Anaerobic treatment of chemical wastewaters :

new technologies bring

new opportunities

Frankfurt; June 19, 2012; 10:30 Jan Pereboom,

Jorien van Geest and Dennis Korthout

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Contents

1. Introduction

2. Anaerobic treatment of Chemical Wastewaters

3. New Developments

4. Conclusion

Biothane: competence centre of Veolia Water

Veolia Water • Revenues 12.6 bln€; 69 countries; 97,000 employees

• Drinking water for 103 mln consumers; sewage of 73 mln inhabitants

Veolia Water Solutions and Technologies (VWS) • Contracting and equipment; 250 proprietary technologies

• Revenue 2.6 bln€; 135 business units; 10,000 employees

Biothane • World market leader for Anaerobic industrial wastewater treatment

• In 35 years some 530 references were established

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Anaerobic versus Aerobic WWT

45% Carbon Dioxide

50% Biomass

BOD Air (O2)

100 kg COD to Aerobic

BOD (25OC – 35OC)

75% Biogas (75% Methane)

5% Biomass

100 kg COD to Anaerobic

Aeration

(100 kWh)

Sludge, 30-60 kg

Heat loss

2-10 kg COD

CH4 26 - 30 Nm3 CO2 5 - 12 Nm3

Sludge, 5 kg

10-20 kg COD

1 kg COD removed 0.35 Nm3 CH4 or 3.8 kWh

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Biothane’s Granular Technologies

Biothane UASB • Granular Sludge Bed

• Up to 15 kg COD/m3/d

Biobed® EGSB • Granular Sludge Bed

• High Rate Process

• Soluble COD removal

• Up to 30 kg COD/m3/d

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Biothane Technologies; non-granular

Biobulk CSTR • Solid waste digestion

• With our without sludge recirculation

• Suitable for high COD / SS / FOG waste(water)

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Upthane™ • Municipal UASB technology for

tropical climates

• Novel design

Memthane ® Anaerobic MBR • New technology for high strength wastewater

• Using Cross-flow UF membranes

• High COD / SS removal efficiencies

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Anaerobic Treatment of Chemical Wastewaters

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Some 50 references in chemical industry

Phenol

PTA

DMT

PET

POM

MSPO

Solvent recovery

Formaldehyde

Oxo – chemicals

Yeast, Biofuel, Palm-oil

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Wastewaters from chemical industry

Typical wastewater characteristics • Composition often well defined

• High concentration of COD

• Mainly soluble COD (low TSS)

• Lack of nutrients

• Biodegradable components

Toxic concentrations

Long adaptation time required

Pre-treatment required

Pilot / laboratory research is key for a successful design!

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Shell Moerdijk; the Netherlands

Production of Methyl-Styrene Propene-Oxide (MSPO)

Wastewater rich in salt and Benzoic Acid

Two years of laboratory research prior to design (1990’s)

Wastewater from wet air oxidation unit treated

More than 20 years in operation

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Operational Results Shell Moerdijk

Design Actual

COD mg/l 20,000 20,000 – 45,000

COD load kg COD/m3/d 14.4 14 – 28

COD removal

% 80 80 – 95

*Based on Frankin et al, 1994 and oral conversation with operators 10

Doubling of the production of Delrin®

Waste water containing Formaldehyde, Acetic Acid,

Formic Acid, Methanol and Octanol

Toxicity tests • Methanol / Formaldehyde and Octanol all

present in toxic concentrations

10 x dilution required!

DuPont; the Netherlands (1)

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Wastewater characteristics DuPont

Average Peak

Flow m3/d 720 840

COD load kg/d 5400 8000

Formaldehyde mg/l 3000 5000

Octanol mg/l 67 350 11

DuPont; the Netherlands (2)

Batch + Continuous tests • Adaptation to octanol after 6 weeks

• Octanol degradation during steady-state

80 - 90%

• Peaks in octanol till 600 ppm are allowed

• COD efficiency > 90% during the entire experiment

• 10 Times dilution required

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0

20

40

60

80

100

1 2 3 4 5 6 7 8 9

CO

D e

ffic

ien

cy (

%)

Octanol Formaldehyde

Time (weeks)

0

20

40

60

80

100

1 2 3 4 5 6 7 8 9

T(S

)CO

D e

ffic

ien

cy (

%)

