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FLUIDIZED AND FIXED BED ION-EXCHANGE COLUMN

Objectives
1. To investigate the rate of exchange of Na+ ions for H+ ions by Dowex-50W resin.
2. To compare the performances of a column under fluidized-bed and fixed-bed
conditions.
3. To investigate the height of a fluidized bed as a function of the superficial
fluidizing velocity.
4. To illustrate the difference between random and systematic errors and propose
ways to minimize both kinds of errors.

Theory
A solution of Na+ ions (as NaCl) is passed through a column containing Dowex-
50W-X8 cation resin (for exchanging positively charged ions) in the form of spherical
beads. The resin is based on a styrene/divinylbenzene copolymer that has been
sulfonated with sulfuric acid; the “X8” denotes 8% divinylbenzene. This resin can
adsorb Na+ ions from solution and return in exchange the same number of H+ ions, so
that the solution maintains electrical neutrality. The process can be represented by:
+ + + +
NaL + HR = NaR + HL , (1)
where the subscripts L and R denote liquid and resin, respectively.
As the solution passes through the column, it becomes more dilute in Na+ and more
concentrated in H+ , a change that can be followed by sampling the H+ concentration in
the exit stream with a pH electrode. Eventually the resin becomes saturated with Na+
ions and further exchange ceases. The ion exchange process is reversible, so that the
resin can be regenerated by allowing it to come in contact with a strong acid (HCl).
The exchange of a Na+ ion for a H+ ion is not instantaneous, since it takes time for
a Na+ ion to diffuse from the bulk of the liquid to the surface of the resin and then to
some position inside the resin where it can exchange for a H+ ion. (And conversely for
the H+ ion, which has to migrate back to the bulk solution.) The rate of exchange is
expected to become slower as the Na+ ion concentration in the resin approaches
saturation. The present investigation attempts to find a correlation for the rate at which
this exchange process occurs.
The bed can be operated either in: (a) upflow, at a liquid velocity such that the
particles are fluidized, or (b) downflow, in which case the bed is fixed. Under condition
(a), the bed is often assumed to be well mixed, and the mathematical treatment is greatly
simplified.

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Upflow. Observe the definitions given in Table 1.

Table 1. Definitions of Symbols.


Symbol Definition of Symbol
c Concentration of Na+ ions in solution leaving the column,
meq/ml. Since the beads and liquid are well stirred by the
fluidizing action, c will also be the concentration of Na+
ions in the solution throughout the column.
co Entering concentration of Na+.
h H+ concentration in the solution leaving the column,
meq/ml.
ho H+ concentration in the solution entering the column,
meq/ml.
H Height of the fluidized bed, cm. The compacted value is Ho.
q Concentration of Na+ ions in the resin, meq/ml of resin.
Again, because of the mixing, this may be assumed constant
throughout the column.
qo Total exchange capacity of the resin. Because of the 1:1
exchange between Na+ and H+ , the concentration of H+ in
the resin is (qo-q).
t Time, s.
v Volumetric flow rate of solution, ml/s.
VR Volume occupied by the resin beads in the column, ml.
VL Volume occupied by the liquid in the column, ml.
ε Bed void fraction. The void fraction εo of the compacted
bed is 0.41.

The following analyses assume perfect mixing — that is, at any instant, each of the
concentrations c in the liquid and q on the resin are uniform throughout the column. Also
note that the rate of desorption of H+ equals the rate of adsorption of Na+ , namely,
dq/dt.
Recognizing the rates of desorption from the resin, outflow from the column, and
accumulation in the liquid, a transient hydrogen-ion balance gives
dq dh
vho + Vr ! vh = Vl (2)
dt dt
Similarly, a transient sodium-ion balance gives
dq dc
vco ! Vr ! vc = Vl (3)
dt dt

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Estimates of the concentrations c, q, and qo can be found as follows. In the
experimental work, the pH value of the exit stream is measured. By definition,
pH = - log10 ( H+ ion concentration ), (4)

