Overview

Placid-A Clean Process for Recycling

Lead from Batteries
Gustavo Diaz and David Andrews

The Placid process is a hydrometallurgi-
cal technique for recovering lead from spent
battery pastes. The process, when used in
combination with a pyrometallurgy process,
has the potential to recover high-purity lead
and offers significant environmental im-
provements.
INTRODUCTION
In June 1995, 15 delegates to the Inter-
national Lead Zinc Study Group Confer-
ence1 visited the R&D Centre of Tecnicas
Reunidas in Torrej6n de Ardoz, near
Madrid, Spain, to observe the operation
of the Placid pilot plant, where a hydro-
metallurgical process for electrowinning
lead has been under intensive develop-
ment for more than two years. The Placid
process is intended primarily for the
recovery of very pure lead from spent
to the leaching bath. The reaction of paste
with brine yields not only soluble lead
chloride, but also sodium sulfate. This is
converted into gypsum by first neutral-
izing the hydrochloric acid with an ex-
cess of milk of lime, forming calcium
chloride and water. The calcium chlo-
ride then reacts with the sodium sulfate
to precipitate gypsum, leaving salt that
is also returned as makeup to the leach-
ing bath. The reaction equations are
shown in Table I.
The Placid process was
;:==================:::;
invented by the techni-
cal team in the R&D Cen-
tre of Tecnicas Reunidas.
A comparison of the pro-
cess with other processes
is shown in Table II, and
the description pub- REAGENT RECYCLING
versity of Alicante, Spain; lNO, Nether-
lands; Quimitecnia, Portugal; and David
Andrews Projects Limited, United King-
dom. Research and development is be-
ing carried out by the LEREFLEOS part-
ners as coordinated by Tecnicas
Reunidas.
THE PRACTICAL CYCLE
In the practical cycle, shown in Figure
1, lead scrap and lead oxide secondary
LEAD
Ioooo--"T""""-.....
POWDER
'"
,
OPTIONAL
...._ _ , . - -... SO,URCE

,,
battery pastes for reuse in the manufac- lished in 19912 remains
ture of new battery pastes. The fourth, substantially unchanged.
_.J
and final, pilot plant campaign con- In January 1993, the
cluded on July 14, 1995, and the process European Union ac-
will be commercially available in 1996. cepted the proposed
Lead Recovery From
THE PROCESS
Lead Oxide Secondaries
Placid (plomo acido) denotes the leach- (LEREFLEOS) project to Figure 1. A block diagram of the Placid process.
ing of lead in warm, slightly acidic, develop the concept
hydrochloric acid brine to form soluble within the CEU Brite ACID ANOLYTE MEMBRANE LEAD METAL
lead chloride. Lead is won from the lead Euram II Programme.
chloride on the cathode of an electrow- Half of the development
inning cell and is collected. Chloride cost incurred is met from
anions are released simultaneously, but that source. The other
then react immediately with hydrogen half, plus preparatory
ions that have been liberated stoichio- and continuation costs,
metrically from water electrolysis in the is being met by the
anolyte and passed into the catholyte LEREFLEOS Consor-
through a membrane. The hydrochloric tium members-Tech-
acid thatis formed is returned as makeup nicas Reunidas S.A.,
Spain; ICAT, University
Table I. The Principal Equations of the of Lisbon, Portugal; Uni- Figure 2. A diagram of the Placid electrowinning cell.
Placid Process
Leaching Reactions Table II. Comparison of the Placid Process with Other Electrowinning Processes3
PbO + 2HCl ~ Pbq + HzO Pb Current
Pb + Pb02 + 4HCl ~ 2PbCl2 + 2HzO Process Electrolyte Additives (gil) Purification Cell Type (A1m2)
PbSO. + 2NaCI ~ PbCl2 + Na2SO. ---
RSR Fluosilicic or >500 ppm As + 70-200 None Simple 100-200
Na2SO. + 2HCl + Ca(OH)2 ~ CaSO. + Fluoboric Acid Boric Acid
2NaCl+ 2HzO
Purification Reactions* USBM* Fluosilicic Acid 3-6 gil H 3PO. + 25-150 None Simple 150-250
MeCl2 + Pb ~ PbCl2 + Me 0.05 gil Bone Glue +
Electrolytic Reactions 4 gil Lignin
Cathodic: PbCl2 + 2e- ~ Pb o + 2Cl- Sulfonate
Anodic: HzO ~ 2H+ + 1/2°2 + 2e- Engitec Fluoboric Acid Glues 50-100 None Composite 320
Overall: PbCl2 + HzO ~ Pbo + 2HCl + Anode
1/2°2 AAS** AAS None ? None Cascaded ?
Global Pastes Reactions Placid HCl None 25 Cementation Ion-Selective 1,200
PbSO. + Ca(OH)2 + HzO ~ Pb + CaSO•. Brine Solution Membrane
2HzO+ 1/2°2
• USBM-U.S. Bureau of Mines
• Me-Any metallic impurity. .. AAS--Ammoniacal Ammonium Sulfate leaching

