CN109399716B - Method for extracting chromium from chromium-containing material by liquid-phase oxidation - Google Patents
Method for extracting chromium from chromium-containing material by liquid-phase oxidation Download PDFInfo
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Abstract
The invention provides a method for extracting chromium from a chromium-containing material by liquid-phase oxidation, which comprises the step of extracting chromium by liquid-phase oxidation by taking the chromium-containing material and alkali as raw materialsThe material also comprises an additive, the additive comprises a compound of transition metal, the additive is preferably black slag and/or a chromium-containing waste catalyst, the black slag is Cr obtained by sorting leaching slag of liquid-phase oxidation chromium extraction2O3Chromium slag with a content higher than 15 wt.%. The method can obviously improve the conversion rate of chromium in the chromium-containing material and ensure higher oxidation rate of the chromium-containing component; and can realize the high-efficient recovery of chromium in chromium-containing materials under mild reaction conditions, and Cr in tailings2O3The content is less than 2 wt.%.
Description
Technical Field
The invention belongs to the technical field of inorganic salt production, and relates to a method for extracting chromium from a chromium-containing material through liquid-phase oxidation.
Background
CN1226512A introduces a clean process for producing sodium chromate by oxidizing and decomposing chromite with NaOH molten salt liquid phase. The method uses NaOH fused salt, the ratio of alkali to ore is 3:1-6:1, the temperature of the NaOH fused salt is 500-. The method has the disadvantages that the reaction temperature is high when NaOH molten salt is used, the concentration of alkali needs to be increased by evaporation when diluted alkali liquor is recycled, and the energy consumption is high; the concentration of the diluted alkali liquor is still very high, the viscosity of the solution is high, and solid-liquid separation is difficult; in a high-temperature and high-alkali environment, equipment is seriously corroded; and the obtained mixed crystals need to be further separated, and the process flow is long.
CN101817561A discloses a method for cleanly producing sodium chromate by pressure leaching of chromite, and particularly discloses a method for reacting chromite with oxidizing gas in NaOH solution, wherein the mass ratio of NaOH to chromite is 2:1-10:1, the concentration of NaOH is 30-80 wt.%, the reaction time is 0.5-10 hours, the reaction pressure is 0.1-5MPa, and the reaction temperature is 180-320 ℃. And (2) obtaining a mixture of sodium chromate, alkali liquor and iron slag after reaction, allowing the sodium chromate to enter a liquid phase after the mixture is subjected to liquid-solid reaction, adding calcium oxide into the separation liquid to remove impurities, evaporating and crystallizing the impurity-removed liquid to obtain sodium chromate crystals and mother liquor, circulating the crystallized mother liquor and the alkali liquor together for decomposition of chromite, and leaching and drying the sodium chromate crystals by using saturated sodium chromate solution to obtain a qualified product. It has the advantages of low reaction temperature (180-320 ℃), high chromium conversion rate and less slag discharge. However, the method still has the problems of long reaction time, high pressure, complex production process and the like.
CN101481144A and CN101659444A disclose that chromite undergoes oxidation reaction in a mixed medium of caustic alkali and nitrate, nitrate is used only as a catalyst, and a mixed reaction product of alkali liquor, chromate and iron slag is obtained after the reaction. The production process has the problems of large circulation amount of caustic alkali and nitrate medium, difficult separation, long reaction time and the like.
