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<a href=Energy 37 (2012) 417 e 429 Contents lists available at S c i V e r s e S c i e n c e D i r e c t Energy journal homepage: www.els evier.com/locate/energy A real column design exergy optimization of a cryogenic air separation unit J. Rizk * , M. Nemer, D. Clodic Mines ParisTech e Center for Energy and Processes, 5 rue Léon Blum, 91120 Palaiseau, France article info Article history: Received 10 March 2011 Received in revised form 4 August 2011 Accepted 6 November 2011 Available online 12 December 2011 Keywords: Exergy analysis Distillation columns Diabatic process Cryogenic air separation abstract Distillation columns are one of the main methods used for separating air components. Their inconve- nient is their high energy consumption. The distillation process is simulated in three types of columns and the exergy losses in the different parts calculated. A sensitivity analysis is realized in order to optimize the geometric and the operational parameters of each type of column. A comparative exergy analysis between the distillation columns considered for cryogenic air separation shows that the exergy ef fi ciency of a double diabatic column, with heat transfer all through the length of the column, is 23% higher than that of the conventional adiabatic double columns. 2011 Elsevier Ltd. All rights reserved. 1. Introduction Three processes for air separation exist: cryogenic distillation, pressure swing adsorption, and membrane separation. The choice of the process to be used is based on the desired products. Cryo- genic air distillation is used when product high purity is needed. It is also advantageous when products are required in liquid form. The pressure swing adsorption process is used for high nitrogen purity (98 e 99.5 volume percentages). The membrane separation process is used for low fl ows and low purities (less than 98 volume percentage). In this article, we consider the cryogenic distillation process, which is the most widely used process for air separation [1] . In order to separate the air components by a distillation process, a feed stream, containing nitrogen, oxygen, and argon is sent into a distillation column, operating between a heat source (boiler at the bottom) and a cold source (partial condenser at the top), and generating mass transfers between a vapor stream fl owing upward and a liquid stream fl owing downward. This type of column, the simple adiabatic column ( Fig. 1 ), constitutes the conventional distillation column, which is the reference for bench marking new distillation concepts. The conventional distillation process is known to be a major source of energy consumption in the chemical industry. Besides, when separating mixtures with low relative volatilities, such as * Corresponding author. Tel.: þ 33 169194247; fax: þ 33 169194501. E-mail address: joelle.rizk@mines-paristech.fr (J. Rizk). 0360-5442/$ e see front matter 2011 Elsevier Ltd. All rights reserved. doi: 10.1016/j.energy.2011.11.012 nitrogen-oxygen mixtures, higher energy consumption is needed [2] . In order to reduce the energy consumption of distillation columns, many new techniques have been proposed since 1950 [3] . These techniques include essentially thermal coupling between two simple columns, or heat-integrated columns. Thermal coupling between columns consists in two counter- current streams, a liquid stream and a vapor stream, connecting the two columns and exchanging heat between them. Several con fi g- urations of thermal coupling between columns are studied and optimal con fi gurations searched for different cases of feed mixtures. Heat-integrated distillation process consists in adding or removing heat from streams all along their fl ow in the column. Flows are in consequence diabatic, and the duties on the top and bottom heat exchangers are reduced, or even totally removed. In this paper, three con fi gurations of cryogenic distillation columns for air separation are studied: a simple adiabatic column, two thermally coupled adiabatic columns, and a diabatic column. In order to compare the three columns, two different approaches could be considered: an energy analysis based on the fi rst law of thermodynamics and an exergy analysis based on the second law of thermodynamics [4] . An exergy analysis is necessary when various forms of energy are used in a process, because it describes the quality of energy, while energy analysis describes only quantitative aspects. In distillation columns, thermal exergy, at the heat exchanger levels, is converted into chemical exergy, during the component separation of the mixture [5] . An exergy analysis will provide information on the quality of the energy involved in the process " id="pdf-obj-0-7" src="pdf-obj-0-7.jpg">

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<a href=Energy 37 (2012) 417 e 429 Contents lists available at S c i V e r s e S c i e n c e D i r e c t Energy journal homepage: www.els evier.com/locate/energy A real column design exergy optimization of a cryogenic air separation unit J. Rizk * , M. Nemer, D. Clodic Mines ParisTech e Center for Energy and Processes, 5 rue Léon Blum, 91120 Palaiseau, France article info Article history: Received 10 March 2011 Received in revised form 4 August 2011 Accepted 6 November 2011 Available online 12 December 2011 Keywords: Exergy analysis Distillation columns Diabatic process Cryogenic air separation abstract Distillation columns are one of the main methods used for separating air components. Their inconve- nient is their high energy consumption. The distillation process is simulated in three types of columns and the exergy losses in the different parts calculated. A sensitivity analysis is realized in order to optimize the geometric and the operational parameters of each type of column. A comparative exergy analysis between the distillation columns considered for cryogenic air separation shows that the exergy ef fi ciency of a double diabatic column, with heat transfer all through the length of the column, is 23% higher than that of the conventional adiabatic double columns. 2011 Elsevier Ltd. All rights reserved. 1. Introduction Three processes for air separation exist: cryogenic distillation, pressure swing adsorption, and membrane separation. The choice of the process to be used is based on the desired products. Cryo- genic air distillation is used when product high purity is needed. It is also advantageous when products are required in liquid form. The pressure swing adsorption process is used for high nitrogen purity (98 e 99.5 volume percentages). The membrane separation process is used for low fl ows and low purities (less than 98 volume percentage). In this article, we consider the cryogenic distillation process, which is the most widely used process for air separation [1] . In order to separate the air components by a distillation process, a feed stream, containing nitrogen, oxygen, and argon is sent into a distillation column, operating between a heat source (boiler at the bottom) and a cold source (partial condenser at the top), and generating mass transfers between a vapor stream fl owing upward and a liquid stream fl owing downward. This type of column, the simple adiabatic column ( Fig. 1 ), constitutes the conventional distillation column, which is the reference for bench marking new distillation concepts. The conventional distillation process is known to be a major source of energy consumption in the chemical industry. Besides, when separating mixtures with low relative volatilities, such as * Corresponding author. Tel.: þ 33 169194247; fax: þ 33 169194501. E-mail address: joelle.rizk@mines-paristech.fr (J. Rizk). 0360-5442/$ e see front matter 2011 Elsevier Ltd. All rights reserved. doi: 10.1016/j.energy.2011.11.012 nitrogen-oxygen mixtures, higher energy consumption is needed [2] . In order to reduce the energy consumption of distillation columns, many new techniques have been proposed since 1950 [3] . These techniques include essentially thermal coupling between two simple columns, or heat-integrated columns. Thermal coupling between columns consists in two counter- current streams, a liquid stream and a vapor stream, connecting the two columns and exchanging heat between them. Several con fi g- urations of thermal coupling between columns are studied and optimal con fi gurations searched for different cases of feed mixtures. Heat-integrated distillation process consists in adding or removing heat from streams all along their fl ow in the column. Flows are in consequence diabatic, and the duties on the top and bottom heat exchangers are reduced, or even totally removed. In this paper, three con fi gurations of cryogenic distillation columns for air separation are studied: a simple adiabatic column, two thermally coupled adiabatic columns, and a diabatic column. In order to compare the three columns, two different approaches could be considered: an energy analysis based on the fi rst law of thermodynamics and an exergy analysis based on the second law of thermodynamics [4] . An exergy analysis is necessary when various forms of energy are used in a process, because it describes the quality of energy, while energy analysis describes only quantitative aspects. In distillation columns, thermal exergy, at the heat exchanger levels, is converted into chemical exergy, during the component separation of the mixture [5] . An exergy analysis will provide information on the quality of the energy involved in the process " id="pdf-obj-0-38" src="pdf-obj-0-38.jpg">

