CN110129799B - Recycling method of tin stripping waste liquid based on sulfuric acid-ferric salt system - Google Patents
Recycling method of tin stripping waste liquid based on sulfuric acid-ferric salt system Download PDFInfo
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Abstract
The invention relates to a recycling method of tin stripping waste liquid based on a sulfuric acid-ferric salt system. The recycling method comprises the following steps: taking the tin stripping waste liquid as electrolyte, taking an electrode material with high hydrogen evolution overpotential as a cathode, taking an electrode material with high oxygen evolution overpotential as an anode, carrying out constant current electrification, and stripping tin simple substance deposited on the cathode. The recycling method provided by the invention can realize the recycling of tin and iron metal resources in the tin stripping waste liquid, the recovery rate of tin and Fe3+The conversion rate of the catalyst is up to more than 70 percent; in addition, compared with the original sulfuric acid-iron salt system tin stripping liquid, the acid value of the treated tin stripping waste liquid is not reduced basically, and simultaneously sulfuric acid and Fe3+Effective tin stripping components such as organic corrosion inhibitor and the like are reserved, so that the recovered tin stripping waste liquid can be reused in the tin stripping process; the recycling method provided by the invention is simple and convenient to operate, does not need a diaphragm, does not introduce other ions, and is convenient for large-scale production.
Description
Technical Field
The invention belongs to the technical field of industrial wastewater treatment, and particularly relates to a recycling method of tin stripping waste liquid based on a sulfuric acid-ferric salt system.
Background
In the manufacturing process of a Printed Circuit Board (PCB), tin stripping is an indispensable one-step process; the tin stripping, as the name implies, is to strip the tin coating covering the copper plate, protecting the copper matrix. The tin stripping liquid widely used at present is based on a nitric acid system, but the tin stripping liquid of the nitric acid system has the defects that harmful gas is easy to generate, sludge is generated, waste water is difficult to treat and the like due to the use of strong oxidizing substances such as nitric acid and the like; in order to overcome the above disadvantages, patent CN105714298A discloses a tin stripping agent based on a sulfuric acid-ferric salt system, which has the characteristics of no generation of harmful gas, only stripping of tin layer, environmental protection and good applicability.
The tin stripping mechanism of the sulfuric acid-iron salt system is shown as the following formula:
2Fe3++Sn＝2Fe2++Sn2+
sn (alloy) + H2SO4＝SnSO4+H2↑
In the tin stripping solution, the sulfuric acid is used for dissolving tin oxide and a tin alloy layer to form soluble sulfate; the iron salt has the function of oxidizing tin into soluble salt through the strong oxidizing property of iron ions so as to achieve the aim of removing tin and a tin alloy layer thereof. Therefore, the ions in the tin stripping waste liquid are mainly Fe2+，Sn2+，H+，SO4 2-With a small amount of Fe3+，Sn4+。
However, the recovery and utilization method of the tin stripping waste liquid published at present is based on a nitric acid system; therefore, in order to promote a more environmentally-friendly and effective tin stripping agent based on a sulfuric acid-iron salt system, a method for recycling tin stripping waste liquid based on the system needs to be explored urgently.
Disclosure of Invention
The invention aims to overcome the defect of the prior art that a recycling method of tin stripping waste liquid based on a sulfuric acid-iron salt system is lacked, and provides a recycling method of tin stripping waste liquid based on a sulfuric acid-iron salt system. The recycling method provided by the invention can realize the recycling of tin and iron metal resources in the tin stripping waste liquid, the recovery rate of tin and Fe3+The conversion rate of the catalyst is up to more than 70 percent; in addition, compared with the original sulfuric acid-iron salt system tin stripping liquid, the acid value of the treated tin stripping waste liquid is not reduced basically, and simultaneously sulfuric acid and Fe3+Effective tin stripping components such as organic corrosion inhibitor and the like are reserved, so that the recovered tin stripping waste liquid can be reused in the tin stripping process; the recycling method provided by the invention is simple and convenient to operate, does not need a diaphragm, does not introduce other ions, and is convenient for large-scale production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for recycling tin stripping waste liquid based on a sulfuric acid-ferric salt system comprises the following steps: tin stripping waste liquid is used as electrolyte, electrode material with high hydrogen evolution overpotential is used as cathode, and electrode material with high oxygen evolution overpotential is usedAs an anode, stripping the tin simple substance deposited on the cathode after constant current electrification; the tin stripping waste liquid is obtained by stripping tin through a sulfuric acid-iron salt system, wherein the sulfuric acid-iron salt system is composed of 150-300 g/L sulfuric acid, 100-200 g/L iron salt, 0.1-1 g/L ferrous sulfate, 0.1-5 g/L organic corrosion inhibitor of copper, 2-10 g/L organic acid complexing agent, 2-3 g/L surfactant and 10-100 g/L accelerator; stripping tin to Fe by the sulfuric acid-iron salt system2+And Sn2+The molar ratio of (A) to (B) is 1: 0.5-1.0 to obtain the tin stripping waste liquid.
