Abstract

In this experiment, there are 4 objectives that have been examined. There are to remove
hydrocarbon (n-hexane or cyclohexane) from a carrier gas stream using an absorber filled with
molecular sieve type. Second objective is to plot the breakthrough curves (for n-hexane and
cyclohexane) experimentally using adsorption. Third objective is to calculate the various
parameters of the adsorption process and the last objective is to examine the effect of carrier gas
flow rate flow rate on the adsorption process. This experimental procedure consists of 3 part;
general start-up procedures, operating procedures and general shut-down procedures. For
operating procedures, the valves are set as given as collect initial concentration. Then depending
on which columns to use for adsorption, set all valves as given. The experiment is repeated using
other hydrocarbon (n-hexane and cyclohexane).

1
Introduction

The term “adsorption” is used to indicate that the adsorbate in the gas or liquid is bound
onto the adsorbent which is solid surface. Adsorption is the adhesion of atoms, ions,
biomolecules or molecules of gas, liquid, or dissolved solids to a surface. This process creates a
film of the adsorbate (the molecules or atoms being accumulated) on the surface of the
adsorbent. It differs from absorption, in which a fluid permeates or is dissolved by a liquid or
solid. The term sorption encompasses both processes, while desorption is the reverse of
adsorption. This term also used to describe the fact that there is a greater concentration of the
adsorbed molecules at the surface of the solid than in the bulk solution. In general, one uses solid
adsorbents of small size and often with surface imperfections such as cracks and holes which
serve to increase the surface area per unit mass greatly over the apparent geometrical
area.Adsorption is present in many natural physical, biological, and chemical systems, and is
widely used in industrial applications such as activated charcoal, capturing and using waste heat
to provide cold water for air conditioning and other process requirements (adsorption chillers),
synthetic resins, increase storage capacity of carbide-derived carbons for tunable nanoporous
carbon, and water purification. Adsorption, ion exchange, and chromatography are sorption
processes in which certain adsorbates are selectively transferred from the fluid phase to the
surface of insoluble, rigid particles suspended in a vessel or packed in a column.This is different
from absorbtion, in which the molecule goes into the interior of the solid. In the case of
adsorption, the process is defined as physisorption if the adsorbate is held by weak, van der
Waals type of forces on the surface. If bond formation between the adsorbate and the adsorbent
is observed, the process is commonly known as chemisorption.
The amount of material which is adsorbed on the surface at a particular temperature
depends upon the amount of that substance in the gas or liquid phase which is in contact with the
surface, and this dependence is called the adsorption isotherm. The isotherm is useful in
determining the interactions between the adsorbate and the adsorbent.

2
 In this gas adsorption unit, molecular sieve 5A in its hydrated form is used as an
adsorbed. Molecular sieve 5A is composed of calcium aluminosilicate Ca 6(AIO2)12.24H2O and
adsorb molecules up to 0.5 nm in diameter. This adsorbent can therefore be used for the selecting
separation of n-paraffins.

There are a few differences between gas adsorption and gas absorption. On the
contrary, adsorption is different from absorption in the sense that it focuses not on the volume
but on the surface. If fluids and gases settle on the surface of another material (liquids or solids)
rather than be diffused into the said material, then this forms a solution. The said process is an
adsorption. To use another explanation, adsorption is the process when an outside contaminant
(atoms) gets attracted to the outside surface of a piece of material while absorption involves the
uptake of the contaminant into the literal structure of the material. Similarly, absorption occurs
when the outside contaminant has merged or has become part of the other material. A similar
analogy occurs when you drink water. In drinking such, you are therefore absorbing fluid making
it a part of you. Adsorption occurs when you accidentally spill water on your shirt. The water did
not actually become part of you but just fell on you. It just bonded physically with a certain
surface (your shirt). Overall, although both absorption and adsorption are sorption processes they
still differ in the following areas such as absorption happens when atoms pass through or enter a
bulky material like sponges and adsorption happens when the atoms settle or accumulate on the
surface of a material rather than literally entering or diffusing into that same material.

3
Objective

 To remove hydrocarbon (n-hexane or cyclohexane) from a carrier gas stream using an

absorber filled with molecular sieve type.
 To plot the breakthrough curves (for n-hexane and cyclohexane) experimentally using
adsorption.
 To calculate the various parameters of the adsorption process.
 To examine the effect of carrier gas flow rate flow rate on the adsorption process.

