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Great Opportunities for
Anaerobic Digestion
Juan M. Lema
Department of Chemical Engineering
University of Santiago de Compostela, Spain
Castelló, 7 de julio de 2016
Enhancing biodegradability
and production of VFA
Very high polluted
Wastewaters
Waste water
Organic suspended solids
+
Wastewaters with toxic compounds
Effluent
ANAEROBIC TREATMENT
Biotransformed effluent
A
B
C
E
Hydrolysis Acidification
Hydrolysis or Acidification or
(Methanogenesis)
Hydrolysis Acidification
(Methanogenesis)
Hydrolysis Acidification
Methanogenesis
N- containing
wastewaters
Wastewaters with organics, sulphate and heavy metals
Effluent
Effluent
D Metal sulphide removal
Denitrification Nitrification
Acidification Sulphate reduction
Methanogenesis
-The core of integrated processes (2001)
(Lema & Omil, Water Sci.Technol 2001)
-Papers on Anaerobic Digestion (Scopus)
0
200
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1600
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1981-85 1986-90 1991-95 1996-2000 2001-05 2006-10 2011-15
-Papers on Anaerobic Digestion (Scopus)
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1600
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1981-85 1986-90 1991-95 1996-2000 2001-05 2006-10 2011-15
Bior.T
WST
WR
WER
WM
-Source
Sewage Treatment Plant
COD, N, P
CO2
Energy
Treated water
Solids Sludge
-Conventional STP
Sewage Treatment Plant
COD, N, P, Solids
Micropollutants
CO2 VOCs GHG
Energy
Reuse water
Biosolids
Recovery products
-A more advanced concept: Eco-Innovation
8
-“3 R” Objectives in WW Treatment
Reduce
Water and sludge of sufficient quality
Energy, Metals Chemicals, Nutrients , Bioplastics, Electricity, Cellulose...
Energy, Sludge, Space, Emissions, CAPEX, OPEX
Re-use
Recover
-“3 R” Innovation in WW Treatment
Retrofit
Re-Think New flowsheets
New conceptions
Include new units
Re-imagine
-New opportunities for AD
Sewage treatment (Retrofit) (Re-think)
Sewage treatment (Re-think)
BioMethane Biorefinery (Re-imagine)
Recover
Reduce
Reuse
Sewage Anaerobic Treatment
Reduce
Primary settler
Influent Effluent
Thickening tank Primary sludge
Sludge digester
Biogas
Thickening tank Secondary sludge
Anoxic Aerobic Activated sludge reactor
Dehydration system
Dehydrated sludge
Secondary settler
Water line Sludge line
Aeration
-Retrofit
13
-Anammox
Partial nitrification
Anammox Two steps
-Nitrogen removal by Anammox
One step.
