Carbon 42 (2004) 1371–1375

www.elsevier.com/locate/carbon

About reactions occurring during chemical activation

with hydroxides
M.A. Lillo-R
odenas, J. Juan-Juan, D. Cazorla-Amor
os, A. Linares-Solano *

Departamento de Quımica Inorganica, Universidad de Alicante, Ap. Correos 99, E-03080 Alicante, Spain
Received 10 July 2003; accepted 28 December 2003

Available online 18 February 2004

Abstract
The chemical activation of anthracites with hydroxides has been shown to be of interest for the production of activated carbons
with a highly microporous structure. In a previous paper, attention was placed on the reactions occurring during the chemical
activation of an anthracite by NaOH and KOH. In the present work, the process of chemical activation by hydroxides has been
extended to different coal precursors to confirm that such a chemical activation process starts through a solid–solid reaction and
continues as a solid–liquid reaction. In such a solid reaction, the reactivity of the solid (precursor) should be a key parameter. The
importance of the carbon reactivity on its reaction with hydroxides has been confirmed: the lowest rank coal reacts much easily and
has a much lower temperature for the beginning of reaction than the highest rank coal.
Ó 2004 Elsevier Ltd. All rights reserved.

Keywords: A. Activated carbon; B. Activation; C. Adsorption, Infrared spectroscopy, Temperature programmed desorption

1. Introduction occurring during the chemical activation with hydrox-

Chemical activation with hydroxides has recently
been of great interest as it permits the preparation of
activated carbons with a highly developed porosity.
Therefore there is an increasing number of studies re-
lated to the preparation of activated carbons by chem-
ical activation with KOH [1–8] and, more recently, also
with NaOH [1,3,5,6,9].
It has been shown [1–4] that some experimental
variables have a great influence on the porosity of the
activated carbons prepared by chemical activation with
hydroxides: the ratio activating agent/coal, the method
of mixing of the activating agent and coal, the temper-
ature and flow of gas during the carbonisation, etc.
Although there exist some studies regarding the effect
of some experimental variables on chemical activation
with hydroxides, there is a lack of information about
how the chemical activation occurs. In a previous study
[10], we analysed some aspects relative to the reactions
*
Corresponding author. Tel.: +34-9-6590-3545; fax: +34-9-6590-
3454.
E-mail address: linares@ua.es (A. Linares-Solano).
0008-6223/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2004.01.008
ides, KOH and NaOH, using anthracite as precursor.
This study led to conclusions related to the solid–
hydroxide reaction, to the products of the reaction and
to the temperature of the process. It also permitted to
understand why some experimental variables have such
an important effect on the final porosity.
The purpose of this work is to further explore the
reactions occurring during chemical activation with ei-
ther NaOH or KOH by extending the study to other
carbon precursors: lignite, subbituminous coal and
anthracite. The activation of lignite will be compared
with that of carbonised lignite, whereas the behaviour of
anthracite is compared with that of the anthracite car-
bonised up to 1000 °C and higher temperatures, to vary
the reactivity behaviour of the precursor.
2. Experimental
TPD experiments have been carried out in a quartz
reactor to study the carbon–hydroxide reactions occur-
ring during the heat-treatment of the sample. The con-
ditions of the heating were: a helium flow (60 ml/min), a
heating rate of 20 °C/min, a maximum temperature of
about 750 °C and a soaking time of 1 h at the maximum
1372 M.A. Lillo-Rodenas et al. / Carbon 42 (2004) 1371–1375

temperature. The evolved gases from these experiments 30

have been analysed by mass spectrometry. All the
samples were identically prepared by a physical mixing 25
H2-Sub/NaOH
of the hydroxide and the carbon in a 1/1 molar ratio,
20
following closely the experimental conditions used dur-

