Beruflich Dokumente
Kultur Dokumente
Department of Chemical Engineering, Hanyang University, Wangsimni-ro 222, Seongdong-gu, Seoul 133-791, Republic of Korea
Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Deajeon 305-343, Republic of Korea
art ic l e i nf o
a b s t r a c t
Article history:
Received 18 February 2015
Received in revised form
6 August 2015
Accepted 10 August 2015
Available online 13 August 2015
Gas separation membranes allow the preferential removal of certain gases from a mixture of gases. If the
separation objective is to obtain high product purity and either high removal efciency or high product
recovery it is often necessary to implement a multi-stage network of membranes. However, in the literature most modelling approaches consider the simulation of single-stage membranes. Hence, the aim
of this study is to identify stable and computationally efcient strategies for simulating complex multistage membrane systems. For this purpose a multi-stage membrane modelling framework is developed
and six different stable solution strategies are evaluated and compared in terms of the computational
effort required to solve the resulting sets of equations. These solution strategies vary according to the
sequence in which the individual membrane models are solved (sequential and simultaneous approaches) and the manner in which those membrane models are initialised. In all these strategies a
NewtonRaphson method is employed to solve the mass balance equations in both single-stage and
multi-stage membrane systems. Comparisons are made using example simulations of 10 different congurations of membranes containing 14 membranes with different numbers of connections and recycle
streams present.
& 2015 Elsevier B.V. All rights reserved.
Keywords:
Multi-stage membranes
Simulation strategy
NewtonRaphson method
Gas separation
1. Introduction
A single-stage membrane used for gas separation will typically
have a single stream of feed gas and two exit streams called the
permeate and retentate as shown in Fig. 1. The permeate stream
contains gases which have passed through the membrane and the
retentate contains any remaining gases from the feed.
For hollow bre membranes there is a choice to be made as to
whether to insert the feed into the bore side (inside the hollow
bre) or the shell side (outside the hollow bre). In either case the
hollow bres will generally be encased in a module containing
multiple bres so that the pressures of both sides of the membrane are contained and pressurised appropriately. Additionally
there are three basic congurations including co-current, countercurrent and cross-ow which vary depending on the direction of
ow, location of the exit streams and the inuence of permeateside mixing.
There have been a number of articles which describe methodology for the simulation of single-stage membranes. The
n
Corresponding author.
E-mail address: jinkukkim@hanyang.ac.kr (J.-K. Kim).
http://dx.doi.org/10.1016/j.memsci.2015.08.023
0376-7388/& 2015 Elsevier B.V. All rights reserved.
459
Permeate outlet
Permeate
Retentate
Feed
Retentate outlet
Fig. 1. Tanks-in-series model representation of a hollow-bre membrane operated in the counter-current conguration.
460
HagenPoiseuille equation.
Dynamic/relaxation-based methods
Sequential -&- repeated use of single-membrane based methods
Simultaneous solution of all membranes
2. Methodology
The modelling equations used here are based on those given by
Katoh et al. [6] and Coker et al. [5]. Hence a (nite difference type)
tanks-in-series model (similar to Katoh et al. [6]) is used here to
represent the two sides of the membrane (see Fig. 1). This can be
used to represent any of the common feed ow patterns (crossow, co-current, counter-current) or any of the less common ow
patterns such as those using a sweep gas stream on the permeate
side. In addition the following assumptions are made:
Assumption 1. Membrane permeances are xed, independent of
temperature, pressure and gas composition.
Assumption 2. The geometry of the hollow bres is unaffected by
high pressures.
Assumption 3. There is no temperature change within the
membranes.
Assumption 4. There is no pressure drop on the feed side of the
hollow bres (shell side).
Assumption 5. The bore side pressure drop is described by the
(1)
(2)
(3)
Cn
Fr, j = Fr, j 1
Specify parameters:
Ji, j, n
(4)
i=1
Cn
Fp, n = Fp, n + 1 +
461
feed
d inner
Ji, j, n
feed
P outlet
feed
d outer
n fibre
(5)
i=1
Eqs. (2) and (3) are ODEs (ordinary differential equations) describing the rate of change of retentate and permeate mole fractions and Eqs. (4) and (5) are algebraic expressions for calculation
of the total gas ow rates Fr and Fp. If the numbers of tanks on each
side of the membrane (Sr and Sp) are not equal then the cross
membrane volume ow rates Ji,j,n should then be added together
appropriately in Eqs. (2)(5) to reect the ow rate of gases passing between adjacent tanks. For example Katoh et al. [6] recommend using a greater number of tanks on the permeate side
for a number of applications. It should also be noted that Eq. (5)
will change depending on the direction of the permeate ow rate.
