CN104743526A - Refining process of crude selenium - Google Patents
Refining process of crude selenium Download PDFInfo
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- CN104743526A CN104743526A CN201510138842.8A CN201510138842A CN104743526A CN 104743526 A CN104743526 A CN 104743526A CN 201510138842 A CN201510138842 A CN 201510138842A CN 104743526 A CN104743526 A CN 104743526A
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- 239000011669 selenium Substances 0.000 title claims abstract description 184
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 183
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 181
- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000007670 refining Methods 0.000 title claims abstract description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000706 filtrate Substances 0.000 claims abstract description 29
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 27
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000005266 casting Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000002386 leaching Methods 0.000 claims abstract description 8
- 238000004064 recycling Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 79
- 238000006243 chemical reaction Methods 0.000 claims description 69
- 230000003020 moisturizing effect Effects 0.000 claims description 35
- 238000001556 precipitation Methods 0.000 claims description 29
- 239000012452 mother liquor Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000010949 copper Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 8
- 235000019738 Limestone Nutrition 0.000 claims description 7
- 239000006028 limestone Substances 0.000 claims description 7
- 239000010413 mother solution Substances 0.000 claims description 7
- 238000004806 packaging method and process Methods 0.000 claims description 7
- 238000005070 sampling Methods 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 7
- 238000005987 sulfurization reaction Methods 0.000 claims description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000010970 precious metal Substances 0.000 abstract description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- 239000013049 sediment Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 15
- 239000012535 impurity Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 239000011133 lead Substances 0.000 description 6
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- -1 tin anhydride Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 235000010269 sulphur dioxide Nutrition 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XYUNNDAEUQFHGV-UHFFFAOYSA-N [Se].[Se] Chemical compound [Se].[Se] XYUNNDAEUQFHGV-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004291 sulphur dioxide Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940056932 lead sulfide Drugs 0.000 description 1
- 229910052981 lead sulfide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention relates to the technical field of extracting and refining of rare precious metals and especially discloses a refining process of crude selenium. The refining process of crude selenium comprises the following steps: washing the crude selenium raw material by water for 2-3 times, wherein the ratio between the crude selenium raw material and the water is 1:1; adding 3-8m<3> sodium sulfite solution into per ton of the filtered filter residue, wherein the concentration of the sodium sulfite solution is 150-300g/L; heating the solution to 95-100 DEG C and reacting for 2-3 hours; then adding ammonium sulfide into the solution until no sediment emerges; filtering the solution and removing the filter residue; cooling the filtrate at normal temperature for 48 hour, so that the refined selenium is separated from the sodium sulfite solution; adding 15-20Kg of washed filter residue into per cubic meter of the solution after the separation out of the refined selenium, so that circulating leaching is continued; washing the separated refined selenium until the pH of the eluate is 7.0-7.5; drying the refined selenium and casting the refined selenium into selenium ingot whose grade is 99.99%; and adding concentrated sulfuric acid into the sodium sulfite solution after 5-7 times of recycling use in the technological process to perform acid hydrolysis, so that the sodium sulfite solution can be recycled after acid hydrolysis and cyclically used. The refining process of crude selenium is simple in technical process, small in raw material consumption, low in production cost, friendly to the environment, high in raw material applicability and very good in economic and social benefits.
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 extract refining containing selenium material.
Background technology
The thick selenium produced in copper anode mud sulfurization roasting process, general containing selenium more than 90%, containing impurity such as copper, lead, silicon-dioxide, current method for purification has rectification method and chemical method usually.
The ultimate principle of rectification method utilizes selenium different from impurity volatility, controls certain rectification temperature, by selenium and magazins' layout.Its process is placed in rectifying tank by thick selenium, carries out rectifying under being heated to the temperature of 700-750 DEG C, enters drainer, and be condensed into solid-state thick selenium after selenium volatilization, thus realize and being separated of the impurity such as selenium, lead, and this technique can obtain the pure selenium of 99.5%.
