#H2S Removal

REMOVAL OF HYDROGEN SULFIDE FROM BIOGAS
USING COW-MANURE COMPOST
A Thesis
Presented to the Faculty of the Graduate School
of Cornell University
in Partial Fulfillment of the Requirements for the Degree of
Master of Science
by
Steven McKinsey Zicari
January 2003
2003 Steven McKinsey Zicari
ABSTRACT
The two-part objective of this study was to determine currently available H2S
removal technologies suitable for use with farm biogas systems, and to test the
feasibility of utilizing on-farm cow-manure compost as an H2S adsorption medium.
Integrated farm energy systems utilize anaerobic digesters to provide a waste
treatment solution, improved nutrient recovery, and energy generation potential in the
form of biogas, which consists mostly of methane and carbon dioxide, with smaller
amounts of water vapor, and trace amounts of H2S and other impurities. Hydrogen
sulfide usually must be removed before the gas can be used for generation of
electricity or heat. Biogas has remained a virtually untapped resource in the United
States due to many factors, including relatively high gas processing costs.
There are many chemical, physical, and biological methods currently available
for removal of H2S from an energy gas stream. Dry based chemical processes have
traditionally been used for biogas applications and remain competitive based on
capital and media costs. Iron Sponge, Media-G2, and potassium-hydroxideimpregnated activated-carbon systems are the most attractive, with estimated capital
costs of $10,000-$50,000 and media costs of $0.35-$3.00/kg H2S removed. These
processes are simple and effective, but also incur relatively high labor costs for
materials handling and disposal. Other significant drawbacks include a continually
produced solid waste stream and growing environmental concern over appropriate
disposal methods. Additions of air (2-6%) to the digester headspace, or iron
compounds introduced directly in the digester, show promise as partial H2S abatement
methods, but have limited and inconsistent operational histories. Liquid based and
membrane processes require significantly higher capital, energy and media costs, and
do not appear economically competitive for selective H2S removal from biogas at this
time. Commercial biological processes for H2S removal are available (Biopuric and
Thiopaq) that boast reduced operating, chemical, and energy costs, but require higher
capital costs than dry based processes.
Initial testing of cow-manure compost indicates that it has potential as an
effective and economic matrix for H2S removal. Polyvinyl-chloride (PVC) test
columns were constructed and a 2:1 biogas-to-air mixture passed through the columns
containing anaerobically digested cow-manure compost. The most significant trials
ran for 1057 hours with an empty-bed gas residence time near 100 seconds and inlet
H2S concentrations averaging 1500 ppm, as measured by an electrochemical sensor
with 40:1 sample dilution.
Removal efficiencies over 80% were observed for a majority of the run time.
Elimination capacities recorded were between 16 118 g H2S/m3 bed/hr. This is
significant considering only minimal moisture, and no temperature or pH controls
were implemented. Temperature in the bed varied from 19-43C and the moisture
contents in the spent column ranged from 41-70%, with pH values from 4.6 to 6.9. It
is not clear whether the major mechanism for sulfur removal from the gas stream was
biological, chemical or physical, but it is known that the sulfur content in the packing
increased by over 1400%, verifying sequestration of sulfur in the compost.
These initial results indicate that future work is warranted for examining the
suitability of cow-manure compost as a biofiltration medium for use with biogas.
BIOGRAPHICAL SKETCH
Steven McKinsey Zicari was born in Rochester, New York, to Richard E. and
D. June Zicari. He grew up with his older brother, Zev, and attended West
Irondequoit public schools through the 12th grade. Steven enrolled at Cornell
University in the fall of 1995, and focused his studies on biological engineering. He
graduated with a Bachelor of Science degree in Agricultural and Biological
Engineering in May, 1999, Cum Laude. As an undergraduate, he also participated in
the alpine ski team, symphonic band, and the engineering co-op program. His co-op
experiences were with Genencor International in Rochester, NY, and Nestle R&D in
New Milford, CT.
After working briefly for the New York State Department of Agriculture and
Markets as a farm products inspector, and also as a ski instructor in Vail, Colorado,
Steven decided to return to Cornell for graduate school in the Fall of 2000. He has
held teaching and research assistant positions in the Department of Biological and
Environmental Engineering and his current research interests include sustainable
development, alternative and renewable energy systems, and biological processes.
iii
To my family
iv
ACKNOWLEDGMENTS
I would like to thank my major advisor, Dr. Norman Scott, for his guidance,
creativity, and tireless effort in researching sustainable development. I have learned a
great deal by working closely with him. I am also grateful to my minor advisor, Dr.
A. Brad Anton, for his helpful insights, positive encouragement, and superb technical
competence. I also extend thanks to committee member Dr. Anthony Hay for his
continual enthusiasm, willingness to help, and for sharing his exceptional
understanding of biological systems.
I acknowledge the Biological and Environmental Engineering department,
especially Dr. Dan Aneshansley and Dr. Michael Walter, for supporting me with
teaching opportunities and sound advice during my studies here. Also the knowledge
and cooperation of Dr. Larry Walker, Doug Caveny and Peter Wright are greatly
valued. Additionally, I greatly appreciate the cooperation of Robert, Wayne, and
Aaron Aman for allowing me to perform tests at AA Dairy.
Special thanks are also given to fellow graduate student John Poe Tyler. His
expert mechanical and engineering skills, as well as determination, were invaluable. I
also thank Tina Jeoh for her constant motivation, encouragement and assistance.
The support of my fellow research-group members, officemates and fellow
graduate students are also greatly appreciated, especially Kristy Graf, Jianguo Ma,
Stefan Minott, Scott Pryor, and Kelly Saikkonen.
Lastly, I would like to thank all of my family and friends for their support,
without which, this would not have been possible.
TABLE OF CONTENTS
BIOGRAPHICAL SKETCH.........................................................................................iii
ACKNOWLEDGMENTS.............................................................................................. v
1. INTRODUCTION ...................................................................................................... 1
2. BACKGROUND........................................................................................................ 3
2.1. INTEGRATED FARM ENERGY SYSTEMS ....................................... 3
2.1.1. AA Dairy .......................................................................................... 4
2.2. ANAEROBIC DIGESTION ................................................................... 6
2.3. BIOGAS COMPOSITION...................................................................... 9
2.4. QUALITY REQUIREMENTS FOR BIOGAS UTILIZATION .......... 10
2.5. TRADITIONAL H2S GAS-PHASE REMOVAL METHODS ............ 12
2.5.1. Dry H2S Removal Processes .......................................................... 13
2.5.1.1. Iron Oxides .............................................................................. 14
2.5.1.2. Zinc Oxides ............................................................................. 22
2.5.1.3. Alkaline Solids ........................................................................ 24
2.5.1.4. Adsorbents............................................................................... 24
2.5.2. Liquid H2S Removal Processes ...................................................... 30
2.5.2.1. Liquid-Phase Oxidation Processes .......................................... 31
2.5.2.2. Alkaline Salt Solutions ............................................................ 35
2.5.2.3. Amine Solutions ...................................................................... 36
2.5.3. Physical Solvents............................................................................ 38
2.5.3.1. Water Washing ........................................................................ 39
2.5.3.2. Other Physical Solvents........................................................... 39
2.5.4. Membrane Processes ...................................................................... 40
2.6. ALTERNATIVE H2S CONTROL METHODS.................................... 41
2.6.1. In-Situ (Digester) Sulfide Abatement............................................. 41
2.6.2. Dietary Adjustment ........................................................................ 42
2.6.3. Aeration .......................................................................................... 43
2.7. BIOLOGICAL H2S REMOVAL METHODS ...................................... 43
2.7.1. History and Development............................................................... 43
2.7.2. Biological Sulfur Cycles................................................................. 45
2.7.3. Example Applications .................................................................... 50
2.8. RESEARCH STATEMENT ................................................................. 54
3. MATERIALS AND METHODS ............................................................................. 55
3.1. REACTORS .......................................................................................... 55
3.1.1. Small Reactors................................................................................ 55
3.1.2. Large Reactors................................................................................ 58
3.2. EXPERIMENTAL SETUP ON SITE ................................................... 60
3.3. GAS SAMPLING AND MEASUREMENT......................................... 64
3.3.1. Electrochemical Sensor .................................................................. 64
3.3.2. Gas Sampling Tubes....................................................................... 66
vi
3.3.3. Gas Chromatography...................................................................... 67

3.4. TEMPERATURE MEASUREMENT................................................... 67
3.5. PRESSURE MEASUREMENT............................................................ 68
3.6. COMPOST CHARACTERIZATION................................................... 68
3.6.1. Moisture Content ............................................................................ 68
3.6.2. Void Fraction:................................................................................. 69
3.6.3. Bulk Density................................................................................... 69
3.6.4. Particle Size Distribution................................................................ 69
3.6.5. pH ................................................................................................... 70
3.6.6. Trace Element Analysis.................................................................. 70
3.6.7. Sulfate Content ............................................................................... 70
3.7. OPERATIONAL PROCEDURES ........................................................ 70
4. RESULTS AND DISCUSSION............................................................................... 72
4.1. ORIGINAL COMPOST CHARACTERISTICS .................................. 72
4.2. OPERATIONAL SUMMARY ............................................................. 74
4.3. PRESSURE MEASUREMENTS.......................................................... 75
4.4. TEMPERATURE MEASUREMENTS ................................................ 77
4.5. HYDROGEN SULFIDE MEASUREMENTS...................................... 84
4.5.1. Electrochemical Sensor .................................................................. 84
4.5.2. Gas Detector Tubes ........................................................................ 90
4.5.3. Gas Chromatography...................................................................... 91
4.6. BIOGAS-EXPOSED-COMPOST ASSESSMENT .............................. 93
4.6.1. Moisture.......................................................................................... 93
4.6.2. pH ................................................................................................... 95
4.6.3. Trace Element Analysis.................................................................. 95
4.7. DISCUSSION........................................................................................ 97
4.8. SCALE-UP CONSIDERATIONS ........................................................ 98
5. SUMMARY AND CONCLUSIONS..................................................................... 102
5.1. CURRENTLY AVAILABLE H2S REMOVAL METHODS............. 102
5.1.1. Dry-Based Processes .................................................................... 102
5.1.2. Liquid-Based Chemical and Physical Processes .......................... 105
5.1.3. Membrane Separation................................................................... 105
5.1.4. In-Situ Digester Sulfide Control................................................... 105
5.1.5. Biogas Aeration ............................................................................ 106
5.1.6. Biological Removal Techniques................................................... 106
5.1.7. Comparison of Characteristics of H2S Removal Processes.......... 106
5.2. TESTING OF COW-MANURE COMPOST ..................................... 108
6. FUTURE WORK AND RECOMMENDATIONS ................................................ 109
APPENDIX A: H2S Scavenger Media Disposal ........................................................ 111
REFERENCES ........................................................................................................... 112
vii
LIST OF TABLES
Table 2.1: Characteristics of Typical Agricultural Anaerobic Digesters ....................... 7
Table 2.2: Physical, Chemical and Safety Characteristics of Hydrogen Sulfide ......... 10
Table 2.3: Biogas Utilization Technologies and Gas Processing Requirements.......... 11
Table 2.4: Principal Gas Phase Impurities ................................................................... 12
Table 2.5: Assumed Biogas Characteristics for Process Comparisons ........................ 13
Table 2.6: Typical Specifications for 15-lb Iron Sponge ............................................. 15
Table 2.7: Iron Sponge Design Parameter Guidelines ................................................. 17
Table 2.8: System Characteristics of 15-lb Iron Sponge Design at AA Dairy............. 18
Table 2.9: System Characteristics of SulfaTreat Design at AA Dairy ....................... 20
Table 2.10: System Characteristics of Sulfur-Rite Design at AA Dairy.................... 21
Table 2.11: System Characteristics of Media-G2 Design at AA Dairy ..................... 22
Table 2.12: Processes for Adsorbent Regeneration...................................................... 25
Table 2.13: Basic Types of Commercial Molecular Sieves ......................................... 26
Table 2.14: Summary of 5A Molecular Sieve Design at AA Dairy............................. 28
Table 2.15: System Characteristics for KOH-Impregnated Activated Carbon at AA
Dairy ..................................................................................................................... 29
Table 2.16: Henrys Law Constants at 25 C and 1-Atmosphere ................................ 39
Table 2.17: Specific Microorganisms Studied for Biofiltration of H2S ....................... 49
Table 2.18: Media Tested for Biofiltration of Hydrogen Sulfide................................. 50
Table 3.1: Cross Sensitivity Data for Electrochemical H2S Sensor ............................. 65
Table 3.2: Summary of Experimental Trial Conditions ............................................... 71
Table 4.1: Cow-Manure Compost Characterization..................................................... 73
Table 4.2: Summary of Temperature Extremes for Trials 3-6 ..................................... 81
Table 4.3: H2S Gas Detector Tube Readings for AA Dairy Raw Digester Gas........... 90
Table 4.4: GC-MS Results for AA Dairy Digester Gas ............................................... 91
Table 4.5: Moisture Contents Along Bed Depth .......................................................... 94
Table 4.6: pH Levels Along Bed Depth ....................................................................... 95
Table 4.7: Elemental Analysis of Raw and Tested Compost ....................................... 96
Table 4.8: Estimated Comparison of Cow-Manure Compost and Iron-Sponge H2SRemoval Systems at AA Dairy........................................................................... 101
Table 5.1: Summary Table Comparing Dry-Based H2S Removal Processes for Farm
Biogas ................................................................................................................. 103
Table 5.2: Summary Table Comparing Dry-Based H2S Removal Processes for AA
Dairy ................................................................................................................... 104
Table 5.3: Summary of H2S Removal Process Characteristics .................................. 107
Table A.1. Approximate Media Change-out and Disposal Costs (1996 est.) ............ 111
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LIST OF FIGURES
Figure 2.1: Schematic of AA Dairy Integrated Farm Energy System............................ 5
Figure 2.2: Anaerobic Digestion Process ....................................................................... 8
Figure 2.3: Equilibrium Constant for the Reaction ZnO + H2S = ZnS + H2O............. 23
Figure 2.4: Adsorption Zones in a Molecular Sieve Bed, Adsorbing Both Water Vapor
and Mercaptans from Natural Gas........................................................................ 27
Figure 2.5: Generic Absorber/Stripper Schematic ....................................................... 30
Figure 2.6: Reduction-Oxidation Cycle of Quinones................................................... 32
Figure 2.7: Conventional Flow Diagram for LO-CAT Process ................................. 33
Figure 2.8: Flow Scheme for Alkanolamine Acid-gas Removal Processes................. 38
Figure 2.9: Biofiltration System Schematic ................................................................. 45
Figure 2.10: The Global Sulfur Cycle. ......................................................................... 46
Figure 2.11: Biological Redox Cycle for Sulfur .......................................................... 47
Figure 2.12: Steps in the Oxidation of Sulfur Compounds by Thiobacillus Species. .. 48
Figure 3.1: Schematic of Small Columns..................................................................... 56
Figure 3.2: Schematic of Small Columns with Leachate Recycle ............................... 57
Figure 3.3: Schematic of Large Columns..................................................................... 59
Figure 3.4: Experimental Setup at AA Dairy ............................................................... 61
Figure 3.5: Humidifier and Air/Biogas Mixing Vessel ................................................ 63
Figure 4.1: AA-Dairy Field of Dreams Cow-Manure Compost ............................... 72
Figure 4.2: Pressure Drop Across Bed for Trials 3-6................................................... 76
Figure 4.3: Temperatures (15-Minute Average) for Column 3 .................................... 78
Figure 4.7: Temperature Difference Between Bed and Inlet-gas for Columns 3-6 ..... 80
Figure 4.8: H2S Concentrations for Trial 3 .................................................................. 85
Figure 4.9: H2S Removal Efficiency During Trial 3.................................................... 86
Figure 4.10: H2S Concentrations for Trial 4 ................................................................ 86
Figure 4.11: H2S Removal Efficiency During Trial 4.................................................. 87
Figure 4.12: H2S Concentrations and Removal Efficiency for Column 5 ................... 89
Figure 4.13: H2S Concentrations and Removal Efficiency for Column 6 ................... 89
Figure 4.14: GC-MS Results for AA Dairy Digester Gas............................................ 92
Figure 4.15: Pictures of Columns after Exposure to Biogas for 1057 hours................ 93
ix
CHAPTER
1. INTRODUCTION
Anaerobic digestion (AD) of agricultural waste has been practiced for many
years and provides a waste treatment solution, improved nutrient recovery, and energy
generation potential. Because of growing environmental constraints, an increase in the
average dairy farm herd size, and rising energy costs from increased demand, dairy
farmers are looking to AD coupled with on-site cogeneration of heat and power in
response to these pressures. However, there are hurdles to implementation of these
systems, including high capital costs, availability of economic and environmentally
acceptable methods of gas processing, and economic means for biogas utilization.
Because of these limitations, agricultural biogas production has remained a virtually
untapped resource in the United States.
Biogas consists mainly of methane (CH4) and carbon dioxide (CO2), with
smaller amounts of water vapor and trace amounts of hydrogen sulfide (H2S), and
other impurities. Various degrees of gas processing are necessary depending on the
desired gas utilization process. Hydrogen sulfide is typically the most problematic
contaminant because it is toxic and corrosive to most equipment. Additionally,
combustion of H2S leads to sulfur dioxide emissions, which have harmful
environmental effects. Removing H2S as soon as possible is recommended to protect
downstream equipment, increase safety, and enable possible utilization of more
efficient technologies such as microturbines and fuel cells.
2
The most commonly used method for H2S removal from biogas involves
adsorption onto chemically active solid media. Though this process is effective, it is
labor intensive and generates a waste stream that poses environmental disposal risks.
These factors led to the identification of an opportunity for testing on-farm
manure compost as the adsorption medium. A similar process, known as biofiltration,
has shown its ability to remove H2S through the microbial action of naturally
occurring bacteria. Biofilters show promise as environmentally friendly, alternative
air pollution control technologies with lower capital, labor, and disposal costs.
The following objectives were specifically addressed in this study:
1) Survey currently available chemical, physical, and biological methods of
H2S removal from agricultural digester biogas.
2) Test the feasibility of utilizing on-farm cow-manure compost for H2S
removal.
AA Dairy farm in Candor, NY, which has produced biogas since 1998,
served as the site for experimental testing. Although removal of water vapor, carbon
dioxide, and other contaminants is also desirable, assessing all of the technologies
required for removal of these compounds is beyond the scope of this project.
It is hoped that this research not only benefits farmers who are looking to
install integrated farm energy systems, but also designers and operators of other
agricultural facilities, landfills, wastewater treatment plants, food-processing facilities,
and pulp and paper mills, where renewable, bio-based energy can be produced.
CHAPTER
2. BACKGROUND
2.1. INTEGRATED FARM ENERGY SYSTEMS

