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

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 SSBT’S 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

Objectives of the Research

The aim of this research is to produce activated carbon from the local agricultural waste which is Karanja Seed oil

Cake. To achieve these, a study was carried out with the

following objectives:

i. To evaluate various operating parameters such as activation temperature and activation time for the

activated carbon produced from Karanja Seed oil

Cake.

ii. To study the effect of chemical activation on the

development of pore structure on the activated carbon

produced.

iii. To examine the characteristic of granular activated carbon produced (i.e. elemental analysis, proximate

analysis, adsorption capacity, surface functionality and

pore size of AC produced).

iv. To evaluate the potential application of locally produced activated carbon in inorganic pollutants such

as its performance in Dye Removal, Waste Water

Treatment.

Scope of the research In this research, the production of activated carbon was

carried out by using chemical activation method. In

chemical activation, the carbonization and activation are

accomplished in a single step by carrying out the thermal

decomposition of the raw material impregnated with certain

activating agents.

After the impregnation step, the samples were carbonized

in the horizontal furnace by varying the operating

parameter such as carbonization temperature and

carbonization time.

The carbonization temperatures of this activation were

varied between 300 to 500 ºC to analyze the effect of

temperature on the yield and pores development of activated carbon.

This work also focuses on optimizing the activation time,

instead to optimizing the activation temperature. The raw

materials that have been activated will be carbonized under

certain temperature with control time of 0.5, 1, 2, 3, 4

hours. After carbonization, the activated carbons produced

were washed with water several times until the residual

activating agent on the surface of activated carbon

completely removed. (Till Constant pH).This stage was

important because during impregnation the activating agent

will penetrate into raw material particles and occupied

substantial volumes. Once they were extracted by intense washing, a large

amount of micro porosity was created.

In order to analyze the activated carbon produced, several

standard analyses were employed to characterize the

product that will meet the condition for commercialization.

Available online at http://www.urpjournals.com

International Journal of Chemical Engineering and Applied Sciences

Universal Research Publications. All rights reserved

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

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 by-

products. 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 by-

products 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 Bio-

Diesel. This species is commonly called pongam, Karanja,

or a derivation of these names.

It is a legume tree that grows to about 15–25 meters (15–80

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 3–4 years. Cropping of pods and

single almond sized seeds can occur by 4–6 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,

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

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 carbon’s 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 600–900 °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

(450–900 °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

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

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, 95–100% 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 80-

mesh 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 8×20, 20×40, or 8×30 for liquid phase

applications and 4×6, 4×8 or 4×10 for vapor phase

applications. A 20×40 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 12×40 and 8×30 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.

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

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 5–10 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–

900°C) under an inert atmosphere

Residual organic gasification by an oxidizing gas

(steam or carbon dioxide) at elevated temperatures

(800°C)

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 5–15 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

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

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 it’s 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 Å, 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 indicating 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 value-

added 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-first-

order, 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 Dubinin-Radushkevich 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.

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

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 0C ,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

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

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, λmax, 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

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

𝑞𝑒 =𝐶0−𝐶𝑒/𝑋

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 20°C. The final dye concentration readings

were taken at 5, 10, 20, 30, 60,120mins. The same

procedure was followed for temperatures 30°C 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) 165

Sample B (Chemical Activation-Sat.

Ammonium Chloride) 180

Sample C (Chemical Activation-

Conc. Sulphuric Acid) 155

Std. Activated Carbon

(commercial) 225

*(Std Methylene Blue Value for Commercial Activated

carbon is given as 250 mg/gm)

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 % Dye Removal Using Sample B

(Ammonium Chloride)

2 11.00

5 22.00

20 40.00

25 53.00

60 77.00

120 86.00

150 87.00

1.2 Effect of Time on dye removal of Congo Redat 250C (Adsorbent dose=0.050g/150ml solution)

Time in minutes % Dye Removal Using Sample B

(Ammonium Chloride)

2 53.00

5 59.00

20 67.00

25 72.00

60 81.00

120 86.00

150 87.00

1.3. Effect of Time on dye removal of Malachite Greenat

250C (Adsorbent dose=0.050g/150ml solution)

Time in minutes % Dye Removal Using Sample B

(Chem. Act-Ammonium Chloride)

2 31.00

5 40.00

20 52.00

25 67.00

60 84.00

120 92.00

150 93.00

22 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 Methylene Blue Congo Red Malachite Green

2 7 28 16

3 12 30 21

5 21 34 27

7 22 34 28

9 23 34.5 29

10 22 34 28

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.

Amount of Adsorbent (gm)

Methylene blue

Congo Red

Malachite Green

0.5 11 53 31

1 12 54 32

2 26 60 42

5 69 79 79

8 78 86 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 40°C 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

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

23 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:-

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products: Preparation, properties and application in cane sugar refining. Bulletinof the Louisiana State

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3. R.F. Rodriguez-Reinoso and A.L. Seleno (1989).

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poisoning: 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)

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Institute of Technology, Rourkela, Orissa,

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10.D. Angelova, S. Uzunova, S. Staykov, I.

UzunovJourna(2010)of the University of Chemical

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13.Suresh Gupta1 and B V Babu*Chemical

Engineering Group, Birla Institute of Technology and

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1879

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