CN101045559A discloses a method for producing sodium chromate by calcium-free roasting of chromite, which comprises the steps of mixing the chromite, sodium carbonate and return slag, carrying out oxidizing roasting, and then carrying out wet sorting or dry sorting to obtain sodium chromate alkaline solution, coarse slag and fine slag, wherein the coarse slag is used as a filler (return slag) for recycling and the fine slag is used as tailings for treatment. The coarse slag components, particularly Cr and Fe, obtained by the method have larger difference, and are directly mixed with chromium ore powder and soda ash to cause instability of raw material components, influence on roasting effect, finally cause unstable production, complex impurity removal process in the subsequent procedure and increase of product cost. Meanwhile, the chromium content in both coarse slag and fine slag is higher:the coarse slag obtained by wet-sorting the roasted product contains 6-7.5% of total chromium and 0.1-0.3% of hexavalent chromium (all according to Cr)2O3The same is measured in the following), dried and used as a return slag circulating ingredient, wherein the fine slag contains 5 to 6 percent of total chromium and 0.1 to 0.2 percent of hexavalent chromium; the coarse slag obtained after dry separation of the roasted product contains 10-14% of total chromium and 0.3-0.5% of hexavalent chromium (all according to Cr)2O3The same is measured in the following), and the dried slag is used as a return slag circulating ingredient, wherein the fine slag contains 5 to 8 percent of total chromium and 0.3 percent of hexavalent chromium. The fine slag has high chromium content. However, the addition amount of the return slag is relatively large, and in addition, the return slag added in the method is coarse slag obtained after the separation of the leaching slag, namely Cr2O3The content is generally 6-14 wt.%, the addition is 1.4-3.0 times of that of chromite, return slag in oxidizing roasting is mainly used as a filler, and a large amount of liquid phase generated in the reaction process is diluted to avoid ring formation of the rotary kiln, so that the rotary kiln can normally run. Therefore, the main function of adding the return slag in the oxidizing roasting is to dilute the liquid phase and avoid ring formation of the rotary kiln. And under the conditions of the liquid phase reaction: (1) the problem of ring formation does not exist, so that the return slag cannot be used for liquid phase oxidation under the inspiration of oxidizing roasting and return slag; (2) the liquid-phase oxidation is a gas-liquid-solid three-phase reaction, if the returned slag is added, the total amount of solids is increased, and if the added liquid-phase amount is not changed, the effective liquid-solid ratio is reduced, so that the gas-liquid-solid three-phase reaction is not facilitated; if the liquid-solid ratio is kept constant, the amount of liquid phase needs to be increased at the same time, and the energy consumption is increased accordingly. Therefore, in the prior art, no report is provided for adding return slag in a method for oxidizing a chromium-containing material in a liquid phase.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for extracting chromium from a chromium-containing material by liquid-phase oxidation, which can obviously improve the conversion rate of chromium in the chromium-containing material and ensure higher oxidation rate of chromium-containing components; and can realize the high-efficient recovery of chromium in chromium-containing materials under mild reaction conditions, and Cr in tailings2O3The content is less than 2 wt.%.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for extracting chromium from a chromium-containing material through liquid-phase oxidation comprises the step of extracting chromium through liquid-phase oxidation by taking the chromium-containing material and alkali as raw materials, wherein the raw materials also comprise an additive, and the additive comprises a transition metal compound.
The transition metal is preferably any one or a combination of at least two of titanium, iron, cobalt, nickel or copper. Typical but non-limiting combinations are titanium and iron, titanium and cobalt, titanium, nickel and copper, cobalt, nickel and copper. I.e. any one or a combination of at least two of a titanium source, an iron source, a cobalt source, a nickel source or a copper source.
According to the method, the additive containing the transition metal compound is added into the raw materials, so that the conversion rate of chromium in the chromium-containing material can be obviously improved, and the high oxidation rate of the chromium-containing component is ensured; and the process condition of extracting chromium by liquid-phase oxidation can be reduced.
The additive is selected from black slag and/or a chromium-containing waste catalyst, and the black slag is Cr obtained by sorting leaching slag obtained by extracting chromium through liquid-phase oxidation2O3Chromium slag in an amount higher than 15 wt.%, such as 15.5 wt.%, 16.8 wt.%, 18 wt.%, 20 wt.%, 21 wt.%, 23 wt.%, 25 wt.%, 28 wt.%, 32 wt.%, 35 wt.%, 40 wt.%, 45 wt.% or 55 wt.%, and the like. The black slag can also be used as a chromium-containing material for extracting chromium by liquid-phase oxidation to directly extract chromium by liquid-phase oxidation. Separating the leached slag of liquid phase oxidation chromium extraction to obtain black slag and red slag, wherein the black slag has high chromium content and is used as additive, and the red slag has chromium content (Cr is used as additive)2O3Calculated) below 2 wt.%, for tailings treatment.
In the method for extracting chromium from chromium-containing materials by calcium-free roasting disclosed by the prior art, the added return slag is coarse slag and Cr obtained after sorting of leached slag2O3The content is generally 6-14 wt.%, the filler is mainly used for diluting a large amount of liquid phase generated in the reaction process, the ring formation of the rotary kiln is avoided, the rotary kiln can normally operate, and the addition amount of the filler is 1.4-3.0 times of that of chromite. The black slag added in the invention has higher chromium content and higher chromium-iron ratio, Cr2O3The content is higher than 15 wt.%, and the ferrochrome spinel structure in the black slag is destroyed in the early reaction process, has higher activity, and has good effect on the iron-chromium-iron-manganeseThe liquid phase oxidation process of the chromium-containing material also has a certain catalytic action, can obviously improve the conversion rate of chromium in the chromium-containing material, ensures higher oxidation rate of chromium-containing components, and can reduce reaction conditions when reaching the same chromium leaching rate as the method for extracting chromium by liquid phase oxidation in the prior art.
