CN108609653B - Method for extracting arsenic from arsenic-nickel-cobalt-containing slag and preparing arsenate - Google Patents
Method for extracting arsenic from arsenic-nickel-cobalt-containing slag and preparing arsenate Download PDFInfo
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- CN108609653B CN108609653B CN201810519109.4A CN201810519109A CN108609653B CN 108609653 B CN108609653 B CN 108609653B CN 201810519109 A CN201810519109 A CN 201810519109A CN 108609653 B CN108609653 B CN 108609653B
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Abstract
The invention discloses a method for extracting arsenic from arsenic-nickel-cobalt-containing slag and preparing arsenate, wherein arsenic-nickel-cobalt-containing slag is added into an alkali solution in a reaction container to obtain slurry, and a gas oxidant is introduced from the bottom of the slurry to carry out normal pressure oxidation under stirring; and performing solid-liquid separation to obtain filter residue and arsenic-containing filtrate, and performing evaporation crystallization on the arsenic-containing filtrate to obtain arsenate crystals. The invention realizes a full mixing tank reaction mechanism under the synergistic effect of a stirring mode, a stirring speed, a gas flow and a gas introduction mode in the oxidation alkaline leaching process. The invention adopts alkaline method to oxidize and leach arsenic-nickel-cobalt-containing slag, adopts cheap raw material gas oxidant (such as air) to leach, can realize high-efficiency leaching under the conditions of normal pressure and low temperature, greatly reduces the difficulty of process production and the process production cost, and has great industrial significance.
Description
Technical Field
The invention relates to the technical field of arsenic-containing nickel cobalt slag treatment, in particular to a method for extracting arsenic from arsenic-containing nickel cobalt slag and preparing arsenate.
Background
Arsenic is a kind of metal element widely distributed in the nature, and is an essential element for human body, and oxides of arsenic and compounds thereof are toxic and harmful to human body. Arsenic can enter human bodies through drinking water and food, can also enter human bodies through respiratory tracts, skin mucous membranes and the like, can cause pathological changes of digestive systems, nervous systems, immune systems, skins and the like of the human bodies, and can cause canceration after being exposed to arsenic-containing environment for a long time. A certain zinc refinery adopts arsenate to remove cobalt, a large amount of arsenic trioxide is required to be consumed every day to form alloys such as arsenic copper, arsenic nickel and the like, the cobalt-removing waste residues cannot be recycled at present, valuable metal resources are wasted, and arsenic causes serious environmental pollution. As the arsenic-containing waste residue belongs to dangerous waste, the investment of the arsenic-containing waste residue needs to be performed to apply a dangerous waste treatment company to recover harmful elements, so that the production cost of a factory is increased.
Resource recovery of arsenic can be divided into two major categories, namely pyrogenic process and wet process. The pyrogenic process mainly comprises modes of oxidizing roasting, vacuum roasting, reducing roasting and the like; the wet method mainly comprises a sulfuric acid leaching method, a copper sulfate replacement method, an iron sulfate method, an alkaline leaching method and the like. The Chinese patent CN201210448673.4 introduces a method for preparing arsenate by using arsenic-containing nickel cobalt slag through a wet alkali method, oxygen is introduced into a high-pressure kettle as an oxidant, and the arsenate is prepared by alkali leaching at the temperature of less than or equal to 300 ℃, so that pollution reduction of arsenic in the arsenic-containing nickel cobalt slag and recycling of the arsenic are realized. However, this patent is carried out in an autoclave, which has a problem of high energy consumption for industrial production and also increases the equipment investment cost. The invention patent CN201310421661.7 of China is an improvement of the previous patent, copper oxide is added as an oxidant, the temperature is controlled to be less than or equal to 300 ℃, and the problem of high energy consumption also exists.
The purification and cobalt removal of the arsenic salt are auxiliary processes of the whole zinc smelting process, the whole energy consumption is not high, and the whole industrial production cost is increased. Therefore, it is urgently needed to develop a more environmentally friendly arsenic removal process with milder conditions to recycle arsenic at normal temperature and pressure, so that the investment of enterprises is low, and the waste of resources of the enterprises can be greatly reduced.
