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Energy Procedia 114 (2017) 2313 – 2321

13th International Conference on Greenhouse Gas Control Technologies, GHGT-13, 14-18

November 2016, Lausanne, Switzerland

Activated carbon from date seeds for CO2 capture applications

Adetola E. Ogungbenro, Dang V. Quang, Khalid Al-Ali, Mohammad R.M. Abu-Zahra*
Department of Chemical and Environmental Engineering, Masdar Institute of Science and Technology,
P.O. Box 54224, Abu Dhabi, United Arab Emirates (UAE)

Abstract

Considerations for reducing global carbon emissions are influencing the development of solid sorbents such as
activated carbons for carbon dioxide (CO2) capture. Adsorption efficiency often relies on method of preparation and
starting or source materials. The use of agricultural wastes such as date seeds are regarded as cost- effective options
to produce activated carbons for carbon capture. However, there has been no published study on the potentials of date
seeds synthesized activated carbon for carbon capture. In preparing activated carbon (AC) from date seeds by physical
activation technique, this study reports on the effects of pyrolysis temperature and activation time on the yield and
adsorption capacities of AC produced. Optimal temperature for pyrolysis was 800°C, while activation temperature
which had the highest CO2 adsorption capacity was 900°C with a loading of 141.14 mg adsorbed CO2/g activated
carbon. Sample characteristics such as surface area and porosity, infrared spectra, and scanning electron microscopic
images were also investigated in this study.
© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
© 2017 The Authors. Published by Elsevier Ltd.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of GHGT-13.
Peer-review under responsibility of the organizing committee of GHGT-13.
Keywords: Solid sorbents; Date seeds; Activated carbon, CO2 Adsorption

1. Introduction

Climate change is a complex and challenging problem in recent decades with many variables; increasing carbon
dioxide emissions, the continuous rise in energy demand and the clear dependency on fossil fuels which are carbon-

* Corresponding author. Tel.: +971-2-810-9333; fax: +971-2-810-9901.

E-mail address: mabuzahra@masdar.ac.ae

1876-6102 © 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of GHGT-13.
doi:10.1016/j.egypro.2017.03.1370
2314 Adetola E. Ogungbenro et al. / Energy Procedia 114 (2017) 2313 – 2321