Chemical purification is divided into again nitric acid oxidation method and dioxygen oxidation method.Nitric acid oxidation method is, with nitric acid, thick selenolite is changed into selenous acid solution, solid-state thick tin anhydride is obtained again through twice evaporation, then thick tin anhydride is loaded in sublimation tank and heat, tin anhydride is distilled and enters tourie, and absorbed generation selenous acid solution by ionized water, then pass into after ammonia is neutralized to pH=6.0-6.5 to selenous acid solution, add ammonium sulfide and remove the impurity such as copper, lead further.Selenous acid solution after purification passes into sulphur dioxide reduction and separates out pure selenium, and the selenium grade of this processing method can reach 99.99%.The advantage of nitric acid oxidation method is that product purity is high, and adaptability to raw material is strong.Shortcoming is long flow path, and operating environment is poor, produces a large amount of oxynitride toxic gas in oxidising process.
Dioxygen oxidation method ultimate principle utilizes the oxide compound of selenium different from the volatility of oxide impurity, and under the condition of oxygen and heating, selenolite turns to volatile tin anhydride, and impurity is then oxidized the oxide compound of difficult volatilization, remains in slag.Its process is melted by thick selenium, oxygen blast oxidation in oxidized still, selenium is that the volatilization of tin anhydride form enters condenser, condensed tin anhydride ionized water absorbs and generates selenous acid solution, the purification of selenous acid solution is identical with above-mentioned nitric acid oxidation method, namely with after ammonia neutralization to pH=6.0-6.5, add impurity such as ammonium sulfide removing copper, lead etc., then separate out pure selenium with sulphur dioxide reduction.This processing method also can obtain 99.99% pure selenium, the method there is long flow path equally, chemical consumption is many, high in cost of production shortcoming.
Summary of the invention
Object of the present invention is exactly to solve existing thick selenium process for refining flow process complexity, the chemical reagent consumed is many, cost is high, produce the problems such as a large amount of toxic and harmfuls simultaneously, provide a kind of flow process simple, the process for refining that thick selenium is separated with metallic impurity can be realized, the present invention can obtain the selenium ingot that purity is 99.99%, cost is low, energy-conservation, reduce discharging, environmental protection, there is good economic and social benefit.
The thick selenium process for refining of one of the present invention, comprises the following steps:
(1) thick selenium washing: by thick selenium raw material and water by weight after add water washing 2-3 time for 1:1, filtration, filter residue is stored up stand-by;
(2) thick selenium leaches: add 3-8m to the filter residue per ton in step (1)
3concentration is the sodium sulfite solution of 150-300g/l, be heated to suitably moisturizing after 95-100 DEG C of reaction 2-3h, add again in ammonium sulfide to solution and produce (desirable supernatant liquor 100ml herein without precipitation, add ammonium sulfide to check and whether remove impurity completely), filter after solution left standstill 2h, filtrate is pending; After filter residue is washed with water to pH=7.0-7.5, elutant gives over to reaction moisturizing;
(3) smart selenium is separated out: above-mentioned filtrate is cooled to after normal temperature through 48h, and smart selenium is separated out from filtrate, and the mother liquor of separating out after smart selenium is stand-by, essence selenium is washed with water to the pH=7.0-7.5 in elutant, elutant does the reaction moisturizing in step (2), and the smart selenium pile of precipitation is deposited, selenium ingot to be cast;
(4) Recycling Mother Solution leaches: add the filter residue 15-20Kg in step (1) to every cubic metre, mother liquor in step (3), be heated to suitably moisturizing after 95-100 DEG C of reaction 2-3h, add in ammonium sulfide to solution again and produce without precipitation, filter after solution left standstill 2h, filtrate is pending; After filter residue is washed with water to pH=7.0-7.5, the reaction moisturizing that elutant walks as this, repeats above-mentioned smart selenium precipitation step, recycle 5-7 time according to this of the mother liquor in step (3);
(5) smart selenium ingot casting: step (3) and the middle smart selenium of separating out of step (4), through fusing, ingot casting, cooling, packaging, warehouse-in, obtain sampling the selenium ingot reaching 99.99%;
(6) acidolysis of sodium sulfite solution and regeneration: the mother liquor in step (3) is after recycle 5-7 time, after foreign ion enrichment finite concentration, quality product will be affected, therefore solution is sent into acidolysis reaction groove, add the vitriol oil to pH=1.0-1.5, be heated to 60-80 DEG C of reaction 2 ~ 3 hours, now smart selenium is separated out from solution, it is in the tail gas absorption tank of 5-10% sodium hydroxide solution that the sulfurous gas that reaction produces is equipped with massfraction by blower fan suction, when the concentration of the S-WAT in tourie reaches 150-300g/l, continue on for thick selenium Leaching reaction; The smart selenium produced and step (3), step (4) output essence selenium are handled together, and acidolysis produces waste liquid limestone vegetation and is disposed to settling tank.
