WEF/AWWA Joint Residuals and Biosolids Management Conference 2007

DIGESTER GAS CLEANING REQUIREMENTS

BASED ON END USE

Hari Santha, James Rowan, Webster Hoener

Black & Veatch Corporation
8400 Ward Parkway, Kansas City, MO 64114

ABSTRACT

The anaerobic digestion process, used for solids stabilization at municipal wastewater treatment
facilities, is a net producer of energy in the form of digester gas that can be used to offset part of
the energy requirements for plant operations. However, there are several challenges associated
with the use of digester gas as an alternate fuel source. As generated from the digesters, the gas
contains several contaminants that can increase the maintenance requirements of the equipment
fueled by the gas. A multi-step cleaning process is often called for to improve the gas quality.
The capacity requirements and costs of the gas treatment system can depend on several variables,
including the quantity of gas treated, the initial concentration of contaminants, and the final
concentration of contaminants in the gas to meet the quality requirements for the gas utilization
equipment. Not all applications require the gas to be of high quality and there can be significant
differences between the gas quality requirements for different gas utilization equipment.

The paper provides an overview of the typical problems associated with handling and using
digester gas without adequate cleaning, a decision matrix to determine the cleaning requirements
based on the end use, and the technologies available for cleaning the gas to meet the specified
quality requirements.

KEYWORDS

Anaerobic Digestion, Biogas, Utilization, Cleaning, Moisture, Hydrogen Sulfide, Siloxanes

INTRODUCTION

The anaerobic digestion process, used for solids stabilization at municipal wastewater treatment
facilities, is a net producer of energy in the form of digester gas that can be used to offset part of
the energy requirements for plant operations. There has been extensive experience with digester
gas collection and utilization technologies over the years and energy recovery from digester gas
is now regarded as one of the more mature and successful waste-to-energy technologies.

The primary driver for digester gas utilization in recent years has been the need to economize the
use of fossil fuels. The most common use of digester gas at municipal wastewater treatment
facilities is as fuel for boilers to generate steam or hot water for process and building heating. If
thermal drying is part of the solids processing operations, then digester gas is first used to offset
part of the energy requirements for drying. The heat recovered from the dryer condensate is used
to provide process and building heat. Increasingly, digester gas is being used in engine

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generators, turbine generators or microturbines to generate electrical power for treatment plant
operations, or for sale or credit to the local power utility. Typically, all the digester gas is used in
engines or turbines to maximize electrical power generation and heat recovered from the power
generation equipment in the form of hot water or steam (combustion turbines only) is used for
digester heating.

There are several challenges associated with digester gas utilization. The gas produced from
anaerobic digesters may not always meet the quality requirements of the gas utilization
equipment and will require cleaning before it can be used effectively for plant energy needs. Gas
cleaning is a capital intensive multi-stage operation that can carry high maintenance costs due to
media replacements and/or power costs.

Given the high cost of gas treatment, wastewater treatment facilities have to be judicious in
determining the extent of gas cleaning required for the utilization equipment to ensure an overall
reduction in operating costs. The gas quality requirements vary for different gas utilization
equipment and not all applications require the same biogas quality. The following sections
provide an overview of the contaminants in digester gas, gas quality requirements for the various
utilization equipment, and the available cleaning technologies.

DIGESTER GAS COMPOSITION & EFFECT OF CONTAMINANTS

The biogas generated during the decomposition of organic materials in anaerobic digesters is
composed primarily of methane and carbon dioxide with smaller quantities of hydrogen sulfide
(H2S). The gas is typically saturated with moisture at the operating temperature of the digesters
and can also contain contaminants, including sediment and siloxanes.

The carbon dioxide present in digester gas is not necessarily a contaminant, but it dilutes the
energy content of the gas and lowers its calorific value. Removal of carbon dioxide from the gas
mixture helps in enriching the fuel value of digester gas. Carbon dioxide removal can be
accomplished by water or chemical scrubbing, by using carbon sieves or by selective permeation
through membranes. All of these technologies are expensive and may be economically feasible
only if the gas is to be upgraded to natural gas quality and sold commercially. The gas
utilization systems, including boilers, thermal dryers, and power generation equipment, designed
specifically for alternative fuels are capable of handling 30 to 50 percent volume of carbon
dioxide in the gas. Therefore, use of digester gas for any of these applications does not call for
carbon dioxide removal.

