CN1073984A - Reclaim the method for low-concentration gold - Google Patents
Reclaim the method for low-concentration gold Download PDFInfo
- Publication number
- CN1073984A CN1073984A CN91112607A CN91112607A CN1073984A CN 1073984 A CN1073984 A CN 1073984A CN 91112607 A CN91112607 A CN 91112607A CN 91112607 A CN91112607 A CN 91112607A CN 1073984 A CN1073984 A CN 1073984A
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- Prior art keywords
- gold
- concentration
- reaction
- reaction solution
- light
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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
Abstract
The invention discloses a kind of method that reclaims low-concentration gold.The present invention adopts ZnFe
2O
4Spinel carries out light-catalyzed reaction to reach the purpose that reclaims gold as catalyzer.Adding catalytic amount is (0.2～2) * 10 of reaction solution weight
-3Doubly, the control reacting liquid pH value is between 3～10, adds small amount of methanol (reaction solution volume 0.006～0.05 times), and (wavelength is all can carry out light-catalyzed reaction under 230～560nm), makes Au in visible light and UV-light
3+Ion (concentration is between 1ppm～100ppm) reduction, the rate of recovery of reacting 1～3 hour gold reaches 90～100%.
Description
The present invention relates to a kind of method that reclaims low-concentration gold, the present invention makes Au in the solution by using a kind of light-catalyzed reaction catalyzer
3+The ion reduction is reclaimed.
From auriferous trade effluent or waste liquid, reclaim gold, on the one hand can resources conseravtion, can eliminate the pollution of metal ion on the other hand to environment.
People adopt chemical method to reclaim with Au usually
3+The gold that ion exists, concrete grammar is to contain Au
3+Add zinc powder, activated aluminum powder, sulphite and organic reducing agent in the ion solution, this method makes reductive agent consumption very big, and expense is higher, when reclaiming gold also easily with other metal recovery.If Au in the solution
3+When ionic concn was low, it is more powerless that chemical method just seems.
Utilize light-catalyzed reaction to reclaim the existing people of gold and carried out preliminary exploration, the photocatalyst of selecting for use usually mostly is photosemiconductor.If photosemiconductor is not caught by the hydrogen ion in the solution at the electronics that conduction band produces by optical excitation, but catch by the metal ion that exists in solution, under the situation that its redox potential is fit to, the light precipitation of some metals on photosemiconductor just can take place.N.Serpone, E.Borgarello and E.Pelizzetti[Photo catalysis(1989) 610～620; J.Photo chem., 36373(1987)] reported semiconductor powders such as adopting titanium dioxide reclaims gold from waste water result, the titanium dioxide good stability, but Eg too wide (3.0ev), bad with the solar spectrum response, only can absorb and account in the sunlight 5 percent UV-light, its quantum yield is not high yet.
The objective of the invention is to avoid above the deficiencies in the prior art part and a kind of method that reclaims low-concentration gold is provided, promptly utilize photocatalytic method to reclaim low-concentration gold, provide a kind of cheap and easy to get, the photocatalyst that catalytic activity is high, can both carry out light-catalyzed reaction under visible light and UV-light, low-concentration gold is reclaimed in reduction.
The object of the present invention is achieved like this:
Photocatalytic method reclaims gold and is based on little multiphase photocatalysis process.The used photocatalyst of the present invention is ZnFe
2O
4Spinel-a kind of composite oxide semiconductor, it have suitable energy gap (2.1～2.4ev) and flat-band potential, can be produced hole-electron pair by excited by visible light.The semiconductive particles photochemical catalysis can be considered the photoelectrochemistrpool pool of short circuit with regard to its charge transfer mechanism.When being subjected to energy greater than the rayed of semi-conductor energy gap, its valence band electronics is stimulated and transits to conduction band, produces electron-hole pair, under the effect of surface field, the different sites of catalyst surface is transferred in electronics and hole respectively, again with solution in species carry out redox reaction.For reduction gold, i.e. Au
3+Obtain the valence band electronics, be reduced to Au, simultaneously the hole pickling agent in the oxidizing water of hole.
Containing Au
3+In the ion low concentration solution, add quantitative photocatalyst-ZnFe
2O
4Spinel under the condition of fully stirring and illumination, just can carry out light-catalyzed reaction, reaches the purpose that reclaims gold.
