PROJECT REPORT ON

Study of Adsorption and Desorption of m-Cresol using activated charcoal

BY

MUDIT JAJODIA
Class Roll No. 095660 Examination Roll No. 09126004051 Registration No. 091260110250 UNDER THE GUIDANCE OF Ms. Sudipta Dey Professor Department of Biotechnology Heritage Institute of Technology, Kolkata
HERITAGE INSTITUTE OF TECHNOLOGY Kolkata 700 107, INDIA Affiliated To:WEST BENGAL UNIVERSITY OF TECHNOLOGY

INDEX
Serial no. 1. 2. 3. 4. Topic Abstract Chapter1:Introduction Chapter2:Experiment Chapter3:Results Discussions 5. 6. Future Prospects References 42. 42.-45. Page no. 4. 6.-13. 14.-20. and 21.-41.

ACKNOWLEDGEMENT
2

It is a pleasure to acknowledge the assistance received from several individuals during the preparation of this project report. First of all, I would like to convey my heartfelt gratefulness to my respected teacher and research supervisor Mrs. Sudipta Dey,Department of Biotechnology, of Heritage Institute of Technology, Kolkata, who introduced me to the world of research and development with great enthusiasm and patience.

I am greatly indebted to Ms.Deepa Hariharan,Technical Assistant,Department of Biotechnology, Heritage Institute of Technology, Kolkata for her kind guidance, valuable suggestions and constant encouragement from the very beginning without which this project would have been an impossible task.

I am also thankful to all faculty members, technical and non technical staff of the same department of their help whenever I needed it. I find no words to express my feelings for my parents and my brother whose moral support, love and constant encouragements have helped me to complete this journey. Their patience and sacrifice have always been a main source of my inspiration motivating me to pursue higher goals. I wish to extend my sincere gratitude to my all relatives for their blessings. Place:Kolkata Date: Mudit Jajodia

ABSTRACT
Fresh water crisis has been emerged as one of the most acute issues in the current global scenario, forcing the waste water reutilization concept a must. The reutilization of waste water again demands proper yet effective treatment. Among organic contaminants of waste water mCresolic compounds are the principal components, which due to its toxic and carcinogenic nature forces people for its removal from waste water. Adsorption being the highly efficient, simple, cost effectiveness and the availability of a wide range of adsorbents is used as one of the most indispensable method for treatment of m-Cresolic waste water. In the present study,different types of activated carbons can be used as adsorbants available from different sources. For batch adsorption process, operating variables studied were adsorbent dose, contact time, initial m-Cresol concentration, and different shaker speed. Sorption experiments indicated that the sorption capacity was dependent on operating variables.Kinetic measurements showed that the process was uniform and rapid. In order to investigate the mechanism of sorption, kinetic data were fitted in pseudo-first-order and pseudo-second-order kinetic equations. Among the kinetic models studied, the pseudo-secondorder equation was the best applicable model to describe the adsorption process of m-Cresol onto the adsorbent. Equilibrium isotherm data were analyzed using the Langmuir, isotherms. Isotherm parameters can also be used to obtain the thermodynamic parameters such as free energy, enthalpy, and entropy of sorption.Desorbtion of m-cresol from the activated charcoal was also done acid and alkaline solution.

This chapter presents the general framework of investigation on m-Cresol.

