CN101289710A - Process for abstracting bismuth by low-temperature alkaline fusion metallurgy of bismuth clean ore - Google Patents
Process for abstracting bismuth by low-temperature alkaline fusion metallurgy of bismuth clean ore Download PDFInfo
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- CN101289710A CN101289710A CNA2008100314874A CN200810031487A CN101289710A CN 101289710 A CN101289710 A CN 101289710A CN A2008100314874 A CNA2008100314874 A CN A2008100314874A CN 200810031487 A CN200810031487 A CN 200810031487A CN 101289710 A CN101289710 A CN 101289710A
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Abstract
The invention provides a method for extracting bismuth from low temperature caustic fusion bismuth refined ores. In the method, under conditions of the low temperature of between 600 and 900 DEG C and the alkalinity, crude bismuth is extracted from bismuth refined ores by smelting and fusion, and sodium carbonate is leached out by ball-milling slag and sulphonium. The method comprises main steps of the caustic fusion, the milling-leaching and the regeneration of alkali. Due to the adoption of the caustic fusion, the method of has the advantages that the temperature of smelting bismuth is greatly lowered, iron filings and reduction coal are not necessary to add, and particularly low-priced sodium carbonate replaces the majority of sodium hydroxide which lowers smelting cost; directly smelting crude bismuth and regenerating sodium hydroxide greatly simplify the whole process and improve the recovery rate, and the environmental pollution of sulfur dioxide is eliminated. The method is very important to the bismuth smelting and the energy conservation and emission reduction.
Description
[technical field]
The present invention relates to a kind of method of abstracting bismuth by low-temperature alkaline fusion metallurgy of bismuth clean ore, belong to the pyrometallurgy 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 ℃, smelting time reached more than 10 hours, and energy consumption is big, operational condition is abominable, and discharged a large amount of low-concentration sulfur dioxide contaminate environment.For this reason, the inventor proposes a kind of novel process of abstracting bismuth by low-temperature alkaline fusion metallurgy of bismuth clean ore.This technology need not be gone back batch additives such as raw coal, iron filings, and smelting temperature has reduced by 450～700 ℃ than traditional bismuth pyrometallurgical smelting temperature, and the time foreshortens to 3～5 hours, and consumption significantly reduces, and does not arrange the sulfur dioxide pollution environment.
[summary of the invention]
The object of the present invention is to provide a kind of method of bismuth concentrate alkalescence refining bismuth.Thick bismuth is directly smelted in the solid sulphur melting of this method low temperature, and decontamination reaches the purpose that bismuth is smelted energy-saving and emission-reduction and cleaner production.Details are as follows for specific embodiment of the present invention and condition:
1. low-temperature alkali melting
The present invention is with soda ash (Na
2CO
3) replace most of caustic soda (NaOH) under 600～900 ℃ temperature, to smelt the bismuth concentrate extracting thick bismuth, smelting time 1～4h, the melting step is: 1. by formula (1) or (2) theory of computation alkali charge, total alkali content is 1.1～4.0 times of theoretical amount, and the mass ratio of additive is: Na
2CO
3: NaOH: NaNO
3=60～100: 50～80: 1～10; 2. strong solution that contains NaOH300～900g/L of earlier need being added and bismuth concentrate mix the kneading grain; 3. the material of will granulating places reactor bottom, covers required Na above
2CO
34. melting heats up; 5. melting was stirred melt 2～5 times in 0.25～0.5 hour before the time; The NaNO3 that adds requirement in passing.The main chemical reactions of fusion process is as follows:
4Bi
2S
3+18NaOH+＝8Bi+6Na
2S+3Na
2S
2O
3+9H
2O (1)
4Bi
2S
3+24NaOH＝8Bi+9Na
2S+3Na
2SO
4+12H
2O (2)
MeS+Na
2CO
3＝MeO+Na
2S+CO
2↑ (3)
5Na
2S+8NaNO
3+4H
2O＝5Na
2SO
4+4N
2↑+8NaOH (4)
2. ball milling leaches
Water leaches the sodium salt in slag and the sulfonium in mechanical milling process, its condition is: 1. liquid-solid ratio is 1～6: 1; 2. temperature is 60～100 ℃; 3. 0.5～5 hour time; 4. hot wash leached mud 2～5 times is to PH=7～8.
3. the regeneration of alkali
Use lime causticization Na
2CO
3Regeneration NaOH:
Ca(OH)
2+Na
2CO
3＝2NaOH+CaCO
3 (5)
NaOH regenerated condition is: 1. Ca (OH)
2Be 1.1～3.0 times of theoretical amount; 2. temperature is 10～100 ℃; 3. the time is 0.5～10.0 hour; 4. causticization liquid is concentrated under 90～100 ℃ and contains NaOH300～900g/L; 5. concentrated solution is cooled to 3～35 ℃ of crystallizations; 6. separate Na
2SO
410H
2O, Na
2S9H2O and Na
2S
2O
35H
2O.
