CN107058750B - Germanic Bellamya aeruginosa comprehensive recycling process - Google Patents

Germanic Bellamya aeruginosa comprehensive recycling process Download PDF

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CN107058750B
CN107058750B CN201611245407.6A CN201611245407A CN107058750B CN 107058750 B CN107058750 B CN 107058750B CN 201611245407 A CN201611245407 A CN 201611245407A CN 107058750 B CN107058750 B CN 107058750B
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liquid
germanium
heavy
tannin
temperature
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CN107058750A (en
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崔志祥
王智
王海滨
张建凯
张坤
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DONGYING LUFANG METAL MATERIAL Co Ltd
SHANDONG FANGYUAN NONFERROUS METALS SCIENCE & TECHNOLOGY Co Ltd
DONGYING FANGYUAN NONFERROUS METALS Co Ltd
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DONGYING LUFANG METAL MATERIAL Co Ltd
SHANDONG FANGYUAN NONFERROUS METALS SCIENCE & TECHNOLOGY Co Ltd
DONGYING FANGYUAN NONFERROUS METALS 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • 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
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
    • 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
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/34—Obtaining zinc oxide
    • 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
    • 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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  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
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Abstract

The present invention provides a kind of germanic Bellamya aeruginosa comprehensive recycling process, while recycling common valuable element therein, increase the recycling to germanium, comprehensive uses Jarosite process except techniques such as iron, tannin method sediments, most suitable processing method is used according to the property of material and feature, the recycling of germanium is made to have reached 70% or more；Advantage is：The effect of acidic leaching reaches best；The loss of germanium reaches minimum；Eliminate the influence that iron extracts germanium；The extraction efficiency for improving germanium, increases economic benefit.

Description

Germanic Bellamya aeruginosa comprehensive recycling process
Technical field
The present invention relates to nonferrous metallurgy fields, more particularly, to a kind of germanic Bellamya aeruginosa comprehensive recycling process.
Background technology
Germanium category dissipated metal, only 7ppm in the earth's crust are most of most of to be present in silicate and metal with dilute bulk state In mine.Its excellent physical and chemical properties with unique, and the high-technology fields such as space flight, electronics are widely used in, It plays an important role in the development strategy of country, therefore the recycling of germanium has obtained great development.At present for the extraction of germanium It is most of basic using zinc mineral as raw material.
Cigarette ash is that the flue dust that smelt stage generates in copper metallurgy industry passes through the electric cigarette ash received that gathers dust, industrial generally to return Receive copper therein, zinc etc..In the produced Copper making cigarette ash of domestic and international copper smelting plant, arsenic content is very high, up to 15-17%, meanwhile, contain There are the valuable metals such as copper, zinc, gold, silver, it is worth mentioning at this point that contain the higher dissipated metal Germanium of content.For many years, not It is handled, storage accumulation.Since arsenic content is very high, secondary arsenic pollution is caused, also overstocks resource fund.
Invention content
It is an object of the invention to solve the deficiencies in the prior art, and provide a kind of germanic Bellamya aeruginosa synthetical recovery work Skill.
The new technical solution of the present invention is：Germanic Bellamya aeruginosa comprehensive recycling process, the technological process roast for Bellamya aeruginosa Cigarette ash sulfuric acid leaching → sulfuric acid leaching slag alkali leaching → alkali phase analysis sulfuric acid and salt Ore Leaching → precipitating alum and removing iron after burning → roasting → After the neutralization of alkali immersion liquid sulfuric acid solution neutralization → alkali immersion liquid after liquid tannin sinking germanium → sulphuric leachate and precipitating alum and removing iron liquid it is mixed The vulcanization for sharing liquid after liquid tannin sinking germanium after the neutralization of lye neutralization → mixed liquor → heavy germanium slag drying calcining → tannin sinking germanium is heavy After copper → synthesis scorodite → arsenic removal zinc oxide is produced with heavy zinc → basic zinc carbonate in liquid；Detailed process is：
