Fluoride-free cleaning agent suitable for aluminum ring-pull cans as well as preparation method and application of fluoride-free cleaning agent

Abstract

The invention discloses a fluoride-free cleaning agent suitable for an aluminum ring-pull can as well as a preparation method and application of the fluoride-free cleaning agent. The fluoride-free cleaning agent comprises the following components in percentage by weight: 30-50wt% of pure water; 2-5 wt% of ferrous sulfate; 40-60 wt% of 75% sulfuric acid; 0.1-1 wt% of 35% hydrogen peroxide; 5 to 10 wt% of a surfactant; 0.1 to 1 wt% of sodium bromide; wherein the surfactant at least comprises alkylphenol polyoxyethylene ether and fatty alcohol-polyoxyethylene ether, and the mass ratio of the alkylphenol polyoxyethylene ether to the fatty alcohol-polyoxyethylene ether is (7: 3)-(6: 4). The fluoride-free cleaning agent provided by the invention can provide an excellent cleaning effect at a lower cleaning temperature, achieves a cleaning level equivalent to that of a fluorine-containing cleaning agent, reduces the wastewater treatment cost and reduces potential pollution to soil and water due to the fact that the cleaning agent does not contain fluorine, and in addition, the fluorine-free cleaning agent has a good application prospect. Ferrous sulfate is added into the formula, and the use amount of an inorganic flocculant in wastewater treatment is reduced, so that the cleaning cost is greatly reduced, and the cleaning agent has huge advantages when being used for replacing a fluorine-containing cleaning agent.

Description

Technical Field

[0001] The present invention relates to the technical field of fluorine-free cleaning agents. More specifically, it relates to a fluorine-free cleaning agent suitable for aluminum cans of aluminum materials, its preparation method and application. Background Art

[0002] Metal profiles have been extremely widely used in all walks of life due to their excellent durability, outstanding decorative properties, and good processing formability. Among the various metal profiles, aluminum materials are particularly noticeable. Aluminum materials have many commendable properties. For example, its processing performance is very excellent. Whether it is stretching, bending or stamping and other processing operations, aluminum materials can easily handle them and can accurately achieve the shape and specifications required by the production process. In addition, aluminum materials are light in weight, and this property makes it stand out in many application scenarios with weight requirements and become an ideal material choice. In terms of the current usage of metal profiles, the usage ratio of aluminum materials exceeds 80%, which undoubtedly establishes the pivotal position of aluminum materials in the field of metal profiles.

[0003] In the use of aluminum materials, special mention should be made of the aluminum cans used for canned beverages and beer, which largely adopt aluminum materials. The number of aluminum cans used in the market is numerous and they are colorful. These colorful and gorgeous aluminum cans are filled on the shelves of shopping malls and small shops on the street. Each of their unique colors and designs seems to be telling different brand stories to people, fully meeting the growing pursuit of product diversification and personalization by people. For the aluminum can manufacturing industry, in order to ensure that high-quality aluminum can products can be obtained, it is an indispensable link to perform necessary surface cleaning treatment on the aluminum cans before the process of coating ink. Among the many cleaning processes, the use of fluorine-containing cleaning agents is the most common pre-treatment cleaning method. Since fluorine-containing cleaning agents can often effectively remove the oil stains, dust and some other impurities on the surface of aluminum cans during the cleaning process, thus providing a relatively clean surface for the subsequent ink coating, and to a certain extent ensuring the good adhesion between the ink and the surface of the aluminum cans.

[0004] However, we must also clearly realize that the harm caused by fluorine should not be underestimated. Fluorine can easily cause serious harm to the entire ecological environment and human health. From an environmental perspective, when fluorine-containing cleaning agents enter the environmental system after use, the fluorine they contain may accumulate in the soil. Over time, the fluorine content in the soil increases until it affects the fertility and structure of the soil, destroys the living environment of microorganisms in the soil, and then affects the growth of crops and the balance of the ecosystem. In terms of water bodies, if fluorine-containing wastewater is discharged into natural water bodies without proper treatment, fluorine may have adverse effects on the physiological functions of aquatic organisms, change the chemical properties of the water body, and pose a potential threat to the entire water ecological environment. As for human health, excessive intake of fluorine may cause health problems such as dental fluorosis and skeletal fluorosis, which seriously affect people's quality of life and physical health. Therefore, in order to protect the environment and human health, the use of fluorine in the cleaning process must be limited or even completely eliminated.

