Experimental

and Numerical

Adsorption/Desorption

Investigation

in Packed

under Ideal and Non-Ideal

of

Sorption

Beds

Flows

H. Mohamadinejad
Boeing Aerospace
Huntsville,

Company

AL

J. C. Knox
Marshall

Space Flight Center

National

Aeronautics

Huntsville,

James.

and Space Administration

AL

E. Smith,

Department

Ph.D

of Chemical

University

of Alabama

Huntsville,

Engineering
in Huntsville

AL
ABSTRACT

The importance
nitrogen,

and water on molecular

dimensional
diameter
partial

of the wall effect

computer

cylindrical
differential

equations

column

(submitted

are solved

to Separatuin

breakthrough

information

Science

results

are presented

measurements

linear driving

and Tchnology)
Additional

effects of carrier

and desorption

cm in radius is examined

using finite differences

non-isothermal,

concentration.

on the interactive

Experimental

with concentration

data with the axial-dispersed,

model

beds in the adsorption

sieve 5A of 0.127

simulations.

column

on packed

gas coadsorption

experimentally

for a 22.5-cm

taken at various

radial

and Newmans's

method.

force model

is required

comparisons

of carbon

of

suggests

for accurate
test

data

and with onelong

by

locations.

4.5-cm

The set of

Comparison

of test

that a two-dimensional

simulation
with

dioxide,

the

of the average
model

with CO2, as well as CO2-H:O

provided

interactions.

Introduction

In a packed
and therefore
increase

bed, the presence

heat and mass transfer

in porosity

particle

diameter

infinite porous
governing

of the confining

walls can have a significant

in the packed

near the wall can have opposing

ratio, R, less than about

medium

influence.

(1,2,3).

Between

bed. The viscous

shear

effects

permeability.

for an R value greater

force

has been shown

of 7 and 30, variations

For R values above 30, the influence

it was found to be important

on overall

7, the permeability
R values

influence

is generally

on the axial flow

along

For values

to increase

in bed packing

considered

than 100 in an adsorption

the wall and the

of tube to

above that of an
may determine

insignificant

the

(3), although

study by Tobis and Vortmeyer

(4).
Wall effects on packed

bed processes

the value of R is frequently

a heater
packed

matrix

results

within this sensitivity

in small rectangular

range.

columns

in heat and mass transfer

Examples
(CDRA

are thermal

refs),

driven

processes,

swing adsorption

wall-cooled

catalytic

since

beds where

reactors

(5) and

bed energy storage units (6).

In this work, we examine

desorption
nitrogen

in a packed
carder

thermal

model

balances

adsorption

The experimental

information

results

for carbon

on the sensitivity

diameter

was developed

(radial

for the pellet,

and axial)

and desorption

dioxide

of the adsorption

ratio, R, of 15. Adsorption

during

and water

adsorption

and

adsorption

to wall effects

breakthrough

in a

in a column

data is presented

of permeability

gas

Station

on the finite-differencing

in a flow-through

and canister,

model

was also

and is described

The test flow rate was scaled

Space

based

and desorption

Experimental

International

on mass and heat transfer

at the bed exit, which can be used as a measure

gas adsorption

dimensional

of wall effects

or channeling

for

along

wall.

A computer
simulates

column.

tube to particle

radial locations

the column

the influence

gas provides

with an intermediate
various

can be significant

and

the momentum

developed

to predict

technique.

and multicomponent
equation
the effect

The model
adsorption;

are included.
of flow

A two-

channeling

on

in a later paper (7).

Apparatus

and Results Adsorption

to give gas velocities

Carbon

bed. Single

numerical

Dioxide

Removal

Test System

similar to that in the proposed

Assembly.

Instrumentation

flight beds for the

of the packed

column

includes
temperature
probesandsampling
tubesformeasurements
atsorbent
material
endpoints
andone
intermediate
point.To attainapproximately
adiabatic
bedconditions,
thecolumnwasfirstcovered
with
Mansfield
Q-fiberfeltinsulation,
thenwrapped
witha thermal
blanketof Mansfield
Min-Kmaterial.For
adsorption
runs,anadditional
jacketfabricated
of STSExternal
Tankinsulating
foamwasattached.
The
insulation,
approximately
3 inches
thickinall,wasusedwithsatisfactory
results.
Instrumentation
wasprovidedfor continuous
measurement
of packedcolumnoutletCO2 andH20
concentration.
Thelocationofsensors
andotherequipment
comprising
theadsorbing
apparatus
areshown
inFigure1.Thecolumnbypass
isused
priortotheteststarttoensure
stable
columninletconditions.
Thegaschromatograph,
a Shimadzu
GC-14AwithCR601integrator,
wasusedto sampleat three
sample
portlocations
to determine
gasconstituent
volumetric
fractionsduringtheadsorption
runs.The
probedepthof thesampling
tubeat thecolumnexit wasadjusted
to obtaina radialprofileof theexit
concentration
duringaseries
ofidentical
CO2adsorption
tests.
Column
A small packed column
2) located
sorbent.

