CN108383278B - The processing method of tin removal waste liquor - Google Patents
The processing method of tin removal waste liquor Download PDFInfo
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- CN108383278B CN108383278B CN201810223839.XA CN201810223839A CN108383278B CN 108383278 B CN108383278 B CN 108383278B CN 201810223839 A CN201810223839 A CN 201810223839A CN 108383278 B CN108383278 B CN 108383278B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
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Abstract
The invention discloses a kind of processing methods of tin removal waste liquor, the processing method of the tin removal waste liquor is the following steps are included: precipitating reagent, flocculant and settling agent are added into tin removal waste liquor, so that the tin in the tin removal waste liquor reacts generation precipitating and rapid subsidence with the precipitating reagent, solidliquid mixture is obtained；The solidliquid mixture is separated by solid-liquid separation, the first filtrate and the first filter residue are obtained；First filter residue is recycled, pink salt is obtained；The concentration of main component in first filtrate is deployed to preset concentration, regeneration tin stripping liquid is obtained.The processing method of tin removal waste liquor provided by the invention is because that can realize simultaneously the recycling of tin and other compositions in tin removal waste liquor, to improve the resource recovery of tin removal waste liquor processing.
Description
Technical field
The present invention relates to the processing methods that waste disposal field more particularly to tin removal waste liquor are produced in printed circuit manufacture.
Background technique
It is the production most common side of outer circuit in print circuit plates making that SES, which (moves back film-alkali etching-and move back tin) technique,
Method, moving back tin is wherein essential critical process, moves back and needs in tin process using tin stripping liquid.Move back tin refer to utilize tin stripping liquid will
Tin coating on workpiece dissolves stripping, and during moving back tin, when the concentration of tin in tin stripping liquid reaches saturation, tin stripping liquid, which is lost, moves back tin
Ability forms tin removal waste liquor.
For tin removal waste liquor in addition to containing a large amount of tin, remaining ingredient is similar to tin stripping liquid.The processing side of current tin removal waste liquor
Method only recycles the tin in tin removal waste liquor, and is not recycled to the other compositions in addition to tin, therefore resource reclaim
Rate is low.
Above content is only used to facilitate the understanding of the technical scheme, and is not represented and is recognized that above content is existing skill
Art.
Summary of the invention
The main purpose of the present invention is to provide a kind of processing methods of tin removal waste liquor, it is intended to solve current tin removal waste liquor
The low problem of processing method resource recovery.
In order to achieve the above object, the present invention provides a kind of processing method of tin removal waste liquor, the processing side of the tin removal waste liquor
Method the following steps are included:
Precipitating reagent, flocculant and settling agent are added into tin removal waste liquor, so that the tin in the tin removal waste liquor sinks with described
Agent reaction in shallow lake generates precipitating and rapid subsidence, obtains solidliquid mixture, wherein the precipitating reagent includes oxalic acid, water-soluble oxalic acid
At least one of salt, phosphoric acid and water-soluble phosphate, the flocculant include aluminium polychloride, polymeric aluminium ferrum silicate, trichlorine
Change at least one of iron, polyacrylamide and heavy metal chelating agent, the settling agent includes sodium peroxydisulfate, sodium chlorate, secondary chlorine
At least one of sour sodium and hydrogen peroxide；
The solidliquid mixture is separated by solid-liquid separation, the first filtrate and the first filter residue are obtained；
First filter residue is recycled, pink salt is obtained；
The concentration of main component in first filtrate is deployed to preset concentration, regeneration tin stripping liquid is obtained.
Preferably, the precipitating reagent includes one of oxalic acid, water soluble oxalate, phosphoric acid and water-soluble phosphate or two
The mixture of kind, mass percent of the precipitating reagent in the tin removal waste liquor are 2%~30%；
The flocculant includes aluminium polychloride, polymeric aluminium ferrum silicate, ferric trichloride, polyacrylamide and heavy metal chelating
The mixture of one or both of agent, mass percent of the flocculant in the tin removal waste liquor are 0.1%~2%；
The settling agent includes the mixture of one or both of sodium peroxydisulfate, sodium chlorate, sodium hypochlorite and hydrogen peroxide,
Mass percent of the settling agent in the tin removal waste liquor is 0.1%~2%.
Preferably, mass percent of the precipitating reagent in the tin removal waste liquor is 4%~15%, and the flocculant exists
Mass percent in the tin removal waste liquor is 0.2%~1.2%, quality percentage of the settling agent in the tin removal waste liquor
Than being 0.1%~1%.
Preferably, the precipitating reagent include: mass percent be 70%~100% oxalic acid, mass percent be 0~
One of 30% water soluble oxalate, phosphoric acid and water-soluble phosphate substance.
