BIOREACTOR FOR THE REMOVAL OF SO2 FROM WASTE AIR

Abstract
Air pollution is increasing day by day due to the rapid
industrialization and urbanization. Sulfur Dioxide is one of most noxious air pollutant,
which is harmful to the habitat and Ecosystem. Different control technologies are being
applied for source reduction and end of the pipe treatment of SO 2. These technologies
cannot reduce the concentration of SO2 to zero level and accordingly, stacks are being
used for discharging the flue gas. Besides this, there is no control on the emissions form
automobile exhaust. The life of SO2 in atmosphere is small because, immediately after
the emission it would be converted to sulfurous acid and results in acid rain due to
photochemical and other reactions. Therefore, treatment of waste gases containing SO2 to
zero level is highly important for ecological balance. Studies are conducted in an
anaerobic batch, semi-continuous and continuous Bioreactor for the treatment of SO2
containing air in order to understand the various parameters. Sulfur dioxide was
generated using copper turnings and sulfuric acid. Media composition is optimized for
growing SRB’s and absorbing Sulfur dioxide. Mixed cultures of SRB’s are isolated &
acclimatized. The study shows that sulfite can be degraded to sulfide to the tune 80-90%
at inlet concentration of approximately 350 mg/L with Hydraulic residence time of 6
days. The reactor was stable in terms of pH and no loss of microbial population is
observed. The batch and semi-continuous reactors are operated repeatedly for number of
cycles in order to understand the reproducibility and stability of the microbes in the
reactor. The studies also show that dynamic equilibrium is establishing for Sulfide in
aqueous phase and H2S in gas phase. Culture showed excellent microbial activity &
specific productivity during the course of study for all the experiments. The studies
revealed that by the application of appropriate Bioreactor, SO2 from the waste gas could
be removed to zero level.
Introduction
Sulfur Dioxide is generated in most of the industries because all of the
industries in one way or other use raw materials or fuels that contain sulfur. Due to this
reason SO2 is invariably emitted from most of the industries. Presently Ambient air
quality standards specify that SO2 concentration should not exceed 80, 60 and 15
microgram/m3 in the industrial, residential and sensitive areas respectively. Therefore, the
industries are following Physico-chemical treatment methods (1) or stack emissions or
combination of both depending upon the level of initial concentration of SO 2 for
discharging the gaseous stream containing SO2 in the atmosphere. The chemical methods,
which are being, practiced produces secondary products that are again pollutants for the
industry. Therefore, chemical methods are producing secondary pollutants leading to a
major disposal problem. In the atmosphere, SO2 can react with various compounds can
form sulfates and sulfuric acid due to photocatalytic or some other reactions. This will
ultimately result in acid rain, which is harmful to the ecosystem. Aerosol (2) formation is
also dependent on amount of SO2 present in the atmosphere. The preset method envisages
abortion of SO2 in the organic liquid media and treatment of same liquid media in
suitable anaerobic reactor with appropriate microbial consortia namely Sulfate Reducing
Bacteria (SRB) (3, 4). Upon absorption in the liquid media, the SO2 is changed to (SO3)-2
and (SO4)-2 as per the following reaction in aqueous phase (4).

SO2 + H2O H2SO3- + H+ (1)

HSO3 + ½ O2  SO42- (2)

When this liquid media containing (SO3)-2 and (SO4)-2 is treated in anaerobic
bioreactor, the Sulfate Reducing Bacteria (SRB’s) (5,6,7,8) present in the
mixed consortia reduces the sulfite and sulfate to sulfide as represented
 below.

HSO3 - + 6 {H}  HS- + 3 H2O (3)

SO42- + 8 {H}  HS- + 3 H2O + OH- (4)
Sulfide formed in the bioreactor due to the above reaction can be either removed by
chemical methods or biological methods as per the process requirement and in situ
conditions. In the present work a continuous bioreactor was developed for the removal of
sulfur dioxide from flue gas.

