Energy

Energy Procedia 4 (2011) 519–524 Procedia

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Energy Procedia 00 (2010) 000–000
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GHGT-10

Experimental studies on removal capacity of carbon dioxide by a

packed reactor and a spray column using aqueous ammonia
Zeng Qing, Guo Yincheng *, Niu Zhenqi 1

Department of Engineering Mechanics, School of Aerospace

Tsinghua University, Beijing 100084, China
Elsevier use only: Received date here; revised date here; accepted date here

Abstract

The absorption of carbon dioxide into ammonia aqueous solution using packed reactor and spray column was investigated. The
removal efficiencies were evaluated over ranges of main operating variables, including CO2 inlet concentration, gas flow rate,
liquid flow rate, concentration of ammonia and temperature. Experimental results showed that the suitable reaction temperatures
are 40ć and 35ć for spray column and packed reactor respectively, and the mole ratio of NH3 to CO2 is a key parameter and
plays an important role on CO2 removal efficiency. Compared with the absorption of CO2 in the spray column, the CO2 removal
efficiency in the packed reactor shows superior performance.
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2011 Elsevier
PublishedLtd.
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Open access under CC BY-NC-ND license.

Keywords: Carbon dioxide; aqueous ammonia; removal efficiency; packed reactor; spray column

1. Introduction

It is well known that carbon dioxide is the major greenhouse gas of which emission should be reduced. Chemical
absorption process is generally recognized as the most effective technology, and the monoethanolamine (MEA)
scrubbing is widely used in the chemical engineering process of carbon dioxide capture [1, 2]. However, the MEA
process suffers the following disadvantages [3], such as low CO2 loading capacity, high equipment corrosion rate,
amine degradation by SO2, NO2, HCl and O2 in the flue gas, high energy consumption during absorption and
regeneration.
Some researchers found that ammonia seems to be an alternative and promising absorbent for removing CO2
from flue gas [4-9]. The absorbent of aqua ammonia is not easy to be degraded and the energy input is much lower
than MEA process, and the solution does not have a corrosion problem. Three major acid gases, SO2, NO2 and CO2,
will be captured in the aqua ammonia process, which is expected to reduce the total cost and complexity of emission
control systems [9]. Bai et al. [4, 6] carried out experimental investigations of the ammonia and MEA capturing CO2 in
a bubble reactor. The tests showed that the ammonia is superior to MEA absorbent in its capacity to absorb and
removal CO2 from flue gas systems. Yeh et al. [10] performed CO2 absorption and regeneration with aqueous

* Corresponding author. Tel.: +86-10-62772112-802; fax: +86-10-62781824.

E-mail address: guoyc@tsinghua.edu.cn.

doi:10.1016/j.egypro.2011.01.083
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ammonia in a semi-continuous flow reactor. It was found that the energy requirement for the regeneration of NH3
was less than that for the regeneration of MEA reagent. Diao et al. [11] studied the mechanism and kinetics of the
reaction between CO2 and NH3 solvent in a sieve-plate tower. Their experiment results showed that the CO2 removal
efficiency reached the highest at 33ć. Niu et al. [12] studied the carbon dioxide absorption into ammonia using a
spray column, the experimental results showed that the ammonia concentration played a very important role, when
the ammonia concentration was 8%, the removal efficiency of carbon dioxide could realize to 98.4%.
In order to improve the carbon dioxide removal efficiency and reduce the cost, apart from choosing good
absorbing liquid, it is very important to select effective reactor and proper operating conditions. The absorption of
CO2 using packed reactor is a well-established technology being used widely in the chemical industrial. However,
packed reactor suffer from various operational problems including high gas phase pressure drop, liquid channelling
and flooding, disintegration of packing materials caused by high temperature gases, and deposition on packings and
clog up of void spaces by solid-laden gases [13]. Thus, many experimental studies focused on the development of
innovative configurations of scrubbing and stripping equipment. Kuntz et al. [14] compared the mass-transfer
efficiency of spray column and packed reactor for carbon dioxide absorption into MEA, the experimental results
showed that the spray column was capable of removing CO2 from gas stream at a higher rate than the packed
column.
In this work, the absorption of carbon dioxide into aqueous ammonia was carried out under various conditions to
reveal effects of process parameters, including CO2 inlet concentration, gas flow rate, liquid flow rate, concentration
of ammonia and temperature. And the removal capacity of CO2 in the packed reactor was compared to that in the
spray column.