The present invention adopts the method for caustic fusion, significantly reduced the smelting temperature of bismuth, do not need to add iron filings and go back raw coal, directly smelt thick bismuth and regeneration NaOH, flow process is greatly simplified, the bismuth rate of recovery significantly improves, and has eliminated the pollution of sulfurous gas to environment, smelts significant for bismuth.
[description of drawings]
Figure-1 is process flow diagram of the present invention.
[embodiment]
With persimmon bamboo plantation bismuth concentrate is the melting test portion, and its chemical ingredients sees Table 1.
Table 1 bismuth concentrate chemical ingredients (%)
| The bismuth concentrate | Bi | Mo | Fe | S | WO3 | SiO2 | CaO | F | BeO |
| A# | 25.02 | 3.17 | 20.68 | 26.5 | 0.43 | 6.33 | |||
| B# | 23.87 | 1.8 | 19.12 | 30.98 | 0.6 | 8.8 | 5.22 | 1.3 | 0.0024 |
Embodiment 1
A: bismuth concentrate caustic fusion
In advance 10 gram caustic soda are dissolved in the water of 15ml, make concentrated alkali solution, mix with 100 gram A# bismuth concentrate again and pinch evenly, place the plumbago crucible bottom, carry out melting after covering 147 gram soda ash above, 20min adds 5 gram NaNO3 before smelting time arrives, at 700 ℃ of following melting 60min, and 750 ℃ of insulation 30min; Obtain the heavy 24.78g of thick bismuth gold, the direct yield of bismuth is 97%, slag and sulfonium 211.74 grams.
B: ball milling leaches
Adding slag and sulfonium 211.74 grams in the little ball mill of 1000mL, steel ball 850 grams, water 500mL, mill soaks 4 hours after-filtration under 90 ℃, uses 100mL hot water washery slag 3 times, and pH value is 7.5, filter residue dry weight 59.1 grams, filtrate 560mL contains Na
2CO
3148.5g/L, NaOH4.1g/L, Na
2SO
411.4g/L, Na
2S96.4g/L, Na
2S
2O3 12.08g/L.
C: alkali regeneration
Get above-mentioned mill immersion liquid 90mL and add Ca (OH)
218.64g, 80～85 ℃ of following causticizations 2 hours, filter, CaCO
3Slag 25g; Filtrate is concentrated into 45mL under 100 ℃; Be cooled to 25 ℃ of crystallizations then and go out sulfur-bearing sodium salt 29.20 grams, comprising Na
2S.9H2O 25.36g, Na
2SO
4.10H
2O 2.21g, Na
2S
2O
3.5H
2O1.63g, sulfur-bearing sodium salt open circuit obtains NaOH strong solution 20mL, contains NaOH 518.45g/L; The immersion liquid of 470mL mill directly is concentrated into 168mL in addition, all becomes metaborate monohydrate salt after the cooling, and weight is 232.3g, comprising Na
2CO
369.8g, Na
2S.9H
2O 139.3g, Na
2SO
4.10H
2O 12.16g, Na
2S
2O
3.5H
2O 8.98g, NaOH 1.93g.
With B# bismuth concentrate is test portion, scale be the 1000g concentrate/time,
A: bismuth concentrate caustic fusion
In advance 100 gram caustic soda are dissolved in the water of 150ml, make concentrated alkali solution, mix with 1000 gram B# bismuth concentrate again and pinch evenly, place the plumbago crucible bottom, carry out melting after covering 1470 gram soda ash above, 20min adds 50 gram NaNO3 before smelting time arrives, at 650 ℃ of following melting 60min, and 700 ℃ of insulation 60min; Obtain the heavy 236.4g of thick bismuth gold, the direct yield of bismuth is 96.5%, slag and sulfonium 2167.4 grams.
B: ball milling leaches
Adding slag and sulfonium 2167.4 grams in the little ball mill of 10L, steel ball 9000 grams, water 6000mL, mill soaks 5 hours after-filtration under 90 ℃, uses 1000mL hot water washery slag 5 times, and pH value is 7.2, filter residue dry weight 641 grams, filtrate 6800mL contains Na
2CO
3140.5g/L, NaOH4.0g/L, Na
2SO
410.4g/L, Na
2S 92.4g/L, Na
2S
2O3 11.42g/L.
C: alkali regeneration
Get above-mentioned mill immersion liquid 900mL and add Ca (OH)
2186.4g, 80～85 ℃ of following causticizations 1.5 hours, filter, CaCO
3Slag 254g; Filtrate is concentrated into 450mL under 100 ℃; Be cooled to 25 ℃ of crystallizations then and go out sulfur-bearing sodium salt 304.2 grams, obtain NaOH strong solution 200mL, contain NaOH 504.45g/L; The immersion liquid of 5900mL mill directly is concentrated into 1700mL in addition, all becomes metaborate monohydrate salt after the cooling, and weight is 2425g.