so that the H+ concentration in eq/l and hence in meq/ml (= h, for example) can be
determined. Differentiation of h plotted against t will also give dh/dt.
The rate of adsorption, dq/dt, can then be found at various times from (2). Next,
equation (3) is rearranged to give the following differential equation for c:
dc 1 # dq &
= %v (c o " c ) " VR (, (5)
dt VL $ dt '
which can be integrated numerically by Euler's method to give c as a function of time.
For example, suppose at any time t the concentration is c and the value of the right-hand
side of (5) is R. Then, the concentration at a later time t + ∆t, is approximately c + R∆t.
! c = 0, and proceeding over several such time steps t, approximate
By starting at t = 0 and
values of c may be determined at subsequent times.
The appropriate manipulation and integration of equation (3) yields:
q t
v
q = ! dq = ! (co " c)dt " VL c. (6)
0
VR o VR
Thus, the concentration q of Na+ ions in the resin at any time t is v/VR times the shaded
area in the plot of c against t (see Fig. 1), less the amount retained in the liquid VLc. In
particular, the total exchange capacity qo can be found by this method. However, can you
devise an alternative and simpler method (still involving integration) for finding q and qo
? (Hint — what did you obtain from Eqn. (2)?

c
co

t
" (c
0 0
! c ) dt

0 t
Fig. 1. Integration to find the degree of adsorption q.

Simpson's rule may be used for numerical integration:

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a
h
" f ( x )dx = 3 ( f o + 4 f1 + f 2 ), (7)
b

where h = (b - a)/2 and the three functional values are at x0= a, x1 = a + h, and x2 = b.
Finally, the void fraction of the bed can be calculated for any known height H from:
!
H
! = 1 " (1" ! o ) o , (8)
H
in which the subscript zero denotes the compacted bed.

Downflow. The theory for downflow, which is considerably more involved, has
not yet been developed in the context of the ChE 360 laboratory. The theory involves the
method of characteristics for solving hyperbolic-type partial differential equations. For
the present, you should only make a qualitative analysis of the fixed-bed operation.

Equipment
A schematic diagram of the equipment is shown in Fig. 2.

Water HCl NaCl


Packing nut
pH
1 2 3
electrode Movable
Mode
retaining screen
selector
valve Variable volume
to Bypass Dowex-50 resin bed
drain valve
Retaining
screen
Pump pH
electrode

Fig. 2. Schematic diagram of the Ion-exchange column.

The equipment consist of the following parts:


• A positive-displacement metering pump with adjustment scale of 0 – 10 for flow
control. The pump inlet and outlet tubing can be easily disconnected from the
system with two quick-disconnect fittings. The pump consists of a Cole-Parmer
drive model FF-07553-70, a pump head model FF-77200-60 and type L/S 16
Viton tubing.
• A Glass column (2.8 cm ID) fitted with a sliding top to allow for a variable
volume chamber. The bed contains Dowex-50W-X8 ion-exchange resin of
nominal capacity 1.7 meq/ml of resin bed. The void fraction in the compacted
bed (before fluidization) is 0.41.
• Three stock jars, containing de-ionized water, HCl, and NaCl solution,

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• Three shut-off valves (glass stopcocks) are provided so that any of the three
liquids can be pumped through the bed. These valves are located in a glass
manifold immediately before the pump. Make sure that all three valves are
closed, or that only one of these valves is open at one time. If more than one
valve is open, liquid from one reservoir can flow into other reservoirs causing
contamination of the feed materials!!
• and two four-way flow-selection valves (Fig. 3), either in upflow or downflow, or
bypass the ion-exchange bed entirely for pH electrode calibration or storage.
• Two pH electrodes (Cole-Parmer model H-05662-53) are located at the bed inlet
and exit for measuring the pH value as a function of time.
• One pH meter (Fisher Scientific Acumet® model AR25). This is a dual-channel
pH meter with a standard RS-232 communications protocol. This communication
mode has the advantage that a calibration is not needed between the pH meter and
the computer since the meter already sends data in numerical format
• A computer equipped with “LabVIEW”i data-acquisition software (see below for
instructions).

B B

A C A C

D D

Ports A-B and Ports A-D and


ports C-D connected ports B-C connected

Fig. 3. Detail of the 4-way flow-selection valve

i
LabVIEW is a Trade Mark of National Instruments Corp. Austin, TX

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Experimental Procedures

Use of Personal Protection Equipment (PPE)


Safety glasses must be worn at all times in the laboratory.
When handling corrosive liquids (such as Hydrochloric Acid solutions)
appropriate rubber gloves should be used. N-Dex nitrile rubber gloves are provided for
this purpose.
When handling a container of more than 1-liter of Concentrated Hydrochloric
Acid (30%). A chemical resistant apron, face shield and heavy resistant gloves should be
used.