[0005] Under this circumstance, fluorine-free cleaning pretreatment technology came into being. This technology is a very environmentally friendly treatment method. It is like a bridge between environmental pollution control and sustainable development of the manufacturing industry, perfectly combining production needs and environmental protection requirements. Fluorine-free cleaning pretreatment technology can replace the traditional fluorine-containing cleaning agent treatment process and can be well applied in the pretreatment process of cans. In the actual operation process, fluorine-free cleaning agents can also effectively remove dirt on the surface of cans through a special chemical action mechanism, providing a good basic surface for the ink coating process, and will not introduce the various hazards caused by the fluorine element, thereby achieving the dual goals of clean production and environmental protection.

[0006] In view of this, in order to meet environmental protection requirements, it is very important for both social environment and human health to develop a new fluorine-free cleaning agent for aluminum substrate cans. Summary of the invention

[0007] In order to solve the problems existing in the prior art, the first object of the present invention is to provide a fluorine-free cleaning agent suitable for aluminum cans.

[0008] The second object of the present invention is to provide a method for preparing the fluorine-free cleaning agent as described above.

[0009] The third object of the present invention is to provide a fluorine-free cleaning agent for use in the pre-treatment cleaning of aluminum cans.

[0010] In order to achieve the above first object, the present invention adopts the following technical scheme:

[0011] The present invention provides a fluorine-free cleaning agent suitable for aluminum cans, comprising the following components in percentage by weight:

[0012]

[0013] Among them, the surfactant at least includes alkylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether, and the mass ratio of alkylphenol polyoxyethylene ether to fatty alcohol polyoxyethylene ether is 7:3 to 6:4.

[0014] Furthermore, the fluoride-free cleaning agent includes the following components in weight percentages:

[0015]

[0016] Furthermore, the alkylphenol polyoxyethylene ether is selected from the non-ionic surfactant TX-10.

[0017] Furthermore, the fatty alcohol polyoxyethylene ether is selected from the non-ionic surfactant AEO-9.

[0018] Furthermore, the alkylphenol polyoxyethylene ether is selected from TX-10 of German Ham Company.

[0019] Furthermore, the fatty alcohol polyoxyethylene ether is selected from AEO-9 of Nanjing Gutian Company.

[0020] To achieve the above second object, the present invention adopts the following technical solution:

[0021] The present invention provides a preparation method for preparing the fluoride-free cleaning agent as described above, including the following steps:

[0022] Add pure water, ferrous sulfate and 75% sulfuric acid in sequence under stirring, and after all are dissolved, heat up to 50 - 60 °C;

[0023] Continue to add 35% hydrogen peroxide, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether and sodium bromide, and after stirring evenly, it is obtained.

[0024] To achieve the above third object, the present invention adopts the following technical solution:

[0025] The present invention provides an application of the fluoride-free cleaning agent as described above in the pre-treatment cleaning of aluminum cans.

[0026] Furthermore, the application specifically is: at a pre-cleaning temperature of 25 - 30 °C and a main cleaning temperature of 60 - 65 °C, perform on-line cleaning on aluminum cans, and the cleaning speed is 2450 - 2500 cans / min.

[0027] Furthermore, during the wastewater treatment process of on-line cleaning, 0.25 - 0.27 kg of inorganic flocculant is consumed per ton of wastewater.

[0028] The beneficial effects of the present invention are as follows:

[0029] The present invention provides a fluorine-free cleaning agent suitable for aluminum beverage cans. This fluorine-free cleaning agent has a high cleaning speed, and the cleaning effect can reach the level equivalent to that of commercially available fluorine-containing cleaning agents, thus completely solving the harm of fluorine-containing cleaning agents to the ecological environment and human health, making it have great advantages in replacing fluorine-containing cleaning agents. Moreover, the fluorine-free cleaning agent can well match the current cleaning pipeline for aluminum beverage cans. It is found that on a cleaning machine production line running continuously for 24 hours, the cleaning speed can reach 2450 - 2500 cans / min, and the consumption of inorganic flocculants in wastewater treatment is also significantly reduced, with 0.25 - 0.27 kg of inorganic flocculants consumed per ton of wastewater.

