CN108728648B - The process of high tin-lead calcium alloy is produced using lead-acid accumulator scrap lead aperture plate - Google Patents
The process of high tin-lead calcium alloy is produced using lead-acid accumulator scrap lead aperture plate Download PDFInfo
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- CN108728648B CN108728648B CN201810518690.8A CN201810518690A CN108728648B CN 108728648 B CN108728648 B CN 108728648B CN 201810518690 A CN201810518690 A CN 201810518690A CN 108728648 B CN108728648 B CN 108728648B
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- calcium
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- 239000002142 lead-calcium alloy Substances 0.000 title claims abstract description 28
- YBOXAZZJNODWJE-UHFFFAOYSA-N [Pb].[Sn].[Ca] Chemical compound [Pb].[Sn].[Ca] YBOXAZZJNODWJE-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000002253 acid Substances 0.000 title claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 85
- DLISVFCFLGSHAB-UHFFFAOYSA-N antimony arsenic Chemical compound [As].[Sb] DLISVFCFLGSHAB-UHFFFAOYSA-N 0.000 claims abstract description 54
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 43
- 239000010949 copper Substances 0.000 claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 claims abstract description 35
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 30
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 19
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010792 warming Methods 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 11
- 230000008018 melting Effects 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000004927 fusion Effects 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims description 53
- 239000011575 calcium Substances 0.000 claims description 22
- 229910052791 calcium Inorganic materials 0.000 claims description 22
- 238000010183 spectrum analysis Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 239000002893 slag Substances 0.000 claims description 19
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- 238000005070 sampling Methods 0.000 claims description 16
- 239000004411 aluminium Substances 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 239000000956 alloy Substances 0.000 claims description 13
- 238000005275 alloying Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 238000007670 refining Methods 0.000 claims description 8
- 238000005336 cracking Methods 0.000 claims description 7
- WVOZQBGJYFSVHF-UHFFFAOYSA-N [Pb].[Sb].[As] Chemical compound [Pb].[Sb].[As] WVOZQBGJYFSVHF-UHFFFAOYSA-N 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 6
- 239000002817 coal dust Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 5
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052683 pyrite Inorganic materials 0.000 claims description 5
- 239000011028 pyrite Substances 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052949 galena Inorganic materials 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000009967 tasteless effect Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract 1
- 229910052797 bismuth Inorganic materials 0.000 description 13
- 229910052709 silver Inorganic materials 0.000 description 13
- 229910052745 lead Inorganic materials 0.000 description 12
- 239000004615 ingredient Substances 0.000 description 7
- 238000010009 beating Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- 229910001245 Sb alloy Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000002140 antimony alloy Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 241000500881 Lepisma Species 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- -1 calcium rare earth Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material 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
- 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
- C22B13/00—Obtaining lead
- C22B13/06—Refining
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C11/00—Alloys based on lead
- C22C11/06—Alloys based on lead with tin as the next major constituent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
A kind of process producing high tin-lead calcium alloy using lead-acid accumulator scrap lead aperture plate, belongs to lead-acid accumulator comprehensive reutilization field.Scrap lead aperture plate cold melt in melting pot, fusion temperature are controlled at 350-500 DEG C, beat lime-ash, and decopper(ing) agent copper removal is added to obtain decopperized lead liquid；Decopperized lead liquid is warming up to 580~650 DEG C, adds except antimony arsenic protects tin agent except antimony arsenic obtains liquid containing tin-lead, then to the purified treatment of liquid containing tin-lead, then prepare high tin-lead calcium alloy.The lead-calcium alloy that the indexs such as high its tensile strength of tin-lead calcium alloy, density, hardness and the corrosion resistance of production are prepared with primary electrolytic lead is almost the same, meets the requirement of accumulator cell lead calcium alloy.Advantage: the simple process, easy to operate, high production efficiency efficiently utilize metallic tin valuable in scrap lead aperture plate, reduce the production cost of lead-calcium alloy preparation, while smoke-free and tasteless, working environment are good except antimony, in arsenic reaction process.
