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ABSTRACT

The performance of a packed bed activated carbon adsorbent in purifying varying


concentrations of dye solution was evaluated in this experiment. The equation correlating the
density and the weight-by-weight percent dye concentration of a reference solution was found
out be y=0.0849x-0.0784. The adsorption isotherm representing the dye adsorption with the
highest coefficient of determination equal to 0.9604 was Freundlich Isotherm and was
represented by the equation w  18.1472175c 0.9834117406 . On the other hand, the effect of bed
height, initial concentration of the solution, and volumetric flowrate on the adsorption process
was also determined. Based on the breakthrough curves obtained, it was said that the 10 cm
bed height, compared to 5 cm, took longer time to make the bed totally saturated due to more
mass transfer zones on the bed. As per the effect of the initial concentration, in 1.0 %w/w
solution, the time when the bed became saturated was reached earlier compared to that of the
0.5 %w/w solution. This was because there is high concentration gradient or driving force
between the bed and the fluid. However, both these can be affected by the volumetric flowrate.
The main reason observed is that the higher the volumetric flowrate, the more mass of solute
will be exposed to adsorbent, taking it lesser time for the bed to be saturated. This accounts to
the random errors propagated during the experiment. Finally, an adsorption column with a
breakthrough concentration of 0.01 capable of operating for 12 hours was designed. It was
found out that the bed height must be 809.32 cm and the bed’s saturation capacity was 0.3555
grams of dye per gram of activated carbon.
TABLE OF CONTENTS

I. INTRODUCTION ............................................................................................................... 1
II. THEORETICAL BACKGROUND ..................................................................................... 2
A. EQUILIBRIUM RELATIONS FOR ADSORBENTS ......................................................................... 2
B. FIXED-BED ADSORPTION COLUMNS ........................................................................................ 3
C. BREAKTHROUGH CONCENTRATION CURVE ............................................................................ 4
D. CAPACITY OF THE COLUMN...................................................................................................... 4

III. MATERIALS AND METHODOLOGY .............................................................................. 6


A. MATERIALS ................................................................................................................................ 6
B. SCHEMATIC DIAGRAM .............................................................................................................. 7
C. METHODOLOGY ....................................................................................................................... 12

IV. RESULTS AND DISCUSSION ......................................................................................... 14


A. DETERMINATION OF EQUATION CORRELATING THE DENSITY AND CONCENTRATION ....... 14
B. DETERMINATION OF ADSORPTION ISOTHERM ....................................................................... 16
C. DETERMINATION OF THE EFFECT OF DIFFERENT PARAMETERS SUCH AS VOLUMETRIC
FLOWRATE, COMPACTED BED HEIGHT, AND INITIAL CONCENTRATION ON THE

ADSORPTION PROCESS ............................................................................................................. 21

D. DESIGN OF FIXED-BED ADSORPTION COLUMN ..................................................................... 29

V. CONCLUSION ................................................................................................................. 32
VI. RECOMMENDATIONS ................................................................................................... 34
VII. STUDY QUESTIONS ....................................................................................................... 35
VIII. REFERENCES ................................................................................................................ 37
IX. APPENDIX ....................................................................................................................... 38

LIST OF FIGURES
Figure 1: Common Types of Adsorption Isotherms (Geankoplis, 1993) ............................................... 2
Figure 2: Concentration profiles for adsorption in a fixed-bed: profiles at various positions and times
in the bed (Geankoplis, 1993). ................................................................................................................ 3
Figure 3: Breakthrough concentration profile in the fluid at outlet of bed (Geankoplis, 1993) ............ 4
Figure 4: Determination of the capacity of column from the breakthrough curve (Geankoplis, 1993). 5
Figure 5: Plot of Density vs Concentration for Dye Solution .............................................................. 15
Figure 6: Plot of Freundlich Isotherm at t = 8 minutes ........................................................................ 19
Figure 7: Plot of Langmuir Isotherm at t = 8 minutes ......................................................................... 20
Figure 8: Breakthrough Curve for the 0.5% Solution and 10 cm Bed Height ..................................... 22
Figure 9: Breakthrough Curve for the 0.5% Solution and 5 cm Bed Height ....................................... 23
Figure 10: Breakthrough Curve for the 1.0% Solution and 10 cm Bed Height ................................... 23
Figure 11: Breakthrough Curve for the 1.0% Solution and 5 cm Bed Height ..................................... 24
Figure 12: Comparison of the Breakthrough Curves at 10cm and 5cm Bed Heights for 0.5% Dye
Solution ................................................................................................................................................. 25
Figure 13: Comparison of the Breakthrough Curves at 10cm and 5cm Bed Heights for 1% Dye
Solution ................................................................................................................................................. 25
Figure 14: Comparison of the Breakthrough Curves at 10cm Bed Height for the Adsorption of 1%
and 0.5% Dye Solutions ........................................................................................................................ 26
Figure 15: Comparison of the Breakthrough Curves at 5cm Bed Height for the Adsorption of 1% and
0.5% Dye Solutions .............................................................................................................................. 27
Figure 16: Schematic diagram of the adsorption column .................................................................... 31

LIST OF TABLES
Table 1: Density Raw Data Using Hydrometer ................................................................................... 14
Table 2: Reference Solutions ............................................................................................................... 14
Table 3: Final Data Used for Equation Determination ........................................................................ 15
Table 4: Density at 0.2 % w/w dye solution ........................................................................................ 16
Table 5: Density at 0.4 % w/w dye solution ........................................................................................ 16
Table 6: Density at 0.6 % w/w dye solution ........................................................................................ 16
Table 7: Density at 0.8 % w/w dye solution ........................................................................................ 16
Table 8: Density at 1.0 % w/w dye solution ........................................................................................ 17
Table 9: Summary of the final densities at different concentration (w/w %) dye solution .................. 18
Table 10: R2 values of the Freundlich and Langmuir Isotherm Plots at different time t ..................... 19
Table 11: Freundlich Isotherm Raw Data at t = 8 minutes .................................................................. 19
Table 12: Langmuir Isotherm Raw Data at t = 8 minutes .................................................................... 20
Table 13: Raw Data Summary for the Adsorption of 0.5% Dye Solution ........................................... 21
Table 14: Densities of Effluent for the Adsorption of 0.5% Solution Using 10 cm Bed Height ......... 21
Table 15: Densities of Effluent for the Adsorption of 0.5% Solution Using 5 cm Bed Height ........... 21
Table 16: Raw Data Summary for the Adsorption of 1.0% Dye Solution ........................................... 21
Table 17: Densities of Effluent for the Adsorption of 1.0% Solution Using 10 cm Bed Height ......... 21
Table 18: Densities of Effluent for the Adsorption of 1.0% Solution Using 5 cm Bed Height ........... 22
Table 19: Determination of the Unusable Heights for the Adsorption Columns ................................. 28
Table 20: Data Assumptions1 .............................................................................................................. 29
Table 21: Data Assumptions 2 ............................................................................................................. 29
Table 22: Mass of Dye Used in Part A ................................................................................................ 35
Table 23: Mass of Dye Used in Part B ................................................................................................. 35
Table 24: Equation Determination Data .............................................................................................. 38
Table 25: Error Calculation Data for Equation Determination ............................................................ 38
Table 26: Error Bars Data .................................................................................................................... 39
Table 27: Final Density at 0.2 % w/w dye solution ............................................................................. 41
Table 28: Final Density at 0.4 % w/w dye solution ............................................................................. 42
Table 29: Final Density at 0.6 % w/w dye solution ............................................................................. 42
Table 30: Final Density at 0.8 % w/w dye solution ............................................................................. 42
Table 31: Final Density at 1.0 % w/w dye solution ............................................................................. 42
Table 32: Summary of calculated data at 0.2 % w/w dye solution ...................................................... 43
Table 33: Summary of calculated data at 0.4 % w/w dye solution ...................................................... 43
Table 34: Summary of calculated data at 0.6 % w/w dye solution ...................................................... 43
Table 35: Summary of calculated data at 0.8 % w/w dye solution ...................................................... 44
Table 36: Summary of calculated data at 1.0 % w/w dye solution ...................................................... 44
Table 37: Calculation of Concentrations in Figure 8 ........................................................................... 48
Table 38: Calculation of C/Co in Figure 8 ........................................................................................... 49
Table 39: Calculation of Concentrations in Figure 9 ........................................................................... 51
Table 40: Calculation of Concentrations in Figure 10 ......................................................................... 51
Table 41: Calculation of Concentrations in Figure 11 ......................................................................... 51
Table 42: Calculation of C/Co in Figure 9 ........................................................................................... 51
Table 43: Calculation of C/Co in Figure 10 ......................................................................................... 51
Table 44: Calculation of C/Co in Figure 11 ......................................................................................... 52
I. INTRODUCTION
Adsorption is a unit operation that exploits the attraction of solutes in a liquid or gas to a
solid surface (Gabelman, 2017). In adsorption, the atoms, ions or molecules adheres from a
gas, liquid or dissolved solid to a surface which creates a film of the adsorbate on the surface
of the adsorbent. This process differs from absorption, in which a fluid (the absorbate) is
dissolved by or permeates a liquid or solid (the absorbent), respectively. Adsorption is a
surface phenomenon, while absorption involves the whole volume of the material. The term
sorption encompasses both processes, while desorption is the reverse of it.

