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Overview
A soil washing and leaching process was ping, secondary smelting, and soil wash- turns only 70% of the original contami-
tested for removing lead from soils. A soil- ing. Solidification/stabilization, vitrifi- nated soil back to its site, while the other
washing circuit, including size and gravity cation, and capping have several inher- 30% of the concentrated soil must be
separations, was employed to remove the ent disadvantages5,6 because they can- shipped to secondary smelters.
coarse metallic lead particles, while the leach- not completely remove hazardous con- Several potential methods have been
ing was applied to remove fine metallic lead taminants, but can only stabilize them in tested for remediating surrogate or real
particles and other lead species. The soil- the contaminated medium. soils. Metal-ion leaching or electrokinetic
washing tests proved that the metallic lead Secondary smelting and soil washing remediation were reported to be effec-
particles larger than 0.15 mm (100 mesh) are more complete methods currently tive for removing absorbed lead ions
could be effectively removed. The sodium- adopted in cleaning lead-contaminated from contaminated soil.12–14 More re-
chloride-based leaching solution with ferric soils, and, at the same time, trying to cently, Li and Li15 developed an enhanced
chloride or sodium hypochlorite as oxidants reclaim the lead. Due to its high energy electrokinetic remediation with continu-
was adopted in the leaching. The leaching requirement, the overall cost of the sec- ous rinsing near the cathodic region.
experimental results indicated that under ondary smelting process could be too This process more effectively removed
the pH of 2 and Eh of 1,300 mV, the metallic high8–10 to be economical for large site lead from a carbonate-rich illitic soil.
lead particles smaller than 0.15 mm and cleanup projects. Soil washing is basi- Several extractants were reported to be
other lead species can be dissolved in the cally a size/classification volume-reduc- effective in removing lead from con-
leaching solution within 60 minutes. tion process. It consists of slurrying the taminated soils.16–18
soil with water and physically concen- The soil washing and leaching pro-
INTRODUCTION
trating the contaminants into a size frac- cess, which could clean the soil effec-
Lead pollution poses a health threat in tion of the original soil volume. The con- tively and be operated at relatively low
many developed and developing coun- centrated soil is usually shipped to sec- cost, was tested and reported in this
tries, especially to children.1 Based on ondary lead smelters. Unfortunately, the paper. This process combined gravity-
the statistics of the U.S. Environmental lead at some sites has proven to be rela- separation technology (soil washing)
Protection Agency (EPA), lead and other tively evenly distributed throughout the with leaching of specific soil fractions.
heavy-metal contamination can be found soil, thus making the soil less amenable
THERMODYNAMICS
at about 50% of that agency’s National to soil washing. Another drawback of
Priority List (NPL) sites—U.S. locations this process is that, even in a very suc- The thermodynamics of the lead dis-
with pollution that is potentially haz- cessful demonstration,11 the process re- solution process were investigated to
ardous to human health and the envi-
ronment.2–4 A similar percentage holds Water
for the EPA’s 2000 Resource Conserva-
tion and Recovery Act (RCRA), which Soil 40,000 g
authorizes the clean-up of hazardous Pb Conc. 750 mg/kg
▼ Pb 30 g Trommet
waste sites. In addition, half of the 7,000
▼▼
▼ Cone Water
Eh (V)
▲
▲
Soil 1,960 g
20% by wt. Cleaned Soil Cake In preliminary leaching tests in chlo-
▲
▲▲ ▲▲ ▲▲
Pb Conc. 2,300 mg/kg 1st Drum ride solution, metallic lead showed
Pb 4.5 g Filter ▲
slower leaching kinetics compared to
Soil 1,960 g
Pb Conc. 83.8 mg/kg other common lead species (i.e., lead
Pb 0.164 g
oxide, lead sulfate, and lead carbonate).