ing the activation process [3].
These experiments provide information about the
temperature for the beginning of the reaction and about
the percentage of hydroxide reacted during the process
of activation. Hence, different variables have been
analysed: the nature of the hydroxide (KOH and
NaOH), the nature of the precursor (lignite, subbitu-
minous and anthracite) and the effect of heat-treatment
of lignite and anthracite (lignite versus carbonised lignite
and anthracite versus heat-treated ones, the temperature
of which is indicated by the number next to A).
Because the heat-treatment of the carbonaceous so-
lid–hydroxide involves essentially a solid–liquid reac-
tion, it has to be related to the reactivity of the carbon
precursor. To confirm such a hypothesis, a study of the
behaviour of the carbon precursor in air has been car-
ried out. Thermogravimetric analysis (TG) of the dif-
ferent precursors has been done in air (60 ml/min), using
a heating rate of 5 °C/min up to 650 °C over different
precursors: anthracite (A), anthracite treated up to 1800
°C (A-1800), subbituminous coal (SB), lignite (L) and
carbonised lignite (LC).
3. Results and discussion
3.1. TPD experiments for the mixtures precursor–
hydroxide
Our study of the reactions occurring during activa-
tion of an anthracite by KOH or NaOH [10] has shown
that chemical activation consists of a reaction between
the carbon and the hydroxide. The reaction products are
the metal carbonate, hydrogen and some metallic com-
pound, in good agreement with the results of Otowa
et al. [7,8] obtained by mixing petroleum cokes and
µmol/sg
15
10
5
0
0 200 400 600
Temperature (ºC)
Fig. 1. Hydrogen evolution in the chemical activation of the subbi-
tuminous coal/NaOH followed by TPD experiment.
for the beginning of the reaction, Ti ) and the extents of
the reaction (carbon reacted deduced from the hydrogen
formation applying reactions (1) and (2)). The experi-
ments were carried out both with NaOH and KOH to
simulate the chemical activation in a furnace.
As an example, Fig. 1 shows the total hydrogen
evolved from a TPD experiment carried out with a
subbituminous coal/NaOH mixture and Figs. 2–4 pres-
ent the H2 evolved up to the activation temperature (750
°C) from different precursor/activating agent mixtures.
From these TPD experiments the data of Table 1
have been obtained for some of the samples studied with
both hydroxides. The beginning of the reaction in Table
1 corresponds to the start of hydrogen appearance.
As shown in Table 1, in all the precursors studied the
starting temperature of the reaction is lower for KOH
than for NaOH, confirming that KOH is a more reactive
agent, in agreement with our previous results [10].
From Table 1 and Fig. 2 it can be seen that the
chemical activation process depends on the rank/reac-
tivity of the coals. As expected, the higher the reactivity
30

KOH. From these reaction products our proposed H2-Lig/NaOH

25
reactions, different from those of Otowa et al. [7] are: H2-Sub/NaOH

6NaOH þ 2C $ 2Na þ 3H2 þ 2Na2 CO3 ð1Þ H2-Ant/NaOH

20
µmol/sg

6KOH þ 2C $ 2K þ 3H2 þ 2K2 CO3 ð2Þ

15
In this type of reaction (solid–hydroxide) the reactivity
of the solid has to be a key factor, as will be shown next 10
by analyzing the different carbon precursors used (lig-
nite, subbituminous, anthracite, heat-treated carbons). 5
It should be noted that the above reactions are global
reactions that do not describe the detailed reaction 0
0 200 400 600
mechanism.
Temperature (ºC)
Over different precursor–hydroxide mixtures, TPD
experiments have been carried out, in order to determine Fig. 2. Effect of the rank coal on the temperature of evolution of
their different reactivities (deduced from the temperature hydrogen for different mixtures coal/NaOH.
 M.A. Lillo-Rodenas et al. / Carbon 42 (2004) 1371–1375 1373

50 The effect of the heat-treatments, which was to

45 modify the reactivity, has also been studied. Figs. 3 and
lignite
40 4 present the evolution of hydrogen versus temperature
carbonised lignite for the pairs lignite–carbonised lignite and anthracite–
35
anthracite treated up to 1000 °C, respectively (see also
30
µmol/sg

