EXPERIMENT 12

ACTIVATED CARBON
ADSORPTION
ISOTHERMS, KINETICS &
CONTINUOUS-FLOW
OPERATION

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SEPARATION PROCESS II
ACTIVATED CARBON ADSORPTIO N, ISOTHERMS, KINETICS & CONTINUOUS-FLOW OPERATION

1.0

Introduction

Adsorption is a unit operation in which surface-active materials in true solution are removed from
the solvent by inter-phase transfer to the surfaces of an adsorbent particle. This process is used in
environmental engineering practice for removal of various pollutants such as soluble organics,
dyes, pesticides, lignin, etc., from wastewaters and for removal of colour and taste and odourproducing substances from natural waters that are to be used as potable water supplies.
Activated carbon in very fine powder or granular form is useful to purify both water and air. It is an
extremely porous material with high ratios of surface area to unit weight up to 100 acres per pound.
Activated carbon has particular affinity to organic materials such as solvents used in printing inks
and common coatings. When the carbon particle becomes saturated with the contaminant, the exit
stream will evidence a "breakthrough" of that contaminant, at which time the canister will be
replaced and/or reactivated (usually by heat).
The objective of this experiment is yo investigate the adsorption properties of activated carbon by
studying the equilibrium isotherms, adsorption kinetics and operational characteristics of a lab-scale
packed-bed reactor.
2.0

Theory

Activated carbon is a highly porous carbonaceous substance with a wide range of applications in
gas, vapor, and liquid treatment. The use of activated carbon dates back to 1500 BC where its use
was discovered in an Egyptians papyrus for medicinal purposes. Activated carbon is used
successfully today, especially in water treatment to remove organic compounds that impart color,
taste and odor to the water. Contaminant removal is achieved through a process called adsorption
by which contaminants adhere to the surface of the carbon and are thus removed from the water.
Adsorption is the process by which Activated Carbon removes substances from water.
Defined, adsorption is "the collection of a substance onto the surface of adsorbent solids." It is a
removal process where certain particles are bound to an adsorbent particle surface by either
chemical or physical attraction. Adsorption is often confused with Absorption, where the substance
being collected or removed actually penetrates into the other solid. The reason that activated
carbon is such an effective adsorbent material is due to its large number of cavernous pores. These

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provide a large surface area relative to the size of the actual carbon particle and its visible exterior
surface. An approximate ratio is 1 gram = 100 m 2 of surface area.
Activated carbon adsorption proceeds through 3 basic steps:
1.

Substances adsorb to the exterior of the carbon granules

2.

Substances move into the carbon pores

3.

Substances adsorb to the interior walls of the carbon

Adsorption efficiency decreases over time and eventually activated carbon will need to be replaced
or reactivated. Isotherms are empirical relations, which are used to predict how much solute can be
adsorbed by activated carbon. The three most well known isotherms are the Freundlich, Langmuir
and Linear. In environmental engineering and specifically drinking water treatment application the
most commonly used isotherm is the Freundlich. Shown to the right is the Freundlich isotherm
equation in general form.
The empirical equation for describing Freudlich isotherm is shown in eq1. where X is the
mass of solute adsorbed, M is the mass of adsorbent, C e is the equilibrium concentration of solute,
and K,n is the experimental constant.
1
X
K * Ce n
M

(1)

The two graphs below illustrate a general Freundlich isotherm equation and a sample
breakthrough curve. Each individual type of GAC has an its own isotherm curve and breakpoint
characteristics. These help to predict the adsorptive capacity of particular activated carbons and
give a design estimate for adsorptive life. Reactivation becomes necessary once the breakpoint
has been reached.

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3.0

3.1

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EXPERIMENT

APPARATUS

The apparatus that used in this experiment are: volumetric flasks, laboratory shaker, balance, glass
column, pump, spectrophotometer, stopwatch, solution holding tank, assorted tubing, and
glassware.
3.2

MATERIALS

1.

Granular activated carbon; sieved, washed of fines, and dried to constant weight at 105C.

2.

Methylene blue.
3.3

EXPERIMENT DESIGN
Each of the adsorption experiments hereinafter, described employ a synthetic aqueous solution
of methylene blue as the test solution. Any other surface-active material or sorbate such as
organic dyes, phenol, substituted phenols, alkyl benzene suffocates, or high molecular weight
alcohols, however, may be substituted as the adsorbate. Further, natural waters or
wastewaters containing dissolved organics may also be employed as test solutions for these
experiments provided that they are first filtered to remove particulates. However, if methylene
blue is replaced by another adsorbate, then, it will be necessary to define appropriate analytical
techniques for whatever adsorbate is utilized.