Moisture and Sediment

The moisture present in digester gas is directly proportional to the temperature of the gas, the
higher the digester operating temperature, the greater the proportion of moisture in the gas. The
moisture, if not removed, will condense and accumulate in the lower sections of piping as the gas
cools and hinder gas flow. The condensed water can impair the operation of valves and cause
increased corrosion by dissolving any hydrogen sulfide that may be present in the gas. Moisture

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in the gas also reduces the ability of the gas to combust efficiently and can also lead to pitting
and cylinder damage in the engine generators if the gas is used for electrical generation.

Foam and entrained particulates in the gas can also pose operational concerns to the gas
collection and handling equipment. Sediments overflowing into the gas piping can restrict flow,
causing higher pressure losses in the piping and higher gas pressure in the digesters.

Hydrogen Sulfide

H2S is an extremely reactive compound that forms an acidic solution with water in the gas
handling and utilization equipment. The acid formed is highly corrosive and can corrode
pipelines, gas storage tanks and gas utilization equipment. The H2S present in digester gas is the
primary contributing factor for the shortened usable life of many of the components in the
digester gas system. In addition, H2S is a dangerous compound that can be lethal at
concentrations above 700 parts per million (ppm).

If there are significant quantities of H2S in the gas, some sulfur typically gets deposited in the
high temperature parts of the gas utilization equipment. This is the amorphous form of sulfur,
which is dense and hard to remove.

Siloxanes

Siloxanes, volatile organic chemicals which contain silicon, are a contaminant of growing
concern for digester gas utilization. Siloxanes are organic silicon polymers that are used in many
forms in a wide range of commercial, personal care, industrial, medical, and even food products.
Personal care products such as shampoos, hair conditioners, cosmetics, deodorants, detergents,
and antiperspirants are thought to be the main sources of siloxanes found in sewage and digester
gas.

A number of wastewater treatment utilities that have logged many years of digester gas
utilization without significant problems are now beginning to observe the effects of siloxanes on
their gas utilization equipment. Current thinking is that the siloxanes in digester gas are in
gaseous form until they are converted to the solid form during combustion. With the increasing
use of siloxanes in manufacturing, their concentration in digester gas and the associated
problems are anticipated to increase.

With moderate heating of the digesters (to 35°C/95°F), the siloxanes are volatized into their
gaseous form and, when burned, gets transformed into a sand-like material (silicon dioxide,
SiO2) that is too small to be captured in ordinary scrubbers and becomes deposited on the cooler
surfaces or in the combustion chambers, resulting in accelerated wear and loss of heat transfer
efficiency. To protect combustion equipment, the siloxanes must be removed from the digester
gas before combustion.

Siloxanes or their effects have been observed in off-gases from processes that involve heating the
sludge.

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ƒ Digester gas used as fuel in boilers has caused accumulations of fine sand-like material on
the exhaust gas side of the boiler tubes, which reduces their heat transfer efficiency and
boiler capacity. The sand-like material is SiO2 produced through oxidation (burning) of the
volatized siloxanes contained in the digester gas. Figure 1 shows siloxane deposition on
boiler tubes.

Figure 1. Silicon Dioxide (SiO2) Deposits on Boiler Tubes

ƒ Thermal dryers using digester gas and natural gas-fired thermal oxidizers have been found
to have accumulation of sand-like material on their heat exchanger surfaces as a result of
burning digester gas containing siloxanes, and the failure of emission control equipment to
collect the SiO2 formed. Figure 2 shows the accumulation of sand-like material on the
packing material in the regenerative thermal oxidizers.

Figure 2. Particulate Deposition in Thermal Oxidizer Packing

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ƒ Engine-generators and engine-blowers burning digester gas are susceptible to

accumulations of SiO2 in their combustion chambers and in their lubrication oil, increasing
maintenance and decreasing time between overhauls. Figures 3 and 4 show the damage
caused to engine generators by a combination of hydrogen sulfide and siloxanes.

