CA1292203C - Electrolytic recovery of lead from scrap - Google Patents
Electrolytic recovery of lead from scrapInfo
- Publication number
- CA1292203C CA1292203C CA 521698 CA521698A CA1292203C CA 1292203 C CA1292203 C CA 1292203C CA 521698 CA521698 CA 521698 CA 521698 A CA521698 A CA 521698A CA 1292203 C CA1292203 C CA 1292203C
- Authority
- CA
- Canada
- Prior art keywords
- lead
- electrolyte
- acid
- concentration
- anode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000011084 recovery Methods 0.000 title claims description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 44
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 9
- 239000007864 aqueous solution Substances 0.000 abstract description 6
- 239000003923 scrap metal Substances 0.000 abstract 1
- 239000008151 electrolyte solution Substances 0.000 description 11
- 229940021013 electrolyte solution Drugs 0.000 description 11
- 229910004039 HBF4 Inorganic materials 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- OGNVQLDIPUXYDH-ZPKKHLQPSA-N (2R,3R,4S)-3-(2-methylpropanoylamino)-4-(4-phenyltriazol-1-yl)-2-[(1R,2R)-1,2,3-trihydroxypropyl]-3,4-dihydro-2H-pyran-6-carboxylic acid Chemical compound CC(C)C(=O)N[C@H]1[C@H]([C@H](O)[C@H](O)CO)OC(C(O)=O)=C[C@@H]1N1N=NC(C=2C=CC=CC=2)=C1 OGNVQLDIPUXYDH-ZPKKHLQPSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FXKCXGBBUBCRPU-GBOPCIDUSA-N 2-[(2r,4ar,8s,8ar)-8-hydroxy-4a,8-dimethyl-1,2,3,4,5,6,7,8a-octahydronaphthalen-2-yl]prop-2-enoic acid Chemical compound C1C[C@@H](C(=C)C(O)=O)C[C@H]2[C@@](C)(O)CCC[C@@]21C FXKCXGBBUBCRPU-GBOPCIDUSA-N 0.000 description 1
- FKOZPUORKCHONH-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid Chemical compound CC(C)CS(O)(=O)=O FKOZPUORKCHONH-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- QNVBIDULDLPCDQ-UHFFFAOYSA-N Ilicic acid Natural products CC1(O)CCC2(C)CCC(CC2C1)C(=C)C(=O)O QNVBIDULDLPCDQ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- HNDXKIMMSFCCFW-UHFFFAOYSA-N propane-2-sulphonic acid Chemical compound CC(C)S(O)(=O)=O HNDXKIMMSFCCFW-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/18—Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Electrolytic Production Of Metals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Lead is recovered from lead-containing scrap metal in an electrolytic process employing an aqueous solution of C1-4 alkanesulfonic acid as the electrolyte at a high concentration, scrap lead as the anode, and an electroconductive cathode, impressing an electromotive force across the solution between the electrodes to provide a specified steady-state concentration of lead salt in the electrolyte, and continuing the process to deplete the anode and collect lead at the cathode.
Lead is recovered from lead-containing scrap metal in an electrolytic process employing an aqueous solution of C1-4 alkanesulfonic acid as the electrolyte at a high concentration, scrap lead as the anode, and an electroconductive cathode, impressing an electromotive force across the solution between the electrodes to provide a specified steady-state concentration of lead salt in the electrolyte, and continuing the process to deplete the anode and collect lead at the cathode.
Description
ELECTROLYTIC RECOVERY OF LEAD FROM SCRAP
I~ 2821 : BACKGROUND OF THE_INVENTION
This invention concerns the recovery of lead from : ~ 5 lead-containing scrap~ preferably lead from spent lead-acid :
storage batteries. More particularly, it concerns ~he rec~very of lead in an electrolytic ~rocess employing : an aqueous Cl 4 alkanesulfonic acid solution as the eLectrolyte at a~concentration of from about;l5 to 70 wei~ht percent and a steady-state concentr~tion of lead salt of ~o ~ ~ : greater than 7057~ ~ased on the weight of the electrolyte.
:: ~$
PRIOR ART
The use of an organic sulfonic acid as an electrolyte in an electrodepository process for the plating o lead is known1. However, the prior art processes employ comparatively high concentrations of lead salts (in excess of 10% by weight) in the elec~rolyte solution9 which is usually prepared by first dissolving lead alkanesulfonate in the aqueous electrolyte up to the concentration of the salt in the bath. The high concentration of lead salt in the electrolyte is stated in the literature to be essential because, while it is necessary to use a reasonable current density in the plating process, the quality of the plate suffers badly if the metal deposition occurs under conditions where the electrode reaction is even partially mass-transfer-con'trolled2, as can occur at low lead ~ concentration. In addition, the high concentrations of lead : ~ salts in the plating process favor high current efficiency becau:se the high ratio of lead ion to hydrogen ian in solution tends to repress hydrogen rel ase at the cathode.
-U.S. Patent No. 2,525,942 Nobel et aI. "High Sp~ed Tin and Tin-Alloy Plating : Sympos:ium, Apr. 1985, Americ~n EIectropla~ers' Socie~y, Inc., Orlando, Fla.
:~ 25 20 - Pletcher,~ Derek "Industrial Electrochemistryt', ~ 1984, Chapman and Hall, London, pp. 181,183.