intensive options needed daily to power global businesses. Among the most promising solutions to mitigate carbon
emissions is Carbon Capture and Storage (CCS). CCS entails several steps that includes effective capture of CO 2 at
its sources, i.e. fossil- fuel powered stations, compression and transport for use or storage in designated places for a
long time. To capture carbon dioxide, it is first separated from the flue gases resulting from combustion or industrial
processes. Various capture routes have been developed, with post- combustion capture systems being recognized as
the most mature, flexible and capable for retrofitting process to the large number of existing fossil- fuel fired power
plants and related infrastructures [1].
There are a number of separation technologies available for CO2 post-combustion capture, especially with amine-
based solvent systems that are commercially used for scrubbing CO2 from industrial flue gases. For a modern
pulverized coal (PC) power plant or a natural gas combined cycle (NGCC) power plant, the lead contending technology
is based on solvent scrubbing using amine solvents (mainly monoethanolamine- MEA) [2]. Process challenges often
encountered include low CO2 partial pressure in the flue gas, high energy demand in the reboiler, solvent losses and
expensive economics. To overcome these challenges, adsorption by solid materials is being considered due to inherent
benefits of low energy requirements, low capital and operating cost and with reduced secondary waste generation [3].
Research studies are being geared towards the development of advanced sorbents with lower regeneration energy, high
adsorption/desorption rates, lower volatility, better stability and less degradation and corrosivity [4].
Numerous factors describe the quality or utility of CO2 adsorbents. Categories include mesoporous and microporous
adsorbents in which a simple physical adsorption process is controlled by the pore characteristics of the sorbents. In
physical adsorption, the size and volume of the pores are important. Micropores are defined as cavities that are less
than 2 nanometers (nm) in size, mesopores are between 2 and 50 nanometer, and macropores are greater than 50 nm
in size [5]. The micropores make better selective adsorption of CO2. In general, fast adsorption and desorption kinetics,
large adsorption capacity, full regeneration capability , chemical and thermal stability, and a wide yet adjustable range
of operating conditions define an ideal, hypothetical adsorbent [6].
A number of physical adsorbents have been proposed for CO 2 adsorption based on characteristic properties. These
include activated carbon [7, 8], zeolites [8, 9], metal organic frameworks [10], fly ash [11], and hydrotalcite- like
compounds [12]. Activated carbon is one promising solid adsorbent that can be utilized to capture CO 2 due to its
numerous benefits such as low cost, easy for regeneration, insensitivity towards moisture, high CO2 adsorption
capacity at ambient condition, high specific surface area, adequate pore size distribution, high mechanical strength as
well as low in energy requirement [13]. The potential of activated carbon in CO2 capture depends on few criteria such
as activation method and nature of starting materials, which in turn affects the porosity and surface chemistry of the
synthesized activated carbon. However, exploitation of activated carbons in capturing CO 2 has not been extensively
evaluated. It has been employed in pilot scale power plants, but not yet on a large scale, therefore, it is necessary to
develop low- cost options for large scale plants [14].
This research work investigates the carbon capture applications of activated carbon produced from seeds of local
date fruits palm (Phoenix dactylifera) in the United Arab Emirates (UAE). The use of biomass residues such as date
seeds to develop sorbents for CO2 capture has attracted significant attention to reduce the total costs of capture [15].
Date seeds are suitable for preparing activated carbon due to its excellent natural structure, lignocellulosic composition
and low ash content [16]. They are composed of cellulose (42%), hemicellulose (18%), sugar and other compounds
(25%), lignin (11%) and ash (4%) [17]. They are also quite ubiquitous in the Middle East and are among the most
common agricultural by-products available in the UAE with a reported fruits yield of 250 thousand tons in 2013 [18].
Date seeds, like other biomass residues, have been employed in preparing activated carbon but limited literature
and information are yet available on the potentials of date seed- synthesized activated carbon for carbon capture
applications. In a study which prepared activated carbon (AC) from Algerian date stones by physical activation, it was
reported that the percentage yield decreased with increase of pyrolysis temperature and hold time. The best specific
surface area (635 m2/g) and microporous volume (0.716 cm3/g) were also obtained when the date stones were grinded,
and pyrolysed at 700°C under a 100 cm3/min nitrogen flow and then activated under water vapor at the same
temperature for 6 hours [16].
Experimental studies from this research work evaluated the CO2 adsorption capacity of activated carbon synthesized
from date seeds. Physical preparation of activated carbon involved pyrolysis of source carbonaceous material at high
temperature (600–900°C) in inert atmosphere in order to eliminate the presence of oxygen and hydrogen elements.
Afterwards, thermal activation at the same pyrolysis temperature and at a higher temperature in the presence of
 Adetola E. Ogungbenro et al. / Energy Procedia 114 (2017) 2313 – 2321 2315

oxidizing gas (CO2) was carried out. Performance of the prepared samples were compared with a base-case of
commercially obtained activated carbons.

2. Experimental

2.1 Materials

Seeds from locally produced date fruits in the UAE were used as starting materials for experimental studies. The
date seeds were cleaned and dried at 140°C for about 16 hours to remove excess moisture and make grinding easier.
Dried seeds were crushed with an electrically powered grinder and sieved to very small particle sizes (< 200μm) more
favored for physical preparation of activated carbon [19].
Pure grade commercially prepared samples of activated carbon were purchased from Sigma-Aldrich.

