Research Article

Received: 5 May 2009 Revised: 10 October 2009 Accepted: 30 October 2009 Published online in Wiley Interscience: 7 December 2009

(www.interscience.wiley.com) DOI 10.1002/jctb.2313

The recovery and recycling of mercury

from fluorescent lamps using photocatalytic
techniques
Juan Bussi,a,b∗ Marı́a Noel Cabrera,a José Chiazzaro,a Carolina Canel,a
Santiago Veiga,b Carlos Florencio,b Enrique A. Dalchielec
and Marcelo Belluzzid

Abstract
BACKGROUND: Release of mercury from fluorescent lamps must be minimized to avoid its hazardous effects on human beings
and other living organisms. Because of this, increasing attention is given to the improvement of existing techniques for its
recovery as well as the development of new ones. This paper describes the application of heterogeneous photocatalysis for
the selective reduction of mercury from fluorescent lamps. The whole process involves mercury chemical extraction using
aqueous solutions of sodium hypochlorite. After pH adjustment of the resulting aqueous solution, the photocatalytic reduction
of mercury is performed in the presence of titanium dioxide and citric acid as an auxiliary organic agent.

RESULTS: Mercury removal from the aqueous solution is higher than 99% and the final residual concentration is 4 ppb. A
mixture of different mercury compounds is obtained in solid form deposited on the titanium oxide photocatalyst which can
easily be redissolved into a small volume of sodium hypochlorite. Metallic mercury could be obtained from the residual Hg(II)
solution by conventional cementation techniques with iron as reducing agent.

CONCLUSION: Results show high efficiencies of the photocatalytic technique for recovery and recycling of mercury from
fluorescent lamps.

c 2009 Society of Chemical Industry

Keywords: fluorescent lamps; mercury; heterogeneous photocatalysis; sodium hypochlorite

INTRODUCTION such as those from chlor-alkali plants.5 – 8 These ‘wet methods’

The increasing use of fluorescent lamps around the world has
caused a growing concern about their proper disposal to avoid
mercury release to the environment once spent lamps are dis-
carded and broken.1,2 Among the different options, recycling
has the advantage of reusing certain raw materials including
mercury. Recycling of fluorescent lamps is performed by a ‘dry
method’ giving four products: mercury-contaminated phosphor
powder, mercury-contaminated filters, crushed glass and alu-
minum end caps. The entire system is operated under negative
pressure to minimize mercury emissions to the atmosphere.
Mercury is then recovered from the contaminated residues by
batch distillation at temperatures higher than 375 ◦ C for 4–20 h.
The vaporized mercury is then condensed and collected in a
decanter.3
Although the dry method can be adjusted to minimize mercury
emissions, the amounts of mercury recovered and which remains
adsorbed onto the glass have not been extensively investigated to
date and only few studies on how much mercury is really collected
have been made.4
Other methods involving leaching with a suitable chemical
reagent followed by adsorption, ion exchange or formation of
highly insoluble mercury compounds are also available and can
478
can operate in a safe way under experimental conditions close
to normal temperature and pressure and at a low cost. They
can operate batch-wise or continuously and can be adapted
to small or large scale and for a wide range of mercury
concentrations.
Heterogeneous photocatalysis (HP) is a novel technique for
the removal of minute amounts of metal ions in aqueous
solutions.9 – 11 In this technique UV–VIS photons are absorbed
∗ Correspondence to: Juan Bussi, Laboratorio de Fisicoquı́mica de Superficies,
Departamento de Experimentación y Teorı́a de Estructura de la Materia y sus
Aplicaciones (DETEMA), Facultad de Quı́mica, Gral. Flores 2124, Montevideo,
Uruguay. E-mail: jbussi@fq.edu.uy
a Instituto de Ingenierı́a Quı́mica, Facultad de Ingenierı́a, Universidad de la
República, Uruguay
b Laboratorio de Fisicoquı́mica de Superficies, Departamento de Experi-
mentación y Teorı́a de Estructura de la Materia y sus Aplicaciones, Facultad de
Quı́mica, Universidad de la República, Uruguay
c InstitutodeFı́sica,FacultaddeIngenierı́a,UniversidaddelaRepública,Uruguay
d Cátedra de Análisis, Departamento Estrella Campos, Facultad de Quı́mica,

be integrated in processes for mercury recovery from solid wastes Universidad de la República, Uruguay