2. Absorption experiment

The gas absorption experimental setup is shown in Figure1. The experiments were carried out in spray column
and packed reactor respectively. The packed reactor and the spray column were made of stainless steel with 100 mm
inner diameter and 500 mm height. In order to keep the reaction temperature, the experiments were carried out under
water bath conditions. The water bath was kept at constant temperature by the temperature controller and an electric
heater. And also, the aqueous ammonia solution and inlet artificial flue gas of CO2 and nitrogen mixture were kept
at the same temperature with the water bath. The mixture of CO 2 and nitrogen was fed into the packed reactor or the
spray column from its bottom.

outlet gas 7
6

Ammonia
solution
8 9
10
1.N2 Cylinder
2 5 2.CO2 Cylinder
3.Mass Flow Controller
4.Gas Heater
4 11 5.CO2 Absorber
6.CO2 Analyzer
7.Wire mesh demister
8.Liquid Heater
3 12 9.Liquid Flow Meter
10.Pump
11.Gas Distribution Plate
13 12.Constant Temperature Controller
13.Valve
14 14.Reservoir

Figure 1 Schematic diagram of experimental setup of CO2 and aqueous ammonia absorption
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For the spray column, the heated aqueous ammonia solution was sprayed into the column at its upper part. For
the packed reactor, the heated aqueous ammonia solution was injected into the packed reactor from its top to the
bottom. So, the CO2 gas and the aqueous ammonia solution were in counter flow pattern, it is beneficial to make
CO2 and aqueous ammonia contact and react thoroughly. As for the spray column reactor, the Sauter Mean
Diameters (SMD) of the aqueous ammonia spray were 30 m to 40 m when the pressure of the pump was 0.69
MPa to 1.11 MPa. In the packed reactor, the packing height of the reactor was 400 mm, and the filler of the packed
column was ceramic Rraschig ring with 8mm inner diameter.
Effects of different operating and design parameters on CO2 removal efficiency were investigated. Detailed
parameters in experiments are given in Table 1.

Table 1 Experimental parameters

Temperature, Ammonia flow Ammonia Total gas flow rate, CO2 inlet
ć rate, L/h concentration %, w/w L/min concentration, %, v/v

20~55 8 8 10 15

20 8~24 8 20 15

20 12 2~16 20 15

20 16 8 10~28 15

20 8 8 20 5~15

3. Results and discussions

The removal efficiency (  ) is determined from the difference between the amounts of CO2 entering and leaving
the column, which can be expressed as
Y Y
  1 2 100% , (1)
Y1
where Y1 and Y2 stand for the mole ratios of CO2 to N2 of the gas phase entering and leaving the absorption column
respectively. And the mole ratio of gas phase CO2, Y, can be expressed as
y
Y , (2)
1 y
where y is the mole fractions of gas phase CO2. Finally, the CO2 removal efficiency can be determined as follows
y1  y2
 100% , (3)
y1 (1  y2 )
where y1 and y2 present the mole fractions of gas phase CO2 entering and leaving the absorption column
respectively.

3.1. Effect of the operating temperature

Figure 2 shows the CO2 removal efficiency profile under different temperatures in the packed reactor and the
spray column. In these cases, the mass concentration of aqueous ammonia solution was 8%, the aqueous ammonia
flow rate was 8 L/h, the total gas flow rate was 10 L/min, and the concentration of CO2 at the inlet was 15%. With
the temperature increasing from 20ć to 40ć, experimental results showed that the CO2 removal efficiency
increased from 82.47% to 90.20% in the spray column. Whereas, when the temperature is higher than 40ć, the CO2
removal efficiency begins to decline. As for the packed reactor, the CO2 removal efficiency increased from 94.28%
to 97.72% when the temperature increasing from 20ć to 35ć, and the CO2 removal efficiency was reduced when
the temperature was higher than 35ć. The temperature plays an important role in diffusion and chemical reactions.
The diffusion rate increases when the temperature increasing, which gives rise to the acceleration the absorption
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process. However, the increase of the temperature also accelerates the decomposition of the reaction product of
ammonium bicarbonate, this gives rise to reduction of the absorption efficiency. Experimental results indicated that
the suitable reaction temperatures are 40ć and 35ć for spray column and packed reactor respectively. This
phenomenon can be attributed to that the reaction of CO2 absorption into ammonia aqueous is reversible, the
forward reactions are dominant at room temperature, the backward reactions occur at temperatures of around 38ć
~60ć [4,15].