INTRODUCTION
5

m-Cresol is a derivative of m-Cresol and is a compound regarded as a priority pollutant by the United States Environmental Protection Agency (USEPA) . Industries such as pulp and paper mills, textile mills, coal gasification units, herbicides and fungicides industry, etc., are mainly responsible for discharging m-cresol in their aqueous effluents . m-Cresol, a methylated derivative of m-Cresol, leads to serious environmental contamination due to its toxicity towards aquatic biota. Mainly due to these reasons, its removal from wastewater before final discharge is required. Activated carbon, also called activated charcoal, is a form of carbon processed to be riddled with small, low-volume pores that increase the surface area available for adsorption.Due to its high degree of microporosity, just one gram of activated carbon has a surface area in excess of 500 m2. Activated Carbon Preparation: Activated carbon preparation is also synonymous as activation. However activated carbons are not cost effective which made the scientists to rethink about the raw materials which will lead to cut down the cost of activated carbons considerably. Among the raw materials animal waste products, plants and agricultural wastes, industrial wastes etc are the potential candidates for the preparation of very low-cost activated carbons. Again there are two standard activation methods exist namely, physical activation and chemical activation.The physical activation process involves carbonization in two steps, in the first step carbonization is done at 400-500 octo eliminate the bulk of the volatile matter and then further heatat 800-1000 oC to develop the porosity and surface area. In the chemical activation process no pre-carbonization step is needed and is usually used for the lingocellulosic raw materials. In this method raw materials are blended with activators and then carbonized at 500-900 oC, the remaining chemicals are removed from the carbon by acid or water wash. Product which is produced is usually in powdered form and is used for aqueousand gas phase adsorption purposes. This method needs a stream of mild oxidizing gases for ensuring uniform pore development during oxidation. Activated carbons produced by this mode are primarily used for gas and vapour adsorption. Flow-sheet representation of methods of carbonization:
RAW MATERIALS

PHYSICAL ACTIVATION

CHEMICAL ACTIVATION

PRE CARBONIZATION

CHEMICAL BLENDING

PARTIAL GASIFICATION

CARBONIZATION

Classification of Activated Carbon:Powdered activated carbon (PAC) Traditionally, active carbons are made in particulate 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. Granular activated carbon is defined as the activated carbon 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.

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 absorption 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 and is also used in rapid mix basins. GAC can be either in granular or extruded form. 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. 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. Bead activated carbon (BAC) Bead activated carbon is made from petroleum pitch and supplied in diameters from approximately 0.35 to 0.80 mm. Similar to EAC, it is also noted for its low pressure drop, high mechanical strength and low dust content, but with a smaller grain size. Its spherical shape makes it preferred for fluidized bed applications such as water filtration.

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. Other 7

Activated carbon is also available in special forms such as cloths and fibres. The "carbon cloth" for instance is used in personnel protection for the military.

Properties of Activated Carbon: A gram of activated carbon can have a surface area in excess of 500 m2, with 1500 m2 being readily achievable. Individual particles are intensely convoluted and display various kinds of porosity; there may be many areas where flat surfaces of graphite-like material run parallel to each other, separated by only a few nanometers or so. These micropores provide superb conditions for adsorption to occur, since adsorbing material can interact with many surfaces simultaneously. Physically, activated carbon binds materials by van der Waals force or London dispersion force. Activated carbon does not bind well to certain chemicals, including alcohols, glycols, strong acids and bases, metals and most inorganics such as lithium, sodium, iron, lead, arsenic, fluorine, and boric acid. Activated carbon does adsorb iodine very well and in fact the iodine number, mg/g, (ASTM D28 Standard Method test) is used as an indication of total surface area. Carbon monoxide is not well adsorbed by activated carbon. This should be of particular concern to those using the material in filters for respirators, fume hoods or other gas control systems as the gas is undetectable to the human senses, toxic to metabolism and neurotoxic. Substantial lists of the common industrial and agricultural gases absorbed by activated carbon can be found online. Activated carbon can be used as a substrate for the application of various chemicals to improve the adsorptive capacity for some inorganic (and problematic organic) compounds such as hydrogen sulfide (H2S), ammonia (NH3), formaldehyde (HCOH), radioisotopes iodine-131(131I) and mercury (Hg). This property is known as chemisorption. Effects of m-Cresol: m-Cresol ,leads to serious environmental contamination due to its toxicity towards aquatic biota. Short-term effects reported include respiratory irritation, headaches, and burning eyes. Chronic effects of high exposures included weakness, muscle pain, anorexia, weight loss, and fatigue; effects of long-term low-level exposures included increases in respiratory cancer, heart disease, and effects on the immune system. Virtually all of the workplace exposures associated with these effects involved exposures to other chemicals; thus, it is difficult to determine whether these are solely due to m-Cresol, or are the result of mixed, multiple, or other chemical exposures.