O2
NH4+
NO2-
Anoxic
Anammox
N2 + NO3
-
Aerobic
Decantación
Primaria
Entrada
Efluente
Espesadores
Fango Primario
Digestor
Anaerobio
Biogás
Tambores Espesado
Fango Secundario
Anóxico Aerobio
Sistema de lodos activos
Centrífugas de
Deshidratación
Lodo
Deshidratado
Decantación
Secundaria
Línea de agua
Línea de lodos
Pozo
Gruesos Bombeo
Pozo de
Fangos mixtos
Arena
Desarenador
Desengrasador Desbaste
Finos
Depósito de
Fangos Secundarios
Finos Gruesos
ELAN®
Cristalizador
NH4MgPO4
- STP Guillarei- Tui
-ELAN®. Guillarei-TUI (Spain)
Curitiba – Brazil
UASB reactors + DAF
• Design population: 600,000 inhabitants
• Flowrate: 1,100 L/s
-Anaerobic treatment of Sewage
-Anaerobic treatment of Sewage at moderate T
Biogas
• Nutrients •CH4 emissions
•Energy savings •Low biomass production
Anaerobic
UASB
Primary treated Urban wastewater
20 – 30 ºC
-Pilot Plant in Rotterdam (main stream)
-Anammox on main stream at low T
Direct growth on wastewater possible until 10 C No direct negative influence of BOD
Lotti et al. ES&T 2014
Temp. RateTot-N RateTot-Nmax qmax
°C g-N L-1 d-1 g-N L-1 d-1 g-N2 g-VSS-1 d-1
20 1.85 2.38 0.60
15 1.19 1.58 0.30
13 0.51 0.69 0.12
10 0.34 0.34 0.06
Primary settler
Influent Effluent
Thickening tank Primary sludge
Sludge digester
Biogas
Thickening tank Secondary sludge
Anoxic Aerobic Activated sludge reactor
Dehydration system
Dehydrated sludge
Secondary settler
Water line Sludge line
Aeration
-Rethinking STPs
22
Primary settler Influent Effluent
Thickening tank
Primary sludge
Sludge digester
Biogas
Thickening tank
Secondary sludge
Aerobic
SRT: 2 d
Dehydration
system
Dehydrated
sludge
Secondary
settler
Water line
Sludge line
ADN
ADN
Increase sludge production Decrease aeration requirements Low extent nitrification
NH4+ removal (suboptimal T)
T- P
Low temperature Anammox system
NH4 + removal (optimal T)
-High Rate (Low SRT) reactor + Anammox
Anammox
Thermal Hydrolysis
Enhanced precipitation (80% TSS removal)
-Enhanced precipitation (EP)
-EP. Plant Wide Modeling Simulation *
Variable Increase/Decrease
Oxygen - 22%
Electricity production +33,6 %
Biogas Production + 35 %
Sludge production - 8%
-60%
-40%
-20%
0%
20%
40%
60%
O2 Sludge Energy BGAS Electr
TPT + ANMX TPT +ENH.PREC.+ANMX TPT + HIGH RATE + ANMX
*
Thanks to Tamara Fernandez-Arévalo
Reduce
-Plant Wide Modeling Simulation
Primary settler
Influent Effluent
Thickening tank Primary sludge
Sludge digester
Biogas
Thickening tank Secondary sludge
Anoxic Aerobic Activated sludge reactor
Dehydration system
Dehydrated sludge
Secondary settler
Water line Sludge line
Aeration
-Re imagining
27
-ALL GAS Project
Influent Preliminary Treatment
Primary Sedimentation
Tank
Effluent Activated Sludge
Sludge Disposal
Dewatering
Thickener
Digester
Biogas
Anaerobic Process
Biogas
Algae Pond
Dewatering
Fertiliser
Waste biomass
Disintegration of solids
-Raceway
-Extension to 4 Ha. 2500 m3/d = 25 % of STP flow
- Granular anaerobic MBR and nutrient absorbers.
