The design for ion exchange column

Jiali Wang + Kenchouw Wu

March 2015

ii

The design for ion exchange column

(Internship report)

Submitted to:
Mr. Harmen van der Laan (Oasen Drinking water company)
Ms. C. Mok Kai Rine (The Hague University)

Submitted by:
Jiali Wang + Kenchouw Wu
BSc. Students Process and Food Technology
The Hague University
Date of submission:
March 2015
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Summary
The aim of the work described in this report was to design an ion exchange column for the
removal of ammonium ions from RO permeate. The ion exchangers used in this research project
were i) clinoptilolite, a naturally occurring zeolite and ii) a resin in H+ form with functional group
sulfonic acid (Lewatit S2568H). A four columns set-up has been designed based previous research
done by Mikkers (2009) in which above described ion exchangers have been used. The main
scope of this report was to look at the influence of surface loading and bed height on the
ammonium removal capacity. Several experiments were conducted with varying bed heights (5
20cm), flow rates per column (12 100L/h) and the two ion exchange media.
The results of experiments were compared with those of the previous research studies done by
KWR (2005) and Ekowati (2014) and were found to be comparable. The zeolite was found to have
a 7 times lower breakthrough capacity compared to the Lewatit resin. The average breakthrough
capacity was found to be 2.17 mg NH4 per gram for the resin. Due to the influence of the film
diffusion, the breakthrough capacity was similar for different surface loading rates.
The results were used to design an ion exchange column for the new to build water treatment at
ZS De Hooge Boom. Using the average breakthrough capacity from the experiments a design was
made for four ion exchange vessels with each a capacity of 120m3/h, a bed height of 2m, and
surface loading of 99m/h, and Empty Bed Contact Time (EBCT) of 1.2minutes and a breakthrough
time of 10 days. The costs were estimated to be 0.014 per m3.
Recommendations for future research are to conduct experiments with higher bed heights (60
100cm) and to use a ammonium dosing in the feed water to vary with different ammonium
concentrations.
Keywords: Ion exchange column, zeolite, resin, surface loading, bed height

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Contents
1. Introduction and research question .............................................................................................. 1
1.1 Oasen Drinking Water Company ............................................................................................. 1
1.2 Drinking water treatment "De Hooge Boom" ......................................................................... 1
1.3 The research project ............................................................................................................... 2
1.4 Previous research .................................................................................................................... 2
1.5 Problem introduction .............................................................................................................. 3
1.6 Boundary conditions ............................................................................................................... 3
1.7 Outline of the report ............................................................................................................... 4
2. Theoretical background ................................................................................................................ 5
2.1 Ion Exchange ........................................................................................................................... 5
2.2 Selectivity of ion exchange ...................................................................................................... 6
2.3 Kinetics of Ion Exchange.......................................................................................................... 7
2.3.1 Kinetics ............................................................................................................................. 7
2.3.2 Parameters in Ion Exchange ............................................................................................. 8
2.3.3 Ion Exchange capacity ...................................................................................................... 9
2.3.4 Breakthrough ................................................................................................................. 10
3. Methods and materials ............................................................................................................... 11
3.1 Set-up .................................................................................................................................... 11
3.2 Materials ............................................................................................................................... 12
3.3 Measurement methods......................................................................................................... 12
3.4 The validation of spectrophotometer Hach-Lang DR 2800 ................................................... 12
3.5 The validation of ammonium analyzer Applikon Colorimeter .............................................. 13
3.6 The validation of ammonium dosing pump .......................................................................... 14
4. Results ......................................................................................................................................... 17
4.1 The performance of 10 and 20 cm Lewatit S2568H .............................................................. 17
4.2 Comparison between Lewatit S2568H and clinoptilolite ...................................................... 20
4.3Comparison between clinoptilolite with different particle size ............................................. 20
5. Discussion.................................................................................................................................... 21
5.1 Influence of bed height ......................................................................................................... 21
5.2 Influence of flow rate ............................................................................................................ 21
5.3 Kinetics .................................................................................................................................. 22
5.4 Performance of zeolite and resin .......................................................................................... 22
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5.5 Influence of particle size. ...................................................................................................... 22

5.6 Difficulties of doing pilot experiments .................................................................................. 22
6. Ion exchange column design calculation ..................................................................................... 23
6.1 Introduction .......................................................................................................................... 23
6.2 Design calculation ................................................................................................................. 23
7. Conclusion and recommendations for future research .............................................................. 27
7.1 Conclusion ............................................................................................................................. 27
7.2 Main uncertainties in the research and design ..................................................................... 28
7.3 Recommendations for future research ................................................................................. 28
Reference ........................................................................................................................................ 29
Appendix A: Drinking water quality standards............................................................................ 30
Appendix B: Schematic drawing Set-up by Yvonne Mikkers ....................................................... 32
Appendix C: Material data sheet................................................................................................. 33
Appendix D: The results of validation of equipments ................................................................ 39
Appendix E: Measuring reports .................................................................................................. 42
Appendix F: The design of future treatment plant ..................................................................... 56
Appendix H: The pressure drop data of Lewatit S2568H ............................................................ 57

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1. Introduction and research question

1.1 Oasen Drinking Water Company
Oasen, is an public drinking water supply company with 130 years history. It offers drinking water to 750.000
people and 7.200 companies in the south east Holland. (Figure 1.1.1) The purpose of Oasen is to make sure that
the water is of impeccable quality and the same level quality of drinking water should be always kept.

Figure 1.1.1 Oasens supply area

Every year, Oasen provides its customers with 48 billion liters of drinking water produced from groundwater.

1.2 Drinking water treatment "De Hooge Boom"

Drinking water treatment plant "De Hooge Boom" is located in Kamerik, South Holland, with total capacity of
3.000.000 m3 per year. In 2013, Oasen started its multi-annual plan Better than Possible, which will be put into
practice at De Hooge Boom in the future. The current treatment processes showed in (Figure 1.2.1 and Figure
1.2.2) have been producing water with good quality that meets the standards.

Figure 1.2.1 Drinking water treatment plant De Hooge Boom

Figure 1.2.2 Treatment scheme in De Hooge Boom treatment plant (Source: Yuli Ekowati, 2014)
Figure 1.2.3 shows the plan of new treatment processes that will be operated in the near future in De Hooge
Boom.

Figure 1.2.3 New treatment scheme for De Hooge Boom treatment plant (Source: Yuli Ekowati, 2014)

1.3 The research project

The raw water at the ZS De Hooge Boom is distracted from a deeper level where the water originates from the
river. This is called river bank filtrate. It does not reach the quality standard of drinking water in the Netherlands
(See Appendix A); even though the groundwater is naturally purified after it moves so slowly in the subsurface.
In the new to build treatment plant de Hooge Boom, the raw water passes through RO (reverse osmosis)
membrane filters first. Then another treatment step is required, because the ammonium removal by the
membrane technique is not good enough at present. It results in the higher concentration of ammonium in the
RO permeate (up to 0.6mg/L), whereas the limit is 0.03mg/L. In order to reach the purpose, ion exchange
technology is selected to be applied in this research project.
This research project focuses on this part of new to build the treatment: the ion exchange step to remove
ammonium.

1.4 Previous research

This research is performed based on previous studies about ion exchangers efficiency and regeneration. In
summary, the research of KWR, Yuli Ekowati and Yvonne Mikkers provide essential ideas and information for this
research project.

KWR, 2005 Research topic: Ammonium removal in drinking water using natural zeolite
In the research experiments, in order to make the experiment condition more persuasive and accurate,
ammonium chloride solution was added in to the dematerialized water.
The KWR research has founded out the two main effects on ammonium removal capacity:
o The grain size of the clinoptilolite (done by feed water with 2 mg NH4+/L)
o The initial ammonium concentration in aqueous solution (done by feed water with 0.05-10 mg
NH4+/L)
It was found that ammonium removal was faster with the smaller grains and a high removal capacity is
obtained quickly. An increase in ammonium concentration in the solution will result in an increasing
ammonium removal capacity by clinoptilolite.

Yvonne Mikkers, 2009 Ammonium removal with zeolite on anaerobic groundwater

In this research, the effectiveness of chemical regeneration of two kind zeolites which were used to
remove ammonium from groundwater has been studied at Oasen.
To perform the experiments, Yvonne designed the set-up (see Appendix B) for pilot scale study from
which the idea for the present researchs column set-up came. In her research experiments, the raw
water with average NH4+ concentration of 6.5 mg/L was used as feed water.

Yuli Ekowati, 2014

In this research, the efficiency of ion exchange resin/zeolite in removing low concentration of
ammonium was investigated at Oasen in Kamerik, as a part of the research program. Based on Yulis
literature research, several adsorption isotherms for calculation of run length for zeolite were found.
According to the experimental data, the KWR report (2005) provides the most accurate/realistic
adsorption isotherm. This adsorption isotherm will be used in the present research for calculating
breakthrough run length of zeolite. Furthermore, she made the present setup, but was not able to reach
the breakthrough of resin.

1.5 Problem introduction

1.5.1 Ammonium in ground water
In the Netherlands, the groundwater is required to be treated before it becomes drinking water. High
ammonium concentration in the groundwater needs to be lower at a certain level. Reason is that the nitrogen
can maybe serve as nutrient for some bacteria. Furthermore, NH4+ can be formed to nitrite which is a cause of
health problems if the amount of nitrite occurred in the drinking water exceed the maximum contaminant level
allowed.
To solve the problem, the ion exchange is regarded as an effective post treatment to remove ammonium.
1.5.2 Research question
The Oasen Drinking Water Company, is planning to build a new treatment plant in De Hooge Boom, Kamerik in
2018. And the new treatment plant will employ ion exchange technique after ground water experiences
filtration of the RO (reverse osmosis) membrane. This effluent called permeate water attains a relative lower
concentration of ammonium, which becomes the influent to pass ion exchange step.
At the beginning, the concentration of ammonium is around 0.1 mg NH4+/L, and the target ammonium
concentration in the outflow is required to achieve <0.03 mg NH4+/L.
At present, resin and zeolite are two main ion exchange materials (see chapter 2) in water treatment. In order to
determine the efficiency of zeolite and resin to be appropriately applied in lower ammonium removal, the
research question is defined as follow:
What should be the design of the ion exchange post treatment step for permeate when it comes to surface
loading and bed height?
Sub questions:

What is the influence of the surface loading (which is flow rate of feed water on the effectiveness
of ammonium removal by ion exchange)?
What is the influence of the bed height of the ion exchange for the effectiveness of ammonium
removal?

1.6 Boundary conditions

For this research project, the limited conditions were described as following. Due to the limited time for only
two months, it was not possible to do experiments related to every parameter that has influence on ammonium
removal in ion exchange process. Based on the plan of action, three main parameters should be considered in
experiments: (1) bed heights of ion exchange, (2) initial concentration of ammonium in feed water and (3) flow
rate of feed water. In literature, the important parameters also include temperature of water, particle size of ion
exchangers, pH level and etc.
In the project, only different bed heights of ion exchangers and different flow rates of permeate water has been
done. For different initial concentration of ammonium, it had been ever planned to utilize a dosing pump for
getting a higher ammonium concentration in feed water. But it was not successful; because the dosing
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ammonium solution didnt mix well with permeate water (see in chapter 3).
Last but not least, the concentration of ammonium after the RO (reverse osmosis) membrane could not maintain
a stable level in the duration of the project. That is due to the groundwater comes from different wells. In this
case, the breakthrough capacities, SFR (service flow rate) and the design of full scale will be influenced (see
chapter 4 and 5).