3.4
A.
1.

EXPERIMENT PROCEDURE
Adsorption Kinetics
Prepare 1 litre of methylene blue solutions in three beakers at the following concentrations: I:
10 mg/l, II: 30 mg/l and III: 60 mg/l.

2.

Place the solutions over magnetic stirrers and start stirring.

3.

At time zero add 100 mg of granular activated carbon to the first, 250 mg of granular
activated carbon to the second and 350 mg of granular activated carbon to the third beaker.

4.

Take samples at 15-minute time intervals, and continue sampling until the systems attain the
equilibrium. If disintegration of the activated carbon should occur, samples may require
centrifugation or filtration.

5.

Determine the remaining methylene blue concentrations, by utilizing the calibration curve
prepared before.

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B. Adsorption Equilibria
1. Prepare a set of eleven 250-ml flasks by placing 100 ml of 125 mg/l of methylene blue
solution and the following weights of the granular activated carbon into the flasks: 0, 15, 20,
25, 30, 40, 50, 70, 100, 150, 200 mg.
2. Cover the flasks with parafilm and agitate them vigorously on a laboratory shaker until the
system in each flask equilibrates. Then settle or filter the suspension to remove the
carbon.
3. Measure the remaining methylene blue concentrations for each flask.
4. Calculate the quantity of methylene blue that was transferred to the surface of activated
carbon for each flask.
C.

Continuous Flow Systems

1.

Place granular activated carbon into the column. Note the dimensions of the column.

2.

Prepare approximately 1500 mg/l methylene blue solution.

3.

Feed the column with stated methylene blue solution at an appropriate rate and record the
time as time zero. Note that the column does not fluidize or expand at that flow rate if the
column is fed upward.

4.

Sample and determine the concentration of methylene blue in the column effluent until
complete breakthrough of the column is attained (C/C o=1).

Results and discussions:

A. Adsorption Kinetics
1.

Plot the normalized solution phase concentration (C/Co) vs. time for each beaker.

2.

Calculate the quantity of methylene blue that was transferred to the surface of the activated
carbon (moles of methylene blue/gram of carbon) for each sample that was collected. Plot
these uptake values vs. time on the same graphs developed in step 6 above.

3.

Check whether the order of the rate of adsorption be defined.

4.

Show that the initial rate of adsorption is proportional to methylene blue concentration and
the concentration of granular activated carbon (note that desorption can be neglected for
initial phases of the process).

5.

Discuss your observations on the rate of adsorption.

B. Adsorption Equilibria
1. Plot the data in a standard adsorption isotherm format.
2. Determine the Freundlich and Langmuir adsorption constants.

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3. Discuss the correspondence between the experimental data and the Langmuir and
Freundlich isotherms.
C. Continuous Flow Systems
1. Plot the breakthrough curve showing the concentration of methylene blue in the column
effluent.
2. Calculate the quantity of methylene blue adsorbed as a function of time by graphically
integrating the area above the curve.
3. What is the capacity of the granular activated carbon according to the breakthrough curve?
4. Compare the capacities predicted from the breakthrough and form the isotherm test.
5. Discuss the results of your experiment in detail.
References:
1.

Association of Environmental Engineering Professors, Environmental Engineering, Unit

Operations and Unit Processes Laboratory Manual, Ed. J.T. O'Connor, Third Edition, May
1984.

2.

Weber, W.J., Jr. Physico-chemical Processes for Water Quality Control.

Wiley-

Interscience, New-York, 1972.

3.

AWWA. Handbook of Public Water Supplies. McGraw Hill, p. 439.

4.

Brown, William H. Introduction to Organic Chemistry. Saunders College Publishing, p. 3.

5.

Clark, Robert M. Granular Activated Carbon: Design, Operation, and Cost. Lewis
Publishers, p. 2, 7, 35, 47-49, 205, 206

6.

Hoehn, Dr. Robert C. Class Notes: CE4104 Water and Wastewater Design. Virginia Tech,
p. 10, 37, 48, 227-236.

7.

Mallevialle, Joel et al. Influence and Removal of Organics in Drinking Water. Lewis
Publishers, p. 36.

8.

Reynolds, Tom D. & Richards, Paul A. Unit Operations and Processes in Environmental
Engineering 2nd ed. PWS Publishing Co, p. 25, 350, 749.

9.

Webster's New World Dictionary. Warner Books, p. 94, 163, 350, 440.

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APPENDIX 1
METHYLENE BLUE CALIBRATION CURVE