4
Theory

(a) Adsorption Isotherms

Adsorption is usually described through isotherms, that is, the amount of adsorbate on the
adsorbent as a function of its pressure (if gas) or concentration (if liquid) at constant
temperature. The quantity adsorbed is nearly always normalized by the mass of the adsorbent
to allow comparison of different materials. The isotherm is useful in determining the
interactions between the adsorbate and the adsorbent. The extent of adsorption is usually
measured by coverage,θ which is given by

θ = (number of surface sites occupied)/(total number of surface sites)

(b)Langmuir Isotherm

It is widely used isotherm is attributed to a pioneer in the study of surface processes. It is a semi-
empirical isotherm derived from a proposed kinetic mechanism. It is based on four assumptions:

1. The surface of the adsorbent is uniform, that is, all the adsorption sites are equivalent.
2. Adsorbed molecules do not interact.
3. All adsorption occurs through the same mechanism.
4. At the maximum adsorption, only a monolayer is formed: molecules of adsorbate do not
deposit on other, already adsorbed, molecules of adsorbate, only on the free surface of the
adsorbent.

Consider the reversible equilibrium below;

A + S ↔ A.S

Where;
A = Free adsorbate
S = Free surface
A.S = Subtrate bound to the surface.

The rate of adsorption is proportional to the fluid concentration, C and the number of vacant sites
for adsorption.

5
(c) Material balance calculations

FA=UOCO

Where;
FA=product of the supertifical velocity, UO and the concentration, CO.

FAtn= UOCOtn = LρO(WS-WO)

tn= LρO(WS-WO)/ UOCO

where;
L and ρO are the length and bulk density of the bed respectively.

 Time equivalent to reach usable capacity, tu

tu = ∫ (1-c/co)dt

 Time equivalent to reach total capacity, tT

tT =∫ (1-c/co)dt
=Total shaded area below the graph
=A + B + C + D +E

 Length of used bed, LB

LB = tu/ tT (LT)

 Length of unused bed, LUB

LUB =(1- tu/ tT )LT
=LT – LB

6
Apparatus

 Gas chromatography
 100 mL beakers (for filtering)
 250 mL beaker
 250 mL Erlenmeyer flasks with rubber stoppers
 125 mL Erlenmeyer flask (for titration)
 Funnels and holder
 Fine porosity filter paper
 Pipets – 10 mL, 25 mL, 50 mL
 Pipet bulbs
 Spatula
 Thermometer
 6 – 100 mL volumetric flasks

7
Procedure

General start-up Procedures

1. Check that all tubings are properly connected.

2. Ensure that the drying columns K3 contain sufficient silica gel.
3. Fill the cold trap W3 with ice or ice water.
4. Check if there is sufficient water level in the thermostat T1 (the heating coil is fully
immersed). Refill is necessary.
5. Open the shut-off valve for three gas cylinder and ensure that each supply pressures is as
follows:
-Nitrogen, N2 – 80psia
-Hydrogen, H2 – 50 psia
-Compressed air – 50 psia
6. Open all valves for the gas supply lines to the chromatograph and the gas adsorption unit.
7. Turn on the power for the control panel.
8. Perform start-up procedures on the gas chromatograph.
9. Ensure that the columns are regenerated prior to running any experiment.
10. The unit is now ready for experiment.

Operating procedures.

1. Perform the general start-up procedures.

2. Check that both adsorption columns are regenerated. Make sure the column bed
temperatures have dropped to room temperature before beginning the experiment.
3. Fill the evaporator B1 with 1.0 L of liquid hydrocarbon (n-hexane or cyclohexane).
4. Set the thermostat T1 temperature 50ºC. Allow the temperature of the hydrocarbon liquid in
the evaporator B1 to reach 50 ºC. (Switch on small heater and allow T1 10 temperature
reach 45 ºC).
5. Open and adjust valve V10 to achieve a N2 gas flow rate of 2LPM.
6. Let the N2 gas stream entering the evaporator B1and bubbling through the hydrocarbon
liquid.
7. Collect the sample from the sampling line at valve V12 and analyses gas composition using
a gas chromatograph. This is the gas load entering the adsorption column (initial
concentration).

8
8. To collect initial concentration, set the entire valve to the following position.
Valve K1(initial concentration) K2(initial concentration)
V1 Closed Closed
V2 closed Closed
V3 To B1 To B1
V4 To K1 To K1
V5 From V4 From V4
V6 From K1 From K1
V7 From K1 From K1
V8 From K1 From K2
V9 From K2 From K2
V10 Valve for N2 gas flow rate Valve for N2 gas flow rate
V11 Closed Closed
V12 To sampling line/cold trap To sampling line/cold trap
V13 V12 V12