Materials and Methods

Generation of sulfurdioxide gas (7)
The sulfur dioxide required for the experimentation is generated using the following
process
Equipment: Heating mantle, glass bottle with provisions for inlet and outlet, round
bottom

Flask, continuous water supply, water jet vacuum pump and silicon tubes as per
requirement.
Chemicals: Concentrated sulfuric acid, copper turnings, and SRB media.
Procedure: Known amount of concentrated sulfuric acid and copper turnings are taken in
the glass bottle, which is placed, on the heating mantle. Stock SRB media which is kept
in refrigerator is taken in the round bottom flask, one end of which is connected for the
collection of generated gas and the other end to the vacuum pump, which helps in
sucking the generated gas into absorbing SRB media. The maximum temperature is
maintained on the mantle in order to improve the reactor yield. After a little while white
fumes are observed which signifies the generation of Sulfur dioxide gas. After certain
period of time the mantle is switched off and the amount of gas absorbed is determined
by analyzing the solution for sulfite ion.
Organic media
Lactic acid that is present in the form of sodium lactate is used as organic source in the
batch and semi-continuous experiments and conditioned organic effluent is used as a
organic source in the continuous experiments.
SRB Consortia
Culture is collected from the existing anaerobic reactor treating sulfate containing
industrial waste water. The sludge is screened with fine mesh in order to remove the
foreign materials. This sludge is grown in SRB growth media and placed for isolation.
The isolated SRB culture is used as seed inoculum for batch, semi-continuos and
continuous reactors.
Analytical Methods
Standards methods (9) are used for the analysis of the sulfite and sulfide in the liquid

R
E
A
C
T
O
R

Figure 2: Semi continuous reactor set up

media and Hydrogen sulfide in the gas media
Batch reactor set up : The batch reactor set up consists of the round bottom flask placed
in the heating mantle. The round bottom flask will be provided with out let, which was
dipped inside the inverted conical flask filled with water. The outlet from the inverted
conical flask is dipped again in the water seal. Due to this arrangement strict anaerobic
condition is prevailed inside the reactor. The increase in water seal level is directly
proportional to the H2S gas generation. The schematic diagram is shown in Fig.1

Batch set up – I : 300 ml of SRB media was taken and sulfur dioxide was absorbed into

R
E
A
C
Batch T
O
reactor R

Figure 1: Batch reactor flow sheet

Figure 3:Continuous reactor set up
the solution. This was mixed with approximately 100ml of SRB consortia and put in the
Batch Reactor. The pH of the reactor contents is adjusted approximately to neutral
&reactor was closed as shown in fig.1 in order to maintain the anaerobic conditions.
Batch set up –II : 300 ml of SRB media was taken and mixed with approximately 100ml
of SRB consortia and put in the Batch Reactor. The pH of the reactor content is adjusted
approximately to neutral &reactor was closed as shown in fig.1 in order to maintain the
anaerobic conditions.
The respective organic media was replaced every 3 days retaining the culture in the
reactor. This was repeated for 5 cycles
Semi-continuos and Continuous reactor set up
The experimental setup will consists of Feed tank, recirculation tank, anaerobic
Bioreactor made up of, gas collection system and peristaltic pumps. Initially reactor is
filled with inoculum, which is described previously. The sulfite containing solution (SRB
media absorbed with SO2) after adjusting the pH in the range of 6.5-7.0 is pumped to the
reactor. The contents are recirculated via peristaltic pump through Bioreactor. Samples
are collected at the start of the experiment and at frequent intervals for analyzing the
various parameters as per the standard procedures. In case of semi-continuous process,
the organic media is replacing at certain intervals of time, whereas in continuous process
organic media is pumped continuously at desired flow rate to the recirculation tank and
same amount of bleed is taken out from the total system. The schematic diagram is shown
in Fig.2&3
Experimental procedure:
Initially reactor is filled with inoculum, which was described previously. The sulfur
oxide, which is absorbed in SRB media, is taken in the reactor or pumped through
peristaltic pump as per the mode of operation of the reactor. The temperature of the
mantle is adjusted such that approximately 350c is maintained in the reactor. The pH
inside the reactor is adjusted in between 6.5 to 7. The initial is taken and samples are
collected every day. In the two batch reactor setups, one contains the SO2 absorbed media
and the other contains the ordinary media. Thus the relative difference in the reduction of
ions is noted. Similarly semi-continuous and continuous reactors are studied.
Results and Discussions

