CN106011487A - Method for recycling rhenium from copper smelting smoke washing waste acid - Google Patents
Method for recycling rhenium from copper smelting smoke washing waste acid Download PDFInfo
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- CN106011487A CN106011487A CN201610493640.XA CN201610493640A CN106011487A CN 106011487 A CN106011487 A CN 106011487A CN 201610493640 A CN201610493640 A CN 201610493640A CN 106011487 A CN106011487 A CN 106011487A
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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
- C22B61/00—Obtaining metals not elsewhere provided for in this subclass
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
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Abstract
The invention provides a method for recycling rhenium from copper smelting smoke washing waste acid. The method includes the steps that A, the copper smelting smoke washing waste acid is filtered, and clear waste acid and selenium mud are obtained; B, the clear waste acid is mixed with a first precipitation agent to react, and copper-removed later liquid and copper-deposited slag are obtained; and C, the copper-removed later liquid is mixed with a second precipitation agent to react, rhenium-deposited later liquid and rhenium-rich slag are obtained, and in the clear waste acid, the copper content ranges from 0.2 g/L to 3 g/L; or the method includes the steps that A, the copper smelting smoke washing waste acid is filtered, and clear waste acid and selenium mud are obtained; and D, the clear waste acid is mixed with a precipitation agent to react, rhenium-deposited later liquid and rhenium-rich slag are obtained, and in the clear waste acid, the copper content is larger than 0 g/L and smaller than 0.2 g/L. According to the method, the high-copper waste liquid is subjected to copper and rhenium deposition step by step, the low-copper waste liquid is subjected to rhenium deposition in one step, only one kind of auxiliary material sodium thiosulfate is needed in the whole process, the copper recycling rate ranges from 95.3% to 99.8%, and the rhenium recycling rate ranges from 99% to 99.53%.
Description
Technical field
The present invention relates to dissipated metal recovery technology field, particularly relate to a kind of Copper making flue dust washing spent acid
The recovery method of middle rhenium.
Background technology
Rhenium is a kind of dissipated metal, and fusing point is high, stable in properties, can be used for petroleum catalyst, high temperature super resistance to
The aspects such as thermalloy.Rhenium metal and alloy thereof can be additionally used in prepares Fountain pen nib and pyrometer couple, with
And make catalyst in dehydrogenating alcohol, synthesis ammonia and the reaction by sulfur dioxide sulfur trioxide.Tungstenic
90%, vanadium 1%, the alloy of rhenium 9% have high temperature resistant character.Rhenium is all to be present in brightness as associated metal
In copper mine, molybdenite, do not find high rhenium-containing ore deposit so far.Therefore, the recovery method of rhenium is particularly important.
The recovery method of rhenium mainly has extraction, ion exchange and chemical precipitation method.Wherein, extraction
There is organic contaminated wastewater and the big problem for the treatment of capacity, ion exchange is unfavorable for applying to extensive work
Industry produces, Integrated comparative, and chemical precipitation method is presently the most conventional method, can be by adding medicament
Control process, the flow process making rhenium obtain enrichment in slag becomes economical and efficient.
At present, domestic and international most enterprise all uses arsenic filter cake to extract or spent acid extraction extracts Copper making cigarette
Rhenium in dirt.Relevant information shows, in arsenic filter cake, rhenium-containing amount is less than 1%, and the organic facies of spent acid extraction processes
The more, and the Rhenium recovery rate of above method is the most not satisfactory for problem.About the method for chemical precipitation rhenium, see
All articles mainly dense less than the low copper of 1g/L, low acid, the processing method dense for high-copper peracid has no
Report.It is higher that the Rhenium recovery that in enrichment slag, copper content is follow-up time higher purifies loss rate, finds suitable work
Process energy-saving and environmental protection, the efficient rhenium that reclaims can be that Copper making finds a preferably Chuan Xiaozhi road.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of Copper making flue dust washing spent acid
The recovery method of middle rhenium, sinks rhenium by the high-copper heavy copper rhenium of substep and a step, to heavy copper ashes and richness after point copper
Rhenium slag uses the method that different purifying technique is separately recovered rhenium, in the case of impurity element fluctuation is relatively big,
In the case of ensureing whole recovery economic benefit, drastically increase Rhenium recovery rate.