Similar to surface tension, adsorption is a consequence of surface energy. In a bulk material,


all the bonding requirements (be they ionic, covalent or metallic) of the constituent atoms of
the material are filled by other atoms in the material. However, atoms on the surface of the
adsorbent are not wholly surrounded by other adsorbent atoms and therefore can attract
adsorbates. The exact nature of the bonding depends on the details of the species involved, but
the adsorption process is generally classified as physisorption (characteristic of weak van der
Waals forces) or chemisorption (characteristic of covalent bonding). It may also occur due to
electrostatic attraction (Ferrari et. al., 2010).

Adsorption is present in many natural, physical, biological and chemical systems and is
widely used in industrial applications such as heterogeneous catalysts, activated charcoal,
adsorption chillers, synthetic resins, increasing storage capacity of carbide-derived carbons and
water purification (Czelej et. al., 2016).

In this experiment, the adsorbate used is activated carbon. Activated carbon is the
collective name for a group of porous carbons, manufactured by the treatment of a char with
oxidizing gases or by carbonization of carbonaceous materials impregnated with dehydrating
chemicals. All these carbons are prepared to exhibit a high degree of porosity and an extended
internal surface area (F.Rodriguez, 2015). It is widely used throughout a number of industries
to remove undesirable components from liquids or gases. It can also be applied to various
number of applications that require the removal of contaminants or undesirable materials,
ranging from water and air purification, to soil remediation, and even gold recovery (Carrie
Carlson).

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II. THEORETICAL BACKGROUND

Adsorption involves, in general, the accumulation (or depletion) of solute molecules at an


interface (including gas-liquid interfaces, as in foam fractionation, and liquid-liquid interfaces,
as in detergency) (Perry & Green, 2008). Here we consider only liquid-solid interfaces, with
solute distributed selectively between the fluid and solid phases.

In commercial processes, the adsorbent is usually in the form of small particles in a fixed
bed. The fluid is passed through the bed and the solid particles adsorb components from the
fluid. When the bed is almost saturated, the flow in this bed is stopped and the bed is
regenerated thermally or by other methods, so desorption occurs. The adsorbed material
(adsorbate) is thus recovered and the solid adsorbent is ready for another cycle of adsorption
(Geankoplis, 1993).

A. Equilibrium Relations for Adsorbents

Figure 1: Common Types of Adsorption Isotherms (Geankoplis, 1993)


1. The classical isotherm for a homogeneous flat surface, and most popular of all nonlinear
isotherms, is the Langmuir isotherm
wis K i ci
wi  (1)
1  K i ci

where wis is the monolayer capacity approached at large concentrations and Ki is an


equilibrium constant. These parameters are often determined by plotting 1/wi versus
1/ci. The derivation of the isotherm assumes negligible interaction between adsorbed
molecules (Perry & Green, 2008).

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2. For a heterogeneous flat surface, a classical isotherm is the Freundlich isotherm
wi  K i cimi (2)

where mi is positive and generally not an integer. The isotherm corresponds


approximately to an exponential distribution of heats of adsorption. Although it lacks
the required linear behavior in the Henry’s law region, it can often be used to correlate
data on heterogeneous adsorbents over wide ranges of concentration (Perry & Green,
2008). Also according to Geankoplis (1993), this isotherm is particularly useful for
liquids.

B. Fixed-Bed Adsorption Columns


A widely used method for adsorption of solutes from liquid or gases employs a fixed
bed of granular particles. The fluid to be treated is usually passed down through a packed
bed at constant flow rate. Mass transfer resistances are important in the fixed-bed process
and the process is unsteady state. The concentrations of the solute in the fluid phase and of
the solid adsorbent phase change with time and also with position in the fixed bed as
adsorption proceeds. At the inlet to the bed the solid is assumed to contain no solute at the
start of the process. As the fluid first contacts the inlet of the bed, most of the mass transfer
and adsorption takes place here. As the fluid passes through the bed, the concentration in
this fluid drops down very rapidly with distance in the bed to zero way before the end of
the bed is reached. The concentration profile at the start at time t1 is shown in Fig. 2, where
the concentration ratio c/co is plotted versus bed length. The fluid concentration co is the
feed concentration and c is the fluid concentration at a point in bed.

Figure 2: Concentration profiles for adsorption in a fixed-bed: profiles at various


positions and times in the bed (Geankoplis, 1993).

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The dashed line for time t3 shows the concentration in the fluid phase in equilibrium
with the solid. The difference in concentrations is the driving force for mass transfer
(Geankoplis, 1993).

C. Breakthrough Concentration Curve


At a given time t3, when almost half of the bed is saturated with solute, the outlet
concentration is still approximately zero, as shown in Fig. 3. This outlet concentration
remains zero until the mass-transfer zone starts to reach the tower outlet at time t4. Then
the outlet concentration starts to rise and at t5 the outlet concentration has risen to cb, which
is called the break point.
The break-point concentration represents the maximum that can be discarded and is
often taken as 0.01 to 0.05 for cb/co. The value cd/co is taken as the point where cd is
approximately equal to co (Geankoplis, 1993).

Figure 3: Breakthrough concentration profile in the fluid at outlet of bed (Geankoplis,


1993)
D. Capacity of the Column

The total or stoichiometric capacity of the packed-bed tower, if the entire bed comes to
equilibrium with the feed, can be shown to be proportional to the area between the curve
and a line at c/co = 1.0 as shown in Fig. 4.

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Figure 4: Determination of the capacity of column from the breakthrough curve
(Geankoplis, 1993).

The total shaded area represents the total or stoichiometric capacity of the bed as follows:

∞ 𝑐
𝑡𝑡 = ∫0 (1 − 𝑐 ) 𝑑𝑡 (3)
𝑜

where tt is the time equivalent to the total or stoichiometric capacity. The usable capacity
of the bed up to the break-point time tb is the crosshatched area.

𝑡 𝑐
𝑡𝑢 = ∫0 𝑏 (1 − 𝑐 ) 𝑑𝑡 (4)
𝑜

where tu is the time equivalent to the usable capacity or the time at which the effluent
concentration reaches its maximum permissible level.

The ratio of tu / tt is the fraction of the total bed capacity or length utilized up to the break
point. Hence, for a total bed length of HT m, HB is the length of bed used up to the break
point,

𝑡𝑢
𝐻𝐵 = 𝐻𝑇 (5)
𝑡𝑡

The length of the unused bed HUNB in is then the unused fraction times the total length.

𝑡
𝐻𝑈𝑁𝐵 = (1 − 𝑡𝑢) 𝐻𝑇 (6)
𝑡

Hence, to obtain the total length of the column:

𝐻𝑇 = 𝐻𝑈𝑁𝐵 + 𝐻𝐵 (7)

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Note that HUNB represents the mass-transfer section or zone. It depends on the fluid velocity
and is essentially independent of the total length of the column (Geankoplis, 1993).

III. MATERIALS AND METHODOLOGY


A. Materials
i. Reagents

REAGENT AMOUNT
Activated carbon 45 grams
Dyeing agent 16.5 grams
Distilled water 2 liters
Filter paper 1 piece

ii. Apparatus

APPARATUS CAPACITY UNCERTAINTY


300 g ± 0.0001 g
Analytical balance 300 g ± 0.005g
50 kg ± 0.01 kg
Beaker 250 mL ± 5 mL
Erlenmeyer flask 250 mL ± 5 mL
Burette 50 mL ± 0.02 mL
25 mL ± 0.5 mL
Graduated cylinder
250 mL ± 0.1 mL
Hydrometer - ± 0.0005
Ruler 30 cm -
Funnel - -
Stirring rod - -
Stopwatch - -

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B. Schematic Diagram
i. Preparation of Reference Solutions

Prepare 0, 0.2, 0.4, 0.6, 0.8 and 1%w/w dye solution.

Determine the density of the individual solution at room


temperature.

Plot the concentrations as a function of density.

Determine the best equation that represents the experimental data.

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ii. Adsorption Isotherm Determination

Load 5 grams of activated carbon into 5 beakers (250 mL).

Pour 200 mL of 0.2, 0.4, 0.6, 0.8 and 1% w/w dye in each beaker, respectively.

Stir the solution every 1 minute.

Measure the density of each setup by determining the weight of the solution every 2
minutes.

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Repeat step 3 and 4 until the density of the liquid remains constant with respect to time.

Correlate the measured density to concentration using the equation obtained from Part A.

Determine the amount absorbed per unit amount of adsorbent (W).

Plot W as a function of the equilibrium concentration.

