Anaerobic treatment of chemical wastewaters : new technologies bring new opportunities

Frankfurt; June 19, 2012; 10:30 Jan Pereboom, Jorien van Geest and Dennis Korthout

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

Anaerobic versus Aerobic WWT

Heat loss CH4 26 - 30 Nm3 CO2 5 - 12 Nm3

BOD 100 kg COD Air (O ) to Aerobic

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45% Carbon Dioxide

50% Biomass

2-10 kg COD

BOD 100 kg COD (25 C 35 C) to Anaerobic

O O

75% Biogas (75% Methane)

5% Biomass

Aeration (100 kWh)

10-20 kg COD

Sludge, 30-60 kg

Sludge, 5 kg 1 kg COD removed 0.35 Nm3 CH4 or 3.8 kWh

Biothanes 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

Biothane Technologies; non-granular

Biobulk CSTR
Solid waste digestion With our without sludge recirculation Suitable for high COD / SS / FOG waste(water)

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

Some 50 references in chemical industry

Phenol PTA DMT PET POM MSPO Solvent recovery Formaldehyde Oxo chemicals Yeast, Biofuel, Palm-oil

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!

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 (1990s) Wastewater from wet air oxidation unit treated More than 20 years in operation
Operational Results Shell Moerdijk Design COD COD load COD removal
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Actual 20,000 45,000 14 28 80 95

mg/l kg COD/m3/d %

20,000 14.4 80

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

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DuPont; the Netherlands (1)

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!
Wastewater characteristics DuPont Average Flow COD load Formaldehyde Octanol
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Peak 840 8000 5000 350

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m3/d kg/d mg/l mg/l

720 5400 3000 67

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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DuPont; the Netherlands (3)

Efficiency Octanol & Formaldehyde + COD removal
100
COD efficiency (%)

80 60 40 20 0 1 2 3 4 5 6 7 8 9

Time (weeks)
Octanol Formaldehyde

T(S)COD efficiency (%)

100 80 60 40 20 0 1 2 3 4
Time (weeks)

TCOD removal

SCOD removal

*Based on Zoutberg, 1997 and internal reports 13

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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:
COOH COOH COOH COOH COOH

COOH COOH
Para Terephthalic acid Mw 166; COD 1.44 g/g Ortho phthalic acid Iso phthalic acid Benzoic acid Mw 166; COD 1.44 g/g Mw 166; COD 1.44 g/g Mw 122; COD 1.97 g/g

COOH COOH

COOH

CH3COOH

Time required to reach 50% degradation in batch mode

Compound Days

COOH
Tri mellitic acid Mw 210; COD 1.14 g/g

CH3
P-Toluic acid Mw 136; COD 2.12 g/g Acetic acid Mw 60; COD 1.07 g/g

Benzoic acid
Orthophthalic acid Terephtalic acid Iso-phtalic acid

4-10
16-49 44-61 74-156
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Adaptation required to phthalic acid isomers:

Biothane references prior to PTA applications

Reference
DSM Shell Petrocel

Country
Netherlands Netherlands Mexico

Industry / Typical components

Benzaldehyde/phenol plant (Benzoic Acid/Phenol) MSPO / Benzoic acid DMT /PTA (mainly DMT)

Year
1985 1986 1994

Volos
Eastman KOSA (Hoechst ) SASA Dupontsa

Greece
Argentina Netherlands Turkey

PET
PET DMT (acetic acid/ formaldehyde/ paraxyleen) DMT / PTA (mainly DMT)

1996
1996 1997 1997

DMT = Di Methyl Terephthalate PET = Poly Ethylene Terephthalate

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Biothane PTA references (3)

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

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Laboratory tests PTA wastewater (4)

100 90 80
Removal efficiency (%)
ortho and para degradation starts benzoate : 100 % conv.

Biobed EGSB Continuous Laboratory Test COD removal efficiencies

para-phthalic acid degradation: ~100 %

25

20

70 60 50

15

40
30 20 10 0 0 50
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10

TCOD removal SCOD removal load SCOD 100 150 200

0 250
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27/06/2012

load kg COD / m3 d

Full scale PTA reference (5)

Biobed EGSB Full scale operation PTA Wastewater
100 90
80 70 20

25
COD reduction

COD Load

60

15

50 40 30 20 10 0 0 100 200 300 400 500 600 0 5 10

Day
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COD load (kg/m3/d)

COD reduction (%)

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

caustic acid N P FeCl3 + micro Ca/Mg/K/YE antifoam Flare

Biogas Scrubber

biogas to use

raw wastewater

Buffer Tank

Conditioning Tank

Biobed EGSB

anaerobic effluent

dilution water (aerobic effluent)

Biomass Storage Tank

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Selection of Biothanes references in chemical industry

Selection of Biothane references Industry
DSM Chemicals Shell Ciba Geigy Baek Hwa Petrocel Eastman Gist brocades Caldic Copenor VPI Borsod Chem DuPont
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in chemical industry Industry

Hoechst Castagna Univel Sam Yang co Eastman Chemicals Orchid chemicals Ciba CKD Biochem InfreServe Hchst Alembic Chemicals SASA India Turkey DMT

Country
Netherlands Netherlands Korea Korea Mexico Argentine Europe Netherlands Brazil Greece Netherlands

Product
Phenol MS/PO Dying Alcohols PTA/DMT PET Pharmaceutical Formaldehyde / methanol Formaldehyde PET TDI Delrin

Country
Netherlands Italy Korea Singapore India India

Product
DMT Solvent recovery PET OXO Pharmaceutical Pharmaceutical Pharmaceutical

Rotopas

Turkey

Solvent recovery
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New Developments
BiobedSMART 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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BiobedSMART 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
Real time video from inside the anaerobic reactor
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BiobedSMART reactor control system (2)

Reactor Feed control Constant COD load
Gas composition indicator

SMART module
Theoretical biogas production Proportionate biogas production Reactor capacity (SMA) Sludge bed height trend

Operational indicators

Service contracts

Camera inspections
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Memthane step-by-step (1)

Conditioning of highstrength 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)

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

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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

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

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