CN105838891B - A kind of method that valuable metal is reclaimed from the low germanium of high silicon, low indium zinc oxide fumes - Google Patents

A kind of method that valuable metal is reclaimed from the low germanium of high silicon, low indium zinc oxide fumes Download PDF

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CN105838891B
CN105838891B CN201610212115.6A CN201610212115A CN105838891B CN 105838891 B CN105838891 B CN 105838891B CN 201610212115 A CN201610212115 A CN 201610212115A CN 105838891 B CN105838891 B CN 105838891B
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germanium
low
indium
silicon
liquid
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CN105838891A (en
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杨建兴
赵德军
赵兵伍
陈长浩
周立雄
赵菊华
赵保灿
陈会东
龙国心
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Yunnan Luoping Zinc & Electricity Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/02—Working-up flue dust
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/04—Obtaining noble metals by wet processes
    • C22B11/042—Recovery of noble metals from waste materials
    • C22B11/044—Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00—Obtaining lead
    • C22B13/04—Obtaining lead by wet processes
    • C22B13/045—Recovery from waste materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B41/00—Obtaining germanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B58/00—Obtaining gallium or indium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • 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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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
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  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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Abstract

A kind of method that valuable metal is reclaimed from the low germanium of high silicon, low indium zinc oxide fumes, its step is：1）Once leach；2）It is secondary to leach；3）The purification and absorption of silicon；4）Neutralize heavy indium；5）Tannin sinks germanium.The present invention uses easier method, is combined the purification open circuit of silicon and the absorption property of amorphous carbon, realizes fully recycling for resource.Utilize the adsorptivity of amorphous carbon, the strainability of solid-liquor separation when preferably improving silica purge, the suspension in solution is set to have effective carrier, so that the limpid no suspended substance of filtrate, this method not only eliminates the influence of silicon and suspension to heavy indium, heavy germanium, meanwhile, added amorphous carbon can also normally play the effect of its combustion heating and reduction during rotary kiln evaporation.Raw material indium, germanium grade it is relatively low and in the case that silica is higher, it is to avoid the interference of silicon and suspension, realize the smooth recovery of germanium, indium.

Description

A kind of method that valuable metal is reclaimed from the low germanium of high silicon, low indium zinc oxide fumes
Technical field
The invention belongs to hydrometallurgy field, and in particular to one kind is reclaimed from the low germanium of high silicon, low indium zinc oxide fumes to be had The method of valency metal.
Background technology
Raw material used in zinc hydrometallurgy contains a certain amount of germanium and indium mostly, have because its content is too low and is difficult to be returned Receive and utilize.In zinc hydrometallurgy production process, raw material germanium and indium major part after neutrality is leached are enriched in leached mud, are leached The valuable metal such as germanium, indium, lead is also volatilized and is enriched in zinc oxide fumes while slag reclaims zinc using rotary kiln evaporation；But Germanium, indium content are too low in some zinc metallurgy raw materials, and germanium, the indium content produced in zinc oxide fumes be not also high.The oxygen that our company is produced Change Zn dust just belong to above-mentioned situation, it not only the low and contained silica of germanium, indium content it is higher, its Main Ingredients and Appearance For：Zinc 50wt% ~ 55wt%, germanium 0.02wt% ~ 0.03wt%, indium 0.015wt% ~ 0.025wt%, lead 6wt% ~ 10wt%, silica 5wt% ~ 8wt%, silver 0.003wt% ~ 0.005wt%, iron 4wt% ~ 6wt%.
Traditional zinc oxide fumes germanium, indium, zinc, lead, the recovery method of silver are that zinc oxide fumes is through an acidleach, control Terminal pH=2.0 ~ 3.5, leachate passes through liquid after the heavy germanium of tannin and output germanium concentrate, heavy germanium and reclaims zinc；Leached mud is again through two Secondary acidic leaching, secondary acid leaching solution uses P204+ kerosene extraction indium, raffinate is returned before zinc oxide fumes once leaches and do Liquid；Lead and Yin Ze are enriched in the slag after secondary pickling to be sold in the form of lead smelting gas.Also another mode is germanium, indium Quan Cuifa, i.e. zinc oxide fumes carry out acidleach, and leachate difference extracted germanium, indium, its raffinate carry out the recovery of zinc；Lead and Yin Ze It is also the sale in the form of lead smelting gas in the slag of enrichment after leaching；But above conventional method be all in zinc oxide fumes germanium, Indium content is of a relatively high and carries out in the case that its silicone content is not high.It is relatively low for germanium, indium content in this case, and titanium dioxide The high raw material of silicone content, it is unpractical to use conventional methods.
Proved by lot of experiments, the zinc oxide fumes, which is used conventional methods, does an acidic leaching, in control tannin On the point that heavy germanium terminal acid pH is required, that is, during pH=2.0 ~ 3.5, germanium only has 20mg/l ~ 30mg/l or so, indium in leachate There is 0.1mg/l ~ 0.2mg/l or so, silica is but up to 4g/l ~ 8g/l, because the silicon being now leached largely forms silica gel, Its solid-liquor separation is very difficult, and the filtrate of institute's output is not limpid, suspension is more；The heavy germanium of tannin is carried out with the filtrate, not only liquid is consolidated Separation is very difficult, and tannin multiplying power is also up to more than 50 times, and the germanic only 3wt% ~ 6wt% of germanium concentrate of output；Quadratic acid Property leaching extraction recovery indium, although solid-liquor separation is not so too difficult, but because its filtrate in be also up to containing silica 4g/l ~ 6g/l, also only has 25mg/l ~ 35mg/l containing indium, causes extraction cycle amount big, and organic phase emulsification is serious, split-phase is difficult, several It can not realize that indium is extracted.In addition, tested using germanium, the full extraction of indium, also in that siliceous height in its solution, and Germanium, indium are relatively low, and extraction cycle amount is big, and organic phase emulsification is serious, split-phase is difficult, it is virtually impossible to realize the extract and separate of germanium, indium.
