WO2022061948A1 - 一种不溶性阳极的甲基磺酸镀层低铅含量镀锡板生产方法及设备 - Google Patents

一种不溶性阳极的甲基磺酸镀层低铅含量镀锡板生产方法及设备 Download PDF

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WO2022061948A1
WO2022061948A1 PCT/CN2020/118977 CN2020118977W WO2022061948A1 WO 2022061948 A1 WO2022061948 A1 WO 2022061948A1 CN 2020118977 W CN2020118977 W CN 2020118977W WO 2022061948 A1 WO2022061948 A1 WO 2022061948A1
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tin
tank
lead
plating solution
pickling
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PCT/CN2020/118977
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English (en)
French (fr)
Inventor
穆海玲
陆永亮
李顺祥
谢志刚
王孝建
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上海梅山钢铁股份有限公司
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Publication of WO2022061948A1 publication Critical patent/WO2022061948A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B1/00—Cleaning by methods involving the use of tools
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B1/00—Cleaning by methods involving the use of tools
    • B08B1/20—Cleaning of moving articles, e.g. of moving webs or of objects on a conveyor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D3/00—Straightening or restoring form of metal rods, metal tubes, metal profiles, or specific articles made therefrom, whether or not in combination with sheet metal parts
    • B21D3/02—Straightening or restoring form of metal rods, metal tubes, metal profiles, or specific articles made therefrom, whether or not in combination with sheet metal parts by rollers
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G3/00—Apparatus for cleaning or pickling metallic material
    • C23G3/02—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/16—Regeneration of process solutions
    • C25D21/18—Regeneration of process solutions of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F7/00—Constructional parts, or assemblies thereof, of cells for electrolytic removal of material from objects; Servicing or operating

Definitions

  • the invention relates to a manufacturing process for a tin-plated plate, in particular to a method for producing a low-lead content tin-plated plate with an insoluble anode methyl sulfonic acid (namely, methyl sulfonic acid for short MSA) process, and belongs to the technical field of metallurgy.
  • Tinplate is still the main food and beverage packaging material, and its application range and amount are increasing. At the same time, people's quality requirements for tinplate are also increasing, especially the lead content in the tin layer.
  • EN10333-2005 "Steel for packaging - Flat steel products intended for food or beverage contact with human and animal diet - Tinplate" is not only specified for the production of plated steel
  • the content of lead and other impurities in the tin ingot of the tin plate total tin is greater than 99.85%, lead content is less than 0.01%, partition content is less than 0.01%, arsenic content is less than 0.03%), and the content in the tin plating layer is also required to be less than 0.01% %.
  • the insoluble anodizing process is the mainstream technology in the current electroplating tin production.
  • the anode In the insoluble anodizing system, the anode only plays a conductive role and does not participate in the electrode reaction.
  • the distance between the anode and the cathode is always kept constant, which is easy to control the current density during the electroplating process. , so its current density is usually higher than that of soluble anodes.
  • the MSA bath is an environment-friendly bath. The conductivity of the two baths is different, and the current density that can be achieved during the electroplating process is also different.
  • the invention of a control technology for the lead content of the tin plating layer of the insoluble anode has important practical significance for the development of tin plating technology.
  • the present invention is aimed at the problems existing in the prior art, and provides a production method of insoluble anode MSA process low lead content tin plate. process, to achieve stable production of low lead content tin plate with insoluble anode MSA process.
  • an insoluble anode tin plate with low lead content the components and contents are as follows: C: 0.003-0.15%, Si: ⁇ 0.03%, Mn: 0.1-1% , P: ⁇ 0.02%, S: ⁇ 0.02%, Cu ⁇ 0.020%, Alt: 0.01-0.2%, the balance is iron and impurities, the lead content of the tinplate coating is controlled below 50mg/kg, of which the thickness of the tinplate It is 0.17-0.55mm, the thickness of the coating is 1.1-11.2g/m 2 , preferably the thickness of the coating is 2.0-8.4g/m 2 .
  • a processing equipment for insoluble anode low lead content tin plate includes an alkaline cleaning device, a straightening machine, a pickling device, an electroplating device and a lead removal system, and the tin-plated substrate passes through the alkaline cleaning device and the straightening machine in sequence. , pickling device, electroplating device, and finally enter the lead removal system;
  • the alkaline cleaning device mainly includes an lye tank, the outlet of which is provided with a brushing tank, and two sets of brush rollers are arranged inside; compared with the conventional alkaline cleaning device, the present invention increases Two sets of brush roller devices are installed. Through the material selection and pressure control of the brush roller, combined with electrolytic alkali cleaning, the residual oil stains on the flat part and the pit part of the tin-plated substrate can be completely removed;
  • the tin-plated substrate is straightened by a multi-roller straightening machine to increase the horizontal and vertical flatness of the tin-plated substrate to obtain a good plate shape, which is used for the subsequent electroplating process and even Downstream users provide protection for painting;
  • the pickling device includes two pickling tanks, and a high-pressure spray device is installed in the pickling tank.
  • the nozzle adopts a fan-shaped nozzle, and a pair of squeeze rollers are arranged on the top of the acid tank with fan-shaped nozzles inside; the pickled strip passes through a In the rinsing tank, two sets of brush rollers and two groups of water nozzles are arranged in the rinsing tank, and the top of the tank is equipped with a pair of squeeze rollers.
  • the invention adds a brush roller device, which can better remove the residual oxide layer of the tin-plated substrate, and has a good effect of activating the tin-plated substrate.
  • the water nozzle adopts a fan-shaped design, which can remove the residual sulfuric acid from the tin-plated substrate, and avoid substituting it into the electroplating solution to cause the imbalance of the components of the electroplating solution and thus affect the electroplating effect;
  • the electroplating device includes an electroplating bath and a tin dissolution tank;
  • the lead removal system includes a hydroxide A barium dissolving tank, a reaction tank, a sedimentation tank, a mud pump and a filter press; the barium hydroxide dissolving tank is sequentially connected to a reaction tank, a sedimentation tank, a mud pump and a filter press, and the lead removal system continuously reduces the lead in the plating solution.
  • the ion concentration plays a vital role.
  • the reasonable structural design of the reaction tank and sedimentation tank of its core components fully exerts the lead removal effect, and reduces the lead ion concentration of the plating solution to the maximum extent below 1.0mg/L, which is a low lead Content tin plate production provides excellent conditions.
  • the filter press in the lead removal system can remove the lead and barium sulfate precipitates generated during the lead removal process together with the tin sludge to achieve the effect of purifying the plating solution, which plays a key role in improving the electroplating effect and surface quality.
  • the main core components of the lead removal system are the reaction tank and the sedimentation tank: a premixing chamber is set inside the reaction tank, and the barium hydroxide is fully mixed with the tin plating solution in the premixing chamber with a stirring device.
  • the width of the premixing chamber is The tank diameter is The stirring speed of the stirring paddle M1 in the premixing chamber is 400-600 rpm.
  • the main reaction chamber the fine barium sulfate continuously adsorbs Pb 2+ in the plating solution
  • the main reactor is provided with a stirring paddle M2, the stirring paddle is a flat paddle, and the width d of the stirring paddle is the diameter of the container
  • the rotational speed of the stirring paddle is 30-60 rpm.
  • the top of the sedimentation tank structure is provided with a liquid inlet pipe, and the bottom is provided with a sewage outlet.
  • the side of the tank is provided with manholes, observation holes and micro-pressure gauges.
  • the diameter d of the main sedimentation section is determined by the processing volume (L) of the tin plating solution, and the relationship between d and L is In the formula: the unit of L is L/h, and the unit of d is mm.
  • the diameter D of the clarification section of the tank is (1.5 ⁇ 2.0)d.
  • the height of the main settlement section (H3) is (1.5 ⁇ 2.0)d
  • the height of the settlement section of the inclined plate (H2) is 1.0 ⁇ 1.5m
  • the height of the clarification section (H1) is 1.5 ⁇ 2.0m
  • the inclination angle of the inclined plate (A1 ) is 60 to 90°.
  • the angle (A3) of the lower cone angle of the settling tank is in the range of 90 to 120°.
  • a central descending pipe is arranged inside the settling tank.
  • the diameter dd of the central descending pipe is related to the diameter of the shell of the main settlement section
  • the depth of the central downcomer inserted into the solution is h
  • the end of the insertion tube is flared
  • the conical section of the tank is provided with a micro differential pressure gauge.
  • the test accuracy of the micro differential pressure gauge is 0.001MPa.
  • the installation height of the micro differential pressure gauge is 300mm from the mud outlet.
  • a production method of a methanesulfonic acid coating low lead content tin plate of an insoluble anode comprising the following steps:
  • Step 1 in the alkaline cleaning process section, the tin-plated substrate is first subjected to electrochemical alkaline cleaning, and the alkaline cleaning solution is a sodium hydroxide solution containing potassium hydroxide; a brushing process is added, and the bristles on the brush roller are nylon materials containing abrasives;
  • Step 2 In the pickling process section, the strip steel after alkaline washing enters the chemical pickling tank.
  • the pickling tank adopts a low-concentration sulfuric acid solution, and is sprayed on the surface of the strip steel by a high-pressure spray device, and a brushing process is added.
  • the bristles on the top are made of pure nylon material;
  • Step 3 In the electroplating process section, after the strip enters the MSA bath system of the insoluble anode, the strip is electroplated at a lower current density, and the tin ions in the bath are regulated by extracorporeal circulation.
  • the plating solution is pumped into the tin dissolving tank through a circulating pump, and the tin particles react with the plating solution injected with oxygen in the tin dissolving tank to increase the concentration of tin ions in the plating solution;
  • Step 4 The plating solution after electroplating enters the lead removal system, and the lead in the plating solution is removed by continuous extracorporeal circulation.
  • the lead content in the tin plating layer is controlled below 50mg/kg.
  • step 1 is as follows:
  • the tin-plated substrate enters the tin-plating unit, and electrolytic alkaline washing is used in the alkaline washing process of the tin-plating production process.
  • Active agent the content of defoamer is 0.01-0.10%wt
  • the content of surfactant is 0.1-1.0%wt
  • the content of sodium hydroxide in the alkaline washing solution is 5-30%wt, (preferably 15-20%)
  • Electrode and strip steel form an electrolytic cell in the alkaline cleaning unit, and the electrode material is made of pure Ti material.
  • the current density of the alkaline washing is controlled at 10-30 A/dm 2
  • the temperature of the alkaline washing solution is controlled at 40-55 °C.
  • the effect of electrolytic alkaline cleaning is better than that of chemical alkaline cleaning.
  • the alkaline cleaning electrode plate coated with a layer of YiO 2 on the surface of pure titanium can improve the effect of electrolytic alkaline cleaning. If the YiO 2 coating is too thick, the purchase cost of the electrode plate will be greatly increased.
  • the thickness of 5-20um is the most cost-effective; the current density of alkaline cleaning is controlled at 10-30A/dm 2 , and the effect of alkaline cleaning is not good if the current density of alkaline cleaning is too small.
  • the temperature of the alkaline washing solution was finally determined to be 40-55 °C.
  • the outlet of the alkali cleaning tank is provided with a brushing tank, and there are two sets of brush rollers in the brushing tank.
  • the rotation direction of the brush rollers is opposite to the running direction of the strip, and the
  • the material is made of nylon material containing abrasive (SiC).
  • the particle size of SiC is between 200 and 800 mesh.
  • the nylon material brush roller is kept in close contact with the strip steel through a pneumatic cylinder. In 200 ⁇ 500N.
  • the roughness of the tin-plated substrate is generally 0.2-1.0um. Adding a brush roller device can remove the residual iron oxide scale, impurities and oil stains on the surface of the tin-plated substrate through mechanical force.
  • the brush wire is made of nylon material containing abrasive (SiC), and the particle size of SiC is between 200 and 800 mesh, which can ensure the flexibility of the brush wire, while ensuring the brushing effect, it can also prolong the service life of the brush roller; the pressure of the brush roller The size directly determines the degree of contact between the tin-plated substrate and the roller surface.
  • SiC nylon material containing abrasive
  • the size directly determines the degree of contact between the tin-plated substrate and the roller surface.
  • the pressure of the brush roller is too small, only the impurities and oil remaining on the surface of the tin-plated substrate can be removed, and the remaining impurities and oil on the surface of the tin-plated substrate with large roughness can be removed.
  • the effect is not good; when the pressure of the brush roller is too high, the contact between the brush wire on the roller surface and the tin-plated substrate is too large.
  • the removal of impurities and oil stains remaining on the tin-plated substrate is
  • the pickling adopts chemical pickling
  • the pickling medium is dilute sulfuric acid
  • the sulfuric acid concentration is 5-20%
  • the temperature of the pickling solution is 40-55°C
  • the pickling medium is dilute sulfuric acid.
  • the process section is provided with two pickling tanks, and the pickling liquid is sprayed onto the surface of the strip through fan nozzles, and the spray volume of each group of nozzles is not less than 10-15m 3 /h.
  • Pickling is mainly to remove a very small amount of iron oxide scale on the front surface of the tin-plated substrate, to achieve the effect of activating the tin-plated substrate, and to provide a highly active surface for the subsequent tin electroplating process. If the concentration and temperature of sulfuric acid are too low, the activation effect will be poor. If the concentration and temperature are too high, the surface state of the tin-plated substrate will be damaged, which is not conducive to the deposition of the tin layer.
  • step 2 the pickled strip passes through a rinsing tank, two sets of brush rolls and two pairs of water nozzles are arranged in the rinsing tank, and a pair of squeeze rollers are arranged on the top.
  • the brush wire is made of nylon material, and the nylon material brush roller is kept in close contact with the strip steel through the pneumatic cylinder.
  • the water nozzles are fan-shaped nozzles, and the spray volume of each group of nozzles is not less than 10-15m 3 /h.
  • the squeeze roller is made of polyurethane material, and the hardness of the polyurethane material is 75-80A.
  • the two sets of brush rollers in the rinsing tank use less pressure to improve the pickling removal ability of the residual oxide layer on the surface of the tin-plated substrate without causing hard scratches on the surface of the tin-plated substrate.
