Post on 13-Dec-2015
In-Situ Transformation of Municipal Sewage Sludge into Biodiesel
Grupo de IngenieríaQuímica y Ambiental
Rebeca Sánchez VázquezI. A. Vasiliadou, Juan A. Melero, F. Martínez,
L. Fernando Bautista, J. Iglesias, G. Morales and R. Molina
In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de
Ingeniería QuímicaY Ambiental
1st generationbiodiesel
O
OPalm Oil
Canola Oil
Sunflower Oil Soya Oil
Castor Oil
Jatropha Oil
The biodiesel production process11stst Generation Biodiesel Generation Biodiesel
In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de
Ingeniería QuímicaY Ambiental
Non-ediblefeedstock
Newtechnologies
Non-foodcrops
Algaeoils
Microbialoil
Wastecooking
oils
Other waste
2nd GenerationBiodiesel
Non-food / landfor fuel
Saferprocess
Greenerprocess
Profitableprocess
High purityby-products
The biodiesel production process22ndnd Generation Biodiesel Generation Biodiesel
Wasteanimal
fats
In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de
Ingeniería QuímicaY Ambiental
Alternative source for oleaginous feedstock
Wastes Large amounts of non-saponifiable compounds
Contact with water High FFA contents due to hydrolysis processes
~ 1.6 MT produced yearly in the EU
Increasing due to incresing urbanization
and industrialization.
~ 10-30 wt% of lipids content
Direct adsorption of lipids onto the sludge.
Cell membrane of microorganisms composed of phospholipids
Sewage sludgesSewage sludges
Experimental
In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de
Ingeniería QuímicaY Ambiental
Oil Extraction
Solvents Diethyl Ether, n-Hexane and methanol
Conditions Temperature: Boiling point of the solventSolvent to Biomass: 10 – 15 mL·g-1
Contact time: 2.5 and 4.0 hours
Drying stageT = 80ºC
P = 0.5 bart = 12 hours
WaterWaterremovalremoval
Solvent refluxingT = Boiling Temp.
P = atm.t = 2.5 – 4.0 hours
ExtractionExtractionof lipidsof lipids
Filtration
SolidsSolidsremovalremoval
EvaporationT = 80ºC
P = 0.2 bar
LipidsLipidsconcentrationconcentration
In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de
Ingeniería QuímicaY Ambiental
Zr-SBA-15Zirconium species
Isomorphic substitution
Mesostructured silica as solid supportHigh surface area. Large pore size.
Lewis-type acid catalyst
Zirconium &zirconium dioxide
species
Zr – SBA-15
Heterogeneous acid catalytic system
Zr loading (wt. %): 8.4SBET (m2/g): 556Vp (cm3/g): 1.35 Dp (nm): 12.9
Si/Zr) EDX 20Si/Zr) bulk –ICP 16Si/Zr) XPS 18
• High incorporation of Zr.
• Textural properties.
• Mesoscopic ordering.
In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de
Ingeniería QuímicaY Ambiental
Temperature(ºC)
Catalyst Loading (wt% on lipid mass)
MeOH/Saponifiable Matter (mol/mol)
209 12.5 50
Catalytic test
Tryglicerides & free fatty acidsMethanol
+
Biodiesel
+
Glycerol
250
20050100 150
Mechanical stirrerTIC
PI
Heating
Stirring system
Reactor vessel
200
250
20050100 150
250
20050100 150
Mechanical stirrerTIC
PI
Heating
Stirring system
Reactor vessel
200
Stirring rate: 2000 rpmHeating ramp: 7ºC/minAutogenous pressure
In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de
Ingeniería QuímicaY Ambiental
7 6 5 4 3 2 1 01H d (ppm)
CH3R…
CH 2
C H2
C
O
...R
C H2
C H2
C
O
O
C H2
C HO...R
C H2
C H2
C
O
C H2
O...R
C H2
C H2
C
O
OH...R
C H2
C H2
C
O
Yield toward FAME: 1H NMR
Results & Discussion
In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de
Ingeniería QuímicaY Ambiental
Oil Extraction:Oil Extraction: PrimaryPrimary - - Sewage SludgesSewage Sludges
n - Hexanen - Hexane
Extr
actio
n Yi
eld
(wt%
)
MethanolMethanolDiethyl etherDiethyl ether
n-Hexane & methanol Very good extraction yields Diethyl ether
Very poor extraction yield.
Discarded solvent.