Figure 3. Damage to Engine Generators by H2S and Siloxanes

Figure 4. Damage to Engine Piston by H2S and Siloxanes

Since siloxanes are highly volatile at relatively low temperatures, the possibility of a relationship
between digester operating temperature and the concentrations of siloxanes in the digester gas
may be implied. There are reasons to believe that where digesters are heated to higher

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temperatures than for mesophilic digestion, additional siloxanes may be found in the digester
gas.

The siloxanes in digester gas are predominantly D4 (Octamethylcyclotetrasiloxane) and D5

(Decamethylcyclopentasiloxane) compounds, accounting for more than 90 percent of the total.
A summary of siloxane concentrations in digester gas from several wastewater treatment plants
is shown in Figure 5. The samples collected in 1999 and earlier were interpreted as D4
siloxanes, but were reported as “total siloxanes”. Total siloxanes is the parameter of interest
when assuming the potential impact of siloxanes on the operation of gas utilization equipment.
The sample sites shown in the Figure are as follows:

ƒ Sites No.1 through 8, 10 and 11 are located in California. Sites 1 through 8 are early data
and are assumed to be D4.

ƒ Sites No. 9 and 12 are Upper Midwestern treatment plants, and the data are more recent.

ƒ Site No. 13 is a plant in the Southwest U.S.

8000

7000

6000
Siloxanes, ppbv

5000

4000

3000

2000

1000

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Site Number

D4 D5 D4 & D5 combined

Figure 5. Siloxanes in Digester Gas at Various Treatment Plants

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DIGESTER GAS CLEANING REQUIREMENTS

Digester gas is suitable for all applications using natural gas. However, the gas quality
requirements can vary depending on the application and will also depend on the concentrations
of the various contaminants in the gas.

Boilers and Thermal Dryers. If digester gas is to be used as fuel in boilers or as energy source
for thermal drying, the quality requirements are comparatively low. However, it is
recommended that the H2S concentrations and moisture in the gas be reduced to avoid
condensation and formation of acidic solutions that can lead to severe corrosion of gas handling
and utilization equipment. Moisture in the gas can also cause problems to valves and the burner
nozzles. If the gas contains high concentrations of siloxanes, it may be advisable to include a
siloxane treatment step to reduce the maintenance requirements on boilers and thermal oxidizers
used for off-gas treatment in drying.

Engine Generators and Turbine Generators. Siloxane limits recommended by engine and
turbine manufacturers range from non-detect [19 to 24 parts per billion by volume (ppbv)
detection limit] to approximately 1,700 ppbv. In general, engine manufacturers’ do not provide a
definition of “total siloxanes”. However, it is understood that the limits would apply to both D4
and D5 siloxanes and any other siloxane compounds above the detection limit.

Since the limits are set at detection concentrations, near complete removal of siloxanes is
recommended. Where siloxanes have been removed, engine owners report maintenance efforts
similar to those for an engine operating on natural gas, a substantial reduction in the frequency
and cost of maintenance compared to operating with raw gas.

Most manufacturers have also established limits on the amount of sulfur compounds, water,
particulates, and heavy tars in the digester gas. Therefore, the use of digester gas as fuel for
power generation would involve cleaning and treatment of the gas to produce a clean, dry fuel.

Figure 6 shows a decision matrix for determining the gas cleaning requirements for different gas
utilization scenarios.

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Figure 6. Digester Gas Cleaning Decision Chart

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GAS DIGESTER CLEANING METHODS

The gas cleaning technology selected will determine the overall capital and operating costs for
the gas handling and utilization system. Following is a discussion of the digester gas cleaning
options for reducing condensation, lowering H2S levels, and removing siloxanes.

Sediment Removal

The first step in the cleaning of digester gas is the separation of foam and sediments from the
gas. This can be accomplished by using a foam separator in the digester gas piping. The foam
separator is a large vessel separated down the middle by a baffle wall. The roof of the vessel is
fitted with water nozzles to provide a continuous spray wash. The foam and sediment laden gas
enters the vessel near the top. The gas must then travel down through the spray wash under the
baffle wall and back up through a second spray wash before exiting the vessel through an
elevated discharge nozzle. The spray wash and the baffle wall produce a foam free gas at the
discharge of the foam separator. Figure 7 shows the cross section of a foam separator.

