CN102502855A - Method for preparing ammonium perrhenate through extracting from coppersmelting exhaust gas washing acid pickle - Google Patents
Method for preparing ammonium perrhenate through extracting from coppersmelting exhaust gas washing acid pickle Download PDFInfo
- Publication number
- CN102502855A CN102502855A CN2011103391342A CN201110339134A CN102502855A CN 102502855 A CN102502855 A CN 102502855A CN 2011103391342 A CN2011103391342 A CN 2011103391342A CN 201110339134 A CN201110339134 A CN 201110339134A CN 102502855 A CN102502855 A CN 102502855A
- Authority
- CN
- China
- Prior art keywords
- rhenium
- washing
- coordination
- phase
- extraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for preparing ammonium perrhenate through extracting from coppersmelting exhaust gas washing acid pickle, which comprises the following steps: extracting and phase-in enriching rhenium for two times through an organic solvent extraction process; using coordination detergent and pure water to wash and purify a loaded organic phase containing rhenium for two times, strip-extracting ammonia rhenium, and finally adding few phase of regulating agent in strip liquor containing rhenium to carry out phase separation and organic phase removal so as to obtain secondary strip liquor containing rhenium with high concentration; and carrying out procedures such as concentration, refrigeration and crystallization to produce ammonium perrhenate crystals with the grade being greater than 98.00 percent. The method is characterized in that: metals such as metal rhenium are extracted through the organic solvent extraction process, and the coordination detergent is used for cleaning and purifying the loaded organic phase containing the rhenium without causing loss of the rhenium; and the process is simple and feasible, the adaptability of raw materials is strong, and the recovery rate is high.
Description
The (1) technical field: the present invention relates to a kind of process method for preparing ammonium perrhenate, specifically is that a kind of the washing from the copper flue gas during smelting extracted the method for preparing ammonium perrhenate the spent acid solution.
The (2) background technology: present domestic preparation ammonium perrhenate product mainly adopts organic solvent extractionprocess, the precipitator method or ion exchange method.For rhenium content higher (minimum reaching more than the 0.015g/L), the rhenium-containing material that impurity component is simple and content is low can obtain the rhenium-containing product than higher-grade through organic solvent extractionprocess, and the science and engineering skill is ripe here.For example: Jiangxi Copper adopts N
235, secondary octanol, kerosene mixed organic solvents rhenium-containing 0.2 ~ 0.3g/L, polynary mixed acid system that foreign matter content is low extracted produce the ammonium perrhenate crystal; The molybdenum rhenium calcine pickle liquor of the about 0.5g/L of rhenium-containing of Dexing copper mine adopts identical organic solvent to extract, and makes the ammonium perrhenate crystal.In the above production technique, the rhenium-containing feed liquid of processing wherein is mainly the influence of molybdenum impurity, and other metal impurity components are simple and more single, and removal of impurities is easier to; But do not relate to the purification and impurity removal research of other metals in the whole extraction process.The simple rhenium-containing material low for rhenium content, that impurity component is few generally adopts traditional precipitator method or ion exchange method etc. to carry out purification and impurity removal.The precipitator method only have stronger removal ability to certain metal, and range of application is narrower, are difficult to accomplish a step removal of impurities; The ion exchange method range of application is wider, but is difficult to make rhenium to separate fully with other foreign metals, and is prone to cause the dispersion of rhenium, causes the rhenium recovery low.
And to the special rhenium-containing material that rhenium content is low, impurity component is complicated, as the copper flue gas during smelting that the present invention relates to washing spent acid solution, wherein there are polyprotonic acid and a large amount of foreign metal ion, system is complicated and changeable.This solution rhenium-containing concentration is about 6ppm; And foreign metal content such as other Bi, Cd, Zn, As, Cu, Mo, Te, Se are all big than rhenium height and fluctuation; The hundred times of that have or even rhenium content, and also contain higher F, Cl ion and sulfur dioxide gas in the solution.Therefore, utilize aforesaid method to be difficult to obtain rhenium-containing product than higher-grade.Because N
235But the rhenium of extraction agent enriching low-concentration, and the most metal negatively charged ion had effect of extracting preferably.Use N
235Rhenium in the extraction agent extracting copper flue gas during smelting washing spent acid solution is also feasible, but because rhenium concentration is low, not high with the separation factor of other metals, N
235Extraction agent in the enrichment rhenium also enrichment a large amount of foreign metals, especially to a large amount of enrichments of foreign metals such as Bi, Cd, As, Zn.The back extraction slag causes organic solvent, slag, the water three-phase is difficult separates because of a large amount of foreign metal ion hydrolysis generate in ammoniacal liquor back extraction process; And the organic extracted species of part is dissolved in the loss that has caused organic solvent in the strip liquor because of hydrophilic phenomenon appears in excessive concentration, finally causes the ammonium perrhenate product grade low, unstable.And the precipitator method or ion exchange method are difficult to make rhenium to separate fully with other foreign metals.So, to the singularity and the complicacy of copper flue gas during smelting of the present invention washing spent acid solution, find out rhenium is separated with other foreign metals fully, and the purifying and impurity-removing method of intermediate product, be the key point that can decision obtain the higher-grade ammonium perrhenate.
The (3) summary of the invention: the object of the invention just provides a kind of the washing from the copper flue gas during smelting and extracts the method for preparing ammonium perrhenate the spent acid solution; This method extracts enrichment rhenium stage by stage for twice with organic solvent extractionprocess; With coordination washing composition, pure water the rhenium-containing load organic phases is carried out washing impurity-removing respectively twice again; Carry out the rhenium back extraction with ammoniacal liquor again, in the rhenium-containing strip liquor, add the secondary that a small amount of phase modifier carries out obtaining at last after the phase-splitting high density and be rich in the rhenium anti-stripping agent; Concentrate respectively again, operation such as freezing, recrystallization produces qualified ammonium perrhenate product; Preferably resolve prior art and use N
235Extraction agent in the enrichment rhenium also enrichment a large amount of foreign metals; The back extraction slag causes organic solvent, slag, the water three-phase is difficult separates because of a large amount of foreign metal ion hydrolysis generate in ammoniacal liquor back extraction process; And the organic extracted species of part is dissolved in the loss that has caused organic solvent in the strip liquor because of hydrophilic phenomenon appears in excessive concentration, and causes low, the problem of unstable of ammonium perrhenate product grade.