15,0
12,5
10,0
7,5
5,0
2,5
0,0
Large amount of UnsaponifiableMatter and Free Fatty Acids
obtained
In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de
Ingeniería QuímicaY Ambiental
% FFA% Gly
Reaction Product (3h)
0
20
40
60
80
100
Mola
r co
mposi
tion (
%)
FA
MEY
ield (%
)
0
20
40
60
80
100
Reuse Product (3h)
Reaction Product (6h)
Transesterification reaction – Transesterification reaction – Primary - Sewage SludgesPrimary - Sewage Sludges
Batch experimentsBatch experiments
High conversion of FFA and TG into FAME after 3h6.0 % of the total sewage sludge is
converted into FAME
In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de
Ingeniería QuímicaY Ambiental
0
20
40
60
80
100
Mola
r co
mposi
tion
(%
)
FAM
EYie
ld (
%)
0
20
40
60
80
100
% FFA% Gly
Transesterification reaction – Transesterification reaction – Primary - Sewage SludgesPrimary - Sewage Sludges
In SituIn Situ Process Process
Blank
Reaction Product (3h)
DB(g)/S(ml) = 0.1
Reaction Product (3h)
Reaction Product (6h)
Reuse Product (3h)
RP (3h) Wet Sludge
DB(g)/S(ml) = 0.25
High FAME yield from
primary sewage sludge
through In situ process
High FAME yield from
sewage sludge without
drying treatment (72 wt%
water content)
In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de
Ingeniería QuímicaY Ambiental
15.5 % of the total sewage sludge is converted into FAME
5.8 % of the total sewage sludge is converted into FAME
Conventional ProcessConventional Process In SituIn Situ Process Process
Transesterification reaction – Transesterification reaction – Primary - Sewage SludgesPrimary - Sewage Sludges
In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de
Ingeniería QuímicaY Ambiental
0%
20%
40%
60%
80%
100%
46,5
17,0
36,5 Glycerides
FFA
UM
Oil Extraction:Oil Extraction: SecondarySecondary - - Sewage SludgesSewage Sludges
Extr
actio
n Yi
eld
(wt%
) n-Hexanen-Hexane
The amount of extracted lipid from
secondary sludge is much lower
3.0
2.5
2.0
1.5
1.0
0.5
0.0
Greater proportion of saponifiable matter and Free Fatty Acids obtained
MethanolMethanol
Com
posi
tion
(%)
0%
20%
40%
60%
80%
100%
46,5
17,0
36,5 Glycerides
FFA
UM62.362.3
20.720.7
16.916.9
In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de
Ingeniería QuímicaY Ambiental
Transesterification reaction – Transesterification reaction – In Situ Process
SecondarySecondaryPrimaryPrimary
World wide production ~ 20.000.000 T / año ~ 4.000.000 T biodiesel
In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de
Ingeniería QuímicaY Ambiental
Ganoderma Ganoderma LucidumLucidum
Trametes Trametes VersicolorVersicolor
Potential oil extraction capacity of Fungal biomassPotential oil extraction capacity of Fungal biomass
Fungal sludge generated during the bio-degradation process was used for biodiesel production by means of one-step direct transformation.
Removal of emerging pharmaceutical pollutants
Alternative biological cultures: White-rot fungi in suspended growth medium with remarkable removal efficiency.
In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de
Ingeniería QuímicaY Ambiental
Oil Extraction:Oil Extraction: Ganoderma Lucidum and Trametes Versicolor Ganoderma Lucidum and Trametes Versicolor
Extr
actio
n Yi
eld
(wt%
)
2.5 h 100 ml Methanol2.5 h 100 ml MethanolRemarkable extraction yieldRemarkable extraction yield
Com
posi
tion
(%)
Large amount of glycerides and Free Large amount of glycerides and Free Fatty Acids obtainedFatty Acids obtained
In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de
Ingeniería QuímicaY Ambiental
0
20
40
60
80
100
Mola
r co
mposi
tion
(%
)
FAM
EYie
ld (
%)
0
20
40
60
80
100
Transesterification reaction – Transesterification reaction – In-Situ ProcessIn-Situ Process
High FAME yield from
fungy biomass through
In-situ process.
% FFA% Gly
Reaction Product (3h)
Reuse Product (3h)
Reaction Product (3h)
Reuse Product (3h)
Trametes VersicolorTrametes Versicolor Ganoderma Lucidum Ganoderma Lucidum
In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de
Ingeniería QuímicaY Ambiental
Trametes VersicolorTrametes Versicolor Ganoderma Lucidum Ganoderma Lucidum
Transesterification reaction – Transesterification reaction – In-Situ ProcessIn-Situ Process
Conclusions
In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de
Ingeniería QuímicaY Ambiental
• Fungus and Sewage Sludge from the primary and secondary treatment unit in waste water treatment plants can be used as alternative feedstock for biodiesel production.
• Extracted highly acidic impure oils can be easily converted into FAME by methanolysis in presence of the highly stable heterogeneous acid catalyst Zr-SBA-15.
• The extraction and conversion into FAME of the lipids contained by Sewage Sludge and fungus can be accomplished in a single step in presence of heterogeneous acid catalysts yielding better results than aplying both techniques separately.
ConclusionsConclusions
In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de
Ingeniería QuímicaY Ambiental
FINANCIAL SUPPORT FROM
IS GRATEFULLY ACKNOWLEDGED
Dr. I. VasileiadouDr. J. A. MeleroDr. F. MartínezDr. F. BautistaDr. J. IglesiasDr. G. MoralesDr. R. Molina
CTQ 2008-01396
S-2009/ENE-1743
In-Situ Transformation of Municipal Sewage Sludge into Biodiesel
Grupo de IngenieríaQuímica y Ambiental
Rebeca Sánchez VázquezI. A. Vasiliadou, Juan A. Melero, F. Martínez,
L. Fernando Bautista, J. Iglesias, G. Morales and R. Molina