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Universitt Duisburg Essen

Fakultt fr Ingenieurwissenschaften
Abteilung Maschinenbau
Institut fr Energie- und Umweltverfahrenstechnik,
Verfahrenstechnik / Wassertechnik
Prof. Dr. Ing. habil. Rolf Gimbel
Dr. Ing. Ralph Hobby
M. Sc. Grit Hoffmann
M. Sc. Mathis Keller
M. Sc. Anik Deutmarg
M. Sc. Lucas Landwehrkamp



Practical Course Technical Engineering Water

Adsorption
First Name: Second Name:
Matriculation number:







2
Content
1. Introduction ................................................................................................................... 3
2. Main goals of the experiments....................................................................................... 9
3. Experimental procedure .............................................................................................. 10
4. Interpretation of data................................................................................................... 16
5. Literature..................................................................................................................... 17
3
1 Introduction
For about 80 years activated carbon has been used for drinking water treatment. The
primary treatment goal was the removal of taste, odour and colour causing
substances and the removal of chlorine.
Over the past 30 years activated carbon has been increasingly used for the removal
of organic micropollutants. These substances are present in quite low concentrations
in surface waters and may also be present in ground water due to a long-term
anthropogenic pollution.
These so called organic micropollutants include: chlorinated carbohydrates,
pesticides, pharmaceuticals and endocrine disrupting compounds.
Activated carbon is used as granular activated carbon in deep bed filters (GAC
adsorber) or as powdered activated carbon (PAC) which is added to the water e. g.
as a suspension. In a GAC-adsorber, the adsorption process occurs if the water
passes the activated carbon layer. Using the conventional PAC, the process PAC is
added at an appropriate point of the water treatment plant. After sufficient contact
time for the adsorption process, PAC is removed from the treated water with
sedimentation and/or a rapid sand filtration (Sontheimer et al., 1985a).
Figure 1 represents schematically the adsorption process for a single substance with
PAC in a continuously stirred tank reactor (CSTR) and for a single substance in a
GAC-adsorber, assuming ideal conditions. Using the PAC process the maximum
solid phase concentration (adsorbed single substance onto the activated carbon)
q
max
,
PAC
can be achieved using the operation line which starts at the influent
concentration c
in
of the CSTR and ends at the adsorption equilibrium point on the
isotherm of the single substance with the effluent concentration c
eff
,
PAC (t=)
. The
concentration c
eff
,
PAC

(t=)
is in equilibrium with the solid phase concentration
q
max
,
PAC
. The slope of the operation line is given by the ratio of the volume of water
V and the mass of PAC m.
In a GAC adsorber the theoretical maximum solid phase concentration is much
higher in comparison to a conventional PAC process. This is due to the filter effect, i.
e. in a GAC layer it is possible to achieve the maximum solid phase concentration
q
max
,
PAC
of a single substance which equilibrates with the influent concentration c
in
.
But, regarding real conditions the maximum solid phase concentration may be
reduced enormously due to preloading effects by natural organic substances which
are present in natural water.
4
0
140
0 1,1
Liquid-phase concentration c
S
o
l
i
d
-
p
h
a
s
e

c
o
n
c
e
n
t
r
a
t
i
o
n

q
Isotherm
q
max, PAC
C
in
C
eff,PAC (t= )
q = f(c)
-V/m
V
m
PAC: Operation line with
slope -V/m
q
max, GAC
V, c
in
V, c
eff, PAC
. .
CSTR with PAC
V, c
in
c
eff, GAC
V
.
.
G
A
C