The chromium-containing waste catalyst also has a certain catalytic action on the liquid-phase oxidation process of the chromium-containing material, so that the conversion rate of chromium in the chromium-containing material is improved, and the reaction conditions can be reduced when the same chromium leaching rate is achieved as that of the method for extracting chromium by liquid-phase oxidation in the prior art.
Preferably, the sorting comprises a reselection and/or a magnetic separation. The separation method has the characteristics of simple operation, good selectivity, reasonable economy and the like, and is beneficial to industrial application and large-scale production.
Preferably, the chromium-containing spent catalyst is selected from Fe for preparing olefin by alkane dehydrogenation2O3-Cr2O3-K2O catalyst, catalyst for dealkylation to produce benzene, CuO-Cr for selective hydrogenation2O3Catalyst, Fe for high temperature conversion2O3-Cr2O3Catalyst system or Fe for medium temperature shift2O3-Cr2O3Any one or a combination of at least two of the above catalysts. Typical but non-limiting combinations are Fe for olefin production by dehydrogenation of alkanes2O3-Cr2O3-K2O catalyst, dealkylation benzene-making catalyst, CuO-Cr for selective hydrogenation2O3Catalyst and Fe for high temperature conversion2O3-Cr2O3Catalyst system, Fe for medium temperature conversion2O3-Cr2O3Catalyst system, Fe for producing olefin by dehydrogenation of alkane2O3-Cr2O3-K2O catalyst and dealkylation benzene-making catalyst. The chromium-containing spent catalyst may also be another chromium-containing catalyst as long as the transition metal-containing compound has an effect of promoting the extraction of chromium by liquid-phase oxidation.
The additive is added in an amount of more than 5 wt.% of the mass of the chromium-containing material, such as 6 wt.%, 8 wt.%, 10 wt.%, 15 wt.%, 18 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 42 wt.%, 48 wt.% or 55 wt.%.
The mass of the particle size D (90) of the raw material is less than or equal to 50 μm and accounts for more than 90 wt.% of the total mass of the raw material, such as 91 wt.%, 92 wt.%, 93 wt.%, 94 wt.%, 95 wt.%, 96 wt.%, 97 wt.%, 98 wt.% or 99 wt.%. D (90) refers to the particle size corresponding to 90% of the cumulative particle size distribution of the sample. D (90) is less than or equal to 50 mu m, namely the granularity of 90 percent of the particles in the sample is less than or equal to 50 mu m (the particles with the granularity of less than or equal to 50 mu m account for 90 percent of the total number of the particles).
The method for extracting chromium from the chromium-containing material by liquid-phase oxidation comprises the following steps: adding chromium-containing materials and alkali into water for reaction, and then carrying out solid-liquid separation to obtain leachate and leaching residues.
The chromium-containing material is selected from any one or a combination of at least two of chromite, ferrochrome or chromium slag, typically but not limited to a combination of chromite and chromite, ferrochrome and chromium slag.
Preferably, the base is selected from sodium hydroxide and/or potassium hydroxide.
The mass ratio of the alkali to the chromium-containing material is 3:1-7:1, such as 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1 or 6.5: 1.
The concentration of the alkali solution in the liquid-phase oxidation chromium extraction is 50 wt.% to 70 wt.%, such as 52 wt.%, 58 wt.%, 60 wt.%, 63 wt.%, 65 wt.%, 68 wt.% or 69 wt.%.
The process conditions for extracting chromium by liquid-phase oxidation are as follows: the stirring speed is 600r/min-800r/min, such as 650r/min, 700r/min or 750r/min, the reaction temperature is 170-320 ℃, such as 180 ℃, 200 ℃, 230 ℃, 250 ℃, 130 ℃, 300 ℃ or 310 ℃, the reaction time is 2h-8h, such as 2.1h, 2.3h, 2.5h, 2.8h, 3h, 3.5h, 4h, 4.5h, 5.5h or 6.5h, the oxygen partial pressure is 0.1MPa-4.0MPa, such as 0.5MPa, 1.0MPa, 1.5MPa, 2.0MPa, 2.5MPa, 3.0MPa or 3.5MPa, etc.