Determine the best isotherm that represents the adsorption process.

iii. Design of Fixed-bed Adsorption Column

Load a predetermined amount of activated carbon in the burette until it


reaches a compacted height of 10 cm.

Record the weight of the activated carbon.

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Set-up the burette in the iron stand.

Fill the graduated cylinder with 1% w/w solution. Note: Stock adequate amount of
1% w/w solution.

Set the stopcock of the burette quarterly open. Start the timer.

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Determine the average volumetric flow rate.

Collect a measurable volume of the effluent every ten minutes from the outlet of the burette.
Note: Don’t get the samples from the bulk of the effluent.

Determine the density of the effluent.

Repeat steps 7 and 8 until the density of the effluent remains constant.

Correlate the densities in terms of concentrations.

Plot the breakthrough curve (C/C0 vs. time).

Compute for the height of used bed (HB) and height of unused bed (HUNB).
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C. Methodology
i. Preparation of Reference Solutions

A 0, 0.2, 0.4, 0.6, 0.8 and 1% w/w dye solution was prepared using distilled water as
the solvent. The solutions were prepared by weighing 0.5, 1.0, 1.5, 2.0 and 2.5 grams of
blue colored dye using an analytical balance with ±0.01 g uncertainty and adding it to
249.50, 249.00, 248.50, 248.00 and 247.50 grams of distilled water in a 500 mL beaker.
After the preparation, the densities of each solution was determined using a hydrometer
(with ±0.0005 g/mL error) starting from the blank solution up to the 1% w/w dye solution.
The actual concentrations were determined by using the blank solution as the reference and
adding the correcting value to the relative density of the solutions. A plot of concentrations
as a function of densities was made including the errors propagated and the best equation
that represents the experimental data was determined by obtaining the coefficient of
determination (R2) of the possible equations. The best equation was selected on the criterion
of which line will pass through 70% of error bars.

ii. Adsorption Isotherm Determination

Five sets of five grams of activated carbon were weighed in analytical balance with
±0.01g uncertainty and was placed in five 250 mL beakers. The procedure started by
pouring 200 mL of 0.2% w/w dye solution in the first beaker with 5 grams of activated
carbon. The solution was stirred for 1 minute and was allowed to rest for 1 minute. Then,
the density of the set-up was determined by obtaining the mass and the volume of the
solution from a sample. The mass of the solution was obtained using an analytical balance
with ±0.0001 g error and subtracting the mass of solution plus the mass of the graduated
cylinder to the mass of the graduated cylinder used. The volume of the solution was
determined using a graduated cylinder with ±0.5 mL uncertainty. After which, the density
of the sample was obtained by dividing the mass of the solution over its volume.
Consequently, the sample was returned to the solution and the process was repeated until
the density of the liquid remained constant. Due to the unavailability of the analytical
balance, the measurement of the mass of the solution every 2 minutes was not met. The
same procedure was performed using 0.4, 0.6, 0.8 and 1 % w/w dye solution. After all set-
up was finished, the amount of dye adsorbed per unit adsorbent was determined. Lastly, a
plot of W and equilibrium concentration was made to determine the best isotherm that
represents the experimental data.

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iii. Design of Fixed Bed Adsorption Column

Two solutions with concentrations of 1 and 0.5% w/w dye solutions were prepared by
weighing 7.0000 and 4.0000 grams respectively for each concentration using an analytical
balance with ±0.0001g uncertainty. The weighed dye were added to 693(±0.0001g) and
796(±0.0001) grams of distilled water to produced 700 and 800 grams of dye solutions.
The bed for the 1% dye solution was prepared by putting the granulated activated carbon
inside the burette until the bed height reached 10 cm using a ruler as guide. The activated
carbon was removed from the burette and its mas was determined. The same procedure was
done to prepare a bed with height of 10 cm for the 0.5% dye solution. Two more beds were
prepared for each solution, this time having a height of 5 cm.

The experiment was performed by setting up the burette on the iron stand and then
pouring the 1% solution into the burette, the stopcock was opened and the timer was started.
The average volumetric flowrate was determined by reading the change in the volume of
the fluid inside the burette for a specific time range. This was performed three times then
the average volumetric flowrate was calculated. After 10 minutes, the effluent was
collected and its mass and volume were determined with the use of analytical balance and
graduated cylinder. From these information, the density of the effluent was calculated.
Effluents were collected every after tem minutes until its density becomes constant. The
bed was replaced with the activated carbon having a height of 5 cm. The same procedure
was performed but opening of the stopcock was changed, thus having a different volumetric
flowrate. This whole experiment was repeated for the 0.5% dye solution for both a bed
height of 10 cm and 5 cm.

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IV. RESULTS AND DISCUSSION
A. Determination of equation correlating the density and concentration
Table 1: Density Raw Data Using Hydrometer
Concentration w/w%, (g/g) Density of dye (g/mL), ±0.0005 g/mL
0 0.9900
0.5 0.9865
1.0 0.9855
1.5 0.9975
2.0 0.9938
2.5 0.9951

The equation correlating the experimental data of the density and concentration was
determined by plotting the density versus concentration in consideration of all errors
propagated during the experiment. In this part, the raw data of densities obtained during the
experiment as tabulated in Table 1, is determined by using a hydrometer. However, the next
parts of the experiment proceeded by using mass over volume in determining the densities.
Since the equation obtained in this step will affect the succeeding calculations, it must be
considered that the inconsistent determination of the densities of the solutions will result to
more error. In solving this problem, a reference data provided is used and tabulated as follows.

Table 2: Reference Solutions


%w/w Weight of Volume of Sample of Mass of
Density
Dye Dye Water Solution Sample
(±0.025g/mL)
Solution (±0.0001g) (±0.1mL) (±0.5 mL) (±0.01 g)
0.0 0.00 200.0 20.0 19.57 0.9650
0.2 0.40 199.6 20.0 19.72 0.9785
0.4 0.80 199.2 20.0 19.77 0.9860
0.6 1.20 198.8 20.0 19.80 0.9885
0.8 2.60 198.4 20.0 19.99 0.9900
1.0 2.00 198.0 20.0 19.30 0.9995

Consequently, the data above was analyzed to determine the equation correlating the
density and the concentration. All calculations and propagated errors are shown in the
Appendix. In obtaining the equation that best represents the experimental data, error bars are
used, according to the Lab Manual presented by University of Pennsylvania, the line must pass
through 70% of the error bars. The final density errors are shown in Table 3 to determine the
final equation.

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Table 3: Final Data Used for Equation Determination
70 % error range
w/w Concentration, g/g Density, g/mL Error bar
Min Max
0.000 0.924 0.924 1.01 0.0591
0.002 0.947 0.937 1.02 0.0595
0.004 0.971 0.944 1.03 0.0597
0.006 0.994 0.947 1.03 0.0597
0.008 1.018 0.948 1.03 0.0598
0.01 1.042 0.958 1.04 0.0600

DENSITY VS CONCENTRATION FOR DYE SOLUTION


0.012
y = 0.0849x - 0.0784
R² = 1
0.01
Concentration, w/w%

0.008

0.006

0.004

0.002

0
0.88 0.9 0.92 0.94 0.96 0.98 1 1.02 1.04 1.06 1.08
Density, g/mL

Figure 5: Plot of Density vs Concentration for Dye Solution

It can be observed that the densities obtained by using the equation of the line fell within
the range of 70% error bar and the line’s coefficient of determination is equal to 1. It can be
said from Table 3 that as the density increases, the concentration also increases. This accounted
to the fact that adding more solute to a solvent changes the composition of particles in a given
volume or mass of solution. This results in the change of concentration that is derived by using
the mass of the solution over the mass or volume of the solvent. The equation obtained as
y=0.0849x-0.0784 in this part will be used in the succeeding calculations.

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B. Determination of adsorption isotherm
As stated from the procedure in Methodology II, the density of the samples was obtained
by dividing the mass of the sample taken from the prepared solutions in Methodology I to its
volume. Once the density at a certain time is approximately equal to its subsequent density
after 2 minutes, the determination of density stops. The following results are shown in the
tables below.

