CN112176184A - Method for removing iron by combining oxygen and hydrogen peroxide - Google Patents
Method for removing iron by combining oxygen and hydrogen peroxide Download PDFInfo
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- CN112176184A CN112176184A CN202010938477.XA CN202010938477A CN112176184A CN 112176184 A CN112176184 A CN 112176184A CN 202010938477 A CN202010938477 A CN 202010938477A CN 112176184 A CN112176184 A CN 112176184A
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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Abstract
The invention belongs to the technical field of hydrometallurgy, and relates to a method for removing iron ions in zinc hydrometallurgy mineral powder by combining oxygen and hydrogen peroxide. The method comprises the following steps: introducing oxygen with the concentration of 99% into the leaching solution of the secondary zinc oxide ore to reduce the iron content in the leaching solution to 1000 mg/L; and introducing hydrogen peroxide into the leachate, adjusting the pH to 3.0-3.5, and removing precipitates to obtain the secondary zinc oxide ore leachate with the iron content of less than 20 mg/L. The utilization rate of oxygen and hydrogen peroxide is improved to 90%, the reaction is fast, the reaction can be finished within 3 hours, the content of ferrous ions in the secondary zinc oxide ore leaching solution can be reduced to be below 20mg/L, and the process requirement is met. The method has the advantages of simple process, high efficiency and higher economic value, and solves the problems of overhigh iron ion content, especially low utilization rate of hydrogen peroxide in the secondary zinc oxide ore leaching solution in the prior art.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy, and relates to a method for removing iron ions in zinc hydrometallurgy mineral powder by combining oxygen and hydrogen peroxide.
Background
Zinc hydrometallurgy mainly comprises the working procedures of roasting, leaching, purification and electrodeposition, zinc concentrate is subjected to neutral leaching by using electrolytic waste liquid after roasting to dissolve most of zinc oxide, obtained ore pulp is separated into supernatant and underflow ore pulp, metal zinc is produced by electrodeposition after the supernatant is purified, fusion casting precipitation is carried out, the underflow ore pulp is subjected to acid leaching to dissolve residual zinc oxide, acid leachate is fed back to the neutral leaching, and acid leaching slag needs to be further treated.
Zinc hydrometallurgy mainly comprises the working procedures of roasting, leaching, purification and electrodeposition, zinc concentrate is subjected to neutral leaching by using electrolytic waste liquid after roasting to dissolve most of zinc oxide, obtained ore pulp is separated into supernatant and underflow ore pulp, metal zinc is produced by electrodeposition after the supernatant is purified, casting ingots are cast, the underflow ore pulp is subjected to acid leaching to dissolve residual zinc oxide, acid leachate is returned to neutral leaching, and acid leaching slag needs further treatment.
90% of iron in the mineral powder enters the solution in the wet zinc smelting process, and an electrolysis system is specially required to open the circuit of iron ions in the solution in the form of iron slag in order to ensure that the iron in the solution is lower than 20mg/L as required by normal production. The iron removal method of the company is goethite at present, and the iron removal process of the goethite requires Fe in solution in the iron removal process3+All the time<1000mg/L, while the iron in the solution is present in divalent form. In the prior art, hydrogen peroxide and potassium permanganate are mostly used as oxidants, for example, a wet separation method of valuable metals in liquid-purifying cobalt slag of a wet zinc smelting system is disclosed in chinese patent CN101838736A, wherein the oxidant used for iron removal is hydrogen peroxide, and the oxidant used for cobalt removal is potassium permanganate, but the use of hydrogen peroxide for iron removal has the following disadvantages: the limit of the process conditions causes the low utilization rate of the hydrogen peroxide, which is only 50-60%, so that the cost is increased.
Disclosure of Invention
In order to solve the problems of overhigh iron ion content and low utilization rate of hydrogen peroxide in the secondary zinc oxide ore leaching solution in the prior art, the invention provides a method for removing iron by combining oxygen and hydrogen peroxide.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for removing iron by combining oxygen and hydrogen peroxide comprises the following steps:
step A, introducing oxygen with the concentration of 99% into the leaching solution of the secondary zinc oxide ore to reduce the ferrous content in the leaching solution to 1000 mg/L;
b, introducing hydrogen peroxide into the leaching solution, and adjusting the pH to 3.0-3.5 to enable Fe3+Removing the precipitate in the form of goethite slag to obtain a slag having an iron content of less than 20mg/LSecondary zinc oxide ore leaching solution.