As a preferred technical scheme, the method for extracting chromium from chromium-containing material by liquid-phase oxidation comprises the following steps:
(1) adding a chromium-containing material, black slag and alkali into water for reaction, wherein the mass ratio of the alkali to the chromium-containing material is 3:1-7:1, the concentration of the alkali solution is 50-70 wt.%, the addition amount of the black slag is more than 5 wt.% of the mass of the chromium-containing material, the stirring speed is 600-800 r/min, the reaction temperature is 170-320 ℃, the reaction time is 2-8 h, and the oxygen partial pressure in the reaction process is 0.1-4.0 MPa; then, carrying out solid-liquid separation to obtain chromium-containing leachate and leaching residues;
(2) separating the leached slag to obtain Cr2O3Black slag and Cr in an amount of more than 15 wt%2O3Red slag with a content of less than 2 wt.%, the black slag being returned to step (1); or the like, or, alternatively,
the method for extracting chromium from the chromium-containing material by liquid-phase oxidation comprises the following steps:
(1) adding a chromium-containing material, a chromium-containing waste catalyst and alkali into water for reaction, wherein the mass ratio of the alkali to the chromium-containing material is 3:1-7:1, the concentration of the alkali solution is 50-70 wt.%, the addition amount of the chromium-containing waste catalyst is more than 5 wt.% of the mass of the chromium-containing material, the stirring speed is 600-800 r/min, the reaction temperature is 170-320 ℃, the reaction time is 2-8 h, and the oxygen partial pressure in the reaction process is 0.1-4.0 MPa; then, carrying out solid-liquid separation to obtain chromium-containing leachate and leaching residues;
(2) separating the leached slag to obtain Cr2O3Black slag and Cr in an amount of more than 15 wt%2O3Red slag with the content of less than 2 wt.%, and the black slag is returned to the step (1) to be used as a raw material for extracting chromium by liquid phase oxidation.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
according to the method for extracting chromium from the chromium-containing material by liquid-phase oxidation, the additive is added into the raw material on the basis of liquid-phase oxidation chromium extraction, so that the conversion rate of chromium in the chromium-containing material can be obviously improved, the higher oxidation rate of chromium-containing components is ensured, and the oxidation rate of chromium is improved by 5-30% under the same process conditions;
the method for extracting chromium from chromium-containing materials by liquid-phase oxidation can reduce the technological conditions of liquid-phase chromium extraction by adding additives into the raw materials, for example, when the leaching rate of chromium is 80%, the reaction temperature is reduced from 230 ℃ to 200 ℃, and the high-efficiency recovery of chromium in chromium-containing materials can be realized under mild conditions, thereby ensuring that the chromium in tailings is recovered2O3With a content of less than 2 wt.%, e.g. leaching residues passing through a hydrocyclone at room temperature to obtain Cr2O325 wt.% black slag and Cr in tailings2O3The content was 1.8 wt.%.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
In the present invention, wt.% means a mass percentage content unless otherwise specified.
The black slag is Cr obtained by sorting leaching slag obtained by extracting chromium through liquid-phase oxidation2O3The content of the red slag is more than 15 wt.%, and the red slag is Cr obtained by sorting leaching slag obtained by extracting chromium through liquid-phase oxidation2O3Slag with a content of less than 2 wt.%.
The chromium leaching rate is the percentage of the chromium content in the leaching solution in the original chromium content (including chromium in raw chromium ore powder and chromium in black slag).
Sorting as described in the following examples includes reselection and/or magnetic separation.
The mass of the particle size D (90) of the raw materials in the following examples is less than or equal to 50 μm and accounts for more than 90 wt% of the total mass of the raw materials.
Example 1
A method for extracting chromium from chromium-containing materials through liquid-phase oxidation comprises the following steps:
(1) mixing raw chromium ore powder (Cr)2O3Content of 45 wt.%), adding caustic soda into water according to a mass ratio of 1:3, and simultaneously adding black slag, wherein the adding amount of the black slag is 10% of the mass of raw material chromium ore powder, and performing liquid-phase leaching under the conditions that the alkali concentration of a solution is 65 wt.%, the stirring speed is 800r/min, the reaction temperature is 200 ℃, the reaction time is 4h, and the oxygen partial pressure is 3.2 MPa;
(2) subjecting the leaching slurry to leachingSolid separation is carried out to obtain leaching liquid and leaching slag, the leaching rate of chromium reaches 85%, the leaching slag is washed and separated to obtain black slag and red slag, the black slag is returned to the step (1) for leaching, the red slag is treated as tailings, wherein Cr in the red slag is2O3The content was 1.8 wt.%.
