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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
Industrial Waste & Wastewater Treatment & Valorization
Europe Africa Asia America
84%
8.5% 5.5%2%
World wide olive oil production
21-23 May 2015 –Athens
Industrial Waste & Wastewater Treatment & Valorization
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
21-23 May 2015 –Athens
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
Industrial Waste & Wastewater Treatment & Valorization
21-23 May 2015 –Athens
Industrial Waste & Wastewater Treatment & Valorization
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
Industrial Waste & Wastewater Treatment & Valorization
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
21-23 May 2015 –Athens
Industrial Waste & Wastewater Treatment & Valorization
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
21-23 May 2015 –Athens
Industrial Waste & Wastewater Treatment & Valorization
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)
21-23 May 2015 –Athens
Industrial Waste & Wastewater Treatment & Valorization
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
21-23 May 2015 –Athens
Industrial Waste & Wastewater Treatment & Valorization
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
21-23 May 2015 –Athens
Industrial Waste & Wastewater Treatment & Valorization
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
21-23 May 2015 –Athens
Industrial Waste & Wastewater Treatment & Valorization
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
21-23 May 2015 –Athens
Industrial Waste & Wastewater Treatment & Valorization
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
21-23 May 2015 –Athens
Industrial Waste & Wastewater Treatment & Valorization
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)
21-23 May 2015 –Athens
Industrial Waste & Wastewater Treatment & Valorization
NET ENERGY PRODUCTION
using anaerobic Digestion
21-23 May 2015 –Athens
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
Industrial Waste & Wastewater Treatment & Valorization
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
21-23 May 2015 –Athens
Industrial Waste & Wastewater Treatment & Valorization
Industrial scale Chania, Creta
Pilot scale Aspropirgos, Attika
Laboratory scale, NTUA
21-23 May 2015 –Athens
Industrial Waste & Wastewater Treatment & Valorization
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
time of oxidation, min
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
time of oxidation, min
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
21-23 May 2015 –Athens
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
Industrial Waste & Wastewater Treatment & Valorization
21-23 May 2015 –Athens
Laboratory scale apparatus for chemical oxidation
Industrial Waste & Wastewater Treatment & Valorization
21-23 May 2015 –Athens
Laboratory scale apparatus for anaerobic digestion activity determination
Industrial Waste & Wastewater Treatment & Valorization
21-23 May 2015 –Athens
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
Industrial Waste & Wastewater Treatment & Valorization
21-23 May 2015 –Athens
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
Industrial Waste & Wastewater Treatment & Valorization
21-23 May 2015 –Athens
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
Industrial Waste & Wastewater Treatment & Valorization
21-23 May 2015 –Athens
Steepest descent method for optimization of %TPC reduction
Industrial Waste & Wastewater Treatment & Valorization
21-23 May 2015 –Athens
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
Industrial Waste & Wastewater Treatment & Valorization
21-23 May 2015 –Athens
Steepest descent method for optimization of %TOC reduction
Industrial Waste & Wastewater Treatment & Valorization
21-23 May 2015 –Athens
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
Industrial Waste & Wastewater Treatment & Valorization
21-23 May 2015 –Athens
Steepest descent method for optimization of anaerobic activity
Industrial Waste & Wastewater Treatment & Valorization
21-23 May 2015 –Athens
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
Industrial Waste & Wastewater Treatment & Valorization
21-23 May 2015 –Athens
Lab scale UASB type continuous operationanaerobic digester for methane production from oxidized OMWW
Industrial Waste & Wastewater Treatment & Valorization
21-23 May 2015 –Athens
Industrial Waste & Wastewater Treatment & Valorization
TeOHFeSOOHk
273
33171925,0
24
4349,0
22max 7744,2
21-23 May 2015 –Athens
Lab scale UASB type continuous operation anaerobic digester for methane
production from oxidized OMWWin NTUA
Industrial Waste & Wastewater Treatment & Valorization
21-23 May 2015 –Athens
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
Industrial Waste & Wastewater Treatment & Valorization
21-23 May 2015 –Athens
Pilot scale anaerobic digestion of OMWW after DetoxificationUsing fentonregents
In Agios Constantinos, Fthiotida
Industrial Waste & Wastewater Treatment & Valorization
21-23 May 2015 –Athens
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
Industrial Waste & Wastewater Treatment & Valorization
21-23 May 2015 –Athens
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
Industrial Waste & Wastewater Treatment & Valorization
21-23 May 2015 –Athens
Sustainable olive oil production by effective utilization of olive mill wastes
Thank you for your attention
21-23 May 2015 –Athens