9. Hydrocarbon is direct to cold trap when the sample is not taken by adjusting V12.
10. Few reading of initial concentration is taken is make sure that the initial concentration is
consistent.
11. Depending on which columns to use for adsorption, set all valves to the following position:
Valve K1(initial concentration) K2(initial concentration)
V1 Closed Closed
V2 closed Closed
V3 To B1 To B1
V4 To K1 To K2
V5 To V4 To V4
V6 From K1 From K2
V7 From K1 From K2
V8 To V9 From K1
V9 From K2 To V12
V10 Valve for N2 gas flow rate Valve for N2 gas flow rate
V11 Closed Closed
V12 To sampling line/cold trap To sampling line/cold trap
V13 V12 V12
12. Collect a sample from the outlet gas stream after 8 minutes and analyses the collected
samples in the gas chromatograph for the hydrocarbon (n-hexane or cyclohexane)
concentration in the gas phase.
13. Continue collecting samples and recording the bed temperatures for every 8 minutes interval
until the reading are constant in the gas composition as analysed using gas chromatograph.
14. Repeat steps 5 to 12 by using the other column. However, adjust valve V10 to give a N2gas
flow rate of 2LPM.
15. Repeat the entire experiment by using a different type of hydrocarbon (n-hexane or
cyclohexane).

9
General shut-down procedures.

1. Switch off the vacuum pump P1, heating sleeves W1 & W2 and thermostat T1.
2. Close valve V10 and the shutoff valve for the compressed air and hydrogen gas cylinders. Do
not close the nitrogen gas cylinder’s shut-off valve yet. This will allow the flow of nitrogen
gas to cool down the gas chromatograph.
3. Discard the remaining hydrocarbon liquid from evaporator B1 when the temperature
indicator (T1 109) decrease to ambient temperature.
4. Discard the ice or ice water from cold trap W3.
5. Shut down the gas chromatograph. Wait until the gas chromatograph is reasonably cool
before closing the shut-off valve on the nitrogen gas cylinder.
6. Turn off the power for the control panel.
7. Close all valves for the gas supply lines.

10
Result

Column for adsorption =K1

Evaporator temperature =50ºC
N2 gas flow rate =2.00 LPM
Hydrocarbon in feed =n-hexane
Initial concentration =0.1224%

Time (min) Concentration, % Concentration ratio, c/co

0 0.0000 0.0000
8 0.0053 0.0433
16 0.0497 0.4060
24 0.0856 0.6985
32 0.0882 0.7041
40 0.0873 0.7130
48 0.0891 0.7278
56 0.0899 0.7345
64 0.1038 0.8465
72 0.1178 0.9618
80 0/1189 0.9711
88 0.1211 0.9894
96 0.1220 0.9966

1.2

0.8

0.6
Concentration ratio, c/co

0.4

0.2

0
0 8 16 24 32 40 48 56 64 72 80 88 96

11
Column for adsorption =K2
Evaporator temperature =50ºC
N2 gas flow rate =2.50 LPM
Hydrocarbon in feed =n-hexane
Initial concentration =0.1294%

Time (min) Concentration, % Concentration ratio, c/co

0 0.0000 0.0000
8 0.0077 0.0594
16 0.0370 0.2859
24 0.0854 0.6599
32 0.0896 0.6919
40 0.0910 0.7032
48 0.1119 0.8648
56 0.1248 0.9638
64 0.1268 0.9792
72 0.1280 0.9889
80 0.1286 0.9936

Concentration ratio, c/co

1.2
1
0.8
Concentration ratio, c/co
0.6
0.4
0.2
0
0 10 20 30 40 50 60 70 80 90

12
Column for adsorption =K1
Evaporator temperature =50ºC
N2 gas flow rate =2.00 LPM
Hydrocarbon in feed =cyclohexane
Initial concentration =0.0735%

Time (min) Concentration, % Concentration ratio, c/co

0 0.0000 0.0000
8 0.0048 0.0648
16 0.0536 0.7297
24 0.0629 0.8588
32 0.0679 0.9245
40 0.0692 0.9421
48 0.0697 0.9488
56 0.0703 0.9575
64 0.0708 0.9631
72 0.0728 0.9910
80 0.0728 0.9904
88 0.0733 0.9972

Concentration ratio, c/co

1.2

0.8
Concentration ratio, c/co
0.6

0.4

0.2

0
0 10 20 30 40 50 60 70 80 90 100

13
Column for adsorption =K1
Evaporator temperature =50ºC
N2 gas flow rate =2.50 LPM
Hydrocarbon in feed =cyclohexane
Initial concentration =0.0704%

Time (min) Concentration, % Concentration ratio, c/co

0 0.0000 0.0000
8 0.0056 0.0783
16 0.0370 0.5252
24 0.0540 0.7574
32 0.0589 0.8377
40 0.0622 0.8842
48 0.0680 0.9384
56 0.0684 0.9718
64 0.0695 0.9870
72 0.0702 0.9992

Concentration ratio, c/co

1.2

0.8
Concentration ratio, c/co
0.6

0.4

0.2

0
0 10 20 30 40 50 60 70 80

14
Sample Calculation

Column for adsorption =K1

Evaporator temperature =50ºC
N2 gas flow rate =2.00 LPM
Hydrocarbon in feed =Cyclohexane
Initial concentration =0.0735%

