An environmentally friendly metal high-efficiency cleaning agent

Abstract

The environmentally friendly metal efficient cleaning agent of the present invention comprises sodium borohydride, sodium dodecylbenzene sulfonate, alcohol ether carboxylate, phytic acid, polymer dispersant, hydrofluoric acid, chelating agent and deionized water. Sodium borohydride is used to decompose micro-nano hydrogen bubbles to completely remove rust from parts, and then sodium metaborate and polymer dispersant are used to improve oil displacement capacity so that oil stains are separated from parts and decomposed, and then boric acid and phytic acid are used to perform rust prevention treatment on parts to avoid secondary oxidation, so as to achieve efficient removal of oil stains and rust on the surface of parts, and avoid the extension of the cycle caused by distribution; in addition, degradable additives with good environmental protection are used to reduce and control the discharge of phosphorus elements to avoid eutrophication of water bodies, and at the same time, metal ions in rust are recycled to achieve efficient and environmentally friendly cleaning process.

Description

Technical Field

[0001] The invention relates to an acid cleaning agent, in particular to an environmentally friendly high-efficiency metal cleaning agent which can effectively take into account the quality of rust and oil removal, avoid excessive corrosion and precision reduction, and is friendly to the environment and operators. Background Art

[0002] As the most commonly used industrial parts, steel metal parts are very susceptible to the influence of the atmospheric environment and corrosion during use due to their relatively active metal materials. Even semi-processed parts have already corroded before subsequent processes such as electroplating or painting, which will affect the quality of surface processing. At this time, metal cleaning agents are often needed to pre-treat the surface. Traditional oil removal and rust removal processes need to be carried out step by step, with large equipment and personnel investment, numerous processes, and a high consumption of water resources. Surfactants often reduce their oil removal ability or the oil displacement ability of bubbles under acidic conditions during use. Problems include the generation of acid mist, which threatens the health of workers and workshop equipment. After the rust is removed, it will produce sedimentation or other iron compounds attached to the parts, resulting in reduced part precision. Traditional pickling processing methods such as high-concentration strong acids such as hydrochloric acid and sulfuric acid are highly corrosive to the human body and can burn the skin.

[0003] Therefore, there is an urgent need for an environmentally friendly and efficient metal cleaning agent that effectively takes into account the quality of rust removal and oil removal, avoids excessive corrosion and reduced precision, and is friendly to the environment and operators. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide an environmentally friendly and efficient metal cleaning agent which effectively takes into account the quality of rust removal and oil removal, avoids excessive corrosion and reduced precision, and is friendly to the environment and operators.

[0005] The present invention discloses an environmentally friendly metal efficient cleaning agent, which is composed of the following materials in parts by weight:

[0006] 3-8 parts of sodium borohydride, 8-16 parts of sodium dodecylbenzene sulfonate, 3-8 parts of alcohol ether carboxylate, 2-10 parts of phytic acid, 3-8 parts of polymer dispersant, 0.5-2 parts of hydrofluoric acid, 0.01-4 parts of complexing agent, and 50-250 parts of deionized water.

[0007] The present invention discloses an environmentally friendly metal efficient cleaning agent, which is composed of the following materials in parts by weight:

[0008] 4-7 parts of sodium borohydride, 10-15 parts of sodium dodecylbenzene sulfonate, 4-7 parts of alcohol ether carboxylate, 6-9 parts of phytic acid, 4-7 parts of polymer dispersant, 0.6-1.5 parts of hydrofluoric acid, 0.05-3 parts of complexing agent, and 60-100 parts of deionized water.

[0009] The present invention discloses an environmentally friendly metal efficient cleaning agent, which is composed of the following materials in parts by weight:

[0010] 5 parts of sodium borohydride, 12 parts of sodium dodecylbenzene sulfonate, 8 parts of alcohol ether carboxylate, 7 parts of phytic acid, 5 parts of polymer dispersant, 0.9 parts of hydrofluoric acid, 0.5 parts of complexing agent, and 80 parts of deionized water.

[0011] The present invention discloses an environmentally friendly metal efficient cleaning agent, and the preparation method thereof comprises:

[0012] Step 1: first add two-thirds of the total amount of deionized water to the reactor, and at 25°C, quickly add phytic acid, hydrofluoric acid, and alcohol ether carboxylate to the reactor according to the mass ratio, and quickly stir during the rapid addition. After each substance is added, stir quickly for 10-20 minutes, let stand for 25-30 minutes, and after all substances are added, stir quickly for 10 minutes, let stand for 10 minutes, and then stir quickly in the opposite direction for 10 minutes, and repeat twice to obtain the first solution;

[0013] Step 2: at 25°C, slowly add sodium borohydride and sodium dodecylbenzene sulfonate to the first agent in the mass ratio in sequence, and slowly stir during the slow addition process. After each substance is added, slowly stir for 30-40 minutes, let stand for 25-30 minutes, and after all substances are added, slowly stir for 20 minutes, let stand for 20 minutes, and then quickly stir in the opposite direction for 20 minutes, and repeat twice to prepare the second agent;

[0014] Step 3: Add the remaining deionized water to the second agent, and quickly add the complexing agent and polymer dispersant at the same time. Slow stirring is also required during the rapid addition process. After each substance is added, stir slowly for 30-40 minutes and let stand for 25-30 minutes. After all substances are added, stir slowly for 30 minutes and let stand at 10°C for 4 hours to prepare the cleaning agent.

