CN111424280B - Regeneration system and method for tin stripping waste liquid - Google Patents
Regeneration system and method for tin stripping waste liquid Download PDFInfo
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- CN111424280B CN111424280B CN202010243868.XA CN202010243868A CN111424280B CN 111424280 B CN111424280 B CN 111424280B CN 202010243868 A CN202010243868 A CN 202010243868A CN 111424280 B CN111424280 B CN 111424280B
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- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
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- C22B25/04—Obtaining tin by wet processes
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- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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Abstract
The invention relates to the field of production waste treatment in printed circuit manufacturing, and discloses a regeneration method of tin stripping waste liquid, which comprises the following steps: completely converting alpha stannic acid into beta stannic acid; coagulation of beta-stannic acid; filtering beta stannic acid; precipitating copper from the filtrate; solid-liquid separation; regenerating the clear liquid; the regeneration system comprises a waste liquid storage tank, a first reaction tank, a precipitation tank, a high-efficiency filtering assembly, a second reaction tank, a filtering device and a regenerated liquid storage tank which are sequentially connected. The method has the advantages that firstly, the tin-stripping waste liquid is pretreated innovatively to convert alpha stannic acid into beta stannic acid, then the beta stannic acid is subjected to coagulation and filtration, the filtrate is subjected to copper precipitation, filtration and sub-liquid regeneration, and copper and tin are separated step by step, so that the consumption of a copper precipitation agent is reduced, the treatment cost is reduced, an alkaline solution is not required in the treatment process, the raw material cost of the regeneration treatment process of the tin-stripping waste liquid is greatly reduced, the treatment process is simplified, the recovery purity of copper and tin products is improved, and the profit of the recovered products is improved.
Description
Technical Field
The invention relates to the technical field of production waste treatment in printed circuit manufacturing, in particular to a regeneration system and method of tin stripping waste liquid.
Background
The tin stripping waste liquid is one of typical wastes in the PCB industry, and the sources of the waste liquid mainly comprise two main types: the tin stripping waste liquid is generated in the tin stripping process of producing the printed circuit board, and is generated in the tin stripping process when the waste circuit board is treated by a wet method to separate components from a substrate. The tin stripping refers to dissolving and stripping the tin coating on the workpiece by using tin stripping liquid, wherein in the tin stripping process, when the tin content of the solution reaches a certain concentration (generally higher than 100g/L), the tin stripping capability is reduced, and the tin stripping liquid is discharged from tin stripping equipment to become tin stripping waste liquid. The tin stripping waste liquid is a dangerous waste liquid which is generated in the PCB production process and has very high acidity, contains a large amount of metal compounds such as tin, copper, iron and the like and a plurality of organic matters such as a stabilizer, a corrosion inhibitor and the like, has complex components, and is generally recycled by enterprises with the treatment and disposal qualification of the dangerous waste according to the requirement of environmental protection management.
Chinese patent CN108383278B discloses a method for treating tin-stripping waste liquid, which comprises adding a precipitant, a flocculant and a precipitation aid into the tin-stripping waste liquid to make tin in the tin-stripping waste liquid react with the precipitant to generate a precipitate, thereby obtaining a solid-liquid mixture; carrying out solid-liquid separation on the solid-liquid mixture to obtain a first filtrate and a first filter residue, and recovering the first filter residue to obtain tin salt; according to the method, a precipitator, a flocculating agent and a precipitation aid are added into the waste liquid simultaneously, so that tin and copper are precipitated simultaneously, tin slag with high copper impurity content is obtained, and the additional value of tin is low.
Disclosure of Invention
The invention aims to provide a regeneration system and a regeneration method of tin stripping waste liquid, which can completely convert alpha stannic acid into beta stannic acid, then modify and filter the beta stannic acid to obtain a crude tin product with relatively high quality, and can efficiently precipitate and separate tin in the tin stripping waste liquid.
The embodiment of the invention is realized by the following steps:
a regeneration method of tin stripping waste liquid comprises the following steps:
(1) pretreatment: completely converting alpha stannic acid into beta stannic acid; (2) beta stannic acid modification: coagulating the beta-stannic acid; (3) filtering beta stannic acid; (4) copper deposition: adding a copper precipitation agent to precipitate copper ions in the solution, and then filtering to obtain a solid and a clear solution; (5) regeneration of clear liquid: and recycling the clarified liquid.
Further, in the step (3), the filtration is carried out by adopting a high-efficiency filtration assembly, the high-efficiency filtration assembly comprises a plurality of filtration devices, the filtration devices are connected in series or in parallel through pipelines, and the filtration pore diameter of a filtration layer in each filtration device is 1-200 nm; the turbid liquid filtered by the filtering device can be circularly filtered again.
Furthermore, the filter layer is made of inert ceramic materials or silicon carbide materials; the shell pipeline of the filtering device is made of an acid and alkali resistant material, and the acid and alkali resistant material comprises a titanium material, glass fiber reinforced plastic or PP; and the filtering device is in a closed state.
Further, the filter layer is made of inert ceramic materials; the pipeline of the filtering device is made of titanium and is in a closed state.