Comparative example 1
A method for extracting chromium from chromium-containing materials through liquid-phase oxidation comprises the following steps:
(1) mixing raw chromium ore powder (Cr)2O3Content 45 wt.%), caustic soda is added into water according to the mass ratio of 1:3, liquid-phase leaching is carried out under the conditions that the alkali concentration of the solution is 65 wt.%, the stirring speed is 800r/min, the reaction temperature is 200 ℃, the reaction time is 4h, and the oxygen partial pressure is 3.2 MPa;
(2) carrying out liquid-solid separation on the leaching slurry to obtain leaching liquid and leaching residues, wherein the leaching rate of chromium reaches 68%, and the leaching residues are washed to obtain tailings Cr2O3The content was 17.4 wt.%.
Comparative example 2
A method for extracting chromium from chromium-containing materials through liquid-phase oxidation comprises the following steps:
(1) mixing raw chromium ore powder (Cr)2O3Content 45 wt.%), caustic soda is added into water according to the mass ratio of 1:3, and liquid-phase leaching is carried out under the conditions that the alkali concentration of the solution is 70 wt.%, the stirring speed is 800r/min, the reaction temperature is 230 ℃, the reaction time is 6h, and the oxygen partial pressure is 4.0 MPa;
(2) carrying out liquid-solid separation on the leaching slurry to obtain leaching liquid and leaching residues, wherein the leaching rate of chromium reaches 85%, and the leaching residues are washed to obtain tailings Cr2O3The content was 6.8 wt.%.
Example 2
A method for extracting chromium from chromium-containing materials through liquid-phase oxidation comprises the following steps:
(1) mixing raw chromium ore powder (Cr)2O3Content of 45 wt.%), caustic soda is added into water according to the mass ratio of 1:7, black slag is added at the same time, the adding amount of the black slag is 5% of the mass of raw material chromium ore powder, the alkali concentration of the solution is 50 wt.%, the stirring speed is 600r/min, the reaction temperature is 220 ℃, the reaction time is 3h, and the oxygen partial pressure is 3hLiquid phase leaching is carried out under the condition of 3.5 MPa;
(2) performing liquid-solid separation on the leaching slurry to obtain leaching liquid and leaching residues, wherein the leaching rate of chromium reaches 87%, the leaching residues are washed and sorted to obtain black residues and red residues, the black residues are returned to the step (1) for leaching, the red residues are treated as tailings, and Cr in the red residues2O3The content was 1.5 wt.%.
Example 3
A method for extracting chromium from chromium-containing materials through liquid-phase oxidation comprises the following steps:
(1) mixing raw chromium ore powder (Cr)2O3Content of 45 wt.%), adding caustic soda into water according to a mass ratio of 1:5, and simultaneously adding black slag, wherein the adding amount of the black slag is 8% of the mass of raw material chromium ore powder, and performing liquid-phase leaching under the conditions that the alkali concentration of a solution is 70 wt.%, the stirring speed is 700r/min, the reaction temperature is 170 ℃, the reaction time is 8h, and the oxygen partial pressure is 4.0 MPa;
(2) performing liquid-solid separation on the leaching slurry to obtain leaching liquid and leaching residues, wherein the leaching rate of chromium reaches 95%, the leaching residues are washed and sorted to obtain black residues and red residues, the black residues are returned to the step (1) for leaching, the red residues are treated as tailings, and Cr in the red residues2O3The content was 0.7 wt.%.
Example 4
A method for extracting chromium from chromium-containing materials through liquid-phase oxidation comprises the following steps:
(1) mixing raw chromium ore powder (Cr)2O339 wt.%), adding potassium hydroxide into water according to the mass ratio of 1:4, and simultaneously adding black slag, wherein the adding amount of the black slag is 13% of the mass of the raw material chromium ore powder, and performing liquid-phase leaching under the conditions that the alkali concentration of the solution is 60 wt.%, the stirring speed is 700r/min, the reaction temperature is 320 ℃, the reaction time is 2h, and the oxygen partial pressure is 0.1 MPa;
(2) performing liquid-solid separation on the leaching slurry to obtain leaching liquid and leaching residues, wherein the leaching rate of chromium reaches 96%, the leaching residues are washed and sorted to obtain black residues and red residues, the black residues are returned to the step (1) for leaching, the red residues are used as tailings for treatment, and Cr in the tailings is2O3The content was 0.5 wt.%.
