CN105543491B - Rhenium, copper, the method for lead and its device are quickly reclaimed from Copper making spent acid - Google Patents
Rhenium, copper, the method for lead and its device are quickly reclaimed from Copper making spent acid Download PDFInfo
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- CN105543491B CN105543491B CN201610126619.6A CN201610126619A CN105543491B CN 105543491 B CN105543491 B CN 105543491B CN 201610126619 A CN201610126619 A CN 201610126619A CN 105543491 B CN105543491 B CN 105543491B
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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
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- C—CHEMISTRY; METALLURGY
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- 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
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0086—Treating solutions by physical methods
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B61/00—Obtaining metals not elsewhere provided for in this subclass
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- 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
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Abstract
The invention discloses rhenium, copper, the method for lead and its device are quickly reclaimed in a kind of spent acid from Copper making, this method obtains rich rhenium slag more than 55% lead skim except lead obtains lead content using Copper making spent acid is filtered as the heavy rhenium of targeting after carrying leady raw materialses, rich rhenium slag leaches to obtain rich rhenium leachate again through hot-pressure oxidation, rhenium being sunk through KCl after evaporation and concentration and potassium perrhenate being made in recrystallization, liquid carries out vulcanizing heavy copper after heavy rhenium；The device includes rhenium copper precipitating reagent storage tank, stillpot, flocculant storage tank, flocculation reaction groove, reactor, crystallizing evaporator, centrifugal separator, spent acid antigravity percolating filter, rich rhenium copper ashes antigravity percolating filter, filter press, rhenium copper stillpot steam-heating system, copper stillpot steam-heating system and Pulp pump.The present invention have invest small, quick short route, it is simple to operate efficiently, clean environment firendly, the high rate of recovery the characteristics of.
Description
Technical field
The present invention relates to rhenium, copper, the method for lead and its device are reclaimed from Copper making spent acid, and in particular to is given up from Copper making
Rhenium, copper, the method for lead and its device are quickly reclaimed in acid.
Background technology
Rhenium be it is a kind of it is dilute dissipate, refractory metal element, in nature without Independent Mineral, generally with the mineral reserve companion such as copper, molybdenum, uranium
It is raw.In the smelting processes such as copper, molybdenum, uranium, rhenium is mainly enriched in volatilization flue dust, flue gas washing liquid or leachate, this intermediate material
The important source material that can be extracted as rhenium.
Copper making spent acid is Copper making process flue gas aqueous medium cleaning solution.During Copper making, dissipated metal in copper concentrate
Rhenium is largely volatized into after flue gas enters spent acid through washing, rhenium concentration about 5-50mg/L in spent acid；It is few in other smoke dust system
Copper, the lead of amount enter spent acid in the lump.Spent acid conventional processes are to sink to arsenic filter cake in the lump through sulfide precipitation, rhenium, copper, lead etc.,
Arsenic filter cake further carries out harmlessness disposing or the more metals resourcesization extractions of rhenium, copper, lead.
In recent years, as waste acid resourceization is goed deep into using technical study, rhenium in Copper making spent acid, copper fractional precipitation and
Rhenium, the exploration technique of copper thiosulfate targeting precipitation have been appeared in the newspapers（A Hou Fuzu of CN 103773963 etc., CN
102628110B Zhou Songlins etc.）, during these methods in Copper making spent acid due to targetting heavy rhenium, heavy process for copper, precipitating reagent is single
Thiosulfate, precipitating reagent addition is caused according to rhenium, copper content adjustment poor controllability, thiosulfate addition in spent acid
Greatly, and reaction speed is slow, low production efficiency, and in the case of especially copper content is too high in spent acid, it is complete that rhenium is difficult to precipitation.
For the processing of arsenic filter cake, Jiangxi Copper group Guixi Smelter is using " acid system high pressure leaches arsenic filter cake-extraction
Take enriching rhenium-prepare rehenic acid ammonium " technique recovery rhenium, rhenium low 600g/t-800g/t, using high pressure high by about 35% containing arsenic in arsenic filter cake
It is arsenic oxide arsenoxide to leach arsenic filter cake main purpose, reclaims arsenic, and rhenium reclaims only as high attached valuable product, therefore in leaching condition, work
Skill equipment aspect mainly carries out research and design according to the purpose of arsenic oxide arsenoxide, and this method has technological process length, acid system
Leach, high to equipment requirement, cost is high, the low shortcoming of Rhenium recovery rate；And the low 4%-5% of rich rhenium slag arsenic of the present invention, rhenium are high
2%-5%, high pressure leach purpose and are oxidation of sulfureted rhenium, and arsenic returns to acid water arsenic removal as discarded object, and the two leaches bar
Very big difference be present in part.