Preferably, it is 80%~100% polyacrylamide, mass percent 0 that the flocculant, which includes: mass percent,
One of~20% aluminium polychloride, polymeric aluminium ferrum silicate, ferric trichloride and heavy metal chelating agent substance.
Preferably, the settling agent include: mass percent be 70%~100% hydrogen peroxide, mass percent be 0~
One of 30% sodium peroxydisulfate, sodium chlorate and sodium hypochlorite substance.
Preferably, the mode that the solidliquid mixture is separated by solid-liquid separation includes centrifugal filtration or plate-frame filtering.
Preferably, described the step of recycling, and obtain pink salt first filter residue, includes:
First filter residue is put into lye and is washed, to remove mantoquita or/and molysite in first filter residue,
Wherein, the lye includes at least one of ammonium hydroxide, soda ash solution or sodium hydroxide solution, and the quality percentage of the lye is dense
Degree is 2%~20%；
After the completion of washing, the solidliquid mixture of first filter residue and the lye is separated by solid-liquid separation, obtains second
Filter residue and the second filtrate；
Second filter residue is recycled, pink salt is obtained.
Preferably, the concentration by main component in first filtrate is deployed to preset concentration, is obtained regeneration and is moved back tin
The step of liquid includes:
Detect the concentration of main component in first filtrate；
Calculate the matter that the concentration of main component in first filtrate is deployed to the additive for needing to be added to preset concentration
Amount；
Additive is added into first filtrate according to the quality for needing the additive being added, so that described first
The concentration of main component reaches preset concentration in filtrate, obtains regeneration tin stripping liquid.
Preferably, main component includes nitric acid, iron ion and corrosion inhibiter in first filtrate, and the additive includes nitre
Acid, ferric nitrate and corrosion inhibiter.
The processing method of tin removal waste liquor provided by the invention, by the way that precipitating reagent is added into tin stripping liquid, so that tin removal waste liquor
In tin and precipitating reagent occur chemical reaction generate precipitating, then by be separated by solid-liquid separation obtain the first filter residue and the first filtrate, return
It receives the first filter residue and obtains pink salt, and the concentration of the main component in the first filtrate deployed and regeneration is prepared to preset concentration moves back
Tin liquor improves resource recovery to realize the recycling of tin and other compositions in tin removal waste liquor simultaneously.
Detailed description of the invention
Fig. 1 is the flow diagram of the processing method for the tin removal waste liquor that the embodiment of the present invention is related to；
Fig. 2 is the refinement schematic diagram of step S30 in the processing method for the tin removal waste liquor that the embodiment of the present invention is related to；
Fig. 3 is the refinement schematic diagram of step S40 in the processing method for the tin removal waste liquor that the embodiment of the present invention is related to.
The embodiments will be further described with reference to the accompanying drawings for the realization, the function and the advantages of the object of the present invention.
Specific embodiment
It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.
Firstly, making an explanation in conjunction with process of the Figure of description to the processing method of tin removal waste liquor of the present invention.
As shown in Figure 1, the processing method of tin removal waste liquor provided by the invention, overall procedure are as follows:
Tin stripping liquid be applied to print circuit plates making move back tin process after, generate tin removal waste liquor.It is provided by the invention to move back tin
Tin in tin removal waste liquor is separated by chemical precipitation method and is recycled by the processing method of waste liquid, after then removing tin again
Liquid formulation at regeneration tin stripping liquid, concrete operations are as follows:
Precipitating reagent, flocculant and settling agent are added into tin removal waste liquor by step S10.
Precipitating reagent is added into tin removal waste liquor, so that the tin in tin removal waste liquor and precipitating reagent occur chemical reaction generation and sink
It forms sediment, obtains solidliquid mixture.The precipitating reagent being added includes in oxalic acid, Soluble oxalate salt, phosphoric acid and soluble phosphate
It is at least one, wherein Soluble oxalate salt includes sodium oxalate, potassium oxalate and ammonium oxalate etc., soluble phosphate include sodium phosphate,
Potassium phosphate, ammonium phosphate etc..To reduce the influence of moving back tin function of the precipitating reagent being added to subsequent regeneration tin stripping liquid, it is preferable that
The precipitating reagent being added includes the mixed of one of oxalic acid, Soluble oxalate salt, phosphoric acid and Soluble oxalate salt or in which two kinds
Close object.In order to further reduce the influence of moving back tin function of the precipitating reagent of addition to subsequent regeneration tin stripping liquid, it is preferable that institute
The precipitating reagent of addition includes following components: the oxalic acid that mass percent is 70%~100%, and mass percent is 0~30%
One of water soluble oxalate, phosphoric acid and water-soluble phosphate substance；It is understood that working as the quality of precipitating reagent mesoxalic acid
When percentage is 100%, precipitating reagent is oxalic acid.
