Coo2 Others

KINETICS OF THE ABSORPTION OF C02INTO MIXED
AQUEOUS LOADED SOLUTIONS OF MONOETHANOLAMINE AND

METHYLDIETHANOLAMINE
A Thesis
Submitted to the Faculty of Graduate Studies and Research
In Partial Fulfillment of the Requirements
for the Degree of
Master of Applied Science
in Industrial Systems Engineering
University of Regina
by
Naveen Ramachandran
Regina, Saskatchewan
January 2004
Copyright 2004: N. Ramachandran
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
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ABSTRACT
Alkanolamines have attained a well-established position in gas treating for the removal of
acid gases like Carbon Dioxide(COi). The widely used alkanolamines are
monoethanolamine (MEA), diethanolamine (DBA) etc. Due to the high increase in the
regeneration costs, the motivation is to develop better processes and efficient gas treating
solvents. Tertiary amines have high equilibrium loading capacity but react slowly with
CO2 whereas primary amines have limited equilibrium loading capacity but react much
faster with CO2 . By varying the compositions of these solvents one can optimize the CO2
removal process. Kinetic studies are very important in the design of the acid gases
treating processes. This masters thesis presents the kinetics of absorption of CO2 in
loaded methyldiethanolamine (MDEA) and MEA solutions.
The work can be divided into two parts: (a) experimental work to obtain reliable date for
the mixed alkanolamine system at various acid gases process treating conditions, (b)
modeling work Ito interpret the experimental absorption data with the help of reaction
models. The experiments were conducted over the temperature range of 298-333K, the
MDEA/MEA wt.% of 27/03, 25/05 and 23/07, total amine concentration of 30wt% and
the CO2 loading from 0.005 to 0.15 mol/mol. Experimental data were obtained in a
laminar jet absorber at various contact-times between the gas and the liquid. The
physical properties like density, viscosity, diffusivity and solubility of the system were
calculated from the published data and/or models. The reaction mechanisms namely
Zwitterion and Teraiolecular were used to interpret the Kinetic data. It was found that
Zwitterion mechanism in its original form could not predict the individual Kinetic rate
constants, Termolecular mechanism with water in the apparent reaction rate term as
suggested by Crooks and Dormellan (1989) did not yield any results as well. A modified
Termolecular mechanism, which included the contribution of hydroxide ions, was able to
predict the kinetics of CO2 loaded mixed alkanolamine solution better. Individual
reaction rate constants were predicted based on the modified Termolecular mechanism.
Also, it was observed MDEA did not participate in MEA kinetics.
ACKNOWLEDGMENTS
The thesis would have been impossible without the following people:
I would like to express my sincere gratitude to Professor Paitoon Tonti wachwuthikul,
thesis supervisor for guidance, encouragement, financial support and the independence to
pursue research. I consider myself fortunate to work with Professor Paitoon whose timely
advice has saved me many times while progressing through the research.
I would like to thank Professor Raphael Mem who is not only serving as a member of the
supervisory committee, but for having read the early draft of the thesis. Professor Mem
have given valuable inputs on each aspect of the project which was very important for the
timely completion.
Dr. Ahmed Abondheir deserves special thanks. Right from initial training as to how to
obtain the most reliable data from the laminar jet apparatus until the analysis of
experimental results, he has taken me step by step to successful completion. Thanks so
much for patiently hearing and answering much number of e-mails, frantic phone calls
that I had made when something went wrong with the apparatus. I wish you had a 1-800
number!
I thank Dr. Arar Henni for guidance. We had very interesting discussions about this
masters project. Thank you David deMontigny for helping me with everything (technical
and non technical). I cherish every moment I was with you in the CO2 lab. Thanks to
Thyagarajan Mathialagan for many rides to my home from P.T.R.C during late nights
and to Asok Kumar Tharanivasan for the great time I had with him at the Petroleum
Technology Research Center and especially for wonderful kichhidi.
Last but not the least, I thank my parents for their never ending love, support, motivation
without which I would have not been what I am today.
ii
TABLE OF CONTENTS
ABSTRACT 09#ae9eeBeeee8aeee#e*asaoe9sasess \
ACKNOWLEDGMENTS II
TABLE OF CONTENTS ....................................... ...................... iii
LIST OF TABLES 9#ee**e9ee V
LIST OF FIGURES .................. .............................. .......................... ............... vii
1. INTRODUCTION...... ....... ........................ .......... ........ 1
1.1 General Booas9e000 0 oeeae0 0 oe0 0 00e000a0a9ei0e00o9ea009Be00 000 0 0 ffl0 Boa0 0 0 0000000 1
1.2 Objectives ...... ............ .. 0 3 3 9 9 9 seea&8e0&$&&&&13
2.THEORY.............. 2
2.1 Chemical Reactions........................................................... 2
2.2 Liquid bulk concentration of all chemical species................................................. 22
23 Kinetics of Reaction.................................................................................................. 27
2.3.1 Reaction rate dependence on MEA 29
2.3.2 Reaction rate dependence on MDEA 3
2.3.3 Overall reaction rate for CO2 with MEA+MDEA+H2 O 31
2.3.4 Termolecular mechanism 31
2.3.5 Methodology to determine kinetics 32
3. PHYSICAL PROPERTIES....................................................................................... 36
3.1 Density 36
3.2 Viscosity..................................................................................................................... 42
3.3 Solubility......................................................................... iaae0eeea9i58B00i!atse(>09*aBe........... 42
3.4 Dtffusfvity of CO2 in mixed amines..... ....... 47
4. LAMINAR JET ABSORPTION EXPEMIEMNTS................................................. 54
HI
4.1 Experimental apparatus and procedure 55
4.2 Calibration of the laminar Jet apparatus aaffi-aaeas<i00ffleaaas0eBa000a09eeea0B8i62
4.3. Results and discussion for COj-MEA-MDEA Absorption.................... 68
5. KINETICS OF ME ACTION...................................................................................... 74
5.1 Interpretation of Experimental kapP........................................................................ 76
5.2 Determination of Kinetics based on the Zwitterion Mechanism Bee&Baae0000000aseasee86
5.3 Determination of Kinetics based on the Termolecular Mechanism ....... 87
5.4 Determination of Kinetics based on the Power law Model................................... 98
6. CONCLUSIONS ................................................... 103
6.1 Recommendations................................................................................................... 104
References .000a00000BBffl0e0e000000e080a000000e0eB0000BB000a0i000ss00.... 106
Appendix A:............................................................... 111
Appendix B o000asseeeoBeeeeeoeesaeeaeeeeseeo000000ae000000000000000000000 .................. 117
^^ppeitclsx L- ..........a..................................................................................................... 130
iv
LIST OF TABLES
Table 1. 1Targets for CO2 removal in process industry (Astarita et ai, 1983)....,.........,,.. 7
Table 1. 2 Guidelines for process selection of CO2 removal process................................. 9
Table 1. 3 Compilation of kinetics of CO2 in mixed amine system................................. 19
Table 3. I Parameters for density correlations.................................................................. 39
Table 3 . 2 Experimental data for absorption rate of CO2 in 1M MEA solution at 298K
and atmospheric pressure.......................................................................................... 49
Table 3. 3 Parameters in the diffusivity correlation (Equations .20) for MEA-HaO solution
(Ko et aL, 2001)........................................................................................................ 51
Table 3.4 Parameters in the diffusivity correlation (Equation 3.21) for MEA-MDEA-
H2O (Li and Lai, 1995).......................................................................,..................,.. 51
Table 4. 1Experimental data for the absorption of CO2 in water at 298K and atmospheric
pressure............................................................................ 63
Table 4. 2 Diffusivity of CO2 in water at 298K and atmospheric pressure...................... 66
Table 5. 1Fitted values of kinetics constants of CO2- absorption into aqueous MDEA-
MEA solution based on the deprotonation of zwitterion mechanism....................... 92
Table C. 1Experimental data for Kinetics for CO2 absorption into aqueous 23 wt. %
MDEA-7 wt.% MEA solutions.............................................. 131
v
Table C. 2 Experimental data for Kinetics for CO2 absorption into aqueous 25 wt %
MDEA- 5 wt.% MEA solutions.............................................................................. 133
Table C. 3 Experimental data for Kinetics for CO2 absorption into aqueous 27 wt, %
MDEA- 3 wt.% MEA solutions.............................................................................. 135
vi
LIST OF FIGURES
Figure 1.1 Emissions by sector in 2010 (Climate change plan for Canada, 2003)............. 5
Figure 2.1 Liquid-phase speciation and concentration in aqueous MDEA-MEA (27wt%-
3wt.%) solution with CO2 loading (a) from Oto 1.0 at 313K. The thermodynamic
model developed in this work predicted the composition of species..... 26
Figure 2. 2 Single step, termolecular reaction mechanism for the formation of carbamate
(Crooks andDonnellan, 1989).................................................................................. 32
Figure 2.3 Flow diagram for overall and apparent kinetics rate constants calculation..... 35
Figure 3. 1The density of aqueous mixed alkanolamine solution as a function of mixed
amine concentration and CO2 loading at 298K......................................................... 40
Figure 3.2 The density of aqueous 23 wt.%MDE A/07 wt.%ME A alkanolamine solution
as a function of temperature and CO2 loading......................................................... 41
Figure 3. 3 Solubility of N2O in MEA-MDEA solutions as function of temperature.
Points are predicted by the model and lines are experimental by Li and Sfaen, 1992.
...................................................................................................................................46
Figure 3.4 Rate of CO2 absorption into 1M MEA solution at 298K and atmospheric
pressure............................................... 52
Figure 4. 1 Schematic drawing of laminar jet apparatus from Aboudheirs Ph.D. Thesis,
2002........................................................................................................................... 57
Figure 4. 2 Volumetric technique for measuring the mass transfer rate in laminar jet
absorber..................................................................................................................... 61
Figure 4. 3 Rate of absorption of CO2 into water at 298K and atmospheric pressure in a
laminar jet absorber. Experimental (points), theoretical (line)................................ 67
Figure 4. 4 Absorption rate of COj into aqueous MEA-MDEA solutions: average
loadings 0.031, T=323K.......................................................................................... 71
Figure 4. 5 Absorption rate of CO2 into aqueous 23wt.% MDEA - 7wt.% MEA solutions:
loading= 0.031 ......... 72
Figure 4. 6 Absorption rate of CO2 into aqueous 23wt.% MDEA - 7wt.% MEA solutions:
T = 323K... .... 73
Figure 5. 1Apparent rate constant k^p for the reaction of CO2 into aqueous 23wt.%
MDEA - 7wt.% MEA solutions as a function of free MEA concentration.............. 78
Figure 5.2 Apparent rate constant kaPPfor the reaction of CO2 into aqueous 25wt.%
MDEA - 5wt.% MEA solutions as a function of free MEA concentration.............. 79
Figure 5. 3 Apparent rate constant kapPfor the reaction of CO2 into aqueous 27wt%
MDEA - 3 wt.% MEA solutions as a function of free MEA concentration.............. 80
Figure 5.4 Apparent rate constant kaPPfor the reaction of CO2 into aqueous MDEA -
MEA solutions as a function of free MEA concentration at 298K........................... 81
Figure 5. 5 Apparent rate constant kapp for the reaction of CO2 into aqueous MDEA -
MEA solutions as a function of free MEA concentration at 303K.. .... 82
viii
Figure 5, 6 Apparent rate constant kapp for the reaction of CO2 into aqueous MDEA -
Figure 5. 7 Apparent rate constant k^p for the reaction of CO2 into aqueous MDEA -
MEA solutions as a function of free MEA concentration at 323K.,............... 84
Figure 5. 9 Apparent rate constant for the reaction of CO2 with 27 wt.% MDEA-3wt.%
MEA solution as a function of free MEA concentration. Solid lines are predicted by
Equation 5.4.................................................................. 94
Figure 5.10 Apparent rate constant for the reaction of CO2 with 25 wt.% MDEA-5wt.%
Equation 5.4......................................................................................... 95
Figure 5. II Apparent rate constant for the reaction of CO2 with 23 wt.% MDEA-7wt.%
Equation 5.4.............................................................................................................. 96
Equation 5.9.............................................................................................................. 99
Figure 5.13 Apparent rate constant for the reaction of CO2 with 25 wt.% MDEA-5wt%
Equation 5.9........................................................................... 100
i x
Figure 5. 14. Apparent rate constant for the reaction of CO2 with 23 wt.% MDEA-7wt%
Equation 5.9......... ................................................................................................. 101
1. INTRODUCTION
1.1 General
The removal of carbon dioxide, from gaseous mixtures not only is important in the field
of sour gas removal, but it is also used to curb emissions of greenhouse gases. The
international community has concluded that there is compelling evidence that human
activities like energy use and deforestation are accelerating the concentration of
greenhouse gases in the earth's atmosphere. There is a general agreement that the world
is experiencing a change in the earths surface temperature. The average increase is
predicted to be 1.4 to 5.8C by 2100 with serious implications regarding global food and
water requirements (Climate change plan for Canada, 2003).
In Canada, some of the observed effects of climate change are:
declining water levels in the Great lakes
increasing number and intensity of heat waves
melting of polar ice cap and changes in marine life
hotter summers and higher levels of smog in major urban centers
extreme weather conditions such as recent droughts in the Prairies, ice storms in
Eastern Canada, flooding in Manitoba and Quebec to name a few.
The immediate impact of these frequently changing climate-related activities are related
for its profound effect on our economy, as well as our health and quality of life.
One of the important methods outlined by the Government of Canada in the recent
approach to curb greenhouse gases is by
promoting new innovation and technologies
1
energy efficient homes and vehicles used in day to day life
The plan involves a three-step approach for achieving Canadas climate change objective
of reducing annual greenhouse gas emissions (GHG) by 240 megatormes. As of today,
there are investments that can address one third of the emission reduction (80MT).
Secondly, the plan enunciates a strategy for a further 100 MT reduction, and finally, it
outlines a number of current and potential actions that should enable Canada to address
the remaining 60 MT reduction. As per the Kyoto Accord of 1997 that Canada ratified
recently, the greenhouse gases including CO2 are to be reduced to 6% below the 1990
levels by 2008 and 2012.
To attain the goal, some of the key means suggested by the plan are:
Emissions reduction targets for large industrial emitters through agreements
with regulations that would create an incentive for shifting to lower-emissions
technologies and energy sources while providing flexibility for emitters through
emissions trading.
Strategic infrastructure investments in innovative climate change proposals
such as urban transit projects, etc.
A coordinated innovation strategy that allows Canada to benefit fully from
innovation possibilities of the climate change agenda
Targeted measures including information, incentives, regulations and tax
measures that will aid achieve climate change objectives in specific sectors
(Climate Change plan for Canada, 2003).
2
Key areas for action in the plan have identified seven initiatives: transportation, housing
and commercial buildings, large scale industrial emitters, renewable energy and cleaner
fuels, small and medium-sized enterprises and fugitive emissions, agriculture, forestry
and landfills, International emission reductions. Though dealing with each topic in detail
is beyond the scope of this thesis, the plan for large industrial emitters and renewable
energy will be dealt with in brief. They are: establishing emissions targets through
covenants, domestic emissions trading, cost-shared strategic investments in the areas like
renewable energy, clean coal demonstration projects, and a CO2 pipeline. Under
renewable energy comes the need for new innovative technologies. To accomplish these
objectives under innovative technologies, new formulated solvents are important in the
removal of CO2 (which is a greenhouse gas). In the industry, chemical solvents such are
alkanolamines are commonly used to aid the absorption process of CO2 . Data available
on the kinetics of absorption of the newly formulated mixed amines are scarce at various
CO2 loadings and for a wide range of temperatures (298K to 333K). This research
involves the study of the Kinetics of CO2 absorption into mixed amine systems at
various process parameters such as temperature, acid gas loadings that will effectively
address CO2 absorption issues as a foundation to formulate amine technologies for CO2
capture. Before delving into the absorption issues, it would be worthwhile to examine
some basic concepts about greenhouse gases and sources of CO2 emissions.
Greenhouse gases
Greenhouses gases occur in nature are mainly water vapor, carbon dioxide, methane,
nitrous oxide and ozone within limits. The list is not exhaustive. Specific human
3
activities that produce these gases can create greenhouse gases that do not occur
naturally. It is Interesting to examine how these gases are released in excess to the
earths atmosphere.
Carbon dioxide: An increasing amount of carbon dioxide is being released by the
combustion of fossil fuels (coal, natural gas and oil) for Industrial purposes,
transportation, heating/cooling of buildings, as well as by deforestation.
Methane: Increasing amounts of methane are being released from landfills,
wastewater treatment, and certain agricultural practices, and from grazing of live
stock.
Nitrous oxide: This is being emitted into the earths atmosphere through the use
of chemical fertilizers and burning of fossil fuels
Apart from these naturally occurring greenhouse gases, man-made gases that are included
in the Kyoto Protocol, hydrochlorofluorocarbons (HFCs), perfluorocarbons (PFCs) and
sulfur hexafluoride (SFg), are generated in variety of industrial processes.
Sources of emissions from large scale industrial establishments
The large Industrial emitters are grouped In three sectors: Power Generation, Oil and Gas,
and Mining and Manufacturing. Industry wise emissions break-up is presented in Figure
1.1. From this figure, it can be observed that approximately 51% of the total COa
emissions are from the sector namely Mining and Manufacturing, Power Generation and
Oil Gas. Cleaner technologies have to developed to target these sectors. Relying on
cleaner technologies and in-plant processing by setting absorption-regeneration systems
4
IAgriculture
10% I Oil and gas
ILandfill Gas
4% ,
ITransportation
25%
Buidsigs
Mining and
Power ~ Mam&cturing
Generation
16%
17%
Figure 1.1 Emissions by sector in 2010 (Climate change plan for Canada, 2003)
can reduce greenhouse gases from electricity sector. For the oil and gas sector, the
potential is by reducing emission intensity of oil and gas distribution.
In the mining and manufacturing sector which is highly diverse, the emissions generally
fall into two categories: those arising from combustion of fossil fuels for energy and
heating, and secondly from industrial processes in which greenhouse gases are emitted as
direct by-products. There has been some successes in this factor in curbing emissions
based on mitigation technologies and increased energy efficiency.
In addition to the climate change problems associated with the greenhouse gas emissions,
the removal of acid gases like CO2 , H2 S etc. is of prime importance in process industry to
meet specific cleanup targets. Some of the industrial applications that entail CO2 removal
are given in Table 1.1. It can be clearly seen from the table that clean up targets for
various process industries are different and are industry specific. For example, CO2
specification may be relatively slack for natural gas (<1%), but for ammonia and LNG
manufacture, CO2 must be reduced to lOppm and SOppm, respectively. Based on the
removal requirements, different industrial techniques are adopted. Some of the industrial
techniques adopted for CO2 emissions reduction in industries are outlined below.
Distillation, which is the commonly used approach for separating fluid mixtures, is not
generally attractive as compared to absorption of the gas into a liquid for acid gas
separation. The parent components of gaseous streams containing acidic impurities are
usually light gases including hydrogen, methane, ethane, etc. whose boiling points are so
low such that cryogenic distillation would be needed
6
Table 1.1 Targets for CO2 removal in process industry (Astarita et al., 1983)
Process Common clean up targets
Hydrogen manufacture <0.1%co2
Ammonia manufacture <16ppm of CO+CO2
Natural gas purification:
Pipeline gas <1%C02
LNG feedstock <50ppm 0 2
Coal gasification 5G0ppm CO2
(Astarita et aL, 1983). Absorption is the most widely used CO2 removal technique. The
main methods of absorption include absorption into a liquid solvent, either physically or
chemically. Common physical solvents include organic liquids such as alcohols, glycols,
propylene carbonate, and pyirolidones. Despite the fact that physical solvents may be
important as the energy costs continue to rise, chemical solvents are most preferred for
low-pressure gas treating (< about 50psi) applications because of the economic viability
of chemical solvent. In the case of physical solvent, the acid gas solubility is small at low
partial pressures and absorption capacity of physical solvent is a function of partial
pressure. A chemical solvent exhibits quite a high loading at low CO2 pressures but
becomes saturated at moderate pressures. Thus, when removing acid gases at low partial
pressure in the feed gas, a chemical solvent is preferred. Adsorption also seems to be a
viable option for carbon dioxide removal when CO2 partial pressure is high in the feed
and the concentration of CO2 in the product required is very small. In small sized plants,
pressure-swing adsorption (PSA) seems to be an attractive choice compared to
absorption. Membrane permeation is an active technology in the field of gas purification.
In this process, polymeric membranes separate gases by selective permeation of one or
more gaseous components from one side of the membrane barrier to the other side.
Hybrid processes are also prevalent where membranes are used for bulk removal of
carbon dioxide and amine process for final clean up (Kohl and Neilsen, 1997). Suitable
gas purification systems can be grouped into six categories based on the plant size and
partial pressure of carbon dioxide in the feed gas stream that is to be treated. Table 1.2
gives the guidelines for selection of CO2 removal process.
8
Table 1.2 Guidelines for process selection of CO2 removal process
(Kohl and Neilsen, 1997)
Type of process Plant Size,m3/day Partial Pressure, kPa
Absorption in Alkaline solution >600,000 <700
Physical absorption >600,000 >700
Membrane permeation <600,000 >700
Hybrid(amine-membrane) <600,000 >700
Adsorption <600,000 >700
Methanation <600,000 <700
9
The most common method for bulk removal of CO2 is by absorption into a solution of
chemical base, and the most widely used of such basic chemical solvents are
alkanolamines and hot potassium carbonate solutions. Common alkanolamines that are
employed for CO2 absorption are monoethanolamine (MEA), diethanolamine (DEA),
methyldiethanolamine (MDEA), triethanolamine (TEA), diisopropanolamine (DIPA) and
Mnderd amines like 2-amino-2-methyl-1-propanol (AMP). Promoted hot carbonate
solutions are potassium carbonate (K2 CO3) and sodium hydroxide (NaOH). Although
TEA was the first alkanolamine to become commercially available, it was displaced by
other alkanolamines due to low capacity (due to high equivalent weight), low reactivity
and relatively poor stability. MEA has been widely used for many years in gas
purification industry for variety of reasons, one of which is that MEA is favored for gas
streams that contain low concentrations of H2 S and CO2 . The low molecular weight of
MEA which results in high solution capacity at moderate concentration, its high
alkalinity, relative ease for reclamation and low solvent costs are some of the advantages
that offset in many cases the inherent disadvantages of MEA (Kohl and Neilsen, 1997).
Selection of the proper solvent depends on the temperature and pressure of the gas that is
to be treated, its composition with respect to major and minor constituents, and as
mentioned earlier, the purity requirements of the treated gas. Additional constraints like
selective removal of one gas or simultaneous removal both gases (H2 S and CO2) also
influence the solvent selection. Other operational issues like corrosion which has a
pronounced effect regarding the MEA-CO2 system at high concentrations (>20%) and at
high loading of the acid gas impose operational constraints. Hence, there is no ideal
10
solution that will give the optimum conditions. Despite these facte, sufficient data and
operating experience with several alkanolamines serve as a benchmark for the selection
of treating solutions for a wide range of conditions (KoM and Neilsen, 1997).
The latest trends on gas treating are mixed amine system where the properties of one of
the amine help to compensate for the undesirable effects of the second amine. It has been
found that small addition of primary amine to the tertiary amine enhances the rate of
absorption of CO2 largely without changing the stripping characteristics. MEA as a
primary amine has several disadvantages. As mentioned earlier, corrosion is a major
problem associated with MEA. The effect of corrosion increases at high acid gas
loading. MEA cannot be loaded beyond 0.5 mol of CO2 per mole of amine as this is
limited by stoichiometry. The advantage of MDEA is that it has high equilibrium loading
capacity (1.0 mol of CO2 per mole of amine). Secondly, MDEA has low corrosion rate at
high loading. MDEA has a low heat of reaction and requires a low heat for regeneration.
MDEA also has a low degradation rate. The vapor pressure of MDEA is very low (0.01
mmffg at 20C) whereas for MEA, it is relatively high (0.36 mmHg at 20C), hence low
solution losses(Kohl and Neilsen, 1997). Some of the disadvantages of using MDEA are
the higher cost, tendency of foaming at high concentrations and slow rate of reaction of
CO2 and high viscosity. When the mixed amine solution reacts with CO2 , the
disadvantages are counteracted. It is found that the higher equilibrium capacity of tertiary
amine combined with the higher reaction rate of primary or secondary amine, results in
improvement in gas absorption of CO2 and greater savings in regeneration costs (Kohl
and Neilsen, 1997). Some of the blends that have been extensively utilized in the industry
11
are MEA-MDEA, MDEA-DEA. A detailed discussion of the reaction kinetics and
absorption of 0 2 into these systems is included in the literature survey part of the
thesis. Although the mixed amine system is of wide interest, data on the absorption,
kinetics, and physico-chemical properties are scarce. Proper understanding of the kinetics
of absorption reaction of mixed amine system is essential for the effective design of
absorption units that use the mixed amine system.
Most of the required kinetic data can be obtained from laboratory scale experiments. The
experiments can be broadly classified into: differential and integral (Astarita et al., 1983).
In a differential experiment, the operating variables (i.e. temperature, pressure,
composition, etc.) are fixed at some unique pre-determined values, the values of some
dependent variables (e.g., absorption rate for laminar jet, wetted wall etc.) that is
presumed to depend on the above operating variables is measured. Some of the physico
chemical properties cannot be measured directly from these experiments, but reliable
absorption rate helps to calculate diffusivity from standard equations for physical
absorption. Also the functional dependency of the dependent variable is determined by
repeating the experiments over a wide range of temperature. An example is the wetted-
wall column where the rate of absorption can be determined at wide range of
temperatures, pressure, and contact time. From the dependency of the absorption rate on
temperature and composition, reaction mechanisms can be elucidated. In an integral
experiment, the operating variables are not constant; their values vary from point to point
in time within a single experiment. A typical example is a pilot plant where the
12
composition, temperature, and pressure have various values at different points in the pilot
plant. Hence, these fundamental data cannot be obtained only from them.
The key parameter required for the design and simulation of an absorber is the reaction
rate data. The absorption of acid gases into aqueous alkanolamine solution is considered
to be a heterogeneous non-catalytic reaction. As mentioned earlier, the reaction rate is
dependent on composition, temperature, pressure, mass transfer and heat transfer rate.
The reaction between CO2 and amines is exothermic and for the reaction to take place
CO2 has to diffuse from the gas phase to the liquid phase. Hence heat and mass transfer
effects play an important in alkanolamine-COa reaction system. In the present work, only
the mass transfer aspects will be considered. The heat effects will not be considered.
1.2 Objectives
It has been found in the literature that there are not enough data to represent the mixed
amine system. Chakravarty et al.( 1985) have suggested blends of primary and tertiary
amines such as MEA+MDEA+H2 O for CO2 removal. Critchfield and Rochelle, 1987
studied the absorption of CO2 into aqueous solutions of MDEA-MEA in a stirred-cell
absorber. However, the kinetics of the reaction of CO2 into mixed amine solution at low
and moderate loadings have not been reported except for Glasscock et al.(1991). The
experimental data obtained by Critchfield and Rochelle, 1987 suggested that a shuttle
mechanism could be used to describe the absorption of CO2 into MEA-MDEA+H2O
