CN109097587A - A kind of method of precious metal in high efficiente callback lead anode slurry - Google Patents
A kind of method of precious metal in high efficiente callback lead anode slurry Download PDFInfo
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- CN109097587A CN109097587A CN201811213429.3A CN201811213429A CN109097587A CN 109097587 A CN109097587 A CN 109097587A CN 201811213429 A CN201811213429 A CN 201811213429A CN 109097587 A CN109097587 A CN 109097587A
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- lead
- anode slurry
- precious metals
- bismuth
- metals containing
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- 239000010970 precious metal Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 65
- 239000006256 anode slurry Substances 0.000 title claims abstract description 56
- 229910052802 copper Inorganic materials 0.000 claims abstract description 62
- 239000010949 copper Substances 0.000 claims abstract description 62
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 57
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052709 silver Inorganic materials 0.000 claims abstract description 52
- 239000004332 silver Substances 0.000 claims abstract description 52
- 238000002844 melting Methods 0.000 claims abstract description 37
- 230000008018 melting Effects 0.000 claims abstract description 37
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 30
- 235000002918 Fraxinus excelsior Nutrition 0.000 claims abstract description 25
- 239000002956 ash Substances 0.000 claims abstract description 25
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 17
- 235000017550 sodium carbonate Nutrition 0.000 claims abstract description 17
- 229910001152 Bi alloy Inorganic materials 0.000 claims abstract description 16
- 239000003500 flue dust Substances 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000010436 fluorite Substances 0.000 claims abstract description 15
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003723 Smelting Methods 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003546 flue gas Substances 0.000 claims description 10
- 239000002918 waste heat Substances 0.000 claims description 7
- 239000010903 husk Substances 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052737 gold Inorganic materials 0.000 abstract description 21
- 239000010931 gold Substances 0.000 abstract description 21
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 238000011084 recovery Methods 0.000 abstract description 13
- 238000005422 blasting Methods 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 47
- 239000002893 slag Substances 0.000 description 24
- 239000002184 metal Substances 0.000 description 11
- 238000012545 processing Methods 0.000 description 10
- 238000005265 energy consumption Methods 0.000 description 9
- 238000004064 recycling Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 238000007664 blowing Methods 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 241000722270 Regulus Species 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000001698 pyrogenic effect Effects 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000007613 slurry method Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241000254158 Lampyridae Species 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- QAAXRTPGRLVPFH-UHFFFAOYSA-N [Bi].[Cu] Chemical compound [Bi].[Cu] QAAXRTPGRLVPFH-UHFFFAOYSA-N 0.000 description 1
- DLISVFCFLGSHAB-UHFFFAOYSA-N antimony arsenic Chemical compound [As].[Sb] DLISVFCFLGSHAB-UHFFFAOYSA-N 0.000 description 1
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940073609 bismuth oxychloride Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- 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
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
- C22B11/023—Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
-
- 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
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
-
- 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
- C22B30/02—Obtaining antimony
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention provides a kind of methods of precious metal in high efficiente callback lead anode slurry, the following steps are included: blasting oxygen-enriched air into oxygen enriched molten bath, excess air coefficient control is 0.5-0.8, again melting in oxygen enriched molten bath is added in lead anode slurry, fluorite, iron filings and soda ash after mixing, obtains a precious metals containing lead；Additive is added in a precious metals containing lead and carries out the de- antimony of copper removal, obtains secondary precious metals containing lead and copper ashes；Secondary precious metals containing lead is evaporated in vacuo, lead bismuth alloy and thick silver are obtained；Lead bismuth alloy is carried out second to be evaporated in vacuo, obtains thick bismuth and lead bullion.Present invention process process is simple, oxygen-enriched air smelting isolates flue dust containing antimony and shoddye, the precious metals containing lead that melting is obtained is added troilite and carries out the de- antimony of copper removal, obtain copper ashes, for lead bismuth alloy by isolated thick bismuth is evaporated in vacuo for the second time, the gold and silver taken away in copper ashes and thick bismuth are less, can be improved the direct yield of gold and silver, and shorten the recovery process of gold, silver, high production efficiency.
