NASA/TM-1998-208752

Carbon

Dioxide

Adsorption in Spacecraft
and Sciences,

on a 5A Zeolite Cabins
Moffett Field, California

Designed

for

CO 2 Removal
Lila M. Mulloth Lockheed John Ames Martin

Engineering

E. Finn Research Center, Moffett Field, California

National Space Ames Moffett

Aeronautics Administration Research Field, Center

and

California

94035-1000

November

1998

Available from: National Technical Information Service

NASA Center for AeroSpace 7121 Standard Drive Hanover, MD 21076-1320

Information

5285 Port Royal Road Springfield, VA 22161

CARBON

DIOXIDE FOR

ADSORPTION

ON

A 5A ZEOLITE CABINS

DESIGNED

CO2 REMOVAL

IN SPACECRAFT

Lila M. Mulloth and John E. Finn SUMMARY Carbon (CDRA) covers loading dioxide adsorption l]linois). data were obtained is planned of the International of 0 to 250C, for a 5A zeolite Space Station. manufactured Dioxide The family of 0.001 by AlliedSignal Removal of adsorption Inc.

(Des Plaines,

The material range

for use in the Carbon range

Assembly isotherms of

for U.S. elements a temperature data.

and a pressure

to 800 ton'. Coefficients from the equilibrium

the Toth equation

are fit to the data. Isosteric

heats of adsorption

are derived

INTRODUCTION The Carbon Dioxide Removal Assemblies (CDRA) to be operated in U.S. segments of the molecular animals with the from

International Space Station will use an adsorption-based device known as a "four-bed sieve," or 4BMS, to remove excess carbon dioxide exhaled by the crew and onboard (ref. media 1). This device, (5A zeolite) operation cycle, shown schematically in figure several 1, uses a packed through bed filled to scrub CO 2 from the air blown and is regenerated the process air stream is diverted it. The bed becomes (and previously concentrated

with a solid sorbent saturated cycle. During dioxide regenerated)

CO 2 during regeneration CO:scrubbing

times a day on a programmed to a second

bed, while heat and vacuum regenerated.

are used to remove

carbon

the bed being

CO2 DESICCANT BED (1)

SORBENT (DESORBING)

BED

(4) ELECTRICAL

sE_MPR

(ADSORBING)

CHECK

HEATERS

OPEN

LOOP

SAVE SG 13X COOLER P

VALVES RETURN SG 13

AIR

BLOWE

DESICCANT (DESORBING)

BED

(3) CO2 SORBENT (ADSORBING) BED (2) SPACE VACUUM

Figure 1. Schematic of the flour-bed molecular sieve" unit planned for use in CDRAs in U.S. elements of the International Space Station (ref. 2). The CO:scrubbing 5A zeolite beds are located in the center of the figure.

Mathematical cycle times

modeling

and simulation parameters.

of the 4BMS The modeling

unit is usefid for efficient effort, performed

optimization Marshall

of its Space

and operational

at NASA

Center, requires accurate adsorption data over a range of temperatures collection and presentation of this data is the subject of this document, previously This report collected data (see for example, the results (ASRT ref. 3). equilibrium experiments

and gas concentrations. The and represents an update to

summarizes media

of adsorption

performed

on a sample planned

of for

the CO 2 sorbent

5A, manufactured

by AlliedSignal,

Inc.) that is currently

use in flight. Single component isotherms were obtained 175 , and 250C over a pressure range of approximately EXPERIMENTS Apparatus

at temperatures of 0 , 25 , 50 , 75 , 100% 0.001 to 800 torr.

Single component adsorption isotherm experiments were performed on an apparatus common static volumetric procedure (see for example, ref. 4). Briefly, the apparatus follows (see fig. 2): a quantity of the adsorptive gas is introduced into a manifold

based on a works as known precise sample, is of

of precisely

volume and is held at a eoustant temperature. The pressure of this gas is measured, allowing calculation of the number of moles of the gas in the chamber through a gas law. The sorbent held in an independent allowed to equilibrate. adsorptive calculated appropriate constant Finally, temperature the sorbent bath, is then exposed is again isolated, to this gas and the system of moles and the final number

gas in the manifold is calculated. The change in the quantity of adsorbed gas can be from the change in the amount of gas in the manifold after exposure to the sorbent, after corrections are made for sample cell volume and te_aperature. All volumes are known precisely.
vacuum

gas

inlet

______

constant temperature environmental chamber

temperature constant bath

____

_, _,_

......

sorbent sample

sample cell

Figure 2. Schematic of apparatus used for measuring single component adsorption equilibria.