TCOD removal SCOD removal

Time (weeks)

DuPont; the Netherlands (3)

13 *Based on Zoutberg, 1997 and internal reports

Efficiency Octanol & Formaldehyde + COD removal

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Biothane in PTA industry (1)

PTA: Purified Terephtalic acid

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Anaerobic treatment of PTA wastewater (2)

Main components wastewater:

Adaptation required to phthalic acid isomers:

COOH

COOH

COOH

COOH

COOH

COOH

COOH

COOH

COOH

COOH

COOH

CH3

CH3COOH

Para Terephthalic acid

Mw 166; COD 1.44 g/g

Ortho phthalic acid

Mw 166; COD 1.44 g/g

Iso phthalic acid

Mw 166; COD 1.44 g/g

Benzoic acid

Mw 122; COD 1.97 g/g

Tri mellitic acid

Mw 210; COD 1.14 g/g

P-Toluic acid

Mw 136; COD 2.12 g/g

Acetic acid

Mw 60; COD 1.07 g/g

Time required to reach 50% degradation in batch mode

Compound Days

Benzoic acid 4-10

Orthophthalic acid

16-49

Terephtalic acid 44-61

Iso-phtalic acid 74-156 15

Reference Country Industry / Typical components

Year

DSM Netherlands Benzaldehyde/phenol plant (Benzoic Acid/Phenol)

1985

Shell Netherlands MSPO / Benzoic acid 1986

Petrocel Mexico DMT /PTA (mainly DMT) 1994

Volos Greece PET 1996

Eastman Argentina PET 1996

KOSA (Hoechst )

Netherlands DMT (acetic acid/ formaldehyde/ paraxyleen)

1997

SASA Dupontsa

Turkey DMT / PTA (mainly DMT) 1997

DMT = Di Methyl Terephthalate PET = Poly Ethylene Terephthalate

Biothane references prior to PTA applications

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Biothane PTA references (3)

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Between 2000 and 2012

15 Full scale plants established in

•China, India, Taiwan and Singapore

•USA and Canada

•Europe

Artenius latest plant in 2012 in Portugal

•5000 m3 anaerobic reactor

Round steel and concrete

Biobed EGSB Continuous Laboratory Test

COD removal efficiencies

0

10

20

30

40

50

60

70

80

90

100

0 50 100 150 200 250

Re

mo

val e

ffic

ien

cy (

%)

0

5

10

15

20

25

load

kg

CO

D /

m3

d

TCOD removalSCOD removalload SCOD

benzoate : 100 % conv.

ortho and para

degradation starts

para-phthalic acid

degradation: ~100 %

Laboratory tests PTA wastewater (4)

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Full scale PTA reference (5)

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0

5

10

15

20

25

0

10

20

30

40

50

60

70

80

90

100

0 100 200 300 400 500 600

CO

D lo

ad

(k

g/m

3/d

)

CO

D re

du

cti

on

(%

)

Day

Biobed EGSB Full scale operation

PTA Wastewater

COD reduction

COD Load

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Anaerobic treatment of PTA wastewater (6)

Latest project for Artenius in Portugal 2012

Anaerobic/aerobic: 70t/day + Cogeneration

Make up Demin 7200m3/d

Cooling towers 3,7MW + 3,4MW

DBFO Multi service contract

5000 m3

13000 m3

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Typical layout Biobed® EGSB plant

Biomass Storage Tank

anaerobic effluent

acid

N

P

FeCl3 + micro

Ca/Mg/K/YE

antifoam

Buffer Tank Conditioning

Tank Biobed® EGSB raw wastewater

Flare

biogas to use

Biogas Scrubber

caustic

dilution water (aerobic effluent)

Selection of Biothane’s references in chemical industry

Selection of Biothane references

Industry Country Product

DSM Chemicals

Netherlands Phenol

Shell Netherlands MS/PO

Ciba Geigy Korea Dying

Baek Hwa Korea Alcohols

Petrocel Mexico PTA/DMT

Eastman Argentine PET

Gist brocades Europe Pharmaceutical

Caldic Netherlands Formaldehyde / methanol

Copenor Brazil Formaldehyde

VPI Greece PET

Borsod Chem TDI

DuPont Netherlands Delrin

in chemical industry

Industry Country Product

Hoechst Netherlands DMT

Castagna Univel Italy Solvent recovery

Sam Yang co Korea PET

Eastman Chemicals

Singapore OXO

Orchid chemicals

India Pharmaceutical

Ciba CKD Biochem

India Pharmaceutical

InfreServe Höchst

Pharmaceutical

Alembic Chemicals

India

SASA Turkey DMT

Rotopas Turkey Solvent recovery

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New Developments

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Biobed®SMART reactor control