Further, the recycling treatment in the step (5) comprises: adjusting the concentration of the main components in the clarified liquid to a preset concentration to obtain a regenerated tin stripping liquid, so that the clarified liquid meets the requirements of regeneration and reuse; the method comprises the following specific steps: detecting the concentration of main components in the clarified liquid; calculating the mass of an additive required to be added when the concentration of the main components in the clarified liquid is adjusted to a preset concentration; adding an additive into the clarified liquid according to the mass of the additive to be added so as to enable the concentration of main components in the clarified liquid to reach a preset concentration, and obtaining a regenerated tin stripping liquid; the main components of the clarifying solution comprise nitric acid, iron ions, a polymer surfactant and a complex compound, and the additive comprises nitric acid and ferric nitrate.
A regeneration system of tin stripping waste liquid comprises a waste liquid storage tank, a first reaction tank, a precipitation tank, a high-efficiency filtering component, a second reaction tank, a filtering device and a regeneration liquid storage tank which are connected in sequence; conveying the waste liquid into a first reaction tank for pretreatment to completely convert alpha stannic acid into beta stannic acid; then the crude tin product is conveyed into a precipitation tank to carry out coagulation on the beta stannic acid, the coagulated solid solution is conveyed into an efficient filtering component to filter the beta stannic acid precipitate, and the filtered crude tin product can be directly reused or sold after being washed, so that the economic benefit is improved; sending the filtrate to a second reaction tank, adding a copper precipitation agent, precipitating a small amount of copper ions in the solution, obtaining copper oxalate precipitate, filtering the copper oxalate precipitate by using a filtering device again to obtain copper oxalate solid and clarified liquid, and washing the copper oxalate solid to directly recycle or sell the copper oxalate solid, so that the economic benefit is improved; and then the clear liquid is conveyed to a regenerated liquid storage tank for treatment and recycling.
A regeneration liquid is prepared by the regeneration method.
The regenerated liquid is applied to the industries of printed circuit manufacturing, metal cleaning, label manufacturing and surface treatment.
The invention has the beneficial effects that:
1. the invention has the innovativeness that firstly, the tin-stripping waste liquid is pretreated to completely convert alpha stannic acid into beta stannic acid, then the beta stannic acid is subjected to coagulation and filtration, then copper precipitation and seed liquid regeneration are performed, copper and tin are separated, tin with higher purity is obtained firstly, then a small amount of copper mixed in the filtrate is subjected to copper precipitation and filtration, the recovery rate of tin is improved, the impurity content is reduced, tin and copper bases can be separated completely, usable regenerated liquid is obtained, the processing cost of tin recovery and regenerated liquid recovery is reduced, and meanwhile, an alkaline solution is not needed in the processing process, so that the raw material cost of the regeneration processing technology of the tin-stripping waste liquid is greatly reduced, the processing procedure is simplified, the pollution to the environment is reduced, the recovery purities of copper and tin products are improved, and the profit of the recovered products is improved.
2. The raw materials added in the tin stripping waste liquid treatment process do not introduce new substances into the subsequent treatment and use of the regeneration liquid, so that the regeneration liquid recovery treatment is simplified, and the effect is stable.
3. According to the invention, in the waste liquid filtering process, the novel efficient filtering component is used, so that the waste liquid can obtain an effective solid-liquid separation effect, the filtering speed is high, the filtering capacity is greatly improved, the filtrate is clearer, and the utilization effect of the recycled liquid is improved.
4. The novel efficient filtering component used in the waste liquid filtering process is corrosion-resistant, high-temperature-resistant, small in occupied area, convenient to assemble, high in mobility and more convenient to use.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
FIG. 1 is a schematic flow chart of a regeneration method of tin stripping waste liquid in an embodiment of the invention;
FIG. 2 is a schematic diagram of a high efficiency filter assembly according to an embodiment of the present invention;
FIG. 3 is a schematic flow chart of a regeneration system of tin stripping waste liquid in the embodiment of the invention.
An icon: 1-a waste liquid tank, 2-a feeding high-pressure pump, 3-a filtering device, 4-a filtering layer, 5-a backwash liquid conveying pump and 6-a clear liquid temporary storage tank.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following describes a system and a method for regenerating a tin stripping waste liquid according to embodiments of the present invention.
The embodiment provides a regeneration method of tin stripping waste liquid, which comprises the following steps:
(1) pretreatment: completely converting alpha stannic acid into beta stannic acid; (2) beta stannic acid modification: coagulating the beta-stannic acid; (3) filtering beta stannic acid; (4) copper deposition: adding a copper precipitation agent to precipitate a small amount of copper ions in the solution, and then filtering to obtain a solid and a clear solution; (5) and (3) seed liquid regeneration: and recycling the clarified liquid.