at Marshall
A 10-inch

with approximate

Space Flight Center

packing

was used

Dynamics

Test Bed

dimensions

of 2 inches

was used. The column

in this study for quicker

Placing 4.75 inches of glass beads at the two ends of the column

in diameter and 20 inches long (Figure

may be packed

results

with up to 20 inches of

and reduced

eliminated

thermal

end effects.

the end effects.

Procedure
Experiments
Nitrogen
bypass

were performed

on the insulated

is the carrier gas. Experiments

as it proceeded

Figure

The sorbent

is a 5A zeolite.

begin with the column at ambient room temperature.

was switched

before exposure

during the test to follow

The column

of the column to the

the sorbate mass transfer

wave

down the bed.

Results
3 shows

the water breakthrough

of gas mixed

gas breaks through

process

rig at MSFC.

shown in Figure 1 was used to obtain intended inlet conditions

inlet gas. The GC sampling location

pressure

fixed-bed

efficiency

by passing

before

through

and Discussion

at the column

glass beads downstream

the gas at the centerline,

for the two-inch

diameter

midpoint

column.

indicating

and outlet. Also shown is the HzO partial

of the sorbent

that channeling

material.

Note the mixed

has a significant

effect on the

To providea measure
of theradialvariationin axialflow, adsorption
testsof CO2andN2were
conducted
repeatedly
withtheexitsampling
tubein differentradialpositions.
Thetestresults,
shownin
Figure4, showa clearrelationship
between
concentration
andradialposition.As observed
for H20
breakthrough
results,
these
resultsindicate
greater
permeability
nearthecolumn
wall.Sincetheheater
core
of the4BMS(FourBedMolecularSievs)sorbent
bedconsists
of channels
roughlyone-halfinchin
diameter,
thechanneling
effecton CO2removalwill likelybe significant.Theresultsof thetwodimensional
modelpresented
in partII alsoconfirmthatchanneling
hasa significant
effecton this
adsorption
process.
Mathematical

Gas/Solid

The
Company

model

discussed

here

(8). Nitrogen

was developed

adsorption

Equilibrium

using

was represented

Model

equilibrium

with the Langmuir

data

provided

by the W.R

Grace

&

expression:

qmiBiPi

(1)

qi = l+BiPi
Carbon dioxide

and water adsorptions

qmiBiPi

qi -

Two approaches

Prasusnitz,

by an iterative

for multiple

procedure

PY i

i=1

t
7rAni

(RTqmiJ

(9):

(2)

1-11 n--_

of gases adsorbed

components.

with the ideal

(10). For the case of the Langmuir-Freundlich

exp(

equation

ni

were used to solve for the amounts

i=n

by the Langmuir-Freundlich

l+BiPini

with the gas phase concentrations

was obtained

were correlated

in the solid phase in equilibrium

For simulations

adsorption

solution

single component

with

and CO 2, the solution

N 2

theory
isotherm,

(IAST)

of Myers

one gets:

1=0

(3)

and

Knowing
estimated
H20,

the total pressure

and solution

will be obtained

and CO2 the approach

based

found to give a more accurate

process

for submision

towards

in details

correlations

predicts

adsorption

is under predicted,

systems

was

of co2/h2o, a paper is in the

the use of IAST and Langmuir-Freundlich

and test results

for components

multicomponent

equilibrium
adsorption

as discussed

model.

equilibria

on the adsorption

of

OuC i

Ox 2

_x

For

adsorptivities.
example,

indicates

low sensitivity

However,

at low

work

humidity

continues

levels,

for CO 2 and H20. At higher humidity

to

levels,

IAST
CO z

by Finn (11).

