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The study on the removal of CO2 using ammonia scrubbing

Hanping Chen, Mou Zhang, Xianhua Wang, Haiping Yang, Shihong Zhang
State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology,
Wuhan, 430074, P. R. China

Abstract:
The paper is focus on the removal of carbon dioxide from flue gas by ammonia
scrubbing, which is novel relative to the MEA process (a process based on chemical
absorption with monoethanolamine). The experiment was conducted under room
temperature. Synthesis-flue gas of CO2 and N2 pass through the ammonia solution
continuously, the ammonia solution concentration is 25 wt%. The inlet and outlet CO2
gas concentrations were measured by portable Fourier transform infrared spectra and
Micro Gas-Chromatograph quantitatively. The inlet concentrations of CO2 were 10, 12,
14, 16 and 18 vol%, respectively. The flow rate of the synthesis gas was kept at
2L/min. The ammonia solution is 200ml. It can be observed that the potential of CO2
reduction by NH3 scrubbing was very promising. The maximum CO2 removal
efficiency by NH3 solvent is over 95% and the CO2 absorption capacity is
approaching to 0.9 kg CO2/kg NH3 under proper operation conditions. Which are
better than those of MEA process (94% and 0.4 kg CO2/kg MEA, respectively).When
the inlet concentrations of CO2 were 10-18 vol%, the removal efficiencies were over
90%. It indicated that the inlet concentration of CO2 did not play great role on the
removal efficiency. Ammonia solution had a fast absorption rate of CO2. The
operation time reaching maximum CO2 removal efficiency is approximately 16 min,
and the high CO2 removal efficiency can be maintained over 1 hour. The main
products of the reaction are ammonium bicarbonate and its crystalline solids. Heated
at temperatures equal to or greater than 50 0C, ammonium bicarbonate can decompose
to CO2, NH3 and H2O. Pure CO2 can be used in the chemical plant, and NH3 can be
circular used to removal of CO2 from flue gas.
Keywords: Carbon dioxide; Ammonia solution; Monoethanolamine; Removal
efficiency; Absorption capacity
1. Introduction
With CO2 emission increasing and global warming, the reducing of greenhouse
gases emissions attracted more and more consideration. The CO2 product by electric
utilities is the major greenhouse gas. Therefore, it is significant to reduce CO2
emission from utility boilers.
There are various technologies used to separate CO2 from flue gas streams.
These include chemical solvent methods, physical absorption methods, cryogenic
methods, membrane systems, biological fixation. The chemical solvent methods have
been studied diffusely at present. But they concentrate on the treatment of SO2 or NOx
mostly. For the study on CO2 begins relatively late, the effective and economic
method is also in exploring at present. Because of the low absorption capacity of the
typical MEA process, the cost of MEA process is relative high. It is not an ideal

method on the removal of CO2 from flue gas.


The paper has introduced a novel and effective method on the removal of CO2.
This method which removes the CO2 by ammonia scrubbing has high removal
efficiency and low cost relatively to the MEA process. The method also can absorb
SO2 and NOx simultaneous. The products of the reaction can be circular used by
treatment. The experimental results show that the maximum CO2 removal efficiency
by NH3 solvent is over 95% and the CO2 absorption capacity is approaching to 0.9
kg CO2/kg NH3 under proper operation conditions.
2. Absorption theory
Generally, CO2 can be absorbed well by ammonia through chemical methods.
The reaction with CO2 and NH3 in the dry condition very easy occurs and forms the
ammonium carbamate (NH2COONH4), it is very soluble in water. Under moist air it
can form ammonium carbonate ((NH4)2CO3), and then converts to ammonium
bicarbonate (NH4HCO3). The above reactions are as follows:
CO2 ( g ) + 2 NH 3 ( g ) NH 2 COONH 4 ( s )

(1)

NH 2 COONH 4 ( s ) + H 2 O( g ) ( NH 4 ) 2 CO3 ( s )

(2)

NH 2 COONH 4 ( s ) + H 2O(l ) NH 4 HCO3 ( s ) + NH 3 ( g )

(3)

Under the state of the ammonia injection, the reaction with CO2, H2O and NH3 is
as follows:
CO2 ( g ) + 2 NH 3 ( g ) CO( NH 2 ) 2 ( s) + H 2 O( g )

(4)

CO 2 ( g ) + 2 NH 3 (l ) NH 4+ (l ) + NH 2 COO (l )

(5)

2 NH 3 ( g ) + CO2 ( g ) + H 2 O ( g ) ( NH 4 ) 2 CO3 ( s )

(6)

NH 3 ( g ) + CO2 ( g ) + H 2 O( g ) NH 4HCO3 ( s)

(7)

2 NH 3 (l ) + CO2 ( g ) + H 2 O(l ) ( NH 4 ) 2 CO3 ( s )

(8)

NH 3 (l ) + CO2 ( g ) + H 2 O(l ) NH 4HCO3 (s)

