Control of Struvite Deposition in

Wastewater Treatment Plants

Paul L. Bishop
Associate Vice President for Research
University of Cincinnati
11th Annual Central States Water Environment Association
Education Conference
April 4, 2006

Typical Municipal WWTP Flow Diagram

Incoming Wastewater

Bar Screen

Dissolved Air
Flotation Tank

Screenings
Gravity
Thickener

Grit Chamber

Grits

Primary
Clarifier
Anaerobic Sludge
Digester

Return Activated Sludge

Aeration Tanks

Secondary
Clarifier

Chlorine Contact Tank

Plant Effluent

Sludge Dewatering
Facility

Sludge to Incinerator,
Farmland or Landfill

Centrate/Filtrate

Further Dewatering

Problems

Anaerobic sludge digestion releases

ammonium, magnesium and phosphate,
which can form struvite in digesters and
downstream dewatering facilities

Can result in scaling in pipelines and on walls

of process equipment

Centrate or filtrate from sludge dewatering

is usually returned to the plant headworks
where it can add to the wastewater burden

Struvite

Magnesium ammonium phosphate

MgNH4PO4 6H2O

Named after Russian diplomat, H.G. von Struve (17721851)

White, yellowish white, or brownish white in color

FW = 245.41

Specific density = 1.7

Very insoluble in water, pKso = 12.6 13.15 at 25oC

Struvite Chemistry
NH4+ NH3 (aq) + H+

pKa=9.3

H3PO4 H2PO4- + H+

pKa1= 2.1

H2PO4- HPO42- + H+

pKa2= 7.2

HPO42- PO43- + H+

pKa3= 12.3

MgOH+ Mg2+ + OH-

pK=2.56

MgNH4PO4.6H2O Mg2+ + NH4+ +PO43- + 6H2O

pK=12.6

Struvite formation occurs when the conditions are

such that the concentration product exceeds the
struvite conditional solubility product

Conditional Solubility of Struvite vs pH

Ps = conditional solubility product

Kso = solubility product

P s C T ,M g C T ,N H 3 C T ,P O 4

K so

M g 2 N H P O 3 M g 2 N H P O 3
4

CT,Mg = total concentration of all soluble magnesium species

CT,NH3 = total concentration of all soluble ammonia species
CT,PO4 = total concentration of all soluble phosphate species
i = ionization fraction for component i
i = activity coefficient for component i

Struvite Formation in Sludge

Dewatering Process
Anaerobically digested sludge, anaerobic supernatant (centrate/filtrate)
Mixing & perturbations
Carbon dioxide stripping
pH elevation
Phosphate equilibrium shifts towards PO43[Mg2+] [NH4+][PO43-] exceeds struvite solubility product (super-saturation)
Nucleation and crystal growth

Struvite precipitates

MgNH4PO4 . 6H2O

Filtrate return line

Struvite encrusted roller

Ball check

Productivity lost!!

(Courtesy Schaners Waste Water Products, Inc.)

Problems with Current Struvite

Control Techniques
Addition of iron chloride to form
vivianite (Fe3(PO4)2 . 8H2O)
Chloride concentration increases
Ferric ion acts as an acid, lowering pH
Large volume inorganic sludge generation
Phosphate recovery from ferric phosphate
salt(s) is nearly impossible
Similar problems with ferric sulfate or alum

Objective
Investigate the use of magnesium
hydroxide to remove nutrients in a
controlled fashion from digested
sludge
Can use waste flue gas desulfurization
sludge as a source of Mg(OH)2

Characterization of Mg(OH)2: Basic

Properties that are Important to
Wastewater Treatment Applications

Magnesium Hydroxide Dissolution Kinetics

10
9.5
9

pH

8.5
8
7.5
7
6.5
6
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00

Time (min)

Titration Curves of Several

Neutralization Chemicals
14
12

pH

10
8
6
C

2
0
0

0.002

0.004

0.006

Titrant Added (eq.)

A = calcium hydroxide; B = pure magnesium
hydroxide; C = sodium carbonate; D = as-received
magnesium hydroxide slurry

1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0

Buffering Capacity(eq/pH)

Relative Neutralization Capacity

Relative Neutralization Capacity and

Buffering Capacity of Several
Neutralization Reagents (at pH = 8.5)
0.0035
0.003
0.0025
0.002
0.0015
0.001
0.0005
0

1 = pure magnesium hydroxide; 2 = sodium carbonate; 3 =

calcium hydroxide; 4 = as-received magnesium hydroxide
slurry.

