CN104743526B - A kind of thick selenium process for refining - Google Patents
A kind of thick selenium process for refining Download PDFInfo
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Abstract
The present invention relates to the extraction of rare precious metal and refining techniques field, be the refined technique of a kind of thick selenium, it be by thick selenium raw material and water by weight washing 23 times for 1:1 after, the filtering residue per ton after filtering adds 3 8m3Concentration is the sodium sulfite solution of 150 300g/l, 2 3h are reacted after solution is heated to 95 100 DEG C, in solution, add ammonium sulfide again produce to without precipitation, filtering residue is discarded after filtration, after filtrate cools down 48h at normal temperatures, essence selenium separates out from sodium sulfite solution, solution after every cubic metre of precipitation essence selenium adds the filtering residue after 15 20Kg washings and continues cycling through leaching, the smart selenium separated out is scrubbed to eluate pH=7.0 7.5, the selenium ingot that grade is 99.99% is cast after drying, sodium sulfite solution after recycling 57 times in technical process acidolysis can regenerate and recycle after adding concentrated sulphuric acid acidolysis；Present invention process flow process is simple, and raw materials consumption is few, and production cost is low, environmentally friendly, the strong adaptability of raw material, has good economic and social benefit.
Description
Technical field
The present invention relates to extraction and the refining techniques field of rare precious metal, specifically a kind of thick selenium process for refining or the thing on selenium
Material extracts refine.
Background technology
The thick selenium produced during copper anode mud sulfating roasting is general containing selenium more than 90%, containing copper, lead, silicon dioxide
Deng impurity, current method for purification generally has rectification method and chemical method.
The ultimate principle of rectification method is to utilize selenium different from impurity volatility, controls certain rectification temperature, by selenium with miscellaneous
Matter separates.Its process is to be placed in rectification tank by thick selenium, is heated at a temperature of 700-750 DEG C carrying out rectification, and selenium volatilization is laggard
Enter drainer, and be condensed into the thick selenium of solid-state, thus realize separate with the impurity such as selenium, lead, this technique can obtain 99.5% pure
Selenium.
Chemical purification is divided into again nitric acid oxidation method and dioxygen oxidation method.Nitric acid oxidation method is to be melted into by thick selenolite with nitric acid
Monohydrated selenium dioxide solution, then obtain the thick selenium dioxide of solid-state through twice evaporation, then thick selenium dioxide is loaded in sublimation tank and heats,
Make selenium dioxide sublimate into tourie, and absorbed generation Monohydrated selenium dioxide solution by ionized water, be then passed through ammonia to Monohydrated selenium dioxide solution
After gas is neutralized to pH=6.0-6.5, adds ammonium sulfide and remove the impurity such as copper, lead further.Monohydrated selenium dioxide solution after purification is passed through two
Sulfur oxide reduction separates out pure selenium, and the selenium grade of this process is up to 99.99%.The advantage of nitric acid oxidation method is product purity
Height, adaptability to raw material is strong.Shortcoming is long flow path, and operating environment is poor, produces a large amount of nitrogen oxides toxic gas in oxidizing process.
Dioxygen oxidation method ultimate principle utilizes the oxide of selenium different from the volatility of oxide impurity, in oxygen and heating
Under conditions of, selenolite turns to volatile selenium dioxide, and impurity then aoxidizes the oxide of difficult volatilization, remains in slag.Its
Process is to be melted by thick selenium, oxygen blast oxidation in oxidation furnace, and selenium is that selenium dioxide form is volatized into condenser, condensed two
Selenium oxide absorbs with ionized water and generates Monohydrated selenium dioxide solution, and the purification of Monohydrated selenium dioxide solution is identical with above-mentioned nitric acid oxidation method, i.e. uses ammonia
After water is neutralized to pH=6.0-6.5, adds ammonium sulfide and remove the impurity such as copper, lead, then separate out pure selenium with sulphur dioxide reduction.This work
Process also can get 99.99% pure selenium, the method equally exist long flow path, chemical consumption is many, high in cost of production shortcoming.
