CN112978897B - Method for removing iron and manganese from zinc smelting process solution - Google Patents
Method for removing iron and manganese from zinc smelting process solution Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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Abstract
The invention provides a method for removing iron and manganese from a zinc smelting process solution. The method comprises the following steps: adding a catalyst into the zinc smelting process solution, and introducing an oxidant into the zinc smelting process solution to enable iron ions and manganese ions in the zinc smelting process solution to perform catalytic oxidation reaction to form slurry containing iron and manganese residues; carrying out solid-liquid separation on the slurry containing the iron-manganese slag to obtain the iron-manganese slag and a liquid after iron and manganese removal; wherein the catalyst is selected from one or more of sulfur dioxide-containing gas and sulfite-containing salt. The method for removing iron and manganese in the zinc smelting process solution provided by the invention has stronger applicability and operability, and can realize catalytic oxidation of iron and manganese elements by one-step method. The compounding of the oxidant and the catalyst promotes the catalytic oxidation speed to be faster, realizes the more effective control of the concentration of iron and manganese ions, shortens the process flow of removing iron and manganese and has lower cost.
Description
Technical Field
The invention relates to the field of zinc smelting, in particular to a method for removing iron and manganese in a zinc smelting process solution.
Background
The existence of manganese element in the zinc smelting process is very important, and the balance of the manganese element plays a key role in the cost control, the process development and the operating environment of the zinc smelting process. The iron element is a harmful element and needs to be removed in the zinc smelting process, and the iron removal is generally realized by adopting an oxidation method, controlling the pH value and other parameters to convert the iron element into different types of precipitates so as to achieve the aim of iron removal.
In the traditional zinc smelting process, the oxide of high valence manganese is mostly adopted as an oxidant to oxidize low valence iron, so that the aim of removing iron elements is fulfilled, and the added manganese elements can be converted into the high valence oxide of manganese for recycling in the electrolytic process. However, if a large amount of high-valence manganese is added for iron removal, the manganese element is excessive, and finally the excessive manganese system cannot achieve the balance of the manganese element in the subsequent process of zinc smelting, so that the excessive manganese needs to be further removed after iron removal. However, because the oxidation potential required for converting manganese into precipitable oxides is relatively high, and no new impurities can be introduced into a zinc smelting system, under the double conditions, less oxidant can be selected in the subsequent manganese removal process, and the manganese oxidation must be carried out by adopting catalytic oxidation.
In a word, different oxidation methods are respectively adopted for removing iron and manganese in the traditional process, the operation is carried out step by step, the process flow is long, and the cost is high. The oxidation of iron is realized by means of the oxidation of the high valence oxide of manganese, which is equivalent to removing iron and simultaneously reintroducing the manganese element into the system, and then subsequently removing the manganese element, so that the consumption of the oxidant is increased, and the number of impurity removal processes and the production cost are increased. In addition, the balance of the manganese element is difficult to control, the process stability is not strong, the method for removing the manganese element is introduced in the prior art, but the process uniformity and optimization are not realized in the integral impurity removal.
For the above reasons, it is necessary to provide a process for removing iron and manganese by catalytic oxidation in zinc smelting, in which iron and manganese ions in a solution are converted into their higher oxides respectively by a one-step method and separated from the solution.
Disclosure of Invention
The invention mainly aims to provide a method for removing iron and manganese in a zinc smelting process solution, which aims to solve the problems of long process flow, difficult control of manganese element balance, low iron and manganese removal efficiency and high cost caused by the step-by-step operation of different oxidation methods for removing iron and manganese in the conventional zinc smelting process.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a method of removing iron and manganese from a zinc smelting process solution. The method comprises the following steps: adding a catalyst into the zinc smelting process solution, and introducing an oxidant into the zinc smelting process solution to simultaneously perform catalytic oxidation reaction on iron ions and manganese ions in the zinc smelting process solution to form slurry containing iron and manganese residues; carrying out solid-liquid separation on the slurry containing the iron-manganese slag to obtain the iron-manganese slag and a liquid after iron and manganese removal; wherein the catalyst is selected from one or more of sulfur dioxide-containing gas and corresponding salt containing sulfite.