[0030] By introducing two types of non-ionic surfactants into the formula of the fluorine-free cleaning agent and using them in combination, it is beneficial to remove different oil stains on the surface of aluminum beverage cans and efficiently improve the cleaning speed.

[0031] By introducing ferrous sulfate into the formula of the fluorine-free cleaning agent, the etching reaction of aluminum can be catalyzed in an acidic environment, enabling recycling. At the same time, it can also reduce the consumption of inorganic flocculants in the wastewater treatment process, thereby reducing the cleaning cost.

[0032] By introducing sodium bromide into the formula of the fluorine-free cleaning agent, the chemical stability of the fluorine-free cleaning agent during storage and use can be effectively improved, and the cleaning activity can be maintained. Brief Description of the Drawings

[0033] Figure 1 Shows the water film photos taken when the fluorine-free cleaning agents prepared in Examples 11 - 15 are used for cleaning experiments after being prepared for 1 month.

[0034] Figure 2 Shows the water film photos taken when the commercially available fluorine-containing cleaning agent in Comparative Example 5 is used for cleaning experiments after being prepared for 1 month. Detailed Description of the Invention

[0035] To more clearly illustrate the present invention, the present invention will be further described below in conjunction with preferred embodiments and the drawings. Those skilled in the art should understand that the content specifically described below is illustrative rather than restrictive, and should not be used to limit the protection scope of the present invention.

[0036] In addition, unless otherwise specified, the raw materials used in the present invention can be obtained through commercial purchase. Any range described in the present invention includes the end values and any numerical value between the end values, as well as any sub-range composed of any numerical value between the end values or the end values.

[0037] From an environmental protection perspective, the present invention aims to develop a fluorine-free cleaning agent suitable for aluminum cans in order to address the potential harm to the ecological environment and human health posed by currently commercially available fluorine-containing cleaning agents. The fluorine-free cleaning agent comprises the following components in weight percentages:

[0038]

[0039] Among them, the surfactant at least comprises alkylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether, and the mass ratio of alkylphenol polyoxyethylene ether to fatty alcohol polyoxyethylene ether is 7:3 to 6:4.

[0040] In the above formula, the surfactant mainly plays a role in cleaning grease. When the two non-ionic surfactants, alkylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether, are used in combination, their cleaning effect is better than that of using them alone. They can remove different oil stains on the surface of aluminum cans, efficiently improve the cleaning speed, and their mass ratio can be 7:3, 7:4, 6:3, 6:4, etc. In a specific embodiment, the alkylphenol polyoxyethylene ether is selected from the non-ionic surfactant TX-10, and the fatty alcohol polyoxyethylene ether is selected from the non-ionic surfactant AEO-9. After screening non-ionic surfactants TX-10 and AEO-9 from different manufacturers, the non-ionic surfactant TX-10 is preferably the TX-10 product of German Ham Company, and the non-ionic surfactant AEO-9 is preferably the AEO-9 product of Nanjing Gutian Company.

[0041] Ferrous sulfate in the formula mainly plays a role in catalytic etching. The reason for this role is that ferrous sulfate can react with hydrogen peroxide under acidic conditions to generate Fe 3+ , and the generated Fe 3+ also participates in the etching reaction of aluminum. After the etching reaction, Fe 3+ is reduced to Fe 2+ , realizing recycling. In order to ensure the etching effect, the weight percentage of ferrous sulfate in the fluorine-free cleaning agent should be controlled at 2-5 wt%. If the addition amount of ferrous sulfate is too low (<2%), it will affect the etching amount of the aluminum can body during the cleaning process; if the addition amount of ferrous sulfate is too high (>5%), on the one hand, it will cause high etching loss of the aluminum can and the problem of over-etching, and on the other hand, it will also affect the cost.