Further, the oxygen is introduced from the bottom of the secondary zinc oxide ore leaching solution.
Furthermore, the introduction amount of the oxygen is 90-95% of the theoretical molar mass, and the theoretical molar mass is Fe2+：O2＝4:1。
Further, the concentration of the hydrogen peroxide is 28%, and the introduction position of the hydrogen peroxide is below 3m of the liquid level of the secondary zinc oxide ore leaching solution.
Further, the molar ratio of the hydrogen peroxide to the ferrous ions in the secondary zinc oxide ore leaching solution is 1: 2.
Further, the reaction time after the hydrogen peroxide is introduced is 3-4 hours.
Compared with the prior art, the invention has the following beneficial effects:
the method adopts the combination of oxygen with the concentration of 99% and hydrogen peroxide with the concentration of 28% to remove iron, and the oxygen and the hydrogen peroxide are introduced into the secondary zinc oxide ore leachate from the liquid level and fully contacted with ferrous ions, so that the utilization rate of the oxygen and the hydrogen peroxide is improved and can reach 90%, the oxidation reaction is fast, the reaction can be completed within 3 hours, and the content of the ferrous ions in the secondary zinc oxide ore leachate is reduced to be less than 20 mg/L; the oxygen and the hydrogen peroxide are matched for use, so that the use amount of the oxidant is reduced, the utilization rate of the oxidant is improved, and the concentration of ferrous ions meets the process requirement. The method has the advantages of simple process, high efficiency, higher specific economic value and popularization and application.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Example 1
A method for removing iron by combining oxygen and hydrogen peroxide comprises the following steps:
in the embodiment, the iron content of the leaching solution of the zinc hypoxide ore is 5g/L, oxygen with the concentration of 99% is introduced into the leaching solution of the zinc hypoxide ore from the bottom to change the leaching solution into a goethite form for removal, ferrous ions in the leaching solution are reduced to 1000mg/L, and the main reaction formula is as follows: 2Fe2++1/2O2+3H2O＝2FeO(OH)↓+4H+Theoretical molar mass of Fe2+：O2The oxygen is introduced in an amount of 90% of the theoretical value in the embodiment as 4: 1;
introducing 28% hydrogen peroxide into the leachate, wherein the introduction position of the hydrogen peroxide is below 3m of the liquid level of the secondary zinc oxide ore leachate, so that the contact between the hydrogen peroxide and the secondary zinc oxide ore leachate is enhanced, the molar ratio of the hydrogen peroxide to ferrous ions in the secondary zinc oxide ore leachate is 1:2, adding an oxidant and slowly using low-lead secondary zinc oxide to adjust the pH to 3.0-3.5, reacting for 3 hours to form brownish red goethite slag and ferric hydroxide, and removing precipitates to obtain the secondary zinc oxide ore leachate with the iron content of 15 mg/L. The main reaction formula of the step is as follows: 2Fe2++2H++H2O2＝2Fe3++2H2O；Fe3++3OH-＝Fe(OH)3↓。
Example 2
In the embodiment, the iron content of the leaching solution of the zinc hypoxide ore is 5g/L, oxygen with the concentration of 99% is introduced into the leaching solution of the zinc hypoxide ore from the bottom to change the leaching solution into a goethite form for removal, ferrous ions in the leaching solution are reduced to 1000mg/L, and the main reaction formula is as follows: 2Fe2++1/2O2+3H2O＝2FeO(OH)↓+4H+Theoretical molar mass of Fe2+：O2The oxygen is introduced in an amount of 95% of the theoretical value in the embodiment as 4: 1;
introducing 28% hydrogen peroxide into the leachate, wherein the introduction position of the hydrogen peroxide is below 3m of the liquid level of the secondary zinc oxide ore leachate, the molar ratio of the hydrogen peroxide to ferrous ions in the secondary zinc oxide ore leachate is 1:2, slowly using low-lead secondary zinc oxide while adding an oxidant to adjust the pH to 3.0-3.5, reacting for 3 hours to form brownish red goethite slag and ferric hydroxide, and removing precipitates to obtain the secondary zinc oxide ore leachate with the iron content of 13 mg/L. The main reaction formula of the step is as follows: 2Fe2++2H++H2O2＝2Fe3++2H2O；Fe3++3OH-＝Fe(OH)3↓。
