optimization of mono-digestion of vinasse in the ... mi triolo.pdf · optimization of...
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Optimization of mono-digestion of
vinasse in the biorefinery chain
1Triolo JM, 2 Moraes BS, 1Lecona VP, 1Sommer SG, 3Zaiat M
1University of Southern Denmark (SDU)
1Brazilian Bioethanol Science and Technology Laboratory (CTBE), Brazilian Center for Research in Energy and Materials (CNPEM)
3São Carlos Engineering School (EESC), University of São Paulo (USP)
University of Southern Denmark
Main Campus Odense
• The 3rd largest city in Denmark
• 200,000 PE.
• Hometown of Hans Christian Andersen
o Researchers : 1,200
o Students : 26034
o Five faculties
Humanities, Science, Engineering, Social Sciences, Health
o 6 Campuses
University of Southern Denmark
Oil crops
Sugar and starch
plants
Solid biomass
(Wood, straw,
etc)
Wet biomass
Vegetable oil Methyl ester
(Biodiesel)
Sugar
Fuel gas (Syngas)
Biogas
Pyrolytic oil
Crushing
Refining
Extraction
Hydrolysis
Hydrolysis
Combustion
Pyrolysis
Gasification
Transesteri-
fication
Ethanol Fermentation Gas,
Liq
uid
bio
fuels
Tra
nsp
ort
Heat
Ele
ctr
icit
y
Anaerobic
digestion
BioGAS from any biomass
Thermochemical
platform
Vinasse
Bagasse
Glycerol Sugar platform
Sugar cane/beet
Bioethanol
Fertiliser
(Field)
Sugar beet
Biogas production
C5 vinasse
Anaeorbic digestion of vinasse in the biorefinery chain
Sugar cane/beet
Bioethanol
C5 vinasse
Biogas production
BioEthanol production
Biogas production
(Bioethanol + biogas model)
5
Biogas production within the bioethanol production chain Biogas production within the bioethanol production chain
CH4
emission
N2O emission
Fertiliser
(Field)
Intergrated Biorefinery
Sequantial biofuels and
biofertiliser production
And less GHG emission
Experimental setup (CSTR)
Continuous Stirred Tank Rectors (2X CSTRs, 20L)
Supply macro- and micronutrients
(Animal manure, biorefinery by-products (Filter cake))
Obtained within the biorefinery boarder:
(more economically advantageous)
CSTR 1: without manure supplement.
Chemical nutrition (FeCl36H2O, nickel and zinc etc),
afterwards, lime fertiliser replaced the chemical nutrition.
CSTR 2: Cattle manure (3wt% )
ORL : up to 3g /L day, HRT: 20 to 36 days.
Add straw (2.9wt%) for balancing C/N ratio (10)
Methods
Phase Description
I Acclimation
II Increase of OLR
III Addition of cellulose for adjustment of C/N ratio (10) and chemical
nutrients supplementation
IV Replacement of cellulose for straw and chemical nutrients by lime
fertilizer
V Increase of OLR
Phase Description
I Acclimation
II Increase of OLR
III Addition of cellulose for adjustment of C/N ratio (10)
IV Replacement of cellulose by straw
V Increase of OLR
CS
TR
-1
CS
TR
-2
Only vinasse
Vinasse + 3%
manure
(○) CSTR-1 (only vinasse) : Methane content 58.3%, Biogas 0.90 L/L day (±0.15) (●) CSTR-2 (manure added): Methane content 58.6%, Biogas 0.97 L/L day (±0.13)
Methane production
replacing straw adding cellulose Increase OLR
BMP of Vinasse (267.4 (±4.5) mL CH4/g VS
Performance
CSTR-1 ~235.7 (± 32.2)mL CH4/g VS
CSTR-2 ~265.2 (± 26.8)mL CH4/g VS
Methane production : very
close to BMP
Acetate/propionate ratio during the operation of (○) CSTR-1 (only
vinasse) and (●) CSTR-2 (vinasse and 3% manure).
A/P ratio > 1.4
AD process stability
To
tal V
FA
(g/l)
Ace
tate
/pro
pio
nate
ra
tio
Conclusions from this study Addition of filter cake
Effective to provide nutritional complementation to this complex substrate, improving methane production.
Addition of Cow manure
More effect for stable AD operation than filter cake
Straw
For sugar beet vinasse : Optimum C/N ratio
Alternative substrate for from January to April (No Vinasse production)
The use of these co-substrates could improve the energy balance in a biorefinery, through optimization of biogas production and reuse of its byproducts.
Mono digestion was successful, but low biogas yields due to high water content of vinasse (60 g VS/L), and longer retention time (20days) using CSTR
Co-digestion with manure or sludge using CSTR would be an option.
(no pH adjust, robust…)
PART II. PRETREAMENT OF LIGNOCELLULOSIC BIOMASS
11
Jin Mi Triolo , Mads Ujarak Sieborg, Brian Dahl Jønson
University of Southern Denmark (SDU)
Methane Potential profile of 92 plant biomass Wheat straw and bagasse are recalcitrant biomass…
12
0
100
200
300
400
500
600
Lignocelluosic biomass
Herbaceous plants
gas potential of straw
App. 200 L CH4 /kg VS
Lignocelluosic
non- Herbaceous biomass
Level of gas potential in plant biomass in plant biomass
CH
4 L
/ k
g O
M
Theoretical BMP
Po
ten
tial to
imp
rove!?
