Ekc 499 Final Year Project

RESEARCH PROPOSAL

Name of Student : Tharveen Raj Rajalingam

Matric Number : 120550

Name of Supervisor : Professor Dr. Mohd. Roslee Bin Othman

Research Title : Purity and Recovery of Carbon Dioxide Gas From Flue Gas Through
Vacuum Pressure Swing Adsorption

Check and approved by,

…………………………

Date:
 TABLE OF CONTENTS

1.0 Research Background ......................................................................................................... 1

2.0 Research Objectives ............................................................................................................ 1

3.0 Literature Review ................................................................................................................ 2

4.0 Research Methodology ........................................................................................................ 4

4.1 Chemical Preparation ................................................................................................................... 4
4.2 Adsorbent Preparation ................................................................................................................. 4
4.2.1 Zeolitic Imidazolate Framework-8 (ZIF-8) Preparation........................................................... 4
4.2.2 Universitetet i Oslo-66 (UiO-66) Preparation .......................................................................... 4
4.3 Experimental Rig Set-Up ............................................................................................................. 5
4.4 Experimental Procedure .............................................................................................................. 5
4.4.1 Characterization of Adsorbent.................................................................................................. 5
4.4.2 Breakthrough Analysis ............................................................................................................. 5
4.4.3 Vacuum Pressure Swing Adsorption ........................................................................................ 6

5.0 Chemicals and Equipment.................................................................................................. 7

6.0 Gantt Chart.......................................................................................................................... 8

7. 0 Reference ............................................................................................................................. 9

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 PURITY AND RECOVERY OF CARBON DIOXIDE GAS FROM FLUE GAS
THROUGH VACUUM PRESSURE SWING ADSORPTION

1.0 Research Background

Carbon dioxide (CO2) emissions to the atmosphere has been acknowledged as a major
contributor to global warming. Sources of CO2 emissions come from the combustion of fossil fuels
which include coal, natural gas and petroleum, and industrial processes such as oil refining,
production of cement, iron and steel. Concentrations of CO2 in coal-fired power plants vary
between 12.5-12.8% while in gas-fired power plants, the concenrations of carbon dioxide can
range from 7.4-7.7%. Thus, considering the abundant sources of CO2 emissions, the strategic
importance of post-combustion capture systems become evident. (Dantas et al., 2011) The
recovery of CO2 from flue gases emitted by power plants, steel mills, cement kilns and
fermentation processes is becoming increasingly viable. (Chue, 1995) Reduction of carbon dioxide
emissions from flue gases can be achieved using post-combustion capture technologies such as
adsorption. (Dantas et al., 2011) Pressure swing adsorption (PSA) is one of the most known
industrial processes for gas separation. In any adsorption-based technology, the most important
decision is the adsorbent selection. The adsorbent should be based on a material that has high
affinity for the gas to be recovered with good sorption capacity as well as desorption capabilities.
(Gomes and Yee, 2002) In this research, zeolitic imidazolate framework-8 (ZIF-8) and
Universitetet i Oslo-66 (UiO-66) are utilized as adsorbents to recover carbon dioxide from flue
gases using vacuum pressure swing adsorption (VPSA). The adsorbents will be used in VPSA to
study and compare the performance of CO2 recovery and purity.

2.0 Research Objectives

This research aims,
i) To characterize and analyse ZIF-8 and UiO-66 adsorbents in terms of surface area, surface
morphology and surface chemistry.
ii) To study the breakthrough analysis of carbon dioxide and nitrogen gas in ZIF-8 and UiO-
66 adosrbents.
iii) To study the performance of vacuum pressure swing adsorption for for carbon dioxide and
nitrogen gas recovery and purity using ZIF-8 and UiO-66 adsorbents.

