Energy Procedia 37 ( 2013 ) 16 24

1876-6102 2013 The Authors. Published by Elsevier Ltd.

Selection and/or peer-review under responsibility of GHGT
doi: 10.1016/j.egypro.2013.05.080
11
th
International Conference on Greenhouse Gas Control Technologies
Kyoto, Japan, 18
th
22
nd
November 2012
Carbon Dioxide Capture from Flue Gases by Solid Sorbents
Mustafa Abunowara
a
and Mohammed Elgarni
b
*
a
Libyan Petroleum Institute, 7Km Ghergarsh Road, Tripoli, 6431,
a
Libya
b
HTC Purenergy Inc.
b
#150-10 Research Drive, Regina, Saskatchewan, Canada
Abstract
An electro balance reactor (thermo gravimetric analyzer) was used to study the reaction rate and
achievable sorbent capacity as a function of carbonation temperature, carbonation gas composition, and
calcination temperature and atmosphere. The first precursor (calcium carbonate) was calcined to calcium
oxide and then converted at temperature ranges (550 mm
o
C ~ 750
o
C) to calcium carbonate (CaCO
3
) and final
absorption capacity of calcium oxide at 700
o
C is 65%. The second precursor (caustic soda) at
temperature ranges (75
o
C ~ 225
o
C) was directly carbonated to sodium carbonate and found that 77%
sodium carbonate hydrate and sodium carbonate 23% at 150
o
C. The final absorption capacity is 25 %
and also caustic soda was directly carbonated to sodium carbonate at 225
o
C and final absorption capacity
is 19.2 %. Lithium orthosilicate at temperature ranges (550
o
C ~ 750
o
C) was directly carbonated to
lithium metasilicate and lithium carbonate and found that the final absorption capacity at 700
o
C is 35%.
Sorbent reproducibility and durability were studied in multi-cycle tests for calcium oxide and lithium
orthosilicate. Electro balance tests show that lithium orthosilicate sample had better performance than
calcium oxide sample for multi-cycle tests.
2013 The Authors. Published by Elsevier Ltd.
Selection and/or peer-review under responsibility of GHGT
Keywords: CO
2
Capture,Calcium oxide looping, Solid sorbents
Introduction
of the major sources of the green house gas CO
2
[1]. It is necessary to develop technologies that will
Available online at www.sciencedirect.com
2013 The Authors. Published by Elsevier Ltd.
Selection and/or peer-review under responsibility of GHGT
Mustafa Abunowara and Mohammed Elgarni / Energy Procedia 37 ( 2013 ) 16 24 17
allow us to utilize the fossil fuels while reducing the emissions of green house gases. Commercial CO
2

capture technology that exists today is expensive as well as energy intensive [2]. Improving technologies
for CO
2
capture are crucial to achieve low energy penalties. However, one of the advanced concepts for
capturing CO
2
is an absorption process with dry regenerable sorbents. Such these processes that have the
potential to reduce efficiency penalties compared to wet absorption processes. The absorbent material
should be largely available for a low price [3]. Calcium Carbonate would be a suitable absorbent material;
it is available in the nature in large quantities [4]. Carbon dioxide separation process at high temperature
is highly desirable in many industrial applications, especially in oil and gas refineries, cement plants, steel
manufactures and coal burning power plants. The flue gas typically contains about 12 % CO
2
, 73 %
nitrogen, 10 % vapor water, 4 % oxygen and less than 1 % various pollutants by volume [6]. As well as
the high temperature carbon dioxide (CO
2
) separation does not need to cool the flue gas to the ambient
temperature or even lower temperature prior to separation, thus reduce the cost caused by heat exchange.
It can also produce concentrated and hot CO
2
that can be subsequently used directly as feedstock for high
temperature chemical synthesis of fuels (e.g. methanol or urea or chemicals) [7].The amount of heat in the
troposphere depends on concentrations of atmospheric greenhouse gasses and the amount of time these
gasses remain in the atmosphere. The most important of green house gasses are carbon dioxide CO
2
,
Chlor-Fluoro-Carbons CFCs, nitrogen oxides and methane. Since the industrial revolution in 1850 began,
human processes have been causing emissions of greenhouse gasses, such as CFCs and carbon dioxide
[6]. This has caused an environmental problem: the amounts of greenhouse gasses grew so extensively,
mate is changing because the temperatures are rising. This unnatural addition to the
greenhouse effect is known as global warming. It is suspected that global warming may cause increases in
storm activity, melting of ice caps on the poles, which will cause flooding of inhabited continents, and
other environmental problems [7]. Furthermore, it has chronic effects on airway and lung function,
particularly in people with asthma [8].