instead of the assumption that the reactions occur In parallel paths. Versteeg et al. (1990)
carried out a study of CO2 absorption into various mixed alkanolamines. The aqueous
mixed alkanolamine systems experimented were MMEA-MDEA, MEA-MDEA, DIPA-
13
MDEA and MEA-DEA-MDEA, The experiments were carried out in a stirred vessel over
a wide range of process conditions. An absorption model was developed taking into
account the phenomenon of mass transfer accompanied by multiple complex parallel
reversible reactions.
Glasscock et al. (1991) investigated the absorption/desorption of aqueous MDEA/MEA
and MDEA/DEA solutions over the range from 288 to 313K with a gas-stirred cell
reactor. Combined mass transfer/equilibrium model based on the zwitterion mechanism
suggested by Danckwerts (1979); Blauwhoff et al.(1984) effectively represented the mass
transfer rate for the mixture of MEA/MDEA and DEA/MDEA. Rangwala et al. (1992)
measured the absorption of CO2 into aqueous blends of MDEA and MEA solutions in a
stirred cell absorber. A modified pseudo-first order model based on film theory was used
to predict the rate of absorption into mixed amine solutions. Bulk liquid concentrations
of various species present were obtained from a simplified thermodynamic model. The
model predicted absorption rates, which were in good agreement with experimental
measurements.
Hagewiesche et al. (1995a) reported the absorption of CO2 into aqueous blends of
MDEA and MEA solutions in a laminar jet apparatus at low contact times. The
experiments were performed at 313K. They proposed a model based on the system of
parallel reversible reactions according to Higbies penetration theory for the predicting
gas absorption rates and enhancement factors.
Rinker et al. (2000) measured the rate of absorption of CO2 into aqueous solution of
MDEA and DEA in a laminar jet absorber and stirred cell absorber. A model based on
14
penetration theory that incorporates an extensive set of important reversible reactions and
takes into account the pairing between the equilibrium constants, mass transfer and
chemical kinetics was developed. Xiao et al. (2000) studied the kinetics of absorption of
CO2 into aqueous blends of MDEA and AMP solutions in a laboratory wetted-wall
column. Ten systems of AMP and MEA of which two were pure aqueous AMP without
the promoter, MEA were used and the experiments were conducted at three different
temperatures (30, 35, 40*C). A simplified hybrid kinetic model was adopted to interpret
the results. The model was found to satisfactorily interpret the experimental results.
Homg and Li, 2002 explored the kinetics of absorption of CO2 into aqueous Mends of
TEA and MEA solutions in a laboratory wetted-wall column. Ten systems of which 0.5
and 1.0 kmoLm'3TEA mixed with various concentrations of MEA (0.1, 0.2, 0.3, 0.4 and
0.5 kmol.m'3) were studied. The experiments were conducted at three different
temperatures (30, 35, 40*C). The overall reaction rate for the system was determined
based on the fast pseudo-first-order reaction regime. A simplified hybrid kinetic model
1.e., a zwitterion mechanism for MEA and a pseudo-first order reaction model for TEA
was adopted to interpret the results. Zhang et al. (2002) measured the absorption rates of
CO2 into aqueous blends MDEA and DEA solutions in a laboratory disk column, and the
kinetics of absorption were studied. A weight ratio of (MDEA/DEA) from 50/3 to 50/10
at a total amine concentration of 3.0M was used. The experiments were conducted at
different temperatures from 313 to 343K. The CO2 absorption was considered as a rapid
pseudo-first-order reversible reaction between CO2 and DEA. A second order-rate
constant between CO2 and DEA was obtained under this condition.
15
Liao and Li, 2002 measured the absorption rates of 02 into aqueous blends of MDEA
and MEA solutions in a laboratory disk column and the kinetics of absorption were
studied. The experiments were performed at 30, 35, 40C. The overall reaction rate for
the system was determined based on the fast pseudo-first-order reaction regime. A
simplified hybrid kinetic model i.e., a zwitterion mechanism for MEA and a pseudo-first
order reaction model for MDEA was adopted to interpret the results.
Details of experiments conducted on the kinetics of COa in mixed amine systems by
various researchers is summarized in Table 1.3. From this table, there is enough scope to
obtain reliable data for various concentrations of mixed amine systems and acid gas
loadings. Secondly, all experiments conducted were either at one temperature
(Hagewiesche et al., 1995a; Zhang et al., 2002) or two or three temperatures (Glasscock
et al, 1991; Homg and Li, 2002; Liao and Li, 2002; Xiao et al., 2000). Since the kinetic
rate constant is not available for a wide range of temperatures (298K to 333K), there can
be some inconsistency in applying the kinetic rate for all temperatures at which an
industrial absorber is operated.
Third, the experiments were not performed for more than three concentrations of mixed
amine solution systems except in two cases: (Homg and Li, 2002; Liao and Li, 2002).
Finally, in most of the above experiments the effect of CO2 loading is not taken into
consideration with the exception of Glasscock et ai.(1991). Even for single amine system,
COa-MEA, Littel et al. (1992b) questioned the data reported by Savage and Kim (1985)
as they did not consider loading effects on the physical properties and kinetics.
16
There are two ways of changing the free amine concentrations: either by varying the
individual amine concentration or the loading of the solution (Aboudheir et al, 2003).
The second method was adopted to change the free amine concentration. For each mixed
amine system five different loaded systems were used to conduct the absorption
experiments. The effect of loading on the physical properties is required to interpret the
kinetics. Based on the above points, there appears a need for obtaining more accurate
experimental data on a laboratory scale to determine the kinetics of the mixed amine
system, by taking the following into consideration:
1. Obtain reliable data on the absorption rate of CO2 into loaded mixed amine
solutions under the condition of no Interfacial turbulence. One of the best apparatus
that can be used to generate reliable absorption data is the laminar jet absorber
because the interfacial area is known accurately. (Danckwerts, 1970; Astarlta et al,
1983).
2. Conduct the kinetics experiments within the typical range of temperature found in
absorber, which Is from 298 to 333K.
3. Develop a kinetic model for absorption of CO2 into loaded MEA-MDEA by
applying the Zwitterion mechanism, Termoleculat Mechanism, and the Power Law
model.
4. Interpret the experimental data of the CO2 -MEA-MDEA system with the aid of the
simplified absorption model. The physical, chemical properties of the system as a
function of temperature, concentration, and loading are used to interpret the
absorption data. It should be mentioned that in previous studies of mixed amines,
17
the effects of loadings on the physico-chemical properties were not
account in the interpretation of the experimental data.
Table 1.3 Compilation of kinetics of CO2 in mixed amine system
Mixed amine
solution
Composition
(mole/L)
Temp.
(Q
Experimental
technique
Calculation
method
Ref.
MDEA+MEA 1.34+0.65 25 Stirred cell Numerical
model
Glasscock et
al., 1991 MDEA +DEA 0.59-1.85+
0.10-0.57
25,40
MDEA+MEA 2.43+0.25
2.30+0.50
2.17+0.75
40 Laminar jet
absorber
Numerical
model
Hagewiesche
et al., 1995a
AMP+MEA 1 .5+0.1,0 .2 ,0 .
3 and 0.4
30,35,40 Wetted wall
column
Simplified
model
Xiao et al.,
2 0 0 0
1.7+0.1,0.2,0.
3 and 0.4
TEA+MEA 0.5+0.1,0.2,0.
3,0.4 and 0.5
column
Simplified
model
Homg and
Li, 2002
1 .0 +0 .1 ,0 .2 ,0 .
3,0.4 and 0.5
MDEA+MEA 1 .0 +0 .1 ,0 .2 ,0 .
3 , 0.4 and 0.5
column
Simplified
model
Liao and Li,
2 0 0 2
1 .5+0.1,0 .2 ,0 .
3,0.4 and 0.5
MDEA+DEA 2 .8 +0 . 2
2.4+0.6
60 Disc column Simplified
model
Zhang et al,
2 0 0 2
2.7+0.3 40,50,60,
70
19
2.THEOMY
The mechanisms for the reaction between carbon dioxide, primary and tertiary amines are
presented, and a vapor-liquid equilibrium (VLE) model to predict the bulk concentrations
of all chemical species is developed. The VLE model is used along with the physical
properties model given in Appendix B to determine the species concentration at various
loadings. In addition to the VLE, a simplified kinetics model will be dealt with in this
chapter. The widely accepted zwitterion mechanism (Danckwerts, 1979) and
termolecular mechanism (Crooks and Donnellan, 1989) are adopted in the kinetic
analysis.
2.1 Chemical Reactions
A generic chemical reaction between carbon dioxide, primary amine such as aqueous
MEA and tertiary amine such as MDEA is given below (Blauwhoff et al., 1984; Versteeg
and van Swaaij, 1988; Littel et al., 1992a; Liao and Li, 2002). This mechanism involves
the reaction of MEA (KNHj) with COa to produce a carbamate (KNH2COO') by the
deprotonation of the zwitterion by the base. Any base present in the solution may
contribute to the deprotonation reaction. The contribution of each base to the overall
reaction rate depends on its concentration as well as its strength. Here R refers to
CH2 CH2 OH. Though zwitterion mechanism is not shown In the generic chemical
reaction given below, it will be shown in detail when the kinetics based on the zwitterion
mechanism for primary amine is discussed in the later part of this chapter. The
contributions to the deprotonation of zwitterion in aqueous solutions of mixed
alkanolamine can be from MDEA, MEA, OH', or H2O (Liao and Li, 2002), though
20
mainly from MDEA and MEA and to a lesser extent from OH', H2O (Hagewiesche et al,
1995a).
The following reactions (which are similar to that of Rinker et al., 2000; Hagewiesche et
al, 1995a; Versteeg et al, 1996) for the reaction of CO2 with primary, secondary' and
tertiary amines) may occur when the CO2 is absorbed into and reacts with aqueous
MDEA-MEA solution. The proposed mechanism for the reaction between CO2 and
tertiary amine represented by reaction 2.5 indicates that they do not react directly with
CO2 . Instead, tertiary amines act as bases, which catalyze the hydration of CO2
(Donaldson and Nguyen, 1980; Versteeg and vanSwaaij, 1988; Littel et al., 1990;
Hagewiesche et al, 1995a).
Ionization of water
H20 < - ^ O H ~ + H+ (2.1)
Dissociation of dissolved carbon dioxide through carbonic acid:
C02+ H20 < ECO; + H+ (2.2)
Dissociation of bicarbonate
hco; CO*'+H+ (2.3)
Formation of bicarbonate
C02+ OH~ < >hco;
(2.4)
Reaction of CO2 with tertiary amine
co2+ rrch3n + h2o<-&->rrch3n h ++hco;
(2.5)
RRCH,N + RRCH.NH*
(2.6)
21
Reaction of CO2 with primary amine
RNH2+ C02<--&** >H *+ RNHCOO- (2.7)
iWif2+ 77+< >RNH3+ (2.8)
RNHCOO~ + i / 20 I M 2+ C03" (2.9)
where K-, is the equilibrium constant, kj is the forward rate coefficient , and Lj is the
backward rate coefficient for the reaction i. Carbamate to bicarbonate reversion (reaction
2.9) is neglected while calculating the bulk concentrations of the species because of low
reaction rates and short contact times which are the characteristics of the laminar jet
absorber, and it has been found that reaction 2.9 does not have a noticeable effect on the
Vapor Liquid Equilibrium (VLE) model and the overall reaction of CO2 in mixed
alkanolamine system (Hagewiesche et ah, 1995a).
2.2 Liquid bulk concentration of all chemical species
A computer thermodynamic model to estimate the liquid bulk concentration of all
chemical species was developed based on the reactions discussed above. The input data
of the model included initial concentration of the MEA and MDEA solution, [MEAjo,
[MDEAJo, initial CO2 loading of the mixed amine solution, a , the equilibrium constants
of the reactions, and the solubility of CO2 into MEA and MDEA solution as a function of
both amine concentration and temperature. AH the chemical reactions are at equilibrium
and the concentration of water is assumed to remain constant because its concentration is
much larger than the concentration of all other chemical species and also due to the short
contact time in the laminar jet absorber. The concentrations for the remaining eight
22
chemical species shown in the above chemical reactions were calculated by solving the
following mass balance equations and the Henrys law correlation:
MEA balance:
[RNH2] + [RNH3 ] + [RNHCOO-] = [MEA\ (2.10)
MDEA balance:
[RRCH3N]+[RRCH.NH+] = [MDEA]0 (2.11)
Carbon balance:
[CO2] + [HC03~] + [C032~] + [RNHCOO ~] = {[MDEA\ +[MEA}0)a (2.12)
Charge balance:
{RNH +] + { RRCHNH+] + [H*] = [RNHCOO-] + [ HCOf ] + 2[C032' ] + [Off~]
(2.13)
Independent equilibrium constants:
Kj=[OH][H+] (2.14)
K3 =[C032l [ H +]/[HC03-] (2.15)
k 5= [ r r c h 3n h +] [ h c o ; ]/[co2] [ r r c h 3n] (2 .1 6 )
K6=[RRCH3NH+]/[RRCH3N] [H+3 (2.17)
K7=[H+][RMHC00-]/[RNH2][C02] (2.18)
Kg=[RNH3+]/[RNH2][H+] (2.19)
In addition to these mass balance equations, Henrys law relationship between the
equilibrium partial pressure and the free concentration of CO2 is required:
23
PMj=He[C02] (2.20)
As mentioned earlier, though K is an independent equilibrium constant, it is not included
while solving the system of equations because of the negligible rate of the carbamate
reversion to bicarbonate reaction at short contact time. To solve these non-linear
algebraic equations for the bulk concentrations, the values of the solubility (in terms of
Henrys law constant, He) and the equilibrium constants are required. The solubility of
CO2 into the mixed amine solution was calculated using the N2O analogy. Details of die
calculation are based on the work of Wang et al. (1992) and are presented in chapter 3.
The equilibrium constants Kj, K3 , K5 , K7, Kg developed by various researchers expressed
as a function of temperature have been adopted here. The equilibrium constants were
programmed in subroutines within a module called Equilibrium-Constants, of Appendix
B. These subroutines are accessible for all the computer programs used in this work.
The eleven nonlinear algebraic equations, Equations 2.10 to 2.20, were solved for the
eleven unknowns of the bulk concentrations and equilibrium partial pressures using a
FORTRAN 90 program called VLE-Model presented in Appendix A. The FORTRAN 90
program utilizes a subroutine called DNEQNF documented in the IMSL MATH/Library
for solving a system of nonlinear algebraic equations. DNEQNF was successfully used
to solve the non-linear equations by Aboudheir et al. (2003). This routine is based on the
MINPACK subroutine HYBRD1, which uses a modification of MJ.D. Powells hybrid
algorithm. The algorithm is a variation of Newtons method, which uses finite difference
approximation to the Jacobian and takes precautions to avoid large step sizes or
increasing residuals ( Visual Numerics, Inc., 1994a). By this technique, it has been found
24
that the program converged to the solution even when the initial guesses of the bulk
concentrations and partial pressure were not close to the solution. The results for bulk
concentrations obtained by the VLE model for aqueous mixed amine system are shown in
Figure 2.1. This figure shows how the species concentration varies with carbon dioxide
loading from 0 to 1 in a 27wt.%MDEA/3wt.%MEA solution at 313K. The speciation
plot given here has a similar trend to those obtained by Austgen et al. (1991) using the
Electrolyte-NRTL model for vapor-liquid equilibrium in acid gas-mixed alkanolamine-
water system.
As shown in Figure 2.1, the main products with high concentrations are ENBV, HCO3",
RNHCOO', RRCH3H+ at loading below 0.5. Though the speciation was developed for the
CO2 loading from 0 to 1 .0 , the experiments were only performed from 0.05 to 0.15 CO2
loading due to the operational constraints imposed by the laminar jet absorber and the
nature of mixed solvent ( the nature of the solvent being it is slow reacting when loaded
with CO2 unlike primary amine) used in this study. It can be observed that the
concentration of free carbon dioxide, [CCy, is found to increase only at loading beyond
0.8 (see Figure 2.1, the solid line increases after a loading of 0.8). Also, there is sharp
increase in the bicarbonate, (HCO3") concentration at loading beyond 0.3, due carbamate
reversion to bicarbonate. Since the experiments were conducted for loadings, < 0.15, the
exclusion of Equation 2.9 for solving the system of equations is acceptable (see Figure
2.1). OH', CO32', FT concentrations are located near the X-axis and are smaller in
magnitude when compared to the species shown in the figure.
25
e
S3
<53
b
a
o
S3
o
3
2.5 HCOs'
RRCttN
2
1.5
1
0.5
0
0
1 0.6 0.8 0.4 0.2
Loading, moles of COj/fnoles of anise
Figure 2.1 Liquid-phase speciation and concentration in aqueous MDEA-MEA
(27wt.%-3wt.%) solution with CO2 loading (a) from 0 to 1.0 at 313K. The
thermodynamic model developed in this work predicted the composition of species.
26
23 Kinetics f Reaction
The reactions between COa and MEA solution have been described in the literature by
two mechanisms namely zwitterion and termolecular mechanisms and the reaction of
CO2 and MDEA solution has been explained based on the base-catalyzed hydration of
COa. The zwitterion mechanism consists of the reaction of CO2 with primary amines like
MEA to form a zwitterion intermediate (RNH2 +COO-) followed by the deprotonation of
the zwitterion by a base to form carbamate (RNHCOO-), where R is CH2 CH2OH.
( Danckwerts, 1979; Blauwhoff et al, 1984; Versteeg and van Swaaij, 1988, Liao and Li,
2002). Any base in the reaction will contribute to the deprotonation of the zwitterion.
The contribution of each base to the reaction rate depends on its concentration as well as
its strength in the reaction. The main contributions for the deprotonation of zwitterion in
aqueous solution of primary and tertiary amine are from the amines (MEA and MDEA),
hydroxide (OH") and water (Blauwhoff et al., 1984; Versteeg and van Swaaij, 1988:
Rinker et al, 2000; Liao and Li, 2002).
For MDEA and CO2, the base catalyzed hydration of COa by the tertiary amines is the
most widely accepted rate mechanism (Donaldson and Nguyen, 1980; Haimour et al.,
1987; Versteeg and vanSwaaij, 1988; Littel et al, 1990 a,b; Hagewiesche et al., 1995a).
It is found that the tertiary amine does not directly react with CO2 . Instead, tertiary amine
acts as a base which catalyses the hydration of CO2 .
The zwitterion mechanism consists of the formation of a complex zwitterions followed
by the deprotonation of the zwitterions by a base (Danckwerts, 1979; Blauwhoff et al.,
27
1984), which can be represented as (refer to Equation 2.7, which is overall carbamate
formation reaction):
where B corresponds to any species in the solution that can act as a base to abstract the
proton from the zwitterions, and in the case of loaded mixed amine solution, such species
are [RNBh], [BqO], [OH"], [R3N], [HCOa"], [CO32' ] . As mentioned earlier, the reaction
with tertiary alkanolamines is essentially a base catalyzed reactions as proposed by
Donaldson and Nguyen, (1980). Based on this, the overall reaction rate of CO2 into
mixed amine system can be expressed as follows (Liao and Li, 2002):
Tov ~ rC02-MEA+ rC02-MDEA+ rco2-OH~ + TC02-H20 (2.23)
where the reaction rates are CO2 with MDEA, MEA, hydroxyl ion and water. Owing to
the insignificant contribution, the reaction of CO2 with water, i.e., rcc>2_Hi0 in Equation
2.23, is usually neglected (Blauwhoff et al., 1984).
The reaction of CO2 with hydroxyl ion is considered as the bicarbonate formation:
This reaction is fast and can enhance mass transfer even when the concentration of the
hydroxyl ion is low. The forward reaction is described (Pinset et al, 1956) as
C 02+ RNH2 r n h 2+coct (2-21)
RNH2+COO~ + B RNHCOO~+ BH+ (2.22)
C02+0H~ *>HC03~ (2.24)
(2.25)
logj0(k*OH_im3kmol~is~l) = 13.63 5 -2895/T(K) (2.26)
28
23.1 Reaction rate dependence on MEA
Carbamate formation occurs when COj reacts with primary and secondary amines:
RNH2+ C02 f f ++ RNHCOO- (2.7)
Zwitterion mechanism, which has been explained above, is generally accepted as reaction
mechanism for Carbamate formation. Zwitterion mechanism has been widely used in
aqueous alkanolamine solutions (Blauwhoff et al., 1984; Barth et al, 1984) as well as in
some organic and viscous solution by Sada et al. (1985) and Versteeg and Van Swaaij
(1988b). As described by reactions 2.21 and 2.22, the steps involve the formation of
zwitterions and subsequent removal of proton by a base B (base catalysis).
Danckwerts (1979) reintroduced the mechanism originally proposed by Captow(1968)
and had derived the reaction rate equation for this reaction as quasi-steady state.
Based on this, the general rate of reaction of CO2 with primary amine solution such as
MEA by the zwitterions mechanism can be given (Blauwhoff et al., 1984: Glasscock et
al., 1991; Versteeg et al, 1996) by:
[CO! ][RNHJ) - - t l - f R N H C O O - ] 2 f A ^ L l
r --------------------------^ tL J (2.27)
1 k , 1 7
--------- 1----------- zJ--------
^2MEA ^2MEA^^b[B]
For the system under consideration, MEA with CO2 since the second term in the
numerator is usually negligible under low loading absorption conditions, the rate of
reaction is given by:
29
rC02AMINE~ f
[C02][MEAj
(2.28)
^2,MEA
1
^2,MA []
/
The zwitterion mechanism covers the shifting reactions orders, i.e., the overall reaction
order changes between two and three, for the reaction of CO2 with primary and secondary
amines. The zwitterion mechanism can be applied in this study, to the reaction between
CO2 with MEA for the CO2 absorption into MEA+MDEA+H2 O. Since the bases B in
Equation 2.22 can be MEA, MDEA, OH", or H2O, the forward reaction rate for CO2-
MEA, i.e., Equation 2.28 becomes
23.2 Reaction rate dependence on MDEA
For the reaction of CO2 with tertiary alkanolamines (R3N), Donaldson and Nguyen,
(1980) proposed the mechanism as given by Equation 2.30. As mentioned earlier, the
mechanism implies that tertiary amines cannot directly react with CO2 . In most of the
literature on CO2 kinetics with aqueous tertiary amine solutions, it is assumed that the
reaction of CO2 with MDEA is a pseudo-first order reaction with respect to CO2
(Blauwhoff et al, 1984; Versteeg and van Swaaij, 1988b;Tomcej and Otto, 1989) as
follows:
[CDJPEAj
1
"*"^2>EA^ce-
(2. 29)
r C02-MDEA 2,MDEA
[C02 ][MDEA] (2.30)
30
The kinetics study based on the pseudo first reaction assumption means that since MDEA
is in large excess there is no concentration gradient of MDEA in the liquid reactant and
therefore the interface conditions can be represented by bulk conditions.
The reaction rate equation, Equation 2.30, will be used in this study to represent the
reaction kinetics of COa with MDEA in ME A+MDE A+H20 .
23.3 Overall reaction rate for CO2 with MEA+MDEA+H2O
Substituting the zwitterion mechanism for CO2 -MEA, i.e., Equation 2.29 and C02-
MDEA, i.e., Equation 2.30 in Equation 2.23,
fov- kovICOa]
(2.31)
%MmEC02)[MDEA]^(1I.[CX^][CIT]
and the apparent rate reaction constant, kappis defined as
kw=kw~k*OT[OHl (232)
kapp-[MEA]/(l/k2>MEA'+(l"Kk2MEAkH2O/^.l)[H203+(k2MEAkoH-^c-l)[0lH']
'+(^23ffiA^MEA^:-l)lMEA]+(k2sMEA^;MDEA^-l)Pv ^ ] +^:2J(EAP^^1]))
(2.33)
The overall reaction rate defined above is based on the zwitterions mechanism. The term-
molecular based kinetics will be incorporated below.
23.4 Termolecular mechanism
Termolecular mechanism assumes that the reaction takes place in one single-step where
the initial product is not a zwitterion, but a loosely- bound encounter complex as shown
31
in Figure 2.2. The complex breaks up to form reactant molecules, few react to form with
a second molecule of amine, or a water molecule, to give ionic products.
R
R N:
/
O
II
B H
Figure 2. 2 Single step, termolecular reaction mechanism for the formation of carbamate
(Crooks and Donndlan. 1989)
Crooks and Donnellan (1989); Versteeg et al. (1996) presented the forward reaction rate
for this mechanism by:
23.5 Methodology to determine kinetics
The rate of absorption of COa into mixed amine system can be obtained from the laminar
jet apparatus. Given the data for physical absorption at short contact time and with an
initial gas-free liquid based on the Higbies penetration theory, specific absorption rate
( N a ) and liquid phase mass transfer for physical absorption of CO2 ( ki) are given by
*-co2=(kH2o[H20 ] + kMEA[MEAj)[MEAj[C02j (2.34)
N A = 2 ( D j / t i t ) l!2 ( p A I H ) (2.35)
32
where r contact time which is defined below, pa, partial pressure of COa, H , Henrys
law constant, Dj diffusivity. x = 7td2U4 Q, d and I are diameter and length of the laminar
jet, Q is the volumetric flow rate.
k \ = z Jd J ttt (2.36)
and the enhancement factor of CO2 is determined by
E- Na/ ( k \ [C02*M C02]b) (2.37)
[C02*], [ C02]b are concentration of C02at the interface and bulk in the liquid, Na is the
average rate of absorption per unit area.
The conditions for the absorption of C02 was selected in such a way as to ensure that
absorption occurs in the fast pseudo-first order regime which is given by:
3 < Ha <E (2.38)
where the Hatta number Ha is
H = ^ kv-Dc.gi. (2.39)
K
and E = Na!k * (C*-C) (2.40)
The specific rate of mass transfer of C02is given by:
[CO,]; J k 0VDC0
Na= ----........ 2 (2.41)
tmh^jKPcoJK)
For Ha>3, tanh Ha approaches one, thus, the specific rate of mass transfer of C02
becomes:
NA- [ CO,1V E ^ - | ^ [ ( V U W ] (2.42)
COj
33
(2.43)
The specific absorption of CO2 (Na) into the MEA+MDEA+H2O can be measured for
various systems at different temperatures and CO2 loadings. The koVis calculated by
Equation 2.43 knowing the diffusivity of CO2 in the solution, Dqqi (refer to section 3.4
for diffusivity), partial pressure of CO2 , Pco2s and the Henrys law constant, Hcq2s in the
solution. Henrys law constant is obtained from Wang et al. (1992) model, which is
discussed in section 3.3. kapp is calculated from koVby Equation 2.32. The values of
experimental kaPPvalues are fitted to the zwitteion ion mechanism rate expression or the
termolecular mechanism rate expression to obtain the individual rate constants,
given by Equation 2.33. The kinetic calculations can be summarized in flow diagram
given below.
MDEA
, k2MDEA in the expression of kapp
34
Evaluate the Statistics
Evaluate kapp
Physical
Properties
Equilibrium
constants
Vapor Liquid
Equilibrium
Regress k^p based on
Zwitterion, Termolecular
mechanisms and Power law
Raw data at a given temperature, loading, and
composition.
( ^ 2,MEA^H20 / ^ -1 ? ^ 2,MEA^OH-
Obtain rate constants
-l*t%'2,MEAt l MEA 1 n--Hn'2,MEAn'MDEA " - I ' 2,MDEA * 2,MBA
Figure 2.3 Flow diagram for overall and apparent kinetics rate constants calculation
35
3. PHYSICAL PROPERTIES
The numerical modeling, simulation and chemical kinetics from experimental absorption-
rate data require knowledge of physico-chemical of solvents and gas, including
diffusivity, solubility, density, viscosity. This chapter presents a compilation of data and
model interpretation of physical properties available in the literature. Each physical
property was programmed in a FORTRAN 90 subroutine within a computer module
called Physical-proper ties (refer to Appendix B).
3.1 Density
As solution density affects the liquid mass transfer coefficient and experimental data
analysis, the solution density is important in mass-transfer modeling. Density is a
function of concentration, temperature, and CO2 loading. Based on the experimental work
and other published data, Weiland et al. (1998) developed an expression to correlate the
density of mixed amines based on their experimental results. Density was found be a
function of temperature, CO2 loading and concentration.
The density of a solution is given by its average molecular weight divided by its total
molar volume:
X A m , M E A ^ A m , M E A + X A m , M D E A A m , M D E A + + X C 0 2^ C 0 2 , , , < v
------------------------------------ y ------------------------------------- ( }
s
where ps is the solution density(g/cm3), Ys is the molar volume of the
solution(cm3/mol), and Xj and fw* are the mole fractions and formula weights, of the
amines, water and carbon dioxide respectively. For ideal solution, the molar volume is
the sum of the partial volumes of the components multiplied by their respective mole
fractions. The loaded amine solutions are non ideal, and they require additional terms to
36
account for the amine+ water and amine + carbon dioxide Interaction In addition to the
use of a molar volume for dissolved CO2, which is unrelated to its pure-component value.
For loaded solutions, Weiland et al. (1998) gave the molar volume for mixed amine
solution as:
^ ~ X M E A ^ M A + X MDEA^MDEA + X H , 0 ^ H , 0 + X CO, f ' ^ C O , MEA + X : 0 , MDEA 1
7 (3.2)
# # ## ##
+ X MEAX H20 V M E A + X MDEAX H20 V MDEA + X MEAX CG2 V M E A + X MDEAX O02 V M D E A
The molar volumes associated with the interaction between water and amine (Vs),
between carbon dioxide and amine (V##), and for dissolved CO2 (Vcoi) are given in Table
3.1. The molar volumes of pure MEA (Vmea)> MDEA, (Vmdea), and water, (Vmo), can
be obtained from:
Vj =fWj / pj (3.3)
where fwj are the molar weights in g/mol of the pure component and V is the molar
volume in cm3/mol. The density of pure components can be calculated from the
expressions developed by Hsu and LI (1997) as follows:
Pj &j + a2T + a3T2 (3.4)
where p. are densities of the pure components in g/cm3, T is the temperature in Kelvin,
and a, are parameters given in Table 3.1. The molar volume associated with the
interaction between carbon dioxide and the amine, V##
V##= d + e Xmdea (3.5)
This density expression covered wide range of temperatures, from 288K to 473K, and
predicts the density with an average absolute deviation of 0.038% from the experimental
data (Hsu and LI, 1997).
37
Equation 3,1 can be used to calculate the mixed alkanolamine solution density with CO2
loadings up to 0.5 mol CCVmol MEA and MDEA and to a maximum temperature of
398K, with a standard deviation of the fits of the experimental data of 0.00221 for MEA
and .0074 for MDEA (Wetland et al., 1998). The density correlation was programmed in
a FORTRAN 90 subroutine called Density-MEA-MDEA-Soln, Part B.2 of Appendix B,
where the input data of the subroutine are the weight percent of MDEA and MEA,
temperature, and CO2 loading. The outputs of the subroutine are presented in Figures 3.1
and 3.2.
Figure 3.1 shows the density change of MEA+ MDEA solution as a function of
concentration and CO2 loading at 298K. The densities of unloaded 23/7 and 27/3 wt. %
MDEA and MEA are 1.0214 and 1.0234 g/cm3 respectively; the amount of increase in
the density is less than 0.19%. If the loading of the solution is 0.3 mol CCVmol
MDEA+MEA, the density is found to decrease by 0.64%, instead of the appreciable
increase (13%) as reported for single amine MEA by Aboudheir et al. (2002).
Figure 3.2 represents the effect of loading and temperature on the density of 23/7
MDEA/MEA solution. At a loading of 0.3 mol CO2 / mol of mixed amine, increasing the
temperature of the 23/7 MDEA/MEA solution from 298 to 333K decreases its density
from 1.0651 to 1.046 g/cm3; the decrease being 1.80%. For the same solution at 313K, a
change in CO2 loading from 0.1 to 0.3 mol of CCVmol of mixed amine, changes the
density from 1.0284 to 1.0575 g/cm3; an increase of 2.75%. Based on this analysis, the
CO2 loading has minimal effect on the solution density of mixed alkanolamines when
compared to a single amine, MEA, (Aboudheir et ah 2002).
38
Table 3.1 Parameters for density correlations
Parameters MEA MDEA h 2o Reference
ai 1.19093 1.22864 0.863559 Hsu and Li, 1997a
a2 -4.29990X10-4 5.4454x1O'4 1.21494xl03 Hsu and Li, 1997a
a3
-5.66040x1 O'7 -3.35930xi0'7 -2.5708XI0*6
Hsu and Li, 1997a
d 12.983
Weiland et al.,1998
e 397.2
Welland et al.,1998
Vc02
0.04747 -2.8558 Weiland et al.,1998
V# -1.8218 -6.65 Weiland et al.,1998
D
e
n
s
i
t
y
,