A real column design exergy optimization of a cryogenic air separation unit

J. Rizk * , M. Nemer, D. Clodic

Mines ParisTech e Center for Energy and Processes, 5 rue Léon Blum, 91120 Palaiseau, France

article info

Article history:

Received 10 March 2011 Received in revised form 4 August 2011 Accepted 6 November 2011 Available online 12 December 2011

Keywords:

Exergy analysis Distillation columns Diabatic process Cryogenic air separation

abstract

Distillation columns are one of the main methods used for separating air components. Their inconve- nient is their high energy consumption. The distillation process is simulated in three types of columns and the exergy losses in the different parts calculated. A sensitivity analysis is realized in order to optimize the geometric and the operational parameters of each type of column. A comparative exergy analysis between the distillation columns considered for cryogenic air separation shows that the exergy efciency of a double diabatic column, with heat transfer all through the length of the column, is 23%

higher than that of the conventional adiabatic double columns.

2011 Elsevier Ltd. All rights reserved.

1. Introduction

Three processes for air separation exist: cryogenic distillation, pressure swing adsorption, and membrane separation. The choice of the process to be used is based on the desired products. Cryo- genic air distillation is used when product high purity is needed. It is also advantageous when products are required in liquid form. The pressure swing adsorption process is used for high nitrogen purity (98 e99.5 volume percentages). The membrane separation process is used for low ows and low purities (less than 98 volume percentage). In this article, we consider the cryogenic distillation process, which is the most widely used process for air separation [1]. In order to separate the air components by a distillation process, a feed stream, containing nitrogen, oxygen, and argon is sent into a distillation column, operating between a heat source (boiler at the bottom) and a cold source (partial condenser at the top), and generating mass transfers between a vapor stream owing upward and a liquid stream owing downward. This type of column, the simple adiabatic column (Fig. 1), constitutes the conventional distillation column, which is the reference for bench marking new distillation concepts. The conventional distillation process is known to be a major source of energy consumption in the chemical industry. Besides, when separating mixtures with low relative volatilities, such as

* Corresponding author. Tel.: þ33 169194247; fax: þ33 169194501. E-mail address: joelle.rizk@mines-paristech.fr (J. Rizk).

0360-5442/$ e see front matter 2011 Elsevier Ltd. All rights reserved.

nitrogen-oxygen mixtures, higher energy consumption is needed [2]. In order to reduce the energy consumption of distillation columns, many new techniques have been proposed since 1950 [3]. These techniques include essentially thermal coupling between two simple columns, or heat-integrated columns. Thermal coupling between columns consists in two counter- current streams, a liquid stream and a vapor stream, connecting the two columns and exchanging heat between them. Several cong- urations of thermal coupling between columns are studied and optimal congurations searched for different cases of feed mixtures. Heat-integrated distillation process consists in adding or removing heat from streams all along their ow in the column. Flows are in consequence diabatic, and the duties on the top and bottom heat exchangers are reduced, or even totally removed. In this paper, three congurations of cryogenic distillation columns for air separation are studied: a simple adiabatic column, two thermally coupled adiabatic columns, and a diabatic column. In order to compare the three columns, two different approaches could be considered: an energy analysis based on the rst law of thermodynamics and an exergy analysis based on the second law of thermodynamics [4]. An exergy analysis is necessary when various forms of energy are used in a process, because it describes the quality of energy, while energy analysis describes only quantitative aspects. In distillation columns, thermal exergy, at the heat exchanger levels, is converted into chemical exergy, during the component separation of the mixture [5]. An exergy analysis will provide information on the quality of the energy involved in the process

418

J. Rizk et al. / Energy 37 (2012) 417e429

418 J. Rizk et al. / Energy 37 (2012) 417 e 429 Fig. 1. Simple adiabatic

Fig. 1. Simple adiabatic column for cryogenic air distillation.

with the location and magnitude of the local exergy losses [4]. Besides, it has been proven that, a distillation process with minimum energy consumption is not necessarily the process with the highest thermodynamic efciency [6]. An exergy analysis is therefore conducted in order to nd the thermodynamic optimum for each conguration considered in this study, dened by its geometric and operating parameters, and to compare their thermodynamic efciencies. The thermodynamic efciency of a distillation column is the ratio of the minimum work required for performing the separa- tion to the effective work required for the separation [6]. The effective work of separation is the sum of the minimum required work and the exergy losses in the system. In order to maximize the thermodynamic ef ciency of distillation schemes, exergy losses are to be minimized, by reducing or eliminating any source of irreversibility in the process. Irreversibility in a conventional distillation scheme occurs in the heat exchangers due to the difference of temperatures between streams, and all through the length of the column due essentially to mass transfers between liquid and vapor ows [7] . Thermally coupled and heat-integrated columns present the advantage of reducing the exergy losses and thus increasing the thermodynamic efciency of the distillation process.

2. Simple adiabatic column

2.1. Simulation of a simple adiabatic column

In order to simulate the distillation process in a simple adiabatic column, an industrial packing (Fig. 2) is considered, with the following characteristics [8]:

Packing surface area a p ¼ 244 m 2 /m 3 . Packing porosity ε ¼ 0.98. Height of the packing element h pe ¼ 0.197 m. Corrugation height h P ¼ 0.012 m. Corrugation base length b P ¼ 0.0225 m. Corrugation side length s P ¼ 0.0165 m. Corrugation angle with the horizontal a ¼ 45 .

The evolution of operating parameters is obtained using a nite volume method. The column is divided into N nite volumes, and the values of the liquid and vapor ow rates, compositions, pres- sures, and temperatures are calculated by resolving the conserva- tion equations on each nite volume. In order to simplify the problem, the feed stream is taken to be a binary mixture of nitrogen and oxygen, with a molar composition of 78.1% of nitrogen and 21.9% of oxygen. Fig. 3 represents a nite volume i, with the different corre- sponding liquid and vapor uxes. On each nite volume, variables to be calculated are those noted in Fig. 3. The main physical phenomenon to be modeled in the distilla- tion column is the mass transfer between the liquid and the vapor. The nitrogen being the more volatile component, it tends to evaporate. The vapor is then enriched with nitrogen while it ows upward (y i > y i 1 ). The oxygen present in the vapor tends to condensate, and the downward liquid ow is enriched with oxygen

(x 0 i > x 0 iþ1 ). Masse ow rates and molar fractions of oxygen and nitrogen are calculated by solving the mass and species conservation equations (Eqs. (1)e(5)). In order to simplify the resolution, it is possible to reduce the number of variables, by adding the two species conservation equations, and using the relation between the mass of nitrogen transferred to the vapor and the mass of oxygen trans- ferred to the liquid (Eq. (6)). Mass conservation:

G i 1 G i þ L iþ1 L i

¼ 0

Nitrogen conservation in liquid:

L iþ1 x iþ1 L i x i

m _ N 2 ¼ 0

Nitrogen conservation in vapor:

G i 1 y i 1 G i y i þ

m _ N 2 ¼ 0

(1)

(2)

(3)

Fig. 1 shows the conventional adiabatic column for air separa- tion. Air in vapor phase is introduced at a feed location F. A nitrogen rich vapor product is collected at the top and an oxygen rich liquid product at the bottom of the column. A heat ow W boil is supplied to the boiler, where a fraction B of the liquid leaving the stage 1 of the column is evaporated and is sent back to the stage. A heat ow W cond is removed from the condenser, where a fraction C of the vapor leaving stage N of the column is condensed and sent back, in liquid form, to stage N. In order to calculate the exergy losses due to mass transfers in the column, the variations of mass ow rates, compositions, temperatures, and pressures of the liquid and the vapor streams have to be known rst. For this aim, the column is rst modeled and its operating parameters calculated. Then the exergy losses are calculated.

