Industrial cleaning agent and preparation method thereof

Abstract

The invention provides an industrial cleaning agent and a preparation method thereof, and the cleaning agent is prepared from the following raw materials by weight: 0.05-0.1% of sodium hydroxide, 0.2-0.3% of sodium gluconate, 1-2% of secondary alkyl sodium sulfonate, 1.5-2% of polyol, 1-1.5% of amino trimethylene phosphonic acid, 0.3-0.6% of gluconic acid-delta-lactone, 0.6-1% of glycerin, 0.8-1.2% of propylene glycol butyl ether, 0.05-0.075% of a modified polyether defoamer, and the balance of water. And the balance of water. The modified polyether defoaming agent is obtained by sequentially reacting alkenyl polyether with # imgabs0 # and hydrogen-containing silicone oil. The cleaning agent provided by the invention has better defoaming effect, lower corrosivity and higher stability, and also has the advantages that the preparation method is simple and easy to operate, and the cleaning agent is suitable for large-scale industrial production.

Description

Technical Field

[0001] The invention belongs to the technical field of cleaning agents, and particularly relates to an industrial cleaning agent and a preparation method thereof. Background Art

[0002] Traditional industrial cleaning agents, primarily based on strong alkaline substances like sodium hydroxide, offer strong cleaning capabilities, but they are also highly corrosive to the metal components of production equipment, and the resulting wastewater requires further harmless treatment. To address these issues, the addition of surfactants, alkaline additives, and defoamers to cleaning agents is often used to reduce the alkaline content and optimize cleaning performance, achieving good results.

[0003] However, in medium- and high-temperature cleaning scenarios, conventional defoamers are prone to problems such as short defoaming time and decomposition failure at high temperatures, seriously affecting cleaning efficiency and the stability of the equipment being cleaned. To address these pain points, the industry urgently needs to develop a cleaning agent that combines efficient cleaning, low corrosion, environmental safety, and excellent temperature-resistant defoaming properties. Summary of the Invention

[0004] In order to solve the problems of poor defoaming, high corrosiveness, and poor stability in the cleaning process of existing industrial cleaning agents, the present invention optimizes the cleaning agent formula to achieve high defoaming and high stability of the cleaning agent, reduce corrosiveness, and improve the safety of the cleaning agent.

[0005] In a first aspect, the present invention discloses an industrial cleaning agent, which is prepared from the following raw materials in weight percentage: 0.05-0.1% sodium hydroxide, 0.2-0.3% sodium gluconate, 1-2% sodium secondary alkyl sulfonate, 1.5-2% polyol, 1-1.5% aminotrimethylenephosphonic acid, 0.3-0.6% glucono-δ-lactone, 0.6-1% glycerol, 0.8-1.2% propylene glycol butyl ether, 0.05-0.075% modified polyether defoamer, and the balance is water; Wherein, the modified polyether defoamer is prepared by sequentially reacting alkenyl polyether with , obtained by reaction of hydrogen-containing silicone oil.

[0006] Furthermore, the preparation method of the modified polyether defoamer comprises the following steps: Step A1: At a temperature of 0-10°C, Add it dropwise to the solution of alkenyl polyether while continuously introducing nitrogen to remove HCl. After the addition is complete, heat to 40-60°C and react for 3-5 hours; Step A2: After the reaction is completed, the temperature is lowered to room temperature, and the pH of the system is adjusted to 6-7 using a saturated sodium carbonate solution. The NaCl precipitate is then removed by filtration, and the filtrate is subjected to reduced pressure distillation to remove the solvent, followed by addition of an ethanol-water mixed solvent for recrystallization; Step A3: Add toluene to the product obtained in step A2, raise the temperature to 80-120°C, add hydrogenated silicone oil dropwise, and then add a catalyst to react for 2-6 hours. After the reaction is completed, reduce the temperature to below 60°C, remove the catalyst, and then perform reduced pressure distillation on the solution to remove the solvent to obtain a modified polyether defoamer.

[0007] Furthermore, in step A1, the The addition time is 1-2h.

[0008] Furthermore, in step A1, the alkenyl polyether is at least one of allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether, and vinyl polyoxyethylene ether.

