See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/263284091

Characterisation of Carbon Dioxide Absorbent Material For Enclosed Space

Applications

Article in Defence S and T Technical Bulletin · April 2012

CITATIONS READS

4 4,801

9 authors, including:

Mahdi Che Isa Nik Hassanuddin

Science and Technology Research Institute for Defence Science and Technology Research Institute for Defence
44 PUBLICATIONS 176 CITATIONS 25 PUBLICATIONS 224 CITATIONS

SEE PROFILE SEE PROFILE

Mohd Subhi bin Din Yati Mohd Moesli Muhammad

Science and Technology Research Institute for Defence Science and Technology Research Institute for Defence
20 PUBLICATIONS 50 CITATIONS 25 PUBLICATIONS 87 CITATIONS

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Ferromagnetic Research View project

New composite coating View project

All content following this page was uploaded by Mohd Moesli Muhammad on 23 June 2014.

The user has requested enhancement of the downloaded file.

 CHARACTERISATION OF CARBON DIOXIDE ABSORBENT
MATERIAL FOR ENCLOSED SPACE APPLICATIONS

Mahdi Che Isa1*, Nik Hassanuddin Nik Yusoff1, Mohd Subhi Din Yati1, Mohd
Moesli Muhammad1, Nor Afizah Salleh2, Mohd Fauzy Mohd Nor2, Azmi Minal2
Hasril Nain3 & Irwan Mohd Nor1

1
Materials Research Group, Maritime Technology Division (BTM)
2
Weapons Technology Division (BTP)
Science & Technology Research Institute for Defence (STRIDE), Ministry of
Defence, Malaysia
3
Ship Silencing Centre (SSC), Royal Malaysian Navy (RMN), Malaysia

*
Email: [email protected]

ABSTRACT

Soda lime is one of the most popular absorbent materials used for eliminating carbon
dioxide (CO2) from contaminated air. Variation in soda lime chemical composition
and physical properties influence its final performance for specific applications.
Parameters such as chemical composition, moisture absorption, loss on dryness,
granules shape, chemical absorbency and particle (dust) sizes play a very important
role in determining the quality and life span of soda lime materials. This paper
discusses the results of characterisation and evaluation conducted by STRIDE on
a commercial soda lime material. This study shows that the sample is a mixture of
calcium hydroxide, sodium hydroxide and moisture. The sample has been produced
to provide soda lime granules with optimised surface area, hardness, and toughness
for resistance to abrasion, uniformity in mesh size, and consistency in quality.

Keywords: Carbon dioxide (CO2); soda lime; submarine atmosphere; air quality;
hardness; chemical composition.

1. INTRODUCTION

The revitalisation of air present in the atmosphere of all natures is of great importance.
This applies for any type of atmosphere, be that of a space capsule, a submarine or
any enclosed compartment (Douglas et al., 1989). The atmosphere factor within the
enclose system is vital for life, and hence air purification has been introduced to
remove contaminants or any types of toxic gases, in order to maintain a healthy
air composition. For example, excess amount of carbon dioxide (CO2 ) should be
removed, and this can be done either by chemical separation technology or physical
adsorption process (Olajire, 2010; Hsu & Chung, 2011).

1
The air purification system employed should be capable of maintaining appropriate
CO2 and oxygen levels so that it will not impair mental and physical performances. At
1% CO2 content, the enclosed environment must be ventilated, and / or preparation
made to remove the gas (Jonathan et al., 2009; Cable, 2008). CO2 absorbent
materials are well known and widely used in a number of applications. They may
include, for example, in a variety of industries, such as anaesthesia, respiratory care,
hyperbaric chambers, military and tourist submarines, underwater diving gear, fire
safety apparatus, and mine rescue equipment. Monoethanolamine (MEA), zeolite
molecular sieves, baralime (a mixture of 80% calcium hydroxide and 20% barium
hydroxide), soda lime and lithium hydroxide (LiOH) are typical absorbents used
to scrub CO2 from the air (Leci et al., 1992; Plaza et al., 2009; Dugas et al., 2009;
Llano-Restrepo, 2010). Of these materials, the most commonly used absorbents in
submarines are MEA and soda lime (Carey et al., 1983; Mazurek, 2005).

