Beruflich Dokumente
Kultur Dokumente
6-12
TI Journals
ISSN:
2306-6474
Copyright 2015. All rights reserved for TI Journals.
M.E.Kenawy
Abu Qir Fertilizer and Chemical Industry Co., Alexandria, Egypt
M.M.Mostafa
Abu Qir Fertilizer and Chemical Industry Co., Alexandria, Egypt
*Corresponding author: eng7ooda@yahoo.com
Keywords
Abstract
Carbon dioxide is undesirable constituent present in practically all synthesis gas mixtures produced form
ammonia manufacture. Presence in the gas stream not only dilutes the synthesis gas and creates operational
problem but also poisons the ammonia synthesis catalyst. Carbon dioxide consider main constituent in urea
manufacture so separation of carbon dioxide from syngas in ammonia manufacture consider as main step.
During the last three decades many liquid absorption processes has been developed for its removal.
The effect of different variables includes solution concentration (5, 7.5 and 10 g/l), gas flow rate (30.24, 60.8 and
97.8 l/hr.) and solution flow rate (24, 36, 48, 60 and 72 l/hr.) on absorption by Benfield process (using K2CO3
solution) are investigated. At the best conditions of solution concentration (7.5 g/l) and gas flow rate (30.24 l/hr.)
and solution flow rate (60 l/hr.), the effect of adding different promoters including Mono ethanolamine (MEA),
Di ethanolamine (DEA) and Piperazine are investigated.
Piperazine is found to have a great effect in % CO2 absorption that it increases the % CO2 absorption about 23%
higher than unprompted K2CO3 solution while MEA increases % CO2 absorption about 13% higher than
unprompted K2CO3 solution and DEA increases % CO2 absorption about 9% higher than unprompted K2CO3
solution.
1.
Introduction
Carbon dioxide is undesirable constituent present in practically all synthesis gas mixtures produced for ammonia manufacture. Its presence in the
gas stream not only dilutes the synthesis gas and creates operational problem but also poisons the ammonia synthesis catalyst. Moreover, its
removal is also essential to avoid solid CO2 plugging in liquid nitrogen wash system and other operational problems during ammonia production.
It must, be reduced to less than 10 ppm. In the fertilizer industry, CO 2 recovery has also assumed great commercial importance because of its use
in the production of urea. During the last three decades, various liquid absorption processes have been developed to remove and recover carbon
dioxide from synthesis streams. [1]
A process based on a pair of columns, one absorber and one stripper achieves carbon dioxide removal industrially. The purpose of the absorber
is to capture the carbon dioxide, whereas the purpose of the stripper is to regenerate the solvent, so that it is ready to be recycled to the absorber.
The absorber has two feeds, at the bottom the flue gas enters the column and flows upwards. The CO 2 content of the feed is changed with the
type of flue gas. Gas turbines produce flue gases with approximately 3-mole % CO2. Natural gas and coal-fired power plants generate more CO2,
with flue gases containing 5-6% and 10-12% of CO2 respectively. [2] These absorption processes may broadly be classified under the following
categories: Chemical absorption processes and divided to Alkanol amines as chemical solvents, in chemical absorption systems, several alkanol
amines have been extensively used for carbon dioxide scrubbing. Each alkanolamine has at least one hydroxyl group and one amine group. The
hydroxyl group serves to reduce the vapor pressure and increase the water solubility while the amine group provides the necessary alkalinity in
water solution to cause the absorption of acid gases by chemical reaction. The rate of absorption of carbon dioxide into an amine solution is
comparable to the rate of absorption into a solution of caustic soda and is much greater than the rate of absorption into a carbonate -bicarbonate
solution in the absence of an activator. The carbonate amine solution can be easily regenerated by heating. The common promoters is
Monoethanol amine (MEA) as a primary amine, Diethanol amine as a secondary amine, Methyl diethanol amine as tertiary amines, Piprazine as
cyclic secondary amine and Hindered amines [1]. Alkaline salt solution as chemical solvent: The hot potassium carbonate solution based
processes are represented in commercial practice by mainly three process, Benfield, Vatrocoke, and Catacarb. The physical absorption processes
have similarly in their principle of operation as well as in their limitations and are different mainly in the specific solvent used. All use some
organic solvent, which depends on selective physical absorption of acid gas rather than chemical reaction. The acid gas loading of the solvent is
