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Available at www.sciencedirect.com

results for the isobaric refueling period

a

India Science Lab, General Motors Global R & D, Creator Building, International Technology Park, Bangalore 560066, India

b

Chemical Sciences and Material Systems Lab, General Motors Global R & D, Warren Technical Center Campus, 30500 Mound Road, Warren,

MI 48090, USA

Article history: We have developed 3-D model equations for a cryo-adsorption hydrogen storage tank,

Received 1 December 2009 where the energy balance accommodates the temperature and pressure variation of all the

Received in revised form thermodynamic properties. We then reduce the 3-D model to the 1-D isobaric system and

7 January 2010 study the isobaric refueling period, for simplified geometry and charging conditions. The

Accepted 8 January 2010 hydrogen capacity evolution predicted by the 1-D axial bed model is significantly different

Available online 13 February 2010 than that predicted by the lumped-parameter model because of the presence of sharp

temperature gradients during refueling. The 1-D model predicts a higher hydrogen capacity

Keywords: than the lumped-parameter model. This observation can be rationalized by the fact that

Hydrogen storage modeling a bed with temperature gradients on equilibration should desorb gas, whenever the

Cryogenic adsorption adsorbed phase entropy is lower than the gas phase entropy. The 1-D analysis of the

Metal-organic frameworks isobaric refueling period does not show any significant difference in hydrogen capacity

Refueling evolution among the axial, single and multicartridge annular bed designs. Hence, a multi-

cartridge annular design, though giving a slightly lower pressure drop, does not offer any

heat and mass transfer enhancement over the single cartridge design. And, the single

cartridge annular design appears to be optimal.

ª 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

20 bar and about 80 K, and a fuel cell operating at about 4 bar.

On-board storage of hydrogen by adsorption at low tempera- The four processes occurring in a cryo-adsorber fuel-tank are:

tures (around 77 K, liquid nitrogen temperature) and moder-

ately high pressures (less than 60 bar) is considered viable and Refueling – A depleted fuel-tank at low pressure (say 4 bar or

competitive with other storage technologies including liquid 1.1 bar) and higher temperature (say 120–140 K) is charged with

hydrogen, compressed gas, and metallic or complex hydrides hydrogen. Heat released during adsorption is removed by the

[1]. Nanoporous metal-organic frameworks (MOFs) as adsor- recirculation of cool hydrogen gas entering at 80 K or below.

bents offer good gravimetric capacity and fast and reversible Discharge – When the vehicle is in motion, the fuel cell stack

kinetics. For example, MOF-5 has a reversible capacity of about demands are met by desorbing hydrogen from the cryo-

6 wt% at 77 K and 50 bar [2]. MOF-5 as an adsorbent material adsorber bed. Desorption is enhanced by the recirculation of

has been studied extensively and we consider it to assess the hot hydrogen gas. The tank pressure may eventually drop to

tank performance in our previous [3] and current works. say 4 bar or 1.1 bar.

E-mail addresses: senthil.v.kumar@gmail.com, senthil.vadivelu@gm.com (V.S. Kumar).

0360-3199/$ – see front matter ª 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

doi:10.1016/j.ijhydene.2010.01.025

Author's personal copy

aPg, kTg isobaric thermal expansion coefficient and

T, P temperature and pressure, K, bar

isothermal compressibility, 1/K, 1/bar

L, R, dp length and radius of the adsorbent bed, pellet

Hg, Hq, Hs specific enthalpy of gas, adsorbate and

diameter, m

adsorbent, J/kg

ms, Vb mass and volume of the adsorbent bed, kg, m3

CPg, CPs specific heat capacity of gas and adsorbent, J/kg/K

U, Q superficial gas velocity and volumetric flow rate

q, q* excess adsorbate concentration and its

through the bed, m/s, m3/s

equilibrium value, kg H2/kg adsorbent

3p, 3b, 3t pellet, bed and total porosities, 3t ¼ 3b þ (1 3b)3p,

qm, b the two Langmuir parameter, kg/kg, 1/bar

m3/m3

DHa heat of adsorption, J/kg H2 adsorbed

rs, rp, rb skeletal, pellet and bed densities, rp ¼ rs(1 3p),

leff effective thermal conductivity of the adsorbent

rb ¼ rp(1 3b), kg/m3

bed, W/m/K

rg, vg gas density and specific volume, vg ¼ 1/rg, kg/m3,

m3/kg

Dormancy & Venting – While the vehicle is parked, due to non-ideal, and its specific heat capacity varies significantly

continuous heat leak into the fuel-tank, its pressure builds with temperature. Hence, in this work we develop a generic

up to vent pressure, say 25 bar, and gas is vented to the fuel form of the 3-D model, which allows variation in all the

cell (or atmosphere). The process of venting is also called thermodynamic properties. We then reduce the 3-D model to

boil-off, in analogy with liquid hydrogen storage systems. the 1-D isobaric system and study the isobaric refueling

The time period till the start of venting is called dormancy. period, for simplified geometry and charging conditions. We

study only the isobaric period of refueling herein, since the

Interestingly these fuel-tank processes occur over different isobaric period is much longer than the initial adsorption

time scales: refueling over a few minutes, discharge over a few period. We have solved these 1-D equations using finite

hours, dormancy over a few days, and venting over a few element method, using the commercial package COMSOLª.

weeks. In [3] we had shown that even the fastest process, i.e.

refueling, is quasi-static i.e. local equilibrium conditions

prevail. Hence, the slower processes are obviously quasi-

static. When the molecular processes are fast, slow processes

are expected to have negligible internal gradients and are

generally amenable for a lumped-parameter analysis. Hence,

we had developed a quasi-static lumped-parameter model for

the cryo-adsorber fuel-tank in [3]. However, one might antic-

ipate that higher dimensional models might be required,

especially for the fastest process i.e. refueling. The refueling

period could be divided into two periods:

pressure is exposed to the high pressure supply, there are

initial pressure transients due to the hydrodynamic filling

of the bed and a rapid initial adsorption leading to

a temperature spike in the bed. Typically this period lasts

a few seconds.

