Electrolytic phosphating supply composition and electrolytic phosphating supply tablet prepared from phosphating waste residues as well as method and application of electrolytic phosphating supply composition and electrolytic phosphating supply tablet

Abstract

The invention relates to the technical field of phosphating waste residue utilization, in particular to an electrolytic phosphating supply composition prepared from phosphating waste residues, an electrolytic phosphating supply tablet prepared from the phosphating waste residues and a method and application of the electrolytic phosphating supply composition and the electrolytic phosphating supply tablet. The invention discloses an electrolytic phosphating supply composition prepared from phosphating residues. The electrolytic phosphating supply composition comprises the following components in percentage by weight: 1-2% of an adhesive, 5-10% of organic acid, 15-30% of sodium bicarbonate, 2-8% of a lubricating release agent and the balance of phosphating residues. According to the electrolytic phosphating supply composition, the electrolytic phosphating supply tablet, the electrolytic phosphating supply composition and the electrolytic phosphating supply tablet which are prepared from the phosphating waste residues by converting the phosphating waste residues generated by traditional dipping phosphating into the electrolytic phosphating supply tablet, and the method and the application of the electrolytic phosphating supply composition and the electrolytic phosphating supply tablet, resource utilization of hazardous wastes is achieved, and environmental pollution and resource waste are reduced.

Description

Technical Field

[0001] The invention relates to the technical field of utilization of phosphating waste residue, and in particular to an electrolytic phosphating replenishing composition and an electrolytic phosphating replenishing tablet prepared by utilizing the phosphating waste residue, and a method and application thereof. Background Art

[0002] As one of the important processes for metal surface treatment, phosphating is widely used in the automotive, home appliance, machinery manufacturing and other industries. The traditional immersion phosphating technology forms a protective phosphating film by immersing the metal material in a specific chemical solution, thereby improving the corrosion resistance, lubricity and wear resistance of the metal material. During the immersion phosphating process, a certain amount of phosphating slag will inevitably be produced. These waste slags contain elements such as phosphorus, zinc, iron, and nickel, and are hazardous wastes with toxicity and corrosiveness. If the phosphating slag is not properly handled, it will cause serious pollution to the environment.

[0003] In recent years, electrolytic phosphating has gradually attracted attention as a new type of phosphating method. Compared with traditional immersion phosphating, electrolytic phosphating uses electrochemical reactions to directly deposit phosphate crystals on the metal surface, which not only achieves slag-free phosphating, but also can accurately control the film-forming process to obtain a more uniform and dense phosphating film layer, significantly improving the protective performance and decorative effect of metal materials. For electrolytic phosphating, in order to maintain the stability of the concentration of film-forming ions in the bath, replenishers need to be added regularly. Due to the problems of easy moisture absorption, low solubility, and easy agglomeration of powder replenishers, the replenishment operation is inconvenient, so most of the existing replenishers are in liquid form. However, liquid replenishers contain a large amount of acid and solvent, which increases logistics costs and environmental pollution risks.

[0004] There are currently no relevant reports on the use of phosphating slag as a replenisher in the electrolytic phosphating process. For this reason, the present application uses the phosphating waste slag produced by traditional immersion phosphating to prepare an electrolytic phosphating replenishing composition, an electrolytic phosphating replenishing tablet, and its method and application. Summary of the invention

[0005] The present application discloses an electrolytic phosphating replenishing composition, an electrolytic phosphating replenishing tablet and a method and application thereof prepared by converting the phosphating waste residue produced by traditional immersion phosphating into electrolytic phosphating replenishing tablets, thereby realizing the resource utilization of hazardous waste and reducing environmental pollution and waste of resources.

[0006] The purpose of the present invention is achieved through the following technical solutions:

[0007] In a first aspect of the present application, there is provided an electrolytic phosphating replenishing composition prepared using phosphating waste residue, comprising the following components in percentage by weight:

[0008] Adhesive 1-2%

[0009] Organic acid 5-10%

[0010] Sodium bicarbonate 15-30%

[0011] Lubricating release agent 2-8%

[0012] The remainder is phosphating slag.

[0013] In some specific embodiments, the binder is any one or any combination of polyvinyl pyrrolidone, hydroxypropyl methylcellulose, and sodium carboxymethyl cellulose.

[0014] In some specific embodiments, the organic acid is any one or more of citric acid, malic acid, tartaric acid and succinic acid.

[0015] In some specific embodiments, the lubricating release agent is any one or any combination of polyethylene glycol 4000, polyethylene glycol 6000, and polyoxyethylene ether.

[0016] In some embodiments, the phosphating slag is from an immersion phosphating process.

[0017] The second aspect of the present application provides a dephosphating replenishment tablet, comprising the electrolytic phosphating replenishment composition described in the first aspect.

[0018] In a third aspect of the present application, there is provided a method for preparing electrolytic phosphating replenishment tablets using the electrolytic phosphating replenishment composition of the second aspect, comprising the following steps:

[0019] 1) Pre-treating the phosphating slag;

[0020] 2) mixing the pretreated phosphating slag with a binder, an organic acid, sodium bicarbonate and a lubricating release agent to obtain an electrolytic phosphating replenishing composition;

[0021] 3) compressing the electrolytic phosphating replenishing composition to obtain electrolytic phosphating replenishing tablets;

[0022] In step 1), the pretreatment process is:

[0023] The phosphating slag is added into phosphoric acid having a concentration of 5% at a mass ratio of 1:0.5 to obtain a phosphating slag solid-liquid mixture;

[0024] adding zinc oxide to the phosphating slag solid-liquid mixture, adjusting the pH value of the phosphating slag solid-liquid mixture to 7, and filtering to obtain phosphating slag wet slag;

[0025] The wet phosphating slag is dried to obtain phosphating slag powder.

[0026] In some specific embodiments, in step 3), the pressing pressure is controlled at 5-15 MPa, and the thickness of the electrolytic phosphating supply tablet is 4-6 mm.

[0027] The fourth aspect of the present application provides the application of electrolytic phosphating replenishment tablets, wherein the electrolytic phosphating replenishment tablets prepared by the method described in the third aspect or the electrolytic phosphating replenishment tablets described in the second aspect are applied to the electrolytic phosphating process.

[0028] In some specific embodiments, the electrolytic phosphating process includes adding electrolytic phosphating replenishing tablets into the electrolyte during the electrolytic phosphating process, and monitoring the composition of the electrolyte.

[0029] The beneficial effects of this application are:

[0030] 1. The electrolytic phosphating replenishing tablets described in the present application realize the resource utilization of hazardous wastes and reduce environmental pollution and waste of resources by converting the phosphating waste residues produced by traditional immersion phosphating into electrolytic phosphating replenishing tablets.

[0031] 2. The electrolytic phosphating replenishing tablets described in the present application can effectively maintain the balance of film-forming ions in the electrolytic phosphating tank liquid, thereby achieving the uniformity and density of the electrolytic phosphating film layer and improving the quality of the electrolytic phosphating film layer.

