WASTE-HEAT DRIVEN THERMAL AMMONIA

STRIPPING AS A MEANS OF AMMONIACAL

NITROGEN CONTROL
R. Eden 1, M. Moulden 1, J. Westwood 1, T. Thomas 2

1
Organics Ltd, University of Warwick Science Park, Coventry, CV47EZ, England
2 Dept of Engineering, University of Warwick, Coventry, CV47AL, England

ABSTRACT: The removal of ammonia from leachate, and wastewater in general, can be accomplished
by means of biological processes or physicochemical process technologies, such as break-point
chlorination. This paper is concerned with thermal ammonia stripping, a technology developed for use
in Hong Kong where the demand for high-concentration ammonia removal, combined with a lack of
space and the plentiful availability of waste-heat, provided the right conditions for this technology to be
applied. High-strength ammonia removal is now becoming more of an issue globally, both with landfill
sites and anaerobic digesters. This paper explains the background to the technology developed in
Hong Kong, explores the basis of improvements in thermal efficiency and reviews novel developments
to capture and recover ammonia for re-use.

Keywords: Leachate, digestate, ammonia, thermal air-stripping, ammonium salt, anhydrous ammonia

1. INTRODUCTION

In aqueous solution, ammonia exists in two forms: unionised ammonia (NH3) and ionised ammonia
(NH4+), with NH3 being the form that is toxic to most fish species, even at extremely low concentrations.
Ammonia is also one of the most commonly produced chemicals in the world, with around 200 million
tonnes produced in 2018. The fertiliser industry uses approximately 85% of global production. The
manufacture of ammonia is, therefore, crucial for the world's agricultural industry. From it, all fertilisers
that contain nitrogen are produced. However, when ammonia penetrates through to parts of the
environment where it is unwanted, it becomes a source of damage to human health and ecosystems.
As such, treatment of ammoniated wastewater streams is a perennial issue to be addressed.
There are many approaches that may be taken to successfully address the problem. The real issue
is not so much what can be done, but which of the available options is the best for the specific
circumstances under consideration.

2. TECHNOLOGIES USED FOR AMMONIA CONTROL

In terms of ammonia removal options, the classic biological nitrogen cycle has provided various
robust approaches employing bacteria, which are well known and widely applied. These biological
nitrogen-removal processes include nitrification, nitritation, and anammox. Oxygen and carbon are

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variously applied (anammox does not require carbon addition) to manage bacterial colonies which will
reduce ammonia concentrations, whilst producing varying amounts of sludge and carbon dioxide.
The alternative approach of physical-chemical ammonia management has had a mixed application
history. These technologies include breakpoint chlorination, ion exchange, electro-dialysis and ammonia
stripping. Each method has its optimum point of application, but the use of any of these is not as
widespread as biological methods.

2.1 Summary of different options for ammonia management

Being a long-term global issue, there have been several different approaches developed over the
years for the removal of ammonia from wastewater. The most often implemented solution has been,
until more recently, the use of bacteria. Whilst the comparatively recent discovery of the Anammox
bacteria demonstrates how much is yet to be understood about the biology, in practice understanding
has been sufficient for theory and empirical implementation to produce robust and reliable approaches.

2.1.1 Biological nitrification

Biological nitrification is widely employed, well understood and generally reliable. The process
involves the nitrification of ammonia into nitrate, a form of fixed nitrogen which is less toxic than
ammonia. Biological nitrification is a two-step process. In the first step, Nitrosomonas bacteria, a family
of nutrient eating bacteria, convert ammonium (NH4+) into nitrite (NO2). In the second step, Nitrobacter
bacteria consume NO2 to produce nitrate (NO3). NO3 is a form of fixed nitrogen that plants and
microorganisms can absorb. It also readily decomposes into nitrogen gas, making it the desired final
product of most biological nitrification processes. Biological nitrification is a simple and cost-effective
ammonia treatment process that is currently widely employed to treat the bulk of ammonia pollution.
With higher-strength ammonia loadings, the system can become less attractive. Large holding
volumes are required, significant air (oxygen) and carbon-source additions are also required. The
process may also produce nitrous oxide (N20), a potent greenhouse gas. This latter issue is becoming
of particular concern to managers addressing the carbon footprint of water treatment works to meet
stringent new requirements. N2O has a Global Warming Potential 265–298 times that of CO2 for a 100-
year timescale. N2O emitted today remains in the atmosphere for more than 100 years, on average.