;
.~ .. ~
::
-' 12 9Z 20 3 Processes for the recovery of lead from spent lead-acid storage batteries are known3. These prior disclosures teach the use of electrolyte solutions including, for example, sulfamic acid, acetic acid, fluoboric acid, fluo~ilicic acid, perchlorates, cyanides, nitrates, oxalates, and pyrophosphates.
Each of these acidic materials demons~rate certain problems which makes replacement thereof in electrolyte solutions at least desirable. For example, sulfamic acid hydroly~es under acidic conditions to ammonium bisulfate. The sulfate precipitates lead as lead sulfate, thereby lowering the lead recovery, making electrolyte filtration necessary, ~nd generating a toxic waste (lead sulfate). Fluoboric acid cannot be discharged into many municipal waste-treatment systems due to restrictions of fluoride and boron discharges.
The lead salt o acetic acid is highly soluble but acetic acid is a weak acid with poor conductivity at high concen-trations leading to excessive power consumption. Fluosilicic acid i5 a toxic material which cannot be discharged to the environment. Other mentioned acidic material previously suggested as electrolyte~ for lead recovery have similar drawbacks and, in addition, may be explosive3 flammable and/or prone to encourage sludge formation and to form ;~ difficult-to-separate lead comple~es. Complexing tendencies .
3. - U.S. Patents No.'s 3,985,630; 49098,658; 4,460,442 ' ~' ~Z 9~ ~3 of some of these acidic materials makes it difficult to sufficiently reduce the lead content of the electrolyte solution in which they are used to avoid it being classified as ha~ardous waste.
STATEMENT OF THE INVENTION
. .
This invention is a process for the electrolytic recovery of scrap lead which comprises utili2ing an aqueous solution of Cl 4 alkanesulfonic acid as the electrolyte at a concentration of about 15 up to about 70% based on the weight of the electrolyte, scrap lead as the anode and an electroconductive material as the cathode, impressing an electromotive force across said electrolyte between the electrodes immersed in said electrolyte to provide a steady-state concentration of lead salt in the electroly~e 1~ ranglng from about 0.2 to about 7.5% based on the weight of~electrolyte solution, and continuing the electrolytic :process to deplete the anode and recover lead at the cathode.
: THE DRAWING
: Figures 1 and 2 of the drawing are graphs of plotted 20 points representir.g measurements of the current density ~ (amps per square meter) a~d current efficiency ~%) at :~ various applied voltages in electrolytic lead recovery : systems as la~er desc~ibed in ~xamples 2 ~nd 3. Data points : ~ in the graphs represent the averages of several runs under 2S each set of experimental conditions of the examples and ~:
: ~:
;2 2(~3 straight lines were fitted using the standard linear least-squares procedure. The standard deviations, calculated from the pooled variances for 25 observations for both MSA and fluoboric acid were +39A/m2 and ~30 % for current density and current efficiency, respectively. Figure 1 compares the current density and current efficiency for a 25 wt% aqueous methanesul~onic acid electrolyte system with a 30 wt%
aqueous fluoboric acid electrolyte system. Figure 2 compares the current density and current efficiency for a 25 wt%
aqueous methanes~lfonic acid electrolyte system with a 50 wt% aqueous fluoboric acid electrolyte system.
DETAILED DESCRIPTION OF IN~ENTION
This is a hydrometallurgical process for recovering lead from lead-containing scrap, preferably from spent lead-acid storage ba~teries. The process employs an aqueous solution of one or a mixture of alkanesulonic aclds having carbon chain lengths o~ l to 4 as the electrolyte. Such sulfonic acids include, for example, methanesulfonic acid, ethanesul~onic acid~, propanesulfonic acid, isopropane-sulfonic acid, butanesulfonic acid and isobutanesulfonic acid.
: The preferred sulfonic acid is methanesulfonic acid (MSA) because of its availabili~y, low molecular weight, high innate solubility in water and high water solubility of its lead salt. The sulfonic acid is employed at a concentration .
125~ 3 of about 15% up to about 70% based on the weight of theelectrolyte solution (155 to 930 grams/liter). Preferably, the sulfonic acid is used in the electrolyte solution at a concentration o~ from about 20 to about 40% (215 to 470 g/l) 3 more preferably at about 25% (275 g/l).
The electromotive force impressed on the electrolytic system is a direct current (DC) voltage ranging Erom about 1 to about 6 volts resulting in a steady-state concentration of lead salt in the electrolyte bath of from about 0.2 to about 7.5% based on the weight of the electrolyte-salt solution (2 to 100 g/l). The optimum voltage for maximum ; current efficiency in this process ranges from about 1 to about 3 with the use of aqueous methanesulfonic acid as the electrolyte.
; L5 In general, for any given electrolyte acid concentration in an electrochemical system, power consumption is minimized ~(optimized) when conductivity is maximlzed, and this occurs when the concentratlon o~ dissolved lead is at a maximum.
~However, in this~ and si=ilar lead recovery processes, the dissoIved lead concentration in the electrolyte is not an independent variable; i~ will depend on elec~rolyte :: ~::: : :
; concentration, choice of electrolyte and opera~ing voltage.
