(PABR)

, 2009

(PABR)

, 2009
2




... .
,
,
, . ,

.
, .
, ,
.
, . ,
.
.
, ,
.


, , , , , ,
, .

.


.


1.

1.1

1.2

1.3

1.3.1.

1.3.2.

1.3.3.1.

1.3.3.2

1.3.3.2.1

1.3.3.2.2

1.4

1.5

1.5.1

10

1.6

12

1.6.1

13

1.6.2

13

2.

15

2.1

15

2.2

15

2.3

16

2.3.1

18

2.3.1.1

18

2.3.1.2

20

2.3.1.3

20

2.3.2
2.4

21
23

2.4.1

23

2.4.2 pH

25

2.4.3

26

2.4.4

27

2.4.5

27
4

2.4.5.1

28

2.4.5.2

28

2.4.5.3

28

2.4.5.4

28

2.4.5.5

28

2.4.5.6

29

2.4.5.7

29

2.4.5.8

29

2.4.5.9

29

2.5

29

2.5.1

30

2.5.2

31

2.5.3

33

2.5.3.1

33

2.5.3.2

35

2.5.3.3

36

2.5.3.4 X

36

2.5.3.5

38

2.5.3.6

39

2.6

41

3.

43

3.1

43

3.2

43

3.3

44

3.4

48

3.4.1 ()

48

3.4.2 ()

48

3.4.3 ()

49

3.4.4 ()

49

3.5

50

4.
4.1

52

4.2 pH

52

4.3

52

4.4

53

4.5 ()

53

4.6 Kjeldahl

54

4.7

55

4.8

56

4.9

56

4.10

57

4.11

57

4.12

58

4.13

58

4.14

59

4.14.1

5.

52

(PABR)

59

4.14.2

61

4.14.3

64

PABR

65

5.1

65

5.2

65

5.3

67

5.4
PABR

71

5.4.1 #1

72

5.4.2 #2

75

79

5.4.4 #4

83

5.4.5 #5

86

5.4.6 #6

89

5.4.3 #3

5.5

5.5.1

92

93

6.

96

98


1.2.1.
1.2.2.
1.4.1.
1.4.2.

2.3.1. .
2.5.1. ) , )

2.5.2. .
2.5.3. ) , )
2.5.4. .
2.5.5. UASB EGSB
2.5.6. ABR SFABR.
2.5.7. .
2.5.8. .
2.5.9. .
3.1.1. ) (complete blocking), )
(standard blocking), ) (intermediate blocking), )
(cake filtration)
5.3.1.
. .
5.3.2.
.
.
5.4.1. ) pH , )
.

 5.4.2. )
, )
(#1). 5.4.3. )
, )
(#1).
5.4.4.
.
5.4.5.
.
5.4.6. ) pH , )
.
5.4.7. )

, )

5.4.8. )
, )

5.4.9. ) pH , )
(#1, #2, #3).
5.4.10. )
, )
(#1, #2, #3).
5.4.11. )

, )
(#1, #2, #3).
5.4.12.
(#1, #2, #3).
5.3.13. ) pH , )
(#1, #2, #3, #4)
5.4.14. )

, )
(#1, #2, #3, #4).

 5.4.15. )
, )
(#1, #2, #3, #4).
5.4.16.
(#1, #2, #3, #4).
5.4.17. ) pH , )
(#1, #2, #3, #4, #5).
5.4.18. )

, )
(#1, #2, #3, #4, #5).
5.4.19. )
, )
, )
(#1, #2, #3, #4, #5).
5.4.20. ) pH , )
(#1, #2, #3, #4, #5, #6).
5.4.21. )
, )
(#1, #2, #3, #4, #5, #6).
5.4.22. )

, )
(#1, #2, #3, #4, #5, #6).
5.4.23.
(#1, #2, #3, #4, #5, #6).
6.1.

10


1.1 (1000 )
1.3.1.
1.3.2.
1.3.3.

2.3.1.

2.3.2.