Zhang Bangqi etc.（CN 104404277 A）The method using rhenium in a kind of Strengthen education richness rhenium slag is proposed, it is used
The method system of " rich rhenium slag soaks with leading to oxygen heating oxidizing roasting-pressurized, heated alkali in a certain amount of sulphur-fixing agent profit mill-tube furnace "
The expensive liquid of standby rhenium-containing, oxidizing roasting high energy consumption be present, big for environment pollution, high pressure base caustic dip consumption is big, the reaction time is long and processing energy
The defects of power is small.
To sum up, prior art is because in the conventional vulcanized depositing technology of Copper making spent acid, the valuable metal such as rhenium, copper, lead is in the lump
Arsenic filter cake is sunk to, causes valuable metal concentration effect poor, subsequent extracted process materials treating capacity is big, technological process length, equipment rule
Mould, amount of investment are big, and arsenic filter cake recycling process is difficult to the processing for avoiding poisonous and hazardous low value-added element arsenic in addition, environmental protection,
Production cost is high.
The content of the invention
It is an object of the invention to provide one kind to invest small, quick short route, efficient, clean environment firendly simple to operate, recovery
Rhenium, copper, the method for lead and its device are quickly reclaimed in the high spent acid from Copper making of rate.
To realize object above, it is by Copper making quickly to reclaim rhenium, copper, the method for lead from Copper making spent acid in the present invention
Spent acid is filtered remove target heavy rhenium after lead, heavy copper obtains rich rhenium copper ashes, the rich pressurized oxygen of rhenium copper ashes leaches to obtain rich rhenium leachate,
Leachate is through being concentrated by evaporation, the heavy rheniums of KCl obtain rehenic acid potassium product, and liquid obtains copper sulfide through vulcanization reaction after heavy rhenium；Operating procedure
It is as follows：
（a）Copper making spent acid is crossed through spent acid antigravity percolating filter and filters out lead, obtains lead content and is more than 55% lead skim conduct
Carry leady raw materialses；
（b）The added thiosulfate of Copper making spent acid that rhenium content is 5mg/L-50mg/L compounds vulcanized sodium as precipitation
After the heavy rhenium of agent targeting, heavy copper, rich rhenium copper ashes is obtained；Rhenium content is 2%-5% in rich rhenium copper ashes, copper content 5-20%, reaction temperature
50-70 DEG C, reaction time 5-15min, thiosulfate addition 2-5g/L, vulcanized sodium addition 10-20mg/L；
（c）By step（b）Gained richness rhenium copper ashes leaches rhenium, copper using pressurised oxygen, and course of reaction is not added in addition to logical oxygen appoints
What oxidant and soda acid, control liquid-solid ratio 4-8:1,130 DEG C -170 DEG C, partial pressure of oxygen 0.3MPa-1.5MPa of extraction temperature, during leaching
Between 1h-5h.
（d）By step（c）Heavy rhenium-the recrystallization of gained leachate concentration prepares pure potassium perrhenate, rich rhenium liquid after control concentration
Rhenium concentration 10g/L-20g/L, KCl, 5 DEG C -15 DEG C of crystallization temperature, sedimentation time 5-40min are added by 15g/L-35g/L；Weight is molten
50 DEG C -100 DEG C of water temperature, liquid-solid ratio 3-6:1, oxidant addition 1g/L-15g/L；After dissolving, control chilling temperature is at -5 DEG C -5
℃；
（e）By step（d）Liquid is placed in heavy copper in the heavy copper groove of vulcanization after the heavy rhenium of gained, and it is theoretical amount to control vulcanized sodium addition
1.1-1.5 times, 60-90 DEG C of reaction temperature, reaction time 1-3h.
