April 2011, Volume 2, No.

2
International Journal of Chemical and Environmental Engineering

Evaluation of Physical Properties of Piperazine

(PZ), PZ Activated Aqueous 2-Amino-2-methyl-1-
propanol (AMP + PZ) for CO2 Removal from
Hydrocarbon Streams
Ghulam Murshid*, Azmi Mohd Shariff, Lau Kok Keong, Muhammad Azmi Bustam & Faizan Ahmad
Universiti Teknologi PETRONAS
Bandar Seri Iskandar
31750, Tronoh, Perak, Malaysia
* Corresponding author: hmurshid@gmail.com

Abstract
In the awake of global response for the protection of environment and sustainable development, the removal, disposal and useful
utilization of CO2 evolved from different sources is becoming a challenge with time. The coming years should find the carbon dioxide
(CO2) use in ever increasing number of applications (e.g. EOR). The major sources of CO2 emission include the burning of fossil fuel,
coal fired power plants, oil refining, hydrogen production, several industrial processes and sweetening of natural gas. There is a need
of developing new design and solvents for CO2 removal. In this paper physical properties, important in design the acid gas contactor
for new potential solvent are experimentally measured. The physical properties such as density (ρ), viscosity (η) and co-efficient of
thermal expansion (α) of aqueous solutions of Piperazine (PZ) and (AMP + PZ) were experimentally measured for a wide range of
temperature (298.15 to 33.15) K. The mass fractions of PZ were varied from (1.74 to 10.35) wt%. The concentrations for aqueous
solutions of (AMP+PZ) were kept higher due to the growing interest in use of concentrated amines in gas processing. The mass
fractions of (AMP + PZ) were varied from (28.26/1.74, 26.55/3.45, 23.12/6.88 to 19.65/10.35) %. All the properties were correlated as
a function of temperature. The measured and correlated values are found to be in good agreement. All measured physical properties
have shown the decreasing effect while increasing the temperature.

Keywords: Phenol biodegradation, Inhibition, Alcaligenes faecalis, Pure culture.

