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Energy Procedia 37 (2013) 417 – 422
GHGT-11
Novel hindered amine absorbent for CO2 capture
Shinji Muraia*, Yasuhiro Katoa, Yukishige Maezawaa, Takehiko Muramatsua,
Satoshi Saitob
a
Toshiba Corporation, 1, Toshiba-cho, Fuchu-Shi, Tokyo, Japan
b
Toshiba Corporation, 2-4, Suehiro-cho, Tsurumi-ku, Yokohama-shi, Kanagawa, Japan
Abstract
We synthesized the sterically hindered amine A by an appropriate placement of alkyl groups. Quantitative
13
C NMR spectroscopy was performed on 30 wt% aqueous solution of the amine A with different amount
of CO2 at 40°C. The results suggested that the amine A only formed the carbonate anion in this system.
Performance evaluations of the absorbent-A containing the amine A were carried out based on their CO2
absorption rate, absorption capacity and heat of reaction measurements. The absorbent-A containing the
amine A showed high absorption capacity and high absorption rate and relative low heat of reaction
compared to 30 wt% MEA solution. The absorbent-A has been selected for further tests in the bench-
scale apparatus. We will evaluate the absorbent-A at Mikawa pilot plant (10 ton/day) owned by
TOSHIBA, using the actual flue gas from Mikawa coal fired power plant in Fukuoka prefecture, Japan.
© 2013
© 2013 The
The Authors.
Authors. Published
Published by
by Elsevier
ElsevierLtd.
Ltd.
Selection and/or
Selection and/or peer-review
peer-review under
under responsibility
responsibilityof
ofGHGT
GHGT
Keywords: carbon dioxide; absorption; loading; 13C NMR; sterically hindered amine; carbamate; carbonate
1. Introduction
In recent years, a greenhouse effect resulting from an increase of CO2 concentration has been pointed
out as a cause of global warming phenomena. Chemical absorption using an aqueous solution of amine
based absorbents is one of the most effective methods to capture CO2 [1]. So, it is essential to reduce the
absorbent regeneration cost by developing novel amine based absorbents because half of the capture cost
is caused by absorbent regeneration. In the previous studies, commercially available amine based
absorbents were widely investigated all over the world on terms of absorption capacity and heat of
reaction of CO2 and so on. A study on particularly alkanolamine having structural steric hindrance was
vigorously tried as the absorbent of acid gas [2, 3]. Alkanolamine having the steric hindrance has merits
that selectivity of acid gas is very high and the energy required for regeneration is small. Then, we
* Corresponding author. Tel.: +81-42-333-2780; fax: +81-42-340-8060.
E-mail address:
[email protected].
1876-6102 © 2013 The Authors. Published by Elsevier Ltd.
Selection and/or peer-review under responsibility of GHGT
doi:10.1016/j.egypro.2013.05.126
418 Shinji Murai et al. / Energy Procedia 37 (2013) 417 – 422
focused on the development of hindered amine based CO2 absorbents that have a low heat of reaction and
high capacity for CO2. We synthesized the new hindered amine (amine A) and the results for the amine A
was then compared with those of the conventional absorbents such as monoethanolamine (MEA), N-
methylethanolamine (MAE), N-isopropylethanolamine (IPAE) to analyse the steric effect of the different
substituents on the relative reactivity of the amino nitrogen. For the development of new absorbent we
thus focused on the absorbents that outperformed MEA in screening tests. The objective of solvent
screening test is to deriver the candidate for further and more detailed test in a bench-scale apparatus and
finally in Mikawa pilot plant.
2. Experimental
2.1 Chemicals
All the amines except the amine A were purchased from Tokyo Chemical Industry Co., Ltd. and
Wako Pure Chemical Industries, Ltd. and were used without further purification. The amine A was
synthesised in our laboratory by the reductive amination [4]. The purity and structure of the amine A was
established by GC and NMR spectroscopy, respectively.
