CN108609653A - A method of it extracting arsenic from the slag of nickel cobalt containing arsenic and prepares arsenate - Google Patents
A method of it extracting arsenic from the slag of nickel cobalt containing arsenic and prepares arsenate Download PDFInfo
- Publication number
- CN108609653A CN108609653A CN201810519109.4A CN201810519109A CN108609653A CN 108609653 A CN108609653 A CN 108609653A CN 201810519109 A CN201810519109 A CN 201810519109A CN 108609653 A CN108609653 A CN 108609653A
- Authority
- CN
- China
- Prior art keywords
- arsenic
- slag
- nickel cobalt
- containing arsenic
- cobalt containing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of arsenic
- C01G28/02—Arsenates; Arsenites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of arsenic
- C01G28/02—Arsenates; Arsenites
- C01G28/023—Arsenates; Arsenites of ammonium, alkali or 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
-
- 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
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of methods extracted arsenic in slag from nickel cobalt containing arsenic and prepare arsenate, and the slag of nickel cobalt containing arsenic is added in the aqueous slkali for being placed in reaction vessel and obtains slurries, be passed through gaseous oxidant from slurries bottom carries out atmospheric pressure oxidation under stiring；It is separated by solid-liquid separation, obtains filter residue and filtrate containing arsenic, the evaporative crystallization of filtrate containing arsenic obtains arsenic acid salt crystal.The present invention is passed through by agitating mode, mixing speed, gas flow, gas under the synergistic effect of mode during alkali oxide soaks, and realizes mixed slot reaction mechanism entirely.The present invention uses the alkaline process Oxidation Leaching slag of nickel cobalt containing arsenic, it is leached using cheap unstrpped gas oxidant (such as air), in the case of atmospheric low-temperature, efficient leaching can be realized, the difficulty and technique productions cost for significantly reducing technique productions, have great industrialization meaning.
Description
Technical field
The present invention relates to the Slag treatment technical fields of nickel cobalt containing arsenic, and in particular to one kind being extracted arsenic and made from the slag of nickel cobalt containing arsenic
The method of standby arsenate.
Background technology
Arsenic is a kind of widely distributed metalloid element of nature, is the indispensable element of human body, the oxide of arsenic and its change
It is toxic to close object, it is harmful.Arsenic can by drinking-water, food enter human body, may also pass through respiratory tract, skin and mucosa etc. into
Enter human body, the lesions such as digestive system, nervous system, immune system and the skin of people can be caused, be chronically exposed under arsenic-containing atmosphere
It can cause canceration.Certain zine-smelting plant, except cobalt daily requirement consumes a large amount of arsenic trioxides, forms the conjunctions such as arsenical copper, arsenic nickel using arsenic
Gold, these are not presently available recycling except cobalt waste residue, cause the valuable metal wasting of resources, wherein arsenic that can cause serious ring
It pollutes in border.Arsenic-containing waste residue belongs to dangerous waste, needs to provide funds to engage dangerous waste processing company recycling harmful element, causes being produced into for factory
This raising.
The resource utilization of arsenic can be divided into pyrogenic process and wet method two major classes.Pyrogenic process mainly includes oxidizing roasting, vacuum baking
With the modes such as reduction roasting；Wet method mainly has vitriol lixiviation method, copper sulphate displacement method, ferric sulfate method and alkaline Leaching etc..In
State patent of invention CN201210448673.4 describes a kind of method preparing arsenate with the wet alkaline process of the slag of nickel cobalt containing arsenic, in high pressure
Lead to oxygen in kettle and make oxidant, alkaline Leaching under the conditions of≤300 DEG C prepares arsenate, realizes arsenic in the slag of nickel cobalt containing arsenic
The recycling of pollution emission reduction and arsenic.But the patent carries out in autoclave, and there is consumed energy for industrial production
High problem, and can also increase equipment investment expense.Chinese invention patent CN201310421661.7 is to a upper patent
It improves and Cu oxide is added as oxidant, temperature is controlled at≤300 DEG C, equally exists the higher problem of energy consumption.
Arsenic Cobalt Purification is the attached technique of entire smelting process, and whole energy consumption is unsuitable excessively high, otherwise can increase whole
A industrial production cost.Therefore, there is an urgent need for a kind of condition milder of exploitation, more environmentally protective arsenic removal process, in room temperature
The recycling of arsenic can be completed under normal pressure, enterprise investment is small, and the wasting of resources situation of enterprise can be greatly reduced.
Invention content
For the deficiency and defect mentioned in background above technology, the object of the present invention is to provide a kind of reaction conditions
Mildly, simple for process, clean environment firendly, the method for extracting arsenic from the slag of nickel cobalt containing arsenic and prepare arsenate for being suitble to commercial Application.