Batch Reactor Studies

The reason for undertaking the two Batch Reactor setups simultaneously as explained

above is as follows. When the fresh SRB media is analyzed for Sulfite and sulfate,it

contains certain amount of SO32-. In order to compare this with the high amount of

Sulfite, the SO2 was absorbed purposefully in the Batch Reactor setup- I. The

experimental runs give us broad idea regarding the functioning of SRB’s at two different

experimental conditions. Three experimental runs are carried out using the Batch-

Reactor setup I & II to assess the Sulfite degradation repeatability &trend. Sulfite

degradation studies in Batch-Reactors I & II is shown in the Fig.4. The trend shows that

Sulfite degradation using the SRB cultures is in the range of 90-80%. The degradation is

higher in Batch Reactor-I compared to Batch Reactor-II. Low initial concentration of

Sulfite in Batch Reactor-II compared to Batch Reactor-I may be the possible reason for

this trend as the driving force availability is comparatively less. The % degradation trend

in Batch I& II shows 90% & 79% respectively. This indicates that Sulfite degradation in
aqueous phase using the SRB culture is efficiently carried out in the batch reactor. The

pH trend shows increasing in nature as the acidic components are getting degraded which

is as expected.

1 60

1 40

1 20

1 00

80

60

40

20

Batch Batch
Reactor - Reactor-
I II

Fig.3 :Batch
I ni tial sul f i de concentr ati on
Reactor Studies
Sul f i te r educti on (%) I nl et pH Outlet pH

Figure 4: Batch reactor studies

This is as expected and in line with the SRB role in degrading the Sulfite to Sulfide.

Similar experimental run in Batch Reactors I&II is carried out at different inlet Sulfite

concentrations. In order to assess the repeatability as well as to assess the degradation

trends at different inlet concentrations of Sulfite. The graph shows degradation trend is

very much depended on the inlet concentration of Sulfite and total driving force

available. However, approximately above 300-400 mg/L of inlet concentration, the

degradation dropped drastically indicating the inhibition of the SRB’s with respect to the

sulfide formed in the reactor. Therefore, the batch reveals that sulfite degradation in the

range of 80-90% is possible at the inlet concentration of sulfite at 300-400 mg/L with in

the appropriate pH range.

Sulfite degradation studies in Semi Continuous Reactor

Continuous operation of the bioreactor is highly essential in order to understand the

various operational and design parameters. Prior to the continuous process, semi-
continuous reactor is operated to understand the total degradation capacity of the

microbial population present in the reactor. The studies also reveal the Hydraulic

Residence Time (HRT) required in the continuous process. The results are shown in the

Fig.5. The graph reveals the fact that degradation is obtained in the same range of 80-

92% in the semi-continuous reactor also. In addition to this, in batch process HRT was 12

days where as it was only 6 days in the semi-continuous reactor. The pH is also in the

stable range indicating the process stability of the reactor in terms of microbial

population available in the reactor. The information available from semi-continuous

results was utilized in the designing and operating the continuous reactor. It can also be

observed from the graph that the sulfite concentration reduced from 450 mg/L to 40

mg/L, which is almost 92% efficiency.

Sulfite Reduction (%)

900 Sul phi te (mg/ l ) 7.65
800 Sul phi te r educti on (%)
7.6
pH
700
7.55
600
500 7.5
400 7.45
300
7.4
200
100 7.35
0 7.3
0 1 2 3 4 5 6 7
Time(days)

Figure 5: Semi-continuous reactor studies

Sulfite Degradation Studies in Continuos Reactor

In the continuous process, all the unit operations are integrated and regular analysis is

carried out to know the inlet and outlet concentration of the sulfite and pH. Hydrogen

sulfide is also measured to make the sulfur balance and it is verified. The results of the

continuous studies are shown in Fig.6. It can be observed from the graph that the inlet

concentration is maintained in the range of 300-400 mg/L and reduction of sulfite is

achieved in the range of 85-90%. The pH is also stable as observed in the previous

studies. The HRT of 6 days is constantly maintained.