100 100

CO2 removal efficiency, %

CO2 removal efficiency, %

90
95
80
90
70
85 60
50 packed reactor
80 packed reactor
40 spray column
spray column
75
30
70 20
20 25 30 35 40 45 50 55 6 8 10 12 14 16 18 20 22 24 26
Temperature,C Ammonia volume flow rate, L/h

Figure 2 Effect of temperature in the reactor Figure 3 Effect of ammonia volume flow rate
on CO2 removal efficiency on CO2 removal efficiency

3.2. Effect of the aqueous ammonia flow rate

The influence of aqueous ammonia solution flow rate on the CO2 removal efficiency was investigated. Figure 3
shows the CO2 removal efficiency profile at different aqueous ammonia solution flow rates. In these cases, the mass
concentration of aqueous ammonia solution was 8%, the total gas flow rate was 20 L/min, the concentration of CO2
at the inlet was 15%, and the temperature was 20ć. When the aqueous ammonia flow rate increasing from 8 L/h to
24 L/h, the CO2 removal efficiency increased from 66.38 % to 73.92% in the spray column. In the packed reactor,
the CO2 removal efficiency increased from 92.54% to 96.01% when the aqueous ammonia flow rate increasing from
8 L/h to 24 L/h.
With the aqueous ammonia flow rate increasing from 8 L/h to 24 L/h, the mole ratios of ammonia to carbon
dioxide increased from 4.6 to 13.8, this indicated that there would be more ammonia molecules can participate in the
reaction of CO2 absorption. Besides, the interfacial area per unit volume increases with increasing aqueous ammonia
flow rate, which is beneficial to enhance absorption ability.

3.3. Effect of the aqueous ammonia concentration

Figure 4 shows the CO2 removal efficiency profile under different concentrations of aqueous ammonia solution.
In these cases, the operating temperature was 20ć, the aqueous ammonia flow rate was 12 L/h, the total gas flow
rate was 20 L/min, and the concentration of CO2 at the inlet was 15%. In the spray column, the CO2 removal
efficiency increased from 38.43 % to 86.07% when the concentration of aqueous ammonia solution increasing from
2% to 16%. In the packed reactor, the CO2 removal efficiency increased rapidly from 52.73% to 94.28% when the
value of concentration of aqueous ammonia solution increasing from 2% to 8%. When the concentration of aqueous
ammonia solution was higher than 8%, the CO2 removal efficiency increased slightly. The CO2 removal efficiency
increased to 99.43% when the ammonia concentration was 16% in the packed reactor.
The mole ratios of ammonia to carbon dioxide increase with the ammonia concentration, this means that
increasing ammonia concentration yields a amount of the active ammonia available to diffuse toward the gas-liquid
interface and to react with CO2, this will promote the enhancement factor, which leads to a higher absorption rate.

3.4. Effect of the total gas flow rate

The effect of the total gas flow rate on the CO2 removal efficiency using aqueous ammonia solution is shown in
Figure 5. The operating temperature was 20ć, the aqueous ammonia flow rate was 16 L/h, the mass concentration
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of aqueous ammonia solution was 8%, and the concentration of CO2 at the inlet was 15%. With the total gas flow
rate increasing from 10 L/min to 28 L/min, experimental results showed that the CO2 removal efficiency decreased
from 98.29% to 91.37 % in packed column. In the spray reactor, the CO2 removal efficiency decreased from 86.07%
to 63.19%. The effect of the gas flow rate on the CO2 removal efficiency in the spray reactor is greater than that in
the packed column.
Increase in the gas flow rate leads to an increase of volumetric overall mass transfer coefficients which gives rise
to the absorption rate increasing. However, the mole ratios of ammonia to carbon dioxide decreases from 18.4 to 6.6
as the total gas flow rate increasing from 10 L/min to 28 L/min, this is the main reason of the reduction of removal
rate. Thus, the mole ratio of NH3 to CO2 flow rate is a key parameter and plays an important role on CO2 removal
efficiency.