Summary of the invention
Present invention aim to solve existing thick selenium process for refining flow process complicated, the chemical reagent of consumption is many, becomes
This height, produces the problems such as substantial amounts of toxic and harmful simultaneously, it is provided that a kind of flow process is simple, it is possible to realize thick selenium and metal impurities
The process for refining separated, the present invention can obtain the selenium ingot that purity is 99.99%, low cost, energy-conservation, reduce discharging, environmental protection, have very well
Economic and social benefit.
A kind of thick selenium process for refining of the present invention, comprises the following steps:
(1) slightly selenium washing: after thick selenium raw material is washed 2-3 time with water by weight adding water for 1:1, filtration filtering residue is stored up and treated
With；
(2) thick selenium leaches: the filtering residue per ton in step (1) adds 3-8m3Concentration is the sodium sulfite of 150-300g/l
Solution, is heated to suitably moisturizing after 95-100 DEG C of reaction 2-3h, adds ammonium sulfide and produces (the most desirable without precipitation to solution
Supernatant 100ml, adds ammonium sulfide and checks whether to completely remove impurity), to filter after solution left standstill 2h, filtrate is pending；Filter
After slag is washed with water to pH=7.0-7.5, eluate is as the reaction moisturizing in step (2)；
(3) essence selenium separates out: above-mentioned filtrate is after 48h is cooled to room temperature, and essence selenium separates out from filtrate, separates out the mother after essence selenium
Liquid is stand-by, and essence selenium is washed with water to the pH=7.0-7.5 of eluate, and eluate makees the reaction moisturizing in step (2), the essence of precipitation
Selenium pile is deposited, selenium ingot to be cast；
(4) Recycling Mother Solution leaches: every cubic metre of mother solution in step (3) adds the filtering residue 15-20Kg in step (1),
It is heated to suitably moisturizing after 95-100 DEG C of reaction 2-3h, adds ammonium sulfide and produce without precipitation, after solution left standstill 2h to solution
Filtering, filtrate is pending；After filtering residue is washed with water to pH=7.0-7.5, the reaction moisturizing that eluate walks as this, repeats above-mentioned
Smart selenium precipitation step, the mother solution in step (3) recycles 5-7 time according to this；
(5) essence selenium ingot casting: the smart selenium separated out in step (3) and step (4) through fusing, ingot casting, cool down, pack, put in storage, must
The selenium ingot of 99.99% is reached to grade；
(6) acidolysis of sodium sulfite solution and regeneration: the mother solution in step (3) after recycling 5-7 time, foreign ion
After enrichment finite concentration, product quality will be affected, therefore solution will be sent into acidolysis reaction groove, addition concentrated sulphuric acid to pH=1.0-
1.5, it is heated to 60-80 DEG C and reacts 2～3 hours, now essence selenium separates out from solution, and the sulfur dioxide that reaction produces is inhaled by blower fan
Enter equipped with in the tail gas absorption tank that mass fraction is 5-10% sodium hydroxide solution, when the concentration of the sodium sulfite in tourie reaches
During to 150-300g/l, continue on for thick selenium and leach reaction；Produced essence selenium is with step (3), step (4) output essence selenium in the lump
Processing, acidolysis produces the neutralization of waste liquid Calx and is emitted into sedimentation tank.
Heretofore described thick selenium raw material is the thick selenium that grade produces during copper anode mud sulfating roasting more than 90%
Or grade other raw materials Han elemental selenium more than 50%；
The preferred concentration of heretofore described sodium sulfite solution is 180-280g/l；
The optimal concentration of heretofore described sodium sulfite solution is 250g/l.
The compound method of the sodium sulfite solution that concentration is 150-300g/l used in the present invention is that sodium sulfite is to adopt
Purchase commercially available commercially pure sodium sulfite solid, weigh appropriate solid sodium sulfite and be dissolved in hot water, after being sufficiently stirred for, draw up clear
Liquid filters.
Ammonium sulfide, sulphuric acid and the sodium hydroxide used in the present invention is all the commercially pure chemical reagent that buying is commercially available.