2.2 Pyrolysis and activation method

Pyrolysis of crushed date seeds was carried out in a Nabertherm High Temperature Furnace with a manual gas
supply system and purge with non- flammable protective or reaction gases. The furnace is suitable for
thermogravimetric analysis and uses high quality molybdenum disilicide heating elements fitted in a fiber- lined box
chamber with temperature controlled by a type B thermocouple. The yield of pyrolysed date seeds (PDS) was
calculated as a ratio of the obtained pyrolysed samples to the crushed seeds. The optimum temperature for pyrolysis
is that temperature at which the yield is lowest i.e. there’s no further significant mass loss at higher temperatures. Two
crucibles containing over 10 grams each of crushed date seeds (CDS) were placed in the middle of the furnace and
heated to different pyrolysis temperatures between 600 - 900°C at 100°C intervals. A slow heating rate of 15°C/min
was applied under nitrogen flow of 150 ml/min. After pyrolysis temperature is reached, the samples were held at this
temperature for 1 hour.
Activation was carried out at the determined optimal pyrolysis temperature (OPT) under CO2 flowing at 150
ml/min. Different activation times of 1hr, 2hrs and 3hrs were used at the same optimal pyrolysis temperature. The
yield of activated carbon was also determined for the optimal activation time (OATm). Final round of pyrolysis and
activation procedures involved heating to the OPT under nitrogen flow for one hour, and then activating at 900°C at
the OATm.

2.3 Characterization

Fourier transform infrared (FTIR) spectroscopy identified the surface functional groups present in the samples.
Infrared transmission spectra from 4000 to 400 cm-1 were obtained by a Bruker Vertex 80v spectrometer. Samples
were prepared using the potassium bromate (KBr) wafer method by mixing about 3mg of sample and 500mg of KBr,
compacted into a pellet with a manual hydraulic press. The control pellet was made of pure KBr powder. For each run,
five hundred scans were taken with a 4 cm-1 resolution.
The morphological structures of crushed date seeds, pyrolysed date seeds and activated carbon samples were
examined using Quanta 250 scanning electron microscope (SEM). Adsorption and desorption analysis of the solid
materials were examined with a Quantachrome NOVA 2000e surface area and pore size analyzer. Porosity was
characterized by nitrogen (N2) physisorption process at -196°C. The samples were initially degassed under vacuum at
300°C for about 6 hrs. This has been correlated to be the optimum conditions for sample pretreatment for pore analysis
[20]. Sorption isotherms were represented by a graph plot of N2 gas adsorbed versus the relative pressure (P/P 0) where
P0 is taken as atmospheric pressure. All measurements were estimated at P/P0 range of approximately 0.01 to 0.1, with
a correlation coefficient of 0.9999 and cross-sectional area of N2 molecule taken as 0.162 nm2. The specific surface
area was evaluated using Brunauer- Emmett- Teller (BET) equation, and the t- plot method to compute the micropore
volume and area.
2316 Adetola E. Ogungbenro et al. / Energy Procedia 114 (2017) 2313 – 2321

2.4 CO2 adsorption

CO2 adsorption or capture was observed using a micro reaction calorimeter (μRC) station. Fig. 1a illustrates the
experimental setup of CO2 adsorption using the μRC. Pyrolysed date seeds (PDS), synthesized activated date seeds
(ADS) and commercial samples were examined for capacity to capture carbon dioxide. Prior to the adsorption process,
the samples were desorbed at 120°C for about four hours to remove any moisture and adsorbed gases. Approximately
0.35 grams of sample was placed into a weighed analysis cell and CO2 was supplied at 0.5 ml/min under isothermal
mode at 20°C and stable power signal. As soon as the CO2 gas is flowed, the power signal starts increasing (Fig. 1b)
and adsorption is completed when the power signal is back to its original steady state level. The CO2 flow is
discontinued and the cell is removed and weighed. The CO2 loading of adsorbent, θ (mg/g), is given by;

(m2  m1 ) *1000 mg
Loading (θ) = ( ) (1)
(m1  m0 ) g

Where m0= mass of empty cell (g)

m1= mass of cell + sample, PDS or activated carbon (g)
m2= mass of cell + sample + adsorbed CO2 (g)

The micro reaction calorimeter allows for simultaneous determination of the heat of CO2 adsorption by integral heat
computation of the signal curve obtained:

Heat of CO2 adsorption, ∆H = Q / 1000 (2)

(kJ / molCO2 )
(m2  m1 ) / 44

Where Q = Total integral heat (Joules)

V3 By-pass
Gas in Gas out
a MFC b
T1 V1 T2 V2
Cap

Shunt

Analysis Reference
D cell cell
Calorimeter

N2 CO2

Fig. 1. (a) An illustration of CO2 adsorption process using a flow micro reaction calorimeter (μRC)
(b) Adsorption data showing power (mW) vs. time (secs)
 Adetola E. Ogungbenro et al. / Energy Procedia 114 (2017) 2313 – 2321 2317

