CN110683585A - Purification method of copper smelting crude ammonium rhenate - Google Patents
Purification method of copper smelting crude ammonium rhenate Download PDFInfo
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- CN110683585A CN110683585A CN201910939501.9A CN201910939501A CN110683585A CN 110683585 A CN110683585 A CN 110683585A CN 201910939501 A CN201910939501 A CN 201910939501A CN 110683585 A CN110683585 A CN 110683585A
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Abstract
The invention provides a method for purifying copper smelting coarse ammonium rhenate, which adopts pure water-nitric acid-ammonia water to purify ammonium rhenate, firstly, the coarse ammonium rhenate is re-dissolved through the pure water, impurity elements are prevented from being brought in, then, the impurity elements in the coarse ammonium rhenate are removed through nitric acid, finally, impurity metal precipitates in a coarse ammonium rhenate solution are removed through the ammonia water, meanwhile, the introduction of the impurity elements is avoided, and high-purity ammonium rhenate crystals can be obtained after crystallization. The method has the advantages of short process flow, less control parameters, simple operation, capability of stably improving the concentration of the ammonium rhenate product and high product recovery rate.
Description
Technical Field
The invention belongs to the technical field of rare metal element recovery, and particularly relates to a method for purifying copper smelting ammonium rhenate.
Background
Rhenium, the most rare element in the earth's crust, has an average content of only parts per billion and is also one of the highest melting and boiling elements. The method is widely accompanied in copper sulfide ores, most domestic copper smelting enterprises have ammonium rhenate production lines at present, but the production methods of the ammonium rhenate are also different according to different raw material components. As the ammonium rhenate is mainly used in high-tech technical industries such as national defense and aerospace industrial alloys, petrochemical catalysts, electrons and medical instruments, the purity of the ammonium rhenate plays a decisive role in the sales benefits of the ammonium rhenate. How to improve the purity of the ammonium rhenate product becomes a key problem restricting the sale of the ammonium rhenate, and the problem of improving the purity of the ammonium rhenate needs to be solved urgently.
The invention patent CN201510054805.9 discloses a method for preparing ammonium perrhenate, which is to purify a rhenium-rich recovery solution obtained by enriching a rhenium-poor stock solution to prepare ammonium perrhenate, and prepare ammonium perrhenate by performing reduced pressure concentration, heating decomposition and dissolution crystallization on the rhenium-rich recovery solution, and the method comprises the following steps: the first step, decompression concentration to prepare concentrated crystal, the second step, heating decomposition to collect rhenium heptoxide solid, the third step, dissolving crystallization to prepare ammonium perrhenate, and the fourth step, molybdenum-rhenium recovery. The method can realize effective separation of molybdenum and rhenium, and prepare high-grade ammonium perrhenate; the poor rhenium stock solution is used as a raw material, the raw material is widely and easily obtained, and the comprehensive recycling of resources is realized.
The crude ammonium rhenate produced by copper smelting contains a large amount of metal impurities and insoluble impurities, and a large amount of raw materials are needed to realize the recovery and purification of the ammonium rhenate in a common recovery method, so that the production cost is increased.
Disclosure of Invention
The invention provides a method for purifying copper smelting coarse ammonium rhenate, aiming at the defects that the prior art is rare and the recovery and purification method of the coarse ammonium rhenate generated by copper smelting is difficult.
The invention is realized by the following technical scheme:
a method for purifying copper smelting crude ammonium rhenate comprises the following steps:
s1: adding 30kg of crude ammonium rhenate into a dissolving kettle, adding 200-250L of pure water, introducing steam, and heating the dissolving kettle to 90-100 ℃ under 0.4-0.5 MPa to obtain a mixed solution I;
s2: standing the mixed solution I for 5-10 min, and then introducing the mixed solution I into a vacuum filter barrel for filtering to obtain a filtrate I;
s3: sending the filtrate I to a nitration kettle, adding 30-45L of nitric acid into the nitration kettle, controlling the temperature in the nitration kettle at 50-70 ℃, stirring for 2-3 h, adding 15-30L of hydrogen peroxide, and continuously stirring for 2h to obtain a mixed solution II;
s4: sending the mixed solution II to a vacuum filter barrel for filtering to obtain a filtrate II;
s5: sending the filtrate II to a neutralization kettle, adding ammonia water to adjust the pH value to 8-9, and stirring for 15-20 min to obtain a mixed solution III;
s6: feeding the mixed solution III into a vacuum filter barrel, and filtering while keeping the temperature of the mixed solution III at 60 ℃ to obtain a refined solution;
s7: delivering the refined solution to a refrigeration house, carrying out freezing crystallization for 24-30 h at the temperature of-4 to-2 ℃, delivering the obtained crystallized solution to a vacuum filter barrel, and carrying out vacuum filtration to obtain crystals and refined filtrate, wherein the crystals are high-purity ammonium rhenate; the refined filtrate is sent back to the nitration kettle for continuous purification.