Health hazards caused by m-Cresol: Exposure mode Effects due to exposure 8

Inhalation

Can irritate the nose, throat, and lungs. Higher exposures may cause a build-up of fluid in the lungs. Ingestion of as little as 1 gram can be fatal to humans. Can also cause blindness. Irritating and corrosive to the skin. Little or no pain may be felt on initial contact due to its local anaesthetic effect. Skin contact will cause the skin to turn white; later severe burns may develop. Rapidly absorbed through the skin; toxic or fatal amounts can be absorbed through relatively small areas. prolonged exposure causes dizziness, vomiting.

Oral Eyes Skin

Chronic exposure

Exposure to m-Cresol: Populations residing near m-Cresol spills, waste disposal sites, or landfill sites may be at risk for higher exposure to m-Cresol than other populations. If m-Cresol is present at a waste site near homes that have wells as a source of water, it is possible that the well water could be contaminated. If m-Cresol is spilled at a waste site, it is possible for a person, such as a child playing in dirt containing m-Cresol, to have skin contact or to swallow soil or water contaminated with m-Cresol. Skin contact with m-Cresol or swallowing products containing m-Cresol may lead to increased exposure. This type of exposure is expected to occur infrequently and generally occurs over a short time period. Adsorption: By definition adsorption is the phenomenon of concentration or assimilation of gas (or liquid) at the surface of a solid (or liquid) with which it is in close proximity or contact called adsorption. Adsorption arises as a result of the unsaturated and unbalanced molecular forces that are present on every solid surface. Thus, when a solid surface is brought into contact with a liquid or gas, there is an interaction between the fields of forces of the surface and that of the liquid or the gas. The solid surface tends to satisfy these residual forces by attracting and retaining on its surface the molecules, atoms, or ions of the gas or liquid, adsorption is associated with decrease in residual surface energy. The molecules which are adsorbed are called adsorbates and the surface is called as adsorbent. This process creates a film of the adsorbate (the molecules or atoms being accumulated) on the surface of the adsorbent. The process of adsorption of gases into the solid surface is called occlusion. The adsorption involves two types of forces: physical forces that may be dipole moments, polarization forces, dispersive forces, or short range repulsive interactions and chemical forces are valency forces arising out of the redistribution of electrons between the solid surface and the adsorbed atoms. Depending upon the nature of the forces involved, the adsorption is of two types: physical adsorption and chemisorption. In the case of physical adsorption, the adsorbate is bound to the surface by relatively weak van der Walls forces, which are similar to the molecular forces of cohesion and are involved in the condensation of vapours into liquids. Chemisorption, on the other hand, involves exchange or sharing of electrons between the adsorbate molecules and the surface of the adsorbent resulting in a chemical reaction. The bond formed between the adsorbate and the adsorbent is essentially a chemical bond and is thus much stronger than in the physiosorption. Physiosorption and chemisorption again differ from each other due to following two differences namely, magnitude of the enthalpy of adsorption, in physical adsorption the enthalpy of adsorption is of the same order as the heat of liquefaction and does not usually exceed 10 to 20 KJ per mol., 9

whereas in chemisorptions the enthalpy change is generally of the order of 40 to 400 KJ per mol. Taking into account specificity physical adsorption is nonspecific and occurs between any adsorbate-adsorbent systems, but chemisorption is specific. Another important point of difference between physiosorption and chemisorption is the thickness of the adsorbed phase although it is multimolecular in physiosorption and is unimolecular in chemisorptions.Some of the potent adsorbents are charcoal, silica gel, clay, fullers earth, alumina gel,zeolites . Desorption: The ability of activated carbon to adsorb compounds at low concentrations has made it common adsorbent in wastewater treatment and other industrial applications. However, the economics of the carbon adsorption process depends very much on the method of regeneration. The reverse process of adsorption is called desorption in which the adsorbed substances are removed from the surface. In case of spent carbon with a large quantity of adsorbate, regeneration by chemical treatment is economically more attractive then commonly employed thermal method. Desorption is a phenomenon whereby a substance is released from or through a surface. The process is the opposite of sorption (that is, either adsorption or absorption). Although adsorption of phenolic compounds onto adsorbents such as granular activated carbon (GAC) and polymeric resins is relatively simple, the process of regenerating the adsorbent by desorption of the organic adsorbate still poses a major challenge to workers in this field, notably because of the high affinity of the compounds to the sorbent surface. The high initial cost of these adsorbents adds to the importance of the problem of sorbent regeneration. The most common techniques for desorption of phenol from activated carbon are thermal regeneration .The thermal regeneration method suffers from severe drawbacks, such as the requirement of high temperatures of the order of 300500C and excessive burnout of the carbon, resulting in capacity losses of 5-15%.Chemical regeneration, the other most common method. Chemical treatment is also more attractive because of its cost effectiveness. In this study, we treated the spent activated carbon with mainly two chemicals i.e. sodium hydroxide solution (NaOH) and hydrochloric acid (HCl).

