A.G. Vlyssides, Ch. Tsiodra and C. Bambalioukasuest.ntua.gr/iwwatv/proceedings/presentations/21_May/SESSION_V/6._iwwtv_international...- In Greece there are 150.000.000 olive trees

21-23 May 2015 –Athens

Industrial Waste & Wastewater Treatment & Valorization

National Technical University of AthensChemical Engineering Department

A.G. Vlyssides, Ch. Tsiodra and C. Bambalioukas


Europe Africa Asia America

84%

8.5% 5.5%2%

World wide olive oil production



SPAIN

ITALY

CREECE

TURKEY

TUNISIA

SYRIA

MAIN OLIVE OIL PRODUCERS (in thousands tons per year)

0 χλμ 500

NATIONAL GEOGRAPHIC MAPS

LYBIA(600 π.Χ.) EGYPT

(1500 π.Χ..)

JORDAN

SYRIA(4000 BC.)

(4000 BC)TURKEY

FRANCE(600 BC)

(600 π.Χ.)

SPAIN

(200 BC)

(600 BC)ALGERIA CYPRUS

TUNISIA

(4000 BC.)ISRAEL

(600 BC)Sicilia

(2000 BC.)Crete(2500 BC)

GREECE(1500 BC.)

(600 BC.)

ITALY

(600 BC)MAROCO


Greek situation

- The olives and olive oil are inextricable part of Greek culture

- In Greece there are 150.000.000 olive trees cultivated in 765.000 hectare

- The annual production of each tree rises up to 300 kg of olives

- The 1/3 of Greek farmers are working on cultivation of olives

- Olives and olive oil production in Greece rise up 1.750.000 tnand 400.000 tn respectively




OlivesOlives

Olive oil

Olive oil

WashingWashing

OMWW

OMWW

Oil

washing

Oil washing

liquid

phase

liquid

phase

Cold

water

Coldwater

Washingwastewater

Washing

wastewater

Hot

waterHotwater

Washing water

Washing water

Crushing and malaxingCrushing and malaxing

Three-phase systemPressing system

(1000 kg)(1000 kg)

(210 kg)

(200 kg)

(1-1.6 tn)

(0.9 tn)

POMACEsolid phase

(550 kg)55% moisture

POMACEsolid phase

(550 kg)55% moisture

Centrifugation(Three-phase

decander)

Pressing

Centrifugation

oily

phase

Washing water

Olives

Olive oil

Washing

OMWW POMACE

Oil washing

ScreeningWooden Stones

oily

phase

sludge phase

Coldwater

Washingwastewater

Crushing and malaxing

Two-phase system

(1000 kg)

(200 kg) (0.2 tn) (800 kg)75% moisture

Centrifugation(Two-phase decander)

SYSTEMS FOR OLIVE OIL EXTRACTION21-23 May 2015 –Athens


Centrifugation

Decanting

(Vertical oil/waterseparator)

WashingOlives/leaves

separator

Pomace

Rawmaterial

Olives

Freshwater

Fresh

water

Olive

oil

Leaves

PRESS OLIVE MILLS

case II

OMW

Crushing &

Malaxation

Line Rate mass/time

1

2

3

4

5

6

7

8

9

10

13

11

12

14

15

200

200

2120

120

2000

2000

2000

920

700

2220

470

1750

50

420

1800

Raw material

Leaves

Olives

Washing water

Wastewater

Olives

Pulp

Fresh water

Pomace

Oil/water

Oil/water

Olive oil

OMW

OMW

Description

Total OMW



Centrifugation

Decanting

(Vertical water/oilseparator)

WashingOlives/leaves separator

Pomace

Raw

material

Olives

Freshwater

Freshwater

Olive oil

Leaves

2 PHASE

OLIVE MILLS

Crushing &Malaxation

LineMass rate mass/time

1

2

3

4

5

6

7

8

9

10

11

12

200

200

2120

120

2000

2000

50

2050

1000

500

50

400

Raw material

Leaves

Olives

Washing water

Wastewater

Olives

Pulp

Pomace

Oil/water

Hot water

Olive oil

OMW

Description



Centrifugation

Decanting

(Vertical water/oilseparator)

