Pre-film agent composition, pre-film agent, and preparation method and application thereof

Abstract

The present application relates to circulating water treatment technical field, disclose a kind of pre-film agent composition, circulating water pre-film agent and its preparation method and application.The composition includes polyepoxysuccinic acid, cathode type corrosion inhibitor, sodium hydroxide, saccharomyces cerevisiae cell wall, water;With the total weight of the composition 100 weight parts as 100 weight parts, the content of the water is 48-53 weight parts, the content of the polyepoxysuccinic acid is 11-15 weight parts, the content of the cathode type corrosion inhibitor is 30-32 weight parts, the content of the sodium hydroxide is 1-3 weight parts, the content of the saccharomyces cerevisiae cell wall is 3-9 weight parts.The pre-film agent is used for the pre-film stage of industrial circulating cooling water system chemical cleaning pre-film, after pre-film of test piece, film is reacted to copper sulfate test film solution and changes color time difference ≥10s.

Description

Technical Field

[0001] This invention relates to the field of circulating water treatment technology, specifically to a pre-filming agent composition, the pre-filming agent, its preparation method, and its application. Background Technology

[0002] Industrial circulating cooling water systems require pre-filming and cleaning before new systems are put into operation, and old systems must undergo pre-filming treatment promptly after cleaning. Pre-filming effectively slows down corrosion rates, extends the service life of pipes and heat exchangers, and ensures normal system operation. The principle behind pre-filming protecting metal surfaces from corrosion is that certain components in the chemical agents form complexes with metal ions in the cooling water, creating a very thin protective film that adheres firmly to the metal surface, thus inhibiting corrosion from the cooling water.

[0003] The types and mechanisms of action of circulating water pre-filming agents are mainly divided into three categories: oxidation film type corrosion inhibitors (pre-filming agents), precipitation film type corrosion inhibitors (pre-filming agents), and adsorption film type corrosion inhibitors (pre-filming agents).

[0004] Oxide film type corrosion inhibitors are also called passivation film type corrosion inhibitors. When the corrosion inhibitor reaches the metal surface, it oxidizes the surface layer of the base metal. This thin film protects the metal and inhibits corrosion. This oxide film (or passivation film) is only a few nanometers thick, generally <0.01μm, and the film is uniformly and densely distributed.

[0005] Precipitated film corrosion inhibitors can form a layer of insoluble precipitate or complex with certain ions in water or with ions from corrosion, depositing on the metal surface to prevent corrosion. These films are relatively thick, reaching up to 0.1 μm, and sometimes their color halo is visible to the naked eye. They are widely used in circulating cooling water systems.

[0006] Adsorption film-type corrosion inhibitors are all organic compounds containing functional groups such as N, S, P, and O. Their structures contain hydrophilic groups that can adsorb onto the metal surface and hydrophobic groups that shield the metal surface. The hydrophilic groups are directionally adsorbed onto the metal surface, while the hydrophobic groups hinder the diffusion of water and dissolved oxygen into the metal, thereby achieving corrosion inhibition.

[0007] Sodium polyepoxysuccinate, a nitrogen-free and phosphorus-free organic compound, possesses both scale inhibition and corrosion inhibition properties. It exhibits good biodegradability and is suitable for water systems with high alkalinity and high metal content, making it a green water treatment chemical. The mechanism of the corrosion inhibition performance of sodium polyepoxysuccinate lies in the fact that the oxygen atoms in its polar groups (-COOH, -OH, -O-, etc.) possess lone pairs of electrons, which can serve as adsorption centers. These centers adsorb metals, forming five- or six-membered cyclic compounds that adhere to the metal surface. Through these interactions, sodium polyepoxysuccinate forms a dense, insoluble adsorption film on the metal surface, isolating corrosive substances from metal ions and increasing the activation energy of the metal ion activation process, thereby achieving a corrosion inhibition effect.