Example 5
A method for extracting chromium from chromium-containing materials through liquid-phase oxidation comprises the following steps:
(1) mixing raw chromium ore powder (Cr)2O339 wt.%), caustic soda is added into water according to the mass ratio of 1:6, black slag is added at the same time, the addition amount of the black slag is 17% of the mass of raw material chromium ore powder, liquid phase leaching is carried out under the conditions that the alkali concentration of the solution is 55 wt.%, the stirring rotation speed is 750r/min, the reaction temperature is 250 ℃, the reaction time is 3h, and the oxygen partial pressure is 2.0 MPa;
(2) performing liquid-solid separation on the leaching slurry to obtain leaching liquid and leaching residues, wherein the leaching rate of chromium reaches 92%, the leaching residues are washed and separated to obtain black residues and red residues, the black residues are returned to the step (1) for leaching, the red residues are treated as tailings, and Cr in the red residues2O3The content was 1.1 wt.%.
Example 6
A method for extracting chromium from chromium-containing materials through liquid-phase oxidation comprises the following steps:
(1) chromium slag (Cr)2O3Content of 20 wt.%), adding caustic soda into water according to a mass ratio of 1:4, and simultaneously adding black slag, wherein the adding amount of the black slag is 21% of the mass of raw material chromium ore powder, and performing liquid-phase leaching under the conditions that the alkali concentration of a solution is 63 wt.%, the stirring speed is 650r/min, the reaction temperature is 200 ℃, the reaction time is 4h, and the oxygen partial pressure is 1.5 MPa;
(2) performing liquid-solid separation on the leaching slurry to obtain leaching liquid and leaching residues, wherein the leaching rate of chromium reaches 89%, the leaching residues are washed and sorted to obtain black residues and red residues, the black residues are returned to the step (1) for leaching, the red residues are treated as tailings, and Cr in the red residues2O3The content was 1.3 wt.%.
Example 7
A method for extracting chromium from chromium-containing materials through liquid-phase oxidation comprises the following steps:
(1) chromium-containing minerals (Cr)2O335 wt.%), caustic soda is added into water according to the mass ratio of 1:5, black slag is added at the same time, the adding amount of the black slag is 26% of the mass of raw material chromium ore powder, the alkali concentration of the solution is 58 wt.%, the stirring speed is 780r/min, the reaction temperature is 230 DEG CCarrying out liquid phase leaching under the conditions that the reaction time is 5 hours and the oxygen partial pressure is 2.5 MPa;
(2) performing liquid-solid separation on the leaching slurry to obtain leaching liquid and leaching residues, wherein the leaching rate of chromium reaches 93%, the leaching residues are washed and sorted to obtain black residues and red residues, the black residues are returned to the step (1) for leaching, the red residues are treated as tailings, and Cr in the red residues2O3The content was 1.0 wt.%.
Example 8
A method for extracting chromium from chromium-containing materials through liquid-phase oxidation comprises the following steps:
(1) chromium-containing minerals (Cr)2O3Content of 35 wt.%), caustic soda is added into water according to the mass ratio of 1:5, and simultaneously Fe for high (medium) temperature conversion accounting for 5 wt.% of the chromium-containing mineral substance is added2O3-Cr2O3The waste catalyst is subjected to liquid phase leaching under the conditions that the alkali concentration of the solution is 58 wt.%, the stirring speed is 780r/min, the reaction temperature is 230 ℃, the reaction time is 5h, and the oxygen partial pressure is 2.5 MPa;
(2) performing liquid-solid separation on the leaching slurry to obtain leaching liquid and leaching residues, wherein the leaching rate of chromium reaches 91%, the leaching residues are washed and sorted to obtain black residues and red residues, the black residues are returned to the step (1) for leaching, the red residues are treated as tailings, and Cr in the red residues2O3The content was 1.2 wt.%.
Example 9
A method for extracting chromium from chromium-containing materials through liquid-phase oxidation comprises the following steps:
(1) mixing raw chromium ore powder (Cr)2O3Content of 45 wt.%), caustic soda is added into water according to the mass ratio of 1:3, and simultaneously Fe for high (medium) temperature conversion accounting for 10 wt.% of the chromium-containing mineral substance is added2O3-Cr2O3The waste catalyst is subjected to liquid phase leaching under the conditions that the alkali concentration of a solution is 65 wt.%, the stirring speed is 800r/min, the reaction temperature is 200 ℃, the reaction time is 4h, and the oxygen partial pressure is 3.2 MPa;
(2) performing liquid-solid separation on the leaching slurry to obtain leaching solution and leaching residues, wherein the leaching rate of chromium reaches 86%, the leaching residues are washed and separated to obtain black residues and red residues, and the black residues are returned to the stepLeaching in the step (1), and treating red slag as tailings, wherein Cr in the red slag is2O3The content was 1.7 wt.%.
