Su Fang Wu Ph.D., Professor
Yu Yao Shi, Rong Wu, Xiao Chong Xue, Yan Wang
Department of Chemical and Biological Engineering
Zhejiang University, Hangzhou, 310027, China Email: [email protected]
http://che.zju.edu.cn/wusf
Nano CaO-based CO2 Adsorbents Evaluation by a Circulating Fluidized Bed System
Main works--- From material to process
ReSER Process for Hydrogen production
CO2 capture in flue gas
Others
Nano CaO-based CO2 adsorbent
2 3CaO CO CaCO+ Û
298 178.8 /H kJ molD = -
1
Related works during 2010-2012 Adsorbent/catalyst developments: Nano CaO reactive with CO2 – New model S. F. Wu, P. Q. Lan, AIChE J. 2012, 58(5): 1570-1577 • Expending pore of nano CaO adsorbent Q. Tang, S. F. Wu, JCESU,2012,12(1) :31-37 • Nano CaO grain characteristics and growth model Y. Q. Zhu, S. F. Wu , X.Q.Wangl, Chem Eng J., 2011,175(15):512-518 • a Ca12Al14O33 Nano-layer and Its Effect on the Attrition Behavior Su F. Wu，Ming Z. Jiang, IEC Res. 2010, 49(23), 12269-12275 • ZrO2-modified Ni–nano-CaO sorption complex catalyst S. F. Wu, L. L. WangInt. J. Hydrogen Energy, 2010,35(13): • CaTiO3/Nano-CaO as a CO2 adsorbent Su. F. Wu, Yan. Q. Zhu, Behavior, IEC Res. 2010,49(6):2701-2706. • A micro-sphere catalyst complex with nano CaCO3 S. F. Wu, L.B. Li,Y. Q. Zhu,X.Q. Wang, Eng. Sci., 2010,8(1):22-26
improve the sorption capacity / durability / attrition lost Increase the sorption rate and decrease the decomposition temperature
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Nano CaO
Micro CaO
Nano CaO-based CO2 adsorbent for CO2 capture/ in ReSER for H2 production
CaO-based CO2 sorbent
Advantages: √ Fast reaction rate
√ More durability of CO2 sorbent
√ Low Attrition lost
√ Continuation of reaction and regeneration
Attrition lost < 3.5% (2012)
CFB for CO2 capture
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Targets:
Establishing a system of circulating fluid bed(CFB) and evaluation the nano CaO-based adsorbent for CO2 capture.
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Reactor：40mm Height：3-5m Regenerator：50mm Height：3-5m
Fig.1 Cold model circulating fluidized bed reactor system
5
The relation of pressure drop and velocity
0.2 0.4 0.6 0.8 1.0 1.2 1.4
0
1
2
3
4
5
6
7
8
9
10
11
P(Kp
a)
V(m/s)
0.25m 0.50m 0.75m 1.00m 1.25m 1.50m
Fig.2 Different height of adsorbent of the reactor 6
The efficiency of the Cyclone separation
0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.10.900
0.902
0.904
0.906
0.908
0.910
0.912
0.914
0.916
V(m/s)
η
Fig.3 Velocity and the efficiency of the cyclone separation
efficiency of the Cyclone separation >90%
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Fluidized bed system for CO2 capture
Capacity: 1000L/hr Fig. 4 8
The test of the adsorbent flux in the regeneration reactor
2.0 2.5 3.0 3.5 4.0 4.5 5.010
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14
16
18
20
22
24
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P1 (k
Pa)
m （kg）
Fig. 5 P1 vs the adsorbent amount in the regeneration reactor
WPS
∆ =
0.166 1 0.418m P= × +
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The cold model experiment in CFB
P3 (kPa)
Circulation quantity(g/min)
P1 (kPa)
Adsorbent amount in the regeneration
reactor（kg） 0.9 412.9 12.5 2.5 0.9 423.5 12.6 2.5 0.9 420.0 12.5 2.5 0.9 423.5 12.6 2.5 1.0 547.8 11.5 2.3 1.1 601.0 6.3 1.5 1.0 526.5 11.7 2.4 1.1 569.1 11.5 2.3
Table 1 The results of the circulation experiments
