CN102115890A - Total recycling method of PCB (printed circuit board) nitric acid type tin-lead stripping waste liquid - Google Patents
Total recycling method of PCB (printed circuit board) nitric acid type tin-lead stripping waste liquid Download PDFInfo
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Abstract
The invention provides a total recycling method of a PCB (printed circuit board) nitric acid type tin-lead stripping waste liquid. Ferrous sulfate is used as a reaction agent and a settling agent to react with the nitric acid type tin-lead stripping waste liquid; a filter cake is acquired from a reaction liquid through filtering separation, and is cleaned for the extraction of solid-phase tin-lead mud; a filter liquid and a cleaning liquid are merged to serve as a mother liquid; then iron is used as a reducing agent and a displacing agent to extract sponge copper from the mother liquid until the residual copper content in the mother liquid is lower than 1mg/L; the sponge copper is rinsed by clear water; after the sponge copper is extracted, the iron content of the residual mother liquid containing a large quantity of ion and acid is regulated through ferric salt or ferrous salt, and the acid content is regulated through acid; and after the residual mother liquid is continuously aerated through air or oxygen gas, ferrous iron is oxidized, hydrolyzed and polymerized, so as to prepare modified polymeric iron which serves as a water purifying agent. Through the method, the nitric acid type tin-lead stripping waste liquid is totally recycled, the extraction rates of tin, lead and copper respectively exceed 99.3 percent, 99.9 percent and 99.0 percent, the yield of the modified polymeric iron reaches 100 percent, and three wastes and efflux are avoided, so that the environment is protected, and sustainable development of the PCB industry is achieved.
Description
Technical field
The present invention relates to the processing and the method for comprehensive utilization of PCB nitric acid type tin-lead soldering waste liquid, be specifically related to the full method of resource of PCB nitric acid type tin-lead soldering waste liquid.
Background technology
Along with deepening continuously and economic stable development of China's reform and opening-up, IT industry has become the important mainstay industry of China.Along with the flourishing emergence of IT industry, printed circuit board (be called for short PCB) production is rapid growth with surprising rapidity also.By 2005, family surplus the PCB enterprise 3500 of the existing different scales of China, the PCB ultimate production breaks through 1.05 * 10
8m
2, become one of global most important PCB manufacturing center.
In the PCB manufacturing processed, zinc-plated lead, the figure etching, operations such as tin-lead soldering need efflux multiple pollutent of different nature, as etching waste liquor, tin-lead soldering waste liquid etc., wherein etching waste liquor is shown great attention to, and obtain than resource utilization recycling fully, the patent application that February 28, disclosed publication number was CN1920071A in 2007, patent application that on March 21st, 2007, disclosed publication number was CN1931720 and the patent application that July 9, disclosed publication number was CN101215062 in 2008, all etching waste liquor is carried out recycling, and be applicable to industrial applications.And tin-lead soldering waste liquid toxicity height, quantity are many, more serious to the harm of ecotope, are a kind of danger wastes that very big recycling is worth that has.
Tin-lead soldering liquid is broadly divided into fluorochemical type and nitric acid type two classes.Fluorochemical type tin-lead soldering liquid is made up of hydrofluoric acid, ammonium bifluoride, superoxide etc., the tin-lead soldering process can be generated heat in a large number, easily cause ageing equipment and damage, and fluorochemical high volatility, toxicity height, pollute very serious, environment, technology, economic target are poor, as the early stage industrial technology of generally using, are eliminated substantially at present; Nitric acid type tin-lead soldering liquid is made up of nitric acid, iron nitrate and auxiliary agent (Huan Shi complexing agent etc.), and it moves back, and the plumbous speed of tin is fast, and little to the corrosion of copper, smooth finish is good, and pollutions such as no fluorochemical are the leading formulations of current PCB industry production.