The inventive method comprises the steps:
(1) single extraction
In rhenium-containing material copper flue gas during smelting washing spent acid solution, add mixed organic solvents, three stage countercurrents extraction under the normal temperature, extraction conditions is: comparing O/A is 1/3-1/5, and the time of mixing is 5min, and starting time is 15min; Phase-splitting keeps the rhenium-containing load organic phases, and raffinate is done WWT; The volume percent of used mixed organic solvents component is: 10-20%N
235, the secondary octanol of 30-40%, 40-60% sulfonated kerosene;
(2) coordination washings, pure water washing:
Earlier the last step is separated the rhenium-containing load organic phases that obtains and carry out the coordination washing;
The coordination wash conditions is: comparing O/A is 1/1-1/2, and normal temperature is washing down; Mixing time is 5min, and starting time is 15min, phase-splitting; Keep the rhenium-containing load organic phases; The liquid recycling of coordination washing back; Said coordination washing composition is for containing EDTA 0.1-1.5mol/L and (NH
4)
2SO
40.2-2mol/L mixed solution; Described coordination washing composition pH of mixed must be controlled to be 5-7; Coordination washing process pH must be controlled to be 3-6.5;
The rhenium-containing load organic phases that again the coordination washing is obtained is carried out the pure water washing;
The pure water wash conditions is: comparing O/A is 1/1-1/2, and normal temperature is washing down, and mixing time is 5min, and starting time is 10min, phase-splitting; Keep the rhenium-containing load organic phases; Pure water washing back liquid is done WWT;
(3) back extractions also purify except that organic phase:
Rhenium-containing load organic phases to obtaining after the pure water washing of last step is carried out back extraction;
The back extraction condition is: make reverse-extraction agent with ammoniacal liquor, comparing O/A is 3/1-5/1, back extraction under the normal temperature, and mixing time is 5min, starting time is 30min; Phase-splitting; Keep the rhenium-containing strip liquor, anti-raffinate is an organic phase, returns and utilizes; Reverse-extraction agent ammoniacal liquor volume(tric)fraction is 10-15%;
In the rhenium-containing strip liquor that obtains, adding volume(tric)fraction is the secondary octanol of 3-10%, and mixing time is 5min, and starting time is 30min, phase-splitting; Keep a rhenium-containing strip liquor that does not contain organic phase; Organic phase is then returned and is utilized;
(4) reextraction, washing, back extraction reach and remove organic phase
Gained of last step is left standstill 20h to slightly acidic except that a rhenium-containing strip liquor after the organic phase; Extraction, washing, the back extraction of carrying out above-mentioned (1) (2) (3) step more respectively remove the organic phase operation; Finally obtain high density secondary rhenium-containing strip liquor, it is following that each goes on foot operational condition:
Extraction conditions is: comparing O/A is 1/3-1/5, and the time of mixing is 3min, and starting time is 15min; The volume percent of used mixed organic solvents component is: 20%N
235, 40% secondary octanol, 40% sulfonated kerosene; Mixed organic solvents in this step needs to be acidified to pH ﹤ 1 with dilute sulphuric acid earlier;
The coordination wash conditions is: comparing O/A is 1/1-1/2, and normal temperature is washing down; Mixing time is 5min, and starting time is 15min, and said coordination washing composition is for containing EDTA 0.1-0.2 mol/L and (NH
4)
2SO
40.2-0.5mol/L mixed solution;
The pure water wash conditions is: compare O/A and be the washing down of 1/1-1/2 normal temperature, mixing time is 5min, and starting time is 10min;
Back extraction removes the organic phase condition: make reverse-extraction agent with ammoniacal liquor, comparing O/A is 3/1-5/1, back extraction under the normal temperature, and mixing time is 5min, starting time is 30min; Reverse-extraction agent ammoniacal liquor massfraction is 10-15%;
In the high density secondary rhenium-containing strip liquor that obtains, add the secondary octanol that volume(tric)fraction is 3%-5% again, the time of mixing is 3min, and starting time is 30min; Phase-splitting; Keep the high density secondary rhenium-containing strip liquor that does not contain organic phase; Organic phase is then returned and is utilized;
(5) concentrated frozen crystallization
The resulting high density secondary of step (4) rhenium-containing strip liquor is carried out the concentrated frozen crystallization, and its processing condition are: thickening temperature is 90～95 ℃, and liquid concentrator volume/concentrate back liquid to amass=2～5/1 adds ammoniacal liquor after concentrating and regulates pH to 8-9; Freezing 18h under≤0 ℃ of condition; Dry 12-24h under≤100 ℃ of conditions promptly gets grade and is＞98.00% ammonium perrhenate crystal.
Described coordination washing composition mixed solution uses ammoniacal liquor adjusting pH to be 5-7.
The extraction agent N that uses in the inventive method
235Through with rhenium-containing material spent acid solution mixing acidifying after with rehenic acid root and other foreign metal coordination ions [M (SO
4)
m N-] take place to react as follows:
N
235Extraction agent has also extracted other foreign metal ions in the extraction rhenium.From the rhenium-containing load organic phases, remove the foreign metal ion, just must use a kind of reagent and foreign metal ion to form more by force more stable compound, extractive reaction is reverse to carry out thereby make, and does not cause the influence to rhenium.This reagent is the EDAT coordination agent, and its coordination reaction is:
The mole proportioning that
EDTA coordination agent and metals ion form stable complex is generally 1:1, and minute quantity is 1:2; Can confirm the concentration of coordination agent according to the foreign metal ion content, add-on is slightly larger than theoretical amount and gets final product.With reference to the sour effect curve of coordination agent EDTA, calculate the coordination equilibrium constant of itself and metals ion, draw the minimum pH value that forms the stable metal title complex, thereby be implemented under this pH coordination washing removal this metal.Therefore it is very crucial to foreign metal ionic washing removal to control the concentration of coordination agent in this coordination washing composition and the pH value in the washing process.
In order to keep the stability of solution, need to add a certain amount of buffer reagent, buffer reagent is (NH
4)
2SO
4, regulate the pH value of coordination washing composition through adding a spot of ammoniacal liquor again.Coordination agent EDTA concentration range is 0.1-1.5mol/L in the coordination washing composition, buffer reagent (NH
4)
2SO
4Concentration range be 0.2-2mol/L.Respectively to once, secondary rhenium-containing load organic phases carries out the washing of coordination washing, pure water, guarantees that rhenium separates with other foreign metal ionic.
For the title complex of avoiding having partial impurities metals ion and EDTA to form after the coordination washing is mixed in the organic solvent, it is mingled with the influence of avoiding follow-up back extraction then need to carry out pure water washing removal.
With weak ammonia the rhenium-containing load organic phases is carried out back extraction, reacts as follows:
Because of N
235Selection of Extractant property is very greatly very wide, in the enrichment rhenium also enrichment other foreign metal ion, cause the part metals extracted species to be dissolved in the strip liquor.Salting-out agent can be added or phase modifier improves to this type of situation; But for avoiding the secondary pollution and the economic consideration of foreign ion; Select to add this phase modifier of secondary octanol at last and handle, do not contained the strip liquor of organic phase and the back extraction dissolving organic phase of easy phase-splitting.
Purifying when removing organic phase, is the phase modifier-secondary octanol that in the rhenium-containing strip liquor, adds 3-10% (volume ratio), occurs noted phase separation phenomena after the stirring.This scheme can be separated out the organic phase in the rhenium-containing strip liquor and separates from strip liquor, thereby realizes the purification oil removing (organic phase) of rhenium-containing strip liquor.