Description
Technical field
The present invention relates to a kind of lead-acid accumulator comprehensive reutilization field more particularly to a kind of useless lead acid storage batteries of utilization
Pond scrap lead aperture plate produces the process of high tin-lead calcium alloy.
Background technique
Lead acid accumulator plate grid is most important inert matter in battery, serves as the important carrier of active material, plays
The effect for conducting and collecting electric current, makes balanced current distribution on active material.Lead-antimony alloy is always the most important choosing of grid
With material, with the appearance of maintenance-free lead-acid battery, lead-antimony alloy has been unable to meet the non-maintaining performance requirement of battery, gradually by
Lead-calcium alloy is substituted, and research finds that lead-calcium alloy has lesser resistivity, good electric conductivity and excellent mechanical strength,
Manufactured lead-acid accumulator dehydration is slow, can achieve few maintenance or non-maintaining technical requirements.Common lead-calcium alloy is general
It is prepared using primary electrolytic lead, certain restriction will necessarily be brought to buying and production, be unfavorable for the control of cost.
Lead-acid accumulator generates following four component after automatic pulverizing separation system is broken, and scrap lead aperture plate, gives up at lead mud
Plastics and separator paper, wherein scrap lead aperture plate accounts for 25-30% or so.Battery of electric vehicle, the positive and negative stereotype grid for communicating the batteries such as energy storage are
It is made of slicker solder calloy, the negative grid having uses low-antimony-lead alloy, and the scrap lead aperture plate generated after cracking and sorting is in melting
Cold melt produces reviver in pot, and ingredient is general are as follows: Pb >=99%, Sb≤0.2%, As≤0.1%, and Fe≤0.005%,
Sn0.30~0.80%, Cu≤0.02%, Cd≤0.02%, Bi≤0.004%, Ag≤0.0008%, when alloyage must to its into
Row refining removal of impurities, traditional method has refinement oxide and basic refining, due to three kinds of antimony, arsenic, tin metallic element chemical property phases
Closely, refining can all be simultaneously removed in dedoping step, all can be by high price in lead bullion when no matter using refinement oxide or basic refining
The metallic tin oxidation of value enters in refining slag, causes tin resource largely to waste, increases production cost.
Summary of the invention
The invention aims to provide a kind of work that high tin-lead calcium alloy is produced using lead-acid accumulator scrap lead aperture plate
Process solves in the prior art, no matter uses refinement oxide or basic refining all cannot be using metallic tin in scrap lead aperture plate
Problem.
The technical scheme of the present invention is realized as follows: technical solution is as follows: scrap lead aperture plate cold melt in melting pot,
Fusion temperature is controlled at 350-500 DEG C, beats lime-ash, and decopper(ing) agent copper removal is added to obtain decopperized lead liquid；Decopperized lead liquid is warming up to 580~
650 DEG C, add except antimony arsenic protects tin agent except antimony arsenic obtains liquid containing tin-lead, then to the purified treatment of liquid containing tin-lead, then prepare high tin-lead calcium
Alloy.