The concept of an integrated farm energy (IFE) system is an embodiment of
principals of industrial ecology, which attempt to improve on the efficiency and
sustainability of a system by optimizing energy and material usage while minimizing
pollution and waste. IFE systems, as referred to here, use anaerobic digestion (AD) to
treat the volatile organic fraction of animal manures, thereby producing biogas and an
improved waste stream. The biogas is then used for on-site heat and/or power
generation, and the digested material is either applied back to the land or processed
further into value-added compost. In 1995, a study estimated that three to five
thousand such systems could be economically installed throughout the next decade in
the U.S. (Lusk 1996). In 1999, there were only 34 operating farm-digester sites
registered with the EPAs AgSTAR program, though this number has since grown
(Roos and Moser 2000). According to one estimate, if all of the dairy manure biomass
in New York state could be collected and processed using anaerobic digestion and
diesel engine generation, an annual energy potential of 280 GWh, enough to support
the electricity demand of about 47,000 households, would be produced in addition to
providing all of the electricity for the farms (Ma 2002).
Extensive research on these integrated systems was done during the 1970s and
1980s by Cornell University researchers, and further information on their
4
development and design can be found in Jewell, et al. (1978), Walker, et al. (1985),
and Pellerin, et al. (1988). The integrated farm energy system used in this study is
operating at AA Dairy in Candor, NY.
2.1.1. AA Dairy
AA Dairy is a 2,200-acre, 500-head milking facility, which installed an
anaerobic digester in 1997. Resource recovery is achieved in part through use of an
anaerobic digester, diesel-engine cogenerator, liquid-solid separator, liquid-waste
storage lagoon, composting process and land application of effluent, as depicted in
Figure 2.1. Most of the cows are housed in a free-stall facility equipped with alley
scrapers for manure collection. A 1330 m3 concrete plug-flow digester, designed by
Resource Conservation Management, operates with approximately a 40-day retention
time and 1300 m3 per day of biogas produced on average. The digested solids are
separated and composted aerobically for a period of 60 days and sold to consumers as
a specialty organic fertilizer. The liquid portion is stored in a lagoon until land
application for nutrient value and water are needed. The biogas is combusted in a
converted Caterpillar 3306B diesel engine, which powers a generator continuously
producing 65 to 75 kW. Electricity unused by the farm (~535 kWh/day average) is
then sold to the local utility (NYSEG). Heat from the engine is currently used to
maintain the digester in its desired mesophillc operating range. The current method
for dealing with biogas impurities, such as hydrogen sulfide, is to perform a 70-quart
oil change weekly. No other gas processing technologies are employed, and the
annual operating cost for the resource recovery system, including labor and engine
maintenance, is estimate as $17,500 (Minott 2002).
LIVESTOCK
ENGINE/GENERATOR
(500 cow
free-stall
milking
facility)
Biogas
(1100-1400 m3/day)
(60-80 kW
continuously)
Heat
(~60% CH4,
~40% CO2
<4000ppm H2S)
Manure
Electricity
(Used to maintain
digester temperature)
LIQUID/SOLID
SEPARATOR
ANAEROBIC DIGESTER
(1330 m3 plug flow
Liquids
Solids
Compost
Irrigated Nutrients
LIQUID STORAGE LAGOON
(9000 m3 capacity)
COMPOSTING FACILITY
(Open windrow system)
Figure 2.1: Schematic of AA Dairy Integrated Farm Energy System
6
There are many benefits to such farm systems, which include (RDA 2000):
Waste treatment benefits: Natural waste treatment process that requires less
land than composting, reduces solid waste volume and weight, and reduces
contaminant runoff.
Energy benefits: Generates a high-quality renewable fuel, which has numerous

end-use applications.
Environmental benefits: Potential to reduce carbon dioxide and methane

emissions, eliminates odors, produces a bio-available nutrient stream, and
maximizes recycling benefits. Reduces dependence on fossil fuels.
Economic benefits: More cost effective than many other treatment options
when viewed from a life-cycle analysis. Typical payback periods of 4-8 years.
2.2. ANAEROBIC DIGESTION

Six to eight million family-sized low-technology digesters are used in China
and India to provide biogas for cooking and lighting. Also, there are over 800 farmbased digesters operating in Europe and North America (Wellinger and Linberg 2000).
Farm-based anaerobic digestion in the U.S. has mainly focused on manures from dairy
and swine operations because they are often liquid or slurry based. Systems have been
designed for poultry manures, but the higher solids content results in precipitation of
solids unless constantly mixed. There are many types of anaerobic digestion systems
for manure, which include batch, mixed-tank, plug-flow, fixed-film, and lagoon
digesters. Table 2.1 describes the different characteristics of 3 typical farm digesters.
Table 2.1: Characteristics of Typical Agricultural Anaerobic Digesters

Covered Lagoon
Complete Mix
Plug Flow
Round/Square
In ground
Vessel
Deep lagoon
In/Above ground Tank rectangular tank
Level of
Low
Medium
Low
Technology
Additional Heat
No
Yes
Yes
Total Solids
0.5-1.5%
3-11%
<11%
HRT (days)
40-60
15+
15+
Farm Type
Dairy/Hog
Dairy/Hog
Dairy only
Optimum Climate Temperate/Warm
All
All
Source: Roos and Moser (2000), AgSTAR Handbook, pgs.1-2
There are two ways to derive methane from biomass, thermally and
biologically. Although thermal conversion is rapid and complete, it is limited in its
application to materials of low water content. This is because large amounts of energy
are needed to vaporize water before reaching substrate-gasification temperature.
Biological conversions, utilizing methanogenic bacteria, are advantageous because
they require less energy and can be applied to wet or dry feedstock on a variety of
scales. Unfortunately, anaerobic digestion is often slow, requires precise solids
loading and an anoxic environment, and is only about 50% effective in its conversion
of organic matter.
The microbial process of anaerobic digestion and methane production occurs
through the complex action of interdependent microbial communities as depicted in
Figure 2.2. The first step involves the hydrolysis of organic compounds, including
carbohydrates, proteins, and lipids, via hydrolytic bacteria. Here, the substrate is
broken down into usable-sized molecules such as organic acids, alcohols, neutral
compounds, hydrogen and carbon dioxide. The second stage, carried out by
transitional bacteria, consists of converting soluble organic matter into methanogenic
substrates such as hydrogen, carbon dioxide and acetate. Lastly, methanogenic
8
bacteria utilize these intermediates for conversion to methane and carbon dioxide
(Chynoweth and Issacson 1987).
Complex
Organic
Carbons
HYDROLYTIC
BACTERIA
Organic
Acids,
Neutral
Compounds
TRANSITIONAL
BACTERIA
Hydrogen Producing
Acetogenic Bacteria
Homoacetogenic
Bacteria
H2, CO2, OneCarbon

Compounds
Acetic Acid
METHANOGENIC
BACTERIA
CH4 + CO2
Figure 2.2: Anaerobic Digestion Process

Source: Chynoweth and Issacson (1987), pg. 3
There are a number of factors which influence the digestion process, including,
temperature, bacterial consortium, nutrient composition, moisture content, pH, and
residence time.
Sulfur is an essential nutrient for methanogens but sulfur levels too high may
limit methanogenesis. Sulfur can enter the digester in the feedstock itself or from
chemicals used in an agricultural environment, such as copper and zinc sulfate
solutions that are used to prevent dairy cow foot-rot, and are inadvertently washed into
9
the digester. Farm animals consume sulfur either in their food source, mostly in the
form of sulfur-containing amino acids such as cystine and methionine, or from their
drinking water source, which may contain significant amounts of sulfate. Sulfur that
is not used by the animal for nutrition is excreted in the manure.
Sulfate-reducing bacteria actually can out-compete methanogens during the
anaerobic digestion process. Therefore, sulfide production generally proceeds to
completion before methanogenesis occurs. The energetics of sulfate reduction with H2
is favorable to the reduction of CO2 with H2, forming either CH4 or acetate (Madigan,
et al. 2000).
The toxic level of total dissolved sulfide in anaerobic digestion is reported as
200-300 mg/l. Also, a head gas concentration of 6% H2S is the upper limit for
methanogenesis, while 0.5% H2S (11.5 mg/l) is optimum (Chynoweth and Issacson
1987).
2.3. BIOGAS COMPOSITION

Biogas composition depends heavily on the feedstock, but mainly consists of
methane and carbon dioxide, with smaller amounts (ppm) of hydrogen sulfide and
ammonia. Trace amounts of organic sulfur compounds, halogenated hydrocarbons,
hydrogen, nitrogen, carbon monoxide, and oxygen are also occasionally present.
Usually, the mixed gas is saturated with water vapor and may contain dust particles
and siloxanes (Wellinger and Linberg 2000). Water-saturated biogas from dairymanure digesters consists primarily of 50-60% methane, 40-50% carbon dioxide, and
less than 1% sulfur impurities, of which the majority exists as hydrogen sulfide
(Pellerin, et al. 1987).
10
Hydrogen sulfide is poisonous, odorous, and highly corrosive. Some
characteristics of H2S are described in Table 2.2. Because of these characteristics,
hydrogen sulfide removal is usually performed directly at the gas-production site.
Table 2.2: Physical, Chemical and Safety Characteristics of Hydrogen Sulfide
Molecular Weight
34.08
Specific Gravity (relative to air)
1.192
Auto Ignition Temperature
250 C
Explosive Range in Air
4.5 to 45.5 %
Odor Threshold
0.47 ppb
8-hour time weighted average (TWA) (OSHA)
10 ppm
15-minute short term exposure limit (STEL) (OSHA)
15 ppm
Immediately Dangerous to Life of Health (IDLH) (OSHA)
300 ppm
Source: OSHA (2002), Occupational Safety and Health Administration, www.OSHA.gov
The actual amount of water vapor entrained in the gas depends on the gas
composition, pressure, and temperature. Approximately 25 kg of water is present in
1400 m3 of saturated natural gas at 21 C and atmospheric pressure (Kohl and Neilsen
1997).
2.4. QUALITY REQUIREMENTS FOR BIOGAS UTILIZATION

Biogas can be used for all applications designed for natural gas, assuming
sufficient purification. On-site, stationary biogas applications generally have fewer
gas processing requirements. A summary of potential biogas utilization technologies
and their gas processing requirements are given in Table 2.3.
11
Table 2.3: Biogas Utilization Technologies and Gas Processing Requirements
Technology
Recommended Gas Processing Requirements
Heating
(Boilers)1
Internal
Combustion
Engines1
H2S < 1000 ppm, 0.8-2.5 kPa pressure, remove condensate

(kitchen stoves: H2S < 10 ppm)
H2S < 100 ppm, 0.8-2.5 kPar pressure, remove condensate,
remove siloxanes (Otto cycle engines more susceptible
to H2S than diesel engines)
H2S tolerant to 70,000 ppm, > 350 BTU/scf, 520 kPa pressure,
remove condensate, remove siloxanes
PEM: CO < 10 ppm, remove H2S
PAFC: H2S < 20 ppm, CO < 10 ppm, Halogens < 4 ppm
MCFC: H2S < 10 ppm in fuel (H2S < 0.5 ppm to stack),
Halogens < 1 ppm
SOFC: H2S < 1 ppm, Halogens < 1 ppm
Microturbines2
Fuel Cells3
Stirling Engines4
Similar to boilers for H2S, 1-14 kPa pressure
Natural Gas
Upgrade1,5
H2S < 4 ppm, CH4 > 95%, CO2 < 2 % volume, H2O < (1*10-4)
kg/MMscf, remove siloxanes and particulates, > 3000
kPa pressure
Sources: 1 Wellinger and Linberg (2000)

2
Capstone Turbine Corp.(2002)
3
XENERGY (2002)
4
STM Power (2002)
5
Kohl and Neilsen (1997)
Technologies such as boilers and Stirling engines have the least stringent gas
processing requirements because of their external combustion configurations. Internal
combustion engines and microturbines are the next most tolerant to contaminants.
Fuel cells are generally less tolerant to contaminants due to the potential for catalytic
poisoning. Upgrading to natural-gas quality usually requires expensive and complex
processing and must be done when injection into a natural-gas pipeline or production
of vehicle fuel is desired.
Although not covered in this study, techniques for removal of CO2 may also
simultaneously reduce H2S levels. Many facilities in Europe have utilized water
scrubbing, polyethylene glycol scrubbing, carbon molecular-sieves or membranes for
upgrading of biogas to natural gas or vehicle fuel. Readers are directed to the
12
following references for more information on these systems: Kohl and Neilsen (1997),
Wellinger and Linberg (2000), CADDET (2001), Eriksen, et al. (1999), (Schomaker,
et al. (2000), and Jensen and Jensen (2000).
2.5. TRADITIONAL H2S GAS-PHASE REMOVAL METHODS

Since biogas is similar in composition to raw natural gas, purification
techniques developed and used in the natural-gas industry can be evaluated for their
suitability with biogas systems. The ultimate process chosen is dependent on the gas
use, composition, physical characteristics, energy and resources available, byproducts
generated, and the volume of gas to be treated.
Principal gas phase impurities that may be present are listed in Table 2.4
below. Other constituents that may be problematic include water or other
condensates, and particulate matter. Hydrocarbons, such as methane, are the desired
product gases.
Table 2.4: Principal Gas Phase Impurities
1. Hydrogen sulfide
2. Carbon dioxide
3. Water vapor
4. Sulfur dioxide
5. Nitrogen oxides
6. Volatile organic compounds (VOCs)
7. Volatile chlorine compounds (e.g., HCl, Cl2)
8. Volatile fluorine compounds (e.g., HF, SiF4)
9. Basic nitrogen compounds
10. Carbon monoxide
11. Carbonyl sulfide
12. Carbon disulfide
13. Organic sulfur compounds
14. Hydrogen cyanide
Source:Kohl and Neilsen (1997), pg 3
13
Gas purification processes generally fall into one of the following five
categories: 1) Absorption into a liquid; 2) Adsorption on a solid; 3) Permeation
through a membrane; 4) Chemical conversion to another compound; or 5)
Condensation (Kohl and Neilsen 1997).
For the purposes of process comparison, gas characteristics similar to those at
AA Dairy, which are typical for a farm digester treating waste from around 500 dairy
cows, will be assumed and summarized as shown in Table 2.5.
Table 2.5: Assumed Biogas Characteristics for Process Comparisons
Gas composition:
~60% CH4
~40% CO2
1000-4000 ppm H2S
Gas flow rate:
~1400 m3/day
Gas pressure:
< 2 kPa
Gas temperature:
~ 25C
Water saturated:
Yes
With the flow rate and sulfur levels above, 1.9 7.7 kg of H2S are present in
the gas stream daily, or 690 2,815 kg yearly. Desirable attributes for a gas
purification system include low capital and operating costs, ease of operation and
media disposal, and minimal material and energy inputs. H2S removal processes will
be divided into dry-based, liquid-based, physical-solvent, membrane, alternative, and
biological processes for this summary. Media disposal costs are not discussed here
but very well may be the most significant costs for a project. For a further discussion
of this point, see Appendix A.
2.5.1. Dry H2S Removal Processes
Dry H2S removal techniques have historically been used at facilities with less
than 200kg S/day in the U.S. All of the dry sorption processes discussed here are
14
configured with the dry media in box or tower type vessels where gas can flow
upwards or downwards through the media. Since all of the dry-sorption media to be
discussed eventually becomes saturated with contaminant and inactive, it is common
to have two vessels operated in parallel so one vessel can remain in service while the
other is offline for media replacement.
2.5.1.1. Iron Oxides
As one of the oldest methods still in practice, iron oxides remove sulfur by
forming insoluble iron sulfides. It is possible to extend bed life by admitting air,
thereby forming elemental sulfur and regenerating the iron oxide, but eventually the
media becomes clogged with elemental sulfur and must be replaced. The most wellknown iron oxide product is called iron sponge. Recently, proprietary iron-oxide
media such as SulfaTreat, Sulfur-Rite, and Media-G2 have been offered as
improved alternatives to iron sponge.
Iron Sponge
Iron-oxide-impregnated wood-chips (generally pine) are used to selectively
interact with H2S and mercaptans. The primary active ingredients are hydrated ironoxides (Fe2O3) of alpha and gamma crystalline structures. Lesser amounts of Fe3O4
(Fe2O3.FeO) also contribute to the activity (Anerousis and Whitman 1985). Typical
specifications for iron sponge are listed below in Table 2.6. Grades of iron sponge
with 100, 140, 190, 240 and 320 kg Fe2O3/m3 are traditionally available, with the 190
kg Fe2O3/m3 (15-lb/bushel) grade being the most common. Bulk density for this grade
is consistently around 800 kg/m3 (50 lb/ft3) in place (Revell 2001).
15
Table 2.6: Typical Specifications for 15-lb Iron Sponge
Source: Kohl and Neilsen,(1997), pg. 1302
The chemical reactions involved are shown in Equations 2.1-2.2:(Crynes 1978)

Fe2O3 + 3H2S Fe2S3 + 3H2O
H= -22 kJ/g-mol H2S
(2.1)
2Fe2S3 + O2 2Fe2O3 + 3S2
H= -198 kJ/g-mol H2S
(2.2)
As seen from Equation 2.1, one kg of Fe2O3 stochiometrically removes 0.64 kg

of H2S. Equation 2.2 represents the highly exothermic regeneration of iron oxide and
16
formation of elemental sulfur upon exposure to air. Iron sponge is also capable of
removing mercaptans via Equation 2.3: (Zapffe 1963)
Fe203 + 6RSH = 2Fe(RS)3 + 3H20
(2.3)
Iron sponge can be operated in batch mode with separate regeneration, or with
a small flow of air in the gas stream for continuous revification. In batch mode,
operational experience indicates that only about 85% (0.56 kg H2S/ kg Fe2O3) of the
theoretical efficiency can be achieved (Taylor 1956).
Spent iron sponge can be regenerated in place by recirculation of the gas in the
vessel adjusted to 8% O2 concentration and 0.3-0.6 m3/m3bed/min space velocity
(Taylor 1956). Alternatively, the sponge can be removed, spread out into a layer 0.15m thick, and kept continually wetted for 10 days. It is imperative to manage the heat
buildup in the sponge during regeneration to maintain activity and prevent combustion
(Revell 1997). Due to buildup of elemental sulfur and loss of hydration water, iron
sponge activity is reduced by 1/3 after every regeneration. Therefore, regeneration is
only practical once or twice before new iron sponge is needed.
Removal rates as high as 2.5 kg H2S/ kg Fe2O3 have been reported in
continuous-revivification mode with a feed-gas stream containing only a few tenths of
a percent of oxygen (Taylor 1956). Equation 2.4 can be used to calculate percent air
recirculation necessary for optimum performance, dependent on inlet H2S
concentration in the gas (Vetter et al. 1990).
% Air recirculation required = 1.90 +(mg/m3 H2S measured)/3024
(2.4)
17
At Huntingtons farm in Cooperstown, N.Y., a removal level of 1.84 kg
H2S/kg Fe2O3 was reported using 140 kg Fe2O3/m3 (12 lb/bushel)-grade sponge and
continuous revivification with 2.29% air recirculation (Vetter et al. 1990).
Because iron sponge is a mature technology, there are design parameter
guidelines that have been determined for optimum operation. Table 2.7, below, is a
comprehensive collection of published design criteria for iron sponge systems.
Table 2.7: Iron Sponge Design Parameter Guidelines
Vessels: Stainless-steel box or tower geometries are recommended for ease of
handling and to prevent corrosion. Two vessels, arranged in series are
suggested to ensure sufficient bed length and ease of handling (Lead/Lag).
Gas Flow: Down-flow of gas is recommended for maintaining bed moisture. Gas
should flow through the most fouled bed first.
Gas Residence Time: A residence time of greater than 60 seconds, calculated using
the empty bed volume and total gas flow, is recommended.1
Temperature: Temperature should be maintained between 18 C and 46 C in
order to enhance reaction kinetics without drying out the media.2
Bed Height: A minimum 3 m (10 ft) bed height is recommended for optimum H2S
removal. A 6 m bed is suggested if mercaptans are present.3 A more
conservative estimate recommends a bed height of 1.2 to 3 meters.4
Superficial Gas Velocity: The optimum range for linear velocity is reported as 0.6-3
m/minute.3
Mass Loading: Surface contaminant loading should be maintained below 10 g
S/min/m2 bed.4
Moisture Content: In order to maintain activity, 40% moisture content, plus or
minus 15%, is necessary. Saturating the inlet gas helps to maintain this.2
pH: Addition of sodium carbonate can maintain pH between 8-10. Some sources
suggest addition of 16 kg sodium carbonate per m3 of sponge initially to
ensure an alkaline environment.2
Pressure: While not always practiced, 140 kPa is the minimum pressure
recommended for consistent operation.3
Sources: 1 Revell (2001), 2 Kohl and Neilsen (1997), 3 Anerousis and Whitman (1985),
4
Maddox and Burns (1968), 5 Taylor (1956)
Using the design constraints described in Table 2.7, a suitable iron sponge
system can be designed for a generic farm biogas application with characteristics
shown in Table 2.5. These results are presented in Table 2.8 below.
18
Table 2.8: System Characteristics of 15-lb Iron Sponge Design at AA Dairy
Number of Vessels
Vessel Dimensions
Empty Bed Residence Time
Gas Flow Rate
Mass of Sponge
Air Recirculation Rate
Expected Bed Life

Annual Sponge Consumed
Annual Sponge Costs
2 in series (Lead/Lag)
0.91 m diameter x 1.52 m high
120 seconds total
0.94 m3/min
800 kg each
2.4% - 3.7%
Performance Estimates
Low Loading
High Loading
(1000 ppm H2S)
(4000 ppm H2S)
72-315 days
930-4070 kg
$250 -$1,075
18-79 days
3,710 16,300 kg
$985-$4,300
Biogas operations currently using iron sponge are located in Cooperstown,