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c 2009 Society of Chemical Industry
Recovery and recycling of mercury from fluorescent lamps www.soci.org

by a semiconductor (SC), whose band gap energy is equal to or

Table 1. Typical composition of inner coating of fluorescent lamps
lower than the energy of the photons. The energy of the absorbed (reference 2)
photons promote the passage of electrons from the valence band
of the semiconductor to its conduction band. Electrons can reach Concentration
Element (mg element kg−1 phosphor powder)
the surface of the semiconductor and can reduce appropriate
species in solution. On the other hand, the holes created in the Aluminium 3000
valence band can also migrate to the surface where they will oxidise Antimony 2300
available species in solution. The net effect is the occurrence of Barium 610
one or more redox chemical reactions in the solution where the Cadmium 1000
irradiated semiconductor plays the same role as a catalyst in a Calcium 170 000
thermally activated chemical reaction. In the case of mercury, Chromium 9
Hg(II) ions present in water can be chemically reduced according Cobalt 2
to the following reaction mechanism.12,13 Copper 70
Iron 1900
hν + SC −−−→ e− (conduction band) Lead 75
+ hvb (valence band) −−−→ recombination (1) Magnesium 1000
Zinc 48
Hg 2+
(aq) −−−→ Hg 2+
(ads) (2)
Manganese 4400
− ◦
Hg 2+
(ads) + 2e −−−→ Hg(ads) (3) Mercury 4700
H2 O −−−→ H+ + OH− (4) Nickel 130
+ − • + Potassium 140
hvb + OH ads (H2 O)ads −−−→ OH (+H ) (5)
Sodium 1700

OH• radicals are very reactive and can give rise to several
reaction products including molecular oxygen according to the
following stoichiometry:
2OH• −−−→ H2 O + 1/2O2
Mercury reduction can be helped by species which are more
oxidizable than water (reactions 4, 5 and 6). This is the case of
several organic agents such as citric acid as reported by Tenakonne
and Ketipearachchi.14 The citrate ion (Cit3− ) formed a complex
anion with Hg2+ of the form [Hg2+ nCit3n− ], which reacts with OH•
radicals as follows:
the mercury from fluorescent lamps. However other elements
are present in the phosphor powder (Table 1) and these could
(6) interfere in the selective separation of mercury by formation of
metal–citrate complexes and/or by competitive adsorption on
the photocatalyst. Therefore the experimental conditions must be
adjusted in order to afford the feasibility of the process.
This paper reports the main results obtained in the experimental
studies dealing with the application of a wet method involving het-
erogeneous photocatalysis for selective reduction and recycling
of mercury from fluorescent lamp residues.