The present invention has advantages of simple technological process, characteristics such as flexible and convenient operation; And can in a big way, (non-alkaline environment) realize Bi, Sn
2+, As, Cd, Al, Zn, Cu, Ni, Co, Ti
3+, Pb, Fe
3+, Fe
2+Etc. a certain proportion of removal of most of metals ion.If foreign metal concentration is higher and have a recovery value in the liquid of coordination washing back, adds sulphur reagent etc. behind the certain pH of adjustable and precipitate recovery.Realize the purification separation of closed cycle, foreign metal open circuit, dissolving organic solvent and the rhenium-containing strip liquor of rhenium in the whole technology, technological process and product have all been played the effect of purification and impurity removal, finally obtained high-grade ammonium perrhenate product.
The (4) description of drawings
Fig. 1 is a process flow diagram of the present invention.
The (5) embodiment
Embodiment 1
In the present embodiment in the handled rhenium-containing material copper flue gas during smelting washing spent acid solution chemical ingredients be (g/L): Re 0.006, Zn 0.652, Bi 0.43, Cd 0.66, As 0.129, Cu 0.273, Mo 0.065, Al 0.045 etc.; The technical scheme of taking to this rhenium-containing material is following:
(1) single extraction
In rhenium-containing material copper flue gas during smelting washing spent acid solution, add mixed organic solvents, three stage countercurrents extraction under the normal temperature, extraction conditions is: comparing O/A is 1/5, and the time of mixing is 5min, and starting time is 15min; Phase-splitting keeps the rhenium-containing load organic phases, and raffinate is done WWT; The volume percent of used mixed organic solvents component is: 15%N
235, 35% secondary octanol, 50% sulfonated kerosene;
(2) coordination washings, pure water washing:
The chemical ingredients of the rhenium-containing load organic phases of gained is (g/L): Re 0.652, and Zn 0.863, and Bi 3.538, and Cd 0.88, and As 0.094, and Cu 0.039, Al 0.056 etc.;
Earlier this rhenium-containing load organic phases is carried out the coordination washing; The coordination wash conditions is: comparing O/A is 1/2, and normal temperature is washing down; Mixing time is 5min, and starting time is 15min, phase-splitting; Keep the rhenium-containing load organic phases; The liquid recycling of coordination washing back; Said coordination washing composition is for containing EDTA 0.1mol/L and (NH
4)
2SO
40.2mol/L mixed solution; Described coordination washing composition pH of mixed is controlled to be 6; Coordination washing process pH is controlled to be 4.5;
The rhenium-containing load organic phases that again the coordination washing is obtained is carried out the pure water washing; The pure water wash conditions is: comparing O/A is 1/1, and normal temperature is washing down, and washing process pH is about 5, and mixing time is 5min, and starting time is 10min, phase-splitting; The branch phase velocity is fast and two-phase interface is clear; Keep the rhenium-containing load organic phases; Pure water washing back liquid is done WWT;
To analyzing the impurities removing efficiency (%) that draws following metal through the rhenium-containing load organic phases after the coordination washing: Zn 95.70, and Bi 95.20, and Cd 92.68, and As 80.56, and Cu 61.83, and Al 84.1, and the rhenium free of losses; Carry out pure water washing again, the rhenium rate of loss is 0.15%, and other metals content impurities are all reduced to the rank of 10ppm, thereby can realize that the back extraction process do not have the back extraction slag, and rhenium and other foreign metal ion isolation are complete;
(3) back extractions also purify except that organic phase:
Rhenium-containing load organic phases to obtaining after the pure water washing of last step is carried out back extraction;
The back extraction condition is: make reverse-extraction agent with ammoniacal liquor, comparing O/A is 3.5/1, back extraction under the normal temperature, and mixing time is 5min, starting time is 30min; Phase-splitting; Keep the rhenium-containing strip liquor, anti-raffinate is an organic phase, returns and utilizes; Reverse-extraction agent ammoniacal liquor massfraction is 12%;
The adding volume(tric)fraction is 5% secondary octanol in the rhenium-containing strip liquor that obtains, and mixing time is 5min, and starting time is 30min, phase-splitting; The branch phase velocity is fast and two-phase interface is clear.Can calculate that the dissolved organic phase is about 19% (volume ratio) in this rhenium-containing strip liquor;
Keep a rhenium-containing strip liquor that does not contain organic phase; Organic phase is then returned and is utilized;
(4) reextraction, washing, back extraction remove organic phase
Gained of last step is left standstill 20h to slightly acidic except that a rhenium-containing strip liquor after the organic phase; Extraction, washing, the back extraction of carrying out above-mentioned (1) (2) (3) step more respectively remove the organic phase operation; Finally obtain high density secondary rhenium-containing strip liquor, it is following that each goes on foot operational condition:
Extraction conditions is: comparing O/A is 1/4.5, and the time of mixing is 3min, and starting time is 15min; The volume percent of used mixed organic solvents component is: 20%N
235, 40% secondary octanol, 40% sulfonated kerosene; Mixed organic solvents in this step needs to be acidified to pH ﹤ 1 with dilute sulphuric acid earlier; The souring operation step: adding massfraction at mixed organic solvents is 5% dilute sulphuric acid, and comparing O/A is 2/1, and the time of mixing is 3min, and starting time is 15min, phase-splitting, and diluted acid water discards, and the organic phase of reservation is mixed organic solvents after the acidifying of pH ﹤ 1.
The coordination wash conditions is: comparing O/A is 1/1, and normal temperature is washing down; Mixing time is 5min, and starting time is 15min, and said coordination washing composition is for containing EDTA 0.1mol/L and (NH
4)
2SO
40.2mol/L mixed solution; Described coordination washing composition pH of mixed is controlled to be 6; Coordination washing process pH is controlled to be 5.5; Washing process does not have visible slag and occurs, and the branch phase velocity is fast and two-phase interface is clear.
The pure water wash conditions is: comparing O/A is 1/1, and normal temperature is washing down, and washing process pH is 5min for the 6-6.5 mixing time, and starting time is 10min; Washing process does not have visible slag and occurs, and the branch phase velocity is fast and two-phase interface is clear.