2.3.4.

2.3.5.

2.3.6.
2.3.7.
2.4.1. pH
2.4.2.
2.6.1.
3.2.1.
3.2.2.
3.2.3.
5.2.1 11/07-1/08
5.3.1.
5.4.1.
5.4.2.
5.5.1.

11


2.3.2.
Cellulomonas

2.3.3. )
, )
2.4.1.
3.1.1.
3.2.2.
3.2.4.
) , ) , )
3.3.1.

3.3.2.
4.11.1.
. .
4.14.1. ) ) PABR
4.14.2. PABR . (1)
, (2) 35C, (3) , (4)
, (5) PABR, (6) , (7)
, (8) , (9)
.
4.14.3. PABR
.
4.14.4.

1)

2)

3)

2)

, 4)

4.14.5.

1)

, 3) , 4) , 5)
, 6) , 7) , 8) , 9) ,
10) , 11)

12

 4.14.6. , 1) , 2)
, 3) , 4) , 5)
, 6) , 7) , 8)
, 9)
5.2.1. 1) decanter, 2)
, 3)
5.5.1. PABR
5.5.2. ) , )
30 bar.
.

13



.
,
95%
.
(

),

.
,
. ,

.

.

.

().


. ,
3.75
8.9 g/L/d
72%.
0.1 g/L .


. ,
,
.

14

Abstract
Olive mill wastewater is the by product of olive oil production. This agricultural
activity with high social and economic impact on the population of olive-producing
countries, are mainly located in the Mediterranean area which approximately 95% of
the worlds olive oil production is derived. It is produced seasonally in large
quantities by a large number of small olive mills and the combination of their
characteristics (very high organic load and phenolic compounds) are the main
difficulties in finding a solution for the management of these wastewaters, which are
dangerous for the environment.
The aim of this study was the combined treatment of olive mill wastewater. The
anaerobic digestion of the olive mill wastewaters took place in a high rate system, the
periodic anaerobic baffled reactor. Application of the membrane system aimed at
purifying the anaerobic effluent.
An increase in the organic loading rate was achieved by increasing the influent COD
and alternatively by decreasing the hydraulic retention time (HRT). The first option
caused process failure, since the volatile fatty acids accumulation resulted in
negligible biogas production. In contrast, the second change led to stable operation
that permitted the reduction of the HRT to 3.75 d and increase of the organic loading
rate to 8.9 gCOD/L/d with satisfactory total COD removal 72%. Further purification
in the membrane units resulted in a final permeate of less than 0.1 gCOD/L.
The anaerobic digestion of olive mill wastewater in a PABR was stable even at high
organic loading rates. Filtering and membrane fractionation of the anaerobic effluent
resulted in a final permeate stream of high quality, suitable for irrigation and reuse for
diluting the wastewater prior to anaerobic digestion.

15

1.
1.1
Oleaceae Olea
30 . , 97%
.
,
80% .
1.1 (1000 ) (IOOC).

1997/98 1998/99 1999/00 2000/01 2001/02 2002/03 2003/04 2006/07

2,116.5

1,707.0

1,878.5

1,940.5

2,463.5

1,942.5

2,307

2,230

15

54

33.5

26.5

25.5

16.5

40

40

6.5

11

10

11

22

14

1.5

2.5

3.5

5.5

6.5

6.5

8.1

4.5

2.5

3.5

2.5

8.5

5.5

14

21.5

6.5

27

14

28

11.5

36

3.5

70

65

40

35

60

45

80

80

5.5

20

18

21.5

16

70

115

81

165

92

165

110

154

93

215

210

130

35

70

180

130

40

170

70

175

65

160

60

140

0.5

0.5

11

0.5

2.5

0.5

1.5

2.5

2.5

2.5

1.5

6.5

6.5

11

16


, , .
,
15% 75%
.
.
130 , 2800
, 500 - 80
(, .., 2000, Award et al.,
2006).
1.2
,
. ,
65-83% .