Figure 7: Cross Section of a Foam Separator

H2S Removal

There are several methods available for removing H2S from digester gas. The following sections
outline the methods available for removing H2S from digester gas.

Ferric Chloride Injection. Ferric chloride injection does not remove H2S in the digester gas, but
reduces the amount of H2S generated in the digesters. Ferric chloride when injected into a
sludge stream reacts with the sulfur present, forming insoluble salts that fall out of solution and
are taken out during dewatering. In documented cases, H2S concentrations in the digester gas

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have been reduced from 3,000 ppm before ferric chloride addition to 200 to 300 ppm after
addition. With ferric chloride addition, the sulfur reacts with iron before it is introduced into the
gas stream. Therefore, odors caused by the presence of H2S are reduced at the digesters.

Ferric chloride has also been shown to reduce the formation of struvite downstream of the anaerobic
digesters. Struvite (magnesium ammonium phosphate, MgNH4PO4.6H2O) is a hard, crystalline
substance that often develops in areas of high turbulence. Struvite precipitation potential increases
with increasing pH. When the digested solids are pumped or mixed, the turbulence created by these
operations strips carbon dioxide from the liquid, increasing pH and promoting struvite deposition.

Any ferric chloride added to the digesters will preferentially react with hydrogen sulfide. If
struvite control is also desired, then sufficient quantities of iron must be added to account for
both sulfide and phosphorus reactions. It may be beneficial to determine the required iron
dosages through bench-scale or full-scale testing. Sulfide reactions typically require a 0.7 to 1
molar ratio of iron to sulfide (0.4 to 1 Fe:S by weight).

Iron Sponge. In this process, digester gas is passed through a permeable bed of iron sponge
(hydrated ferric oxide). The hydrated ferric oxide media used is in the form of iron-dipped wood
chips, soaked in water. As H2S passes through the iron media, an exothermic (heat-producing)
reaction takes place, converting H2S to ferric sulfide (black solid) and water.

Fe2O3.H2O + 3H2S Æ Fe2S3 + 4H2O

This is a passive chemical reaction. There are no mechanical parts or operator interfaces
required to make the sulfide removal process work. One advantage of the process is that the iron
sponge can be regenerated and reused more than once before replacement. The exhausted media
is usually a combination of ferric sulfide and wood chips. This is not a hazardous waste and can
be taken to any landfill for disposal. However, the process of removing the media and refilling
the vessel can be messy and labor intensive.

Another potential problem is that the process of regenerating the iron sponge is a highly
exothermic reaction that uses water and air to release sulfur from the iron and reform the
hydrated ferric hydroxide. If not submerged in a flowing water bath and controlled properly, the
iron chips can get very hot and combust spontaneously. This becomes even more dangerous if
all of the digester gas has not been removed from the vessel.

Proprietary Scrubber Systems. In proprietary systems, the H2S laden digester gas is passed
through a bed of media that selectively reacts with H2S in the gas. There are several differences
between the proprietary systems and the iron sponge system. The proprietary systems use a
media that is a free-flowing granular substance that will not ignite or “cement up” like the iron
sponge media, but typically the media cannot be regenerated. In order to increase media life and
improve treated gas quality, these systems have multiple vessels arranged in a lead/lag setup.
The dirty gas passes through the lead vessel first where it reacts with the media to remove most
of the H2S. Subsequently, the gas flows through the lag vessel. The gas exiting the lag vessel
will be nearly free of H2S. Once the media in the lead vessel is used up, the vessel is taken off
line and the media is replaced. While the lead vessel is off line, the lag vessel becomes the

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primary scrubber. After media replacement, the original vessel is returned to service in backup
capacity. The advantage to these systems is that it requires only two vessels, which greatly
reduces the required footprint. However, since there is less media volume, and the media are not
regenerated, the proprietary systems require more frequent media replacement. Figure 8
illustrates a proprietary scrubbing system.