[0015] The difference between the environmentally friendly and efficient metal cleaning agent of the present invention and the prior art is that the present invention promotes the decomposition of sodium borohydride to generate sodium metaborate and micro-nano hydrogen bubbles through high-frequency vibration. After the bubbles are generated, they rub and remove rust on the surface of parts under high-frequency vibration; the byproduct sodium metaborate can effectively prevent oil stains from precipitating or adhering to the surface of parts, and it acts as an interface enhancer and synergistically with surfactants to enhance the oil-displacing ability of the bubbles, so that the oil stains are driven away from the surface of the parts to the upper part of the liquid surface more quickly to complete the oil removal; sodium metaborate undergoes a reversible reaction under acidic conditions to generate sodium ions and boric acid, and the boric acid protects the polymer compound by blocking free radicals so that the macromolecular sediment is no longer adsorbed on the surface of the parts, and the boric acid can directly act on the surface of the parts for rust prevention, avoiding secondary oxidation, thereby completing the rust removal, oil removal and rust prevention of the parts in the cleaning agent, compared with the traditional step-by-step process. The method is more efficient in cleaning parts and thus speeding up production; at the same time, sodium dodecylbenzene sulfonate decomposes into sodium bisulfate under high-frequency vibration conditions. Sodium bisulfate can promote the dissolution and effectively slow down the generation of hydrofluoric acid mist. Sodium bisulfate reacts reversibly with hydrofluoric acid in the solution to generate a certain amount of sulfuric acid and sodium fluoride. The phosphorus in phytic acid complexes the iron ions to form stable ferric phosphate. Ferric phosphate can exist in liquid form in sulfuric acid, thereby avoiding re-adherence to the surface of parts. After the treatment is completed, only water needs to be added to dilute the waste liquid or a small amount of nitric acid can be added to re-precipitate the ferric phosphate, thereby removing the phosphorus element in the waste liquid and recovering the iron at the same time, reducing the pollution of water resources or the proliferation of algae caused by the phosphorus element in the waste liquid, reducing the treatment cost of the waste liquid, and recovering the metal elements in the waste liquid through the corresponding circular economy, and making the treated waste liquid more environmentally friendly and more environmentally friendly.

[0016] The following is a further description of an environmentally friendly metal efficient cleaning agent of the present invention in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is a statistical chart of the average weight loss of parts in each group of environmentally friendly and efficient metal cleaning agents;

[0018] Figure 2 It is a statistical chart of the cleaning power of each group of environmentally friendly and efficient metal cleaning agents. DETAILED DESCRIPTION

[0019] The present invention discloses an environmentally friendly metal efficient cleaning agent, which is composed of the following materials in parts by weight:

[0020] 3-8 parts of sodium borohydride, 8-16 parts of sodium dodecylbenzene sulfonate, 3-8 parts of alcohol ether carboxylate, 2-10 parts of phytic acid, 3-8 parts of polymer dispersant, 0.5-2 parts of hydrofluoric acid, 0.01-4 parts of complexing agent, and 50-250 parts of deionized water.

[0021] The difference between the environmentally friendly metal efficient cleaning agent of the present invention and the prior art is that the present invention promotes the decomposition of sodium borohydride to generate sodium metaborate and micro-nano hydrogen bubbles through high-frequency vibration. After the bubbles are generated, the high-frequency vibration is used to rub and remove rust on the surface of the parts with the help of the grinding aid of sodium citrate; the byproduct sodium metaborate can effectively prevent oil stains from precipitating or adhering to the surface of the parts, and it acts as an interface enhancer and synergistically with surfactants to enhance the oil displacement ability of the bubbles, so that the oil stains are driven away from the surface of the parts to the upper part of the liquid surface more quickly to complete the oil removal; sodium metaborate undergoes a reversible reaction under acidic conditions to generate sodium ions and boric acid, and the boric acid blocks free radicals and protects the polymer compound so that the macromolecular sediment is no longer adsorbed on the surface of the parts, and the boric acid can directly act on the surface of the parts for rust prevention, avoiding secondary oxidation, and thus completing the rust removal, oil removal and rust prevention of the parts in the cleaning agent. Compared with the traditional step-by-step method, the parts are cleaned more efficiently and the production is accelerated; As surfactants, alcohol ether carboxylates and sodium dodecylbenzene sulfonate can effectively remove oil stains. At the same time, sodium dodecylbenzene sulfonate decomposes into sodium bisulfate under high-frequency vibration conditions. Sodium bisulfate can promote the dissolution and effectively slow down the generation of hydrofluoric acid mist. Sodium bisulfate reacts reversibly with hydrofluoric acid in the solution to generate a certain amount of sulfuric acid and sodium fluoride. Phosphorus ions in phytic acid complex iron ions under the action of polymer dispersants to form stable ferric phosphate. Ferric phosphate can exist in liquid form in sulfuric acid, thereby avoiding re-attachment to the surface of parts. After the treatment is completed, only water needs to be added to dilute the waste liquid or a small amount of nitric acid can be added to re-precipitate the ferric phosphate, thereby removing the phosphorus element in the waste liquid and recovering the iron, reducing the pollution of water resources or algae caused by the phosphorus element in the waste liquid, reducing the treatment cost of the waste liquid, and recovering the metal elements in the waste liquid through the corresponding circular economy, and making the treated waste liquid more environmentally friendly and more environmentally friendly.

