CN101984097A - Method for comprehensive recovery of heavy metal from spent solder stripper - Google Patents
Method for comprehensive recovery of heavy metal from spent solder stripper Download PDFInfo
- Publication number
- CN101984097A CN101984097A CN2010105575191A CN201010557519A CN101984097A CN 101984097 A CN101984097 A CN 101984097A CN 2010105575191 A CN2010105575191 A CN 2010105575191A CN 201010557519 A CN201010557519 A CN 201010557519A CN 101984097 A CN101984097 A CN 101984097A
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- filtrate
- tin
- filter residue
- heavy metal
- sodium hydroxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a method for comprehensive recovery of a heavy metal from a spent solder stripper, which mainly comprises steps as follows: a first step: adding pure ammonia to the spent solder stripper and adjusting pH to 9-10 to cause tin and iron to generate precipitation; a second step: obtaining a filter residue and a filtrate by filtration, wherein the main component of the filtrate is a copper ammonia solution; a third step: firstly breaking the filter residue obtained in the second step into small particles, then adding a sodium hydroxide solution to the filter residue under stirring conditions, finally reacting the tin with the sodium hydroxide completely to generate sodium stannate; a fourth step: obtaining the filtrate by filtering; a fifth step: adding sodium sulfide to the filtrate under stirring conditions, then making the solution rest and precipitating the solution; a sixth step: obtaining the filtrate by filtration; a seventh step: dewatering the filtrate obtained in the sixth step to obtain the sodium stannate. The spent solder stripper with high heavy metal content, great danger, complex component and big disposal difficulty is taken as an object. The spent solder stripper can be directly employed after the tin in the spent solder stripper is recovered. The method has good economic benefits and environmental benefits.
Description
Technical field
The present invention relates to the comprehensive method that reclaims of heavy metal in a kind of useless tin stripping liquid, belong to technical field of waste water processing.
Background technology
Printed-wiring board (PWB) (PCB) industry is the basis of hyundai electronics and information industry, along with the development of high-tech industry, the demand of wiring board is increased year by year.The making processes of PCB has more than 20 procedures, wherein can produce a large amount of waste liquids that comprises useless tin stripping liquid.By every production 1000m
2Wiring board consumes 0.75m at least
3Tin stripping liquid calculates, the whole world year consumption 5 * 10
5m
3Tin stripping liquid, China's year consumes tin stripping liquid 6 * 10
4m
3, and increase progressively with fast speeds.Useless tin stripping liquid is by the red-tape operati time, is only dissolving the waste liquid that tin produced that covers on the copper layer under the situation of not damaging the copper base material by tin stripping liquid.At present, the tin stripping liquid of Xiao Shouing can be divided into fluorochemical type, nitric acid type and nitric acid-alkylsulphonic acid type 3 classes by its composition and mode of action difference on the market.Fluorochemical type tin stripping liquid has become superseded formulation owing to fluorochemical high volatility, pollution extremely heavily wait reason.The technical feature of nitric acid type and nitric acid-alkylsulphonic acid type tin stripping liquid is close, is the leading formulation that current PCB produces.In the useless tin stripping liquid that produces, heavy metal concentration is higher, and wherein tin content is every liter of 40～100g, and the content of copper is every liter of 5～15g, and a spot of iron etc.If with its random discharging, not only contaminate environment but also cause the wasting of resources.
The annual growth of global in recent years tin Chemicals is that total tin amount of 18%, 2009 year useless tin stripping liquid is about 4500 tons, can produce the tin Chemicals more than 6000 tons.Since useless tin stripping liquid heavy metal content height, the pollution index height, and free acidity is big, and employing ordinary method intractability is big, cost is high.How effectively handling useless tin stripping liquid, regeneration wherein valuable resource becomes the difficult problem that PCB faces.Traditional treatment process mainly is to add alkali to carry out neutralization precipitation, filters then, and filter cake tin mud send smeltery's pyrometallurgical smelting, and filtrate then adds discharges after sulfide reclaims copper.This not only produces a large amount of waste residues, and the utilization of resources is insufficient, and water quality is difficult to reach emission standard, and processing costs is higher.In recent years, distillation absorption method, acidic precipitation agent facture, preparation stannic acid product, electrolytic process and ion exchange method etc. have appearred again in succession, a large amount of other waste liquids of these technological methods or generation and mud, caused secondary pollution, and complex process, condition are controlled strictness, processing cost is high, or only consider to reclaim metallic tin in the tin stripping liquid, can not realize the comprehensive reutilization of heavy metal resources.Therefore, the development research treatment effect is good, and economically viable useless tin stripping liquid comprehensive cyclic utilization technology and technology are the main flow directions that useless tin stripping liquid is administered.
