CN101914694B - Refining method of crude bismuth containing high silver and high copper - Google Patents
Refining method of crude bismuth containing high silver and high copper Download PDFInfo
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- CN101914694B CN101914694B CN2010102752673A CN201010275267A CN101914694B CN 101914694 B CN101914694 B CN 101914694B CN 2010102752673 A CN2010102752673 A CN 2010102752673A CN 201010275267 A CN201010275267 A CN 201010275267A CN 101914694 B CN101914694 B CN 101914694B
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- bismuth
- liquation
- silver
- thick
- sulphur
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 175
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 239000010949 copper Substances 0.000 title claims abstract description 47
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 47
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000004332 silver Substances 0.000 title claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000007670 refining Methods 0.000 title claims abstract description 27
- 239000000460 chlorine Substances 0.000 claims abstract description 54
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 52
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 45
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000005864 Sulphur Substances 0.000 claims abstract description 41
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 239000002893 slag Substances 0.000 claims description 35
- 238000010792 warming Methods 0.000 claims description 27
- 239000011133 lead Substances 0.000 claims description 25
- 239000003513 alkali Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000005660 chlorination reaction Methods 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000004458 analytical method Methods 0.000 claims description 9
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052785 arsenic Inorganic materials 0.000 claims description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052714 tellurium Inorganic materials 0.000 claims description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 5
- 238000005422 blasting Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000011701 zinc Substances 0.000 abstract description 5
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 description 49
- 239000000047 product Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- -1 continues to heat Substances 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- QGWDKKHSDXWPET-UHFFFAOYSA-E pentabismuth;oxygen(2-);nonahydroxide;tetranitrate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[O-2].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QGWDKKHSDXWPET-UHFFFAOYSA-E 0.000 description 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the field of metal refining, and particularly to a refining method of crude bismuth containing high silver and high copper, comprising four steps of adding sulphur for copper removal, adding zinc for silver removal, introducing chlorine for zinc and lead removal, and refining by oxidation. The method of the invention can realize refining of the crude bismuth containing high silver and high copper via high standard, and has the advantages of simple technology, strong controllability and safety.
Description
Technical field
The present invention relates to the refining of metal field, particularly relate to a kind of method of refining of crude bismuth containing high silver and high copper.
Background technology
Bismuth has been widely used: bismuth metal can be made low melting point alloy, is used for safety shutoff or type metal; Bismuthyl carbonate and bismuthyl nitrate are as medicine; Bismuth oxide is used for glass, china and pottery industry; Bismuth compound is added in the makeup as SYNTHETIC OPTICAL WHITNER and pearling agent.The content of bismuth in the earth's crust is seldom seen independent primary natural bismuth mineral only for very low, mostly with metalliferous mineral symbiosis such as tungsten, molybdenum, lead, copper, iron.So generally all reclaim bismuth in the by product in other main metal smelting process.Bismuth is to exist with high-copper, high silver-colored bismuth alloy form at the byproduct of some metal smelting technology.The general method of refining of thick bismuth have strict requirement to the impure unit of thick bismuth in the past.
Summary of the invention
The method of refining that the purpose of this invention is to provide a kind of crude bismuth containing high silver and high copper.