Back extraction removes the organic phase condition: make reverse-extraction agent with ammoniacal liquor, comparing O/A is 3.5/1, back extraction under the normal temperature, and mixing time is 5min, starting time is 30min; Reverse-extraction agent ammoniacal liquor massfraction is 15%;
In the high density secondary rhenium-containing strip liquor that obtains, add volume(tric)fraction again and be 3% secondary octanol, the time of mixing is 3min, and starting time is 30min; Phase-splitting; The branch phase velocity is fast and two-phase interface is clear.Can calculate that the dissolved organic phase is about 5% (volume ratio) in this secondary rhenium-containing strip liquor.Keep the high density secondary rhenium-containing strip liquor that does not contain organic phase; Organic phase is then returned and is utilized;
(5) concentrated frozen crystallization
The resulting high density secondary of step (4) rhenium-containing strip liquor chemical ingredients is (mg/L): Re 16310 as follows, and Zn 7, and Bi 5, and Cd 2, and As 3, and Cu 9, organic phase＜50.Wherein rhenium rate of loss＜0.5% carries out the concentrated frozen crystallization with this solution, and its processing condition are: thickening temperature is 95 ℃, and liquid concentrator volume/concentrate back liquid to amass=2/1 adds ammoniacal liquor after concentrating and regulates pH to 8; Freezing 18h under≤0 ℃ of condition; Dry 20h under≤100 ℃ of conditions promptly gets grade and is 98.86% ammonium perrhenate crystal.
Embodiment 2
In the present embodiment in the handled rhenium-containing material copper flue gas during smelting washing spent acid solution chemical ingredients be (g/L): Re 0.007, Zn 2.352, Bi 1.34, Cd 1.116, As 2.506, Cu 4.371, Mo 0.012, Fe 0.318, Al 0.011 etc.
The technical scheme of taking to this rhenium-containing material is following:
(1) single extraction
In rhenium-containing material copper flue gas during smelting washing spent acid solution, add mixed organic solvents, three stage countercurrents extraction under the normal temperature, extraction conditions is: comparing O/A is 1/3, and the time of mixing is 5min, and starting time is 15min; Phase-splitting keeps the rhenium-containing load organic phases, and raffinate is done WWT; The volume percent of used mixed organic solvents component is: 20%N
235, 40% secondary octanol, 40% sulfonated kerosene;
(2) coordination washings, pure water washing:
The chemical ingredients of the rhenium-containing load organic phases of gained is (g/L): Re 0.689, and Zn 3.218, and Bi 28.775, and Cd 4.326, and As 0.063, and Cu 0.239, and Fe 0.023, and Al 0.068, Mo 0.006 etc.;
Earlier this rhenium-containing load organic phases is carried out the coordination washing; The coordination wash conditions is: comparing O/A is 1/2, and normal temperature is washing down; Mixing time is 5min, and starting time is 15min, phase-splitting; Keep the rhenium-containing load organic phases; The liquid recycling of coordination washing back; Said coordination washing composition is for containing EDTA 0.8mol/L and (NH
4)
2SO
41.0mol/L mixed solution; Described coordination washing composition pH of mixed is controlled to be 6; Coordination washing process pH is controlled to be 5;
The rhenium-containing load organic phases that again the coordination washing is obtained is carried out the pure water washing;
The pure water wash conditions is: comparing O/A is 1/2, and normal temperature is washing down, and washing process pH is about 5, and mixing time is 5min, and starting time is 10min, phase-splitting; The branch phase velocity is fast and two-phase interface is clear; Keep the rhenium-containing load organic phases; Pure water washing back liquid is done WWT;
To analyzing the impurities removing efficiency (%) that draws following metal through the rhenium-containing load organic phases after the coordination washing: Zn 98.31, and Bi 98.92, and Cd 97.11, and As 87.27, and Cu 90.53, and Fe 75.24%, and Al 84.16%, and the rhenium rate of loss is 0.41%; Carry out pure water washing again, the rhenium rate of loss is 0.03%, and other metals content impurities are all reduced to the rank of 10ppm, thereby can realize that the back extraction process do not have the back extraction slag, and rhenium and other foreign metal ion isolation are complete;
(3) back extractions also purify except that organic phase:
Rhenium-containing load organic phases to obtaining after the pure water washing of last step is carried out back extraction;
The back extraction condition is: make reverse-extraction agent with ammoniacal liquor, comparing O/A is 4/1, back extraction under the normal temperature, and mixing time is 5min, starting time is 30min; Phase-splitting; Keep the rhenium-containing strip liquor, anti-raffinate is an organic phase, returns and utilizes; Reverse-extraction agent ammoniacal liquor massfraction is 12%;
The adding volume(tric)fraction is 4.5% secondary octanol in the rhenium-containing strip liquor that obtains, and mixing time is 5min, and starting time is 30min, phase-splitting; The branch phase velocity is fast and two-phase interface is clear.Can calculate that the dissolved organic phase is about 18% (volume ratio) in this rhenium-containing strip liquor.
Keep a rhenium-containing strip liquor that does not contain organic phase; Organic phase is then returned and is utilized;
(4) reextraction, washing, back extraction remove organic phase
Gained of last step is left standstill 20h to slightly acidic except that a rhenium-containing strip liquor after the organic phase; Extraction, washing, the back extraction of carrying out above-mentioned (1) (2) (3) step more respectively remove the organic phase operation; Finally obtain high density secondary rhenium-containing strip liquor, it is following that each goes on foot operational condition:
Extraction conditions is: comparing O/A is 1/3.5, and the time of mixing is 3min, and starting time is 15min; The volume percent of used mixed organic solvents component is: 20%N
235, 40% secondary octanol, 40% sulfonated kerosene; Mixed organic solvents in this step needs to be acidified to pH ﹤ 1 with dilute sulphuric acid earlier; The souring operation step: adding massfraction at mixed organic solvents is 15% dilute sulphuric acid, and comparing O/A is 2/1, and the time of mixing is 3min, and starting time is 15min, phase-splitting, and diluted acid water discards, and the organic phase of reservation is the organic phase after the acidifying of pH ﹤ 1;
The coordination wash conditions is: comparing O/A is 1/1, and normal temperature is washing down; Mixing time is 5min, and starting time is 15min, and said coordination washing composition is for containing EDTA 0.1mol/L and (NH
4)
2SO
40.4mol/L mixed solution; Described coordination washing composition pH of mixed is controlled to be 6.5; Coordination washing process pH is controlled to be 5.0; Washing process does not have visible slag and occurs, and the branch phase velocity is fast and two-phase interface is clear;
The pure water wash conditions is: comparing O/A is 1/1, and normal temperature is washing down, and washing process pH is 6, and mixing time is 5min, and starting time is 10min; Washing process does not have visible slag and occurs, and the branch phase velocity is fast and two-phase interface is clear;
Back extraction removes the organic phase condition: make reverse-extraction agent with ammoniacal liquor, comparing O/A is 3.5/1, back extraction under the normal temperature, and mixing time is 5min, starting time is 30min; Reverse-extraction agent ammoniacal liquor massfraction is 12%;
In the high density secondary rhenium-containing strip liquor that obtains, add volume(tric)fraction again and be 3% secondary octanol, the time of mixing is 3min, and starting time is 30min; Phase-splitting; The branch phase velocity is fast and two-phase interface is clear.Can calculate that the dissolved organic phase is about 5% (volume ratio) in this secondary rhenium-containing strip liquor.Keep the high density secondary rhenium-containing strip liquor that does not contain organic phase; Organic phase is then returned and is utilized;
(5) concentrated frozen crystallization
The resulting high density secondary of step (4) rhenium-containing strip liquor chemical ingredients is (mg/L): Re 14780 as follows, and Zn 11, and Bi 3, and Cd 2, and As 8, and Cu 9, and Se 10, and Fe 2, and Al 2, organic phase＜50.Wherein rhenium rate of loss＜0.5% carries out the concentrated frozen crystallization with this solution, and its processing condition are: thickening temperature is 90 ℃, and liquid concentrator volume/concentrate back liquid to amass=2/1 adds ammoniacal liquor after concentrating and regulates pH to 8.5; Freezing 18h under≤0 ℃ of condition; Dry 18h under≤100 ℃ of conditions promptly gets grade and is 98.07% ammonium perrhenate crystal.
