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Simulation of an Oshore Natural Gas Purication Process for CO

2
Removal with GasLiquid Contactors Employing Aqueous Solutions
of Ethanolamines
Jose Luiz de Medeiros,* Andressa Nakao, Wilson M. Grava, Jailton F. Nascimento,
and Ofe lia de Queiroz F. Arau jo
Escola de Qumica, Federal University of Rio de Janeiro, Av. Hora cio Macedo, 2030, Centro de Tecnologia, EIlha do Funda o, Rio
de Janeiro-RJ, 21941-909, Brazil
*S Supporting Information
ABSTRACT: In the scenario of oshore rigs angular indierence, modularity, and compactness strongly inuence selection of
technology for natural gas purication. Gasliquid contactors have such attributes and perform gas absorption without the
concerns of packing columns like weight, ooding, gravitational alignment, and water saturation. This paper proposes a model for
gasliquid hollow ber contactors using aqueous alkanolamines for CO
2
removal from high pressure natural gas. The model
assumes high-pressure compressible ows of both permeate and retentate with full thermodynamics via equations of state.
Permeate is approached as a reactive vaporliquid equilibrium ow of solvent with CO
2
/CH
4
from membrane uxes. Phase
change and reactive heat eects are modeled via mass, energy, and momentum balances written for permeate/retentate as a
dierential-algebraic system for dependent variables temperature, pressure, and component ows. Proles are obtained via
numerical spatial integration with algebraic resolution imbedded, accounting for permeate reactive vaporliquid equilibrium with
only the molecular species incorporated into a Chemical Theory framework.
1. INTRODUCTION
Separation unit operations in any kind of process have always to
be chosen judiciously and carefully, otherwise they may become
burdensome appendices undermining the protability, controll-
ability, safety, and simplicity of the plant. Nevertheless, even
when properly selected, separations usually raise concerns like
energy consumption, utilities, chemicals demands, size and
weight, construction restraints, operational hazards, etc. In oil
and natural gas (NG) deep-water oshore rigs, an issue in the
processing of large volumes of NG with high CO
2
/CH
4
ratios
vis-a -vis climate concerns, involves large capacity CO
2
separators,
whose targets are exportation of saleable NG via long pipelines
and alimentation of enhanced oil recovery (EOR) systems with
hyperpressurized CO
2
. In this scenario, robustness, angular
indierence, modularity, and compactness also inuence the
selection of technology, so that membrane permeation modules
are usually favored against the traditional absorbing towers with
alkaline solvents.
1,2
On the other hand, large permeation
batteries also have their own shortcomings, mostly related to
the permselective dense (nonporous) skin over the microporous
substrate, that is, lowuxes, lowcapacity per unit area, CO
2
/CH
4
limited selectivity, feed dew-point conditioned, high P,
continuous inspection for membrane bursts, and high con-
sumption of power for permeate recompression and recycles.
1
Gasliquid contactors (GLC) are versatile membrane
operations for CO
2
removal from NG capable to outperform
nonporous permeators in terms of capacity per unit area while
sustaining high CO
2
/CH
4
selectivity. High uxes are possible in
GLC because the membrane does not have to be selective, since
selectivity is imposed by the solvent in the permeate side cutting
the necessity of high P.
3,4
At the same time, GLC absorbs gas
without typical concerns of packing towers like weight, ooding,
tall setups, gravitational alignment, water-saturated products,
entrainment, phase distributors, and foaming.
14
In summary,
GLC for CO
2
/NG cuts oers the advantages of both membrane
and absorption technologies, but leaving behind the respective
drawbacks. GLC combines membrane separation and chemical
absorption, using a physically and chemically active solvent
4
for
selective CO
2
capture, and a membrane standing as a physical
barrier against the unnecessary mixing of gas and liquid. Further
advantages of GLC
5
are independent liquid and gas ow
manipulation, larger gasliquid interfaces, exibility to scale up
or down, no dew-point conditioning, and modularity.
These advantages have motivated a rush of papers on hollow
ber membrane (HFM) contactors in the last decades.
18
In the
literature HFMGLCs are generally congured in parallel ow
with gas and liquid on the opposite HFM sides. The gas phase
can oweither outside (shell) or inside (lumen) the HFM, but in
the majority of studies liquid ows in the inner HFMside and gas
in the shell side. An aspect that soon became clear was that
membrane pores should remain lled with gas, that is, a
nonwetted condition, giving low mass transfer resistance.
Otherwise, if HFM pores saturate with a stagnant liquid, that
is, a wetted condition, mass transfer resistance increases,
lowering uxes and destroying the economic leverage of GLC.
This entails that long-term operation of GLC implies utilization
Special Issue: PSE-2012
Received: September 25, 2012
Revised: February 12, 2013
Accepted: February 13, 2013
Published: February 13, 2013
Article
pubs.acs.org/IECR
2013 American Chemical Society 7074 dx.doi.org/10.1021/ie302507n | Ind. Eng. Chem. Res. 2013, 52, 70747089
of hydrophobic HFM.
3,4
Initial studies on absorption with
hydrophobic HFM were conducted by Zhang and Cussler.
6,7
Karoor and Sirkar
8
conducted experiments on CO
2
and SO
2
absorption through hydrophobic HFM, concluding that mass
transfer rates can be 10 times higher than analogous packed
towers. On the other hand, problems with hydrophobic HFM
derive from partial wetting and lumen gas bubbles. Partial
wetting has been reported with polypropylene (PP) and
polyvinylidene uoride (PVDF) hydrophobic HFMs and also
due to alkanolamines which decrease surface tension and
facilitate wetting.
4
Bubbling in the inner HFM is viewed,
4
in
principle, as a bad feature that creates stagnation and hindrance
to mass transfer. But, it is arguable that depending on the design,
geometry, and pressures on the HFM sides, inner gas is not
necessarily bad since it can accelerate the solvent as a two-phase
nonstratied ow, destroying stagnation, increasing turbulence,
and enhancing mass transfer coecients.
Concerning the solvent, the advantages of the chemical
absorption of acid gases by aqueous alkanolamines are well-
known: they are weak acids and such solvents are weak alkali,
such that bonding between them is reversibly broken at high
temperatures and low partial pressures, leading to ecient gas
stripping and solvent regeneration. That is, GLC is suited to
separations with acid gas, water and alkanolamines, or AGWA
systems. An AGWAsystemmay include one or more acid gas(es)
and one or more alkanolamine(s), but water is mandatory. An
AGWAsystemis normally in a reactive vaporliquid equilibrium
(RVLE), under pressures from a few mmHg up to 200 bar and
temperatures up to 180 C. Primary alkanolamines (e.g.,
monoethanolamine, MEA), secondary alkanolamines (e.g.,
diethanolamine, DEA), tertiary alkanolamines (e.g., methyl-
diethanolamine, MDEA) are common in AGWA systems and
their properties and comparative advantages can easily be found
in the literature.
9
Blends of alkanolamines for conjugating
desirable qualities have been tried to obtain solvents with good
reactivity and lower costs of regeneration and corrosion as in the
case of blends MDEA+MEA, which indicate gains relatively to
individual amines.
10
The design of high capacity GLC experiences a relative
unavailability of pilot data and/or reliable mathematical
modeling of CO
2
separation from high pressure NG. In the
last 10 years there were innumerable papers in the GLC
literature. But the great majority of them avoided basic facets of
industrial NG purication like high loadings, heat eects,
temperature proles, high pressures, two-phase reactive
permeate, and the use of equations of state (EOS) replacing
ideal gas. Instead, typical GLC references mostly concentrate on
mass transfer idiosyncrasies of HFM.
35,1113
Such works
normally formulate three O(2) mass transfer boundary value
problems (BVP) in cylindrical geometry, respectively, for inner
liquid, outer vapor, and HFM, using three sets of diusivities in
axial and radial directions, and nonhomogeneity terms (in the
inner BVP) accounting for chemical reactions. When used,
partial or full pore wetting is accounted via boundary conditions
on the outer HFMand by modifying the HFMBVP. The reactive
permeate adopts a set of ionic, ideal solution, chemical
equilibrium (ChE) reactions based on Zwitterion,
14
leading to
rate formulas in concentrations of amine and CO
2
. All these
works adopt similar modeling simplications; that is, all of them
used several (declared or not) assumptions in the following list:
(i) negligible external and permeate-retentate heat transfers; (ii)
negligible heat eects of phase and chemical changes; (iii) no
enthalpy formalism; (iv) isothermal permeate/retentate ows;
(v) ideal gas phase; (vi) Henrys Law for CO
2
VLE at interface;
(vii) single-liquid phase permeate; (viii) ideal solution behavior
(including ions) in the liquid; (ix) no energy/momentum
balances for permeate/retentate; (x) no temperature proles;
(xi) parabolic velocity prole for inner liquid; (xii) no
compressible or two-phase ow formalisms; (xiii) no fugacity
formalism in ChE, VLE, or driving forces. The reiterated use of
such assumptions can be inferred fromthe comprehensive review
on GLC by Mansourizadeh and Ismail,
12
which states that GLC
models systematically considered (1) isothermal condition; (2)
parabolic velocity prole in the lumen; (3) negligible axial
diusion; (4) ideal gas phase; (5) low pressure; and (6) Henrys
Law at interface. Perhaps the rst exception to this trend, was the
work of Marzouk et al.
15
on experiments for CO
2
removal from
NG (90.5% CH
4
+ 9.5% CO
2
) up to 50 bar, using expanded
PTFE HFM (non elective microporous) for physical absorption
with H
2
Oand physicalchemical absorption with H
2
O+ NaOH,
H
2
O + MEA, H
2
O + DEA, H
2
O + TETA in several
concentrations at pressures 0.5 bar above gas pressure. Despite
its potential of interest, they did not report thermal eects or
temperature distributions, probably because they used high
solvent/gas volumetric ratios from 1:8 to 1:2 (in typical packed
columns this ratio ranges from 1:100 to 1:10).
The point here is that bold issues in high capacity GLCs
cannot be left without attention, for example, thermal eects,
temperature proles, high density compressible ows, RVLE
permeate, whereas certain intricate, but localized, theoretical
items can be replaced by short-cut formulas as done in
conventional unit operation design, such as radial incompressible
velocity prole replaced by axial compressible plug ow, O(2)
BVP for ux calculations replaced by equivalent permeancy times
fugacity dierences between outer and inner sides, and 2D
spatiality replaced by 1D axial description. To accomplish this,
this work addresses a model for CO
2
separation from high
pressure NG in HFMGLC with aqueous MEA/MDEA blends,
assuming (i) 1D high-pressure parallel compressible ows of
permeate and retentate, without velocity presumptions, but with
full thermodynamics via EOS (PR/SRK), (ii) permeate as a
RVLE two-phase ow of solvent with CO
2
+ CH
4
from
membrane uxes, (iii) mass, energy, and momentum balances
written for permeate/retentate, expressed as a dierential-
algebraic system, (iv) spatial integration with algebraic resolution
imbedded, accounting for RVLE permeate with only molecular
species incorporated into a VLE+ChE framework proposed in de
Medeiros et al.
16,17
This is a Chemical Theory
18
approach where
complex species are formed in liquid phase via ChE reactions
from real species CO
2
, H
2
S, H
2
O, MEA, MDEA. Complexes are
reversibly created in absorption and destroyed in stripping. The
limited knowledge to handle the numerous possible ions, is
circumvented via such nonionic, nonvolatile complexes, with the
advantage that model tuning requires only VLE AGWA data,
more available than nonequilibrium counterparts. The nonionic
assumption relies on the weakness of AGWA electrolytes, all
created by incomplete dissociations.
The rest of this work is organized as follows: section 2
describes the RVLE formalism for AGWA systems; section 3
approaches the modeling of HFMGLC with RVLE permeate
ow; section 4 simulates a GLC owsheet for CO
2
removal from
NG in oshore rigs including a solvent regeneration stripper also
in RVLE mode; section 5 ends the paper with its conclusions.
Industrial & Engineering Chemistry Research Article
dx.doi.org/10.1021/ie302507n | Ind. Eng. Chem. Res. 2013, 52, 70747089 7075
2. EQUILIBRIUM MODEL FOR AGWA SYSTEMS WITH
H
2
S/CO
2
/H
2
O/MEA/MDEA
Following the Chemical Theory,
16,18
the RVLE approach to
AGWA systems superimposes VLE onto ChE for a complete set
of molecular chemical reactions, creating a thermodynamically
sound tunable framework reproducing physicochemical changes.
Since thermodynamics does not need knowledge of the internal
structure of phases, the approach is molecular, with ctitious
species in the liquid phase, the complexes, replacing the actual
weak AGWA ions. Like ions, complexes are nonvolatile, not
acting in the VLE, but inuencing liquid properties. This
framework is tuned to data, with the following assumptions: (i)
species divided into two groups: complex and real; real species
comprise solutes CO
2
and H
2
S, amines MEA, MDEA and water;
(ii) each complex reaction has as reactants an acid gas, water, and
an amine with unitary coecients; (iii) Only real species are
subjected to VLE; (iv) complexes CO
2
H
2
OMEA, CO
2

