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Bash Kova 2009
Bash Kova 2009
Bash Kova 2009
The effects of urea modication and heat treatment on the process of NO2
removal by wood-based activated carbon
Svetlana Bashkova, Teresa J. Bandosz
Department of Chemistry, The City College of New York, 160 Convent Avenue, New York, NY 10031, USA
a r t i c l e
i n f o
a b s t r a c t
Article history:
Received 17 November 2008
Accepted 26 January 2009
Available online 29 January 2009
Keywords:
Urea
Activated carbon
Nitrogen
Heat treatment
NO2 adsorption
NO
The removal of NO2 on urea-modied and heat-treated wood-based activated carbons was studied. From
the obtained results it was found that these modications, especially when done at 950 C, have a positive
effect on NO2 adsorption and on the retention of NO (the product of NO2 reduction by carbon). The
presence of moisture in the system enhances the removal of NO2 but negatively affects the retention
of NO. It is possible that the formation of active centers on the carbon surface and some increase in
the volume of supermicropores during the high temperature treatment play a signicant role in these
removal processes. The surface of the carbons was analyzed in terms of the pK a distributions. The
qualitative and quantitative analyses of the NO2 adsorption products were carried out by means of FTIR
and TA techniques, respectively. The main products found on the carbon surface were the NO3 and NO2
species.
2009 Elsevier Inc. All rights reserved.
1. Introduction
The two most prevalent oxides of nitrogen are nitrogen dioxide (NO2 ) and nitric oxide (NO). Nitrogen oxide emissions contribute to the formation of smog, acid rain, and particulate matter
through chemical reactions in the atmosphere [1]. Although NO is
a main component released into the atmosphere from the combustion of fossil fuels, it is easily converted to the more harmful
NO2 . The latter one could also form when the heat from res
and explosives combines nitrogen and oxygen from air. Thus, military personnel could easily be exposed to high concentrations of
NO2 in battleeld situations. Civilians could also be exposed as a
result of terrorist bombings or if trapped in a re. Long-term exposure to NO2 causes adverse health effects. Government industrial
health regulations limit workplace exposures to 5 parts per million
(ppm).
Therefore, the removal of NOx is extremely important and has
been a subject of interest of many research groups [215]. Although, a selective catalytic reduction (SCR) process has been
widely applied in the denitrication of ue gases [10,11], it has
disadvantages, which include high reaction temperature and unreacted reductants such as ammonia and hydrocarbons. As an effective alternative to SCR, activated carbons have been used. Recently,
Grzybek et al. [12] showed that modication of active carbon with
N-precursors such as gaseous ammonia (at high temperature) and
aqueous solution of urea (followed by curing in air or nitrogen at
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S. Bashkova, T.J. Bandosz / Journal of Colloid and Interface Science 333 (2009) 97103
2. Experimental
2.1. Materials
A wood-based activated carbon BAX-1500 (MeadWestvaco Corporation) was used in this study. The initial sample was designated
B. The carbon was modied to introduce nitrogen into its structure. A 5 g sample was impregnated with urea by stirring it with a
saturated aqueous solution of urea (30 ml) for 5 h. Then it was
heated in nitrogen by raising its temperature (at 10 C/min) to
450 C and 950 C and holding it at these temperatures for 1 h.
The treated carbon samples were washed with water to remove
urea decomposition products and dried. The nitrogen-modied carbons were designated BU450 and BU950. Heat treatment (at
10 C/min) to 950 C was also applied to the initial BAX-1500 carbon and the product was designated B950.
2.2. Methods
2.2.1. Evaluation of NO2 sorption capacity
Evaluation of NO2 sorption capacity was conducted in a laboratory-scale, xed-bed reactor system. Carbon samples (12 mm
particle size) were loaded into the glass column, 370 mm long
by 9 mm diameter, such that the volume of the carbon bed was
about 2 cm3 (measured in a graduated cylinder). A dry air (DA)
or moist air (70%) (MA) with 0.1% of NO2 was passed through
the column of adsorbent. Downward gas and air ow rates were
controlled by ow meters (Cole Palmer). The breakthrough of NO2
and the concentration of NO were monitored using multiple gas
monitor with electrochemical sensors (RAE Systems, MultiRAE Plus
PGM-50/5P). The tests were conducted until the concentrations of
NO2 and NO reached the electrochemical sensors upper limit values of 20 ppm and 200 ppm, respectively. The experiments were
conducted at room temperature and atmospheric pressure with a
total gas ow rate of 0.45 L/min.
2.2.2. Surface area and pore size distribution measurements
The nitrogen adsorption isotherms on the carbon samples
were determined at 196 C using an ASAP 2010 instrument (Micromeritics). The samples were outgassed at 120 C to a constant
vacuum (104 Torr) immediately prior to the isotherm measurements. The specic surface area (S BET ) was calculated from the
isotherm data using the Brunauer, Emmet and Teller (BET) model
[18]. Total pore volume (V tot ), micropore volume (V mic ), mesopore
volume (V mes ), and volume of pores less than 1 nm (V <1 nm ) were
calculated using the density functional theory approach (DFT) [19].
2.2.3. Characterization of carbon surface chemistry
The surface chemical properties were evaluated using potentiometric titration procedure [20]. Automatic titrator (Metrohm,
DMS Titrino 716) was rst set to collect the equilibrium pH of
the sample. Carbon sample (0.1 g) was placed in a thermostatted (at 298 K) container, containing 50 ml of 0.01 M solution of
sodium nitrate, and equilibrated overnight. The equilibrated carbon
suspension was then acidied (pH 3.19) with hydrochloric acid
(0.01 N). The suspension was titrated with a standardized NaOH
(0.1 M) until its pH reached about 10. During the titration the suspension was continuously stirred and purged with nitrogen gas.