[0009] Furthermore, in step A1, the The molar ratio of the polyol to the alkenyl polyether is 1:1.05-2.3.

[0010] Furthermore, in step A1, the solution of the alkenyl polyether uses at least one of anhydrous dichloromethane, toluene, and tetrahydrofuran as a solvent.

[0011] Furthermore, in the solution of the alkenyl polyether, the mass of the solvent is 2-5 times the mass of the alkenyl polyether.

[0012] Furthermore, in step A3, the molar ratio of the hydrogen-containing silicone oil to the alkenyl polyether is 1.05-1.1:1.

[0013] It should be noted that, when calculating the molar ratio of hydrogenated silicone oil to alkenyl polyether in the present invention, the molar mass of hydrogenated silicone oil is calculated according to Si-H, and the molar mass of alkenyl polyether is calculated according to C=C.

[0014] Furthermore, in step A3, the catalyst is a Karstedt catalyst, i.e., a platinum-vinylsiloxane complex, wherein the Pt content is 2-3 wt %.

[0015] Furthermore, the amount of the catalyst added is 10-15 ppm of the total mass of the product obtained in step A2 and the hydrogen-containing silicone oil.

[0016] In a second aspect, the present invention discloses a method for preparing an industrial cleaning agent, comprising the following steps: Step S1: add water to a reaction kettle, add sodium hydroxide, sodium gluconate, sodium secondary alkyl sulfonate and polyol at room temperature, and stir thoroughly for 10-30 minutes; Step S2, adding aminotrimethylenephosphonic acid, glucono-δ-lactone, glycerol, propylene glycol butyl ether and modified polyether defoamer to a reaction kettle at room temperature, and stirring thoroughly until completely dissolved; Step S3: After the reaction is completed, the mixture is naturally cooled to room temperature and allowed to stand for 5-15 minutes to obtain an industrial cleaning agent.

[0017] Compared with the existing technology, the present invention improves environmental protection, cleaning performance, metal compatibility and stability in use by controlling the raw material components and ratios. The specific beneficial effects are as follows: 1. The present invention does not add a phosphorus auxiliary agent separately, and adopts aminotrimethylenephosphonic acid and glucono-δ-lactone instead of sodium tripolyphosphate, which can avoid eutrophication of water bodies; in addition, while ensuring a good cleaning effect, the amount of sodium hydroxide is reduced, and sodium gluconate is used to adjust the alkalinity, thereby reducing the difficulty of wastewater treatment and the risk of environmental pollution.

[0018] 2. The present invention utilizes the synergistic effect of sodium secondary alkyl sulfonate and polyol to quickly penetrate and emulsify and decompose oil stains; in addition, aminotrimethylenephosphonic acid and glucono-δ-lactone can effectively chelate calcium and magnesium ions in water to prevent precipitation, ensuring thorough cleaning and low dirt residue rate.

[0019] 3. The present invention adds low alkali in combination with sodium gluconate to play a corrosion inhibition role, significantly reducing the corrosion of sensitive metals such as aluminum alloys and copper, extending the service life of the equipment, and is applicable to a wide range of metal materials.

[0020] 4. The modified polyether defoamer added in the present invention contains benzene rings and silicone, which can improve the high temperature resistance and stability of the modified polyether defoamer, so that the prepared cleaning agent still has excellent defoaming and anti-foaming properties under medium and high temperature environments, solves the problem of high temperature failure of traditional defoamers, and ensures that dynamic cleaning processes such as high-pressure spraying are carried out smoothly.

[0021] 5. The glycerol and propylene glycol butyl ether added in the present invention serve as solvents to enhance the oil dissolving power and improve the temperature resistance and fluidity of the cleaning agent. The components cooperate with each other to maintain a stable cleaning effect under different temperature and water quality conditions. DETAILED DESCRIPTION

