Separation and Purification Technology 52 (2006) 191–195

Short communication

Cu(II) Removal from lithium bromide refrigerant by chemical

precipitation and electrocoagulation
Hefa Cheng ∗
Department of Environmental Science and Technology, East China Normal University, Shanghai 200062, China

Abstract
A combination of chemical precipitation and electrocoagulation was used to remove Cu(II) from lithium bromide refrigerant, and factors affecting
the treatment efficiency were also studied. The corrosion inhibitor, Li2 CrO4 , was first precipitated from the refrigerant by reaction with Ba(OH)2 ,
which also increased the refrigerant alkalinity to 30.0 meq/L. Significant Cu(II) and Fe(II,III) removals also occurred through adsorption and
co-precipitation. The pretreated refrigerant was further treated in an electrocoagulation cell using iron electrodes, where Cu(II) removal occurred
through coagulation, adsorption on and co-precipitation with ferrous and ferric hydroxides. Fe(II,III) concentration and alkalinity of the refrigerant
did not change significantly during the electrochemical treatment. The optimal laboratory electrocoagulation conditions for the pretreated refrigerant
were: current density at 4.0 mA/cm2 and for 3.0 min. Up to 98.5% of Cu(II) in the contaminated refrigerant could be removed by the combined
treatments.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Cu(II) removal; Electrocoagulation; Lithium bromide refrigerant; Precipitation; Corrosion control

1. Introduction The presence of Cu(II) in lithium bromide refrigerant result-

Lithium bromide (LiBr) solution is widely used as a refrig-
erant for absorption-type air-conditioning and industrial drying
systems due to its highly hygroscopic property [1–3]. Neutral
lithium bromide brine at 55% has a very low solution alkalinity,
and it is highly corrosive and attacks the copper and ferrous parts
of the systems. A solution to inhibit the lithium bromide corro-
sion problem is to increase the alkalinity (and pH) of the brine
through addition of lithium hydroxide (LiOH), which moder-
ates the mild steel attack [1,2]. However, the higher alkalinity
causes rapid deterioration of the copper parts of the systems.
Consequently, corrosion trade-off is made in the refrigerant com-
position by keeping at lower solution alkalinity to protect the
copper and adding an inhibitor to protect the mild steel [1].
Chromate is an excellent corrosion inhibitor for iron systems,
and lithium chromate (Li2 CrO4 ) coupled with very low solu-
tion alkalinity levels have proven to be the corrosion inhibition
scheme of choice for heat-driven absorption systems [1].
∗ Present address: Department of Civil and Environmental Engineering, Stan-
ford University, Stanford, CA 94305, United States. Tel.: +1 650 723 1478;
fax: +1 650 725 3162.
E-mail address: cheng533@stanford.edu.
ing from corrosion of copper parts can cause galvanic corrosion
of ferrous parts in the absorption system. Reduction of Cu(II)
by zero valent iron produces micro-scale copper deposits on
steel surfaces. When oxygen leaks into the system, these copper
deposits serve as cathodes, while the steel parts are corroded
functioning as anodes. The corrosion occurs (at least initially)
at microscopic anodes and cathodes, and macroscopic anodes
and cathodes can develop as corrosion damage progresses with
time [4]. It is necessary to remove Cu(II) from the contaminated
lithium bromide refrigerant to minimize galvanic corrosion.
High concentration of LiBr in the refrigerant complicates
removal of Cu(II). Adsorption by fly ash and reduction by zero
valent iron showed very little Cu(II) removal and no Cu(II)
reduction in the preliminary experiments of this study (data
not shown). Based on its LiBr content (∼55%) and density
(1.62 kg/L), lithium bromide refrigerant has an ionic strength
of ∼10.3 mol/L. The strong competition from the excessive
amount of Li+ resulted in very little Cu(II) retention on the
cationic adsorption or exchange sites on the fly ash. Further-
more, only a small fraction of Cu(II) in the refrigerant existed as
simple ionic species (hexaaquacopper(II) ion), which rendered
most Cu(II) unavailable for adsorption, ion exchange, or redox
reaction. Therefore, it is expected that conventional methods
used for heavy metal removals from waste streams may not be
effective at removing Cu(II) from lithium bromide refrigerant.

