CN101956084A - Low temperature molten salt clean metallurgy method of bismuth - Google Patents
Low temperature molten salt clean metallurgy method of bismuth Download PDFInfo
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- CN101956084A CN101956084A CN2010102110900A CN201010211090A CN101956084A CN 101956084 A CN101956084 A CN 101956084A CN 2010102110900 A CN2010102110900 A CN 2010102110900A CN 201010211090 A CN201010211090 A CN 201010211090A CN 101956084 A CN101956084 A CN 101956084A
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- bismuth
- molten salt
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Abstract
The invention discloses a low temperature molten salt clean metallurgy method of bismuth, including that bismuth sulphide concentrate is smelted in low temperature inertia molten salt, and crude bismuth is obtained by one-step refining. Metal oxide is taken as sulphur-capturing agent, smelting product includes liquid metal bismuth and solid sulphur-capturing metal sulphide, and the later and solid unreacted reactant are all called solid object. Most of inertia molten salt is separated with solid object and returned to smelting process in thermal state, the rest of inertia molten salt bonded by solid object is recycled by virtue of wet processing. The solid object after the molten salt is removed by soaking is subject to mineral separation, so as to recycle sulphur-capturing metal sulphide, the sulphide is roasted for desulphurization, smoke is used for preparing acid, and oxide calcine is returned to the smelting process, so as to be used as sulphur-capturing agent. The invention greatly lowers the temperature in bismuth smelting, crude bismuth is produce in one step, sulphur recovery and utilization of sulphide energy resource are realized, process is simple, cost is low, and direct yield of bismuth is greatly improved, pollution of low concentration SO2 smoke to the environment is thoroughly eliminated, and pollution of beryllium to peripheral soil and underground water in the traditional high temperature bismuth smelting process is avoided.
Description
Technical field
The present invention relates to a kind of clean metallurgical method for low-temperature molten salt of bismuth, belong to the Non-ferrous Metallurgy field.
Background technology
Traditional bismuth Metal smelting divides wet method and pyrogenic process; Wet method refining bismuth mainly contains FeCl
3Leaching-iron replacement method, FeCl
3Leaching-septum electrode method, FeCl
3Bismuth method, chlorine gas selecting lixiviation process, hydrochloric acid-nitrous acid lixiviation process, chloride-hydrolysis, slurry electrolysis etc. are sunk in leaching-hydrolysis, and wet method refining bismuth technology investment is big, cost is higher, especially produces a large amount of waste residues and waste water, and hazardness is big, need curb environmental pollution.Pyrogenic process refining bismuth mainly adopts reverberatory smelting, after being about to batch mixes such as bismuth concentrate and reductive agent coal dust, iron filings, flux soda ash, add reverberatory smelting, output slag, matte and thick bismuth, smelting temperature is up to 1300～1350 ℃, melting was refined bismuth more than 10 hours under so high temperature, have following four outstanding problems: (1) coal consumption is big, cost is high.The persimmon bamboo plantation non-ferrous metal 10m of company limited of bismuth smelting enterprise with domestic maximum
2Reverberatory furnace 1# is an example, and every production 1t bismuth need consume the above high-quality of 3t " Datong District " coal.(2) produce low concentration SO
2The smoke pollution environment.(3) pollution of plumbous mist.Usually also contain a certain amount of lead in the bismuth sulfide concentrate, and lead is volatile heavy metal, its vapour pressure is index multiplication length with the increase of temperature.Thereby under the high melt condition (＞1250 ℃), the lead of association volatilization degree sharply increases in the bismuth concentrate.Lead steam that evaporates and the disperse plumbous mist in the high-altitude causes the severe contamination at factory's surrounding area air, soil and water source.Plumbous mist is different with flue dust, and flue dust can be collected by dust collecting system, and plumbous mist can not be collected by dust collecting system.(4) potentially contaminated of beryllium.Go back association in the bismuth sulfide concentrate beryl Be is arranged
3Al
2[Si
6O
18], behind the high temperature pyrometallurgical smelting, originally the beryllium that existed with stable states such as beryls in the bismuth concentrate is converted into active beryllium oxide big, soluble in water and enters slag, this slag is put in open-air slag field or carries in follow-up wet method and will cause beryllium constantly to run off in the molybdenum operation, enter peripheral underground water and soil, the chronic pollution environment.Beryllium is one of the most malicious element, and very low to people's lethal quantity, its highest permission content is the same with the organic mercury of severe toxicity, is 1/5 of mercury, 1/50 of thorium.
