CN108754148A - A kind of processing method of cupric, manganese, cobalt, zinc, nickel heavy metal waste slag recycling - Google Patents
A kind of processing method of cupric, manganese, cobalt, zinc, nickel heavy metal waste slag recycling Download PDFInfo
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- CN108754148A CN108754148A CN201810588703.9A CN201810588703A CN108754148A CN 108754148 A CN108754148 A CN 108754148A CN 201810588703 A CN201810588703 A CN 201810588703A CN 108754148 A CN108754148 A CN 108754148A
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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
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
- C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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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
- C22B47/00—Obtaining manganese
- C22B47/0018—Treating ocean floor nodules
- C22B47/0045—Treating ocean floor nodules by wet processes
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a kind of cuprics, manganese, cobalt, zinc, the processing method of nickel heavy metal waste slag recycling, technique is leached using sulfate reduction, Extraction electrodeposition carries copper, neutralize removal of impurities, the heavy cobalt of vulcanization, the heavy manganese of carbonization, solution is evaporated crystallization, can the valuable metal in solid slag extraction be maximized to recycle, and technological process is simple, it is easy to operate, cost of disposal is low, it is a kind of economy, low consumption, the rate of recovery is high, recycle smelting cupric, manganese, the heavy metal solid slags treatment process such as cobalt, achieve the purpose that maximize and has economized on resources and reduce production run cost, realize country about waste treatment " minimizing, it recycles, the principle of recycling ", maximumlly accomplish to cupric, manganese, the comprehensive utilization of the heavy metal solid slags such as cobalt, substantially accomplished " eating dry bleed "；The minimizing of waste is realized, waste " zero-emission " is greatly advanced, greatly reduces ultimate waste disposal amount.
Description
Technical field
The invention belongs to contain heavy metal waste slag processing technology field, and in particular to a kind of cupric, manganese, cobalt, zinc, nickel weight
The processing method of metal waste residue recycling.
Background technology
Current China's industrial production is due to the fast development of early period, and the industrial solid wastes generated are also quick
It is incremented by, these wastes such as cannot be disposed effectively, not only polluted environment but also needed the stockyard of large area, while having wasted money
Source.Therefore, from the point of view of slowing down Resource exhaustion and resource reutilization, more metal hazardous industry solid wastes such as cupric, manganese, cobalt, zinc
Belong to the metals resources that can be developed and used.In the past 10 years, China's non-ferrous metal metallurgy Industry Quick Development, 10 kinds have coloured gold
Belong to yield to rank first in the world for continuous 11 years, the wherein heavy metals yield such as copper, lead, zinc is already expired ten million ton；The thing followed is a huge sum of money
Also cumulative year after year, current year yield cross ten million ton, the several hundred million tons of volume of cargo in storage over the years to the production discharge capacity of category melting waste slag.That stores up is big
It measures heavy metal and smelts solid waste not only land occupation, but also wherein containing As, Cd, Cr, Cu, Ni, Pb and Zn etc., there is height to move
The heavy metal and toxic element of shifting property cause greatly pollution and potential threat to environment, are the main of Heavy-metal Polluted Environment
One of form.
Features more for heavy metal waste slag, numerous, miscellaneous, several allusion quotations generated during thering is research to have chosen nonferrous smelting
Type solid waste of heavy metal is process object, has carried out heavy metal and has smelted solid waste stabilization processes research, has developed lead-zinc smelting wastewater
It neutralizes slag and zinc leaching residue hydro-thermal vulcanization stabilizing surface treatment, stablize containing arsenic smoke dust and zinc abstraction volatilization kiln slag mechanical force and chemical
Change treatment technology, waste acid system slag sulphur fixing process technology, high arsenic smoke dust hot pressing melting and solidification treatment technology, is heavy metal
The further research for smelting the innoxious safe handling disposal technology of solid waste provides new approaches and reference.What lead-zinc smelting generated
Stabilization processes are vulcanized by hydro-thermal with slag and zinc leaching residue in waste water, the stabilization of Heavy Metals is realized in water-heat process
Change transformation, Leaching of Heavy Metals concentration greatly reduces in waste residue after processing, meets state control standard；Containing arsenic smoke dust and zinc smelting
Refining volatilization kiln slag has occurred the self-propagating reaction of mechanical force induction, realizes waste residue by mechanical force and chemical stabilization processes
The stabilisation of middle Heavy Metals changes；Waste acid system slag use sulphur fixing process, realize heavy metal physically encapsulation and
The stabilisation of chemical form changes, and there are firming body long-time stability, compression strength to reach 21.9MPa, can be used as sulphur building materials money
Sourceization utilizes；High arsenic smoke dust is handled by hot pressing melting and solidification, and the height of arsenic in cigarette ash can be realized under lower solidification temperature
Immobilization is imitated, firming body is fine and close and has gloss, can be fabricated to crystal class product.These achievements in research will attach most importance to metal smelt
The stabilisation safe handling disposition of waste residue provides new way, for the safe handling for the hazardous waste that nonferrous smelting industry generates
Disposition provides reference, has ensured the sustainable development of nonferrous smelting industry.