Thick selenium raw material described in the present invention be the thick selenium that produces in copper anode mud sulfurization roasting process more than 90% of grade or grade more than 50% other containing elemental selenium raw material;
The preferred concentration of sodium sulfite solution described in the present invention is 180-280g/l;
The optimal concentration of sodium sulfite solution described in the present invention is 250g/l.
The compound method of the sodium sulfite solution that the concentration used in the present invention is 150-300g/l is, S-WAT is the commercially available commercially pure S-WAT solid of buying, takes appropriate solid sodium sulfite and is dissolved in hot water, after fully stirring, takes out supernatant liquid filtering.
The ammonium sulfide used in the present invention, sulfuric acid and sodium hydroxide are all purchase commercially available commercially pure chemical reagent.
Chemical principle of the present invention is: the selenium in filter residue reacts with S-WAT and generates seleno S-WAT under 95-100 DEG C of high temperature, and during normal temperature cooling, sodium thiosulfate decomposes again generation selenium simple substance, sees reaction (1) and (2) formula,
Se+Na
2sO
3→ Na
2seSO
3(intensification) (1)
Na
2seSO
3→ Se ↓+Na
2sO
3(cooling) (2)
Ammonium sulfide and the beavy metal impurity such as copper, lead react, and generate cupric sulfide and lead sulfide precipitation, reaction (3) and (4) formula,
S
2-+ Cu
2+→ CuS↓ （3）
S
2- + Pb
2+→ PbS↓ （4）
Sodium sulfite solution and sulfuric acid reaction generate sulfur dioxide gas, separate out smart selenium simultaneously, see reaction (5) formula,
Na
2SeSO
3+ H
2SO
4→ SO
2↑+ Na
2SO
4+ H
2O + Se↓ （5）
Sulfurous gas is become sodium sulfite solution by sodium hydroxide solution absorption and regeneration, sees reaction (6) formula, the sodium sulfite solution in retort after acidolysis, reacts and neutralizes, see reaction (7) formula with lime (calcium oxide).
SO
2+ 2NaOH → Na
2SO
3+ H
2O （6）
H
2SO
4+ CaO → CaSO
4↓+ H
2O （7）
The present invention, compared with traditional thick selenium process for refining, has following advantage:
(1) under the prerequisite ensureing thick selenium and magazins' layout technical indicator, enormously simplify technical process, and the sodium sulfite solution in recycle process, raw materials consumption is few, reduce production cost, energy-saving and emission-reduction, little to the pollution of environment, and traditional thick selenium process for refining flow process is complicated, in technological process, produce the gas harmful to environmental toxic;
(2) to the strong adaptability of thick selenium raw material, the present invention be applicable to thick selenium content be greater than 50% containing selenium raw material, easy to operate, there is good economic and social benefit.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Embodiment 1
See Fig. 1, the thick selenium raw material in the present embodiment is the thick selenium selenium content produced in copper anode mud sulfurization roasting process is 50%, and technique of the present invention comprises the following steps:
(1) thick selenium washing: by thick selenium raw material and water by weight after add water washing 2-3 time for 1:1, filtration filter residue is stored up stand-by;
(2) thick selenium leaches: add 3m to the filter residue per ton in step (1)
3concentration is the sodium sulfite solution of 150g/l, is heated to suitably moisturizing after 95-100 DEG C of reaction 2-3h, then adds in ammonium sulfide to solution and produce without precipitation, and filter after solution left standstill 2h, filtrate is pending; After filter residue is washed with water to pH=7.0-7.5, elutant is as the reaction moisturizing in step (2);
(3) smart selenium is separated out: above-mentioned filtrate is cooled to after normal temperature through 48h, and smart selenium is separated out from filtrate, and the mother liquor of separating out after smart selenium is stand-by, essence selenium is washed with water to the pH=7.0-7.5 of elutant, elutant does the reaction moisturizing in step (2), and the smart selenium pile of precipitation is deposited, selenium ingot to be cast;
