ELEMENTAL AND PHYSICAL EFFECT OF CARBON FROM DATES FROND AFTER ACTIVATION BY PHOSPHORIC ACID

Norasyikin Mohd Mustapha 1, Abdul Rahim Yacob 1*, Hassan M Al Swaidan 2

1. Chemistry Department, Faculty of Science, Universiti Teknologi Malaysia, 81310 Skudai, Johor, Malaysia; 2. Chemistry Department, College of Science, King Saud University, P.O.Box 245, Riyadh, 11451, Saudi Arabia;

Received June 5, 2009; accepted September 9, 2009; published January 8, 2010. Abstract: Date frond, a low-cost agricultural by-product abundant in Saudi Arabia was used as a precursor for the production of
porous carbons by chemical activation using phosphoric acid. The developed surface morphology was studied using Thermogravimetry Analysis (TGA), Fourier Transform Infrared Spectroscopy (FTIR) and Single Point BET Surface Area. The result obtained from TGA indicates major weight loss is during heating before 400oC. In this study, thus this temperature was chosen to carbonize the date frond after the chemical activation using phosphoric acid (H3PO4) at various concentrations. FTIR results show that the sample is successfully converted from raw material to pure high surface area carbon. This study also shows that chemical activation at 60% H3PO4 gives the highest surface area of 1138.0 m2g-1. FESEM EDAX on the other hand shows that chemical activation will wash away some minerals during activation to create the high surface area activated. Key words: : Date fronds, Chemical activation, Phosphoric acid, Activated carbon, FESEM-EDAX.

1. Introduction
Saudi Arabia is one of the world largest exporters of dates. It is estimated that twelve million date-palm trees exist in Saudi Arabia. Every year, about three million trees were cut and pruned. Pruning process of dates tree is estimated to yield a flow of about 75,000 tons of fronds including thorn and foliar every year [1]. This has little economical value and are sometimes disposed off as waste or burnt and this might be harmful to the environment. The abundance and availability of agricultural by-product make them good source as the raw materials for activated carbon production. Activated Carbon (AC) is well known for high porosity and widely used as adsorbent, catalyst and support. They can be prepared from variety of precursor by chemical or physical activation. Previous study by Yacob et al, physical activation of frond, thorn and foliar, showed the presence of foreign materials during analysis [2]. Chemical activation on the other hand, consists of impregnation of the raw material with a strong dehydrating agent and then heating the mixture to form activated carbon. In this study, chemical activation is carried out using Saudi Arabia date frond waste using phosphoric acid. Advantage using phosphoric acid is that the activation temperature is relatively low 400oC, while the product yield is comparatively higher [3].
*Corresponding author: Abdul Rahim Yacob (1960), male, Ph.D., Assoc. Professor, Research field: Physical chemistry, Email: manrahim@kimia.fs.utm.my.

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The main objective of this study is to utilize date frond for the production of high surface area activated carbon by chemical activation with different concentration of H 3PO4 acid and to investigate the morphology and minerals after washing.

2. Experiment
The preparation of activated carbon involves selection of raw material, raw material analysis and preparation of activated carbon. 2.1 Selections of Raw Materials The raw material obtained was date-palm tree part after pruning, which consists of dates fronds from Riyadh, Kingdom of Saudi Arabia. The sample obtained was cut to small pieces of about 1 to 2 cm in size. 2.2 Raw Materials Analysis 2.2.1 Thermogravimetric Analysis. Thermogravimetric analysis (TGA) of dates fronds was carried using Mettler-TA 4000 Analysis. Approximately, 5 mg to 10 mg of the samples was heated from 40 to 900 oC with the heating rate 20oC per minute under controlled atmosphere of nitrogen flow. 2.3 Preparation of Activated Carbon 2.3.1 Phosphoric acid Activation effect on Surface 5 g of samples dates frond was weight and mixed with 15 ml of 10%, 20%, 30%, 40%, 50%, 60%, 70% and 80% H3PO4 acid respectively. After that, the samples were impregnated in muffle furnace at 110 oC for 1 hour. The process was then followed by activation for 3 hours at 400oC still in the furnace. Washing of prepared sample was carried to clean the acid content of the prepared activated carbon. The washing process was continued until pH 7 was attained. The samples were then dried in oven at 110oC to remove any moisture content. 2.4 Characterization Several techniques were used to characterize the prepared activated carbon. 2.4.1 Fourier Transform Infrared Spectroscopy (FTIR) analysis About 1 mg of the solid samples before and after activation was carried. The samples were grinded and milled with 100 mg potassium bromide (KBr) to form a fine powder. This powder was then compressed into a thin pellet less than 7 tons for 5 minutes. The sample was then analyzed using Shimadzu 8300 spectrometer and the spectrum was recorded in a spectral range of 400-4000 cm-1. 2.4.2 FESEM and EDAX analysis The FESEM analysis was employed to study the surface morphology and the porosity of the activated carbon. The surface morphology and element composition of the sample was analyzed using FESEM 6701F

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microscope with energy of 15.0 V couple with EDX analyzer. The grounded sample was sputtered on aluminium stub that covered with carbon cement tape. The stub was place into the vacuum chamber of FESEM instrument. The morphology scanning was done in different magnification to obtain clear images.

