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International Journal of Chemical Engineering and Applied Sciences

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ISSN 2278 1366 Original Article ADSORBENTS FROM KARANJA SEED OIL CAKE AND APPLICATIONS
ASHISH S. SAKSULE, PALLAVI A. KUDE. Department of Chemical Engineering, NBA Re-Accredited SSBTS College of Engineering & Technology, Bambhori, Jalgaon. (M.S.) Affiliated To NORTH MAHARASHTRA UNIVERSITY, JALGAON (M.S.) (NAAC Re-Accredited B Grade) (2011-2012) Email: ashishsaksule@gmail.com, pearlkude@gmail.com Received 28 June 2012; accepted 07 September 2012 Abstract Activated Carbon is predominantly amorphous solid that has extraordinary large internal surface area and pore volume. These unique pore structures play an important role in many different liquid and gas phase applications because of their association with adsorptive properties. Although most types of industrial activated carbons are produced from naturally occurring carbonaceous materials such as coal, wood and coconut shells by activation Process. Here some Agro-industrial by-products can be used as precursor material for preparing activated carbons in the laboratory. Karanja Seed Oil Cake is by-product after oil extraction, which otherwise goes waste or as fertilizers, is used as Precursor for Activated Carbon Preparations. Adsorbent from Karanja seed oil cake is prepared in laboratory by various Chemical and Physical Activation Processes and is studied for adsorptions of Dyes and Waste Water Treatment. 2011 Universal Research Publications. All rights reserved decomposition of the raw material impregnated with certain Objectives of the Research The aim of this research is to produce activated carbon activating agents. from the local agricultural waste which is Karanja Seed oil After the impregnation step, the samples were carbonized Cake. To achieve these, a study was carried out with the in the horizontal furnace by varying the operating parameter such as carbonization temperature and following objectives: i. To evaluate various operating parameters such as carbonization time. activation temperature and activation time for the The carbonization temperatures of this activation were activated carbon produced from Karanja Seed oil varied between 300 to 500 C to analyze the effect of temperature on the yield and pores development of Cake. activated carbon. ii. To study the effect of chemical activation on the This work also focuses on optimizing the activation time, development of pore structure on the activated carbon instead to optimizing the activation temperature. The raw produced. materials that have been activated will be carbonized under iii. To examine the characteristic of granular activated certain temperature with control time of 0.5, 1, 2, 3, 4 carbon produced (i.e. elemental analysis, proximate hours. After carbonization, the activated carbons produced analysis, adsorption capacity, surface functionality and were washed with water several times until the residual pore size of AC produced). activating agent on the surface of activated carbon iv. To evaluate the potential application of locally completely removed. (Till Constant pH).This stage was produced activated carbon in inorganic pollutants such important because during impregnation the activating agent as its performance in Dye Removal, Waste Water will penetrate into raw material particles and occupied Treatment. substantial volumes. Once they were extracted by intense washing, a large Scope of the research In this research, the production of activated carbon was amount of micro porosity was created. carried out by using chemical activation method. In In order to analyze the activated carbon produced, several chemical activation, the carbonization and activation are standard analyses were employed to characterize the accomplished in a single step by carrying out the thermal product that will meet the condition for commercialization. International Journal of Chemical Engineering and Applied Sciences 2012; 2(3): 13-23

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The characterization of the activated carbon produced were performed by using several analyses such as the elemental analysis, proximate analysis, pore size analysis, surface functional groups analysis and adsorption capacity. 2. INTRODUCTION The annual harvest and processing of various crops in India yield considerable amount quantities of agricultural byproducts. There are no reliable production statistics of crops in India and no data exist on the quantities of byproducts generated by these crops. Typical crops capable of yielding large quantities of byproducts are given in Table 1 [1]. These agricultural by-products have little are no economic value and present environmental disposal problems. Abundance and low cost of agricultural byproducts make them suitable precursors of activated carbon. Conversion of these agricultural by products into carbonaceous adsorbents would add value to these agricultural commodities, and provide a cheap alternative to existing commercial carbonaceous adsorbents. Table 1: Typical crops and by-products for use as adsorbent materials Crops By-products Karanja Seed cake Maize Cob, stalk Melon Seed husk Groundnut Husk Coconut Shell , coir Rice Husk Rubber Seed shell 2. 1KARANJA SEED PLANT. Non-edible oils like jatropa, Karanja and mahua contain 30% or more oil in their seed, fruit or nut. India has more than 300 species of trees, which produce oil bearing seeds. Milletiapinnata is a species of tree in the pea family, Fabaceae, native in tropical & temperate Asia including parts of India, China, Japan, Malaysia, Australia & Pacific islands [5, 6]. It is often known by the synonym Pongamiapinnata and it was moved to the genus Milletia only recently. Pongamiapinnata is one of the few nitrogen fixing trees (NFTS) to produce seeds containing 30-40% oil. It is often planted as an ornamental and shade tree but now-a-days it is considered as alternative source for BioDiesel. This species is commonly called pongam, Karanja, or a derivation of these names. It is a legume tree that grows to about 1525 meters (1580 ft.) in height with a large canopy which spreads equally wide. It may be deciduous for short periods. The leaves are soft, shiny burgundy in early summer and mature to a glossy, deep green as the season progresses. Flowering starts in general after 34 years. Cropping of pods and single almond sized seeds can occur by 46 years. Small clusters of white, purple, and pink flowers blossom on their branches throughout the year, maturing into brown seed pods. The tree is well suited to intense heat and sunlight and its dense network of lateral roots and its thick, long taproot make it drought-tolerant. The dense shade it provides slows the evaporation of surface water and its root nodules promote nitrogen fixation, a symbiotic process by which gaseous nitrogen (N2) from the air is converted into ammonium.