* Corresponding author. Tel.: +21826-4830022; fax: +2184836820.
E-mail address: abunowara80@yahoo.com.

Nomenclature
CO
2
Carbon Dioxide
GHGs Greenhouse Gases
SO
2
Sulfur Dioxide
N
2
Nitrogen Dioxide
NaHCO
3
Sodium Bicarbonate
Li
2
ZrO
3
Lithium Zirconate
Li
2
CO
3
Lithium carbonate
Li
2
SiO
3
Lithium metasilicate
CaCO
3
Limestone or Calcium Carbonate
N
2
Nitrogen
CaO Calcium oxide
NaOH Caustic soda
Li
4
SiO
4
Lithium orthosilicate
18 Mustafa Abunowara and Mohammed Elgarni / Energy Procedia 37 ( 2013 ) 16 24
TG Thermogravimetric Analysis
DTA Differential Thermal Analysis
DSC Differential Scanning Calorimetry
The Material and Methods
Solid alkali Sorbents
The first but the foremost material is limestone (CaCO
3
), the purity of this procures is 99.999% (metal
basis), and was supplied from MINDEX LIMITED, HORLEY RH6 7YH.U.K. The second material
which was used sodium hydroxide hydrate (NaOH) was obtained from the ADWIC Company. Finally,
the third material which was used lithium orthosilicate, the purity of this material is 99.9% (metals basis)
was supplied from Alfa Aesar, A Johnson Matthey Company.
Gases
Pure nitrogen gas (N
2
) (99.999%) which was used as neutral gas (sweeping gas) for calcination cycle and
pure carbon oxide (CO
2
) (99.9%) as active gas for carbonation cycle.

Table.1 the physical properties of the chemical substances


Molecular
formula

Density


Appearance

Melting point

Molar mass

Boiling point

Solubility in
water

CaO

3350 kg/m
3


White solid

2572
o
C (2845K)

56.1 g/mol

2850
o
C

Reacts

NaOH

2.1g/cm
3



White solid

318
o
C (591K)

39.9971 g/mol

1390
o
C

111g/100
ml(20
o
C)

Li
4
SiO
4


2.4 g/cm
3


White crystalline
powder

1255
o
C

119.854
g/mol

Do not determined

Insoluble in
H
2
O at 20
o
C

CaCO
3


2.83g/cm
3


White powder

825
o
C

100.087 g/mol

Decomposes

Insoluble

CO
2


1.600kg/m
3
, solid;
1.98 kg/m
3
,gas

Colorless gas

57 C (216 K)
(under pressure)


44.0095 g/mol

-78(195K)
sublimes

1.45kg/m
3


N
2


(0
o
C,101.325
kpa)1.251g/L

Colorless Gas
63.15K (40.00
o
C,
-346.42
o
F)

28g/mol

-195.79 C

Insoluble

Carbon dioxide absorbed Instruments

The Labsys TG SETARAM instrument is being used in thermal analysis and calorimetry for gas solid
reactions and in thermal degradation. The balance can accurately measure up to one microgram and the
weight of the sample was recorded every second.
Mustafa Abunowara and Mohammed Elgarni / Energy Procedia 37 ( 2013 ) 16 24 19
Sorbent Reactivity Testing and Structural Analysis