2.1.2 Anaerobic ammonium oxidation (Anammox)

In 1995 researchers discovered that Anammox, a previously unknown bacterium, was converting
ammonia directly into N2 in a fluidised bed reactor. Anammox biological treatment is, therefore, a
relatively new method of biologically processing ammonia and nitrites directly into N2. Contrasted with
biological nitrification, which is a two-step process, anammox bacteria convert ammonia and nitrites
directly into N2 and H2O, bypassing the traditional denitrification process.
Anammox is largely compatible with many existing biological nitrification facilities, thus permitting
existing facilities to be retrofitted with anammox technology. The bacteria involved have several distinct
advantages over other forms of biological nitrification. For example, far less sludge is produced that by
conventional biological nitrification. This is because fewer bacteria are required for the anammox
process. The process can be carried out in smaller tanks. Fewer consumable chemicals, such as for pH
adjustment and nutrient addition, are required to maintain the process. Oxygen consumption is up to
60% less and no organic carbon is required to sustain anoxic bacteria.
However, set against these advantages, anammox bacteria multiply at a slower rate than
Nitrosomonas bacteria. They are slower to rebound from a system upset. The low growth rate of the
bacteria can reduce the rate at which ammonia is processed. The use of Anammox bacteria therefore
requires a higher level of process supervision and risk-management.

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2.1.3 Breakpoint chlorination
Breakpoint chlorination removes ammonia by converting it into various chloramines, dependant upon
the pH of the water. Chloramines are mild, non-toxic disinfectants that contribute to the overall free
residual chlorine level in water. However, a ratio of approximately 8:1, chlorine to ammonia, is required
to convert all of the ammonia into chloramines. In this application, chlorination occurs when enough
chlorine is present in the water to react with all of the free organics and the targeted ammonia.
Breakpoint chlorination can completely remove free ammonia from wastewater, removing any costs
and environmental hazards associated with disposing of a waste product.
The major limiting factor, apart from the need to control the water temperature and pH, is
consumption of free chlorine by other contaminants, such as organic compounds, as measured by BOD
and COD. It is also noted that breakpoint chlorination cannot remove nitrate and nitrites from
wastewater.

2.1.4 Zeolite ion exchange

Zeolites work by trapping targeted ions and releasing sodium ions in their place. Many everyday
laundry and dishwasher detergents contain zeolites to remove calcium and magnesium, thereby
softening water so they work more effectively. The same functionality is employed to remove ammonia
from wastewater streams, by swapping the ammonium ions in the wastewater with other cations
(usually sodium) held in the zeolite.
There are multiple methods of regenerating zeolite, depending on the system and type of zeolite
used. In general, the trapped ions are released and replaced with sodium ions. In the case of ammonia
removal, an ammonia wastewater stream may be produced which, in turn will require treatment. Thus,
simply displacing the treatment of ammonia. Zeolites can remove virtually all of the ammonia present in
wastewater. For this reason, final polishing steps in ammonia removal systems often use zeolites. The
capacity limits of zeolites, combined with the need to treat ammonia after regeneration, make the
application of zeolites specific to small-scale situations, such as aquaculture and swimming pools.

2.1.5 Membrane ion exchange

An ion-exchange membrane is a semi-permeable membrane that transports certain dissolved ions,
while blocking other ions or neutral molecules. Ion-exchange membranes are electrically conductive.
They are often used in desalination and chemical recovery applications, moving ions from one solution
to another with little passage of water.
Ammonium passes through a membrane into an ionic fluid, driven by means of electrical power.
Ammonium ion may be recovered from the fluid or converted to nitrogen gas. As such membrane ion
exchange may be viewed as a concentrating technology. When combined with sulphuric acid, a salt can
be produced which may have some value. The focus here is on power consumption. Reported figures
are to the order of 8.5 kWhr/kg of ammonia removed. On this basis, a facility treating 10 tonnes per day
of ammonia would have an electrical load for the membrane of approximately 3.5 MW.

