practical experience of landfill gas desulfurization
TRANSCRIPT
Thiopaq®
Practical experience of landfill gas
desulfurization
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Who is Paques?
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A FAMILY own business founded in 1960, 20% shares owned by S. Klatten
a worldwide presence through a network of regional offices and partners
LEADING TECHNOLOGIES
BIOLOGICAL
TREATMENT WASTEWATERS
BIOGAS
BALK
CHENNAI
KUALALUMPUR
PIRACICABA
BOSTON
BUENOSAIRES
FRANKFURT
MOSCOW
BOGOTA
BANGKOK
GUANGDONG
CHANGCHUN
SHANGHAI
>60COUNTRIESWORLDWIDE
>400EMPLOYEES
> 2500WORLDWIDEREFERENCES
Paques
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Natural biotechnology to treat waste
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References in anaerobic digestion
References in ammonium removal
References in gas desulfurization
1000+
50+
230+
New Bioplastic production
Landfill gas
• Large quantities of waste generate vast quantities of methane
• 12% of anthropogenic methane emissions are from landfills
• Different regulations specify that LFG should be collected and treated
• Landfill owners are looking at robust and cost efficient gas treatment solutions
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CH4
Household gas Electricity generation Heating Gas-to-grid
CO2
Potentially can be another revenue stream
H2S
Must be removed and can be recovered as S (fertilizer)
Biogas desulfurization
Carbon Zeolites
Lo-cat Sulferox
MEA Sulfinol Caustic scrubber Sulfreen
Sulfatreat
Scavengers
Liquid redox
Absorption
Thiopaq®
Adsorption
Dry oxidation
Trickling filters
Ferrosorp
Thiopaq®
• Originally developed at the University of Wageningen (WUR)
• Pilot on biogas in Eerbeek, Netherlands in 1991
• Full scale in 1993 (the first commercial biogas Unit)
• Currently > 230 units in operation around the world
• First Thiopaq in Landfill in 2001 (Ecopark de Wierde)
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Sulfur oxidizing bacteria Photo: A Jansen
Bioreactor liquid sample
Thiopaq®
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H2S + OH- →
HS- + H2O
HS- + ½ O2 →
S0 + OH-
LFG Biogas Syngas Others
Gas use
Concentrated Sulfur
Vent
Caustic Nutrimix™
Make-up water
Air
Absorber BioReactor
Biosulfur separation
Thiopaq® Typical Layout
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Control room
Absorption column
BioReactor
Solid separation
0 5 10 15 20 25
The Netherlands
Belgium
Finland
Spain
India
Brazil
France
Canada
China
U.S.A.
Korea
S load Units
Landfill gas and Thiopaq®
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Thiopaq® references
86%
Thiopaq® in landfills
14%
THIOPAQ REFERENCES
Thiopaq® references Thiopaq® in landfills
235 TOTAL 39 LFG 44,4 tones Sulfur are
recovered every day from Landfills using Thiopaq!
Landfill in Canada
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• 60% in a cogeneration unit of 10MW
• 40% biogas upgrade-to-grid with a membrane technology
In 2015 the existing technology based on granular iron oxide adsorbent was replaced with a THIOPAQ® that came in operation in 2016. After getting familiar with the process, EBI managed to keep the process up and running and take advantage of its performance.
Parameter Range
Gas flow [Nm3/h]
6,000-12,000
Typical gas composition
55-58% CH4 35-40% CO2 0.12-0.15% H2S
Average treated gas quality
25-75 ppm H2S no addition of N2 or O2
Chemical consumption
10-30 mL Nutrimix/kgS 0.5 kg100%NaOH/ kgS
600 kgS/day capacity
Saint Thomas, CA
Landfill in Canada
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100 ppm
1500 ppm
25 ppm
2017 2018 2019
1000 ppm
Landfill in Canada
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0
100
200
300
400
500
600
700
800
900
1000
18-aug-16 1-nov-16 15-jan-17 31-mrt-17 14-jun-17 28-aug-17 11-nov-17 25-jan-18 10-apr-18 24-jun-18 7-sep-18 21-nov-18 4-feb-19 20-apr-19
NaOH and Nutrimix
3 years
0,7 Euro/kgS removed
Landfill in Canada
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Column Diameter 3m Bioreactor 60 m3 Sulfur slurry dewater to 65% DS Old Scavengers
Landfill in Brazil
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• 5.500 tons of waste collected at the Municipal Sanitary Landfill West of Caucaia (ASMOC)
• August 2017 up to 150,000 m3 of biomethane per day (6250 Nm³/h) are processed.
• Second largest in Brazil, adapting to the National Policy on Solid Waste, approved in 2010.
• The Ceará Gas Company is responsible for the distribution of the biogas, which already has Cerbras as its first customer.
Parameter Range
Gas flow [Nm3/h]
6,000-10,000
Typical gas composition
55-58% CH4 35-40% CO2 0.10-0.15% H2S
Average treated gas quality
25-100 ppm H2S no addition of N2 or O2
Chemical consumption
10-30 mL Nutrimix/kgS 0.5 -0.7 kg100%NaOH/ kgS
Fortaleza, BR 500 kgS/day capacity
Landfill in Brazil
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100 ppm
1500 ppm
25 ppm
2017 2018 2019
1000 ppm
Landfill in Brazil
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0,7 Euro/kgS removed
Landfill in Brazil
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Column Diameter 3m Control screen Bioreactor 60 m3
Landfill in the Netherlands
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Installed over 10 years ago, the installation keeps performing to the
design expected performance making use of the treated gas in an
engine of 0.5MW.
Parameter Range
Gas flow [Nm3/h]
200-300
Typical gas composition
50-60% CH4 30-40% CO2 0.14-0.22% H2S
Average treated gas quality
5-30 ppm H2S no addition of N2 or O2
Chemical consumption
10-30 mL Nutrimix/kgS 0.5 -1 kg100%NaOH/ kgS
Amersfoort, NL
85 kgS/day capacity
~1 Euro/kgS removed
Landfill in the Netherlands
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Column Diameter 1m Bioreactor 10 m3
Conclusions
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Conclusions
• 20 kg Sulfur/day – 12.000 kgS/day
• Low cost per kg S removed
• Easy operation and high availability.
• Proven constant high H2S removal efficiency: 97-99%
• Can work with different biogas upgrade methods: • membrane units • high pressure absorption
• Minimum generated waste. Sulfur recovery ~95%
• bioSulfur can be further used as agricultural fertilizer.
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THIOPAQ® is a powerful alternative to other conventional desulfurization processes
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Other Thiopaq® units
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Landfill in Long Island, New York 3 tonS/day
Landfill in Las Vegas 2,3 tonS/day
Landfill in Seoul, 10 tonS/day
Landfill in France 200-300 kgS/day