[0022] Among them, the complexing agent is preferably sodium citrate.

[0023] Among them, the polymer dispersant is preferably polyethylene glycol 2000.

[0024] The present invention discloses an environmentally friendly metal efficient cleaning agent, which is composed of the following materials in parts by weight:

[0025] 4-7 parts of sodium borohydride, 10-15 parts of sodium dodecylbenzene sulfonate, 4-7 parts of alcohol ether carboxylate, 6-9 parts of phytic acid, 4-7 parts of polymer dispersant, 0.6-1.5 parts of hydrofluoric acid, 0.05-3 parts of complexing agent, and 60-100 parts of deionized water.

[0026] The present invention reduces the use range of each component material of the detergent by optimizing the above-mentioned component ratio, which is beneficial for each component in the detergent to exert its product performance. At the same time, the synergistic effect between the additive components in the detergent is more obvious due to the optimization of the component ratio.

[0027] The present invention discloses an environmentally friendly metal efficient cleaning agent, which is composed of the following materials in parts by weight:

[0028] 5 parts of sodium borohydride, 12 parts of sodium dodecylbenzene sulfonate, 8 parts of alcohol ether carboxylate, 7 parts of phytic acid, 5 parts of polymer dispersant, 0.9 parts of hydrofluoric acid, 0.5 parts of complexing agent, and 80 parts of deionized water.

[0029] The present invention further optimizes the component ratio to make the dosage of each component material of the cleaning agent more precise. At the same time, thanks to the synergy and compatibility between the additive components in the cleaning agent, the product performance of the cleaning agent is further improved and fully utilized.

[0030] Preferably, the preparation method of the environmentally friendly metal efficient cleaning agent comprises:

[0031] Step 1: first add two-thirds of the total amount of deionized water to the reactor, and at 25°C, quickly add phytic acid, hydrofluoric acid, and alcohol ether carboxylate to the reactor according to the mass ratio, and quickly stir during the rapid addition. After each substance is added, stir quickly for 10-20 minutes, let stand for 25-30 minutes, and after all substances are added, stir quickly for 10 minutes, let stand for 10 minutes, and then stir quickly in the opposite direction for 10 minutes, and repeat twice to obtain the first solution;

[0032] The invention promotes dissolution by rapidly adding substances such as phytic acid, hydrofluoric acid, alcohol ether carboxylate and the like, and simultaneously rapidly stirring during the adding process.

[0033] Wherein, the rotation speed during the rapid stirring is 150-200 r / min.

[0034] Wherein, the dropping speed during the rapid addition is 10 ml / min.

[0035] The reactor used is a 20L frame-type double-layer glass reactor of "Jinfu Brand" model S212.

[0036] Step 2: at 25°C, slowly add sodium borohydride and sodium dodecylbenzene sulfonate to the first agent in the mass ratio in sequence, and slowly stir during the slow addition process. After each substance is added, slowly stir for 30-40 minutes, let stand for 25-30 minutes, and after all substances are added, slowly stir for 20 minutes, let stand for 20 minutes, and then quickly stir in the opposite direction for 20 minutes, and repeat twice to prepare the second agent;

[0037] The invention ensures dissolution by slowly adding sodium borohydride and sodium dodecylbenzene sulfonate, and avoids high rotation speed by intermittent slow stirring, thereby preventing sodium borohydride and sodium dodecylbenzene sulfonate from being decomposed by high-frequency and long-term vibration before use, thereby reducing the cleaning effect of the detergent.

[0038] Wherein, the rotation speed during the rapid stirring is 50-80 r / min.

[0039] Wherein, the dropping speed during the rapid addition is 1-2 drops / s.

[0040] Step 3: Add the remaining deionized water to the second agent, and quickly add the complexing agent and polymer dispersant at the same time. Slow stirring is also required during the rapid addition process. After each substance is added, stir slowly for 30-40 minutes and let stand for 25-30 minutes. After all substances are added, stir slowly for 30 minutes and let stand at 10°C for 4 hours to prepare the cleaning agent.

