Pilot-Scale Biological Sulfide Oxidation Process for Treating Effluent

from Rayon Industry

Maung Myo Kyaw and Prof. Ajit P.Annachhatre

Environmental Engineering and Management, School of Environment, Resources and

Development, Asian Institute of Technology, Thailand, May 2008

Abstract

This investigation was involved the design of pilot scale biological sulfide oxidation
concentric draught-tube internal-loop airlift reactor based on the available laboratory scale
experiment. This pilot scale biological sulfide oxidation airlift reactor was fabricated and
installed at Thai Rayon Industry. The sulfide oxidation airlift bioreactor which contained
mixed cultured of sulfide oxidizing bacteria oxidized sulfide to elemental sulfur and sulfate.
The purpose of this experiment was to investigate the optimum oxygen supply for
maximum sulfide removal and sulfur recovery as well as sulfide loading rate. In this
research, the concentric draft-tube internal-loop bioreactor was used because of its good
mixing property. Thus a high recirculation inside the reactor was achieved and most of
sulfide was converted to elemental sulfur which was settled down in the secondary
sedimentation tank. The biological sulfide oxidation was investigated under the optimal
operating conditions for maximizing sulfide removal and sulfur production during the
steady state conditions. The airlift bioreactor was operated under optimum pH (7.5-8) and
ambient temperature (30-40 ºC). The flow rate and HRT were maintained 600 L/day and 4
hrs respectively. The sulfide loading rate steadily increased up to 4.38 kg HS-/m3-day by
increasing the influent sulfide concentrations up to 730 mg/L. The DO concentrations were
maintained less than 0.2 mg/L during the whole process. In addition, cost benefit analysis
(CBA) was compared base on economic and environmental aspects between conventional
treatment and developed technology.

Keywords: sulfide oxidation, sulfur recovery, airlift bioreactor, sulfide loading rate,
dissolved oxygen concentration
Introduction

The anaerobic treatment of wastewaters containing partially oxidized sulfur components

such as thiosulfate, sulfite, or sulfate, causes the reduction of these compounds to sulfide.
Such types of wastewaters are produced from different industries like the petrochemical,
the photographic processing, and the pulp-paper industries and those wastewaters are
called “sour water” (Kuenen, 1975) which was originated to describe a waste contaminated
with sulfide. Sour water streams in the refineries are generated from sour stream
condensates from distillation, thermal or hydrogen cracking operations, and product
heating process (Berne and Cordonnier, 1995).

Sulfide oxidation under sufficient conditions of oxygen or nitrate, the oxidation of sulfide
can proceed spontaneously. Biological oxidation of sulfide can be proceeds under aerobic,
anoxic and anaerobic conditions. In the presence of oxygen or nitrate, the colorless sulfur
bacteria oxidize sulfide to sulfur or sulfate. Anaerobic sulfide oxidation is performed by
the green and purple phototrophic bacteria, using the sulfide electrons for the reduction and
assimilation of CO2 and gaining energy from the sunlight.

Hydrogen sulfide is toxic to aquatic animal life in very low concentrations. The threshold
limit value for fresh or salt water fish is 0.5 ppm. Sulfide in wastewater is also corrosive
and has a very unpleasant odor and sulfide has a high oxygen demand of 2 mol O2/mol S2-
resulting in depletion of oxygen where sour wastewater is discharged (Kobayashi et al.,
1982).

Biological treatment for sulfate rich wastewater consists of two main processes namely
sulfate reduction and sulfide oxidation, which take place in separate reactors. First, the
sulfate is converted into sulfide in sulfate reduction process and some of this sulfide is used
for heavy metal precipitation. The metals precipitate as metal sulfides, which are separately
removed. It is possible to selectively recover different metals from the contaminated water
based on the principle of different solubility of metal sulfides at different pH. This way it is
possible to selectively recover, for example, Cu2+, Pb 2+ and Zn2+ with compared to
precipitation of metals with lime, much lower effluent concentrations can be achieved (ppb
level) by using biotechnology due to the much lower solubility of metal sulfides (Buisman.,
et al., 1999).

