CN106521162B - The method that valuable element is reclaimed from acidic arsenic-containing, iron, sulphur biological oxidation solution - Google Patents

The method that valuable element is reclaimed from acidic arsenic-containing, iron, sulphur biological oxidation solution Download PDF

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CN106521162B
CN106521162B CN201610965387.3A CN201610965387A CN106521162B CN 106521162 B CN106521162 B CN 106521162B CN 201610965387 A CN201610965387 A CN 201610965387A CN 106521162 B CN106521162 B CN 106521162B
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iron
arsenic
oxidation solution
reclaimed
sulphur
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CN106521162A (en
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张世镖
王秀美
郑晔
郝福来
赵俊蔚
赵国惠
李健
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Changchun Gold Research Institute
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Changchun Gold Research Institute
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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
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • 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
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/04—Obtaining arsenic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The present invention relates to a kind of method that valuable element is reclaimed from acidic arsenic-containing, iron, sulphur biological oxidation solution, belong to field of hydrometallurgy.By oxidation solution and extractant through three-level counter-current extraction, the iron ion in oxidation solution is set to enter organic phase and separate and recover；Precipitating reagent is added into the raffinate after separation iron, and the enrichment of element such as arsenic, sulphur and micro copper, lead, zinc, iron in solution is in and in slag；The neutralization slag that separation of solid and liquid obtains obtains calcium sulfate product after sulfuric acid solution leaching arsenic, copper, lead, zinc, iron plasma, through separation of solid and liquid；Vulcanized sodium is added into sulphuric leachate, the arsenic ion in solution is precipitated in the form of arsenones, after separation of solid and liquid, arsenic is reclaimed in the form of arsenones product；The arsenic process for leaching and neutralizing in slag is returned after the added sulfuric acid of acidic liquid after heavy arsenic.Advantage be it is raw materials used easily take, inexpensively, technological process is simple and practical, and valuable element comprehensive recovery is high, can realize waste zero-emission.

Description

The method that valuable element is reclaimed from acidic arsenic-containing, iron, sulphur biological oxidation solution
Technical field
The invention belongs to technical field of wet metallurgy, refer in particular to from acidic arsenic-containing, iron, sulphur plasma biological oxidation solution The method of middle synthetical recovery valuable element.
Background technology
PREPROCESSING OF A REFRACTORY GOLD technique is the novel process to begin one's study the eighties in last century, mainly utilizes chemautotrophy Bacterium and its sulfide mineral of the parcel gold such as the effect of metabolite ferric sulphate, oxidation Decomposition pyrite, mispickel, so that goldc grains Exposure, enables gold grain to be contacted with leaching agent, so as to improve the leaching rate of gold.
Bacterial oxidation method is typical green metallurgical process, it the advantages of be that small investment, production cost be low, technique side Method is simple and convenient to operate.The country has built up more than ten manufacturing enterprise using biological oxidation technique at present, main to include the Liao Dynasty Ning Tianli companies, Jiangxi three and Jin Ye Co., Ltds, crow draw loud, high-pitched sound Mining Limited Company, Jin Feng gold Co., Ltd Deng.In biological oxidation process, the sulfide mineral such as pyrite, mispickel, chalcopyrite, galena, zincblende in Gold Concentrate under Normal Pressure is through thin Entered after bacterium oxidation with iron ion, arsenic ion, copper ion, lead ion, zinc ion, sulfate ion etc. in oxidation solution, and aoxidized The pH value of liquid is strongly acid wastewater in 0.6-1.5, can not be discharged without processing.And for the Gold Concentrate under Normal Pressure of different business processes Minerals composition is different, and the fluctuation of concentration of each ion is also bigger in caused biological oxidation solution, general iron content 20-40g/L, Arsenic 5-15g/L, sulphur 15-35g/L, and a small amount of copper, lead, zinc ion.
The method of conventional process acidic oxidation liquid is lime molysite neutralization precipitation method, i.e., with milk of lime neutralize containing iron ion, The oxidation solution of arsenic ion and sulfuric acid, forms compound stablize, free of contamination, and the method that most manufacturing enterprises' processing neutralize slags is Store up Tailings Dam.
After the neutralized processing of biological oxidation solution, arsenic, iron, sulphur in oxidation solution can be with shapes such as ferric arsenate, calcium arsenate, calcium sulfate Formula is present in neutralization slag, neutralizes slag during Tailings Dam is stored up for a long time, and part arsenic can change with external environment condition and micro- life The effect of thing and dissolve, cause secondary pollution.