[0041] The present invention ensures that sodium borohydride and sodium dodecylbenzene sulfonate are not decomposed during the slow stirring process by adding a complexing agent and a polymer dispersant. At the same time, the complexing agent and the polymer dispersant make the structures of sodium borohydride and sodium dodecylbenzene sulfonate more stable in a low-frequency vibration or shaking environment, thereby facilitating the handling and transportation of the detergent.

[0042] Component Analysis:

[0043] Sodium borohydride: It can react slowly with substances containing hydroxyl groups, including water, to release hydrogen, and it hardly reacts under acidic conditions. The loss of sodium borohydride under normal storage conditions is negligible, and vibration is used to accelerate the reaction during use. The sodium borohydride generates sodium metaborate and micro-nano hydrogen bubbles under high-speed vibration. The micro-nano bubbles rub against parts under the action of high-speed vibration to release energy, thereby removing rust on the metal surface. Compared with traditional methods such as grinding or adding silica sol, which are highly destructive to the workpiece, it not only saves the subsequent steps of removing impurities, but also avoids excessive wear of parts or affecting the accuracy of parts. Compared with the use of bubbles that generate carbon dioxide, the nano-level hydrogen bubbles with smaller particle size have a stronger grinding effect and a higher surface polishing degree. Carbon dioxide is oxidizing and will promote metal oxidation, resulting in a reduced rust removal effect, while hydrogen bubbles are reducing and therefore will not oxidize and corrode metals, thereby improving the grinding effect while avoiding secondary oxidation of the metal after rust removal.

[0044] The equation for the decomposition of sodium borohydride under high-frequency vibration is:

[0045] NaBH4+2H2O = NaBO2+4H2 ↑

[0046] Among them, after the hydrogen bubbles rise, they can be collected by a fan and then centrally incinerated.

[0047] Sodium metaborate: As a by-product produced during the vibration process, it has the properties of a wear-resistant agent and a dispersant. It is often used in lubricating oils, oil collection and other fields. It can prevent oil from settling or adhering to the surface of parts. At the same time, it acts as an interface enhancer and synergistically with surfactants to effectively reduce the oil-water cross-sectional tension, thereby allowing stable hydrogen bubbles to form in deeper areas. Different from traditional surfactants that form bubbles by affecting the upper liquid surface and air, the bubbles generated by the solution in the deep area play an oil-displacing role in the process of rising continuously to remove the oil attached to the surface of the parts, so that the bubbles can first remove the rust and then remove the oil from the surface of the parts through oil-displacing properties.

[0048] Boric acid: Sodium metaborate undergoes a reversible reaction under acidic conditions to generate sodium ions and boric acid. Boric acid can act as a thermal oxidation stabilizer and rust inhibitor. When micron-sized hydrogen bubbles are generated and rub against the surface of parts, a large number of free radicals will be generated. These free radicals can cause a chain reaction of polymer degradation, rendering the polymer compounds in the solution ineffective. Boric acid, as a thermal oxidation stabilizer, can effectively block free radicals, thereby protecting the physical structure and chemical properties of the polymer compounds from being changed. At the same time, boric acid can perform rust prevention treatment on the surface of parts, so that the parts can be rust-proofed in the solution after rust removal and degreasing, thus avoiding the occurrence of secondary oxidation.

[0049] Wherein, the reversible reaction equation of the sodium metaborate under acidic conditions is:

[0050] NaBO2+H + +H2O ⇌ Na + +B(OH)3

[0051] Among them, after the hydrogen bubbles rise, they can be collected by a fan and then centrally incinerated.

[0052] Sodium metaborate: As a by-product produced during the vibration process, it has the properties of a wear-resistant agent and a dispersant. It is often used in lubricating oils, oil collection and other fields. It can prevent oil from settling or adhering to the surface of parts. At the same time, it acts as an interface enhancer and synergistically with surfactants to effectively reduce the oil-water cross-sectional tension, thereby allowing stable hydrogen bubbles to form in deeper areas. Different from traditional surfactants that form bubbles by affecting the upper liquid surface and air, the bubbles generated by the solution in the deep area play an oil-displacing role in the process of rising continuously to remove the oil attached to the surface of the parts, so that the bubbles can first remove the rust and then remove the oil from the surface of the parts through oil-displacing properties.

[0053] Boric acid: Sodium metaborate undergoes a reversible reaction under acidic conditions to generate sodium ions and boric acid. Boric acid can act as a thermal oxidation stabilizer and rust inhibitor. When micron-sized hydrogen bubbles are generated and rub against the surface of parts, a large number of free radicals will be generated. These free radicals can cause a chain reaction of polymer degradation, rendering the polymer compounds in the solution ineffective. Boric acid, as a thermal oxidation stabilizer, can effectively block free radicals, thereby protecting the physical structure and chemical properties of the polymer compounds from being changed. At the same time, boric acid can perform rust prevention treatment on the surface of parts, so that the parts can be rust-proofed in the solution after rust removal and degreasing, thus avoiding the occurrence of secondary oxidation.

