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.

Copyright 2006 Water Environment Foundation. All Rights Reserved

3541

WEFTEC.06

TABLE 1 Alternative Biogas Treatment Process Technologies Process Technology Precipitation/Scavenging Caustic Scrubbing Caustic Scrubbing/ Biological Oxidation Caustic Scrubbing/ Chemical Oxidation Reactions Precipitates with iron or zinc compounds Use alkaline to react with acid gas of H2S Biological oxidation of H2S to sulfur and sulfuric acid Use chemical oxidation of H2S to sulfur and sulfuric acid Representing Process Iron sponge, Sulfa Treat, Sulfur-Rite, Media-G2 Sulfint, Sulferox, and many other nonproprietary systems THIOPAQ, Biopuric*

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.

Copyright 2006 Water Environment Foundation. All Rights Reserved

3542

WEFTEC.06

BIOLOGICAL H2S REMOVAL SYSTEM

CONDENSER / DRYER
S

S WATER SUPPLY

FIQ BIOGAS FROM DIGESTER No. 4 SAMPLE POINT

PI

TI

BLOWER

H2S REMOVAL TANK

PI RECIRC PUMP TI

NPK NUTRIENTS

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
Copyright 2006 Water Environment Foundation. All Rights Reserved

3543

WEFTEC.06

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.
Digester 4 H2S and Ferric Addition
1000 800 H2S (ppmv) 600 400 200 0
7/ 1/ 05 7/ 6/ 0 7/ 5 11 /0 7/ 5 16 /0 7/ 5 21 /0 7/ 5 26 /0 7/ 5 31 /0 5 8/ 5/ 05 8/ 10 /0 8/ 5 15 /0 8/ 5 20 /0 8/ 5 25 /0 8/ 5 30 /0 5 9/ 4/ 05 9/ 9/ 0 9/ 5 14 /0 9/ 5 19 /0 9/ 5 24 /0 9/ 5 29 /0 10 5 /4 /0 10 5 /9 10 / 05 /1 4 10 /0 5 /1 9 10 /0 5 /2 4/ 05

500 400 300 200 100 0 Ferric (gpd)

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.

Copyright 2006 Water Environment Foundation. All Rights Reserved

3544

WEFTEC.06

Digester 4 H2S and Ferric Addition

1000 800
H2S (ppmv)

500 400 300 200 100 0

Ferric (gpd)

600 400 200 0

7/ 1/ 05 7/ 11 /0 5 7/ 21 /0 5 7/ 31 /0 5 8/ 10 /0 5 8/ 20 /0 5 8/ 30 /0 5 9/ 9/ 05 9/ 19 /0 5 9/ 29 /0 5 10 /9 /0 5 10 /1 9/ 05 10 /2 9/ 05 11 /8 /0 5 11 /1 8/ 05 11 /2 8/ 05 12 /8 /0 5 12 /1 8/ 05 12 /2 8/ 05

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.

Copyright 2006 Water Environment Foundation. All Rights Reserved

3545

WEFTEC.06

H2S Scrubber Performance

1200 1000 H2S (ppm) 800 600 400 200 0 10/2/05 10/7/05 11/1/05 11/6/05 12/1/05 10/12/05 10/17/05 10/22/05 10/27/05 11/11/05 11/16/05 11/21/05 11/26/05 12/6/05 9/22/05 9/27/05 12/11/05 12/16/05 12/21/05 12/26/05 12/31/05 42 35 28 21 14 7 0 Recirculation T (C)

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

Copyright 2006 Water Environment Foundation. All Rights Reserved

3546

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.

Copyright 2006 Water Environment Foundation. All Rights Reserved

3547