3. Results and discussion

3.1 Thermogravimetric analysis of Raw Materials Thermogravimetry analysis have been widely used to study the thermal behavior of agricultural by-products. This is therefore posible that thermal analysis would also make an important contribution to knowlegde of thermal behavior of biomass such as this date trees fronds. Figure 1 is the percentage weight loss during thermalgravimetry analysis for palm dates frond. This bar graph illustrate the weight lost that took place. The first range of decomposition happened at 100-200oC, which represent 2.68% weight lost and is most probably due to the surface moisture released by the sample during heating. Second is from 200-300 oC, which indicates further moisture, some bonded water and any light hydrocarbon. The major weight lost of about 38.26% then occurred at temperature range of 300-400oC. This is most probably represented by chemical bonded water and the break down or the decomposition of cellulose, hemicellulose and lignin to carbon. Futher heating above 400 oC with weight loss about 11.07% indicates the formation of volatile materials from the activated carbon produced, like CO and CO2 [2,4,5,6]. Thus, further heating will just reduce the quantity of pruducts of the high surface area carbon produced.
45 40 35 30 25 20 15 10 5 0

38.26

Weight Lost (%)

14.43 2.68 6.04 3.02 2.01

100-200

200-300

300-400

400-500

500-600

600-700

Temperature Range (C)

Fig. 1 Thermogravimetric analysis of date fronds

3.2 Fourier Transform Infrared Spectroscopy (FTIR) analysis Results from thermogravimetry analysis shows that any excess of activation temperature above 400 oC will transform the cellulose, hemicellulose and lignin to volatile materials [2]. Thus, for chemical activation the temperature use was kept contact at 400oC. Figure 2 shows the comparison FTIR spectra of raw date frond (Raw-DF), chemical activated carbon of date frond at 60% concentration of H 3PO4 acid (AC-60%) and commercial activated carbon (AC-C) for comparison.

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Raw date frond (DF) in Figure 2 shows the most complicated and apparent spectrum. A strong and broad adsorption peak appeared at 3434.06 cm-1, which corresponds to the stretching of O H functional group and this indicates the presence of bonded hydroxide in the raw sample. There was another peak observed at 2930.44 cm-1 corresponding to the C H sp3 stretching. A strong conjugated C=C peak also observed around 1633.83 1638.32 cm-1. This sample also shows four important absorption peaks at 1251.06, 1160.53, 1113.89 and 1053.53 cm-1 respectively which represent the stretching of C O functional group. From the spectrum, it can be suggested that the main oxygen groups present in the raw-DF are carbonyl, ethers and alcohols group which are normally present in plant cellulose.

Fig. 2

FTIR Spectra for (a) Raw-DF, (b) AC-60%, (c) AC-C

In contrast to the FTIR spectrum shown by raw -DF, the spectrum AC-60% and AC-C illustrate less absorption peaks, clearly, most of the absorption peaks of functional groups were diminished. Although the samples were prepared both by different activation methods, there seem similarities in the vibration patterns. Basically all the samples show a weak broad peak around 3425.12 3440.32 cm-1, which indicates the presence of hydroxide group in the samples. It is most probably of the R-OH bonded like molecule in carbon.
Table 1 Sample Raw Date Fronds Wave number of some functional groups present in the samples Wave Number (cm-1) 3434.06 2930.44 1635.58 1251.06,1160.53, 1113.89, 1053.53 AC-60% AC-C 3425.12 3430.56 O H stretching O H stretching Functional Group O H stretching C H (sp3) stretching C = C (conjugated) stretching C O stretching