Fig 1 : Karanja Tree with fruits 2.1 Uses 2.1.1 Wood: Pongam is commonly used as fuel wood. Its wood is medium to coarse textured. However, it is not durable, is susceptible to insect attack, and tends to split when sown. Thus the wood is not considered a quality timber. The wood is used for cabinet making, cart wheels, agricultural implements, tool handles and combs (GOI 1983). 2.1.2 Oil: A thick yellow-orange to brown oil is extracted from seeds. Yields of 25% of volume are possible using a mechanical expeller. The oil has a bitter taste and a disagreeable aroma, thus it is not considered edible. In India, the oil is used as a fuel for cooking and lamps. The oil is also used as a lubricant, water-paint binder, pesticide, and in soap making and tanning industries. The oil is known to have value in herbal medicine for the treatment of rheumatism, as well as human and animal skin diseases. It is effective in enhancing the pigmentation of skin affected by leucoderma. The oil of Pongam is also used as a substitute for diesel. 2.1.3 Fodder and feed: The leaves are eaten by cattle and readily consumed by goats. However, in many areas it is not commonly eaten by farm animals. Its fodder value is greatest in arid regions. The oil cake, remaining when oil is extracted from the seeds, is used as poultry feed. 2.1.4Medicinal properties: Although all parts of the plant are toxic and will induce nausea and vomiting if eaten. The fruits and sprouts, along with the seeds, are used in many traditional remedies. Juices from the plant, as well as the oil, are antiseptic and resistant to pests. Like, neem oil, it is excellent for skin and hair and used in the manufacture of soaps, creams, lotions and other skin and hair care products. A mixture containing equal amounts of neem and Karanja oil is very effective on animals for skin problems. 2.1.5 Other uses: Dried leaves are used as an insect repellent in stored grains. The oil cake, when applied to the soil, has pesticidal value, especially against nematodes and also improves soil fertility. Pongam is often planted in homesteads as a shade or ornamental tree and in avenue plantings along roadsides and canals. It is a preferred species for controlling soil erosion and binding sand dunes because of its dense network of lateral roots. Its root, bark,

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leaf, sap, and flower also have medicinal properties. The oil of the Karanja or Pongam is used in pharmacy and in agriculture. The wood is said to be beautifully grained but splits easily when sawn thus relegating it to firewood, posts, and tool handles. Its dense network of lateral roots makes this tree ideal for controlling soil erosion and binding sand dunes. 2.2 ACTIVATED CARBON The process of preparing activated carbons involves activation and carbonization of the precursor material. Activation can be a physical process with the use of carbon dioxide, steam or ammonia as activating agents, or a chemical process employing activating agents such as phosphoric acid, zinc chloride or potassium salts[2] During the activation process, the spaces between the elementary crystallites become cleared of less organized, loosely bound carbonaceous material [1]. The resulting channels through the graphitic regions, together with fissures within and parallel to the graphitic planes constitute the porous structure with large internal surface area [3]. The extensive use of activated carbon is generally attributed to the large surface area, which can attain values up to 2000m2/g, making it a powerful adsorbent [1]. Thus activated carbons are commonly used in water and wastewater treatment, in food processing industry, and in pharmaceutical purification. The objectives of this project include the preparation and determination of surface area of the powdered activated carbon from Karanja oil seed cake, using ammonium chloride as chemical activating agent and evaluation of the pH of the activated carbon. 2.2.1. Activated carbon Activated carbon (AC) is the carbonaceous material which plays an important role in adsorption process. Its ability to remove organic and inorganic chemical waste, odor, color and taste from any kind of chemical industry process is based on their amazing properties. Activated carbon has high degree of surface reactivity which can influence its interaction with polar or no polar adsorbents. Besides, it also has higher surface area and micro porous structure. Activated carbon are widely use in wastewater treatment to remove harmful chemicals and heavy metal, industrial waste water or industrial flue gas. Their application in industry includes removing organic and inorganic pollutants from drinking water, industrial wastewater treatment, decolorizing of syrups and purification of air and pharmaceutical product. Because of their wide usage in industry, the demand of the activated carbon is increasing year by year. Commercial activated carbon is quite expensive. As such industry now seeks for the cheapest activated carbon derive from agriculture waste or residuals. The residuals can be seed cakes rice husk, sawdust or other carbonaceous material. The raw material were processed and optimized to obtain excellent adsorptive properties. 2.2.2 Definition of Activated Carbon Activated carbon is the carbonaceous material that is very effective adsorbents for organic compounds. Activated carbon is versatile adsorbents. It can be produced from carbonaceous material in order to provide adsorptive properties. The adsorptive properties depend on their high

surface area, micro porous structure and high degree of surface reactivity. The chemical structure on the carbon surface will influence the interaction between polar and nonpolar adsorbates. Activated carbon can be used to adsorb organic and inorganic species either from gaseous and aqueous phases. Activated carbons properties depend on: 1. Chemical and porous structure of carbon (nature and concentration of surface chemical groups). 2. The polarity of the surface. 3. The carbon surface area. 4. Pore size distribution. 5. Physical and chemical characteristics of adsorbents.

Activation of the compound Activated carbon is carbon produced from carbonaceous source materials like nutshells, peat, wood, biomass, lignite, coal and petroleum pitch. It can be produced by one of the following processes: 1. Physical Reactivation: The precursor is developed into activated carbons using gases. This is generally done by using one or a combination of the following processes: Carbonization:Material with carbon content is pyrolyzed at temperatures in the range 600900 C, in absence of oxygen (usually in inert atmosphere with gases like argon or nitrogen) Activation/Oxidation:Raw material or carbonized material is exposed to oxidizing atmospheres (carbon monoxide, oxygen, or steam) at temperatures above 250 C, usually in the temperature range of 600 1200 C. Chemical activation: Prior to carbonization, the raw material is impregnated with certain chemicals. The chemical is typically an acid, strong base, or a salt (phosphoric acid, potassium hydroxide, sodium hydroxide, ammonium chloride, respectively). Then, the raw material is carbonized at lower temperatures (450900 C). It is believed that the carbonization / activation step proceeds simultaneously with the chemical activation. Chemical activation is preferred over physical activation owing to the lower temperatures and shorter time

