CIE4485

Wastewater Treatment
Dr.ir. Tommaso Lotti

2. New perspective for N removal: The anammox process

1
New perspective for N removal:
the anammox process

15-11-2012
CITG TU-Delft

Dr. Ir. Tommaso Lotti

email: [email protected]

Delft
University of
Technology

Challenge the future

Sergei Winogradski
1856-1953
Nitrogen Cycle

• 1880: Winogradski - Zurich

 Nitrifying bacteria
• ± 1900: Beijerinck - Delft
 Denitrifying bacteria
 Nitrogen fixing bacteria Martinus Willem Beijerinck
1951-1931

Anammox process 2 | 47
Nitrogen cycle has become a Nitrogen Web

Marc Strous - Bremen

Anammox process 3 | 47

Anammox history
• 60s to 80s
Regular reports of “unexpected nitrogen loss”
Usually interpreted as: Nitrogen removal by
nitrifiers or aerobic deammonification
Likely often due to diffusion limitation and Anammox Bacteria

• 80s: Pilot at Gist brocades Delft with

“unexpected nitrogen loss”
Arnold Mulder/Gijs Kuenen: must be different
organism

• 90s: Recognition of Anammox bacteria made

Anammox processes possible to design and
reliable operate

Anammox process 4 | 47
 Origin of Anammox – Pilot Gist-brocades
CO2 / CH4 / H2S CO2 / CH4 / H2S N2 / CO2 S2- SO42-
gas gas gas NO3- N2
CH2O CO2 + H2O

NH4+, SO42-

Waste Water Fatty Acids NO3-

Kj-N, SO42-, COD NH4+, S2-

Acidification Methanogenesis Denitrification

Anammox process 5 | 47

Anammox
ANaerobic AMMonium OXidation

Predicted in 1979 (based on thermodynamics + evolution)

Discovered by Mulder/Kuenen in 1988/1995 in Delft

Order: Planctomycetales
Characteristic feature: internal compartment, ladderanes

Genetic Diversity:
-Brocadia, Kuenenia (fresh water: several WWTP’s)
-Scalindua (marine conditions: Black sea, Golfo dulce)

Autotrophic (CO2 as carbon source, extremely low growth rate)

Minimal doubling time = 1 week

Anammox process 6 | 47
 HISTORY AND STATUS ANAMMOX - 2007

1999
Worldwide licence Paques BV 2005
1992 1996 2nd full scale
Start development TU Delft Cultivation 1998 Anammox
1988 1995 Anammox Discription of 2002 2006
First Observation First anammox First Full scale 1st full scale
at Gist Brocades Publication microorganism ANAMMOX® Canon

1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006

1988 2007

Anammox process 7 | 47

Anammox process 8 | 47
 Geographic distribution of Anammox bacteria

?
?
?
?

?
?

? Not confirmed “Kuenenia” “Brocadia”

Anammox process“Scalindua”
9 | 47

Geographic distribution of Anammox bacteria

2001: Black Sea:
?
anammox plays
? a role in N2 production
?

2004: Golfo
?
dulce: anammox plays a
significant role in N2 production
2006: Anammox might be responsible for
50 % of the ?denitrification process
?

? Not confirmed “Kuenenia” “Brocadia”

Anammox process“Scalindua”
10 | 47
 GROWTH STOICHIOMETRY

Catabolism: NH4+ + NO2-  N2 + 2 H2O

Anabolism: CO2 + 2 NO2-  CH2O + 2 NO3-

NH4+ + 1.3 NO2- + 0.066 HCO3- + 0.15 H+

1 N2 + 0.3 NO3- + 2 H2O + 0.066 CH2O0,5N0,15

Nitrate Production is Measure for Growth

Anammox process 11 | 47

ANAMMOX PRINCIPLE
Short cut in N-removal

Less Oxygen  less Energy

No Organic Carbon  more Biogas

BUT:
Need for preventing nitrite (NO2-)
oxidation

Very slow growing organism

(approx. 10 times slower)
 Need for good biomass retention

Anammox process 12 | 47
CONVENTIONAL AMMONIUM REMOVAL

Nitrification: 2 NH3 + (3+1) O2  2 NO3- + 2 H+ + 2 H2O

Denitrification: 2 NO3- + 8g COD + 2 H+  N2 + 3g SLUDGE

2 NH3- + 4 O2 + 8g COD  N2 + 3g SLUDGE

AUTOTROPHIC AMMONIUM REMOVAL

Nitritation: NH3 + 1.5 O2  NO2- + H+ + H2O

Anammox: NO2- + NH3 + H+  N2 + 2 H2O

2 NH3- + 1.5 O2  N2

Anammox process 13 | 47

Nitrification/ Nitritation/
NH4+ Denitrification Anammox
aeration aeration
(2.8 kWh/kg N) NH4+
(1 kWh/kg N)