[0022] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0023] Preparation of modified polyether defoamer Step A1, press The molar ratio of allyl polyoxyethylene ether is 1:1.05. At a temperature of 5°C, Add dropwise to the toluene solution of allyl polyoxyethylene ether (m toluene: m allyl polyoxyethylene ether = 3:1), control the addition time to 1.5h, and continuously introduce nitrogen to remove HCl. After the addition is completed, heat to 50°C and react for 4h; Step A2: After the reaction is completed, the temperature of the system is lowered to room temperature, and a 30 wt % sodium carbonate solution is added dropwise to adjust the pH of the system to 7. The NaCl precipitate is then removed by filtration, and the filtrate is subjected to reduced pressure distillation to remove the solvent. The residue is then recrystallized by adding an ethanol-water mixed solvent (volume ratio 1:1); Step A3: Toluene is added to the solid product obtained in the above step A2, and the temperature is raised to 100° C. Hydrogenated silicone oil (calculated as Si-H) and allyl polyoxyethylene ether (calculated as C=C) are added dropwise at a molar ratio of 1.1:1. Karstedt catalyst is then added and reacted for 4 hours (the amount of catalyst added is 15 ppm based on the total mass of the solid product and the hydrogenated silicone oil). After the reaction is completed, the system temperature is lowered to below 60° C., the catalyst is removed by activated carbon adsorption, and the solution is then subjected to reduced pressure distillation to remove the solvent to obtain a modified polyether defoamer.

[0024] The allyl polyoxyethylene ether used was purchased from Guangdong Yunxing Biotechnology Co., Ltd.

[0025] By infrared spectroscopy monitoring, the hydroxyl peak disappears and the phosphate peak ( , P=O stretching vibration) appears, indicating that the modified polyether defoamer contains phosphate groups; in addition, the Si-H peak and C=C double bond peak The disappearance of indicates that a hydrosilylation reaction has occurred.

[0026] Example 1 An industrial cleaning agent is prepared from the following raw materials in percentage by weight: 0.05% sodium hydroxide, 0.3% sodium gluconate, 1.5% sodium secondary alkyl sulfonate, 1.5% polyol, 1% aminotrimethylenephosphonic acid, 0.5% glucono-δ-lactone, 1% glycerol, 1% propylene glycol butyl ether, 0.05% modified polyether defoamer, and the balance water. The preparation process is as follows: Step S1: add water to a reaction kettle, add sodium hydroxide, sodium gluconate, sodium secondary alkyl sulfonate and polyol at room temperature, and stir thoroughly for 20 minutes; Step S2, adding aminotrimethylenephosphonic acid, glucono-δ-lactone, glycerol, propylene glycol butyl ether and modified polyether defoamer to a reaction kettle at room temperature, stirring thoroughly until completely dissolved, and a clear and transparent solution indicates that the reaction is complete; Step S3: The system is naturally cooled to room temperature and allowed to stand for 15 minutes to obtain an industrial cleaning agent.

[0027] Example 2 An industrial cleaning agent is prepared from the following raw materials in percentage by weight: 0.1% sodium hydroxide, 0.2% sodium gluconate, 1% sodium secondary alkyl sulfonate, 2% polyol, 1.5% aminotrimethylenephosphonic acid, 0.5% glucono-δ-lactone, 1% glycerol, 1% propylene glycol butyl ether, 0.075% modified polyether defoamer, and the balance water. The preparation process is described in Example 1.

[0028] Example 3 An industrial cleaning agent is prepared from the following raw materials in percentage by weight: 0.08% sodium hydroxide, 0.25% sodium gluconate, 2% sodium secondary alkyl sulfonate, 2% polyol, 1.2% aminotrimethylenephosphonic acid, 0.5% glucono-δ-lactone, 1% glycerol, 1% propylene glycol butyl ether, 0.06% modified polyether defoamer, and the balance water. The preparation process is described in Example 1.

[0029] Example 4 An industrial cleaning agent is prepared from the following raw materials in percentage by weight: 0.05% sodium hydroxide, 0.23% sodium gluconate, 1% sodium secondary alkyl sulfonate, 2% polyol, 1.4% aminotrimethylenephosphonic acid, 0.5% glucono-δ-lactone, 1% glycerol, 1% propylene glycol butyl ether, 0.05% modified polyether defoamer, and the balance water. The preparation process is described in Example 1.