SRB
SO42- + 4H2 H2S + 4H2O Eq. 1

Metal + sulfide metal-sulfide↓ Eq. 2

Remaining sulfide is partially oxidized and converted to settleable oxidized sulfur cake
which is easily to remove in process. Other advantages are no chemical addition required
and can be reused for the raw material of sulfuric acid or it can be used as fertilizer. The
reuse of metal sulfides depends on the type of metals. If for example only Zn2+ is
precipitated, it can be recovered in zinc refineries. In case of H2S removal from wastewater,
the influent sulfide is oxidized into sulfur and hydroxide and this alkalinity forming is
reused from the effluent. The most two important biological conversions of an aerobic
sulfide removal system are outlined as follow.
 SOB
2HS- + O2 2S0 + 2OH- ∆Gº = -210.81 kJ/mol Eq. 3

SOB
2HS- + 4O2 2SO42- + 2H+ ∆Gº = -796.48 kJ/mol Eq. 4

And other researcher, Gonzalez et al., 2005, found that thiosulfate was converted to
elemental sulfur under limited oxidation and converted to thiosulfate under excess amount
of oxygen.

SOB
S2O32- + ½ O2 S0 + SO42- ∆Gº = -231 kJ/mol Eq. 5

SOB
S2O32- + 2O2 + H2O 2SO42- + 2H+ ∆Gº = -739 kJ/mol Eq. 6

Objectives of study

The objectives of this study were to design pilot scale sulfide oxidation air lift reactor
based on data from laboratory investigation and to start up the biological sulfide oxidation
process in airlift reactor by using acclimatized seed sludge and then, to optimize the
operating parameters such as sulfide loading rate, dissolved oxygen concentration and pH
to get the maximum sulfur recovery.

Materials and Methods

The wastewater from spinning process in Thai Rayon Industry was containing high
concentration of sulfate and metal zinc. In sulfate reducing gaslift reactor, sulfate was
reduced by sulfate reducing bacteria (SRB) by using hydrogen gas as an electron donor and
sulfate reduced to sulfide. One portion of these sulfides was used for Zn removal and the
remaining sulfide was fed to bottom part of the concentric draught tube internal loop airlift
reactor for sulfide oxidation process and recovered sulfide as sulfur by using sulfur
oxidation bacteria (SOB) in airlift reactor, which can be further used as raw material for
sulfuric acid production.

The Pilot scale sulfide oxidation airlift reactor was operated under ambient temperature to
treat the sulfide rich wastewater (effluent from sulfate reduction gaslift reactor). The waste
stream was continuously fed to the bottom part of the airlift reactor and air was sparged at
the bottom of the draft tube and creating air bubble up to top of the draft tube by using air
diffuser. The wastewater and air were completely mixed through the draft tube and to
create the airlift condition. Because of different gas holdup between upper and bottom
parts of the reactor, the liquid circulation was well promoted and the biomass and
wastewater were completely mixed throughout the reactor working volume while DO
concentration increased through the draft tube from the bottom to the top by aeration and
decreased along the down comer from the top to the bottom due to oxygen consumption of
activated sludge.
The DO concentration inside the reactor was controlled to favor the partial oxidation of
sulfide to elemental sulfur by the group of colorless sulfur oxidizing bacteria. The
operation was carried out to obtain optimum operating conditions to get the maximum
sulfur recovery. The biologically produced sulfur was settled down to the bottom part of
the reactor by gravitationally and removed from sludge drain out pipe. The airflow meter
was set up to control the air fed into the reactor. The pH was maintained within 7.5 to 8 by
adding hydrochloric acid. Sodium bicarbonate used as carbon source was provided for
sulfur oxidizing bacteria and the nutrient solution was supplied for the growth of bacteria.
The sedimentation tank was provided in the downstream of the airlift reactor to recover the
biologically produced sulfur. The process diagram for pilot scale sulfide oxidation airlift
reactor is illustrated in Figure 1.
Air

Airlift Settler
Reactor
Effluent

HCl
Nutrient
+
NaHCO3

Tap
Water

Synthetic
Wastewater Sulfur
Sludge
`

Air
Feeding
Flow
Tank
Meter

Feeding
Air
Pump
Sulfur
Sludge

Figure 1: Process Flowchart for Sulfide Oxidation in Airlift Reactor

Internal-loop airlift reactor configuration

The fiber reinforced plastic (FRP) reactor with working volume of 100 L and total volume
of 246 L (excluded settling zone) is provided. The 65 mm-inner diameter acrylic draft tube
with the length of 2710 mm is concentrically inserted into the 217 mm-inner diameter
reactor. Air is supplied from elevation tank and controlled by airflow meter. The air is
sparged thoroughly through inside the reactor by using air diffuser at the bottom of the
draft tube. Air was creating air bubble up to top of riser. The bottom clearance (50 mm) is
sufficiently provided for recirculation of wastewater from downcomer. The settling zone is
provided at the bottom part of the reactor to settle biologically produced sulfur that was
removed weekly at the bottom port. The design parameter of sulfide oxidation airlift
reactor is mentioned in table 1.