NY, Little York, NY, and Chino, CA, among others. H2S levels at one farm digester
were consistently reduced from as high as 3600 ppm (average 1350 ppm) to below 1
ppm using a 1.5 m diameter x 2.4 m deep iron sponge reactor (Vetter et al. 1990).
Commercial sources for iron sponge include Connelly GPM, Inc., of Chicago,
IL, and Physichem Technologies, Inc., of Welder, TX. Both companies provide media
for around $6 per bushel (~50 lb), and note that shipping costs may be more
significant than actual media costs. Varec Vapor Controls, Inc., sells their Model-235
treatment units for around $50,000, including the cost of initial media. Such a unit
could last up to two years before change-out would be necessary (Wang 2000).
While the benefits of using iron sponge include simple and effective operation,
there are critical drawbacks to this technology that have lead to decreased usage in
recent years. The process is highly chemical intensive, the operating costs can be
high, and a continuous stream of spent waste material is accumulated. Additionally,
the change-out process is labor intensive and can be troublesome if heat is not
dissipated during regeneration. Perhaps most importantly, safe disposal of spent iron
sponge has become problematic, and in some instances, spent media may be
19
considered hazardous waste and require special disposal procedures. Landfilling onsite is still practiced, but has become riskier due to fear of the need for future
remediation.
SulfaTreat
SulfaTreat is a proprietary sulfur scavenger, consisting mainly of Fe2O3 or
Fe3O4 compounds coated onto a proprietary granulated support and marketed by the
SulfaTreat Company of St. Louis, MO. SulfaTreat is used similarly to iron sponge
in a low-pressure vessel with down-flow of gas and is effective with partially or fully
hydrated gas streams.
Conversion efficiency in commercial systems is in the range of 0.55 - 0.72 kg
H2S/kg iron oxide, which is similar to, or slightly higher than, values reported for
batch operation of iron sponge (Kohl and Neilsen 1997). Particles range in size from
4 to 30 mesh with a bulk density of 1120 kg/m3 in place, and sell for roughly $0.88/kg
(Taphorn 2000).
Multiple benefits over iron sponge are claimed due to uniform structure and
free-flowing nature. SulfaTreat is reportedly easier to handle than iron sponge, thus
reducing operating costs, labor for change-out, and pressure drops in the bed. Also,
SulfaTreat claims to be non-pyrophoric when exposed to air and thus does not pose a
safety hazard during change-out. Buffering of pH and addition of moisture are not
necessary as long as the inlet gas is saturated.
Drawbacks associated with this product are similar to iron sponge; the process
is non-regenerable, chemically intensive, and spent product can be problematic or
expensive to dispose of properly. The manufacturer has suggested that spent product
may be used as a soil amendment or as a raw material in road or brick making, but
20
they state that every customer must devise a spent-product disposal plan in accordance
with local and state regulations.
For AA Dairy, a two-vessel arrangement (series) is proposed by the SulfaTreat
Company to ensure maximum removal while maintaining manageable bed sizes.
Proprietary rectangular vessels in a Lead/Lag arrangement, with the most fouled bed
contacting the gas first, are used (Taphorn 2000). Transportation, installation, and
disposal costs are not included in the system as described in Table 2.9 below.
Table 2.9: System Characteristics of SulfaTreat Design at AA Dairy
Number of Vessels
1.22 m x 1.65 m x 1.83 m
Vessel Dimensions
$8,000 for two
Vessel Costs
0.94 m3/min
Gas Flow Rate
3,636 kg each
Mass of SulfaTreat
2.4%
Low Loading
High Loading
Expected Bed Life (one vessel)
Total Pressure Drop (kPa)
Annual SulfaTreat Consumed
Annual SulfaTreat Costs
(1000 ppm H2S)
(4000 ppm H2S)
345 days
0.4
3,850 kg
$3,400
86 days
0.4
15,450 kg
$13,500
Sulfur-Rite
Sulfur-Rite is also a dry-based iron-oxide product offered by GTP-Merichem.
Sulfur-Rite is unique in their claim that insoluble iron pyrite is the final end product.
Sulfur-Rite systems come in prepackaged cylindrical units that are recommended for
installations with less than 180 kg sulfur/day in the gas and flow rates below 70
m3/min. Company literature claims spent product is non-pyrophoric and landfillable
and has 3-5 times the effectiveness of iron sponge. Sulfur-Rite also has many of the
21
disadvantages of the iron-oxide scavengers previously mentioned. System design and
cost estimates for an installation similar to AA dairy are presented in Table 2.10.
Table 2.10: System Characteristics of Sulfur-Rite Design at AA Dairy
Number of Vessels
Vessel Dimensions
Vessel Costs
Gas Flow Rate
Mass of Sulfur-Rite
1-Carbon Steel unit

$43,600 (vessel only)
0.94 m3/min
9,100 kg
Low Loading
High Loading
Expected Bed Life

Annual Product Consumption
Annual Sulfur-Rite Costs
(1000 ppm H2S)
(4000 ppm H2S)
420 days
7,900 kg
$5,560
98 days
33,900 kg
$23,840
Media-G2
Media-G2 is an iron-oxide-based adsorption technology originally developed
by ADI International, Inc., for removal of arsenic from drinking water. Recently ADI
has begun testing Media-G2 for the removal of H2S from gas streams with promising
results. Landfill gas and biogas installations will serve as the primary market for their
technology, which incorporates iron oxides onto a diatomaceous support.
Lab scale and pilot scale trials indicate that treatment of up to 30,000 ppm H2S
is possible, spent product is non-hazardous, and Media-G2 can remove up to 560 mg
H2S/g solid. This is achieved by being able to regenerate the matrix with air up to 15
times. Each adsorption cycle removes about 35-40 mg H2S/g media. A two-vessel
system design (parallel) is recommended for continuous operation, as 8-hour
regeneration cycles are estimated at full scale. Vessels are designed for approximately
60-second empty-bed residence times. Approximate product costs are estimated at
$1060/m3.
22
Only two full-scale plants have been installed to date; Brookhaven Landfill in
NY, and a farm based anaerobic digester installed by Enviro-Energy Corporation in
Tillamook, OR (McMullin 2002). Although no full scale operational results were
available, a system design summary is proposed in Table 2.11 below.
Table 2.11: System Characteristics of Media-G2 Design at AA Dairy

Number of Vessels
Vessel Dimensions
Gas Flowrate
Empty Bed Residence Time
Mass of Media-G2
2 in parallel
0.94 m3/min
62 seconds (with one offline)
760 kg each
2.4%
Low Loading
High Loading

Annual Media-G2 Consumption
Annual Media-G2 Costs
(1000 ppm H2S)
(4000 ppm H2S)
190 days
1,460 kg
$2,050
47 days
5,900 kg
$8,290
2.5.1.2. Zinc Oxides

Zinc oxides are preferred for removal of trace amounts of hydrogen sulfide
from gases at elevated temperatures due to their increased selectivity over iron oxide
(Chiang and Chen 1987). Typically in the form of cylindrical extrudates 3-4 mm in
diameter and 8-10 mm in length, zinc oxides are used in dry-box or fluidized-bed
configurations. Hydrogen sulfide reacts with zinc oxide to form an insoluble zinc
sulfide via Equation 2.5 (Kohl and Neilsen 1997).
ZnO + H2S = ZnS + H2O
The equilibrium constant for the reaction is given with Equation 2.6.
(2.5)
23
Kp = PH2O/PH2S
(2.6)
Where: PH2O is the partial pressure of water vapor in the gas phase
PH2S is the partial pressure of hydrogen sulfide in the gas phase
As shown in Figure 2.3, the equilibrium constant decreases rapidly with

temperature. Therefore, at very high temperatures equilibrium is approached, but as
temperature decreases, reaction kinetics are drastically reduced to impractical levels.
Figure 2.3: Equilibrium Constant for the Reaction ZnO + H2S = ZnS + H2O.
Source: Kohl and Neilsen (1997) pg. 1307.
Zinc-oxide processes are available in several forms for operation at

temperatures from about 200 C to 400 C. Maximum sulfur loading is typically in
the range of 30-40 kg sulfur/100 kg sorbent for these processes. Puraspec, marketed
by IC Industries of Great Britain, is a proprietary combination of zinc oxides that
boasts more effective performance in the temperature range of 40 C to 200 C.
Nevertheless, performance is preferable at 200 C to 40 C, so operation below 150 C
is rarely practiced. Spent product may also contain over 20% sulfur (by weight).
Formation of zinc sulfide is irreversible and zinc oxide is not very reactive with
24
organic sulfur compounds. If removal of mercaptans is also desired, catalytic
hydrodesulfurization to convert these compounds to the more reactive hydrogen
sulfide is needed first (Kohl and Neilsen 1997).
2.5.1.3. Alkaline Solids
Alkaline substances, such as hydrated lime, will react with acid gases like H2S,
SO2, CO2, carbonyl sulfides and mercaptans in neutralization reactions. Usually
liquid-based scrubbers are used, but fixed-beds of alkaline granular solid can also be
used in a standard dry box arrangement with up-flow of gas. Molecular Products Ltd.,
of Great Britain, markets a product called Sofnolime-RG, which is claimed to be a
synergistic mixture of hydroxides that react with acid gases. Predominant reactions
are shown in Equations 2.7-2.8 (Kohl and Neilsen 1997)
2NaOH + H2S Na2S +2H20
(2.7)
Ca(OH)2 + CO2 CaCO3 + H2O
(2.8)
To achieve significant removal of H2S, CO2 must also be concurrently reduced

at the cost of extremely high product utilization. Sofnolime can remove about 180 L
of CO2/kg of media. At this efficiency, it would require over 3,020 kg/day of
Sofnolime to remove all of the CO2 from 1350 m3 biogas/day, assuming 40% CO2
concentration by volume.
2.5.1.4. Adsorbents
Adsorbents rely on physical adsorption of a gas-phase particle onto a solid
surface, rather than chemical transformation as discussed with the previous dry
sorbents. High porosity and large surface areas are desirable characteristics, enabling
25
more physical area for adsorption to occur. Media eventually becomes saturated and
must be replaced or regenerated. If regeneration of the media is economical or
desirable, it can be achieved by using one of the processes described in Table 2.12
below. During regeneration, H2S rich gas is released and must be exhausted
appropriately or subjected to another process for sulfur recovery (Yang 1987).
Table 2.12: Processes for Adsorbent Regeneration
Regeneration
Process
Description
Regeneration takes place primarily through heating. The

differences between the equilibrium loadings at the two
temperatures represent net removal capacity. Considerable
energy and time are required to heat and cool the bed. TSA is
often achieved by preheating a purge gas.
Regeneration is achieved by lowering the pressure of the bed
and allowing the adsorbate to desorb. Typically adsorption
Pressure Swing
takes place at elevated pressures to allow for regeneration at
Adsorption (PSA)
atmospheric pressure or under slight vacuum. PSA is
relatively fast compared to TSA
A non-adsorbing gas containing very little of the impurity is
Inert Purge
passed through the bed, reducing the partial pressure of
adsorbate in the gas-phase so that desorption occurs.
A purge gas that is more strongly adsorbed than the impurity is
used to desorb the original contaminant. Steam regeneration,
Displacement
while mostly a thermal process, also regenerates through
Purge
displacing some of the original adsorbate.
Temperature
Swing Adsorption
(TSA)
Molecular Sieves (Zeolites)

Zeolites are naturally occurring or synthetic silicates with extremely uniform
pore sizes and dimensions and are especially useful for dehydration or purification of
gas streams. Polar compounds, such as water, H2S, SO2, NH3, carbonyl sulfide, and
mercaptans, are very strongly adsorbed and can be removed from such non-polar
systems as methane. About 40 different zeolite structures have been discovered and
properties of the four most common ones are described in the Table 2.13.
26
Table 2.13: Basic Types of Commercial Molecular Sieves

Source: Kohl and Neilsen, (1997), pg. 1043
Adsorption preference, from high to low, is: H2O, mercaptans, H2S, and CO2.
Not all mercaptans are adsorbable on type 4A or 5A molecular sieves because of pore
size limitations. Consequently, 13X is preferred for complete sulfur removal from
natural-gas streams. Because contaminants are essentially competing for the same
active adsorption spots, a graphical representation of multiple adsorption zones in a
molecular sieve bed might occur as in Figure 2.4.
27
Figure 2.4: Adsorption Zones in a Molecular Sieve Bed, Adsorbing Both Water
Vapor and Mercaptans from Natural Gas.
Source: Kohl and Nielsen, (1997), pg 1071
A design method for natural-gas purification by 5A molecular sieves,

developed by Chi and Lee (1973), can be used to estimate approximate bed-sizes and
media-life for a zeolites process at AA Dairy. Minimum pressures of 3500 kPa, and
maximum CO2 concentration of 5%, were verified for their model, but for the
following calculations a 40% CO2 concentration is used (Chi and Lee 1973). Table
2.14 shows characteristics for a sample 5A-molecular-sieve system for AA Dairy.
28
Table 2.14: Summary of 5A Molecular Sieve Design at AA Dairy
High Loading
Low Loading
(units)
(1000 ppm H2S)
(4000 ppm H2S)
Gas Flow rate
Operating Pressure
Operating Temp.
Bed Life
Bed Height
Bed Diameter
Bed Volume
Bed Wt.
1,400
500
25
24
1.4
0.6
0.39
262
1,400
500
25
24
2.0
0.6
0.58
391
m3/day
psig
C
hours
m
m
m3
kg
As calculated, roughly 250-400 kg of zeolite would be needed on a daily basis,

and therefore would not be economical without a regeneration process.
Activated Carbon
Granular activated carbon (GAC) is a preferred method for removal of volatile
organic compounds from industrial gas streams. Heating carbon-containing materials
to drive off volatile components forms GACs, which have a highly porous adsorptive
surface. Utilization of GACs for removal of H2S has been limited to removing small
amounts, and primarily from drinking water. If H2S is the selected contaminant to be
removed, GACs impregnated with alkaline or oxide coatings are utilized.
Impregnated Activated Carbons
Coating GACs with alkaline or oxide solids enhance the physical adsorptive
characteristics of the carbon with chemical reaction. Sodium hydroxide, sodium
carbonate, potassium hydroxide (KOH), potassium iodide, and metal oxides are the
most common coatings employed.
Distributors of impregnated activated carbon include Calgon Carbon
Corporation (Type FCA carbon), Molecular Products, Ltd. (Sofnocarb KC), US
29
Filter-Westates, and Bay Products, Inc. Typically, 20-25% loading by weight of H2S
can be achieved, which is up from 10% as seen with regular GAC.
An example of particular interest was the use of a non-regenerable KOHactivated-carbon bed (Westates) for removal of H2S from anaerobic-digester and
landfill gas for use in a fuel cell. Oxygen (0.3-0.5% by volume) was added to facilitate
conversion of H2S to elemental sulfur. Two beds, 0.6 m in diameter by 1.5 m high,
were piped in series and run with space velocities of 5300/hr. Inlet H2S concentration
ranged from 0.7-50 ppm, averaging 24.1 ppm, and 98+% removal was demonstrated.
A loading capacity of 0.51 g S/g carbon was reported, which is substantially greater
than the normally reported range of 0.15 - 0.35 g S/g carbon for KOH-carbon. Media
costs were estimated at $5/kg for the adsorbent. Pretreatment system capital costs
(including sulfur removal, blowers and coalescing filters) were estimated to be
$500/kW (Spiegel, et al. 1997; Spiegel and Preston 2000).
Assuming loading capability of 25% and design with a 100 kW generator,
costs and performance might appear as represented in Table 2.15.
Table 2.15: System Characteristics for KOH-Impregnated
Activated Carbon at AA Dairy
Number of Vessels
Vessel Dimensions
$50,000
System Capital Cost
0.94 m3/min
Gas Flow Rate
250 kg each
Mass of Carbon
0.3%
O2 Recirculation Rate
High Loading
Low Loading
Annual Carbon Consumption
Annual Carbon Costs
(1000 ppm H2S)
(4000 ppm H2S)
340 days
270 kg
$1,250
85 days
1075 kg
$5,435
30
2.5.2. Liquid H2S Removal Processes
Liquid-based H2S removal processes have replaced many dry-based
technologies for natural-gas purification due to reduced ground-space requirements,
reduced labor costs, and increased potential for elemental-sulfur recovery. Gas-liquid
contactors, or absorbers, are used which increase surface area and optimize gas contact
time. If a reversible reaction is employed, regeneration columns are operated in
conjunction with the absorber to facilitate continuous processing. A generic
absorber/regenerator flow scheme is presented in Figure 2.5.
Clean Gas Out
Stripping
Solution
Stripping
Gas Out
Stripping
Gas In
Sour Gas In
Figure 2.5: Generic Absorber/Stripper Schematic

As indicated, the stripper gas contains the displaced H2S if it has not been
converted to elemental sulfur in the process. When the sulfide level is high, the sour
stripping gas can be sent to a Claus plant for elemental-sulfur recovery. When the
reaction is irreversible, a simpler bubble column may be used in place of an absorber.
Liquid-based H2S removal processes can be grouped into liquid-phase oxidation
processes, alkaline-salt solutions, and amine solutions. Physical adsorption of H2S
into a liquid, such as water, is discussed in the next section.
31
2.5.2.1. Liquid-Phase Oxidation Processes
Iron- and Zinc-Oxide Slurries
Iron-oxide slurry processes historically mark the transition between dry-box
technologies and modern liquid-redox processes. The basic chemistry is similar to
that for the dry oxide reactions. H2S is reacted with an alkaline compound in solution
and then iron oxide to form iron sulfide, as shown in Equations 2.9-2.10.
Regeneration is achieved by aeration, converting the sulfide to elemental sulfur, as
shown in Equation 2.11 (Kohl and Neilsen 1997).
H2S + Na2CO3 = NaHS + NaHCO3
(2.9)
Fe2O3.3H2O + 3NaHS + 3 NaHCO3 = Fe2S2.3H2O + 3 Na2CO3 + 3H2O (2.10)

2Fe2S2.3H2O +3O2 = 2Fe2O3.3H2O + 6S
(2.11)
Several side reactions can occur, forming thiosulfates and thiocyanates, which
continually deplete the active iron oxide supply. Commercial processes that were
available in the past include the Ferrox (1926), Gluud (1927), Burkheiser (1953),
Manchester (1953), and Slurrisweet (1982) processes (Kohl and Neilsen 1997).
A zinc-oxide liquid-based process, known as Chemsweet (Natco, Inc.), has
achieved some success in more recent years. The proprietary powder, consisting of
zinc oxide, zinc acetate, and dispersant, is mixed with water and used in a simple
bubble column. The reaction mechanisms are presented in Equations 2.12-2.14 below
(Kohl and Neilsen 1997).
ZnAc2 + H2S = ZnS +2HAc
(2.12)
ZnO + 2HAc = ZnAc2 + H2O
(2.13)
ZnO + H2S = ZnS +H2O
(2.14)
32
Low pH is maintained to avoid CO2 absorption and vessel corrosion while
encouraging RSH and COS removal. Pipeline-gas specifications are easily met, but
the high cost of non-regenerable reactant usually limits use of this process to removing
trace amounts of sulfur.
Quinone and Vanadium Metal Processes
The redox cycle shown in Figure 2.6 depicts how hydrogen sulfide is
converted to elemental sulfur using quinones.(Kohl and Neilsen 1997)
+ H2S
+ O2
Reduction
Oxidation
+S
+ H2O
Figure 2.6: Reduction-Oxidation Cycle of Quinones
Processes using quinones with vanadium salts, such as the Stretford process,
account for a large portion of the liquid-based natural-gas purification market today,
although chelated-iron processes are surpassing them. Because of high capital and
operating costs and significant thiosulfate byproduct formation, quinone-based H2S
technologies are generally not used for smaller gas streams.
Chelated-Iron Solutions
Chelated-iron solutions utilize iron ions bound to a chelating agent and are
gaining popularity for H2S removal. The LO-CAT (US Filter/Merichem) and
SulFerox (Shell) processes currently dominate the chelated-iron H2S removal market.
Basic redox reactions employed for adsorption and regeneration are as shown in
Equations 2.15-2.16.
33
2Fe3+ + H2S = 2Fe2+ + S + 2H+
(2.15)
2Fe2+ +(1/2)O2 + H2O = 2Fe3+ + 2OH-
(2.16)
The LO-CAT process is potentially attractive for biogas applications because

it is 99+% effective, the catalyst solution is nontoxic, and it operates at ambient
temperatures, requiring no heating or cooling of the media. Multiple configurations of
the LO-CAT process are available and Figure 2.7 below depicts a standard system.
Figure 2.7: Conventional Flow Diagram for LO-CAT Process

