CN109133190B - Processing method of pyrrhotite - Google Patents
Processing method of pyrrhotite Download PDFInfo
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- CN109133190B CN109133190B CN201810876483.XA CN201810876483A CN109133190B CN 109133190 B CN109133190 B CN 109133190B CN 201810876483 A CN201810876483 A CN 201810876483A CN 109133190 B CN109133190 B CN 109133190B
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- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
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Abstract
The invention discloses a processing method of pyrrhotite, which comprises the following steps: 1) reacting pyrrhotite with ferric nitrate to obtain a gas-phase product and a liquid-solid mixture, carrying out solid-liquid separation on the liquid-solid mixture to obtain a ferric nitrate solution and a ferric hydroxide solid, and recycling the ferric nitrate solution; 2) mixing the gas-phase product with air, absorbing the mixture by using concentrated sulfuric acid, diluting the mixture to obtain a concentrated sulfuric acid product, and taking part of the concentrated sulfuric acid product to be recycled for absorbing the gas-phase product obtained in the step 1); 3) mixing the gas-phase product which is not absorbed in the step 2) with excess air, fully oxidizing, absorbing by using part of ferric hydroxide in the step 1) to obtain ferric nitrate solution, and circularly using the ferric nitrate solution to react with pyrrhotite; 4) mixing the rest ferric hydroxide with concentrated sulfuric acid, adding reduced iron powder for reaction, filtering, evaporating and crystallizing to obtain ferrous sulfate heptahydrate crystal. The processing method has low production cost and low energy consumption, reduces by-products, and provides an effective and feasible utilization way for pyrrhotite.
Description
Technical Field
The invention relates to the field of mineral processing, in particular to a method for processing pyrrhotite.
Background
Pyrrhotite is a sulfide mineral of iron in the pyrite family, and its S content is generally higher than the theoretical content of FeSThe content of the pyrrhotite is 39-40%, the pyrrhotite is often associated with pyrite and has low yield, and the pyrrhotite is mainly used for preparing sulfuric acid, but the pyrrhotite is compared with the pyrite FeS2The sulfur content is much lower and its economic value is far less than that of pyrite ore.
Because the economic value of the pyrrhotite is low, the pyrrhotite and the pyrite are not generally separated industrially, but in order to improve the grade of copper concentrate, a copper ore production enterprise separately separates the pyrrhotite by magnetic separation, so that the problems of high processing cost, high energy consumption and extremely low economic benefit exist when the pyrrhotite is separately processed by a calcination method to produce sulfuric acid subsequently.
In addition, ferric nitrate is a strong oxidant and reacts with pyrrhotite to form nitrogen oxides, sulphur dioxide and ferric hydroxide, but the following problems exist when pyrrhotite is treated in this way: the ferric nitrate reduction product contains nitrogen oxides such as nitric oxide, nitrogen dioxide and the like, and the nitrogen oxides are industrially absorbed by adopting a sodium hydroxide solution, so that the cost is high, and the byproducts are impure sodium nitrate and sodium nitrite.
Disclosure of Invention
The invention aims to provide a method for processing pyrrhotite, which has low production cost and energy consumption and reduces byproducts.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for processing pyrrhotite comprises the following steps:
1) reacting pyrrhotite with an iron nitrate solution at a certain temperature to obtain a gas-phase product and a liquid-solid mixture, carrying out solid-liquid separation on the liquid-solid mixture to obtain an iron nitrate solution and an iron hydroxide solid, and recycling the iron nitrate solution for reacting with pyrrhotite;
2) mixing the gas-phase product obtained in the step 1) with a certain amount of air, absorbing the mixture by using concentrated sulfuric acid, diluting the mixture to obtain a concentrated sulfuric acid product, and taking part of the concentrated sulfuric acid product to be recycled for absorbing the gas-phase product obtained in the step 1);
3) mixing the gas-phase product which is not absorbed in the step 2) with excess air, fully oxidizing, absorbing part of ferric hydroxide solid in the step 1) to obtain ferric nitrate solution, and recycling the ferric nitrate solution for reacting with pyrrhotite;
4) mixing the residual ferric hydroxide solid with part of concentrated sulfuric acid products in the step 2), adding reduced iron powder for reaction, filtering, evaporating and crystallizing to obtain ferrous sulfate heptahydrate crystals.
Further, in the step 1), the reaction temperature of pyrrhotite and the ferric nitrate solution is 80-110 ℃, and the concentration of the ferric nitrate solution is 1-2 mol/L.
Further, in the step 2), the obtained gas-phase product is mixed with a certain amount of air, and the volume ratio of the gas-phase product to the air in a standard state is 0.1-10.
Further, in the step 3), when the iron hydroxide solid is used for absorbing the gas-phase product after air oxidation, the temperature in the absorption process is controlled to be 20-60 ℃.
Further, in the step 4), the molar ratio of the ferric hydroxide solid to the reduced iron powder is 1.9-2.1.