.
: 50% , 22% , 19% ,
1.6% , ,
, , .

.

.

. 96-98%
(, .., 2000).
1.3
:

( )

( )

( )

17

( )

,
,
(Petrakis, 2006),
.
1.3.1.
,

.

.
.
1.3.2.

,
,
.


.
30-35 C.
1.3.3.1.
,
.
.

.

.

18

(. )

1.2.1. .
1.3.3.2

1970 .
1.3.3.2.1

(decanter)
, , .

.
.
1.3.3.2.2
,

.

19

 -
( ).
,
,
(Petrakis, 2006).
.

(. )

(. )
(. )

1.2.2.

20

1.4

.
:

pH

.

(Niaounnakis and Halvadakis, 2006) :

, :
o
o
o
o
o
o

o ,
. ,

,
.

o
,
( ),
.

21

 1.3.1 1.3.2 1.3.3 ,

,
,
.
1.3.1. (Azbar et al., 2004).

0.1-0.12 m3

~200

~400

(25% +
40-63 kWh

6% )

~600

(88% +
+ )

200

0.1-0.12 m3

500-600

(50% +

(decanter)

0.5-1 m3

4% )

1000-1200

(94% +
~10 l

1% )

90-117 kWh
1

200

0.1-0.12 m3

800-950

> 90-117 kWh

(60% +
3% )

22

 1.3.2. (Sierra et
al., 2001).

pH

4.5-6

35-100

(5 g/l)
, (

40-195

g/l)
, (TOC g/l)

22-64

(g/l)

0.3-23

(g/l)

5-14

(g/l)

3-24

N (g/l)

5-15

P (g/l)

0.3-1.1

K (g/l)

2.7-7.2

Ca (g/l)

0.12-0.75

Mg (g/l)

0.10-0.40

Na (g/l)

0.04-0.90

5.5-17.6

1.3.3.
(Kapellakis et al., 2007)

pH

4.5-5.5

4.7-5.2

120-130

60-180

90-100

20-55

0.1

0.9

12

P
, ( g/l)
, (5
g/l)
(%)
(%)

23

 (%)

2-8

0.5-2.6

0.5-2

0.1-0.3

0.1-1.5

0.2-0.4

1-1.5

0.3-0.5

1-1.5

0.2-0.5

2-2.4

0.3-0.8

0.03-1

0.5-2.3

0.11

0.03

0.72

0.27

Ca

0.07

0.02

Mg

0.04

0.01

Na

0.09

0.03

Cl

0.03

0.01

(%)

,
.
,
,
.
(Tsagaraki et al.,
2006), .
, ( 55-75%)

.
1.5

, .
,
.

24

.
o .
o .
o (
)
(Kapellakis et al., 2007).
o

) (Kapellakis et al., 2007).

o (Niaounnakis and Halvadakis, 2006).
o (Kotsou et al., 2003).
o .
.
.
( ) (DAnnibale
et al., 2003).

.
1.5.1

.
, ,
(Vermerris and Nickolson, 2006).

.
(
(, 2000).

25


.
,

( 1.4.1).

1.4.1. (Niaounnakis and

Halvadakis, 2006).
Hamdi
, ) ,
)

(Hamdi, 1992).

1.4.2.

26

 1.4.2.
(Niaounnakis and Halvadakis, 2006).

.

, [(Vermerris and Nickolson, 2006,
Shahidi and Naczk, 2004)].
1.6

, .
.

27

1.6.1

:

, :
.
(Tsagaraki
et al., 2006).

: ,

(Paraskeva and Diamadopoulos, 2006).

: ,
, ,
(, ) (Paraskeva and Diamadopoulos,
2006).

:
(Paraskeva et
al., 2006).

: (Mitrakas et al.,
1996).

: ,

(Azabou et al., 2007).

1.6.2

.

,

.
:

28

: [..
Pleurotus ostreatus (Fountoulakis et al., 2002)]

:
, (
).

, ,
.
, ,
.

(Di Giovacchino et al.,
2002). , ,

.

