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Removal of Hydrogen Sulfide From Biogas Using Cow-Manure Compost
Removal of Hydrogen Sulfide From Biogas Using Cow-Manure Compost
A Thesis
of Cornell University
Master of Science
by
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
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
impregnated activated-carbon systems are the most attractive, with estimated capital
processes are simple and effective, but also incur relatively high labor costs for
produced solid waste stream and growing environmental concern over appropriate
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
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
ran for 1057 hours with an empty-bed gas residence time near 100 seconds and inlet
Removal efficiencies over 80% were observed for a majority of the run time.
were implemented. Temperature in the bed varied from 19-43°C 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
These initial results indicate that future work is warranted for examining the
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
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
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
iii
To my family
iv
ACKNOWLEDGMENTS
I would like to thank my major advisor, Dr. Norman Scott, for his guidance,
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
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
Special thanks are also given to fellow graduate student John Poe Tyler. His
also thank Tina Jeoh for her constant motivation, encouragement and assistance.
graduate students are also greatly appreciated, especially Kristy Graf, Jianguo Ma,
Lastly, I would like to thank all of my family and friends for their support,
v
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
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
vii
LIST OF TABLES
viii
LIST OF FIGURES
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
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
acceptable methods of gas processing, and economic means for biogas utilization.
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
1
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.
has shown its ability to remove H2S through the microbial action of naturally
air pollution control technologies with lower capital, labor, and disposal costs.
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
and pulp and paper mills, where renewable, bio-based energy can be produced.
CHAPTER
2. BACKGROUND
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 EPA’s 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
Extensive research on these integrated systems was done during the 1970’s and
3
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
2.1.1. AA Dairy
Figure 2.1. Most of the cows are housed in a free-stall facility equipped with alley
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
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
ANAEROBIC DIGESTER
(1330 m3 plug flow
Liquids Solids
Compost
Irrigated Nutrients
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.
end-use applications.
• Economic benefits: More cost effective than many other treatment options
when viewed from a life-cycle analysis. Typical payback periods of 4-8 years.
and India to provide biogas for cooking and lighting. Also, there are over 800 farm-
based 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.
7
There are two ways to derive methane from biomass, thermally and
application to materials of low water content. This is because large amounts of energy
they require less energy and can be applied to wet or dry feedstock on a variety of
loading and an anoxic environment, and is only about 50% effective in its conversion
of organic matter.
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
bacteria utilize these intermediates for conversion to methane and carbon dioxide
Complex
Organic
Carbons HYDROLYTIC
BACTERIA
Organic
Acids,
Neutral
Compounds
TRANSITIONAL Hydrogen Producing
BACTERIA Acetogenic Bacteria
Homoacetogenic
Bacteria
H2, CO2, One- Acetic Acid
Carbon
Compounds
METHANOGENIC
BACTERIA
CH4 + CO2
There are a number of factors which influence the digestion process, including,
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
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
et al. 2000).
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).
methane and carbon dioxide, with smaller amounts (ppm) of hydrogen sulfide and
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 dairy-
manure 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
The actual amount of water vapor entrained in the gas depends on the gas
1400 m3 of saturated natural gas at 21° C and atmospheric pressure (Kohl and Neilsen
1997).
Biogas can be used for all applications designed for natural gas, assuming
Technologies such as boilers and Stirling engines have the least stringent gas
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
processing and must be done when injection into a natural-gas pipeline or production
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,
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
Principal gas phase impurities that may be present are listed in Table 2.4
condensates, and particulate matter. Hydrocarbons, such as methane, are the desired
product gases.
Gas purification processes generally fall into one of the following five
AA Dairy, which are typical for a farm digester treating waste from around 500 dairy
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
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
to have two vessels operated in parallel so one vessel can remain in service while the
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 well-
known iron oxide product is called “iron sponge.” Recently, proprietary iron-oxide
Iron Sponge
interact with H2S and mercaptans. The primary active ingredients are hydrated iron-
oxides (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
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
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
Spent iron sponge can be regenerated in place by recirculation of the gas in the
(Taylor 1956). Alternatively, the sponge can be removed, spread out into a layer 0.15-
m 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
a percent of oxygen (Taylor 1956). Equation 2.4 can be used to calculate percent air
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).
guidelines that have been determined for optimum operation. Table 2.7, below, is a
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
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
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 on-
site is still practiced, but has become riskier due to fear of the need for future
remediation.