418 J. Rizk et al. / Energy 37 (2012) 417 e 429 Fig. 1. Simple adiabatic

Fig. 2. Basic geometry and dimensions of the packing [5].

J. Rizk et al. / Energy 37 (2012) 417e429

419

J. Rizk et al. / Energy 37 (2012) 417 e 429 419 Fig. 3. Liquid and

Fig. 3. Liquid and vapor ow rates in a nite volume i.

Oxygen conservation in liquid:

L iþ1 x iþ1 0 L i x 0

i þ

m _ O 2 ¼ 0

 

Oxygen conservation in vapor:

G i 1 y i 0 1 G i y 0

i

m _ O 2 ¼ 0

 

Relation

between

mass

ows

transferred:

 

_

h fg;N 2

m O 2

¼

m _ N 2

 

h fg;O 2

 

(4)

(5)

of oxygen and

nitrogen

(6)

Adding Eqs. (2) and (3) to Eqs. (4) and (5) respectively, and using Eq.

(6), eliminates the oxygen molar fractions and transferred ow rate

from the variables to be calculated. Eqs. (7) and (8) replace Eqs. (4)

and (5) in the system to be solved.

L iþ1 L i m N 2 þ h fg;N 2

h fg;O 2

m _ N 2 ¼ 0

G i 1 G i þ m N 2

h fg;N 2

h fg;O 2

m _ N 2 ¼ 0

(7)

(8)

The nitrogen molar ow transferred from the liquid to the vapor

is calculated using Ficks law for mass transfer [9].

dN N 2

dS i

k L

¼ k G P y N 2 y N 2 ¼ V m x N 2 x N 2

*

*

(9)

On a nite volume i, the mass transfer equation gives the mass

of nitrogen transferred m _ N 2 as a function of the nitrogen molar

fractions in the liquid, the vapor and on the vapor/liquid interfacial

surface.

m _ N 2 ¼ k G S i P i y y i

*

i

¼

k

V m S i x i x

L

*

i

(10)

In Eqs. (9) and (10), x * and y * are the equilibrium molar fractions

of nitrogen at the vapor/liquid interfacial surface. They are related

by Henrys law (Eq. (11)), K i being the Henrys constant [9].

*

y ¼ K i x

i

*

i

(11)

Three more parameters should be evaluated in order to calculate

the mass of nitrogen transferred to the vapor ow: the mass

transfer coefcient in the liquid k L , the mass transfer coefcient in

the vapor k G , and the interfacial surface S i . These parameters are

correlated in many studies, and similar values are calculated using

different correlations. In this study, equations of the mass transfer

coefcients are those presented in [8] and the equation for the

interfacial surface is the one presented in [10].

The mass transfer coefcient in the vapor k G , is represented as

an average value between a laminar coefcient and a turbulent

coefcient (Eq. (12) [8]). The laminar and turbulent Sherwood

numbers are expressed by the VDI-Wärmeatlas correlations (Eq.

(13)). In Eqs. (12) and (13), Sc G is the vapor Schmidt number, (d h /

l G,pe ) is the ratio of the hydraulic diameter to the length of vapor

ow channel within a packing element, Re G,rv is the vapor Reynolds

number, calculated with the relative velocity (v G,e þ v L,e ), and g is

the contact angle. The liquid/vapor friction factor x GL , is correlated

using the Colebrook equation for the friction factor in circular

channels, modied to have an explicit expression (Eq. (14) [11]) and

the hydraulic diameter d h (Eq. (15)) is calculated as a function of the

packing geometric parameters and the liquid lm thickness, given

by Nusselt formula for falling lms on inclined wall situation (Eq.

(16)).

q ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi q ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi D 2 2 G 2 2 k G ¼ k ¼ Sh
q ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
q ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
D
2
2
G
2
2
k G ¼
k
¼
Sh
G;lam þ k G;turb
G;lam þ Sh G;turb
d
s ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
h
(12)
d
1=3
h
Sh G;lam ¼ 0:664Sc
Re G;rv
G
l
G;pe
x
GL f
Re G;rv Sc G
d
8
h
r ffiffiffiffiffiffiffiffiffiffi
" 1 þ
(13)
Sh G t ;urb ¼
x
Sc 2=3
l G;pe ! 2=3 #
GL f
1 þ 12:7
G
8
5:02
14:5
x GL ¼ 2log d=d h
þ
(14)
3:7
Re
3:7
Re
G;rv log d=d h
G;rv 2
b p
h p
2ds p 2
bh
(15)
d h ¼
b p h p 2ds p 2 þ b p h p 2ds p 2 0:5 þ b p h p 2ds p
2h p
b p
2h p
3m L
v
Ls
(16)
d L ¼
r L ga p sin a 1=3
The mass transfer coefficient in the liquid is correlated by Bravo
et al., based on the penetration theory [8].
s ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
D L v Lf
k L ¼ 2
(17)
0:9pd h
The evaluation of the interfacial surface S i between the liquid
and the vapor flow should take into consideration the liquid
distribution. It is equal to the wetted surface of the packing,
calculated as a function of the flow characteristics (the dimen-
sionless numbers) and the packing characteristics. Eq. (18) [10] is
then used to calculated the interfacial surface; the factor F SE
accounts for variations in surface enhancement, and the contact
angle g accounts for the surface wettability. For the packing
considered in this study, with a surface area of 244 m 2 /m 3 and
a porosity of 0.98, F SE ¼ 0.35 and cos(g) ¼ 0.9 [10].
0:15 s 0:359
29:12ðWe L þ Fr Þ
S i
L
p
(18)
¼ F SE
Re 0:2
a p
ε 0:6 ð1 0:93cos gÞðsin aÞ 0:3
L

420

J. Rizk et al. / Energy 37 (2012) 417e429

Replacing m _ N 2 by its values (Eq. (10)) in Eqs. (2), (3), (7), and (8)

gives the four equations (Eqs. (19)e(22)) used in the system to be

solved to calculate the variables of the nite volume.

L iþ1 x iþ1 L i x i k L ;i S i

x i x

*

i

V

i

¼ 0

G i 1 y i 1

G i y i þ k G;i S i P i y

*

i

y i ¼ 0

L iþ1 L i k L ;i S i

x i x

*

i

V

i

þ

k L ;i S i

h

fg;N

2

h

fg;O

2

x i x

*

i

V

i

¼ 0

(19)

(20)

(21)

G i 1 G i þ k G;i S i P i y y i k G;i S i P i

*

i

h

fg;N

2

h

fg;O

2

y y i ¼ 0

*

i

(22)

When the conservation equations are to be written at the stage F

where the feed is introduced to the column, Eqs. (19)e(22) are

replaced by Eqs. (19a)e(22a) in order to take into account the ow

rates added.