[Hg+2 nCit3n− ] + (3n − 2)H+ + (18n − 2) OH•

−−−→ 6nCO2 + (13n − 2)H2 O + Hg
◦ EXPERIMENTAL
where Hg2+ is reduced by photo-generated electrons as shown in
Equation (3).
Because of the slight solubility of the reduced mercury com-
pounds from the photocatalytic reaction, mercury is continuously
separated from the aqueous solution during the HP process.
In earlier work, the HP technique was applied to the removal of
mercury from hazardous solid wastes from a chlor-alkali plant.15
There, a combined process involving leaching with a suitable
acid/oxidant reagent and further photocatalytic treatment led to
the selective precipitation of reduced mercury as mercurous oxide
(Hg2 O), mercurous chloride (Hg2 Cl2 ) and metallic mercury (Hg◦ ),
while the other metal compounds remain in solution, mainly in
their ionic form (Ca2+ , Mg2+ , Fe3+ ). In spite of the large excess of
non-reducible metal ions, 100 times or more on a molar basis,
more than 99% of the mercury initially present in the solid
wastes was removed. Competitive adsorption of the different
metal compounds on the SC surface led to lower rates of mercury
reduction. This combined process can be an efficient alternative
method for mercury separation because the final effluents reach
a quality close to the standards legally imposed by international
environmental agencies.
A similar process combining metal leaching and heterogeneous
Leaching extraction
Experiments were performed on crushed lamps as received
from a local fluorescent lamp recycling enterprise. Two types
of reagent were used for the attack on crushed lamps: a mixture
of hydrochloric and nitric acids (3/1 v/v) and an aqueous solution
of sodium hypochlorite. Borosilicate glass vessels were used for all
the experiments and special care was taken to control potential
adsorption on glass walls. Solutions obtained after filtering were
stored in closed vessels together with the rinse waters. More
specific details about experimental conditions are included in the
corresponding tables of results.
Photocatalytic experiments
These were performed in a recirculating system (flow rate =
40 mL min−1 ) consisting of a tubular borosilicate glass reactor
(diameter 1.8 cm, length 60 cm), a peristaltic pump and a glass
vessel open to air. Two UV lamps (Philips ‘TL’D 18/08), 18 W each
with a radiation peak value of approximately 360 nm were placed
around the photoreactor as source illumination. Titanium dioxide
(TiO2 ) Degussa P-25 was used as the photocatalyst in all the
experiments. Reactions were performed with filtered solutions
from leaching treatment of fluorescent lamps with the HCl-HNO3
mixture and the NaOCl-pH 5.5 solutions. In all cases, a known
479

photocatalytic treatment could be applied to the separation of amount of citric acid was added to the solution and its pH

J Chem Technol Biotechnol 2010; 85: 478–484

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 www.soci.org J Bussi et al.

adjusted to 5.5 using 1 mol L−1 solutions of HCl and NaOH. The
final volume of solution was adjusted with distilled water and
the resultant dilution factor is reported in the corresponding
Figure. A known amount of the photocatalyst was added to
the solution and kept in suspension by magnetic stirring for
15 min before starting the irradiation. This suspension was fed
continuously to the photoreactor and recirculated to the flask
with a peristaltic pump. All the experiments were performed
at room temperature. More specific details about experimental
conditions are included in the corresponding figures. Samples
of the solution were periodically withdrawn and filtered through
a 0.45 µm Millipore filter. The mercury content in the filtered
solutions was analyzed by atomic absorption spectroscopy, using
both flame ionization and cold vapour methods. X-ray diffraction
of mercuric deposits after the photocatalytic treatment were
performed with a Philips PW3 710 diffractometer using CuKα
radiation. Calcium and magnesium ion content in the filtered
solutions was determined by conventional complexometric
titration with ethylenediamminetetraacetic acid (EDTA) and
results are reported as concentration of calcium carbonate
(g L−1 ).16
Cementation experiments
Recovery of metallic mercury from Hg(II) solutions was performed
by reducing with metallic iron as reported by Twidwell and
Thompson.8 Hg(II) solutions were obtained by HgCl2 dissolution
with water and, when stated, by oxidation of known amounts of
Hg◦ with a NaOCl aqueous solution, 14 g.L−1 , pH 5.5. The amount
of iron used was twice the stoichiometric amount.
RESULTS AND DISCUSSION
Leaching extraction
Tables 2 to 4 show the results of leaching tests performed with the
first series of samples of crushed lamps. Using both a non-diluted
mixture of the two concentrated acids (HCl + HNO3 ) and one with
a dilution factor 1 : 2 led to high amounts of extracted mercury
in the 20 min leaching tests at ambient temperature. A second
treatment of the same sample revealed much lower concentration
of mercury in the order of that found in the distilled water rinsings.
Leaching tests with NaOCl at ambient temperature and no
adjustment of the initial pH showed only partial leaching of
mercury even with a higher leaching time (120 min). Mercury

Table 2. Mercury leaching tests with 3 : 1 v/v hydrochloric and nitric acid mixture
Leaching solution
Acid mixture volume/lamp residues Leached Hg Leached Hg
Test N◦ dilution weight (mL g−1 ) Treatment1 (mg kg−1 glass) (mg kg−1 phosphor)2

1 – 50/10 Single 73 1781

2 1/5 50/10 Single 32 781
3 1/5 50/20 Double 31 756
4 1/2 50/20 Single 81/63/59 1976/1537/1439
5 1/2 50/45 Double 47 1146
6 – 40/40 Column 37 902
7 – 50/40 Double 54 1317
8 – 50/20 Single 49 1195
9 1/2 50/40 Single 54/52 1317/1269
Contact time: 20 minutes.

