Professional Documents
Culture Documents
Abstract
Voltammetric investigations into the process of anodic decomposition of urea using Ti/Pt, Ti/(Pt–Ir)70:30 , Ti/RuO2 , Ti/(RuO2 –TiO2 )40:60 ,
Ti/(RuO2 –TiO2 –IrO2 )20:60:20 , Ti/(Ta2 O5 –IrO2 )70:30 electrodes have been carried out. Two anodes namely (Ti/(Pt–Ir)70:30 and Ti/(Ta2 O5 –IrO2 )70:30 )
were found to be stable enough and indicated the required activity to produce non-toxic N2 and CO2 in place of nitrites and nitrates, the commonly
reported electrochemical urea oxidation products. The kinetics of the process in question using the above two electrodes was further examined in a
periodic electrolyzer. The effect of the anodic current density (j = 2–10 A/dm2 ), initial urea concentration (c0M = 1–10 g/dm3 ) and the concentration
of sodium chloride (cNaCl = 1–10 g/dm3 ) on basic process indices (average rate of urea decomposition, a; current efficiency, Wp , and unit DC power
consumption, Zj ) was discussed.
© 2006 Elsevier Ltd. All rights reserved.
1. Introduction urea oxidation as well as the possibility for applying the urea
electrochemical decomposition process for the regeneration of
The industrial synthesis of urea involves the reac- dialyzate in artificial kidney design. They were carried out using
tion of ammonia and carbon dioxide under high pressure potentiostatic techniques and were limited only to platinum elec-
(p = 10–25 MPa) and temperature (T = 420–480 K). The process trodes of small surface area. It has been there found that anodic
can be divided into the following steps: synthesis, decomposi- oxidation of urea depends on anode potential, kind and com-
tion of byproducts, concentration of urea solution, crystallization position of the basic electrolyte, urea concentration, pH and
and granulation. The above process results in large quantities temperature of the solution. Different conditions of the treatment
of wastewaters of varying urea concentration, usually purified result in different products of urea decomposition (CO2 , N2 , H2 ,
by hydrolysis [1,2], however, other methods for urea removal CNO− , NO3 − , NO2 − , [N2 O2 ]− , N2 O, NO2 , NH2 CONH2 •+ ).
from aqueous solutions are also described [3–7]. The latter are At high potentials (over 1.7 V versus SCE) in the acidic envi-
considered to be either costly, because of the requirement of ronment, urea is decomposed by a direct oxidation at electrode
sophisticated apparatus, and thus are not suitable for the indus- surface primarily to CO2 and N2 [8,9], while at lower poten-
trial scale or are still being tested. tials (below 1.6 V versus SCE), urea reacts with an OH• radical
Anodic oxidation is an alternative method for treating the and the decomposition products remain in the solution [10]. In a
wastewater produced during urea manufacture and may results phosphate buffer solution, the limiting factor at high potentials is
in not-toxic products (CO2 , N2 , H2 ). Most of the investigations the urea decomposition to CO2 and N2 , and the process rate does
into the anodic decomposition of urea described in the litera- not depend on pH of the solution [11]. The authors of paper [12]
ture were aimed at determining the mechanism and products of have found that urea decomposition to nitrate(III) and (V) ions is
the predominant process at high potentials in neutral solutions.
