CN111850323A - Method for refining crude bismuth step by step and continuous vacuum furnace used by same - Google Patents
Method for refining crude bismuth step by step and continuous vacuum furnace used by same Download PDFInfo
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- CN111850323A CN111850323A CN202010739997.8A CN202010739997A CN111850323A CN 111850323 A CN111850323 A CN 111850323A CN 202010739997 A CN202010739997 A CN 202010739997A CN 111850323 A CN111850323 A CN 111850323A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/06—Obtaining bismuth
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/05—Refining by treating with gases, e.g. gas flushing also refining by means of a material generating gas in situ
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
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Abstract
The invention relates to the technical field of metal smelting, and discloses a method for refining crude bismuth step by step, which comprises the following process steps: melting and fishing slag, putting the crude bismuth into a refined bismuth pot, heating by adopting natural gas, and fishing out the melting slag when the temperature is raised to 600 ℃; reducing the temperature to 500 ℃, and removing copper slag by fishing; and then cooling to 280-330 ℃, adding sulfur powder for decoppering, wherein the using amount of the sulfur powder is about 0.2%, stirring for about 2-4 hours, and then fishing out slag for the second time, wherein the slag is collectively called copper-removing slag, and returning to the blast furnace for batching. This method of crude bismuth step refining and continuous type vacuum furnace who uses thereof through the substep reaction for the output precision of crude bismuth is higher, and the follow-up waste material that also can use respectively of the difference of every step output different mills to process the energy saving consumption, also does benefit to the protection of environment simultaneously, and the generating device who has every output step is inconsistent again, can practice thrift the time of waiting for the cooling, shortens the length of production, improves production efficiency.
Description
Technical Field
The invention relates to the technical field of metal smelting, in particular to a method for refining crude bismuth step by step and a continuous vacuum furnace used by the method.
Background
Bismuth can be made into low-melting-point alloy and used in an automatic closer or a type alloy; bismuth oxycarbonate and bismuth oxynitrate as medicaments; bismuth oxide is used in the glass and ceramic industries; bismuth compounds are added into cosmetics as bleaching agents and pearling agents, the content of bismuth in the earth crust is only about 10-6%, single primary natural bismuth ore is rarely seen, most bismuth ore coexists with metal minerals such as tungsten, molybdenum, lead, copper, iron and the like, so that bismuth is generally recovered from byproducts in the refining process of other main metals, the byproducts of bismuth in certain processes exist in the form of high-copper and high-silver bismuth alloys, and the conventional general crude bismuth refining method has strict requirements on impurity elements in crude bismuth, so that the crude bismuth refining device has higher requirements, and therefore, a crude bismuth step-by-step refining method and a continuous vacuum furnace used by the method are provided.
Disclosure of Invention
The invention provides a method for refining crude bismuth step by step and a continuous vacuum furnace used by the method, which have the advantage of removing impurities by multi-step operation and solve the problems of poor impurity removal effect and low purity of produced refined bismuth.
The invention provides the following technical scheme: a method for refining crude bismuth step by step comprises the following process steps:
melting and fishing slag, putting the crude bismuth into a refined bismuth pot, heating by adopting natural gas, and fishing out the melting slag when the temperature is raised to 600 ℃; reducing the temperature to 500 ℃, and removing copper slag by fishing;
cooling to 280-330 ℃, adding sulfur powder for decoppering, wherein the amount of the sulfur powder is about 0.2%, stirring for about 2-4 hours to obtain slag for the second time, wherein the slag is totally called copper-removing slag, and returning to a blast furnace for batching;
and (3) oxidizing and refining, namely heating the bismuth liquid to 680-750 ℃ after copper removal, and blowing compressed air to perform oxidation and impurity removal.
And lead-removing refining, namely controlling the temperature of the antimony-removed bismuth liquid to be 450-480 ℃, introducing chlorine gas into the bismuth liquid through a gas transmission pipeline, and reacting lead in the bismuth liquid with the chlorine to generate lead chloride.
Alkaline refining, heating the lead-removed bismuth solution to 500-520 ℃, adding sodium hydroxide, introducing compressed air into the bismuth solution to react tellurium with oxygen in the air to produce tellurium dioxide, and reacting tellurium which does not react with the compressed air with alkali to generate Na2TeO3Both of which are in solid phase, from bismuth solutionsIs separated out.