– Without dilution.
1 Single: one attack with the indicated acid volume to lamp residues mass ratio.

Double: the total volume of the acid mixture is used to treat a first fraction of the residues. The resulting solution is used for the attack of the second
fraction of residues.
Column: the test is performed by passing the acid mixture through a glass column packed with lamp residues. Experimental conditions: elution rate:
22 mL min−1 ; numbers of elutions: 7; column diameter: 2.5 cm.
2 The weight of phosphor in lamp residues is determined by weight difference before and after the acid attack.

Table 3. Mercury leaching tests with NaClO solutions

Leaching solution
volume/lamp residues Leached Hg Leached Hg
◦
Test N [ClO-] g L−1 (1) weight (mL g−1 ) Treatment1 (mg kg−1 glass) (mg kg−1 phosphor)

1 72 50/20 Simple 37 902

2 36 50/20 Simple 23/26 561/634
3 18 50/20 Simple 13 317
4 36 50/20 Simple2 61 1488
5 36 20/20 Simple 26 634
1 Commercial sodium hypochlorite has 100 g L−1 of active chlorine.
2 Tests are carried out at ambient temperature except for test n◦ 4 which was carried out at 100 ◦ C.
Initial pH of NaOCl solutions: 11.
Contact time: 120 min.
480

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Recovery and recycling of mercury from fluorescent lamps www.soci.org

Table 4. Leaching tests with NaClO at pH = 5.5 and 80 ◦ C

Leached Hg

Leaching solution volume/lamp

[ClO− ] residues weight Time
Test N◦ (g L−1 )1 (mL g−1 ) (min) (mg L−1 )1 (mg kg−1 glass) (mg kg−1 phosphor)

1 7 40/20 20 43 87 2116
2 14 200/200 25 57 79 1918
3 14 50/20 30 16 52 1266
4 28 20/20 20 33 48 1175
1Adjustment to pH=5.5 is performed with addition of 1 mol L−1 HCl. Final pH close to 4.
Temperature kept in 80 ◦ C during all the leaching treatment.

Table 5. Standard reduction potentials (E◦ ) and reduction potential (E) for Hg extraction by NaOCl leaching solutions at 25 ◦ C

Half reaction E◦ (V) ENernst

HClO(aq) + H+ (aq) + e− → 1/2Cl2 (g) + H2 O(l) +1.63 +1.63 − 0.059 log (pCl2 1/2 /aHClO .aH+ )
ClO− (aq) + H2 O(l) + 2e− → Cl− (aq) + 2OH− (aq) +0.89 +0.89 − (0.059/2) log (aCl− .aOH− 2 /aClO− )
1/2Cl2 (g) + e− → Cl− (aq) +1.359 +1.359 − 0.059 log (aCl− /pCl2 1/2 )
Hg2+ + 2e− → Hg(l) +0.85 +0.85 − (0.059/2) log (aHg2+ )

leaching increased when the temperature was raised, as is shown 20°C

80°C
in test N◦ 4 performed at 100 ◦ C, although it still remains lower 45
than the maximum obtained in the acid leaching. 40
The addition of hydrochloric acid to the NaOCl and heating 35
improves its ability to extract Hg. Results obtained in 20 min tests 30
[Hg] mg.L-1

