CN114540629A - Method for extracting and recovering heavy metal chromium from metallurgical waste slag based on crystalline phase regulation - Google Patents
Method for extracting and recovering heavy metal chromium from metallurgical waste slag based on crystalline phase regulation Download PDFInfo
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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
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Abstract
The invention discloses a method for extracting and recovering heavy metal chromium from metallurgical waste slag based on crystalline phase regulation. Crushing and sieving metallurgical waste residues to obtain waste residue powder, mixing the waste residue powder with sodium carbonate or caustic soda and adding sodium chloride for uniform mixing, roasting in an air atmosphere, washing and filtering the roasted and cooled waste residues, and separating to obtain a chromium extraction solution and dechromization residues. The invention promotes the oxidation of chromium in the metallurgical waste residue with high silicon content by sodium chloride and sodium carbonate or caustic soda, wherein the sodium chloride is used as a template bearing agent and Na+The orientation growth of the sodium silicate crystal can be accelerated and controlled by the transport carrier, the wrapped chromium oxide phase is released, the influence of the contact resistance of reaction substrates is reduced, the formed large pore channel provides an oxygen transfer channel, the content of reaction oxygen is improved, and the oxidation efficiency of chromium is accelerated. Adopt the bookThe method has the advantages that the extraction rate of chromium in the chromium-containing metallurgical waste residue is more than 95 percent, the resource recycling of chromium is realized, and the method has good social and economic benefits and ecological environmental benefits.
Description
Technical Field
The invention belongs to the field of resource recovery of heavy metal chromium in metallurgical waste residues, and particularly relates to a method for extracting and recovering heavy metal chromium from metallurgical waste residues based on crystalline phase regulation.
Technical Field
In the smelting process of ferrochromium, silicochrome, iron-nickel and other alloys, a great deal of industrial waste, namely metallurgical waste slag, can be generated. These metallurgical slags often contain about 10% by weight of the heavy metal chromium. The amount of metallurgical waste slag discharged in continental areas of China is as high as ten million tons every year, but open-air stockpiling is still the main reason for waste slag disposal. The method not only occupies a large land area, but also is exposed in wind and rain to easily generate heavy metal-containing dust and leachate, thereby causing huge burden on the surrounding ecological environment. Chromium, on the other hand, is a strategic resource metal, and one million tons of chromium resources will be lost each year, calculated as 10 wt% chromium content. Therefore, the recycling of the chromium resource in the metallurgical waste residue has an extremely important strategic position.
The fire roasting extraction technology of heavy metal chromium is developed from the earliest chromium extraction from chromite by calcium roasting to chromium extraction by calcium-free roasting (sodium roasting: Chinese patent 'method and device for preparing sodium bichromate by one step by taking chromite as raw material'; Chinese patent 'method for extracting chromium by chromite by calcium-free roasting'), the main reactive substance of sodium roasting is soda or caustic soda, and oxygen is taken as an important oxidant to participate in the reaction, and the reaction formula in the whole process is as follows: 2FeCr2O4+4Na2CO3+3.5O2(g)＝4Na2CrO4+Fe2O3+4CO2(g)；2FeCr2O4+8NaOH+3.5O2(g)＝4Na2CrO4+Fe2O3+4H2O (g). The reaction is gas-solid-liquid (gas: O)2(ii) a Fixing: chromite; liquid: molten state Na2CO3Or molten state NaOH), and one of the keys determining the reaction rate is the oxygen supply in the reaction systemThis, in turn, directly affects the chromium oxidation extraction yield. The traditional sodium method roasting is often limited by oxygen mass transfer to cause low extraction efficiency of chromium, and in order to improve the chromium oxidation rate, Chinese patent 'a method for preparing sodium chromate by chromite low-nitrogen roasting and clinker continuous leaching' provides a roasting mode of total oxygen combustion to improve the chromium oxidation rate.
