Insights

Insights into
into the
the sorptive
sorptive removal
removal properties
properties of
of various
various
adsorbent
adsorbent against
against gaseous
gaseous sulfur
sulfur compounds
compounds

Presented
PresentedBy
By::
Kowsalya
KowsalyaVellingiri
Vellingiri

Adviser:
Adviser:
Ki-Hyun
Ki-HyunKim
Kim

Air
Airpollution
pollutionmanagement
managementlaboratory,
laboratory,Department
Departmentof
ofCivil
Civiland
andEnvironmental
Environmental
Engineering,
Engineering,Hanyang
HanyangUniversity,
University,Korea
Korea

1. Background
The mitigation and control of sulfur compounds in the atmosphere are important due to their well-known
strong malodourous properties, even typically at sub-ppb concentration level.

For example, the odour thershold values of sulfur compounds were Hydrogen sulfide (H2S)=0.41 ppb and
Methyl mercaptan (CH3SH) = 0.07 ppb. Even in this low concentration it will produce strong rotten-egg and
distinctive putrid smell.

Moreover, sulfur compounds have varying degrees of deleterious effects on human health, if they are
present above certain threshold values. For instance, dimethyl disulfide (DMDS) can be toxic if inhaled or
adsorbed through the skin, even moderate concentrations of sulfur dioxide (SO2) result in a decrease in lung
function, and CH3SH is responsible for bad breathe.

Most of the above mentioned sulfur compounds also showed various environmental damages. The SO2 acts
a secondary pollutant in the production of the acid rain that can cause significant ecological damage to
lakes and forests, CH3SH can be converted into DMS and DMDS during LPG production processes and it
makes the disturbance in the cycles of aquatic ecosystem.

2. Purpose
According to the WHO, US EPA, and KMOE indoor air is more polluted than the outdoor air. Most of
the pollutant in an indoor is emitted from the degradation of vegetables and fruits.
The charcterized main pollutant in the indoor includes sulfur compounds including H2S, CH3SH, DMS,
DMDS, and SO2 where it has well known source region from rotten egg and rotten cabbages.

Rotten egg
H 2S

Rotten cabbage
CH3SH

Asparagus
DMS

Canned corn
DMS

Black current
DMS

Onion like
DMDS

Hence it is important to find out suitable adsorbent to reduce the concentration levels of reduced and
oxidized sulfur species in both indoor and outdoor environment.

Synthetic
zeolite
A4 was used
as an adsorbent
to remove
concentration
(ppb)ofgaseous
mixture of four
WHO:
World Health
Organisation,
EPA: Environmental
protection
agency, low
and KMOE:
Korean Minstry
Environment
reduced (H2S, CH3SH, DMS, and DMDS) and one oxidized sulfur species (SO2).

3. Meterials and methods

Synthetic zeolite A4 (Na2O . AI2O3 . 2SiO2 . 4.5H2O)

Zeolites are crystalline alumino silicates with an ordered frame work structures built by
corner sharing of SiO4 and AlO4 units.
The window like structure of the zeolite ( and cages) responsible for the adsorption
characteristics under identical conditions.
Zeolites are a cheap source of materials with high thermal and chemical stability. In
addition usually their pore opening were below 1 nm which makes them perfect solids for
gas phase reactions.

4 (a). Experimental sequence

Stage 1: Examination of the sampling bag quality and
preparation of the gaseous working standard (G-WS)
Experiment-1
(Calibration
experiment)

Stage 2: AS/TD based calibration of G-WS (4 point

calibration with the fixed sampling flow rate 50 mL
min-1)
Stage 3: Basic quality assurance (MDL and RSE)
experiment

(1) RSC working standard for analysis

5

(2) Silicon tube

(3) Airserver line
(4) Air Server (AS)/ Thermal desorption (TD) system
(5) Connector line
(6) Flame Photometric Detector (FPD) system
6

1
4

Figure 1(a). A basic flow chart of an experimental approach used for the calibration experiment

4 (b). Experimental sequence

Stage 1: The tube sampler was prepared using 100 mg
of untreated zeolite (as received) and glass wool as a
supporting material
A. Preliminary steps

Stage 2: The prepared sampler tube subjected to blank

analysis by passing ultra pure N2 at the fixed sampling
flow rate (50 mL min-1) for 10 min

Experiment - 2
(Experimental approach for
the sorptive removal of
sulphur compound)

Stage 1: (Increasing loading (IO) approach)

By passing G-WS through zeolite tube sampler in an ascending
order to derive 4 point calibration (4 consecutive runs with the
sampling interval of 2, 4, 10, and 20 min at the sampling flow
rate of 50 mL min-1)

B. Experimental approach

Stage 2: (Decreasing loading (DO) approach)

By passing G-WS through same zeolite tube sampler in an
descending order to derive 4 point calibration
(4 consecutive runs with the sampling interval of 20, 10, 4, and
2 min at the sampling flow rate of 50 mL min-1)
2

