36 Indo. J. Chem.

, 2010, 10 (1), 36 - 40

SHORT COMMUNICATION
ACTIVATED CARBON FROM DURIAN SEED BY H3PO4 ACTIVATION:
PREPARATION AND PORE STRUCTURE CHARACTERIZATION

Amri Ismail1.*, Hanggara Sudrajat2, and Desi Jumbianti3

1
Department of Chemical Engineering, Faculty of Engineering, Malikussaleh University, Lancang Garam,
Lhokseumawe 24351, Indonesia
2
Graduate Student, Department of Chemical Engineering, Faculty of Engineering, Universitas Gadjah Mada,
Yogyakarta 55281, Indonesia
3
Biomolecular Engineering Research Institute, 6-2-3 Furuedai, Suita 565-0874, Japan

Received January 25, 2010; Accepted February 10, 2010

ABSTRACT

Activated carbons have been produced from the natural biomaterial durian (Durio zibethinus) seed, using
phosphoric acid (H3PO4) as the activating agent. The effects of impregnation ratio, activation temperature, heating
rate on the carbon surface area, porosity and mass yield are presented. A two step process has been used, the first
step was a low temperature impregnation at 150 °C using phosphoric acid and the second step was the
carbonization at high temperatures, namely, 600 and 900 °C. The most outstanding carbon with the highest surface
2
area of 2123 m /g was prepared using an impregnation ratio of 2, an activation temperature of 600 °C for 4 h and a
heating rate of 1 °C/min.

Keywords: activated carbon, durian seed, phosphoric acid activation

INTRODUCTION new pores so that the adsorptive power of the

carbonization product is enhanced [3-6].
Activated carbons are the most versatile and Activation can be carried out by chemical or
commonly used adsorbents because of their extremely physical means. Generally within chemical activation
high surface areas and micropore volumes [1], large process, carbonization and activation take place
adsorption capacities, fast adsorption kinetics, and simultaneously as facilitated by chemical activating
relative ease of regeneration [2]. Precursors used for the agents, i.e. dehydrating agents and oxidants. On the
production of activated carbons are organic materials other hand for physical activation, carbonization of a
that are rich in carbon, such as coal, lignite, and wood. precursor occurs in priori followed by their activation at
Although coal is the most commonly used as precursor, elevated temperature in the presence of suitable
agricultural by-products in certain condition are a better activating agents, i.e. carbon dioxide or steam. It has
choice [1,3]. Many agricultural by-products such as been noticed that chemical activation process normally
coconut shell, grain sorghum, coffee bean husks, rubber takes place at a temperature lower than physical
wood sawdust, chestnut wood, and fruit stones, have activation process [1]. The impregnation of precursor
been discovered to be suitable precursors for activated materials with chemical agents such as ZnCl2 and KOH
carbon due to their high carbon and low ash contents [5]. can inhibit tar formation while also reduce the volatile
Agricultural wastes are considered to be a very matter evolution resulting in high precursor to carbon
important feedstock because of especially two facts: conversion. Therefore, the development of a porous
they are renewable sources and low cost materials [4-5]. structure is improved with chemical activation process
Activated carbons are generally obtained using two [1]. Among the chemical activating agents, zinc
main steps, e.g. carbonization of the raw materials below chloride (ZnCl2) in particular is the most frequently used
1000 °C in an inert atmosphere followed by activation of chemical in activated carbon preparation. Nowadays
the resulting char in the presence of suitable oxidizing however, zinc chloride is less employed due to its
agents. In carbonization, most of the non-carbon environmental damage. In addition, activated carbons
elements like hydrogen and oxygen are being removed chemically activated with zinc chloride are not suitable
onto gaseous form by pyrolytic decomposition resulting in pharmaceutical and food industries due to its
in a carbon with fixed mass and a rudimentary pore possibility to contaminate products. Another more
structure. The following activation step is then employed favorable agent, H3PO4 has been claimed to be the
to enlarge the diameter of fine pores and also create most effective acid for activated carbons production.
* Corresponding author. Tel/Fax : +62811678692/+6264543040
Email address : [email protected]

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 Indo. J. Chem., 2010, 10 (1), 36 - 40 37

