Proceedings of the ENCIT 2012 14th Brazilian Congress of Thermal Sciences and Engineering

Copyright
c 2012 by ABCM November 18-22, 2012, Rio de Janeiro, RJ, Brazil

MODELING AND SIMULATION OF HMT ON NATURAL GAS

DEHYDRATION USING SOLID DESICCANTS
J. D. Benther, [email protected]
L. A. Sphaier, [email protected]
Laboratrio de Mecnica Terica e Aplicada, Programa de Ps-Graduao em Engenharia Mecnica, Departamento de Engenharia
Mecnica, Universidade Federal Fluminense
Rua Passo da Ptria 156, bloco E, sala 216, Niteri, RJ, 24210-240, Brazil

Abstract: Natural gas is the fastest growing primary energy source and its use is expected to almost double to 2020,
providing a relatively more clean fuel for the worldwide energy demand. Some contaminants, such as water vapor, have
to be removed before its use. Dehydration of natural gas is of extreme importance to avoid the formation of hydrates
and other associated problems. Different dehydration methods exist; however the solid desiccant approach can dehydrate
natural gas to levels of water vapor lower than other methods. This paper presents a simple formulation for simulating
the dehydration of a wet methane stream flowing though a porous medium composed of hygroscopic particles. The model
assumes small resistance to diffusion within particles and takes heat and mass transfer rates into account by employing
constant transfer coefficients. The formulation was developed based in the traditional mass and energy conservation
principles, considering a one-dimensional transient scenario. A dimensional analysis is also performed and relevant
dimensionless groups are introduced. The set of dimensionless parameters are similar to effectiveness-NTU groupings,
widely used in heat exchangers. Despite its simplicity, the proposed formulation presents a new contribution since similar
analysis is apparently unavailable in the gas dehydration literature. Finally, in order to illustrate the effect of varying the
dimensionless groups the formulation is solved using a combined finite-volumes/method-of-lines approach. The results
example how the dimensionless parameters can influence the dehydration process.

Keywords: Natural Gas, Adsorption, Dehydration, Solid Desiccant, Dehumidification.

1. NOMENCLATURE

A area Subscripts
cp constant pressure specific heat adv advective
hh convective heat transfer coefficient b bed
hm convective mass transfer coefficient closed pore
i specific enthalpy e effective or apparent
00
j mass flux g natural gas
L cylinder height in inlet
m mass i process gas flow
m mass flow rate l adsorbed water (liquid phase)
t time max maximum
T temperature min minimum
vi process gas flow velocity op operation
vb bulk velocity out exit
x distance from the cylinder entrance p particle
W dry basis adsorbed water concentration pore
Y dry basis vapor concentration s solid phase or surface
Greek Symbols v water vapor
density Superscripts
 total porosity dimensionless quantity
periodical time dry basis
Proceedings of the ENCIT 2012 14th Brazilian Congress of Thermal Sciences and Engineering
Copyright
c 2012 by ABCM November 18-22, 2012, Rio de Janeiro, RJ, Brazil

2. INTRODUCTION

From the standpoint of processing and conditioning of natural gas, it should be brought to water levels established by
oil and natural gas standards in order to prevent the formation and deposition of solid hydrates (Carroll, 2009) that may
in the long run reduce the useful diameter of pipes (Jassim et al., 2010; Mokhatab et al., 2007). Furthermore, it can block
partly or wholly valves, corrosion formation (Obanijesu et al., 2011) and reduce equipments life expectancy.
To prevent hydrate formation, different techniques may be used. Among them, there are processes more widespread
such as liquid and solid desiccant for gas dehumidification.
Work made by Gandhidasan et al. (2001) performs a study on the use of solid desiccants based on silica gel regarding
the effects in various parameters changes. Moreover, a study was developed on the efficiency, i.e. to estimate the energy
required in the regeneration process. Recently, Nastaj and Ambrozek (2009) performed a theoretical analysis of the
adsorptive drying process of gases in a cyclic temperature swing adsorption system with two fixed bed adsorption columns
using silica gel as solid desiccant. The computer simulations results are used to study the effects of the inlet gas relative
humidity on the breakthrough curves in the adsorption step and purge gas temperature on the breakthrough curves in the
desorption step.
Apparently, a notable feature of previous works on dehydration of natural gas using solid desiccant is a few develop-
ment compared to other methods of natural gas dehydration. In this context, this work presents a mathematical formulation
for heat and mass transfer for desiccant dehydration of natural gas. The formulation herein presented is based on normal-
ized dimensionless groups used in studies like those developed for heat and mass exchangers (Sphaier and Worek, 2009)
and for storage of adsorbed natural gas (da Silva and Sphaier, 2010).