a
d
s
o
r
b
e
r
C
eff,GAC (t=0)
C
eff,GAC (t= )
PAC

Figure 1: Schematic view of the adsorption process using PAC in a CSTR and using a GAC
adsorber assuming ideal conditions
For the understanding and for the design of an adsorption process with activated
carbon, it is essential to know about the:
special characteristics of activated carbon,
adsorption equilibrium,
adsorption kinetics,
process design
The raw material and the conditions of the activation process influence the structure
of the pore system, the inner surface and also the adsorption characteristics of an
activated carbon. One very important adsorption characteristic is the adsorption
equilibrium, which will be described in the following chapter.
1.1 Description of adsorption equilibria
1.1.1 Adsorption equilibria of single substances
For the design and operation of an adsorption process for water treatment it is
necessary to characterise the raw water as well as the activated carbon. Thus, it is
necessary to know the adsorption capacity of the activated carbon and also the
adsorption kinetic. The adsorption capacity can be determined by an adsorption
isotherm. An adsorption isotherm describes the adsorption equilibrium in a closed
system, which consists of a solution with a single dissolved organic substance and
5
an amount of activated carbon brought in contact with the solution. If adsorption
equilibrium is reached after sufficient contact time, a constant concentration of the
substance remains in the solution. There is also a constant solid-phase
concentration of the substance, which has been adsorbed on the activated carbon.
To evaluate an adsorption isotherm defined quantities m
i
of activated carbon are
added to several bottles containing the same defined volumes V of solution with a
single substance initial concentration c
0
. The solutions with the activated carbon are
mixed intensively to bring the carbon into contact with the solution. The adsorption
equilibrium is usually reached after a contact time of about 24 to 72 hours. In the
solution remains an equilibrium concentration c of the single substance and a solid-
phase concentration q, which describes the quantity of the adsorbed substance. This
can be described by the following mass balance
V c m q V c m q
o o
+ = + (1.1.1)
If the initial solid-phase concentration of the unused carbon q
o
= 0 then
( ) q
V
m
c c
o
= (1.1.2)
A single adsorption equilibrium point is shown in Figure 2.

Figure 2: Determination of an equilibrium point of an adsorption isotherm
6
The figure shows the solid-phase concentration of an adsorbable single substance
as a function of the liquid-phase concentration. At starting point the concentration in
the liquid phase is equal c
0
(c=c
0
) and the solid-phase concentration q
0
=0.
Depending on contact time the liquid-phase concentration becomes lower and the
solid-phase concentration increases according the mass balance 1.1.2. This
relationship is described by an operation line with the slope of V/m, which connects
the point c
0
on the abscissae and the equilibrium point q=f (c). In figure 1.1.2. can be
seen, that several equilibrium points are necessary to determine an adsorption
isotherm. In this case equilibrium points were determined by the variation of the ratio
V/m resp. the slope of the operation lines.

Figure 3: Adsorption isotherm and equilibrium points which are obtained by the variation of the
ratio V/m with constant initial concentration c
o
7
There are different equations to describe the measured adsorption equilibrium
points. In the following the so-called Langmuir isotherm equation and the
Freundlich isotherm equation are described.
The Langmuir isotherm equation can be derived based on two kinetic equations
according equations 1.1.3 and 1.1.4. Equation 1.1.3 describes the rate of adsorption
dependent on free adsorption sites of the activated carbon resp. the difference
between the maximum solid phase concentration q
m
and the occupied adsorption
sites given by q. Equation 1.1.4 describes the rate of desorption dependent on the
solid-phase concentration resp. the occupied adsorption places. K
1
and K
2
are rate
constants.
( ) r K q q c
Ads m
=
1
(1.1.3)
r K q
Des
=
2
(1.1.4)
If equilibrium is reached adsorption rate is equal desorption rate

Des Ads
r r = (1.1.5)
and the Langmuir isotherm equation is given by equation 1.1.6:
q q
K c
K c
m
L
L
=

+ 1
, K
K
K
L
=
1
2
(1.1.6)
K
L
is the Langmuir-constant, q
m
the maximum solid-phase concentration if a
monomolecular layer on the carbon surface is assumed, c is the liquid-phase
concentration at adsorption equilibrium point and q is the solid-phase concentration
at adsorption equilibrium point. For the experimental evaluation of K
L
and q
m
a
linearisation of equation 1.1.6. is useful

c q K q q
m L m
1 1 1 1

+ = (1.1.7)
This regression is strongly biased toward fitting the data in the low concentration
range. Another possible linearisation (1.1.8) should also be considered. It has some
bias toward fitting the data in the middle and high concentration range.
(1.1.8)
8
The Langmuir isotherm equation has two limits:

( ) limq c q K c
c o
m L
=

(linear isotherm) (1.1.9)



( ) limq c q
c
m
=

(horizontal isotherm) (1.1.10)
The linear range of the isotherm is also called as the Henrys law range, because
equation 1.1.9 is similar to Henrys law which describes the solubility of gases in
liquids. At high liquid-concentrations the solid-phase concentration is not dependent
on the liquid-phase concentration. Thus the adsorption isotherm becomes horizontal.
Because of these two limits it becomes evident, that the description of experimentally
determined equilibrium points is often not exactly enough by the use of Langmuir
isotherm equation.
More often the Freundlich isotherm equation is used to describe the adsorption
isotherm for a single substance.
q K c
F
n
= , (1.1.11)
Therein K
F
is the Freundlich constant and n is the Freundlich exponent. These two
parameters can be determined easily by nonlinear regression or by linear regression
of equation 1.1.11 which has to be transformed to
lg lg lg q K n c
F
= + (1.1.12)
The Freundlich isotherm equation allows very often a better description of an
adsorption isotherm in a wide concentration range.



9
2 Main goals of the experiments
The main goals of the experiments are to:
Determine the adsorption isotherm for two different activated carbons to get
information about the potential to remove a single organic substance (Diclofenac)
from water
Evaluate the results using the Freundlich as well as the Langmuir equation and
compare which equation is more suitable related to your results
Define the Freundlich exponent n and the Freundlich constant K
F
as well as the
Langmuir constant K
L
and the maximum solid-phase concentration q
m

10
3. Experimental Procedure
3.1 Materials
Hach-Lange DR5000 spectrophotometer
balance
volumetric flasks (100 ml, 2 L)
powdered activated carbon: NORIT SA-UF (Suspension) 200 mg/L
powdered activated carbon: Jacobi PAC-MG (Suspension) 200 mg/L
Schott bottles
lab gloves
multi magnetic stirrer and stir bars
pipettes and pipette tips
dispenser (100 ml)
narrow neck bottles (100 ml)
filtration unit suction pump, glass fibre filters
ultrapure water
beakers
stopwatch
diclofenac (DFC) stock solution 0.4 g/L
NaHCO
3
solution 0.05 mol/L
MgSO
4
solution 0.02 mol/L
CaCl
2
solution 0.03 mol/L
1 M HCL / 1 M NaOH
11
3.2 Guidelines for carrying out the experiments
3.2.1 Preparation of synthetic drinking water
All experiments are carried out in synthetic drinking water. Although it is suitable for human
consumption, tap water still contains a residual concentration of natural organic matter
(NOM). This NOM is also adsorbed on activated carbon. Therefore, the use of tap water for
the experiment would lead to a so called multisolute system, in which the substances
compete with one another for the adsorption sites on the activated carbon surface. Synthetic
drinking water in contrast contains no NOM, thus, it is possible to create a system that
contains just one adsorbable substance (in our case diclofenac).
Preparation of 5 L synthetic drinking water: Use a 5 L volumetric flask to prepare the
synthetic drinking water. Add ~2 L of ultrapure water into the volumetric flask, then pipette
the right amounts of NaHCO
3
solution, MgSO
4
solution and CaCl
2
solution into the volumetric
flask and fill it up to the mark with ultrapure water. Do not mix the salt solutions undiluted, as
precipitation might occur!
Adjust the pH-value of the synthetic drinking water to 7.5 by dropwise addition of
hydrochloric acid / sodium hydroxide solution.
Calculation of the right amount of salt stock solution: The concentrations of different ions in
synthetic drinking water are listed in table 1.
Table 1: Ion concentration
Ion
Concentration
[mg/L]
Na
+
11.5
Ca
2+
12
Mg
2+
5
HCO
3
-
30.5
Cl
-
21
SO
4
2-
19

Calculate the ion concentration in the synthetic drinking water in mol /L.
Calculate the right volume of stock solution you have to add for the preparation of 5 L
synthetic drinking water (for concentrations of salt stock solutions see section 3.1).
You may find figure 4 helpful in case you have problems with the calculation.
12