Soda lime, the most popular absorbent, was originally developed by Prof. Robert E.
Wilson of Massachusetts Institute of Technology (MIT) in the year 1917 to meet
the urgent need for an effective absorbent in military gas masks to absorb soldiers’
exhaled CO2 (Moore & Campbell, 1983). When exposed to atmospheric CO2 under
moist conditions, soda lime reacts and converts into calcium carbonate as a result of
carbonation. Soda lime is an absorbent material which contains a certain composition
of calcium hydroxide (slaked lime), metal oxide and water contents. As it reacts with
CO2, it forms a stable solid which is retained within the absorbent canister (Lillo et
al., 1996; Renato et al., 2006). For safety reasons, an appropriate reserve quantity of
soda lime is essential if CO2 content reaches 1% of any enclose space volume and the
removal process of CO2 should then start to progress.

Particle size and shape, porosity, and bulk density are particularly important in terms
of the performance of an absorbent material in its intended application. Most soda lime
grades are now produced with shapes that offer high surface to volume ratio. These
carefully engineered shapes ensure maximum CO2 penetration into the particles, by
minimising the distance to the centre of the particles, thereby increasing the CO2
capacity of the product. Variations in conditions, such as humidity, can significantly
affect the predicted life expectancy and performance of the absorbent (Shunji et
al., 2003; Klos, 2008). Another key factor in determining absorbent performance is
particle size distribution. Particle size has an effect on the speed of reaction, which
in turn affects the volume of the reaction zone and the capacity of the absorbent. In
general terms, the smaller the particle size, the smaller the reaction zone volume that
results to higher reactions. However, the smaller the particle size, the greater the
pressure-drop across the absorbent, which may affect absorption efficiency and other
characteristics (Mazurek, 2005).

The aims of this study are to determine the chemical composition of a selected
commercial soda lime material and to characterise its physical properties, with
respect to granules size distribution, hardness, moisture contents and chemical

2
reactivity. The data obtained from this study will be compared with standards of
the same product for the purpose of air regeneration process in enclosed spaces,
particularly for submarine applications.

2. MATERIALS & METHODS

A commercial 4.5 kg soda lime sample obtained from Scientific Engineering &
Technology Services (SETS), Rawalpindi, Pakistan, was selected for this study. The
physical appearance of its granules was observed using a normal digital camera,
while the sizes of the granules were determined using a stereomicroscope with image
analyser (Carl Zeiss Axio Vision). Particle or dust size measurement was carried out
by screening 100 g of the sample for 5 min using a mechanical shaker, with a Num.
45 (355 µm) standard-mesh sieve. The hardness of the sample was determined by
shaking 200 g on a sieve with size 425 micron for 5 min using a mechanical sieve
shaker. Of the retained material, 50 g was placed in a hardness pan having a concave
brass bottom, diameter of 20 cm, thickness of 7.9 mm at the circumference and 3.2
mm at the centre, and inside spherical radius of curvature of 109 cm. A total of 15
steel balls with diameter of 7.9 mm were added and the mechanical sieve shaker was
operated for 30 min. The steel balls were removed, and the contents of the pan were
transferred to the sieve and shaked on the mechanical sieve shaker for 5 min. The
material retained on the sieve was weighed.

The loss on drying test was carried out by placing 10 g of the sample in an oven for
2 h at 105 °C. For the moisture absorption test, 10 g is placed in a 50 ml weighing
bottle, having diameter of 50 mm and height of 30 mm, and its cover removed.
The bottle was stored for 24 h in a closed container in which the atmosphere was
maintained at 85% relative humidity (RH) by being in equilibrium with sulfuric acid
having a specific gravity of 1.16, which is the requirement set by USP-NF (2010).
The final weight of the sample was recorded.

The phases presence in the soda lime material were determined using an X-ray
diffractometer (XRD) (Bruker D8-Advanced) housed at the School of Applied
Physics, National University of Malaysia (UKM). The diffractogram was generated
using a Cu Kα ( λ = 1.543 Å) radiation source at scanning rate of 0.002 °/s with 2θ
from 20º to 60º.

The elemental composition of the material was analysed using a wavelength dispersive
X-ray fluorescence (XRF) spectrometer (Bruker SP 4 Pioneer, WDXRF) equipped
with an Rh X-ray tube and 4 kW generator. The X-ray generator was operated at
voltage of 20 - 50 kV and current of 5-20 mA.To prepare the XRF-pellet, a small
metallic sample holder made of aluminium with diameter of 3 cm was used. The
pellets were pressed for 30 s with pressure of 10 tons/cm2 using the Specac hydraulic
press machine. From this process, the total mass of each pellet gained was 10.8 g.

3
Quantitative calculations were made using the accompanied software. The results of
the analysis were expressed in weight percentage (wt.%).