In addition to the gas ow rates this model also requires
knowledge and calculation of pressures on both sides of the
membrane. Here it is assumed that there is no pressure drop on
the retentate side while the permeate side change in pressure
(from one tank to the next) is calculate based on the HagenPoiseuille relation [5] in Eq. (6).
(6)
Initialise
x , y , F r , F p , Pp
for all tanks
Calculate
Calculate
F r , F p , Pp
dx
dt
dy
dt
and
x = x + dx
dt
y = y + dy
dt
No
Converged?
Yes
Fig. 2. Relaxation-based solution strategy for simulation of gas separation
membranes.
time step.
Alternative more complex relaxation strategies such as that of
Kundu et al. [4] could also be implemented using backward differential methods which simultaneously solve the algebraic
equations while integrating the ODEs. This could increase the
computational efciency but would require the calculation of an
initial point which satises the algebraic equations. However, in
this study the modied explicit Euler method is used because our
goal when using relaxation is to obtain a solution in a simple
manner. Although explicit methods are less stable than implicit
methods small time steps can be used to make this simpler explicit
method more stable and reliable.
2.2. NewtonRaphson solution strategy for single-stage membranes
In order to obtain solutions in a quick and efcient manner we
consider the use of a NewtonRaphson algorithm in order to
462
0=
0=
x , y , F r , F p , Pp
Initialise
(7)
= ( x , y , F r , F p , Pp )
Set
(8)
Cn
0 = Fr, j 1 Fr, j
Ji, j, n
(9)
i=1
Cn
0 = Fp, n + 1 Fp, n +
Specify parameters:
F
feed
feed
d inner
Ji, j, n
P outlet
feed
d outer
n fibre
Q
L
(10)
i=1
(11)
F(Z)
Jac ( Z )
Gaussian elimination
Jac
Update
Z,
-F(Z)
including damping
Z = Z + ( damp
Z )
No
Converged?
Yes
Fig. 3. NewtonRaphson solution strategy for simulation of gas separation
membranes.
4) xi, j = xi, feed , yi, n = xi, feed , Fr, j = Fr, feed, Fp, n = 0 (i = 1, Cn; j = 1,
Sr ; n = 1, Sp )
5) xi, j = xi, feed , yi, n = 0, Fr, j = Fr, feed, Fp, n = Fr, feed (i = 1, Cn; j = 1,
Sr ; n = 1, Sp )
where options 25 are simple initial guesses and options 1 require
a relaxation-based simulation.
To quantify the stability of these different initialisation approaches the maximum allowed damping coefcient (damp, as
shown in Fig. 3) which can be used to converge to a real physical
solution is determined. The use of a smaller damping coefcient in
the NewtonRaphson method (in the range 0 odamp r1 ) allows
for a more stable convergence by reducing the size of the steps
taken. For example this is useful for cases where very high (0.9 4 )
or very low (0.1 o) stage cut ( total permeate outlet ow/total
feed ow) simulations (or any cases involving numerical stiffness)
463
Simultaneous
Simple initialisation
Sequential initialisation
Set Recycle Flow Rates = 0
Steady-state Simulation
of 1st
Membrane
Steady-state Simulation
of 1st Membrane
Steady-state Simulation
of NM th
Membrane
Steady-state Simulation
of NM th
Membrane
No
Converged?
Simultaneous
Steady-state
464
sequence.
A. Direct substitution
B. Wegstein
C. NewtonRaphson
D. Broyden
The four methods considered here include the simple direct
substitution method where the recycle streams are set equal to the
relevant calculated membrane outlets. This method is the most
basic which generally requires large numbers of iterations and so
the other three methods are intended to accelerate convergence
by improving the estimation of these recycle stream conditions
after each sequence of calculations. In the Wegstein method this is
achieved using a simple set of equations which use the values
obtained from previous iterations to improve the estimation of
these unknown recycle stream conditions in subsequent iterations.