1.7 Outline of the report

In chapter 2 the general theory of ion exchange will be presented. Chapter 3 will go about the description of
pilot setup, materials, and measurement methods. The experiment results will be shown in chapter 4. In chapter
5 the results will be discussed and compared with previous research studies. And the difficulties of doing pilot
scale will be discussed as well. In chapter 6 the ion exchange design will be given and finally, in chapter 7 the
conclusion of this report will be presented.

2. Theoretical background
2.1 Ion Exchange
Ion exchange is used in water treatment to remove the unwanted soluble ionized substances from water being
treated. Ion exchange resins can be divided into two groups. One is the polymer on which the fixed groups are
permanently ionized at. The fixed groups are positive or negative charged. To keep the resin electrical neutral,
ions of opposite charge have to attached on it. The ions of opposite charge are unlike the fixed groups, exchange
with mobile ions from water, are so called counter-ion. The ions that have the same charge as that of the fixed
groups (exchange sites) are known as co-ions. Figure 2.1 shows an example of cation exchange resin bead.

Na+ = mobile ions (counter-ions)

SO3- =fixed group
Dark line = polymeric skeleton
Figure 2.1. Schematic cation exchange resin bead (Rohm and Haas, 2008)

An ion exchange that is capable of exchanging cations are known as cation exchange, and capable of exchanging
anions are known as anion exchange.
An overview of the compositions can be made as follows:
Type
Fixed groups
Counterions
Cation exchange
+
Anion exchange
+
-

Coions
+

Another one is the inorganic ion exchange. The inorganic materials initially used were natural crystalline
aluminosillicates which had cation exchange properties. (B.A.Bolto and L.Pawlowski,1987). Ammonium can be
removed from water by strongly acidic cation resins or by zeolites. The most used zeolite type for the application
in removing ammonium is clinoptlolite. They remove ammonium more selectively with little competition from
other cations (George J. Crits, 2012). The matrix made of aluminum, silicates and oxygen is highly negatively
charged, because of the shared oxygen atoms between aluminum and silicon. To keep electrical neutrality, the
zeolites are commonly neutralized with sodium, potassium and calcium. It is of importance that the zeolite
prefers ammonium ion over them.
The adsorbent is exchanged for an unwanted ion (for example NH4+ ions) in the water. For the sake of
accomplishing the exchange reaction, a packed bed of ion-exchange resin beads or zeolite is used. Raw water is
continually passed through the bed in a down flow or up flow mode until the adsorbent is exhausted, as
evidenced by the appearance (breakthrough) of the unwanted contaminant at an unacceptable concentration in
the effluent. Also, it is regarded that the most effective ion exchange reactions are reversible.
Zeolite is inorganic and other important kind of ion exchangers in ion exchange application for water treatment.
There is one sample of zeolite show in figure 2.2 about the ion exchange process.

Figure 2.2 Ion-Exchange on a zeolite (Source: Schmidt, 2008)

In figure 2.2, the mobile ions are sodium that is loosely held by the zeolite. The fixed ions are aluminosilicates.
To remove ammonium ions (NH4+), the groundwater is passed through a column filled with sodium (Na+) form
zeolites. So ammonium ions going into the zeolite will be replaced by sodium ions getting out of it and dissolving
in the water.
In above process, the exchange reaction can be written as:
(R- Na+) + NH4+ (R- NH4+) + Na+
The brackets represents the zeolite matrix phase, R- is aluminosillicates.From the reaction equation it can be
seen that the salinity of the water remain the same, only the composition of the salinity is changed at the end of
the process.
Of course, the exchange is limited. The total ion-exchange capacity is determined by the concentration of fixed
charges. It describes the maximum amount of unwanted substances which have been replaced and there is no
place more for removing more.
In other word, ion exchange is an intrinsic property of ion exchange material. There are two necessary
requirements for ion exchange reaction: (1) the ion exchange material immerses in solution, and (2) the solution
contains unwanted ions.

2.2 Selectivity of ion exchange

The ion exchange can only work efficiently when there is a difference in affinity for counterions in the resin and
those in the external solution. In the zeolites, ammonium ions can be removed selectively from water, because
zeolites have more affinity for the ammonium than for the sodium ions.
The selectivity of a variety of cations on clinoptilolite shows (Langwaldt, 2008):
Cs+> Rb+ > K+ > NH4+> Ba2+ > Sr2+ > Na+ > Ca2+ > Fe3+> Al3+ > Mg+ > Li+
Fortunately, there are no Cs+, Rb+ , K+ presented in the permeate at De Hooge Boom.The selectivity for a certain
ion is determined by the selectivity coefficient Ks applied to the cation exchange in the reaction equation as
follows:
(R- A+) + B+ (R- B+) + A+
[(R B+ )] [A+ ]

Ks=[(R

A+ )] [B+ ]

The Ks describes how counterions are present in the exchange beads and solution when the exchange in the A+
form is placed in a solution having B+ ions. The value of Ks might be dependent on the porosity and the
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concentration of the solution. From the equation, it seems that the affinity of zeolite for ammonium increases as
the concentration of it increases in the solution.
Also, the selectivity coefficient Ks relies on various factors (Kunin R, 1951):
1. Higher valence ions are more preferred:
Tetravalent > Trivalent > Divalent > Monovalent
Th4+>Fe3+>Ca2+>K+
PO43->SO42->Cl2. Least hydrated ion is the most preferred:
The higher the ionic radius, the lower is the radius of the hydrated ion.
Cs+>Rb+>K+>Na+>Li+
SCN->ClO4->I->NO3->Br->CN3. Ions with greater ability to polarize are preferred:
NO3-> Br-> NO2-> Cl4. Ions with least tendency to form complexes in solution:
Cl-> HCO3-> CH3COO-> OH->F-

2.3 Kinetics of Ion Exchange

2.3.1 Kinetics
The kinetic mechanism is important factor to consider when it comes to mass transfer. The main mechanism in
ion exchange is summarized as follows (also see Figure 2.3.1.1):

Ions in solution travel through the bulk of the solution (diffusion in solution)
Diffusion of the specific ions from bulk liquid to a boundary layer surrounding the bead.
(film diffusion)
Diffusion through the boundary layer to the outer surface of the bead.
Diffusion from the bead surface into the pores of the bead. (particle diffusion)
Exchanging of counterions at the fixed site.

Film diffusion

Particle
diffusion

Film

Diffusion in
solution

(Resin)

(Solution)
Film

Figure 2.3.1.1 Schematic description of ion exchange process (source: Wang, 2015)
The rate is determined by the slowest kinetic step, thus the ion exchange reaction will not be taken into
consideration. Depending on the conditions, either film diffusion or particle diffusion is rate controlling. The
7

other factors are insignificant and can be ignored. (Tony C. Jorgensen, 2002)

2.3.2 Parameters in Ion Exchange

Ion exchanger type
On the basis of origin, there are two general types of ion exchange materials, they are resins and natural
exchangers; for the former one, the majority are synthetic polymers available in cationic and anionic forms
whereas the latter exists in cation-exchange form only (e.g., zeolites and betonites). Thus, synthetic ion exchange
materials can be cationic, anionic, and combined cationic/anionic (amphoteric) exchangers considering the
nature of fixed ion exchange sites (functional groups).
pH
The performance of ion exchange is influenced by the pH of the solution. In the experiments done by
(R.R.Harries, 1988), it can be concluded that anion exchange is faster in an acidic medium and cation exchange is
more rapid in alkaline medium.
Anion exchange
To find the relation between anion exchange kinetics and pH, the mass transfer coefficient of chloride and
sulphate were tested in the condition where strong base resin was used. Its found that there is a strong
decrease in chloride or sulphate exchange kinetics in moving from an acidic influent to a neutral or alkaline
influent.
The reaction occurring during the exchange can be represented by the following equation:
(R+ OH-) + A- (R+ A-) + OHR+ is the charged matrix and A- is chloride or sulphate.
Based on the above, anion exchange is more favorable under acidic environment. The reaction will be more
shifted towards the right when there are enough H+ reacting with OH- .
Cation exchange
The variation of cation exchange kinetics with pH was carried out. Sodium and ammonium ions were tested in
the condition where strong acid resin was used. There was an increase in exchange rate as the pH was increased.
If the permeate has a pH of 5 which is basic, it would help to increase the pH. Thus it would also to increase ion
exchange rate.
Initial ammonium concentration
In the presence of low ammonium concentration, the running time will be very long. When the concentration is
high, the ion exchange reaches the breakthrough quickly which results in high demand of regenerates to
uneconomical levels. Besides the high affinity discussed before, it also has influence on the particle diffusion.
In dilute solutions (usually below 0.001M), film diffusion is rate controlling. In this research project, the film
diffusion is expected to be rate determined. In more concentrated solutions (usually above 0.1 M), particle
diffusion is a rate determined factor. (B.A. Bolto and L. Pawlowski, 1987) This can be explained that dilute
solutions increase the flow rate of water through the pores of the bead.
Particle size
From described above, it can be seen that the exchange rate in concentrated solutions can be improved by the
decreasing of the particle size. Higher productivity can be obtained by using smaller particle size which provides
a larger surface area. But the particle is allowed to reduce to a certain size, because of a high pressure lose in the
process. The rate is inversely proportional to the particle radius when film diffusion dominated, and inversely
proportional to the square of the radius when the rate-limiting step is particle diffusion.(Helfferich,F., 1962)
In this project, the chosen particle size range of zeolite is 1.0-2.5 mm or 0.3-1.0 mm. Lewatit S2568H has its
8

mean bead size of 0.65 mm. The smaller particle size of Lewatit S2568H could increase its ion exchange rate.
Volumetric flow rate
At a low flow rate, there is a static water layer around the resin held by friction. The diffusion of ions through
the matrix of the resin is faster than the diffusion of ions across the static film. The film diffusion is a rate
determining factor and the film becomes denuded of ammonium.
In an example of ammonium containing solution flowing down resin in H+ form, there would be a lot of
difference of components between an upper layer of resin in the ammonium form and a down layer of resin in
the H+ form. The upper layer is surrounded by ammonium ions and the lower layer is surrounded by H +. It could
happen when the flow is so slow that the rate of arrival of ammonium ions is similar to that of diffusion through
the static film. Thus, there is no need for ammonium ions to enter another lower layer of resin. Another reason
might be the low flow rate increases the contact time.
In comparison to it, the rate of ammonium ions arrives on the resin is faster than the rate of diffusion through
the static film at a certain high flow rate. As a consequence, the sharp distinction between layers in H + form and
Na+ form will be disappeared.
Therefore, the breakthrough point at a low flow rate is higher than that at the higher flow rate. Also the quality
of effluent is obtained as the contact time increases with a decrease in flow rate. However the total ion
exchange capacity would be the same under both conditions after passage of excess solution. In the practice of
water treatment, it is recommended to terminate the run at the breakthrough point. By combining the flow rate
and ionic concentration of the water, the breakthrough curve is plotted. (T.V.Arden, et al., 1968)
Regeneration
At a certain point, the resins are saturated with unwanted substances, they can be used again by bring them
back to the fresh state. Since a suitable time is needed for the required degree of regeneration, the best way of
regenerating resins is to let regenerant go through columns with deep beds. The deeper the bed, the more
efficient of the regenerant. Because the resin can have more time in contact with regenerant.
For example, Zeolite is regenerated with sodium ions obtained by NaCl. The regeneration reaction:
RNH4 + NaCl RNa + NH4Cl
Ammonium ions within the zeolite are released into the solution and replaced by sodium ions from the NaCl
solution. For this regeneration, high concentration of NaCl is required since the reaction is reversible.
Regeneration not only optimizes the exchange capacity but also reduces the ion leakage. The concentrated NaCl
helps to remove contaminants at the bottom of the resin effectively within a short time. After regeneration
rinsing is required. In this case, the remained Cl- and Na+ have to be removed.