The invention provides the recovery method of rhenium in a kind of Copper making flue dust washing spent acid, including:
A) Copper making flue dust washing spent acid is filtered, obtain clarifying spent acid and selenium mud；
B) by described clarification spent acid and the first precipitant mix, reaction, liquid and heavy copper ashes after decopper(ing) is obtained；
C) by liquid after described decopper(ing) and the second precipitant mix, reaction, liquid and rich rhenium slag after heavy rhenium is obtained；
In described clarification spent acid, copper content is 0.2g/L～3g/L；
Or including:
A) Copper making flue dust washing spent acid is filtered, obtain clarifying spent acid and selenium mud；
D) by described clarification spent acid and precipitant mix, reaction, liquid and rich rhenium slag after heavy rhenium is obtained；
In described clarification spent acid, copper content is more than 0, less than 0.2g/L.
Preferably, described first precipitant, the second precipitant, precipitant are sodium thiosulfate.
Preferably, described step B) in, the quality of the first precipitant contains the ratio of copper mass with clarifying in spent acid
Example is (6～10): 1.
Preferably, described step C) in, after the second precipitant and decopper(ing), the mass ratio of liquid is (2～3):
1。
Preferably, described step D) in, precipitant is (2～5) with the mass ratio of clarification spent acid: 1.
Preferably, described step A) in, the temperature of filtration is 50～60 DEG C.
Preferably, described step B) in, the temperature of reaction is 60～65 DEG C, the time of reaction be 25～
35 minutes.
Preferably, described step C) in, the temperature of reaction is 65～75 DEG C, the time of reaction be 45～
70 minutes.
Preferably, described step D) in, the temperature of reaction is 65～75 DEG C, the time of reaction be 45～
70 minutes.
Preferably, described Copper making flue dust washing spent acid includes: copper 0g/L～3g/L, and rhenium is more than 1mg/L,
Arsenic 0g/L～5g/L, acid dense 0%～30%.
Compared with prior art, the invention provides the recovery side of rhenium in a kind of Copper making flue dust washing spent acid
Method, including: A) Copper making flue dust washing spent acid is filtered, obtain clarifying spent acid and selenium mud；B) by institute
State clarification spent acid and the first precipitant mix, reaction, obtain liquid and heavy copper ashes after decopper(ing)；C) by described de-
Liquid and the second precipitant mix, reaction after copper, obtain liquid and rich rhenium slag after heavy rhenium；In described clarification spent acid,
Copper content is 0.2g/L～3g/L；Or including: A) Copper making flue dust washing spent acid is filtered, obtain clear
Stripping acid and selenium mud；D) by described clarification spent acid and precipitant mix, reaction, liquid and richness after heavy rhenium is obtained
Rhenium slag；
The present invention is first by spent acid heat filtering, during high-copper, uses clarification spent acid to add precipitant first and first enters
Row decopper(ing) operation, obtains liquid after heavy copper ashes and decopper(ing), and after decopper(ing), liquid obtains rich rhenium by addition precipitant again
After slag and heavy rhenium, the substep of liquid sinks the method for copper；During low copper, then a step is used to sink rhenium technique, clear at low copper
Stripping acid adds precipitant and directly obtains liquid after rich rhenium slag and heavy rhenium.The heavy copper ashes obtained and rich rhenium slag lead to
Later continuous purifying technique can produce rhenium product salt or produce rhenium powder, rhenium bar further.Heavy by substep
Copper rhenium, copper rhenium is enriched in heavy copper ashes and rich rhenium slag, follow-up carries out rhenium therein with different process respectively
Reclaim.Recovery method technological process disclosed by the invention is short, and treating capacity is big, and equipment and raw material put into cheap,
Only need to can carry out at ambient pressure.Owing to simply adding a step chemical precipitation in spent acid conventional processes,
The system processing whole spent acid does not affect, and this technique does not has environmental issue.Test result indicate that,
It is suitable for the spent acid of low rhenium high-copper, the present invention is by optimizing technology controlling and process, and whole process only needs
Want sodium thiosulfate one adjuvant, the recovery method of the rhenium that the present invention provides, the response rate of copper be 95.3%～
99.8%, Rhenium recovery rate is 99%～99.53%, and outer row sinks after rhenium that liquid cupric is less than 0.01g/L, and rhenium-containing is little
In 0.0001g/L.
Accompanying drawing explanation
In the recovery method of the rhenium that Fig. 1 provides for the present invention, the process chart of high-copper spent acid；
In the recovery method of the rhenium that Fig. 2 provides for the present invention, the process chart of low copper spent acid.