The lowest potentials result in a radical cation—NH2 CONH2 •+ ,
∗ Corresponding author. Tel.: +48 32 237 26 05; fax: +48 32 237 22 77. which may polymerize [15]. An increase in temperature as well
E-mail address: wojciech.simka@polsl.pl (W. Simka). as the increase in acidity increase the rate and efficiency of urea
0013-4686/$ – see front matter © 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2006.12.017
W. Simka et al. / Electrochimica Acta 52 (2007) 5696–5703 5697
2. Methods
2.2. Investigations into kinetics of anodic decomposition of
urea
2.1. Voltammetric examination of anodic decomposition of
urea
The electrolysis was carried out in a 1.5-dm3 electrolyzer
made of polymethyl methacrylate (Fig. 1). Two cathodes made
The voltammetric cell consisted of two compartments with
of a platinum coated titanium grid were placed inside and sep-
the tested electrode (titanium modified with active coatings),
arated with an anode. The gap between the anode and cathodes
auxiliary platinum electrode and Haber–Lugin capillary with
was 6 mm thick. The anode materials used were: Ti/(Pt–Ir)70:30 ,
a saturated calomel electrode (SCE) reference electrode placed
with surface area of s = 1.87 dm2 and Ti/(Ta2 O5 –IrO2 )70:30 (of
inside. The cell was powered through a potentiostat (AUTOLAB
s = 1.61 dm2 ).
PGSTAT 30), operated by General Purpose Electrochemical
The electrochemical decomposition of urea was conducted
System (GPES) software.
at a constant current intensity for 3 h. During the measurements,
The voltammetric examination of the following anode mate-
samples of the liquid phase were collected from the electrolyzer
rials was conducted:
at fixed intervals to determine pH, urea concentration and
hypochlorite. Urea was analysed spectrophotometrically [28]
- titanium coated with platinum, Ti/Pt;
while hypochlorite iodometrically [29]. Constant measurements
- titanium coated with Pt–Ir at a molar ration of 70:30,
of the voltage drop, current intensity and temperature of elec-
Ti/(Pt–Ir)70:30 ;
trolyte with accuracy of ± 0.1 V, ± 0.1 A, ± 0.1 ◦ C, respectively,
- titanium coated with ruthenium oxide, Ti/RuO2 ;
were carried out.
- titanium coated with RuO2 –TiO2 at a molar ratio of 40:60,
The results of the above measurements were used to calculate
Ti/(RuO2 –TiO2 )40:60 ;
the following process indices for electrochemical decomposition
- titanium coated with RuO2 –TiO2 –IrO2 at a molar ratio of
of urea:
20:60:20,Ti/(RuO2 –TiO2 –IrO2 )20:60:20 ;
- titanium coated with Ta2 O5 –IrO2 at a molar ratio of
70:30,Ti/(Ta2 O5 –IrO2 )70:30 . – average rate of urea decomposition:
Ti/Pt electrode was made by Pt electrodeposition [21–24]. mri
a [g/(h dm2 )] = (1)
The others were prepared by thermal decomposition of τs
5698 W. Simka et al. / Electrochimica Acta 52 (2007) 5696–5703
Table 1
The influence of urea content on electric current density at 2.0 V
Electrode material j [A/cm2 ]
where mri is the weight of urea decomposed in time τ (g); 3. Results and discussion
mri the weight of urea decomposed in time τ (g)
3.1. Voltammetric investigations into anodic decomposition
mri (g) = Vr (CUi−1 − CUi ) (2) of urea
τ is the electrolysis time in h; s the electrode surface area in 3.1.1. Ti/Pt electrode
dm2 ; (cUi−1 − cUi ) the change in urea concentration over time At a constant concentration of sodium chloride, an increase
τ in g/dm3 ; Vr is the current volume of urea solution. in urea concentration caused a considerable decrease in current
The average urea decomposition rate was defined as the density (Table 1), the largest one being found for urea concentra-
decrease in urea mass during unit time per unit electrode sur- tion of 10 g/dm3 . This is suspected to be the result of adsorption
face area. The average rate defined in the above manner is of urea on the electrode surface and its resulting blockage of
formally based on the system mass balance and for adiabatic electrode active sides for chloride oxidation [30]. However, an
electrolyzer, no correction for temperature was required. addition of urea does not affect the potential at which sodium
chloride decomposition takes part (approximately 1.1 V versus
– current efficiency related to the total urea decomposition reac- SCE).
tion:
3.1.2. Ti/(Pt–Ir)70:30 electrode
NH2 CONH2 + H2 O → N2 + 3H2 + CO2 (3) Similarily to Ti/Pt electrode, an increase in urea concentra-
tion at constant NaCl content caused the Ti/(Pt–Ir)70:30 electrode
Σmri active sides blockage which leads to the decrease in chlorine
Wp = × 100% (4)
mt release and consequent decrease in current density (Table 1).
