CN101948133B - Method for co-producing sodium stannate and stannic oxide by solder removing liquid - Google Patents
Method for co-producing sodium stannate and stannic oxide by solder removing liquid Download PDFInfo
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- CN101948133B CN101948133B CN201010521861.6A CN201010521861A CN101948133B CN 101948133 B CN101948133 B CN 101948133B CN 201010521861 A CN201010521861 A CN 201010521861A CN 101948133 B CN101948133 B CN 101948133B
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- acid
- sodium stannate
- tindioxide
- filter cake
- stripping liquid
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Abstract
The invention discloses a method for co-producing sodium stannate and stannic oxide by solder removing liquid, comprising the following steps: separating tin in the solder removing liquid, recovering copper, transforming copper into sodium stannate, preparing sodium stannate and preparing stannic oxide. The method of the invention features in low processing cost, simple technical process and device structure, and high product purity and can prepare sodium stannate and stannic oxide.
Description
Technical field
The present invention relates to a kind of method of utilizing tin stripping liquid coproduction sodium stannate and tindioxide, particularly a kind of method of utilizing non-fluoridate type printed board tin stripping liquid coproduction sodium stannate and tindioxide.
Background technology
PCB(printed circuit board) enterprise is one and produces liquid/solid trade waste quantity larger industry, the class I liquid I waste (referred to as waste liquid) producing, be to produce when the scrapping or change cylinder of liquid in the work nest of each operation, be characterized in that Pollutant levels are high, type is many, complicated component.In Tui Xishi PCB enterprise, produce the operation of wastewater flow rate maximum, the tin stripping liquid heavy metal content that produces high (tin copper content can reach 100g/L more than), pollution index is high, and free acid acidity is large, complicated component, generally contain the Multiple components such as acids (nitric acid, sulfuric acid, hydrochloric acid and other organic acid), promotor, tensio-active agent, oxynitride inhibitor, heavy metal complexing agent, copper inhibitor, be difficult to process by ordinary method.How effectively to process a difficult problem that waste tin stripper Cheng Liao PCB enterprise faces.
Application number is the recovery method that 200910301263.5 Chinese patent application discloses a kind of tin in tin-stripping waste liquid, adopt sodium carbonate solution neutralization to move back tin waste liquid, add again alkali and be converted into sodium stannate at 102 DEG C of-115 DEG C of temperature, after filtration, in filtrate, pass into carbonic acid gas, make sodium stannate be converted into metastannic acid, after filtration, produce tindioxide through washing, calcining.The method does not adopt Distillation recovery nitric acid, need a large amount of use sodium carbonate go in and nitric acid, increased production cost, simultaneously by the SODIUMNITRATE of new increase (containing some other soluble impurity) waste water, this part waste water needs further to process, and has further increased production cost.The method passes into carbonic acid gas sodium stannate is transformed back to metastannic acid, then is sintered into tindioxide, and the finished product are only tindioxide, has lost and has separated the chance that obtains sodium stannate.
Application number is that 200810065305.5 Chinese patent application discloses a kind of method of utilizing circuit board tin-stripping wastewater to prepare sodium stannate, the method that tin-stripping wastewater neutralization precipitation gained tin mud is adopted to high-temperature roasting, is converted into resolvability sodium stannate by insoluble β-stannic acid, sub-stannic acid.The method need to be used sodium carbonate to go neutralization to move back tin waste liquid equally, has increased production cost; Adopt the method for high-temperature fusion to transform β-stannic acid, need to adopt high-temperature fusion equipment, this device structure is more complicated, and equipment material requirement is special, operation is more complicated, risk level is high, and cost is higher; Adopt counter-current lixiviate sodium stannate, then through press filtration, concentrated, filtration, wash to obtain product, in the sodium stannate that concentration process obtains, contain relatively large sodium hydroxide, be through the sodium hydroxide solution washing of 10% left and right concentration, could obtain qualified product, complex technical process.
Summary of the invention
The object of the invention is to overcome that tin stripping liquid processing cost in prior art is high, the deficiency of technological process and device structure complexity, a kind of method of utilizing tin stripping liquid coproduction sodium stannate and tindioxide is provided.The method processing cost is low, technological process and device structure is simple, product purity is high, can prepare sodium stannate and tindioxide simultaneously.