Figure 8. Proprietary Scrubbing System

Moisture Reduction

To reduce the impact of moisture in digester gas, dryers are employed which cool the gas to
condense the moisture. The new saturation temperature is that to which the gas has been cooled.
The drying process includes reheating step, where the temperature of the gas is increased to
provide a cushion that allows the gas to be piped without additional moisture dropping out, as
long as the temperature is above the saturation temperature. There are two variations of dryers
used for digester gas drying:

ƒ Refrigerant dryers use the compression and expansion of a refrigerant to cool the gas
directly in a heat exchanger. These units typically use the heat removed from the gas in the
drying process to reheat the cooled gas above the saturation temperature. Typical dryers
cool to a saturation temperature (pressure dew point) of 35 to 40 oF. Lower temperatures
are available and may be used as a combination dryer and siloxanes removal device. These
units typically cool to -10 to -20 oF for removal of siloxanes. Digester gas refrigerant
dryers must use corrosion resistant materials in contact with the digester gas. The dryers are
nearly the same as air dryers but with corrosion resistant materials.

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ƒ The second type dryer employs a more conventional chiller that uses a refrigerant to cool a
liquid which in turn is used to cool gas using a liquid to gas heat exchanger. A second heat
exchanger is also used to reheat the gas using heat taken from the gas in the first heat
exchanger. The chiller is the same as used for building cooling systems. The heat
exchangers are built of corrosion resistant materials in contact with the gas. Typical
saturation temperatures of 35 to 40 oF are used.

The second dryer type is typically used in conjunction with a carbon scrubber for removal of
siloxanes. Refrigerant dryers can also be used with a carbon scrubber. Selection of dryers
should be based on the anticipated dryness needed and the potential need for siloxanes
scrubbing. In addition to the gas dryer, a gas booster is often required to overcome the pressure
losses associated with the dryer.

Corrosion from condensing acid can be minimized by removing H2S from the gas prior to
drying. Without moisture, any remaining H2S will combust in the engine cylinder or pass
through the engine exhaust without reacting.

Siloxane Removal Options

The following sections provide details of three types of siloxane removal systems: gas dryers,
activated carbon scrubbers, and carbon dioxide (CO2) wash.

Gas Drying. Siloxanes are relatively heavy volatile compounds that tend to adhere to the water
vapor in the digester gas stream. Therefore, a significant fraction of the siloxanes can be
removed along with the moisture when the gas is dried. To achieve a level of drying that will
remove most of the siloxanes, the gas must be dried to a dew point temperature –10°F or lower.
The equipment consists of a refrigerant-type dryer that cools the digester gas as it passes through
the dryer. The dryers typically include a heat recovery system that uses the heat removed from
the incoming gas to raise its outgoing temperature above the dew point for extra protection from
moisture condensation. While gas drying systems are relatively simple in concept, those that
operate at -10°F or lower have the disadvantage of being subject to significant amounts of ice
formation. If the ice is not removed, it can cause the pipes to burst, damaging the refrigeration
system.

At some facilities, the digester gas used to fuel the engine-generators is dried by a refrigerant
dryer that cools it to 40°F pressure dew point. At this temperature, up to about 40 percent
removal of siloxanes has been reported.

Activated Carbon Scrubbers. The carbon scrubbers used to remove siloxanes from digester gas
operate according to the same principles as the carbon scrubbers used in many wastewater
treatment plants for odor control. The digester gas is passed through a vessel filled with
activated carbon media. The organics (including siloxanes), hydrogen sulfide (H2S), and several
other compounds in digester gas are adsorbed onto the carbon. With proper maintenance and
periodic replacement of the carbon media, the residual siloxanes in the digester gas would be
anticipated to be below detection limits. However, since activated carbon is not selective for

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siloxanes, it would have to be replaced frequently unless the organics were removed from the gas
before it reached the carbon scrubber.

If used in conjunction with a gas dryer, activated carbon could be a cost-effective means of
removing siloxanes from digester gas. In this application, chilling the gas to 40°F with a
refrigerant dryer would remove some of the water and heavy organics. The activated carbon
scrubbers would then be used to remove the remaining compounds, extending the life of the
carbon media to an acceptable period. Typically, the media has to be replaced once a year.