NH4+ NO2-
NO3-
methanol methanol
(3 kg/kg N) (0 kg/kg N)
sludge no sludge
N2

N2 1-3 €/kg N
3-5 €/kg N
0.7 ton CO2/ton N
>4.7 ton CO2/ton N

Anammox process 14 | 47
 Why Nitrogen Removal?
Eutrophication

• Bad Water
• Smell
• Toxic compounds
• Danger for drinking water

Anammox process 15 | 47

GENERAL PROBLEM for WATER TREATMENT:

Increasing standards for nutrient removal

POTENTIAL SOLUTION:

Treatment of NUTRIENTS in flows from

SLUDGE TREATMENT (side stream)
10-30% of N-load (in a small flow)

Anammox process 16 | 47
 NITROGEN REMOVAL IN SIDE STREAMS

SIDE STREAM CHARACTERISTICS:

HIGH concentration SMALL tank volume

HIGH temperature SHORT SRT possible

No absolute need for good effluent

POTENTIALITY:
Remove Nitrogen in compact reactor

Anammox process 17 | 47

APPLICATION IN SIDE STREAM TREATMENT

COD removal N/P
Settler removal Settler

NO3-
N2

Anammox
P.N. Dewatering Digester
NH4+

Water line
NH4+, NO2-
Sludge line
Sludge Digestate
disposal

Anammox process 18 | 47
 Sluisjesdijk-Dokhaven,
WWTP Rotterdam
ROTTERDAM DOKHAVEN
ANAMMOX
2-stage
system PARTIAL
NITRITATION

Water line

Sludge line Sludge line

Anammox process 19 | 47

Anammox® Scale-up

• First application in IC®-reactor  Known

• No sludge available
• Cost of pilot operation relatively high
• Decided to build directly full scale
(from 15 litres to 70 m3)

Anammox process 20 | 47
 Sluisjesdijk-Dokhaven, Rotterdam
800
ANAMMOX FIRST START-UP
700
N load (kg/d) 600
500
400
300
200
100
0
jan-02 jan-03 jan-04 dec-04 jan-06

Anammox process 21 | 47

Sluisjesdijk-Dokhaven, Rotterdam

Anammox process 22 | 47
 Sluisjesdijk-Dokhaven, Rotterdam

Stable operation since

early 2006

7 kgN/m3.day
800 kg/day

Anammox process 23 | 47

Integrating Nitritation/Anammox

1 mm

Anammox process 24 | 47
Integrating Nitritation/Anammox

O2

NO2-
NH4+
N2

NO3-
NH4+
NH4+

2 NH3 + 1.7 O2  1.14 NO2- + 0.86 Anammox

NH3  process
0.88 N2 +250.24
| 47 NO
3

One Reactor Anammox systems

(1-stage partial nitritation-anammox)

Essentially based on UASB technology with:

- Fine bubble aeration
- Simple tilted plate settlers (TPS)
- No need for influent distribution

Process control based on:

- Measurement of Ammonium
- Influencing DO by variable aeration

Anammox process 26 | 47
 Anammox granular sludge reactor
Spec. volume load: 2 kg N/m3/d
TSS: 10 kg ds/m3

effluent

pH

O2

Digestor effluent NO2-N

air NH4-N

Anammox process 27 | 47

Impression of the internals

Anammox process 28 | 47
 2 different configurations applied
for partial nitritation - anammox
divided in 2 reactor all in one single reactor

different biomass

Anammox process 29 | 47

Current Anammox Based Technologies

Implemented at Full Scale
• Flocculent - SBR (Switzerland, EAWAG)
• Flocs/Granular (Austria, Bernard Wett)
• Biofilm on carrier - MBBR (Sweden, Anox-Kaldness; AnitaMOX, Veolia;
DeAmmon Purac)
• Granular (Netherlands/China, Paques)

Anammox process 30 | 47
 Which to chose ???

2-stage (2 distinct reactors):

• the partial nitritation and the anammox step can be optimized individually,
including nitratation suppression in the first stage
• lower risk for anammox to be overgrown by heterotrophs
• smaller inoculum needed
• no risk for oxygen inhibition

1-stage (only 1 reactor):

• investment costs are significantly lower
• the process control is less complex
• lower risk for nitrite inhibition
• less N2O emissions: 0.4-1.3 vs 2.3-6.6% of N-load

Anammox process 31 | 47

Flocs or biofilm (granules) ???

