CHEMICAL PHOSPHOROUS

REMOVAL AND ONLINE

ANALYSIS
This Presentation:
– Overview of Chemical Treatment Fundamentals
– Chemical Control Strategy
– Online Analyzer Evaluation
 Statement of the Problem
Controlling phosphorous discharged from municipal and
industrial wastewater treatment plants is a key factor in
preventing eutrophication of surface waters.

Phosphorous is one of the major nutrients contributing in the

increased eutrophication of lakes and natural waters. Its
presence causes many water quality problems:
• increased purification costs
• decreased recreational and conservation value of an
impoundment
• loss of livestock and the possible lethal effect of algal
toxins on drinking water.
Municipal wastewaters may contain from 5 to 20 mg/l of
total phosphorous, of which 1-5 mg/l is organic and the rest
in inorganic form.
– Orthophosphates: available for biological metabolism without
further breakdown
– Polyphosphates: molecules with 2 or more phosphorous atoms,
oxygen and in some cases hydrogen atoms combine in a
complex molecule. Usually polyphosphates undergo hydrolysis
and revert to the orthophosphate forms. This process is usually
quite slow.
 Chemical Treatment
Chemical treatment for phosphorus removal involves the addition of
metal salts to react with soluble phosphate to form solid precipitates
that are removed by solids separation processes including clarification
and filtration The most common metal salts used are :

• Alum (aluminum sulfate), sodium aluminate

• Calcium (lime)

• Ferric chloride, ferric sulfate and ferrous chloride

Chemical treatment is the most common method used for phosphorus
removal to meet effluent concentrations below 1.0 mg/L.
 Aluminum
Alum or hydrated aluminum sulphate is widely used precipitating
phosphates and aluminum phosphates (AlPO4). The basic reaction is:

Al3+ + HnPO43-n ↔ AlPO4 + nH+

The dosage rate required is a function of the phosphorous removal
required. The efficiency of coagulation falls as the concentration of
phosphorous decreases. In practice, an 80-90% removal rate is
achieved at coagulant dosage rates between 50 and 200 mg/l.
 Calcium
Usually added in the form of lime Ca(OH)2. It reacts with the natural alkalinity in the
wastewater to produce calcium carbonate, which is primarily responsible for
enhancing SS removal.
Ca(HCO3)2 + Ca(OH)2 à 2CaCO3 ↓+ 2H2O
As the pH value of the wastewater increases beyond about 10, excess calcium ions
will then react with the phosphate, to precipitate in hydroxylapatite:
10 Ca2+ + 6 PO43- + 2 OH- ↔ Ca10(PO4)*6(OH)2 ↓

Because the reaction is between the lime and the alkalinity of the wastewater,
the quantity required will be, in general, independent of the amount of
phosphate present. It will depend primarily on the alkalinity of the wastewater.
The lime dose required can be approximated at 1.5 times the alkalinity as
CaCO3. Neutralisation may be required to reduce pH before subsequent
treatment or disposal. Re-carbonation with carbon dioxide (CO2) is used to
lower the pH value.
 Iron Salts
Ferric chloride or sulphate and ferrous sulphate are all widely used for
phosphorous removal, although the actual reactions are not fully
understood. The basic reaction is:

Fe3+ + HnPO43-n ↔ FePO4 + nH+

Ferric ions combine to form ferric phosphate. They react slowly with the
natural alkalinity and so a coagulant aid, such as lime, if added, would
raise the pH and enhance the coagulation.
 Chemical Dose
The required chemical dose is related to the liquid phosphorus
concentration. For target concentrations above 2 mg/L (appropriate for
chemical addition to a primary clarifier), a dose of 1.0 mole of aluminum
or iron per mole of phosphorus is sufficient.

For lower phosphorus concentrations in the range of 0.3 – 1.0 mg/L,

the dose can be in the range of 1.2 to 4.0 moles aluminum or iron per
mole of phosphorus.