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3.0 Literature Review
Adsorbents are susbstances, usually porous in nature with high surface areas. Adsorbents
adsorb other substances or compounds, known as adsorbates onto its surface by intermolecular
forces. A more rcent addition to these porous materials is the class of metal-organic frameworks
(MOF). These materials are formed via coordination between metal clusters and organic linkers.
(Rowsell and Yaghi, 2004) Advtangaeous characteristics of MOFs include their large surface areas
and the relative ease in which their pore sizes and chemical functionaility can be controlled to suit
specfic applications. (McEwen et al., 2013) In more recent years, extensive research has been
conducted out on the adsorptive properties of MOFs for gas separation. (Li et al., 2009)

Zeolitic imidazolate frameworks (ZIFs) come from a MOF sub-class which have
tetrahedral networks analagous to zeolites but use imidazolate ligands linked-transition metal.
(Park et al., 2006) ZIF’s and in particular ZIF-8 show exceptional thermal, chemical and water
stabilities under a range of conditions which indicates great promise for industrial adsorption
applications. (McEwen et al., 2013) Several studies have reported the experimental adsorption
results of CO2 on ZIFs. Adsorption of CO2 using ZIF-69 indicated that ZIF-69 had a large
adsorption capacity of 82.6L/L at a low pressure of 1atm at 298K. CO2 adsorption performance of
ZIF-78 was also studied and it was discovered that ZIF-78 exhibits a remarkable capacity of 60.2
cm3/g at 273K and 1 atm. (Banerjee et al., 2008) ZIF-78 displays extraordinary ability of storing
CO2 compared to other industrial adsorbents. However, the cost of synthesizing ZIF-78 is too high,
especially comparing its commercial potential. (Liu et al., 2013) The quantify of CO2 adsorbed on
ZIF-8 at lower pressure was lower than that on ZIF-69. However, at higher pressures, ZIF-8
achieves a higher capacity. These phenomenon is explained by the fact that the total pore volumes
of ZIF-8 is bigger than than ZIF-69. This indicates that ZIF-8 is a promising candidate for CO2
capture. (Pérez-Pellitero et al., 2010)

UiO-66 is a zirconium-based metal-organic frameworks (Zr-MOFs). This compound has

exceptional stabilities comporated to those of other common MFOs. It is stable up to 500°C in air
and stable in most chemical solvents. It also posses excellent mechanical stabilities, in particular,
high resistance to shear stress. (Wu et al., 2013) Previous studies have shown UiO-66 used as a
composite with graphene oxide (GO-5) to adsorb carbon dioxide. The results have shown
favourable results with higher adsorption capacities of carbon dioxide when compared to

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TiO2/GO-0.1 composite. Based on the Dubinin-Ashtakov isotherm model, the value of the mean
free energy adsorbed per molecule of adsorbate for carbon dioxide adsorption onto the UiO66/GO-
5 composite shows ideal regeneration stability and recyclability of it. Thus, this composite is a
favourite medium for CO2 capture. The theoretical results verify the experimental data which
reports that carbon dioxide adsorption on this adsorbent is reversible. Thus, this adsorbent is
favourable for CO2 adsorption in pressure swing adsorption process. (Noorpoor and Nazari
Kudahi, 2016)

With the concern of increased global warming, more and more attention has been paid to
the capture of CO2 from flue gases emitted by power plants. These emissions account for a large
chunk of overall CO2 emission. CO2 capture by vacuum pressure swing adsorption (VPSA) is a
promising option for separating carbon dioxide from flue gas since it has a high number of
advatanges. Those advtanges include low energy requirements, low capital investments costs and
easy to achieve automated operations.VPSA processes in particular with the use of novel adsorbent
materials have attracted much research effort. (Shen et al., 2011) At pressures above 4 bars, the
adsorption capacities of activated carbons are greater than zeolites. For a mixture of CH4 and CO2,
it is possible to obtain a fairly pure gas during the adsoption phas of VPSA. Experimentaly data
has shown, for the mixture of CH4 and CO2, and an efficient separation with a concentration of
more than 95% of CH4 can be obtained in the purified gas. (Kacem et al., 2015) Flue gas from
power plants typically have CO2 concentrations of 15% and the balance of the gas occupied by N2.
A study done using a three-bed VSA cycle has indicated that with a vacuum pressure of 10kPa,
CO2 can be purified upto 95.3% with a recovery of 98.2%. (Ling et al., 2016) Therefore, there is
a need for CO2 capture using adsorbents with more than suitable characteristics through vacuum
pressure swing adsorption. In this study, an attempt is made to use ZIF-8 and UiO-66 as the
adsorbents for CO2 capture using VPSA.