The invention carries out electrolytic treatment on the tin stripping waste liquid (such as CN105714298A) of a sulfuric acid-iron salt system, obtains a tin simple substance reduced and deposited on the surface of an electrode on a cathode, and carries out oxidation reaction on an anode to react Fe2+Oxidation to Fe3+By controlling Fe after stripping2+And Sn2+Molar amount of (3) to realize Sn2+Recovery of (2) and Fe3+Conversion of (3), recovery of tin and Fe3+The conversion rate of the catalyst is up to more than 70 percent.
In addition, effective tin stripping components such as sulfuric acid, organic corrosion inhibitor and the like are reserved in the electrolytic process, and Fe3+Content of (B) and Fe in the original tin stripping solution3+The content of the tin is similar, the acid value is not reduced basically, so that the composition and the performance of the tin stripping waste liquid after electrolysis are kept consistent with those of the original tin stripping liquid basically, and the tin stripping waste liquid can be used for a tin stripping procedure.
The recycling method provided by the invention is simple and convenient to operate, does not need a diaphragm, does not introduce other ions, and is convenient for large-scale production.
The selection of the electrode materials of the cathode and the anode can be selected according to the existing electrolytic materials to realize the deposition of tin and Fe2+The oxidation of (1) is sufficient.
Preferably, the cathode is made of copper, tin, cadmium, graphite, silver, iron, zinc, nickel or lead.
Preferably, the anode is made of graphite, lead, gold, silver or platinum.
The electrified current can be based on the potential of the cathode to separate out tin, and the anode Fe2+Conversion to Fe3+And its corresponding current density.
Preferably, the electrified current density is 40-80 mA/cm2And electrifying for 10-20 hours.
More preferably, the current for electrifying is 60mA/cm2The energization time was 18 hours.
Preferably, Fe in the tin stripping waste liquid2+Is 0.4 to 1mol/L, Sn2+The concentration of (b) is 0.2 to 0.5 mol/L.
Preferably, Fe in the tin stripping waste liquid2+And Sn2+Is 1: 0.5.
Preferably, the electrolyte after energization is used as a tin stripping liquid.
Due to sulfuric acid, Fe3+Effective tin stripping components such as ions, organic corrosion inhibitors and the like are reserved, so that the electrolyzed electrolyte can be recycled as the tin stripping liquid.
More preferably, the electrified electrolyte comprises 150-300 g/L concentrated sulfuric acid, 150-200 g/L ferric salt, 0.5-1.0 g/L ferrous sulfate and Sn2+0.03-0.08 mol/L, 0.1-5 g/L of organic corrosion inhibitor of copper, 2-10 g/L of organic acid complexing agent, 2-3 g/L of surfactant, 10-100 g/L of accelerator and the balance of water.
Compared with the prior art, the invention has the following beneficial effects:
the recycling method provided by the invention can realize the recycling of tin and iron metal resources in the tin stripping waste liquid, the recovery rate of tin and Fe3+The conversion rate of the catalyst is up to more than 70 percent; in addition, compared with the original sulfuric acid-iron salt system tin stripping liquid, the acid value of the treated tin stripping waste liquid is not reduced basically, and simultaneously sulfuric acid and Fe3+Effective tin stripping components such as organic corrosion inhibitor and the like are reserved, so that the recovered tin stripping waste liquid can be reused in the tin stripping process; the recycling method provided by the invention is simple and convenient to operate, does not need a diaphragm, does not introduce other ions, and is convenient for large-scale production.