2. Isobaric adsorption period. During which pressure transients

are negligible and the bed is getting cooled by and adsorbs

further hydrogen from the recirculating cool hydrogen gas.

This period is considered isobaric, since the bed is already

filled hydrodynamically in the former period and the pres-

sure drop across the highly porous beds are generally

negligible. Typically this period extends over a few minutes.

swing adsorption are widely reported in literature [4,5]. These

models generally involve approximations like ideal gas

behavior, constant specific heat capacities, constant heat of

adsorption etc. However, for example, we know that hydrogen

at high pressures and cryogenic temperatures is quite Fig. 1 – Longitudinal view of an axial packed bed.

Author's personal copy

ered in this work: axial, single cartridge annular and the

multicartridge annular beds. Section 3 describes the compu-

tation of steady-state pressure drop across these bed designs.

Section 4 describes the 3-D model development, and in

Section 5 it is reduced to the 1-D isobaric system. Section 6 Distribution tube

describes the 1-D axial bed results, and compares these

results with the lumped-parameter model predictions.

Section 7 describes the results for the annular bed designs and Packed bed

compares the three designs. Section 8 studies the effect of

feed flow rate on refueling time. The Appendix describes the Collection tube

various input data used in the 1-D isobaric refueling period

simulations. And, the support material details the derivation

Insulation

of the basic forms of transient mass and energy balances used

in Section 5.

2. Packed-bed designs

Exit

A fixed mass of adsorbent can be packed within a pressure Fig. 2 – Longitudinal and cross-sectional views of a single

vessel in various ways. The classical style is the axial bed, annular packed bed.

shown in Fig. 1, where the gas flows axially through a cylin-

drical bed. An alternative design, giving lower pressure drop,

is the annular backed bed, shown in Fig. 2, where the gas is in its pores. The gaseous hydrogen stored in the dead-spaces

ideally expected to flow radially. Hence, an annular bed design around the packed bed but within the pressure vessel (for

is often used in industrial adsorption or catalytic systems; see example, space between the cartridges, header and collector

for example the metal hydride beds [6,7], adsorption refrig- spaces etc.) are not considered.

eration systems [8], catalytic reactors [9], chromatographic

columns [10] etc. However, it is well-known, both through

simulations and experiments that annular packed beds are

3. Pressure drops for three packed-bed

more prone to flow maldistribution than axial packed beds

designs

[11,12]. The presence and effect of flow maldistribution can be

systematically studied only in a two-dimensional model. The

We compute the steady-state pressure drop for a non-

CFD studies [13,14] show that having the inlet and outlet ports

adsorbing hydrogen gas flow of 120 g/s through these three

on the same side, such that the inner and outer flows are anti-

beds at 20 bar and 80 K. To compute the pressure drop across

parallel gives low flow maldistribution. Note that this design is

different from that given in Fig. 2. Such design variations will

be considered in our future two-dimensional studies.

Instead of arranging the whole bed as a single annular bed,

one could arrange the adsorbent bed into multiple cartridges,

as in Fig. 3. In this work, we study the relative advantages of

these three different designs, especially in the context of

isobaric refueling period. In particular, we seek to answer the

following questions: for a fixed mass of adsorbent, is there any

process advantage (in heat and mass transfer sense) in

increasing the number of cartridges or is there an optimum

number of cartridges? These questions cannot be addressed

within the premise of a lumped-parameter model, since all

the designs are equivalent at that level, and we need at least

a one dimensional model.

In our earlier work [3] we had considered a MOF of bulk

density 385.05 kg/m3 and a bed of 90.37 kg mass and 0.2347 m3

volume. We consider packed beds of the same mass and

volume in this study. For all the designs we fix the bed length

at 1 m and back calculate the bed diameter from the bed

volume. For single and 7-cartridge annular beds, assuming the

distribution diameter to be 1 cm, the outer bed diameters are

respectively 0.5467 m and 0.2068 m. While comparing

different bed designs, we consider only the hydrogen capacity Fig. 3 – Cross-sectional view of a 7-cartridge annular

in the bed, both adsorbed hydrogen and the gaseous hydrogen packed bed.

Author's personal copy

a bed for an unidirectional axial flow the widely used form of values for bed density and total porosity, we have the general

Ergun equation is [15, p. 191], form of mass balance as:

DP vq vrg / !

¼ amg U þ brg U2 ; (1) rb þ 3t þ V $ U rg ¼ 0: (9)

L vt vt

where Expanding the gradient term we have

150ð1 3b Þ2 rb

vq

þ 3t

vrg ! / / !