In order to solve the above-mentioned technical problem, technical solution proposed by the present invention is：
A method of it extracting arsenic from the slag of nickel cobalt containing arsenic and prepares arsenate, include the following steps：
The slag of nickel cobalt containing arsenic is added in the aqueous slkali for being placed in reaction vessel and obtains slurries, gas oxidation is passed through from slurries bottom
Agent carries out atmospheric pressure oxidation under stiring；It is separated by solid-liquid separation after reaction a period of time, obtains filter residue and filtrate containing arsenic, the filtrate containing arsenic
Evaporative crystallization obtains arsenic acid salt crystal；
It is 0.03~0.06L by the every gram of slag of nickel cobalt containing arsenic flow per minute for being passed through gaseous oxidant；
The rotating speed of the stirring is 50~250r/min；
The grain size of the slag of nickel cobalt containing arsenic is 1~100 μm.
Due to except in cobalt nickel waste residue cobalt, nickel, copper and arsenic form complicated alloy.Being difficult using simple acidleach processing will be golden
Belong to ion to be dissolved in solution；And when leaching by acid system, it is easy to form arsenic hydride severe toxicity gas in acid system.
The present invention use alkali and gaseous oxidant, normal pressure, less than 100 DEG C at a temperature of carry out oxidation leaching to containing arsenic nickel cobalt slag
Go out, the arsenic in the slag of nickel cobalt containing arsenic, by Oxidation Leaching, is formed arsenate and entered in leachate, after heat filtering in the form of pentavalent arsenic
Arsenic filtrate will be contained again and be evaporated crystallization, obtain arsenic acid salt crystal, arsenate is primary raw material of the arsenic purification except nickel cobalt, is realized
The efficient circulation of arsenic utilizes, and arsenic is free of in obtained filter residue, can be directly entered in copper metallurgy industry.The present invention utilizes alkaline process
Normal pressure leaching avoids the danger for generating hypertoxic arsine gas, and the leaching rate of Leach reaction mild condition, arsenic is high, and arsenic is followed
Ring uses, and has reached green metallurgical, will not cause secondary arsenic pollution.This method is easy to operate, energy consumption and at low cost, wiper ring
It protects, is suitable for being widely used in industry.
The main chemical reactions occurred during Oxidation Leaching of the present invention are as follows：
It can be seen that by the above thermodynamical equilibrium equation, it is assumed that arsenic is all oxidized to the positive pentavalent of highest valence state in system, reaction
Gibbs function be negative value, it is seen that the method with arsenic in the alkaline Leaching slag of nickel cobalt containing arsenic be thermodynamically it is feasible, so
And the reaction can not be but completed under field conditions (factors), main cause may be above-mentioned reaction under field conditions (factors) in dynamics
Upper speed is slow.
Technical scheme of the present invention, by agitating mode, mixing speed, the collaboration that gas flow, gas are passed through mode is made
Under so that fluid molecule and infinitesimal are farthest ensured to fill in reactor in gas, liquid, solid reaction system of the invention
Divide mixing, it is equal for the flow regime, each component concentration, temperature of the fluid of any time in all positions in the space of reactor
It is identical.Technical solution i.e. through the invention, it can be achieved that mix slot reaction mechanism entirely.Therefore it is provided for above-mentioned arsenic alloy Leach reaction
Dynamic conditions, allow reaction normal pressure, less than 100 DEG C at a temperature of carry out, and using air as oxidant.This method is anti-
Answer mild condition, it is simple for process, at low cost, do not introduce new impurity, non-secondary pollution, be suitable for commercial Application.
As a preferred option, the bottom of the reaction vessel is equipped with air inlet endless tube, and n are provided on the air inlet endless tube
Venthole, n >=1, the gaseous oxidant are passed through by venthole in slurries.
As further preferred, 4~10 ventholes of every 15 centimetres of settings on the air inlet endless tube, venthole is into compression ring
It is evenly arranged on pipe.
As further preferred, 4~6 ventholes of every 15 centimetres of settings on the air inlet endless tube.
As a further preference, the venthole and reaction container bottom horizontal plane are in α angles, and the 30 °≤α≤
60 °, a diameter of 2mm~6mm of venthole.In this angular range, the air-flow of gaseous oxidant can be made to form helical form
Be conducive to further increase mass transfer power, and flow spiral direction and agitating paddle direction of rotation are on the contrary, simultaneously in this pore diameter range
It is interior, it is ensured that enough Jet Penetration Depths, it is broken that the two can be such that bubble is more easy to, and reduces spill-out, increases reacting dose.Simultaneously
Local turbulence is formed in reactor bottom, mass transfer enhancement reduces bottom solid reaction substance residual, keeps reaction more complete.