In the prior art, when the tin stripping waste liquid is regenerated, the precipitant, the flocculating agent and the precipitation assisting agent are directly added into the tin stripping waste liquid at the same time, so that the added raw materials are greatly wasted, and particularly, the consumption of the precipitant is greatly increased. In the prior art, oxalic acid is basically used as a precipitator when tin stripping waste liquid is regenerated, and the oxalic acid and the like as the precipitator can react with the tin stripping waste liquid as follows:
Cu 2 +H 2 C 2 O 4 →CuC 2 O 4 +2H +
α-SnO 2 ·3H 2 O+2H 2 C 2 O 4 →Sn(C 2 O 4 ) 2 +5H 2 O
from the above reaction, it can be seen that: if a precipitator, a flocculating agent and a settling agent are directly and simultaneously added into the tin stripping waste liquid, alpha stannic acid cannot be converted into acid-insoluble beta stannic acid for precipitation in time, and a large amount of oxalic acid precipitator is consumed by the alpha stannic acid, so that the cost of raw materials is greatly increased; finally, the copper-tin coprecipitation is treated again by using an alkaline solution to remove copper salt and iron salt impurities in the tin salt, so that a large amount of cost is further increased, and the process is more complicated.
The invention innovatively converts alpha stannic acid into beta stannic acid completely through pretreatment, then performs coagulation and filtration on the beta stannic acid, and then performs copper precipitation, filtration, seed solution regeneration and other steps on the filtrate to separate copper and tin, the stannic acid is basically and completely precipitated in the early stage of treatment, and then a small amount of copper ions possibly existing in the filtrate are removed, so that the recovery rate of tin is improved, the impurity content is reduced, and simultaneously tin and copper are separated completely; and the using amount of the copper precipitation agent is greatly reduced, and meanwhile, alkaline solution is not needed to be used for carrying out copper-tin separation on tin mud, so that the raw material cost of the regeneration treatment process of the tin-stripping waste liquid is greatly reduced, the treatment process is simplified, the recovery purity of copper and tin products is improved, and the profit of the recovered products is improved.
Firstly, adding one or more of nitric acid, oxygen and ozone as an oxidant into the tin stripping waste liquid, and simultaneously aerating to provide oxygen for a system solution and standing for heat preservation treatment, wherein the specific aeration is carried out for 1-2 hours at the temperature of 30-40 ℃ so that alpha stannic acid in the waste liquid is converted into beta stannic acid; alpha stannic acid and beta stannic acid in general tin stripping liquid coexist, so that the subsequent sedimentation and filtration are facilitated, the invention innovatively pretreats the tin stripping liquid, and the alpha stannic acid is completely converted into the beta stannic acid by adding nitric acid, oxygen or ozone, wherein substances such as hydrogen peroxide or sodium chlorate and the like are not used in the step, i.e., new substances are not introduced into the tin stripping liquid, and the negative influence on the recycling of the subsequent tin stripping liquid is avoided;
further, the coagulation method in step (2) comprises: a. adding a coagulant into the waste liquid; b. heating the waste liquid to 30-40 ℃, preserving heat, and standing for 8-12 hours; the coagulant comprises strong electrolyte and anionic surfactant; the beta stannic acid forms colloid in the solution, is uniformly dispersed in the solution and is difficult to filter, so that the beta stannic acid colloid needs to be coagulated, and the subsequent filtration is convenient; the beta stannic acid is ultrafine particles which are insoluble in water, acid and alkali, are dissolved in concentrated hydrochloric acid and molten alkali under heating, and are peptized under the action of dilute acid and alkali.
Further, the strong electrolyte is one or more of sulfuric acid, hydrochloric acid, chloric acid and perchloric acid.
Further, the anionic surfactant is one or more of fatty acid salt, sulfonate and sulfate.
According to the invention, the crude tin product with relatively high quality is obtained by directly filtering the modified beta-stannic acid, wherein the copper-containing impurities are few, and the crude tin product can be directly used for producing metastannic acid products, so that the cost control of the subsequent smelting process is facilitated; or the tin coarse product can be directly sold, and the economic benefit is improved.
When the beta stannic acid is filtered, a filter press is basically adopted for filtering in the prior art, filtrate is turbid, the filtering speed is low, and the production requirement cannot be met, the filtering in the step (3) of the invention adopts the high-efficiency filtering assembly shown in FIG. 2 for filtering, the high-efficiency filtering assembly comprises a plurality of filtering devices 3, the plurality of filtering devices 3 are connected in series or in parallel through pipelines, the filtering amount can be increased or decreased according to the waste liquid amount, and the filtering amount is greatly increased; the filtering pore diameter of the filtering layer 4 in the filtering device 3 is 1-200nm, and ultrafine particles such as beta stannic acid and the like can be filtered; the turbid liquid filtered by the filtering device 3 can be circularly filtered again, so that the filtered liquid is clearer and is not turbid. When the pretreated beta stannic acid in the waste liquid is filtered, the waste liquid in the waste liquid tank 1 passes through the feeding high-pressure pump 2 and is filtered by the filter device 3 to respectively obtain turbid liquid and clear liquid; returning the turbid liquid to the waste liquid tank 1 through the original pressure of the feeding high-pressure pump 2 for circulating filtration again, and allowing the clear liquid to enter a clear liquid temporary storage tank 6 for subsequent use; meanwhile, clear liquid can be used as backwash liquid by the filtering equipment and is conveyed to the filtering equipment by a backwash liquid conveying pump 5 for cleaning, and the cleaning liquid enters the waste liquid tank 1 after backwashing for secondary circulating filtration, so that the filtering liquid is clear and not turbid, and the utilization effect of the recycled liquid is improved; the shell pipeline of the whole filtering device 3 is made of acid and alkali resistant materials, wherein the acid and alkali resistant materials comprise titanium materials, glass fiber reinforced plastics, PP and the like; moreover, the whole filtering device 3 works in a closed state, no harmful gas overflows, and the environment is protected; the filter layer 4 is made of inert ceramic materials or silicon carbide materials, and has stable chemical performance, acid resistance and alkali resistance; the efficient filtering component has small occupied area; and a plurality of filter devices 3 are connected in series or in parallel through pipelines, so that the device is convenient to assemble and high in mobility, the device can enter the field to work after being assembled before use, the device does not need to be assembled on the field, the device can start to work after entering the field to connect electricity and the pipelines, and the device is convenient to move, carry and transfer and is more convenient to use.