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needed for activating material. The adsorption process depends on the following factors: 1. Physical properties of activated carbon , such as pore size distribution and surface area; 2. The chemical nature of the carbon source, or the amount of oxygen or hydrogen associated with it; 3. Chemical composition and concentration of the contaminants. 4. The flow rate or exposure time of the contaminants to the activated carbon 5. The temperature and pH of the water. Physical properties The amount and distribution of the pores play key role in determining how well contaminants are filtered. The best filtration occurs when pores are barely large enough to admit contaminant molecules. As contaminants come in different sizes they are attracted differently depending on the pre size of filter. Chemical properties The filter surface may actually interact chemically with organic molecules. Also electrical forces between the activated carbon surface and some contaminants may result in adsorption or ion exchange. Adsorption is also affected by the chemical nature of the adsorbing surface. The chemical properties of the adsorbing surface are decided by large extent by the activation process. Activated carbon material are formed from different activation processes will have chemical properties that make them more or less attractive to various contaminants .for example, chloroform is adsorbed best by activated carbon that has the least amount of oxygen associated with the pore surfaces[6]. Exposure time The process of adsorption is also influenced by length of time that the activated carbon is in contact with contaminants in the water. Increasing contact time allows greater amount of the contaminant t be removed by increasing the amount of activated carbon in the filter and reducing the flow rate of water through the filter. 3. CLASSIFICATION Activated carbons are complex products which are difficult to classify on the basis of their behavior, surface characteristics and preparation methods. However, some broad classification is made for general purpose based on their physical characteristics. 3.1 Powdered activated carbon (PAC) Active carbons are made in particular form as powders or fine granules less than 1.0 mm in size with an average diameter between .15 and .25 mm. Thus they present a large surface to volume ratio with a small diffusion distance. PAC is made up of crushed or ground carbon particles, 95100% of which will pass through a designated mesh sieve or sieve. Granular activated carbon is defined as the activated carbon being retained on a 50-mesh sieve (0.297 mm) and PAC material as finer material, while ASTM classifies particle sizes corresponding to an 80mesh sieve (0.177 mm) and smaller as PAC. PAC is not commonly used in a dedicated vessel, owing to the high head loss that would occur. PAC is generally added directly to other process units, such as raw water intakes, rapid mix basins, clarifiers, and gravity filters.

3.2 Granular activated carbon (GAC) Granular activated carbon has a relatively larger particle size compared to powdered activated carbon and consequently, presents a smaller external surface. Diffusion of the adsorbate is thus an important factor. These carbons are therefore preferred for all adsorption of gases and vapors as their rate of diffusion are faster. Granulated carbons are used for water treatment, deodorization and separation of components of flow system. GAC can be either in the granular form or extruded. GAC is designated by sizes such as 820, 2040, or 830 for liquid phase applications and 46, 48 or 410 for vapor phase applications. A 2040 carbon is made of particles that will pass through a U.S. Standard Mesh Size No. 20 sieve (0.84 mm) (generally specified as 85% passing) but be retained on a U.S. Standard Mesh Size No. 40 sieve (0.42 mm) (generally specified as 95% retained). AWWA (1992) B604 uses the 50-mesh sieve (0.297 mm)as the minimum GAC size. The most popular aqueous phase carbons are the 1240 and 830 sizes because they have a good balance of size, surface area, and head loss characteristics. 3.3 Extruded activated carbon (EAC) Extruded activated carbon combines powdered activated carbon with a binder, which are fused together and extruded into a cylindrical shaped activated carbon block with diameters from 0.8 to 130 mm. These are mainly used for gas phase applications because of their low pressure drop, high mechanical strength and low dust content. 3.4 Impregnated carbon Porous carbons containing several types of inorganic impregnant such as iodine, silver, cations such as Al, Mn, Zn, Fe, Li, Ca have also been prepared for specific application in air pollution control especially in museums and galleries. Due to antimicrobial/antiseptic properties, silver loaded activated carbon is used as an adsorbent for purification of domestic water. Drinking water can be obtained from natural water by treating the natural water with a mixture of activated carbon and Al (OH)3, a flocculating agent. Impregnated carbons are also used for the adsorption of H2S and thiols. Adsorption rates for H2S as high as 50% by weight have been reported. 3.5 Polymer coated carbon This is a process by which a porous carbon can be coated with a biocompatible polymer to give a smooth and permeable coat without blocking the pores. The resulting carbon is useful for hemoperfusion. Hemoperfusion is a treatment technique in which large volumes of the patient's blood are passed over an adsorbent substance in order to remove toxic substances from the blood. 3.6 Other: Activated carbon is also available in special forms such as cloths and fibers. The "carbon cloth" for instance is used in personnel protection for the military. 4. Applications Activated carbon is used in gas purification, gold purification, metal extraction, water purification, medicine, sewage treatment, air filters in gas masks and respirators, filters in compressed air and many other applications.