Non- oxidizing component when cigarette ash is after 300 ~ 350 DEG C roast 2h in cigarette ash is aoxidized, and is stirred for 1 ~ 2 time during drying It mixes；
The cigarette ash of oxidation is subjected to acidic leaching beginning acid 50 ~ 70g/L, L using sulfuric acid:S=4~6:1；90 ~ 95 DEG C of temperature, Mechanical agitation 2h, germanium respectively enter in leachate and leached mud；
Leached mud is leached into germanium in slag and liquid using alkaline leaching respectively, 150 ~ 200g/L of NaOH concentration；Temperature 90 ~ 95 ℃；Mechanical agitation 2h；
Alkali leaching liquor leaches the acid concentration that wherein begins by nitration mixture：H2SO4170g/L, NaCl：30g/L, NaClO3：20g/ L, CaCl2：20g/L；L:S=5:1；Temperature：80~84℃；Mechanical agitation 2 hours；
The nitration mixture leachate caustic lye of soda of 180 ~ 200g/L adjusts pH value to 1.5 ~ 1.8, removes iron ion；
Alkali immersion liquid adjusts pH value to 2.5 ~ 3.0, during alkali immersion liquid is carried out with sulfuric acid solution with a concentration of 180 ~ 200g/L sulfuric acid With no precipitation generation；Tannin sinking germanium after next step tannin sinking germanium neutralizes directly is carried out, germanium concentrate is obtained after drying calcining；In It is 25 ~ 30 times in solution containing germanium amount with tannin amount is added in rear liquid, by tannin according to liquid-solid ratio 3:1 in 40 ~ 50 DEG C of temperature Left and right water dissolution；Liquid is warming up to 50 ~ 55 DEG C after neutralization, and tannin solution is added, and mechanical agitation reacts 30 minutes, reaches terminal Germanic standard filters, and liquid carries out vulcanizing heavy copper process after heavy germanium, and heavy germanium slag send drying, and calcining sequence；
Drying calcining：Heavy germanium slag is dried in an oven, removes moisture；It is put into Muffle furnace and is calcined, temperature is at 550 DEG C ~ 600 DEG C, stirring in every 30 minutes is primary, and for time control at 4 hours, taking-up was air-cooled to room temperature；
Liquid is by heavy copper after heavy germanium；It is passed through H2S gases, detection in every 20 minutes are primary；Terminal cupric：≤0.01g/L；Machinery Stirring, 300 ~ 360r/min of rotating speed；
Heavy arsenic：Fe/As=1.5（Molar ratio）；H2O2The Fe contained in oxidation solution2+→Fe3+、As3+→As5+Meet synthesis The requirement of scorodite technology；NaOH adjusts pH value to 3.0 ~ 4.0；Temperature：90℃±5℃；Time：2 ~ 3 hours；Terminal contains arsenic：≤ 0.01g/L；Mechanical agitation, 100 ~ 120r/min of rotating speed；
Heavy zinc：NaOH adjusts pH value to 5 or so；Na2CO3PH value is adjusted to 7.0 ~ 7.2；Temperature：50℃±5℃；Time： 30 minutes；Mechanical agitation, 100 ~ 120r/min of rotating speed；
Terminal contains zinc：≤ 0.01g/L, obtains sulfuric acid monohydrate zinc product and waste water, and waste water send wastewater treatment.
The Bellamya aeruginosa roasting：Cigarette ash is packed into iron pan and is put into Muffle kiln roasting, controls 300 DEG C ± 20 DEG C of temperature, phase Between stirring in every 30 minutes it is primary, prevent from luming, react fully progresss, after reaction 2 hours, takes out and is air-cooled to room temperature；
Cigarette ash sulfuric acid leaching after the roasting：Claim fired slags weight, according to liquid-solid ratio 5:1 adds water in a reservoir, adds Sulfuric acid stirs, and fired slags are added and are warming up to 95 DEG C of ± 5 DEG C of beginning timing, and reaction is filtered after 2 hours, wet slag dried, solution Retain；
The sulfuric acid leaching slag alkali leaching：After acid leaching residue drying, by grinding, according to liquid-solid ratio 5:1 calculates addition water Amount, the alkali number calculated with water dissolution after acid leaching residue is added for stirring, are warming up to 95 DEG C ± 5 DEG C, keep temperature 2 hours, mistake Filter, the drying of alkali phase analysis, alkali immersion liquid retain；
The alkali phase analysis sulfuric acid and salt Ore Leaching：According to liquid-solid ratio 5:1 calculates addition water, and solvent is added in water H2SO4And auxiliary material NaCl, CaCl2Dissolving is added alkali phase analysis and is warming up to 80 ~ 84 DEG C, divides 4 times and NaClO is averagely added3, keep temperature Degree 2 hours, filtering, the drying of nitration mixture leached mud, leachate retain；
The precipitating alum and removing iron：Iron ion containing high concentration in nitration mixture leachate removes iron, first by solution using Jarosite process 90 DEG C ± 5 DEG C are warming up to, pH value is adjusted to 1.5 ~ 1.8 with lye, reacts 2 hours, reach terminal iron content standard, filter, filter residue Drying obtains iron vitriol slag, and liquid retains；