1383-5866/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2006.03.021
192 H. Cheng / Separation and Purification Technology 52 (2006) 191–195
Proprietary treatment methods [5–8] have been developed for
removing Cu(II) and other heavy metal ions from inorganic and
organic refrigerants, but their efficiencies are unknown.
Recently, an electrochemical method using iron or aluminum
electrodes has attracted significant attention for heavy metal
removal process due to its operational simplicity [9,10]. During
electrocoagulation, sacrificial anodes corrode to release active
coagulant precursors (usually Fe2+ or Al3+ ) into of the pol-
luted solution [11]. The coagulating ions are produced in situ
and the treatment process involves many chemical and physi-
cal phenomena, such as discharge, anodic oxidation, cathodic
reduction, coagulation, electrophoretic migration, and adsorp-
tion [12,13]. This method has been demonstrated to efficiently
remove heavy metals from wastewaters [9,10,14,15].
Removal of heavy metal ions from concentrated brines by
electrocoagulation has not been reported before, and the effect
of highly concentrated LiBr in the refrigerant on electrochemical
treatment remains unknown. In this study, the efficacy of elec-
trocoagulation for removing Cu(II) from lithium bromide refrig-
erant was investigated, and factors influencing Cu(II) removal
were also studied. The results show that Cu(II) in lithium bro-
mide refrigerant could be efficiently removed by a combination
of chemical precipitation and electrocoagulation, and that elec-
trocoagulation is particularly effective in dealing with heavy
metals in brines with high ionic strengths.
2. Experimental
2.1. Experimental setup and procedures
The experimental setup for electrocoagulation studies is
shown in Fig. 1. A 50 mL beaker was used as the electroco-
agulation cell, with two 2.5 cm × 5.0 cm × 0.2 cm A4 carbon
steel plates used as the anode and cathode, respectively. The
carbon steel plates were suspended in parallel such that the
electrode area immersed in refrigerant was 2.5 cm × 2.5 cm, and
their distance was kept at 1.0 cm. The anode and cathode were
connected to a DJS-292 potentiostat/galvanostat (Cany Instru-
ments, Shanghai) with a saturated calomel electrode used as the
Fig. 1. Schematic diagram of the experimental setup for electrocoagulation treat-
ment.
Table 1
Compositions of lithium bromide refrigerant before and after treatments
Refrigerant Contaminated Pretreateda Treatedb
Density (kg/L) 1.62 1.51 1.51
Cr(III,VI) concentration (mg/L) 1.3 × 103c N/D N/D
Cu(II) concentration (mg/L) 143.6 78.3 2.1
Fe (II,III) concentration (mg/L) 13.0 10.2 10.4
Alkalinity (meq/L) 0.7 30.0 30.0
Note: N/D—below the detection limit of 0.1 mg/L.
a After Ba(OH) pretreatment.
2
b After electrocoagulation treatment at 4.0 mA/cm2 for 3 min.
c Measured after dilution by 200 times.
reference electrode. All electrochemical treatments were con-
ducted at constant currents of 6.25–62.5 mA. A magnetic stirrer
kept the solution in the electrocoagulation cell gently mixed dur-
ing the experiments.
The contaminated lithium bromide refrigerant was obtained
from the absorption chiller of a shopping mall in Shanghai,
China. It had a light orange color with a low level of tur-
bidity. Table 1 lists the compositions of the contaminated
lithium bromide refrigerant. The corrosion inhibitor, Li2 CrO4
(∼0.2%), was first removed from the refrigerant by adding
saturated barium hydroxide (Ba(OH)2 ) solution to precipitate
chromate from the solution as barium chromate (BaCrO4 ). The
precipitate was removed by vacuum filtration using a 1.6 ␮m
filter paper (Grade 43, Whatman) in a Buchner funnel. The
electrocoagulation cell was filled with 50 mL of pretreated
refrigerant, which was treated for 1.0–6.5 min. The treated
refrigerant was obtained after removing the flocs produced in
the electrocoagulation cell by vacuum filtration. Concentrations
of residual Cu(II) and Fe(II,III), and alkalinity of the pretreated
and treated refrigerants were measured to evaluate the treatment
results.