g
/
c
m
1.10
1.09
1.08
1.07
23/07
25/05
27/03
1.06
1.05
1.04
1.03
1.02
1.01
0.1 0.2 0.3 0.4 0.5 0.6 0
Loading, mol CCVCmoIe MEA+MDEA)
Figure 3.1 The density of aqueous mixed aikanofamine solution as a function of mixed
amine concentration and COa loading at 298K.
40
D
e
n
s
i
t
y

,
g
/
c
m
1.07 i
&-
1.06 -
1.05
~A
1.04 -
1.03 -
1.02 H
1.01
335 320 325 330 310 315 300 305 295
Temperature, K
Figure 3 . 2 The density of aqueous 23 wi%MDEA/07wt%MEA alkanolamine solution
as a function of temperature and COa loading.
3.2 Viscosity
Viscosity like Density is an important parameter in the naass-transfer rate modeling of
absorbers and regenerators as it affects the liquid-film mass transfer coefficient and
solubility in amines. Solution viscosity was affected by the concentration, temperature
and CO2 loading. Weiland et al.(1998) combined their experimental viscosity data for
partially loaded amines with literature data and reported a useful correlation to calculate
the viscosity of mixed amines at various temperatures. The implemented program for
the viscosity calculations is attached in Appendix B. Viscosity of the solution was not
required to determine the absorption or kinetics.
3.3 Solubility
To model and simulate CO2 absorption into amines, it is necessary to use the free-gas
solubility of CO2 in amine solutions at various amine concentrations and temperatures.
The solubility is also required to calculate the diffosivity and the kinetics of reactions
between the absorbed gas and liquid. Due to the chemical reaction of CO2 with amines, a
common practice is to use N2O analogy to determine the free- gas solubility of CO2 in
amine solutions (Clarke, 1964; Laddha and Danckwerts, 1981; Versteeg and van Swaaij,
1988; Al-Ghawas et al., 1989; Liao and Li., 2002; Aboudheir et ah, 2003). The solubility
may be defined in different ways, but the definition that is used in this work is the form
of Henrys law, which relates the equilibrium concentration of the gas in the liquid as a
function of its partial pressure in the gas phase:
42
He, - Pjf Cei (3.6)
Here Het is the Henry's law constant for the gas i, and Ceiis equilibrium concentration of
the absorbed gas i in the liquid, which is calculated from the total moles of gas physically
absorbed in a volume of absorbed liquid, (Al-Ghawas et al, 1989).
The N2O analogy for solubility of CO2 in amine solutions, Heco2, can be presented as
follows:
Heco2=HeN20 (Hecoa/HeNio) water (3.7)
where Hcn2o is solubility of N2O in amine solution. The solubility of NaO and CO2 in
water can be obtained from the following correlation developed by Versteeg and van
Swaaij (1988), based on published experimental data:
(HecoaW = 2.82 x 106 exp(-2044/T) (3.8)
(HeN2o)water = 8.55 x 106exp(-2284/T) (3.9)
Here solubility is in kPa.m3.kmol'1(kPa.dm3.moF1) and temperature is in K. Substituting
the free gas solubility from equations 3.8 and 3.9 into 3.7 gives the free gas solubility of
CO2 in amine solution.
The solubility of N2O in amine solutions can be calculated from a semi-empirical model
of the excess Henrys law constant that was proposed by Wang et al. (1992).
Wangs model was programmed in a subroutine called Solubility CO2-MEA-MDEA Soln
(see Appendix B) for the solubility prediction of the CO2 and N2O in mixed amine
solutions. The model equations implemented in the computer program are:
The solubility of N2O in mixed amine solutions is given by:
43
I n f e M=J?234+ ; # , J n i f e , y (3.10)
> 2
Here the subscripts 1 represents N2O absorbed gas, and 2 stands for pure amine (MEA)
and water and 4 stands for another amine solvent (MDEA), S stands for aqueous amine
solution. The volume fraction is calculated by the following equation using the density
subroutines that are called in the program:
4
= * / , / ! > / . , p - 11)
2
The excess Henry's quantity for the ternary system is defined as a function of volume
fraction:
i?234 = 2^3^23 + 24&24 ^3^4^34 **"^2*^3 4^234 (3.12)
where the two-body and three-body interaction parameters are considered to contribute
to the excess free energy of the ternary solvent system. The two-body interaction
parameters are assumed to be temperature dependent and the three-body interaction
parameter is independent of temperature and is a constant which is unique for a ternary
system (Wang et al, 1992). Hence, the effect of temperature on the three-body
interaction parameter was neglected by Wang et al.(1992). The temperature dependent
two-body interaction parameter is given by:
a 23=a , +b, / TK (3.13)
The parameters au bi for the binary system and the parameters aa, bi, as, bs used in
a 3Aa 24 for binary interactions between MEA and MDEA, MDEA and water are also
taken from Wang et al.(1992). The solubility of N2O in pure MEA and MDEA required
44
by Equation 3.04 can be calculated from the following expressions, with less than 1.6%
average regression deviation from the experimental data (Wang et al., 1992):
(Hei2>MEA~l .2075 x 105exp (-1136.5/TK) (3.14)
(Hei2)MDEA= 1.524X 105exp (-1312.7/TK) (3.15)
where the units of the solubility are in kPa.dm3/moi and temperature is in Kelvin.
The accuracy of the N20 solubility predictions in amine solutions was found to be
satisfactory based on the model output that was compared with experimental results at
various concentrations of aqueous mixed amine solution. As shown in Figure 3.3, the
model predictions are compared with the published experimental data of Li and Shen
(1992) at various mixed amine (MEA+MDEA) solution systems for three temperatures
and an AAD of 0.62% is reported in the case of aqueous MEA-MDEA solution. The
predicted solubility of N20 in amine solution from Equation 3.10 will be used in
subsequent analyses in order to predict the C02 in amine solution according to the N20
analogy (Equation 3.7).
45
H
e
/
1
0
0
0
,

k
P
a
.
m

.
k
m
o
f
6.5
6
5.5
5
4.5
4
.
o-
' _
" -A-..
24MDEA/6MEA
A 18MDEA/12MEA
O 12MDEA/18MEA
+ 6MDEA/24MEA
30MDEA/0MEA
-4-
3.5
3.15 3.2 3.25
1000/TpC1)
3.3 3.35
Figure 3 . 3 Solubility of NaO in MEA-MDEA solutions as function of temperature.
Points are predicted by the model and lines are experimental by Li and Sfaen, 1992.
3.4 Diffusivity of COa in mixed amines
The molecular diffusivity of the absorbed COa in mixed amine solution is required for
the modeling and simuatlon of gas absorption process. Due to the chemical reaction of
CO2 in amines, the N2O analogy is a common approach used to determine the molecular
diffiislvlty of CO2 In amine solutions (Clarke, 1964; Versteeg and van Swaaij, 1988),
similar to solubility.
Li et al. (1995) performed diffusivity experiments using wetted wall column apparatus.
The diffusivity was calculated by knowing the Henrys law constant, specific gas
absorption rate, the contact time, density and viscosity of the solution.
The N2O analogy for diffusivity of CO2 in amine solutions, Hecoa, can be presented as
follows:
D c02= D n20 ( D c0 2 / D n2o) water ( 3 . 1 6 )
where Dn2 0 is solubility of N2O in amine solution. The diffusivity of N2O and CO2 in
water can be obtained from the following correlation developed by Versteeg and van
Swaaij (1988), based on published experimental data:
{Dco2 W = 2 . 3 5 X iO'2exp{-2119/T) (3.17)
(Dn2o W = 5.07 X 10"2exPC-2371/T) (3.18)
where diffusivity is in cm /s and temperature is in Kelvin. Substituting equations 3.17
and 3.18 in equation 3.16 gives the diffusivity of CO2 in mixed amine solution.
There is a direct method called Protonation Method as cited by Abu-Arab! et al.( 2001) to
measure the diffusivity of CO2 in alkanolamine solutions. The diffusivity of CO2 in 1M
MEA solution at 298K was measured in the laminar jet apparatus used in this work (refer
47
to Chapter 4 for detailed explanation about the apparatus) by protonation method instead
of calculating the diffusivity using the N2O analogy. For the measurement of diffusivity
by N2O analogy using a laminar jet apparatus, (refer to Aboudheir, 2002).
The protonation of alkanolamine is a method by which the reactivity of alkanolamine
solution is eliminated. The alkanolamine solution was protonated using Hydrochloric
acid (HC1) before contacting with CO2 . The procedure is described in brief here. For
detailed information, refer to Abu-Arab! et al. (1989). HC1 (12M) is added to the solution
until the end-point was reached. The protonated 1M MEA solution thus obtained, was the
feed solution to the laminar jet apparatus to measure the diffusivity. The end point was
carefully monitored with the help of a pH meter. This method was not extended to mixed
amine systems as the protonated solution was very corrosive and extremely hard to
operate by a laminar jet because of high viscosity and low rate of absorption. Only a
single experiment was performed for 1M MEA solution at 298K.
The absorption rates ( R a ) of CO2 reported in Table 3.2 were measured at different gas
contact time(t) ranging from 6 to 26 ms(miiiiseconds) by varying both the jet length(h),
liquid flow rate(L), Each absorption rate reported in this table was an average of 5 to 8
measurements.
48
Table 3.2 Experimental data for absorption rate of CO2 in 1M MEA solution at 298K
and atmospheric pressure
L H d t
R a
Ccm3/s) (n) (cm) (sec) (mol/s)
0.613 2.335 0.047 0.0268 5.748E-07
0.613 2.120 0.049 0.0261 5.123E-07
0.613 1.663 0.051 0.0219 4.854E-07
0.613 1.345 0.051 0.0177 4.533E-07
0.613 0.981 0.051 0.0129 3.868E-07
0.694 2.448 0.047 0.0248 6.460E-07
0.694 1.802 0.049 0.0196 5.418E-07
0.694 1.297 0.051 0.0151 4.523E-07
0.694 0.921 0.051 0.0107 3.863E-07
0.694 0.579 0.051 0.0067 2.9! IE-07
49
In the absence of reaction, the total rate of absorption into the jet can be presented
theoretically by the following expression, derived from penetration theory (Astarita,
1967; Danckwerts, 1970):
Ra =4Ce\ /DLh (3.19)
where Ce* is the interfacial-equilibrium concentration of the gas ( CO2) in the liquid
phase. C" can be calculated as explained in the previous section of solubility, section 3.3.
A plot of the experimental data shown in Figure 3.4 of RAagainst VEh , at various flow-
rates and jet-lengths, should be straight line through the origin with a slope equal to
4Ce*-s/D . From Figure 3.4, the value of the slope for the experimental data was found to
be 4.812xl0'7. The solubility, 3.07x1 O'5mole/cm3and the slope were used to determine
the experimental diffusivity. The experimental diffusion coefficient of CO2 in 1M MEA
3 ?
solution at 298K determined by the protonation method is 1.53 xlG' cm /s. The results
thus obtained for diffusivity were compared with the diffusivity values obtained by
substituting in Equation 3.16. The correlation for prediction of N2O diffusivity in amine
is given by Ko et al. (2001):
P n ;0 =(b,+b,M-|-b;Mi )xexpf-b-A ^1 (3.20)
V *
The correlation (Equation 3.20) is a function of amine concentration in terms of molarity
(M) and temperature.
50
Table 3,3 Parameters in the diffusivity correlation (Equations.20) for MEA-HjO
solution (Ko et al., 2001)
Parameters Value
b0
5.07x1 O' 2
bs
8.65xl0"3
b2
2.78xl0'3
b3
-2371.0
b4
-93.4
Table 3. 4 Parameters in the diffusivity correlation (Equation 3.21) for MEA-MDEA-
H20 (Li and Lai, 1995)
Parameters mea+m dea+h2o
bo
-1.89645x1 O'7
bn
2.44679x1c4
bi2
-2.71690xl0'8
b2s
3.98653xl0'7
b22
-8.96763x1O'8
ci2
-8.75280x108
c
-1644.00
Mi
61.08
m2
119.17
R
a
,

