt% of NaOH solution is added, the pH value of the composite coacervation product is adjusted to 9-11, and then 2-3mL of formaldehyde is added and solidified for 10-12h to obtain a corrosion type grey water scale inhibition dispersant.

[0035] As another aspect of the present application, the preparation method of the corrosion-inhibiting type grey water scale inhibition dispersant.

[0036] The present application has the following advantages:

[0037] 1、The composite scale inhibition dispersant prepared by the present application is prepared by using polyaspartic acid, modified corrosion inhibitor and vanillin modified chitosan as monomers, the central atom N of the triazole contains an unshared electron pair, when the metal has an empty d orbital, the lone pair of electrons of the central atom N of the triazole can form a coordination bond with the empty d orbital and be adsorbed on the metal surface, the adsorption is chemical adsorption, and it is difficult to desorb after adsorption, the triazole is reacted with ethyl chloroacetate and hydrazine hydrate in sequence to obtain a modified corrosion inhibitor containing imino and amino functional groups, which can react with other monomers, chitosan is an oligosaccharide formed by 2-10 amino glucose connected by glycosidic bonds, contains a large number of hydroxyl and amino functional groups, is non-toxic to the environment, and can be completely degraded by microorganisms or fungi, and therefore is an environmentally friendly green corrosion inhibitor;

[0038] The chitosan is modified by vanillin to increase carbon-nitrogen double bonds and hydroxyl groups, the carbon-nitrogen double bonds contain lone pairs of electrons and have electron-donating properties, so they can also form coordination bonds with the empty d orbital of the metal and be adsorbed, improving the corrosion inhibition performance of chitosan, polyaspartic acid is a polycarboxylic acid polymer, and has both acidic carboxyl and basic amide groups in the molecular structure, so polyaspartic acid has both neutral and anionic scale inhibitor properties, can effectively inhibit calcium carbonate, calcium sulfate, calcium phosphate and barium sulfate scale through condensation and dispersion, lattice distortion, complexation and solubilization, and exhibits excellent polymerization effect, the modified corrosion inhibitor, vanillin modified chitosan and polyaspartic acid are reacted to prepare a composite scale inhibition dispersant with excellent corrosion inhibition effect.

[0039] 2、In order to improve the durability and stability of the prepared composite scale inhibition dispersant, the present application embeds the composite scale inhibition dispersant into the synthesized polymer material wall material as a core material to improve the stability of the material and control the release rate of the material, and the present application polymerizes styrene, acrylamide and acrylic acid monomers to obtain a polymer material polymer wall material, disperses the core material into an aqueous solution of the polymer wall material to obtain a self-assembled microcapsule, the shell layer of the microcapsule has uniformly distributed pores and can embed small molecule substances, and the release effect is durable and stable, in addition, the amide group and carboxyl group contained in the wall material have adsorption properties for calcium sulfate and calcium carbonate, so that the wall material and the core have excellent scale inhibition performance, realizing double scale inhibition and release scale inhibition. DETAILED DESCRIPTION

[0040] The technical solutions of the present application will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0041] Embodiment 1

[0042] The present embodiment provides a preparation method of a composite scale and dispersion inhibitor for an inhibition type grey water scale and dispersion inhibitor, comprising the following steps:

[0043] A1, a 250 mL four-port reaction bottle is provided with a stirrer and a reflux condenser, 7 g of triazole, 150 mL of acetone, 10 g of potassium carbonate and 20 mL of ethyl chloroacetate are added into the four-port reaction bottle, the four-port reaction bottle is transferred to a water bath, and then the four-port reaction bottle is sealed, heated under reflux at 90 DEG C for 12 h to obtain a mixture; the mixture is filtered, and the filtrate is collected; the filtrate is distilled under reduced pressure, and the pressure of the reduced pressure distillation is-0.1 MPa to obtain a white solid intermediate A.

[0044] A2, 25 g of intermediate A, 5 mL of hydrazine hydrate and 100 mL of ethanol are added into a 250 mL four-port reaction bottle, the four-port reaction bottle is provided with a stirrer, a reflux condenser and a thermometer, the four-port reaction bottle is sealed, and reflux reaction is carried out at 70 DEG C and 100 r / min for 10 h to obtain a reaction liquid; the reaction liquid is distilled at 75 DEG C until the volume of the precipitated solid is constant, and the solid is collected; the solid is dried in a vacuum oven at 70 DEG C to constant weight to obtain a modified corrosion inhibitor.