For enable generate precipitating quickly reunite and settle, into tin removal waste liquor be added precipitating reagent while, also plus
Enter flocculant and settling agent.The flocculant include aluminium polychloride, polymeric aluminium ferrum silicate, ferric trichloride, polyacrylamide and
At least one of heavy metal chelating agent, the settling agent include in sodium peroxydisulfate, sodium chlorate, sodium hypochlorite and hydrogen peroxide extremely
Few one kind.To reduce the flocculant being added and settling agent to the subsequent influence moved back tin recovered liquid and move back tin function, it is preferable that be added
Flocculant include one of aluminium polychloride, polymeric aluminium ferrum silicate, ferric trichloride, polyacrylamide and heavy metal chelating agent
Or in which two kinds of mixture；The settling agent being added includes one of sodium peroxydisulfate, sodium chlorate, sodium hypochlorite and hydrogen peroxide
Or two kinds of mixture.Tin function is moved back to the subsequent tin recovered liquid that moves back in order to further reduce flocculant and the settling agent of addition
Influence, it is preferable that the flocculant being added includes following components: mass percent is 80%~100% polyacrylamide, quality
One of aluminium polychloride, polymeric aluminium ferrum silicate, ferric trichloride and the heavy metal chelating agent that percentage is 0~20% substance；
It is understood that flocculant is polyacrylamide when the mass percent of polyacrylamide in flocculant is 100%.
The settling agent being added includes following components: mass percent be 70%~100% hydrogen peroxide, mass percent be 0~
One of 30% sodium peroxydisulfate, sodium chlorate and sodium hypochlorite substance；It is understood that when the matter of hydrogen peroxide in settling agent
When amount percentage is 100%, settling agent is hydrogen peroxide.
The solidliquid mixture generated in step S10 is separated by solid-liquid separation by step S20.
The resulting solidliquid mixture of above-mentioned steps is separated by solid-liquid separation, respectively to the first filtrate and the first filter residue, i.e.,
Realize the purpose for separating the tin in tin removal waste liquor, wherein the main component of the first filter residue is pink salt.It is separated by solid-liquid separation
Mode mainly includes centrifugal filtration or deckle board filtering, it is to be understood that also may be selected that its realized and be separated by solid-liquid separation
He carries out solid-liquid separation treatment at mode.
Step S30 recycles first filter residue.
It is pink salt in the main component for the first filter residue that step S20 is separated by solid-liquid separation, which is recycled, i.e.,
The recycling of tin in tin removal waste liquor is realized, can also be used to be further processed to obtain pure tin after pink salt recycling.
Step S40 carries out ingredient allotment to first filtrate, to prepare regeneration tin stripping liquid.
Separation and recovery of the processing method of tin removal waste liquor provided by the invention in addition to realizing tin in tin removal waste liquor, further includes reality
The recycling of other compositions in existing tin removal waste liquor.Concrete operations are as follows: by be separated by solid-liquid separation in step S20 to first filtrate in
The concentration of main component deploys to preset concentration to arrive regeneration tin stripping liquid, and then the regeneration tin stripping liquid can be used for move back tin
Process, to realize the recycling of the other compositions in addition to tin in tin removal waste liquor.It is understood that the type of main component
It can voluntarily select, be not particularly limited herein according to the actual situation, the preset concentration of the main component is main in tin stripping liquid
The concentration of ingredient is wanted, the tin stripping liquid which can prepare according to actual needs is voluntarily selected, and is not also done herein specific
Limitation.
It is to be appreciated that step S30 and step S40 is respectively the processing to the first filter residue and the first filtrate, with respectively
It realizes recycling and the preparation regeneration tin stripping liquid of tin, has no sequencing between two steps.
Further, referring to figure 2., purer pink salt in order to obtain, needs to utilize lye to carry out first filter residue
Cleaning, specifically, as shown in Fig. 2, i.e. step S30 includes:
Step S31 washs first filter residue using lye；
Corroded due in moving back tin process, having a small amount of copper by tin stripping liquid, there can be a small amount of copper ion in tin removal waste liquor,
Furthermore there is also iron ions in itself in tin stripping liquid, therefore the precipitating (i.e. the first filter residue) generated after precipitating reagent is added in tin removal waste liquor
In except largely be pink salt in addition to, there is also a small amount of mantoquita and molysite.Therefore, for removal the first filter residue in mantoquita and molysite it is miscellaneous
Matter obtains purer pink salt, needs to wash filter residue.Therefore, it is separated by solid-liquid separation, obtains by resulting solidliquid mixture
To after the first filtrate and the first filter residue, the first filter residue of gained is put into stirring and washing half an hour in lye, lye used at
Dividing includes: mass percent for 50%~100% ammonium hydroxide, the soda ash solution and sodium hydroxide that mass percent is 0~50%
One of solution substance；It is understood that when the mass percent of ammonium hydroxide in lye used is 100%, lye used
As ammonium hydroxide.The mass percentage concentration of lye used is 2%~20%, i.e., ammonia and soda ash in the lye (or ammonia and hydroxide
Sodium) gross mass percentage concentration be 2%~20%.