[0008] Zinc salts are the most commonly used cathodic corrosion inhibitors in circulating cooling water systems, with zinc ions playing a vital role. Zinc ions can rapidly form a zinc hydroxide precipitate film in the high pH region of the cathode. While zinc salts form a film quickly, they also have some drawbacks: firstly, they are soft and not durable; secondly, zinc salts are unstable at high pH values, leading to precipitation and the formation of zinc scale.

[0009] Microbial surface adsorption research is an increasingly important focus in environmental and ecological sciences. Microorganisms exhibit adsorption properties for metal ions, primarily through the formation of complexes between charged functional groups on their cell walls and metal ions, thereby immobilizing heavy metals.

[0010] The main components of yeast cell walls are glucan, mannan, protein, glucosamine, phosphate, and lipids. Rich in functional groups such as N, S, P, and O, they can serve as adsorption centers for metal ions. The hydrophilic groups in their structure can adsorb onto metal surfaces, while the hydrophobic groups hinder the diffusion of water and dissolved oxygen to the metal. Therefore, they have the potential to serve as pre-filming agents.

[0011] CN101746899A discloses a novel corrosion and scale inhibitor, which is composed of the following weight ratios: sodium polyepoxysuccinate: 1-16; sodium polyaspartate: 1-18; hydrolyzed maleic anhydride: 1-13; sodium gluconate: 1-25; acrylic acid-acrylate-sulfonate terpolymer: 1-18; zinc sulfate: 1-8; benzotriazole: 1-12; NaOH: 0.5-2. This corrosion and scale inhibitor exhibits good corrosion and scale inhibition effects at temperatures below 150℃ and pH below 12, enabling the Ca(OH)₂ SO₂ removal process to operate normally in small and medium-sized boiler rooms, and providing protection for equipment with copper or copper alloy structures. However, it does not offer protection against microbial corrosion. In addition, although the corrosion inhibition mechanism of scale and corrosion inhibitors is also mainly film formation to prevent corrosion, the film formed by pre-filming agents is thicker, and pre-filming agents are used for chemical cleaning and pre-filming in water treatment, while scale and corrosion inhibitors are used for normal operation of circulating water. The two have different uses. Summary of the Invention

[0012] This invention provides a pre-filming agent that requires a small amount, forms a film quickly, and achieves a good film-forming effect.

[0013] The inventors of this invention discovered during their research that a compound of sodium polyepoxysuccinate, zinc sulfate, polymaleic acid, and a carboxylic acid-sulfonate copolymer exhibits excellent corrosion inhibition properties. Furthermore, by increasing the concentration of the compound and reducing the water flow rate, it also shows potential as a pre-filming agent for chemical cleaning of circulating water. However, in actual industrial circulating water systems, especially in online chemical cleaning pre-filming processes, high compound concentrations increase cleaning costs, and achieving low flow rates in production facilities is difficult. Additionally, sodium polyepoxysuccinate has an alkaline pH, while polymaleic acid and the carboxylic acid-sulfonate copolymer have acidic pH values; these three compounds may react when compounded, reducing the effectiveness of the compound. In view of this, after in-depth research, the inventors discovered that by adjusting sodium polyepoxysuccinate to polyepoxysuccinic acid through acidification, and then compounding it with the cell wall of Saccharomyces cerevisiae and a cathodic corrosion inhibitor composed of zinc sulfate, carboxylic acid-sulfonate copolymer, and polymaleic acid in a mass ratio of 1:1.4-1.6:2.5-2.8, the compatibility of the compounding components and the agent's tolerance to high water flow rates can be improved, and the amount of agent used can be reduced. This allows it to be used as a pre-filming agent for chemical cleaning of industrial circulating water.

[0014] To achieve the above objectives, a first aspect of the present invention provides a pre-filming agent composition comprising the following components: polyepoxysuccinic acid, sodium hydroxide, a cathodic corrosion inhibitor, a Saccharomyces cerevisiae cell wall, and water;

[0015] Based on 100 parts by weight of the total composition, the water content is 48-53 parts by weight, the polyepoxysuccinic acid content is 11-15 parts by weight, the cathodic corrosion inhibitor content is 30-32 parts by weight, the sodium hydroxide content is 1-3 parts by weight, and the Saccharomyces cerevisiae cell wall content is 3-9 parts by weight.