In the bulk stream of the gas within the bed, the material

_2C i

using these correlations

with differing

Mass Balance

Boundary

with N 2,

(4)

gas/solid

accurately

- Dl

for multicomponent

rc is

ni

of simulation

a comprehensive

Ot

equation

pressure

For the simulations

l+_Bjpjnj
J

agreement

_C i

for the spreading

until Eq. 3 is satisfied.

on the Langmuir-Freundlich

qmiBiPi

qi

of these

by iteration

a value

on the 5a :

limitations

temperature,

results than lAST model based on the non-ideality

to discuss

CO2/Nz and H20/CO2/N2

The favorable

and the solid

1-e

Equation

balance

for the adsorbate

concentration

d _"

is

(5)

and initial conditions:

att <O,C i =Ci, O forO<

x< L

att <O, qi =qi, o forO<

x< L
(6)

att>O,C

i =Ci, i forx=O

att >_O,_C.i =O for x= L

OX

The axial diffusion,

Assuming
into an overall

Dl, was calculated

the ideal gas

mass balance

law

Ci

equation,

using an equation

P]

RT

from Edward

and knowing

and Richardson

equation

Z Yi = 1, the above equation

(12).
can be recast

o_P _ D

32 P

dP

_ o_

dF
(7)

azr

ar _Rrl-= ?eq-]

t 6-_ --+u ax"

e i="l a

This equation was used to compute

axial velocity

Gas Phase
The change
convection

of gas temperature

with respect

of heat due to the fluid flow, as shown

aTg
at

pgCpg

_ kf

a 2Tg
ax 2

in the bed.

Energy

Equation

to time is due to heat flux from the solid to the gas plus
by the following

UpgCpg

equation:

aTg
--_-x +

(8)
1 -e e hsas (T s _ rg ) -_-_-(rg

Boundary

- rw)

and initial conditions:

att <O, Tg =Tg, o forO<

att>O,

Tg=T

att >O,

%._=O

x< L
(9)

forx=O
for x= L

OX

Note that Tw is calculated

in Eq 12.

Solid Phase
The energy

equation for the solid phase includes

phase plus heat generation

Energy

Equation

the term for heat flux from the solid phase to the gas

due to adsorption.

aT s

a2Ts

p sC ps -'_-t = k s 7

Boundary

d qi

+ hsa s (Tg - Ts ) - i=1

]_ AHi _

(10)

and initial conditions:

att <O,T s =Ts, 0 forO<

att>O,

Ts=T

att>-O,--_-=O

x<L
(11)

forx=O
forx=

Column
The wall temperature

Wall Energy

Equation

T w is given by:

(12)

PwC pw --3Tw -_ 2rtR ihw (T_ - T,, ) - 2nR o h o (Tw - TO)

3t
Initial condition:
at t < O,T w = Tw, 0

Axial

conduction

magnitude

is neglected

(13)

since

the area of heat

larger than the area in the axial direction.

dP _
dx

(13,14)

is used to estimate

from

This is analogous

Momentum
The Ergun equation

transfer

the fluid to the wall is an order

to heat conduction

in a slab.

Equation

the pressure

drop,

It u- pCu 2
K

where C is the inertial

(14)

coefficient.

by Ergun for flow in a packed

The empirical

bed of spherical

coefficients

K and C are given by relations

developed

particle;

d2 3

K -

of

(15)

15o0- )2

C = 1.75(1- e)
dE 3
Using gas velocity

(16)

as calculated

in Eq. 7, the total pressure

Solid Phase
Mass

transfer

of solute

adsorbed

quantity

versus the quantity

transfer

mechanism

adsorption
diffusion

of an adsorption

rates as discussed

amount of binder.

sorbents

Transport

Equation

from the bulk gas to sorbed

rate, and surface

Zeolite

was found with Eq. 14.

diffusion.

state

that would be adsorbed

process

includes

Adsorption

is driven

at equilibrium

four

steps:

by the difference
conditions.

fluid-film

rate can be neglected

since

in the actual

In general,

diffusion,

pore

it is much

greater

the mass
diffusion,
than the

by Yang, (15).
consist of crystals,

Macropore

(spaces

between

in the size range of 1-9 lam, which are pelletized

the crystals)

and micropore

(intracrystalline)

with a small
diffusion

must

ingeneral
beconsidered.
However,
formolecules
inthesizerangeofCO2adsorbing
onto5Athediffusion
rateinsidethepellethasbeenshown
tobecontrolled
byintracrystalline
diffusion(16).
Assuming
theintracrystalline
diffusiongoverns
the overallmasstransfer,
thelineardrivingforce
(LDF)modelbased
onGlueckauf,
(17)maybeused:
--_-=kefas(q;-qi)

wherekej

is obtained

assuming

a linear

established

by experimental
diving

force

by other researchers
Gas to pellet

and N2 x were
coefficients

(17)

to model

and a, is the interfacial

the adsorbed

such as, (16,21,22,23)

heat transfer

.0875,

procedure

.1002,

coefficients

and

using the LDF model

.0844

concentration

in the solid

from the Petrovic

respectively.

for CO2, H20, and N_ were

mass transfer

The

empirically

mass transfer

rate from the gas phase to the pellet surface, the latter was neglected.

rate is three orders

Numerical

model will require

equations

and equilibrium

heat balance
In

this

equation
work,

approximation
were

used

simultaneously
steep gradient
50 nodes
solution
point.
step.

the solution

numerically.

of several

differential

isotherms,

the overall

PDE's

were

spacial

coordinates.

by an implicit

method.

of mass concentration
represented

progressed.