[0045] A3, 20 g of chitosan, 15 g of vanillin and 100 mL of anhydrous ethanol are mixed and added into a 250 mL three-port flask, a stirrer is arranged inside the three-port flask, a reflux condenser is connected to one end of the three-port flask, then the three-port flask is transferred to a water bath, the temperature of the water bath is set to 70 DEG C, the three-port flask is sealed, reflux reaction is carried out at 200 r / min for 2 h, then reduced pressure filtration is carried out to obtain a solid; the solid is vacuum dried at 70 DEG C to constant weight to obtain vanillin modified chitosan.

[0046] A4, 30 g of polyaspartic acid, 30 g of modified corrosion inhibitor, 30 g of vanillin modified chitosan and 200 mL of 40 wt% ethanol solution are added into a 500 mL four-port reaction bottle, then the four-port reaction bottle is sealed; reflux reaction is carried out at 70 DEG C for 10 h with 200 r / min mechanical stirring, after the reaction is completed, distillation is carried out at 100 DEG C until all the liquid is volatilized, and the obtained solid is the composite scale and dispersion inhibitor.

[0047] Embodiment 2

[0048] The embodiment provides a preparation method of a composite scale and dispersion inhibitor for an inhibition type grey water scale and dispersion inhibitor.

[0049] A1, 250mL of a four-port reaction bottle is provided with a stirrer and a reflux condenser, 10g of triazole, 150mL of acetone, 8g of potassium carbonate and 17mL of ethyl chloroacetate are added into the four-port reaction bottle, the four-port reaction bottle is transferred to a water bath, then the four-port reaction bottle is sealed, heated at 85 DEG C under reflux, and reacts for 11h to obtain a mixture; the mixture is filtered, and the filtrate is collected; the filtrate is distilled under reduced pressure, the pressure of the reduced pressure distillation is-0.1MPa, and a white solid intermediate A is obtained.

[0050] A2, 30g of the intermediate A, 6mL of hydrazine hydrate and 100mL of ethanol are added into a 250mL four-port reaction bottle, the four-port reaction bottle is provided with a stirrer, a reflux condenser and a thermometer, the four-port reaction bottle is sealed, refluxed at 75 DEG C and 150r / min for 11h to obtain a reaction liquid; the reaction liquid is distilled at 76 DEG C until the volume of the precipitated solid is constant, and the solid is collected; the solid is dried in a vacuum oven at 75 DEG C until the weight is constant, and a modified corrosion inhibitor is obtained.

[0051] A3, 30g of chitosan, 20g of vanillin and 100mL of anhydrous ethanol are mixed and added into a 250mL three-port flask, a stirring rod is arranged in the three-port flask, a reflux condenser is connected to one end of the three-port flask, then the three-port flask is transferred to a water bath, the temperature of the water bath is set to 75 DEG C, the three-port flask is sealed, refluxed at 250r / min for 2.3h, then filtered under reduced pressure, and a solid is obtained; the solid is dried in a vacuum oven at 72 DEG C until the weight is constant, and vanillin modified chitosan is obtained.

[0052] A4, 40g of polyaspartic acid, 35g of the modified corrosion inhibitor, 35g of vanillin modified chitosan and 200mL of 45wt% ethanol solution are added into a 500mL four-port reaction bottle, then the four-port reaction bottle is sealed; under mechanical stirring at 220r / min, refluxed at 73 DEG C for 11h, then distilled at 105 DEG C until all the liquid is volatilized, and a solid obtained is a composite scale and dispersion inhibitor.

[0053] Embodiment 3

[0054] The embodiment provides a preparation method of a composite scale and dispersion inhibitor for an inhibition type grey water scale and dispersion inhibitor, including the following steps:

[0055] A1, 250 mL of four-port reaction bottle is provided with a stirrer, reflux condenser, 14 g of triazole, 150 mL of acetone, 10 g of potassium carbonate and 20 mL of ethyl chloroacetate are added to the four-port reaction bottle, the four-port reaction bottle is transferred to a water bath, then the four-port reaction bottle is sealed, heated to reflux at 90°C for 12 h to obtain a mixture; the mixture is filtered, and the filtrate is collected; the filtrate is distilled under reduced pressure, and the pressure of the reduced pressure distillation is -0.09 MPa to obtain a white solid intermediate A.