Disclosure of Invention
Aiming at the defects and shortcomings in the background art, the invention aims to provide the method for extracting arsenic from arsenic-nickel-cobalt-containing slag and preparing arsenate, which has the advantages of mild reaction conditions, simple process, cleanness, environmental protection and suitability for industrial application.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for extracting arsenic from arsenic-nickel-cobalt-containing slag and preparing arsenate comprises the following steps:
adding arsenic-containing nickel cobalt slag into an alkali solution in a reaction container to obtain slurry, and introducing a gas oxidant from the bottom of the slurry to carry out normal pressure oxidation under stirring; after reacting for a period of time, carrying out solid-liquid separation to obtain filter residue and arsenic-containing filtrate, and evaporating and crystallizing the arsenic-containing filtrate to obtain arsenate crystals;
the flow of the gas oxidant per gram of arsenic-nickel-cobalt-containing slag per minute is 0.03-0.06L;
the stirring speed is 50-250 r/min;
the grain size of the arsenic-nickel-cobalt-containing slag is 1-100 mu m.
The cobalt, nickel, copper and arsenic in the cobalt and nickel removing waste slag form complex alloy. Metal ions are difficult to dissolve in the solution by adopting simple acid leaching treatment; and when the arsenic is leached by an acid method, arsenic hydride highly toxic gas is easily formed in an acid system.
The arsenic-containing nickel-cobalt slag is subjected to oxidation leaching by adopting alkali and a gas oxidant at normal pressure and at a temperature of less than 100 ℃, arsenic in the arsenic-containing nickel-cobalt slag is subjected to oxidation leaching in the form of pentavalent arsenic to form arsenate, the arsenate enters a leaching solution, and the arsenic-containing filtrate is subjected to evaporation crystallization after being subjected to thermal filtration to obtain arsenate crystals, wherein the arsenate is a main raw material for purifying the arsenate to remove the nickel-cobalt, so that the high-efficiency recycling of the arsenic is realized, and the obtained filter residue does not contain the arsenic and can directly enter a copper smelting system. The invention utilizes the alkaline method to leach under normal pressure, avoids the danger of generating virulent arsine gas, has mild leaching reaction conditions and high arsenic leaching rate, recycles the arsenic, achieves green metallurgy and does not cause secondary arsenic pollution. The method is simple to operate, low in energy consumption and cost, clean and environment-friendly, and suitable for wide industrial application.
The main chemical reactions occurring in the oxidation leaching process of the invention are as follows:
from the above thermodynamic equation, it can be seen that, assuming that all arsenic in the system is oxidized into the maximum valence state of positive pentavalent state and the gibbs function of the reaction is negative, it can be seen that the method of leaching arsenic from arsenic-containing nickel-cobalt slag by the alkaline method is thermodynamically feasible, however, the reaction cannot be completed under natural conditions, and the main reason may be that the reaction is kinetically slow under natural conditions.
According to the technical scheme, the fluid molecules and microelements in the gas, liquid and solid reaction system are fully mixed in the reactor to the maximum extent under the synergistic action of a stirring mode, a stirring speed, a gas flow rate and a gas introduction mode, and the flowing state, the concentration and the temperature of each component of the fluid at any time are the same at all positions in the space of the reactor. Namely, the technical scheme of the invention can realize a full mixing tank reaction mechanism. Therefore, kinetic conditions are provided for the arsenic alloy leaching reaction, the reaction can be carried out at normal pressure and the temperature of less than 100 ℃, and air is used as an oxidant. The method has the advantages of mild reaction conditions, simple process, low cost, no introduction of new impurities, no secondary pollution and suitability for industrial application.
Preferably, the bottom of the reaction vessel is provided with a gas inlet ring pipe, the gas inlet ring pipe is provided with n vent holes, n is more than or equal to 1, and the gas oxidant is introduced into the slurry through the vent holes.
Preferably, the air inlet ring pipe is provided with 4-10 vent holes per 15cm, and the vent holes are uniformly distributed on the air inlet ring pipe.
More preferably, the air inlet ring pipe is provided with 4-6 vent holes per 15 cm.
Preferably, the vent hole and the horizontal plane of the bottom of the reaction vessel form an included angle of α, the included angle is equal to or less than 30 degrees and equal to or less than α degrees and equal to or less than 60 degrees, the diameter of the vent hole is 2 mm-6 mm, the gas flow of the gas oxidant can form a spiral shape within the angle range, mass transfer power is further increased, the spiral direction of the gas flow is opposite to the rotating direction of the stirring paddle, sufficient jet depth can be ensured within the aperture range, the gas flow and the stirring paddle can be broken easily, the overflow amount is reduced, the reaction amount is increased, meanwhile, local turbulence is formed at the bottom of the reactor, mass transfer is enhanced, the residue of solid reaction substances at the bottom is reduced, and the reaction is more complete.