  • the water nozzle and the squeezing roller on the top can remove the residual sulfuric acid solution on the surface of the steel plate, so as to avoid the residual sulfuric acid solution and the steel plate before the strip steel enters the electroplating tank to generate iron ions and bring it into the electroplating tank.
  • the electrode material used in the electroplating process is pure Ti+YiO 2 electrode, the thickness of YiO 2 is 10-20 ⁇ m, and the concentration of tin ions in the plating solution is controlled at 16-20 g /L, the current density is controlled at 15 ⁇ 25A/dm 2 , and the temperature of the bath is controlled at 40 ⁇ 50°C; the lead ion concentration in the bath is controlled by the lead removal system, which includes reaction, adsorption, precipitation, separation, etc. In the process, the lead ion concentration of the plating solution is controlled below 1.0mg/L after the lead removal system.
  • the same principle as the electrolytic alkaline cleaning plate, pure Ti+YiO 2 plate can improve the electroplating effect.
  • Increasing the concentration of tin ions can inhibit the deposition of lead ions into the coating, but if the concentration of tin ions is too high, the content of tin sludge in the plating solution will increase sharply.
  • the current density is controlled at 15-25A/dm 2 , and the temperature of the plating solution is controlled at 40-50°C, so that a dense coating can be obtained. If the temperature is too low, the electrochemical reaction efficiency will decrease, and if the temperature is too high, the organic components in the plating solution will degrade and lose their activity. If the current density is too low, the high-speed and stable production of the unit will be affected. If the current density is too high, the grains of the coating will be coarse and uneven.
  • Barium hydroxide addition amount (g/L) K*lead content in tin raw material (mg/kg), K value range: (0.015 ⁇ 0.020).
  • the sources of lead ions in the plating solution are mainly tin raw materials and pickling solution.
  • the pickling solution is in a stable state, while the lead content of the tin raw material fluctuates greatly. Therefore, the lead content of the tin raw material directly affects the concentration of lead ions in the plating solution.
  • the principle of barium hydroxide reducing lead is that barium hydroxide and sulfuric acid in the plating solution generate barium sulfate, and the lead ions in the plating solution are wrapped by barium sulfate to form a co-precipitation, which is removed by a filter press.
  • the addition amount of barium hydroxide (g/L) K*the lead content in the tin raw material (mg/kg), and the value range of K is: (0.015 ⁇ 0.020).
  • Appropriate addition of barium hydroxide can remove the lead ions in the plating solution to the greatest extent, so that the concentration of lead ions in the plating solution is controlled below 1.0mg/L, and at the same time, it will not add too much barium hydroxide to the plating solution.
  • Excessive production of barium sulfate results in the enrichment of barium ions in the plating solution and affects the electroplating effect.
  • the lead removal process is as follows: adding an appropriate amount of barium hydroxide solution to the plating solution under stirring, and adding the barium hydroxide to the plating solution under stirring
  • the sulfuric acid reacts to generate fine barium sulfate particles, and the fine barium sulfate adsorbs the lead ions in the plating solution under stirring.
  • the plating solution enters the vertical flow sedimentation tank by overflowing. After sedimentation, the clear liquid overflows into the plating bath through the upper part of the sedimentation tank, and the mud at the bottom of the sedimentation tank is pumped into the filter press through the mud pump.
  • the clear liquid is returned to the plating bath, and the mud cake is recycled as solid waste.
  • the stirring state within 60 to 90 minutes, the speed of barium hydroxide and sulfuric acid in the plating solution to generate barium sulfate, and the sufficient adsorption of barium sulfate and lead ions in the plating solution can be ensured.
  • the supernatant liquid is returned to the plating bath, and after repeated and continuous lead reduction treatment processes, the purpose of rapidly reducing the lead ions in the plating solution is achieved.
  • the present invention has the following advantages: 1) The technical scheme can make the coating of different tin-plated products have good adhesion between the coating and the substrate, and can realize the stable control of the lead content in the coating. The purity is 99.9%.
  • the lead ion concentration of the plating solution can be stably controlled below 1.0 mg/L after the lead removal system, which greatly reduces the requirements for tin raw materials in order to obtain a plating solution with low lead content, and reduces production costs; 2 )
  • the lead content in the tin-plated layer can be controlled below 50 mg/kg, so as to realize the stable production of low-lead-content tin-plated sheets, and enhance the low-lead content tin-plated sheets in metal.
  • the invention adds a brush roller device, which can better remove the residual oxide layer of the tin-plated substrate, and has a good effect of activating the tin-plated substrate.
  • the water nozzle adopts a fan-shaped design, which can remove the residual sulfuric acid of the tin-plated substrate, and avoid substituting it into the plating solution to cause the imbalance of the plating solution components and thus affect the plating effect;
  • the lead removal system plays an important role in continuously reducing the concentration of lead ions in the plating solution. It plays a vital role.
  • the filter press in the lead removal system can remove the lead and barium sulfate precipitates generated during the lead removal process together with the tin sludge to achieve the effect of purifying the plating solution and improve the electroplating efficiency and surface quality.
  • Fig. 1 is the overall flow schematic diagram of the present invention
  • FIG. 2 structure diagram of reaction tank in lead removal system
  • FIG. 3 is a structural diagram of the sedimentation tank in the lead removal system
  • the lead content of the tinplate coating is controlled below 50mg/kg, wherein the thickness of the tinplate is 0.17-0.55mm, and the thickness of the coating is 1.1-11.2g/m 2 , preferably the thickness of the coating requires 2.0- 8.4g/m 2 .
  • the thickness of the tin plate is preferably 0.20mm, 0.25mm, 0.30mm, 0.43mm, 0.50mm, 0.55mm, etc.
  • the thickness of the coating is 2.5g/m 2 , 3.0g/m 2 , 4.5g/ m 2 , 5.6 g/m 2 , 7.5 g/m 2 , 8.0 g/m 2 , 8.5 g/m 2 , 9.8 g/m 2 , 11.0 g/m 2 , and the like.
  • the technical scheme can make the product with different tin plating amount have good adhesion between the coating and the substrate, and can realize the stable control of the lead content in the coating.
  • the lead ion concentration of the plating solution can be stably controlled below 1.0 mg/L, which greatly reduces the requirements for tin raw materials in order to obtain a plating solution with low lead content, and reduces the production cost.
  • Example 2 Referring to Figures 1 to 3, a processing equipment for insoluble anode low lead content tinplate, the processing equipment includes an alkaline cleaning device, a straightening machine, a pickling device, an electroplating device and a lead removal system.
  • the tin substrate passes through the alkaline cleaning device, the straightening machine, the pickling device, the electroplating device in sequence, and finally enters the lead removal system;
  • the alkaline cleaning device mainly includes an lye tank, the outlet of which is provided with a brushing tank, and two sets of brush rollers are arranged inside; compared with the conventional alkaline cleaning device, the present invention adds two sets of brush roller devices. Control, combined with electrolytic alkali cleaning, can completely remove the residual oil on the flat part and the pit part of the tin-plated substrate;
  • the tin-plated substrate is straightened by a multi-roller straightening machine to increase the horizontal and vertical flatness of the tin-plated substrate to obtain a good plate shape, which is used for the subsequent electroplating process and even Downstream users provide protection for painting;
  • the pickling device includes two pickling tanks, and a high-pressure spray device is installed in the pickling tank.
  • the nozzle adopts a fan-shaped nozzle, and a pair of squeeze rollers are arranged on the top of the acid tank with fan-shaped nozzles inside; the pickled strip passes through a In the rinsing tank, two sets of brush rollers and two groups of water nozzles are arranged in the rinsing tank, and the top of the tank is equipped with a pair of squeeze rollers.
  • the invention adds a brush roller device, which can better remove the residual oxide layer of the tin-plated substrate, and has a good effect of activating the tin-plated substrate.
  • the water nozzle adopts a fan-shaped design, which can remove the residual sulfuric acid from the tin-plated substrate, and avoid substituting it into the electroplating solution to cause the imbalance of the components of the electroplating solution and thus affect the electroplating effect;
  • the electroplating device includes an electroplating bath and a tin dissolution tank;
  • the lead removal system includes a hydroxide A barium dissolving tank, a reaction tank, a sedimentation tank, a mud pump and a filter press; the barium hydroxide dissolving tank is sequentially connected to a reaction tank, a sedimentation tank, a mud pump and a filter press, and the lead removal system continuously reduces the lead in the plating solution.
  • the ion concentration plays a vital role.
  • the reasonable structural design of the reaction tank and sedimentation tank of its core components fully exerts the lead removal effect, and reduces the lead ion concentration of the plating solution to the maximum extent below 1.0mg/L, which is a low lead Content tin plate production provides excellent conditions.
  • the filter press in the lead removal system can remove the lead and barium sulfate precipitates generated during the lead removal process together with the tin sludge to achieve the effect of purifying the plating solution, which plays a key role in improving the electroplating effect and surface quality.
  • the main core components of the lead removal system are the reaction tank and the sedimentation tank: a premixing chamber is set inside the reaction tank, and the barium hydroxide is fully mixed with the tin plating solution in the premixing chamber with a stirring device.
  • the width of the premixing chamber is The tank diameter is The stirring speed of the stirring paddle M1 in the premixing chamber is 400-600 rpm.
  • the main reaction chamber the fine barium sulfate continuously adsorbs Pb 2+ in the plating solution
  • the main reactor is provided with a stirring paddle M2, the stirring paddle is a flat paddle, and the width d of the stirring paddle is the diameter of the container
  • the rotational speed of the stirring paddle is 30-60 rpm.
  • the structure of the settling tank is shown in the figure, the top is provided with a liquid inlet pipe 1, the bottom is provided with a sewage outlet 10, the side of the tank is provided with a manhole 6, an observation hole 9 and a micro-differential pressure gauge 7, settling
  • the tank body is provided with top cover 2, clarification section (H1), inclined plate settlement section (H2) and main settlement section (H3) in sequence from top to bottom.
  • the diameter d of the main settlement section is determined by the processing capacity of the tin plating solution (L ), the relationship between d and L is In the formula: the unit of L is L/h, and the unit of d is mm.
  • the diameter D of the clarification section of the tank is (1.5 ⁇ 2.0)d
  • the overflow weir 3 is arranged in the clarification section of the tank
  • the height of the main settlement section (H3) is (1.5 ⁇ 2.0)d
  • the height of the settlement section of the inclined plate (H2 ) is 1.0 ⁇ 1.5m
  • the inclined plate 4 is arranged in the settlement section of the inclined plate
  • the height (H1) of the clarification section is 1.5 ⁇ 2.0m
  • the inclination angle (A1) of the inclined plate is 60 ⁇ 90°.
  • the angle (A3) of the lower cone angle of the settling tank is in the range of 90 to 120°.
  • a central descending pipe 5 is arranged inside the settling tank, and the diameter dd of the central descending pipe 5 is related to the diameter of the shell of the main settling section,
  • the depth of the central downcomer 5 inserted into the solution is h
  • the end of the insertion tube is flared
  • the conical section of the tank body is provided with a micro differential pressure gauge 7, the test accuracy of the micro differential pressure gauge 7 is 0.001MPa, and the installation height of the micro differential pressure gauge 7 is 300mm from the mud outlet. Once the micro differential pressure gauge 7 detects that the pressure is higher than the initial pressure When the value increases by 15%, the mud pump starts.
  • the mud pump body stops working; the sediment at the bottom of the tank is pumped by the mud pump. Go, the mud pump starts and stops in a timing mode, and the extracted sediment passes through the filter press, which uses nylon filter cloth with a filtration accuracy of 1 ⁇ m.
  • Embodiment 3 Referring to Figure 1, a method for producing a tin-plated plate controlled by a low lead content of a methanesulfonic acid (MSA) coating of an insoluble anode, the process comprises the following steps:
  • Step 1 in the alkaline cleaning process section, the tin-plated substrate is first subjected to electrochemical alkaline cleaning, and the alkaline cleaning solution is a sodium hydroxide solution containing potassium hydroxide; a brushing process is added, and the bristles on the brush roller are nylon materials containing abrasives;
  • Step 2 In the pickling process section, the strip steel after alkaline washing enters the chemical pickling tank.
  • the pickling tank adopts a low-concentration sulfuric acid solution, and is sprayed on the surface of the strip steel by a high-pressure spray device, and a brushing process is added.
  • the bristles on the top are made of pure nylon material;
  • Step 3 In the electroplating process section, after the strip enters the MSA bath system of the insoluble anode, the strip is electroplated at a lower current density, and the tin ions in the bath are regulated by extracorporeal circulation.
  • the plating solution is pumped into the tin dissolving tank through a circulating pump, and the tin particles react with the plating solution injected with oxygen in the tin dissolving tank to increase the concentration of tin ions in the plating solution;
  • Step 4 The plating solution after electroplating enters the lead removal system, and the lead in the plating solution is removed by continuous extracorporeal circulation.
  • the lead content in the tin plating layer is controlled below 50mg/kg.
  • step 1 is as follows:
  • the tin-plated substrate enters the tin-plating unit, and electrolytic alkaline washing is used in the alkaline washing process of the tin-plating production process.
  • Active agent the content of defoamer is 0.01-0.10%wt, the content of surfactant is 0.1-1.0%wt, the content of sodium hydroxide in the alkaline washing liquid is 5-30%wt, preferably 15-20%wt and the content of potassium hydroxide is 0.1 ⁇ 5%wt;
  • Electrode and strip steel form an electrolytic cell in the alkaline washing unit, and the electrode material is made of pure Ti material.
  • a layer of YiO 2 is plated on the surface of the Ti material, and the thickness of YiO 2 is 5-20 ⁇ m , the alkaline washing current density is controlled at 10-30A/dm 2 , and the temperature of the alkaline washing solution is controlled at 40-55°C.
  • the effect of electrolytic alkaline cleaning is better than that of chemical alkaline cleaning.
  • the alkaline cleaning electrode plate coated with a layer of YiO 2 on the surface of pure titanium can improve the effect of electrolytic alkaline cleaning. If the YiO 2 coating is too thick, the purchase cost of the electrode plate will be greatly increased.