To determine the chemical absorbency of the sample, an amount of 33.3 g is placed

inside a U-tube with 10 g of calcium chloride (CaCl2 ) to trap the moisture produced
by the neutralisation reaction and to simulate dry environments. 99.5% purified CO2
gas was injected/inserted/ through the U-tube at the rate of 1,000 ml per minutes for
five minutes to allow it to cool down. The initial and final weights of the U-tube were
recorded to determine the permissible quantity of CO2 which had been absorbed by
the soda lime.

3. RESULTS & DISCUSSION

The physical appearance of the soda lime granules is shown in Figure 1. The granules
have non-uniform, irregular shapes with diameters in the range of 3-7 mm as shown
in Figure 2. Table 1 shows various distribution size of granules. It was observed that
76.8% of granules were in the range of 2.36 - 4.75 mm in diameter. The current size
distribution of the granules can be considered as a compromise between resistance to
air flow and absorptive capacity of the soda lime material.

Figure 1: Photograph of the near white or greyish white soda lime granules.

4
 (a) 4.29 mm (b) 5.24 mm

(c) 3.69 mm and 6.48 mm (d) 3.21 mm and 5.99 mm

Figure 2: Variations of the soda lime granules’ diameters.

Table 1: The soda lime granules’ size distribution.

Granule size (diameter) %
More than 5.6 mm 0.7
4.75-5.60 mm 21
2.36-4.75 mm 76.8
0.60-2.36 mm 1
Less than 0.6 mm 0.5

The particle size determination results in Table 2 showed that not more than 2.0%
of the sample (average of only 0.64%) passed through a Num. 45 standard-mesh
sieve (USF-NF, 2010). The presence of dust in the sample is also in good agreement
with the specification set by NATO (2006), which requires that not more than 1%
of the particles should be below 600 µm. The low dust content indicates that there
was only a small amount of sharp edges of the granules which rubbed against one
another during processing, transporting and storing activities. The hardness test
conducted gave a result of 81.16%, which is in compliance with USP-NF (2010),
indicating that the sample is not too soft or friable, and not easily broken down to
form underparticles or dust.

5
Table 2: Results of the particle size test using a Num. 45 (355 µm) standard mesh sieve.
No. of tests % pass through
1 0.4251
2 0.7807
3 0.7265
Total 1.9323
Average 0.6441

The sample recorded 13.45 % loss of weight on drying. This is within the tolerance
of soda lime specifications that requires 12 to 19 % of weight at 105 °C for 2 h..
In addition, for storage purposes and shelf life of soda lime, its weight shall not
increase more than 7.5% after being stored in a closed container for 24 h. The sample
only undergoes 0.86% weight increase, which satisfies the requirement of USP-NF
(2010).

The elemental composition of soda lime is shown in Table 3. The main metal oxides
determined by the WDXRF machine were calcium hydroxide (Ca(OH)2 ) (87.0%),
sodium hydroxide (NaOH) (10.2%) and silicon dioxide (SiO2 ) (0.9%). In this sample,
we believe a small amount of Si was added to produce calcium and sodium silicate.
This addition produces a harder and more stable soda lime granule, and thereby,
reduces dust formation as recorded in Table 2. Elements other than Ca, Na and Si
were also detected, which are impurities from raw materials, strongly believed to be
from the grades of purity of calcium oxide (CaO) used in the soda lime manufacturing
process.

Table 3: The elemental composition of the sample

No. Elements wt.%
1. Calcium (Ca) 87.0
2. Sodium (Na) 10.2
3. Silicon (Si) 0.9
4. Magnesium (Mg) 0.5
5. Strontium (Sr) 0.4
6. Aliminium (Al) 0.1
7. Iron (Fe) 0.2
8. Sulphur (S) 0.2
9. Others (total) 0.5

Figure 3 shows the XRD spectrum for the sample with the presence of major peaks
for the Ca(OH)2 and NaOH phases. Based on the XRD results, it can be concluded
that the sample consists of a mixture of Ca(OH)2 and NaOH. However, the XRD
spectrum also shows a very broad diffraction pattern where the presence of low
intensity peaks identified as vaterite phase (µe-CaCO3 ; JCPDS* 33-0268) can be
clearly seen. Vaterite is associated to the presence of monohydrocalcite (CaCO3.H2O;
* Joint Committee on Powder Diffraction Standards

6
JCPDS 29-0306) and a small amount of calcite (CaCO3; JCPDS 01-086-2342 R-3c)
(Lopez-Arce et al., 2010). The presence of the vaterite phase in the sample can be
attributed to the reaction between CO2 in the air and Ca(OH)2 in the sample.