High accuracy is obtained in this apparatus through careful measurements of volumes, pressures, and temperatures, and through maintaining a low leak rate. Volumes are known to within 0.01%, pressures to 0.15%, and temperatures to 0.1 C (0.04% and beaer for these experiments). The helium leak rate of the system is approximately 1 x 10 -7 cc-atm/sec.

Materials The sample of ASRT 5A zeolite sorbent was provided by NASA Marshall Space Flight Center. It has the form of light beige, brittle, cylindrical pellets approximately 1/16-inch diameter and roughly 1/8-inch long. The gas used in the experiments Matheson Gas Products, Inc. Procedure Approximately by placing connected one gram of sorbent a trickle sample was used for each experiment. at 320C. The cell containing cell at the temperature of the sample Samples were prepared sample was was 99.99% pure CO 2, obtained from

them under to the system,

flow of helium The system

the sorbent

and the free space

of the experiment of helium

was determined from the sample

using helium. was observed.

was then evacuated

at 150C until no outgassing

Experiments performed at 0C used water-ice in the constant temperature bath. Experiments 50 , and 75C used an automatically controUed constant temperature water bath. Experiments 100C and higher The criterion minutes. required DATA A family of CO 2 adsorption isotherms for ASRT 5A from 0 to 250C of the Toth equation pt)-x/, is shown (ref. 5) in figure Time longer Data points used an automatically controlled fluidized sand bath. in pressure depending in a single over a period

at 25 , at

for equilibrium needed were obtained equilibration

for the experiment sequentially,

was 0.1% change

of 5

for equilibration

varied from

10 to 30 minutes pressures,

on the pressure. run. Initial points

from low to higher

times than points obtained

later in the run.

3. The raw

data are tabulated

in the Appendix.

Coefficients

q = raP(b+

(1)

where q is quantity adsorbed, P is pressure, and m, b, and t are adjustable data; these curve fits are shown as lines on figure 3. The Toth coefficients are also tabulated in the Appendix.

constants, were fit to the for the seven isotherms

10

0.1

:I:t

! ! !!!!!!
i o i i i i!iii

.,!!
iili_

0.01
! : :::i_ !i!i:: : :::::: i _ i i i !ii!i! i i iii!!i _ ! i!iii!

0.001

0.0001 0.001 0.01 0.1 1 CO 2 pressure (tort) 10 100 1000

Figure 3. CO2 adsorption equilibrium isotherms for ASRT 5A from 0 to 250C. Toth equation fits to the data are shown as lines.

The isosteric as a function temperature using Figure Ruthven

heat of adsorption of loading at constant loading

required

for the energy

balance

in a flow system, reciprocal

can be determined absolute linearity. reported by

by obtaining to interpolate

the slopes of plots of laP versus between data points;

(ref. 6). Figure 4 illustrates from the slopes

the_e plots for a wide range of loadings, thert_ is generally excellent of taese lines. The limit of the isosteric

the Toth equation 5 shows

the isosteric

heats obtained

heat at zero loading, (ref. 7).

44.9 kJ/mol,

is in good agreement

with a figure of 45.2 kJ/mol

_2

"_

-2:

_o

.z

-{

.......................... ]............................. i.................. i............................. _olo2__

I
2.8

................
I
3.6 3.8x10 "3

-8 2.6

I
3.0

i
3.2 reciprocal temperature, K"1

i
3.4

Figure 4. Plots of InPversus reciprocal absolute temperature for Ioadings ranging from 0.02 to 7.4 weight percent. Isosteric heat as a function of loading calculated from the slopes.

50

'

'

' '' '''1 i f i iii_

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

'

_ :
I

I I ; l I: I I " :: i :: i :: I

'
k--

'....... ' _ i
_.......

' ' ''' ( i iii'

'. i i _i-

---------..-,-,-,.,-----,--

_--o-_'-!-_!-iQ

.....