In the present invention, the production method of high tin-lead calcium alloy is as follows:
Step (1), cold melt scrap lead aperture plate；The lead that the cracking and sortings such as useless battery of electric bicycle, maintenance-free battery go out
Aperture plate cold melt in melting pot, temperature control obtain lead bullion liquid at 350-500 DEG C, beat grey Slag treatment to lead bullion liquid, then use
Lead pump is pumped into copper removal pot, or is transported to copper removal pot by keeping the temperature sheath；
Step (2) carries out decopper(ing) processing in copper removal pot；Temperature is controlled at 330-550 DEG C, decopper(ing) agent copper removal is added, so
After sample, spectrum analysis is carried out to sample, when reaching Cu≤0.001%, ash Slag treatment is beaten to decopperized lead liquid, reusable lead is pumped into
Kier；
Step (3) carries out handling except antimony arsenic in kier；Sampling carries out spectrum analysis to sample, obtains the antimony in pot
Arsenic total content is warming up to 580-650 DEG C, then will protect tin agent except antimony arsenic and be added into kier, except antimony arsenic protects what tin agent was added
Amount is calculated by 1-1.5 times of antimony arsenic total content；Blender is opened, stirring lead liquid generates vortex, and investment protects the speed of tin agent except antimony arsenic
Measurement should not influence the normal presence of whirlpool, be combined to antimonide except antimony arsenic is protected tin agent and fused into antimony arsenic in lead liquid and float on lead liquid
Liquid level, add except antimony arsenic protect tin agent after continue 10~60min of stirring；Cooling is stood, the lead liquid temperature after reaction is down to 480
DEG C hereinafter, coal dust is added or sawdust stirring removes remaining calcium, aluminium, until white paste slag becomes loose black powdery；
Sampling, carries out spectrum analysis to sample, and Sb≤0.0005%, As≤0.0005% in lead liquid beat grey Slag treatment, then removes antimony arsenic
Lead liquid is pumped into alloy pot with lead pump；
Alloying element Alloying Treatment is added in alloy pot for step (4), be warming up to 580-680 DEG C of addition lead calcium master alloy,
Or calloy or aluminium, calcium carry out Alloying Treatment, and pure tin then is added further according to Customer Standard and adjusts Theil indices, samples, into
Row spectrum analysis；
Step (5), is cooled to 480-600 DEG C, is pumped into casting machine with lead pump, ingot casting is at high tin-lead calcium alloy finished product.
The scrap lead aperture plate is lead grid net, the lead part of battery of electric bicycle, maintenance-free battery cracking and sorting out.
The decopper(ing) agent is sulfur granule, pyrite, red phosphorus, one kind of galena or several constituted mixtures.
The antimony arsenic guarantor's tin agent that removes is on the basis of its gross mass by the aluminium of 10~30wt%, the calcium of 65~85wt%, 1
The compound that the coke powder of~10wt% and the lead powder of 1~2wt% are constituted.
Beneficial effect, simple process of the invention, easy to operate, high production efficiency as the above scheme is adopted, effectively
Ground utilizes metallic tin valuable in scrap lead aperture plate.Except antimony arsenic protects coke powder in tin agent used by technical process, it can avoid lead liquid and exist
Slag making under high temperature, is conducive to prevent the oxidation of lead, and a small amount of lead powder can make sufficiently quickly to be dissolved in lead liquid except the guarantor's tin agent of antimony arsenic；
Except antimony arsenic protects calcium, aluminium in tin agent, it can be reacted at high temperature with antimony, arsenic and generate antimonide, arsenide；Except the process of antimony, arsenic
In, antimonide, the arsenide fusing point of generation are high, and the dissolubility in lead liquid is very low, its density is less than lead, can be precipitated from lead liquid
On float on and become dross above lead liquid, with the reduction of temperature, antimonide arsenide is further under the action of blender stirring
The emersion from lead liquid and remove, reaching antimony, arsenic and the depth of lead liquid separates, can by lead liquid antimony, arsenic content is 0.0005%
Hereinafter, and Theil indices are basically unchanged.The lead calcium rare earth alloy prepared using scrap lead aperture plate production reviver is through domestic large-scale electric power storage
The detection of pond producer uses, and reaction effect is good.Detected the indexs such as its tensile strength, density, hardness and corrosion resistance with it is primary
The lead-calcium alloy that electrolytic lead is prepared is almost the same, can satisfy the requirement of battery electric property completely.
It solves in the prior art, no matter uses refinement oxide or basic refining all cannot be using metallic tin in scrap lead aperture plate
The problem of, reach the purpose of the present invention.
Advantage: 1, optionally removing antimony, arsenic, greatly retains the valuable metal tin in lead, reduces alloyage
Production cost.
2, antimony, arsenic content are far below national standard, antimony arsenic removal rate is high down to 0.0005% in lead.
3, except antimony, arsenic reaction are fast, reagent dosage is few, and slag making amount is few.