[0054] Wherein, the reversible reaction equation of the sodium metaborate under acidic conditions is:

[0055] NaBO2+H + +H2O ⇌ Na + +B(OH)3

[0056] Sodium dodecylbenzene sulfonate: As a surfactant, it can enhance the wettability of the surface of parts. As an environmentally friendly and degradable organic penetrant, it is conducive to the uniform distribution of polymer compounds in the solution, helping acids to increase the cleaning speed. At the same time, it decomposes into sodium bisulfate under high-frequency vibration conditions. Sodium bisulfate can promote the dissolution and effectively slow down the generation of hydrofluoric acid mist, which can avoid polluting the atmosphere and achieve environmental protection effects. It is not only beneficial to protect the health of workshop personnel and reduce corrosion to workshop equipment. Compared with the direct addition of sodium bisulfate, the reaction of sodium dodecylbenzene sulfonate is incomplete, so that the remaining sodium dodecylbenzene sulfonate can assist other surfactants to improve the degreasing effect. Sodium bisulfate reacts reversibly with hydrofluoric acid in the solution to generate a certain amount of sulfuric acid and sodium fluoride. Sulfuric acid provides a dissolving environment for the ferric phosphate produced by phytic acid, avoiding the ferric phosphate from adhering to the surface of parts again, realizing the dissolution of iron ions of rust and the conversion of new substances. There are no by-products on the surface of the treated parts, improving the effect of the cleaning agent, and there is no strong acid such as sulfuric acid before formal use, making transportation and storage safer.

[0057] Wherein, the equation for decomposition of the sodium dodecylbenzene sulfonate under high-frequency vibration is:

[0058] 3R12-Ph-SO3Na+H2O → R12-Ph+NaHSO4

[0059] Among them, the equation for the reversible reaction of sodium bisulfate and hydrofluoric acid is:

[0060] HF+NaHSO4 ⇌ H2SO4+NaF

[0061] Phytic acid: As a metal corrosion inhibitor, it can not only cooperate with sodium bisulfate to inhibit the generation of hydrofluoric acid mist, but also cooperate with the anti-rust ability of boric acid to prevent parts from being excessively corroded and affecting the accuracy of parts. It mainly reacts with metal ions, especially with iron ions. It has a strong complexing ability with iron ions. It can quickly remove oxidized iron scale and complex the iron ions in the dissolved rust into more stable ferric phosphate. Since ferric phosphate is insoluble in cold water and nitric acid but soluble in dilute sulfuric acid, it can effectively complex iron ions after sodium dodecylbenzene sulfonate produces sulfuric acid to prevent ferric phosphate from adhering to the surface of parts again. After the treatment is completed, you only need to dilute the waste liquid with water or add a small amount of nitric acid to re-precipitate the ferric phosphate, thereby removing the phosphorus element in the waste liquid and recovering the iron, reducing the pollution of water resources caused by the phosphorus element in the waste liquid or causing algae to proliferate.

[0062] Polyethylene glycol 2000: It specifically forms an adsorption layer on the surface of solid particles, increases the charge on the surface of solid particles, and improves the reaction force between particles that form three-dimensional hindrance. It mainly acts to prevent the sediment particles generated by nano-scale hydrogen bubbles after treating rust from being adsorbed on the surface of parts again; at the same time, a double-layer structure is formed on the surface of solid particles. The polar end of the outer dispersant has a strong affinity with water, which increases the degree of wetting of solid particles by water, promotes the rust particles to be surrounded by the solution, and then accelerates the dissolution of the rust particles in the solution, speeds up rust removal, avoids sedimentation, and helps phytic acid to complex iron ions faster. At the same time, in the process of waste liquid treatment, only cationic polyacrylamide needs to be added to greatly promote the flocculation effect of the former, quickly complete the flocculation and purification of the waste liquid, and achieve environmental protection effects.

[0063] Alcohol ether carboxylate: As a multifunctional anionic surfactant, it can effectively adapt to acidic conditions. Due to the structure of the embedded EO chain, it has a highly efficient synergistic effect with sodium dodecylbenzene sulfonate. It not only has excellent oil removal ability, but also does not cause excessive corrosion to metals. It is mild to human skin and does not contain phosphorus, which is very friendly to the environment. The degradation rate of the OECD verification test is 98%, and it can be completely degraded into carbon dioxide and water in the natural environment.

[0064] Hydrofluoric acid: When the concentration is low, it has weak acidity due to the formation of hydrogen bonds, but when it is concentrated (above 5 mol / L), it will undergo self-ionization and become a strong acid. As one of the acids for auxiliary treatment of rust, it has a strong cleaning ability for iron oxide even in a weak acid state. It can not only remove rust but also react with sodium bisulfate to promote the complexation of iron ions and accelerate the conversion of iron ions, thereby improving the cleaning quality of the surface of parts.