1996 January • JOM 29


Figure 3. The electrowinning cell developed for the pilot plant.
materials are fed into the leaching bath,
and the lead metal combines with chlor-
ine. The dilute lead-chloride solution
passes to the purification step, wherein
lead powder is added to form cements of
any metallic impurities for disposal.
Pure catholyte passes to the electrow-
inning cell, and the won lead is removed
by a conveyor belt for compaction into
briquettes, which are easily melted into
lead ingots. Spent catholyte is divided
into two streams; most goes directly to
the leaching bath, but a portion is di-
verted to a clean-up circuit, from which
usable reagents are returned.
At the heart of the process is the elec-
trowinning cell, illustrated in Figure 2.
Figure 3 is a photograph of the cell de-
veloped for the pilot plant. The anodic
and cathodic electrolytes are treated
separately and kept apart by membranes
that are permeable by the proton ions
(H+) liberated on the anode. Within the
catholyte, proton ions combine with the
negatively charged chloride ions liber-
ated from the lead chloride on the cath-
ode, thereby reforming the hydrochloric
acid required for leaching.
The pilot plant for the process was
designed to produce 400 kg of pure lead
a day, a capacity that was limited by the
capacities of the transformer and recti-
fier available. The electrowinning cell
was designed to accept five double-sided
cathodes of 0.8 m 2 each, but when the
current density was increased from 1,000
A/m2 to 1,200 A/m2, one was removed.
There are five anodes. It is envisaged
that a production version of this cell
would be similar, but with 20 or more
cathodes instead of four. This would
give a minimum output capacity of 730
tonnes a year per cell.
COMBINED CYCLES
Economic considerations suggested
that it would be sensible to use electrow-
30
inning only for the recovery of lead from
lead pastes, thereby providing the pure
lead required for the manufacture of
new paste. Computer modeling of a va-
riety of configurations showed thatthere
would be major advantages in operating
the Placid process and a pyrometallurgi-
cal process (now just a melter) together.
Figure 4. The combined process of the Placid process used with a pyrometallurgical process.
Figure 4 shows such a combined cycle
concept. The classification step is refined
to separate the pastes from the grids and
supports; the pastes go to the Placid
process and the solid lead goes to the
melter. There are four major advantages
to this combination.
First, the temperature of the furnace
can be reduced from present values
(variously quoted as 850-1,100°C) to just
above the melting point of lead (Le.,
about 370°C). Furnace life is extended,
fume emission is reduced, and problems
like the accumulation of cadmium (from
undetected nickel-cadmium batteries) in
bag filters are eliminated.
Second, the fumes, slags, and drosses
from the melter can be passed to the
Placid process, which is better able to
extract the lead, while the cements of
impure metals can be returned to the
melter.
Third, the purity of the Placid-pro-
cessed lead can be increased to above
99.99%. Representative impurity levels
in the lead sponge produced in pilot
plant operations, measured in parts per
million, were <5 Ag, <5 As, <1 Bi, <10 Fe,
<10 Cu, <20 Sb, <2 Sn, and <5 Zn. The
purity of ingot lead is expected to be
better. Lead produced by the process
should be suitable for the most demand-
THE PLACID PROCESS
IMPORTED FUMES
RESIDUALS
4.62
LEACHING OF
26.5
26.5
LEAD-ACID
ELEC1ROWlNNING
26.5
1.5
LEAD
COMPACTION
25
EXISTING
MELTING
INGOTS >99.99% PURE
JOM • January 1996
ing of applications.
Fourth, hazardous wastes are elimi-
nated and the total amount of waste that
must be disposed of is reduced approxi-
mately by half.
ENVIRONMENTAL
ADVANTAGES
The principal waste rejected by the