Table 4: Density at 0.2 % w/w dye solution


Mass of Sample (g) Volume of Sample (mL)
Time, min Density, g/mL
(±0.0001 g) (±0.5 mL)
2 23.8011 24.5 0.971
4 24.1042 25.0 0.964
6 22.9829 24.0 0.958
8 23.4442 24.5 0.957
10 22.9516 24.0 0.957

Table 5: Density at 0.4 % w/w dye solution


Mass of Sample (g) Volume of Sample (mL)
Time, min Density, g/mL
(±0.0001 g) (±0.5 mL)
2 23.7699 24.5 0.970
4 23.5209 24.5 0.960
6 23.4521 24.5 0.957
8 22.9204 24.0 0.955
10 22.9314 24.0 0.955

Table 6: Density at 0.6 % w/w dye solution


Mass of Sample (g) Volume of Sample (mL)
Time, min Density, g/mL
(±0.0001 g) (±0.5 mL)
2 24.6025 25.1 0.926
4 24.0780 24.9 0.913
6 24.0808 25.0 0.910
8 24.0840 25.0 0.909

Table 7: Density at 0.8 % w/w dye solution


Mass of Sample (g) Volume of Sample (mL)
Time, min Density, g/mL
(±0.0001 g) (±0.5 mL)
2 24.0017 24.8 0.969
4 22.6296 23.9 0.947
6 22.6042 24.0 0.942
8 22.7964 24.2 0.942

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Table 8: Density at 1.0 % w/w dye solution
Mass of Sample (g) Volume of Sample (mL)
Time, min Density, g/mL
(±0.0001 g) (±0.5 mL)
2 23.8011 24.5 0.971
4 24.1042 25.0 0.964
6 22.9829 24.0 0.958
8 23.4442 24.5 0.957
10 22.9516 24.0 0.956

To put things simply, the density of the dye solution changes with time as adsorption
proceeds. As time passes by, it can be observed that the density in each concentration (0.2%,
0.4%, 0.6%, 0.8% and 1.0 %) is decreasing. The reason for this is that the dye that was
dissolved in the water is slowly being adsorbed in the activated carbon, causing its mass to
gradually decrease. However, certain factors can also be considered like the adsorption
capacity of the filter paper used in the separation of the sample from the solution and small
losses of activated carbon granules during this process. It was due to this that the densities
obtained are assumed to be inaccurate.

Another observation is that at the initial times from 2 to 4 minutes, sudden changes in
densities at two significant figures are shown, while the next passing minutes have small
changes, having difference only at 3 significant figures. According to Geankoplis (1993), when
the fluid is passed through the bed, the solid particles adsorb components from the fluid. When
the bed is almost saturated, the concentration would remain almost constant and the flow in the
bed is stopped. This is of somewhat similar case with that of obtained densities in the
experiment. At time 2 to 4 minutes, the activated carbon just continuously adsorbs dye solute
in the solution, however at the subsequent minutes; the adsorbent slowly becomes saturated
causing a decreasing change in the densities. Once it is fully saturated, the density remains
almost constant from its previous density, hence stopping the whole process. In the 0.2%, 0.4%
and 1.0% w/w dye solutions, the density became constant at 10 minutes, while it was 8 minutes
for both 0.6% and 0.8% w/w dye solutions.

A more in-depth explanation is expounded in the study of (Chattopafhyahya, 2017),


according to him the removal of dye is rapid in initial stages but when it approaches
equilibrium, it slows down gradually. This is due to the availability of vacant surface sites
during the preliminary stage of adsorption, and after a certain period of time the vacant sites
are occupied by dye molecules, which lead to create a repulsive force between the adsorbate
on the adsorbent surface and in bulk phase. In the experiment, the attainment of equilibrium

17
takes place after agitating the solutions containing the adsorbent up to 8-10 minutes and once
equilibrium was attained, the percentage of adsorption of dye did not show any appreciable
change with time. This suggests that after equilibrium is attained, further treatment does not
provide more removal.

However, since the hydrometer is not used in determining the densities, certain errors can
be derived in its calculation, proving them inaccurate. To compensate for this, the propagation
of errors, as shown in Appendix B, were calculated, acquiring the density error and its
minimum and maximum corrected value. With the help of this data, the final density is
determined from the corrected range of errors.

Table 9: Summary of the final densities at different concentration (w/w %) dye solution
Time (min) 0.20% 0.40% 0.60% 0.80% 1.00%
2 0.939 0.941 0.944 0.948 0.945
4 0.932 0.931 0.931 0.925 0.938
6 0.925 0.928 0.927 0.928 0.931
8 0.92 0.925 0.927 0.928 0.930
10 0.924 0.926 ------- ------- 0.929

Note that the final density is merely an approximate. This density is used to determine the
final concentration of the dye solution after the adsorption process using the equation
correlating the density and concentration in Results A. Ideally, in an adsorption process, the
concentration obtained must be less than the initial concentrations (0.2%, 0.4%, 0.6%, 0.8%
and 1.0 %) of the solution. Nevertheless, by approximately calculating the final density through
the corrected range of errors using Excel®, the final density that is less than its initial value
can be obtained, creating a decreasing trend in concentration. Another basis of this is also the
percentage removal of the adsorbent. In the study of (Chattopafhyahya, 2017), it was stated
that when the initial concentration of dye solution increases, the percentage removal of the
adsorption process decreases. The same goes in the study of (Sharma & Uma, 2009), stating
that for low concentration ranges, the percentage removal of the dye is higher. That said,
assuming that the optimum percentage removal to be greater than 95%, the initial assumption
from 0.2% is greater than 95% followed by a decreasing trend up to 1.0%. Overall, by using
this method, the final concentrations obtained has approximately ±0.0016 error.

18
Afterwards, the mass of dye per volume of solution, c, and the mass of dye adsorbed per
mass of activated carbon, w, were calculated. A plot of c versus w was done to determine
whether it is a Freundlich Isotherm. Alternatively, a plot of 1/c versus 1/w was also done for
Langmuir Isotherm. This was done on time 2, 4, 6, and 8 minutes. Since both 0.6% and 0.8%,
w/w dye solutions became constant at 8 minutes, the data from time t = 10 minutes are not
considered.

Table 10: R2 values of the Freundlich and Langmuir Isotherm Plots at different time t
Time (minutes) Freundlich Isotherm Langmuir Isotherm
2 0.7444 0.6829
4 0.0044 0.1054
6 0.7729 0.8558
8 0.9604 0.8541

Optimum results were shown at t = 8 minutes, having high values of R2 for both Freundlich
and Langmuir Isotherm. Others, especially at t = 4 minutes, have points that are too far away
from each other to form a line, thus, only t = 8 minutes will be further discussed.

Table 11: Freundlich Isotherm Raw Data at t = 8 minutes


Concentration of Dye c w
Solution, w/w % ( g dye/mL solution ) ( g dye adsorbed/g AC )
1 0.000532887 0.010134648
0.8 0.000389761 0.008164909
0.6 0.000280309 0.006146290
0.4 0.000151895 0.004145200
0.2 0.000123100 0.002018277

Figure 6: Plot of Freundlich Isotherm at t = 8 minutes

19
Table 12: Langmuir Isotherm Raw Data at t = 8 minutes
Concentration of Dye Solution, 1/c 1/w
w/w % ( mL solution/g dye ) ( g AC / g dye adsorbed )
1 1876.571 98.67140835
0.8 2565.677 122.4753418
0.6 3567.489 162.6997654
0.4 6583.494 241.2428659
0.2 8123.466 495.4722064

Figure 7: Plot of Langmuir Isotherm at t = 8 minutes

Comparing both plots, the isotherm with the highest R2 is the Freundlich isotherm, having
a value equal to 0.9604, while Langmuir isotherm has only 0.8541, thus, the Freundlich
isotherm fitted better since it is more accurate. Taking this into consideration, the adsorption
isotherm involved in the process is hence the Freundlich Isotherm. This is considered
reasonable since Geankoplis (1993) stated that this isotherm is particularly useful for liquids.
By further calculations and simplifications, the Freundlich Isotherm equation is determined to
be w  18.1472175c 0.9834117406 .

20
C. Determination of the effect of different parameters such as volumetric flowrate,
compacted bed height, and initial concentration on the adsorption process
i. Raw data for 0.5 %w/w dye solution

Table 13: Raw Data Summary for the Adsorption of 0.5% Dye Solution
Flowrate (ml/sec) 10 cm bed height 5 cm bed height
Trial 1 0.1143 0.1220
Trial 2 0.1111 0.1027
Trial 3 0.1010 0.0877
Average Flowrate 0.1088 0.1041

Table 14: Densities of Effluent for the Adsorption of 0.5% Solution Using 10 cm Bed Height
Mass of Solution, g Volume, mL
Time(min) Density(g/mL) Density error(±)
(±0.0001 g) (±0.5 mL)
10 48.6454 52.5 0.927 0.00882
20 65.9183 69.0 0.955 0.00692
30 73.8450 75.5 0.978 0.00648
40 91.8353 93.5 0.982 0.00525
50 86.0423 87.6 0.982 0.00561

Table 15: Densities of Effluent for the Adsorption of 0.5% Solution Using 5 cm Bed Height
Mass of Solution, g Volume, mL
Time(min) Density(g/mL) Density error(±)
(±0.0001 g) (±0.5 mL)
10 50.5915 54.5 0.928 0.00852
20 51.603 53.5 0.965 0.00901
30 60.3173 61.5 0.981 0.00797
40 57.4055 58.5 0.981 0.00839

ii. Raw data for 1.0 %w/w dye solution


Table 16: Raw Data Summary for the Adsorption of 1.0% Dye Solution
Flowrate (ml/sec) 10 cm bed height 5 cm bed height
Trial 1 0.0980 0.0816
Trial 2 0.2041 0.0758
Trial 3 0.1887 0.0717
Average Flowrate 0.1636 0.0764