Comparative example 3
A method for extracting chromium from chromium-containing materials through liquid-phase oxidation comprises the following steps:
(1) mixing raw chromium ore powder (Cr)2O3Content of 45 wt.%), caustic soda is added into water according to the mass ratio of 1:3, liquid-phase leaching is carried out under the conditions that the alkali concentration of the solution is 65 wt.%, the stirring speed is 800r/min, the reaction temperature is 240 ℃, the reaction time is 4h, and the oxygen partial pressure is 3.5 MPa;
(2) performing liquid-solid separation on the leaching slurry to obtain leaching liquid and leaching residues, wherein the leaching rate of chromium reaches 84%, the leaching residues are washed and separated to obtain black residues and red residues, the black residues are returned to the step (1) for leaching, the red residues are treated as tailings, and Cr in the red residues2O3The content was 6.7 wt.%.
Example 10
A method for extracting chromium from chromium-containing materials through liquid-phase oxidation comprises the following steps:
(1) mixing raw chromium ore powder (Cr)2O3Content of 45 wt.%), caustic soda is added into water according to the mass ratio of 1:7, and simultaneously, Fe for high (medium) temperature conversion accounting for 20 wt.% of the chromium-containing mineral substance is added2O3-Cr2O3The waste catalyst is subjected to liquid phase leaching under the conditions that the alkali concentration of a solution is 50 wt.%, the stirring speed is 600r/min, the reaction temperature is 220 ℃, the reaction time is 3h, and the oxygen partial pressure is 3.5 MPa;
(2) performing liquid-solid separation on the leaching slurry to obtain leaching liquid and leaching residues, wherein the leaching rate of chromium reaches 90%, the leaching residues are washed and sorted to obtain black residues and red residues, the black residues are returned to the step (1) for leaching, the red residues are treated as tailings, and Cr in the red residues2O3The content was 1.3 wt.%.
Example 11
A method for extracting chromium from chromium-containing materials through liquid-phase oxidation comprises the following steps:
(1) mixing raw chromium ore powder (Cr)2O3Content 45 wt.%), caustic soda is added into water according to the mass ratio of 1:4,simultaneously adding 15 wt.% of Fe for high (medium) temperature conversion based on the mass of the chromium-containing minerals2O3-Cr2O3The waste catalyst is subjected to liquid phase leaching under the conditions that the alkali concentration of a solution is 50 wt.%, the stirring speed is 600r/min, the reaction temperature is 320 ℃, the reaction time is 2h, and the oxygen partial pressure is 0.1 MPa;
(2) performing liquid-solid separation on the leaching slurry to obtain leaching liquid and leaching residues, wherein the leaching rate of chromium reaches 93%, the leaching residues are washed and sorted to obtain black residues and red residues, the black residues are returned to the step (1) for leaching, the red residues are treated as tailings, and Cr in the red residues2O3The content was 1.0 wt.%.
Example 12
A method for extracting chromium from chromium-containing materials through liquid-phase oxidation comprises the following steps:
(1) mixing raw chromium ore powder (Cr)2O3Content of 45 wt.%), caustic soda is added into water according to the mass ratio of 1:6, and simultaneously, Fe for high (medium) temperature conversion accounting for 20 wt.% of the chromium-containing mineral substance is added2O3-Cr2O3The waste catalyst is subjected to liquid phase leaching under the conditions that the alkali concentration of the solution is 70 wt.%, the stirring speed is 800r/min, the reaction temperature is 170 ℃, the reaction time is 6h, and the oxygen partial pressure is 4.0 MPa;
(2) performing liquid-solid separation on the leaching slurry to obtain leaching liquid and leaching residues, wherein the leaching rate of chromium reaches 92%, the leaching residues are washed and separated to obtain black residues and red residues, the black residues are returned to the step (1) for leaching, the red residues are treated as tailings, and Cr in the red residues2O3The content was 1.1 wt.%.