SulfaTreat®
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
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
Drawbacks associated with this product are similar to iron sponge; the process
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
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.
Sulfur-Rite®
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
and has 3-5 times the effectiveness of iron sponge. Sulfur-Rite® also has many of the
21
cost estimates for an installation similar to AA dairy are presented in Table 2.10.
Media-G2®
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
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
regeneration cycles are estimated at full scale. Vessels are designed for approximately
$1060/m3.
22
Only two full-scale plants have been installed to date; Brookhaven Landfill in
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
The equilibrium constant for the reaction is given with Equation 2.6.
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
Figure 2.3: Equilibrium Constant for the Reaction ZnO + H2S = ZnS + H2O.
Source: Kohl and Neilsen (1997) pg. 1307.
the range of 30-40 kg sulfur/100 kg sorbent for these processes. Puraspec®, marketed
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
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.,
synergistic mixture of hydroxides that react with acid gases. Predominant reactions
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
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
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).
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
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
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
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
Activated Carbon
to drive off volatile components forms GAC’s, which have a highly porous adsorptive
surface. Utilization of GAC’s for removal of H2S has been limited to removing small
amounts, and primarily from drinking water. If H2S is the selected contaminant to be
Coating GAC’s with alkaline or oxide solids enhance the physical adsorptive
carbonate, potassium hydroxide (KOH), potassium iodide, and metal oxides are the
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.
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
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
Stripping Stripping
Solution Gas Out
Clean Gas Out
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
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.
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).
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
the high cost of non-regenerable reactant usually limits use of this process to removing
The redox cycle shown in Figure 2.6 depicts how hydrogen sulfide is
+ H2S +S
Reduction
+ O2 + H2O
Oxidation
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
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
the LO-CAT® process are available and Figure 2.7 below depicts a standard system.
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
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® iron-
chelate 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
Nitrite solutions are sometimes used when simple process configurations are
hazardous 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
3.) 6.3×10-6 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.
traces of H2S. Spent media is also non-regenerable and the high costs of chemicals
As with alkaline solids, acid gases such as H2S and CO2 react readily with
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 non-
this specialty.
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.
The Seaboard process (ICF Kaiser) was the first commercially applied liquid
process for H2S removal and used a sodium-carbonate absorbing-solution with air
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
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
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
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
without regeneration, and media consumption was around 5.3×10-6 - 6.7×10-6 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 Dairy’s. Further
information on the design and operation of alkanolamine plants can be found in Gas
Purification, Kohl and Nielsen (1997).
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
driving forces, some product will invariably be lost, especially at higher pressures.
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 Henry’s law constants for biogas
components in water.
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).
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).
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
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
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
reliability.
41
membranes operating at 25°C, 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
specifically for upgrading of biogas and operate at around atmospheric pressure and
25°C –35°C. 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
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 HS-
concentrations in the digester via Equations 2.24 and 2.25 (Jewell, et al. 1993).
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).
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
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
generally not used for sulfide reduction because diets are typically optimized for
product yields and animal health, rather than sulfur levels in the excrement.
containing chemicals or high sulfate content waters from inadvertently entering the
2.6.3. Aeration
air/oxygen dosing into the biogas. Air is carefully admitted to the digester or biogas
reduction, down to 20-100 ppm, by adding <5% air with a simple air pump. Yellow
must also be taken to avoid explosive gas mixtures (Nijssen, et al. 1997).
began to be used in the 1920’s and industrial soil biofilters first appeared in the United
44
States during the 1950’s, but operation was not well understood (Carlson and Leiser
1966). Sulfur compounds are a major component of malodor in gases and are
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
as sulfides), which supply energy to cells and produce odorless compounds like
bioreactors have recently been tested for simultaneous removal of H2S and NH3 with
volatile organic compounds and H2S in the same biofilter (Devinny, et al. 1999).
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
biofilters for pollution control, including TRG biofilters, Bohn Biofilter Corporation,
Transformations take place at significant rates both chemically and biologically. The
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
Once present, other microorganisms can use H2S oxidation to gain energy.
Various groups of organisms can oxidize reduced sulfur compounds under aerobic or
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
seen in Equation 2.27. Sulfide oxidation often occurs in steps with elemental sulfur as
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
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
Desirable attributes for biofilter support media include high surface area, low
active environment, can provide a source of nutrients for an active biolayer, and
populations and form extremely active biolayers, but degrade quickly at low pH and
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
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 10–45 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
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
waste and horse-manure composts for biofiltration of VOC’s and found that the horse-
manure compost had higher microbial activity and shorter acclimation time, but was
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
compost, used as a control, showed only 60% H2S removal under similar conditions.