L F þ1 x F þ1 L F x F k L ;F S i

x F x

*

F

V

F

¼ 0

(19a)

G F 1 y F 1 G F y F þ k G;F S i P F y

F y F þ m _ F y F ¼ 0

*

L F þ1 L F k L ;F S i

x F x

*

F

V

F

þ k L ;F S i

h

fg;N

2

x F x

*

F

h

fg;O

2

V

F

¼ 0

(20a)

(21a)

G F 1 G F þ k G;F S i P F y

F y F k G;F S i P F

*

h

fg;N

2

h

fg;O

2

þ m _ F ¼ 0

y F y F

*

(22a)

The evolution of the pressure in the column is function of the

pressure drop on each nite volume. Many studies have been

realized in order to correlate the pressure drop in structured

packing [12e14]. They correlate the pressure drop using the linear

pressure drop in a dry channel and applying corrections to the

vapor velocity and the friction factor.

A correlation for the vapor velocity correction, as a function of

the liquid and vapor properties and of the liquid velocity is

proposed by Woerlee et al. [13]: two types of corrections are

applied to the velocity, a static correction, related to the decrease of

the channel section due to the liquid ow, and a dynamic correc-

tion, related to the interfacial velocity. Fernandez et al. [14] ach-

ieved CFD simulations of countercurrent liquid and vapor ows in

a structured packing, by correcting the vapor ow velocity, stati-

cally and dynamically. Values of the pressure drop calculated when

applying both corrections on the vapor velocity did not differ much

from those obtained when applying the static correction only.

Using this result, only a static correction is applied to the vapor

velocity in this study.

Two correlations for the correction of the friction factor are

proposed in the literature in [12,14]. The friction factors

calculated by each correlation are compared, and their values did

not differ signi cantly. The correlation proposed by Darcy and

Weisbagh (Eq. (23)) calculates this factor as a function of the liquid

holdup [12]. The liquid holdup, dened as the fraction of liquid

occupying an element of vertical pipe, is given in Eq. (24), within

a 15% error, as a function of the liquid Reynolds number (correla-

tion of Collodziej).

DP ¼ 1:941h 0:446 f rg

L

v

2

d

h

h L ¼ 0:0273Re 0:331

L

(23)

(24)

The friction coefcient in Eq. (23) is calculated as a function of

the vapor Reynolds number, as follows [12]:

f ¼ 8:02Re

G

10

5

þ 0:364;

1:43Re G 10 6 þ 0:266;

if

if

Re

G

< 1500

Re G 1500

(25)

It is remarkable that equations for the pressure drop, the mass

transfer coefcient, and the interfacial surface require the vapor

and the liquid thermodynamics properties. These properties being

function of variables to be calculated (molar fractions, pressures,

and temperatures), an iterative procedure is used. It could be

summarized by the following steps.

1.

Given the feed mass ow and molar composition, assume

constant mass ow rates of liquid and vapor and linear varia-

tions of the liquid and vapor compositions through the N nite

volumes.

2.

Given the pressure at the boiler, assume constant pressure on

all nite volumes.

3.

Using the pressure and the molar fractions from 1 and 2,

calculate the thermodynamic properties of ows at the liquid

saturation temperature, using REFPROP 8.0.

4.

Using the vapor mass ow rates from 1 and the thermody-

namic properties from 3, evaluate the pressure drop using Eq.

5.

(23).

Using the new pressure prole from 4 and the molar fractions

from 1, calculate the liquid saturation temperatures and new

thermodynamic properties for the mixtures.

6.

Using thermodynamic properties from 5, calculate mass

transfer coefcients and interfacial surface.

At this stage, six variables are to be found for each nite volume (G i ,

L i , x i , y i , x i *, y i *). The total number of variables is 6N. At the 1st and

the Nth nite volumes, four variables are added: the liquid ow

sent to volume N (L Nþ1 , x Nþ1 ) and the vapor ow sent to volume 1

(G 0 , y 0 ). Equations needed to calculate these variables are the mass

and species conservation at the boiler and the condenser:

G 0 ¼ BL 1

y 0 ¼ x 1

L N þ1 ¼ CG N

x N þ1 ¼ y N

(26)

The iterative procedure continues after step 6 by the following:

  • 7. Write a (6N þ 4) (6N þ 4) matrix A , with Eqs. (1), (11), (19)e(22) written for each nite volume, and Eq. (26). Write a (6N þ 4) vector B, with constant values at the feed location.

  • 8. Resolve the system AX ðit Þ ¼ B.

  • 9. Using the mass ow rates and molar fractions from 8, repeat steps 3e8. Calculate a new vector X (itþ1) .

  • 10. Calculate the relative differences between each line of vectors X (it) and X (itþ1)

.

11. If the maximum of the relative differences is less than 10 4 , go

to step 12. Else, go back to step 9, using the vector X (itþ1) .

  • 12. Exergy analysis, as shown in Section 2.2.

2.2. Exergy analysis of a simple adiabatic column

The exergy analysis of a simple adiabatic column accounts

for exergy losses due to mass transfer in each nite volume and

J. Rizk et al. / Energy 37 (2012) 417e429

421

for exergy losses due to heat transfer in the boiler and the

condenser [6] .

On a nite volume i, exergy losses are calculated by an exergy

balance between the inlet ows and the outlet ows (Eq. (27) [7]).

Ex i loss ¼ L iþ1 Ex L

iþ1 þ G i 1 Ex

G

1 L i Ex L G i Ex

i

i

G

i

(27)

The exergy of a uid is dened as the maximum useful work

possible during a process that brings it to its equilibrium state [15]:

Ex ¼ h h ref T ref s s ref

The exergy loss in the condenser is:

(28)

Ex loss;cond ¼ m cool Ex cool;in Ex cool;out þ L N þ1 Ex

_

N Ex L

G

N þ1

(29)

And the exergy loss in the boiler is:

Ex loss;boil ¼ G 0 Ex 1 L

Ex

G

0

þ W boil 1

T boil

T ref

(30)

The thermodynamic efciency of the column equals the ratio of

the minimum work required to the distillation process to the

effective work required (Eq. (31) [16]). The minimum work is

calculated by the column exergy balance (Eq. (32) [17]).

h ¼

W min

W min þ P Ex loss

W min ¼ X Ex out X Ex in

(31)

(32)

Before comparing the simple adiabatic column to thermally

coupled and heat-integrated distillation columns, an optimum

conguration, dened by geometric and operating parameters, is

searched for the simple conguration. Parameters to be optimized

conditions on the liquid product (mass ow rate and purity). Exergy

losses in the process are only evaluated for the columns providing

the desired product. These conditions allow the algorithm to

reduce the list of parameters, as follows:

  • 1. For a combination of H, F, P 0 , B, and C, initialize M feed for 5000 tons per day of the liquid product.

  • 2. Estimate the diameter d for reduced total pressure drop.

  • 3. Solve the equation AX ¼ B (by applying all steps listed in the previous paragraph).

  • 4. If maximum pressure drop exceeds 500 paper meter, correct d.

  • 5. If (1 B)L 1 s 5000 tons per day, correct M feed .

  • 6. Repeat 3e5 until convergence.

  • 7. If oxygen molar fraction in the liquid at the bottom >95%, calculate exergy losses and duties of the boiler and the condenser. Save the results.

The algorithm output data are exergy losses for each combina-

tion of the above parameters. Before proceeding to the overall

optimization of the exergy losses in the simple adiabatic distillation

column, a sensitivity analysis shows the inuence of each param-

eter on the total exergy losses in the column and on the distribution

of losses in the different parts of the column.

2.2.1. Sensitivity analysis

In order to study the effect of each parameter on the exergy

losses in the process of cryogenic separation of air components in

a simple adiabatic distillation column, each parameter is varied

alone for a set of xed values of the others.