Decanting

(Vertical oil/waterseparator)

Crushing &

MalaxationWashing

Olives/leaves separator

Pomace

Raw

material

Olives

Fresh

water

Freshwater

Olive

oil

Olive oil

Hotfresh

water

Hotfresh

water

Leaves

LineMass rate mass/time

1

2

3

4

5

6

7

8

9

10

13

11

12

14

19

16

17

200

200

2120

120

2000

2000

740

2050

1000

50

40

1040

350

400

1400

360

700

Raw material

Leaves

Olives

Washing water

Wastewater

Olives

Pulp

Pomace

Oil/water

Oil/water

Hot water

Hot water

Hot water

Olive oil

Olive oil

OMW

Total OMW

Description

(Alfa Laval)



olive treesPruning biomass

olives1500 kg

2500 kg

1 hectare

Olive oil

pomace

stones

pomace oil

pomacedry residue

wastewater

500 kg

298kg

440 kg

2250 kg

1375 kg

65 kg

pressOlive oil

pomace

stones

pomace oil

pomacedry residue

wastewater

400 kg

270 kg

1375 kg

55 kg

4000 kg

525 kg

III-phaseOlive oil

pomace

stones

pomace oil

pomacedry residue

wastewater

2000 kg

180 kg

280 kg

65 kg

1300 kg

500 kg

II-phase

wastewater treatmentis the major problem



Characteristics of OMWW

Parameter Press III phases II phases

Quantity, tn/tn of olives 0.9 1,6 0.2

1 pH 4,50 4,8 4,5

2 BOD5, g/l 38,71 25,5 28,2

3 COD, g/l 158,18 92,5 120,30

4 Phenolic Compounds , g/l 17,15 10,65 18.20

5 Conductivity , mmhos/cm 18,00 12 25,00

6 COD/BOD ratio 4.15 3.68 4.2



East Macedonia and Thrace

Thessaly

Ionian

West Greece

Central Greece

Attica

Peloponnese

North Aegean

Crete

Central Macedonia

West Macedonia

South Aegean

Greek Olive Mills percentagedistribution

- There are 2.633 olive oil mills- 2,152 centrifugal systems (mostly III-phases)

- 481 traditional (pressure squeezing)

- There are 19 pomace processing plants

Greek situation



olives1000 kg

1360 m31412 kg VOCs125.5 kg CO2

air emissions

Waste Water 1634 kg

water vapors237.6 kg

480 m3

wooden stones 180 kg

pomace oil40 kg

olive oil

214 kg water1344 kg

hexane 1.5 kg

air 1327 kg

ash 3.07 kg

(130.4 )kg net production220 000 kcal

164 kcal 000

electric energy 20.5 kwh

thermal energy) (olive mill190 kwh

III-phase olive mill

Pomace Processing industry

TOTAL MASS & ENERGY BALANCE for a III phases Olive oil extraction

process



OLIVE MILL-ΙΙΙ phases

10 tn olives0

134.4 tn water

21.4 tn olive oil

49.6 tn pomace

163.4 tn wastewater

Total Solids 63.5 (TS) g/lTotal Suspended Solids (TSS) 2.8 g/lTotal Volatile Solids (TVS) 57.37 g/lAsh g/l6.13 Total Organic Carbon TOC) 39.82 g/l (Total Organic Nitrogen g/l (ΤΚΝ) 0.76 Total Phosphorus P O g/l ( ) 0.53 2 5

pH 4.8BOD 45.5 g/l5

COD 92.5 g/lolive oil 15 g/lConductivity mmhos/cm 12 Total Phenolic Compounds TPCs) 10.65 g/l (Potasium g/l (Κ Ο) 2.37 2