During neutralisation treatment biological oxidation solution, usually add milk of lime prepared by calcium oxide and neutralized, made Effects of ion concentration reaches certain standard, and the liquid after neutralization, which returns, to be used or discharge.In the mistake of processing biological oxidation solution Cheng Zhonghui consumes substantial amounts of calcium oxide, increases production cost for manufacturing enterprise, while cause the waste of the resources such as arsenic, iron.If will Valuable element synthetical recovery in biological oxidation solution, can not only reduce the waste to resource, moreover it is possible to which being brought for manufacturing enterprise can The economic benefit of sight.
The content of the invention
The present invention provides a kind of method that valuable element is reclaimed from acidic arsenic-containing, iron, sulphur biological oxidation solution, it is therefore an objective to makes Acidic bio oxidation solution reaches completely innoxious, and realizes comprehensive utilization of resources, reduces the production cost of biological oxidation enterprise, system Standby product is that enterprise brings additional economic benefit.
The present invention adopts the technical scheme that：Comprise the following steps：
（1）The volume ratio of addition oxidation solution and extractant into extraction reactor, organic phase and aqueous phase is 1:0.5~1:3, After being sufficiently mixed 3-15min, aqueous phase and organic phase are separated, through three-level counter-current extraction, makes the Fe in oxidation solution3+Ion enters organic Phase, after back washing agent is stripped, iron is reclaimed the organic phase of load iron in the form of iron chloride, the organic phase circulation profit after back extraction With；
（2）Add precipitating reagent into the raffinate after separation iron, make system pH be 7-10, reaction temperature is 15-50 DEG C, Stirring intensity is 600-800r/min, precipitates the ion contained in raffinate under the conditions of 2 ~ 10h of stirring, and valuable element fully enters Neutralize in slag, through separation of solid and liquid, realize the concentration and separation of the elements such as arsenic in oxidation solution, sulphur, copper, lead, zinc, iron, after precipitating ion Neutralizer return to biological oxidation work cycle and utilize；
（3）The sulfuric acid solution that concentration is 2 ~ 20% is added in slag to neutralizing, is 1 in solid-to-liquid ratio:3-1:10th, stirring intensity is 500-800r/min, reaction temperature be 15-50 DEG C under the conditions of leach neutralize slag, extraction time 2-10h, neutralize slag in arsenic, Copper, lead, zinc, ferro element enter in liquid phase, through separation of solid and liquid, obtain calcium sulfate product；
（4）The arsenic in vulcanized sodium progress precipitation solution is added into pickle liquor, the amount for adding vulcanized sodium is amount of calculation 1.2-1.8 times, carry out under the conditions of stirring intensity 400-600r/min, reaction time 30-120min, reaction is consolidated after terminating Liquid is separated, and arsenic is reclaimed in the form of arsenones in pickle liquor；
（5）The added sulfuric acid of tail washings after heavy arsenic adjusts be 2 ~ 20% to sulfuric acid concentration after, return to acidleach process.
Extraction reactor of the present invention is mixer-settler extractor, extraction tower or centrifugal extractor.
Extractant of the present invention is 2- ethylhexyl phosphoric acid list -2- ethylhexyls, three pungent decyl tertiary amines or phosphoric acid Di-isooctyl.
Back washing agent of the present invention is 3-8mol/L hydrochloric acid；
Precipitating reagent of the present invention is milk of lime；
Iron in biological oxidation solution of the present invention, arsenic, sulphur rate of recovery difference >=95%, >=98%, >=99%.
Iron speciation >=20g/L in products obtained therefrom ferric chloride solution of the present invention.
Purity by weight >=98% of products obtained therefrom calcium sulfate of the present invention.
Purity by weight >=92% of products obtained therefrom arsenones of the present invention.
The method of the present invention this have the advantage that relative to other method：It is raw materials used easily to take, preserve well, the technique of use Simple and practical flow, the synthetical recovery of valuable element can be realized, production cost is relatively low, and equipment investment is few；The product of acquisition is pure Degree is high, and element recovery rate is high, and product quality is stable；And do not produce secondary pollution；Waste zero-emission can be realized.
The inventive method achieves the comprehensive utilization of resource, can be that gold biological oxidation enterprise brings additional economy Benefit, have a good application prospect.
Brief description of the drawings
Fig. 1 is the flow reference chart of the present invention.