The heavy metal waste slags such as cupric, manganese, cobalt result from the waste residue after the purification and impurity removal in nonferrous smelting industry, these contain
There is the sludge of heavy metal to have the characteristics that easily to accumulate, is unstable, being easy to run off, if do not dealt carefully with, the dirt of serious environment can be caused
Dye.Although these cuprics, manganese, cobalt waste residue belong to hazardous industry solid waste, waste residue cupric grade after drying process exists
Between 8%~13%, wherein also containing the dilute expensive and non-ferrous metals such as copper, manganese, cobalt, zinc.
Now in the solidification disposal of waste technique of hazardous industry containing heavy metal, common method of disposal mainly have security landfill,
Pyrogenic process disposition, wet method are disposed and wait three kinds of disposing techniques, wherein：1, security landfill method not only land occupation, causes the wave of resource
Take, returns the hidden danger that offspring leaves huge environmental pollution；2, although existing pyrogenic process disposing technique has by different dangerous solid wastes
Kind, which is concentrated, carries out high-volume disposition, generates the short advantage of harmless clinker, flow, but there is also following 3 problems：Flue gas is dirty
It is low to contaminate big, high energy consumption, recovery rate of valuable metals, is unfavorable for resource and maximally utilizes；Wet method disposing technique is directed to different danger
Solid waste kind needs to use different wet method disposal process, it is difficult to accomplishes to concentrate the cooperative disposal of " high-volume, multi items ", and
Waste water that production process generates, waste residue still fall within hazardous waste, be not achieved " pollution treatment do not produce dirty, profit it is useless do not produce it is useless " it is innoxious
Effect.
The patent application of Publication No. CN102230086A discloses a kind of from manganese ore leaching technique removing heavy metals vulcanized slag
In simultaneously leaching cobalt, nickel method, belong to cobalt, nickel recovery technology field.The present invention basic step be：In the reactor plus
Enter vulcanized slag, nitration mixture solution is then added, is 2 with water modulation ore pulp liquid-solid ratio:1~7:1；45~100
Be stirred to react at a temperature of DEG C and obtain within 20~120 minutes reaction leachate, cobalt, nickel leaching rate be more than 90%, but this method only needle
To cobalt, nickel recycling, cyclic utilization rate is relatively low, and at present there is no the relevant technologies can from heavy metal waste slag and meanwhile recycle copper,
Manganese, cobalt, zinc etc. is dilute expensive and non-ferrous metal.
Invention content
Technical problem to be solved by the present invention lies in existing shortcoming and defect for the above-mentioned prior art, provide one
The processing method of the high cupric of kind economy, low consumption, the rate of recovery, manganese, cobalt, zinc, nickel heavy metal waste slag recycling.
In order to achieve the above object, the present invention is achieved by the following scheme：
The processing method of a kind of cupric, manganese, cobalt, zinc, nickel heavy metal waste slag recycling is handled according to following process and is completed：
Cobalt → heavy manganese-evaporation is sunk in acidleach → Extraction electrodeposition → neutralization → vulcanization.
Preferably, the acidleach process is as follows：
It is after pretreatment to contain heavy metal first with water by cupric, manganese, cobalt, zinc, nickel heavy metal waste slag material pulping and washing
Raw material slag presses liquid-solid ratio 2-4 again after metering:1 is added water, starts stirring pulp, is slowly added to metallic element in heavy metal slag
98% sulfuric acid of 1.0-1.2 times of content molar ratio, then it is interior by oxidized metal constituent content molar ratio 1 by heavy metal slag：1 is added
Reducing agent controls the pH value of the solution as reaction end when 1.5-2.0 is constant, leaches slurry and pressurizes through plate and frame filter press and filters
Separation, filter cake slag is another after being washed with water to be used, and wash water, which is back to, leaches dispensing section reuse, and filtrate raffinate allotment after extracting copper is dilute
It is 10-12g/L to release to copper ion concentration, is sent to Extraction electrodeposition process.
It is further preferred that the reducing agent in the acidleach process is ammonium sulfite, ammonium bisulfite, ammonium pyrosulfite
With one or more of oxalic acid mixture.
It is further preferred that the reaction temperature control in the acidleach process is at 70-80 DEG C, reaction time 1.5-2.5h.
Preferably, the Extraction electrodeposition process is as follows：
After acidleach process, it will be sent to extracting system with the qualified filtrate of raffinate allotment, carry out copper extraction and separation, it is described
For extracting system using three extractions, two back extraction, two washings, extractant selects hydroximic species of extractants, and raffinate, which returns, leaches dispensing and tune
With extraction stoste, extraction cycle 2-5 time sends to electrodeposition workshop section and produces electrodeposition copper coin when sulfuric acid copper content is up to >=45g/L.
It is further preferred that in the copper extraction process：Stoste extracts Cu content 10-12g/L, and temperature is controlled at 25-40 DEG C
Between, wash water acidity 4-6g/L, back extraction acidacidity is 170-190g/L,
Further preferably, the extractant is Lix984N.