2.3.3 Ion Exchange capacity

The exchange capacity of an ion exchange material is a measurement of the ability, in which of an insoluble
material to experience replacement of ions previously attached and loosely incorporated into its structure, by
oppositely charged ions present in the surrounding solution. It is a constant value for a given exchange material.
The unit is expressed as mg/g of dry resin.
There are two capacity parameters to characterize ion exchangers: the total static capacity and the dynamic
capacity. The former is determined under static conditions, while the latter is determined by passing the
solution through a bed of the exchanger (usually a packed bed or a in a column).
Actually, in practice, this capacity can never be exploited due to interference from coexisting counterions. In a
column type exchanger, the operating capacity or the breakthrough capacity bases on the concentration of the
ions being removed, the effects of interfering ions, ionic size, ionic valence, design of the column, and operating
parameters.
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2.3.4 Breakthrough
A plot (see Figure 2.3.4.1) between the concentrations of the removed ions in the effluent (ordinate) versus the
effluent volume (abscissa) is drawn. The breakthrough is defined as the point where the unwanted ions in the
effluent appear in appreciable quantity. (c, start of breakthrough). The extent of breakthrough rises to a point e
where no more ion exchange occurs, that is, the effluent includes the original concentration of the ions. This
point records the stage at which the ion exchanger is completely exhausted and must be regenerated or
replaced. In order to enhance the extent of column utilization, it is always beneficial to get as steep a
breakthrough curve (adce).

Effluent volume

Figure 2.3.4.1 Schematic representation of breakthrough curve (Source: Inamuddin, 2012)

In Figure 2.3.4.1, Co means the initial influent concentration of ammonium; Cx means the instantaneous effluent
concentration of ammonium.

Figure 2.3.4.2 Breakthrough curve showing the outlet concentration (source: Tony C. Jorgensen, 2002)

In Figure 2.3.4.2, it illustrates a normal breakthrough curve at three different flow-rates. A high flow-rate is
related with early breakthrough and a gentle breakthrough curve. Low flow-rates may be related with later
breakthrough and a narrow breakthrough curve. At low flow-rates, a greater volume of water may be treated
until breakthrough occurs.
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3. Methods and materials

For this project, a column set-up was designed and two kinds of materials were chosen for the experiments.

3.1 Set-up
To determine the breakthrough capacity of Lewatit and zeolite, a four-column set-up was designed to perform
the experiments. The conditions were that the feed water (RO permeate) had an ammonium concentration
around 0.1 mg and average temperature of 12oC. The ammonium concentration of effluent was not allowed
more than 0.03 mg/L which was considered as a breakthrough point. The schematic overview of the set-up is
presented in Figure 3.1.1.

Figure 3.1.1: Schematic overview of the set-up

Specifications of the pilot column setup

Number of columns: 4, diaphanous PVC
4 columns for ion exchange beds
Column height: 1 m, Inner diameter: 34 mm
Filter plates holes: 0.4 mm
Taps at the top and bottom of the columns
Feed water: RO permeate
Direction of flow: inflow and outflow
Sampling points and codes
Column 1: influent = XKMKOX01A effluent= XKMKOX01Z
Column 2: influent = XKMKOX02A effluent= XKMKOX02Z
Column 3: influent = XKMKOX03A effluent= XKMKOX03Z
Column 4: influent = XKMKOX04A effluent= XKMKOX04Z
The feed water flows through the gate valve followed by the column and out to drain. The selected resin/zeolite
should be placed in the column with a designed height for testing. Filter plates are at the top and bottom of the
columns. To prevent the material flow out of the columns, the filter stone (3 cm height) is put at the bottom of
11

the column and continued with three layers of sand filter (h=3,3,5cm and size range of 1.0-2.0, 0.8-1.25,0.4-0.8
mm ) on the top of each other.
Before running the column, water flows upward through the bed for 5 minutes, causing the bed expansion. In
this manner, the smaller beads will be brought to the top and the larger bead to the bottom. This provides a
better distribution. Another purpose for doing this is to get air and dirt particles out of the column.

3.2 Materials
For the ion-exchange, both resin and zeolite are used. The synthetic ion exchange resin, Lewatit S2568H is a
cation exchange resin in the hydrogen form with functional group sulfonic acid provided by Lanxess. Zeolite is in
the form of natural clinoptilolite received from Zeolite Products. The color of the zeolite is yellow and green.
The chosen size for zeolite is 0.3-1.0 mm and 1.0-2.5 mm. The particle size of resin has a mean bead size of
0.67mm (+/-0.05). For more information about the material, it is to be found in Appendix.

3.3 Measurement methods

The ammonium analyses were performed by spectrophotometer Hach-Lang DR 2800 using Hach-Lang cuvettes
LCK 304. The detection range of ammonium concentration is from 0.02 to 2.5 mg/L. One of the columns can be
connected to analyzer Applikon Colorimeter from which more continuous data will be obtained. The limit of
detection for ammonium is 0.01-1.00 mg/L. For the validation of equipments samples were analyzed by the
Vitens Drinking water Laboratories.

3.4 The validation of spectrophotometer Hach-Lang DR 2800

To calibrate the spectrophotometer Hach-Lang DR 2800, samples were measured under different conditions and
also sent to the Vitens lab to for comparison.
One measurement was done by spectrophotometer Hach-Lang DR 2800. The sample was tested twice at
different time to see if the equipment works properly. One was tested after a reaction time of 15 minutes.
Another one was tested after 30 minutes. And from the manual of the tester, the final absorbance is reached
after a reaction time of 15 min and then remains constant for a further 15 min. Therefore, one was tested after a
reaction time of 15 minutes. Another one was tested after 30 minutes. If it works well, the ammonium
concentration of both being measured should be the same. The other measurement was done by Vitens
Laboratories to see if the results matched with each other. (see Table 3.4.1 in Appendix C and Figure 3.4.1)

Column 2 5cm Lewatit S2568H

0,12
NH4 concentration
(mg/L)

0,1
0,08

R.T t=15min

0,06

R.T t=30min

0,04

t=15min

0,02

t=30min

0
-0,02 0

10

20
30
Time (h)

40

50

Vitens lab data

Figure 3.4.1: 5 cm bed height Lewatit S2568H with flow rate of 12L/h, about 0.1 mg/L NH4+ feed water
measured by Spectrophotometer Hach-Lang DR 2800 and Vitens lab
12

From the data, it can be seen there was a big difference between the two measurements at different time. The
reason might be the sample was not kept at 20 C according to the manual of Hach-Lang DR 2800. To find out
the influence of temperature, new measurement was done with one of the samples kept at room temperature.
The result shows the accuracy of measurement is strongly depended on temperature. The measured results
from Vitens Laboratories matched better with the results measured by spectrometer when the samples kept at
room temperature. In case of not working at the right recommended temperature an incorrect result may be
obtained. Therefore it is recommended to keep samples in a water bath at 20 C before measuring.
Sample in water bath
The permeate samples were kept in the water bath at a constant temperature of 20 C. The measuring results
were obtained as follows in table 3.4.2:
t=15 min
t=20 min
t=25 min
t=30 min
NH4+ (mg/L)
0.116
0.123
0.125
0.125
+
NH4 (mg/L)
0.108
0.112
0.112
0.114
NH4+ (mg/L)
0.115
0.12
0.118
0.12
Table 3.4.2: permeate measured by Spectrophotometer Hach-Lang DR 2800
The spectrometer provides now much more stable measuring results than before. The results were quite stable
at t=20 min. Therefore, the ammonium concentration will be recorded after a reaction time of 20 minutes.

3.5 The validation of ammonium analyzer Applikon Colorimeter

In order to examine the accuracy of ammonium analyzer Applikon Colorimeter, some samples were taken for
Vitens Laboratories.
At the same time, two samples were respectively taken from column 4 for lab test every hour. The ammonium
analyzer Applikon Colorimeter measured automatically the ammonium concentration of effluent every 5
minutes.

Comparison of Vitens and Applikon Colorimeter

0,1
0,09

NH4 concentration(mg/L)

0,08
0,07
0,06
0,05

Vitens

0,04

Applikon Colorimeter

0,03
0,02
0,01
0
0

100

200

300

400

500

600

700

Effluent volume(L)

Figure 3.5.2 Comparison of Vitens and Applikon Colorimeter data from column 4 (5 cm bed height Lewatit
S2568H with flow rate of 12L/h, about 0.1 mg/L NH4+ feed water)
13

Conclusion
According to (Table 3.5.1 and Table 3.5.2 in Appendix D), there were 6 times that the lab data didnt match with
the Applikon Colorimeter data (The red shows lab data in table 2). However, the data in blue color that were just
taken after a few minutes matched better with the one in red. This appearance was probably caused by the
measuring process of analyzer which analyzed samples every 5 minutes. The biggest difference in measuring
results was at 10:45 15th January 2015. It might be regarded as the error of ammonium analyzer Applikon
Colorimeter, because the ammonium concentration was zero at 10:35 and 0.076 mg/L at 10:55, which totally
didnt make any sense.
Based on the figure 3.5.2, the results obtained by analyzer Applikon Colorimeter were different from those by
Vitens Laboratories, when the concentration of ammonium was low in effluent. The difference might due to the
limit of detection in Vitens Laboratories for ammonium. When the concentration of ammonium was high in
effluent, the results of the two measurements were almost the same. Therefore, the result of ammonium
analyzer Applikon Colorimeter is reliable.