For achieving the above object, the technical solution adopted for the present invention to solve the technical problems is:
A method of utilizing tin stripping liquid coproduction sodium stannate and tindioxide, comprises the following steps:
A, by tin stripping liquid at temperature 50-70 DEG C, pressure 0.1 × 1.03 × 10
5-0.4 × 1.03 × 10
5under Pa, carry out underpressure distillation and reclaim nitric acid, more than steaming, in liquid, add ionogen, electrolytical dosage is 20-60g/L tin stripping liquid, after sedimentation completes, and press filtration, filter cake press dry after washing;
B, the filtrate obtaining in steps A and washings are added to alkali neutralization, control pH at 6-8, then add sodium sulfide solution to precipitating not regeneration, filter, filter cake is cupric sulfide, and filtrate is sent to Sewage treatment systems;
C, by steps A to filter cake send into reactor, the solid alkali that to add with filter cake mol ratio be 1:2-1:3.5, under agitation be warming up to 98-105 DEG C, insulation 1-2h, makes β-metastannic acid and α-metastannic acid be converted into sodium stannate, then the water that to add with sodium stannate mass ratio be 1:3-1:5, stir, constant temperature 2-4h at 96-100 DEG C of temperature, filters, and filter cake is sent to iron recovery system;
D, by step C to filtrate heating be concentrated into crystal and occurred after, stop heating, natural cooling crystallization, filters, dry cake obtains sodium stannate;
E, by step D filter after mother liquid obtained acid neutralization, through centrifugal, press filtration, washing obtain metastannic acid, metastannic acid, at 200-400 DEG C of roasting temperature, is obtained to tindioxide.
As optimal way, in described steps A, ionogen is selected from Na
2sO
4, Na
3pO
4, K
2sO
4or K
3pO
4in one or more.
As optimal way, in described step C, alkali is selected from NaOH, KOH, Na
2cO
3or NH
3h
2one or more in O.
As optimal way, in described step e, acid is selected from one or more in hydrochloric acid, sulfuric acid, carbonic acid or phosphoric acid.
The tin stripping liquid of the present invention after nitric acid is reclaimed in underpressure distillation, after adding ionogen, there is sedimentation, copper retains in solution with ionic state, and the small part copper adsorbing in filter residue can reclaim through washing, and a small amount of remaining copper is converted into insoluble copper hydroxide and separates in the step of sodium stannate conversion.The filter residue settling down is beyond after alkali transforms, deleading, aluminium exist with acid salt form, and other impurity conversion is insoluble oxyhydroxide, is adding flooding Na
2snO
4after filtration procedure insoluble oxyhydroxide can be removed, utilize the gluey feature of oxyhydroxide, effectively Adsorption part aluminium, silicate impurity simultaneously.
Na of the present invention
2snO
4with SnO
2the analysis indexes of product is in table 1,2.
Table 1 Na
2snO
4the analysis indexes of product
Table 2 SnO
2the analysis indexes of product
The present invention first adopts underpressure distillation to reclaim nitric acid, then carries out potential of hydrogen adjusting, has both reclaimed nitric acid, realizes recycling, has reduced production cost, avoids again producing a large amount of SODIUMNITRATE waste water, has reduced discharge of wastewater and environmental pollution.
The present invention adopts solid NaOH to react with metastannic acid, controls temperature at 95-105 DEG C, is converted into solubility stannate with higher transformation efficiency, has avoided high-temperature operation, has reduced the usage quantity of alkali, and technology and equipment is simple in structure, has reduced production cost.The present invention adopts flooding sodium stannate, has avoided adopting that the lixiviate of alkali strong solution brings at finished product Na
2snO
4in the problem of remaining a large amount of NaOH, can disposablely reach Na
2snO
4commercially available specification of quality.
The present invention will produce Na
2snO
4after mother liquor with after acid neutralization, through centrifugal, calcining, grind, washing, dry, produce SnO
2, solve the problem that mother liquor stockpiles, obtain again SnO simultaneously
2fine chemistry product, has fully realized the resource utilization of useful component, has avoided the pollution to environment.