'~Steady-state" as used herein means ~he concentration of lead saLts in the electrolyte when the rate of dissolution 25~ of the lead from the anode equals the rate of deposition of :
~ ~ the lead metal on the cathode in a system operating at a 21~3 specified impressed voltage and electrolyte concentration.
The steady-state concentration (and hence the power efficiency) may be increased up to the point where poor quality lead deposits or the upper operating limi~s of the equipment are reached.
The anode for the process of this invention is scrap lead of any desired shape which may contain up to 20% of other metals including, for example J antimony, copper, tin, titanium, calcium and arsenic. In a more preferable embodi-men~, the scrap lead anode is the electrode or electrodes oflead-acid storage batteries and, in the most preferable embodiment, at least one assembled or par~ially assembled lead-acid storage ba~tery comprising a series of electronically connected positive and negative couples of lead~containing electrodes as disclosed in U.S. Patents Nos. 3,985,630 and 4,098,658.
The cathode of this invention may be any elec~rocon-ductive material in any desired shape which is substantially ~ ~nsoluble in the electrolyte under the condi~ions of the ~: ~
, , ! "
-` ~2~22~)3 process. Typical cathode materials are lead and graphite preferably fabricated in a flat shape.
The temperature at which ~his process is operated is ~ot critical. Preferably, it is carried ou~ at ambient S temperature although, due to a moderate exotherm during operation, the temperature may rise. Temperatures generally do not exceed 40-50 C and external cooling is typically not required.
The electrolytic cell-of this invention includes a tank or vessel of a suitable size and shape in which the electrolytic process may be operated in the desired fashion.
The material from which the tank is fabricated may be non-electrically conductive or electrically conductive, if properly insulated, as is well known in this art.
The concentration of lead ions (dissolved lead salt) in the electrolyte solu$ion is determined by the chemical compos1tion of the electrolyte (acid type and its concen-tration in the solution) and the applied voltage on the electrolytic system. Th~s, for example, the employment of methanesulfonic acid at a concentration of 25 b and an applied DC voltage of 3.5 will produce a steady-state con-ce~trati~on of lead in the electrolyte bath of about 1.26 %
(See Table 1). At a given voltage,~the bath conductance and~
conscquently, the power costs, are, in part, determined by the concentration of lead ions in the bath. Experiments have shown that, at any specified vol~age, a higher steady-.
"~ 2~ 2 ~ 3 state concen~ration of lead ions is reached with a 25 wt%aqueous MSA electrolyte solution than with a 50 wt% aqueous fluoboric acid (HBF~) electroly~e solution (a preferred electrolyte of the prior art for scrap lead recovery) when S scrap lead anodes were subjected, under otherwise similar conditions, to currents over the range of from 1 to 5 volts.
At these higher steady-state lead ion concentrations obtained with an MSA electrolyte solution, current densities in the MSA system unexpectedly approach or are equal to those of the HBF4 system at voltages of between 1 and 5 despite the known higher conductivity of aqueous HBF4 versus aqueous MSA
(See Figure 2). Since the cost of MSA (on a 100% weight basis) is lower than that of HBF4, the alkanesulfonic acid-based process of this invention achieves substantial raw material cost savings, both by virtue of the lower cost per pound and by the use of a lower preferred concentration, over the presently pre~erred electrolyte acid for scrap lead recovery.
An important further advantage of the lower-alkane-sulfonic acld electrolyte solutions over the electrolyte ~ ~olutions previously disclosed in the art for lead recovery : is the ease with which the spent sulfonic acid electrolyte can be disposed. The lead ion concentration of ~he alkane-sulonic acid elec~rolyte can be reduced to well below 1 part per million (ppm~ simply by adjusting the pH to 8-~.
The lower al~ane-sulfonic acid, after neutxalization~ can 2~3 . ` 10 be easily disposed of without causing significant environmental pollution.
The current densities reported in the following examples were determined by measuring the current with an ammeter and the result, averaged over the course of a run, was divided by the surface area of the cathode. The current efficiencies were computed from the averaged current in amperes (C), time [duration in seconds (T) of the deposition process] and quantity in grams (W) of lead recovered at the : 10 cathode using th following equation:
Current Efficiency (/O) = W x 96,500 x 100 C x T x 103.6 To establish a comparison between the steady-sta~e 15~ concentration of lead salt for MSA (methanesulfonic acid) an~ HBF4 (fluoboric acid~ electrolytes ln the recovery of lead::from lead scrap, an electrolytic recovery operation employing s:crap:lead as the:anode, lead foil as th~e cathode~
: ~a~voltage~of 3.5~and an aqueous electrolyte containing 25% ~ ~: 20~ MSA,:based on the weight of the electrolyte solution~ was ca~ried out. The current density was 185 amps/square meter : a~d:the current efficiency was 87%. Another electrolytic lead recovery ope~ation was carried out utilizin~ the same system and conditions~except that th~ electrolyte was an : : 25 : aqueous solution contalning 50% of HBF4 based on the weight :
:: ::
: :~ : : : :
~2~ 2 ~03 of the solution. In this system9 the current density was 165 amps/square meter and the current efficiency 70%.
The current densities and current efficiencies reported above were obtained from single-run data. The following table shows the lead ion concentration (wt.%) formed in the electrolyte over a time per~od of 3600 seconds.