Table 1: Design Parameter of Sulfide Oxidation Internal-loop Airlift Reactor

Parameter Values
(Volumetric Sulfide Loading Rate)design 6 kgHS-/m3-day
Flow Rate (Qavg) 0.6 m3/day
Flow rate (Qmax) 1 m3/day
Reactor Working Volume 0.1 m3
Total Volume 0.247 m3
Draft Tube Length 2.71 m
Draft Tube Diameter (Dd) 0.065 m
Column Diameter (DCi) 0.217 m
Column Height 2.59 m
Upper Column Diameter 0.67 m
Upper Column Height 0.42 m
Baffle diameter 0.217 m
Baffle height 0.55 m
Settling Basin Height 0.132 m
Maximum air flow rate 10 L/min

Preparation for start up

Biomass: The reactor was started up by using activated sludge from Thai Rayon Industry
in Thailand. The active sludge was acclimatized by feeding with sulfide-containing
synthesis wastewater (Na2S.3H2O) and mixed with NaHCO3 (carbon source) in the ratio of
4.309: 1(mol S2-/mol Carbon) in an open tank.

Wastewater: The synthesis wastewater (Na2S.3H2O) was provided to biological sulfide

oxidation airlift reactor. NaHCO3 was used as a carbon source in a ratio of 4.309: 1 (mol
S2-/mol Carbon). The concentric hydrochloric acid (38% W/W) was added to synthetic
wastewater tank to adjust the optimum pH.

Nutrient Solution: The nutrient solution composed with NH4Cl and KH2PO4 was
provided with the C: N: P ratio of 100: 5: 1 (by weight) mentioned in Table 2;

Table 2: Chemical Composition for biological sulfide oxidation process

Composition Quantity
Feed concentration for start up Up to 200 mg HS/L
Feed concentration for steady state Up to 730 mg HS/L
NaHCO3 4.309: 1 (mol S2-/mol Carbon)
C:N:P 100:5:1
Adjust pH 7.5-8 with 38% HCl (W/W)
Laboratory analytical methods

Sulfide and Sulfate: Sulfide and sulfate were measured by Standard Methods for
Examination of Water and Wastewater, 20 th Edition, 1998 (APHA-AWWA-WEF, 1998)

Sulfide: Sulfide was analyzed by iodometric method, Method LWI-5001/ETM 112 for
water, wastewater analysis according to standard method, 1998.

Sulfate: Sulfate was analyzed by Turbidimetric method by method 4500 and by using
HACH-2100P Turbidimeter.

Sulfite: Sulfite was analyzed by Thai Rayon Laboratory Standard Method. The brief
description for this method was mentioned in appendix A.

Thiosulfate: Thiosulfate was analyzed by iodometric method, Method LWI-5003/ETM

304 (Scrubber Liquor Analysis).

TSS and VSS: TSS and VSS were measured by solid determination methods, method
numbers 2540 B and 2540 E mentioned in Standard Methods for Examination of Water
and Wastewater, 20th Edition, 1998 (APHA-AWWA-WEF, 1998).

Sulfur Mass Balance in Sulfur Oxidation Process: The amount of biologically produced
sulfur (S0) can be calculated by subtracting the produced amount of S2-- sulfur, SO42--sulfur,
S2O32--sulfur, SO32--sulfur from the sulfide conversion. Concentration of sulfate resulting
from the addition of nutrient solution into the reactor was subtracted from the total sulfate
concentration determined in the reactors. The mass balance for sulfur production is
expressed as following equation:

(HS--S + SO4 2—S + S203 2--S+ (HS--S+ SO4 2--S+ S20 3 2--S+ SO32--S)out Eq. 7
=
SO32--S) in *Qin * Qout + S0

S0 * 100
% Sulfur Production = Eq. 8
(HS--S + SO4 2--S + S20 3 2--S+ SO32--S) in *Qin
2-