[0016] The cathode corrosion inhibitor is composed of zinc sulfate, carboxylic acid-sulfonate copolymer, and polymaleic acid in a mass ratio of 1:1.4-1.6:2.5-2.8.

[0017] A second aspect of the present invention provides a method for preparing a pre-filming agent, the method comprising using the components of the composition described in the first aspect, including:

[0018] (1) Sodium polyepoxysuccinate is first mixed with an acid to obtain polyepoxysuccinic acid; and

[0019] Zinc sulfate is mixed with polymaleic acid and carboxylic acid-sulfonate copolymer to obtain a cathodic corrosion inhibitor.

[0020] (2) In the presence of water, polyepoxysuccinic acid, cathodic corrosion inhibitor and sodium hydroxide are mixed in a third step to obtain mixture I;

[0021] (3) The cell wall of the brewer's yeast is mixed with the mixture I for the fourth time to obtain the pre-filming agent.

[0022] A third aspect of the present invention provides a pre-filming agent prepared by the method described in the second aspect.

[0023] The fourth aspect of this invention provides the application of the pre-filming agent described in the third aspect in the pre-filming of heat exchange equipment and pipelines in industrial circulating cooling water systems.

[0024] The pre-filming agent provided by this invention exhibits excellent film-forming properties through the synergistic effect of components such as polyepoxysuccinic acid, cathodic corrosion inhibitor, sodium hydroxide, Saccharomyces cerevisiae cell wall, and water. Furthermore, the biodegradable Saccharomyces cerevisiae cell wall enhances the precipitation and adsorption film-forming capabilities of the pre-filming agent. Simultaneously, the inventors discovered during their research that when the cathodic corrosion inhibitor is composed of zinc sulfate, carboxylic acid-sulfonate copolymer, and polymaleic acid in a mass ratio of 1:1.4-1.6:2.5-2.8, better film-forming effects and faster film formation are achieved. When used in the pre-filming stage of chemical cleaning in industrial circulating cooling water systems, the pre-filming agent provided by this invention results in a color change time difference of ≥10 seconds between the membrane and the copper sulfate test solution after pre-filming. Attached Figure Description

[0025] Figure 1 This is a visual image of the film formed after the pre-filming agent prepared in Example 1 was used for pre-filming.

[0026] Figure 2 This is a visual image of the film formed after the pre-filming agent prepared in Comparative Example 5 was used for pre-filming. Detailed Implementation

[0027] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0028] As previously described, a first aspect of the present invention provides a pre-filming composition comprising the following components: polyepoxysuccinic acid, a cathodic corrosion inhibitor, sodium hydroxide, a cell wall of Saccharomyces cerevisiae, and water;

[0029] Based on 100 parts by weight of the total composition, the water content is 48-53 parts by weight, the polyepoxysuccinic acid content is 11-15 parts by weight, the cathodic corrosion inhibitor content is 30-32 parts by weight, the sodium hydroxide content is 1-3 parts by weight, and the Saccharomyces cerevisiae cell wall content is 3-9 parts by weight.

[0030] The cathode corrosion inhibitor is composed of zinc sulfate, carboxylic acid-sulfonate copolymer, and polymaleic acid in a mass ratio of 1:1.4-1.6:2.5-2.8.

[0031] Preferably, the pH value of the pre-filming agent is 5.5-6.5.

[0032] Preferably, the carboxylic acid-sulfonate copolymer has a weight-average molecular weight of 4500-6000 g / mol and a density of ≥1.15 g / cm³ at 20°C. 3 The solid content is 42.0-44.0 wt%; the pH value is 3.8-4.6. The inventors of this invention have found that, under this preferred condition, the pre-filming agent has a better film-forming effect.

[0033] It should be noted that this pH value refers to the pH value when the concentration of the carboxylic acid-sulfonate copolymer aqueous solution is 1 wt%.