Figure 4: Instruction for the calculation of different parts for preparing a solution
Table 2: Calculated volumes
Stock solution
volume needed for
preparation of 5 L synthetic
drinking water [mL]
NaHCO
3
0.05 mol/L FILL IN RIGHT VOLUME
MgSO
4
0.02 mol/L FILL IN RIGHT VOLUME
CaCl
2
0.03 mol/L FILL IN RIGHT VOLUME


3.2.2 Calibration
Perform a 6-point calibration using DFC concentrations between 0 and 5 mg/L. The
absorption maximum of DFC is at 276 nm; accordingly you have to adjust the
spectrophotometer to that wavelength (ask supervisor). The DFC stock solution has a
concentration of 0.4 g/L. Prepare standard solutions in the concentration range mentioned
above:
use one volumetric flask to prepare a dilution of the stock solution if necessary
add the (calculated) volume of DFC stock solution into a volumetric flask (100 ml)
fill it up to the mark with synthetic drinking water
prepare also one flask without DFC for the blank
After carefully shaking the flasks, measure the extinction of each standard solution using the
spectrophotometer. Note the displayed extinction. Plot a calibraton curve to get the
13
calibration function and discuss the important characteristics of the calibration (correlation
coefficient ).
3.2.3 Experiment 1 Adsorption of Diclofenac using PAC NORIT-SA-UF
In this experiment, information about the equilibrium and the kinetic for the adsorption of
DFC using the PAC SA-UF by NORIT should be collected.
The equilibrium experiment should be started first to save time. Take a Schott bottle filled
with 2000 ml of a solution of DFC with a concentration of 5.55 mg/L. Use a 2 L volumetric
flask to prepare the DFC solution. Attention: Use your synthetic drinking water to prepare the
DFC solution! After filling it into the Schott bottle, place the dispenser on the Schott bottle
and discard the first ~ 20 ml to ensure that residual air in the pipe of the dispenser is
removed.
Fill 20 narrow neck bottles (No. 0 9 and No. K0 K9) with 90 ml of your DFC solution
(concentration = 5.55 mg/L). Work slowly when using the dispenser to avoid air bubbles,
especially when adding the last 20 ml. When finished, put a stir bar into the bottles, place
them on the magnetic stirrer and switch it on.
Now you can start part 1 of the experiment for the determination of the adsorption isotherms:
Add different volumes of PAC suspension (NORIT PAC SA-UF) into the bottles No. 0 - No. 9
and fill up with synthetic drinking water to a total volume of 100 ml. See Figure 5 for a better
understanding. Start the stop watch when adding the suspension to the first bottle.
Figure 5: Experimental procedure for the determination of adsorption isotherms

This experiment is stopped as soon as equilibrium is reached. To get information about the
time which is required to reach the equilibrium start now part 2, the kinetic experiment using
14
the bottles No. K 0 No. K 9. Add the volume of PAC suspension to get a concentration of
10 mg PAC/L in each bottle with a time delay of 30 seconds. Than take samples after 2.5, 5,
10, 15, 30, 60, 90, 120 and 150 minutes contact time. For a better understanding see
Figure 6. The procedure of taking a sample is described in the next chapter.

Figure 6: Experimental procedure for kinetic experiment
Stop this experiment when adsorption equilibrium is reached (that is the case when the
extinction of a sample is equal or higher than the extinction of the sample measured before).
The samples (No. 0 No. 9), prepared in part 1 of the experiment have also reached
adsorption equilibrium now (stop experiment, measure samples).
15
3.2.4 Sampling
To take a sample, prepare the filtration unit (see figure 7) as follows:







Figure 7: Filtration unit
place the filtration unit on an empty narrow neck bottle, put a glass fibre filter and the
sample reservoir on the filter holder and fix them with the clamp
switch on the suction pump and close the aeration valve and filter your sample
place the filtration unit on the wash bottle and rinse the sample reservoir with ~ 20 ml
water
use a new glass fibre filter and filter the next sample into another empty narrow neck
bottle
measure the extinction of the filtrate
3.2.5 Experiment 2: Adsorption of Diclofenac using Jacobi PAC MG
Repeat experiment 1 using the second activated carbon Jacobi PAC MG.
16
4. Interpretation of data
For the first and the second experiment plot the adsorption kinetics for each carbon type,
check the time which is necessary to reach the equilibrium and compare the two different
activated carbon brands (Discuss the results in a few sentences!). Are there differences?
Why?
Furthermore plot and discuss the adsorption isotherms for each carbon type solid-phase
concentration, q [g DFC/kg PAC] against liquid-phase concentration, c [mg DFC/L].
Make a linear regression using the Langmuir equation as well as the Freundlich equation for
each carbon brand and discuss which model is more suitable to describe the adsorption of
DFC onto PAC. Please keep in mind that there are two types of Langmuir regression.
Calculate the maximum solid-phase concentration q
max
and the Langmuir constant K
L
as well
as the Freundlich exponent n and the Freundlich constant K
F
for each carbon brand and
compare both carbon brands using these values, especially with respect to their adsorption
capacity. If there are any differences, how can they be explained concerning the different
characteristics (see data sheet for each carbon brand in appendix and check the meaning of
different carbon characteristics in the literature or the internet)?
Your report should include group colour, all necessary graphs and your discussion.
17
5. Literature
Sontheimer, H., Frick, B.R., Fettig, J., Hrner, G., Huebele, C., Zimmer, G. (1985):
Adsorptionsverfahren zur Wasserreinigung
DVGW Forschungsstelle am Engler Bunte Institut der Universitt Karlsruhe (TH)

von Kienle, H., Bder, E. (1980): Aktivkohle und ihre industrielle Anwendung
Ferdinand Enke Verlag


017687A
Date Issued
Customer
Quantity
Certificate of Analysis
Lot #
w w w . j a c o b i . n e t
Product
PO #
AquaSorb 5000, PAC-MG
Parameter Method Value Unit
Iodine number ASTM D4607 1470 mg/g
Moisture content (as packed) ASTM D2867 4,6 %
Total ash content ASTM D2866 12,4 %
Particle size by Laser
- 325 ( - 0.045) 100
US mesh mm %


Universitt Duisburg
Muster
03 August 2010
No Match
Certified by NSF to
ANSI/NSF Standard 61
J acobi Carbons
is certified to
ISO 9002:2000
......................................................................................
Karl Krause, Quality Manager
Datenblatt
Wasser
Dokument-Nummer
SAUF
Produkt / Anwendung
Aktivkohlepulver
Version
10 Februar 2010
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NoritSAUF
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ultrafeineTeilchenstrukturzurckzufhrensind.NoritSAUFbesitzteinsehrhohes
AdsorptionsvermgenfreineReihevonVerbindungenundfindetbesondersAnwendunginder
Trinkwasserbehandlung.Dastrengeberkorn-Anforderungengelten,eignetsichNoritSAUF
besondersinKombinationmitHohlfaser-Ultrafiltrationsmembranen.NoritSAUFwirdmittels
DampfaktivierungausausgewhltenRohstoffenhergestellt.
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entsprechendeZertifikatderRegistrierungistaufAnfrageerhltlich.
SPEZIFIKATIONEN
Jodzahl

min.1000

Korngre>400m

max.0.0

Gew.-%

Korngre>180m

max.0.1

Gew.-%

Feuchte(verpackt)

max.5

Gew.-%

ALLGEMEINEEIGENSCHAFTEN
Jodzahl

1100

Methylenblauadsorption

24

g/100g

Phenoladsorption

Gew.-%

InnereOberflche(B.E.T.)

1200

m
2
/g

Schttdichte(gestampft)

225

kg/m
3

KorngreD
50

Aschegehalt

10

Gew.-%

pH

alkaline

Feuchte(verpackt)

Gew.-%

HINWEISE
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ISO9001.
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VERPACKUNG
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- Schttgut-Tankfahrzeugen
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