By the full resource utilization of industrialization means realization tin-lead soldering waste liquid, the protection environment is realized the Sustainable development of PCB industry, is a major issue with strategic importance.For a long time, at nitric acid type tin-lead soldering waste liquid (being called for short WSP), the starting point both domestic and external concentrates on the recycling of tin lead and copper substantially, generally adopts chemical precipitation method, electrolytic process, absorption method, ion exchange method and biochemical process.Wherein, chemical precipitation method technology is simple, easy handling, and processing cost is lower, and is most widely used general; Absorption method, ion exchange method and biochemical process inadequately still can't industrialization because of cost and technology maturation; Electrolytic process is especially noticeable with its bright prospect, the patent application that February 4, disclosed publication number was CN1472362 in 2004, utilize low-temperature electrolytic reduction cupric ion to be steps such as the oxide compound of tin and lead and precipitation of hydroxide thing exactly for metallic copper and high-temperature electrolysis reduction stannous ion and lead ion, and with the cupric ion in the waste liquid, tin ion and lead ion are removed, make the fresh waste liquid behind these positively charged ions of removal be used to prepare new stripping tin or tin-lead soldering waste liquid, realize the full resource utilization of waste liquid, but because of electrolytic process is invested big, potential safety hazard is many, produce new impurity and impurity is gathered, the PCB scrap rate is improved, produce such environmental effects enterprise cleaner productions such as acid mist, and still do not have application value at present.As for the WSP circulation and regeneration technology that is full of intention, from WSP, take out tin, lead and copper office and add each component of shortcoming by the original formulation of tin-lead soldering liquid again, imagine finely, but regeneration tin-lead soldering liquid complicated component (exist impurity to gather and make a variation tendency) certainly will increase the useless plate rate of PCB, and PCB processing belongs to the sophisticated manufacturing of IT industry, the added value height, material cost is big, and tooling cost is little, so the increase of useless plate rate is intolerable, is difficult to practice.With traditional acid-base neutralisation art breading WSP, alkali consumption is big, and the rate of recovery of tin, lead and copper is low.The application documents that January 26, disclosed publication number was CN1569644 in 2005 have carried out regeneration to waste tin stripper, prepare the outstanding electronic-grade barium stannate of quality.Though improved the added value of product of tin, cost is also high, and the rate of recovery of tin, lead and copper is still low; Recapture agent or sodium sulphite of employing extracts metal, because of WSP comprises a large amount of high ferros and strong oxidizer nitric acid, cause the medicament loss very big, and the subsequent disposal of each metal is extremely difficult in the mixed sediment, and waste water more is difficult to innoxious; Add sulfuric acid to WSP and can improve plumbous extraction, but the sour molten aggravation of the decomposition of nitric acid and stannic acid not only worsens operating environment, and greatly increased the weight of follow-up water treatment load and difficulty; Earlier steam nitric acid from WSP by distil process, take chemical precipitation technology to separate tin, lead and copper again, the recycling rate of WSP is greatly improved, but facility investment is big, and energy consumption is many, the comprehensive cost height, and severe operational environment is polluted still very serious.The research and development situation of comprehensive recent two decades both at home and abroad and current industry are actual, consider that WSP mainly comprises tin lead salt, mantoquita, molysite, nitric acid (salt) and auxiliary agent (inhibition complexing agent etc.), these components have very high value as resource, then belong to Hazardous wastes as pollutent, need high processing costs, and have potential safety hazard such as secondary pollution.Therefore, handle WSP and must establish the idea that integration is recycled, thoroughly eliminate environment hidden danger.
Summary of the invention
The present invention is directed to the prior art deficiency, the full method of resource of PCB nitric acid type tin-lead soldering waste liquid is provided.The present invention is to be reagent and settling agent with the ferrous sulfate, react with PCB nitric acid type tin-lead soldering waste liquid, the isolating after filtration filter cake of reaction solution extracts the plumbous mud of solid phase tin through cleaning, filtrate and scavenging solution merge as mother liquor, mother liquor is copper bearing acidic solution, be that reductive agent, displacer fully extract copper sponge again with iron from mother liquor, extraneous copper content is lower than 1mg/L in mother liquor, and copper sponge is through the clear water rinsing; Carry behind the copper the last raffinate that comprises a large amount of iron and acid and regulate iron level with molysite or ferrous salt again, regulate acid content, by to gas or oxygen continuous aeration, ferrously prepare water purification agent through oxidation, hydrolysis, polymerization with acid---modified polyiron.