Embodiment
Contain the elements such as Fe, As, S, Cu, Pb, Zn, its content difference in the biological oxidation solution used in the embodiment of the present invention For 22.18g/L, 9.97g/L, 20.36g/L, 0.048g/L, 0.013g/L, 0.063g/L, but this should not be interpreted as to the present invention Above-mentioned content is only limitted to, wherein sulphur and arsenic exists in the form of sulfate radical and arsenate respectively, and iron majority is with Fe3+Form is deposited It is 0.8 in the pH value of, biological oxidation solution.
Embodiment 1
（1）It is 2- ethylhexyl phosphoric acid list -2- ethyl hexyls that oxidation solution and extractant, extractant are added in mixer-settler extractor The volume ratio of ester, organic phase and aqueous phase is 1:0.5,3min is stirred at normal temperatures, then clarifies 15min, through three stage countercurrents Extract, the Fe in oxidation solution3+Ion enters in organic phase, carries iron organic phase and uses concentration to be stripped for 3mol/L hydrochloric acid solution Take, reclaim the iron in organic phase, organic phase recycles, and the rate of recovery of iron is 95.06%；
（2）Milk of lime is added into raffinate, the pH value for adjusting solution is 7, and temperature is 15 DEG C, stirring intensity 600r/ 10h is stirred under the conditions of min, after the completion of carry out separation of solid and liquid, all enter with raw material that slag is acidleach process, valuable element in solid Enter to neutralize in slag, through separation of solid and liquid, realize the concentration and separation of the elements such as arsenic in oxidation solution, sulphur, copper, lead, zinc, iron, precipitating ion Neutralizer afterwards returns to biological oxidation work cycle and utilized, and arsenic, the rate of recovery of sulphur are respectively 98.56%, 99.02%；
（3）The sulfuric acid solution that concentration is 2% is added in slag to neutralizing, is 1 in solid-to-liquid ratio:3rd, stirring intensity 500r/min, Reaction temperature leaches the elements such as the arsenic neutralized in slag, copper, lead, zinc, iron under the conditions of being 15 DEG C, solid-liquid is carried out after Leach reaction 10h Separation, obtain product calcium sulfate；
（4）The arsenic in vulcanized sodium progress precipitation solution is added into pickle liquor, the amount for adding vulcanized sodium is the 1.2 of amount of calculation Times, carried out under the conditions of stirring intensity 400r/min, reaction time 120min, reaction carries out separation of solid and liquid after terminating, and solid is Product arsenones, the rate of deposition of arsenic is 99.89%；
（5）The added sulfuric acid of tail washings after heavy arsenic adjusts be 2% to sulfuric acid concentration after, return to acidleach process；
The product of gained, iron speciation is 20.00g/L in ferric chloride solution, the purity by weight of calcium sulfate >= 98.00%, purity by weight >=93.68% of arsenones.
Embodiment 2
（1）It is 2- ethylhexyl phosphoric acid list -2- ethyl hexyls that oxidation solution and extractant, extractant are added in mixer-settler extractor The volume ratio of ester, organic phase and aqueous phase is 1:1.0,5min is stirred at normal temperatures, then clarifies 15min, through three stage countercurrents Extract, the iron in oxidation solution enters in organic phase, carries iron organic phase and uses concentration to be stripped for 4mol/L hydrochloric acid solution, recovery Iron in organic phase, organic phase recycle, and the rate of recovery of iron is 96.58%；
（2）Milk of lime is added into raffinate, the pH value for adjusting solution is 8, and temperature is 20 DEG C, stirring intensity 650r/ 8h is stirred under the conditions of min, after the completion of carry out separation of solid and liquid, all enter with raw material that slag is acidleach process, valuable element in solid Enter to neutralize in slag, through separation of solid and liquid, realize the concentration and separation of the elements such as arsenic in oxidation solution, sulphur, copper, lead, zinc, iron, precipitating ion Neutralizer afterwards returns to biological oxidation work cycle and utilized, and arsenic, the rate of recovery of sulphur are respectively 98.96%, 99.37%.
（3）The sulfuric acid solution that concentration is 6% is added in slag to neutralizing, is 1 in solid-to-liquid ratio:5th, stirring intensity 600r/min, Reaction temperature leaches the elements such as the arsenic neutralized in slag, copper, lead, zinc, iron under the conditions of being 20 DEG C, solid-liquid point is carried out after Leach reaction 8h From acquisition product calcium sulfate；
（4）The arsenic in vulcanized sodium progress precipitation solution is added into pickle liquor, the amount for adding vulcanized sodium is the 1.3 of amount of calculation Times, carried out under the conditions of stirring intensity 450r/min, reaction time 90min, reaction carries out separation of solid and liquid after terminating, solid is production Thing arsenones, the rate of deposition of arsenic is 99.31%；
（5）The added sulfuric acid of tail washings after heavy arsenic adjusts be 6% to sulfuric acid concentration after, return to acidleach process；
The product of gained, iron speciation is 22.31g/L in ferric chloride solution, the purity by weight of calcium sulfate >= 98.65%, purity by weight >=92.00% of arsenones.