The content of the invention
It is an object of the invention to provide a kind of method that valuable metal is reclaimed from the low germanium of high silicon, low indium zinc oxide fumes, Specifically include following steps：
1）Once leach：Zinc oxide fumes is pressed 6 ~ 7 with pulp liquid：1 liquid-solid ratio carries out pulp, slurry time 20 ~ 30 Minute, with the concentrated sulfuric acid adjustment begin acid 120g/l ~ 130g/l, 75 DEG C ~ 85 DEG C of control process temperature, extraction time 1.0 ~ 1.5 hours, Filtering 1, filtering No. 1 leached mud of 1 output and No. 1 leachate are carried out behind terminal pH=1.1 ~ 1.5, No. 1 leached mud carries out secondary leaching Go out, No. 1 leachate carries out the purification and absorption of silicon；
2）It is secondary to leach：4 ~ 5 are pressed to No. 1 leached mud with industrial water or zinc electrolytic waste liquid：1 liquid-solid ratio is starched Change, with concentrated sulfuric acid adjustment beginning acid 130g/l ~ 140g/l, 90 DEG C ~ 95 DEG C of control process temperature, extraction time 3.0 ~ 4.0 hours, end Filtering 2, filtering No. 2 leached muds of 2 output and No. 2 leachates are carried out after 50 ~ 60g/l of point acid, No. 2 leached muds do lead silver preparation concentrate and gone out Sell, No. 2 leachates, which return once to leach, does pulp liquid；
3）The purification and absorption of silicon：Preceding liquid is done with No. 1 leachate, 70 DEG C ~ 75 DEG C is warming up to, adds ox glue solution, plus Enter amount for ox glue：Amount=1 ~ 1.5 of silica in solution：1, it is slowly added to while stirring during addition, adds 20 ~ 30 points of stirring After clock, amorphous carbon is added, addition is 0.85 ~ 0.95kg/m3, be stirred for 15 ~ 20 minutes, static 40 ~ 50 minutes it is laggard Row filter 23, No. 3 silicon breezes of filter 23 output and No. 3 filtered fluids, No. 3 silicon breezes send rotary kiln evaporation to reclaim valuable gold therein Category, No. 3 filtered fluids carry out the heavy indium of neutralization of next step；
4）Neutralize heavy indium：With No. 3 filtered fluids after silica purge, 65 DEG C ~ 70 DEG C are warming up to, is slowly added to what is prepared 15wt% ~ 20wt% aqueous sodium carbonate, is filtered after solution acidity pH value is adjusted to 3.0 ~ 3.5, static 20 ~ 30 minutes 4, filter No. 4 indium concentrate of 4 output and carry out liquid after No. 4 heavy indiums of the heavy germanium of next step；
5）Tannin sinks germanium：With liquid after No. 4 heavy indiums, be warming up to 60 DEG C ~ 70 DEG C, 30 ~ 35 times of tannic acid multiplying power, stirring 30 ~ 35 Filtering 5 is carried out after minute, filtering 5 obtains liquid power transmission Zn system after liquid after No. 5 tannin germanium slags and No. 5 heavy germanium, No. 5 heavy germanium and reclaimed Zinc, and No. 5 tannin germanium slags are produced in liquid-solid ratio 3 ~ 4：1st, filtering 6, mistake are carried out after being washed 30 ~ 40 minutes at 65 DEG C ~ 75 DEG C of temperature Filter 6 obtains No. 6 and washes rear tannin germanium slag and No. 6 germanium wash heat water, washes rear tannin germanium slag and send the calcination of calcination workshop to obtain germanium concentrate for No. 6 Sell, No. 6 germanium wash heat water, which return once to leach, does pulp liquid.
Compared with prior art, the present invention has following technique effect：
1st, the invention provides a kind of high efficiente callback germanium from the low germanium of high silicon, low indium zinc oxide fumes, indium, zinc, lead, silver Method；By two-stage leaching, the leached mud of output is that lead silver preparation concentrate is sold, and passes through from a leachate silicon and suspension Open circuit, make indium, germanium reclaim become easier to；Raw material indium, germanium grade it is relatively low and in the case that silica is higher, it is to avoid The interference of silicon, to realize low germanium, low indium can smoothly reclaim, output 4wt% containing indium ~ 5wt% indium concentrate and germanic 17wt% ~ 18wt% germanium concentrate, makes the valuable metal in low content obtain preferable comprehensive reutilization, it also avoid remaining during extraction The influence that organic matter is produced to electric zinc；
2nd, the present invention is calculated from whole flow process, and the rate of recovery of germanium is in more than 87.50wt%；The rate of recovery of indium is in 93.90wt% More than；Whole zinc, germanium, indium removal process, the rate of recovery of zinc in more than 95.70wt%, the rate of recovery of lead in more than 99.90wt%, The rate of recovery of silver is in more than 96.30wt%；
3rd, the characteristics of present invention is maximum is to use easier method, makes purification open circuit and the absorption of amorphous carbon of silicon Performance is combined, and realizes fully recycling for resource；Because make use of amorphous carbon surface hole to be added in liquid has Certain absorption property, makes the suspension in solution have effective carrier, so that the limpid no suspended substance of filtrate, and produced Filter residue namely No. 3 evacuations of silicon breeze, water contents are low, are compared with amorphous carbon absorption is added without, low 3 ~ 5 wt% of moisture content, for the slag Next step carries out rotary kiln and waved with there is provided preferable condition；This method not only eliminates silicon and suspension to heavy indium, the germanium that sinks Influence；Meanwhile, added amorphous carbon can also normally play the effect of its combustion heating and reduction during rotary kiln evaporation； Liquid is after adding ox glue purification silicon and amorphous carbon absorption before heavy indium, and silica is almost removed totally, and heavy silicon rate reaches More than 98.50wt%；
4th, leachate of the present invention, using the hydrolytic precipitation of indium, carries out indium after silicon is opened a way from the feed liquid of low content Enrichment is effectively reclaimed, is the supplement reclaimed to indium tradition；
5th, using the technique, its leached mud rate is smaller, only 29.0wt% or so；This causes Zn content in produced lead smelting gas Relatively low, only 6.0wt% ~ 6.5wt% also allows lead silver to obtain preferable enrichment while effectively increasing zinc recovery, and slag contains Lead reaches 0.01wt% ~ 0.017wt% up to 22.50wt% ~ 35.50wt%, slag argentiferous, leached mud is done silver-colored when lead silver preparation concentrate is sold obtain Valuation is arrived；
6th, it is of the invention compared with traditional recovery process, new waste water,waste gas and industrial residue is not produced, meets national synthetical recovery Utilize, recycling economy and the requirement of sustainable development.
