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WEFTEC.

06

DEVELOPMENT AND APPLICATION OF BIOLOGICAL H2S SCRUBBERS


FOR TREATMENT OF DIGESTER GAS
Fred Soroushian1, Yun Shang2, Eliza Jane Whitman3, Gaspar Garza4 and Zhiqin Zhang5
1&2
CH2M HILL, 3 Hutton Center Drive, Suite 200, Santa Ana, CA 92707
1
Tel: 714-435-6232, Fac: 714-424-2232, Email: fsoroush@ch2m.com
3&4
Inland Empire Utilities Agency (IEUA)
5
California Energy Commission (CEC)
ABSTRACT
As part of the California Energy Group (Former California Energy Commission) Public Interest
Energy Research (PIER) Program, biological hydrogen sulfide (H2S) biogas cleaning was
evaluated. The biological H2S scrubber uses bacteria to oxidize the sulfide to produce both
elementary sulfur and sulfuric acid. This system was tested at the Inland Empire Utilities
Agencys Regional Plant 1 (IEUA RP-1) in Ontario, California.
The biological H2S scrubber demonstrated good performance throughout the testing phase.
Based on the field measurements, The system required only a few days for startup and
acclamation. The scrubber, under normal operating conditions, maintained treated biogas H2S
levels below the target level of 40 ppmv.
KEYWORDS
Biological H2S scrubber, biogas, digestion, ferric chloride, biosolids, manure
INTRODUCTION
Biogas from anaerobic digestion of wastewater sludge or animal waste (i.e., manure) typically
contains 500 to 3,000 ppmv of hydrogen sulfide (H2S), depending on the solids composition.
Removing H2S is needed to reduce air pollution, protect power generation equipment, and
increase safety of the operations. The processes commercially used for desulfurizing biogas are
presented in Table 1.
The most commonly used methods for H2S control in wastewater treatment plants is sulfide
abatement through adding ferric chloride or pickle liquor to the wastewater or directly to the
digesters. The iron precipitates out the sulfur and prevents the production of H2S in the digesters.
In Southern California, to meet air quality requirements (40 ppmv H2S level), biogas is further
polished using the iron sponge process.

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TABLE 1
Alternative Biogas Treatment Process Technologies
Process Technology

Reactions

Representing Process

Precipitation/Scavenging

Precipitates with iron or


zinc compounds

Iron sponge, Sulfa Treat,


Sulfur-Rite, Media-G2

Caustic Scrubbing

Use alkaline to react with


acid gas of H2S

Sulfint, Sulferox, and many


other nonproprietary systems

Caustic Scrubbing/ Biological


Oxidation

Biological oxidation of
H2S to sulfur and sulfuric
acid

THIOPAQ, Biopuric*

Caustic Scrubbing/ Chemical


Oxidation

Use chemical oxidation of


H2S to sulfur and sulfuric
acid

LO-CAT, Apollo, and


CrystaSulf

* Detailed information not available

Biological H2S removal is attractive because of low energy and chemical usage requirements,
easy and automated operation, long life expectancy of system elements, potential for elemental
sulfur recovery, and no solid waste stream requiring discharge or disposal. In the biological
process, H2S from the gas stream is removed by facultative bacteria of the genus thiobacillus;
sulfur and sulfuric acid is produced from this biological H2S oxidation reaction. The key to
obtaining an efficient reaction is to provide an ideal habitat for the growth of sulfide-oxidizing
bacteria, to the exclusion of competing microbes, which normally predominate in aerobic
treatment processes. The bacteria are capable of oxidizing H2S at low pH levels. To grow, they
need oxygen/air, nutrients, and humidity. Efficient removal of H2S requires media with enough
surface area to maintain a large population of sulfide-oxidizing microbes.
Two commercial biological systems, THIOPAQ (PAQUES) and Biopuric (Biothane
Corporation), were designed for removing H2S from the sour gas. The THIOPAQ process uses
caustic to adsorb the H2S under alkaline conditions (pH 8 to 9) and aeration, in the presence of
thiobacillus bacteria, to oxidize the H2S to elemental sulfur. The Biopuric process is a
combination of a conventional chemical scrubber and a biological tricking filter. Both systems
have been reported to achieve over 90 percent removal, but both are two-stage processes and
require chemicals and significant capital investment.
IEUA RP-1 BIOLOGICAL H2S REMOVAL SCRUBBER SETUP
The biological H2S scrubber developed for testing at IEUA RP-1 is a single-stage scrubber,
consisting of a fiberglass tank packed with plastic media, a makeup water recirculation pump,
and an air blower. The system setup is illustrated in Figure 1.