In order to realize the object of the invention, the technical solution used in the present invention is:
A kind of method of refining of crude bismuth containing high silver and high copper may further comprise the steps:
The first step adds the sulphur copper removal
Bismuth liquid is warming up to 550-650 ℃, in thick bismuth liquation, blasts air, make sulphur residual in the bismuth liquid generate gas and overflow;
Second step, the zincification desilver
To pump into second kier through the thick bismuth liquation that adds the sulphur copper removal, be warming up to 500 ℃, add zinc ingot metal, continue to heat, melt back cooling fully to zinc ingot metal, pull silver-colored slag out, be warming up to 400-450 ℃ after having dragged for slag, get the bismuth sample and analyze Ag, Cu, the massfraction of Ag, Cu is respectively Ag≤0.003%, Cu≤0.001% and o'clock stops to heat up to the bismuth liquid;
In the 3rd step, logical chlorine dezincifies, lead
With the bismuth liquid in second kier, be cooled to 300-350 ℃, feed chlorine, when the pot face begins to occur the Dark grey slag, the chlorination cadmia is scooped out; Continue logical chlorine, service temperature begins to be controlled at 350-400 ℃, when temperature rises to more than 500 ℃, the chlorination lead skim is scooped out, and continues logical chlorine 1-2 hour, stops logical chlorine, and the scum silica frost of pot face is dragged for only;
The 4th step, oxidation refining
To pump into the 3rd kier through the thick bismuth liquation after three step process in front, temperature is controlled at 650-750 ℃, adding quality is the sheet alkali of bismuth liquid quality 1-2%, blasting pressurized air in the bismuth liquid in the 3rd kier stirred 1.5-3 hour, drag for slag then, getting the bismuth sample analyzes plumbous, silver, chlorine is worked as lead, silver, the massfraction of chlorine is respectively Pb≤0.001%, Ag≤0.004%, Cl≤0.0015% is qualified, adding quality again is the sheet alkali of bismuth liquid quality 0.05-0.5%, and the sheet alkali fusionization is covered in the bismuth liquid level, is cooled to 330-450 ℃, drag for slag, sample thief carries out total analysis in pot, qualified after, promptly get and make with extra care the bismuth liquation.
The sulphur that adds of the described the first step removes in the process for copper, adds before the sulphur, and thick bismuth liquation is cooled to 290-330 ℃.
The sulphur that adds of the described the first step removes in the process for copper, SULPHUR POWDER is added in the thick bismuth liquation vortex core of stirring.
The sulphur that adds of the described the first step removes in the process for copper, adds excessive SULPHUR POWDER, to reacting completely.
The zincification in described second step removes in the silver process, adds excessive zinc ingot metal, to reacting completely.
In described second step, be warming up to 400-420 ℃ after having dragged for silver-colored slag.
Before feeding chlorine in described the 3rd step bismuth liquid in second kier is cooled to 320-340 ℃.
The temperature that adds the before thick bismuth liquation of sheet alkali in described the 4th step is controlled at 680-720 ℃, after the adding quality is the sheet alkali of bismuth liquid quality 1-2%, blasting pressurized air in the bismuth liquid in the 3rd kier stirred 1.5-2 hour, drag for slag then, get the bismuth sample and analyze plumbous, silver-colored, chlorine, to Pb≤0.001%, Ag≤0.004%, Cl≤0.0015%, the sheet alkali fusionization that adds quality again and be bismuth liquid quality 0.1-0.2% is covered in bismuth liquid surface, is cooled to 350-420 ℃.
Beneficial effect of the present invention:
1, the refining of the thick bismuth of the high-level realization of energy.
2, technology is simple, and controllability is strong, and is safer.
Thick bismuth, product, operative norm GB/T915-1995 trade mark Bi 99.99 triangular contrast (massfractions: %)
Wherein, " product " refers to the bismuth that adopts method of refining of the present invention to obtain.
Embodiment
Embodiment one:
Adopting present method to carry out the process that thick bismuth refining obtains bismuth ingot realizes through following steps:
The first step adds the sulphur copper removal
Be cooled to about 280 ℃ after dragging for slag, start stirrer, the leaf bar of stirrer stirs thick bismuth liquation, adds sulphur while stirring, excessive SULPHUR POWDER is added in the thick bismuth liquation vortex core of stirring.
Main reaction formula is:
2Bi+3S=Bi
2S
3
Bi
2S
3+6Cu=2Bi?+3Cu
2S?(S)
Progressively be warming up to about 500 ℃ after adding sulphur, continue stirring and stop after 20 minutes stirring, because Cu
2The fusing point of S is 1100
0More than the C, so the copper in the thick bismuth is with Cu
2The pressed powder of S or bits form are present in the thick bismuth liquation, and Cu
2The proportion of S can swim in the surface of thick bismuth liquation, with Cu less than the proportion of Bi
2S pressed powder or bits are pulled out with the leakage wooden dipper;
Drag in the bismuth liquid behind the slag and contain residual sulphur in the thick bismuth liquation, bismuth liquid is warming up to 550 ℃, in thick bismuth liquation, blast air, make residual sulphur oxidation be SO
2Gaseous state is overflowed.