Brief description of the drawings
Fig. 1 is process chart of the invention.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is further illustrated, but the present invention is not subject in any way Limitation, any change or replacement according to the teachings of the present invention made belongs to protection scope of the present invention.
A kind of method that valuable metal is reclaimed from the low germanium of high silicon, low indium zinc oxide fumes, be the step of methods described：
1）Once leach：Zinc oxide fumes is pressed 6 ~ 7 with pulp liquid：1 liquid-solid ratio carries out pulp, slurry time 20 ~ 30 Minute, with the concentrated sulfuric acid adjustment begin acid 120g/l ~ 130g/l, 75 DEG C ~ 85 DEG C of control process temperature, extraction time 1.0 ~ 1.5 hours, Filtering 1, filtering No. 1 leached mud of 1 output and No. 1 leachate are carried out behind terminal pH=1.1 ~ 1.5, No. 1 leached mud carries out secondary leaching Go out, No. 1 leachate carries out the purification and absorption of silicon；
2）It is secondary to leach：4 ~ 5 are pressed to No. 1 leached mud with industrial water or zinc electrolytic waste liquid：1 liquid-solid ratio is starched Change, with concentrated sulfuric acid adjustment beginning acid 130g/l ~ 140g/l, 90 DEG C ~ 95 DEG C of control process temperature, extraction time 3.0 ~ 4.0 hours, end Filtering 2, filtering No. 2 leached muds of 2 output and No. 2 leachates are carried out after 50 ~ 60g/l of point acid, No. 2 leached muds do lead silver preparation concentrate and gone out Sell, No. 2 leachates, which return once to leach, does pulp liquid；
3）The purification and absorption of silicon：Preceding liquid is done with No. 1 leachate, 70 DEG C ~ 75 DEG C is warming up to, adds ox glue solution, plus Enter amount for ox glue：Amount=1 ~ 1.5 of silica in solution：1, it is slowly added to while stirring during addition, adds 20 ~ 30 points of stirring After clock, amorphous carbon is added, addition is 0.85 ~ 0.95kg/m3, be stirred for 15 ~ 20 minutes, static 40 ~ 50 minutes it is laggard Row filter 23, No. 3 silicon breezes of filter 23 output and No. 3 filtered fluids, No. 3 silicon breezes send rotary kiln evaporation to reclaim valuable gold therein Category, No. 3 filtered fluids carry out the heavy indium of neutralization of next step；
4）Neutralize heavy indium：With No. 3 filtered fluids after silica purge, 65 DEG C ~ 70 DEG C are warming up to, is slowly added to what is prepared 15wt% ~ 20wt% aqueous sodium carbonate, is filtered after solution acidity pH value is adjusted to 3.0 ~ 3.5, static 20 ~ 30 minutes 4, filter No. 4 indium concentrate of 4 output and carry out liquid after No. 4 heavy indiums of the heavy germanium of next step；
5）Tannin sinks germanium：With liquid after No. 4 heavy indiums, be warming up to 60 DEG C ~ 70 DEG C, 30 ~ 35 times of tannic acid multiplying power, stirring 30 ~ 35 Filtering 5 is carried out after minute, filtering 5 obtains liquid power transmission Zn system after liquid after No. 5 tannin germanium slags and No. 5 heavy germanium, No. 5 heavy germanium and reclaimed Zinc, and No. 5 tannin germanium slags are produced in liquid-solid ratio 3 ~ 4：1st, filtering 6, mistake are carried out after being washed 30 ~ 40 minutes at 65 DEG C ~ 75 DEG C of temperature Filter 6 obtains No. 6 and washes rear tannin germanium slag and No. 6 germanium wash heat water, washes rear tannin germanium slag and send the calcination of calcination workshop to obtain germanium concentrate for No. 6 Sell, No. 6 germanium wash heat water, which return once to leach, does pulp liquid.
The described low germanium of high silicon, low indium zinc oxide fumes are 50wt% containing zinc ~ 55wt%, germanium 0.02wt% ~ 0.03wt%, indium 0.015wt% ~ 0.025wt%, silica 5wt% ~ 8wt%.
Pulp liquid described in step 1 is one in industrial water, zinc electrolytic waste liquid, No. 2 leachates, No. 6 germanium wash heat water Plant or several；The leachate obtained when No. 2 leachates herein are secondary leaching by filtering 2, No. 6 germanium wash heat water are heavy for tannin The germanium wash heat water obtained during germanium by filtering 6.
Terminal pH=1.2 ~ 1.4 described in step 1.
Ox glue solution addition described in step 3 is ox glue：Amount=1.2 ~ 1.4 of silica in solution：1.
Ox glue solution described in step 3 is configured to 20wt% ~ 30wt%'s to take ox glue to be added in 50 DEG C ~ 60 DEG C water The aqueous solution.
Amorphous carbon described in step 3 is the one or more in coke, activated carbon, charcoal.
Amorphous carbon addition described in step 3 is 0.90kg/m3。
Amorphous carbon described in step 3 was the amorphous carbon of 80 eye mesh screens.
Tannic acid multiplying power described in step 5 is 32 ~ 34 times.
Leaded 22.50wt% ~ the 35.50wt% of lead silver preparation concentrate, argentiferous 0.01wt% ~ 0.017wt% described in step 2.
1.50wt% containing zinc ~ 2.00wt%, germanic 0.002wt% ~ 0.003wt% in indium concentrate described in step 4, containing indium 4.00wt%~5.00wt%。
Germanic 17wt% ~ 18wt% in germanium concentrate described in step 5.
Embodiment 1
The oxidation that the rotary kiln evaporation carried out using Yunnan Luoping Zinc ＆ Electricity Co., Ltd.'s zinc hydrometallurgy leached mud is produced 20000.00 grams of division sample preparation is stand-by after Zn dust, drying, and its composition is：Zinc 50.18wt%, germanium 0.0208wt%, indium 0.0153wt%, lead 6.58wt%, silica 5.43wt%, silver 0.0030wt%, iron 4.27wt%.
