Advanced post-ccombustion CO2 capture syystem usin

ng novel p
polyaminee-based
soolid sorben
nts

Yamada1, Shin
Hidetaka Y S Yamammoto1, Junpeei Fujiki2, Firoz
F owdhury1, N
A. Cho Nobuyuki Takayama
T 1
,
Kazuya GGoto1, Katsuuhiro Yoshiizawa3, Takkeshi Okumu ura3, Ryoheei Numagucchi3, Shoheii Nishibe3,
Kaatsunori Yogo1
1
Researchh Institute of
o Innovativ
ve Technoloogy for the Earth
E (RITE
E), 9-2 Kizuugawadai, Kizugawa,
K
Kyotoo 619-0292,, Japan
2
G
Graduate Scchool of Bio
o-Applicatioon and Systtems Engineeering, Tokyyo Universiity
of Agriculture
A and
a Technollogy, Kogan nei, Tokyo 184-8588, JJapan
3
Kaw
wasaki Heavvy Industriees (KHI), Lttd. 1-1 Kaw
wasaki, Akasshi, Hyogo 673-8666, Japan
J

Abstract
CO2 captuure using am mine solid sorbents iss an alternaative method that avoiids the enerrgy penaltyy
associated with conveentional liqu uid absorbeents, becausse solid sorb
bents have the advantaages of low
w
specific heeat and low volatility [1
1-3]. The Reesearch Insttitute of Inn
novative Tecchnology fo
or the Earthh
(RITE) hass been deveeloping an amine-based
a d solid sorbeent system since
s 2010 on the basiss of RITE’ss
novel aminne absorbennt [4-6] and d porous addsorbent [7] technologies. The sysstem targetss large CO2
emission soources suchh as coal-fired power pllants, as shoown in the project
p roaddmap (Figurre 1).

Figure 1 Project roaadmap.

To ensure that the am mines used for solid soorbents havve low volaatility, polyaamines with
h relativelyy
high moolecular weights,
w such
s as commerciially avaiilable pollyethyleneim mine andd
tetraethylennepentaminne (TEPA), were seleccted for im mpregnating porous suppports [1]. In order too
effectivelyy reduce thee regeneration energy aand avoid amine
a degraadation, we demonstraate a uniquee
strategy foor adoptingg low-temp perature proocesses thro
ough the modification
m n of a pollyamine byy
attaching hhindered funnctional grooups such aas isopropy
yl (IP) to the terminal pprimary am
mino groupss

1
(Figure 2). Quantum m chemicaal calculattions [8-11 1]
showed thhat the amineCO
a 2 reaction product is i
moderatelyy destabilissed owing to this m modificationn,
which lowwers the reggeneration energy of the sorbentt.
Molecular simulations and spectroscopic m measurementts
revealed tthat CO2 diffusion
d iss also enhhanced afteer
modificatioon with IP groups
g [12].

To examinne the effeect of mod dification, mmesocellulaar

silica foam
m was impregnated witth IP-introdduced TEPA A
(IP-TEPA)) or TEPA. Then, thee IP-TEPA A and TEPA A
solid sorbeents were evaluated
e in
n terms of C CO2 capturre Figure 2 Modificattion of polyamine.
performancce on a lab-scale
l th
hree-columnn fixed-bed
system (Fiigure 3) usiing simulateed flue gass (10% CO2,
50% relattive humidity) and a steam-aidded vacuum m
swing adsoorption proocess [13]. The amoun unt of steam m
supplied foor sorbent regeneration
r n strongly affected the
CO2 recovvery rate foor both sorrbents, conffirming thaat
steam effeectively aidds CO2 desorption. Thhe IP-TEPA A
sorbent achieved a reecovery ratee of >90% with >95% %
purity withh a steam supply
s at 60 0 C (Figurre 4), which h
correspondded to a regeneration en nergy of appproximately y
1.5 GJ/tonn-CO2. In coontrast, the CO2 recovvery rate fo or
the TEPA A sorbent was
w <60% even at aan operating g
Figure 3 Three-coluumn fixed-beed system.
temperaturre of 70 CC, indicating g the positiive effect of
o
the IP grouups.

Figurre 4 CO2 capture perform

mance of IP-T
TEPA and TE
EPA solid soorbents.