m
o
l
/
s
7.0E-07
5.0E-07
4.0E-07
3.0E-07
1.0E-O7
0.0E+00
1 1.2 1.4 0.4 0.8 0.6 0 0.2
, vl/2 2 -1/2
(Li) , cm s
Figure 3.4 Rate of CO2 absorption into 1M MEA solution at 298K and atmospheric
pressure
52
The deviation between the experimental diffusivity values and with those calculated with
the help of the N2O analogy is about 11%. The reason for the deviation can be explained
because the predicted values were obtained based on the N2O analogy where the
diffusivity of CO2 in primary amines cannot be measured directly.
For mixed alkanolamine system, Li et al. (1995) observed that for the total amine weight
percent of 30, the diffusivity was highest for MEA system alone and lowest for aqueous
MDEA system. When a small amount of MEA was added to MDEA, the diffusivity
increased dramatically and diffusivity values lied in between pure MEA and MDEA
systems. Hagewiesche et al. (1995b) also observed the same trend for
MDEA+MEA+H2 O system where the total amine concentrations were 30 and 40 wt.%
respectively.
Li et al. (1995) developed a correlation for diffusivity of N2O in (MEA+MDEA+H2O)
and (MEA+AMP+H2O) systems. The experiments were performed at 30, 35, 40 C and
total solution concentration 30 % wt. The correlation for determining the diffusivity of
N2O in mixed amine solution is given by:
Dn2q = (b0 +b!1M1+b!2M12 +b21M2 +b22M22+ b22M22+ c12M,M2)exp (-c/T) (3.21)
where bo, bn, bo, bat, bn, C21, c are constants specific for each amine system, Mi, M2 are
individual molarities of the amines, T Is the temperature. The correlation has the
molarities of two reacting amines and is a function of temperature. The parameters in the
Equation 3.21 were given in Table 3.4. Equation 3.21 will be used to estimate the
diffusivity of mixed amine for the determination of the kinetics.
53
4, LAMINAR J I T ABSORPTION EXPERIEMNTS
Absorption experiments are performed to obtain reliable data of CO2 absorption into
aqueous solution of partly loaded MEA-MDEA. The experimental data obtained and
discussed in this chapter are under the conditions of no interfacial turbulence(Aboudfaeir,
2002). The data thus generated were obtained by the dynamic method, in which a jet of
liquid moves continuously though the gas for a known contact time. From the literature,
it is observed that only few experiments were performed in the area of chemical
absorption of CO2 into MEA and MDEA. Most of these experiments were restricted only
to aqueous solution mixtures without CO2 loading and only two or three temperatures.
In this study, three different mixed amine ratios (27wt.%/ 3wt.%, 25wt.%/5wt.% 23wt.%/
7wt%) were considered. The CO2 loading into the solution was varied from 0.0095 to
0.1427 moles of CO2 per mol of amine. The absorption rates were utilized to determine
the kinetics of the reaction. The absorption rates were measured with a digital soap-film
meter.
This section is organized in the following order.
The design and method of operation of laminar jet absorber will be discussed. Second,
generating the physical absorption data for CC^-water for the calibration of the apparatus
and calculating the molecular diffiisivities and; generating the absorption data of CO2 into
loaded mixed MEA-MDEA solution for studying the kinetics of the reaction are outlined.
54
4.1 Experimental apparatus and procedure
The schematic of the laminar jet apparatus used for the measurements of absorption rates
is presented in the Figure 4.1. The apparatus was designed by Dr. Ahmed Aboudheir
based on the work of Danckwerts, 1970, Astarita et al., 1983, and Al-Ghawas et al, 1989.
The absorbing liquid constant-head system was fed by gravity through a constant-
temperature bath. The constant-head system was used in order to maintain a constant
liquid flow rate without any ripples. A jet of liquid is issued from a circular nozzle,
flowed downward through an atmosphere of the absorbing gas, was collected in a
capillary receiver. The absorbed gas was supplied from a pressure cylinder and was
saturated with water vapor at the experimental temperature before entering the absorber
chamber.
Jet Chamber Assembly: The jet chamber was a 25.0 cm long, 5.0 cm inside diameter,
acrylic cylinder and was enclosed in a constant temperature jacket, with dimension 25.0
cm in length and 15 cm in inside diameter, acrylic cylinder. The two cylinders were held
between aluminum flanges, and the ends were sealed with rubber gaskets. The nozzle
was mounted at the end of 0.64 mm insider diameter acrylic delivery tube, which passed
through a swage-lock nut in the aluminum flange. The delivery tube can glide in a
vertical direction, which facilitates the change of jet-lengtfa and can be locked in position
by the Swage-lock nut. The jet chamber was provided with a gas entry near the bottom,
gas outlet at the top, a manometer port, a receiver tube, 0.64-cm inside diameter, fitted
into a funnel shaped base.
55
A hole in the base allows the draining of the any liquid overflow through the overflow
port. To avoid vibration, the jet absorber was placed on an anti-vibration pad and all
lines leading to the jet absorber were made from flexible tubing.
Nozzle.- The most important part of the laminar jet apparatus is the nozzle, which
produces the liquid jet. For details regarding the design of the nozzle, refer to Aboudheir
(2002). The extent of departure of behavior of the jet from an ideal rod-like flow depends
on the shape of the nozzle or the orifice from where the liquid-jet is formed,
(Danckwerts, 1970). The nozzle used for the current absorption studies had a circular-
hole orifice of diameter 0.63mm. The circular hole was made in a thin sheet of thickness
0.07Q.005 mm.
Receiver: The receiver was a capillary-fade drilled in an acrylic rod (Aboudheir, 2002).
The length and diameter of the hole were 2.0 and 0.1cm respectively. The receiver
assembly was fitted onto the end of the receiver tube by two o-rings. The downstream
end of the receiver was connected to a constant-level device, which was mounted on a
vertical slide rod and provided with a fine-adjustment leveling screw
56
Gas purge
Soap film meter
:
Constant
head
system
A
Saturator inside
water jacket
Water lacket
Constant level
device
M2
Balloon
Gas feed
Jet chamber inside
water jacket
Exit Liquid Liquid feed
gas flow, ------- - liquid flow
Figure 4.1 Schematic drawing of laminar jet apparatus
from Aboudheir5s Ph.D. Thesis, 2002.
Operation &f the laminar l et apparatus: The absorbing liquid was degassed by spraying
it into a vacuum and kept under a blanket of nitrogen. The liquid was fed by gravity to
the jet chamber from a constant-head system, located about 3.9 m above the absorption
chamber. This was to provide sufficient head for the required rate of flow. The constant
-5
head system is a 200 cm capacity cup provided with a liquid inlet and outlet ports.
During the liquid feed operation, the inlet flow rate was kept higher than the outlet
flowrate and the overflow from the cup was returned to the feed tank. The liquid in both
the constant-head system and the feed tank is kept under the blanket of nitrogen. The
nitrogen supply that replaces the used liquid in the liquid feed tank was stored in a
balloon connected to the feed tank and the constant-head system. The flow rate of the
liquid was controlled by rotameter. The actual flow rate of the liquid was determined by
weighing the liquid discharged in a timed interval during each experiment. A 1000 cmJ
volumetric flask was used to collect the discharged liquid. The constant-liquid level is
used to adjust the liquid level in the receiver. Some of the operational problems due to
high liquid levels and low liquid levels are: not all liquid-jet is collected in the receiver,
some of the jet overflowed and the free jet continued several millimeters down into the
receiver and for low liquid levels the small gas bubbles were entrained in the rapidly
moving liquid inside the receiver. The two aforementioned conditions yielded erroneous
gas absorption rates. The level was adjusted to attain the condition in which there is
neither spillover of the liquid nor entrainment of the gas. A two dimensional traveling
microscope was used to measure the jet-length to a precision of one hundredth of a
millimeter and the jet diameter to a precision of thousandth of a millimeter. The gas from
58
a pressure cylinder was saturated with water vapor at the experimental temperature before
entering the jet chamber. For the determination of the gas absorption rate, a volumetric
technique was used which will be presented in the following section. Temperature of the
liquid entering and leaving the jet chamber were controlled within 0.3C. This was
achieved by having two separate heating/cooling circular units, one for controlling the
gas-stream temperature and the other for controlling the liquid-stream temperature.
The choice of the operating conditions of the laminar jet is based on a number of design
constraints (mainly the design of the nozzle and the receiver). First, the length of the jet
cannot be varied over a range. If the jet is too short, end effect becomes too important; if
it is too long, operation of the receiver becomes difficult. Secondly, the liquid flow rate
can be changed only over a limited range: a lower limit is imposed by the requirement of
avoiding dripping and an upper limit being imposed to avoid turbulence (Aboudheir,
2002). As a result, the former constraint restricts the range of the interfacial area and the
latter limits the range of mass transfer coefficient (Astarita et al., 1983).
Mass flow rate measurements: The best method for measuring the mass transfer rate is
the volumetric technique, which has been used by other authors (Astarita et al, 1983; Al-
Ghawas et al., 1989; Sinker et al., 1995). A schematic diagram, Figure 4.2 can illustrate
the technique used in this work. After obtaining a stable jet -flow, a stream consisting
only of the gas to be absorbed was forced to flow through the absorption chamber of the
laminar jet and purged through a digital flow meter (soap-film meter). The flow meter
was designed to measure flows from 0.1 to 50 cm3/min with an accuracy of 3% of
readings. After sufficient time had elapsed to make sure that the jet chamber, the soap
59
meter, and the long-purge U-tube had been filled with the gas, the gas feed-vaive is
closed. At this point, the flow rate of the gas that was indicated by the soap film meter
equals the volumetric rate of absorption. Experiments were repeated several times and
average was taken.
60
Gas purge
A
%
Oq
aQ
3o
oO
oos
O o
>
oO
180
0*
O 0 C
oOoC
00
4o
0O
oO
lO
0Q
00
] O O S Q Q O G Q O O Q D O u %
O^ Q
Soap
film
meter
Liquid Feed
*3 Gas Feed
Absorption
chamber of the
laminar jet
Exit Liquid
Figure 4. 2 Volumetric technique for measuring the mass transfer rate in laminar jet
absorber
61
42 Calibration of the laminar Jet apparatus
The laminar jet absorber designed in this work was initially tested by absorbing CO2 in
water which is a standard method for testing this type of apparatus as the solubility and
the diffusivity of CO2 in water are very well known (Astarita et al., 1983, Al Ghawas et
al, 1989). When there is no chemical reaction, the total absorption into the jet can be
calculated theoretically from the following equation (Danckwerts, 1970; Astarita et al.,
1983);
Ra =4C/VDLh (4.1)
where RAis the total rate of absorption of gas, Ce *is the equilibrium concentration of gas
at the interface, D is the diffusivity of gas in die liquid, L is the liquid flow rate, fa is the
jet length. A plot of Ra against (Lh)m at various flow-rates and jet lengths, should give
straight line though the origin with a slope equal to 4CeDm.
The main operating variables are the temperatures (T, K), the jet length (fa, cm), and the
liquid flow rate (L, cm3/s). The absorption experiments were carried out at the
temperatures of 298 and 318K to confirm the proper functioning of the laminar jet. As
the experiments were performed at other temperatures and data were compiled by
Aboudheir (2002), they were not repeated in this study. The proper partial pressure of
carbon dioxide, used for calculating the absorption rate, is equal to the total pressure less
than the vapor pressure of water, at the temperature of the experiment. The water vapor
pressure was calculated from the Antoine equation at the experimental temperature.
62
Table 4 . 1 Experimental data for the absorption of CO2 in water at 298K and atmospheric
pressure
L
(cm3/s)
h
(cm)
Ra
(mol/s)
0.836 2.429 8.253E-07
0.836 2.145 7.742E-07
0.836 1.859 7.232E-07
0.836 1.574 6.701E-07
0.836 1.176 5.736E-07
0.769 2.510 7.969E-07
0.769 2.223 7.647E-07
0.769 1.917 7.005E-07
0.769 1.672 6.561E-07
0.769 1.363 5.852E-07
63
The data for absorption at 298K and atmospheric pressure are summarized in Table
4.1.Each absorption rate value reported in this table was an average of 6 to 7
measurements. The experimental data as well as the theoretical predictions of the
absorption rate are shown in Figure 4.3. The points are the experimental and the line is
calculated by Equation 4.1. The diffusivity and solubility of carbon dioxide in water used
in this equation at 298K and lOIJkPa were taken as 1.96x1 O'5 cm2/s and 3.29x1 O5
mol/cm3 respectively (Perry and Green, 1997). There is an agreement between the
measured and calculated absorption rates over various flow-rates and jet lengths with an
average absolute deviation of 0.5%. This indicates that the reliability of the experimental
apparatus, which can be adopted for chemical absorption experiments for kinetics.
The average experimental value found for the diffusion coefficient of CO2 in water at
298K and atmospheric pressure was 1.93x1 O'5 cm2/s. This value is calculated from the
slope of the experimental data which is 5.79xl0"7 and solubility of water at 298K. The
experimental diffusivity values obtained by this work shows a good agreement with that
available in literature, as shown in Table 4.2.
The behavior of the laminar jet absorber was tested as a function of temperature. The
experiments were done at 318K. The experimental diffusivity values were compared with
predicted diffusivity developed by Versteeg and van Swaaij, 1988 as a function of
temperature based on the experimental data published in the open literature
fj
(Temperature in K and diffusivity in cm /s).
D= 2.35xl0"2 exp(-2119/T) (4.2)
64
Excellent agreement between the predicted and experimental diffusivity was obtained.
The average absolute deviation of the measured from predicted diffusivity for two
temperatures 298 and 318K is 2.2%. This is an indication that the laminar jet apparatus
can be operated without any difficulty at this temperature range to determine absorption
rates or kinetics.
65
Table 4.2 Diffusivity of CO2 in water at 298K and atmospheric pressure.
D, cm2/s Reference
1.95x1 O'5 Al-Ghawas et al., 1989
1.96x1 O'5
Perry and Green, 1997
1.94x1 O'5
Tamimi et al, 1994
1.96x1 O'5
AboudWer, 2002
L93xlCT5 This work
R
a
m
o
l
/
s
0.0000009
0.0000008
0.0000007
0.0000006
0.0000005
0.0000004
0.0000003
0.0000002
0.0000001
2 1.5 1 0.5 0
r t u l/2 2/1/2
(Lli) , cm is
Figure 4.3 Rate of absorption of COa into water at 298K and atmospheric pressure in a
laminar jet absorber. Experimental (points), theoretical (line).
67
4.3. Results and discussion for CO2-MEA-MDEA Absorption
The rate of gas absorption was measured in a laminar jet absorber using CO2, MEA,
MDEA. CO2 with the purity of 99.9% was purchased from PRAXAIR. MEA with a
purity of 99.0% was purchased from Fischer Scientific and MDEA with purity of 99.0+%
was purchased from Sigma Aldrich and were used without any further purification.
Typical analysis for the MEA and MDEA based on the information provided by the
respective companies were:
Name 2-Aminoethanol Diethanolmethylamine
Chemical Formula HOCH2CH2NH2 C5H13NO2
Packaging 4 liter, Amber Glass 18 liter, Container
Molecular Weight 61.08 119.16
Assay, % 99.0 99.0+
Molarity, mol/1 16.5
Specific gravity 1.016-1.019 1.04 g/cm3
Water, % 0.3
The experimental data for absorption rate of CO2 into MEA-MDEA solutions at various
concentrations and contact times using the jet apparatus are documented in Appendix C.
The mixed alkanolamine solution was prepared by weight from distilled water, MEA and
MDEA. Routines were written in FORTRAN, which calculated the molarity based on the
weight percent of MDEA and MEA. The total volume of solution used for absorption
experiments is fixed and the density of mixed alkanolamine solution is determined at the
68
solution concentration and loading (refer Chapter 3). These data provide the total weight
of the solution in kg. For each set of experiments, the weight percent of MEA and
MDEA is fixed and from the total weight of the solution, the weights of pure MEA and
MDEA required are known. These quantities are weighed and added to the solution with
the remaining being made up of distilled water. The gas phase was pure CO2 saturated
with water vapor at the temperature of the experiment. The aqueous solutions were in the
concentration range of 0.490M to 1.147M for MEA and 1.996M to 2.316M for MDEA.
Both unloaded (fresh) and loaded solutions were used for the experiments. It was found
that even the unloaded solution contained very small amounts of CO2 , which is absorbed
during solution preparation. This small amount is also taken into account and reported as
the initial loading.
The solution was loaded by spraying the aqueous alkanolamine solution in a closed loop
in a solution through which CO2 was bubbled. The loading of the solutions ranged from
0.0097 to 0.1427 mol CO2 / mol amine. The loading was determined by decomposing the
sample with 2N HC1 and the volume of the liberated CO2 was measured using a Cfaittick
Carbon dioxide Analyzer as specified by Horowitz , 1975. The prepared solution was
mixed thoroughly and kept under a blanket of nitrogen for several hours in order to
ensure equilibrium. All experiments were conducted at temperatures ranging from 298 to
333K and were performed without operational problems like high viscosity at lower
temperatures. Experimental results for the absorption of CO2 into aqueous solutions of
MEA and MDEA in the jet apparatus are shown in Figures 4.4 to 4.6, where the average
absorption rate N is plotted against the contact time x on logarithmic co-ordinates.
69
Figures 4.4 and 4.5 show an increase in the absorption rate as the concentration of MEA
in the mixture and temperature of the solution increases. This is as a result of an increase
in the rate of the reaction that is proportional to the addition of MEA in the blend and
temperature. Figure 4.6 shows a decrease in the absorption rate as the loading of CO2
increases. This is as a consequence of the decrease of free MEA and MDEA
concentration due to increased loading.
The experimental data for kinetics are analyzed and interpreted using the termolecular
and zwitterion mechanisms as well as the power law model The kinetics data are
included in Appendix C.
70
1.0E-07
0.01 ).l
T, S
Figure 4.4 Absorption rate of CO2 into aqueous MEA-MDEA solutions: average
loadings 0.031, T =323K
N
,

m
o
l
/
c
m

s
1.0E-O5
L0E-06
a 313
1.0E-O7
0.01
0.1
T,S
Figure 4. 5 Absorption rate of CO2 into aqueous 23wt.% MDEA - 7wt.% MEA
solutions: loading= 0.031
N
,

m
o
l
/
c
m
2
!
1.0E-O5
1.0E-06
1.0E-07
0.01
Loading = O.OlmoFmoI
Loading =0.054moFmol
Loading = 0. 101 mol/mol
Loading =0.141 mol/mol
0.1
x , s
Figure 4 . 6 Absorption rate of CO2 into aqueous 23wt.% MDEA - 7wt.% MEA
solutions: T = 323K
5. KINETICS OF REACTION
The kinetics of reaction for absorption of COa in mixed alkanolamine system is discussed
in detail in this chapter. The mixed amine solution systems considered were 27 wt. %
MDEA/ 03 wt. % MEA, 25 wt. % MDEA /05 wt. % MEA, and 23wt.% MDEA /07wt%
MEA. For each of this system, five CO2 loadings were considered to change the free
amine concentration (Sada et al., 1985). The total weight percent of the mixed amine
solutions was set at 30. The concentration was fixed as a result of operational problems
involving the laminar jet due to high viscosity of the solution at a higher concentration of
MDEA. The temperature range, 298 - 333K considered was typically found in an
industrial absorber. A recent study done by Liao and Li (2002) considered only three
temperatures and unloaded mixed alkanolamine system, which is not the case in actual
industrial practice.
The individual species concentrations at a given CO2 loading and temperature were
determined with the help of the Vapor-Liquid equilibrium (VLB) model mentioned in
Chapter 2. Since the loading of the solution is also considered, vapor liquid equilibrium
model was used for species concentration prediction instead of directly using the
molarities of the mixed amines as done by Liao and Li (2002). The specific rate of
absorption of CO2 ( N a ) in mixed amine solution was measured by the laminar jet
apparatus. From Equation 2.43 (Chapter 2) the overall rate constant, koVfor the reaction
can be calculated by knowing the partial pressure of CO2, the Henrys law constant and