H
2
OMDEA, H
2
SH
2
OMEA, H
2
SH
2
OMDEA are cre-
ated by eq 1, which displays ChE constants and standard states as
pure saturated liquid (liq) at T for complexes and pure ideal gas
(g) at T and 1 bar for real species:
+ +

+ +

+ +

+ +





g g
g g
g g
g g
CO ( ) H O(g) MEA( )
CO H O MEA(liq)
CO ( ) H O(g) MDEA( )
CO H O MDEA(liq)
H S( ) H O(g) MEA( )
H S H O MEA(liq)
H S( ) H O(g) MDEA( )
H S H O MDEA(liq)
K
K
K
K
2 2
2 2
2 2
2 2
2 2
2 2
2 2
2 2
1
2
3
4
(1)
(v) No ions are present, phases are molecular and treated via
EOS SRK/PR up to high pressures and all compositions,
provided critical constants (T
C
, P
C
, ) and normal boiling point
(T
B
) of complexes are available and compatible with negligible
vapor pressures as given in Table 1 via the Joback contribution
method;
19
(vi) All species participate in 4 ChE constraints
written for eq 1 with stoichiometric matrix (n n
C
) for real
species [CO
2
H
2
S H
2
O MEA MDEA ] given by
=




1 1 0 0
0 0 1 1
1 1 1 1
1 0 1 0
0 1 0 1 (2)
Calibration of this RVLE model demands VLE data with CO
2
,
H
2
S, H
2
O, MEA, MDEA for an implicit parameter estimation of
ChE constants K
1
, K
2
, K
3
, K
4
. The procedure is detailed in de
Medeiros et al.
16
and is only sketched here. All data used in this
procedure belong to the AGWA VLE database gathered by these
authors. The various sources of this data can be found in this
reference and are not cited here.
Labels A, S, C, V, L refer to amines, solutes, complexes, vapor,
liquid. An experiment contacts L mols of CO
2
, H
2
S, H
2
O, MEA,
MDEA at T. After VLE, pressure P is established with X, Y, X
C
, L
L
,L
V
, P
S
,
S
, namely, liquid and vapor fractions of real species,
liquid fractions of complexes, mols of liquid and vapor, solute
partial pressures and loadings. The experiment constraints are:
eq 3 as mass balances of real species (n eqs); eqs (4) as
normalizations (2 eqs); eqs 5 and 6 for solute partial pressures
and loadings (2n
S
eqs); eq 7 for VLE of real species (n eqs); and
eq 8 for ChE (n
C
eqs).
+ = L L X L X L Y ( ) 0
L C L V
(3)
+ =
= =
X X 1 0
j
n
j
k
n
k
1 1
C
C
(4a)
=
=
Y 1 0
j
n
j
1 (4b)
= P PS Y 0
S
S
(5)
+ = L S Y S L S L (1 ) 0
V
S
T
A
S
S
(6)



= f f ln ln 0
V L
(7)
+

= X f K T ln ln ln ( ) 0
C
T
L
(8)
Experiment variables and constraints (eqs 3 to 8) are put as in eq
9. Parameters ( = K ) are the ChE constants at the chosen
temperature (n

= n
C
= 4), where CO
2
, H
2
S, H
2
O, MEA, MDEA
the maximum numbers of variables and constraints per
experiment are n
Z
= 3n + 4 + n
C
+ 2n
S
= 27 and n
F
= 2n + 2 +
n
r
+ 2n
S
= 20. Thus, at a chosen temperature, one has to estimate
n

= n
C
= 4 parameters using a set of runs each one with about 27
variables and 20 constraints.
= Z T P L X Y X P L L [ ]
T
S
T
S
T T T T
C
T
V L
(9a)
= F Z ( , ) 0 (9b)
Let an extract of n
E
isothermal AGWA run. The goal is to
estimate its four ChE constants by an implementation of the
maximum likelihood criterion for implicit parameter estimation
known as the method of estimated deviations,
16
which can
estimate model parameters (

) and all variables (



Z
i
(i = 1, ...,
n
E
)). This implementation was successful and capable to handle
AGWA NLPs with outstanding numbers of variables and
constraints. Thermodynamic properties of both phases were
calculated with PR EOS. The optimization formulation is
expressed in eq 10:
Table 1. Nominal Constants of Complexes via Joback
Method
19
complex
MW
(g/mol) T
C
(K) P
C
(bar) T
B
(K)
CO
2
H
2
OMEA 123.11 845.75 61.244 1.699 659.27
CO
2
H
2
O
MDEA
181.19 880.41 42.579 1.991 714.24
H
2
SH
2
OMEA 113.18 758.39 60.183 1.154 560.55
H
2
SH
2
OMDEA 171.26 794.1 42.214 1.630 628.27
Industrial & Engineering Chemistry Research Article
dx.doi.org/10.1021/ie302507n | Ind. Eng. Chem. Res. 2013, 52, 70747089 7076


= =

Z Z W Z Z
Z Z
F Z i n
min
1
2
( ) ( )
{ , , ..., }
s.t.
( , ) 0 ( 1 )
i
n
i i
i
i i
nE
i i
E T E
1
E
E
(10)
It can be proved
16
that the best estimator of fundamental
variance (
E
2
) in this problem is given by