Description
Technical field
The invention belongs to non-ferrous metal smelting technologies, and in particular to precious metal in a kind of high efficiente callback lead anode slurry
Method.
Background technique
Mainly containing metallic elements such as gold, silver, bismuth, lead, copper, arsenic, antimony in lead anode slurry.Currently, the processing base of lead anode slurry
There are three types of modes in sheet: first is that thermal process；Second is that Whote-wet method technique；Third is that the wet method combined technique of pyrogenic process-.Wet processing examination
Agent consumption is big, and equipment seriously corroded, maintenance load are big, and liquid waste processing process is complicated, and labor productivity is low, production cost
Height, technique is tediously long, is only suitable for small-scale production；The wet method combined process costs of pyrogenic process-are high, and wastewater flow rate is big, exist simultaneously exhaust gas and return
Difficulty is received, and wet process slag needs the techniques such as dry, broken more complex when returning to processing；Now use more category thermal process.
Mostly using lead anode slurry as raw material, the auxiliary materials such as the high silver ore in part and part coking coal, soda ash that may arrange in pairs or groups carry out reduction melting
Output precious metals containing lead, then refinement oxide is carried out to precious metals containing lead, silver electrolysis is sent by making the thick silver of antimony slag, bismuth slag, the final output of copper ashes.The life
In industry industrialization is extensive for production. art, but have the following deficiencies: 1. the time cycle it is too long, if the ordinary circumstance earth of positive pole feeds intake
10-15 tons, recovery time 18-22h, precious metals containing lead puts into 20-26 tons, and the refinement oxide time is 40-60h；2. complex process, especially
It is refinement oxide process, labor intensity of workers is big, and metal recovery rate is low；3. the various slag charge output objects of refinement oxide are more, throwing object is returned
Expect more；4. the gold, silver that by-product antimony slag, bismuth slag, copper ashes are taken away are high, even if the later period is recyclable by subsequent technique, but also can
There is certain loss, and elongated the recovery process of precious metal especially gold, silver, extends when occupying of Company capital
It is long.
In recent years, China has researched and developed the methods of oxygen-enriched bottom-blowing, side-blown melting processing lead anode slurry technique, but still
The problems such as there are energy consumptions high, recovery process complexity, low poor metal recovery rate.Number of patent application CN201310336279.6 is disclosed
A kind of method using top blast furnace comprehensive high-efficiency processing lead anode slurry include mixture preparation, a reduction melting, reduction catch it is golden,
Secondary blowing, recycling arsenic antimony process, i.e., uniformly mix to obtain mixed material by dry weight lead anode slurry, slag former, returning charge, reducing agent；
It being sprayed into top blast furnace molten bath by fuel of the weight of material than 1~10%, control top blast furnace smelting temperature is 900 DEG C~1200 DEG C,
It sufficiently floats after reaction and forms slag blanket recycling processing after discharge outlet is discharged；It is reduced the lead trapping gold, silver that agent restores
Sink to forming precious metals containing lead layer afterwards, is released after further being strengthened blowing through discharge outlet and continue essence refining；High-temperature smoke is returned through waste heat
Receiving apparatus cools down after dedusting, obtains As and Sb flue dust.It is needed in the invention by melting once and secondary blowing, complex process, and
And energy consumption is high, the rate of recovery of precious metal is low.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide precious metal in a kind of high efficiente callback lead anode slurry
Method.
The present invention provides a kind of methods of precious metal in high efficiente callback lead anode slurry, comprising the following steps:
1) oxygen-enriched air is blasted into oxygen enriched molten bath, excess air coefficient control is 0.5-0.8, then by lead anode slurry, firefly
Melting in oxygen enriched molten bath is added in stone, iron filings and soda ash after mixing, obtains a precious metals containing lead；
2) additive is added in a precious metals containing lead and carries out the de- antimony of copper removal, obtains secondary precious metals containing lead and copper ashes；
3) secondary precious metals containing lead is evaporated in vacuo, vacuum degree 10-15Pa, temperature is 900-1100 DEG C, obtains the conjunction of lead bismuth
Golden and thick silver；
4) lead bismuth alloy is carried out second to be evaporated in vacuo, vacuum degree is 6-10Pa, and temperature is 450-600 DEG C, is obtained
Thick bismuth and lead bullion.