Sulfite reduction(%)
400 7.65

350 7.6

7.55
300
7.5
250
7.45
200
Sulphi te (mg/ l ) 7.4
Sulphi te r educti on (%)
150
pH 7.35
100 7.3

50 7.25

0 7.2
1 2 3 4 5 6 7 8
Time(days)

Figure 6: Continuous reactor studies

Conclusions

Sulfur dioxide was generated using copper turnings and Sulfuric Acid. Media

composition was optimized for growing SRB’s and absorbing Sulfur dioxide. Mixed

cultures of SRB’s were isolated & acclimatized. Batch, semi-continuous and continuous

reactor studies are carried out to assess the possibility of sulfite degradation to Sulfide

under anaerobic condition. The study shows that sulfite can be degraded to sulfide to the

tune of 80-90% inlet concentration of approximately 350 mg/L with Hydraulic residence

time of 6 days. The reactor was stable in terms of pH and no loss of microbial population
is observed. The batch and semi-continuous reactors are operated repeatedly for number

of cycles in order to understand the reproducibility and stability of the microbes in the

reactor. The studies also show that dynamic.

equilibrium is establishing for Sulfide in aqueous phase and H2S in gas phase. The

Sulfide formed due to degradation of Sulfite is escaping through gaseous phase. In the

process excellent microbial activity & specific productivity during the course of study is

observed.

Reference:
1. Johns Eow, Recovery Of Sulfur From Sour Acid Gas: A Review Of The Technology,
Vol.21, No.3, Pp 143-162, 2002.
2. Charlson, R.J., Schwartz, S.E., Hales, J.M., Cess, R.D., Coakley, J., Hansen, J.E. And
Hofman D.J (1992) Climate Forcing By Anthropogenic Aerosols, Science, 255, 423-
430
3. Postgate Jr (1984) The Sulfate Reducing Bacteria, 2nd Ed, Cambridge University
Press, Cambridge, Uk
4. Widdel, F (1988) Microbiology And Ecology Of Sulfate And Sulfur Reducing
Bacteria, P469-586. In. A.J.B. Zehnder (Ed), Biology And Anaerobic
Microorganisms, Wiley And Sons, New York.
5. Dasu, B.N., Deshmane, V., Shanmugasundaram, R., Lee, C.M., And Sublette, K.L.
“Microbial Reduction Of Sulfur Dioxide And Nitric Oxide”, Fuel, Vol.72, No.12, Pp
1705-1714, (1993)
6. Kaufman,E.N., Little, M.H. And Selvaraj, P.T. (1996) A Biological Process For The
Reclamanation Of Flue Gas Desulfurization Using Mixed Sulfate Reducing Bacteria
With Inexpensive Carbon Sources, Appl Biochem Biotechnol 63-65, 677-693
7. S.Dutta, R.Chowdhury and P.Bhattacharya ( 2002) SO2 removal through microbial
routes-Experiments and mathemetical modelling, CHEMCON-2002, Hyderabad,India
8. Van Houten, R.T., Hulshoff Pol, L.W & Lettinga G (1994) Biological Sulfate
Reduction Using Gas Lift Reactors Fed With Hydrogen And Carbon Dioxide As
Energy And Carbon Source, Biotec And Bioeng 44, 586-594
9. Standard methods for examination of water and wastewater, 18th editon.APHA-
AWWA-WPCF.2000

Document By
SANTOSH BHARADWAJ REDDY
Email: help@matlabcodes.com
1.Engineeringpapers.blogspot.com
2.www.matlabcodes.com
3.microcontroller-project-codes.blogspot.com
4.microcontroller-library.blogspot.com
5.arduino-projects-here.blogspot.com
6.labview-projects.blogspot.com
7.java-basics.blogspot.com
8.itsnanoworld.blogspot.com
More Papers,Projects and Presentations available on above sites.