And finally, refining, namely controlling the temperature of the bismuth liquid for removing tellurium at 680-720 ℃, adding sodium hydroxide with the weight of 0.5-1% of the material weight, blowing compressed air into the bismuth liquid, stirring for 2 hours, then sampling and analyzing, obtaining refined bismuth when the lead content in the bismuth liquid is less than 0.001% and the silver content in the bismuth liquid is less than 0.003%, and cooling to 320-400 ℃ to cast a bismuth ingot by using a vertical die.
Preferably, in the oxidation refining process, when the smoke gas amount is reduced and a small amount of lead oxide appears on the surface of the bismuth liquid, the antimony removal end point is obtained, and the time is 4-10 hours.
Preferably, in the lead-removing refining process, the number of the gas transmission pipelines is six, and the depth is 300-400 mm.
Preferably, in the alkaline refining process, the adding amount of the sodium hydroxide is 1.5-2% of the weight of the material, the time is 6-10 hours, and the tellurium removal end point is obtained when the added solid alkali is not dried any more under the stirring of compressed air.
A continuous vacuum furnace for refining crude bismuth step by step mainly comprises: the device comprises a smelting pot, a heating device, a temperature control device, a ventilation device, a stirring device, a slag dragging device and a feeding device, wherein the heating device is arranged below the smelting pot, the temperature control device and the stirring and feeding device are arranged beside the smelting pot, the temperature control device triggers the slag dragging device when the temperature in a refining container reaches 300-400 ℃ and 600-700 ℃, the ventilation device comprises an air blower and a bismuth liquid surface air guide pipe inserted into the smelting pot, the temperature control device triggers the feeding device to add alkali or wood dust when the temperature in the smelting pot reaches 450-550 ℃, and the smelting pot is a cast iron pot or a cast steel pot; the stirring device and the slag dragging device are the same device, and the heating device is an electric heating device, a fuel oil heating device or a coal heating device.
The invention has the following beneficial effects:
this method of crude bismuth step refining and continuous type vacuum furnace who uses thereof through the substep reaction for the output precision of crude bismuth is higher, and the follow-up waste material that also can use respectively of the difference of every step output different mills to process the energy saving consumption, also does benefit to the protection of environment simultaneously, and the generating device who has every output step is inconsistent again, can practice thrift the time of waiting for the cooling, shortens the length of production, improves production efficiency.
Drawings
FIG. 1 is a schematic flow chart of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, a method for refining crude bismuth step by step includes the following process steps:
step 1, melting and dragging slag and oxidizing refining
Putting the crude bismuth into a refined bismuth pot, heating by adopting natural gas, and fishing out molten slag when the temperature is 600 ℃;
reducing the temperature to 500 ℃, and removing copper slag by fishing;
and then cooling to 280-330 ℃, adding sulfur powder for decoppering, wherein the using amount of the sulfur powder is about 0.2%, stirring for about 2-4 hours, and then fishing out slag for the second time, wherein the slag is collectively called copper-removing slag, and returning to the blast furnace for batching.