▲
▲
Slurry 1st-Stage 2nd-Stage Filtrate Thus, the leaching kinetics of metallic
Tank Reactor Reactor Tank lead was investigated because, when
Filtrate
metallic lead was leached, the other lead
Pb Conc. 554 mg/kg/Pb wt. 4.3 g
Sulfide Solution
species would also be leached. Follow-
ing are some results of the leaching tests.
∑ When the speed of stirring was un-
▲▲ Filtrate der 800 rpm, the kinetics of lead
leaching were controlled by diffu-
▲
▲
2nd Drum
Filter sion. Increasing the speed of stir-
Pb Cake to Smelter ring increased the rate of leaching.
Pb wt. 4.27 g
▲
Filtrate
Precipitation Tank was above 800 rpm, the kinetics were
Reactor Regenerated Solution controlled by chemical reaction and
Pb Conc. 4.4 mg/kg / Pb wt. 0.03 g stirring speed had no effect on the
leaching rate.
Figure 3. The soil-leaching test for soil sample #1.
∑ Since, in heterogeneous reactions
like lead leaching, the reaction oc-
obtain a guide for finding the optimum ride ion and Eh should be avoided in the curs on the surface of lead particles,
lead dissolution conditions. The data of design of a practical lead leaching reac- the rate of reaction will depend on
standard free energies of formation of tion. At a relatively low chloride concen- the surface area of the interface. At
lead species existing in leaching solution tration, lead oxide or hydroxide could a stirring speed above 800 rpm, the
and the equations used to calculate the form to slow the leaching. When the leaching rate follows the shrinking
equilibrium concentration distribution activity of chloride ion is increased to particle model of 1-(1-R)1/3 = (k/r0)t,
of lead species were given in Man’s the- around 2M and the Eh is above –0.25 V, where R is the fraction of lead
sis.19 Also shown were the equations for PbCl3– and PbCl42-– exist in the solution, leached; k is the reaction constant; r0
building the Eh-Log[Cl–] diagram of the which favors lead dissolution thermo- is the initial radius of lead particle,
Pb-Cl–-H2O system and the lead species dynamically, because of their complex and t is the reaction time. The slope
distribution. The Eh-Log[Cl–] diagram ion effects. It is clear in the Eh-Log[Cl–] is in proportion to 1/r0.
of the Pb-Cl–-H2O system is shown in diagram that the optimum ranges of chlo- ∑ The rate of the lead leaching in-
Figure 1. ride-ion concentration and Eh are around creases with an increase in tempera-
It is obvious from the Eh-Log[Cl–] dia- 2M and above –0.25 V, respectively. For ture. The apparent activation en-
gram that the lead species are stable in materials and methods of the study, see ergy calculated from the Arrhenius
the Pb-Cl–-H2O system. The equilibrium the sidebar. plot is 46 kj/mol (11.00 kcal/mol).
potential between metallic lead and
leadchloro-complexes becomes more
negative along with the increase in chlo- Water
ride ion activity. In addition, the dia- Soil 13,000 g
gram shows that cathodic reduction of Pb Conc. 5721 mg/kg
Pb 74.38 g
lead species from the solution would be ▼ Pb Debris 60.68 g
Trommet
▼▼
Conveyer Tank
also shows that various lead species form Feeder Pb Conc. 139 mg/kg
▼ Pb 0.25 g
at various Eh and [Cl–], and that Pb2+ is
Soil 11,200 g
restricted to the range of high Eh and Cleaned Soil
low concentration of chloride ion. Vari- Pump Stockpile
ous lead species predominate as the Eh ▼
and the activity of chloride ion vary. To Leaching Circuit
Elutriator
▼
▲
Beltfilter
▲
drogen electrode. The plot of Log k Cleaned Soil Cake
▲
▲ ▲ ▲▲ ▲▲
1st Drum
vs. Log E gives a straight line with a Filter ▲
slope of 1, indicating that the lead
▲ Soil 5.4 TPH
Water Pb Conc. 80 mg/kg
leaching reaction is a first order re- 9.43 TPH Pb 0.39 g
▲
action with respect to solution po-
▲
Slurry 1st-Stage 2nd-Stage Filtrate
tential. Tank Reactor Reactor Tank
∑ The insoluble lead hydrolytic prod-
ucts form a thin film, which adheres Filtrate 12.6 TPH Pb 1.93 kg/h Pb Conc. 170 mg/kg
to the surface of lead at low chlo- Sulfide Solution
ride-ion concentration, thus retard-
ing further dissolution of lead. When ▲▲ Filtrate
the solution contains high chloride ▲
▲
concentrations, lead chloro-com- 2nd Drum
Filter
plexes form instead of lead hydro- Pb Cake to Smelter
Pb 1.89 kg/h
▲
lytic products, thus increasing the
▲
Filtrate
rate of the lead leaching reaction. Precipitation Tank
∑ The higher the concentration of chlo- Reactor
Regenerated Solution 12.6 TPH
ride ion, the greater the extraction Pb 0.05 kg/h Pb Conc. 4 mg/kg
rate. The lead leaching reaction fol-
lows the shrinking particle model at Figure 6. The soil-washing circuit of a design 50 t/h soil-washing and leaching process.