Source: Kohl and Nielsen (1997), pg 809.
LO-CAT systems are currently only recommended and economical for

facilities with over 200 kg S/day. Landfills and wastewater treatment plant digesters
have implemented LO-CAT H2S removal systems successfully, and LO-CAT plants
producing less than 500 kg of S/day are designed to produce thickened slurry, so use
of a separate thickener vessel is not required. The thickened slurry may have some
value as a fertilizer amendment in certain agricultural applications. The two principal
34
operating costs are for power for pumps and blowers, and chemicals for catalyst
replacement due to losses via thiosulfate and bicarbonate production (Kohl and
Neilsen 1997).
Le Gaz Integral Enterprise of France markets the Sulfint and SulFerox ironchelate processes targeted for gas streams with 100-20,000 kg S/day and high
CO2/H2S ratios. CO2 will not be removed significantly and 50% -90% of mercaptans
can be removed with either low or high-pressure applications. Sulfur removal with
SulFerox costs around $0.24-$0.3 per kg, and filtration using a plate-and-frame filter
is sufficient to recover elemental sulfur (Smit and Heyman 1999).
Other Liquid-Based Processes
Nitrite solutions are sometimes used when simple process configurations are
desired, requiring only a bubble-column contactor and mist eliminator. An overall
reaction is represented with Equation 2.17.
3H2S + NaNO2 = NH3 + 3S + NaOH + some NOx
(2.17)
In the presence of CO2, the NaOH is neutralized to produce sodium carbonate

and bicarbonate. As seen, the reaction products are ammonia and NOx, which may be
just as problematic as H2S to deal with. Nevertheless, the spent slurry is nonhazardous and non-corrosive, the equipment is simple and low cost, and change-out of
spent adsorbent is easy. Sulfa-Check (NL Industries, Inc.) and Hondo HS-100
(Hondo Chemicals, Inc.) are two commercially available nitrite-based media. Design
guidelines include: (Kohl and Neilsen 1997)
1.) Optimum efficiency in the temperature range of 24 C to 43 C.
2.) Maximum superficial velocity of gas should be below 0.05 m/sec.
3.) 6.310-6 liters of solution are required per m3 of gas per ppm of H2S.
35
4.) Liquid height in meters should be 0.76 times the logarithm of H2S
concentration in ppm.
Using these criteria and gas characteristics described in Table 2.5, a vessel 0.61
meters in diameter, and 2.3 2.7 meters in liquid height should be employed.
Permanganate and dichromate solutions can also be used to completely remove
traces of H2S. Spent media is also non-regenerable and the high costs of chemicals
limit the use of this process.
2.5.2.2. Alkaline Salt Solutions
As with alkaline solids, acid gases such as H2S and CO2 react readily with
alkaline salts in solution. Regenerative processes employ alkaline salts including
sodium and potassium carbonate, phosphate, borate, aresenite, and phenolate, as well
as salts of weak organic acids. Since H2S is adsorbed more rapidly than CO2 by
aqueous alkaline solutions, some partial selectivity can be attained when both gases
are present by ensuring fast contact times at low temperatures (Kohl and Neilsen
1997).
Caustic Scrubbing
Hydroxide solutions are very effective at removing CO2 and H2S, but are nonregenerable. Mercaptans form less-strongly-bound mercaptides, which are
regenerable at high temperatures, and commercial caustic-plants have operated with
this specialty.
The Dow Chemical Company developed a low-residence-time absorber for the
selective removal of H2S. Tests indicated reduction of 1000 ppm H2S to less than 100
ppm (in the presence of 3.5% CO2 @ 1400 m3/day), with a gas-residence time of 0.02
sec, pressure drop of 14 kPa, and liquid-to-gas ratio of 0.004 l/m3. Disposal of the
36
liquid effluent was a major problem. Also, the presence of higher CO2 concentrations
would lead to higher chemical utilization.
Other Alkaline Salt Processes
The Seaboard process (ICF Kaiser) was the first commercially applied liquid
process for H2S removal and used a sodium-carbonate absorbing-solution with air
regeneration. The overall chemical reaction is shown in Equation 2.18:
Na2CO3 + H2S = NaHCO3 + NaHS
(2.18)
Removal efficiencies of 85% 95% were realized, but the occurrence of side
reactions and problems with disposal of the foul air, containing H2S, has restricted use
of this process. Variations on the Vacuum Carbonate process (ICF Kaiser), which also
employ carbonates, have replaced the Seaboard process by enabling vacuum capture
of the foul stripping-gas and reducing the steam requirement needed for regeneration.
Many other processes are available at ambient and elevated temperatures that
use alkaline-salt solutions for removal of CO2 and H2S from gas streams. However,
the complexity of these processes makes them unattractive for H2S removal from
small biogas streams.
2.5.2.3. Amine Solutions
Amine processes constitute the largest portion of liquid-based natural-gas
purification technologies for removal of acid gases. They are attractive because they
can be configured with high removal efficiencies, designed to be selective for H2S or
both CO2 and H2S, and are regenerable. Drawbacks of using an amine system, as with
most liquid-based systems, are more complicated flow schemes, foaming problems,
chemical losses, higher energy demands, and how to dispose of foul regeneration air.
37
Alkanolamines generally contain a hydroxl group on one end and an amino
group on the other. The hydroxyl group lowers the vapor pressure and increases water
solubility, while the amine group provides the alkalinity required for absorption of
acid gases. The dominant chemical reactions occurring are as shown in Equations
2.192.23 (Kohl and Neilsen 1997).
H2O = H+ + OH-
(2.19)
H2S = H+ + HS-
(2.20)
CO2 + H2O = HCO3- + H+
(2.21)
RNH2 + H+ = RNH3+
(2.22)
RNH2 + CO2 = RNHCOO- + H+
(2.23)
Typically used amines include monothanolamine (MEA), diethanolamine

(DEA), methyldiethanloamine (MDEA), and diisopropanolamine (DIPA). Adsorption
is typically conducted at high pressures with heat regeneration in the stripper. Glycol
solutions, mentioned in the next section, are also employed to enhance physical
absorption characteristics of the acid gases. The basic flow-scheme for an
alkanolamine acid-gas removal process is depicted in Figure 2.8.
38
Figure 2.8: Flow Scheme for Alkanolamine Acid-gas Removal Processes

Source: Kohl and Nielsen (1997), pg 58
Sulfa-Scrub (Quaker Chemical Company) is a triazine-based sorbent

developed to selectively remove H2S from gas streams with minimal corrosion and
non-hazardous spent media. Sulfa-Scrub has been used in scavenging applications
without regeneration, and media consumption was around 5.310-6 - 6.710-6 l/m3 per
ppm of H2S in the feed gas. This corresponds to generation of 10-40 liters per day of
spent non-regenerable slurry from an operation similar to AA Dairys. Further
information on the design and operation of alkanolamine plants can be found in Gas
Purification, Kohl and Nielsen (1997).
2.5.3. Physical Solvents
When acid gases make up a large proportion of the total gas stream, the cost of
removing them with heat-regenerable processes, such as amines, may be out of line
with the value of the treated gas. Physical solvents, where the acid gases are simply
39
dissolved in a liquid and flashed off elsewhere by reducing the pressure, have been
employed with limited success. Since these processes depend on partial-pressure
driving forces, some product will invariably be lost, especially at higher pressures.
2.5.3.1. Water Washing
Liquids with increased solubilities for CO2 and H2S are typically chosen over
water, but the principal advantages of water as an absorbent are its availability and low
cost. Absorption of acid gas produces mildly corrosive solutions that can be damaging
to equipment if not controlled. Table 2.16 indicates Henrys law constants for biogas
components in water.
Table 2.16: Henrys Law Constants at 25 C and 1-Atmosphere
CH4
CO2
H2S
1.5 x 10-4 M/atm

3.6 x 10-2 M/atm
8.7 x 10-2 M/atm
As seen, H2S has a slightly higher solubility than CO2, but costs associated
with selective removal of H2S using water scrubbing have not yet shown competitive
with other methods. Therefore, water scrubbing will probably only be considered for
the simultaneous removal of both H2S and CO2. Experimentally derived equilibrium
constants for mixtures of CH4, CO2, and H2S have been determined and can be used to
calculate water and gas flow rates, as well as vessel dimensions (Froning, et al. 1964).
2.5.3.2. Other Physical Solvents
Solvents such as methanol, propylene carbonate, and ethers of polyethylene
glycol, among others, are offered as improved physical solvents. Criteria for solvent
selection include high absorption capacity, low reactivity with equipment and gas
40
constituents, and low viscosity. Thermal regeneration techniques are still needed in
most cases to achieve pipeline-quality gas. Additionally, loss of product can be higher
with these solvents, as levels as high as 10% have been reported (Kohl and Neilsen
1997).
The Selexol process (Union Carbide) utilizes dimethylether of polyethylene
glycol (DMPEG) as a purely physical solvent. In 1992, Union Carbide reported 53
Selexol plants operating, of which 15 were designed for selective removal of H2S and
8 were in service for landfill-gas purification. Like water scrubbing, the cost for
selective H2S removal has not yet shown to be competitive and this process will most
likely only be considered for applications in which upgrading to relatively pure
methane is desired (Wellinger and Linberg 2000).
The Sulfinol Process (Shell Oil Company) is unique because it couples
improved physical solvents with chemical amine agents to boost removal efficiencies.
This method can easily produce pipeline-quality gas, but has yet to be demonstrated as
economical for small-scale biogas H2S removal.
2.5.4. Membrane Processes
Membranes operate based on differing rates of permeation through a thin
membrane, as dictated by partial pressure. Because of this, 100% removal efficiency
is not possible in one stage, and some product will inevitably be lost. Two types of
membrane systems exist: high pressure with gas phase on both sides, and low pressure
with a liquid adsorbent on one side. Membranes are generally not used for selective
removal of H2S from biogas but are becoming more attractive for upgrading of biogas
to natural-gas standards because of attributes such as reduced capital investment, ease
of operation, low environmental impact, gas dehydration capability, and high
reliability.
41
Kayhanian and Hills (1987) studied high-pressure membrane purification
specifically for the purification of anaerobic-digester gas. Cellulose acetate
membranes operating at 25C, 550 kPa, and a stage cut (ratio of permeate flow rate to
non-permeate flow rate) of 0.45 performed the best for removal of CO2 and H2S, and
reduced 1000 ppm H2S to 430 ppm (Kayhanian and Hills 1988). Three-stage units
treating landfill gas have achieved product gases with over 96% CH4 but utilize
separate H2S removal systems to extend the membrane life, which is typically in the
range of three to five years (Wellinger and Linberg 2000).
Low-pressure gas-liquid membrane processes have recently been developed
specifically for upgrading of biogas and operate at around atmospheric pressure and
25C 35C. Initial trials indicate that 2% H2S concentrations can be reduced to less
than 250 ppm using NaOH or coral solutions for the liquid. Amine solutions can be
employed for preferential CO2 removal and traditional liquid regeneration techniques
employed for the solvent. This process is still in a developmental stage but may prove
to be desirable in the future (Eriksen, et al. 1999).
2.6. ALTERNATIVE H2S CONTROL METHODS

2.6.1. In-Situ (Digester) Sulfide Abatement
Iron chlorides, phosphates, and oxides can be added directly to the digester to
bind with H2S and form insoluble iron sulfides. McFarland and Jewell (1989) studied
the effects of digester pH and addition of insoluble iron phosphate directly to
digesters, pointing out that addition of FeCl3, although regularly practiced, is often
inconsistent and inconclusive for reducing H2S. Lab studies showed that increasing
pH from 6.7 to 8.2 through the addition of phosphate buffers reduced gaseous sulfide
emissions from 2900 to 100 ppm, while increasing soluble sulfide concentrations from
42
18 to 61 mg/l. Soluble sulfide levels around 120 mg/l begin to inhibit CH4 production.
Addition of insoluble iron (3+) phosphate up to FePO4-Fe:SO42--S ratios of 3.5,
reduced gaseous sulfide levels from 2400 to 100 ppm (McFarland and Jewell 1989).
Ferric phosphate (FePO4) and ferric oxide (Fe2O3) are able to lower HSconcentrations in the digester via Equations 2.24 and 2.25 (Jewell, et al. 1993).
2 FePO4 H2O + 3 H2S Fe2S3 + 2 H3PO4 + 2 H2O
(2.24)
Fe2O3 H2O + 3 H2S Fe2S3 + 4 H2O
(2.25)
This method may be effective as a partial removal process for reducing high
H2S levels, but usually must be used in conjunction with another technology for
removal down to about 10 ppm H2S. Concern also exists that accumulation of
insoluble iron sulfides might cause premature buildup in a digester (Jewell, et al.
1993).
Richards, et al. (1994), studied a unique, in-situ, method for methane
enrichment whereby the leachate from a semi-continuously fed and mixed (SCFM)
reactor was purged of CO2 in an external, air-purged, stripper. This process took
advantage of differing solubilities for CO2 and methane, and it produced gas with over
98% CH4. No monitoring of H2S was conducted. This process has limited application
to SCFM or CSTR reactors, and further testing is needed to determine practical design
and operating requirements for larger-scale operation (Richards, et al. 1994).
2.6.2. Dietary Adjustment
Diet composition influences sulfur content in animal wastes, which directly
impact sulfides emitted from anaerobically digested manure. Sulfur is a required
nutrient for animal health and cannot be completely eliminated from a diet. Shurson,
et al. (1998), have reduced H2S levels from anaerobic swine-manure lagoons by 30%
43
through careful manipulation of a nutritional swine diet. Animal performance and
ammonia emissions were not studied in this experiment. Dietary adjustment is
generally not used for sulfide reduction because diets are typically optimized for
product yields and animal health, rather than sulfur levels in the excrement.
Furthermore, a complete reduction in H2S can never be effected, so additional H2S
abatement processes are needed (Shurson, et al. 1998). However, limiting sulfur
containing chemicals or high sulfate content waters from inadvertently entering the
digester could be a simple way to reduce H2S emissions somewhat.
2.6.3. Aeration
A simple technique for H2S reduction, now practiced in Europe, includes
air/oxygen dosing into the biogas. Air is carefully admitted to the digester or biogas
storage tank at levels corresponding to 2-6% air in biogas. It is believed effectiveness
is based on biological aerobic oxidation of H2S to elemental sulfur and sulfates.
Inoculation is not required, as Thiobacillus species are naturally occurring at aerobic
liquid-manure-wetted surfaces. Full scale digesters have claimed 80-99% H2S
reduction, down to 20-100 ppm, by adding <5% air with a simple air pump. Yellow
clusters of sulfur are deposited on surfaces, increasing chances of corrosion. Care
must also be taken to avoid explosive gas mixtures (Nijssen, et al. 1997).
2.7. BIOLOGICAL H2S REMOVAL METHODS

2.7.1. History and Development
To biologically address the problem of malodorous air, open-bed soil filters
began to be used in the 1920s and industrial soil biofilters first appeared in the United
44
States during the 1950s, but operation was not well understood (Carlson and Leiser
1966). Sulfur compounds are a major component of malodor in gases and are
produced during biochemical reduction of inorganic or organic sulfur compounds.
Many soils do exhibit a small chemical adsorption capacity for H2S that is heavily
dependent on the iron content of the soil (Bohn and Fu-Yong 1989). It has since been
determined that sustained effectiveness of soil or other biofiltration beds arises
primarily from microbial oxidation of organic compounds, leading to biomass
formation and nontoxic odorless products, or oxidation of inorganic compounds (such
as sulfides), which supply energy to cells and produce odorless compounds like
elemental sulfur and sulfate in the process (Ottengraf 1986).
Biologically active agents have since been used in a variety of process
arrangements, such as biofilters, fixed-film bioscrubbers, and suspended-growth
bioscrubbers (Dawson 1993). These processes may also be effective at removing
multiple contaminants from a gas stream, increasing their functionality. Fluidized-bed
bioreactors have recently been tested for simultaneous removal of H2S and NH3 with
promising results (Chung, et al. 2001). It is also possible to achieve co-treatment of
volatile organic compounds and H2S in the same biofilter (Devinny, et al. 1999).
Reviews on exhaust gas purification for odor control, microbiological
treatment of H2S containing gases, and biofiltration for air pollution control have been
published that summarize the current state of the art (Ottengraf 1986, Jensen and
Webb 1995, Devinny, et al. 1999). A general biofiltration process may include the
elements illustrated in Figure 2.9.
45
Figure 2.9: Biofiltration System Schematic

Source: Swanson and Loehr (1997)
There are many companies specializing in the design and operation of

biofilters for pollution control, including TRG biofilters, Bohn Biofilter Corporation,
Biorem Technologies, Biocube, Inc., and Envirogen, among others.
2.7.2. Biological Sulfur Cycles
Sulfur exists in many oxidation states from +6 (SO4) to 2 (H2S).
Transformations take place at significant rates both chemically and biologically. The
global balance of sulfur is depicted in the Figure 2.10.
46
Figure 2.10: The Global Sulfur Cycle.

(Artificial emissions are derived from human activities. An asterisk indicates a
process that is partially or solely due to microbial action.)
Source: Madigan, et al.(2000), pg 688.
Most sulfur in the Earths crust is contained in sulfate minerals, such as

gypsum, and sulfide minerals, such as iron pyrite. The oceans constitute the most
significant reservoir for sulfur, mostly in the form of inorganic sulfate. The biological
sulfur-cycle due to microbial involvement is depicted in Figure 2.11.
47
Figure 2.11: Biological Redox Cycle for Sulfur

Source: Madigan, et al. (2000), pg 687.
H2S is produced from bacterial sulfate-reduction in Desulfovibrio,

Desulfobacter, Desulfuromonas, and many other hyperthermophilic Archaea, via the
overall pathway shown in Equation 2.26.
SO42- + 8 H H2S + 2 H2O + 2 OH-
(2.26)
Once present, other microorganisms can use H2S oxidation to gain energy.
Various groups of organisms can oxidize reduced sulfur compounds under aerobic or
anaerobic conditions, including:
Colorless sulfur bacteria (aerobic, i.e.: Thiobacillus, Beggiatoa, Thiothrix, etc.)
Green sulfur bacteria (anaerobic, phototrophic, i.e.: Chlorobium, etc.)
Purple sulfur bacteria (anaerobic, phototrophic, i.e.: Chromatium, Thiocapsa, etc.)
48
Colorless sulfur-oxidizing bacteria are most widely used to oxidize H2S using
oxygen as an electron acceptor. This process is preferred because growth rates are
significantly higher and there are no light intensity requirements. Thiobacillus species
are thought to account for a majority of sulfide oxidation, via the sulfite-oxidase
pathway as described in Figure 2.12 below.
Figure 2.12: Steps in the Oxidation of Sulfur Compounds by Thiobacillus Species.