This is consistent with the data presented in [30].
M
mt (g) = mh Iτ = Iτ (5)
nF 3.1.3. Ti/RuO2 electrode
As for the previous electrodes, in the case of Ti/RuO2 the urea
where mt the theoretical weight of decomposed urea in g; mh supplement in the range of 0.1–10.0 g/dm3 caused the blockage
the electrochemical equivalent in g/Ah; M the molar mass of the electrode active sites and resulted in a decrease in cur-
of urea (M = 60.06 g/mol); I the current intensity in A; n the rent density and chlorine release (Fig. 2, Table 1). The peak of
number of electrons exchanged during reaction (3), n = 6; F adsorbed chlorine reduction observed during the decomposition
is the Faraday constant (Ah/mol);
– unit DC power consumption:
Ez × 100
Zj [kWh/kg] = (6)
Wp mh
Table 2
Process indices for anodic decomposition of urea, c0U = 10 g/dm3 , cNaCl = 5 g/dm3 , τ = 180 min using the examined electrodes
j [A/dm2 ] Ti/(Pt-Ir)70:30 Ti/(Ta2 O5 –IrO2 )70:30
of pure NaCl at a potential close to 1.0 V disappears at urea applied to for sodium hypochlorite obtaining from dilute NaCl
concentrations higher than 0.1 g/dm3 . solutions. Another material without the above shortcoming is a
titanium electrode coated with tantalum and iridium oxides, the
3.1.4. Ti/(RuO2 –TiO2 )40:60 electrode that oxidizes urea directly.
For RuO2 –TiO2 mixture layered Ti electrode the supplement When considering the above, and the available literature, the
of urea at constant sodium chloride concentration caused an following electrodes were selected for further kinetic investiga-
increase in current density which indicates a direct urea oxida- tions: Ti/(Pt–Ir)70:30 , Ti/(Ta2 O5 –IrO2 )70:30 .
tion on the electrode surface (Table 1). However, the destructive
action of urea on electric current density was noted since the 3.2. Investigations into kinetics of anodic decomposition of
increase in urea content caused the decrease in electric current. urea
3.1.5. Ti/(RuO2 –TiO2 –IrO2 )20:60:20 3.2.1. The influence of anodic current density on the urea
An increase in urea concentration from 0.1 to 10.0 g/dm3 decomposition rate
caused a decrease in current density (Table 2). Again, this was The rate of anodic decomposition of urea was found to depen-
found to be the results of the adsorption of urea on the electrode dent strongly on current density (Fig. 3) when Ti/(Pt–Ir)70:30
surface. electrode is applied. An increase in density from 2 to 10 A/dm2
caused an increase in the average rate of urea decomposition
3.1.6. Ti/(Ta2 O5 –IrO2 )70:30 electrode from 0.94 to 2.04 g/h dm2 and unit power consumption from 8.2
An increase in urea concentration from 0.1 to 1.0 g/dm3 to 35.4 kWh/kg (Table 2). At the same time current efficiency
caused an increase in current density (Table 2). At higher urea decreased more than two times. At current density of 2 A/dm2 ,
content, of 10.0 g/dm3 , current density exhibits a decreasing ten- NO2 − and NO3 − ions were found, which indicates an excessive
dency, yet it is still higher than the current density observed for oxidation of urea and prevents its industrial application since
the decomposition of the base electrolyte (NaCl). This indicates these ions are serious and toxic contaminants of water. The
a direct oxidation of urea on the electrode surface. electric current efficiency at 2 A/dm2 current density exceeded
In the presence of sodium chloride, urea becomes directly 100%, when Eq. (3) was applied for Wp determination, since
decomposed on Ti/(RuO2 –TiO2 )40:60 and Ti/(Ta2 O5 –IrO2 )70:30 the number electrons exchanged to oxidize urea to nitrogen
electrodes. The rate of electrochemical decomposition of urea is much smaller than the value for nitrite or nitrate obtaining
increases with increasing anode potential. For other electrode (see Table 2). In this case urea may be oxidized by eventually
materials, in the presence of NaCl, the adsorption of urea on formed hydroxyl radicals and nitrites or nitrates may be
the electrode was observed, causing the blockage of its surface produced.