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Finally, the spectra for the prepared activated carbon from dates frond chemical activated at 60% phosphoric acid when comparable to the commercial activated carbon, there seem a great similarity. This might indicate that the prepared activated carbon is of similar in grade and standard of that the commercial prepared carbon. The functional groups present in the samples were tabulated in Table 1. 3.3 Influence of the H3PO4 Concentration on Surface In this study, the surface area for the raw date fronds was only 4.6 m2g-1. Figure 3 illustrate the surface area of activated carbon produced at different concentration of H3PO4 acid. It was shown that the surface area of activated carbon produced increase with the increases of phosphoric acid concentration. It may be spaculated that higher acid concentration, would enhance porosity development. From the graph, it shows that the highest surface area, 1139m2g-1 of activated carbon produced is belong to 60% of H3PO4 (AC-60%) acid used during the activation process. A decrease in surface area is noticed at 70% and 80% H3PO4 acid, which may attributed to the rupture of activated carbon morphology and also the formation of a layer of polyphosphate (a skin) over the developing pore structure protecting it from excessive gasification. This result is supported by Girgis, which indicate that higher acid concentration were not accompanied by a respective improvement in porosity, however collaption of the structured pore of the activated carbon. The washing process on the activated carbons produced play important role of porosity evolution. After activation, most of the activant is still in the particle and intense washing to eliminate it produces the porosity. It was found by Girgis that there is a good agreement between the volume of micropores and the volume occupied by the acid phase existing at the activation temperature. The entrapped polyphosphates in the final product will appear in the form of high ash content as well as impart an acidic character on the carbon product. The high content of ash will be responsible lower the surface area of activated carbons produced. Finally, to overcome this, washing process was done until pH 7 is achieved which indicate all the acid content were successfully removed from the activated carbon.

Fig. 3

Single point BET surface area of activated carbon at different concentration of H 3PO4

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3.4 FESEM analysis The FESEM micrographs provide information on the structural changes in the palm date frond for anatomy during the activation process. Figure 4 shows raw palm date frond (R-PDF) before and after activation. Figure 4 (a) shows the micrograph of R-PDF at 500x magnification. The surface of R-PDF is curly form resulted from the presence of cellulose, hemicelluloses and lignin in the raw material without any cracks and crevices. This would account for its poor or negligible BET surface area.

(a)
Fig. 4

(b)
FESEM of (a) R-PDF and (b) AC-60% H3PO4 Acid

The framework development was so rapid in Figure 4 (b), resulting in too much cavities and leads to crack formation. Due to this well developed pores, the AC-60% possessed high BET surface area. Figure 4 (b) shows the micrograph of AC-60% at 5000x magnification. The micrograph magnifies the internal cavities, which are now clearly visible. Direct measurement from the micrograph shows that the average pore diameter is 5.23 m. The surface of the AC-60% seems to be clearer and smoother than R-PDF surface due to the removal of volatile compounds and impurities during the activation process and followed by phosphoric acidwash. It can bee seen that there are solid appeared in the pores of AC-60% where some small white particles are scattered on the surface of the carbon, probably due to the residue of the activating agent, phosphoric acid which was not washed all out during the activation process. 3.5 EDAX analysis Energy Dispersive X-ray (EDX) analysis was carried out on the surface of activated carbons. The value or the data obtained with EDX analysis is only a rough estimation of the surface elemental composition. It should not be regarded as an absolute composition of the activated carbon. The results on surface composition of EDAX for raw R-PDF and activated carbon AC-60% samples was shown by Figure 5 (a) and (b) respectively, while the elemental before and after washing is tabulated by Table 1. Figure 5 (a) shows, before activation, raw materials contain the highest amount of elements other than carbon, such as oxygen, sodium, magnesium, silica, chlorine and etc. These elements however, are washed and diminished during the chemical activation process. EDAX analysis in Figure 5 (b), shows that after the activation
6

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process, there present only four elements comprising of carbon (77.3%), oxygen (20.6%), silica (0.2%) and phosphorus (1.8%) respectively. In Table 2, the appearance of phosphorus elements after activation can be explain by the use of phosphoric acid as the activating agent in the activation process. Thus, the phosphate ions in the carbon come from the phosphoric acid used. (a)
016 2400 2100 6400 1800
Counts

(b)
011 8000

7200

O
Counts

5600 4800 4000 3200 Cl Pt Cl K Ca K Ca Pt Cu 2400 Cu Pt 1600 800 0 O Si P

1500 1200 900 600 300 0 0.00 1.00 2.00 3.00 4.00 5.00 keV 6.00 7.00 8.00 9.00 10.00 Cu Cu Mg Pt Na Si Pt

0.00

0.80

1.60

2.40

3.20

4.00 keV

4.80

5.60

6.40

7.20

Fig. 5

EDAX (a) before and (b) after activation using H3PO4 Acid

Table 2: Elemental Analysis before and after Chemical Activation using H 3PO4 Acid Elements C O Na Mg Si Cl K Ca Cu Pt P Before Washing % 59.17 34.66 0.32 0.4 0.29 1.34 0.91 0.64 0.96 1.32 After Washing % 77.28 20.64 0.2 1.87

4. Conclusions
The TGA results demonstrate that the best temperature for activation is 400C and any temperature above might affect the product activated carbon. Single point BET surface area for the activated carbons prepared via different concentration of phosphoric acid indicate AC-60% shows the highest surface area of 1139 m2g-1 compared to the raw date fronds of only 4.6 m2g-1 which is slightly better to the commercial activated carbon. Finally, high surface area carbon can be obtain by washing with phosphoric and also purify the activated carbon.

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Acknowledgments
The work was funded by the Engineering and Physical Science Research Council.

References
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