At above problem, we have proposed the application for a patent for invention (application number: CN200810031487.4) of " a kind of low temperature alkaline process melting bismuth concentrate extracts the method for thick bismuth ", but the regeneration of the alkali of this patent application is returned must be all through the wet processing process, and sodium salt such as the sodium sulfate of will opening a way, there is wet processing process complexity, problems such as working cost height.
Summary of the invention
The object of the present invention is to provide a kind of clean metallurgical method for low-temperature molten salt of bismuth.This method significantly reduces the bismuth smelting temperature, the various disadvantages of avoiding existing high melt process to cause, and the thick bismuth of energy one step output, this method is made sulphur-fixing agent with the oxide compound of a kind of and the avidity of the sulphur metal more much bigger than bismuth, realization melting, solid sulphur and alkali regeneration are carried out synchronously, the all recyclable utilization of the sulphur and the sulfide energy when simplifying flow process, reducing cost, significantly improve the bismuth direct yield, is thoroughly eliminated low concentration SO
2Flue gas, heavy metal and beryllium etc. are to the pollution of environment, have low-carbon (LC), cleaning, advantage such as efficient, finally realize the target of thorough reform traditional refining bismuth technology.
The objective of the invention is to realize in the following manner:
A kind of clean metallurgical method for low-temperature molten salt of bismuth may further comprise the steps:
1) make sulphur-fixing agent with metal oxide, the bismuth sulfide concentrate is carried out solid sulphur retailoring in low temperature inertia fused salt, a step is refined thick bismuth, and obtains the mixture of inertia fused salt and solids; Thick bismuth is emitted and natural separation by siphon in the bottom of the mixture of inertia fused salt and solids;
2) then the inertia fused salt is separated the back with solids with the hot fusion process that returns step 1), the isolated solids of water logging;
3) to step 2) the water logging slag carry out ore dressing, obtain solid sulfur metal sulfide product, perhaps further will consolidate sulfur metal sulfide desulfurization with roasting technique, flue gas acid preparing, the oxide compound calcining that obtains returns the fusion process of step 1) and makes sulphur-fixing agent; To step 2) infusion in feed the carbonic acid gas precipitate sodium bicarbonate, the sodium bicarbonate that obtains returns the fusion process of step 1), and mother liquor returns step 2) the water logging process.
The metal oxide of making sulphur-fixing agent described in the step 1) comprises secondary zinc oxide or zinc-oxide calcine, or cupric oxide material or cupric oxide calcining.
Described inertia fused salt is the fused salt mixt of yellow soda ash fused salt or yellow soda ash and sodium hydroxide, and the sodium hydroxide mass content is not higher than 10% in the fused salt mixt.
The described solid sulphur retailoring condition of step 1) is: 1. temperature is 800～950 ℃, 2. time 1～5h, 3. admittedly sulfur metal oxide compound consumption is 1～1.5 times of theoretical amount, 4. make reductive agent with fine coal or coke powder, the reductive agent consumption is 5～15% of a bismuth concentrate quality, and 5. inertia fused salt consumption is 2～6 times of all reactant quality.
Described step 2) adopt fining process to separate inertia fused salt and solids in, actual conditions is: 1. temperature is 800～950 ℃, 2. time 0.5～5h, and top clarification fused salt 3. slowly comes down in torrents.
Described step 2) solids water logging process condition is in: 1. temperature is 10～100 ℃, 2. time 0.5～6h, and 3. liquid-solid volume mass ratio is 1～8: 1ml/g, water washing leached mud 3～5 times is to washings pH=7～8.
The condition of precipitate sodium bicarbonate process is in the described step 3): 1. temperature 10-95 ℃, 2. the time is 0.5-10h, 3. CO
2Volumetric usage is 1.05-2 a times of theoretical amount, 4. reacts to pH=3～8.