Preferably, the neutralization step is as follows：
Extraction extraction raffinate to neutralizing zone after the completion of Extraction electrodeposition process carries out the removal of impurities before cobalt, manganese separation, is first exposed
Gas aoxidizes 25-35 minutes, and slowly the uniform lime that is added adjusts pH to 3.5-4.0 under stirring, and temperature is controlled in 55-
It 65 DEG C, reacts 1.5-2.5 hours, is not separated by solid-liquid separation after variation after pH, filter cake slag is another after being washed with water to be used, and filtrate is standby
With.
Preferably, the heavy cobalt process of the vulcanization is as follows：
Filtrate obtained by neutralized process is sent to vulcanization process and carries out cobalt separation and Extraction, under stirring slowly uniformly with
The mode of spray is added by 1.2-1.4 times of mole ratio and prepares the sodium sulfide solution that mass concentration is 18%-22% in advance,
At 70-80 DEG C, pH is controlled within the scope of 4.4-5.4 for temperature control, reaction time 0.5-2 hour, then is carried out through plate and frame filter press
It is separated by solid-liquid separation, measures and be packaged after the new water washing of filter cake slag, filtrate send to heavy manganese-evaporization process the recycling for carrying out manganese.
Preferably, the heavy manganese-evaporization process is as follows：
Filtrate after the heavy cobalt process of vulcanization carries out the recycling of manganese, slowly uniformly by manganese ion in solution under stirring
0.8-1.5 times of the ammonium hydrogen carbonate that mole is added in manganese ion content is added in content, and temperature is controlled at 45-55 DEG C, when in solution
Manganese content≤2mg/L when be separated by solid-liquid separation through plate and frame filter press, filtrate is sent to vapo(u)rization system, be evaporated crystallization recycling
Ammonium sulfate, evaporation condensed water return system circulation and utilize.
Present invention has the advantages that：
The processing method of the heavy metal waste slag recycling of the present invention using sulfate reduction leaching, Extraction electrodeposition carry copper, in
With removal of impurities, the heavy cobalt of vulcanization, the heavy manganese of carbonization, solution is evaporated crystallization, can maximize the valuable metal in solid slag and carry
Recycling is taken, and technological process is simple, easy to operate, cost of disposal is low, the advantage for having economy, low consumption, the rate of recovery high,
It can recycle and smelt the heavy metal solid slags techniques such as cupric, manganese, cobalt, reach maximization and economized on resources and reduce life
The purpose of operating cost is produced, realizes principle of the country about waste treatment " minimizing, recycling, recycling ", maximumlly
Accomplish, to the comprehensive utilization of the heavy metal solid slags such as cupric, manganese, cobalt, substantially to have accomplished " eating dry bleed "；Realize waste
Minimizing greatly advances waste " zero-emission ", greatly reduces ultimate waste disposal amount.
The separation of the processing method of the heavy metal waste slag recycling of the present invention, cobalt manganese is detached using precipitation, introduces system
Water it is smaller and be back to leach process recycle, it can be achieved that water zero-emission, not only reduce cost, but also economize on resources, really
Resource reclaim, energy-saving and emission-reduction, environmental protection.
Description of the drawings
Fig. 1 is the process flow of a kind of cupric of the present invention, manganese, cobalt, zinc, nickel heavy metal waste slag recycling.
Specific implementation mode
It is the specific embodiment of the content of present invention below, for illustrating the technical problem of being solved in present specification
Technical solution contributes to those skilled in the art understand that the content of present invention, but the realization of technical solution of the present invention is not limited to this
A little embodiments.
The processing method of 1 cupric of embodiment, manganese, cobalt, zinc, nickel heavy metal waste slag recycling
Cupric, manganese, cobalt, zinc, nickel heavy metal waste slag material are handled according to following process and completed：Acidleach → Extraction electrodeposition
Cobalt → heavy manganese-evaporation is sunk in → neutralization → vulcanization.
The processing method of 2 cupric of embodiment, manganese, cobalt, zinc, nickel heavy metal waste slag recycling
Cupric, manganese, cobalt, zinc, nickel heavy metal waste slag material are handled according to following process and completed：
(1) acidleach process
It is after pretreatment to contain heavy metal first with water by cupric, manganese, cobalt, zinc, nickel heavy metal waste slag material pulping and washing
Raw material slag presses liquid-solid ratio 2 again after metering:1 is added water, starts stirring pulp, is slowly added to metallic element in heavy metal slag and contains
98% sulfuric acid of 1.0 times of molar ratio is measured, then interior by oxidized metal constituent content molar ratio 1 by heavy metal slag：1 is added sulfurous acid
Ammonium, it is to react when 1.5-2.0 is constant that reaction temperature, which controls the pH value that solution is controlled at 70-80 DEG C, reaction time 1.5h,
Terminal leaches slurry through plate and frame filter press pressurization filter separation, and rear another use is washed with water in filter cake slag, and wash water is back to leaching dispensing
Duan Huiyong, filtrate raffinate allotment after extracting copper are diluted to copper ion concentration as 10-12g/L, send to Extraction electrodeposition process.