（1）Once leach：Preceding liquid is made of industrial water, 72 liters are taken, zinc oxide fumes is added and is starched for 12000.0 grams Change, slurry time 20 minutes, with the concentrated sulfuric acid adjustment begin acid arrive 120g/l, 75 DEG C of control process temperature, extraction time 1.0 hours, Filtering 1 is carried out behind terminal pH=1.1.Filter No. 1 leached mud of 1 output and carry out secondary leaching and 107.67g/l containing zinc, indium 0.021g/ L, the g/l of silica 6.54, germanium 0.028g/l, the g/l of lead 0.0026, silver 0.00019g/l, ferrous iron 7.14g/l, ferric iron 0.024g/l 48.50 liters of No. 1 leachate.
（2）It is secondary to leach：38 liters of industrial waters are added to No. 1 leached mud and carry out pulp, are adjusted after stirring with the concentrated sulfuric acid Whole beginning acid 130g/l, heating is caused after 90 DEG C, extraction time 3.0 hours, and filtering 2 is carried out after terminal acid 50g/l.Filter 2 outputs Water content 22.58wt%, 6.46wt% containing zinc, germanium 0.0076wt%, indium 0.003wt%, lead 22.68wt%, silica 4.70wt%, Silver-colored 0.010wt%, iron 1.40wt% No. 2 4495 grams of wet slags of leaching do lead silver preparation concentrate and sold and 16.42g/l containing zinc, indium 0.019g/ L, silica 4.88g/l, germanium 0.025g/l, lead 0.0013g/l, silver 0.000086g/l, ferrous iron 3.27g/l, ferric iron 0.039g/l 35.00 liters of No. 2 leachates, which return once to leach, does pulp liquid.
（3）The purification and absorption of silicon：Preceding liquid is done with No. 1 47.50 liters of leachate, 70 DEG C is warming up to, added ox glue is amounted to 360 grams are added to and are made into the 20wt% aqueous solution in 50 DEG C of water and are slowly added into the solution of silicon to be sunk, stirring while adding, plus Continue to stir 20 minutes after entering, add the coke of 42.75 grams of eye mesh screens of mistake 80, stir 15 minutes, static 40 minutes filter 23s； Filter 23 output water content 37.25wt%, 6.41wt% containing zinc, germanic 0.0012wt%, containing the wt% of indium 0.00016, leaded 0.030wt%, 74.14wt% containing silica, argentiferous 0.0022wt%, iron content 0.67wt% 661 grams of No. 3 silicon charcoal wet slags and containing zinc 108.71g/l, 0.0213g/l containing indium, silica 0.06g/l, germanium 0.0283g/l, ferrous iron 7.20g/l, ferric iron No. 3 micro heavy 46.8 liters of silicon filtered fluids of 0.012g/l, lead silver；No. 3 silicon breezes send rotary kiln evaporation to reclaim valuable gold therein Category, No. 3 heavy silicon filtered fluids carry out the heavy indium of neutralization of next step；
（4）Neutralize heavy indium：With 46.0 liters of No. 3 filtered fluids after silica purge, 65 DEG C are warming up to, is slowly added to what is prepared 15wt% aqueous sodium carbonate, solution acidity pH value is adjusted to behind 3.0, static 20 minutes carry out filtering 4；4 outputs are filtered to contain Moisture content 51.64wt%, 1.54wt% containing zinc, germanic 0.002wt%, containing the wt% of indium 4.02,8.61wt% containing silica, iron content 5.33wt% 50.25 grams of No. 4 indium concentrate weight in wet bases and 109.42g/l containing zinc, 0.00006g/l containing indium, silica 0.015g/l, 45.7 liters of liquid after germanium 0.0285g/l, ferrous iron 7.23g/l, ferric iron 0.001g/l No. 4 heavy indiums, No. 4 indium concentrate are sold or entered Liquid carries out the heavy germanium of next step after one step recovery indium, No. 4 heavy indiums.
（5）Tannin sinks germanium：With 44 liters of liquid after No. 4 heavy indiums, be warming up to 60 DEG C, 37.62 grams of tannic acid with 20wt% concentration It is dissolved in 50 DEG C ~ 60 DEG C of water and is added slowly in the case of stirring in the solution of heavy germanium, continues to stir after adding Filtering 5 is carried out after 30 minutes, filtering 5 obtains tannin germanium slag and 110.34g/l containing zinc, silica 0.011g/l, germanium Liquid power transmission Zn system after 43.60 liters of liquid after No. 5 micro heavy germanium of 0.00013g/l, ferrous iron 7.27g/l, ferric iron, No. 5 heavy germanium Zinc is reclaimed, and tannin germanium slag is in liquid-solid ratio 3:1st, filtering 6 is carried out after being washed 30 minutes at 65 DEG C of temperature, filtering 6 obtains water content 64.35wt%, 3.45wt% containing zinc, germanium 3.12wt%, No. 6 of silica 0.45wt% wash 112 grams of rear tannin germanium slag weight in wet base and contain Zinc 3.68g/l, 0.001g/l containing silica, germanic 0.0008g/l, 0.25g/l containing ferrous iron, the 0.001g/l containing ferric iron No. 6 0.67 liter of germanium wash heat water；No. 6 germanium wash heat water, which return once to leach, does adjusting slurry, washes after rear tannin germanium slag is dried at 105 DEG C simultaneously Calcination obtains 18.53wt% containing zinc, germanic 17.01wt%, silica 2.34wt%, sulphur after causing weight at 550 ~ 600 DEG C 7.3 grams micro of germanium concentrate of 1.28wt%, iron 14.02wt%, lead is to be vended.
It is by can be calculated each economic target：
1. the leaching process of the zinc oxide fumes：Lead recovery 99.97wt%, silver raising recovery rate are 96.66wt%, the leaching of zinc Extracting rate is that 96.26wt%, the leaching rate 74.89wt% of silica, the leaching rate of germanium are that 89.30wt%, the leaching rate of indium are 94.33wt%, the leaching rate of iron are 90.46wt%.