Claims (1)
1. a low temperature alkaline process melting bismuth concentrate extracts the method for thick bismuth, it is characterized in that: with soda ash Na
2CO
3Replace most of caustic soda NaOH to smelt the bismuth concentrate under 600～900 ℃ temperature and extract bismuth, main process comprises that melting, mill soak and the regeneration of alkali, and concrete technology is:
(1) melting places reactor bottom with additive NaOH strong solution and the mixed kneading grain of bismuth concentrate earlier, covers Na more in the above
2CO
3, heating up at last, melting caustic fusion condition is: 1. temperature is 600～900 ℃; 2. the reaction times is 1～4 hour; 3. additive is by Na
2CO
3, NaOH and NaNO
3Form, total alkali content is counted theoretical 1.1～4.0 times of forming with soda ash; Its ratio is: Na
2CO
3: NaOH: NaNO
3=64～90: 7～32: 1.5～16;
(2) mill soak the mill immersion liquid add Ca (OH)
2After the causticization, elimination CaCO
3Slag separates Na with the filtrate condensing crystal
2SO
410H
2O, NaS9H
2O and Na
2S
2O
35H
2O, regeneration NaOH liquid Returning smelting process, it is 60～100 ℃ that ball milling leaches the sodium salt temperature, and the time is 0.5～5 hour, and liquid-solid ratio is 1～6.0: 1; Ratio of grinding media to material is 3～10: 1, and hot wash leached mud 3～5 times is to PH=7～8;
(3) the NaOH regeneration condition is: 1. Ca (OH)
2Be 1.1～3.0 times of theoretical amount; 2. temperature is 10～100 ℃; 3. the time is 0.5～10.0 hour; 4. causticization liquid is concentrated under 90～100 ℃ and contains NaOH300～900g/L; 5. concentrated solution is cooled to 5～35 ℃.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101956084A (en) * | 2010-06-28 | 2011-01-26 | 中南大学 | Low temperature molten salt clean metallurgy method of bismuth |
| CN101760612B (en) * | 2008-12-24 | 2011-08-31 | 深圳市东江环保股份有限公司 | Method for recovering bismuth from secondary zinc oxide slag |
| CN102296180A (en) * | 2011-09-05 | 2011-12-28 | 中南大学 | Method for separating tungsten, molybdenum and bismuth in bismuth sulfide ore concentrate |
| CN102703719A (en) * | 2012-07-03 | 2012-10-03 | 阳谷祥光铜业有限公司 | Technology for recovering valuable metals from noble metal slag |
| 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 |
| CN103993184A (en) * | 2014-04-18 | 2014-08-20 | 江西铜业股份有限公司 | High-antimony bismuth-containing material treatment technology |
| CN106498186A (en) * | 2016-12-06 | 2017-03-15 | 湖南工业大学 | A kind of method that bismuth sulfide material reduction sulphur fixing roast is directly produced bismuth metal |
-
2008
- 2008-06-16 CN CNA2008100314874A patent/CN101289710A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101760612B (en) * | 2008-12-24 | 2011-08-31 | 深圳市东江环保股份有限公司 | Method for recovering bismuth from secondary zinc oxide slag |
| CN101956084A (en) * | 2010-06-28 | 2011-01-26 | 中南大学 | Low temperature molten salt clean metallurgy method of bismuth |
| CN101956084B (en) * | 2010-06-28 | 2012-07-25 | 中南大学 | Low temperature molten salt clean metallurgy method of bismuth |
| CN102296180A (en) * | 2011-09-05 | 2011-12-28 | 中南大学 | Method for separating tungsten, molybdenum and bismuth in bismuth sulfide ore concentrate |
| CN102703719A (en) * | 2012-07-03 | 2012-10-03 | 阳谷祥光铜业有限公司 | Technology for recovering valuable metals from noble metal slag |
| 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 |
| CN103993184A (en) * | 2014-04-18 | 2014-08-20 | 江西铜业股份有限公司 | High-antimony bismuth-containing material treatment technology |
| CN103993184B (en) * | 2014-04-18 | 2015-10-14 | 江西铜业股份有限公司 | A kind for the treatment of process of high antimony bismuth-containing material |
| CN106498186A (en) * | 2016-12-06 | 2017-03-15 | 湖南工业大学 | A kind of method that bismuth sulfide material reduction sulphur fixing roast is directly produced bismuth metal |
| CN106498186B (en) * | 2016-12-06 | 2018-10-30 | 湖南工业大学 | A kind of method that bismuth sulfide material reduction sulphur fixing roast directly produces bismuth metal |
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Open date: 20081022 |