Preferably the venthole and reaction container bottom horizontal plane are in α angles as further, and the 45 °≤α≤
60 °, a diameter of 2mm~3mm of venthole.
In actual mechanical process and production process, m root air inlet endless tubes are set gradually since reaction container bottom, it is described
m≥1.The case where 1 m ＞ to increase with the volume of reaction vessel, only from bottom by gaseous oxidant, gas flowing
It is used when cannot be satisfied mixed slot reaction model entirely.
As a preferred option, the stirring uses mechanical linkage paddle agitator.
In practical operation and production process, single-layer or multi-layer paddle can be used in the mechanical linkage paddle agitator.
As a further preference, the rotating speed of the stirring is 100~250r/min.
As further preferably, the rotating speed of the stirring is 200~250r/min.
Inventor find, the present invention gas, liquid, solid reaction system under, if mixing speed is too fast, will make solid matter with
During being moved with the movement of water, increase unstable liquid stream, substantially reduces the effect of stirring, reduce reaction effect instead.
As a preferred option, by the every gram of slag of nickel cobalt containing arsenic flow per minute for being passed through gaseous oxidant be 0.05~
0.06L；
Above-mentioned preferred speed of agitator and preferred gaseous oxidant are passed through under flow, the leaching rate higher of arsenic.
Preferred scheme, the slag of nickel cobalt containing arsenic is first through broken, fine grinding, screening process.
The grain size of preferred scheme, the slag of nickel cobalt containing arsenic is 1~50 μm.
As a further preference, the grain size of the slag of nickel cobalt containing arsenic is 1~40 μm.
Preferred scheme, the slag of nickel cobalt containing arsenic are that arsenic method removes waste residue caused by nickel cobalt process in zinc metallurgical process.
As a preferred option, aqueous slkali uses sodium hydroxide solution or potassium hydroxide solution.
As a preferred option, a concentration of 2mol/L~10mol/L of aqueous slkali.As a further preference, the alkali
A concentration of 4mol/L~5mol/L of solution.
As a preferred option, the liquid of aqueous slkali and the slag of nickel cobalt containing arsenic is consolidated mass ratio and is controlled in (2~10):1.As into one
What is walked is preferred, and the liquid of the aqueous slkali and the slag of nickel cobalt containing arsenic is consolidated mass ratio and controlled in (4~5):1.
The temperature of preferred scheme, Oxidation Leaching is 60 DEG C~85 DEG C.
Preferred scheme, time >=6 hour of Oxidation Leaching.
As a further preference, the time of Oxidation Leaching is 6~48h.
As it is further preferably, time of Oxidation Leaching is 8~for 24 hours.
As a preferred option, gaseous oxidant is air or oxygen rich gas.
As a further preference, the gaseous oxidant is air.
In the present invention, used is normal pressure leaching mode, and the final efficient leaching that can be achieved only to arsenic and zinc contains arsenic
Contain arsenate and zincate in filtrate, since the content in zincate is few, and also has very under the crystallization temperature of arsenate
Big solubility, thus can simply realize being kept completely separate for arsenate and zincate, finally obtain high-purity arsenic acid salt crystal.
It can also be achieved the recycling of zinc simultaneously.
The slag of nickel cobalt containing arsenic handled by the present invention is the heavy metal material containing arsenic, including arsenic method removes nickel in zinc metallurgical process
Waste residue caused by cobalt process.
Compared with the prior art, the advantages of the present invention are as follows：
The present invention under normal pressure, realizes the efficient selective Oxidation Leaching of arsenic, not only significantly reduces under this condition
Equipment, operation requirement, and in the conditions of the invention, by under simple evaporative crystallization, you can obtain high-purity arsenic acid
Salt crystal.
The present invention is passed through the association of mode during alkali oxide soaks by agitating mode, mixing speed, gas flow, gas
Same-action so that fluid molecule and infinitesimal are sufficiently mixed at once in reactor in gas, liquid, solid reaction system of the invention,
Make all positions in the space of reactor, for the flow regime, each component concentration, temperature all same of the fluid of any time.I.e.
Technical solution through the invention, it can be achieved that mix slot reaction mechanism entirely.Therefore for arsenic alloy Leach reaction provide it is dynamic
Mechanical condition makes alkali oxide leaching that can be carried out under less than 100 DEG C, normal pressure, and this method reaction condition is mild, at low cost, green
It is environmentally friendly, easy to operate, be suitable for industrial applications.