The reactivity testing of calcium oxide (CaO), lithium orthosilicate (Li
4
SiO
4
), and caustic soda (NaOH)
sorbents for carbonation process were carried out separately in a Labsys (TG) thermo gravimetric
analyzer (TGA) apparatus. The balance can accurately measure up to one microgram. As well as, a small
sample of the sorbent (65 mg) is roughly placed in a platinum crucible and the weight of the sample was
recorded every second.
Procedures of absorption experiments

1. Calcination and carbonation cycle of the calcium oxide sorbent (CaO): Calcination and
carbonation cycle of the calcium oxide sorbent (CaO Scanning rate at 10
o
C/min and start heating
from 30
o
C to 1000
o
C and after that start the decarbonation cycle for CaCO
3
to assure that the
material (calcium carbonate) fully decomposed to CaO [CaCO
3

2
(g)], and
after that cool down until reach the required temperature (550, 600, 650, 700, and 750
o
C) to start
the isotherm cycle for one hour, hence finishing the decarbonation and isotherm cycles under
nitrogen gas switch on to carbon dioxide gas to start the carbonation cycle [CaO (s) + CO
2
(g)
3
(s)] for three hours. Finally, rapid cooling from required temperature down to 25
o
C at
scanning rate 30
o
C/min is needed.
2. Carbonation cycle of the caustic soda (NaOH):
3. Start the scanning rate at 10
o
C/min and start heating from 25
o
C to the required temperature
ranges (75, 100, 125, 175, 200 and 225
o
C) and after that start the isotherm cycle for one half
hour, hence finishing heating and isotherm cycles under nitrogen gas switch on carbon dioxide
gas to start the carbonation cycle for one hour [2NaOH + CO
2

2
CO
3
+ H
2
O]. Finally, rapid
cooling from required temperature down to 25
o
C at scanning rate 30
o
C/min is needed.
4. Calcination and carbonation cycle of the lithium orthosilicate (Li
4
SiO
4
): Scanning rate at
10
o
C/min and start heating from 30
o
C to the required temperature At the required temperature
ranges (550, 600, 650, 700, and 750
o
C) start the isotherm cycle for one hour, hence finishing the
calcination and isotherm cycles under nitrogen gas switch on to carbon dioxide gas to start the
carbonation cycle [Li
4
SiO
4
(s) + CO
2

2
CO
3
(s) + Li
2
SiO
3
(s)] for three hours. Finally,
rapid cooling from required temperature down to 25
o
C at scanning rate 30
o
C/min is needed.
Results and Discussion

The decomposition of the calcium carbonate (green curve) starts around 850
o
C (red curve) as shown in
figure 1. Firstly, the sample was heated up to 1000
o
C under nitrogen gas to ensure that the calcium
carbonate sample fully decomposed (represented in 48% losses of the original sample). In addition, the
transition accompanied with drop in heat flow (blue curve) starts at -5 V ends at -25 V (endothermic
reaction). Secondly, after calcination stage, the furnace started cooling down the sample to the required
temperature followed by the isotherm condition for one hour. Finally, the flow automatically was
switched on pure carbon dioxide CO
2
stream to start the carbonation cycle for three hours. This transition
accompanied with gain in the heat flow (blue curve) starts at 5 V ends at 250 V (strongly exothermic
reaction)

20 Mustafa Abunowara and Mohammed Elgarni / Energy Procedia 37 ( 2013 ) 16 24


Figure 1 decomposing cycle of the calcium carbonate at around 850 C and carbonation cycle of calcium
oxide started at 700C

Figure 2 depicts the weight gain present at three difference temperatures (550C, 700C, and 750C). As
shown, the sorption rate increases substantially as temperature increases (550C, 700C, and 750C).
Furthermore, the absorption capacities of calcium oxide (CaO) at three difference temperatures are 31.3
% mg CO
2
/mg CaO, 46.5 % mg CO
2
/mg CaO, and 57.3 % mg CO
2
/mg CaO respectively.




