4, operating method is simple and reliable, applied widely, smoke-free and tasteless in reaction process, and working environment is good.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Method of the invention is: scrap lead aperture plate cold melt in melting pot, and fusion temperature is controlled at 350-500 DEG C, beats
Lime-ash adds decopper(ing) agent copper removal to obtain decopperized lead liquid；Decopperized lead liquid is warming up to 580~650 DEG C, adds except antimony arsenic protects tin agent except antimony arsenic obtains
Tin-lead liquid must be contained, then to the purified treatment of liquid containing tin-lead, then prepare high tin-lead calcium alloy.
In the present invention, the production method of high tin-lead calcium alloy is specific as follows:
Step (1), cold melt scrap lead aperture plate；The lead that the cracking and sortings such as useless battery of electric bicycle, maintenance-free battery go out
Aperture plate cold melt in melting pot, temperature control obtain lead bullion liquid at 350-500 DEG C, beat grey Slag treatment to lead bullion liquid, then use
Lead pump is pumped into copper removal pot, or is transported to copper removal pot by keeping the temperature sheath；
Step (2) carries out decopper(ing) processing in copper removal pot；Temperature is controlled at 330-550 DEG C, decopper(ing) agent copper removal is added, so
After sample, spectrum analysis is carried out to sample, when reaching Cu≤0.001%, ash Slag treatment is beaten to decopperized lead liquid, reusable lead is pumped into
Kier；
Step (3) carries out handling except antimony arsenic in kier；Sampling carries out spectrum analysis to sample, obtains the antimony in pot
Arsenic total content is warming up to 580-650 DEG C, then will protect tin agent except antimony arsenic and be added into kier, except antimony arsenic protects what tin agent was added
Amount is calculated by 1-1.5 times of antimony arsenic total content；Blender is opened, stirring lead liquid generates vortex, and investment protects the speed of tin agent except antimony arsenic
Measurement should not influence the normal presence of whirlpool, be combined to antimonide except antimony arsenic is protected tin agent and fused into quickly with antimony arsenic in lead liquid and float on
The liquid level of lead liquid adds and continues 10~60min of stirring after protecting tin agent except antimony arsenic；Cooling is stood, the lead liquid temperature after reaction is dropped
To 480 DEG C hereinafter, coal dust or the remaining calcium of sawdust stirring removing, aluminium is added, until white paste slag becomes loose black powdery
Until；Sampling, carries out spectrum analysis to sample, and Sb≤0.0005%, As≤0.0005% in lead liquid beat grey Slag treatment, then
Except antimony arsenic lead liquid is pumped into alloy pot with lead pump；
Alloying element Alloying Treatment is added in alloy pot, is warming up to 580-680 DEG C of addition lead calcium master alloy for step (4)
Or calloy or aluminium, calcium carry out Alloying Treatment, and pure tin then is added further according to Customer Standard and adjusts Theil indices, samples, into
Row spectrum analysis；
Step (5), is cooled to 480-600 DEG C, is pumped into casting machine with lead pump, ingot casting is at high tin-lead calcium alloy finished product.
The scrap lead aperture plate is lead grid net, the lead part of battery of electric bicycle, maintenance-free battery cracking and sorting out.
The decopper(ing) agent is sulfur granule, pyrite, red phosphorus, one kind of galena or several constituted mixtures.
The antimony arsenic guarantor's tin agent that removes is on the basis of its gross mass by the aluminium of 10~30wt%, the calcium of 65~85wt%, 1
The compound that the coke powder of~10wt% and the lead powder of 1~2wt% are constituted.
Technical solution of the present invention is further illustrated with reference to the accompanying drawing:
Embodiment 1: scrap lead aperture plate melts in melting pot at 410 ± 20 DEG C, beats after lime-ash lead liquid with lead pump and is pumped into copper removal
Pot, sampling spectral analysis, ingredient: Sb 0.132%, As 0.0051%, Sn 0.71%, Cu 0.013%, Bi 0.0031%, Ag
0.00062%, Pb surplus；490 ± 20 DEG C are heated to, pyrite dust copper removal is added, samples direct reading spectrometry, ingredient is as follows:
Sb 0.130%, As 0.0051%, Sn 0.70%, Cu 0.0005%, Bi 0.0031%, Ag 0.00062%, Pb surplus.
Decopperized lead liquid with lead pump is pumped into kier after beating lime-ash.