Table 17: Densities of Effluent for the Adsorption of 1.0% Solution Using 10 cm Bed Height
Mass of Solution, g Volume, mL
Time(min) Density(g/mL) Density error(±)
(±0.0001 g) (±0.5 mL)
10 55.1610 61.1 0.9028 0.0074
20 84.5213 89.9 0.9402 0.0052
30 84.6612 84.5 1.0019 0.0059
40 103.1106 102.1 1.0099 0.0049

21
Table 18: Densities of Effluent for the Adsorption of 1.0% Solution Using 5 cm Bed Height
Mass of Solution, g Volume, mL
Time(min) Density(g/mL) Density error(±)
(±0.0001 g) (±0.5 mL)
10 50.0552 55.0 0.91009455 0.0083
20 49.2982 49.5 0.99592323 0.0101
30 58.8783 58.1 1.01339587 0.0087
40 61.0800 60.2 1.01461794 0.0084

The tables above show the raw data for 0.5 and 1.0 %w/w dye solution comprising of the
volumetric flowrates and densities obtained after carrying the steps specified in Methodology
III. Due to the error incurred by using the relationship of mass over volume, the relative error
on the calculated densities were also determined. It can be said based on Tables 14, 15, 17 and
18 that a common trend is observed in the densities obtained in both 5 and 10 cm bed height.
The densities showed an increasing trend until densities obtained on two consecutive time
periods became constant or approximately equal to each other. The reason for this phenomena
is explained and discussed on the generation of breakthrough curves for each process.

iii. Breakthrough curve generation

BREAKTHROUGH CURVE FOR 10 CM BED


HEIGHT
1.2

0.8

0.6
C/Co

0.4

0.2

0
0 10 20 30 40 50 60
-0.2
Time(min)

Figure 8: Breakthrough Curve for the 0.5% Solution and 10 cm Bed Height

22
BREAKTHROUGH CURVE FOR 5CM BED
HEIGHT
1.2

0.8
C/Co

0.6

0.4

0.2

0
0 5 10 15 20 25 30 35 40 45
Time(min)

Figure 9: Breakthrough Curve for the 0.5% Solution and 5 cm Bed Height

BREAKTHROUGH CURVE FOR 10 CM BED


HEIGHT
1.2

0.8
C/Co

0.6

0.4

0.2

0
0 5 10 15 20 25 30 35 40 45
Time(min)

Figure 10: Breakthrough Curve for the 1.0% Solution and 10 cm Bed Height

23
BREAKTHROUGH CURVE FOR 5 CM BED
HEIGHT
1.2

0.8
C/Co

0.6

0.4

0.2

0
0 5 10 15 20 25 30 35 40 45
Time(min)

Figure 11: Breakthrough Curve for the 1.0% Solution and 5 cm Bed Height
The figures above show the breakthrough curves for the adsorption of dye solutions using
fixed beds with known heights. These figures show the change in the concentration of the
effluent from the burette with time by determining first the concentration of the effluents with
the use of its correlation with density and plotting the solid concentration ratio versus time. It
can be observed that it shows the same trend as the change in the density of the effluent shown
in the raw data table where the values calculated continue to rise until they reach a point where
they become constant. This is due to the linear relationship between density and concentration
as previously determined on the first part of this experiment.

For the adsorption process, it can be observed from the curves that at the start of the
operation, the ratio of the concentration of the effluent and feed is equal to zero which denotes
that during this period no solute is present on the effluent, at the same time, none was also
adsorbed on the column. In the beginning, the layer of the bed which comes in contact with the
fluid called the Mass Transfer Zone adsorbs the solute from the fluid. As time passes, this
previous layers will be saturated and less effective for further adsorption so whatever escapes
from this will be trapped on the next zones. A plot showing the change in the concentration of
the solute is given by Figure 4, where at a given time, the concentration of the solute decreases
until it reaches zero as it flows through the bed. It is also shown on the plot that there will come
a time when the concentration of the effluent is no longer zero. The time when the concentration
starts to rise is called the breakpoint for which C/Co is set to be 0.01 to 0.05. After this period,
the effluent’s concentration will continue to rise rapidly until it reaches the time when the

24
concentration of the feed and effluent will be equal. For the generated breakthrough curves
above, the appearance of the curve and their breakpoints depend on the total length of the bed
and initial concentration. The effect of bed height and initial concentrations will be discussed
separately.

iv. Effect of bed height on bed breakthrough curve

BREAKTHROUGH CURVES OF 10CM AND 5CM


BED HEIGHT
1.2

0.8

0.6
C/Co

5 cm
0.4
10 cm
0.2

0
0 10 20 30 40 50 60
-0.2
Time(min)

Figure 12: Comparison of the Breakthrough Curves at 10cm and 5cm Bed Heights for 0.5%
Dye Solution

BREAKTHROUGH CURVE FOR 10CM AND 5CM


BED HEIGHT
1.2

0.8
C/Co

0.6
10cm
0.4 5cm

0.2

0
0 10 20 30 40
Time (min)

Figure 13: Comparison of the Breakthrough Curves at 10cm and 5cm Bed Heights for 1%
Dye Solution

25
Figures 12 and 13 show the comparison between the generated breakthrough curves for
different bed heights at the same feed concentration. As discussed on the breakthrough curve
of each solution, most of the bed will be saturated by the time that the C/Co reaches 1. Based
on the graph on Figure 12, the bed having a height of 5 cm reached its saturation point earlier
compared to the bed with 10 cm height. The concentration profile given by Figure 3 can be
used to describe this situation where it showed that a bed with larger height can actually be
used longer given that the feed concentration and flow rate is held constant. This is due to more
mass transfer zones on the bed that it would take longer to make the bed totally saturated. On
the other hand, Figure 13 didn’t show the same trend. This is because it was affected by the
volumetric flowrate. Due to the small volumetric flow rate on the 5 cm bed, it took a longer
time to start becoming saturated. The main reason is that the higher the volumetric flowrate the
more mass of solute will be exposed to adsorbent and it will take lesser time for the bed to be
saturated.

v. Effect of initial concentration on breakthrough curves

BREAKTHROUGH CURVES FOR THE


ADSORPTION OF 1% AND 0.5% SOLUTION
1.2

0.8

0.6
C/Co

0.5% Soln
0.4
1% Soln
0.2

0
0 10 20 30 40 50 60
-0.2
Time (min)

Figure 14: Comparison of the Breakthrough Curves at 10cm Bed Height for the Adsorption
of 1% and 0.5% Dye Solutions

26
BREAKTHROUGH CURVES FOR THE
ADSORPTION OF 1% AND 0.5% SOLUTION
1.2

0.8
C/Co

0.6
5% Soln
0.4
1% Soln
0.2

0
0 10 20 30 40 50
Time (min)

Figure 15: Comparison of the Breakthrough Curves at 5cm Bed Height for the Adsorption of
1% and 0.5% Dye Solutions
These figures show the effect of the initial concentration of the feed on the breakthrough
curve. It can be observed based on Figure 14 that in the bed for the 1.0 %w/w solution, the time
when the bed became saturated is reached earlier compared to that of the 0.5 %w/w solution.
This is accounted that for the lower concentration feed, there is lower concentration gradient
or driving force between the bed and the fluid. This causes a slower transport due to the
decrease in the mass transfer coefficient. It should be seen from the graphs that the breakpoint
time for the 1% solution is faster because of a higher concentration gradient which would result
to a faster mass transport from the fluid to the bed. However, in Figure 15, during the time that
the fluid is fed, the bed got disturbed where some granules floated and some blocked the exit
of the fluid. This caused a difference in the flowrate of the effluent which affected the
breakthrough curve.

27
vi. Usable and unusable bed height determination

Table 19: Determination of the Unusable Heights for the Adsorption Columns
0.5% Solution 1.0% Solution
Bed Height 10 cm 5 cm 10 cm 5 cm
C/Co 0.05 0.05 0.05 0.05
Tb(mins) 9.18 9.65 10.62 10.32
Tu(mins) 9.53 10.36 10.47 11.15
Ttotal(mins) 13.08 19.48 16.00 16.81
Husable(cm) 7.29 2.66 6.54 3.32
Hunusable(cm) 2.71 2.34 3.46 1.68

These results show the breakpoint times, total time of adsorption and the usable and
unusable heights of the beds. From the previous discussions, it was discussed that the effective
operation of the adsorbent would be affected by the bed height and initial concentration. A
longer bed corresponds to greater mass transfer zones and a lower feed concentration
corresponds to weaker driving force which would cause slower mass transfer. As a result, the
bed with a larger height and fed with a less concentrated fluid will have longer time before
reaching its saturation point and higher adsorption efficiency. These results can only be attained
if the flowrate was controlled to be constant for the different operations. From the results above
in 0.5 % w/w solution, it can be observed that the breakpoint time for the 5 cm bed is higher
than that of the 10 cm bed. This is due to the small volumetric flow rate on the 5 cm bed that it
took a longer time to get to its break point. In this case, two concentrations exposed into two
different bed heights have different flow rates and that results into inconsistent Tb. This effect
is also true for the usable height of the beds. The determination of the usable height was based
on the time that the bed can be effectively used and therefore, the effect of flowrate on the
breakpoint time would also affect the height of usable bed. All calculations are shown in the
Appendix.

