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mppatilmayur1679Korean J. Chem. Eng.
, 36(7), 1090-1101 (2019) pISSN: 0256-1115
DOI: 10.1007/s11814-019-0296-9 eISSN: 1975-7220
INVITED REVIEW PAPER INVITED REVIEW PAPER
Kinetic effect and absorption performance of piperazine activator into aqueous
solutions of 2-amino-2-methyl-1-propanol through post-combustion CO2 capture
Anoar Ali Khan*,†, Gopinath Halder**,†, and Asit Kumar Saha***
*Department of Chemical Engineering, Vignan’s Foundation for Science, Technology and Research,
Andhra Pradesh-522213, India
**Department of Chemical Engineering, National Institute of Technology Durgapur-713209, India
***Department of Chemical Engineering, Haldia Institute of Technology, Haldia-721657, India
(Received 16 February 2019 • accepted 9 May 2019)
AbstractThe current study investigates the absorption kinetics of carbon dioxide (CO2) released from power plant
exhaust using activated mixture of 2-amino-2-methyl-1-propanol (AMP) upgraded by piperazine (PZ). An absorption
experiment of (AMP+PZ+H2O) was conducted in a wetted wall column absorber with a temperature variation of 298-
313 K and CO2 partial pressure of 5-15 kPa. PZ is considered to be a rate promoter by adjustable mass proportion
varying from 2 to 10 wt%, while the concentration of entire amine solution remained constant at 30 wt%. Based on the
Zwitterions mechanism, an overall reaction pattern of (AMP+PZ+H2O) with CO2 was designed. Considering pseudo-
first order reaction criteria, the kinetic rate factors and the overall second order rate constants were calculated. The
overall rate constant (kOV) experienced a significant enhancement with a small addition of PZ into aqueous AMP solu-
tion. The observed second-order rate constants (k2, PZ) in this experimental study were 60,403, 81,925, 98,591 and
116,521 m3 ·kmol1 ·s 1 at 298, 303, 308 and 313 K correspondingly. The experimental specific rate of absorption into
(AMP+PZ+H2O) in connection with the model anticipated rate was determined with deviation of around 4.86% aver-
age absolute deviation (AAD).
Keywords: CO2 Capture, Absorption, Kinetics, (AMP+PZ+H2O), Flue Gas
INTRODUCTION di-isopropanolamine (DIPA), N-methyldiethanolamine (MDEA),
tri-ethanolamine (TEA), 2-amino-2-methyl-1-propanol (AMP) are
Gradual escalation of anthropogenic CO2 emissions around the the widest range of industrially accepted chemical absorbents for
world from different point sources is having the largest impact arresting the CO2 from industrial flue gas [6-9]. Remarkably, there
towards global warming. The present situation demands dedicated is no distinct solvent available which possesses entire excellent fea-
efforts of researchers and scientists throughout the world to com- tures for CO2 capture through absorption method. Consequently,
bat the hostile effects of global warming. The most recent report of significant investigations are headed for advancement of suitable
CO2 intensity worldwide substantiates a continuous rise of 408.50 solvent owing to the features of elevated rate kinetics and higher CO2
ppm as of November 23, 2018, which is highly associated with 316 loading capacity with advantage of reduced energy demand for sol-
ppm on the year 1958 [1]. Based on the assessment of the Inter- vent regeneration and lesser operational expenses. The main ob-
governmental Panel on Climate Change report, the worldwide aver- jective of this study was the selection of an optimum solvent blend
age surface temperature has increased progressively from 1.4 to 5.8 oC with good physico-chemical properties: high CO2 loading capaci-
from 1990 to 2100 [2]. The reduction of CO2 emissions has received ties, low vapor pressure, reasonable viscosity, thermal and chemi-
significant attention and one of the most obvious pathways for CO2 cal stability and higher rate kinetics of absorption. The basics of
capture, utilization and storage (CCUS) from coal-fired power plant solvent blend are the combination of appreciative qualities of dif-
exhaust gases along with the improvement of global climate in view ferent single amines, for instance, the advantage of superior CO2
of stabilizing the concentration of atmospheric CO2 towards im- loading capacity of tertiary amines as well as benefit of moderately
provement of global climate [3]. The most efficient and economi- reduced energy needed for solvent regeneration along with faster
cal technique for CO2 capture is the well-established chemical sorp- reaction rate kinetics of primary or/and secondary amines [10-18].