The alkali immersion liquid is neutralized with sulfuric acid solution：Alkali immersion liquid adjusts pH value to 2.5 ~ 3.0 with a concentration of 200g/L sulfuric acid, Alkali immersion liquid is neutralized with sulfuric acid solution, and no precipitation generates；
Liquid tannin sinking germanium after the neutralization of the alkali immersion liquid：It is the germanium amount contained in solution that tannin amount is added after neutralization in liquid 30 times, by tannin according to liquid-solid ratio 3:1 in temperature 50 C or so water dissolution；Liquid is warming up to 50 ~ 55 DEG C after neutralization, is added red Peaceful solution, mechanical agitation react 30 minutes, reach the germanic standard of terminal, filter, and liquid send synthesis scorodite process after heavy germanium, sinks Germanium slag send drying, and calcining sequence；
The mixed liquor of liquid is neutralized with lye after the sulphuric leachate and precipitating alum and removing iron：Sulphuric leachate and precipitating alum and removing iron Afterwards after liquid mixing with the sodium hydroxide of 200 ± 50g/L adjusting pH value to 2.5 ~ 3.0, liquid after sulphuric leachate and precipitating alum and removing iron Mixed liquor neutralized with lye, filter, neutralize slag send to copper smelting by pyrometallurgy, after neutralization liquid carry out next step tannin sinking germanium；
Liquid tannin sinking germanium after the neutralization of the mixed liquor：It is to contain germanium amount in solution that tannin amount is added after neutralization in liquid 30 times, by tannin according to liquid-solid ratio 3:1 after temperature 50 C or so water dissolution, neutralization liquid be warming up to 50 ~ 55 DEG C, tannin is added Solution, mechanical agitation react 30 minutes, reach the germanic standard of terminal, filter, and liquid carries out vulcanizing heavy copper process after heavy germanium, heavy germanium Slag send drying, and calcining sequence；
The heavy germanium slag drying calcining：Heavy germanium slag is dried in an oven, is removed moisture, is put into Muffle furnace and is forged It burns, for temperature at 550 DEG C ~ 600 DEG C, stirring in every 30 minutes is primary, and for time control at 4 hours, taking-up was air-cooled to room temperature；
The heavy copper of the vulcanization of liquid after the tannin sinking germanium：Contain valuable element copper after tannin sinking germanium in liquid, is passed through H2S gas Body carries out vulcanizing heavy copper, and temperature is room temperature, is carried out in the good draught cupboard of performance of ventilating, and detection in every 20 minutes is primary, and about 3 Hour terminates, and terminal cupric≤0.01g/L stoppings are passed through hydrogen sulfide gas, filter, and send pyrogenic process to melt copper, liquid after vulcanization copper ashes drying Body is further processed；
The synthesis scorodite：Liquid after liquid after the heavy germanium of the neutralization of alkali immersion liquid and the heavy copper of vulcanization is mixed, is rubbed according to iron arsenic You are than being added a certain amount of iron, to ensure that iron is positive trivalent and arsenic is positive pentavalent, hydrogen peroxide oxidation is added, then titration detects Completely whether conversion is qualified for iron, arsenic, adjusts pH value to 3.0 ~ 4.0 with sodium hydroxide, is warming up to 90 DEG C ± 5 DEG C, keeps temperature 2 ~ 3 Hour, terminal filters after containing arsenic≤0.01g/L, and the drying of scorodite slag, liquid carries out the next step after arsenic removal；
After the arsenic removal in liquid and heavy zinc：Liquid sodium hydroxide adjusts pH value to 5 or so after arsenic removal, and carbonic acid is then added Sodium adjusts pH value to 7.0 ~ 7.2, and heating is heated to 50 DEG C ± 5 DEG C, keeps temperature, stirs 30 minutes, and terminal contains zinc≤0.01g/ L, filtering, filtrate carry out wastewater treatment, and basic carbonate cadmia carries out drying calcination processing；
The basic zinc carbonate produces zinc oxide：Basic carbonate cadmia is put into Muffle furnace, 550 DEG C of temperature of control ± 20 DEG C, the time is set as 3 hours, and stirring in every 30 minutes is primary, finally carries out air-cooled obtaining wet oxidation zinc.The present invention's is beneficial Effect is：The sulfide in cigarette ash is changed into oxide by roasting, the effect of acidic leaching is made to reach best；In entire work Multiple workshop sections of skill recycle germanium, it is ensured that the loss of germanium reaches minimum；Because iron is affected to extraction germanium, use Jarosite process can remove iron to≤0.5g/L except iron, eliminate the influence that iron extracts germanium；Using tannin method sink germanium, can by germanium from It is extracted into tannin in solution, makes Ge content≤1mg/L in solution；The extraction efficiency of germanium can be reached to 70%, increase warp Ji benefit.