[0042] Sodium bromide can play a role in inhibiting oxidation reactions, preventing the active ingredients in the cleaning agent from becoming ineffective during storage or use, thereby extending the service life of the cleaning agent and maintaining its activity. This effect is specifically reflected in that the active ingredients in the cleaning agent (such as hydrogen peroxide) are easily catalytically decomposed by metal ions (Fe 2+ ), and sodium bromide can fix Fe 2+ through complexation., to protect hydrogen peroxide from being rapidly consumed. At the same time, the free radicals generated during the decomposition of active ingredients (such as hydrogen peroxide) will trigger a chain reaction, attacking other ingredients (such as the hydrocarbon chain of surfactant TX-10), resulting in its oxidative degradation, while Br - can react with free radicals to generate bromine free radicals with lower activity, blocking the chain propagation and maintaining the emulsifying and penetrating functions of the surfactant. Therefore, sodium bromide systematically blocks the oxidation reaction chain through the mechanisms of complexing metal ions and scavenging free radicals, thereby protecting active ingredients such as hydrogen peroxide and surfactant to maintain chemical stability during storage and use. In addition, sodium bromide also has a certain bactericidal effect. In a specific embodiment, the weight percentage of the sodium bromide in the fluoride-free cleaning agent is controlled at 0.1-1 wt%. If the proportion is too low, it will affect the storage stability and fail to achieve the effect of inhibiting the oxidation reaction. The cleaning effect will be reduced after a long storage time. If the proportion is too high, it will affect the cost.

[0043] The present invention also exemplarily provides a preparation method of the fluoride-free cleaning agent as described above, including the following steps:

[0044] (1) Add pure water into the drawing tank, start the disperser, adjust the rotation speed from slow to fast, and finally control the rotation speed at 500 revolutions per minute;

[0045] (2) Add ferrous sulfate under stirring. After all the ferrous sulfate is dissolved and the solution is visually clear and transparent, continue stirring for 5 minutes;

[0046] (3) Add 75% sulfuric acid under stirring. After all the 75% sulfuric acid is dissolved and the solution is visually clear and transparent, continue stirring for 5 minutes;

[0047] (4) Raise the temperature to 50°C - 60°C and maintain the temperature;

[0048] (5) Slowly add 35% hydrogen peroxide under stirring. After all the 35% hydrogen peroxide is dissolved and the solution is visually clear and transparent, continue stirring for 1 hour;

[0049] (6) Add surfactants (i.e., alkylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether) under stirring. After all the surfactants are miscible and the solution is visually clear and transparent, continue stirring for 30 minutes;

[0050] (7) Add sodium bromide under stirring. After all the sodium bromide is dissolved and the solution is visually clear and transparent, continue stirring for 5 minutes to obtain.

[0051] The technical solutions of the present invention will be further described below in conjunction with specific embodiments.

[0052] Surfactant screening

[0053] Examples 1-10

[0054] This example provides a fluorine-free cleaning agent, which is composed of the following components by weight percentage:

[0055]

[0056] Wherein, the surfactant formula is prepared according to the following Table 1.

[0057] Table 1 (parts by mass)

[0058]

[0059] Note: The cleaning effect is determined by cleaning the surface of the aluminum can at a main cleaning temperature of 60°C and visually inspecting the water film after cleaning.

[0060] The following is an exemplary method for producing a fluorine-free cleaning agent, comprising the following steps:

[0061] (1) Add pure water into the pull cylinder, start the disperser, adjust the speed from slow to fast, and finally control the speed at 500 rpm;

[0062] (2) Add ferrous sulfate while stirring, and continue stirring for 5 minutes after the ferrous sulfate is completely dissolved and the solution becomes clear and transparent;

[0063] (3) Add 75% sulfuric acid while stirring, and continue stirring for 5 minutes after the 75% sulfuric acid is completely dissolved and the solution becomes clear and transparent;

[0064] (4) Raise the temperature to 50°C to 60°C and maintain the temperature;

[0065] (5) Slowly add 35% hydrogen peroxide while stirring, and continue stirring for 1 hour after the 35% hydrogen peroxide is completely dissolved and the solution becomes clear and transparent visually;

[0066] (6) adding a surfactant (i.e., alkylphenol polyoxyethylene ether and / or fatty alcohol polyoxyethylene ether) under stirring, and continuing stirring for 30 minutes after the surfactant is completely dissolved and the solution is visually clear and transparent;

[0067] (7) Add sodium bromide while stirring, and continue stirring for 5 minutes after the sodium bromide is completely dissolved and the solution becomes clear and transparent.