Embodiment 3
In the present embodiment in the handled rhenium-containing material copper flue gas during smelting washing spent acid solution chemical ingredients be (g/L): Re 0.006, Zn 1.367, Bi 0.87, Cd 1.069, As 1.378, Cu 2.566, Mo 0.027, Fe 0.106, Al 0.078 etc.
The technical scheme of taking to this rhenium-containing material is following:
(1) single extraction
In rhenium-containing material copper flue gas during smelting washing spent acid solution, add mixed organic solvents, three stage countercurrents extraction under the normal temperature, extraction conditions is: comparing O/A is 1/5, and the time of mixing is 5min, and starting time is 15min; Phase-splitting keeps the rhenium-containing load organic phases, and raffinate is done WWT; The volume percent of used mixed organic solvents component is: 20%N
235, 40% secondary octanol, 40% sulfonated kerosene;
(2) coordination washings, pure water washing:
The chemical ingredients of the rhenium-containing load organic phases of gained is (g/L): Re 0.676, and Zn 2.173, and Bi 16.579, and Cd 4.165, and As 0.082, and Cu 0.188, and Fe 0.037, Al 0.033 etc.;
Earlier this rhenium-containing load organic phases is carried out the coordination washing.The coordination wash conditions is: comparing O/A is 1/2, and normal temperature is washing down; Mixing time is 5min, and starting time is 15min, phase-splitting; Keep the rhenium-containing load organic phases; The liquid recycling of coordination washing back; Said coordination washing composition is for containing EDTA 0.5mol/L and (NH
4)
2SO
41.0mol/L mixed solution; Described coordination washing composition pH of mixed is controlled to be 6; Coordination washing process pH is controlled to be 4.5;
The rhenium-containing load organic phases that again the coordination washing is obtained is carried out the pure water washing;
The pure water wash conditions is: comparing O/A is 1/2, and normal temperature is washing down, and washing process pH is about 5.5, and mixing time is 5min, and starting time is 10min, phase-splitting; The branch phase velocity is fast and two-phase interface is clear; Keep the rhenium-containing load organic phases; Pure water washing back liquid is done WWT;
To analyzing the impurities removing efficiency (%) that draws following metal through the rhenium-containing load organic phases after the coordination washing: Zn 98.62, and Bi 99.88, and Cd 99.16, and As 89.02, and Cu 90.96, and Fe 75.68, and Al 75.76, and the rhenium rate of loss is 0.3%; Carry out pure water washing again, the rhenium free of losses, other metals content impurities are all reduced to the rank of 10ppm, thereby can realize that the back extraction process do not have the back extraction slag, and rhenium and other foreign metal ion isolation are complete;
(3) back extractions also purify except that organic phase:
Rhenium-containing load organic phases to obtaining after the pure water washing of last step is carried out back extraction;
The back extraction condition is: make reverse-extraction agent with ammoniacal liquor, comparing O/A is 3/1, back extraction under the normal temperature, and mixing time is 5min, starting time is 30min; Phase-splitting; Keep the rhenium-containing strip liquor, anti-raffinate is an organic phase, returns and utilizes; Reverse-extraction agent ammoniacal liquor massfraction is 15%;
The adding volume(tric)fraction is 3% secondary octanol in the rhenium-containing strip liquor that obtains, and mixing time is 5min, and starting time is 30min, phase-splitting; The branch phase velocity is fast and two-phase interface is clear.Can calculate that the dissolved organic phase is about 15% (volume ratio) in this rhenium-containing strip liquor;
Keep a rhenium-containing strip liquor that does not contain organic phase; Organic phase is then returned and is utilized;
(4) reextraction, washing, back extraction remove organic phase
Gained of last step is left standstill 20h to slightly acidic except that a rhenium-containing strip liquor after the organic phase; Extraction, washing, the back extraction of carrying out above-mentioned (1) (2) (3) step more respectively remove the organic phase operation; Finally obtain high density secondary rhenium-containing strip liquor, it is following that each goes on foot operational condition:
Extraction conditions is: comparing O/A is 1/5, and the time of mixing is 3min, and starting time is 15min; The volume percent of used mixed organic solvents component is: 20%N
235, 40% secondary octanol, 40% sulfonated kerosene; Mixed organic solvents in this step needs to be acidified to pH ﹤ 1 with dilute sulphuric acid earlier; The souring operation step: adding massfraction at mixed organic solvents is 15% dilute sulphuric acid, and comparing O/A is 2/1, and the time of mixing is 3min, and starting time is 15min, phase-splitting, and diluted acid water discards, and the organic phase of reservation is the organic phase after the acidifying of pH ﹤ 1;
The coordination wash conditions is: comparing O/A is 1/2, and normal temperature is washing down; Mixing time is 5min, and starting time is 15min, and said coordination washing composition is for containing EDTA 0.1mol/L and (NH
4)
2SO
40.4mol/L mixed solution; Described coordination washing composition pH of mixed is controlled to be 6; Coordination washing process pH is controlled to be 5.0; Washing process does not have visible slag and occurs, and the branch phase velocity is fast and two-phase interface is clear;
The pure water wash conditions is: comparing O/A is 1/2, and normal temperature is washing down, and washing process pH is 5min for the 6-6.5 mixing time, and starting time is 10min; Washing process does not have visible slag and occurs, and the branch phase velocity is fast and two-phase interface is clear;
Back extraction removes the organic phase condition: make reverse-extraction agent with ammoniacal liquor, comparing O/A is 3.5/1, back extraction under the normal temperature, and mixing time is 5min, starting time is 30min; Reverse-extraction agent ammoniacal liquor massfraction is 12%;
In the high density secondary rhenium-containing strip liquor that obtains, add volume(tric)fraction again and be 3% secondary octanol, the time of mixing is 3min, and starting time is 30min; Phase-splitting; The branch phase velocity is fast and two-phase interface is clear.Can calculate that the dissolved organic phase is about 5% (volume ratio) in this secondary rhenium-containing strip liquor.Keep the high density secondary rhenium-containing strip liquor that does not contain organic phase; Organic phase is then returned and is utilized;
(5) concentrated frozen crystallization
The resulting high density secondary of step (4) rhenium-containing strip liquor chemical ingredients is (mg/L): Re 15044 as follows, and Zn 9, and Bi 1, and Cd 2, and As 5, and Cu 7, and Fe 3, and Al 1, organic phase＜50.Wherein rhenium rate of loss＜0.5% carries out the concentrated frozen crystallization with this solution, and its processing condition are: thickening temperature is 90 ℃, and liquid concentrator volume/concentrate back liquid to amass=2/1 adds ammoniacal liquor after concentrating and regulates pH to 8.5; Freezing 18h under≤0 ℃ of condition; Dry 18h under≤100 ℃ of conditions promptly gets grade and is 98.34% ammonium perrhenate crystal.