directly proportional to pressure applications and the mainly processes is water, Rectisol, Purisol, Fluor solvent and Selexol. [1]
Chemical and Physical Absorption Process: When a general need developed for removing acidic components at high partial pressure from gas
streams Sulfinol solvent formulation are used . Sulfnol is consists of a mixture of sulfolane (tetrahydrothoiphene 1, 1-dioxide), an alkanolamine
(most often di-isopropanolamine) and water, in various proportions depending upon the application. A typical formulation contains 40 percent
wt. of sulfolane, 45 percent wt. of di-isopropanolamine and 15 percent wt. of water. The process is unique in that it combines the characteristics
of a physical solvent process and amine process. The choice of a specific carbon dioxide solvent system depends on the partial pressure of
carbon dioxide in the feed gas and the total pressure of absorption; degree of carbon dioxide removal required; nature of sulfur compounds and
other impurities present in the feed gas; availability and cost of solvent and utilities and, finally, how well a specific process can be integrated
with the rest of the design of the ammonia plant. [3]
The hot potassium carbonate process is effectively used in many ammonia, hydrogen, ethylene oxide and natural gas plants. To improve CO2
absorption mass transfer and to inhibit corrosion, proprietary activators and inhibitors are added. These systems are known as activated hot
potassium carbonate (AHPC) systems. The accepted mechanism of CO2 absorption into water consists of two parallel mechanisms: [4] [3]
(fast)
(instant)
(1)
(2)
(slow)
(instant)
(3)
(4)
According to Astarita and Savage [5], the predominant mechanism at pH > 10 is reaction (4). The reaction rate at 105C is not high enough to be
considered instantaneous. Carbon dioxide is absorbed in an unpromoted solution of potassium carbonate and bicarbonate; it reacts according to
the following overall reaction
CO2 + K2CO3 + H2O 2 KHCO3
(5)
Promotion of mass-transfer rates, through additives of K2CO3 solution, has been reported in the literature. Astarita [6] has discussed the most
recent theory. It is assumed that the role of additives is that of a catalyst in the reaction rather than a modifier of vapor-liquid equilibrium for rate
promotion with the help of amino compounds, the reaction that takes place at the gas-liquid interface
CO2 + RRNH RRCOOH
(Amine) (carbamate)
(6)
Reversion of the carbonate to bicarbonate ion takes place in the bulk of the liquid as follows:
RRCOOH + OH HCO3 + RRNH2
(7)
At ambient temperatures, reaction (6) is much faster than reaction (7), and the so-called Shuttle mechanism is operative in which the
carbamate diffuses into the bulk where it reacts with OH ion to regenerate the amine, which then diffuses back to the interface to react with
more carbon dioxide. However, at higher temperature, in the range of industrial operation, the rate of reaction (7) increase significantly and it
follows reaction (6) immediately and locally, the system is better represented by the homogeneous catalysis mechanisms. This mechanism may
shoot up the overall reaction rate to an instantaneous regime. In the hot potassium carbonate process of Benfield [7], the alkanolamine DEA is
used as the activator of the process, but Bartoo [8] discovered a new organic promoter. This new activator has a better absorption rate than DEA,
at lower vapor pressure. Another advantage is the excellent chemical stability the activator is called ACT-1. The addition of a primary or
secondary amine to a tertiary has found widespread application in the absorption and removal of CO2 from process gases. The success of these
solvents is due to the high rate of reaction of the primary or secondary amine with CO2 combined with the low heat of reaction of the tertiary
amine. By adding small amounts of the primary or secondary amine, a high rate of absorption is seen in the absorber, while a low energy of
regeneration is required in the stripper. One such blend of amines is piperazine (PZ) activated methyl di ethanolamine (MDEA). These solvents
have been used successfully for high capacity CO2 removal in ammonia plants. The rate of absorption decreases as the CO 2 content in the
solution approaches equilibrium. Therefore, a practical set of operating conditions must be chosen to give an optimum between low solvent
circulation rate at maximum absorption and low contact time at minimum absorption. It is affected by temperature, % conversion of carbonate,
CO2 concentration in the gas, solvent concentration, the viscosity of the solvent, the gas flow rate and the liquid flow rate and the type of solvent.