28
D. Design of Fixed-bed Adsorption Column
i. Design problem
Design a fixed-bed adsorber that is capable of operating for 12 hours. Target break through
concentration ratio is 0.01. State your assumptions clearly.

ii. Assumptions
The initial data will be based from the data of Results C and is tabulated as follows:

Table 20: Data Assumptions1


Bed Height 10
Weight of Activated Carbon (g) 4.4154
Feed Density (g/mL) 0.999
Volumetric Flowrate (mL/sec) 0.1636
Ttotal (min) 16

Basing on the breakthrough curve shown in Figure 8, we can determine the following data:

Table 21: Data Assumptions 2


C/Co 0.05
Tb(mins) 10.62
Tu(mins) 10.47
Ttotal(mins) 16.00
Husable(cm) 6.54
Hunusable(cm) 3.46

iii. New total height of Fixed bed


Using the data determined from the breakthrough curve, solve for the new height of
adsorption bed:

T
Husable ( New )  b new ( H usable/ old )
Tb old
720 min utes
Husable ( New )  ( 6.54 cm )
5.85 min utes
H usable (New)= 805.86 cm

HT ( New )  H usable  H unusable


 805.86 cm  3.46 cm
HT (New)=809.32 cm

29
iv. Saturation capacity determination
With the data assumed, the calculation of saturation capacity of the up-scaled
adsorption bed can be performed:

Flowrate  (Volumetric flowrate )(  feed )


mL g
Flowrate  ( 0.1636 )( 0.9995 )
sec mL
g
Flowrate=9.811
min

Total Dye Adsorbed  ( Concentration )( Flowrate )( tt )


0.01 g dye g sol' n
Total Dye Adsorbed  ( )( 9.811 )( 16 min)
g sol' n min
Total Dye Adsorbed= 1.56976 g dye
wt. dye adsorbed
Saturation Capacity 
wt. activated carbon
1.56976 g dye
Saturation Capacity 
4.4154 g AC
g dye
Saturation Capacity=0.3555
g AC

30
v. Schematic diagram of adsorption column

C0 = 1 %w/w dye solution


Flowrate = 9.811 mL/min

Husable = 805.86 cm
HTotal = 809.32 cm

Hunusable = 3.46 cm

C/C0 = 0.01

Saturation Capacity = 0.3555g dye/ g AC

Figure 16: Schematic diagram of the adsorption column

31
V. CONCLUSION
In this experiment, the performance of a packed bed of activated carbon adsorbent to purify
or cleanse varying concentrations of dye solution is evaluated. Starting with the determination
of relationship of the densities of the reference solution versus the concentration, a linear
relationship with the equation y=0.0849x-0.0784 is obtained. This equation was used to
determine the final concentrations after obtaining the final densities as shown in the appendix.

Secondly, in the determination of adsorption isotherm, different concentrations of 0.2, 0.4,


0.6, 0.8 and 1 %w/w solution were poured in 5 grams of activated carbon and the densities of
the solutions every after two minutes were determined. It was observed that, the density of dye
solution decreases with time as the adsorption proceeds. It was generalized that at the first two
to four minutes that the changes in density were two significant figures until it was observed
that the density changes became smaller and became constant. This observation proves the
theory specified by (Geankoplis, 1993) that when a fluid is passed through a bed, the solid
particles adsorb components from the fluid. When the bed is almost saturated, the concentration
would remain almost constant and the flow in the bed is stopped. Consequently, the mass of
dye per volume of solution, c, and the mass of dye adsorbed per mass of activated carbon, w,
were calculated. A plot of c versus w was done to determine whether it is a Freundlich Isotherm.
Alternatively, a plot of 1/c versus 1/w was also done for Langmuir Isotherm. It was found that
the optimum results of coefficient determination were determined at time equal to 8 minutes.
A Freundlich isotherm with the equation w  18.1472175c 0.9834117406 is chosen as the best
isotherm that fits the exprimental data with a coefficient of determination equal to 0.9604. This
is considered reasonable since Geankoplis (1993) stated that this isotherm is particularly useful
for liquids.

The effect of different parameters such as bed height, volumetric flowrate and initial
concentration on the adsorption process were determined. Breakthrough curves were generated
to show the relationship between the ratio of the concentration at a specific time over the initial
concentration versus time. It was concluded that a bed with larger height can be used longer
given that the feed concentration and volumetric flow rate are held constant. This is due to
more mass transfer zones on the bed that it would take longer to make the bed totally saturated.
As per the effect of the initial concentration, it was determined that for lower concentration of
the feed, there is lower concentration gradient or driving force between the bed and the fluid.
This causes a slower transport due to the decrease in the mass transfer coefficient. However,
the results obtained in Results C-v showed that the 0.5 %w/w dye solution reached the

32
breakpoint time faster which is unideal. This error is accounted to the fact that when the dye
solutions are fed, the bed got disturbed and some granules floated and blocked the exit of the
fluid.

In addition, in the calculation of the usable and unusable bed height, it was found out that
in the breakpoint times for 0.5 % w/w solution, the 5 cm bed was higher compared to that of
10 cm bed. This is due to the small volumetric flow rate on the 5 cm bed that it took a longer
time to get to its break point. It was also observed that for usable and unusable bed height, the
heights calculated were a function of flowrate and breakpoint time.

In the design problem specified, it was found out that for new operating time of 12 hours
with a target breakthrough of 0.01, the new bed height calculated was 809.32 cm. By assuming
that the operating conditions were the same with that of 1.0 %w/w dye solution at 10 cm bed
height, the flowrate of the feed is computed as 9.811 g/min and the bed’s saturation capacity is
0.3555 grams of dye/ grams of activated carbon.

33
VI. RECOMMENDATIONS
In view of more precise and accurate results, the researchers would like to recommend the
following:

1. Consistency of the method used in determination of the densities of the solutions


 This is very important for the accuracy of the data gathered in the experiment.
Throughout the experiment, the method for determining the densities varied from
using the hydrometer to using the relationship of mass over volume. In effect, the
data gathered in the Part A became unusable due to inconsistencies of results. If
possible, one method must be used and using the hydrometer is preferable.

2. Proper calibration and selection of equipment


 All equipment must be properly calibrated and one equipment must be used to
measure the mass of all reagents and chemicals used. In the experiment, due to the
insufficient equipment, the determination of weights were made by using different
types of weighing scale with different uncertainties. For the sake of uniformity and
precision, one equipment must be used to measure one specific parameter.

3. Enough equipment and apparatus for the experiment


 This will remove the extra time the groups spend to wait for their turns to use an
equipment. In effect, the experimental procedures will be carried out based on
specific instructions and will not be delayed.

4. Use of Commercial Activated Carbon


 In the experiment, the source of activated carbon was not specific and its
commercial specifications were unknown. Due to this, it was difficult for the
researchers to identify if the activated carbon was properly activated and if it can
actually be used as an adsorbent.

5. Use of other Adsorbents


 To compare the adsorption efficiency of the activated carbon, other adsorbents may
be used to achieve this objective.

34
VII. STUDY QUESTIONS
1. How much dye is needed for the whole experiment?
A. Determination of densities of solution and adsorption isotherms

Table 22: Mass of Dye Used in Part A


% w/w Concentration Mass of Dye ±0.01 g
0.2 0.50
0.4 1.00
0.6 1.50
0.8 2.00
1 2.50
Total mass of Dye 7.50 g ±0.01 g

B. Determination of adsorption Bed length and dye solution concentration in the


adsorption

Table 23: Mass of Dye Used in Part B


% w/w Concentration Height of Bed (cm), ±0.01 cm Mass of Dye(g), ±0.01 g
10.00 2.50
x1.00
5.00 2.50
10.00 1.25
0.5
5.00 1.25
Total mass of Dye 7.50 g ±0.01 g

The total amount of dye is solved as

Total mass of Dye  7.50 g  7.50 g


Total mass of Dye =15.0 g

The error in obtaining the amount of dye is

z   x 2   y 2
z  0.012  0.012
z=0.01

Final amount of dye used

Total mass of Dye =15.0 g  0.01g

Ideally, the amount of dye that must be used is 15.0g± 0.01 g, however, two sets of
concentrations (0.2 and 0.4 %w/w) was repeated due to random errors. The theoretical total
dye used is 16.5g ± 0.01g.

35
2. How do you separate powdered adsorbent from the fluid to get desired volume/density
of effluent?

