CN107311130B - Comprehensive recycling method of ferric salt containing nitrogen and sulfur - Google Patents
Comprehensive recycling method of ferric salt containing nitrogen and sulfur Download PDFInfo
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- CN107311130B CN107311130B CN201710552001.0A CN201710552001A CN107311130B CN 107311130 B CN107311130 B CN 107311130B CN 201710552001 A CN201710552001 A CN 201710552001A CN 107311130 B CN107311130 B CN 107311130B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a comprehensive recycling method of ferric salt containing nitrogen and sulfur, belonging to the technical field of secondary resource recycling. Drying and denitrifying the ferric salt containing nitrogen and sulfur to obtain flue gas containing nitrogen oxide and ferric salt containing sulfur, and realizing the separation of nitrogen element from iron and sulfur elements; recovering flue gas containing nitric oxide, then using the flue gas to prepare nitric acid, and carrying out ammonia leaching on ferric sulfate salt to obtain iron ore concentrate and a solution after ammonia leaching, thereby realizing the separation of sulfate radicals and iron; directly carrying out external selling on the iron ore concentrate, evaporating and crystallizing the solution after ammonia leaching to obtain ammonium sulfate and condensed water, carrying out external selling on the ammonium sulfate, and recycling the condensed water. The whole process recovers the waste water without waste residue, and realizes the harmless and clean treatment of the ferric salt containing nitrogen and sulfur. The method has the advantages of short process flow, easy control of technical conditions and simple operation, and realizes the resource recycling of iron, sulfur and nitrogen in the nitrogenous and sulfur-containing ferric salt.
Description
Technical Field
The invention belongs to the technical field of secondary resource recycling, and particularly relates to a comprehensive recycling method of ferric salt containing nitrogen and sulfur.
Background
The traditional method for removing iron from nickel electrolyte mostly adopts a jarosite method, the method has high iron and alkali consumption, the obtained jarosite slag has high content of valuable metals, and the valuable metals such as nickel, iron and the like in the jarosite slag cannot be recycled, so that the direct yield of metals is obviously reduced. In order to reduce the cost of the iron removal process of the nickel electrolysis wet method and improve the direct recovery rate of valuable metals, the traditional process adopts the pyrogenic process for iron removal to obtain secondary nickel concentrate with the iron content of less than 3 percent, but because the properties of iron and cobalt are similar, a large amount of cobalt enters slag along with iron in the pyrogenic process iron removal process, so that the recovery rate of the cobalt is linearly reduced. In view of this, the new nickel smelting process adopts a nitric acid leaching method to treat iron-containing nickel-copper sulfide, SO that all iron in the nickel-copper sulfide is leached into a leaching solution, and a pyrolysis iron removal method is adopted for the leaching solution to convert iron in the solution into a nitrogen-containing sulfur-containing iron salt, wherein the nitrogen-containing sulfur-containing iron salt contains 30-50% of Fe and 30-50% of SO4 2-5-45%、NO3 -5-20%, can not be directly sold, and if the solid waste is piled up, the environmental pollution is caused and the resource is seriously wasted.
Disclosure of Invention
The invention aims to provide a comprehensive recycling method of nitrogenous and sulfurous iron salt, which has the advantages of short process flow, simple operation and environmental protection, and realizes the resource utilization of nitrogenous and sulfurous iron salt.
The invention relates to a comprehensive recycling method of ferric salt containing nitrogen and sulfur, which adopts the following technical scheme: drying and denitrifying the ferric salt containing nitrogen and sulfur to obtain flue gas containing nitrogen oxide and ferric salt containing sulfur, and realizing the separation of nitrogen element from iron and sulfur elements; recovering flue gas containing nitric oxide, then using the flue gas to prepare nitric acid, and carrying out ammonia leaching on ferric sulfate salt to obtain iron ore concentrate and a solution after ammonia leaching, thereby realizing the separation of sulfate radicals and iron; directly carrying out external selling on the iron ore concentrate, evaporating and crystallizing the solution after ammonia leaching to obtain ammonium sulfate and condensed water, carrying out external selling on the ammonium sulfate, and recycling the condensed water. The method specifically comprises the following steps:
a. drying and denitrifying the ferric salt containing nitrogen and sulfur to obtain flue gas containing nitrogen oxide and ferric salt containing sulfur;
b. recovering the flue gas containing the nitrogen oxides in the step a for preparing nitric acid;
c. b, carrying out ammonia leaching on the ferrous salt containing sulfur in the step a, wherein the mass ratio of ammonia water to the ferrous salt containing sulfur in the ammonia leaching process is 1.5-3:1, so as to obtain iron ore concentrate and a solution after ammonia leaching;
d. and d, evaporating and crystallizing the solution after ammonia leaching in the step c to obtain ammonium sulfate crystals and condensed water.