the diffusivity of CO2 in MEA+MDEA+H2O. The partial pressure of CO2 is calculated
by subtracting the vapor pressure from total pressure which is recorded for each run.
74
The solubility of COa in mixed amine is calculated at the temperature at which the gas
reacts with the liquid using Wang model (see solubility, Chapter 3). Formation of
bicarbonate by the reaction of CO2 with hydroxyl ion, OH' (see Equation 2.4) is
considered in the overall rate expression given by Equation 2.23. Even at low
concentration of alkanolamines, the bicarbonate formation reaction contributes
significantly to the absorption rates and the overall reaction rate constant (Blauwhoff et
al., 1984). Hence, to obtain apparent rate constant, kapp, the contribution of bicarbonate
formation reaction is deducted from the overall rate of reaction.
The experimental kapp and the concentration of free MEA were plotted for all the three-
mixed amine concentrations (27/03, 25/05, 23/07). The experimental kapp obtained are
classified in the tables C.l to C.3. Though experiments were performed at three different
heights (three different contact times), it was observed that the gas absorption data
measured for the smallest height was not reliable due to the end effects (Astarita et
al.,1983). The result is higher gas absorption rates and erroneous experimental kapp.
Therefore, only the two longest heights were included and data for the shortest heights
were eliminated. Few longest heights were also excluded based on the malfunction of the
jet, which were observed and recorded during the time of experimentation. Malfunction
of the jet means the sudden loss of the jet caused by external disturbance like vibrations,
improper positioning of the constant-level device which can cause sudden drop of the
liquid level in the receiver and sometimes even loss of the liquid jet.
The other causes of malfunction are due to oscillatory movement of the jet in the
receiver, over flow in the receiver, which results in abnormally high gas absorption rate.
75
kapp for the two longest heights were plotted against the free MEA concentration and the
equation of the best fit curve for each temperature was obtained. The free MEA
concentrations were substituted in the equations of best fit and average kapp were
calculated. The average kapp are compiled in the Tables C.l to C.2 (last column in the
table). For the analysis henceforth, the average kapp is used to determine the individual
rate constants based on the zwitterion, termoiecular and power law model.
5.1 Interpretation of Experimental kgpp
Figure 5.1 shows a temperature dependence of the apparent rate constant at five
temperatures as a function of the free MEA concentration at the total mixed amine
concentration of 27/03. The raw data of these figures and the results are presented in
Appendix C, Table C.l to C.3. Figures 5.2 and 5.3 show experimental results for the
apparent rate constant kapp for CO2 reaction at total amine concentrations of 25/05 and
23/07. From the Figures 5.1 to 5.3, a temperature dependence of the apparent reaction
rate can be observed for all the five temperatures studied. The kapp vs. concentration of
MEA is not linear and it follows an exponential trend. Similar trends were observed by
Liao and Li 2002 for unloaded mixture of MDEA and MEA at various concentrations and
three different temperatures.
Secondly, it was observed that the kapp decreases with increasing CO2 loading in the
liquid (refer to Figures 5.1 to 5.3). This can be explained by the decrease in free MEA
with an increase in CO2 loading in the solution. The apparent reaction rate also increased
with the increase in temperature and the increment in the MEA concentration by 2 wt.%
(the total wt.% of the mixture was fixed at 30 for all the three systems) in the mixture.
76
kapp for 23/07 > 25/05> 27/03 for any given temperature, kapp at 333K > 323K > 313K >
303K> 298K for any given concentrations (23/07, 25/05, 27/03) of the amine mixtures
(refer to Figures 5.4 to 5.8).
77
25000 -i
20000
- 15000
m
&
a.
10000
5000
0
0.000 0.200
333
0
323
A 313
303
298
0.400 0.600 0.800 1.000 1.200
MEA, mol f 1
Figure 5.1 Apparent rate constant kaPPfor the reaction of COi into aqueous 23wt.%
MDEA - 7wt.% MEA solutions as a function of free MEA concentration.
78
25000
m
2 0 0 0 0 -
^ 15000 -
2
m
0
333
0 323
a
^ 1 0 0 0 0 -
<
O
O
a 313
303
& 4
o 298
5000 -
w H
O A O
& QQ
O*
0
0.000 0.200 0.400 0.600
[MEA], moll1
0.800 1.000
Figure S. 2 Apparent rate constant k^p for the reaction of CO2 into aqueous 25wt.%
79
a
p
p
,
18000
16000
14000
12000
10000
8000
6000
4000
2000
0
0.100
O A
, 0 A
m
333
O
0 323
O A
a 313
4
303
o298
& a
0.200 0.300 0.400 0.500
MEA, moll'1
Figure 5.3 Apparent rate constant km for the reaction of CO2 into aqueous 27wt.%
80
6000 -
5000
4000
t
m
1
2 3000
2000
1000
0
A
23/07
a 27/03
0.000 0.200 0.400 0.600 0.800 1.000 1.200
MEA, mol r1
Figure 5.4 Apparent rate constant k^,p for the reaction of CO2 into aqueous MDEA
MEA solutions as a function of free MEA concentration at 298K.
81
I
9000
8000
7000
6000
5000
4000
3000
2000
1000
0
0.000
23/07
25/05
* 27/03
0.200 0.400 0.600 0.800 1.000 1.200
MEA, mol f 1
82
14000
12000
10000
v 8000
I
J 6000
4000
2000
0
&
23/07
a 27/03
0.000 0.200 0.400 0.600 0.800 1.000 1.200
MEA, moll1
Figure 5.6 Apparent rate constant kapp for the reaction of CO2 into aqueous MDEA
83
2 0 0 0 0 -i
18000 -
16000 -
m
14000 -
- 12000 -
A "
1 1 0 0 0 0 -
23/07
^ 8000 -
A
a
2 5 / 0 5
6000 -
A
a 27/03
m
4000 -
A
A
2000 -
A
U ..... r... r.... 1 1 1 1
0.000 0.200 0.400 0.600 0.800 1.000 1.200
MEA, mol r1
Figure 5. 7 Apparent rate constant km for the reaction of CO2 into aqueous MDEA
25000 -
20000 -
- 15000
Wi
I
^ 10000
5000
0 H i i i i i i
0.000 0.200 0,400 0,600 0,800 L000 1.200
MEA, mol r 1
Figure 5.8 Apparent rate constant k^p for the reaction of CO2 into aqueous MDEA
23/07
25/05
a 27/03
5.2 Determination of Kinetics based on the Zwitterion Mechanism
In chapter 2, reactions 2.21 and 2.22 describe the formation and deprotonation of the
zwitterion. Danckwerts (1979) had developed an overall reaction rate for the zwitterion
mechanism involving the formation and deprotonation of the base based on Caplows
work (Caplow, 1968).
For the mixed amine system under investigation, the expression is given by:
the contributions of these species to the zwitterion deprotonation is negligible (Rinker et
al.s2000) due to the short contact time in the laminar jet. Hence, they are not included in
above expression. The experimental kgpp at each temperature (see Tables C.l to C.3)
individual reaction rate constants k2MEA>^h2o kOH- 5 *^mdea *The nonlinear regression
procedure was based on the modified Levenburg-Marquardt algorithm. The subroutine
DBCLSF documented in the IMSL MATH/library (Visual Numerics Inc., 1994a) was
used to obtain the fitting parameters (individual rate constants). This algorithm proved to
be efficient and has been adopted by Aboudheir et al. (2003). Equation 5.3 was used to
fit and obtain the five parameters. No meaningful values were obtained for all or any of
k
+ ^2MDEA [MDEA]
V 2MEA
(5.1)
where A=
k_j
(k2K C A k f c A [ M E A ] +k2fVAk0fr [GET]+k2IvEAkMcmp4DEA])
Though BCO2 ,COs2 are among the bases contributing to the zwitterion mechanism,
were fitted to the expression given above using a nonlinear regression procedure to obtain
86
the five parameters k2MEA, kHjC, kQH_, , ^ mdea ^ was thus concluded that the
Zwitterion mechanism was not applicable for the loaded mixed amine system under
investigation. Though Liao and Li (2002) could predict the kinetics of absorption of CO2
in aqueous MDEA-MEA by the Zwitterion mechanism, the mixed amine solutions used
in their study were not loaded. Secondly, the equipment for their experiment was the
wetted wall column. For a slow reacting system like the MDEA-MEA, the wetted wall
column may be a more suitable experimental apparatus to investigate kinetics because of
the longer contact times the wetted wall column provides, and hence, the possibility of
better measurements of gas absorption rates.
5 3 Determination of Kinetics based on the Termolecuiar Mechanism
The rate of reaction expression using the termolecuiar mechanism for the reaction of
MEA with CO2 was presented in Chapter 2 by Equation 2.35 as:
rC02 = (kH2J H 20] + k MEA[MEA] + k MDEA[MDEA])[MEA][C02] (5.2)
The apparent rate constant for the mixed alkanolamine is given by:
kgpp = (k0}r [OH- ] + kH20 [H20 ] + [MEA] + [MDEA])MEA + k 2MDEA[MDEA]
(5.3)
Before discussing about the predicted kapp based on the modified termolecuiar
mechanism, it is interesting to examine two asymptotic situations of the zwitterion
mechanism. There are two asymptotic situations for the Equation 5.1 (Zwitterion
mechanism) resulting in:
87
The second term in the denominator, A of Equation 5.1 is I / I ^ m e a - This results
in simple second-order kinetics and the zwitterion formation reaction is rate
limiting.
The second term in the denominator, A of Equation 5.1 is 1/1c2mea- This results
in the following expression and zwitterion deprotonation is the rate determining
and the overall reaction order is three.
In the transition region between the two asymptotic cases, the overall reaction order
changes between two and three. Zwitterion mechanism proposed by Danckwerts (1979)
covers the shifting reaction orders between two and three.
The termolecuiar mechanism was used to fit the experimental apparent rate constants,
kapp (see Tables C.l to C.3). Multiple linear regression was used to fit equation 5.3 and to
determine individual rate constants kH2 0 ,kMEA5k0 H_,kMDEAat each temperature. The
subroutine called RLSE documented in the IMSL STAT/library (Visual Numerics Inc.,
1994b) was used to obtain the optimum fitting parameters. This routine was successfully
utilized by Aboudheir et al. (2003) for a single aqueous primary amine, MEA. In
Equation 5.3, water is an integral part of the reaction rate. Unfortunately, there were no
meaningful results obtained when all the contributing bases (which incorporated water)
were included. Hence, it was concluded that the termolecuiar mechanism as proposed by
Crooks and Donnellan (1989) could not adequately predict the kinetics of the CO2 loaded
mixed aqueous MDEA-MEA solution. Littei et al. (1992a) have observed that kinetics of
CO2 in blends of secondary and tertiary amine cannot be understood in terms of the
88
termolecular mechanism. This scenario is contrary to what has been observed by Crooks
and Doimellan (1989) and Aboudheir et a!. (2003) for single alkanolamine system.
When all the experimental apparent reaction-rate constants( kapp, average data, Tables C.l to
C.3, Appendix C) were fitted to the termolecular expression, Equation 5.3, by a multiple
linear regression procedure, only two parameters, kQH_ and kMEAwere found to fit the
experimental data for kapp. For the system of MDEA-MEA under investigation, if H2O
was substituted with OH' ions in Equation 5.3, Equation 5.4 is obtained.
kapp= O w f H' i + WMEA])[MEA] + k2MDEA[MDEA] (5.4)
This is the modified termolecular mechanism. Henceforth for all discussions and the
prediction of kapp, the modified termolecular mechanism will be utilized.
The multiple linear regression routine RLSE was used to fit Equation 5.4. Equation 5.4 is
identical to the second case of the zwitterion mechanism, when deprotonation of
zwitterion is rate determining. Though previous researchers (Blauwhoff et al, 1984;
Versteeg and van Swaaij, 1988a; Littel et al., 1992a) have found that H2O contributes to
the deprotonation of zwitterion and Crooks and Donnellan (1989); Aboudhier et al.
(2003) have found that HaO contributes to the termolecular mechanism as well, it was
found in this work that the inclusion of H2O for regression yielded meaningless results. A
possible reason is that the deprotonation reaction of the zwitterion by water is a very slow
reaction. Given the short contact time of the absorption experiments in a laminar jet
absorber, a slow reaction is not expected to have an effect in the overall reaction rate
(Rinker et al, 1996). Aboudheir et al. (2003) found that H2O was contributing to the
overall reaction rate using a laminar jet apparatus, the system investigated was
89
monoethanoiamine which is fast reacting with COa when compared to the slow reacting
mixed amine system, MEA-MDEA, OH' ions were found to contribute to the apparent
reaction rate for CO2 loaded mixed alkanolamine system of MEA and MDEA because
the mixed alkanolamine solution used were loaded instead of unloaded solution. For
loaded solution the free amine available is very small. Also, when the partial pressure of
CO2 is low (at low loading), the hydroxide (Off) concentration at the interface increases.
Therefore, Off is found to influence the apparent reaction rate and has a presence in the
apparent rate constant equation in Equation 5.4. Since, the studies conducted by Liao and
Li (2002) were on unloaded solution, they did not consider it necessary to include Off
ions in obtaining the predicted kapp. Blauwhoff et al. (1984) have reported that the data on
the CO2 absorption in single alkanolamines had a significant dependence on Off and
hence incorporated hydroxide ions in the reaction mechanism. In this study, when
MDEA was included in the termolecular mechanism term (refer to Equation 5.3) for the
multiple linear regressions, the results were meaningless. Hence, MDEA was excluded
from the mechanism term in this work. The exclusion of MDEA is supported by the
following reasons: The contribution of MDEA to the termolecular mechanism in mixed
alkanolamine system is highly debatable. Littel et al. (1992a) reported that MDEA has a
measurable contribution to the deprotonation of zwitterion (since the deprotonation of
zwitterion is similar to the termolecular mechanism) for CO2 absorption into aqueous
blends of DEA and MDEA. On the contrary, Rinker et al. (2000) found that when the
rates of absorption were predicted by excluding of the contribution of MDEA to the
zwitterion ion deprotonation, there was a good agreement between the predicted and
90
experimental absorption rates suggesting that MDEA does not significantly contribute to
the deprotonation of zwitterion. Littel et al. (1992a) have used a stirred cell reactor,
which operates under transient conditions and oyer much longer contact time that may
facilitate the deprotonation reaction by MDEA, whereas the laminar jet operates at very
short contact times. In addition, the laminar jet apparatus does not require calibration
whereas the stirred cell reactor does. This makes the stirred cell reactor more error prone
(Rinker et al, 2000) than the laminar jet apparatus. Since the experimental conditions
were identical (laminar jet was used in both cases) for the current study and the work by
Rinker et al. (2000), the exclusion of MDEA in the deprotonation reaction is justifiable.
Glasscock et al. (1991) have also demonstrated that MDEA does not participate in the
MEA reaction rate in the aqueous blend of MDEA-MEA system. The multiple linear
regression based on the modified termolecular mechanism was performed at each
temperature (298K to 333K) for all concentrations of the amine under consideration (27
wt.% MDEA/03 wt.% MEA, 25 wt.% MDEA/05 wt.% MEA, 23 wt.% MDEA/07 wt.%
MEA). The results obtained are given in Table 5.L The average absolute deviation
(AAD) between the experiments and fitted model for each temperature are shown, which
indicates that all experimental kinetics data of this work are fitted with an AAD of 19%
by the rate constants reported in the Table 5.1. The AAD for the current study is
comparable with less than 16% reported for loaded MEA system by Aboudheir et al.
(2003).
91
Table 5.1 Fitted values of kinetics constants of CO2 - absorption into aqueous MDEA-
MEA solution based on the deprotonation of zwitterion mechanism
Temperature, 298 303 313 323 333
turn, l2/mot2s
2056 3884 6790 7868 8586
/con-* i2/moi2s
72420 94087 112497 299192 469037
kMDEA>1/mols 963 1068 1799 2325 3540
AAD% in kapp 18 16 22.8 15.5 23
92
The rate constants estimates from this work were fitted as a function of temperature by
the following Arrhenius equations:
q -3802 4
kwEA - 9,56x10 e x p ( ~ ) (5.5)
kOH' = 5.04x 1 01 2 exp( ) (5.6)
kwoEA = 2 . 5 8 x l Q g e x p ( ' 37| 6 -5 ) (5.7)
where the reaction rate constants for Icmea, kofr are in Fmol'V1and for kMDEAin
I molds' 1 and the temperature is in Kelvin.
The individual reaction rate constants were substituted in the Equation 5.4 and the
predicted kapp was determined for each temperature and free amine concentration.
The predicted and experimental kapp values were plotted as a function of MEA
concentration at each temperature for all the three mixed amine concentrations in Figures
5.9 to 5.11.
93
a.
18000 -
16000 -
333
323
A 313
X303
0 298
14000 -
12000 -i
10000
8000 J
6000
4000 -
---
2000
T
0.100 0.200 0.300 0.400 0.500
MEA, mol/1
Equation 5.4
94
* 333
323
A 313
15000
X 303
o 298
oooo -
Q_5-
QX'
T
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
MEA, mol/1
Figure 5.10 Apparent rate constant for the reaction of CO2 with 25 wt.% MDEA-5wt.%
Equation 5.4
95
3 5 0 0 0 i
30000 i
333
323
313
303
298
25000 -
20000 -
1 5 0 0 0
10000 -
x
5000
o
0 .3 0.5 0.7 0.9
MEA, mol/1
1.1
Figure 5 . 11 Apparent rate constant for the reaction of CO2 with 23 wt.% MDEA-7wt.%
Equation 5.4
96
Figures 5.9 to 5.11 illustrate that there is a temperature dependence, suggesting that
zwitterion deprotonation is rate determining (Littel et al, 1992b). Also termolecular
mechanism is equivalent to the zwitterion deprotonation case. The average absolute
deviation between the experimental and predicted kapp for all temperatures of the
experiments for 27 wt.% MDEA-3 wt.% MEA was 32%. For 25 wt.% MDEA-5 wt.%
MEA, and 23 wt.% MDEA - 7 wt.% MEA, the AAD were 13.1 and 12.1% respectively.
The predicted and experimental kapp values correlate well at lower temperatures (see
Figures 5,9 to 5.11). At higher temperatures, the difference between the experimental
and predicted kapp values may be explained as follows: The simplified model was
developed based on the assumption that the reaction happens in the pseudo first order
regime (see Equation 2.39). Versteeg et al. (1996) have cited that at higher temperatures
for aqueous solutions of single alkanolamines, substantial deviation occurs from the
pseudo first order regime. The reason is the reaction rate increases with the temperature
while the equilibrium constants decrease. Since the solutions used for the experiments
were loaded, the equilibrium constants are very critical in determining the species at any
given loading. Hence, any effect of temperature (especially at higher temperatures) on
equilibrium constants might prove detrimental for kinetics rate determination. At higher
temperatures, the experimental and predicted kapp values for 23 wt.% MDEA-7 wt.%
MEA correlate slightly better than the corresponding values for the mixed amine
concentration of 27 wt.% MDEA- 3 wt.% MEA, and 25 wt.% MDEA-5 wt.% MEA. The
possible reason is that more free MEA is available in the former than the latter two.
97
Consequently, for the short contact time available, the reaction would be faster and less
error prone in terms of experimental gas absorption measurements.
5.4 Determination of Kinetics based on the Power law Model
It was decided to improve the predictive accuracy of the results for kapp by using the
Power Law model. The power law model was used because it can aid in the elucidation
of the mechanism for the reaction system. It determines the sensitivity of each species in
the apparent reaction rate constant, kapp. The expression for kapp by Power Law model is
given by:
kapp= k0e'E/RT][MEA3m[MDEA]n[OHl0 [C0 3 2'F[HC0 3"]q (5.8)
where m ,n, o, p, q are order of each species which are constants that to determined, E is
the activation energy and R is the Universal Gas constant.
The reaction orders of the individual species were determined by performing linear
regression analysis by using the "least squares" method on the values kapp. The
experimental values of kapp for all temperatures and concentrations of the mixed
alkanolamines were fitted to Equation 5.8 to obtain the predicted kapp and orders of the
reaction of the species.
kapp* ko[e"34868-OT][MEA]L52[MDEA]3'90[OHl'6 -97[CO32- f 26 [ H C O / f 10 (5-9)
The experimental and predicted kapp are plotted in Figures 5.12 to 5.14, The average
absolute deviation between the experimental and predicted kapp for all temperatures by
Power law model for 27 wt.% MDEA-3 wt.% MEA was 11%. For 25 wt.% MDEA-5
wt.%MEA, and 23 wt.% MDEA - 7 wt.%MEA, the AAD were 8.96 and 8.75 %
respectively.
98
a
p
p
12000 -
6000 -
4000
2000
333
323
A 313
X303
298
0.100
X-
0.200 0.300 0.400 0.500
Figure 5.12 Apparent rate constant for the reaction of COa with 27 wt.% MDEA-3wt%
9\
25000 i
20000 J
333
323
313
303
298
- 15000 J
10000
5 0 0 0
0 0.2 0.4 0.6 0.8 1
MEA, mol/1
Figure 5.13 Apparent rate constant for the reaction of COa with 25 wt.% MDEA-5wt.%
Equation 5.9
100
k
a
p
p
,