  • the thickness of 5-20um is the most cost-effective; the current density of alkaline cleaning is controlled at 10-30A/dm 2 , and the effect of alkaline cleaning is not good if the current density of alkaline cleaning is too small. If the current density is too large, it will cause discoloration of the tin-plated substrate and affect the quality of subsequent electroplating. According to the empirical formula of Arrhenius reaction rate, increasing the solution temperature can improve the degreasing effect of tin-plated substrates. At the same time, in order to avoid the degradation of components such as defoamer and surfactant in the alkaline washing solution due to the high temperature and affecting the alkaline washing effect, the temperature of the alkaline washing solution was finally determined to be 40-55 °C.
  • the outlet of the alkali cleaning tank is provided with a brushing tank, and there are two sets of brush rollers in the brushing tank.
  • the rotation direction of the brush rollers is opposite to the running direction of the strip steel, and the material of the brush wire is made of nylon containing abrasive (SiC). Material, the particle size of SiC is between 200 and 800 mesh, and the nylon material brush roller is kept in close contact with the strip steel through a pneumatic cylinder.
  • the roughness of the tin-plated substrate is generally 0.2-1.0um. Adding a brush roller device can remove the residual iron oxide scale, impurities and oil stains on the surface of the tin-plated substrate through mechanical force.
  • the brush wire is made of nylon material containing abrasive (SiC), and the particle size of SiC is between 200 and 800 mesh, which can ensure the flexibility of the brush wire, while ensuring the brushing effect, it can also prolong the service life of the brush roller; the pressure of the brush roller The size directly determines the degree of contact between the tin-plated substrate and the roller surface.
  • SiC nylon material containing abrasive
  • the size directly determines the degree of contact between the tin-plated substrate and the roller surface.
  • the pressure of the brush roller is too small, only the impurities and oil remaining on the surface of the tin-plated substrate can be removed, and the remaining impurities and oil on the surface of the tin-plated substrate with large roughness can be removed.
  • the effect is not good; when the pressure of the brush roller is too high, the contact between the brush wire on the roller surface and the tin-plated substrate is too large.
  • the removal of impurities and oil stains remaining on the tin-plated substrate is
  • the pickling adopts chemical pickling
  • the pickling medium is dilute sulfuric acid
  • the sulfuric acid concentration is 5-20%
  • the temperature of the pickling solution is 40-55°C
  • the pickling process section is provided with two picklings.
  • the pickling solution is sprayed onto the surface of the strip steel through fan nozzles, and the spray volume of each group of nozzles is not less than 10-15m 3 /h.
  • Pickling is mainly to remove a very small amount of iron oxide scale on the front surface of the tin-plated substrate, to achieve the effect of activating the tin-plated substrate, and to provide a highly active surface for the subsequent tin electroplating process. If the concentration and temperature of sulfuric acid are too low, the activation effect will be poor. If the concentration and temperature are too high, the surface state of the tin-plated substrate will be damaged, which is not conducive to the deposition of the tin layer.
  • the pickled strip passes through a rinsing tank, two sets of brush rolls and two pairs of water nozzles are arranged in the rinsing tank, and a pair of squeeze rollers are arranged on the top.
  • the brush wire is made of nylon material, and the nylon material brush roller is kept in close contact with the strip steel through the pneumatic cylinder.
  • the water nozzles are fan-shaped nozzles, and the spray volume of each group of nozzles is not less than 10-15m 3 /h.
  • the squeeze roller is made of polyurethane material, and the hardness of the polyurethane material is 75-80A.
  • the two sets of brush rollers in the rinsing tank use a small pressure to improve the pickling removal ability of the residual oxide layer on the surface of the tin-plated substrate without causing hard scratches on the surface of the tin-plated substrate.
  • the two pairs of water nozzles in the rinsing tank and the squeezing roller at the top can remove the residual sulfuric acid solution on the surface of the steel plate, so as to prevent the residual sulfuric acid solution and the steel plate from generating iron ions before the strip enters the electroplating tank, which will be brought into the electroplating tank.
  • the electrode material used in the electroplating process is pure Ti+YiO 2 electrode, the thickness of YiO 2 is 10-20 ⁇ m, the concentration of tin ions in the plating solution is controlled at 16-20 g/L, and the current density is controlled at 15 ⁇ m. ⁇ 25A/dm 2 , the temperature of the bath is controlled at 40 ⁇ 50°C; the concentration of lead ions in the bath is controlled by the lead removal system.
  • the lead removal system includes reaction, adsorption, precipitation, separation and other processes. After the lead removal system The concentration of lead ions in the plating solution is controlled below 1.0 mg/L.
  • pure Ti+YiO 2 plate can improve the electroplating effect.
  • Increasing the concentration of tin ions can inhibit the deposition of lead ions into the coating, but if the concentration of tin ions is too high, the content of tin sludge in the plating solution will increase sharply.
  • the current density is controlled at 15-25A/dm 2 , and the temperature of the plating solution is controlled at 40-50°C, so that a dense coating can be obtained. If the temperature is too low, the electrochemical reaction efficiency will decrease, and if the temperature is too high, the organic components in the plating solution will degrade and lose their activity. If the current density is too low, the high-speed and stable production of the unit will be affected. If the current density is too high, the grains of the coating will be coarse and uneven.
  • step 4 what is used for removing lead is barium hydroxide solution, and the addition amount of barium hydroxide is determined according to the lead content in the tin raw material, and the relational formula therebetween is:
  • Barium hydroxide addition amount (g/L) K*lead content in tin raw material (mg/kg), K value range: (0.015 ⁇ 0.020).
  • the sources of lead ions in the plating solution are mainly tin raw materials and pickling solution.
  • the pickling solution is in a stable state, while the lead content of the tin raw material fluctuates greatly. Therefore, the lead content of the tin raw material directly affects the concentration of lead ions in the plating solution.
  • barium hydroxide reducing lead The principle of barium hydroxide reducing lead is that barium hydroxide and sulfuric acid in the plating solution generate barium sulfate, and the lead ions in the plating solution are wrapped by barium sulfate to form a co-precipitation, which is removed by a filter press.
  • the addition amount of barium hydroxide (g/L) K*the lead content in the tin raw material (mg/kg), and the value range of K is: (0.015 ⁇ 0.020).
  • barium hydroxide can remove the lead ions in the plating solution to the greatest extent, so that the concentration of lead ions in the plating solution is controlled below 1.0mg/L, and at the same time, it will not add too much barium hydroxide to the plating solution. Excessive production of barium sulfate results in the enrichment of barium ions in the plating solution and affects the electroplating effect.
  • the lead removal process is as follows: adding an appropriate amount of barium hydroxide solution into the plating solution under stirring, and reacting the barium hydroxide with the sulfuric acid in the plating solution under stirring to generate fine barium sulfate. Particles, the fine barium sulfate adsorbs the lead ions in the plating solution in a state of stirring, after 60-90 minutes of adsorption process, the plating solution enters the vertical flow sedimentation tank through overflow, and the clear liquid passes through the sedimentation tank after sedimentation. The upper part overflows into the plating bath, and the mud at the bottom of the sedimentation tank is pumped into the filter press through the mud pump.
  • the start and stop of the mud pump is controlled by the differential pressure gauge at the bottom.
  • the mud cake is recycled as solid waste.
  • the speed of barium hydroxide and sulfuric acid in the plating solution to generate barium sulfate, and the sufficient adsorption of barium sulfate and lead ions in the plating solution can be ensured.
  • the supernatant liquid is returned to the plating bath, and after repeated and continuous lead reduction treatment processes, the purpose of rapidly reducing the lead ions in the plating solution is achieved.
  • the structure size of the reaction tank is shown in Figure 2, the mixing and stirring paddles are inclined paddles with a certain degree of shearing function to ensure that the fine barium sulfate and the plating solution are fully mixed, and the rotating speed of the stirring paddles is 600rmp.
  • the rotating speed of the precipitation stirring paddle is 60 rpm to prevent the sedimentation of the fine barium sulfate during the adsorption process, and the adsorption time of the plating solution in the tank is 1 hour.
  • the solution after the adsorption reaction is overflowed to the settling tank.
  • the structure size of the settling tank is shown in Figure 3, and the relationship between the diameter D and L of the tank is:
  • the diameter of the settling tank d 2000 mm.
  • the angle A3 of the cone angle of the lower part of the settling tank is taken as 120°.
  • the end of the insertion tube is horn-shaped, the diameter of the bell mouth is 100mm, and the bottom is provided with a sewage outlet 10.
  • the installation height of the micro differential pressure gauge 7 is 300 mm.
  • Application Example 1 Production of tin-plated products with a coating thickness of 1.1 g /m and below with low lead content:
  • a tin plating unit with an annual output of 200,000 tons adopts an insoluble anode tin plating process.
  • the plating solution is an environmentally friendly MSA plating solution. Products with a coating thickness of 1.1g/m 2 and below are the mainstream products produced by this unit. To produce tin-plated products with low lead content, the following production processes are used:
  • the tin-plated substrate adopts electrolytic alkaline cleaning in the alkaline cleaning process section of the tin-plating unit.
  • the alkaline cleaning solution is a mixed solution of potassium hydroxide and sodium hydroxide containing defoaming agent and surfactant.
  • the content is 13%wt, the content of potassium hydroxide is 2%wt, the content of defoamer is 0.03%wt, and the content of surfactant is 0.5%wt;
  • the electrode material is Ti+YiO 2 , the thickness of YiO 2 is 5 ⁇ m, the alkaline cleaning current density is controlled at 20A/dm 2 , and the temperature of the alkaline cleaning solution is controlled at 40°C;
  • the brush wire is made of nylon material containing abrasive (SiC), and the particle size of SiC is in 200 mesh, nylon material brush roller is kept in close contact with the strip through the pneumatic cylinder, the rotation speed of the brush roller is 300 rpm, and the pressure is controlled at 500 N;
  • the pickling adopts chemical pickling.
  • the pickling medium is sulfuric acid, the concentration of sulfuric acid is 5%, and the temperature of the pickling solution is 55 °C.
  • the pickled strip passes through a rinsing tank, two sets of brush rollers and two pairs of water nozzles are arranged in the rinsing tank, and a pair of squeeze rollers are equipped on the top.
  • the material of the brush wire is nylon material, and the nylon material brush roller is kept in close contact with the strip steel through the pneumatic cylinder.
  • the rotation speed of the brush roller is 200rpm and the pressure is controlled at 200N.
  • the water nozzles are fan-shaped nozzles, and the spray volume of each group of nozzles is not less than 10m 3 /h.
  • the squeeze roller is made of polyurethane material, and the hardness of the polyurethane material is 75A;
  • the electrode material used in the electroplating process is Ti+YiO 2 , the thickness of YiO 2 is 10 ⁇ m, the concentration of tin ions in the plating solution is 16 g/L, the current density is 15 A/dm 2 , and the temperature of the plating solution is controlled at 50°C;
  • the plating solution enters the lead removal system, and 1.0g/L of barium hydroxide is added to the reaction vessel (prepared to a concentration of 2%, and the preparation temperature is 70°C).
  • the residence time in the tank is 60 minutes, and the plating solution after the reaction enters the vertical flow sedimentation tank by means of overflow, and the residence time of the plating solution in the sedimentation tank is 4 hours, and the clear liquid overflows through the upper part of the sedimentation tank after the sedimentation.
  • the mud at the bottom of the settling tank is pumped into the filter press through the mud pump, the start and stop of the mud pump is controlled by the pressure differential gauge at the bottom, the clear liquid obtained by the pressure filtration is returned to the plating bath, and the mud cake is Solid waste recycling.
  • the lead ion concentration in the plating solution can be stably controlled below 1.0mg/L, and the lead content of tinplates with different coating thicknesses can be stably controlled below 50mg/kg to achieve stable production of tinplates with low lead content.
  • the tin plate with a coating thickness of 2.0g/m 2 is a tin plate with a medium amount of tin plating.
  • the tin plating unit of insoluble anode and MSA plating solution when producing tin products with low lead content of this specification, the following production is used. Craft:
  • the tin-plated substrate adopts electrolytic alkaline cleaning in the alkaline cleaning process section of the tin-plating unit.
  • the alkaline cleaning solution is a mixed solution of potassium hydroxide and sodium hydroxide containing defoaming agent and surfactant.
  • the content is 18%wt, the content of potassium hydroxide is 3%wt, the content of defoamer is 0.05%wt, and the content of surfactant is 0.8%wt;
  • the electrode material is Ti+YiO 2
  • the thickness of YiO 2 is 10 ⁇ m
  • the current density of the alkaline cleaning is controlled at 10A/dm 2
  • the temperature of the alkaline cleaning solution is controlled at 55°C;
  • the rotation direction of the brush rollers is opposite to the running direction of the strip steel.
  • the particle size is 300 mesh, the nylon material brush roller is kept in close contact with the strip steel through the pneumatic cylinder, the rotation speed of the brush roller is 180 rpm, and the pressure is controlled at 400 N;
  • the pickling adopts chemical pickling, the pickling medium is sulfuric acid, the concentration of sulfuric acid is 10%, and the temperature of the pickling solution is 55 °C.
  • the pickling solution is sprayed through the fan nozzle To the surface of the strip, the spray volume of each group of nozzles is not less than 15m 3 /h;
  • the pickled strip passes through a rinsing tank, two sets of brush rollers and two pairs of water nozzles are arranged in the rinsing tank, and a pair of squeeze rollers are equipped on the top.
  • the material of the brush wire is nylon material.
  • the nylon material brush roller is kept in close contact with the strip steel through the pneumatic cylinder.
  • the rotation speed of the brush roller is 250rpm and the pressure is controlled at 250N.
  • the water nozzles are fan-shaped nozzles, and the spray volume of each group of nozzles is not less than 15m 3 /h.