[0034] More preferably, the carboxylic acid-sulfonate copolymer is a carboxylic acid-sulfonate copolymer with the brand name TH-2000 produced by Shandong Taihe Technology Co., Ltd.

[0035] Preferably, the polymaleic acid has a relative molecular weight of 400-800 and a density of 1.22-1.25 g / cm³ at 20°C. 3 The pH value is 2.0-3.0, the bromine value is ≤50mg / g, and the solid content is ≥50wt%. The inventors of this invention have discovered that, under this preferred condition, the obtained pre-filming agent has better film-forming effect and faster film formation.

[0036] More preferably, the polymaleic acid is polymaleic acid HPMA produced by Shandong Taihe Technology Co., Ltd.

[0037] Preferably, the sodium hydroxide is an aqueous solution of sodium hydroxide with a mass fraction of 25-30 wt%.

[0038] According to a preferred embodiment, the polyepoxysuccinic acid is obtained by mixing an acid with sodium polyepoxysuccinate.

[0039] Preferably, the sodium polyepoxysuccinate has a relative molecular weight of 400-1500 and a density of ≥1.3 g / cm³ at 20°C. 3 .

[0040] In a preferred embodiment, the mass ratio of the acid to sodium polyepoxysuccinate is 1-3:1. The inventors of this invention have found that, under this preferred embodiment, the obtained pre-filming agent exhibits better and faster film-forming performance.

[0041] Preferably, the acid is selected from at least one of hydrochloric acid, sulfuric acid, and aminosulfonic acid.

[0042] In a preferred embodiment, the hydrochloric acid has a mass concentration of 31-37 wt%, the sulfuric acid has a mass concentration of 60-80 wt%, and the aminosulfonic acid has a mass concentration of 5-10 wt%.

[0043] As previously described, a second aspect of the present invention provides a method for preparing a pre-filming agent, the method being carried out using the components of the composition described in the first aspect, comprising:

[0044] (1) Sodium polyepoxysuccinate is first mixed with an acid to obtain polyepoxysuccinic acid; and

[0045] Zinc sulfate is mixed with polymaleic acid and carboxylic acid-sulfonate copolymer to obtain a cathodic corrosion inhibitor.

[0046] (2) In the presence of water, polyepoxysuccinic acid, cathodic corrosion inhibitor and sodium hydroxide are mixed in a third step to obtain mixture I;

[0047] (3) The cell wall of the brewer's yeast is mixed with the mixture I for the fourth time to obtain the pre-filming agent.

[0048] It should be noted that the definitions and amounts of sodium polyepoxysuccinate, acid, zinc sulfate, polymaleic acid, carboxylic acid-sulfonate copolymer, sodium hydroxide, and Saccharomyces cerevisiae cell wall described in this invention are the same as those of the corresponding components described in the first aspect, and will not be repeated here. Those skilled in the art should not understand this as a limitation of the invention.

[0049] According to a preferred embodiment, the conditions for the first mixing include: a temperature of 20-30°C, a time of 60-120 min, and a rotation speed of 80-110 rpm.

[0050] According to another preferred embodiment, the conditions for the second mixing include: a temperature of 20-30°C, a time of 60-120 min, and a rotation speed of 150-250 rpm.

[0051] Preferably, the conditions for the third mixing include: a temperature of 20-30°C, a time of 60-120 min, and a rotation speed of 150-250 rpm.

[0052] In a preferred embodiment, the conditions for the fourth mixing include: a temperature of 20-30°C, a time of 60-120 min, and a rotation speed of 40-60 rpm.

[0053] As previously stated, a third aspect of the present invention provides a pre-filming agent prepared by the method described in the second aspect.

[0054] As previously stated, the fourth aspect of the present invention provides the application of the pre-filming agent described in the third aspect in the pre-filming of heat exchange equipment and pipelines in industrial circulating cooling water systems.

[0055] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, all reagents used are commercially available chemical reagents of industrial grade purity.

[0056] Zinc sulfate: purchased from Hengyang Yuxing Chemical Co., Ltd.