Main reaction formula is:
S+O
2=SO
2 á?(g)
Second step, the zincification desilver
To pump into second kier through the thick bismuth liquation that adds the sulphur copper removal, be warming up to 500 ℃, add zinc ingot metal, insulation, melting the back fully to zinc ingot metal lowers the temperature, zinc and silver can generate compound between a series of infusible Ag-Zn, are the scum silica frost form and separate with bismuth liquid, and insulation treats that zinc ingot metal melts fully, silver-colored slag is dragged in cooling, be warming up to 400 ℃ after having dragged for slag, get the bismuth sample and analyze Ag, Cu, the massfraction of Ag, Cu is respectively Ag≤0.003%, Cu≤0.001% and o'clock stops to heat up to the bismuth liquid; Add excessive zinc ingot metal in this step, react completely with assurance.
The principal reaction formula:
Ag+αZn=?Ag?Zn
α
In the 3rd step, logical chlorine dezincifies, lead
Bismuth liquid after will handling through two steps of front is cooled to 300 ℃, feeds chlorine, the chlorination cadmia is less because of proportion, and come-up covers liquid level, forms the canescence thin film layer at the pot face, when the pot face begins to occur the Dark grey slag, then be the dezincification terminal point, scoop out the chlorination cadmia of liquid state this moment; Continue logical chlorine and carry out the deleading operation, service temperature begins to be controlled at 350 ℃, and logical chlorine deleading process kettle temperature can progressively raise, and when temperature rises to 500 ℃, the chlorination lead skim is scooped out.Continued logical chlorine 1 hour, and got the bismuth sample and analyze Pb, stop logical chlorine, the scum silica frost of pot face is dragged for only.
The principal reaction formula:
Zn+Cl
2=ZnCl
2
Pb+Cl
2=PbCl
2
2BiCl
3+3Zn=3ZnCl
2?+2Bi
2BiCl
3+3Pb=3PbCl
2?+2Bi
The 4th step, oxidation refining
This step mainly is in order to remove the vestige element of the residual easier oxidation of ratio bismuth, as chlorine, arsenic, antimony, tellurium, iron etc.
To pump into the 3rd kier through the thick bismuth liquation after three step process in front, temperature is controlled at 650 ℃, adding quality is the sheet alkali of bismuth liquid quality 1%, the effective constituent of sheet alkali is sodium hydroxide, blast pressurized air in the bismuth liquid in the 3rd kier and stirred 1.5 hours, drag for slag then, get the bismuth sample and analyze plumbous, silver, chlorine, work as lead, silver, the massfraction of chlorine is respectively Pb≤0.001%, Ag≤0.004%, Cl≤0.0015% is qualified, adding quality again is the sheet alkali of bismuth liquid quality 0.05%, the sheet alkali fusionization is covered in the bismuth liquid level, be cooled to 330 ℃, drag for slag, sample thief carries out total analysis in pot, after qualified, promptly get and make with extra care the bismuth liquation.Bismuth liquid is emitted, pump into mold by liquid pump and water and build up bismuth ingot.
In the bismuth product that obtains in the present embodiment, the output of bismuth ingot is 865 kilograms, and the massfraction of bismuth is 99.992% in the product bismuth ingot.
Embodiment two: the something in common of present embodiment and embodiment one is not given unnecessary details, and difference only is
Add sulphur in the first step and remove in the process for copper, thick bismuth is packed in first kier, the fusing that heats up, temperature rises to about 600 ℃;
The sulphur that adds of the described the first step removes in the process for copper, adds before the sulphur, and thick bismuth liquation is cooled to 350 ℃, adds SULPHUR POWDER while stirring in thick bismuth liquation; After adding SULPHUR POWDER, progressively be warming up to 550 ℃, continue stirring and stop after 30 minutes stirring, solid or bits are pulled out; After dragging for slag bismuth liquid is warming up to about 650 ℃, in thick bismuth liquation, blasts air, make sulphur residual in the bismuth liquid generate gas and overflow;
The zincification in described second step removes in the silver process, will pump into second kier through the thick bismuth liquation that adds the sulphur copper removal, is warming up to 550 ℃, adds zinc ingot metal, continues to heat, and melts the back fully to zinc ingot metal and lowers the temperature, and pulls silver-colored slag out, is warming up to 450 ℃ after having dragged for slag.