Table 1).
25
As it is well-known [13], the heat-treatment of a given
20 carbon material causes a decrease in its reactivity, in
15 agreement with data compiled in Table 1 and with data
10 plotted in Figs. 3 and 4 (shown by an increase in the
5 initial reaction temperature). In the case of anthracite
0
heat-treated up to temperatures higher than 1000 °C, the
0 200 400 600 hydrogen evolution can not be followed, nor can it be
activated, as it can be seen from Table 2 which includes
Temperature (ºC)
the BET surface areas for these samples prepared using
Fig. 3. Comparison in the evolution of hydrogen versus temperature either NaOH or KOH. The higher the temperature of
for the lignite and the carbonised lignite. the treatment, the lower the amount of H2 evolved and
the less the resulting activation.
10 These data corroborate the suggestion that the
9 beginning of the reaction depends on the reactivity of
8
H2-Ant/NaOH the materials used in the mixture and that the activation
process of a coal–hydroxide mixture is a reaction be-
7 H2-Ant-1000/NaOH
tween a solid (the coal) and the hydroxide (which
6
µmol/sg

according to its melting point will be liquid) producing

5 hydrogen.
4 From TPD experiments the quantification of hydro-
3 gen evolved during the activation process can be as-
2 sessed. Table 3 compiles the results obtained in the case
1
of NaOH, for some of the samples studied. We can
observe that the H2 evolution decreases with the rank/
0
0 200 400 600 reactivity.
Temperature (ºC) If we assume that the hydrogen evolved from the
mixtures comes from the conversion of the hydroxides,
Fig. 4. Comparison in the evolution of hydrogen versus temperature according to reactions (1) and (2), the percentage of
for the raw anthracite and the anthracite-1000.

Table 2
Table 1 BET surface area for anthracite and heat-treated anthracites chemi-
Temperatures for the start of the reaction for different precursor– cally activated with NaOH and KOH
hydroxide mixtures Sample BET surface area, m2 /g
Precursor Temperature Temperature Samples activated Samples activated
(NaOH reaction), °C (KOH reaction), °C with NaOH with KOH
L 250 225 A 1630 2326
LC 450 250 A-1000 58 77
SB 375 325 A-1800 10 9
A 475 375 A-2500 4 6
A-1000 575 550

of the coal, the lower is the temperature for the begin- Table 3
ning of the reaction both by NaOH and KOH. Hydrogen evolved in the TPD experiments carried out over the mix-
Such hydrogen evolution is in agreement with the for- ture precursor–NaOH and % of reacted carbon
mer studies of Yamashita and Ouchi [11,12] obtained by Precursor H2 evolution, % wt. of reacted
studying the carbonisation process of different precursors lmol/g carbon
heat-treated with NaOH. However, their proposed reac- L 22,759 9.0
tions, based on dehydrogenation through active methy- SB 13,563 6.0
lene groups causing condensation reactions, differ A 3860 2.0
A-1000 680 0.3
considerably from the one we propose in reaction (1).
1374 M.A. Lillo-Rodenas et al. / Carbon 42 (2004) 1371–1375

reacted carbon has been calculated for the different
mixtures. From this quantification, compiled in Table 3
for the mixtures precursor/NaOH, we observe that the
percentage of reacted carbon decreases as the rank in-
creases. The same trend is observed for KOH activation.
It should be noted that carbon is only removed from
the solid carbon sample as a carbonate of sodium, or
potassium. In this paper, and in a previous one [10] no
CO and CO2 evolution were detected at temperatures
below 750 °C but only H2 was measured. Only at higher
temperatures does carbonate decomposition occur pro-
ducing CO and CO2 .
3.2. Study of the reactivity of the different precursors
To confirm that the carbon–hydroxide reaction, in
terms of the importance of the solid reactivity, does not
differ from the well-known air–carbon reaction, TG
experiments have been done on the different samples.
Fig. 5 includes the TG curves for the anthracite (A),
100
90
80 L LC
70
% weight loss
subbituminous coal (SB), lignite (L) and carbonised
lignite.
As observed, and following the logical order for the
well-known air–coal reaction [14], the most reactive is
the lignite coal, whereas the anthracite is the less reactive
one. The air reaction of the lignite (L) has been com-
pared with that of the carbonised lignite (LC). As ob-
served, the carbonised lignite is less reactive than the
pristine one, showing similar behaviour to that of the
subbituminous coal.
The air reaction of the pristine anthracite (A) has also
been compared with that of the anthracite carbonised to
1000 °C (A-1000) and 1800 °C (A-1800). The order, as
expected, shows that the pristine anthracite is the most
reactive among the three (see Fig. 6).
4. Conclusions
An analysis of the chemical activation of different
precursors (coals) with hydroxides (NaOH and KOH)
has confirmed that the heat-treatment of a carbon in the
presence of an hydroxide, produces hydrogen and oc-
curs via a solid–liquid reaction in which the reactivity of
SB A the starting solid is a key parameter that controls the
extent of the reaction and the starting temperature for
the reaction. Such hydrogen evolution, examined by

