An Overview of

Ammonia and Nitrogen Removal

in Wastewater Treatment
Tim Constantine, CH2M HILL Canada

February 19th, 2008

Knowledge Commitment... Integrity at Your Service

Presentation Overview
Ammonia Removal

Why remove it?

Regulations
Nitrification biochemistry and factors
Design considerations and example

N-Removal

Why remove it?

Regulations
Denitrification biochemistry and factors
Design considerations and example

Return liquors from dewatering

2

Ammonia Removal

Introduction
Why removal ammonia?
A nutrient, so can promote algae growth
Can exert oxygen demand in receiver
Free or un-ionized fraction is toxic to aquatic life

What technologies remove ammonia?

Breakpoint Chlorination
Air stripping
Ion exchange
Biological methods

Focus of this presentation will be biological methods

Uptake of ammonia during biological growth (heterotrophs)
Biological nitrification
4

Regulations and Basis for Limits

In certain cases, effluent ammonia limits based on
limiting oxygen demand in receiver
More often, limits set based on toxicity to aquatic life
Free ammonia fraction is toxic:
Chronic toxicity limit ~ 0.02 mg/L (after mixing in receiver)
Acute toxicity limit ~ 0.1 mg/L (at end of pipe)
+
NH4+
NH
+
H
3

Dissociation constant pKa = 9.24

Impacted by pH and temperature
At pH 7.5, 15oC, about 1% of TAN is NH3-N
So to achieve 0.1 NH3, need to be below 10 mgN/L
5

Nitrification Biochemistry
Nitrification is a two-step reaction:
+

AOB

NOB

NH4 + 1.5O2 NO2- + 2H+ + H2O

NO2 + 0.5O2 NO3 More about the nitrification reaction:

Nitrifiers do not use organic carbon as basis for growth

Building blocks for growth from alkalinity
4.57 g O2 consumed per g ammonia oxidized to nitrate
Acid formed, consumes alkalinity, 7.14 g alkalinity per g NO3
Nitrite intermediate almost never stable, nitrite oxidizers grow
faster than ammonia oxidizers at typical WW temperatures

What Impacts Nitrification?

pH
Optimal pH for nitrification between 7 - 8.5
pH below 6 can lead to inhibition

Alkalinity
Alkalinity is the carbon source for nitrifier growth
Do not want to go below 50 mg/L as CaCO3, or pH
For 21 mg/L ammonia nitrified, require 200 mg/L alkalinity
7.14 x 21 +50 ~ 200 mg/L

Low Oxygen
Nitrifiers are strict aerobes, inhibited at very low DO levels
As long as DO > 2 mg/L, little impact on nitrifier growth rate
7

What Impacts Nitrification?

Inhibitory substances

Nitrifiers can be sensitive to a number of compounds

Can impact growth rate
Higher concentration = Lower growth rate or complete loss
Classic example is free ammonia and nitrous acid inhibition

Solids Retention Time (SRT) and nitrifier growth

Concept of minimum SRT is really important!

Min. SRT =

1
max,N - bN

If operating SRT > min. SRT, nitrification takes place

If operating SRT< min. SRT, no nitrification
8

The Washout Phenomenon of Nitrification

30

T = 12oC
Effluent Ammonia [mgN/L]

25

20

15

10

0
9

Design
SRT

Minimum
SRT

Solids Retention Time [days]

What Impacts Nitrification?

Wastewater Temperature
Single greatest impact on nitrification
Nitrifiers are much more sensitive to temperature than
heterotrophic bacteria
Drives the design sizing of aeration tanks in colder climates

10

Temperature Effect on Minimum SRT

30

Effluent Ammonia [mgN/L]

25

20

15

10

Design
SRT

Minimum
SRT

11

Lower
Temp

Higher
Temp

Solids Retention Time [days]

Temperature Effect on Nitrification

Solids Retention Time [days]

12

10

Design SRT
6

Minimum SRT
10

12

12

14

16

Wastewater Temperature [oC]

18

20

Design Considerations for

Nitrification
What do we need to select/determine?
Bioreactor volume requirements
Tank configuration
Oxygen requirements

13

Bioreactor Volume for Nitrification

Critical parameters for bioreactor volume sizing:
Design aerobic SRT
Raw wastewater characteristics
Selected operating MLSS