s
'
30000
25000
333
323
313
303
298
20000
15000
10000
5000 -
0 0.2 0.4 0.6 0.8 1 1.2
MEA, mol/1
Figure 5.14. Apparent rate constant for the reaction of CO2 with 23 wt.% MDEA-7wt%
Equation 5.9
101
From figures 5.12 to 5.14 and the average absolute deviations, it may be observed that
Power law model correlates better than the deprotonation of the zwitterion. Since Power
law does not restrict any order or mechanism unlike Zwitterion or Termolecular
mechanism, it resulted in better prediction of the values of kapp. The most widely
accepted Zwitterion mechanism cannot accurately predict the reaction rate constants. The
possible reason could be the overall order of the reaction for the kinetics for loaded
MDEA-MEA system may exceed three. The modified Termolecular mechanism could
predict the kapp with an AAD of about 19%. The zwitterion mechanism in its original
form (see Equation 5.1) and the two asymptotic cases (zwitterion formation and
deprotonation) cover the reactions
mechanism needs to be developed
aqueous MDEA-MEA system.
102
orders from two to three. This shows that a new
to accurately describe the kinetics of COj loaded
6* CONCLUSIONS
In this work, the experiments were done for three different mixed amine concentrations
of 27/03,25/05, 23/07(wt.% MDEA/ wt.% MEA) and comprehensive data were obtained.
The CO2 loading of the solution ranged from ~ 0.0097 to 0.1424 moles CCVmol amine
and the absorption temperatures ranged from 298K to 333K. The data obtained from the
absorption experiments were utilized to explain the Kinetics. Prior to the absorption
studies for mixed alkanolamine system, the laminar jet apparatus was tested for physical
absorption system, CO2 -Water as a part of the calibration of the apparatus. Excellent
results were obtained for the diffusivity of CO2 into water at 298K. A new method called
the protonation method was tried to measure the diffusivity of the CO2 in amine directly
in lieu of the N2O analogy and results were reported.
All possible reactions were taken into account and Vapor Liquid Equilibrium (VLE)
model was developed for the mixed alkanolamine system to calculate the species. New
sets of kinetics data were obtained for the reactions of CO2 in loaded MDEA-MEA using
highly accurate steady-state absorption techniques (laminar jet apparatus).
A new kinetic model of the CO2 absorption in loaded aqueous MDEA-MEA solution was
developed. The kinetic model is based on the modified termolecular mechanism.
Reaction rate model is given by:
rC02 = (kOH_[OH-] + k^[MEA])MEA + k2MDEA[MDEA])C02 ( 6 . 1 )
with the following three reaction-rate constants:
o 1a8 , - 3802. 4.
kMEA = 9 . 5 6 x 10 e x p ( - ------) (6.2)
103
koH = S . 0 4 x l 0 12 e x p ( - - - | ---) (6.3)
kMDE* = 2. S8xl 08 exp( (6.4)
where the reaction rate constants for kmA, koe' are in PmofV1 and for ^mdea in
1molds' 1 and the temperature is in Kelvin.
It was observed that water did not contribute to the zwitterion deprotonation reaction
unlike observed by previous researchers. OH- was found to contribute to the apparent rate
constant. The reaction-rate model developed could predict the kinetics of CO2 loaded
MDEA-MEA system.
6.1 Recommendations
Its proven beyond doubt that laminar jet apparatus is the most accurate for the gas
absorption experiments and kinetics studies (Westerterp et ahs 1984). Laminar Jet is
suitable for systems like aqueous MEA system or MDEA-MEA systems that have higher
concentration of MEA. Higher concentration of MEA in the alkanolamine mixture
results in higher values for gas absorption, which can be accurately, measured within the
short contact time available in a laminar jet apparatus.
It is recommended as fixture work to extend the Kinetics study to fast reacting mixed
alkanolamine systems. There is scope to find out a new mechanism, which can
adequately predict the kinetics of the loaded mixed alkanolamine (MDEA-MEA) system.
Also a comprehensive absorption-rate /kinetics model for the absorption of CO2 with
104
chemical reaction can be developed which will take into account the chemical
equilibrium, mass transfer and chemical kinetics of all possible reactions.
105
References
Aboudheir, A.; Tontiwachwuthikul, P.; Chakma, A. Idem, R. Kinetics of reactive
absorption of carbon dioxide in high CCh-loaded, concentrated aqueous
monoethanolamiae solutions. Chem. Eng. Set 2003, 58 ( 23), 5195-5210
Aboudheir, A. Kinetics, Modeling and Simulation of Carbon Dioxide Absorption into
highly concentrated aqueous monoethanolamine solutions. PhD. Thesis, 2002,
University of Regina, SK, Canada
Abu-Arabi, M.K.; Tamimi, A.; Al-Jarrah, A.M. Solubility and Diffusivity of CO2 in
Triethanolamine solution. J. Chem. Eng. Data. 2001,46,1125-1129
Al-Ghawas, H.; Hagewiesche, D.; Ruiz-Ibanez, G.; Sandall, O.C. Physicochemical
properties important for carbon dioxide absorption in aqueous
methyldiethanolamine. J. Chem. Eng. Data. 1989, 34,385-391
Astarita, G.; Savage, D.; Bisio, A. Gas treating with Chemical Solvents; John Wiley
& Sons: New York, 1983
Austgen, D.M.; Rochelle, G.T. Model of Vapor-Liquid Equilibria for Aqueous Acid
Gas-Alkanolamine Systems. Representation of H2S and CO2 Solubility in Aqueous
MDEA and CO2 solubility in Aqueous Mixtures of MDEA with MEA or DEA.
Ind. Eng. Chem. Res. 1991,30, 543-555
Barth, D.; Tondre, C,; Delpuech, J. J. Kinectis and mechanisms of the reactions of
Carbon dioxide with alkanolamines: a discussion concerning the cases of MDEA
and DEA. Chem. Eng. Set 1984,39(12), 1753-1757
Blauwhoff, P.M.; Versteeg, G. F.; van Swaaij. W. M. A study on the reaction
between Carbon dioxide and alkanolamines in aqueous solutions. Chem. Eng. Sci.
1984,39(2), 207-225
Clarke, J.K.A. Kinetics of absorption of carbon dioxide in Monoethanolamine
solutions at short contact times, I & EC Fundamentals. 1964, 3(3), 239-245
Caplow, M. Kinetics of carbamabte formation and Breakdown. J. Am. Chem. Soc.
1968, 90, 6795-6803
Charkravarty, T.; Phuken, U.K. Reaction of Acid gases with mixtures of amines.
Chem. Eng. Progress. 1985, 40, 32-36
106
Critcfafield, J.; Rochelle, G.T. Absorption of Carbon dioxide in Aqueous MDEA and
MDEA/MEA Solutions. Presented at the AIChE National Meeting, Houston, TX,
March 30,1987
Crooks, I.E.; Donnellan, J.P. Kinetics and Mechanism of the reaction between
Carbon dioxide and Amines in Aqueous Solution. J. Chem. Soc. Perkin Trans.II.
1989, 331-333
Climate Change Plan for Canada, Government of Canada, 2003
Danckwerts, P. V. Gas liquid reactions; McGraw Hill: New York, 197
Danckwerts, P. V. The reaction of carbon dioxide with ethanolamines. Chem . Eng.
Sci. 1979, 34(4), 443-446
Donaldson, T.L.; Nguyen, Y.N. Carbon Dioxide Reaction Kinetics and Transport in
Aqueous Amine Membranes. Ind. Eng. Chem Fundam. 1980, 10,260-266
Glasscock D.A.; Critchfield. I.E.; Rochelle, G.T. Absorption of Carbon dioxide in
mixtures of MDEA with MEA or DEA. Chem. Eng. Sci. 1991,46(11), 2829-2845
Hairaour, N.; Sandall, O.C. Absorption of Carbon dioxide into aqueous
Methyldiethanolamine. Chem. Eng. Sci. 1984, 39(12), 1791-1796
Haimour, N.; Bidarian, A.; Sandall, O.C. Kinetics of the reaction between Carbon
dioxide and Methyldiethanolamine. Chem. Eng. Sci. 1987,42,1393-1398
Hagewiesche, D.P.; Ashour, S.S.; Al-Ghawas, H.A.; Sandall, O.C. Absoprtion of
Carbon dioxide into aqueous blends of Monoethanolamone and N-
Methyldiethanolamine. Chem . Eng. Sci. 1995a, 50(7), 1071-1079
Hagewiesche, D.P.; Ashour, S.S.; Sandall, O.C. Solubility and diffusivity of Nitrous
oxide in Ternary mixtures of water, MEA and MDEA and solution densities and
viscosities. J. Chem. Eng. Data. 1995b, 40,627-629
Horowitz, W. Official Methods of Analysis of the Association of Official Analytical
Chemists(AOAC). 12th ed., George Banta: Washington D.C., 1975.
Homg, S-Y.; Li Meng-Hui. Kinetics of absorption of carbon dioxide into aqueous
solutions of Monoethanolamine + Triethanolamine Ind. Eng. Chem. Res. 2002, 41,
257-266
Hsu, C.; Li, M. Densities of Aqueous Blended Amines. J. Chem . Eng. Data. 1997,
42,502-507
107
Jon, F-Y; Otto, F.D.; Mather, A.E, Yapor-Liquid Equilibrium of 02 in aqueous
mixtures of Monoethanolamine and Methyldiethanolamine, Ind. Eng. Chem. Res.
1994,33, 2002-2005
Ko, J-J.; Tsai T-C.; Lin Wang, H-M.; Li, M-H. Diffusivity of Nitrous oxide in
aqueous alkanolamines. J. Chem. Eng. Data. 2001,46,160-165
Kohl, A.; Nielsen, R. Gas Purification. Gulf Publishing Company: Houston, Texas.
Fifth edition, 1997
Laddha. S.S; Danckwerts, P.V. Reaction of C02 with ethanolamines: Kinetics from
gas-absorption. Chem. Eng. Sci. 1981,36(3), 479-482
Littel, R.J.; Versteeg, G.F.; Van Swaaij, W.P.M. Kinetics of CO2 with primary and
secondary amines in aqueous solutionsI. Zwitterion deprotonation kinetics for
DEA and DIPA in aqueous blends of alkanolamines, Chem. Eng. Sci. 1992a,
47(8), 2027-2035
Littel, R.J.; Versteeg, G.F.; Van Swaaij, W.P.M. Kinetics of CO2 with Primary and
Secondary Amines in aqueous solutions-II. Influence of temperature on zwitterion
formation and deprotonation rates. Chem. Eng. Sci. 1992b, 47(8), 2037-2045
Littel, R.J.; Van Swaaij, W.P.M.; Versteeg, G.F. Kinetics of CO2 with Tertiary
amines in aqueous solutions. A.I.Ch.E. Journal. 1990,36(11), 1633-1640
Li, M-H.; Shen, K.P. Densities and Solubilities of solutions Carbon Dioxide of
MEA+ MDEA. J . Chem. Eng. Data. 1 9 9 2 , 37,288
Li, M-H.; Lio Y-C. Densities and viscosities of solutions of MEA+ MDEA+ water
and MEA+AMP+Water. J . Chem . Eng. Data. 1994, 39,444-447
Li, M-H.; Lai, M-D. Solubility and diffusivity of Nitrous oxide and 02 in
(MEA+MDEA+water) and (MEA+AMP+Water). J. Chem . Eng. Data. 1995, 40,
486-492
Liao, C-H; Li, M-H. Kinetics of absorption of Carbon Dioxide into aqueous solutions
of monoethanolamine +N-metfayldiethanoiamine, Chem. Eng. Sci., 2002, 5 7 ( 2 1 ) ,
4569-4582
Mandal, B.P.; Guha, M.; Biswas, A.K.; Bandopadhyay, S.S. Removal of Carbon
Dioxide by absoprtion in mixed amines: modeling of absorption in aqueous
MDEA/MEA and AMP/MEA solutions. Chem . Eng. Sci. 2001, 56(21-22), 6217-
6224
108
Perry, R.H.; Green, D.W. Perrys Chemical Engineer Handbook. 7thedition; McGraw
Hill: New York, I f f ?
Pinset, B.R.W.; Pearson, L.; Roughton, FJ.W. The kinetics of Combination of
Carbon Dioxide with Hydroxide ions. Trans. Faraday. Soc., 1956, 79,1512-1520
Rinker, E.B.; Ashour, S.S.; Sandall, O.C. Kinetics and Modeling of Carbon dioxide
into aqueous solutions of Diethanolamine. Ind. Eng. Chem. Res. 1996, 35(4),
1107-1114
Rinker, E.B.; Ashour, S.S.; Sandall, O.C. Kinetics and modeling of Carbon dioxide
into aqueous solutions of N-Methyldiethanolamine. Chem. Eng. Sci. 1995, 50(5),
755-768
Rinker, E.B.; Ashour, S.S.; Al-Ghawas, H.A.; Sandall, O.C. Absorption of Carbon
dioxide into aqueous blends of Diethanolamine and Methyldiethanolamine. Ind.
Eng. Chem. Res. 2000, 39,4346-4356
Rangwaia, H.A.; Morrell, B.R.; Mather, A.E. Absorption of CO2 into aqueous tertiary
amine/MEA solutions. The Canadian Journal of Chemical Engineering, 1992, 70,
482-490
Sada, E.; Hidehiro, K.; Han, Z.Q.; Matsuyama, H. Chemical kinetics of the reaction
of Carbon Dioxide with ethanoiamine in Non-aqueous Solvents. A.I.Ch.E Journal,
1985,31 (8), 1297-1303
Shen, K.P.; Li, M-H. Solubility of carbon dioxide in aqueous mixtures of
monoethanolamine with methyldiethanolamine. J . Chem . Eng. Data. 1992, 37,
96-100
Shen, K.P.; Li, M-H. Densities and Solubilities of solutions of carbon dioxide in
water + monoethanolamine + methyldiethanolamine. J . Chem . Eng. Data. 1992,
37,288-290
Tamimi, A.; Rinker, E.B.; Sandall, O.C. Diffusion coefficiemts for hydrogen Sulfide,
Carbon Dioxide, and Nitrous Oxide in Water over temperatures range 298-368K.
J.Chem. Eng. Data. 1994,39 (2), 330-332
Tomcej, R.; Otto, F. Absorption of CO2 and N2O into aqueous Methyldiethanolamine.
A.I.CkE. Journal. 1989, 35(5), 861-864
109
Versteeg, G.F.; Van Dijck, A.J.; van Swaaij, W.P.M. On the kinetics between CO2
and alkanolamines both in aqueous and non-aqueous solutions. An Overview.
Chem. Eng. Comm. 1996, 144, 113-158
Versteeg, G.F.; Van Swaaij, W.P.M. On the kinetics between 02 and alkanolamines
both in aqueous and non-aqueous solutions-!. Primary and secondary amines.
Chem. Eng. Sci.,. 1988a, 43(3), 573-585
Versteeg, G.F.; Van Swaaij, W.P.M. On the kinetics between C02 and alkanolamines
both in aqueous and non-aqueous solutions-II. Tertiary amines. Chem. Eng. Sci.,.
1988b, 43(3), 587-591
Versteeg, G.F.; Kuipers, J.A.M.;van Beckum, F.P.M.; van Swaaij, W.P.M. Mass
Transfer with complex reversible reactions -II Parallel reversible reactions. Chem .
Eng. Sci.,. 1990,45(1), 183-197
Visual Numerics Inc. IMSL MATH/LIBRARY: Fortran Subroutines for
Mathematical Applications. Visual Numerics Inc.: Texas, 1994a
Visual Numerics Inc. IMSL STAT/LIBRARY: Fortran Subroutines for Statistical
Applications. Visual Numerics Inc.: Texas, 1994b
Xiao. I.; Li Chih-Wei; Li Meng-Hui. Kinetics of absorption of carbon dioxide into
aqueous solutions of monoethanolamine + 2-amino-2-methyl-1-propanol, Chem.
Eng. Sci, 2000, 55(1), 161-175
Wang.Y.W.; Otto, D.; Mather, A.E. Solubility of N20 in aqueous mixtures of
alkanolamines and in mixed solvents, Chem. Eng. J., 1992,48, 31-40
Westerterp, K. R.; Van Swaaij, W. P. M.; Beenackers, A. A. C. M.Chemicai Reactor
Design and Operation, 1996, 2nd Edition, John Wiley, New York
Weiland, R.; Dingman, J.; Cronin, D.; Browning, G. Density and Viscosity of Some
Partially Carbonated Aqueous Alkanolamine Solutions and their Blends. J.Chem.
Eng. Data, 1998, 43, 378-382
Zhang, X.; Zhang C-F.; Liu. Y. Kinetics of absorption of carbon dioxide into aqueous
solution of Methyldiethanolamine blended with Diethanolamine Ind. Eng. Chem.
Res. 2002, 41, 1135-1141
110
Appendix A:
For Vapor Liquid Equilibrium(VLE) model developed in Chapter 2
Part A.1 Main programs
PROGRAM VLE
I PS. Tested on experimental data on April 2 2 , 2001. Excellent results.
! The nine nonlinear algebraic equations of bulk concentration of MEA solution were
Ssolved for the unknowns of the bulk concentrations using Subroutine called
I DNEQNF documented in the IMSL library (Visual Numerics, Inc., 1994). This Routine
i is based on the MINPACK subroutine HYBRD1, which uses a modification of
! M J.B. Powell's hybrid algorithm.
! This algorithm is a variation of Newton's method, which uses a fmite-diflerence
! approximation to the Jacobian and takes precautions to avoid large step sizes or
! increasing residuals (More et al., 1980; Visual Numerics, Inc., 1994). Since a
Sfinite-difference method is used to estimate the Jacobian, double precision
! calculation was applied in order to get an accurate Jacobian, which will assist to
! arrive at the exact root.
i rr-T=m;z=========^====^ ^ Declare modules used
USE MSIMSLMD ! use the double precision subroutines from IMSL Library
USE VLEOutputData Smodule for output data of the bulk concentrtion
i l ^ = = = input data of the nonlinear equations - -
IMPLICIT NONE
CHARACTER (LEN=10) :: RunNumber = '2703L8' 1enter the Run number
EXTERNAL FCN ! user-supplied SUBROUTINE to evaluate the
system of equations
INTEGER, PARAMETER:: N = l l ! number of equations and variables
DOUBLE PRECISION :: ERRREL = 1.0E-5 ! stopping criterion
INTEGER:: ITMAX = 10000 ! the maximum number of iterations
! Set values of initial guess
! [C02] [RNH2] [RNH3+] [HC03-] [OH-] [C03-] JH+] [RNHCOO-] Pe [R3N] [R3NH+]
DATA CGUESS/8.16E-06,1.140E-00,4.88E-05,2.80E-05,0.85E-03,1.09E-03,1.54E-10,L44E-02,9.90E
03,1.980E-OO,2.31E-01/
I-- : -- end of input data ........................... ..
! INTEGER K ! counter for output
DOUBLE PRECISION :: FNORM ! a scalar that have a value F(l)2+...+F(N) at point x
DOUBLE PRECISION :: C(N) ! the point at which the function is evaluated
DOUBLE PRECISION :: CGUESS(N) ! a vector of length N, input guess.
! Find the solution
CALL DNEQNF (FCN, ERRREL, N, ITMAX, CGUESS, C, FNORM)
1.............. .....................= Output Presentation;..................................... ;.........
CALL OutputData (RunNumber, N, CGUESS, C)
DO K= 1, N
WRITE(*, *) K,-', C(K)
END DO
1=======================^^ end Output presentation -
!END PROGRAM VLE
Part A.2.User-sapplled subroutine called FCN:
SUBROUTINE FCN (C, F, N)
USE VLEJtaputData ! module for input data of the solution of run # M101
! module for the Ke and He of Li and Shen. 1993. USE EqaiIibmim_Constants
IMPLICIT NONE
DOUBLE PRECISION TK
DOUBLE PRECISION CO
DOUBLE PRECISION 01
DOUBLE PRECISION WO
DOUBLE PRECISION W01
DOUBLE PRECISION Alpha
DOUBLE PRECISION He
! loading of the amine solution, mol CG2/mol amine
! Henry's law constant, kPa/(mol/L)
! solution temperature, K
! molarity of the MEamine solution, mol/L
I molarity of the MDEamine solution, mol/L
DOUBLE PRECISION Ke8,Ke3, Ke5, Ke6, Ke7,Kel ! equil. const.
INTEGER N
DOUBLE PRECISION C(N), F(N)
CALL InputData (TK, CO,01, WO, WO 1, Alpha)
CALL Ke_5 (TK,Ke5)
CALL Ke_8 (TK, Ke8)
CALL Ke_3 (TK, Ke3)
CALL Ke_6 (TK, Ke6)
CALL Ke_7 (TK, Ke7)
CALL Ke_l (TK, Kel)
CALL Solubility J302_MEA_MDEAso!n (TK,W0,W01, He)
He=He/1000
F( 1) = CO 1-C( 10)-C( 11)
F(2) = C0-C(2)-C(3)-C(8)
P(3) =(C(H-C01)* Alpfaa-C( 1}-C(4)-C(6)-C(8)
F(4) = C(3)+C{11)+C(7)-C(S)-C(4)-2.0*C(6)- C(5)
F(5) = Ke5 *C( 1)*( 10)-C( 11)*C(4)
F(6) = Ke8*C(l)*C(2)- C(7)*C(8) !(Hageweshwsiche 1995)
F(7) = C(9)-He*C(l)
F(8) = Ke3*C(4)- C(7)*C(6)
F(9) = Ke6*C(10)*C(7)- C(11)
F(10)= Ke7*C(7)*C(2>- C(3)
F(1 Vf= Kel*C(5)*C(7)-1
RETURN
END SUBROUTINE FCN
! - rim-==3=as==T~T^: -!:^==arrr 0f User-defined subroutine = = = = =
112
Part A J . Input data module;
MODULE VLEJtaputData
CONTAINS
SUBROUTINE InputData (TK, C0,COI,W0,W81Alptm)
IMPLICIT NONE
DOUBLE PRECISION:: TK
DOUBLE PRECISION:: CO
DOUBLE PRECISION:: 01
DOUBLE PRECISION:: WO
DOUBLE PRECISION:: WOi
DOUBLE PRECISION:: Alpha
TK =298.00
CO =0.4900
01 =2.316
WG= 0.03
W01= 0.27
Alpha =0.30
! solution temperature. K
! molarity of the MEamine solution, mol/L
! molaiity of the MDEamine solution, mol/L
i weight fraction MEA
! weight fraction MDEA
! loading of the amine solution, mol C02/mol amine
113
Part A.4. Output date module:
MODULE VLE_OutputData
CONTAINS
SUBROUTINE OutputData (RunNumber, N, CGUESS, C)
USE VLE_InputData
USE Equiiibrium_Constants
IMPLICIT NONE
ivariables declaration
! titles of output data and tables
CHARACTER <LEN=10) :: C1 = '[C02] '
CHARACTER (LEN=10):: C2 = [RNH2] '
CHARACTER (LEN=10) :: C3 = [RNH3+] '
CHARACTER(LEN=10) : : C4 = [HC03-]
CHARACTER (LEN=10) :: 5 = [OH-]
CHARACTER (LEN=10) :: C6 = [ 0 3 - ] 1
CHARACTER (LEN=IO):: C7 = [H+] '
CHARACTER (LEN=10):: C8 = [RNHCOO-]'
CHARACTER (LEN-10) :: C9 = ' P e !
CHARACTER (LEN=10):: CIO = [R3N]'
CHARACTER (LEN=10) :: Cl 1 = {R3NH+]'
CHARACTER (LENN10):: Titfel= 'Loading '
CHARACTER (LEN=10) :: line = ----------
CHARACTER (LEN=10):: RunNumber
INTEGER:: K! counter for output
INTEGER:: N ! number of variables
DOUBLE PRECISION :: C(N)S values of solution
DOUBLE PRECISION :: CGUESS(N)! initial guess for concentrations
DOUBLE PRECISION :: TK! solution temperature, K
DOUBLE PRECISION :: CO ! molarity of die MEamine solution, mol/L
DOUBLE PRECISION :: CQ1 ! molarity of the MDEamine solution, mol/L
DOUBLE PRECISION :: WO ! Wt% MEamine solution
DOUBLE PRECISION :: W01 ! Wt% MDEamine solution
DOUBLE PRECISION :: Alpha! loading of the amine solution, mol C02/mol amine
DOUBLE PRECISION :: Kel ! equilibrium constant of reaction 1
DOUBLE PRECISION:: Ke3
DOUBLE PRECISION :: Ke5 ! equilibrium, const, of reactions 2
DOUBLE PRECISION:: Ke6 ! equilibrium constant of reaction 3
DOUBLE PRECISION :: Ke? ! equilibrium constant of reaction 4
DOUBLE PRECISION :: Ke8 ! equilibrium constant of reaction 5
DOUBLE PRECISION :: He ! Henrys low constant, kPa/(mol/L)
OPEN(UNIT=6, FILE=RunNumber ,STATUS=REPLACE')i
CALL InputData (TK, C0,C01, W0.W01 Alpha)! input data
CALL Ke_5 (TK, Ke5)
CALL Ke_8 (TK, Ke8)
CALL Ke_3 (TK, Ke3) ! Li and Sfaen, 1993
CALL Ke_6 (TK, Ke6)
CALL Ke_7 (TK, Ke7)
CALL Ke_l (TK, Kel)
CALL Solubiiity_CO2_MEA_MDEAsoln(TK,W0,W01,He)
He=He/100Q ! conversion from kPacm3/mol to kPaL/mol
! printing the input data in unit # 6
WRITE(6, (5X, A10, 5X, A10)) Run # RunNumber
WRITE(6, (5x, A10)) Line
WRITE(6, (5X, A10)) Input Data
WRITE(6, '(5x, A10)') Line
114
WR!TE(6 (5X, AIO, 5X, F10.1, SX, AlO)') 'TK = , TK, *K
W1ITE(6, '(5X, AID, 5X, FI0.4, 5X, AIO)') 'CO = , CO, 'moVcmS '
WRITE(6, '{SX, AIO, 5X, F10.4, 5X, AIO)') 'Cl = ' , C01, 'mol/cmS
WR1TE(6, (5X, AIO, 5X, FI0.4, SX, AIO)) WO =, WO, WtMEA
WRTTE(6, (5X, AIO, 5X, F I0.4, 5X, AIO)') W01 = ' , W01, WtMDEA
WRITE(6, (5X, AIO, 5X, F10.4, 5X, AIO)) Loading = , Alpha, moymol
WRITE(6, '(5X, AIO, 5X, 1PE10.4)) 'CGUESS 1', CGUESS(i)
WRITER, '(5X, AIO, 5X, 1PE10.4)') 'CGUESS2', CGUESS(2)
WRITE(6) '(5X, AIO, SX, 1PE10.4)') CGUESS3, CGUESS(3)
WRITE(6, '(5X, AIO, 5X, 1PE10.4)') 'CGUESS4', CGUESS(4)
WMTE(6, {5X, AIO, 5X, 1PE10.4)') 'CGUESS5', CGUESS(5)
WRITE(6, '(5X, AIO, 5X, 1PE10.4)') 'CGUESS6', CGUESS(6)
WRITE(6, '{5X, AIO, 5X, 1PE10.4)') 'CGUESS7', CGUESS(7)
WRITE(6, {5X, AIO, 5X, 1PE10.4)') CGUESS8, CGUESS(8)
WRITE(6, (5X, AIO, 5X, 1PE10.4)) CGUESS9, CGUESS{9)
WRITER, (SX, AIO, 5X, 1PE10.4)) CGUESS 10, CGUESS(IO)
WRITE(6, (5X, AIO, 5X, 1PE10.4)) 'CGUESS11, CGUESS(ll)
I printing results for unit # 6
WRITE(6, (5x, AIO)') Line
WRITE(6, '(5X, AIO)') Results'
WRITE{6, '(5x, AIO)) Line
WRITE(6, '(5X, AIO, 5X, 1PE10.4, 5X, AIO)') 'Ke5 = ' , Ke5, 'mol/L
WRITE(6, '(5X, AIO, 5X, 1PE10.4, 5X, AIO)') 'Ke8 =', Ke8, 'mol/L'
WRITE(6, {5X, AIO, 5X, 1PE10.4, 5X, AIO)') *Ke3 = ' , Ke3, 'mol/L'
WRITE(6, *{5X, AIO, 5X, 1PE10.4, 5X, AIO)') Ke6 =', Ke6, 'mol/L'
WR!TE(6, '(5X, AIO, 5X, 1PE10.4, 5X, AIO)) !Ke7 = ' , Ke7, '(mol/L)2'
WRITE(6, '(5X, AIO, 5X, 1PE10.4, 5X, AIO)') 'Kel =', Kel, 'mol/L'