Dry mater (DM) 22.4 tnTotal Organic Carbon (TOC) 9.5 tnkernel oil 1 tn



Treatment methods applied as case studies in GreecePhysical methods

Evaporation ponds Land disposal

Biological methodsAnaerobic digestionAerobic digestion Nitrogen fixation

Physicochemical methodsMembrane’s technologyWet oxidation EvaporationElectrochemical oxidationEvaporation

Combined methodsWet oxidation following by membrane technologies (EHO method)Nitrogen fixation following by aerobic digestion (Bio-wheel method)



NET ENERGY PRODUCTION

using anaerobic Digestion


ANAEROBIC DIGESTION

οC35

OMWW 1.6 m3100 kg COD

100 kg 0 olives

10 kg COD

10 kg COD

efluent

anaerobic sludge

31 m 3 CH4

autoheatingmax 195 kwh

net energy production

max 78 kwh


0

0.2

0.4

0.6

0.8

1

1.2

0 500 1000 1500 2000 2500 3000 3500 4000 4500

Maximum decompsition rate factor (kmax)

phenolic compounds conc., mg/l

facto

r Maximum decomposition rate factor fk

0

1

2

3

4

5

6

0 500 1000 1500 2000 2500 3000 3500 4000 4500

Deth coefficient factor (b)

phenolic compounds conc., mg/l

facto

r

Death rate factor fb

0

50

100

150

200

250

0 500 1000 1500 2000 2500 3000 3500 4000

limit for SRT(Solid Retention Time)

phenolic compounds conc., mg/lda

ys

Lim(SRT)SRT=Solid Retention Time

kinetics for anaerobic digestion of OMWW

KPh= 1600 mg/l

Kdp =920 mg/l

-1kmax = 6.7 d

Y= 0.08 g/g CODr

-1b=0.03 d

fb = K dp

Kdp

[Ph] +

fk = KPh

KPh[Ph] +

lim(SRT) = [Y kmax fk-fb b]-1



Industrial scale Chania, Creta

Pilot scale Aspropirgos, Attika

Laboratory scale, NTUA



0

2000

4000

6000

8000

10000

12000

14000

16000

0 20 40 60 80 100 120

time of oxidation, min

Tota

l phenolic

Com

pounds,

mg/l

H2O2 60%

3 ml/l

2 ml/l

4 ml/l5 ml/l

0

20000

40000

60000

80000

100000

0 20 40 60 80 100 120


CO

D,

mg/l

H2O2 60%

2 ml/l

4 ml/l

3 ml/l

5 ml/l

15000

19000

23000

27000

0 20 40 60 80 100 120


BO

D5, m

g/l

H2O2 60%

2 ml/l

3 ml/l

5 ml/l

4 ml/l

The higher the use initial H2O2 dosagethe higher the achieved in COD, BOD and TPCs reduction


Characteristics of III-phases OMWW before and after Fenton oxidation treatment

Parameter Before

(mg/ L)

After

(mg/ L)

pH 4.8 3.2

BOD5 25500 35850

COD 92500 60250

Total Suspended Solids 4580 880

Total Volatile Suspended Solids 4024 790

Total phosphorous 870 270

Total Kjeldahl Nitrogen 1150 940

Total Phenolic Compounds (TPC) 10650 420

COD/BOD ratio 3.68 1.6



Laboratory scale apparatus for chemical oxidation



Laboratory scale apparatus for anaerobic digestion activity determination



Area selection for the 24 experimental design

Η2Ο2mg/l(X1)

FeSO4 7H2Omg/l(X2)

pH

(X3)

Temprature(Τ) οC(X4)