[0032] 3. The electrolytic phosphating replenishment tablets described in the present application reduce the use of water and solvents, and are in solid form for transportation and storage. Compared with liquid preparations, they reduce the volume and weight of the product, thereby reducing logistics costs and storage space.

[0033] 4. When the electrolytic phosphating replenishing tablets described in the present application are used, during the electrolytic phosphating tank liquid replenishing operation, the problems of easy moisture absorption, low solubility and easy agglomeration of the powder preparation are avoided, and the solubility and dispersibility of the replenishing agent in the electrolytic phosphating tank liquid are improved.

[0034] 5. The electrolytic phosphating replenishment tablets described in the present application have the characteristics of accurate dosage, stable quality, and convenient storage and transportation of solid preparations, which makes the replenishment process of the electrolytic phosphating process more convenient and improves the production efficiency and operational convenience of the electrolytic phosphating process. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] The present invention is further described below in conjunction with the accompanying drawings and embodiments.

[0036] Figure 1 This is a metallographic microscope photo of the phosphating film obtained in Example 3;

[0037] Figure 2 This is a metallographic microscope photo of the phosphating film obtained in Comparative Example 1;

[0038] Figure 3 This is a metallographic microscope photograph of the phosphating film obtained in Comparative Example 6. DETAILED DESCRIPTION

[0039] In order to facilitate the understanding of those skilled in the art, the present invention is further described below in conjunction with embodiments, and the contents mentioned in the implementation modes are not intended to limit the present invention.

[0040] As used herein, "and / or" includes the term of any and all combinations of one or more associated listed items. The terms used herein are only used to describe specific embodiments and are not intended to limit the present invention. As used herein, the singular forms "a", "an", "an" and "the" are also intended to include the plural forms, unless the context clearly indicates otherwise. It is further understood that "including", when used in this specification, specifies the stated features, integers, steps, operations, elements and / or compositions, but does not exclude the existence or addition of one or more other features, integers, steps, operations, elements, compositions and / or combinations thereof.

[0041] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. It is further understood that terms, such as defined in commonly used dictionaries, are interpreted in accordance with their meanings in the context of the relevant art and are not in an idealized or overly formal sense unless explicitly so defined herein.

[0042] The exemplary invention described herein may appropriately lack any one or more element limitations that are not specifically disclosed herein. Therefore, the terms "comprise", "include", "contain", etc. should be understood broadly and non-restrictively. In addition, the terminology used herein is used as a description, not a limitation, and it is unintentional to use these terminology expressions that do not include any equivalent characteristics, but only describe some of their characteristics, but various modifications are possible within the scope of the present invention according to the rights. Therefore, although the present invention has been specifically disclosed by preferred embodiments and optional features, the modifications disclosed herein to embody the changes of the present invention may be recorded by those skilled in the art, and such modifications and changes will be considered to be within the scope of the present invention.

[0043] The raw materials or reagents used in the embodiments of the present invention and the comparative examples are all purchased from mainstream manufacturers in the market. The manufacturer or concentration is not specified, and they are all analytically pure raw materials or reagents that can be routinely obtained. As long as the expected effect can be achieved, there is no particular restriction. The instruments and equipment used in the present embodiment are all purchased from major manufacturers in the market. As long as the expected effect can be achieved, there is no particular restriction. If specific techniques or conditions are not specified in the present embodiment, the techniques or conditions described in the literature in this area or according to the product specification are carried out.

[0044] In the process practice of electrolytic phosphating, it is necessary to regularly add supplements containing elements such as phosphorus, zinc, and iron to the electrolytic phosphating bath to maintain the normal use of the process. Since the powder preparations of film-forming cations have the disadvantages of easy moisture absorption, low solubility, and easy agglomeration when added to the bath, the electrolytic phosphating supplements on the market are generally in the form of liquid. In addition, in order to maintain the full dissolution of film-forming cations such as zinc, iron, and manganese, a large amount of acid agents such as phosphoric acid and nitric acid need to be additionally compounded to make the electrolytic phosphating supplement have high acidity. During the continuous addition and use, the free acid of the electrolytic phosphating solution will gradually increase, which will lead to an imbalance of ions in the electrolytic phosphating solution and poor film application effect. In addition, in order to maintain the precipitation of other effective ingredients in the electrolytic phosphating liquid supplement, the supplement formula also contains a large amount of water and solvents. These solvents do not participate in electrolytic phosphating, but occupy a large amount of mass and volume, which also leads to high logistics costs. The main components of the current phosphating slag include phosphorus, zinc, iron, nickel and other elements. It is classified as HW17 surface treatment waste in the "National List of Hazardous Wastes". It is toxic and corrosive, and direct discharge will cause environmental pollution. At present, common treatment methods include neutralization precipitation, adsorption, ion exchange, etc. The resource utilization process is complex and the cost of harmless disposal is high. If these phosphating slags are simply treated as hazardous waste, it will not only increase safety hazards, but also lead to a huge waste of resources.

[0045] To this end, the present application provides an electrolytic phosphating replenishing composition prepared using phosphating waste residue, comprising the following components in percentage by weight:

[0046] Adhesive 1-2%

[0047] Organic acid 5-10%

[0048] Sodium bicarbonate 15-30%

[0049] Lubricating release agent 2-8%

[0050] The remainder is phosphating slag.

[0051] Specifically, the binder is any one or any combination of polyvinyl pyrrolidone, hydroxypropyl methylcellulose, and sodium carboxymethyl cellulose.

[0052] In this application, the role of the binder is to ensure that the phosphating waste residue powder can be effectively bonded to form tablets with a certain strength and shape. The selection of binders such as polyvinyl pyrrolidone, hydroxypropyl methylcellulose, sodium carboxymethyl cellulose, etc. can provide good bonding properties, so that the tablets can stably release the active ingredients during the subsequent electrolytic phosphating process.

[0053] In some embodiments, the weight percentage of the binder is 1-2%, for example, the weight percentage of the binder is any value of 1%, 1.2%, 1.5%, 1.8%, 2%, within 1-2% (including the endpoint values). The weight percentage of the binder is 1-2%, which can ensure that the tablet has sufficient mechanical strength without being too hard or too brittle. If the weight percentage of the binder is less than 1%, it may not provide sufficient bonding force, resulting in the tablet being fragile; if the weight percentage of the binder exceeds 2%, it may cause the tablet to be too hard, affecting its disintegration rate.

[0054] Specifically, the organic acid is any one or more of citric acid, malic acid, tartaric acid and succinic acid.

[0055] In this application, the role of organic acid is to effectively buffer the free acid in the phosphating solution, achieve precise control of the acidity of the electrolytic phosphating tank solution, and ensure that the electrochemical state is optimal during the electrolytic phosphating process. Acidity control is a key factor affecting the uniformity and quality of the film layer. By compounding a combination of various organic acids such as citric acid, malic acid, tartaric acid and succinic acid, the microstructure of the electrolytic phosphating film layer can be optimized, the electrolytic phosphating effect can be enhanced, the porosity and cracking phenomenon can be reduced, and the appearance quality of the electrolytic phosphating film layer can be improved.