According to the method, the coarse ammonium rhenate crystals are re-dissolved through pure water, so that the introduction of impurity elements is avoided, the solubility product is unbalanced after the nitric acid and the hydrogen peroxide are dissolved, insoluble impurities (insoluble electrolyte) are precipitated and removed, the solution is neutralized by adding ammonia water, and the ammonia water is combined with metal ion impurities in the solution to generate precipitates and remove metal ions, so that the addition of the impurity elements is avoided. The solution after freezing and crystallizing is continuously purified, so that the discharge is reduced, and the recovery rate is improved.
As a further improvement of the invention, the nitric acid, the hydrogen peroxide and the ammonia water are all in analytical pure grades;
the adding amount of the nitric acid is that 1-1.5L of nitric acid is added into each kilogram of crude ammonium rhenate;
the addition amount of the hydrogen peroxide is 0.5-1L of hydrogen peroxide added into each kilogram of coarse ammonium rhenate.
The filtrate I is in a supersaturated state due to the addition of hydrogen peroxide, so that the combination of nitric acid and insoluble impurities (insoluble electrolyte) can be promoted to generate precipitates, and the efficiency of removing the insoluble impurities is improved.
As a further improvement of the method, in the step S1, the addition amount of pure water is 7-9L per kilogram of crude ammonium rhenate.
As a further improvement of the invention, the mesh number of the filter cloth of the vacuum filter barrel is 130-200 meshes; the vacuum filter barrel is vacuumized through a water ring vacuum pump and participates in the filtering operation in the whole process.
As a further improvement of the invention, the dissolving kettle, the nitration kettle and the neutralization kettle are enamel reaction kettles and are provided with heating jackets.
The invention has the beneficial effects that:
1. according to the method, the crude ammonium rhenate is purified by adopting pure water, the nitric acid with the analyzed purity, hydrogen peroxide and ammonia water, and impurity elements are not carried in the whole process, so that the complexity of operation is reduced.
2. The refined filtrate after crystallization is continuously returned for purification, so that the discharge is reduced, and the recovery rate of ammonium rhenate and the consumption of reagents are improved.
3. The method has short process flow, the crude ammonium rhenate can be purified through redissolution, nitration, neutralization and freezing crystallization, and the purity of the purified ammonium rhenate crystal can reach more than 99.99 percent.
Drawings
FIG. 1 is a flow chart of the purification process of the present invention.
Reference numerals: 1-dissolution kettle, 2-vacuum filter barrel, 3-nitration kettle, 4-neutralization kettle and 5-water ring vacuum pump.
Detailed Description
The invention will be further explained with reference to the drawings.
Example 1
A method for purifying copper smelting crude ammonium rhenate comprises the following steps:
s1: adding 30kg of crude ammonium rhenate into a dissolving kettle 1, adding 200L of pure water, introducing steam, and heating the dissolving kettle to 90 ℃ under 0.4MPa to obtain a mixed solution I;
s2: standing the mixed solution I for 5min, and then introducing the mixed solution I into a vacuum filter barrel 2 for filtering to obtain a filtrate I;
s3: sending the filtrate I to a nitration kettle 3, adding 30L of nitric acid into the nitration kettle 3, controlling the temperature in the nitration kettle at 50-70 ℃, stirring for 2-3 h, adding 15L of hydrogen peroxide, and continuously stirring for 2h to obtain a mixed solution II;
s4: sending the mixed solution II to a vacuum filter barrel for filtering to obtain a filtrate II;
s5: sending the filtrate II to a neutralization kettle 4, adding ammonia water to adjust the pH value to 8, and stirring for 15min to obtain a mixed solution III;
s6: feeding the mixed solution III into a vacuum filter barrel 2, and filtering while keeping the temperature of the mixed solution III at 60 ℃ to obtain a refined solution; the vacuum filter barrel 2 needs to be heated in advance;
s7: delivering the refined solution to a refrigeration house, carrying out freezing crystallization for 24h at-2 ℃, delivering the obtained crystallized solution to a vacuum filter barrel 2 for vacuum filtration to obtain crystals and refined filtrate, wherein the crystals are high-purity ammonium rhenate; the refined filtrate is sent back to the nitration kettle 3 for continuous purification;
the mesh number of the filter cloth of the vacuum filter barrel 3 is 130 meshes; the vacuum filter barrel 3 is vacuumized by a water ring vacuum pump 5 and participates in the filtering work in the whole process;
the dissolving kettle 1, the nitration kettle 3 and the neutralization kettle 4 are all enamel reaction kettles and are provided with heating jackets.
