CN102352441A - Method for recycling silver from waste fixer - Google Patents
Method for recycling silver from waste fixer Download PDFInfo
- Publication number
- CN102352441A CN102352441A CN2011103215266A CN201110321526A CN102352441A CN 102352441 A CN102352441 A CN 102352441A CN 2011103215266 A CN2011103215266 A CN 2011103215266A CN 201110321526 A CN201110321526 A CN 201110321526A CN 102352441 A CN102352441 A CN 102352441A
- Authority
- CN
- China
- Prior art keywords
- silver
- waste fixer
- solution
- sulfide
- waste
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for recycling silver from waste fixer, thus the toxic gas hydrogen sulfide can not be generated in the precipitation process. The method comprises the following steps: dropping enough hydrogen peroxide aqueous solution in the waste fixer under stirring to ensure that no new Ag2S which is a black precipitate is generated, and stopping dropping and stirring; and standing the reaction solution to fully precipitate, performing suction filtering, washing to ensure that the filtrate is neutral, and treating the obtained silver sulfide precipitate to obtain silver. By adopting the method provided by the invention, the toxic gas hydrogen sulfide can not be generated in the reaction process and the damages to the environment and the operator can be eliminated. The content of silver in the waste fixer and the purity of the obtained silver are measured by the atomic absorption spectrometry, and the recovery rate of silver is up to above 98% and the purity is up to above 99.5%.
Description
Technical field
The invention belongs to field of fine chemical, be specially a kind of method that from waste fixer solution, reclaims silver.
Background technology
Silver is a kind of precious metal, and its standing stock and output all are limited, and cost an arm and a leg.Along with development of modern science and technology, the whole world grows with each passing day to the demand of silver, and the silver of industry consumption has a big chunk to be used to make sensitive materials.Current waste fixer solution is not only from photography and cinefilm, and the composing of computer and offset printing process also have generation; Sensitive materials is after exposure, development, photographic fixing, and most of silver enters into stop bath; Waste fixer solution is not as handling, contaminate environment not only, but also can cause the wasting of resources; In the waste fixer solution, silver is with thiosulfuric acid silver complex [Ag (S
2O
3)
2]
3-Form exist, the concentration of silver is 2 ~ 9g/L, the pH value is between 4 ~ 10.Therefore, the recovery of silver receives domestic and international relevant person's generally attention always in the waste fixer solution.The method that from waste fixer solution, reclaims silver mainly contains: the precipitator method, reduction method, air supporting method, electrolytic process, ion exchange method etc.Wherein the precipitator method are in waste fixer solution, to add a certain amount of precipitation agent sodium sulfide solution, because the instability constant K of silver thiosulfate coordination ion
UnstableBe 3.5*10
-11, silver sulfide is to be difficult to one of dissolved silver salt, its solubility product K
SpBe 6.3*10
-50, be far smaller than the instability constant K of silver thiosulfate coordination ion
Unstable, after adding an amount of sodium sulphite of people, just produce the silver sulfide black precipitate.Chemical equation is:
2[Ag（S
2O
3）
2]
3-?+?S
2-?→?Ag
2S↓?+?4S
2O
3 2-
After reacting completely, leave standstill, suction filtration, washing, drying obtains clean silver sulfide deposition, adopts sodium carbonate fusion or active metal reduction method etc. to obtain silver through melting then.The shortcoming of this method is to produce a large amount of hydrogen sulfide toxic gases in the precipitation process, and environment and operator are polluted and damage.
Summary of the invention
The purpose of this invention is to provide a kind of method that from waste fixer solution, reclaims silver, this method can be avoided hydrogen sulfide toxic gas generation in the precipitation process.
Be the realization above-mentioned purpose, the technical scheme that the present invention adopts is: a kind of method that from waste fixer solution, reclaims silver, the aqueous hydrogen peroxide solution of dropping capacity in waste fixer solution adds the dropping limit and stirs, up to no new Ag
2After producing, the S black precipitate stops to drip, stopping to stir; Reaction solution is left standstill, and deposition is back suction filtration, washing fully, is neutral until filtrating, will obtain silver after the gained silver sulfide precipitation process again.