The chemical principle of the present invention is: the selenium in filtering residue reacts generation selenium under 95-100 DEG C of high temperature with sodium sulfite
For sodium sulfite, during room temperature cooling, sodium thiosulfate decomposes again generation selenium simple substance, sees reaction (1) and (2) formula,
Se + Na2SO3 → Na2SeSO3(intensification) (1)
Na2SeSO3→Se↓+ Na2SO3(cooling) (2)
Ammonium sulfide reacts with the beavy metal impurity such as copper, lead, generates copper sulfide and vulcanized lead precipitation, reacts (3) and (4) formula,
S2- + Cu2+→ CuS ↓ (3)
S2- + Pb2+→ PbS ↓ (4)
Sodium sulfite solution and sulfuric acid reaction generate sulfur dioxide gas, separate out essence selenium simultaneously, see reaction (5) formula,
Na2SeSO3 + H2SO4 → SO2↑+ Na2SO4 + H2O+Se ↓ (5)
Sulfur dioxide is become sodium sulfite solution by sodium hydroxide solution absorption and regeneration, sees reaction (6) formula, acidolysis in retort
After sodium sulfite solution, react neutralization with Calx (calcium oxide), see reaction (7) formula.
SO2 + 2NaOH → Na2SO3 + H2O (6)
H2SO4 + CaO → CaSO4↓+ H2O (7)
The present invention, compared with traditional thick selenium process for refining, has several advantages that
(1) on the premise of ensureing thick selenium and magazins' layout technical specification, enormously simplify technological process, and recycle
During sodium sulfite solution, raw materials consumption is few, reduces production cost, energy-saving and emission-reduction, and the pollution to environment is little, and passes
The thick selenium process for refining flow process of system is complicated, produces the gas harmful to environmental toxic in technical process；
(2) strong adaptability to thick selenium raw material, the present invention is applicable to thick Se content more than 50%, easy to operate, has
Well economic and social benefit.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention.
Detailed description of the invention
Embodiment 1
Seeing Fig. 1, the thick selenium raw material in the present embodiment is that the thick selenium produced during copper anode mud sulfating roasting is containing selenium
Amount is 50%, and the technique of the present invention comprises the following steps:
(1) slightly selenium washing: after thick selenium raw material is washed 2-3 time with water by weight adding water for 1:1, filtration filtering residue is stored up and treated
With；
(2) thick selenium leaches: the filtering residue per ton in step (1) adds 3m3Concentration is the sodium sulfite solution of 150g/l, adds
Heat is suitable moisturizing after reacting 2-3h to 95-100 DEG C, adds ammonium sulfide and produces without precipitation to solution, mistake after solution left standstill 2h
Filter, filtrate is pending；After filtering residue is washed with water to pH=7.0-7.5, eluate is as the reaction moisturizing in step (2)；
(3) essence selenium separates out: above-mentioned filtrate is after 48h is cooled to room temperature, and essence selenium separates out from filtrate, separates out the mother after essence selenium
Liquid is stand-by, and essence selenium is washed with water to the pH=7.0-7.5 of eluate, and eluate makees the reaction moisturizing in step (2), the essence of precipitation
Selenium pile is deposited, selenium ingot to be cast；
(4) Recycling Mother Solution leaches: every cubic metre of mother solution in step (3) adds the filtering residue 15Kg in step (1), heating
Suitably moisturizing to 95-100 DEG C of reaction 2-3h, adds ammonium sulfide and produces without precipitation to solution, filter after solution left standstill 2h,
Filtrate is pending；After filtering residue is washed with water to pH=7.0-7.5, the reaction moisturizing that eluate walks as this, repeats above-mentioned smart selenium
Precipitation step, the mother solution in step (3) recycles 5-7 time according to this；
(5) essence selenium ingot casting: the smart selenium separated out in step (3) and step (4) through fusing, ingot casting, cool down, pack, put in storage, must
The selenium ingot of 99.99% is reached to grade；
(6) acidolysis of sodium sulfite solution and regeneration: solution, after recycling 5-7 time, is sent by the mother solution in step (3)
Entering acidolysis reaction groove, addition concentrated sulphuric acid, to pH=1.0-1.5, is heated to 60-80 DEG C and reacts 2～3 hours, and now essence selenium is from solution
Middle precipitation, the sulfur dioxide that reaction produces is sucked equipped with the tail gas absorption tank that mass fraction is 5% sodium hydroxide solution by blower fan
In, when the concentration of the sodium sulfite in tourie reaches 150g/l, continue on for thick selenium and leach reaction；Produced essence selenium with
Step (3), step (4) output essence selenium are handled together, and acidolysis produces the neutralization of waste liquid Calx and is emitted into sedimentation tank.