[0056] In some embodiments, the weight percentage of the organic acid is 5-10%, for example, the weight percentage of the organic acid is any value of 5%, 6%, 7%, 8%, 9%, 10%, within 5-10% (including the endpoint values). The weight percentage of the organic acid is 5-10%, which can maintain appropriate acidity, promote film-forming reaction and improve the quality of the film layer. When the weight percentage of the organic acid is less than 5%, it may not be enough to adjust the acidity, affecting the uniformity and density of the film layer; when the weight percentage of the organic acid exceeds 10%, it may cause excessive acidification and damage the film layer structure.

[0057] Specifically, the lubricating release agent is any one or any combination of polyethylene glycol 4000, polyethylene glycol 6000, and polyoxyethylene ether.

[0058] In this application, the role of the lubricating release agent is to reduce the friction between the tablet and the mold, facilitate the molding and demolding of the tablet, enable smooth discharging and tableting during the tableting process, and reduce sticking. The reasonable combination of lubricating release agents such as polyethylene glycol 4000, polyethylene glycol 6000, polyoxyethylene ether, etc. can ensure that the tablet has good fluidity and formability during the production process, effectively reduce the friction between the tablet and the mold, and ensure the smoothness of the tablet during the molding and demolding process, thereby improving production efficiency and product quality.

[0059] In some embodiments, the weight percentage of the lubricating release agent is 2-8%, for example, the weight percentage of the lubricating release agent is any value of 2%, 3%, 4%, 5%, 6%, 7%, 8%, within 2-8% (including the endpoint value). The weight percentage of the lubricating release agent is 2-8%, which ensures good fluidity and formability. If the weight percentage of the lubricating release agent is less than 2%, demoulding is difficult and easy to stick; if the weight percentage of the lubricating release agent is higher than 8%, the tablet surface may be too smooth, affecting subsequent processing.

[0060] Specifically, the phosphating slag comes from an immersion phosphating process.

[0061] In the present application, the phosphating slag powder is derived from the waste slag produced in the traditional immersion phosphating process. After treatment, the effective components in the phosphating slag powder are retained, realizing the resource utilization of the waste slag and reducing environmental pollution. At the same time, this recycling strategy provides the necessary supplement for the electrolytic phosphating process, further enhancing the practical value and environmental significance of the present invention.

[0062] Specifically, sodium bicarbonate acts as a disintegrant, and its mechanism of action is to react with organic acids and free acids in the electrolytic phosphating tank to generate carbon dioxide gas. This reaction occurs rapidly when the tablet contacts the electrolytic phosphating tank, allowing the tablet to disintegrate rapidly. The electrolytic phosphating supply tablet itself is dry and does not contain water. When the tablet is put into the electrolytic phosphating tank, sodium bicarbonate and organic acids are ionized and reacted under the combined action of water and free acids in the electrolytic phosphating tank, producing a large amount of carbon dioxide, causing the tablet to disintegrate and melt rapidly. The bubbles generated by the disintegration will also cause the tablet to roll up and down in the electrolytic phosphating tank, accelerating its disintegration and melting, thereby quickly releasing the active ingredients in the tablet and improving the solubility and dispersibility of the supply tablet.

[0063] In some embodiments, the weight percentage of sodium bicarbonate is 15-30%, for example, the weight percentage of sodium bicarbonate is any value of 15%, 16%, 17%, 18%, 19%, 20%, within 15-30% (including the endpoint values). The weight percentage of sodium bicarbonate is 15-30% to ensure rapid disintegration. If the weight percentage of sodium bicarbonate is less than 15%, the disintegration speed may not be fast enough, affecting the replenishment efficiency; if the weight percentage of sodium bicarbonate is more than 30%, it may cause unnecessary bubbles to be generated, interfering with the electrolysis process.

[0064] The second aspect of the present application provides a dephosphating replenishment tablet, comprising the electrolytic phosphating replenishment composition described in the first aspect.

[0065] In a third aspect of the present application, there is provided a method for preparing electrolytic phosphating replenishment tablets using the electrolytic phosphating replenishment composition of the second aspect, comprising the following steps:

[0066] 1) Pre-treating the phosphating slag;

[0067] 2) mixing the pretreated phosphating slag with a binder, an organic acid, sodium bicarbonate and a lubricating release agent to obtain an electrolytic phosphating replenishing composition;

[0068] 3) compressing the electrolytic phosphating replenishing composition to obtain electrolytic phosphating replenishing tablets;

[0069] In step 1), the pretreatment process is:

[0070] The phosphating slag is added into phosphoric acid having a concentration of 5% at a mass ratio of 1:0.5 to obtain a phosphating slag solid-liquid mixture;

[0071] adding zinc oxide to the phosphating slag solid-liquid mixture, adjusting the pH value of the phosphating slag solid-liquid mixture to 7, and filtering to obtain phosphating slag wet slag;

[0072] The wet phosphating slag is dried to obtain phosphating slag powder.

[0073] In some specific embodiments, in step 3), the pressing pressure is controlled at 5-15 MPa, and the thickness of the electrolytic phosphating supply tablet is 4-6 mm.

[0074] Specifically, the preparation method of the electrolytic phosphating replenishment tablets comprises the following steps:

[0075] S101. Add the phosphating slag into 5% dilute phosphoric acid at a mass ratio of 1:0.5, raise the temperature to 40-60° C., and continue stirring for 2 hours to obtain a phosphating slag solid-liquid mixture.

[0076] S102. Add zinc oxide to the phosphating slag solid-liquid mixture in small amounts and several times, adjust the pH value of the phosphating slag solid-liquid mixture to 7, raise the temperature to 60-80 ° C, stir for 4 hours, filter while hot to obtain wet phosphating slag;

[0077] S103. The wet phosphating slag was put into a dryer for drying and dried at a temperature of 120 ° C for 6h to obtain a phosphating slag powder;

[0078] S104. According to the weight percentage of the corresponding raw materials, the materials are prepared and stored in a dryer to obtain a dry raw material powder, wherein the moisture content of the dry raw material powder is less than 1%;

[0079] S105. The dried binder, organic acid, sodium bicarbonate, lubricating release agent, phosphating slag powder was added to the mill, the grinding fineness was 80-100 mesh; fully grinded and mixed, sieved, the sieve aperture was 80-120 mesh, to obtain electrolytic phosphating supply powder;

[0080] S106. The electrolytic phosphating replenishment powder is put into a tablet press, and the tablet is compressed. The pressure is controlled at 5-15 MPa, and the tablet thickness is 4-6 mm to obtain electrolytic phosphating replenishment tablets.

[0081] In the present application, the phosphating waste residue is put into dilute phosphoric acid to obtain a phosphating waste solid-liquid mixture. The purpose of this step is to make the impurities in the phosphating waste residue fully react with the dilute phosphoric acid to form a uniform solid-liquid mixture, providing a stable reaction matrix for subsequent treatment.