[6]
2.
Methodology
12
1. Valve 1 on solution outlet
2. Valve on gas outlet
3. Gas flowmeter
4. Gas inlet to column
5. Gas cylinder
6. Solution tank
7. Valve on by-pass of solution pump
8. Valve on discharge of solution pump
9. Solution pump
10. Absorption column
11. Solution flowmeter
12. Solution inlet to column
11
10
8
4
bypass
7
1
3
5
6
9
Solution
sample
2.5.4.2. Di ethanolamine
The effect of DEA of different concentration (0.005, 0.03, 0.06 & 0.08 gmol/l) as promoter for potassium carbonate on the CO 2 absorption,
efficiency & KHCO 3 formed studied. The solution flow rate (60 l/hr.) and the gas flow rate (30.24 l/hr.) and K2 CO3 concentration of 7.5 g/l were
kept constant for any run at different period of time (10, 20, 30 and 80 min).
2.5.4.3. Piperazine
The effect of Piperazine of different concentration (0.005, 0.03, 0.06 & 0.08 gmol/l) as promoter for potassium carbonate on the CO 2 absorption,
efficiency & KHCO 3 formed studied. The solution flow rate (60 l/hr.) and the gas flow rate (30.24 l/hr.) and K2 CO3 concentration of 7.5 g/l were
kept constant for any run at different period of time (10, 20, 30 and 80 min).
3.
70%
% absorption
60%
50%
K2CO3
concentration
5 g/l
40%
30%
7.5 g/l
20%
10 g/l
10%
0%
0
10
20
30
40
50
60
70
80
90
time (min.)
Figure 2. Effect of varying concentration of K2CO3 solution on the % absorption of
CO2 at constant gas flow rate of 30.24 l/h and constant liquid flow rate of 48 l/h.
60%
% absorption
50%
40%
30%
30.24 L/H
20%
60.8 L/H
10%
97.8 L/H
0%
0
10
20
30
40
50
60
70
80
90
time (min.)
Figure 3. Effect of varying gas flow rate on the % absorption of CO2 at constant
K2CO3 concentration of 7.5 g/l and constant solution flow rate of 48 l/h.
10
70%
solution
flow rate
% absorption
60%
50%
48 L/H
40%
60 L/H
30%
72 L/H
20%
24 L/H
10%
36 L/H
0%
0
10
20
30
40
50
60
70
80
90
time (min.)
% absorption
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
MEA concentratiob
0.005 mol/L
0.03 mol/L
0.06 mol/L
0.08 mol/L
0
10
20
30
40
50
60
70
80
90
time (min.)
Figure 5. Effect of varying concentration of MEA on the % absorption of CO2 at the optimized conditions
of K2CO3 concentration (7.5 g/l) and gas flow rate (30.24 l/h) and solution flow rate (60 l/h)
11
be attributed to that increasing the promoter concentration reflects a higher enhancement factor in the liquid phase , which is directly
proportional to the overall mass transfer in the case of liquid phase controlled mass transfer. With more increasing the promoter concentration,
the gas phase mass transfer will be the major factor controlling the absorption processes, so the CO 2 removal is unaffected by increasing the
promoter concentration in this case.
80%
70%
% absorption
60%
DEA concentration
50%
0.005 mol/L
40%
0.03 mol/L
30%
0.06 mol/L
20%
0.08 mol/L
10%
0%
0
10
20
30
40
50
60
70
80
90
time (min.)