Embodiment 2
Seeing Fig. 1, the thick selenium raw material in the present embodiment is that the thick selenium produced during copper anode mud sulfating roasting is containing selenium
Amount is 62%, and the technique of the present invention comprises the following steps:
(1) slightly selenium washing: after thick selenium raw material is washed 2-3 time with water by weight adding water for 1:1, filtration filtering residue is stored up and treated
With；
(2) thick selenium leaches: the filtering residue per ton in step (1) adds 4m3Concentration is the sodium sulfite solution of 180g/l, adds
Heat is suitable moisturizing after reacting 2-3h to 95-100 DEG C, adds ammonium sulfide and produces without precipitation to solution, mistake after solution left standstill 2h
Filter, filtrate is pending；After filtering residue is washed with water to pH=7.0-7.5, eluate is as the reaction moisturizing in step (2)；
(3) essence selenium separates out: above-mentioned filtrate is after 48h is cooled to room temperature, and essence selenium separates out from filtrate, separates out the mother after essence selenium
Liquid is stand-by, and essence selenium is washed with water to the pH=7.0-7.5 of eluate, and eluate makees the reaction moisturizing in step (2), the essence of precipitation
Selenium pile is deposited, selenium ingot to be cast；
(4) Recycling Mother Solution leaches: every cubic metre of mother solution in step (3) adds the filtering residue 16Kg in step (1), heating
Suitably moisturizing to 95-100 DEG C of reaction 2-3h, adds ammonium sulfide and produces without precipitation to solution, filter after solution left standstill 2h,
Filtrate is pending；After filtering residue is washed with water to pH=7.0-7.5, the reaction moisturizing that eluate walks as this, repeats above-mentioned smart selenium
Precipitation step, the mother solution in step (3) recycles 5-7 time according to this；
(5) essence selenium ingot casting: the smart selenium separated out in step (3) and step (4) through fusing, ingot casting, cool down, pack, put in storage, must
The selenium ingot of 99.99% is reached to grade；
(6) acidolysis of sodium sulfite solution and regeneration: solution, after recycling 5-7 time, is sent by the mother solution in step (3)
Entering acidolysis reaction groove, addition concentrated sulphuric acid, to pH=1.0-1.5, is heated to 60-80 DEG C and reacts 2～3 hours, and now essence selenium is from solution
Middle precipitation, the sulfur dioxide that reaction produces is sucked equipped with the tail gas absorption tank that mass fraction is 6% sodium hydroxide solution by blower fan
In, when the concentration of the sodium sulfite in tourie reaches the concentration requirement of step (2), continue on for thick selenium and leach reaction；Institute
The smart selenium produced is handled together with step (3), step (4) output essence selenium, and acidolysis produces the neutralization of waste liquid Calx and is emitted into precipitation
Pond.