(9)

At room temperature and atmospheric pressure, the formation of ammonium


( N H 4+ ) and carbamate (NH2COO-) ions is very fast, and reaction equation (5) is
irreversible. On the other hand, reaction equation (6)-(9) are reversible, with
ammonium carbonate ((NH4)2CO3) and ammonium bicarbonate (NH4HCO3) as the
products. The forward reactions are dominant at room temperature. The backward
reactions occur at temperatures of around 38-60. The solid ammonium carbonate
and bicarbonate can exist in an aqueous solution as crystalline solids.
Although reaction equation (1) may also be used to reduce CO2 emission, the

process needs a large amount of NH3, which leads to the increase of operation cost.
When the concentration of CO2 in flue gas is high, it will explode with the dry
CO2-NH3 reaction if the process is designed improperly. Therefore, the wet method is
employed in this study. Reaction equations (8) and (9) are the most probable in this
study.
3. Experimental method
The schematic diagram of the experimental system is show in Fig.1. The
reactions of CO2 and NH3 occur at room temperature and atmospheric pressure.
Synthesis-flue gas of CO2 and N2 pass through the ammonia solution continuously.
The inlet concentrations of CO2 were 10, 12, 14, 16 and 18 vol%, respectively. The
flow rate of the synthesis gas was kept at 2L/min. The reactor contained 200ml of a
25% (w/w) ammonia solution. The gas after reaction was discharged after dryness.
The outlet CO2 gas concentration was measured by portable Fourier transform
infrared spectra and Micro Gas-Chromatograph quantitatively. The experiment was
conducted under room temperature(251).

Fig.1 Schematic diagram of carbon dioxide scrubbing by ammonia solution

4. Experimental results and discussion


The first we have an experiment when the concentration of the inlet CO2 is 16%
with 25% ammonia solution under room temperature. The gas flow rate is 2 l/min.
Fig.2 shows the CO2 removal efficiency as a function of operation time. As can be
seen that the reaction can reach a high removal efficiency in a short operation time.
After 15 min the CO2 removal efficiency is quite stable in the range from 90 to 95%,
the maximum CO2 removal efficiency is about 95%. This indicates that an ammonia
solution with a high potential scrubbing capacity has a fast absorption rate. The CO2
absorption capacity can be gained by calculation. When the outlet concentration of
CO2 equals to the inlet concentration, it indicates that the experiment is terminated,
we note the time of the experiment from begin to end. Then the total quantity of CO2
removal is calculated, and the CO2 absorption capacity expressed in kg CO2/kg NH3 is
obtained, which is around 0.87 kg CO2/kg NH3, it far higher than those of the MEA
process (0.36kg CO2/kg MEA). And the purchase price for ammonia solution is
approximately one-sixth of that for MEA solution at the same weight basis in the
market. Therefore, it is economical using ammonia scrubbing CO2 relative to the

MEA process.
1.0
0.9

co2 removal efficiency (%)

0.8

16% co2

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0

10

12

14

16

18

20

operation time (min)

Fig.2 CO2 removal efficiency as a function of operation time

Considering the different concentrations of CO2 in flue gas, we select 10, 12, 14,
16, 18% (v/v) of CO2 concentration as reaction gas. Other conditions do not be
changed. Fig.3 is a plot of CO2 removal efficiency as a function of operation time for
various CO2 inlet concentrations. As can be seen in Fig.3, the CO2 removal
efficiencies decrease with increasing CO2 concentration. When the inlet concentration
of CO2 are 10%, 12%, 14%,16%,18%, respectively, the CO2 removal efficiency are
more than 90%, the effect of inlet CO2 concentration on its removal efficiency is
minimal.
1.0
0.9

co2 removal efficiency (%)

0.8
0.7
0.6
0.5
10% co2

0.4

12% co2
14% co2

0.3

16% co2

0.2

18% co2

0.1
0.0
0

10

12

14

16

18

20

operation time (min)

Fig.3 CO2 removal efficiency as a function of reaction time for various CO2 inlet concentrations

Besides different concentration of CO2, we have experimented with various


ammonia solution concentrations. The concentrations of ammonia solution are 20%,
25%, 28%, 30%, respectively. The CO2 concentration is 16%. Fig.4 is a plot of CO2

removal efficiency as a function of operation time for various ammonia solution


concentrations. As can be seen from the plot, the larger the ammonia solution
concentration is, the higher the CO2 removal efficiency is. But the CO2 absorption
capacity decreases with increasing the ammonia solution concentration. And the
downtrend is slow. When the ammonia solution concentration is 28%, the removal
efficiency is around 90%, and the increase trend begins to decrease with the time.
Considering synthetically, it has the best removal efficiency when the ammonia
solution concentration is 28%.
1.0
0.9

co2 removal efficiency (%)

0.8
0.7
0.6
0.5
20% NH3

0.4

25% NH3

0.3

28% NH3
30% NH3

0.2
0.1
0.0
0

10

12

14

16

18

20

operation time (min)