Embodiment 4
In the present embodiment in the handled rhenium-containing material copper flue gas during smelting washing spent acid solution chemical ingredients be (g/L): Re 0.007, Zn 0.684, Bi 1.47, Cd 0.266, As 1.311, Cu 0.857, Mo 0.026, Fe 0.272, Al 0.058 etc.
The technical scheme of taking to this rhenium-containing material is following:
(1) single extraction
In rhenium-containing material copper flue gas during smelting washing spent acid solution, add mixed organic solvents, three stage countercurrents extraction under the normal temperature, extraction conditions is: comparing O/A is 1/4, and the time of mixing is 5min, and starting time is 15min; Phase-splitting keeps the rhenium-containing load organic phases, and raffinate is done WWT; The volume percent of used mixed organic solvents component is: 20%N
235, 40% secondary octanol, 40% sulfonated kerosene;
(2) coordination washings, pure water washing:
The chemical ingredients of the rhenium-containing load organic phases of gained is (g/L): Re 0.657, and Zn 1.796, and Bi 25.145, and Cd 4.566, and As 0.042, and Cu 0.107, and Fe 0.049, and Al 0.026, Mo 0.016 etc.;
Earlier this rhenium-containing load organic phases is carried out the coordination washing.The coordination wash conditions is: comparing O/A is 1/1, and normal temperature is washing down; Mixing time is 5min, and starting time is 15min, phase-splitting; Keep the rhenium-containing load organic phases; The liquid recycling of coordination washing back; Said coordination washing composition is for containing EDTA 1.5mol/L and (NH
4)
2SO
42.0mol/L mixed solution; Described coordination washing composition pH of mixed is controlled to be 6.5; Coordination washing process pH is controlled to be 4.5;
The rhenium-containing load organic phases that again the coordination washing is obtained is carried out the pure water washing;
The pure water wash conditions is: comparing O/A is 1/2, and normal temperature is washing down, and washing process pH is about 5.5-6, and mixing time is 5min, and starting time is 10min, phase-splitting; The branch phase velocity is fast and two-phase interface is clear; Keep the rhenium-containing load organic phases; Pure water washing back liquid is done WWT;
To analyzing the impurities removing efficiency (%) that draws following metal through the rhenium-containing load organic phases after the coordination washing: Zn 97.16, and Bi 99.27, and Cd 93.85, and As 78.78, and Cu 84.38, and Fe 75.53, and Al 69.37, and Mo 68.84; And the rhenium rate of loss is 0.43%; Carry out pure water washing again, the rhenium rate of loss is 0.05%, and other metals content impurities are all reduced to the rank of 10ppm, thereby can realize that the back extraction process do not have the back extraction slag, and rhenium and other foreign metal ion isolation are complete;
(3) back extractions also purify except that organic phase:
Rhenium-containing load organic phases to obtaining after the pure water washing of last step is carried out back extraction;
The back extraction condition is: make reverse-extraction agent with ammoniacal liquor, comparing O/A is 5/1, back extraction under the normal temperature, and mixing time is 5min, starting time is 30min; Phase-splitting; Keep the rhenium-containing strip liquor, anti-raffinate is an organic phase, returns and utilizes; Reverse-extraction agent ammoniacal liquor massfraction is 10%;
The adding volume(tric)fraction is 10% secondary octanol in the rhenium-containing strip liquor that obtains, and mixing time is 5min, and starting time is 30min, phase-splitting; The branch phase velocity is fast and two-phase interface is clear.Can calculate that the dissolved organic phase is about 18% (volume ratio) in this rhenium-containing strip liquor;
Keep a rhenium-containing strip liquor that does not contain organic phase; Organic phase is then returned and is utilized;
(4) reextraction, washing, back extraction remove organic phase
Gained of last step is left standstill 20h to slightly acidic except that a rhenium-containing strip liquor after the organic phase; Extraction, washing, the back extraction of carrying out above-mentioned (1) (2) (3) step more respectively remove the organic phase operation; Finally obtain high density secondary rhenium-containing strip liquor, it is following that each goes on foot operational condition:
Extraction conditions is: comparing O/A is 1/3, and the time of mixing is 3min, and starting time is 15min; The volume percent of used mixed organic solvents component is: 20%N
235, 40% secondary octanol, 40% sulfonated kerosene; Mixed organic solvents in this step needs to be acidified to pH ﹤ 1 with dilute sulphuric acid earlier; The souring operation step: adding massfraction at mixed organic solvents is 15% dilute sulphuric acid, and comparing O/A is 2/1, and the time of mixing is 3min, and starting time is 15min, phase-splitting, and diluted acid water discards, and the organic phase of reservation is the organic phase after the acidifying of pH ﹤ 1;
The coordination wash conditions is: comparing O/A is 1/1, and normal temperature is washing down; Mixing time is 5min, and starting time is 15min, and said coordination washing composition is for containing EDTA 0.2mol/L and (NH
4)
2SO
40.5mol/L mixed solution; Described coordination washing composition pH of mixed is controlled to be 6.5; Coordination washing process pH is controlled to be 5.0; Washing process does not have visible slag and occurs, and the branch phase velocity is fast and two-phase interface is clear;
The pure water wash conditions is: comparing O/A is 1/2, and normal temperature is washing down, and washing process pH is 5min for the 6-6.5 mixing time, and starting time is 10min; Washing process does not have visible slag and occurs, and the branch phase velocity is fast and two-phase interface is clear;
Back extraction removes the organic phase condition: make reverse-extraction agent with ammoniacal liquor, comparing O/A is 5/1, back extraction under the normal temperature, and mixing time is 5min, starting time is 30min; Reverse-extraction agent ammoniacal liquor massfraction is 8%;
In the high density secondary rhenium-containing strip liquor that obtains, add volume(tric)fraction again and be 5% secondary octanol, the time of mixing is 3min, and starting time is 30min; Phase-splitting; The branch phase velocity is fast and two-phase interface is clear.Can calculate that the dissolved organic phase is about 6% (volume ratio) in this secondary rhenium-containing strip liquor.Keep the high density secondary rhenium-containing strip liquor that does not contain organic phase; Organic phase is then returned and is utilized;
(5) concentrated frozen crystallization
The resulting high density secondary of step (4) rhenium-containing strip liquor chemical ingredients is (mg/L): Re 19584 as follows, and Zn 7, and Bi 1, and Cd 2, and As 4, and Cu 5, and Fe 2, and Al 3, organic phase＜50.Wherein rhenium rate of loss＜0.5% carries out the concentrated frozen crystallization with this solution, and its processing condition are: thickening temperature is 90 ℃, and liquid concentrator volume/concentrate back liquid to amass=2/1 adds ammoniacal liquor after concentrating and regulates pH to 9; Freezing 18h under≤0 ℃ of condition; Dry 24h under≤100 ℃ of conditions promptly gets grade and is 99.21% ammonium perrhenate crystal.