A Henry’s law calculation indicated that the abiotic removal efficiency cannot come
52
only from H2S absorption into water, but must also be from chemisorption (Degorce-
Dumas, 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
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%
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).
porous lava rock. The rock showed favorable moisture retention and resisted
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
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
Anaerobic bacteria have also been used for H2S oxidation from gas streams.
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;
standard cubic meters for gas desulfurization has been made (Basu, et al. 1996).
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 (1500–7000 m3 gas/day and 1000–27000 ppm H2S) with
consistent removal efficiencies over 97%. These systems generally cost $75,000–
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
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
With integrated farm energy systems, the opportunity exists for improvements
in gas processing by utilizing on-farm compost and biological processes for H2S
knowledge, exist where anaerobically digested and composted dairy-manure has been
tested for its capability to selectively remove H2S, often at elevated levels, from
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
engine room.
3.1. 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 (¼ 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
55
56
0.05 m
OUT T
1
0.5 m
G
3 T 0.3 m
T
IN 1 0.05 m
0.1 m
LEGEND:
T = Thermocouple 1 - PVC End Caps
G = Gas Sampling Port 2 - Top of Bed
IN = Gas Sample Inlet 3 – PVC Pipe
OUT = Gas Sample Outlet 4 – Wire Screen
0.05 m
OUT T
1
4
0.5 m
G
2
0.3 m
3 T
T
IN 1
0.05 m
5
0.1 m
LEGEND:
T = Thermocouple 1 - PVC End Caps
G = Gas Sampling Port 2 - Top of Bed
IN = Gas Sample Inlet 3 - PVC Pipe
OUT = Gas Sample Outlet 4 - Wire Screen
5 – Peristaltic Pump
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,
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
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
T 0.05 m
OUT 1
G
1.5 m
3 T
0.3 m
T
0.4 m
T
2
G
T
IN
1 0.05 m
LEGEND:
T = Thermocouple 1 - PVC End Caps
G = Gas Sampling Port 2 - Wire Screen
IN = Gas Sample Inlet 3 - PVC Pipe
OUT = Gas Sample Outlet 4 – Plastic Latches
5 – PVC Couplers
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 0.75–1 .0 kPa to enter three 250-
W 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 end-
cap 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.
40, 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
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
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
Compressed air was available at the test site and regulated by a single-stage
meters, or “rotameters” (Dwyer Instruments, Inc.). Biogas and air were mixed
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
Biogas Inlet
Inlet Mixed
Sample
Gas
Outlet
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
Gas flow rates were controlled with Gilmont Accucal™ variable-area flow-
meters (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
measuring gases other than air under non-standard conditions: (Gilmont 1993)
0 . 00120 (3.1)
q G0 = q 0A
ρ G0
ρ G0 = ∑1 xi ρ i0
i
(3.2)
P 530
qG' = qG0 ⋅ (3.3)
760 T
64
dioxide ( ρ CO
0
2
= 0.00198 gm/ml), the corrected rotameter value calculated with
Equation 3.1, for biogas, becomes qG0 = 0.992 q A0 . Therefore, readings for air and
Flexible PVC sample lines (6.35 mm ID) were run from the column gas
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.
for H2S monitoring. The detector was equipped with a 0-100 ppm 4HS CiTiceL® H2S
65
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.
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
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.
2) Adjust gas sample flow rate from outlet of multi-position valve to 0.1 lpm
4) Let gas mix and allow meter reading to stabilize (~4 minutes)
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
detector-tubes (Kitagawa type 120SA) with a measuring range from 100-2000 ppm
were utilized. The scale on the detector tube is calibrated for 20°C and atmospheric
electrochemical sensor.
67
analysis on one sample of raw digester gas. The sample was delivered in a 0.3 liter
Gas temperatures before and after each column, bed temperatures, and ambient
acquisition system. The hardware and software systems used are modified versions of
ends were inserted into the center of the reactor cylinders at locations previously
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
(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,
The compost tested in this study was taken from the “finished compost” pile
solids 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
exposure to biogas may be from a specific part of the test column or from a well-
and then into an 85°C 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,
Janni (2001), was utilized to determine percent void fraction. The following
1) A plastic pail was filled with 5 liters of water and a “full” line marked on
2) The pail was filled about 1/3 full with compost and dropped ten times from
3) Compost was added to fill the pail 2/3 full. The pail was again dropped ten
4) Compost was added to the full line and dropped ten times again.
