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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: barnardjl@bv.com