However, chromium-containing metallurgical slags have a lower chromium content (Cr content of about 10 wt.%) compared to chromite (Cr content of about 40 wt.%), and are characterized by a high silicon content (Si content ≥ 20 wt.%), containing a large amount of silicate phase and amorphous glass phase. The chromium phase in the chromium-containing metallurgical slag is distributed thinly and is wrapped by the silicate phase and the amorphous glass phase, so that the contact of a reaction substrate is hindered, and meanwhile, the silicon phase is easy to form viscous eutectic liquid at the high temperature of over 900 ℃, so that the transmission of oxygen is further hindered, and the chromium extraction efficiency of the metallurgical slag by the traditional sodium method roasting is greatly reduced.
Disclosure of Invention
One of the objectives of the present invention is to overcome the difficulty of difficult access to the reaction substrates. Based on a crystal phase regulation and control thought, by improving Na content of a reaction system+The concentration promotes the silicate phase to grow towards the sodium silicate crystal phase, and the wrapped chromium oxide is released to participate in the oxidation reaction.
The invention also aims to overcome the difficulty of insufficient oxygen transfer in the reaction process caused by high silicon content. The Na is promoted by using sodium chloride at the temperature higher than 801 ℃ to form molten salt+The transport reduces the formation of a passivation layer, and simultaneously plays a role of a template to promote the waste residue to form a large pore channel structure and improve the oxygen transfer.
The invention provides a method for extracting and recovering heavy metal chromium from metallurgical waste slag based on crystalline phase regulation. The method can greatly reduce the addition of soda ash or caustic soda, has extremely high oxidation efficiency on the scattered chromium in the metallurgical waste residue with high silicon content, and can realize deep extraction and separation of the chromium in the metallurgical waste residue. The method has the advantages of simple process, low cost, large treatment capacity, no secondary pollution and the like.
The purpose of the invention is realized by the following technical scheme:
a method for extracting and recovering heavy metal chromium from metallurgical slag based on crystalline phase regulation comprises the following steps:
(1) crushing and sieving metallurgical waste residues to obtain waste residue powder;
(2) mixing the waste residue powder obtained in the step (1) with sodium chloride and sodium carbonate or mixing the waste residue powder obtained in the step (1) with sodium chloride and caustic soda to obtain a uniform material;
(3) feeding the uniform material obtained in the step (2) into a furnace for roasting in an air atmosphere;
(4) and (4) washing and filtering the roasted slag sample in the step (3), and separating to obtain a chromium-containing extracting solution and residues.
Further, the metallurgical slag in the step (1) is chromium-containing slag generated in the alloy pyrometallurgical process, and the chromium-containing slag includes but is not limited to more than one of iron-nickel alloy slag, ferrochrome alloy slag, stainless steel slag and the like.
Further, the metallurgical waste residue in the step (1) is chromium-containing waste residue generated in the alloy smelting process by a pyrogenic process, and comprises ferroalloy waste residue and stainless steel slag;
further, the waste residue powder in the step (1) is controlled to be not less than 100 meshes (not more than 149 mu m);
further, the waste residue powder in the step (2) comprises (0.1-0.4) sodium chloride and (0.1-0.63) sodium carbonate in a mass ratio;
further, the waste residue powder in the step (2) comprises (0.1-0.4) sodium chloride and (0.1-0.5) sodium hydroxide in a mass ratio;
further, the roasting temperature in the step (3) is 600-1000 ℃;
further, the roasting temperature in the step (3) is 800-900 DEG C
Further, the roasting time in the step (3) is 60-240 min;
further, the solvent used in the washing in the step (4) is pure water;
further, the number of washing in step (4) is at least 3.
Further, the number of washing in step (4) is 3.