3. PROBLEM FORMULATION

In this section, the main formulations for the dehydration of natural gas using solid adsorbents are presented. The
reservoir has only one entrance and one exit for the natural gas flow. Initially, the reservoir is empty and the pressure
and temperature are equal to the surroundings. Then, as the natural gas with higher levels of water vapor flows into the
reservoir the process of dehumidification begins.

Figure 1. Volume, porous area view and dehydration cycle configuration

According to figure 1, two steps are done over dehydration cycle: adsorption and regeneration. The former intend to
reduce the natural gas water vapor concentration and the latter is required to remove water of the solid desiccant providing
the possibility of restarting the cycle.
The simplifying assumptions considered in the derivation of the current model are described such as: natural gas as
water vapor and methane; incompressible flow; negligible pressure drop or loss; unidirectional flow; constant specific
Proceedings of the ENCIT 2012 14th Brazilian Congress of Thermal Sciences and Engineering
Copyright
c 2012 by ABCM November 18-22, 2012, Rio de Janeiro, RJ, Brazil

heats; radiation effects are negligible due to the relatively low temperature differences; there is no chemical reaction nor
any internal energy generation of any form; isotropic medium; no phase change besides that resulting from adsorption;
and no heat losses to the environment.

3.1 Mass Balance

Since the mass of the solid portion and that of the natural gas are assumed invariable only a mass balance for water
is required. Denoting V as a portion of the vessel volume (that includes all volumes) and S as its bounding surface, an
integral mass balance is written as:
Z x1
d
(b v,i + (1 b ) p v, + l ) Ax dx = j 00v,i n Ax + j 00v,i n Ax



x=x1 x=x0
(1)
dt x0

where j 00v,i = v,i v b = b v,i v i = g Y v b and S = As /V

Finally, simplification yields:

Y Yp b W Y
b + (1 b ) p + + vb = 0 (2)
t t g t x

A general mass balance for the particles volume is given by:

Z x1 Z x1
d
(l + (1 b ) p v, ) Ax dx = hm g (Y Yp ) S Ax dx (3)
dt x0 x0

After simplifications, one can conclude that:

b W Yp
+ (1 b ) p = hm S (Y Yp ) (4)
g t t

Subtracting equation (4) from (2) yields a mass balance for the process gas flow:

Y Y
b + vb = hm S (Y Yp ) (5)
t x

3.2 Energy Balance

Since pressure variations are assumed negligible, the following relations apply:
Z x1
d
(b g (ig + iv,i Y ) + (1 b ) p g (ig + iv, Yp ) + il b W + is b ) Ax dx =
dt x0

= (g (iv,i Y + ig ) (v b n) Ax )x=x1 + (g (iv,i Y + ig ) (v b n) Ax )x=x0 (6)

Finally, simplification yields:

b b is
b (ig + iv,i Y ) + (1 b ) p (ig + iv, Yp ) + (il W ) + + vb (iv,i Y + ig ) = 0 (7)
t t g t g t x

The energy balance for the particles is more simple, because there is only vapor diffusion and it is given by:
Z x1
d
((1 b )p (ig g + iv, v, ) + il l + is b ) Ax dx =
dt x0
Z x1
= (iv,f hm g (Y Yp ) + hh (T Tp )) S Ax dx (8)
x0
Proceedings of the ENCIT 2012 14th Brazilian Congress of Thermal Sciences and Engineering
Copyright
c 2012 by ABCM November 18-22, 2012, Rio de Janeiro, RJ, Brazil

Lastly, simplification yields:

 
b b is hh
(1 b )p (ig + iv, Yp ) + (il W ) + = iv,f hm (Y Yp ) + (T Tp ) S (9)
t g t g t g

Subtracting equation (9) from (7) yields a energy balance for the process gas flow:
 
hh
b (ig + iv,i Y ) + vb (ig + iv,i Y ) = iv,f hm (Y Yp ) + (T Tp ) S (10)
t x g

3.3 Simplified Energy Balances in Terms of Temperatures

Defining dry-basis specific heats, an effective (apparent) density and introducing the heats of sorption, respectively as:
 
g c = g cp g + Y cp v (11)

e ce = b (cs + cl W ) + g (cp g + Yp cp v ) (1 b ) p (12)

e = b + (1 + b ) p g (13)
ipsor = iv, il , iisor = iv,i iv, , isor = ipsor + iisor = iv,i il (14)

Using the definitions of specific heats for perfect gases and incompressible substances, expanding equations (9) and
(10), using and multiplying the mass conservation equations (4) and (5) by iv, and iv,i , for particles and process gas flow
equations, respectively, yields:
 
e Tp i hh b p W
ce = isor hm (Y Yp ) + (T Tp ) S + i (15)
g t g g sor t
   
T T i hh
c b + vb = (1 ) isor hm (Y Yp ) (T Tp ) S (16)
t x g

where is the fraction of iisor that contributes directly to heating (or cooling) the process gas flow; conversely, 1 is
the fraction of iisor that contributes directly to heating (or cooling) the adsorbent particles.