Further, the sulfur dioxide containing gas is selected from sulfur dioxide or a flue gas containing sulfur dioxide.
Preferably, the corresponding salt containing sulfite is selected from one or more of zinc sulfite, sodium sulfite, calcium sulfite and sodium bisulfite.
Further, the catalyst is selected from one or more of sulfur dioxide, flue gas containing sulfur dioxide, zinc sulfite, sodium sulfite, calcium sulfite and sodium hydrogen sulfite.
Preferably, the catalyst is selected from one or more of sulfur dioxide, flue gas containing sulfur dioxide, zinc sulfite, sodium sulfite, calcium sulfite and sodium bisulfite.
More preferably, the catalyst is sulfur dioxide or flue gas containing sulfur dioxide, or a mixture of zinc sulfite and sodium sulfite in a weight ratio of (1-3): 1, or a mixture of zinc sulfite, sodium sulfite and calcium sulfite in a weight ratio of (1-2): 1, or a mixture of zinc sulfite, calcium sulfite and sodium bisulfite in a weight ratio of (1-1.5): 1.
Further, the oxidizing agent is selected from one or more of an oxygen-containing gas, an oxidizing liquid, and a solid peroxide.
Preferably, the oxygen-containing gas is selected from one or more of oxygen, compressed air, oxygen-enriched air, ozone.
Preferably, the oxidizing liquid is selected from hydrogen peroxide.
Preferably, the solid peroxide is selected from sodium peroxide.
Further, when the catalyst is selected from sulfur dioxide or flue gas containing sulfur dioxide, the introduction amount of the catalyst is 1.5-10 times of the total mole number of iron ions and manganese ions in the solution in the zinc smelting process; when the catalyst is selected from salts corresponding to sulfite-containing anions, the amount of the catalyst is 1-25% of the weight of the solution in the zinc smelting process.
Preferably, the dosage of the catalyst is 1.7-8 times of the total weight of iron ions and manganese ions in the solution in the zinc smelting process.
Further, the reaction temperature in the catalytic oxidation process is 30-200 ℃, preferably 30-90 ℃, and more preferably 50-90 ℃. Preferably, the reaction pressure in the catalytic oxidation process is 0.01-2.3 MPa, and more preferably 0.8-1.2 MPa.
Further, the pH value of the reaction system in the catalytic oxidation process is 0.5-6.
Preferably, when the catalyst is zinc sulfite, sodium sulfite, calcium sulfite or sodium bisulfite, the pH value is 4-6; when the catalyst is sulfur dioxide-containing gas or sulfur dioxide-containing flue gas, the pH value of a reaction system in the catalytic oxidation process is 2.5-4.
Further, the method further comprises: and returning part of the ferro-manganese slag to a reaction system of the catalytic oxidation reaction to be used as seed crystals. Preferably, the seed ratio of the seed to be added is (0.2-10): 1, more preferably (1.5-3): 1.
Further, the solid-liquid separation mode is selected from concentration separation, sedimentation separation, centrifugal separation, adsorption separation or cyclone separation. Preferably, after the ferro-manganese slag is obtained, the method further comprises the step of washing the ferro-manganese slag, and more preferably, the weight ratio of the washing agent to the ferro-manganese slag is (0.5-6): 1.
Further, the zinc smelting process solution is selected from iron-manganese-containing solution, washing water, ore pulp or slag pulp in the zinc smelting process; preferably, the zinc smelting process is a zinc concentrate smelting process, and more preferably a high manganese zinc concentrate smelting process with the manganese content of 0.3% -6%. Preferably, the zinc smelting process solution contains 50-160 g/L of zinc ions, 1-8 g/L of divalent iron ions and 5-30 g/L of divalent manganese ions.