Source: Yang (1992), pg 24.
The most energy is released when sulfide is oxidized completely to sulfate as

seen in Equation 2.27. Sulfide oxidation often occurs in steps with elemental sulfur as
an intermediate product, as seen with Equations 2.28-2.29, and in oxygen-limited
environments, oxidation may proceed only to elemental sulfur, producing less energy.
Cells can either deposit sulfur inside or outside of their cell membranes. Other
reduced sulfur compounds, such as thiosulfate, can also be oxidized for energy as seen
in Equation 2.30.
49
H2S + 2 O2 SO42- + 2 H+
(G0 = -798.2 kJ/rxn)
(2.27)
HS- + O2 + H+ S0 + H2O
(G0 = -209.4 kJ/rxn)
(2.28)
S0 + H2O + 1 O2 SO42- +2 H+
(G0 = -587.1 kJ/rxn)
(2.29)
S2O32- + H2O + O2 SO42- + H+
(G0 = -409.1 kJ/rxn)
(2.30)
Table 2.17 references several studies on biofiltration of H2S with specific

bacterial populations.
Table 2.17: Specific Microorganisms Studied for Biofiltration of H2S

MICROORGANISM
Thiobacillus species
Thiobacillus thioxidans
Thiobacillus denitrificans
Thiobacillus thioparus
Thiobacillus ferrooxidans
Thiobacillus novellas
Thiobacillus versutus
Thiobacillus neopolitanus
Pseudomonas putida
Hyphomicrobium
Xanthamonas species DY44
REFERENCE
Degorce-Dumas, et al. (1997), Nishimura and Yoda
(1997), Koe and Yang (2000), Oh, et al. (1998)
Cho, et al. (2000), Cadenhead and Sublette (1990)
Sublette, et al. (1994), Sublette and Sylvester
(1987a, 1987b)
Cho, et al. (1992), Cadenhead and Sublette (1990)
Jensen and Webb (1995)
Chung, et al. (1998)
Cadenhead and Sublette (1990)
Cadenhead and Sublette (1990)
Chung, et al. (1996, 2001)
Zhang, et al. (1991)
Cho, et al. (1992)
Reaction products from many of these microorganisms include sulfates and H+,
which form sulfuric acid in the leachate and reduce the pH. Some Thiobacillus
species are acidophilic and therefore function adequately at low pH, but organic media
tends to degrade under these conditions causing plugging and increased pressure drop.
Investigations of different media have been done with respect to H2S removal in
biofilters, as summarized in Table 2.18.
50
Table 2.18: Media Tested for Biofiltration of Hydrogen Sulfide

ORGANIC MEDIA
Soil
Peat
Compost
Sludge
Pig Manure/Sawdust
Wood Bark and Waste
Activated Carbon
Rock Wool
INORGANIC MEDIA
Lava Rock
Poly-propylene Rings
Calcium-alginate Beads
Fuyolite and Ceramics
REFERENCE
Carlson and Leiser (1966)
Furusawa, et al. (1984), Hartikainen, et al. (2001),
Kim, et al. (1998), Zhang, et al. (1991), DegorceDumas, et al. (1997), Cho, et al. (1992)
Rands, et al. (1981), Yang (1992), Wani, et al.
(1999), Sun, et al. (2000)
Yang (1992), Degorce-Dumas, et al. (1997)
Elias, et al. (2002)
Langenhove, et al. (1986), (Wani, et al. (1999)
Oh, et al. (1998)
Kim, et al. (1998)
REFERENCE
Cho, et al. (2000)
Koe and Yang (2000)
Chung, et al. (1996)
Kim, et al. (1998)
Desirable attributes for biofilter support media include high surface area, low
pressure-drop characteristics, good moisture retention properties, durable in their
active environment, can provide a source of nutrients for an active biolayer, and
support a diverse community of microbes. The trade-off between organic and
inorganic media is traditionally that organic composts have vibrant microbial
populations and form extremely active biolayers, but degrade quickly at low pH and
have higher pressure-drops than some inorganic carriers.
2.7.3. Example Applications
A comprehensive study of operational parameters, design, and basic kinetic
modeling for removing H2S from air with composted sewage sludge and yard waste
was conducted by Yang and Allen (1994). Variables studied include temperature,
residence time, concentration, loading rate, compost sulfate level, acidity, and water
51
content. H2S removal efficiencies greater than 99.9% were noted using yard waste
composts and inlet concentrations ranging from 5 to 2650 ppm. Maximum
elimination capacities for the composts ranged from 11.5 to 130 g S/m3-solids/hr
(Yang and Allen 1994a, 1994b).
Elias, et al. (2002), operated an H2S biofilter using compressed composted pig
manure and sawdust for 2500 hours with over 90% removal efficiency. H2S loading
in air was in the range of 1045 g H2S/m3-solids/hr with empty-bed residence times of
13-27 seconds. No chemical additions were needed for buffering or nutritive reasons
during operation. Elemental sulfur was the main sulfur product accumulated (87.5%
of sulfur) in the bed. Only a small pH drop was noticed, so leaching of heavy metals
was not significant (Elias, et al. 2002).
Manure composts have been used for biofiltration of other compounds as well.
Chou and Cheng (1997) tested composted pig- and cow-manure media, mixed with
woodchips and activated sludge, for removing methyl ethyl ketone (MEK), and
achieved removal rates of around 50 g/m3-solids/hr (Chou and Cheng 1997).
Cardenas-Gonzalez, et al. (1995), compared properties of immature and mature yardwaste and horse-manure composts for biofiltration of VOCs and found that the horsemanure compost had higher microbial activity and shorter acclimation time, but was
not as stable for long term operation (Cardenas-Gonzalez, et al. 1999).
Degorce-Dumas, et al. (1997), tested biofilter columns with peat and dry
wastewater sludge on actual biogas (characterized as 50-60% CH4, 40-50% CO2, and
0.5-2.0% H2S), mixed 2:1 with air. The H2S concentration in the gas stream was
measured at 3260 mg/m3 (2375 ppm), and the column maintained 100% removal
efficiency for 10 days at a loading rate of 129 g H2S/m3-solids/hr. Autoclaved
compost, used as a control, showed only 60% H2S removal under similar conditions.
A Henrys law calculation indicated that the abiotic removal efficiency cannot come
52
only from H2S absorption into water, but must also be from chemisorption (DegorceDumas, et al. 1997).
Gadre (1989) also passed actual biogas from a lab scale anaerobic digester
(~55% CH4, ~42.5% CO2, and 2.04% H2S) through a 50-mL glass-bead-packed
biotrickling filter washed with innoculum isolated from distillery wastewater. The
collection vessel for the wastewater was open to the atmosphere and assumed to
contain aerobic Thiobacillus species due to a pronounced drop in pH to 3.0. 69.5%
H2S removal was achieved at a loading rate of 187 mg H2S/day (Gadre 1989).
Nishimura and Yoda (1997) performed a similar experiment with a more methane rich
biogas (~80% CH4, ~20% CO2, and 2000 ppm H2S), and were able to achieve 99.5%
reduction in H2S with a gas flow of 40 m3/hr in a 3 m3 bubble column reactor
(Nishimura and Yoda 1997).
A German patent issued to Neumann, et al. (1990), describes a method for
removal of H2S from biogas utilizing Thiobacillus ferooxidans in a packed bed of peat
or refuse-compost. Although flow rates and oxidation rates are not mentioned,
experimental results indicate a product gas with 59.8% CH4, 30.8% CO2, undetectable
H2S, 9.1% N2, and 0.5% O2, was produced from an inlet gas with 65% CH4, 34.0%
CO2, 1.0% H2S, 0.0% N2, and 0.0% O2 (Jensen and Webb 1995).
To investigate inorganic media supports for durability during low-pH H2S
biofiltration, Cho, et al. (2000), specifically immobilized Thiobacillus thioxidans on
porous lava rock. The rock showed favorable moisture retention and resisted
excessive pressure drops. Increased removal capacities up to 428 g S/m3-solids/hr
were reported with space velocities of 300-hr-1 (Cho, et al. 2000). In a previous study,
Cho, et. al. (1992), reported 89%+ removal of dimethyl-sulfide, methanethiol,
dimethyl-disulfide, and H2S with a Thiobacillus thioparus biofilter treating exhaust
gas from a night-soil (septic sludge) treatment plant (Cho, et al. 1992).
53
Koe and Yang (2000) also tested Thiobacillus thioxidans with plastic packing
and found that for gas-retention times greater than five seconds and a loading rate
below 90 g S/m3-solids/hr, 99% H2S removal was obtained (Koe and Yang 2000).
H2S levels up to 10,000 ppm were oxidized by Sublette, et. al. (1994), with
pure cultures of Thiobacillus denitrificans in less than 2 seconds under anoxic
conditions. Here, added nitrate, rather than oxygen, served as the terminal electron
acceptor. These reaction times indicated that limitations in H2S removal were due to
mass transfer rather than biological limitations. Up to 97% reduction in inlet H2S
levels were achieved (Sublette, et al. 1994).
Anaerobic bacteria have also been used for H2S oxidation from gas streams.
Cork, et al. (1983), provided the first demonstration of photoautotrophic growth of a
Chlorobium species with continuous inorganic gas feed (3.9% H2S, 9.2% CO2, 86.4%
N2, and 0.5% H2). The reaction was completed in a 1-L clear vessel with an external
light source. With a removal efficiency of 99.6% H2S, elemental sulfur and biomass
were the main reaction products (Cork, et al. 1983). Subsequent work with
Chlorobium species has been done (Kim, et al. 1997; Henshaw and Zhu 2001;
Kobayashi, et al. 1983) and an economic estimate of $2.82$4.24 per thousand
standard cubic meters for gas desulfurization has been made (Basu, et al. 1996).
A few commercial biological processes exist specifically for energy gas
desulfurization. The Biopuric process (Biothane Corporation) has designed and tested
systems for H2S removal from gas streams similar to those found at agricultural
anaerobic-digestion facilities (15007000 m3 gas/day and 100027000 ppm H2S) with
consistent removal efficiencies over 97%. These systems generally cost $75,000
$100,000 for capital investments alone (Lanting and Shah 1992).
Another biological process targeted at sour gas desulfurization is the Thiopaq
Process (UOP). SO2 and H2S are absorbed in a traditional chemical scrubber with
54
sodium bicarbonate solution (Ruitenberg, et al. 1999). Pressures in the scrubber are
often elevated to 6000 kPa to enhance absorption (Janssen, et al. 2000). The spent
liquid is then regenerated in a separate bioreactor, producing elemental sulfur. 99%
H2S removal is reported and 90-95% of the sulfur is recoverable. A $1.7 million
Thiopaq installation removed 2.76% H2S from 2000 m3 gas/hr to less than 10 ppm,
while recovering 96% of the sulfur. Operating costs were estimated at $65/day for
nutrients, 75 kWh/hr of electricity, and 180 kg/day of NaOH (UOP 2000).
2.8. RESEARCH STATEMENT

With integrated farm energy systems, the opportunity exists for improvements
in gas processing by utilizing on-farm compost and biological processes for H2S
removal. While there is a wealth of operational and research experience on
biofiltration for odor control, there is a relatively limited amount of information on
biofiltration for gas processing to purify biogas. No studies, to this authors
knowledge, exist where anaerobically digested and composted dairy-manure has been
tested for its capability to selectively remove H2S, often at elevated levels, from
biogas. The following research directly addresses this need.
CHAPTER
3. MATERIALS AND METHODS
An experimental approach was used to investigate the suitability of digested

cow-manure compost for removal of H2S from biogas. Test reactors were constructed,
packed with compost, and exposed to actual biogas on-site at AA Dairy. The
experimental setup was located in the enclosed, but non-environmentally controlled,
engine room.
3.1. REACTORS
3.1.1. Small Reactors
Four reactor columns were built using 0.10 m (4 inch) ID, schedule-40 white
polyvinyl chloride (PVC) pipe. Each reactor is 0.5 m in length with female adapters
and male cleanout plugs on each end. Although clear pipe would have been desirable
for observing the compost, white pipe was used due to budget limitations. Type 316
stainless steel woven wire discs (0.032 inch wire with 8 x 8 wires per inch) were glued
into the columns 0.1 m from the end for packing support. Plastic 6.35 mm ( inch)
barbed fittings were placed in the center of each cleanout plug and 0.05 m from the
column ends for gas delivery and sampling with 6.35 mm flexible PVC tubing. The
small reactors are depicted in Figure 3.1. Two of the small reactors were equipped
with liquid leachate recycle capability using a Cole-Parmer peristaltic pump with dual
heads, as shown in Figure 3.2. Three-millimeter holes were drilled in all small
columns at 0.05, 0.25, and 0.45 m lengths for thermocouple insertion.
55
56
OUT
0.05 m
1
0.5 m
G
2
0.3 m
G
IN
0.05 m
0.1 m
LEGEND:
T = Thermocouple
G = Gas Sampling Port
IN = Gas Sample Inlet
OUT = Gas Sample Outlet
1 - PVC End Caps

2 - Top of Bed
3 PVC Pipe
4 Wire Screen
Figure 3.1: Schematic of Small Columns
57
0.05 m
OUT
0.5 m
G
2
0.3 m
G
IN
0.05 m
5
0.1 m
LEGEND:
T = Thermocouple
1 - PVC End Caps

2 - Top of Bed
3 - PVC Pipe
4 - Wire Screen
5 Peristaltic Pump
Figure 3.2: Schematic of Small Columns with Leachate Recycle
58
3.1.2. Large Reactors
Two identical 0.16 m (6.355 inch) ID by 1.5 m length clear PVC (ALSCO
Industrial Products, Inc.) columns were constructed with 3.175 mm wall thickness.
Each column was divided into three sections for easy inter-column gas sampling,
accessible compost loading, and to prevent compaction, as seen in Figure 3.3.
Specially constructed couplers lathed from 0.15 m (6 inch) ID schedule-40 white-PVC
pipe were used in conjunction with plastic draw latches and neoprene O-rings (size
362) to seal the sections. The same stainless steel screen used in the small reactors
were reinforced with 6.35 mm aluminum bars and glued into place as a bed support.
Silicone sealant was used to seal any leaks because of insufficient o-ring seating.
Barbed plastic fittings (6.35 mm) were installed before and after each bed
section for gas sampling with 6.35 mm clear-PVC flexible tubing. Inlet and outlet gas
ports were 6.35 mm plastic ball valve fittings. Thermocouples were inserted into the
center of each bed section and near the gas inlet and outlet ports for temperature
measurement.
PVC and 316 stainless steel materials were chosen because they are not
affected by exposure to methane, carbon dioxide, hydrogen sulfide, or dilute
concentrations (<75%) of sulfuric acid (Cole Parmer 2002). All reactors were
pressure tested in the laboratory to 34.5 kPa using compressed air, and no leaks were
detected.
59
OUT
0.05 m
G
1.5 m
3
G
0.3 m
T
5
G
0.4 m
T
2
G
IN
0.05 m
LEGEND:
T = Thermocouple
1 - PVC End Caps

2 - Wire Screen
3 - PVC Pipe
4 Plastic Latches
5 PVC Couplers
Figure 3.3: Schematic of Large Columns
60
3.2. EXPERIMENTAL SETUP ON SITE
Piping was established so that a small portion of biogas could be diverted to
the test columns and returned to the original pipeline upstream of the engine, as shown
in Figure 3.4. Existing piping enabled digester gas at 0.751 .0 kPa to enter three 250W blowers, boosting the pressure to around 3 kPa. From here gas passed through a
solenoid valve that regulated the positive pressure of the engine intake to about 1.5
kPa. As shown in Figure 3.4, a 5 cm (2 inch) PVC tee was installed with a ball valve
(Banjo Corporation) between the blowers and the solenoid valve. 5 cm ID PVC
piping was run approximately 5 m to the column test area and terminated with an endcap with 6.35 mm barbed fitting installed. From here, pumps were used to boost gas
pressure and the biogas stream could be split, as needed, depending on the
experimental configuration.
An exhaust manifold consisting of 3 m of 3.173 mm (1.25 inch) ID, schedule40, white PVC pipe was installed. A specially constructed steel box, containing a
rectangular automobile air filter element, was placed downstream of the manifold to
protect the engine from any particulate blow-over from the experimental columns.
The tested biogas was then returned to the main biogas pipeline downstream of the
solenoid valve. Another Banjo ball valve was placed at the return intersection to
enable complete shut-off of the experiment stream when not in use.
Figure 3.4: Experimental Setup at AA Dairy
62
Two vacuum pumps were used to provide the additional head needed for the
experimental columns; a larger pump and a smaller pump for use with respective
columns. The larger pump was a 370-W Sargent-Welch 1402 Duoseal single-phase
pump. Biogas was fed to the vacuum inlet of the pump through a 3 m length of 6.35
mm ID brass tubing and exhausted to a multi-ported manifold on the positive pressure
side of the pump. A Speedaire airline oil-removal filter and pre-filter were installed
on the inlet side of the pump to remove oil, particulates and some moisture. The pump
is specified to deliver 9.5 m3/hr at standard temperature and pressure, but only
delivered 3.3 m3/hr due to resistance on the inlet side. The original pump configuration
produced a significant amount of oil mist in the outgoing gas stream. A mist
eliminator was designed, constructed, and installed on the outlet side of the pump by
John Poe Tyler (Tyler 2001). The smaller pump was a Neptune Dyna-Pump vacuum
diaphragm pump and was operated without inlet or outlet filters.
Compressed air was available at the test site and regulated by a single-stage
Speedaire regulator before being delivered to a block of multiple,variable-area flowmeters, or rotameters (Dwyer Instruments, Inc.). Biogas and air were mixed
together at a tee connector on the inlet side of the humidification vessels.
To humidify the incoming gas, all inlet gas streams were bubbled through 1-L
plastic Nalgene bottles initially filled with 750 ml of distilled and deionized water. A
schematic of the simple humidification and mixing vessel is provided in Figure 3.5.
63
Air
Inlet
Biogas
Inlet
Mixed
Sample
Gas
Outlet
Figure 3.5: Humidifier and Air/Biogas Mixing Vessel

Two of the smaller columns were outfitted with a leachate recycle loop
consisting of a Cole-Parmer peristaltic pump with dual heads, as shown in Figure 3.2.
With a tubing size of 1/16, flow rates up to 7 ml/min were achievable. The pump
forced liquid to the top of the column where a drop would form. Another stainless
steel screen was placed 0.05 m below the recycle inlet port to disperse the droplet as it
fell across the top of the media.
Gas flow rates were controlled with Gilmont Accucal variable-area flowmeters (Barnant Company). Rates are measured by visually correlating the center of
the float with a graduated scale, calibrated for liters per minute of air at standard
temperature and pressure. Correction Equations 3.1-3.3 can be applied when
measuring gases other than air under non-standard conditions: (Gilmont 1993)
0 . 00120
q G0 = q 0A
G0
G0 = 1 xi i0
i
qG' = qG0
P 530
760 T
(3.1)
(3.2)
(3.3)
64
Where qG0 = Standard gas flow
q A0 = Standard air flow reading from meter

qG' = Gas flow at P (operating pressure) and T (operating temperature)
with volume corrected to measurement at standard conditions
G0 = Density of gas in g/ml at standard conditions

xi = Mole fraction of ith gas component
i0 = Density of ith gas component in g/ml at standard conditions
Assuming measurement at standard temperature and pressure, and

0
approximating biogas as 60% methane ( CH
= 0.00072 gm/ml), and 40% carbon
4
0
dioxide ( CO
= 0.00198 gm/ml), the corrected rotameter value calculated with
2
Equation 3.1, for biogas, becomes qG0 = 0.992 q A0 . Therefore, readings for air and
biogas are nearly the same.
3.3. GAS SAMPLING AND MEASUREMENT

Flexible PVC sample lines (6.35 mm ID) were run from the column gas
sampling ports to the inlet ports of a 16-channel multi-position valve (Valco
Instruments Co., Inc.). The desired sample line was selected with a digital controller,
and the outlet line from the switching valve was connected through a rotameter to the
H2S detector. Since the columns were operated under slight positive pressure, opening
the appropriate sample path allowed gas flow to the detector.
3.3.1. Electrochemical Sensor
An electrochemical, Toxi-Plus single gas detector (Biosystems, Inc.) was used
for H2S monitoring. The detector was equipped with a 0-100 ppm 4HS CiTiceL H2S
65
sensor (City Instruments, Inc.). A plastic calibration adapter provided by Biosystems,
Inc., enabled direct sampling of a gas stream, provided a flow rate near 1 liter per
minute.
The electrochemical sensor has been carefully designed to minimize the effects
of common interfering gases, but some interfering gases may still have either a
positive or negative effect on the sensor readings. Table 3.1 indicates deviation of
measured H2S values with respect to a number of substances. The table is not meant
to be complete, as there may be other gases to which the sensor responds.
Table 3.1: Cross Sensitivity Data for Electrochemical H2S Sensor