Technological process principle of the present invention
In the low temperature inertia fused salt based on yellow soda ash, bismuth sulfide in the bismuth concentrate and reductive agent and ZnO or CuO produce solid sulphur reduction reaction under 650～950 ℃ of temperature:
2Bi
2S
3+6ZnO+3C＝4Bi+6ZnS+3CO
2 (1)
2Bi
2S
3+6CuO+3C＝4Bi+6CuS+3CO
2 (2)
If also contain molybdenum glance in the bismuth concentrate, then molybdenum glance is converted to Sodium orthomolybdate and enters in the slag
2MoS
2+4NaOH+O
2+4ZnO＝2Na
2MoO
4+4ZnS+2H
2O (3)
2MoS
2+2Na
2CO
3+O
2+4ZnO＝2Na
2MoO
4+4ZnS+2CO
2 (4)
FeS
2Also change into FeO and ZnS:
FeS
2+2ZnO＝FeO+2ZnS (5)
Bismuth oxide in the bismuth concentrate then is reduced:
2Bi
2O
3+3C＝4Bi+3CO
2 (6)
At the melting initial stage, the sodium bicarbonate after returning decomposes:
2NaHCO
3＝Na
2CO
3+H
2O+CO
2 (7)
In infusion, feed the carbonic acid gas precipitate sodium bicarbonate:
2NaOH+CO
2＝NaHCO
3+H
2O (8)
Na
2CO
3+CO
2+H
2O＝2NaHCO
3 (9)
SiO in the furnace charge
2, Al
2O
3, CaCO
3, MgCO
3, FeO, CuS etc. are inert substance, do not participate in reaction, it forms the fused salt slag with ZnS or CuS that melting generates as solids.
In sum, the present invention is by a low-temperature molten salt metallurgical method that relates to the gas, liquid, solid three-phase equilibrium, this method is made sulphur-fixing agent with the oxide compound of a kind of and the avidity of the sulphur metal more much bigger than bismuth, the all recyclable utilization of the sulphur and the sulfide energy is carried out in realization melting, solid sulphur and alkali regeneration synchronously.This method has significantly reduced the bismuth smelting temperature, and a step is produced thick bismuth, when simplifying flow process, reducing cost, significantly improve the bismuth direct yield, thoroughly eliminates low concentration SO
2Flue gas is to the pollution and the mist pollution of low latitude lead dust lead of environment and beryllium pollution periphery soil and the phreatic potentially dangerous of avoiding conventional high-temperature refining bismuth technology to exist, have low-carbon (LC), cleaning, advantage such as efficient, technical progress and the energy-saving and emission-reduction that promote China's bismuth metallurgy industry are significant.
Description of drawings
Fig. 1 is a schematic flow sheet of the present invention.
Embodiment
Following examples are intended to further specify the present invention, and unrestricted the present invention.
Embodiment 1
The chemical constitution of bismuth sulfide concentrate is (%): Bi 23.87, Fe 19.12, S 30.98, Cu 0.49, Pb 0.79, Mo1.80, As 0.29, SiO
28.80, CaO 5.22, the chemical constitution of fine coal is (%): C 82.33, S 3.01, SiO
26.66, CaO 0.83, Al
2O
34.81.Take by weighing 100g bismuth sulfide concentrate, 9.23g fine coal, 280g technical grade yellow soda ash respectively and contain the secondary zinc oxide 80.2g uniform mixing of Zn78.33%, compound is packed into behind the plumbago crucible, again at its surface coverage 74.26g technical grade yellow soda ash.Plumbago crucible is pushed in the resistance furnace, and at 900 ℃ of following melting 2h, output contains the thick bismuth 24.16g of Bi 97.81%, and the direct yield of bismuth reaches 99.00%; Obtain the solids slag 155.93g of fusion yellow soda ash 301.5g and bonding small portion yellow soda ash behind the hot fused salt clarification separate solid thing, leach under the condition of 85 ℃ of temperature, time 3h with the 300mL tap water, must do leached mud 104.74g, contain Zn59.98%, S29.58%, the nearly a hundred per cent of sulfur-fixing rate; Filtrate volume is 360mL, contains Na
2CO
3200.5g/L, at room temperature feed CO
2, eutectoid goes out NaHCO
392.30g, get mother liquor 330ml. and contain NaHCO
357g/L.