(1) RSC working standard for analysis

(2) Silicon tube

(3) Sorbent tube (Quartz wool : Zeolite : Quartz wool)
(4) Silicon tube connected with AS/TD
(5) Air Server (AS)/ Thermal desorption (TD) system
(6) Connector line

(7) Flame Photometric Detector (FPD) system

Figure 1(b). A basic flow chart of an experimental approach used for the sorptive removal experiment

5. Methods
Table 1. Summary of mass concentrations of sulfur gases (SO2 and four RSCs) and their basic QA/QC test investigated in
this study
Order

WS
Conc.
(ppb)

Loading
Time
(min)

Volume
(mL)

Reduced sulfur compounds

SO2

H2S

CH3SH DMS

DMDS

Calibration experiment
a. Calibration standard
(ppb)
1

10

10.3

10.4

10.0

10.4

10.1

20

20.5

20.7

20.0

20.7

20.2

50

51.3

51.8

50.0

51.8

50.5

100

103

104

100

104

101

b. Injected mass

10

Objective:

To detect the stability of the Zeolite between

two different loading approaches.
20

To find out the interactive relationship

between zeolite and diverse sulfur gases.

Variation in the adsorption characteristics

with respect to initial concentration levels.
7

50

100

2.61

1.44

2.03

2.56

3.94

200

5.23

2.88

4.06

5.12

7.88

10

500

13.1

7.20

10.2

12.8

19.7

20

1000

26.1

14.4

20.3

25.6

39.4

100

5.23

2.88

4.06

5.12

7.88

200

10.5

5.76

8.13

10.2

15.8

10

500

26.1

14.4

20.3

25.6

39.4

20

1000

52.3

28.8

40.6

51.2

78.8

100

13.1

7.20

10.2

12.8

19.7

200

26.1

14.4

20.3

25.6

39.4

Results and discussion

Before starting the calibration experiments the instrument

performance was detected and the RF values was determined
using,

Quadratic plot

(i) Linear plot

P0.5 = RF * m
P0.5 = Square root the peak area
RF = Response frequency
M = Slope
(ii) Quadratic plot
P0.5 = RF*m + b*m2
B = Second order co-efficent
(iii) The measured RF was verified by calcultaing relative molar response factor
This comparison is similar to the the effective carbon
number (ECN) concept of the flame ionization
detector (FID).
This results supports that GC-FPD is an sulfur
number (SN) counter analogous to the carbon number
(CN) counting capability of the FID.
This supports SN agreement is excellent for CH3SH
and DMS where as moderate for H2S, SO2, and
DMDS.

Linear plot

Results and discussion

Figure 2. Plot of (A) loaded vs. unadsorbed mass (ng) detected between two consecutive sample loading (IO
and DO) approaches of SO2 and four RSCs

Results and discussion

Table 2. Comparison of the consistency of the removal efficiency between the two consecutive adsorption runs by loading standards
with increasing orders (IO) and with decreasing orders (DO) of concentration
Mean

SD

SO2

Reduced sulfur compounds

H2S
CH3SH
DMS

Cal

27.3

51.0

32.7

25.7

38.1

35.0

10.2

IO

0.00

25.9

20.3

20.3

24.6

18.2

10.5

DO

0.00

26.2

20.2

20.5

25.5

18.5

10.7

Cal

27.3

51.0

32.7

25.7

38.1

35.0

10.2

IO

0.00

32.7

27.1

10.9

26.1

19.4

13.5

DO

3.52

32.3

27.3

22.7

26.8

22.5

11.1

Cal

27.3

51.2

32.7

25.7

36.6

34.7

10.2

IO

2.63

18.5

19.0

16.7

18.6

15.1

7.02

DO

2.27

17.9

18.5

16.0

19.1

14.8

7.09

Cal

27.3

51.2

32.7

25.7

36.6

34.7

10.2

IO

4.91

20.4

19.7

16.6

17.7

15.9

6.30

DO

5.67

21.1

20.3

17.3

19.4

16.7

6.42

0.43

0.04

0.41

0.41

0.39

0.49

0.46

DMDS

Findings

The removal of SO2 maintain a very low

RF value at all concentration levels.

In contrast, all four RSCs were not

removed that effectively to show
relatively high RF values.

This may be due to the increased

diffusivity of the A4 zeolite at lower
concentrations.

H2S, CH3SH, and DMS showed no

significant differences between IO and
DO and it indicates that there was no
significant variation in challenges at
lower mass loadings.

The stastically significant variation (10

ppb: p > 0.1 and 100 ppb: p < 0.05) of
SO2 indicates the increased soild/gas

A. Response factor (RF)

10

20

50

100

B. Paired t test analysis

(i) 10 ppb

p value

partitioning between zeolite and SO2 .

Results and discussion

Table 3. Summary of the removal efficiency of zeolite against diverse sulfur species

Observations

For all sulfur species the removal efficiency was identical between two sample loading approaches at lower
concentrations.

The removal of H2S, DMS, and DMDS at higher concentration is significant.