3. Results

3.1 Pyrolysis

Experimental runs were conducted at different temperatures (600, 700, 800, 900°C) to determine the optimal
pyrolysis temperature (OPT) at which the yield is lowest. Table 1 displays the yield percentage for the pyrolysis tests.
As the temperature increased from 600 to 800 °C, the yield of PDS decreased as a result of partial decomposition of
date seeds in liquid and gaseous products. The yield became fairly constant at above 800 °C, indicating this
temperature as the optimal point. Activation is thereafter carried out at 800 °C.

3.2 Activated carbon

Activation of pyrolysed date seeds with CO 2 was carried out at the determined OPT of 800 °C. Varying holding
times of 1hr, 2hrs and 3hrs were examined for the yield of activated carbon. The longer the holding time, the more the
volatile matter released. Activation time of 1hr therefore gave the highest yield. At this constant holding time,
activation was carried out at a higher temperature of 900 °C after sample had been pyrolysed at 800°C (OPT).

Table 1. Temperature effect on yield of Table 2. Effect of holding time and activation
pyrolysed date seeds temperature on activated carbon yield
Sample Pyrolysis Yield Sample Yield (%)
Temperature (%)
(°C) ADS-800-1H 7.96
PDS 600 600
18.81 ADS-800-2H 1.28
PDS 700 700
17.67
ADS-800-3H 1.15
PDS 800 800
14.54
PDS 900 900 ADS-900-OPT- 7.25
14.42
1H

Table 2 shows the effect of the holding times and activation temperature on the yield of AC. As activation
commences, low burn- off causes partial pore development with further breakdown of cellulose and hemicellulose
creating porosity in the date seeds which increases its adsorption capacity. Increased temperature and time results in
wider micropore development giving larger surface areas and pore volumes. However, with prolonged activation time,
micropore widening mutates to pore collapse causing particle sintering and cyclic formation of mesopores or
macropores. At activation temperature 900°C, there is no appreciable decrease in the yield of AC as the remnant
component is lignin which is more difficult to decompose [16, 21].

3.3 FTIR analysis

Fourier transform infrared (FTIR) transmission spectra were obtained to evaluate the functional groups at the
surface of the crushed, pyrolysed and activated carbon samples as shown in Fig. 2. The CDS samples contained more
absorption bands than the PDS and ADS samples. This is a reflection of the lignocellulosic composition of date seeds
and the presence of functional groups alkene, ester, aromatic, alkanone, alcohol, hydroxyl, ether and carboxyl [21].
The IR band 3457 cm-1 indicates presence of hydroxyl group (O-H stretching 3560 to 3419 cm-1) and it is prevalent
only in the raw date seeds. As pyrolysis occurs, certain bands (3457, 2924, and 2854 cm -1) disappear with reduction
in moisture content and aliphatic compounds in the date seeds. Activation process introduces stretching of the carbonyl
group observed in the C=O band at 1640cm-1 with similar trend observed in the range 1430 to 1300 cm-1 due to C-H
bending.
2318 Adetola E. Ogungbenro et al. / Energy Procedia 114 (2017) 2313 – 2321

0.5

CDS

0.4 PDS 700

PDS 800

PDS 900
Transmission Ratio

0.3
ADS-800-1H

0.2

0.1

0
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1)

Fig. 2. FTIR Spectra of CDS, PDS (700, 800, 900), and ADS-800-1H

3.4 Scanning electron microscopy

Fig. 3 shows the scanning electron microscope (SEM) images of the raw crushed date seed (Fig. 3a), pyrolysed
samples (Fig. 3b at 600°C & Fig. 3c at 900°C), and date-seed synthesized activated carbons at 800°C for 1hr (Fig.
3d). The crushed date seeds surface were characterized by presence of a few macropores. As pyrolysis progresses
from 600- 900°C, porosity results. Pore development during pyrolysis is an important step to enhance surface area
and pore volume of the activated carbon by promoting the diffusion of activating CO 2 molecules into the pores, and
thereby increasing the CO2–carbon reactions which would create more pores in the activated carbon.
Large and well-developed pores were clearly found on the surface of the activated carbon sample (Fig. 3d). These
well-developed pores on the prepared AC would be the main factor that will be responsible for adsorption of CO 2.