different chloride concentrations.
∑ Test results indicate that low pH lead sulfide. A lower chloride concen-
density was about 30% solid by weight
facilitates better extraction and en- tration facilitates better lead precipita-
in both leaching stages, while the solu-
hances reaction speed. The reason tion. The reason is that high [Cl–] helps to
tion potential was about 1.3 V and 0.6 V
for this is that the oxidation of lead form stable lead chloride complexes, as
in first and secondary stage leaching,
by hypochlorite is more favorable shown in Figure 1.
respectively. The retention time of each
in acidic conditions: ClO– + H2O +
Soil Washing and Leaching Tests leaching stage was 15–20 minutes.
2e = Cl– + 2OH–. Also, lead chloride,
The resulting filtrate of the leaching
oxide, or hydroxide film is less likely Two soil samples were tested for soil
slurry was directed to the lead precipita-
to form in acidic conditions. washing and leaching, according to the
tion circuit. The solution pH of the lead
flowsheets shown in Figures 2–5. Metal-
Lead Precipitation from Solution precipitation circuit is about 2.0. A sto-
lic lead could be seen in both soil samples.
ichiometric amount of sulfur ion added
A high pH is favorable to obtaining Based on the results of lead leaching and
as sodium sulfide was pumped to the
the better precipitation results when a lead precipitation discussed in the pre-
precipitation circuit, with a retention time
stoichiometric amount of sulfide ion is vious section, the chloride ion concen-
of ten minutes.
added. At a solution with lower pH, tration in both leaching stages was ad-
The results of soil washing and leach-
hydrogen sulfide is more likely to form justed to about 2.0 M with the pH of 1.5
ing are shown in Figures 2–5. The soil-
when sulfide ion is added, thus consum- in first-stage leaching and the pH of 2.0
leaching circuit reduces lead content to
ing the sulfide ion needed to precipitate in secondary-stage leaching. The pulp
about 80 mg/kg in both soil samples.
This low lead content will meet toxicity
▲ Rinse (Water) characteristic leaching procedure tests.
Oxidants/Acid
Soils From In some cases, an additional jig may be
Washing Circuit Slurry Lime
needed in the soil washing circuit to
▲
▲
30% by wt. Cleaned Soil Cake reduce lead to less than 100 mg/kg.