The principle of the invention is as follows:
the invention is based on a crystal phase regulation idea, and utilizes sodium chloride as Na+The transportation carrier plays a role of a template agent to promote the growth of an amorphous glass phase and a silicate phase to a sodium silicate crystal phase and form a large pore channel, and release a coated chromium oxide phase, so that the influence of the blocked contact of reaction substrates is reduced, meanwhile, the large pore channel provides a channel for oxygen transfer, the content of reaction oxygen is improved, the oxidation efficiency of chromium is accelerated, and the constructed large pore channel also enables the leaching of soluble hexavalent chromium to be easier. The reactions involved in the overall process are as follows,
(1)MSiO4(M＝Mg,Al,etc.)→Na2-xMxSiO4(Na1.74Mg0.79Al0.15Si1.06O4)；
(2)Cr2O3+2Na2CO3+NaCl+1.5O2(g)＝2Na2CrO4+NaCl+2CO2(g)；
(3)Cr2O3+4NaOH+NaCl+1.5O2(g)＝2Na2CrO4+NaCl+2H2O(g)。
the method of the invention has the following advantages and beneficial effects:
(1) the invention provides a method for greatly promoting the oxidation efficiency of chromium in metallurgical waste residues by utilizing sodium chloride, and the extraction rate is more than 95%.
(3) The method promotes the growth of silicate phase to sodium silicate crystal phase based on crystalline phase regulation and control in principle, and can realize the efficient oxidation extraction and recovery of the scattered chromium in the metallurgical waste residue with high silicon content (more than or equal to 20 wt%).
(2) The metallurgical waste residue treated by the method has a large-pore channel, and is favorable for quick leaching and deep recovery of the oxidized chromium.
Drawings
FIG. 1 is a scanning electron microscope image and an elemental surface scan image of a polished cross section of chromium-containing metallurgical slag according to an embodiment of the present invention.
Figure 2 is a scanning electron microscope image of slag powder larger than 100 mesh after sieving.
FIG. 3 is a scanning electron microscope photograph of the residue after washing and separation of the chromium-containing metallurgical waste sample after calcination in example 10.
FIG. 4 is a scanning electron microscope photograph of the residue after washing and separation of the chromium-containing metallurgical waste sample after calcination in example 21.
FIG. 5 is a scanning electron microscope photograph of the residue after washing and separation of the chromium-containing metallurgical waste sample calcined in comparative example 1.
FIG. 6 is a scanning electron microscope photograph of the residue after washing and separation of the chromium-containing metallurgical waste sample calcined in comparative example 3.
FIG. 7 is a scanning electron microscope photograph of the residue after washing and separation of the chromium-containing metallurgical waste sample calcined in comparative example 5.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
In the embodiment, the content of chromium-containing metallurgical slag elements is as follows: si is 26.15 wt%; 5.95 wt% of Cr; scanning Electron Microscopy (SEM) of polished cross-section of chromium-containing metallurgical slag As shown in a of FIG. 1, it can be observed from A of FIG. 1 that the slag mainly contains three phases, namely a silicate phase, a glass phase, and a spinel phase, wherein the spinel phase is sparsely distributed and encapsulated by the glass phase and the silicate phase. B in FIG. 1 is a scanning view of the chromium element in the chromium-containing metallurgical slag, and it can be observed from B in FIG. 1 that chromium is mainly concentrated in the spinel phase and a small amount of doping is distributed in the silicate phase in the glass phase.
Pretreatment of metallurgical waste residues: the chromium-containing metallurgical slag is mechanically crushed and sieved by a 100-mesh sieve, the obtained slag powder is ready to be processed, a scanning electron microscope picture of the slag powder is shown as figure 2, and a sample is observed to be in a plate shape of less than 149 mu m after being crushed from the figure 2.
Example 1
(1) Uniformly mixing chromium-containing metallurgical waste residue powder with sodium chloride and sodium carbonate according to the mass ratio of 1:0.1:0.1 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 180min at 800 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and measuring and analyzing the chromium content by using an inductively coupled plasma emission spectrometer (ICP-OES).
The final chromium extraction from the chromium containing metallurgical slag of example 1 was 28.1%.
Example 2
(1) Uniformly mixing chromium-containing metallurgical slag powder with sodium chloride and sodium carbonate according to the mass ratio of 1:0.2:0.32 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 180min at 800 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction from the chromium-containing metallurgical slag of example 2 was 51.2%.
Example 3
(1) Uniformly mixing chromium-containing metallurgical waste residue powder with sodium chloride and sodium carbonate according to the mass ratio of 1:0.3:0.53 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 180min at 800 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction from the chromium-containing metallurgical slag of example 3 was 68.0%.
