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Present and Future Technologies for Nutrient Removal
James L Barnard, Ph.D., D.Ing. h.c. BCEE, WEF Fellow, Dist. MASCE
Ohio Water Environment Association
Contents
Problems relating to NutrientsWastewater as ResourceBasics of present nutrient removal and
recovery Future developmentsNutrient Roadmap
Microcystis Poisoning
Dr. Anthony Turton, Keynote Address CSIR RSA November 18, 2008
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Fishkill
Photo by Gerald Simons
Ocean life on the brink of mass
extinctions… overfishing, excessive nutrients causing ‘dead zones’…. News Daily Posted 2011/06/21 at 5:50 am EDT
Lee Kuan Yew Water Prize 2011
Olympic Sailing Craft in Algae at Qingdao
Foreign Policy – May/June 2011
As the new year begins, the price of wheat is setting an all-time high in the United Kingdom. Food riots are spreading across Algeria. Russia is importing grain to sustain its cattle herds until spring
grazing begins. India is wrestling with an 18-percent annual food inflation rate,
sparking protests. China is looking abroad for potentially massive quantities of wheat
and corn. The Mexican government is buying corn futures to avoid
unmanageable tortilla price rises. the U.N. Food and Agricultural organization announced that its food
price index for December hit an all-time high.” Increased cost of Fertilizer
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BNR
Possible Resource Recovery
Cooling TowersPotable Water
Heat Recovery
Composting PelletizationIncineration
Irrigation
Used Water
UrineSeparation
PowerProtein Recovery
Gas
Fertilizer
B&V -8
Comparative Energy Requirement
Energy used for kWh/c/a
BNR Wastewater Treatment 40
Average pumping for 21 treatment plants 69
Switching one lamp to low energy fixtures (Saving/lamp/a)
102
Pumping water from Missouri River to Kansas City 60
Pumping water from north to south of California 355
Desalination of brackish water 200
Desalination of seawater 525
Office lights for one person at 12 hours per day 1,750
Household per person (2 persons) 9,600
Heat recovery from effluent
Community College
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Nitrification
Nitrifyingbacteria
Ammonification
The Nitrogen Cycle
Decomposers
(aerobic andanaerobic bacteriaand fungi)
Ammonium (NH4+) Nitrites (NO2
‐)
Nitrates (NO3‐)Nitrogen‐fixing
bacteria inroot nodulesof legumes
Precipitation
Plants
Nitrogen‐fixing soil bacteria
Assimilation
Nitrogen in atmosphere (N2)
Denitrifyingbacteria
Nitrifying bacteria
Nitrogen removal
The Nitrogen Cycle
N/DN Uses O2 for NN and Carbon for DN
Can be reduced if not going all the way to Nitrate
Anammox bacteria can eliminate carbon while reducing oxygen to 60%
H-B Process
2.8 gO/gN
1.7 gO/gN
4.77gC/g N
Nitrification by slow growing temperature sensitive autotrophs
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Conversion of Nitrates to Nitrogen gas
What is denitrification
Carbon Dioxide + WaterCO2 + H2O
Oxygen O2
Nitrogen gas N2
Nitrates NO3
BacteriumSugarC12 H22 O11
Suspended growth systems
MLEBardenpho Channel systemsMBRSBRGranular activated sludge
Single Stage Denitrification
ANOXIC AEROBIC CLARIFIER
MIXED LIQUOR RECYCLE
RETURN ACTIVATED SLUDGE WASTE SLUDGE
Q
4Q
NH3 < 0.5 mg/L
NOx < 6 mg/L
TN < 8 mg/L
MBE (MLE)
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Bardenpho Process
Anaerobic
Settled Used Water
Aerobic Anoxic Aerobic
P
PAir
Waste Solids with Phosphate
Methanol Optional
Air
N GasN Gas
Effluent
Anoxic
Optional Carbon
EffluentAmmonia N = 0.5 mg/ℓTN < 3 mg/ℓ TP < 1 mg/ℓ
Anaerobic Aerobic Post Anoxic
Water Sludge
Anoxic
Membrane Tank
The future in BNR
Cauley Creek Membrane BNR Bioreactor
DeOx/DeNit
Anaerobic
Anoxic
Aerobic
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Vienna plant uses SND- Saves energy
Fixed Film ProcessesNitrification Biological Aerated Filter (Biofor, Biostyr) MBBR Trickling Filter Fluidized Bed
Denitrification Biological Filter (Biofor, Biostyr) MBBR Deep Bed Sand Filter (Tetra) Upflow Fluidized Bed (Envirex)
Multi-stage N/DN
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Add on N/DN Systems
Methanol
BAFTetra
Sand FilterHigh RateActivated Sludge
Nitrogen recovery
Only viable if less energy is used than fixing Nitrogen from the atmosphere
Can only be considered from high concentration return streams – Cambi as high as 2,000 mg/ℓ
Methods used Ion ExchangeStripping and capture of ammonia
Haber-Bosch process uses about 12 kWh/kg nitrogen fertilizer
Anammox – Demon – Anitamox make recovery even less viable
`
Clinoptilolite Ion Exchange for Ammonia Recovery
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Ammonia Stripping and capture from return streams - Oslo Norway From Evans 2009
HNO3 used for
absorption
Lower portion of adsorption column
Final Product 54% NH4 NO3
90% nitrogen removal
1.7 gO/gN
0 gC/g N
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Phosphorus removal Options
Biological or chemical
Chemical Phosphorus Removal Add chemical to precipitate
soluble phosphorus Alum, ferric chloride, ferrous
chloride, magnesium hydroxide, polyaluminum chloride, etc.