S
n n
Z Z W Z Z
1
( ) ( )
i
n
i i
n
i i
i
i i
E
2
R
2
E
F
E
E T E
(11)
where W
i
is a known weighting (diagonal) matrix
16
for variables
of run i belonging to an extract with n
E
isothermal runs. Table 2
presents results for the estimated four ChE constants in eq 1 at
temperatures of 40, 60, 80, and 100 C, totaling 16 estimated
parameters by means of four isothermal maximum likelihood
searches. Figure 1 depicts objects belonging to the parameter
estimation of ChE constants in eq 1 at 40 Cusing 230 runs from
the literature cited in de Medeiros et al.
16
Figure 1a depicts a
logarithm plot of predicted versus observed loadings and partial
pressures of CO
2
and H
2
S, with good coalescence on the
diagonal. Figure 1b depicts a 3D projection of the 99%
probability condence hyper-ellipsoid for the correct triad
K
CO
2
MEA
, K
CO
2
MDEA
, K
H
2
SMEA
expressed as percent deviations
(%K
CO
2
MEA
%K
CO
2
MDEA
%K
H
2
SMEA
) from the estimated
values, showing that correct ChE constants dier less than 15%
from estimated ones. Figure 1 panels c and 1d, respectively,
present predicted and observed CO
2
loadings and CO
2
partial
pressures (included limits of 3 standard deviations and 99%
condence) versus run number, showing also reasonable
agreement between predictions and observations.
The four estimated ChE constants for the reactions in eq 1, ln
K
k
EST
(k = 1, ..., 4), depicted in Table 2, were tted by three
parameter formulas in terms of absolute temperature as shown in
Table 3. The strong exothermic absorption of CO
2
/H
2
S in
aqueous alkanolamines is coherently reproduced by the RVLE
model. As shown in Figure 2a for the CO
2
MEA reaction and in
Figure 2b for CO
2
MDEAreaction, the estimated (Table 2) and
regressed (Figure 2 and Table 3) ChE constants monotonously
decrease with temperature implying negative standard enthalpies
Table 2. Summary of Parameter Estimation of ChE Constants
in eq 1
T = 40 C T = 60 C T = 80 C T = 100 C
no. expt (n
E
) 230 90 87 140
no. variables (27 n
E
) 6210 2430 2349 3780
no. constraints (20 n
E
) 4600 1800 1740 2800
estimated ChE constants in eq 1
K
CO2MEA
(K
1
) 1313.48 55.712 10.622 1.552
K
CO2MDEA
(K
2
) 708299.1 8345.0 57.263 4.18
K
H2SMEA
(K
3
) 4999.7 155.53 10.025 1.241
K
H2SMDEA
(K
4
) 875532.0 7241.7 245.34 19.77
estimator of fundamental variance in eq 11
S
R
2
4.81 11.37 13.11 6.15
Figure 1. Estimation of ChE constants at T = 40 C: (a) predicted vs
observed loadings (mol/mol), and partial pressures (bar) of CO
2
and
H
2
S; (b) 99% condence ellipsoid for correct values in %K
CO
2
MEA
, %
K
CO
2
MDEA
, %K
H
2
SMEA
; (c) predicted and observed CO
2
loading (mol/
mol); (d) predicted and observed CO
2
partial pressure (bar) [with limits
of 3 standard deviations and 99% condence].
Industrial & Engineering Chemistry Research Article
dx.doi.org/10.1021/ie302507n | Ind. Eng. Chem. Res. 2013, 52, 70747089 7077
of reaction (H
0
), since d ln K/dT = H
0
/(RT
2
) < 0. This
behavior, valid for all reactions in eq 1, is a prerequisite for
consistency of the RVLE model. The temperature dependence of
ChE constants in Table 3 can be further processed
16
for
conversion of the standard state of complexes from(liq) to (g) in
order to get ideal gas properties of formation at T
0
= 298.15 K
(e.g., G
f
0,(g)
, H
f
0,(g)
) and ideal gas heat capacity (C
P
0,(g)
(T) = + T
+ T
2
). These properties (not shown here, see de Medeiros et
al.
16
) are vital to access ideal gas enthalpy of complex species,
which when complemented by residual enthalpy from EOS,
allow us to correctly address heat eects and energy balances in
AGWA operations.
3. MODELING OF PARALLEL FLOW GLC WITH
HOLLOW FIBER MEMBRANE
Figure 3 brings two sketchesboth aligned with axial coordinate
z for GLC modeling with HFM. Figure 3a depicts the spatial
allocation of ows with respect to the HFM, showing (i) two-
phase ow inside HFM for the RVLE permeate (L); (ii) trans-
membrane uxes (N); and (iii) parallel compressible gas ow of
retentate (V). Figure 3b sketches a parallel GLC (resembling a
shell and tube exchanger) with the bundle of HFMs axially
aligned in the shell and xed by perforated plates. The parallel
ows greatly facilitate the mathematics making unnecessary BVP
strategies (e.g., nite dierences) or shooting methods. Indexes k
= 1 ..., n and j = 1, ..., n
C
point to real and complex species.
Subscripts L, V designate permeate and retentate; whereas
Superscripts L
L
, L
V
designate liquid and vapor phases in the
permeate L. Since complex species only exist in the permeate
after some course of reactions, the concept of equivalent moles
Table 3. Regressed ChE Constants vs T (K) (ln K
k
= A
k
+ B
k
/T
+ C
k
ln T)
complex k A
k
B
k
C
k
CO
2
H
2
OMEA 1 800.3318 51085.431 112.1179
CO
2
H
2
OMDEA 2 857.6953 63723.504 116.208
H
2
SH
2
OMEA 3 779.3461 52941.595 107.680
H
2
SH
2
OMDEA 4 1511.997 93647.363 213.448
Figure 2. Regressions of estimated ChE constants vs T (K): (a) ln
K
CO
2
MEA
= 800.332 + 51085.43/T + 112.118 ln T; (b) ln K
CO
2
MDEA
=
857.695 + 63723.504/T + 116.208 ln T [est, estimated ChE constant].
Figure 3. HFMGLCmodeling (z is axial position, is inclination): (a)
trans-membrane uxes, RVLE permeate, and retentate ows relative to
HFM; (b) HFMGLC module.
Industrial & Engineering Chemistry Research Article
dx.doi.org/10.1021/ie302507n | Ind. Eng. Chem. Res. 2013, 52, 70747089 7078
without reaction (EMWR) will be invoked for real species: Let L
the vector of EMWR rates (mol/s) of real species that have been
introduced into the permeate up to the axial position z assuming
that no reaction has occurred (Figure 3a). The concept of
EMWR mols was also used in RVLE experiments in section 2, eq
3. EMWR is granted by Duhems Theorem, in the sense that if
two RVLE problems have the same specication of EMWR rates
of real species, with two more equal coordinates (e.g., T, P), they
will have the same RVLE state. V and N are also vectors of real
species designating, respectively, retentate species rates (mol/s)
and HFM species uxes (mol/sm
2
). Vector designates n
C
complex forming reaction rates (mol/s). Y, X, X
C
designate mol
fractions of real species in the vapor and liquid permeate phases
and of complexes in this liquid. T
L
, P
L
, T
V
, and P
V
are
temperatures (K) and pressures (bar) of L and V, whereas
L
,

V
designate rates of enthalpy (kW) carried by L and V. EMWR
allows permeate species balances to be written only for real
species, with the RVLE resolution done a posteriori. By applying
ChE + VLE onto an EMWRspecication of real species (L), with
two more specications (e.g., T
L
, P
L
), Duhems Theoremleads to
the entire set of RVLE permeate variables (L, L
L
, L
V
, Y, X, X
C
, T
L
,
P
L
,
L
).
3.1. RVLE Model for Reactive VaporLiquid Permeate.
On the basis of Figure 3a and Duhems Theorem, two
implementations of a RVLE permeate were developed to deal
with the algebraic part of the GLC model; namely, RVLE-T and
RVLE-H. Both solve a RVLE permeate: RVLE-T with
specications L, T
L
, P
L
, whereas RVLE-H uses specications L,

L
, P
L
; that is, enthalpy rate replaces temperature as a Duhem
specication. This is expressed in eqs 12 and 13:
=

T P L k n L L Y X X , , ( 1, ..., ) , , , , , ,
k
RVLE T
L L L L V C (12)
=

P L k n L L Y X X T , , ( 1, ..., ) , , , , , ,
k
RVLE
L L L
H
L V C (13)
3.1.1. RVLE-T Implementation. The vector of n + 2 Duhem
RVLE-T specications is U
T
= [P
L
T
L
L
T
]. The 2n + 2n
C
+ 2
RVLE-T state variables include Y, X , X
C
,

, L
L
, L
V
and the set of
2n + 2n
C
+ 2 RVLE-T constraints comprises real and complex
mass balances (eqs 14a, 14b), normalizations (eqs 14c, 14d),
VLE (eqs 14e and ChE 14f):
+

= L X L Y L 0
L V (14a)