6) Water was added to saturate the compost to the “full” line and the volume
The void fraction is calculated by dividing the volume of water added by the
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
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.
submitted.
(Syracuse, NY).
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
et al. (1997), was chosen for two major reasons: 1) To ensure an aerobic environment
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.
These flow rates and empty-bed residence times were picked to maintain H2S
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
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
Table 4.1 summarizes the results from characterization of the manure compost
72
73
Trials 1 and 2, using the larger columns, were run for 16 hours during June 10-
12, 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,
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 pump’s 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
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 Dyna-
Pump 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
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
once after 700 hours of operation. Condensation was also evident in the clear PVC
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
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
3.5
3
Column 3 - No leachate Recycle
2.5 Column 4 - No leachate Recycle
Pressure (in. H2O)
0.5
0
0 200 400 600 800 1000
Run Time (total hrs)
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:
2) Porosity
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.
= + (4.1)
L ε 3 (ΦD p )2 ε 3 (ΦD p )
∆P
Where = Pressure drop per unit length
L
µ = Gas viscosity ≈ 1240x10-7 Poise @ 20°C
ε = Porosity ≈ 0.35
v 0 = Superficial gas velocity ≈ 0.19 m/min
Dp = Characteristic dimension of particle ≈ 2.5 mm
Φ = Particle sphericity ≈ 0.7 for activated carbon
ρ = Gas density ≈ 1.16 kg/m3 @ 20°C
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
operating properly. Unfortunately, interruptions to the power supply caused data loss
on multiple occasions and prevented any data collection after hour 431. The
Temperature - Column 3
45
40
Temp. (C) (15 minute average)
35
30
25
20
Inlet Gas Media
15
Outlet Gas Ambient
10
0 50 100 150 200 250 300 350 400 450
Run Time (hrs)
Temperature - Column 4
45
40
Temp (C) (15 minute average)
35
30
25
20
Inlet Gas Media
15
Outlet Gas Ambient
10
0 50 100 150 200 250 300 350 400 450
Run Time (hrs)
Temperature - Column 5
45
40
Temp (C) (15 minute average)
35
30
25
Inlet Media
20
Outlet Ambient
15
0 5 10 15 20 25 30 35 40 45 50
Run Time (hrs)
Temperature - Column 6
40
35
Temp (C) (15 minute average)
30
25
20
Inlet Media
Outlet Ambient
15
0 20 40 60 80 100 120 140 160 180 200
Run Time (hrs)
temperature was recorded inside of the engine room and is different than actual
temperature lower than ambient temperature. In all trials, it is observed that the bed
temperature is typically between 0-12°C 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
14
12
Column 5
10 Column 6
Temp. Diff. (Bed-Inlet) [C] .
Column 3
8
Column 4
6
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.
Literature indicates that the optimum range for biological H2S oxidation is in
the range of 30 – 40°C. In general, severe reduction in activity occurs below 10°C and
more moderate reduction of activity above 50°C (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.
dTbed
ρC p = UA p (Tamb − Tbed ) + G ' ( ρ in hin − ρ out hout ) + (4.3)
dt
GAo Qw ( y in − y out ) − Q gen
82
1
U = ≈ 2.29 J m - 2 s -1 K -1 (4.4)
1 1 δ
+ +
hi ho k
Where hi = Inside film coefficient
ho = Outside film coefficient
δ = 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
0.365
λg DpG
hi = 3.6 ≈ 42.65 J m -2 s -1 K -1 (4.5)
D p µ g ε
Where λg = Gas thermal conductivity ≈ 0.027 J m-1 s-1 K-1 @ 30°C
µg = Gas viscosity ≈ 1275x10-7 Poise @ 30°C
ε = Porosity ≈ 0.35
G = Gas mass velocity ≈ 0.0023 kg m-2 s-1
Dp = Characteristic dimension of particle ≈ 2.5 mm
Dr G
Re =
µ g ≈ 1.8 (4.6)
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).