  • the squeeze roller is made of polyurethane material, and the hardness of the polyurethane material is 80A;
  • the electrode used in the electroplating process is Ti+YiO 2 , the thickness of YiO 2 is 20 ⁇ m, the concentration of tin ions in the plating solution is 20 g/L, the current density is 15 A/dm 2 , and the temperature of the plating solution is controlled at 45°C;
  • the unit adopts tin raw material with a purity of 99.9% (the lead content is greater than 0.01%), the plating solution after passing through the tin dissolution system enters the lead removal system, and 1.2g/L of barium hydroxide (prepared) is added to the reaction vessel. Add into a concentration of 2%, the preparation temperature is 70 ° C), the residence time of the plating solution in the reaction tank is 90 minutes, the plating solution after the reaction enters the vertical flow sedimentation tank by overflowing, and the plating solution settles The residence time in the tank is 6 hours. After sedimentation, the clear liquid overflows into the plating bath through the upper part of the sedimentation tank. The mud at the bottom of the sedimentation tank is pumped into the filter press by the mud pump. Differential meter control, the clear liquid obtained by pressure filtration is returned to the plating tank, and the mud cake is recycled as solid waste.
  • the lead ion concentration in the plating solution can be stably controlled below 1.0mg/L, and the lead content of tinplates with different coating thicknesses can be stably controlled below 50mg/kg to achieve stable production of tinplates with low lead content.
  • the tinplate with a coating thickness of 2.8g/m 2 is a tinplate with a medium amount of tin plating.
  • the following production is used. Craft:
  • the tin-plated substrate adopts electrolytic alkaline cleaning in the alkaline cleaning process section of the tin-plating unit.
  • the alkaline cleaning solution is a mixed solution of potassium hydroxide and sodium hydroxide containing defoaming agent and surfactant.
  • the content is 20%wt, the content of potassium hydroxide is 1%wt, the content of defoamer is 0.01%wt, and the content of surfactant is 1.0wt%;
  • the electrode material is Ti+YiO 2
  • the thickness of YiO 2 is 10 ⁇ m
  • the current density of the alkaline cleaning is controlled at 15A/dm 2
  • the temperature of the alkaline cleaning solution is controlled at 50°C;
  • the rotation direction of the brush rollers is opposite to the running direction of the strip steel.
  • the particle size is 500 mesh, the nylon material brush roller is kept in close contact with the strip steel through the pneumatic cylinder, the rotation speed of the brush roller is 200 rpm, and the pressure is controlled at 450 N;
  • the pickling adopts chemical pickling, the pickling medium is sulfuric acid, the concentration of sulfuric acid is 20%, and the temperature of the pickling solution is 40°C.
  • the pickling solution is sprayed through the fan-shaped nozzle To the surface of the strip, the spray volume of each group of nozzles is not less than 13m 3 /h;
  • the pickled strip passes through a rinsing tank, two sets of brush rollers and two pairs of water nozzles are arranged in the rinsing tank, and a pair of squeeze rollers are equipped on the top.
  • the material of the brush wire is nylon material, and the nylon material brush roller is kept in close contact with the strip steel through the pneumatic cylinder.
  • the rotation speed of the brush roller is 200rpm and the pressure is controlled at 300N.
  • the water nozzles are fan-shaped nozzles, and the spray volume of each group of nozzles is not less than 12m 3 /h.
  • the squeeze roller is made of polyurethane material, and the hardness of the polyurethane material is 78A;
  • the electrode used in the electroplating process is Ti+YiO 2 , the thickness of YiO 2 is 15 ⁇ m, the concentration of tin ions in the plating solution is 18 g/L, the current density is 25 A/dm 2 , and the temperature of the plating solution is controlled at 50 °C;
  • the unit adopts tin raw material with a purity of 99.9% (the lead content is greater than 0.01%), the plating solution after passing through the tin melting system enters the lead removal system, and 1.5g/L of barium hydroxide (prepared) is added to the reaction vessel.
  • the concentration of 2% is added, the preparation temperature is 75 ° C), the residence time of the plating solution in the reaction tank is 70 minutes, and the plating solution after the reaction enters the vertical flow sedimentation tank by means of overflow, and the plating solution settles
  • the residence time in the tank is 4.5 hours.
  • the clear liquid overflows into the plating tank through the upper part of the sedimentation tank.
  • the mud at the bottom of the sedimentation tank is pumped into the filter press through the mud pump. Differential meter control, the clear liquid obtained by pressure filtration is returned to the plating tank, and the mud cake is recycled as solid waste.
  • the lead ion concentration in the plating solution can be stably controlled below 0.8mg/L, and the lead content of tinplates with different coating thicknesses can be stably controlled below 30mg/kg to achieve stable production of tinplates with low lead content.
  • Application Example 4 Production of tin-plated products with a coating thickness of 5.6g/m 2 and above:
  • Tin-plated sheets with a coating thickness of 5.6g/m 2 and above are products with high tin-plating content, and are often used in the packaging of milk powder cans and fruit and vegetable cans.
  • insoluble anodes and MSA bath tinning units the following production processes are used when producing tin-plated products with low lead content of this specification:
  • the tin-plated substrate adopts electrolytic alkaline cleaning in the alkaline cleaning process section of the tin-plating unit.
  • the alkaline cleaning solution is a mixed solution of potassium hydroxide and sodium hydroxide containing defoaming agent and surfactant.
  • the content is 15%wt, the content of potassium hydroxide is 5%wt, the content of defoamer is 0.04%wt, and the content of surfactant is 0.7%wt;
  • the electrode material is Ti+YiO 2 , the thickness of YiO 2 is 15 ⁇ m, the current density of the alkaline cleaning is controlled at 25A/dm 2 , and the temperature of the alkaline cleaning solution is controlled at 40°C;
  • the pickling adopts chemical pickling, the pickling medium is sulfuric acid, the concentration of sulfuric acid is 20%, and the temperature of the pickling solution is 45°C.
  • the spray volume of each group of nozzles is not less than 15m 3 /h;
  • the pickled strip passes through a rinsing tank, two sets of brush rollers and two pairs of water nozzles are arranged in the rinsing tank, and a pair of squeeze rollers are equipped on the top.
  • the material of the brush wire is nylon material, and the nylon material brush roller is kept in close contact with the strip steel through the pneumatic cylinder.
  • the rotation speed of the brush roller is 250rpm and the pressure is controlled at 200N.
  • the water nozzles are fan-shaped nozzles, and the spray volume of each group of nozzles is not less than 15m 3 /h.
  • the squeeze roller is made of polyurethane material, and the hardness of the polyurethane material is 78A;
  • the electrode used in the electroplating process is Ti+YiO 2 , the thickness of YiO 2 is 10 ⁇ m, the concentration of tin ions in the plating solution is 20 g/L, the current density is 15 A/dm 2 , and the temperature of the plating solution is controlled at 45°C;
  • the unit uses tin raw material with a purity of 99.9% (the lead content is greater than 0.01%), the plating solution after passing through the tin melting system enters the lead removal system, and 1.3g/L of barium hydroxide (prepared) is added to the reaction vessel. A concentration of 2% was added, and the preparation temperature was 65° C.), the residence time of the plating solution in the reaction tank was 80 minutes, and the plating solution after the reaction entered the vertical flow sedimentation tank by overflowing. The residence time in the tank is 5.5 hours. After sedimentation, the clear liquid overflows into the plating bath through the upper part of the sedimentation tank. The mud at the bottom of the sedimentation tank is pumped into the filter press by the mud pump. Differential meter control, the clear liquid obtained by pressure filtration is returned to the plating tank, and the mud cake is recycled as solid waste.
  • the lead ion concentration in the plating solution can be stably controlled below 0.5mg/L, and the lead content of tinplates with different coating thicknesses can be stably controlled below 20mg/kg to achieve stable production of tinplates with low lead content.
  • Application Example 5 Production of tin-plated products with a coating thickness of 8.4g/m 2 and above:
  • the tin plate with a coating thickness of 8.4g/m 2 and above is a product with a high amount of tin plating.
  • the tin plating unit of insoluble anode and MSA plating solution when producing this specification of tin plating products with low lead content, the following production is used Craft:
  • the tin-plated substrate adopts electrolytic alkaline cleaning in the alkaline cleaning process section of the tin-plating unit.
  • the alkaline cleaning solution is a mixed solution of potassium hydroxide and sodium hydroxide containing defoaming agent and surfactant.
  • the content is 20%wt, the content of potassium hydroxide is 1%wt, the content of defoamer is 0.02%wt, and the content of surfactant is 0.8%wt;
  • the electrode material is Ti+YiO 2
  • the thickness of YiO 2 is 20 ⁇ m
  • the current density of the alkaline cleaning is controlled at 30A/dm 2
  • the temperature of the alkaline cleaning solution is controlled at 40°C;
  • the rotation direction of the brush rollers is opposite to the running direction of the strip steel.
  • the particle size is 700 mesh, the nylon material brush roller is kept in close contact with the strip steel through the pneumatic cylinder, the rotation speed of the brush roller is 250 rpm, and the pressure is controlled at 200 N;
  • the pickling adopts chemical pickling, the pickling medium is sulfuric acid, the concentration of sulfuric acid is 15%, and the temperature of the pickling solution is 50°C.
  • the spray volume of each group of nozzles is not less than 10m 3 /h;
  • the pickled strip passes through a rinsing tank, two sets of brush rollers and two pairs of water nozzles are arranged in the rinsing tank, and a pair of squeeze rollers are equipped on the top.
  • the material of the brush wire is nylon material, and the nylon material brush roller is kept in close contact with the strip steel through the pneumatic cylinder.
  • the rotation speed of the brush roller is 150rpm and the pressure is controlled at 200N.
  • the water nozzles are fan-shaped nozzles, and the spray volume of each group of nozzles is not less than 15m 3 /h.
  • the squeeze roller is made of polyurethane material, and the hardness of the polyurethane material is 80A;
  • the electrode used in the electroplating process is Ti+YiO 2 , the thickness of YiO 2 is 15 ⁇ m, the concentration of tin ions in the plating solution is 20 g/L, the current density is 20 A/dm 2 , and the temperature of the plating solution is controlled at 50 °C;
  • the unit uses tin raw material with a purity of 99.9% (the lead content is greater than 0.01%), the plating solution after passing through the tin melting system enters the lead removal system, and 1.1g/L of barium hydroxide (prepared) is added to the reaction vessel. Add into a concentration of 2%, the preparation temperature is 60 ° C), the residence time of the plating solution in the reaction tank is 75 minutes, the plating solution after the reaction enters the vertical flow sedimentation tank by means of overflow, and the plating solution settles The residence time in the tank is 5 hours. After sedimentation, the clear liquid overflows into the plating bath through the upper part of the sedimentation tank. The mud at the bottom of the sedimentation tank is pumped into the filter press through the mud pump. Differential meter control, the clear liquid obtained by pressure filtration is returned to the plating tank, and the mud cake is recycled as solid waste.
  • the lead ion concentration in the plating solution can be stably controlled below 0.4mg/L, and the lead content of tinplates with different coating thicknesses can be stably controlled below 15mg/kg to achieve stable production of tinplates with low lead content.
  • the coating and the substrate of products with different coating thicknesses can have good adhesion properties
  • the lead ion concentration in the plating solution can be stably controlled below 1.0mg/L
  • the lead content of tin-plated sheets with different coating thicknesses can be stably controlled. Below 50mg/kg, the stable production of tinplate with low lead content is realized.