þ U $ V rg þ rg ðV $ U Þ ¼ 0: (10)

a¼ (2) vt vt

33b d2p

gas and the adsorbate are in local equilibrium. This statement

1:75ð1 3b Þ implies that any change in the property of gas or the adsorbate

b¼ : (3)

33b dp at any location is solely due to the temperature and pressure

As in [3] we assume a bed porosity of 3b ¼ 0.36 and a pellet change at that location. For example, with gas density we have

diameter of dp ¼ 1.0 mm. From the NIST web book [16], we get

rg ð!

r ; tÞ ¼ rg ½Tð!

r ; tÞ; Pð!

r ; tÞ; (11)

hydrogen gas density and viscosity at 80 K and 20 bar as

rg ¼ 6.2070 kg/m3 and mg ¼ 3.7453 106 Pa s. Using these

and then the temporal and spatial derivatives of density could

values, we get a pressure drop of 1417.33 Pa across the axial

be written in terms of those of temperature and pressure

bed.

using the chain rule as:

Ergun equation is generalized for a three dimensional flow

in a differential element as [17, p. 48], vrg vT vP

¼ rg aPg þ rg kTg ; (12)

vt vt vt

/ ! !!

V P ¼ amg U þ brg j U j U : (4)

and

For a radial flow in a differential element this equation

/ / /

becomes V rg ¼ rg aPg V T þ rg kTg V P: (13)

¼ amg Ur þ brg U2r ; (5)

vr approximated to the equilibrium adsorbate concentration at

where that location i.e.

Q r ; tÞzq ½Tð!

qð! r ; tÞ; Pð!

r ; tÞ; (14)

Ur ¼ (6)

2prL

and

is the radial superficial velocity. Note that in a radial flow the

superficial velocity varies with radial location. Integrating this vq vq

z : (15)

equation for an annular bed from the inner radius ri to the vt vt

outer radius ro gives The Langmuir adsorption isotherm is

2

Q ro Q 1 1 q bP

Po ¼ Pi amg ln brg : (7) ¼ : (16)

2pL ri 2pL ri ro qm 1 þ bP

Using this equation, the pressure drop across a single and Temperature dependence of the two Langmuir parameters are

seven cartridge annular beds are 337.72 Pa and 12.05 Pa, represented as in [3] as

respectively. These calculations show that there is significant

B

reduction in pressure drop as we move from axial bed design b ¼ b0 exp (17)

T

to single cartridge annular bed design to seven cartridge

annular bed design. and

qm0

qm ¼ ; (18)

f ðTÞ

4. Development of 3-D model equations with

Then, we have

The basic form of the transient mass balance (derivation

details are in the supporting material) is vq vq vT vq vP

¼ þ

vt vT P vt vP T vt

v / !

0

r q þ 3t rg þ V $ U rg ¼ 0: (8) f ðTÞ B vT q vP

vt b ¼ q þ þ ; (20)

2

f ðTÞ ð1 þ bPÞT vt ð1 þ bPÞP vt

The adsorbate diffusion in and out of the element is generally

negligible compared to the convective component, and hence see [3] for the intermediate steps. Using these expressions in

it is typically neglected in the literature [4]. Assuming constant the mass balance, we have

Author's personal copy

a11 þ a12 rg aPg U $ V T þ rg kTg U $ V P þ rg ðV $ U Þ ¼ 0; (21) 3t rg þ rb q þ rb þ rb DHa 3t þ rg U $ V Hg

vt vt vt vt vt vt vt

where

/ / vq vrg / !

þ V $ leff V T þ Hg rb þ 3t þ V $ U rg

vt vt

0 ¼ 0: (29)

f ðTÞ B

a11 ¼ rb q þ rg aPg 3t (22)

f ðTÞ ð1 þ bPÞT2 Noting that the coefficient of gas enthalpy in the above

equation is identically zero from the mass balance equation

and

(9), we have

vH

rb q g vHs vq vP ! /

a12 ¼ þ rg kTg 3t : (23) 3t rg þ rb q þ rb þ rb DHa 3t þ rg U $ V Hg

ð1 þ bPÞP vt vt vt vt

/ /

þ V $ leff V T ¼ 0: (30)

the numerical evolution of the above equation is obviously

4.2. Transient energy balance

independent of the reference states assumed for computing

the enthalpies.

The basic form of the transient energy balance (derivation

Now, as in mass balance, let us introduce the quasi-static

details are in the supporting material, see also [15, p. 335]) is

approximations. Assuming local equilibrium we have

v vP / !

vt

3t rg Hg þ rb qHq þ rb Hs 3t þ V $ U rg Hg

vt Hx ð!

r ; tÞ ¼ Hx ½Tð!

r ; tÞ; Pð!

r ; tÞ; (31)

/ /

þ V $ leff V T ¼ 0: (24) and hence, we have

¼ CPg þ vg 1 aPg T ; (32)

packed beds, local thermal equilibrium could typically be vt vt vt

assumed for physisorption scenarios and hence one single

energy balance could be used, instead of a separate energy / / /

V Hg ¼ CPg V T þ vg 1 aPg T V P; (33)

balance for the gas and solid phases, further details are

available in [3, Section 4].

vHs vT vP

Assuming constant bed density and total porosity, the ¼ CPs þ vs ; (34)

vt vt vt

above equation is expanded as follows:

see for example Section 2.1 of Ahluwalia and Peng [18].

vHg vrg vHq vq vHs vP ! / Using these results in Eq. (30) and simplifying we have,