[0082] In the present application, zinc oxide is added to the phosphating slag solid-liquid mixture in small amounts and multiple times to adjust the pH of the phosphating slag solid-liquid mixture. The purpose of this step is to adjust the pH value by gradually adding zinc oxide, promote the consumption of free acid in the solid-liquid mixture, and improve the purity and performance of the product. Zinc oxide is added in small amounts each time to ensure that the reaction is fully carried out while accurately controlling the pH value.

[0083] In the present application, the wet phosphating slag is put into a dryer for drying to obtain the phosphating slag powder. The function of this step is to remove the moisture in the wet phosphating slag to obtain dry powder, which is convenient for subsequent mixing and processing.

[0084] In the present application, the materials are prepared according to the weight of the corresponding raw materials in the weight percentage, and are stored in a dryer to obtain raw material dry powder. The purpose of this step is to ensure that each raw material remains dry, prevent the raw material from absorbing moisture, and avoid the tablet from disintegrating before use, which affects the product quality.

[0085] In the present application, the raw material dry powder is pre-dried at a temperature not exceeding 60°C, and the raw material dry powder stored in the dryer needs to be turned over regularly. The purpose of this step is to avoid thermal decomposition of the raw material, prevent agglomeration, and ensure uniform drying.

[0086] In the present application, dry binder, organic acid, sodium bicarbonate, lubricating release agent, and phosphating slag powder are added to a grinding machine, fully ground and mixed, and sieved to obtain electrolytic phosphating replenishment powder. The function of this step is to prepare a powder with uniform particle size and consistent component distribution, providing qualified raw materials for the tableting process.

[0087] In the present application, the electrolytic phosphating supply powder is put into a tablet press and compressed to obtain electrolytic phosphating supply tablets. The function of this step is to solidify the powder into tablets with certain strength and dispersibility through the tableting process, which is convenient for storage, transportation and use.

[0088] The third aspect of the present application provides the application of electrolytic phosphating replenishment tablets, and the electrolytic phosphating replenishment tablets prepared by the method described in the third aspect or the electrolytic phosphating replenishment tablets described in the third aspect are applied to the electrolytic phosphating process.

[0089] In some specific embodiments, the electrolytic phosphating process includes adding electrolytic phosphating replenishing tablets into the electrolyte during the electrolytic phosphating process, and monitoring the composition of the electrolyte.

[0090] Specifically, the electrolytic phosphating process includes the following steps:

[0091] S201. The anode plate is installed in the electrolytic phosphating tank, connected to the positive electrode of the electrolytic power supply, and the conductive voltage wheel is connected to the negative electrode of the electrolytic power supply;

[0092] S202. The electrolytic phosphating solution is injected into the electrolytic phosphating tank, heated and stirred;

[0093] S203. The raw material coil wire is sequentially connected to the straightening machine, the abrasive belt machine, the conductive voltage wheel, the washing tank, the electrolytic phosphating tank, the post-washing tank, the hot air dryer, and the inverted wire take-up machine;

[0094] S204. Set the current density and wire speed, turn on the electrolytic phosphating power supply and inverted wire collection, and perform electrolytic phosphating treatment on the raw wire.

[0095] S205. During the electrolytic phosphating process, regularly replenish the electrolytic phosphating supply tablets and monitor changes in the composition of the electrolyte.

[0096] More specifically, the electrolytic phosphating process includes the following steps:

[0097] S201. The anode plate is installed in the electrolytic phosphating tank, connected to the positive electrode of the electrolytic power supply, and the conductive voltage wheel is connected to the negative electrode of the electrolytic power supply;

[0098] S202. The electrolytic phosphating solution is injected into the electrolytic phosphating tank, heated, the heating temperature is 40-60 ° C, stirred, and the stirring speed is maintained at 100-200r / min;

[0099] S203. The raw material coil wire is sequentially connected to the straightening machine, the abrasive belt machine, the conductive voltage wheel, the washing tank, the electrolytic phosphating tank, the post-washing tank, the hot air dryer, and the inverted wire take-up machine;

[0100] S204. Set the current density and wire speed, turn on the electrolytic phosphating power supply and inverted wire collection, and set the current density to 5-25A / dm 2 , the wire speed is maintained at 0.6-1.6m / s, and the raw wire is electrolytically phosphated.

[0101] S205. During the electrolytic phosphating process, every 1m 2 Surface area wire, supplement 2-3g of electrolytic phosphating supply tablets, and monitor the changes in the composition of the electrolyte.

[0102] In the present application, the electrolytic phosphating solution is heated and stirred. The function of this step is to promote sufficient mass transfer of the electrolytic phosphating solution and uniform distribution of film-forming ions.

[0103] In this application, the raw material coiled wire is connected to the straightener, the sanding machine, the conductive voltage wheel, the water washing tank, the electrolytic phosphating tank, the post-water washing tank, the hot air dryer, and the inverted wire take-up machine in sequence. The role of this step is to ensure the cleanliness of the wire surface through the pretreatment steps (straightening, removing the oxide layer, water washing, etc.), to ensure that the wire surface is free of impurities, to prepare for electrolytic phosphating, and to improve the adhesion and uniformity of the phosphating film layer.

[0104] In this application, the current density and the wire speed are set, the electrolytic phosphating power supply is turned on, and the wire is inverted and taken up, and the electrolytic phosphating treatment is performed. The role of this step is to control the parameters of the electrolytic phosphating process, ensure the formation speed and quality of the phosphating film on the surface of the wire, and maintain production efficiency.

[0105] The electrolytic phosphating replenishing composition and electrolytic phosphating replenishing tablet of the present invention are further described below in conjunction with specific embodiments and comparative examples:

[0106] In the following examples and comparative examples, the specifications and sources of some raw materials are as follows:

[0107] Polyvinylpyrrolidone, CAS number: 9003-39-8.

[0108] Polyoxyethylene ether, CAS number: 9004-95-9.

[0109] Example 1

[0110] The electrolytic phosphating replenishing composition prepared by using phosphating waste residue comprises the following raw materials by weight percentage:

[0111] Polyvinyl pyrrolidone 1%, hydroxypropyl methylcellulose 1%, citric acid 5%, malic acid 2.5%, tartaric acid 1.5%, succinic acid 1%, sodium bicarbonate 30%, polyethylene glycol 4000 4%, polyethylene glycol 6000 2%, polyoxyethylene ether 2%, the balance is phosphating slag powder;

[0112] The electrolytic phosphating replenishing tablet comprises the electrolytic phosphating replenishing composition described above; the preparation process of the electrolytic phosphating replenishing tablet comprises the following steps:

[0113] S101. Add the phosphating slag into 5% dilute phosphoric acid at a mass ratio of 1:0.5, raise the temperature to maintain at 60°C, continue stirring for 2 hours at a stirring speed of 160r / min, and obtain a phosphating slag solid-liquid mixture.