(Number reported is sensor response to 100 ppm of selected test gas)
Compound
CH4
CO2
CO
Cl2
(CH3)S
CH3SH
H2
NO2
O3
SO2
Response
0
0
<2
-20
10
45
< 0.5
-20
-30
< 20
Source:City Technolgy Limited (2002)
Calibration of the sensor is recommended on a daily basis and was done with
certified-standard 24.7 ppm H2S in nitrogen (Empire AirGas, Elmira, NY) supplied in
a size-33A cylinder containing 850 liters of product. A dual-stage, stainless-steel
regulator (CGA #330: Matheson Tri-Gas) delivered calibration gas to the sensor.
Since H2S concentrations in the biogas were outside the range of the sensor, an
air dilution method was developed and utilized. Compressed air delivered through a
rotameter at 3.9 liters per minute was continuously combined with 0.1 liters per
minute of sample gas at a plastic tee, creating a 40-fold dilution of the sample stream.
66
The gas mixture then entered a 1-liter sealed plastic mixing vessel similar to the
humidification vessel depicted in Figure 3.5, but without water. The effluent from the
mixing vessel was sent directly to the electrochemical sensor for measurement.
The H2S measurement protocol with the electrochemical sensor was as
follows:
1) Select desired sample channel from multi-position valve
2) Adjust gas sample flow rate from outlet of multi-position valve to 0.1 lpm
3) Adjust air flow rate to 3.9 lpm
4) Let gas mix and allow meter reading to stabilize (~4 minutes)
5) Repeat steps 1-4 for additional sample streams
3.3.2. Gas Sampling Tubes
Gas detection tubes employing chemical reaction with lead acetate (Sensidyne)
were used for additional measurement of H2S in the sample streams. The reaction in
Equation 3.4 occurs in the detector tube, causing a brown stain to form that can be
directly read for H2S concentration.
H2S + Pb(CH3COO)2 PbS + 2CH3COOH
(3.4)
A model 8014-400A (Matheson-Kitagawa) hand aspirated pump was used to

draw known volumes of sample through the detector tubes. Hydrogen-sulfide
detector-tubes (Kitagawa type 120SA) with a measuring range from 100-2000 ppm
were utilized. The scale on the detector tube is calibrated for 20C and atmospheric
pressure. The manufacturer provides a temperature correction table and pressure
correction equation for measurements at non-standard conditions. H2S gas detector
tubes also exhibit cross-sensitivity interferences similar to those described for the
electrochemical sensor.
67
3.3.3. Gas Chromatography
The Mass Spectrometry Facility, Department of Chemistry and Chemical
Biology, at Cornell University performed gas chromatography/mass spectrometry
analysis on one sample of raw digester gas. The sample was delivered in a 0.3 liter
Tedlar gas sampling bag with a rubber septum valve (Cole-Parmer).
3.4. TEMPERATURE MEASUREMENT

Gas temperatures before and after each column, bed temperatures, and ambient
air temperatures were monitored with thermocouples and a computerized data
acquisition system. The hardware and software systems used are modified versions of
those described by Hall (1998).
Data acquisition hardware components from Computer Boards, Inc., were
utilized. Type-T (copper-constantan) thermocouples with welded and silicone coated
ends were inserted into the center of the reactor cylinders at locations previously
displayed Figures 3.1-3.3. Thermocouple wires were then connected to an EXP-32
thermocouple multiplexor board capable of handling 32 differential inputs and
equipped with onboard amplification and cold junction compensation. A CIO-DAS08, 12-bit analog-to-digital conversion board was installed in a Gateway PC with
Pentium I processor for multiplexor control and data acquisition.
A software program was written in Pascal 6.0, using the DOS 3.1 operating
system, to display and log desired temperatures. Temperatures are recorded into
temporary storage every 15 seconds for 15 minute periods. After each period, the
average, standard deviation, maximum, and minimum for each input channel are
stored into a computer data file and the cycle is repeated. Further documentation of the
software is provided in the program itself.
68
3.5. PRESSURE MEASUREMENT
Pressure measurements were made using Magnehelic analog pressure sensors
(Dwyer Instruments, Inc.) with 0-1 H2O, 0-2 H20, and 0-5 psi ranges. Pressure drop
across a bed section was easily measured by disconnecting the appropriate sample
lines entering the multi-position valve and connecting them across the pressure sensor,
as shown in Figure 3.4.
3.6. COMPOST CHARACTERIZATION

The compost tested in this study was taken from the finished compost pile
on-site at AA Dairy. This medium consists only of anaerobically-digested separatedsolids that have been composted, using an outdoor windrow system, for at least 60
days. Samples from three spots around the pile were mixed together in a 15-liter
plastic pail to create representative samples. Tests performed on compost after
exposure to biogas may be from a specific part of the test column or from a wellmixed sample of the entire contents, as stated in each method.
3.6.1. Moisture Content
Approximately 10 grams of sample were placed in aluminum weighing dishes,
and then into an 85C oven for 24 hours. Weights of the samples before and after
were compared to determine percent moisture content. Samples from the tested
columns were taken from the external surface of the column cores at 0.05 m, 0.15 m,
and 0.25 m along its length.
69
3.6.2. Void Fraction:
A modified version of the 5-gallon pail method, as described by Nicolai and
Janni (2001), was utilized to determine percent void fraction. The following
procedure was used to test the fresh compost:
1) A plastic pail was filled with 5 liters of water and a full line marked on
the inside of the pail. The water was then removed.
2) The pail was filled about 1/3 full with compost and dropped ten times from
a height of 15 cm onto the floor.
3) Compost was added to fill the pail 2/3 full. The pail was again dropped ten
times from 15 cm onto the floor.
4) Compost was added to the full line and dropped ten times again.
5) Compost was added to the full line once more.
6) Water was added to saturate the compost to the full line and the volume
of water was recorded.
The void fraction is calculated by dividing the volume of water added by the
original solids volume.
3.6.3. Bulk Density
Similarly, the density of 5-liters of fresh compost was determined by weighing
it in an unpacked form and packed form, as described above.
3.6.4. Particle Size Distribution
Distributions of particles were determined by passing them through a stack of
sieves arranged in decreasing mesh-size order and recording the weight retained on
70
each sieve. The mesh-sizes of each sieve were 9.52 mm, 2.36 mm, 1.168 mm, and 0.5
mm. The compost was placed in the largest sieve first and shaken for 2 minutes.
3.6.5. pH
The pH value for the compost was determined by mixing 20 ml of sample with
20 ml of distilled and deionized water in a 100 ml beaker and using a calibrated
Beckman 200 pH meter to determine the pH of the solution. As with moisture
analysis, samples from the biogas-exposed compost were taken from the external
surface of the column cores at 0.05 m, 0.15 m, and 0.25 m along the length.
3.6.6. Trace Element Analysis
The Cornell Nutrient Analysis Laboratory (CNAL) performed trace element
analyses by total microwave digestion on 1-liter media samples. For analysis of
biogas-exposed compost, representative mixtures of the entire column contents were
submitted.
3.6.7. Sulfate Content
Samples of fresh compost were tested for sulfate concentrations by ProDairy
(Syracuse, NY).
3.7. OPERATIONAL PROCEDURES

Columns were packed with compost according to steps 2-5 in the void
fraction measurement protocol. Each section of bed was filled to 30.5 cm (12
inches), creating bed volumes of 2.47 liters for the small columns and 6.24 liters for
each section of the larger columns, or 18.71 liters for the entire large columns.
71
In all of the trials, a 2:1 mixture of biogas-to-air was used as the test gas for the
columns. This formulation, similar to that tested in peat biofilters by Degorce-Dumas,
et al. (1997), was chosen for two major reasons: 1) To ensure an aerobic environment
to facilitate microbial oxidation with thiobacillus, pseudomonas, or other species that
may exist in composts, and 2) To maintain safe operation outside of the explosion
limits for methane (5-15% in air) and hydrogen sulfide (4-45% in air).
Six different trials were run in these experiments, as described in Table 3.2.
Trial
1
2
3
4
5
6
Table 3.2: Summary of Experimental Trial Conditions

Bed
Total
Empty Bed Linear
Biogas
Air
Leachate
Volume
Flow
Flow
Flow
Residence Velocity
Recycle
(lpm)
(l)
(lpm)
(lpm)
Time (sec) (m/min)
18.7
11.2
7.5
3.7
98
0.55
No
18.7
11.2
7.5
3.7
98
0.55
No
2.45
1.5
1.0
0.5
98
0.19
No
2.45
1.5
1.0
0.5
98
0.19
No
2.45
1.5
1.0
0.5
98
0.19
Yes
2.45
1.5
1.0
0.5
98
0.19
Yes
These flow rates and empty-bed residence times were picked to maintain H2S
contaminant loading between 50 150 g/m3-solids/hr with expected H2S inlet
concentrations varying from 1000 3000 ppm.
In order to test the dilution method and column apparatus, a smaller column
without packing was run with 2:1 biogas-to-air mixture at 1.5 liters per minute for
three hours. Inlet and outlet H2S concentrations were compared using the
electrochemical sensor method previously described.
CHAPTER
4. RESULTS AND DISCUSSION
4.1. ORIGINAL COMPOST CHARACTERISTICS

The finished manure compost was dark brown in color and moist, but not
dripping, when squeezed by hand. The particles of fresh compost crumbled apart like
wet soil when touched. The odor characteristics changed from pungent and offensive
as fresh manure to earthy and soil-like as finished compost.
Figure 4.1: AA-Dairy Field of Dreams Cow-Manure Compost

Table 4.1 summarizes the results from characterization of the manure compost
as used in the columns.
72
73
Table 4.1: Cow-Manure Compost Characterization
Specification
Value Std. Dev.
Water Content (Loss on drying, wt%)
72.9%
0.9%
0.35
0.05
Void Fraction
Density (g/L)
Unpacked
604
13
Packed
757
18
Particle Size Distribution (wt % retained on sieves)
Sieve
Sieve Size (mm)
3/8 in.
9.52
16%
#7
2.8
62%
#8
2.36
9%
#14
1.168
10%
#35
0.5
3%
pH (in solution)
7.19
0.04
Trace Element Analysis (g/g dry basis)
Sulfur
7,316
Aluminum
2,145
Arsenic
< det.
Boron
67
Cadmium
< det.
Calcium
49,910
Chromium
2
Cobalt
2
Copper
479
Iron
5,487
Lead
< det.
Magnesium
13,615
Manganese
500
Molybdenum
11
Nickel
39
Phosphorous
11,869
Potassium
13,548
Sodium
3,277
Vanadium
7
Zinc
347
Note: <det = below analyte detection limit
Std. Deviations below 1% of reading for all values.
Sulfur Analysis (g/g dry basis)
Sulfate
73
=
Sulfide as S2
579
74
4.2. OPERATIONAL SUMMARY
Trials 1 and 2, using the larger columns, were run for 16 hours during June 1012, 2002. Trials 3 and 4, utilizing the smaller columns with no leachate recycle, were
operated for 1,057 continuous hours from July 5 through August 19, 2002. Trials5
and 6, using the smaller columns with leachate recycle, were also started July 5, 2002,
and run for 50.5 and 216.5 hours, respectively.
Due to safety concerns during trials 1 and 2, the 370-W pump was not operated
while unattended. The high output of the pump could create an asphyxiating or
explosive air safety problem in the event of a leak. During operation, moisture would
accumulate in the pumps inlet oil-filter bowl and have to be emptied every 4 hours.
Moisture also quickly appeared in all of the variable-area flow meters, causing
oscillation of flow. The flow meters were left at their original setting during this
oscillation. Despite attempts to seal large reactor joints with silicone sealant, gas and
liquid leaks were noticed at various times during operation. Because of this
observation, no data is reported for trials 1 and 2.
Trials 3-6 were started simultaneously using the 370-W vacuum pump, but, in
order to allow unattended operation, it was replaced with the smaller Neptune DynaPump after 10 hours of operation. Results from trials 3 and 4 are the major focus of
the following discussion because prolonged and consistent operation was logged.
Additionally, only compost from trials 3 and 4 were analyzed for chemical
composition after the trials. Trials 5 and 6, which included leachate recycle, were both
terminated prematurely due to increasing pressure drop in the bed and the inability to
provide sufficient flow to all columns with the smaller pump.
Moisture also condensed in the variable-area flow meters within the first hour
of trials 3-6. Flow rates were double-checked daily by temporarily inserting a clean,
75
dry, flow meter into the sample line. A small and unmeasured amount of liquid was
periodically lost during manual removal of sample lines to attach pressure sensors or
flow meters. The moisture was in the form of water vapor expelled due to the sudden
drop in column pressure to atmospheric, and estimated to be a less than a milliliter per
day per column.
The humidification flasks had to be replenished with 500 ml of water only
once after 700 hours of operation. Condensation was also evident in the clear PVC
lines to and from the columns.
4.3. PRESSURE MEASUREMENTS

For both columns 3 and 4, the pressure drop measured across the bed was
consistently 0.1 inches of H2O, the smallest graduation on the analog pressure scale.
Maximum pressure drops of 0.25 inches of H2O were recorded during the first few
hours only. Column 5, which included leachate recycle, displayed an increase in
pressure drop across the bed from 0.1 to 2.0 inches of H2O during operation.
Similarly, column 6 also displayed an increase in pressure loss from 0.1 to 3.0 inches
of H2O during the first 50 hours of operation. The pressure difference then receded to
around 1.0 inch of H2O for the rest of the trial. Pressure drops across beds are
depicted in Figure 4.2.
76
Pressure Drop Across Bed - Trials 3-6

3.5
3
Column 3 - No leachate Recycle
Pressure (in. H2O)
2.5
Column 4 - No leachate Recycle

Column 5 - Leachate Recycle
Column 6 - Leachate Recycle
1.5
1
0.5
0
0
200
400
600
800
1000
Run Time (total hrs)
Figure 4.2: Pressure Drop Across Bed for Trials 3-6
The decreases in observed pressure drops are most likely due to the
development of preferential flow patterns within the bed. The pressure range of 0.1-3
inches H20/ft for a 0.2 m/mim linear gas velocity corresponds with published compost
pressure drop data (Yang 1992); Nicolai and Janni 2001).
The following physical factors determine pressure drop across the filter bed:
1) Particle size distribution
2) Porosity
3) Particle shape and orientation
4) Gas viscosity and density
5) Superficial gas velocity
6) Height of the bed
77
Many empirical models have been developed to predict pressure drop through
a stationary bed of particles. The most well know models include the Ergun, Hukill,
and Shedd relations (McGuckin, et al. 1999). The Ergun equation, Equation 4.1
below, can be used to calculate expected pressure drop, including associated values.
P 150 (1 ) v0 1.75(1 )v 02
=
+
L
3 (D p )
3 (D p )2
2
Where
(4.1)
P
= Pressure drop per unit length
L
= Gas viscosity 1240x10-7 Poise @ 20C
= Porosity 0.35
v 0 = Superficial gas velocity 0.19 m/min
Dp = Characteristic dimension of particle 2.5 mm
= Particle sphericity 0.7 for activated carbon
= Gas density 1.16 kg/m3 @ 20C
With these parameters, the calculated pressure drop for compost is 19.4 Pa/m,
or 0.078 inches of H20/m. This is lower than pressure drops measured experimentally.
Using a characteristic dimension (Dp) of 1.0 mm for particle size resulted in a
calculated pressure drop of 0.15 inches H20/ft, which is in closer agreement with the
measured data. The relatively low gas velocities used here resulted in minimal
pressure drops and did not require the use of bulking agents, as might be necessary in
larger reactors or those with decreased gas residence times.
4.4. TEMPERATURE MEASUREMENTS

The temperature measurement system logged data every 15 minutes when
operating properly. Unfortunately, interruptions to the power supply caused data loss
on multiple occasions and prevented any data collection after hour 431. The
temperature data collected for each column are in Figures 4.3-4.6.
78
Temperature - Column 3
45
Temp. (C) (15 minute average)
40
35
30
25
20
15
Inlet Gas
Media
Outlet Gas
Ambient
10
0
50
100
150
200
250
300
350
400
450
Run Time (hrs)
Figure 4.3: Temperatures (15-Minute Average) for Column 3

45
Temp (C) (15 minute average)
40
35
30
25
20
Inlet Gas
Media
15
Outlet Gas
Ambient
10
0
50
100
150
200
250
300
350
400
Run Time (hrs)
450
79
45
40
35
30
25
20
Inlet
Media
Outlet
Ambient
15
0
10
15
20
25
30
35
40
45
50
Run Time (hrs)

40
35
30
25
20
Inlet
Media
Outlet
Ambient
15
0
20
40
60
80
100
120
140
160
180
Run Time (hrs)
200
80
The cyclical variation is due to diurnal temperature fluctuation. The ambient
temperature was recorded inside of the engine room and is different than actual
outdoor temperatures. Outdoor temperature, as well as the digester temperature,
influences the inlet-gas temperature, which is why it is possible to observe an inlet-gas
temperature lower than ambient temperature. In all trials, it is observed that the bed
temperature is typically between 0-12C higher than the inlet temperatures, as shown
in Figure 4.7. This is an indication of heat being generated in the bed, which may be
attributed to an exothermic biological, chemical, or physical adsorption reaction, and
could potentially be used to track bed activity or viability.
Difference Between Bed Temperature and Inlet-Gas Temperature For

Trials 3-6
14
Temp. Diff. (Bed-Inlet) [C] .
12
Column 5
Column 6
Column 3
Column 4
10
8
6
4
2
0
0
5000
10000
15000
20000
25000
-2
-4
Time (minutes)
Figure 4.7: Temperature Difference Between Bed and Inlet-gas for Columns 3-6
81
Table 4.2 below summarizes the maximum and minimum temperatures seen in
each trial.
Table 4.2: Summary of Temperature Extremes for Trials 3-6
Trial
Ambient Temperature
Inlet Temperature
Bed Temperature
#
Max(C)
Min(C) Max(C) Min(C) Max(C)
Min(C)
16.7
36.5
13.9
37.8
20.6
42.0
Column 3
16.7
36.5
15.4
38.9
21.5
43.3
Column 4
22.5
33.6
21.4
35.0
24.7
41.9
Column 5
16.7
33.6
14.8
34.5
19.1
39.5
Column 6
Literature indicates that the optimum range for biological H2S oxidation is in
the range of 30 40C. In general, severe reduction in activity occurs below 10C and
more moderate reduction of activity above 50C (Yang 1992). Therefore, these
experiments were operated in the mid-to-high range of known optimum temperature
conditions.
A simplified heat balance can be written to estimate the heat generation in the
bed. Heat accumulation within a packed bed can be written as the sum of the
individual conductive, convective, evaporative and metabolic heat contributions.
Radiation losses are neglected and the media is assumed to maintain its uniform
structure. The overall relation is described by Equation 4.2.
Qaccumulation = Qconduction + Qconvection + Qevaporation - Qgeneration
(4.2)
Considering only maximal gradients, unsteady-state heat accumulation can be

written as Equation 4.3 (Gutierrez-Rojas, et al. 1996).
dTbed
= UA p (Tamb Tbed ) + G ' ( in hin out hout ) +
dt
GAo Qw ( y in y out ) Q gen
C p
(4.3)
82
Where: b = Bulk comp0st density, packed 750 g L-1

Cp = Medium heat capacity
U = Overall heat transfer coefficient
Ap = Specific heat transfer area parallel to gas flow
104 m2 m-3media
Tamb = Ambient Temperature of air 30C
Tbed = Bed Temperature 33C
G = Specific gas flow rate 0.01 m3gas m-3bed s-1
in = Inlet gas density 1.09 kg m-3 @ 30C
out = Outlet gas density 1.08 kg m-3 @ 33C
hin = Inlet gas enthalpy (@ Tin = 30C) 744,080 J kg-1
hout = Outlet gas enthalpy (@ Tout = 33C) 744,302 J kg-1
G = Gas mass velocity 0.0023 kg m-2 s-1
A0 = Specific heat transfer perpendicular to gas flow
Ap 104 m2 m-3media
Qw = Latent heat of vaporization 2430 kJ kg-1 @ 30C
yin = Water mass fraction of inlet gas 0.028 kgwater kg-1gas
yout = Water mass fraction of outlet gas 0.028 kgwater kg-1gas
Qgen = Heat generation from reaction in the bed
t = Time, seconds
Assuming heat accumulation is zero at steady state, and representative steadystate temperatures (Tamb and Tbed) are grossly estimated from the temperature data for
column 6 (hour 50), many of the physical parameters can be determined. The overall
heat transfer coefficient (U) can be calculated with Equation 4.4 and stated values.
U =
1
2.29 J m - 2 s -1 K -1
1 1
+ +
hi ho k
(4.4)
Where hi = Inside film coefficient

ho = Outside film coefficient
= Reactor wall thickness 0.00635 m
k = Reactor wall thermal conductivity 0.17 J m-1 s-1 K-1
The inside film coefficient (hi) for packed bed columns with laminar
airflow (Re<2000) was calculated with Equation 4.5-4.6 (Perry, et al. 1997)
83
g DpG
hi = 3.6
D p g
0.365
42.65 J m -2 s -1 K -1
(4.5)
Where g = Gas thermal conductivity 0.027 J m-1 s-1 K-1 @ 30C

g = Gas viscosity 1275x10-7 Poise @ 30C
= Porosity 0.35
G = Gas mass velocity 0.0023 kg m-2 s-1
Dp = Characteristic dimension of particle 2.5 mm
Re =
Dr G
g 1.8
(4.6)
Where Re = Reynolds number, dimensionless