Quickly recovery rhenium, copper, the device of lead include from Copper making spent acid in the present invention：Rhenium copper precipitating reagent storage tank one, rhenium
Copper precipitating reagent storage tank two, rhenium copper stillpot, flocculation reaction groove one, compressive reaction kettle, evaporate-crystallization device, centrifugal separator, copper sink
Shallow lake agent storage tank, copper stillpot, flocculant storage tank, flocculation reaction groove two, spent acid antigravity percolating filter, rich rhenium copper ashes antigravity
Percolating filter, filter press one, filter press two, rhenium copper stillpot steam-heating system, copper stillpot steam-heating system and slag
Stock pump；It is characterized in that the flocculant storage tank is in relatively high-order and connects flocculation reaction groove one and wadding in relatively low position
Solidifying reactive tank two, copper precipitating reagent storage tank position are higher than and connect copper stillpot, and rhenium copper precipitation groove location is higher than and connects flocculation instead
Groove one is answered, to realize flocculant, medicament gravity flow and reaction ore pulp overflow；Rhenium copper precipitating reagent storage tank one and rhenium copper precipitating reagent storage tank two
Mixed export, spent acid antigravity percolating filter filtrate (liquid be connected to rhenium copper stillpot middle and lower part, on rhenium copper stillpot
Portion sets overfall, the top of overfall connection flocculation reaction groove one；Rich rhenium copper ashes antigravity percolating filter slag notch connection pressurization
Reactor charging aperture, bottom connection Pulp pump and filter press one realize the filtering for leaching slurry, and the liquid outlet of filter press one connects successively
Connect evaporate-crystallization device, centrifugal separator, centrifugal separator clear liquid overfall connection copper stillpot middle and upper part, copper precipitation trench bottom
Connect Pulp pump and filter press two.
Quickly recovery rhenium, copper, the method for lead and its device have the following effects that in the above-mentioned spent acid from Copper making：
（1）Realization and acid, the separation of arsenic, enrichment before copper, rhenium refining, material handling capacity is few, and investment of production is small, environmental protection
It is good；
（2）Rich rhenium copper ashes uses pressure leaching technique, no acid and alkali consumption, and the direct evaporative crystallization of leachate obtains the production of rehenic acid potassium
Product；
（3）Rhenium, copper, lead recovery process are short, simple in construction；Whole process rhenium, copper, lead recovery reach more than 99%；
（4）Spent acid, rich rhenium copper ashes slurry filtration use antigravity percolating filter, effectively solve low-solid content, high disposal
Filtration problem under the conditions of amount.
Brief description of the drawings
Fig. 1 is the present invention quickly apparatus structure signal of recovery rhenium, copper, the method for lead and its device from Copper making spent acid
Figure.
Fig. 2 is the present invention quickly technological process signal of recovery rhenium, copper, the method for lead and its device from Copper making spent acid
Figure.
Reference：Rhenium copper precipitating reagent storage tank 1, rhenium copper precipitating reagent storage tank 22, rhenium copper stillpot 3, flocculation reaction groove one
4th, compressive reaction kettle 5, evaporate-crystallization device 6, centrifugal separator 7, copper precipitating reagent storage tank 8, copper stillpot 9, flocculant storage tank 10,
Flocculation reaction groove 2 11, spent acid antigravity percolating filter 12, rich rhenium copper ashes antigravity percolating filter 13, filter press 1,
Filter press 2 15, rhenium copper stillpot steam-heating system 16, copper stillpot steam-heating system 17, Pulp pump 18, Copper making give up
Liquid 33, rich rhenium copper ashes 34, rich rhenium copper liquid 35, leached mud 36, potassium chloride 37, thick potassium perrhenate after acid 31, lead filter cake 32, heavy rhenium
38th, sink rhenium after liquid 39, crystalline mother solution 40, potassium perrhenate 41, vulcanization copper ashes 42 and heavy copper after liquid 43.
Embodiment
Quickly reclaim the side of rhenium, copper, lead from Copper making spent acid to the present invention with reference to the accompanying drawings and detailed description
Method and its device are described in further detail.
Quickly recovery rhenium, copper, the device of lead include the present invention shown in Fig. 1 from Copper making spent acid：Rhenium copper precipitating reagent storage tank
One 1, rhenium copper precipitating reagent storage tank 22, rhenium copper stillpot 3, flocculation reaction groove 1, compressive reaction kettle 5, evaporate-crystallization device 6, centrifugation
Seperator 7, copper precipitating reagent storage tank 8, copper stillpot 9, flocculant storage tank 10, flocculation reaction groove 2 11, spent acid antigravity penetrate
Filter 12, rich rhenium copper ashes antigravity percolating filter 13, filter press 1, filter press 2 15, rhenium copper stillpot steam heating system
System 16, copper stillpot steam-heating system 17 and Pulp pump 18；The flocculant storage tank 10 is in relatively high-order and connected and is in
With respect to the flocculation reaction groove 1 and flocculation reaction groove 2 11 of low level, the position of copper precipitating reagent storage tank 8 is higher than and connects copper stillpot 9,
The position of rhenium copper stillpot 3 is higher than and connects flocculation reaction groove 1, to realize flocculant, medicament gravity flow and reaction ore pulp overflow；Rhenium
Mixed export, spent acid antigravity 12 filtrate (liquids of percolating filter of copper precipitating reagent storage tank 1 and rhenium copper precipitating reagent storage tank 22 are equal
The middle and lower part of rhenium copper stillpot 3 is connected to, the top of rhenium copper stillpot 3 sets overfall, the top of overfall connection flocculation reaction groove 1；
The rich charging aperture of the slag notch of rhenium copper ashes antigravity percolating filter 13 connection compressive reaction kettle 5, bottom connection Pulp pump 18 and press filtration
Machine 1 realizes the filtering for leaching slurry, and the liquid outlet of filter press 1 is sequentially connected evaporate-crystallization device 6, centrifugal separator 7, from
The middle and upper part of the clear liquid overfall of centrifugal separator 7 connection copper stillpot 9, the bottom of copper stillpot 9 connection Pulp pump 18 and filter press 2 15.