The present invention under the process conditions of atmospheric low-temperature, in alkaline solution with cheap gaseous oxidant (such as air) into
Row leaches, and in the preferred scheme, the leaching rate of arsenic is up to 99% or more, and gained filtrate obtains high-purity arsenic acid through evaporative crystallization
Salt crystal realizes the recycling of arsenic, and entire processing procedure is environmentally protective, will not cause secondary arsenic pollution.
The mode of low-temperature atmosphere-pressure of the present invention, realization arsenic-selective that can be more controllable leaches, and avoids leaching
Other impurity so that subsequent purification process significantly simplifies.
The reaction condition of the atmospheric low-temperature of the present invention significantly reduces the difficulty and technique productions cost of technique productions, tool
There is great industrialization meaning.
Description of the drawings
Fig. 1 is the XRD diagram of 1 gained evaporative crystallization product of the embodiment of the present invention, and product is arsenate as can be seen from Figure.
Fig. 2 is the reaction vessel schematic diagram in the embodiment of the present invention；
Wherein：1, reaction vessel；2, stirring slurry；3, snorkel, 4 air pumps；5, air inlet endless tube.
Specific implementation mode
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face, careful description, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
The main constituents of the slag of nickel cobalt containing arsenic in various embodiments of the present invention and comparative example are：Cu:47.27%, As:
10.67%, Zn:5.78%, Co:2.43%, Ni:0.47%.The raw material is provided by certain zine-smelting plant, is arsenic in zinc metallurgical process
Method purification is except waste residue caused by nickel cobalt process.
Embodiment 1
The slag material of nickel cobalt containing arsenic that the grain size of 60g is 1 μm is added into the 5M NaOH solutions of 300mL, forms mixture
Slurry, mixed slurry is placed in reactor, reactor is heated under 85 DEG C of water-baths；The bottom of reactor is equipped with Zhou Changwei 15cm
Air inlet endless tube, be uniformly arranged 6 ventholes on the air inlet endless tube, aperture 3mm, and on the air inlet endless tube on same cross section
Venthole and reaction container bottom horizontal plane are in 45 °, and from being passed through air in venthole into reactor, the flow that is passed through of air is
3.5L/min, while reaction 8h is stirred under 250r/min rotating speeds using dasher, it realizes to the slag of nickel cobalt containing arsenic
Alkali oxide soaks；Gained solid phase is that Cu, Ni and Co is enriched with slag, and liquid phase is the leachate of zinc-rich arsenic, and the main component of the leachate is arsenic acid
Leachate containing arsenic is evaporated crystallization and obtains natrium arsenicum product by sodium and sodium zincate.Through analyzing, the leaching of arsenic in the slag of nickel cobalt containing arsenic
Extracting rate is 99.84%, and the leaching rate of zinc is 99.92%.
Embodiment 2
The slag material of nickel cobalt containing arsenic that the grain size of 60g is 40 μm is added into the 5M NaOH solutions of 300mL, forms mixture
Slurry, mixed slurry is placed in reactor, reactor is heated under 80 DEG C of water-baths；The bottom of reactor is equipped with Zhou Changwei 15cm
Air inlet endless tube, be uniformly arranged 6 ventholes on the air inlet endless tube, aperture 3mm, and on the air inlet endless tube on same cross section
Venthole and reaction container bottom horizontal plane are in 45 °, and from being passed through air in venthole into reactor, the flow that is passed through of air is
3.5L/min, while reaction is stirred for 24 hours under 250r/min rotating speeds using dasher, it realizes to the slag of nickel cobalt containing arsenic
Alkali oxide soaks；Gained solid phase is that Cu, Ni and Co is enriched with slag, and liquid phase is the leachate of zinc-rich arsenic, and the main component of the leachate is arsenic acid
Leachate containing arsenic is evaporated crystallization and obtains natrium arsenicum product by sodium and sodium zincate.Through analyzing, the leaching of arsenic in the slag of nickel cobalt containing arsenic
Extracting rate is 99.56%, and the leaching rate of zinc is 99.42%.Fig. 1 is the XRD diagram of evaporative crystallization product, as seen from the figure, gained evaporation
The main component of crystallized product is Na3AsO4·12H2O.