After the beta stannic acid is filtered, a crude tin product with higher purity and a clear solution are obtained, the clear solution contains a small amount of copper impurities, and a small amount of copper ions in the solution are precipitated by adding a copper precipitation agent into the solution; in order to not influence the precipitation of copper ions under an acidic condition, oxalic acid is added in the step (4) of the invention as a copper precipitation agent, and because the waste liquid system is acidic, the addition of oxalic acid does not influence the reaction of the copper ions and the oxalic acid to generate copper oxalate precipitate, the copper oxalate is obtained and then filtered by using the high-efficiency filtering component of the invention, so that copper oxalate solid and clear liquid are obtained, and the copper oxalate solid can be directly recycled after being washed, so that the economic benefit of the copper oxalate solid is improved.
After the concentration of the main components in the clarified liquid is detected, the amount of corresponding additives required to be added for adjusting the concentration of the main components in the clarified liquid to the preset concentration is calculated, the additives are added into the clarified liquid according to the calculated corresponding additive amount, the concentration of the main components in the clarified liquid is adjusted to the preset concentration, the regenerated tin stripping liquid is obtained, and the regenerated tin stripping liquid can be used for a tin stripping process, so that the recovery and utilization of other components except tin and copper in the tin stripping waste liquid are realized. It is understood that the preset concentration of the main component is the concentration of the main component in the tin stripping solution, and the preset concentration can be selected according to the tin stripping solution prepared according to the actual needs, and is not particularly limited herein, for example, the main component includes 20% -30% nitric acid, 10-15g/L iron ions, and a small amount of polymer surfactant and complex; the preset concentration may be: the concentration of nitric acid is 4.5-6.5mol/L, the concentration of iron ions is 16-20g/L, the concentration of copper ions is less than 2g/L, and the concentration of tin ions is less than 4 g/L.
Example 1
The embodiment provides a high-efficiency filtering assembly, which comprises a plurality of filtering devices 3, wherein the filtering devices 3 are connected in series or in parallel through pipelines, so that the filtering amount can be increased or decreased according to the waste liquid amount, and the filtering amount is greatly increased; the filtering pore diameter of the filtering layer 4 in the filtering device 3 is 1-200nm, and ultrafine particles such as beta stannic acid and the like can be filtered; the turbid liquid filtered by the filtering device 3 can be circularly filtered again, so that the filtered liquid is clearer and is not turbid. When the pretreated beta stannic acid in the waste liquid is filtered, the waste liquid in the waste liquid tank 1 passes through the feeding high-pressure pump 2 and is filtered by the filter device 3 to respectively obtain turbid liquid and clear liquid; returning the turbid liquid to the waste liquid tank 1 through the original pressure of the feeding high-pressure pump 2 for circulating filtration again, and allowing the clear liquid to enter a clear liquid temporary storage tank 6 for subsequent use; meanwhile, clear liquid can be used as backwash liquid by the filtering equipment and is conveyed to the filtering equipment by a backwash liquid conveying pump 5 for cleaning, and the cleaning liquid enters the waste liquid tank 1 after backwashing for secondary circulating filtration, so that the filtering liquid is clear and not turbid, and the utilization effect of the recycled liquid is improved; the shell pipeline of the whole filtering device 3 is made of acid and alkali resistant materials, wherein the acid and alkali resistant materials comprise titanium materials, glass fiber reinforced plastics, PP and the like; the whole filtering device 3 works in a closed state, no harmful gas overflows, and the environment is protected; the filter layer 4 is made of inert ceramic materials or silicon carbide materials, and has stable chemical performance, acid resistance and alkali resistance; the efficient filtering component has small occupied area; and a plurality of filter devices 3 are connected in series or in parallel through pipelines, so that the device is convenient to assemble and high in mobility, the device can enter the field to work after being assembled before use, the device does not need to be assembled on the field, the device can start to work after entering the field to connect electricity and the pipelines, and the device is convenient to move, carry and transfer and is more convenient to use.
Example 2
The tin-stripping waste liquid used in the embodiment is detected to have the following contents/concentrations of components: the tin content is 100g/L, the copper ion content is 6g/L, the iron ion content is 16g/L, and the residual amount of nitric acid is 25%.
