Revista ALEIQ

Revista de la Asociación Latinoamericana de Estudiantes

de Ingeniería Química y Ramas Afines

Volumen 1, Número 1

2010
 SOME CHANGES IN ADSORPTION PROPERTIES ON TREATED-COAL

Nicole D. Miranda, Fernando E. Vallejos-Burgos, Alejandro Karelović and Alfredo L. Gordon

Department of Chemical Engineering, University of Concepción, Concepción, Chile

Received April 30th, 2009

Abstract
The texture and surface of active carbon (AC) defines the adsorption properties used
in applications such as catalyst support, filters, reactant and others. The enhancement
in the preparation of carbon supports using acid treatment oxidation and partial
gasification with CO2 for different activation times was studied. Comparing solely
activated carbon with samples treated with nitric acid it was possible to confirm by
TPD that generation of carboxylic, lactone, phenol and quinone surface groups occur.
BET surface area decreased between 21 and 42 % after the oxidation process for all
samples due to functionalization. Wettability with water was also affected by the
addition of these hydrophilic groups and contact angle was found to decrease from
88.6 º to 14.8º with acid treatment on similar samples. Thus, intermolecular forces
(hydrogen bonds) appear to increase due to these hydrophilic groups that enhance
carboneous support adsorption and wettability properties.

Keywords: Coal; activated carbon; functional groups; oxidation treatment; surface

treatment.

1. INTRODUCTION reactions and controlling metal impregnation

Active carbon’s convenient porous structure has
shown advantages that have been widely used in
many fields such as pollution control, water
filtration, air purification, groundwater
remediation, pharmaceutical production, fuel
cells, selective hydrochlorination and as catalyst
support [13,17]. Its properties are constantly being
studied by multidisciplinary professionals,
including chemical engineers, in order to optimize
its uses.
Pure carbon presents a hydrophobic behavior
shown in its poor wettability [3,9]. This can be
overcomed by adding acidic carbon-oxygen
groups to its surface which make intermolecular
forces (Van der Waals and hydrogen bonds)
appear while increasing hydrophilic and polar
characteristic [3,4]. Thus, AC’s chemical
adsorption may be controlled by the presence of
these functional groups.
Specifically, in catalysis, increasing chemical
adsorption capacity of AC can have positive
effects in their use as supports (e.g.: using ion
exchange preparation, improving water media
[13]). Functionalization of AC surface through
acid treatment has proven to be a way of
manipulating adsorption properties [13]. For
example, oxidation procedures have shown
advantages in conversion of NO and N2O
decompositions using carbon-supported copper
catalyst and can be effective in lowering
environmental impact of these greenhouse gases
[17]. Also, adding functional groups to the surface
show improvements in adhesion between fibers
and matrix in composite materials, as well as
increasing metal dispersion on carbon surface
[13].
Using nitric acid on carbon sample, will oxidize
the surface by increasing the amount of acidic
surface groups [16]. CO2 desorbing complexes are
generated by the heating of the carbon when it
contains functional groups such as carboxyl
anhydrides, carboxylic acids, anhydride groups
[11] and lactone groups [17]. A product which
contain the latter groups is named acidic carbon
[2].
Previous studies demonstrated that, by applying
acid treatment (HCl) to active carbons, an increase