TIME(SEC.) 25% MSA 50% HBF4 .049 .069 120 .105 .109 600 ~ .518 .382 90~ .738 .476 1200 .933 _ _ .522 1800 1 1.2~ .604 2400 1.27 ~ .798l 3000 1 1.26 .723 3600 l-l.23 _ _ 744l In the above table, the concentrations e~veloped by the dashed llne represent the steady-state concentrations formed in each system when subject to the same operating conditions except for the electrolyte and its concentra-tion. Unexpectedly, the 25% MSA system developed a current density at its higher steady-state concentration which density is essentially equivalent to that o~ the 50% HBF4 electrolyte system at its lower steady-state concentration.
A lead a~ode taken from a discharged and recharged motorcycle bat~ery consisting of a soft lead paste supported on a hard lead grid was electrolyzed in a bath containing a :
o~
25% by weight aqueous solution of MSA using lead foil for the cathode. The electrode areas were initially each about 25 square centimeters and the dis~ance between the immersed electrodes was 12 centimeters. The bath was agitated using 5 a magnetic s~irrer. In the same procedure as recited above, hydrometallurgical lead recovery was carried out except that a 30% by weight aqueous solution of HBF4 was used in place of the 25% MSA electrolyte solution. For each procedure, the cathode current density and cathode current efficiency were measured as-a function of the applied voltage and the measured data plotted in Fi~ure 1 of the drawing. These data show that the two electrolyte solutions behave in an unexpectedly similar fashion, especially as regards current efficiency, despite the large differences in conductivity observed for both the free acids and their respective lead salts.
The current density and efficiency performances of a 25% by weight aqueous MSA solution and 50% by weight HBF4 20 ~ solution as electrolytes in the hydrometallurgical recovery of lead undcr the condition~ described in Example 2 were compared and the measured data plotted in the graph of Figure 2 of the drawing. Again9 the data show unexpectedly similar density and efficiency performances for the two electrolytes Z5~ 3 despite the significantly greater conductivity for both HBF4 and its lead saLt.
: , :
:
:: :
: ::
: :
I~ 2821 : BACKGROUND OF THE_INVENTION
This invention concerns the recovery of lead from : ~ 5 lead-containing scrap~ preferably lead from spent lead-acid :
storage batteries. More particularly, it concerns ~he rec~very of lead in an electrolytic ~rocess employing : an aqueous Cl 4 alkanesulfonic acid solution as the eLectrolyte at a~concentration of from about;l5 to 70 wei~ht percent and a steady-state concentr~tion of lead salt of ~o ~ ~ : greater than 7057~ ~ased on the weight of the electrolyte.
:: ~$
PRIOR ART
The use of an organic sulfonic acid as an electrolyte in an electrodepository process for the plating o lead is known1. However, the prior art processes employ comparatively high concentrations of lead salts (in excess of 10% by weight) in the elec~rolyte solution9 which is usually prepared by first dissolving lead alkanesulfonate in the aqueous electrolyte up to the concentration of the salt in the bath. The high concentration of lead salt in the electrolyte is stated in the literature to be essential because, while it is necessary to use a reasonable current density in the plating process, the quality of the plate suffers badly if the metal deposition occurs under conditions where the electrode reaction is even partially mass-transfer-con'trolled2, as can occur at low lead ~ concentration. In addition, the high concentrations of lead : ~ salts in the plating process favor high current efficiency becau:se the high ratio of lead ion to hydrogen ian in solution tends to repress hydrogen rel ase at the cathode.
-U.S. Patent No. 2,525,942 Nobel et aI. "High Sp~ed Tin and Tin-Alloy Plating : Sympos:ium, Apr. 1985, Americ~n EIectropla~ers' Socie~y, Inc., Orlando, Fla.
:~ 25 20 - Pletcher,~ Derek "Industrial Electrochemistryt', ~ 1984, Chapman and Hall, London, pp. 181,183.
;
.~ .. ~
::
-' 12 9Z 20 3 Processes for the recovery of lead from spent lead-acid storage batteries are known3. These prior disclosures teach the use of electrolyte solutions including, for example, sulfamic acid, acetic acid, fluoboric acid, fluo~ilicic acid, perchlorates, cyanides, nitrates, oxalates, and pyrophosphates.
Each of these acidic materials demons~rate certain problems which makes replacement thereof in electrolyte solutions at least desirable. For example, sulfamic acid hydroly~es under acidic conditions to ammonium bisulfate. The sulfate precipitates lead as lead sulfate, thereby lowering the lead recovery, making electrolyte filtration necessary, ~nd generating a toxic waste (lead sulfate). Fluoboric acid cannot be discharged into many municipal waste-treatment systems due to restrictions of fluoride and boron discharges.
The lead salt o acetic acid is highly soluble but acetic acid is a weak acid with poor conductivity at high concen-trations leading to excessive power consumption. Fluosilicic acid i5 a toxic material which cannot be discharged to the environment. Other mentioned acidic material previously suggested as electrolyte~ for lead recovery have similar drawbacks and, in addition, may be explosive3 flammable and/or prone to encourage sludge formation and to form ;~ difficult-to-separate lead comple~es. Complexing tendencies .
