In-Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química y...

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



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



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



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



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.



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



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



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



% 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)


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



0

20

40

60

80

100

Mola

r co

mposi

tion

(%

)

FAM

EYie

ld (

%)

0

20

40

60

80

100

% FFA% Gly


In SituIn Situ Process Process

Blank


DB(g)/S(ml) = 0.1



Reuse Product (3h)

RP (3h) Wet Sludge

DB(g)/S(ml) = 0.25

High FAME yield from

primary sewage sludge

through In situ process


sewage sludge without

drying treatment (72 wt%

water content)



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




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



Transesterification reaction – Transesterification reaction – In Situ Process

SecondarySecondaryPrimaryPrimary

World wide production ~ 20.000.000 T / año ~ 4.000.000 T biodiesel



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.



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



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


fungy biomass through

In-situ process.

% FFA% Gly


Reuse Product (3h)


Reuse Product (3h)

Trametes VersicolorTrametes Versicolor Ganoderma Lucidum Ganoderma Lucidum



Trametes VersicolorTrametes Versicolor Ganoderma Lucidum Ganoderma Lucidum

Transesterification reaction – Transesterification reaction – In-Situ ProcessIn-Situ Process

Conclusions



• 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



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

In-Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química y...

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