The

equations:

the

The method

length.

was assumed

Here, C is the gas phase concentration,

mass transfer

smaller

than the calculated

mixture,

the momentum

the numerical

equations,
equation,

n rate
and the

wall.

finite

difference

method.

The

first

order

nodes and second order internal nodes

discretized

finite

of Newman

(19,20)

along the bed length, Newman,

the column

Convergence

using

of

(18), for CO 2, H_O,

n-1 mass balance

equation,

First order boundary

set

well

5, and 3.75x10 "4crndsec,

For an n component

mass balance

discretized

was used for the time dimension.

for

of magnitudes

each for the fluid phase, gas phase, and column

the

of

Solution

must be obtained
coupled

has been

obtained

1.27x10 -4, 2.625x10

Since the overall

of this system

phase

and Thodos

respectively.

The solution

area. The justification

to name a few.

obtained

cm/sec,

surface

difference
was found

1967and

The time step was increased

equations

was

to be effective

solved
for the

1968.
from 3.6 to 60 seconds

as the

when (C_I+C_)/C "*l was less than 1.0xl0 -4 for each grid
n indicates

the previous

time step, and n+l the current

time

Results

In this section

we present

critical adsorption
on an ALPHA
sorbent

processes,

modeling

and comparisons

VAX computer.

is a 5A zeolite.

results

illustrate

of model

Experiments

Nitrogen

which

results

were performed

is the carrier

the importance

of accurately

with test data. Simulations

on the insulated

gas. Experiments

begin

simulating

were performed

fixed-bed

rig at MSFC.

with the column

at ambient

The
room

temperature.

Thermal
Heat transfer

coefficients

are found by comparison

column with an inert gas, shown in Figure

Nitrogen
markers
results

was heated

are the measured

from simulation.

canister

temperatures
Resultant

described

nitrogen
centerline

at 6.2

clearly

model

with heating

of the sub-scale

of 350F

and passed

heat transfer

coefficients

2 from the canister

through

an initially

cold

and exit of the column.

are 2.5 BTU/hr-ft

wall to the atmosphere.

column.

The lines are the

2 from the fluid stream

These

The

values

to the

are used in the

below.

of not neglecting

mmHg

was analyzed

with simulations

of the thermal

at the inlet, midpoint,

Nitrogen
The importance

Modeling

5.

to a temperature

wall, and 0.25 BTU/hr-fl

simulations

Effects

the nitrogen

was passed

through

periodically

at the column

that either included

has a noticeable

Coadsorption

effect;

Effects

co-adsorption

an initially

clean

with CO2 is shown

zeolite

inlet, midpoint,

(solid lines) or neglected

however

Modeling

the simulations

column.

and outlet.

(dashed

in Figure

The

gas

These results

at the column
are compared

lines) the effect of nitrogen.

that included

N2 adsorption

6. CO 2 in

Nitrogen

over-predicted

the

effect slightly.
The thermal

sensitivity

heat of adsorption

of nitrogen

data and the simulation,

bed temperatures

to N2 co-adsorption

through

is included.

A decrease

due to N 2 displacement
desorption.

is shown

in Figure

7. The agreement

in temperature

by CO2 and N2 reduces

occurs

is much better when the

at 0.15 hours in both the test

the bed capacity

and lower overall

Water
Verification
illustrate

of the model for

testing and simulation

carrier gas of nitrogen.

Figure

8 illustrates

All figures

midpoint

as shown by test data.

pressure

the inlet level

diameter

roughly

inch in diameter,

the two-dimensional
adsorption

process.

as adsorbed

Finally,

Since

shown

Figure

should

midpoint

indicating

the heater

here)

off by water,

be larger

effect on CO2 removal

outlet

than

material.

Note the mixed

is significant

along the walls

sorbent

bed consists

will be significant.

channeling

10 shows the temperatures

at the column

of the sorbent

that channeling

that

and the CO2 partial

and outlet. Also shown is the H20 partial

core of the 4BMS

confirm

data as lines.