The chemical equation of the method for the invention is:
2[Ag（S
2O
3）
2]
3-?+?12H
2O
2?→?Ag
2S
2O
3↓?+?6SO
4 2-?+?6H
+?+?9H
2O
Ag
2S
2O
3?+?H
2O?→?Ag
2S↓?+?H
2SO
4
Hydrogen peroxide generates the silver thiosulfate deposition and the sodium sulfate of white with the oxidation of dithio sulfato silver, and silver thiosulfate decomposes rapidly in solution, color through yellow, brown, generate the black silver sulfide at last and precipitate.Should present blue look with starch-kalium iodide test paper check reaction solution test paper, show that precipitin reaction is complete.With the method for silver sulfide precipitation process Cheng Yin is the common practise of this area, like sodium carbonate fusion and active metal reduction method.
Dripping before the aqueous hydrogen peroxide solution, in waste fixer solution, add bromogeramine, is for the silver sulfide particle being increased, being convenient to filter.The chemistry of bromogeramine is called dodecyl dimethyl benzyl ammonium bromide, is a kind of known tensio-active agent.
As a kind of preferred version; The described method that silver sulfide is processed into silver is that gained silver sulfide deposition is dry; Sneak into the smelting agent of silver sulfide quality 20 ~ 30%; Pack in the crucible; It is silver-colored to place 1200 ℃ of High Temperature Furnaces Heating Apparatus meltings promptly to get after 2 hours, and smelting agent is to be mixed by yellow soda ash and the borax mass ratio with 3:1.
Method of the present invention toxic gas such as no hydrogen sulfide in reaction process produces, and has eliminated to the pollution of environment with to operator's infringement.With the content of silver and the purity of gained silver in the aas determination waste fixer solution, the rate of recovery of silver reaches more than 98%, and purity reaches more than 99.5%.
Analyze with detection method and be:
Adopt atomic absorption spectrophotometry to analyze and detect, at first prepare the AgNO of different concns
3Standard model is surveyed its absorbancy, the drawing standard curve; As shown in Figure 1, curvilinear equation is: A=0.083
C-0.0078 (wherein A is an absorbancy;
CConcentration for silver-colored solution), relation conefficient=0.99920.
With embodiment 2 is example, respectively silver in the waste fixer solution and the silver in the recovery sample is measured, and it is following to measure the result:
(1) detection of silver in the waste fixer solution: after 12500 times of waste fixer solution dilutions, recording absorbance A is 0.050, and the content that calculates silver in the former waste fixer solution according to curvilinear equation is 8.705g L
-1
(2) reclaim detection silver-colored in the gained sample: fetch and receive gained sample 0.2500g; Dissolving also is settled to 1L; With recording absorbancy behind 250 times of the solution dilutions behind the constant volume is 0.075, calculates according to curvilinear equation that silver is 0.2493g in the recovery sample, and purity is 99.7%.
Description of drawings
The typical curve of drafting when Fig. 1 analyzes and detects for adopting atomic absorption spectrophotometry.
Embodiment
Embodiment 1
The waste fixer solution (silver content is 8.705g/L) of measuring 100mL slowly drips 30% the aqueous hydrogen peroxide solution of 13mL in the beaker of 200mL, stir while dripping, up to no new Ag
2After producing, the S black precipitate stops to drip, stopping to stir.Standing over night, deposition be the back suction filtration fully, and washing is neutral up to filtrating.With gained silver sulfide deposition drying, sneak into the smelting agent (yellow soda ash mixes with the mass ratio of borax with 3:1) of silver sulfide quality 20 ~ 30%, in the crucible of packing into, place 1200 ℃ of High Temperature Furnaces Heating Apparatus meltings 2 hours, get silver 0.7359g.