3t rg þ 3t Hg þ rb q þ rb Hq þ rb 3t þ rg U $ V Hg

vt vt vt vt vt vt

/ ! / / vT vP ! / ! /

þ Hg V $ U rg þ V $ leff V T a21 þ a22 þ rg CPg U $ V T þ 1 aPg T U $ V P

vt vt

/ /

¼ 0: þ V $ leff V T ¼ 0; (35)

(25)

where

In this form we see that the gas and adsorbate enthalpies 0

f ðTÞ B

appear as coefficients of derivatives, which at the outset could a21 ¼ 3t rg þ rb q CPg þ rb CPs q rb DHa þ ;

absurdly mean that the numerical evolution of this equation f ðTÞ ð1 þ bPÞT2

depends on the reference state assumed for the computation (36)

of these enthalpies. We will now demonstrate that it is not so. and

The adsorbate enthalpy is obtained from the definition of heat

of adsorption as q rb DHa

a22 ¼ 3t þ rb vg q 1 aPg T þ ð1 23t Þ þ : (37)

ð1 þ bPÞP

Hq ¼ Hg þ DHa : (26)

We have used

This study assumes a constant average heat of adsorption,

independent of temperature and pressure. Hence,

rb

r b vs ¼ ¼ 1 3t (38)

vHq vHg rs

z : (27) during the above simplifications.

vt vt

Note that this development of transient energy balance

Using these results, we have

does not contain the heat leak into the system. The heat leak

vHg vrg vHg vq vHs vP term should be considered in the energy balance for the

3t rg þ 3t Hg þ rb q þ rb Hg þ DHa þ rb 3t

vt vt vt vt vt vt structural steel domain and not the adsorbent bed domain,

! / / ! / /

þ rg U $ V Hg þ Hg V $ U rg þ V $ leff V T with a heat flux continuity boundary condition at the interface

allowing the heat exchange between the two domains. The

¼ 0: (28)

energy balance developed above is only for an element in the

Collecting all the terms having gas enthalpy as their coeffi- adsorbent bed. For the system considered herein, during

cient gives refueling or discharge, the heat effects due to adsorption or

Author's personal copy

U ¼ 2ð V PÞ

the tank. Hence, the heat leak can be neglected. For example, rﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ (42)

/

for an adsorbent with 4 kJ/mol heat of adsorption, adsorbing amg þ a2 m2g þ 4brg jV Pj:

5 kg of hydrogen in 5 min, the average rate of heat generation

is about 33.3 kW. While typical heat leaks are of the order of This expression is used in the mass and energy balances Eqs.

a few Watts. Thus, for these two fast processes, i.e. refueling (21) and (35), to eliminate superficial velocity in terms of

and discharge, it is not necessary to draw two separate energy pressure gradient. Then, we solve the coupled mass and

balances for the structural steel and adsorbent bed domains. energy balances for the variables ( T,P).

However, to estimate the impact of heat leak, one could

4.5. Comparison with literature

‘‘numerically’’ add that heat to the feed gas and study the bed

dynamics. For the slow processes, i.e. dormancy and venting,

The mass balance and steady-state momentum equations

the lumped-parameter description uses a single energy

described in Mota et al. [4] are identical to our Eqs. (9) and (4).

balance which contains the heat leak term. In fact in these

The energy balance equation of [4], in our notation is

processes, the heat leak drives the tank dynamics.

4.3. Steady-state momentum balance v h i vq vP vT / !

CPg 3t rg þ rb q T þ rb DHa 3t þ rb CPs þ CPg V $ Trg U

vt vt vt vt

/ /

Using Ergun equation (4) i.e. the steady-state momentum V $ leff V T

equation locally for the pressurization of adsorber gives ¼ 0:

numerical results comparable to that of the unsteady (43)

mechanical energy balance (which is merely a dot product of

the unsteady momentum balance equation and velocity) [19]. We will recover the above equation from Eq. (24) by stating the

Hence, in adsorption literature it is common to use the Ergun assumptions systematically. Using the adsorbate enthalpy

equation locally even when flow and pressure transients exist. definition Eq. (26), assuming a constant average heat of

adsorption Eq. (27), and a constant bed density, Eq. (24)

4.4. General solution procedure simplifies to

g vq vHs vP

Hg 3t rg þ rb q þ 3t rg þ rb q þ rb DHa þ rb 3t

We solve the mass and energy balances, Eqs. (21) and (35), vt vt vt vt vt

!

coupled with Ergun equation (4) for the variables ð U ; T; PÞ. / ! / /

þ V $ U rg Hg V $ leff V T ¼ 0: (44)

Simplistically, it could be stated that the mass balance

describes the flow rate or velocity changes due to adsorption,

the energy balance describes the temperature changes due to Assuming that the effect of pressure on the gas and solid

the heat released on adsorption, and the Ergun equation enthalpies are negligible in the given operating range of

describing the pressure drop due to flow. The coupled effects pressures, and that the specific heat capacities of the gas and

like pressure changes in the gas phase due to adsorption, flow solid are constants i.e. they do not vary with temperature, we

rate or density changes due to temperature gradient etc. are of have,

course built into the model exactly. dHg ¼ CPg dT; (45)

Ergun equation expresses pressure gradient in terms of the gives

superficial velocity. It can be inverted to express superficial

velocity in terms of the pressure gradient as follows. Taking Hg ¼ Hg0 þ CPg ðT T0 Þ: (46)

modulus of Eq. (4) gives Similarly, for the adsorbent enthalpy we have

/ ! !

jV Pj ¼ amg j U j þ brg j U j2 : (39) dHs ¼ CPs dT: (47)

! Using these results in Eq. (44), and simplifying we have

This quadratic equation in j U j is solved to get

/ !

rﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ v v h i

! /

Hg0 CPg T0 3t rg þrb q þ V $ U rg þCPg 3t rg þrb q T

j U j ¼ amg þ a2 m2g þ 4brg jV Pj vt vt

(40) vq vT vP / !