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Environmental applications

Activated carbon is usually used in water filtration systems. In this illustration, the activated carbon is in the fourth level (counted from bottom).Carbon adsorption has numerous applications in removing pollutants from air or water streams both in the field and in industrial processes such as: Groundwater remediation water filtration Air purification Volatile organic compounds capture from painting, dry cleaning, gasoline dispensing operations, and other processes. Fuel storage Research is being done testing various activated carbons' ability to store natural gas and hydrogen gas. The porous material acts like a sponge for different types of gasses. The gas is attracted to the carbon material via Van der Waals forces. Some carbons have been able to achieve bonding energies of 510 kJ per mol. The gas may then be desorbed when subjected to higher temperatures and either combusted to do work or in the case of hydrogen gas extracted for use in a hydrogen fuel cell. Gas storage in activated carbons is an appealing gas storage method because the gas can be stored in a low pressure, low mass, low volume environment that would be much more feasible than bulky on board compression tanks in vehicles. Gas purification Filters with activated carbon are usually used in compressed air and gas purification to remove oil vapors, odors, and other hydrocarbons from the air. The most common designs use a 1 stage or 2 stage filtration principle in which activated carbon is embedded inside the filter media. Activated charcoal is also used in spacesuit Primary. Activated charcoal filters are used to retain radioactive gases from a nuclear boiling water reactor turbine condenser. The air vacuumed from the condenser contains traces of radioactive gases. The large charcoal bed adsorbs these gases and retains them while they rapidly decay to non-radioactive solid species. The solids are trapped in the charcoal particles, while the filtered air passes through. Distilled alcoholic beverage purification Activated carbon filters can be used to filter vodka and whiskey of organic impurities which can affect color, taste, and odor. Passing organically impure vodka through an activated carbon filter at the proper flow rate will result in

vodka with an identical alcohol content and significantly increased organic purity, as judged by odor and taste Thermal regeneration The most common regeneration technique employed in industrial processes is thermal regeneration. The thermal regeneration process generally follows three steps Adsorbent drying at approximately 105 C High temperature desorption and decomposition (500 900C) under an inert atmosphere Residual organic gasification by an oxidizing gas (steam or carbon dioxide) at elevated temperatures (800C) The heat treatment stage utilizes the exothermic nature of adsorption and results in desorption, partial cracking and polymerization of the adsorbed organics. The final step aims to remove charred organic residue formed in the porous structure in the previous stage and re-expose the porous carbon structure regenerating its original surface characteristics. After treatment the adsorption column can be reused. Per adsorption-thermal regeneration cycle between 515 wt% of the carbon bed is burnt off resulting in a loss of adsorptive capacity. Thermal regeneration is a high energy process due to the high required temperatures making it both an energetically and commercially expensive process. Plants that rely on thermal regeneration of activated carbon have to be of a certain size before it is economically viable to have regeneration facilities onsite. As a result it is common for smaller waste treatment sites to ship their activated carbon cores to a specialized facility for regeneration, increasing the processes already significant carbon footprint. 3. Literature review F.E. Okieimen, F.I. Ojokoh, C.O. Okieimen and R.A. Wuana prepared adsorbent by steeping rice husks and rubber seed shells in saturated ammonium chloride solution at 300C for 8h followed by carbonization at 5000C for 2h. The activated carbons produced were characterized in terms of pH, bulk density, surface area, porosity, resistance to mechanical abrasion and total surface charge. It was found that the measured characteristics of the activated carbon prepared from the agricultural waste products compared favorably with those of some commercial grade activated carbons. The adsorptive properties of the activated carbons were evaluated from the adsorption characteristics, measured in terms of efficiency and effectiveness of sorption of Zn (II) ions and polar organic compounds, methanol, ethanol and n-propanol. The sorption data fitted the Langmuir model and the constant of isotherm equation obtained indicated that the sorption of the metal ions and organic compounds unto the activated carbons was favorable. These data suggest that rice husks and rubber seed shells are suitable precursor materials for the production of activated carbons.[8] Mishra.S.,Prakash. D.J., Ramakrishna.G. studied the physico-chemical characteristics of low-cost Mahua Oil Cake(MOC) for the adsorption of Congo Red dye. At initial pH-2.0, with 6g/L of MOC concentration and 50mg/L of Congo Red concentration, maximum adsorption was obtained. The adsorption of dyes on MOC was a gradual process and quasi-equilibrium reached in 2 hours. The

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adsorption kinetics followed pseudo-first-order kinetics. R2 values showed that Langmuir isotherm represented the equilibrium adsorption data of Congo Red dye very well. Thermodynamic studies indicate the exothermic reaction of Congo Red adsorption by MOC. The desorption study of dye from adsorbed MOC using different solvents viz. water, acids and alkalis was not that much effective.[9] D. Angelova, S. Uzunova, S. Staykov, I. Uzunov prepared carbon/SiO2 based material by pyrolysis of rice husks at 4500c and its use as adsorbent for cleaning of crude oil and petroleum products spills. The phase composition, microstructure and morphology of the composite material C/SiO2 prepared by pyrolysis of rice husks were investigated by X-ray diffraction analysis, FTIR spectrometry and thermal analysis ( DTA, TG and DTG). Bulk density, porosity and specific surface area of the carbonized rice husks were also determined. The sorption capacities of the raw rice husks and the adsorbent obtained from them were compared in relation to different petroleum products and evaluated their possible practical use for water cleanup from oil spills.[10] Savita R. Kamath and Andrew Proctor worked on adsorbent preparation from hulls, a waste coproduct of the rice industry, is composed of 20% silica. The objectives of this study were to develop a method to recover silica from rice hull ash and produce silica gel, and to determine the physical and chemical properties of the rice hull silica gel (RHSG) relative to Trisyl 300, a commercial silica gel. Rice hull ash consisting of 61% silica and 36% carbon was dispersed in sodium hydroxide to dissolve the silica and produce a sodium silicate solution. The latter was titrated to pH 7 with 1M sulfuric acid to obtain a gel at neutral pH. The RHSG was aged, washed, and dried under specific conditions to get a final product that was slightly basic and had a moisture content >65%. Energy dispersive X-ray spectrometry indicated that silicon was the most abundant element present in RHSG and Trisyl 300. Elemental analyses by inductively coupled plasma emission spectroscopy indicated a greater concentration of sodium and sulfur in RHSG relative to that in Trisyl 300. RHSG surface area was 258 m2/g, which was slightly more than half that of Trisyl 300 particles; the particle pore diameter was 121 , which was more than twice that of Trisyl 300. Fourier transform infrared spectroscopy showed similarities in chemical structures for both the silica gel samples with respect to siloxane bonds, surface silanol groups, and adsorbed water. X-ray diffraction patterns for both the samples showed a broad peak between 15 and 35 2diffraction angle indica ting their amorphous nature. Scanning electron micrographs revealed that RHSG particles ranged in sizes from <5 to >40 m, whereas Trisyl 300 particles were smaller, ranging in sizes from <5 to 25 m and had a more uniform appearance. Silica gel production from rice hull ash alleviates the rice hull waste disposal problem and creates a commercially viable valueadded product. RHSG has wide-ranging applications in a variety of industries, such as vegetable oil refining, pharmaceuticals, cosmetics, and paints.[11] Nevine Kamal Amin worked on Bagasse pith, which is the main waste from sugarcane industry in Egypt, has been