Embodiment 2
The chemical constitution of moly-sulfide bismuth concentrate is (%): Bi 25.02, Mo 3.17, Fe 20.68, S 26.5, Cu 0.21, Pb 0.43, As 0.09, SiO
26.33, CaO 1.45, MgO 0.85, the chemical constitution of fine coal is (%): C82.33, S 3.01, SiO
26.66, CaO 0.83, Al
2O
34.81.Take by weighing 100g moly-sulfide bismuth concentrate, 10g fine coal, 300g technical grade yellow soda ash respectively and contain the secondary zinc oxide 68.82g uniform mixing of Zn78.33%, compound is packed into behind the plumbago crucible, again at its surface coverage 100g technical grade yellow soda ash.Plumbago crucible is pushed in the resistance furnace, and at 850 ℃ of following melting 2.5h, output contains the thick bismuth 25.29g of Bi98.32%, and the direct yield of bismuth reaches 99.4%; Obtain the solids slag 149.3g of fusion yellow soda ash 349.3g and bonding small portion yellow soda ash behind the hot fused salt clarification separate solid thing, leach under the condition of 80 ℃ of temperature, time 3h with tap water, must do leached mud 90.71g, contain Zn 59.43%, S29.55%, the nearly a hundred per cent of sulfur-fixing rate; Contain Na in the filtrate
2CO
3190.5g/L, contain Sodium orthomolybdate 24.4g/L.At room temperature feed CO
2, eutectoid goes out NaHCO
3102.90g, mother liquor NaHCO
3About 60g/L.
Embodiment 3
The chemical constitution of bismuth sulfide concentrate is identical with embodiment 1, and coke powder contains C 82%, ash content 10% as reductive agent.Take by weighing 1000g bismuth sulfide concentrate, 80g coke respectively and contain the cupric oxide cigarette ash 861.2g uniform mixing of Cu70.86%, compound is packed into behind the plumbago crucible, adds the fusion yellow soda ash 3010.5g that returns by embodiment 1 technology, covers the NaHCO that embodiment 1 returns again
3920.1g and technical grade yellow soda ash 220g.Plumbago crucible is pushed in the resistance furnace, and at 870 ℃ of following melting 1.5h, output contains the thick bismuth 252.02g of Bi 98.78%, and the direct yield of bismuth reaches 99.5%; Obtain the solids slag 1750.43g of fusion yellow soda ash 2960.5g and bonding small portion yellow soda ash behind the hot fused salt clarification separate solid thing, leach under the condition of 90 ℃ of temperature, time 2h with the 4000mL tap water, must do leached mud 1050.25g, contain Cu58.10%, S29.50%, the nearly a hundred per cent of sulfur-fixing rate; Filter gained filtrate and contain Na
2CO
3185g/L at room temperature feeds CO
2, eutectoid goes out NaHCO
32090.63g the residue mother liquor contains NaHCO
355.3g/L.
Claims (7)
1. the clean metallurgical method for low-temperature molten salt of a bismuth is characterized in that, may further comprise the steps:
1) make sulphur-fixing agent with metal oxide, the bismuth sulfide concentrate is carried out solid sulphur retailoring in low temperature inertia fused salt, a step is refined thick bismuth, and obtains the mixture of inertia fused salt and solids; Thick bismuth is emitted and natural separation by siphon in the bottom of the mixture of inertia fused salt and solids;
2) then the inertia fused salt is separated the back with solids with the hot fusion process that returns step 1), the isolated solids of water logging;
3) to step 2) the water logging slag carry out ore dressing, obtain solid sulfur metal sulfide product, perhaps further will consolidate sulfur metal sulfide desulfurization with roasting technique, flue gas acid preparing, the oxide compound calcining that obtains returns the fusion process of step 1) and makes sulphur-fixing agent; To step 2) infusion in feed the carbonic acid gas precipitate sodium bicarbonate, the sodium bicarbonate that obtains returns the fusion process of step 1), and mother liquor returns step 2) the water logging process.
2. according to the clean metallurgical method for low-temperature molten salt of the described a kind of bismuth of claim 1, it is characterized in that: the metal oxide of making sulphur-fixing agent described in the step 1) comprises secondary zinc oxide or zinc-oxide calcine, or cupric oxide material or cupric oxide calcining.
3. according to the clean metallurgical method for low-temperature molten salt of the described a kind of bismuth of claim 1, it is characterized in that: described inertia fused salt is the fused salt mixt of yellow soda ash fused salt or yellow soda ash and sodium hydroxide, and the sodium hydroxide mass content is not higher than 10% in the fused salt mixt.