Screen Primary
Sedimentation
Raw wastewater
anMBR
1 ry / 2 ry
sludge Thickener
Sludge supernatant ( Return liquor )
Stabilised sludge to land
Anaerobic digester
Sludge recirculation loop to heat exchanger
Gas engine
Imported grid electricity
Digested sludge pump
Primary sludge pump
Thickened Primary sludge pump
Disposal of gross solids
Produced biogas
Treated effluent
Nutrient rich eluent
N - C
o n
t a c
t o r
P - C
o n
t a c
t o r
Sewage Anaerobic Treatment
Reuse
-Anaerobic + Aerobic MBR (for water reuse)
•Low-strength •Ambient temperature
UASB
•Energy savings •Low biomass production
MBR
Air
High quality effluent (COD, SS, microbiology)
Permeate
CH4 emissions
25-50% CH4
(dissolved)
Biogas
Primary treated Urban wastewater
10 – 20 ºC
Anaerobic
50-75% CH4
(biogas)
25-50% CH4
(dissolved)
Anoxic Aerobic
pe
rme
ate
NO3-
NH4+
NH4+
O2
CH4 + NO3
N2
wa
ste
wate
r
CH4 (GHG)
Aerobic
CH4 global warming potential of 25
-SIAM ® Concept
Denitrification coupled to methane oxidation
Aerobic pathway Anaerobic pathway
35
With 25 mg CH4·L-1
NC10
ANME-2 + Anammox
Methanotrophs + denitrifiers
35 mgTN·L-1 removed
58 mgTN·L-1 removed NO2
NO3
118 mgTN·L-1 removed NO3
-Background: CH4 & N removal
17 mgTN·L-1 removed
-Pilot plant (SIAM)
1
3 2
1 UASB reactor (141 L) 2 Anoxic Chamber (42 L) 3 Aerobic Membrane Chamber (22 L)
Supplier Zenon
Type Hollow fiber
Matherial PVDF
Pore size 0.04 µm
Area 0.9 m2
Support
-CH4 released
0
10
20
30
40
50
60
0 50 100 150 200 250 300
CH
4 (
mg·
L-1
)
Time (d)
CH4 influent CH4 Permeate
VIII I II III IV VI VII
-SIAM- MBR Comparison
AnMBR MBR SIAM
Flux (L/m2·h) 5-10 16-24 12-17
Energy (kWh/m3) -0.5/-0.7 0.2/0.4 -0.5/-0.7
Energy membrane 0.8/ 1.2 0.4/0.6 0.5/ 0.7
Total Energy 0.3/ 0.5 0.6/1.0 -0.2/ 0.2
CH4 emissions Yes Yes No
Denitrification No Yes Yes
Sludge surplus (kg SST/m3)
0.08/0.16 0.2/0.3 0.08/0.16
J. Garrido et al, 2015)
-Pilot plant (SIAM)
(STP Cartagena, Murcia, Spain)
1.- Biomethane
Recover
Biogas
production in
Europe (2014)
Anaerobic (co) Digestion
Quality? Maximum production?
Proportions? Loading rate?
-Co-substrates blending... Let’s try!
-A more rational approach
DIAGNOSIS CONTROLLER
FILTER BLENDER
Indicator C
Mo
dif
ica
tio
n o
f o
pe
rati
on
al
rest
rict
ion
s
fCH4
fRatio
Alkalinity Ratio
Flow CH4
Linear Programming Optimisation method
xi (% vol.)
HRT
Linear restriction LOW HIGH
OLR (g COD/L·d) 0 5
N-TKN (g N/L) 0.2 4
Moisture (kg H2O/kg) 0.85 1.0
Lipids (g/L) 0 10
Alkalinity (g CaCO3/L) 2 8
Na+ (g/L) 0 3
Biogas quality (ppm H2S) 0 10,000
Digestate quality (g COD/L) 0 6
dt
dttRatioRatio
)(
dt
dttQQ
CH
CH
)(4
4
Ratio* QCH4* Control cycle = ¼ HRT
Ratio
QCH4
(Set Points)
0
0· 4
RatioRatio
RatioCHRatio
fiff
fifffCIndicator
LOWHIGHCURRENT LimitLimitCLimit ·Limit NEW
Apply to most active restriction
-Closed-loop control strategy
ANAEROBIC DIGESTER
(García-Gen et al , Water Research, 2015)
-Operational strategy: Industrial pilot plant
(EDAR de BENS. A Coruña, Spain
-Change of substrates fraction and OLR optimization
0
1
2
3
4
5
0
10
20
30
40
50
60
70
80
90
100
0 129 139 150 160 170 180 190 200 213 221 230 238 247
OL
R (
g D
QO
/L·d
)
% S
us
tra
te
(%C
OD
)
(days)
(García-Gen et al, 2015)
-OLR perturbations
0
1
2
3
4
5
6
7
8
0,0
1,5
3,0
4,5
6,0
7,5
9,0
10,5
12,0
100 120 140 160 180 200 220 240
Ace
tic
and
pro
pio
nic
co
nce
ntr
atio
n (
g L-1
)
O
LR (
g C
OD
L-1
d-1
); B
ioga
s (L
L-1
d-1
)
Time (d)
(Regueiro et al. XXXXXXX 2015) Regueiro et al. Biores.Technol. (2015)
-Microbiome as an “early indicator”?