60
TPD, allows us to assess both the initial reaction tem-
50
perature and the extent of the carbon reacted during the
40
activation process.
30 It has been seen that for the more reactive coals (the
20 lower rank ones), the carbon–hydroxide reaction begins
10 at lower temperatures than for higher rank coals. The
0 extent of such a reaction also depends on the reactivity
0 100 200 300 400 500 600 700 of the starting carbon, decreasing from lignite to sub-
Temperature (ºC) bituminous coal to anthracite. In addition, heat-treat-
Fig. 5. TG curves for four of the precursors.
ment prior to activation reduces considerably the ease
of the reaction, as also happens in the carbon–gas
reactions, and hence it makes its activation process
100 difficult.
90
80
70 Acknowledgements
% weight loss

60
The authors thank MCYT (Project MAT 2000-0621)
50
for financial support. M.A. Lillo-R
odenas thanks GV
40 for a thesis grant.
A-1800
30
A-1000
20
A References
10
0
0 100 200 300 400 500 600 700 [1] Illan-G
omez MJ, Garcıa-Garcıa A, Salinas-Martınez de Lecea C,
Temperature (ºC) Linares-Solano A. Activated carbons from Spanish coals. 2.
Chemical activation. Energy Fuels 1996;10(5):1108–14.
Fig. 6. TG curves for the anthracite (A), for the anthracite carbonised [2] Lozano-Castell o D, Lillo-R odenas MA, Cazorla-Amor os D,
up to 1000 °C (A-1000) and for the anthracite carbonised up to 1800 Linares-Solano A. Preparation of activated carbons from Spanish
°C (A-1800). anthracite. I. Activation by KOH. Carbon 2001;39(5):741–9.
 M.A. Lillo-Rodenas et al. / Carbon 42 (2004) 1371–1375
[3] Lillo-R
odenas MA, Lozano-Castell o D, Cazorla-Amor os D,
Linares-Solano A. Preparation of activated carbons from Spanish
anthracite. II. Activation by NaOH. Carbon 2001;39(5):751–
9.
[4] Teng H, Hsu L. High-porosity carbons prepared from bituminous
coal with potassium hydroxide activation. Ind Eng Chem Res
1999;38(8):2947–53.
[5] Evans MJB, Halliop E, MacDonald JAF. The production of
chemically-activated carbon. Carbon 1999;37(2):269–74.
[6] Lee SH, Choi CS. Chemical activation of high sulfur petroleum
cokes by alkali metal compounds. Fuel Process Technol
2000;64(1):141–53.
[7] Otowa T, Tanibata R, Masao I. Production and adsorption
characteristics of MAXSORB: high-surface-area active carbon.
Gas Separation Purificat 1993;7(4):241–5.
[8] Otowa T, Nojima Y, Miyazaki T. Development of KOH activated
high surface area carbon and its application to drinking water
purification. Carbon 1997;35(9):1315–9.
1375
[9] Hayashi J, Watkinson AP, Teo KC, Takemoto S, Muroyama K.
Production of activated carbon from Canadian coal by chemical
activation. Coal Sci 1995;1:1121–4.
[10] Lillo-Rodenas MA, Cazorla-Amor os D, Linares-Solano A.
Understanding chemical reactions between carbons and NaOH
and KOH: an insight into the chemical activation mechanism.
Carbon 2003;41(2):267–75.
[11] Yamashita Y, Ouchi K. Influence of Alkali on the carbonization
process. I. Carbonization of 3,5-dimethylphenolformaldehyde
resin with NaOH. Carbon 1982;20(1):41–5.
[12] Yamashita Y, Ouchi K. Influence of Alkali on the carbonization
process. II. Carbonization of various coals and asphalt with
NaOH. Carbon 1982;20(1):47–53.
[13] Radovic LR, Walker Jr PL, Jenkins RG. Importance of carbon
active sites in the gasification of coal chars. Fuel 1983;62:849–56.
[14] Mahajan OP, Walker Jr PL, Karr Jr C, editors. Reactivity of heat
treated coals. Analytical methods for coal and coal products, vol.
II. New York: Academic Press Publisher; 1978. p. 465–94.