To obtain very specific materials with a given pore under vacuum at 200 °C for 6 h before measurements
size distribution from low cost precursors at low were made. The specific surface area was calculated
temperature is considered a challenge. Thus, in this using the Brunauer–Emmett–Teller (BET) equation
work, durian seed as precursors used for the production (SBET) and αs method (Sα) using the standard as data
of derived activated carbons are produced and their reported by Katsumi Kaneko from the adsorption data
characteristic properties have been determined. of N2 at -196 °C [7]. The total pore volume (Vp) was
Preparation details including the effect of various estimated from the amount of nitrogen adsorbed at a
0
parameters onto surface development and relative pressure of P/P = 0.97 and the average pore
characteristics are also given because of their important diameter was calculated from Dp = 4 Vp/SBET. Pore size
roles in adsorption. distribution was estimated using the αs method (for
micropore analysis) and the Barrett-Joyner-Helenda
EXPERIMENTAL SECTION (BJH) model (mesopore analysis). For microporous
adsorbents, αs method was employed to analyse the
Preparation of adsorbents micropore volume (Vmicro) and mesopore volume
(Vmeso = Vp - Vmicro). For mesoporous adsorbents, the αs
Durian seed collected from local durian processing method was employed to analyse the micropore
industry was used as a precursor for preparing activated volume and the BJH method was employed to estimate
carbon. The contents of carbon, hydrogen, nitrogen and the mesopore volume. BJH method was also applied to
sulphur in the ultimate analysis were determined by an estimate the pore size distribution of the adsorbents.
elemental analyzer (Vario EL III) and were found to be SEM images were recorded using JEOL JSM-
47.32, 8.44, 0.26 and 0.04% (w/w) respectively. The ash 6400F field emission SEM. A thin layer of platinum was
content was determined by heating the raw material to sputter-coated on the samples for charge dissipation
650 °C for 4 h and equaled to 1.95% by weight. The during SEM imaging. The sputter coater (Eiko IB-5
results indicated that this precursor is suitable for the Sputter Coater) was operated in an argon atmosphere
preparation of activated carbon because of its high using a current of 6 mA for 3 min. The coated samples
carbon content and low ash content. were then transferred to the SEM specimen chamber
The durian seed was dried at 100 °C in an oven for and observed at an accelerating voltage of 20.00 kV.
12 h and subsequently crushed and sieved to a particle
size fraction of 500–710 μm. About 10–20 g of the RESULT AND DISCUSSION
resultant durian seed was impregnated with 85%
phosphoric acid to the desired acid to durian seed ratio, Characteristics of durian seed activated carbon
Xp, (weight of 85% H3PO4 used/weight of durian seed
used). The mixture was then subjected to low T600/R1/X2 seemed to be a mixed-type of I + II of
temperature treatment at 150 °C in the muffle furnace the BDDT classification [8]. This indicates that the
under the flowing of nitrogen at atmospheric pressure for carbon is mainly micro and mesoporous in character
2 h, and then final heat treatment at a temperature up to with a minor presence of wider pores where capillary
600 °C or 900 °C for 4 h with different heating rates. condensation occurred. T600/R1/X4 and T600/R1/X6
After the heat treatment, the carbon was cooled to room exhibited type II behaviour of the BDDT classification
temperature in the same flow of nitrogen. The excess which is indicative of the multiplayer adsorption
phosphoric acid was washed off by hot deionised water process due to the nonporous surfaces. The hysteresis
until the pH of the wash water became 6 which is the pH loop in the N2 adsorption/desorption isotherm indicates
of deionised water. After washing, the carbons were the presence of mesopores. Other biomaterials
dried at 105 °C for further analysis and characterization. converted into active carbons include; sugar beet pulp
The following parameters were varied: Xp (1, 2, 4, 6); activated with carbon dioxide with surface areas
2
heating rate (1 and 5 °C/min); activation temperature 200–900 m /g [9]; palm shell activated with potassium
2
(600 °C and 900 °C). Sample name, T600/R1/X2, means carbonate with surface areas 248–1170 m /g [10] and
that the activated carbon was produced at 600 °C with a rice bran activated with sulphuric acid with surface
2
heating rate of 1 °C/min and with Xp = 4. areas 200–700 m /g [11]. These BET values are lower
than the durian seed activated carbons produced in the
Characterization of textural properties present study.
Different methods can be employed to analyze
The textural properties of the adsorbents were the surface area and pore size distribution of porous
performed by determining the nitrogen solids. Although, the BET model has some limitations
adsorption/desorption isotherms at -196 °C using a for the surface area assessment, it is still used as a
Quantachrome Autosorb 1. The samples were degassed standard procedure for surface area determination as it

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38 Indo. J. Chem., 2010, 10 (1), 36 - 40