(4) Recycling Mother Solution leaches: add the filter residue 15Kg in step (1) to every cubic metre, mother liquor in step (3), be heated to suitably moisturizing after 95-100 DEG C of reaction 2-3h, add in ammonium sulfide to solution again and produce without precipitation, filter after solution left standstill 2h, filtrate is pending; After filter residue is washed with water to pH=7.0-7.5, the reaction moisturizing that elutant walks as this, repeats above-mentioned smart selenium precipitation step, recycle 5-7 time according to this of the mother liquor in step (3);
(5) smart selenium ingot casting: step (3) and the middle smart selenium of separating out of step (4), through fusing, ingot casting, cooling, packaging, warehouse-in, obtain sampling the selenium ingot reaching 99.99%;
(6) acidolysis of sodium sulfite solution and regeneration: the mother liquor in step (3) is after recycle 5-7 time, solution is sent into acidolysis reaction groove, add the vitriol oil to pH=1.0-1.5, be heated to 60-80 DEG C of reaction 2 ~ 3 hours, now smart selenium is separated out from solution, it is in the tail gas absorption tank of 5% sodium hydroxide solution that the sulfurous gas that reaction produces is equipped with massfraction by blower fan suction, when the concentration of the S-WAT in tourie reaches 150g/l, continues on for thick selenium Leaching reaction; The smart selenium produced and step (3), step (4) output essence selenium are handled together, and acidolysis produces waste liquid limestone vegetation and is disposed to settling tank.
Embodiment 2
See Fig. 1, the thick selenium raw material in the present embodiment is the thick selenium selenium content produced in copper anode mud sulfurization roasting process is 62%, and technique of the present invention comprises the following steps:
(1) thick selenium washing: by thick selenium raw material and water by weight after add water washing 2-3 time for 1:1, filtration filter residue is stored up stand-by;
(2) thick selenium leaches: add 4m to the filter residue per ton in step (1)
3concentration is the sodium sulfite solution of 180g/l, is heated to suitably moisturizing after 95-100 DEG C of reaction 2-3h, then adds in ammonium sulfide to solution and produce without precipitation, and filter after solution left standstill 2h, filtrate is pending; After filter residue is washed with water to pH=7.0-7.5, elutant is as the reaction moisturizing in step (2);
(3) smart selenium is separated out: above-mentioned filtrate is cooled to after normal temperature through 48h, and smart selenium is separated out from filtrate, and the mother liquor of separating out after smart selenium is stand-by, essence selenium is washed with water to the pH=7.0-7.5 of elutant, elutant does the reaction moisturizing in step (2), and the smart selenium pile of precipitation is deposited, selenium ingot to be cast;
(4) Recycling Mother Solution leaches: add the filter residue 16Kg in step (1) to every cubic metre, mother liquor in step (3), be heated to suitably moisturizing after 95-100 DEG C of reaction 2-3h, add in ammonium sulfide to solution again and produce without precipitation, filter after solution left standstill 2h, filtrate is pending; After filter residue is washed with water to pH=7.0-7.5, the reaction moisturizing that elutant walks as this, repeats above-mentioned smart selenium precipitation step, recycle 5-7 time according to this of the mother liquor in step (3);
(5) smart selenium ingot casting: step (3) and the middle smart selenium of separating out of step (4), through fusing, ingot casting, cooling, packaging, warehouse-in, obtain sampling the selenium ingot reaching 99.99%;
(6) acidolysis of sodium sulfite solution and regeneration: the mother liquor in step (3) is after recycle 5-7 time, solution is sent into acidolysis reaction groove, add the vitriol oil to pH=1.0-1.5, be heated to 60-80 DEG C of reaction 2 ~ 3 hours, now smart selenium is separated out from solution, it is in the tail gas absorption tank of 6% sodium hydroxide solution that the sulfurous gas that reaction produces is equipped with massfraction by blower fan suction, when the concentration of the S-WAT in tourie reaches the concentration requirement of step (2), continue on for thick selenium Leaching reaction; The smart selenium produced and step (3), step (4) output essence selenium are handled together, and acidolysis produces waste liquid limestone vegetation and is disposed to settling tank.