2.2. Chemical analyses
An analytical method that could accurately measure the
low concentrations of Cu(II) in lithium bromide refrigerant
was critical for evaluating Cu(II) removal. Due to the inter-
ference from the high concentration of LiBr, quantification
of trace levels of Cu(II) by conventional atomic absorption
spectroscopy was not precise enough for this study. Instead,
Cu(II) concentration was measured by sodium diethyldithio-
carbamate spectrophotometry [16]. The refrigerant was diluted
by 2500–5000 times with deionized water, Cu(II) concen-
tration was then analyzed by using solvent extraction of
the highly colored Cu(II) complex with diethyldithiocarba-
mate followed by light absorbance measurements at 430 nm
wavelength. Because only Cu(II)–diethyldithiocarbamate
complexes were extracted into the organic solvent (carbon
tetrachloride), no interference from LiBr was observed, and
the detection limit for Cu(II) in the refrigerant was lower than
0.02 mg/L.
Concentrations of Fe(II,III) and Cr(III,VI) in the refrigerant
were measured after dilution with deionized water (5–10 times)
by flame atomic absorption spectrophotometry according to the
 H. Cheng / Separation and Purification Technology 52 (2006) 191–195
Fig. 2. Concentrations of Cu(II) and Fe(II,III) in the electrochemically treated refrigerant influenced by: (a) refrigerant alkalinity, and (b) current density.
standard methods [17,18]. Due to the interference from LiBr,
detection limits of Fe(II,III) and Cr(III,VI) in the refrigerant were
both only around 0.1 mg/L, which were sufficient for the purpose
of this study. For all measurements, linear calibration curves
(R2 > 0.999) were obtained with standards and blanks. Duplicate
samples were measured with the average values reported here.
In the highly concentrated lithium bromide refrigerant, activities
of H+ and OH− were significantly suppressed. Consequently,
alkalinity, instead of pH, was used to represent the quantity of
OH− in the refrigerant. The refrigerant alkalinity was measured
by titration of diluted refrigerant solution (by 15 times) with
0.092 mol/L sulfuric acid using both pH meter and pH paper for
indication of the neutral end point.
3. Results and discussion
3.1. Chemical precipitation pretreatment
During electrocoagulation, Li2 CrO4 in the refrigerant could
also be reduced by Fe2+ released from the anode, and could
subsequently precipitate as Cr(OH)3 [9,10,15]. However,
a chemical precipitation pretreatment was chosen because
removal of Cr(VI) (0.026 mol/L) by the electrochemical
processes would require very long time (>8 h to reduce the
Cr(VI) in 50 mL of pretreated refrigerant at a current density
of 4.0 mA/cm2 ) and produce a large amount of flocs containing
Cr(OH)3 , Fe(OH)3 , Fe(OH)2 , and their mixed hydroxides.
Saturated Ba(OH)2 solution was added into the refrigerant until
the light orange color completely disappeared and overdosed
a little bit. After separation of the yellow BaCrO4 precipitate,
residual Cr(III,VI) concentration was below 0.1 mg/L and
the refrigerant appeared clear and colorless. The pretreatment
results are also shown in Table 1. Cu(II) concentration decreased
by ∼45% after the pretreatment, and reduction in Fe(II,III)
concentration also occurred. Removals of Cu(II) and Fe(II,III)
are attributed to adsorption on the large amount of BaCrO4
precipitated, and possible co-precipitation in the forms of
hydroxides. Alkalinity of the refrigerant was increased from
0.7 to 30.0 meq/L after Ba(OH)2 addition, which was bene-
ficial for subsequent electrocoagulation treatment (discussed
later).