Heating the bismuth liquid to 680-750 ℃ after decoppering, blowing compressed air for oxidation and impurity removal, wherein the difference between the free enthalpies of oxides of metal impurities such as antimony and bismuth oxides is large, so that the metal impurities such as antimony are preferentially oxidized and separated from bismuth in oxidation refining, most of antimony oxide volatilizes into gas, and if the blown compressed air is too large, more bismuth is oxidized, so that the reaction process must be strictly controlled, generally, when the smoke gas quantity is reduced and a small amount of lead oxide appears on the surface of the bismuth liquid, the antimony removal end point is regarded as the antimony removal end point, the time is 4-10 hours, and the main reaction formula of the oxidation refining is as follows:
4Bi+3O2＝2Bi2O3
4Sb+3O2＝2Sb2O3
Sb2O3+O2＝Sb2O5
Bi2O3+2Sb＝Sb2O3+2Bi
step 2, lead removal refining
Controlling the temperature of the antimony-removed bismuth liquid at 450-480 ℃, introducing 6 glass tubes into each pot, wherein the depth of each pot is 300-400 mm, introducing chlorine into the bismuth liquid, reacting lead with the chlorine to generate lead chloride, and repeatedly performing lead removal operation, wherein the main reaction formula of lead removal refining is as follows:
Cl2+Pb＝PbCl2
2Bi+3Cl2＝2BiCl3
step 3, alkaline refining
The purpose of the alkaline refining is to remove tellurium. Heating the bismuth liquid to 500-520 ℃, adding sodium hydroxide, introducing compressed air into the bismuth liquid to react tellurium with oxygen in the air to produce tellurium dioxide, and reacting tellurium which does not react with the compressed air with alkali to generate Na2TeO3, wherein the tellurium dioxide and the tellurium are solid phases which are separated from the bismuth liquid, and the main reaction formula of alkaline refining is as follows:
Te+O2＝TeO2,
TeO2+2NaOH＝Na2TeO3+H2O
tellurium, which has not reacted with compressed air, reacts with alkali as follows:
3Te+6NaOH＝2Na2Te+Na2TeO3+3H2O
the adding amount of the sodium hydroxide is 1.5-2% of the weight of the material, the tellurium removal time is about 6-10 h, and the tellurium removal end point is obtained when the added solid alkali is not dried any more under the stirring of compressed air.
Step 4, final refining
In order to remove residual trace elements which are easier to oxidize than bismuth, such as chlorine, zinc, antimony, tellurium, iron, lead and the like, final refining is carried out, the temperature of bismuth liquid is controlled to be 680-720 ℃, sodium hydroxide with the weight of 0.5-1% of the material weight is added, compressed air is blown into the bismuth liquid to be stirred for 2 hours, then sampling analysis is carried out, when the lead content in the bismuth liquid is less than 0.001% and the silver content in the bismuth liquid is less than 0.003%, refined bismuth is obtained, and after the temperature is reduced to 320-400 ℃, bismuth ingots are cast by a vertical die.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The method for refining the crude bismuth step by step is characterized by comprising the following process steps of:
melting and fishing slag, putting the crude bismuth into a refined bismuth pot, heating by adopting natural gas, and fishing out the melting slag when the temperature is raised to 600 ℃; reducing the temperature to 500 ℃, and removing copper slag by fishing;
cooling to 280-330 ℃, adding sulfur powder for decoppering, wherein the amount of the sulfur powder is about 0.2%, stirring for about 2-4 hours to obtain slag for the second time, wherein the slag is totally called copper-removing slag, and returning to a blast furnace for batching;
and (3) oxidizing and refining, namely heating the bismuth liquid to 680-750 ℃ after copper removal, and blowing compressed air to perform oxidation and impurity removal.
2. The method for fractional refining of crude bismuth as claimed in claim 1, wherein: and lead-removing refining, namely controlling the temperature of the antimony-removed bismuth liquid to be 450-480 ℃, introducing chlorine gas into the bismuth liquid through a gas transmission pipeline, and reacting lead in the bismuth liquid with the chlorine to generate lead chloride.
3. The method for fractional refining of crude bismuth as claimed in claim 2, wherein: alkaline refining, heating the lead-removed bismuth solution to 500-520 ℃, adding sodium hydroxide, introducing compressed air into the bismuth solution to react tellurium with oxygen in the air to produce tellurium dioxide, and reacting tellurium which does not react with the compressed air with alkali to generate Na2TeO3Both of which are solid phases, separated from the bismuth solution.
4. The method for fractional refining of crude bismuth as claimed in claim 3, wherein: and finally, refining, namely controlling the temperature of the bismuth liquid for removing tellurium at 680-720 ℃, adding sodium hydroxide with the weight of 0.5-1% of the material weight, blowing compressed air into the bismuth liquid, stirring for 2 hours, then sampling and analyzing, obtaining refined bismuth when the lead content in the bismuth liquid is less than 0.001% and the silver content in the bismuth liquid is less than 0.003%, and cooling to 320-400 ℃ to cast a bismuth ingot by using a vertical die.
5. The method for fractional refining of crude bismuth as claimed in claim 1, wherein: in the oxidation refining process, when the amount of flue gas is reduced and a small amount of lead oxide appears on the surface of the bismuth liquid, the antimony removal end point is obtained, and the time is 4-10 hours.
