CN101403048A - Sulphuric acid solvent extraction method for recycling indium from germanium distillation waste acid - Google Patents
Sulphuric acid solvent extraction method for recycling indium from germanium distillation waste acid Download PDFInfo
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- CN101403048A CN101403048A CNA2008100229655A CN200810022965A CN101403048A CN 101403048 A CN101403048 A CN 101403048A CN A2008100229655 A CNA2008100229655 A CN A2008100229655A CN 200810022965 A CN200810022965 A CN 200810022965A CN 101403048 A CN101403048 A CN 101403048A
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- indium
- acid
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- sulfuric acid
- distillation waste
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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
A sulfuric acid leaching method for recovering indium from germanium distilled acid relates to a method for recovering indium from germanium distilled acid, belonging to the technical field of chemical metallurgy, which comprises the following steps of: mixing indium-enriched oxide with water, adding sulfuric acid for a plurality of times to leach, adding hydrogen peroxide in the leaching process, controlling the terminal pH value to 1.0, standing and fetching a primary leaching supernatant to extract the indium. The technical indexes acquired from sulfuric acid leaching are as follows: the leaching rate of the indium is larger than 98 percent, the content of the indium in the leaching slag is less than 800g/t, and the content of the indium in the primary leaching liquid is 3-8g/l. The method of the invention is an important step for avoiding secondary pollution in the entire production process and realizing high recovery rate.
Description
Technical field
The present invention relates to a kind of method, particularly sulphuric acid solvent extraction method wherein that from germanium distillation waste acid, reclaims indium, belong to the chemical metallurgy technical field.
Background technology
Distillation waste acid is the residual acid of germanium still-process, because of also containing a certain amount of indium in germanium concentrate or the germanium enrichment flue dust except that germanium, so with in the hydrochloric acid system distillation germanium process, the indium major part is dissolved and finally enters distillation waste acid, has certain recovery value.The distillation waste acid complicated component is embodied in the acidity height, generally contains sour 6-8mol/l, contains plurality of impurities such as tin, antimony, bismuth, lead, zinc, magnesium, aluminium, silicon simultaneously, and make indium reclaim and have bigger technical difficulty, and also uneconomical.The indium recovery technology that is seen in report has:
1, spent acid neutralization-acidleach is got--indium is reclaimed in extraction: its process be with alkali directly in and spent acid, after press filtration, obtain containing the indium slag, leach with sulfuric acid the washing back, the indium leach liquor is used 30%P after adjusting PH
2O
4+ kerosene extraction obtains the acid chlorization solution of indium after the hydrochloric acid back extraction, obtain the sponge indium with aluminium sheet or photo zincography displacement, and the sponge indium covers fusion with alkali, and casting obtains thick indium product after the skimming.This technology is that common indium reclaims technology, and have following shortcoming but be applied to distillation waste acid recovery indium: the quantity of alkali consumption with spent acid in (1) is big; Requirement acidity was big when (2) sulfuric acid leached, temperature is high, the indium leaching yield is low, need the repeated multiple times leaching just can make slag contain indium and meet the requirements, acidleach goes out process can only do simple separation to the insoluble impurity of sulfuric acid such as lead, and major parts such as tin, antimony, bismuth, zinc, magnesium, aluminium, silicon enter leach liquor; (3) extraction process phenomenons such as third phase, emulsification occur easily because of the influence of impurity such as tin, antimony, silicon, brings to extraction to seriously influence; (4) chloride higher because of containing the indium slag, acidleach often causes indium residual in the raffinate higher when going out to be converted under the sulfuric acid system condition extraction; (5) extraction agent need often carry out manipulation of regeneration; (6) impurity concentration is higher in the indium strip liquor, directly influences the quality of thick indium.
2, spent acid TBP coextraction-selection back extraction-P
2O
4Indium is reclaimed in extraction: its process is directly to use TBP+ octanol+kerosene extraction under high acidity condition, and indium is extracted with iron, antimony, tin etc. in the extraction process.With hydrochloric acid back extraction indium, iron, use P after the reduction of back extraction indium liquid
2O
4+ kerosene carries out indium extraction, and carry out back extraction with the hydrochloric acid of 6mlo/l and obtain the indium chloride strip liquor, again through replacing--founding obtains thick indium product.The regeneration of TBP+ octanol+kerosene organic phase comprises first back extraction antimony, back extraction tin again, and the organic phase after the regeneration is all returned coextraction.P
2O
4The regeneration of+kerosene organic phase is to carry out the organic phase regenerated from washing with 60g/l oxalic acid, and the organic phase after the regeneration is all returned extraction of indium.Have data to show that this technological process indium recovery is higher, mainly there is following shortcoming in the industrialization but technology still is unrealized: acid waste gas brings adverse influence to extraction equipment and site environment in (1) distillation waste acid; (2) organism and silicic acid jelly bring adverse influence to extraction process in the distillation waste acid.