Description of the drawings
Fig. 1 is the process flow chart of the present invention.
Specific implementation mode
The present invention will be further described below with reference to the drawings.
Germanic Bellamya aeruginosa comprehensive recycling process, the cigarette ash sulfuric acid leaching after the technological process Bellamya aeruginosa roasting → roasting → sulfuric acid leaching slag alkali leaching → alkali phase analysis sulfuric acid and salt Ore Leaching → precipitating alum and removing iron → alkali immersion liquid sulfuric acid solution neutralization → alkali After the neutralization of immersion liquid after liquid tannin sinking germanium → sulphuric leachate and precipitating alum and removing iron the mixing of liquid in lye neutralization → mixed liquor With liquid after the heavy copper → synthesis scorodite → arsenic removal of vulcanization of liquid after rear liquid tannin sinking germanium → heavy germanium slag drying calcining → tannin sinking germanium It neutralizes heavy zinc → basic zinc carbonate and produces zinc oxide；Detailed process is：
Non- oxidizing component when cigarette ash is after 300 ~ 350 DEG C roast 2h in cigarette ash is aoxidized, and is stirred for 1 ~ 2 time during drying It mixes；
The cigarette ash of oxidation is subjected to acidic leaching beginning acid 50 ~ 70g/L, L using sulfuric acid:S=4~6:1；90 ~ 95 DEG C of temperature, Mechanical agitation 2h, germanium respectively enter in leachate and leached mud；
Leached mud is leached into germanium in slag and liquid using alkaline leaching respectively, 150 ~ 200g/L of NaOH concentration；Temperature 90 ~ 95 ℃；Mechanical agitation 2h；
Alkali leaching liquor leaches the acid concentration that wherein begins by nitration mixture：H2SO4170g/L, NaCl：30g/L, NaClO3：20g/ L, CaCl2：20g/L；L:S=5:1；Temperature：80~84℃；Mechanical agitation 2 hours；
The nitration mixture leachate caustic lye of soda of 180 ~ 200g/L adjusts pH value to 1.5 ~ 1.8, removes iron ion；
Alkali immersion liquid adjusts pH value to 2.5 ~ 3.0, during alkali immersion liquid is carried out with sulfuric acid solution with a concentration of 180 ~ 200g/L sulfuric acid With no precipitation generation；Tannin sinking germanium after next step tannin sinking germanium neutralizes directly is carried out, germanium concentrate is obtained after drying calcining；In It is 25 ~ 30 times in solution containing germanium amount with tannin amount is added in rear liquid, by tannin according to liquid-solid ratio 3:1 in 40 ~ 50 DEG C of temperature Left and right water dissolution；Liquid is warming up to 50 ~ 55 DEG C after neutralization, and tannin solution is added, and mechanical agitation reacts 30 minutes, reaches terminal Germanic standard filters, and liquid carries out vulcanizing heavy copper process after heavy germanium, and heavy germanium slag send drying, and calcining sequence；
Drying calcining：Heavy germanium slag is dried in an oven, removes moisture；It is put into Muffle furnace and is calcined, temperature is at 550 DEG C ~ 600 DEG C, stirring in every 30 minutes is primary, and for time control at 4 hours, taking-up was air-cooled to room temperature；
Liquid is by heavy copper after heavy germanium；It is passed through H2S gases, detection in every 20 minutes are primary；Terminal cupric：≤0.01g/L；Machinery Stirring, 300 ~ 360r/min of rotating speed；
Heavy arsenic：Fe/As=1.5（Molar ratio）；H2O2The Fe contained in oxidation solution2+→Fe3+、As3+→As5+Meet synthesis The requirement of scorodite technology；NaOH adjusts pH value to 3.0 ~ 4.0；Temperature：90℃±5℃；Time：2 ~ 3 hours；Terminal contains arsenic：≤ 0.01g/L；Mechanical agitation, 100 ~ 120r/min of rotating speed；
Heavy zinc：NaOH adjusts pH value to 5 or so；Na2CO3PH value is adjusted to 7.0 ~ 7.2；Temperature：50℃±5℃；Time： 30 minutes；Mechanical agitation, 100 ~ 120r/min of rotating speed；
Terminal contains zinc：≤ 0.01g/L, obtains sulfuric acid monohydrate zinc product and waste water, and waste water send wastewater treatment.