Alternatively the NewtonRaphson method can be implemented
for the calculation/convergence of these recycle streams (a nested
approach where the NewtonRaphson method is used twice: for
the solution of single-stage membranes and for the solution of
recycle streams). However, the calculation of the Jacobian for this
NewtonRaphson method requires the calculation of derivatives
using a numerical differences method (not shown in Fig. 4) which
is known to be computationally intensive. For this reason the
Broyden method is also considered which includes a simpler
method for the approximate calculation of the Jacobian allowing
for faster iterations. A description of these methods which are
commonly used in process simulators can be found in the book of
Turton et al. [19].
P2
Membrane 3
Membrane 2
P1
R2
Z 3 = ( x 3 , y3 , Fr 3 , F p 3 , P p 3 )
Z 2 = ( x 2 , y2 , F r 2 , F p 2 , P p 2 )
Membrane 1
R1
Z 1 = ( x 1 , y1 , Fr 1 , F p 1 , P p1 )
Fig. 5. Example of a multi-stage membrane system with three membranes including recycle streams.
Recycle Terms
Membrane 2
465
Recycle Terms
Membrane 1
Membrane 3
Membrane 1
Membrane 1
Derivatives
Z1
F Z1
Membrane 2
Connection Terms
Membrane 1
Z2
Derivatives
F Z2
Membrane 3
Connection Terms
Membrane 2
Membrane 2
Z3
Derivatives
Membrane 3
Jacobian
F Z3
Fig. 6. NewtonRaphson method for simultaneous solution of multi-stage membrane system (in this case using 3 counter-current membranes with recycles).
zero) the connection/recycle terms inside the Jacobian (e.g. see the
connection/recycle terms in Fig. 6).
Hence, two different multi-stage simulation strategies are
recommended:
E. Simultaneous Sequential initialisation
(without damping and including all connection/recycle terms in
the multi-stage Jacobian)
F. Simultaneous Simple initialisation
(with damping and excluding all connection/recycle terms in
the multi-stage Jacobian)
Where strategy E takes advantage of the good initialisation
point provided by the sequential initialisation and hence does not
require any further steps to enhance stability. While Strategy F
starts from a simpler initial point and uses both the stability enhancing modications mentioned above.
Table 1
Parameters used for validation cases.
Number
of bres
Case 1a
20
Case 2b 368
*
a
b
Outer
diameter
(m)
Inner diameter
(m)
Feed
pressure
(kPa)
Permeate
outlet
pressure
(kPa)
0.15
0.25
200
160
80
80*
3528.0
690.0
92.8
100.0
Assumed value.
Pan [1].
Feng et al. [20].
Table 2
Membrane permeance values and feed composition used in validation.
Permeances (GPU)
CH4
C2H6
C3H8
0
0
40.0478
1.8
9.3
0
Feed composition (% volume)
1.1124
0
0.3059
0
0.0596
0
N2
O2
CO2
CH4
C2H6
C3H8
0
79.5
0
20.5
48.5
0
27.9
0
16.26
0
7.34
0
N2
Effective
length
(m)
Case 1a
Case 2b
Case 1
Case 2b
a
b
O2
CO2
Pan [1].
Feng et al. [20].