In the logical chlorine dezincification in described the 3rd step, the plumbous step,, be cooled to 350 ℃, feed chlorine the bismuth liquid in second kier; Scoop out the follow-up continuous logical chlorine of chlorination cadmia, service temperature begins to be controlled at 400 ℃, when temperature rises to more than 500 ℃, the chlorination lead skim is scooped out, and continues logical chlorine 2 hours, stops logical chlorine, and the scum silica frost of pot face is dragged for only.
In the oxidation refining technology in described the 4th step, thick bismuth liquation is pumped into the 3rd kier, temperature is controlled at 750 ℃, adding quality is the sheet alkali of bismuth liquid quality 2%, blast pressurized air in the bismuth liquid in the 3rd kier and stirred 3 hours, drag for slag then, get the analysis of bismuth sample, work as lead, silver, the massfraction of chlorine is respectively Pb≤0.001%, Ag≤0.004%, Cl≤0.0015% is qualified, adding quality again is the sheet alkali of bismuth liquid quality 0.5%, the sheet alkali fusionization is covered in the bismuth liquid level, be cooled to 450 ℃, drag for slag, sample thief carries out total analysis in pot, after qualified, promptly get and make with extra care the bismuth liquation.
In the bismuth product that obtains in the present embodiment, the output of bismuth ingot is 858 kilograms, and the massfraction of bismuth is 99.995% in the product bismuth ingot.
Embodiment three:The something in common of present embodiment and embodiment one is not given unnecessary details, and difference only is
Add sulphur in the first step and remove in the process for copper, thick bismuth is packed in first kier, the fusing that heats up, temperature rises to about 560 ℃;
The sulphur that adds of the described the first step removes in the process for copper, adds before the sulphur, and thick bismuth liquation is cooled to 340 ℃, adds SULPHUR POWDER while stirring in thick bismuth liquation; After adding SULPHUR POWDER, progressively be warming up to 520 ℃, continue stirring and stop after 30 minutes stirring, solid or bits are pulled out; After dragging for slag bismuth liquid is warming up to about 610 ℃, in thick bismuth liquation, blasts air, make sulphur residual in the bismuth liquid generate gas and overflow;
The zincification in described second step removes in the silver process, will pump into second kier through the thick bismuth liquation that adds the sulphur copper removal, is warming up to 520 ℃, adds zinc ingot metal, continues to heat, and melts the back fully to zinc ingot metal and lowers the temperature, and pulls silver-colored slag out, is warming up to 440 ℃ after having dragged for slag.
In the logical chlorine dezincification in described the 3rd step, the plumbous step,, be cooled to 305 ℃, feed chlorine then the bismuth liquid in second kier; Scoop out the follow-up continuous logical chlorine of chlorination cadmia, service temperature begins to be controlled at 380 ℃, when temperature rises to more than 500 ℃, the chlorination lead skim is scooped out, and continues logical chlorine 1.8 hours, stops logical chlorine, and the scum silica frost of pot face is dragged for only.
In the oxidation refining technology in described the 4th step, thick bismuth liquation is pumped into the 3rd kier, temperature is controlled at 670 ℃, adding quality is the sheet alkali of bismuth liquid quality 2%, blast pressurized air in the bismuth liquid in the 3rd kier and stirred 2.5 hours, drag for slag then, get the analysis of bismuth sample, work as lead, silver, the massfraction of chlorine is respectively Pb≤0.001%, Ag≤0.004%, Cl≤0.0015% is qualified, adding quality again is the sheet alkali of bismuth liquid quality 0.3%, the sheet alkali fusionization is covered in the bismuth liquid level, be cooled to 450 ℃, drag for slag, sample thief carries out total analysis in pot, after qualified, promptly get and make with extra care the bismuth liquation.
In the bismuth product that obtains in the present embodiment, the output of bismuth ingot is 872 kilograms, and the massfraction of bismuth is 99.994% in the product bismuth ingot.