at pH 5.5 (Table 4) show that the leached Hg can attain values of

the same order as those found with the acid treatment. The better
performance of the acidified NaOCl is for several reasons. On the
one hand addition of HCl will favour the formation of hypochlorous
acid, which has a higher standard reduction potential (Table 5).
In addition a more acidic medium will increase the reduction
potential both of hypochlorous acid and hypochlorite ions
according to the Nernst equation for the corresponding half
reaction. On the other hand, the higher concentration of chloride
ions will favour the formation of the HgCl4 2− complex, which is
highly soluble and has a large formation constant (log Kf = 6.74).
Because of this, the dissolution of elemental mercury by oxidation
to Hg(II) will be favoured by the decrease of the reduction potential
for the corresponding half reaction. Thus the reaction: Hg +
NaOCl + 3HCl → HgCl4 2− + H2 O + H+ + Na+ , will become
thermodynamically favourable over a wide range of pH values and
solution potentials.8 In addition, the acidic medium also avoids the
formation of mercury hydroxides and oxides, which are scarcely
soluble in a basic medium.
It must be pointed out that the higher Hg removal reached in
these leaching experiments (2116 mg kg−1 phosphor) was lower
than those reported in Table 1 (4700 mg kg−1 phosphor). This is
ascribed to losses of Hg vapour during the previous processing of
the lamps (crushing and extraction under negative pressure) and
subsequent storage. According to the literature the release of Hg
vapour to the atmosphere appears to be a function of a number
of factors, especially time and temperature.17
A second series of leaching tests shows the influence of contact
time and temperature on the Hg removed with the different
leaching solutions (Fig. 1). Very little increase in Hg concentration
was observed with the HCl + HNO3 and the NaOCl-pH 5.5 solutions
25
20
15
10
5
0
0 50 100 150 200 250
Time (min)
Figure 1. Hg removal by leaching at different contact times and temper-
atures.
HCl-HNO3 ;  NaOCl-pH 5.5;  NaOCl. Solution volume = 0.25 L;
weight of lamp residues = 0.25 kg.
Hg can still be removed after temperature was increased to 80 ◦ C.
The same behaviour was observed for the NaOCl solution at 20 ◦ C,
although higher amounts of Hg were removed at 80 ◦ C.
Photocatalytic experiments
These were performed with solutions from the HCl + HNO3 and
the NaOCl-pH 5.5 treatment. Several differences can be observed
between the behaviour of these solutions (Fig. 2). On one hand the
presence of a yellowish gelatinous precipitate was observed for
the acid solution after the addition of NaOH for pH adjustment. This
was ascribed to the formation of hydroxy compounds of aluminium
and iron, which are present in the lamp residues and were dissolved
during acid leaching.18 The amount of Hg(II) in the gel was found to
be no more than 2% of the amount in the filtered solution. Accord-
ing to the literature, adsorption of Hg(II) on hydrous oxide gels is
considerably reduced by formation of HgCl4 2− complexes, which is
favoured by a high Cl− /Hg(II) ratio in solution.19 Contrarily, no pre-
481

after a contact time of 1 h at 20 ◦ C, although small amounts of cipitates were formed after pH adjustment of the solution from the

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 www.soci.org J Bussi et al.

1.2
(a)
1

0.8
[Hg] mg.L-1

0.6

0.4

0.2

0
0 10 20 30 40 50 60
Time (min)

Figure 2. Photocatalytic reduction of mercury in leaching solutions.

HCl-HNO3 without filtration, [Hg]o = 7.2 mg L−1 (dilution factor = 0.28);
 HCl-HNO3 with further filtration, [Hg]o = 3.5 mg L−1 (dilution factor
= 0.28);  NaOCl-pH 5.5, [Hg]o = 24.1 mg L−1 (dilution factor = 0.80).
Solution volume = 0.5 L, [TiO2 Degussa P-25] = 1 g L−1 ; [citric acid] =
(b)
10 g L−1 .