3.6 The validation of ammonium dosing pump

Dosing ammonium to the RO permeate was attempted to get a higher ammonium concentration in influent in
order to obtain a breakthrough curve in a short time. The validation of ammonium dosing pump was done by
comparing the results of different experiment set-ups.
For the sake of dosing ammonium concentration, it was divided into several steps. At first, it was required to
figure out the size of tubes and their flow rate. A 10 ml measuring column and a timer were used. The record
shows in table 3.6.1.
Table 3.6.1.Calibration of pump
Rotating speed
Flow rate of
(rpm)
tube 1 (mL/min)
100
4.2
50
2.0

Flow rate of
tube 2 (mL/min)
4.4
2.0

Flow rate of
tube 3 (mL/min)
4.2
2.0

Flow rate of
tube 4 (mL/min)
4.3
2.2

According to the measured results above, the diameter of tubes should be 0.76 mm which provides flow rate of
4.2 mL/min at 100 rpm and 2.1 mL/min at 50 rpm. However, the actual flow rate is depended on how the pump,
tube and solution tank are placed.
3.6.1 Experiment set-up
Experiment 1
The second step was to calculate the amount of required dosing ammonium concentration.
The required ammonium dosing concentration to reach an influent concentration of 40 mg/L NH4+ is calculated
as follows:
Condition:
Pump: 100rpm=4.20 mL/min =0.252 L/h
Flow rate of feed water: 12L/h
Ammonium concentration of feed water: 0.1mg/L
Dosing NH4+ concentration: X
mg
L
mg
40 *12.252 =490.08
L

mg

0.252 * X
mg

mg

mg

+ 12 * 0.1
h

=490.08

X=1940 L =1.94g/L
NH4+ occupies 34% in ammonia chloride.
NH4Cl =1.94g/L /34%=5.71 g/L.
The next step was to check the accuracy of dosing ammonium concentration.
14

In the next experiments, an ammonium dosing solution was made using the same method to get an effluent of
10 mg/L.
Experiment 2
Tried to make a better mixing; a few joints were connected with each other (figure 3.6.2).
Experiment 3
The one way direction valve was taken off that the tube was directly connected with the tube of feed water (see
figure 3.6.3).

Figure 3.6.1 Experiment 1

Figure 3.6.2: Experiment 2

Figure 3.6.3 Experiment 3

Results
Experiment 1
Instead of 5.71 g/L NH4Cl, 1.94g/L NH4Cl was prepared by mistaking the mass of NH4Cl the same as that of NH4+.
In this case, dosing NH4+ together with RO permeate should give 13.7 mg/L as influent ammonium
concentration. The sample of influent was taken and diluted 20 times. The results was 0.454 mg/L. But it should
be 0.685 mg/L.
Experiment 2
No.
1
2
3
4
5

Experiment 3
NH4+
(mg/L)
5.55
3.65
3.52
3.67
6.04

Experiment 2:
Average=4.486 mg/L
Experiment 3:
Average=8.96 mg/L

No.
1
2
3
4
5
6
7

NH4+
(mg/L)
8.60
7.70
8.79
9.51
9.76
9.37
8.28

Minimum=3.52 mg/L

Maximum=6.04 mg/L

STD=5.84

Minimum=7.70 mg/L

Maximum=9.76 mg/L

STD=2.86

Conclusion/Discussion
Due to the measuring range of ammonium analyzer Applikon Colorimeter is from 0 to 1 mg/L, which means it
could not provide a complete breakthrough curve. As the ammonium concentration was so high, the ammonium
analyzer Applikon Colorimeter might just record the beginning part of the curve.
From the results, it can be concluded the tube without one way direction valve gave the most stable ammonium
concentration in comparison with other methods. This method might provide a better mixing and more
continuous water flow. To improve the experiment setup, it is recommended to use a tube with a bigger
diameter.
15

16

4. Results
The main purpose of this research is to design an ion exchange column for the ammonium removal of feed water
(RO permeate). Therefore, the optimum volumetric flow rate should be determined during the experiments over
a range of choices which would provide a maximum breakthrough capacity. Since there was a limitation of time,
it would take too long to determine the breakthrough capacity at a high bed height. Its easier to find the
relation between the bed height and the breakthrough capacity. A complete list of results can be found in the
measuring results in Appendix E.

4.1 The performance of 10 and 20 cm Lewatit S2568H

For each flow rate the breakthrough capacity was compared at the same bed height. Also, the performance of
different bed height was compared at the same flow rate. The overview of the results is presented in Table 4.1.1
and Figure 4.1.1.
Bed
height
(cm)

Flow
rate
(L/h)
10
10
10
10
20
20
20
20
20

Surface
loading
(m/s)

40
60
80
100
12
40
60
80
100

441
661
881
1101
66
220
330
441
551

Average
permeate
concentration
(NH4 mg/L)
0.136
0.129
0.126
0.125
0.136
0.14
0.142
0.136
0.132

Breakthrough
capacity (mg/L)

Breakthrough
capacity (mg/g)

Breakthrough
time (h)

1399
1608
1079
1134
1448
1784
1525
1487
1784

1.89
2.17
1.46
1.53
1.96
2.41
2.06
2.01
2.41

26
22
12
10
1833
62
37
30
27

Table 4.1.1 Breakthrough capacity of Lewatit S2568H at different bed heights and flow rates

Breakthrough capacity (mg/g)

Breakthrough capacity of Lewatit S2568H

3,00
2,50
2,00
1,50

10 cm resin

1,00

20 cm resin

0,50
0,00
0

20

40

60

80

100

120

Flow rate (L/h)

Figure 4.1.1 Breakthrough capacity of Lewatit S2568H at different bed heights and flow rates

17

The breakthrough capacity is calculated as follows, in the following example:

NH4 concentration(mg/L)

Breakthrough curve of 20cm Lewatit S2568H with 100L/h permeate

water
0,05
0,045
0,04
0,035
0,03
0,025
0,02
0,015
0,01
0,005
0

y = 1E-15x4 - 3E-12x3 + 4E-09x2 - 2E-06x + 0,0075

Breakthrough point

20cm resin 100L/h

500

1000

1500

2000

2500

3000

3500

Effluent volume(L)

The area beneath the curve is calculated by integrating the equation of the best fit curve as following:
y = 1E-15x4 - 3E-12x3 + 4E-09x2 - 2E-06x + 0.0075
2658
y = 1E-15/5x5 - 3E-12/4x4 + 4E-09/3x3 - 2E-06/2x2 + 0.0075x=27
0
Average concentration of feed water=0.132 mg/L
Breakthrough capacity=0.132*2658-27=324 mg
324 mg/0.18 L=1784 mg/L =2.41 mg/g
It was expected the trend of breakthrough capacity over a range of flow rates would be similar at different bed
height. Unfortunately, the results from the measurements showed differently.
Figure 4.1 shows that the optimum breakthrough capacity was at flow rate of 60 L/h in a resin column with bed
height of 10 cm, while in a resin column with bed height of 20 cm the optimum breakthrough capacity was at
flow rate of 40 L/h or 100 L/h. If 10 cm resin bed was compared to 20 cm resin bed, it shows that the capacity of
20 cm resin bed is getting bigger as the flow rate increases above 60L/h, while the performance of 10 cm resin
bed didnt demonstrate the similar trend. At flow rate of 60L/h, both resin columns with different bed height
have almost the same breakthrough capacity. If two different bed heights of resin columns were compared
though, it can be seen that the capacity of resin increased with 38% at flow rate of 80L/h and 57% at flow rate of
100 L/h, when the bed height was increased from 10 cm to 20 cm. This indicates that the breakthrough capacity
is related to the bed height. Whether the increasing rate of capacity is proportional to the bed height cannot be
told though.

18

Breakthrough curve of 20cm Lewatit S2568H

0,14

NH4 concentration (mg/L)

0,12
0,1
20cm resin 60L/h

0,08

20cm resin 40L/h

0,06

20cm resin 80L/h

20cm resin 100L/h

0,04

20cm resin 12L/h

Breakthrough point

0,02
0
0

1000

2000

3000

4000

5000

6000

Effluent volume (L)

Figure 4.1.2: Breakthrough curve of 20 cm Lewatit S2568H with different flow rte measured by ammonium analyzer Applikon Colorimeter and Hach
Lang spectrometer DR 2800 (flow rate of 12L/h)

Breakthrough curve of 10cm Lewatit S2568H

0,14
NH4 concentration(mg/L)

0,12
0,1
10cm resin 60L/h

0,08

10cm resin 100L/h

0,06

10cm resin 40L/h

0,04

10cm resin 80L/h

0,02

Breakthrough point

0
0

1000

2000

3000

4000

5000

6000

Effluent volume(L)
Figure 4.1.3Breakthrough curve of 10 cm Lewatit S2568H with different flow rate measured by ammonium analyzer Applikon Colorimeter

Figure 4.1.2 and Figure 4.1.3 give an overview of the breakthrough curves of resin at different flow rates. The
breakthrough curves demonstrate the similar trend. Only at 10 cm bed height, there was an obvious difference
between flow rate of 60L/h and the rest. Compared with other flow rates, the flow rate of 40L/h for 20cm bed
height might provide the most steep breakthrough curve. Since the complete curve was not obtained, this
inference was based on the distribution and characteristics of the data values.

19

4.2 Comparison between Lewatit S2568H and clinoptilolite

Breakthrough curve of 20cm clinoptilolite and Lewatit S2568H
NH4 cncentration (mg/L)

0,09
0,08
0,07
0,06

20cm resin 80L/h

0,05

20cm resin 100L/h

0,04
0,03

20cm zeolite 80L/h

0,02

20cm zeolite 100L/h

0,01
0
0

1000

2000
3000
Effluent volume(L)

4000

Figure 4.1.4 Breakthrough curve of 20 cm Lewatit S2568H measured by ammonium analyzer Applikon Colorimeter and that of clinoptilolite by Hach
Lang spectrometer DR 2800

The chosen particle size range here for the zeolite is 0.3-1.0 mm. Figure 4.1.4 shows that the performance of
resin is much better than that of zeolite. The zeolite reached the breakthrough at effluent volume of around 150
L, while the resin at effluent volume of around 2500 L. This is probably 17 times better. The breakthrough times
for zeolite were 1.7 h and 1.3 h and for resins were 30 h and 26 h at flow rate 80 L/h and 100 L/h respectively.

4.3Comparison between clinoptilolite with different particle size

zeolite
1.0-2.5mm
zeolite
0.3-1.0mm

duration (h)
NH4 (mg/L)
duration (h)
NH4 (mg/L)

2
0.02
17
0.012

23
0.014

42
0.018

45
0.013

64
0.017

66
0.013

70
0.012

Table 4.3.1 Performance of zeolites in different particle size at bed height of 30 cm, flow rate of 12L/h (measured by Hach Lang spectrometer DR
2800

Two kind of zeolite with different particle sizes were used. One has a range between 0.3-1.0 mm; the other has a
range between 1.0-2.5 mm. As expected, it is advantageous to use smaller particle size grading. (see paragraph
2.3.2). In a condition where 30 cm bed height zeolite was at flow rate of 12 L/h, the zeolite of big particle size
reached 0.02 mg NH4+ in effluent after 2 hours. For zeolite of small particle size, the ammonium concentration in
effluent was under measuring range even after 70 hours. (see Table 4.3.1)

20

5. Discussion
5.1 Influence of bed height
In ion exchange, if the separation factor for the unwanted ion to be removed is greater than 1, the mass transfer
zone length or exchange zone will be relatively small in comparison with the column height. (John C. Ctrittenden
et al., 2015). This indicates that an increase in bed height for the column at the same flow rate will not change
the breakthrough capacity. From the literature, it shows that the NH4+/H+ separation factor is 1.9. Since the
separation factor is greater than 1, it was expected that the breakthrough capacity would remain the same for
different bed height. Unfortunately, the results showed differently. Some studies recommend doing column
experiments at a reasonable height between 0.6 to 1m. This is probably due to the fact that the feed water
would flow downward along with the column walls, which results in less efficient contact with the resin when
the bed height is not high enough. From the Figure 4.1.1, it can be seen that the resin with a higher bed height
also has a higher breakthrough capacity. But it was expected that the rate of an increase in breakthrough
capacity would be lower as the bed height increases. At a certain bed height, the influence of it on breakthrough
capacity would be neglected.