Embodiment 3
See Fig. 1, the thick selenium raw material in the present embodiment be the selenium content produced during earth of positive pole oxidizing roasting be 91%,
The technique of the present invention comprises the following steps:
(1) slightly selenium washing: after thick selenium raw material is washed 2-3 time with water by weight adding water for 1:1, filtration filtering residue is stored up and treated
With；
(2) thick selenium leaches: the filtering residue per ton in step (1) adds 8m3Concentration is the sodium sulfite solution of 250g/l, adds
Heat is suitable moisturizing after reacting 2-3h to 95-100 DEG C, adds ammonium sulfide and produces without precipitation to solution, mistake after solution left standstill 2h
Filter, filtrate is pending；After filtering residue is washed with water to pH=7.0-7.5, eluate is as the reaction moisturizing in step (2)；
(3) essence selenium separates out: the filtrate in step (2) is after 48h is cooled to room temperature, and essence selenium separates out from filtrate, separates out essence
Mother solution after selenium is stand-by, and essence selenium is washed with water to the pH=7.0-7.5 of eluate, and eluate makees the reaction moisturizing in step (2),
The smart selenium pile separated out is deposited, selenium ingot to be cast；
(4) Recycling Mother Solution leaches: every cubic metre of mother solution in step (3) adds the filtering residue 17Kg in step (1), heating
Suitably moisturizing to 95-100 DEG C of reaction 2-3h, adds ammonium sulfide and produces without precipitation to solution, filter after solution left standstill 2h,
Filtrate is pending；After filtering residue is washed with water to pH=7.0-7.5, the reaction moisturizing that eluate walks as this, repeats above-mentioned smart selenium
Precipitation step, the mother solution in step (3) recycles 5-7 time according to this；
(5) essence selenium ingot casting: the smart selenium separated out in step (3) and step (4) through fusing, ingot casting, cool down, pack, put in storage, must
The selenium ingot of 99.99% is reached to grade；
(6) acidolysis of sodium sulfite solution and regeneration: solution, after recycling 5-7 time, is sent by the mother solution in step (3)
Entering acidolysis reaction groove, addition concentrated sulphuric acid, to pH=1.0-1.5, is heated to 60-80 DEG C and reacts 2～3 hours, and now essence selenium is from solution
Middle precipitation, the sulfur dioxide that reaction produces is sucked equipped with the tail gas absorption tank that mass fraction is 8% sodium hydroxide solution by blower fan
In, when the concentration of the sodium sulfite in tourie reaches 250g/l, continue on for thick selenium and leach reaction；Produced essence selenium with
Step (3), step (4) output essence selenium are handled together, and acidolysis produces the neutralization of waste liquid Calx and is emitted into sedimentation tank.
Embodiment 4
See Fig. 1, the thick selenium raw material in the present embodiment be the selenium content produced during earth of positive pole oxidizing roasting be 80%,
The technique of the present invention comprises the following steps:
(1) slightly selenium washing: after thick selenium raw material is washed 2-3 time with water by weight adding water for 1:1, filtration filtering residue is stored up and treated
With；
(2) thick selenium leaches: the filtering residue per ton in step (1) adds 5m3Concentration is the sodium sulfite solution of 300g/l, adds
Heat is suitable moisturizing after reacting 2-3h to 95-100 DEG C, adds ammonium sulfide and produces without precipitation to solution, mistake after solution left standstill 2h
Filter, filtrate is pending；After filtering residue is washed with water to pH=7.0-7.5, eluate is as the reaction moisturizing in step (2)；
(3) essence selenium separates out: above-mentioned filtrate is after 48h is cooled to room temperature, and essence selenium separates out from filtrate, separates out the mother after essence selenium
Liquid is stand-by, and essence selenium is washed with water to the pH=7.0-7.5 of eluate, and eluate makees the reaction moisturizing in step (2), the essence of precipitation
Selenium pile is deposited, selenium ingot to be cast；
(4) Recycling Mother Solution leaches: every cubic metre of mother solution in step (3) adds the filtering residue 18Kg in step (1), heating
Suitably moisturizing to 95-100 DEG C of reaction 2-3h, adds ammonium sulfide and produces without precipitation to solution, filter after solution left standstill 2h,
Filtrate is pending；After filtering residue is washed with water to pH=7.0-7.5, the reaction moisturizing that eluate walks as this, repeats above-mentioned smart selenium
Precipitation step, the mother solution in step (3) recycles 5-7 time according to this；
(5) essence selenium ingot casting: the smart selenium separated out in step (3) and step (4) through fusing, ingot casting, cool down, pack, put in storage, must
The selenium ingot of 99.99% is reached to grade；
(6) acidolysis of sodium sulfite solution and regeneration: solution, after recycling 5-7 time, is sent by the mother solution in step (3)
Entering acidolysis reaction groove, addition concentrated sulphuric acid, to pH=1.0-1.5, is heated to 60-80 DEG C and reacts 2～3 hours, and now essence selenium is from solution
Middle precipitation, the sulfur dioxide that reaction produces is sucked equipped with the tail gas absorption tank that mass fraction is 9% sodium hydroxide solution by blower fan
In, when the concentration of the sodium sulfite in tourie reaches 300g/l, continue on for thick selenium and leach reaction；Produced essence selenium with
Step (3), step (4) output essence selenium are handled together, and acidolysis produces the neutralization of waste liquid Calx and is emitted into sedimentation tank.