Claims (2)
1. one kind is extracted the method for preparing ammonium perrhenate from copper flue gas during smelting washing spent acid solution, it is characterized in that comprising the steps:
(1) single extraction
In rhenium-containing material copper flue gas during smelting washing spent acid solution, add mixed organic solvents, three stage countercurrents extraction under the normal temperature, extraction conditions is: comparing O/A is 1/3-1/5, and the time of mixing is 5min, and starting time is 15min; Phase-splitting keeps the rhenium-containing load organic phases, and raffinate is done WWT; The volume percent of used mixed organic solvents component is: 10-20%N
235, the secondary octanol of 30-40%, 40-60% sulfonated kerosene;
(2) coordination washings, pure water washing:
Earlier the last step is separated the rhenium-containing load organic phases that obtains and carry out the coordination washing; The coordination wash conditions is: comparing O/A is 1/1-1/2, and normal temperature is washing down; Mixing time is 5min, and starting time is 15min, phase-splitting; Keep the rhenium-containing load organic phases; The liquid recycling of coordination washing back; Said coordination washing composition is for containing EDTA 0.1-1.5mol/L and (NH
4)
2SO
40.2-2mol/L mixed solution; Described coordination washing composition pH of mixed must be controlled to be 5-7; Coordination washing process pH must be controlled to be 3-6.5;
The rhenium-containing load organic phases that again the coordination washing is obtained is carried out the pure water washing;
The pure water wash conditions is: comparing O/A is 1/1-1/2, and normal temperature is washing down, and mixing time is 5min, and starting time is 10min, phase-splitting; Keep the rhenium-containing load organic phases; Pure water washing back liquid is done WWT;
(3) back extractions also purify except that organic phase:
Rhenium-containing load organic phases to obtaining after the pure water washing of last step is carried out back extraction;
The back extraction condition is: make reverse-extraction agent with ammoniacal liquor, comparing O/A is 3/1-5/1, back extraction under the normal temperature, and mixing time is 5min, starting time is 30min; Phase-splitting; Keep the rhenium-containing strip liquor, anti-raffinate is an organic phase, returns and utilizes; Reverse-extraction agent ammoniacal liquor massfraction is 10-15%;
In the rhenium-containing strip liquor that obtains, adding volume(tric)fraction is the secondary octanol of 3-10%, and mixing time is 5min, and starting time is 30min, phase-splitting; Keep a rhenium-containing strip liquor that does not contain organic phase; Organic phase is then returned and is utilized;
(4) reextraction, washing, back extraction reach and remove organic phase
Gained of last step is left standstill 20h to slightly acidic except that a rhenium-containing strip liquor after the organic phase; Carry out extraction, washing, the back extraction of above-mentioned (1) (2) (3) step more respectively and remove the organic phase operation; Finally obtain high density secondary rhenium-containing strip liquor, it is following that each goes on foot operational condition:
Extraction conditions is: comparing O/A is 1/3-1/5, and the time of mixing is 3min, and starting time is 15min; The volume percent of used mixed organic solvents component is: 20%N
235, 40% secondary octanol, 40% sulfonated kerosene; Mixed organic solvents in this step needs to be acidified to pH ﹤ 1 with dilute sulphuric acid earlier;
The coordination wash conditions is: comparing O/A is 1/1-1/2, and normal temperature is washing down; Mixing time is 5min, and starting time is 15min, and said coordination washing composition is for containing EDTA 0.1-0.2 mol/L and (NH
4)
2SO
40.2-0.5 the mixed solution of mol/L; Described coordination washing composition pH of mixed must be controlled to be 5-7; Coordination washing process pH must be controlled to be 3-6.5;
The pure water wash conditions is: comparing O/A is 1/1-1/2, and normal temperature is washing down, and mixing time is 5min, and starting time is 10min;
Back extraction removes the organic phase condition: make reverse-extraction agent with ammoniacal liquor, comparing O/A is 3/1-5/1, back extraction under the normal temperature, and mixing time is 5min, starting time is 30min; Reverse-extraction agent ammoniacal liquor massfraction is 10-15%;
In the high density secondary rhenium-containing strip liquor that obtains, add the secondary octanol that volume(tric)fraction is 3%-5% again, the time of mixing is 3min, and starting time is 30min; Phase-splitting; Keep the high density secondary rhenium-containing strip liquor that does not contain organic phase; Organic phase is then returned and is utilized;
(5) concentrated frozen crystallization
The resulting high density secondary of step (4) rhenium-containing strip liquor is carried out the concentrated frozen crystallization, and its processing condition are: thickening temperature is 90～95 ℃, and liquid concentrator volume/concentrate back liquid to amass=2～5/1 adds ammoniacal liquor after concentrating and regulates pH to 8-9; Freezing 18h under≤0 ℃ of condition; Dry 12-24h under≤100 ℃ of conditions promptly gets grade and is＞98.00% ammonium perrhenate crystal.
