Welcome to Scribd, the world's digital library. Read, publish, and share books and documents. See more
Download
Standard view
Full view
of .
Save to My Library
Look up keyword
Like this
0Activity
0 of .
Results for:
No results containing your search query
P. 1
Effect of methanol addition on water–CO2–diethanolamine system Influence on CO2 solubility and on liquid phase speciation

Effect of methanol addition on water–CO2–diethanolamine system Influence on CO2 solubility and on liquid phase speciation

Ratings: (0)|Views: 63|Likes:
Published by Mehdi Alizad
Effect of methanol addition on water–CO2–diethanolamine system Influence on CO2 solubility and on liquid phase speciation
Effect of methanol addition on water–CO2–diethanolamine system Influence on CO2 solubility and on liquid phase speciation

More info:

Published by: Mehdi Alizad on Jul 11, 2013
Copyright:Attribution Non-commercial

Availability:

Read on Scribd mobile: iPhone, iPad and Android.
download as PDF, TXT or read online from Scribd
See more
See less

05/14/2014

pdf

text

original

 
chemical engineering research and design 86 (2008)
592–599
available at www.sciencedirect.com journal homepage: www.elsevier.com/locate/cherd
Effect of methanol addition on water–CO
2
–diethanolaminesystem: Influence on CO
2
solubility and on liquid phasespeciation
 A. Archane, L. Gicquel, E. Provost, W. F¨ urst
UER Chimie et proc´ ed´ es, Ecole Nationale Sup´ erieure de Techniques Avanc´ ees, 32 Boulevard Victor, 75739 Paris Cedex 15, France
a r t i c l e i n f o
 Article history:
Received 2 October 2007Accepted 10 March 2008
Keywords:
AbsorptionAcid gasAlcanolamineCarbamatesCarbon dioxideEOS
a b s t r a c t
The aim of this study is the characterisation of VLE and chemical equilibria for the sys-tem CO
2
 /diethanolamine (DEA)/H
2
O/methanol. The effect of MeOH composition has beenstudied using four compositions (from 0 to 30wt% of methanol with a fixed composition(30wt%) of DEA), the measurement being made at
=298.15K and at various CO
2
loadings(from 0.2 to 0.8). An original experimental device was used. This device combines a FT-IRspectroscopy analysis of the liquid phase with a VLE measurement cell.The data base obtained, including the new solubility data and the liquid phase com-position, allows the modelling of the system CO
2
 /DEA/H
2
O/methanol using an electrolyteequation of state [F ¨ urst, W., Renon, H., 1993, Representation of excess properties of elec-trolyte solutions using a new equation of state, AIChE J, 39(2): 335–343] representing theequilibrium properties of the system and the liquid phase speciation.© 2008 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
1. Introduction
Absorption of acid gases (CO
2
and H
2
S) in alkanolamine solu-tion is widely used in many gas purification processes. Theseprocesses are based on chemical absorption. The chemicalequilibria involved in the systems are as follows:waterdissociation : 2H
2
O
H
3
O
+
+
OH
aminedissociation :
R
1
R
2
R
3
N
+
H
3
O
+
R
1
R
2
R
3
NH
+
+
H
2
Ocarbondioxidehydrolysis : CO
2
+
2H
2
O
HCO
3
+
H
3
O
+
hydrogen-carbonatehydrolysis :HCO
3
+
H
2
O
CO
32
+
H
3
O
+
carbamateshydrolysis :
R
1
R
2
NH
+
HCO
3
R
1
R
2
NCOO
+
H
2
O(secondaryandprimaryamine)
Corresponding author
.E-mail address:Walter.Furst@ensta.fr(W. F ¨ urst).
Hence the solutions resulting from the absorption of acidgasesarecomplexonesandcontainionicaswellasmolecularsolutes.In this case, i.e. when the species present in the liquidphase are connected by chemical reactions, it is known thatthemodelsusingparametersadjustedonlyonthepressurevs.CO
2
solubility data lead to non-realistic representations of theliquid phase composition. Consequently, even if the represen-tation of the solubility data is correct, any extrapolation of themodel beyond the range of experimental values used for theadjustment may conduct to large deviations. Moreover, theincorporation of such thermodynamic approach in a modelused to represent the absorption kinetics is not very reliable.The need of speciation data could be illustrated by theresults we obtained studying a much more simple system(Passarello and F ¨ urst, 1996).In the case of water–nitric acid system the data treatment of experimental values for waterand nitric acid partial pressures conducted to a bad rep-resentation of acid dissociation. But when the speciationdata are included in the database, a precise representa-tion of both type of data (VLE and speciation) could beobtained.
0263-8762/$ – see front matter © 2008 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.doi:10.1016/j.cherd.2008.03.005
 