Embodiment 5
See Fig. 1, the thick selenium raw material in the present embodiment be the selenium content produced during earth of positive pole oxidizing roasting be 70%,
The technique of the present invention comprises the following steps:
(1) slightly selenium washing: after thick selenium raw material is washed 2-3 time with water by weight adding water for 1:1, filtration filtering residue is stored up and treated
With；
(2) thick selenium leaches: the filtering residue per ton in step (1) adds 6m3Concentration is the sodium sulfite solution of 280g/l, adds
Heat is suitable moisturizing after reacting 2-3h to 95-100 DEG C, adds ammonium sulfide and produces without precipitation to solution, mistake after solution left standstill 2h
Filter, filtrate is pending；After filtering residue is washed with water to pH=7.0-7.5, eluate is as the reaction moisturizing in step (2)；
(3) essence selenium separates out: above-mentioned filtrate is after 48h is cooled to room temperature, and essence selenium separates out from filtrate, separates out the mother after essence selenium
Liquid is stand-by, and essence selenium is washed with water to the pH=7.0-7.5 of eluate, and eluate makees the reaction moisturizing in step (2), the essence of precipitation
Selenium pile is deposited, selenium ingot to be cast；
(4) Recycling Mother Solution leaches: every cubic metre of mother solution in step (3) adds the filtering residue 20Kg in step (1), heating
Suitably moisturizing to 95-100 DEG C of reaction 2-3h, adds ammonium sulfide and produces without precipitation to solution, filter after solution left standstill 2h,
Filtrate is pending；After filtering residue is washed with water to pH=7.0-7.5, the reaction moisturizing that eluate walks as this, repeats above-mentioned smart selenium
Precipitation step, the mother solution in step (3) recycles 5-7 time according to this；
(5) essence selenium ingot casting: the smart selenium separated out in step (3) and step (4) through fusing, ingot casting, cool down, pack, put in storage, must
The selenium ingot of 99.99% is reached to grade；
(6) acidolysis of sodium sulfite solution and regeneration: solution, after recycling 5-7 time, is sent by the mother solution in step (3)
Entering acidolysis reaction groove, addition concentrated sulphuric acid, to pH=1.0-1.5, is heated to 60-80 DEG C and reacts 2～3 hours, and now essence selenium is from solution
Middle precipitation, the sulfur dioxide that reaction produces is sucked equipped with the tail gas absorption tank that mass fraction is 10% sodium hydroxide solution by blower fan
In, when the concentration of the sodium sulfite in tourie reaches 280g/l, continue on for thick selenium and leach reaction；Produced essence selenium with
Step (3), step (4) output essence selenium are handled together, and acidolysis produces the neutralization of waste liquid Calx and is emitted into sedimentation tank.
By the preparation technology of the preparation technology of embodiment of the present invention 1-5 and prior art at time-consuming, cost, raw-material suitable
Whether producing the factors such as waste gas in answering property and technical process to compare, concrete data see table.
As can be seen from the above table, rectification method is the shortest, and cost is relatively low, produces without waste gas, but raw-material adaptability
Difference, and it is only suitable for small-scale scientific research, be not suitable for large-scale commercial production.Embodiments of the invention 1-5 is time-consumingly
In the case of being more or less the same, the aspect such as waste gas produced in cost, raw-material adaptability and technical process is superior to existing
Preparation technology.