,
.

,
,
(Dionisi et al., 2005),
(Molina Alcaide and Nefzaoui, 1996),

(Agalias et al., 2007),
(Paraskeva et al., 2006),
,
.
,
, ,
.

29

2.
2.1

(CH4) (CO2)
,
(O2).
10 ,
. , 17
, Alessandro Volta
,
.
. , 1890

.
.
,
.

.
(Lettinga, G.,
1995).

,
)
, ) , )
, ) .
2.2
:

30


(Bitton, 2005).

(Gray,
2004).

(3-20
(Gerardi, 2003)

,
(, ) .

(Gray, 2004).

,
, ( ) (Lettinga, 1995)

(Gerardi, 2003).

(Bitton, 2005).

(Bitton, 2005).

(Gray, 2004).

(Seghezzo et al., 1998).

2.3

(Ahring, 2003).
2.3.1.
, (, ,
)

31

 (, , ), .
,
, ,
, , .

, .
, ,
,

.

: , , ,

: , , ,

, , H2, CO2

(H2, CO2, ,
, ,
)

2.3.1. .
32

2.3.1

,
.
, ,

(Hobson et al., 1974).

2.3.1.
(Bitton, 2005, Gray, 2004, ,
2007).

Bacteroides

Clostridium

Erysipelothrix

Lactobacillus

Peptococcus

Ruminococcus

Saccharomyces

Sarcina

Salmonella

Peptostreptococcus

Eubacterium

Micrococus

Staphylococcus

Selenomonas

Vibrio

Bacillus

2.3.1.1

.

,
(Gerardi, 2006).



-

33


. 2.3.2.
2.3.2. (Bitton,
2005).

2.3.2.
Cellulomonas

(Gerardi 2003).

34


, pH,
, ,
.. (Anderson et al., 2003).
2.3.1.2


, CO2 H2.
+ + . + + CO2 + H2
.

(, , pH)
(Gerardi 2003). O 90%
(Bitton, 2005).
2.3.1.3

,
.
+ + CO2 + H2
,
,

.

(Bjornsson et al., 2001).
, ,
:
2 CO2 + 4 H2 CH3COOH + 2 H2O
4 CO + 2 H2 CH3COOH + 2 CO2
4 CH3OH + 2 CO2 3 CH3COOH + 2 H2O

35

 max=1 g * h-1

max=0,04 g * h-1 (Bitton, 2005).
2.3.2

.

[(extremophiles) ( ,
)].

.
,
RNA, F420,
, ..
(McCarty, 2001). ,
.
,
.

( 2.3.3, 2.3.4).

2.3.3. )
, ) (Gerardi, 2003).

36

2.3.4.

(Gerardi, 2003).

Methanobacterium

Methanobrevibacter

Methanosarcina

Methanococcus

Methanomicrobium

Methanospirillum

, ,
.

, , , , ,
( 2.3.5).
2.3.5.

CH3COOH

CO2

CO

HCOOH

H2

CH3OH

CH3H2

. ) ,
, ) ,

37

 ) ,
(CH3) .

2.3.6.
2.3.6. (Anderson et al., 2003).

Methanobacteriales

Methanobacteriaceae

Methanobacterium

formcicum

Methanococcales

Methanococcaceae

Methanococcus

vannielli

halophilus

Methanomicrobiale

Methanomicrobiaceae

Methanomicrobium

mobile

Methanosarcinaceae

Methanothrix

soehngenii

2/3

.

(Bitton, 2005).
2.2.7. .
4 HCOOH CH4 + 3CO2 + 2H2O
4H2 + CO2 CH4 + 22O
4CH3OH 3CH4 + CO2 +22O
2.4
.

.
2.4.1

.

38

 : ) >80 oC,
65-75 oC, 30-40 oC, 20-30 oC, 10-20 oC
(-, 1999).

.


.

,
: ) , )

, ) )
. ,
,

(Ward, 2007, , 2007).

2.4.1.
(Ostream, 2004).