10

Figure showing the process of adsorption and desorption

11

12

Materials Required in carrying out the process:

m-Cresol. 4-Aminoantipyrene. Liquour Ammonia. Potassium Ferricyanide. Spectrophotometer. Shaker-set at different speed. pH paper.

Sample Preparations: 1)Reagents:

(i)4-Aminoantipyrene=0.4gm in 20ml of water(20%). (ii)Ammonium hydroxide=1.0ml in 49.0ml of water. (iii)Potassium ferricyanide=1.6gm in 20ml of water(8%). (iv)Stock solution=0.2gm of m-Cresol in 100ml of water.

2)Solutions: (ii)Basic solution(NaOH solution):

Stock solution was prepared using 2gm of NaOH pellets in 100gm of water.

(iii)Acidic solution(HCl solution):

Stock solution was prepared using 0.8ml of HCl mixed with 99.2ml of water.

Standard for whole experiment: Concn.

100ppm 200ppm 300ppm 400ppm 500ppm 600ppm 700ppm 800ppm 900ppm 1000ppm

Water
95.0ml 90.0ml 85.0ml 80.0ml 75.0ml 70.0ml 65.0ml 60.0ml 55.0ml 50.0ml

Stock solution of m-Cresol

5.0ml 10.0ml 15.0ml 20.0ml 25.0ml 30.0ml 35.0ml 40.0ml 45.0ml 50.0ml

Reagents addition:
1.25ml of Sodium hydroxide. 0.5ml of 4-Aminoantipyrene. 0.5ml of Potassium ferricyanide. 13

Methods:
1.For standard curve of m-cresol:
Stock solutions of 4-aminoantipyrene(20%),m-Cresol(2%),liquid ammonia,Potassium ferrocyanide(8%) was prepared. m-Cresol of 100ml is prepared. 3 flasks are taken separately in which-0.3gm,0.6gm and 0.9gm of activated charcoal are added. The mouth of the flasks are covered and they are kept on the shaker. After 15 minutes on the shaker,5ml of the samples is taken out by pipette.Whatman paper is used to filter out the charcoal deposits. 45 ml of Water is added to the sample. To each sample,first 1.25ml of ammonia solution is added. Then solution of antipyrene is added,0.5ml. Then to them is Potassium Ferricyanide is added. A reddish tinge is obtained. O.D. value is measured at 490nm.

2.For Adsorbtion process:

In conical flasks,stock solution of m-Cresol and water was added(according to the required concetration). Then charcoal was added according to the required concentration.The whole setup is then kept on a shaker for 15 minutes and rpm is set. After 15minutes,5ml of that sample is filtered out.To that clear solution,1.25ml of liquid Ammonia,0.5ml 0f 4-Aminoantipyrene and 0.5ml of Potassium ferricyanide was added. A red coloured tinge is obtained which is dependent and proportional to the concentration of m-Cresol being added. Meanwhile,a Blank is also prepared which should not have a red tinge.Then the O.D. Value is calculated on a spectrophotometer at 490nm. This experiment is repeated for every batch until the equilibrium or steady state is occurred. Varying m-cresol conc.-300,500,600,700 ppm Variyng Charcoal conc.-0.3 gm and 0.6 gm Variyng shaker speed-48 and 76 rpm

3.For Desorption process: For alkaline pH Different m-Cresol solution was prepared and 0.3 gm charcoal was added. The conical flask was kept in shaker at constant speed until maximum adsorbtion is achieved. The solution was filtered in another flask with the help of whatmann filter paper. The filter paper used for adsorption was dipped in alkaline solution at pH 10. Than OD was measured at 280nm in uv spectrophotometer. The same process was repeated for different m-cresol solution of concentration -300,500,600,700 ppm

14

For Basic pHThe step was same as that of alkaline pH except that the adsorbed whatmann paper was dipped in a basic solution at pH 2.