During work, flocculant precipitates from flocculation reaction groove 1, flocculation reaction groove 2 11, copper precipitating reagent is flowed into from copper is flowed into
Groove 9, rhenium copper precipitation slurry enter flocculation reaction groove 1 by overfall overflow；Spent acid filters through antigravity percolating filter 12
Clear liquid and rhenium copper precipitating reagent are flowed into by the middle and lower part of rhenium copper stillpot 3 afterwards, and rhenium copper precipitates ore pulp through the top overfall of rhenium copper stillpot 3
Overflow is to flocculation reaction groove 1；It is defeated through pipeline that rhenium copper precipitates slurry slag after the filtering of rich rhenium copper ashes antigravity percolating filter 13
Compressive reaction kettle 5 is delivered to, slurry is delivered to the filtering of the realization leaching slurry of filter press 1 through bottom Pulp pump 18 after reaction, obtains
To rich rhenium liquid；Rich rhenium liquid obtains rehenic acid potassium, centrifugal separator 7 after evaporate-crystallization device 6 evaporates, crystallized into centrifugal separator 7
Clear liquid enters copper stillpot 9 through overfall, and after sulfide precipitation reacts, Pulp pump 18 and press filtration are connected through the bottom of copper stillpot 9
Machine 2 15 obtains copper-rich product.
The quickly technological process of recovery rhenium, copper, lead from Copper making spent acid of the present invention shown in Fig. 2, is exemplified below five realities
Apply example to be described further the technique, each embodiment uses Fig. 1 shown devices, and applicable technological parameter is：
The heavy rhenium condition of targeting：50-70 DEG C of reaction temperature, reaction time 5-15min, thiosulfate addition 2-5g/L,
Vulcanized sodium addition 10-20mg/L；
Hot-pressure oxidation leaches rhenium：Liquid-solid ratio 4-8:1, extraction temperature control is at 130 DEG C -170 DEG C, partial pressure of oxygen 0.3MPa-
1.5MPa, extraction time 1h-5h；
The rich heavy rhenium-recrystallization of rhenium leachate concentration：Rich rhenium liquid rhenium concentration 10g/L-20g/L, KCl addition is after concentration
15g/L-35g/L, 5 DEG C -15 DEG C of crystallization temperature, sedimentation time 5-40min；50 DEG C -100 DEG C of the molten water temperature of weight, liquid-solid ratio 3-6:1,
Oxidant addition 1g/L-15g/L, -5 DEG C of recrystallization temperature -5 DEG C；
The heavy copper of vulcanization：Vulcanized sodium addition is 1.1-1.5 times of copper content, -90 DEG C of temperature 60 C, reacts 1h-3h.
Embodiment 1
Handled Copper making spent acid sulfuric acid concentration 73.48g/L, rhenium concentration 17.94mg/L, copper concentration in this example
33.48mg/L, arsenic concentration 7.58g/L, handling process, effect are as follows：
（1）By Copper making spent acid through antigravity permeation filtration, remove lead suspension in spent acid and send rhenium copper stillpot, obtain lead
Slag ingredient is：Lead 52.3%, copper 0.1%, bismuth 0.5%, arsenic 0.1%.