Example 4
(1) Uniformly mixing chromium-containing metallurgical waste residue powder with sodium chloride and sodium carbonate according to the mass ratio of 1:0.4:0.63 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 180min at 800 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction from the chromium containing metallurgical slag of example 4 was 72.2%.
Example 5
(1) Uniformly mixing chromium-containing metallurgical waste residue powder with sodium chloride and sodium carbonate according to the mass ratio of 1:0.3:0.53 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 60min at 800 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction from the chromium containing metallurgical slag of example 5 was 56.9%.
Example 6
(1) Uniformly mixing chromium-containing metallurgical waste residue powder with sodium chloride and sodium carbonate according to the mass ratio of 1:0.3:0.53 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 120min at 800 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction from the chromium-containing metallurgical slag of example 6 was 63.5%.
Example 7
(1) Uniformly mixing chromium-containing metallurgical waste residue powder with sodium chloride and sodium carbonate according to the mass ratio of 1:0.3:0.53 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting at 800 ℃ for 240min, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction from the chromium containing metallurgical slag of example 7 was 73.7%.
Example 8
(1) Uniformly mixing chromium-containing metallurgical waste residue powder with sodium chloride and sodium carbonate according to the mass ratio of 1:0.3:0.53 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 180min at 600 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction from the chromium containing metallurgical slag of example 8 was 24.2%.
Example 9
(1) Uniformly mixing chromium-containing metallurgical waste residue powder with sodium chloride and sodium carbonate according to the mass ratio of 1:0.3:0.53 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 180min at 700 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction of the chromium containing metallurgical slag of example 9 was 50.5%.
Example 10
(1) Uniformly mixing chromium-containing metallurgical waste residue powder with sodium chloride and sodium carbonate according to the mass ratio of 1:0.3:0.53 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 180min at 900 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction from the chromium containing metallurgical slag of example 10 was 95.5%. The scanning electron microscope image of the residue after washing and separating the chromium-containing metallurgical waste sample roasted in example 10 is shown in fig. 3, and from a and B in fig. 3, it can be observed that the residue has a structure formed by aggregation of small spherical particles and has a porous characteristic, and a 3D spherical structure (C in fig. 3) in which a silicic acid phase and an amorphous glass phase are converted into a sodium silicate phase can be seen at a high magnification.
Example 11
(1) Uniformly mixing chromium-containing metallurgical waste residue powder with sodium chloride and sodium carbonate according to the mass ratio of 1:0.3:0.53 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 180min at 1000 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction from the chromium containing metallurgical slag of example 11 was 92.5%.
Example 12
(1) Uniformly mixing chromium-containing metallurgical waste residue powder with sodium chloride and sodium hydroxide according to the mass ratio of 1:0.1:0.1 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 180min at 800 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction from the chromium containing metallurgical slag of example 12 was 35.7%.
Example 13
(1) Uniformly mixing chromium-containing metallurgical waste residue powder with sodium chloride and sodium hydroxide according to the mass ratio of 1:0.2:0.2 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 180min at 800 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction from the chromium containing metallurgical slag of example 13 was 63.5%.
Example 14
(1) Uniformly mixing chromium-containing metallurgical waste residue powder with sodium chloride and sodium hydroxide according to the mass ratio of 1:0.3:0.4 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 180min at 800 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction from the chromium containing metallurgical slag of example 14 was 82.1%.
Example 15
(1) Uniformly mixing chromium-containing metallurgical waste residue powder with sodium chloride and sodium hydroxide according to the mass ratio of 1:0.4:0.5 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 180min at 800 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction from the chromium containing metallurgical slag of example 15 was 83.5%.
Example 16
(1) Uniformly mixing chromium-containing metallurgical waste residue powder with sodium chloride and sodium hydroxide according to the mass ratio of 1:0.3:0.4 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 60min at 800 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction from the chromium containing metallurgical slag of example 16 was 60.9%.