The solidliquid mixture of first filter residue and the lye is separated by solid-liquid separation by step S32；
Step S33 recycles the second filter residue.
After the completion of cleaning, the solidliquid mixture of first filter residue and the lye is carried out by solid-liquid point by centrifugal filtration
From the second filter residue and the second filtrate is obtained, the second filter residue is the pink salt purified, to realize the recycling of tin, the pink salt of purification is returned
It can also be used to be further processed to obtain pure tin after receipts.It is understood that resulting second filtrate (lye) of filtering is repeatable to be made
With continuing on for the cleaning of the first filter residue.
Further, referring to figure 3., Fig. 3 is the tool of preparation regeneration tin stripping liquid in the processing method of tin removal waste liquor of the present invention
The flow diagram of body.Above-mentioned first filtrate is prepared into regeneration tin stripping liquid, it is necessary first to obtain main component in the first filtrate
Concentration, deployed on the basis of this concentration, specifically, as shown in figure 3, i.e. step S40 includes:
Step S41 detects the concentration of the first filtrate main component；
Utilize the concentration of main component in the first filtrate obtained by corresponding chemical analyzer analysis detection, it is possible to understand that
It is that the type of the main component detected can be selected voluntarily according to the actual situation, is not particularly limited herein, for example, carries out
The main component of detection may include nitric acid, iron ion and corrosion inhibiter.
Step S42 calculates the amount for the additive that need to be added；
Additive is added according to resulting amount is calculated in step S43.
In detecting the first filtrate after the concentration of main component, calculate the concentration of the main component in the first filtrate
It deploys to the amount of the respective additive of addition needed for preset concentration, adds according to calculated respective additive amount into the first filtrate
Enter additive, the concentration of main component in the first filtrate is deployed to preset concentration, that is, obtain regeneration tin stripping liquid, and then can will again
Raw tin stripping liquid is for moving back tin process, to realize the recycling of the other compositions in addition to tin in tin removal waste liquor.It is understood that
It is that the preset concentration of the main component is the concentration of main component in tin stripping liquid, which can be according to actual needs
The tin stripping liquid of preparation is voluntarily selected, and is not particularly limited herein, for example, main component may include nitric acid, iron ion and
Corrosion inhibiter；Preset concentration can be with are as follows: 5.3~6.7mol/L of nitric acid, 18~25g/L of iron ion, 10~15g/L of corrosion inhibiter；Accordingly
Additive can be nitric acid, ferric nitrate and corrosion inhibiter.
Embodiment 1:
Tin removal waste liquor used in the present embodiment is as follows through detection each component content/concentration: stanniferous amount is 97.2g/L, and acidity is
4.6mol/L, iron ion content 18.7g/L, corrosion inhibiter 9.8g/L.
The oxalic acid that mass percent is 2%, the polyacrylamide that mass percent is 0.1% are added into the tin removal waste liquor
And (mass percent refers to is added the percentage that material mass accounts for tin removal waste liquor quality to the hydrogen peroxide that mass percent is 0.1%
Than), first time centrifugal filtration is carried out after stirring half an hour, obtains the first filtrate and the first filter residue.The first filtrate tin is detected to contain
Amount is 4.2g/L, and the rate of recovery of tin is 95.6%.
The first filter residue of gained carry out second after washing half an hour repeatedly with the ammonium hydroxide that mass percentage concentration is 2%
Centrifugal filtration obtains the second scruff, is 41% through Theil indices in the second scruff of detection.
Using the concentration of nitric acid, iron ion and corrosion inhibiter in the first filtrate of chemical analysis instrument analysis detection, calculate the
The concentration of nitric acid, iron ion and corrosion inhibiter is deployed to the nitric acid, ferric nitrate and corrosion inhibiter of addition needed for following concentration in one filtrate
Amount: 5.3~6.7mol/L of nitric acid, 18~25g/L of iron ion, 10~15g/L of corrosion inhibiter.According to calculating resulting amount to first
Nitric acid, ferric nitrate and corrosion inhibiter are added in filtrate, the concentration of nitric acid, iron ion and corrosion inhibiter in the first filtrate can be deployed to
Regeneration tin stripping liquid is prepared in above-mentioned concentration.
It uses infusion method move back tin experiment to the regeneration tin stripping liquid and moves back tin performance to detect it, control moves back tin temperature about
30 DEG C, experimental result is as follows: moving back tin rate and reaches 12 μ/min, moves back tin capacity greater than 120g/L, the above performance and new tin stripping liquid base
This is consistent, can satisfy the production requirement for moving back tin process.