and decrease in current density. The results for Ti/Pt elec- The process is accompanied by a drastic increase in temper-
trode are consistent with the results given in paper [30] which ature of the solution—from 20 to approximately 90 ◦ C, being
shows that urea adsorbs on the surface of platinum and hinders approximately constant after 20 min. At the end of the process,
the adsorption of chloride ions. On the other hand, the results when urea concentration reached the lowest values, the con-
obtained for Ti/(RuO2 –TiO2 )40:60 electrode are consistent with
the results from paper [18–20] which reveal that urea is decom-
posed directly on the anode to non-toxic products (N2 , CO2 ,
H2 ).
Since the rate of electrochemical decomposition of urea
increases with increasing electrode potential, the process of
anodic decomposition should be conducted at the highest anodic
potential possible. This excludes the electrodes whose coating
contains RuO2 since it is oxidized to volatile RuO4 when its
potential exceed 1.45–1.50 V versus SHE that result the elec-
Fig. 3. Kinetic curves of anodic decomposition of urea at varying electric
trode deactivation. No such limitation is observed for highly current densities for Ti/(Pt–Ir)70:30 electrode; c0U = 10 g/dm3 , cNaCl = 5 g/dm3 ,
corrosion resistant Ti/(Pt–Ir)70:30 electrode, which is commonly τ = 180 min.
5700 W. Simka et al. / Electrochimica Acta 52 (2007) 5696–5703
Fig. 4. Kinetic curves of anodic decomposition of urea at varying electric current Fig. 6. Kinetic curves of anodic decomposition of urea at varying initial urea
densities for Ti/(Ta2 O5 -IrO2 )70:30 electrode; c0U = 10 g/dm3 , cNaCl = 5 g/dm3 , concentration for Ti/(Ta2 O5 –IrO2 )70:30 electrode; j = 8 A/dm2 , cNaCl = 5 g/dm3 ,
τ = 180 min. τ = 180 min.
Table 3
Process indices for anodic decomposition of urea, j = 8 A/dm2 , cNaCl = 5 g/dm3 , τ = 180 min. using the examined electrodes
c0U [g/dm3 ] Ti/(Pt–Ir)70:30 Ti/(Ta2 O5 –IrO2 )70:30
Table 4
Process indices for anodic decomposition of urea, c0U = 5 g/dm3 , j = 8 A/dm2 , τ = 180 min. using the examined electrodes
cNaCl [g/dm3 ] Ti/(Pt–Ir)70:30 Ti/(Ta2 O5 –IrO2 )70:30
a [g/h dm2 ] Wp [%] Zj [kWh/kg] a [g/h dm2 ] Wp [%] Zj [kWh/kg]
Table 5
The analysis of the reproducibillity of the examined process, c0U = 5 g/dm3 , cNaCl = 5 g/dm3 , j = 8 A/dm2 , τ = 180 min.