[0114] S102. Zinc oxide was added to the solid-liquid mixture of phosphating slag several times, 10 g each time, the pH value of the solid-liquid mixture of phosphating slag was adjusted to 7, the temperature was raised, the temperature was maintained at 80 ° C, stirring was continued for 4 h, the stirring speed was 200 r / min, and the hot filtration was maintained at 70 ° C to obtain wet phosphating slag;

[0115] S103. The wet phosphating slag is put into a dryer for drying at 120° C. for 6 h. The rotation speed of the dryer is controlled at 60 r / min to obtain phosphating slag powder.

[0116] S104. According to the weight percentage of the corresponding raw materials, the materials were prepared and stored in a dryer below 60 ° C to obtain a raw material dry powder, the moisture content of the raw material is less than 1%;

[0117] S105. The dried binder, organic acid, sodium bicarbonate, lubricating release agent, phosphating slag powder was added to the grinding mill, the grinding fineness was 100 mesh, the mixture was fully ground and mixed, and sieved, the mesh size was 120 mesh, and the electrolytic phosphating supply powder was obtained;

[0118] S106. The electrolytic phosphating replenishment powder is put into a tablet press and compressed into tablets at a pressure of 15 MPa. The tablet thickness is 6 mm to obtain electrolytic phosphating replenishment tablets.

[0119] An electrolytic phosphating process using the electrolytic phosphating replenishing tablets described above comprises the following steps:

[0120] S201. The anode plate is installed in the electrolytic phosphating tank, connected to the positive electrode of the electrolytic power supply, and the conductive voltage wheel is connected to the negative electrode of the electrolytic power supply;

[0121] S202. The electrolytic phosphating solution is injected into the electrolytic phosphating tank, heated, the heating temperature is 60 ° C, stirred, and the stirring speed is maintained at 200r / min;

[0122] S203. The raw material coil wire is sequentially connected to the straightening machine, the abrasive belt machine, the conductive voltage wheel, the washing tank, the electrolytic phosphating tank, the post-washing tank, the hot air dryer, and the inverted wire take-up machine;

[0123] S204. Set the current density and wire speed, turn on the electrolytic phosphating power supply and inverted wire collection, and set the current density to 25A / dm 2 The wire speed is maintained at 1.6 m / s, and the raw wire is electrolytically phosphated.

[0124] S205. During the electrolytic phosphating process, every 1m 2 Surface area wire, supplement with 3g electrolytic phosphating supply tablets, and monitor the changes in the composition of the electrolyte.

[0125] Example 2

[0126] The electrolytic phosphating replenishing composition prepared by using phosphating waste residue comprises the following raw materials by weight percentage:

[0127] Polyvinyl pyrrolidone 1%, citric acid 2%, malic acid 2%, tartaric acid 1%, sodium bicarbonate 15%, polyethylene glycol 6000 1%, polyoxyethylene ether 1%, and the balance is phosphating slag powder;

[0128] The electrolytic phosphating replenishing tablet comprises the electrolytic phosphating replenishing composition described above; the preparation process of the electrolytic phosphating replenishing tablet comprises the following steps:

[0129] S101. Add the phosphating slag into 5% dilute phosphoric acid at a mass ratio of 1:0.5, raise the temperature and maintain it at 40°C, continue stirring for 2 hours at a stirring speed of 100 r / min, and obtain a phosphating slag solid-liquid mixture.

[0130] S102. Zinc oxide was added to the solid-liquid mixture of phosphating slag several times, 5 g each time, the pH value of the solid-liquid mixture of phosphating slag was adjusted to 7, the temperature was raised, the temperature was maintained at 60 ° C, stirring was continued for 4 h, the stirring speed was 160 r / min, and the hot filtration was maintained at 60 ° C to obtain wet phosphating slag;

[0131] S103. The wet phosphating slag is put into a dryer for drying at 120° C. for 6 h. The rotation speed of the dryer is controlled at 30 r / min to obtain phosphating slag powder.

[0132] S104. According to the weight percentage of the corresponding raw materials, the materials were prepared and stored in a dryer below 60 ° C to obtain a raw material dry powder, the moisture content of the raw material is less than 1%;

[0133] S105. The dried binder, organic acid, sodium bicarbonate, lubricating release agent, phosphating slag powder was added to the grinding mill, the grinding fineness was 80 mesh, the mixture was fully ground and mixed, and the sieve had a sieve aperture of 80 mesh to obtain an electrolytic phosphating supply powder;

[0134] S106. The electrolytic phosphating replenishment powder is put into a tablet press and compressed into tablets at a pressure of 5 MPa. The tablet thickness is 4 mm to obtain electrolytic phosphating replenishment tablets.

[0135] An electrolytic phosphating process using the electrolytic phosphating replenishing tablets described above comprises the following steps:

[0136] S201. The anode plate is installed in the electrolytic phosphating tank, connected to the positive electrode of the electrolytic power supply, and the conductive voltage wheel is connected to the negative electrode of the electrolytic power supply;

[0137] S202. The electrolytic phosphating solution is injected into the electrolytic phosphating tank, heated, the heating temperature is 40 ° C, stirred, and the stirring speed is maintained at 100r / min;

[0138] S203. The raw material coil wire is sequentially connected to the straightening machine, the abrasive belt machine, the conductive voltage wheel, the washing tank, the electrolytic phosphating tank, the post-washing tank, the hot air dryer, and the inverted wire take-up machine;

[0139] S204. Set the current density and wire speed, turn on the electrolytic phosphating power supply and inverted wire collection, and set the current density to 5A / dm 2 The wire speed is maintained at 0.6m / s, and the raw wire is electrolytically phosphated.

[0140] S205. During the electrolytic phosphating process, every 1m 2 Surface area wire, supplement with 2g electrolytic phosphating supply tablets, and monitor the changes in the composition of the electrolyte.

[0141] Example 3

[0142] The electrolytic phosphating replenishing composition prepared by using phosphating waste residue comprises the following raw materials by weight percentage:

[0143] Polyvinyl pyrrolidone 0.5%, hydroxypropyl methylcellulose 0.5%, sodium carboxymethyl cellulose 0.5%, citric acid 2.5%, tartaric acid 2.5%, succinic acid 2.5%, sodium bicarbonate 22.5%, polyethylene glycol 4000 2.5%, polyoxyethylene ether 2.5%, and the balance is phosphating slag powder;

[0144] The electrolytic phosphating replenishing tablet comprises the electrolytic phosphating replenishing composition described above; the preparation process of the electrolytic phosphating replenishing tablet comprises the following steps:

[0145] S101. Add the phosphating slag into 5% dilute phosphoric acid at a mass ratio of 1:0.5, raise the temperature to maintain at 50°C, continue stirring for 2 hours at a stirring speed of 130 r / min, and obtain a phosphating slag solid-liquid mixture.

[0146] S102. Zinc oxide was added to the solid-liquid mixture of phosphating slag several times, 7.5 g each time, the pH value of the solid-liquid mixture of phosphating slag was adjusted to 7, the temperature was raised, the temperature was maintained at 70 ° C, stirring was continued for 4 h, the stirring speed was 180 r / min, and the hot filtration was maintained at 65 ° C to obtain wet phosphating slag;

[0147] S103. The wet phosphating slag is put into a dryer for drying at 120° C. for 6 h. The rotation speed of the dryer is controlled at 45 r / min to obtain phosphating slag powder.