Embodiment 2:
Tin removal waste liquor used in the present embodiment is as follows through detection each component content/concentration: stanniferous amount is 97.2g/L, and acidity is
4.6mol/L, iron ion content 18.7g/L, corrosion inhibiter 9.8g/L.
The phosphoric acid that mass percent is 4%, the heavy metal chelating that mass percent is 0.2% are added into the tin removal waste liquor
Agent, the sodium peroxydisulfate that mass percent is 0.5%, the mass percent refer to that material mass, which is added, accounts for the hundred of tin removal waste liquor quality
Divide ratio, carries out first time centrifugal filtration after stirring half an hour, obtain the first filtrate and the first filter residue.The first filtrate tin is detected to contain
Amount is 3.9g/L, and the rate of recovery of tin is 95.9%.
The soda ash solution for being 5% by ammonium hydroxide and mass percentage concentration that the first filter residue of gained is 5% with mass percentage concentration
Mixed solution (wherein, the mass ratio of ammonium hydroxide and soda ash solution be 9:1) wash repeatedly carry out after half an hour second from
The second scruff is obtained by filtration in the heart, is 42.4% through Theil indices in the second scruff of detection.
Using the concentration of nitric acid, iron ion and corrosion inhibiter in the first filtrate of chemical analysis instrument analysis detection, calculate the
The concentration of nitric acid, iron ion and corrosion inhibiter is deployed to the nitric acid, ferric nitrate and corrosion inhibiter of addition needed for following concentration in one filtrate
Amount: 5.3~6.7mol/L of nitric acid, 18~25g/L of iron ion, 10~15g/L of corrosion inhibiter.According to calculating resulting amount to first
Nitric acid, ferric nitrate and corrosion inhibiter are added in filtrate, the concentration of nitric acid, iron ion and corrosion inhibiter in the first filtrate is deployed to above-mentioned
Regeneration tin stripping liquid is prepared in concentration.
It uses infusion method move back tin experiment to the regeneration tin stripping liquid and moves back tin performance to detect it, control moves back tin temperature about
30 DEG C, experimental result is as follows: moving back tin rate and reaches 12.5 μ/min, moves back tin capacity greater than 120g/L, the above performance and new tin stripping liquid
It is almost the same, it can satisfy the production requirement for moving back tin process.
Embodiment 3:
Tin removal waste liquor used in the present embodiment is as follows through detection each component content/concentration: stanniferous amount is 120.1g/L, and acidity is
4.1mol/L, iron ion content 18.5g/L, corrosion inhibiter 9.6g/L.
Into the tin removal waste liquor be added mass percent be 10% oxalic acid and water soluble oxalate mixture (wherein,
The water soluble oxalate is sodium oxalate, potassium oxalate or ammonium oxalate；Oxalic acid and the mass ratio of water soluble oxalate are 7:3), quality
Mixture (wherein, polyacrylamide and the polymeric aluminium ferrum silicate of polyacrylamide and polymeric aluminium ferrum silicate that percentage is 0.7%
Mass ratio be 19:1), the mixture of the hydrogen peroxide and sodium chlorate that mass percent is 1% (wherein, hydrogen peroxide and sodium chlorate
Mass ratio is 19:1), the mass percent, which refers to, is added the percentage that material mass accounts for tin removal waste liquor quality, after stirring half an hour
First time centrifugal filtration is carried out, the first filtrate and the first filter residue are obtained.It is 3.8g/L through the first filtrate Theil indices of detection, tin returns
Yield is 96.8%.
The hydroxide for being 10% by ammonium hydroxide and mass percentage concentration that the first filter residue of gained is 10% with mass percentage concentration
It is laggard that the mixed solution (wherein, the mass ratio of ammonium hydroxide and sodium hydroxide solution is 4:1) of sodium solution carries out washing half an hour repeatedly
Second of centrifugal filtration of row obtains the second scruff, is 41.9% through Theil indices in the second scruff of detection.
Using the concentration of nitric acid, iron ion and corrosion inhibiter in the first filtrate of chemical analysis instrument analysis detection, calculate the
The concentration of nitric acid, iron ion and corrosion inhibiter is deployed to the nitric acid, ferric nitrate and corrosion inhibiter of addition needed for following concentration in one filtrate
Amount: 5.3~6.7mol/L of nitric acid, 18~25g/L of iron ion, 10~15g/L of corrosion inhibiter.According to calculating resulting amount to first
Nitric acid, ferric nitrate and corrosion inhibiter are added in filtrate, the concentration of nitric acid, iron ion and corrosion inhibiter in the first filtrate is deployed to above-mentioned
Regeneration tin stripping liquid is prepared in concentration.
It uses infusion method move back tin experiment to the regeneration tin stripping liquid and moves back tin performance to detect it, control moves back tin temperature about
30 DEG C, experimental result is as follows: moving back tin rate and reaches 11 μ/min, moves back tin capacity greater than 120g/L, the above performance and new tin stripping liquid base
This is consistent, can satisfy the production requirement for moving back tin process.