Figure 3: XRD spectrum for the sample.

The CO2 absorption reaction occurred according to Equation 1 in which CO2 reacts
with Ca(OH)2 to produce vaterite or calcium carbonate, and water. This reaction took
place during the sample preparation and / or during exposure to atmosphere during the
XRD testing procedures (Randell & Clarke, 2003). Based on this, it can be concluded
that XRD analysis is capable of revealing the fast transformation or reaction of the
sample with CO2 in the air to form vaterite (metastable CaCO3), monohydrocalcite
(CaCO3.H2O) and calcite (CaCO3) in high humidity conditions (RH 80%).

CO2 (g) + Ca(OH)2 (s) → CaCO3 (s) + H2O (g, l) + Heat (1)

The presence of strong alkali hydroxides (NaOH) allows the sample to absorb CO2
more quickly and with greater capacity than mixtures containing only lime and
water. The absorption performance of soda lime is very important, thus the scrubbing
capacity and life expectancy shall be predicted based on a given set of conditions.
Variations in conditions of flow rate, CO2 concentration, temperature, pressure,
humidity etc. can significantly affect the predicted life expectancy (Randel et al.,
2003).

One of the important properties of soda lime granules is morphology (physical form
and shape) because the surface to volume ratio is very important in determining
how fast the material can react and chemical absorption capacity. To produce good
gas-solid interaction behaviour, more surface path for the gas through the granules
with less straight channels should be designed. For some granules with very uniform
shape, this can readily lead to large straight channels forming, which tend to leave
unreacted material at its centre as it is a long way from the surface to the centre
(Audrius et al., 1996).

7
Therefore, in order to minimise the unreacted zone, the irregular shaped granules
in the sample can provide an absorbent material which can provide higher surface
area, facilitate more reaction sites, and increase reaction rates. Based on the results
of the chemical absorbency test (Table 4), the sample achieved the minimum CO2
absorption specified by USP-NF (2010), which states that the weight increment of
the sample after test shall be not less than 19%. The optimum physical properties
together with the presence of alkali metal hydroxides in the sample are believed to
contribute towards the improvement of absorbency of CO2 (Baum & Woehlck, 2003).
This finding is in good agreement with studies conducted by previous researchers
which have claimed that CO2 absorbents that contain small amounts of NaOH (3.2%)
have greater CO2 absorption capacity than absorbents that do not contain NaOH
(Stabernack et al., 2000).

Table 4: Results of the chemical absorbency test.

Num. of tests % of weight increment

1 21.36
2 22.28
3 20.68
Average 21.44

4. CONCLUSION

The results obtained from our characterisation works show that the quality of the
selected commercial soda lime product used as a CO2 absorbent material complies
with the requirements set by many industries, particularly for use in enclosed spaces
and military applications. The sample is a mixture of Ca(OH)2 , NaOH and water,
which has been produced in irregular shaped solid granules in order to maximise
CO2 absorption in the air. This study also shows that proper storing will prolong the
sample’s shelf life by minimising the amount of moisture absorbed, loss of weight
during drying, and formation small sized particle (soda lime dust).

ACKNOWLEDGEMENT

The authors would like to thank the Government of Malaysia for financing this
R&D project under the 10th Malaysia Plan. We also greatly appreciate Datuk Dr.
Abdul Ghaffar bin Ramli, Director-General of STRIDE, for his support, ideas,
and a series of meaningful and fruitful discussions. We wish to thank the Weapons
Technology Division, STRIDE, for conducting the granules’ size test, and Prof.
Mohd Ambar Yarmo, from the Faculty of Science & Technology, UKM, for assisting
and conducting the XRD test. We are pleased to acknowledge SETS, Pakistan, for

8
providing the soda lime samples, and Dr. Assanah Mohd Mydin from Caidmark Sdn.
Bhd. for participating in this work. The cooperation and technical assistance given
by STRIDE’s officers and staff in improving the quality of this manuscript is also
highly appreciated.