As a further preference, the vent hole and the horizontal plane at the bottom of the reaction vessel form an included angle of α, the included angle is equal to or larger than 45 degrees and equal to or smaller than α degrees and equal to or smaller than 60 degrees, and the diameter of the vent hole is 2 mm-3 mm.
In the actual operation process and the production process, m gas inlet circular pipes are sequentially arranged from the bottom of the reaction container, wherein m is more than or equal to 1. The case where m > 1 is adopted when the gas flow is not satisfactory for the full mixing tank reaction model only by passing the gas oxidizing agent from the bottom as the volume of the reaction vessel increases.
Preferably, the stirring is performed by a mechanical link paddle stirrer.
In actual operation and production process, the mechanical link paddle type stirrer can adopt single-layer or multi-layer paddles.
More preferably, the rotation speed of the stirring is 100 to 250 r/min.
More preferably, the rotation speed of the stirring is 200 to 250 r/min.
The inventor finds that in the gas, liquid and solid reaction system of the invention, if the stirring speed is too high, unstable liquid flow is increased in the process of enabling solid substances to move along with the movement of water, so that the stirring effect is greatly reduced, and the reaction effect is reduced.
As a preferable scheme, the flow of the gas oxidant introduced per gram of arsenic-nickel-cobalt-containing slag per minute is 0.05-0.06L;
the leaching rate of arsenic is higher under the preferable stirring speed and the preferable gas oxidant introduction flow.
In a preferred scheme, the arsenic-nickel-cobalt-containing slag is subjected to crushing, fine grinding and screening treatment.
In a preferable scheme, the grain size of the arsenic-nickel-cobalt-containing slag is 1-50 μm.
More preferably, the grain size of the arsenic-nickel-cobalt-containing slag is 1 to 40 μm.
In a preferred scheme, the arsenic-nickel-cobalt-containing slag is waste slag generated in a nickel-cobalt removing process by an arsenic salt method in a zinc smelting process.
Preferably, the alkali solution is sodium hydroxide solution or potassium hydroxide solution.
Preferably, the concentration of the alkali solution is 2mol/L to 10 mol/L. Further preferably, the concentration of the alkali solution is 4mol/L to 5 mol/L.
Preferably, the liquid-solid mass ratio of the alkali solution to the arsenic-nickel-cobalt-containing slag is controlled to be (2-10): 1. More preferably, the liquid-solid mass ratio of the alkali solution to the arsenic-nickel-cobalt-containing slag is controlled to be (4-5): 1.
In the preferable scheme, the temperature of the oxidation leaching is 60-85 ℃.
In the preferable scheme, the time of the oxidation leaching is more than or equal to 6 hours.
Preferably, the time of the oxidation leaching is 6-48 h.
As a further preference, the time of the oxidation leaching is 8-24 h.
Preferably, the gaseous oxidant is air or oxygen-enriched gas.
As a further preference, the gaseous oxidant is air.
In the invention, the normal pressure leaching mode is adopted, so that the high-efficiency leaching of only arsenic and zinc can be finally realized, the arsenic-containing filtrate contains arsenate and zincate, and the arsenate and the zincate have low content and high solubility at the crystallization temperature of the arsenate, so that the arsenate and the zincate can be simply and completely separated, and the high-purity arsenate crystal can be finally obtained. Meanwhile, the recovery of zinc can be realized.
The arsenic-nickel-cobalt-containing slag treated by the method is a heavy metal material containing arsenic, and comprises waste slag generated in a nickel-cobalt removing process by an arsenic salt method in a zinc smelting process.
Compared with the prior art, the invention has the advantages that:
the invention realizes the efficient selective oxidation leaching of arsenic under normal pressure, greatly reduces the requirements of equipment and operation under the condition, and can obtain high-purity arsenate crystals under the condition of simple evaporative crystallization.
In the oxidation alkaline leaching process, fluid molecules and microelements in the gas, liquid and solid reaction system are fully mixed in the reactor at once through the synergistic effect of the stirring mode, the stirring speed, the gas flow rate and the gas introduction mode, so that the flowing state, the concentration and the temperature of each component of the fluid at any time are the same at all the positions in the space of the reactor. Namely, the technical scheme of the invention can realize a full mixing tank reaction mechanism. Therefore, a dynamic condition is provided for the arsenic alloy leaching reaction, so that the oxidation alkaline leaching can be carried out at the temperature of less than 100 ℃ and under normal pressure, and the method has the advantages of mild reaction condition, low cost, environmental protection, simple and convenient operation and suitability for industrial application.