Table 1. Experimental conditions, yield, BET surface area (SBET), total surface area (Sα), micropore volume (Vmicro),
mesopore volume (Vmeso) and average pore diameter (Dp) of phosphoric acid activated carbon from durian seed.
Yield SBET Sα Vmicro Vmeso Dp
Sample 2 2 3 3
(%) (m /g) (m /g (cm /g) (cm /g) (nm)
T600/R1/X1 35.98 1559 1791 0.738 0.056 2.04
T600/R1/X2 38.85 2123 2147 0.586 0.904 2.80
T600/R1/X4 39.37 1410 1430 0.265 1.385 4.89
T600/R1/X6 38.03 1399 1422 0.140 1.801 5.32
T600/R5/X1 46.82 1129 1362 0.544 0.076 2.20
T600/R5/X2 44.58 1337 1403 0.342 0.738 3.27
T600/R5/X4 40.70 1198 1248 0.225 1.316 5.05
T600/R5/X6 40.57 1305 1338 0.209 1.598 5.39
T900/R5/X1 21.73 1474 1651 0.705 0.111 2.21
T900/R5/X2 17.00 1628 1659 0.374 0.997 3.38
T900/R5/X4 16.27 1356 1381 0.297 1.256 4.39
T900/R5/X6 15.57 697 694 0.156 0.727 4.18

Based on the observations on the shape of the

adsorption isotherm, the αs theory was used to
determine micropore volume and mesopore volume of
T600/R1/X1 which is a microporous carbon. The
mesopore volume can be calculated from the
subtraction micropore volume from the total pore
volume because the macropore volume is negligible for
a Type I isotherm which has a distinct plateau and the
total pore volume can be determined accurately at a
0
certain predetermined P/P (i.e. 0.97).
The αs method and the BJH method were applied
to estimate the micropore volume and mesopore
volume of T600/R1/X2, T600/R1/X4 and T600/R1/X6
which are mesoporous activated carbons. The αs
Fig 1. SEM images activated carbons at T600/R1/X2 method is not used to estimate the mesopore volume
as there is no distinct plateau on the adsorption
can give an accurate assessment of surface area in isotherm which indicates the presence of non-porosity
many types of adsorption isotherms if there is no or macroporosity in the activated carbon. The surface
significant primary micropore filling contribution and the area, micropore volume, mesopore volume, average
structure of the completed monolayer does not vary from pore size and the preparation conditions of phosphoric
one surface to another [1]. The αs method can provide acid activated carbons are summarized in Table 1.
more accurate assessment of higher surface area Scanning electron micrographs of the surface
instead of the BET method by comparison between the morphology of sample of the activated carbons are
test isotherm and the reference isotherm. Therefore, the given in Fig 1. This figure shows the external surfaces
surface area obtained from αs method can be used to of the activated carbons prepared at T600/R1/X2. From
check the surface area obtained from the BET method. this figures, it is obvious that the activated carbon has
For the pore size distribution analysis, the BJH cavities on their external surface. It seems that the
method has been widely used for mesopore analysis, cavities on the surfaces of carbons resulted from the
however, it is limited to only mesopores due to ambiguity evaporation of the activating agent in this case is
of the meniscus in the Microporous region [12]. phosphoric acid during carbonization, leaving the
Therefore, the αs method was also employed to estimate space previously occupied by the activating agent.
the micropore volume. The as method is a comparison
plot in which the amount adsorbed against standard data Effect of impregnation ratio
determined on a non-porous reference material and is a
common and safe method to determine the micropore The effect of impregnation ratio was studied using
volume. The surface area can be estimated from the carbons activated at 600 °C for 4 h at four different
slope of first linear section connecting to the origin and impregnation ratios ranging between 1 and 6. The
the micropore volume can be determined from the heating rate is 1 °C/min. The results show that the
intercept of the second linear section. surface area increased initially, reached maximum at

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 Indo. J. Chem., 2010, 10 (1), 36 - 40 39