Detailed description of the invention
The invention provides the recovery method of rhenium in a kind of Copper making flue dust washing spent acid, including:
A) Copper making flue dust washing spent acid is filtered, obtain clarifying spent acid and selenium mud；
B) by described clarification spent acid and the first precipitant mix, reaction, liquid and heavy copper ashes after decopper(ing) is obtained；
C) by liquid after described decopper(ing) and the second precipitant mix, reaction, liquid and rich rhenium slag after heavy rhenium is obtained；
In described clarification spent acid, copper content is 0.2g/L～3g/L；
Or including:
A) Copper making flue dust washing spent acid is filtered, obtain clarifying spent acid and selenium mud；
D) by described clarification spent acid and precipitant mix, reaction, liquid and rich rhenium slag after heavy rhenium is obtained；
In described clarification spent acid, copper content is more than 0, less than 0.2g/L.
Invention is first by spent acid heat filtering, during high-copper, uses clarification spent acid to add precipitant first and first carries out
Decopper(ing) operation, obtains liquid after heavy copper ashes and decopper(ing), and after decopper(ing), liquid obtains rich rhenium slag by addition precipitant again
The method of copper is sunk with the substep of liquid after heavy rhenium；During low copper, then use a step to sink rhenium technique, clarify at low copper
Spent acid adds precipitant and directly obtains liquid after rich rhenium slag and heavy rhenium.The heavy copper ashes obtained and rich rhenium slag pass through
Follow-up purifying technique can produce rhenium product salt or produce rhenium powder, rhenium bar further.By the heavy copper of substep
Rhenium, copper rhenium is enriched in heavy copper ashes and rich rhenium slag, follow-up carries out back rhenium therein with different process respectively
Receive.Recovery method technological process disclosed by the invention is short, and treating capacity is big, and equipment and raw material put into cheap,
Only need to can carry out at ambient pressure.Owing to simply adding a step chemical precipitation in spent acid conventional processes,
The system processing whole spent acid does not affect, and this technique does not has environmental issue.Test result indicate that,
It is suitable for the spent acid of low rhenium high-copper, the present invention is by optimizing technology controlling and process, and whole process only needs
Want sodium thiosulfate one adjuvant, the recovery method of the rhenium that the present invention provides, the response rate of copper be 95.3%～
99.8%, Rhenium recovery rate is 99%～99.53%, and outer row sinks after rhenium that liquid cupric is less than 0.01g/L, and rhenium-containing is little
In 0.0001g/L.
In the present invention, described Copper making flue dust washing spent acid includes: copper 0g/L～3g/L, and is not 0, rhenium
More than 1mg/L, arsenic 0g/L～5g/L, acid dense 0%～30%.
First Copper making flue dust washing spent acid is carried out heat filtering, obtain clarifying spent acid and selenium mud.
The temperature of described filtration is preferably 50～60 DEG C, more preferably 54～58 DEG C, in some of the present invention
In specific embodiment, the temperature of described filtration is 55 DEG C.
Described acid dense more preferably 7%～30%, in some specific embodiment, described acid is dense is 7.1%,
8.5% or 15.3%.
The present invention there is no particular determination to described filter type, the mistake that can be well known to those skilled in the art
Filter mode, the present invention is preferably filter pressing.
The selenium mud grade that the present invention obtains is 52%～83%, can purify further and obtain thick selenium.Obtain is clear
In stripping acid, selenium content is 0～0.05g/L, except selenium ratio reaches 53.5%～65.8%.
When the clarification spent acid obtained is high-copper clarification spent acid, in the most described clarification spent acid, copper content is
During 0.2g/L～3g/L, described clarification spent acid is carried out successively decopper(ing), heavy rhenium operation.
Concrete, first by described clarification spent acid and the first precipitant mix, reaction, carry out reducing heavy copper
Process, obtain liquid and heavy copper ashes after decopper(ing)；
The quality of described first precipitant and clarification spent acid contain the ratio of copper mass preferably (6～10):
1, those skilled in the art can select according to the practical situation of clarification spent acid composition and adjust the first precipitant
Consumption.When the copper content of described clarification spent acid is 0.2g/L～1.0g/L, during acid dense 0%～20%, first
The quality of precipitant and clarification spent acid contain the ratio of copper mass preferably (6～8): 1；When described clarification
The copper content of spent acid is 0.2g/L～1.0g/L, and during acid dense 20%～30%, the quality of the first precipitant is with clear
In stripping acid, the ratio containing copper mass is preferably (8～10): 1；When the copper content of described clarification spent acid is
1.0g/L～3.0g/L, during acid dense 0%～30%, the quality of the first precipitant contains copper mass in clarification spent acid
Ratio be preferably (8～10): 1.