chemical engineering research and design 86 (2008)
592–599
593
Nomenclature
 A
peak area (A.U)
b
covolume
c
volume translation factor
C
concentration (mol/L)
D
dielectric constant of the solution
e
protonic charge
k
response coefficient
n
number of moles
N
Avogadro number
P
pressure (kPa)
R
gas constant
temperature (K)
v
molar volume of the solution
volume (L)
interaction parameter (defined in Eq.(3))
x
mole fraction
x
app
apparent mole fraction
Z
ionic charge
Greek letters
˛
loading 
 
the shielding parameter (defined inAppendixB)
correlation parameter (defined in Eq.(3))
 
diameter
 
H
2
O
solvated diameter by water
 
mel
solvated diameter in mixture
 
NRTL parameter
Subscripts
c critical property
i
,
 j
relative to ionic speciesLR long-range termRF repulsive forces termSOL solutionSR1 non-electrolyte short-range termSR2 ionic short-range termHowever,althoughthereisastronglinkbetweenthedevel-opment of a realistic model and the use of experimentalinformation about the liquid phase speciation, the equi-librium data available in the literature are essentially VLEdata (Lawson and Garst, 1976; Lee et al., 1972; Rogers et al.,1997).Very few are related to the liquid phase composition(Poplsteinova Jakobsen et al., 2005; B ¨ ottinger et al., 2008).Thisconducted us to develop an original device that combines aFT-IR spectroscopic analysis of the liquid phase with a VLEmeasurement cell (Sidi-Boumedine, 2003).Since several years, processes using physical solvents aswell as chemical solvents were developed (Isaacs et al., 1977:sulfinol solution;Henni and Mather, 1995:MDEA+methanol; Tounsi et al., 2005:DEA+methanol). This explains that, as apart of our laboratory’s experimental work is devoted to thedetermination of the speciation in electrolyte systems, weinitiated the determination of the effect of adding a phys-ical solvent (methanol) on the liquid phase composition of CO
2
 /alkanolamine/water system. This mixed solvent systemhas been studied as a possible solvent for acid gas absorptionprocess and some experimental values for solubility of CO
2
and H
2
S have been already published (Tounsi et al., 2005).
2. Methods and materials
2.1. Apparatus
The experimental device used in this work consists in twoparts: the equilibrium cell, where the solubility of the CO
2
ismeasuredandanexternalanalyticalloop,wherethecomposi-tion of the liquid phase is determined. This device, presentedinFig. 1,allows the measurement of liquid–vapor equilibria as well as the liquid phase composition for pressure rangefrom0to200kPaandfortemperaturesbetween280and350K.The equilibrium cell is a double-jacketed glass reactor (vol-ume=460mL), equipped with a pressure transducer (PTX 611from Druck) and temperature probe (Pt 100, from TC SA). Theuncertainties in pressure and temperature are
±
0.1kPa and
±
0.1K, respectively and the maximum pressure is 200kPa aswe are using a glass cell. The stainless lid is maintained at atemperatureslightlyhigherthanthecelltemperaturetoavoidcondensation phenomena. The liquid phase analysis is real-ized using an infrared spectrometer with an ATR (attenuatedtotal reflectance) cell. During the measurement, the liquidphase is pumped out from the equilibrium cell to the ATR cellby HPLC pump, and then returns to the equilibrium cell. Thetemperature of the circulation loop (global volume: 3mL) ismaintained at the temperature of the equilibrium cell with anaccuracy of 
±
0.8K.
2.2. Experimental procedure
CO
2
with a purity of 99.9%, supplied by Air Liquide, was used.The solutions are prepared by weighting, using solvents indi-vidually degassed. Distilled water and solvents with purity of +99% were used (methanol and diethanolamine (DEA) fromSigma Aldrich). The final degassed solution, containing water,methanol and DEA, is transferred into the equilibrium cell.Once the thermal equilibrium is reached, the corresponding solvent vapor pressure
P
vapsol
is measured. CO
2
, contained in areservoir, is then loaded into the cell. Both amounts of CO
2
and alkanolamine solution introduced in the cell are knownbyweightingtheirreservoirsbeforeandaftertheintroduction.The precision of weighting is 0.001g. Pressure and IR spec-tra are regularly checked and when no change occurs within1h, we assume that the equilibrium is reached. The equilib-rium pressure and the IR spectra are then recorded, the IR
Fig. 1 – Schematic diagram of the apparatus.
 