Embodiment 2
The waste fixer solution (silver content is 8.705g/L) of measuring 100mL slowly drips 30% the aqueous hydrogen peroxide solution of 15mL in the beaker of 200mL, stir while dripping, up to no new Ag
2After producing, the S black precipitate stops to drip, stopping to stir.Standing over night, suction filtration, washing is neutral up to filtrating.With gained silver sulfide deposition drying, sneak into the smelting agent (yellow soda ash mixes with the mass ratio of borax with 3:1) of silver sulfide quality 20 ~ 30%, in the crucible of packing into, place 1200 ℃ of High Temperature Furnaces Heating Apparatus meltings 2 hours, get silver 0.8640g.
Embodiment 3
The waste fixer solution (silver content is 8.705g/L) of measuring 100mL slowly drips 30% the aqueous hydrogen peroxide solution of 17mL in the beaker of 200mL, stir while dripping.Up to no new Ag
2After producing, the S black precipitate stops to drip, stopping to stir.Standing over night, suction filtration, washing is neutral up to filtrating.With gained silver sulfide deposition drying, sneak into the smelting agent (yellow soda ash mixes with the mass ratio of borax with 3:1) of silver sulfide quality 20 ~ 30%, in the crucible of packing into, place 1200 ℃ of High Temperature Furnaces Heating Apparatus meltings 2 hours, get silver 0.8623g.
Claims (3)
1. one kind is reclaimed silver-colored method from waste fixer solution, it is characterized in that: the mass concentration that in waste fixer solution, drips capacity is 30% aqueous hydrogen peroxide solution, adds to drip the limit stirring, up to no new Ag
2After producing, the S black precipitate stops to drip, stopping to stir; Reaction solution is left standstill, and deposition is back suction filtration, washing fully, is neutral until filtrating, will obtain silver after the gained silver sulfide precipitation process again.
2. the method that from waste fixer solution, reclaims silver according to claim 1 is characterized in that: drip before the aqueous hydrogen peroxide solution, in waste fixer solution, add bromogeramine.
3. the method that from waste fixer solution, reclaims silver according to claim 1 and 2; It is characterized in that: the described method that silver sulfide is processed into silver is that gained silver sulfide deposition is dry; Sneak into the smelting agent of silver sulfide quality 20 ~ 30%; Pack in the crucible; It is silver-colored to place 1200 ℃ of High Temperature Furnaces Heating Apparatus meltings promptly to get after 2 hours, and smelting agent is to be mixed by yellow soda ash and the borax mass ratio with 3:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103215266A CN102352441A (en) | 2011-10-21 | 2011-10-21 | Method for recycling silver from waste fixer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103215266A CN102352441A (en) | 2011-10-21 | 2011-10-21 | Method for recycling silver from waste fixer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102352441A true CN102352441A (en) | 2012-02-15 |
Family
ID=45576077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103215266A Pending CN102352441A (en) | 2011-10-21 | 2011-10-21 | Method for recycling silver from waste fixer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102352441A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104640806A (en) * | 2012-08-21 | 2015-05-20 | 托普索公司 | A method for recovering hydrogen from hydrogen sulfide |
| CN107746960A (en) * | 2017-11-28 | 2018-03-02 | 青海黄河上游水电开发有限责任公司光伏产业技术分公司 | A kind of method that aluminium and silver are reclaimed from photovoltaic module |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW469261B (en) * | 1997-11-05 | 2001-12-21 | Jing-Shiung Jang | Method and apparatus for treating wastewater from film development |
| CN101086036A (en) * | 2007-04-19 | 2007-12-12 | 方孝玲 | Process for recovering silver from waste fixer solution |
-
2011