Figure 2 weight gain % vs. time/min of three temperatures at 550 C, 700 C and 750 C
Time/s 0 2500 5000 7500 10000 12500 15000 17500 20000
Furnace temperature /C
0
100
200
300
400
500
600
700
800
900
1000
HeatFlow/V
-25
0
25
50
75
100
125
150
175
200
225
TG/mg
35
40
45
50
55
60
65
Figure:
23/04/2007 Mass (mg): 60
Crucible:PT 100 l Atmosphere: CO2 Experiment:NewBlank_D+A at_700_1_1
Procedure: 30 - 700 (Zone 1)
Labsys TG
Exo
0
10
20
30
40
50
60
70
0 50 100 150 200
W
e
i
g
h
t

g
a
i
n
%
Time/min
Temperature 750
Temperature 700
Temperature 550
Mustafa Abunowara and Mohammed Elgarni / Energy Procedia 37 ( 2013 ) 16 24 21

One of the possible hurdles in the utilization of metal oxides for the carbonation and calcination reaction
scheme is its vulnerability to sintering due to the thermal cycling imposed by the cyclical nature of these
reactions. Cyclical studies were carried out to quantify any loss in reactivity of this sorbent upon multiple
cycles. However, the temperature chosen for cyclical studies was 750 C and this temperature is sufficient
to achieve carbonation cycle. As well as, the precursor was first calcined under nitrogen at 1000 C and
after that the sample cooled down to 750
o
C for isotherm condition for one hour. The gas was then
switched to pure CO
2
and the weight gain continuously tracked for one hour. This process was repeated
for 2, 3, 4, and 5 cycles as shown in figure 3. The data obtained on CaCO
3
undergoing this cyclical study
are the capacity for the five cycles are 65.6% mg CO
2
/mg CaO

and 48.6% mg CO
2
/mg CaO

and 41.8%
mg CO
2
/mg CaO

and 38.5% mg CO
2
/mg CaO

and 36.5% mg CO
2
/mg CaO

respectively. It can be seen
that the reactivity of CaCO
3
exhibited a gradual decrease even after the first cycle. It can be seen that the
sorbent reactivity remained high and if enough reaction time is provided, the conversion could reach
higher than get at every cycle.




Figure 3 the multi cycles of CaO-CO
2
absorption reaction at 750 C

The sample was heated up to the desire temperature 225
o
C (red curve) under nitrogen gas as shown in
figure 4. When furnace temperature reached 100
o
C, the sample started losing its weight was 6 mg from
original sample due to the nature of the sample. Secondly, start the isotherm condition one hour under
nitrogen gas as well. Finally, the flow was switched on pure carbon dioxide (CO
2
) stream to start the
carbonation cycle for one hour as well. This change accompanied with gain in the heat flow (blue curve)
starts at 12.5 V ends at 375 V (extremely exothermic reaction).
Time/s 0 5000 10000 15000 20000 25000 30000
Furnace temperature /C
50
100
150
200
250
300
350
400
450
500
550
600
650
700
750
800
850
HeatFlow/V
-100
-50
0
50
100
150
200
250
TG/mg
35
40
45
50
55
60
Figure:
27/06/2007 Mass (mg): 45
Crucible:Al 100 l Atmosphere: N2 Experiment:adsorption of CO2--7
Procedure: CO2 (Zone 1)
Labsys TG
Exo
22 Mustafa Abunowara and Mohammed Elgarni / Energy Procedia 37 ( 2013 ) 16 24



Figure 4 absorption reaction cycle of the caustic soda with the pure carbon dioxide at 225C

The endothermic peak appears on the heat flow chart (blue curve) from -5 V to 12.5 V. This could be
due to the hydrate of elastic caustic soda. As well as, exothermic peak appears on the heat flow chart
(blue curve) at 125
o
C released heat 12.5 V to 375 V and this pick up in the weight (green curve) of the
elastic caustic soda sample due to the reaction of elastic caustic soda with carbon dioxide at of a part of
first minute and the finally the absorption capacity of calcium oxide at 225
o
C is 19.2 % mg CO
2
/mg
NaOH.