Carbon Dioxide (CO2) Wash. A CO2 wash process has also been used to-date, primarily on
landfill gas and other high-volume contaminated gases, for siloxane removal. It is typically used
for methane recovery, but also strips siloxanes from digester gas. It works on the basic principle
that refrigeration combined with compression cools the gas to the point where the CO2 in the gas
becomes a liquid. The liquid CO2 causes a washing effect, which draws the heavy organic
compounds and siloxanes out of the gas and into the waste CO2 stream. The waste CO2
containing the contaminants is then sent to a flare to be thermally oxidized. The remaining gas is
primarily methane that can be used as engine fuel.

This system has several disadvantages. First, because of the amount of equipment required, it is
not cost-effective unless both pure CO2 and methane can be recovered. Second, the system uses
a large amount of electrical energy to compress the gas to the 300 to 400 pounds per square inch
gauge (psig) needed to produce the CO2 wash and to generate the refrigeration effect. Finally,
the equipment cost alone for even the smallest system would be very high. Therefore, CO2 wash
is not an attractive option for removing siloxanes from the digester gas at wastewater treatment
facilities. Figure 9 is an illustration of the CO2 wash system.

Figure 9. CO2 Wash System

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A schematic identifying the steps involved in removing all the contaminants of concern from
digester gas is shown in Figure 10. The system includes a sediment trap for removing foam
and/or any entrained particulates, a H2S scrubber, a dryer for condensing moisture and some of
the siloxanes, and an activated carbon system for removing the remaining siloxanes.

Figure 10. Overall Gas Treatment Schematic

Conclusions

The typical digester gas cleaning steps for the eliminating moisture and lowering H2S and
siloxane levels in the gas include:

H2S Removal. Ferric chloride injection to the digester feed is the most cost effective H2S control
strategy. However, it has the lowest sulfide removal efficiency of all systems. The chemical
feed rates also have to be adjusted based on the variations in flow, requiring more operator
attention.

Iron sponge and proprietary chemical scrubbers are established technologies for sulfide removal.
While proprietary systems may have smaller footprints and lower capital costs than the iron
sponge system, the annual operating costs may be higher as it can require more frequent media
replacement.

If H2S concentrations are high, it may be cost effective to add ferric chloride to the digesters to
lower H2S concentrations before the sulfide removal systems. This would lower the overall
sulfur removal costs by prolonging the life of the media used. It may also be possible to enhance
media performance by adding air to the digester gas upstream of the gas cleaning system. Air
catalyzes the reaction of H2S with the media and improves reaction kinetics. However, the
volume of air added has to be carefully controlled to avoid forming an explosive mixture with
methane.

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Gas Drying. Reduces the moisture content in the digester gas. Besides moisture removal, some
siloxane reduction can also be achieved by drying the gas to 40°F. The requirement for an
additional treatment step would depend on the quantity of siloxanes present in the digester gas.
The best available treatment technology for siloxane removal is a combination of gas drying and
activated carbon adsorption. Digester gas is first chilled to 40º F which condenses a large
portion of the water and 30 to 40 percent of the siloxanes in the gas. The dried gas passes
through a bed of activated carbon which adsorbs the remaining siloxanes. The H2S
concentrations in the gas have to be reduced prior to carbon adsorption.

One of the concerns with drying of digester gas is that straight-chain hydrocarbons, such as
ethane, propane, and butane that have high boiling points can condense when chilled. These
appear as odorous, tar-like materials in the condensate from the gas chilling equipment and have
been noted at some locations. Prior to design of the siloxane treatment system, a detailed
characterization of digester gas is recommended to identify the types of siloxanes and other
volatile organic carbons (VOC) present in the gas.

Finally, prior to determining the cleaning requirements for a particular utilization scenario, a
detailed gas sampling and analysis program should be undertaken to quantify the contaminants
under various conditions. The gas composition, especially the concentrations of hydrogen
sulfide and siloxanes, can change with time depending on the feed characteristics and operating
conditions of the digesters. Consequently, gas samples should be analyzed over a period of time
to identify the variations in gas composition and define design parameters for the gas cleaning
system.

Proper determination of the cleaning steps required and selection of the appropriate treatment
technology for each contaminant will impact the overall costs for the gas cleaning operation.

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