The method for removing iron and manganese in the zinc smelting process solution provided by the invention has stronger applicability and operability, and can realize catalytic oxidation of iron and manganese elements by one-step method. The compounding of the oxidant and the catalyst promotes the catalytic oxidation speed to be faster, realizes the more effective control of the concentration of iron and manganese ions, shortens the process flow of removing iron and manganese and has lower cost.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a schematic flow diagram of a method for removing iron and manganese from a zinc smelting process solution according to the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As described in the background art, in the prior art, the removal of iron and manganese in the zinc smelting process is performed step by using different oxidation methods, and the problems of long process flow, difficult control of manganese element balance, low iron and manganese removal efficiency and poor process stability exist. In order to solve the problem, the invention provides a method for removing iron and manganese in a zinc smelting process solution, which comprises the following steps as shown in figure 1: adding a catalyst into the zinc smelting process solution, and introducing an oxidant into the zinc smelting process solution to enable iron ions and manganese ions in the zinc smelting process solution to perform catalytic oxidation reaction to form slurry containing iron and manganese residues; carrying out solid-liquid separation on the slurry containing the iron-manganese slag to obtain the iron-manganese slag and a liquid after iron and manganese removal; wherein the catalyst is selected from one or more of sulfur dioxide-containing gas and sulfite-containing salt.
Firstly, adding a catalyst into a zinc smelting process solution, introducing an oxidant into the zinc smelting process solution to enable iron ions and manganese ions in the zinc smelting process solution to perform catalytic oxidation reaction to form slurry containing iron and manganese residues, and performing solid-liquid separation on the slurry containing iron and manganese residues to obtain iron and manganese residues and a liquid after iron and manganese removal. The method has stronger applicability and is suitable for any feed liquid containing iron and manganese in the zinc smelting process. Meanwhile, the catalytic oxidation of the iron and manganese elements is realized by the one-step method, and the impurities can be fully removed. In addition, in the catalytic oxidation reaction process, iron ions can be preferentially oxidized to be fully precipitated and removed, and then manganese ions are reacted, so that the removal rate of the manganese ions can be stably controlled, complete impurity removal of iron and manganese can be realized, the residual quantity of the manganese ions can be controlled according to the requirements of the subsequent process, and the solution after iron and manganese removal meeting the subsequent requirements can be directly obtained. Therefore, the method has stronger operability, and realizes effective control of manganese ion concentration through effective control of oxidation-reduction potential of reaction. In addition, the process flow for removing iron and manganese is shorter, the cost is lower, and the process stability is stronger. In particular, the catalyst is selected from one or more of sulfur dioxide-containing gas, salts corresponding to sulfite-containing anions. Under the oxygen-rich environment, the complex use of the catalyst promotes the catalytic oxidation to be fast, the oxygen capturing effect is better, and the concentration of the residual manganese ions can be more effectively controlled.
In a word, the method for removing iron and manganese in the zinc smelting process solution provided by the invention has stronger applicability and operability, realizes the catalytic oxidation of iron and manganese elements by a one-step method, and has better potential controllability in the reaction process. The compounding of the oxidant and the catalyst promotes the catalytic oxidation speed to be faster, realizes the more effective control of the concentration of iron and manganese ions, shortens the process flow of removing iron and manganese and has lower cost.
Preferably, the sulphur dioxide containing gas is selected from sulphur dioxide or a sulphur dioxide containing flue gas. More preferably, the catalyst contains one or more of zinc sulfite, sodium sulfite, calcium sulfite and sodium bisulfite corresponding to sulfite radical, and under the oxygen-rich environment, the catalyst has the advantages of high catalytic oxidation speed, better oxygen capturing performance and better control effect on the concentration of iron and manganese ions based on the compound use of the preferred catalyst.
In a preferred embodiment, the catalyst is one or more selected from sulfur dioxide, flue gas containing sulfur dioxide, zinc sulfite corresponding to sulfite, sodium sulfite, calcium sulfite and sodium bisulfite, more preferably, the catalyst is sulfur dioxide or flue gas containing sulfur dioxide, or a mixture of zinc sulfite and sodium sulfite in a weight ratio of (1-3): 1, or a mixture of zinc sulfite, sodium sulfite and calcium sulfite in a weight ratio of (1-2): 1, or a mixture of zinc sulfite, calcium sulfite and sodium bisulfite in a weight ratio of (1-1.5): 1.