Beneficial effect of the present invention is: processing cost of the present invention is low, technological process and device structure is simple, product purity is high, can prepare sodium stannate and tindioxide simultaneously.
Embodiment
Disclosed all features in this specification sheets, or step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way.
Get five kinds of different tin stripping liquids, its moiety is in table 3.
Contents of Main Components in table 3 water sample
Embodiment 1: a kind of method of utilizing tin stripping liquid coproduction sodium stannate and tindioxide, comprises the following steps: A, by tin stripping liquid at temperature 70 C, pressure 0.1 × 1.03 × 10
5under carry out underpressure distillation and reclaim nitric acid, add Na steaming in remaining liquid
2sO
4, electrolytical dosage is 30g/L tin stripping liquid, after sedimentation completes, and press filtration, filter cake press dry after washing;
B, the filtrate obtaining in steps A and washings are added to alkali neutralization, control pH at 6-8, then add sodium sulfide solution to precipitating not regeneration, filter, filter cake is cupric sulfide, and filtrate is sent to Sewage treatment systems;
C, by steps A to filter cake send into reactor, the solid NaOH that to add with filter cake mol ratio be 1:2, under agitation be warming up to 98 DEG C, insulation 2h, makes β-metastannic acid and α-metastannic acid be converted into sodium stannate, then the water that to add with sodium stannate mass ratio be 1:3, stir, constant temperature 4h at 96 DEG C of temperature, filters, and filter cake is sent to iron recovery system;
D, by step C to filtrate heating be concentrated into crystal and occurred after, stop heating, natural cooling crystallization, filters, dry cake obtains sodium stannate;
E, by step D filter after mother liquid obtained acid neutralization, through centrifugal, press filtration, washing obtain metastannic acid, metastannic acid, at 300 DEG C of roasting temperatures, is obtained to tindioxide.
Embodiment 2: a kind of method of utilizing tin stripping liquid coproduction sodium stannate and tindioxide, comprises the following steps:
A, by tin stripping liquid at temperature 50 C, pressure 0.4 × 1.03 × 10
5under Pa, carry out underpressure distillation and reclaim nitric acid, more than steaming, in liquid, add Na
3pO
4, Na
3pO
4dosage be 60g/L tin stripping liquid, after sedimentation completes, press filtration, filter cake through washing after press dry;
B, the filtrate obtaining in steps A and washings are added to alkali neutralization, control pH at 6-8, then add sodium sulfide solution to precipitating not regeneration, filter, filter cake is cupric sulfide, and filtrate is sent to Sewage treatment systems;
C, by steps A to filter cake send into reactor, the solid KOH that to add with filter cake mol ratio be 1:3.5, under agitation be warming up to 105 DEG C, insulation 1h, makes β-metastannic acid and α-metastannic acid be converted into sodium stannate, then the water that to add with sodium stannate mass ratio be 1:5, stir, constant temperature 2h at 100 DEG C of temperature, filters, and filter cake is sent to iron recovery system;
D, by step C to filtrate heating be concentrated into crystal and occurred after, stop heating, natural cooling crystallization, filters, dry cake obtains sodium stannate;
E, by step D filter after mother liquid obtained acid neutralization, through centrifugal, press filtration, washing obtain metastannic acid, metastannic acid, at 200 DEG C of roasting temperatures, is obtained to tindioxide.