3. - U.S. Patents No.'s 3,985,630; 49098,658; 4,460,442 ' ~' ~Z 9~ ~3 of some of these acidic materials makes it difficult to sufficiently reduce the lead content of the electrolyte solution in which they are used to avoid it being classified as ha~ardous waste.
STATEMENT OF THE INVENTION
. .
This invention is a process for the electrolytic recovery of scrap lead which comprises utili2ing an aqueous solution of Cl 4 alkanesulfonic acid as the electrolyte at a concentration of about 15 up to about 70% based on the weight of the electrolyte, scrap lead as the anode and an electroconductive material as the cathode, impressing an electromotive force across said electrolyte between the electrodes immersed in said electrolyte to provide a steady-state concentration of lead salt in the electroly~e 1~ ranglng from about 0.2 to about 7.5% based on the weight of~electrolyte solution, and continuing the electrolytic :process to deplete the anode and recover lead at the cathode.
: THE DRAWING
: Figures 1 and 2 of the drawing are graphs of plotted 20 points representir.g measurements of the current density ~ (amps per square meter) a~d current efficiency ~%) at :~ various applied voltages in electrolytic lead recovery : systems as la~er desc~ibed in ~xamples 2 ~nd 3. Data points : ~ in the graphs represent the averages of several runs under 2S each set of experimental conditions of the examples and ~:
: ~:
;2 2(~3 straight lines were fitted using the standard linear least-squares procedure. The standard deviations, calculated from the pooled variances for 25 observations for both MSA and fluoboric acid were +39A/m2 and ~30 % for current density and current efficiency, respectively. Figure 1 compares the current density and current efficiency for a 25 wt% aqueous methanesul~onic acid electrolyte system with a 30 wt%
aqueous fluoboric acid electrolyte system. Figure 2 compares the current density and current efficiency for a 25 wt%
aqueous methanes~lfonic acid electrolyte system with a 50 wt% aqueous fluoboric acid electrolyte system.
DETAILED DESCRIPTION OF IN~ENTION
This is a hydrometallurgical process for recovering lead from lead-containing scrap, preferably from spent lead-acid storage ba~teries. The process employs an aqueous solution of one or a mixture of alkanesulonic aclds having carbon chain lengths o~ l to 4 as the electrolyte. Such sulfonic acids include, for example, methanesulfonic acid, ethanesul~onic acid~, propanesulfonic acid, isopropane-sulfonic acid, butanesulfonic acid and isobutanesulfonic acid.
: The preferred sulfonic acid is methanesulfonic acid (MSA) because of its availabili~y, low molecular weight, high innate solubility in water and high water solubility of its lead salt. The sulfonic acid is employed at a concentration .
125~ 3 of about 15% up to about 70% based on the weight of theelectrolyte solution (155 to 930 grams/liter). Preferably, the sulfonic acid is used in the electrolyte solution at a concentration o~ from about 20 to about 40% (215 to 470 g/l) 3 more preferably at about 25% (275 g/l).
The electromotive force impressed on the electrolytic system is a direct current (DC) voltage ranging Erom about 1 to about 6 volts resulting in a steady-state concentration of lead salt in the electrolyte bath of from about 0.2 to about 7.5% based on the weight of the electrolyte-salt solution (2 to 100 g/l). The optimum voltage for maximum ; current efficiency in this process ranges from about 1 to about 3 with the use of aqueous methanesulfonic acid as the electrolyte.
; L5 In general, for any given electrolyte acid concentration in an electrochemical system, power consumption is minimized ~(optimized) when conductivity is maximlzed, and this occurs when the concentratlon o~ dissolved lead is at a maximum.
~However, in this~ and si=ilar lead recovery processes, the dissoIved lead concentration in the electrolyte is not an independent variable; i~ will depend on elec~rolyte :: ~::: : :
; concentration, choice of electrolyte and opera~ing voltage.
'~Steady-state" as used herein means ~he concentration of lead saLts in the electrolyte when the rate of dissolution 25~ of the lead from the anode equals the rate of deposition of :
~ ~ the lead metal on the cathode in a system operating at a 21~3 specified impressed voltage and electrolyte concentration.
The steady-state concentration (and hence the power efficiency) may be increased up to the point where poor quality lead deposits or the upper operating limi~s of the equipment are reached.
The anode for the process of this invention is scrap lead of any desired shape which may contain up to 20% of other metals including, for example J antimony, copper, tin, titanium, calcium and arsenic. In a more preferable embodi-men~, the scrap lead anode is the electrode or electrodes oflead-acid storage batteries and, in the most preferable embodiment, at least one assembled or par~ially assembled lead-acid storage ba~tery comprising a series of electronically connected positive and negative couples of lead~containing electrodes as disclosed in U.S. Patents Nos. 3,985,630 and 4,098,658.
The cathode of this invention may be any elec~rocon-ductive material in any desired shape which is substantially ~ ~nsoluble in the electrolyte under the condi~ions of the ~: ~
, , ! "
-` ~2~22~)3 process. Typical cathode materials are lead and graphite preferably fabricated in a flat shape.
The temperature at which ~his process is operated is ~ot critical. Preferably, it is carried ou~ at ambient S temperature although, due to a moderate exotherm during operation, the temperature may rise. Temperatures generally do not exceed 40-50 C and external cooling is typically not required.
The electrolytic cell-of this invention includes a tank or vessel of a suitable size and shape in which the electrolytic process may be operated in the desired fashion.