The pH value is an important factor for efficient removal of phosphorus

using alum or other salts, as the solubility of their precipitates vary with
pH. Phosphorus removal is most efficient in the pH range of 5 to 7 for
alum and of 6.5 to 7.5 for ferric salts..
 The first process is included in the
general category of chemical precipitation
processes. Phosphorous is removed with
90% efficiency and the final P
concentration can be lower than 1.0 mg/l.

The coprecipitation process is particularly

suitable for active sludge plants, where
the chemicals are fed directly in the
aeration tank or before it. The continuous
sludge recirculation, together with the
coagulation-flocculation and adsorption
process due to active sludge, allows a
reduction in chemical consumption.

The postprecipitation is treatment of a

secondary effluent, usually using only
metallic reagents. It is the process that
gives the highest efficiency in
phosphorous removal. Efficiency can
reach 95%, and P concentration in the
effluent can be lower than 0.5 mg/l.
Postprecipitation gives also a good
removal of the SS that escape the final
sedimentation of the secondary process.
 Chemical Addition Pros and Cons
PRO
• – reliable
• – low levels of P in effluent possible
• – Retrofit for existing plant likely possible

CON
• – cost of chemical feed system
• – cost of chemicals
• – substantial additional sludge production
• – chemical sludge reuse or disposal may be more difficult
• – may need to adjust pH
 Sludge Production
With chemical addition, sludge production will
increase in the wastewater treatment unit process
where the chemical is applied. Sludge production
has been noted to increase:

• by 40 percent in the primary treatment process

• 26 percent in activated sludge plants
 Chemical Dose Determination
The most important component of a control strategy for chemical
phosphorous removal is the calculation of coagulant dosage. Dosage
rates for aluminum salts or for iron salts are based on the molar ratio of
available metal ion to phosphorous.

Theoretically to remove 1 mg/L of PO4-P you need

•
9.6 mg/L of Alum
•
5.2 mg/L of Ferric Chloride

Real life requires 0.5 to 15 times as much

 Chemical Dose Determination
Jar Testing or Bench Testing – using a simple method to determine wastewater
characteristics and real metal to phosphorus ratios required at different chemical injection
locations.

Historical Trending – if historical data is sufficient to demonstrate hourly, daily or monthly

phosphorus loading patterns, the varying chemical dosing levels can be configured via
with the plant’s SCADA system using these trends.

Third party laboratory analysis – data used for reporting purposes. This data can also be
used to fine-tune chemical dosage, but the long wait times are a problem for “real time”
control. Increasing analysis costs are another concern if multiple sample locations are
monitored.

Plant’s lab analysis – chemical dosage is adjusted based on the data collected and
analyzed in laboratory by the plant staff. This is a labor consuming process and difficult
for the “real time” process adjustments.
 Chemical Dose Determination
Proper control is difficult to achieve using manual techniques such as
grab samples and periodic jar tests. There are several reasons for this
difficulty:
• incoming phosphate concentrations can vary in unpredictable ways as a
result of industrial contributions.
• incoming phosphate concentrations are RARELY in proportion to flow
• conversion of polyphosphate to orthophosphate prior to coagulant addition
will affect coagulation efficiency. Process conditions, particularly pH and
temperature, can significantly influence polyphosphate conversion.
• if reclaimed products such as pickle liquor are used as a coagulant, the
concentration of available metal ion will also be variable. This will result in a
highly variable phosphate coagulation rate and, in the absence of on-line
monitoring, will require frequent manual adjustments to avoid overfeed or
underfeed.
 Chemical Dose Determination
Insufficient coagulant dosages can produce an effluent with excessive
turbidity, but excessive coagulant dosage can also produce the same
result. Surplus coagulants can also have an adverse effect on
disinfection processes, by exerting an oxidation demand. Surplus
metal salts can coat ultraviolet disinfection tube surfaces. Thus, it is
important that the process be well controlled.
 Solids Separation
As effluent permit limits for phosphorus are commonly
expressed as total phosphorus, precipitation of the soluble
phosphorus (orthophosphates) into a particulate form is
only a part of the job.