[0057] Carboxylic acid-sulfonate copolymer I: weight average molecular weight 4500-5000 g / mol, density ≥1.15 g / cm³ at 20℃ 3 The solid content is 42.0-44.0 wt%; the pH value is 3.8-4.6, the model is TH-2000, and it was purchased from Shandong Taihe Technology Co., Ltd.

[0058] Carboxylic acid-sulfonate copolymer II: molecular weight 11000 g / mol, density at 20℃ ≥1.10 g / cm³ 3 The solid content is 36.5-37.5 wt%; the pH value is 4.5-5.5, the model is KR-2100, and it was purchased from Shandong Kairui Chemical Co., Ltd.

[0059] Carboxylic acid-sulfonic acid-nonionic terpolymer: viscosity of 100-300 cps at 25℃, density ≥1.15 g / cm³ 3 Solid content 42-44wt%, pH value 2.1-3.0, model TH-3100, purchased from Shandong Taihe Technology Co., Ltd.

[0060] Acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer (AA / AMPS): density at 20℃ ≥1.05 g / cm³ 3 Free monomer (based on acrylic acid) ≤0.2%, solid content ≥30wt%, limiting viscosity at 30℃ 0.055-0.1dl / g, purchased from Shandong Taihe Technology Co., Ltd.

[0061] Polymaleic acid I: relative molecular weight 400-800, density at 20℃ 1.22-1.25 g / cm³ 3 The pH value is 2.0-3.0, the bromine value is ≤50mg / g, and the solid content is ≥50wt%. It was purchased from Shandong Taihe Technology Co., Ltd.

[0062] Polymaleic acid II: relative molecular weight 400-800, density at 20℃ 1.18 g / cm³ 3 The bromine value is 80 mg / g, and the solid content is ≥48 wt%. It was purchased from Shandong Aike Water Treatment Technology Co., Ltd.

[0063] Sodium polyepoxysuccinate: relative molecular weight 400-1500, density at 20℃ ≥1.3g / cm3, pH value 10-12, purchased from Shandong Taihe Technology Co., Ltd.

[0064] Saccharomyces cerevisiae cell wall: purchased from Zhuhai Wenqi Biotechnology Co., Ltd.

[0065] Hydrochloric acid: purchased from Sinopec Hunan Petrochemical Co., Ltd., and the concentration used in the experiment was 32 wt%.

[0066] Sodium hydroxide: purchased from Sinopec Hunan Petrochemical Co., Ltd., and the concentration of the sodium hydroxide solution used in the experiment was 30 wt%.

[0067] Example 1

[0068] A method for preparing a pre-filming agent, the method comprising the following steps:

[0069] (1) 350g of sodium polyepoxysuccinate and 650g of hydrochloric acid were mixed in a first step to obtain polyepoxysuccinic acid I; and

[0070] A second mixture of 195g zinc sulfate, 293g polymaleic acid I, and 512g carboxylic acid-sulfonate copolymer I (i.e., the mass ratio of zinc sulfate to polymaleic acid I and carboxylic acid-sulfonate copolymer I is 1:1.5:2.63) is carried out to obtain a cathodic corrosion inhibitor.

[0071] The conditions for the first mixing were: temperature 25℃, time 60 min, and rotation speed 100 rpm.

[0072] The conditions for the second mixing were: temperature 25℃, time 120 min, and rotation speed 200 rpm.

[0073] (2) Take 119g of the polyepoxysuccinic acid prepared in step (1), 317g of the cathode type corrosion inhibitor prepared in step (1), 501g of water, and 15g of sodium hydroxide solution and mix them for the third time to obtain mixture I;

[0074] The conditions for the third mixing are: temperature 25°C, time 120 min, and rotation speed 200 rpm.

[0075] (3) Mix 48g of Saccharomyces cerevisiae cell wall with the mixture I for the fourth time to obtain a pre-filming agent, named pre-filming agent A;

[0076] The conditions for the fourth mixing are: temperature 25°C, time 120 min, and rotation speed 50 rpm.