2. in silica purge and adsorption process, the rate of deposition of silicon reaches 98.96wt%, is adsorbed due to adding coke, mistake Filter performance is substantially improved, liquid also special limpid, no suspended substance after the heavy silicon produced, completely eliminate silicon to heavy indium, heavy germanium and The influence of filtering；While realizing effective recovery indium, also improve the quality of produced germanium concentrate, make germanium concentrate reach it is superfine with On grade, and added coke gets back during next step rotary kiln evaporation and makes full use of.
3. whole synthetical recovery process zinc loss 4.29wt%, i.e. zinc recovery 95.71wt%.
4. whole synthetical recovery process germanium rate of recovery 87.53wt%.
5. whole synthetical recovery process indium recovery 93.98wt%
Embodiment 2
The oxidation that the rotary kiln evaporation carried out using Yunnan Luoping Zinc ＆ Electricity Co., Ltd.'s zinc hydrometallurgy leached mud is produced 18000.00 grams of division sample preparation is stand-by after Zn dust, drying, and its composition is：Zinc 55.08wt%, germanium 0.0306wt%, indium 0.0249wt%, silica 8.08wt%, lead 9.96wt%, silver 0.0048wt%, iron 5.94wt%.
（1）Once leach：Preceding liquid is made of industrial water, 70 liters are taken, zinc oxide fumes is added and is starched for 10000.0 grams Change, slurry time 30 minutes, with the concentrated sulfuric acid adjustment begin acid arrive 130g/l, 85 DEG C of control process temperature, extraction time 1.5 hours, Filtering 1 is carried out behind terminal pH=1.5；No. 1 leached mud of output carries out secondary leaching and 100.79g/l containing zinc, indium 0.0301g/l, two The g/l of silica 9.06, germanium 0.0358g/l, lead 0.0027g/l, silver 0.0002g/l, ferrous iron 8.55g/l, ferric iron 0.025g/l 47.0 liters of No. 1 leachate；
（2）It is secondary to leach：37 liters of industrial waters are added to No. 1 leached mud and carry out pulp, are adjusted after stirring with the concentrated sulfuric acid Whole beginning acid 140g/l, is warming up to after 95 DEG C, leaches 4.0 hours, and filtering 2 is carried out after terminal acid 60g/l；Filter 2 outputs aqueous Part 23.15wt%, 5.89wt% containing zinc, germanium 0.0088wt%, indium 0.0035wt%, lead 35.56wt%, silica 6.82wt%, silver 0.017wt%, iron 1.91wt% No. 2 3643 grams of wet slags of leaching do lead silver preparation concentrate and sold and 16.38g/l containing zinc, indium 0.0264g/ L, silica 5.53g/l, germanium 0.0306g/l, lead 0.0014g/l, silver 0.000091g/l, ferrous iron 4.02g/l, ferric iron 0.02g/l 34.00 liters of No. 2 leachates, which return once to leach, does pulp liquid；
（3）The purification and absorption of silicon：Preceding liquid is done with No. 1 46.5 liters of leachate, 75 DEG C is warming up to, added ox glue is amounted to 632 grams are added to and are made into the 30wt% aqueous solution in 60 DEG C of water and are slowly added into the solution of heavy silicon, stirring while adding, add Continue to stir 30 minutes afterwards, the coke of 41.85 grams of eye mesh screens of mistake 80 is added, 3 after stirring 20 minutes, filtering in static 50 minutes； It is filter 23 output water content 39.25wt%, 4.12wt% containing zinc, germanic 0.0011wt%, 0.00015wt% containing indium, leaded 0.021wt%, 69.03wt% containing silica, argentiferous 0.0015wt%, iron content 0.56wt% 999 grams of No. 3 silicon charcoal wet slags and containing zinc 101.78g/l, 0.0305g/l containing indium, silica 0.05g/l, germanium 0.0362g/l, ferrous iron 8.63g/l, ferric iron No. 3 micro heavy 45.8 liters of silicon filtered fluids of 0.001g/l, lead silver；No. 3 silicon breezes send rotary kiln evaporation to reclaim valuable gold therein Category, No. 3 heavy silicon filtered fluids carry out the heavy indium of neutralization of next step；
（4）Neutralize heavy indium：With 45.0 liters of No. 3 filtered fluids after silica purge, 70 DEG C are warming up to, is slowly added to be configured to 20wt% aqueous sodium carbonate, solution acidity pH value is adjusted to behind 3.5, static 30 minutes carry out filtering 4；4 outputs are filtered to contain Moisture content 53.16wt%, 2.08wt% containing zinc, germanic 0.0022wt%, containing the wt% of indium 4.98,5.78wt% containing silica, iron content 7.65wt% 58.49 grams of No. 4 indium concentrate weight in wet bases and 102.68g/l containing zinc, 0.00018g/l containing indium, silica 0.015g/l, 44.6 liters of liquid after germanium 0.0365g/l, ferrous iron 8.66g/l, ferric iron 0.001g/l No. 4 heavy indiums；No. 4 heavy indium concentrate sell or Liquid carries out the heavy germanium of next step after further recovery indium, No. 4 heavy indiums.
（5）Tannin sinks germanium：With 43.5 liters of liquid after No. 4 heavy indiums, be warming up to 70 DEG C, 55.57 grams of tannic acid with the dense of 20wt% Degree is dissolved in 50 DEG C ~ 60 DEG C of water and is added slowly in the case of stirring in the solution of germanium to be sunk, and continues after adding Stirring carries out filtering 5 after 35 minutes, filtering 5 obtains tannin germanium slag and 103.77g/l containing zinc, silica 0.01g/l, germanium 43.0 liters of liquid after 0.00014g/l, ferrous iron 8.73g/l, trivalent 0.001g/l No. 5 heavy germanium.Liquid power transmission zinc system after No. 5 heavy germanium System reclaims zinc, and tannin germanium slag is in liquid-solid ratio 4:1st, filtering 6 is carried out after being washed 40 minutes at 75 DEG C of temperature, filtering 6 obtains aqueous Part 65.28wt%, 3.38wt% containing zinc, germanic 3.24wt%, 0.45wt% containing silica, No. 6 of iron content 2.38wt% wash rear tannin 112 grams of germanium slag weight in wet base and 3.45g/l containing zinc, 0.001g/l containing silica, germanic 0.0001g/l, 0.21g/l containing ferrous iron, No. 6 0.84 liter of the germanium wash heat water of the 0.001g/l containing ferric iron.No. 6 germanium wash heat water, which return once to leach, does pulp liquid, washes rear tannin germanium 18.54wt% containing zinc, germanic 18.04wt%, two are obtained after slag is dried at 105 DEG C and at 550 ~ 600 DEG C after calcination cause weight 8.72 grams micro of germanium concentrate of silica 2.49wt%, iron 13.25wt%, sulphur 1.31wt%, lead is to be vended.