Fig. 4(a) shows the effect of the reux ratio at the bottom of the

column, B, on the total exergy losses. Fixed values of the rest of the

parameters are listed below. Unless different values are given, these

xed values are the one used all through the sensitivity analysis for

the simple adiabatic distillation column.

 

are as follows:

H ¼ 10 m;

 

d ¼ 18 m;

Column diameter, d.

F ¼ 1 m;

Feed location from the bottom, F.

P 0 ¼ 110 kPa;

Pressure at the boiler, P 0 .

C ¼ 0.4.

Reux ratio at the bottom of the column, B.

Reux ratio at the top of the column, C.

The molar composition of the feed stream is 78.1% of nitrogen

and 21.9% of oxygen. The desired product is low pressure, oxygen

rich liquid (>95% of oxygen). The mass ow rate of products is that

of an actual distillation unit, 5000 tons per day.

Parameters listed above are the input data of the simulation

algorithm. Once step 11 is achieved, the algorithm veries

The feed mass ow rate varies with the reux ratio at the

bottom of the column and when B increases the feed mass ow rate

increases. This leads to an increase in the energy needed to separate

the feed mixture components on one hand, and on another hand,

an increase in the pressure drop in the column. Consequently, total

exergy losses in the column increase. The thermodynamic ef-

ciency of the column decreases from 29% to 15.2% when varying the

reux ratio at the bottom from 0.56 to 0.83. It should be noted that,

J. Rizk et al. / Energy 37 (2012) 417 e 429 421 for exergy losses due

Fig. 4. Total exergy losses in the column, (a) as a function of the reux ratio at the boiler stage, (b) as a function of the reux ratio at the condenser stage.

422

J. Rizk et al. / Energy 37 (2012) 417e429

for lower values of B, the purity of 95% of oxygen in the liquid

product could not be reached.

Fig. 4(b) shows the variation of exergy losses with the reux

ratio at the top of the column, for a xed value of B of 0.6 and a 20-

m column diameter. An increase in the reux ratio at the top of the

column causes an increase in the nitrogen rich uxes in the

column; exergy losses during the separation increase.

The pressure inuence on total exergy losses in the distillation

process is showed in Fig. 5, for reux ratios B ¼ 0.6 and C ¼ 0.3. In

order to explain the decreasing value of exergy losses when the

pressure level increases, the distribution of exergy losses in the

different components of the column (boiler, column, condenser,

and compressor) are calculated for each pressure level. Fig. 6 shows

these exergy losses as a function of the pressure. It is remarkable

that exergy losses in the compressor represent a maximum ratio of

13% from total exergy losses. The highest contribution is that of the

column, presenting a minimum ratio of 50% from total exergy

losses. These ratios explain the decrease of the exergy losses when

the pressure increases: even though the exergy losses in the

compressor increase, their contribution in the total exergy losses is

signicantly less than that of the column, where exergy losses

decrease with the pressure level.

The feed location inuence on exergy losses is represented in

Fig. 7, for C ¼ 0.3 and B ¼ 0.6. The total pressure drop in the column

decreases from 5 kPa for a feed at 2 m from the bottom to 3.5 kPa

for a feed at 5 m from the bottom. Less pressure drop leads to less

exergy losses, and an increasing thermodynamic efciency is

calculated. It increases from 0.27 to 0.29 when the feed was moved

from 2-m height from the bottom of the column to 5-m height.

Fig. 8 represents the variation of exergy losses with the diameter

of the column with a xed value of the column height of 10 m. A

larger diameter of the column causes lower pressure losses in

the column and thus lower exergy losses for the same separation

work.

422 J. Rizk et al. / Energy 37 (2012) 417 e 429 for lower values of

Fig. 6. Distribution of the exergy losses in the column for different pressure levels.

calculated. This minimum value of the exergy losses is calculated in

a 20-m diameter, 10-m height column, where the feed ow is

introduced at a 1-m height from the bottom. This columns operates

at 110 kPa with a reux B ¼ 0.6 at the boiler and a reux C ¼ 0.3 at

the condenser.

Fig. 10 shows the contribution of each component of the distil-

lation scheme considered in total exergy losses. The column has the

highest exergy losses (57%), followed by the condenser (29%), then

the boiler (11%), and the compressor (3%).

This distribution shows that a possible decrease in total exergy

losses is achieved by reducing exergy losses on heat exchangers and

the irreversibility in the distillation column. Reducing or elimi-

nating heat exchangers leads to the conguration of thermally

coupled distillation columns. Reducing the irreversibility in the

column is achieved by making the heat transfers all along the

column.

2.2.2. Overall optimization of column

In order to choose the geometric and operating parameters of

the column leading to minimum exergy losses, an overall optimi-

zation (based on a genetic algorithm) of the column is realized. For

each combination of the parameters cited above, total exergy losses

are calculated. A decreasing curve is obtained (Fig. 9) and the

optimal congurations deduced.

Fig. 9 shows that the minimum exergy losses in simple adiabatic

distillation columns producing 5000 ton per day of oxygen rich

low-pressure liquid are close to 30,000 kW. The thermodynamic

efciencies could be deduced and values close to 29% are

422 J. Rizk et al. / Energy 37 (2012) 417 e 429 for lower values of

Fig. 5. Inuence of the pressure on the total exergy losses.

3. Thermally coupled distillation column

Because of the high energy consumption and the low thermo-

dynamic efciency of the conventional distillation schemes,

researches are realized to nd methods to improve performances of

distillation processes [18]. Besides, in the exergy analysis of the

simple adiabatic column, the cold source for the condenser at the

top is considered to be free, which is not true in real applications.

The liquid nitrogen necessary for condensation is produced in

a separate process, which exergy losses and performances should

be taken into consideration for the optimization. To include the

production of the cold source for the condenser in the process

422 J. Rizk et al. / Energy 37 (2012) 417 e 429 for lower values of

Fig. 7. Inuence of the feed location on total exergy losses.

J. Rizk et al. / Energy 37 (2012) 417e429

J. Rizk et al. / Energy 37 (2012) 417 e 429 Fig. 8. In fl uence

Fig. 8. Inuence of the column diameter on total exergy losses.

J. Rizk et al. / Energy 37 (2012) 417 e 429 Fig. 8. In fl uence

Fig. 10. Contribution of components in total exergy losses.

423

study, it is considered produced in a distillation column, at low

pressure, thermally coupled with a higher pressure column.

Thermal coupling between adiabatic conventional columns has

been studied since the early fties. It consists in eliminating the

boiler or/and the condenser in one distillation column and

replacing it by countercurrent connections with the second

column. Fig. 11 shows a fully thermally coupled distillation process

of a ternary mixture, also called a Petlyuk column [19].

Based on the Petlyuk conguration, many alternative schemes

have been proposed to improve the thermodynamic efciencies of

the thermally coupled columns, for ternary mixtures distillation

[6,19e21]. Optimal congurations are searched for different rela-

tive volatilities and feed compositions, and some of the proposed

congurations provide similar or even higher efciencies than

those of the Petlyuk columns. Besides, Jiménez et al. note in their

study [19] that the Petlyuk column, because of its interconnections,

requires that the pressure at the bottom of column 1 (to the left) be

lower than the pressure at the bottom of column 2 (to the right),

while the pressure at the top of column 1 should be higher than the

pressure at the top of column 2.

Attempts have been made to introduce the Petlyuk column

conguration into cryogenic air separation applications [6]. A

thermodynamic efciency of 14.9% was calculated, when the

thermodynamic efciency of a single coupling column reaches

44.5%. Therefore, the Petlyuk conguration has not found applica-

tion in cryogenic air separation.