The cold model experiment in CFBR
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Blank experimental results of CO2 content
40 60 80 100 120 140 160 180 2000
1
2
3
4
5
6
7
8
C CO
2（ %）
t(s)
CCO2=7.7%
40 60 80 100 120 140 160 1800
5
10
15
20 CCO2=20%
C CO2
（ %）
t(s)
Fig. 6 The experimental data in empty tower
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Adsorption conditions of the hot experiments
Sorption temperature 550℃±5℃ 600℃±5℃
Weight of adsorbent /
CO2 partial pressure
400g/ 0.0077MPa 300g/ 0.0077MPa
400g/ 0.0077MPa
500g/ 0.0077MPa
500g/ 0.0077MPa
500g/ 0.02MPa
600g/ 0.02MPa
Table 2 The sorption situation in a single tower
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60 80 100 120 140 160 180 200 220 240 260 2800
1
2
3
4
5
6
7
8 500g，0.0077MPa
550℃ 600℃
C CO
2(%
)
t(s)
Fig. 7 The output concentration of CO2 at different temperatures（500g,0.0077MPa）
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The hot experimental results in CFBR
0.02MPa 0.0077MPa
Time（s） Adsorption efficiency （%）
Time（s） Adsorption efficiency （%）
70 88.4 80 92.8 99 73.0 165 87.4 133 22.9 195 50.7 190 18.9 233 25.3 268 6.4
Table 3 Adsorption efficiency to CO2 under different CO2 partial pressures （500g,600℃）
The sorption experiment in a single tower
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60 80 100 120 140 160 180 200 220 240 260 2800
1
2
3
4
5
6
7
8
600℃，0.0077MPaC C
O2(
%)
t(s)
300g 400g 500g
Fig. 8 The output concentration of CO2 with different qualities of adsorbent(600℃，0.0077MPa）
300g 400g 500g
Time （s）
Adsorption efficiency （%）
Time （s）
Adsorption efficiency （%）
Time （s）
Adsorption efficiency （%）
72 92.2 67 85.6 80 92.8
95 75.3 95 39.5 165 87.4
128 7.4 138 17.5 195 50.7
160 7.2 168 11.1 233 25.3
202 0.3 193 0.4 268 6.4
Table 4 Adsorption efficiency to CO2 with different qualities of adsorbent(600℃，0.0077MPa）
The sorption experiment in a single tower
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The CO2 capture experimental results using an CO2 online monitor
Fig. 9 16
time/s temperature ℃
CO2content %
CO2 content (blank data) %
CO2 adsorption efficiency %
80 592 600 0.12 0 84.4 165 590 598 1.01 7.3 81.6 233 589 598 5.9 7.7 23.3 268 589 598 7.29 7.7 5.3
Table 6 adsorbent 500g (temperature 600℃,CO2 content 7.7%)
time/s temperature ℃
CO2content %
CO2 content (blank data) %
CO2 adsorption efficiency,%
72 594 599 0.08 0 98.9 95 593 598 0.79 2.85 72.9 128 593 598 5.79 5.82 0.55 160 593 599 6.91 7.43 7.52 202 593 600 7.69 7.7 0.14
Table 5 Adsorbent 300g (temperature 600℃,CO2 content 7.7%)
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CFBR FBR
Gas velocity(m/s) 0.13 0.0027
Residence time(s) 30.8 4 Input CO2
concentration(%) 7.7 20
W/V (g min ml-1) 0.06 0.064
Output CO2 concentration (%) <1 0
Adsorption efficiency(%) >85 100%
Table 7 The best result comparison of the circulating fluidized bed reactor(CFBR) and the fixed bed reactor (FBR)
The sorption experiment in a single tower
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Summary:
1. The nano CaO-based CO2 adsorbent can be used in circulating fluid bed system for CO2 capture.
2. In the CFBR, CO2 content in the out flow gas is lower than 1%, and CO2 sorption efficiency is over 85%.
3. An continues CO2 capture was achieved by a CFBR.
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Thank you for your attention!