WRITE(6, (5X, AIO, SX, 1PE10.4, 5X, AIO)') He = , He, 'kPa.L/mol
Sprinting the title of the table in unit # 6
WRITE(6, *(2(5x, AIO))') Line, Line
WRITE(6, '(5X, AIO, SX, F10.4)') Title!, Alpha
WRITE(6, (2(5x, AIO))') Line, Line
WRITE(6, '(5X, AIO, 5X, 1PE10.4)') Cl, C(l)
WRITE(6, '(SX, AIO, SX, IPE10.4)') C2, C(2)
WRITE(6, (5X, AIO, SX, 1PE10.4)) C3, C(3)
WRITE(6, (5X, AIO, SX, 1PE10.4)') C4, C(4)
WRITE(6, '{SX, AIO, SX, IPE10.4)) C5, C{5)
WRITE(6, (SX, AIO, 5X, 1PE10.4)) C6, C(6)
WRITE(6, '(SX, AIO, 5X, IPE10.4)') Cl, C(7)
WRITE{6, '(SX, AIO, SX, 1PE10.4)') C8, C(8)
WR1TE(6, '(SX, AIO, SX, 1PE10.4, 5X, AIO)') C9, C(9), 'kPa
WRITE(6, '(SX, AIO, 5X, 1PEI0.4)) CIO, C(10)
WRITE(6, (SX, AIO, SX, 1PE10.4)) Cl 1, C(11)
! Screen output
print*, 'Run # =', RunNumber
print*, 'TK = TK
print*, 'CO =', CO
print*, Cl =', CO!
print*, 'WO =', WO
print*, 'W01 =', W01
print*, 'Alpha = Alpha
print*, KeS =', Ke5
print*, 'Ke8 =', Ke8
print*, 'Ke3 = Ke3
print*,'Ke6 = ',Ke6
print*, 'Ke7 =', Ke7
115
print*, 'Kel = Kel
print*, He = He
DO K= 1, N
print*, 'C\ K/=, C(K)
END DO
END SUBROUTINE OutpntData
END MODULE VLE_OutputData
116
Appendix B:
The physical property correlations were programmed in FORTRAN 90.
B.l A module which comprises of Equilibrium constants called Equitibrium constants.
This module has the subroutines to calculate all equlibrium constants.
B.2 A module for physical properties called Physical-Properties. In this module there are
subroutines to calculate the required physical properties such as solubility, density and
dlffusivity. The subroutines to compute the molarity given the weight percent of each
amine is also included.
117
Part B.1 Equilibrium constants module:
MODULE Equilibriiim_Constants
! this module contains the calculation of the Equilibrium constants
! and Henry's constant obtained from the paper of Li and Sfaen, 1993
CONTAINS
SUBROUTINE Ke_8 (TK,Ke8)
IMPLICIT NONE
Keg =10**(-!0.5492 + 1526.27/TK)
END SUBROUTINE Ke 8
! temperature, K
I equilibrium constant of reaction 1
SUBROUTINE Ke_3(TK,Ke3)
IMPLICIT NONE
Ke3 = exp{-12431.7/TK-35.4819*log(IK)+220.0S7)! Edwards et al 1978
END SUBROUTINE Ke 3
SUBROUTINE Ke_6 (TK, Ke6)
IMPLICIT NONE
Ke6=EXP(-9.4165-4234.9S/TK)
Ke6=l/Ke6
END SUBROUTINE Ke 6
! temperature, K
! equilibrium constant of reaction 5
!developed by Schwabe et al 1959
IMPLICIT NONE
Ke7 = exp(2.1211-8189.38/TK-0.007484)
Ke7=l/Ke7
END SUBROUTINE Ke 7
temperature, K
equilibrium constant of reaction 6
SBates 1951
SUBROUTINE Ke_l (TK, Kel)
IMPLICIT NONE
DOUBLE PRECISION :: TK ! temperature, K
DOUBLE PRECISION :: Kel Sequilibrium constant of reaction 7
Kel = exp(-13445.9/TK-22.4773*log(TK)+140.932)! Edwards et al 1978
Kel=l/Kel
END SUBROUTINE Ke 1
Stemperature, K
! equilibrium constant of reaction 1
IMPLICIT NONE
CALL Ke_6 (TK, Ke6)
Ke5 = 10**(179,648 + 0.019244*TK -67.341 *log!0(TK) - (7495.441/TK) )*Ke6
END SUBROUTINE Ke_5
END MODULE Equilibrium_Constants
Part B.2 Physical properties module:
SUBROUTINE Solubility_C02JMEA_MDEAsoln(TK,WtMEA, WtMDEA, HeC02_MEA_MDEAsoln)
IMPLICIT NONE
DOUBLE PRECISION::TK
DOUBLE PRECISION::WtMEA
DOUBLE PRECISION::WlMDEA
DOUBLE PRECISION: :HeC02_MEA_MDEAsoln
DOUBLE PRECISI0N::HeC02_H20
DOUBLE PRECISI0N::HeN20_H20
DOUBLE PRECISION::HeN20_MEA_MDEAsoln
CALL SolubiIity_C02_H20(TKHe02_H20)
CALL Solubility_N20_H20(TKJIeN20_H20)
CALL Solubility_N20_MEA_MDEAsoln(TK, WtMEA, WtMDEA, HeN20_MEA_MDEAsoIn)
HeC02_MEA_MDEAsoln= HeN20_MEA_MDEAsoln *(HeC02_H20/HeN20_H20)
!Print,'soIubiIity-Co2-H20>kPa.cm3/mol-,HeC02_H20
!Print*/soluWlify-N20-H20skPa.cm3/moI-!HeN20_H20
!Print* 5'soIubility-N20_MEA_MDEAsoln, kPa.cm3/moI=',HeN20_MEA_MDEAsoln
!Print*,'solubility-Co2-MEA-MDEA solution, kPa.cm3/mol=',HeC02_MEA_MDEAsoin
END SUBROUTINE Solubility_C02_MEA_MDEAsoln
.(SUBROUTINE Solubility_N20_MEA_MDEAsoIn(T,Ml,M2,He 1S)
SUBROUTINE Solubility_N2O_MEA_MDEAsoln(TK,W0,W01,HelS)
IMPLICIT NONE
DOUBLE PRECISION: :TK
(DOUBLE PRECISION::Ml
(DOUBLE PRECISION: :M2
DOUBLE PRECISION,PARAMETER: :Fw2=61.08
DOUBLE PRECISION,PARAMETER::Fw3=18.016
DOUBLE PRECISION,PARAMETER::Fw4=l 19.17
(Parameters in excess Henrys constant for MEA-H2o, Tsai et al.2000
!DOUBLE PRECISION,PARAMETER::al=4.793
!DOUBLE PRECISION,PARAMETER::bl=-7.4463E-3
(DOUBLE PRECISION,PARAMETER::c 1=0.0
(.DOUBLE PRECISION,PARAMETER: :dl=-2.201
! Parameters in excess Henrys constant for MEA-H2o, Li et a l l 995
DOUBLE PRECISION,PARAMETER::al=-5.9535
DOUBLE PRECISION,PARAMETER::bl=1938.24
SParameters in excess Henry's constant for MEA-MDEA, Li et al.1995
DOUBLE PRECISION,PARAMETER::a2=36.8828
DOUBLE PRECISION,PARAMETER::b2=-1637.43
DOUBLE PRECISION,PARAMETER::c2=0.0
DOUBLE PRECISION,PARAMETER::d2=0.0
'Parameters in excess Henry's constant for MDEA-H2o, Li et al.1995
DOUBLE PRECISION,PARAMETER::a3=-2.8999
DOUBLE PRECISION,PARAMETER: *3=1405.43
DOUBLE PRECISION,PARAMETER: :c3=0.0
DOUBLE PRECISION,PARAMETER: :d3=0.0
DOUBLE PRECISION::HelS Ssolubility of N20 in amine solution
DOUBLE PRECISION::He 12 'solubility of N20 in pure MEA
119
DOUBLE PRCISION::Hel3 Isolubility of N20 in water
DOUBLE PRECISION::Hel4 isolubility of N20 in pure MDEA
DOUBLE PRECISION::x2 Imole fraction of MEA
DOUBLE PRECISION::x3 imole fraction of H20
DOUBLE PRECISION::x4 imole fraction of MDEA
DOUBLE PRECISION: :Rho2 Idensity of pure MEA,g/cm3
DOUBLE PRECISION::Rho3 idensity of H20, g/cm3
DOUBLE PRECISION: :Rho4 Idensity of pure MDEA
DOUBLE PRECISION::WO
DOUBLE PRECISION::WOi
DOUBLE PRCISION::Y2 Imolar volume of MEA
DOUBLE PSECISION::V3 Imolar volume of H20
DOUBLE PRECISION::V4 Imolar volume of MDEA
DOUBLE PRECISION::Phi2 Ivolume fraction of MEA
DOUBLE PRECISION: :PM3 Ivolume fraction of H20
DOUBLE PRECISI0N::Phi4 Ivolume fraction of MDEA
DOUBLE PRECISION::A23 Itwo body interaction parameter as a function of temperature for MEA&H2o
DOUBLE PRECISION::A24 Itwo body interaction parameter for MEA, MDEA
DOUBLE PRECISION: :A34 Itwo body interaction parameter for H20&MDEA
DOUBLE PRECISION::A234 !three-body interaction parameter for H20&MDEA
DOUBLE PRECISION: :R234 ! excess henry's law constant for temay system, MEA-MDEA-H20
CALL Mole_Fraction_MEA_MDEA_Soln(WO,WO 1,x2,x4)
x3=1.0-x2-x4
CALL Density_MEA_Pure(TK,Rho2)
CALL Density_MDEA_Pure(TK,Rho4)
CALL DensityJH20(TK,Kho3)
V2= Fw2/Rho2
V3= Fw3/Rho3
V4= Fw4/ Rho4
PM2=x2*V2/(x2JiIY2+x3 * V3+x4* V4)
Phi3=x3*V3/(x2*V2+x3*V3+x4*Y4)
Phi4=x4*V4/{x2*V2+x3*V3+x4*V4)
ICaluclate the excess Henrys law constant for MEA-MDEA-H20
!A23=al+MT+cl*T**2-Hl*PM3
A23=al+bl/TK
A24=a2+b2/TK
A34= a3+b3/TK
A234= -45.8808
R234= Phi2*Phi3*A23+ Phi2"Phi4*A24+Phi3*Phi4*A34+Phi2*Phi3*Phi4*A234
! calculation of the solubility of N20 in water and pure amine
CALL SolubilityJ42Q_H20(TK,Hel3)
CALL SolubilityJN20_MEApure(TK.,He 12)
CALL SolubiUty_N20_MDEApure(TKLHe 14)
HelS= exp(R234+(PM2*log(Hel2)+Phi3*log(HeI3)-t-PM4*log(Hel4)))
END SUBROUTINE Solubility_N20_MEA_MDEAsoln
SUBROUTINE Mole_Fraction_MEA_MDEA_Soln(WtMEA,WtMDEA,xMEA,xMDEA)
IMPLICIT NONE
DOUBLE PRECISION:: smMEA
DOUBLE PRECISION:: WtMEA
DOUBLE PRECISION:: smMDEA
DOUBLE PRECISION:: WtMDEA
DOUBLE PRECISION:: xMEA
120
DOUBLE PRECISION:: xMDEA
DOUBLE PRECISION:: FwMEA=6t.08
DOUBLE PRECISION:: FwMDEA=l 19.17
smMEA=WtMEA* lOOO.0/(FwMEA*(l- (WtMEA+ WtMDEA)))
smMDEA=WtMDEA*1000.0/(FwMDEA*(l- (WtMEA+ WtMDEA)))
xMEA=smMEA/( smMEA+smMDEA+55.506)
xMDEA=smMDEA/( smMEA+smMDEA+55.506)
print*,'weight percent of MEA-,WtMEA
print*,weight percentof MDEA-,WtMDEA
print*,'mole fraction of MEA- ,xMEA
print*,'mole fraction of MDEA-,xMDEA
END SUBROUTINE Mole_Fraction_MEA_MDEA_Soln
SUBROUTINE Density_MEA_Pure(T!vRhoMEApBre)
IMPLICIT NONE
DOUBLE PRECISION::RhoMEApure
!parameters for pure density of MEA, from Table 6, Hsu et al.,1997
DOUBLE PRECISION,PARAMETER::A1=1.19093
DOUBLE PRECISION,PARAMETER::A2=-4.2999E-4
DOUBLE PRECISION,PARAMETER::A3=-5,6604E-7
RhoMEApure=A 1+A2TK+A3 *TK* *2
END SUBROUTINE Density_MEA_Pure
SUBROUTINE Density_MDEA_Pure(TK,RhoMDEApure)
IMPLICIT NONE
DOUBLE PRECISION::RhoMDEApure
'parameters for pure density of MDEA, from Table 6, Hsu et al.,1997
DOUBLE PRECISION,PARAMETERS 1=1.22864
RhoMDEApure=Al+A2*TK-fA3*TK**2
END SUBROUTINE Density_MDEA_Pure
SUBROUTINE Density_H20(TK,RhoH20)
IMPLICIT NONE
DOUBLE PRECISION: :RhoH20
Sparameters for pure density of MEA, from Table 6, Hsu et al.,1997
DOUBLE PRECISION,PARAMETER::A1=8.63559E-1
DOUBLE PRECISION,PARAMETER: :A2=1.21494E-3
DOUBLE PRECISION,PAKAMETER::A3=-2.5708E-6
RhoH20=Al+A2*TK+A3*TK**2
END SUBROUTINE Density_H20
SUBROUTINE SolubiIity_C02_H20(TK,He)
IMPLICIT NONE
!calculation of solubility of N20 in water versteeg 1988
DOUBLE PRECISION:: He
He=2.82E9*exp(-2044.0/TK)
END SUBROUTINE Solubility_C02_H20
SUBROUTINE SolubilityJ420_H20(TK,He)
IMPLICIT NONE
!calculation of solubility of N20 in water versteeg 1988
He=8.55E9*exp(-2284.0/TK)
END SUBROUTINE Soiubifity_N20JK20
SUBROUTINE Solubility_N20_MEApure(TK,He)
IMPLICIT NONE
!calculation of solubility ofN20 in MEA Wang 1992
He=l ,207E8*exp(-1136.5/TK)
END SUBROUTINE Solubility_N20_MEApure
SUBROUTINE Solubility_N20_MDEApure(TK1He)
IMPLICIT NONE
! calculation of solubility ofN20 in MDEA Wang 1992
He=l .524E8*exp(-1312.7/TK)
END SUBROUTINE Solubility_N20_MDEApure
IMPLICIT NONE
DOUBLE PRECISION: :TK =298
DOUBLE PRECISION::Alpha =0.5
DOUBLE PRECISION:: WO =.03
DOUBLE PRECISION::W1 =.27
DOUBLE PRECISION: :Rho
CALL Density_MEA_MDEAsoln(TK,WO,W1, Alpha, Rho)
END
SUBROUTINE Density_MEA_MDEAsoln(TK,WtMEA5WtMDEA, Alpha, RhoMEA_MDEASoln)
IMPLICIT NONE
DOUBLE PRECISION::Alpha
DOUBLE PRECISION::WtMDEA
DOUBLE PRECISION: :RhoMEA_MDEASo!n
DOUBLE PRECISION::RhoH20
DOUBLE PRECISION: :xMEA
DOUBLE PRECISION: :xMDEA
DOUBLE PRECISION: :xH20
DOUBLE PRECISION::YMEA
DOUBLE PRECISION: :VMDEA
DOUBLE PRECISION:: VH20
DOUBLE PRECISION::Vsoln
DOUBLE PRECISION,PARAMETER:: VCO2MEA=.04747
DOUBLE PRECISION,PARAMETER:: VC02MDEA=-2.8558
DOUBLE PRECISION, PARAMETER::VstarMEA=-1.8218
DOUBLE PRECISION, PARAMETER: :VstarMDEA=-6.65
DOUBLE PRECISION::xC02
DOUBLE PRCISION::FwMEA=61.08
DOUBLE PRECISION::FwMDEA=l 19.17
DOUBLE PRECISION:: VDstarMDEA
DOUBLE PRECISION:: d=12.983
DOUBLE PRECISION:: e=397.72
DOUBLE PRECISION::FwH20=l 8.016
DOUBLE PRECISION: :FwCO2=44.01
CALL Mole_Fraction_MEA_MDEA_Soln(WtMEA,WtMDEA, xMEA,xMDEA)
xC02=(xMEA+xMDEA)* Alpha
xH20= 1,0-xCO2-xMEA-xMDEA
CALL Density_MEA_Pure(TK,RhoMEApure)
CALL DensityJMDEA_Pure(TK,RhoMDEApure)
CALL Density_H20(TK,RhoH20)
VDstarMDEA= d+e*xMDEA
VMEA = FwMEA/RhoMEApure
VMDEA = FwMDEA/RhoMDEApure
VH20= FwH20/RhoH20
Vsoto=xMEA*VMEA+xMDEA*VMDEA+-xH20*VH20+xC02*(VC02MEA+VC02MDEA)+xMEA*x
H20*VstarMEA+xMDEA*xH20*VstarMDEA+xMDEA*xC02,|i VDstarMDEA
RhoMEA_MDEASoln=(xMEA*FwMEA+xMDEA',!FwMDEA+xH20*FwH20+xC02*FwC02)/Vsolii
print*,'Density of MEA JMDEA Solution , RhoMEA_MDEASoln
END SUBROUTINE Density_MEA_MDEAsoln
SUBROUTINE Density_MEA_Pure(TK,RhoMEApure)
IMPLICIT NONE
DOUBLE PRECISION: :RhoMEApure
.parameters for pure density of MEA, from Table 6, Hsu 1997
DOUBLE PRECISION,PARAMETER: :A2=-4.2999E-4
DOUBLE PRECISION PARAMETER:: A3=-5.66040E-7
RhoMEApure=Al+A2*TK+A3*TK**2
IMPLICIT NONE
DOUBLE PRECISION: :EhoMDEApre
!parameters for pure density of MDEA, from Table 6, Hsu 1997
RhoMDEApure=A1+A2*TK+A3 * TK* *2
IMPLICIT NONE
123
! parameters for pare density of MEA, from Table 6, Hsxi et al.,1997
DOUBLE PRECISIONJARAMETER::A2=l .21494E-3
DOUBLE PRECISION,PARAMETER::A3==-2,570gE6
RhoH20=A 1+A2*TK+A3*TK* *2
SUBROUTINE Mole_Fraction_MEA_MDEA_Soln(WtMEA,WtMDEA,xMEA,xMDEA)
IMPLICIT NONE
DOUBLE PRECISION:: WtH20
DOUBLE PRECISION:: MMEA
DOUBLE PRECISION:: MMDEA
DOUBLE PRECISION:: MH20
DOUBLE PRECISION:: WMEA
DOUBLE PRECISION:: WMDEA
DOUBLE PRECISION:: WH20
DOUBLE PRECISION:: FwMEA=61.08
DOUBLE PRECISION:: FwMDEA=I 19.17
DOUBLE PRECISION:: FwH20=18.G6
WtH20=l -WlMEA-WtMDEA
WMEA=100* WtMEA
WMDEA=!00* WtMDEA
WH2O=10Q* WtH20
MMEA=WMEA/ FwMEA
MMDEA=WMDEA/ FwMDEA
MH20=WH20/ FwH20
xMEA= (MMEA/(MMEA+MMDEA+MH20))
XMDEA=(MMDEA/(MMEA+MMDEA+MH20))
print*,'weight percent of MEA-, WtMEA
print*,'weight percentof MDEA-,WtMDEA
print*,'mole fraction of MEA- ,xMEA
END SUBROUTINE Mole_Fraction_MEA__MDEA_Soln
IMPLICIT NONE
DOUBLE PRECISION: :TK=303.00
DOUBLE PRECISION::CO= 0.981
DOUBLE PRECISION: :C01= 2.04
DOUBLE PRECISION::
CALL Diflusivity_C02_MEAJMDEASoln(TK,C0,C01, D)
END
SUBROUTINE Diffasivity_C02_MEA_MDEASoln(TK,MMEA,MMDEA, D_C02_MEA_MDEAsoin)
IMPLICIT NONE
DOUBLE PRECISION::MMEA
DOUBLE PRECISION: :MMDEA
DOUBLE PRECISION: :D_C02_MEA_MDEAsoln
DOUBLE PRECISION::
DOUBLE PRECIS ION: :D_N20_H20
124
DOUBLE PRECIS ION: :D_C02_H20
CALL Diffusivity_N20_MEA_MDEASoln (TK,MMEA,MMDEA, D)
CALL Diffusivity_N20_H20 (TK, D_N20_H20)
CALL Diffusivity_C02_H20 (TK, D_C02_H20)
D_C02_MEA_MDEAsotn= D *( D_C02_H20/ D_N20_H20)
PRINT* .Diffusivity of C02_MEA_MDEAsoln,m2/s- ,D_C02_MEA_MDEAso1e
END SUBROUTINE Diffusivtty_C02_MEA_MDEASoln
SUBROUTINE Diffusivity_N20_MEA_MDEASofa (TK,MMEA,MMDEA, D)
IMPLICIT NONE
DOUBLE PRECISION: MMEA
DOUBLE PRECISION::MMDEA
DOUBLE PRECISION::
DOUBLE PRECISION,PARAMETER: :b0 =-1.89645E-07
DOUBLE PRECISION,PARAMETER:*! !=2.44679E-07
DOUBLE PRECISION,PARAMETER::bl2=-2.71690E-08
DOUBLE PRECISION,PARAMETER::b21=3.98653E-07
DOUBLE PRECISION,PARAMETER::b22=-8.96763E-08
DOUBLE PRECISION,PARAMETER::cl2=-8.75280E-08
DOUBLE PRECISION,PARAMETER::c=1644.03
D=(bO+bi 1*MMEA+b 12*MMA*MMEA+b21*MMDEA+b22*MMDEA*MMDEA+c 12*MMEA*MM
DEA)*EXP(-c/TK)
PRINT* ,,DIffiisivityN20_MEA_MDEAsoln,m2/s=',D
END SUBROUTINE Difiusivity_N20_MEA_MDEASoIn
SUBROUTINE Difiusivity_N20_H20 (TK,D)
IMPLICIT NONE
DOUBLE PRECISION: :D
D=5,07E-6*EXP(-2371,0/TK)
PRINT* ,DIffiisivIty-N20-H20,m2/s=', D
END SUBROUTINE DIIfusIvity_N20_H20
SUBROUTINE Dif&sivity_C02_H20 (TK,D)
IMPLICIT NONE
DOUBLE PRECISION::
D=2.35E-6*EXP(-2119.0/TK)
PRINT*,T)iffusivity-C02-H20jn2/s-, D
END SUBROUTINE Diffiisivity_C02_H20
IMPLICIT NONE
DOUBLE PRECISION: :TK =298.0
DOUBLE PRECISION::Alpha =0.000
DOUBLE PRECISION::W1 =.24 1.399785452
DOUBLE PRECISION::Fl=l 19.17
DOUBLE PRECISION: :M 1
CALL MoIarity_MDEA(W1,TK, Alpha, FI, Ml)
END
Molarity of MDEA and MEA
SUBROUTINE Molarity_MDEA(WtMDEA,TK, Alpha, FwMDEA, MMDEA)
125
IMPLICIT NONE
DOUBLE PRECISION:: MMDEA
DOUBLE PRECISION::FwMDEA
DOUBLE PRECISION:: Alpha
DOUBLE PRECISION::RhoMDEA_Soln
CALL Density_MDEA_soln(TK, WtMDEA,Alpha,FwMDEA, RhoMDEA_Soln)
MMDEA= WtMDEA* RtioMDE A_Soln* 1000/(FwMDEA)
print*,'Molarity of MDE A_Solution =', MMDEA
END SUBROUTINE Molarity_MDEA
SUBROUTINE DensityjVfDEAjsoIn(TK, WtMDEA,Alpha,FwMDEA, RhoMDEA_Soln)
IMPLICIT NONE
DOUBLE PRECISION::WtMDEA
DOUBLE PRECISION::RhoMDEA_Soln
DOUBLE PRECISION::RhoH20
DOUBLE PRECISION::xMDEA
DOUBLE PRECISION::xH20
DOUBLE PRECISION::VMDEA
DOUBLE PRECISION:: VH20
DOUBLE PRECISION::Vsoln
DOUBLE PRECISION,PARAMETER:: VC02MDEA=-2.8558
DOUBLE PRECISION, PARAMETER:: VstarMDEA=-6.65
DOUBLE PRECISION: :xC02
DOUBLE PRECISION: :FwMDEA
DOUBLE PRECISION: :FwH20=l 8.016
DOUBLE PRECISION:: VDstarMDEA
DOUBLE PRECISION:: d=12.983
DOUBLE PRECISION:: e=397.72
CALL DensityJMDEAJPure(TKJRhoMDEApure)
CALL DensityJ120(TK,RhoH20)
CALL MoIe_Fraction_MDEA_Soln(WtMDEA,FwMDEA, xMDEA)
xC02=xMDEA*Alpha
xH20=l .0-xCO2-xMDEA
CALL Density_MDEA_Pure(TK,RIioMDEApiire)
CALL Density_H20(TKJRhoH20)
VDstarMDEA= d+e*xMDEA
VMDEA = FwMDEA/RhoMDEApure
VH20= FwH20/RhoH20
Vsoln=3cMDEA*VMDEA+xH20*VH20+xC02*VC02MDEA+xMDEA*xH20*VstarMDEA+xMDEA*
xC02*VDstarMDEA
RhoMDEA_Soln=(xMDEA*FwMDEA+xH20*FwH20+xC02*FwC02)Wsota
Sprint*,'Density of MDEA_Soiution =, RhoMDEA_Soln
END SUBROUTINE Density_MDEA_soin
IMPLICIT NONE
126
!parameters for pure density of MDEA, from Table 6, Hsu 1997
SDOUBLE PRECISION,PARAMETER::A=-4.86099E-7
{DOUBLE PRECISION, PARAMETER::B=-4.24935E-4
! DOUBLE PRECIS10N,PARAMETER::C=1.20528
!RhoMDEApure=<A*TK**2)+{B*TK)+C
RhoMDEApure=Al+A2*TK+A3*TK**2
IMPLICIT NONE
DOUBLE PRECISION::RboH20
!parameters for pure density of H20, from Table 6, Hsu et al.,1997
RhoH20=Al +A2*TK+A3 *TK* *2
SUBROUTINE Mole_Fraction_MDEA_Soln(WtMDEA,FwMDEA, xMDEA)
IMPLICIT NONE
DOUBLE PRECISION:: smMDEA
DOUBLE PRECISION: :FwMDEA
smMDEA=WtMDEA* 1000.0/(FwMDEA*( 1- WtMDEA) )
xMDEA=smMDEA/( smMDEA+55.506)
print*,weight percent of MDEA-, WtMDEA
END SUBROUTINE MoIe_Fraction_MDEA_Soln
IMPLICIT NONE
DOUBLE PRECISION::TK =298.0
DOUBLE PRECISION: :Alpha =0.000
DOUBLE PRECISION::W0 = 06
DOUBLE PRECISION: :F0=61.08
DOUBLE PRECISION::M0
CALL Molarity_MEA(W0,TK, Alpha, F0, M0)
END
SUBROUTINE MoIarity_MEA(WtMEA,TK, Alpha, FwMEA, MMEA)
IMPLICIT NONE
DOUBLE PRECISION:: MMEA
DOUBLE PRECISION::FwMEA
DOUBLE PRECISION::RhoMEA_SoIn
CALL Density_MEA_soln(TK, WtMEA,Alpha,FwMEA,RhoMEA_Soln)
127
MMEA= WtMEA*RhoMEA_Soln* 1000/(FwMEA)
print*/Molarity of MEAJSolutionMMEA
END SUBROUTINE Molarity_MEA
SUBROUTINE Density_MEA_soln(TK,WtMEA,AIpha,FwMEA, RhoMEA_Soln)
IMPLICIT NONE
DOUBLE PRECISION: :AIpha
DOUBLE PRECISION: :RhoMEA_Soln
DOUBLE PRECISION::xMEA
DOUBLE PRECISI0N::xH20
DOUBLE PRECISION:: VMEA
DOUBLE PRECISI0N::VH20
DOUBLE PRECISION-Vsota
DOUBLE PRECISION,PARAMETER:: VCO2MEA=.04747
DOUBLE PRECISION, PARAMETER: :VstarMEA=-1.8218
DOUBLE PRECISION: :xC02
DOUBLE PRECISION::FwMEA
DOUBLE PRECISION: :FwH20= 18.016
CALL Mole_Fraction_MEA_SoIn(WtMEA,FwMEA, xMEA)
xC02=xMEA* Alpha
xH20=l .0-xCO2-xMEA
CALL DensityJVIEA_Pure(TK,RhoMEApure)
CALL Density_H20(TK,RhoH20)
VMEA - FwMEA/RhoMEApure
VH20= FwH20/RhoH20
Vsoln=xMEA*VMEA+xH20*VH20+xC02*VC02MEA+xMEA*xH20*VstarMEA
RhoMEA_Scln=(xMEA*FwMEA+xH20,,!FwH20+xC02!!FwC02)A^soln
print*,'Density of MEA_ Solution =', RhoMEA_Soln
END SUBROUTINE Density_MEA_soln
SUBROUTINE Deiisity_MEA_Piire(TK,RlioMEApure)
IMPLICIT NONE
iparameters for pure density of MEA, from Table 6, Hsu 1997
DOUBLE PRECISION,PARAMETER:Al=l. 19093
DOUBLE PRECISION,PARAMETER:: A3=-5.66G40E-7
RhoMEApure=A1+A2*TK+A3 * TK* * 2
IMPLICIT NONE
iparameters for pure density of MEA, from Table 6, Hsu et al.,1997
DOUBLE PRECISION,?ARAMETER::A1=8.63559E-1
DOUBLE PRECISION,PARAMETER::A2=i .2I494E-3
RhoH20=A I +A2*TK+A3*TK* *2
SUBROUTINE Moie_Fraction_MEA_Soln(WtMEA,FwMEAs xMEA)
IMPLICIT NONE
DOUBLE PRECISION:: smMEA
DOUBLE PRECISION:: FwMEA
smMEA=W!MEA* 100O.O/(FwMEA*( I - WtMEA))
xMEA=smMEA/( smMEA+55.506)
print*,'weight percent of MEA-,WtMEA
print*,'mole fraction of MEA=',xMEA
END SUBROUTINE Mole_Fraction_MEA_Soln
Appendix
Raw experimental data of 0 2 absorption into MDEA-MEA solutions using
laminar Jet
The experimental data obtained from the laminar jet for the absorption rate of CO2 into
aqueous solution MEA-MDEA solution over a wide range of operating conditions are
compiled in this appendix. The conditions include concentration of the solutions ranging
from 27 wt.% - 23 wt.% for MDEA and 03 wt.%- 07 wt.% MEA respectively. The
temperatures for experiments ranged from 293 to 333K and were performed at various
contact times. The total CO2 loading ranged from 0.0095 to 0.1427 mol CO2 /mol amine.
The data in the Tables C.l to C.3 were utilized to explain the kinetics of the reaction
between CO2 and aqueous MEA-MDEA solutions in Chapter 5.
130
Table C. 1 Experimental data for Kinetics for CO2 absorption into aqueous 23 wt. %
MDEA- 7 wt.% MEA solutions
Temperature Molarity Loading
P CO!
L h a
(K) MDEA MEA (mol/mol) (kPa) (cm3/$) (cm) (cm) (mol/s)
(mol/1) (mol/1)
298 1.996 1.147 0.0100 92.54 0.423 1.958 0.0577 2.837E-06
1.996 1.147 0.0100 92.54 0.423 2.406 0.0583 3.297E-06
1.996 1.147 0.0305 92.16 0.397 2.177 0.0570 2.523E-06
1.996 1.147 0.0305 92.16 0.397 2.504 0.0560 2.763E-06
1.996 3.147 0.0541 91.93 0.388 1.986 0.0578 2.212E-06
1.996 1.147 0.0541 91.93 0.388 2.324 0.0580 2.450E-06
1.996 1.147 0.1012 91.86 0.391 2.112 0.0597 1.887E-06
1.996 1.147 0.1012 91.86 0.391 2.425 0.0590 2.502E-06
1.996 1.147 0.1411 92.12 0.412 2.348 0.0590 1.815E-06
1.996 1.147 0.1411 92.12 0.412 2.539 0.0593 1.92 IE-06
303 1.996 1.147 0.0100 91.19 0.4279 2.057 0.0567 3.402E-06
! 1.996 1.147 0.0100 91.19 0.4279 2.440 0.0603 3.765E-06
1.996 1.147 0.0305 91.19 0.3442 2.063 0.0555 2.857E-06
1.996 1.147 0.0305 91.19 0.3442 2.457 0.0553 3.257E-06
1.996 1.347 0.0541 90.81 0.3728 2.142 0.0597 2.901E-06
1.996 1.147 0.0541 90.81 0.3728 2.401 0.0587 3.176E-06
1.996 1.147 0.1012 90.71 0.3704 1.777 0.0587 2.064E-06
1.996 1.147 0.1012 90.71 0.3704 2.076 0.0560 2.262E-06
1.996 1.147 0.1411 91.03 0.3879 2.098 0.0590 2.067E-06
1.996 1.147 0.1411 91.03 0.3879 2.374 0.0573 2.320E-06
313 1.996 1.147 0.0100 87.99 0.418 2.052 0.0537 3.586E-06
1.996 1.147 0.0100 87.99 0.418 2.431 0.0513 4.022E-06
1.996 1.147 0.0305 87.83 0.381 2.118 0.0550 3.337E-06
1.996 1.147 0.0305 87.83 0.381 2.591 0.0577 4.095E-06
1.996 1.147 0.0541 87.83 0.363 2.070 0.0573 3.084E-Q6
1.996 1.147 0.0541 87.83 0.363 2.382 0.0560 3.452E-06
1.996 1.147 0.1012 87.59 0.375 2.114 0.0560 2.619E-06
1.996 1.147 0.1012 87.59 0.375 2.437 0.0567 2.973E-06
1.996 i.147 0.1411 87.91 0.369 2.382 0.0577 3.097E-06
1.996 1.147 0.1411 87.91 0.369 1.663 0.0600 2.336E-06
323 1.996 1.147 0.0100 83.17 0.406 1.998 0.0580 3.702E-06
1.996 1.147 0.0100 83.17 0.406 2.355 0.0573 4.285E-06
1.996 1.147 0.0305 83.17 0.390 2.024 0.0590 3.482E-06
1.996 1.147 0.0305 83.17 0.390 2.467 0.0580 4.189E-06
1.996 1.147 0.0541 82.66 0.365 2.148 0.0575 3.468E-06
1.996 1.147 0.0541 82.66 0.365 2.429 0.0583 3.921E-06
1.996 1.147 0.1012 82.72 0.366 2.112 0.0587 2.894E-06
1.996 1.147 0.1012 82.72 0.366 2.430 0.0593 3.304E-06
1.996 1.147 0.1411 82.45 0.406 2.106 0.0555 2.296E-06
1.996 1.147 0.1411 82.45 0.406 2.383 0.0538 2.527E-06
333 1.996 1.147 0.0100 75.79 0.394 2.042 0.0583 3.561E-06
1.996 1.147 0.0100 75.79 0.394 2.473 0.0577 4.223E-06
1.996 1.147 0.0305 75.14 0.379 2.088 0.0568 3.485E-06
1.996 1.147 0.0305 75.14 0.379 2.373 0.0550 3.809E-06
1.996 1.147 0.1012 75.19 0.393 2.101 0.0563 2.905E-06
1.996 1.147 0.1012 75.19 0.393 2.385 0.0573 3.285E-06
1.996 1.147 0.1411 74.86 0.407 2.158 0.0565 2.540E-06
1.996 1.147 0.1411 74.86 0.407 2.366 0.0553 2.703E-06
131
Table C.l. (Continued.,.)
8