2.1.6 Membrane contactors

With membrane contractors, ammonia gas is diffused through a hydrophobic membrane into
sulphuric acid under osmotic pressure. The wastewater pH needs to be increased to c.10 in order to
break the ammonium ion bond and produce ammonia gas. As with membrane ion exchange, the
product ammonium sulphate may be a product with commercial value, thereby reducing the net process
cost.

2.1.7 pH driven air stripping

Ammonia removal from wastewater can be facilitated by means of raising the pH of wastewater. This
adjustment to pH will convert the ammonium ion to ammonia gas, permitting the stripping of the

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ammonia gas from the wastewater with air. This approach requires a pH of over 10, leading to a
potentially significant operating cost for chemicals. Where the pH must be less than 10 for discharge,
further chemicals will be required to reduce the pH. A large air flow is necessary to achieve stripping by
this means, usually in the region of 3000:1, air to wastewater. Whilst in theory it is possible to achieve
high removal rates, in practice it is difficult to achieve better than 80%. Once ammonia has been so
removed from wastewater, it must be removed from the stripping air. The main options here are acid
scrubbing and catalytic combustion.

2.1.8 Thermally driven air stripping

Ammonia removal from wastewater can also be facilitated by mean of raising the wastewater
temperature. As with pH adjustment, the addition of heat will assist with breaking the ammonium ion
bond, making the ammonia gas available for removal by means of air stripping. Where waste heat is not
available, either in the form of a waste fuel-gas or thermal energy, heating will lead to significant
operational costs and render the process non-viable.

3. THEORY BEHIND THERMAL AMMONIA STRIPPING

Ammonia stripping entails the passage of a gas, usually air, counter-current to a liquid stream to
release and remove ammonia gas. The problem is, however, that ammonia is held as an ion, NH 4+, in
wastewater when at around a neutral pH. At ambient temperatures and neutral pH, the ammonium ion
bond will not break to release ammonia gas, NH3. It is, therefore, locked in. The solution to this problem
is to either raise the pH or the temperature of the wastewater, or both. An elevated temperature or pH
will break the ammonium ion bond and release the ammonia gas into solution, ready for removal.

3.1 Basic Equations

The equation governing the relationship between ammonia gas and the ammonium ion may be written
as follows:

NH4+ + OH-  NH3 + H2O

Dissociated ammonia ion (NH4+) is converted to undissociated ammonia gas (NH3) by the addition of a
base (OH-), such as sodium hydroxide. As the temperature of the water increases, so the amount of
free ammonia gas also increases.

The ratio of ammonia in the gas phase to the total ammoniacal nitrogen, referred to as ‘f‘, may be
expressed as follows:

f = [NH3] / [NH3] + [NH4+]

The relationship between pH, temperature and ‘f‘ takes the general form represented in Figure 1
below.
In practice, as well as the conversion of NH4+ to NH3, there is a considerable amount of related
chemical activity taking place in a thermal ammonia stripper. Heating a wastewater will generally reduce
its pH. At 25oC, the pH of pure water is 7. If the temperature is increased to 100oC, the pH of pure water
is 6.14. This drop in pH mitigates against thermal stripping and may lead to the rapid precipitation of
solids.
However, as well as ammonia, thermal stripping removes carbon dioxide. The relationship between
pH, alkalinity and carbon dioxide is a complex one. The pH of a wastewater stream will decrease as the

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carbon dioxide content increases. This results from carbon dioxide reacting with water to form carbonic
acid. Similarly, the pH of wastewater will increase as carbon dioxide is removed, which enhances the
conversion of ammonium ions to ammonia gas.

Figure 1. Relationship between pH, temperature and ‘f’

4. OPTIMUM USE OF THERMAL AMMONIA STRIPPING

As will be apparent from the range of technologies available for ammonia removal from wastewater,
there is not one technical solution to suit all situations where ammonia requires treatment. Each
situation has its unique demands, which in turn suggests that all technologies have an optimum point of
application. That is certainly the case for thermal ammonia stripping, where key aspects may make this
approach highly suitable or render it inappropriate.

4.1 Key requirements for thermal ammonia stripping

Being a thermal process, the most important requirement is that there should exist a source of heat
which with not incur a premium-fuel charge. Approximately 25.0 kWhr thermal is required per kg of
ammonia removed. This figure is subject to the wastewater concentration of ammonia, making the
process more suitable for high-strength ammonia concentrations. For a facility rated at 3.0 tonnes per
day ammonia removal and destruction, this would equate to approximately 3.0 MW thermal. As well as
ammonia concentration, this figure is a function of initial pH and alkalinity.