193
3.2. Performance of electrocoagulation
During electrocoagulation at a current density of 4.0 mA/
cm2 , the pretreated refrigerant quickly became turbid with the
appearance of light green to brown flocs, which was caused
by oxidation of ferrous iron and precipitation of ferrous and
ferric hydroxides. Constant production of hydrogen gas bubbles
at the cathode was also observed, while visual inspection
of the cathode found no copper deposit even after 10 min
of electrolysis. This is attributed to the fact that Cu(II) was
rapidly removed from the refrigerant through coagulation by
the newly formed Fe(II) species and through adsorption on and
co-precipitation with the ferrous and ferric hydroxides. The
conclusion that Cu(II) removal occurred through mechanisms
other than electrodeposition is also supported by the fact that
it would take ∼8 min to supply enough electrons for reducing
all the Cu(II) (5.9 × 10−5 mol) in 50 mL of contaminated
refrigerant during electrolysis at 25 mA (current density:
4 mA/cm2 ). In contrast, Cu(II) concentration in the refrigerant
decreased rapidly from 78.3 to 2–3 mg/L within 3.0 min
of electrocoagulation treatment under almost all conditions
studied.
Coagulation process is strongly pH dependent because Fe2+
and Fe3+ are difficult to aggregate under acidic conditions, while
complexes such as Fe(OH)6 3− can form at alkaline pH. It has
been found that lowest residual Fe(II,III) concentrations existed
in the pH range of 6–8 during electrocoagulation [15]. Saturated
LiOH solution (5.3 mol/L) and HCl (6.0 mol/L) were added to
adjust the refrigerant alkalinity to 133.9 and 1.8 meq/L, respec-
tively. Fig. 2a shows the residual concentrations of Cu(II) and
Fe(II,III) in the refrigerants with alkalinities of 1.8, 30.0, and
133.9 meq/L as a function of treatment time. The lowest Cu(II)
concentrations were observed in the refrigerant with the highest
alkalinity, and the residual Fe(II,III) concentrations in it were
also the lowest. This can be explained by the fact that higher
OH− concentration allowed Cu(II) and Fe(II,III) to precipitate
more easily. Measurements showed no appreciable refrigerant
alkalinity change (data not shown) throughout the electrochem-
ical treatment. This can be explained by the fact that Fe2+ and
OH− were produced at stoichiometrically identical amounts in
the electrolysis process, and they both left the solution in the
form of Fe(OH)2 precipitate. Only a small fraction of Fe(II)
194 H. Cheng / Separation and Purification Technology 52 (2006) 191–195
could be oxidized before precipitation in the short treatment
times (≤6.0 min), so H+ produced from Fe(II) oxidation did
not change the refrigerant alkalinity. Possible precipitation of a
small amount of Cu(II) in form of Cu(OH)2 could not change
the alkalinity, either. Overall, alkalinity did not show a signif-
icant impact on Cu(II) removal, and it was not cost-effective
to adjust the refrigerant alkalinity to achieve the slightly higher
(1.9–2.7%) Cu(II) removals.
Current density determines the amount of iron coagulant pro-
duced in the electrochemical process because the iron anode
loses electrons and dissolves into solution as Fe2+ . Fig. 2b shows
the current density effect on Cu(II) concentration in the treated
refrigerant as a function of time. There was a weak trend of less
residual Cu(II) with higher current density, but current density
higher than ∼4.0 mA/cm3 did not improve Cu(II) removal. Over-
all, Cu(II) concentration decreased rapidly within the first minute
of treatment, followed by a more gradual decrease between 1.0
and 3.0 min. Treatment time longer than 3.0 min did not bring
more Cu(II) removal, either. More iron hydroxide flocs were
produced at higher current density and longer treatment time,
but it appears that there was a practical limit on Cu(II) removal
by electrocoagulation. From these observations, it can be con-
cluded that the rapid Cu(II) removal was caused by the Fe2+
released from the anode oxidation during electrolysis, which
neutralized the charges of the Cu(II) hydroxide colloids and
thereby initiated coagulation. Discharge of the colloidal par-
ticles in the applied electric filed [13] possibly contributed to
coalesce and coagulation, too. Cu(II) removal also occurred
through adsorption on and co-precipitation with ferrous and fer-
ric hydroxides. Fe(II,III) concentration remained between 10.1
and 10.6 throughout the treatment under the above conditions,
and the refrigerant alkalinity (data not shown) did not change
significantly either.