With regard to the characteristics of germanium distillation waste acid, as adopt traditional sulfuric acid system extraction process to reclaim indium, need emphasis to solve following problem: (1) acidity is high and too high with cost in causing; (2) problem that influences that plurality of impurities such as tin, arsenic, antimony, bismuth, lead, zinc, magnesium, aluminium, silicon, organism extract indium in the distillation waste acid; (3) be converted into the influence problem of chlorine root to extracting in the sulfuric acid system by hydrochloric acid system; (4) problem of environmental pollution that brings of the volatility of hydrochloric acid.
Now invented a kind ofly with the method that concentrates, processes such as alkalization, washing, sulfuric acid leaching, indium extraction, aluminium sheet displacement, founding reclaim indium from germanium distillation waste acid, this method overcomes prior art defective, rate of recovery height, does not produce secondary pollution.
Summary of the invention
The object of the invention is to invent the sulphuric acid solvent extraction method in a kind of aforesaid method, is beneficial to the processing of later process, realizes that finally preparation process does not produce secondary pollution, goal of the invention that the rate of recovery is high.
It is that oxide compound with the enrichment indium mixes the back gradation and adds the sulfuric acid leaching with water that sulfuric acid of the present invention leaches, and adds hydrogen peroxide in the leaching process, and controlling the terminal point pH value is 1.0, gets after leaving standstill once to leach supernatant liquor and be used to extract indium.
Leaching the technical indicator that is obtained through sulfuric acid is: the indium leaching yield is greater than 98%, and leached mud contains indium less than 800g/t.One time leach liquor contains indium 3-8g/l.The present invention realizes that whole process of production does not produce the important step of secondary pollution, high-recovery.
Hydrogen peroxide add-on of the present invention is the 5kg/m of reaction total amount
3
Leaching process of the present invention slowly adds hydrogen peroxide.
The present invention also can add the prime cement that once leaches water and sulfuric acid and carry out the secondary leaching, and control terminal point sulfuric acid concentration 0.5mol/l filters slurries the leached mud washing.The secondary leach liquor contains indium 1-3g/l (the secondary leach liquor returns once and leaches).
Embodiment
1, concentrate:
With the distillation waste acid airtight concentration kettle of packing into, continue heating with steam and concentrate distillation waste acid, feed pressurized air simultaneously to improve evaporation rate, sour gas is introduced in the hydrochloric acid absorption unit, returns Distallation systm through the hydrochloric acid of acquisition about 30% after the gas-water separation and utilizes again.Liquid of the concentrated end after concentrating is long-pending to be reduced to originally 20%, and the salt acidacidity is reduced to below the 1mol/l by 6～8mol/l, and indium concentration increases 5 times, and indium is free of losses in concentration process.After meeting the requirements, the acidity of liquid of the concentrated end send alkalinisation treatment.
Its technical qualification are: thickening temperature: 100～120 ℃; Concentration kettle internal pressure: 0.2～0.3kPa, velocity of evaporation: 200L/h.
2, alkalization:
Concentrate end liquid and enter in the reactor, directly add sodium hydroxide, SODIUMNITRATE, stir and the high temperature alkalization, add hydrogen peroxide in the alkalization process to promote reaction, can be with impurity removals such as the tin more than 50～70%, lead, arsenic, aluminium, zinc, silicon.Iron, antimony, bismuth etc. form oxide compound with indium and go into slag.
The alkalization technical qualification are: sodium hydroxide concentration: 100～150kg/m
3Concentrate end liquid; SODIUMNITRATE consumption: 6kg/m
3Concentrate end liquid; Hydrogen peroxide consumption: 15kg/m
3Concentrate end liquid.90～100 ℃ of alkalization temperatures; Alkalization time 3h.
By alkalization, resulting technical indicator is: impurity removal percentage 50～85%; Indium is gone into the slag rate: 98%; Oxide compound contains indium: 2～5%.