[0148] S104. According to the weight percentage of the corresponding raw materials, the materials were prepared and stored in a dryer below 60 ° C to obtain a raw material dry powder, the moisture content of the raw material is less than 1%;

[0149] S105. The dried binder, organic acid, sodium bicarbonate, lubricating release agent, phosphating slag powder was added to the grinding mill, the grinding fineness was 90 mesh, the mixture was fully ground and mixed, and the sieve had a mesh size of 100 mesh to obtain an electrolytic phosphating supply powder;

[0150] S106. The electrolytic phosphating replenishment powder is put into a tablet press, and tablets are pressed at a pressure of 10 MPa. The tablet thickness is 5 mm, and electrolytic phosphating replenishment tablets are obtained.

[0151] An electrolytic phosphating process using the electrolytic phosphating replenishing tablets described above comprises the following steps:

[0152] S201. The anode plate is installed in the electrolytic phosphating tank, connected to the positive electrode of the electrolytic power supply, and the conductive voltage wheel is connected to the negative electrode of the electrolytic power supply;

[0153] S202. The electrolytic phosphating solution is injected into the electrolytic phosphating tank, heated, the heating temperature is 50 ° C, stirred, and the stirring speed is maintained at 150r / min;

[0154] S203. The raw material coil wire is sequentially connected to the straightening machine, the abrasive belt machine, the conductive voltage wheel, the washing tank, the electrolytic phosphating tank, the post-washing tank, the hot air dryer, and the inverted wire take-up machine;

[0155] S204. Set the current density and wire speed, turn on the electrolytic phosphating power supply and inverted wire collection, and set the current density to 15A / dm 2 The wire speed is maintained at 1.1m / s, and the raw wire is electrolytically phosphated.

[0156] S205. During the electrolytic phosphating process, every 1m 2 Surface area wire, supplement with 2.5g electrolytic phosphating supply tablets, and monitor the changes in the composition of the electrolyte.

[0157] Example 4

[0158] The electrolytic phosphating replenishing composition prepared by using phosphating waste residue comprises the following raw materials by weight percentage:

[0159] Polyvinyl pyrrolidone 1%, hydroxypropyl methylcellulose 1%, citric acid 5%, malic acid 2.5%, tartaric acid 1.5%, succinic acid 1%, sodium bicarbonate 30%, polyethylene glycol 4000 4%, polyethylene glycol 6000 2%, polyoxyethylene ether 2%, the balance is phosphating slag powder;

[0160] The electrolytic phosphating replenishing tablet comprises the electrolytic phosphating replenishing composition described above; the preparation process of the electrolytic phosphating replenishing tablet comprises the following steps:

[0161] S101. Add the phosphating slag into 5% dilute phosphoric acid at a mass ratio of 1:0.5, raise the temperature and maintain it at 40°C, continue stirring for 2 hours at a stirring speed of 100 r / min, and obtain a phosphating slag solid-liquid mixture.

[0162] S102. Zinc oxide was added to the solid-liquid mixture of phosphating slag several times, 5 g each time, the pH value of the solid-liquid mixture of phosphating slag was adjusted to 7, the temperature was raised, the temperature was maintained at 60 ° C, stirring was continued for 4 h, the stirring speed was 160 r / min, and the hot filtration was maintained at 60 ° C to obtain wet phosphating slag;

[0163] S103. The wet phosphating slag is put into a dryer for drying at 120° C. for 6 h. The rotation speed of the dryer is controlled at 30 r / min to obtain phosphating slag powder.

[0164] S104. According to the weight percentage of the corresponding raw materials, the materials were prepared and stored in a dryer below 60 ° C to obtain a raw material dry powder, the moisture content of the raw material is less than 1%;

[0165] S105. The dried binder, organic acid, sodium bicarbonate, lubricating release agent, phosphating slag powder was added to the grinding mill, the grinding fineness was 80 mesh, the mixture was fully ground and mixed, and the sieve had a sieve aperture of 80 mesh to obtain an electrolytic phosphating supply powder;

[0166] S106. The electrolytic phosphating replenishment powder is put into a tablet press and compressed into tablets at a pressure of 5 MPa. The tablet thickness is 4 mm to obtain electrolytic phosphating replenishment tablets.

[0167] An electrolytic phosphating process using the electrolytic phosphating replenishing tablets described above comprises the following steps:

[0168] S201. The anode plate is installed in the electrolytic phosphating tank, connected to the positive electrode of the electrolytic power supply, and the conductive voltage wheel is connected to the negative electrode of the electrolytic power supply;

[0169] S202. The electrolytic phosphating solution is injected into the electrolytic phosphating tank, heated, the heating temperature is 40 ° C, stirred, and the stirring speed is maintained at 100r / min;

[0170] S203. The raw material coil wire is sequentially connected to the straightening machine, the abrasive belt machine, the conductive voltage wheel, the washing tank, the electrolytic phosphating tank, the post-washing tank, the hot air dryer, and the inverted wire take-up machine;

[0171] S204. Set the current density and wire speed, turn on the electrolytic phosphating power supply and inverted wire collection, and set the current density to 5A / dm2 The wire speed is maintained at 0.6m / s, and the raw wire is electrolytically phosphated.

[0172] S205. During the electrolytic phosphating process, every 1m 2 Surface area wire, supplement with 2g electrolytic phosphating supply tablets, and monitor the changes in the composition of the electrolyte.

[0173] Example 5

[0174] The electrolytic phosphating replenishing composition prepared by using phosphating waste residue comprises the following raw materials by weight percentage:

[0175] Polyvinyl pyrrolidone 1%, citric acid 2%, malic acid 2%, tartaric acid 1%, sodium bicarbonate 15%, polyethylene glycol 6000 1%, polyoxyethylene ether 1%, and the balance is phosphating slag powder;

[0176] The electrolytic phosphating replenishing tablet comprises the electrolytic phosphating replenishing composition described above; the preparation process of the electrolytic phosphating replenishing tablet comprises the following steps:

[0177] S101. Add the phosphating slag into 5% dilute phosphoric acid at a mass ratio of 1:0.5, raise the temperature to maintain at 60°C, continue stirring for 2 hours at a stirring speed of 160r / min, and obtain a phosphating slag solid-liquid mixture.

[0178] S102. Zinc oxide was added to the solid-liquid mixture of phosphating slag several times, 10 g each time, the pH value of the solid-liquid mixture of phosphating slag was adjusted to 7, the temperature was raised, the temperature was maintained at 80 ° C, stirring was continued for 4 h, the stirring speed was 200 r / min, and the hot filtration was maintained at 70 ° C to obtain wet phosphating slag;

[0179] S103. The wet phosphating slag is put into a dryer for drying at 120° C. for 6 h. The rotation speed of the dryer is controlled at 60 r / min to obtain phosphating slag powder.