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1D
ay1
50
Day
16
8
Day
17
2
Day
17
4
Day
17
9
Day
18
1
Day
18
9
Day
20
0
Day
21
0
Day
21
7
Cu
mu
lati
ve p
rop
ort
ion
at
fam
ily le
vel
f_[Cloacamonaceae]
f_Pseudomonadaceae
f_Actinomycetaceae
f_Dethiosulfovibrionaceae
f_Anaerobaculaceae
f_Bacteroidaceae
o__Bacteroidales
f_Porphyromonadaceae
o_Clostridiales
o_MBA08
f_Peptococcaceae
f_Acholeplasmataceae
f_Lachnospiraceae
f_Caldicoprobacteraceae
o_Clostridiales
f_Peptostreptococcaceae
f_Ruminococcaceae
f_Erysipelotrichaceae
f_Syntrophomonadaceae
f_Carnobacteriaceae
f_Clostridiaceae
f_[Tissierellaceae]
OLR
5
OLR
2
OLR
2
OLR
5
OLR
10
(Regueiro et al. Biores.Technol. 2015)
(Carballa et al. Current Opinion Biotechnol. 2015)
-Biogas upgrading to Biomethane
-Biomethane plant
-Biogas upgrading plants (2012)
http://www.iea-biogas.net/files/daten-redaktion/download/Technical%20Brochures/biomethane-status-2014.pdf
277 plants
-Commercial Technologies
- Scrubbing (Water or Organic solvents)
(Yang, Ge et al. 2014)
-Pressure Swing Adsorption
Biogas upgrading plant Mühlacker, GE (1000m³/h)
-Membrane separation
-CAPEX
Sun Li et al Renewable and Sustainable Energy Reviews, 2015
4 H2 + CO2 CH4 + 2 H2O
PATENT
PA: 61/563,247
Feed and produced CH4 are sparged through the membrane module to
create fine bubbles
-Lab-Scale Biological Upgrading
Díaz, I et al . Biores.Technol.. (2015)
T
P
BIOMETHANE
LIQUID EFFLUENT
GAS FLOWMETER
SAMPLING
POINT
GAS
CYLINDERS
H 2
METHANOGENIC
BIOREACTOR
CO 2
GAS FLOW
CONTROLLERS
BIOGAS
RECIRCULATION
GAS
PREHEATER
HOLLOW FIBRE
MEMBRANE MODULE
SAMPLING POINT
GAS
FILTER
70
75
80
85
90
95
100
0 0.5 1 1.5 2 2.5
Fin
al C
H4
con
cen
trat
ion
(%
v.)
𝐐𝐑𝐂,𝐆/𝐐𝐈𝐍,𝐆
50/5060/4070/30
Initial conc. (CH4/CO2)
4 H2 + CO2 CH4 + 2 H2O
Time (h)
0 50 100 150 200 250 300 350 400
mm
ols
CH
40
2
4
6
8
10
12
14
16Test 1
Test 2
Test 3
Test 4
Test 5 - OCV
Test 11
(Colprim et al. 2015)
-Microbial electrosynthesis (MES)
2. Biorefinery
RECOVER
-Biorefinery
R. Kleerebezem et al. Reviews in Environmental Science and Bio/Technology. (2015)
-Biorefinery
VFA
Bioplastics
Energy
n-Caproate, n-Caprylic acid, etc
Fuels (e.g. butanol) Raw chemicals (e.g. VFA, esters, etc)
[Electrosynthesis]
[Reverse β oxidation]
Chain elongation
[Organic chemistry]
[Organic chemistry]
-Bottlenecks
Selectivity: Obtain certain
VFAs and the desired amount of each one.