The above results suggest that the optimal operating condi-
tions for electrocoagulation in the experimental setup were at
current density of 4.0 mA/cm2 for 3 min, and without alkalinity
adjustment. Compositions of the treated refrigerant are also
included in Table 1. Under the optimal treatment conditions,
as high as 97.3% of Cu(II) in the pretreated lithium bromide
refrigerant could be removed by electrocoagulation, which led
to an overall 98.5% Cu(II) removal from the contaminated
refrigerant. A small amount of Fe(II,III) was introduced
during electrocoagulation, but Fe(II,III) concentration in the
treated refrigerant was still lower than that in the contaminated
one.
3.3. Power consumption and applicability
The power consumption of electrocoagulation can be calcu-
lated from the electrolysis current and the cell voltage (measured
between the cathode and anode), and the results are shown in
Fig. 3. High power consumption occurred at high current den-
sity, and an approximately linear relationship between the power
consumption and current density was observed. The high LiBr
concentration made the refrigerant highly conductive, and the
electrocoagulation treatment only consumed little electricity.
Under the optimal treatment conditions (4.0 mA/cm2 for 3 min),
Fig. 3. Power consumption () of the electrocoagulation cell and the cell voltage
(♦) as a function of current density during electrocoagulation of the pretreated
refrigerant.
the power consumption for per cubic meter of pretreated refrig-
erant should be less than 75 kJ (0.0208 kWh).
Cost and operational simplicity are important considerations
for the application of any method for removing Cu(II) from the
contaminated refrigerant. No chemical addition is required in the
electrocoagulation treatment, and the iron electrode consumed
is cheap and readily available. The electric field is applied to the
refrigerant for only a short time, and the power consumption is
very low. On large scale operations, Cu(II) removal can be easily
achieved in a continuous flow system with a relatively short res-
idence time, and the treated dispersion can be transferred to an
integrated clarifier system to separate the flocs from the treated
refrigerant. Addition of Ba(OH)2 solution during pretreatment
made the treated refrigerant a little less concentrated compared to
the contaminated one. However, this does not complicate reuse
of the treated refrigerant because heat-driven absorption systems
concentrate lithium bromide refrigerant through the internal heat
exchange process [1,19]. On the other hand, addition of Li2 CrO4
(corrosion inhibitor) and HBr (alkalinity reduction) are neces-
sary to adjust the composition of the treated refrigerant.
4. Conclusion
Cu(II) removal from lithium bromide refrigerant was success-
fully achieved by pretreatment with Ba(OH)2 solution followed
by electrocoagulation using carbon steel plates as electrodes.
Cu(II) concentration decreased by ∼45% after the pretreat-
ment due to adsorption on and co-precipitation with BaCrO4 .
Removal of Cu(II) from the pretreated refrigerant occurred
through coagulation by the electrochemically formed Fe2+
and adsorption on and co-precipitation with ferrous and ferric
hydroxides. No significant changes in Fe(II,III) concentration
and alkalinity of the refrigerant occurred during the electroco-
agulation treatment. Refrigerant alkalinity did not significantly
affect the treatment efficiency, and current densities greater than
4.0 mA/cm2 and treatment times longer than 3.0 min did not
improve the treatment results. Residual Cu(II) and Fe(II,III) con-
centrations were 2.1 and 10.4 mg/L in the refrigerant under the
following optimal electrocoagulation conditions: current density
of 4.0 mA/cm2 and 3.0 min treatment time. The concentrated
 H. Cheng / Separation and Purification Technology 52 (2006) 191–195
LiBr in the refrigerant did not complicate the electrocoagula-
tion treatment, but made the electrochemical treatment highly
efficient by increasing the conductivity. Results of this study
indicate that electrocoagulation has great promise for removing
Cu(II) from lithium bromide refrigerant, and for removing other
heavy metal ions from high ionic strength solutions.
Acknowledgements
This study was conducted as part of the author’s B.S. thesis
research between September 1997 and June 1998. Support from
the Department of Environmental Science and Technology, East
China Normal University, is appreciated.
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