Soil 8,000 g
▲
▲▲ ▲▲ ▲▲
Pb Conc. 830 mg/kg 1st Drum
Pb 6.64 g Filter ▲
Soil 8,000 g
ECONOMIC EVALUATION
Pb Conc. 81 mg/kg
Pb 0.648 g A portable soil washing and leaching
▲
Slurry 1st-Stage 2nd-Stage Filtrate washing and leaching tests of the two
Tank Reactor Reactor Tank
Filtrate soil samples. Efficiencies similar to the
Pb Conc. 318 mg/kg/Pb wt. 5.99g
test unit operations were used for the
Sulfide Solution design. Many factors in metallurgical
plant operation were also included in
the design.20–26 The designed flowsheet
▲▲ Filtrate ▲ of 50 tonnes per hour is presented in
▲
2nd Drum
Figure 6 and Figure 7. An economic
Filter analysis and evaluation was made based
Pb Cake to Smelter on a 50 tonne per hour portable soil
Pb wt. 5.92 g
▲
Filtrate
Precipitation Tank signed plant consists of a gravity circuit
Reactor Regenerated Solution
and a leaching circuit to treat lead-con-
Pb Conc. 3.6 mg/kg / Pb wt. 0.07g
taminated soils. The gravity circuit
Figure 5. The soil-leaching test for soil sample #2.
handles metallic lead with particle sizes
1997).
20. N.L. Weiss, ed., SME Mineral Processing Handbook (New
Loader
▲
York: Soc. Mining Eng., 1985), section 4, p. 13.
▲
Slurry Soil 31.25 TPH 21. R.O. Burt, Gravity Concentration Technology (Amsterdam:
Hopper Conveyer Tank Jig
Feeder
▲ Pb Conc. < 10 mg/kg Elsevier, 1984), pp. 213–214.
Soil 18.75 TPH Water 0.97 TPH 22. D.E. Walsh, P.D. Rao, and D.J. Cook, Study of a Static
Pb Conc. 1,600 mg/kg Screen, Jig, Spiral, and a Compound Water Cyclone in a Placer
Pb 29.9 kg/h
▲ Cleaned Soil Gold Recovery Plant, MIRL Report No. 73 (Fairbanks, AK:
Pump Stockpile Mineral Industry Res. Lab., 1987), pp. 13–44.
Water 43.75 TPH
▲ Pb Con
23. A.L. Mular and R.B. Bhappu, eds., Mineral Processing
1st Jig Makeup Water Plant Design (New York: Soc. Mining Eng., 1980), p. 366.
Makeup Water
▲
22.5 TPH 24. N.L. Weiss, ed., SME Mineral Processing Handbook (New
▲ ▲ ▲ York: Soc. Mining Eng., 1985), section 3D, pp. 38–49.
▲ Sandscrew Soil 13.3 TPH 25. N.L. Weiss, ed., SME Mineral Processing Handbook (New
to Water Sump Pb Conc. 80 mg/kg York: Soc. Mining Eng., 1985), section 9, p. 27.
To Water Sump Pb 1.11 kg/h 26. Bureau of Mines Cost Estimating System Handbook, IC 9143
▲
15.04 TPH
▲
Dewater Cone ▲ Water 3.33 TPH (Washington, D.C.: U.S. Bureau of Mines, 1987), pp. 47–451.
Water 39.44 TPH
▲
27. F.J. Stermole and M.S. Stermole, Self Teaching Manual for
▲
▲
Control the Text-Economic Evaluation and Investment Decision Methods
Valve Water (Golden, CO: Investment Evaluations Corp., 1990), pp. 30–
▲ Sump/Pump Dewater Cleaned Soil Dozer 35.
2nd Jig Cyclone Stockpile
Makeup Water H.K. Lin, X.D. Man, and D.E. Walsh are with the
▲
Water
▲
Soil 0.047 TPH To Leaching Circuit
Dewater Pb Conc. 56.38% Soil 5.4 TPH
Bin Pb 26.5 kg/h Pb Conc. 490 mg/kg For more information, contact H.K. Lin, Mineral
Water 0.893 TPH Pb 2.32 kg/h Industry Research Laboratory, University of
Water 10.03 TPH Alaska Fairbanks, Fairbanks, AK 99775-7240;
(907) 474-6347; fax (907) 474-5400; e-mail: ffhkl@
Figure 7. The soil-leaching circuit of a design 50 t/h soil-washing and leaching process. aurora.alaska.edu.