Embodiment 3: a kind of method of utilizing tin stripping liquid coproduction sodium stannate and tindioxide, comprises the following steps:
A, by tin stripping liquid at temperature 60 C, pressure 0.3 × 1.03 × 10
5under Pa, carry out underpressure distillation and reclaim nitric acid, more than steaming, in liquid, add K
2sO
4, K
2sO
4dosage be 40g/L tin stripping liquid, after sedimentation completes, press filtration, filter cake through washing after press dry;
B, the filtrate obtaining in steps A and washings are added to alkali neutralization, control pH at 6-8, then add sodium sulfide solution to precipitating not regeneration, filter, filter cake is cupric sulfide, and filtrate is sent to Sewage treatment systems;
C, by steps A to filter cake send into reactor, the solid NH that to add with filter cake mol ratio be 1:3
3h
2o, is under agitation warming up to 100 DEG C, and insulation 1.5h, makes β-metastannic acid and α-metastannic acid be converted into sodium stannate, then the water that to add with sodium stannate mass ratio be 1:4, stir, and constant temperature 3h at 98 DEG C of temperature, filtration, filter cake is sent to iron recovery system;
D, by step C to filtrate heating be concentrated into crystal and occurred after, stop heating, natural cooling crystallization, filters, dry cake obtains sodium stannate;
E, by step D filter after mother liquid obtained acid neutralization, through centrifugal, press filtration, washing obtain metastannic acid, metastannic acid, at 400 DEG C of roasting temperatures, is obtained to tindioxide.
Embodiment 4: a kind of method of utilizing tin stripping liquid coproduction sodium stannate and tindioxide, comprises the following steps:
A, by tin stripping liquid at 65 DEG C of temperature, pressure 0.3 × 1.03 × 10
5under Pa, carry out underpressure distillation and reclaim nitric acid, more than steaming, in liquid, add K
3pO
4, K
3pO
4dosage be 50g/L tin stripping liquid, after sedimentation completes, press filtration, filter cake through washing after press dry;
B, the filtrate obtaining in steps A and washings are added to alkali neutralization, control pH at 6-8, then add sodium sulfide solution to precipitating not regeneration, filter, filter cake is cupric sulfide, and filtrate is sent to Sewage treatment systems;
C, by steps A to filter cake send into reactor, the solid NaOH that to add with filter cake mol ratio be 1:3, under agitation be warming up to 102 DEG C, insulation 2h, makes β-metastannic acid and α-metastannic acid be converted into sodium stannate, then the water that to add with sodium stannate mass ratio be 1:4, stir, constant temperature 3h at 100 DEG C of temperature, filters, and filter cake is sent to iron recovery system;
D, by step C to filtrate heating be concentrated into crystal and occurred after, stop heating, natural cooling crystallization, filters, dry cake obtains sodium stannate;
E, by step D filter after mother liquid obtained acid neutralization, through centrifugal, press filtration, washing obtain metastannic acid, metastannic acid, at 350 DEG C of roasting temperatures, is obtained to tindioxide.
Embodiment 5: step is with embodiment 4.
In embodiment 1-5, add the rate of descent of tin after ionogen in table 4.
Table 4 adds the rate of descent of tin after ionogen
In embodiment 1-5, the rate of descent of tin is all higher than 99.5%, and the separation rate of tin is high, has fully reclaimed valuable tin element in tin stripping liquid, has significant economic benefit and social benefit.
The present invention is not limited to aforesaid embodiment.The present invention expands to any new feature or any new combination disclosing in this manual, and the arbitrary new method disclosing or step or any new combination of process.
Claims (4)
1. utilize a method for tin stripping liquid coproduction sodium stannate and tindioxide, it is characterized in that comprising the following steps:
A, by tin stripping liquid at temperature 50-70 DEG C, pressure 0.1 × 1.03 × 10
5-0.4 × 1.03 × 10
5under Pa, carry out underpressure distillation and reclaim nitric acid, more than steaming, in liquid, add ionogen, electrolytical dosage is 20-60g/L tin stripping liquid, after sedimentation completes, and press filtration, filter cake press dry after washing;
B, the filtrate obtaining in steps A and washings are added to alkali neutralization, control pH at 6-8, then add sodium sulfide solution to precipitating not regeneration, filter, filter cake is cupric sulfide, and filtrate is sent to Sewage treatment systems;
C, the filter cake obtaining in steps A is sent into reactor, the solid alkali that to add with filter cake mol ratio be 1:2-1:3.5, under agitation be warming up to 98-105 DEG C, insulation 1-2h, makes β-metastannic acid and α-metastannic acid be converted into sodium stannate, then the water that to add with sodium stannate mass ratio be 1:3-1:5, stir, constant temperature 2-4h at 96-100 DEG C of temperature, filters, and filter cake is sent to iron recovery system;
D, the filtrate heating obtaining in step C has been concentrated into crystal and has occurred after, stop heating, natural cooling crystallization, filters, dry cake obtains sodium stannate;
E, by step D filter after mother liquid obtained acid neutralization, through centrifugal, press filtration, washing obtain metastannic acid, metastannic acid, at 200-400 DEG C of roasting temperature, is obtained to tindioxide.