The material from which the tank is fabricated may be non-electrically conductive or electrically conductive, if properly insulated, as is well known in this art.
The concentration of lead ions (dissolved lead salt) in the electrolyte solu$ion is determined by the chemical compos1tion of the electrolyte (acid type and its concen-tration in the solution) and the applied voltage on the electrolytic system. Th~s, for example, the employment of methanesulfonic acid at a concentration of 25 b and an applied DC voltage of 3.5 will produce a steady-state con-ce~trati~on of lead in the electrolyte bath of about 1.26 %
(See Table 1). At a given voltage,~the bath conductance and~
conscquently, the power costs, are, in part, determined by the concentration of lead ions in the bath. Experiments have shown that, at any specified vol~age, a higher steady-.
"~ 2~ 2 ~ 3 state concen~ration of lead ions is reached with a 25 wt%aqueous MSA electrolyte solution than with a 50 wt% aqueous fluoboric acid (HBF~) electroly~e solution (a preferred electrolyte of the prior art for scrap lead recovery) when S scrap lead anodes were subjected, under otherwise similar conditions, to currents over the range of from 1 to 5 volts.
At these higher steady-state lead ion concentrations obtained with an MSA electrolyte solution, current densities in the MSA system unexpectedly approach or are equal to those of the HBF4 system at voltages of between 1 and 5 despite the known higher conductivity of aqueous HBF4 versus aqueous MSA
(See Figure 2). Since the cost of MSA (on a 100% weight basis) is lower than that of HBF4, the alkanesulfonic acid-based process of this invention achieves substantial raw material cost savings, both by virtue of the lower cost per pound and by the use of a lower preferred concentration, over the presently pre~erred electrolyte acid for scrap lead recovery.
An important further advantage of the lower-alkane-sulfonic acld electrolyte solutions over the electrolyte ~ ~olutions previously disclosed in the art for lead recovery : is the ease with which the spent sulfonic acid electrolyte can be disposed. The lead ion concentration of ~he alkane-sulonic acid elec~rolyte can be reduced to well below 1 part per million (ppm~ simply by adjusting the pH to 8-~.
The lower al~ane-sulfonic acid, after neutxalization~ can 2~3 . ` 10 be easily disposed of without causing significant environmental pollution.
The current densities reported in the following examples were determined by measuring the current with an ammeter and the result, averaged over the course of a run, was divided by the surface area of the cathode. The current efficiencies were computed from the averaged current in amperes (C), time [duration in seconds (T) of the deposition process] and quantity in grams (W) of lead recovered at the : 10 cathode using th following equation:
Current Efficiency (/O) = W x 96,500 x 100 C x T x 103.6 To establish a comparison between the steady-sta~e 15~ concentration of lead salt for MSA (methanesulfonic acid) an~ HBF4 (fluoboric acid~ electrolytes ln the recovery of lead::from lead scrap, an electrolytic recovery operation employing s:crap:lead as the:anode, lead foil as th~e cathode~
: ~a~voltage~of 3.5~and an aqueous electrolyte containing 25% ~ ~: 20~ MSA,:based on the weight of the electrolyte solution~ was ca~ried out. The current density was 185 amps/square meter : a~d:the current efficiency was 87%. Another electrolytic lead recovery ope~ation was carried out utilizin~ the same system and conditions~except that th~ electrolyte was an : : 25 : aqueous solution contalning 50% of HBF4 based on the weight :
:: ::
: :~ : : : :
~2~ 2 ~03 of the solution. In this system9 the current density was 165 amps/square meter and the current efficiency 70%.
The current densities and current efficiencies reported above were obtained from single-run data. The following table shows the lead ion concentration (wt.%) formed in the electrolyte over a time per~od of 3600 seconds.
TIME(SEC.) 25% MSA 50% HBF4 .049 .069 120 .105 .109 600 ~ .518 .382 90~ .738 .476 1200 .933 _ _ .522 1800 1 1.2~ .604 2400 1.27 ~ .798l 3000 1 1.26 .723 3600 l-l.23 _ _ 744l In the above table, the concentrations e~veloped by the dashed llne represent the steady-state concentrations formed in each system when subject to the same operating conditions except for the electrolyte and its concentra-tion. Unexpectedly, the 25% MSA system developed a current density at its higher steady-state concentration which density is essentially equivalent to that o~ the 50% HBF4 electrolyte system at its lower steady-state concentration.
A lead a~ode taken from a discharged and recharged motorcycle bat~ery consisting of a soft lead paste supported on a hard lead grid was electrolyzed in a bath containing a :
o~
25% by weight aqueous solution of MSA using lead foil for the cathode. The electrode areas were initially each about 25 square centimeters and the dis~ance between the immersed electrodes was 12 centimeters. The bath was agitated using 5 a magnetic s~irrer. In the same procedure as recited above, hydrometallurgical lead recovery was carried out except that a 30% by weight aqueous solution of HBF4 was used in place of the 25% MSA electrolyte solution. For each procedure, the cathode current density and cathode current efficiency were measured as-a function of the applied voltage and the measured data plotted in Fi~ure 1 of the drawing. These data show that the two electrolyte solutions behave in an unexpectedly similar fashion, especially as regards current efficiency, despite the large differences in conductivity observed for both the free acids and their respective lead salts.