Where;
HS--Sin = influent sulfide concentration (mg HS-/L)
-
HS -Sout = effluent sulfide concentration (mg HS-/L)
SO42--Sin = influent sulfate concentration (mg SO42-/L)
2-
SO4 -Sout = effluent sulfate concentration (mg SO42-/L)
2-
SO3 -Sin = influent sulfite concentration (mg SO32-/L)
2-
SO3 -Sout = effluent sulfite concentration (mg SO32-/L)
S2O32--Sin = influent thiosulfate concentration (mg S2O32-/L)
SO3 -Sout= effluent sulfite concentration (mg SO3 2-/L)
2-

S0 = biologically produced sulfur (g/day)

Qin = influent flow rate (L/day)
Qout = effluent flow rate (L/day)
Result and Discussion

This chapter discusses on the result of pilot scale investigation of biological sulfide
oxidation process in airlift reactor which conducted to sulfate reduction process in Thai
Rayon Industry. The pilot plant was continuously operated for 72 days and the experiments
were investigated into 2 main parts:

Start up and steady state operation of the biological sulfide oxidation process by
using synthesis wastewater mixed with industrial wastewater, and

Steady state operation of biological sulfide oxidation process by using synthesis

wastewater mixed with tap water.

Pilot scale biological sulfide oxidation process

For biological sulfide oxidizing process, the main important biological conversions of an
aerobic sulfide removal system are outlined as following: (Buisman et al., 1990)

2HS- + O2 2S0 + 2OH- ∆Gº = -210.81 kJ/mol Eq. 9

2HS- + 4O2 2SO42- + 2H+ ∆Gº = -796.48 kJ/mol Eq. 10

At dissolved oxygen concentration below 0.1 mg/L (oxygen limiting condition), sulfur is
the major end product of the sulfide oxidation (Eq. 4.1), while sulfate is formed under
excess oxygen circumstances (Eq. 4.2). Since elemental sulfur is easier to be removed and
sulfate formation leads to four-fold higher oxygen consumption and consequently a higher
energy demand, the formation of elemental sulfur is preferable (Janssen et al., 1995). Apart
from the biological sulfide oxidation, the chemical oxidation of sulfide has to be accounted
as well. In case of highly loaded bioreactors, not all sulfides would be converted into sulfur
due to a limitation in biological activity. The chemical auto-oxidation of sulfide to
thiosulfate becomes relatively important as indicated below (Chen & Morris et al., 1972):

2HS- + 2O2 H2O + S2O32- ∆Gº = -387.34 kJ/mol Eq. 11

And other researcher, Gonzalez et al., 2005, found that thiosulfate was converted to
elemental sulfur under limited oxidation and converted to thiosulfate under excess amount
of oxygen (Eq. 4.4 and Eq.4.5).

SOB
S2O32- + ½ O2 S0 + SO42- ∆Gº = -231 kJ/mol Eq. 12

SOB
S2O32- + 2O2 + H2O 2SO42- + 2H+ ∆Gº = -739 kJ/mol Eq. 13
Reactor startup

After 10 days of cultivation, 40 L (40 % capacity of reactor) of sludge which contained

VSS concentration of 4,000 mg/l was filled in the airlift bioreactor with 60 L tap water.
And the sulfide containing synthesis wastewater was mixed with effluent from sulfate
reducing process in feeding tank and then fed into the reactor with the flow rate of 600 L/d.
The sulfide influent concentrations were steadily increased from 50 mg/L to 100 mg/L
(loading rate up to 0.67 kg HS-/m3-day) and influent flow rate was maintained 600 L/d
during startup period for 15 days and the hydraulic retention time (HRT) was 4 hrs. The
temperature was between the ranges of 25 to 40 ºC (ambient temperature) and pH was
maintained 7.5 to 8 by adding with concentrated HCl (38 % W/W).
.
The nutrient solution (NH4Cl and KH2PO4) was provided as the ratio of C: N: P = 100: 25:
5 to growth of bacteria and NaHCO3 was supplied the ratio of 4 g of Na2S/g of NaHCO3.
Both of nutrient solution and NaHCO3 were prepared in a same tank.

During the start up period, DO concentrations were maintained less than 0.1 mg/L by
providing the air flow rate between 0.3 to 0.5 L/min and controlled by an air-flow
controller. The operation parameter of sulfide oxidation airlift reactor at start up condition
was shown in table 3.