A regeneration method of tin stripping waste liquid comprises the following steps: adding nitric acid into the tin-stripping waste liquid, and simultaneously aerating for 1h and standing and preserving the temperature for 30 ℃ to completely convert alpha stannic acid in the waste liquid into beta stannic acid; then adding hydrochloric acid and sulfonate into the waste liquid, simultaneously heating to 30-40 ℃, preserving heat and standing for 8 hours; coagulating the beta-stannic acid in the waste liquid; the beta stannic acid precipitate is filtered by adopting a high-efficiency filtering component, the recovery rate of tin is 95.9 percent, and the impurity content is 1.4 percent; then adding oxalic acid to precipitate a small amount of copper ions in the solution, and filtering by using a high-efficiency filtering assembly again to obtain copper oxalate solid and clear liquid;
analyzing and detecting the concentrations of nitric acid, iron ions, polymer surfactant and complex in the clarified liquid by using a chemical analyzer, and calculating the amount of the nitric acid, the ferric nitrate, the polymer surfactant and the complex which are required to be added for adjusting the concentrations of the nitric acid, the iron ions, the polymer surfactant and the complex in the clarified liquid to the following concentrations: 20% -30% of nitric acid, 10-15g/L of iron ions and a small amount of polymer surfactant and complex. Adding nitric acid with the concentration of 4.5-6.5mol/L, iron ion with the concentration of 16-20g/L, copper ion with the concentration of less than 2g/L and tin ion with the concentration of less than 4g/L into the clear liquid according to the calculated amount, and then adjusting the concentrations of nitric acid, iron ion, a small amount of polymer surfactant and complex in the clear liquid to the concentrations to prepare the regenerated tin stripping liquid.
And carrying out a tin stripping experiment on the regenerated tin stripping solution by adopting a soaking method to detect the tin stripping performance, controlling the tin stripping temperature to be about 30 ℃, and obtaining the following experimental results: the tin stripping rate reaches 10 mu/min, the tin dissolving amount can reach 120g/L, the copper etching rate is less than 1 mu m/min, the performances are basically consistent with those of the new tin stripping liquid, the circuit board function is basically not influenced, and the regeneration and reuse requirements can be met.
Example 3
The tin-stripping waste liquid used in the embodiment is detected to have the following contents/concentrations of components: the tin content reaches more than 110g/L, the copper ion content is 8g/L, the iron ion content is 17g/L, and the residual nitric acid content is 24%.
A regeneration method of tin stripping waste liquid comprises the following steps: introducing ozone into the tin stripping waste liquid, and simultaneously aerating for 1.5h and standing and preserving the temperature for 35 ℃ to ensure that alpha stannic acid in the waste liquid is completely converted into beta stannic acid; then adding sulfuric acid and sulfate into the waste liquid, simultaneously heating to 35 ℃, preserving heat, and standing for 9 hours to perform coagulation on beta stannic acid in the waste liquid; the beta stannic acid precipitate is filtered by adopting a high-efficiency filtering component, the recovery rate of tin is 96.3 percent, and the impurity content is 1.2 percent; then adding oxalic acid to precipitate a small amount of copper ions in the solution, and filtering by using a high-efficiency filtering assembly again to obtain copper oxalate solid and clear liquid;
analyzing and detecting the concentrations of nitric acid, iron ions, polymer surfactant and complex in the clear liquid by using a chemical analyzer, and calculating the amount of the nitric acid, the iron nitrate, the polymer surfactant and the complex which are required to be added for adjusting the concentrations of the nitric acid, the iron ions, the polymer surfactant and the complex in the clear liquid to the following concentrations: 20% -30% of nitric acid, 10-15g/L of iron ions and a small amount of polymer surfactant and complex. Adding nitric acid with concentration of 4.5-6.5mol/L, iron ion with concentration of 16-20g/L, copper ion with concentration of less than 2g/L and tin ion with concentration of less than 4g/L into the clarified liquid according to the calculated amount, and then adjusting the concentrations of nitric acid, iron ion and a small amount of polymer surfactant and complex in the clarified liquid to the above concentrations to prepare the regenerated tin stripping liquid.
And carrying out a tin stripping experiment on the regenerated tin stripping solution by adopting a soaking method to detect the tin stripping performance, controlling the tin stripping temperature to be about 30 ℃, and obtaining the following experimental results: the tin stripping rate reaches 12 mu/min, the tin dissolving amount can reach 130g/L, the copper etching rate is less than 1 mu m/min, the performances are basically consistent with those of a new tin stripping solution, the circuit board function is basically not influenced, and the regeneration and reuse requirements can be met.
Example 4
The tin-stripping waste liquid used in the embodiment is detected to have the following contents/concentrations of components: the content of tin is more than 125g/L, the content of copper ions is 10g/L, the content of iron ions is 17g/L, and the residual quantity of nitric acid is 27%.