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4.0 Research Methodology
4.1 Chemical Preparation
Preparation of simulated flue gas with compositions similar to that in the real world are
performed using the mass flow controller in the vacuum pressure swind adsorption unit. Pure
carbon dioxide and nitrogen concentrations are varied according to experiment cycles and fed
based on manipulated and controlled variable values.

4.2 Adsorbent Preparation

4.2.1 Zeolitic Imidazolate Framework-8 (ZIF-8) Preparation

Solution A is produced when 0.60g of zinc nitrate hexahydrate, Zn(NO3)2.6H2O is
added to a solution containing 10mL of methanol, CH3OH. The mixture is stirred for
approximately 30 minutes. In a separate solution, Solution B, 0.24g of 2-methylimidazole
(2-Hmim), C4H6N9 and 0.136g of sodium formate, HCOONa is added to a solution
containing 10mL of methanol, CH3OH. The mixture is stirred for approximately 30
minutes as well. Next, Solution A and Solution B are both mixed and stirred for another
20 minutes. Then, thermal treatment is applied to the mixed solution. The mixture is heated
at 70°C for 1, 2 and 3 hours respectively. The synthesized adsorbent is then washed using
methanol and dried slowly under saturated conditions at 55°C overnight.

The molar ratio of the precursor solution is Zn2+:2-Hmim:Sodium Formate:Methanol

= 1.000:1.450:0.992:245.000

4.2.2 Universitetet i Oslo-66 (UiO-66) Preparation

Solution A is produced when 1.06g of zirconium (IV) chloride, ZrCl4 is added to a
solution containing 30mL of dimethylformamide (DMF). The mixture is stirred for
approximately 30 minutes. In a separate solution, Solution B, 0.78g of 1,4
benzenediarboxylic acid (BDC) is added to a solution containing 30mL of DMF at room
temperature in a volumetric flask. The mixture is stirred for approximately 30 minutes.
Next, Solution A and Solution B are both mixed and stirred together with 2mL of deionized
water and then placed in an oil bath. Then, thermal treatment is applied to the mixed
solution. The mixture is heated at 80°C, 100°C , 120°C and 140°C for 30 minutes

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 respectively. The solution is cooled down in air to room temperature for 2 hours. The
resulting precipitate is filtered and repeatedly washed with absolute ethanol for 3 times.
The synthesized adsorbent is then dried at 70°C overnight.

4.3 Experimental Rig Set-Up

The experimental VPSA set-up contains 2 main sections:

(1) The mixture section consists of two mass flow controllers, M1 and M2, a mixing unit,
M100, six isolation valves and a solenoid valve, VF after M100. M1 and M2 are connected to
cylinder units of pure carbon dioxide and nitrogen respectively. The isolation valves are present
after the mass flow controllers to prevent the opposite flows of gas through M1 and M2.

(2) The VPSA column section consits of two column beds for adsorption, Bed A and Bed
B, two mass flow meters, M3 and M4 and seven regulating solenoid valves. This section consists
of two sampling points as well. A vacuum pump is also fixed to allow ultimate pressure of vacuum
and the columns have inner tubes filled with adsorbents.

4.4 Experimental Procedure

4.4.1 Characterization of Adsorbent

The surface area, surface morphology and surface chemistry of the adsorbents are
chracterized using principles of x-ray diffusion (XRD), thermogravimetric analysis (TGA),
scanning electron microscope (SEM) and Brunauer-Emmett-Teller (BET) equations. The
BET surface area of the adsorbents are measured from adsorption isotherms using the BET
equation. The surface morphology of the adsorbents are eamined using a SEM. TGA and
XRD measurements are carried out to further charaterize the adsorbents.

4.4.2 Breakthrough Analysis

The breakthrough curves will be determined beforehand using carbon dioxide and
nitrogen gas components to determine the necessary time parameters needed for the
experiment.