Embodiment 3
The slag material of nickel cobalt containing arsenic that the grain size of 60g is 40 μm is added into the 5M NaOH solutions of 300mL, forms mixture
Slurry, mixed slurry is placed in reactor, reactor is heated under 85 DEG C of water-baths；The bottom of reactor is equipped with Zhou Changwei 15cm
Air inlet endless tube, be uniformly arranged 6 ventholes on the air inlet endless tube, aperture 3mm, and on the air inlet endless tube on same cross section
Venthole and reaction container bottom horizontal plane are in 45 °, and from being passed through air in venthole into reactor, the flow that is passed through of air is
3.5L/min, while reaction 8h is stirred under 250r/min rotating speeds using dasher, it realizes to the slag of nickel cobalt containing arsenic
Alkali oxide soaks；Gained solid phase is that Cu, Ni and Co is enriched with slag, and liquid phase is the leachate of zinc-rich arsenic, and the main component of the leachate is arsenic acid
Leachate containing arsenic is evaporated crystallization and obtains natrium arsenicum product by sodium and sodium zincate.Through analyzing, the leaching of arsenic in the slag of nickel cobalt containing arsenic
Extracting rate is 98.56%, and the leaching rate of zinc is 99.92%.
Embodiment 4
The grain size that 60g is added into the 4M NaOH solutions of 240mL is 20 μm of slag materials of nickel cobalt containing arsenic, forms mixed slurry,
Mixed slurry is placed in reactor, reactor is heated under 60 DEG C of water-baths；The bottom of reactor is equipped with Zhou Changwei 15cm's
Air inlet endless tube has been uniformly arranged 4 ventholes, aperture 2mm on the air inlet endless tube, and has led on the air inlet endless tube on same cross section
Stomata and reaction container bottom horizontal plane are in 60 °, and from being passed through air in venthole into reactor, the flow that is passed through of air is
3L/min, while reaction 48h is stirred under 200r/min rotating speeds using dasher, realize the oxygen to the slag of nickel cobalt containing arsenic
Choline soaks；Gained solid phase is that Cu, Ni and Co is enriched with slag, and liquid phase is the leachate of zinc-rich arsenic, and the main component of the leachate is natrium arsenicum
And sodium zincate, the leachate containing arsenic is evaporated crystallization and obtains natrium arsenicum product.Through analysis, the leaching of arsenic in the former slag of nickel cobalt containing arsenic
Extracting rate is 99.13%, the leaching rate 98.64% of zinc.
Embodiment 5
The grain size that 60g is added into the 3M NaOH solutions of 200mL is 30 μm of slag materials of nickel cobalt containing arsenic, forms mixed slurry,
Mixed slurry is placed in reactor, reactor is heated under 95 DEG C of water-baths；The bottom of reactor is equipped with Zhou Changwei 15cm's
Air inlet endless tube, has been uniformly arranged 6 ventholes on the air inlet endless tube, leads on the air inlet endless tube on aperture 4mm and same cross section
Stomata and reaction container bottom horizontal plane are in 30 °, and from being passed through air in venthole into reactor, the flow that is passed through of air is
2L/min, while reaction 6h is stirred under 100r/min rotating speeds using dasher, realize the oxygen to the slag of nickel cobalt containing arsenic
Choline soaks, and gained solid phase is that Cu, Ni and Co is enriched with slag, and liquid phase is the leachate of zinc-rich arsenic, and the main component of the leachate is natrium arsenicum
And sodium zincate, the leachate containing arsenic is evaporated crystallization and obtains natrium arsenicum product.Through analysis, the leaching of arsenic in the former slag of nickel cobalt containing arsenic
Extracting rate is 92.13%, the leaching rate 90.79% of zinc.
Embodiment 6
The grain size that 10g is added into the 2M NaOH solutions of 100mL is 50 μm of slag materials of nickel cobalt containing arsenic, forms mixed slurry,
Mixed slurry is placed in reactor, reactor is heated under 95 DEG C of water-baths；The bottom of reactor is equipped with Zhou Changwei 15cm's
Air inlet endless tube has been uniformly arranged 6 ventholes, aperture 5mm on the air inlet endless tube, and has led on the air inlet endless tube on same cross section
Stomata and reaction container bottom horizontal plane are in 30 °, and from being passed through air in venthole into reactor, the flow that is passed through of air is
3.5L/min, while reaction 12h is stirred under 250r/min rotating speeds using dasher, it realizes to the slag of nickel cobalt containing arsenic
Alkali oxide soaks, and gained solid phase is that Cu, Ni and Co is enriched with slag, and liquid phase is the leachate of zinc-rich arsenic, and the main component of the leachate is arsenic acid
Leachate containing arsenic is evaporated crystallization and obtains natrium arsenicum product by sodium and sodium zincate.Through analysis, arsenic in the former slag of nickel cobalt containing arsenic
Leaching rate is 94.17%, the leaching rate 89.12% of zinc.
