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Energy Procedia 114 (2017) 2336 – 2340

13th International Conference on Greenhouse Gas Control Technologies, GHGT-13, 14-18

November 2016, Lausanne, Switzerland

CO2 Sorption Characteristics of Various Sorbents in the Bubbling

Fluidized-Bed
Young Cheol Parka*, Sung-Ho Joa, Seung-Yong Leea, Jong-Ho Moona, Hyunuk Kima,
Chang-Keun Yia, Chengong Sunb, Hao Liub, and Colin E. Snapeb
a
Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Daejeon 34129, Republic of Korea
b
University of Nottingham, Faculty of Engineering, The Energy Technologies Building, Triumph Road, Nottingham, NG7 2TU, United Kingdom

Abstract

This study reports the performance of base-impregnated silica and activated carbons supplied by the University of Nottingham
(UNOTT) have been tested in the bubbling fluidized-bed reactor and the two interconnected bubbling fluidized-beds in a
continuous system. UNOTT has published several papers with polyethyleneimine (PEI)-silica sorbents using a bubbling
fluidized-bed reactor, reporting that the average working capacity was around 8.0 wt.% and the regeneration heat was around 3.3
GJ/tCO2 based on the cycle tests. In order to verify the performance of this silica adsorbent and to draw comparison with
activated carbons that potentially offer have lower regeneration energies, KIER has carried out cycle experiments using a
bubbling fluidized bed reactor and also used a continuous CO2 capture system which consists of a bubbling fluidized-bed-type
absorption and regeneration reactors. Further, the sorption characteristics, including equilibrium capacity, kinetics, surface area,
pore size distribution, were determined using a volumetric (BET) and a gravimetric (MSB, magnetic suspension balance
methods. The sorption mechanism of CO2 on the sorbent surface was investigated by in situ FT-IR. The optical, physical and
chemical characteristics were examined by SEM- EDAX, TGA before and after the sorption - desorption cyclic tests. Particle
size distribution of the sorbent was also analyzed by laser diffraction particle size analyzer.
© 2017
© 2017TheTheAuthors.
Authors.Published
Publishedby by Elsevier
Elsevier Ltd.Ltd.
This is an open access article under the CC BY-NC-ND license
Peer-review under responsibility of the organizing committee of GHGT-13.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of GHGT-13.
Keywords: silica-PEI; KOH-AC; Cycle test; Sorption characteristics; Physical properties

* Corresponding author. Tel.: +82-42-860-3072; fax: +82-42-860-3134.

E-mail address: [email protected]

1876-6102 © 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of GHGT-13.
doi:10.1016/j.egypro.2017.03.1367
 Young Cheol Parka et al. / Energy Procedia 114 (2017) 2336 – 2340 2337

1. Introduction

In order to develop post-combustion dry-sorbent CO2 capture technologies, various kinds of sorbents have been
developed for several decades. KEPCO-RI has developed alkali or alkali-earth based dry sorbents since 2002 using
sodium or potassium as the active material for CO2 sorption with suitable supports for providing mechanical
strength. In 2012, 0.5 MW-scale test-bed which is installed at Hadong coal-fired power plant has been continuously
operated successfully using KEP-CO2P2 composed of 35 wt.% K2CO3 and 65 wt.% support [1]. They have now
provided the same sorbents for the 10 MW-scale pilot unit to optimize the performance. The physical and chemical
characteristics of KEP-CO2P2 has been proved satisfactory to be applied at this scale, but the energy consumption
for sorbent regeneration may be higher than for other adsorbents, including base-impregnated silicas and activated
carbons. Thus, the Korea Institute of Energy Technology Evaluation and Planning (KETEP) commenced a new
government project last year to develop a new dry-sorbent CO2 capture technology, which can reduce the energy
consumption compared by 20% for current 10 MW-scale pilot plant. To achieve the project goal, the Korea Institute
of Energy Research (KIER) joined the project to improve the process and the University of Nottingham to develop
base-impregnated silica and activated carbon adsorbents that can be manufactured on the scale required. Also,
Yonsei University and PSE Korea are participating in the project to achieve the project goal.
Zhang et al. reported polyethyleneimine-silica(PEI-silica) adsorbents which were applied for CO2 capture from
ambient air [2] and flue gas [3]. He also reported the parametric study on the regeneration heat requirement heat
requirement of an amine-based solid adsorbent process [4]. Liu et al. reported the activated carbon adsorbents for
CO2 capture from flue gas [5]. UNOTT has supplied two kinds of adsorbents so that KIER has tested them in a
fixed-bed CO2 capture system in order to evaluate the CO2 sorption capacity. For PEI-silica adsorbents, KIER has
also performed cyclic adsorption-regeneration experiments using a bubbling fluidized-bed reactor.

2. Experimental

2.1. Apparatus

Fig. 1 (a) shows the fixed-bed system [6] and Fig. 1(b) shows the bubbling fluidized-bed reaction system [7]. The
details of both apparatus have been illustrated in each reference.