3. Results and discussion
3.1 CO2 absorption properties
To clarify the steric effect of the different substituents on the relative reactivity, the absorption
capacity and the absorption rate were determined for each amine. Absorption performance was evaluated
by measuring the CO2 concentration in the gas at an exit of the test tube by using an infrared gas
concentration measurement device (manufactured by Shimadzu Corporation, name of article: “CGT-
700”). Figure 1 illustrates the experimental system for the CO2 absorption properties. A Teflon tube
(inside diameter: 1.59 mm, outside diameter: 3.17 mm) of 1/8 inches was set at a gas introducing port to
the amine solution in the test tube. A water solution of 50 ml (hereinafter, referred to as an absorbing
liquid) was prepared by dissolving 30 mass % of each amine in water. After this absorbing liquid was
filled in a test tube and heated to 40°C , mixed gas containing 10 vol% CO2 and 90vol% N2 gas was
aerated at a flow rate of 500 mL/min. The CO2 concentration in the absorbing liquid was measured by
using the infrared gas concentration measurement device to evaluate absorption performance. The
equilibrium was determined when the CO2 analyzer indicated a constant CO2 concentration in the outlet
gas. An absorption rate is obtained by differentiating the absorption capacity with respect to the
absorption time.
mass flow
mass flow meter CO2
sensor
controller
Dimroth condenser
CO2
in
N2
heater
100m䌌 water bath
test tube
magnetic
stirrer
Figure 1. Illustration of laboratory experimental system
Shinji Murai et al. / Energy Procedia 37 (2013) 417 – 422 419
㪇㪅㪇㪈㪇
㪘㪹㫊㫆㫉㫇㫋㫀㫆㫅㩷㫉㪸㫋㪼㩷㩿㫄㫆㫃㪆㫄㫆㫃㪆㫄㫀㫅㪀
㪇㪅㪇㪇㪏
㪇㪅㪇㪇㪍
㪇㪅㪇㪇㪋
㪇㪅㪇㪇㪉
㪇㪅㪇㪇㪇
㪇 㪇㪅㪉 㪇㪅㪋 㪇㪅㪍 㪇㪅㪏
㪣㫆㪸㪻㫀㫅㪾㩷㩿㫄㫆㫃㪆㫄㫆㫃㪀
Amine A IPAE MAE MEA
Figure 2. Absorption rate versus amount of CO2 absorbed at 40°C
Figure 2 demonstrates that the result of saturated CO2 loading and absorption rates of MEA, MAE,
IPAE and amine A at 40°C, respectively. Figure1 clearly shows that the absorption rates of MAE, IPAE,
the amine A are higher than that of MEA. It is observed that the rate for amine A was slightly higher than
IPAE. The amine A shows a good CO2 absorption capacity as IPAE. These results provided clear trends
on the structural effects of alkanolamine. Methyl group was found to be suitable functional group for the
enhancement of initial absorption rate, but decreased CO2 capacity [5]. An increase in steric hindrance
for alkyl groups mostly decreases the absorption rate but increases the capacity.
3.2 Quantitative 13C NMR
The quantitative 13C NMR provides speciation information and is useful in the calculation of the mole
percentage of each species relative to the total amine concentration [6, 7]. 13C NMR spectral was obtained
using a JEOL GSX-270 with a capillary sealed DMSO-d6 as an external standard at 25°C. To obtain
quantitative spectra, the inverse gate decoupling technique was used with a delay of 30 s, a pulse width of
8.4Ǵs. The samples containing different amount of dissolved CO2 in 30 wt㧑 aqueous amine are
prepared by changing the absorption time. The absorption of CO2 at 40°C clearly shows their speciation
through 13CNMR spectra. Due to the fast exchange of protons, it was not possible to distinguish signals
of carbonate anion and bicarbonate anion, and signals of unprotonated and protonated amines from NMR
spectra [8]. The results are shown in Figure 3. MEA only formed the carbamate anion at lower CO2 molar
loading and then converted partially to bicarbonate anion. In MAE, MAE also formed the carbamate
anion and this intermediate converted to bicarbonate anion faster than MEA. The amount of the
carbamate anion is almost the same as that of the carbonate anion. In IPAE, IPAE mainly formed the
carbonate anion with a slight amount of carbamate anion during the CO2 absorption. In amine A, the
amount of the carbonate anion increased with the increase in the loading from 0 to 0.75 mol CO2/mol CO2
and no carbamate anion was observed in the solution even at loading of 0.75 mol CO2/mol CO2.