Embodiment four:The something in common of present embodiment and embodiment one is not given unnecessary details, and difference only is
Add sulphur in the first step and remove in the process for copper, thick bismuth is packed in first kier, the fusing that heats up, temperature rises to about 535 ℃;
The sulphur that adds of the described the first step removes in the process for copper, adds before the sulphur, and thick bismuth liquation is cooled to 300 ℃, adds SULPHUR POWDER while stirring in thick bismuth liquation; After adding SULPHUR POWDER, progressively be warming up to 535 ℃, continue stirring and stop after 25 minutes stirring, solid or bits are pulled out; After dragging for slag bismuth liquid is warming up to about 570 ℃, in thick bismuth liquation, blasts air, make sulphur residual in the bismuth liquid generate gas and overflow;
The zincification in described second step removes in the silver process, will pump into second kier through the thick bismuth liquation that adds the sulphur copper removal, is warming up to 510 ℃, adds zinc ingot metal, continues to heat, and melts the back fully to zinc ingot metal and lowers the temperature, and pulls silver-colored slag out, is warming up to 410 ℃ after having dragged for slag.
In the logical chlorine dezincification in described the 3rd step, the plumbous step,, be cooled to 330 ℃, feed chlorine the bismuth liquid in second kier; Scoop out the follow-up continuous logical chlorine of chlorination cadmia, service temperature begins to be controlled at 360 ℃, when temperature rises to more than 500 ℃, the chlorination lead skim is scooped out, and continues logical chlorine 1.5 hours, stops logical chlorine, and the scum silica frost of pot face is dragged for only.
In the oxidation refining technology in described the 4th step, thick bismuth liquation is pumped into the 3rd kier, temperature is controlled at 700 ℃, adding quality is the sheet alkali of bismuth liquid quality 2%, blast pressurized air in the bismuth liquid in the 3rd kier and stirred 1.8 hours, drag for slag then, get the analysis of bismuth sample, work as lead, silver, the massfraction of chlorine is respectively Pb≤0.001%, Ag≤0.004%, Cl≤0.0015% is qualified, adding quality again is the sheet alkali of bismuth liquid quality 0.15%, the sheet alkali fusionization is covered in the bismuth liquid level, be cooled to 450 ℃, drag for slag, sample thief carries out total analysis in pot, after qualified, promptly get and make with extra care the bismuth liquation.
In the bismuth product that obtains in the present embodiment, the output of bismuth ingot is 873.8 kilograms, and the massfraction of bismuth is 99.997% in the product bismuth ingot.
Embodiment five:The something in common of present embodiment and embodiment one is not given unnecessary details, and difference only is in the present embodiment 1 ton of thick bismuth packed in first kier, represents with massfraction, contains Cu:2%, Ag:1.5%, and Bi:94.8%, surplus is arsenic, antimony, tellurium, iron;
In the bismuth product that obtains in the present embodiment, the output of bismuth ingot is 921 kilograms, and the massfraction of bismuth is 99.994% in the product bismuth ingot.
Claims (8)
1. the method for refining of a crude bismuth containing high silver and high copper is characterized in that, may further comprise the steps:
The first step adds the sulphur copper removal
Thick bismuth is packed in first kier, the fusing that heats up, temperature rises to 500-600 ℃, treat that thick bismuth melts fully after, drag for unfused residue, the consisting of of described thick bismuth,
Represent with massfraction, contain Cu:0.5-5%, Ag:1-4%, Bi:75-95%, surplus is arsenic, antimony, tellurium, iron;
Second step, the zincification desilver
To pump into second kier through the thick bismuth liquation that adds the sulphur copper removal, be warming up to 500-550 ℃, add zinc ingot metal, continue to heat, melt back cooling fully to zinc ingot metal, pull silver-colored slag out, be warming up to 400-450 ℃ after having dragged for slag, get the bismuth sample and analyze Ag, Cu, the massfraction of Ag, Cu is respectively Ag≤0.003%, Cu≤0.001% and o'clock stops to heat up to the thick bismuth liquation;
In the 3rd step, logical chlorine dezincifies, lead
Thick bismuth liquation with in second kier is cooled to 300-350 ℃, feeds chlorine, when the pot face begins to occur the Dark grey slag, the chlorination cadmia is scooped out; Continue logical chlorine, service temperature begins to be controlled at 350-400 ℃, when temperature rises to more than 500 ℃, the chlorination lead skim is scooped out, and continues logical chlorine 1-2 hour, stops logical chlorine, and the scum silica frost of pot face is dragged for only;
The 4th step, oxidation refining
To pump into the 3rd kier through the thick bismuth liquation after three step process in front, temperature is controlled at 650-750 ℃, adding quality is the sheet alkali of thick bismuth liquation quality 1-2%, blasting pressurized air in the thick bismuth liquation in the 3rd kier stirred 1.5-3 hour, drag for slag then, getting the bismuth sample analyzes plumbous, silver, chlorine is worked as lead, silver, the massfraction of chlorine is respectively Pb≤0.001%, Ag≤0.004%, Cl≤0.0015% is qualified, adding quality again is the sheet alkali of thick bismuth liquation quality 0.05-0.5%, and the sheet alkali fusionization is covered in thick bismuth liquation face, is cooled to 330-450 ℃, drag for slag, sample thief carries out total analysis in pot, qualified after, promptly get and make with extra care the bismuth liquation.