tion using aqueous amine solutions, since it has superiority in In recent days, there has been attention towards reaction rate pro-
selective capture performance of CO2 coming out from industrial moted amine solution through a reaction rate accelerator, e.g., PZ
exhaust comprising relatively higher volume and low CO2 partial (piperazine). PZ promoted aqueous AMP solution for CO2 absorp-
pressure [4,5] Monoethanolamine (MEA), diethanolamine (DEA), tion acquires advantages of higher rate of reaction of CO2 with PZ
and also with the superior CO2 loading capacity [19-22]. Nowa-
†
To whom correspondence should be addressed. days, accomplishing higher overall reaction rate kinetics for CO2
E-mail: gopinathhaldar@gmail.com, anoaralikhan@gmail.com capture and considerably lesser regeneration energy requirement
Copyright by The Korean Institute of Chemical Engineers. employing activated solvent blend such as piperazine (PZ) activated
1090
Absorption performance of CO2 into piperazine activated 2-amino-2-methyl-1-propanol 1091
AMP or MDEA for CO2 removal by absorption technique has been ferent mass percentage combination of. 28/2, 25/5, 22/8 and 20/10
a subject of paramount interest. Gordesli et al. investigated the mix- of (AMP+PZ) was considered as activated absorbent possessing
ing effect of activating agent PZ into sterically-hindered amines an overall concentration of 30 wt% in blended solution, and ab-
AMP and tertiary amines MDEA [23]. They experienced that addi- sorption study was carried out in a wetted wall column. Physical
tion of PZ enhances the rate of reaction prominently in case of solubility and diffusivity of all individual (AMP+PZ) blends were
AMP and a higher equilibrium CO2 loading capacity achieved for evaluated using N2O analogy. Here, kinetics of CO2 absorption into
activated MDEA. The improved performance related to solvent (AMP+PZ+H2O) are described and the various kinetic parameters
blend is due to a sterically hindered structure where unstable car- determined on the basis of pseudo-first-order reaction specifica-
bamate formation leads to free amine generation, which enhances tion from observed experimental rate at each parametric situation.
the CO2 absorption performance along with a drawback of rela-
tively slower reaction rate. In addition of a reaction rate promoter, THEORETICAL BACKGROUND
i.e., piperazine (PZ) possessing very fast reaction kinetics within
the aqueous solution of AMP could compensate this shortcoming 1. Reaction Scheme
of AMP alone [24]. Gordesli et al. informed that the pseudo-first- When CO2 gas is dissolved into the aqueous mixture of (AMP+
order rate constant of CO2 into (AMP+PZ+H2O) is relatively very PZ), many reversible reaction stages are observed to proceed through
high as compared to each individual amine and considerably higher the absorption method. The reactions of CO2- (AMP+PZ+H2O)
than that of conventional monoethanolamine (MEA) for CO2 cap- schemes are described in our previous work [27] as suggested by [26].
ture [23]. In the activated MDEA process of BASF, PZ is treated as 2. Reaction Procedure
a rate accelerator during absorption of CO2 as described by [25], In case of AMP, which is sterically hindered in nature, the im-
and it is conveyed that PZ acts as an impressive rate accelerator portant reaction with CO2 is proposed to be hydration of CO2 which
than the conventional one [19]. Dash et al. found that addition of is catalyzed by AMP and the CO2 molecule is transformed into
small quantities of PZ into aqueous solution of AMP, e.g., (28 wt% bicarbonate ion. In this case, stability of carbamate formation is very
AMP+2 wt% PZ), considerably enhances the rate of CO2 absorp- less and the formation of carbamate is insignificant. Therefore, it
tion and also the enhancement factor during the absorption pro- can be ignored as well.
cess [26]. Although the activated solutions like (AMP+PZ+H2O) The probable reaction procedure associated with CO2 and PZ
and (MDEA+PZ+H2O) offer very efficient CO2 removal charac- consists of two steps: the construction of a complex chemical termed
teristics through absorption process, yet literature on CO2 capture as zwitterion (CO2, PZ and PZCOO ); after that, the base cata-
using such solutions is very scant. Hence, the present research work lyzed deprotonation of this zwitterion through a base (AMP, PZ
was performed to contribute some knowledge to this area. and PZCOO ) to generate PZ-monocarbamate, PZ-dicarbamate
In the current study, the absorption characteristics of CO2 into and protonated base [28-30]. The Zwitterion mechanism was ini-
aqueous amine blend were performed considering a temperature tially suggested by Caplow [31] and re-established by Danckwerts
range of 298-313 K and CO2 partial pressure of 5-15 kPa. The rate [32]. It states that the deprotonation of zwitterions can take place
of specific absorption over (AMP+PZ+H2O) along with different through some base existing in the solution. The reaction between
solvent characteristics--density, viscosity, physical solubility and dif- CO2 and PZ is enhanced catalytically due to the existence of notice-
fusivity of CO2 of this blended solvent--was determined. Four dif- ably more AMP concentration in (AMP+PZ+H2O) solution. The