5.2 Influence of flow rate

Normally, in the case of strong acid resin in dilute solutions, the flow rate of ions arrived on the beads is faster
than ions diffuse through the film. As described in paragraph (2.3.2), the distinction between H+ form and NH4+
form resin will not be obvious. Thus, the breakthrough capacity is expected to be lower at a higher flow rate. If
the thickness of the film remains the same, the breakthrough capacity would decrease proportional to the flow
rate. In fact, the thickness of the film wouldnt stay unchanged; it decreases with an increase in flow rate.
Therefore, the rate of arrival of ions would be faster. But the loss of breakthrough capacity would be minimized
by the thicker flim. This helps to explain why Figure 4.1 shows that the flow rates over a range between 12 and
100L/h do not have significantly impact on the breakthrough capacity of the resin. This also implies that the
breakthrough time is long enough for the ion exchange process to happen in the resin. The resin is at equilibrium
with the solution.

Breakthrough capacity (mg/g)

Breakthrough time (h)
Flow rate L

Figure 5.1 Effect of breakthrough time and flow rate on the breakthrough capacity
The Figure 5.1 presents how the relation between breakthrough capacity and flow rate and breakthrough time
could look like. At a certain short breakthrough time and high flow rate, the time required for ions diffuse
through the film is longer than that for ions to be presented to the resin beads. Thus, the film diffusion begins to
take the effect.

21

5.3 Kinetics
The figures 4.2 and 4.3 also indicate that the film diffusion is rate controlling. As the ion concentration in the
feed water increases, the rate of film diffusion increases and becomes even faster than the rate of particle
diffusion. The overall rate of ion exchange process is determined by the particle diffusion. If it is so, the
breakthrough capacity would increase proportional to the flow rate. In other word, the film diffusion is rate
controlling in the diluted solution. In the experiment condition, the feed water had only ammonium
concentration of around 0.1 mg/L. The concentration of other ions should be very low, because the feed water
was obtained after the RO membrane process. Therefore, the feed water was a diluted solution, in which the
rate of ion exchange process was film diffusion determined.

5.4 Performance of zeolite and resin

The resin performed much better than zeolite. This might because the surface of zeolite was much rougher than
that of resin. Therefore, there was an increase in thickness of the film and ammonium need more time to diffuse
through the surrounding film. Lewatit S 2568H is a cation exchange resin in the hydrogen form. Zeolite is in the
form of clinoptilolite with Na+ as counter-ions. Since the size of H+ is smaller than that of Na+, it might easier for
H+ to diffuse from the beads to the bulk solution.
In the comparison of the previous research done by Ekowati, the results were the same. The resin performed
better than zeolite. In her research, no breakthrough of the resin was observed until the experiments were
stopped.
But when it comes to the run length of the zeolite, the results were not comparable. The run lengths calculated
base on the KWR isotherm were 18h and 14h at flow rate 80 L/h and 100 L/h. According to the experiment
results, they were 1.7 h and 1.3 h. This might because the bed height was too low to prevent the feed water
flows down along with the walls effectively.

5.5 Influence of particle size.

Reaction is a function of particle size. As explained in paragraph 2.2.3, the smaller particle size provides a larger
surface area. The time an ion needs to travel through the resin bead itself decreases with decreasing particle size.
From the experiments, it can be seen that the results were comparable to that found in KWR report. In this
report, its concluded that ammonium removal is faster with the smaller grains.

5.6 Difficulties of doing pilot experiments

The ammonium concentration of feed water was not so stable during the experiments. In the extreme case, the
lowest concentration was 0.08 NH4+ mg/L and the highest concentration was 0.16 NH4+ mg/L. If the experiments
were done at different bed heights, more data would be obtained to help investigate the relation between the
bed height and the breakthrough capacity. But, its not possible to do due to the time limitation. A higher bed
height would require more time to run the experiment. Sometimes, it was not possible to get a complete and
reliable breakthrough curve by using Hach Lang spectrometer DR 2800, because the breakthrough point
occurred during the night. It was planned to increase the NH4+ concentration in feed water by doing pump.
Unfortunately, it was not succeeding and the mixing problem still has to be dissolved.

22

6. Ion exchange column design calculation

6.1 Introduction
For the up-scaling calculation it is required to know how much water is produced. Drinking water treatment
plant De Hooge Boom in Kamerik is designed to have an average production of 300m3/hour with a peak
production of 420m3/hour. From this and other boundary conditions the preliminary design of the membrane
filtration step is to have 4 stacks of each a capacity of 120m3/hour. Following the first treatment, every
succeeding step in the treatment plant will consist of 4 unit with each a capacity of 120m3/hour (see Appendix
F).
Based on the results of the experiments, it was found that Lewatit S2568H resin is more effective than
clinoptilolite for the removal of ammonium ions from permeate.
To design ion exchange columns there are some aspects that should be taken into consideration, such as the
volume of resin, the surface area of resin, the height of columns, the number of columns and the pressure drop.
The data obtained from small-column (1.0 to 5.0 cm inside diameter) can be scaled up directly to full-scale
design if the surface loading rate and empty bed contact time are the same. (John C. Ctrittenden et al., 2015)
This rule can be applied to scale-up this design, because the diameter of columns is 3.4 cm. To get the above
described parameters, the optimum volumetric flow rate should be determined during the experiments over a
range of choices to find out if there is a maximum breakthrough capacity at a certain flow rate. According to
John C. Ctrittenden, the minimum bed height used in the industry is 0.75 m, and the maximum 3 m. The
maximum bed height is established to prevent the big pressure drop that would affect the stability of the resin.
From the results, it can be seen that by increasing the bed height at the same flow rate the breakthrough
capacity would be increased. Thus, a higher bed height is preferred but not exceeds the maximum. Based on
manufactures production information, the minimum bed depth for Lewatit S2568H is 800mm.

6.2 Design calculation

Since the experiment results show that the breakthrough capacity was quite stable over a range of flow rate
between 12L/h and 100L/h, the following assumptions are made:
-

The maximum capacity is all used.

Average breakthrough capacity of 2.17 mg/g (1606 mg/L) at 20 cm bed height is used for calculation for
different bed heights. It is assumed that the breakthrough capacity remains the same.
The ammonium concentration of permeate is 0.14 mg/L.

An example of calculation for the column design

In this example a flow rate of 100L/h is taken.
Pressure drop
Based on the manufactures data, the maximum pressure drop for the resin bed is 300kPa. Both of surface
loading and bed height have impact on pressure drop through the resin. The relevant information can be found
in pressure drop formula sheet (Appendix B) provided by manufacture.
The pressure drop of ion exchange resin beds is calculated according the following formula:
p [kPa] = h [m] x v [m/h] x FV x FT x FR
h = Resin bed depth [m]
v = Linear velocity [m/h]
FV = Velocity factor (from diagram 6.1 and Appendix C)
FT = Temperature factor (Appendix C)
FR = Resin factor (specific pressure drop [kPa x m-2 x h]

23

velocity factor of Lewatit S2568H

1,8
y = 4E-05x2 + 0,003x + 0,919

Velocity Factor

1,7
1,6
1,5
1,4
1,3

velocity factor

1,2
1,1
1
20

30

40

50

60

70

80

90 100 110 120

Flow rate (m/h)

Diagram 6.1 Velocity factor

FR in this case is 0.8 [kPa x m-2 x h]
FT=1.1
Linear velocity/surface loading (m/h)= 100/1000/(*0.017^2)=110 m/h
Maximum resin bed height (m)
h= 300/(110*(4*(10^-5)*110^2+0.003*110+0.919)*1.1*0.8)=1.8m
Service flow rate
The volume of the bed occupied by the resin:
BV=area depth=(0.17dm)218dm=1.63L
SFR=100L/h1BV/1.63L=61BV/h
Volume of resin
Treated water flow rate=120 m3/h
Treated water flow rate 120L/h

Total required resin volume=

SFR

=61 BV/h==2.0 m3

Surface area of resin required

Resin volume 2.0 m3

Total required surface area=

Resin depth

Diameter= (1.1 m2/)^0.5*2=1.2m

= 1.8 m =1.1m2

Breakthrough time
L
mg
mg
L
Approximate breakthrough time= 2.0 m3*1000m3*1606 L /0.14 L /120000h=186h=7.7days
Cost of material
If the exhausted resin is replaced by new resin after each 7.7 days without considering regeneration, the total
cost per year would be:
Lewatit S2568H= 2.55 euro per Liter
euro
L
Total cost= =2.55 L *2.0 m3*1000m3/(7.7days/365days)=233673 euro
m3

Total produced water per year= 130 *4*24*365=4555200 m3

h
The cost per m3 water produced would be 233673 euro/4555200 m3 =0.06 euro
This price is also for flow rate between 12-100L/h, because the breakthrough capacities are almost the same.
24

Column height
As there is bed expansion during backwashing with considerable risk of resin loss, an extra space is needed. The
bed expansion is about 70% at the flow rate of 12 L and the water temperature is 12.
The required height for backwashing= 1.8m*70%=1.26 m
The minimum column height without considering of the height for resin support and inlet distributor should be:
1.8m+1.26m=2.06 m.
An over view of column design
Flow
rate

Surface
loading

Resin
SFR
Required Required
Diameter
bed
resin
surface
height
volume
area
(L/h)
(m/h)
(m)
(BV/h)
(m3)
(m2)
(m)
12
13
27
0.5
243
9.1
3.4
20
22
15
1.4
84
5.4
2.6
30
33
10
3.4
35
3.6
2.2
40
44
6.9
6.4
19
2.7
1.9
50
55
5.1
10.7
11
2.2
1.7
60
66
4.0
16.6
7
1.8
1.5
70
77
3.2
24.2
5
1.6
1.4
80
88
2.6
34.0
4
1.4
1.3
90
99
2.1
46.4
3
1.2
1.2
100
110
1.8
61.7
2
1.1
1.2
Table 6.1 overview of column design with maximum resin bed height

BreakThrough
Time
(h)
23183
8023
3373
1785
1070
693
474
337
247
186

BreakThrough
time
(days)
966.0
334.3
140.6
74.4
44.6
28.9
19.7
14.0
10.3
7.7

Material
cost
per year
(euro)
233673
233673
233673
233673
233673
233673
233673
233673
233673
233673