Summary of the invention
The invention provides the comprehensive method that reclaims of heavy metal in a kind of useless tin stripping liquid.
For achieving the above object, the technical solution used in the present invention is: the comprehensive method that reclaims of heavy metal in a kind of useless tin stripping liquid, mainly form by following steps:
The first step: in useless tin stripping liquid, add pure ammoniacal liquor and regulate pH to 9～10, make tin and iron generate precipitation;
Second step: suction filtration obtains filter residue and filtrate, and this filtrate main component is a copper ammon solution;
The 3rd step: at first in second filter residue that obtain of step, add sodium hydroxide solution, under agitation condition, be broken into small-particle earlier then, under heating condition, make tin and sodium hydroxide fully react the generation sodium stannate again; The solute in the described sodium hydroxide solution and the mol ratio of the tin in the filter residue are 8～9:1, and the weight ratio of solvent in the described sodium hydroxide solution and filter residue dry weight is 4～5:1;
The 4th step: filter and obtain filtrate;
The 5th step: under agitation condition, in filtrate, add sodium sulphite, staticly settle then;
The 6th step: suction filtration obtains filtrate;
The 7th step: the filtrate dehydration with the 6th step obtained obtains sodium stannate.
Related content in the technique scheme is explained as follows:
1, in the such scheme, the alkali that adds of the filtrate that obtains in described second step is reconciled the pH value more than 11, at first utilizes blow-off method to remove ammonia, adds sodium sulphite then and generates copper sulfide precipitation, promptly gets copper sludge after the filtration.
2, in the such scheme, described blow-off method is to make the ammonium ion big portion under the condition of high pH value in the solution be transformed into ammonia:
NH
4 +＋OH
-=NH
3↑＋H
2O
Be under 7,9,11 the condition in 25 ℃ of temperature and pH value, NH in the solution
4 +With NH
3Partition ratio be respectively 180,1.8 and 0.018, so blow-off method is denitrogenated optimum pH value about 11.Sewage is transferred to high like this pH value sends in the stripping tower later, spray from top to bottom and flow, ammonia is blown out with making progress the flowing air counter current contact.The efficient of denitrogenating of blow-off method mainly is subjected to Temperature Influence.When being 20 ℃ and 10 ℃ at temperature, nitrogen-removing rate is respectively 95% and 75%.
Because the technique scheme utilization, the present invention compared with prior art has following advantage and effect:
The heavy metal content height that the present invention produces with wiring board enterprise, harm are big, complicated component and the high useless tin stripping liquid of intractability are object, with the theory of cleaner production and resource recovery, mainly with the give up comprehensive reutilization processing of heavy metal in the tin stripping liquid of chemical neutralisation.Tin, copper and iron in the waste liquid are effectively separated, and realize recycling, this technology has good economic benefit and environmental benefit.
Description of drawings
Accompanying drawing 1 is schema of the present invention.
Embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one: the comprehensive method that reclaims of heavy metal in a kind of useless tin stripping liquid
Shown in accompanying drawing 1, in useless tin stripping liquid, add pure ammoniacal liquor and carry out precipitin reaction, regulate between the pH to 9.5, make tin and iron finish precipitation earlier.After reaction is finished, carry out suction filtration and separate, filtrate is mainly copper ammon solution, and tin and iron rule generate insolubles and stay in the precipitation, and this step reaction is main to be separated the copper and tin in the waste liquid, iron earlier, and the separation rate of copper can reach more than 98%.