Selection of Design Aerobic SRT

Almost always based on coldest wastewater temperature
If good historical data available, use minimum week effluent
temperature
Aerobic SRT selection might be impacted by effluent limits, but
not normally
Typical coldest temperature in Ontario is 10oC
In this case, design aerobic SRT of 8-10 days is typical
14

Bioreactor Volume for Nitrification

Raw wastewater (or primary effluent) characteristics:

Can have major impact on sizing of tankage

Nitrifiers only make up ~1-2% of MLSS
TSS/BOD feed to bioreactor is most important
Should do rigorous review of historical data to determine design
characteristics
For bioreactor sizing, look at peak month characteristics
At times, peak month loading can coincide with minimum
wastewater temperature
Good example is a university town, where population is higher in
winter/spring
Peak month loading of 1.2x average annual is typical

15

Bioreactor Volume for Nitrification

Design MLSS concentration:
Optimal in terms of aeration tankage and secondary clarifier
sizing is 2,500 3,000 mg/L
Higher MLSS values can be used, but usually means very large
secondary clarifier to account for higher solids loading

16

Design Example (Guelph Plant 4)

Design Conditions:
Average design flow = 22 MLD
Minimum week WW temperature = 10oC
Design Aerobic SRT = 9 days
Average Primary Effluent cBOD5 = 140 mg/L
Peak Month Loading factor = 1.3
Design MLSS = 2,500 mg/L (2.5 kg/m3)

Used process model, but simple design shown below

17

MLSS yield (from model) = 0.9 mgMLSS / mg cBOD5

ML Mass Required = 0.9 * (22 MLD) * (140 mg/L) * (1.3) * (9 d)
ML Mass Required = 32,500 kg
Volume = 32,500 kg / 2.5 kg/m3 = 13,000 m3
HRT = 13,000 / 22,000 m3/d = 14 hours

Bioreactor Volume
Plant 1 = 4,350 m3
Plant 4 = 13,000 m3
Plant 4

Plant 3
Plant 2
Plant 1

Same Secondary
Clarifier Size
18

Bioreactor Oxygen Requirements

Aeration is required for:
Supply oxygen for biological processes
Mixing

For mixing, minimum requirements:

Mechanical aeration = 5 W / m3 of tankage
Diffused air = 0.3 L/s per m3 of tankage

Oxygen specifically used for:

Oxidation of organic matter (BOD)
Nitrification
Endogenous decay

19

Actual Oxygen Requirements [kgO2/day]

SRT/nitrification Impact on O2 Demand

Including
Nitrification

Without
Nitrification

T = 20oC
1

20

Solids Retention Time [days]

10

Bioreactor Oxygen Requirements

Other design considerations:
Dont forget about recycle streams
Need sufficient oxygen transfer for to meet peak diurnal oxygen
demand during peak day loading
Dont forget about minimum mixing criteria, especially in last
pass of an aeration tank
Consider using fine bubble aeration

21

Aeration Efficiency

1.6

1.6
1.4
1.2
1
Efficiency
0.8
(kg O2/kWh)
0.6
0.4

1.2
0.8

0.2
0
Coarse Bubble
Spiral Roll

Mechanical
Aeration

Fine Bubble

Fine bubble aeration can reduce aeration energy by 25 to 50%

22

Bioreactor Oxygen Requirements

Other design considerations:
Dont forget about recycle streams
Need sufficient oxygen transfer for to meet peak diurnal oxygen
demand during peak design period
Dont forget about minimum mixing criteria, especially in last
pass of an aeration tank
Consider using fine bubble aeration
Consider providing DO sensors with feedback loop to blowers

23

DO Control can Provide Savings

No DO Control (47 kW)

50

45

40

With DO Control (35 kW)

Aeration Energy Required (kW)

35

30

25

20

15

10

24

10

15
Time (hours)

20

Bioreactor Oxygen Requirements

Other design considerations:
Dont forget about recycle streams
Need sufficient oxygen transfer for to meet peak diurnal oxygen
demand during peak design period
Dont forget about minimum mixing criteria, especially in last
pass of an aeration tank
Consider using fine bubble aeration
Consider providing DO sensors with feedback loop to blowers
Do provide tapering of air diffusers, typically:
Pass 1 = 50% of O2 demand
Pass 2 = 30% of O2 demand
Pass 3 = 20% of O2 demand
25