Summary
Mg(OH)2 has unique features compared with other
commonly used chemicals:
slow dissolution process
high neutralization capacity
high buffering intensity

Sludge Digestion Enhancement

Using Mg(OH)2

NH3-N, PO43--P, Mg2+, Ca2+ and SO42- Changes

During Anaerobic Sludge Digestion

Biogas Production Profiles During

Anaerobic Sludge Digestion

Summary
Applying magnesium hydroxide into an anaerobic
sludge digester can:

Result in greater destruction of COD and SS

Enhance the production rate of biogas
Increase overall treatment efficiency
Reduce level of nutrients in the supernatant that must
be
returned to the plants headworks
Increase the nutrient content in the generated biosolids
for agricultural use
Improved sludge dewaterability, which will ease the
operation of the down stream sludge dewatering
facilities

Nutrient Removal from Anaerobically

Digested Sludge and Sludge Supernatant
Using Mg(OH)2

Nutrient Removal from Digested Sludge

Pilot Scale Experimental Results on

Phosphate Removal from Centrate

Total phosphorus mass balance without metal phosphate precipitation from centrate/filtrate
Influent

310

100

effluent

Primary + secondary
treatment systems

10

300
Sludge digester

300
Filtrate/centrate

210

sludge cake

Sludge dewatering

90

Total phosphorus mass balance with metal phosphate precipitation from centrate/filtrate
Influent

100
Treated filtrate/
centrate

107
7

effluent

Primary + secondary
treatment systems

10

97
Sludge digester

97
Metal phosphate
precipitation reactor

Filtrate/centrate

68

Sludge dewatering

P-containing chemical sludge

61

sludge cake +
chemical sludge

29

90

Summary

Use of Mg(OH)2 to remove nutrients from

anaerobically digested sludge is effective
only if the sludge is well digested.

Removing phosphate from the side waste

stream will:

reduce the nutrient load to the headworks of the

treatment plant (this is a current practice that
adversely affects the overall treatment efficiency)

lower the potential for struvite formation, which is

a frequently occurring O&M problem in many
municipal wastewater treatment plants

generate a slow release fertilizer

Improving the Settleability and

Dewaterability of Activated Sludge:
Applications of Mg(OH)2

350

700

300

600

250

500

200

400

150

300

100

200

50

100

0
0

20

40

60

80

Mg(OH)2 Dosage (mg/L)

100

0
120

SV(ml/L)

SVI

Effect of Mg(OH)2 on Activated

Sludge Settleability

Surface Charge Density Changes vs

Mg(OH)2 Dosage
COO-

---Mg2+ ---

OOC

Relative Surface Charge

NH3

NH3

2
1
0
-1 0

20

40

60

80

100

-2
-3
-4
-5
-6
-7

Magnesium Hydroxide Addition (mg/L)

Mixed Liquor Sedimentation Curves under

Different Mg(OH)2 Dosage Conditions
Height of water/sludge interface (cm)

180
160

Mg(OH)2: 0 mg/L
Mg(OH)2: 100 mg/L

140

Mg(OH)2: 300 mg/L

Mg(OH)2: 500 mg/L

120
100
80
60
40
0:00:00

0:14:24

0:28:48

0:43:12

0:57:36

Time (hour:minute:second)

1:12:00

1:26:24

Sludge Dewaterability Changes with the

Addition of Mg(OH)2
CST (seconds)

290
285
280
275
270
265
260
255
0

50

100

150

Mg(OH)2 Dosage (mg/L)

200

Summary

By charge neutralization, sweep

flocculation and Mg2+ bridging between the
EPS matrices of the microorganisms,
Mg(OH)2 is effective in improving the
settleability of activated sludge
Besides enhancing the overall sludge
digestion process efficiency, Mg(OH)2
application to anaerobic sludge digester
can also generate a digested sludge that
is easier to dewater

Conclusions
Mg(OH)2 improved the biological phosphate uptake
and release behavior of activated sludge
Mg2+ was found to stimulate the phosphate uptake
during aeration periods
The pH increase caused by Mg(OH)2 addition
enhanced phosphate release during the anaerobic
sedimentation period
Research results provide supporting evidence for the
potential application of Mg(OH)2 in EBPR processes

Conclusions

Magnesium hydroxide can effectively improve the

settleability of mixed liquor during sedimentation in
secondary clarifier and the dewaterability of
anaerobically digested sludge in sludge dewatering

Magnesium hydroxide can enhance the overall

process efficiency of anaerobic sludge digestion due
to improved pH/alkalinity and the supplementation
of Mg2

Conclusions

Magnesium hydroxide is effective in removing nutrients

from anaerobic supernatant, thus reducing the nutrient load
returned to the headworks of the plant

It minimizes the risk of struvite formation and generates a

good plant fertilizer

Magnesium hydroxide is superior to other commonly used

chemicals in this regard FeCl3, alum and lime.

Aeration (for mixing) plus magnesium chloride (Mg 2+

source) plus struvite seeding proves to be a good process
for controlled struvite crystallization.

Potential Mg(OH)2 Application Locations

in Municipal WWTP