Xp = 2 and then decreased. The total pore and paper. Previous work reporting surface area values
mesopore volume increased with the increase in only for durian seed carbons, include surface area
2
impregnation ratio but the micropore volume decreased values around 400–500 m /g [15], steam activation
2
with the increase in impregnation ratio. At Xp = 1, the produced values of 1038 m /g [16] but with alkaline
2
activated carbon is microporous, and developed into potassium hydroxide, surface area values of 1413 m /g
mesoporous when Xp increases. [17]. The last value is the highest value reported. In the
The porosity developed is due to the formation of present study using phosphoric acid, most surface
2
phosphate linkages such as phosphate and areas were greater than 1000 to over 2000 m /g with
polyphosphate esters which can serve to connect and mass recovery yields of 35–47% w/w.
crosslink biopolymers. These linkages expand the
structure of the durian seed and phosphate compounds CONCLUSION
retained in the expanded structure and hinder the
shrinkage at high temperature treatment. Activated A series of activated carbons has been produced
carbons prepared from pecan shell using phosphoric using durian seed as a raw material. A two step
acid activation showed a maximum BET surface area of process has been used, the first step is a low
2
900 m /g at an impregnation ratio of 1.5 [13]. temperature impregnation at 150 °C using phosphoric
acid and the second step is the carbonization at high
Effect of activation temperature temperatures, namely, 600 and 900 °C. Heating rate,
impregnation ratio and activation temperature are all
The effect of heating temperature was studied sensitive conditions for the surface area development.
using carbons activated at 600 °C and 900 °C. The For carbon producing at 600 °C, decreasing the
heating rate is 5 °C/min and the impregnation ratio used heating rate can increase the surface area. Increasing
is 2. It was found that the yield of activated carbon the impregnation ratio can increase the surface area
prepared at 900 °C is around 20% which is 20% lower initially and then decrease the surface area. For carbon
than the yield of activated carbon prepared at 600 °C. It production with a heating rate of 5 °C/min, increasing
was due to (i) the loss of most of the volatile matter, (ii) activation temperature can increase the surface area
the loss of phosphate compounds, and (iii) the resultant when the impregnation used is less than 4. The most
carbon volatilization once the formerly protecting outstanding carbon with the highest surface area of
2
phosphate compounds are lost. Under high activation 2123 m /g was prepared using an impregnation ratio of
temperature and high impregnation ratio, the porosity 2, an activation temperature of 600 °C for 4 h and a
and surface area decreased sharply as a considerable heating rate of 1 °C/min.
portion of phosphate compounds volatilise when the
temperature is above 800 °C. Although, it was found the REFERENCES
volatilization can produce new pores and increased
porosity at high activation temperature, this 1. Do, D.D., 1998, Adsorption Analysis: Equilibria and
enhancement may be limited only to the activated Kinetics, Imperial College Press, London, UK.
carbon with low impregnation ratio [13]. During the 2. Hu, Z. and Srinivasan, M.P., 1999, Microporous
production of activated carbons from cassava peel, Mesoporous Mater., 27, 11-18.
increasing temperature from 450 °C continually 3. Stavropoulos, G.G. and Zabaniotou, A.A., 2005,
increased surface area development from 972 to Microporous Mesoporous Mater., 83, 79-85.
2
1378 m /g [14]. 4. Mozammel, H.M., Masahiro, O., and Bhattacharya,
S.C., 2002, Biomass Bioenergy, 22, 397-400.
Effect of heating rate 5. Puziy, A.M. and Poddubnaya, O.I., 2005, Carbon,
43, 2857-2868.
Carbons were activated at 600 °C for 4 h at two 6. Hu, Z., Srinivasan, M.P., and Ni, Y., 2001, Carbon,
heating rates which are 1 and 5 ºC/min. The results 39, 877-886.
showed that a slower heating rate can enhance the 7. Kaneko, K., 1994, J. Membr. Sci., 96, 59-89.
development of microporosity and hence enhance the 8. El-Hendawy, A.N.A., 2003, Carbon, 41, 713-722.
development of surface area. The increase in surface 9. Mudoga, H.L., Yucel, H., and Kincal, N.S., 2008,
area at a lower heating rate may probably be due to the Bioresour. Technol., 99, 3528-3533.
longer contact time for the phosphoric acid and the 10. Adinata, D., Daud, W.M.A.W., and Aroua, M.K.,
biopolymer to react before the contraction temperature is 2007, Bioresour. Technol., 98, 145-149.
reached. There are very few references in the literature 11. Suzuki, R.M., Andrade, A.D., Sousa, J.C., and
referring to durian seed derived activated carbons Rollemberg, M.C., 2007, Bioresour. Technol., 98,
despite the encouraging results reported in the present 1985-1991.

Amri Ismail et al.

40 Indo. J. Chem., 2010, 10 (1), 36 - 40

12. Rouquerol, F., Rouqueol, J., and Sing, K., 1999, 15. Mizuta, K., Matsumoto, T., Hatate, Y., Nishihara,
Adsorption by Powders and Porous Solids, K., and Nakanishi, T., 2004, Bioresour. Technol.,
Academic Press, London, UK. 95, 255-257.
13. Guo, Y. and Rockstraw, D.A., 2007, Bioresour. 16. Wu, F.C., Tseng, R.L., and Juang, R.S., 1999, J.
Technol., 98, 1513-1521. Environ. Sci. Health A, 34, 1753-1775.
14. Sudaryanto, Y., Hartono, S.B., Irawaty, W., 17. Kim, Y.J., Lee, B.J., Suezaki, H., Chino, T., Abe,
Hindarso, H., and Ismadji, S., 2006, Bioresour. Y., Yanagiura, T., Park, K.C., and Endo, M., 2006,
Technol., 97, 734–739. Carbon, 44, 1592-1595.

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