No measurement Ti/(Pt–Ir)70:30 Ti/(Ta2 O5 –IrO2 )70:30
determined for different initial concentrations of urea (Fig. 6). - Ti/(Pt–Ir)70:30 anode may be applied to the removal of urea
They also prove that the reaction of urea decomposition takes from aqueous solutions by electrochemical method on an
place directly at the anode. industrial scale;
- current density of 8 A/dm2 and sodium chloride concentration
3.2.4. The reproducibility of anodic urea decomposition of 5 g/dm3 are optimum process parameters.
The reproducibility of anodic urea decomposition utilizing
Ti/(Pt–Ir)70:30 i Ti/(Ta2 O5 –IrO2 )70:30 electrodes was examined. The investigations into the kinetics of anodic decomposi-
In order to attain that, the experiments were multiplied (Table 5) tion of urea in a periodic electrolyzer on Ti/(Ta2 O5 –IrO2 )70:30
[31]. The low values of variance (Sx̄2 ) and standard deviation (Sx ) electrode have yielded the following results:
indicate that the experiments are fully reproducible.
- urea reaction with chlorine adsorbed on the surface of the
4. Conclusions electrode predominated the anodic decomposition of urea;
- non-toxic N2 , CO2 , H2 , are major products of anodic decom-
The process of anodic decomposition of urea in the presence position of urea;
of chloride ions may be the result of direct electrode reaction, - Ti/(Ta2 O5 –IrO2 )70:30 anode may be applied to the removal of
reaction with hypochlorite produced during the process or a urea from aqueous solutions by electrochemical method;
reaction with chlorine adsorbed on the surface of the electrode. - current density of 8 A/dm2 and sodium chloride concentration
Usually, all these reactions occur simultaneously, however, often of 5 g/dm3 are optimum process parameters.
one of them being predominant depending on the conditions.
Although numerous investigations into anodic oxidation of urea The comparison of the basic indicators of anodic decom-
have been carried, its mechanism has not been explained fully position of urea for Ti/(Pt–Ir)70:30 and Ti/(Ta2 O5 –IrO2 )70:30
yet. Nor have the optimum process parameters for anodic decom- electrodes in the periodic electrolyzer at optimum process
position of urea to non-toxic and volatile products (N2 , CO2 , parameters has revealed that the former electrode is more favor-
H2 ), which might help develop a technology for removing urea able.
from aqueous solutions by the electrochemical oxidation. Due
to a lot of discrepancies in the literature, there was a need for Acknowledgement
a thorough examination of anodic decomposition of urea over
a wide range of parameters. Thus, voltammetric tests on anodic The research was financed by the state within the 2005–2006
decomposition of urea on different anode materials and exami- budget for research projects.
nation of the kinetics of the process on selected electrodes have
been carried out. References
The voltammetric tests have revealed the following findings:
[1] I. Kroschwitz, M. Howe-Grant, Kirk Othmer Encyclopedia of Chemical
- urea adsorbs on the surface of the following anode materials: Technology, fourth ed., Wiley, New York, 1995 (Supplement).
Ti/Pt, Ti/(Pt–Ir)70:30 , Ti/RuO2 , Ti/(RuO2 –TiO2 –IrO2 )20:60:20 [2] M.R. Rahimpour, Chem. Eng. Process. 43 (2004) 1299.
[3] S.K. Gupta, R. Sharma, Wet. Res. 30 (3) (1996) 593.
in the presence of sodium chloride (electrolyte aiding solution [4] R. Hüttl, K. Bohmhammel, G. Wolf, R. Oehmgen, Thermochim. Acta. 250
conductivity); (1995) 1.
- urea undergoes a direct electrode reaction on the following [5] W. Zaborska, M.J. Leszko, Pol. J. Chem. 68 (1994) 2733.
anode materials Ti/(RuO2 –TiO2 )40:60 , Ti/(Ta2 O5 –IrO2 )70:30 [6] A. Robak, J. Piotrowski, Chem. Inż. Ekol. 7 (1–2) (2000) 79.