0.59kair 1
L3 ρ air
2
gβ∆T
Gr = ≈ 1.02x107 (4.8)
µ 2
air
C pair µ air
Pr = ≈ 0.72 (4.9)
k air
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
σH 2S
= 1600 + (2.42 ⋅ 10−4 )(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.
2500
H2S in
2000 H2S out
H2S (ppm)
1500
1000
500
0
0 200 400 600 800 1000
Run Time (total hrs)
100%
90%
80%
Removal Eff. (%)
70%
60%
50%
40%
30%
20%
10%
0%
0 200 400 600 800 1000
Run Time (total hrs)
2500
H2S in
2000 H2S out
H2S (ppm)
1500
1000
500
0
0 200 400 600 800 1000
Run Time (total hrs)
100%
80%
Removal Eff. (%)
60%
40%
20%
0%
0 200 400 600 800 1000
Run Time (total hrs)
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
25°C. 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
2500 100%
1500 60%
Removal Eff
1000 40%
500 20%
0 0%
0 10 20 30 40 50
Run Time (total hrs)
3000 100%
2500 80%
2000 H2S in Removal Eff. (%)
H2S (ppm)
0 0%
0 50 100 150 200
Run Time (total hrs)
Gas samples from AA Diary were sporadically tested for H2S using lead-
acetate 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
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.
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
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.
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.
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.
The results for the trace element analysis are shown in the Table 4.7.
96
As seen, the original total sulfur content of the compost is about 7000 µg/g
(0.7%) on a dry basis. Columns 3 and 4 average around 110,000 µg/g for total sulfur
content. This indicates a net increase of about 100,000 µg/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 µg/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 re-
generation 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 30-40°C 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?
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 change-
outs 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 EUAC’s 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
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.
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-$23,840 per year.
Relatively high labor costs for materials handling and disposal are incurred. Major
drawbacks include a continually produced waste stream of spent media, and growing
environmental concern over appropriate waste disposal methods. The most
competitive products appear to be Iron sponge, Media-G2®, and KOH-impregnated
activated carbon. Molecular sieves may be competitive with an appropriately
designed regeneration step. Table 5.1 summarizes dry-based, H2S removal processes
and Table 5.2 summarizes estimated costs for application at AA Dairy.
102
Table 5.1: Summary Table Comparing Dry-Based H2S Removal Processes for Farm Biogas
Operating Compounds Regen- Media Costs
Packing ($/kg H2S Notes
Conditions Removed erable? removed)
Changeout can be labor intensive.
Ambient Temp. (65- 2-3 times in
Iron Sponge H2S and Variability in process efficiency but
115 F), Wet gas, 60 batch mode 0.35 - 1.55
(Iron Oxide) mercaptans much practical experience with
sec residence time only
digester gas
Ambient Temp. (65- Non-pyrophoric and easier handling
Sulfa Treat® H2S and
115 F), Wet gas, 60 No 4.85 - 5.00 characteristics compared to iron
(Iron Oxide) mercaptans
sec residence time sponge
Ambient Temp. (65-
Sulfur Rite® H2S and Available in prepackaged modules,
115 F), Wet gas, 60 No 7.95 - 8.50
(Iron Oxide) mercaptans Forms iron pyrite
sec residence time
Ambient Temp. (65- 15 times in
Media-G2® H2S and Requires multiple regenerations to
115 F), Wet gas, 60 batch mode 2.90 - 3.00
(Iron Oxide) mercaptans obtain estimated removal efficiency
sec residence time only
Removes all water before sulfur
Ambient Temp., Water,mercap-
Molecular Sieve compounds. The proposed design
High Pressure (500 tans, H2S, Yes
(Adsorbent) would have a 1-day bed life operated
psig+) slight CO2
at 500 psi
Impregnated
Ambient Temp. and H2S and KOH carbon has been used
Activated Carbon No 1.75 - 2.00
Pressure mercaptans successfully for anaerobic digester gas
(Adsorbent)
Continuous or batch processes are
Estimated Cow-
Ambient Temp. and envisioned (Table 4.8). It is not clear
Manure Compost H2S No 0.03 – 0.29
Pressure whether other compounds are
Processes
oxidized in addition to H2S.