Embodiment 3
（1）It is 2- ethylhexyl phosphoric acid list -2- ethyl hexyls that oxidation solution and extractant, extractant are added in mixer-settler extractor The volume ratio of ester, organic phase and aqueous phase is 1:1.5,7min is stirred at normal temperatures, then clarifies 15min, through three stage countercurrents Extract, the iron in oxidation solution enters in organic phase, carries iron organic phase and uses concentration to be stripped for 5mol/L hydrochloric acid solution, recovery Iron in organic phase, organic phase recycle, and the rate of recovery of iron is 96.28%；
（2）Milk of lime is added into raffinate, the pH value for adjusting solution is 8, and temperature is 25 DEG C, stirring intensity 700r/ 6h is stirred under the conditions of min, after the completion of carry out separation of solid and liquid, all enter with raw material that slag is acidleach process, valuable element in solid Enter to neutralize in slag, through separation of solid and liquid, realize the concentration and separation of the elements such as arsenic in oxidation solution, sulphur, copper, lead, zinc, iron, precipitating ion Neutralizer afterwards returns to biological oxidation work cycle and utilized；Arsenic, the rate of recovery of sulphur are respectively 99.03%, 99.64%；
（3）The sulfuric acid solution that concentration is 10% is added in slag to neutralizing, is 1 in solid-to-liquid ratio:6th, stirring intensity 650r/ Min, reaction temperature leach the elements such as the arsenic neutralized in slag, copper, lead, zinc, iron under the conditions of being 25 DEG C, consolidated after Leach reaction 6h Liquid separates, and obtains product calcium sulfate；
（4）The arsenic in vulcanized sodium progress precipitation solution is added into pickle liquor, the amount for adding vulcanized sodium is the 1.4 of amount of calculation Times, carried out under the conditions of stirring intensity 500r/min, reaction time 75min, reaction carries out separation of solid and liquid after terminating, solid is production Thing arsenones, the rate of deposition of arsenic is 98.99%；
（5）The added sulfuric acid of liquid adjusts after heavy arsenic be 10% to sulfuric acid concentration after, return to acidleach process；
The product of gained, iron speciation is 35.42g/L in ferric chloride solution, the purity by weight of calcium sulfate >= 99.06%, purity by weight >=95.27% of arsenones.
Embodiment 4
（1）Add oxidation solution and extractant in extraction tower, extractant is three pungent decyl tertiary amines, organic phase and aqueous phase Volume ratio is 1:1.8,9min is stirred at normal temperatures, then clarifies 15min, through three-level counter-current extraction, the iron in oxidation solution Into in organic phase.Carrying iron organic phase uses concentration to be stripped for 6mol/L hydrochloric acid solution, reclaims the iron in organic phase, organic Mutually recycle, the rate of recovery of iron is 97.63%；
（2）Milk of lime is added into raffinate, the pH value for adjusting solution is 9, and temperature is 33 DEG C, stirring intensity 700r/ 5h is stirred under the conditions of min, after the completion of carry out separation of solid and liquid, all enter with raw material that slag is acidleach process, valuable element in solid Enter to neutralize in slag, through separation of solid and liquid, realize the concentration and separation of the elements such as arsenic in oxidation solution, sulphur, copper, lead, zinc, iron, precipitating ion Neutralizer afterwards returns to biological oxidation work cycle and utilized；Arsenic, the rate of recovery of sulphur are respectively 98.64%, 99.21%；
（3）The sulfuric acid solution that concentration is 11% is added in slag to neutralizing, is 1 in solid-to-liquid ratio:7th, stirring intensity 650r/ Min, reaction temperature leach the elements such as the arsenic neutralized in slag, copper, lead, zinc, iron under the conditions of being 33 DEG C, consolidated after Leach reaction 6h Liquid separates, and obtains product calcium sulfate；
（4）The arsenic in vulcanized sodium progress precipitation solution is added into pickle liquor, the amount for adding vulcanized sodium is the 1.5 of amount of calculation Times, carried out under the conditions of stirring intensity 500r/min, reaction time 75min, reaction carries out separation of solid and liquid after terminating, solid is production Thing arsenones, the rate of deposition of arsenic is 99.67%；
（5）The added sulfuric acid of tail washings after heavy arsenic adjusts be 11% to sulfuric acid concentration after, return to acidleach process；
The product of gained, iron speciation is 29.15g/L in ferric chloride solution, the purity by weight of calcium sulfate >= 98.74%, purity by weight >=94.88% of arsenones.