Embodiment 4:
Tin removal waste liquor used in the present embodiment is as follows through detection each component content/concentration: stanniferous amount is 120.1g/L, and acidity is
4.1mol/L, iron ion content 18.5g/L, corrosion inhibiter 9.6g/L.
The mixture of oxalic acid and water-soluble phosphate that mass percent is 15% is added into the tin removal waste liquor (wherein,
The water-soluble phosphate is sodium phosphate, potassium phosphate or ammonium phosphate, and the mass ratio of oxalic acid and water-soluble phosphate is 3:1), quality
Mixture (wherein, the mass ratio of polyacrylamide and ferric trichloride of polyacrylamide and ferric trichloride that percentage is 1.2%
For mixture (wherein, the matter of hydrogen peroxide and sodium hypochlorite of 9:1), the hydrogen peroxide that mass percent is 1.2% and sodium hypochlorite
Amount is than being 17:3), the mass percent, which refers to, is added the percentage that material mass accounts for tin removal waste liquor quality, and stirring half an hour is laggard
Row first time centrifugal filtration, obtains the first filtrate and the first filter residue.It is 3.3g/L, the recycling of tin through the first filtrate Theil indices of detection
Rate is 97.2%.
The soda ash for being 15% by ammonium hydroxide and mass percentage concentration that the first filter residue of gained is 15% with mass percentage concentration is molten
The mixed solution (wherein, the mass ratio of ammonium hydroxide and soda ash solution is 7:3) of liquid carry out second after washing half an hour repeatedly
Centrifugal filtration obtains the second scruff, is 45% through Theil indices in the second scruff of detection.
Using the concentration of nitric acid, iron ion and corrosion inhibiter in the first filtrate of chemical analysis instrument analysis detection, calculate the
The concentration of nitric acid, iron ion and corrosion inhibiter is deployed to the nitric acid, ferric nitrate and corrosion inhibiter of addition needed for following concentration in one filtrate
Amount: 5.3~6.7mol/L of nitric acid, 18~25g/L of iron ion, 10~15g/L of corrosion inhibiter.According to calculating resulting amount to first
Nitric acid, ferric nitrate and corrosion inhibiter are added in filtrate, the concentration of nitric acid, iron ion and corrosion inhibiter in the first filtrate is deployed to above-mentioned
Regeneration tin stripping liquid is prepared in concentration.
It uses infusion method move back tin experiment to the regeneration tin stripping liquid and moves back tin performance to detect it, control moves back tin temperature about
30 DEG C, experimental result is as follows: moving back tin rate and reaches 12 μ/min, moves back tin capacity greater than 120g/L, the above performance and new tin stripping liquid base
This is consistent, can satisfy the production requirement for moving back tin process.
Embodiment 5:
Tin removal waste liquor used in the present embodiment is as follows through detection each component content/concentration: stanniferous amount is 150.3g/L, and acidity is
3.4mol/L, iron ion content 17.9g/L, corrosion inhibiter 9.1g/L.
Mixture (wherein, oxalic acid and the phosphorus of oxalic acid and phosphoric acid that mass percent is 20% are added into the tin removal waste liquor
The mass ratio of acid is 17:3), the mixture (polypropylene of polyacrylamide and heavy metal chelating agent that mass percent is 1.5%
The mass ratio of amide and heavy metal chelating agent is 17:3) and mass percent be 1.5% hydrogen peroxide and sodium peroxydisulfate mixing
Object (mass ratio of hydrogen peroxide and sodium peroxydisulfate is 3:1), the mass percent refer to that material mass, which is added, accounts for tin removal waste liquor quality
Percentage.First time centrifugal filtration is carried out after stirring half an hour, obtains the first filtrate and the first filter residue.Detected the first filtrate
Theil indices are 5.1g/L, and the rate of recovery of tin is 96.6%.
The hydroxide for being 20% by ammonium hydroxide and mass percentage concentration that the first filter residue of gained is 20% with mass percentage concentration
It is laggard that the mixed solution (wherein, the mass ratio of ammonium hydroxide and sodium hydroxide solution is 3:2) of sodium solution carries out washing half an hour repeatedly
Second of centrifugal filtration of row obtains the second scruff, is 45.2% through Theil indices in the second scruff of detection.
Using the concentration of nitric acid, iron ion and corrosion inhibiter in the first filtrate of chemical analysis instrument analysis detection, calculate the
The concentration of nitric acid, iron ion and corrosion inhibiter is deployed to the nitric acid, ferric nitrate and corrosion inhibiter of addition needed for following concentration in one filtrate
Amount: 5.3~6.7mol/L of nitric acid, 18~25g/L of iron ion, 10~15g/L of corrosion inhibiter.According to calculating resulting amount to first
Nitric acid, ferric nitrate and corrosion inhibiter are added in filtrate, the concentration of nitric acid, iron ion and corrosion inhibiter in the first filtrate is deployed to above-mentioned
Regeneration tin stripping liquid is prepared in concentration.