（2）The spent acid crossed after filtering out lead is pumped in rhenium copper stillpot, by measuring pump with 1m3Spent acid adds 20% sulphur
Sodium thiosulfate 20L, vulcanized sodium 15g, 70 DEG C are steam heated to, stirring reaction 5min；Gained richness rhenium slag ingredient is rhenium 2.56%, arsenic
32.18%, copper 8.34%；Rhenium rate of deposition is 99.8%, arsenic rate of deposition only 2.97%, copper rate of deposition 99.6%.（3）By step（2）Gained
Rich rhenium slag carries out pressurised oxygen leaching, and leaching condition is：Liquid-solid ratio is 6:1,170 DEG C, partial pressure of oxygen 0.3MPa of extraction temperature, during leaching
Between 3h；Steep cencentration is：Rhenium 7.48g/L, copper 24.32g/L, sulfuric acid 35g/L；Rhenium leaching rate is 99.7%, copper leaching rate
99.6%。
（4）By step（3）Gained richness rhenium leachate is concentrated by evaporation laggard to rhenium concentration about 20g/L in evaporate-crystallization device
Row freezing and crystallizing, 10 DEG C, crystallization time 30min, potassium chloride addition 25g/L of crystallization temperature, the thick potassium perrhenate purity of gained are
99.2%, rhenium percent crystallization in massecuite 93%.（5）By step（4）Gained potassium perrhenate is in the containers such as beaker plus 100 DEG C of hot water weights are molten, and liquid is solid
Than 3:1, oxidant addition is 15g/L, dissolves and is recrystallized after -5 DEG C, crystallization time 40min, and gained potassium perrhenate is pure
Spend for 99.99%, recrystallization ratio 99.0%.
（6）To step（3）In heavy rhenium after liquid addition copper content 1.1 times of vulcanized sodium, control 90 DEG C of temperature, reaction
1h；Filtering can obtain copper sulfide precipitation, rate of deposition 97%.
Embodiment 2
Handled Copper making spent acid sulfuric acid concentration 73.48g/L, rhenium concentration 17.94mg/L, copper concentration in this example
33.48mg/L, arsenic concentration 7.58g/L, handling process, effect are as follows：
（1）By Copper making spent acid through antigravity permeation filtration, remove lead suspension in spent acid and send rhenium copper stillpot, obtain lead
Slag ingredient is：Lead 52.3%, copper 0.1%, bismuth 0.5%, arsenic 0.1%.（2）The spent acid crossed after filtering out lead is pumped to rhenium copper stillpot
It is interior, by measuring pump with 1m3Spent acid adds 20% sodium thiosulfate 25L, vulcanized sodium 20g, is steam heated to 65 DEG C, stirring reaction
15min；Gained richness rhenium slag ingredient is rhenium 2.55%, arsenic 22.18%, copper 8.28%；Rhenium rate of deposition is 99.2%, and arsenic rate of deposition is only
2.05%, copper rate of deposition 99.1%.（3）By step（2）Gained richness rhenium slag carries out pressurised oxygen leaching.Leaching condition is：Liquid-solid ratio is
8:1,130 DEG C, partial pressure of oxygen 1.5MPa, extraction time 5h of extraction temperature；Steep cencentration is：Rhenium 6.33g/L, copper 20.56g/L,
Sulfuric acid 33g/L.Rhenium leaching rate is 99.3%, copper leaching rate 99.2%.
（4）By step（3）Gained richness rhenium leachate is concentrated by evaporation laggard to rhenium concentration about 15g/L in evaporate-crystallization device
Row freezing and crystallizing, 5 DEG C, crystallization time 5min, potassium chloride addition 15g/L of crystallization temperature, the thick potassium perrhenate purity of gained are
99%, rhenium percent crystallization in massecuite 91%.（5）By step（4）Gained potassium perrhenate adds 50 DEG C of molten, liquid-solid ratioes 6 of hot water weight in the containers such as beaker:
1, oxidant addition is 10g/L, dissolves and is recrystallized after 0 DEG C, crystallization time 20min, and gained potassium perrhenate purity is
99.99%, recrystallization ratio 98.4%.
（6）To step（3）In heavy rhenium after liquid addition copper content 1.3 times of vulcanized sodium, control temperature 60 C, reaction
5h；Filtering can obtain copper sulfide precipitation, rate of deposition 95%.
Embodiment 3
Handled Copper making spent acid sulfuric acid concentration 73.48g/L, rhenium concentration 17.94mg/L, copper concentration in this example
33.48mg/L, arsenic concentration 7.58g/L, handling process, effect are as follows：
（1）By Copper making spent acid through antigravity permeation filtration, remove lead suspension in spent acid and send rhenium copper stillpot, obtain lead
Slag ingredient is：Lead 52.3%, copper 0.1%, bismuth 0.5%, arsenic 0.1%.（2）The spent acid crossed after filtering out lead is pumped to rhenium copper stillpot
It is interior, by measuring pump with 1m3Spent acid adds 20% sodium thiosulfate 10L, vulcanized sodium 10g, is steam heated to 50 DEG C, stirring reaction
15min；Gained richness rhenium slag ingredient is rhenium 4.06%, arsenic 30.36%, copper 12.46%；Rhenium rate of deposition is 90.5%, and arsenic rate of deposition is only
1.6%, copper rate of deposition 85.4%.（3）By step（2）Gained richness rhenium slag carries out pressurised oxygen leaching, and leaching condition is：Liquid-solid ratio is 4:
1,150 DEG C, partial pressure of oxygen 1.0MPa, extraction time 3h of extraction temperature；Steep cencentration is：Rhenium 9.57g/L, copper 28.73g/L, sulphur
Sour 37g/L；Rhenium leaching rate is 94.3%, copper leaching rate 92.2%.