The current density and efficiency performances of a 25% by weight aqueous MSA solution and 50% by weight HBF4 20 ~ solution as electrolytes in the hydrometallurgical recovery of lead undcr the condition~ described in Example 2 were compared and the measured data plotted in the graph of Figure 2 of the drawing. Again9 the data show unexpectedly similar density and efficiency performances for the two electrolytes Z5~ 3 despite the significantly greater conductivity for both HBF4 and its lead saLt.
: , :
:
:: :
: ::
: :
Claims (7)
1. A process for the electrolytic recovery of scrap lead which comprises utilizing an aqueous C1-4 alkanesulfonic acid as the electrolyte at a concentration of about 15 to about 70% based on the weight of the electrolyte, scrap lead as the anode and an electroconductive material as the cathode, impressing an electromotive force across said electrolyte between the electrodes immersed in said electrolyte to thereby provide a steady state concentration of lead salt in the electrolyte ranging from about 0.2 to about 7.5 % based on the weight of the electrolyte-salt solution, and continuing the electrolytic process to deplete the anode and recover lead at the cathode.
2. The process of Claim 1 wherein the C1-4 alkanesulfonic acid is methanesulfonic acid.
3. The process of Claim 2 wherein the concentration of methanesulfonic acid is from about 20 to about 40%.
4. The process of Claim 2 wherein said electromotive force is a voltage ranging from about 1 to about 3.
5. The process of Claim 4 wherein the concentration of methanesulfonic acid is from about 20 to about 40%, and the anode is at least one electrode of a lead-acid storage battery.
6. The process of Claim 5 wherein said anode is at least one lead acid storage battery composed of a series of electronically-connected positive and negative couples of lead-containing electrodes.
7. The process of Claim 6 wherein there are at least two of said storage batteries connected in series to one another.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/842,578 US4650553A (en) | 1986-03-21 | 1986-03-21 | Electrolytic recovery of lead from scrap |
| US842,578 | 1986-03-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1292203C true CA1292203C (en) | 1991-11-19 |
Family
ID=25287697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 521698 Expired - Lifetime CA1292203C (en) | 1986-03-21 | 1986-10-29 | Electrolytic recovery of lead from scrap |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4650553A (en) |
| EP (1) | EP0238714B1 (en) |
| JP (1) | JPS62230994A (en) |
| AU (1) | AU586045B2 (en) |
| BR (1) | BR8701266A (en) |
| CA (1) | CA1292203C (en) |
| DE (1) | DE3674194D1 (en) |
| DK (1) | DK166735B1 (en) |
| ES (1) | ES2017917B3 (en) |
| IN (1) | IN166444B (en) |
| MX (1) | MX168069B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2353685C1 (en) * | 2007-10-08 | 2009-04-27 | Государственное образовательное учреждение высшего профессионального образования Дагестанский государственный университет | Method of lead utilisation |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5120409A (en) * | 1989-08-08 | 1992-06-09 | Recytec S.A. | Process for recycling an unsorted mixture of spent button cells and/or other metallic objects and for recovering their metallic components |
| IT1245449B (en) * | 1991-03-13 | 1994-09-20 | Ginatta Spa | HYDRO-METALLURGICAL PROCEDURE FOR THE PRODUCTION OF LEAD IN THE FORM OF METAL FROM MATERIALS CONTAINING OXIDES, PARTICULARLY FROM THE ACTIVE SUBSTANCE OF THE ACCUMULATORS |
| US5262020A (en) * | 1991-03-13 | 1993-11-16 | M.A. Industries, Inc. | Hydrometallurgical method of producing metallic lead from materials containing oxides, particularly from the active material of accumulators |
| AU651909B2 (en) * | 1992-09-08 | 1994-08-04 | M.A. Industries, Inc | A hydrometallurgical method of producing metallic lead from materials containing oxides, particularly from the active material of accumulators |
| TR26430A (en) * | 1992-09-10 | 1995-03-15 | Ma Ind Inc | A HYDROMETALLURGICAL PROCEDURE TO PRODUCE METALLIC COURSE FROM MATERIALS THAT REQUIRE OXIDES, INCLUDING ACTIVE MATERIALS OF ACCUMULATORS. |
| US5520794A (en) * | 1995-05-15 | 1996-05-28 | Elf Atochem North America, Inc. | Electrowinning of lead |
| US6428676B1 (en) | 2000-11-08 | 2002-08-06 | Enthone Inc. | Process for producing low alpha lead methane sulfonate |
| RU2245393C1 (en) * | 2003-09-22 | 2005-01-27 | Дагестанский государственный университет | Method of processing of the waste lead storage batteries |