Fig. 1. Experimental apparatus. (a) A fixed-bed system; (b) A bubbling fluidized-bed system.
2338 Young Cheol Parka et al. / Energy Procedia 114 (2017) 2336 – 2340

2.2. Conditions

UNOTT supplied two adsorbents such as PEI-silica sample and KOH-treated activated carbon (AC) sample. The
PEI-silica sample of which PEI content is 40 wt.% has been tested in a bubbling fluidized-bed system and the KOH-
treated AC sample which was made using coconut shell in a fixed-bed system. The experimental conditions are
listed in Table 1.

Table 1. Experimental conditions of PEI-silica and KOH-treated AC sample.

PEI-silica KOH-treated AC
Absorption Regeneration Adsorption Desorption
Pressure [bar] 1 1 1 1
Temperature [oC] 50 ~ 80 ~130 22 ~ 25 ~130
Inlet CO2 Concentration [vol.%] 15.0 0.0 15.0 0.0
Inlet gas flow rate [l/min] (N2-balance) 5.0 5.0 1.0 1.0

3. Results

Fig. 2 shows the absorption and regeneration cyclic experimental results of CO2 concentration and reactor
temperature using PEI-silica sample in a bubbling fluidized-bed system.

N2 purge N 2 purge

AB RE AB RE
15
Outlet CO2 Concentration [%]

12

9
Reactor
Cooliing
6

0
Absorption Absorption

Regeneration Regeneration
125
Temperature [ C]
o

100

75

50
AB RE AB RE

0 10 20 30 40 50 60 70 80 90 100 110 120

Time [min] CO 2 Conc.

Temperature

Fig. 2. The absorption and regeneration cyclic experimental results of PEI-silica sample.
 Young Cheol Parka et al. / Energy Procedia 114 (2017) 2336 – 2340 2339

Fig. 3 shows the breakthrough time and the CO2 uptake for each absorption cycle. The CO2 uptake has been
maintained at the level of 2.5 mmol/g, which is approximately 11.0 wt.% while the breakthrough time decreased as
cycle number increased. However, the sample has not been fully regenerated at the regeneration cycle so that the
CO2 uptake will be decreased as the cycle increased. The reason and the solution of these phenomena have been
explained by Zhang et al. [4].

amount of absorp.1
amount of absorp.2
170 3.0

Amount of CO2 absorption [mmol/g]

2.523 2.517
2.5
Breakthrough Time [sec]

160
150 2.0
150
140 1.5
140
1.0
Breakthough Time
130
0.5

120 0.0
1 2 1 2
Cycle [NO.] Cycle [NO.]
Fig. 3. Cyclic experimental results of PEI-silica sample. (a) Breakthrough time; (b) CO2 uptake.

Fig. 4 shows the adsorption and desorption cyclic experimental results of CO2 concentration and reactor
temperature using KOH-treated AC sample in a fixed-bed system.

AD DE AD DE AD DE AD 15
15
Outliet CO2 Concentration [vol.%]
Outlet CO2 Concentration [%]

12
12 Adsorp.-1
Adsorp.-2
Adsorp.-3
9 9
Adsorp.-4

6 6

3 3

0 0
0 10 20 30 40 50 60
140
Time [min]
120
Temperature [ C]

6
o

Outliet CO2 Concentration [vol.%]

100
Adsorp.-1
5
Adsorp.-2
80 Adsorp.-3
4 Adsorp.-4

60 3

40 2

Breakthrough time
1
20
0
0 2 4 6 8
0 60 120 180 240 300 360 420 480 540 600 660 720 780
Time [min]
CO2 Conc. Time [min]

Fig. 4. The adsorption and desorption cyclic experimental results of KOH-treated AC sample.
2340 Young Cheol Parka et al. / Energy Procedia 114 (2017) 2336 – 2340

Fig. 5 shows the breakthrough time and the CO2 uptake for each adsorption cycle. The CO2 uptake has been
slightly decreased to the level of 1.72 mmol/g, which is approximately 7.6 wt.% and the breakthrough time also
decreased as cycle number increased. However, both seem to be maintained after 2nd cycle.

8 2.5

Amount of CO2 adsorption [mmol/g]

7.00 1.94
1.78 1.76 1.72
Breakthrough Time [min]

7 2.0

6.17 6.00
5.83 1.5
6

1.0
5 Breakthough Time (TSA)

0.5
4

0.0
1 2 3 4 1 2 3 4
Cycle [NO.] Cycle [NO.]
Fig. 5. Cyclic experimental results of KOH-treated AC sample. (a) Breakthrough time; (b) CO2 uptake.

4. Conclusions

In this study, we tested PEI-silica sample in a bubbling fluidized-bed system and KOH-treated AC sample in a
fixed-bed system, respectively. Based on cyclic sorption and desorption test, PEI-silica sample showed
approximately 11 wt.% of CO2 uptake in the temperature range of 50 ~ 80 oC, while KOH-treated AC sample
showed 7 wt.% at the room temperature. We plan to analyze CO2 sorption performance of PEI-silica sample which
was made at kg-scale in a two-interconnected bubbling fluidized-bed continuous system. Also, KOH-treated AC
sample from coconut shell or phenolic resin has been prepared for the application of the continuous system.

Acknowledgements

This work was supported by the Korea Institute of Energy Technology Evaluation and Planning(KETEP) and the
Ministry of Trade, Industry & Energy(MOTIE) of the Republic of Korea (No. 20158510011280).

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