used as a raw material for the preparation of different activated carbons. Activated carbons were prepared from bagasse pith by chemical activation with 28% H3PO4 (AC1), 50% ZnCl2 (AC2) followed by pyrolysis at 600C and by physical activation at 600C in absence of air (AC3). Different activated carbons have been used for the removal of reactive orange (RO) dye from aqueous solutions. Batch adsorption experiments were performed as a function of initial dye concentration, contact time, adsorbent dose and pH. Adsorption data were modeled using the Langmuir and Freundlich adsorption isotherms. Adsorption kinetic data were tested using pseudo-firstorder, pseudo-second-order and intraparticle diffusion models. Kinetic studies showed that the adsorption followed pseudo-second-order reaction with regard to the intraparticle diffusion rate.[12] Suresh Gupta and B V Babu prepared the presence of toxic heavy metals such as chromium (VI) contaminants in aqueous streams, arising from the discharge of untreated metal containing effluents into water bodies, is one of the most important environmental problems. Adsorption is one of the effective techniques for chromium (VI) removal from wastewater. In the present study, adsorbent is prepared from tamarind seeds and studies are carried out for chromium (VI) removal. Tamarind seeds are activated with the use of concentrated sulfuric acid (98% w/w). Batch adsorption studies demonstrate that the adsorbent prepared from tamarind seeds has a significant capacity for adsorption of chromium (VI) from aqueous solution. The parameters investigated in this study include contact time, adsorbent dosage, initial chromium (VI) concentration and pH. The adsorption process of chromium (VI) is tested with Langmuir and Freundlich isotherm models. Application of the Langmuir isotherm to the systems yielded maximum adsorption capacity of11.08 mg/g at a solution pH of 7. The adsorption of chromium (VI) was found to be maximum at low values of pH in the range of 1-3.[13] C.KARTHIKA , N.VENNILAMANI , S.PATTABHI , M. SEKARThe effectiveness of a carbonaceous sorbent prepared from sago waste for the removal of Pb (II) ions from aqueous solution and industrial effluent was studied as a function of agitation time, adsorbent dosage, particle size and pH. Through Scanning Electron Microscopy (SEM), X-ray Photo electron Spectroscopy (XPS) and Fourier Transform Infra-red (FTIR) spectroscopy analysis, the surface properties of the adsorbent were studied. The experimental isotherm data were analyzed using Langmuir, Freundlich, Redlich Peterson, Temkin and DubininRadushkevich equations. The maximum adsorption capacity (Q0) was found to be 14.35 mg g-1 at an initial pH of 3.5. The Lagergren rate constant for adsorption was found to be constant for various initial concentrations of Pb(II) ions which imply that adsorption follows first order kinetics. Since the raw material used in the preparation of activated carbon is available abundantly, the resulting carbon is expected to be economically viable.[14] 4. MATERIALS AND METHOD All the cake is collected from the Karanja oil mill. This cake is first dried in the sunlight for 20 days.

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Figure 2: (a) Karanja Fruit(b) Huck (c) Seed Karanja seed oil cake is obtained after extracting oil from the Karanja seeds.

Experimental Details: The parameter chosen for the study and their variation on the adsorption are depicted in the following manner. The parameters are 1. carbonization temperature 2. Surface area of the adsorbent 3. pH of the adsorbent Effect of carbonization temperature One of the most important parameter affecting the surface characteristics of the carbon is the carbonaceous temperature. The carbonization carried out at 400 0C, 450 0 C ,5000C and 550 0C. At 550 0C the material gets converted into complete ash form while at remaining temperature carbon formation occurred . On sieve analysis two particle size got i.e. through and above 250 mesh size from 400 0C to 550 0C, the material gets converted into ash it means that the adsorption characteristics increases with increases in temperature Adsorption Studies: 1. Effect of contact time 2. Effect of initial pH 3. Effect of adsorbent dose 4. Effect of temperature Preparation of carbon: Material:The material used for preparation of activated carbon is Karanja oil cake

