MAP: MAGNESIUM AMMONIA PHOSPHATE

STRUVITE FOULANT

CHEM 409
Group: 21
Natasha Born
Claire Delaney
Aditi Dwibedi
Farhana Karim
Pankti Shah

Executive Summary:
Struvite is a foulant that forms in equimolar ratios of magnesium, ammonia, and phosphate.
This report focuses on struvite formation and removal in pipes of wastewater treatment
plants. The following topics are discussed in the report: formation condition, physical and
chemical properties, control, and recovery of struvite. Chemical methods of controls and
recovery includes chemical treatments, crystallization processes, inhibitors, and enhanced
biological phosphorus removal. Non-chemical methods such as mechanical grinding, hydro-
jetting, and static magnetic fields are are also mentioned. The application of the recovered
struvite as an effective fertilizer and environmental impacts are examined.

Introduction
Struvite, a foulant, forms when there is an equimolar ratio of magnesium, ammonia and
phosphate (MAP) (Doyle et al. 2002). Fouling is the mineral accumulation on the surfaces of
pipes, pumps, valves and other equipment that constricts the flow. Struvite is a crystalline
structure that occurs naturally in rotting organic material such as animal wastes and cow
manure (Su et al. 2014).

Struvite is a type of phosphate-based precipitate and is a nuisance in industrial operations as

it clogs piping and damages equipments. Economically, it is not favourable because of the
associated maintenance and removal costs (Struvite Removal, 2016). In most instances, the
formation and build-up of struvite within the treatment plant goes unnoticed until it reaches a
critical stage where the only option is replacement of the clogged pipes. A method to control
this problem is to regularly monitor the conditions that influence struvite buildup and taking
the appropriate actions as soon as possible. Observing changes in concentration of
phosphorus can provide valuable information on potential struvite formation. The
uncontrolled growth of struvite plagues the wastewater treatment industry, reducing the
plant’s operational efficiency, hydraulic capacity, and increases the maintenance cost.
Appropriate measures must be taken to manage struvite accumulation.

MAP Mechanism

Figure 1

Struvite forms under a wide range of alkaline

conditions with equimolar concentrations of
magnesium, ammonium and phosphate combined
with six water molecules (MgNH4PO4·6H2O) as
shown in Figure 1 (Fattah, 2012). It is an
insoluble salt that can precipitate in places such
as pipes, aerators and pumps, hindering
operations in industrial processes, including
wastewater treatment facilities.

One of the key physical properties of struvite is

its low solubility of 23 mg/L in water (Fattah
2012). It is deposited when the combined
concentration of Mg2+, NH4+ and P043- in
solution exceed this solubility limit. Chemically,
it is very soluble in acidic media and sparingly
soluble under neutral conditions. Pure struvite
occurs as white crystalline powder that can be
found as either tight aggregates of fine crystals,
irregularly shaped coarse crystals, or elongated structures as shown in Figure 2. Variation in
struvite crystal sizes depend on the production conditions and were found to be from 15 μm
to 3.5 mm in length. Morphologies of MAP crystals are identified by scanning electron
microscopy (SEM), but the compositional quality of the crystals can be identified via X-ray
diffraction (XRD) as shown in Figure 2.

Materials

Factors that influence struvite production in pipelines include high surface-area to volume
ratio, pipe material, and surface roughness. Pipelines can be made from metal or plastic
materials. A study comparing struvite buildup in stainless steel, Teflon, and acrylic plastic
pipe coupons revealed that stainless steel had a much higher scaling rate than the two plastics.
Additionally, the scaling rate in the stainless-steel pipe increased dramatically over time
compared to that of the plastic pipes (Doyle et al. 2002). Pipes with rougher surfaces offer
more sites for crystals to grow, increasing struvite production. Therefore, smoother pipes
decrease the mass of struvite formed and prevent the increase in scaling rate over time (Doyle
et al. 2002).

MAP Controls & Recovery

Struvite forms at high turbulence locations such as pipe elbows or pumps, which restricts the
flow and increases the pipeline pressures (Struvite Removal, 2016). Industries usually
implement a formation strategy to predetermine fouling regions. Multiple measures are taken
to control the formation of struvite in addition to the selection of the materials.