The catalyst and the oxidant are compounded to have better catalytic oxidation effect, and the oxidant is preferably one or more of oxygen-containing gas, oxidizing liquid and solid peroxide. Including but not limited to one or more of the above, are more available, are less costly, and do not introduce new impurities. More preferably, in one embodiment, the oxygen-containing gas is selected from one or more of oxygen, compressed air, oxygen-enriched air, ozone, the oxidizing liquid is selected from hydrogen peroxide, and the solid peroxide is selected from sodium peroxide. The oxidant can be added directly into the reactor, or added from a stirrer or other parts, or added into the reactor after being made into a multi-phase medium by adopting a dispersing device, the adding position can be the top, the bottom or the side part of the reactor, and water, solution or ore pulp meeting various process requirements (meeting process parameters of the process, such as temperature, pH and concentration; required to be added in the balance of the production process, such as production water, return liquid after process treatment; and materials to participate in the reaction in the process, such as the diversion of the solution or the ore pulp) can be used as a carrier for adding the oxidant, and the method also comprises the step of directly adding the oxidant without the carrier. The dispersing equipment includes pumps, pressure tanks, etc. which can prepare multiphase coexisting equipment, but is not limited to the list items. The reactor can be selected from a stirring normal pressure reaction tank or a pressure reaction kettle, which can be selected by the person skilled in the art and is not described in detail herein.
In order to make the distribution concentration of the catalyst more suitable, promote the growth of precipitated crystals and avoid resource waste, preferably, when the catalyst is selected from sulfur dioxide or gas containing sulfur dioxide, the introduction amount of the catalyst is 1.5-10 times of the total mole of iron ions and manganese ions in the zinc smelting process solution; the zinc smelting solution contains salts corresponding to sulfite anions, the dosage of the catalyst is 1-25% of the weight of the zinc smelting solution, and the dosage of the catalyst is 1.7-8 times of the total weight of iron ions and manganese ions in the zinc smelting solution. In the range, the concentration of the catalyst in the solution is more suitable, the oxygen capturing effect is better, the catalytic oxidation speed is high, the reaction is easier to control, and the concentration of the iron and manganese ions can be more effectively controlled. Meanwhile, the precipitation efficiency is higher, the dispersion degree of the precipitate in the solution is better, and the size of the precipitate is more suitable.
In order to effectively perform the catalytic oxidation reaction, the reaction temperature in the catalytic oxidation process is preferably 30-200 ℃, preferably 30-90 ℃, and more preferably 50-90 ℃; preferably, the reaction pressure in the catalytic oxidation process is 0.01-2.3 MPa, and more preferably 0.8-1.2 MPa. Under the reaction conditions, the catalytic oxidation reaction is more stable, the yield is higher, and the precipitation efficiency is higher.
More preferably, the pH value of the reaction system in the catalytic oxidation process is 0.5-6; preferably, when the catalyst is a salt corresponding to sulfite, the pH value of a reaction system in the catalytic oxidation process is 4-6; when the catalyst is sulfur dioxide or flue gas containing sulfur dioxide, the pH value of a reaction system in the catalytic oxidation process is 2.5-4. The pH value is controlled in the range, the catalytic oxidation reaction is more stable, the precipitate is more easily generated, the dispersion degree of the precipitate in the system is better, and the size is more suitable. Meanwhile, the concentration of iron and manganese ions can be more effectively controlled.
In a preferred embodiment, the method further comprises: returning part of the ferro-manganese slag to a reaction system of the catalytic oxidation reaction to be used as seed crystals; preferably, the seed ratio of the seed to be added is (0.2-10): 1, more preferably (1.5-3): 1. The seed ratio is defined as follows: the ratio of the seed crystal addition weight to the weight of the newly produced pig iron manganese slag. And returning part of the ferro-manganese slag to a reaction system of the catalytic oxidation reaction to be used as a seed crystal, wherein the availability is higher, the operability is stronger, the ferro-manganese slag is used as a precipitation initiator, the addition seed crystal ratio of the seed crystal is (0.2-10): 1, the precipitation effect is better, the ferro-manganese slag is easier to grow crystals, and the precipitation size is more appropriate, and is more preferably (1.5-3): 1.