= L X I 0
L C (14b)
+ = X X 1 1 1 0
T T
C
(14c)
= Y 1 1 0
T
(14d)

+

= Y X ln ln ln ln 0
L L
V L
(14e)
+ +

= X K X P ln ln ln ln 0
C
T T
L
L
L
(14f)
After replacing mol fractions by unbounded variables (Y =
exp(
Y
), X = exp(
X
), X
C
= exp(
C
)), eqs 15a and 15b express
the working vectors of 2n + 2n
C
+ 2 RVLE-T state variables and
2n + 2n
C
+ 2 RVLE-T constraints. Equation 15b can be
numerically solved if U is known.
=

E L L [ ]
X Y
T T T
C
T T
L V (15a)
= F E U ( , ) 0 (15b)
3.1.2. RVLE-H Implementation. The vector of n + 2 Duhem
RVLE-H specications is U
T
= [P
L

L
L
T
]. The 2n + 2n
C
+ 3
RVLE-H variables are Y, X , X
C
,

, L
L
, L
V
, T
L
and the set of 2n +
2n
C
+ 3 RVLE-H constraints comprises the same eqs 14a to 14f
with the addition of the energy constraint for RVLE permeate
(eq 16):
+ = L H L H 0
L L L V L
L V
(16)
After the same transformation of mol fractions to unbounded
variables above, eqs (17) express the working vectors of 2n + 2n
C
+ 3 RVLE-H state variables and 2n + 2n
C
+ 3 RVLE-H
constraints. Equation 17b can be numerically solved if vector Uis
known.
=

E L L T [ ]
X Y
T T T
C
T T
L V L (17a)
= F E U ( , ) 0 (17b)
3.1.3. Numerical Solution of RVLE-H and RVLE-T. Since
RVLE-T and RVLE-H are reactive versions of ash problems,
only the RVLE-H resolution is detailed here. The Newton
Raphson method (NRM) with analytical jacobians is used.
Iterations normally start from a previous solved state (E *, U *)
seeking for a new state E at a new specication U . First an initial
estimate is created with eq 18a; then NMR iterations proceed
until convergence via eq 18b. Jacobians J
E/U
, J
E
, calculated at
E
(n)
, express the inuence of Uon E and the inuence of E on the
RVLE constraints (eqs 17b), and are described in Appendix Afor
RVLE-H (see Supporting Information).
= * + * E E J U U ( )
(0)
E/U (18a)

=
|| ||
+
+
E E J F E U
E E
[ ] ( , )
{until
n n n
n n
( 1) ( )
E
1 ( )
( 1) ( )
(18b)
3.1.4. Inuence Terms via Dierential Coecients from
Jacobian Terms. Inuence terms, under the form of RVLE
dierential coecients, can be extracted from the jacobians at a
RVLE solution. These terms are RVLE rst order properties that
can be used as measures of the inuence of specications (U) on
the RVLE state (E). Several examples of such coecients are
derived in Appendix Bfor RVLE-Hand RVLE-T(see Supporting
Information). As an informal and clearer representation, symbols
of variables replace the respective index ranges of J
E/U
in the
RHS of eqs (19):

T
J T ( , )
P L
L
L
,
E/U
L L
L
(19a)

J ( , )
P L
L
,
E/U
L
L
(19b)

L
J L ( , )
P L
L
L
,
E/U
L L
L
(19c)

X
X J [diag( )] ( , )
P L
X
L
,
E/U
L
L
(19d)
Industrial & Engineering Chemistry Research Article
dx.doi.org/10.1021/ie302507n | Ind. Eng. Chem. Res. 2013, 52, 70747089 7079

Y
Y J [diag( )] ( , )
P L
Y
L
,
E/U
L
L
(19e)
3.1.5. Example 1: RVLE-T and RVLE-H Loci for Reactive VLE
Permeate. A RVLE system with nine real species was created by
mixing 14 mol/s of an AGWA solvent (2 mol/s MEA, 2 mol/s
MDEA, 10 mol/s H
2
O) with 12.006 mol/s of NG (10
3
mol/s
C
2
H
6
, 10
3
mol/s C
3
H
8
, 2.10
3
mol/s C
4
H
10
, 2.10
3
mol/s
C
5
H
12
, 10 mol/s CH
4
, 2 mol/s CO
2
) so that the corresponding
vector L of EMWR species rates is L
T
= [2 2 10
3
, 10
3
, 0.002,
0.002, 10, 2, 10] (MEA, MDEA, C
2
H
6
, C
3
H
8
, C
4
H
10
, C
5
H
12
,
CH
4
, CO
2
, H
2
O). Without H
2
S, there are only two active
chemical reactions in this system, namely eqs (1a) and (1b),
producing complexes CO
2
H
2
OMEA and CO
2
H
2
O
MDEA with ChE constants given as functions of temperature
in Table 3; that is, n
C
= 2 and the stoichiometric matrix in eqs
Figure 4. Example 1: RVLE-T and RVLE-H loci: (a) Y
CO
2
vs (T, P); (b) Loading
CO
2
(mol/mol) vs (T, P); (c) L
L
(mol/s) vs (T,P); (d) (HT)
P,L
(kJ/
molK) vs (T, P), (e) Y
CO
2
vs (
L
, P); (f) Loading
CO
2
(mol/mol) vs (
L
, P); (g) L
L
(mol/s) vs (
L
, P); (h) (T/
L
)
P,L
(K/kW) vs (
L
, P) [
L
(kW), P
(bar), T (C)].
Industrial & Engineering Chemistry Research Article
dx.doi.org/10.1021/ie302507n | Ind. Eng. Chem. Res. 2013, 52, 70747089 7080
(14) should be understood with only the two rst columns of eq
2. Properties of formation of complexes in the ideal gas state (g)
were recovered from data in Table 3 as observed in section 2 (de
Medeiros et al.
16
). Enthalpy is calculated with reference to
elemental substances in standard states at 298.15 Kand 1 bar. PR
EOS was used for thermodynamic properties with common
binary parameters.
18,19
An initial RVLE state is found as a RVLE-
T solution at T
L
= 320 K, P
L
= 1 bar giving 52.71% mol vapor
phase. Excursions were conducted fromthis initial state exploring
RVLE-T and RVLE-H in 2D domains of specications. Figure 4
depicts four views of RVLE-T excursions and another four views
of RVLE-H excursions with the same reactive mixture
aforementioned with 26.006 mol/s EMWR. Figure 4 panels a
d depict 2D behaviors, generated with RVLE-T excursions in the
domain T[20 C, 100 C], P [1 bar, 20 bar], respectively, for
equilibrium mol fraction of CO
2
in vapor phase (Y
CO
2
), CO
2
loading (mol/mol) in liquid phase (Loading
CO
2
), total mol rate
(mol/s) of liquid (L
L
) and molar isobaric RVLE (two-phase and
reactive) heat capacity H T ( / )
P L ,
(kJ/molK). The best zones
for CO
2
absorption are clearly identied in Figure 4a,b as high
pressure and low temperature sectors, whereas the best zones for
CO
2
stripping are identied with the breakage of complexes at
low pressures and high temperatures. The zones of high liquid
content (L
L
) are identied in Figure 4c at high pressures and
moderately high temperatures, which combine reduced vapor-
ization of liquids with the breakage of complexes creating more
liquid (Eqs. 1a,b), whereas, liquid is destroyed at high
temperatures and low pressures. Figure 4d interestingly reveals
that enthalpy changes more rapidly at the borders of the
absorption zones; that is, just where the breakage of complexes
and reduction of loading initiates. Figure 4 panels e, f, g, and h
depict 2D behaviors, generated with RVLE-H excursions in the
domain
L
[5950 kW, 5290 kW], P [1 bar, 20 bar],
respectively for vapor mol fraction of CO
2
(Y
CO
2
), CO
2
loading
(mol/mol), total molar rate (mol/s) of liquid (L
L
) and the
isobaric derivative of RVLE temperature with enthalpy rate (T/

L
)
P,L
(K/kW). The inuence of enthalpy rate in the RVLE is
similar to the temperature inuence, but with distortions. Thus,
the best zones for CO
2
absorption are identied in Figure 4e,f at
high pressure and low enthalpy rates, whereas the best zones for
CO
2
stripping are identied with the breakage of complexes at
low pressures and high enthalpy rates. The zones with highest
liquid rate (L
L
) are identied in Figure.4g at moderate enthalpy
rates, whereas liquid disappears at high enthalpy rates and lower
pressures. Figure 4h is also interesting, revealing that temper-
ature changes more rapidly with enthalpy rate in the intermediate
region between absorption and stripping zones, that is, where the
breakage of complexes and loading reductions initiate more
vigorously.
3.2. HFM-Contactor Model with Reactive Vapor
Liquid Permeate. Figures 3a and 3b sketch a HFMGLC
with inclination and parallel ows of gas retentate and RVLE
permeate. RVLE-T and/or RVLE-H solvers are necessary to
access the permeate RVLE state corresponding to the dependent
variables, which comprise: retentate temperature, pressure, and
EMWR rates of real species (T
V
, P
V
, V
1
, ..., V
n
); and permeate
temperature, pressure, and EMWR rates of real species (T
L
, P
L
,
L
1
, ..., L
n
). The choice of EMWR rates of real species implies that
conservation principles must be written only for real species in
retentate and permeate in EMWR mode. In the permeate, the
EMWR rates serve, jointly with T
L
, P
L
, as specications U
T
= [P
L
,
T
L
, L
1
, ..., L
n
] for a RVLE-T resolution to access the RVLE state
variables inside the HFM, namely, L
L
, L
V
, Y, X , X
C
,