580 ± 20 DEG C are warming up to by decopperized lead liquid is removed in kier, is protected by 1.1 times of calculating of antimony arsenic total amount using except antimony arsenic
The amount of tin agent opens blender, and stirring lead liquid generates vortex, puts into speed not influence the normal presence of whirlpool, except antimony arsenic is protected
Tin agent is fused into quickly is combined to antimonide emersion lead liquid with antimony arsenic in lead liquid, continue to stir 30min after adding.
Cooling is stood, the lead liquid temperature after reaction is down to 480 DEG C hereinafter, addition coal dust or sawdust stirring removing are remaining
Calcium, aluminium, until white paste slag becomes loose black powdery, sampling spectral analysis: Sb 0.00041%, As 0.0002%,
Sn 0.69%, Cu 0.0005%, Bi 0.0031%, Ag 0.00063%, Pb surplus；It beats after lime-ash except antimony arsenic lead liquid is pumped with lead pump
Enter alloy pot.
620 ± 20 DEG C are heated to, calloy alloying is added, pure tin is added by tin by consumer product standard requirements
It is adjusted in 1.2 ± 0.05% standards, sampling spectral analysis: Sn 1.21%, Cu 0.0005%, Ca 0.07%, Al
0.022%, Sb 0.00042%, As 0.0002%, Bi 0.0032%, Ag 0.00063%, Pb surplus；Cooling is cast into high tin
Ingot of Pb-Ca Alloy.
Embodiment 2: scrap lead aperture plate melts in melting pot at 370 ± 20 DEG C, beats after lime-ash lead liquid with lead pump and is pumped into copper removal
Pot, sampling spectral analysis, ingredient: Sb 0.08%, As 0.009%, Sn 0.61%, Cu 0.013%, Bi 0.004%, Ag
0.00078%, Pb surplus；360 ± 20 DEG C are cooled to, red phosphorus copper removal is added, samples direct reading spectrometry, ingredient is as follows: Sb
0.081%, As 0.0081%, Sn 0.592%, Cu 0.0004%, Bi 0.004%, Ag 0.00078%, Pb surplus.
Decopperized lead liquid with lead pump is pumped into kier after beating lime-ash.
570 ± 20 DEG C are warming up to by decopperized lead liquid is removed in kier, is protected by 1.5 times of calculating of antimony arsenic total amount using except antimony arsenic
The amount of tin agent opens blender, and stirring lead liquid generates vortex, puts into speed not influence the normal presence of whirlpool, except antimony arsenic is protected
Lead liquid is fused into tin agent quickly and antimony arsenic is combined to antimonide emersion lead liquid, continues to stir 30min after adding.
Cooling is stood, the lead liquid temperature after reaction is down to 480 DEG C hereinafter, addition coal dust or sawdust stirring removing are remaining
Calcium, aluminium, until white paste slag becomes loose black powdery, sampling spectral analysis: Sb 0.00041%, As 0.0001%,
Sn 0.59%, Cu 0.00042%, Bi 0.0039%, Ag 0.00078%, Pb surplus；It beats after lime-ash except antimony arsenic lead liquid is pumped with lead pump
Enter alloy pot.
610 ± 20 DEG C are heated to, calloy alloying is added, pure tin is added by tin by consumer product standard requirements
It is adjusted in 1.3 ± 0.05% standards, sampling spectral analysis: Sn 1.29%, Cu 0.00042%, Ca 0.08%, Al
0.025%, Sb 0.00041%, As 0.0001%, Bi 0.0039%, Ag 0.00079%, Pb surplus；Cooling is cast into high tin
Ingot of Pb-Ca Alloy.
Embodiment 3: scrap lead aperture plate melts in melting pot at 430 ± 20 DEG C, beats after lime-ash lead liquid with lead pump and is pumped into copper removal
Pot, sampling spectral analysis, ingredient: Sb 0.07%, As 0.01%, Sn 0.45%, Cu 0.014%, Bi 0.004%, Ag
0.0008%, Pb surplus；480 ± 20 DEG C are heated to, pyrite dust copper removal is added, samples direct reading spectrometry, ingredient is as follows:
Sb 0.069%, As 0.0091%, Sn 0.45%, Cu 0.00046%, Bi 0.004%, Ag 0.00079%, Pb surplus.
Decopperized lead liquid with lead pump is pumped into kier after beating lime-ash.
580 ± 20 DEG C are warming up to by decopperized lead liquid is removed in kier, is protected by 1.4 times of calculating of antimony arsenic total amount using except antimony arsenic
The amount of tin agent opens blender, and stirring lead liquid generates vortex, puts into speed not influence the normal presence of whirlpool, removes antimony, arsenic group
Conjunction object fuses into quickly is combined to antimonide emersion lead liquid with antimony arsenic in lead liquid, continue to stir 50min after adding.
Cooling is stood, the lead liquid temperature after reaction is down to 480 DEG C hereinafter, addition coal dust or sawdust stirring removing are remaining
Calcium, aluminium, until white paste slag becomes loose black powdery, sampling spectral analysis: Sb 0.0005%, As 0.0001%,
Sn 0.44%, Cu 0.0005%, Bi 0.004%, Ag 0.00079%, Pb surplus；It beats after lime-ash except antimony arsenic lead liquid is pumped into lead pump
Alloy pot.
630 ± 20 DEG C are heated to, calloy alloying is added, pure tin is added by tin by consumer product standard requirements
It is adjusted in 1.0 ± 0.05% standards, sampling spectral analysis: Sn 0.98%, Cu 0.0005%, Ca 0.08%, Al
0.026%, Sb 0.0005%, As 0.0001%, Bi 0.004%, Ag 0.0008%, Pb surplus；Cooling is cast into high tin-lead calcium
Alloy pig.
Claims (4)
1. a kind of process for producing high tin-lead calcium alloy using lead-acid accumulator scrap lead aperture plate, it is characterized in that: scrap lead grid
Net cold melt in melting pot, fusion temperature are controlled at 350-500 DEG C, beat lime-ash, and decopper(ing) agent copper removal is added to obtain decopperized lead liquid；
Decopperized lead liquid is warming up to 580~650 DEG C, add except antimony arsenic protect tin agent except antimony arsenic obtain liquid containing tin-lead, then to the purification of liquid containing tin-lead at
Reason, then prepares high tin-lead calcium alloy；
What technical process was utilized removes coke powder in the guarantor's tin agent of antimony arsenic, can avoid the slag making at high temperature of lead liquid, is conducive to prevent lead
Oxidation, a small amount of lead powder can make sufficiently quickly to be dissolved in lead liquid except the guarantor's tin agent of antimony arsenic；It, can except antimony arsenic protects calcium, aluminium in tin agent
Antimonide, arsenide are generated to react at high temperature with antimony, arsenic；During antimony, arsenic, antimonide, the arsenide of generation are molten
Point is high, and the dissolubility in lead liquid is very low, its density is less than lead, can become dross above lead liquid from being precipitated to float in lead liquid,
With the reduction of temperature, under the action of blender stirring antimonide arsenide further from lead liquid emersion and remove, reach
It is separated to antimony, arsenic with the depth of lead liquid；
It is described except antimony arsenic protect tin agent be on the basis of its gross mass by the aluminium of 10~30wt%, the calcium of 65~85wt%, 1~
The compound that the coke powder of 10wt% and the lead powder of 1~2wt% are constituted.
2. a kind of technique side for producing high tin-lead calcium alloy using lead-acid accumulator scrap lead aperture plate according to claim 1
Method, it is characterized in that: the production method of high tin-lead calcium alloy is as follows:
Step (1), cold melt scrap lead aperture plate；The lead grid net that useless battery of electric bicycle and maintenance-free battery cracking and sorting go out exists
Cold melt in melting pot, temperature control obtain lead bullion liquid at 350-500 DEG C, beat grey Slag treatment to lead bullion liquid, are then pumped with lead pump
Enter copper removal pot, or is transported to copper removal pot by keeping the temperature sheath；
Step (2) carries out decopper(ing) processing in copper removal pot；Temperature is controlled at 330-550 DEG C, and decopper(ing) agent copper removal is added, then takes
Sample carries out spectrum analysis to sample, when reaching Cu≤0.001%, beats grey Slag treatment to decopperized lead liquid, reusable lead is pumped into refining
Pot；
Step (3) carries out handling except antimony arsenic in kier；Sampling carries out spectrum analysis to sample, and the antimony arsenic obtained in pot is total
Content is warming up to 580-650 DEG C, then will protect tin agent except antimony arsenic and be added into kier, and protect the amount that tin agent is added except antimony arsenic and press
1-1.5 times of antimony arsenic total content calculates；Open blender, stirring lead liquid generate vortex, investment except antimony arsenic protect tin agent speed with
The normal presence for not influencing whirlpool protects tin agent except antimony arsenic and fuses into lead liquid the liquid for being combined to antimonide with antimony arsenic and floating on lead liquid
Face adds and continues 10~60min of stirring after protecting tin agent except antimony arsenic；Stand cooling, by the lead liquid temperature after reaction be down to 480 DEG C with
Under, coal dust is added or sawdust stirring removes remaining calcium, aluminium, until white paste slag becomes loose black powdery；Sampling,
Spectrum analysis is carried out to sample, Sb≤0.0005%, As≤0.0005% in lead liquid beat grey Slag treatment, then removes antimony arsenic lead liquid
Alloy pot is pumped into lead pump；
Alloying element Alloying Treatment is added in alloy pot, is warming up to 580-680 DEG C of addition lead calcium master alloy or calcium for step (4)
Aluminium alloy or aluminium, calcium carry out Alloying Treatment, and pure tin is then added and adjusts Theil indices, sampling carries out spectrum analysis；
Step (5), is cooled to 480-600 DEG C, is pumped into casting machine with lead pump, ingot casting is at high tin-lead calcium alloy finished product.
3. a kind of work for producing high tin-lead calcium alloy using lead-acid accumulator scrap lead aperture plate according to claim 1 or 2
Process, it is characterized in that: the lead grid net that the scrap lead aperture plate is battery of electric bicycle, maintenance-free battery cracking and sorting goes out,
Lead part.
4. a kind of work for producing high tin-lead calcium alloy using lead-acid accumulator scrap lead aperture plate according to claim 1 or 2
Process, it is characterized in that: the decopper(ing) agent is sulfur granule, one kind of pyrite, red phosphorus, galena or several is constituted
Mixture.
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| CN201810518690.8A CN108728648B (en) | 2018-05-25 | 2018-05-25 | The process of high tin-lead calcium alloy is produced using lead-acid accumulator scrap lead aperture plate |
| PCT/CN2019/086507 WO2019223560A1 (en) | 2018-05-25 | 2019-05-12 | Technique for producing lead-calcium alloy using waste lead grids of waste lead-acid storage batteries |
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| CN201810518690.8A CN108728648B (en) | 2018-05-25 | 2018-05-25 | The process of high tin-lead calcium alloy is produced using lead-acid accumulator scrap lead aperture plate |
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| WO2019223560A1 (en) * | 2018-05-25 | 2019-11-28 | 江苏新春兴再生资源有限责任公司 | Technique for producing lead-calcium alloy using waste lead grids of waste lead-acid storage batteries |
| CN108707761B (en) * | 2018-05-25 | 2019-10-29 | 江苏新春兴再生资源有限责任公司 | A kind of selectivity for regenerating the refining of lead bullion protects tin agent and application method except antimony arsenic |
| CN112899494B (en) * | 2021-01-27 | 2022-11-01 | 河南豫光金铅股份有限公司 | Method for continuous refining and decoppering of lead bullion and producing high-grade matte |
| CN113684386A (en) * | 2021-08-17 | 2021-11-23 | 尤全仁 | Method for refining secondary lead-tin-based multi-element alloy by using crude lead |
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| CN106367593A (en) * | 2016-08-25 | 2017-02-01 | 安徽华铂再生资源科技有限公司 | Process of producing lead-tin alloy from high-tin regenerated lead |
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