3, washing:
The alkalization slurries add hot water earlier and carry out first wash, and the first wash number of times is 2 times, leaves standstill behind agitator treating, takes out supernatant and send water treatment; Prime cement adds water again and carries out second wash, is neutral back and becomes limpid transparent until washing water, filters the oxide compound that obtains the enrichment indium, and washing water return the first wash recycling.
The technical qualification of first wash are: volume ratio; Water: slurries=3: 1, temperature: 80～90 ℃, sedimentation time 8 hours.
The technical qualification of second wash: volume ratio: water: slurries=5: 1, temperature are normal temperature, settling time 8 hours.
Washing terminal point PH=6.5～7.0, washing water chlorion, nitrate ion content are less than 50mg/l.
4, sulfuric acid leaches:
Indium oxide leaches with sulfuric acid, and once leaching liquid-solid ratio is 5: 1, and the terminal point pH value is 1.0, slowly adds hydrogen peroxide in the leaching process promoting reaction, after reaction finishes, leaves standstill and then extracts supernatant liquor in 5 hours out and send extraction.Prime cement adds water again and adds sulfuric acid and carry out secondary and leach, and it is 3: 1 that secondary leaches liquid-solid ratio, and leaching the terminal point sulfuric acid concentration is 0.5mol/l; Slurries filter, the leached mud washing, and secondary leach liquor and washing water return once and leach.Through twice leaching, the indium leaching yield is greater than 98%.
Sulfuric acid leaching-out technique condition: once leach: the sulfuric acid gradation adds, and stops to add acid, hydrogen peroxide add-on: 5kg/m at 1.0 o'clock to the solution PH value stabilization
3Liquid-solid ratio 5: 1; Temperature 80-90 ℃, extraction time 2h, time of repose 5 hours; Secondary leaches the terminal point sulfuric acid concentration: 0.5mol/l, hydrogen peroxide add-on: 5kg/m
3Liquid-solid ratio: 3: 1,80～90 ℃ of temperature, time 2h.
Leaching the technical indicator that is obtained through sulfuric acid is: the indium leaching yield is greater than 98%, and leached mud contains indium less than 800g/t.One time leach liquor contains indium 3～8g/l.Secondary leach liquor 1～3g/l (the secondary leach liquor returns once and leaches).
5, reduction acid-adjusting: its objective is the ferric iron in leach liquor is reduced to ferrous iron, simultaneously solution PH is adjusted to 1.5, for follow-up extraction provides satisfactory feed liquid.
One time leach liquor reduces with S-WAT, detects no ferric iron with ferron and is advisable, and adjusts PH to 1.5 with alkali lye again, and limpid the contain solution of indium of supernatant liquor behind the cotton filter fine filtering send extraction and extract indium after overcooling is left standstill.Slag of a small amount of end returns sulfuric acid and leaches.
The reduction acid-adjusting technical qualification are: S-WAT consumption: S-WAT: iron=1.25: 1 (weight ratio); Acid adjustment concentration of lye: 30%; Terminal point PH1.5, reduction acid-adjusting controlled temperature are 50～60 ℃, then are cooled to normal temperature.
The technical indicator that obtains through reduction acid-adjusting is: indium is gone into the slag rate less than 1%, and ferric iron content is less than 10mg/l in the solution of indium.
6, indium extracts: adopt conventional extraction--displacement--founding technology.The technical indicator that the indium leaching process is obtained is: the indium total yield: 93%, and thick indium contains indium greater than 99%.
Indium leaching process technical qualification and technical indicator are as follows:
6.1 indium extraction: extraction agent 25～30%P
2O
4+ kerosene is compared A/O=2/1,3 grades of counter-current extraction progression, and temperature: 25～35 ℃, aqueous phase flow rate; 5～8m
3/ (m
2.h), mixing time: 3～5 minutes, the phase-splitting time: 5～8 minutes.Raffinate indium concentration is less than 50mg/l.Recovery of extraction 99%.
6.2 indium back extraction:
The pickling condition: 1.0～1.5mol/l sulfuric acid washing, 2 grades of pickling progression are compared: O/A=4/1, organic phase flow velocity: 0.5m
3/ (m
2.h).Pickle solution indium concentration is returned sulfuric acid and is leached operation less than 0.1g/l.
The back extraction condition: 3 grades of back extraction progression, compare: O/A=4: 1, organic phase flow velocity: 0.5m
3/ (m2.h), concentration of hydrochloric acid: 6mol/l, strip liquor indium concentration: 40-60g/l.