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
Packing Bed Life (days) Capital Suppliers
and Sizes Consumption (kg) Costs ($)
Cost
(D=diameter, Low High Low High Low High (Vessels (Low loading=1000ppm
H=Height) loading Loading loading Loading loading Loading Only) ($) High loading=4000 ppm)
two - 0.91 m Connelly GPM,
Iron Sponge 930 - 3,710 - 250 - 985- 10,000 -
D x 1.52 m H 72 - 315 18 - 79 Physichem, Varec
(Iron Oxide) 4,070 16,300 1,075 4,300 50,000
each Vapor Control
two - 1.2 m
Sulfa Treat®
x1.6 m x 1.8 345 86 3,850 15,450 3,400 13,500 12,000 SulfaTreat
(Iron Oxide)
m each
®
Sulfur Rite one – 2.3 m
420 98 7,900 33,900 5,560 23,840 43,600 US Filter/ Merichem
(Iron Oxide) D x 3.4 m H
two - 0.91 m
Media-G2® 10,000 -
D x 1.52 m H 190 47 1,460 5,900 2,050 8,290 ADI International
(Iron Oxide) 50,000
each
Molecular
one – 0.6 m Many - See
Sieve 24 hours 24 hours 250/day 400/day n/a n/a n/a
Dx2mH Thomasregister.com
(Adsorbent)
Impregnated
two – 0.6 m
Activated Many - See
D x 1.5 m H 340 85 270 1075 1250 5435 <50,000
Carbon Thomasregister.com
each
(Adsorbent)
Estimated one or two – Note: (low and high
Cow-Manure 0.91 m D x 10,000 – loading values are for
40 360 1720 15480 35 300
Compost 1.77 m H 50,000 batch and continuous
Processes each process, respectively)
105
These processes have not traditionally been used for low-flow and low-
pressure applications due to increased costs of operating at high pressure, high energy-
requirements 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.
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.
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
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)
111
REFERENCES
Anerousis, J. P. and S. K. Whitman (1985). "Iron Sponge: Still a Top Option for Sour
Gas Sweetening." Oil and Gas Journal February 18: 71-76.
Bohn, H. L. and H.-C. Fu-Yong (1989). "Hydrogen Sulfide Sorption by Soils." Soil
Sci. Soc. Am. J. 53: 1914-1917.
CADDET (2001). Upgrading of Biogas to Natural Gas - Technical Brochure No. 154.
Centre for Renewable Energy (CADDET), Oxfordshire, UK: 4 p. www.caddet-
re.org/assets/no154.pdf
Carlson, D. A. and C. P. Leiser (1966). "Soil Beds for the Control of Sewage Odors."
Journal of Water Pollution Control Federation 38(5): 829-840.
Chi, C. W. and H. Lee (1973). "Natural Gas Purification by 5A Molecular Sieves and
its Design Method." AIChE Symposium Series 134(69): 95-101.
112
113
City Technolgy Limited (2002). Cross Sensitivity Table for 7H Series Electrochemical
H2S Sensors. Portsmouth, UK: 1 p.
Cole Parmer (2002). Chemical Resistance Chart from the Cole-Parmer Catalog
Vernon Hills, IL: R17-R26.
Devinny, J. S., M. A. Deshusses, et al. (1999). Biofiltration for Air Pollution Control.
Boca Raton, FL, Lewis Publishers: 299 p.
Elias, A., A. Barona, et al. (2002). "Evaluation of a packing material for the
biodegradation of H2S and product analysis." Process Biochemistry 37(8): 813-820.
Froning, H. R., R. H. Jacoby, et al. (1964). "New K-Data Show Value of Water
Wash." Hydrocarbon Processing and Petroleum Refiner 43(4): 125-130.
Gabriel, D., J. Brown, et al. (2002). "Short Contact Time Biotrickling Filter for Odor
Treatment." Proceedings of the 2002 USC-TRG Conference on Biofiltration, Newport
Beach, CA: 267-276.
Hartikainen, T., et al. (2001). "Carbon Disulfide and Hydrogen Sulfide Removal with
a Peat Biofilter." Journal of the Air and Waste Management Association 51: 387-392.
Janssen, A. J. H., H. Dijkman, et al. (2000). "Novel biological processes for the
removal of H2S and SO2 from gas streams." Chapter in Environmental Technologies
to Treat Sulfur Pollution. P. N. L. Lens and L. H. Pol (Eds.). IWA Publishing,
London, UK: 547 p.
Jensen, J. K. and A. B. Jensen (2000). "Biogas and Natural Gas Fuel Mixture for the
Future." Written for the 1st World Conference and Exhibition on Biomass For Energy
and Industry, Sevilla: 8 p. http://uk.dgc.dk/pdf/Sevilla2000.pdf.
