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SEPARATION PROCESS II

LABORATORY REPORT

CBB 2063
ACTIVATED CARBON
24th AUGUST 2010
Group A2
ARIFF FIKRI BIN MOHAMED ZIKRI

11895

ABDUL RAHIM BIN ZAINI

11844

FATIN ELLIYA BINTI ZAILAN

11926

HON LIAN HUNG

11940

MOHD IKRAM SOLEHUDDIN BIN BORHAN

12022

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TABLE OF CONTENTS

Contents
Objectives
Introduction
Theory
Procedure
Results
Discussions
Conclusions
References

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OBJECTIVES

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The objective of this experiment is to investigate the adsorption


properties of activated carbon by studying the equilibrium isotherms,
adsorption kinetics and operational characteristics of a lab scale packedbed reactor.

INTRODUCTION

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 for
adsorption or chemical reactions. 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

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contaminant, at which time the canister will be replaced and/or


reactivated (usually by heat).
The word activated in the name is sometimes replaced with active.
Due to its high degree of microporosity, just 1 gram of activated carbon
has a surface area in excess of 500 m2 (about one tenth the size of a
football field), as determined typically by nitrogen gas adsorption.
Sufficient activation for useful applications may come solely from the high
surface area, though further chemical treatment often enhances the
absorbing properties of the material. Activated carbon is usually derived
from charcoal.
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.

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
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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 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 acti vated
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 Freundlich isotherm is shown in eq1.
where X is the
mass of solute adsorbed, M is the mass of adsorbent, Ce is the equilibrium
concentration of solute, and K,n is the experimental constant.
X /M = K * Ce (1/n)
The two graphs below illustrate a general Freundlich isotherm equation
and a sample
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breakthrough curve. Each individual type of GAC has its own isotherm
curve and breakpoint
characteristics. These help to predict the adsorptive capacity of particular
activated carbons andgive a design estimate for adsorptive life.
Reactivation becomes necessary once the breakpoint has been reached.

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PROCEDURES

This experiment is divided into 2 sub-experiments:


1. Adsorption kinetics
2. Adsorption equilibria
Experiment 1 : Adsorption Kinetics
1. 1 litre of methylene blue solutions was prepared in three beakers at
the following concentrations :
a. I: 10 mg/l, II: 30 mg/l and III: 50 mg/l.
2. The solutions were palced over magnetic stirrers and start stirring.
3. At time zero 150 mg of granular activated carbon was added to the
first, 350 mg of granular activated carbon to the second and 400 mg
of granular activated carbon to the third beaker.
4. Samples were taken at 15-minute time intervals, and samplings
were continued until the systems attain the equilibrium.
5. The remaining methylene blue concentrations were determined , by
utilizing the calibration curve prepared before.
Experiment 2 : Adsorption Equilibria
1. 5 set of 200 ml of methylene blue solution with 30 mg/l concentration
were prepared. 20, 30, 40, 50, and 55 mg of granular activated carbon
was added into the flasks accordingly.

2. The flasks were covered 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. The remaining methylene blue concentrations were measured for
each flask.
4. The quantity of methylene blue that was transferred to the surface
of activated carbon are determined for each flask.

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RESULTS
RESULTSAND
ANDDISCUSSION
DISCUSSION

Results and Discussion Part 1, Adsorption Kinetics


In Part 1 the goal is

To determine the qualitative effect of initial concentration on the initial rate of adsorption.
To observe if the initial concentration has any effect on the qualitative amount of adsorbate
adsorbed.
To determine if the simple rate law can adequately describe adsorption.

It is assumed that the adsorbate does not leave the adsorbent once it is adsorbed (no desorption).
The adsorption is carried out at room temperature (25 C).
Adsorbate: Methylene blue
Adsorbent: Activated carbon
Due to time constraints, the adsorption processes for all three beakers were conducted
simultaneously, with a five minute window in between (i.e. beaker 1 starts at 0 min, beaker 2 starts
and 5 min, beaker 3 starts at 10 min). Concentration data is obtained every 15 minutes of the
adsorption process. Data collection is stopped when all the three beakers exhibit similar reading with
the previously obtained reading for that beaker.
Determination of Initial Concentration
100 mg was added to 1 L, in volumetric flask
Current concentration is 100 mg/L
Divided to three beakers in different amounts
Beaker 1 has 10 ml, i.e. has 100 mg/L 0.01 L = 1 mg solute
This is further diluted to 1 L, so concentration is now 1 mg/L
Beaker 2 has 30 ml; similarly, the concentration is 3 mg/L
Beaker 3 has 50 ml; similarly, the concentration is 5 mg/L
The amount of activated carbon added to the all three beakers is the same, 10mg.