Example 17
(1) Uniformly mixing chromium-containing metallurgical waste residue powder with sodium chloride and sodium hydroxide according to the mass ratio of 1:0.3:0.4 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 120min at 800 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction from the chromium containing metallurgical slag of example 17 was 72.5%.
Example 18
(1) Uniformly mixing chromium-containing metallurgical waste residue powder with sodium chloride and sodium hydroxide according to the mass ratio of 1:0.3:0.4 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting at 800 ℃ for 240min, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction of the chromium containing metallurgical slag of example 18 was 83.7%.
Example 19
(1) Uniformly mixing chromium-containing metallurgical waste residue powder with sodium chloride and sodium hydroxide according to the mass ratio of 1:0.3:0.4 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 180min at 600 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction from the chromium containing metallurgical slag of example 19 was 47.9%.
Example 20
(1) Uniformly mixing chromium-containing metallurgical slag powder with sodium chloride and sodium hydroxide according to the mass ratio of 1:0.3:0.4 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 180min at 700 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction from the chromium containing metallurgical slag of example 20 was 61.5%.
Example 21
(1) Uniformly mixing chromium-containing metallurgical waste residue powder with sodium chloride and sodium hydroxide according to the mass ratio of 1:0.3:0.4 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 180min at 900 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction from the chromium containing metallurgical slag in example 21 was 91.2%. The scanning electron microscope image of the residue after washing and separating the chromium-containing metallurgical waste sample roasted in example 21 is shown in FIG. 4, and from A and B in FIG. 4, it can be observed that the residue is composed of spherical particles and has a loose structure, and the collapse of the structure of the silicic acid phase and the amorphous glass phase converted into the sodium silicate phase can be seen at a high magnification (C in FIG. 4).
Example 22
(1) Uniformly mixing chromium-containing metallurgical waste residue powder with sodium chloride and sodium hydroxide according to the mass ratio of 1:0.3:0.4 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 180min at 1000 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, separating to obtain a chromium-containing extracting solution, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) to analyze the chromium content.
The final chromium extraction from the chromium containing metallurgical slag of example 22 was 90.1%.
Comparative example 1
(1) Uniformly mixing chromium-containing metallurgical slag powder and sodium chloride according to the mass ratio of 1:0.3 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace at 900 ℃ for roasting for 180min, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) determination on the obtained chromium-containing solution to analyze the chromium content.
The extraction rate of chromium of the chromium-containing metallurgical slag sample in comparative example 1 was 4.6%, and the scanning electron microscopy of the residue separated by washing the chromium-containing metallurgical slag sample after calcination in comparative example 1 is shown in FIG. 5. from A and B in FIG. 5, it can be observed that the residue still exhibits a plate structure, and only the formation of a small amount of nanorod structures is seen at a high magnification and the reaction is prevented from further proceeding (C in FIG. 5).
Comparative example 2
(1) Uniformly mixing chromium-containing metallurgical slag powder and sodium carbonate according to the mass ratio of 1:0.53 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 180min at the temperature of 900 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) determination on the obtained chromium-containing solution to analyze the chromium content.
The chromium extraction of the chromium containing metallurgical slag sample treated at 900 c in comparative example 2 was 62.5%.
Comparative example 3
(1) Uniformly mixing chromium-containing metallurgical slag powder and sodium carbonate according to the mass ratio of 1:0.53 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 180min at the temperature of 1000 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) determination on the obtained chromium-containing solution to analyze the chromium content.
The extraction rate of chromium of the slag sample treated at 1000 ℃ in comparative example 3 was 81.3%, and the scanning electron micrograph of the residue separated by washing the chromium-containing metallurgical slag sample calcined in comparative example 3 is shown in FIG. 6. from A and B in FIG. 6, it can be observed that the sintering phenomenon occurred on the surface of the residue, and only the aggregation of particles and the occurrence of sintered particles were observed at a high magnification (C in FIG. 6).
Comparative example 4
(1) Uniformly mixing chromium-containing metallurgical slag powder and sodium hydroxide according to the mass ratio of 1:0.4 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 180min at the temperature of 900 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) determination on the obtained chromium-containing solution to analyze the chromium content.