I. Data Acquisition with “LabVIEW”


®
“LabVIEW” operates under Microsoft WINDOWS XP operating system. To
start the program, turn the computer on (if it is not already) and select the “Chelab” user
account. Double-click on the "ION EXCHANGE" folder if it is not open already. This
folder contains icons for the control setup and a folder for the storage of the data from the
experimental runs. In order to start the data acquisition and control program double-click
on the "IonExchange.vi" icon. A product identification screen appears and the LabVIEW
setup will start the data acquisition and control functions.
The setup produces a display screen with the values for all the sensor outputs on
the right-hand side of the screen, and analog traces for the sensor outputs on the left-hand
side of the screen. A file named “IonExchange_nnn.xls” is generated every time
the data acquisition program is invoked. The “nnn” indicate the numerical order of the
file and it is incremented by one each time a new file is saved. All the temperature,
pressure, and time values are stored in this file every 10 seconds. Note: The data that are
written to the file are not the actual readings at every 10-second mark. Instead, they are
the calculated average of the values read over the previous 10 seconds.
To Start the data acquisition click on the Start button located on the leftmost position of
the menu bar (see figure 1 for details).
To stop the data acquisition click on the red “STOP” located on the upper left corner of
the user interface. A new file is generated each time the Start button is pressed.
If a faster rate of data acquisition is desired, click on the “ACQUISITION RATE”
toggle-switch located on the lower-right corner of the screen so it changes status from the
SLOW to the FAST position. While this switch is in the FAST position, all values are
recorded to the file every second. It is recommended that fast acquisition is used only
when necessary since it will create very large data files in a relatively short period of
time.

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Start Button Stop Button

Figure 1: User interface for the Ion Exchange setup

To retrieve these files at the end of your work, double-click on the “DATA” icon
in the "ION EXCHANGE" folder. The files list can be sorted by date with the most
recently created file at the top of the list. Your files can be recognized by their creation
date and time, and by the “File Name Out” shown in the user interface window.
When you are done with the computer, please do not shut down the computer.
There is an anti-virus program that is set to run every night at midnight so it is important
that the computers be left on for this event.

II. Calibration of the pH Electrodes


In order to calibrate the pH electrodes, a two-point calibration is generally carried
out with the help of two standard buffer solutions of known pH. This type of calibration
generally produces a straight-line correlation between the pH electrode response to pH of
the solution and the pH meter output. Note that this type of calibration will not correct

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for any non-linearity of the electrode response. Standard buffer solutions are provided
for this calibration.
All the functions of the pH meter are accessible trough a “Touch-Screen” user-
interface. This screen requires only gentle touches of the desired icons (or “virtual
buttons”) in order to select the desired functions. Please note that the sensitive part of the
touch screen is a small area to the right of the virtual buttons (between the button and the
frame of the screen).
Please help keep the instrument working properly by avoiding rough treatment
of the unit. If at the beginning of the lab period the instrument is on “standby” (only
shows the brand name and the time), touch the screen gently to bring the meter on line,
then press the button to display both pH values.

In order to standardize the pair of pH electrodes between pH 7 and other pH value,


use the following procedure:
1. Place the 4-way bypass valve in the "Bypass" position (no liquid flow through
the ion-exchange bed)
2. Make sure that all tree valves in the glass manifold immediately before the pump
are in the closed position.
3. Disconnect the pump inlet from the inlet manifold and connect it to a short piece
of tubing with the mating part of the quick-connect fitting.
4. Fill a 250-ml beaker with 200 ml of DI water and pump the water through the
electrode holder loop in order to rinse both pH electrodes.
5. Lift the inlet tubing from the beaker and allow air to displace the water from the
electrode holder loop.
6. Fill a 50 ml beaker with Standard buffer pH = 7. Insert the pump inlet tubing in
the beaker and pump the buffer solution through the electrode holder loop until it
completely fills with the buffer and approximately 10 ml have flowed to the
drain. Then insert the drain tube into the beaker containing the buffer to circulate
through the electrode holder loop.

7. When the pH readings are stable select the “Channel 1 standardization menu”
pressing the button on the pH meter screen display.

8. Press the button and clear the previous calibration parameters by pressing
the clear button.

9. Press the button again and enter the buffer pH value when the keypad
appears on the screen, then press the button. The keypad will appear only
when the pH reading is stable.

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10. Select the “Channel 2 standardization menu” by successively pressing the
button, the channel button, the button and the button.

