§§ Something water related

Timothy Lebrecht, Air Products, USA, and Neil Hannay, Air Products,
UK, offer several ways to treat H2S in wastewater and discuss the benefits
and drawbacks of each.

S
ulfur species are typically treated within a process and
managed through reaction engineering. But what happens
when small concentrations of sulfur species make their way
into wastewater? For many substances, the result is the
creation of hydrogen sulfide (H2S), a dangerous, odorous substance.
This article looks at various ways to handle sulfur species,
particularly H2S, and offers specific treatment methods, along with
the benefits and drawbacks of each method. Although sulfur
treatment can be a significant challenge, a cost effective solution is
available through the creative use of oxygen based chemistry.

What is H2S?
H2S is a flammable, colourless gas that smells like rotten eggs. It
occurs both naturally and from manmade processes. H2S can be
released from volcanoes, sulfur springs, undersea vents, swamps,
stagnant bodies of water and, most commonly, in areas with crude
petroleum and natural gas production and refining. Other industries
that have to manage the creation and treatment of sulfur are water
treatment, landfill gas processing, manure handling, and pulp and
paper. In all of these areas, sulfur species continue to be difficult to
isolate and manage.
In wastewater treatment, sulfur and H2S concentrations tend to
be relatively low, yet high enough to cause issues with safety,
corrosion and odour complaints. This article will review some
techniques for treating sulfur species in wastewater and help
identify the most effective way to manage this odorous gas when it
occurs in the process.

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 Table 1. Methods of sulfur control
Method of Methods Action Main sulfur Further Process Typical Comments
control compounds treatment application requirement,
produced required area lb/lb H2S
pH control Acid dose for Removal H2S dissolved Gas stream H2S Effluent flow pH and stripping
acid stripping pH<5 by pushing removal control can
equilibrium to be difficult to
H2S (sol) maintain at
equilibrium, plus
H2S is highly
soluble.
pH control Base dosing for Control by HS Neutralisation In lagoon pH too high for
alkali maintaining in pushing for discharge biological activity.
solution pH>9 equilibrium
to HS
Redox/ORP Oxygen (as Prevention, SO Maintenance Effluent flow Must be
control air or pure removal and SO4 of high redox/ and in lagoon maintained to
oxygen) control ORP prevent reduction
Nitrate of S and SO4
Oxidation H2O2 Removal and S Removal of Effluent flow Expensive;
Permanganate control SO solid and/or and in lagoon undesirable
Chlorine SO4 prevention of organic reactions;
Chlorine reconversion toxic chemical
dioxide to H2S handling
Hypochlorite considerations.
Ozone
Stripping Air Gas H2S in carrier Gas collection Effluent flow Low pH
CO2 stripping for gas and scrubbing maintenance
downstream required for
gas phase effective full
treatment sulfide removal;
CO2 carrier gas
is therefore
preferable to air.
Precipitation Ferrous sulfate Reaction Fe2S3 solid Solids removal Effluent flow 4 - 15
to solid and disposal
precipitate
Bactericidal Acid/alkali Kill all n/a Ongoing Effluent flow Applicable for
Chlorine bacteria requirement corrosion and
Permanganate to remove to ensure no odour control in
biological biological pipelines.
reduction of activity
sulfur species

An example from the refining industry is the Claus reaction,

Issues with H2S
H2S is a chemical that comes with severe dangers. It is a strong acid
when dissolved, extremely flammable and highly toxic. Since this
article focuses on wastewater, the flammability hazard is not part
of the discussion. However, the toxicity and odour of the
substance cause this material to be one of the most challenging to
handle. For example, elevated H2S levels can cause headaches and
nausea at just 5x the odour detection threshold, assuming a
detection threshold of 8 ppb (toxicity issue threshold would then
be 40 ppb). H2S has been lethal to humans at acute concentrations
generally exceeding 500 ppm.
H2S removal versus control
In general, companies are very aware of processes that can
generate or accumulate sulfur and H2S. The dangers associated with
H2S, as well as the extreme odour, have companies doing what
they can to make sure they remove as much of the material as
possible within the process. Treating in process is the best way to
address H2S.
which transforms H2S to elemental sulfur. Sour water can be
encountered and will need to be treated, but the vast majority of
H2S is handled outside of the wastewater process. Treatment
through specific reactions is most commonly done when volumes
are large and there can be another use for the sulfur. The challenges
become greater when H2S exists in small quantities. Developing a
way to cost effectively manage the substance is challenging, but
possible.
In general, sulfur is an element that is necessary to sustain life.
When sulfur is within an aerobic digestion wastewater system, it is
readily converted to an odourless sulfate. When sulfurs are present
in an anaerobic process, such as anaerobic digestion, however, H2S,
mercaptans or thiols can be formed. The odours associated with
sulfides can range from the smell of garlic to rotten eggs and worse.
The wastewater team at a given facility needs a strategy to
actively treat H2S in the wastewater stream, rather than wait for it
to become an issue that can create problems at the facility or in
the community. There are several good ways to treat H2S, each
with its own advantages and disadvantages. These strategies may