In obtaining samples from the solution to determine the density of the effluent, the
researchers made used of two methods: decantation and filtration. However, the
methods posed two different disadvantages. The disadvantage of decanting a sample is
that some activated carbon were accidentally incorporated in the sample. Due to this,
when the researches tried to separate the activated carbon, some dye and solution
adhered to the fingers of the researches. Consequently, it must be noted that this
potentially deviates the results from correctly obtaining the density of the effluent. On
the other hand, using a filter paper filters the powdered dye and also creates errors in
obtaining the density of the samples. Although both methods poses disadvantages,
separating the powdered adsorbent must be done by decantation. This method is chosen
because it produces less error compared to filtration.

36
VIII. REFERENCES
[1] Carrie Carlson, W. H. (n.d.). FEECO international, inc. Introduction to Activated CArbon.
Retrieved from FEECO interntional: http://feeco.com/introduction-to-activated-carbon/

[2] Chattopafhyahya, M. &. (2017). Adsorption characteristics for t-producthe removal of a


toxic dye, tartrazine from aqeous solutions by a low cost agricultural . Arabian Journal of
Chemistry.

[3] Czelej et. al., K. (2016). Czelej, K., Cwieka,CO2 stability on the Ni low-index surfaces:
Van der Waals corrected DFT analysis. 33-38.

[4] F.Rodriguez, R.-A. (2015). Activated Carbon and Adsorption.

[5] Ferrari et. al., L. (2010). Ferrari, L.; Kaufmann, JInteraction of cement model systems with
superplasticizers investigated by atomic force microscopy, zeta potential, and adsorption
measurements.

[6] Gabelman, A. P. (2017). Adsorption Basics.

[7] Geankoplis, C. J. (1993). Transport Processes and Unit Operations. University of


Minnesota: Prentice-Hall International, Inc.

[8] Perry, R. H., & Green, D. W. (2008). Perry’s Chemical Engineers’ Handbook (8th ed.).
United States of America: McGraw-Hill Companies, Inc.

[9] Seader, J. a. (1998). Separation Process Principles.

[10] Sharma, Y., & Uma. (2009). Optimization of parameters for the adsorpton of Methylene
Blue on low cost activated carbon. Journal of Chemical & Engineering Data, 435-439.

37
IX. APPENDIX
A. Determination equation of line
Table 24: Equation Determination Data
%w/w Weight of Volume of Sample of Mass of
Density
Dye Dye Water Solution Sample
(±0.025g/mL)
Solution (±0.0001g) (±0.1mL) (±0.5 mL) (±0.01 g)
0.0 0.00 200.0 20.0 19.57 0.9650
0.2 0.40 199.6 20.0 19.72 0.9785
0.4 0.80 199.2 20.0 19.77 0.9860
0.6 1.20 198.8 20.0 19.80 0.9885
0.8 2.60 198.4 20.0 19.99 0.9900
1.0 2.00 198.0 20.0 19.30 0.9995

Table 25: Error Calculation Data for Equation Determination


Not corrected Corrected
Corrected
min max min max
1.0135 0.9535 1.0035 0.9185 1.0385
1.0210 0.9610 1.0110 0.9260 1.0460
1.0235 0.9635 1.0135 0.9285 1.0485
1.0250 0.9650 1.0150 0.9300 1.0500
1.0345 0.9745 1.0245 0.9395 1.0595
1.0000 0.9400 0.9900 0.9050 1.0250
Error 0.0350

The error obtained in this step is obtained as

Error  Standard  water  Actual  water


g g
Error  1.000  0.9650
mL mL
g
Error=0.0350
mL
i. Calculation of actual density error

2 2
z  x   y 
    
z  x   y 
2 2
 x   y 
z  z     
 x   y 
2 2
 0.01   0.5 
z  0.965    
 19.3   20 
z=0.024

38
ii. Calculation of 70% error range
Error   0.70  density error  correction factor 
Error   0.70  0.024  0.0350 
Error=0.024

Table 26: Error Bars Data


Not corrected Corrected 70% error range
Density error Corrected density
min max min max min max
0.024 1.000 0.941 0.989 0.906 1.024 0.924 1.006
0.024 1.014 0.954 1.003 0.919 1.038 0.937 1.020
0.025 1.021 0.961 1.011 0.926 1.046 0.944 1.028
0.025 1.024 0.964 1.013 0.929 1.048 0.947 1.031
0.025 1.025 0.965 1.015 0.930 1.050 0.948 1.032
0.025 1.035 0.975 1.024 0.940 1.059 0.958 1.042

iii. Calculation of actual concentration error

2 2
z  x   y 
    
z  x   y 
2 2
 x   y 
z  z     
 x   y 
2 2
 0.0001   0.1 
z  0    
 0   200 
z=0.0

Since the concentration is equal to 0, it did not affect the vertical error and was
neglected.

iv. Equation of the line


The line was defined using two points, the maximum and minimum values that fell
within the range of 70% error. After obtaining the equation, it was used to determine
the densities given the concentration.
Equation of line:
y  0.0849 x  0.0784
Solving x in terms of y

39
y  0.0849 x  0.0784
y  0.0784
x
0.0849
Solving the density at 0.004 w/w concentration
y  0.0849 x  0.0784
0.004  0.0784
x
0.0849
x=0.971
To show that density accurately, the number of significant figures used in this
calculation is three.
v. Excel Files

40
B. Determination of the Adsorption Isotherm
i. Calculation of actual density error
At initial concentration of 0.2% w/w dye solution:

2 2
z  x   y 
    
z  x   y 
2 2
 x   y 
z  z     
 x   y 
2 2
 0.0001   0.5 
z  0.97147    
 23.8011   24.5 
z=0.01982599
The same method is done in 0.4%, 0.6%, 0.8% and 1.0 % w/w concentrations.

ii. Calculation of final density


At initial concentration of 0.8% w/w dye solution:
final density  Corrected min  (density factor )  density error  correction factor 
final density  0.91665   0.415 0.01982599  0.0350 
g
final density=0.939400265
mL
Note that the density factor varies depending on the final concentration and
percentage removal of the adsorbent.

Table 27: Final Density at 0.2 % w/w dye solution


Not Corrected Corrected
Final Density, g/mL
Density error min max min max
0.019825990 0.951647 0.991299 0.916647 1.026299 0.939400265
0.019283360 0.944885 0.983451 0.909885 1.018451 0.932412234
0.019950434 0.93767 0.977571 0.90267 1.012571 0.925474829
0.019528697 0.937377 0.976435 0.902377 1.011435 0.925006835
0.019923264 0.936393 0.97624 0.901393 1.01124 0.924186557

41
Table 28: Final Density at 0.4 % w/w dye solution
Not Corrected Corrected
Final Density, g/mL
Density error min max min max
0.019800000 0.9504 0.99 0.9154 1.025 0.940608
0.019592587 0.940444 0.979629 0.905444 1.014629 0.930556738
0.019535277 0.937693 0.976764 0.902693 1.011764 0.927779522
0.019896181 0.93512 0.974913 0.90012 1.009913 0.925372729
0.019905730 0.935569 0.975381 0.900569 1.010381 0.925825906

Table 29: Final Density at 0.6 % w/w dye solution


Not Corrected Corrected
Final Density, g/mL
Density error min max min max
0.019525484 0.960654 0.999705 0.925654 1.034705 0.943647209
0.019417429 0.947571 0.986405 0.912571 1.021405 0.930528274
0.019264640 0.943967 0.982497 0.908967 1.017497 0.926874691
0.019267200 0.944093 0.982627 0.909093 1.017627 0.927000976

Table 30: Final Density at 0.8 % w/w dye solution


Not Corrected Corrected
Final Density, g/mL
Density error min max min max
0.019512309 0.948298 0.987323 0.913298 1.022323 0.946550684
0.019808477 0.927037 0.966654 0.892037 1.001654 0.925469882
0.019621702 0.92222 0.961463 0.88722 0.996463 0.928186241
0.019462810 0.922537 0.961463 0.887537 0.996463 0.928384297

Table 31: Final Density at 1.0 % w/w dye solution


Not Corrected Corrected
Final Density, g/mL
Density error min max min max
0.01982599 0.951647 0.991299 0.916647 1.026299 0.944608734
0.01928336 0.944885 0.983451 0.909885 1.018451 0.937569153
0.019950434 0.93767 0.977571 0.90267 1.012571 0.93069512
0.019528697 0.937377 0.976435 0.902377 1.011435 0.930187061
0.019923264 0.936393 0.97624 0.901393 1.01124 0.929404267

iii. Calculation of the final concentration


At initial concentration of 0.8% w/w dye solution:
y  0.0849 x  0.0784
final concentration  0.0849  final density   0.0784
final concentration  0.0849  0.946550684   0.0784
final concentration=0.001962153

The same method is done in 0.4%, 0.6%, 0.2% and 1.0 % w/w concentrations.