Long Storage reduces methane yield
13
0
50
100
150
200
250
Just after harvested straw Straw after 10 monthes of
storage
15 day
25 day
60 day
• 4 months : 7.4 % loss (Ma et al., 2013)
• 2 months : no clear effect (SDU data) Results from batch reactor
CH
4 L
/ k
g O
M
14
Winter reed canary grass
Sometimes, I see a sample
with critically low biogas potential
79%
21% Methane potential
104 m3 /ton OM
Autumn reed canary grass Summer harvested
52% 59% 296m3 /ton OM
258m3 /ton OM
48% 41%
Underutilised waste biomass
Non biodegradable
Non biodegradable
Non biodegradable
Straw - Alternative biomass for biodigestion ( Very typical lignocellulosic biomass )
15
15
0
50
100
150
200
250
300
350
400
450
500
Barely straw Wheat straw1
Wheat straw2
Pretreatment is needed
Theoretical gas potentential
≈ 65% of carbon NOT to biogas
Lignocellulose metrix Confidential data
CH
4 L
/ kg
OM
Cellulose 48% Hemicellu
lose 28%
Lignin 12%
Non-fiber 9%
Ash 3%
Oil crops
Sugar and starch plants
Solid biomass (Wood, straw, etc)
Wet biomass
Vegetable oil Methyl ester (Biodiesel)
Sugar
Fuel gas (Syngas)
Biogas
Pyrolytic oil
Crushing
Refining
Extraction
Hydrolysis
Hydrolysis
Combustion
Pyrolysis
Gasification
Transesteri-
fication
Ethanol Fermentation Gas
, Liq
uid
bio
fue
ls
Tran
spo
rt
He
at
Ele
ctri
city
Anaerobic
digestion
Bagasse would be for biogas production?
Thermochemical
platform Bagasse
Sugar platform
Pretreatment
Bagasse
Cellulose 50%
Hemicellulose 23%
Lignin 22%
Ash 5%
Wheat straw
Cellulose 48%
Hemicellulose
28%
Lignin 12%
Non-fiber 9%
Ash 3%
Lignocelluloses in Bagasse
Recalcitrant carbon- lignocellulose
18
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1
15 20 30 45 Average
Lipid
Protein
Lignocellulose
-10%
0%
10%
20%
30%
40%
50%
15 20 30 45 Average
Hemicellulose
Cellulose
Lignin
Retention time (Day)
Retention time (Day)
Very simplified lignocellulos structure
Destruction rate (%) of Lignocelluloses
Destruction rate (%) of organic carbon
100
80
60
40
20
0
Vazifehkhoran and Triolo, 2014
Straw for biogas production and its
pretreatment effect?
19
Before Pretreatment
170
450
theoretical BMP
37% for biogas
170
XX Pretreatment
Pretreatment effect 30%
221
49% for biogas
170
XX Pretreatment
Pretreatment effect 100%
340
75% for biogas
Cost-effective?
Energy efficient?
Any toxic by-products from
severe treatment?
Unit ; CH4 NL/kg VS
What if we apply more pretreatment
methods to co-ensiled straw???
Biological pretreatment?
Hydro (Thermal pretreatment?)
Mechanical (Phsical pretreatment?)
Chemical Pretreament?
20
21
Wheat straw
Hydrothermal
Pretreatment
Physical
Pretreatment
Increases in:
- Accessible surface
area.
- Size of pores.
- Partial
solubilisation.
Decreases in:
- Viscosity.
Partial degradation of
hemicellulose
Increases in:
- Accessible surface
area due to swelling.
- Porosity
Decreases in:
- Degree of
Polymerisation
- Crystallinity
Hemicellulose and
lignin degradation
Increases in:
- Accessible surface
area
- Size of pores
Decreases in:
- Degree of
Polymerisation
- Crystallinity
- Viscosity
Chemical
Pretreatment
Pretreatment
effect?
22
Pretreatment
design
340
75% for biogas
Unit ; CH4 NL/kg VS
450
theoretical BMP
23
180 214 223 234
050
100150200250300350400450
M M+T M+T+C M
+Combined
(C and T)
Comparison of BMP (CH4 Nl /kg VS)
19 24 30
0
10
20
30
40
M+T M+T+C M +Combined (Cand T)
Treatment effect %
Pretreatment results
(Wheat straw) M: Milling
T: Thermal
C: Chemical
Methane production (CH4 nL/kg VS)
24
Pretreatment results
(Co-ensiled straw)
No Pretreatment effect!
Effect of ensiling
andpretreatments overlap
25
Scanning electron microscope
(SEM) analysis
A: Untreated straw.
C: Thermal and chemical pretreated straw. B: Co-ensiled straw
26
Low-cost co-ensiling may replace
expensive conventional pre-
treatment methods!
Summing-up