It is by can be calculated each economic target：
1. the leaching process of the zinc oxide fumes：Lead recovery 99.98wt%, silver raising recovery rate are 97.34wt%, the leaching of zinc Extracting rate is that 97.01wt%, the leaching rate 75.97wt% of silica, the leaching rate of germanium are that 91.99wt%, the leaching rate of indium are 96.04wt%, the leaching rate of iron are 90.97wt%.
2. in silica purge and adsorption process, the rate of deposition of silicon reaches 99.46wt%, is adsorbed due to adding coke, mistake Filter performance is substantially improved, liquid also special limpid, no suspended substance after the heavy silicon produced, completely eliminate silicon to heavy indium, heavy germanium and The influence of filtering；While realizing effective recovery indium, also improve the quality of produced germanium concentrate, make germanium concentrate reach it is superfine with On grade, and added coke gets back during next step rotary kiln evaporation and makes full use of.
3. whole synthetical recovery process zinc loss 3.57wt%, i.e. zinc recovery 96.43wt%.
4. whole synthetical recovery process germanium rate of recovery 90.62wt%.
5. whole synthetical recovery process indium recovery 95.40wt%.
Embodiment 3
The oxidation that the rotary kiln evaporation carried out using Yunnan Luoping Zinc ＆ Electricity Co., Ltd.'s zinc hydrometallurgy leached mud is produced Zn dust, wherein 50wt% containing zinc, germanium 0.02wt%, indium 0.015wt%, lead 6wt%, silica 5wt%, silver 0.003wt%, iron 4wt%。
1）Once leach：Zinc oxide fumes is pressed 6 with zinc electrolytic waste liquid：1 liquid-solid ratio carries out pulp, 25 points of slurry time Clock, was carried out after adjusting the acid 125g/l that begins, 80 DEG C of control process temperature, extraction time 1.2 hours, terminal pH=1.2 with the concentrated sulfuric acid Filter 1, filtering No. 1 leached mud of 1 output and No. 1 leachate, No. 1 leached mud carry out secondary leaching, and No. 1 leachate carries out the purification of silicon And absorption；
2）It is secondary to leach：4 are pressed to No. 1 leached mud with industrial water：1 liquid-solid ratio carries out pulp, is adjusted and begun with the concentrated sulfuric acid Filtering 2 is carried out after sour 135g/l, 92 DEG C of control process temperature, extraction time 3.5 hours, terminal acid 55g/l, 2 output 2 is filtered Leached mud and No. 2 leachates, No. 2 leached muds do the sale of lead silver preparation concentrate, and No. 2 leachates, which return once to leach, does pulp liquid；
3）The purification and absorption of silicon：Preceding liquid is done with No. 1 leachate, 72 DEG C is warming up to, adds ox glue solution, addition is Ox glue：Amount=1.5 of silica in solution：1, be slowly added to while stirring during addition, add stirring 25 minutes after, add The activated carbon of 80 eye mesh screens is crossed, addition is 0.85kg/m3, filter 23, filter 23 are carried out after being stirred for 18 minutes, static 45 minutes No. 3 silicon breezes of output and No. 3 filtered fluids, No. 3 silicon breezes send rotary kiln evaporation to reclaim valuable metal therein, and No. 3 filtered fluids enter The heavy indium of the neutralization of row next step；
4）Neutralize heavy indium：With No. 3 filtered fluids after silica purge, 68 DEG C are warming up to, the 18wt%'s for being slowly added to have prepared Aqueous sodium carbonate, solution acidity pH value is adjusted to behind 3.2, static 25 minutes carry out filtering 4, filters No. 4 indium concentrate of 4 output With liquid after No. 4 heavy indiums for carrying out the heavy germanium of next step；
5）Tannin sinks germanium：With liquid after No. 4 heavy indiums, be warming up to 65 DEG C, 30 times of tannic acid multiplying power, stirring carried out after 32 minutes Filter 5, filtering 5 obtains liquid power transmission Zn system after liquid after No. 5 tannin germanium slags and No. 5 heavy germanium, No. 5 heavy germanium and reclaims zinc, and produces No. 5 lists Peaceful germanium slag is in liquid-solid ratio 3.5：1st, filtering 6 is carried out after being washed 35 minutes under temperature 70 C, filtering 6 obtains No. 6 and washes rear tannin germanium slag With No. 6 germanium wash heat water, No. 6 are washed the germanium concentrate sale that rear tannin germanium slag drying, calcination obtain germanic 17.58wt%, No. 6 germanium slags Wash water is returned once to leach and sized mixing.
It is by can be calculated each economic target：
1. the leaching process of the zinc oxide fumes：Lead recovery 99.99wt%, silver raising recovery rate are 97.54wt%, the leaching of zinc Extracting rate is that 97.10wt%, the leaching rate 76.97wt% of silica, the leaching rate of germanium are that 92.99wt%, the leaching rate of indium are 96.24wt%, the leaching rate of iron are 91.09wt%.
2. in silica purge and adsorption process, the rate of deposition of silicon reaches 99.50wt%, is adsorbed due to adding activated carbon, Strainability is substantially improved, and liquid also special limpid, no suspended substance, completely eliminates silicon to heavy indium, heavy germanium after the heavy silicon produced And the influence of filtering.While realizing effective recovery indium, the quality of produced germanium concentrate is also improved, germanium concentrate is reached superfine More than grade, and added activated carbon gets back during next step rotary kiln evaporation and makes full use of.
3. whole synthetical recovery process zinc loss 3.72wt%, i.e. zinc recovery 96.28wt%.
4. whole synthetical recovery process germanium rate of recovery 90.52wt%.
5. whole synthetical recovery process indium recovery 95.33wt%.