Multiple dosing locations Increases sludge production,
consumes alkalinity
Effluent
FiltersInfluent
WAS
RAS
Aeration
Raw PS
SCPC Tertiary P removal
Alum Dosage vs. Target Effluent Phosphorus
0.0
1.0
2.0
3.0
4.0
5.0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Effluent OP, mg/L
Al3
+/O
P R
atio Median Literature
Dosage
Benefits of Combined systems It is practically possible to reduce soluble phosphorus
to levels as low as 0.07 to 1.1 mg/L biological means only in phosphorus removal plants
Further polishing with chemicals in tertiary treatment can reduce this to an effluent total P of less than 0.05 mg/L
Durham, OR used 175 mg/L of Alum when operating chemical only, added to primary, aeration and post treatment
Reduced to 25 mg/l when applying biological plus chemical polishing to get 0.07 mg/L as P
Pinery Water achieves LT 0.03 mg/L TP with a biological/chemical sequence
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Microbiology
3/12
Bio-P Organisms Store PHB and Release P in the Anaerobic Zone
PHB
Poly-P
VolatileFatty Acids
Phosphate
Energy
Facultative heterotrophsFacultative heterotrophs
RbCOD
Influent
Influent
No dissolved oxygen or nitrates
These are obligate aerobes. They can store but not process
VFA from outside source or MLSS fermention
Poly-P
Poly-P
PHB
Electron microscope –Poly stains black, PHB stains white
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Bio-P Organisms Oxidize PHB and Remove P in the Aerobic Zone
PHB
Poly-P
Phosphate
Oxygen
Carbon Dioxide +H2O
Energy
(Nitrate)
Stored in anaerobic zone.
Consumed in aeration basin providing energy for storage of phosphorus
Phosphorus taken up to <0.1 mg/L
Poly-P
Pol
y-ph
osph
ate
stor
ed in
the
aero
bic
zone
.
Pho
spho
rus
is r
emov
ed w
ith
the
WA
S
Biological Phosphorus Removal
Fuhs & Chen, 1975
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Typical Flow sheets
When using SND much simpler process flow sheets are possible
VFA and rbCOD Requirements for P Removal
0.0
5.0
10.0
15.0
20.0
25.0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Fraction of rbCOD that is VFA
rbC
OD
/P r
atio
Eagle’s Point
w/o fermenter
With Fermenter
Durham
VIP
Reedy Creek SC
McDowell Creek
At this point all rbCOD is VFA
At this point there is no VFA
This line is used in BNR models
These plants are getting fantastic results
Fermenters
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Static Fermenter
to digesters
Anoxic
anaerobic
VFA
Oversized Thickener – retain sludge for 6 to 8 days
VFA to anaerobic zone
Primary tank
Westbank BC
Grimstad Norway
08/06/08
Primary Anaerob Anoxic 1 Anoxic 2 Anoxic 3 Aerobic 1 Aerobic 2 Aerobic 35.36 20.56 2.20 1.84 1.60 0.50 0.20 0.03Bioreactor Profile
Phosphorus by Zone
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
Pri
mar
y
An
aero
b
An
oxic
1
An
oxic
2
An
oxic
3
Aer
obic
1
Aer
obic
2
Aer
obic
3
Ph
osp
hor
usm
g/L
Westbank WWTP
Note P uptake in Anoxic Zone
Unconventional Flow-sheets
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Bio-P through Operations
0
2
4
6
8
10
12
14
1/1/
024/
11/0
27/
20/0
210
/28/
022/
5/03
5/16
/03
8/24
/03
12/2
/03
3/11
/04
6/19
/04
9/27
/04
1/5/
054/
15/0
57/
24/0
511
/1/0
52/
9/06
5/20
/06
8/28
/06
12/6
/06
3/16
/07
6/24
/07
10/2
/07
1/10
/08
4/19
/08
7/28
/08
11/5
/08
Eff
luen
t Tot
al P
(m
g/L)
Total P 30-day Moving Avg (Total P)
St. Cloud, MN(turning the air down in the first pass)
Fermentation of Secondary Sludge
Pinery Water CO
Truckee Meadows NV
Sludge partially settled in this zone and fermented, providing VFA