The chromium extraction of the chromium containing metallurgical slag sample treated at 900 c in comparative example 4 was 68.1%.
Comparative example 5
(1) Uniformly mixing chromium-containing metallurgical slag powder and sodium hydroxide according to the mass ratio of 1:0.4 to obtain a uniform material;
(2) placing the uniform material obtained in the step (1) in a furnace, roasting for 180min at the temperature of 1000 ℃, and cooling to room temperature to obtain a treated waste residue sample;
(3) and (3) washing the waste residue sample roasted in the step (2) for 3 times by using pure water, filtering, and carrying out ICP-OES (inductively coupled plasma-optical emission spectrometry) determination on the obtained chromium-containing solution to analyze the chromium content.
The extraction rate of chromium was 85.8% in comparative example 5 in which the chromium-containing metallurgical slag sample was treated at 1000 ℃ and the scanning electron micrograph of the residue separated by washing from the chromium-containing metallurgical slag sample calcined in comparative example 5 is shown in FIG. 7. from A and B in FIG. 7, it was observed that the surface sintering of the residue was remarkable and only the particles closely accompanied with the sintered particles were observed at a high magnification (C in FIG. 7).
The oxidation rate of chromium-containing metallurgical waste residue subjected to roasting treatment by independently adding sodium chloride is extremely low; when sodium carbonate or sodium hydroxide alone is added, the extraction yield is only about eighty percent even if the temperature is raised to 1000 ℃. When the combined additive of sodium chloride and sodium hydroxide or sodium chloride and sodium carbonate is used, the efficiency of extracting chromium from metallurgical waste residue with high silicon content by oxidation is greatly improved, and the energy consumption is greatly reduced compared with single sodium carbonate or sodium bicarbonate.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for extracting and recovering heavy metal chromium from metallurgical slag based on crystalline phase regulation is characterized by comprising the following steps:
(1) crushing and sieving metallurgical waste residues to obtain waste residue powder;
(2) mixing the waste residue powder obtained in the step (1) with sodium chloride and sodium carbonate or mixing the waste residue powder obtained in the step (1) with sodium chloride and caustic soda to obtain a uniform material;
(3) feeding the uniform material obtained in the step (2) into a furnace for roasting in an air atmosphere;
(4) and (4) washing and filtering the roasted slag sample in the step (3), and separating to obtain a chromium-containing extracting solution and residues.
2. The method for extracting and recovering heavy metal chromium from metallurgical slag based on crystalline phase regulation and control as claimed in claim 1, wherein the metallurgical slag in the step (1) is chromium-containing slag generated in a pyrometallurgical alloy smelting process, and comprises more than one of ferroalloy slag and stainless steel slag.
3. The method for extracting and recovering heavy metal chromium from metallurgical slag based on crystalline phase regulation and control as claimed in claim 1, wherein the slag powder in the step (1) is controlled to be not less than 100 meshes in size.
4. The method for extracting and recovering heavy metal chromium from metallurgical slag based on crystalline phase regulation and control as claimed in claim 1, wherein in the step (2), the weight ratio of slag powder, sodium chloride and sodium carbonate is 1 (0.1-0.4) to (0.1-0.63).
5. The method for extracting and recovering heavy metal chromium from metallurgical slag based on crystalline phase regulation and control as claimed in claim 1, wherein in step (2), the mass ratio of slag powder, sodium chloride and sodium hydroxide is 1 (0.1-0.4) to 0.1-0.5.
6. The method for extracting and recovering heavy metal chromium from metallurgical slag based on crystalline phase regulation and control as claimed in claim 1, wherein the roasting temperature in the step (3) is 600-1000 ℃.
7. The method for extracting and recovering heavy metal chromium from metallurgical slag based on crystalline phase regulation and control as claimed in claim 1, wherein the roasting time in the step (3) is 60-240 min.
8. The method for extracting and recovering heavy metal chromium from metallurgical slag based on crystalline phase regulation as claimed in claim 1, wherein the solvent used in the washing in step (4) is pure water.