Embodiment 4
The oxidation that the rotary kiln evaporation carried out using Yunnan Luoping Zinc ＆ Electricity Co., Ltd.'s zinc hydrometallurgy leached mud is produced Zn dust, wherein 55wt% containing zinc, germanium 0.03wt%, indium 0.025wt%, lead 10wt%, silica 8wt%, silver 0.005wt%, iron 6wt%。
1）Once leach：Pulp liquid is done with zinc electrolytic waste liquid and No. 2 leachates, No. 6 germanium wash heat water, zinc oxide fumes is pressed 7：1 liquid-solid ratio carries out pulp, slurry time 25 minutes, with concentrated sulfuric acid adjustment beginning acid 125g/l, 80 DEG C of control process temperature, leaching Go out and filtering 1 is carried out behind 1.4 hours time, terminal pH=1.4, filtering No. 1 leached mud of 1 output and No. 1 leachate, No. 1 leached mud enter Row is secondary to be leached, and No. 1 leachate carries out the purification and absorption of silicon；
2）It is secondary to leach：5 are pressed to No. 1 leached mud with zinc electrolytic waste liquid：1 liquid-solid ratio carries out pulp, is adjusted with the concentrated sulfuric acid Begin acid 135g/l, carries out filtering 2 after 94 DEG C of control process temperature, extraction time 3.5 hours, terminal acid 55g/l, filters 2 outputs 2 Number leached mud and No. 2 leachates, No. 2 leached muds do the sale of lead silver preparation concentrate, and No. 2 leachates, which return once to leach, does pulp liquid；
3）The purification and absorption of silicon：Preceding liquid is done with No. 1 leachate, 70 DEG C is warming up to, adds ox glue solution, addition is Ox glue：Amount=1.2 of silica in solution：1, be slowly added to while stirring during addition, add stirring 25 minutes after, add The charcoal of 80 eye mesh screens is crossed, addition is 0.90kg/m3, it is stirred for after 18 minutes, static 45 minutes carrying out filter 23, filter 23 production Go out No. 3 silicon breezes and No. 3 filtered fluids, No. 3 silicon breezes send rotary kiln evaporation to reclaim valuable metal therein, and No. 3 filtered fluids are carried out The heavy indium of the neutralization of next step；
4）Neutralize heavy indium：With No. 3 filtered fluids after silica purge, 65 DEG C are warming up to, the 18wt%'s for being slowly added to have prepared Aqueous sodium carbonate, solution acidity pH value is adjusted to behind 3.2, static 25 minutes carry out filtering 4, filters No. 4 indium concentrate of 4 output With liquid after No. 4 heavy indiums for carrying out the heavy germanium of next step；
5）Tannin sinks germanium：With liquid after No. 4 heavy indiums, be warming up to 60 DEG C, 35 times of tannic acid multiplying power, stirring carried out after 32 minutes Filter 5, filtering 5 obtains liquid power transmission Zn system after liquid after No. 5 tannin germanium slags and No. 5 heavy germanium, No. 5 heavy germanium and reclaims zinc, and produces No. 5 lists Peaceful germanium slag is in liquid-solid ratio 3.5：1st, filtering 6 is carried out after being washed 35 minutes under temperature 70 C, filtering 6 obtains No. 6 and washes rear tannin germanium slag With No. 6 germanium wash heat water, No. 6 are washed the germanium concentrate sale that rear tannin germanium slag drying, calcination obtain germanic 18.12wt%, No. 6 germanium slags Wash water is returned once to leach and sized mixing.
It is by can be calculated each economic target：
1. the leaching process of the zinc oxide fumes：Lead recovery 99.95wt%, silver raising recovery rate are 97.48wt%, zinc leaching Rate is that 97.13wt%, silica leaching rate 76.78wt%, the leaching rate of germanium are that 92.85wt%, the leaching rate of indium are 96.19wt%, the leaching rate of iron are 91.67wt%.
2. in silica purge and adsorption process, the rate of deposition of silicon reaches 99.48wt%, is adsorbed due to adding charcoal, mistake Filter performance is substantially improved, liquid also special limpid, no suspended substance after the heavy silicon produced, completely eliminate silicon to heavy indium, heavy germanium and The influence of filtering.While realizing effective recovery indium, also improve the quality of produced germanium concentrate, make germanium concentrate reach it is superfine with On grade, and added charcoal gets back during next step rotary kiln evaporation and makes full use of.
3. whole synthetical recovery process zinc loss 3.94wt%, i.e. zinc recovery 96.06wt%.
4. whole synthetical recovery process germanium rate of recovery 90.15wt%.
5. whole synthetical recovery process indium recovery 95.36wt%.