The Bellamya aeruginosa roasting：Cigarette ash is packed into iron pan and is put into Muffle kiln roasting, controls 300 DEG C ± 20 DEG C of temperature, phase Between stirring in every 30 minutes it is primary, prevent from luming, react fully progresss, after reaction 2 hours, takes out and is air-cooled to room temperature；
Cigarette ash sulfuric acid leaching after the roasting：Claim fired slags weight, according to liquid-solid ratio 5:1 adds water in a reservoir, adds Sulfuric acid stirs, and fired slags are added and are warming up to 95 DEG C of ± 5 DEG C of beginning timing, and reaction is filtered after 2 hours, wet slag dried, solution Retain；
The sulfuric acid leaching slag alkali leaching：After acid leaching residue drying, by grinding, according to liquid-solid ratio 5:1 calculates addition water Amount, the alkali number calculated with water dissolution after acid leaching residue is added for stirring, are warming up to 95 DEG C ± 5 DEG C, keep temperature 2 hours, mistake Filter, the drying of alkali phase analysis, alkali immersion liquid retain；
The alkali phase analysis sulfuric acid and salt Ore Leaching：According to liquid-solid ratio 5:1 calculates addition water, and solvent is added in water H2SO4And auxiliary material NaCl, CaCl2Dissolving is added alkali phase analysis and is warming up to 80 ~ 84 DEG C, divides 4 times and NaClO is averagely added3, keep temperature Degree 2 hours, filtering, the drying of nitration mixture leached mud, leachate retain；
The precipitating alum and removing iron：Iron ion containing high concentration in nitration mixture leachate removes iron, first by solution using Jarosite process 90 DEG C ± 5 DEG C are warming up to, pH value is adjusted to 1.5 ~ 1.8 with lye, reacts 2 hours, reach terminal iron content standard, filter, filter residue Drying obtains iron vitriol slag, and liquid retains；
The alkali immersion liquid is neutralized with sulfuric acid solution：Alkali immersion liquid adjusts pH value to 2.5 ~ 3.0 with a concentration of 200g/L sulfuric acid, Alkali immersion liquid is neutralized with sulfuric acid solution, and no precipitation generates；
Liquid tannin sinking germanium after the neutralization of the alkali immersion liquid：It is the germanium amount contained in solution that tannin amount is added after neutralization in liquid 30 times, by tannin according to liquid-solid ratio 3:1 in temperature 50 C or so water dissolution；Liquid is warming up to 50 ~ 55 DEG C after neutralization, is added red Peaceful solution, mechanical agitation react 30 minutes, reach the germanic standard of terminal, filter, and liquid send synthesis scorodite process after heavy germanium, sinks Germanium slag send drying, and calcining sequence；
The mixed liquor of liquid is neutralized with lye after the sulphuric leachate and precipitating alum and removing iron：Sulphuric leachate and precipitating alum and removing iron Afterwards after liquid mixing with the sodium hydroxide of 200 ± 50g/L adjusting pH value to 2.5 ~ 3.0, liquid after sulphuric leachate and precipitating alum and removing iron Mixed liquor neutralized with lye, filter, neutralize slag send to copper smelting by pyrometallurgy, after neutralization liquid carry out next step tannin sinking germanium；
Liquid tannin sinking germanium after the neutralization of the mixed liquor：It is to contain germanium amount in solution that tannin amount is added after neutralization in liquid 30 times, by tannin according to liquid-solid ratio 3:1 after temperature 50 C or so water dissolution, neutralization liquid be warming up to 50 ~ 55 DEG C, tannin is added Solution, mechanical agitation react 30 minutes, reach the germanic standard of terminal, filter, and liquid carries out vulcanizing heavy copper process after heavy germanium, heavy germanium Slag send drying, and calcining sequence；
The heavy germanium slag drying calcining：Heavy germanium slag is dried in an oven, is removed moisture, is put into Muffle furnace and is forged It burns, for temperature at 550 DEG C ~ 600 DEG C, stirring in every 30 minutes is primary, and for time control at 4 hours, taking-up was air-cooled to room temperature；