9. The method for extracting and recovering heavy metal chromium from metallurgical slag based on crystalline phase regulation as claimed in claim 1, wherein the number of washing in step (4) is at least 3.
10. The method for extracting and recovering heavy metal chromium from metallurgical slag based on crystalline phase regulation as claimed in any one of claims 1 to 9, wherein the whole process of the method involves the following reactions:
(1)MSiO4(M＝Mg,Al,etc.)→Na2-xMxSiO4(Na1.74Mg0.79Al0.15Si1.06O4)；
(2)Cr2O3+2Na2CO3+NaCl+1.5O2(g)＝2Na2CrO4+NaCl+2CO2(g)；
(3)Cr2O3+4NaOH+NaCl+1.5O2(g)＝2Na2CrO4+NaCl+2H2O(g)。
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1940097A (en) * | 2005-09-29 | 2007-04-04 | 宝山钢铁股份有限公司 | Extraction of chromium from mud containing chromium by sodium-salt calcination |
| CN104745826A (en) * | 2015-04-01 | 2015-07-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for implementing chromium extraction by performing sodium-modified pellet roasting on chromium slags |
| CN106676290A (en) * | 2017-03-15 | 2017-05-17 | 东北大学 | Method for roasting chromium-containing vanadium slag by adding mixed sodium hydroxide and sodium chloride |
| CN106947875A (en) * | 2017-03-15 | 2017-07-14 | 东北大学 | The mixing of a kind of use NaOH and sodium chloride with addition of and the new baking modes method that is calcined the slag containing chrome alum |
| CN108179265A (en) * | 2018-01-29 | 2018-06-19 | 东北大学 | A kind of method from separation and Extraction vanadium in material containing chrome alum |
| CN108531718A (en) * | 2018-04-23 | 2018-09-14 | 东北大学 | A method of producing chrome green using tailings in vanadium extraction |
| RU2726540C1 (en) * | 2018-10-25 | 2020-07-14 | Паньган Груп Паньчжихуа Айрон Энд Стил Рисёч Инститьют Ко., Лтд. | Method of extracting vanadium and chromium from vanadium-chromium slag |
-
2021
- 2021-12-30 CN CN202111668808.3A patent/CN114540629A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1940097A (en) * | 2005-09-29 | 2007-04-04 | 宝山钢铁股份有限公司 | Extraction of chromium from mud containing chromium by sodium-salt calcination |
| CN104745826A (en) * | 2015-04-01 | 2015-07-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for implementing chromium extraction by performing sodium-modified pellet roasting on chromium slags |
| CN106676290A (en) * | 2017-03-15 | 2017-05-17 | 东北大学 | Method for roasting chromium-containing vanadium slag by adding mixed sodium hydroxide and sodium chloride |
| CN106947875A (en) * | 2017-03-15 | 2017-07-14 | 东北大学 | The mixing of a kind of use NaOH and sodium chloride with addition of and the new baking modes method that is calcined the slag containing chrome alum |
| CN108179265A (en) * | 2018-01-29 | 2018-06-19 | 东北大学 | A kind of method from separation and Extraction vanadium in material containing chrome alum |
| CN108531718A (en) * | 2018-04-23 | 2018-09-14 | 东北大学 | A method of producing chrome green using tailings in vanadium extraction |
| RU2726540C1 (en) * | 2018-10-25 | 2020-07-14 | Паньган Груп Паньчжихуа Айрон Энд Стил Рисёч Инститьют Ко., Лтд. | Method of extracting vanadium and chromium from vanadium-chromium slag |
Non-Patent Citations (4)
| Title |
|---|
| 付自碧等: "钒铬渣钠化焙烧同步提取钒和铬", 《钢铁钒钛》 * |
| 宋桂颖等: "钒渣焙烧工艺钠盐附加剂的选择", 《煤炭与化工》 * |
| 温守东等: "影响钒渣焙烧转化率的因素探讨", 《承德石油高等专科学校学报》 * |
| 王金超: "钙对钒渣提钒的影响", 《四川有色金属》 * |
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