11. Repeat steps 7 and 8.


12. Lift the inlet tubing from the beaker and allow air to displace the buffer from the
electrode holder loop. Insert the pump inlet tubing into a beaker with 200 ml of
DI water and pump the water through the electrode holder loop to rinse the
electrodes.
13. Fill a 50 ml beaker with another standard buffer (i.e. pH = 4 or pH = 2). Insert
the pump inlet tubing in the beaker and pump the buffer solution through the
electrode holder loop until it completely fills with the buffer and approximately
10 ml have flowed to the drain. Then insert the drain tube into the beaker
containing the buffer to allow the buffer to circulate through the electrode holder
loop.
14. When the pH reading is stable press the button to enter the standardization
menu, press the button again, enter the new pH value and then the
button.

15. Select the “Channel 1 standardization menu” by successively pressing the


button, the channel button, the button and the button.

16. Press the button to enter the standardization menu, press the button
again, enter the new pH value when the keypad appears, and then press the
button.

17. Reset the dual mode of the instrument by pressing the button, channel button,
and the button successively.

The instrument is now standardized and ready to send data to the computer. Note that
attempting to calibrate the instrument while the data acquisition program is running will
produce an error message in the computer. This is because the pH meter does not send
any data when in the calibration mode.
The electronic signal produced by the pH meter is sent to the computer via RS-232
data protocol in numerical form so there is no need to further process the signal. The pH
values displayed and store by the computer should be identical to the ones shown in the
pH meter screen.

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III. Ion Exchange Column Characterization
Caution: Since the pump is positive displacement, you must make sure that there is
always a free path to the drain; otherwise, pressure will build up and something may
“blow.” Make sure, especially in downflow, that air has been removed from all lines
before starting the sodium chloride flow; air can be removed by bleeding (to drain) each
of the sections of the tube in turn.
You may need to make up additional 0.4 N (normal) NaCl solution during the
laboratory session, in that case, please make sure that the concentration you prepare is
correct because other groups may be relying on the accuracy of your solution.
1. For a typical run, select the position of the four-way mode-selector valve, either
to upflow or to downflow (fluidized- or packed-bed operation, respectively, as
appropriate). Warning: Never change the position of this valve when the
pump is in operation. This will close the pump outlet and produce high
pressure in the tubing causing it to burst.
2. Open one of the valves of the fluid-selector manifold to choose between water,
the HCl solution, and the NaCl solution, as needed. Only one of the valves in
manifold should be open to prevent cross-contamination of the feedstock.
3. Position the four-way bypass valve so the liquid flows through the ion-exchange
bed. Warning: Never change the position of this valve when the pump is in
operation. This will close the pump outlet and produce high pressure in the
tubing causing it to burst.
4. Turn on the pump by switching to forward. Turn it off by switching back to the
neutral position. Never switch it to reverse, because you will contaminate the
stock tanks and probably blow the fuse. If you accidentally blow the fuse, notify
your laboratory supervisor.
5. Continuously monitor the pH of the inlet and exit streams to and from the bed.
6. Using water, calibrate the speed-control setting on the pump against the flow rate
(ml/s) for the range in which the bed is fluidized.
7. Measure the bed height (cm) as a function of flow rate.
8. First, operate the bed in upflow, so that it is fluidized. Be careful to adjust the
flow rate so that the resin does not significantly impact on the screen above the
bed.
9. Pass the hydrochloric acid solution up through the bed to regenerate the resin to
its H+ form. Since regeneration is dependent on mass transfer rate, make sure
that enough H+ have had a chance to be in contact with the resin (perhaps as
much as 10 times excess or more, depending on flow rate). When steady state
has been reached (no further mass transfer occurs), the resin is saturated with H+
ions.
10. Switch the flow to water until the free hydrochloric acid solution has been
purged from the column.

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11. Switch the flow to the sodium chloride solution and continue until the H+
concentration of the exit stream shows negligible change. Check the exit flow
rate periodically by direct volumetric measurement over a known time.
12. Perform a second upflow run under conditions of your choice.
13. Repeat one run in downflow or fixed-bed operation.
14. Determine the mean particle terminal velocity by timing the rate of descent of
several resin particles in a vertical tube of water; then take the average.

pH Electrode Storage
When all your daily experiments have been completed the pH electrodes must be
stored in pH Electrode Storage Solution. In order to accomplish this use the following
procedure:
1. Place the 4-way bypass valve in the "Bypass" position (no liquid flow through
the ion-exchange bed)
2. Disconnect the pump inlet from the inlet manifold and connect it to a short piece
of tubing with the mating part of the quick-connect fitting.
3. Fill a 250 ml beaker with 200 ml of DI water and pump the water through the
electrode holder loop in order to rinse both pH electrodes.
4. Lift the inlet tubing from the beaker and allow air to displace the water from the
electrode holder loop.
5. Fill a 50 ml beaker with pH Electrode Storage Solution or Buffer 4.0 solution.
Insert the pump inlet tubing in the beaker and pump the storage solution through
the electrode holder loop until it completely fills with the solution and
approximately 10 ml have flowed to the drain. Then insert the drain tube into the
beaker containing the buffer to allow the buffer to circulate through the electrode
holder loop for a few seconds.
6. Turn the pump off.