The present invention specifically realizes as follows:
(1) extraction of tin lead, separation: a certain amount of WSP is pumped into reaction tank, start stirrer, add copperas solution under agitation condition in WSP, the ferrous sulfate molar weight in the copperas solution is Pb
2+1.0～3.0 times of molar weights, continue stirring reaction and got reaction solution in 0.5～2.0 hour, reacting liquid filtering separate filter cake and filtrate, filter cake cleans with clear water, get plumbous mud of solid phase tin and scavenging solution, filtrate and scavenging solution merge as mother liquor and move into Buffer Pool, and mother liquor is copper bearing acidic solution, substantially not stanniferous and lead.
(2) extraction of copper: mother liquor constantly contacts, reacts, separates out copper sponge by acid-resistant ceramic pump at contact reactor with iron, and copper sponge compiles and discharge regularly at Buffer Pool, and through the clear water rinsing; Put forward the copper process and need regularly add iron, when copper content is less than 1mg/L in mother liquor, close the preceding valve of acid-resistant ceramic pump, open residual-gas valve subsequently, the raffinate that will comprise a large amount of iron and acid pumps into polymerization reaction kettle.The rinse water of rinsing copper sponge gained can be used for the preparation of copperas solution in the step (1).
(3) preparation of modified polyiron: the raffinate of step (2), regulate iron level with molysite or ferrous salt respectively, regulate acid content with acid, by the air or oxygen continuous aeration, ferrous again through reactions such as oxidation, hydrolysis, polymerizations, can prepare the water purification agent modified polyiron.
WSP of the present invention can be any nitric acid type tin-lead soldering waste liquid of producing PCB, or any mixing of multiple PCB nitric acid type tin-lead soldering waste liquid.
The plumbous mud of above-mentioned steps (1) gained tin gets the tin lead pig through roasting, blast furnace smelting; Step (2) gained copper sponge obtains the high purity copper cake by reducing roasting.
The ferrous sulfate of above-mentioned steps (1) is ferrous sulfate product or sulfur acid ferrous waste material; Be preferably iron vitriol.
The iron of above-mentioned steps (2) is iron plate, iron mud, iron powder or iron plane flower; Be preferably bigger scrap iron skin of specific surface area or scrap iron powder.
The molysite of above-mentioned steps (3) is an iron trichloride, and ferrous salt is more than one of ferrous sulfate, iron protochloride, is preferably iron vitriol.
The acid of above-mentioned steps (3) is mineral acid or organic acid; Mineral acid is more than one of sulfuric acid, hydrochloric acid, phosphoric acid; Organic acid is more than one of citric acid, thionamic acid; Be preferably sulfuric acid.
The present invention makes that each effective constituent gets utilization among the WSP, wherein the extraction yield of tin surpasses 99.3%, and plumbous extraction yield surpasses 99.9%, and the extraction yield of copper also can reach more than 99.0%, the yield rate 100% of modified polyiron, entire operation flow process do not have the three wastes to produce and efflux.
Core procedure of the present invention is the extraction of tin lead, and the introducing of ferrous sulfate is most important, and excessive sulfate radical is not only with the complete sedimentation of lead, and ferrous ion can effectively reduce the acidity and the oxidisability of solution system, disintegrates the sour molten environment around the stannic acid.Weaken in lead sulfate sedimentation, acidity and oxidisability, the high price iron ion increases etc. under the multiple short heavy factor affecting, tin will be with the abundant sedimentation of stannic acid form.Specifically comprise following chemical reaction:
Pb
2++SO
4 2-＝＝＝PbSO
4↓ ①
3Fe
2++4H
++NO
3 -＝＝＝3Fe
3++2H
2O+NO ②
Sn
4++4H
2O＝＝＝H
2SnO
3↓+4H
+ ③
Fe
2++SO
4 2-+NO＝＝＝Fe(NO)SO
4 ④
Obviously, the dosage of ferrous sulfate must surpass Pb
2+Molar weight just can guarantee plumbous by sedimentation fully, but excessive molysite, the ferrous salt content that certainly will increase solution system too much, and then influence the follow-up copper process of putting forward.Actual mechanical process is more appropriate with 1.0～3.0 times of configuration ferrous sulfate of stoichiometric number.