2brg : þrb DHa þrb CPs 3t þCPg V $ U rg T

vt vt vt

Here, we use the positive sign for the square root so that the / /

V $ leff V T ¼0: (48)

modulus is non-negative. This expression is substituted in the

vector equation and rearranged to get Note that the above equation is identical to that in [4] except

for the first term, which is identically zero from the mass

/ ! !! ! !

V P ¼ amg U þ brg j U j U ¼ amg þ brg j U j U balance equation (9). Thus, our model reduces to that of [4]

rﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ when the effect of pressure on enthalpies is negligible and

0 / 1

amg þ a2 m2g þ 4brg jV Pj ! specific heat capacities and heat of adsorption are constant.

¼@ AU: ð41Þ The model developed herein is quite generic with rigorous

2

accounting of the temperature and pressure dependence of all

Hence, we have the thermodynamic properties.

Author's personal copy

5. Reduction of 3-D model to 1-D isobaric the literature; see for example [21,22]. However, we observe that

system the Danckwerts’ boundary condition is used widely in the

adsorption literature, see for example [23,24].

For an isobaric system, we drop the Ergun equation (4) and the

temporal and spatial derivatives of pressure in the mass and

energy balances (21) and (35), and solve the coupled mass and

! 6. Results & discussion for axial bed design

energy balances for ð U ; TÞ i.e. mass balance describes the flow

rate or velocity changes due to adsorption and energy balance

The whole bed is initially at 140 K. As the 80 K feed gas starts

describes the temperature changes due to the heat released

blowing through the bed simultaneous cooling and adsorption

on adsorption. For the isobaric system, mass balance equation

takes place. For example, in the temperature evolution in

(21) reduces to

Fig. 4 at t ¼ 0.5 min, one could see three regions existing within

vT ! / / ! the bed. The region 0–A is the part of the bed which has

a11 rg aPg U $ V T þ rg ðV $ U Þ ¼ 0; (49)

vt already cooled to 80 K and it has got saturated to its capacity at

where a11 is given by Eq. (22). For unidirectional axial flow, it 80 K. The region A–B is the region where simultaneous cooling

reduces to and adsorption are currently taking place. Here, the temper-

atures are between the initial bed temperature and the feed

vT vT vUx gas temperature. As the gas flows through this region it gets

a11 rg aPg Ux þ rg ¼ 0: (50)

vt vx vx heated up. At about point B, the gas gets heated up to 140 K,

For unidirectional radial flow, in cylindrical coordinates, it

reduces to

vT vT 1 v a

a11 rg aPg Ur þ rg ðrUr Þ ¼ 0: (51) 140

vt vr r vr B

t = 0.5 min

Expanding the last term gives

1.0 min

vT vT vUr rg Ur 120

a11 rg aPg Ur þ rg þ ¼ 0: (52)

vt vr vr r

1.5 min

T (K)

assumption of constant effective thermal conductivity, 2.0 min

reduces to 100

2.5 min

vT ! /

a21 þ rg CPg U $ V T leff V2 T ¼ 0; (53) 3.0 min

vt A

80

where a21 is given by Eq. (36). For unidirectional axial flow it

reduces to 0 0.5 1

x (m)

vT vT v2 T

a21 þ rg CPg Ux leff 2 ¼ 0: (54)

vt vx vx

b 120

For unidirectional radial flow, in cylindrical coordinates, it A 3.0 min

reduces to

2.5 min

mass flow rate (g/s)

vT vT 1 v vT

a21 þ rg CPg Ur leff r ¼ 0: (55)

vt vr r vr vr 110 2.0 min

Expanding the last term and rearranging we have 1.5 min

vT leff vT v2 T

a21 þ rg CPg Ur leff 2 ¼ 0: (56)

100

1.0 min

vt r vr vr

We solve the coupled mass and energy balance equations in t = 0.5 min

COMSOLª, with the initial conditions: U ¼ 0 and T ¼ T0, all over B

the domain at t ¼ 0, and the boundary conditions U ¼ Uf and T ¼ Tf

90

at the feed side, and vT=vx ¼ 0 or vT=vr ¼ 0 at the exit side. This 0 0.5 1

Neumann-type exit boundary condition for flow systems is x (m)

popularly known as the Danckwerts’ boundary condition [20].

Theoretically, this boundary condition can be applied only for Fig. 4 – (a) Temperature and (b) mass flow rate evolution in an

a steady system. For an unsteady system, this boundary condition axial flow bed. At t [ 0.5 min, the region 0–A is the saturated

is believed to suppress the gradients near the exit or induce region at feed temperature (80 K), the region A–B is the

numerical instability. However, in Section 6, we observe that adsorption zone where the bed is simultaneously cooling

there is no perceptible gradient suppression near exit in our (from 140 K to 80 K) and adsorbing, and the region B–1 is the

results, even when the adsorption front is moving out of the bed. non-adsorbing region at initial bed temperature (140 K).