The temperature of described reaction is preferably 60～65 DEG C, and those skilled in the art can become according to clarification spent acid
The practical situation divided selects and adjusts reaction temperature.When the copper content of described clarification spent acid be 0.2g/L～
1.0g/L, during acid dense 0%～20%, reaction temperature preferably 62～65 DEG C；When the copper of described clarification spent acid contains
Amount is 0.2g/L～1.0g/L, during acid dense 20%～30%, reaction temperature preferably 60～62 DEG C；When described clear
The copper content of stripping acid is 1.0g/L～3.0g/L, during acid dense 0%～30%, and reaction temperature preferably 60～62 DEG C.
The time of described reaction is preferably 25～35 minutes, and those skilled in the art can be according to clarification spent acid
The practical situation of composition selects and adjusts the response time.When the copper content of described clarification spent acid be 0.2g/L～
1.0g/L, during acid dense 0%～20%, preferably 30～35 minutes response time；Copper when described clarification spent acid
Content is 0.2g/L～1.0g/L, during acid dense 20%～30%, and preferably 25～30 minutes response time；When
The copper content of described clarification spent acid is 1.0g/L～3.0g/L, and during acid dense 0%～30%, the response time is preferred
25～30 minutes.
The present invention, by above-mentioned decopper(ing) operation, makes the copper of 91%～98.3% in spent acid first sink to copper ashes
In, the rhenium of 5%～25% enters heavy copper ashes and reclaims rhenium, and the rhenium of 75%～95% enters next step heavy rhenium technique.
Then by liquid after described decopper(ing) and the second precipitant mix, reaction, the heavy rhenium that carries out reducing processes,
Liquid and rich rhenium slag after heavy rhenium.
After the quality (g) of described second precipitant and decopper(ing) the ratio of the volume (L) of liquid be preferably (2～
3): 1, those skilled in the art can select according to the practical situation of liquid composition after decopper(ing) and adjust second
Precipitant consumption.When, in liquid after described decopper(ing), copper content is 0g/L～0.1g/L, and be not 0, acid dense 0%～
When 20%, after the quality (g) of described second precipitant and decopper(ing), the ratio of the volume (L) of liquid is preferably
(2～3): 1；When, in liquid after described decopper(ing), copper content is 0g/L～0.1g/L, acid dense 20%～30%
Time, after the quality (g) of described second precipitant and decopper(ing) the ratio of the volume (L) of liquid be preferably (2.5～
3.5): 1；When, in liquid after described decopper(ing), copper content is 0.1g/L～0.2g/L, during acid dense 0%～20%,
After described second precipitant quality (g) and decopper(ing), volume (L) ratio of liquid is preferably (3～4): 1；
When, in liquid after described decopper(ing), copper content is 0.1g/L～0.2g/L, during acid dense 20%～30%, described second
After precipitant quality (g) and decopper(ing), volume (L) ratio of liquid is preferably (4～5): 1.
The temperature of described reaction is preferably 65～75 DEG C, and those skilled in the art can become according to liquid after decopper(ing)
The practical situation divided selects and adjusts reaction temperature.When in liquid after described decopper(ing), copper content be 0g/L～
0.1g/L, during acid dense 0%～20%, reaction temperature preferably 65～70 DEG C；When in liquid after described decopper(ing), copper
Content is 0g/L～0.1g/L, during acid dense 20%～30%, and reaction temperature preferably 65～68 DEG C；When described
After decopper(ing) in liquid, copper content is 0.1g/L～0.2g/L, acid dense 0%～20% time, reaction temperature preferably 68～
72℃；When, in liquid after described decopper(ing), copper content is 0.1g/L～0.2g/L, during acid dense 20%～30%, instead
Answer temperature preferably 72～75 DEG C.