100
100

CO2 removal efficiency , %

90
CO2 removal efficiency, %

90
80
80
70 70
60 60
50 50
40 40
30 packed reactor 30 packed reactor
20 spray column 20 spray column
10 10
0 0
0 2 4 6 8 10 12 14 16 18 8 10 12 14 16 18 20 22 24 26 28 30
Ammonia concentration, % Gas flow rate, L/min

Figure 4 Effect of ammonia concentration Figure 5 Effect of total gas flow rate
on CO2 removal efficiency on CO2 removal efficiency

3.5. Effect of the inlet concentration of carbon dioxide

The influence of CO2 inlet concentration on the CO2 removal efficiency was also investigated. Figure 6 shows the
CO2 removal efficiency profile when the inlet concentration of CO 2 increased from 5% to 15%. According to two-
film theory, the gas phase driving force and the gas phase mass transfer coefficient will increase with the increasing
CO2 partial pressure, which is beneficial to enhance absorption rate. Logically, an increase in the CO2 partial
pressure allows more CO2 molecules to travel from gas bulk to the gas-liquid interface, which would result in higher
removal efficiency. Whereas, the mole ratios of ammonia to carbon dioxide decreased from 13.78 to 4.59 as the CO2
inlet concentration increasing from 5% to 15%, which gave rise to the reduction of removal efficiency. Thus, the
CO2 removal efficiency decreased a little with the inlet concentration of CO 2 increasing both in the packed reactor
and spray column.

100
100
CO2 removal efficiency, %

CO2 removal efficiency , %

90
90
80
80
70
70
60
50 60
packed reactor
40 packed reactor 50 spray column
30 spray column 40
20 30
4 6 8 10 12 14 16 0 3 6 9 12 15 18 21
CO2 inlet concentration, % mole ratio of ammonia to CO2 ( mol/mol)

Figure 6 Effect of inlet concentration of carbon dioxide Figure 7 Effect of mole ratio of ammonia to carbon
on CO2 removal efficiency dioxide on CO2 removal efficiency
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3.6. Effect of the mole ratio of ammonia to carbon dioxide

According to the experimental parameters, mole ratios of NH 3 to CO2 were calculated. Figure 7 shows the effect
of mole ratio of NH3 to CO2 on CO2 removal efficiency. It can be seen that the mole ratio of NH3 to CO2 is a key
parameter when comparing CO2 removal efficiency at different experimental conditions. With the mole ratio of NH3
to CO2 increasing from 2.3 to 7.7, the CO2 removal efficiency increased from 52.73% to 93.12% in the packed
reactor, and the CO2 removal efficiency increased from 38.43% to 86.07% in the spray column. However, under the
lager values of the mole ratio of NH3 to CO2, the growth rate of the CO2 removal efficiency is changing slowly,
especially when the mole ratio of NH3 to CO2 exceeds 9.2 in packed column.

4. Conclusions

The removal efficiencies for CO2 absorption into aqueous ammonia were investigated in both of a spray column
and a packed reactor. The CO2 removal efficiency increases with the concentration of aqueous ammonia solution
and the aqueous ammonia flow rate, and decreases with increasing gas flow rate. Experimental results indicated that
the temperature plays an important role in CO2 absorption into aqueous ammonia, and the suitable reaction
temperatures are 40ć and 35ć for the spray column and the packed reactor respectively. Experimental results also
showed that the mole ratio of NH3 to CO2 flow rate is a key parameter and plays an important role on CO2 removal
efficiency. Compared with the spray column, the removal efficiency for CO2 absorption into aqueous ammonia in
the packed reactor shows superior performance.

Acknowledgment

This research was supported by Beijing Municipal Commission for Science & Technology under Grant
No.Z08040902950803.

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