Results:
Table.1:
To plot the standard curve for m-Cresol,the following datas were obtained: Sl no. Concn. of m- Vol. of m- Vol. of water O.D. Cresol Cresol 1 5ppm 0.01ml 50.0ml 0.01 2 10ppm 0.25ml 49.75ml 0.24 3 20ppm 0.50ml 49.50ml 0.37 4 30ppm 0.75ml 49.25ml 0.74 5 40ppm 1.00ml 49.00ml 1.30 From the standard curve,the following results were obtained: Charcoal OD Concn. O.D. Concn. O.D. concn. 15 of 30 of 45 mmcresol cresol 0.3gm 0.20 0.19 0.07 0.02 0.01 0.6gm 0.08 0.04 0.02 0.01 0.03 0.9gm 0.10 0.08 0.09 0.06 0.00 Concn. of mcresol 0 0.01 0 O.D. 60 0.01 0.03 0.00 Concn. of mcresol 0 0.01 0

After doing the assay of m-Cresol,the activity of adsorption of m-Cresol at different concentrations and at different speed were studied.The results which were obtained were as follows: Table.2: (i) Concn. 300ppm 500ppm 600ppm 700ppm

0.3gm of charcoal at 48rpm OD at 15 0.48 0.65 0.58 0.84

OD at 30 0.00 0.00 0.58 0.78 OD at 30 0.18 0.19

OD at 45 0.61 0.73 OD at 45 0.09 0.15 OD at 45 OD at 60

OD at 60 0.58 0.73 OD at 60 0.00 0.06

(ii)0.3gm of charcoal at 76rpm Concn. OD at15 300ppm 0.00 500ppm 0.08 600ppm 0.16 700ppm 0.54 (iii)0.6gm of charcoal at 48rpm Concn. OD at15 300ppm 0.11

OD at 30 0.31-0.30=0.01 15

500ppm 600ppm 700ppm

0.78 0.22 0.88

0.32 0.36-0.30=0.06 0.66 OD at 30 0.00 0.00

0.09 0.25

0.22 0.33 OD at 45 0.00 0.00

0.04 0.15 OD at 60 0.00 0.00

(iv)0.6gm of charcoal at 76rpm Concn. OD at15 300ppm 0.00 500ppm 0.05 600ppm 0.04 700ppm 0.02 Table.3: Standard curve for Desorption study: Concn. Of m-cresol Water 10ppm 99.5ml 20ppm 99.0ml 30ppm 98.5ml 40ppm 98.0ml 50ppm 97.5ml

Stock of m-cresol 0.5ml 1.0ml 1.5ml 2.0ml 2.5ml

O.D. value 0.05 0.11 0.20 0.26 0.32

Table.4: Study of desorption using NaOH solution at pH=10 and charcoal taken was 0.3gm at 76rpm Concentration O.D after 1hour O.D. at 24hrs after 300ppm 500ppm 600ppm 700ppm Table.5: Study Of desorption using acidic solution ( HCl solution) at pH=1.5 and charcoal taken was 0.3gm at 76rpm. Concentration O.D. at 1hour O.D.value after 24hrs 300ppm 0.075 0.094 500ppm 0.224 0.245 600ppm 0.373 0.391 700ppm 0.068 0.129 0.742 0.566 0.885 0.914 dilution 0.451 0.772 0.973 0.552 50%

16

17

The standard curve :

A standard curve is a general method for determining the concentration of a substance in an unknown sample by comparing the unknown to a set of standard samples of known concentration. For adsorption:

For desorption:

The percentage removal of m-cresol was calculated by the following equation,

18

%R=((C0-Ct))*100 C0 where, C0=initial m-Cresol concentration. Ct=final m-Cresol concentration. %R=percentage of adsorption.
For Adsorption: Study of various parametric effects on adsorption of m-cresol onto activated charcoal A: Effect of phenol concentration on its own adsorption: Percentage(%)recovery: (i)0.3gm of charcoal at 48rpm: Initial concentration Final concentration % adsorption 300ppm 20ppm 93.33% 500ppm 27ppm 94.60% 600ppm 24ppm 96.00% 700ppm 30ppm 95.71%