Table 3: Operation parameter at start up condition

Parameter Amount
3
Flow rate 0.6 m /day
Feed concentration 50 to 100 mg HS-/L
Volumetric sulfide loading rate Up to 0.67 kg HS-/m3.day
HRT 4 hrs
DO ≤ 0.1 mg/L
Air flow rate 0.3 to 0.5 L/min
pH 7.5-8.5
Temperature 25-40 ºC (Ambient temperature)
Start up period 15 days

In startup period, the sulfide removal efficiencies were between the ranges of 80% to 96%
and effluent pH was slightly lower than influent pH and acidity was generated (Figure: 2).
In this period, most of the influent sulfide was converted to sulfate and sulfur was not
produced and sulfate was the major end product.

Steady state operation

The sulfide removal efficiency for the biological sulfide oxidation process in airlift
bioreactor was investigated by using synthesis wastewater mixed with industrial
wastewater. Firstly, metal zinc was removed from industrial wastewater because of its
toxicity to microorganism. So some of the sulfide containing synthesis wastewater (100
L/day) from feeding tank was recycled to mixing tank and zinc was precipitated as zinc
sulfide in primary sedimentation tank and zinc concentration was reduced to less than 3
mg/L after precipitation. The steady state operation parameters for using synthesis
wastewater mixed with industrial wastewater were mention in table 4.
Table 4: The steady state operation parameter for Phase I
Parameter Amount
Flow rate 0.6 m3/day
Feed concentration 100 to 710 mg HS-/L
Volumetric sulfide loading rate Up to 4.26 kg HS-/m3.day
HRT 4 hrs
DO ≤ 0.2 mg/L
Air flow rate 1 to 4 L/min
pH 7.5-8.5
Temperature 25-40 ºC (Ambient temperature)
Steady state period 22 days
Carbon source (NaHCO3) 4.309: 1 (mol S2-/mol Carbon)
Nutrient solution (C:N:P) 100:5:1
Adjust pH 7.5-8 with 38% HCl
(W/W)

The sulfide loading rates were steadily increased from 0.77 kg HS-/m3-day to 4.26 kg HS-
/m3-day by increasing the influent concentration from 112 mg/L to 710 mg/L and the flow
rate and HRT were maintained 600 L/day and 4 hrs respectively. DO concentration were
maintained less than 0.2 mg/L by adjust the air flow rate during this period (Figure 3).
After 17 days running, the effluent pH was slightly higher than influent pH and alkalinity
was started to generated and sulfur was started to produce. After 45 days running, when
sulfide loading rate was over 2.5 kg HS-/m3-day, effluent pH were sharply higher than
influent pH (Figure 2).

Inf pH Eff pH Temp:

14 45

13 40
Influence & Effluence pH

12 35
30
Temperature
11
25
10
20
9
15
8 10
7 5
6 0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70
Days

Figure 2: Temperature and pH monitoring for sulfide oxidation process

 DO
2

DO concentration (mg/l)
1.8
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70
Days
Figure 3: DO monitoring for sulfide oxidation process

Inf Sulfide Eff Sulfide

800
Inf & Eff Sulfide Concentration

700
Phase I Phase II
600
500
(mg/l)

400
300
200
100
0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70
Days

Figure 4: Influent and Effluent Sulfide Concentration on Phase I & II Operations

During 30 days operation, the influent sulfide concentration started from 80.5 mg/L and
then steadily increased up to 700 mg/l and the flow rate was maintained 600 L/day. And
the sulfide removal efficiency was between the ranges of 87% to 100% during the
operation period (Figure 5). During the first 10 days reactor operation, the sulfide removal
efficiencies were the range between 95% to 100% and the volumetric sulfide loading rate
was steadily increased up to 2.73 kg HS-/m3-day and the sulfur was produced up to 579
g/day. After this period, the TSS concentration was very high (11.5 g/L) because of the
biologically produced sulfur inside the reactor, and these sulfur particles were interfered to
oxygen respiration to microorganism and the sulfide removal efficiencies were decreased
and also sulfur production declined to 480.5 g/day. So some amount of sludge (10 L of
sludge) was removed from the reactor after 10 days operation.
 5 100%
4.5 90%