The surface chemistry was assessed assuming that the population of surface sites is described by continuous pK a distribution,
f (pK a ). The experimental data was transformed into a protonbinding isotherm, Q , representing the total amount of deprotonated sites.
Q (pH) =
(1)
S. Bashkova, T.J. Bandosz / Journal of Colloid and Interface Science 333 (2009) 97103
99
Fig. 1. The outlet concentrations as a function of time for B, B950, BU450, and BU950 of: (A) NO2 in dry air, (B) NO in dry air, (C) NO2 in moist air and (D) NO in moist air.
(2)
(3)
(4)
(5)
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S. Bashkova, T.J. Bandosz / Journal of Colloid and Interface Science 333 (2009) 97103
Table 1
NO2 breakthrough capacities and surface pH values for the carbon samples.
Sample
pHin a /pHE b
BDA
B950DA
BMA
B950MA
BU450DA
BU450MA
BU950DA
BU950MA
6.0/2.4
7.2/2.3
6.0/1.9
7.2/1.6
7.0/2.2
7.0/1.9
7.0/1.9
7.0/1.8
35
23
71
93
45
135
66
140
a
b
Table 2
Surface area, pore volumes, and mean pore width of activated carbons examined.
Sample
S BET
(m2 /g)
V tot
(cm3 /g)
V mic
(cm3 /g)
V mes
(cm3 /g)
V <1 nm
(cm3 /g)
V mic / V tot
B
BDA
BMA
2116
1593
1385
1.23
0.87
0.74
0.50
0.44
0.39
0.73
0.43
0.35
0.12
0.15
0.15
0.41
0.51
0.53
B950
B950DA
B950MA
1591
1528
1364
0.84
0.81
0.73
0.42
0.40
0.38
0.42
0.41
0.35
0.19
0.18
0.19
0.50
0.49
0.52
BU450
BU450DA
BU450MA
1835
1653
1389
1.04
0.93
0.77
0.46
0.41
0.39
0.58
0.52
0.38
0.13
0.13
0.15
0.44
0.44
0.51
BU950
BU950DA
BU950MA
1533
1477
1402
0.81
0.80
0.75
0.40
0.39
0.40
0.41
0.41
0.35
0.19
0.19
0.19
0.49
0.49
0.53
marized in Table 1. It is apparent from these data that NO2 breakthrough capacities of the carbons in a dry air were smaller than
the corresponding NO2 capacities in a moist air, with the highest
capacity found for BU950. The pH values of the carbons after the
adsorption of NO2 were between 1.6 and 2.4 with the lower values
received in a moist air. These low pH values are likely the result
of oxidation of the carbon surface by HNO3 and the formation of
acidic nitrogen oxides.
The structural parameters of activated carbons in terms of the
surface area, pore volume distribution and relative microporosity
(V mic / V tot ) are presented in Table 2. From these data, it is seen
that the surface area, total pore volume, and micropore volume of
the carbons decreased after the heat treatment and urea modication. Nevertheless, some increase in the volume of supermicropores (V <1 nm ) [24] was noticed for the high temperature treated
carbons. A decrease in the porosity of B carbon upon the high temperature treatment is due to the fact that the initial B carbon was
prepared at a low temperature.
Putting aside a role of nitrogen and a possible contribution of a
mineral matter (the ash content of BAX is about 3%), two carbons
were chosen for comparison, B and B950. Analyzing the performance of these carbons for the adsorption of NO2 in a dry air,
no signicant changes were noticed. In fact, some decrease in the
capacity of NO2 upon the heat treatment was found. On the contrary, the retention of NO signicantly increased. Such an increase
in the retention of NO upon the heat treatment could mostly be
related to the removal of oxygen functional groups and the formation of active sites on the carbon surface [5,25]. However, some
contribution from the supermicropores, which were found to increase the adsorption of NO on the activated carbons and activated
carbon bers [23], is also possible. When moisture is present in
the system, the active sites are likely to be covered by water [5]
and/or oxidized by the products of NO2 adsorption, and therefore,
no longer be involved in the adsorption of NO. On the other hand,
S. Bashkova, T.J. Bandosz / Journal of Colloid and Interface Science 333 (2009) 97103
Fig. 2. The pK a distributions of B, BU450, BU950, and B950 carbons before and after the adsorption of NO2 from dry and moist air.
Fig. 3. The FTIR spectra of B, BU450, B950 and BU950 carbons before and after the adsorption of NO2 from dry and moist air.
101
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S. Bashkova, T.J. Bandosz / Journal of Colloid and Interface Science 333 (2009) 97103
Table 3
The amount of NO2 adsorbed from breakthrough tests and the weight loss of activated carbons after the adsorption of NO2 from a thermal analysis.
Sample
%NO2
breakthrough
%Weight loss
(30200 C) TA
BDA
B950DA
BU450DA
BU950DA
BMA
B950MA
BU450MA
BU950MA
3.5
2.3
4.5
6.6
7.1
9.3
13.5
14.0
3 .8
3 .4
5 .0
13.0
45.2
40.2
41.0
45.0
Fig. 4. The DTG curves in N2 of B, BU450, BU950, and B950 carbons before and after
the adsorption of NO2 from dry and moist air.
S. Bashkova, T.J. Bandosz / Journal of Colloid and Interface Science 333 (2009) 97103
oxidation of carbon surface is clearly observed from the pK a distributions. As a result of the oxidation, the carbon/nitrogen active
centers are no longer available for the adsorption of NO, which results in its early release from the carbon surface.
The variety of products was found on the surface of carbons
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