[0056] A2, 35 g of intermediate A, 10 mL of hydrazine hydrate and 100 mL of ethanol are added to a 250 mL four-port reaction bottle, the four-port reaction bottle is provided with a stirrer, reflux condenser and thermometer, the four-port reaction bottle is sealed, and reflux reaction is carried out at 80°C and 200 r / min for 12 h to obtain a reaction liquid; the reaction liquid is distilled at 80°C until the volume of the precipitated solid is constant, and the solid is collected; the solid is dried in a vacuum oven at 80°C to constant weight to obtain a modified corrosion inhibitor.

[0057] A3, 40 g of chitosan, 25 g of vanillin and 100 mL of anhydrous ethanol are mixed and added to a 250 mL three-port flask, which is provided with a stirrer inside, one end of the three-port flask is connected to a reflux condenser, then the three-port flask is transferred to a water bath, the temperature of the water bath is set to 80°C, then the three-port flask is sealed, and reflux reaction is carried out at 300 r / min for 3 h, then reduced pressure filtration is carried out to obtain a solid; the solid is vacuum dried at 80°C to constant weight to obtain vanillin modified chitosan.

[0058] A4, 50 g of polyaspartic acid, 40 g of modified corrosion inhibitor, 40 g of vanillin modified chitosan and 200 mL of 50%wt ethanol solution are added to a 500 mL four-port reaction bottle, then the four-port reaction bottle is sealed; with 300 r / min mechanical stirring, reflux reaction is carried out at 80°C for 12 h, after the reaction is completed, distillation is carried out at 110°C until all the liquid is volatilized, and the obtained solid is the composite scale inhibition dispersant.

[0059] Example 4

[0060] The present embodiment provides a preparation method of an inhibition type grey water scale inhibition dispersant, comprising the following steps:

[0061] 1, styrene, acrylamide and acrylic acid are respectively passed through 300 mesh basic alumina filler to remove the polymerization inhibitors carried by each monomer. A 250 mL four-port flask is selected, the four-port flask is connected to a reflux condenser and a stirring paddle, nitrogen is introduced into the four-port flask until the inside of the four-port flask is filled with nitrogen, 5 mL of styrene, 20 g of acrylamide, 20 mL of acrylic acid and 100 mL of deionized water are added to the four-port flask, and mixed stirring is carried out at 400 r / min for 10 min to obtain a mixture.

[0062] 2. Add 0.15 g of sodium dodecyl sulfate and 0.3 g of potassium persulfate into the four-necked flask, continue to react for 10 h to obtain a product. Transfer the product into a dialysis bag, dialyze for 3 d to remove unreacted monomers and related auxiliaries, and prepare a polymer wall material.

[0063] 3. Dissolve 10 g of the composite scale and dispersant prepared in Example 1 in ethanol to prepare a 10% wt. core material solution; dissolve 20 g of the polymer wall material in deionized water at 45 °C to prepare a 10% wt. wall material solution; transfer 100 mL of the core material solution into a 250 mL four-necked flask, heat the four-necked flask in a water bath to 40 °C, and then add the wall material solution dropwise into the four-necked flask through a constant-pressure dropping funnel to obtain a mixed solution; then add 5% wt. glacial acetic acid dropwise into the four-necked flask to adjust the pH value of the mixed solution to 3.5, stir for 10 min, and obtain a composite coacervate; then naturally cool the four-necked flask to room temperature, cool to 10 °C using an ice water bath, add 10% wt. NaOH solution into the four-necked flask to adjust the pH value of the composite coacervate to 9, and then add 2 mL of formaldehyde and solidify for 10 h to obtain an inhibited scale and dispersant for grey water.

[0064] Example 5

[0065] The present example provides a preparation method of an inhibited scale and dispersant for grey water, comprising the following steps:

[0066] 1. Pass styrene, acrylamide and acrylic acid through 300 mesh basic alumina filler respectively to remove the polymerization inhibitors carried by each monomer. Select a 250 mL four-necked flask, connect a reflux condenser and a stirring paddle to the four-necked flask, introduce nitrogen into the four-necked flask until the inside of the four-necked flask is filled with nitrogen, and then add 6 mL of styrene, 25 g of acrylamide, 25 mL of acrylic acid and 100 mL of deionized water into the four-necked flask, and mix and stir at 450 r / min for 15 min to obtain a mixture.