[0065] Sodium citrate: Citrate is environmentally friendly, pollution-free, easy to maintain, has low corrosion, and has certain grinding properties. It can help micro-nano-level hydrogen bubbles to accelerate the treatment of rust and improve the surface processing quality of parts.

[0066] Experimental data

[0067] Now, 600 parts from the same batch of replacements with similar corrosion and rust levels are selected and divided into 6 groups, each with 100 parts. The artificial oil stains are treated with N46HL hydraulic oil according to the national standard. Each kilogram of cleaning agent is used to clean 10 square meters of surfaces with oil stains and rust. The control group and the embodiment group are used for cleaning, respectively. The experimental data are as follows:

[0068] The preparation method of the cleaning agent used in the control group 1 is:

[0069] Step 1: first add two-thirds of the total amount of deionized water to the reactor, and at 25°C, quickly add phytic acid, hydrofluoric acid, and alcohol ether carboxylate to the reactor according to the mass ratio, and quickly stir during the rapid addition. After each substance is added, stir quickly for 10-20 minutes, let stand for 25-30 minutes, and after all substances are added, stir quickly for 10 minutes, let stand for 10 minutes, and then stir quickly in the opposite direction for 10 minutes, and repeat twice to obtain the first solution;

[0070] Step 2: at 25°C, add sodium borohydride and sodium dodecylbenzene sulfonate to the first agent in the mass ratio in sequence, and stir rapidly during the slow and rapid addition. After each substance is added, stir rapidly for 30-40 minutes, let stand for 25-30 minutes, and after all substances are added, stir rapidly for 20 minutes, let stand for 20 minutes, and then stir rapidly in the opposite direction for 20 minutes. Repeat twice to obtain the second agent.

[0071] Step 3: Add the remaining deionized water to the second agent, and quickly add the complexing agent and polymer dispersant at the same time. Rapid stirring is also required during the rapid addition process. After each substance is added, stir quickly for 30-40 minutes and let stand for 25-30 minutes. After all substances are added, stir quickly for 30 minutes and let stand at 10°C for 4 hours to prepare the cleaning agent.

[0072] The preparation methods of the cleaning agents used in the control groups 2 and 3 and the example groups are:

[0073] Step 1: first add two-thirds of the total amount of deionized water to the reactor, and at 25°C, quickly add phytic acid, hydrofluoric acid, and alcohol ether carboxylate to the reactor according to the mass ratio, and quickly stir during the rapid addition. After each substance is added, stir quickly for 10-20 minutes, let stand for 25-30 minutes, and after all substances are added, stir quickly for 10 minutes, let stand for 10 minutes, and then stir quickly in the opposite direction for 10 minutes, and repeat twice to obtain the first solution;

[0074] Step 2: at 25°C, slowly add sodium borohydride and sodium dodecylbenzene sulfonate to the first agent in the mass ratio in sequence, and slowly stir during the slow addition process. After each substance is added, slowly stir for 30-40 minutes, let stand for 25-30 minutes, and after all substances are added, slowly stir for 20 minutes, let stand for 20 minutes, and then quickly stir in the opposite direction for 20 minutes, and repeat twice to prepare the second agent;

[0075] Step 3: Add the remaining deionized water to the second agent, and quickly add the complexing agent and polymer dispersant at the same time. Slow stirring is also required during the rapid addition process. After each substance is added, stir slowly for 30-40 minutes and let stand for 25-30 minutes. After all substances are added, stir slowly for 30 minutes and let stand at 10°C for 4 hours to prepare the cleaning agent.

[0076] Control group 1: 4 parts of sodium borohydride, 10 parts of sodium dodecylbenzene sulfonate, 4 parts of alcohol ether carboxylate, 6 parts of phytic acid, 4 parts of polymer dispersant, 0.6 parts of hydrofluoric acid, 0.05 parts of complexing agent, and 60 parts of deionized water.

[0077] Immerse the parts with oil and rust in the working fluid for 15 minutes, rinse the workpieces twice with clean water, and then dry the workpieces with 50°C hot water to complete the cleaning. Visually, the surface of the workpiece is clean, and the water film evenly covers the surface of the workpiece. The number of parts with a metal corrosion level higher than zero is 4, the average weight loss ratio of the parts is 2.4%, the number of parts with rust spots is 9, and the cleaning power is 78%.

[0078] Control group 2: 8 parts of sodium borohydride, 16 parts of sodium dodecylbenzene sulfonate, 8 parts of alcohol ether carboxylate, 1 part of phytic acid, 8 parts of polymer dispersant, 2 parts of hydrofluoric acid, 4 parts of complexing agent, and 250 parts of deionized water.

[0079] Immerse the parts with oil and rust in the working fluid for 15 minutes, rinse the workpieces twice with clean water, and then dry the workpieces with 50°C hot water to complete the cleaning. Visually, the surface of the workpiece is clean, the water film evenly covers the surface of the workpiece, the number of parts with metal corrosion level higher than zero is 6, the average weight loss ratio of the parts is 4.1%, the number of parts with rust spots is 0, and the cleaning power is 85%.