Main tin oxide hydrate and the ionic state tin (Sn of tin in the useless tin stripping liquid to suspend
2+, Sn
4+) the form existence.Copper is mainly with Cu
2+, Cu
+Ionic condition exists, and iron is mainly with Fe
3+Form exist.Because tin is amphoteric, tin in pH=1～2 o'clock with insoluble stannic hydroxide (Sn (OH)
2, Sn (OH)
4) or tin dioxide hydrate (be mainly H
2SnO
3) begin precipitation, be deposited in pH〉12 o'clock can exist with ionic condition again.Ferric iron can precipitate in pH=3～4, and copper is at NH
4 +Exist down, best precipitation pH=5.5, and at excessive N H
4 +Down, precipitation can be reacted the generation cupric ammine complex again.Principal reaction is as follows:
The copper ammon solution that suction filtration goes out at first utilizes blow-off method to remove ammonia nitrogen by after adding alkali and regulating pH, adds an amount of sodium sulphite then and carries out flocculation sediment, and press filtration generates copper sludge again, and the unit that copper sludge can be delivered to qualification carries out recycling disposal, but filtrate qualified discharge then.Its reaction is as follows:
It is under alkaline condition that blow-off method is removed ammonia nitrogen, utilizes the phase concentrations of ammonia nitrogen and the vapor-liquid equilibrium relationship between the liquid concentration to carry out isolating a kind of method.Ammonia nitrogen in the water is mostly with ammonium ion (NH
4 +) and free ammonia (NH
3) keep the equilibrated state and exist, its balanced relationship is:
This relational expression is influenced by the pH value, and when the pH value increases to more than 11, balance moves right, the large percentage of free ammonia, and under the aeration state, the ammonia that is unbound state is easy to overflow.As long as this adopt, and the method for common air stripping just can be carried out.
Insolubles, moisture and other the impurity etc. that comprise tin and iron in the precipitation behind the suction filtration.Add proper amount of sodium hydroxide sheet and water in the precipitation behind an amount of suction filtration,, under alkaline condition, can dissolve the generation stannate because stannic hydroxide is an amphoteric hydroxide.In the sodium hydroxide of getting and the precipitation mol ratio of tin be 8: 1, water is 4: 1 with the weight ratio of the precipitation of getting (with oven-dried weight calculating).At first must stir makes precipitation be broken into small-particle fully, to prevent in the heated and boiled process because the inhomogeneous generation bumping that is heated, then behind the about 1h of heated and boiled (keeping little boiling), the about 1h of hot dipping in 100 ℃ of left and right sides water-baths again, add less water after the cooling and continue to stir 30min, and then carry out filtering separation, and the water flushing repeatedly, tin is isolated fully, and the separation rate of tin reaches more than 95%.Stannic hydroxide in the precipitation generates sodium stannate in reaction process, ironic hydroxide does not react under alkaline condition, stays in the filter residue.Its reaction is as follows:
Sodium stannate solution adds sodium sulphite, after fully stirring, allows it staticly settle, to remove beavy metal impurities such as copper possible residual in the solution, iron.To obtain three hydration sodium stannate crystal through the solution of impurity and purification behind evaporation concentration, centrifugal drying, purity can reach product requirement.
The filter residue that contains ironic hydroxide, because alkalescence is higher, and the content of iron is lower again, recovery value is little.Therefore, the unit that this part filter residue is delivered to qualification carries out harmlessness disposing.
1, the method for heavy metal comprehensive reutilization in a kind of useless tin stripping liquid is characterized in that: mainly be made up of following steps:
The first step: in useless tin stripping liquid, add pure ammoniacal liquor and regulate between the pH to 10, make tin and iron generate precipitation;
Second step: suction filtration obtains filter residue and filtrate, and this filtrate main component is a copper ammon solution;
The 3rd step: at first the filter residue that second step was obtained is broken into small-particle fully, adds sodium hydroxide solution then under agitation condition in filter residue, makes tin and sodium hydroxide fully react the generation sodium stannate again under heating condition; The solute in the described sodium hydroxide solution and the mol ratio of the tin in the filter residue are 9:1, and the weight ratio of solvent in the described sodium hydroxide solution and filter residue dry weight is 5:1;
The 4th step: filter and obtain filtrate;
The 5th step: under agitation condition, in filtrate, add sodium sulphite, staticly settle then;
The 6th step: suction filtration obtains filtrate;
The 7th step: the filtrate dehydration with the 6th step obtained obtains sodium stannate.
The alkali that adds of the filtrate that obtains in described second step is reconciled pH value to 11, at first utilizes blow-off method to remove nitrogen, adds sodium sulphite then and generates copper sulfide precipitation, promptly gets copper sludge after the filtration.