2. a kind of method of utilizing tin stripping liquid coproduction sodium stannate and tindioxide as claimed in claim 1, is characterized in that: in described steps A, ionogen is selected from Na
2sO
4, Na
3pO
4, K
2sO
4or K
3pO
4in one or more.
3. a kind of method of utilizing tin stripping liquid coproduction sodium stannate and tindioxide as claimed in claim 1, is characterized in that: in described step C, solid alkali is selected from NaOH, KOH or Na
2cO
3in one or more.
4. a kind of method of utilizing tin stripping liquid coproduction sodium stannate and tindioxide as claimed in claim 1, is characterized in that: in described step e, acid is selected from one or more in hydrochloric acid, sulfuric acid, carbonic acid or phosphoric acid.
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|---|---|---|---|
| CN201010521861.6A CN101948133B (en) | 2010-10-28 | 2010-10-28 | Method for co-producing sodium stannate and stannic oxide by solder removing liquid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010521861.6A CN101948133B (en) | 2010-10-28 | 2010-10-28 | Method for co-producing sodium stannate and stannic oxide by solder removing liquid |
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| CN101948133B true CN101948133B (en) | 2014-08-06 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923764B (en) * | 2012-10-25 | 2014-07-30 | 中南大学 | Method for preparing sodium stannate from stannic oxide and sodium salt in reduction roasting manner |
| 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 |
| WO2016184249A1 (en) * | 2015-05-21 | 2016-11-24 | 成都虹华环保科技股份有限公司 | Nitric acid tin-stripping liquid treatment system |
| CN104894599A (en) * | 2015-06-23 | 2015-09-09 | 成都虹华环保科技股份有限公司 | Recycling process of tin-removing waste liquid |
| 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 |
| CN105293454B (en) * | 2015-10-27 | 2017-03-29 | 盛隆资源再生（无锡）有限公司 | A kind of method that spent solder stripper prepares dust technology, spongy tin and aluminium polychlorid |
| CN108070720B (en) * | 2017-11-10 | 2019-03-26 | 河海大学 | A kind of comprehensive recovering process of tin removal waste liquor |
| CN109633076A (en) * | 2018-12-10 | 2019-04-16 | 广东省佛山地质局(广东省佛山地质灾害应急抢险技术中心) | The measuring method of Theil indices in the preprocess method and tin stripper of tin stripper |
| CN109536982B (en) * | 2018-12-27 | 2021-04-13 | 广东先导稀材股份有限公司 | Preparation method of nano tin dioxide |
| CN115232985B (en) * | 2022-07-01 | 2024-01-16 | 清远市中宇环保实业有限公司 | Alkaline leaching-crystallization preparation process of tin in tin-containing sludge |
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| CN1530466A (en) * | 2003-03-11 | 2004-09-22 | 湖南高奇实业有限公司 | Recovery of tin from waste liquid of tin and lead |
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| CN101497458A (en) * | 2008-01-30 | 2009-08-05 | 深圳市东江环保股份有限公司 | Method for preparing sodium stannate using circuit board tin-stripping wastewater |
| CN101532096A (en) * | 2009-04-01 | 2009-09-16 | 深圳市危险废物处理站有限公司 | A recovery method of tin in tin-stripping waste liquid |
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- 2010-10-28 CN CN201010521861.6A patent/CN101948133B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1530466A (en) * | 2003-03-11 | 2004-09-22 | 湖南高奇实业有限公司 | Recovery of tin from waste liquid of tin and lead |
| CN1569644A (en) * | 2004-04-30 | 2005-01-26 | 深圳市危险废物处理站 | Method for preparing barium stannate trihydrate using stannum in waste tin stripper |
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