a b
 Adetola E. Ogungbenro et al. / Energy Procedia 114 (2017) 2313 – 2321 2319

c d

Fig. 3. SEM images of (a) CDS, (b) PDS 600, (c) PDS 900 (d) ADS-800-1H

3.4 Nitrogen adsorption isotherms

Surface area and pore characteristics of the samples were examined using N 2 adsorption isotherms. Fig. 4 shows
the adsorption isotherms for the prepared and commercial activated carbon samples. The BET surface area and t-plot
method micropore area and volume are given in Table 3. As expected, the ADS samples exhibited the sorption
isotherms of Type I according to the International Union of Pure and Applied Chemistry (IUPAC) classification for
microporous structure with a narrow pore size distribution [21]. From Table 3, increase in pyrolysis temperature led
to porosity increase as seen in specific surface areas of 265.42 and 502.70 m2/g for PDS 600 and 800 respectively. At
temperatures greater than the OPT, pore collapse results, hence, the reduced surface area for PDS 900°C. Activation
causes greater porosity with surface release to form more pores in the structure.

450

400
ADS-800-1H
350 ADS-900-OPT-1H
Vol. N2 adsorbed (cm3/g)

Comm AC
300

250

200

150

100

50

0
0.00 0.20 0.40 0.60 0.80 1.00
Relative Pressure (P/Po)

Fig. 4. N2 adsorption isotherm

2320 Adetola E. Ogungbenro et al. / Energy Procedia 114 (2017) 2313 – 2321

Table 3. Surface area and pore characteristics

ADS-800- ADS-900-
Parameter PDS 600 PDS 800 PDS 900 1H OPT-1H Comm. AC
BET Surface
Area (m2/g) 265.42 502.70 449.81 627.15 723.72 698.72
Micropore
Area (m2/g) 268.38 483.78 416.51 593.71 678.87 474.58
Micropore
Volume
(cm3/g) 0.10 0.192 0.17 0.23 0.268 0.21

3.5 CO2 capture

The CO2 adsorption capacities and heats of adsorption of the PDS and ADS samples are given in Table 4. . As pyrolysis
temperature increased to the OPT, there was more adsorption potential shown in CO2 loading of 64.96, 85.52 and
91.12 mg/g for PDS 600, 700 and 800 respectively. This became diminished as the optimum is exceeded from 800 to
900°C as a result of collapsing pores and more ash content.

Table 4. CO2 capture capacities of adsorbents

CO2 loading Adsorption heat
Sample
(mg/g) (kJ/mole)
PDS 600 64.96 33.39
PDS 700 85.52 24.32
PDS 800 91.12 21.39
PDS 900 68.14 35.95
ADS-800-1H 97.15 29.16
ADS-900-OPT- 1H 141.14 13.62
Comm. AC 96.29 36.69

Synthesized activated carbons generally showed better adsorption performance than the pyrolysed samples. ADS-
800-1H had a similar loading capacity of 97.15 mg/g to the commercially obtained sample of 96.29 mg/g. Sample
pyrolysed at 800°C but activated at 900°C (ADS-900-OPT-1H) gave the best CO2 loading capacity of 141.14 mg/g.
All solid sorbents prepared had lower heats of adsorption relative to conventional amine-MEA solutions [22].

4. Conclusion

The potentials of date seeds to produce activated carbon for CO2 capture has been examined in this research work.
Activation via physical method was employed and the effects of pyrolysis temperature on yield of activated carbon.
Results indicated that pyrolysis at 800°C followed by CO2 activation at 900°C and holding time for one hour is the
most optimal condition for CO2 adsorption.
Further research work may consider other means of physical activation e.g. hydrothermal testing, chemical activation
and amines impregnation to assess efficiencies of date seed-synthesized activated carbon to capture carbon dioxide.
 Adetola E. Ogungbenro et al. / Energy Procedia 114 (2017) 2313 – 2321 2321

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