In the step a, the drying denitrification temperature is preferably 450-550 ℃, nitrate radicals in iron salts can be deeply removed, and qualified raw materials are provided for producing pure ammonium sulfate; the drying time is preferably 0.5-1.0h, the excessive length is high in energy consumption, and the purpose of deep nitrate radical removal cannot be achieved due to the excessively short length.
In the step c, the ammonia leaching temperature is preferably 90-110 ℃, so that the high-efficiency removal of sulfate radicals can be realized; the ammonia leaching time is preferably 0.5-1.5h, and the ammonia leaching time is too long and energy consumption is high, so that the sulfur content in the iron ore concentrate is increased due to too short ammonia leaching time.
The comprehensive recycling method of the ferric salt containing nitrogen and sulfur has the following advantages:
1. according to the invention, nitrogen and sulfur containing ferric salt is subjected to denitrification, ammonia leaching and evaporative crystallization treatment in sequence, so that high-grade iron ore concentrate and ammonium sulfate crystals can be used as product export sales, flue gas containing nitrogen oxide generated in the denitrification process is recycled and then used for preparing nitric acid, condensed water generated in the evaporative crystallization process is recycled, no waste residue and waste water is generated in the whole process, and harmless and clean treatment of the nitrogen and sulfur containing ferric salt is realized.
2. The method has the advantages of short process flow, easy control of technical conditions and simple operation, and realizes the resource recycling of iron, sulfur and nitrogen in the nitrogenous and sulfur-containing ferric salt.
Detailed Description
The method for comprehensively recycling the ferric salt containing nitrogen and sulfur according to the present invention will be further described with reference to the following specific examples.
Example 1
In this embodiment, the nitrogen-containing and sulfur-containing iron salt comprises the following components (by mass): fe 30% and SO4 2- 45%、NO3 - 5%；
100g of the iron salt containing nitrogen and sulfur is taken to denitrify for 1.0h at 450 ℃, and flue gas containing nitrogen oxide and 93g of iron salt containing sulfur are obtained. Recovering flue gas containing nitrogen oxides for preparing nitric acid; the sulfur-containing iron salt comprises the following components in percentage by mass: fe 32.81%, SO4 2- 48.87%、NO3 -< 0.001%, yield 93%. 300g of ammonia water was added to the sulfur-containing iron salt and reacted at 90 ℃ for 0.5h to obtain 53.29g of iron concentrate and 600ml of ammonia-leached solution. The iron ore concentrate comprises the following components: fe 61.57%, SO4 2- 0.11%、NO3 -0.04%, yield 57.30%; the solution after ammonia leaching contains SO4 2- 97.39 g/L、NO3 - ＜0.001 g/L、NH4 +43.98 g/L. Evaporating and crystallizing the solution after ammonia leaching to obtain ammonium sulfate crystals and condensed water. The content of impurity elements Fe and Ni in ammonium sulfate crystallization is less than 0.001%, and the impurity elements Fe and Ni are directly sold out, so that condensed water can be recycled. The removal rate of sulfate radicals in the whole process is 99.67 percent, and the removal rate of nitrate radicals is more than 99.99 percent.