Fe for high (medium) temperature conversion in examples 8 to 122O3-Cr2O3Replacement of spent catalyst with other chromium-containing spent catalyst, e.g. Fe for dehydrogenation of alkanes to olefins2O3-Cr2O3-K2O catalyst, catalyst for dealkylation to produce benzene or CuO-Cr for selective hydrogenation2O3One or the combination of at least two of the catalysts has the leaching rate of the chromium of 85 to 93 percent and the Cr in the red slag2O3The content is 1.2-1.7 wt.%.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (12)
1. A method for extracting chromium from a chromium-containing material by liquid-phase oxidation comprises the step of extracting chromium by liquid-phase oxidation by using the chromium-containing material and alkali as raw materials, and is characterized in that the raw materials also comprise an additive, and the additive comprises a compound of transition metal; the additive is selected from black slag and/or a chromium-containing waste catalyst, and the black slag is Cr obtained by sorting leaching slag obtained by extracting chromium through liquid-phase oxidation2O3Chromium slag with a content higher than 15 wt.%.
2. The method of claim 1, wherein the sorting comprises reselection and/or magnetic separation.
3. The method of claim 1, wherein the chromium-containing spent catalyst is selected from the group consisting of Fe for olefin production by alkane dehydrogenation2O3-Cr2O3-K2O catalyst, catalyst for dealkylation to produce benzene, CuO-Cr for selective hydrogenation2O3Catalyst, Fe for high temperature conversion2O3-Cr2O3Catalyst system or Fe for medium temperature shift2O3-Cr2O3Any one or a combination of at least two of the above catalysts.
4. The method of claim 1, wherein the additive is added in an amount of greater than 5 wt.% based on the mass of the chromium-containing material.
5. The method according to claim 1, characterized in that the mass of the particle size D90 ≤ 50 μm of the feedstock accounts for more than 90 wt.% of the total mass of the feedstock.
6. The method of claim 1, wherein the method for extracting chromium from the chromium-containing material by liquid phase oxidation comprises the following steps: adding the chromium-containing material, alkali and the additive into water for reaction, and then carrying out solid-liquid separation to obtain the chromium-containing material and leaching residues.
7. A process according to claim 1 wherein the chromium containing material is selected from any one of chromite, ferrochrome or chromium slag or a combination of at least two thereof.
8. The method according to claim 6, wherein the base is selected from sodium hydroxide and/or potassium hydroxide.
9. The method of claim 6, wherein the mass ratio of base to chromium containing material is from 3:1 to 7: 1.
10. The method of claim 1, wherein the concentration of the alkali solution in the liquid phase oxidation chromium extraction is 50 wt.% to 70 wt.%.
11. The method according to claim 1, wherein the process conditions for extracting chromium by liquid-phase oxidation are as follows: the stirring speed is 600r/min-800r/min, the reaction temperature is 170-320 ℃, the reaction time is 2-8 h, and the oxygen partial pressure is 0.1-4.0 MPa.
12. The method of any one of claims 1 to 11, wherein the liquid phase oxidation chromium extraction method comprises:
(1) adding a chromium-containing material, black slag and alkali into water for reaction, wherein the mass ratio of the alkali to the chromium-containing material is 3:1-7:1, the concentration of the alkali solution is 50-70 wt.%, the addition amount of the black slag is more than 5 wt.% of the mass of the chromium-containing material, the stirring speed is 600-800 r/min, the reaction temperature is 170-320 ℃, the reaction time is 2-8 h, and the oxygen partial pressure in the reaction process is 0.1-4.0 MPa; then, carrying out solid-liquid separation to obtain chromium-containing leachate and leaching residues;
(2) separating the leached slag to obtain Cr2O3Black slag and Cr in an amount of more than 15 wt%2O3Red slag with a content of less than 2 wt.%, the black slag being returned to step (1); or the like, or, alternatively,
the method for extracting chromium by liquid-phase oxidation comprises the following steps:
(a) adding a chromium-containing material, a chromium-containing waste catalyst and alkali into water for reaction, wherein the mass ratio of the alkali to the chromium-containing material is 3:1-7:1, the concentration of the alkali solution is 50-70 wt.%, the addition amount of the chromium-containing waste catalyst is more than 5 wt.% of the mass of the chromium-containing material, the stirring speed is 600-800 r/min, the reaction temperature is 170-320 ℃, the reaction time is 2-8 h, and the oxygen partial pressure in the reaction process is 0.1-4.0 MPa; then, carrying out solid-liquid separation to obtain chromium-containing leachate and leaching residues;
(b) separating the leached slag to obtain Cr2O3Black slag and Cr in an amount of more than 15 wt%2O3Red slag with a content of less than 2 wt.%, said black slag being returned to step (a) for use as a feedstock for liquid phase oxidative chromium extraction.
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