[0068] The fluorine-free cleaning agent was respectively formulated into a cleaning agent bath solution with a free acid value of 17. The same aluminum cans were used for soaking and shaking cleaning (the main cleaning temperature was 60 °C). After 1 minute, they were taken out and cleaned with pure water, and the cleaning effect was observed. Among them, the free acid value was detected according to the following steps: 1) Accurately pipette 10 ml of the cleaning agent bath solution into a conical flask with a pipette; 2) Add 5 drops of phenolphthalein indicator, and then add about 2 g of NaF, and shake to dissolve it; 3) Titrate the above solution with 0.1 N NaOH standard solution until it turns light pink. At this time, the number of milliliters of 0.1 N NaOH standard solution consumed is the free acid value.

[0069] After the preliminary screening of surfactants, it was finally determined to use the combination of TX-10 from German Ham Company and AEO-9 from Nanjing Gutian Company in a mass ratio of 7:3 for subsequent research.

[0070] Example 11

[0071] This example provides a fluorine-free cleaning agent, which is composed of the following components by weight percentage:

[0072]

[0073] Among them, the surfactant is selected from the mixture of TX-10 brand from German Ham Company and AEO-9 brand from Nanjing Gutian Company, and their mass ratio is 7:3.

[0074] The production method of the fluorine-free cleaning agent is the same as that of Example 1.

[0075] Example 12

[0076] This example provides a fluorine-free cleaning agent, which is composed of the following components by weight percentage:

[0077]

[0078] Among them, the surfactant is selected from the mixture of TX-10 brand from German Ham Company and AEO-9 brand from Nanjing Gutian Company, and their mass ratio is 7:3.

[0079] The production method of the fluorine-free cleaning agent is the same as that of Example 1.

[0080] Example 13

[0081] This example provides a fluorine-free cleaning agent, which is composed of the following components by weight percentage:

[0082]

[0083] Among them, the surfactant is selected from the mixture of TX-10 brand from German Ham Company and AEO-9 brand from Nanjing Gutian Company, and their mass ratio is 7:3.

[0084] The production method of the fluorine-free cleaning agent is the same as that of Example 1.

[0085] Example 14

[0086] This example provides a fluorine-free cleaning agent, which is composed of the following components by weight percentage:

[0087]

[0088] Among them, the surfactant is selected from the mixture of the TX-10 brand of German Ham Company and the AEO-9 brand of Nanjing Gutian Company, and the mass ratio is 7:3.

[0089] The production method of the fluorine-free cleaning agent is the same as that of Example 1.

[0090] Example 15

[0091] This example provides a fluorine-free cleaning agent, which is composed of the following components by weight percentage:

[0092]

[0093] Among them, the surfactant is selected from the mixture of the TX-10 brand of German Ham Company and the AEO-9 brand of Nanjing Gutian Company, and the mass ratio is 7:3.

[0094] The production method of the fluorine-free cleaning agent is the same as that of Example 1.

[0095] Comparative Example 1

[0096] Compared with Example 11, the only difference is that ferrous sulfate is not added, and the lack of ferrous sulfate is made up with water. The specific formula is as follows:

[0097]

[0098] Among them, the surfactant is selected from the mixture of the TX-10 brand of German Ham Company and the AEO-9 brand of Nanjing Gutian Company, and the mass ratio is 7:3.

[0099] Comparative Example 2

[0100] Compared with Example 11, the only difference is that the dosage of ferrous sulfate is adjusted to 1 wt%, and the specific formula is as follows:

[0101]

[0102]

[0103] Among them, the surfactant is selected from the mixture of the TX-10 brand of German Ham Company and the AEO-9 brand of Nanjing Gutian Company, and the mass ratio is 7:3.