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Abstract

本发明涉及一种不溶性阳极的甲基磺酸镀层低铅含量镀锡板生产方法，该方法包括以下步骤：步骤1：碱洗工艺段，钢基板先经过电化学碱洗，碱洗液采用含氢氧化钾的氢氧化钠溶液；包含刷洗，刷辊上的刷毛为含磨料的尼龙材料；步骤2：酸洗工艺段，经碱洗后的带钢进入到化学酸洗槽，酸洗槽采用低浓度的硫酸溶液，采用高压喷射装置喷射到带钢的表面，并包含刷洗工艺，刷辊上的刷毛纯尼龙材料；步骤3：电镀工艺段，采用低电流密度，高锡离子浓度，高镀液温度，控制镀液中铅离子的沉积；步骤4：镀液中的铅通过不断体外循环进行除铅；将镀锡层中的铅含量控制在50mg/kg以下，实现低铅含量镀锡板的稳定生产，满足食品包装材料安全性的需求。

Description

一种不溶性阳极的甲基磺酸镀层低铅含量镀锡板生产方法及设备 技术领域
本发明涉及一种镀锡板制造工艺，具体涉及一种不溶性阳极甲基磺酸(即methyl sulfonic acid简称MSA)工艺低铅含量镀锡板的生产方法，属于冶金技术领域。
背景技术
镀锡板依然是主要食品和饮料包装材料，其应用范围和用量日益增长，与此同时，人们对镀锡板的质量要求也日益增加，特别是镀锡层中的铅含量。对于镀锡板的镀锡层中铅含量的控制指标，EN10333-2005“包装用钢-预期用于接触人类和动物饮食的食品或饮料的扁钢制品-镀锡板”不仅规定用于生产镀锡板的锡锭中的铅和其它杂质含量(总锡大于99.85％，铅含量小于0.01％，隔含量小于0.01％，砷含量小于0.03％)，而且还要求镀锡层中的含量也小于0.01％。中国国家标准于2017年开始实施的GB/T2520“冷轧电镀锡钢板及钢带”也从镀锡基板、镀锡原料和镀锡层中的有害元素含量进行了严格限制，最终规定镀锡层中的铅含量不大于0.01％，即基于镀层的质量分数不大于100mg/kg。
由于铅和锡是同族元素，电镀锡的过程中自然而然还形成锡和铅的共镀，从而造成镀层中铅含量的超标，为生产低铅含量的镀锡板，目前常用方法是采用低铅含量的锡原料，为制备低铅含量的锡原料，需要采用特殊的净化工艺，提高锡原料的价格，大幅增加生产成本。
不溶性阳极电镀工艺是当前电镀锡生产中的主流技术，在不溶性阳极电镀体系中，阳极只是起导电作用，不参与电极反应，阳极和阴 极间的距离始终保持恒定，容易控制电镀过程中的电流密度，因此其电流密度通常要比可溶性阳极高。与PSA镀液相比，MSA镀液属于环保型镀液，这二种镀液的导电性存在一定的差异，电镀过程所能实现的电流密度也不同。
对于不溶性阳极的MSA电镀锡工艺，控制镀层中的铅含量，不仅需要从锡锭原料中的铅含量源头进行控制，还需从镀液中铅含量的去除，镀锡过程中碱洗和酸洗的方法，以及电镀工艺等方面进行控制，才能得到低铅含量的镀锡产品。
为此针对具有环保属性的MSA镀液系统，发明一种不溶性阳极的镀锡层铅含量的控制技术，对于镀锡技术的发展具有重要的现实意义。
发明内容
本发明正是针对现有技术中存在的问题，提供一种不溶性阳极MSA工艺低铅含量镀锡板的生产方法，该技术方案从镀液的净化开始，建立合适的碱洗、酸洗和电镀工艺，实现不溶性阳极MSA工艺低铅含量镀锡板的稳定生产。
为了实现上述目的，本发明的技术方案如下，一种不溶性阳极低铅含量镀锡板，所述组分及含量如下：C:0.003～0.15％、Si:≤0.03％、Mn：0.1～1％、P：≤0.02％、S：≤0.02％、Cu≤0.020％、Alt：0.01～0.2％，余量为铁和杂质，镀锡板镀层铅含量控制在50mg/kg以下，其中镀锡板厚度为0.17—0.55mm，镀层的厚度为1.1—11.2g/m 2，优选为镀层的厚度要求2.0—8.4g/m 2。
一种不溶性阳极低铅含量镀锡板的加工设备，所述加工设备包括碱洗装置、矫直机、酸洗装置、电镀装置以及除铅系统，镀锡基板依次经过碱洗装置、矫直机、酸洗装置、电镀装置，最后进入除铅系统；其中，碱洗装置主要包括碱液槽，其出口设置刷洗槽，内设置有两组刷辊；与常规碱洗装置相比，本发明增加了两组刷辊装置，通过刷辊材质选择和压力控制，配合电解碱洗，可以较为彻底的去除镀锡基板平面部位和凹坑部位残留的油污；
矫直机：经碱洗后的镀锡基板，经过多辊矫直机对镀锡基板进行矫直，增加镀锡基板横向和纵向的平整度，获得良好的板型，为后续电镀锡工序乃至下游用户涂装提供保障；
酸洗装置包括两个酸洗槽，所述酸洗槽内设置有高压喷射装置，喷嘴采用扇形喷嘴，酸槽顶部设置有一对挤干辊，内有扇形喷嘴；酸洗后的带钢经过一个漂洗槽，漂洗槽内布置二组刷辊和二组水喷嘴，槽顶部配备有一对挤干辊。
本发明增加了刷辊装置，可以较好的去除镀锡基板残留的氧化层，起到良好的活化镀锡基板的效果。同时水喷嘴采用扇形设计，可以去除镀锡基板残留的硫酸，避免代入到电镀液中造成镀液组分失衡进而影响电镀效果；电镀装置包括电镀液槽和锡溶解罐；除铅系统包括氢氧化钡溶解罐、反应罐、沉降罐、泥浆泵以及压滤机；所述氢氧化钡溶解罐依次连接反应罐、沉降罐、泥浆泵以及压滤机，该除铅系统在持续降低镀液中铅离子浓度起到了至关重要的作用，其核心组件反应罐和沉降罐合理的结构设计，充分发挥了除铅效果，最大程度的 将镀液铅离子浓度降低至1.0mg/L以下，为低铅含量镀锡板生产提供优异条件。同时除铅系统中的压滤机可将除铅过程中生成的硫酸铅钡沉淀与锡泥一同去除，达到净化镀液的效果，为提升电镀效果和表面质量发挥了关键作用。
除铅系统的主要核心部件为反应罐和沉降罐：在反应罐内部设置有一预混室，氢氧化钡在带有搅拌装置的预混室中与镀锡溶液充分混合，预混室的宽度为罐体直径为
Figure PCTCN2020118977-appb-000001
预混室中搅拌桨M1的搅拌转速为400～600rpm。在主反应室中微细硫酸钡不断吸附镀液中的Pb 2+，主要反应器设置有搅拌桨M2，搅拌桨采用平桨，搅拌桨的宽度d为容器直径的
Figure PCTCN2020118977-appb-000002
搅拌桨的转速为30～60rpm。
沉降罐结构的最上方设置有进液管，最下方设置有排污口，罐体的侧面设置有人孔、观察孔以及微压差计，沉降罐罐体从上往下依次设置有顶盖、澄清段(H1)、斜板沉降段(H2)以及主沉降段(H3)。主沉降段的直径d由镀锡溶液的处理量(L)决定，d与L之间的关系为
Figure PCTCN2020118977-appb-000003
式中：L的单位L/h，d的单位为mm。罐体澄清段的直径D为(1.5～2.0)d。主沉降段高度(H3)为(1.5～2.0)d，斜板沉降段的高度(H2)为1.0～1.5m，澄清段的高度(H1)为1.5～2.0m，斜板的倾斜角(A1)为60～90°。沉降罐下部锥角的角度(A3)的范围在90～120°。沉降罐内部设置有中心下降管。中心下降管的直径dd与主沉降段壳体的直径有关，
Figure PCTCN2020118977-appb-000004
中心下降管插入到溶液的深度为h，
Figure PCTCN2020118977-appb-000005
插入管的端部呈喇叭状，喇叭口的直径B＝(2～4)dd。罐体锥形段设置有微压差计，微压差计 的测试精度为0.001MPa，微压差计的安装高度距离泥浆出口为300mm，微压差计一旦检测到压力比初始值增加15％，泥浆泵即启动，当微压差计检测到压力下降10％，后抽取镀液的总量在2m 3后，泥浆泵体停止工作。罐底的沉降物采用泥浆泵抽走，泥浆泵采用定时模式启停，所抽取的沉淀物通过压滤机，压滤机采用尼龙过滤布，过滤精度为1μm。
一种不溶性阳极的甲基磺酸镀层低铅含量镀锡板的生产方法，所述方法包括以下步骤：
步骤1：碱洗工艺段，镀锡基板先经过电化学碱洗，碱洗液采用含氢氧化钾的氢氧化钠溶液；增设刷洗工艺，刷辊上的刷毛为含磨料的尼龙材料；
步骤2：酸洗工艺段，经碱洗后的带钢进入到化学酸洗槽，酸洗槽采用低浓度的硫酸溶液，采用高压喷射装置喷射到带钢的表面，并增设刷洗工艺，刷辊上的刷毛纯尼龙材料；
步骤3：电镀工艺段，带钢进入到不溶性阳极的MSA镀液系统后，带钢在较低的电流密度下进行电镀，镀液中的锡离子通过体外循环的方式进行调节，电镀槽中的镀液通过循环泵打入到锡溶解罐，锡粒与注入氧气的镀液在锡溶解罐中反应，提高镀液中锡离子的浓度；
步骤4：完成电镀后的镀液进入到除铅系统，镀液中的铅通过不断体外循环进行除铅，
通过调节生产过程中的这些工艺参数和增设相应的设备，将镀锡层中的铅含量控制在50mg/kg以下。
作为本发明的一种改进，所述步骤1：具体如下：
镀锡基板进入到镀锡机组，在镀锡生产工艺的碱洗环节采用电解碱洗，碱洗采用的碱洗液为含氢氧化钾的氢氧化钠溶液，溶液中还含有消泡剂和表面活性剂，消泡剂含量0.01～0.10％wt，表面活性剂含量0.1～1.0％wt，碱洗液中氢氧化钠的含量5～30％wt，(优选15～20％)氢氧化钾的含量0.1～5％wt；碱洗机组中电极与带钢形成电解池，电极材料采用纯Ti材料，为提高电极材料的电导率，在Ti材表面镀一层YiO 2，YiO 2的厚度在5～20μm，碱洗电流密度控制在10～30A/dm 2，碱洗液的温度控制在40～55℃。电解碱洗较化学碱洗效果更佳，采用纯钛表面镀有一层YiO 2的碱洗极板，可以提高电解碱洗效果。YiO 2涂层过厚则会大幅增加极板的采购成本，厚度在5～20um性价比最高；碱洗电流密度控制在10～30A/dm 2，碱洗电流密度太小则碱洗效果不佳，电流密度过大，则会造成镀锡基板变色而影响后续电镀质量。根据Arrhenius反应速率经验公式，提高溶液温度可以提升镀锡基板除油效果。同时，为了避免温度过高造成碱洗液中消泡剂和表面活性剂等组分发生降解而影响碱洗效果，最终确定了碱洗液的温度为40～55℃。
作为本发明的一种改进，所述步骤1中，碱洗槽的出口带有一个刷洗槽，刷洗槽内带有两组刷辊，刷辊的转动方向与带钢运行方向相反，刷丝的材料采用含磨料(SiC)尼龙材料，SiC的粒度在200～800目之间，尼龙材料刷辊通过气压缸保持与带钢的紧密接触，刷辊工作时的转动速度为100～300rpm，压力控制在200～500N。镀锡基板粗糙度一般为0.2～1.0um，增加刷辊装置可以通过机械力去除镀锡基板表面残留的氧化铁皮、杂质和油污。刷丝材质为含磨料(SiC)尼龙材料，且SiC的粒度在200～800目之间，可以确保刷丝的柔韧性，在确保刷洗效果的同时，还可以延长刷辊使用周期；刷辊压力大小直 接决定了镀锡基板与辊面的接触程度，当刷辊压力太小时，仅能去除镀锡基板表面残留的杂质和油污，对粗糙度较大的镀锡基板表面残留的杂质和油污去除效果不佳；当刷辊压力太大时，辊面刷丝与镀锡基板接触程度过大，虽然对镀锡基板残留的杂质和油污去除效果更佳，但是会造成镀锡基板表面硬划伤，影响后续镀锡产品的表面质量。
作为本发明的一种改进，所述步骤2中，酸洗采用的是化学酸洗，酸洗介质为稀硫酸，硫酸浓度5～20％，酸洗液的温度为40～55℃，酸洗工艺段设置有2个酸洗槽，酸洗液通过扇形喷嘴喷射到带钢的表面，每组喷嘴的喷射量不小于10～15m 3/h。酸洗主要是去除镀锡基板前表层极微量的氧化铁皮，达到活化镀锡基板的效果，为后续电镀锡过程提供高活性的表面。硫酸浓度和温度过低，活化效果不佳，浓度和温度过高则会破坏镀锡基板的表面状态，不利于锡层的沉积。
作为本发明的一种改进，所述步骤2中，酸洗后的带钢经过一个漂洗槽，漂洗槽内布置二组刷辊和二对水喷嘴，顶部配备有一对挤干辊。刷丝的材料采用尼龙材料，尼龙材料刷辊通过气压缸保持与带钢的紧密接触，刷辊工作时的转动速度为100～300rpm，压力控制在200～300N。水喷嘴采用扇形喷嘴，每组喷嘴的喷射量不小于10～15m 3/h。挤干辊采用的是聚氨酯材料，聚氨酯材料的硬度在75-80A。漂洗槽内的两组刷辊，采用较小的压力，在不对镀锡基板表面产生硬擦伤的前提下，又可以提升对镀锡基板表面残余氧化层的酸洗去除能力；漂洗槽中两对水喷嘴以及顶部的挤干辊可以将钢板表面的残留硫酸溶液去除，避免带钢在进入到电镀槽之前残留的的硫酸溶液与钢板生成铁离子，带入到电镀槽中。