Thermally coupled columns used for cryogenic air separation

are usually simple coupled congurations [22e24]. They are based

on a low- and a high-pressure distillation column. The condenser of

the high-pressure column HP is cooled by the boiler of the low-

J. Rizk et al. / Energy 37 (2012) 417 e 429 Fig. 8. In fl uence

Fig. 9. Total exergy losses in different congurations of simple adiabatic columns.

pressure column LP. Fig. 12 shows a representative scheme of the

coupled column.

In this scheme, the air compressing unit has the largest contri-

bution in the total exergy losses (nearly 20% [1]). The pressure in

the HP column is 620 kPa. An improvement could be realized by

reducing the operating pressure.

In this paper, the thermally coupled column of Fig. 12 is ther-

modynamically optimized. Geometric and operating parameters

leading to the minimum total exergy losses are dened.

3.1. Simulation of a thermally coupled adiabatic column

The simulation algorithm of the simple adiabatic column is

modied and used for the simulation and the exergy analysis of the

double column. The HP column has the same structure as the

simple adiabatic column; it has a boiler at the bottom and

a condenser at the top and the distillation products are an oxygen

rich liquid at the bottom and a nitrogen rich vapor at the top. It

differs from the simple adiabatic column only by the operating

pressure. In the LP column, a liquid air feed is sent to the column. At

the top of the column, no condenser is used. A fraction (1-B 1 ) of the

liquid collected at the bottom of the HP column is expanded and

J. Rizk et al. / Energy 37 (2012) 417 e 429 Fig. 8. In fl uence

Fig. 11. Representative scheme of a Petlyuk distillation column [19].

424

J. Rizk et al. / Energy 37 (2012) 417e429

in each configuration. As stated in Section 2.2.1, the feed mass flow rates are subject to
in each configuration. As stated in Section 2.2.1, the feed mass flow
rates are subject to variation in order to ensure the energy balance
at the intermediate heat exchanger condition and the 5000 tons/
day liquid product mass flow rate. These two parameters are
therefore function of other parameters listed and will not be
considered in the optimization procedure. The algorithm for
calculating exergy losses in the column for each combination of
parameters includes the following steps:
1.
For a given combination of the reflux ratios at the top and at the
bottom of columns, estimate initial values for M feed,HP and
M feed,LP , considering a liquid low-pressure product of
5000 tons/day and the energy balance at the intermediate heat
exchanger.
2.
Simulate high-pressure column and then low-pressure column.
3.
When convergence is obtained, correct M feed,HP and M feed,LP ,
considering the 5000 tons/day liquid product flow rate and the
energy balance at the intermediate heat exchanger.
4.
If the new values of the feed flow rates calculated differ from
previous values (relative difference > 10 4 ), go back to step 2.
Else, go to step 5.
5.
If the oxygen molar fraction in the low-pressure liquid product
exceeds 95%, calculate the exergy losses in the column. Save the
results.

Fig. 12. Thermally coupled column for cryogenic air distillation.

sent at the top of the LP column. Eq. (26) of Section 2.1 are therefore

replaced by Eq. (33) for the low-pressure column resolution:

G 0 ¼ BL 1

y 0 ¼ x 1

L N

þ1

¼

ð1 B 1 Þ L 1;HP

x N

þ1

¼ x 1;HP

(33)

An additional condition is to be added while simulating the

double adiabatic column. The energy balance at the intermediate

heat exchanger should be veried (Eq. (34)).

B 2 L 1;LP h fg;LP ¼ CG N;HP h fg;HP

(34)

Mass ow rates of feeds in the two columns are determined

regarding the energy balance Eq. (34) and the 5000 tons/day liquid

product ow rate needed.

3.2. Exergy analysis of thermally coupled columns

Exergy losses in this column conguration are due to mass

transfer in the two columns, the heat transfer in the boiler and in

the intermediate heat exchanger, and in the air compressor

providing the high-pressure vapor stream.

Exergy losses in the compressor are:

Ex loss;comp ¼ M feed T s comp;out s comp;in

(35)

Besides the geometric parameters, the operating parameters to

be optimized in this column conguration are the followings:

As for the simple adiabatic column, a sensitivity analysis is

realized in order to study the effect of each parameter on the total

exergy losses in the column. Then the overall optimization of the

performance of the column gives the combination of parameters

leading to minimum exergy losses in the distillation column.

3.2.1. Sensitivity analysis

Fig. 13 shows total exergy losses in the column as a function of

the reux ratios at the bottom and at the top of the high-pressure

column, B 1 and C respectively. Fixed values of other parameters are

as follows. Geometric parameters are chosen in such a way to

minimize pressure drop in the gas ow.

High-pressure HP ¼ 550 kPa.

Low pressure LP ¼ 110 kPa.

High-pressure column height H HP ¼ 10 m.

Low pressure column height H LP ¼ 10 m.

Reux ratio at the bottom of the low pressure column

B 2 ¼ 0.8.

Feed location in the high-pressure column F 1 ¼ 1 m.

Feed location in the low pressure column F 2 ¼ 9 m.

High-pressure column diameter d HP ¼ 19 m.

Low pressure column diameter d LP ¼ 12 m.

when B 1 increases, the liquid introduced at the top of the low-

pressure column decreases. In order to ensure the 5000 tons/day

product ow rate, M feed,LP increases, causing higher exergy losses in

the low-pressure column and thus higher exergy losses in the

column (Fig. 13(a)).

On another hand, when the reux ratio at the top of the high-

pressure column increases, the liquid introduced to the top of the

The reux ratio at the HP boiler, B 1 .

low-pressure column increases too. This causes a decrease in the

The reux ratio at the top of the HP column, C.

liquid feed mass ow rate and thus the decrease of total exergy

The reux ratio at the bottom of the LP column, B 2 .

losses.

The low pressure, LP.

Fig. 14 shows the inuence of the reux ratio B 2 at the bottom of

The high pressure HP.

The above listed parameters are the input data of the algorithm

used to simulate the columns and calculate the total exergy losses

the low-pressure column on total exergy losses, for reux ratios at

the bottom and at the top of the high-pressure column of 0.4. Total

exergy losses in the column increase when B 2 increases because the

feed mass ow rates increase.

J. Rizk et al. / Energy 37 (2012) 417e429

425

J. Rizk et al. / Energy 37 (2012) 417 e 429 425 Fig. 13. In fl

Fig. 13. Inuence of the reux ratios in the high-pressure column on the total exergy losses, (a) effect of the reux ratio at the bottom, (b) effect of the reux ratio at the top.

Fig. 15 shows the effect of pressure levels in the columns on total

exergy losses. Since a constant temperature difference of 5 K is

assumed at the intermediate heat exchanger between the high-

pressure vapor condensation and the low-pressure liquid evapo-

ration, the pressure level of the high-pressure column is calculated

for each value of the low-pressure to ensure this condition. An

increase in the low-pressure column is followed by an increase in

the high-pressure column causing an increase in the compressor

exergy losses. The compressor contribution in total exergy losses in

the double adiabatic column being the highest (50e 60%), total

exergy losses will increase due to the increase in the compressor

exergy losses.

For the double adiabatic column, the geometric parameters

(diameters and heights of columns and feed locations) present the

same effect as for the simple adiabatic column. Total exergy losses

decrease when the column diameters increase because the pres-

sure drop decreases. The feed location, in both columns, has very

little effect on total exergy losses.