(2) Extraction electrodeposition process
After acidleach process, it will be sent to extracting system with the qualified filtrate of extraction extraction raffinate allotment, carry out copper extraction and separation, institute
Extracting system is stated using three extractions, two back extraction, two washings, every end is respectively provided with defecator, and extractant selects Lix984N, raffinate
Liquid, which returns, leaches dispensing and allotment extraction stoste, in copper extraction process：Stoste extracts Cu content 10-12g/L, and temperature is controlled in 25-
Between 40 DEG C, wash water acidity 6g/L, back extraction acidacidity is 170g/L, and extraction cycle 2 times is sent when sulfuric acid copper content is up to >=45g/L
Electrodeposition workshop section is gone to produce electrodeposition copper coin.
(3) neutralization step
Extraction extraction raffinate to neutralizing zone after the completion of Extraction electrodeposition process carries out the removal of impurities before cobalt, manganese separation, is first exposed
Gas aoxidizes 25 minutes, and slowly the uniform lime that is added adjusts pH to 3.5-4.0 under stirring, and temperature is controlled at 55 DEG C, instead
It answers 1.5 hours, is not separated by solid-liquid separation after variation after pH, filter cake slag is another after being washed with water to be used, and filtrate is spare.
(4) heavy cobalt process is vulcanized
Filtrate obtained by neutralized process is sent to vulcanization process and carries out cobalt separation and Extraction, under stirring slowly uniformly with
The mode of spray is added by 1.2 times of mole prepares the sodium sulfide solution that mass concentration is 18% in advance, and temperature control exists
70-80 DEG C, pH is controlled within the scope of 4.4-5.4,0.5 hour reaction time, then is separated by solid-liquid separation through plate and frame filter press, is filtered
It measures and is packaged after the new water washing of cake slag, filtrate send to heavy manganese-evaporization process the recycling for carrying out manganese.
(5) heavy manganese-evaporation
Filtrate after the heavy cobalt process of vulcanization carries out the recycling of manganese, slowly uniformly by manganese ion in solution under stirring
0.8 times of ammonium hydrogen carbonate of mole is added in content, and temperature is controlled at 45-55 DEG C, as manganese content≤2mg/L in solution
It is separated by solid-liquid separation through plate and frame filter press, filtrate is sent to vapo(u)rization system, and crystallization recycling ammonium sulfate, evaporation condensed water are evaporated
System circulation is returned to utilize.
The processing method of 3 cupric of embodiment, manganese, cobalt, zinc, nickel heavy metal waste slag recycling
Cupric, manganese, cobalt, zinc, nickel heavy metal waste slag material are handled according to following process and completed：
(1) acidleach process
It is after pretreatment to contain heavy metal first with water by cupric, manganese, cobalt, zinc, nickel heavy metal waste slag material pulping and washing
Raw material slag presses liquid-solid ratio 4 again after metering:1 is added water, starts stirring pulp, is slowly added to metallic element in heavy metal slag and contains
98% sulfuric acid of 1.2 times of molar ratio is measured, then interior by oxidized metal constituent content molar ratio 1 by heavy metal slag：1 is added sulfurous acid
Hydrogen ammonium, reaction temperature are controlled at 70-80 DEG C, reaction time 2.5h, and the pH value for controlling solution is as anti-when 1.5-2.0 is constant
Terminal is answered, leaches slurry through plate and frame filter press pressurization filter separation, rear another use is washed with water in filter cake slag, and wash water is back to leaching and matches
Expect that section reuse, filtrate raffinate allotment after extracting copper are diluted to copper ion concentration as 10-12g/L, send to Extraction electrodeposition process.
(2) Extraction electrodeposition process
After acidleach process, it will be sent to extracting system with the qualified filtrate of raffinate allotment, carry out copper extraction and separation, it is described
Extracting system is respectively provided with defecator using three extractions, two back extraction, two washings, every end, and extractant selects Lix984N, raffinate
It returns and leaches dispensing and allotment extraction stoste, in copper extraction process：Stoste extracts Cu content 10-12g/L, and temperature is controlled in 25-40
Between DEG C, wash water acidity 4g/L, back extraction acidacidity is 190g/L, and extraction cycle 5 times is sent to when sulfuric acid copper content is up to >=45g/L
Electrodeposition workshop section produces electrodeposition copper coin.
(3) neutralization step
Extraction extraction raffinate to neutralizing zone after the completion of Extraction electrodeposition process carries out the removal of impurities before cobalt, manganese separation, is first exposed
Gas aoxidizes 35 minutes, and slowly the uniform lime that is added adjusts pH to 3.5-4.0 under stirring, and temperature is controlled at 65 DEG C, instead
It answers 2.5 hours, is not separated by solid-liquid separation after variation after pH, filter cake slag is another after being washed with water to be used, and filtrate is spare.
