Develop Activated Carbon from Rice Husk by Using Acid Hydrochloric (HCL) K. L.

Chong School of Civil Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, MALAYSIA. Email: catherine_cho28@yahoo.com

Abstract Rice husk is a by-product of rice milling process and are a major waste product of the agricultural industry. Rice husk ash is the natural sheath that forms on rice grains during their growth and it has no commercial value.Rice husk is low cost raw material and it can be activated as carbon precursor as a solution to reduce the agricultural waste. An effort was made to produce an activated carbon precursor from the rice husk an agricultural waste and acid hydrochloric (HCL). The effects of different preparation parameters which were activation temperature and impregnation ratio were investigated. Various reaction temperatures and impregnation ratio were used to obtain the best removal efficiency and surface area. The optimum activation temperature at impregnation ratio 1.0 is 600C. By referring to BET, specific surface area that success obtained at 600C is the highest among the others which is 164.6m2/g and micropore volume is 0.05578cm3/g. Based on the analysis data shows activation temperature and impregnation ratio strongly affect the characteristics of rice husk activated carbon. Keywords: Rice husk, activated carbon, acid hydrochloric, surface area.

1.0 Introduction Activated carbon (AC) defined as a porous highly adsorptive form of carbon used to remove colour or impurities from liquids and gases, in the separation and extraction of chemical compounds, and in the recovery of solvents. The basis for modern industrial production of active carbons was established in 19001901 to replace bone char in the sugar refining process (Bansal et. al, 1988). Powdered activated carbon was first produced commercially in Europe in the early 19th century, using wood as a raw material. The use of activated carbon for the water treatment in the United States was first reported in 1930, for the elimination of taste and odor from contaminated water (Mantell et. al, 1968). Activated carbon is a crude form of graphite with a random or amorphous structure, which is highly porous, exhibiting a broad range of pore

sizes, from visible cracks, crevices and slits of molecular dimensions (Hamerlinck et. al, 1994). Active carbons have been prepared from coconut shells, wood char, lignin, petroleum coke, bone char, peat, sawdust, carbon black, rice hulls, sugar, peach pits, fish, fertilizer waste, waste rubber tire, etc. (Table 1.1). Wood (130,000 tonnes/year), coal (100,000 tonnes/year), lignite (50,000 tonnes/year), coconut shell (35,000 tonnes/year), and peat (35,000 tonnes/year) are most commonly used (Pollard et. al, 1992). Activated carbons adsorptive properties are due to such factors as surface area, a micro-porous structure, and a high degree of surface reactivity. Activated carbon surfaces have a pore size that determine its adsorption capacity, a chemical structure that influences its interaction with polar and non-polar adsorbents, and active sites
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which determine the type of chemical reactions with other molecules. Due to their adsorption properties, Activated Carbons are used for the removal of a wide range of pollutants from wastewaters, such as heavy metals, phenols, dyes and other polar and nonpolar organic substances. (Khalderis, 2008) In addition, AC has been demonstrated to have excellent effectiveness in the removal of organic matter and nitrogenous substances in landfill leachates. Landfill leachate might have negative impact on the domestic wastewater treatment system, as leachate is a highly concentrated wastewater both in terms of inorganic and organic pollutants. A recent research revealed that the negative impact of leachate on a municipal wastewater treatment system could be prevented by the addition of PAC (powdered activated carbon). Abundant of agricultural byproducts such as sugarcane bagasse, rice straw, soybean hulls, rice hulls, and nutshells are lignocellusic wastes that may offer an inexpensive and renewable additional source of activated carbon (Ahmedna, 2000). Rice husk ash is the natural sheath that forms on rice grains during their growth and it has no commercial value. In Malaysia, rice husk is produced in abundance after every paddy harvesting season and contributes to major agricultural waste. According to the statistics compiled by the Malaysian Ministry of Agriculture, there are 408,000tonnes of rice husk produced in Malaysia (Chuah et. al, 2005; MOG, 2011). The husks are eliminated by burning them in the field at high temperature leaving behind a white blackish powder which is the constituents of silica. The presence of the silica ash