Preferably, the solid-liquid separation mode is selected from concentration separation, sedimentation separation, centrifugal separation, adsorption separation or cyclone separation; preferably, after the ferro-manganese slag is obtained, the method further comprises the step of washing the ferro-manganese slag, and more preferably, the weight ratio of the washing agent to the ferro-manganese slag is (0.5-6): 1. The solid-liquid separation mode has better separation effect, and the obtained ferro-manganese slag has less impurity content. Washing the iron-manganese slag, wherein the weight ratio of the washing agent to the iron-manganese slag is (0.5-6): 1, the washing effect is better, and the utilization rate of the washing liquid subsequently returned to the zinc smelting system is higher.
Preferably, the zinc smelting process solution is selected from iron and manganese containing solutions, wash water, ore pulp or slag pulp in a zinc smelting process; preferably, the zinc smelting process is a zinc concentrate smelting process, more preferably a high manganese zinc concentrate smelting process; preferably, the zinc smelting process solution contains 50-160 g/L of zinc ions, 1-8 g/L of divalent iron ions and 5-30 g/L of divalent manganese ions.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
The raw material is high manganese zinc concentrate smelting process liquid, and the process position is a liquid purification process.
In the smelting process liquid: zn2+ 140~150g/L，Mn2+ 11~12g/L，Fe2+ 1g/L，SO4 2- 220~230g/L。
Adding flue gas containing sulfur dioxide into the zinc smelting process solution as a catalyst, introducing the flue gas with the introduction amount being 1.5 times of the total mole number of iron ions and manganese ions in the zinc smelting process solution, dispersing oxygen-enriched air (the oxygen volume concentration is 25%) from the bottom of a reactor through a gas distribution device to be used as an oxidant, wherein the reaction temperature is 50 ℃, the reaction pressure is 0.3MPa, the pH value of a reaction system is 4.0, and the reaction time is 3 hours, and carrying out catalytic oxidation reaction to form slurry containing iron and manganese residues; taking the ferro-manganese slag as a seed crystal and returning the ferro-manganese slag to a reaction system of the catalytic oxidation reaction, wherein the seed crystal ratio is 3; carrying out concentration separation and filtration separation on the slurry containing the iron-manganese slag to obtain iron-manganese slag and a liquid after iron and manganese removal; washing the iron-manganese slag, wherein the ratio of the condensate or the produced new water to the solid is 2: 1.
the removal rate of manganese was 87% and the removal rate of iron was 98%.
Example 2
The raw material is high manganese zinc concentrate smelting process liquid, and the process position is a leaching process.
In the smelting process liquid: zn2+ 140~150g/L， Mn2+ ~20g/L，Fe2+ 4~5g/L， SO4 2- 250~270g/L。
Adding flue gas containing sulfur dioxide as a catalyst into the zinc smelting process solution, wherein the flux is 1.4mol/L, directly adding oxygen-enriched air as an oxidant from the bottom of the reactor, the reaction temperature is 90 ℃, the reaction pressure is 0.3MPa, the pH value of the reaction system is 4.0, the reaction time is 2h, and carrying out catalytic oxidation reaction to form slurry containing iron-manganese slag; taking the ferro-manganese slag as a seed crystal to return to a reaction system of the catalytic oxidation reaction, wherein the seed crystal ratio is 2: 1; carrying out concentration separation and filtration separation on the slurry containing the iron-manganese slag to obtain iron-manganese slag and a liquid after iron and manganese removal; washing the iron-manganese slag, wherein the ratio of the condensate or the produced new water to the solid is 3: 1.
the removal rate of manganese is 85 percent, and the removal rate of iron is 98 percent.
Example 3
The raw material is zinc smelting process liquid, and the process position is waste liquid treatment.
In the smelting process liquid: zn2+ 50~55g/L， Mn2+ 5~7g/L，Fe2+ 0.5~0.6g/L，SO4 2- 84~95g/L。
Adding sulfur dioxide serving as a catalyst into the zinc smelting process solution, wherein the flux is 0.35mol/L, preparing oxygen-enriched air and the smelting process solution into a multi-phase medium by adopting dispersion equipment, adding the multi-phase medium into a reactor serving as an oxidant, reacting at the temperature of 30 ℃, under the pressure of 0.3MPa, and under the conditions that the pH value of a reaction system is 4.0 and the reaction time is 3 hours, and carrying out catalytic oxidation reaction to form slurry containing iron-manganese slag; taking the ferro-manganese slag as a seed crystal to return to a reaction system of catalytic oxidation reaction, wherein the seed crystal ratio is 3: 1; carrying out concentration separation and filtration separation on the slurry containing the iron-manganese slag to obtain iron-manganese slag and a liquid after iron and manganese removal; washing the iron-manganese slag, wherein the ratio of process condensate or new production water to solid is 3: 1.
the removal rate of manganese was 80% and the removal rate of iron was 95%.