The foregoing description only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the personage who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalences that spirit is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (2)
1. the comprehensive method that reclaims of heavy metal in the useless tin stripping liquid is characterized in that: mainly be made up of following steps:
The first step: in useless tin stripping liquid, add pure ammoniacal liquor and regulate pH to 9～10, make tin and iron generate precipitation;
Second step: suction filtration obtains filter residue and filtrate, and this filtrate main component is a copper ammon solution;
The 3rd step: at first in second filter residue that obtain of step, add sodium hydroxide solution, under agitation condition, be broken into small-particle earlier then, under heating condition, make tin and sodium hydroxide fully react the generation sodium stannate again; The solute in the described sodium hydroxide solution and the mol ratio of the tin in the filter residue are 8～9:1, and the weight ratio of solvent in the described sodium hydroxide solution and filter residue dry weight is 4～5:1;
The 4th step: filter and obtain filtrate;
The 5th step: under agitation condition, in filtrate, add sodium sulphite, staticly settle then;
The 6th step: suction filtration obtains filtrate;
The 7th step: the filtrate dehydration with the 6th step obtained obtains sodium stannate.
2. the method for heavy metal comprehensive reutilization in the useless tin stripping liquid according to claim 1, it is characterized in that: the alkali that adds of the filtrate that obtains in described second step is reconciled the pH value more than 11, at first utilize blow-off method to remove ammonia, add sodium sulphite then and generate copper sulfide precipitation, promptly get copper sludge after the filtration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105575191A CN101984097A (en) | 2010-11-24 | 2010-11-24 | Method for comprehensive recovery of heavy metal from spent solder stripper |
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|---|---|---|---|
| CN2010105575191A CN101984097A (en) | 2010-11-24 | 2010-11-24 | Method for comprehensive recovery of heavy metal from spent solder stripper |
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|---|---|
| CN101984097A true CN101984097A (en) | 2011-03-09 |
Family
ID=43641267
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|---|---|---|---|
| CN2010105575191A Pending CN101984097A (en) | 2010-11-24 | 2010-11-24 | Method for comprehensive recovery of heavy metal from spent solder stripper |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531027A (en) * | 2012-02-07 | 2012-07-04 | 樊余杰 | Method for preparing heavy basic copper carbonate |
| CN102775197A (en) * | 2012-08-13 | 2012-11-14 | 深圳市危险废物处理站有限公司 | Method for preparing fertilizer-grade ammonium nitrate concentrated solution by use of mother liquid after immersion tin of tin-stripping waste liquid of circuit board |
| CN103145267A (en) * | 2013-03-20 | 2013-06-12 | 李杨 | Method for recovering copper sulfide and ferric hydroxide in auricupride acid wastewater through sulfidization method |
| CN103172109A (en) * | 2013-03-13 | 2013-06-26 | 东江环保股份有限公司 | Method for preparing sodium stannate by utilizing tin-removed wastewater |
| CN103172108A (en) * | 2011-12-20 | 2013-06-26 | 财团法人工业技术研究院 | Method and system for separating metal sulfide from waste liquid and recovering ammonia water |
| CN103388074A (en) * | 2012-05-09 | 2013-11-13 | 荆门市格林美新材料有限公司 | Method for treating spent tin stripping solution of waste circuit board |
| CN103911513A (en) * | 2013-01-06 | 2014-07-09 | 中石化上海工程有限公司 | Solder stripping waste liquid treatment method |
| CN104152701A (en) * | 2014-08-18 | 2014-11-19 | 汨罗市绿岩金属有限公司 | Method for recycling tin from coarse tin refining slag |
| CN105460972A (en) * | 2015-12-28 | 2016-04-06 | 广州科城环保科技有限公司 | Recycling method of circuit board solder stripping waste liquid |
| 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 |