Claims (9)

1. a kind of method that valuable metal is reclaimed from the low germanium of high silicon, low indium zinc oxide fumes, it is characterised in that the high silicon is low Germanium, low indium zinc oxide fumes 50wt% containing zinc ~ 55wt%, germanium 0.02wt% ~ 0.03wt%, indium 0.015wt% ~ 0.025wt%, titanium dioxide The step of silicon 5wt% ~ 8wt%, methods described is：
1）Once leach：Zinc oxide fumes is pressed 6 ~ 7 with pulp liquid:1 liquid-solid ratio progress pulp, slurry time 20 ~ 30 minutes, With concentrated sulfuric acid adjustment beginning acid 120g/l ~ 130g/l, 75 DEG C ~ 85 DEG C of control process temperature, extraction time 1.0 ~ 1.5 hours, terminal Filtering 1, filtering No. 1 leached mud of 1 output and No. 1 leachate are carried out behind pH=1.1 ~ 1.5, No. 1 leached mud carries out secondary leaching, No. 1 Leachate carries out the purification and absorption of silicon；
2）It is secondary to leach：4 ~ 5 are pressed to No. 1 leached mud with industrial water or zinc electrolytic waste liquid:1 liquid-solid ratio carries out pulp, uses Concentrated sulfuric acid adjustment beginning acid 130g/l ~ 140g/l, 90 DEG C ~ 95 DEG C of control process temperature, extraction time 3.0 ~ 4.0 hours, terminal acid Filtering 2, filtering No. 2 leached muds of 2 output and No. 2 leachates are carried out after 50 ~ 60g/l, No. 2 leached muds do the sale of lead silver preparation concentrate, No. 2 Leachate, which returns once to leach, does pulp liquid；
3）The purification and absorption of silicon：Preceding liquid is done with No. 1 leachate, 70 DEG C ~ 75 DEG C is warming up to, adds ox glue solution, addition For ox glue:Amount=1 ~ 1.5 of silica in solution:1, be slowly added to while stirring during addition, add stirring 20 ~ 30 minutes it Afterwards, amorphous carbon is added, addition is 0.85 ~ 0.95kg/m3, carried out after being stirred for 15 ~ 20 minutes, static 40 ~ 50 minutes Filter 3, No. 3 silicon breezes of filter 23 output and No. 3 filtered fluids, No. 3 silicon breezes send rotary kiln evaporation to reclaim valuable metal therein, No. 3 Filtered fluid carries out the heavy indium of neutralization of next step；
4）Neutralize heavy indium：With No. 3 filtered fluids after silica purge, be warming up to 65 DEG C ~ 70 DEG C, be slowly added to the 15wt% that has prepared ~ 20wt% aqueous sodium carbonate, solution acidity pH value is adjusted to behind 3.0 ~ 3.5, static 20 ~ 30 minutes carry out filtering 4, filtering Liquid after No. 4 heavy indiums of the 4 indium concentrate of output 4 and the heavy germanium of progress next step；
5）Tannin sinks germanium：With liquid after No. 4 heavy indiums, be warming up to 60 DEG C ~ 70 DEG C, 30 ~ 35 times of tannic acid multiplying power, stirring 30 ~ 35 minutes Filtering 5 is carried out afterwards, and filtering 5 obtains liquid power transmission Zn system after liquid after No. 5 tannin germanium slags and No. 5 heavy germanium, No. 5 heavy germanium and reclaims zinc, and No. 5 tannin germanium slags are produced in liquid-solid ratio 3 ~ 4:1st, filtering 6 is carried out after being washed 30 ~ 40 minutes at 65 DEG C ~ 75 DEG C of temperature, filtering 6 is obtained Rear tannin germanium slag and No. 6 germanium wash heat water are washed to No. 6, rear tannin germanium slag is washed for No. 6 and send the calcination of calcination workshop to obtain germanium concentrate sale, 6 Number germanium wash heat water, which returns once to leach, does pulp liquid.
2. reclaiming the method for valuable metal from the low germanium of high silicon, low indium zinc oxide fumes according to claim 1, its feature exists In step 1）The pulp liquid is the one or more in industrial water, zinc electrolytic waste liquid, No. 2 leachates, No. 6 germanium wash heat water.
3. reclaiming the method for valuable metal from the low germanium of high silicon, low indium zinc oxide fumes according to claim 1, its feature exists In step 1）Terminal pH=1.2 ~ 1.4.
4. reclaiming the method for valuable metal from the low germanium of high silicon, low indium zinc oxide fumes according to claim 1, its feature exists In step 3）The ox glue solution addition is ox glue:Amount=1.2 ~ 1.4 of silica in solution:1.
5. reclaiming the method for valuable metal from the low germanium of high silicon, low indium zinc oxide fumes according to claim 1, its feature exists In step 3）The ox glue solution is to take ox glue to be added to the aqueous solution for being configured to 20wt% ~ 30wt% in 50 DEG C ~ 60 DEG C water.
6. reclaiming the method for valuable metal from the low germanium of high silicon, low indium zinc oxide fumes according to claim 1, its feature exists In step 3）The amorphous carbon is the one or more in coke, activated carbon, charcoal.
7. reclaiming the method for valuable metal from the low germanium of high silicon, low indium zinc oxide fumes according to claim 1, its feature exists In step 3）The amorphous carbon addition is 0.90kg/m3。
8. reclaiming the method for valuable metal from the low germanium of high silicon, low indium zinc oxide fumes according to claim 1, its feature exists In step 3）The amorphous carbon was the amorphous carbon of 80 eye mesh screens.
9. reclaiming the method for valuable metal from the low germanium of high silicon, low indium zinc oxide fumes according to claim 1, its feature exists In step 5）The tannic acid multiplying power is 32 ~ 34 times.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101638725A (en) * 2009-08-14 2010-02-03 扬州宁达贵金属有限公司 Method for enriching germanium concentrates from low-germanium coal dust
CN102618721A (en) * 2012-02-24 2012-08-01 云南五鑫实业有限公司 Method for extracting germanium, indium and zinc from high iron, silicon and manganese materials containing germanium, indium and zinc
CN102703707A (en) * 2012-06-15 2012-10-03 广西金山铟锗冶金化工有限公司 Method for recovering indium and germanium from zinc leaching residue
CN103045863A (en) * 2013-01-25 2013-04-17 株洲冶炼集团股份有限公司 Method for pretreating indium-containing zinc oxide acid supernatant
JP2013540206A (en) * 2010-10-12 2013-10-31 オウトテック オサケイティオ ユルキネン Method for treating zinc sulfate containing solution
CN104451172A (en) * 2014-08-26 2015-03-25 云南罗平锌电股份有限公司 Method for comprehensively recovering valuable metals from zinc hydrometallurgy high-temperature purification slags

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101638725A (en) * 2009-08-14 2010-02-03 扬州宁达贵金属有限公司 Method for enriching germanium concentrates from low-germanium coal dust
JP2013540206A (en) * 2010-10-12 2013-10-31 オウトテック オサケイティオ ユルキネン Method for treating zinc sulfate containing solution
CN102618721A (en) * 2012-02-24 2012-08-01 云南五鑫实业有限公司 Method for extracting germanium, indium and zinc from high iron, silicon and manganese materials containing germanium, indium and zinc
CN102703707A (en) * 2012-06-15 2012-10-03 广西金山铟锗冶金化工有限公司 Method for recovering indium and germanium from zinc leaching residue
CN103045863A (en) * 2013-01-25 2013-04-17 株洲冶炼集团股份有限公司 Method for pretreating indium-containing zinc oxide acid supernatant
CN104451172A (en) * 2014-08-26 2015-03-25 云南罗平锌电股份有限公司 Method for comprehensively recovering valuable metals from zinc hydrometallurgy high-temperature purification slags

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
沉淀分离法回收真空炼锌渣中铟的研究;王吉华等;《云南冶金》;20160229;第45卷(第1期);第35-36页 *

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