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BIOLOGICAL H2S REMOVAL SYSTEM


CONDENSER
/ DRYER

S
WATER
SUPPLY

FIQ

PI

TI

BLOWER

NPK
NUTRIENTS

H2S REMOVAL
TANK
PI

TI

RECIRC PUMP
BIOGAS
FROM
DIGESTER No. 4
SAMPLE
POINT

H2SREDUCED
BIOGAS
TO
BIOGAS
HEADER

SAMPLE
POINT
TO
DISPOSAL
CONDENSATE
SAMPLE POINT

FIGURE 1
Biological H2S Removal System Setup at the IEUA RP-1
The air compressor supplying the necessary air to the process was controlled by an oxygen
sensor. If the oxygen sensor reached the high level setpoint, the air compressor would stop
operation. The pH of the fluid was also measured, and make-up water was added to the tank if
the pH sensor reached the low setpoint. The overflow system allowed excess condensate to drain.
A power meter with a totalizer was used to measure the electricity consumed by the system. The
reading and recording of this parameter were done manually. Pressure gauges and thermowells
were used to measure the pressure and temperature of the biogas. The reading and recording of
these parameters were done manually. A thermal mass flowmeter with a totalizer was used to
measure the flow of biogas. The reading and recording of this parameter were done manually.
EXISTING GAS TREATMENT METHODS AT IEUA RP-1
RP-1 has seven digesters. During this study, Digester 4 was used for manure digestion while the
remaining digesters were used for biosolids digestion. Currently, RP-1 uses the following
methods for H2S biogas treatment:

Ferric chloride addition to headworks


Ferric chloride addition directly to Digester 4
Iron sponges for polishing the combined digester biogas stream

To minimize the impact on the plant, Digester 4 was selected for testing. Because this digester is
used for manure digestion, the ferric feed to this digester could be stopped without impacting the
overall plant operation. Additionally, the literature data indicated that biogas from manure
digestion would contain similar or higher levels of H2S compared to biogas from biosolids
digestion. The biogas from Digester 4, therefore, was directed to the scrubber. The treated biogas
was then returned to the plant biogas collection system. The H2S scrubber was designed for a gas
flow rate in the range of 70 to 120 standard cubic feet per minute (scfm), an H2S inlet
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concentration in the range of 100 to 1,500 ppmv and with an air addition rate of less than
5 percent by volume.
DIGESTER 4 BIOGAS H2S CONCENTRATION
The IEUA RP-1 Digester 4 is used to process dairy manure. Ferric chloride is directly added to
the digester to control the H2S in the biogas. Digester 4 was isolated from the rest of the
digestion and gas system during the biological H2S scrubber pilot testing.
This existing method for removal of H2S in Digester 4 was monitored to establish the baseline
removal efficiency for the pilot testing. Subsequently, the impact of ferric chloride addition on
the H2S gas concentration was evaluated. Ultimately, ferric feed was gradually stopped to elevate
H2S concentrations to acclimate the scrubber to higher H2S levels.
Figure 2 shows the biogas H2S concentration and the daily ferric chloride feed rate to Digester 4.
Ferric chloride feed rate to Digester 4 averaged about 140 gallons per day (gpd), which is
approximately 1,700 pounds per day (lb/d) with a 40 percent active solution. The average cost of
ferric chloride was estimated to be about $7,000 per month. H2S in the biogas ranged from 40 to
80 ppmv with an average of about 60 ppmv. Additionally, IEUA commenced food waste
codigestion with manure during April 2005. The types of food wastes used included salad
dressing, lactose, and ice cream wastes.

1000

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10 5
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/9
10 / 05
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4
10 /0 5
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10 /0 5
/2
4/
05

Ferric (gpd)

H2S (ppmv)

Digester 4 H2S and Ferric Addition

Dig. 4 H2S ppm

Ferric gpd

FIGURE 2
Digester 4 and H2S Gas Levels in Presence of Ferric Feed
Ferric injection to Digester 4 was stopped on October 25, 2005. An increase in Digester 2 biogas
H2S concentration was observed, starting at the end of October. Figure 3 shows Digester 4
biogas H2S concentration for the months of September through December 2005. As shown, in
the absence of ferric chloride injection to Digester 4, the H2S concentration increased to above
500 ppmv, which was the upper limit of the hand-held H2S meter used for monitoring biogas
H2S levels.