Method: 1. Using ammonium chloride: Activated carbon was prepared from the Karanja oil cake using the method described by Namasivayam and Kadirvelu. The agricultural by-products were steeped in saturated ammonium chloride for 8h and then carbonized at 500 0C for 2h. The activated carbon obtained was powdered and sieved, the portion that passed through a 250 mesh screen was used for the study . 2. By hydrochloric acid: The Karanja Oil Cake was collected from the nearby oil extraction industry. Itssize was reduced by mechanical grinding. It was washed with distilled water for 7 to 8times to remove the adhering foreign materials. The cake was then digested with dilute HCl (0.1N) for 24 hrs and was subsequently washed with distilled water till a constant pH of the washed water was achieved. The material was then dried for 2 days and kept in an air tight container. The particle size of the adsorbent was estimated using screening as 250 mesh size followed by carbonization at 450 0C. 3. Using concentrated sulphuric acid: The crushed raw material (100g) was treated with concentrated sulphuric acid (70 ml) and kept in an oven at 120 0C for six hours. The carbonized material was then washed with distilled water to get it free from acid and dried at 105 0C for 18 hours. The dried treated material (TM)was grounded and sieved to get uniform size (250 mesh). 4. By direct carbonization : The adsorbent prepared by carbonization of Karanja oil cake at a temperature of 4500C for 2 hours. In order to remove mechanical impurities Karanja oil cake washed several time with distilled water and then dried at 110 0C. The temperature of the furnace increase linearly from room temperature up to the value needed for carbonization. Preparation of Activated Carbon Run no. 1 By Saturated Ammonium chloride (Chemical Activation) 1) 100 gm of Karanja oil cake in Petri dish. 2) 70ml saturated ammonium chloride added in Karanja oil cake. The addition is done in slow manner to avoid splashing. The addition of ammonium chloride in Karanja oil cake took about 45 seconds. 3) During the addition of saturated ammonium chloride foam formed. After the addition this mixture kept for the foam settling. 4) Foam settles completely after 1 hour. 5) This was kept for drying in Petri dish for 8 hr in dryer. 6) Weight of sample before oven = 121.34 grams. 7) The material kept for oven drying at 30 0C for 8 hrs. a. Starting time = 10:00 am. b. End time = 6.00 pm. 8) Weight of sample after oven drying = 82. 54 grams * Carbonization of sample 1) Weight of sample after oven drying found to be 82.54 gm. 2) Starting time = 3: 25 pm. 3) Temperature set at 500 0C for carbonization 4) Carbonization applied for 2hours after attaining

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constant temperature . 5) End Time =5.30 pm. 6) Weight of the carbonized material found to be 28.88 gm. 7) Activated Carbon is collected in Petri Dish, 2-3 Runs By same Procedure is done for more sample. 8) Collected Sample is Washed several time with Distilled Water to get normal constant pH. 9) pH of the carbonized material = 7.14. Run no. 2 By Hydrochloric acid (Chemical Activation) 1) 100 gm of Karanja oil cake in Petri dish. 2) It was washed with distilled water for 7 to 8 times to remove the adhering foreign materials. 3) 0.1N dilute hydrochloric acid added in Karanja oil cake. The addition is done in slow manner to avoid splashing. The addition of (0.1N) dilute hydrochloric acid in Karanja oil cake took about 45 seconds. 4) During the addition of acid, foam formed. After the addition this mixture keeps for the foam settling. 5) Weight of sample before drying = 115.43 grams. 6) The material was then dried for 2 days and kept in an air tight container. 7) Weight of sample after drying = 87. 44grams. Carbonization of sample 1) Weight of sample after oven drying found to be 87.44 gm. 2) Starting time = 2: 35 pm. 3) Temperature set at 450 0C for carbonization. 4) Carbonization applied for 2 hours after attaining constant temperature 5) Weight of the carbonized material found to be 26.17 gm. 6) pH of the carbonized material = 5.57. Washing of the carbonized material 1) The carbonized material washed with distilled water for 8 times, the pH observed to be gradually decreases from 5.57 to 6.89. Washing carried out with hot water by taking 70 ml every time Run no. 3 By Direct carbonization (Physical Activation) 1) 1)100 gm of Karanja oil cake in Petri dish. 2) Karanja oil cake washed several time with distilled water to remove mechanical impurities. 3) This was kept in Petri dish for drying at 110 0C. 4) Weight of sample before oven = 112.93 grams. 5) The material kept for oven drying at 110 0C for 3 hrs at constant temperature range. a) Starting time = 11: 30am b) End time = 2.30 pm 6) Weight of sample after oven drying = 85. 77 grams Carbonization of sample 1) Weight of sample after oven drying found to be 85.77 grams. 2) Starting time = 1: 55 pm 3) temperature set at 450 0C for carbonization. 4) Carbonization applied for 2 hours after attaining constant temperature. 5) End Time =4.00 pm 6) Weight of the carbonized material found to be 32.84 g.

7) pH of the carbonized material = 8.44 Washing of the carbonized material 1) The carbonized material washed with distilled water for 10 times, the pH observed to be gradually decreases from 8.44 to 6.97. Washing carried out with hot water followed by drying at 110 0C for 3 hrs. Run no. 4 By Concentrated Sulphuric Acid (Chemical Activation) 1) 100 gm of powdered Karanja oil cake in Petri dish. 2) It was washed with distilled water for 7 to 8 times to remove the adhering foreign materials. 3) Raw Material is treated with concentrated sulphuric acid (70 ml).Concentrated Sulphuric acid is to be added very carefully. 4) This Treated Material is kept in an oven at 120 0C for six hours. a. Starting Time = 10.30 am. b. End time = 4.30 pm. 5) The carbonized material was then washed with distilled water to get it free from acid. 6) The carbonized material is then dried at 105 0C for 18 hours. A. DETERMINATION OF M.B. VALUE OF ACTIVATED CARBON (METHYLENE BLUE VALUE) REAGENT: Methylene Blue Solution Dissolve 0.15 gram of Methylene blue confirming to in 100 ml of Distilled Water (Distilled water having pH value 7.0). PROCEDURE: Weigh accurately about 0.1 gram of the material, as received, with accuracy of 0.01 gram and transfer to 50 ML Glass stoppered flask. Add from a burette 10 ml of Methylene blue solution and shake for 5 minutes. After the first 10 ml are decolorized continue to add Methylene blue solution (1 ml at a time) till the blue color disappears for 5 minutes. Decolorizing power of Activated Carbon is expressed in terms of milligrams of Methylene blue adsorbed by 1 gram of activated carbon. (This value is MB value). Where V = volume in ml of Methylene blue solution consumed, and M = mass in gram of the material taken for the test. A. Adsorption Studies: 1. Effect of contact time: 150 ml of dye solution with dye concentration (50mg/L) is to be prepared in a conical flask with adsorbent concentration (0.5g/150ml) and kept inside the shaker. Dye concentration to be estimated spectrophotometrically at the wavelength corresponding to maximum absorbance, max, using a spectrophotometer (Systronic Spectrophotometer). The samples to be withdrawn from the incubator shaker (Environmental orbital Shaker Incubator,) at predetermined time intervals and the dye solution should be separated from the adsorbent by the help of a micropipette. The absorbance of solution is then measured. The dye concentration is to be measured after 5, 10, 20, 30, 60, 90,120mins until equilibrium reaches. A graph is to be plotted with qe vs. time. The qe is expressed as