作为本发明的一种改进，所述步骤3中，电镀过程中采用的电极 材料为纯Ti+YiO 2电极，YiO 2的厚度在10～20μm，镀液中锡离子的浓度控制在16～20g/L，电流密度控制在15～25A/dm 2，镀液的温度控制在40～50℃；镀液中铅离子浓度通过除铅系统来控制，除铅系统包括反应、吸附、沉淀、分离等工艺过程，经除铅系统后镀液铅离子浓度控制在1.0mg/L以下。与电解碱洗极板原理相同，纯Ti+YiO 2极板可以提高电镀效果。提高锡离子浓度可以抑制铅离子沉积到镀层中，但是锡离子浓度过高，会造成镀液中锡泥含量的急剧增加。电流密度控制在15～25A/dm 2，镀液的温度控制在40～50℃，可以获得致密的镀层。温度过低电化学反应效率下降，温度过高会造成镀液中的有机组分降解而失去活性。电流密度过低则影响机组高速稳定生产，电流密度过高则镀层晶粒粗大且不均匀。
作为本发明的一种改进，所述步骤4中，除铅采用的是氢氧化钡溶液，氢氧化钡的加入量根据锡原料中铅含量而定，其间的关系式为：
氢氧化钡添加量(g/L)＝K*锡原料中的铅含量(mg/kg)，K取值范围：(0.015～0.020)。
镀液中铅离子的来源主要有锡原料和酸洗液，酸洗液中处于稳定状态，而锡原料铅含量波动较大，因此锡原料铅含量直接影响着镀液铅离子浓度。氢氧化钡降铅的原理是氢氧化钡与镀液中硫酸生成硫酸钡，硫酸钡包裹镀液中的铅离子形成共沉淀，经过压滤机去除。根据生产经验得出如下公式，氢氧化钡添加量(g/L)＝K*锡原料中的铅含量(mg/kg)，K取值范围：(0.015～0.020)。氢氧化钡合适的添加量可以最大程度的去除镀液中的铅离子，使得镀液铅离子浓度控制在1.0mg/L以下，同时又不会在镀液中因加入过多的氢氧化钡而生产过多的硫酸钡，造成镀液中钡离子的富集而影响电镀效果。
作为本发明的一种改进，所述步骤4中，除铅过程为：将适量的 氢氧化钡溶液在搅拌的状态下加入到镀液中，在搅拌的状态下氢氧化钡与镀液中的硫酸反应，生成细微的硫酸钡颗粒，在搅拌的状态下微细硫酸钡吸附镀液中的铅离子，经60～90分钟的吸附过程后，镀液通过溢流的方式进入到竖流式沉降罐，沉降后清液通过沉降罐上部溢流到镀液槽中，沉降罐底部的泥浆通过泥浆泵打入到压滤机中，泥浆泵的启停由底部的压差计控制，压滤得到的清液回到镀液槽，泥饼作为固体废弃物回收利用。搅拌状态下，在60～90分钟内，可以确保氢氧化钡与镀液中硫酸生成硫酸钡的速度，以及硫酸钡与镀液中的铅离子的充分吸附。上层清液回流到镀液槽中，经过多次、持续不断的降铅处理过程，达到快速降低镀液铅离子的目的。
相对于现有技术，本发明具有如下优点，1)该技术方案可使得不同镀锡量产品镀层与基体间具有良好的附着力，可实现镀层中铅含量的稳定控制，用纯度为99.9％的锡粒原料所制备的镀液，经除铅系统后镀液铅离子浓度可以稳定控制在1.0mg/L以下，大幅降低为得到低铅含量的镀液对锡原料的要求，降低生产成本；2)采用该镀液通过调节生产过程中各工艺参数，可以将镀锡层中的铅含量控制在50mg/kg以下，实现低铅含量镀锡板的稳定生产，增强低铅含量镀锡板在金属包装行业的竞争力；3)本发明增加了刷辊装置，可以较好的去除镀锡基板残留的氧化层，起到良好的活化镀锡基板的效果。同时水喷嘴采用扇形设计，可以去除镀锡基板残留的硫酸，避免代入到电镀液中造成镀液组分失衡进而影响电镀效果；4)该除铅系统在持续降低镀液中铅离子浓度起到了至关重要的作用，其核心组件反应罐 和沉降罐合理的结构设计，充分发挥了除铅效果，最大程度的将镀液铅离子浓度降低至1.0mg/L以下，为低铅含量镀锡板生产提供优异条件。同时除铅系统中的压滤机可将除铅过程中生成的硫酸铅钡沉淀与锡泥一同去除，达到净化镀液的效果，起到提升电镀效率和表面质量的作用。
附图说明
图1为本发明整体流程示意图；
图2除铅系统中反应罐结构图；
图3除铅系统中沉降罐结构图；
图中：1、进液管，2、顶盖，3、溢流堰，4、斜板，5、中心下降管，6、人孔，7、微压差计，8、出料口，9、观察孔，10、排污口，H1、澄清段，H2、斜板沉降段，H3、主沉降段，H4、沉降罐底部锥形部分距离排泥口的垂直高度，H5、微压差计距离排泥口的垂直高度。
具体实施方式
为了加深对本发明的理解，下面结合附图对本实施例做详细的说明。
实施例1：
方案1：一种不溶性阳极低铅含量镀锡板，所述组分及含量如下：C:0.003、Si:0.01％、Mn：0.1％、P：0.01％、S：0.01％、Cu:0.010％、Alt：0.01％，余量为铁和杂质；
方案2：一种不溶性阳极低铅含量镀锡板，所述组分及含量如下：C:0.15％、Si:0.03％、Mn：1％、P：0.02％、S：0.02％、Cu：0.020％、Alt：0.2％，余量为铁和杂质；
方案3：一种不溶性阳极低铅含量镀锡板，所述组分及含量如下：C:0.008％、Si:0.02％、Mn：0.5％、P：0.01％、S：0.01％、Cu：0.005％、Alt：0.15％，余量为铁和杂质；
上述三个方案中，镀锡板镀层铅含量控制在50mg/kg以下，其中镀锡板厚度为0.17—0.55mm，镀层的厚度为1.1—11.2g/m 2，优选为镀层的厚度要求2.0—8.4g/m 2。在实际的应用中，镀锡板厚度优选为0.20mm、0.25mm、0.30mm、0.43mm、0.50mm、0.55mm等，镀层的厚度为2.5g/m 2、3.0g/m 2、4.5g/m 2、5.6g/m 2、7.5g/m 2、8.0g/m 2、8.5g/m 2、9.8g/m 2、11.0g/m 2等。该技术方案可使得不同镀锡量产品镀层与基体间具有良好的附着力，可实现镀层中铅含量的稳定控制，用纯度为99.9％的锡粒原料所制备的镀液，经除铅系统后镀液铅离子浓度可以稳定控制在1.0mg/L以下，大幅降低为得到低铅含量的镀液对锡原料的要求，降低了生产成本。
实施例2：参见图1-图3，一种不溶性阳极低铅含量镀锡板的加工设备，所述加工设备包括碱洗装置、矫直机、酸洗装置、电镀装置以及除铅系统，镀锡基板依次经过碱洗装置、矫直机、酸洗装置、电镀装置，最后进入除铅系统；
其中，碱洗装置主要包括碱液槽，其出口设置刷洗槽，内设置有两组刷辊；与常规碱洗装置相比，本发明增加了两组刷辊装置，通过 刷辊材质选择和压力控制，配合电解碱洗，可以较为彻底的去除镀锡基板平面部位和凹坑部位残留的油污；
矫直机：经碱洗后的镀锡基板，经过多辊矫直机对镀锡基板进行矫直，增加镀锡基板横向和纵向的平整度，获得良好的板型，为后续电镀锡工序乃至下游用户涂装提供保障；
酸洗装置包括两个酸洗槽，所述酸洗槽内设置有高压喷射装置，喷嘴采用扇形喷嘴，酸槽顶部设置有一对挤干辊，内有扇形喷嘴；酸洗后的带钢经过一个漂洗槽，漂洗槽内布置二组刷辊和二组水喷嘴，槽顶部配备有一对挤干辊。
本发明增加了刷辊装置，可以较好的去除镀锡基板残留的氧化层，起到良好的活化镀锡基板的效果。同时水喷嘴采用扇形设计，可以去除镀锡基板残留的硫酸，避免代入到电镀液中造成镀液组分失衡进而影响电镀效果；电镀装置包括电镀液槽和锡溶解罐；除铅系统包括氢氧化钡溶解罐、反应罐、沉降罐、泥浆泵以及压滤机；所述氢氧化钡溶解罐依次连接反应罐、沉降罐、泥浆泵以及压滤机，该除铅系统在持续降低镀液中铅离子浓度起到了至关重要的作用，其核心组件反应罐和沉降罐合理的结构设计，充分发挥了除铅效果，最大程度的将镀液铅离子浓度降低至1.0mg/L以下，为低铅含量镀锡板生产提供优异条件。同时除铅系统中的压滤机可将除铅过程中生成的硫酸铅钡沉淀与锡泥一同去除，达到净化镀液的效果，为提升电镀效果和表面质量发挥了关键作用。
除铅系统的主要核心部件为反应罐和沉降罐：在反应罐内部设 置有一预混室，氢氧化钡在带有搅拌装置的预混室中与镀锡溶液充分混合，预混室的宽度为罐体直径为
Figure PCTCN2020118977-appb-000006
预混室中搅拌桨M1的搅拌转速为400～600rpm。在主反应室中微细硫酸钡不断吸附镀液中的Pb 2+，主要反应器设置有搅拌桨M2，搅拌桨采用平桨，搅拌桨的宽度d为容器直径的
Figure PCTCN2020118977-appb-000007
搅拌桨的转速为30～60rpm。
参见图3，沉降罐的结构如图所示，最上方设置有进液管1，最下方设置有排污口10，罐体的侧面设置有人孔6、观察孔9以及微压差计7，沉降罐罐体从上往下依次设置有顶盖2、澄清段(H1)、斜板沉降段(H2)以及主沉降段(H3)，主沉降段的直径d由镀锡溶液的处理量(L)决定，d与L之间的关系为
Figure PCTCN2020118977-appb-000008
式中：L的单位L/h，d的单位为mm。罐体澄清段的直径D为(1.5～2.0)d，罐体澄清段内设置有溢流堰3，主沉降段高度(H3)为(1.5～2.0)d，斜板沉降段的高度(H2)为1.0～1.5m，斜板沉降段中设置有斜板4，澄清段的高度(H1)为1.5～2.0m，斜板的倾斜角(A1)为60～90°。沉降罐下部锥角的角度(A3)的范围在90～120°。沉降罐内部设置有中心下降管5，中心下降管5的直径dd与主沉降段壳体的直径有关，
Figure PCTCN2020118977-appb-000009
中心下降管5插入到溶液的深度为h，
Figure PCTCN2020118977-appb-000010
Figure PCTCN2020118977-appb-000011
插入管的端部呈喇叭状，喇叭口的直径B＝(2～4)dd。罐体锥形段设置有微压差计7，微压差计7的测试精度为0.001MPa，微压差计7的安装高度距离泥浆出口为300mm，微压差计7一旦检测到压力比初始值增加15％，泥浆泵即启动，当微压差计7检测到压力下降10％，后抽取镀液的总量在2m 3后，泥浆泵体停止工作；罐底的沉降物采用泥浆泵抽走，泥浆泵采用定时模式启停，所抽取的沉淀物 通过压滤机，压滤机采用尼龙过滤布，过滤精度为1μm。
实施例3：参见图1，一种不溶性阳极的甲基磺酸(MSA)镀层低铅含量控制的镀锡板的生产方法，所述工艺包括以下步骤：
步骤1：碱洗工艺段，镀锡基板先经过电化学碱洗，碱洗液采用含氢氧化钾的氢氧化钠溶液；增设刷洗工艺，刷辊上的刷毛为含磨料的尼龙材料；
步骤2：酸洗工艺段，经碱洗后的带钢进入到化学酸洗槽，酸洗槽采用低浓度的硫酸溶液，采用高压喷射装置喷射到带钢的表面，并增设刷洗工艺，刷辊上的刷毛纯尼龙材料；
步骤3：电镀工艺段，带钢进入到不溶性阳极的MSA镀液系统后，带钢在较低的电流密度下进行电镀，镀液中的锡离子通过体外循环的方式进行调节，电镀槽中的镀液通过循环泵打入到锡溶解罐，锡粒与注入氧气的镀液在锡溶解罐中反应，提高镀液中锡离子的浓度；
步骤4：完成电镀后的镀液进入到除铅系统，镀液中的铅通过不断体外循环进行除铅，
通过调节生产过程中的这些工艺参数和增设相应的设备，将镀锡层中的铅含量控制在50mg/kg以下。
其中，所述步骤1：具体如下：
镀锡基板进入到镀锡机组，在镀锡生产工艺的碱洗环节采用电解碱洗，碱洗采用的碱洗液为含氢氧化钾的氢氧化钠溶液，溶液中还含有消泡剂和表面活性剂，消泡剂含量0.01～0.10％wt，表面活性剂含量0.1～1.0％wt，碱洗液中氢氧化钠的含量5～30％wt，优选15～20％wt氢氧化钾的含量0.1～5％wt；碱洗机组中电极与带钢形成电解池，电 极材料采用纯Ti材料，为提高电极材料的电导率，在Ti材表面镀一层YiO 2，YiO 2的厚度在5～20μm，碱洗电流密度控制在10～30A/dm 2，碱洗液的温度控制在40～55℃。电解碱洗较化学碱洗效果更佳，采用纯钛表面镀有一层YiO 2的碱洗极板，可以提高电解碱洗效果。YiO 2涂层过厚则会大幅增加极板的采购成本，厚度在5～20um性价比最高；碱洗电流密度控制在10～30A/dm 2，碱洗电流密度太小则碱洗效果不佳，电流密度过大，则会造成镀锡基板变色而影响后续电镀质量。根据Arrhenius反应速率经验公式，提高溶液温度可以提升镀锡基板除油效果。同时，为了避免温度过高造成碱洗液中消泡剂和表面活性剂等组分发生降解而影响碱洗效果，最终确定了碱洗液的温度为40～55℃。
所述步骤1中，碱洗槽的出口带有一个刷洗槽，刷洗槽内带有两组刷辊，刷辊的转动方向与带钢运行方向相反，刷丝的材料采用含磨料(SiC)尼龙材料，SiC的粒度在200～800目之间，尼龙材料刷辊通过气压缸保持与带钢的紧密接触，刷辊工作时的转动速度为100～300rpm，压力控制在200～500N。镀锡基板粗糙度一般为0.2～1.0um，增加刷辊装置可以通过机械力去除镀锡基板表面残留的氧化铁皮、杂质和油污。刷丝材质为含磨料(SiC)尼龙材料，且SiC的粒度在200～800目之间，可以确保刷丝的柔韧性，在确保刷洗效果的同时，还可以延长刷辊使用周期；刷辊压力大小直接决定了镀锡基板与辊面的接触程度，当刷辊压力太小时，仅能去除镀锡基板表面残留的杂质和油污，对粗糙度较大的镀锡基板表面残留的杂质和油污去除效果不佳；当刷辊压力太大时，辊面刷丝与镀锡基板接触程度过大，虽然对镀锡基板残留的杂质和油污去除效果更佳，但是会造成镀锡基板表面硬划伤，影响后续镀锡产品的表面质量。