3.2.2. Overall optimization of the column

Several possible combinations of geometric and operating

parameters are considered and total exergy losses are calculated for

each combination. A decreasing curve is obtained (Fig. 16) and

optimal congurations are deduced. Minimum exergy losses of

31.4 kW/kg of vapor feed are calculated for a conguration where

the low-pressure column operates at 110 kPa and the high-pressure

column at 750 kPa. The columns are 22-m diameter and 10-m

length each. The reux ratios are as follows: 0.1 at the high-

pressure boiler, 0.6 at the high-pressure condenser and 0.8 at the

low-pressure condenser. The vapor feed in the high-pressure

column is introduced at a 1-m height from the bottom of the

column and the liquid feed in the low-pressure column at a 9-m

height from the bottom.

4. Diabatic distillation column

The thermal coupling between adiabatic columns includes an

intermediate heat exchanger where low-pressure liquid evaporates

and high-pressure vapor condensates. Further thermodynamic

improvements could be achieved in the distillation processes by

distributing this thermal coupling over the height of the columns.

Instead of increasing the high-pressure in the column in order to

ensure a 5-K pinch at the intermediate heat exchanger, a lower

value of the pressure could be tested if the heat exchange between

the columns is still achieved through wall contacts of the two

columns.

The rst approach for creating diabatic ows in distillation

columns was by adding sequential heat exchangers all through the

column height [5,7,22,25,26]. Fig. 17 shows heat exchangers, adding

heat to the stripping section of the column, and removing heat from

the rectifying section. In this conguration, the exergy destruction,

located principally in the boiler and the condenser, is distributed on

trays [5]. As a result, the diabatic column destructs half the exergy

a conventional column would destroy for the same separation.

Rivero et al. [22,25] searched for the optimal allocation of the

sequential heat exchangers leading to the best thermodynamic

performances, and calculated 39% exergy loss decrease in the dia-

batic column, compared to the conventional column.

Recently, a new type of diabatic distillation column was pre-

sented. Known as internally heat-integrated distillation column, it

has the same approach of adding and removing heat through the

column height, but the stripping section and the rectifying section

J. Rizk et al. / Energy 37 (2012) 417 e 429 425 Fig. 13. In fl

Fig. 14. Effect of the bottom reux ratio in the low-pressure column on exergy losses.

J. Rizk et al. / Energy 37 (2012) 417 e 429 425 Fig. 13. In fl
J. Rizk et al. / Energy 37 (2012) 417 e 429 425 Fig. 13. In fl

Fig. 15. Effect of pressures in the columns on total exergy losses.

426

J. Rizk et al. / Energy 37 (2012) 417e429

426 J. Rizk et al. / Energy 37 (2012) 417 e 429 Fig. 16. Total exergy
426 J. Rizk et al. / Energy 37 (2012) 417 e 429 Fig. 16. Total exergy

Fig. 16. Total exergy losses in different congurations of double adiabatic columns.

are put into contact and form a heat exchanger, where heat is

transferred from the hot source (the HP rectifying section) to the

cold sink (the LP stripping section) [2,3,27]. The ideal conguration

of the internally heat-integrated columns contains neither boiler

nor condenser. Therefore, it reduces the total exergy losses in the

column and increases its efciency.

In this paper, an ideal internally heat-integrated distillation

column is considered and represented in Fig. 18.

The simulation of the diabatic column operation differs from the

previous studied adiabatic columns, where an industrial packed

column was considered. The conservation equations should be

adapted to take into account the additional heat transfers through

the column.

4.1. Simulation of the diabatic distillation column

In order to simulate the diabatic column, we assume that the

distillation process is realized in a heat exchanger which surface

contact area is sufcient to exchange heat between the low-

pressure mixtures and the high-pressure mixtures.

In this distillation conguration, mass ow rates of the liquid

and vapor mixtures vary more markedly, due to condensation of

426 J. Rizk et al. / Energy 37 (2012) 417 e 429 Fig. 16. Total exergy

Fig. 17. Heat exchanger sequence in a HIDiC.

426 J. Rizk et al. / Energy 37 (2012) 417 e 429 Fig. 16. Total exergy

Fig. 18. Ideal internally heat integrated distillation column.

the high-pressure vapor and the evaporation of the low-pressure

liquid. On the nite volume iof Fig. 3, an additional variable, the

heat transferred, is to be added.

To calculate the amount of heat transferred, an overall heat

transfer coefcient is rst correlated. It takes into account

a convective heat transfer coefcient during the condensation of

vapor mixtures at high pressure, a convective heat transfer coef-

cient during the evaporation of liquid mixtures at low-pressure and

a conductive heat transfer coefcient through the heat exchanger

wall. Correlations for convective heat transfer coefcients are

detailed in [28]. Thome correlation for evaporation in the low-

pressure column and Ackers correlation for the condensation in

the high-pressure column are used in this study. When the overall

heat transfer coefcient is evaluated, the heat exchanged is calcu-

lated as a function of the temperature difference between the two

columns.

The conservation equations with heat transfer are replacing Eqs.

(19)e(22), and give Eqs. (36)e(39).

 

*

L iþ1 x iþ1 L i x i k L ;i S i

x i x

i

Q i

 

(36)

 

V

i

¼ x eq

h fg;eq

 

G i 1 y i 1

G i y i þ k G;i S i P i y

*

y i ¼

 

Q i

(37)

i

x eq

h fg;eq

 

*

*

¼

Q i

 

L iþ1 L i k L ;i S i

x i x

i

þ k L ;i S i

h fg;N 2

x i x

i

(38)

V

i

h fg;O 2

V

i

h fg;eq

G i 1 G i þ k G;i S i P i y y i k G;i S i P i

*

i

h fg;N 2

h fg;O 2

Q i

¼

h fg;eq

y y i

*

i

(39)

In Eqs. (36)e(39), h fg,eq is the heat of vaporization of the mixture in

equilibrium with the vapor at high pressure or with the liquid at

low-pressure. x eq is the nitrogen molar fraction in the mixture.

The pressure drop in the heat exchanger considered for the

diabatic distillation is calculated by applying the corrections to the

vapor velocity and to the friction factor in the linear pressure drop

equation [13].

J. Rizk et al. / Energy 37 (2012) 417e429

427

The method of simulation of the diabatic distillation process in

a heat exchanger is as follows:

  • 1. The feed mass ow rate and molar composition being known, assume a linear variation of the liquid and the vapor mass ow rates and compositions.

  • 2. Assume a linear variation of the pressures.

  • 3. Calculate liquid saturation temperatures using REFPROP 8.0 with compositions and pressures from 1 and 2.

  • 4. Calculate thermodynamic properties of liquid and vapor mixtures on both pressure levels.

  • 5. Calculate pressure drops using properties from 4.

  • 6. Calculate corrected thermodynamic properties using pressures from 5.

  • 7. Calculate heat transfer coefcients and heat exchanged.

  • 8. Calculate mass transfer coefcients.

  • 9. Write 6N equations for the high-pressure column and resolve

determine the number of passes needed to ensure the 5000 tons

per day of the liquid product.

Before proceeding to the general optimization of the process,

a sensitivity analysis is achieved, to study the effect of each

parameter on total exergy losses in the column, producing 5000

tons per day of oxygen rich liquid at low-pressure.

4.2.1. Sensitivity analysis

The effect of each parameter on total exergy losses in the dia-

batic column is now studied, by choosing xed values for other

parameters.

First, the effect of pressure levels on each side of the column is

studied. Fig. 19 shows the effect of the pressure ratio between the

two sides of the heat exchanger on the total exergy losses.