Fermenting portion of RAS
Changed from Pho-strip to this
0
100
200
300
400
500
600
700
800
900
1000
0
2
4
6
8
10
12
14
19811982198319841985198619871988198919901991199219931994199519961997199819992000200120022003
Mill
ion
Gal
lon
s F
low
Met
ric
To
ns
To
tal
P
City of KalispellWWTP Yearly Phosphorus Loading
to Flathead Lake
Metric Tons Total P Million Gallons Flow Linear (Million Gallons Flow)
Phosphate detergent ban;alum addition
BNR Planton-line 10-22-92
I d D OImproved D.O. Control
FlowTrendline
From Joni Emrick
EBPR Operation at Kalispell, MT
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Future Roadmap Where are we
and where would we like to be
Aerobic Nitrifying treatment(Rock Media TF or other?)
Recycle Pump with high DO + nitrate rich effluent(Bio-gas powered?!)
Anaerobic Zone
Biogas to vent or use?
Flow forced through settled
sludge by baffles
High void-space rock media growing methanotrophic and other denitrifying biomass biofilm
“Lo-Tech” Option
UASB
A-recycle
Blower
?
MBBR
Air
Gas Generator/Flare
Biogas
Methanotrophic Denitrification using Biofilm Reactor (Anoxic MBBR or SAF)
“Hi-Tech” Option
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McCarty fluidized bed membrane reactor
Anaerobic Fluidized MembraneBioreactor (AFMBR)
Concerns
Since most all the carbon is removed – how to remove nutrients
Utilize methane remaining in the effluent of the anaerobic process
Convert to methanol and use for denitrification Use chemicals for phosphorus removal Alternatively use dedicated Ion Exchange for
nitrogen and phosphorus removal with recovery of the nutrients
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The Ultimate in SNDGranular activated sludge
SBRs with feed during decant, leading to SND and P removal
Nereda TechnologyNereda Websitehttp://www.dutchwatersector.com
Granular activated sludge
Dublin 160 mgd plant uses same technology
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Epe - Netherlands
Present Dublin Plant
Fill during decant
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Fill during decant
Fill during decant
Fill during decant
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SBR Operation
Four basins operated in series all a the same level with fixed weirs
Two basins aerated at any timeOne basin in sedimentation modeOne basin in fill/decant. Flow automatically goes
where valves are open for decanting Continuous flow Black & Veatch design/operating a plant treating a
maximum flow of 260 mgd Very good settling sludge SVI 60 mℓ/g Could be operated to produce granular sludge.
Anammox for side-stream and main stream treatment
Return StreamCharacteristics Temperature is high, 30‐38° C Ammonia concentration is high Typically 800‐1000 mg/L NH4‐N
Higher concentrations for high solids digesters Low alkalinity Typical side=stream contains 50% alkalinity needed
for nitrification of the ammonia ~3.5 mg Alkalinity as CaCO3/mg NH4‐N
Relatively low BOD (or COD)
Recycle nitrogen constitutes 15‐25% of nitrogen in the influent
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1.7 gO/gN
0 gC/g N
Anammox Physiology
Anammox bacteria: Form biofilms and are often
observed as suspended granules or on the surface of synthetic media.
Are strictly anaerobic - reversibly inhibited by DO concentrations as low as 0.03 mg/L.
Are inhibited by high NO2-, but the
threshold concentration is controversial.
Have a remarkably slow growth rate. Reported doubling times are often as slow as 10 to 20 days.