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 in surface area is observed [6]. On the other hand,
for xerogel carbon, nitric acid may increase SBET
values at high concentrations (0.10-0.30 mol/L,
473 K) up to 28%, but will not notoriously change
its textural properties at lower concentrations
(<0.10 mol/L) and oxidation temperatures (393 K)
[13].
The objectives of this work are to study (i) the
textural (e.g.: porosity) changes regarding CO2
activation time and (ii) chemical changes on the
surface of AC obtained by applying HNO3
treatment to coal from the southern part of Chile.
These effects have been previously studied for
other activated carbons [5,7,10] resulting in
property changes (BET surface area, ash content,
PZC, among others) [10,14].
2. EXPERIMENTAL
2.1 Chemicals and reagents
Coal was obtained from the Pecket mine in the
southern region of Chile near Punta Arenas city.
Hydrochloric acid (5 N), hydrofluoric acid (29 N)
and nitric acid (7.5 M) were purchased from
Merck KGaA.
2.2 Sample preparation
The coal was grounded, sieved to 53 and 180 µm.
For the demineralization, procedure described by
Vallejos (2006) [15] was followed.
To accomplish the pyrolysis, 10 g of the
demineralized coal were loaded in a ceramic
crucible and heated in N2 in a tubular furnace up
to desired temperature (1000 °C) with a heating
rate of 5 °C/min. The samples obtained were
labeled Dem-C-1000 (demineralized carbon
treated to 1000ºC) and were used for contact angle
measurements.
After, 3 g of Dem-C-1000 samples were activated
in a CO2 flow during 6, 12.5 and 24 hours (50%
burn off in 24 h), labeled 6h, 12h and 24 h,
respectively.
For acid oxidation, 1 g of each pyrolized and
activated sample was mixed during 3 hours at 90
°C with nitric acid. The samples were then
washed with double distilled water until no further
pH change, and dried overnight at 105 °C. These
were labeled followed by “-OX”.
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2.3 Characterization methods
To study the functional groups produced on the
carbon surface by the acid treatment temperature
programmed desorption (TPD) of two 50 mg
samples (24 h and 24 h-OX) were carried out in
plug flow reactor. Nitrogen (500 mL/min) was
flown through the reactor and heated from room
temperature to 900 °C at a rate of 15 °C/min. The
CO and CO2 produced were detected in a Horiba
VA-3000 infrared gas analyzer.
To determine the BET surface area, samples were
degassed overnight at 150 °C and 30 Pa.
Adsorption isotherm was obtained in a volumetric
absorber apparatus (Micromeritics Gemini) using
liquid nitrogen (-196 °C). Measurements ranged
from 0.010 to 0.99 atm.
Contact angle to determine wettability of samples
were measured using a KSV Sigma 300 model
tensiometer and KSV Instruments® software.
3. RESULTS AND DISCUSSION
3.1 Presence of functional groups on the AC
surface
Desorption of CO and CO2 during TPD assay is
based on the different bond strength of functional
groups to the carbon surface. Thus, this study
presents a qualitative analysis based on previous
research [8,14].
By analyzing CO and CO2 concentration
development during the TPD of 24 h and 24 h-OX
samples it is possible to identify (and after some
calculation, quantify) the functional groups added
to the surface.
As presented in Figure 1, two peaks appear in CO2
after acid treatment. The first, and most important
in this case, is detected at approximately 270 °C
revealing the presence of carboxylic acid while
the second (~430 °C) corresponds to lactone
desorption [8].
Integration and convolution of CO2 desorption for
the 24 h-OX sample leads to 39% (of the total
desorbed) attributed to carboxylic acid, which
means that this surface group is present in the
amount of 0.44 mmol/g. Previous studies report 3-
4 mmol/g of carboxylic acid groups for a low rank
carbon [12]. The difference may be related to the
 pyrolisis procedure which eliminates initial Structural changes can be studied by comparing
surface groups. isotherms of 24 h and 24 h-OX samples (Figure
3). It is observed that though the quantity of pores
decreases after acid treatment (adsorbed amount),
0,040 the type of pore (micropores) maintains (the shape
0,035 of the isotherms at low pressures is not
0,030 notoriously effected).
CO2 (%vol)

24 h-OX
0,025
0,020
24 h
0,015 400
0,010

Adsorbed volume (cm3/g STP)

0,005 350
0,000
0 100 200 300 400 500 600 700 800 300

Temperature (°C) 250

200
Figure 1. CO2 desorption on 24 h samples
150
0,040
0,035 100
0,030
CO (%vol)

0,025 24 h-OX 50
0,020 24 h
0,015 0
0,010 0 0.2 0.4 0.6 0.8 1
0,005
0,000 Pressure ratio
0 100 200 300 400 500 600 700 800
Figure 3. N2 adsorption isotherms for 24h-OX and
Temperature (°C) non-treated samples.
Figure 2. CO desorption on 24 h samples As activation time increases, the BET surface area
difference also does (Table 1). This is explained
In the desorption of CO (Figure 2) phenol could by the presence of larger amount of micropores
be identified by the peak at ~500 ºC while the produced during activation at longer times.
peak observed at ~700 °C may be attributed to Observing the type I isotherms in Figure 3 for the
quinone groups [8]. three oxidized AC samples it is possible to verify
the existence of micropores and how the
3.2 Nitrogen adsorption analysis activation time increases their presence.

BET surface area changes are presented
in Table 1 in which it is observed that all
samples present a decrease after oxidation
treatment, presumably due to the occupation of
functional groups in the surface, thus decreasing
the pore diameter.
These results are in contrast with functionalization
of xerogel carbons with nitric acid, which have
shown an increase in micro and mesopore
quantity [13], presumably due to higher oxidation
temperature (473 K) that affects formation of new
pores and opens inaccessible ones.

3.3 Effect of acid treatment on coal wettability

Table 1. BET surface area (m2/g) before and after
oxidation with acid treatment. To study the effect of surface functionalization on
Activation SBET 24 h (m2/g) SBET 24 h OX wettability, contact angles were compared, in a
time (m2/g) parallel experiment, for pyrolized carbon with and
6h 511 381 without oxidation treatment.
12.5 h 697 554
Wettability measurement for granulated materials
24 h 1293 755
differs from classic techniques used on

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 macroscopic samples [1]. Therefore, contact
angles have been calculated using the Washburn
correlation based on the capillarity of carbon
samples. The contact angles on sample-water
interface are shown in Table 2.
Table 2. Contact angle results
Acid treated carbon 14.8
Solely pyrolized carbon 88.6
From Table 2, the contact angle decreases in 83 %
with oxidation procedure. Thus, addition of
hydrophilic functional groups clearly improves
the wettability of carbon. This is evidence of the
increase of intermolecular forces (hydrogen
bonds) between water and the carbon-oxygen
groups added, as mentioned before.
4. CONCLUSIONS
CO2 activation time has effect on changing the
micropore volume but does not increase the pore
size.
Textural changes produced by acid treatment on
the carbon surface have been detected through
decreasing of SBET (21-42%) and increasing of
contact angle of wettability of samples in 83%.
This is explained by the addition of hydrophilic
functional groups detected by TPD.
For future research on AC it would be interesting
to study the acid treatment as a tool to increase
wettability properties and adsorption capacity, for
example, in different catalyst support preparation
methods.
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