Example 2
In this embodiment, the nitrogen-containing and sulfur-containing iron salt comprises the following components (by mass): fe 50% and SO4 2- 5%、NO3 - 20%；
100g of the iron salt containing nitrogen and sulfur is taken and denitrified for 1.0h at 550 ℃ to obtain flue gas containing nitrogen oxide and 73g of iron salt containing sulfur. Recovering flue gas containing nitrogen oxides for preparing nitric acid; sulfur-containing iron salt component (mass percent)Comprises the following steps: fe 56% and SO4 2-6.8%、NO3 -< 0.001%, yield 73%. 150g of ammonia water was added to the sulfur-containing iron salt and reacted at 110 ℃ for 1.5h to obtain 65.88g of iron concentrate and 550ml of post-ammonia leaching solution. The iron ore concentrate comprises the following components: fe 62.05%, SO4 2- 0.18%、NO3 -0.03%, yield 90.24%; the solution after ammonia leaching contains SO4 2- 13.06 g/L、NO3 - ＜0.001 g/L、NH4 +6.12 g/L. Evaporating and crystallizing the solution after ammonia leaching to obtain ammonium sulfate crystals and condensed water. The content of impurity elements Fe and Ni in ammonium sulfate crystallization is less than 0.001%, and the impurity elements Fe and Ni are directly sold out, so that condensed water can be recycled. The removal rate of sulfate radicals in the whole process is 99.95 percent, and the removal rate of nitrate radicals is more than 99.99 percent.
Example 3
In this embodiment, the nitrogen-containing and sulfur-containing iron salt comprises the following components (by mass): fe 40% and SO4 2- 35%、NO3 - 10%；
100g of the iron salt containing nitrogen and sulfur is taken, and denitrification is carried out for 45min at 500 ℃ to obtain flue gas containing nitrogen oxide and 86g of iron salt containing sulfur. Recovering flue gas containing nitrogen oxides for preparing nitric acid; the sulfur-containing iron salt comprises the following components in percentage by mass: fe 45% and SO4 2-38%、NO3 -< 0.001%, yield 86%. 220g of ammonia water was added to the sulfur-containing iron salt and reacted at 100 ℃ for 1 hour to obtain 64.25g of iron concentrate and 600ml of ammonia-leached solution. The iron ore concentrate comprises the following components: fe 60.23%, SO4 2- 0.23%、NO3 -0.03%, yield 74.71%; the solution after ammonia leaching contains SO4 2- 75.55 g/L、NO3 - ＜0.001 g/L、NH4 +34.20 g/L. Evaporating and crystallizing the solution after ammonia leaching to obtain ammonium sulfate crystals and condensed water. The content of impurity elements Fe and Ni in ammonium sulfate crystallization is less than 0.001%, and the impurity elements Fe and Ni are directly sold out, so that condensed water can be recycled. The removal rate of sulfate radicals in the whole process is 99.72 percent, and the removal rate of nitrate radicals is more than 99.99 percent.
Claims (4)
1. The comprehensive recycling method of the ferric salt containing nitrogen and sulfur is characterized by comprising the following steps:
a. drying and denitrifying the nitrogenous and sulfureous iron salt at the temperature of 450-550 ℃ to obtain flue gas containing nitrogenous oxides and sulfureous iron salt;
b. recovering the flue gas containing the nitrogen oxides in the step a for preparing nitric acid;
c. b, carrying out ammonia leaching on the ferrous salt containing sulfur in the step a, wherein the mass ratio of ammonia water to the ferrous salt containing sulfur in the ammonia leaching process is 1.5-3:1, so as to obtain iron ore concentrate and a solution after ammonia leaching;
d. evaporating and crystallizing the solution after ammonia leaching in the step c to obtain ammonium sulfate crystals and condensed water;
the novel process for smelting nickel by using the nitrogen-containing and sulfur-containing ferric salt is used for treating the iron-containing nickel-copper sulfide by adopting a nitric acid leaching method, SO that all iron in the nickel-copper sulfide is leached into a leaching solution, and the leaching solution is subjected to a pyrolysis iron removal method to convert iron in the solution into the nitrogen-containing and sulfur-containing ferric salt, wherein the nitrogen-containing and sulfur-containing ferric salt contains 30-50% of Fe and 30-50% of SO4 2- 5-45%、NO3 - 5-20%。
2. The comprehensive recycling method of iron salts containing nitrogen and sulfur according to claim 1, characterized in that: in the step a, the drying time is 0.5-1.0 h.
3. The comprehensive recycling method of iron salts containing nitrogen and sulfur according to claim 1, characterized in that: in the step c, the ammonia leaching temperature is 90-110 ℃.
4. The comprehensive recycling method of iron salts containing nitrogen and sulfur according to claim 1, characterized in that: in the step c, the ammonia leaching time is 0.5-1.5 h.
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