Figure 6. Effect of varying concentration of DEA on the % absorption of CO2 at the optimized conditions
of K2CO3 concentration (7.5 g/l) and gas flow rate (30.24 l/h) and solution flow rate (60 l/h)
3.4.3. Piperazine:
The results presented in fig. (7) Shows that for promoted K2CO3 solution with piperazine an increase in the promoter concentration first increase
the overall mass transfer until reached to promoter concentration 0.06 mole/l while raising the promoter content beyond this concentration has no
effect on the exit CO 2 concentration. These results agrees with results obtained when using mono ethanolamine and di ethanolamine promoters.
-
90%
80%
% absorption
70%
Piperazine
concentration
0.005 mol/L
60%
50%
40%
0.03 mol/L
30%
0.06 mol/L
20%
0.08 mol/L
10%
0%
0
10
20
30
40
50
60
70
80
90
time (min.)
Figure 7. Effect of varying concentration of piperazine on the % absorption of CO2 at the optimized
conditions of K2 CO3 concentration (7.5 g/l) and gas flow rate (30.24 l/h) and solution flow rate (60 l/h)
12
% CO2 absorption
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
MEA
DEA
piperazine
10
20
30
40
50
60
70
80
90
time (min.)
Figure 8. Effect of varying promoters on the % absorption of CO2 at the optimized conditions
of K2CO3 concentration (7.5 g/l) and gas flow rate (30.24 l/h) and solution flow rate (60 l/h)
3.6. Comparison
The following fig. no. (9) Compare between different promoters and unprompted solution of potassium carbonate.
90%
% CO2 ABSORPTION
80%
70%
60%
40%
unpromoted
solution
MEA
30%
DEA
50%
20%
10%
0%
0
10
20
30
40
50
60
70
80
90
TIME (MIN.)
4.
Conclusion
The absorption of CO2 in K2CO3 solution of concentration 7.5 g/l gives best results and better than 10 g/l due to low material consumption and
ease of pumping and minimize corrosion problems and reduce consumption of corrosion inhibitor and low difference in effect between the two
concentrations. The best gas flow rate is 30.24 l/hr. Solution flow rate (60 l/hr.) is the best condition and better than concentration of 72 l/hr. due
to saving pumping cost and initial pump cost and no difference between the two flow rates. Piperazine with concentration 0.06 mole/l shows a
great effect on % CO2 absorption and increase it with 23% over the best conditions of unprompted K2CO3 solution while MEA increases the %
CO2 absorption by 17% and DEA by 9%
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
Appl, M., "Ammonia Principles and Industrial practice", Wiley-VCH, Germany, 1999.
Kothandaraman, A., "Carbon Dioxide Capture by Chemical Solvent: A solvent Comparison Study", Massachusetts Institute of Technology, JUNE 2010.
Kenawy, M., "Development of A mathematical Model for Carbon Dioxide Gas Absorption", Ph.D. Thesis, Alexandria University, Egypt, 2009.
Pudjiastuti,L., Altway,A. and Soewarno,N., "Carbon Dioxide Absorption into Aqueous Potassium Carbonate Promoted with Methyl di ethanolamine
MDEA", International Journal of Academic Research, 3(3), May.2011, 1 part .
Asarita, G., Savage, D. "Gas Treating with Chemical Solvents", John Wiley, New York, 1983.
Asarita, G., Savage, D. and Joshi, S., "Chemical Absorption and Desorption of Carbon Dioxide from Hot Carbonate solutions", Chemical Engineering
Journal, 35, 1980, pp.1513-1522.\
Benson, S., Field, J., and Jimeson, R., "Carbon Dioxide Absorption Employing Hot Potassium Carbonate Solutions", Chem. Eng. Prog., 50, 1954, pp.356364.
Bartoo, R., Ruzick, S., "Recent improvements to the Benfield Process Extend its use", Nitrogen Conference, 91, 1991.