The invention leaches in alkaline solution with cheap gas oxidant (such as air) under the process conditions of normal pressure and low temperature, in the preferred proposal, the leaching rate of arsenic is up to more than 99 percent, the obtained filtrate is evaporated and crystallized to obtain high-purity arsenate crystal, thereby realizing the recycling of arsenic, the whole treatment process is green and environment-friendly, and no secondary arsenic pollution is caused.
The low-temperature normal-pressure mode adopted by the invention can realize the arsenic selective leaching more controllably, and avoid leaching other impurities, so that the subsequent purification process is greatly simplified.
The reaction conditions of normal pressure and low temperature greatly reduce the difficulty and cost of process production, and have great industrial significance.
Drawings
FIG. 1 is an XRD pattern of the evaporative crystalline product obtained in example 1 of the present invention, from which it can be seen that the product is arsenate.
FIG. 2 is a schematic view of a reaction vessel in an embodiment of the present invention;
wherein: 1. a reaction vessel; 2. stirring the slurry; 3. a breather pipe and a 4 air pump; 5. an air inlet loop pipe.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described in more complete detail with reference to the drawings and preferred embodiments, but the scope of the invention is not limited to the following specific embodiments.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The arsenic-nickel-cobalt-containing slag in each embodiment and comparative example of the invention mainly comprises the following components: 47.27% of Cu, 10.67% of As, 5.78% of Zn, 2.43% of Co and 0.47% of Ni. The raw material is provided by a zinc refinery and is used for purifying waste residues generated in the nickel cobalt removing process by an arsenic salt method in the zinc smelting process.
Example 1
Adding 60g of arsenic-nickel-cobalt-containing slag material with the particle size of 1 mu M into 300mL of 5M NaOH solution to form mixed slurry, placing the mixed slurry into a reactor, and heating the reactor in water bath at 85 ℃; the bottom of the reactor is provided with an air inlet ring pipe with the circumference of 15cm, the air inlet ring pipe is uniformly provided with 6 vent holes with the aperture of 3mm, the vent holes on the air inlet ring pipe on the same cross section and the horizontal plane of the bottom of the reaction container form 45 degrees, air is introduced into the reactor from the vent holes, the introduction flow of the air is 3.5L/min, and simultaneously, a paddle type stirrer is adopted to stir and react for 8 hours at the rotating speed of 250r/min, so that the oxidation alkaline leaching of arsenic-containing nickel-cobalt slag is realized; the obtained solid phase is copper nickel cobalt enriched slag, the liquid phase is a leaching solution rich in zinc and arsenic, the main components of the leaching solution are sodium arsenate and sodium zincate, and the leaching solution containing arsenic is evaporated and crystallized to obtain a sodium arsenate product. Analysis shows that the leaching rate of arsenic in the arsenic-nickel-cobalt slag is 99.84 percent, and the leaching rate of zinc is 99.92 percent.
Example 2
Adding 60g of arsenic-nickel-cobalt-containing slag material with the particle size of 40 mu M into 300mL of 5M NaOH solution to form mixed slurry, placing the mixed slurry into a reactor, and heating the reactor in water bath at 80 ℃; the bottom of the reactor is provided with an air inlet ring pipe with the circumference of 15cm, the air inlet ring pipe is uniformly provided with 6 vent holes with the aperture of 3mm, the vent holes on the air inlet ring pipe on the same cross section and the horizontal plane of the bottom of the reaction container form 45 degrees, air is introduced into the reactor from the vent holes, the introduction flow of the air is 3.5L/min, and simultaneously, a paddle type stirrer is adopted to carry out stirring reaction for 24 hours at the rotating speed of 250r/min, so that the oxidation alkaline leaching of arsenic-containing nickel-cobalt slag is realized; the obtained solid phase is copper nickel cobalt enriched slag, the liquid phase is a leaching solution rich in zinc and arsenic, the main components of the leaching solution are sodium arsenate and sodium zincate, and the leaching solution containing arsenic is evaporated and crystallized to obtain a sodium arsenate product. Through analysis, the leaching rate of arsenic in the arsenic-nickel-cobalt slag is 99.56 percent, and the leaching rate of zinc is 99.42 percent. FIG. 1 is an XRD pattern of the evaporative crystalline product, from which it can be seen that Na is the main component of the evaporative crystalline product obtained3AsO4·12H2O.