（4）By step（3）Gained richness rhenium leachate is concentrated by evaporation laggard to rhenium concentration about 10g/L in evaporate-crystallization device
Row freezing and crystallizing.15 DEG C, crystallization time 40min, potassium chloride addition 35g/L of crystallization temperature, the thick potassium perrhenate purity of gained are
99%, rhenium percent crystallization in massecuite 91%.（5）By step（4）Gained potassium perrhenate adds 70 DEG C of molten, liquid-solid ratioes 4 of hot water weight in the containers such as beaker:
1, oxidant addition is 1g/L, dissolves and is recrystallized after 5 DEG C, crystallization time 30min, and gained potassium perrhenate purity is
99.99%, recrystallization ratio 98.5%.
（6）To step（3）In heavy rhenium after liquid addition copper content 1.2 times of vulcanized sodium, control temperature 70 C, reaction
3h；Filtering can obtain copper sulfide precipitation, rate of deposition 95%.
Embodiment 4
Handled Copper making spent acid sulfuric acid concentration 89.36g/L in this example, rhenium concentration 45.83mg/L, arsenic concentration 8.61g/
L, copper concentration 500.8mg/L, handling process, effect are as follows：
（1）By Copper making spent acid through antigravity permeation filtration, remove lead suspension in spent acid and send rhenium copper stillpot, obtain lead
Slag ingredient is：Lead 52.3%, copper 0.1%, bismuth 0.5%, arsenic 0.1%.（2）The spent acid crossed after filtering out lead is pumped to rhenium copper stillpot
It is interior, by measuring pump with 1m3Spent acid adds 25% sodium thiosulfate 20L, vulcanized sodium 20g, is steam heated to 65 DEG C, stirring reaction
15min；Gained richness rhenium slag ingredient is rhenium 2.28%, arsenic 23.34%, copper 24.84%；Rhenium rate of deposition is 99.9%, and arsenic rate of deposition is only
2.71%, copper rate of deposition 99.8%.（3）By step（2）Gained richness rhenium slag carries out pressurised oxygen leaching, and leaching condition is：Liquid-solid ratio is
5,160 DEG C, partial pressure of oxygen 1MPa, extraction time 3h of extraction temperature；Steep cencentration is：Rhenium 8.09g/L, sulfuric acid 42g/L, copper
87.27g/L.Rhenium leaching rate is 99.5%, copper leaching rate 99.7%.（4）By step（3）Gained richness rhenium leachate is in evaporate-crystallization
Freezing and crystallizing is carried out after being concentrated by evaporation in device to rhenium concentration about 13g/L, 5 DEG C of crystallization temperature, crystallization time 30min, potassium chloride adds
Dosage 30g/L, the thick potassium perrhenate purity of gained are 99.3%, rhenium percent crystallization in massecuite 92%.（5）By step（4）Gained potassium perrhenate is in burning
Add 70 DEG C of molten, liquid-solid ratioes 5 of hot water weight in the containers such as cup:1, oxidant addition is 5g/L, dissolves and is recrystallized after 3 DEG C,
Crystallization time 40min, gained potassium perrhenate purity are 99.99%, recrystallization ratio 98.5%.
（6）To step（3）In heavy rhenium after liquid addition copper content 1.4 times of vulcanized sodium, control temperature 70 C, reaction
1h；Filtering can obtain copper sulfide precipitation, rate of deposition 96%.