CH3SH showed almost similar removal throught the concentrations (except 20 ppb)

Results and discussion

Figure 3. Plot of average unadsorbed mass of SO2 and

four RSCs on Zeolite surface determined from AS-TD
mode analysis

Observations

The slope value of the SO2 = 0.1812 (0.9205). It demonstrate high sorptive removal performance (overall 91.3).

The overall removal efficiency between the RSCs,

H2S > DMDS > CH3SH > DMS.

The adsorption behavior of SO2 towards zeolite was almost independent of sample loading approach and/or concentration
levels.
RSCs showed different removal profiles with respect to concentration and mass loading approaches.
The estimated average unadsorbed mass slope showed very good correlation coefficient value (R 2 = >0.99) for all reduced
sulfur species.

Results and discussion

Findings
Constant removal efficiency
Constant removal efficiency

Constant removal efficiency

Constant removal efficiency

H2S, CH3SH, DMS, and

DMDS showed consistent
removal efficiency (~50 %) at
high volume loadings of high
concentration.

For
lower
volumes
it
decreased to a constant value
of ~10-40%.

SO2 showed initially complete

removal (~100%) at low mass
loadings and for higher mass
loadings it decresaed to ~8090%.

This results confirms that

zeolite was effective to
remove the oxidized sulfur
species at low concentration
levels
effectively and
consistently.

Constant removal efficiency

Results and discussion

Findings

The 10% BTV was estimated

by drawing vertical line to the
x-axis where the removal
efficiency reaches ~90%

The 10% BTV of SO2 at 20

and 100 ppb was ~20 and 6 L.

The BTV volume of RSCs at

lower concentration ranges
were ~1.8 L (20 ppb) and ~4
to 5 L (10 ppb).

There was no detected BTV

for
RSCs
at
higher
concentration
(exteremely
small).

Overall no steep decrease in

the BTV instead it maintains
constant removal after certain
loadings.

Summary and conclusion

There was clear notable differences between the sorption characteristics of oxidized
(SO2) and reduced sulfur species (H2S, CH3SH, DMS, and DMDS).

Hence, SO2 has a relatively large BTV and its removal efficiency was 100% at lower
concentrations (and volume loadings).
On the other hand, RSCs showed constant removal efficiency 30-60%

The overall removal effectiveness of SO2 was slightly affected with increase in
concentrations, whereas RSCs showed enhanced removal efficiency at high
concentrations.
To this end, oxidation state of target is one of the sensitive parameters to determine
sorptive removal capacity of zeolite.

Future research plan

As from my previous research, zeolite is mainly suitable for the oxidized species and it also have some
limitation with the long-term addition of the sulfur compounds.

In addition, the meso porous materials (zeolite) is not effective to adsorb sulfur compounds due its
smaller pore size (1 nm).

In my next plan I want to try new synthetic materials having high pore volume and surface area with
exceptionally high selectivity towards the sulfur compounds.

In that category recently Metal Organic Framework (MOF) is a superior microporous adsorbent
materials, recently widely used for the sorption and storage processes.

The key differences between Zeolite and MOFs are,

Order

Properties

Zeolites

MOF

Crystalline

Yes

Yes

Homogeneous active sites

Yes

Yes

Surface area

<600 m2 g-1

Up to 10400 m2 g-1

Cavity size

< 1nm

Up to 4 nm

Diffusivity

Low

Low to high

Thermal stability

High

Low to medium

Chemical stability

High

Variable

Chemical versatility

Low

High

Ranocchiari et.al (2011)

Future research plan

Preparation of MOFs
For that sorptive removal experiment 4 different types of MOFs were synthesized. The formed MOFs include,

Future research plan

In this experiment we planned to study the sulfur sorptive removal properties of MOF along with Zeolite as
reference material.
The experimental scheme for this experiment as follows,

Zeolite

(1) Sulfur Working standard

(2) Silicon tube used for connection
(3) Sorbent tube containing MOF (Glass wool : Cu (BTC) : Glass wool)
(4) Airserver (AS) connector line
(5) AS/Thermal desorber (TD) system
(6) Connector line
(7)Agilent GC

MOF

Future research plan

The above method of sorptive removal in the next step was verified using the areal agricultral samples
collected from the pigpen (Pigpen solid and liquid wastes).
The experimental scheme for this experiment as follows,
Sample collection

Sorptive removal analysis

Real
samples

(1) Sulfur Working standard

(1) Ultra pure nitrogen gas (99.999%)
(2) Silicon tube used for connection
(2) Air flow regulator
(3) Sorbent tube containing MOF (Glass wool : Cu (BTC) : Glass wool)
(3) Impinger bottle

(4) Airserver (AS) connector line

(4) Glass tubing with a bubbler tip to evenly distribute the diluent gas
(5) AS/Thermal desorber (TD) system
(5) Aluminum container
(6) Connector line
(6) Water heated to 30
(7)Agilent GC
(7) Heater

Thank for your kind attention

Any questions or commands or suggestions?