Fig.4 CO2 removal efficiency as a function of reaction time for various NH3 concentrations
Fig.5 shows the effect of synthesis-flue gas flow rate on the CO2 removal
efficiency. The gas flow rates evaluated in this paper are in the range of 1-5 l/min. The
CO2 inlet concentration is 16% (v/v), the ammonia solution concentration is 25%
(w/w). It can be observed that the gas flow rate has a biggish influence on the CO2
removal efficiency. The maximum removal efficiencies decrease from 95% to 81%
for gas flow rates increase from 1 to 5 l/min. On the other hand, the gas flow rate has
a slight influence on the CO2 absorption capacity. The CO2 absorption capacity
decreases from 0.92 to 0.81 CO2/kg NH3.

max.co2 removal efficiency (%)

1.00

0.95

0.90

0.85

0.80

0.75
0

gas flow rate (L/m)

Fig.5 The effects of gas flow rate on CO2 removal efficiency

5. Conclusions
From the above experimental results we know that the removal of CO2 using
ammonia scrubbing has certain advantages compare with the MEA process. The
results show that the ammonia solution is superior to MEA solution in its capacity to
absorb and remove CO2 from flue gas. The CO2 removal efficiency for the ammonia
solution can be as high as 95% under proper operation conditions. And the CO2
absorption capacity of ammonia scrubbing can be 0.9 kg CO2/kg NH3. On the other
hand, the maximum CO2 removal efficiency and absorption capacity using the MEA
solution are 94% and 0.4 kg CO2/kg MEA, respectively. And the purchase price for
ammonia solution is approximately one-sixth of that for MEA solution at the same
weight basis in the market. In this way, we can reduce the cost largely using the
ammonia scrubbing. And the reaction of CO2 and NH3 is fast, the products of the
reaction can be circular used by treatment.
There are some factors influencing the removal of CO2 from flue gas using
ammonia scrubbing. Among them, the effect of inlet CO2 concentration on its removal
efficiency is minimal. The CO2 removal efficiency is quite stable high. The CO2
removal efficiencies increase with increasing ammonia solution concentration. But the
CO2 absorption capacity decreases with increasing the ammonia solution
concentration. It has the best removal efficiency when the ammonia solution
concentration is 28%. The gas flow rate has a biggish influence on the CO2 removal
efficiency while a slight influence on the CO2 absorption capacity. In order to remove
CO2 better, the gas flow rate must be controlled reasonably.
The preliminary results have shown that the potential for removing CO2 by
ammonia scrubbing may be very promising. Next work we will study how to make
use of ammonia solution circularly. We plan to divide the process of the removal of
CO2 into three parts: pre-absorption, decomposition and purification, re-absorption. It
is a continuous reaction system. The CO2 has been absorbed by ammonia solution
first and forms the ammonium carbonate or bicarbonate. These crystalline solids have
been filtrated and heated in the regenerative reactor. Then the ammonium carbonate
and bicarbonate decompose to CO2, NH3 and H2O. After bathing the gaseous product,
pure and thick CO2 can be got. NH3 is soluble in water and forms ammonia solution,
which will be sent to pre-absorption reactor and used circularly. The pure and thick
CO2 will be sent to re-absorption reactor, which makes the course of re-absorption
restrict by the CO2 solubility in water no longer. It improves the removal of CO2
greatly. The final products are crystalline solids of ammonium bicarbonate. A
simplified diagram of the CO2 scrubbing and regeneration system is shown in Fig.6.

Outlet gas

CO 2,NH3
concentration
m onitor
NH3
solution
W ater

NH3
solution

W ater
W ater

Gas
m ixer

MFC

MFC

MFC

Steam

Stirring

Stirring

Stirring
W ater
Separator

N2

O2

CO2

Scrubber

Regenerator

Reactor

Fig.6 A simplified diagram of the CO2 scrubbing and regeneration system

References
1 Bai, H.; Yeh, A. C.

Removal of CO2 Greenhouse Gas by Ammonia Scrubbing, Industrial

and Engineering Chemistry Research, 1997, 36(6), 2490-2493.


2 Yeh, A.C. and H.Bai, Comparison of Ammonium and Monoethanolamine Solvents to
Reduce CO2 Greenhouse Gas Emission, The Science of Total Environment, 1999, 228, 121-133.
3 Yeh, J. T., et al.

Aqua Ammonia Process for Simultaneous Reduction of CO2, SO2, and

NOx, Proceedings, 19th Annual International Pittsburgh Coal Conference, Pittsburgh, PA, USA,
September 23-27, 2002 .
4 Yeh, J.T.and Pennline, H. W. Absorption and Regeneration Studies for CO2 Capture by
Aqueous Ammonia. The Third Annual Conference on Carbon Sequestration, Alexandra, VA,
USA, May 3-8, 2004.