Embodiment 5
（1）Add oxidation solution and extractant in extraction tower, extractant is three pungent decyl tertiary amines, organic phase and aqueous phase Volume ratio is 1:2.5,12min is stirred at normal temperatures, then clarifies 15min, through three-level counter-current extraction, the iron in oxidation solution Into in organic phase, carry iron organic phase and use concentration to be stripped for 7mol/L hydrochloric acid solution, reclaim the iron in organic phase, it is organic Mutually recycle, the rate of recovery of iron is 97.50%；
（2）Milk of lime is added into raffinate, the pH value for adjusting solution is 9, and temperature is 40 DEG C, stirring intensity 750r/ 4h is stirred under the conditions of min, after the completion of carry out separation of solid and liquid, all enter with raw material that slag is acidleach process, valuable element in solid Enter to neutralize in slag, through separation of solid and liquid, realize the concentration and separation of the elements such as arsenic in oxidation solution, sulphur, copper, lead, zinc, iron, precipitating ion Neutralizer afterwards returns to biological oxidation work cycle and utilized；Arsenic, the rate of recovery of sulphur are respectively 98.86%, 99.72%；
（3）The sulfuric acid solution that concentration is 17% is added in slag to neutralizing, is 1 in solid-to-liquid ratio:9th, stirring intensity 750r/ Min, reaction temperature leach the elements such as the arsenic neutralized in slag, copper, lead, zinc, iron under the conditions of being 40 DEG C, consolidated after Leach reaction 4h Liquid separates, and obtains product calcium sulfate；
（4）The arsenic in vulcanized sodium progress precipitation solution is added into pickle liquor, the amount for adding vulcanized sodium is the 1.6 of amount of calculation Times, carried out under the conditions of stirring intensity 550r/min, reaction time 45min, reaction carries out separation of solid and liquid after terminating, solid is production Thing arsenones, the rate of deposition of arsenic is 99.37%；
（5）The added sulfuric acid of tail washings after heavy arsenic adjusts be 17% to sulfuric acid concentration after, return to acidleach process.
The product of gained, iron speciation is 40.62g/L in ferric chloride solution, the purity by weight of calcium sulfate >= 99.56%, purity by weight >=93.24% of arsenones.
Embodiment 6
（1）It is di (isooctyl) phosphate, organic phase and aqueous phase that oxidation solution and extractant, extractant are added in centrifugal extractor Volume ratio be 1:3.0,15min is stirred at normal temperatures, then clarifies 15min, through three-level counter-current extraction, in oxidation solution Iron enters in organic phase, carries iron organic phase and uses concentration to be stripped for 8mol/L hydrochloric acid solution, reclaims the iron in organic phase, have Machine mutually recycles, and the rate of recovery of iron is 98.97%；
（2）Milk of lime is added into raffinate, the pH value for adjusting solution is 10, and temperature is 50 DEG C, stirring intensity 800r/ 2h is stirred under the conditions of min, after the completion of carry out separation of solid and liquid, all enter with raw material that slag is acidleach process, valuable element in solid Enter to neutralize in slag, through separation of solid and liquid, realize the concentration and separation of the elements such as arsenic in oxidation solution, sulphur, copper, lead, zinc, iron, precipitating ion Neutralizer afterwards returns to biological oxidation work cycle and utilized；Arsenic, the rate of recovery of sulphur are respectively 98.94%, 99.17%；
（3）The sulfuric acid solution that concentration is 20% is added in slag to neutralizing, is 1 in solid-to-liquid ratio:10th, stirring intensity 800r/ Min, reaction temperature leach the elements such as the arsenic neutralized in slag, copper, lead, zinc, iron under the conditions of being 50 DEG C, consolidated after Leach reaction 2h Liquid separates, and obtains product calcium sulfate；
（4）The arsenic in vulcanized sodium progress precipitation solution is added into pickle liquor, the amount for adding vulcanized sodium is the 1.8 of amount of calculation Times, carried out under the conditions of stirring intensity 600r/min, reaction time 30min, reaction carries out separation of solid and liquid after terminating, solid is production Thing arsenones, the rate of deposition of arsenic is 99.11%；
（5）The added sulfuric acid of tail washings after heavy arsenic adjusts be 20% to sulfuric acid concentration after, return to acidleach process；
The product of gained, iron speciation is 34.38g/L in ferric chloride solution, the purity by weight of calcium sulfate >= 98.24%, purity by weight >=92.98% of arsenones.