The time of described reaction is preferably 45～70 minutes, and those skilled in the art can be according to liquid after decopper(ing)
The practical situation of composition selects and adjusts the response time.When in liquid after described decopper(ing), copper content be 0g/L～
0.1g/L, during acid dense 0%～20%, preferably 50～60 minutes response time；When in liquid after described decopper(ing),
Copper content is 0g/L～0.1g/L, during acid dense 20%～30%, and preferably 45～55 minutes response time；When
After described decopper(ing) in liquid, copper content is 0.1g/L～0.2g/L, and during acid dense 0%～20%, the response time is excellent
Select 55～65 minutes；When, in liquid after described decopper(ing), copper content is 0.1g/L～0.2g/L, acid dense 20%～
When 30%, preferably 65～70 minutes response time.
The present invention is operated by above-mentioned heavy rhenium, and after making decopper(ing), in liquid, the rhenium of 94.94%～99.53% is enriched to richness
Rhenium slag enters next step purify.
The present invention by above-mentioned substep sink copper rhenium operate, will be with being enriched with respectively, to rhenium therein
Follow-up employing different process carries out remove impurity recovery, and the response rate of copper is 95.3%～99.8%, and Rhenium recovery rate is
99%～99.53%.
When the clarification spent acid obtained is low copper clarification spent acid, in the most described clarification spent acid, copper content is more than 0,
During less than 0.2g/L, by described clarification spent acid and precipitant mix, directly obtain liquid and rich rhenium slag after heavy rhenium.
Precipitant is preferably (2～5) with the mass ratio of clarification spent acid: 1.
The temperature of above-mentioned reaction is preferably 65～75 DEG C, and the time of reaction is preferably 45～70 minutes.
The present invention sinks rhenium by an above-mentioned step and operates, and makes the rhenium of more than 99% in spent acid be enriched in rich rhenium slag
Enter next step to purify.
Liquid after the heavy rhenium that the present invention obtains, can enter spent acid processing center and process, will not give sulfate system
Bring any burden, and valuable metal copper is reclaimed indirectly in the process, serve good economy
Benefit and environmental benefit.
In the present invention, described first precipitant, the second precipitant, precipitant are sodium thiosulfate.
The present invention have employed the technique for reclaiming rhenium of sodium thiosulfate first, initially with the heavy copper rhenium of substep
Method, spent acid first decopper(ing), again sinks rhenium, is enriched to rhenium in heavy copper ashes and rich rhenium slag be separately recovered rhenium.
Can be good at solving the difficult enrichment of rhenium and subsequent treatment problem, simultaneously by heavy coppersmith during Rhenium recovery
Copper metal in spent acid is reclaimed by skill further, reclaims the valuable metal in spent acid to greatest extent
And utilization.
The present invention gives concrete control technique to low rhenium, high-copper, Rhenium recovery in the case of peracid is dense,
Reclaim rhenium effect preferable.
The present invention does not has any restriction to mentioned reagent source, can be that market is bought, or pass through ability
Field technique personnel's customary preparation methods prepares.
The present invention only uses sodium thiosulfate as precipitant, without other medicament, passes through technological operation
Controlling, precipitation and filter effect are good.
Mentioned reagent purity is not particularly limited by the present invention, the present invention preferably industry top grade product.
In order to further illustrate the present invention, the Copper making flue dust provided the present invention below in conjunction with embodiment is washed
Wash the recovery method of rhenium in spent acid to be described in detail.
Embodiment 1
1, spent acid filters
The spent acid of Copper making flue dust washing in spent acid storage tank is heated to 55 DEG C, and heat filtering, by heat filtering
Clarification spent acid carries out assay, and analysis result is shown in Table 1-1.
Table 1-1 clarification spent acid composition (g/L)
| Cu | Fe | As | Re | Mo | Se |
| 0.35 | 0.30 | 0.98 | 0.0077 | 0.012 | 0.027 |
After testing, clarification spent acid acid dense 8.5%.
2, decopper(ing) operation
The clarification spent acid obtained is heated to 65 DEG C, according to precipitant and cupric mass ratio in clarification spent acid
7.3:1 adds sodium thiosulfate, reacts 30 minutes, obtains liquid and heavy copper ashes after decopper(ing), enters liquid after decopper(ing)
Row component analysis, the results are shown in Table 1-2.
Liquid composition (g/L) after table 1-2 decopper(ing)
| Cu | Fe | As | Re | Mo | Se |
| 0.0096 | 0.28 | 0.96 | 0.007 | 0.010 | 0.0034 |
Copper extrusion rate 97.26% in liquid after decopper(ing), the Rhenium recovery rate 90.91% of heavy copper step, the rhenium of 9.09%
Entering after decopper(ing) slag enters next step point of copper and reclaim rhenium, after decopper(ing), liquid enters next step.