The ammonium rhenate crystal purity obtained in this example was 99.98%.
Example 2
A method for purifying copper smelting crude ammonium rhenate comprises the following steps:
s1: adding 30kg of crude ammonium rhenate into a dissolving kettle 1, adding 250L of pure water, introducing steam, and heating the dissolving kettle to 100 ℃ under 0.5MPa to obtain a mixed solution I;
s2: standing the mixed solution I for 10min, and then introducing the mixed solution I into a vacuum filter barrel 2 for filtering to obtain a filtrate I;
s3: sending the filtrate I to a nitration kettle 3, adding 45L of nitric acid into the nitration kettle 3, controlling the temperature in the nitration kettle at 70 ℃, stirring for 3 hours, then adding 30L of hydrogen peroxide, and continuing stirring for 2 hours to obtain a mixed solution II;
s4: sending the mixed solution II to a vacuum filter barrel for filtering to obtain a filtrate II;
s5: sending the filtrate II to a neutralization kettle 4, adding ammonia water to adjust the pH value to 9, and stirring for 15min to obtain a mixed solution III;
s6: feeding the mixed solution III into a vacuum filter barrel 2, and filtering while keeping the temperature of the mixed solution III at 60 ℃ to obtain a refined solution; the vacuum filter barrel 2 needs to be heated in advance;
s7: delivering the refined solution to a refrigeration house, carrying out freezing crystallization for 30h at-4 ℃, delivering the obtained crystallized solution to a vacuum filter barrel 2 for vacuum filtration to obtain crystals and refined filtrate, wherein the crystals are high-purity ammonium rhenate; the refined filtrate is sent back to the nitration kettle 3 for continuous purification;
the filter cloth mesh number of the vacuum filter barrel 3 is 200 meshes; the vacuum filter barrel 3 is vacuumized by a water ring vacuum pump 5 and participates in the filtering work in the whole process;
the dissolving kettle 1, the nitration kettle 3 and the neutralization kettle 4 are all enamel reaction kettles and are provided with heating jackets.
The ammonium rhenate produced in this example had a crystal purity of 99.99%.
Example 3
A method for purifying copper smelting crude ammonium rhenate comprises the following steps:
s1: adding 30kg of crude ammonium rhenate into a dissolving kettle 1, adding 240L of pure water, introducing steam, and heating the dissolving kettle to 95 ℃ under 0.5MPa to obtain a mixed solution I;
s2: standing the mixed solution I for 8min, and then introducing the mixed solution I into a vacuum filter barrel 2 for filtering to obtain a filtrate I;
s3: sending the filtrate I to a nitration kettle 3, adding 35L of nitric acid into the nitration kettle 3, controlling the temperature in the nitration kettle at 65 ℃, stirring for 2.5 hours, then adding 20L of hydrogen peroxide, and continuously stirring for 2 hours to obtain a mixed solution II;
s4: sending the mixed solution II to a vacuum filter barrel for filtering to obtain a filtrate II;
s5: sending the filtrate II to a neutralization kettle 4, adding ammonia water to adjust the pH value to 8.5, and stirring for 15min to obtain a mixed solution III;
s6: feeding the mixed solution III into a vacuum filter barrel 2, and filtering while keeping the temperature of the mixed solution III at 60 ℃ to obtain a refined solution; the vacuum filter barrel 2 needs to be heated in advance;
s7: delivering the refined solution to a refrigeration house, carrying out freezing crystallization for 25h at-3 ℃, delivering the obtained crystallized solution to a vacuum filter barrel 2 for vacuum filtration to obtain crystals and refined filtrate, wherein the crystals are high-purity ammonium rhenate; the refined filtrate is sent back to the nitration kettle 3 for continuous purification;
the filter cloth mesh number of the vacuum filter barrel 3 is 150 meshes; the vacuum filter barrel 3 is vacuumized by a water ring vacuum pump 5 and participates in the filtering work in the whole process;
the dissolving kettle 1, the nitration kettle 3 and the neutralization kettle 4 are all enamel reaction kettles and are provided with heating jackets.