4. according to the clean metallurgical method for low-temperature molten salt of claim 1 or 2 or 3 described a kind of bismuths, it is characterized in that: the described solid sulphur retailoring condition of step 1) is: 1. temperature is 800～950 ℃, 2. time 1～5h, 3. admittedly sulfur metal oxide compound consumption is 1～1.5 times of theoretical amount, 4. make reductive agent with fine coal or coke powder, the reductive agent consumption is 5～15% of a bismuth concentrate quality, and 5. inertia fused salt consumption is 2～6 times of all reactant quality.
5. according to the clean metallurgical method for low-temperature molten salt of the described a kind of bismuth of claim 1, it is characterized in that: adopt fining process to separate inertia fused salt and solids described step 2), actual conditions is: 1. temperature is 800～950 ℃, 2. time 0.5～5h, and top clarification fused salt 3. slowly comes down in torrents.
6. according to the clean metallurgical method for low-temperature molten salt of the described a kind of bismuth of claim 1, it is characterized in that: solids water logging process condition is described step 2): 1. temperature is 10～100 ℃, 2. time 0.5～6h, 3. liquid-solid volume mass ratio is 1～8: 1ml/g, water washing leached mud 3～5 times is to washings pH=7～8.
7. according to the clean metallurgical method for low-temperature molten salt of the described a kind of bismuth of claim 1, it is characterized in that: the condition of precipitate sodium bicarbonate process is in the described step 3): 1. temperature 10-95 ℃, 2. the time is 0.5-10h, 3. CO
2Volumetric usage is 1.05-2 a times of theoretical amount, 4. reacts to pH=3～8.
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|---|---|---|---|
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|---|---|---|---|
| CN2010102110900A CN101956084B (en) | 2010-06-28 | 2010-06-28 | Low temperature molten salt clean metallurgy method of bismuth |
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| CN101956084A true CN101956084A (en) | 2011-01-26 |
| CN101956084B CN101956084B (en) | 2012-07-25 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534257A (en) * | 2012-02-15 | 2012-07-04 | 四会市鸿明贵金属有限公司 | Novel bismuth smelting separation method |
| CN103305707A (en) * | 2013-06-25 | 2013-09-18 | 湖南柿竹园有色金属有限责任公司 | Method for smelting bismuth-molybdenum or bismuth-tungsten concentrates |
| CN108118158A (en) * | 2018-02-01 | 2018-06-05 | 长沙有色冶金设计研究院有限公司 | The method that valuable metal is extracted from vulcanized slag and blast furnace dust |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1124297A (en) * | 1994-12-08 | 1996-06-12 | 景治熙 | Technique for producing metal by directly smelting sulphide ore |
| CN101289710A (en) * | 2008-06-16 | 2008-10-22 | 中南大学 | Process for abstracting bismuth by low-temperature alkaline fusion metallurgy of bismuth clean ore |
-
2010
- 2010-06-28 CN CN2010102110900A patent/CN101956084B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1124297A (en) * | 1994-12-08 | 1996-06-12 | 景治熙 | Technique for producing metal by directly smelting sulphide ore |
| CN101289710A (en) * | 2008-06-16 | 2008-10-22 | 中南大学 | Process for abstracting bismuth by low-temperature alkaline fusion metallurgy of bismuth clean ore |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534257A (en) * | 2012-02-15 | 2012-07-04 | 四会市鸿明贵金属有限公司 | Novel bismuth smelting separation method |
| CN103305707A (en) * | 2013-06-25 | 2013-09-18 | 湖南柿竹园有色金属有限责任公司 | Method for smelting bismuth-molybdenum or bismuth-tungsten concentrates |
| CN108118158A (en) * | 2018-02-01 | 2018-06-05 | 长沙有色冶金设计研究院有限公司 | The method that valuable metal is extracted from vulcanized slag and blast furnace dust |
| CN108118158B (en) * | 2018-02-01 | 2020-04-21 | 长沙有色冶金设计研究院有限公司 | Method for extracting valuable metals from sulfide slag and blast furnace gas ash |
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|---|---|
| CN101956084B (en) | 2012-07-25 |
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