Leaching process at step (2) copper, the present invention is exactly still to comprise partial oxygen voltinism material (as nitric acid and high price iron ion) in the reaction system of the present invention with the different of leaching process maximum described in the patent application that on February 28th, 2007, disclosed publication number was CN1920071, so this operation " sacrifice " part iron is earlier eliminated its oxidisability, just can displace copper sponge afterwards.It is as follows to react ten thousand formulas:
Fe+2Fe
3+＝＝＝3Fe
2+ ⑤
3Fe+8H
++2NO
3 -＝＝＝3Fe
2++4H
2O+2NO ⑥
Fe+Cu
2+＝＝＝Fe
2++Cu ⑦
The NO that 6. reaction produces will be absorbed by ferrous sulfate by reaction form 4. in liquid phase immediately, and Fe (NO) SO4 plays katalysis and is stored in solution system in preparation modified polyiron process.
Plumbous or prepare other tin products, plumbous product as for the plumbous mud tin metallurgy of tin, copper sponge copper metallurgy or prepare other copper products, and the raffinate that comprises a large amount of iron and acid prepares modified polyiron, can adopt Metal smelting, chemical treatment, reducing roasting to cooperate the present common technology realizations in this area such as high-temperature fusion electrolysis, seldom give unnecessary details herein.
The present invention compared with prior art has following advantage or characteristics:
(1) the present invention is that reagent and settling agent extract tin lead with the ferrous sulfate from WSP, and cost is low, and few, easily separated, the purifying of the plumbous mud impurity of tin because the solubility product of lead sulfate is minimum, can be guaranteed plumbous by " fully " sedimentation; The effect of settling of lead sulfate is very good, and the water-sol of tin is had the heavy effect that helps; And ferrous sulfate is oxidized, needs to consume a large amount of acid, impels system acidity to fall greatly, destroys the colloidal stability of the water-sol in system of tin, makes the extraction yield of tin surpass 99.3%, and plumbous extraction yield surpasses 99.9%; And traditional technology reclaims tin, lead, copper by chemical precipitation means such as acid-base neutralisations, product exists with the mixed precipitation form, impurity is many, the tin and the plumbous rate of recovery only are respectively 65～95% and 60～80%, and traditional technology is left over a large amount of lead containing sludge and waste water (belonging to high malicious danger wastes), and secondary pollution is serious.
(2) the present invention extracts copper sponge by the metallic iron substitution method from WSP, and the rate of recovery of copper can reach more than 99.0%; And traditional technology is to extract with tin, lead by coprecipitation method, and copper is eliminated with impurity forms such as slags in the subsequent disposal of mixed precipitation substantially, and not only without any economic return, and its comprehensive cost also exceeds more than 1 times than the technology of the present invention.
(3) handle WSP per ton, but 0.7～1.5 ton of modified polyiron of the technology of the present invention coproduction is equivalent to 700～1500 yuan of newly-increased incomes; And traditional technology need efflux 3～10 tons of poisonous waste water of high density and 0.1 ton of left and right sides slag or other solid waste approximately, these pollutents of harmless treatment need about 300～1000 yuan of additional cost, efflux 1～3 ton of soluble compounds (inorganic salt etc.) and volatile gases (acid mist, ammonia etc.) simultaneously, its pollution and harm to ecotope is still very surprising.
(4) the present invention will carry the raffinate behind the copper, by the air or oxygen continuous aeration, ferrously can directly prepare modified polyiron through oxidation, hydrolysis, polymerization, the yield rate 100% of modified polyiron; This production method has realized the full resource utilization of WSP effective constituent, and not only itself produces and efflux without any the three wastes, but and a large amount of environmental protection medicaments of by-product---modified polyiron.Traditional technology but needs the poisonous waste water of a large amount of high densitys of harmless treatment, waste residue and volatile gases, not only wastes resource, and processing costs is high, and has quite serious secondary pollution and potential safety hazard.
Embodiment
Make below in conjunction with 1～5 couple of the present invention of embodiment and to further specify.