. Although
the GLC model uses only EMWR dependent variables, the
RVLE-T search is necessary to access thermodynamic properties
of RVLE permeate, like fugacities of real and complex species f

k
L
(k = 1, ..., n), f

j
L
(j = 1, ..., n
C
), enthalpy rate
L
, RVLE heat
capacity C
P
L
= (H
L
/T
L
)
P
L
,L
, density
L
= P
L
M
L
/(Z
L
RT
L
),
RVLE isothermal compressibility
P
L
= (
L
/P
L
)
T
L
,L
, RVLE
isobaric expansivity
T
L
= (
L
/T
L
)
P
L
,L
and RVLE composi-
tional expansivity
L
k
= (
L
/L
k
))
T
L
, P
L
, L
ik
. An analogous set of
properties are calculated for the retentate, but now via a direct
application of EOS with T
V
, P
V
, V
1
, ..., V
n
, leading to fugacities of
real species f

k
V
(k = 1, ..., n), enthalpy rate
V
, heat capacity C
P
V
=
(H
L
/T
V
)
P
V
,V
, density
V
= P
V
M
V
/(Z
V
RT
V
), isothermal
compressibility
P
V
= (
V
/P
V
)
T
V
,V
, isobaric expansivity
T
V
=
(
V
/T
V
)
P
V
,V
and compositional expansivity
V
k
= (
V
/
V
k
)
T
V
, P
V
, V
ik
. The modeling of HFMGLC uses the following
premises: (i) steady state; (ii) 1D axial coordinate z (m) for shell
and HFM ows; (iii) 1D parallel compressible plug ows for
retentate (gas phase) and permeate (two-phase) including RVLE
eects, heat transfer terms, shear terms, and compressibility
(monophasic or reactive biphasic) terms; (iv) permeate
properties in RVLE context; (v) thermodynamic properties of
all phases via cubic EOS (PR/SRK); (vi) high pressure gas
viscosity via ChungReichenbergWilke
19
and liquid viscosity
via mixing rules;
19
(vii) real species CO
2
, CH
4
, etc., allowed to
pass through HFM with uxes given as products of equivalent
permeancies (
k
) with dierences of fugacities on both sides;
and (viii) 1D mass, energy, and momentum balances for
permeate and retentate ows. GLC specications and physical
parameters for simulation are (i) initial value of dependent
variables z = 0: P
V
(0)
, T
V
(0)
, P
L
(0)
, T
L
(0)
, L
k
(0)
, V
k
(0)
(k = 1, ..., n); (ii)
permeancies of real species
k
; (iii) heat transfer parameters T
E
,
,
E
; (iv) battery parameters D, Z
C
, , N
M
; (v) roughness of
surfaces
L
,
V
; and (vi) HFM parameters d, d
o
, Z
HF
, N
HF
.
3.2.1. Spatial Dependence of Densities. A basic step to
develop a thermodynamically sound GLC model is to correctly
express the spatial dependences of retentate and RVLE permeate
densities (
V
,
L
). First, dierential forms of
V
,
L
on dependent
variables are written in EMWR context:

T
T
P
P
V
V
d d d
d
P V T V
k
n
k
P T V
k
V
V
V
,
V
V
V
,
V
V
, ,
i k
V V
V V (20a)

T
T
P
P
L
L
d d d
d
L
P L T L
k
n
k
P T L
k
L
L
,
L
L
L
,
L
L
, ,
i k
L L
L L (20b)
With eqs (20) and above denitions of dierential coecients of

V
,
L
, it is straightforward to write total derivatives for
V
,
L
with respect to the independent axial coordinate z according to

= + +
z
T
z
P
z
V
z
d
d
d
d
d
d
d
d
T P
k
n
V
k V V V
k V V
(21a)
Industrial & Engineering Chemistry Research Article
dx.doi.org/10.1021/ie302507n | Ind. Eng. Chem. Res. 2013, 52, 70747089 7081

= + +
z
T
z
P
z
L
z
d
d
d
d
d
d
d
d
T P
k
n
L
k L L L
k L L
(21b)
Equations (21) are valid even for RVLE, provided L
1
, ..., L
n
are
EMWR interpreted, and are extensively used in retentate and
permeate balances. Retentate coecients in eq 21a are given
analytically via EOS. RVLE permeate coecients in eq 21b use
analytical dierentiation via EOS and J
E/U
, the jacobian of E
regarding U (Appendices A and B in Supporting Information).
3.2.2. Mass Flow Rates and Mass Flux. Due to invariance of
mass in chemical reactions, mass ow rates (kg/s) are invariant
whether expressed in EMWR or not. Thus retentate (q
V
) and
permeate (q
L
) mass ow rates are expressed using only the
simpler EMWR formulas in eqs 22:
= = q M V q M L ,
k
n
k k
k
n
k k
V L
(22)
whence,
= =
q
z
M
V
z
q
z
M
L
z
d
d
d
d
,
d
d
d
d
k
n
k
k
k
n
k
k V L
(23)
Analogously, the total trans-membrane mass ux is written as
= q M N
k
n
k k
(24)
3.2.3. Velocities and Shear Terms. Hydrodynamic terms in
permeate and retentate ows are addressed. Velocities and ow
cross sections are rst given by eqs (25):
= = q S S N d /( ), /4
L
L L
L L HF
2
(25a)
= = q S S S N d /( ), /4
V
V V
V V HF o
2
(25b)
Then Reynolds Numbers, ow perimeters and hydraulic
diameters follow by eqs (26):

= = = e
q
dN D S
4
, , 4 /
L
L
L
L
L HF L L L


(26a)

= = + = e
q
D d N D S
4
, , 4 /
V
V
V
V
V o HF V V V


(26b)
Friction factors and shear stresses are given, respectively, by
Churchill
20
and Darcy formulas:
= = f f e D f ( , / ), /8
L L
L L L L
L L
L
2

(27a)
= = f f e D f ( , / ), /8
V V
V V V V
V V
v
2

(27b)
Churchill
20
factor, originally for gas or liquid, is used for RVLE
permeate (eq 27a) by a conservative averaged two-phase
viscosity with
2
= L
V
2
/(L
V
+ L
L
)
2
the squared RVLE vapor
fraction:
= + T P X X T P Y (1 ) ( , , , ) ( , , )
L
2
LL
L L C
2
LV
L L
(28)
3.2.4. Thermodynamic Properties of Retentate and RVLE
Permeate. Momentum and energy balances require O(1) and
O(2) thermodynamic properties for retentate and RVLE
permeate. The RVLE permeate uses EMWR-dependent
variables, thus thermodynamics must also operate in EMWR.
A key concept is partial molar EMWR property (PMP
EMWR
), an
extension of the standard partial molar property (PMP) for
RVLE. For retentate, PMP and PMP
EMWR
are exactly the same;
they only dier for RVLE permeate, where chemical changes
occur via RVLE-T. Appendix C (see Supporting Information)
addresses eq (C8) for PMP
EMWR
using RVLE-T state E, matrix
J
E/U
and analytical EOS gradients of properties for RVLE phases.
Formulas below use strict SI units (pressure, Pa; energy, Pam
3
/
mol; density, kg/m
3
; molar mass, kg/mol) with index k referring
to real species.
3.2.4.1. Retentate Properties. Given by EOS using eqs (29)
on dependent variables [P
V,
T
V
, V
1,
..., V
n
]. PMP energy (eq 29c)
is the sum of PMP enthalpy with kinetic and potential molar
terms.
=
= H H T P V V H ( , , ), ( )
k
n
k V V V V V V
(29a)
=

C
H
T
H
V
,
P V
k
k
T P V
P
V V
V
,
V V
, ,
i k V V V (29b)

= + + E H M M g h z
2
( )
k k k k
V V V
2
(29c)
= T P V ( , , )
V V
V V (29d)

T P
V
, ,
T
P V
P
T V
V
V
k
T P V
V
V
,
V
V
,
, ,
k
i k
V
V
V
V
V V (29e)
3.2.4.2. Permeate Properties. RVLE-T is rst solved at U
T
=
[P
L
, T
L
, L
1,
..., L
n
] with real species EMWR rates, giving X, X
C
, Y,
, L
L
, L
V
. RVLE enthalpy, density, enthalpy rate, and molar
masses of RVLE phases are then calculated via eqs 30a30d.
PMP
EMWR
enthalpies H
k
L,EMWR
are given by eq (C8) in eq 30e,
and then used in PMP
EMWR
energies via eq 30f. The informal
representation (Section 3.1.4 and Appendix B in Supporting
Information) is used to access subelds of J
E/U
in eqs 30g30j.
=
+