COz is driven

glass beads downstream

the channeling

(not

and simulation

The effect

at the column

through

column.

model

is shown in figures 8 to 10. These three figures

of water at 6.3 mmHg and CO 2 at 2.89 mmHg in a

before the gas at the centerline,

of the two-inch
one-half

co-adsorption

temporarily.

the water breakthrough

through

Effects Modeling

show test data as markers

of gas mixed by passing

gas breaks

the roll-up phenomenon

rises

9 shows

CO2]I--I20]N

runs for adsorption

pressure

Figure

above

Coadsorption

has

a significant

of the bed at midpoint

of channels
The results
effect

of

on this

and outlet.

Bed Regeneration
Desorption

of CO 2 test results

12. After the bed was saturated

gas. As it shown
breakthrough
finally

fiats out

reaches

coefficient

the effluent

in comparison

concentration

predicts

in comparison
of H20

and temperature

phase.

coefficient

Even

was used. Generally,

with this large

mass

as large
there

transfer

and the slope of the

is due to heat of desorption

and

and breakthrough

fairly well. The lAST

with the model are shown by the solid lines in Figures

with the test data. The model

adsorption,

by using N 2 as the purge

of CO2/N 2

of the partial pressure

transfer

11 and

of CO2 from the bed. The same mass transfer

both temperature

not in good agreement

A mass

was started

drop in temperature

when there is no depletion

was used to predict the mixtureisotherm

of H20 test results

process

by the solid lines in Figures

of CO2 has sharp drop at first few minutes

as time goes by. The initial

the inlet condition

and 14. The results

are shown

with CO2, the regeneration

of .017 was used. The model

Desorption

with model

profile of this 1-D desorption

shows a fast reduction

as .04 ft/hr, in contrast

shouldn't

coefficient

be such a large
the desorption
10

of H20

with .0035

difference
of H20

from

13

model are

partial pressure

in gas

ft/hr in the case of H20

between

the two coefficients.

the bed was insufficient

to

increase
the H20 partialpressure
in the gasphase.In contrastwith adsorption
process,
anysmall
discrepancy
of H20partialpressure
withtestdatawill remainasaerrorthroughout
thecompletion
of the
test.In adsorption
anysmallerroratany pointin thebed,if it is caused
bytheisotherm
atsomepartial
pressure
ofthefeedwill beeliminated
ata latertimebecause
of thecorrectvalueof isotherm
ata larger
partialpressure
ofthefeed.Thiscanbeseen
fromtheearlybreakthrough
observed
byotherresearcher.
The
obvious
reason
isthattheequilibrium
isotherm
atlowpartialpressures
arebeingunderestimated.
It is also
possible
thattheequilibrium
isotherm
of H20 on 5A materialshowshysteresis
so thatthe apparent
equilibrium
pressure
observed
inadsorption
anddesorption
experiment
aredifferent.
Theconcentration
ofa
keycomponent,
CO2,is affected
by thepresence
of thenon-key
component,
N2,in CO2/N2
adsorption.
CO2effluentconcentration
overshoots
itsinletconcentration
because
of H20displacement
(moreeasily
adsorbed)
component.
Theheightof this roll-upis increased
with the inletconcentration
of H20
component.
Themostsignificant
contribution
tothedifference
in modelandexperimental
resultsof H20
desorption
pretend
to thatfactthattheduration
of anH20adsorption
runtakesaboutfifteenhoursfor
completion
of a test.Also,thedesorption
runduration
takestentotwelvehours.Duringthislongduration
thetemperature
of location
wherethetesttookplacevariedabout10-15degree
F,duringthenight.Thisin
turnaffectsthesaturated
airthatwasusedtosaturate
thecolumn.
Therefore
it is accurate
toconclude
the
amount
ofH20adsorbed
onthebedislessthanwhatisassumed
inmodel.
Onthebasisof thedatapresented
here,andothercomparisons
between
desorption
testdataand
simulation
results
notyetpublished,
thiscomputer
modelmeets
itsprimaryobjective
- achieving
predictive
capability.
Enhancements
tothemodelasdiscussed
shouldincrease
itsaccuracy.
Effortsarecontinuing
to
develop
ontheintegrated
4BMSsimulation,
equilibrium
isotherms,
heatandmasstransfer
coefficients,
and
verification
data.
Conclusions

Based
following

on

analytical

conclusions

The experimental

investigation

of convective

flows

in porous

media

the

are drawn:
results from the laboratory

the one-dimensional
obtained

and experimental

by test result

model

at the column

deviates

scale-fixed
center.

from the column

bed adsorber

The average
center

concentration

concentration

11

are quantitatively

consistent

of cross

appreciably.

sectional

This indicates

with
bed
the

strongeffectsof porosityvariationalongtheradialdirectionof columnbedon thetemperature,

concentration,
andvelocityfield.Results
fromthemodelwereencouraging
andcontributed
to the
decision
tomodelthedynamic
behavior
ofthecolumnintwo-dimensions.
A lineardrivingforcemasstransfer
modelprovides
areasonable
fit toexperimental
adsorption
data.
Theconcentration
ofakeycomponent,
CO2,isaffected
bythepresence
ofthenon-key
component,
N2,
in CO2/N
2 adsorption.
CO2effluentconcentration
overshoots
itsinletconcentration
because
of H20
displacement
(moreeasilyadsorbed)
component.
Theheightofthisroll-upis increased
withtheinlet
concentration
ofH20component.