6. The method for fractional refining of crude bismuth as claimed in claim 2, wherein: in the lead-removing refining process, the number of the gas transmission pipelines is six, and the depth of the gas transmission pipelines is 300-400 mm.
7. The method for fractional refining of crude bismuth as claimed in claim 3, wherein: in the alkaline refining process, the adding amount of sodium hydroxide is 1.5-2% of the weight of the material, the time is 6-10 hours, and the tellurium removal end point is obtained when the added solid alkali is not dried any more under the stirring of compressed air.
8. The continuous vacuum furnace for the fractional refining of crude bismuth according to claim 1, characterized in that the apparatus mainly comprises: the device comprises a smelting pot, a heating device, a temperature control device, a ventilation device, a stirring device, a slag dragging device and a feeding device, wherein the heating device is arranged below the smelting pot, the temperature control device and the stirring and feeding device are arranged beside the smelting pot, the temperature control device triggers the slag dragging device when the temperature in a refining container reaches 300-400 ℃ and 600-700 ℃, the ventilation device comprises an air blower and a bismuth liquid surface air guide pipe inserted into the smelting pot, the temperature control device triggers the feeding device to add alkali or wood dust when the temperature in the smelting pot reaches 450-550 ℃, and the smelting pot is a cast iron pot or a cast steel pot; the stirring device and the slag dragging device are the same device, and the heating device is an electric heating device, a fuel oil heating device or a coal heating device.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010739997.8A CN111850323A (en) | 2020-07-28 | 2020-07-28 | Method for refining crude bismuth step by step and continuous vacuum furnace used by same |
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| CN202010739997.8A CN111850323A (en) | 2020-07-28 | 2020-07-28 | Method for refining crude bismuth step by step and continuous vacuum furnace used by same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115354172A (en) * | 2022-08-01 | 2022-11-18 | 河南豫光金铅股份有限公司 | Method for improving direct yield in tellurium removal process in high-tellurium crude bismuth pot refining |
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| US3010821A (en) * | 1959-11-16 | 1961-11-28 | American Smelting Refining | Refining of bismuth |
| CN101914694A (en) * | 2010-09-08 | 2010-12-15 | 江西稀有金属钨业控股集团有限公司 | Refining method of crude bismuth containing high silver and high copper |
| CN102329969A (en) * | 2011-09-30 | 2012-01-25 | 江西稀有金属钨业控股集团有限公司 | Refining method of high-tellurium crude bismuth |
| CN203923333U (en) * | 2014-06-20 | 2014-11-05 | 罗文洲 | Multifunctional resistance vacuum continuous still battery parting furnace |
| CN207749167U (en) * | 2017-11-10 | 2018-08-21 | 贵溪三元金属有限公司 | A kind of rare metal bismuth Refining device |
-
2020
- 2020-07-28 CN CN202010739997.8A patent/CN111850323A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3010821A (en) * | 1959-11-16 | 1961-11-28 | American Smelting Refining | Refining of bismuth |
| CN101914694A (en) * | 2010-09-08 | 2010-12-15 | 江西稀有金属钨业控股集团有限公司 | Refining method of crude bismuth containing high silver and high copper |
| CN102329969A (en) * | 2011-09-30 | 2012-01-25 | 江西稀有金属钨业控股集团有限公司 | Refining method of high-tellurium crude bismuth |
| CN102796886A (en) * | 2011-09-30 | 2012-11-28 | 江西稀有金属钨业控股集团有限公司 | Method and system for refining high-tellurium coarse bismuth |
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| CN207749167U (en) * | 2017-11-10 | 2018-08-21 | 贵溪三元金属有限公司 | A kind of rare metal bismuth Refining device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115354172A (en) * | 2022-08-01 | 2022-11-18 | 河南豫光金铅股份有限公司 | Method for improving direct yield in tellurium removal process in high-tellurium crude bismuth pot refining |
| CN115354172B (en) * | 2022-08-01 | 2024-01-23 | 河南豫光金铅股份有限公司 | Method for improving direct yield of tellurium removal process in refining of high tellurium crude bismuth pot |
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