Drawings
FIG. 1 is a schematic diagram of an electrolytic apparatus according to the present invention;
wherein, 1 is cathode electrode material, 2 is anode electrode material, and 3 is HDV-7C transistor potentiostat.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
The tin stripping waste liquid (including tin stripping waste liquid 1 and tin stripping waste liquid 2) in each example is prepared by the following method.
1.1 preparation of tin stripping solution 1
Preparing a tin stripping solution 1 based on a sulfuric acid-ferric salt system, wherein the tin stripping solution comprises the following components in percentage by weight: 150g/L of sulfuric acid, 100g/L of ferric sulfate, 0.5g/L of ferrous sulfate, 1g/L of benzotriazole, 5g/L of methanesulfonic acid, 2g/L of polyethylene glycol (6000), 10g/L of hydrogen peroxide and the balance of water.
The preparation method comprises the following steps: dissolving ferric sulfate in water, adding sulfuric acid, stirring until the ferric sulfate is completely dissolved, cooling to normal temperature, adding benzotriazole, methanesulfonic acid, polyethylene glycol (6000) and hydrogen peroxide, stirring until the benzotriazole, the methanesulfonic acid, the polyethylene glycol (6000) and the hydrogen peroxide are completely dissolved, and metering the volume to 1 liter by using deionized water to obtain the tin stripping liquid 1 of a sulfuric acid-ferric salt system.
1.2 stripping of tin
Preparing a plurality of copper-clad pure tin plates with the size of 5 cm multiplied by 5 cm and the average tin plating thickness of 10 microns, controlling the temperature of a tin stripping process at 30 ℃, putting the pure tin plates into 100mL of tin stripping solution 1, continuously shaking the tin plates, and removing tin completely after 2 minutes to expose bright copper plates without generating toxic gas in the process.
The tin stripping waste liquid 1 is determined to have the following composition: sulfuric acid 140g/L, Fe3+＝0.01mol/L，Fe2+＝0.444mol/L，Sn2+0.222mol/L, 0.8g/L of benzotriazole, 4.5g/L of methanesulfonic acid, 2g/L of polyethylene glycol (6000), 8g/L of hydrogen peroxide and the balance of water.
2.1 preparation of tin stripping solution 2
Preparing a tin stripping solution 2 based on a sulfuric acid-ferric salt system, wherein the tin stripping solution comprises the following components in percentage by weight: 150g/L of sulfuric acid, 100g/L of ferric sulfate, 0.5g/L of ferrous sulfate, 1g/L of benzotriazole, 5g/L of methanesulfonic acid, 2g/L of polyethylene glycol (6000), 10g/L of hydrogen peroxide and the balance of water.
The preparation method comprises the following steps: dissolving ferric sulfate in water, adding sulfuric acid, stirring until the ferric sulfate is completely dissolved, cooling to normal temperature, adding benzotriazole, methanesulfonic acid, polyethylene glycol (6000) and hydrogen peroxide, stirring until the benzotriazole, the methanesulfonic acid, the polyethylene glycol (6000) and the hydrogen peroxide are completely dissolved, and metering the volume to 1 liter by using deionized water to obtain the tin stripping liquid 2 of a sulfuric acid-ferric salt system.
2.2 stripping of tin
Preparing a plurality of copper-clad pure tin plates with the size of 5 cm multiplied by 5 cm and the average tin plating thickness of 10 microns, controlling the temperature of a tin stripping process at 30 ℃, putting the pure tin plates into 100mL of tin stripping liquid 2, continuously shaking the tin plates, and removing tin completely after 2 minutes to expose bright copper plates without generating toxic gas in the process.
The tin stripping waste liquid 2 is determined to have the following composition: sulfuric acid 140g/L, Fe3+＝0.005mol/L，Fe2+＝0.444mol/L，Sn2+0.444mol/L, 0.8g/L of benzotriazole, 4.5g/L of methanesulfonic acid, 2g/L of polyethylene glycol (6000), 8g/L of hydrogen peroxide and the balance of water.
Example 1
This example provides a method for recycling tin-stripping waste liquid 1 based on a sulfuric acid-iron salt system, and the preparation process thereof is as follows.
As shown in figure 1, 1100 mL of tin stripping waste liquid is taken and placed in an electrolytic tank, a Cu electrode is used as a cathode, a graphite electrode is used as an anode, and 40mA/cm is used2The constant current is electrified and electrolyzed for 14 hours, a tin simple substance which is reduced and deposited on a Cu electrode is obtained on a cathode, and the oxidation reaction is carried out on an anode to lead Fe2+Oxidation to Fe3+The tin-stripping waste liquid 1 turned slightly yellow from blue-green, and the tin simple substance on the cathode was scraped off and weighed to obtain 1.89 g.