As shown in figure 5. Firstly, the sample was heated up to 700
o
C under nitrogen gas. Secondly, when the
sample reached the required temperature, then the system switched on the isotherm cycle for one hour and
a half under nitrogen gas. In addition to, the sharp drop of the mass loss (green curve) starts at 100
o
C up
to 700
o
C indicates that decomposition of the lithium orthosilicate (represented in 10.5 % losses of the
original sample) accompanied with drop in the heat flow (blue curve) starts at 3.5 V ends at -23.5 V
(endothermic reaction). Finally, the flow was switched on pure carbon dioxide stream (CO
2
) to start the
carbonation cycle for one hour and a half. As well as, this change accompanied with gain in the heat flow
(blue curve) starts at -15 V ends at 68V (extremely exothermic reaction).






Time/s 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500
Furnace temperature /C
20
40
60
80
100
120
140
HeatFlow/V
0
25
50
75
100
125
150
175
200
225
250
275
TG/mg
41
42
43
44
45
46
47
48
49
50
Figure:
13/06/2007 Mass (mg): 54.27 Molar mass: 40
Crucible:PT 100 l Atmosphere: N2 Experiment:Adsorption of CO2 by NaOH at __ __150 C -4
Procedure: 20- 150 (Zone 1)
Labsys TG
Exo
Mustafa Abunowara and Mohammed Elgarni / Energy Procedia 37 ( 2013 ) 16 24 23


Figure 11 absorption reaction cycle of lithium orthosilicate with pure carbon dioxide at 700C

On the other hand, the exothermic peak appears on the heat flow chart (blue curve) at 700
o
C released
heat -15 V to 68 V and this pick up in the weight (one shot and after that the weight gain started
increasing very slow) of the lithium orthosilicate sample due to the starving reaction of lithium
orthosilicate with carbon dioxide at first minute. Finally, absorption capacity of lithium orthosilicate at
700
o
C is 35.8% mg CO
2
/mg Li
4
SiO
4
.
Conclusions

The investigated materials were selected among minerals, such as calcium carbonate, lithium orthosilicate
for high temperature ranges (550
o
C ~ 750
o
C), and caustic soda for low temperature ranges (75
o
C ~ 225
o
C). The ability of the calcium oxide to regenerate the carbonate decreases strongly with the increasing
number of cycles compared with lithium orthosilicate which is has stable durability but calcium oxide has
absorption capacity of capturing carbon dioxide higher than lithium orthosilicate at high temperature
ranges. Caustic soda sorbent was tested at low temperature ranges. (75
o
C ~ 225
o
C) and found that its
ability for absorbing pure carbon dioxide increase with increasing temperature ranges.
Time/s 0 2000 4000 6000 8000 10000
Furnace temperature /C
50
100
150
200
250
300
350
400
450
500
550
600
650
700
HeatFlow/V
-20
-10
0
10
20
30
40
50
60
70
TG/mg
62.5
65.0
67.5
70.0
72.5
75.0
77.5
80.0
82.5
85.0
Figure:
08/07/2007 Mass (mg): 100
Crucible:Al 100 l Atmosphere: N2 Experiment:Adsorption of CO2 by Lithium Orthasilicate at 700
Procedure: (Zone 1)
Labsys TG
Exo
24 Mustafa Abunowara and Mohammed Elgarni / Energy Procedia 37 ( 2013 ) 16 24
Acknowledgements

The author is grateful to Dr. Mohammed Elgarni for his supervision during MSc dissertation and BSc
project, Dr. Fawzi M. Elfeghi and Eng. Muheddin Jaloul for their assistance and helpful discussions. This
work was supported by Libyan Petroleum Institute (LPI).
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