1. Introduction primary amines and therefore high removal of acid gases

Alkanolamines are being used for the removal of acid
gases such as carbon dioxide, (CO2) and hydrogen
sulphide (H2S) from the process of different industrial
gaseous streams through absorption process. The most
industrially used alkanolamines include; mono-
ethanolamine (MEA), di-ethanolamine (DEA), N-
methyldiethanolamine (MDEA) and 2-amino-2-methyl-1-
propanol (AMP) [1]. AMP belongs to a new class of
amines which is called sterically hindered amines. This
hindrance is caused by the presence of bulky group
adjacent to the amino group. Sterically hindered amine
(AMP) is the potential absorbent for CO2 removal with
relatively high CO2 loading, selectivity and efficient
regeneration due to unstable carbamate formation.[2-3]
To get the higher CO2 removal, low regeneration energy
and to cope with economic and environmental limitations
the blends of primary and tertiary amines or secondary
and tertiary amines are suggested [4,5]. These blends
combine the properties of higher absorption capacity of
tertiary amines with higher reaction rate of secondary or
can be achieved [6]. The use of an activator is also getting
significant attraction to enhance the absorption capacity
and rate of reaction. PZ is being used as an activator for
CO2 removal. PZ activated aqueous AMP system for CO2
removal has been studied by researchers in the recent
times [7,8]. Kinetic study shows that the introduction of
small amount of PZ to the aqueous solution of AMP
significantly increases the rate of absorption [9,10].
Therefore the Piperazine activated AMP solution could be
one of the potential solvent for the bulk removal of CO2
from the gaseous streams of industrial interests.
The knowledge of physical properties such as density,
viscosity and co-efficient of thermal expansion is
essential to design the absorption system for acid gas
removal. [11,12] Despite of the immense importance,
literature review shows [4, 11, 13-14] that this data of
AMP , PZ and aqueous solution of (AMP + PZ) is scarce
and limited to certain concentrations and temperatures.
Moreover, the co-efficient of thermal expansion values of
aqueous solution of PZ and aqueous solution of (AMP +
 PZ) are not available in the open literature. In this work,
the experimental density, viscosity and the derived
thermal property values of aqueous solutions of PZ and
aqueous solution of (AMP + PZ) reported at a wide range
of temperatures and concentrations to contribute the
existing absorbent properties. The surface tension and
refractive data is correlated as a function of temperature.
2. Materials and Methods
Piperazine with a purity of 99.9 % (GC, area %) and
AMP 95 % (GC area %) were purchased from Merck,
Malaysia and were used without further purification. The
bi-distilled water was used to prepare solutions. All the
solutions were prepared gravimetrically using an
analytical balance (Mettler Toledo AS120S) with a
measuring accuracy of ±0.0001 g. The total amine
concentrations were also experimentally determined by
titration with 0.5 M HCl using methyl orange indicator
and the concentrations were accurate with in ± 0.1 %.
2.1 Density
The densities of aqueous solutions of PZ and (AMP + PZ)
were measured using a digital vibrating glass U-tube
densitometer (DMA 5000, Anton Paar) with the
measuring accuracy of ± 0.000005 g.m-3. The density
meter was calibrated before and after each measurement
with water of Millipore quality. All the densities were
measured at a temperature range of (298.15 to 333.15) K
with a temperature controlled accuracy of ±0.01 K (PT
100). The reported densities were measured after
achieving thermal equilibrium and the equipment was set
to slow mode for better accuracy. Each reported data is
the average of at least three data points. The experimental
uncertainty of measured density was estimated
± 5. 10-6 g . cm-3
2.2 Viscosity
The viscosities of aqueous solutions were measured using
a calibrated Ubbelohde viscometer of sizes. The
viscometer containing amine solutions was immersed in
thermostatic bath (Tamson, TVB445) with built in stirring
system with temperature controlled accuracy of ± 0.01 K.
The bath temperature was regulated with Pt-100
temperature probe. The kinematic viscosities were
calculated by multiplying the efflux time with the
viscometer constant with the following 1
  Ct (1)
Where υ is the kinematic viscosity in centistokes (cSt), C
is the viscometer constant (cSt . s-1) and t is the efflux
time in seconds (s). The dynamic viscosities of the
aqueous amine solutions were calculated by multiplying
the corresponding densities with the measured kinematic
viscosities with an uncertainty of ± 0.028 mPa. S.
109
2.3 Co-efficient of Thermal Expansion
The co-efficient of thermal expansion is a derived thermal
property form the measured density data of the aqueous
solutions of PZ and (AMP + PZ). The co-efficient of
thermal expansion values are used to set the feasible
temperature of the acid gas absorber. The following
correlation is used to calculate these co-efficients 2.
 p  1 /  ( / T ) p   A1 /( A0  T ) (2)
Where αp is the co-efficient of thermal expansion, ρ is the
density of aqueous solutions, Ao, A1 are the fitting
parameters and T is the temperature in K.
3. Results and Discussion
The experimentally measured physical property
density, and viscosity values of aqueous PZ are presented
in Table 1. The measured values for PZ activated aqueous
amine solution (AMP + PZ) are presented in Table 2. The
data is also plotted as a function temperature and
presented from Fig 1 to Fig 4. It can be observed from the
Fig 1 to Fig. 4 that all the measured properties decrease
with increasing temperature. However, density and
viscosity of PZ and activated (AMP + PZ) values increase
by the addition of both PZ and AMP to the aqueous
solutions. The co-efficient of thermal expansion is
presented in Table 3. It can be observed from Table 3 that
this thermal property is independent of the temperature.
The density and viscosity data were correlated as function
of temperature as per following 3 x 4.
Z  Ao  A1 / T (3)
log( )  Ao  A1 / T (4)
Where Z is density and η is the viscosity, Ao, A1 are the
fitting parameters and T is the temperature in K. These
parameters were calculated using the method of least
square. These parameters for density are tabulated in table
4.
 Table 1. Physical Properties of Aqueous Solutions of Piperazine (PZ)
Aqueous PZ (Wt %)
-3
Density (g/cm ) Viscosity (mPa.S)
T 1.74 3.45 6.88 10.35 1.74 3.45 6.88 10.35
298.15 0.99775 0.99852 1.00018 1.00223 0.87 0.94 1.08 1.29
303.15 0.99637 0.99708 0.99869 1.00064 0.78 0.85 0.96 1.18
308.15 0.99474 0.99543 0.99697 0.99884 0.71 0.75 0.86 1.04
313.15 0.99291 0.99359 0.99507 0.99686 0.64 0.69 0.78 0.90
318.15 0.99090 0.99156 0.99299 0.99473 0.59 0.63 0.71 0.84
323.15 0.98872 0.98935 0.99074 0.99239 0.54 0.57 0.65 0.78
328.15 0.98637 0.98698 0.98833 0.98992 0.50 0.52 0.58 0.68
333.15 0.98383 0.98446 0.98577 0.98730 0.46 0.48 0.54 0.62
Table 2. Physical Properties of Aqueous Solutions of 2-Amino-2-methyl-1- propanol & Piperazine (PZ) (AMP + PZ)
Aqueous AMP/PZ (Wt %)
Density (g/cm-3) Viscosity (mPa.S)
T 28.26/1.74 26.55/3.45 23.12/6.88 19.65/10.35 28.26/1.74 26.55/3.45 23.12/6.88 19.65/10.35
298.15 0.99815 0.99948 1.00229 1.00488 3.24 3.33 3.46 4.12
303.15 0.99537 0.99671 0.99954 1.00217 2.74 2.75 2.89 3.68
308.15 0.99246 0.99381 0.99666 0.99932 2.31 2.33 2.42 3.25
313.15 0.98944 0.99080 0.99366 0.99637 1.96 2.01 2.07 2.89
318.15 0.98631 0.98768 0.99056 0.99330 1.65 1.75 1.80 2.55
323.15 0.98308 0.98446 0.98735 0.99012 1.42 1.51 1.57 2.19
328.15 0.97975 0.98113 0.98404 0.98678 1.29 1.35 1.36 1.88
333.15 0.97631 0.97770 0.98062 0.98343 1.16 1.18 1.23 1.61
Table 3. Co-efficient of Thermal Expansion of Aqueous Solutions of PZ and (AMP + PZ)
-4/ -1
αp. 10 K
PZ (AMP+PZ)
T 1.74 3.45 6.88 10.35 28.26/1.74 26.55/3.45 23.12/6.88 19.65/10.35
298.15 3.96 3.96 5.10 5.03 5.81 5.81 5.80 5.80
303.15 3.97 3.96 5.11 5.05 5.81 5.81 5.80 5.80
308.15 3.98 3.97 5.12 5.06 5.81 5.81 5.80 5.80
313.15 3.99 3.98 5.13 5.07 5.81 5.81 5.80 5.80
318.15 4.00 3.99 5.15 5.08 5.81 5.81 5.80 5.80
323.15 4.00 4.00 5.16 5.10 5.81 5.81 5.80 5.80
328.15 4.01 4.00 5.17 5.11 5.81 5.81 5.80 5.80
333.15 4.02 4.01 5.19 5.12 5.81 5.81 5.80 5.80