+
H L H T P Y L H T P X X
L L
( ( , , ) ( , , , ))
/( )
L V LV L L L LL L L C
V L
(30a)

q
L M
T P Y
L M
T P X X
/
( , , ) ( , , , )
L L
V LV
LV
L L
L LL
LL
L L C
(30b)
=
+
L H T P Y L H T P X X ( , , ) ( , , , )
L V LV L L L LL L L C
(30c)
= = + M Y M M X M X M ,
k
n
k k
k
n
k k
j
nc
j j LV LL C
(30d)
=

H
L
k
k
T P L
L,EMWR L
, ,
i k L L (30e)

= + + E H M M g h z
2
( )
k k k k
L,EMWR L,EMWR L
2
(30f)
Industrial & Engineering Chemistry Research Article
dx.doi.org/10.1021/ie302507n | Ind. Eng. Chem. Res. 2013, 52, 70747089 7082
=

C
H
T
H
T
H J T ( ) (: , )
P
P L P E
L L
L
,
L
L
,
E L
T
E/U
L
L L
(30g)

=

T T
J T ( ) (: , )
T
P L P E
L
L
,
L
L
,
E
L
T
E/U
L
L
L L
(30h)

=

P P
J P ( ) (: , )
P
T L T E
L
L
,
L
L
,
E
L
T
E/U
L
L
L L
(30i)

L
J L ( ) (: , )
k
T P L
k L
L
, ,
E
L
T
E/U
k
i k L L (30j)
3.2.5. Trans-Membrane Fluxes of Real Species. Real species
uxes are given by species equivalent permeancies times the
respective fugacity dierences across HFM:
=



N f f ( )
k k
k k
V L
(31)
3.2.6. HFMGLC Model Equations. The GLC model
comprises real species (k = 1, ..., n) EMWR mass balances and
momentum/energy balances along the axial direction, written for
retentate and RVLE permeate with the terms discussed from
sections 3.2.1 to 3.2.5.
3.2.6.1. Real Species EMWR Mass Balances for Retentate
and Permeate.
= =
V
z
SaN
L
z
SaN
d
d
,
d
d
k
k
k
k
(32)
3.2.6.2. Momentum Balances for Retentate and Permeate.



+ +
= +
+

T
z
P
z
V
z
g
S
qSa
D Sa
S
{ }
d
d
{ 1}
d
d
{ }
d
d
sen
k
n
k
T V
2 V
P V
2 V
V V
2
V
V
V
V
V
V V k
(33a)


+ +
= + +

+

T
z
P
z
L
z
g
S
qSa
S
qSa
Sa
S
{ }
d
d
{ 1}
d
d
{ }
d
d
sen
T P
k
n
k
L
2 L
L
2 L
L L
2
L
L
L
L V
L
L
L
k L L
(33b)
3.2.6.3. Energy Balances for Retentate and Permeate.

+ +

= +

C
M
T
z
T P
z
V
z
S
qSa g
D
q
T T
Sa
q
T T
d
d
1
d
d
{ }
d
d
sen ( )
( ))
T
V
T P
k
n
V
k
V
P
V
V
V
2 V
V
V
2 V
V
2
V
V
V
E
V
V
E V
V
V
V L
k
V V V
(34a)

+ +

= +

C
M
T
z
T P
z
L
z
S
qSa g
Sa
q
T T
Sa
q
N E E
d
d
1
d
d
{ }
d
d
sen ( )
( )
T
L
T P
k
n
L
k
k
n
k k k
L
P
L
L
L
2 L
L
L
2 L
L
2
L
L
L
L
L
V L
L
L
V L,EMWR
k
L L L
(34b)
3.3. Numerical Resolution of HFMGLC Model. The set
of 2n + 4 ODEs in eqs 32 to 34 for 2n + 4 variables [T
V
, P
V
, V
1
, ...,
V
n
, T
L
, P
L
, L
1
, ..., L
n
], is an algebraic-dierential system with an
embedded algebraic RVLE-T problem for 2n + 2n
C
+ 2 RVLE E
variables. It was integrated numerically from z = 0 to z = Z
C
via
the IVP gear method for sti ODE keeping the algebraic RVLE-T
always solved for each proposed [T
L
, P
L
, L
1
, ..., L
n
] from the IVP
layer. This strategy was able to simulate GLC in all tested cases,
generating meaningful proles for all retentate and permeate
variables.
4. SIMULATION OF NG PURIFICATION FLOWSHEET
WITH HFMGLC
Figure 5 depicts data pertinent to a GLC process, candidate for
oshore deployment, for high pressure NG purication with a
battery of 40 HFMGLC for CO
2
removal. The NG feed is
labeled GN-CONTACT-1 with (% mol): 1MMNm
3
/d (516.4
mol/s), T = 300 K, P = 50 bar, 73.22% CH
4
, 10.19% CO
2
, 9.09%
C
2
H
6
, 4.25% C
3
H
8
, 1.78% C
4
H
10
, 1.47% C
5
H
12
,
V
= 55.9 kg/m
3
,
Z
V
= 0.823,
V
= 58322 kW, C
P
V
= 0.0523 kJ/(molK). Battery is
fed with solvent mrSOLV3 with (% mol): 17651 kg/h (104.61
mol/s), T = 300 K, P = 5 bar, 20% MEA, 20% MDEA, 60% H
2
O,

L
= 943.2 kg/m
3
, Z
L
= 0.01014,
L
= 33279 kW, C
P
L
= 0.146
kJ/(molK). PR EOS is used with all phases. Figure 5 panels a, b,
and c depict three property diagrams for GN-CONTACT-1,
respectively, C
P
(T, P) (kJ/(molK)), Z(T,P) and H
P
(T, P) (kJ/
mol), with bubble, dew, and critical loci superimposed (T
[150 C, 120 C], P [0 bar, 200 bar]). CO
2
freeze-out is an
issue below 80 C, but was not checked since GLC works at
warm conditions. Figure 5 panels ac depict property surfaces in
terms of color, covering subcooled liquid, supercritical uid and
superheated vapor, with the two-phase dome left empty. Despite
that rst order Z and H (Figure 5b,c) do not denote anything
special in the critical neighborhood, the situation is quite
dierent for second order properties like C
P
, which literally
ames illuminating the supercritical uid region in Figure 5a
due to a O(2) critical transition. Figure 5d describes the
purication owsheet targeting on the nal NG with 3.5% mol
CO
2
, comprising (i) GLC battery (labeled GLC) with 40 HFM
vertical modules detailed in Table 4; (ii) RVLE-H stripper
(MR1) at 1 bar and 4300 kW of duty; (iii) phase separator (S1)
at 1 bar; (iv) RVLE-H makeup mixer, pump, and cooler (MR2)
at 5 bar and 460 kW of duty. GLC permeate and retentate are
labeled with L@ and V@ followed by feed label. Other units
label products similarly.
4.1. Simulation of HFMGLC Unit. Sequential owsheet
calculations initiate with the simulation of the GLC unit (section
3.3) since all its feeds are known. Results for HFMGLC
simulation comprises proles of retentate and RVLE permeate
properties across the axial length Z
C
= 2 m. Several proles are
Industrial & Engineering Chemistry Research Article
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shown in Figures 6 and 7, where the GLClength was divided into
0.5 m segments under distinct background colors for easy
recognition of details. Proles are respectively depicted in Figure
6 panels a and b for EMWR rates (mol/s) of CO
2
and CH
4
in the
retentate and permeate, and in Figure 6 panels c and d for % mol
of CO
2
and CH
4
in retentate and in the two permeate phases.
Figure 6e depicts proles of % recovery of CO
2
and CH
4
. Figure
6f shows proles of % mol of all species in vapor (Y
k
) and liquid
(X
k
, X
Cj
) permeate phases, where liquid mol fractions (X
Cj
) of
complexes CO
2
H
2
OMEA and CO
2
H
2
OMDEA play
central roles. Figure 6f should be analyzed accompanied by the
proles of reaction rates (mol/s) (
1
,
2
) forming CO
2
H
2
O
MEA and CO
2
H
2
OMDEA shown in Figure 6h. By last,
Figure 6g reports proles of molar rates of permeate liquid (L
L
)
and vapor (L
V
), showing that the owrate of liquid stabilizes near
the middle of the unit, whereas the ow of gas increases
monotonously. Figure 6 panels a to h all reveal an euorescent
idiosyncrasy of GLCs which was intentionally seeded in this
owsheet and is also a syndrome of NG purication with
membrane permeators. The point is that separation can be
spoiled by excess of equipment size, that is, by excess of contact
area of HFM. In other words, overdesigned GLC batteries gain
capacity, but severely lose selectivity comparatively to tight
designs. This is more evident in Figure 6b,d, fh, which subtly
report that the majority of favorable separation has occurred by
the middle of the second GLC quarter; that is, the rest of the unit
only serves to spoil separation by allowing CH
4
to trespass into
the permeate with a practically constant ux accompanied by a
decreasing faint ux of CO
2
. This is corroborated by Figure 6b,e,
and g, showing that CH
4
, which has a practically constant and
large driving force (see Figure 7c,d), accesses the permeate under
constant ux, that is, giving linear proles of permeate mol/s rate
(L
CH
4
, Figure 6b), % recovery (Figure 6e), and permeate gas rate
(L
V
, Figure 6g), while CO
2
rapidly loses driving force and is
surpassed by CH
4
in the permeate by the end of the third quarter.
Even worse, the excess of area allows excessive bubbling of CH
4
into the permeate, producing more bubbling via CO
2
stripping as
shown in Figure 6f,h, that is, chemical reactions extensions and
liquid phase complex compositions retrocede. In other words,
CO
2
is converted in the rst GLC quarter to the liquid phase
under the form of complexes; and, after the middle of the second
quarter, is gradually released to the permeate vapor as the
breakage of complexes proceeds via stripping action caused by
CH
4
. Figure 7 panels ae address spatial proles not directly
related to material balances, but also of paramount signicance.
Figure 7a reports the GLCtemperature proles, showing that the
heating of permeate and retentate is under progress as occurs in
AGWAabsorbers. The RVLE AGWAmodel calibrated in section
2 with only VLE data (i.e., no thermal data used) was capable,
thanks to the inexorable consistence of thermodynamics, to
reproduce a reasonable increase of 12 C in the temperature of
GLC products. This heating is created by the exothermal CO
2
Figure 5. Natural gas GN-Contact-1: diagrams with bubble and dewloci
(a) C
P
(kJ/(molK)) vs (T, P), (b) Z vs (T, P), (c) H(kJ/mol) vs (T, P),
(d) owsheet for CO
2
removal with HFMGLC.
Table 4. Parameters of HFMGLC Modules in Figure 5d
object item value item value
GLC /2 rd T
E
27 C
GLC D 0.8 m
E
5 W/(m
2
K)
GLC Z
C
2 m 2 W/(m
2
K)
GLC volume 1.005 m
3
gas feed GN-Contact-1
GLC N
M
40 solvent mrSOLV3
HFM d 0.5 mm
CO2
1.7 10
4
mol/sm
2
bar
HFM d
o
0.502 mm
CH4
5.8 10
6
mol/(sm
2
bar)
HFM N
HF
2.188 10
6