| CN109534856A (en) * | 2018-12-21 | 2019-03-29 | 深圳市星河环境技术有限公司 | A method of the total nitrogen zero-emission suitable for tin removal waste liquor |
| CN110182840A (en) * | 2019-06-24 | 2019-08-30 | 深圳市海文环保技术有限公司 | Move back tin waste treatment processes |
| CN110284000A (en) * | 2019-07-23 | 2019-09-27 | 盛隆资源再生（无锡）有限公司 | A method of tin, iron, nickel, zinc in the stanniferous waste water of reuse respectively |
| CN112663092A (en) * | 2020-12-10 | 2021-04-16 | 广东臻鼎环境科技有限公司 | Method for treating methanesulfonic acid type tin stripping waste liquid |
| CN113073204A (en) * | 2021-03-31 | 2021-07-06 | 江西省江铜百泰环保科技有限公司 | Method for recovering copper from low-concentration acidic wastewater |
| 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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Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172108B (en) * | 2011-12-20 | 2015-11-04 | 财团法人工业技术研究院 | Method and system for separating metal sulfide from waste liquid and recovering ammonia water |
| CN103172108A (en) * | 2011-12-20 | 2013-06-26 | 财团法人工业技术研究院 | Method and system for separating metal sulfide from waste liquid and recovering ammonia water |
| CN102531027A (en) * | 2012-02-07 | 2012-07-04 | 樊余杰 | Method for preparing heavy basic copper carbonate |
| CN103388074A (en) * | 2012-05-09 | 2013-11-13 | 荆门市格林美新材料有限公司 | Method for treating spent tin stripping solution of waste circuit board |
| CN103388074B (en) * | 2012-05-09 | 2015-01-21 | 荆门市格林美新材料有限公司 | Method for treating spent tin stripping solution of waste circuit board |
| CN102775197B (en) * | 2012-08-13 | 2014-06-11 | 深圳市危险废物处理站有限公司 | Method for preparing fertilizer-grade ammonium nitrate concentrated solution by use of mother liquid after immersion tin of tin-stripping waste liquid of circuit board |
| CN102775197A (en) * | 2012-08-13 | 2012-11-14 | 深圳市危险废物处理站有限公司 | Method for preparing fertilizer-grade ammonium nitrate concentrated solution by use of mother liquid after immersion tin of tin-stripping waste liquid of circuit board |
| CN103911513A (en) * | 2013-01-06 | 2014-07-09 | 中石化上海工程有限公司 | Solder stripping waste liquid treatment method |
| CN103911513B (en) * | 2013-01-06 | 2016-03-23 | 中石化上海工程有限公司 | Move back the treatment process of tin waste liquid |
| CN103172109A (en) * | 2013-03-13 | 2013-06-26 | 东江环保股份有限公司 | Method for preparing sodium stannate by utilizing tin-removed wastewater |
| CN103145267A (en) * | 2013-03-20 | 2013-06-12 | 李杨 | Method for recovering copper sulfide and ferric hydroxide in auricupride acid wastewater through sulfidization method |
| CN104152701B (en) * | 2014-08-18 | 2017-06-13 | 汨罗市绿岩金属有限公司 | The method that tin is reclaimed from tin refinement slag |
| CN104152701A (en) * | 2014-08-18 | 2014-11-19 | 汨罗市绿岩金属有限公司 | Method for recycling tin from coarse tin refining slag |
| CN105460972A (en) * | 2015-12-28 | 2016-04-06 | 广州科城环保科技有限公司 | Recycling method of circuit board solder stripping waste liquid |
| 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 |
| CN109534856A (en) * | 2018-12-21 | 2019-03-29 | 深圳市星河环境技术有限公司 | A method of the total nitrogen zero-emission suitable for tin removal waste liquor |
| CN109534856B (en) * | 2018-12-21 | 2021-03-05 | 深圳市星河环境技术有限公司 | Method suitable for zero emission of total nitrogen in tin stripping waste liquid |
| CN110182840A (en) * | 2019-06-24 | 2019-08-30 | 深圳市海文环保技术有限公司 | Move back tin waste treatment processes |
| CN110284000A (en) * | 2019-07-23 | 2019-09-27 | 盛隆资源再生（无锡）有限公司 | A method of tin, iron, nickel, zinc in the stanniferous waste water of reuse respectively |
| CN112663092A (en) * | 2020-12-10 | 2021-04-16 | 广东臻鼎环境科技有限公司 | Method for treating methanesulfonic acid type tin stripping waste liquid |
| CN113073204A (en) * | 2021-03-31 | 2021-07-06 | 江西省江铜百泰环保科技有限公司 | Method for recovering copper from low-concentration acidic wastewater |
| CN113073204B (en) * | 2021-03-31 | 2023-02-10 | 江西省江铜百泰环保科技有限公司 | Method for recovering copper from low-concentration acidic wastewater |
| 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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Application publication date: 20110309 |