+1 4000 3500 4,5 35

0 2250 2000 3,75 27,5

-1 500 500 3 20



Results of experimental designY1

% reduction ofTPC

Y2% reduction of

TOC

Y3kmax,

L CH4/gVSS-d-1

1 53,7 27,8 3,89

2 31,1 4,5 3,55

3 50,6 2,2 4,63

4 33,1 8 3,53

5 70,6 36,6 4,92

6 40,8 5,9 3,95

7 66,5 2,8 5,92

8 43,5 10,5 3,94

9 49,7 25,8 3,73

10 28,8 4,2 3,47

11 46,8 2 4,4

12 30,6 7,4 3,45

13 85,9 44,5 6,97

14 49,7 7,2 4,4

15 80,9 3,5 7,82

16 52,9 12,7 4,42



Linear mathematical models for (%TPC∞,r), (%TΟC∞,r) and (kmax)

(%TPC∞) = 50.95 + 12.14[Η2Ο2] -10.4pH

(%TΟC∞) = 12.85 +5.3[Η2Ο2] +6.71pH –8.81[Η2Ο2][FeSO4]

(kmax) = 4.56 + 0.723[Η2Ο2] -0.73pH



Steepest descent method for optimization of %TPC reduction



Optimum results for %TPC reduction

Maximum redaction TPC∞ = 92 %

Conditions:

Initial conc of H2O2 : 3.037 g/l

Initial conc of Fe++ : 0.44 g/l

pH : 0.86

Temperature oC : 21.3 οC



Steepest descent method for optimization of %TOC reduction



Optimum results for %TOC reductionMaximum reduction of TOC∞ = 54 %

Conditions for fenton oxidation:

Initial conc for H2O2 : 1.58 g/l

Initial conc for Fe++ : 0.947 g/l

pH : 3.22

Temperature oC : 26.4 οC



Steepest descent method for optimization of anaerobic activity



Optimum results for kmax increasing

Maximum kmax,∞ = 0.9 L CH4/g VSS-d

conditions for fenton oxidation:

Initial conc of H2O2 : 3.2 g/l

Initial conc of Fe++ : 0.06 g/l

pH : 1.75

Τ : 15.7 οC



Lab scale UASB type continuous operationanaerobic digester for methane production from oxidized OMWW




TeOHFeSOOHk

273

33171925,0

24

4349,0

22max 7744,2


Lab scale UASB type continuous operation anaerobic digester for methane

production from oxidized OMWWin NTUA



PpHIC

TIC

TIC

ΑναερόβιαΧώνευση

GLS-201E

PHIC-201

TIC-201

TIC-202

P-201 A

FS

FS-201

Vv-226

M

PIE

PIE

PIE

P-202 P-203MR-202

MR-203

MR-201

E-205

E-203

E-204

PI-202

PI-203

M-203

PP- 012

V- 052

LSFIR

GAIR

Αεριοφυ- λάκειο

Καμινάδα

E

Από boiler

Προς boiler

E-201

E-202

M

FIR-201

GAIR-201

V-202

V-203

Gas AnalyserHLS

HLS-201

Προς κομποστοποίηση

M CR

M-201

CR-201

M-202PI

PI-204

V-204

Δοχείοφραγής

ΔοχείοΔιαχωρισμού υγρασίας

προς αντλία Ρ-104

από Ρ-104

PI

PI

ΡΙ-205

P&I DIAGRAM OF THE PILOT SCALE ANAEROBIC DIGESTION OF OMWW



Pilot scale anaerobic digestion of OMWW after DetoxificationUsing fentonregents

In Agios Constantinos, Fthiotida



Biogasflare

Bio-refinery pilot scale plant for a feasible utilizationof olive mill wastes and zero discharges

Olive oil and sludge Separation from Olive Mill WasteWater



Conclusions

The fenton oxidation is a key for effective detoxification of OMWW

After detoxification the anaerobic digestion could be used for effective

energy production from Olive Mill Wastewater



Sustainable olive oil production by effective utilization of olive mill wastes

Thank you for your attention


Documents

A.G. Vlyssides, Ch. Tsiodra and C. Bambalioukasuest.ntua.gr/iwwatv/proceedings/presentations/21_May/SESSION_V/6._iwwtv_international...- In Greece there are 150.000.000 olive trees