It uses infusion method move back tin experiment to the regeneration tin stripping liquid and moves back tin performance to detect it, control moves back tin temperature about
30 DEG C, experimental result is as follows: moving back tin rate and reaches 11.5 μ/min, moves back tin capacity greater than 120g/L, the above performance and new tin stripping liquid
It is almost the same, it can satisfy the production requirement for moving back tin process.
Embodiment 6:
Tin removal waste liquor used in the present embodiment is as follows through detection each component content/concentration: stanniferous amount is 150.3g/L, and acidity is
3.4mol/L, iron ion content 17.9g/L, corrosion inhibiter 9.1g/L.
Mixture (wherein, oxalic acid and the phosphorus of oxalic acid and phosphoric acid that mass percent is 30% are added into the tin removal waste liquor
The mass ratio of acid is 19:1), mixture (wherein, the polypropylene of polyacrylamide and aluminium polychloride that mass percent is 2%
The mass ratio of amide and aluminium polychloride is 4:1), mixture (its of hydrogen peroxide and sodium hypochlorite that mass percent is 2%
In, the mass ratio of hydrogen peroxide and sodium hypochlorite is 7:3), the mass percent refers to that material mass, which is added, accounts for tin removal waste liquor quality
Percentage.First time centrifugal filtration is carried out after stirring half an hour, obtains the first filtrate and the first filter residue.Detected the first filtrate
Theil indices are 4.3g/L, and the rate of recovery of tin is 97.1%.
The hydroxide for being 20% by ammonium hydroxide and mass percentage concentration that the first filter residue of gained is 20% with mass percentage concentration
It is laggard that the mixed solution (wherein, the mass ratio of ammonium hydroxide and sodium hydroxide solution is 1:1) of sodium solution carries out washing half an hour repeatedly
Second of centrifugal filtration of row obtains the second scruff, is 45.7% through Theil indices in the second scruff of detection.
Using the concentration of nitric acid, iron ion and corrosion inhibiter in the first filtrate of chemical analysis instrument analysis detection, calculate the
The concentration of nitric acid, iron ion and corrosion inhibiter is deployed to the nitric acid, ferric nitrate and corrosion inhibiter of addition needed for following concentration in one filtrate
Amount: 5.3~6.7mol/L of nitric acid, 18~25g/L of iron ion, 10~15g/L of corrosion inhibiter.According to calculating resulting amount to first
Nitric acid, ferric nitrate and corrosion inhibiter are added in filtrate, the concentration of nitric acid, iron ion and corrosion inhibiter in the first filtrate is deployed to above-mentioned
Regeneration tin stripping liquid is prepared in concentration.
It uses infusion method move back tin experiment to the regeneration tin stripping liquid and moves back tin performance to detect it, control moves back tin temperature about
30 DEG C, experimental result is as follows: moving back tin rate and reaches 12.7 μ/min, moves back tin capacity greater than 120g/L, the above performance and new tin stripping liquid
It is almost the same, it can satisfy the production requirement for moving back tin process.
It should be noted that, in this document, the terms "include", "comprise" or its any other variant are intended to non-row
His property includes, so that the process, method, article or the system that include a series of elements not only include those elements, and
And further include other elements that are not explicitly listed, or further include for this process, method, article or system institute it is intrinsic
Element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that including being somebody's turn to do
There is also other identical elements in the process, method of element, article or system.
The serial number of the above embodiments of the invention is only for description, does not represent the advantages or disadvantages of the embodiments.
The above is only optimised process embodiment of the invention, therefore all according to structure described in present patent application range
It makes, the equivalent change or modification that feature and principle are done, is included in the scope of the patent application of the present invention.
Claims (7)
1. a kind of processing method of tin removal waste liquor, which is characterized in that the processing method of the tin removal waste liquor the following steps are included:
Precipitating reagent, flocculant and settling agent are added into tin removal waste liquor, so that tin and the precipitating reagent in the tin removal waste liquor
Reaction generate precipitating and rapid subsidence, obtain solidliquid mixture, wherein the precipitating reagent include mass percent be 70%~
95% oxalic acid, one of water soluble oxalate, phosphoric acid and water-soluble phosphate that mass percent is 5%~30% object
Matter, the flocculant include that mass percent is 80%~95% polyacrylamide, the polymerization that mass percent is 5%~20%
One of aluminium chloride, polymeric aluminium ferrum silicate, ferric trichloride and heavy metal chelating agent substance, the settling agent include quality percentage
Than the hydrogen peroxide for 70%~95%, mass percent is one in 5%~30% sodium peroxydisulfate, sodium chlorate and sodium hypochlorite
Kind substance；
The solidliquid mixture is separated by solid-liquid separation, the first filtrate and the first filter residue are obtained；
First filter residue is recycled, pink salt is obtained；
The concentration of main component in first filtrate is deployed to preset concentration, regeneration tin stripping liquid is obtained.