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4.4.3 Vacuum Pressure Swing Adsorption
Step (1) of VPSA is the pressurization/blowdown step. Bed A undergoes
pressurization while Bed B goes through a blowdown stage. It is operated by first opening
valve 5 and closing valve 4 so that the adsorbate in Bed 2 can be drawn out at P blow = 0.1
bar into a waste tank using a vacuum pump. Bed 1 is then pressurized by closing valve 2
and 7 and opening valve 1 and VF. This is to allow the multicomponent gas feed at set flow
rates containing the composition of gas required at different concentrations.

Step (2) of VPSA is the adsorption/purge step. Bed A undergoes adsorption while
bed B goes through purging (regeneration). Once PH = 8 bars is reached in Bed A and Pblow
= 0.1 bar in Bed B, valve 8 is closed while valve 7 and 9 are opened to allow the CO2 rich
product to flow into a product tank. The pressure is mainained at 8 bars for the duration of
adsorption time (420s). During adsorption time, CO2 in the feed is captured by the
adsorbent in bed 1 and N2 rich product stream is collected in the product tank. Meanwhile
Bed 2 is purged and the purged gas is sent to a waste tank.

Step (3) of VPSA is the depressurization/equalization step. Depressurization occurs

in Bed A while equalization in Bed B. After adsorbent is saturated with carbon dioxide,
the feed is stopped by closing valve 1, 4, 5 and 7 and differential pressure, while opening
valve M3 and M4 to direct the flow of product stream from Bed A into Bed B until pressure
in both beds equalize. (4 bars). The operation is in a closed loop and there is neither product
nor feed leaving or entering PSA during this cycle.

Step (4) of VPSA is blowdown/pressurization step. During this step, valve 5 is

closed and valve 4 opened to allow adsorbate in Bed A to be drawn out at P blow = 0.1 bar
into a waste tank using vacuum pump. Bed B is then pressurized by closing valve 8 and
opening valve 2 so that the multicomponenet gas feed containing carbon dioxide can flow
into Bed B until pressure in the bed reaching PH = 8 bars.

Step (5) of VPSA is desorption/adsorption step. Bed A undergoes desorption while

Bed B undergoes adsorption. Once PH = 8 bars is reached in Bed B and Pblow = 0.1 bar is
reached in Bed A, valve 8 is opened to allow N2 rich product to flow into product tank. The
pressure is maintained at 8 bars for the duration of adsorption.

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 Step (6) of VPSA shows the equalization step for Bed A and depressurization step
for Bed B. After the adsorbent is saturated with carbon dioxide in Bed B, the feed is stopped
and valves 4, 5 and 8 and differential pressures are closed. Valve M3 and M4 are opened
to direct the flow of product stream from Bed B into Bed A until the pressure in both beds
equalize at 4 bars. This cycle operates in a closed loop and there is neither product coming
out nor feed entering the PSA.

5.0 Chemicals and Equipment

List of chemicals:

 Carbon dioxide gas (99.9% purity)

 Nitrogen gas (99.9% purity)
 ZIF-8 adsorbent
 UiO-66 adsorbent

List of equipments:

 Thermal gravimetric analysis (TGA)

 Scanning electron microscope (SEM)
 X-ray powder diffraction (XRD)
 Brunauer-Emmett-Teller (BET)
 Gas chromatography (GC)
 Vacuum pressure swing adsorption (VPSA)

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6.0 Gantt Chart

2016 2017
No. Tasks
October November December January February March April May

1. Research proposal. 

2. Chemical preparation. 

3. Adsorbent preparation. 
Adsorbent
4. characterization and
breakthrough curve plot.

Vacuum pressure swing
5. adsorption performance
study.


6. Thesis writing and Viva. 

 Milestones, completion of tasks.

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7. 0 Reference
BANERJEE, R., PHAN, A., WANG, B., KNOBLER, C., FURUKAWA, H., O'KEEFFE, M. & YAGHI,
O. M. 2008. High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to
CO2 Capture. Science, 319, 939-943.