C2H6
10
8
mol/(sm
2
bar)
HFM N
HF
MAX
2.303 10
6

C3H8
10
9
mol/(sm
2
bar)
HFM total area 6901.4 m
2

C4H10
Industrial & Engineering Chemistry Research Article
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absorption into the permeate, and then, via heat transfer across
HFM, it is propagated to the retentate also heating it. Figure 7a
corroborates the oversizing of the GLC battery because the
heating eect ceases by the middle of the second quarter with
maxima in the permeate and retentate temperatures, which then
go slowly down due to reverse absorption caused by CH
4
stripping (endothermic) and cooling to the environment via
external heat transfer. As a consequence of parallel ow and high
contact area, retentate and permeate emerge on the other side
practically at the same temperature. Figure 7a also discards, as
totally unnecessary, dew-point adjustment of the gas feed since,
contrary to membrane permeators, GLC promotes much more
chemical heating than Joule-Thomson cooling via gas expansion
through HFM. Figure 7b tested the consistency of the GLC
model showing that, despite the reversed curvatures of the
proles of retentate and permeate energy rates, their sum is
almost constant, with a very subtle fall due to small loss of energy
via cooling through the external heat transfer. The prole of
retentate energy rate goes up due to the removal of CO
2
which
has a very negative enthalpy of formation, while the permeate
Figure 6. GLCproles (k = 1, ..., n, j = 1, ..., n
C,
L permeate, Vretentate): (a) V
k
(mol/s), (b) L
k
(mol/s), (c) %mol V
k
, (d) %mol L
k
, (e) %recovery,
(f) % mol Y
k
, X
k
, X
Cj
, (g) L
L
, L
V
(mol/s), (h)
1
,
2
(mol/s).
Industrial & Engineering Chemistry Research Article
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prole goes down by the opposed reason. Figure 7 panels c and d
portrait proles of fugacities (bar) in retentate and RVLE
permeate, showing that, as said before, the driving force of CO
2
reaches something near zero by the middle of the unit, whereas
the CH
4
driving force remains almost constant above 30 bar.
Figure 7e presents pressure proles of retentate and permeate,
showing that the correspondent head losses are less than 0.2 bar
both for retentate and permeate. Figure 7 panels f and g are
similar to Figure 6 panels d and f. Finally, Figure 7h corroborates
the previous discussion showing the fall, after the rst quarter, of
the CO
2
/CH
4
selectivity dened as (REC
CO
2
/REC
CH
4
)/(Y
CO
2
V
/
Y
CH
4
V
) where REC
CO
2
and REC
CH
4
are absolute recoveries in
mol/s. The retentate euent leaves the HFMGLC at 38.8 C,
49.85 bar, with 0.83 MMNm
3
/d and with 76.5%CH
4
, 3.5%CO
2
,
11% C
2
H
6
, 5.1% C
3
H
8
, 2.2% C
4
H
10
, and 1.8% C
5
H
12
.
4.2. Simulation of MR1, S1 and MR2 Units. Separator S1
is merely a physical splitter of liquid and vapor phases already in
RVLE as imposed by MR1. MR1 and MR2 are reactive ashes
with specied pressure and heat duty, both solved via RVLE-H
algorithm (section 3.1) after the resolution of GLC. The liquid
Figure 7. GLC proles (k = 1, ..., n, j = 1, ..., n
C,
L permeate, V retentate): (a) T
L
,T
V
(C), (b) energy rate (kW), (c) V fugacities (bar), (d) L
fugacities (bar), (e) P
L
,P
V
(bar), (f) X
k
, X
Cj
, (g) Y
k
, (h) CO
2
/CH
4
selectivity.
Industrial & Engineering Chemistry Research Article
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product of MR2 was considered recycle converged with
mrSOLV3 in the rst trial. MR1 is a reactive, low pressure, one
stage stripper for solvent recovery at 1 bar with a heat duty of
4300 kW, resulting in T = 100.51 C and 78.13% vapor. The
vapor phase of S1 has 3.9% MEA, 33.6% CH
4
, 24.9% CO
2
, and
37.6% H
2
O, whereas its liquid product has 35.4% MEA, 49.5%
MDEA, 14.4% H
2
O, 0.1% CO
2
, 0.02% CH
4
, 0.56% complex
CO
2
H
2
OMEA, and 0.02% complex CO
2
H
2
OMDEA.
MR2 is a makeup mixer and cooler, pumping recomposed
solvent at 5 bar back to the GLC. It is fed with 42.08 mol/s of
liquid from S1 at 100.51 C, makeup streams at 27 C of MEA
and H
2
O, respectively, with 5.84 and 56.67 mol/s, and a cooling
of 460 kW, resulting in a liquid very similar to mrSOLV3 at 27.4
C. Appendix D (see Supporting Information) presents
complementary stream data for units GLC, MR1, S1 and MR2,
and also conveys selected gures in this analysis of GLC
owsheet for NG purication.
5. CONCLUDING REMARKS
This work presents a complete modeling approach focusing on a
gasliquid contactor (GLC) with hollow ber membranes
(HFM) for CO
2
removal from high pressure CO
2
-rich natural
gas (NG). This model comprises (i) an entirely novel
16,17
AGWAequilibrium model, based on the Chemical Theory, using
nonionic complex forming ChE chemical reactions, capable of
reproducing chemical absorption and desorption of CO
2
(and
H
2
S) in aqueous solutions of alkanolamines, from low to high
pressures, which was calibrated in terms of ChE constants with
VLE AGWA data from the literature; (ii) two RVLE numerical
solvers, namely, RVLE-Tand RVLE-H, which are appropriate for
RVLE AGWA problems at high pressure using state specica-
tions, respectively, centered in temperature and enthalpy rate;
(iii) a 1D parallel ows, HFMGLC model assuming two-phase
compressible plug owof RVLE permeate and compressible plug
owof retentate gas, built with 1Dmass, energy, and momentum
balances for retentate and permeate, allowing heat and mass
interfacial transfers, shear and compressibility terms, with all
properties of all phases involved rigorously calculated via
conventional EOS like PR and SRK. The HFMGLC model
has as dependent variables temperature, pressure, and EMWR
rates of real species of retentate and permeate. It is an algebraic-
dierential system which was numerically integrated by an IVP
gear method with numerical resolution of an RVLE-T problem
embedded. This HFMGLC model was able to soundly
reproduce several interesting behaviors inside high capacity,
high pressure contactors, such as (i) strong reactive and phase
change thermal eects, resulting that permeate and retentate
temperatures increase along the GLC length, making totally
unnecessary any kind of pretreatment of the NG feed for dew-
point adjustment or water removal; (ii) intense, fugacity driven,
trans-membrane ux of CO
2
pulled by the ChE interaction with
the solvent and the fugacity driving force between retentate and
permeate, showing high concentration of heat release at the more
intense absorbing zones; (iii) almost invariant trans-membrane
ux of CH
4
due to an extremely inertial, relatively high, driving
force (since CH
4
strongly dominates the NG retentate) with the
consequence that, if GLC is oversized concerning the CO
2
capture target, CH
4
will linearly bubble into the permeate,
despite the vanishing presence of CO
2
in the trans-membrane
ux, entailing loss of valuable CH
4
, selectivity degradation of
CO
2
and CO
2
stripping from the liquid permeate, which
increases the gas fraction in the permeate ow and hinders the
performance of the operation; (iv) equilibrium shifts and reverse
absorption heat eects in the RVLE permeate ow as
consequence of the CH
4
intrusion; (v) accurate prediction of
head losses associated with the compressible ows of retentate
and permeate. The HFMGLC model was used in the
simulation of a small owsheet for CO
2
withdrawal from 1
MMNm
3
/d of a CO
2
-rich NG with an approximately 100%
oversized battery of 40 GLC modules with 6901.4 m
2
each. This
analysis conrmed the expected HFMGLC eects like
temperature increase, inertial dominance of the CH
4
driving
force entailing losses of CH
4
to the permeate, creating stripping
of CO
2
in the permeate due to CH
4
intrusion, and higher losses
of MEA and water during solvent regeneration at 1 bar due to the
high content of light gases in the permeate euent.