NaOCl-pH 5.5 leaching. The much lower acidity of this solution does
not allow significant dissolution of metals such as aluminium and
iron. On the other hand, differences were also observed between
the two leaching solutions during the photocatalytic experiments.
No significant removal of the dissolved Hg took place in the acid
leaching solutions separated by gravity from the gel. The presence
of this residual gelatinous precipitate could be the cause of the inef-
fectiveness of the photocatalytic treatment during the 1 h run. Con-
trarily, the removal of dissolved Hg was observed in the solution
that had previously been separated from the gel by filtration. Tak-
ing into account that the initial and the final Hg(II) concentrations
were 3.58 and 0.019 mg L−1 , respectively, the total Hg removal
from the solution was 99.4%. The photocatalytic treatment was
also effective for the removal of Hg from the NaOCl-pH 5.5 leaching
solution. More than 99.9% of the initial Hg(II) ions (24.1 mg L−1 ) Figure 3. X-ray diffraction pattern of a Degussa P-25 TiO2 sample (a) before
and (b) after the photocatalytic process has been carried out. () diffraction
was removed and the final Hg(II) concentration was less than
peaks corresponding to the Hg2 Cl2 phase (tetragonal phase, calomel)
4 ppb, which is in the order of the mercury concentration imposed (JCPDS #04-0581), other diffraction peaks TiO2 anatase phase.
by current environmental regulations. Another aspect to be noted
is concerned with the rate of the photocatalytic reactions. On the
one hand, a first-order kinetic expression fits well with the concen- and confirms that mercury reduction takes place by a successive
tration vs time results for both leaching solutions (Fig. 2), in agree- two thermodynamically allowed one-electron transfer steps.13
ment with that reported by De la Fournière et al. for Hg(II) concen- Reuse of the photocatalyst was tested with solutions from a
trations lower than 100 mg L−1 (0.5 mmol L−1 ).13 Nevertheless, the NaOCl-pH 5.5 leaching extraction. For this, four photocatalytic
first order kinetic constant for the NaOCl-pH 5.5 solution was higher runs were performed using the TiO2 photocatalyst for the first one
than that for the acid solution (0.194 min−1 and 0.0916 min−1 , re- and the residues containing both TiO2 and accumulated solid mer-
spectively). Differences in the reaction rate can be related with cury compounds for the following three runs. As shown in Fig. 4,
competitive adsorption of other metal compounds on the photo- very different behaviour was observed between these tests during
catalyst sites. Indeed, in previous studies an increase in the con- the initial 15 min in the dark. For the first one the Hg concentration
centration of calcium salts led to a significant decrease of the pho- in solution remained almost constant, which indicates a very low
tocatalytic Hg removal rate.15 In this case, the higher reaction rate capacity of the photocatalyst to adsorb Hg(II) ions from solution.
observed for NaOCl-pH 5.5 solution can be ascribed to the lower Contrarily, the Hg concentration was significantly reduced with the
concentration of calcium and magnesium ions (0.90 g L−1 ) com- reused photocatalyst (from 35.8 to 11.6 mg L−1 , 35.6 to 3.0 mg L−1
pared with that of the hydrochloric/nitric acid mixture (3.49 g L−1 ). and 35.5 to 3.6 mg L−1 for tests 2, 3 and 4, respectively). This is
X-ray diffraction analysis of the solid residue obtained by de- ascribed to the adsorption of Hg(II) ions on the Hg2 Cl2 precip-
cantation after the photocatalytic treatment and further drying at itate, which was formed in the preceding tests. Concerning the
110 ◦ C revealed the presence of Hg2Cl2 (Fig. 3). The presence of Hg◦ behaviour during the illumination period, a final Hg(II) concentra-
could not be confirmed probably due to volatilization during heat- tion lower than 0.004 mg.L−1 was observed in all four reuse tests
ing and/or difficulty of its detection by this technique. In spite of after 1 h. Although no significant loss of catalytic activity could be
this, the greyish colour of the solid suggests that metallic Hg could observed for the reused TiO2 , deactivation is expected to occur
also be present at least in minor amounts together with Hg2 Cl2 . This after some time as a consequence of blockage of active sites on
482

result is in agreement with that reported by De la Fournière et al. the TiO2 surface and to diminution of light transmittance through

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Recovery and recycling of mercury from fluorescent lamps www.soci.org