causes a number of problems to the environment that causes pollution and disposal problems because of its nonbiodegradable property. In the past, rice husk was mostly dumped as waste that caused waste disposal problem for the mills. Also, when rice husk is fermented by microorganisms, methane is emitted contributing to global warming problem. Rice husk is a fine and light particle and can cause breathing problems (Chungsangunsit et al, 2004). The objectives of my study are to develop activated carbon from rice husk and determine the characteristics of activated carbon developed. Besides, I also investigate the optimal condition such optimum temperature with different impregnated ratio and adsorption efficiency of activated carbon. 2.0 Experimental 2.1 Materials The materials used in this investigation are rice husk (Bernas Kuala Perlis), 3M acid hydrochloric. The rice hull as received was first washed with distilled and deionized water and dried in oven at 105C for one day. This process was taken in order to void parallax error including effect of moisture during carbonization. As in the same time during this stage the other bigger size of contaminant such stone or trap insect also been removed. 2.2 Preparations The activation process as the 100g rice husks was then impregnated with 3M acid hydrochloric, at temperature 105C with 24hours in oven (Model Memmert 600, Germany). This action is a dehydrating purpose. The effects of different carbonized temperature effect and impregnation ratio were observed. For
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the carbonization process, temperatures that been used were 500C, 600C, and 700C with soaking time 1 hour and nitrogen gas used to cooled activated carbon to room temperature. Sample was taken out from the reactor and washed sequentially several times with hot distilled water in order to eliminate the residual organic and mineral matter. Washing with water easily removed most of residues from activating agent. The completion of washing was done when the final pH of washing water was neutral. It was then dried at 105 C for 24 hour and stored in air tight bottles for further tests. 2.3 Characterization 2.3.1 Surface Area (BET) The N2 adsorption-desorption isotherms of the activated carbon were measured using an automatic adsorption instrument (AutoSorb 1, Quantachrome) at liquid nitrogen temperature (77K). The specific surface areas (SBET) of the activated carbon were calculated using the Brunauer-Emmett-Teller (BET) equation by assuming the area of the nitrogen molecule to be 0.162nm2. The micropore volume and microporous surface area were determined by the t-plot method (LopezRamon et al., 1999). The determination of the specific surface of powdered substances is based on a low temperature gas absorption process introduced by Brunauer, Emett and Teller (BET) model AutoSorb 1, Quantachrome was used to measure the specific surface of powder solid. A defined amount of sample is weight into a tubular glass cuvette. Using a closed apparatus, the sample is then continuously gassed with a mixture of 30% nitrogen and 70% helium. After that, the sample is immersed into a dewar jar containing liquid nitrogen

and cooled down to -196C. This process is accompanied by the formation of monomolecular nitrogen layer on the surface of analyze. Once the equilibrium state is reached complete desorption is induced by heating the sample. The amount of nitrogen set free is quantitatively determined with the aid of thermal conductivity determined with aid of thermal conductivity detector and converted into a surface on basis of the BET equation. 2.3.2 Morphology (SEM)

Scanning Electron Microscopy (SEM) model JEOL JSM-6460LA was used to observe the morphology. The magnification used were 1000x, 5000x and 10000x. The SEM create magnified images by using electron instead of light waves and shows very detail 3-dimentional images at higher magnification than possible with light microscope. The image that created were in white and black form depend on the density of the material been observe. The sample needs to be prepared carefully to withstand the vacuum inside the microscope. Due to the fact that the SEM analysis illuminates with electron, they also need to be coated with thin layer of gold-palladium. The microscope is then place inside the microscope vacuum column through an air tight door. After the air was pump out of the column, an electron gun at the top emits a beam of high energy of high- energy electron. The elemental compositional test also been done. 4.0 Results and discussion 4.1 Characteristics of Activated Carbon The The BET (Brunauner, Emmett, and Teller) isotherm assumes the partitioning of a compound between liquid and solid phases. This isotherm assumes multi-layer adsorption of solute occurs (Weber, 1972; Brunauner et al., 1972).
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Various sorbents have been compared based on percent removal. This is a crude and rather inaccurate misleading approach. Isotherms are always (Langmuir) more accurate than percentage removal to compare two sorbents because isotherms have more experimental points.
Table 4.1: BET result for activation temperature 500C, impregnation ratio 1.0. Surface Area Data Multi Point BET Langmuir Surface area t-method external surface area DR method micropore area 47.93 m2/g 111.1 m /g 47.93 m /g 68.75 m /g
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Pore Size Data Average pore Diameter DR method micropore Pore width DA method pore Diameter (Mode) HK method pore Diameter (Mode) SF method pore Diameter (Mode) 2.118 nm 2.535 nm 1.360 nm 0.3675 nm 0.4523 nm

Table 4.3: BET result for activation temperature 700C, impregnation ratio 1.0. Surface Area Data Multi Point BET Langmuir Surface area t-method external surface area t-method micropore surface area DR method micropore area 67.81 m2/g 107.1 m2/g 23.27 m2/g 44.53 m2/g 105.1 m2/g

Pore Volume Data Total pore volume for pores with Diameter less than 2.57nm at 0.01934 cc/g 0.02443 cc/g 0.01236 cc/g 0.01313 cc/g