[0180] S104. According to the weight percentage of the corresponding raw materials, the materials were prepared and stored in a dryer below 60 ° C to obtain a raw material dry powder, the moisture content of the raw material is less than 1%;

[0181] S105. The dried binder, organic acid, sodium bicarbonate, lubricating release agent, phosphating slag powder was added to the grinding mill, the grinding fineness was 100 mesh, the mixture was fully ground and mixed, and sieved, the mesh size was 120 mesh, and the electrolytic phosphating supply powder was obtained;

[0182] S106. The electrolytic phosphating replenishment powder is put into a tablet press and compressed into tablets at a pressure of 15 MPa. The tablet thickness is 6 mm to obtain electrolytic phosphating replenishment tablets.

[0183] An electrolytic phosphating process using the electrolytic phosphating replenishing tablets described above comprises the following steps:

[0184] S201. The anode plate is installed in the electrolytic phosphating tank, connected to the positive electrode of the electrolytic power supply, and the conductive voltage wheel is connected to the negative electrode of the electrolytic power supply;

[0185] S202. The electrolytic phosphating solution is injected into the electrolytic phosphating tank, heated, the heating temperature is 60 ° C, stirred, and the stirring speed is maintained at 200r / min;

[0186] S203. The raw material coil wire is sequentially connected to the straightening machine, the abrasive belt machine, the conductive voltage wheel, the washing tank, the electrolytic phosphating tank, the post-washing tank, the hot air dryer, and the inverted wire take-up machine;

[0187] S204. Set the current density and wire speed, turn on the electrolytic phosphating power supply and inverted wire collection, and set the current density to 25A / dm 2 The wire speed is maintained at 1.6 m / s, and the raw wire is electrolytically phosphated.

[0188] S205. During the electrolytic phosphating process, every 1m 2 Surface area wire, supplement with 3g electrolytic phosphating supply tablets, and monitor the changes in the composition of the electrolyte.

[0189] Comparative Example 1

[0190] No sodium bicarbonate was added to the raw materials of the electrolytic phosphating replenishment tablets, and the other conditions were the same as those in Example 3.

[0191] Comparative Example 2

[0192] No organic acid was added to the raw materials of the electrolytic phosphating replenishment tablets, and the other conditions were the same as those in Example 3.

[0193] Comparative Example 3

[0194] No binder was added to the raw materials of the electrolytic phosphating replenishment tablets, and the other conditions were the same as those in Example 3.

[0195] Comparative Example 4

[0196] When preparing the electrolytic phosphating replenishment tablets, the grinding and screening step S105 is not performed, and the other conditions are the same as those in Example 3.

[0197] Comparative Example 5

[0198] When preparing the electrolytic phosphating replenishment tablets, the tablet pressing pressure in step S106 is set to 50 MPa, the tablet thickness is 2 mm, and the other conditions are consistent with Example 3.

[0199] Comparative Example 6

[0200] During the electrolytic phosphating process (the electrolytic phosphating process of the electrolytic phosphating replenishing tablets described above), step S205 is performed for every 1 m of electrolytic phosphating. 2 Surface area wire, supplemented with 0.03g electrolytic phosphating supply tablets, and the other conditions were consistent with Example 3.

[0201] The technical indicators and test results of the electrolytic phosphating replenishing tablets and the electrolytic phosphating wire rod phosphating films prepared in the above embodiments and comparative examples are summarized as follows:

[0202] 1. The electrolytic phosphating replenishment tablets prepared in Examples 1-5 and Comparative Examples 1-6 were subjected to a dispersibility test:

[0203] 100 g of the electrolytic phosphating replenishing tablets prepared in the above embodiments and comparative examples were respectively dissolved in a YX-702# electrolytic phosphating bath solution with a mass of 1 kg, a free acidity of 16 pt and a temperature of 45°C. After standing for 1 hour, the state of the electrolytic phosphating bath solution was observed, filtered, the filter residue was obtained, and dried.

[0204] The dispersibility is expressed as the percentage of the weight of the dissolved portion of the tablet in the tank solution to the total weight of the tablet, that is, by [(total weight of electrolytic phosphating replenishment tablets - weight of filter residue) / total weight of electrolytic phosphating replenishment tablets × 100%]. The larger the value, the better the dispersibility of the electrolytic phosphating replenishment tablet. The results are shown in Table 1.

[0205] Table 1

[0206] sample Bath liquid appearance Dispersibility (%) Example 1 clarify 98.4 Example 2 clarify 96.9 Example 3 clarify 97.3 Example 4 clarify 99.2 Example 5 clarify 96.2 Comparative Example 1 There is a lot of sediment at the bottom of the tank 22.5 Comparative Example 2 There is sediment at the bottom of the tank and aggregates are floating in the tank 73.4 Comparative Example 3 Slightly turbid 86.5 Comparative Example 4 Slightly turbid 87.1 Comparative Example 5 There is sediment at the bottom of the tank and aggregates are floating in the tank 72.4

[0207] The results in Table 1 show that the dispersibility of the electrolytic phosphating replenishing tablets in the comparative example in the bath solution is significantly lower than that of the samples in the examples.

[0208] In Comparative Example 1, the electrolytic phosphating supply tablets failed to disintegrate effectively in the electrolytic phosphating tank solution because sodium bicarbonate was not added. Sodium bicarbonate, as a disintegrant, reacts with organic acids and free acids in the electrolytic phosphating tank solution to generate carbon dioxide gas, and this reaction is the key to enabling the tablets to disintegrate rapidly. Without sodium bicarbonate, the tablets could not disintegrate rapidly, resulting in the formation of a large amount of precipitation at the bottom of the tank solution, and the effective ingredients in the tablets could not be effectively released, so the dispersibility was significantly lower than that of the examples.

[0209] In Comparative Example 2, since no organic acid was added, sodium bicarbonate could only react with the free acid in the electrolytic phosphating bath, so that the tablet could only be gradually disintegrated from the outside. This disintegration process from the outside to the inside was not as good as the effect of simultaneous disintegration from the inside to the outside, so the dispersibility was poor. This affected the stability and dispersibility of the tablet in the bath, resulting in precipitation at the bottom of the bath, agglomerates floating in the bath, and although the tablet was partially dissolved, the overall dispersibility was poor.

[0210] In Comparative Example 3, the lack of a binder results in the ineffective bonding of the phosphating waste slag powder. Although this does not directly affect the disintegration of the tablets, it will affect the formability of the tablets. The tablets may partially disintegrate in the electrolytic phosphating bath, causing slight turbidity, which is worse than the embodiment in which a binder is added.

[0211] In Comparative Example 4, the grinding and screening steps were omitted, resulting in uneven particle size and inconsistent component distribution of the electrolytic phosphating replenishment powder, which made the tablets not dissolved evenly in the tank liquid, causing slight turbidity, indicating that although most of the tablets could be dissolved, the dispersion was still not ideal due to uneven particle size.

[0212] In Comparative Example 5, the tableting pressure was too high and the tablets were too thin, resulting in a too dense tablet structure. This made it difficult for the tablets to disintegrate in the electrolytic phosphating bath, causing precipitation at the bottom of the bath and agglomerates floating in the bath, indicating that the tablets failed to disintegrate and disperse effectively.