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 =0/ Where, qe = Amount of dye adsorbed per unit mass of adsorbent (mg/g). C0= Initial dye concentration (mg/L). Ce= Final dye concentration (mg/L). X = Dose of adsorbent (g/L). 2. Effect of initial pH: 150ml of dye solution was prepared in a conical flask with dye conc. 50mg/L and Adsorbent conc. (1g/150ml) and initial pH of the conical flask is to be measured. The pH of the dye solutions was adjusted with dilute HCl (0.05N) or KOH (0.05N) solution by using a pH meter (EUTECH Instrument, pH 510).150 ml of dye solution was prepared taking three dyes and the pH of solution is changed from 2 to 10.The flasks were put inside the incubator shaker 14 (120rpm fixed throughout the study) maintained at 27oC and the final concentration of dye was measured using UV spectrophotometer and the calibration plot of the dye after 2 hours. A graph is to be plotted with qe vs. initial pH. 3. Effect of adsorbent dose: 150ml of dye solution was prepared in different conical flasks with dye conc. (50mg/L) and adsorbent concentration 0.5, 1, 2, 5,8g/150ml. The final dye concentration readings were taken after putting the 4 flasks inside the shaker for 2 hours. A plot of qe vs. adsorbent dose is taken. 4. Effect of temperature: 150 ml of dye solution was prepared in conical flask with dye concentration 50mg/L and adsorbent dose (1g/L) and put inside the incubator shaker. The temperature was maintained at 20C. The final dye concentration readings were taken at 5, 10, 20, 30, 60,120mins. The same procedure was followed for temperatures 30C and 40 C. A plot of qe vs. time at different temperatures is obtained. 5.RESULTS AND DISCUSSIONS A.METHYLENE BLUE VALUE. REAGENT: Methylene Blue Solution Dissolve 0.15 gram of Methylene blue confirming to in 100 ml of Distilled Water (Distilled water having pH value 7.0). Where V = volume in ml of Methylene blue solution consumed, and M = mass in gram of the material taken for the test. Result: Methylene blue value Sample M..B. Value Sample A (physical Activation) Sample B (Chemical Activation-Sat. Ammonium Chloride) Sample C (Chemical ActivationConc. Sulphuric Acid) 165 180 155

B. Adsorption Studies: 1.1 Effect of Contact time: The effect of contact time can be seen from Fig.1.1.1. for the dyes. It is clear that the extent of adsorption is rapid in the initial stages and becomes slow in later stages till saturation is allowed. The final dye concentration did not vary significantly after 2 hours from the start of adsorption process. This shows that equilibrium can be assumed to be achieved after 2 hours (120 min). It is basically due to saturation of the active site which does not allow further adsorption to take place. 1. Effect of Time on dye removal of Methylene blue at 250C (Adsorbent dose=0.050g/150ml solution)
Time in minutes 2 5 20 25 60 120 150 % Dye Removal Using Sample B (Ammonium Chloride) 11.00 22.00 40.00 53.00 77.00 86.00 87.00

1.2 Effect of Time on dye removal of Congo Redat 250C (Adsorbent dose=0.050g/150ml solution)
Time in minutes 2 5 20 25 60 120 150 % Dye Removal Using Sample B (Ammonium Chloride) 53.00 59.00 67.00 72.00 81.00 86.00 87.00

1.3. Effect of Time on dye removal of Malachite Greenat 250C (Adsorbent dose=0.050g/150ml solution)
Time in minutes 2 5 20 25 60 120 150 % Dye Removal Using Sample B (Chem. Act-Ammonium Chloride) 31.00 40.00 52.00 67.00 84.00 92.00 93.00

Std. Activated Carbon 225 (commercial) *(Std Methylene Blue Value for Commercial Activated carbon is given as 250 mg/gm)

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International Journal of Chemical Engineering and Applied Sciences 2012; 2(3): 13-23

1.2 Effect of initial pH of the solution: The effects of initial pH on dye solution of three dyes removal were investigated by varying the pH from 2 to 10. At pH - 2 the removal was minimum but it increased along with increasing initial pH of dye solution. For Malachite Green it was maximum at pH = 9 as we see in the fig 1.2.1. In case of Methylene blue higher the pH, greater is removal by adsorption .For Congo Red there is no significant change in amount adsorbed after pH 7. In fact adsorption found to decrease with increase in pH of solution. The adsorption of these positively charged dye groups on the adsorbent surface is primarily influenced by the surface charge on the adsorbent which in turn is influenced by the solution pH. The result showed that availability of negatively charged groups at the adsorbent surface is necessary for the adsorption of basic dyes to proceed which we see at pH -2 is almost unlikely as there is a net positive charge in the adsorption system due to the presence of H30+ .Thus as the pH increased, more negatively charged surface was available thus facilitating greater dye removal .We see that the trend is increasing with increasing pH. 2.Effect of Change in pH on Adsorption of Dyes at conc.50mg/l
Ph 2 3 5 7 9 10 Methylene Blue 7 12 21 22 23 22 Congo Red 28 30 34 34 34.5 34 Malachite Green 16 21 27 28 29 28

Amount of Adsorbent (gm) 0.5 1 2 5 8

Methylene blue 11 12 26 69 78

Congo Red 53 54 60 79 86

Malachite Green 31 32 42 79 87

1.4 Effect of Temperature: The effect of temperature on adsorption of dye solution with initial concentration of 50mg/L at pH=solution pH at temperatures 20, 30 and 40C on has been determined. The result of time rate studies for the adsorption of the three dyes Malachite Green, Methylene blue and Congo Red at different temperature has been shown in the figures below.