Table 4. Fitting Parameters of Eq. 1 to Calculate Co-efficient of Thermal Expansion

PZ (AMP+PZ)
1.74 3.45 6.88 10.35 28.26/1.74 26.55/3.45 23.12/6.88 19.65/10.35

A0 1.1282 1.1304 1.1355 1.1424 1.2042 1.205 1.2068 1.2075

A1 -0.0004 -0.0004 -0.0005 -0.0005 -0.0007 -0.0007 -0.0007 -0.0007

110

Fig 1. Density of aqueous PZ at various compositions of PZ from
298.15 K to 333.15 K
Fig 2. Viscosity of aqueous PZ at various compositions of PZ from
298.15 K to 333.15 K
T (K)
Fig 3. Density of aqueous (AMP +PZ) at various compositions of PZ
& AMP from 298.15 K to 333.15 K
111
Fig 4. Viscosity of aqueous (AMP +PZ) at various compositions of
PZ & AMP from 298.15 K to 333.15 K
4. Conclusion
Physical properties like density and viscosity of aqueous
solutions of PZ and aqueous solutions of (AMP + PZ)
were measured over the entire range of temperature
(298.15 to 333.15) K. The measured and correlated values
are in good agreement. Both the physical properties have
shown the decreasing effect while increasing the
temperature. The values of co-efficient of thermal
expansion were derived from the density data and all the
co-efficients of the studied systems are found to be
independent of temperature. This physical and thermal
property data will be helpful in better designing of acid
gas removal system
ACKNOWLEDGEMENT
The authors would like to thank CO2 absorption research
group & Universiti Teknologi PETRONAS for providing
funding and research facilities to conduct the research work
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