2. the method for refining of a kind of crude bismuth containing high silver and high copper according to claim 1 is characterized in that: the sulphur that adds of the described the first step removes in the process for copper, adds before the SULPHUR POWDER, and thick bismuth liquation is cooled to 290-330 ℃.
3. the method for refining of a kind of crude bismuth containing high silver and high copper according to claim 1 is characterized in that: the sulphur that adds of the described the first step removes in the process for copper, SULPHUR POWDER is added in the thick bismuth liquation vortex core of stirring.
4. the method for refining of a kind of crude bismuth containing high silver and high copper according to claim 1 is characterized in that: the sulphur that adds of the described the first step removes in the process for copper, adds excessive SULPHUR POWDER, to reacting completely.
5. the method for refining of a kind of crude bismuth containing high silver and high copper according to claim 1 is characterized in that: the zincification in described second step removes in the silver process, adds excessive zinc ingot metal, to reacting completely.
6. the method for refining of a kind of crude bismuth containing high silver and high copper according to claim 1 is characterized in that: in described second step, be warming up to 400-420 ℃ after having dragged for silver-colored slag.
7. the method for refining of a kind of crude bismuth containing high silver and high copper according to claim 1 is characterized in that: before feeding chlorine in described the 3rd step thick bismuth liquation in second kier is cooled to 320-340 ℃.
Figure 9C...
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| 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 |
| CN102747232A (en) * | 2012-07-06 | 2012-10-24 | 赵志强 | Method for treating refined copper bismuth dross by electric induction furnace |
| CN102732732B (en) * | 2012-07-10 | 2014-06-11 | 赵志强 | Method for depleting lead copper matte and bismuth copper matte by using induction electric furnace |
| CN104357682B (en) * | 2014-12-09 | 2016-04-06 | 山东恒邦冶炼股份有限公司 | The method of the efficient copper removal of a kind of thick bismuth bismuth kettle refining |
| CN105112688A (en) * | 2015-09-10 | 2015-12-02 | 昆明理工大学 | Fire-refining method of crude bismuth |
| CN107746961B (en) * | 2017-12-04 | 2019-12-03 | 黄可忠 | A method of recycling antimony from antimony slag |
| CN109536730B (en) * | 2018-10-30 | 2020-11-06 | 金川集团股份有限公司 | Method for extracting lead-bismuth alloy from copper anode slime smelting waste residues |
| CN111850323A (en) * | 2020-07-28 | 2020-10-30 | 贵溪三元金属有限公司 | Method for refining crude bismuth step by step and continuous vacuum furnace used by same |
| CN112176204A (en) * | 2020-08-13 | 2021-01-05 | 郴州雄风环保科技有限公司 | Copper and tellurium removal process for noble bismuth |
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| CN100413984C (en) * | 2006-09-26 | 2008-08-27 | 郴州市三和有色金属有限公司 | Impurity removing refining process of high pure bismuth |
| CN100595339C (en) * | 2008-03-07 | 2010-03-24 | 湖南昭山冶金化工有限公司 | Method for producing bismuth and enriched silver from high-silver bismuth alloy |
| CN101525694B (en) * | 2009-04-17 | 2011-01-19 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | Separation process for material containing lead, antimony, copper, bismuth and silver |
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