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 Table 2. Comparison of redox control methods
Method Efficiency Typical Typical Typical Mechanism Side Effect on Benefits Issues
of redox losses w/ energy method of dose reactions ecosystem
control ea 1 mg/l required application rates
DO rise for quantity
above 0 dissolution required
(power)
Pure 2% 0.0 - 0.3 Continuous 8 - 10 g Maintains Biological Improves High Good
oxygen kW/kg dissolved O2/m3 high dissolved BOD removal. biodiversity efficiency. dissolution
oxygen; 5 - 10 lb/ oxygen Promotes and aerobic Low required
automatically lb H2S preventing bacterial treatment. agitation of to ensure
controlled reduction of activity. High basin. economics.
injection sulfur species. dissolved Small
Local oxygen footprint.
oxidation of for final No
sulfur species discharge. chemical
by biological handling.
and chemical Fully
processes to automated.
H2SO4, SO4 Low power.
and S.
Air 10% 0.8 kW/kg Continuous 50 - 100 g Maintains Biological Improves Low Dissolution
surface O2/m3 dissolved BOD removal. biodiversity technology rates drop
aeration (150 - 300 g oxygen levels Stripping of and aerobic investment. in warm
air/m3) > 0.5 mg/l dissolved treatment. weather,
preventing H2S due to when
reduction of nitrogen biological
sulfur species. waste gas. activity
increases.
Waste
nitrogen
gas can
cause over
mixing and
exacerbate
the release
of H2S from
the system.
Air will
strip H2S
at effluent
inlet due to
high volume
waste
nitrogen.
H2O2 N/A N/A Batch N/A Local Chemical Effectively Emergency Biological
delivery and reaction chemical oxidation disinfects control of destruction
application not DO reaction to S. of organic local H2S levels. stimulates
rise 1 - 5 Stochiometric compounds injection increased
lb/lb 1:1 but in and biological region activity and
@ 100% process nearer components. entirely anaerobic
H2O2 5:1. Decomposes stopping processes
to oxygen and water once
water. treatment. oxidation
potential
lost.
Hazardous
chemical
handling.
Usually
very local
injection
required.

vary by treatment type and include equalisation ponds, anaerobic
ponds and deep storage industrial ponds.
In general, the goal for H2S control in an equalisation pond is
to keep organic material in solution and move it along quickly so
that anaerobic conditions do not develop. Anaerobic ponds are
the largest challenge, as sulfide gas bubbles (most commonly H2S)
can rise from the pond. Strategies to eliminate this include pH
control, stripping with scrubbing, and oxidation reduction
potential (ORP) control/oxidation. Deep industrial ponds can
encounter the same issues as anaerobic ponds, but on a more
seasonal basis. In general, the concepts of pH control, stripping
and scrubbing, and ORP control/oxidation are the best means to
control sulfur in wastewater.
The level of acidity in the treatment basin can be a key way
to make sure H2S does not leave the basin. When wastewater has
a pH level of >9, nearly all H2S will stay in solution as HS and