A regeneration method of tin stripping waste liquid comprises the following steps: introducing oxygen into the tin stripping waste liquid, and simultaneously aerating for 2 hours and standing and preserving the temperature for 40 ℃ to ensure that the alpha stannic acid in the waste liquid is completely converted into beta stannic acid; adding chloric acid and fatty acid salt into the waste liquid, heating to 40 ℃, preserving heat, and standing for 10 hours to perform coagulation on beta stannic acid in the waste liquid; the beta stannic acid precipitate is filtered by adopting an efficient filtering component, the recovery rate of tin is 95.9 percent, and the impurity content is 1.5 percent; then adding oxalic acid to precipitate a small amount of copper ions in the solution, and filtering by using a high-efficiency filtering assembly again to obtain copper oxalate solid and clear liquid;
analyzing and detecting the concentrations of nitric acid, iron ions, polymer surfactant and complex in the clarified liquid by using a chemical analyzer, and calculating the amount of the nitric acid, the ferric nitrate, the polymer surfactant and the complex which are required to be added for adjusting the concentrations of the nitric acid, the iron ions, the polymer surfactant and the complex in the clarified liquid to the following concentrations: 20% -30% of nitric acid, 10-15g/L of iron ions and a small amount of polymer surfactant and complex. Adding nitric acid with concentration of 4.5-6.5mol/L, iron ion with concentration of 16-20g/L, copper ion with concentration of less than 2g/L and tin ion with concentration of less than 4g/L into the clarified liquid according to the calculated amount, and then adjusting the concentrations of nitric acid, iron ion and a small amount of polymer surfactant and complex in the clarified liquid to the above concentrations to prepare the regenerated tin stripping liquid.
And carrying out a tin stripping experiment on the regenerated tin stripping solution by adopting a soaking method to detect the tin stripping performance, controlling the tin stripping temperature to be about 30 ℃, and obtaining the following experimental results: the tin stripping rate reaches 15 mu/min, the tin dissolving amount can reach 125g/L, the copper etching rate is less than 1 mu m/min, the performances are basically consistent with those of a new tin stripping solution, the circuit board function is basically not influenced, and the regeneration and reuse requirements can be met.
Example 5
The tin stripping waste liquid used in the embodiment is detected to have the following contents/concentrations of components: the tin content reaches more than 120g/L, the copper ion content is 10g/L, the iron ion content is 18g/L, and the residual amount of nitric acid is 25 percent.
A regeneration method of tin stripping waste liquid comprises the following steps: adding nitric acid into the tin-stripping waste liquid, and simultaneously aerating for 1.5h and standing and preserving the temperature for 35 ℃ to completely convert alpha stannic acid in the waste liquid into beta stannic acid; adding perchloric acid and sulfate into the waste liquid, heating to 35 ℃, preserving heat, and standing for 10 hours to perform coagulation on beta stannic acid in the waste liquid; the beta stannic acid precipitate is filtered by adopting a high-efficiency filtering component, the recovery rate of tin is 97.3 percent, and the impurity content is 1.6 percent; then adding oxalic acid to precipitate a small amount of copper ions in the solution, and filtering by using a high-efficiency filtering assembly again to obtain copper oxalate solid and clear liquid;
analyzing and detecting the concentrations of nitric acid, iron ions, polymer surfactant and complex in the clarified liquid by using a chemical analyzer, and calculating the amount of the nitric acid, the ferric nitrate, the polymer surfactant and the complex which are required to be added for adjusting the concentrations of the nitric acid, the iron ions, the polymer surfactant and the complex in the clarified liquid to the following concentrations: 20% -30% of nitric acid, 10-15g/L of iron ions and a small amount of polymer surfactant and complex. Adding nitric acid with concentration of 4.5-6.5mol/L, iron ion with concentration of 16-20g/L, copper ion with concentration of less than 2g/L and tin ion with concentration of less than 4g/L into the clarified liquid according to the calculated amount, and then adjusting the concentrations of nitric acid, iron ion and a small amount of polymer surfactant and complex in the clarified liquid to the above concentrations to prepare the regenerated tin stripping liquid.
And carrying out a tin stripping experiment on the regenerated tin stripping solution by adopting a soaking method to detect the tin stripping performance, controlling the tin stripping temperature to be about 30 ℃, and obtaining the following experimental results: the tin stripping rate can reach 12 mu/min, the tin dissolving amount can reach 80g/L, the copper etching rate is less than 1 mu m/min, the performances are basically consistent with those of the new tin stripping liquid, the circuit board function is basically not influenced, and the regeneration and reuse requirements can be met.
Example 6
The tin-stripping waste liquid used in the embodiment is detected to have the following contents/concentrations of components: the tin content reaches more than 110g/L, the copper ion content is 5g/L, the iron ion content is 16g/L, and the residual quantity of nitric acid is 23%.