42
iv. Calculation of percentage removal
At initial concentration of 0.8% w/w dye solution:
initial concentration  final concentration
% removal   100
initial concentration
0.002  0.001962153
% removal   100
0.002
%removal=1.8923%

The same method is done in 0.4%, 0.6%, 0.2% and 1.0 % w/w concentrations.

v. Calculation of concentration error


At initial concentration of 0.8% w/w dye solution:
Concentration error  0.0849  density error
\ Concentration error  0.0849  0.019512309
Concentration error=0.0017
The same method is done in 0.4%, 0.6%, 0.2% and 1.0 % w/w concentrations.

Table 32: Summary of calculated data at 0.2 % w/w dye solution


Final concentration, w/w dye solution Percentage Removal Concentration Error
0.001355083 32.2458731 0.00168323
0.000761799 61.910066 0.00163716
0.000172813 91.3593502 0.00169379
0.00013308 93.3459862 0.00165799
6.34387E-05 96.8280654 0.00169149

Table 33: Summary of calculated data at 0.4 % w/w dye solution


Final concentration, w/w dye solution Percentage Removal Concentration Error
0.001457619 27.119041 0.00168102
0.000604267 69.7866481 0.00166341
0.000368481 81.5759307 0.00165855
0.000164145 91.7927657 0.00168919
0.000202619 89.869029 0.00169

Table 34: Summary of calculated data at 0.6 % w/w dye solution


Final concentration, w/w dye solution Percentage Removal Concentration Error
0.001715648 14.2175999 0.00165771
0.000601850 69.9074757 0.00164854
0.000291661 85.416937 0.00163557
0.000302383 84.8808581 0.00163579

43
Table 35: Summary of calculated data at 0.8 % w/w dye solution
Final concentration, w/w dye solution Percentage Removal Concentration Error
0.001962153 1.8923484 0.00165659
0.000172393 91.3803501 0.00168174
0.000403012 79.8494061 0.00166588
0.000419827 79.0086575 0.00165239

Table 36: Summary of calculated data at 1.0 % w/w dye solution


Final concentration, w/w dye solution Percentage Removal Concentration Error
0.001797282 10.1359221 0.00168323
0.001199621 40.0189438 0.00163716
0.000616016 69.1992137 0.00169379
0.000572881 71.355926 0.00165799
0.000506422 74.678886 0.00169149

vi. Calculation of mass of dye per volume of solution, c


At initial concentration of 0.2% w/w dye solution:
c   final concentration  final density 
c   0.001355083 0.939400265 
g
c=0.001272965
mL
The same method is done in 0.4%, 0.6%, 0.8% and 1.0 % w/w concentrations.

vii. Calculation of mass of dye adsorbed per mass of activated carbon, w


At initial concentration of 0.2% w/w dye solution:
initial concentration  final concentration
w
final density
0.002  0.001355083
w
0.939400265
g
w=0.00068652
g

The same method is done in 0.4%, 0.6%, 0.8% and 1.0 % w/w concentrations.

44
viii. Calculation of mass of dye per volume of solution error, c error
At initial concentration of 0.2% w/w dye solution:

2 2
z  x   y 
    
z  x   y 
2 2
 x   y 
z  z     
 x   y 
2 2
 0.035  density error   concentration error 
z  c    
 final density   final concentration 
2 2
 0.035  0.019512309   0.00165659 
z  0.001857277    
 0.946550684   0.001962153 
z=0.00157
The same method is done in 0.4%, 0.6%, 0.8% and 1.0 % w/w concentrations.

ix. Determination of the Freundlich Adsorption Isotherm Equation


Calculations and simplifications was done using fx-991ES Plus Casio Calculator.
The following commands were first clicked:
Mode  3  7

From the equation y  Ax B , which is similar to the Freundlich Adsorption Isotherm in


Equation 2, let y = w
A=k
x=c
B=m
Then put the following data on the table,

X y
( g dye/mL solution ) ( g dye adsorbed/g AC )
0.000532887 0.010134648
0.000389761 0.008164909
0.000280309 0.006146290
0.000151895 0.004145200
0.000123100 0.002018277

Afterwards, Click the following commands to determine A and B:


Shift  1  5  1 : For A

Shift  1  5  2 : For B

45
Simplifying these give the Freundlich Isotherm equation: w  18.1472175c 0.9834117406 .

x. Plotting of Isotherms

46
C. Design of Fixed Bed Adsorption Column
i. Density of Effluent
From the raw data Table 14, the density of the effluent is calculated using the
following:
(mass of solution)
density of solution =
(volume of solution)

( mass of bea ker  solution )-( mass of bea ker)


density of solution 
( volume of solution )
101.5931g - 52.9477 g
density of solution 
52.5 mL
density of solution  0.927 g / mL

The same method is done in the determination of densities from Table 15.

ii. Density Error

2 2
z  x   y 
     
z  x   y 
 2 2 
  x   y  
z  z        
  x   y  
 
 2 2 
   0.5  
z  0.927  
0.0001

  101.5931  52.9477   
 52.5  
 
z= ±0.00882

47
iii. Minimum and Maximum Densities
The maximum and minimum densities of the effluent were calculated by either adding
or subtracting the density error.

  0.927 g / mL
 min  0.927  0.00882  0.918 g/mL
 max  0.927  0.00882  0.935 g/mL

The same method was used in calculating the densities of the effluents for the
succeeding time periods as well as those from Table 17 and 18.

iv. Concentration of the Effluent


Using the equation correlating density and concentration from part A, the concentration
of the effluent in each time period was calculated.
From Part A:
Concentration  0.0849density   0.0784
For the Effluent time t = 10 minutes:
Concentration  0.0849  0.927   0.0784
C oncentration=0.00027

Table 37: Calculation of Concentrations in Figure 8


Density(g/mL) Concentration(w/w%)
0.927 0.00027
0.955 0.00271
0.978 0.00464
0.982 0.00499
0.982 0.00499

v. Generation of the Breakthrough Curves


In the Breakthrough curve, time was on the x-axis while c/co on the y-axis:
C0 = 0.005
At time t = 10 minutes:
C 0.00027

Co 0.005
C
= 0.053
Co

Hence, for the Breakthrough Curve at Figure 8, the following data are calculated,

48
Table 38: Calculation of C/Co in Figure 8
Time(min) C/Co
0 0
10 0.053
20 0.542
30 0.928
40 0.998
50 0.998

Same method is done in the data of Figures 9, 10 and 11.

vi. Breakpoint Time


For the bed with a height of 10 cm:

BREAKTHROUGH CURVE FOR 0.5% SOLUTION


1.2

0.8

0.6
C/Co

0.4

0.2 y = 1E-08x5 + 2E-07x4 - 0.0001x3 + 0.0058x2 - 0.0396x - 4E-11


R² = 1
0
0 10 20 30 40 50 60
-0.2
Time(min)

where: y = c/co
x = time
Setting the Breakpoint time at c/co = 0.05
0.05  1  10 8 x 5  2  10 7 x 4  0.0001x 3  0.0058 x 2  0.0396 x  4  10 11
x  9.18
tb  9.18 minutes
vii. Calculation of Usable Time
tb  C 
tusable  0
1 
 Co 
 dt

 
9.18
tusable  0
1  1  108 x5  2  107 x 4  0.0001x3  0.0058 x 2  0.0396 x  4  1011 dt
 
t usable = 9.53 min

49
viii. Total time

tT  A1  A2
A1  6( 1 )
A1  6.00


A2  ( 36  6 )( 1 )  636 1  1108 x5  2 107 x4  0.0001x3  0.0058 x2  0.0396 x  4 1011
 dt
A2 =7.07577
tT  6.00  7.07577
tT = 13.08 min

ix. Usable Height

t 
H u  HT  u 
 tT 
 9.53 
H u 10  
 13.08 
H u =7.29 cm

x. Unusable Height

HUNB  HT  HU
HUNB 10  7.29
HUNB = 2.71cm

50
xi. Other Tables of Concentration Calculated from Their Densities

Table 39: Calculation of Concentrations in Figure 9


Density(g/mL) Concentration(w/%)
0.928 0.000411346
0.965 0.003489621
0.981 0.004867297
0.981 0.004911572

Table 40: Calculation of Concentrations in Figure 10


Density(g/mL) Concentration(w/%)
0.9304 0.000591878
0.9699 0.003948009
1.0310 0.009130138
1.0400 0.009891968

Table 41: Calculation of Concentrations in Figure 11


Density(g/mL) Concentration(w/%)
0.9368 0.001136099
1.0209 0.008271303
1.0397 0.009868385
1.0412 0.009997106

xii. Other Tables for the Values of C/Co in the Generation of Breakthrough Curves

Table 42: Calculation of C/Co in Figure 9


Time(min) C/Co
0 0
10 0.082269174
20 0.697924112
30 0.973459415
40 0.982314359

Table 43: Calculation of C/Co in Figure 10


Time(min) C/Co
0 0
10 0.059187798
20 0.394800884
30 0.913013784
40 0.989196781

51
Table 44: Calculation of C/Co in Figure 11
Time(min) C/Co
0 0
10 0.11360994
20 0.82713028
30 0.98683849
40 0.99971058

52