40
Table 6. Recovery of Hg◦ by cementation with iron, initial Hg(II)
35 concentration: 0.15 mol L−1 ; initial pH: 5.5
30 Initial Hg amount (g) Hg◦ recovered (g) Hg recovered (%)
[Hg] mg.L-1

25
1.0964 0.9222 84
20 0.8696 0.6610 76
15 1.0990 0.8078 74
1.1017 1.0078 92
10
0.7390∗ 0.5787 78
5
∗ Starting from metallic mercury dissolved with NaOCl solution at initial
0 pH 5.5.
-20 0 20 40 60 Temperature: 20 ◦ C; contact time: 18 h.
Time (min)

Figure 4. Photocatalytic reduction of mercury in the NaOCl-pH 5.5 leaching

solution. Reuse tests of the TiO2 Degussa P-25.
first;  second:  third;
cementation by Anacleto and Carvalho.20 Further adjustments
fourth test. Solution volume = 0.5 L [TiO2 Degussa P-25] = 1 g L−1 ; [citric
acid] = 10 g L−1 . of the technique could allow mercury yields close to 100% to
be obtained while the residual solution could be discarded or
recycled in the same process.
40

35
CONCLUSIONS
30
Mercury from fluorescent lamps could be recovered by using
[Hg] mg.L-1

25 a combined process involving extraction with an oxidant and

20
15
10
5 suitable amount of citric acid makes the formation of the different
0
-20 0 20 40 60 80 100
Time (min)
Figure 5. Hg(II) ions adsorption on TiO2 +Hg2 Cl2 residues after a typical
photocatalytic experiment with a NaOCl-pH 5.5 solution. Solution volume
= 0.5 L.
TiO2 +UV-light;  TiO2 +Hg2 Cl2 residues.
the suspension from the increasing amount of solid mercury com-
pounds present as very fine particles. Another test was carried
out to check the effectiveness of Hg removal by adsorption onto
Hg2 Cl2 precipitates. As shown in Fig. 5, TiO2 + Hg2 Cl2 residues
from a typical photocatalytic experiment did not display the same
efficiency to remove Hg(II) ions when no UV-light was used.
Concerning the separation of Hg2 Cl2 precipitates from the TiO2 ,
the addition of a small volume of NaOCl solution at pH 5–5.5 was
sufficient to dissolve mercury compounds by oxidation to Hg(II)
thus permitting easy regeneration of the photocatalyst together
with a small volume of a concentrated Hg(II) aqueous solution.
Cementation experiments
A series of cementation experiments with concentrated Hg(II)
solutions showed that significant amounts of metallic mercury can
be recovered (Table 6). After nearly 3 h, mercury droplets were
observed and were easily separated from the reactant system
at the end of the test (18 h) in spite of significant amounts of
Fe(III) precipitates (hydroxides). According to the literature, the
formation of Fe(III) precipitates can be minimized by avoiding
an excess of hypochlorite in solution.8 In this way during the
cementation process Fe(II) is the main oxidation product. The
highest yield (92%) was obtained when the initial pH was adjusted
further treatment of the aqueous solution by heterogeneous
photocatalysis. NaOCl at pH 5.5 was the most effective leaching
reagent leading to complete dissolution of mercury and further
selective precipitation during the photocatalytic treatment. A
mercury-citrate complexes possible thus avoiding interferences
120 of a high amount of calcium and other metal ions. In this
way, more than 99.9% of mercury could be recovered as solid
compounds, which were easily redissolved in a small volume of an
aqueous NaOCl solution. Metallic mercury could then be obtained
from the concentrated Hg(II) solution by cementation with
metallic iron as reducing agent. Further studies are proceeding to
optimize experimental conditions leading to the highest amount
of recovered metallic mercury as well as the minimum amount of
residual Hg in the aqueous effluents.
ACKNOWLEDGEMENTS
The authors wish to acknowledge the financial support of
Programa de Desarrollo para las Ciencias Básicas (PEDECIBA) and
Comisión Sectorial de Investigación Cientı́fica (CSIC), Universidad
de la República (UdelaR).
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