6.3 indium displacement: aluminium sheet displacement, displacement liquid PH1.0～1.5; 80～90 ℃ of temperature, time swap 8～15 hours, displaced liquid contains indium less than 50mg/l, and the indium replacement recovery rate is greater than 98%
6.4 indium founding: sodium hydroxide covers, 200～300 ℃ of melt temperatures, alkali add-on: be advisable so that slag is thin.Returning sulfuric acid after the water washing of founding alkaline residue leaches.The thick indium ingot of casting after the skimming.The alkaline residue that skims returns the alkalization process and handles.
The thick indium product recovery rate 96% of fusion-casting process.
Claims (4)
1, from germanium distillation waste acid, reclaims the sulphuric acid solvent extraction method of indium, it is characterized in that it is that oxide compound with the enrichment indium mixes the leaching of back gradation adding sulfuric acid with water that sulfuric acid leaches, add hydrogen peroxide in the leaching process, control terminal point pH value is 1.0, gets after leaving standstill once to leach supernatant liquor and be used to extract indium.
2, according to the described sulphuric acid solvent extraction method that from germanium distillation waste acid, reclaims indium of claim 1, it is characterized in that the 5kg/m of hydrogen peroxide add-on for the reaction total amount
3
3, according to the described sulphuric acid solvent extraction method that from germanium distillation waste acid, reclaims indium of claim 1, it is characterized in that leaching process slowly adds hydrogen peroxide.
4, according to claim 1 or the 2 or 3 described sulphuric acid solvent extraction methods that from germanium distillation waste acid, reclaim indium, it is characterized in that the prime cement that once leaches adds water and sulfuric acid carries out the secondary leaching, control terminal point sulfuric acid concentration 0.5mol/l filters slurries the leached mud washing.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100229655A CN101403048A (en) | 2008-07-04 | 2008-07-04 | Sulphuric acid solvent extraction method for recycling indium from germanium distillation waste acid |
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| CNA2008100229655A CN101403048A (en) | 2008-07-04 | 2008-07-04 | Sulphuric acid solvent extraction method for recycling indium from germanium distillation waste acid |
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| CN101403048A true CN101403048A (en) | 2009-04-08 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106834755A (en) * | 2016-12-28 | 2017-06-13 | 呼伦贝尔驰宏矿业有限公司 | A kind of technique of the concentration and separation of oxygen leaching liquid containing indium indium |
| CN111270091A (en) * | 2020-02-29 | 2020-06-12 | 河南豫光锌业有限公司 | Method for reducing indium content in indium leaching slag |
-
2008
- 2008-07-04 CN CNA2008100229655A patent/CN101403048A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106834755A (en) * | 2016-12-28 | 2017-06-13 | 呼伦贝尔驰宏矿业有限公司 | A kind of technique of the concentration and separation of oxygen leaching liquid containing indium indium |
| CN111270091A (en) * | 2020-02-29 | 2020-06-12 | 河南豫光锌业有限公司 | Method for reducing indium content in indium leaching slag |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Yangzhou Ningda Noble Metal Co., Ltd. Assignor: Fan Hongjie Contract record no.: 2010320001097 Denomination of invention: Sulphuric acid solvent extraction method for recycling indium from germanium distillation waste acid License type: Exclusive License Open date: 20090408 Record date: 20100826 |
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| ASS | Succession or assignment of patent right |
Owner name: HU NAN QIU ZEYOU PATENT STRATEGIC PLANNING CO., LT Free format text: FORMER OWNER: QIU ZEYOU Effective date: 20101027 |
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| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 410011 28/F, SHUNTIANCHENG, NO.59, SECTION 2 OF FURONG MIDDLE ROAD, CHANGSHA CITY, HU NAN PROVINCE TO: 410205 JUXING INDUSTRY BASE, NO.8, LUJING ROAD, CHANGSHA HIGH-TECH. DEVELOPMENT ZONE, YUELU DISTRICT, CHANGSHA CITY, HU NAN PROVINCE |
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| TA01 | Transfer of patent application right |
Effective date of registration: 20101104 Address after: 225231 No. 1, industrial concentration area, Yiling Town, Jiangdu City, Jiangsu Province Applicant after: Yangzhou Ningda Noble Metal Co., Ltd. Address before: 225231 No. 1, industrial concentration area, Yiling Town, Jiangdu City, Jiangsu Province Applicant before: Fan Hongjie |
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Open date: 20090408 |