Placid process is gypsum containing
refractories from the raw materials. The
lead content is less than 1.5%, and stan-
dard tests have shown that it is nonhaz-
ardous and acceptable for landfills. The
quantity of gypsum is directly deter-
mined by the amount of sulfate to be
disposed.
The amount of effluent, consisting only
of brine and soluble alkaline chloride
salts, is negligible in quantity and could
be considered as a by-product reagent
for use in other industries. The only gas-
eous emission is oxygen, although envi-
ronmental regulations require precau-
tions to be taken in case minute quanti-
ties of chlorine are released.
Because the maximum temperature in
the Placid process is 80°C, there is no
significant emission oflead fumes. Quali-
tative evidence for this has been pro-
vided by the pilot plant campaigns. No
special precautions had been taken to
remove fumes from the vicinity of any
part of the process, but air samples from
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contact the TMS Circulation
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pubs/journals/JEM/jem.html
all areas, including the leaching area and
the electrowinning cell area, were tested
by an independent laboratory. The lead
concentration in every case was found to
be below 40 micrograms per cubic meter.
This compares with the permitted limit
in the United Kingdom of 150 micro-
grams per cubic meter, which is attained
by smelters only with some difficulty.
The emission of fumes from melting
operations will be reduced, as compared
with smelting operations, as a result of
the greater than 500°C reduction in fur-
nace temperature. It is anticipated that
the implementation of the combined pro-
cess will lead to a major reduction in the
lead blood counts of personnel.
ECONOMIC ADVANTAGES
It is impossible to give a general as-
sessment of the economic return that
would result from the installation and
use of the Placid process in any particu-
lar instance; much depends on the prices
of lead and scrap batteries, local condi-
tions, and accidental opportunities.
However, it need not be punitive.
The process is efficient, with the result
that the total electrical consumption is
only 1,300 kWh per tonne of lead prod-
uct. The imported materials-other than
batteries and lead scrap-are mainly
lime. Operating costs are slightly lower
than for the pyrometallurgical equiva-
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lent. The capital cost, based on a good
engineering standard, has been esti-
mated at $900 per tonne of lead product
per annum as a maximum, including a
contingency allowance of 25 percent. A
large part of this is the cost of the elec-
trolysis system. In one case study, it was
estimated that even with generous cost
allowances for uncertainties, the inter-
nal rate of return would be 30 percent
and the pay-back period at the then-
price of lead would be 3.5 years.
References
1. International Lead-Zinc Study Group Conference, Madrid,
1&--23 June 1995.
2. Daniel Martin San Lorenzo and Gustavo Diaz Nogueira,
"Hydro metallurgical Treatment ofLead Secondaries: The PLACID
Process", International Lead-Zinc Study Group Conference,
Rome, June 1991.
3. R. David Prengaman, "Recovering Lead from Batteries,"
JOM, 47 Oanuary 1995), pp. 31-33.
ABOUT THE AUTHORS
Gustavo Dfaz earned his B.S. in industrial
chemistry at the University of Valladolid in
1975. He is currently R&D division director at
Tecnicas Reunidas, S.A.
David Andrews is a chartered engineer in
both mechanical and aeronautical engineer-
ing. He is currently a consultant in project
management.
For more information, contact Gustavo Diaz,
Technicas Reunidas, S.A., R&D Centre, clo Si-
erra Nevada 16, Po. Ind. San Fernando II, 28850
Torrejon de Ardoz, Madrid, Spain; telephone 34-
1-6757700; fax 34-1-6757821.
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