A regeneration method of tin stripping waste liquid comprises the following steps: adding nitric acid into the tin stripping waste liquid, and simultaneously aerating for 1.5h and standing and preserving the temperature for 35 ℃ to completely convert alpha stannic acid in the waste liquid into beta stannic acid; adding perchloric acid into the waste liquid, heating to 35 ℃, preserving heat, and standing for 11 hours to perform coagulation on beta stannic acid in the waste liquid; the beta stannic acid precipitate is filtered by adopting a high-efficiency filtering component, the recovery rate of tin is 97.6 percent, and the impurity content is 1.3 percent; then adding oxalic acid to precipitate a small amount of copper ions in the solution, and filtering by using a high-efficiency filtering assembly again to obtain copper oxalate solid and clear liquid;
analyzing and detecting the concentrations of nitric acid, iron ions and a small amount of complex in the clarified liquid by using a chemical analyzer, and calculating the amounts of the nitric acid, the iron ions and the small amount of complex which are required to be added for adjusting the concentrations of the nitric acid, the iron ions and the small amount of complex in the clarified liquid to the following concentrations: 20% -30% of nitric acid, 10-15g/L of iron ions and a small amount of complex. Adding nitric acid with the concentration of 4.5-6.5mol/L, iron ion with the concentration of 16-20g/L, copper ion with the concentration of less than 2g/L and tin ion with the concentration of less than 4g/L into the clarified liquid according to the calculated amount, and adjusting the concentrations of nitric acid, iron ion and a small amount of complex in the clarified liquid to the concentrations to prepare the regenerated tin stripping liquid.
And carrying out a tin stripping experiment on the regenerated tin stripping solution by adopting a soaking method to detect the tin stripping performance of the regenerated tin stripping solution, controlling the tin stripping temperature to be about 30 ℃, and obtaining the following experimental results: the tin stripping rate reaches 15 mu/min, the tin dissolving amount can reach 120g/L, the copper etching rate is less than 1 mu m/min, the performances are basically consistent with those of a new tin stripping solution, the circuit board function is basically not influenced, and the regeneration and reuse requirements can be met.
Example 7
The tin stripping waste liquid used in the embodiment is detected to have the following contents/concentrations of components: the tin content reaches more than 130g/L, the copper ion content is 8g/L, the iron ion content is 16g/L, and the residual amount of nitric acid is 25 percent.
A regeneration method of tin stripping waste liquid comprises the following steps: adding nitric acid into the tin stripping waste liquid, and simultaneously aerating for 2 hours and standing and preserving the temperature for 35 ℃ to ensure that alpha stannic acid in the waste liquid is completely converted into beta stannic acid; then adding hydrochloric acid, chloric acid, fatty acid salt and sulfate into the waste liquid, simultaneously heating to 35 ℃, preserving heat and standing for 10 hours to ensure that beta stannic acid in the waste liquid is subjected to coagulation; the beta stannic acid precipitate is filtered by adopting a high-efficiency filtering component, the recovery rate of tin is 97.8 percent, and the impurity content is 1.7 percent; then adding oxalic acid to precipitate a small amount of copper ions in the solution, and filtering by using a high-efficiency filtering assembly again to obtain copper oxalate solid and clear liquid;
analyzing and detecting the concentrations of nitric acid, iron ions, polymer surfactant and complex in the clarified liquid by using a chemical analyzer, and calculating the amount of the nitric acid, the ferric nitrate, the polymer surfactant and the complex which are required to be added for adjusting the concentrations of the nitric acid, the iron ions, the polymer surfactant and the complex in the clarified liquid to the following concentrations: 20% -30% of nitric acid, 10-15g/L of iron ions and a small amount of polymer surfactant and complex. Adding nitric acid with concentration of 4.5-6.5mol/L, iron ion with concentration of 16-20g/L, copper ion with concentration of less than 2g/L and tin ion with concentration of less than 4g/L into the clarified liquid according to the calculated amount, and then adjusting the concentrations of nitric acid, iron ion and a small amount of polymer surfactant and complex in the clarified liquid to the above concentrations to prepare the regenerated tin stripping liquid.
And carrying out a tin stripping experiment on the regenerated tin stripping solution by adopting a soaking method to detect the tin stripping performance, controlling the tin stripping temperature to be about 30 ℃, and obtaining the following experimental results: the tin stripping rate reaches 13 mu/min, the tin dissolving amount can reach 125g/L, the copper etching rate is less than 1 mu m/min, the performances are basically consistent with those of a new tin stripping solution, the circuit board function is basically not influenced, and the regeneration and reuse requirements can be met.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Comparative example 1
The tin-stripping waste liquid used in the comparative example is detected to have the following components/concentrations: the tin content is 97.2g/L, the acidity is 4.6mol/L, the iron ion content is 18.7g/L, and the corrosion inhibitor content is 9.8 g/L.
Adding 2 mass percent of oxalic acid, 0.1 mass percent of polyacrylamide and 0.1 mass percent of hydrogen peroxide into the tin stripping waste liquid (the mass percent refers to the mass percent of the added substances in the tin stripping waste liquid), stirring for half an hour, and performing first centrifugal filtration to obtain a first filtrate and first filter residue. The detection proves that the tin content of the first filtrate is 4.2g/L, the recovery rate of tin is 95.6 percent, and the impurity content is 15.1 percent. Repeatedly washing the obtained first filter residue for half an hour by using ammonia water with the mass percentage concentration of 2%, and then carrying out second centrifugal filtration to obtain second tin slag, wherein the tin content in the second tin slag is 41% through detection.