Example 3
Adding 60g of arsenic-nickel-cobalt-containing slag material with the particle size of 40 mu M into 300mL of 5M NaOH solution to form mixed slurry, placing the mixed slurry into a reactor, and heating the reactor in water bath at 85 ℃; the bottom of the reactor is provided with an air inlet ring pipe with the circumference of 15cm, the air inlet ring pipe is uniformly provided with 6 vent holes with the aperture of 3mm, the vent holes on the air inlet ring pipe on the same cross section and the horizontal plane of the bottom of the reaction container form 45 degrees, air is introduced into the reactor from the vent holes, the introduction flow of the air is 3.5L/min, and simultaneously, a paddle type stirrer is adopted to stir and react for 8 hours at the rotating speed of 250r/min, so that the oxidation alkaline leaching of arsenic-containing nickel-cobalt slag is realized; the obtained solid phase is copper nickel cobalt enriched slag, the liquid phase is a leaching solution rich in zinc and arsenic, the main components of the leaching solution are sodium arsenate and sodium zincate, and the leaching solution containing arsenic is evaporated and crystallized to obtain a sodium arsenate product. Through analysis, the leaching rate of arsenic in the arsenic-nickel-cobalt slag is 98.56 percent, and the leaching rate of zinc is 99.92 percent.
Example 4
Adding 60g of arsenic-nickel-cobalt-containing slag material with the particle size of 20 mu M into 240mL of 4M NaOH solution to form mixed slurry, placing the mixed slurry into a reactor, and heating the reactor in water bath at 60 ℃; the bottom of the reactor is provided with an air inlet ring pipe with the circumference of 15cm, the air inlet ring pipe is uniformly provided with 4 vent holes with the aperture of 2mm, the vent holes on the air inlet ring pipe on the same cross section and the horizontal plane of the bottom of the reaction container form 60 degrees, air is introduced into the reactor from the vent holes, the introduction flow of the air is 3L/min, and simultaneously, a paddle type stirrer is adopted to carry out stirring reaction for 48 hours at the rotating speed of 200r/min, so that the oxidation alkaline leaching of arsenic-containing nickel-cobalt slag is realized; the obtained solid phase is copper nickel cobalt enriched slag, the liquid phase is a leaching solution rich in zinc and arsenic, the main components of the leaching solution are sodium arsenate and sodium zincate, and the leaching solution containing arsenic is evaporated and crystallized to obtain a sodium arsenate product. Through analysis, the leaching rate of arsenic in the original arsenic-nickel-cobalt slag is 99.13%, and the leaching rate of zinc is 98.64%.
Example 5
Adding 60g of arsenic-nickel-cobalt-containing slag material with the particle size of 30 mu M into 200mL of 3M NaOH solution to form mixed slurry, placing the mixed slurry into a reactor, and heating the reactor in a water bath at 95 ℃; the bottom of the reactor is provided with an air inlet ring pipe with the circumference of 15cm, 6 vent holes are uniformly distributed on the air inlet ring pipe, the vent holes on the air inlet ring pipe with the aperture of 4mm and the same cross section form a 30-degree plane with the horizontal plane of the bottom of the reaction container, air is introduced into the reactor from the vent holes, the air introduction flow is 2L/min, a paddle stirrer is adopted to carry out stirring reaction for 6 hours at the rotating speed of 100r/min, the oxidation alkaline leaching of the arsenic-nickel-cobalt slag is realized, the obtained solid phase is copper-nickel-cobalt-enriched slag, the liquid phase is a zinc-arsenic-rich leachate, the main components of the leachate are sodium arsenate and sodium zincate, and the leachate containing arsenic is evaporated and crystallized to obtain a sodium arsenate product. Through analysis, the leaching rate of arsenic in the original arsenic-nickel-cobalt slag is 92.13%, and the leaching rate of zinc is 90.79%.