Figure 4.1 1 Effect Of Temperature on Absorption Of Dyes 1.3 Effect of adsorbent dosage: From fig 4.1.3.1 we see that the optimum dose for the dye is 6g/150ml. Though at 8g/150ml, there is slight increase in qe value but if we get nearly the same result as we get at adsorbent dosage of 5g/150ml then going for 8g/150ml will be expensive and loss of adsorbent. It is obvious as with increasing amount the active sites for adsorption of mixture of three dyes increases which results in an increase in removal efficiency. The decrease in adsorption capacity with an increase in the adsorbent concentration could be ascribed to the fact that some of the adsorption sites remained unsaturated during the process. Results indicate that the adsorption capacity of activated carbon for the three dyes (Methylene blue, Malachite Green and Congo Red) increased with temperature. This may be a result of increase in the mobility of the large dye ion with temperature. An increasing number of molecules may also acquire sufficient energy to undergo an interaction with active sites at the surface. Furthermore, increasing temperature may produce a swelling effect within the internal structure of the activated carbon enabling large dyes to penetrate further. 6.CONCLUSION Removal of dyes, mixture of Methylene blue, Malachite Green and Congo Red from aqueous solutions by

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International Journal of Chemical Engineering and Applied Sciences 2012; 2(3): 13-23

adsorption with activated carbon has been experimentally determined and the following observations are made: The percentage of color removed increase with increasing adsorbent dosage, increase with increasing contact time and varied with dye solution pH. The adsorption rates increases with increasing temperatures due to increase in the mobility of the large dye ion with temperature. Optimum contact time for equilibrium to be achieved is found to be 2 hours (120 min). It is basically due to saturation of the active site which does not allow further adsorption to take place. For Malachite Green maximum adsorption found to be at pH = 9. In case of Methylene blue higher the pH, greater is removal by adsorption .For Congo Red there is no significant change in amount adsorbed after pH 7. In fact adsorption found to decrease with increase in pH of solution. The adsorption of these positively charged dye groups on the adsorbent surface is primarily influenced by the surface charge on the adsorbent which in turn is influenced by the solution pH. The result showed that availability of negatively charged groups at the adsorbent surface is necessary for the adsorption of basic dyes to proceed which we see at pH -2 is almost unlikely as there is a net positive charge in the adsorption system due to the presence of H30+ .Thus as the pH increased, more negatively charged surface was available thus facilitating greater dye removal. Optimum adsorbent dose for the dye is 6g/150ml. It is obvious as with increasing amount the active sites for adsorption of mixture of three dyes increases which results in an increase in removal efficiency. The decrease in adsorption capacity with an increase in the adsorbent concentration could be ascribed to the fact that some of the adsorption sites remained unsaturated during the process and agglomeration of activated carbons as a result all the surface area is not available for adsorption process. Optimum temperature is 40 'C .The adsorption capacity of activated carbon for the three dyes (Methylene blue, Malachite Green and Congo Red) increased with temperature. This may be a result of increase in the mobility of the large dye ion with temperature. An increasing number of molecules may also acquire sufficient energy to undergo an interaction with active sites at the surface. Furthermore, increasing temperature may produce a swelling effect within the

internal structure of the activated carbon enabling large dyes to penetrate further. 7. References: 1. M. Ahmedna, W.E. Marshall and R.M. Rao(2000). Granulated activated carbons fromagricultural byproducts: Preparation, properties and application in cane sugar refining. Bulletinof the Louisiana State University Agricultural Centre. 2. W.T Tsai, C.Y. Chang, S.Y. Wang. C.F. Chang, S.F. Chien and H.F. Sun (2001).BioresouceTechnol. Journali,78,203-208 3. R.F. Rodriguez-Reinoso and A.L. Seleno (1989). Microporous structure of activated carbons as revealed by adsorption methods. In Chemistry Preparation and evaluation of activated carbon ChemClassand Physics of Carbons.Vol. 21, Ch.1. (P.A.Thrower, Ed) Marcel Dekker, Inc. New York. 4. J.E. Rivera-Utrilla, E. Uterere-Utrilla, M.A. FerroGarcia and C. Moreno-Castella(1991).Carbon preparation 29(4-5) 5. C. Namasivayam and K. Kadirvelu(1999).Carbon,37,79-84 6.Chandrasekhar S, Pramada P. N. Adsorption.. (2006) 12,27-43 7.Eddleston M, Juszczak E, Buckley NA, et al.(2008). "Multiple-dose activated charcoal in acute selfpoisoning: a randomised controlled trial"579-587. 8. F.E. Okieimen, F.I. Ojokoh, C.O. Okieimenand R.A. WuanaPreparation (2004)and evaluation of activated carbon from rice husk and rubber seed shel (lChemClass Journal,)2004 (191-196) 9.Mishra.S., Prakash. D.J., Ramakrishna.G.(2008) Department of Chemical Engineering, National Institute of Technology, Rourkela, Orissa, India.ISHN 1579-4377 10.D. Angelova, S. Uzunova, S. Staykov, I. UzunovJourna(2010)of the University of Chemical Technology and Metallurgy..25-32 11. Savita R. Kamathand Andrew Proctor Silica Gel from Rice Hull Ash: Preparation and Characterization.Cereal Chem.484-487 12. Nevine Kamal AminDesalination. (2008)151-161 13.Suresh Gupta1 and B V Babu*Chemical Engineering Group, Birla Institute of Technology and Science, Pilani-333 031, Rajasthan, India. 14.C.KARTHIKA, N.VENNILAMANI, S.PATTABHI, M. SEKARInternational(2010) Journal of Engineering Science and Technology.VOL2 18671879

Source of support: Nil; Conflict of interest: None declared

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