Embodiment 3
See Fig. 1, the thick selenium raw material in the present embodiment is the thick selenium produced in anode sludge oxidizing roasting process, and selenium content is 91%, and technique of the present invention comprises the following steps:
(1) thick selenium washing: by thick selenium raw material and water by weight after add water washing 2-3 time for 1:1, filtration filter residue is stored up stand-by;
(2) thick selenium leaches: add 8m to the filter residue per ton in step (1)
3concentration is the sodium sulfite solution of 250g/l, is heated to suitably moisturizing after 95-100 DEG C of reaction 2-3h, then adds in ammonium sulfide to solution and produce without precipitation, and filter after solution left standstill 2h, filtrate is pending; After filter residue is washed with water to pH=7.0-7.5, elutant is as the reaction moisturizing in step (2);
(3) smart selenium is separated out: the filtrate in step (2) is cooled to after normal temperature through 48h, and smart selenium is separated out from filtrate, and the mother liquor of separating out after smart selenium is stand-by, essence selenium is washed with water to the pH=7.0-7.5 of elutant, elutant does the reaction moisturizing in step (2), and the smart selenium pile of precipitation is deposited, selenium ingot to be cast;
(4) Recycling Mother Solution leaches: add the filter residue 17Kg in step (1) to every cubic metre, mother liquor in step (3), be heated to suitably moisturizing after 95-100 DEG C of reaction 2-3h, add in ammonium sulfide to solution again and produce without precipitation, filter after solution left standstill 2h, filtrate is pending; After filter residue is washed with water to pH=7.0-7.5, the reaction moisturizing that elutant walks as this, repeats above-mentioned smart selenium precipitation step, recycle 5-7 time according to this of the mother liquor in step (3);
(5) smart selenium ingot casting: step (3) and the middle smart selenium of separating out of step (4), through fusing, ingot casting, cooling, packaging, warehouse-in, obtain sampling the selenium ingot reaching 99.99%;
(6) acidolysis of sodium sulfite solution and regeneration: the mother liquor in step (3) is after recycle 5-7 time, solution is sent into acidolysis reaction groove, add the vitriol oil to pH=1.0-1.5, be heated to 60-80 DEG C of reaction 2 ~ 3 hours, now smart selenium is separated out from solution, it is in the tail gas absorption tank of 8% sodium hydroxide solution that the sulfurous gas that reaction produces is equipped with massfraction by blower fan suction, when the concentration of the S-WAT in tourie reaches 250g/l, continues on for thick selenium Leaching reaction; The smart selenium produced and step (3), step (4) output essence selenium are handled together, and acidolysis produces waste liquid limestone vegetation and is disposed to settling tank.