Example 6
Adding 10g of arsenic-nickel-cobalt-containing slag material with the particle size of 50 mu M into 100mL of 2M NaOH solution to form mixed slurry, placing the mixed slurry into a reactor, and heating the reactor in a water bath at 95 ℃; the bottom of the reactor is provided with an air inlet ring pipe with the circumference of 15cm, 6 vent holes are uniformly distributed on the air inlet ring pipe, the aperture is 5mm, the vent holes on the air inlet ring pipe on the same cross section and the horizontal plane of the bottom of the reaction container form 30 degrees, air is introduced into the reactor from the vent holes, the introduction flow rate of the air is 3.5L/min, a paddle stirrer is adopted to carry out stirring reaction for 12 hours at the rotating speed of 250r/min, the alkaline oxidation leaching of the arsenic-nickel-cobalt slag is realized, the obtained solid phase is copper-nickel-cobalt-enriched slag, the liquid phase is a leachate rich in zinc and arsenic, the main components of the leachate are sodium arsenate and sodium zincate, and the leachate containing arsenic is evaporated and crystallized to obtain a sodium arsenate product. Through analysis, the leaching rate of arsenic in the original arsenic-nickel-cobalt slag is 94.17%, and the leaching rate of zinc is 89.12%.
Example 7
Adding 10g of arsenic-nickel-cobalt-containing slag material with the particle size of 40 mu M into 50mL of 1M NaOH solution to form mixed slurry, placing the mixed slurry into a reactor, and heating the reactor in a water bath at 20 ℃; the bottom of the reactor is provided with an air inlet ring pipe with the circumference of 15cm, 6 vent holes with the aperture of 6mm are uniformly distributed on the air inlet ring pipe, the vent holes on the air inlet ring pipe on the same cross section and the horizontal plane of the bottom of the reaction container form 30 degrees, air is introduced into the reactor from the vent holes, the introduction flow rate of the air is 4L/min, a paddle stirrer is adopted to carry out stirring reaction for 72 hours at the rotating speed of 50r/min, the oxidation alkaline leaching of the arsenic-nickel-cobalt-containing slag is realized, the obtained solid phase is copper-nickel-cobalt-enriched slag, the liquid phase is a leachate rich in zinc and arsenic, the main components of the leachate are sodium arsenate and sodium zincate, and the leachate containing arsenic is evaporated and crystallized to obtain a sodium arsenate. Through analysis, the leaching rate of arsenic in the original arsenic-nickel-cobalt slag is 94.33%, and the leaching rate of zinc is 83.78%. The leaching rate of zinc is mainly influenced by the concentration of the alkali solution.
Comparative example 1
Other conditions of this comparative example were the same as those of example 1 except that the stirring speed during the alkaline oxidation leaching was 20 r/min. Through analysis, the leaching rate of arsenic in the original arsenic-nickel-cobalt slag is 67.75%, and the leaching rate of zinc is 80.34%.
Comparative example 2
The other conditions of this comparative example were the same as those of example 1 except that the stirring speed during the alkaline oxidation leaching was 800 r/min. Through analysis, the leaching rate of arsenic in the original arsenic-nickel-cobalt slag is 54.92%, and the leaching rate of zinc is 68.41%.
Comparative example 3
Other conditions of this comparative example were the same as those of example 1 except that the flow rate of air introduced during the alkaline oxidation leaching was 0.01L/min. Through analysis, the leaching rate of arsenic in the original arsenic-nickel-cobalt slag is 78.93%, and the leaching rate of zinc is 92.74%.
Comparative example 4
Other conditions of this comparative example were the same as those of example 1 except that air was introduced from the top of the slurry during the alkaline oxidation leaching, and the leaching rate of arsenic and zinc in the original arsenic-nickel-cobalt slag was 20.62% and 99.31%, respectively, by analysis.
Comparative example 5
Other conditions of this comparative example were the same as those of example 1 except that the flow rate of air introduced during the alkaline oxidation leaching was 8L/min. In the reaction process, gas overflows and brings water out of the reaction system, so that the system balance is influenced.
Comparative example 6
Other conditions of the comparative example are the same as those of example 1, except that the particle size is further reduced, and the dipping effect is not further improved after the particle size is slightly smaller than 1 μm, but the ore grinding energy consumption is increased, and when the particle size of the arsenic-nickel cobalt slag is further reduced to a nanometer level, slurry solution appears in a slurry system, and the slurry solution is not sufficiently dispersed during stirring, so that the reaction cannot be fully completed.
Comparative example 7
The other conditions of this comparative example were the same as those of example 1 except that the grain size of the arsenic-nickel-cobalt-containing slag material was 200 μm or more. Through analysis, the leaching rate of arsenic in the original arsenic-nickel-cobalt slag is 77.21%, and the leaching rate of zinc is 99.52%.