Embodiment 1
The composition analysis of WSP is as shown in table 1:
Table 1
The above-mentioned WSP of 25368kg is imported band stir (7.5kW, 30m 16rpm)
3Buried reaction tank, adding 2400kg concentration under agitation condition is the iron vitriol solution of 50wt%, finish in 1 hour, continuation is stirred, reaction got reaction solution in 0.5 hour, reaction solution is through flame filter press filtering separation solid-liquid phase, the gained filter cake cleans with the 1000kg clear water again, and filtered liquid and scavenging solution are merged into mother liquor, and filter cake is the plumbous mud of tin.The plumbous mud total amount of tin 12294kg, stanniferous 9.839wt%, leaded 6.619wt% (corresponding tin, plumbous extraction yield are respectively 99.38% and 99.93%); With total amount is 16447kg (cupric 0.5617wt%, iron content 4.585wt%) mother liquor moves into Buffer Pool, fill up contact reactor with 1000kg iron plane flower, starting acid-resistant ceramic pump then makes mother liquor constantly contact, react, separate out copper sponge, circulation with the iron plane flower, copper sponge compile in Buffer Pool bottom and regularly take out, drain, the clear water rinsing, the rinse water of rinsing copper sponge gained are used to prepare aforementioned iron vitriol solution.The iron plane flower is constantly added in operating process, and pays close attention to the extraneous copper content of circulating mother liquor; When mother liquor extraneous copper content during less than 1mg/L, close valve before the contact reactor immediately, open residual-gas valve subsequently, the raffinate that will comprise a large amount of iron and acid pumps into polymerization reaction kettle.Carry the total iron consumption amount 1103kg of copper process, can extract the copper sponge 102.6kg (extraction yield 99.59% of copper) of cupric 89.68wt%; Raffinate total amount 17285kg, wherein iron content 10.74wt%; Add the 9650kg iron vitriol and regulate iron level and 1500kg vitriol oil adjusting acid content, the oxygen valve of slowly outwarding winding then, use the oxygen continuous aeration, ferrously can make about 28400kg modified polyiron through oxidation, hydrolysis, polyreaction, its iron level 13.33wt%, basicity 18.58%, density are 1554kg/m
3
Modified polyiron preparation process among embodiment 2～embodiment 5 is all as described in the embodiment 1.
Embodiment 2
Implementation method and step wherein continue to stir 1 hour behind the adding iron vitriol solution in WSP with embodiment 1, and the composition analysis of WSP is as shown in table 2:
Table 2
Wherein WSP is 24983kg, 50wt% iron vitriol solution 3600kg, the plumbous mud total amount of tin 14408kg, stanniferous 9.958wt% wherein, leaded 6.237wt% (tin, plumbous extraction yield are respectively 99.67% and 99.97%); Mother liquor total amount 15672kg, cupric 0.6423wt% wherein, iron content 4.591wt%.Carry total iron consumption amount 1135kg of copper process, copper sponge 113.8kg, cupric 88.01wt% (extraction yield 99.50% of copper); Raffinate total amount 15540kg, wherein iron content 11.93wt%.Add the 11550kg iron vitriol and the 2000kg vitriol oil can make about 29000kg modified polyiron to system, its iron level 14.36wt%, basicity 15.45%, density is 1683kg/m
3
Embodiment 3
Implementation method and step wherein continue to stir 2 hours behind the adding iron vitriol solution in WSP with embodiment 1, and the composition analysis of WSP is as shown in table 3:
Table 3
WSP is 25143kg, and 50wt% iron vitriol solution 5300kg extracts the plumbous mud total amount of tin 13542kg, stanniferous 10.79wt% wherein, leaded 5.395wt% (extraction yield 99.92% of tin, plumbous extraction yield 99.99%); The mother liquor total amount of extracting behind the plumbous mud of tin is 18506kg, cupric 0.4992wt% wherein, iron content 4.369wt%.Carry total iron consumption amount 1048kg of copper process, copper sponge 122.2kg, cupric 75.10wt% (extraction yield 99.35% of copper); Carry raffinate total amount 19387kg, wherein iron content 9.575wt% behind the copper.Add the 5000kg iron vitriol and the 1500kg vitriol oil can make about 25800kg modified polyiron to system, its iron level 11.07wt%, basicity 13.78%, density is 1457kg/m
3
Embodiment 4
Implementation method and step wherein continue to stir 1..5 hour behind the adding iron vitriol solution in WSP with embodiment 1, and the composition analysis of WSP is as shown in table 4:
Table 4