Dr = Reactor diameter 0.1 m
The outside film coefficient (ho) for a vertical cylinder exposed to natural
convection is determined with Equations 4.7-4.9 (Perry, et al. 1997).
ho =
1
4
0.59kair
(Gr Pr ) 2.66 J m- 2 s-1 K -1
L
(4.7)
Where kair = Thermal conductivity of air 0.26 J m-1 s-1 K-1

L = Length of heat transfer surface = 0.3 m
Gr =
2
L3 air
gT
2
air
1.02x107
(4.8)
Where Gr = Grashoff number, dimensionless

air = Ambient air density 1.16 kg m-3 @ 30C
g = Acceleration due to gravity 9.81 m s-2
= Volumetric coefficient of Thermal Expansion
= Tamb-1 0.0033 K-1
T = Temperature difference 33C 30C = 3C
air = Viscosity of ambient air 1860x10-7 Poise @ 30C
Pr =
C pair air
k air
0.72
(4.9)
Where Pr = Pandtl number, dimensionless

Cpair = Heat capacity of air 1.007 J g-1 K-1
Plugging these calculated and assumed values into Equation 4.3, the heat
generated by reaction can be estimated as:
84
Qgen =7.68x104 J s-1 m3bed
Equation 2.27, in chapter 2, gives the theoretical maximum energy produced

from stoichiometric oxidation of H2S. Assuming that all of this energy is given off to
the bed (which is clearly an over-assumption, as 60% of energy is typically utilized by
the cell for growth and maintenance), it is estimated that a maximum of 4.85x102 J s-1
m3bed may be generated solely from oxidation of 1500 ppm H2S to sulfate. This is
much lower than the calculated heat generation value and indicates that there are likely
additional or different exothermic reactions occurring. This is expected since compost
and other organic compounds in the gas are known to degrade in aerobic
environments. Assuming a worst-case scenario where all of this heat is derived from
the oxidation of methane (Hrxn = -8.9x105 J/mol CH4), 47% of the methane would be
consumed. This calculation indicates that there is the potential for significant methane
reduction, but further testing is needed to determine the fate of CH4 as methane was
not monitored and no temperature controls were practiced in this experiment.
4.5. HYDROGEN SULFIDE MEASUREMENTS

4.5.1. Electrochemical Sensor
To quantify the error attributed to the electrochemical sensor and dilution

method, linear error propagation can be done. Summing the variances from the sensor
reading and the flow-meter readings for air and gas entering the dilution chamber, the
cumulative standard deviation, neglecting any cross sensitivity interference, given by
Equation 4.10.
2S
= 1600 + (2.42 104 )(Sensor Reading) 2 40 [ppm]
(4.10)
85
Interference would likely raise this error, but the actual amount is difficult to
calculate without knowing all biogas components.
Results from testing the column without packing showed that the inlet and
outlet concentrations remained equal, indicating no apparent interference from the
column materials.
Columns 3 and 4 operated continuously for 1057 hours with an average inlet
H2S concentration around 1500 ppm. Removal efficiency is calculated by dividing the
difference between the inlet and outlet concentrations by the inlet concentration (in
ppm). Similarly, linear error analysis including only instrument variances indicates
that standard deviation for removal efficiency is less than 1.41%. The concentrations
and removal efficiencies for columns 3 and 4 (with associated error bars) are given
with Figures 4.8-4.11.
H2S Concentrations - Column 3
2500
H2S in
H2S (ppm)
2000
H2S out
1500
1000
500
0
0
200
400
600
800

Figure 4.8: H2S Concentrations for Trial 3
(lines are polynomial fits meant only to guide the eye)
1000
86
Removal Eff. (%)
Removal Efficiency - Column 3
100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
0
200
400
600
800
1000

Figure 4.9: H2S Removal Efficiency During Trial 3
(line is polynomial fit meant only to guide the eye)
H2S Concentrations - Column 4

2500
H2S in
H2S (ppm)
2000
H2S out
1500
1000
500
0
0
200
400
600
800

Figure 4.10: H2S Concentrations for Trial 4
1000
87
Removal Efficiency - Column 4
Removal Eff. (%)
100%
80%
60%
40%
20%
0%
0
200
400
600
800
1000

Figure 4.11: H2S Removal Efficiency During Trial 4
(line is polynomial fit meant only to guide the eye)
Column 3 operated consistently above 80% removal efficiency until the last
150 hours when efficiencies declined to 50%. Column 4 started off with high removal
efficiency for the first 250 hours but then dipped to around 50% efficiency by 500
hours. Expecting to see a continued reduction, column 4 was allowed to continue
running but displayed a temporary rebound in removal efficiency to 80% by hour 900.
Similarly to column 3, a drop in efficiency occurred for the last 150 hours of operation
and both columns were shut down for media inspection when the removal efficiency
of both columns dropped below 50%.
The elimination capacity of columns 3 and 4 ranged from 24 112 and 16
118 g H2S/m3-solids/hr, respectively, as calculated assuming atmospheric pressure and
25C. The total mass of H2S removed from the gas during these experiments are 135
and 127 g H2S, respectively for columns 3 and 4. An average flowrate and
concentration per sampling interval were used for calculation. This elimination
88
capacity approaches the maximum of 130 g H2S/m3-solids/hr reported for organic
media (Yang and Allen 1994; Degorce-Dumas, et al. 1997).
It is not clear why one column behaved differently than the other under similar
conditions. One possible explanation could assume inherent variability due to
biological systems. The fact that a rebound in removal efficiency occurred in column
4 may support the idea of biological system upset and recovery. A purely chemical
breakthrough would not be expected to behave in this manner.
The dip in efficiency in column 4 around hour 500 is also accompanied by a
lesser dip in efficiency in column 3. The exact reason for these reductions are not
known, but maximum bed-temperatures during this time exceeded 40C, which may
have disrupted a biological or physical adsorption mechanism. Temporarily
insufficient moisture availability may also be a possible explanation.
It appears that the simultaneous decline in removal efficiencies of both
columns after hour 900 occurs in conjunction with a measured increase in inlet gas
H2S concentration. At hour 900, a minimum inlet H2S concentration of 480 ppm was
recorded, followed by an increase to over 2000 ppm in 6 days. This quick increase in
loading may also have had the effect of upsetting the system and leading to decreased
removal efficiency. It is also possible that the chemical or physical reaction
mechanism was becoming exhausted at this point.
The inlet and outlet H2S concentrations and removal efficiencies for columns 5
and 6 (with associated error bars) are represented in Figures 4.12-4.13. Removal
efficiencies were above 90% and 87% for columns 5 and 6, respectively, throughout
their operation.
89
H2S Concentrations and Removal Efficiency - Column 5

100%
2500
H2S in
H2S out
Removal Eff
1500
80%
Removal Eff. (%)
H2S (ppm)
2000
60%
1000
40%
500
20%
0%
0
0
10
20
30
40
50

Figure 4.12:H2S Concentrations and Removal Efficiency for Column 5
3000
100%
2500
80%
H2S in
H2S out
Removal Eff.
2000
1500
60%
40%
1000
20%
500
0%
0
0
50
100
150
200
Figure 4.13:H2S Concentrations and Removal Efficiency for Column 6

Removal Eff. (%)
H2S (ppm)
H2S Concentrations ad Removal Efficiency - Column 6
90
4.5.2. Gas Detector Tubes
Gas samples from AA Diary were sporadically tested for H2S using leadacetate H2S detector tubes since November 2000. Table 4.3 shows H2S readings in the
gas prior to the experiments, and more frequently during the experiments (July-Aug.).
Table 4.3: H2S Gas Detector Tube Readings for AA Dairy Raw Digester Gas
November 13, 2000
3600
March 4, 2001
2200
July 1, 2001
3400
July 13, 2002
1400 (660)
July 15, 2002
1400 (1380)
July 20, 2002
1300 (1680)
July 27, 2002
1150 (1440)
August 5, 2002
1200 (1280)
August 19, 2002
1700 (1900)
August 22, 2002
1900
Note: Numbers in (parentheses) are H2S levels determined by the electrochemical
sensor on a 2:1 biogas:air sample. Provided for comparison.
Levels as high as 3600 ppm have been measured. H2S levels in the digester
gas during the experiment appear significantly lower than in the past. This difference
may be due to seasonal variation, variability in the feedstock, chemical differences in
the digester, or sampling error.
The readings from the gas detector tubes are consistently lower that expected
when compared with the electrochemical sensor method. One would expect the
electrochemical sensor method to produce a reading value 2/3 lower than the detector
tube, because the gas sample measured by the electrochemical sensor is diluted with
air, and the H2S detector tubes are always used to measure raw biogas. The low
readings might be attributed to normal error within the reported +/- 25% for the gas
detector tubes, or additionally from an incomplete seal from the sampling port to the
tube itself, allowing for gas to bypass the tube, resulting in a lower reading.
91
4.5.3. Gas Chromatography
A calibration standard gas was not tested with the biogas sample so
quantitative levels of each gas component are not accessible. Rather, a qualitative
assessment of the major gas components in biogas was completed, as follows.
By taking the relative contributions of the peak readings, rough estimates of
gas composition can be determined, as presented in Table 4.4.
Table 4.4: GC-MS Results for AA Dairy Digester Gas
Component
Peak Height
% Total
% Dry Basis
8
Total
1.80*10
--56.24%
62.49%
Methane
1.01*108
33.33%
37.04%
Carbon dioxide
6.00*107
5
0.33%
0.36%
Hydrogen sulfide
5.90*10
1.75*105
0.10%
0.11%
NH3 and CH4 isotopes
2
<0.01%
<0.01%
Dimethyl Sulfide
6.60*10
10.00%
-Water
1.80*107
As seen here, the relative moisture content of the gas in this sample is about
10%. On a dry-basis, the methane and carbon dioxide concentrations are about what
was expected, ~60% and ~40%, respectively. The H2S content is also in the range of
a few tenths of a percent, which is in agreement with the other testing methods used
here. Other compounds were not identified due to the absence of specific calibration
gases for testing these compounds.
Figure 4.14 depicts the actual GC-MS results for the digester gas. Each graph
is for a specific mass element. Results for H2S, CO2, total gas, and water are
represented from top to bottom, respectively. Similar results for dimethyl sulfide and
ammonia are not shown here. Each graph is scaled to 100% of the signal intensity,
and the peak height value is given with the scales to the right.
H2 S
CO2
Total
H2 O
Figure 4.14: GC-MS Results for AA Dairy Digester Gas.
93
4.6. BIOGAS-EXPOSED-COMPOST ASSESSMENT

Columns 3 and 4 were opened 7 days after shutdown for compost inspection.
The solids slid out of the columns easily and appeared dry and whitish-yellow in color
as seen in Figure 4.15. No testing was done to determine if this coloration had any
correlation to sulfur content. The smell of rotten eggs was evident during opening.
Figure 4.15: Pictures of Columns after Exposure to Biogas for 1057 hours.
4.6.1. Moisture
The outer layers of the columns were crumbly to the touch and showed definite
signs of drying. Both compost volumes were sliced lengthwise for examination. In
94
both instances, the cores of the columns were darker brown in color, moist to the
touch, and appeared similar to the original compost.
Moisture measurements from 0.05, 0.15, and 0.25 m along the column lengths
are shown in the Table 4.5.
Table 4.5: Moisture Contents Along Bed Depth
Sample / Location Bottom Middle
Top
73%
73%
73%
Fresh Compost
44%
63%
76%
Column 3
41%
69%
60%
Column 4
As seen, there is moisture loss near the inlet, down from an original content of
~70%. As expected with a temperature rise in the bed, humidification of the inlet gas
was not sufficient for maintaining moisture in the compost. Also, the evidence of
localized drying indicates preferential gas flow around the edges of the column.
Water content is an indirect measurement of water availability, whereas water
activity measurements are more useful, but difficult to obtain. Sufficient water
availability is critical for proper biological function and may have the greatest
detrimental effect on biofilter performance if inadequate (Mysliwiec, et al. 2001).
Studies by Yang and Allen (1994) indicate that removal efficiency drops linearly
below 30% wet weight water content in H2S biofilters. Although no water content this
low was measured, it is reasonable to assume that better performance could be
achieved with more uniform and increased wetting. Additionally, an improved water
management technique is desirable because organic media are known to become
hydrophobic when dried, making them hard to rewet and maintain acceptable water
potentials (Bohn and Bohn 1999).
95
4.6.2. pH
As with the moisture content, pH samples from 0.05, 0.15 and 0.25 m along
the column lengths were recorded and Table 4.6 shows these results.
Table 4.6: pH Levels Along Bed Depth
Sample / Location
Bottom Middle
Top
7.2
7.2
7.2
Fresh Compost
6.9
4.9
4.6
Column 3
6.7
7.1
4.6
Column 4
The most significant pH drops are noticed in the upper half of the beds. The
largest pH decreases are noticed where moisture contents remained higher. A drop in
pH is an indication of possible sulfate formation in the bed, which is a major
biological pathway for sulfide oxidation. One possible explanation for this might be
that biological activity, and thus sulfate formation, was curtailed by low moisture
content.
An extreme pH drop, as seen with some H2S biofilters (Devinny, et al. 1999),
was not noticed here. This may be due to the incomplete oxidation to elemental sulfur
or natural buffering capacity of the compost. Additional buffering to maintain a
neutral pH was not practiced, but could easily be achieved via crushed limetone
addition in the bed.
4.6.3. Trace Element Analysis
The results for the trace element analysis are shown in the Table 4.7.
96
Table 4.7: Elemental Analysis of Raw and Tested Compost
Element
Compost*
Sample 3*
Sample 4*
Sulfur
7,316
103,752
121,490
Aluminum
2,145
774
849
Arsenic
< det.
< det.
< det.
Boron
67
43
47
Cadmium
< det.
< det.
< det.
Calcium
49,910
28,884
35,858
Chromium
2
< det.
0.1
Cobalt
2
< det.
< det.
Copper
479
332
359
Iron
5,487
2,160
2,481
Lead
< det.
< det.
< det.
Magnesium
13,615
8,892
11,934
Manganese
500
320
353
Molybdenum
11
15
21
Nickel
39
25
28
Phosphorous
11,869
7,261
8,068
Potassium
13,548
9,412
10,020
Sodium
3,277
2,356
2,528
Vanadium
7
3
3
Zinc
347
236
256
* all values in ug/g dry basis
< det. = below analyte detection limit
As seen, the original total sulfur content of the compost is about 7000 g/g
(0.7%) on a dry basis. Columns 3 and 4 average around 110,000 g/g for total sulfur
content. This indicates a net increase of about 100,000 g/g of total sulfur in the
media itself during operation, and final sulfur content over 10% dry basis. These
results are encouraging because they confirm that sulfur is being removed from the gas
stream and being sequestered in the bed through biological, chemical or physical
mechanisms.
Besides an average 1440% increase in sulfur, molybdenum is the only other
element with a measured increase (66% average). All the remaining measured
97
elements decreased by less than 100% on a dry basis. Some metal leaching is
expected to occur in acidic biological environments, but was not measured here.
Yang and Allen (1994) have shown that sulfate levels above 30 mg/g inhibit
H2S biofilter performance. The original level in the compost (<100 g/g) was well
below this threshold. Sulfate levels in the used composts were not measured.
An accurate sulfur balance is hard to accomplish because the final dry mass of
the columns and sulfur levels in leachate were not measured. The amount of sulfur
removed from the gas stream using the electrochemical measurement method is
calculated as 127 15 g for column 3, and 120 15 g for column 4. Assuming that
the dry mass of the columns stayed the same throughout operation, the trace element
analysis would predict an expected removal of 175 and 207 g S for columns 3 and 4,
respectively. The discrepancy may be due to a decrease in total dry matter during
operation, or significant loss of sulfur in the leachate. Also, the detected smell of H2S
during column opening might be an indication of sulfur reduction occurring and regeneration of H2S while the columns were no longer exposed to an oxygen source.
4.7. DISCUSSION
These results indicate that a simple and minimally managed system, comprised
of passing a mixture of 2:1 biogas-to-air through cow-manure compost, can be
effective in removing sulfur from a biogas stream. Although using an electrochemical
sensor is affordable and good for tracking relative changes in concentration, it is
limited in measuring absolute concentrations because of cross-sensitivity interference
and dilution error. H2S gas detector tubes and a GC-MS analysis corroborate the
readings from the electrochemical sensor.
98
It is not clear from this study whether sulfur removal is due mostly to
biological, chemical, or physical phenomena, but sulfur is clearly being removed from
the gas stream and accumulated in the compost. The upset and recovery trend in
removal efficiency for column 4, noticeable pH drops, prolonged performance, and
relatively high elimination capacities are suggestive of a biological mechanism.
The fact that significant removal rates were achieved with minimal moisture
control and no temperature or pH controls indicate that further research on system
capacity and optimization are warranted. Initial progress is predicted simply by
maintaining temperature between 30-40C and moisture contents above 50%. Other
researchers have achieved biological H2S removal with residence times as low as 1.6
seconds, indicating that higher elimination capacities may be possible with lower gas
residence times (Gabriel, et al. 2002). Major questions to be answered include: What
happens to methane during this process? What is the upper elimination capacity? What
sulfur products are formed? How does the compost change during the process? What
is the microbial makeup? And what are the optimum operating conditions?
4.8. SCALE-UP CONSIDERATIONS

These experiments were conducted on biogas side-streams containing roughly
1/1000 of the full-scale gas flow. 2.5-liter reaction columns with 100-second emptybed residence times for 2:1 biogas-to-air mixtures produced the aforementioned
results. Assuming linear scale-up for discussion, a 2500 L, or 2.5 m3, bed volume
might produce similar results. Although linear scaling would most likely not apply,
there are many reasons to believe that performance can be improved by optimizing
temperature, moisture, loading, and pH conditions.
99
Additionally, in these experiments, excess oxygen (in air) was added, but the
critical amount of air required may be substantially less. Reduced oxygenation levels
and empty-bed residence times, as determined with further testing, would decrease bed
size, as long as the maximum H2S elimination capacity was not exceeded.
Unfortunately, lower gas-residence times may require bulking of the compost to keep
pressure drops reasonable, and bed sizes would then need to be increased.
In scaling-up, there are two potential process-configurations that can be
envisioned with cow-manure compost. Ideally, a biological process with a stable
microbial environment would be established to promote continuous and prolonged
H2S removal. In this scenario, required nutrients are available in the compost or gas,
or added periodically, and sulfates and other metabolites are removed, when
necessary, with a water-rinse. Labor and media costs are lower because bed changeouts would only be necessary less than once a year. A second configuration is
envisioned where the cow-manure compost is placed in a vessel with relatively few
process controls, operated until the bed is completely ineffective, and replaced with
fresh compost as a batch process. The loss in efficacy may be from exhaustion of
chemical or physical adsorption capacity, loss of biological activity from insufficient
nutrients, or because of increased pressure drop from compost degradation or plugging
of the void spaces with sulfur or biomass.
A comparison of these compost-based processes with an iron sponge system,
sized for AA Dairy, is included in Table 4.8. Media costs for the compost are based
on the average market value of $0.02/kg for AA Dairy cow-manure compost.
Transportation costs are zero for the compost, whereas the iron sponge has a
transportation cost for shipping from Chicago, IL. As seen, both manure processes
show potential for improvement over iron sponge. The Equivalent Uniform Annual
Cost (EUAC) is calculated assuming a $30,000 capital cost for all systems, 20-year
100
system life cycle, and 8% interest rate and including all other annual costs (Newnan
2000). The iron sponge system has an EUAC from $4,437 - $15,057 per year or $5.35
- $6.43 per kg H2S removed. The cow-manure systems have estimated EUACs of
$6,527 and $3,832 per year, respectively, or $6.30 and $3.70 per kg H2S removed.
There is a range of costs for the iron sponge system due to variations from low (1000
ppm H2S) to high (4000 ppm H2S) loading. Since only one concentration level (1500
ppm H2S average) was tested here, it is not clear how the cow-manure compost
systems would respond, and subsequently how costs would vary, based on different
loadings. Therefore, the symbol is used to remind the reader of this variability in
Table 4.8. As indicated here and in the table, the continuous cow-manure system
appears to provide the most significant improvement and savings over the iron sponge
system.
101
Table 4.8: Estimated Comparison of Cow-Manure-Compost and Iron-Sponge