| FR2907352B1 (en) * | 2006-10-20 | 2009-02-20 | Terra Nova | PROCESS FOR PROCESSING WASTE CONTAINING PRECIOUS METALS AND DEVICE FOR CARRYING OUT SAID METHOD |
| KR20090094143A (en) * | 2006-12-15 | 2009-09-03 | 오스람 게젤샤프트 미트 베쉬랭크터 하프퉁 | Led module with dedicated colour regulation and corresponding method |
| JP4406845B2 (en) * | 2007-02-20 | 2010-02-03 | トヨタ自動車株式会社 | Release agent for secondary battery electrode material and method for treating secondary battery using the release agent |
| US20090134039A1 (en) * | 2007-11-28 | 2009-05-28 | Mehlin Dean Matthews | System and method for isotope selective chemical reacations |
| CN102618884B (en) * | 2012-03-16 | 2014-12-31 | 北京化工大学 | Lead regeneration method for recovering lead paste from waste lead acid storage battery by wet method |
| US9322104B2 (en) * | 2012-11-13 | 2016-04-26 | The University Of British Columbia | Recovering lead from a mixed oxidized material |
| DE102013009586A1 (en) | 2013-02-26 | 2014-08-28 | Ulrich Loser | Hydrometallurgical process for the recovery of lll-V, ll-Vl or l-lll-Vl2 compound semiconductor materials from high-tech or green-tech waste or electrical and electronic waste |
| KR101739414B1 (en) | 2013-11-19 | 2017-05-24 | 아쿠아 메탈스 인크. | Devices and method for smelterless recycling of lead acid batteries |
| CA2968064C (en) * | 2013-11-19 | 2021-08-03 | Aqua Metals Inc. | Improved devices and method for smelterless recycling of lead acid batteries |
| CN104711637B (en) * | 2013-12-12 | 2017-05-10 | 沈阳有色金属研究院 | Method for recovering metal lead from solid lead oxide |
| KR102242697B1 (en) | 2015-05-13 | 2021-04-20 | 아쿠아 메탈스 인크. | Closed loop systems and methods for recycling lead acid batteries |
| EP3294931A4 (en) * | 2015-05-13 | 2018-12-26 | Aqua Metals Inc. | Electrodeposited lead composition, methods of production, and uses |
| JP6805240B2 (en) | 2015-05-13 | 2020-12-23 | アクア メタルズ インコーポレーテッドＡｑｕａ Ｍｅｔａｌｓ Ｉｎｃ． | Systems and methods for the recovery of lead from lead acid batteries |
| US10316420B2 (en) | 2015-12-02 | 2019-06-11 | Aqua Metals Inc. | Systems and methods for continuous alkaline lead acid battery recycling |
| FR3060610B1 (en) * | 2016-12-19 | 2020-02-07 | Veolia Environnement-VE | ELECTROLYTIC PROCESS FOR EXTRACTING TIN AND / OR LEAD INCLUDED IN A CONDUCTIVE MIXTURE |
| CN113832344B (en) * | 2020-06-08 | 2022-06-14 | 中南大学 | Method for recovering copper and cobalt from copper-cobalt slag |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1486738A (en) * | 1974-07-25 | 1977-09-21 | Ginatta M | Process for the electrochemical extraction of the metals contained in spent electric storage batteries |
| IT1139420B (en) * | 1981-09-02 | 1986-09-24 | Umberto Ducati | HYDRO-METALLURGICAL PROCEDURE FOR THE RECOVERY OF METALLIFERAL MATERIALS FROM EXHAUSTED LEAD ACID ACCUMULATORS |
| DE3402338A1 (en) * | 1984-01-24 | 1985-07-25 | HAGEN Batterie AG, 4770 Soest | METHOD FOR RECOVERING LEAD FROM OLD LEAD ACCUMULATORS SCRAP AND REDUCTION PLATE HERE |
-
1986
- 1986-03-21 US US06/842,578 patent/US4650553A/en not_active Expired - Lifetime
- 1986-10-21 IN IN766/CAL/86A patent/IN166444B/en unknown
- 1986-10-28 AU AU64461/86A patent/AU586045B2/en not_active Ceased
- 1986-10-29 CA CA 521698 patent/CA1292203C/en not_active Expired - Lifetime
- 1986-10-31 ES ES86114518T patent/ES2017917B3/en not_active Expired - Lifetime
- 1986-10-31 DE DE8686114518T patent/DE3674194D1/en not_active Expired - Fee Related
- 1986-10-31 EP EP19860114518 patent/EP0238714B1/en not_active Expired - Lifetime
- 1986-11-25 DK DK564386A patent/DK166735B1/en not_active IP Right Cessation
- 1986-12-18 MX MX471586A patent/MX168069B/en unknown
-
1987
- 1987-03-17 JP JP62060238A patent/JPS62230994A/en active Pending
- 1987-03-20 BR BR8701266A patent/BR8701266A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2353685C1 (en) * | 2007-10-08 | 2009-04-27 | Государственное образовательное учреждение высшего профессионального образования Дагестанский государственный университет | Method of lead utilisation |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62230994A (en) | 1987-10-09 |
| AU6446186A (en) | 1987-09-24 |
| ES2017917B3 (en) | 1991-03-16 |
| EP0238714B1 (en) | 1990-09-12 |
| US4650553A (en) | 1987-03-17 |
| DE3674194D1 (en) | 1990-10-18 |
| DK564386A (en) | 1987-09-22 |
| EP0238714A1 (en) | 1987-09-30 |
| BR8701266A (en) | 1987-12-29 |
| DK166735B1 (en) | 1993-07-05 |
| AU586045B2 (en) | 1989-06-29 |
| MX168069B (en) | 1993-05-03 |
| IN166444B (en) | 1990-05-12 |
| DK564386D0 (en) | 1986-11-25 |
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