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Figure 1. Air Products' Halia® mixer aeration
system, consisting of oxygen supply, either as
liquid oxygen or onsite generation, combined with
OxyMix® technology jointly developed by
Aqua-Aerobic Systems, Inc. and Air Products.
Figure 2. OxyMix® technology installed in a
wastewater treatment tank.
will not exit the treatment area. This may sound like a simple
approach, however, in biological wastewater, the micro
organisms are the key to treatment. These organisms cannot
live in such a high pH environment. The challenge is that for
these organisms to be healthy, pH must be much closer to
neutral. Doing so keeps the bacteria healthy, but it does not
keep the H2S in solution.
Another means of controlling H2S is stripping it from the
stream with air or CO2 and then scrubbing the H2S. This tends to
be a costly approach due to the large volume of water that
would need to be stripped of H2S, as well as the operating cost
of a scrubber. In most instances, this is not the chosen path of
treatment.
The most common approach in water treatment is ORP
control/oxidation. Oxidation involves the reaction of H2S with
oxygen (O2) to form sulfur (S), sulfate (SO4), sulfuric acid (H2SO4)
or other soluble sulfur compounds. In this way, the challenge of
H2S is changed to an alternate chemical that is more simply
treated or controlled. The issue with oxidation is that it requires
the oxygen molecule in the wastewater at a concentration high
enough to react with the H2S without slipping into anaerobic
conditions. Ponds or treatment basins try to maintain dissolved
oxygen (DO) content at an acceptable level, but due to process
variation and seasonality, DO levels will vary.
A summary of the different types of control for sulfur species
odour is shown in Table 1. As described above, there are multiple
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paths to consider, but the most common path, especially when
anaerobic issues are the root cause, is oxidation.
When employing oxidation or ORP control techniques,
process demand variance or seasonality require a dynamic way to
control the input of oxygen. These variations can be controlled
proactively or reactively. A proactive approach is to install the
necessary wastewater equipment to make sure that the dissolved
oxygen level is relatively consistent. A reactive approach is to
wait for the pond or treatment basin to be overcome with an
impurity and then treat on an as needed basis. The reactive
approach can be lower cost if H2S does not start to leave the
treatment system. However, if the levels of the gas leave the
water and create a toxic or odorous environment, the price can
be quite high both in cost and company image.
Oxidation and ORP control
The most common way of controlling sulfur species in a
lagoon or treatment pond is through oxidation or redox/ORP
control. Achieving the necessary level of dissolved oxygen in
the pond or treatment basin requires air, pure oxygen or
hydrogen peroxide. Each of these substances has pros and
cons, which are compared in Table 2.
Air typically has the lowest operating cost; however, due
to the way oxygen is added to the treatment pond, air can
actually cause more H2S to leave the pond than it stops
through reaction with the oxygen. Typically, air is not a
reliable means for control due to the possibility of stripping
and the seasonal variability of O2 retention with temperature.
Although oxygen in air is readily available, the challenge
is getting it into the water solution. Large air based mixers
and aerators can require large horsepower motors and
significant capital to get enough oxygen into the water
solution. One issue this may create is an increase in overall
VOCs into the atmosphere by stripping the treatment pond
of impurities and pushing them into the air. Additionally, over
mixing the pond can exacerbate the release of H2S because
of the high volume of waste nitrogen coupled with increased
sediment disturbance in lagoon type basins. Also, dissolution
efficiency rates tend to drop in warm weather when
biological activity increases, requiring even more energy. For
H2S, the air based approach needs to be handled carefully, as
the solution may cause more issues than the initial problem
or vary by season.
Pure oxygen requires unique equipment to ensure
appropriate mixing and distribution in the treatment ponds.
Good dissolution is required to ensure the economics make
sense for oxygen. The safety of oxygen also needs to be
carefully understood, and special consideration of the
handling and care for the equipment is necessary. Oxygen
based equipment can add the product without stripping the
VOCs. Several methods involve adding the O2 under water in
ways that increase its ability to mix with the wastewater
based on a sensor’s measurement of dissolved oxygen.
Lastly, hydrogen peroxide (H2O2) can offer a solution.
Typically, H2O2 is used as a reactive approach to water
treatment. Ongoing supply can be challenging to distribute
appropriately, which lends itself to be more of a reactive
means of control. Since distribution and control are
challenges, the cost in terms of product, labour and yield are
significant issues. Due to the substance’s high degree of
reactivity, H2O2 can react with Table 3. Choosing the right oxygen supply mode
impurities other than H2S, Supply features
thereby reducing its ability to Flow range (tpd)
effectively treat H2S. One of
Commitment
these side reactions is biological
destruction of organisms in the Time to implement (months)