The ZnFe that the present invention is used
2O
4Spinel catalyst prepares with coprecipitation method.Preparation process is such: take by weighing a certain amount of Zn(NO by stoichiometric ratio
3)
26H
2O, Fe(NO
3)
39H
2O, soluble in water, add an amount of ammoniacal liquor and make its precipitation fully, filtering-depositing, and with distilled water wash for several times, placed at normal temperatures 10-20 hour, dry down at 100 ℃, activate 9～11 hours down at 650 ℃～900 ℃ then, room temperature to be naturally cooled to, standby after pulverizing.Specific surface area of catalyst is 6～10 meters
2/ gram, catalyst activation temperature is preferably in 700～800 ℃.
The method of recovery low-concentration gold of the present invention, the light-catalyzed reaction that relates to is to ZnFe
2O
4The mechanism of action can do following statement:
1, photo-induced generation hole-electron pair:
2, photo catalytic reduction
The present invention can be to the Au of concentration range at 1ppm～100ppm
3+Ion reclaims.
Photocatalyst-ZnFe that the present invention is used
2O
4The spinel consumption is reaction solution weight (0.2～2) * 10
-3Doubly.
Under UV-light and radiation of visible light, carry out light-catalyzed reaction and reclaim low-concentration gold, ZnFe
2O
4Can both show good photoreduction gold ability, it is to carry out light-catalyzed reaction under 230～560nm that the present invention is adapted at wavelength.
Reaction solution is controlled at appropriate pH value scope can makes light-catalyzed reaction complete, the reduction that helps gold is reclaimed, and method of the present invention must be controlled at the pH value of reaction soln between 3～10.
The used hole pickling agent of the present invention is a methyl alcohol, and methyl alcohol can be eliminated in the enrichment of the hole of semiconductor surface, and light-catalyzed reaction adds a spot of hole pickling agent can make gold reclaim fully, shortens the reaction times.The add-on of methyl alcohol of the present invention is 0.006～0.05 times of reaction solution volume.
The reaction times that the present invention suits is 1～3 hour.
When the method for recovery low-concentration gold of the present invention, light-catalyzed reaction reclaim gold, there is no other side reaction and take place, in the solution if Cu is arranged
2+, Fe
3+, Zn
2+When waiting other metal ion to exist, these metal ions of reaction back are not seen reduction.
ZnFe
2O
4Spinel catalyst is difficult for being seen Table 1 by photoetch, reaction back Fe
3+, Zn
2+The ion content changing conditions:
Table 1: Fe in the solution of reaction back
3+, Zn
2+Ion content
| Catalyzer | ZnFe 2O 4 |
| Fe 3+ | 0.056ppm |
| Zn 2+ | 0 |
1ppm＝1μg/ml
Below in conjunction with embodiment the present invention is further specified:
Example 1: get 150 gram Zn(NO
3)
26H
2O, 400 gram Fe(NO
3)
39H
2O is dissolved in 1 liter of distilled water, adding concentration with fast speed under constantly stirring is 13%(weight) ammoniacal liquor, make pH value reach 9～10, filter, for several times with distilled water wash, filter cake placed room temperature following 15 hours, through 100 ℃ of dryings, activate 10 hours down at 700 ℃ then, naturally cool to room temperature, be ground into 200 order powder, promptly get ZnFe
2O
4Spinel catalyst is measured through BET, and specific surface area is a 6-10 rice
2/ gram; Get catalyzer and put into Au for 50 milligrams
3+Concentration is (following examples reaction solution volume of the present invention is 25 milliliters) in 25 ml solns of 100ppm, adds 1 milliliter of methyl alcohol, and the control pH value is 3.0, uses 250 watts of mercury lamp illumination reactions 120 minutes under constantly stirring, and gold recovery is 99.8%.
Example 2: changing light source is 750 watts of xenon lamps, and other condition is identical with example 1, and gold recovery is 100%.
Example 3: changing the reaction solution pH value is 10, and other condition is with example 1, and the rate of recovery of gold reaches 96%.
Example 4: changing catalyst levels is 20 milligrams, and other condition is identical with example 1, and the rate of recovery of gold is 90%.
Example 5: changing methanol usage is 0.6 milliliter, and other condition is with example 1, the rate of recovery 98% of gold.
Example 6: with example 1, changing methanol usage is 0.5 milliliter, and the rate of recovery of gold is 96%.
Example 7: change Au
3+Ionic concn is 1ppm, and other condition is with example 1, and the rate of recovery of gold reaches 100%.
Example 8: change Au
3+Ionic concn is 10ppm, and other condition is with example 1, and the rate of recovery of gold is 98%.
Example 9: with example 1, changing light application time is 60 minutes, and the rate of recovery of gold is 90%.
Example 10: with example 9, changing light source is 750 watts of xenon lamps, and the rate of recovery of gold is 96%.