Controls: Chemical Treatments

Chemical treatments are commonly used methods of removing struvite build-ups to decrease
the pipeline pressure and increase flow rates (Fattah 2012). Chemical treatments directly
affect several physical and chemical properties of struvite, including its solubility and pH.
These methods remove phosphate ions and inhibit the growth of struvite crystals.
Furthermore, lowering the pH through hydrochloric acid washes creates an acidic
environment that promotes the breakdown of the chemical constituents present in struvite
(Doyle et al. 2002). Dosing with metal salts can mitigate struvite formation as it reduces
phosphate concentrations. Non-corrosive biodegradable organic acids are the most effective
struvite removers in the market today because they are less likely to corrode pipe materials.
Organic acids are often recirculated throughout the system to remove struvite scaling and
prevent future occurrences of fouling. In summary, biodegradable struvite removers dissolve
mineral scaling without contaminating the pipe materials. However, high chemical dosages
are often required, increasing the costs associated with chemical treatments.
Crystallization processes transform the struvite sludge into smaller sized pellets in a fluidized
bed reactor (Su et al. 2014). Fluidized bed reactors have a standard columnar reactor with a
seed material placed on it where the struvite precipitates. The seed materials are commonly
composed of quartz and silica sand that support the crystallization of struvite into small and
larger size pellets. The smaller sized pellets are dissolved further, while the larger sized
pellets release recoverable nutrients such as phosphorous, that can be used in fertilizers.
These methods of phosphate removal are beneficial as they are cost effective, efficient, and
result in products of high purity (Su et al. 2014).

Another method to control struvite formation is to alter the growth mechanisms of these solid
precipitates using inhibitors (Doyle et al. 2002). Sodium hydrogen diphosphate and sodium
polyphosphate are inhibitors that sequester the magnesium present in struvite. The removal
of the magnesium ions prevent the formation of struvite in the reaction as seen in Figure 1.
As per Le Chatelier’s removal of the magnesium ions shifts the reaction to the left. Adding
magnesium ions into the sludge encourages phosphate precipitation and increases the Ksp
(solubility product) at a designated location (Su et al., 2014). Alternatively, enhanced
biological phosphorous removal (EBPR) is a biochemical method that employs the use of
bacteria to selectively remove large chains of phosphates (Doyle et al. 2002). The bacteria
can aggregate the large chains of phosphates within their cells.

Controls: Non - Chemical Treatments

Non-chemical treatments to control and remove struvite include mechanical grinding, which
is physically scraping the struvite (Struvite Removal, 2016). Removal of struvite with hydro-
jetting involves washing the pipelines using high pressure streams of water. Sometimes,
replacement of pipe segments may be necessary. The newest emerging technologies are static
magnetic fields and ultrasonic sound waves that generate vibrations and heat around the
struvite (Bhagat et al. 2015). Drawbacks to mechanical methods are that they require
operations to be stalled, making components affected by struvite inaccessible for long periods
of time.

Recovery

Struvite recovery has proven to be an efficient nutrient recycling method. Boiling struvite in
excess water will result in the loss of five water molecules from its structure forming the
chemical dittmarite. Dittmarite is a monohydrate chemical that contains high levels of
phosphate (Rahman et al. 2013). The conversion of struvite to dittmarite can be exploited to
enhance phosphate recovery from wastewater. However, the economics associated with this
process have not been proven to be cost-effective. Phosphorus recovered from struvite can be
used in the agricultural industry as a fertilizer. Struvite based fertilizers release phosphates at
a slower rate, decreasing the potential for leaching and making it an effective fertilizer (El
Diwani et al. 2006). Controlled production of struvite has economic benefits, as the
maintenance costs for the treatment plants decreases.
Environment Impact of MAP

When struvite is removed from the pipe by chemical means, its physical and chemical
properties change. Through the acid treatment, solid crystal aggregates form sludge that is
easily removed from pipes, pumps, or other affected areas. There are several environmental
concerns associated with discarding the struvite sludge into the sewage system or an aquatic
ecosystem. The struvite sludge discharge contains heavy metal salts such as magnesium, and
high phosphorus bio-wastes that contaminate the aquatic ecosystems through eutrophication
(Su et al. 2014). Eutrophication is excessive richness of nutrients in a lake or other body of
water, frequently due to runoff from the land, that causes a dense growth of plant life and
death of animal life from lack of oxygen. These wastes can also accumulate in soils near
aquatic systems and cause water quality problems. Environmental impacts of struvite sludge
can be reduced through methods of phosphate recovery.

Conclusions
Struvite is a fouling problem mainly in wastewater treatment facilities. The crystalline
properties cause it to attach to surfaces such as pipes, and obstruct the flow. The
accumulation of struvite can lead to higher maintenance costs for wastewater facilities and
other industries affected by this problem. It reduces the flow rates, increases the pressure and
shear stress in the pipe, and affects regular operations. Several measures are taken to control
the formation of struvite such as selection of materials, manipulation of chemical properties,
crystallization, or physical removal. Struvite is an example of a foulant with components that
can be recovered and reused in other applications.

References

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