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1000

500

800

400

600

300

400

200

200

100
0

7/
1/
05
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/1
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/2
8/
05

Ferric (gpd)

H2S (ppmv)

Digester 4 H2S and Ferric Addition

Dig. 4 H2S ppm

Ferric gpd

FIGURE 3
Digester 4 Biogas H2S Gas Levels in Absence of Ferric Feed
BIOLOGICAL H2S SCRUBBER
The biological H2S scrubber system was sized to remove H2S from the digester gas (in absence
of ferric feed) and produce a treated gas with H2S concentration of less than 40 ppmv. The
biological scrubber performance is illustrated in Figure 4. As discussed previously, the hand-held
gas monitoring kit could not measure H2S levels above 500 ppmv. Therefore, some laboratory
analysis was conducted to establish the biogas H2S concentrations above 500 ppmv. Table 2
presents the laboratory data for H2S concentration for the scrubber inlet and outlet gas streams.
As shown, the scrubber acclimated within days and removed H2S effectively. The laboratory
results confirmed that the H2S levels in the outlet biogas were maintained below 40 ppmv
regardless of the high H2S concentrations in the inlet biogas.
Figure 4 also presents the recirculation water temperature during the testing phase. The system
upset in early December may have been related to a number of operating parameters, including
lower temperature, nutrient deficiency, or lower recirculation water pH. Figure 4 illustrates a
gradual temperature drop from over 28 degrees Celsius (C) in early October to below 22C in
early December due to lower ambient temperatures. The lower recirculation water temperature
periods coincide with the increase in the H2S level in the scrubber outlet, suggesting the
biological scrubber efficiency could be impacted by fluctuations in the recirculation water
temperature.
The performance upset also may have been caused by nutrient deficiency because no
supplemental nutrient was added to the scrubber from the start of the test until deterioration in
scrubber performance was observed in December. A combination of low temperature and
nutrient deficiency could have lowered the microbial activities and consequently reduced the rate
of the oxidation process in the scrubber. A drop in the pH of the recirculation water also was
observed in December. The pH drop, however, may have been caused by deterioration of the
biological activity in the scrubber.

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Scrubber Inlet

Scrubber Outlet

Temperature

FIGURE 4
H2S Scrubber Performance
TABLE 2
H2S Concentrations Laboratory Data
Scrubber Inlet
Date
ppmv
11/10/2005
11/10/2205
11/10/2005
11/16/2005
11/16/2005
11/22/2005
11/29/2005
11/30/2005
12/06/2005
12/07/2005
12/14/2005
12/20/2005

4000 +
1139
414
586
1937
788
63
102
577
186
424
589

Scrubber Outlet
ppmv
NS
2
NS
0.001
NS
0.02
46
31
15
1
21
12

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12/31/05

12/26/05

12/21/05

12/16/05

12/11/05

12/6/05

12/1/05

Recirculation T (C)

0
11/26/05

0
11/21/05

11/16/05

200

11/6/05

14

11/11/05

400

11/1/05

21

10/27/05

600

10/22/05

28

10/17/05

800

10/12/05

35

10/7/05

1000

10/2/05

42

9/27/05

1200

9/22/05

H2S (ppm)

H2S Scrubber Performance

WEFTEC.06

CONCLUSIONS
The biological H2S scrubber demonstrated good performance throughout the testing phase and
eliminated the need for ferric chloride addition to Digester 4. The system required a few days for
startup and acclamation. The treated biogas H2S levels were maintained at below the 40-ppmv
target level by the scrubber under normal operating conditions.
System performance deterioration was observed in late November to early December. Reduction
in the recirculation water temperature appeared to impact the biological activity and the scrubber
efficiency. The lower recirculation water temperature was due to the lower ambient air
temperature. Water pipe and tank insulation can reduce the adverse impact of outdoor
temperature variations on the process performance. Other factors affecting performance of the
scrubber could include nutrient deficiency and recirculation water pH. No supplemental nutrient
was added to the scrubber from the start of the test until deterioration in scrubber performance
was observed in December. A combination of low temperature and nutrient deficiency could
have lowered the microbial activities and resulted in a drop in the pH of the recirculation water.

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