% adsorption
100 % adsorption 95 90 85 80 300 500 600 700 m-cresol conc.(ppm)
From the graph it is otained that at 600 ppm maxium adsorption of m-cresol take place i.e 96%.for 600ppm and 700 ppm the adsorbtion was nearly equal.as conc of m-cresol increase adsorption process is also increase.

ii)0.6gm of charcoal at 48rpm: Initial concentration 300ppm 500ppm 600ppm Final concentration 1ppm 4ppm 4ppm 19 % adsorption 99.60% 99.20% 99.30%

700ppm

7ppm % adsorption
100

99.00%

% adsorption

95 90 85 80 300 500 600 700 m-cresol conc.(ppm)

For 0.6 gm charcoal conc at 48rpm,the %adsorption of m-cresol was almost same for the diff. m-cresol conc.the maximum %adsorbtion was take place for 300ppm m-cresol conc.further increase in conc. The %adsorbtion of m-cresol was decrease .

(iii)0.3gm of charcoal at 76rpm:

Initial concentration 300ppm 500ppm 600ppm 700ppm Final concentration 0ppm 4ppm 5ppm 4ppm % adsorption 100.00% 99.20% 99.17% 99.43%

% adsorption
100 % adsorption 95 90 85 80 300 500 600 700 m-cresol conc.(ppm)

20

For 0.3 gm charcoal at 76 rpm,adsorbtion of m-cresol is 100% for 300ppm of m-cresol,,further increase in concentration the adsorbtion of m-cresol was decrease very minutely.

(iv)0.6gm of charcoal at 76rpm:

Initial concentration 300ppm 500ppm 600ppm 700ppm Final concentration 0ppm 2ppm 4ppm 1ppm % adsorption
100 % adsorption 95 90 85 80 300 500 600 700 m-cresol conc.(ppm)

% adsoption 100.00% 99.60% 99.33% 99.86%

For 0.6 gm charcoal conc at 76rpm,the %adsorption of m-cresol was almost equal for the diff. m-cresol conc.the maximum %adsorbtion was take place for 300ppm m-cresol conc. : Effect of Contact time for adsorption of m-cresol onto activated charcoal : Adsorption of 0.3 gm charcoal at 46 rpm-

21

adsorption of 500ppm m-crersol

adsorption of 300ppm m-cresol 350 300 250 adsorbed m-cresol conc.(ppm) 200 150 100 50 0 o 15 30 time(min) 45 60

600 500 400 300 200 100 0 o 15 30 45 60

adsoption 0f 600ppm m-cresol 700 adsorbed conc. of m-cresol(ppm) adsorbed conc. of m-cresol(ppm) 600 500 400 300 200 100 0 o 15 30 time(min) 45 60 800 700 600 500 400 300 200 100 0 o

adsorption of 700ppm m-cresol

15

30 time(min)

45

60

The results showed that equilibrium time required for the adsorption of m-cresol onto activated charcoal was 30min . However, the results also indicated that up to 95% of the total amount of phenol uptake was found to occur in the first 15.

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Adsorption of 0.3 gm charcoal at 76 rpm:

adsorption of300ppmm -cresol 350

adsorption of 500ppm m-cresol 600

300

adsorbed conc. of m-cresol(ppm)

250 200 1 50 1 00 50 0 o 1 5 30 time(min) 45 60

500 400 300 200 100 0 o 15 30 tim e(m in) 45 60

adsorption of 500ppm m-cresol 700 adsorbed conc. of m-cresol(ppm) 600 500 400 300 200 100 0 o 15 30 time(min) 45 60 800 700 600 500 400 300 200 100 0

adsorption of 700ppm m-cresol

adsorbed conc. of m-cresol(ppm)

15

30 tim e(m in)

45

60

The results showed that equilibrium time required for the adsorption of m-cresol onto activated charcoal was 15min. The result also showed that upto 600ppm ,100%(approx) adsorption take place.