The heavy copper of the vulcanization of liquid after the tannin sinking germanium：Contain valuable element copper after tannin sinking germanium in liquid, is passed through H2S gas Body carries out vulcanizing heavy copper, and temperature is room temperature, is carried out in the good draught cupboard of performance of ventilating, and detection in every 20 minutes is primary, and about 3 Hour terminates, and terminal cupric≤0.01g/L stoppings are passed through hydrogen sulfide gas, filter, and send pyrogenic process to melt copper, liquid after vulcanization copper ashes drying Body is further processed；
The synthesis scorodite：Liquid after liquid after the heavy germanium of the neutralization of alkali immersion liquid and the heavy copper of vulcanization is mixed, is rubbed according to iron arsenic You are than being added a certain amount of iron, to ensure that iron is positive trivalent and arsenic is positive pentavalent, hydrogen peroxide oxidation is added, then titration detects Completely whether conversion is qualified for iron, arsenic, adjusts pH value to 3.0 ~ 4.0 with sodium hydroxide, is warming up to 90 DEG C ± 5 DEG C, keeps temperature 2 ~ 3 Hour, terminal filters after containing arsenic≤0.01g/L, and the drying of scorodite slag, liquid carries out the next step after arsenic removal；
After the arsenic removal in liquid and heavy zinc：Liquid sodium hydroxide adjusts pH value to 5 or so after arsenic removal, and carbonic acid is then added Sodium adjusts pH value to 7.0 ~ 7.2, and heating is heated to 50 DEG C ± 5 DEG C, keeps temperature, stirs 30 minutes, and terminal contains zinc≤0.01g/ L, filtering, filtrate carry out wastewater treatment, and basic carbonate cadmia carries out drying calcination processing；
The basic zinc carbonate produces zinc oxide：Basic carbonate cadmia is put into Muffle furnace, 550 DEG C of temperature of control ± 20 DEG C, the time is set as 3 hours, and stirring in every 30 minutes is primary, finally carries out air-cooled obtaining wet oxidation zinc.The present invention's is beneficial Effect is：The sulfide in cigarette ash is changed into oxide by roasting, the effect of acidic leaching is made to reach best；In entire work Multiple workshop sections of skill recycle germanium, it is ensured that the loss of germanium reaches minimum；Because iron is affected to extraction germanium, use Jarosite process can remove iron to≤0.5g/L except iron, eliminate the influence that iron extracts germanium；Using tannin method sink germanium, can by germanium from It is extracted into tannin in solution, makes Ge content≤1mg/L in solution；The extraction efficiency of germanium can be reached to 70%, increase warp Ji benefit.

Claims (2)

1. germanic Bellamya aeruginosa comprehensive recycling process, it is characterised in that：The technological process is after Bellamya aeruginosa roasting → roasting Cigarette ash sulfuric acid leaching → sulfuric acid leaching slag alkali leaching → alkali phase analysis sulfuric acid and salt Ore Leaching → precipitating alum and removing iron → alkali immersion liquid sulfuric acid The mixing of liquid is neutralized with lye after liquid tannin sinking germanium → sulphuric leachate and precipitating alum and removing iron after the neutralization of solution neutralization → alkali immersion liquid Liquid tannin sinking germanium → heavy germanium slag dries the smelly green onion of the heavy copper → synthesis of vulcanization of liquid after calcining → tannin sinking germanium after the neutralization of → mixed liquor After stone → arsenic removal zinc oxide is produced with heavy zinc → basic zinc carbonate in liquid；Detailed process is：
（1）Non- oxidizing component when cigarette ash is after 300 ~ 350 DEG C roast 2h in cigarette ash is aoxidized, and is stirred for 1 ~ 2 time during drying It mixes；
（2）The cigarette ash of oxidation is subjected to acidic leaching beginning acid 50 ~ 70g/L, L using sulfuric acid:S=4~6:1；90 ~ 95 DEG C of temperature, machine Tool stirs 2h, and germanium respectively enters in leachate and leached mud；
（3）Leached mud is leached into germanium in slag and liquid using alkaline leaching respectively, 150 ~ 200g/L of NaOH concentration；Temperature 90 ~ 95 ℃；Mechanical agitation 2h；
（4）Alkali leaching liquor leaches the acid concentration that wherein begins by nitration mixture：H2SO4170g/L, NaCl：30g/L, NaClO3：20g/ L, CaCl2：20g/L；L:S=5:1；Temperature：80~84℃；Mechanical agitation 2 hours；
