Biogas Upgrading and CO2 Seperation

New Trends
in
Biogas Upgrading
The potential of biogas
▪ Biogas is the by-product from AD with the highest valorization potential
HOUSEHOLD
HEAT
FINE & BULK CHEMICAL
BIOCONVERSION
ELECTRICITY
&
INDUSTRIAL HEAT
BIOgas
VEHICLE FUEL
FUEL CELLS
INJECTION INTO
NATURAL GAS GRIDS
▪ Huge potential for Biogas production in Europe
2016
16.1 Millions Toe in the EU28
Biogas Electricity 62.5 TWh
EuroObserv’er 2017
EuroObserv’er 2017
▪ Production of Biogas in the EU28 will reach 18-20 billions Nm3 by 2030 (EBA)
The need for biogas upgrading
▪ Biogas composition depends on the RedOx state of the organic matter and the
type of AD process Decrease in the specific
calorific value
Component Landfill Gas WWTP/FoodWaste/Manure
Explosion risk
CH4 35-65% 53-70%
CO2 15-50% 30-47%
Decrease in CH4 concentration
N2 5-40% 0-3%
O2 0-5% 0-1% Corrosion in pipelines,
H2 0-3% - compressors, engines
CO 0-3% -
H2S 0-100 ppmv 0-10.000 ppmv Silicone oxide deposits:
NH3 0-5 ppmv 0-100 ppmv Abrasion & malfunctioning of
Engines
Siloxanes 0-50 mg Si m-3 0-41 mg m-3
Halocarbons 20-200 ppmv Cl -/F- -
VOCs 0-4500 mg m-3 0-200 mg m-3
Persson et al, 2006; Bailón and Hinge, 2012
▪ Biogas upgrading is a function of the specifications of the final use of Biomethane
Household Internal Combustion Micro-

Turbines Fuel Cells
Heat Engines turbines
H2S < 1000 ppmv < 200-1000 ppmv < 10000 ppmv < 70000 ppmv < 10 ppmv
Siloxanes - < 9-44 ppmv < 0.0068 ppmv 0.005 ppmv 1 ppmv
Bailon and Hinge (2012)
▪ No CO2 removal required in internal combustion engines, turbines or micro-

turbines & fuel cells
▪ Higher Technical specifications for Biomethane for injection into natural gas
grids or use as vehicle fuel
The biogas upgrading market
▪ The number of biogas upgrading plants in the world
▪ Distribution of Biogas upgrading plants in the world
(IEA Bioenergy 2018)

2012 2016
(IEA Bioenergy 2014) (IEA Bioenergy 2018) 11

The cost of biomethane production
▪ Cost of biogas upgrading = 0.2 € m-3
10
8
Operation cost (Cts € kwh-1)
Biogas Production Biogas Upgrading Biomethane Injection Total Cost of Biomethane

Production
(IEA Bioenergy 2014)

CO2
r
colum
Absorpt
Gas
conditioning
column
Physical/Chemical CO2 removal Technologies
Flash
Upgraded Raw Compressor
A biogas
biogas
Scrubbing (CH4 96-98.5 %) Air withCondensate

desorbed
CO2
Absorption
Upgraded C Upgraded
Desorption
A
column
biogas
P↓↓
column
biogas Off-gas
Air with
column
desorbed
Flash
CO2
Absorption
Air
P↓
Cooler
Desorption
Stripper
column
Absorber
column
Compressor
Water
column
Raw biogas Make-up bleed

Flash
water
Air
Hot water/oil
Compressor or steam
BWater Upgraded
H2biogas
SRaw Heater Reboiler
HS
Raw 2
biogas Make-up bleed
biogas
water
Pressurized Water Off-gas Alcanol Amines

B (1-2 bar)
Heater
Cooler
(6-8 bar) Upgraded
Desorption
biogas Absorption
column
column
Gas
conditioning
column
Flash
Off-gas
H2S + H2O Stripper
Heater
gas
Cooler
Desorption
Raw Compressor
Absorption
column
biogas
column
Gas
conditioning Condensate
column
Flash
Stripper
gas
Raw Compressor C Polyethyleneglycol-based
Upgraded solvents
PSA Adsorption (CH4: 96-98 %)