Author's personal copy

the initial bed temperature. Hence, beyond point B, the gas Once we have the temperature and pressure evolution of the

just passes through the bed without cooling the bed any bed, integrating this expression over the entire length of the

further. Thus, in the region B–1 the bed is saturated at its bed gives the total hydrogen content of the bed at any time.

initial temperature. As time progresses region A–B, the We define the refueling time as the time at which the total

adsorption zone, moves downstream, leaving the bed hydrogen content of the bed is 5 kg (as mentioned in Section 2,

upstream fully saturated at 80 K. In the flow rate evolution we do not consider the gaseous hydrogen storage in the dead-

within the bed in Fig. 4, the same inferences could be seen. In spaces). For the isobaric axial bed, with a 120 g/s feed at 80 K

the adsorption zone A–B flow rate decreases due to adsorp- and 20 bar, we found the refueling time to be 135.8 s or

tion, and in the saturated zones 0–A and B–1 the flow rate 2.26 min. From Fig. 4, we can see that even by the end of

remains constant. Once the bed is fully saturated, gas merely refueling significant temperature gradients (about 40 K) exist

passes through the bed without change in flow rate. Fig. 5 within the bed. We will return to this observation later in this

shows the gas density and velocity evolution within the bed. section.

Density changes almost by a factor of two within the bed,

showing that the temperature dependence of thermodynamic

properties should be properly accounted. In the adsorption 6.1. Comparison of 1-D axial bed model and 0-D

zone, it is seen that the gas velocity increases steeply due to model results

sharp rise in temperature and consequent fall in density,

occurring within the adsorption zone. Fig. 6 shows the hydrogen capacity evolution predicted by the

Consider a circular slice of the axial bed at x, of elemental 1-D axial bed model and by the lumped-parameter model for

thickness Dx. Its total hydrogen content is obtained by summing the isobaric refueling period. The respective isobaric refueling

up the adsorbed phase and gas phase contributions as: times are 5.86 and 2.26 min. (Note that this 0-D result is

without the steel thermal mass and heat leak into the system,

pR2 Dxrb q ½Tðx; tÞ; Pðx; tÞ þ pR2 Dx3t rg ½Tðx; tÞ; Pðx; tÞ: (57)

so that the 0-D and 1-D results can be compared on a common

basis.) Such a large discrepancy in the hydrogen capacity

evolution and hence the refueling time is due to the significant

temperature gradients existing within the bed during the

isobaric refueling period, as seen in Fig. 4. We expect lesser

disparity between the 0-D and the 1-D models for slower

processes like discharge, dormancy and venting, since the

temperature gradients are expected to be milder.

In order to check this large discrepancy between the 0-D

and 1-D models during the isobaric refueling period, we

implemented a tanks-in-series model (not reported here).

A 0-D model is a single tank model, while the 1-D model is

equivalent to a sufficiently large number of tanks-in-series. In

fact, serially coupled 0-D models lead to a tanks-in-series

model. A tanks-in-series model showed that the two curves

shown in Fig. 6 can be smoothly interpolated as the number of

tanks increases from 1 to about 25.

4

H load (kg)

3

2

2 0−D

1

0 2 4 6

time (mins)

Fig. 5 – (a) Density and (b) superficial gas velocity evolution model and 1-D axial bed model during the isobaric

in an axial bed. refueling period.

Author's personal copy

Interestingly, from Fig. 6, we see that a 0-D model always from the bed and back into the gas phase, resulting in a slight

predicts lower hydrogen capacity than a 1-D model. The basic increase in the gas pressure.

distinction between the 0-D and 1-D models is the presence of Earlier in this section, we noted that even at the end of

temperature gradients in the latter. The presence of tempera- refueling significant temperature gradients, up to 40 K temper-

ture gradient in a 1-D model facilitates higher hydrogen ature difference exists within the bed. If the tank is isolated after

capacity than the 0-D model. This can be demonstrated by the refueling, with the temperature gradient slowly equilibrating, as

heuristic model shown in Fig. 7. Consider a kilogram of MOF at we note in this section, due to desorption back into the gas phase

80 K and another kilogram of MOF at 120 K being brought in there can be a slight overshoot in the tank pressure.

thermal contact. Assuming that their specific heat capacities

do not change significantly, we could say that the equilibrium

temperature of the composite block (neglecting for the 7. Results for annular bed designs and

moment, the energetics of adsorption or desorption) will be comparison of the three bed designs

about 100 K. From the adsorption data in the Appendix, one

could compute the excess adsorbed hydrogen at 20 bar in 1 kg Figs. 8 and 9 show the simulation results for the single cartridge

MOF at 80 K as 49.73 g, 1 kg of MOF at 120 K as 19.15 g and 2 kg of annular bed. Similar result hold seven cartridge annular bed