[0067] 2. Add 0.2 g of sodium dodecyl sulfate and 0.4 g of potassium persulfate into the four-necked flask, continue to react for 11 h to obtain a product. Transfer the product into a dialysis bag, dialyze for 3 d to remove unreacted monomers and related auxiliaries, and prepare a polymer wall material.

[0068] 3. 15 g of the composite scale and corrosion inhibitor prepared in Example 2 was dissolved in ethanol to prepare a 10% wt. core material solution; 26 g of the polymer wall material was dissolved in deionized water at 46 °C to prepare a 10% wt. wall material solution; 100 mL of the core material solution was transferred to a 250 mL four-necked flask, which was heated in a water bath to 42 °C, and then 100 mL of the wall material solution was added dropwise to the four-necked flask through a constant pressure dropping funnel to obtain a mixed solution; 6% wt. glacial acetic acid was then added dropwise to the four-necked flask to adjust the pH of the mixed solution to 3.8, and stirring was performed for 12 min to obtain a composite coacervate; the four-necked flask was then naturally cooled to room temperature, and then cooled to 12 °C in an ice water bath; 10% wt. NaOH solution was then added to the four-necked flask to adjust the pH of the composite coacervate to 10, and then 2.3 mL of formaldehyde was added and cured for 11 h to obtain the corrosion-inhibiting scale and corrosion inhibitor for grey water.

[0069] Example 6

[0070] The present example provides a method for preparing a corrosion-inhibiting scale and corrosion inhibitor for grey water, comprising the following steps:

[0071] 1. Styrene, acrylamide and acrylic acid were each passed through a 300 mesh basic alumina filler to remove the polymerization inhibitors present in each monomer. A 250 mL four-necked flask was selected, the four-necked flask was connected to a reflux condenser and a stirring paddle, nitrogen was introduced into the four-necked flask until the interior of the four-necked flask was filled with nitrogen, 10 mL of styrene, 30 g of acrylamide, 30 mL of acrylic acid and 100 mL of deionized water were added to the four-necked flask, and the mixture was stirred at 500 r / min for 20 min to obtain a mixture.

[0072] 2. 0.3 g of sodium dodecyl sulfonate and 0.5 g of potassium persulfate were added to the four-necked flask, and the reaction was continued for 12 h to obtain a product. The product was transferred to a dialysis bag and dialyzed for 3 d to remove unreacted monomers and related auxiliaries to prepare the polymer wall material.

[0073] 3. 20 g of the composite scale and corrosion inhibitor prepared in Example 3 was dissolved in ethanol to prepare a 10% wt. core material solution; 30 g of the polymer wall material was dissolved in deionized water at 50°C to prepare a 10% wt. wall material solution; 100 mL of the core material solution was transferred to a 250 mL four-necked flask, which was heated to 45°C in a water bath, and then 100 mL of the wall material solution was added dropwise to the four-necked flask through a constant pressure dropping funnel to obtain a mixed solution; 10 wt. of glacial acetic acid was then added dropwise to the four-necked flask to adjust the pH of the mixed solution to 4, and stirring was performed for 15 min to obtain a composite coacervate; the four-necked flask was then naturally cooled to room temperature, and then cooled to 15°C in an ice water bath; 10% wt. of NaOH solution was then added to the four-necked flask to adjust the pH of the composite coacervate to 11, and then 3 mL of formaldehyde was added and cured for 12 h to obtain the corrosion type grey water scale and corrosion inhibitor.

[0074] Comparative Example 1

[0075] In this comparative example, compared with Example 6, the polymer wall material was prepared using styrene and acrylic acid monomers.

[0076] Comparative Example 2

[0077] In this comparative example, compared with Example 6, no modified corrosion inhibitor was added during preparation of the composite scale and corrosion inhibitor.

[0078] Comparative Example 3

[0079] In this comparative example, compared with Example 6, the chitosan was not modified with vanillin during preparation of the composite scale and corrosion inhibitor.