Example 4
The difference from the example 1 is only that the catalyst is sulfur dioxide flue gas, and the pH value of the reaction system in the catalytic oxidation process is 5.
The removal rate of manganese is 85%, and the removal rate of iron is 95%.
Example 5
The difference from the example 1 is only that the catalyst is sulfur dioxide flue gas, the dosage of the catalyst is 18 percent of the weight of the solution in the zinc smelting process, and the pH value of the reaction system in the catalytic oxidation process is 5.
The removal rate of manganese is 85%, and the removal rate of iron is 95%.
Example 6
The difference from example 1 is only that the catalyst is a mixture of zinc sulfite and sodium sulfite with a weight ratio of 2:1, the amount of the catalyst is 15% of the weight of the solution in the zinc smelting process, and the pH value of the reaction system in the catalytic oxidation process is 5.
The removal rate of manganese was 83%, and the removal rate of iron was 93%.
Example 7
The only difference from example 1 is that the catalyst is zinc sulfite and calcium sulfite in a weight ratio of 2:1, the amount of the catalyst is 10 percent of the weight of the solution in the zinc smelting process.
The removal rate of manganese is 80%, and the removal rate of iron is 90%.
Example 8
The only difference from example 1 is that the catalyst is zinc sulfite and sodium bisulfite in a weight ratio of 2:1 and the amount of the catalyst is 20 percent of the weight of the solution in the zinc smelting process.
The removal rate of manganese is 85%, and the removal rate of iron is 96%.
Example 9
The only difference from example 1 is that the catalyst is a mixture of zinc sulfite, sodium sulfite and calcium sulfite in a weight ratio of 1:1:1, and the amount of the catalyst is 1% of the weight of the zinc smelting process solution.
The removal rate of manganese was 72% and the removal rate of iron was 83%.
Example 10
The only difference from example 1 is that the catalyst is a mixture of zinc sulfite, sodium sulfite and calcium sulfite in a weight ratio of 1.5:1.5:1, and the amount of the catalyst is 5% by weight of the zinc smelting process solution.
The removal rate of manganese is 75%, and the removal rate of iron is 85%.
Example 11
The only difference from example 1 is that the catalyst is zinc sulfate and sodium bisulfite in a weight ratio of 2:1 and the amount of the catalyst is 12 percent of the weight of the solution in the zinc smelting process.
The removal rate of manganese was 78% and the removal rate of iron was 90%.
Example 12
The only difference from example 1 is that the catalyst is zinc sulphate and sodium sulphite in a weight ratio of 2:1 and the amount of the catalyst is 25 percent of the weight of the solution in the zinc smelting process.
The removal rate of manganese is 85%, and the removal rate of iron is 95%.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: the invention provides a method for removing iron and manganese in a zinc smelting process solution, which effectively solves the problems of long process flow, difficult control of manganese element balance, low iron and manganese removal efficiency and high cost caused by respectively adopting different oxidation methods to remove iron and manganese in the conventional zinc smelting process step by step.