Embodiment 4
See Fig. 1, the thick selenium raw material in the present embodiment is the selenium content produced in anode sludge oxidizing roasting process is 80%, and technique of the present invention comprises the following steps:
(1) thick selenium washing: by thick selenium raw material and water by weight after add water washing 2-3 time for 1:1, filtration filter residue is stored up stand-by;
(2) thick selenium leaches: add 5m to the filter residue per ton in step (1)
3concentration is the sodium sulfite solution of 300g/l, is heated to suitably moisturizing after 95-100 DEG C of reaction 2-3h, then adds in ammonium sulfide to solution and produce without precipitation, and filter after solution left standstill 2h, filtrate is pending; After filter residue is washed with water to pH=7.0-7.5, elutant is as the reaction moisturizing in step (2);
(3) smart selenium is separated out: above-mentioned filtrate is cooled to after normal temperature through 48h, and smart selenium is separated out from filtrate, and the mother liquor of separating out after smart selenium is stand-by, essence selenium is washed with water to the pH=7.0-7.5 of elutant, elutant does the reaction moisturizing in step (2), and the smart selenium pile of precipitation is deposited, selenium ingot to be cast;
(4) Recycling Mother Solution leaches: add the filter residue 18Kg in step (1) to every cubic metre, mother liquor in step (3), be heated to suitably moisturizing after 95-100 DEG C of reaction 2-3h, add in ammonium sulfide to solution again and produce without precipitation, filter after solution left standstill 2h, filtrate is pending; After filter residue is washed with water to pH=7.0-7.5, the reaction moisturizing that elutant walks as this, repeats above-mentioned smart selenium precipitation step, recycle 5-7 time according to this of the mother liquor in step (3);
(5) smart selenium ingot casting: step (3) and the middle smart selenium of separating out of step (4), through fusing, ingot casting, cooling, packaging, warehouse-in, obtain sampling the selenium ingot reaching 99.99%;
(6) acidolysis of sodium sulfite solution and regeneration: the mother liquor in step (3) is after recycle 5-7 time, solution is sent into acidolysis reaction groove, add the vitriol oil to pH=1.0-1.5, be heated to 60-80 DEG C of reaction 2 ~ 3 hours, now smart selenium is separated out from solution, it is in the tail gas absorption tank of 9% sodium hydroxide solution that the sulfurous gas that reaction produces is equipped with massfraction by blower fan suction, when the concentration of the S-WAT in tourie reaches 300g/l, continues on for thick selenium Leaching reaction; The smart selenium produced and step (3), step (4) output essence selenium are handled together, and acidolysis produces waste liquid limestone vegetation and is disposed to settling tank.
Embodiment 5
See Fig. 1, the thick selenium raw material in the present embodiment is the thick selenium produced in anode sludge oxidizing roasting process, and selenium content is 70%, and technique of the present invention comprises the following steps:
(1) thick selenium washing: by thick selenium raw material and water by weight after add water washing 2-3 time for 1:1, filtration, filter residue is stored up stand-by;
(2) thick selenium leaches: add 6m to the filter residue per ton in step (1)
3concentration is the sodium sulfite solution of 280g/l, is heated to suitably moisturizing after 95-100 DEG C of reaction 2-3h, then adds in ammonium sulfide to solution and produce without precipitation, and filter after solution left standstill 2h, filtrate is pending; After filter residue is washed with water to pH=7.0-7.5, elutant is as the reaction moisturizing in step (2);
(3) smart selenium is separated out: above-mentioned filtrate is cooled to after normal temperature through 48h, and smart selenium is separated out from filtrate, and the mother liquor of separating out after smart selenium is stand-by, essence selenium is washed with water to the pH=7.0-7.5 of elutant, elutant does the reaction moisturizing in step (2), and the smart selenium pile of precipitation is deposited, selenium ingot to be cast;
(4) Recycling Mother Solution leaches: add the filter residue 20Kg in step (1) to every cubic metre, mother liquor in step (3), be heated to suitably moisturizing after 95-100 DEG C of reaction 2-3h, add in ammonium sulfide to solution again and produce without precipitation, filter after solution left standstill 2h, filtrate is pending; After filter residue is washed with water to pH=7.0-7.5, the reaction moisturizing that elutant walks as this, repeats above-mentioned smart selenium precipitation step, recycle 5-7 time according to this of the mother liquor in step (3);
(5) smart selenium ingot casting: step (3) and the middle smart selenium of separating out of step (4), through fusing, ingot casting, cooling, packaging, warehouse-in, obtain sampling the selenium ingot reaching 99.99%;
(6) acidolysis of sodium sulfite solution and regeneration: the mother liquor in step (3) is after recycle 5-7 time, solution is sent into acidolysis reaction groove, add the vitriol oil to pH=1.0-1.5, be heated to 60-80 DEG C of reaction 2 ~ 3 hours, now smart selenium is separated out from solution, it is in the tail gas absorption tank of 10% sodium hydroxide solution that the sulfurous gas that reaction produces is equipped with massfraction by blower fan suction, when the concentration of the S-WAT in tourie reaches 280g/l, continues on for thick selenium Leaching reaction; The smart selenium produced and step (3), step (4) output essence selenium are handled together, and acidolysis produces waste liquid limestone vegetation and is disposed to settling tank.