REFERENCES

Audrius M., Jolanta L. & Arunas Š. (1996). Regulation of cellulose-based absorbent

granule morphology. J Chrom. A, 746: 147-160.
Baum, J. A. & Woehlck, H. J. (2003). Interaction of inhalational anaesthetics with
CO2 absorbents. Best Prac. Res. & Cl. An., 17: 63-76.
Cable, J. (2008). NIOSH Report Details The Dangers of Carbon Dioxide in Confined
Spaces. Available online at: http://www.occupationalhazards.com /News/
Article/37358 (Last access date: 24 December 2009).
Carey, R., Gomezplata, A. & Sarich, A. (1983). An overview into submarine CO2
scrubber development. Ocean Eng., 10: 227-233.
Douglas, R. K., Donald, V. T., Jeffry, S. B., O’Neill, H. J. & Gordon, S. M. (1989).
Submarine atmospheres. Toxicol. Lett., 49: 243-251.
Dugas, R., Alix, P., Lemaire, E., Broutin, P. & Rochelle, G. (2009). Absorber model
for CO2 capture by monoethanolamine - application to CASTOR pilot
results. Energy Procedia 1: 103-107.
Hsu H. C. & Chung S. T. (2011). Removal of CO2 from indoor air by alkanolamine
in a rotating packed bed. Sep.Purif. Technol., 82:156-166.
Jonathan L. S., David G. K. & Randal J. K. (2009). Occupational hazards of carbon
dioxide exposure. J. Chem. Health Safety, 16:18-22.
Klos, R. (2008). Removal of oxidable contaminations contained in submarine
atmosphere. Polish Maritime Res., 3: 67-69.
Leci, C.L. & Goldthorpe, S.H. (1992). Assessment of CO2 removal from power
station flue gas. Energy Converse. Manage., 33: 477-485.
Lillo, R.S., Ruby, A., Gummin, D.D., Porter, W.R. & Caldwell, J.M. (1996). Chemical
safety of U.S. Navy fleet soda lime. Undersea Hyperbaric Med., 23: 43-53.
Llano-Restrepo, M. (2010). Accurate correlation, structural interpretation, and
thermochemistry of equilibrium adsorption isotherms of carbon dioxide in
zeolite NaX by means of the GSTA. Fluid Phase Equilibr., 293: 225-236.
López-Arce, P., Gomez-Villalba, L.S., Pinho, L., Fernández-Valle, M.E., Álvarez
de Buergo, M. & Fort, R. (2010). Influence of porosity and relative humidity
on consolidation of dolostone with calcium hydroxide nanoparticles:
Effectiveness assessment with non-destructive techniques. Mat. Charac.,
61: 168-184.
Mazurek, W. (2005). Submarine atmosphere. In Hocking, M.B. & Hocking, D.
(Eds.), The Handbook of Environmental Chemistry: Vol. 4, Part H (Air
Quality in Airplane Cabins and Similar Enclosed Spaces). Springer-Verlag
Berlin Heiderberg, Germany, pp. 351-382.

9
Moore, L.W & Campbell, D.L. (1983). Robert Erastus Wilson. In National Academy
of Sciences (Ed.), Biographical Memoir. National Academy of Sciences,
Washington D.C., pp. 409-433
North Atlantic Treaty Organization (NATO) (2006). NATO STANAG 1411: Standard
to Quantify the Characteristics of Carbon Dioxide (CO2 ) Absorbent Material
for Diving, Submarine and Marine Applications. North Atlantic Treaty
Organization (NATO), Brussels.
Olajire, A.A. (2010). CO2 capture and separation technologies for end-of-pipe
applications – A review. Energy, 35: 2610-2628.
Plaza, J.M., Wagener, D.V. & Rochelle, G.T. (2009). Modeling CO2 capture with
aqueous monoethanolamine. Energy Procedia, 1: 1171-1178
Randell D.J. & Clarke, M. (2003). Fourth International Conference on Submarine
Air Monitoring And Air Purification (SAMAP), Emden, Germany
Renato, B., Giuseppe, S. & Marco, M. (2006). Process design and energy requirements
for the capture of carbon dioxide from air. Chem. Eng. & Process., 45; 1047
– 1058.
Rendell, D.J., Clarke, M. & Evans, M.. (2003). The effect of environmental conditions
on the absorption of carbon dioxide using soda lime. 39th International
Conference on Environmental Systems, 12-16 July 2009, Hyatt Regency,
Savannah, Georgia.
Shunji, K, Hiromichi, B. Takasumi, K. & Shigehito, S. (2003). Effect of humidity
in the circuit on the CO2 absorption capacity of Amsorb and Sodasorb II. J
Anesth, 17: 145-146
Stabernack, C.R., Brown, R., Laster, M.J., Dudziak, R. & Eger, E. (2000) Absorbents
differ enormously in their capacity to produce compound A and carbon
monoxide. Anesth Analg., 90:1428–1435
USP–NF. (2010). United States Pharmacopeia (USP) and the National Formulary
(NF). Available online at: http://www.usp.org/USPNF (Last access date: 26
August 2010).

10
 11

View publication stats