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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 (

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

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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

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(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

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= + +

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

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=

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

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)

, ,

parameters (n

1)

x

,

y

,

c

= unbounded mol fraction variables in RVLE-Tand

RVLE-H

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Carbon Dioxide Emitting Industries. Sep. Sci. Technol. 2009, 44, 1273.

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Abdullatif, N.; Ismail, Z. M. Removal of Carbon Dioxide from

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CH

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Gas Mixture Using Hollow Fiber Membrane

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