Particularly, the invention adds a catalyst into the zinc smelting process solution, and introduces an oxidant into the zinc smelting process solution to enable iron ions and manganese ions in the zinc smelting process solution to carry out catalytic oxidation reaction to form slurry containing iron and manganese residues, and carries out solid-liquid separation on the slurry containing iron and manganese residues to obtain iron and manganese residues and a liquid after iron and manganese removal. The method has stronger applicability and is suitable for any feed liquid containing iron and manganese in the zinc smelting process. Meanwhile, the catalytic oxidation of the iron and manganese elements is realized by the one-step method, and the impurities can be fully removed. In addition, in the catalytic oxidation reaction process, iron ions can be preferentially oxidized to be fully precipitated and removed, and then manganese ions are reacted, so that the removal rate of the manganese ions can be stably controlled, complete impurity removal of iron and manganese can be realized, the residual quantity of the manganese ions can be controlled according to the requirements of the subsequent process, and the solution after iron and manganese removal meeting the subsequent requirements can be directly obtained. Therefore, the method has stronger operability, promotes better potential controllability in the reaction process, and realizes effective control of manganese ion concentration. In addition, the process flow for removing iron and manganese is shorter, the cost is lower, and the process stability is stronger. In particular, the catalyst is selected from one or more of sulfur dioxide-containing gas, salts corresponding to sulfite-containing anions. Under the oxygen-rich environment, the complex use of the catalyst promotes the catalytic oxidation to be fast, the oxygen capturing effect is better, and the concentration of the residual manganese ions can be more effectively controlled.
More particularly, as can be seen from the data in the examples, the sulfur dioxide-containing gas is selected from sulfur dioxide or a sulfur dioxide-containing flue gas; preferably, the salt corresponding to the sulfite-containing anion is selected from one or more of zinc sulfite, sodium sulfite, calcium sulfite and sodium bisulfite; the dosage of the catalyst is 1-25% of the weight of the solution in the zinc smelting process. Under the oxygen-rich environment, the compound use based on the optimized catalyst promotes the catalytic oxidation to be fast, the performance of capturing oxygen is better, and the control effect on the concentration of iron and manganese ions is better.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to 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 (6)
1. The method for removing iron and manganese in the zinc smelting process solution is characterized in that the zinc smelting process solution contains 50-160 g/L of zinc ions, 1-8 g/L of ferrous ions and 5-30 g/L of divalent manganese ions; the method comprises the following steps:
adding a catalyst into the zinc smelting process solution, introducing an oxidant into the zinc smelting process solution, and simultaneously carrying out catalytic oxidation reaction on iron ions and manganese ions in the zinc smelting process solution by controlling the oxidation-reduction potential of a system in an oxygen-enriched environment to form slurry containing iron-manganese slag;
carrying out solid-liquid separation on the slurry containing the iron-manganese slag to obtain iron-manganese slag and a liquid after iron and manganese removal;
the catalyst is sulfur dioxide or flue gas containing sulfur dioxide, or salt corresponding to sulfite anions;
the salt corresponding to the sulfite-containing anion is a mixture of zinc sulfite and sodium sulfite with the weight ratio of (1-3): 1, or a mixture of zinc sulfite, sodium sulfite and calcium sulfite with the weight ratio of (1-2): 1, or a mixture of zinc sulfite, calcium sulfite and sodium bisulfite with the weight ratio of (1-1.5): 1;
when the catalyst is selected from the sulfur dioxide or the flue gas containing the sulfur dioxide, the introduction amount of the catalyst is 1.5-10 times of the total mole number of iron ions and manganese ions in the zinc smelting process solution; when the catalyst is selected from the salts corresponding to the sulfite-containing anions, the amount of the catalyst is 1-25% of the weight of the zinc smelting process solution;
the reaction temperature in the catalytic oxidation process is 50-90 ℃;
returning part of the iron-manganese slag to a reaction system of the catalytic oxidation reaction to be used as seed crystals; the seed crystal addition ratio of the seed crystal is (0.2-10): 1.
2. The method of claim 1, wherein the sulfur dioxide-containing gas is selected from sulfur dioxide or a flue gas containing sulfur dioxide.
3. The method of claim 1, wherein the catalyst is selected from one or more of the group consisting of the sulfur dioxide, the sulfur dioxide-containing flue gas, the zinc sulfite, the sodium sulfite, the calcium sulfite, and the sodium bisulfite.
4. The method of claim 1 or 2, wherein the oxidising agent is selected from one or more of an oxygen-containing gas, an oxidising liquid and a solid peroxide.
5. The method for removing iron and manganese in the zinc smelting process solution according to claim 1, wherein the pH value of a reaction system in the catalytic oxidation process is 0.5-6.
6. The method of removal of iron and manganese from a zinc smelting process solution according to claim 1 or 2, wherein the zinc smelting process solution is selected from iron and manganese containing solutions, wash water, ore pulp or slag pulp in a zinc smelting process.
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