3, heavy rhenium operation
Liquid after decopper(ing) is heated to 70 DEG C, according to liquid long-pending (L) ratio after precipitant quality (g) and decopper(ing)
Example 3:1 adds sodium thiosulfate, reacts 60 minutes, obtains liquid and rich rhenium slag after heavy rhenium, to liquid after heavy rhenium
Carry out component analysis, the results are shown in Table 1-3.
Table 1-3 sinks liquid composition (g/L) after rhenium
| Cu | Fe | As | Re | Mo | Se |
| 0.0002 | 0.23 | 0.67 | 0.0001 | 0.0027 | <0.00050 |
Copper extrusion rate 97.92% in liquid, heavy rhenium Rhenium recovery rate 98.57% after heavy rhenium.After the heavy rhenium of gained, liquid returns
Returning sulfuric acid waste processing system, rich rhenium slag enters bottom operation, and the copper-contained tailings after rich rhenium slag carries rhenium returns molten
Refining system.
In sum, in described removal process, copper recovery 99.94%, decopper(ing) slag and rich rhenium slag enter respectively
Enter next step and reclaim rhenium, Rhenium recovery rate 98.7%.
Embodiment 2
1, spent acid filters
The spent acid of Copper making flue dust washing in spent acid storage tank is heated to 55 DEG C, and heat filtering, by heat filtering
Clarification spent acid carries out assay, and analysis result is shown in Table 2-1.
Table 2-1 clarification spent acid composition (g/L)
| Cu | Fe | As | Re | Mo | Se |
| 1.9 | 0.68 | 1.04 | 0.016 | 0.016 | 0.0078 |
After testing, clarification spent acid acid dense 15.3%.
2, decopper(ing) operation
The clarification spent acid obtained is heated to 61 DEG C, according to precipitant and cupric mass ratio in clarification spent acid
9:1 adds sodium thiosulfate, reacts 27 minutes, obtains liquid and heavy copper ashes after decopper(ing), carries out liquid after decopper(ing)
Component analysis, the results are shown in Table 2-2.
Liquid composition (g/L) after table 2-2 decopper(ing)
| Cu | Fe | As | Re | Mo | Se |
| 0.044 | 0.66 | 1.03 | 0.014 | 0.017 | <0.00050 |
Copper extrusion rate 97.68% in liquid after decopper(ing), the Rhenium recovery rate 87.5% of heavy copper step, the rhenium of 12.5% enters
Entering after decopper(ing) slag enters next step point of copper and reclaim rhenium, after decopper(ing), liquid enters next step.
3, heavy rhenium operation
Liquid after decopper(ing) is heated to 72 DEG C, according to liquid long-pending (L) ratio after precipitant quality (g) and decopper(ing)
Example 3:1 adds sodium thiosulfate, reacts 55 minutes, obtains liquid and rich rhenium slag after heavy rhenium, to liquid after heavy rhenium
Carry out component analysis, the results are shown in Table 2-3.
Liquid composition (g/L) after table 2-3 decopper(ing)
| Cu | Fe | As | Re | Mo | Se |
| 0.0029 | 0.67 | 1 | 0.0001 | 0.011 | <0.00050 |
Copper extrusion rate 93.41% in liquid, heavy rhenium Rhenium recovery rate 99.29% after heavy rhenium.After the heavy rhenium of gained, liquid returns
Returning sulfuric acid waste processing system, rich rhenium slag enters bottom operation and reclaims rhenium, and rich rhenium slag carries the cupric tail after rhenium
Slag returns smelting system.
In sum, in described removal process, copper recovery 99.85%, decopper(ing) slag and rich rhenium slag enter respectively
Enter next step and reclaim rhenium, Rhenium recovery rate 99.37%.
Embodiment 3
1, spent acid filters
The spent acid of Copper making flue dust washing in spent acid storage tank is heated to 55 DEG C, and heat filtering, by heat filtering
Clarification spent acid carries out assay, and analysis result is shown in Table 3-1.
Table 3-1 clarification spent acid composition (g/L)
| Cu | Fe | As | Re | Mo | Se |
| 0.0026 | 0.016 | 1.59 | 0.014 | 0.0023 | 0.034 |
After testing, clarification spent acid acid dense 7.1%.