4.2 Enhancing attributes

As well as constraints to beneficial implementation, there are a number of attributes which indicate
situations of optimum deployment.
• High removal rates in a relatively small footprint
• No major costs for chemical additions
• Mitigation of Green House Gas production by avoiding nitrous oxide formation (N2O)
• Relatively rapid start-up, when compared to biological processes
• No risk of biological failure
• No sludge formation
• The system is relatively easy to operate, compared to biological processes
• Substantial savings may be available from avoidance of carbon-source costs

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 One of the major attractions of the thermal ammonia stripping route is that large quantities of
ammonia that can be removed from liquid streams in a relatively small footprint. The first Hong Kong
facility, for example, was designed to remove 12 tonnes per day of ammonia in a footprint of
approximately 170 square metres. This was with a feed concentration of 6,700 mg/L, reducing to an
effluent concentration of less than 100 mg/L.
It is a significant added benefit that, where applied, no major costs are incurred for chemical
additions. It is usually not necessary to adjust the pH, although pH, and alkalinity in particular, are
factors that impact upon performance. Leachate, anaerobic digestate effluent and anaerobic digester
side-stream flows, have a pH and alkalinity which do not require adjustment. With regards to carbon-
source, it is not necessary to add any at all. This latter can represent a considerable saving in situations
where carbon-source is expensive to procure.
Nitrous oxide is an undesirable by-product of the biological ammonia treatment cycle. When
removed by conversion of the ammonium ion to ammonia gas, nitrous oxide is not created.
Start-up is measured in minutes or hours, rather than days or weeks. Being a physical chemical
process, once the operating conditions are achieved the plant will start performing. A typical start-up
may be in less than one hour for smaller units and less than two hours for larger systems.
The absence of a biological dimension to the treatment process means there is no risk of poisoning.
With Anamox bacteria, for example, bacteriological failure can lead to a considerable loss of processing
capacity. The absence of bacteria also means that is no sludge formation and no sludge disposal
problem.

4.3 Detracting attributes

As well as the requirement for a viable thermal source of process heat, there are other issues which
need to be managed and which may detract from the attractiveness of the process in certain situations
and applications.
• Requirement for acid scrubbing or commercial ammonia capture, where combustion is not an option
• Scale formation on packing surfaces
• Intensive electro-mechanical process

Where waste heat, or an alternative viable source of heat, is not available, the significant thermal
load would normally render thermal ammonia stripping too costly to operate.
Where waste heat is available in the form of steam, or heat from an engine exhaust, for example,
there will be, subsequent to removal, a requirement to remove ammonia gas from stripping air by either
acid scrubbing, ammonia capture, or a catalytic converter. Using biogas or syngas as a source of heat
is, therefore, preferred. Here, by means of thermal oxidation, ammonia removed from wastewater can
be converted directly into nitrogen and water.
A notable feature of thermal ammonia stripping is packing scaling, usually in the form of magnesium
or calcium carbonate. Whilst it is possible to reduce the impact of this problem, by reducing carbonate
alkalinity in the feedwater, such an approach would lead to a reduction in pH and necessitate the
addition of chemicals to raise the pH for the stripping process to proceed. In practice it has been found
that the preferred solution is to design speedy packing removal and replacement systems. A shut down
of one or two days can usually be accommodated in the largest industrial scale plant, where
maintenance shutdowns can be planned ahead.
Whilst for many this may not be a decisive negative attribute, there is no doubt that thermal ammonia
stripping represents an intensive thermo-mechanical process. Noise is not generally an issue but there
are many moving parts which need to be monitored and maintained.

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5. HONG KONG EXPERIENCE WITH THERMAL AMMONIA STRIPPING

In 1997, following extensive pilot trials and process evaluation, air stripping was eventually chosen
as the core nitrogen removal process for the West New Territories (WENT) landfill site in Hong Kong,
currently operated by Suez. The plant has been operational since 1998 and has a design flow rate of
1,800 m3/day, recently upgraded to 3,350 m3/day. (Figure 2) The initial design duty for this first plant
was with an influent of 6,700 mg/L, to be reduced to an effluent of 100 mg/L. The WENT facility now
removes 14.5 tonnes of ammonium ion per day. Subsequently, similar processes have been installed
on six additional sites around Hong Kong, with largest single unit having a capacity of 2,600 m3/day,
with one other site having a total installed treatment capacity of 4,000 m3/day. The thermal stripping
process was installed as a front-end add-on to an existing biological leachate treatment plant at the
North East New Territories (NENT) landfill, where a change in the consented discharge concentration
required considerably lower effluent total nitrogen (Figure 3).