Pore Volume Data Total pore volume for pores with Diameter less than 2.60nm at 0.03625 cc/g 0.02466 cc/g 0.03736 cc/g 0.03412 cc/g 0.03441 cc/g

P/P0=0.297781 DR method micropore volume HK method cumulative pore volume SF method cumulative pore volume

P/P0=0.302030 t-method micropore volume DR method micropore volume HK method cumulative pore volume SF method cumulative pore volume

Pore Size Data Average pore Diameter DR method micropore Pore width DA method pore Diameter (Mode) HK method pore Diameter (Mode) SF method pore Diameter (Mode) 1.614 nm 6.670 nm 2.600 nm 0.3675 nm 0.4523 nm Pore Size Data Average pore Diameter DR method micropore Pore width DA method pore Diameter (Mode) HK method pore Diameter (Mode) SF method pore Diameter (Mode) Table 4.2: BET result for activation temperature 600C, impregnation ratio 1.0. Surface Area Data Multi Point BET Langmuir Surface area t-method external surface area t-method micropore surface area DR method micropore area 164.6 m2/g 258.9 m2/g 63.25 m2/g 101.3 m2/g 253.7 m2/g 2.138 nm 2.407 nm 1.320 nm 0.3675 nm 0.4523 nm

Pore Volume Data Total pore volume for pores with Diameter less than 2.58nm at 0.08715 cc/g 0.05578 cc/g 0.09017 cc/g 0.08152 cc/g 0.08229 cc/g

P/P0=0.299194 t-method micropore volume DR method micropore volume HK method cumulative pore volume SF method cumulative pore volume

Table above show data obtained from BET for activated carbon with impregnation ratio 1.0 and different activation temperature. Refer to the Table 4.1, 4.2 and 4.3 shows that surface area increase proportional to the activation temperature. However, at activation temperature 700C, surface area gradually decreasing which is from 164.4m2/g to 67.81m2/g. From this, it can be conclude that at impregnation ratio 1.0, activation temperature 600C is the optimum and provide the best surface area. It was found that low heating temperature could not sufficiently produce activated carbon with pre-developed porosity.

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SEM image of Rice husk raw with magnification of on 1000X.

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SEM image of Rice husk activated with temperature 500C, impregnated ratio 3.0 with magnification of on 1000X.

5.0 Conclusions In conclusion, the experimental result shows activation temperature and impregnation ratio strongly affect the characteristics of rice husk activated carbon. The optimum activation temperature at impregnation ratio 1.0 is 600C. By referring to BET, specific surface area that success obtained at 600C is the optimum compared to the others which is 164.6m2/g and micropore volume is 0.05578cm3/g. References 1. Ahmedna, M., Marshall, W. E., Rao, R. M. (2000). Production of granular activated carbons from select agricultural by-products and evaluation of their physical, chemical and adsorption properties. 71, 113-123. 2. Bansal, R.P., Donnet, J.P., Stoeckli, F. (1988). Activate Carbon. New York: Marcel Dekker Inc. 3. Brunauner, S., Emmett, S.P.H., Teller, E. (1972). Adsorption of Gases in 11. 8.

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Multi-molecular Layers. Journal of Am. Chem. Soc, 60, 309-319. Chuah, T. G., Jumasiah, A., Azni, I., Katayon, S., Thomas, C. (2005). Rice Husk As A Potentially Low Cost Biosorbent for Heavy Metal and Dye Removal: An Overview. Desalination, 175, 305-316. Chungsanggunsit, T., Gheewala, S.H., Patumsawad, S. (2004). Environmental Assessment of Electricity Production from Rice Husk: A Case Study in Thailand. Electricity Supply Industry in Transition: Issues and Prospect for Asia, 51-62 Hamerlinck, Y., Mertens, D.H. (1994). Activated Carbon Principles in Separation Technology. Kalderis, D., Koutoulakis, D., Paraskewa, P., Diamadopoulos, E. (2008). Adsorption of Polluting Substances on Activated Carbons Prepared from Rice Husk and Sugarcane Bagasse. Chemical Engineering Journal, 144, 42-50. Lopez-Ramon, M. V., Stoeckli, F., Moreno-Castilla, Carrasco-Marin, F. (1999). On the Characterization of Acidic and Basic Surface Sites on Carbons by Various Technique. Carbon, 37, 1215-1221. Mantell, C. L. (1968). Carbon and Graphite Handbook. New York: Interscience. Pollard, S. J. T., Fowler, G.D., Sollars, C.J., Perry, R. (1992). Low Cost Adsorbents for Waste and Wastewater Treatment: A Review. Sci. Tot. Environ, 116, 31-52. Weber Jr, W. (1972). In Physicochemical Processes for Water Quality Control (pp. 207-270). New York: Wiley Interscience.