11. it is preferred, it include the metallic element of following weight percent content: lead in lead anode slurry described in step 1)
5%-30%, silver-colored 1%-20%, bismuth 1%-20%, copper 1%-10%, antimony 1%-50%.
Preferably, the mass ratio of lead anode slurry described in step 1), fluorite, iron filings and soda ash is 100:0.5:1:5.
Preferably, smelting temperature described in step 1) is 1050-1250 DEG C.
Preferably, flue dust and shoddye are also obtained after melting described in step 1).
Preferably, flue dust described in step 1) obtains flue gas and stibium trioxide after waste heat recycling, purifying and dedusting.
Preferably, additive described in step 2) is troilite or husk.
Preferably, the addition quality of additive described in step 2) is the 0.1-0.3% of a precious metals containing lead quality.
Preferably, it is 600-800 DEG C that copper removal described in step 2), which takes off the temperature of antimony,.
Preferably, mass fraction≤2% containing copper in secondary precious metals containing lead described in step 2), the mass fraction of lead element
≤ 5%.
The present invention controls FeO and SiO in a precious metals containing lead by the way that fluorite and iron filings is added2Mass ratio 1.5-1.8:1, CaO
And SiO2Mass ratio be 0.5-1.0:1.
The shoddye that step 1) of the present invention obtains returns to melting in melting pond.
Mainly containing the metallic elements such as gold, silver, bismuth, lead, copper, arsenic, antimony in lead anode slurry, need noble metal therein and its
He recycles valuable metal, comprehensive utilization.Mostly lead anode slurry is handled using thermal process at present, traditional pyrogenic process work
Skill handles the earth of positive pole there are concentration of precious metal degree is low, and return slag amount is big, and operation mode is discontinuous operation, and automatization level is low, furnace
Son is not closed tight, and environment protecting is poor, and energy consumption is higher, and production cost is smaller with respect to Whote-wet method and pyrogenic process-wet processing.In recent years
Come, China has researched and developed the methods of oxygen-enriched bottom-blowing, side-blown melting processing lead anode slurry technique, number of patent application
Copper ashes and bismuth slag are isolated using reduction melting in CN201310336279.6, gold is caught using reduction and obtains precious metals containing lead layer, precious metals containing lead
Layer obtains As and Sb flue dust by secondary blowing post-processing, needs by melting once and secondary blowing, complex process, and energy consumption
Height, the gold, silver that bismuth slag, copper ashes are taken away are high, even if the later period is recyclable by subsequent technique, but also have certain loss, and
The recovery process of precious metal especially gold, silver is extended, production efficiency is low.
The present invention melting in oxygen enriched molten bath by lead anode slurry, fluorite, iron filings and soda ash first obtains a precious metals containing lead, then
Troilite is added in precious metals containing lead or husk carries out copper removal and takes off antimony, obtains secondary precious metals containing lead, by-product copper ashes enters copper system system recycling,
Secondary precious metals containing lead obtains thick silver by vacuum distillation and carries out bessemerizing output slightly silver-colored, then send silver-colored electrolysis, vacuum distillation volatile matter is cold
It coagulates for lead bismuth alloy, lead bismuth alloy respectively send lead electrolysis and bismuth smart by isolated lead bullion and thick bismuth are evaporated in vacuo for the second time
Refining system.The process flow is simple, efficiently separates copper in lead anode slurry, antimony, and oxygen-enriched air smelting isolates cigarette containing antimony
Dirt and shoddye, silver-colored content is seldom in shoddye, and only 0.03% or so, and shoddye returns to further melting in molten bath,
Gold, silver obtain efficient rapidly extracting, and copper and bismuth do not directly obtain copper ashes and bismuth slag by melting, one that melting is obtained
Troilite is added in secondary precious metals containing lead or husk carries out copper removal and takes off antimony, obtains copper ashes, and lead bismuth alloy is separated by second of vacuum distillation
Into thick bismuth, with number of patent application CN201310336279.6, copper ashes and bismuth slag phase ratio, copper of the invention are isolated in direct melting
Less, the especially silver-colored content of the gold and silver taken away in slag and thick bismuth, can be improved the direct yield of gold and silver, and shorten gold,
The recovery process of silver, high production efficiency；In addition lead anode slurry is handled using the method for oxygen-enriched air smelting, controls excess air
Coefficient is 0.5-0.8, and the thermal efficiency greatly improves, and energy consumption substantially reduces, and accelerates the burn-off rate of lead anode slurry, greatly improves melting
Efficiency effectively reduces the generation of exhaust gas, improves waste gas recovery rate.