Jewell, W. J., R. J. Cummings, et al. (1993). Energy and Biomass Recovery from
Wastewater. Cornell University, Ithaca, NY: 370 p. GRI Report #93/0192.
Kim, B. W., K. W. Chang, et al. (1997). "Effect of light source on the microbiological
desulfurization in a Photobioreactor." Bioprocess Engineering 17: 342-348.
Kim, N. J., M. Hirai, et al. (1998). "Comparison of Organic and Inorganic Carriers in
Removal of Hydrogen Sulfide in Biofilters." Environmental Technology 19: 1233-
1241.
116
Koe, L. C. C. and F. Yang (2000). "A Bioscrubber for Hydrogen Sulphide Removal."
Water Science and Technology 41(6): 141-145.
Kohl, A. and R. Neilsen (1997). Gas Purification. Golf Publishing Company, Houston,
Texas: 1395 p.
Ma, J. (2002). Spatial Analysis of the Potential for Dairy Manure as a Renewable
Energy Resource in New York State. M.S. Thesis in Biological and Environmental
Engineering. Cornell University, Ithaca, NY: 108 p.
McGuckin, R. L., M. A. Eiteman, et al. (1999). "Pressure Drop through Raw Food
Wast Compost Containing Synthetic Bulking Agents." Journal of Agricultural
Engineering Research 72: 375-384.
Minott, S. J. (2002). Feasibility of Fuel Cells for Energy Conversion on the Dairy
Farm. M.S. Thesis in Biological and Environmental Engineering. Cornell University,
Ithaca, NY: 130 p.
117
Perry, R. H., D. W. Green, et al., Eds. (1997). Perry's Chemical Engineers Handbook.
McGraw Hill, New York: 2640 p.
Rands, M. B., D. E. Cooper, et al. (1981). "Compost Filters for H2S Removal from
Anaerobic Digestion and Rendering Exhausts." Journal of Water Pollution Control
Federation 53: 185-189.
Revell, C. (1997). Dear Mr. Iron Sponge Plant Operator. Connelly-GPM, Inc.,
Chicago, IL: 9 p.
Roos, K. F. and M. A. Moser (Eds.) (2000). The AgSTAR Handbook, Prepared for the
US Environmental Protection Agency, Washington, D.C.:EPA#430B9715.
Ruitenberg, R., H. Dijkman, et al. (1999). "Biologically Removing Sulfur from Dilute
Gas Flows." Journal of Materials May: 45.
Spiegel, R. J. and J. L. Preston (2000). "Test Results for Fuel Cell Operation on
Anaerobic Digester Gas." Journal of Power Sources 86: 283-288.
Spiegel, R. J., J. C. Trocciola, et al. (1997). "Test Results for Fuel-Cell Operation on
Landfill Gas." Energy 22(8): 777-786.
STM Power (2002). Pure Energy on Demand, Brochure for STM Stirling Engines.
STM Power, Ann Arbor, MI: 6 p.
www.stmpower.com/Markets/STMPureEnergyBrochure.pdf
Sun, Y., C. J. Clanton, et al. (2000). "Sulfur and Nitrogen Balaces in BIofiltes for
Odorous Gas Emission Control." Transactions of the ASAE 43(6): 1861-1875.
Taylor, D. K. (1956). "Natural Gas Desulfurization (Parts 1-4)." Oil and Gas Journal
(November 5, 19, and December 3, 10): 4 p.
UOP (2000). THIOPAQ Process Technical Data Sheet. Paques Biosystems, The
Netherlands: 3 p. www.uop.com/techsheets/thiopaq.pdf.
Vetter, R. L., D. J. Friederick, et al. (1990). Full Scale Anaerobic Digester and Waste
Management System for a 300 Cow Dairy. Proceedings of the Sixth International
Symposium on Agriculture and Food Processing Wastes, ASAE, Chicago, IL: 236-
249.
Wang, E. (2000). Personal Communication with S. Zicari. Varec Vapor Control, Inc.,
Cypress, CA.
XENERGY, Inc. (2002). Toward a Renewable Power Supply: The Use of Bio-based
Fuels in Stationary Fuel Cells. Prepared for the Northeast Regional Biomass Program,
Washington, D.C.: 63 p.
120
Zapffe, F. (1963). "Iron Sponge Removes Mercaptans." Oil and Gas Journal August
19.