[0077] Example 2

[0078] A method for preparing a pre-filming agent, the method comprising the following steps:

[0079] (1) Mix 500g of sodium polyepoxysuccinate with 500g of hydrochloric acid to obtain polyepoxysuccinic acid;

[0080] A second mixing was performed on 193g of zinc sulfate, 271g of polymaleic acid I, and 536g of carboxylic acid-sulfonate copolymer I (i.e., the mass ratio of zinc sulfate to polymaleic acid I and carboxylic acid-sulfonate copolymer I was 1:1.4:2.78) to obtain a cathodic corrosion inhibitor.

[0081] The conditions for the first mixing were: temperature 25℃, time 100min, and rotation speed 80rpm.

[0082] The conditions for the second mixing were: temperature 25℃, time 90 min, and rotation speed 250 rpm.

[0083] (2) Take 130g of the polyepoxysuccinic acid prepared in step (1), 300g of the cathode type corrosion inhibitor prepared in step (1), and mix them with 480g of water and 20g of sodium hydroxide solution to obtain mixture I.

[0084] The conditions for the third mixing are: temperature 25°C, time 120 min, and rotation speed 150 rpm.

[0085] (3) Mix 70g of Saccharomyces cerevisiae cell wall with the mixture I for the fourth time to obtain a pre-filming agent;

[0086] The conditions for the fourth mixing are: temperature 25°C, time 120 min, and rotation speed 60 rpm.

[0087] Example 3

[0088] A method for preparing a pre-filming agent, the method comprising the following steps:

[0089] (1) 250g of sodium polyepoxysuccinate and 750g of hydrochloric acid were mixed in a first step to obtain polyepoxysuccinic acid; and

[0090] A second mixing was performed on 197g of zinc sulfate, 310g of polymaleic acid I, and 493g of carboxylic acid-sulfonate copolymer I (i.e., the mass ratio of zinc sulfate to polymaleic acid I and carboxylic acid-sulfonate copolymer I was 1:1.57:2.50) to obtain a cathodic corrosion inhibitor.

[0091] The conditions for the first mixing were: temperature 25℃, time 60 min, and rotation speed 100 rpm.

[0092] The conditions for the second mixing were: temperature 25℃, time 120 min, and rotation speed 200 rpm.

[0093] (2) Take 110g of the polyepoxysuccinic acid prepared in step (1), 300g of the cathode type corrosion inhibitor, and mix them with 530g of water and 20g of sodium hydroxide solution to obtain mixture I;

[0094] The conditions for the third mixing are: temperature 25°C, time 120 min, and rotation speed 200 rpm.

[0095] (3) Mix 40g of Saccharomyces cerevisiae cell wall with the mixture I for the fourth time to obtain a pre-filming agent;

[0096] The conditions for the fourth mixing are: temperature 25°C, time 120 min, and rotation speed 50 rpm.

[0097] Example 4

[0098] This embodiment uses a method similar to that of Example 1, except that in this embodiment, polymaleic acid II of equal mass is used to replace polymaleic acid I.

[0099] The remaining steps are the same as in Example 1.

[0100] Example 5

[0101] This embodiment uses a method similar to that of Example 1, except that an equal mass of carboxylic acid-sulfonate copolymer II is used to replace carboxylic acid-sulfonate copolymer I.

[0102] The remaining steps are the same as in Example 1.

[0103] Comparative Example 1

[0104] This comparative example was conducted using a method similar to that of Example 1, except that an equal mass of water was used to replace the cell walls of the Saccharomyces cerevisiae in Example 1 in this comparative example.

[0105] The remaining steps are the same as in Example 1; a pre-filming agent is obtained and named pre-filming agent B.

[0106] Comparative Example 2

[0107] This comparative example was conducted using a method similar to that of Example 1, except that the amount of Saccharomyces cerevisiae cell wall used in this comparative example was 100g and the amount of water used was 449g.

[0108] The remaining steps are the same as in Example 1.