2, heavy rhenium operation
Clarification spent acid is heated to 68 DEG C, according to precipitant quality (g) and clarification spent acid volume (L) ratio
Example 2.5:1 adds sodium thiosulfate, reacts 50 minutes, obtains liquid and rich rhenium slag after heavy rhenium, to liquid after heavy rhenium
Carry out component analysis, the results are shown in Table 3-2.
Table 3-2 sinks liquid composition (g/L) after rhenium
| Cu | Fe | As | Re | Mo | Se |
| 0.0001 | 0.013 | 1.29 | 0.0001 | 0.0013 | 0.0050 |
Copper recovery 96.15%, Rhenium recovery rate 99.29% in liquid after heavy rhenium.After the heavy rhenium of gained, liquid returns sulfur
Acid spent acid processing system, rich rhenium slag enters bottom operation, and the copper-contained tailings after rich rhenium slag carries rhenium returns melting system
System.
Copper recovery 96.15% in sum, Rhenium recovery rate 99.29%.
From above-described embodiment, the recovery method of rhenium in the Copper making flue dust washing spent acid that the present invention provides,
There is higher Rhenium recovery rate.
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.Should
Point out, for those skilled in the art, under the premise without departing from the principles of the invention,
The present invention can also be carried out some improvement and modification, these improve and modification also falls into right of the present invention and wants
In the protection domain asked.
Claims (10)
1. the recovery method of rhenium in a Copper making flue dust washing spent acid, it is characterised in that including:
A) Copper making flue dust washing spent acid is filtered, obtain clarifying spent acid and selenium mud；
B) by described clarification spent acid and the first precipitant mix, reaction, liquid and heavy copper ashes after decopper(ing) is obtained；
C) by liquid after described decopper(ing) and the second precipitant mix, reaction, liquid and rich rhenium slag after heavy rhenium is obtained；
In described clarification spent acid, copper content is 0.2g/L～3g/L；
Or including:
A) Copper making flue dust washing spent acid is filtered, obtain clarifying spent acid and selenium mud；
D) by described clarification spent acid and precipitant mix, reaction, liquid and rich rhenium slag after heavy rhenium is obtained；
In described clarification spent acid, copper content is more than 0, less than 0.2g/L.
Recovery method the most according to claim 1, it is characterised in that described first precipitant,
Two precipitant, precipitant are sodium thiosulfate.
Recovery method the most according to claim 1, it is characterised in that described step B) in, the
In the quality of one precipitant and clarification spent acid, the ratio containing copper mass is (6～10): 1.
Recovery method the most according to claim 1, it is characterised in that described step C) in, the
After two precipitant and decopper(ing), the mass ratio of liquid is (2～3): 1.
Recovery method the most according to claim 1, it is characterised in that described step D) in, heavy
Shallow lake agent is (2～5) with the mass ratio of clarification spent acid: 1.
Recovery method the most according to claim 1, it is characterised in that described step A) in, mistake
The temperature of filter is 50～60 DEG C.
Recovery method the most according to claim 1, it is characterised in that described step B) in, instead
The temperature answered is 60～65 DEG C, and the time of reaction is 25～35 minutes.
Recovery method the most according to claim 1, it is characterised in that described step C) in, instead
The temperature answered is 65～75 DEG C, and the time of reaction is 45～70 minutes.
Recovery method the most according to claim 1, it is characterised in that described step D) in, instead
The temperature answered is 65～75 DEG C, and the time of reaction is 45～70 minutes.
Recovery method the most according to claim 1, it is characterised in that described Copper making flue dust is washed
Washing spent acid to include: copper 0g/L～3g/L, rhenium is more than 1mg/L, arsenic 0g/L～5g/L, acid dense 0%～30%.
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| CN107299222A (en) * | 2017-06-28 | 2017-10-27 | 阳谷祥光铜业有限公司 | A kind of method that rhenium, copper, selenium and sulphur are reclaimed in rhenium concentrate |
| CN107354300A (en) * | 2017-07-19 | 2017-11-17 | 福州大学 | A kind of method of enriching rhenium in spent acid from Copper making |
| CN109626414A (en) * | 2019-01-31 | 2019-04-16 | 广州大学 | A method of thallium and rhenium being recycled in waste acid from smelting |
| CN110468277A (en) * | 2019-09-05 | 2019-11-19 | 紫金矿业集团股份有限公司 | The method of rhenium is recycled from Copper making waste acid |
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