- 2011-10-21 CN CN2011103215266A patent/CN102352441A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW469261B (en) * | 1997-11-05 | 2001-12-21 | Jing-Shiung Jang | Method and apparatus for treating wastewater from film development |
| CN101086036A (en) * | 2007-04-19 | 2007-12-12 | 方孝玲 | Process for recovering silver from waste fixer solution |
Non-Patent Citations (6)
| Title |
|---|
| 区端力: "快速沉淀法回收废定影液中的银", 《感光材料》 * |
| 方忠才: "过氧化氢还原法回收金属银", 《金属制品》 * |
| 熊道陵等: "从废感光材料中制备硝酸银的新方法", 《化工进展》 * |
| 熊道陵等: "废定影液中银的回收与提纯", 《黄金》 * |
| 韩志萍等: "从彩印漂定液废水中回收银和制备纳米银粉技术的研究", 《贵金属》 * |
| 魏剑英等: "从废旧X光胶片中回收银", 《感光材料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104640806A (en) * | 2012-08-21 | 2015-05-20 | 托普索公司 | A method for recovering hydrogen from hydrogen sulfide |
| CN107746960A (en) * | 2017-11-28 | 2018-03-02 | 青海黄河上游水电开发有限责任公司光伏产业技术分公司 | A kind of method that aluminium and silver are reclaimed from photovoltaic module |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2065479C (en) | Ferrous dithionite process and compositions for removing heavy metals from water | |
| CN104316643B (en) | Three element assay methods of nickel-cobalt-manganese ternary material | |
| Koyanaka et al. | Quantitative correlation between Li absorption and H content in manganese oxide spinel λ-MnO2 | |
| CN108190938A (en) | It is a kind of to give up the method that silver paste prepares high purity silver nitrate from photovoltaic | |
| CN101065518A (en) | Gold plating liquid and gold plating method | |
| JP4981749B2 (en) | Method and system for quantitative analysis of selenium | |
| CN105784696B (en) | The analysis determining method of each valence state sulphur in a kind of sodium aluminate solution | |
| CN110658143A (en) | Method for measuring contents of trace elements of bismuth, cadmium, chromium, copper, iron, lead, zinc, nickel, cobalt and manganese in high-concentration brine | |
| CN102352441A (en) | Method for recycling silver from waste fixer | |
| Grano et al. | Solution interaction of ethyl xanthate and sulphite and its effect on galena flotation and xanthate adsorption | |
| Banijamali et al. | Leaching behavior of silver sulfide in the sodium thiosulfate-copper sulfate-sodium metabisulfite system | |
| Zhao et al. | Clean and effective removal of Cl (-I) from strongly acidic wastewater by PbO2 | |
| Palanivelu et al. | A chemical enhancement method for the spectrophotometric determination of trace amounts of arsenic | |
| Adeloju et al. | Adsorptive cathodic stripping voltammetric determination of ultra-trace concentrations of vanadium on a glassy carbon mercury film electrode | |
| CN111208032A (en) | Method for measuring and analyzing content of calcium sulfite and calcium sulfide | |
| Willie et al. | The voltammetric determination of Mo in seawater after adsorptive accumulation of the Eriochrome Blue Black R complex | |
| CN102392137A (en) | Method for recovering silver from waste fixer by using acid as precipitant | |
| CN105671335A (en) | Method of breaking gel of cyanogen containing solution and recycling cyanogen containing solution | |
| CN102616963B (en) | Photocatalytic treatment method of sensitive material waste | |
| CN106380015B (en) | A method of copper ion in bluestone waste of the removal containing nitric acid | |
| Kashiwagi et al. | Selective Determination of Selenium (IV) and Selenium (Vl) in Waste Water by Graphite Furnace AAS after Reductive Coprecipitation on Tellurium Collector by Ascorbic Acid, Tin (II) Chloride and Hydrazinium Sulfate | |
| CN107188219B (en) | A method of silver sulfate is recycled from CODCr measurement waste liquid | |
| CN116376545B (en) | Preparation of N, S co-doped red light carbon dot material and application of N, S co-doped red light carbon dot material in visual detection of heavy metal ions | |
| TW201412380A (en) | Trihalomethane control in wet flue gas desulfurization | |
| CN109626411A (en) | A kind of production technology of anhydrous stannous chloride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120215 |