Raw Data
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Time (min)
0
15
30
45
60
75

1 mg/L Beaker
0.024
0.013
0.003
0.002
0.002
0.002

Spectrophotometer Reading
3 mg/L Beaker
0.069
0.064
0.050
0.040
0.012
0.011

5 mg/L Beaker
0.119
0.084
0.059
0.046
0.039
0.039

The spectrophotometer reading does not match the calibration curve given. The lab is inaccessible
after lab hours. A new calibration curve will have to be plotted with just three points above (where time
is 0 min). This is the best that can be done. We also know that the calibration curve should be linear
with an intercept of 0.

With this, the raw data can be processed appropriately.

Processed Data
Time

1 mg/L

C/Cinit

Concentration
3 mg/L
C/Cinit
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5 mg/L

C/Cinit

(min)
0
15
30
45
60
75

Beaker

Beaker

Beaker

(mg/L)
1.043
0.565
0.130
0.087
0.087
0.087

(mg/L)
3.000
2.783
2.174
1.739
0.522
0.478

(mg/L)
5.174
3.652
2.565
2.000
1.696
1.696

1.00
0.54
0.13
0.08
0.08
0.08

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1.00
0.93
0.72
0.58
0.17
0.16

1.00
0.71
0.50
0.39
0.33
0.33

Plots

Apparently there is some problem with the 3 mg/L beaker, most likely errors in sampling.
From the plots, we see that the initial rate of adsorption (the slope of the graph) increases as the
concentration of adsorbate increases. [Objective 1 accomplished]
In addition, we see that as the concentration of the adsorbate increases, the amount that could be
adsorbed by the activated carbon increases as well, since it is an equilibrium-driven reaction.
[Objective 2 accomplished]

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A simple rate law has the feature of a constant order of reaction. Therefore, next is to find the order of
reaction, if it exists. Using the differential method, we can express the general form of the rate law as
follows.

We see that alpha can be obtained as the gradient of a plot of (ln dC/dt) vs. (ln C).
dC/dt can be obtained by first obtaining a polynomial fit of the graph C against t, then differentiating it.
1 mg/L Beaker
y = -3E-06x3 + 0.0005x2 - 0.047x + 1.061
dy/dx = -9E-06x2 + 0.001x - 0.047
3 mg/L Beaker
y = 1E-05x3 - 0.001x2 + 0.001x + 2.992
dy/dx = 3E-05x2 - 0.002x + 0.001
5 mg/L Beaker
y = -2E-08x4 - 1E-06x3 + 0.001x2 - 0.119x + 5.176
dy/dx = -8E-08x3 - 3E-06x2 + 0.002x 0.119

Time (min)
0
15
30
45
60
75

1 mg/L
-0.047
-0.034
-0.025
-0.020
-0.019
-0.023

dC/dt
3 mg/L
0.001
-0.022
-0.032
-0.028
-0.011
0.020

5 mg/L
-0.119
-0.090
-0.064
-0.042
-0.027
-0.020

1 mg/L
0.043
-0.571
-2.037
-2.442
-2.442
-2.442

ln C
3 mg/L
1.099
1.023
0.671
0.553
-0.651
-0.738

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5 mg/L
1.644
1.295
0.942
0.693
0.528
0.528

1 mg/L
-3.058
-3.381
-3.685
-3.901
-3.942
-3.789

ln -(dC/dt)
3 mg/L
#
-3.805
-3.442
-3.567
-4.510
#

5 mg/L
-2.129
-2.409
-2.751
-3.161
-3.609
-3.931

In column 9 (ln -dC/dt for 3 mg/L) the natural logarithm could not be computed since it does not exist
for negative values. This can be blamed on inaccurate collection of data.
From the plot, we observe that the gradient is different for different initial concentrations of adsorbate.
Therefore, no simple order of reaction exists and it has to be determined experimentally to obtain a
correlation with the initial concentration of adsorbate. This is probably why instead of using rate laws
to describe the adsorption process, isotherms have been developed. [Objective 3 accomplished]
We could have added another objective, to determine if the initial concentration of adsorbate has any
effect on the time required for the adsorption process to reach equilibrium, but this proves difficult
because the concentration time data was collected every 15 minutes (increment is too large to be
accurate). However, a preliminary guess is that it has no effect on the time, since all three beakers
achieve equilibrium at about the same time (near 60 75 min)
In short, for the adsorption of methylene blue on activated carbon,

A higher initial concentration of adsorbate will result in a higher initial rate of adsorption.
A higher initial concentration of adsorbate will result in more methylene blue being adsorbed
because of the shift in equilibrium.
The process of adsorption cannot be described by a simple rate law.