WSP is 24565kg, and 50wt% iron vitriol solution 5000kg extracts the plumbous mud total amount of tin 14952kg, stanniferous 9.738wt% wherein, leaded 5.933wt% (extraction yield 99.90% of tin, plumbous extraction yield 99.98%); Mother liquor total amount 15600kg, cupric 0.8102wt% wherein, iron content 6.509wt%.Carry total iron consumption amount 1244kg of copper process, copper sponge 157.0kg, cupric 80.05wt% (extraction yield 99.42% of copper); Carry raffinate total amount 16573kg, wherein iron content 13.63wt% behind the copper.Add 750kg strong phosphoric acid (85wt%) to system and can make about 17300kg modified polyiron, its iron level 13.06wt%, basicity 17.26%, density is 1531kg/m
3
Embodiment 5
Implementation method and step wherein continue to stir 1 hour behind the adding iron vitriol solution in WSP with embodiment 1, and the composition analysis of WSP is as shown in table 5:
Table 5
WSP is 25951kg, and 50wt% iron vitriol solution 7000kg extracts the plumbous mud total amount of tin 14094kg, stanniferous 9.800wt% wherein, leaded 6.252wt% (extraction yield 99.95% of tin, plumbous extraction yield 99.99%); Mother liquor total amount 19850kg, cupric 0.6057wt% wherein, iron content 5.725wt%.Carry total iron consumption amount 1039kg of copper process, copper sponge 168.4kg, cupric 70.79wt% (extraction yield 99.15% of copper); Carry raffinate total amount 20640kg, wherein iron content 10.54wt% behind the copper.Add the 1000kg vitriol oil to system and can make about 21620kg modified polyiron, its iron level 10.06wt%, basicity 16.22%, density is 1337kg/m
3
The technology of the present invention is converted into tin, lead, copper and modified polyiron with WSP, has realized the full resource utilization of WSP effective constituent, does not have the three wastes to produce and effluxes.
Tin, lead, copper are important non-ferrous metals, have application, especially metallic copper widely in fields such as national defence, industry and daily lifes, china natural resources is in short supply, all need spend a large amount of foreign exchange imports every year, and often be subjected to coercing or extorting under false pretense of international speculation fund.High efficiency extraction tin, lead, copper from WSP, except economy, environmental protection factor, all significant to industry, the social safety of safeguarding China.
Modified polyiron is a kind of important environmental protection medicament, and belonging to new sections is inorganic high molecular water purifier, and superior performance has no side effect, and has vast market prospect and economic worth in China.According to preresearch estimates, China is annual to need all kinds of water purification agents more than 5,000 ten thousand tons, current main employing aluminium series water purifier, but the aluminium series water purifier is relatively poor to the removal effect of COD, colourity etc., and the aluminium poison manifests day by day to the potential threat of human body.The raffinate that the present invention utilizes WSP to carry behind tin lead, the copper prepares modified polyiron, and with low cost, its market outlook are more wide, and it is back to the IT industry, is a major action that realizes the Sustainable development of IT industry.The modified polyiron that the present invention produces is applied in numerous sewage treatment projects.Table 6 (* is this enterprise actual consumption and technical monitoring data in the past) is the comparative test result (primary conditions such as water quality, facility all do not change) of Guangdong PCB enterprise composite wastewater purifying treatment:
The water quality and the water yield (comprehensively mixing well the pond): pH 2.4,1100NTU (turbidity), COD=960mg/L, Q=4500m
3/ d.
Treatment process: tube settling, kerve (ditch) automatic mud removing, mean residence time 3.5h.
Flocculation agent: according to change of water quality, the commercially available polymerize aluminum chloride (Al of former usefulness
2O
3Content 9.31%, 64.80%, 900 yuan/ton of basicity) or solid ferric polysulfate (Fe
3+Content 28～30%, basicity 9～12%, 2800 yuan/ton); Now use the modified polyiron of embodiment 1,2,3,4,5 preparations instead.
Alkaline agent and polymer coagulant aids: lime, sloid alcali sulphide are industrial goods; Cationic PAM, molecular weight 1,200 ten thousand, CIBA produce.
The former employing bodied ferric sulfate of this enterprise and polymerize aluminum chloride are handled composite wastewater, are often warned by city Environmental Protection Agency and impose a fine because of COD and cupric ion exceed standard.The modified polyiron excellent property of the inventive method preparation, its purifying water effect obviously improves, and can replace the similar flocculation agent of producing with industrial raw material (bodied ferric sulfate and polymerize aluminum chloride) fully, makes the comprehensive wastewater stably reaching standard, makes a silk purse out of a sow's ear.