The tin stripping waste liquid 1 after electrolysis is determined to have the following composition: sulfuric acid 140g/L, Fe3+＝0.328mol/L，Fe2+＝0.0126mol/L，Sn2+＝0.0657mol/L，0.8g/L of benzotriazole, 4.5g/L of methanesulfonic acid, 2g/L of polyethylene glycol (6000), 8g/L of hydrogen peroxide and the balance of water.
After the electrolytic treatment, the recovery rate of tin is 70.8 percent, and Fe3+The conversion was 71.6%.
Example 2
This example provides a method for recycling tin-stripping waste liquid 1 based on a sulfuric acid-iron salt system, and the preparation process thereof is as follows.
Placing 1100 mL of tin stripping waste liquid in an electrolytic cell, taking a Cu electrode as a cathode and a graphite electrode as an anode, and taking 60mA/cm2The electrolytic bath is electrified and electrolyzed for 18 hours at constant current, after the reaction is completed, a tin simple substance which is reduced and deposited on a Cu electrode is obtained on a cathode, the oxidation reaction is carried out on an anode to oxidize ferrous ions into ferric ions, the tin stripping waste liquid 1 turns dark yellow from blue-green, the tin simple substance on the cathode is scraped off, and 2.24g is weighed.
The tin stripping waste liquid 1 after electrolysis is determined to have the following composition: sulfuric acid 140g/L, Fe3+＝0.39mol/L，Fe2+＝0.064mol/L，Sn2+0.036mol/L, 0.8g/L of benzotriazole, 4.5g/L of methanesulfonic acid, 2g/L of polyethylene glycol (6000), 8g/L of hydrogen peroxide and the balance of water.
After the electrolysis treatment, the recovery rate of tin was 84.0% and the conversion rate was 85.6%.
Example 3
This example provides a method for recycling tin-stripping waste liquid 1 based on a sulfuric acid-iron salt system, and the preparation process thereof is as follows.
1100 mL of tin stripping waste liquid is placed in an electrolytic tank, a Cu electrode is used as a cathode, a graphite electrode is used as an anode, and 80mA/cm is used2The electrolytic bath is electrified and electrolyzed for 10 hours at constant current, after the reaction is completed, a tin simple substance which is reduced and deposited on a Cu electrode is obtained on a cathode, the oxidation reaction is carried out on an anode to oxidize ferrous ions into ferric ions, the tin stripping waste liquid turns yellow-green from blue-green, the tin simple substance on the cathode is scraped, and 2.06g is weighed.
The tin stripping waste liquid 1 after electrolysis is determined to have the following composition: sulfuric acid 140g/L, Fe3+＝0.358mol/L，Fe2+＝0.096mol/L，Sn2+0.0514mol/L benzene0.8g/L of triazole, 4.5g/L of methanesulfonic acid, 2g/L of polyethylene glycol (6000), 8g/L of hydrogen peroxide and the balance of water.
After the electrolysis treatment, the recovery rate of tin was 77.1% and the conversion rate was 78.4%.
Example 4
This example provides a method for recycling tin-stripping waste liquid 2 based on a sulfuric acid-iron salt system, and the preparation process is as follows.
Placing 2100 mL of the tin stripping waste liquid in an electrolytic cell, taking a Cu electrode as a cathode and a graphite electrode as an anode, and taking 65mA/cm2The electrolytic bath is electrified and electrolyzed for 18 hours at constant current, after the reaction is completed, a tin simple substance which is reduced and deposited on a Cu electrode is obtained on a cathode, the oxidation reaction is carried out on an anode to oxidize ferrous ions into ferric ions, the tin stripping waste liquid turns yellow-green from blue-green, the tin simple substance on the cathode is scraped, and the weight is 3.95 g.
The tin stripping waste liquid 2 after electrolysis is determined to have the following composition: sulfuric acid 140g/L, Fe3+＝0.225mol/L，Fe2+＝0.101mol/L，Sn2+0.111mol/L, 0.8g/L of benzotriazole, 4.5g/L of methanesulfonic acid, 2g/L of polyethylene glycol (6000), 8g/L of hydrogen peroxide and the balance of water.