[0109] Comparative Example 3

[0110] This comparative example was conducted using a method similar to that of Example 1, except that the amount of cathodic corrosion inhibitor used in this comparative example was 330g, and the amount of water used was 488g.

[0111] The remaining steps are the same as in Example 1.

[0112] Comparative Example 4

[0113] This comparative example was carried out using a method similar to that of Example 1. The difference was that in step (1), 195g of zinc sulfate and 805g of carboxylic acid-sulfonate copolymer I were mixed for the second time to obtain a cathodic corrosion inhibitor.

[0114] The remaining steps are the same as in Example 1.

[0115] Comparative Example 5

[0116] This comparative example was carried out using a method similar to that of Example 1. The difference was that in step (1), 180g of zinc sulfate was mixed with 270g of polymaleic acid I and 550g of carboxylic acid-sulfonate copolymer I (that is, the mass ratio of zinc sulfate to polymaleic acid and carboxylic acid-sulfonate copolymer was 1:1.5:3.05) to obtain a cathodic corrosion inhibitor.

[0117] The remaining steps are the same as in Example 1.

[0118] Comparative Example 6

[0119] This comparative example was conducted using a method similar to that of Example 1, except that an equal mass of carboxylic acid-sulfonic acid-nonionic terpolymer was used to replace carboxylic acid-sulfonate copolymer I.

[0120] The remaining steps are the same as in Example 1.

[0121] Comparative Example 7

[0122] This comparative example was conducted using a method similar to that of Example 1, except that an equal mass of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer was used to replace carboxylic acid-sulfonate copolymer I.

[0123] The remaining steps are the same as in Example 1.

[0124] Test Example 1

[0125] The performance of the pre-filming agent prepared in the above examples was tested using a cooling water dynamic simulation device according to standard HG / T 3778-2005. The parameters of the cooling water dynamic simulation device are shown in Table 1, and the water quality of the test water during the pre-filming treatment is shown in Table 2. Specific test results are shown in Tables 3 and 4.

[0126] Table 1

[0127] Dynamic simulation device Model: Gaoyou Qinyou Instrument & Chemical Co., Ltd. QYDM water flow velocity 0.5-1.5m / s System volume 70L Inlet water temperature ≤32℃ Steam temperature 99.8-100.0℃ Specifications of 20# carbon steel test tubes: Ф10mm×1mm×680mm

[0128] Table 2

[0129]

[0130]

[0131] Table 3

[0132]

[0133] This invention provides, by way of example, spectral images of test pieces after pre-filming with the pre-filming agents prepared in Example 1 and Comparative Example 5 (e.g., Figure 1 , Figure 2 (as shown), Figure 1 The film-forming test piece showed a colored halo, indicating that the pre-filming agent provided by this invention can be used for chemical cleaning pre-filming of industrial circulating cooling water systems, and its film-forming effect is excellent. Figure 2 The presence of localized corrosion on the intermediate film-forming test piece indicates that the cathodic corrosion inhibitor in the pre-filming agent is composed of zinc sulfate, carboxylic acid-sulfonate copolymer, and polymaleic acid in a mass ratio of 1:1.4-1.6:2.5-2.8. It can only achieve excellent pre-filming effect after being compounded with polyepoxysuccinic acid, sodium hydroxide, Saccharomyces cerevisiae cell wall, and water.

[0134] Table 4

[0135]

[0136]

[0137] By comparing the experimental results of test pieces 1, 3, 5, 7, 9, 11, 13, 15, 17, and 19, it can be seen that the color change time of the test film solution of the pre-filming agent test piece provided by the present invention is relatively long, far exceeding the color change time of the test film solution specified in HG / T3778-2005.

[0138] The comparison of test pieces 1 to 12 shows that, under the same test conditions, provided that the color change time of the test film solution is ≥10s (HG / T 3778-2005), the concentration of the agent containing Saccharomyces cerevisiae cell wall in the pre-filming agent is lower than that without Saccharomyces cerevisiae cell wall.