CHUE, K. T. K., J. N.; YOO, Y. J.; CHO, S. H. & YANG, R. T. 1995. Comparison of Activated Carbon
and Zeolite 13X for CO2 Recovery from Flue Gas by Pressure Swing Adsorption. Ind. Eng. Chem.
Res, 34, 591-598.

DANTAS, T. L. P., LUNA, F. M. T., SILVA JR, I. J., TORRES, A. E. B., DE AZEVEDO, D. C. S.,
RODRIGUES, A. E. & MOREIRA, R. F. P. M. 2011. Carbon dioxide–nitrogen separation through
pressure swing adsorption. Chemical Engineering Journal, 172, 698-704.

GOMES, V. G. & YEE, K. W. K. 2002. Pressure swing adsorption for carbon dioxide sequestration from
exhaust gases. Separation and Purification Technology, 28, 161-171.

KACEM, M., PELLERANO, M. & DELEBARRE, A. 2015. Pressure swing adsorption for CO2/N2 and
CO2/CH4 separation: Comparison between activated carbons and zeolites performances. Fuel
Processing Technology, 138, 271-283.

LI, J. R., KUPPLER, R. J. & ZHOU, H. C. 2009. Selective gas adsorption and separation in metal-organic
frameworks. Chemical Society Reviews, 38, 1477-1504.

LING, J., XIAO, P., NTIAMOAH, A., XU, D., WEBLEY, P. & ZHAI, Y. 2016. Strategies for CO2 capture
from different CO2 emission sources by vacuum swing adsorption technology. Chinese Journal of
Chemical Engineering, 24, 460-467.

LIU, D., WU, Y., XIA, Q., LI, Z. & XI, H. 2013. Experimental and molecular simulation studies of CO2
adsorption on zeolitic imidazolate frameworks: ZIF-8 and amine-modified ZIF-8. Adsorption, 19,
25-37.

MCEWEN, J., HAYMAN, J.-D. & OZGUR YAZAYDIN, A. 2013. A comparative study of CO2, CH4 and
N2 adsorption in ZIF-8, Zeolite-13X and BPL activated carbon. Chemical Physics, 412, 72-76.

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NOORPOOR, A. R. & NAZARI KUDAHI, S. 2016. Analysis and study of CO2 adsorption on UiO-
66/graphene oxide composite using equilibrium modeling and ideal adsorption solution theory
(IAST). Journal of Environmental Chemical Engineering, 4, 1081-1091.

PARK, K. S., NI, Z., CÔTÉ, A. P., CHOI, J. Y., HUANG, R., URIBE-ROMO, F. J., CHAE, H. K.,
O'KEEFFE, M. & YAGHI, O. M. 2006. Exceptional chemical and thermal stability of zeolitic
imidazolate frameworks. Proceedings of the National Academy of Sciences of the United States of
America, 103, 10186-10191.

PÉREZ-PELLITERO, J., AMROUCHE, H., SIPERSTEIN, F. R., PIRNGRUBER, G., NIETO-DRAGHI,

C., CHAPLAIS, G., SIMON-MASSERON, A., BAZER-BACHI, D., PERALTA, D. & BATS, N.
2010. Adsorption of CO2, CH4, and N2 on Zeolitic Imidazolate Frameworks: Experiments and
Simulations. Chemistry – A European Journal, 16, 1560-1571.

ROWSELL, J. L. C. & YAGHI, O. M. 2004. Metal–organic frameworks: a new class of porous materials.
Microporous and Mesoporous Materials, 73, 3-14.

SHEN, C., YU, J., LI, P., GRANDE, C. A. & RODRIGUES, A. E. 2011. Capture of CO2 from flue gas by
vacuum pressure swing adsorption using activated carbon beads. Adsorption, 17, 179-188.

WU, H., CHUA, Y. S., KRUNGLEVICIUTE, V., TYAGI, M., CHEN, P., YILDIRIM, T. & ZHOU, W.
2013. Unusual and Highly Tunable Missing-Linker Defects in Zirconium Metal–Organic
Framework UiO-66 and Their Important Effects on Gas Adsorption. Journal of the American
Chemical Society, 135, 10525-10532.

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