• Sludge water: Suspended COD
 Biofilm or Granular sludge to prevent accumulation
of inert sludge

• Oxygen Control
 Biofilm or Granular Sludge allow higher DO (1 mgO2/l) and continuous aeration
(cost of aeration equipment)

• Volume
 Granular sludge allows more compact reactor design
Pure Anammox > 10 kgN/m3.day
Nitritation/Anammox ~ 3 - 4 kgN/m2.day

• Start-up
 Granular Sludge/Carriers – longer startup from scratch
but easier to transport/long life time

FLOCCULENT BIOFILM
Biomass Retention - +
Reactor Volume - +
Process Stability
- +
(COD, solids)
Startup + +Anammox
- process 32 | 47
 Recent Startup in China
Largest load: 11 ton N/d

Volume:
6700 m3

Load:
1.7 kgN/m3.day

Startup time:
1 month
(95% conversion)

Anammox process 33 | 47

16 ANAMMOX® references - spring 2012

• STW Rotterdam (NL) 700 kg N/d
• Semiconductor Industry (JP) 220 kg N/d
• Tannery (NL) 325 kg N/d
• STW Switzerland (CH) 60 kg N/d
• STW Olburgen (NL) 1200 kg N/d
• Yeast Industry (CN) 1000 kg N/d
• Fermentation Industry (CN) 11000 kg N/d
• Fermentation Industry (CN) 9000 kg N/d
• Fermentation Industry (CN) 10700 kg N/d
• Yeast Industry (CN) 7000 kg N/d
• Distillery (PL) 1200 kg N/d
• STW Zwolle (NL) 660 kg N/d */**
• Food Industry (CN) 2200 kg N/d **
• Food Industry (CN) 6100 kg N/d **
• STW Minworth (UK) 4000 kg N/d **
• Winery (CN) 900 kg N/d
• * Conversion of existing Sharon into One Step Anammox
Anammox process 34 | 47
 Side Stream Treatment - last note

Usually only 10-15 % of total N-load

More measures needed to really improve effluent concentration

• WWTP optimization:
- Improve COD removal by precipitation/flocculation
- Effluent recycle for extra denitrification
- Better sludge thickening

 Increased N-load to side stream treatment

Anammox process 35 | 47

Is this all anammox can do ??

Anammox process 36 | 47
 New frontier: anammox in the main-stream

Conventional Municipal WWTP

Main pollutants
• Organic matter
• Nitrogen
• Phosphorus

Anammox process 37 | 47

Conventional Municipal WWTP

WATER LINE
Organic matter:
C + O2 → CO2 (Activated sludge)
Nitrogen:
N + O2 → NO3 (Nitrification)
NO3 + COD → N2 (Denitrification)
Phosphorus:
P-incorporated in biomass → Sludge disposal (P-removal)

SLUDGE LINE
Primary settler + Excess biomass (sludge) → CH4 + CO2
(Anaerobic Digestion)

Anammox process 38 | 47
 Conventional Municipal WWTP

..different approach..

Organic carbon in wastewater = chemical energy

Maximize the yield of the COD removal process to

maximize biogas production
( i.e. A-stage in A-B concept )
Benefits:
• higher methane production
• less oxygen consumption
• less CO2 emissions

Anammox process 39 | 47

Conventional Municipal WWTP

Organic carbon in wastewater = energy (biogas)

Maximize the yield of the COD removal process to

maximize biogas production

Drawbacks: N-pollution problem

• no COD left for Denitrification → or
high N-removal costs

Autotrophic nitrogen removal !!!

Anammox process 40 | 47
 Anammox process in the side-stream
TU-Delft proposal

• High volumetric rates

• Biomass retention at short HRT
• Low maintenance operation
• CANON with Granular Sludge
• No complex process control
( self-aggregated biofilm)
• No prone to nitrite inhibition
• No prone to solids/COD shock-loads
• Integrated settler

Anammox process 41 | 47

Anammox process in the main-stream

case study: Dokhaven WWTP, Rotterdam

(620000 p.e.)

Nitrogen removal issue:

• A-stage/B-stage configuration
• Built in the late 70s → no strict limit on N
• no Denitrification-step in original design
• underground plant → no space for new reactor-tank
• 17 mgNO3-N/L in the effluent

Anammox process 42 | 47
 Anammox process in the main-stream

A-stage B-stage
COD oxidation Settler NH4 oxidation Settler

Aerated tank Aerated tank

Anammox
P.N. Dewatering Digester

Water line
Sludge line
Sludge disposal Digestate

Anammox process 43 | 47

Anammox process in the main-stream

A-stage B-stage
COD oxidation Settler NH4 oxidation Settler

Aerated tank Aerated tank

Anammox
P.N. Dewatering Digester

Water line
Sludge line
Sludge disposal Digestate

Anammox process 44 | 47
 Anammox process in the main-stream
B-stage
A-stage
Autotrophic N
COD oxidation Settler Settler
removal

Aerated tank CANON

Anammox

X P.N. Dewatering Digester

Water line
Sludge line
Sludge disposal Digestate

Anammox process 45 | 47

NET ENERGY (calculations)

Conventional Treatment

-44 Wh p-1 d-1

Optimized treatment with anammox in

the main-stream

+24 Wh p-1 d-1

Anammox process 46 | 47
 …on going research…

Anammox process 47 | 47

ANAMMOX, take-home message

• Fully developed technology

• Several Suppliers
• Applied on a wide scale of wastewaters
• Focus on Main Stream Applications

Anammox process 48 | 47
 Once upon a time …
… it was
nitification/denitrification

Dr. Ir. Tommaso Lotti

email: [email protected]

Anammox process 49 | 47