Further, in the step 2), the gas-phase products are nitrogen oxides and sulfur dioxide.
Further, in the step 1), unabsorbed gas-phase products are nitrogen oxides.
Further, in the step 2), the obtained concentrated sulfuric acid is diluted to 98% by water to obtain a concentrated sulfuric acid product.
Further, in the step 1), the molar ratio of the ferric nitrate to the sulfur element in pyrrhotite is 0.01-1.0.
Furthermore, in the step 4), the molar ratio of the ferric hydroxide to the concentrated sulfuric acid is 0.1-10.0.
Compared with the prior art, the invention has the following advantages:
firstly, the invention introduces ferric nitrate as a transition oxidant, realizes the oxidation process of pyrrhotite and air under the soft chemical condition, avoids the large investment and high energy consumption of processing pyrrhotite by a calcination method, greatly reduces the cost under the condition of small processing amount, and provides an effective and feasible utilization way for the pyrrhotite.
Secondly, the invention uses the intermediate product ferric hydroxide generated in the reaction process to absorb the nitrogen oxide and can be recycled in the oxidation process of pyrrhotite, thereby avoiding using sodium hydroxide to absorb the nitrogen oxide, further reducing the production cost and avoiding generating byproducts.
Thirdly, the sulfuric acid and the intermediate product ferric hydroxide generated in the reaction process are used, and the reduced iron powder is added to obtain the product ferrous sulfate heptahydrate, so that the generation of byproducts is reduced, and the purity of the obtained ferrous sulfate heptahydrate crystal after drying is 98.0-99.999%.
Drawings
FIG. 1 is a scanning electron micrograph of an intermediate product, iron hydroxide, in example 1 of the present invention.
Detailed Description
The invention will be more clearly understood from the following detailed description of the invention taken in conjunction with the accompanying drawings and specific examples, which are not to be construed as limiting the invention.
Example 1
A method for processing pyrrhotite comprises the following steps:
1) reacting pyrrhotite with ferric nitrate with the concentration of 2mol/L at the temperature of 100 ℃, wherein the molar ratio of the ferric nitrate to sulfur in the pyrrhotite is 0.01-1.0, preferably 2: 9, obtaining a gas-phase product and a liquid-solid mixture, carrying out solid-liquid separation on the liquid-solid mixture to obtain a ferric nitrate solution and a ferric hydroxide solid, wherein the ferric nitrate solution is circularly used for reacting with pyrrhotite;
2) mixing the gas-phase product obtained in the step 1) with air according to a volume ratio of 2 in a standard state (20 ℃, 1 standard atmospheric pressure), absorbing by using concentrated sulfuric acid, wherein the unabsorbed gas-phase product is nitrogen oxide, diluting the obtained concentrated sulfuric acid to 98% by using water to obtain a part of concentrated sulfuric acid product, and recycling other concentrated sulfuric acids for absorbing the gas-phase product obtained in the step 1);
3) mixing the gas-phase product not absorbed in the step 2) with excess air, fully oxidizing, and absorbing by using part of the ferric hydroxide solid (shown in figure 1) in the step 1) to obtain ferric nitrate solution, wherein the temperature in the absorption process is controlled at 30 ℃, and the ferric nitrate solution is circularly used for reacting with pyrrhotite;
4) mixing the residual ferric hydroxide solid in the step 3) with part of concentrated sulfuric acid products in the step 2), adding reduced iron powder for reaction, wherein the mass ratio of the ferric hydroxide to the reduced iron powder is 2, the molar ratio of the ferric hydroxide to the concentrated sulfuric acid is 0.1-10.0, and preferably 2: 3, filtering, evaporating and crystallizing to obtain ferrous sulfate heptahydrate crystals.
Example 2
A method for processing pyrrhotite comprises the following steps:
1) reacting pyrrhotite with ferric nitrate with the concentration of 2mol/L at the temperature of 80 ℃, wherein the molar ratio of the ferric nitrate to sulfur in the pyrrhotite is 0.01-1.0, so as to obtain a gas-phase product and a liquid-solid mixture, performing solid-liquid separation on the liquid-solid mixture to obtain a ferric nitrate solution and a ferric hydroxide solid, and recycling the ferric nitrate solution for reacting with the pyrrhotite;
2) mixing the gas-phase product obtained in the step 1) with air according to a volume ratio of 0.1 in a standard state, absorbing by using concentrated sulfuric acid, wherein the unabsorbed gas-phase product is nitrogen oxide, diluting the obtained concentrated sulfuric acid to 98% by using water to obtain a part of concentrated sulfuric acid product, and recycling other concentrated sulfuric acids for absorbing the gas-phase product obtained in the step 1);
3) mixing the gas-phase product which is not absorbed in the step 2) with excess air, fully oxidizing, and absorbing by using part of ferric hydroxide solid in the step 1) to obtain ferric nitrate solution, wherein the temperature in the absorption process is controlled at 20 ℃, and the ferric nitrate solution is circularly used for reacting with pyrrhotite;
4) mixing the residual ferric hydroxide solid in the step 3) with part of concentrated sulfuric acid products in the step 2), adding reduced iron powder for reaction, wherein the mass ratio of the ferric hydroxide to the reduced iron powder is 1.9, the molar ratio of the ferric hydroxide to the concentrated sulfuric acid is 0.1-10.0, and filtering, evaporating and crystallizing to obtain ferrous sulfate heptahydrate crystals.