Data Analysis
Items 1 – 5 relate to the runs in which the bed is fluidized:
1. Convert all pH values into concentrations h of H+ ion, using equation (4).
2. Plot h against t and comment on the shape of the curve.
3. By following the theory, determine values for dq/dt, c, and q, at several intermediate
values of time. Evaluate qo.
4. Plot c and q against time.
5. Try to develop a correlation, preferably in the form of a fairly simple equation, that
gives the rate of exchange as a function of one or more of c, q, co, qo, and t. You
may wish to view equation (1) as a reversible chemical “reaction.” For example, an

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obvious restriction for the forward “reaction” (adsorption of Na+ ) is that your
correlation must reduce to dq/dt = 0 when either the resin is saturated or when there
is no Na+ in solution; thus, factors such as c, (qo - q), or c(qo - q) might be
indicated.
Alternately, the following analysis was suggested by Dr. Maurice Allen to Professor
Wilkes: Assume that c, h, and q are known as functions of time t from the existing
analysis of the fluidized bed ion-exchange column.

qs Surface Concentration

q c Liquid Concentration

Interior Concentration
Fig. 4 Notation for Sodium Ions concentrations.

As shown in Fig. 4, we first recognize a difference in the sodium ion concentration


c (in the liquid), q (in the solid), and qs (at the surface of the resin bead). If we
make the simplifying assumption that ignores the concentration gradient within the
resin, we can assume that the rate of increase of sodium inside the resin is
proportional to the “driving force” qs – q.
dq
= k1 (qs ! q) . (9)
dt
Also, paralleling the concept of “relative volatility” for a binary mixture in
distillation columns, the ratio of sodium ions to hydrogen ions in the surface of the
resin is assumed to be proportional to the corresponding ratio in the liquid:
qs c
= k2 . (10)
q0 ! qs h
Eliminating qs from Eqns. (9) and (10) yield:
# &
dq % q0 (
= k1% " q( . (11)
dt %1+ h (
% (
$ k 2c '
and since h, c, q, and dq/dt are tabulated as function of t, and if q0 is known, the
constants k1 and k2 can then be determined in order to give the best fit of the data.
Note that this model
! does not account for possible diffusion effects in the liquid
surrounding the resin bead.
6. For the fixed-bed operation, give a qualitative explanation of your observations. If
they differ from the fluidized-bed results, point out the differences and attempt to
explain them.

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7. Plot the bed void fraction against superficial velocity, and attempt to develop a
correlation in the form of an equation that relates the two. Include on the plot a
point that corresponds to the mean terminal velocity of the particles.

Questions for Consideration


1. What precaution should you take when turning off the pump?
2. What are the definitions of pH, normality, molarity, equivalent, mole, and formula-
weight?
3. For each Na+ ion bonded by the resin, how many H+ ions are released?
4. How can you prove equation (8)?
5. What is meant by terminal velocity?
6. What causes fluidization to occur?
7. What correlation might you reasonably try for the rate of adsorption dq/dt of Na+
ions by the resin?
8. What degree of polynomial will Simpson's rule integrate exactly?
9. Why is the last term in equation (2) likely to be relatively small?

References:
1. Dowex Ion Exchange, The Dow Chemical Company, Midland, MI (any edition).
2. Sujata, A.D., Rates of Ion Exchange in the Sodium/Potassium/Dowex-50 System,
Ph.D. Dissertation, Department of Chemical Engineering, University of Michigan,
Ann Arbor, MI (1952). (Prof. Wilkes has a copy.)
3. Gilliland, E.R., and Baddour, R.F., Ind. Eng. Chem., 45, p. 330 (1953).
4. Cole-Parmer Instrument Company, Cole-Parmer 1994-1995, Laboratory
Equipment and instrumentation Catalog
5. Dr. Maurice Allen, Department of Chemical and Process Engineering at the
University of Canterbury, Christchurch, New Zealand:

J.O. Wilkes, P. La Valle, January 3, 2006

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