Figure 2. WENT Ammonia Stripping Plant rated at 3,250 m3/day

Figure 3. NENT Ammonia Stripping Plant rated at 2,500 m3/day

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 The air-stripping process used at all six sites incorporates two defining features:
• the process is carried out at elevated temperatures, avoiding the need for alkali addition
• the stripped ammonia is oxidised thermally to nitrogen gas, avoiding the more typical route of
scrubbing with sulphuric acid and the consequent problem of its disposal.
In Hong Kong, being a densely populated area, there is generally a shortage of available land on
which to build biological wastewater treatment facilities. Historically, there has also been a great deal of
landfill gas available. The instruction with the first unit constructed was to use as much landfill gas as
possible, the balance being simply flared. In the event the unit was designed with a landfill gas flow rate
of 6,000 cubic metres per hour.
Clearly, this is not a replicable situation, except for in Hong Kong. Landfill gas was seen to be more
of a nuisance than an opportunity. The electrical grid in Hong Kong is supported by a significant excess
capacity, meaning that in 1997 additional small-scale electricity generation was not encouraged.
This position has gradually changed over the years, the Hong Kong authorities having moved to
encourage the production of renewable energy. The landfill sites in question have seen their landfill gas
production rates decline with time. The issue of thermal load has moved from a requirement to
maximise gas-use to one of minimisation.

6. RECENT DEVELOPMENTS

As stated above, it is possible to remove ammonia gas from stripping air with an acid scrubber.
Where such an approach is feasible, the form of waste-heat used to drive the process will not need to
be a combustible gas. The problem here, however, is that comparatively large quantities of acid will be
required on a daily basis. As an indication of quantum, 1 tonne per day of ammonia removal with
require approximately 2 tonnes per day of phosphoric acid or 3 tonnes per day of sulphuric acid.
In conjunction with staff from the University of Warwick Department of Engineering, a process has
been developed which involves recovery of either ammonium hydroxide or the production of anhydrous
ammonia. This approach further develops two key process themes: employing waste heat and avoiding
the use of chemicals. Ammonia-water systems are well understood and widely applied in refrigeration
and adsorption cooling. The Process Flow Diagram (PFD) for a system recovering ammonia is provided
in Figure 4 below. Clean, cold water is used to remove ammonia from stripping air. The water is then
heated to concentrate the ammonia gas as ammonium hydroxide. Additional concentration and
separation will lead to the production of anhydrous ammonia.

Figure 4. Ammonia recovery process PFD

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7. FUTURE POSSIBILITIES

The possibility of producing anhydrous ammonia leads on to the question of what to do with it. There
exist many options, from simple combustion on site to beneficial use. Ammonia is used in a wide range
of applications, from pharmaceuticals and agriculture, to industrial cleaning and explosives. Ammonia
can exist either as a gas or a liquid. Under pressure it actually has no smell at all. However, once
exposed to the air, it’s impact on human physiology can be so strong that prolonged exposure will
desensitise the human nose.
The energy content of liquid ammonia is 11.5 MJ/L, or approximately 30% that of diesel. Ammonia
may be used in fuel-cells, which offers the potential for a local, beneficial means of disposal. Ammonia
may also be used in engines, with ammonia as the fuel. During World War II ammonia was used to
power buses in Belgium.
Ammonia has been proposed as a practical alternative to fossil fuel for internal combustion engines.
Its high-octane rating of 120 and low flame temperature allows the use of high compression ratios
without the penalty of high NOx production. Since ammonia contains no carbon, its combustion cannot
produce carbon dioxide, carbon monoxide, hydrocarbons, or soot.
Ammonia is joining the growing list of substances which need to be prevented from polluting the
environment and, where practical, can be recycled. Using waste heat to meet these objectives assists
with ensuring a long-term sustainable solution to the challenge of ammonia pollution.

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