[0104] Comparative Example 3

[0105] Compared with Example 11, the difference is only that the dosage of ferrous sulfate is adjusted to 5.1 wt%, and the specific formulation is as follows:

[0106]

[0107] Among them, the surfactant is selected from the mixture of TX-10 brand of German Ham Company and AEO-9 brand of Nanjing Gutian Company, and the mass ratio is 7:3.

[0108] Comparative Example 4

[0109] Compared with Example 11, the difference is only that sodium bromide is not added, and the specific formulation is as follows:

[0110]

[0111] Among them, the surfactant is selected from the mixture of TX-10 brand of German Ham Company and AEO-9 brand of Nanjing Gutian Company, and the mass ratio is 7:3.

[0112] Comparative Example 5

[0113] The commercially available fluorine-containing cleaning agent SCL NHC260 was used as a comparison.

[0114] Performance Test

[0115] Laboratory stage data

[0116] The cleaning agents of the above Examples 11-15 and Comparative Examples 1-5 were subjected to a cleaning test. The cleaning steps were the same as those in Example 1, except that the main cleaning temperature was adjusted to 65 °C.

[0117] 1) Observe the integrity of the surface water film and evaluate the cleaning effect. If the surface water film does not spread evenly, it proves that the cleaning is unqualified. Repeat the above cleaning process after storing for one month and observe the cleaning effect.

[0118] 2) Etching amount test process: The fluorine-free cleaning agent was respectively configured into a cleaning agent bath solution with a free acid value of 17. The surface oil and dirt of the aluminum can were scrubbed manually with dishwashing liquid, then rinsed with pure water, dried in an 80 °C oven, weighed, and the data M1 was recorded. Then the above aluminum substrate was immersed in the configured cleaning agent bath solution, taken out after 1 minute, rinsed with pure water, dried in an 80 °C oven, weighed, and the data M2 was recorded. The surface area S of the aluminum substrate was measured, and the etching amount data was calculated according to the formula (M1 - M2) / S.

[0119] The test results are shown in Tables 2 and 3.

[0120] Table 2

[0121]

[0122] Table 3

[0123]

[0124] From the data in Table 2 and Table 3, in terms of the cleaning effect, when the types and dosages of surfactants did not change significantly, the cleaning effects between the examples and the comparative examples were basically the same, and the cleaning level of the commercially available fluorine-containing cleaning agent could be achieved. Moreover, the cleaning agent of the present invention was more environmentally friendly and had a lower main cleaning temperature (it was found during the production line cleaning that the commercially available fluorine-containing cleaning agent in Comparative Example 5 had a problem of discontinuous water film at a main cleaning temperature of 65°C). There was a storage problem in Comparative Example 4 because the sodium bromide component was not introduced into the formula, rendering the active ingredients in the cleaning agent ineffective.

[0125] Figure 1 The following are the water film photos taken when the fluorine-free cleaning agent prepared in Example 11 was used for the cleaning experiment again after 1 month of preparation. The water film situation was the same as that in Comparative Example 5 (see Figure 2 ), both were 100% continuous water films, indicating that the fluorine-free cleaning agent of the present invention had good chemical stability.

[0126] Production line cleaning data

[0127] The following exemplarily compares the fluorine-free cleaning agent prepared in Example 11 with the commercially available fluorine-containing cleaning agent in Comparative Example 5 for production line cleaning. The production line cleaning process is as follows:

[0128] The control tank of the cleaning machine production line operates in a 24-hour continuous operation mode, and the cleaning agent is quantitatively added to the main cleaning tank through an automatic dosing system. The free acid value of the bath solution is monitored in real time and maintained in the range of 15 - 19. The working spray pump is started to implement cyclic spraying operations, and at the same time, the bath solution temperature and conductivity are dynamically monitored through an intelligent dosing system. When the detected parameters exceed the standard range, the system automatically triggers the cleaning agent replenishment program to keep the active ingredients in the bath solution stable. During the cleaning process, the oil stains and other impurities peeled off from the surface of the tank body will float on the surface of the working fluid and be discharged to the sewage treatment system through overflow. The overflow water generated at other workstations of the production line also flows into this treatment system for centralized disposal. During the production operation, the wastewater flow rate of the total discharge pipe of the cleaning machine, the dosage of inorganic flocculant, and the process qualification rate data of the ink spraying on the tank body after cleaning are recorded. The specific relevant data are shown in Table 4 below.