Analyzing and detecting the concentrations of nitric acid, iron ions and corrosion inhibitor in the first filtrate by using a chemical analyzer, and calculating the amount of the nitric acid, the iron ions and the corrosion inhibitor which are required to be added for adjusting the concentrations of the nitric acid, the iron ions and the corrosion inhibitor in the first filtrate to the following concentrations: 5.3-6.7 mol/L of nitric acid, 18-25 g/L of iron ions and 10-15g/L of corrosion inhibitor. And adding nitric acid, ferric nitrate and a corrosion inhibitor into the first filtrate according to the calculated amount, so as to adjust the concentrations of the nitric acid, the ferric ions and the corrosion inhibitor in the first filtrate to the above concentrations, and preparing the regenerated tin stripping solution.
And carrying out a tin stripping experiment on the regenerated tin stripping solution by adopting a soaking method to detect the tin stripping performance, controlling the tin stripping temperature to be about 30 ℃, and obtaining the following experimental results: the tin stripping rate reaches 12 mu/min, and the tin stripping capacity is more than 120 g/L.
The above results show that, by adopting the regeneration method and the regeneration system of the embodiment of the invention, firstly, the tin-stripping waste liquid is pretreated to completely convert the alpha stannic acid into the beta stannic acid, then the beta stannic acid is subjected to coagulation and filtration, and then the filtrate is subjected to copper precipitation, filtration, seed liquid regeneration and other steps to separate copper and tin; or the product can be sold directly, so that the income of the company can be improved, and the cost control of the subsequent smelting process of a purchaser is facilitated; the recovery rate of tin can reach 95-98%, the impurity content is less than 2%, the recovery rate of tin is improved, the impurity content is reduced, tin and copper can be completely separated, usable regeneration liquid is obtained, the treatment cost of tin recovery and regeneration liquid recovery is reduced, alkaline solution is not needed to be used for carrying out copper-tin separation on tin mud in the simultaneous treatment process, the raw material cost of a tin stripping waste liquid regeneration treatment process is greatly reduced, the treatment process is simplified, the pollution to the environment is reduced, the recovery purity of copper and tin products is improved simultaneously, and the profit of recovered products is improved.
Claims (2)
1. The regeneration method of the tin stripping waste liquid is characterized by comprising the following steps:
(1) pretreatment: adding nitric acid into the tin stripping waste liquid, and continuously aerating for 1-2 hours to completely convert alpha stannic acid into beta stannic acid;
(2) beta stannic acid modification: performing coagulation on beta-stannic acid, wherein the coagulation method comprises the following steps: a. adding strong electrolyte and anionic surfactant into the waste liquid; the strong electrolyte is one or more of sulfuric acid, hydrochloric acid, chloric acid and perchloric acid; the anionic surfactant is one or more of fatty acid salt, sulfonate and sulfate salt; b. heating, preserving heat and standing the waste liquid;
(3) beta stannic acid filtration: filtering by adopting a high-efficiency filtering assembly, wherein the high-efficiency filtering assembly comprises a plurality of filtering devices which are connected in series or in parallel through pipelines, and the filtering aperture of a filtering layer in each filtering device is 1-200 nm; the turbid liquid filtered by the filtering device can be circularly filtered again;
(4) copper deposition: adding oxalic acid to precipitate copper ions in the solution, and then filtering to obtain a precipitate solid and a clear solution;
(5) regeneration of clear liquid: recycling the clarified liquid; and after the concentration of the main components in the clear liquid is detected, calculating the amount of corresponding additives required to be added for regulating the concentration of the main components in the clear liquid to the preset concentration, adding the additives into the clear liquid according to the calculated corresponding additive amount, and regulating the concentration of the main components in the clear liquid to the preset concentration to obtain the regenerated tin stripping liquid.
2. The regeneration method of the tin-stripping waste liquid as claimed in claim 1, wherein the filter layer is made of inert ceramic material; the shell pipeline of the filtering device is made of an acid and alkali resistant material, and the acid and alkali resistant material comprises a titanium material, glass fiber reinforced plastics or PP; and the filtering device is in a closed state.
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| CN112321047A (en) * | 2020-10-12 | 2021-02-05 | 光大绿色环保管理（深圳）有限公司 | Device and method for recycling nitric acid type tin stripping waste liquid |
| CN113832359B (en) * | 2021-08-30 | 2023-02-28 | 深圳市环保科技集团股份有限公司 | Method for preparing tin concentrate by using tin-containing sludge |
| CN114317969A (en) * | 2021-11-26 | 2022-04-12 | 江西瑞亿电子科技有限公司 | Method for recycling tin and copper from PCB tin waste liquid in recycling mode |
| CN114277249A (en) * | 2021-11-26 | 2022-04-05 | 江西瑞亿电子科技有限公司 | Treatment method for recycling tin, copper and waste gas from PCB tin waste liquid in recycling mode |
| CN114107675A (en) * | 2021-11-29 | 2022-03-01 | 深圳中科欧泰华环保科技有限公司 | Novel method and device for recovering metal palladium |
| CN115058762B (en) * | 2022-08-11 | 2022-11-08 | 深圳市板明科技股份有限公司 | Tin settling agent for electrotinning process and use method thereof |
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