4. NORMALIZATION

4.1 Dimensionless groups

The first dimensionless groups are the dimensionless dependent and independent variables involved in the studied
problem:

(Tp Tref ) (T Tref ) Yp Y W

Tp = , T = , Yp = , Y = , W = (17)
T T Ymax Ymax Wmax
t x
t = , x = (18)
L

where T = Tmax Tmin and Tref = Tmin .

The next groups are the dimensionless parameters, such as the dimensionless dwell time (residence period), volumetric
and heat capacities ratios, dimensionless numbers of transfer units, dimensionless concentration of water in the adsorbent,
dimensionless heat of adsorption and heat capacity ratios, expressed respectively as:

L res V cb b L Ax
res = b , res = , Vr = , V = vb Ax , Cr = (19)
vb
Proceedings of the ENCIT 2012 14th Brazilian Congress of Thermal Sciences and Engineering
Copyright
c 2012 by ABCM November 18-22, 2012, Rio de Janeiro, RJ, Brazil

Vr Cr c e ce hh As
C = g v b Ax c p g , Vr = , Cr = , Xi = , Xp = , Nhtu = (20)
V C c pg b cb C

hm As b Wmax g Ymax g Ymax

Nm
tu = , = , ip p
sor = isor , ii i
sor = isor (21)
V g Ymax b cb T b cb T

4.2 Dimensionless governing equations

For the mass balance of the particles, the dimensionless equation yields:

W Yp
Vr + (1  b )  p V
r = Nm
tu (Y Yp ) (22)
t t

For the mass balance of the process gas flow, the dimensionless equation is written as:

Y Y
res + = Nm
tu (Yp Y ) (23)
t x

For the energy balance for the particles, the dimensionless equation is given by:

Tp Nm
tu i Nhtu p W

p = isor (Y Yp ) + (T Tp ) + isor (24)
t Vr Cr t

For the energy balance of the process gas flow, the dimensionless equation results:

T T Cr i
 

i res + = ( 1) Nm
tu i (Y Y ) + Nhtu (Tp T ) (25)
t x Vr sor p

4.3 Performance Assessment

The performance of the dehydration process is assessed by the dehydration effectiveness (m ) and it has been employed
for assessing the performance of desiccant wheels (Nbrega and Brum, 2011; Niu and Zhang, 2002). The formulation

comprises a measure of the level of dehydration of the gas stream with the ideal parameter Yout,min = 0:

(Yin Yout

)
m = (26)
(Yin Yout,min )

5. RESULTS AND DISCUSSION

To solve the equations, it was used the Finite Volume Method (Patankar, 1980) with a uniformly spaced mesh following
the methodology presented in Sphaier and Worek (2009), and the entire implementation was done in the Mathematica
system (Wolfram, 2003). To express the relationship between the quantity adsorbed W , humidity and temperature of gas
in equilibrium with this phase, we used the following adsorption isotherm:

1 Yp pop v,g Mv
W Tp , Yp =


, = (Tp , Yp ) = v,g , rM = (27)
1 r + r/ rM + Yp pvs (Tp ) Mg

where is the relative humidity of natural gas presented in references (ASHRAE, 2005), r is the separation factor
v,g
of the adsorption isotherm (Basmadjian, 1997) and rM is the relation between vapor and dry natural gas molecular
masses (Friend et al., 1989; Kohl and Nielsen, 1997).
The density of the gas was calculated assuming pure methane gas with ideal gas behavior. Table 1 presents the
numerical data (engel and Boles, 1998) used in the simulations assuming silica gel as solid dehydration medium (Hubard,
1954).
Proceedings of the ENCIT 2012 14th Brazilian Congress of Thermal Sciences and Engineering
Copyright
c 2012 by ABCM November 18-22, 2012, Rio de Janeiro, RJ, Brazil

Table 1. Values Used in the Numerical Solution

Parameters Symbols Values
Minimum Temperature (K) Tmin 300
Specific Mass of Methane (kg/m3 ) g 5.512106 pop
Specific Heat of Methane (J/kgK) cpg 2253.7
Specific Heat of Adsorbent (J/kgK) cb , cs 921
Specific Heat of Liquid Water (J/kgK) cl 4180
Specific Heat of Water Vapor (J/kgK) cp v 1872.3
Maximum Concentration of Water on Adsorbent (kg/kg) Wmax 0.45
Molecular Mass of Methane (kg/kmol) Mg 16.043
Molecular Mass of Water (kg/kmol) Mv 18.015
Methane Gas Constant (J/kgK) Rg 518.35
Particle Porosity p 0.366
Bed Porosity b 0.3
Maximum Concentration of Vapor (g/kg) Ymax 32.1
Adsorption Heat (J/kg H2 O) isor 2.7 106
Heat Capacity Ratio Cr 101
Volumetric Capacity Ratio Vr 5701 Cr