Fluorite is added in the present invention and iron filings control FeO and SiO in a precious metals containing lead2Mass ratio 1.5-1.8:1, CaO and SiO2
Mass ratio be 0.5-1.0:1, can make a precious metals containing lead subsequent copper removal take off antimony and vacuum distillation separation process in your each gold
The separation for belonging to element is simpler, and separative efficiency is higher, and separation is more thorough, substantially reduces separation process.
Secondary precious metals containing lead of the invention separates lead, bismuth and silver by being evaporated in vacuo twice, obtains lead bullion, thick bismuth and thick silver,
And be in the prior art usually that silver and bismuth etc. are isolated using leaching and neutralization method, such as number of patent application
The heavy silver of vulcanized sodium is added in CN201010179026.9 into melting leached mud, obtains thick silver, adds sodium carbonate and neutralized
Heavy bismuth obtains bismuth oxychloride, the method complex process after separation of solid and liquid, and silver is low with the rate of recovery of bismuth, and side reaction is more, after
Phase processing is complicated, low separation efficiency.The present invention is separated using physical method, and operating process is simple, and low energy consumption, is saved a large amount of
Manpower and material resources, easily realize production industrialization.
The beneficial effects of the present invention are:
1, present invention process process is simple, and oxygen-enriched air smelting isolates flue dust containing antimony and shoddye, and silver-colored content is seldom in shoddye,
Only 0.03% or so, and shoddye returns to further melting in molten bath, and gold, silver obtain efficient rapidly extracting, copper and bismuth
Copper ashes and bismuth slag are not directly obtained by melting, troilite is added in the precious metals containing lead that melting obtains or husk removes
Copper takes off antimony, obtains copper ashes, lead bismuth alloy by isolated thick bismuth is evaporated in vacuo for the second time, the gold taken away in copper ashes and thick bismuth and
Silver is less, especially silver-colored content, can be improved the direct yield of gold and silver, and shorten the recovery process of gold, silver, production efficiency
It is high.
2, the present invention is handled lead anode slurry using the method for oxygen-enriched air smelting, and control excess air coefficient is 0.5-
0.8, the thermal efficiency greatly improves, and energy consumption substantially reduces, and accelerates the burn-off rate of lead anode slurry, greatly improves smelting efficiency, effectively
The generation for reducing exhaust gas improves waste gas recovery rate.
3, lead of the invention, bismuth obtain efficiently separating purification, which has efficiently quickly separated and recovered lead anode
Various precious metals in mud, use scope is extensive, there is very strong industrialization prospect.
4, lead, bismuth and silver are separated by being evaporated in vacuo twice, obtain lead bullion, thick bismuth by the secondary precious metals containing lead that the present invention obtains
With thick silver, using physical separation method, operating process is simple, and low energy consumption, saves a large amount of manpower and material resources, easily realizes production industry
Change.
5, the invention has the advantages of low raw material cost, simple process, high production efficiency, and entire treatment process is safe and efficient, no nocuousness
Gas generates, and noise is far below national standard, and no noxious waste pollution is conducive to environmental protection, realizes safety in production.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this hair
Bright further description.