Embodiment 5
Handled Copper making spent acid sulfuric acid concentration 67.28g/L in this example, rhenium concentration 9.97mg/L, arsenic concentration 5.51g/
L, copper concentration 213.32mg/L, handling process, effect are as follows：
（1）By Copper making spent acid through antigravity permeation filtration, remove lead suspension in spent acid and send rhenium copper stillpot, obtain lead
Slag ingredient is：Lead 50.4%, copper 0.1%, bismuth 0.4%, arsenic 0.1%.（2）The spent acid crossed after filtering out lead is pumped to rhenium copper stillpot
It is interior, by measuring pump with 1m3Spent acid adds 20% sodium thiosulfate 10L, vulcanized sodium 20g, is steam heated to 60 DEG C, stirring reaction
15min；Gained richness rhenium slag ingredient is rhenium 1.2%, arsenic 25.63%, copper 26.65%；Rhenium rate of deposition is 99.5%, and arsenic rate of deposition is only
1.86%, copper rate of deposition 99.2%.（3）By step（2）Gained richness rhenium slag carries out pressurised oxygen leaching.Leaching condition is：Liquid-solid ratio is
4,150 DEG C, partial pressure of oxygen 1.5MPa, extraction time 5h of extraction temperature；Steep cencentration is：Rhenium 6.7g/L, copper 142.17g/L, sulphur
Sour 39g/L.Rhenium leaching rate is 99.3%, copper leaching rate 99.2%.（4）By step（3）Gained richness rhenium leachate is in evaporate-crystallization
Freezing and crystallizing is carried out after being concentrated by evaporation in device to rhenium concentration about 10g/L, 15 DEG C of crystallization temperature, crystallization time 30min, potassium chloride adds
Dosage 25g/L, the thick potassium perrhenate purity of gained are 99.1%, rhenium percent crystallization in massecuite 90%.（5）By step（4）Gained potassium perrhenate is in burning
Add 50 DEG C of molten, liquid-solid ratioes 6 of hot water weight in the containers such as cup:1, oxidant addition is 3g/L, dissolves and is recrystallized after 5 DEG C,
Crystallization time 30min, gained potassium perrhenate purity are 99.99%, recrystallization ratio 99.1%.
（6）To step（3）In heavy rhenium after liquid addition copper content 1.4 times of vulcanized sodium, control temperature 60 C, reaction
1h；Filtering can obtain copper sulfide precipitation, rate of deposition 95.3%.
The all technical of five embodiments of the above is to such as table 1.
Each embodiment Detection results contrast table of table 1
Compare that the overall target that five embodiments of the above can be seen that embodiment 1 is best, and the embodiment is most preferably to implement
Example.
The present invention quickly reclaims in the method for rhenium, copper, lead from Copper making spent acid and targets the main affecting parameters of precipitation process
For reaction temperature, time, precipitating reagent addition：If can slowly be precipitated less than above-mentioned reaction temperature lower limit copper rhenium, precipitation effect is influenceed
Rate, accelerate higher than said temperature upper limit precipitation medicament selfdecomposition speed, it is necessary to increase pharmaceutical quantities；If less than under the above-mentioned reaction time
It is complete to limit copper rhenium unreacted, influences rate of deposition, higher than the above-mentioned reaction time upper limit, a small amount of precipitating reagent not consumed is possible to arsenic
Precipitate；If complete less than above-mentioned precipitating reagent addition lower limit copper rhenium unreacted, rate of deposition is influenceed, is added higher than above-mentioned precipitating reagent
Enter amount lower limit, excessive precipitating reagent precipitates arsenic, influences rhenium grade in rich rhenium slag.Rich rhenium slag uses autoclave hot-pressure oxidation
Leaching the main affecting parameters of rhenium includes liquid-solid ratio, extraction temperature, partial pressure of oxygen and extraction time：When liquid-solid ratio is less than lower limit, no
Contacted beneficial to medium with oxidant, influence leaching rate, during higher than the upper limit, leachate volume increases greatly to your follow-up liquid concentration
Add difficulty；During less than lowest temperature, leaching rate reduces, and during higher than temperature upper limit, causes high energy consumption, and autoclave temperature limitation is unsuitable
It is too high；When pressing the upper limit less than oxygen, reaction rate is slow, and oxidation is incomplete, when pressing the upper limit higher than oxygen, excessive oxygen, and the wasting of resources, medicine
Agent and equipment investment are big.
The application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, is not departing from the present invention
On the premise of principle, it can also according to the above description be improved or be modified, all these improvement or modification should all fall into this hair
In bright scope of the claims.