MOF at 100 K as 61.69 g. This calculation indicates that 7.19 g of (figures not shown), except that one seventh of the total flow is

hydrogen is returned to the gas phase when the temperature apportioned to each cartridge. The phenomenon of simulta-

gradients equilibrate within the composite block. Note that neous cooling and adsorption in annular beds is similar to that

this heuristic model does not capture the ‘‘secondary’’ effects in the axial bed, except for the geometric effects. From Fig. 8, it

which occur in reality, but illustrates the fact that a bed with can be seen that the adsorption zone moves rapidly near the

gradients has more adsorbed hydrogen than a bed at its inner diameter and slowly near the periphery. In Fig. 9, at long

equilibrated temperature, and thus it explains qualitatively the times the superficial gas velocity approaches a rectangular

discrepancy between the lumped-parameter and 1-D models. hyperbola, since for the non-adsorbing case the radial velocity

We can understand the above fact from a thermodynamic at any location is given by Eq. (6).

perspective too. If an adsorbent bed with internal temperature

gradients is isolated from its environment, the second law of

thermodynamics dictates that, on equilibration the system

a

140

entropy should increase. In most cases of gas physisorption,

the entropy of the adsorbed phase is lesser than that of the gas t = 0.5 min

phase. (If the adsorbed molecule dissociates on the surface, it

could favor an increase in entropy. But compared to the gas 120 1.0 min

phase, typically an adsorbed phase has much lower degrees of

T (K)

tion, more often the adsorbed phase entropy is lower than

that of the gas phase, leading to the commonly observed 100

2.0 min

exothermic adsorption. However, in special cases of disso-

ciative adsorption, if the entropy of the adsorbed phase is 2.5 min

higher than the fluid phase, there can be an endothermic

80

adsorption, see [25] for example.) Hence, on equilibration of 3.0 min

the temperature gradient some quantity of gas gets desorbed 0.05 0.1 0.15 0.2 0.25

r (m)

b

49.73 g H2 19.15 g H2 3.0 min

120

1 kg MOF 1 kg MOF

2.5 min

+

mass flow rate (g/s)

20 bar 20 bar 2.0 min

110

1.5 min

1.0 min

100

2 kg MOF Returned

at 100 K & to

t = 0.5 min

20 bar gas phase

61.69 g H2 7.19 g H2 90

0.05 0.1 0.15 0.2 0.25

r (m)

Fig. 7 – Heuristic model to demonstrate that a bed with

temperature gradients contains more adsorbed hydrogen Fig. 8 – (a) Temperature and (b) mass flow rate evolution in

than the bed at its average temperature. a single cartridge annular bed.

Author's personal copy

a

3.0 min

5

6

2.5 min

2.0 min 4

H load (kg)

(kg/m )

3

5

1.5 min 3

2

g

Axial

1.0 min Annular−1

4 2

Annular−7

t = 0.5 min

1

3 0 1 2 3

0.05 0.1 0.15 0.2 0.25 time (mins)

r (m)

Fig. 10 – Hydrogen capacity evolution among the different

packed-bed designs.

b 0.6

0.035

t = 0.5 min

0.03

flow maldistribution. The material cost increases with the

0.025 number of cartridges due to an increase in the mass of

0.4 1.0 min structural steel (increased diameter of pressure vessel and

U (m/s)

1.5 min Since flow is routed parallel in a multicartridge design, a flow

0.015 2.0 min

short circuit to the outer header in a cartridge will lead to

0.2 2.5 min

3.0 min significant flow maldistribution. As the number of cartridges

0.01

0.1 0.15 0.2 0.25 increases, the radial thickness of the bed in a cartridge

decreases and the chances of short circuiting or flow maldis-

tribution increase. Thus, a single cartridge annular bed offers

0 the advantages of radial flow system, without increasing the

0.05 0.1 0.15 0.2 0.25

material cost, fabrication complexity and flow maldistribution

r (m)

as in a multicartridge annular bed design.

Fig. 9 – (a) Density and (b) superficial gas velocity evolution

in a single cartridge annular bed.

Fig. 10 compares the hydrogen capacity among the three The results presented in above sections are for a constant feed

different packed-bed designs under consideration. Surpris- flow rate of 120 g/s. Now we present the refueling time at

ingly, there is negligible difference between the three designs different feed flow rates, for the three designs under consid-

in terms of hydrogen capacity evolution. This observation eration, in Table 1. Especially, in the axial bed results, we see

may be explained as follows: since the internal surface area that doubling the feed flow rate approximately halves the

within the pellets is very high, the adsorbent is already in refueling time. This scaling can be reasoned as follows: in this

intimate contact with the gas. Hence, rearranging the bed isobaric model, effective thermal conductivity of the bed is the

geometry does not make much difference in the rate at which only transport property which contains the dimension of

adsorption happens.

The primary motivation of this study was to answer the

following questions: for a fixed mass of adsorbent, is there any

process advantage in increasing the number of cartridges in Table 1 – Refueling time for the three bed designs at

an annular bed design and is there an optimum number of various feed flow rates.

cartridges during the isobaric refueling period? Since we do Feed flow Refueling time (s)

not find significant difference in the hydrogen capacity rate (g/s)

evolution, we infer that there is no significant heat and mass Axial bed Single cartridge Seven cartridge

annular bed annular bed

transfer advantage in moving from axial bed to single

cartridge annular bed or to seven cartridge annular bed 240 68.0 68.2 69.5

designs. Hence, the only difference in these design enhance- 120 136.1 136.9 141.8

ments is the decrease in pressure drop, as we noted in Section 60 272.4 275.7 294.0