Embodiment 1
1) oxygen-enriched air is blasted into oxygen enriched molten bath, excess air coefficient control is 0.6, then by lead anode slurry, fluorite, iron
Bits and soda ash are added melting in oxygen enriched molten bath after mixing, and temperature control is 1150 DEG C, obtain a precious metals containing lead, flue dust and dilute
Slag, flue dust recycle through waste heat, obtain flue gas and stibium trioxide after purifying and dedusting, and flue gas can be directly discharged in air, and stibium trioxide is recyclable
It utilizes, shoddye, which returns, continues melting in oxygen enriched molten bath；The wherein metal member in lead anode slurry including following weight percent content
Element: lead 10.21%, silver 6.38%, bismuth 11.66%, copper 4.19%, antimony 37.27%；Lead anode slurry, fluorite, iron filings and soda ash
Mass ratio is 100:0.5:1:5；
2) precious metals containing lead carries out the de- antimony of copper removal in melting pot, and troilite is added, and temperature control is 650 DEG C, obtains secondary
Precious metals containing lead and copper ashes, the addition quality of the troilite are the 0.1% of a precious metals containing lead quality, and copper ashes enters copper system system recycling, secondary
Containing mass fraction≤2% of copper, mass fraction≤5% of lead element in precious metals containing lead；
3) secondary precious metals containing lead is evaporated in vacuo, vacuum degree 12Pa, temperature is 1050 DEG C, and volatile matter condenses to obtain lead bismuth
Alloy, remaining slag charge are thick silver, and thick galactic longitude is crossed to bessemerize send silver-colored electrolysis again；
4) lead bismuth alloy is carried out second to be evaporated in vacuo, vacuum degree 7Pa, temperature is 550 DEG C, and lead and bismuth are isolated
Thick bismuth and lead bullion, thick bismuth send bismuth to refine, and lead bullion send lead to be electrolysed.
Embodiment 2
1) oxygen-enriched air is blasted into oxygen enriched molten bath, excess air coefficient control is 0.8, then by lead anode slurry, fluorite, iron
Bits and soda ash are added melting in oxygen enriched molten bath after mixing, and temperature control is 1050 DEG C, obtain a precious metals containing lead, flue dust and dilute
Slag, flue dust recycle through waste heat, obtain flue gas and stibium trioxide after purifying and dedusting, and flue gas can be directly discharged in air, and stibium trioxide is recyclable
It utilizes, shoddye, which returns, continues melting in oxygen enriched molten bath；The wherein metal member in lead anode slurry including following weight percent content
Element: lead 28.56%, silver 2.24%, bismuth 18.32%, copper 1.55%, antimony 11.25%；Lead anode slurry, fluorite, iron filings and soda ash
Mass ratio is 100:0.5:1:5；
2) precious metals containing lead carries out the de- antimony of copper removal in melting pot, and troilite is added, and temperature control is 600 DEG C, obtains secondary
Precious metals containing lead and copper ashes, the addition quality of the husk are the 0.2% of a precious metals containing lead quality, and copper ashes enters copper system system recycling, secondary expensive
Containing mass fraction≤2% of copper, mass fraction≤5% of lead element in lead；
3) secondary precious metals containing lead is evaporated in vacuo, vacuum degree 15Pa, temperature is 1100 DEG C, and volatile matter condenses to obtain lead bismuth
Alloy, remaining slag charge are thick silver, and thick galactic longitude is crossed to bessemerize send silver-colored electrolysis again；
4) lead bismuth alloy is carried out second to be evaporated in vacuo, vacuum degree 10Pa, temperature is 600 DEG C, and lead and bismuth separate
To thick bismuth and lead bullion, thick bismuth send bismuth to refine, and lead bullion send lead to be electrolysed.