Volumetric Sulfide Loading Rate

4 80%

% Removal Efficiency
3.5 70%
(kg HS-/m3-d)
3 60%
2.5 50%
2 40%
1.5 30%
1 20%
0.5 10%
0 0%
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70
Days
VSLR % Removal Efficiency

Figure 5: Sulfide Loading Rate & Sulfide Removal Efficiency monitoring on Phase I &
Phase II Operations

During the operation, when the sulfide loading rates were lower than 3 kg HS-/ m3-day,
sulfur productions were 70% to 80% and sulfate productions were 20% to 30%. When
sulfide loading rate was higher than 3 kg HS-/ m3-day, sulfur productions were increased
up to 90 % and sulfate production were decreased below 20%. So from this experiment, at
high sulfide loading rate, the sulfur is the major end product. And also other researchers,
Annachhatre and Suktrakoolvait, 2001, found that more sulfur was produced when sulfide
loading rate was started to raise from 1.3 kg HS-/ m3-day.

% sulfur production % Sulfate production VSLR

100% 5
90% 4.5
% Sulfur & Sulfate production

80% 4
70% 3.5

60% 3
50% 2.5
40% 2
30% 1.5
20% 1
10% 0.5
0% 0
0 5 10 15 20 25 30
Days

Figure 6: The sulfide loading rate and % Sulfur & Sulfate Production from influent sulfur
species monitoring for Phase II operation
During the Phase II operation, the influent sulfide concentrations were steadily increased
up to 730 mg/L and the influent sulfate concentrations were less than 30 mg/L. The
effluent sulfide concentrations were less than 50 mg/L and the effluent sulfate
concentrations were between 200 mg/L to 400 mg/L during the process. After 15 days
period, although the sulfide loading rates were raised, the effluent sulfate concentrations
were declined below 350 mg/L. That was meant that, when the high sulfide loading rate,
the sulfur was the major end product.

In Phase II operation, at low sulfide loading rate and DO concentration less than 0.2 mg/L,
most of the sulfide was converted to sulfate and sulfur production was low during the first
5 days operation. When sulfide loading rate was higher than 2.5 kg HS-/ m3-day and DO
concentration still maintained less than 0.2 mg/L, though the sulfur production was sharply
high, sulfate formations in effluent were lower than the low sulfide loading rate operation.
According to the stoichiometry equations of sulfide and thiosulfate aerobic oxidation
reactions, oxygen requirement for sulfur production was fourfold less than the oxygen
requirement for sulfate formation. So oxygen was the key parameter for sulfur recovery
and maintains the optimum DO concentration was also essential. In this research, DO
concentrations for both Phase I and Phase II operations were carefully maintained the
optimum condition (DO < 0.2 mg/L). From this experiment, when DO concentration was
less than 0.15 mg/L, the sulfur was the main product and when DO concentrations were
maintained around 0.1 mg/L, the maximum sulfur productions were occurred. When DO
concentrations were higher than 0.15 mg/L, the sulfur formations were significantly high.

Conclusion

This study was shown that the biological sulfide oxidation process in the airlift reactor was
more satisfactory for sulfide removal efficiency and elemental sulfur production than the
conventional methods. The sulfide oxidation process was strongly depended on the
parameters of volumetric sulfide loading rate, DO concentration, pH and temperature. The
airlift bioreactor was operated under optimum pH (7.5-8) and ambient temperature (30-40
ºC) and influent wastewater flow rate and HRT were maintained 600 L/day and 4 hrs
respectively. The DO concentrations were maintained less than 0.2 mg/L during the
process and the sulfide loading rate steadily increased up to 4.38 kg HS-/m3-day. Under
steady state condition, the elemental sulfur was successfully produced and which is heavier
than the sludge and easily to settle inside the reactor. Based on the experiment results
investigated from this research, the following conclusions are given as follow:

1. Under the oxygen limited conditions (DO less than 0.2 mg/L), the sulfide removal
efficiencies were between 88% to 100% and elemental sulfur were produced 70 %
to 90% of influent sulfur species.

2. At the low sulfide loading rate (0.48-1.25 kg HS -/m3-day), sulfate was the major
end product and when sulfide loading rate higher than 1.25 kg HS-/m3-day, the
elemental sulfur production gradually increased.