Table 6
Claims (8)
1.PCB the full method of resource of nitric acid type tin-lead soldering waste liquid, it is characterized in that with the ferrous sulfate being reagent and settling agent, react with PCB nitric acid type tin-lead soldering waste liquid, the isolating after filtration filter cake of reaction solution extracts the plumbous mud of solid phase tin through cleaning, filtrate and scavenging solution merge as mother liquor, and mother liquor is copper bearing acidic solution; Be that reductive agent and displacer fully extract copper sponge again with iron from mother liquor, carry in the copper process and add iron that be lower than 1mg/L up to mother liquor extraneous copper content, copper-extracting process finishes, copper sponge is regularly discharged and through the clear water rinsing; The last raffinate that comprises a large amount of iron and acid is regulated iron level with molysite or ferrous salt again after carrying copper, regulates acid content with acid, through oxidation, hydrolysis, polyreaction, and preparation water purification agent modified polyiron.
2. the full method of resource of PCB nitric acid type tin-lead soldering waste liquid according to claim 1, it is characterized in that concrete technology may further comprise the steps: separation, the extraction of (1) tin lead: with the ferrous sulfate is reagent and settling agent, add copperas solution under agitation condition in nitric acid type tin-lead soldering waste liquid, the ferrous sulfate molar weight in the copperas solution is pb
2+1.0～3.0 times of molar weights continued stirring reaction 0.5～2.0 hour, got reaction solution, reacting liquid filtering separate filter cake and filtrate, filter cake cleans with clear water, plumbous mud of solid phase tin and scavenging solution, filtrate and scavenging solution merge as mother liquor immigration Buffer Pool, and mother liquor is copper bearing acidic solution; (2) extraction of copper: mother liquor is that reductive agent, displacer fully extract copper sponge with iron by acid-resistant ceramic pump in contact reactor, carry in the copper process and add iron, extraneous copper content is lower than 1mg/L in mother liquor, copper-extracting process finishes, copper sponge compiles and discharge regularly at Buffer Pool, and through the clear water rinsing; Close the preceding valve of acid-resistant ceramic pump, open residual-gas valve, the last raffinate that comprises a large amount of iron and acid after carrying copper is pumped into polymerization reaction kettle; (3) preparation of modified polyiron: the raffinate of step (2) gained is regulated iron level with molysite or ferrous salt, regulate acid content with acid after, by the air or oxygen continuous aeration, ferrously prepare the water purification agent modified polyiron through oxidation, hydrolysis, polymerization.
3. the full method of resource of PCB nitric acid type tin-lead soldering waste liquid according to claim 1 is characterized in that the described ferrous sulfate of step (1) adopts sulfur acid ferrous waste material.
4. the full method of resource of PCB nitric acid type tin-lead soldering waste liquid according to claim 1 is characterized in that the described iron of step (2) is more than one of iron plate, iron mud, iron powder or iron plane flower.
5. the full method of resource of PCB nitric acid type tin-lead soldering waste liquid according to claim 1 is characterized in that the described molysite of step (3) is an iron trichloride, and ferrous salt is more than one of ferrous sulfate, iron protochloride.
6. the full method of resource of PCB nitric acid type tin-lead soldering waste liquid according to claim 1 is characterized in that the rinse water that obtain after described step (2) the copper sponge rinsing are used for the preparation of the described copperas solution of step (1).
7. the full method of resource of PCB nitric acid type tin-lead soldering waste liquid according to claim 1 is characterized in that the described acid of step (3) is mineral acid or organic acid; Mineral acid is more than one of sulfuric acid, hydrochloric acid, phosphoric acid; Organic acid is more than one of citric acid, thionamic acid.