所述步骤2中，酸洗采用的是化学酸洗，酸洗介质为稀硫酸，硫酸浓度5～20％，酸洗液的温度为40～55℃，酸洗工艺段设置有2个酸洗槽，酸洗液通过扇形喷嘴喷射到带钢的表面，每组喷嘴的喷射量不小于10～15m 3/h。酸洗主要是去除镀锡基板前表层极微量的氧化铁皮，达到活化镀锡基板的效果，为后续电镀锡过程提供高活性的表面。硫酸浓度和温度过低，活化效果不佳，浓度和温度过高则会破坏镀锡基板的表面状态，不利于锡层的沉积。
所述步骤2中，酸洗后的带钢经过一个漂洗槽，漂洗槽内布置二组刷辊和二对水喷嘴，顶部配备有一对挤干辊。刷丝的材料采用尼龙材料，尼龙材料刷辊通过气压缸保持与带钢的紧密接触，刷辊工作时的转动速度为100～300rpm，压力控制在200～300N。水喷嘴采用扇形喷嘴，每组喷嘴的喷射量不小于10～15m 3/h。挤干辊采用的是聚氨酯材料，聚氨酯材料的硬度在75～80A。漂洗槽内的两组刷辊，采用较小的压力，在不对镀锡基板表面产生硬擦伤的前提下，又可以提升对镀锡基板表面残余氧化层的酸洗去除能力。漂洗槽中两对水喷嘴以及顶部的挤干辊可以将钢板表面的残留硫酸溶液去除，避免带钢在进入到电镀槽之前残留的的硫酸溶液与钢板生成铁离子，带入到电镀槽中。
所述步骤3中，电镀过程中采用的电极材料为纯Ti+YiO 2电极，YiO 2的厚度在10～20μm，镀液中锡离子的浓度控制在16～20g/L，电流密度控制在15～25A/dm 2，镀液的温度控制在40～50℃；镀液中铅离子浓度通过除铅系统来控制，除铅系统包括反应、吸附、沉淀、分离等工艺过程，经除铅系统后镀液铅离子浓度控制在1.0mg/L以下。与电解碱洗极板原理相同，纯Ti+YiO 2极板可以提高电镀效果。 提高锡离子浓度可以抑制铅离子沉积到镀层中，但是锡离子浓度过高，会造成镀液中锡泥含量的急剧增加。电流密度控制在15～25A/dm 2，镀液的温度控制在40～50℃，可以获得致密的镀层。温度过低电化学反应效率下降，温度过高会造成镀液中的有机组分降解而失去活性。电流密度过低则影响机组高速稳定生产，电流密度过高则镀层晶粒粗大且不均匀。
所述步骤4中，除铅采用的是氢氧化钡溶液，氢氧化钡的加入量根据锡原料中铅含量而定，其间的关系式为：
氢氧化钡添加量(g/L)＝K*锡原料中的铅含量(mg/kg)，K取值范围：(0.015～0.020)。镀液中铅离子的来源主要有锡原料和酸洗液，酸洗液中处于稳定状态，而锡原料铅含量波动较大，因此锡原料铅含量直接影响着镀液铅离子浓度。氢氧化钡降铅的原理是氢氧化钡与镀液中硫酸生成硫酸钡，硫酸钡包裹镀液中的铅离子形成共沉淀，经过压滤机去除。根据生产经验得出如下公式，氢氧化钡添加量(g/L)＝K*锡原料中的铅含量(mg/kg)，K取值范围：(0.015～0.020)。氢氧化钡合适的添加量可以最大程度的去除镀液中的铅离子，使得镀液铅离子浓度控制在1.0mg/L以下，同时又不会在镀液中因加入过多的氢氧化钡而生产过多的硫酸钡，造成镀液中钡离子的富集而影响电镀效果。
所述步骤4中，除铅过程为：将适量的氢氧化钡溶液在搅拌的状态下加入到镀液中，在搅拌的状态下氢氧化钡与镀液中的硫酸反应，生成细微的硫酸钡颗粒，在搅拌的状态下微细硫酸钡吸附镀液中的铅离子，经60～90分钟的吸附过程后，镀液通过溢流的方式进入到竖 流式沉降罐，沉降后清液通过沉降罐上部溢流到镀液槽中，沉降罐底部的泥浆通过泥浆泵打入到压滤机中，泥浆泵的启停由底部的压差计控制，压滤得到的清液回到镀液槽，泥饼作为固体废弃物回收利用。搅拌状态下，在60～90分钟内，可以确保氢氧化钡与镀液中硫酸生成硫酸钡的速度，以及硫酸钡与镀液中的铅离子的充分吸附。上层清液回流到镀液槽中，经过多次、持续不断的降铅处理过程，达到快速降低镀液铅离子的目的。
所述步骤4中，反应罐的结构尺寸如图2所示，混合搅拌桨采用斜桨，带有一定程度的剪切功能，确保微细硫酸钡与镀液充分混合，搅拌桨的转速为600rmp。沉淀搅拌桨的转速为60rpm，防止微细硫酸钡在吸附的过程中发生沉降，镀液在该罐中的吸附时间为1小时。吸附反应后的溶液通过溢流到沉降罐。
所述步骤4中，沉降罐的结构尺寸如图3所示，罐子的直径D与L之间的关系为
Figure PCTCN2020118977-appb-000012
为此沉降罐的直径d＝2000mm。罐体沉降段的高度H3为筒体直径1.5d，H3＝3000mm。沉降罐下部锥角的角度A3取120°。沉降罐内部中心下降管5的直径d取50mm，中心下降管5插入到溶液的深度为H2＝2500mm。插入管的端部呈喇叭状，喇叭口的直径100mm，其底部设置有排污口10，微压差计7的安装高度为300mm，，微压差计7一旦检测到压力比初始值增加15％，泥浆泵即启动，当为微压差计7检测到压力下降10％，后抽取镀液的总量在2m 3后，泥浆泵体停止听工作。罐底的沉降物采用泥浆泵抽走，泥浆泵采用定时模式启停，所抽取的沉淀物通过压滤机，压滤机采用尼龙过滤布，过滤精度为1μm。
应用实施例1：镀层厚度1.1g/m 2及以下低铅含量镀锡产品的生产：
某年产量20万吨的镀锡机组，采用的是不溶性阳极镀锡工艺，镀液为环保型的MSA镀液，镀层厚度在1.1g/m 2及以下的产品是该机组生产的主流产品，为生产低铅含量的镀锡产品，采用如下的生产工艺：
1、镀锡基板在镀锡机组的碱洗工艺段采用电解碱洗，碱洗液为含有消泡剂和表面活性剂的氢氧化钾和氢氧化钠混合溶液，碱洗液中氢氧化钠的含量13％wt，氢氧化钾的含量2％wt，消泡剂含量0.03％wt，表面活性剂含量0.5％wt；
2、碱洗工艺中电极材料为Ti+YiO 2，YiO 2的厚度5μm，碱洗电流密度控制在20A/dm 2，碱洗液的温度控制在40℃；
3、碱洗槽的出口带有一个刷洗槽，刷洗槽内带有二组刷辊，刷辊的转动方向与带钢运行方向相反，刷丝采用含磨料(SiC)尼龙材料，SiC的粒度在200目，尼龙材料刷辊通过气压缸保持与带钢的紧密接触，刷辊工作时的转动速度为300rpm，压力控制在500N；
4、酸洗采用的是化学酸洗，酸洗介质为硫酸，硫酸的浓度为5％，酸洗液的温度为55℃，酸洗工艺段共有2个酸洗槽，酸洗液通过扇形喷嘴喷射到带钢的表面，每组喷嘴的喷射量不小于10m 3/h；
5、酸洗后的带钢经过一个漂洗槽，漂洗槽内布置二组刷辊和二对水喷嘴，顶部配备有一对挤干辊。刷丝的材料采用尼龙材料，尼龙材料刷辊通过气压缸保持与带钢的紧密接触，刷辊工作时的转动速度为200rpm，压力控制在200N。水喷嘴采用扇形喷嘴，每组喷嘴的喷射量不小于10m 3/h。挤干辊采用的是聚氨酯材料，聚氨酯材料的硬度在75A；
6、电镀过程中采用的电极材料为Ti+YiO 2，YiO 2的厚度10μm，镀液中锡离子的浓度为16g/L，电流密度为15A/dm 2，镀液的温度控制在50℃；
7、经溶锡系统后的镀液进入到除铅系统，在反应容器中加入1.0g/L的氢氧化钡(配制成浓度为2％的浓度加入，配制温度70℃)，镀液在反应罐中的停留时间为60分钟，反应后的镀液通过溢流的方式进入到竖流式沉降罐，镀液在沉降罐中的停留时间为4小时，沉降后清液通过沉降罐上部溢流到镀液槽中，沉降罐底部的泥浆通过泥浆泵打入到压滤机中，泥浆泵的启停由底部的压差计控制，压滤得到的清液回到镀液槽，泥饼作为固体废弃物回收利用。
镀液中的铅离子浓度可稳定控制在1.0mg/L以下，不同镀层厚度镀锡板铅含量稳定控制在50mg/kg以下，实现低铅含量镀锡板的稳定生产。
应用实施例2：镀层厚度2.0g/m 2镀锡产品的生产：
镀层厚度为2.0g/m 2的镀锡板是中等镀锡量的镀锡板，对于不溶性阳极、MSA镀液的镀锡机组在生产这个规格低铅含量的镀锡产品时，采用如下的生产工艺：
1、镀锡基板在镀锡机组的碱洗工艺段采用电解碱洗，碱洗液为含有消泡剂和表面活性剂的氢氧化钾和氢氧化钠混合溶液，碱洗液中氢氧化钠的含量18％wt，氢氧化钾的含量3％wt，消泡剂含量0.05％wt，表面活性剂含量0.8％wt；
2、碱洗工艺中电极材料为Ti+YiO 2，YiO 2的厚度在10μm，碱洗电流密度控制在10A/dm 2，碱洗液的温度控制在55℃；
3、碱洗槽的出口带有一个刷洗槽，刷洗槽内带有二组刷辊，刷辊的转动方向与带钢运行方向相反，刷丝的材料采用含磨料(SiC) 尼龙材料，SiC的粒度在300目，尼龙材料刷辊通过气压缸保持与带钢的紧密接触，刷辊工作时的转动速度为180rpm，压力控制在400N；
4、酸洗采用的是化学酸洗，酸洗介质为硫酸，硫酸浓度为10％，酸洗液的温度为55℃，酸洗工艺段共有2个酸洗槽，酸洗液通过扇形喷嘴喷射到带钢的表面，每组喷嘴的喷射量不小于15m 3/h；
5、酸洗后的带钢经过一个漂洗槽，漂洗槽内布置二组刷辊和二对水喷嘴，顶部配备有一对挤干辊。刷丝的材料采用尼龙材料，尼龙材料刷辊通过气压缸保持与带钢的紧密接触，刷辊工作时的转动速度为250rpm，压力控制在250N。水喷嘴采用扇形喷嘴，每组喷嘴的喷射量不小于15m 3/h。挤干辊采用的是聚氨酯材料，聚氨酯材料的硬度在80A；
6、电镀过程中采用的电极为Ti+YiO 2，YiO 2的厚度在20μm，镀液中锡离子的浓度为20g/L,电流密度为15A/dm 2，镀液的温度控制在45℃；
7、机组采用纯度为99.9％的锡原料(其中的铅含量大于0.01％)，经溶锡系统后的镀液进入到除铅系统，在反应容器中加入1.2g/L的氢氧化钡(配制成浓度为2％的浓度加入，配制温度70℃)，镀液在反应罐中的停留时间为90分钟，反应后的镀液通过溢流的方式进入到竖流式沉降罐，镀液在沉降罐中的停留时间为6小时，沉降后清液通过沉降罐上部溢流到镀液槽中，沉降罐底部的泥浆通过泥浆泵打入到压滤机中，泥浆泵的启停由底部的压差计控制，压滤得到的清液回到镀液槽，泥饼作为固体废弃物回收利用。
镀液中的铅离子浓度可稳定控制在1.0mg/L以下，不同镀层厚度镀锡板铅含量稳定控制在50mg/kg以下，实现低铅含量镀锡板的稳定生产。
应用实施例3：镀层厚度2.8g/m 2镀锡产品的生产：
镀层厚度为2.8g/m 2的镀锡板是中等镀锡量的镀锡板，对于不溶性阳极、MSA镀液的镀锡机组在生产这个规格低铅含量的镀锡产品时，采用如下的生产工艺：
1、镀锡基板在镀锡机组的碱洗工艺段采用电解碱洗，碱洗液为含有消泡剂和表面活性剂的氢氧化钾和氢氧化钠混合溶液，碱洗液中氢氧化钠的含量20％wt，氢氧化钾的含量1％wt，消泡剂含量0.01％wt，表面活性剂含量1.0wt；
2、碱洗工艺中电极材料为Ti+YiO 2，YiO 2的厚度在10μm，碱洗电流密度控制在15A/dm 2，碱洗液的温度控制在50℃；
3、碱洗槽的出口带有一个刷洗槽，刷洗槽内带有二组刷辊，刷辊的转动方向与带钢运行方向相反，刷丝的材料采用含磨料(SiC)尼龙材料，SiC的粒度在500目，尼龙材料刷辊通过气压缸保持与带钢的紧密接触，刷辊工作时的转动速度为200rpm，压力控制在450N；
4、酸洗采用的是化学酸洗，酸洗介质为硫酸，硫酸浓度为20％，酸洗液的温度为40℃，酸洗工艺段共有2个酸洗槽，酸洗液通过扇形喷嘴喷射到带钢的表面，每组喷嘴的喷射量不小于13m 3/h；
5、酸洗后的带钢经过一个漂洗槽，漂洗槽内布置二组刷辊和二对水喷嘴，顶部配备有一对挤干辊。刷丝的材料采用尼龙材料，尼龙材料刷辊通过气压缸保持与带钢的紧密接触，刷辊工作时的转动速度为200rpm，压力控制在300N。水喷嘴采用扇形喷嘴，每组喷嘴的喷射量不小于12m 3/h。挤干辊采用的是聚氨酯材料，聚氨酯材料的硬度在78A；
6、电镀过程中采用的电极为Ti+YiO 2，YiO 2的厚度在15μm，镀液中锡离子的浓度为18g/L,电流密度为25A/dm 2，镀液的温度控制 在50℃；