After the electrolysis treatment, the recovery rate of tin was 75% and the conversion rate was 77.2%.
Example 5
The embodiment provides a recycling method of tin stripping waste liquid 1.
Taking the tin stripping waste liquid 1 after the electrolysis of the example 2 as a tin stripping liquid, carrying out tin stripping treatment on a copper-clad pure tin plate with the size of 5 cm multiplied by 5 cm and the average tin plating thickness of 10 microns, wherein the conditions of the treatment process are as follows: the tin stripping process controls the temperature at 30 ℃, and the pure tin plate is put into 100mL of tin stripping liquid and continuously shaken. After treatment, the tin coating on the surface layer of the copper plate is removed completely, a bright copper plate is exposed, and toxic gas is not generated in the process.
Therefore, the recycling method provided by the invention can realize the recycling of tin and iron metal resources in the tin stripping waste liquid, the recovery rate of tin and Fe3+The conversion rate of the catalyst is up to more than 70 percent; in addition, the treated tin stripping waste liquidCompared with the tin stripping liquid of the original sulfuric acid-iron salt system, the acid value is not reduced basically, and simultaneously sulfuric acid and Fe3+Effective tin stripping components such as organic corrosion inhibitor and the like are reserved, so that the recovered tin stripping waste liquid can be reused in the tin stripping process; the recycling method provided by the invention is simple and convenient to operate, does not need a diaphragm, does not introduce other ions, and is convenient for large-scale production.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A method for recycling tin stripping waste liquid based on a sulfuric acid-ferric salt system is characterized by comprising the following steps: taking tin stripping waste liquid as electrolyte, taking an electrode material with high hydrogen evolution overpotential as a cathode, taking an electrode material with high oxygen evolution overpotential as an anode, carrying out constant current electrification, and stripping tin simple substance deposited on the cathode; the tin stripping waste liquid is obtained by stripping tin through a sulfuric acid-iron salt system, wherein the sulfuric acid-iron salt system is composed of 150-300 g/L of concentrated sulfuric acid, 100-200 g/L of iron salt, 0.1-1 g/L of ferrous sulfate, 0.1-5 g/L of organic corrosion inhibitor of copper, 2-10 g/L of organic acid complexing agent, 2-3 g/L of surfactant and 10-100 g/L of accelerator; stripping tin to Fe by the sulfuric acid-iron salt system2+And Sn2+The molar ratio of (A) to (B) is 1: 0.5-1.0 to obtain the tin stripping waste liquid.
2. The recycling method according to claim 1, wherein the cathode is made of copper, tin, cadmium, graphite, silver, iron, zinc, nickel or lead.
3. The recycling method according to claim 1, wherein the anode is made of graphite, lead, gold, silver or platinum.
4. The recycling method according to claim 1, wherein the current density of the current is 40 to 80mA, and the time of the current is 10 to 20 hours.
5. The recycling method according to claim 4, wherein the electrified current density is 60mA/cm2The energization time was 18 hours.
6. The recycling method according to claim 1, wherein Fe in the tin-stripping waste liquid2+Is 0.4 to 1mol/L, Sn2+The concentration of (b) is 0.2 to 0.5 mol/L.
7. The recycling method according to claim 1, wherein Fe in the tin-stripping waste liquid2+And Sn2+Is 1: 0.5.
8. The recycling method according to claim 1, wherein the electrolytic solution after the energization is used as a tin stripping solution.
9. The recycling method according to claim 8, wherein the electrified electrolyte comprises 150-300 g/L concentrated sulfuric acid, 150-200 g/L ferric salt and 0.5-1 g/L, Sn ferrous sulfate2+0.03-0.08 mol/L, 0.1-5 g/L of organic corrosion inhibitor of copper, 2-10 g/L of organic acid complexing agent, 2-3 g/L of surfactant and 10-100 g/L of accelerator.
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| CN110760922B (en) * | 2019-10-30 | 2021-08-17 | 昆山金易得环保科技有限公司 | Tin stripping liquid, method for removing tin-containing layer on substrate and method for recovering tin |
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| CN105714298A (en) * | 2016-03-23 | 2016-06-29 | 广东工业大学 | Tin stripping agent based on sulfuric acid-ferric salt system and preparing method of tin stripping agent |
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