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C: Effect of shaker speed in adsorption of m-cresol onto activated charcoal:

120 100 80 %adsorption 76 rpm %adsorption 60 40 20 0 0 10 20 time,min 30 40 50 48 rpm 120 100 80 60 40 20 0 0 10 20 30 40 50 60 70 time,min 48rpm 76rpm

Fig 1:adsorption of 500ppm mcresol

120 100 80 %adsorption 60 40 20 0 0 10 20 30 40 50 60 70 time,min

fig 2:adsorbtion of 600ppm m-cresol

48rpm 76rpm

Fig 3:adsorption of 700ppm m-cresol

From the fig1,2,3 ,it is evident that as the speed of shaker is increased for the same amt of charcoal and the mcresol,the adsorption of m-cresol onto the surface of activated charcoal was increased.So it is clear that speed of shaker has significant effect on the adsorbtion of m-cresol.

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D:Effect of adsorbent dose on adsorbtion:

adsorbtion of 300ppm m-cresol
305 300 295 adsorbed m-cresol conc.(min) 285 280 275 270 15 30 time(min) 45 0.6 gm adsorbed m-cresol conc.(ppm) 290 0.3 gm 605 600 595 590 585 580 575 570 565 560 15 30 time(min) 45 60

adsorbtion of 600ppm m-cresol

0.3 gm 0.6 gm

Fig.4:Adsorbtion of m-cresol at varying charcoal conc.

Fig.5:Adsorbtion of m-cresol at varying charcoal conc.

adsorbtion of 700ppm m-cresol

700 adsorbed m-cresol conc.(ppm) 690 680 670 660 650 15 30 time(min) 45 60 0.6gm Series3

Fig.6:Adsorbtion of m-cresol at varying charcoal conc.

From the above fig.4,5,6 it is evident that as the adsorbant conc. i.e charcoal conc. is increase,the adsorbtion of m-cresol is also increased and the time required for equilibrium or maximum adsorbtion or to reach the steady state is also decresed as charcoal conc. is increased.this is due to the reason that for the same amount of mcresol large number of adsorption sites are found.at the same time,it is also evident that the effect of adsorbant conc. on the process is minimum but it greatly effect the time of process. 25

For Desorption:
(i)Using Basic Solution(pH=10) Initial concentation 300ppm 500ppm 600ppm 700ppm Initial concentration 300ppm 500ppm 600ppm 700ppm % recovery % recovery after 1hr after 24hrs. 28% 18% 22% 20.7% 39% 24.8% 26% 25% (ii)Using Alkaline solution(pH=2)

% recovery % recovery after 1hr after 24hrs. 4.33% 7.20% 10.00% 10.2% 5.67% 8.0% 10.9% 11.4%

Fig.7:desorption of m-cresol in basic solution

fig.8:desorption of m-cresol in acidic solution

26

As we see from the above graph the desorption process of m-cresol is maximum in case of basic solution. As the concn. of m-cresol is increase,the % desorption is decrease in basic solution. But for desorption study in acidic solution it was found that with increase in initial m-cresol concentration, % desorption increased and became steady at 500 and 700 ppm.

Langmuir isotherm model:

The most widely used isotherm equation for modelling of the adsorption data is the Langmuir equation, which is valid for monolayer sorption onto a surface with a finite number identical site and is given by following equation, qe=qoKLCe 1+KLCe Where , qo and Kl = Langmuir parameters related to maximum adsorption capacity and free energy of adsorption, respectively. C =equilibrium concentration in the aqueous solution and x =equilibrium adsorption capacity of adsorbent. The linearized form of Langmuir equation can be written as, 1/x=1/ q0+(1/qoKL).1/C The Langmuir constant q0 and KL can be calculated by plotting 1/qe versus 1/Ce . Table: Study Of Langmuir Isotherm O.3gm charcoal at 48rpm X 1/X 93.33 0.01 157.6 0.006 192 0.005 223 0.004 0.3gm charcoal at 76rpm: X 1/X 100.0 0.01 165.3 0.006 198.3 0.005 232 0.004 C 20 27 24 30 C 1 4 5 4 27 1/C 0.05 0.04 0.04 0.03 1/C 1.00 0.25 0.2 0.25

0.6gm charcoal at 48rpm: X 1/X 49.83 0.02 82.6 0.01 99.3 0.01 115.5 0.008 0.6gm of charcoal at 76rpm: X 1/X 50 0.02 83.0 0.01 99.3 0.01 116.5 0.008