Example 3
A method for processing pyrrhotite comprises the following steps:
1) reacting pyrrhotite with ferric nitrate with the concentration of 1mol/L at the temperature of 110 ℃, wherein the molar ratio of the ferric nitrate to sulfur in the pyrrhotite is 0.01-1.0, so as to obtain a gas-phase product and a liquid-solid mixture, performing solid-liquid separation on the liquid-solid mixture to obtain a ferric nitrate solution and a ferric hydroxide solid, and recycling the ferric nitrate solution for reacting with the pyrrhotite;
2) mixing the gas-phase product obtained in the step 1) with air according to a volume ratio of 10 in a standard state, absorbing by using concentrated sulfuric acid, wherein the unabsorbed gas-phase product is nitrogen oxide, diluting the obtained concentrated sulfuric acid to 98% by using water to obtain a part of concentrated sulfuric acid product, and recycling other concentrated sulfuric acids for absorbing the gas-phase product obtained in the step 1);
3) mixing the gas-phase product which is not absorbed in the step 2) with excess air, fully oxidizing, and absorbing by using part of ferric hydroxide solid in the step 1) to obtain ferric nitrate solution, wherein the temperature in the absorption process is controlled at 60 ℃, and the ferric nitrate solution is circularly used for reacting with pyrrhotite;
4) mixing the residual ferric hydroxide solid in the step 3) with part of concentrated sulfuric acid products in the step 2), adding reduced iron powder for reaction, wherein the mass ratio of the ferric hydroxide to the reduced iron powder is 2.1, the molar ratio of the ferric hydroxide to the concentrated sulfuric acid is 0.1-10.0, and filtering, evaporating and crystallizing to obtain ferrous sulfate heptahydrate crystals.
Claims (8)
1. A processing method of pyrrhotite is characterized in that: the method comprises the following steps:
1) reacting pyrrhotite with an iron nitrate solution at a certain temperature to obtain a gas-phase product and a liquid-solid mixture, carrying out solid-liquid separation on the liquid-solid mixture to obtain an iron nitrate solution and an iron hydroxide solid, and recycling the iron nitrate solution for reacting with pyrrhotite;
2) mixing the gas-phase product obtained in the step 1) with a certain amount of air, absorbing the mixture by using concentrated sulfuric acid, diluting the mixture to obtain a concentrated sulfuric acid product, and taking part of the concentrated sulfuric acid product to be recycled for absorbing the gas-phase product obtained in the step 1);
3) mixing the gas-phase product which is not absorbed in the step 2) with excess air, fully oxidizing, absorbing part of ferric hydroxide solid in the step 1) to obtain ferric nitrate solution, and recycling the ferric nitrate solution for reacting with pyrrhotite;
4) mixing the remaining ferric hydroxide solid with part of concentrated sulfuric acid products in the step 2), adding reduced iron powder for reaction, filtering, evaporating and crystallizing to obtain ferrous sulfate heptahydrate crystals;
in the step 1), the reaction temperature of pyrrhotite and the ferric nitrate solution is 80-110 ℃, and the concentration of the ferric nitrate solution is 1-2 mol/L;
the molar ratio of the ferric nitrate to the sulfur element in the pyrrhotite is 2/9-1.0.
2. The pyrrhotite processing method according to claim 1, characterized in that: in the step 2), the obtained gas-phase product is mixed with a certain amount of air, and the volume ratio of the gas-phase product to the air in a standard state is 0.1-10.
3. The pyrrhotite processing method according to claim 1, characterized in that: in the step 3), when the ferric hydroxide solid is used for absorbing the gas-phase product after air oxidation, the temperature in the absorption process is controlled to be 20-60 ℃.
4. The pyrrhotite processing method according to claim 1, characterized in that: in the step 4), the molar ratio of the ferric hydroxide solid to the reduced iron powder is 1.9-2.1.
5. The pyrrhotite processing method according to claim 1, characterized in that: in the step 2), the gas-phase products are nitrogen oxide and sulfur dioxide.
6. The pyrrhotite processing method according to claim 1, characterized in that: in the step 3), unabsorbed gas-phase products are nitrogen oxides.
7. The pyrrhotite processing method according to claim 1, characterized in that: in the step 2), the obtained concentrated sulfuric acid is diluted to 98% by water to obtain a concentrated sulfuric acid product.
8. The pyrrhotite processing method according to claim 1, characterized in that: in the step 4), the molar ratio of the ferric hydroxide to the concentrated sulfuric acid is 0.1-10.0.
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