2. a kind of the washing from the copper flue gas during smelting according to claim 1 extracted the method for preparing ammonium perrhenate the spent acid solution, it is characterized in that: described coordination washing composition mixed solution uses ammoniacal liquor adjusting pH to be 5-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103391342A CN102502855A (en) | 2011-11-01 | 2011-11-01 | Method for preparing ammonium perrhenate through extracting from coppersmelting exhaust gas washing acid pickle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103391342A CN102502855A (en) | 2011-11-01 | 2011-11-01 | Method for preparing ammonium perrhenate through extracting from coppersmelting exhaust gas washing acid pickle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102502855A true CN102502855A (en) | 2012-06-20 |
Family
ID=46215006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103391342A Pending CN102502855A (en) | 2011-11-01 | 2011-11-01 | Method for preparing ammonium perrhenate through extracting from coppersmelting exhaust gas washing acid pickle |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102502855A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172122A (en) * | 2013-02-28 | 2013-06-26 | 江西铜业股份有限公司 | Method for purifying high purity ammonium rhenate from liquid containing ammonium rhenate |
| CN104030254A (en) * | 2014-06-12 | 2014-09-10 | 白银有色集团股份有限公司 | Fluorine-chlorine removal and recovery device in copper smelting smoke acid making system and recovery method thereof |
| CN104630509A (en) * | 2015-02-03 | 2015-05-20 | 嵩县开拓者钼业有限公司 | Method for preparing ammonium perrhenate |
| CN105671324A (en) * | 2016-03-07 | 2016-06-15 | 紫金矿业集团股份有限公司 | Method for preparing ammonium rhenate from rhenium-enriched slags |
| CN105714123A (en) * | 2016-05-04 | 2016-06-29 | 中条山有色金属集团有限公司 | Method for preparing ammonium rhenate from rhenium-rich slag |
| CN107460320A (en) * | 2017-06-30 | 2017-12-12 | 铜陵有色金属集团股份有限公司 | The new technology of rhenium metal is reclaimed in a kind of Copper making spent acid |
| CN108929960A (en) * | 2018-07-23 | 2018-12-04 | 安徽华西稀有金属材料有限公司 | A method of ammonium perrhenate is prepared from rhenium-containing solution |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4923081A (en) * | 1972-06-07 | 1974-03-01 | ||
| CN101240378A (en) * | 2007-02-07 | 2008-08-13 | 江西铜业集团公司 | Technique for reclaiming rhenium from multiple mixed acid system |
| JP2011178573A (en) * | 2010-02-26 | 2011-09-15 | Sumitomo Metal Mining Co Ltd | Method for producing ammonium perrhenate |
-
2011
- 2011-11-01 CN CN2011103391342A patent/CN102502855A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4923081A (en) * | 1972-06-07 | 1974-03-01 | ||
| CN101240378A (en) * | 2007-02-07 | 2008-08-13 | 江西铜业集团公司 | Technique for reclaiming rhenium from multiple mixed acid system |
| JP2011178573A (en) * | 2010-02-26 | 2011-09-15 | Sumitomo Metal Mining Co Ltd | Method for producing ammonium perrhenate |
Non-Patent Citations (4)
| Title |
|---|
| GHIASVAND ET AL.: "Selective Solid Phase Extraction and Preconcentration of Ultra Trace Molybdenum Using Modified C18 Membrane Disks", 《ASIAN JOURNAL OF CHEMISTRY》, vol. 17, no. 4, 31 December 2005 (2005-12-31), pages 2143 - 2151 * |
| 牟婉君等: "聚乙二醇-(NH4)2SO4-结晶紫体系中铼的萃取性能研究", 《福建分析测试》, vol. 18, no. 1, 31 December 2009 (2009-12-31), pages 1 - 3 * |
| 高天星等: "从冶炼废液中回收铼方法研究", 《铜陵学院学报》, no. 4, 31 December 2008 (2008-12-31) * |
| 高志正: "从净化洗涤污酸中提取金属铼的试验研究", 《中国有色冶金》, no. 6, 31 December 2008 (2008-12-31), pages 68 - 70 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172122A (en) * | 2013-02-28 | 2013-06-26 | 江西铜业股份有限公司 | Method for purifying high purity ammonium rhenate from liquid containing ammonium rhenate |
| CN104030254A (en) * | 2014-06-12 | 2014-09-10 | 白银有色集团股份有限公司 | Fluorine-chlorine removal and recovery device in copper smelting smoke acid making system and recovery method thereof |
| CN104030254B (en) * | 2014-06-12 | 2016-02-24 | 白银有色集团股份有限公司 | In copper blast furnace off-gas acid making system, fluorine chlorine removes retrieving arrangement and recovery method thereof |
| CN104630509A (en) * | 2015-02-03 | 2015-05-20 | 嵩县开拓者钼业有限公司 | Method for preparing ammonium perrhenate |
| CN105671324A (en) * | 2016-03-07 | 2016-06-15 | 紫金矿业集团股份有限公司 | Method for preparing ammonium rhenate from rhenium-enriched slags |
| CN105714123A (en) * | 2016-05-04 | 2016-06-29 | 中条山有色金属集团有限公司 | Method for preparing ammonium rhenate from rhenium-rich slag |
| CN107460320A (en) * | 2017-06-30 | 2017-12-12 | 铜陵有色金属集团股份有限公司 | The new technology of rhenium metal is reclaimed in a kind of Copper making spent acid |
| CN108929960A (en) * | 2018-07-23 | 2018-12-04 | 安徽华西稀有金属材料有限公司 | A method of ammonium perrhenate is prepared from rhenium-containing solution |
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102502855A (en) | Method for preparing ammonium perrhenate through extracting from coppersmelting exhaust gas washing acid pickle | |
| CN109097599B (en) | Method for separating manganese, calcium and magnesium by synergistic extraction | |
| CN102021335B (en) | Method for separating zirconium from hafnium by using elution extraction method | |
| CN108220597A (en) | The method of extracting and separating zirconium and hafnium in nitric acid medium | |
| CN112522512B (en) | Method for preparing battery-grade cobalt sulfate by using organic cobalt slag of zinc smelting plant | |
| CN105712383A (en) | Method for removing calcium and magnesium impurities in lithium-rich solution by extraction process | |
| Li et al. | Purification of wet process phosphoric acid by solvent extraction using cyclohexanol | |
| CN102888513A (en) | Method of fully separating copper, manganese, zinc, cobalt and calcium chloride solution | |
| CN112520790A (en) | Method for producing cobalt sulfate by using organic cobalt slag of zinc smelting plant | |
| Ma et al. | Extraction of germanium (IV) from acid leaching solution with mixtures of P204 and TBP | |
| WO2023045331A1 (en) | Method for selectively recovering valuable metal in waste lithium battery | |
| CN102701263B (en) | Method for preparing copper sulfate in mode that stanniferous copper slag is leached in selective mode and free of evaporation | |
| CN107236872A (en) | A kind of method that rhenium is reclaimed in the difficult poor rhenium slag from high-sulfur high-arsenic | |
| CN108950249A (en) | A kind of vanadium aluminum separation method of vanadium-containing shale pickle liquor | |
| CN102925685B (en) | Compound solvent for extraction separation of tungsten and molybdenum and using method thereof | |
| CN102634668B (en) | Roasting-free evaporation-free method for producing cupric sulfate from zinc hydrometallurgy acid-wash copper dross | |
| CN103526052B (en) | Method for recovering tungsten from tungsten-containing fluorite ore | |
| CN112322901B (en) | Method for selectively leaching rhenium from molybdenum concentrate roasting soot | |
| CN102887534A (en) | Method for recovering reagent level anhydrous sodium sulfate from raffinate obtained in process of extracting nickel from nickel sulfate solution | |
| CN104445425A (en) | Preparation method of high-purity manganese sulfate | |
| CN102703716B (en) | Method for extracting rhenium from rhenium-containing smoke tail gas | |
| CN110643811A (en) | Clean smelting process for nickel-molybdenum ore by full-wet method | |
| CN104069646B (en) | A kind of extractant of purification of wet process phosphoric acid and the method with its extraction phosphoric acid by wet process | |
| CN113373323B (en) | Method for recovering indium from high-iron indium-containing waste liquid | |
| CN111348633A (en) | Wet phosphoric acid purifying process and its extraction liquid regenerating method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120620 |