（5）The nitration mixture leachate caustic lye of soda of 180 ~ 200g/L adjusts pH value to 1.5 ~ 1.8, removes iron ion；
（6）Alkali immersion liquid adjusts pH value to 2.5 ~ 3.0, during alkali immersion liquid is carried out with sulfuric acid solution with a concentration of 180 ~ 200g/L sulfuric acid With no precipitation generation；Tannin sinking germanium after next step tannin sinking germanium neutralizes directly is carried out, germanium concentrate is obtained after drying calcining；In It is 25 ~ 30 times in solution containing germanium amount with tannin amount is added in rear liquid, by tannin according to liquid-solid ratio 3:1 in 40 ~ 50 DEG C of temperature Use water dissolution；Liquid is warming up to 50 ~ 55 DEG C after neutralization, and tannin solution is added, and mechanical agitation reacts 30 minutes, it is germanic to reach terminal Standard filters, and liquid carries out vulcanizing heavy copper process after heavy germanium, and heavy germanium slag send drying, and calcining sequence；
（7）Drying calcining：Heavy germanium slag is dried in an oven, removes moisture；Be put into Muffle furnace and calcined, temperature 550 DEG C ~ 600 DEG C, stirring in every 30 minutes is primary, and for time control at 4 hours, taking-up was air-cooled to room temperature；
（8）Liquid is by heavy copper after heavy germanium；It is passed through H2S gases, detection in every 20 minutes are primary；Terminal cupric：≤0.01g/L；Machinery stirs It mixes, 300 ~ 360r/min of rotating speed；
（9）Heavy arsenic：Molar ratio=1.5 Fe/As；H2O2The Fe contained in oxidation solution2+→Fe3+、As3+→As5+Meet and synthesizes smelly green onion Stone technique requirement；NaOH adjusts pH value to 3.0 ~ 4.0；Temperature：90℃±5℃；Time：2 ~ 3 hours；Terminal contains arsenic：≤ 0.01g/L；Mechanical agitation, 100 ~ 120r/min of rotating speed；
（10）Heavy zinc：NaOH adjusts pH value to 5；Na2CO3PH value is adjusted to 7.0 ~ 7.2；Temperature：50℃±5℃；Time：30 points Clock；Mechanical agitation, 100 ~ 120r/min of rotating speed；
Terminal contains zinc：≤ 0.01g/L, obtains sulfuric acid monohydrate zinc product and waste water, and waste water send wastewater treatment.
2. germanic Bellamya aeruginosa comprehensive recycling process according to claim 1, it is characterised in that：
（1）The Bellamya aeruginosa roasting：Cigarette ash is packed into iron pan and is put into Muffle kiln roasting, controls 300 DEG C of temperature, during which every 30 points Clock stirring is primary, prevents from luming, and react fully progress, and after reacting 2 hours, taking-up is air-cooled to room temperature；
（2）Cigarette ash sulfuric acid leaching after the roasting：Claim fired slags weight, according to liquid-solid ratio 5:1 adds water in a reservoir, adds sulphur Acid stirring, and fired slags are added and are warming up to 95 DEG C of beginning timing, reaction filters after 2 hours, wet slag is dried, and solution retains；
（3）The sulfuric acid leaching slag alkali leaching：After acid leaching residue drying, by grinding, according to liquid-solid ratio 5:1 calculates addition water Amount, the alkali number calculated with water dissolution after acid leaching residue is added for stirring, are warming up to 95 DEG C, keep temperature 2 hours, filtering, alkali leaching Slag is dried, and alkali immersion liquid retains；
（4）The alkali phase analysis sulfuric acid and salt Ore Leaching：According to liquid-solid ratio 5:1 calculates addition water, and solvent is added in water H2SO4And auxiliary material NaCl, CaCl2Dissolving is added alkali phase analysis and is warming up to 80 ~ 84 DEG C, divides 4 times and NaClO is averagely added3, keep temperature Degree 2 hours, filtering, the drying of nitration mixture leached mud, leachate retain；
（5）The precipitating alum and removing iron：Iron ion containing high concentration in nitration mixture leachate removes iron, first by solution using Jarosite process 90 DEG C ± 5 DEG C are warming up to, pH value is adjusted to 1.5 ~ 1.8 with lye, reacts 2 hours, reach terminal iron content standard, filter, filter residue Drying obtains iron vitriol slag, and liquid retains；
（6）The alkali immersion liquid is neutralized with sulfuric acid solution：Alkali immersion liquid adjusts pH value to 2.5 ~ 3.0 with a concentration of 200g/L sulfuric acid, Alkali immersion liquid is neutralized with sulfuric acid solution, and no precipitation generates；