3. When sulfide loading rate was higher than 3 kg HS-/m3-day and DO concentration
less than 0.15 mg/L (the optimum DO was around 0.1 mg/L), the sulfur was the
major end product (80% to 90% sulfur conversion) and the sulfate conversions
were reduced below 20% of influent sulfur species.
 4. The biologically produced sulfur was accumulated inside the reactor during the
steady state operation and which interfered the sulfur production and sulfide
removal process. So this biosulfur inside the reactor should be removed regularly
during operation.

5. Finally, the biological sulfide oxidation in the concentric draught tube internal loop
airlift bioreactor showed the satisfactory results for sulfide removal and sulfur
recovery. In addition, the sulfate reduction process followed by sulfide oxidation
process is very suitable treatment for sulfate rich wastewater and which is a
beneficial choice for environmental aspect as well as economic aspect.

List of Abbreviations

°C Degree Celsius
dc Column diameter or equivalent hydraulic diameter
dD Draught-tube diameter
dO Diameter of sparger hole
DO Dissolved oxygen concentration
e- Electron
FRP Fiber reinforced plastic
g Gram
∆G° Gibb’s free energy
h Overall reactor height
H Henry law constant
hr Hour
kJ Kilojole
Kg Kilogram
L Liter
m Meter
mg Milligram
min Minute
mm Millimeter
mol Mole
Q Volumetric flow rate
r Rate of reaction
s Second
SOB Sulfide oxidizing bacteria
SRB Sulfate reducing bacteria
T Temperature
TDS Total dissolved solid
TSS Total suspended solid
V Volume
Zn Zinc
 References

Annachhatre A.P.1; Suktrakoolvait S.1, Biological Sulfide Oxidation in a Fluidized Bed

Reactor, Environmental Technology, Volume 22, Number 6, 1 June 2001 , pp. 661-
672(12) Publisher: Selper Ltd.

Buisman, C.N.J. (1989). Biotechnological sulfide removal with oxygen. PhD thesis,
Wageningen Agricultural University, Wageningen, The Netherlands.

Buisman, C.N.J., Geraats, B.G., Ijspeert, P., and Lettinga, G. (1990). Optimization of
sulfur production in biotechnological sulfide removing reactor. Biotech. Bioeng 35,
50-56.

Buisman, C.J.N., Geraats, B.G., Ijspeert, P., and Lettinga, G., 1990a. Optimization of
Sulfur Production in a Biotechnological Sulfide-Removing Reactor. Biotech. Bioeng,
35:50-56.

Buisman C.J.N. *, S.H.J. Vellinga**, G.H.R. Janssen* and H. Dijkman*, (1999).

Biological sulfide production for metal recovery, *PAQUES, B.V., P.O. Box 52,
8560 AB Balk, Netherlands, http://www.paques.nl/?pid=101

Chen, K.Y. & Morris, J.C. (1972). Kinetic of oxidation of aqueous sulfide by O2. Environ
Sci Technol, 6, 529-537.

Chisti, M.Y. (1989). Airlift Bioreactors, Elsevier Science Publishers Ltd., New York.

Chisti, M.Y., and Moo-Young, M., (1987a), in Bioreactor and Biotransformations, Elsevier
(London), pp. 335-349

Gonzalez. A, Alcantara. S, Razo-Flores. E, and Revah. S., 2005, Oxygen Transfer and
Consumption in a Thiosulfate Oxidizing Bioreactor with Sulfur Production, The
Society for applied Microbiology, letters in Applied Microbiology, 41, 141-146

Jensen, A.B., Webb, C. (1995). Treatment of H2S containing gases: a review

ofmicrobiological alternatives. Enzyme Microbiol Technology. 17, 2-10.

Janssen, A.J.H., Ma, S.C., Lens, P., and Lettinga, G. 1997. Performance of a Sulfide-
Oxidizing Expanded-Bed Reactor Supplied with Dissolved Oxygen. Biotech. Bioeng.
53: 32-40.

Kuenen, J.G. (1975). Colorless Sulfur Bacteria and their Role in the Sulfur Cycle. Plant
Soil, 43, 49-76.

Lee, C. & Sublette, K.L. (1993). Microbial Treatment of Sulfide-Laden Water. Wat Res
27(5), 839-846.

Standard Methods for the Examination of Water and Wastewater, 20th Edition, 1998.
American Public Health Association, 1015 Fifteenth Street, NW, Washington, DC
20005-2605