Embodiment 3
1) oxygen-enriched air is blasted into oxygen enriched molten bath, excess air coefficient control is 0.5, then by lead anode slurry, fluorite, iron
Bits and soda ash are added melting in oxygen enriched molten bath after mixing, and temperature control is 1250 DEG C, obtain a precious metals containing lead, flue dust and dilute
Slag, flue dust recycle through waste heat, obtain flue gas and stibium trioxide after purifying and dedusting, and flue gas can be directly discharged in air, and stibium trioxide is recyclable
It utilizes, shoddye, which returns, continues melting in oxygen enriched molten bath；The wherein metal member in lead anode slurry including following weight percent content
Element: lead 6.41%, silver 18.25%, bismuth 5.68%, copper 8.45%, antimony 27.11%；Lead anode slurry, fluorite, iron filings and soda ash
Mass ratio is 100:0.5:1:5；
2) precious metals containing lead carries out the de- antimony of copper removal in melting pot, and troilite is added, and temperature control is 800 DEG C, obtains secondary
Precious metals containing lead and copper ashes, the addition quality of the troilite are the 0.3% of a precious metals containing lead quality, and copper ashes enters copper system system recycling, secondary
Containing mass fraction≤2% of copper, mass fraction≤5% of lead element in precious metals containing lead；
3) secondary precious metals containing lead is evaporated in vacuo, vacuum degree 10Pa, temperature is 900 DEG C, and volatile matter condenses to obtain lead bismuth
Alloy, remaining slag charge are thick silver, and thick galactic longitude is crossed to bessemerize send silver-colored electrolysis again；
4) lead bismuth alloy is carried out second to be evaporated in vacuo, vacuum degree 6Pa, temperature is 450 DEG C, and lead and bismuth are isolated
Thick bismuth and lead bullion, thick bismuth send bismuth to refine, and lead bullion send lead to be electrolysed.
Comparative example 1
1) oxygen-enriched air is blasted into oxygen enriched molten bath, excess air coefficient control is 0.8, then by lead anode slurry, fluorite, iron
Bits and soda ash are added melting in oxygen enriched molten bath after mixing, and temperature control is 1050 DEG C, obtain a precious metals containing lead, flue dust and dilute
Slag, flue dust recycle through waste heat, obtain flue gas and stibium trioxide after purifying and dedusting, and flue gas can be directly discharged in air, and stibium trioxide is recyclable
It utilizes, shoddye, which returns, continues melting in oxygen enriched molten bath；The wherein metal member in lead anode slurry including following weight percent content
Element: lead 28.56%, silver 2.24%, bismuth 18.32%, copper 1.55%, antimony 11.25%；Lead anode slurry, fluorite, iron filings and soda ash
Mass ratio is 100:0.5:1:5；
2) precious metals containing lead carries out the de- antimony of copper removal in melting pot, and troilite is added, and temperature control is 600 DEG C, obtains secondary
Precious metals containing lead and copper ashes, the addition quality of the troilite are the 0.2% of a precious metals containing lead quality, and copper ashes enters copper system system recycling, secondary
Containing mass fraction≤2% of copper, mass fraction≤5% of lead element in precious metals containing lead；
3) hydrochloric acid solution and vulcanized sodium are added in secondary precious metals containing lead, stirs 20-30min, silver precipitating is made to obtain silver-colored slag；
4) industrial sodium carbonate will be added in the liquid through the heavy silver of sodium persulfide and after isolating silver, adjustment solution ph is
2.0-3.0 neutralizes heavy bismuth, until bismuth precipitating is completely, is separated by solid-liquid separation, obtains bismuth slag.
Comparative example 2
Lead anode slurry is handled using the method in number of patent application CN201310336279.6.
Using the method for embodiment 1 from lead anode slurry high efficiente callback precious metal, each metal in obtained each regulus
The content of element such as table 1.
The mass percentage of each metallic element in each regulus of table 1
| Regulus title | Lead element (%) | Silver element (%) | Bismuth element (%) | Copper (%) | Antimony element (%) |
| Thick silver | 0.08 | 99.1 | 0.2 | 0.1 | — |
| Thick bismuth | 1.8 | 0.2 | 95.6 | 1.3 | — |
| Lead bullion | 97.4 | 0.03 | 0.23 | 0.25 | — |
| Copper ashes | — | 0.01 | — | 28.9 | 14.8 |
| Shoddye | 2.7 | 0.03 | 0.5 | 0.9 | 1.3 |
| Stibium trioxide | — | 0.01 | — | — | 73.2 |
From the data in table 1 it is found that using the processing method of embodiment 1 from lead anode slurry high efficiente callback precious metal,
The content of other metallic elements is seldom in each regulus, some metallic elements are even without silver-colored content reaches 99% in thick silver
More than, the content of lead reaches 97.4% in lead bullion, illustrates each metal being recovered to from lead anode slurry using the method for embodiment 1
Direct yield is high, especially the direct yield of lead and silver.