The influence of different surface loadings on the design is presented in table 6.1. The resin bed height above
presented the maximum bed height a column can have without exceeding the limited pressure drop. As the
surface loading increases, the size of the column and breakthrough time decrease. Although, a smaller column
requires replacement or regeneration of resin more frequently, it saves the space and equipment investment
and maintenance cost.
Recommendation
It was noticed that the breakthrough time for each flow rate above is quite long. It is considerable to replace
with the new resin after each service run, if the financial aspect is not considered. However, in real life it is
always good to have a cost as low as possible while maintaining quality. The material cost of 6 cents per m3
water is a bit too expensive. The ion exchange process with regeneration might be a good solution.
The following assumptions are made:
-

Bed height is 2m (feasible, a common bed height for ion exchange)

Regeneration cost is maximum 25% of the resin cost

An overview of column design at bed height of 2 m is shown in Table 6.1. Flow rate at 100L/h is not excluded
from the calculation table, because its maximum allowed bed height is 1.8 m.The calculation method is the same
as before. The material cost per m3 produced water is calculated as follows:
For example at flow rate of 90 L/h
Material cost per year=
euro
L
euro
L
2.55 L *2.42m3*1000m3+2.55 L *2.42m3*1000m3*0.25*365days/9.6days= 64596 euro
Material cost per m3 produced water=
64596 euro/4555200 m3=0.014euro

25

flow
rate

linear
velocity

Resin
SFR
Required Required Diameter
Bed
resin
surface
Height
volume
area
(L/h)
(m/h)
(m)
(BV/h)
(m3)
(m2)
(m)
12
13
2
6.6
18.16
9.1
3.4
20
22
2
11.0
10.90
5.4
2.6
30
33
2
16.5
7.26
3.6
2.2
40
44
2
22.0
5.45
2.7
1.9
50
55
2
27.5
4.36
2.2
1.7
60
66
2
33.0
3.63
1.8
1.5
70
77
2
38.5
3.11
1.6
1.4
80
88
2
44.1
2.72
1.4
1.3
90
99
2
49.6
2.42
1.2
1.2
Table 6.1 overview of column design with 2m resin bed height

Breakthrough
time
(days)
72.3
43.4
28.9
21.7
17.4
14.5
12.4
10.8
9.6

Material
cost per
year
(euro)
104722
86201
76940
72309
69531
67679
66356
65364
64592

Material
cost per
m3 water
(euro)
0.023
0.019
0.017
0.016
0.015
0.0149
0.0146
0.0143
0.0142

From the table, it can be seen that the size of column and material cost decrease as the flow rate (surface
loading) decreases. Thus, for a 2 m bed height column, its best to operate at a surface loading of 99 m/h. Both
equipment cost and material cost would be the lowest.
The empty bed contact time is calculated with the formula:
H

EBCT= V
EBCT=empty bed contact time (h)
V=surface loading (m/h)
H=bed height (m)
The EBCT would be: EBCT=

2m
99m/h

=0.02 h= 1.2 minutes

The minimum column height without considering of the height for resin support and inlet distributor would be:
2.0m(1+70%)=3.4 m.

26

7. Conclusion and recommendations for future research

7.1 Conclusion
The goal of this research project is to design ion exchange column for the future full scale treatment plant De
Hooge Boom in Kamerik. In order to reach this goal the following research questions were asked and needed to
be answered.
What is the influence of the surface loading (which is flow rate of feed water on the effectiveness of
ammonium removal by ion exchange)?
It was expected that the breakthrough capacity would increase as the flow rate increases. However, the
results showed differently. The breakthrough curves demonstrated the similar trend at the flow rate
between 12L/h and 100L/h. The possible explanation for this phenomenon was discussed in chapter 6. If
the thickness of the film remains the same, the breakthrough capacity would be lower at a higher flow rate.
In fact, the thickness of the film wouldnt remain unchanged; it decreases with an increase in flow rate. This
results in faster arrival of ions on the beads. But the loss of breakthrough capacity would be minimized or
avoided by the thicker film. For the ion exchange column design, the average breakthrough capacity of 2.17
mg/g (1606 mg/L) was used.

What is the influence of the bed height of the ion exchange for the effectiveness of ammonium removal?
From the results, it can be concluded that the ion exchanger with a higher bed height also has a higher
breakthrough capacity. This is because the column walls are every smooth in comparison with the bed so
that the feed water would flow downward along with the column walls. The feed water would have less
contact with the ion exchanger. But it was expected that the rate of an increase in breakthrough capacity
would be lower as the bed height increases. At a certain bed height, the influence of it on breakthrough
capacity would be neglected.
What would the design in the future treatment plant look like?
Based on the experiment results and calculation, the ion exchange is design as follows:
Number of vessels: 4 each with a capacity of 120m3/h
Bed height: 2m
Column height (without considering of the height for resin support and inlet distributor)=3.4m
Surface loading: 99m/h
EBCT: 1.2 minutes
Breakthrough time: 10 days
Material cost of resin per m3 water produced: 0.014

27

7.2 Main uncertainties in the research and design

One of the main uncertainties would be the relation between the flow rate and the breakthrough capacity. From
the experiment results, the breakthrough capacities were quite similar between 12L/h and 100L/h. But, what
will happen with the breakthrough capacity at a higher flow rate still need to be tested through experiments.
Another uncertainty was the influence of bed height on the breakthrough capacity and to what degree.

7.3 Recommendations for future research

Its recommended to do experiments at higher bed heights, for example at 80 cm. The effect of less contact time
with the ion exchanger that caused by the fact that water flows down along with the column walls would be
minimized in this manner. Since the ammonium concentration of feed water was not constant, its better to
measure the concentration more frequently. Higher flow rate can be tried in the future research to see how it
will affect the breakthrough capacity. It is also interesting to dose an ammonium concentration to the feed water
to see how NH4+ concentration related to the breakthrough capacity at the same flow rate.

28

Reference
B.A.Bolto and L.Pawlowski (1987) wastewater treatment by ion exchange., E.& F. N. Spon
George J. Crits (2012) Crits Notes on Water and Ion Exchange., Chemical Publishing
Helfferich,F. (1961) Ion exchange, McGraw-Hill, pp250-319.
Inamuddin Mohammad Luqman (2012) Ion exchange technology I theory and materials, Springer, London.
pp.22.
John C. Ctrittenden, R.R.Trussell, D.W.Hand, K.J.Howe, G.Tchobanoglous (2015) John Wiley & Sons, Inc, Water
treatment, principles and design. MWH. Second edition. P.1406-1426.
Kiwa N.V. (2005) Ammonium removal in drinking water using natural zeolite
Kunin R (1951) Ion exchange. Ind Eng Chem 43:102108
Langwaldt, J. R. (2008) Ammonium Removal From Water by Eight Natural Zeolites: A Comparative Study.
Separation Science and Technology, 43, 2166 - 2182.
Rohm and Haas (2008) Ion exchange introduction
R.R.Harries. (1988) The role of pH in ion exchange kinetics, Ion Exchange for Industry, Nottingham NG11 OEE, UK,
pp.314-325
Schmidt, W (2008) http://www.mpimuelheim.mpg.de/kofo/institut/arbeitsbereiche/schmidt/zeolites_ee.html.
Tony C. Jorgensen (2002) Removal of ammonia from wastewater by ion exchange in the presence of organic
compounds. Master of Engineering, University of Canterbury.
T.V.Arden., F.R.I.C.,M.I.M.M., P.A.I.W.E (1968) Water purification by ion exchange., Plenum Press
Yuli Ekowati (2014) From RO permeate to an impeccable drinking water and biologically stable water.
Oasen&UNESCO-IHE Institute for Water Education.
Yvonne Mikkers (2009) Regeneration of zeolites used for ammonium removal from anaerobic groundwater.
Oasen&Master of Science in civil engineering, Delft University of Technology.

29

Appendix A: Drinking water quality standards

The following environmental quality standards are target values which relate to surface water used for the
preparation of drinking water.
Parameter

Unit

Standard

acidity

pH

7,0 8,5

suspended solids

mg/l

25

Conductivity electricity

mS/m at 20C

100

Odor dilution factor at 20 C

chloride

mg/l Cl

150

sulphate

mg/l SO4

100

fluoride

mg/l F

0,7

ammonium

mg/l N

0,2

Organic nitrogen

mg/l N

nitrate

mg/l NO3

25

dissolved oxygen

mg/l O2

>6

Chemical oxygen demand

mg/l O2

30

Biochemical oxygen demand

mg/l O2

sodium

mg/l Na

90

Iron resolved

mg/l Fe

0,1

manganese

g/l Mn

50

buyer

g/l Cu

20

zinc

g/l Zn

200

drill

g/l B

1000

arsenic

g/l As

10

cadmium

g/l Cd

Chromium (total)

g/l Cr

20

lead

g/l Pb

30

selenium

g/l Se

10

mercury

g/l Hg

0,3

barium

g/l Ba

100

cyanide

g/l CN

50

Surface-active substances which react with methyleenblau

g/l

200

Water vapor volatile phenols

g/l C6H5OH

mineral oil

g/l

50

Polycyclic aromatic hydrocarbons

g/l

0,2

Human toxicological relevant plant protection products, biocides, and their relevant g/l
degradation products (sum)

0,5

Pesticides, biocides and their relevant degradation products per individual g/l
substance

0,1

Choline-esterase inhibitors,

g/l

1,0

Coliform bacteria (total)

number per 100 50

ml
30

Parameter

Unit

Thermo-tolerant coliform bacteria

number per 100 20

ml

fecal streptococce

number per 100 20

ml

algae Biomass

g/l chlorofyl-a

Standard

100

Table 1. Environmental quality standards with respect to surface water used for the preparation of drinking water

31

Appendix B: Schematic drawing Set-up by Yvonne Mikkers

32

Appendix C: Material data sheet

33

PRODUCT INFORMATION

LEWATIT S 2568 H

Lewatit S 2568 H is a food grade, macroporous, monodisperse, strongly acidic cation exchange resin
based on a styrene-divinylbenzene copolymer.

Lewatit S 2568 H is especially applicable for:

the decationization of solutions of organic products, e.g. sugar beet, sugar cane, starch sugar, glycerine,
gelatine, whey and food acids etc.
the extraction of amino acids, e.g. lysine
mixed bed polishing

Lewatit S 2568 H is adding special features to the resin bed:

high exchange flow rates during regeneration and loading
a good utilization of the capacity, low rinse water demand
a homogeneous throughput of regenerants, water and solutions; therefore an homogeneous working zone
a nearly linear pressure drop gradient for the whole bed depth; therefore an operation with higher bed
depth possible
a good separation behaviour of the components in a mixed bed application

If using Lewatit S 2568 H to treat potable water and the aqueous solutions listed above, special care should
be given to the initial cycles of the new resin. Please refer to the recommended start-up conditions available
on request.

The special properties of this product can only be fully utilized if the technology and process used correspond
to the current state-of-the-art. Further advice in this matter can be obtained from Lanxess, Business Unit
Liquid Purification Technologies (LPT).