The regeneeration enerrgy of amine-based liquuid absorbeents has beeen reported tto be in thee range 2.3––
4.0 GJ/tonn-CO2 [144,15]. Receent analysiis has dem monstrated that the minimum achievablee
regeneratioon energy in i an absorp ption-basedd process in
n a conventional configguration for coal-firedd
plant flue ggas is in thee range 2.3–
–2.5 GJ/tonn-CO2 [16]. On the oth
her hand, Grray et al. esstimated thee
potential reegenerationn heat duty to
t be 1.2–2 .3 GJ/ton-CCO2 for amine-based soolid sorbentts [17]. Ourr
result, 1.5 GJ/ton-CO O2 using steeam at 60 C, demonsstrates that the regeneeration perfformance iss

2
greatly impproved by chemical
c modification
m n of the amiino function
nal groups of amine-im
mpregnatedd
solid sorbeents.

Currently, Phase II of
o the projeect is beingg carried ou ut by RITE and Kawaasaki Heavy y Industriess
(KHI), Ltdd. (Figure 1)). In this ph
hase, we appply RITE’ss solid sorbeents to KHII’s moving--bed systemm
(KCC systtem, Figure 5 [18]). We W used porrous silica supports
s suiitable for thhe moving-bed systemm
while mainntaining thee abovemen ntioned CO2 capture peerformance. We also ooptimised th he synthesiss
methods too produce ouur novel po olyamine annd solid sorb
bent based on
o detailed chemical an nalysis [19]].
Now we hhave established a pracctical proceess to produ uce our solid sorbents on the scalle of 10 m3
(Figure 6).

Figure 5 K
KCC bench teesting plant. Figure 6 Scale-up synthesis of RITE’s
R aminne and solid sorbent.
s

In Septembber 2017, RIIE,

R KHI, and
a Kansai Electric Po ower Co (KKEPCO), Incc. announceed that theyy
will installl a 40 tonn-CO2/day capture plaant in KEP PCO’s 180 00-MW coaal-fired pow wer stationn
(Maizuru ppower statiion) for pillot-scale deemonstration
n tests postt 2019. Forr the scale--up design,,
bench-scalle tests captturing a few
w tons COO2/day from coal-comb bustion exhaaust gases are now inn
operation oon the KCCC moving-beed system uusing RITE’s solid sorbents.

Acknowledgement
This projecct is supportted by Miniistry of Ecoonomy, Trad
de and Industry (METII), Japan.

Referencees
[1] J. Wangg et al. Enerrgy Environ Sci 7, 3478 (2014). [2] A. Samantaa et al. Ind E Eng Chem Res
R 51, 14388
(2012). [3] H. Yamadaa et al. Sep SciS Technol 50, 2948 (2 2015). [4] K.K Goto et all. Int J Greeenhouse Gass
Control 5, 1214 (2011). [5] H. Yamada et all. Int J Greeenhouse Gass Control 177, 99 (2013 3). [6] F. A..
Chowdhuryy et al. Ind Enng Chem Ress 52, 8323 (22013). [7] N.. Hiyoshi et al.
a Microporr Mesopor Mater
M 84, 3577
(2005). [8] H. Yamada et al. Ind En ng Chem Reses 49, 2449 (2010).
( [9] H.
H Yamada eet al. J Phys Chm A 115,,
3079 (2011)). [10] H. Yaamada et al. J Mol Modell 19, 4147 (22013). [11] H.H Yamada J Phys Chm B 120, 105633
(2016). [12]] H. Yamadaa et al. Fuel 214,
2 14 (201 8). [13] J. Fu ujikki et al. Chem
C Eng J 307, 273 (20017). [14] K..
Goto et al. A
Appl Energyy 111, 710 (22013). [15] P
P. Singh et all. Energy Pro ocedia 37, 20021 (2013). [16] H. Kim
m
& K. S. Leee Int J Greeenhouse Gass Control 47 , 291 (2016)). [17] M. L. Gray et al.. Energy Fueels 23, 48400
(2009). [18]] T. Okumurra et al. Enerrgy Procediaa 114, 2322 (2017).
( [19] R. Numagucchi et al. Eneergy Technoll
5, 1186 (2017).