Embodiment 7
The grain size that 10g is added into the 1M NaOH solutions of 50mL is 40 μm of slag materials of nickel cobalt containing arsenic, forms mixed slurry,
Mixed slurry is placed in reactor, reactor is heated under 20 DEG C of water-baths；The bottom of reactor is equipped with Zhou Changwei 15cm's
Air inlet endless tube has been uniformly arranged 6 ventholes, aperture 6mm on the air inlet endless tube, and has led on the air inlet endless tube on same cross section
Stomata and reaction container bottom horizontal plane are in 30 °, and from being passed through air in venthole into reactor, the flow that is passed through of air is
4L/min, while reaction 72h is stirred under 50r/min rotating speeds using dasher, realize the oxygen to the slag of nickel cobalt containing arsenic
Choline soaks, and gained solid phase is that Cu, Ni and Co is enriched with slag, and liquid phase is the leachate of zinc-rich arsenic, and the main component of the leachate is natrium arsenicum
And sodium zincate, the leachate containing arsenic is evaporated crystallization and obtains natrium arsenicum product.Through analysis, the leaching of arsenic in the former slag of nickel cobalt containing arsenic
Extracting rate is 94.33%, the leaching rate 83.78% of zinc.The leaching rate of zinc is main to be influenced by alkaline concentration.
Comparative example 1
The other conditions of the comparative example are same as Example 1, and only the speed of agitator during alkali oxide leaching is 20r/
min.Through analysis, the leaching rate of arsenic is 67.75% in the former slag of nickel cobalt containing arsenic, and the leaching rate of zinc is 80.34%.
Comparative example 2
The other conditions of the comparative example are same as Example 1, and only the speed of agitator during alkali oxide leaching is 800r/
min.Through analysis, the leaching rate of arsenic is 54.92% in the former slag of nickel cobalt containing arsenic, and the leaching rate of zinc is 68.41%.
Comparative example 3
The other conditions of the comparative example are same as Example 1, and only the flow that is passed through of air is in the dipped journey of alkali oxide
0.01L/min.Through analysis, the leaching rate of arsenic is 78.93% in the former slag of nickel cobalt containing arsenic, and the leaching rate of zinc is 92.74%.
Comparative example 4
The other conditions of the comparative example are same as Example 1, only will only in the dipped journey of alkali oxide air from slurries top
Portion is passed through, and through analysis, the leaching rate of arsenic is 20.62% in the former slag of nickel cobalt containing arsenic, and the leaching rate of zinc is 99.31%.
Comparative example 5
The other conditions of the comparative example are same as Example 1, and only the flow that is passed through of air is 8L/ in the dipped journey of alkali oxide
min.During the reaction, gas overflowing, and take moisture content out of reaction system, influence system balance.
Comparative example 6
The other conditions of the comparative example are same as Example 1, and only particle is further reduced, after discovery is slightly less than 1 μm,
Dipping effect is not promoted further, but can increase the energy consumption of ore grinding, when the slag particle diameter of nickel cobalt containing arsenic further reduces
It to nanoscale, can make in slurry system mud character solution occur, it is fully dispersed when not utilizing stirring so that reaction
Part reaction can not be filled to complete.
Comparative example 7
The other conditions of the comparative example are same as Example 1, and only the slag of nickel cobalt containing arsenic material particular diameter is >=200 μm.Through dividing
It analyses, the leaching rate of arsenic is 77.21% in the former slag of nickel cobalt containing arsenic, and the leaching rate of zinc is 99.52%.
Comparative example 8
The other conditions of the comparative example are same as Example 1, and only air inlet endless tube venthole aperture is 10mm.Through analyzing,
The leaching rate of arsenic is 80.21% in the original slag of nickel cobalt containing arsenic, and the leaching rate of zinc is 99.62%.
Comparative example 9
The other conditions of the comparative example are same as Example 1, and only air inlet endless tube venthole aperture is 1mm.It is former through analysis
The leaching rate of arsenic is 65.21% in the slag of nickel cobalt containing arsenic, and the leaching rate of zinc is 99.48%.
Comparative example 10
The other conditions of the comparative example are same as Example 1, are tangentially only 90 ° in α angles by venthole and annulus.Instead
Device bottom is answered to have remaining solid, reaction incomplete.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, any made by repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of method extracted arsenic in slag from nickel cobalt containing arsenic and prepare arsenate, it is characterised in that：Include the following steps：
The slag of nickel cobalt containing arsenic is added in the aqueous slkali for being placed in reaction vessel and obtains slurries, being passed through gaseous oxidant from slurries bottom exists
Under stirring atmospheric pressure oxidation leaching is carried out in 20 DEG C~100 DEG C；It is separated by solid-liquid separation, obtains filter residue and filtrate containing arsenic, the filtrate containing arsenic
Evaporative crystallization obtains arsenic acid salt crystal；
It is 0.03~0.06L by the every gram of slag of nickel cobalt containing arsenic flow per minute for being passed through gaseous oxidant；
The rotating speed of the stirring is 50~250r/min；
The grain size of the slag of nickel cobalt containing arsenic is 1~100 μm.