Claims (2)
1. rhenium, copper, the method for lead are quickly reclaimed in a kind of spent acid from Copper making, it is characterized in that：Remove Copper making spent acid is filtered
The heavy rhenium of targeting, heavy copper obtain rich rhenium copper ashes after lead, and the rich pressurized oxygen of rhenium copper ashes leaches to obtain rich rhenium leachate, and leachate is through evaporation
Concentration, the heavy rheniums of KCl obtain rehenic acid potassium product, and liquid obtains copper sulfide through vulcanization reaction after heavy rhenium；Operating procedure is as follows：
（a）Copper making spent acid is crossed through spent acid antigravity percolating filter and filters out lead, obtains lead content and carries lead more than the conduct of 55% lead skim
Raw material；
（b）The added thiosulfate of Copper making spent acid that rhenium content is 5mg/L-50mg/L compounds vulcanized sodium as precipitating reagent target
To after heavy rhenium, heavy copper, rich rhenium copper ashes is obtained；Rhenium content is 2%-5%, copper content 5-20%, reaction temperature 50- in rich rhenium copper ashes
70 DEG C, reaction time 5-15min, thiosulfate addition 2-5g/L, vulcanized sodium addition 10-20mg/L；
（c）By step（b）Gained richness rhenium copper ashes leaches rhenium, copper using pressurised oxygen, and course of reaction does not add any oxygen in addition to logical oxygen
Agent and soda acid, control liquid-solid ratio 4-8:1,130 DEG C -170 DEG C, partial pressure of oxygen 0.3MPa-1.5MPa of extraction temperature, extraction time
1h-5h；
（d）By step（c）Heavy rhenium-the recrystallization of gained leachate concentration prepares pure potassium perrhenate, and rich rhenium liquid rhenium is dense after control concentration
10g/L-20g/L is spent, KCl, 5 DEG C -15 DEG C of crystallization temperature, sedimentation time 5-40min are added by 15g/L-35g/L；The molten water temperature of weight
50 DEG C -100 DEG C, liquid-solid ratio 3-6:1, oxidant addition 1g/L-15g/L；After dissolving, control chilling temperature is at -5 DEG C -5 DEG C；
（e）By step（d）Liquid is placed in heavy copper in the heavy copper groove of vulcanization after the heavy rhenium of gained, controls vulcanized sodium addition as theoretical amount
1.1-1.5 times, 60-90 DEG C of reaction temperature, reaction time 1-3h.
2. it is a kind of realize described in claim 1 from Copper making spent acid quick recovery rhenium, copper, lead method device, its feature
It is：It includes rhenium copper precipitating reagent storage tank one, rhenium copper precipitating reagent storage tank two, rhenium copper stillpot, flocculation reaction groove one, compressive reaction
Kettle, evaporate-crystallization device, centrifugal separator, copper precipitating reagent storage tank, copper stillpot, flocculant storage tank, flocculation reaction groove two, spent acid
Antigravity percolating filter, rich rhenium copper ashes antigravity percolating filter, filter press one, filter press two, rhenium copper stillpot steam add
Hot systems, copper stillpot steam-heating system and Pulp pump；It is characterized in that the flocculant storage tank is in relatively high-order and connected
Flocculation reaction groove one and flocculation reaction groove two in relative low level are connect, copper precipitating reagent storage tank position is higher than and connects copper precipitation
Groove, rhenium copper precipitation groove location are higher than and connect flocculation reaction groove one, to realize flocculant, medicament gravity flow and reaction ore pulp overflow；
Mixed export, the spent acid antigravity percolating filter filtrate (liquid of rhenium copper precipitating reagent storage tank one and rhenium copper precipitating reagent storage tank two connect
Rhenium copper stillpot middle and lower part is connected to, rhenium copper stillpot top sets overfall, the top of overfall connection flocculation reaction groove one；Rich rhenium copper
Slag antigravity percolating filter slag notch connects compressive reaction kettle charging aperture, and bottom connection Pulp pump and filter press one, which are realized, to be leached
The filtering of slurry, the liquid outlet of filter press one are sequentially connected evaporate-crystallization device, centrifugal separator, centrifugal separator clear liquid overfall
Connect copper stillpot middle and upper part, copper precipitation trench bottom connection Pulp pump and filter press two.
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| CN112870844A (en) * | 2021-03-12 | 2021-06-01 | 中国恩菲工程技术有限公司 | Filtration recovery system and method |
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| CN103773963A (en) * | 2014-01-28 | 2014-05-07 | 白银有色集团股份有限公司 | Method for efficiently recovering copper and rhenium from copper smelting waste acid |
| CN104017996A (en) * | 2014-06-06 | 2014-09-03 | 白银有色集团股份有限公司 | Comprehensive recovery device and method for valuable metal in copper smelting acidic wastewater |
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| CN103773963A (en) * | 2014-01-28 | 2014-05-07 | 白银有色集团股份有限公司 | Method for efficiently recovering copper and rhenium from copper smelting waste acid |
| CN104017996A (en) * | 2014-06-06 | 2014-09-03 | 白银有色集团股份有限公司 | Comprehensive recovery device and method for valuable metal in copper smelting acidic wastewater |
| CN105274348A (en) * | 2015-11-23 | 2016-01-27 | 金川集团股份有限公司 | Method for extracting rhenium from copper smelting flue gas wet dust collecting liquid |
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