NOMENCLATURE

Surface area of pellets

Surface area ft 2

Langmuir

Constant

Gas stream concentration,

Cie

Gas phase concentration

Cip

Volume

c;

Gas phase concentration

of ith component

at the surface of the solid phase lb mole/ft 3

C_,o

Gas phase concentration

of ith component

at boundary

per unit volume

of pellet fi2/ft3

constant
in Darcy equation

average

Ib mole/ft 3
of ith component

in the pores of particles,

pore Gas phase concentration

Heat capacity

of gas phase, Btu/lbm-R

cp,

Heat capacity

of solid particle,

Btu/lbm-R

Cpw

Heat capacity

of column

Btu/lbm-R

diffusivity,

DI

Axial diffusion,

no

Effective

Hw

Heat transfer coefficient

wall,

of ith component

ib mole/ft 3

i, lb mole/ft 3

or initial lb mole/ft 3

ft2/hr
ft2/hr

Heat transfer

coefficient

between

for column

insulation,

Btu/ft2-hr

the gas stream and the column

12

wall, Btu/ft2-hr

ns

Heat transfer

coefficient

between

AH

Heat of Adsorption,

Constant

K:

axial conductivity

Ks

Solid thermal

Mi

Molecular

Number

Total pressure,

mmHg or ibf/ft 2

Pi

Partial

of component

Amount

qi

Solid phase concentration

qmi

Langmuir

Ideal gas constant

Ri

Inside wall diameter

Ro

Outside

wall diameter

Rp

Particle

radius,

Time,

Temperature

To

Ambient

the gas stream and the sorbent,

Btu/lb mole

in Darcy equation
of fluid flow,

conductivity,

weight

Btu/ft-hr-R

Btu/ft-hr-R

of adsorbate

i, lb/Ib mole

of component

pressure
adsorbed

i, mmHg or Ibf/ft 2

in the solid, Ib moles/ft 3 of solid

of ith component

in equilibrium

constant
555 mm Hg ft3llb mol R
of column,

ft

of column,

ft

ft

hr
R

temperature,

gas temperature,

T_

Wall temperature,

T_

Solid temperature,

Interstitial

velocity,

ft/hr

Greek Letters

Ppg

External

Density

Btu/ft2-hr

bed void volume

of gas phase, lb mole/ft 3

13

with gas phase, lbs moles/ft 3 of solid

Ps

Density

of solid phase, lbs/ft 3

Pw

Density

of column

/F

Constant

AH

Heat of adsorption,

wall, lb mole/ft 3

or spreading

pressure

BTU/Ib

of solid

Subscripts

ith component

Effective

Outside,

Pg

Gas phase

ps

Solid phase

Surface

total

Wall

initial

Superscripts

Average value
Equilibrium

value

REFERENCES

1-

Nield, D. A., "Alternative

AIChEJ.,

2-

Cohen,

29, 688,

Model

for Wall Effect in Laminar

Flow of Fluid through

a Packed Column",

1983.

Y., and Metzner,

A. B. "Wall

Effect in Laminar

Flow of Fluids through

Packed Beds,"

AIChe

J., 27, 705, 1981.

3-

Chu, C.F.,
AIChEJ.,

and Ng, K.M.,

35, 148-158,

"Flow

in Packed

Tubes

with a Small

1989.

14

Tube

to Particle

Diameter

Ratio",

4- Tobis,J.andVortmeyer,
D.,"NearWallChanneling
EffectonIsothermal
Constant-Pattern
Adsorption,
Chem. Eng. Sci., 1363-1369,
5-

Cheng,

P. and Zhu, H., "Effects

in Cylindrical
6-

Beasley,

Packed Tubes,"

of Radial Thermal
J. Heat Mass

7-

Mohamadinejad,

8-

"Davison

Molecular

Baltimore

Maryland.

Langmuir,

27, 1659-1669,

Dispersion

Transfer,

D. E., and Clark, J. A., "Transient

J. Heat Mass Transfer,

9-

1988.
on Fully-Developed

30, 2373-2383,

Response

of a

Forced

Convection

Packed

1987.
Bed for Thermal

Energy

Storage,"

1984.