420 Shinji Murai et al. / Energy Procedia 37 (2013) 417 – 422
㪈㪅㪇 㪈㪅㪇
MEA MAE
㪇㪅㪏 㪇㪅㪏
㪚㪦㪉㩷㫄㫆㫃䋦
㪚㪦㪉㩷㫄㫆㫃䋦
㪇㪅㪍 㪇㪅㪍
㪇㪅㪋 㪇㪅㪋
㪇㪅㪉 㪇㪅㪉
㪇㪅㪇 㪇㪅㪇
㪇 㪇㪅㪉 㪇㪅㪋 㪇㪅㪍 㪇㪅㪏 㪇 㪇㪅㪉 㪇㪅㪋 㪇㪅㪍 㪇㪅㪏
㪚㪦㪉㩷㪣㫆㪸㪻㫀㫅㪾㩷㩿㫄㫆㫃㪆㫄㫆㫃㪀 㪚㪦㪉㩷㪣㫆㪸㪻㫀㫅㪾㩷㩿㫄㫆㫃㪆㫄㫆㫃㪀
㪈㪅㪇 㪈㪅㪇
IPAE Amine A
㪇㪅㪏 㪇㪅㪏
㪚㪦㪉㩷㫄㫆㫃䋦
㪚㪦㪉㩷㫄㫆㫃䋦
㪇㪅㪍 㪇㪅㪍
㪇㪅㪋 㪇㪅㪋
㪇㪅㪉 㪇㪅㪉
㪇㪅㪇 㪇㪅㪇
㪇 㪇㪅㪉 㪇㪅㪋 㪇㪅㪍 㪇㪅㪏 㪇 㪇㪅㪉 㪇㪅㪋 㪇㪅㪍 㪇㪅㪏
㪚㪦㪉㩷㪣㫆㪸㪻㫀㫅㪾㩷㩿㫄㫆㫃㪆㫄㫆㫃㪀 㪚㪦㪉㩷㪣㫆㪸㪻㫀㫅㪾㩷㩿㫄㫆㫃㪆㫄㫆㫃㪀
carbonate carbamate free amine
Figure 3. Plots of mole ratio of chemical species as a function of CO2 loading
3. 3 Vapor-liquid equilibrium
As the amine A showed
superior performance in the 㪇㪅㪇㪋
screening test, the absorbent-
A containing amine
㪇㪅㪇㪊
㪘㪹㫊㫆㫉㫇㫋㫀㫆㫅㩷㫉㪸㫋㪼
A was further investigated by
㩿㫄㫆㫃㪆㫄㫆㫃㪆㫄㫀㫅㪀
measuring their vapour-liquid
equilibrium along with both
absorbent-B containing IPAE
㪇㪅㪇㪉
and 30 wt% MEA solution.
Absorption performance at 㪇㪅㪇㪈
40°C was conducted in a
similar manner as above.
Besides, the absorbent after 㪇㪅㪇㪇
the mixed gas was absorbed at 㪇 㪇㪅㪉 㪇㪅㪋 㪇㪅㪍 㪇㪅㪏
40°C as stated above was
heated to 120°C, 10 vol% CO2 㪣㫆㪸㪻㫀㫅㪾㩷㩿㫄㫆㫃㪆㫄㫆㫃㪀
and 90 vol% N2 was aerated at a Absorbent-A Absorbent-B MEA
flow rate of 100mL/min, and the
CO2 concentration in the Figure 4. Absorption rate versus amount of CO2 absorbed at 40°C
Shinji Murai et al. / Energy Procedia 37 (2013) 417 – 422 421
absorbing liquid was measured by using the infrared gasconcentration measurement device to evaluate
release performance. These temperatures are regarded as typical conditions for the chemical process.
The absorption rates versus loading curves for three absorbents are shown in Figure 4. Figure 4
clearly shows that the absorption rates of absorbent-A and absorbent-B are much higher than that of 30
wt% MEA solution. Absorbent-A showed a similar behaviour to absorbent-B. The absorption rate of
absorbent-A is almost the same as that of absorbent-B and the absorbent-A shows a good CO2 absorption
capacity along with the absorbent-B.