This document contains important information

and must be read in its entirety.
Edition: 2014-05-22
Previous Edition: 2014-01-16

1/5

34

PRODUCT INFORMATION

LEWATIT S 2568 H
General Description
+

Ionic form as shipped

Functional group
Matrix
Structure
Appearance

H
Sulfonic acid
Crosslinked polystyrene
Macroporous
Beige-grey, opaque

Specified Data
Uniformity Coefficient
Mean bead size
Total capacity

metric units
max.
mm
min. eq/l

1.1
0.67 (+/- 0.05)
1.6

metric units
g/l
approx. g/ml
wt. %

740
1.18
54 - 60

Physical and Chemical Properties

Bulk density
Density
Water retention

(+/- 5 %)

Volume change
Stability

H --> Na
at pH-range

max. vol. %

-8
0 - 14

Stability
Storability
Storability

temperature range
of the product
temperature range

C
max. years
C

-20 - +120
2
-20 - +40

This document contains important information

and must be read in its entirety.
Edition: 2014-05-22
Previous Edition: 2014-01-16

2/5

35

PRODUCT INFORMATION

LEWATIT S 2568 H
Recommended Operating Conditions*
metric units
OPERATION
Operating temperature
Operating pH-range
Bed depth

max. C

120
0 - 14
800

min. mm

Specific pressure drop

Pressure drop
REGENERATION,
COUNTER-CURRENT
Regenerant

(15 C)

Regenerant

quantity

approx. g/l

Regenerant

concentration

wt. %

approx. kPa*h/m
max. kPa

type

Linear velocity

approx. m/h

Linear velocity
rinsing
Rinse water requirement slow / fast

approx. m/h
approx. BV

REGENERATION, COCURRENT
Regenerant

type

Regenerant

quantity

approx. g/l

Regenerant

concentration

approx. wt. %

Linear velocity
Linear velocity
Bed expansion
Freeboard

0.8
300

HCl
H2SO4
NaCl
HCl 60
H2SO4 100
NaCl 100
HCl 4 - 6
H2SO4 1.5 / 3**
NaCl 8 - 10
HCl 5
H2SO4 10 - 20
NaCl 5
5
2.5

HCl
H2SO4
NaCl
HCl 100
H2SO4 150
NaCl 200
HCl 4 - 6
H2SO4 1.5 / 3**
NaCl 8 - 10
10 - 12
5
4
60

backwash (20 C)
approx. m/h
rinsing
approx. m/h
(20 C, per m/h)
approx. vol. %
backwash
vol. %
(extern / intern)
* The recommended operating conditions refer to the use of the product under normal operating
conditions. It is based on tests in pilot plants and data obtained from industrial applications. However,
This document contains important information
and must be read in its entirety.
Edition: 2014-05-22
Previous Edition: 2014-01-16

3/5

36

PRODUCT INFORMATION

LEWATIT S 2568 H
additional data are needed to calculate the resin volumes required for ion exchange units. These data are
to be found in our Technical Information Sheets.
** Regeneration progressive

This document contains important information

and must be read in its entirety.
Edition: 2014-05-22
Previous Edition: 2014-01-16

4/5

37

PRODUCT INFORMATION

LEWATIT S 2568 H
Additional Information & Regulations
Safety precautions
Strong oxidants, e.g. nitric acid, can cause violent reactions if they come into contact with ion exchange
resins.
Toxicity
The safety data sheet must be observed. It contains additional data on product description, transport,
storage, handling, safety and ecology.
Disposal
In the European Community Ion exchange resins have to be disposed, according to the European waste
nomenclature which can be accessed on the internet-site of the European Union.
Storage
It is recommended to store ion exchange resins at temperatures above the freezing point of water under
roof in dry conditions without exposure to direct sunlight. If resin should become frozen, it should not be
mechanically handled and left to thaw out gradually at ambient temperature. It must be completely thawed
before handling or use. No attempt should be made to accelerate the thawing process.

This information and our technical advice whether verbal, in writing or by way of trials
are given in good faith but without warranty, and this also applies where proprietary rights
of third parties are involved. Our advice does not release you from the obligation to check
its validity and to test our products as to their suitability for the intended processes and
uses. The application, use and processing of our products and the products manufactured
by you on the basis of our technical advice are beyond our control and, therefore, entirely
your own responsibility. Our products are sold in accordance with the current version of
our General Conditions of Sale and Delivery.

Edition: 2014-05-22

LANXESS Deutschland GmbH

BU LPT
D-51369 Leverkusen
www.lewatit.com
www.lanxess.com

5/5

38

Appendix D: The results of validation of equipments

Column 2 Lewatit S2568H with bed height of 5cm
Datum :13-01-2015
Time Taking
T=15 min NH4+ (mg/L)
T=30 min NH4+ (mg/L)
Temperature (C)
Lab data NH4+ (mg/L)
11:45
0.011
0.029 R.T
11:45
-0.006
0.001
12:45
0.012
0.023 R.T
0.0045
12:45
-0.003
0.016
13:45
0.027
0.031 R.T
0.0011
13:45
0.004
0.018
14:45
0.013
0.015 R.T
0.0016
14:45
-0.002
0.014
15:25
0.005
0.014 R.T
0.0031
15:25
-0.005
0.01
Datum :14-01-2015
8:45
0.008
0.032 R.T
0.016
8:45
-0.004
0.02
9:45
0.023
0.034 R.T
0.025
9:45
0.007
0.032
10:45
0.025
0.052 R.T
0.028
10:45
0.010
0.041
13:45
0.040
0.053 R.T
0.034
13:45
0.038
0.049
Datum :15-01-2015
9:45
0.073
0.086 R.T
0.072
9:45
0.044
0.074
10:45
0.071
0.090 R.T
0.075
10:45
0.043
0.079
11:45
0.073
0.090 R.T
0.078
11:45
0.044
0.083
12:45
0.074
0.096 R.T
0.074
12:45
0.041
0.078
Negative value: under measuring range (0.02 - 2.5 mg/L ammonium) R.T= Room temperature
Table 3.4.1: (5 cm bed height Lewatit S2568H with flow rate of 12L/h, about 0.1 mg/L NH4+ feed water measured by Spectrophotometer
Hach-Lang DR 2800 and Vitens lab)
39

Date

time

Parameter

laboratory

Validated

Value

13/1/2015

12:45

Ammonium - mg/l NH4 - 0271

Vitens

0.006

13/1/2015

13:45

Ammonium - mg/l NH4 - 0271

Vitens

Yes
Yes

13/1/2015
13/1/2015
14/1/2015
14/1/2015
14/1/2015
14/1/2015
14/1/2015
14/1/2015
15/1/2015
15/1/2015
15/1/2015
15/1/2015
15/1/2015
15/1/2015

14:45
15:25
08:45
09:45
10:45
11:45
12:45
13:45
09:45
10:45
11:45
12:45
13:45
14:45

Ammonium - mg/l NH4 - 0271

Ammonium - mg/l NH4 - 0271
Ammonium - mg/l NH4 - 0271
Ammonium - mg/l NH4 - 0271
Ammonium - mg/l NH4 - 0271
Ammonium - mg/l NH4 - 0271
Ammonium - mg/l NH4 - 0271
Ammonium - mg/l NH4 - 0271
Ammonium - mg/l NH4 - 0271
Ammonium - mg/l NH4 - 0271
Ammonium - mg/l NH4 - 0271
Ammonium - mg/l NH4 - 0271
Ammonium - mg/l NH4 - 0271
Ammonium - mg/l NH4 - 0271

Vitens
Vitens
Vitens
Vitens
Vitens
Vitens
Vitens
Vitens
Vitens
Vitens
Vitens
Vitens
Vitens
Vitens

Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes

0.009
0.011
0.011
0,035
0,036
0,041
0.003
0,046
0,042
0,069
0,073
0,073
0,073
0,073
0,076

Table 3.5.1: Data of column 4 (5 cm bed height Lewatit S2568H with flow rate of 12L/h, about 0.1 mg/L NH 4+ feed water measured by
Spectrophotometer Hach-Lang DR 2800 and Vitens lab)

40

Date and time

2015/1/13 12:45
2015/1/13 13:45
2015/1/13 14:45
2015/1/13 15:25
2015/1/14 8:45

Status
OK
OK
OK
OK
OK

Value
0.011
0.016
0.011
0.019
0.033
0.025
2015/1/14 9:45
OK
0.04
0.022
2015/1/14 10:45
OK
0.04
2015/1/14 10:50
OK
0.04
0.042
2015/1/14 11:45
OK
<0.03
0.037
2015/1/14 12:45
OK
0.05
2015/1/14 13:45
OK
0.041
OK
0
2015/1/15 10:35
0.003
2015/1/15 10:45
OK
0.07
OK
0.076
2015/1/15 10:55
OK
0.076
2015/1/15 10:55
2015/1/15 11:45
OK
0.068
2015/1/15 12:45
OK
0.07
2015/1/15 13:45
OK
0.071
0.072
2015/1/15 14:45
OK
0.08
OK
0.08
2015/1/15 14:50
Table 3.5.2:Data of column 4 (5 cm bed height Lewatit S2568H with flow rate of 12L/h, about 0.1 mg/L NH4+ feed water measured
ammonium analyzer Applikon Colorimeter and shows in black and blue.

41

Appendix E: Measuring reports

5 cm Lewatit S2568H
Condition:
Feed water = RO permeate with probably 0.1 mg/L ammonium concentration
Temperature of feed water= 12 0C
Flow rate =12L/h

Breakthrough curve
0,1
0,09

NH4 concentration
(mg/L)

0,08
0,07
0,06
0,05

Exp2 NH4(mg/L)

0,04

Exp1.NH4(mg/L)

0,03

breakthrough

0,02
0,01
0
0

500

1000

1500

2000

Time(minutes)

Graph 1: Experiment 1 and experiment 2 (5 cm resin with flow rate of 12L/h measured by analyzer
Applikon Colorimeter)
The ion exchange experiments with resin bed height of 5cm were done twice. Both gave the similar
results. The breakthrough curves were expected to be constant at the beginning and sharp later on. In
fact, the ammonium concentration already started to increase when the experiment began. A lot of
peaks and dips can be recognized. The value of zero ammonium in effluent seems very strange. It looks
like the resin was regenerated during the experiment. Thus, it could be considered as measuring error.
Despite of these inconsistencies a general trend in ammonium concentration in effluent can be
recognized. From the graphics, it can be seen the ammonium concentration was increasing linearly with
the effluent volume. A reason for this could be the bed height is too short or the flow rate is too high.

42

1 cm Clinoptilolite (1.0-2.5 mm)

Condition:
Feed water = RO permeate with probably 0.1 mg/L ammonium concentration
Temperature of feed water= 12 0C
Flow rate =12L/h

Breakthrough curve of 1 cm clinoptilolite with 12L/h permeate water

0,1
0,09

NH4 concentration
(mg/L)

0,08
0,07
0,06
0,05
0,04

NH4 concentration

0,03
0,02

Breakthrough

0,01
0
0

1000

2000

3000

4000

5000

time (minutes)

Graph 2: 1cm zeolite with flow rate of 12L/h measured by analyzer Applikon Colorimeter
From Graph 2, the beginning concentration of ammonium was 0.07 mg/L. As the permeate inflow was
0.1 mg/L, it could be considered that ion exchange was not complete. That is to say, at the begging, it
reached at the breakthrough point. The bed height of zeolite was only 0.01m that was the main reason
of 0.07 mg/L ammonium concentration at the start point.
Specifically, the graph of ammonium concentration fluctuated between 0.06 mg/L and 0.1 mg/L. Some
moment even reached at 0 mg/L. The above breakthrough curve was absolutely different as the usual
one.
Reason: Due to the shearing strength, the flow rate was different among the middle and the wall of the
column. Specifically, the velocity of middle equaled to the inflow rate and should be much higher than
the velocity of the columns wall. But in fact, the bed height of zeolie was only 1cm.
The bed which contains zeolite has very rough surface. In comparison with that, the column wall is very
smooth. Because of this, the water flow rate should be the highest along with the wall and slowest in
the zeolite. In case of 1 cm of zeolite bed, water might go through the column too fast without enough
contact time with zeolite to perform ion exchange. Therefore, the effluent already reached
breakthrough at the beginning.