The ammonium rhenate produced in this example had a crystal purity of 99.99%.
The above embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and the scope of the present invention is defined by the claims. Various modifications and equivalents may be made thereto by those skilled in the art within the spirit and scope of the present invention, and such modifications and equivalents should be considered as falling within the scope of the present invention.
Claims (5)
1. A method for purifying copper smelting coarse ammonium rhenate is characterized by comprising the following steps: the method comprises the following steps:
s1: adding 30kg of crude ammonium rhenate into a dissolving kettle (1), adding 200-250L of pure water, introducing steam, and heating the dissolving kettle to 90-100 ℃ under 0.4-0.5 MPa to obtain a mixed solution I;
s2: standing the mixed solution I for 5-10 min, and then introducing the mixed solution I into a vacuum filter barrel (2) for filtering to obtain a filtrate I;
s3: sending the filtrate I to a nitration kettle (3), adding 30-45L of nitric acid into the nitration kettle (3), controlling the temperature in the nitration kettle at 50-70 ℃, stirring for 2-3 h, adding 15-30L of hydrogen peroxide, and continuously stirring for 2h to obtain a mixed solution II;
s4: sending the mixed solution II to a vacuum filter barrel for filtering to obtain a filtrate II;
s5: sending the filtrate II to a neutralization kettle (4), adding ammonia water to adjust the pH value to 8-9, and stirring for 15-20 min to obtain a mixed solution III;
s6: feeding the mixed solution III into a vacuum filter barrel (2), and filtering while keeping the temperature of the mixed solution III at 60 ℃ to obtain a refined solution; the vacuum filter barrel (2) needs to be heated in advance;
s7: delivering the refined solution to a refrigeration house, carrying out freezing crystallization for 24-30 h at the temperature of-4 to-2 ℃, delivering the obtained crystallized solution to a vacuum filter barrel (2) for vacuum filtration to obtain crystals and refined filtrate, wherein the crystals are high-purity ammonium rhenate; the refined filtrate is sent back to the nitration kettle (3) for continuous purification.
2. The method for purifying copper smelting ammonium rough rhenate as claimed in claim 1, is characterized in that: the nitric acid, the hydrogen peroxide and the ammonia water are all in analytical grade;
the adding amount of the nitric acid is that 1-1.5L of nitric acid is added into each kilogram of crude ammonium rhenate;
the addition amount of the hydrogen peroxide is 0.5-1L of hydrogen peroxide added into each kilogram of coarse ammonium rhenate.
3. The method for purifying the copper smelting ammonium rough rhenate as claimed in claim 1 or 2, is characterized in that: in the step S1, the addition amount of pure water is 7-9L per kilogram of crude ammonium rhenate.
4. The method for purifying copper smelting ammonium rough rhenate as claimed in claim 3, is characterized in that: the mesh number of the filter cloth of the vacuum filter barrel (3) is 130-200 meshes; the vacuum filter barrel (3) is vacuumized by a water ring vacuum pump (5) and participates in the filtering operation in the whole process.
5. The method for purifying the copper smelting ammonium rough rhenate according to any one of claims 1 to 4, characterized by comprising the following steps: the dissolving kettle (1), the nitration kettle (3) and the neutralization kettle (4) are all enamel reaction kettles and are provided with heating jackets.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111874952A (en) * | 2020-07-29 | 2020-11-03 | 铜陵铜冠优创特种材料有限公司 | Purification process of copper smelting byproduct ammonium perrhenate |
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| CN111874952A (en) * | 2020-07-29 | 2020-11-03 | 铜陵铜冠优创特种材料有限公司 | Purification process of copper smelting byproduct ammonium perrhenate |
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