2. the method extracted arsenic in a kind of slag from nickel cobalt containing arsenic according to claim 1 and prepare arsenate, feature exist
In：
It is 0.05~0.06L by the every gram of slag of nickel cobalt containing arsenic flow per minute for being passed through gaseous oxidant；
The rotating speed of the stirring is 100~250r/min；
The grain size of the slag of nickel cobalt containing arsenic is 1~50 μm.
3. the method extracted arsenic in a kind of slag from nickel cobalt containing arsenic according to claim 1 and prepare arsenate, feature exist
In：The bottom of the reaction vessel is equipped with air inlet endless tube, is provided with n venthole on the air inlet endless tube, n >=1 is described
Gaseous oxidant is passed through by venthole in slurries.
4. the method extracted arsenic in a kind of slag from nickel cobalt containing arsenic according to claim 3 and prepare arsenate, feature exist
In：4~10 ventholes of every 15 centimetres of settings, the venthole carry out uniform cloth on air inlet endless tube on the air inlet endless tube
It sets.
5. the method extracted arsenic in a kind of slag from nickel cobalt containing arsenic according to claim 4 and prepare arsenate, feature exist
In：The venthole is in α angles, 30 °≤α≤60 ° with reaction container bottom horizontal plane；The aperture of the venthole is
2mm~6mm.
6. the method extracted arsenic in a kind of slag from nickel cobalt containing arsenic according to claim 5 and prepare arsenate, feature exist
In：4~6 ventholes of every 15 centimetres of settings on the air inlet endless tube；The venthole is pressed from both sides with reaction container bottom horizontal plane in α
Angle, 45 °≤α≤60 °, a diameter of 2mm~3mm of venthole.
7. the method extracted arsenic in a kind of slag from nickel cobalt containing arsenic according to claim 1 and prepare arsenate, feature exist
In：The aqueous slkali is sodium hydroxide solution or potassium hydroxide solution；A concentration of 2mol/L~10mol/L of aqueous slkali；It is described
The liquid of aqueous slkali and the slag of nickel cobalt containing arsenic is consolidated mass ratio and is controlled in (2~10):1.
8. the method extracted arsenic in a kind of slag from nickel cobalt containing arsenic according to claim 1 and prepare arsenate, feature exist
In：A concentration of 4mol/L~5mol/L of the aqueous slkali；
The liquid of the aqueous slkali and the slag of nickel cobalt containing arsenic is consolidated mass ratio and is controlled in (4~5):1.
9. the method extracted arsenic in a kind of slag from nickel cobalt containing arsenic according to claim 1 and prepare arsenate, feature exist
In：Time >=6h that the atmospheric pressure oxidation leaches.
10. the method extracted arsenic in a kind of slag from nickel cobalt containing arsenic according to claim 1 and prepare arsenate, feature exist
In：The temperature that the atmospheric pressure oxidation leaches is 60 DEG C~85 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810519109.4A CN108609653B (en) | 2018-05-28 | 2018-05-28 | Method for extracting arsenic from arsenic-nickel-cobalt-containing slag and preparing arsenate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810519109.4A CN108609653B (en) | 2018-05-28 | 2018-05-28 | Method for extracting arsenic from arsenic-nickel-cobalt-containing slag and preparing arsenate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108609653A true CN108609653A (en) | 2018-10-02 |
| CN108609653B CN108609653B (en) | 2020-06-23 |
Family
ID=63664221
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810519109.4A Active CN108609653B (en) | 2018-05-28 | 2018-05-28 | Method for extracting arsenic from arsenic-nickel-cobalt-containing slag and preparing arsenate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108609653B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111074073A (en) * | 2020-01-08 | 2020-04-28 | 昆明理工大学 | Method for purifying and removing cobalt in zinc hydrometallurgy |
| CN112226623A (en) * | 2020-10-16 | 2021-01-15 | 烟台中科恩吉科创新产业园管理有限公司 | Method for separating and recovering zinc and cobalt in cobalt slag |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586604A (en) * | 2011-01-18 | 2012-07-18 | 郴州市金贵银业股份有限公司 | Technology for wet-processing anode mud containing arsenic and lead |
| CN102925701A (en) * | 2012-11-09 | 2013-02-13 | 中国科学院过程工程研究所 | Method using wet alkaline process of cobalt-nickel (Co-Ni) residue containing arsenic to prepare arsenate |