7、机组采用纯度为99.9％的锡原料(其中的铅含量大于0.01％)，经溶锡系统后的镀液进入到除铅系统，在反应容器中加入1.5g/L的氢氧化钡(配制成浓度为2％的浓度加入，配制温度75℃)，镀液在反应罐中的停留时间为70分钟，反应后的镀液通过溢流的方式进入到竖流式沉降罐，镀液在沉降罐中的停留时间为4.5小时，沉降后清液通过沉降罐上部溢流到镀液槽中，沉降罐底部的泥浆通过泥浆泵打入到压滤机中，泥浆泵的启停由底部的压差计控制，压滤得到的清液回到镀液槽，泥饼作为固体废弃物回收利用。
镀液中的铅离子浓度可稳定控制在0.8mg/L以下，不同镀层厚度镀锡板铅含量稳定控制在30mg/kg以下，实现低铅含量镀锡板的稳定生产。
应用实施例4：镀层厚度5.6g/m 2及以上镀锡产品的生产：
镀层厚度为5.6g/m 2及以上的镀锡板为高镀锡量的产品，常用于奶粉罐和果蔬罐的包装。对于不溶性阳极、MSA镀液的镀锡机组在生产这个规格低铅含量的镀锡产品时，采用如下的生产工艺：
1、镀锡基板在镀锡机组的碱洗工艺段采用电解碱洗，碱洗液为含有消泡剂和表面活性剂的氢氧化钾和氢氧化钠混合溶液，碱洗液中氢氧化钠的含量15％wt，氢氧化钾的含量5％wt，消泡剂含量0.04％wt，表面活性剂含量0.7％wt；
2、碱洗工艺中电极材料为Ti+YiO 2，YiO 2的厚度在15μm，碱洗电流密度控制在25A/dm 2，碱洗液的温度控制在40℃；
3、碱洗槽的出口带有一个刷洗槽，刷洗槽内带有二组刷辊，刷辊的转动方向与带钢运行方向相反，刷丝的材料采用含磨料(SiC)尼龙材料，SiC的粒度在600目，尼龙材料刷辊通过气压缸保持与带 钢的紧密接触，刷辊工作时的转动速度为250rpm，压力控制在250N；
4、酸洗采用的是化学酸洗，酸洗介质为硫酸，硫酸的浓度为20％，酸洗液的温度为45℃，酸洗工艺段共有2个酸洗槽，酸洗液通过扇形喷嘴喷射到带钢的表面，每组喷嘴的喷射量不小于15m 3/h；
5、酸洗后的带钢经过一个漂洗槽，漂洗槽内布置二组刷辊和二对水喷嘴，顶部配备有一对挤干辊。刷丝的材料采用尼龙材料，尼龙材料刷辊通过气压缸保持与带钢的紧密接触，刷辊工作时的转动速度为250rpm，压力控制在200N。水喷嘴采用扇形喷嘴，每组喷嘴的喷射量不小于15m 3/h。挤干辊采用的是聚氨酯材料，聚氨酯材料的硬度在78A；
6、电镀过程中采用的电极为Ti+YiO 2，YiO 2的厚度在10μm，镀液中锡离子的浓度20g/L,电流密度为15A/dm 2，镀液的温度控制在45℃；
7、机组采用纯度为99.9％的锡原料(其中的铅含量大于0.01％)，经溶锡系统后的镀液进入到除铅系统，在反应容器中加入1.3g/L的氢氧化钡(配制成浓度为2％的浓度加入，配制温度65℃)，镀液在反应罐中的停留时间为80分钟，反应后的镀液通过溢流的方式进入到竖流式沉降罐，镀液在沉降罐中的停留时间为5.5小时，沉降后清液通过沉降罐上部溢流到镀液槽中，沉降罐底部的泥浆通过泥浆泵打入到压滤机中，泥浆泵的启停由底部的压差计控制，压滤得到的清液回到镀液槽，泥饼作为固体废弃物回收利用。
镀液中的铅离子浓度可稳定控制在0.5mg/L以下，不同镀层厚度镀锡板铅含量稳定控制在20mg/kg以下，实现低铅含量镀锡板的稳定生产。
应用实施例5：镀层厚度8.4g/m 2及以上镀锡产品的生产：
镀层厚度为8.4g/m 2及以上的镀锡板为高镀锡量的产品，对于不溶性阳极、MSA镀液的镀锡机组在生产这个规格低铅含量的镀锡产品时，采用如下的生产工艺：
1、镀锡基板在镀锡机组的碱洗工艺段采用电解碱洗，碱洗液为含有消泡剂和表面活性剂的氢氧化钾和氢氧化钠混合溶液，碱洗液中氢氧化钠的含量20％wt，氢氧化钾的含量1％wt，消泡剂含量0.02％wt，表面活性剂含量0.8％wt；
2、碱洗工艺中电极材料为Ti+YiO 2，YiO 2的厚度在20μm，碱洗电流密度控制在30A/dm 2，碱洗液的温度控制在40℃；
3、碱洗槽的出口带有一个刷洗槽，刷洗槽内带有二组刷辊，刷辊的转动方向与带钢运行方向相反，刷丝的材料采用含磨料(SiC)尼龙材料，SiC的粒度在700目，尼龙材料刷辊通过气压缸保持与带钢的紧密接触，刷辊工作时的转动速度为250rpm，压力控制在200N；
4、酸洗采用的是化学酸洗，酸洗介质为硫酸，硫酸的浓度为15％，酸洗液的温度为50℃，酸洗工艺段共有2个酸洗槽，酸洗液通过扇形喷嘴喷射到带钢的表面，每组喷嘴的喷射量不小于10m 3/h；
5、酸洗后的带钢经过一个漂洗槽，漂洗槽内布置二组刷辊和二对水喷嘴，顶部配备有一对挤干辊。刷丝的材料采用尼龙材料，尼龙材料刷辊通过气压缸保持与带钢的紧密接触，刷辊工作时的转动速度为150rpm，压力控制在200N。水喷嘴采用扇形喷嘴，每组喷嘴的喷射量不小于15m 3/h。挤干辊采用的是聚氨酯材料，聚氨酯材料的硬度在80A；
6、电镀过程中采用的电极为Ti+YiO 2，YiO 2的厚度在15μm，镀液中锡离子的浓度20g/L,电流密度为20A/dm 2，镀液的温度控制在50℃；
7、机组采用纯度为99.9％的锡原料(其中的铅含量大于0.01％)，经溶锡系统后的镀液进入到除铅系统，在反应容器中加入1.1g/L的氢氧化钡(配制成浓度为2％的浓度加入，配制温度60℃)，镀液在反应罐中的停留时间为75分钟，反应后的镀液通过溢流的方式进入到竖流式沉降罐，镀液在沉降罐中的停留时间为5小时，沉降后清液通过沉降罐上部溢流到镀液槽中，沉降罐底部的泥浆通过泥浆泵打入到压滤机中，泥浆泵的启停由底部的压差计控制，压滤得到的清液回到镀液槽，泥饼作为固体废弃物回收利用。
镀液中的铅离子浓度可稳定控制在0.4mg/L以下，不同镀层厚度镀锡板铅含量稳定控制在15mg/kg以下，实现低铅含量镀锡板的稳定生产。
通过上述应用实施例，可使得不同镀层厚度产品的镀层与基体间具有良好的附着性能，镀液中的铅离子浓度可稳定控制在1.0mg/L以下，不同镀层厚度镀锡板铅含量稳定控制在50mg/kg以下，实现低铅含量镀锡板的稳定生产。
需要说明的是上述实施例，并非用来限定本发明的保护范围，在上述技术方案的基础上所作出的等同变换或替代均落入本发明权利要求所保护的范围。

Claims (10)

  1. 一种不溶性阳极的甲基磺酸镀层低铅含量镀锡板，所述组分及含量如下：C:0.003～0.15％、Si:≤0.03％、Mn：0.1～1％、P：≤0.02％、S：≤0.02％、Cu≤0.020％、Alt：0.01～0.2％，余量为铁和杂质，其特征在于，镀锡板镀层铅含量控制在50mg/kg以下，其中镀锡板厚度为0.17—0.55mm，镀层的厚度为1.1—11.2g/m 2。
  2. 根据权利要求1所述的不溶性阳极的甲基磺酸镀层低铅含量镀锡板，其特征在于，镀层的厚度为2.0—8.4g/m 2。
  3. 一种不溶性阳极的甲基磺酸镀层低铅含量镀锡板的加工设备，其特征在于，所述加工设备包括碱洗装置、矫直机、酸洗装置、电镀装置以及除铅系统，镀锡基板依次经过碱洗装置、矫直机、酸洗装置、电镀装置，最后进入除铅系统；
    其中，碱洗装置主要包括碱液槽，其出口设置刷洗槽，内有两组刷辊；
    矫直机，经碱洗后的镀锡基板，经过多辊矫直机对镀锡基板进行矫直；酸洗装置包括两个酸洗槽，所述酸洗槽内设置有高压喷射装置，顶部设置有挤干辊，内有扇形喷嘴；酸洗后的带钢经过一个漂洗槽，漂洗槽内布置二组刷辊和二对水喷嘴，顶部配备有一对挤干辊,电镀装置包括电镀液槽和锡溶解罐；除铅系统包括氢氧化钡溶解罐、反应罐、沉降罐、泥浆泵以及压滤机；所述氢氧化钡溶解罐依次连接反应罐、沉降罐、泥浆泵以及压滤机。
  4. 根据权利要求3所述的不溶性阳极的甲基磺酸镀层低铅含量镀锡 板的加工设备，其特征在于，在反应罐内部设置有一预混室，氢氧化钡在带有搅拌装置的预混室中与镀锡溶液充分混合，预混室的宽度为反应罐罐体直径为
    Figure PCTCN2020118977-appb-100001
    预混室中搅拌桨M1的搅拌转速为400～600rpm，主反应器设置有搅拌桨M2，搅拌桨采用平桨，搅拌桨的宽度d为容器直径的
    Figure PCTCN2020118977-appb-100002
    搅拌桨的转速为30～60rpm。
  5. 制备不溶性阳极的甲基磺酸镀层低铅含量镀锡板的生产方法，其特征在于，所述方法包括以下步骤：
    步骤1：碱洗工艺段，镀锡基板先经过电化学碱洗，碱洗液采用含氢氧化钾的氢氧化钠溶液；增设刷洗工艺，刷辊上的刷毛为含磨料的尼龙材料；
    步骤2：酸洗工艺段，经碱洗后的带钢进入到化学酸洗槽，酸洗槽采用低浓度的硫酸溶液，采用高压喷射装置喷射到带钢的表面，并增设刷洗工艺，刷辊上的刷毛纯尼龙材料；
    步骤3：电镀工艺段，带钢进入到不溶性阳极的MSA镀液系统后，带钢在较低的电流密度下进行电镀，镀液中的锡离子通过体外循环的方式进行调节，电镀槽中的镀液通过循环泵打入到锡溶解罐，锡粒与注入氧气的镀液在锡溶解罐中反应，提高镀液中锡离子的浓度；
    步骤4：完成电镀后的镀液进入到除铅系统，镀液中的铅通过不断体外循环进行除铅，
    通过调节生产过程中的这些工艺参数和增设相应的设备，将镀锡层中的铅含量控制在50mg/kg以下。
  6. 根据权利要求5所述的低铅含量镀锡板的生产方法，其特征在于， 所述步骤1：具体如下：
    镀锡基板进入到镀锡机组，在镀锡生产工艺的碱洗环节采用电解碱洗，碱洗采用的碱洗液为含氢氧化钾的氢氧化钠溶液，溶液中还含有消泡剂和表面活性剂，消泡剂含量0.01～0.10％wt，表面活性剂含量0.1～1.0％wt,碱洗液中氢氧化钠的含量5～30％wt，氢氧化钾的含量0.1～5％wt；
    碱洗机组中电极与带钢形成电解池，电极材料采用纯Ti材料，为提高电极材料的电导率，在Ti材表面镀一层YiO 2，YiO 2的厚度在5～20μm，碱洗电流密度控制在10～30A/dm 2，碱洗液的温度控制在40～55℃；
    所述步骤1中，碱洗槽的出口带有一个刷洗槽，刷洗槽内带有两组刷辊，刷辊的转动方向与带钢运行方向相反，刷丝的材料采用含磨料(SiC)尼龙材料，SiC的粒度在200～800目之间，尼龙材料刷辊通过气压缸保持与带钢的紧密接触，刷辊工作时的转动速度为100～300rpm，压力控制在200～500N。
  7. 根据权利要求5所述的低铅含量镀锡板的生产方法，其特征在于，所述步骤2中，酸洗采用的是化学酸洗，酸洗介质为稀硫酸，硫酸浓度5～20％，酸洗液的温度为40～55℃，酸洗工艺段设置有两个酸洗槽，酸洗液通过扇形喷嘴喷射到带钢的表面，每组喷嘴的喷射量不小于10～15m 3/h。
  8. 根据权利要求5所述的低铅含量镀锡板的生产方法，其特征在于，所述步骤2中，酸洗后的带钢经过一个漂洗槽，漂洗槽内布置二组刷辊和二对水喷嘴，顶部配备有一对挤干辊,刷丝的材料采用尼龙材料， 尼龙材料刷辊通过气压缸保持与带钢的紧密接触，刷辊工作时的转动速度为100～300rpm，压力控制在200～300N，水喷嘴采用扇形喷嘴，每组喷嘴的喷射量不小于10～15m 3/h，挤干辊采用的是聚氨酯材料，聚氨酯材料的硬度在75-80A。
  9. 根据权利要求5所述的低铅含量镀锡板的生产方法，其特征在于，所述步骤3中，电镀过程中采用的阳极材料为纯Ti+YiO 2，YiO 2的厚度在10～20μm，镀液中锡离子的浓度控制在16～20g/L，电流密度控制在15～25A/dm 2，镀液的温度控制在40～50℃。
  10. 根据权利要求5或6或7或8或9所述的低铅含量镀锡板的生产方法，其特征在于，所述步骤4中，除铅采用的是氢氧化钡溶液，氢氧化钡的加入量根据锡原料中铅含量而定，其间的关系式为：氢氧化钡添加量(g/L)＝K*锡原料中的铅含量(mg/kg)，镀液中铅离子浓度通过除铅系统来控制，除铅系统包括反应、吸附、沉淀、分离工艺过程，经除铅系统后镀液铅离子浓度控制在1.0mg/L以下；其中，K取值范围：0.015～0.020；
    所述步骤4中，除铅过程为：将适量的氢氧化钡溶液在搅拌的状态下加入到镀液中，在搅拌的状态下氢氧化钡与镀液中的硫酸反应，生成细微的硫酸钡颗粒，在搅拌的状态下微细硫酸钡吸附镀液中的铅离子，经60～90分钟的吸附过程后，镀液通过溢流的方式进入到竖流式沉降罐，沉降后清液通过沉降罐上部溢流到镀液槽中，沉降罐底部的泥浆通过泥浆泵打入到压滤机中，泥浆泵的启停由底部的压差计控制，压滤得到的清液回到镀液槽，泥饼作为固体废弃物回收利用。
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