Dimensionless Period of Residence res 0.3 Vr
Dimensionless Concentration of Water in Adsorbent 19557
Dimensionless Heat of Adsorption ii
sor 0

The dimensionless inlet values, Yin and Tin , can assume different values for each process, but for the studied cases it

was assumed Yin = 1 and Tin = 0 at adsorption process and Yin = 1 and Tin = 1 at regeneration process, as observed
in figure 1. For the adsorption processes, the inlet condition describes that the fluid is totally saturated with water and the
temperature is the minimum established. For the regeneration process, the absolute humidity of the gas is the same as the
adsorption process inlet, however the temperature is the maximum stipulated.
For the first studied case with separation factor r = 0.1 and maximum temperature Tmax = 400 K as shown in
figure 2, the dehydration effectiveness (m ) increases with pressure (p) and number of transfer unit (Nhtu ). Nearly by
Nhtu = 4, it is observed a non increasing behavior of m , so one can considered it as a best point operation. At some
pressure value there is not significant m increase, as result the pressure can be limited to an operation value with minimum
waste of compression power.

Tmax = 400 K, r = 0.1

1.0

0.8

0.6
p = 1 atm
m

0.4
p = 3 atm

0.2 p = 6 atm

0.0
0 5 10 15 20 25
NTUh
Figure 2. Variation of m with respect to Nhtu for r = 0.1

In figure 3 with separation factor r = 1 and Tmax = 400 K, the m also increases with p and Nhtu . About Nhtu = 4,
Proceedings of the ENCIT 2012 14th Brazilian Congress of Thermal Sciences and Engineering
Copyright
c 2012 by ABCM November 18-22, 2012, Rio de Janeiro, RJ, Brazil

it is observed a non increasing behavior of m , so one can considered it as a good region of operation. At some pressure
value there is not significant m increase, as result the pressure can be limited to an operation value with minimum waste
of compression power. Relatively to the case shown in figure 3, it is identified a better m response to higher pressures,
thus a solid desiccant with r = 1 is foremost to operate.

Tmax = 400 K, r = 1
1.0

0.8

0.6 p = 1 atm
m

p = 3 atm
0.4
p = 6 atm
0.2

0.0
0 5 10 15 20 25
NTUh
Figure 3. Variation of m with respect to Nhtu for r = 1

For the last case as shown in figure 4 with separation factor r = 10 and Tmax = 400 K, it is noted one more time that
the m increases with p and Nhtu . About Nhtu = 5, it is observed a constante behavior of m , so one can considered it as
a good operation parameter. In this case, the pressure variation has more significance than the last two cases, however for
lower pressures the m is not relatively fine.

Tmax = 400 K, r = 10
1.0

0.8

0.6
p = 1 atm
m

0.4 p = 3 atm

0.2 p = 6 atm

0.0
0 5 10 15 20 25
NTUh
Figure 4. Variation of m with respect to Nhtu for r = 10

6. CONCLUSIONS

This study presented a simple mathematical model for simulating the process of natural gas dehydration using solid
desiccants. A system of one-dimensional governing equations for heat and mass transfer within the adsorbent material
were obtained. Dimensionless groups associated to this problem were presented and the formulation was normalized using
these groups. A numerical solution of the problem was implemented using the Finite Volumes Method combined with
the Method of Lines. Then, simulation results were carried-out to illustrate the effect of varying the operation pressure
on the dehydration effectiveness. The results show that for the simulated conditions, bigger pressures results in better
Proceedings of the ENCIT 2012 14th Brazilian Congress of Thermal Sciences and Engineering
Copyright
c 2012 by ABCM November 18-22, 2012, Rio de Janeiro, RJ, Brazil

dehydration effectiveness. For most studied cases, there are betters regions to operate such as between Nhtu = 4 and
Nhtu = 5. For higher operation pressures, it is better to use solid desiccants with higher r to obtain greater m , however
for lower pressures, it is recommended to use lower r to gain greater m . In spite of the relevance of this study, the results
are still preliminary and future research should definitely be conducted.

7. ACKNOWLEDGEMENTS

Sincere thanks to FAPERJ, CAPES, CNPQ and Universidade Federal Fluminense.

8. REFERENCES

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9. RESPONSIBILITY NOTICE

The authors are the only responsible for the printed material included in this paper.