Upgraded biogas
4-10 Purge gas
bar
Depressurization
Pressurization
Adsorption
Desorption
PSA
columns
Vacuum
pump
Waste
Compressor gas
H2S + H2O
Raw
biogas
Siloxanes
Separation based on size exclusion

and differential affinity for CO2/CH4
Membrane separation (CH4: 96-98 %)

I Waste gas
Raw Upgraded
biogas biogas
HWater
2S + and
H2O
H2S removal
Siloxanes II CO2 and CH4 for
Waste gas recirculation
Particles
Membranes
Raw Upgraded
biogas biogas
Raw III
Waste gas
biogas
CO2 and CH4 for
recirculation
Compression
Raw Upgraded
biogas biogas
(Bauer et al. 2013)

Energy demand: 3-12 % energy content of Biogas
0.55 kWh Nm-3
0.4-0.51 kWh Nm-3
(Bauer et al. 2013)

http://iqtma.uva.es/envtech/
Biomethane Cost- Low
Biological CO2 removal Technologies
O2-free CH4 (g)

Treated
Water
SO42- (L) Microalgae

O2 (L) Biomass
CO2 (L) H2S (L)

CO2 (g)
H2S (g)
CH4 (g)
Wastewater
Photosynthetic Upgrading
Upgraded
biogas
Absorption
column
Microalgae
recycling
Raw
biogas
Nutrient
solution HRAP Sedimentation
tank
CH4 > 95 %, CO2 < 1 %, N2 < 3%, O2< 0.5 %

Upgraded
biogas
Absorption
column
Microalgae
recycling
L
Raw G
biogas
Nutrient
tank
Key operational parameter: Recycling Liquid/Biogas ratio

Upgrading- photosynthetic biogas
Demo plant at Chiclana de la Frontera

32 m2
(m (Nm /h) treated b
Investment c
5000
(€ (Nm /h) treated

400
-1 4000 Upgrading
Land
-1
300
3
3000 200
3
2000 100
2
1000
0.4
0.2
0 0.0
HRAP-AC ACF-WS HRAP-AC ACF-WS
b)
b)
0.35
0.25
0.30
(KW-h (Nm ) treated biogas)

0.20
(€ (Nm ) treated biogas)
0.25
Operating costs
0.20
Energy
0.15
3 -1
3 -1
0.15
0.10
0.10
0.05
0.05
0.00 0.00
HRAP-AC ACF-WS HRAP-AC ACF-WS
Hydrogenotrophic Upgrading
Wind power
Electric grid
Electricity CH4
BIOGAS
Anaerobic
digester
Electricity
ORGANIC
MATTER NUTRIENTS
ELECTROLYSIS
OF WATER H2 H2O
Storage & utilization
Hydrogenotrophic
▪ CO2 used reactor
as C source and e- acceptor and
problems
H2 used as e- donor
O2
CO2 + 4 H2 → CH4 + 2H2O
▪ Implemented at Demo Scale
Hydrogenotrophic Upgrading
Power-to-gas plant produces about 1,000

metric tons of e-gas per year, chemically
binding some 2,800 metric tons of CO2.
H2S
Physical/Chemical H2S removal Technologies
Chemical precipitation
FeCl2, FeCl3, FeSO4
▪ Based on the low solubility of FeS
▪ Suitable for high [H2S]
▪ Upgraded biogas with [H2S]< 150 ppmv

▪ High operating cost
Physical/Chemical H2S removal Technologies
Adsorption
Upgraded
biogas
Regeneration
Adsorption
Raw
biogas
▪ Adsorbents: Fe2O3, Fe(OH)3, ZnO, Activated
Carbon
▪ Typical EBRT ≈ 1-15 min (H2S-RE > 99%)
▪ Prohibitive operating costs in large digesters

Biological H2S removal Technologies
Aerobic
Biotrickling Filtration
Upgraded
biogas
Anoxic
Biotrickling
filter
Raw biogas
Nitrate solution
pH control Nutrient ▪ Based on the action of lithoautotrophs: H2S
HCl/NaOH solution as energy source & CO2 carbon source
▪ e- acceptor: O2 or NO3-
O2/NO3
-
▪ No significant CO2 associated
▪ EBRT: 2-16 min (H2S-RE: 99%)
▪ Full Scale Technology
O2-free CH4 (g)
Treated
Water
SO42- (L) Microalgae