Whether the preparation technology of embodiment of the present invention 1-5 and the preparation technology of prior art are produced the factors such as waste gas in consuming time, cost, raw-material adaptability and technological process compare, concrete data see the following form.
As can be seen from the above table, rectification method is consuming time shorter, and cost is lower, produces without waste gas, but raw-material bad adaptability, and be only suitable for small-scale scientific research, be not suitable for large-scale industrial production.Embodiments of the invention 1-5 is when consuming time being more or less the same, and at cost, the aspect such as waste gas produced in raw-material adaptability and technological process is all better than existing preparation technology.
Claims (4)
1. a thick selenium process for refining, is characterized in that comprising the following steps:
(1) thick selenium washing: by thick selenium raw material and water by weight after add water washing 2-3 time for 1:1, filtration, filter residue is stored up stand-by;
(2) thick selenium leaches: add 3-8m to the filter residue per ton in step (1)
3concentration is the sodium sulfite solution of 150-300g/l, is heated to suitably moisturizing after 95-100 DEG C of reaction 2-3h, then adds in ammonium sulfide to solution and produce without precipitation, and filter after solution left standstill 2h, filtrate is pending; After filter residue is washed with water to pH=7.0-7.5, elutant gives over to reaction moisturizing;
(3) smart selenium is separated out: above-mentioned filtrate is cooled to after normal temperature through 48h, and smart selenium is separated out from filtrate, and the mother liquor of separating out after smart selenium is stand-by, essence selenium is washed with water to the pH=7.0-7.5 in elutant, elutant is as the reaction moisturizing in step (2), and the smart selenium pile of precipitation is deposited, selenium ingot to be cast;
(4) Recycling Mother Solution leaches: add the filter residue 15-20Kg in step (1) to every cubic metre, mother liquor in step (3), be heated to suitably moisturizing after 95-100 DEG C of reaction 2-3h, add in ammonium sulfide to solution again and produce without precipitation, filter after solution left standstill 2h, filtrate is pending; After filter residue is washed with water to pH=7.0-7.5, the reaction moisturizing that elutant walks as this, repeats above-mentioned smart selenium precipitation step, recycle 5-7 time according to this of the mother liquor in step (3);
(5) smart selenium ingot casting: step (3) and the middle smart selenium of separating out of step (4), through fusing, ingot casting, cooling, packaging, warehouse-in, obtain sampling the selenium ingot reaching 99.99%;
(6) acidolysis of sodium sulfite solution and regeneration: the mother liquor in step (3) is after recycle 5-7 time, solution is sent into acidolysis reaction groove, add the vitriol oil to pH=1.0-1.5, be heated to 60-80 DEG C of reaction 2 ~ 3 hours, now smart selenium is separated out from solution, it is in the tail gas absorption tank of 5-10% sodium hydroxide solution that the sulfurous gas that reaction produces is equipped with massfraction by blower fan suction, when the concentration of the S-WAT in tourie reaches 150-300g/l, continues on for thick selenium Leaching reaction; The smart selenium produced and step (3), step (4) output essence selenium are handled together, and acidolysis produces waste liquid limestone vegetation and is disposed to settling tank.
2. the thick selenium process for refining of one according to claim 1, is characterized in that: described thick selenium raw material be the thick selenium that produces in copper anode mud sulfurization roasting process more than 90% of grade or grade more than 50% other containing elemental selenium raw material.
3. the thick selenium process for refining of one according to claim 1, is characterized in that: the concentration of described sodium sulfite solution is 180-280g/l.
4. the thick selenium process for refining of one according to claim 1, is characterized in that: the concentration of described sodium sulfite solution is 250g/l.
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| 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 | A kind of Na2SeSO3 solution efficient method for removing lead |
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