594
chemical engineering research and design 86 (2008)
592–599
spectra being used for the determination of the liquid phasespeciation.The measurements have been made at
=298.15K and atvariousCO
2
loadings(thenumberofmolesofCO
2
intheliquidphase, divided by the number of alkanolamine moles in theliquid phase) from 0.2 to 0.8 for every studied system.
2.2.1. Partial pressure and CO
2
loading determination
The CO
2
partial pressure
P
CO
2
is calculated from the totalpressure
P
tot
and the saturated vapor pressure of the gas-freesolvent
P
vapsol
applying Raoult’s expression:
P
CO
2
=
P
tot
P
VAPSOL
(1
x
appCO
2
) (1)where
x
appCO
2
is the apparent molar fraction of CO
2
in the liquidphase.To study the solubility of CO
2
in the solution, the partialpressure of carbon dioxide in the reactor is presented as afunction of the CO
2
loading 
˛
CO
2
. Thus to calculate the CO
2
loading, it is necessary to know the global mole numbers of amines and CO
2
in the liquid phase from the total amount of CO
2
in the cell at equilibrium temperature and pressure. Asthe amine is a non-volatile compound, the total mole numberof amine in the liquid phase corresponds to what has beenintroducedinthecellandisknownbyweighting.Ontheotherhand,CO
2
ispresentinbothvaporandliquidphasesandacor-rection of vapor phase is necessary for calculation of the CO
2
loading. Finally we have
˛
CO
2
=
n
CO
2
,
in
[(
reactor
solution
)
/V 
molCO
2
,
gas
]
n
Am
,
in
(2)where
n
CO
2
,
in
is the total number of CO
2
introduced,
reactor
the volume of the reactor,
solution
the volume of the solutionand
molCO
2
,
gas
is the molar volume of CO
2
in the vapor phase(deduced from the partial pressure of CO
2
in the vapor phaseby applying the ideal gas expression). The accuracy on theloading is 1%.
2.2.2. IR peak identification and determination of theconcentration
Fig. 2presents the IR spectrum obtained for a water/DEA solu-tionloadedwithCO
2
.Threepeaksareparticularlyinteresting:the peak observed at 2340cm
1
is specific to molecular CO
2
,the peak at about 1530cm
1
is representative of carbamatesand the one at 1360cm
1
is characteristic of HCO
3
. In orderto get quantitative results from the treatment of IR spectra, it
Fig. 2 – Infrared spectrum of a DEA solution charged withCO
2
.
is necessary to determine the area of each peak. For HCO
3
and carbamate, a deconvolution is necessary. The concentra-tion
C
i
of a specie
i
is then proportional to the corresponding peak area
A
i
by:
C
i
=
k
i
 A
i
(mol/L) where
k
i
has to be determinedthrough calibration experiments.
Molecular CO
2
concentration determinationFromFig. 2it could be observed that the CO
2
peak is locatedin spectrum range where no other significant absorption ispresent. It may be easily integrated. The validity of a linearrelationship between the CO
2
peak and the CO
2
concentra-tion
C
CO
2
,molec
=
k
CO
2
Area
CO
2
was checked by the analysisof the water/CO
2
system (Sidi-Boumedine et al., 2005).The accuracy on
C
CO
2
is 15%.In this system, the dissolved CO
2
concentration (molecularform) is perfectly known as a function of temperature andpressure (Carroll et al., 1991).Knowing the peak area and the concentration, the authors have determined the
k
CO
2
value. In the present study, this value is used to determinethe molecular CO
2
concentration from its IR peak area.
HCO
3
and carbamate concentration determinationThe study of MDEA–H
2
O–CO
2
system allows to determinethe coefficient
k
HCO
3
connecting the HCO
3
peak area toits concentration. In this case, the HCO
3
concentration isthe difference between the introduced CO
2
concentrationand the molecular CO
2
. In a second step, the analyses of the spectra of DEA–H
2
O–CO
2
system allows to determinethe coefficient
k
carbamate
connecting the carbamates peakarea to its concentration. This concentration is calculatedby subtraction of the HCO
3
concentration and the molecu-larCO
2
concentrationfromtheapparentCO
2
concentration.These calibrations have been done and the determinationof the HCO
3
and carbamates peak areas in the systemscontaining methanol will make it possible to know theirconcentration.
3. Results and analyses
The aim of this work is to study the effect of methanol–watersystem on the equilibrium properties in the presence of DEAand CO
2
. This effect has been studied using different solventcompositions(from0to30wt%ofmethanolwithfixedcompo-sition (30wt%) of DEA), the measurement being made at fixedtemperature (
=298.15K):
methanol: 0wt%; water: 70wt%; DEA: 30wt%
methanol: 10wt%; water: 60wt%; DEA: 30wt%
methanol: 20wt%; water: 50wt%; DEA: 30wt%
methanol: 30wt%; water: 40wt%; DEA: 30wt%
3.1. Solubility
In order to compare CO
2
solubility of the various studied sys-tems,werepresentedinthesamefigure(Fig.3)theevolutionof  CO
2
partial pressure (determined from the reactor total pres-sure by application of Eq.(1))with the CO
2
loading at differentcompositions.Inallthecases,thevariationoftheCO
2
pressureisverylowfor loadings lower than 0.5. Beyond this value, the solubility of CO
2
decreases (the CO
2
partial pressure increases) with theincrease in the CO
2
loading, even if we remain clearly belowthe amine saturation. In fact when the CO
2
loading increases,the carbamate is transformed gradually into HCO
3
. At fixed

You're Reading a Free Preview

Download
/*********** DO NOT ALTER ANYTHING BELOW THIS LINE ! ************/ var s_code=s.t();if(s_code)document.write(s_code)//-->