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Results and Discussion Part 2, Adsorption Equilibrium


In Part 2 the goal is

To determine the effect of the amount of adsorbent used on the amount of adsorbate that
could be adsorbed.
To determine which isotherm suits this adsorption process better, Freundlich or Langmuir,
since the use of simple rate law has failed (Part 1).

The initial concentration of adsorbate is constant. The experiment is started simultaneously with the
experiment in Part 1 using another stirring machine. The experiment is conducted for 105 minutes, by
which we are quite confident that equilibrium has been achieved, even if there is desorption. The time
frame was guessed using the time data from Part 1. Laboratory session time constraints had its effect.
Initial concentration is 10 mg/L. The adsorption is carried out at room temperature (25 C).
Raw data is processed using the calibration curve from Part 1.
Amount of Activated

Spectrophotometer Reading

Final Concentration

Amount

Carbon (mg)
20
30
40
50
55

(after 105 min)


0.046
0.026
0.020
0.015
0.011

(mg/L)
2.000
1.130
0.870
0.652
0.478

Adsorbed (mg/L)
8.000
8.870
9.130
9.348
9.522

Indeed, we see that as the amount of adsorbent is increased, the amount adsorbed increases almost
linearly as well.
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Plot the Freundlich isotherm

Where q is the loading and c is the concentration; k and n are temperature-dependent constants
ln c
0.693
0.123
-0.140
-0.427
-0.738

ln q
-0.91629
-1.21857
-1.47727
-1.67688
-1.75376

The line of best fit is y = 0.622x - 1.347


Therefore n = 0.622 and k = 0.2600 for the current set of units (mg/L)

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Plot the Langmuir isotherm

c
2.000
1.130
0.870
0.652
0.478

c/q
5.000
3.824
3.810
3.488
2.763

The line of best fit is y = 1.302x + 2.440


Therefore qmax = 0.768 and k = 0.534 for the current set of units (mg/L)

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The Freundlich isotherm has a lower R-squared value, and is a better representation of experimental
data. Therefore, the adsorption of methylene blue onto activated carbon at room temperature is better
described by the Freundlich isotherm.
In short,

An increase in the amount of activated carbon will result in more methylene blue being
adsorbed.
The adsorption process at room temperature is better described by the Freundlich isotherm
compared to the Langmuir isotherm.

CONCLUSION

Based to this experiment, water softening and water decationization using


the cationic resins are done.

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The objective of this experiment is to investigate the adsorption


properties of activated carbon by studying the equilibrium isotherms,
adsorption kinetics and operational characteristics of a lab scale packedbed reactor.
After conducting the experiment, it is observed that the
concentration of methylene blue as absorbent is decreasing through time
due to adsorption process by activated carbon. Activated carbon is the
absorbent. As in part 1, the final amount of beaker with concentration
1mL, 3mL, and 5mL after 75 minutes are: 0.087, 0.478, and 1.696 mL
respectively. The process cant be described by a simple rate law.
It is also proved that the higher the amount of activated carbon
used, the higher the rate of adsorption. Part to gives final concentration of
2.0 mL, 1.13 mL, 0.87 mL, 0.652 mL, and 0.478 mL for 20,30,40,50, and
55 mg of activated carbon used respectively, after 105 minutes. Plotting
Freudlich graph suit the best isotherm as it gives straight line with slope
0.6227 and intercept at (0,1.3476). The R2 value of 0.976. This value is
better than plotted again Langmuir as shown in the calculation.
Methylene blue is used as the absorbate because of its property of
visibility and can the concentration can be checked using
spectrophotometer.
Smaller adsorbate with more porous is better absorbent than those
with large size. In this case, activated carbon is such a good adsorbent.

REFERENCES

http://www.remco.com/ix.htm

Geankoplis, C.J., Transport Processes & Unit Operations, 3rd edition, Prentice Hall,
1995.

Lab Manual EXPERIMENT 3, ADSORPTION ACTIVARED CARBON


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