1
!
[RNH2]
(mol/I)
PC031
(mol/1)
{OITJ
(mol/1)
[COs2!
(mW)
IR3N]
(mol/1)
P # J
(mol/i)
kapp,experimental
rsw dais
(1/s)
average
(1/s)
4.06E-10 1.085 3.17E-04 1.89E-02 2.80E-02 1.977 39.64 6117 5287
4.06E-10 1.085 3.17E-Q4 1.89E-02 2.8OE-02 1.977 39.64 5323
6.48E-09 0.995 2.08E-G3 7.73E-03 7.50E-02 1.950 39.76 4077 4412
6.48E-09 0.995 2.08E-03 7.73E-03 7.5GE-02 1.950 39.76 3824
3.23E-08 0.889 5.80E-03 4.33E-03 1.I7E-01 1.916 39.89 3707 3554
3.23E-08 0.889 5.80E-03 4.33E-03 1.17E-01 1.916 39.89 3289
2.18E-07 0.688 1.88E-02 2.08E-O3 1.82E-01 1.836 40.15 2243 2367
2.18E-07 0.688 I.88E-02 2.08E-03 1.82E-01 1.836 40.15 3066
6.84E-07 0.539 3.70E-02 1.30E-03 2.25E-01 1.753 40.38 1709 1752
6.84E-07 0.539 3.70E-02 1.30E-03 2.25E-01 1.753 40.38 1624
7.48E-10 1.088 4.20E-04 I.86E-02 2.78E-02 1.974 39.55 9273 7896
7.48E-10 1.088 4.20E-04 1.86E-02 2.78E-02 1.974 39.55 7063
1.17E-08 1.003 2.72E-03 7.64E-03 7.39E-02 1.943 39.67 6846 6827
1.17E-08 1.003 2.72E-03 7.64E-03 7.39E-02 1.943 39.67 6304
5.70E-08 0.901 7.47E-03 4.33E-03 1.15E-01 1.905 39.80 5736 5736
5.70E-08 0.901 7.47E-03 4.33E-03 1.15E-01 1.905 39.80 5660
3.66E-07 0.710 2.35E-02 2.12E-03 1.77E-01 1.818 40.06 4392 4136
3.66E-07 0.710 2.35E-02 2.12E-03 1.77E-01 1.818 40.06 4240
1.1QE-06 0.568 4.50E-02 1.36E-03 2.18E-01 1.731 40.29 3102 3243
I.10E-06 0.568 4.50E-02 1.36E-03 2.18E-01 1.731 40.29 3242
2.40E-09 1.095 7.14E-04 1.81E-02 2.72E-02 1.967 39.36 14427 12686
2.40E-09 1.095 7.14E-04 1.81E-02 2.72E-02 1.967 39.36 14128
3.59E-08 1.019 4.46E-03 7.58E-03 7.09E-02 1.929 39.48 11368 11361
3.59E-08 1.019 4.46E-03 7.58E-03 7.09E-02 1.929 39.48 10389
1.65E-07 0.928 1.18E-02 4.37E-03 1.09E-01 1.882 39.61 9402 9959
1.65E-07 0.928 1.18E-02 4.37E-03 1.09E-01 1.882 39.61 9324
9.61E-07 0.756 3.51E-02 2.22E-03 1.63E-01 1.784 39.87 6877 7762
9.61E-07 0.756 3.51E-02 2.22E-03 1.63E-01 1.784 39.87 6510
2.64E-06 0.627 6.40E-02 1.47E-03 1.98E-0I 1.693 40.1 7111 6438
2.64E-06 0.627 6.40E-02 1.47E-03 1.98E-01 1.693 40.1 7666
7.08E-09 1.103 1.16E-03 1.80E-02 2.63E-02 1.961 39.15 17831 18162
7.08E-09 1.103 1.16E-03 1.80E-02 2.63E-02 1.961 39.15 17581
9.92E-08 1.036 6.92E-03 7.66E-03 6.68E-02 1.915 39.27 15207 15744
9.92E-08 1.036 6.92E-03 7.66E-03 6.68E-02 1.915 39.27 15324
4.33E-07 0.954 1.77E-02 4.49E-03 1.00E-01 1.862 39.40 14391 13248
4.33E-07 0.954 1.77E-02 4.49E-03 1.00E-01 1.862 39.40 13970
2.31E-06 0.800 4.94E-02 2.35E-03 1.46E-01 1.754 39.66 9976 9533
2.31E-06 0.800 4.94E-02 2.35E-03 1.46E-01 1.754 39.66 9608
5.96E-06 0.682 8.66E-02 1.60E-03 1.74E-0I 1.659 39.88 7108 7417
5.96E-06 0.682 8.66E-02 1.60E-03 1.74E-01 1.659 39.88 7171
1.93E-08 1.109 1.80E-03 1.8 IE-02 2.52E-02 1.955 38.93 21101 22347
1.93E-08 1.109 1.80E-O3 1.81E-02 2.52E-02 1.955 38.93 20618
2.51E-07 1.051 1.02E-02 7.87E-03 6.17E-02 1.903 39.04 21595 20189
2.51E-07 1.051 1.02E-O2 7.87E-03 6.17E-02 1.903 39.04 21251
5.13E-06 0.840 6.61E-02 2.50E-03 1.28E-01 1.730 39.43 15334 14032
5.13E-06 0.840 6.61E-02 2.50E-03 1.28E-01 1.730 39.43 14678
1.25E-05 0.733 1.12E-01 1.73E-03 I.49E-01 1.633 39.65 11111 11661
1.25E-05 0.733 1.12E-01 1.73E-03 1.49E-01 1.633 39.65 10921
132
Temperature
m
Molarity Loading
(raol/mol)
PC02
(kPa)
L
( c i b 3/ s )
b
(cm)
d
(cm) (mol/s)
MDEA
(mol/i)
MEA
(mol/1)
298
2.141 0.818 0.0109 91.11 0.427 2.108 0.0610 2.691 E-06
2.141 0.818 0.0109 91.31 0.427 2.441 0.0607 2.973E-06
2.141 0.818 0.0442 91.70 0.415 1.795 0.0590 2.054E-06
2.141 0.818 0.0442 91.70 0.415 2.294 0.0583 2.463E-06
2.141 0.818 0.0574 92.16 0.377 2.004 0.0567 2.389E-06
2.141 0.818 0.0574 92.16 0.377 2.384 0.0578 2.596E-06
2.141 0.818 0.0922 93.20 0.403 2.120 0.0570 2.08 IE-06
2.141 0.818 0.0922 93.20 0.403 2.394 0.0580 2.149E-06
2.141 0.818 0.1427 90.47 0.382 2.000 0.0570 1.486E-06
2.141 0.818 0.1427 90.47 0.382 2.341 0,0573 1.589E-06
303 2.141 0.818 0.0109 89.55 0.797 1.918 0.0600 2.449E-06
2.141 0.818 0.0109 89.55 0.397 2.386 0.0587 2.950E-06
2.141 0.818 0.0442 90.56 0.408 2.212 0.0570 2.563E-06
2.141 0.818 0.0442 90.56 0.408 2.372 0.0570 2.68 IE-06
2.141 0.818 0.0574 91.15 0.403 2.177 0.0588 2.398E-06
2.141 0.818 0.0574 91.15 0.403 2.410 0.0597 2.63GE-06
2.141 0.818 0.0922 91.92 0.385 1.973 0.0603 1.99QE-06
2.141 0.818 0.0922 91.92 0.385 2.305 0.0597 2.176E-06
2.141 0.818 0.1427 89.59 0.376 1.989 0.0603 1.453E-Q6
2.141 0.818. 0.1427 89.59 0.376 2.392 0.0595 1.754E-06
313
2.141 0.818 0.0109 86.79 0.402 1.799 0.0575 2.620F-06
2.141 0.818 0.0109 86.39 0.402 2.229 0.0582 3.081E-06
2.141 0.818 0.0442 86.39 0.386 1.800 0.0585 2.348E-06
2.141 0.818 0.0442 86.39 0.386 2.211 0.0585 2.839E-06
2.141 0.818 0.0574 88.07 0.383 1.864 0.0580 2.488E-06
2.141 0.818 0.0574 88.07 0.383 2.227 0.0577 2.779E-06
2.141 0.818 0.0922 88.93 0.392 2.119 0.0573 2.365E-06
2.141 0.818 0.0922 88.93 0.392 2.468 0.0573 2.680E-06
2.141 0.818 0.1427 86.25 0.349 2.111 0.0580 2.0Q3E-06
2.141 0.818 0.1427 86.25 0.349 2.362 0.0563 2.003E-06
323 2.141 0.818 0.0109 82.29 0.786 2.040 0.0571 1.174E-06
2.141 0.818 0.0109 82.29 0.386 2.349 0.0580 3.666E-06
2.141 0.818 0.0442 82.53 0.375 2.200 0.0590 3.121E-06
2.141 0.818 0.0442 82.53 0.375 2.425 0.0597 3.357E-06
2.141 0.818 0.0574 82.53 0.384 1.913 0.0550 2.496E-06
2.141 0.818 0.0574 82.53 0.384 2.425 0.0550 3.159E-06
2.141 0.818 0.0922 83.48 0.408 2.048 0.0590 2.288E-06
2.141 0.818 0.0922 83.48 0.408 2.491 0.0590 2.699E-06
2.141 0.818 0.1427 81.43 0.380 1.927 0.0560 1.654E-06
2.141 0.818 0.1427 81.43 0.380 2.380 0.0538 2.035E-O6
333
2.141 0.818 0.0109 74.70 0.412 1.950 0.0540 2.979F.-06
2.141 0.818 0.0109 74.70 0.412 2.234 0.0518 3.359E-06
2.141 0.818 0.0442 74.59 0.394 1.951 0.0563 2.904E-06
2.141 0.818 0.0442 74.59 0.394 2.233 0.0540 3.263E-Q6
2.141 0.818 0.0574 75.56 0.413 2.235 0.0563 2.881E-06
2.141 0.818 0.0574 75.56 0.413 2.541 0.0540 3.277E-06
2.141 0.818 0.0922 75.99 0.375 2.087 0.0577 2.223E-06
2.141 0.818 0.0922 75.99 0.375 2.491 0.0587 2.704E-06
2.141 0.818 0.1427 73.80 0.343 2.095 0.0560 1.840E-G6
2.141 0.818 0.1427 73.80 0.343 2.349 0.0587 1.993E-06
Table C.2. (Continued...)
fCOjJ
(mol/i)
fMNHJ
(mol/1)
P C 0 31
(mol/1)
[OH1
(moW)
fC032"]
(mol/1)
{RjNl
(mol/1)
p 20]
(mel/I)
kapp, experimental
raw data average
(1/s) (1/s)
6.4OP.-10 0.764 4.06E-04 1.53F.-02 2.90F-O2 2.116 39.69 4658 5105
6.40E-10 0.764 4.06E-04 1.53E-02 2.90E-02 2.116 39.69 4273
2.59E-08 0.641 4.75E-03 4.43E-03 9.84E-02 2.057 39.86 4033 3849
2.59E-08 0.641 4.75E-03 4.43E-03 9.84E-02 2.057 39.86 3632
5.59E-08 0.593 7.72E-03 3.34E-03 1.20E-01 2.031 39.93 4716 3448
5.59E-08 0.593 7.72E-03 3.34E-03 1.20E-01 2.031 39.93 3783
2.44E-07 0.476 1.92E-02 1.90E-03 1.71E-01 1.955 40.12 3092 2635
2.44E-07 0.476 1.92E-02 1.90E-03 1.71E-01 1.955 40.12 2495
i.lQE-06 0.338 4.73E-02 1.04E-03 2.30E-01 1.823 40.38 1881 1916
1.10E-06 0.338 4.73E-02 1.04E-03 2.30E-01 1.823 40.38 1551
1.15E-09 0.767 5.30E-04 1.53E-02 2.8 RE-02 2.112 39.60 5444 6045
1.15E-09 0.767 5.30E-04 1.53E-02 2.88E-02 2.112 39.60 5341
4.44E-08 0.652 6.05E-03 4.50E-03 9.69E-02 2.047 39.77 4972 4418
4.44E-08 0.652 6.05E-03 4.50E-03 9.69E-02 2.047 39.77 4727
9.41E-08 0.607 9.73E-03 3.42E-03 1.18E-01 2.018 39.84 4178 3908
9.41E-08 0.607 9.73E-03 3.42E-03 1.18E-01 2.018 39.84 3975
3.93E-07 0.497 2.36E-02 1.98E-03 1.66E-01 1.938 40.02 3275 2893
3.93E-07 0.497 2.36E-02 1.98E-03 1.66E-01 1.938 40.02 2932
1.66E-06 0.364 5.60E-02 1.12E-03 2.22E-01 1.805 40.29 1813 2015
1.66E-06 0.364 5.60E-02 1.12E-03 2.22E-01 1.805 40.29 1873
3.45F.-09 0.775 8.74E-04 1.54E-02 2.83E-02 2.105 39.41 9677 9593
3.45E-09 0.775 8.74E-04 1.54E-02 2.83E-02 2.105 39.41 8467
L22E-07 0.675 9.40E-03 4.71E-03 9.27E-02 2.027 39.58 7685 7559
1.22E-07 0.675 9.40E-03 4.71E-03 9.27E-02 2.027 39.58 7440
2.50E-07 0.636 1.48E-02 3.62E-03 1.12E-01 1.995 39.65 7902 6877
2.50E-07 0.636 1.48E-02 3.62E-03 1.12E-01 1.995 39.65 6979
1.19E-06 0.519 3.90E-02 I.99E-03 1.63E-01 1.890 39.85 5559 5208
L19E-06 0.519 3.90E-02 1.99E-03 1.63E-01 1.890 39.85 5261
3.63E-06 0.416 7.60E-02 1.28E-03 2.03 E-01 1.774 40.1 4177 4072
3.63E-06 0.416 7.60E-02 1.28E-G3 JL03E-Q1 1.774 40.1 3543
9.59F.-09 0.782 1.38F-03 1.5RF.-02 2.75E-02 2.098 39.20 14008 14634
9.59E-09 0.782 1.38E-03 1.58E-02 2.75E-02 2.098 39.20 13756
3.O5E-07 0.696 1.39E-02 4.99E-03 8.71E-02 2.010 39.37 11284 10900
3.05E-07 0.696 1.39E-02 4.99E-03 8.71E-02 2.010 39.37 10498
6.09E-07 0.661 2.14E-02 3.87E-03 1.05E-01 1.976 39.44 11036 9680
6.09E-07 0.661 2.14E-02 3.87E-03 1.05E-01 1.976 39.44 11002
2.19E-06 0.574 4.73E-02 2.38E-03 1.42E-01 1.884 39.62 6868 7187
2.19E-06 0.574 4.73E-02 2.38E-03 1.42E-01 1.884 39.62 6458
7.55E-06 0.464 9.93E-02 1.44E-03 1.81E-01 1.749 39.88 4743 4921
7.55E-06 0.464 9.93E-02 1.44E-03 .. 1J1E-01 1.749 39.88 5116
2.48F.-08 0.788 2.09E-03 1.64E-02 2.65E-02 2.092 38.97 20959 23586
2.48E-08 0.788 2.09E-03 1.64E-02 2.65E-02 2.092 38.97 22174
7.O8E-07 0.714 I.95E-02 5.34E-03 8.02E-02 1.997 39.15 19116 16636
7.08E-07 0.714 1.95E-02 5.34E-03 8.02E-02 1.997 39.15 20079
1.37E-06 0.684 2.95E-02 4.18E-03 9.51E-02 1.961 39.21 13954 14417
1.37E-06 0.684 2.95E-02 4.18E-03 9.5 IE-02 1.961 39.21 15236
4.64E-06 0.607 6.24E-02 2.61E-03 1.26E-01 1.866 39.39 8999 10023
4.64E-06 0.607 6.24E-02 2.61E-03 1.26E-01 1.866 39.39 9034
1.49E-05 0.507 1.25E-01 1.62E-03 1.56E-01 1.731 39.66 6932 6247
1-49E-05.. 0.507 1.25E-01 I.62E-03 1.56F.-01 1.731 39.66 5872
134
Temperature
(K)
Melarity Loading
Pt2
L h d
Kap i
MDIA
(mol/1)
MEA
(mel/1) (mol/mo!) (kPa) (a n 3/s) (cm) (cm) (mel/s)
298 ' 2.116 0.490 0.0097 90.61 0.455 1.946 0.0580 1.860K-06
2.316 0.490 0.0097 90.61 0.455 2.416 0.0595 2.230E-06
2.316 0.490 0.0293 90.50 0.468 1.651 0.0580 I.583E-06
2,316 0.490 0.0293 90.50 0.468 2.524 0.0603 2.260E-06
2.316 0.490 0.0557 91.26 0.396 1.763 0.0545 1.578E-06
2.316 0.490 0.0557 91.26 0.396 2.172 0.0553 1.783E-06
2.316 0.490 0.0965 92.22 0.469 2.039 0.0560 1.550E-O6
2.316 0.490 0.0965 92.22 0.469 2.507 0.0557 1.677E-06
2,316 0.490 0.1240 92.22 0.419 1.784 0.0565 1.063E-06
2.316 0.490 0.1240 92.22 0.419 2.151 0.0597 1.180E-06
102 2.116 0.490 0.0097 89.55 0.465 2.057 0.0595 2.141F.-06
2.316 0.490 0.0097 89.55 0.465 2.440 0.0577 2.389E-G6
2.316 0.490 0.0293 89.49 0.486 2.460 0.0530 2.372E-06
2.316 0.490 0.0293 89.49 0.486 2.134 0.0537 2.079E-06
2.316 0.490 0.0557 90.17 0.388 1.746 0.0570 1.543E-06
2.316 0.490 0.0557 90.17 0.388 2.294 0.0557 1.827E-06
2.316 0.490 0.0965 91.14 0.466 2.197 0.0550 1.717E-06
2.316 0.490 0.0965 91.14 0.466 2.523 0.0547 1.895E-06
2.316 0.490 0.1240 90.79 0.416 1.992 0.0600 1.039E-06
2.316 0.490 . 0.1240 90.79 .... 0.416 2.338 0.0593 I.218E-06
111 2.116 0.490 0.0097 86.19 0.455 2.017 0.0517 2.507F.-06
2.316 0.490 0.0097 86.39 0.455 2.476 0.0513 2.862E-06
2.316 0.490 0.0293 86.31 0.430 1.841 0.0513 1.874E-06
2.316 0.490 0.0293 86.31 0.430 2.513 0.0520 2.481E-06
2.316 0.490 0.0557 87.19 0.368 1.789 0.0580 1.700E-06
2.316 0.490 0.0557 87.19 0.368 2.223 0.0578 2.018E-06
2.316 0.490 0.0965 87.91 0.414 1.758 0.0530 1.343E-06
2.316 0.490 0.0965 87.91 0.414 2.356 0.0550 1.733E-06
2.316 0.490 0.1240 87.66 0.406 1.838 0.0600 1.070E-06
2.316 0.490 0.1240 87.66 0.406 2.299 0.0587 1.334E-06.
121 2.116 0.490 0.0097 81.09 0.446 2.020 0.0517 2.51 IE-06
2.316 0.490 0.0097 83.09 0.446 2.572 0.0523 3.154E-06
2.316 0.490 0.0293 81.49 0.364 1.751 0.0588 I.970E-06
2.316 0.490 0.0293 81.49 0.364 2.163 0.0587 2.398E-06
2.316 0.490 0.0557 82.46 0.377 1.800 0.0595 1.883E-06
2.316 0.490 0.0557 82.46 0.377 2.236 0.0580 2.215E-06
2.316 0.490 0.0965 83.10 0.417 1.701 0.0523 1.299E-06
2.316 0.490 0.0965 83.10 0.417 2.320 0.0537 1.774E-06
2.316 0.490 0.1240 81.97 0.425 2.086 0.0563 1.422E-06
2.316 0.490 0.1240 81.97 0.425 2.320 0.0580 1.562E-06
111 2.116 0.490 0.0097 71.74 0.447 2.120 0.0515 2.657E-06
2.316 0.490 0.0097 73.74 0.447 2.503 0.0528 3.25OE-06
2.316 0.490 0.0293 73.91 0.382 1.727 0.0570 1.918E-06
2.316 0.490 0.0293 73.91 0.382 2.238 0.0555 2.373E-06
2.316 0.490 0.0557 73.82 0.372 1.893 0.0573 1.823E-06
2.316 0.490 0.0557 73.82 0.372 2.198 0.0590 2.050E-06
2.316 0.490 0.0965 75.44 0.396 2.138 0.0557 1.647E-06
2.316 0.490 0.0965 75.44 0.396 2.493 0.0583 1.934E-06
2.316 0.490 0.1240 74.32 0.400 2.141 0.0590 1.512E-06
2.316 0.490 0.1240 74.32 0.400 2,493 0.0570 1.632E-06
135
Table .3, (Continued.,.)
fCOji
(mol/1)
|RNH21
(ijioI/1)
f.HCOi | [Off]
(mol/i)
ICOj2!
(mol/1)
IR3N]
(mol/1)
[H20]
(moM)
kapp,experimental
Raw Data
(1/s)
Average
(1/s)
7.23F.-10 0.453 4.01F.-04 1.34F.-02 2.52F.-02 2.285 19.72 3177 3501
7.23E-10 0.453 4.01E-04 1.34E-02 2.52E-02 2.285 39.72 2805
1.30E-O8 0.401 2.83E-03 5.23E-03 6.91E-02 2.239 39.82 3275 2900
1.30E-08 0.401 2.83E-03 5.23E-03 6.91E-02 2.239 39.82 2631
8.64E-08 0.332 9.51E-03 2.66E-03 I.18E-01 2.168 39.95 3199 2272
8.64E-08 0.332 9.51E-03 2.66E-03 1.18E-01 2.168 39.95 2606
4.92E-07 0.244 2.80E-02 1.38E-03 1.80E-01 2.047 40.15 2143 1661
4.92E-07 0.244 2.80E-02 1.38E-03 1.80E-O1 2.047 40.15 1677
1.14E-06 0.198 4.68E-02 9.89E-04 2.17E-01 1.958 40.29 1294 1410
1.14E-06 0.198 4.68E-02 9.89E-04 2.17E-01 1.958 40.29 981
1.23F.-09 0.457 5.12F.-04 1.37F.-02 2.51 F.-02 2.282 89.63 3977 4842
1.23E-09 0.457 5.I2E-04 1.37E-02 2.51E-02 2.282 39.63 3737
2.I4E-08 0.409 3.53E-03 5.45E-03 6.85E-02 2.231 39.72 4421 3778
2.14E-08 0.409 3.53E-03 5.45E-03 6.85E-02 2.231 39.72 4398
1.36E-07 0.345 1.16E-02 2.82E-03 1.16E-01 2.157 39.85 3177 2726
1.36E-07 0.345 1.16E-02 2.82E-03 1.16E-01 2.157 39.85 2700
7.31E-07 0.262 3.31E-02 1.50E-03 1.76E-01 2.034 40.06 2623 1778
7.3 IE-07 0.262 3.31E-02 1.50E-03 1.76E-01 2.034 40.06 2448
1.64E-06 0.217 5.42E-02 1.09E-03 2.10E-01 1.946 40.19 982 1410
L64E-06 0.217 5.42E-02 1.09E-03 2.10E-01 1.946 40.19 1003
3.37F.-09 0.463 8.08E-04 1.46E-02 2.47F.-02 2.275 39.44 8795 8658
3.37E-09 0.463 8.08E-04 1.46E-02 2.47E-02 2.275 39.44 8299
5.45E-08 0.423 5.33E-03 5.96E-03 6.67E-02 2.218 39.53 6574 6450
5.45E-08 0.423 5.33E-03 5.96E-03 6.67E-02 2.218 39.53 6018
3.22E-07 0.369 1.68E-02 3.17E-03 1.12E-01 2.138 39.66 4423 4325
3.22E-07 0.369 1.68E-02 3.17E-03 1.12E-01 2.138 39.66 4065
1.57E-06 0.295 4.51E-02 1.75E-03 1.66E-01 2.012 39.86 3381 2505
1.57E-06 0.295 4.51E-02 1.75E-03 1.66E-01 2.012 39.86 2905
3.32E-06 0.254 7.12E-02 1.31E-03 1.95E-01 1.926 40 1528 1840
3.32E-06 0.254 7.12E-02 1.31E-03 1.95E-01 1.926 40 ... 1591
8.68E-09 0.468 1.23F.-03 1.56F.-02 2.42F.-02 2.269 39.23 11661 10648
8.68E-09 9.468 1.23E-03 1.56E-02 2.42E-02 2.269 39.23 11002
L30E-07 0.436 7.74E-03 6.57E-03 6.40E-02 2.207 39.32 7844 8555
1.30E-07 0.436 7.74E-03 6.57E-03 6.40E-02 2.207 39.32 7634
7.17E-07 0.390 2.33E-02 3.57E-03 1.05E-01 2.123 39.45 6546 6289
7.17E-07 0.390 2.33E-02 3.57E-03 1.05E-01 2.123 39.45 6171
3.2 IE-06 0.325 5.94E-02 2.03E-03 1.52E-01 1.997 39.65 4470 4065
3.21E-06 0.325 5.94E-02 2.03E-03 1.52E-01 1.997 39.65 4246
6.50E-06 0.286 9.10E-02 1.54E-03 1.76E-01 1.913 39.79 3154 3146
6.50E-06 0.286 9.10E-02 1.54E-03 1.76E-01 1.913 39.79 2889
2.12E-08 0.473 1.82F.-03 1.67F.-02 2.3.6F.-02 2.264 39.01 17169 15313
2.12E-08 0.473 1.82E-03 1.67E-02 235E-02 2.264 39.01 17555
2.90E-07 0.446 1.08E-02 7.25E-03 6.06E-02 2.199 39.10 11251 12138
2.90E-07 0.446 1.08E-02 7.25E-03 6.06E-02 2.199 39.10 10796
1.51E-06 0.407 3.12E-02 4.O2E-03 9.67E-02 2.114 39.23 8513 8662
1.5 IE-06 0.407 3.12E-02 4.02E-03 9.67E-02 2.114 39.23 7496
6.30E-06 0.349 7.56E-02 2.33E-03 1.36E-01 1.988 39.43 5554 5287
6.30E-06 0.349 7.56E-02 2.33E-03 1.36E-01 1.988 39.43 5113
1.23E-05 0.315 1.13E-01 1.79E-03 1.56E-01 1.906 39.56 4277 3922
1.23E-05 0.315 1.13E-01 1.79E-03 1.56E-01 1.906 39.56 . 3929.....
136

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KINETICS OF THE ABSORPTION OF C02INTO MIXED

AQUEOUS LOADED SOLUTIONS OF MONOETHANOLAMINE AND

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