(4) heavy cobalt process is vulcanized
Filtrate obtained by neutralized process is sent to vulcanization process and carries out cobalt separation and Extraction, under stirring slowly uniformly with
The mode of spray is added by 1.4 times of mole prepares the sodium sulfide solution that mass concentration is 22% in advance, and temperature control exists
70-80 DEG C, pH is controlled within the scope of 4.4-5.4,2 hours reaction time, then is separated by solid-liquid separation through plate and frame filter press, filter cake
It measures and is packaged after the new water washing of slag, filtrate send to heavy manganese-evaporization process the recycling for carrying out manganese.
(5) heavy manganese-evaporation
Filtrate after the heavy cobalt process of vulcanization carries out the recycling of manganese, slowly uniformly by manganese ion in solution under stirring
1.5 times of ammonium hydrogen carbonate of mole is added in content, and temperature is controlled at 45-55 DEG C, as manganese content≤2mg/L in solution
It is separated by solid-liquid separation through plate and frame filter press, filtrate is sent to vapo(u)rization system, and crystallization recycling ammonium sulfate, evaporation condensed water are evaporated
System circulation is returned to utilize.
The processing method of 4 cupric of embodiment, manganese, cobalt, zinc, nickel heavy metal waste slag recycling
Cupric, manganese, cobalt, zinc, nickel heavy metal waste slag material are handled according to following process and completed：
(1) acidleach process
It is after pretreatment to contain heavy metal first with water by cupric, manganese, cobalt, zinc, nickel heavy metal waste slag material pulping and washing
Raw material slag presses liquid-solid ratio 3 again after metering:1 is added water, starts stirring pulp, is slowly added to metallic element in heavy metal slag and contains
98% sulfuric acid of 1.1 times of molar ratio is measured, then interior by oxidized metal constituent content molar ratio 1 by heavy metal slag：1 is added sulfurous acid
Ammonium, it is to react eventually when 1.5-2.0 is constant that reaction temperature, which controls the pH value that solution is controlled at 70-80 DEG C, reaction time 2h,
Point leaches slurry through plate and frame filter press pressurization filter separation, and filter cake slag another use after being washed with water, wash water, which is back to, leaches dispensing section
Reuse, filtrate raffinate allotment after extracting copper are diluted to copper ion concentration as 10-12g/L, send to Extraction electrodeposition process.
(2) Extraction electrodeposition process
After acidleach process, it will be sent to extracting system with the qualified filtrate of extraction extraction raffinate allotment, carry out copper extraction and separation, institute
Extracting system is stated using three extractions, two back extraction, two washings, every end is respectively provided with defecator, and extractant selects Lix984N, raffinate
Liquid, which returns, leaches dispensing and allotment extraction stoste, in copper extraction process：Stoste extracts Cu content 10-12g/L, and temperature is controlled in 25-
Between 40 DEG C, wash water acidity 5g/L, back extraction acidacidity is 180g/L, and extraction cycle 3 times is sent when sulfuric acid copper content is up to >=45g/L
Electrodeposition workshop section is gone to produce electrodeposition copper coin.
(3) neutralization step
Raffinate to neutralizing zone after the completion of Extraction electrodeposition process carries out the removal of impurities before cobalt, manganese separation, is first aerated
Oxidation 30 minutes, slowly the uniform lime that is added adjusts pH to 3.5-4.0 under stirring, and temperature is controlled at 60 DEG C, reaction
It 2 hours, is not separated by solid-liquid separation after variation after pH, filter cake slag is another after being washed with water to be used, and filtrate is spare.
(4) heavy cobalt process is vulcanized
Filtrate obtained by neutralized process is sent to vulcanization process and carries out cobalt separation and Extraction, under stirring slowly uniformly with
The mode of spray is added by 1.3 times of mole prepares the sodium sulfide solution that mass concentration is 20% in advance, and temperature control exists
70-80 DEG C, pH is controlled within the scope of 4.4-5.4,1 hour reaction time, then is separated by solid-liquid separation through plate and frame filter press, filter cake
It measures and is packaged after the new water washing of slag, filtrate send to heavy manganese-evaporization process the recycling for carrying out manganese.
(5) heavy manganese-evaporation
Filtrate after the heavy cobalt process of vulcanization carries out the recycling of manganese, slowly uniformly by manganese ion in solution under stirring
1.1 times of ammonium hydrogen carbonate of mole is added in content, and temperature is controlled at 45-55 DEG C, as manganese content≤2mg/L in solution
It is separated by solid-liquid separation through plate and frame filter press, filtrate is sent to vapo(u)rization system, and crystallization recycling ammonium sulfate, evaporation condensed water are evaporated
System circulation is returned to utilize.
5 cupric of embodiment, manganese, cobalt, zinc, the experiment of nickel heavy metal waste slag recycling
Cupric, manganese, cobalt, zinc, nickel heavy metal waste slag material are handled according to following process and completed：
(1) acidleach process
Acid, which is mainly added, in the process makes the valuable heavy metal in waste residue maximumlly leach, due to cobalt, the manganese in waste residue
With the presence of by high price too in the form of, so suitable reducing agent that is added can greatly improve the leaching of each metal in leaching process
Rate.