Precious metal, the direct yield of each metal are recycled from lead anode slurry using the method for embodiment 1-3 and comparative example 1-2
Such as table 2.
The direct yield of each metallic element of table 2
From the data in table 2 it is found that using method of the invention from from lead anode slurry high efficiente callback precious metal, each gold
The direct yield of category is higher, and the direct yield for all having reached 90% or more, especially silver element substantially has reached 98% or more；And it compares
The direct yield of each metallic element is lower in example 1 and 2, illustrates that method of the invention can be improved the direct yield of each metallic element, raw
Produce high-efficient, and secondary precious metals containing lead separates lead, bismuth and silver by being evaporated in vacuo twice, obtains lead bullion, thick bismuth and thick silver, phase
Compared with silver and bismuth is isolated using leaching and neutralization method in the prior art, the present invention is separated using physical method, is operated
Process is simple, and low energy consumption, and the direct yield of lead, silver and bismuth element is higher, saves a large amount of manpower and material resources, easily realizes production industry
Change.
Claims (10)
1. a kind of method of precious metal in high efficiente callback lead anode slurry, which comprises the following steps:
1) oxygen-enriched air is blasted into oxygen enriched molten bath, excess air coefficient control is 0.5-0.8, then by lead anode slurry, fluorite, iron
Melting in oxygen enriched molten bath is added in bits and soda ash after mixing, obtains a precious metals containing lead；
2) additive is added in a precious metals containing lead and carries out the de- antimony of copper removal, obtains secondary precious metals containing lead and copper ashes；
3) secondary precious metals containing lead is evaporated in vacuo, vacuum degree 10-15Pa, temperature be 900-1100 DEG C, obtain lead bismuth alloy and
Thick silver；
4) lead bismuth alloy is carried out second to be evaporated in vacuo, vacuum degree is 6-10Pa, and temperature is 450-600 DEG C, obtains thick bismuth
And lead bullion.
2. the method for precious metal in high efficiente callback lead anode slurry as described in claim 1, which is characterized in that described in step 1)
It include the metallic element of following weight percent content: lead 5%-30%, silver-colored 1%-20%, bismuth 1%-20% in lead anode slurry,
Copper 1%-10%, antimony 1%-50%.
3. the method for precious metal in high efficiente callback lead anode slurry as described in claim 1, which is characterized in that described in step 1)
Lead anode slurry, fluorite, iron filings and soda ash mass ratio be 100:0.5:1:5.
4. the method for precious metal in high efficiente callback lead anode slurry as claimed in claim 1 or 2, which is characterized in that in step 1)
The smelting temperature is 1050-1250 DEG C.
5. the method for precious metal in high efficiente callback lead anode slurry as claimed in claim 1 or 2, which is characterized in that in step 1)
Flue dust and shoddye are also obtained after the melting.
6. the method for precious metal in high efficiente callback lead anode slurry as claimed in claim 5, which is characterized in that described in step 1)
Flue dust recycles through waste heat, obtains flue gas and stibium trioxide after purifying and dedusting.
7. the method for precious metal in high efficiente callback lead anode slurry as claimed in claim 1 or 2, which is characterized in that in step 2)
The additive is troilite or husk.
8. as described in claim any one of 1-3 in high efficiente callback lead anode slurry precious metal method, which is characterized in that step
2) the addition quality of additive described in is the 0.1-0.3% of a precious metals containing lead quality.
9. as described in claim any one of 1-3 in high efficiente callback lead anode slurry precious metal method, which is characterized in that step
2) temperature that copper removal described in takes off antimony is 600-800 DEG C.
10. as described in claim any one of 1-3 in high efficiente callback lead anode slurry precious metal method, which is characterized in that step
It is rapid 2) described in mass fraction≤2% containing copper, mass fraction≤5% of lead element in secondary precious metals containing lead.
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| CN115627367A (en) * | 2022-10-14 | 2023-01-20 | 北京科技大学 | Method for lead and antimony co-smelting |
| CN116426766A (en) * | 2023-06-12 | 2023-07-14 | 昆明理工大学 | Method for extracting silver from complex lead bullion |
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