Memthane® Anaerobic MBR

Future trends in wastewater treatment

Resource Recovery & Water Re-use

From a traditional wastewater treatment plant…

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Future trends in wastewater treatment

Resource Recovery & Water Re-use

…to a Biorefinery

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Biobed®SMART reactor control system (1)

Sludge Management and Reactor Control Techniques

Objectives : • Achieve more stable reactor operation

• Achieve higher COD removal efficiency

• Reduce operating costs

Elements : • On-line COD estimation for Dynamic reactor control

• Biogas production and concentration feed-back

• Reactor capacity measurement

• Online Sludge Bed Level measurement

• In-situ sludge inspection by video camera

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“Real time video from inside the anaerobic reactor”

Biobed®SMART reactor control system (2)

SMART

module

Operational indicators

Gas composition indicator

Theoretical biogas production

Proportionate biogas production

Reactor capacity (SMA)

Sludge bed height trend

Reactor Feed control

Constant COD load

Service contracts

Camera inspections

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Memthane® step-by-step (1)

Conditioning of high- strength wastewaters.

Influent is fed to the anaerobic bioreactor where the organic components are converted into energy-rich biogas.

Cleaning In Place (CIP)

After anaerobic treatment, the UF membrane unit separates the clean permeate from the biomass.

If required, several polishing techniques are available to further treat the suspended solids free effluent for reuse or recovery of nutrients, while the low COD permeate is often clean enough for direct discharge to sewer.

Biomass is returned to the bioreactor, while a small amount of biomass is removed from the system and discharged after dewatering.

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Memthane®: Features (2)

Treat high-strength effluent previously considered untreatable

• High concentrated streams : COD 15,000 – 250,000 ppm

• Superb effluent quality

• Create product for nutrient recovery

Maximize renewable green energy production

• Generates biogas from wastewater

• Minimizes carbon footprint and water footprint

Remove COD efficiently

• Avoids costly aerobic post treatment

• Generates more biogas

Reduce OPEX

• Reduces disposal costs while generating biogas

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Memthane®; Applications (3)

High concentrated streams (COD 15,000 ~ 250,000) such as

Dairies

• Whey, Milk Processing

Ethanol Facilities

• Pot Ale, Spent Wash, (Thin) Stillage and Vinasse

Food wastewaters containing Fat Oil and Grease (FOG)

• Ice cream

Wastewaters containing high COD

• Bio-ethanol, Biodiesel, Chemical Wastewaters

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Memthane®; Track record (4)

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Proven Innovation • 6 full-scale Memthane® plants

• 4 years of full-scale industrial operation

• 14 pilot plant tests

Implemented in: • Dairy industries

• Bioethanol plant

• Cellulosic Bioethanol plant

• Biodiesel plant

• Food processing

Memthane®; Chemical application (5)

Methyl-Styrene Propene-Oxide (MSPO): • Various highly concentrated wastewaters streams

• High and Low salt streams; with very different chemical composition

Recent lab scale research showed: • 30~40 % of overall COD can be degraded anaerobically

Conclusion • Treatment of source separated streams is essential

• One or more anaerobic reactors: modular Memthane®

• High loaded aerobic + low loaded aerobic polishing

• Only small remaining stream would be incinerated

• Enormous saving in operation cost

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Conclusions

4

Conclusion

Anaerobic treatment is well established in chemical industry

Key to a good design is laboratory / pilot research

Anaerobic treatment important part of Biorefinery concept

New technologies bring new opportunities

• Biobed® SMART brings better control and lower OPEX

• Memthane® is creative new tool for high concentrated waters

Reducing CAPEX and OPEX

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“Aerobic treatment can also have problems; next to high Capex en Opex”

Thanks for your attention For further information or questions Please contact: Jan Pereboom; Marketing Manager at Biothane jan.pereboom@veoliawater.com or visit our booth: 6.1 B98

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