Feedstock analysis：Main chemical elements composition (see the table below 1) containing heavy metal waste slag.
1 bronze medal manganese slag of table analyzes data
It is after pretreatment to contain heavy metal first with water by cupric, manganese, cobalt, zinc, nickel heavy metal waste slag material pulping and washing
Raw material slag presses liquid-solid ratio 3 again after metering:1 is added water, starts stirring pulp, is slowly added to metallic element in heavy metal slag and contains
98% sulfuric acid of 1.1 times of molar ratio is measured, then interior by oxidized metal constituent content molar ratio 1 by heavy metal slag：1 is added sulfurous acid
Ammonium, it is to react eventually when 1.5-2.0 is constant that reaction temperature, which controls the pH value that solution is controlled at 70-80 DEG C, reaction time 2h,
Point leaches slurry through plate and frame filter press pressurization filter separation, and filter cake slag another use after being washed with water, wash water, which is back to, leaches dispensing section
Reuse, filtrate raffinate allotment after extracting copper are diluted to copper ion concentration as 10-12g/L, send to Extraction electrodeposition process.
Leach analysis data (see the table below 2 and table 3)
Table 2 leaches filtrate analysis data
3 filter cake slag of table analyzes data
This technique is leached using sulfate reduction, and reducing agent is used as using ammonium sulfite, height that can be in great reduced waste residue
Valence metal ion is improved its leaching rate, and is existed in solution in the form of ammonium sulfate after ammonium sulfite reaction, and postorder can be straight
Evaporative crystallization recycling is connect, secondary pollution is not brought into total system；The leaching rate of copper can reach 98% or more in leaching process,
The leaching rate of manganese reaches 98%, and cobalt recycling can reach 96% or more, and the quantity of slag can greatly leach useless metal in the dreg in 10-15%
Ion, content of beary metal can be reduced to 0.5 or less in the slag after leaching.
(2) Extraction electrodeposition process
After acidleach process, it will be sent to extracting system with the qualified filtrate of extraction extraction raffinate allotment, carry out copper extraction and separation, institute
Extracting system is stated using three extractions, two back extraction, two washings, every end is respectively provided with defecator, and extractant selects Lix984N, raffinate
Liquid, which returns, leaches dispensing and allotment extraction stoste, in copper extraction process：Stoste extracts Cu content 10-12g/L, and temperature is controlled in 25-
Between 40 DEG C, wash water acidity 5g/L, back extraction acidacidity is 180g/L, and extraction cycle 3 times is sent when sulfuric acid copper content is up to >=45g/L
Electrodeposition workshop section is gone to produce electrodeposition copper coin.
Extracting system is respectively provided with defecator using three extractions, two back extraction, two washings, every end in this process, can reach more
Good split-phase effect, extraction process control exist：Stoste extracts Cu contents：10~12g/L, temperature are controlled between 25-40 DEG C, are washed
Acidity of water 5g/L, back extraction acidacidity are 180g/L, and raffinate, which returns, leaches dispensing and allotment extraction stoste, recycles 3 times, you can
Reduce the dosage of the new water of entire technique, and can reach the enrichment of manganese, cobalt, can smaller next step separation of cobalt from manganese recycling disposal cost,
Improve whole economic efficiency.Raffinate is through after extracting stage circulation collection, manganese can reach 80~120g/L, 9~15g/L of cobalt, sulphur
Sour copper content reaches >=45g/L or more when send to electrodeposition workshop section production electrodeposition copper coin.
(3) neutralization step
Extraction extraction raffinate to neutralizing zone after the completion of Extraction electrodeposition process carries out the removal of impurities before cobalt, manganese separation, is first exposed
Gas aoxidizes 30 minutes, and slowly the uniform lime that is added adjusts pH to 3.5-4.0 under stirring, and temperature is controlled at 60 DEG C, instead
It answers 2 hours, is not separated by solid-liquid separation after variation after pH, filter cake slag is another after being washed with water to be used, and filtrate is spare.
Manganese therein has been enriched with to 80g/L or more after raffinate recycles three times, is sent before carrying out cobalt, manganese separation to neutralizing zone
Removal of impurities.First carrying out aerating oxidation 30 minutes, (directly rousing compressed air) will be therein ferrous oxidising to trivalent.After testing,
In and during manganese loss 5% or so, cobalt loss is less than 1%.It neutralizes slag analysis data and is shown in Table 4.
In table 4 and slag analyzes data
(4) heavy cobalt process is vulcanized
Filtrate obtained by neutralized process is sent to vulcanization process and carries out cobalt separation and Extraction, under stirring slowly uniformly with
The mode of spray is added by 1.3 times of mole prepares the sodium sulfide solution that mass concentration is 20% in advance, and temperature control exists
70-80 DEG C, pH is controlled within the scope of 4.4-5.4,1 hour reaction time, then is separated by solid-liquid separation through plate and frame filter press, filter cake
It measures and is packaged after the new water washing of slag, filtrate send to heavy manganese-evaporization process the recycling for carrying out manganese.Vulcanized slag analyzes data
It is shown in Table 5.