Fig. 19 (a) represents the total exergy losses per kg of high-

pressure vapor feed and Fig. 19 (b) represents them per kg of

low-pressure liquid product. The xed values of other parameters

the system AX ¼ B.

are xed to:

  • 10. Using L 1 and x 1 at high pressure, write 6 N equations for the

low-pressure columns and resolve the system AX ¼ B .

H ¼ 10 m

  • 11. Calculate the relative differences for both columns.

d LP ¼ 44 mm

d HP ¼ 44 mm

  • 12. If maximum relative difference higher than 10 4 , repeat from

step 4. Else, proceed to exergy analysis.

4.2. Exergy analysis of the diabatic column

Exergy losses in the diabatic distillation column are due to

irreversibility on each nite volume and to the air compression.

On each nite volume, exergy losses are calculated by an

exergy balance, with the heat transfer taken into account

(Eq. (40) ).

Ex

loss

i

¼ L iþ1 Ex L

iþ1 þ G i 1 Ex

1 L i Ex L þ G i Ex L þ Q i 1

V

i

i

i

T ref

T i

(40)

Optimal geometric and operating parameters, leading to

minimum exergy losses, are calculated. Parameters to be optimized

are:

M feed ¼ 0.1 kg/s/pass.

When studying the dependence of the total exergy losses as

a function of the pressure ratio for a given high-pressure feed, an

increasing curve is observed. In fact, exergy losses in the

compressor are proportional to the high-pressure level and those in

expansion valve are proportional to the pressure ratio. They both

cause an increase in total exergy losses for a given feed mass ow

rate.

On another hand, when the pressure ratio increases, the amount

of heat exchanged between the high- and the low-pressure uxes

increases, and the amount of low-pressure liquid collected at the

bottom of the low-pressure column for a given vapor feed mass

ow rate increases. As a result, the number of passes needed to

ensure 5000-ton per day of pure oxygen decreases and total exergy

losses too (Fig. 19(b)).

Graphs of Fig. 20 show the effect of geometric parameters

(height of the column and diameter of the low-pressure pass).

When the column height increases, the pressure drop in the

Column height, H.

columns and the quantity of heat exchanged increase. Both

Hydraulic diameter at low-pressure, d LP .

pressure drop and heat increase exergy losses ( Fig. 20 ).

Pressure ratio HP/LP.

In order to simplify the optimization procedure, the column is

considered as a two-pass heat exchanger, one pass at each pressure

level. For each mass ow rate of the feed, simulation results

An increase in the column diameter leads to a decrease in the

pressure drop and to improvement in mass transfers between the

liquid and vapor mixtures (higher interfacial surfaces). This

explains the decrease in exergy losses when the diameter increases,

Fig. 20(b).

J. Rizk et al. / Energy 37 (2012) 417 e 429 427 The method of simulation

Fig. 19. Exergy losses as a function of the pressure ratio, (a) per kg of vapor feed, (b) per kg of liquid product.

428

J. Rizk et al. / Energy 37 (2012) 417e429

428 J. Rizk et al. / Energy 37 (2012) 417 e 429 Fig. 20. Exergy losses

Fig. 20. Exergy losses as a function of geometric parameters, (a) as a function of the column height, (b) as a function of low-pressure pass diameter.

4.2.2. Overall optimization of the column

As for adiabatic columns, exergy losses are calculated only when

the desired purity of the liquid product is achieved. A decreasing

curve is obtained (Fig. 21), representing the exergy losses per kg of

feed mass ow rate. A 20.7-m diameter, 10-m height column,

operating at a high pressure of 450 kPa and a low-pressure of

150 kPa, leads to the minimum exergy losses of 24 kW/kg of feed.

By comparing the optimal values in Fig. 21 and those plotted in

Fig. 16, a relative decrease of 23% in the total exergy losses are

calculated between the optimal conguration of the double adia-

batic column and the optimal conguration in the diabatic column.

6. Concluding remarks

In this study, optimal congurations for minimal total exergy

losses of three types of cryogenic distillation columns are calcu-

lated. The columns considered for the comparison are the simple

adiabatic column, the double adiabatic column, and the internally

heat-integrated column (diabatic column). The double diabatic

column presents 23% less exergy losses than the double adiabatic

column. It should be noted that a general optimization of the global

process including the distillation columns will lead to more specic

results and comparisons.

5. Comparison of the three types of cryogenic distillation

columns

Performances of double adiabatic columns and diabatic columns

are compared regarding total exergy losses calculated in optimal

congurations. A total of 23% decrease in total exergy losses are

calculated when replacing the local intermediate heat exchanger of

the double adiabatic column by an overall heat transfer between

the columns. This decrease is due mainly to the decrease in the

pressure in the high-pressure column (from 750 kPa to 450 kPa),

decreasing exergy losses in the compressor. It is also due to the

decrease in irreversibilities in the column due to heat transfers.

The comparison with the simple adiabatic column cannot be

made on a similar basis since the products of the simple adiabatic

column distillation are different from those of the double column

(presence of a high-pressure nitrogen rich vapor product in the

double columns). Besides, the simple adiabatic column has no

compressors and the production of the cold source for the

condensation at the top is not considered.

428 J. Rizk et al. / Energy 37 (2012) 417 e 429 Fig. 20. Exergy losses
428 J. Rizk et al. / Energy 37 (2012) 417 e 429 Fig. 20. Exergy losses

Fig. 21. Exergy losses in the diabatic column for different congurations.

Notation

a

P

b

P

B

Packing surface area (m 2 /m 3 )

Corrugation base length (m)

Reux at the boiler

  • C Reux at the condenser

  • d Column diameter (m)

d h

Hydraulic diameter (m)

  • D Diffusion coefcient (m 2 /s)

Ex

f

F

h

h

fg

h L

h

P

h

pe

H

k

K

l G,pe

Exergy (W)

Friction factor

Feed location (m)

Enthalpy (J/kg)

Heat of vaporization (J/kg)

Liquid holdup

Corrugation height (m)

Height of the packing element (m)

Column height (m)

Mass transfer coefcient

Henry constant

Length of the vapor ow channel within a packing

element (m)

  • L Liquid mass ow rate (kg/s)

  • m Mass ow rate (kg/s)

_

P

Q

Pressure (bar)

Heat (W)

s

s P

S i

T

Entropy (K/kg.K)

Corrugation side length (m)

Interfacial surface (m 2 )

Temperature (K)

  • v Velocity (m/s)

  • V Vapor mass ow rate (kg/s)

V m

Molar volume (m 3 /mol)

  • x Nitrogen molar fraction in the liquid

x 0

Oxygen molar fraction in the liquid

J. Rizk et al. / Energy 37 (2012) 417e429

429

x*

Nitrogen molar fraction in the liquid at the interface

y

Nitrogen molar fraction in the vapor

y 0

Oxygen molar fraction in the vapor

y*

Nitrogen molar fraction in the vapor at the interface

W

Work (W)

Greek letters

a

Corrugation angle with the horizontal ( )

g

Contact angle ( )

d

Liquid lm thickness (m)

ε

Porosity

h

Efciency

r

Density (kg/m 3 )

m

Viscosity (Pa s)

  • 4 Fraction of the triangular ow channel occupied by liquid

x GL

Liquid/vapor friction factor

Non-dimensional numbers

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Reynolds number

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Schmidt number

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Sh

Sherwood number

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Boiler

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Boiler

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C

Condenser

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Condenser

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Effective

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eq

Equilibrium

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Vapor

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High pressure

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Liquid

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Laminar

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LP

Low pressure

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Relative velocity

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s

Supercial

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turb

Turbulent

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