[0030] Comparative Example 1 There is a certain brand of industrial cleaning agent with the following formula: 0.28% flake caustic soda, 2% sodium secondary alkyl sulfonate, 2% copolymer of polyether polyol (C10-15), 1.5% sodium tripolyphosphate, 2% glycerol, 0.075% silicone defoamer, and the balance is water.

[0031] Comparative Example 2 (defoaming agent modified only with phosphate ester) The difference from Example 1 is that the defoaming agent is different. The preparation method of the defoaming agent in this comparative example is as follows: Step A1, press The molar ratio of allyl polyoxyethylene ether is 1:1.05. At a temperature of 5°C, Add dropwise to the toluene solution of allyl polyoxyethylene ether (m toluene: m allyl polyoxyethylene ether = 3:1), control the addition time to 1.5h, and continuously introduce nitrogen to remove HCl. After the addition is completed, heat to 50°C and react for 4h; Step A2: After the reaction is completed, the temperature of the system is lowered to room temperature, and a 30 wt % sodium carbonate solution is added dropwise to adjust the pH of the system to 7. The NaCl precipitate is then filtered to remove the solvent. The filtrate is subjected to reduced pressure distillation to remove the solvent. The residue is added to an ethanol-water mixed solvent (volume ratio of 1:1) for recrystallization to obtain a defoamer modified only with phosphate.

[0032] By infrared spectroscopy monitoring, the hydroxyl peak disappears and the phosphate peak ( , P=O stretching vibration) appears, indicating that the obtained modified polyether contains phosphate groups.

[0033] According to the formulation and preparation process in Example 1, an industrial cleaning agent was prepared using the above-mentioned defoamer modified only with phosphate.

[0034] Comparative Example 3 (defoaming agent modified with hydrogenated silicone oil only) The difference from Example 1 is that the defoaming agent is different. The preparation method of the defoaming agent in this comparative example is as follows: The toluene solution of allyl polyoxyethylene ether was heated to 100°C, and hydrogenated silicone oil was added dropwise at a molar ratio of hydrogenated silicone oil (calculated as Si-H) to allyl polyoxyethylene ether (calculated as C=C) of 1.1:1. Then, Karstedt catalyst was added and reacted for 4 hours (the amount of catalyst added was 15 ppm based on the total mass of allyl polyoxyethylene ether and hydrogenated silicone oil). After the reaction, the system temperature was lowered to below 60°C, the catalyst was removed by activated carbon adsorption, and the solution was distilled under reduced pressure to remove the solvent to obtain a defoaming agent modified only with hydrogenated silicone oil.

[0035] By infrared spectroscopy monitoring, Si-H peak and C=C double bond peak The disappearance of indicates that a hydrosilylation reaction has occurred.

[0036] According to the formula and preparation process in Example 1, an industrial cleaning agent was prepared using the above-mentioned defoaming agent modified with only hydrogen silicone oil.

[0037] Performance Testing The cleaning agents in the above embodiments and comparative examples all adopt the following cleaning method: 1. After cleaning the spray cleaning tank, prepare the cleaning agent into a 5wt% working solution according to the mass concentration; 2. Raise the working fluid temperature to 60°C; 3. Spray the working fluid onto the workpiece to be cleaned through a high-pressure pump. The cleaning time is 3 minutes. 4. Rinse the cleaned workpiece with tap water through a water pump for 1 minute; 5. The workpiece is subjected to performance testing after rust-proof treatment.

[0038] The test results are shown in Table 1, where the dirt residue rate was tested in accordance with GB / T 23436-2009; the defoaming rate was tested in accordance with the Roche foam tester method (ASTM D1173 standard); and the corrosion performance was tested in accordance with the standard method ASTM G31. Carbon steel Q235 was selected as the corrosion test piece, and a carbon steel corrosion rate of ≤0.05mm / year was considered acceptable.