[0080] Performance test:

[0081] 1. According to GB / T 16632-2008 “Determination of scale inhibition performance of water treatment agent - calcium carbonate deposition method”, the scale inhibition rates of the corrosion type grey water scale and corrosion inhibitors prepared in Examples 4-6 and Comparative Examples 1-3 on calcium carbonate at 6 h and 12 h were calculated; wherein the dosage of the scale inhibitor was 15 mg / L.

[0082] 2. The calcium chloride standard solution and the sodium sulfate standard solution prepared in advance were respectively mixed with the corrosion type grey water scale and corrosion inhibitors prepared in Examples 4-6 and Comparative Examples 1-3 in a certain volume, and then added to a 500 mL volumetric flask, diluted with deionized water, and shaken to obtain a solution with a final Ca 2+ concentration of 2000 mg / L and a SO4 2- concentration of 4800 mg / L; the prepared solution was transferred to a conical flask, and then sequentially placed at 70°C in a constant temperature water bath for 6 h and 12 h; after natural cooling, 3 mL of the filtrate was taken and added to a conical flask containing 30 mL of water, and then the Ca 2+The concentration of calcium sulfate is recorded respectively, and the scale inhibition rate of calcium sulfate is calculated by the same calculation formula of the scale inhibition rate of calcium carbonate.

[0083] 3. 7B04 aluminum alloy is used as the sample, and the size of the sample is 1 cm x 1 cm x 0.5 cm; before the experiment, the aluminum alloy sample is ultrasonically cleaned in alcohol to remove surface grease; then it is soaked in a solution containing 60 mg / L corrosion-inhibiting gray water scale and dispersant and 3.5%wt NaCl for 14 days, and then the corrosion inhibition rate is calculated by electrochemical detection. The calculation formula of the corrosion inhibition rate is as follows:

[0084] η = (I 0 corr -I corr ) / I corr

[0085] In the formula, I 0 corr and I corr respectively represent the corrosion current in the blank solution and the test solution.

[0086] Table 1 - Sample performance test data table

[0087]

[0088]

[0089] Data analysis:

[0090] Comparative analysis of the data in Table 1 shows that the corrosion-inhibiting gray water scale and dispersant prepared in Examples 4-6 has excellent scale inhibition efficiency for calcium carbonate and calcium sulfate and the scale inhibition effect is sustained. Acrylamide and acrylic acid have opposite charges and can interact through electrostatic interaction, which improves the firmness of the prepared polymer wall material and further improves the release effect of the prepared corrosion-inhibiting gray water scale and dispersant. The prepared corrosion-inhibiting gray water scale and dispersant has excellent scale inhibition efficiency for calcium carbonate and calcium sulfate at 12 h. However, in Comparative Example 1, no acrylamide monomer is added when preparing the polymer wall material, which reduces the firmness and stability of the polymer wall material and weakens the release effect. The scale inhibition efficiency is high in a short time, but the scale inhibition efficiency does not improve further after 12 h.

[0091] The corrosion-inhibiting type grey water scale inhibition dispersant prepared in the embodiments 4-6 of the present application takes the composite scale inhibition dispersant as a core material, and the modified corrosion inhibitor constituting the composite scale inhibition dispersant has a certain corrosion inhibition effect; however, in the comparative example 2, the modified corrosion inhibitor is not added when the composite scale inhibition dispersant is prepared, the modified corrosion inhibitor contains a nitrogen azole group and has a corrosion inhibition effect itself, which leads to the decrease of the corrosion inhibition rate of the corrosion-inhibiting type grey water scale inhibition dispersant prepared in the comparative example 2; in the comparative example 3, the vanillin modification is not used for chitosan when the composite scale inhibition dispersant is prepared, and the carbon-nitrogen double bond itself has an electron-donating property, which can improve the corrosion inhibition performance of chitosan, so that the corrosion inhibition efficiency of the composite scale inhibition dispersant prepared in the comparative example 3 is reduced, which is manifested as the decrease of the corrosion inhibition rate.

[0092] The above is only an example and description of the structure of the present application, and those skilled in the art can make various modifications or supplements or use similar ways to replace the described specific embodiments, as long as the modifications or supplements or replacements do not deviate from the structure of the present application or exceed the scope defined by the present claims, and should belong to the protection scope of the present application.

[0093] In the description of the present specification, the description of the terms "one embodiment", "example", "specific example" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative description 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.