Claims (4)
1. a thick selenium process for refining, it is characterised in that comprise the following steps:
(1) thick selenium washing: after thick selenium raw material is washed 2-3 time with water by weight adding water for 1:1, filter filtering residue and store up stand-by；
(2) thick selenium leaches: the filtering residue per ton in step (1) adds 3-8m3Concentration is the sodium sulfite solution of 150-300g/l,
It is heated to suitably moisturizing after 95-100 DEG C of reaction 2-3h, adds ammonium sulfide and produce without precipitation, after solution left standstill 2h to solution
Filtering, filtrate is pending；After filtering residue is washed with water to pH=7.0-7.5, eluate is as the reaction moisturizing in step (2)；
(3) essence selenium separates out: above-mentioned filtrate is after 48h is cooled to room temperature, and essence selenium separates out from filtrate, separates out the mother solution after essence selenium and treats
With, essence selenium is washed with water to the pH=7.0-7.5 of eluate, and eluate is as the reaction moisturizing in step (2), the smart selenium of precipitation
Store up, selenium ingot to be cast；
(4) Recycling Mother Solution leaches: every cubic metre of mother solution in step (3) adds the filtering residue 15-20Kg in step (1), heating
Suitably moisturizing to 95-100 DEG C of reaction 2-3h, adds ammonium sulfide and produces without precipitation to solution, filter after solution left standstill 2h,
Filtrate is pending；After filtering residue is washed with water to pH=7.0-7.5, the reaction moisturizing that eluate walks as this, repeats above-mentioned smart selenium
Precipitation step, the mother solution in step (3) recycles 5-7 time according to this；
(5) essence selenium ingot casting: in step (3) and step (4) the smart selenium of precipitation through fusing, ingot casting, cool down, pack, put in storage, obtain product
Position reaches the selenium ingot of 99.99%；
(6) acidolysis of sodium sulfite solution and regeneration: solution, after recycling 5-7 time, is sent into acid by the mother solution in step (3)
Solving reactive tank, addition concentrated sulphuric acid, to pH=1.0-1.5, is heated to 60-80 DEG C and reacts 2～3 hours, and now essence selenium is analysed from solution
Going out, the sulfur dioxide that reaction produces is sucked equipped with in the tail gas absorption tank that mass fraction is 5-10% sodium hydroxide solution by blower fan,
When the concentration of the sodium sulfite in tourie reaches 150-300g/l, continue on for thick selenium and leach reaction；Produced essence selenium
Handling together with step (3), step (4) output essence selenium, acidolysis produces the neutralization of waste liquid Calx and is emitted into sedimentation tank.
One the most according to claim 1 thick selenium process for refining, is characterized in that: described thick selenium raw material be grade 90% with
The thick selenium produced during upper copper anode mud sulfating roasting or grade other raw materials Han elemental selenium more than 50%.
One the most according to claim 1 thick selenium process for refining, is characterized in that: the concentration of described sodium sulfite solution is
180-280g/l。
One the most according to claim 1 thick selenium process for refining, is characterized in that: the concentration of described sodium sulfite solution is
250g/l。
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| CN109231175A (en) * | 2018-11-14 | 2019-01-18 | 昆明理工大学 | A method of impure selenium is purified with dehydrated alcohol |
| CN110817811A (en) * | 2019-12-12 | 2020-02-21 | 昆明冶金研究院有限公司 | Preparation method of high-purity selenium powder with uniform particle size distribution |
| CN111874878A (en) * | 2020-08-13 | 2020-11-03 | 昆明冶金研究院有限公司 | Na2SeSO3Method for efficiently removing lead from solution |
| CN114852970B (en) * | 2022-05-30 | 2024-03-29 | 铜陵有色金属集团股份有限公司 | Short-process preparation method of refined selenium |
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| JPH07126772A (en) * | 1993-11-04 | 1995-05-16 | Sumitomo Metal Mining Co Ltd | Production of high purity metallic selenium |
| CN102363522B (en) * | 2011-11-21 | 2013-09-25 | 郴州雄风稀贵金属材料股份有限公司 | Technology for extracting selenium from low-grade selenium-containing material |
| CN102491287B (en) * | 2011-12-11 | 2014-03-26 | 郴州市金贵银业股份有限公司 | Process for separating and recovering selenium from selenium-containing material |
| CN103555962B (en) * | 2013-10-23 | 2015-06-03 | 北京矿冶研究总院 | Method for comprehensively recovering selenium, vanadium and silver from vanadium-silver-selenium polymetallic ore by wet method |
| CN103771357B (en) * | 2014-01-28 | 2015-09-30 | 白银有色集团股份有限公司 | Thick selenium is prepared the oxidized still of tin anhydride and is prepared the method for tin anhydride |
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