466
100
100
CO (model)
CO (experiment)
2
98
95
90
85
80
75
96
94
92
90
86
84
70
65
0.35
82
0.4
0.45
0.5
0.55
0.6
0.65
Countercurrent (model)
Countercurrent (experiment)
Cocurrent (model)
Cocurrent (experiment)
88
0.7
0.1
0.2
0.3
0.4
0.5
Stage cut
0.6
80
N2 recovery
20
CH4 (experiment)
C2H6 (model)
C2H6 (experiment)
15
0.9
Countercurrent (model)
Countercurrent (experiment)
Cocurrent (model)
Cocurrent (experiment)
90
25
0.8
100
Stage cut
CH (model)
0.7
70
60
50
40
C H (model)
3 8
30
C H (experiment)
3 8
20
82
84
86
10
88
90
92
94
96
N2 composition of rententate outlet (%vol)
98
100
0.4
0.45
0.5
0.55
0.6
0.65
0.9
0.7
Stage cut
least stable. The most stable initialisation options are two of the
simpler options (2 and 3) which are shown to require little or no
damping allowing the maximum damping coefcient to be used
for a wide range of conditions. However, all methods are shown to
require smaller damping coefcients in order to converge at very
high stage cuts. In principle the initialisation using a solution from
the relaxation method calculated at conditions close to those being
simulated with the NewtonRaphson method should be a very
stable approach. However, it is shown here in Fig. 9 that the initialisation using a single solution from the relaxation method is
less stable at feed conditions with stage cut much higher and
much lower than that used to provide the initialisation. So for
example initialisation option 1 which is calculated here at conditions giving stage cut 0.53 is less stable for much lower and
much higher stage cut simulations. Hence, for this reason and
because the relaxation method requires more computational effort
it is only recommended if convergence issues are found using
options 2 or 3 at some certain feed conditions.
Initialisation option 1
Initialisation option 2
Initialisation option 3
Initialisation option 4
Initialisation option 5
0.8
Maximum damping coefficient
0
0.35
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
Stage cut
0.7
0.8
0.9
467
Fig. 10. Ten congurations used to test multi-stage membrane simulation strategies.
( )
A estimate m2 =
Ffeed N m3 s1
(12)
( )
A estimate m2 =
Ffeed N m3 s1
(13)
468
Q av (GPU) =
Table 3
Membrane areas used for the simulation of 10 different membrane congurations.
i =n 1 Q ixi, feed
C
i =n 1 Q i
(14)
Area (m2)
Memb
Memb
Memb
Memb
Memb
1
2
3
4
5
5.548 106
5.548 105
5.548 105
5.548 104
5.548 104
1.123 107
1.123 106
1.123 106
1.123 105
1.123 105
Jacobian. This is found to be a stable strategy because the sequential initialisation provides a good initialisation.
Alternatively, strategy F uses only a simple initialisation of the
recycle streams which is a relatively poor initial starting point.
Hence this strategy is implemented initially using damping in the
multi-stage NewtonRaphson method and excluding the connection/recycle terms from the Jacobian. As with the single-stage
damping damp is initially set equal to 0.1 and later changed to
1 when the method reaches a certain convergence criteria (norm
(Z*) divided by the number of unknown variables o0.1). After
meeting this criterion the connection/recycle terms are also reinserted into the Jacobian to accelerate convergence. Complete
convergence for the multi-stage simulations (in strategies E and F)
is assumed when norm (Z*) divided by the total number of unknowns in all membranes is less than 1 10 6.
The above strategies (AF) were found to be stable converging
to the same physical solutions for each of the ten congurations.
However, it is worth noting that there are a number of alternatives
strategies which are less stable. In particular it was found that:
Strategy D using a unity matrix as an initial Jacobian (a common practise when using the Broyden method) leads to convergence problems and hence the implementation used here involves the calculation of a Jacobian for the rst step using a numerical difference method.
All strategies using single-membrane NewtonRaphson method failed without damping (i.e. if damp 1 starting from the initial
point).
Also, the multi-stage NewtonRaphson method used in strategy F failed to converge for all cases without damping and for
some cases if the connection/recycle terms in the Jacobian are
included from the start.
Example simulation results are given for conguration 9 in
Fig. 11. These example results show that with this conguration a
very high purity of CO2 is achieved with a ow rate of approximately 10% of the feed.
The resulting CPU times required by each strategy for each of
the 10 congurations are shown in Figs. 12 and 13 for the sequential and simultaneous strategies using the small membranes
case and in Figs. 14 and 15 for the sequential and simultaneous
strategies using the large membranes case. It is clear from these
gures that while the sequential strategies are shown to be fast for
congurations 14 which do not contain any recycles they are an
order of magnitude slower than the simultaneous strategies for
congurations 510.
