Innovative technologies for biogas upgrading: from basic ...
Transcript of Innovative technologies for biogas upgrading: from basic ...
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J. Colprim; María J. Martín ; M.D. Balaguer; J. Comas; M.Poch; S.Puig
Innovative technologies for biogas upgrading:
from basic research to technology assessment
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Biogas upgrading?
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What about biogas upgrading plants in Europe?
Upgrading and injection, Project map. Source: Platform biogas partner. http://www.biogaspartner.de/en/project-map.html
Source: IEA Bioenergy, Task 37. http://www.iea-biogas.net/plant-list.html (19/08/2014)
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What about biogas upgrading plants in Europe?
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Biogas components
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Biogas to biomethane: what to clean?
Water contents.
condensation (plus ammonia removal)
hygroscopic salts, glycol solutions, …
Hydrogen sulphide (H2S)
precipitation
Adsorption on A.C.
Chemical Absortion (NaOH)
Biological treatment
Siloxanes
Adsoption (A.C. or zeolites)
And CO2! To increase methane contents.
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Biogas to biomethane: requirements
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Biogas components solubility for water as solvent
H2S > CO2 > CH4 > Si (Lx or Dx)
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PSA: pressure swing adsorption.
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Water scrubbing
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Physical Absortion
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Chemical absorption
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Membrane separation.
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Biogas upgrading tecnologies. Key parameters
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Treatment cost? CAPEX vs. OPEX
Capex comparison:
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Treatment costs: PSA
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Treatment costs: water scrubber
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Treatment costs: Genosorb® scrubbers
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Treatment costs: amine scrubbers
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Treatment costs: membrane separation
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Biogas upgrading. BiogasApp CTQ2014-53718-R
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Removal of siloxanes
AD biogas
On-site experimentation
Storage ΔP (<40 bar)
SYN-ADG
affordable cost
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Removal of siloxanes
0,0
0,5
1,0
1,5
2,0
2,5
0 100 200 300 400 500 600 700
C/C
0
Time (min)
0,0
0,5
1,0
1,5
2,0
2,5
3,0
0 100 200 300 400 500 600 700
C/C
0
Time (min)
L2 Tolue D4 Llimonene D5
EBCT= 0,2s
Q=200 STPmL N2/min
H3PO4
Multicomponent adsorption
breaktrough curves
STEAM CHEMICAL
COMPOUND [C] (mg m-3)
L2 380
D4 1892
D5 2064
Toluene 3886
Limonene 752
Steam
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Removal of siloxanes: treatment costs.
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Removal of siloxanes: biological treatment?
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Removal of siloxanes: biological treatment?
P
MD
S m
em
bra
ne
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Removal of siloxanes: biological treatment?
Cyclic volatile siloxanes are (fast enough?) biodegradable
PDMS membranes are efficient for siloxane removal
AC efficiently concentrates VSiC on its surface
AC catalyzes siloxane bond cleavage
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Removal of siloxanes: biological treatment?
Insoluble
/bound
siloxanes
0-120 d
30ºC Inocula
Supernatant
THF extraction
Soluble
products
zeolite
AC2
AC1
Batch tests
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Conversion of CO2 to CH4?
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Microbial electrotechnologies (MET): what’s that?
From where comes MET ?
Rabaey and Rozendal (2010) Nature Reviews Microbiology 8, 706-716
Driving force: ΔG Cathode: reduction
Anode: oxidation Membrane: charge balance
ΔG<0
ΔG>0
- Oxidation environment
- (Biotic) Organic matter oxidation
(removal COD)
- (Abiotic) water electrolysis, H2
oxidation
- Reduction environment
- (Biotic) reduction of :
CO2 Prod. ; NO3- N2
- (Abiotic) Chemical e- acceptor:
O2 H2O
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Microbial electrotechnologies (MET): what’s that?