Comparative example 8
The other conditions of this comparative example were the same as example 1 except that the hole diameter of the intake loop vent hole was 10 mm. Through analysis, the leaching rate of arsenic in the original arsenic-nickel-cobalt slag is 80.21%, and the leaching rate of zinc is 99.62%.
Comparative example 9
The other conditions of this comparative example were the same as example 1 except that the hole diameter of the intake loop vent hole was 1 mm. Through analysis, the leaching rate of arsenic in the original arsenic-nickel-cobalt slag is 65.21%, and the leaching rate of zinc is 99.48%.
Comparative example 10
The comparative example was otherwise identical to example 1 except that the vent was oriented at an angle of α degrees from the tangential direction to the circle at 90 degrees.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for extracting arsenic from arsenic-nickel-cobalt-containing slag and preparing arsenate is characterized in that: the method comprises the following steps:
adding arsenic-containing nickel cobalt slag into an alkali solution in a reaction vessel to obtain slurry, and introducing a gas oxidant from the bottom of the slurry to perform atmospheric oxidation leaching at 20-100 ℃ under stirring; carrying out solid-liquid separation to obtain filter residue and arsenic-containing filtrate, and evaporating and crystallizing the arsenic-containing filtrate to obtain arsenate crystals;
the flow of the gas oxidant per gram of arsenic-nickel-cobalt-containing slag per minute is 0.03-0.06L;
the stirring speed is 50-250 r/min;
the grain size of the arsenic-nickel-cobalt-containing slag is 1-100 mu m;
the bottom of the reaction vessel is provided with a gas inlet ring pipe, the gas inlet ring pipe is provided with n vent holes, n is more than or equal to 1, and the gas oxidant is introduced into the slurry through the vent holes;
the vent hole and the horizontal plane at the bottom of the reaction container form an included angle of α, α is more than or equal to 30 degrees and less than or equal to 60 degrees, and the aperture of the vent hole is 2-6 mm.
2. The method for extracting arsenic from arsenic-nickel-cobalt-containing slag and preparing arsenate according to claim 1, wherein the method comprises the following steps:
the flow rate of introducing a gas oxidant per gram of arsenic-nickel-cobalt-containing slag per minute is 0.05-0.06L;
the rotating speed of the stirring is 100-250 r/min;
the grain size of the arsenic-nickel-cobalt-containing slag is 1-50 mu m.
3. The method for extracting arsenic from arsenic-nickel-cobalt-containing slag and preparing arsenate according to claim 1, wherein the method comprises the following steps: 4-10 vent holes are arranged on the air inlet ring pipe every 15cm, and the vent holes are uniformly distributed on the air inlet ring pipe.
4. The method for extracting arsenic from arsenic-nickel-cobalt-containing slag and preparing arsenate according to claim 3, wherein 4-6 vent holes are arranged on each 15cm of the air inlet ring pipe, the included angle between each vent hole and the horizontal plane of the bottom of the reaction vessel is α, the included angle is equal to or larger than 45 degrees and equal to or smaller than α degrees and equal to or smaller than 60 degrees, and the diameter of each vent hole is 2-3 mm.
5. The method for extracting arsenic from arsenic-nickel-cobalt-containing slag and preparing arsenate according to claim 1, wherein the method comprises the following steps: the alkali solution is a sodium hydroxide solution or a potassium hydroxide solution; the concentration of the alkali solution is 2-10 mol/L; the liquid-solid mass ratio of the alkali solution to the arsenic-nickel-cobalt-containing slag is controlled to be (2-10): 1.
6. The method for extracting arsenic from arsenic-nickel-cobalt-containing slag and preparing arsenate according to claim 1, wherein the method comprises the following steps: the concentration of the alkali solution is 4-5 mol/L;
the liquid-solid mass ratio of the alkali solution to the arsenic-nickel-cobalt-containing slag is controlled to be (4-5): 1.
7. The method for extracting arsenic from arsenic-nickel-cobalt-containing slag and preparing arsenate according to claim 1, wherein the method comprises the following steps: the time of the atmospheric oxidation leaching is more than or equal to 6 hours.
8. The method for extracting arsenic from arsenic-nickel-cobalt-containing slag and preparing arsenate according to claim 1, wherein the method comprises the following steps: the temperature of the atmospheric oxidation leaching is 60-85 ℃.
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| 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 |
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| 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 |
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