H., Knox, J., "

Sieves Adsorption

I., " The Adsorption

Equilibria",

W. R. Grace & Co., Davison

of Gases on Plane Surface

of Glass,

Chemical

Mica, Platinum,"

Division,

J. Amer.

Chem.

Soc., 40, 1361 (1918).

10- Myers,

A. L.,

and

J. M., Prausnitz,

"Thermodynamics

of

Mixed-Gas

Adsorption,"

AICHE

J.,

11,121,1965.
11- Finn, J.E."4BMS

Adsorption

Field, California,
12- Edwards,

Characterization

Project

Status

Report",

Ames Research

Center,

Moffet

1996.

M. F., and J. F. Richardson,

"Gas Dispersion

in Packed

Beds,"

Chem.

Eng. Sci.,

23,

109,

1968.
13- Ergun, S.,
14- Beavers,

"Fluid Flow Through

G.S.

Mech.,

and Sparrow,

36, 711-714,

York,

E.M.,

Column,"

Chem. Eng. Prog.,

"Non-Darcy

Flow

through

48, 89-94,

Fibrous

1952.

Porous

Media,"

J. Applied

1969.

15- Yang, R. T., Gas Separation

16- Ruthven,

Packed

D. M., Principle

by Adsorption
of Adsorption

Process,

Butterworths,

and Adsorption

Boston,

Processes,

1987.

John Wiley

& Sons,

Inc., New

1984.

17Glueckauf.

E., "Theory

18- Petrovic,

L. J., and G. Thodos,

Chem. Fundam.,
19-Newman,
Lawrence

of Chromatography-Part

10," Trans. Faraday.

"Mass Transfer

Soc., 51, 1540,

in the Flow of Gases through

1955.

Packed

Bed," Ind. Eng.

7, 2, 274, 1968.

J., "Numerical
Radiation

Solution

Laboratory,

Of

University

Coupled,

Ordinary

of California,

Differential

Berkeley,

15

August,

Equations",
1967.

UCRL-17739,

20-Newman,
J.,"Numerical
Solution
ofCoupled,
Ordinary
Differential
Equations,"
Ind

and Eng. Chem. "

Fund, 7, 514-5 ! 7, 1968.

21- DO, D.D., "Sorption
Engineering

Science",

of Bimodal

23- Sargent,

Curves,"

Chemical

Engineering

Sieve II, "Advances

Science,"

Series

Dependence

Vol. 27, pp. 417-423,

C. J., 1971, Diffusion

in Chemistry

Isotherm,"

Chemical

1989.

D.M., "The Effect of Concentration

R. W. H. and Whitford,

in Molecular

Solids With an Irreversible

Vol. 44, No. 8, pp. 1707-1713,

22- Grag, D. R., and Ruthven,

Sorption

Microporous

of Carbon

Dioxide

102, American

DC.

16

of Diffusivity

on Zeolitic

1972.
in type 5A Molecular

Chemistry

Society,

Sieve,

Washington,

i_

- TH EIIbl ()C()II'I.E
- _lJl_

TIIh,/I_I)IJC"IR

- FLOW
DI_W POINT
,UI)NTROLLIII
SEN_OR
I
I

' --I I
I
C.4_m

Bptm m

_1 ---

"_
I

,,,,,

f"
I

. SATURATOR

lip _r,
M.c;I..bVmgW

,,

_"_

. FI_

. PP_ollE

WM IgTEII

VENT
_

- VAL_,Ig

r
v

.__

Figure

1: Adsorption

17

Test System

- QC STEM

G AUG E

AA "_----

I.d

20

I-

S,T

in.

S,T

S,T

A_ "_-"--

Thermocouple

Viox AA

Prbe

Figure

__

2:

Column

A_

Sensor

and Sampling

18

Tube

Location

.....................................

ti .................

' ............

a-_-!
a

r-1

..................
"
,

[]

VI

................................
.o.
................................
o-.......
7.................

El

&

',

.......
,:,
.........
:.................
z_

3
n

t,:
n

..................
..................
'..................
'_
............
[]

[]

.................

: ..................
E1
i

[]

',

t,

',

6
Time,

Figure

3:H20

midpoint

exit

mixed

inlet

O
I

exp. ppH20,

,_...............................

Breahthrough

19

hours

for Co2/H20/N2

Coadsorption

10

o
---o---

3/8" from Wall at Exit

!/8" from Wall at Exit

t_
q

O
L_

3/4" from Wall at Exit

Inlet
Glass Beads at Exit

Time, Hours
Figure 4:CO2

Breakthrough

for Various

20

Radial Positions

250
I

..............................................