]
=o

40

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

-_----J..-.._---_-- ._-_ ........................... .L

: : : ; : : i

-_ ....... _----.;,..-;---L-_,--;-_ ..................

: ', ; " : : : i

:.......... i....... ;---, .;...4----;-.,i-_

: ; : : _}: "

! i i iii

':

i ; i i 11!

i i i l;i

E.
@
r,o

_o......................... _ _-iili'_........................... ...... i.......?!iii................................... ! ......... . 1,_,_-_**'-

_: _ i ::::_:_

ilil

i i :,iiii

::::

i iiil

:::

'......................... ............................. i ..... ........................... . iii!ii! i...... ?fi!iii iiii!i

: : 1 : : : : :

i!"i !i!iiiiill

i i!i ! !ii !:i

! i i!! ii!

i 2 3

i 4

! ! ! i 2

i 3

i 4

i 5

i i ! i 2 3

! 4

i 5

i 678

i [ i

56789

6789

0.01

0.1

10

C02 loading (g C02/100 g sorbent)

Figure 5. Isosteric heats calculated

at various Ioadings from the isotherm data shown in figure 3. The here to be 44.9 kJ/mol.

dashed line is the intercept in the limit of zero loading; calculated

CONCLUSION Adsorption equilibrium isotherms were obtained for the system CO2-ASRT 5A zeolite over the

temperature range 0 to 250C for the purpose of supporting modeling of the Carbon Dioxide Removal Assembly for the htemational Space Station. The data are fit well by the Toth equation. Isostedc adsorption CO2-5A heats of adsorption zeolite system. were derived from the equilibrium well with previously loading data, and the heat of results for another in the limit of zero loading agrees published

REFERENCES 1. Boeing Company, U.S. Lab Architecture Revision New, D683-14719-1-9, Control Document, Volume November 27, 1996. 9: Air Revitalization System

2. Mohamadinejad, H., et al., "Hardware-independent mathematical and numerical modeling of a four-bed molecular sieve - part 1," 26th International Conference on Environmental Systems, Paper 3. Wright, No. 961405, Monterey, California, of design July 1996. for molecular-sieve Company, NASA type regenerative Contractor Report No.

R. M., et al., "Development systems," 1973.

information

CO2-removal CR-2277,

AiResearch

Manufacturing

4. Adamson, A. W., Physical 1990. 5. Toth, J.,Acta Chim. Acad.

Chemistry_

of Surfaces,

5th ed., John Wiley

& Sons,

New

York,

Sci. Hung., of Act_orption

69, 311,

1971. Processes, John Wiley & Sons, New

6. Ruthven, York, 7. Ruthven,

D. M., Principles 1984. D. M., Loughlin,

and Adsorption

K. F., and Derrah,

R. I., Adv.

Chem.,

121,

330,

1973.

APPENDIX Tabulated weight adsorption data for CO 2 on ASRT 5A, with fitted Toth equation below. Toth parameters have units consistent Note that these coefficients isotherms). parameters (see equation and 1

in the text) are presented % for loading. for the higher temperature

with torr for pressure

are valid only for interpolation

of data (especially

Ooc

25C pressure (torr) loading (wt%) 0.0132 0.0318 0.122 0.341 0.855 2.13 3.79 5.28 10.1 12.9 15.5 15.8 uni_ofto_,wt% 20.8173 1.66122 0.403689

pressure (torr) 0.00098 0.00248 0.00785 0.0254 0.0873 0.834 38.1 156 467 763 Toth coefficients,
m

loading (wt%) 0.0182 0.0560 0.165 0.437 1.15 3.67 11.4 15.2 16.5 16.8 units of torr, wt% 17.867 0.853206 0.444986

0.00247 0.00699 0.0277 0.0952 0.316 1.24 3.70 8.00 51.1 146 569 768 Tothcoefficients, m b t

b t

500C loadinR 0.0169 0.0428 0.124 0.386 1.45 4.94 8.13 10.6 12.1 13.5 14.7 units of torr, wt% 20.9923 3.56105 0.447872 (wt %)

75C ioadinR (wt%)

pressure (torr) 0.00583 0.0142 0.0371 0.120 0.462 2.59 24.5 72.0 168 279 500 784 Toth coefficients, m b t