[0080] Control group 3: 8 parts of sodium borohydride, 5 parts of sodium dodecylbenzene sulfonate, 8 parts of alcohol ether carboxylate, 10 parts of phytic acid, 8 parts of polymer dispersant, 2 parts of hydrofluoric acid, 4 parts of complexing agent, and 250 parts of deionized water.

[0081] Immerse the parts with oil and rust in the working fluid for 15 minutes, rinse the workpieces twice with clean water, and then dry the workpieces with 50°C hot water to complete the cleaning. Visually, the surface of the workpiece is clean, the water film evenly covers the surface of the workpiece, the number of parts with metal corrosion level higher than zero level is 3, the average weight loss ratio of the parts is 2.1%, the number of parts with rust spots is 6, and the cleaning power is 81%.

[0082] Example group, Example 1: 8 parts of sodium borohydride, 16 parts of sodium dodecylbenzene sulfonate, 8 parts of alcohol ether carboxylate, 10 parts of phytic acid, 8 parts of polymer dispersant, 2 parts of hydrofluoric acid, 4 parts of complexing agent, and 250 parts of deionized water.

[0083] Immerse the parts with oil and rust in the working fluid for 15 minutes, rinse the workpieces twice with clean water, and then dry the workpieces with 50°C hot water to complete the cleaning. Visually, the surface of the workpiece is clean, the water film evenly covers the surface of the workpiece, the number of parts with metal corrosion level higher than zero level is 2, the average weight loss ratio of the parts is 1.6%, the number of parts with rust spots is 1, and the cleaning power is 86%.

[0084] Example 2: 3 parts of sodium borohydride, 8 parts of sodium dodecylbenzene sulfonate, 3 parts of alcohol ether carboxylate, 2 parts of phytic acid, 3 parts of polymer dispersant, 0.5 parts of hydrofluoric acid, 0.01 parts of complexing agent, and 50 parts of deionized water.

[0085] Immerse the parts with oil and rust in the working fluid for 15 minutes, rinse the workpieces twice with clean water, and then dry the workpieces with 50°C hot water to complete the cleaning. Visually inspect the surface of the workpiece to be clean, the water film evenly covers the surface of the workpiece, the number of parts with a metal corrosion level higher than zero is 1, the average weight loss ratio of the parts is 1.3%, the number of parts with rust spots is 1, and the cleaning power is 88%.

[0086] Example 3: 5 parts of sodium borohydride, 12 parts of sodium dodecylbenzene sulfonate, 8 parts of alcohol ether carboxylate, 7 parts of phytic acid, 5 parts of polymer dispersant, 0.9 parts of hydrofluoric acid, 0.5 parts of complexing agent, and 80 parts of deionized water.

[0087] Immerse the parts with oil and rust in the working fluid for 15 minutes, rinse the workpieces twice with clean water, and then dry the workpieces with 50°C hot water to complete the cleaning. Visually, the surface of the workpiece is clean, the water film evenly covers the surface of the workpiece, the number of parts with metal corrosion level higher than zero is 0, the average weight loss ratio of the parts is 1.2%, the number of parts with rust spots is 0, and the cleaning power is 89%.

[0088] Data analysis

[0089] The specific experimental data of each group are shown in Table 1 below:

[0090]