Product inhibition: Extract the product to let the fermentation keep going.
-VFA: Why is selectivity important?
Acetate Butyrate Propionate Valerate
PHB PHV
Brittle and stiff P(3HB-co-3HV)
More flexible and tougher
Lee et al.: Chemical Engineering Journal (2013)
-Increasing selectivity
pH
Feeding pattern
Substrate concentration
(co) Substrate
HRT Temp
-Influence of pH on selectivity
Temudo, M.: Appl. Microbiol. Biotechnol. (2008)
0
10
20
30
40
50
60
70
80
90
35 °C 45 °C 55 °C
%
Acetate
Propionate
Butyrate
Valerate
Jiang et al. Bioresource Technology 2013)
-Influence of T on selectivity
-Effect of Electrochemical coupling and HRT
Zhang et al.: Bioresource Technology (2015)
-Thermodynamic-based Model for Products Yielding
Prediction
Hypothesis: The species able to harvest more energy in the imposed conditions will dominate the process.
-
39-
Gonzalez-Cabaleiro et al. Plos One (2015)
-Acidogenic Fermentation.
pH
-
38-
Butyrate
Acetate
Ethanol
Product Yield
Propionate
Gonzalez-Cabaleiro et al. Plos One (2015)
- VFA continuous removal
Ludo Diels (VITO, Belgiumi. http://www.water4crops.org
-VFA Removal Technology: Electrodialysis
Reduced 1500 mg/l VFA (acetic, propionic, butyric & valeric) by up to 99% in 60 minutes.
Jones et a. Bioresource Technol. (2015)
-In Situ Product Recovery (ISPR)
0
2
4
6
8
10
Without ISPR With ISPR
Pro
du
ctiv
ity
(g/L
·h)
Succinate (Cell recycle +mono+-polar ectrodialysis,Meynial-Salles, 2008)
Lactate (Electrodialysis, Min-tial, 2004)
Lactate (Electrodialysis, Min-tial, 2005)
ABE (Gas stripping, Xue, 2013)
ABE (Gas stripping, Ezeji 2003)
Van Hecke et al.: Biotechnology advances 2014
- Wastewater to Bioplastics
Step 1. Natural Selection
STRATEGY: Feast-Famine regime
Enrichment reactor
PHA production during the feast
phase
PHA consumption during the famine
phase
Very fast substrate uptake
DO profile
Step 2. PHA production
Time [h]0 5 10 15 20 25 30
Biop
last
ic [w
t%]
0
20
40
60
80
100
80 wt% Bioplastic
-Wastewater to Bioplastics
-Pilot plant of PHA (Aquiris. Brussels)
-Pilot plant at Mars chocolate. Veghel (NL)
- Production at industrial location at
1 kg/day scale
- Reactor volumen: 300 L.
- The production has to be optimized
to bring down the production costs
of currently about 8 euro/kilogram to
2 euro/kilogram.
Princess Aurora
Maleficent
-The sleeping beauty…
0
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1981-85 1986-90 1991-95 1996-2000 2001-05 2006-10 2011-15
… and the Prince
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1200
1400
1600
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1981-85 1986-90 1991-95 1996-2000 2001-05 2006-10 2011-15
Who is the Prince?
-Sustainability -Resource recovery
-Anammox -..............
Brilliant future !!
-The A(co)D team
Juan M. Lema Marta Carballa Jorge Rodríguez
Iván Rodríguez
Alberte Regueira Antón Taboada
Leticia Regueiro Rebeca González
Lorena González
Santiago García
Chiara Pedizzi
-The (bio) Group USC
Great Opportunities for
Anaerobic Digestion
Juan M. Lema
Department of Chemical Engineering
University of Santiago de Compostela, Spain
Castelló, 7 de julio de 2016
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