2. the processing method of tin removal waste liquor as described in claim 1, which is characterized in that
Mass percent of the precipitating reagent in the tin removal waste liquor is 2%~30%；
Mass percent of the flocculant in the tin removal waste liquor is 0.1%~2%；
Mass percent of the settling agent in the tin removal waste liquor is 0.1%~2%.
3. the processing method of tin removal waste liquor as claimed in claim 2, which is characterized in that the precipitating reagent is in the tin removal waste liquor
In mass percent be 4%~15%, mass percent of the flocculant in the tin removal waste liquor be 0.2%~
1.2%, mass percent of the settling agent in the tin removal waste liquor is 0.1%~1%.
4. the processing method of tin removal waste liquor as claimed in any one of claims 1 to 3, which is characterized in that described by the solid-liquid
The mode that mixture is separated by solid-liquid separation includes centrifugal filtration or plate-frame filtering.
5. the processing method of tin removal waste liquor as claimed in any one of claims 1 to 3, which is characterized in that described by described first
The step of filter residue is recycled, and pink salt is obtained include:
First filter residue is put into lye and is washed, to remove mantoquita or/and molysite in first filter residue,
In, the mass percentage concentration of the lye is 2%~20%, and the lye includes: the ammonia that mass percent is 50%~100%
Water, one of soda ash solution and sodium hydroxide solution that mass percent is 0~50% substance；
After the completion of washing, the solidliquid mixture of first filter residue and the lye is separated by solid-liquid separation, the second filter residue is obtained
With the second filtrate；
Second filter residue is recycled, pink salt is obtained.
6. the processing method of tin removal waste liquor as claimed in any one of claims 1 to 3, which is characterized in that described by described first
The concentration of main component is deployed to preset concentration in filtrate, obtain regeneration tin stripping liquid the step of include:
Detect the concentration of main component in first filtrate；
Calculate the quality that the concentration of main component in first filtrate is deployed to the additive for needing to be added to preset concentration；
Additive is added into first filtrate according to the quality for needing the additive being added, so that first filtrate
The concentration of middle main component reaches preset concentration, obtains regeneration tin stripping liquid.
7. the processing method of tin removal waste liquor as claimed in claim 6, which is characterized in that main component packet in first filtrate
Nitric acid, iron ion and corrosion inhibiter are included, the additive includes nitric acid, ferric nitrate and corrosion inhibiter.
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| CN111924999A (en) * | 2020-07-03 | 2020-11-13 | 昆山中环实业有限公司 | Wet tin stripping waste liquid treatment method |
| CN112250208A (en) * | 2020-08-31 | 2021-01-22 | 金禄电子科技股份有限公司 | Tin stripping waste liquid treatment method and device |
| CN112573698B (en) * | 2020-11-26 | 2022-12-27 | 苏州美源达环保科技股份有限公司 | Method for recovering tin in PCB production process |
| CN113754130B (en) * | 2021-09-30 | 2022-10-04 | 广东中奕环保科技有限公司 | Tin stripping waste liquid recycling and regeneration treatment system and method |
| 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 |
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| CN102191383A (en) * | 2011-04-22 | 2011-09-21 | 深圳市格林美高新技术股份有限公司 | Treatment method for waste printed circuit board |
| CN204727953U (en) * | 2015-04-10 | 2015-10-28 | 李玉明 | A kind of useless tin Water Sproading recycles production line |
| CN106186420A (en) * | 2016-08-04 | 2016-12-07 | 深圳市洁驰科技有限公司 | A kind of waste tin stripper processing system and processing method |
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| FI120052B (en) * | 2007-04-13 | 2009-06-15 | Yara Suomi Oy | A method for treating and reusing an etching solution |
| CN103436885A (en) * | 2013-09-25 | 2013-12-11 | 深圳市瑞世兴科技有限公司 | Method for recycling tin removal waste liquor |
| CN104986892A (en) * | 2015-07-02 | 2015-10-21 | 清远市新绿环境技术有限公司 | Tin stripping waste liquid treating method |
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| CN102191383A (en) * | 2011-04-22 | 2011-09-21 | 深圳市格林美高新技术股份有限公司 | Treatment method for waste printed circuit board |
| CN204727953U (en) * | 2015-04-10 | 2015-10-28 | 李玉明 | A kind of useless tin Water Sproading recycles production line |
| CN106186420A (en) * | 2016-08-04 | 2016-12-07 | 深圳市洁驰科技有限公司 | A kind of waste tin stripper processing system and processing method |
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