Nitrogen Removal

26

Introduction
Why remove nitrogen?
A requirement for biological phosphorus removal
High nitrate levels associated with methemoglobinemia (blue baby
syndrome)
A nutrient, can lead to growth harmful algal blooms and hypoxic
conditions

Many jurisdictions now have effluent TN limits:

EU countries 70-80% N removal but varies
Bubble Limits in sensitive watersheds (e.g. Chesapeake Bay)

Canada now has effluent nitrate limits

13 mg/L as nitrate ion after mixing
Equivalent to 2.9 mgN/L nitrate
27

Nitrogen Removal Intro

There are a number of technologies capable of removing
nitrogen:

Breakpoint chlorination of ammonia

Ion exchange (ammonia or nitrate)
Air stripping of ammonia
Biological removal

How is nitrogen removed in biological systems?

A certain amount of nitrogen is required for biomass growth
By nitrification / denitrification
By deammonification (Anammox)

28

Nitrogen Removal - Denitrification

Denitrification is defined as growth of bacteria when nitrate is
used as the terminal electron acceptor:
Organic
Compound

+ NO3 Biomass + CO2 + N2

Different from aerobic growth in that nitrate is used instead of

oxygen
Majority of heterotrophic bacteria in WW treatment can use
both oxygen and nitrate
If oxygen is present, it will be used before nitrate
Oxygen inhibits denitrification
29

Consequences of Denitrification
Reduction in total oxygen required, as part of organic
material is oxidized using nitrate
Nitrification:
Denitrification:

4.57 mgO2/mgN
2.86 mgO2/mgN

63% savings

Actual O2 savings depends on:

Raw WW characteristics
Process configuration and process design

Alkalinity is formed during denitrification!

Recover 50% of alkalinity lost through nitrification
More stable pH, since alkalinity serves as pH buffer

30

Requirements for Denitrification

Need nitrate to be formed
Nitrate is formed during nitrification
As long as system is nitrifying, this criterion is met

Need denit or anoxic zone in system:

31

Nitrate
Bacteria
Substrate
No oxygen, but mixing to retain biomass in suspension

re
-

ae
ra
tio
n

The Wuhrmann process

NH3NO3
Aerobic

32

NO3N2
Anoxic

Process can virtually removal all nitrogen

Substrate for denitrification via endogenous decay
For high N-removal, anoxic zone very large
In practice, re-aeration step is usually added

The Ludzack-Ettinger process

NO3N2

NH3NO3

Anoxic

Aerobic

Readily biodegradable substrate used for denitrification

Significantly higher denitrification rate compared to
Wurhmann
Only removes nitrate associated with the RAS
If RAS = Qave, 50% nitrate removal if carbon not limiting
33

Modified Ludzack-Ettinger process

NO3N2

NH3NO3

Anoxic

Aerobic

MLE process includes recirculation to bring greater

quantities of nitrate back for denitrification
Much higher levels of nitrate removal possible
Very popular process alternative today
34

Impact of Recycle Rate on MLE

90%

80%

Nitrate Removal [%]

70%

60%

50%

40%

30%

20%

10%

100%

35

200%

300%

400%

Recirculation Rate [% of influent flow]

500%

4-Stage Bardenpho process

re

-a
er
at
io
n

MeOH

Anoxic

Aerobic

Anoxic

Combination of MLE and Wuhrmann process

Very high levels of nitrate reduction possible
External carbon source (methanol) often added to
increase second stage denitrification rate
36

Design Considerations for

Denitrification
Do not take away required aerobic SRT to provide
anoxic zones
Unless providing only seasonal denitrification via swing
zones

Size anoxic zones appropriately and provide mixing

Minimum SRT for MLE anoxic zone ~ 1.5 days

Kinetics of denitrification are fairly complex, and very

dependent on nature of COD (readily biodegradable,
slowly biodegradable)
Carry out raw wastewater characterization
Use a process model to assist in design sizing

37

Design zones to allow free flowing surface

Minimize O2 return in recycle streams

Sidestream Treatment

38

Centrate Characteristics / Impacts

Parameter
Flow:
TSS:
BOD5:
Phosphorus:
Ammonia:
Temperature:

Centrate
1,750 mg/L
200 mg/L
200 mg/L
1,000 mg/L
~35C

% of Influent
0.5%
4.0%
0.5%
19.0%
20.0%
-

Major impacts:
Increased oxygen demand
Increased carbon requirements for denitrification
Can lead to bleed through of NH3 / NO3 if not equalized
39