| CN105154679A (en) * | 2015-09-22 | 2015-12-16 | 中南大学 | Treatment method for separating copper and arsenic in arsenic filter cakes |
| CN106834708A (en) * | 2016-12-21 | 2017-06-13 | 中南大学 | A kind of integrated conduct method of arsenic-containing smoke dust |
| CN106834715A (en) * | 2016-12-21 | 2017-06-13 | 中南大学 | A kind of method of comprehensive utilization of arsenic-containing material |
-
2018
- 2018-05-28 CN CN201810519109.4A patent/CN108609653B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586604A (en) * | 2011-01-18 | 2012-07-18 | 郴州市金贵银业股份有限公司 | Technology for wet-processing anode mud containing arsenic and lead |
| CN102925701A (en) * | 2012-11-09 | 2013-02-13 | 中国科学院过程工程研究所 | Method using wet alkaline process of cobalt-nickel (Co-Ni) residue containing arsenic to prepare arsenate |
| CN105154679A (en) * | 2015-09-22 | 2015-12-16 | 中南大学 | Treatment method for separating copper and arsenic in arsenic filter cakes |
| CN106834708A (en) * | 2016-12-21 | 2017-06-13 | 中南大学 | A kind of integrated conduct method of arsenic-containing smoke dust |
| CN106834715A (en) * | 2016-12-21 | 2017-06-13 | 中南大学 | A kind of method of comprehensive utilization of arsenic-containing material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111074073A (en) * | 2020-01-08 | 2020-04-28 | 昆明理工大学 | Method for purifying and removing cobalt in zinc hydrometallurgy |
| CN112226623A (en) * | 2020-10-16 | 2021-01-15 | 烟台中科恩吉科创新产业园管理有限公司 | Method for separating and recovering zinc and cobalt in cobalt slag |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108609653B (en) | 2020-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105039713A (en) | Method for leaching solid arsenic out of arsenic sulfide slag through one step and enriching valuable metal | |
| CN107202333A (en) | A kind of sulfur-bearing VOC method for innocent treatment | |
| CN110983060B (en) | Method for resource utilization of arsenic filter cake and white smoke | |
| CN108588436A (en) | One kind removing cobalt slag recovery and treatment method containing arsenic | |
| CN108609653A (en) | A method of it extracting arsenic from the slag of nickel cobalt containing arsenic and prepares arsenate | |
| CN104762474B (en) | Method for preparing ammonium molybdate through molybdenite | |
| CN103194768A (en) | Method for preparing electrolytic manganese metal by using high-iron and high-phosphor manganese ores | |
| CN110129552A (en) | A method of vanadic sulfide material is prepared using containing vanadium leachate | |
| CN102226234A (en) | Integrated reactor suitable for purifying and impurity-removing of pyrolusite leachate | |
| CN108315553A (en) | A kind of leaching method of copper cobalt sulfide ore | |
| CN106669591B (en) | It is a kind of for adsorbing the processing method of xanthate in waste water | |
| CN106636661B (en) | A kind of method of Selective Separation recycling tellurium and antimony in slag from tellurium | |
| CN117025983B (en) | Method for realizing vanadium-chromium oxidation leaching by adopting combination of ultrasonic external field and micro-bubbles | |
| CN109554539A (en) | A kind of method of bismuth and copper and iron in pressurized acid leaching separation of Bismuth concentrate | |
| WO2023186027A1 (en) | Environmentally friendly gold leaching method for gold ore containing carbon, sulfur and arsenic | |
| CN105983707B (en) | A method of high-purity rhenium powder is prepared from rhenium-containing high arsenic-and copper-bearing sulfide | |
| CN105256135A (en) | Method for recovering phosphorus resource in high-phosphorus iron ore through ball-milling acid leaching-biological adsorption | |
| CN103194767A (en) | Method for preparing manganese sulfate electrolyte by using high-iron and high-phosphor manganese ores | |
| CN113072211B (en) | Method for treating high-arsenic ferrate wastewater and recovering copper and iron | |
| CN112646976B (en) | Method for synergistically leaching nickel, cobalt and manganese by utilizing waste lithium ion battery black powder and nickel cobalt sulfide ore and application | |
| CN108658133A (en) | A kind of quick dissolution method of insoluble metal iridium | |
| CN211235213U (en) | Dynamic and static combined stirring system | |
| CN103288133A (en) | Method for preparing arsenic trioxide from black copper sludge | |
| CN1164775C (en) | Ammonium salt liquid phase oxidation direct leaching method for nonferrous metal sulfide mineral | |
| CN103484693A (en) | Harmlessness method for treating arsenic in antimony oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |