CN101220412B - Set technique for extracting cadmium from waste and old nickel-cadmium battery, and producing ferro-nickel alloy - Google Patents
Set technique for extracting cadmium from waste and old nickel-cadmium battery, and producing ferro-nickel alloy Download PDFInfo
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- CN101220412B CN101220412B CN2007101910536A CN200710191053A CN101220412B CN 101220412 B CN101220412 B CN 101220412B CN 2007101910536 A CN2007101910536 A CN 2007101910536A CN 200710191053 A CN200710191053 A CN 200710191053A CN 101220412 B CN101220412 B CN 101220412B
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- cadmium
- temperature
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- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 66
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000002699 waste material Substances 0.000 title abstract description 7
- 229910000863 Ferronickel Inorganic materials 0.000 title abstract description 6
- 229910045601 alloy Inorganic materials 0.000 title abstract 3
- 239000000956 alloy Substances 0.000 title abstract 3
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 title description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- 239000000284 extract Substances 0.000 claims abstract description 5
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 4
- 230000002829 reductive effect Effects 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- 238000013467 fragmentation Methods 0.000 claims description 8
- 238000006062 fragmentation reaction Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000007670 refining Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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Classifications
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- 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 discloses a complete set of technique which can extract cadmium and produce ferronickel alloy from waste nickel to cadmium cell. The invention crushes the waste nickel to cadmium cell and then put the waste nickel to cadmium cell into a low temperature roasting kiln to carry out preroast, and the roasted materials and the reducing agent are mixed to conduct vacuum distillation to collect the product of cooling section and after refining, excellent cadmium is produced; the materials that are not vaporized can produce ferronickel alloy after being refined. The technique realizes the separation and exaction of cadmium and ferronickel in the waste nickel to cadmium cell; wherein, the cadmium recycle ratio with the high efficiency cadmium recycle technology can reach 99.8 percent, and the cadmium purity is more than 99.9 percent. Metal cadmium is completely recycled, thus the waste is fully used and no secondary pollution is formed and considerable economic benefit and good social benefit are created.
Description
Technical field
The invention belongs to resource and reclaim the field, be specifically related to a kind of set technique that from abandoned nickel and cadmium cell, extracts cadmium, produces Rhometal.
Background technology
Contain a large amount of nickel and cadmium (containing Ni 116～556 grams, Cd 11～173 grams in every kilogram of refuse battery) in the abandoned nickel and cadmium cell; if these heavy metals are revealed; will produce very big harm to human body and environment; even bring some catastrophic crises; for example occur in public hazard incident-" itai-itai " incident in basin, magic river, Toyama County, Japan in the period of 1955～1972, because cadmium exceeds standard and causes.
At present, there have been many investigators that the recovery of nickel-cadmium cell is explored, method now commonly used mainly contains two kinds of pyrogenic process and wet methods, pyrogenic process, wet method combined flow process are also arranged, wherein can be divided into the selective extraction etc. that selectivity leaches cadmium, selective precipitation cadmium, cadmium because of the difference of technology again in the wet method.Mainly there are low, the problems such as the rate of recovery is low, poor operability of metal purity that reclaim in existing treatment process.
Summary of the invention
To the objective of the invention is on the basis of pilot scale, provide a kind of fully closed vacuum metallurgy technology in order to extract cadmium and nickel from abandoned nickel and cadmium cell, realized the separation and the extraction of cadmium, nickel, has better economic and be worth and environmental benefit.
Purpose of the present invention can reach by following measure:
A kind of set technique that from abandoned nickel and cadmium cell, extracts cadmium, produces Rhometal, its concrete steps are:
Step 1: with the abandoned nickel and cadmium cell fragmentation; This step can adopt multiple mode with battery crushing, and its ground grains is more little, and is abundant more with the reductive agent reaction.As adopting scissor-type crusher with the abandoned nickel and cadmium cell fragmentation, the outlet particle diameter is about 5mm; Directly ionogen is separated after also can utilizing the puncture roll type crusher with the battery case fragmentation;
Step 2: with the battery preroasting after the fragmentation; Wherein pre-calcination temperature is preferably 200～450 ℃, and roasting time 5～10h is preferably 7～8h; This step can be carried out in the low-temperature bake kiln, can utilize multiple mode to heat, and preferably adopts the high-temperature furnace gas heating (as in the step 3) that produces in the vacuum distilling;
Step 3: the material after the roasting is mixed with reductive agent, vacuum distilling, the cadmium vapor condensation with producing obtains thick cadmium; Wherein reductive agent is preferably powdered carbon, and the mass ratio of itself and raw material is 1: 50～100; Wherein the temperature of vacuum distilling is preferably 900～1000 ℃, and vacuum tightness is preferably 20～200Pa, and time 5～10h is preferably 7～8h.
Step 4: thick cadmium is mixed with reductive agent, vacuum distilling, the cadmium vapor condensation with producing obtains pure cadmium; Wherein the temperature of vacuum distilling is preferably 500～600 ℃, and vacuum tightness is preferably 20～200Pa, and the time is 0.5～5h, is preferably 1～2h; Wherein reductive agent is preferably powdered carbon, and the mass ratio of itself and raw material is 1: 5～20.
Step 5: the material that is not vaporized in the vacuum distilling is mixed with reductive agent, and high temperature melting is produced Rhometal; This step can be utilized the medium-frequency induction furnace heating, and wherein temperature is preferably 1700～1800 ℃, and calcination time is preferably 4～5h.Wherein reductive agent is preferably powdered carbon, and the mass ratio of itself and raw material is 1: 5～20.Vacuum tightness described in the present invention is the perfect vacuum degree.
The present invention has realized from abandoned nickel and cadmium cell that cadmium and nickel are high efficiency and has separated and extraction.Abandoned nickel and cadmium cell is pulverized, most of ionogen is separated with battery container; Send into preroasting in the low-temperature bake stove, remove moisture, organic substances such as charing wrapping paper, plastics change reductive agent into; Raw material after the roasting mixes with reductive agent, carry out vacuum distilling, at high temperature, Cadmium oxide and reductive agent reaction, generate cadmium simple substance, be vaporized, diffuse to low pressure area, through the condensation segment condensation, and the boiling point of nickel is up to 2920 ℃, even air pressure reduces, gasification temperature has been realized separating of cadmium and nickel thus still than furnace temperature height; Collect the product in the condensation segment,, produce the pure cadmium product through refining; The material that is not vaporized mainly contains the ferronickel metal, through refining, can produce Rhometal.
A kind of set technique method of from abandoned nickel and cadmium cell, extracting cadmium, producing Rhometal of the present invention, realized separating and extraction of cadmium and nickel, wherein efficient cadmium reclaims technology, the cadmium rate of recovery is more than 99.8%, cadmium purity is more than 99.9%, and the metallic nickel full dose reclaims, and can make full use of waste, non-secondary pollution, and create considerable economic benefit and good social benefit.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Among the figure solid line be efflux of solids to, dotted line is a flow direction, short-term is gas flow.
Embodiment
Below by example in detail processing step of the present invention:
Embodiment 1:
(1) utilize scissor-type crusher with the abandoned nickel and cadmium cell fragmentation, keeping the outlet particle diameter more than 80% is 5mm.
(2) nickel-cadmium cell after the fragmentation is filled to the low-temperature bake roasting in kilns, batch operation, roasting time is 7～8h.The heated air inlet temperature is 400 ℃, and temperature out is 200 ℃, and along with operation is carried out, temperature out can increase to some extent, but does not influence dry and charing effect.
H
2O
(l)→H
2O
(g)
Organic substance → C+H
2O
(g)+ other materials
(3) be to mix at 100: 1 the battery after the roasting and powdered carbon according to mass ratio, carry out a vacuum distilling, keeping calcining temperature is 900～1000 ℃, and vacuum tightness is 100Pa, and distillation time is 7～8h, and the cadmium steam utilization water that distills out carries out condensation.Burner hearth adopts coal to act as a fuel, and design temperature is 1200 ℃.
CdO+C→Cd
(g)+CO
(4) collecting thick cadmium, is 1: 10 interpolation powdered carbon according to mass ratio, carries out the secondary vacuum distillation, and keeping calcining temperature is 500～600 ℃, and vacuum tightness is 100Pa, and calcination time is 1～2h, the cadmium steam utilization water condensation that distills out.After distillation finishes, collect pure cadmium, send into smelting furnace,, produce cadmium ingot 400～500 ℃ of following fusions.This process section utilizes the electric energy heating, and the design furnace temperature is 600 ℃; The cadmium slag that produces is as a vacuum distilling raw material.
CdO+C→Cd+CO
The material main component that is not vaporized in (5) vacuum distilling is the ferronickel metal, is 1: 5 interpolation powdered carbon according to mass ratio, utilizes medium-frequency induction furnace to heat up and melts, keeping calcining temperature is 1700～1800 ℃, calcination time is 4～5h, produces Rhometal, as the raw material of special steel.
NiO+C→Ni+CO
Fe
2O
3+3C→2Fe+3CO
(6) high-temperature furnace gas of vacuum distillation furnace burning generation, through the interchanger heat exchange, the recovered steam energy, furnace temperature is reduced to 400 ℃, as low-temperature bake kiln heated air.
(7) the cadmium waste gas that contains that the low-temperature bake kiln produces adopts the washing tower carrying out washing treatment, and operating method is the secondary washing.Design one-level washing tower gas inlet temperature is 400 ℃, and mist eliminator is not established on top, and secondary washing tower gas inlet temperature is 100 ℃, and top is provided with mist eliminator, carries out gas-water separation.Washing water enter washing pond precipitation, and clear liquid returns in the washing tower and recycles, after the body refuse dehydration, as the raw material of vacuum distilling; Waste gas is by smoke stack emission.
The cadmium rate of recovery is 99.9% in this technology, and cadmium purity is 99.97%, and nickel recovery is 100%, and iron and nickel account for 95% in the Rhometal.
Embodiment 2:
Other condition is constant, changes crumbling method in (1) of embodiment 1 into the puncture roll type crusher in crushing, changes the vacuum tightness of vacuum distilling into 80Pa, the final cadmium rate of recovery 99.5%, and cadmium precision 99.9%, nickel recovery 100%, iron and nickel account for 91% in the Rhometal.
Claims (2)
1. set technique that from abandoned nickel and cadmium cell, extracts cadmium, produces Rhometal, its concrete steps are:
Step 1: with the abandoned nickel and cadmium cell fragmentation, keeping the outlet particle diameter more than 80% is 5mm;
Step 2: the battery after the fragmentation is filled to preroasting in the low-temperature bake kiln; Roasting time is 7～8h, and the heated air inlet temperature is 400 ℃, and temperature out is 200 ℃;
Step 3: is to mix at 100: 1 the material after the roasting and reductive agent powdered carbon according to mass ratio, and keeping calcining temperature is that 900～1000 ℃, vacuum tightness are that 100Pa carries out vacuum distilling, and distillation time is 7～8h, and the cadmium vapor condensation with producing obtains thick cadmium;
Step 4: collecting thick cadmium, is to add powdered carbon at 1: 10 according to mass ratio, and keeping calcining temperature is that 500～600 ℃, vacuum tightness are that 100Pa carries out the secondary vacuum distillation, vacuum distilling, and calcination time is 1～2h, the cadmium vapor condensation with producing obtains pure cadmium;
Step 5: the material that is not vaporized in the vacuum distilling is mixed with the reductive agent powdered carbon, is 1: 5 interpolation powdered carbon according to mass ratio, utilizes medium-frequency induction furnace to keep calcining temperature to be 1700～1800 ℃ and carries out high temperature melting, and calcination time is 4～5h, produces Rhometal.
2. technology according to claim 1 adopts the high-temperature furnace gas that vacuum distilling produces in the step 3 to heat when it is characterized in that preroasting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101910536A CN101220412B (en) | 2007-12-07 | 2007-12-07 | Set technique for extracting cadmium from waste and old nickel-cadmium battery, and producing ferro-nickel alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101910536A CN101220412B (en) | 2007-12-07 | 2007-12-07 | Set technique for extracting cadmium from waste and old nickel-cadmium battery, and producing ferro-nickel alloy |
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| Publication Number | Publication Date |
|---|---|
| CN101220412A CN101220412A (en) | 2008-07-16 |
| CN101220412B true CN101220412B (en) | 2010-09-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101910536A Expired - Fee Related CN101220412B (en) | 2007-12-07 | 2007-12-07 | Set technique for extracting cadmium from waste and old nickel-cadmium battery, and producing ferro-nickel alloy |
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| Country | Link |
|---|---|
| CN (1) | CN101220412B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942564B (en) * | 2010-08-21 | 2013-09-25 | 赵志强 | Process for producing pure cadmium by continuous reduction and distillation of zinc cadmium slag and sponge cadmium |
| CN102776374B (en) * | 2011-05-09 | 2014-02-26 | 深圳市格林美高新技术股份有限公司 | Treatment method of nickel-cadmium slag |
| CN110451556B (en) * | 2019-08-22 | 2022-02-25 | 李道斌 | Production process of secondary zinc oxide, zinc sulfate and nano zinc oxide |
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2007
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Granted publication date: 20100915 Termination date: 20101207 |