[0094] The preferred embodiments of the present application disclosed above are only used to help explain the present application. The preferred embodiments do not describe all the details and limit the present application to the specific embodiments. Obviously, many modifications and changes can be made according to the content of the present specification. The present specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present application, so that those skilled in the art can well understand and utilize the present application. The present application is only limited by the claims and their entire scope and equivalents.

Claims

1. A method for preparing an inhibitive scale dispersant for grey water, characterized in that, The method comprises the following steps: S1, uniformly mixing styrene, acrylamide, acrylic acid and deionized water to obtain a mixture; adding a dispersant and an initiator into the mixture, and then reacting at room temperature for 10-12 hours to obtain a product; transferring the product into a dialysis bag, and dialyzing for 3 days to obtain a polymer wall material; S2, dissolving the composite scale and corrosion inhibitor in ethanol to prepare a 10wt% core material solution; dissolving the polymer wall material in deionized water to prepare a 10wt% wall material solution; heating 100mL of the core material solution to 40-45℃, and then adding 100mL of the wall material solution drop by drop into the core material solution to obtain a mixed solution; adding 5-10wt% of glacial acetic acid into the mixed solution to adjust the pH value of the mixed solution to 3.5-4, stirring for 10-15 minutes, and obtaining a composite coacervation product; The composite coacervation product is naturally cooled to room temperature, and then cooled to 10-15℃ by using an ice water bath, and then 10wt% of NaOH solution is added to adjust the pH value of the composite coacervation product to 9-11, and then 2-3mL of formaldehyde is added and cured for 10-12 hours to obtain the corrosion type grey water scale and corrosion inhibitor; The method for preparing the composite scale and corrosion inhibitor comprises the following steps: A1, mixing chitosan, vanillin and anhydrous ethanol, refluxing and reacting at 70-80℃ for 2-3 hours, and then performing vacuum filtration under reduced pressure to obtain a solid; vacuum drying the solid at 70-80℃ until the weight is constant to obtain vanillin modified chitosan; A2, mixing polyaspartic acid, modified corrosion inhibitor, vanillin modified chitosan and 40-50wt% of ethanol solution, refluxing and reacting at 70-80℃ for 10-12 hours, and then distilling at 100-110℃ until all the liquid is volatilized to obtain a solid, which is the composite scale and corrosion inhibitor; The method for preparing the modified corrosion inhibitor comprises the following steps: B1, mixing triazole, acetone, potassium carbonate and ethyl chloroacetate in a closed system, refluxing and reacting at 80-90℃ for 10-12 hours to obtain a mixture; performing filtration on the mixture to collect a filtrate; distilling the filtrate under reduced pressure at-0.1MPa to-0.09MPa to obtain a white solid intermediate A; B2, mixing the intermediate A, hydrazine hydrate and ethanol, refluxing and reacting at 70-80℃ for 10-12 hours to obtain a reaction liquid; distilling the reaction liquid at 75-80℃ until the volume of the precipitated solid is constant, and collecting the solid; vacuum drying the solid at 70-80℃ until the weight is constant to obtain the modified corrosion inhibitor.

2. The method according to claim 1, characterized in that, In step A1, the amount ratio of chitosan, vanillin and anhydrous ethanol is 20-40g:15-25g:100mL; in step A2, the amount ratio of polyaspartic acid, modified corrosion inhibitor, vanillin modified chitosan and ethanol solution is 30-50g:30-40g:30-40g:200mL.

3. The method according to claim 1, characterized in that, In step B1, the amount ratio of triazole, acetone, potassium carbonate and ethyl chloroacetate is 7-14g:150mL:5-10g:15-20mL; in step B2, the amount ratio of intermediate A, hydrazine hydrate and ethanol is 25-35g:5-10mL:100mL.

4. The method according to claim 1, characterized in that, In step S1, the ratio of the amount of styrene, acrylamide, acrylic acid and deionized water is 5-10 mL: 20-30 g: 20-30 mL: 100 mL; the dispersant is sodium dodecyl sulfonate, and the amount is 0.15-0.3 g; the initiator is potassium persulfate, and the amount is 0.3-0.5 g.

5. An inhibitor type grey water scale control dispersant characterized in that, The corrosion-inhibiting scale and fouling dispersant for grey water is prepared by the method of any one of claims 1-4.

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