The solids separation step (clarification and/or filtration)

must be capable of removing the effluent TSS. The more
TSS removed the lower concentration of Total
Phosphorous.
 Monitoring Strategy
The monitoring strategy will depend on the chemical addition point and
on the control strategy to be employed.

• Orthophosphate should be monitored at frequent timed intervals from a point in the process prior
to coagulant addition. The sample point should be after the point at which polyphosphate has
been converted to orthophosphate. This is usually not at the headworks, but after primary
clarification or immediately after influent addition to the aeration tanks. Filtration of suspended
solids may be required prior to analysis, but should not affect accuracy, since the soluble
phosphate is the parameter of interest.

• A sample point following coagulation can be selected to monitor the efficacy of the coagulation
process. The sample point may be the effluent from a final clarifier, or effluent filtration.
Orthophosphate measured at this sample point represents the fraction of dissolved phosphate that
remains after coagulation. Typically 60-80% of the total phosphorous.
A PROPOSED SOLUTION – ONLINE ORTHO
PHOSPHATE ANALYZER

– Online Phosphorus Analyzer

• Real time
• Continuous monitoring
• SCADA-linked for automatic dosing control
• Flexible for “feed forward” or “feed back” control
• Assure Permit Compliance
– Key – Chemical Saving
 Ortho-P vs. Total-P
– Total Phosphorus
• Organic portion
• inorganic portion
– Why measure ortho-P in process control
• Ortho-P is dissolved portion
• Chemical precipitation removes Ortho-P
• Relationship between ortho-P and Total-P
– Clarifier or filtration performance is important
Phosphorus Analyzer
Selection
– Check References
• Confirm reliability
• Maintenance requirements
– Interference compensation
– Self-cleaning and self-zeroing
• Prevents optical cell fouling
• Self –zeroing restores background
Phosphorus Analyzer
Selection
– Sample handling
• High turbidity samples may require filtering
• Filter cleaning requirements
– Maintenance requirement
• Weekly, monthly, annual
– Overall cost of ownership
• Cost of reagents, spare parts, cleaning
chemicals
 Effluent Sampling
Effluent Sampler Effluent Reuse or (W3)
 On Line Analysis
In general, phosphate analyzers are the complex
integrations of chemical, electrical and mechanical
technologies:
– Labor saving
– Speed of data acquisition
– Consistency, reliability and accuracy

But saving labor and acquiring data are not justified if the
online analyzer only adds a maintenance burden or if the
analyzer is not reliable.
Installations & Case Histories
Sheboygan, Wisconsin
– WWTP servicing population of 50,000 - EBPR
– Current phosphorus limit was 1.0 mg/l
– Ferric chloride spending $160,000 annual at the 1.0 mg/L
limit
– First online phosphate analyzer installed in 2010
– Second online phosphate analyzer installed in 2012
– data “feed back” to SCADA for ferric chloride dosing
control
– Chemical savings $$$ paid for analyzer in 4 months.
Installations & Case Histories
New London, Wisconsin
• 2 MGD design activated sludge process plant
• Phosphorus permit limit 1.0 mg/l
• Online analyzer data “feed back” direct to
chemical feed pump for ferric chloride dosing
control
• $900 per month chemical expense saving
Installations & Case Histories
– Kiel, Wisconsin
• 0.9 MGD activated sludge process
• Phosphorus permit limit 1.0 mg/l
• A cheese packaging factory is the major
contribution source
• Online analyzer data “feed back” to SCADA for
ferrous sulfate dosing
• 20% chemical expense saving
 In Conclusion
Meeting tightening discharge limitation with
chemical phosphorous removal can require:
• Quick response to concentration changes
• Respond to process changes
• Chemical cost savings
• Reduce of maintenance burden