8. the full method of resource of PCB nitric acid type tin-lead soldering waste liquid according to claim 1, it is characterized in that described PCB nitric acid type tin-lead soldering waste liquid is any nitric acid type tin-lead soldering waste liquid of producing PCB, or any mixing of multiple PCB nitric acid type tin-lead soldering waste liquid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100007609A CN102115890B (en) | 2011-01-04 | 2011-01-04 | Total recycling method of PCB (printed circuit board) nitric acid type tin-lead stripping waste liquid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100007609A CN102115890B (en) | 2011-01-04 | 2011-01-04 | Total recycling method of PCB (printed circuit board) nitric acid type tin-lead stripping waste liquid |
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| Publication Number | Publication Date |
|---|---|
| CN102115890A true CN102115890A (en) | 2011-07-06 |
| CN102115890B CN102115890B (en) | 2012-12-05 |
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| CN2011100007609A Expired - Fee Related CN102115890B (en) | 2011-01-04 | 2011-01-04 | Total recycling method of PCB (printed circuit board) nitric acid type tin-lead stripping waste liquid |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102912352A (en) * | 2012-11-08 | 2013-02-06 | 上海绿澄环保科技有限公司 | Method for recycling acidic copper-etching waste solution |
| CN103627903A (en) * | 2013-11-01 | 2014-03-12 | 遵义市金狮金属合金有限公司 | Recovery method for recycling lead in waste lead-acid storage batteries |
| CN104818385A (en) * | 2015-04-10 | 2015-08-05 | 吴江市松陵镇氧化铜厂 | Energy-saving, environmental-protection and zero-discharge technology of acidic waste etching solution resource recycling treatment |
| CN105217759A (en) * | 2015-10-23 | 2016-01-06 | 苏州书瑞环保科技有限公司 | A kind of waste water detin agent and preparation method thereof |
| CN105541056A (en) * | 2016-03-03 | 2016-05-04 | 杭州启澄科技有限公司 | Treatment method for removing tin in PCB industrial wastewater |
| CN105541055A (en) * | 2016-03-03 | 2016-05-04 | 杭州启澄科技有限公司 | Treatment system for removing tin in PCB industrial wastewater |
| CN107986571A (en) * | 2016-03-15 | 2018-05-04 | 杭州启澄科技有限公司 | A kind of processing method of the electroplating wastewater containing antimony |
| CN110228889A (en) * | 2019-07-11 | 2019-09-13 | 中山市中环环保废液回收有限公司 | A kind of processing method and stream treatment line of tin removal waste liquor |
| CN111320326A (en) * | 2020-03-12 | 2020-06-23 | 无锡中天固废处置有限公司 | Method for treating complex tin stripping waste liquid |
| CN115449634A (en) * | 2022-08-26 | 2022-12-09 | 湖北永绍科技股份有限公司 | Treatment method for recycling tin stripping waste liquid |
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| CN102912352A (en) * | 2012-11-08 | 2013-02-06 | 上海绿澄环保科技有限公司 | Method for recycling acidic copper-etching waste solution |
| CN103627903A (en) * | 2013-11-01 | 2014-03-12 | 遵义市金狮金属合金有限公司 | Recovery method for recycling lead in waste lead-acid storage batteries |
| CN103627903B (en) * | 2013-11-01 | 2015-08-19 | 遵义市金狮金属合金有限公司 | Recovery method plumbous in a kind of waste and old lead acid accumulator |
| CN104818385A (en) * | 2015-04-10 | 2015-08-05 | 吴江市松陵镇氧化铜厂 | Energy-saving, environmental-protection and zero-discharge technology of acidic waste etching solution resource recycling treatment |
| CN105217759A (en) * | 2015-10-23 | 2016-01-06 | 苏州书瑞环保科技有限公司 | A kind of waste water detin agent and preparation method thereof |
| CN105541056A (en) * | 2016-03-03 | 2016-05-04 | 杭州启澄科技有限公司 | Treatment method for removing tin in PCB industrial wastewater |
| CN105541055A (en) * | 2016-03-03 | 2016-05-04 | 杭州启澄科技有限公司 | Treatment system for removing tin in PCB industrial wastewater |
| CN107986571A (en) * | 2016-03-15 | 2018-05-04 | 杭州启澄科技有限公司 | A kind of processing method of the electroplating wastewater containing antimony |
| CN110228889A (en) * | 2019-07-11 | 2019-09-13 | 中山市中环环保废液回收有限公司 | A kind of processing method and stream treatment line of tin removal waste liquor |
| CN111320326A (en) * | 2020-03-12 | 2020-06-23 | 无锡中天固废处置有限公司 | Method for treating complex tin stripping waste liquid |
| CN115449634A (en) * | 2022-08-26 | 2022-12-09 | 湖北永绍科技股份有限公司 | Treatment method for recycling tin stripping waste liquid |
| CN115449634B (en) * | 2022-08-26 | 2024-02-09 | 湖北永绍科技股份有限公司 | Treatment method for recycling tin stripping waste liquid |
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