Claims (9)

  1. A kind of 1. method that valuable element is reclaimed from acidic arsenic-containing, iron, sulphur biological oxidation solution, it is characterised in that：Including following Step：
    （1）The volume ratio of addition oxidation solution and extractant into extraction reactor, organic phase and aqueous phase is 1:0.5~1:3, fully After mixing 3-15min, aqueous phase and organic phase are separated, through three-level counter-current extraction, makes the Fe in oxidation solution3+Ion enters organic phase, After back washing agent is stripped, iron is reclaimed the organic phase of load iron in the form of iron chloride, and the organic phase after back extraction recycles；
    （2）Precipitating reagent is added into the raffinate after separation iron, makes system pH be 7-10, reaction temperature is 15-50 DEG C, stirring Intensity is 600-800r/min, precipitates the ion contained in raffinate under the conditions of 2 ~ 10h of stirring, and valuable element fully enters neutralization In slag, through separation of solid and liquid, the concentration and separation of arsenic in oxidation solution, sulphur, copper, lead, zinc, ferro element is realized, the neutralization after precipitating ion Liquid returns to biological oxidation work cycle and utilized；
    （3）The sulfuric acid solution that concentration is 2 ~ 20% is added in slag to neutralizing, is 1 in solid-to-liquid ratio:3-1:10th, stirring intensity 500- 800r/min, reaction temperature be 15-50 DEG C under the conditions of leach neutralize slag, extraction time 2-10h, neutralize slag in arsenic, copper, Lead, zinc, ferro element enter in liquid phase, through separation of solid and liquid, obtain calcium sulfate product；
    （4）The arsenic in vulcanized sodium progress precipitation solution is added into pickle liquor, the amount for adding vulcanized sodium is the 1.2-1.8 of amount of calculation Times, being carried out under the conditions of stirring intensity 400-600r/min, reaction time 30-120min, reaction carries out separation of solid and liquid after terminating, Arsenic is reclaimed in the form of arsenones in pickle liquor；
    （5）The added sulfuric acid of tail washings after heavy arsenic adjusts be 2 ~ 20% to sulfuric acid concentration after, return to acidleach process.
  2. 2. a kind of method that valuable element is reclaimed from acidic arsenic-containing, iron, sulphur biological oxidation solution according to claim 1, It is characterized in that：The extraction reactor is mixer-settler extractor, extraction tower or centrifugal extractor.
  3. 3. a kind of method that valuable element is reclaimed from acidic arsenic-containing, iron, sulphur biological oxidation solution according to claim 1, It is characterized in that：Described extractant is 2- ethylhexyl phosphoric acid list -2- ethylhexyls, and three pungent decyl tertiary amines or di(2-ethylhexyl)phosphate are different Monooctyl ester.
  4. 4. a kind of method that valuable element is reclaimed from acidic arsenic-containing, iron, sulphur biological oxidation solution according to claim 1, It is characterized in that：Described back washing agent is 3-8mol/L hydrochloric acid.
  5. 5. a kind of method that valuable element is reclaimed from acidic arsenic-containing, iron, sulphur biological oxidation solution according to claim 1, It is characterized in that：Described precipitating reagent is milk of lime.
  6. 6. a kind of method that valuable element is reclaimed from acidic arsenic-containing, iron, sulphur biological oxidation solution according to claim 1, It is characterized in that：Iron in the biological oxidation solution, arsenic, sulphur rate of recovery difference >=95%, >=98%, >=99%.
  7. 7. a kind of method that valuable element is reclaimed from acidic arsenic-containing, iron, sulphur biological oxidation solution according to claim 1, It is characterized in that：Iron speciation >=20g/L in products obtained therefrom ferric chloride solution.
  8. 8. a kind of method that valuable element is reclaimed from acidic arsenic-containing, iron, sulphur biological oxidation solution according to claim 1, It is characterized in that：Purity by weight >=98% of products obtained therefrom calcium sulfate.
  9. 9. a kind of method that valuable element is reclaimed from acidic arsenic-containing, iron, sulphur biological oxidation solution according to claim 1, It is characterized in that：Purity by weight >=92% of products obtained therefrom arsenones.
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