[0139] The experiments comparing test pieces 13 to 20 show that the pre-filming agent containing the cell wall of Saccharomyces cerevisiae has a stronger adaptability to water flow rate. When the flow rate reaches 1.5 m / s, the pre-filming agent without the cell wall of Saccharomyces cerevisiae, at a concentration of 300 mg / L, cannot meet the standard requirement of a color change time of ≥10 s (HG / T 3778-2005) for film formation.

[0140] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A pre-filming agent composition, characterized in that, The composition comprises the following components: polyepoxysuccinic acid, sodium hydroxide, cathodic corrosion inhibitor, Saccharomyces cerevisiae cell wall, and water; Based on 100 parts by weight of the total composition, the water content is 48-53 parts by weight, the polyepoxysuccinic acid content is 11-15 parts by weight, the cathodic corrosion inhibitor content is 30-32 parts by weight, the sodium hydroxide content is 1-3 parts by weight, and the Saccharomyces cerevisiae cell wall content is 3-9 parts by weight. The cathode corrosion inhibitor is composed of zinc sulfate, carboxylic acid-sulfonate copolymer, and polymaleic acid in a mass ratio of 1:1.4-1.6:2.5-2.

8. The carboxylic acid-sulfonate copolymer has a weight-average molecular weight of 4500-6000 g / mol and a density of ≥1.15 g / cm³ at 20°C. 3 The solid content is 42.0-44.0 wt%; the pH value is 3.8-4.

6. The polymaleic acid has a relative molecular weight of 400-800 and a density of 1.22-1.25 g / cm³ at 20°C. 3 pH value is 2.0-3.0, bromine value is ≤50mg / g, and solid content is ≥50wt%.

2. The composition according to claim 1, wherein, The sodium hydroxide is an aqueous solution of sodium hydroxide with a mass fraction of 25-30 wt%.

3. The composition according to claim 1 or 2, wherein, The polyepoxysuccinic acid is obtained by mixing an acid with sodium polyepoxysuccinate.

4. The composition according to claim 3, wherein, The sodium polyepoxysuccinate has a relative molecular weight of 400-1500 and a density of ≥1.3 g / cm³ at 20°C. 3 .

5. The composition according to claim 4, wherein, The mass ratio of the acid to sodium polyepoxysuccinate is 1-3:

1.

6. The composition according to any one of claims 3-5, wherein, The acid is selected from at least one of hydrochloric acid, sulfuric acid, and aminosulfonic acid; The hydrochloric acid has a mass concentration of 31-37 wt%, the sulfuric acid has a mass concentration of 60-80 wt%, and the aminosulfonic acid has a mass concentration of 5-10 wt%.

7. A method for preparing a pre-filming agent, characterized in that, This method is performed using any of the components in the composition according to any one of claims 1-6, comprising: (1) Sodium polyepoxysuccinate is first mixed with an acid to obtain polyepoxysuccinic acid; and Zinc sulfate is mixed with carboxylic acid-sulfonate copolymer and polymaleic acid to obtain a cathodic corrosion inhibitor. (2) In the presence of water, polyepoxysuccinic acid, cathodic corrosion inhibitor and sodium hydroxide are mixed in a third mixture to obtain mixture I; (3) The cell wall of the brewer's yeast is mixed with the mixture I for the fourth time to obtain the pre-filming agent.

8. The method according to claim 7, wherein, The conditions for the first mixing include: a temperature of 20-30°C, a time of 60-120 min, and a rotation speed of 80-110 rpm; The conditions for the second mixing include: a temperature of 20-30°C, a time of 60-120 min, and a rotation speed of 150-250 rpm; The conditions for the third mixing include: a temperature of 20-30°C, a time of 60-120 min, and a rotation speed of 150-250 rpm; The conditions for the fourth mixing include: a temperature of 20-30℃, a time of 60-120 min, and a rotation speed of 40-60 rpm.

9. A pre-filming agent prepared by the method of claim 7 or 8.

10. The application of the pre-filming agent according to claim 9 in the pre-filming of heat exchange equipment and pipelines in industrial circulating cooling water systems.

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