[0213] 2. Perform electrolytic phosphating operation according to the requirements of each embodiment and comparative example. 2 After the Q235 substrate with a surface area of ​​1.5 mm was prepared, the technical indicators of the phosphating films of Examples 1-5 and Comparative Examples 1-6 were tested. The test results are shown in Table 2.

[0214] The specific detection methods or detection conditions are:

[0215] ① Adhesion, according to GB / T 1720-2020 paint film circle test

[0216] ②Corrosion resistance, copper sulfate pitting test, drop the pitting solution on the sample and observe the time when the red corrosion spot appears. The pitting solution is: 41g copper sulfate pentahydrate, 35g sodium chloride, 13mL 0.1mol / L hydrochloric acid, and dilute to 1L with distilled water.

[0217] ③ Soak in sodium chloride solution: immerse the phosphating sample (at room temperature) in a 3% sodium chloride aqueous solution, keep it at room temperature for a specified time, and visually inspect whether there is any rust on the phosphating surface.

[0218] ④ For indoor rust prevention, the dried test pieces should be stored at room temperature with a relative humidity not exceeding 70% and no corrosive gases, and the storage time should be recorded.

[0219] Table 2

[0220]

[0221]

[0222] According to Table 2, we can see that the phosphating film obtained in the embodiment has excellent performance in thickness, adhesion, corrosion resistance, resistance to sodium chloride solution immersion and indoor rust prevention, and the film is densely crystalline, continuous and uniform. This shows that the electrolytic phosphating supply tablets prepared using phosphating waste residue can effectively maintain the stability of the concentration of film-forming ions in the electrolytic phosphating tank liquid, thereby achieving the uniformity and density of the electrolytic phosphating film layer and improving the quality of the electrolytic phosphating film layer.

[0223] In contrast, the phosphating film obtained in the comparative example is inferior to the film obtained in the example in all indicators, which indicates that factors such as not adding sodium bicarbonate, organic acid, adhesive or grinding and screening steps, as well as excessive tableting pressure and insufficient supply will affect the quality and application effect of the electrolytic phosphating film.

[0224] 3. Perform electrolytic phosphating operation according to the requirements of each embodiment and comparative example. 2 After the surface area of ​​the Q235 substrate was measured, the effects of the phosphating films obtained in Example 3, Comparative Example 1 and Comparative Example 6 were observed by metallographic microscope;

[0225] Figure 1 This is a metallographic microscope photo of the phosphate film obtained in Example 3. The results show that the electrolytic phosphate film layer exhibits excellent uniformity and integrity. The surface of the film layer is smooth, without obvious pores or defects, indicating that the electrolytic phosphating supply tablets can evenly replenish the effective ingredients in the electrolyte and promote the formation of a dense and uniform phosphate film. The film layer tightly covers the surface of the wire, showing excellent protective performance, can effectively resist the erosion of the external environment, and ensure the durability and protectiveness of the Q235 substrate.

[0226] Figure 2 This is a metallographic microscope photo of the phosphating film obtained in Comparative Example 1, which shows that the film quality is poor. Due to the lack of sodium bicarbonate, the disintegration rate of the electrolytic phosphating supply tablets is too slow, the effective ingredients are not fully released, and the insufficiently disintegrated supply tablets are adsorbed on the surface of the substrate to form sediments. The surface of the substrate is covered with sediments, and the growth of the phosphating film is hindered, forming uneven hole areas. These uneven areas may become the starting point of corrosion, reducing the overall corrosion resistance. In addition, the integrity of the film layer is insufficient, and some areas may be exposed to corrosion risks due to insufficient protection.

[0227] Figure 3 This is a metallographic microscope photo of the phosphating film obtained in Comparative Example 6. The results show that the phosphating film has obvious defects. Since the amount of electrolytic phosphating replenishment tablets added is too small, the concentration of active ingredients in the electrolyte is insufficient, and a continuous and uniform phosphating film cannot be formed, which directly affects the protective performance of the film and increases the possibility of corrosion of the substrate.

[0228] The above embodiments are preferred implementation schemes of the present invention. In addition, the present invention may also be implemented in other ways. Any obvious replacement without departing from the concept of the present invention is within the protection scope of the present invention.

Claims

1. An electrolytic phosphating replenishing composition prepared using phosphating waste residue, characterized in that: The composition comprises the following weight percentages: Adhesive 1-2% Organic acid 5-10% Sodium bicarbonate 15-30% Lubricating release agent 2-8% The remainder is phosphating slag.

2. The electrolytic phosphating replenishing composition according to claim 1, characterized in that: The binder is any one or any combination of polyvinyl pyrrolidone, hydroxypropyl methylcellulose and sodium carboxymethyl cellulose.

3. The electrolytic phosphating replenishing composition according to claim 1, characterized in that: The organic acid is any one or more of citric acid, malic acid, tartaric acid and succinic acid.

4. The electrolytic phosphating replenishing composition according to claim 1, characterized in that: The lubricating release agent is any one or any combination of polyethylene glycol 4000, polyethylene glycol 6000 and polyoxyethylene ether.

5. The electrolytic phosphating replenishing composition according to claim 1, characterized in that: The phosphating slag is obtained from an immersion phosphating process.

6. A dephosphorization supplement tablet, characterized in that: The invention comprises the electrolytic phosphating replenishing composition as described in any one of claims 1 to 5.

7. The method for preparing electrolytic phosphating replenishing tablets using the electrolytic phosphating replenishing composition according to claim 6, characterized in that: The following steps are involved: 1) Pre-treating the phosphating slag; 2) mixing the pretreated phosphating slag with a binder, an organic acid, sodium bicarbonate and a lubricating release agent to obtain an electrolytic phosphating replenishing composition; 3) compressing the electrolytic phosphating replenishing composition to obtain electrolytic phosphating replenishing tablets; In step 1), the pretreatment process is: The phosphating slag is added into phosphoric acid having a concentration of 5% at a mass ratio of 1:0.5 to obtain a phosphating slag solid-liquid mixture; adding zinc oxide to the phosphating slag solid-liquid mixture, adjusting the pH value of the phosphating slag solid-liquid mixture to 7, and filtering to obtain phosphating slag wet slag; The wet phosphating slag is dried to obtain phosphating slag powder.

8. The method according to claim 6, characterized in that In step 3), the pressing pressure is controlled at 5-15 MPa, and the thickness of the electrolytic phosphating supply tablet is 4-6 mm.

9. Application of electrolytic phosphating replenishment tablets, characterized in that: The electrolytic phosphating replenishing tablets prepared by the method described in any one of claims 7 to 8 or the electrolytic phosphating replenishing tablets described in claim 6 are applied to the electrolytic phosphating process.

10. The use according to claim 9, characterized in that: In the electrolytic phosphating process, electrolytic phosphating replenishing tablets are added to the electrolyte during the electrolytic phosphating process, and the composition of the electrolyte is monitored at the same time.

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