ASSOCIATED CONTENT
*S Supporting Information
Appendix A: Jacobian matrices for NewtonRaphson method
on RVLE-H, with eqs (A1), (A2), (A3), (A4), (A5), (A6), (A7),
(A8), (A9). Appendix B: Dierential inuence terms from
Jacobian Terms, with eqs (B1), (B2), (B3), (B4), (B5), (B6),
(B7), (B8), (B9), (B10), (B11), (B12), (B13), (B14), (B15) and
(B16). Appendix C: Derivation of partial molar EMWR
properties, PMP
EMWR
, with eqs (C1), (C2), (C3), (C4), (C5),
(C6), (C7) and (C8). Appendix D: Selected gures, simulation
of GLC Flowsheet for NG Purication [GN-Contact-1]. This
material is available free of charge via the Internet at http://pubs.
acs.org.

AUTHOR INFORMATION
Corresponding Author
*Tel.: +5521 2562-7535. E-mail: jlm@eq.ufrj.br.
Notes
The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
J.L. de Medeiros and O.Q.F. Araujo gratefully acknowledge
CNPq-Brazil for nancial support.

ABBREVIATIONS
AGWA = acid gas, water, alkanolamine
BVP = boundary value problem
ChE = chemical equilibrium
EMWR = equivalent moles without reaction
EOR = enhanced oil recovery
EOS = equation of state
GLC = gasliquid contactor
HFM = hollow ber membrane
IVP = initial value problem
NG = natural gas
NLP = nonlinear programming
NRM = NewtonRaphson method
ODE = ordinary dierential equation
PMP = partial molar property
PMP
EMWR
= partial molar EMWR property
PR = PengRobinson
RHS = right hand side
RVLE = reactive vaporliquid equilibrium
SRK = SoaveRedlichKwong
VLE = vaporliquid equilibrium
1D = one dimensional
2D = two dimensional
Industrial & Engineering Chemistry Research Article
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Nomenclature
a = interfacial area per unit of volume (m
1
) of GLC shell
C
P
L
, C
P
V
= molar heat capacities of permeate (RVLE) and
retentate (gas) (J/mol.K)
diag(.) = diagonal matrix creator operator
d, d
O
= HFM internal and external diameters (m)
D, D
L
, D
V
= shell diameter and hydraulic diameters of
permeate and retentate ows (m)
E = vector of state variables in RVLE-T and RVLE-H
E
k
V,EMWR
, E
k
L,EMWR
= PMP
EMWR
energies of k in retentate and
permeate (J/mol)
f
L
, f
V
= Darcy friction factors in permeate and retentate ows

f
L
L
,

f
L
V
= vectors of real species fugacities in liquid and vapor
RVLE phases (bar)
F(Z , ) = 0 = vector of experiment constraints with correct
variables and parameters
F(E , U ) = 0 = vector of constraints for reactive VLE permeate
in RVLE-T and RVLE-H
g = gravity acceleration (9.81 m/s
2
)
h(z) = elevation at axial position z in the ow (m)
H
L
, H
V
= molar enthalpies of permeate and retentate (J/mol)
H
L
L
, H
L
V
= molar enthalpies of liquid and vapor RVLE phases
(J/mol)
H
k
V,EMWR
, H
k
L,EMWR
= PMP
EMWR
enthalpies of k in retentate and
permeate (J/mol)
I = identity matrix
J
E
, J
U
= Jacobians of RVLE-T or RVLE-H constraints
regarding E and U
J
E/U
= Jacobian of E with respect to U in RVLE-T or RVLE-H
K
k
, K = ChE constant of reaction k and the vector (n
C
1) of
ChE constants
L = vector (n 1) of EMWR rates of real species in RVLE
permeate (mol/s)
L
L
, L
V
= total mol rate of liquid and vapor phases belonging to
permeate (mol/s)
M
k
= molar mass of real species k (kg/mol)
M
L
, M
V
= EMWR molar masses of permeate and retentate
(kg/mol)
M
LV
, M
LL
= molar masses of liquid and vapor phases in the
permeate (kg/mol)
n, n
C
, n
A
, n
S
, n
E
= no. of real and complex species, amines,
solutes, and AGWA experiments
n

, n
Z
, n
F
= no. of parameters, experiment variables, and
experiment constraints
N
HF
, N
HF
MAX
, N
M
= no. of HFMs and its maximal value; no. of
GLC modules in the battery
N
k
= trans-membrane ux of real species k (mol/(sm
2
))
P, P
V
, P
L
= absolute pressure, retentate and permeate absolute
pressures (Pa)
P
S
= vector (n
s
1) of partial pressures of solutes (bar)
q
V
, q
L
, q = mass ow rates of retentate and permeate (kg/s);
HFM mass ux (kg/(m
2
s))
Q , Q
LV
, Q
LL
= molar property Q and molar property Q of
liquid and vapor phases in permeate
Q
k
, Q
k
EMWR
= PMP and PMP
EMWR
Q property for real species k
L,
V
, e
L
, e
V
= ow perimeters and Reynolds numbers of
permeate and retentate (m)
R = ideal gas constant (8.314 Pam
3
/(molK))
S = D
2
/4 = section of GLC shell (m
2
)
S
L
, S
V
, Sa = N
HF
d
O
= sections of permeate and retentate ows
(m
2
); interfacial area per length (m)
S
A
, S
S
= selection matrices of amines (n
A
n) and solutes (n
S

n)
S
R
2
= statistic weighted sum of squares of residues of variables
T, T
E
, T
V
, T
L
= temperature, external temperature, retentate
and permeate temperatures (K)
T
C
, P
C
, , T
B
= critical temperature and pressure, acentric
factor, normal boiling point (K)
X , Y = mol fraction vectors (n 1) of real species in liquid and
vapor RVLE phases
X
C
= vector (n
c
1) of mol fractions of complex species in
liquid RVLE phase
U = specication vector (n + 2 1) of RVLE permeate in
RVLE-T and RVLE-H
V = vector (n 1) of retentate molar rates of real species
(mol/s)
Z, Z
C
, Z
HF
= axial GLC coordinate and lengths of GLC and
HFM (Z
C
= Z
HF
) (m)
Z , Z
E
,

Z = vector of correct, observed and estimated AGWA
experiment variables
Z, Z
L
, Z
V
= compressibility factor, permeate and retentate
compressibility factors
W
i
= diagonal weight matrix of experiment i
Greek Symbols

S
= vector (n
s
1) of solute loadings (mol/mol amine) in
liquid phase
= L
V
/(L
V
+ L
L
) = vapor mol fraction of RVLE permeate

V
,
L
= contact surface roughness for retentate and permeate
ows (m)
,
MIN
= porosity of HFM bed and its minimal value

= rates of reaction extensions in RVLE permeate (mol/s)

k
= equivalent permeancy of species k (mol/(sm
2
bar))

L
L
,

L
V
= fugacity coecients of k in liquid and vapor RVLE
phases

P
L
,
P
V
= isothermal compressibility of RVLE permeate and
retentate (kg/(Pam
3
))

T
L
,
T
V
= isobaric expansivity of RVLE permeate and
retentate (kg/(Km
3
))

L
k
,
V
k
= Species k mol expansivity of RVLE permeate and
retentate (kg.s/(molm
3
))

V
,
L
,
V
,
L
= velocities (m/s) and densities (kg/m
3
) of
retentate and permeate ows

V
,
L
,
LV
,
LL
= dynamic viscosity of retentate, permeate,
vapor, liquid RVLE phases (kg/(ms))
,
E
= internal and external heat transfer coecients (W/
(m
2
K))
= real species stoichiometric matrix (n n
c
) for complex
forming reactions

V
,
L
= shear stress on contact surfaces in retentate and
permeate ows (Pa)

E
2
= fundamental variance in the estimation process

L
,
V
= enthalpy rates in permeate and retentate ows
(kW)
, ,

= inclination of GLC(rd); correct and estimated model


parameters (n

1)

x
,
y
,
c
= unbounded mol fraction variables in RVLE-Tand
RVLE-H

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