Secondary Effluent Ammonia [mgN/L]

Impact of Centrate on Performance

10
With Centrate added
over 8 hours

No Centrate

0:00

12:00

0:00

Time of Day
40

12:00

Centrate Management Alternatives

Centrate Management
Alternatives

Separate
Treatment

No Separate
Treatment
- Do Nothing
- Centrate Equalization

Phys-Chem
Treatment
- Hot Air/Steam Stripping
- Ion Exchange
- Breakpoint Chlorination
- Struvite Precipitation

41

Biological
Treatment
- Suspended Growth Activated Sludge
- Fixed Film
- Bioaugmentation (e.g. BABE, InNitri)
- Nitritation (e.g. SHARON, AT-3, others)
- Anammox (deammonification)

Process Overview - Bioaugmentation

What is it?
Side-stream treatment process to treat centrate
Produces enriched population of nitrifiers
Nitrifiers seeded to mainstream plant

Benefit:
Reduce ammonia (nitrogen) load on mainstream plant
Allows improved nitrification in mainstream plant

A number of treatment processes:

InNitri (Inexpensive Nitrification)
BABE (Bio-Augmentation Batch Enhanced)
Nitrification in RAS reaeration (ScanDeNi, Prague)
42

Process Overview - Bioaugmentation

Influent

PC

SC

Bioreactor

Effluent

RAS
RAS

RAS
InNitri
BABEreaeration
Process

43

Nitrifiers

25oC
30
Sidestream
System

Dewatering
Centrate
Alkalinity/
Methanol

Improved mainstream nitrification efficiency

Typically allows 30% less bioreactor volume
Requires supplemental chemicals
Process still emerging some full scale
installations

Bioaugmentation Benefits Mainstream

Effluent Ammonia [mgN/L]

12

10

Without
Bioaugmentation

Effluent with
Bioaugmentation
4

Design basis: 10oC

1

Mainstream Aerobic SRT [days]

44

10

Process Overview - Nitritation

What is it?
Process that converts ammonia to nitrite (NH3 NO2)
Partial nitrification in side-stream system

Benefits:
Reduced O2 (25% less than full nitrification)
Reduced chemicals (e.g. 40% less MeOH for denitrification)
Less tankage than bioaugmentation

A number of treatment processes:

Solids retention time control (SHARON Process)
Toxicity control (e.g. AT-3 process)
Dissolved oxygen control
45

Process Overview - SHARON

Solids Retention Time [days]

NO3

Nitrite
Oxidizers

Ammonia
Oxidizers

NO2

NH3
10

15

20

25

Temperature [oC]
46

30

35

40

Process Overview - Anammox

Anammox:
Anaerobic Ammonium Oxidation

New organisms discovered - Anammox bacteria

NH4-N + NO2-N

N2 + 2H2O

Notable properties of anammox bacteria:

Very low growth rate (1/10th that of nitrifiers!)
Inhibited by oxygen even at very low levels

Key: Generate both NH3 and NO2

47

Process Overview - Anammox

SHARON
Reactor
Alkalinity?
Methanol ?

30oC

Dewatering
Centrate

N2
NH
30o3C
NO2
Anammox
Reactor

Effluent

Influent
WAS

RAS

Efficient N-removal:
60% savings in oxygen, 100% savings in carbon

Long start-up, requires good solids retention

Full-scale: Rotterdam, Strass
48

Centrate Processes - Which is best?

Example 1:
Limitations in nitrification or denitrification capacity
Low cost secondary treatment expansion
Bioaugmentation may be best

Example 2:
No Limitation on nitrification or denitrification capacity
Limitation in influent carbon or want to limit operating costs
Nitritation or Anammox may be best

Example 3:
No major limitations in nit/denit capacity
Equalization
49

Summary
There will continue to be increased needs in
providing nitrification and N-removal
Many options available for both systems
Good process design practice should include:
Raw WW characterization
Process simulation

Centrate treatment alternatives emerging, may solve

upgrade challenges for nitrification or N-removal

50

An Overview of
Ammonia and Nitrogen Removal
in Wastewater Treatment
Tim Constantine, CH2M HILL Canada

Thank you for your attention!

February 19th, 2008

Knowledge Commitment... Integrity at Your Service