Example 3
In the embodiment, the iron content of the leaching solution of the zinc hypoxide ore is 5g/L, oxygen with the concentration of 99% is introduced into the leaching solution of the zinc hypoxide ore from the bottom to change the leaching solution into a goethite form for removal, ferrous ions in the leaching solution are reduced to 1000mg/L, and the main reaction formula is as follows: 2Fe2++1/2O2+3H2O＝2FeO(OH)↓+4H+Theoretical molar mass of Fe2+：O2The oxygen is introduced in an amount of 90% of the theoretical value in the embodiment as 4: 1;
introducing 28% hydrogen peroxide into the leachate, wherein the introduction position of the hydrogen peroxide is below 3m of the liquid level of the secondary zinc oxide ore leachate, the molar ratio of the hydrogen peroxide to ferrous ions in the secondary zinc oxide ore leachate is 1:2, slowly using low-lead secondary zinc oxide while adding an oxidant to adjust the pH to 3.0-3.5, reacting for 4 hours to form brownish red goethite slag and ferric hydroxide, and removing precipitates to obtain the secondary zinc oxide ore leachate with the iron content of 15 mg/L. The main reaction formula of the step is as follows: 2Fe2++2H++H2O2＝2Fe3++2H2O；Fe3++3OH-＝Fe(OH)3↓。
Example 4
This example explores the optimal oxygen concentration. The volume of the leachate in this example was 45m3The content of ferrous ions is 5g/L, and oxygen is added from the bottom of the leaching solution. Table 1 shows the effect data after the implementation.
TABLE 1 Effect of oxygen of different concentrations on the removal of ferrous ions from leach liquors
| Serial number | Oxygen concentration | Dosage of | Working time | Oxidized iron |
| 1 | 99％ | 24kg | 3h | 0.7g/L |
| 2 | 90％ | 27kg | 4h | 0.8g/L |
| 3 | 80％ | 30kg | 4h | 0.9g/L |
| 4 | 40％ | 80kg | 8h | 0.85g/L |
| 5 | 20% (air) | 200kg | 10h | 0.5g/L |
As can be seen from Table 1, the low-concentration oxygen has a slow oxidation speed and a large consumption, the oxidation time can reach as long as 10 hours, which leads to the increase of the iron removal cost, and the operation time can be effectively reduced by adopting the oxygen with the concentration of 99 percent.
Example 5
The embodiment shows the effect of using different oxidants for the leaching solution of the secondary zinc oxide ore. The reaction can be carried out only when the pH value of the manganese dioxide iron removal solution is about 1.5, while the pH value of the iron removal solution is 4.0-5.0, and manganese dioxide is not considered as an oxidant. The volume of the leachate in this example was 45m3The content of ferrous ions was 5g/L, and each oxidizing agent was added from below the liquid surface. Table 2 shows the effect data after the implementation.
TABLE 2 removal of ferrous ions from leach liquors by combination of different oxidants
As can be seen from Table 2, the experiment group 1 only adds oxygen with 99% concentration, and the contact chance between the oxygen and ferrous iron is reduced due to the reduction of the ferrous iron concentration in the later period, even if oxygen is continuously introduced, the final iron removal rate is still not high, the minimum value is 0.9g/L, and 20mg/L which cannot meet the process requirement; the experimental group 2 independently adopts 28% hydrogen peroxide, and ferrous ions reach below 20mg/L after reaction for 3 hours, but the hydrogen peroxide has more dosage, low utilization rate and high cost; the experimental group 3 adopts oxygen and potassium permanganate for composite use, the utilization rate reaches 90%, but the reaction time is long, the cost of the potassium permanganate is high, and the potassium permanganate belongs to dangerous goods and is avoided as much as possible; the experimental group 4 adopts oxygen and hydrogen peroxide to be matched, the content of ferrous ions can be reduced to 15mg/L after reaction for 3 hours, the addition amount is not high, and the utilization rate of the oxidant is high.