H2S-Removal Systems at AA Dairy
Cow-Manure
Cow-Manure
Iron Sponge
(Batch)
(Continuous)
CHARACTERISTICS
2 (Lead/Lag)
2 (Lead/Lag)
2 (Series)
# Vessels
0.91 m ID x 1.77 m 0.91 m ID x1.77 m
high (1.15 m3 each) high (1.15 m3 ea.)
Vessel Sizes
0.91 m ID x 1.52 m
high (0.99 m3 each)
Biogas Flow Rate
0.94 m3/min
0.94 m3/min
0.94 m3/min
Air Addition Rate
2.4 3.7 %
< 33 %
< 33 %
Total Flow Rate

Empty-Bed
Residence Time
0.97 m /min
60 sec (1-bed)
120 sec (both beds)
1.41 m /min
49 sec (1-bed)
98 sec (both beds)
1.41 m3/min
49 sec (1-bed)
98 sec (both beds)
Mass of Bed
800 kg each
860 kg each
860 kg
18 - 315 days
40 days
> 1 year
930 16,300 kg
15,480 kg
< 1720 kg
Capital
$10,000-$50,000
$10,000-$50,000
$10,000-$50,000
Media (per year)

Transportation
(per year)
$250 - $4,300
$300
$35
$500 - $2,500
$500 - $3,000
(1-20 change-outs
@ 12 hrs. ea. +
blower electric)
$1,000
(9 change-outs @
8 hrs. ea. + blower
electric + H2O)
$500
(1 change-out @ 8
hrs. + blower
electric + H2O +
nutrients)
$130 - $2,200
$2,170
$240
$5.35-6.43
$6.30
$3.70
Bed Life
Annual Media
Utilization
COSTS
Operating and
Labor (per year)
Media Disposal
(per year)*
TOTALS
Total EUAC**
($/kg H2S
removed)
* Kellog (1996) estimated disposal costs of $0.14/kg-spent media. It is assumed here that disposal
costs for all three processes would be the same. Costs may be higher or lower depending on whether
the material is disposed of on-site or if it is transported to a landfill and treated as hazardous waste.
(See Appendix A).
** EUAC = Equivalent Uniform Annual Cost assuming $30,000 capital cost, 8% interest rate, and 20
year life-cycle.
CHAPTER
5. SUMMARY AND CONCLUSIONS
The two-part objective of this study was to determine currently available H2S
removal technologies suitable for use with farm biogas systems, and to test the
feasibility of utilizing on-farm cow-manure compost as an H2S adsorption medium.
There are many chemical, physical, and biological methods currently available for
removal of H2S from an energy gas stream, as summarized below.
5.1. CURRENTLY AVAILABLE H2S REMOVAL METHODS

5.1.1. Dry-Based Processes
Traditionally, dry-based chemical methods have been used for sulfur removal
from gas streams with less than 200 kg S/day, and still appear to be competitive
because they are simple and effective. Estimated capital costs for farm systems are
around $10,000-$50,000 and media costs estimated between $250-$23,840 per year.
Relatively high labor costs for materials handling and disposal are incurred. Major
drawbacks include a continually produced waste stream of spent media, and growing
environmental concern over appropriate waste disposal methods. The most
competitive products appear to be Iron sponge, Media-G2, and KOH-impregnated
activated carbon. Molecular sieves may be competitive with an appropriately
designed regeneration step. Table 5.1 summarizes dry-based, H2S removal processes
and Table 5.2 summarizes estimated costs for application at AA Dairy.
102
Table 5.1: Summary Table Comparing Dry-Based H2S Removal Processes for Farm Biogas
Compounds
Regen- Media Costs
Operating
Notes
Packing
($/kg H2S
Conditions
Removed
erable?
removed)
Iron Sponge
(Iron Oxide)
Sulfa Treat
(Iron Oxide)
Sulfur Rite
(Iron Oxide)
Media-G2
(Iron Oxide)
Molecular Sieve
(Adsorbent)
Ambient Temp. (65115 F), Wet gas, 60

sec residence time
sec residence time
sec residence time
sec residence time
H2S and
mercaptans
0.35 - 1.55
H2S and
mercaptans
No
4.85 - 5.00
H2S and
mercaptans
No
7.95 - 8.50
Available in prepackaged modules,

Forms iron pyrite
H2S and
mercaptans
15 times in
batch mode
only
2.90 - 3.00
Requires multiple regenerations to

obtain estimated removal efficiency
Ambient Temp., Water,mercaptans, H2S,

High Pressure (500
slight CO2
psig+)
Impregnated
Ambient Temp. and
Activated Carbon
Pressure
(Adsorbent)
Estimated CowAmbient Temp. and
Manure Compost
Pressure
Processes
Changeout can be labor intensive.

Variability in process efficiency but
much practical experience with
digester gas
Non-pyrophoric and easier handling
characteristics compared to iron
sponge
2-3 times in
batch mode
only
H2S and
mercaptans
H2S
Removes all water before sulfur

compounds. The proposed design
would have a 1-day bed life operated
at 500 psi
Yes
KOH carbon has been used

successfully for anaerobic digester gas
No
1.75 - 2.00
No
Continuous or batch processes are

envisioned (Table 4.8). It is not clear
0.03 0.29
whether other compounds are
oxidized in addition to H2S.
Packing
Table 5.2: Summary Table Comparing Dry-Based H2S Removal Processes for AA Dairy
AA DAIRY ESTIMATES (all costs do not include taxes, shipping, installation or operation)
Estimated
# of Vessels
Annual Media
Annual Media
Suppliers
Bed Life (days)
Capital
and Sizes
Consumption (kg)
Costs ($)
Cost
(D=diameter,
H=Height)
Low
loading
High
Loading
Low
loading
High
Loading
two - 0.91 m
930 3,710 Iron Sponge
D x 1.52 m H 72 - 315 18 - 79
4,070
16,300
(Iron Oxide)
each
two - 1.2 m
Sulfa Treat
x1.6 m x 1.8
345
86
3,850
15,450
(Iron Oxide)
m each
Sulfur Rite one 2.3 m

420
98
7,900
33,900
(Iron Oxide) D x 3.4 m H
two - 0.91 m
Media-G2
D x 1.52 m H
190
47
1,460
5,900
(Iron Oxide)
each
Molecular
one 0.6 m
24 hours 24 hours 250/day 400/day
Sieve
Dx2mH
(Adsorbent)
Impregnated
two 0.6 m
Activated
D x 1.5 m H
340
85
270
1075
Carbon
each
(Adsorbent)
Estimated one or two
Cow-Manure 0.91 m D x
40
360
1720
15480
Compost
1.77 m H
Processes
each
Low
loading
High
Loading
(Vessels
Only) ($)
(Low loading=1000ppm
High loading=4000 ppm)
250 1,075
9854,300
10,000 50,000
Connelly GPM,
Physichem, Varec
Vapor Control
3,400
13,500
12,000
SulfaTreat
5,560
23,840
43,600
US Filter/ Merichem
2,050
8,290
10,000 50,000
ADI International
n/a
n/a
n/a
Many - See
Thomasregister.com
1250
5435
<50,000
Many - See
Thomasregister.com
300
10,000 loading values are for

50,000 batch and continuous
Note: (low and high
35
process, respectively)
105
5.1.2. Liquid-Based Chemical and Physical Processes

These processes have not traditionally been used for low-flow and lowpressure applications due to increased costs of operating at high pressure, high energyrequirements for recirculation pumps and regeneration vessels, and higher media
costs. The LO-CAT iron-chelate process shows potential for being viable with small
biogas systems, especially if the thickened sulfur-slurry produced has agricultural
value. Also, nitrate solutions, such as Sulfa-Scrub, should be investigated for system
suitability. Water scrubbing and the Selexol Process are both used for upgrading of
biogas to natural gas but do not appear economically competitive for selective H2S
removal at this time.
5.1.3. Membrane Separation
Selective H2S removal from biogas is not yet practical with this technology,
but upgrading of biogas to natural gas is an emerging market for membrane processes.
Low-pressure gas-liquid membrane systems are in the developmental stage and show
promise for the future.
5.1.4. In-Situ Digester Sulfide Control
Research has shown that addition of iron compounds to the digester effectively
inhibits some H2S production, but this method may only be considered a partial
removal process, requiring another technology for removal down to about 10 ppm.
Also, there is concern about solids buildup in the digester using this method.
106
5.1.5. Biogas Aeration
Digestion facilities in Europe have reported significant H2S removal by adding
small amounts of air (2-6%) to the digester headspace or storage tank. This extremely
simple and affordable technique is believed to be biological in nature, and may reduce
initial H2S levels to around 100 ppm. This process requires further testing in the
United States as it shows great promise.
5.1.6. Biological Removal Techniques
Operational experience with biological oxidation of H2S from gas streams is
growing and there are companies, such as Biothane and UOP, who specialize in this
area. Currently available systems are more capital intensive than available dry-based
systems, but offer advantages of lower labor costs and improved environmental
impact. The research in the second part of this study examined the feasibility of using
cow-manure compost as an economic and effective H2S removal process for integrated
farm energy systems.
5.1.7. Comparison of Characteristics of H2S Removal Processes
Table 5.3 summarizes the characteristics of available H2S removal processes
from biogas.
107
Table 5.3: Summary of H2S Removal Process Characteristics
Removal
Technique
Iron Oxides
Zinc Oxides
Alkaline Solids
Impregnated
Activated
Carbons
Molecular Sieves
Chelated Iron
Solutions
Nitrite Solutions
Alkaline Salt
Solutions
Amine Solutions
Water Scrubbing
Physical Solvent
Scrubbing
Membrane: Low
Pressure
Membrane: High
Pressure
Digester pH
Control
Digester Iron
Addition
Dietary
Adjustment
Air Dosing to
Biogas
Commercial
Biological
Processes
Estimate CowManure Compost
Processes
Operating/
Applicability
Capital
for farm
Media
Costs
biogas
Costs
Ease of
operation
Regenerable
H2S < Environ250

mental
ppm
impact
(+=high)
(+=low)
(+=low)
(+=easy)
(+=yes)
(+=yes)
(+=low)
+
-
+
+
+
+/-
+/+/+/-
+/-
+
+
+
+/-
+/-
+/-
+/-
+/-
+/-
+/-
+/-
+/-
+/-
+/-
+/-
+
+
+
+/-
+/-
+/-
+/-
+/-
+/-
+/-
+/-
+/-
+/-
+/-
n/a
+/-
+/-
+/-
+/-
n/a
+/-
n/a
+/-
+/-
+/-
n/a
n/a
+/-
+/-
+/-
+/-
+/-
n/a
n/a = not applicable

+/- = neutral
desirable
- = undesirable
108
5.2. TESTING OF COW-MANURE COMPOST
Initial testing of cow-manure compost indicates that it has potential as an
effective and economic medium for H2S removal. PVC test columns were constructed
and a 2:1 biogas-to-air mixture passed through the columns containing anaerobically
digested cow-manure compost. The tests of most significance were run for 1057
hours with an empty-bed gas-residence time near 100 seconds and inlet H2S
concentrations averaging 1500 ppm, as measured by electrochemical sensor with a
40:1 sample dilution.
Removal efficiencies over 80% were recorded for the majority of the trial.
Elimination capacities recorded were between 16118 g H2S/m3-solids/hr. This is
significant considering only minimal moisture and no temperature or pH controls were
implemented. Temperature in the bed varied from 19-43C and the moisture contents
in the spent column ranged from 41-70%, with pH values from 4.6 to 6.9. It is not
clear whether the major mechanism for sulfur removal from the gas stream is
biological, chemical or physical, but it is known that the sulfur content in the compost
increased by over 1400%, verifying sequestration of sulfur in the solid. These initial
results indicate that future work is warranted for examining the suitability of cowmanure compost as a biofiltration medium for use with biogas.
Two potential process-configurations are envisioned for scale-up with cowmanure compost. In one, continuous biological activity is promoted by optimizing
process conditions for long-term operation. In the other, a relatively simpler batch
system with fewer process controls is established, where the compost is used for its
chemical, physical, or neglected biological activity, and changed-out more frequently.
Both processes compare favorably to other dry-based process, as illustrated in Tables
4.8, 5.1, 5.2, and 5.3, assuming minimal methane oxidation.
CHAPTER
6. FUTURE WORK AND RECOMMENDATIONS
Although the present study partially fulfills its objectives, there are limitations
that should be addressed and new directions to be explored in future research. The
biogas summary completed in the background section of this study could be expanded
in the following areas:
A Life Cycle Assessment (LCA) comparison of the economic, environmental

and social impacts for the most competitive H2S removal technologies should
be performed. Operation and maintenance costs, as well as appropriate
disposal costs, should be included.
Alternative disposal and reuse techniques for spent adsorption media should be
studied. The agricultural nutrient-value of spent media and biological
regeneration techniques for sulfur clogged iron sponge should be investigated.
An LCA for other biogas purification processes, such as CO2 reduction, water
removal, particulate filtration and removal of other gas contaminants, should
be conducted.
The processing requirements for specific gas-utilization technologies should be

compiled. Specific uses should include biogas in boilers, engines,
microturbines, fuel cells, Stirling engines, upgrading biogas to natural-gas
quality or using biogas for hydrogen production, among others
This study was also effective as a proof-of-concept, indicating that cow-
manure compost can be used as economical and effective H2S adsorption media.
109
110
Further testing and verification of these results are necessary and the following
experimental modifications are recommended:
Measurement of gaseous sulfur compounds should be done via gas

chromatography with a flame photometric detector for increased accuracy.
Experiments should take place in a controlled temperature environment to

minimize variation due to temperature fluctuations.
Moisture should be maintained around 50% wet basis. The implementation of

downward water flush could maintain bed moisture and serve to rinse out any
sulfur accumulating in the bed.
Clear columns should be used to observe any drying or microbial plugging that
might be occurring.
Additional testing needs to be done to better determine and quantify the
reactions taking place. The following tests should be performed.
The fate of methane during operation should be monitored and determined.
The sulfur species in the medium and effluent gas, including sulfates and
elemental sulfur, should be measured to account for sulfur reactions.
Jar tests should be performed on abiotic samples of cow-manure compost in

order to assess the purely physical and chemical adsorption capacity for H2S.
The effect of aeration of the biogas should be quantified.
A biological assessment of the major active microbial communities should be

performed.
An assessment of the agricultural nutrient value, compost stability, and metal

leaching in the spent filter media could be performed.
Further long-term operation and bench-scale optimization are desired before
scale-up to pilot and full scales. A life cycle assessment should then be conducted for
determining overall economic and environmental benefits.
APPENDIX A: H2S Scavenger Media Disposal

A study by the Gas Research Institute estimated 1996 change-out and disposal
costs for various media as follows (Kellog 1996). These costs are merely given in
Table A.1. to show that disposal costs can easily exceed media costs, as are expected
for transportation, installation and operating costs.
Table A.1. Approximate Media Change-out and Disposal Costs (1996 est.)
Caustic
$0.25/gal
Triazines
$1.00-2.00/gal
Non-regenerable Amines
$1.00-2.00/gal
SulfaTreat
$0.10-0.30/lb
SulfaScrub(Nitrates)
$0.10-0.20/lb
Iron Sponge
$0.10-0.30/lb
Source: Kellog (1996)
The Gas Research Institute sponsored extensive research on economic analysis

of sulfur scavenging processes for gas streams with low sulfur production in the early
to mid 1990s. The reader is directed to three papers for further information: 1)
Evaluation of H2S Scavenger Technologies, (Foral and Al-Ubaidi 1994). 2) GRI Field
Evaluation of Liquid-Based H2S Scavengers in Tower Applications at a Natural-Gas
Production Plant in South Texas, (Fisher and Dalrymple 1994). 3) Field Evaluation of
Solid-Based H2S Scavengers for Treating Sour Natural Gas, (Fisher and Shires 1995).
These works resulted in a design program, GRI-CalcBase, which can be used

for economic evaluation of different scavengers with various plant configurations.
Results of running the program with the system parameters from AA Dairy indicated
that dry scavengers such as Iron Sponge and SulfaTreat were the most promising to
investigate further.
111
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REMOVAL OF HYDROGEN SULFIDE FROM BIOGAS

USING COW-MANURE COMPOST

2003 Steven McKinsey Zicari

3.3.3. Gas Chromatography...................................................................... 67

2.1. INTEGRATED FARM ENERGY SYSTEMS

Energy benefits: Generates a high-quality renewable fuel, which has numerous

Environmental benefits: Potential to reduce carbon dioxide and methane

2.2. ANAEROBIC DIGESTION

Table 2.1: Characteristics of Typical Agricultural Anaerobic Digesters

H2, CO2, OneCarbon

Figure 2.2: Anaerobic Digestion Process

2.3. BIOGAS COMPOSITION

2.4. QUALITY REQUIREMENTS FOR BIOGAS UTILIZATION

Recommended Gas Processing Requirements

H2S < 1000 ppm, 0.8-2.5 kPa pressure, remove condensate

Similar to boilers for H2S, 1-14 kPa pressure

Sources: 1 Wellinger and Linberg (2000)

2.5. TRADITIONAL H2S GAS-PHASE REMOVAL METHODS

The chemical reactions involved are shown in Equations 2.1-2.2:(Crynes 1978)

H= -22 kJ/g-mol H2S

2Fe2S3 + O2 2Fe2O3 + 3S2

H= -198 kJ/g-mol H2S

As seen from Equation 2.1, one kg of Fe2O3 stochiometrically removes 0.64 kg

Fe203 + 6RSH = 2Fe(RS)3 + 3H20

Expected Bed Life

(4000 ppm H2S)

Biogas operations currently using iron sponge are located in Cooperstown,

(1000 ppm H2S)

(4000 ppm H2S)

1-Carbon Steel unit

Expected Bed Life

(1000 ppm H2S)

(4000 ppm H2S)

Table 2.11: System Characteristics of Media-G2 Design at AA Dairy

Expected Bed Life (one vessel)

(1000 ppm H2S)

(4000 ppm H2S)

2.5.1.2. Zinc Oxides

As shown in Figure 2.3, the equilibrium constant decreases rapidly with

Zinc-oxide processes are available in several forms for operation at

Ca(OH)2 + CO2 CaCO3 + H2O

To achieve significant removal of H2S, CO2 must also be concurrently reduced

Regeneration takes place primarily through heating. The

Molecular Sieves (Zeolites)

Table 2.13: Basic Types of Commercial Molecular Sieves

A design method for natural-gas purification by 5A molecular sieves,

As calculated, roughly 250-400 kg of zeolite would be needed on a daily basis,

(1000 ppm H2S)

(4000 ppm H2S)

Clean Gas Out

Figure 2.5: Generic Absorber/Stripper Schematic

Fe2O3.3H2O + 3NaHS + 3 NaHCO3 = Fe2S2.3H2O + 3 Na2CO3 + 3H2O (2.10)

ZnO + 2HAc = ZnAc2 + H2O

ZnO + H2S = ZnS +H2O

Figure 2.6: Reduction-Oxidation Cycle of Quinones

2Fe3+ + H2S = 2Fe2+ + S + 2H+

2Fe2+ +(1/2)O2 + H2O = 2Fe3+ + 2OH-

The LO-CAT process is potentially attractive for biogas applications because

Figure 2.7: Conventional Flow Diagram for LO-CAT Process

LO-CAT systems are currently only recommended and economical for

In the presence of CO2, the NaOH is neutralized to produce sodium carbonate

CO2 + H2O = HCO3- + H+

RNH2 + CO2 = RNHCOO- + H+

Typically used amines include monothanolamine (MEA), diethanolamine