0.00570

pressure (torr) 0.0192 0.0244 0.0515 0.120 0.310 0.610 4.16 27.2 75.5 132 292 572 780 Toth coefficients
nl

0.00354 0.00806 0.0163 0.0371 0.0876 0.156 0.759 2.73 4.67 6.24 9.45 11.8 13.3 units ofto_,wt% 39.939 5.23465 0.356774

b t

IO0oC

175C

pressure (torr) 0.00979 0.0338 0.0827 0.260 0.725 2.34 6.24 13.1 67.3 151 317 478 622 815 Tothcoefficients, m b t

loading (wt%) 0.00121 0.00483 0.0116 0.0325 0.0822 0.229 0.500 0.895 3.04 4.64 7.06 8.64 9.68 10.8 units ofto_,wt% 45.9782 8.23681 0.367554

pressure (torr) 0.0250 0.0596 0.153 0.374 1.09 4.82 16.3 31.4 120 252 575 806 Toth coefficients, m b t

loading (wt%) 0.000175 0.000569 0.00173 0.00405 0.0115 0.0472 0.154 0.286 0.873 1.65 3.08 3.89 units of torr, wt% 15.5414 141.673 0.672267

250C

pressure 4.98 32.2 226 799

(torr)

loading (wt%) 0.0162 0.0906 0.459 1.43 units of torr, wt% 6125.71 16.8625 0.20097

Toth coefficients, m b t

Form

Approved

REPORT DOCUMENTATION

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1. AGENCY

USE ONLY

(Leave

blank)

| 2. REPORT

DATE

3. REPOI:_"

TYPE

AND DATES

COVERED

I
4. TITLE AND SUBTITLE

November

1998

Technical
S.

Memorandum
FUNDING NUMBERS

Carbon Removal
6. AUTHOR(S)

Dioxide

Adsorption

on a 5A Zeolite

Designed

for CO 2

in Spacecraft

Cabins

Lila M. Mulloth*

and John E. Finn

7.

PERFORMING

ORGANIZATION

NAME(S)

AND ADDRESS(ES)

8. PERFORMING ORGANIZATION REPORT NUMBER

Ames Research Center Moffett Field, CA 94035-1000

* Lockheed Martin Moffett Field, CA 94035-1000

A9800125

9.

SPONSORING/MONITORING

AGENCY

NAME(S)

AND

ADDRESS(ES)

10.

SPONSORING/MONITORING

AGENCY

REPORT

NUMBER

National

Aeronautics DC

and Space Administration NASA/TM-1998-208752

Washington,

20546-0001

11.

SUPPLEMENTARY

NOTES

Point

of Contact:

John E. Finn, Ames (650) 604-1028

STATEMENT

Research

Center,

MS 239-15,

Moffett

Field,

CA

94035-1000

12e.

DISTRIBUTION/AVAILABILITY

12b.

DISTRIBUTION

CODE

Unclassified-Unlimited Subject
Availability:
13. ABSTRACT

Category
NASA CASI
200

- 25
(301)
words)

621.4D90

Distribution: Standard

(Maximum

Carbon (CDRA) covers

dioxide

adsorption Illinois).

data were obtained is planned of the International of 0 to 250C,

for a 5A zeolite Space Station.

manufactured Dioxide The family

by AlliedSignal Removal of adsorption

Inc.

(Des Plaines,

The material range

for use in the Carbon range

Assembly isotherms

for U.S. elements a temperature data.

and a pressure

of 0.001 to 800 ton'. Coefficients are derived from the equilib-

of the Toth equation rium loading

are fit to the data. Isosteric

heats of adsor_gtion

14.

SUBJECT

TERMS

15.

NUMBER

OF

PAGES

14 Carbon
17. SECURITY OF REPORT

dioxide

removal,

Air revitalization,
18. SECURITY OF THIS

Carbon

dioxide
19.

adsorption

16.

PRICE

CODE

A03
CLASSIFICATION CLASSIFICATION PAGE

SECURITY CLASSIFICATION OF ABSTRACT

20.

LIMITATION

OF

ABSTRACI

Unclassified NSN7_O-O_-2BO-SSOO

Unclassified
Standard
Prescribed 298-102

Form

298

(Rev.

2-89)

by ANSI Std. Z39-18