（7）Liquid tannin sinking germanium after the neutralization of the alkali immersion liquid：It is the germanium amount contained in solution that tannin amount is added after neutralization in liquid 30 times, by tannin according to liquid-solid ratio 3:1 in temperature 50 C water dissolution；Liquid is warming up to 50 ~ 55 DEG C after neutralization, and it is molten that tannin is added Liquid, mechanical agitation react 30 minutes, reach the germanic standard of terminal, filter, and liquid send synthesis scorodite process, heavy germanium slag after heavy germanium Send drying, and calcining sequence；
（8）The mixed liquor of liquid is neutralized with lye after the sulphuric leachate and precipitating alum and removing iron：Sulphuric leachate and precipitating alum and removing iron Afterwards after liquid mixing with the sodium hydroxide of 200 ± 50g/L adjusting pH value to 2.5 ~ 3.0, liquid after sulphuric leachate and precipitating alum and removing iron Mixed liquor neutralized with lye, filter, neutralize slag send to copper smelting by pyrometallurgy, after neutralization liquid carry out next step tannin sinking germanium；
（9）Liquid tannin sinking germanium after the neutralization of the mixed liquor：It is to contain germanium amount in solution that tannin amount is added after neutralization in liquid 30 times, by tannin according to liquid-solid ratio 3:1 after temperature 50 C water dissolution, neutralization liquid be warming up to 50 ~ 55 DEG C, it is molten that tannin is added Liquid, mechanical agitation react 30 minutes, reach the germanic standard of terminal, filter, and liquid carries out vulcanizing heavy copper process after heavy germanium, heavy germanium slag Send drying, and calcining sequence；
（10）The heavy germanium slag drying calcining：Heavy germanium slag is dried in an oven, is removed moisture, is put into Muffle furnace and is forged It burns, for temperature at 550 DEG C ~ 600 DEG C, stirring in every 30 minutes is primary, and for time control at 4 hours, taking-up was air-cooled to room temperature；
（11）The heavy copper of the vulcanization of liquid after the tannin sinking germanium：Contain valuable element copper after tannin sinking germanium in liquid, is passed through H2S gases, It carries out vulcanizing heavy copper, temperature is room temperature, is carried out in the good draught cupboard of performance of ventilating, and detection in every 20 minutes is primary, is tied within 3 hours Beam, terminal cupric≤0.01g/L stoppings are passed through hydrogen sulfide gas, filter, and send pyrogenic process to melt copper after vulcanization copper ashes drying, liquid carries out It handles in next step；
（12）The synthesis scorodite：Liquid after liquid after the heavy germanium of the neutralization of alkali immersion liquid and the heavy copper of vulcanization is mixed, is rubbed according to iron arsenic You are than being added a certain amount of iron, to ensure that iron is positive trivalent and arsenic is positive pentavalent, hydrogen peroxide oxidation is added, then titration detects Completely whether conversion is qualified for iron, arsenic, adjusts pH value to 3.0 ~ 4.0 with sodium hydroxide, is warming up to 90 DEG C ± 5 DEG C, keeps temperature 2 ~ 3 Hour, terminal filters after containing arsenic≤0.01g/L, and the drying of scorodite slag, liquid carries out the next step after arsenic removal；
（13）After the arsenic removal in liquid and heavy zinc：Liquid sodium hydroxide adjusts pH value to 5 after arsenic removal, and sodium carbonate tune is then added PH value is saved to 7.0 ~ 7.2, heating is heated to 50 DEG C ± 5 DEG C, keeps temperature, stirs 30 minutes, and terminal contains zinc≤0.01g/L, mistake Filter, filtrate carry out wastewater treatment, and basic carbonate cadmia carries out drying calcination processing；
（14）The basic zinc carbonate produces zinc oxide：Basic carbonate cadmia is put into Muffle furnace, 550 DEG C of temperature of control ± 20 DEG C, the time is set as 3 hours, and stirring in every 30 minutes is primary, finally carries out air-cooled obtaining wet oxidation zinc.
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