5 vulcanized slag of table analyzes data
Sulfurization-precipitation method detaches cobalt, manganese ion, is that the solubility product based on each heavy metal sulfide is different, in certain item
Metal ion is detached with vulcanizing agent under part, considers that the high cobalt of characteristic manganese of this material is low, therefore this technique is heavy using vulcanization
Form sediment separation cobalt manganese, this technological process is simple, easy to operate, and cost is low, and for the low leachate separating effect of the high cobalt of manganese
It is good preferable.Manganese loss is in 4-6% or so during cobalt is sunk in vulcanization, and the recycling of cobalt is up to 95% or more.
(5) heavy manganese-evaporation
Filtrate after the heavy cobalt process of vulcanization carries out the recycling of manganese, slowly uniformly by manganese ion in solution under stirring
The ammonium hydrogen carbonate of 1.1 times of mole is added in content, and temperature is controlled at 45-55 DEG C, passed through as manganese content≤2mg/L in solution
Plate and frame filter press is separated by solid-liquid separation, and filtrate is sent to vapo(u)rization system, is evaporated crystallization recycling ammonium sulfate, and evaporation condensed water returns
System circulation utilizes.Manganese carbonate analysis data are shown in Table 6.
6 manganese carbonate of table analyzes data
Claims (10)
1. the processing method of a kind of cupric, manganese, cobalt, zinc, nickel heavy metal waste slag recycling is handled according to following process and is completed：Acid
Cobalt → heavy manganese-evaporation is sunk in leaching → Extraction electrodeposition → neutralization → vulcanization.
2. the processing method of cupric, manganese, cobalt, zinc, nickel heavy metal waste slag recycling according to claim 1, it is characterised in that
The acidleach process is as follows：It is after pretreatment first with water by cupric, manganese, cobalt, zinc, nickel heavy metal waste slag material pulping and washing
The slag of raw material containing heavy metal presses liquid-solid ratio 2-4 again after metering:1 is added water, starts stirring pulp, is slowly added in heavy metal slag golden
98% sulfuric acid for belonging to 1.0-1.2 times of constituent content molar ratio is pressed in heavy metal slag further according to experimental data by oxidized metal element
Content molar ratio 1：1 is added reducing agent, controls the pH value of the solution as reaction end when 1.5-2.0 is constant, leaches slurry warp
Plate and frame filter press pressurization filter separation, filter cake slag is another after being washed with water to be used, and wash water, which is back to, leaches dispensing section reuse, and filtrate is through extracting copper
It is 10-12g/L that raffinate allotment, which is diluted to copper ion concentration, afterwards, is sent to Extraction electrodeposition process.
3. the processing method of cupric, manganese, cobalt, zinc, nickel heavy metal waste slag recycling according to claim 2, it is characterised in that
Reducing agent in the acidleach process is that one or more of ammonium sulfite, ammonium bisulfite, ammonium pyrosulfite and oxalic acid are mixed
And object.
4. the processing method of cupric, manganese, cobalt, zinc, nickel heavy metal waste slag recycling according to claim 2, it is characterised in that
Reaction temperature control in the acidleach process is at 70-80 DEG C, reaction time 1.5-2.5h.
5. special according to the processing method of any cuprics of claim 1-4, manganese, cobalt, zinc, nickel heavy metal waste slag recycling
Sign is that the Extraction electrodeposition process is as follows：After acidleach process, it will be sent to extracting system with the qualified filtrate of raffinate allotment,
Copper extraction and separation are carried out, the extracting system selects hydroximic species of extractants, raffinate using three extractions, two back extraction, two washings, extractant
Liquid return leach dispensing and allotment extraction stoste, extraction cycle 2-5 time, sulfuric acid copper content reach >=45g/L when send to electrodeposition workshop section
Produce electrodeposition copper coin.
6. the processing method of cupric, manganese, cobalt, zinc, nickel heavy metal waste slag recycling according to claim 5, which is characterized in that
In the copper extraction process：Stoste extracts Cu content 10-12g/L, and temperature controls between 25-40 DEG C, wash water acidity 4-6g/L, instead
Extraction acidacidity is 170-190g/L.
7. the processing method of cupric, manganese, cobalt, zinc, nickel heavy metal waste slag recycling according to claim 5, which is characterized in that
The extractant is Lix984N.
8. special according to the processing method of any cuprics of claim 1-7, manganese, cobalt, zinc, nickel heavy metal waste slag recycling
Sign is that the neutralization step is as follows：Before extraction extraction raffinate to neutralizing zone after the completion of Extraction electrodeposition process carries out cobalt, manganese separation
Removal of impurities, first carries out aerating oxidation 25-35 minutes, and slowly the uniform lime that is added adjusts pH to 3.5-4.0, temperature under stirring
Degree control is reacted 1.5-2.5 hours, is not separated by solid-liquid separation after variation after pH at 55-65 DEG C, and filter cake slag is another after being washed with water
With filtrate is spare.
