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Pereboom Anaerobic Treatment of Chemical Wastewaters ACHEMA 2012
Citation preview
Anaerobic treatment of chemical wastewaters :
new technologies bring
new opportunities
Frankfurt; June 19, 2012; 10:30 Jan Pereboom,
Jorien van Geest and Dennis Korthout
2
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
3 3
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
4 4
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
5 5
Biothane Technologies; non-granular
Biobulk CSTR • Solid waste digestion
• With our without sludge recirculation
• Suitable for high COD / SS / FOG waste(water)
6
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
6
Anaerobic Treatment of Chemical Wastewaters
2
Some 50 references in chemical industry
Phenol
PTA
DMT
PET
POM
MSPO
Solvent recovery
Formaldehyde
Oxo – chemicals
Yeast, Biofuel, Palm-oil
8
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!
9 9
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
10
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)
11
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
27/06/2012 12 12
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
13
Biothane in PTA industry (1)
PTA: Purified Terephtalic acid
14 14
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
16
Biothane PTA references (3)
17
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)
27/06/2012 18 18
Full scale PTA reference (5)
27/06/2012 19
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
19
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
20
21
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
22 22
New Developments
3
Biobed®SMART reactor control
Memthane® Anaerobic MBR
Future trends in wastewater treatment
Resource Recovery & Water Re-use
From a traditional wastewater treatment plant…
24 24
Future trends in wastewater treatment
Resource Recovery & Water Re-use
…to a Biorefinery
27/06/2012 25 25
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
26 26
“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
27
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.
28
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
29
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
30
Memthane®; Track record (4)
31
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
32
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
34 34
“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 [email protected] or visit our booth: 6.1 B98
35