The reason why the best effect is achieved by matching 99% oxygen and 28% hydrogen peroxide is that: the higher the concentration of the two reactants is, the faster the theoretical reaction speed is, but the slow reaction of oxygen in the later stage of iron removal (ferrous ions are less than 1000mg/l), the hydrogen peroxide is added at the moment, the temperature of the whole goethite iron removal process is required to be 70 ℃, and the characteristic of the hydrogen peroxide is easily decomposed by heat, so that the effect of reducing the amount of the hydrogen peroxide and promoting the oxidation of the oxygen is achieved, the reaction speed and the loss (decomposition part) are improved by combining the two reactants, and the utilization rate is naturally improved.
The above-mentioned embodiments only express one embodiment of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (6)
1. A method for removing iron by combining oxygen and hydrogen peroxide is characterized by comprising the following steps:
step A, introducing oxygen with the concentration of 99% into the leaching solution of the secondary zinc oxide ore to reduce the ferrous content in the leaching solution to 1000 mg/L;
b, introducing hydrogen peroxide into the leaching solution, and adjusting the pH to 3.0-3.5 to enable Fe3+Removing the precipitate in the form of goethite slag to obtain the leaching solution of the zinc hypoxide ore with the iron content lower than 20 mg/L.
2. The method for removing iron by combining oxygen and hydrogen peroxide as claimed in claim 1, wherein the oxygen is introduced from the bottom of the leaching solution of the secondary zinc oxide ore.
3. The method for removing iron by combining oxygen and hydrogen peroxide as claimed in claim 1, wherein the introduction amount of the oxygen is 90-95% of the theoretical molar mass, and the theoretical molar mass is Fe2+：O2=4:1。
4. The method for removing iron by combining oxygen and hydrogen peroxide as claimed in claim 1, wherein the concentration of the hydrogen peroxide is 28%, and the introducing position of the hydrogen peroxide is below 3m of the liquid level of the secondary zinc oxide ore leaching solution.
5. The method for removing iron by combining oxygen and hydrogen peroxide as claimed in claim 1, wherein the molar ratio of the hydrogen peroxide to ferrous ions in the secondary zinc oxide ore leaching solution is 1: 2.
6. The method for removing iron by combining oxygen and hydrogen peroxide as claimed in claim 1, wherein the reaction time after the hydrogen peroxide is introduced is 3-4 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206760A (en) * | 2011-03-31 | 2011-10-05 | 株洲冶炼集团股份有限公司 | Method for haydrometallurgy of zinc |
| CN102676815A (en) * | 2012-06-08 | 2012-09-19 | 大兴安岭云冶矿业开发有限公司 | Method for removing iron from leach liquor at two stages |
| EP2703503A1 (en) * | 2012-09-04 | 2014-03-05 | Canbekte, Hüsnü Sinan | Method of precipitation of iron from leach solutions |
| CN103773957A (en) * | 2014-01-28 | 2014-05-07 | 白银有色集团股份有限公司 | Vitriol precipitating and Fe removing process in zinc hydrometallurgy technology |
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- 2020-09-09 CN CN202010938477.XA patent/CN112176184A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206760A (en) * | 2011-03-31 | 2011-10-05 | 株洲冶炼集团股份有限公司 | Method for haydrometallurgy of zinc |
| CN102676815A (en) * | 2012-06-08 | 2012-09-19 | 大兴安岭云冶矿业开发有限公司 | Method for removing iron from leach liquor at two stages |
| EP2703503A1 (en) * | 2012-09-04 | 2014-03-05 | Canbekte, Hüsnü Sinan | Method of precipitation of iron from leach solutions |
| CN103773957A (en) * | 2014-01-28 | 2014-05-07 | 白银有色集团股份有限公司 | Vitriol precipitating and Fe removing process in zinc hydrometallurgy technology |
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Application publication date: 20210105 |