9. special according to the processing method of any cuprics of claim 1-8, manganese, cobalt, zinc, nickel heavy metal waste slag recycling
Sign is that the heavy cobalt process of the vulcanization is as follows：Filtrate obtained by neutralized process is sent to vulcanization process and carries out cobalt separation and Extraction, is stirring
It is 18%- to mix and preparation mass concentration in advance uniformly slowly is added by 1.2-1.4 times of mole in a manner of spray under state
22% sodium sulfide solution, at 70-80 DEG C, pH is controlled within the scope of 4.4-5.4 for temperature control, reaction time 0.5-2 hour, then
It is separated by solid-liquid separation through plate and frame filter press, measures and be packaged after the new water washing of filter cake slag, filtrate is sent to heavy manganese-evaporization process and carried out
The recycling of manganese.
10. special according to the processing method of any cuprics of claim 1-9, manganese, cobalt, zinc, nickel heavy metal waste slag recycling
Sign is that the heavy manganese-evaporization process is as follows：Filtrate after the heavy cobalt process of vulcanization carries out the recycling of manganese, under stirring slowly
0.8-1.5 times of ammonium hydrogen carbonate of mole is uniformly added by manganese ion content in solution, temperature is controlled at 45-55 DEG C, when molten
It is separated by solid-liquid separation through plate and frame filter press when manganese content≤2mg/L in liquid, filtrate is sent to vapo(u)rization system, is evaporated and crystallizes back
Ammonium sulfate is received, evaporation condensed water returns system circulation and utilizes.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110512082A (en) * | 2019-09-20 | 2019-11-29 | 常州工学院 | A kind of recovery method of discarded metal sludge |
| CN111100992A (en) * | 2019-12-31 | 2020-05-05 | 荆门市格林美新材料有限公司 | Treatment method of nickel wet refining tailings based on high-temperature reduction |
| CN111850305A (en) * | 2020-07-28 | 2020-10-30 | 昆明理工大学 | Method for leaching cobalt and manganese from manganese-rich cobalt slag |
| CN112553478A (en) * | 2020-12-02 | 2021-03-26 | 金川集团镍盐有限公司 | Method for quickly leaching nickel hydroxide cobalt sulfuric acid system |
| CN113845455A (en) * | 2021-10-12 | 2021-12-28 | 兰州大学 | Method for recycling Fumei slag |
| CN114231746A (en) * | 2021-11-30 | 2022-03-25 | 西北矿冶研究院 | Method for recovering copper from copper smelting waste acid and gypsum slag |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021331A (en) * | 2010-12-11 | 2011-04-20 | 付春平 | Processing method for comprehensively recovering high manganese asbolite |
| CN105256141A (en) * | 2015-10-26 | 2016-01-20 | 广西银亿再生资源有限公司 | Electroplating-sludge resourceful treatment and comprehensive recycling method |
-
2018
- 2018-06-08 CN CN201810588703.9A patent/CN108754148B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021331A (en) * | 2010-12-11 | 2011-04-20 | 付春平 | Processing method for comprehensively recovering high manganese asbolite |
| CN105256141A (en) * | 2015-10-26 | 2016-01-20 | 广西银亿再生资源有限公司 | Electroplating-sludge resourceful treatment and comprehensive recycling method |
| CN105256141B (en) * | 2015-10-26 | 2017-12-19 | 广西银亿再生资源有限公司 | A kind of electric plating sludge resource processing and the method for comprehensive reutilization |
Non-Patent Citations (1)
| Title |
|---|
| 李卫民: "巴甲矿业公司埃尔波利奥项目铜、钻、锌、锰回收的湿法冶金处理", 《国外工程技术》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110512082A (en) * | 2019-09-20 | 2019-11-29 | 常州工学院 | A kind of recovery method of discarded metal sludge |
| CN110512082B (en) * | 2019-09-20 | 2020-11-03 | 常州工学院 | Recovery method of waste metal sludge |
| CN111100992A (en) * | 2019-12-31 | 2020-05-05 | 荆门市格林美新材料有限公司 | Treatment method of nickel wet refining tailings based on high-temperature reduction |
| CN111850305A (en) * | 2020-07-28 | 2020-10-30 | 昆明理工大学 | Method for leaching cobalt and manganese from manganese-rich cobalt slag |
| CN112553478A (en) * | 2020-12-02 | 2021-03-26 | 金川集团镍盐有限公司 | Method for quickly leaching nickel hydroxide cobalt sulfuric acid system |
| CN113845455A (en) * | 2021-10-12 | 2021-12-28 | 兰州大学 | Method for recycling Fumei slag |
| CN113845455B (en) * | 2021-10-12 | 2022-06-14 | 兰州大学 | Recycling method of Fumei slag |
| CN114231746A (en) * | 2021-11-30 | 2022-03-25 | 西北矿冶研究院 | Method for recovering copper from copper smelting waste acid and gypsum slag |
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