Example 11: get 10 milligrams of catalyzer, 0.4 milliliter of methyl alcohol, Au
3+Concentration 50ppm, making the solution pH value is 6, is to react 3 hours under 750 watts of xenon lamp irradiations at light source, gold recovery is 98%.
Example 12: get 30 milligrams of catalyzer, Au
3+Concentration is 20ppm, adds 0.2 ml methanol, makes solution PH=7, is illumination reaction 2.5 hours under 250 watts of mercury lamps at light source, gold recovery 100%.
Example 13: get catalyzer and add Au for 40 milligrams
3+Concentration is in the solution of 70ppm, and making pH value is 5, and with 750 watts of xenon lamp irradiations 1 hour, gold recovery was 95%.
Example 14: at Au
3+Concentration is 80ppm, Cu
2+Concentration is to add 20 milligrams of catalyzer, 1 milliliter of methyl alcohol in the solution of 100ppm, and the control pH value is 8, and reaction is 3 hours under 750 watts of xenon lamps irradiations, and the rate of recovery of gold is 97%, does not see Cu
2+Reduction.
Example 15: at Au
3+Concentration is 100ppm, Fe
3+Concentration is to add 50 milligrams of catalyzer, 0.3 milliliter of methyl alcohol in the solution of 100ppm, control PH=4, and reaction is 3 hours under 250 watts of mercury lamps irradiations, and gold recovery is 100%, does not see Fe
3+Reduction.
Example 16: at Au
3+Concentration is 100ppm, Zn
2-Concentration is 100ppm, Mg
2+Concentration is to add 9 milligrams of catalyzer, 0.8 milliliter of methyl alcohol in the solution of 100ppm, and the control pH value is 5,750 watts of xenon lamps according under reaction 2 hours, gold recovery is 93%, does not see Zn
2+, Mg
2+Reduction.
Claims (5)
1, a kind of method that reclaims low-concentration gold, comprising: (1) is with Au
3+Use photocatalyst in the solution that ion exists.(2) carry out illumination reaction under fully stirring, it is characterized in that: (1) photocatalyst is 2nFe
2O
4Spinel.Consumption is reaction solution weight (0.2～2) * 10
-3Doubly; (2) illumination wavelength is between 230～560nm.
2, as the said method of claim 1, it is characterized in that in reaction solution, adding methyl alcohol, consumption is 0.006～0.05 times of reaction solution volume.
3,, it is characterized in that the reaction solution pH value is controlled between 3～10 as the said method of claim 1.
4,, it is characterized in that the reaction times is 1～3 hour as the said method of claim 1.
5, as the said method of claim 1, it is characterized in that Au in the reaction solution
3+Ionic concn is reacted under 1ppm～100ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91112607A CN1032597C (en) | 1991-12-26 | 1991-12-26 | Method for recovering low-concentration gold |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91112607A CN1032597C (en) | 1991-12-26 | 1991-12-26 | Method for recovering low-concentration gold |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1073984A true CN1073984A (en) | 1993-07-07 |
| CN1032597C CN1032597C (en) | 1996-08-21 |
Family
ID=4910965
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91112607A Expired - Fee Related CN1032597C (en) | 1991-12-26 | 1991-12-26 | Method for recovering low-concentration gold |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1032597C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111500871A (en) * | 2020-04-13 | 2020-08-07 | 云南师范大学 | Method for extracting gold, platinum and palladium by utilizing sunlight enrichment and separation |
| WO2020206962A1 (en) * | 2019-04-12 | 2020-10-15 | 上海师范大学 | Photocatalysis method for dissolving metal |
| CN113088689A (en) * | 2021-03-24 | 2021-07-09 | 上海师范大学 | Method for dissolving noble metal in aqueous solution in photocatalytic selective manner |
-
1991
- 1991-12-26 CN CN91112607A patent/CN1032597C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020206962A1 (en) * | 2019-04-12 | 2020-10-15 | 上海师范大学 | Photocatalysis method for dissolving metal |
| US11920212B2 (en) | 2019-04-12 | 2024-03-05 | Shanghai Normal University | Method for dissolving metals by photocatalysis |
| CN111500871A (en) * | 2020-04-13 | 2020-08-07 | 云南师范大学 | Method for extracting gold, platinum and palladium by utilizing sunlight enrichment and separation |
| CN111500871B (en) * | 2020-04-13 | 2022-06-21 | 云南师范大学 | Method for extracting gold, platinum and palladium by utilizing sunlight enrichment and separation |
| CN113088689A (en) * | 2021-03-24 | 2021-07-09 | 上海师范大学 | Method for dissolving noble metal in aqueous solution in photocatalytic selective manner |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1032597C (en) | 1996-08-21 |
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