Principle One Step Anammox® Pacques presentation
2 NH3 + 1.7 O2 1.14 NO2- + 0.86 NH3 0.88 N2 + 0.24 NO3
-
NH3
NH3
NH3
NO3-
NO2-
N2
O2
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DEMON installation with cyclones for separating the Anammox granules for return to the process
Benefits of One Step ANAMMOX®
B&V DESIGNING BLUE PLAINS WWTPFILTRATE TREATMENT FACILITY: DEMON ® PROCESS
69
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Largest Anammox installation in the US designed to: Treat 1 MGD from liquid stream filtrate of sludge
processing facility Removal rate: 12,400 kg-N/day
Schedule: Design to be completed by late 2013 Final completion date in 2016
Estimate of Probable Construction Cost $ 47-53 Million
BLUE PLAINS WWTPANAMMOX: DEMON ® PROCESS
70
Influent 1Aviko
Steenderen
UASB(3*1200 m3)
PHOSPAQ(2*300 m3)
One-Step ANAMMOX®
(600 m3)
THIOPAQ® Scrubber
Sulphur (S°)
Magnesium-oxide (MgO)
Struvite(MgNH4PO4.6H2O)
CHP (600 kWe)
Biogas withSulphide (H2S)
Cleaned Biogas
AirAir
Influent 2Rejectwater
Sewage Works Olburgen
CleanedEffluent to
Sewage Works
Paques Plant - Rijn & IJsel –Olburgen STW
Performance PHOSPAQ & ANAMMOX - effluent to STW:
COD removal 50 %P removal 80 %TKN removal 90 %
P.E. 8,600
Influent PHOSPAQ & ANAMMOX: UASB Effluent Reject water
Flow 3,000 360 m³/dCOD 2,000 200 kg/dTKN 1,000 250 kg/dPO4-P 225 20 kg/d
P.E. 47,500 10,000
Characteristics
CASE STUDY: Rijn & IJsel –Olburgen STW
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Application of Anammox to Main-stream plant
Full-Plant Deammonificationfor Energy PositiveNitrogen Removal
Joint WERF/WEF WebcastThursday, November 7th, 20131:00 – 3:00 pm Easter
For more information see
Concept – Energy efficient nitrogen removal
Grow Anammox bacteria in side-stream at high temperature Waste surplus Anammox bacteria to main
stream plantUse some selection process such as
cyclones to concentrate Anammox bacteria from the waste activated sludge Feed back to main plant
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Hi-rate A-B Process used in the Strass plant
Plant is energy self-sufficient Second stage SND plant achieves denitrification with minimal energy
input Side-stream DEMON process for energy efficient ammonia removal Successful experiments with main plant nitrogen removal
enhancement with surplus DEMON organisms
Future choices for Nutrient removal
BNR with MBR with little chemicalsAnaerobic membrane with IE for nutrient
reduction and captureA-B process with chemicals for
phosphorus removal but energy self-sufficientGranular activated sludge with little
chemicals and possible phosphorus recovery
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Membrane Bioreactor (MBR)
Developed technology for N and P removal to very low levels Small footprintHigh quality effluent Replaces final clarifiers, filters and
disinfectionDisadvantage Energy intensive
Anaerobic membrane reactor
Produces energy Very little sludge productionMethane in solution could be used for
denitrification Needs further polishing for low levels of N
& PPhosphorus must be removed by
chemicals thus no recovery
A-B process with SND
Energy self-sufficientEstablished technologyNormal footprintApplicable to existing high rate plantsNeeds further polishing for low levels of NPhosphorus removal by chemicals –
recovery expensive
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Granular activated sludge New but proven technologySmall footprintReduced energy use Very simple operation – low level of
mechanical equipmentSND a biological phosphorus removal Allow for phosphorus recoveryNeeds some filtration to reduce effluent
TSS and nutrients
Phosphorus Recovery
Phosphorus is a limited resourceUS produces 25% of world resourcesMorocco has 6 times the deposits of the USProduction limited to a few countries In less than 50 years high grade ore will run outAt the present rate of consumption we may have
enough for another 200 yearsThe USA has stopped exporting phosphorus We cannot afford to use it once and waste it
It is irreplaceable
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Future Scenarios
Towards global phosphorus security: A systems framework for phosphorus recovery and reuse options D. Cordell, A. Rosemarin, J.J. Schröder , A.L. Smit - Chemosphere 84 (2011) 747–758
North AmericaStruvite
Mg.NH4.PO4. 6 H2O
Also recovers up to 20% of nitrogen
Incinerator Ash
Deposit in dedicated site for future recovery
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SummaryConventional BNR systems have served us
well but uses energy and may have a large footprintFootprint becomes an issue for larger
plantsEnergy and chemical use needs to be
reducedAlternatives exist for most starting pointsPhosphorus recovery is serious
Personal Information
James L. Barnard, Ph.D., D.Ing. hc., BCEE, WEF Fellow, Dist MASCE
Global Practice and Technology LeaderBlack & Veatch
12869 Cambridge Terrace, Leawood KS 66209
Telephone Work 913-458 3387Mobile 913-963 9498
Email: [email protected]
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