Considering the different sequential strategies the Wegstein
and Broyden methods are shown to give the best computational
efciencies for these cases. The NewtonRaphson method is slow
here mainly because of the computational effort required for the
calculation of the Jacobian derivatives using numerical differences
which increases the computational effort required, in particular for
cases with multiple recycles. The direct substitution method is also
shown to be relatively slow, due to the large number of iterations
required.
The two simultaneous methods are shown to give relatively
F
x CO
x CH
47
0.9989
0.0011
x C2 H =
6
xC H =
3
Nm s
469
-1
F
x CO
0.0000
x CH
0.0000
x C2 H
100
P2
kPa
xC
0.9711
x CH
0.0245
0.0040
3H 8
0.0003
100
=
=
0.0322
0.0052
3H 8
0.0005
400
-1
kPa
-1
400
x C2 H
xC
Nm s
190
Nm s
0.9621
F
x CO
143
kPa
R2
Membrane 2
P1
kPa
400
0.9536
x CH
0.0394
x C2 H
kPa
P3
xC
R1
x CH
500
0.4850
Nm s
0.2790
0.1626
3H 8
0.0734
400
x C2 H
xC
Nm s
0.0065
3H 8
0.0006
100
-1
kPa
Membrane 3
Feed
F
x CO
14
P
Membrane 1
F
x CO
F
x CO
-1
x CH
Nm s
467
-1
F
x CO
2
4
0.4472
x CH
0.2998
x C2 H
x C2 H =
6
xC H =
3
kPa
R3
0.1743
xC
0.0786
400
453
0.4318
Nm s
0.3078
0.1794
3H 8
0.0810
400
kPa
-1
kPa
Fig. 11. Sample calculation results based on conguration 9 shown in Fig. 10.
104
35
Simultaneous - Sequential initialisation
Simultaneous - Simple initialisation
30
103
102
Sequential - Direct substitution
20
15
10
Sequential - Wegstein
Sequential - Newton-Raphson
101
100
25
Sequential - Broyden
5
6
7
Membrane configuration
10
Fig. 13. Comparison of CPU times required for the simulation of 10 different congurations the small membranes using different simultaneous strategies.
1
5
6
7
Membrane configuration
10
Fig. 12. Comparison of CPU times required for the simulation of 10 different congurations the small membranes using different sequential strategies.
fast convergence for all 10 congurations and for both of the different membrane area cases (large and small). However, it is
shown that the strategy with sequential initialisation method is
faster for most of the congurations with the exception of conguration 6. It is presumed that the simple initialisation approach
is faster only for this conguration because conguration 6 has a
very small recycle ow rate compared to the other congurations.
Hence, the simple initialisation which uses a starting point with
zero ow rate is a good initial point for this conguration (under
the operating conditions used here).
For all other congurations the sequential initialisation approach is shown to give slightly faster convergence for the small
membranes case. Considering the large membranes case (excluding conguration 6) the sequential initialisation is shown to
give signicantly faster convergence for congurations which include one or more recycle streams. Hence, the simultaneous
strategy with sequential initialisation is considered to be the most
computationally efcient approach for use in the design and optimisation of complex multi-stage membrane systems.
470
10 4
10 3
10 2
Sequential - Direct substitution
Sequential - Wegstein
Sequential - Newton-Raphson
Sequential - Broyden
10 1
10 0
10
Membrane configuration
Fig. 14. Comparison of CPU times required for the simulation of 10 different congurations the large membranes using different sequential strategies.
55
50
Simultaneous - Sequential initialisation
Simultaneous - Simple initialisation
45
40
35
30
25
20
15
10
5
Acknowledgements
1
5
6
Membrane configuration
10
Fig. 15. Comparison of CPU times required for the simulation of 10 different congurations the large membranes using different simultaneous strategies.
This work was supported by the Korea CCS R&D Center (KCRC)
grant funded by the Korea government (Ministry of Science, ICT &
Future Planning) (No.2014M1A8A1049338)
Nomenclature
Am
S
t
T
V
xi
yi
Z
Greek characters
n
Pn
Subscripts
i
j
n
p
r
feed
total
outlet
ith component
jth permeate tank
nth retentate tank
permeate
retentate
membrane feed (in the retentate)
total gas ow (considering all the membrane bres
combined)
membrane outlet (in the permeate)
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
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[19]
[20]
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471
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