[0091] Table 1

[0092] See also Figure 1 , 2 , It can be seen from the above experimental data that, in the control groups 2, 3 and the embodiment group in Table 1, the control group 2 has too little phytic acid content, resulting in a decrease in the degree of over-corrosion protection of the parts, which in turn significantly increases the number of parts with a metal corrosion level higher than level zero and the average weight loss ratio of the parts compared with other groups; the control group 3 has too little sodium dodecylbenzene sulfonate content, resulting in a significant decrease in the cleaning power of the parts relative to the control group 2 and the embodiment group. In addition, due to the small amount of sulfuric acid generated by sodium dodecylbenzene sulfonate, the ferric phosphate in the solution cannot be dissolved and adsorbed on the surface of the parts in time, resulting in a large number of parts with rust spots; and the control group 1 uses a method of rapid addition and rapid stirring when adding sodium borohydride and sodium dodecylbenzene sulfonate, resulting in a large amount of decomposition of the two before formal use, resulting in a decrease in rust removal ability and cleaning power; compared with the control group, the embodiment group not only effectively improves the cleaning power of oil stains under the same conditions and environment, see Figure 2, the cleaning power of Example 3 exceeds the national standard Q / CR468-2015 by nine percentage points, which can effectively remove the oil stains on the parts and facilitate subsequent processing. In terms of the degree of rust removal and the degree of protection of the precision of the parts, the number of parts with a metal corrosion level higher than zero in Example 3 is 0 and the number of parts with rust spots is also 0, that is, through the ratio, it can be achieved that the precision of the parts is effectively guaranteed to be intact on the basis of ensuring the removal of rust, which is more conducive to the multiple applications of the parts, and the average weight loss ratio is 1.2%, which is less than 2% specified in Q / CR468-2015. It can be concluded from Table 2 that Example 3 meets the industry standards in multiple indicators. Example 3 comprehensively removes rust from parts at the micro-nano level with hydrogen bubbles, then improves the oil displacement capacity through sodium metaborate and polymer dispersants to make the oil stains separate from the parts and decompose, and then performs rust prevention treatment on the parts through boric acid and phytic acid to avoid secondary oxidation to achieve efficient removal of oil stains and rust on the surface of the parts, avoiding the extension of the cycle caused by the distribution. At the same time, the polymer dispersant polyethylene glycol 2000 in the detergent only needs to add cationic polyacrylamide to the waste liquid during the waste liquid treatment process to greatly promote the flocculation effect of the former, quickly complete the flocculation and purification of the waste liquid to meet the discharge standard; while the alcohol ether carboxylate is warm to human skin and does not contain phosphorus, which is very friendly to the environment. The degradation rate of the OECD verification test is 98%, and it can be completely degraded into carbon dioxide and water in the natural environment. At the same time, the phosphorus ions in the phytic acid complex the iron ions in the rust to form a stable ferric phosphate. Sodium dodecylbenzene sulfonate provides sulfuric acid solution for ferric phosphate through the reaction, so that the ferric phosphate obtains an environment in which it exists in a liquid state in the solution, avoiding the iron ions from attaching to the parts again and causing secondary oxidation. For the waste liquid containing sulfuric acid and ferric phosphate, the ferric phosphate can be re-precipitated by adding nitric acid or diluting. At this point, the recovery of iron elements is completed and can be reused for the second time. The precipitation treatment of phosphorus elements is conducive to the subsequent environmentally friendly discharge of waste liquid, avoiding the eutrophication of water bodies caused by excessive phosphorus content in the waste liquid.

[0093] The industry standards and test results of Example 3 are shown in Table 2 below:

[0094]

[0095] Table 2

[0096] The embodiments described above are merely descriptions of preferred implementation modes of the present invention and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.

Claims

1. An environmentally friendly metal efficient cleaning agent, characterized in that: It is composed of the following materials by weight: 3-8 parts of sodium borohydride, 8-16 parts of sodium dodecylbenzene sulfonate, 3-8 parts of alcohol ether carboxylate, 2-10 parts of phytic acid, 3-8 parts of polymer dispersant, 0.5-2 parts of hydrofluoric acid, 0.01-4 parts of complexing agent, 50-250 parts of deionized water; The environmentally friendly metal efficient cleaning agent is prepared as follows: Step 1: First, add two-thirds of the total amount of deionized water to the reactor. At 25°C, quickly add phytic acid, hydrofluoric acid, and alcohol ether carboxylate to the reactor according to the mass ratio. Rapid stirring is also required during the rapid addition process. After each substance is added, stir rapidly for 10-20 minutes and let stand for 25-30 minutes. After all substances are added, stir rapidly for 10 minutes, let stand for 10 minutes, and then stir rapidly in the opposite direction for 10 minutes. Repeat twice to prepare the first agent. Step 2: at 25°C, slowly add sodium borohydride and sodium dodecylbenzene sulfonate to the first agent in the mass ratio in sequence, and slowly stir during the slow addition process. After each substance is added, slowly stir for 30-40 minutes, let stand for 25-30 minutes, and after all substances are added, slowly stir for 20 minutes, let stand for 20 minutes, and then quickly stir in the opposite direction for 20 minutes, and repeat twice to prepare the second agent; Step 3: Add the remaining deionized water to the second agent, and quickly add the complexing agent and the polymer dispersant at the same time. Slow stirring is also required during the rapid addition process. After each substance is added, stir slowly for 30-40 minutes and let stand for 25-30 minutes. After all substances are added, stir slowly for 30 minutes and let stand at 10°C for 4 hours to obtain an environmentally friendly and efficient metal cleaning agent.

2. An environmentally friendly metal efficient cleaning agent according to claim 1, characterized in that: It is composed of the following materials by weight: 4-7 parts of sodium borohydride, 10-15 parts of sodium dodecylbenzene sulfonate, 4-7 parts of alcohol ether carboxylate, 6-9 parts of phytic acid, 4-7 parts of polymer dispersant, 0.6-1.5 parts of hydrofluoric acid, 0.05-3 parts of complexing agent, and 60-100 parts of deionized water.

3. An environmentally friendly metal efficient cleaning agent according to claim 2, characterized in that: It is composed of the following materials by weight: 5 parts of sodium borohydride, 12 parts of sodium dodecylbenzene sulfonate, 8 parts of alcohol ether carboxylate, 7 parts of phytic acid, 5 parts of polymer dispersant, 0.9 parts of hydrofluoric acid, 0.5 parts of complexing agent, and 80 parts of deionized water.

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