(a) Breakpoint time, to =7 minutes

(b) Time equivalent to reach usable capacity, tu

tu = ∫ (1-c/co)dt
=7 x 1
=7 minutes

(c) Time equivalent to reach total capacity, tT

tT =∫ (1-c/co)dt
=Total shaded area below the graph
=A + B + C + D +E
=1/4(0.5 x 13) + ¾(13 x 0.38) + (0.5 x 13) + (0.88 x 62) + ½(0.12 x 62)
=1.625 + 3.705 + 6.5 + 54.56 + 3.72
= 70.11minutes

(d) Length of used bed, LB

LB = tu/ tT (LT)
=7/70.11(40cm)
=3.99cm
=4cm

(e) Length of unused bed, LUB

LUB =(1- tu/ tT )LT
=LT – LB
=40cm – 4cm
=36cm

15
Discussion

Gas adsorption is a process in which one or more components from a gas stream are
absorbed on the surface of a solid. Separation process is accomplished because differences in
molecular weight, shape or polarity give rise to some molecules being held more strongly on the
surface than others or because the pores are too small to admit the larger molecules.

The experiments have been done successfully. Remove hydrocarbon (n-hexane or

cyclohexane) from a carrier gas stream using an absorber filled with molecular sieve type. They
are successfully done by using absorber filled containing with molecular sieve type. This is can
be obtain from the result which is that product obtain from the valve. Referred at the initial
concentration for K1 (n-hexane) with 0.1224%, the final concentration is 0.0000%. It is same
with other K2 (n-hexane), K1 (cyclohexane) and K2 (cyclohexane).

Next, to plot the breakthrough curves (for n-hexane and cyclohexane) experimentally
using adsorption. From the result that we obtain in the graph, for K1 (n-hexane) with initial
concentration 0.1224%. The graph shows that concentration ratio, C/Co is directly proportional to
the time. Highers the concentration ratio, C/Co, the time also is increased. The graph shows the
same result as K1 (n-hexane). It can be show that the area between the curve and the C/C O line at
1.0 is proportional to the total surface adsorbed if the entire bed reaches equilibrium with the
feed. The ideal adsorption time for a vertical breakthrough curve is taken at time t o, in which the
rectangular area to the left of to is proportional to the amount adsorbed. For a symmetrical curve,
to is the time when C/CO reaches 0.5.

For the adsorption parameters, the breakpoint time, t o be 7 minutes. This can be
calculated using time equivalent to reach usable capacity, tu. The actual amount of solute
adsorbed up to the break point can be determined by integrating the breakthrough curve up to the
time to. If the mass transfer zone is narrow relative to the bed length, the breakthrough curve wil
be steep and most of the capacity of the solid will be utilized at break point. This condition is
desirable to allow for the efficient use of the adsorbent and reduce the energy costs for
regeneration.

16
Conclusion

As a conclusion, overall experiment, the experiment has been successfully done by

completing the objective given. First objective was done by removing the hydrocarbob (n-hexane
and cyclohexane) depend on its concentration. The initial concentration is more that final
concentration. It is same for all hydrocarbons. For second objective, for the graph plotted in the
result section, the concentration ratio is directly proportional to the time. As the concentration
ratio is higher, the time also increased. The third objective was to calculate the various parameter
of the adsorption process by using a few formulas given in the theory. They are time equivalent
to reach usable capacity, tu, time equivalent to reach total capacity, tT , length of used bed, LB and
length of unused bed, LUB . For time equivalent to reach usable capacity is actually to find the
breakpoint time. We get 7 minutes then for time equivalent to reach total capacity, we get
70.11minutes. Then, the length of used bed is 4cm and the last one is length of unused bed,
36cm. the last objective was to examine the effect of carrier gas flow rate on the adsorption
process. It can be conclude that the higher the effect of carrirer gas flow rate. The adsorption
processes occur also higher.

17
Recommendations

 Do not touch the hot components of the unit.

 Do not use any coarse or abrasive cleaners on glass components.
 Leaking couplings should be carefully retightened. Replace any gaskets or seals if
necessary.
 Restore the system to operating conditions after any repair job.
 Feed stock which severely affects PTFE and PFA are not to be used.
 Make sure wear gloves and wear goggle to avoid any accident to happen.

18
Reference

 http://www.che.ufl.edu/courses/ech4404L/GasAbsorption/GA%20Theory.pdf 7
March/6pm
 http://en.wikipedia.org/wiki/Adsorption 7 March/7pm
 http://www.tau.ac.il/~phchlab/experiments/adsorption/index.htm 7 March/9pm
 http://www.ncnr.nist.gov/summerschool/ss07/DCS_ss07.pdf 8 March/5pm

19
Appendices

Brunauer, Emmett and Teller's model of multilayer adsorption is a random distribution of

molecules on the material surface.

20