basin, which can stimulate a Location limitations
second activity in anaerobic Application best fit
processes once oxidation Flow
potential is lost. The safety of
Use pattern
using H2O2, which requires
hazardous chemical handling, *Gas piped in from remote air seperation plant
also increases the cost of this
option.
As illustrated in Table 2, oxidation through the use of pure
oxygen creates the safest and lowest cost option.
Oxygen injection
Pure oxygen can be injected into wastewater in a number of
ways. For years, this approach has been used in activated sludge
systems to boost the dissolved oxygen content when other
means have been exhausted. Oxygen tends to be a way to boost
a treatment pond’s performance without increasing its size.
These same methods are also good for the treatment of H2S. In
the treatment of H2S, oxygen tends to be better because it does
not lift impurities in the air through stripping, and most of the
O2 is injected into the water without significant agitation of the
pond.
Some typical ways of adding oxygen are: diffusion into a
pipeline, diffusion into a grid in the treatment pond, a floating mixer
aerator unit or a floating diffuser based system. Each of these
systems varies in yield and complexity. The simplest way to add the
pure O2 is through basic diffusion. This can be done by adding O2
through a lance into a line of water that feeds the treatment basin.
Another simple way is to have a static diffusion grid in the treatment
pond bubbling oxygen through the depth of the pond. Each way has
definite limits on efficiency. Typically, only 10 - 15% of the oxygen
put into the pipe or diffusion grid is captured by the water, and the
rest escapes into the atmosphere.
There are several other approaches that use a more complex
method for adding oxygen. Diffusion based forced water/oxygen
systems can be operated. Industrial gas companies like Air Products
offer this type of equipment. Oxygen efficiency can reach up to 90%
under specific operating parameters. Air Products offers such items
as the Halia® Mixer Aerator and the Halia® Venturi Aerator units for
both deep and shallow treatment pond conditions. These units,
pictured below, can add up to 10 000 lb/d of oxygen per unit to a
treatment zone.
Oxygen supply
The supply of oxygen is also an area where great expertise is needed.
Oxygen can be provided from a liquid oxygen tank or an onsite
generator.
The most common mode of supply for delivered oxygen is via on
road liquid oxygen tankers from a central manufacturing facility. The
oxygen is stored as a liquid at the site in an insulated tank and
vaporised at the time of use. This is the most flexible mode of supply.
Oxygen can also be generated onsite using cryogenic or
adsorption technologies. At locations in the vicinity of an oxygen
pipeline, supply via pipeline could be the most cost effective and
Liquid oxygen Onsite generation Pipeline*
0 - 50 50 - 150+ 100+
Low High Medium
1 - 2 10 - 18 6-8
Yes No Yes
Low Medium/high High
Variable Steady Variable/steady
flexible source of oxygen. Evaluating the optimal mode of supply
requires the review of a host of factors, including:
nn Size of the oxygen requirement (average and peak demand).
nn Expected use pattern (continuous, seasonal, erratic).
nn Presence of other nearby oxygen consuming applications, such
as ozone.
nn Power availability and cost.
nn Proximity of delivered oxygen source.
Table 3 provides rough guidance about the best mode of
supply in the context of these parameters. From the early stages of
the project, an industrial gas company like Air Products will work
closely with a wastewater treatment plant to jointly determine the
best mode of oxygen supply.
Conclusion
Sulfur species are problematic for many industries. However, there
is hope for a way to control this substance even when treatment
conditions are variable. Equipment designed to use pure oxygen
with an accompanying DO probe and a programmable logic
controller can maintain the necessary dissolved oxygen content
required to transition H2S and other sulfur species into treatable
sulfates. Other types of treatment can prove to be more costly or
create more problems than they solve. For example, temporary
fixes, such as hydrogen peroxide, do not solve the issue. Use of
H2O2 is costly, creates safety challenges, and is not a permanent
solution. The more practical solution is pure oxygen, which
provides a continuous supply to a treatment pond without
exposure to a hazardous chemical for workers and without danger
of hurting or causing an issue with the planned biological treatment
of the wastewater.
References
1. Hydrogen Sulfide; MSDS No. 300000000081; Air Products: Allentown,
Pa., February 8, 2014.
2. MOUSSAVI et al., The Removal of H2S from Process Air by Diffusion
into Activated Sludge, Env Tech, Vol 28, pp. 987 - 993, 2007.
3. HJORTH et al., Redox Potential as a Means to Control the Treatment of
Slurry to Lower H2S Emissions, Sensors 2012, 12,
pp. 5349 - 5362.
4. Septicity in Sewers: Causes, Consequences and Containment, Boon
1995, Water Sci tech, Vol 31, No 7, pp. 237 - 253.
5. Metcalf and Eddy Wastewater Engineering 2003 Fourth Edition.
6. EPA: Process Design Manual for Sulfide Control in Sanitary Sewerage
Systems 1974.
7. Economical, Efficient and Effective Mixing: Three Approaches to
Controlling Odor in Wastewater Treatment Ponds – White Paper
Medora Corp.
8. NIELSEN at al., Aerobic and Anaerobic Transformations of Sulphide in
a Sewer, WEFTEC 2006.
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