_
.o

O: ......

o
e-

._ ---':-.... i--::::

.D _

<>..-"

'/

12_

"

O"
200

C)

:
-O"
. -o
_ - 0---- -- _F--l:_:::

o-

.........................

150

:.... 9-: .... -_:""::

.......................

Q
,,
[.,

,,

j"

:,"

_-

.....
.....
.........

inlet temperature,
midpoint
exit

0
[]
O

10o

'L
......................

,
,'" :
r"l . ."
:

simulation

inlet temperature, experimental

midpoint
exit

--_ .... :--_5

50

0.5

5: Thermal

Model

21

1.5

Time, Hours
Figure

Validation

O
o

<>

,'

i/

0
r..)

ca,.

ta.,

--

sim. ppCO2, inlet, with N2 adsorption

---

midpoint
exit

experimental

[]
O

midpoint
exit

.........
.........
.........
I

0.5
Figure

6: Effect of Nitrogen

1
Time, hours
Coadsorption

22

ppCO2, inlet

sim. ppCO2, inlet, no N2 adsorption

midpoint
exit
I

1.5
on CO2 breakthrough

I05
--

sim. temp.,

--

midpoint

--

exit

inlet, with N2 adsorption

I00
0

<>

',

95

.........

:': ......

',,"
._,
..........

90

[]

midpoint

<>

exit

_ .........

'",,

<>
" :

experimental

sim. temp.,

temperature,

inlet, no N2 adsorption

-........midpoint
.........

",i
<>

exit

E
0

[-

'"

,,

:
85

:
:

<>

4..............

<>
"',

;-'-,:-i .............

80

I
I

75

0.5

1
Time,

Figure

7:

Heat

Transfer

Effect

23

1.5

hours
of Nitrogen

Coadsorption

inlet

3.5

-_o=i....... __

..t..............................................
i...................................
_

2.5

E
E

..............
i-_-_--i ---
.........
J

0
9

1.5

simulated

midpoint

CO2 partial

pressure,

inlet

exit

1
O

experimental

CO2 partial

pressure,

inlet

0.5
]<>
<>

, i , , ,t

-0.5
2

6
Time,

Figure

8:

CO2

breakthrough

for CO2/H20/N2

24

hours
Coadsorption

10

..

cL
3

.............

:--

----

o
m
o
zx

-1
2

breakthrough

for CO2/H20/N2

25

at inlet

exp. ppH20,
midpoint
exit
mixed

inlet

Time, hours
Figure 9:H20

sim. ppH20
midpoint
exit

Coadsorption

10

120

110

o
n
o

....................................................
[]

simulated temperature, inlet

midpoint
exit
experimental temperature, inlet
midpoint
exit

[]

100

2
[]

90

80
O
o
0

0 :0

70

O0

Time, hours
Figure

10: Heat Transfer

for CO2/H20/N2

26

Coadsorption

10

exit
"1"
E
E
q
O
O

............................................

_-/i _

[]

exp.
ppCO2
midpointSim"
ppCO2
Outlet

at
at midpoint
inlet

QI.
t-i

[]

LJ

0.5

!tzb

1.5

2.5

Time, Hours
Figure

l l : CO2

Depletion

for CO2/N2

27

desorption

3.5

78/

....

76

i ....
i

............

_ ....
i

.....

i ....
i

! _.*_"

i ....
i

_ ....
!

i ....
i

'] .............

::.............

i ...........

i ............

i .............

!...........

::

::

,_
74

............

,....... o-- --i.............

[L

72 ...........iI

70
68

....i_, ........i

....i...........

i'-'-'--"-'-'-'-'-'-

"-'-'-'-'-'-'-'-'-

i.

-1

"-'-'--

Figure 12: Heat Transfer

.....,,,,,,,,,,1

Time, Hours
Effects of CO2 depletion

28

for CO2/N2

desorption

qfrl

FII_

ii1_

lift

sim. H20 partial pressure at inlet

--------Elm midpoint
_
exit

__..............................
15

iiii

!
!

exp. H20 partial pressure, midpoint

exit

::

mixed

...........

::

5 L_.'_-:---_---!.-.-_ .....i_._i.................. i.................. :.................

I -'_

__,,

0
0

Time, Hours
Figure

13:H20

Depletion

29

for H20/N2

desorption

75

70

.....

,q),
mm

65

60

8.
IKI

E-

55

50

sim. temperature,
midpoint
exit

inlet

exp. temperature,
midpoint
exit

inlet

45
-1

2
Time,

Figure

14:

Heat

Transfer

Effects

Hours

of H2Odepletion

30

for H20/N2

desorption