[0039] Table 1

[0040] As can be seen from the above table, the cleaning agent prepared by the method of the present invention has good cleaning effect, defoaming effect and low corrosiveness; the alkaline substance content in Comparative Example 1 is high and the corrosiveness is relatively high; since the phosphate defoamer is highly water-soluble, it is easily diluted by water in the system, resulting in poor defoaming persistence, and the hydrogenated silicone oil can reduce the surface tension through the siloxane segment after modification, thereby improving the defoaming efficiency and stability. Therefore, the defoamer in Comparative Example 2 is only modified with phosphate, but not with hydrogenated silicone oil. The defoaming effect of the obtained cleaning agent is relatively poor, and the decontamination performance is relatively reduced; phosphate can be used as an emulsifier to enhance the oil dispersion ability, and complement the defoaming effect of hydrogenated silicone oil. Due to the lack of phosphate, the emulsification effect of the cleaning agent on oily stains is reduced, resulting in reduced decontamination performance. Therefore, the defoamer in Comparative Example 3 is only modified with hydrogenated silicone oil, but not with phosphate, and the defoaming effect is relatively poor, and the decontamination performance is relatively reduced.

Claims

1. An industrial cleaning agent, characterized in that The invention is prepared from the following raw materials in weight percentage: 0.05-0.1% sodium hydroxide, 0.2-0.3% sodium gluconate, 1-2% sodium secondary alkyl sulfonate, 1.5-2% polyol, 1-1.5% aminotrimethylenephosphonic acid, 0.3-0.6% glucono-δ-lactone, 0.6-1% glycerol, 0.8-1.2% propylene glycol butyl ether, 0.05-0.075% modified polyether defoamer, and the balance is water; Wherein, the modified polyether defoamer is prepared by sequentially reacting alkenyl polyether with , obtained by reaction of hydrogen-containing silicone oil.

2. The industrial cleaning agent according to claim 1, characterized in that The preparation method of the modified polyether defoamer comprises the following steps: Step A1: At a temperature of 0-10°C, Add it dropwise to the solution of alkenyl polyether while continuously introducing nitrogen to remove HCl. After the addition is complete, heat to 40-60°C and react for 3-5 hours; Step A2: After the reaction is completed, the temperature is lowered to room temperature, and the pH of the system is adjusted to 6-7 using a saturated sodium carbonate solution. The NaCl precipitate is then removed by filtration, and the filtrate is subjected to reduced pressure distillation to remove the solvent, followed by addition of an ethanol-water mixed solvent for recrystallization; Step A3: Add toluene to the product obtained in step A2, raise the temperature to 80-120°C, add hydrogenated silicone oil dropwise, and then add a catalyst to react for 2-6 hours. After the reaction is completed, reduce the temperature to below 60°C, remove the catalyst, and then perform reduced pressure distillation on the solution to remove the solvent to obtain a modified polyether defoamer.

3. The industrial cleaning agent according to claim 2, characterized in that In step A1, the The addition time is 1-2h.

4. The industrial cleaning agent according to claim 2, characterized in that In step A1, the alkenyl polyether is at least one of allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether, and vinyl polyoxyethylene ether.

5. The industrial cleaning agent according to claim 2, characterized in that In step A1, the The molar ratio of the polyol to the alkenyl polyether is 1:1.05-2.

3.

6. The industrial cleaning agent according to claim 2, characterized in that In step A1, the solution of the alkenyl polyether uses at least one of anhydrous dichloromethane, toluene, and tetrahydrofuran as a solvent.

7. The industrial cleaning agent according to claim 6, characterized in that In the solution of the alkenyl polyether, the mass of the solvent is 2-5 times the mass of the alkenyl polyether.

8. The industrial cleaning agent according to claim 2, characterized in that In step A3, the molar ratio of the hydrogenated silicone oil to the alkenyl polyether is 1.05-1.1:

1.

9. A method for preparing the industrial cleaning agent according to any one of claims 1 to 8, characterized in that: The steps include: Step S1: add water to a reaction kettle, add sodium hydroxide, sodium gluconate, sodium secondary alkyl sulfonate and polyol at room temperature, and stir thoroughly for 10-30 minutes; Step S2, adding aminotrimethylenephosphonic acid, glucono-δ-lactone, glycerol, propylene glycol butyl ether and modified polyether defoamer to a reaction kettle at room temperature, and stirring thoroughly until completely dissolved; Step S3: After the reaction is completed, the mixture is naturally cooled to room temperature and allowed to stand for 5-15 minutes to obtain an industrial cleaning agent.

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