Table 1. Experimental results for vapour-liquid equilibrium
㪘㫄㫀㫅㪼㩷㪘㪹㫊㫆㫉㪹㪼㫅㫋㫊 㪣㫆㪸㪻㫀㫅㪾㪸 㪣㫆㪸㪻㫀㫅㪾㪹 㪚㫐㪺㫃㫀㪺㩷㪚㪸㫇㪸㪺㫀㫋㫐㪺
㫄㫆㫃㪆㫄㫆㫃 㫄㫆㫃㪆㫄㫆㫃 㫄㫆㫃㪆㫄㫆㫃
㪘㪹㫊㫆㫉㪹㪼㫅㫋㪄㪘 㪇㪅㪍㪈 㪇㪅㪈㪈 㪇㪅㪌㪇
㪘㪹㫊㫆㫉㪹㪼㫅㫋㪄㪙 㪇㪅㪍㪉 㪇㪅㪇㪍 㪇㪅㪌㪍
㪤㪜㪘㩷㪊㪇㫎㫋䋦㩷㫊㫆㫃㫌㫋㫀㫆㫅 㪇㪅㪌㪍 㪇㪅㪉㪈 㪇㪅㪊㪌
a b
Maximum CO2 loading at 40°C, Maximum CO2 loading at 120°C,
c
Difference of CO2 loading between 40°C and 120°C
The results in table 1 show the summary of vapour liquid equilibrium characteristics for absorbent-A
and absorbent-B and 30 wt% MEA solution. Both absorbent-A and absorbent-B have the large cyclic
capacity compared with 30 wt% MEA solution. The cyclic capacity of the absorbent-A has 1.4 times that
of 30 wt% MEA solution.
3.4 Heat of reaction
Heat of reaction of the CO2 absorption for both the absorbent-A and 30 wt% MEA solution was
measured with a differential reaction calorimeter “DRC” (product name, manufactured by SETRAM
Company) composed of a glass reaction vessel and a reference vessel with the same shape installed in a
thermostatic oven. The reaction vessel and the reference vessel were each filled with a 100 mL absorbing
liquid, and 40°C constant-temperature water was circulated in jacket portions of the vessels. In this state,
CO2 gas with a 50% concentration was blown to the absorbing liquid in the reaction vessel at a flow rate
of 200 mL/min, a temperature increase of the liquid was continuously recorded by a thermograph until the
CO2 absorption was finished, and the heat of reaction was calculated by using an overall heat transfer
coefficient between the reaction vessel and the jacket water which was measured in advance.
The heat of reaction for absorbent-A is smaller than that of MEA solution. The heat of reaction of the
CO2 absorption for 30 wt% MEA solution and absorbent-A is 70.5 kJ/mol and 64.0 kJ/mol, respectively.
In general, amine absorptions with higher absorption rates usually show higher heat of reaction, but
absorbent-A has properties opposite to the 30 wt% MEA solution.
4. Conclusion
We synthesized the amine A with specific steric hindrance substituent and it formed only carbonate
anion in the CO2 loaded aqueous solution. It was proved that the amine A had a unique characteristic
different from other amines in terms of CO2 chemical species by quantitative 13C NMR spectroscopy. The
absorption rates of MAE, IPAE, the amine A were higher than that of MEA. The rate for amine A was
slightly higher than IPAE. The amine A showed a good CO2 absorption capacity as IPAE. The absorbent
422 Shinji Murai et al. / Energy Procedia 37 (2013) 417 – 422
containing the amine A showed higher absorption capacity and relative lower heat of reaction compared
to 30 wt% MEA solution. As a result of the screening test for the absorbents, the absorbent-A has been
selected for further tests in the bench-scale apparatus. We will evaluate the absorbent-A at Mikawa pilot
plant (10 ton/day) owned by TOSHIBA using the actual flue gas from Mikawa coal fired power plant in
Fukuoka prefecture, Japan [9]. Higher CO2 absorption capacity and relative lower heat of reaction
characteristics will reduce the regeneration energy.
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[2] Sartori, Guido; Savage, David W. Sterically hindered amines for carbon dioxide removal from gases.
Industrial 㧒 Engineering Chemistry Fundamentals, 1983, 22(2), 239-249
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