43

10 cm Clinoptilolite (1.0-2.5 mm)

Condition:
Feed water = RO permeate with probably 0.1 mg/L ammonium concentration
Temperature of feed water= 12 0C
Flow rate =12L/h

Breakthrough curve of 10 cm clinoptilolite with 12L/h permeate water

0,1

Permeate

0,09
NH4
Concentration (mg/L)

0,08
0,07
0,06
0,05
0,04

NH4

0,03
0,02

breakthrough

0,01
0
0

200

400

600

800

1000

Effluent volume (L)

Graph 3: 10 cm clinoptilolite at flow rate of 12L/h measured by ammonium analyzer Applikon

Colorimeter
The Graph 3 shows that at the beginning, the ammonium concentration of effluent had exceeded
breakthrough point (0.03 mg/L) and started at 0.06 mg/L, this is due to some not exchanged feed water
exited in the pipe. And the ammonium analyzer Applikon Colorimeter directly tested it at first. Besides
of this element, the experiment 4 still can reach at breakthrough start point quickly, the zeolite might
be consumed very soon and the roughness of zeolite will influence the ion exchange efficiency.

44

20 cm Clinoptilolite (1.0-2.5 mm)

Condition:
Feed water = RO permeate with probably 0.1 mg/L ammonium concentration
Temperature of feed water= 12 0C
Flow rate =12L/h
Breakthrough curve of 20 cm clinoptilolite with 12L/h permeate water
0,12

NH4 concentration (mg/L)

0,1
Permeate
0,08
0,06
Column 2 20cm zeolite

0,04

Column 3 20cm zeolite

Breakthrough

0,02
0
0

50

100

150
200
Effluent volume (L)

250

300

350

Graph 4: (20 cm bed height zeolite clinoptilolite with flow rate of 12L/h measured by Spectrophotometer
Hach-Lang DR 2800)
The samples were checked every 1 hour for the first two hours and then the columns left running
overnight. The ammonium concentration was very low at the beginning and started to increase slowly
to the breakthrough point. The breakthrough is when the effluent volume is between 150L and 200L.
After this, the concentration was increasing faster than before and tending to reach the ammonium
concentration of influent. From the tendency, its been estimated the concentration of 0.1 mg/L will be
reached at effluent volume of 400 L.
Remark: At t=0 the measured NH4+ concentration in effluent were very close to that in influent. There
might be influent left in the tubes where samples were taken.

45

1, 10 and 20 cm Clinoptilolite (1.0-2.5 mm) in comparison

Condition:
Feed water = RO permeate with probably 0.1 mg/L ammonium concentration
Temperature of feed water= 11 0C
Flow rate =12L/h

Breakthrough curve of
1, 10 and 20 cm clinoptilolite with 12L/h permeate water

0,12
0,1

Permeate
0,08
1 cm zeolite

Ammonium
concentration0,06
in
effluent (mg/L)

10 cm zeolite
Column 2 20cm zeolite
Column 3 20cm zeolite

0,04

Breakthrough
0,02
0
0

200

400
600
Effluent volume (L)

800

1000

Graph 5: 1 cm, 10 cm and 20cm zeolite clinoptilolite with flow rate of 12L/h measured by ammonium
analyzer Applikon Colorimeter
Graph 5 shows breakthrough curve of clinoptilolite at three different bed heights, it can be seen that a
higher bed height gives a better ion exchange result. Mainly, the ammonium concentration in effluent
wont start at high value that exceeds the breakthrough point. Also, the results provide a good
explanation for the assumption that water might leak along with the wall.

46

10 cm Lewatit S2568H at flow rate of 40L/h

Condition:
Feed water = RO permeate with average ammonium concentration of 0.136 mg/L
(STD 0.02mg/L)
Temperature of feed water= 12.0oC on average
Flow rate =40L/h

Breakthrough curve of 10cm Lewatit S2568H with 40L/h permeate water

0,16
0,14

NH4 concentration (mg/L)

0,12

y = 9E-21x6 - 5E-17x5 + 8E-14x4 - 1E-11x3 - 8E-09x2 + 7E-06x + 0,0062

0,1
0,08

10cm resin 40L/h

Permeate water (average)

0,06
0,04

Breakthrough

0,02
0
0

500

1000

1500
2000
Effluent volume (L)

2500

3000

Graph 6: 10 cm Lewatit S2568H with flow rate of 40L/h measured by ammonium analyzer Applikon
Colorimeter

47

10 cm Lewatit S2568H at flow rate of 60L/h

Condition:
Feed water = RO permeate with average ammonium concentration of 0.129 mg/L
(STD 0.006mg/L)
Temperature of feed water= 12.1oC on average

Breakthrough curve of 10cm Lewatit S2568H with 60l/h permeate water

0,14

NH4 concentration(mg/L)

0,12

y = 2E-18x5 - 2E-14x4 + 7E-11x3 - 8E-08x2 + 4E-05x + 0,0086

0,1
0,08
10cm resin 60L/h
0,06
0,04

Breakthrough

0,02
0
0

500

1000

1500

2000

2500

3000

3500

4000

4500

Effluent volume(L)

Graph 7: 10 cm Lewatit S2568H with flow rate of 60L/h measured by ammonium analyzer Applikon
Colorimeter

48

10 cm Lewatit S2568H at flow rate of 80L/h

Condition:
Feed water = RO permeate with average ammonium concentration of 0.126 mg/L
(STD 0.006mg/L)
Temperature of feed water= 12.0oC on average

Breakthrough curve of 10cm Lewatit S2568H with 80L/h permeate

water

0,14

NH4 concentration(mg/L)

0,12
0,1
0,08
0,06

10cm resin 80L/h

0,04

Breakthrough

0,02
0
0

1000

2000

3000
4000
Effluent volume(L)

5000

6000

Graph 8: 10 cm Lewatit S2568H with flow rate of 80L/h measured by ammonium analyzer Applikon
Colorimeter

49

Breakthrough curve for breakthrough capacity calculation

NH4 concentration(mg/L)

Breakthrough curve of 10cm Lewatit S2568H with 80L/h permeate

water
0,05
0,045
0,04
0,035
0,03
0,025
0,02
0,015
0,01
0,005
0

10cm resin 80L/h

y = 1E-11x3 + 2E-09x2 + 3E-06x + 0,0152

500

1000

1500

2000

Breakthrough

2500

Effluent volume(L)

50

10 cm Lewatit S2568H at flow rate of 100L/h

Condition:
Feed water = RO permeate with ammonium concentration of 0.125 mg/L
(only measured once)
Temperature of feed water= 11.9oC

0,14

Breakthrough curve of 10cm Lewatit S2568H with 100L/h permeate

water

NH4 concentration(mg/L)

0,12
0,1
0,08

y = 3E-08x2 - 1E-05x + 0,0159

0,06

10cm resin 100L/h

0,04

Permeate water (average)

0,02
0
0

500

1000

1500

2000

Effluent volume(L)

Graph 8: 10 cm Lewatit S2568H with flow rate of 100L/h measured by ammonium analyzer Applikon
Colorimeter

51

20 cm Lewatit S2568H at flow rate of 40L/h

Condition:
Feed water = RO permeate with average ammonium concentration of 0.140 mg/L
(STD 0.001mg/L)
Temperature of feed water= 11.9oC on average

Breakthrough curve of 20cm Lewatit S2568H with 40L/h permeate water

0,16

NH4 concentration(mg/L)

0,14
0,12
0,1
y = 1E-15x4 - 2E-12x3 + 1E-09x2 - 2E-06x + 0,0102
20cm resin 40L/h

0,08
0,06

permeate water (average)

0,04
0,02
0
0

500

1000

1500

2000

2500

3000

Effluent volume(L)

Graph 9: 20 cm Lewatit S2568H with flow rate of 40L/h measured by ammonium analyzer Applikon
Colorimeter

52

20 cm Lewatit S2568H at flow rate of 60L/h

Condition:
Feed water = RO permeate with average ammonium concentration of 0.142 mg/L
(STD 0.02mg/L)
Temperature of feed water= 11.8oC on average

Breakthrough curve of 20cm Lewatit S2568H with 60L/h permeate water

0,16

NH4 concentration(mg/L)

0,14
y = 4E-19x5 - 5E-15x4 + 2E-11x3 - 2E-08x2 + 3E-06x + 0,0132

0,12
0,1

Breakthrough

0,08
20cm resin 60L/h
0,06
Permeate water
(average)

0,04
0,02
0
0

1000

2000

3000

4000

5000

6000

Effluent volume(L)

Graph 10: 20 cm Lewatit S2568H with flow rate of 60L/h measured by ammonium analyzer Applikon
Colorimeter

53

20 cm Lewatit S2568H at flow rate of 80L/h

Condition:
Feed water = RO permeate with average ammonium concentration of 0.136 mg/L
(STD 0.003mg/L)
Temperature of feed water= 11.8oC on average

Breakthrough curve of 20cm Lewatit S2568H with 80L/h permeate water

0,16

NH4 concentration(mg/L)

0,14
0,12
0,1 y = -2E-18x5 + 1E-14x4 - 3E-11x3 + 2E-08x2 - 4E-06x + 0,0065
0,08
20cm resin 80L/h

0,06

Breakthrough

0,04

Permeate water (average)

0,02
0
0

1000

2000
Effluent volume(L)

3000

4000

Graph 11: 20 cm Lewatit S2568H with flow rate of 80L/h measured by ammonium analyzer Applikon
Colorimeter

54

20 cm Lewatit S2568H at flow rate of 100L/h

Condition:
Feed water = RO permeate with average ammonium concentration of 0.136 mg/L
(STD 0.003mg/L)
Temperature of feed water= 12.0oC on average

Breakthrough curve of 20cm Lewatit S2568H with 100L/h permeate

water

0,16

NH4 concentration(mg/L)

0,14
0,12
0,1
20cm resin 100L/h

0,08
0,06

y = 1E-15x4 - 3E-12x3 + 4E-09x2 - 2E-06x + 0,0075

Permeate water (average)

0,04
0,02

Breakthrough

0
0

500

1000

1500

2000

2500

3000

3500

Effluent volume(L)

Graph 12: 20 cm Lewatit S2568H with flow rate of 100L/h measured by ammonium analyzer Applikon
Colorimeter

55

Appendix F: The design of future treatment plant

56

Appendix H: The pressure drop data of Lewatit S2568H

57

58