C 1 4 4 7 C 1 2 4 5

1/C 1.0 0.25 0.25 0.18 1/C 1 0.5 0.25 0.2

Graphs for Langmuir Isotherm: 1. Varying The rpm(48rpm and 76rpm) at constant amount of charcoal(0.3 gm)

Datas obtained: qo 232 KL 0.8 2.Varying the rpm(48rpm and 76rpm) at constant amount of charcoal(0.6gm)

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Datas obtained: qo 200 KL 0.3848

Study of reaction kinetics: Adsorption kinetics study for m-cresol on activated charcoal: 0.3 gm at 48 rpm:
0.4 0.35 0.3 0.25 t/q 0.2 0.15 0.1 0.05 0 0 10 20 30 t 40 50 60 70 y = 0.005x + 0.0277 R2 = 0.7101 y = 0.0045x + 0.0003 R2 = 1 y = 0.0052x + 0.0001 R2 = 1 y = 0.006x + 0.0018 R2 = 0.9987
300 PPM 500 PPM 600 PPM 700 PPM Linear (300 PPM) Linear (500 PPM) Linear (600 PPM) Linear (700 PPM)

Data obtained: C 300 500 qe,exp 100 166.7 qe,cal 200 166.7 29 R2 0.7101 0.9987 K 0.0009 0.019

600 192 192.3 1 0.027 700 223.3 222.3 1 0.067 From the above graph and calculated data it is obtain that q e,exp and qe,cal value are almost same except for 300ppm m-cresol conc. And value of R 2 is obtained 1 for all other conc. except for 300ppm.So for 0.3 gm charcoal conc. at 48 rpm the reaction kinetic follow second order kinetic.

0.3gm at 76 rpm:
0.7 0.6 0.5 t/q 0.4 0.3 0.2 0.1 0 0 20 40 t 60 80 y = 0.0101x + 0.0048 R2 = 0.9997
700 Linear (600) Linear (700)

y = 0.01x + 0.0028 R2 = 0.9998

600

Data obtained:
C 600 700 qe,exp 100 99 qe,cal 100 99 R2 0.9998 0.9997 K 0.035 0.021

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From the graph and obtained data it is clear that for 0.3 gm charcoal conc. at 76 rpm,adsorbtion process follow second order kinetic and the value of R2 is 1.

0.6 gm at 48 rpm:
1.8 1.6 1.4 1.2 t/q 1 0.8 0.6 0.4 0.2 0 0 10 20 30 40 t 50 60 70 80 y = 0.0201x + 0.0013 R2 = 0.9999 y = 0.0202x + 0.0003 R2 = 1 y = 0.0189x + 0.0554 R2 = 0.9463 y = 0.0201x + 0.0169 R2 = 0.9993
300 500 600 700 Linear (300) Linear (500) Linear (600) Linear (700)

Datas obtained:
C 300 500 600 700 qe,exp 49.83 49.66 49.5 49 qe,cal 49.75 49.75 49.5 R2 0.3108 0.0239 1.36 0.006 K 0.9999 0.9993 1 0.9463

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From the above graph and obtained data,it is seen that for 0.6gm charcoal conc at 48 rpm,the value of q e,exp and the value of qe,cal is almost equal and the value of k is 1.hence for 0.6 gm charcoal conc. At 48 rpm,the adsorbtion process follow second order kinetic.

Conclusions
As the shaker speed increase,the adsorption of m-cresol on activated charcoal was increased and the time required for maximum adsorbtion is decrease. Adsorbant conc. also effect the adsorbtion process. As m-cresol conc. increase,the % adsorbance is also increase. With the lower charcoal concentration and higher speed of rotation, % adsorption is more. With the higher charcoal concentration and lower speed of rotation, % adsorption is less. With the higher charcoal concentration and higher speed, % adsorption is more. The kinetics studies confirmed that Phenol-GAC adsorption system can be described by pseudo- second-order kinetics model. Over all analysis of equilibrium model analysis indicates the fitness of Langmuir isotherm model to Phenol-GAC adsorption system, suggesting a monolayer adsorption of phenol on the surface of GAC. Desorption is very less at acidic pH activity and moderate in alkaline solution.

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