Source and products within MET: a biocathode reaction
Cathode: reduction
CO2
Valuable products:
Anode: oxidation
- Carboxylic acids: acetate, propionate, … - Methane - Alcohols: ethanol, butanol, …
Why it works:
- Anode: water oxidation - Cathode: CO2 reduction, biocathode - Energy: power supply - Membrane: C/A membrane or membrane less (study)
Driving force
e-
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Microbial electrotechnologies (MET): what’s that?
Rabaey and Rozendal, 2010. Nature Rev Microbiol
Ecell < 0
∆G > 0
Non spontaneous
Energy required
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Microbial electrotechnologies (MET): Methane Driving force
e-
Batlle-Vilanova et al. 2015
RSC Adv., 2015, 5, 52243 Doi:10.1039/c5ra09039c
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MET: CO2 to Methane
Lab scale BES
Electrochemical & Microbiological characterisation Reaction mechanism
Batch operation
Vcat= 0,4L
Feed: CO2-saturated mineral solution Cathode potential: -0,8V
Continuous
operation
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MET: the pilot
Inoculum from AD
Biocathode volume 0,42 L
Electrode surface 0,57 m2
Operation Batch / Continuous (HRT=18,3h)
Cathode potential -800 mV vs SHE
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36
The reactions…
CO2 + 8H+ + 8e− → CH4 + 2H2O
CO2 + 4H2 → CH4 + 2H2O
2H+ + e− → 4H2
E’0 = -0,24
E’0 = -0,41
Electromethanogenesis
Hydrogenotrophic methanogenesis
Ecell = Ecat − Ean
∆G = −n ∙ F ∙ Ecell
Thermodynamics
BIOCATHODE
ANODE
Water electrolysis
2H2O → O2 + 4H+ + 4e− E’0 = +0,82
∆G > 0 Energy required
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First results….. Current demand
(A mNCC-3)
pH Prod rate
(mM C d-1) CE (%)
201.7 ± 18.1 7.1 ± 0.2 15.4 ± 0.0 68.9 ± 0.8
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38
First results….. – Microbial community
Bacteria 45 %
Archaea 55 %
Methanobacterium sp. Cheng et al., 2009, ES&T
Van Eerten-Jansen et al., 2013, Archaea Villano et al., 2010, BITE
Clostridium sp.
Methylocystis sp.
Anaerophaga sp.
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CO2 + 8H+ + 8e− → CH4 + 2H2O
CO2 + 4H2 → CH4 + 2H2O
2H+ + e− → 4H2
E’0 = -0,24
E’0 = -0,41
Electromethanogenesis
Hydrogenotrophic methanogenesis
BIOCATHODE
Results – Microbial community
Anode Biocathode
H+
H+
H2O
O2
e-
CO2
CH4
e- e-
e-
e-
e-
Electrochemical characterisation
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Batlle-Vilanova et al., 2015, RSC Advances
Anode Biocathode
H+
H+
H2O
O2
e-
e- e-
H2
H+
CO2
e-
e-
e-
O2
H2O
CH4
CH4
CO2
Methanobacterium sp.
Methylocystis sp.
SO42-
H2S
Anaerophaga sp.
Clostridium sp.
Med
Results – Methane production mechanism
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Other products from CO2?
1st Proof of concept:
Bioalcohols production
Ganigué et al. LEQUIA. (2015) Chem. Commun.
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CO2: Biological transformation
CO2
Acetate (C2) Ethanol (C2)
Butyrate (C4) Butanol (C4)
Caproate (C6)
Caprilic (C8)
Hexanol (C6)
Octanol (C8)
Chain elongation
Biofuels production
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Upgrading plants
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Upgrading plants
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Upgrading plants
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Take home message
Biogas Upgrading:
- cleaning process: stablished.... To be optimized?
Alternatives for SiO removal? Biological?
- Increase methane contents:
CO2 removal vs. CO2 recovery
CO2 conversion to methane as energy storage
Why not to convert to other valuable products?
- Which is the best option?
a DSS to assess process scheme definition
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J. Colprim; María J. Martín ; M.D. Balaguer; J. Comas; M.Poch; S.Puig
Innovative technologies for biogas upgrading:
from basic research to technology assessment