[7] L.V. Konyk, P.N. Taran, Khim. Tekhn. Vody 11 (7) (1989) 604.
in the presence of sodium chloride (electrolyte aiding solution
[8] V.A. Gromyko, T.B. Tsygankova, V.B. Gaidadymov, Yu.B. Vasil’ev, V.S.
conductivity); Bagotskii, Elektrokhimiya 10 (1) (1974) 57.
- the following anode materials are suitable for anodic decom- [9] A.C.S. Bezerra, E.L. de Sá, F.C. Nart, J. Phys. Chem. B 101 (1997) 6443.
position of urea: Ti/(Pt–Ir)70:30 , Ti/(Ta2 O5 –IrO2 )70:30 . [10] V.A. Gromyko, T.B. Tsygankova, V.B. Gaidadymov, Yu.B. Vasil’ev, Elek-
trokhimiya 11 (4) (1975) 589.
[11] V.A. Gromyko, T.B. Tsygankova, V.B. Gaidadymov, Yu.B. Vasil’ev, Elek-
The investigations into the kinetics of anodic decomposition trokhimiya 11 (3) (1975) 491.
of urea in a periodic electrolyzer on Ti/(Pt–Ir)70:30 electrode [12] N.W. Osetrova, A.M. Skundin, Elektrokhimiya 30 (10) (1994) 1257.
have yielded the following results: [13] G.D. Levina, S.S. Surzhenko, G.M. Kolosova, M.M. Senyavin, Elek-
trokhimiya 11 (11) (1975) 1644.
[14] A.E. Bolzan, T. Iwasita, Electrochim. Acta 33 (1) (1988) 109.
- urea is oxidized to nitrate(III) and (V) ions at current density [15] N.W. Osetrova, A.M. Skundin, Elektrokhimiya 38 (3) (2002) 304.
lower than 4 A/dm2 which prevents from the application of [16] N.W. Osetrova, A.M. Skundin, Elektrokhimiya 38 (7) (2002) 886.
low current densities in anodic decomposition of urea; [17] M. Fels, Med. Biol. Eng. Comput. 16 (1978) 25.
- the reaction of urea and chlorine produced during the process [18] J.C. Wright, A.S. Michaels, A.J. Appleby, AIChE J. 32 (9) (1986) 1450.
[19] J. Piotrowski, W. Simka, A. Koszałka, Chem. Inż. Ekol. 10 (S1) (2003)
predominates the anodic decomposition of urea. It takes place
131.
in the entire volume of the solution; [20] J. Piotrowski, W. Simka, J. Schlesinger, Chem. Inż. Ekol. 10 (S2) (2003)
- non-toxic N2 , CO2 , H2 , are major products of anodic decom- 327.
position of urea; [21] G. Nawrat, W. Simka, Ł. Nieużyła, Chemik 58 (6) (2005) 373.
W. Simka et al. / Electrochimica Acta 52 (2007) 5696–5703 5703
[22] G. Nawrat, W. Simka, Ł. Nieużyła, L. Swadźba, Przem. Chem. 85 (8–9) [27] H.B. Beer, USA Patent No. 3,632,498 (1972).
(2006) 858. [28] G.W. Watt, J.D. Crisp, Anal. Chem. 3 (26) (1954) 452.
[23] J.F. Patzer, J. Mol. Catal. 70 (2) (1991) 217. [29] J. Minczewski, Z. Marczenko, Analytical Chemistry, vol. 2, PWN, Warsaw,
[24] J.F. Patzer, J. Mol. Catal. 70 (2) (1991) 231. 2001.
[25] F. Hine, M. Yasuda, T. Yoshida, J. Eletrochem. Soc. 124 (4) (1977) [30] V.A. Gromyko, T.B. Tsygankova, V.B. Gaidadymov, Yu.B. Vasil’ev, V.S.
500. Bagotskii, Elektrokhimiya 9 (11) (1973) 1685.
[26] H.B. Beer, British Patent No. 1,147,442 (1969). [31] M. Krzysztofiak, A. Luszniewicz, Statistics, PWE, Warsaw, 1979.