[0129] Table 4

[0130] Test item Example 11 Comparative example 5 Example 11 Comparative example 5 Pre - cleaning temperature 30℃ 65℃ 30℃ 65℃ Main - cleaning temperature 65℃ 75℃ 65℃ 75℃ Cleaning speed 2450 cans / min 2550 cans / min 2500 cans / min 2400 cans / min Cleaning time 24h 24h 24h 24h Number of cans cleaned 3.38 million cans 3.51 million cans 3.45 million cans 3.31 million cans Usage amount of inorganic flocculant during wastewater treatment 60 Kg 100 Kg 70 Kg 75 Kg Cleaning effect 100％ 100％ 100％ 100％ Qualified rate of finished products 100％ 100％ 100％ 100％ Wastewater generation amount 230T 290T 280T 220T

[0131] Note: The qualified rate of finished products refers to the adhesion of color printing ink, and there is no phenomenon of missing printing or falling off; if the surface of the can is not cleaned well and the water film is not continuous, the ink on the can body is likely to leak and fall off, resulting in a decrease in the qualified rate of finished products.

[0132] It is not difficult to find from the data in Table 4 that in production line cleaning, the fluorine-free cleaning agent of the present invention has equivalent cleaning effect and cleaning speed to the commercially available fluorine-containing cleaning agent, indicating that the cleaning ability of the fluorine-free cleaning agent of the present invention is at least equivalent to that of the commercially available fluorine-containing cleaning agent. However, the present invention is superior to the commercially available fluorine-containing cleaning agent in terms of pre-cleaning temperature, main cleaning temperature, and the amount of inorganic flocculant used in wastewater treatment, which is beneficial to reducing the cleaning cost of the enterprise and alleviating the pressure of the enterprise's sewage treatment.

[0133] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. A fluorine-free cleaning agent applicable to aluminum cans, characterized in that, Comprising components in the following weight percentages: Among them, the surfactant at least comprises alkylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether, and the mass ratio of alkylphenol polyoxyethylene ether to fatty alcohol polyoxyethylene ether is 7:3 to 6:

4.

2. The fluorine-free cleaning agent according to claim 1, wherein, The fluorine-free cleaning agent comprises components in the following weight percentages:

3. The fluorine-free cleaning agent according to claim 1, wherein, The alkylphenol polyoxyethylene ether is selected from the non-ionic surfactant TX-10.

4. The fluorine-free cleaning agent according to claim 1, wherein The fatty alcohol polyoxyethylene ether is selected from the non-ionic surfactant AEO-9.

5. The fluorine-free cleaning agent according to claim 1, wherein The alkylphenol polyoxyethylene ether is selected from TX-10 of German Ham Company.

6. The fluorine-free cleaning agent according to claim 1, wherein The fatty alcohol polyoxyethylene ether is selected from AEO-9 of Nanjing Gutian Company.

7. The preparation method of the fluorine-free cleaning agent according to any one of claims 1-6, characterized in that, Comprising the following steps: Under stirring, pure water, ferrous sulfate and 75% sulfuric acid are added in sequence. After all are dissolved, the temperature is raised to 50 - 60 °C; 35% hydrogen peroxide, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether and sodium bromide are continuously added. After stirring evenly, it is obtained.

8. Use of the fluorine-free cleaning agent according to any one of claims 1 - 6 in the pre-treatment cleaning of aluminum cans.

9. The application according to claim 8, wherein The specific use is: at a pre-cleaning temperature of 25 - 30 °C and a main cleaning temperature of 60 - 65 °C, the aluminum cans are cleaned on the production line, and the cleaning speed is 2450 - 2500 cans / min.

10. The application according to claim 9, wherein During the wastewater treatment process of the production line cleaning, 0.25 - 0.27 kg of inorganic flocculant is consumed per ton of wastewater.

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