Biomass
▪ The high pH value→ High H2S mass transfer
O2 (L)
CO2 (L) H2S (L)

▪ RE-H2S > 99 %
H2S (g)
CH4 (g)
CO2 (g)
Wastewater
Upgraded
biogas
Absorption
column
Microalgae
recycling
Raw
biogas
Nutrient
tank
Microaerobic AD
H2S- free Biogas
O2
▪ No need for external desulfurization

▪ No impact in AD
▪ EBRT > 5 h for H2S-RE > 97 %

▪ Periodical cleaning of AD headspace
2.5
Anaerobic O2 supply into O2 supply into
2.0 Feeding Pipeline Headspace
H2S concentration (% )
1.5 H2S
1.0 O2
0.5
0.0
0 20 40 60 80 100 120
Time (d)
75
CH4 and CO2 (%)
60
CH4
45
30
CO2
15
0
0 20 40 60 80 100 120
Time (d) http://iqtma.uva.es/envtech/
Take home message
Biogas Upgrading market dominated by physical/chemical

Technologies → High Operating Cost & Environmental Impact
✓ Biological Processes have shown similar CO2 and H2S removals

but at:
▪ Lower operating costs and environmental impacts
▪ No need for previous removal of particles/H2O/siloxanes
▪ Tested at pilot and full scale
▪ Use of residual nutrients from digestate
✓ Photosynthetic upgrading allows for simultaneous H2S & CO2
removal
http://gastreatment-microalgaeresearchgroup.blogspot.com.es/
Muñoz R*, Meier L., Diaz I, Jeison D (2015) A critical review on the state-of-the-art of
physical/chemical and biological technologies for an integral biogas upgrading. Reviews in
Environmental Science and Bio/Technology
Follow us Twitter: @VOC_Odours

Visit our Facebook site: facebook.com/VocOdoursGroup
University of Valladolid

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New Trends

16.1 Millions Toe in the EU28

Biogas Electricity 62.5 TWh

▪ Biogas upgrading is a function of the specifications of the final use of Biomethane

Household Internal Combustion Micro-

▪ No CO2 removal required in internal combustion engines, turbines or micro-

(IEA Bioenergy 2018)

(IEA Bioenergy 2014) (IEA Bioenergy 2018) 11

Biogas Production Biogas Upgrading Biomethane Injection Total Cost of Biomethane

(IEA Bioenergy 2014)

Scrubbing (CH4 96-98.5 %) Air withCondensate

Raw biogas Make-up bleed

Pressurized Water Off-gas Alcanol Amines

PSA Adsorption (CH4: 96-98 %)

Separation based on size exclusion

Membrane separation (CH4: 96-98 %)

(Bauer et al. 2013)

Energy demand: 3-12 % energy content of Biogas

0.55 kWh Nm-3

0.4-0.51 kWh Nm-3

(Bauer et al. 2013)

O2-free CH4 (g)

SO42- (L) Microalgae

CO2 (L) H2S (L)

CH4 > 95 %, CO2 < 1 %, N2 < 3%, O2< 0.5 %

Key operational parameter: Recycling Liquid/Biogas ratio

Demo plant at Chiclana de la Frontera

(€ (Nm /h) treated

(KW-h (Nm ) treated biogas)

Power-to-gas plant produces about 1,000

FeCl2, FeCl3, FeSO4

▪ Based on the low solubility of FeS

▪ Suitable for high [H2S]

▪ Upgraded biogas with [H2S]< 150 ppmv

▪ Prohibitive operating costs in large digesters

SO42- (L) Microalgae

CO2 (L) H2S (L)

H2S- free Biogas

▪ No need for external desulfurization

▪ EBRT > 5 h for H2S-RE > 97 %

Biogas Upgrading market dominated by physical/chemical

✓ Biological Processes have shown similar CO2 and H2S removals

Follow us Twitter: @VOC_Odours

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