30 545.6 557.8 625.0

3. Increase in the number of cartridges in an annular design

15 1093.6 1140.1 1380.5

results in higher material cost, fabrication complexity and

Author's personal copy

time, and all the remaining properties are thermodynamic or For all the bed designs, we find that the product of refueling

material properties which do not contain the dimension of time and feed flow rate is approximately constant for a given

time. When the effective thermal conductivity is low, as in feed temperature and pressure, i.e. doubling the feed flow rate

MOF, it does not significantly contribute to the thermal halves the refueling time. This scaling, though approximate,

diffusion of the adsorption front through the bed, leaving helps us in estimating the refueling time at arbitrary flow rates

superficial gas velocity or flow rate as the main variable given the refueling time at a flow rate.

scaling the refueling time. This scaling, though approximate,

helps us in estimating the refueling time at arbitrary feed flow

rates given the refueling time at a flow rate, since the product

Acknowledgments

of refueling time and feed flow rate is approximately

a constant, for a given feed temperature and pressure.

The authors would like to thank Raghunathan K, Michael

Compared to the axial bed, the single cartridge annular bed

Herrmann, Scott Jorgensen, Ulrich Eberle, Dieter Hasenauer,

design has a lower flow path length. As the number of

Rainer Immel, Gregory Meisner, Anne Dailly and Eric Poirier

cartridges increases, the radial thickness of the bed and hence

for technical data and/or valuable suggestions during the

the flow path length decreases. As flow path length decreases,

course of model development. Senthil Kumar would like to

the effect of thermal conductivity of the adsorbent on the

acknowledge constructive comments from his group

thermal diffusion of the adsorption front increases. Hence, we

members at India Science Lab during his presentations while

can see that the above scaling is less accurate as we move

the model development was in progress.

from the axial bed to single cartridge annular bed to seven

cartridge annular bed designs.

Appendix A. Simulation input data

9. Conclusions

We have employed the isobaric thermodynamic properties of

hydrogen gas at 20 bar from the NIST web book [16], in the

We have developed generalized 3-D model equations for the

temperature range 60–300 K, and fitted the expressions shown

cryo-adsorber, accommodating the temperature and pressure

below.

variation of all the thermodynamic properties. We have shown

that in the limiting case of negligible temperature and pressure vg ¼ vg0 þ vg1 T þ vg2 T2 þ vg3 T3 þ vg4 T4 (A.1)

dependence of the thermodynamic properties and a constant

heat of adsorption the derived energy balance equation reduces

vg0 ¼ 0:042693; vg1 ¼ 0:0028869; vg2 ¼ 5:5122e 6; vg3

to that reported in the literature. We then reduce the 3-D model

¼ 1:6913e 8; vg4 ¼ 1:9513e 11;

to the 1-D isobaric system and study the isobaric refueling

period, for simplified geometry and charging conditions. We where vg is the specific volume in m3/kg and T in K. We get the

have considered three packed-bed designs: an axial bed, single isobaric thermal expansion coefficient as

cartridge annular bed and a seven cartridge annular bed design.

The hydrogen capacity evolution predicted by the 1-D axial 1 vvg vg1 þ 2vg2 T þ 3vg3 T2 þ 4vg4 T3

aPg ¼ ¼ ; (A.2)

bed model is significantly different from that predicted by the vg vT P vg

lumped-parameter model, since sharp temperature gradients

exist within the bed during refueling. We observe that the lum- 2 exp fT2

f2 T

ped-parameter model predicts a lower hydrogen capacity than CPg ¼ f1 h i2 þ f3 þ f4

T 100

the 1-D model. This observation can be explained by the fact that exp fT2 1

due to the second law of thermodynamics, on equilibration an 2 2

T 100 100

isolated bed with temperature gradients should desorb gas þ f5 þf6 þ f7 ; (A.3)

100 T T

whenever the adsorbed phase entropy is lower than the gas phase

entropy. We expect lesser disparity for the slower processes, since f1 ¼ 4:788937e þ 03; f2 ¼ 5:229983e þ 02;

the temperature gradients are expected to be milder. f3 ¼ 1:496674e þ 04; f4 ¼ 1:204579e þ 03;

During the isobaric refueling period, we did not find any f5 ¼ 8:489895e þ 01; f6 ¼ 5:356621e þ 03;

significant difference in hydrogen capacity evolution among

f7 ¼ 2:625154e þ 03:

the axial bed, single cartridge annular bed and multicartridge

annular bed designs. From this observation we conclude the where CPg is the isobaric specific heat capacity in J kg1 K1

following: annular bed design gives a lower pressure drop and T in K.

than an axial bed design but it does not enhance the heat and

mass transfer processes. A multicartridge annular bed design A.2. Adsorption/adsorbent data

gives a lower pressure than a single cartridge annular bed

design but again increase in the number of cartridges does not For the Langmuir adsorption model, Eqs. (16)–(19), the parame-

enhance the heat and mass transfer processes. Hence a single ters used are: b0 ¼ 2.8164 108 Pa1, B ¼ 332.0158 K,

cartridge annular bed design offers the advantages of the qm0 ¼ 11.7134 10 kg H2/kg MOF and A ¼ 131.3231 106 K2.

2

annular bed design without increasing the material cost, As in [3], the remaining adsorbent parameters are

fabrication complexity and flow maldistribution. DHa ¼ 4:0 kJ=mol ¼ 2 106 J=kg, leff ¼ 0:32 W=m=K, and

Author's personal copy

X

8

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