39

2.4.2 pH

pH.
pH 5,
pH 6.6 (Angelidaki, et
al., 2003).
,
pH 6.8 7.4,
pH 3.5
(Kotsyurbenko et al., 2004). 2.4.1 pH
.
2.4.1. pH

pH

Methanosphaera

6,8

Methanogenium

7,0

Methanospirillium

7,0-7,5

Methanococcoides

7,0-7,5

Methanohalobium

6,5-7,5

Methanothrix

7,1-7,8

Methanolobus

6,5-6,8

, .



.
.
pH
HCO3- ( HCO3-

),

40

 pH.
, mg CaCO3/l 3000-6000
CaCO3/l (Standards Methods for the Examination of Water and Wastewater).

{Ca(OH)2}, (NaOH),
(NaHCO3), (NH3),
(NH4HCO3), (CO3). pH

.
2.4.3


.

.
, ,
(Bitton, 2005).
(N)
(P) ( ), (S).
,
.


(Fe), (Co), (Mo), (Ni), (Mg),
(Ca), (Na), (Cu), (Ba), (Se)
(Zn).

(Gerardi, 2003). ,

(Kotz et al., 1969).

41

 2.4.2.
(Gerardi, 2003).

(%
)

3-4

0,5-1

0,2

0,01

0,2

0,001

2.4.4
(Hydraylic Retention Time, HRT )
,
: HRT = VR/Fw VR
Fw .


.
,
.

.
2.4.5
.

, ,

.
.
.

42

2.4.5.1

,
.
2.4.5.2
.
,
pH. 4 g/l
pH.
.

),

(4-6 g/l)
(Gallert et al., 1997).
2.4.5.3
.
,
(HS-). 200 mg/l
(, 1998).
2.4.5.4
( Cu2+, Cd2+,Cr6+, Pb2+, Ni2+, Zn2+, Fe3+, Mn2+,
Co2+) .
.
,
.
2.4.5.5

.
18mg/l 50% (, 1998).

43

2.4.5.6
100 mg/l. H
(Hickey et al., 1987)
2.4.5.7
,
. ,
.
Smith, .,

(Smith et al., 2005).
2.4.5.8
Na+, K+,Ca+2 Mg+2
(De Baere et al., 1984).
2.4.5.9
(. , , , ),
8-18 .
(Koster, 1987).

.

(Gerardi, 2006).
, ,

pH . , ,
(Anderson, 2003).
2.5

,
.

44


, ,
.
Lettinga,
(Lettinga, 1995):

,
.

, .

2.5.1

, 2.5.1 (, 1998).

.

.

45

2.5.1. ) , )


(Hall, 1992):




.
:

,

46

2.5.2

, ,
2.5.2 (, 1998).
, (
) .
,
.

2.5.2. .

(Hall, 1992):
.
.
.
.
.

47

 :
.
.

.
2.5.3


,
.
(biofilm)
.

,
.
2.5.3.1
, 2.5.3 (, 1998),

,
.

.
,
.

48

 2.5.3. ) , ) .
,
(Hall, 1992):

.
:



,


.

49

2.5.3.2


,
.
0.2 0.5 .
,
15 % 30 %,
, 25 %
300 % ( 1999).

(Hall, 1992):

,




.
:







.

50

2.5.3.3
,
(Hall, 1992).

, 2.5.4 (, 1998).

2.5.4. .
2.5.3.4 X
(Upflow Anaerobic Sludge
Blanket Reactor, UASBR) ,
, ,
,
.
UASBR
(Expanded Granular Sluge Bed Reactor, EGSBR)
UASBR
. UASBR,
,
.
(Seghezzo et al., 1998).

51

 2.5.5. UASB EGSB (Seghezzo et al., 1998).

UASB (Hall, 1992):

.
.
.
.
.
,
.

.
.
UASBR :
.
.

.

52

2.5.3.5
(Anaerobic Baffled Reactor, ABR),

,
.
,
.
,
.
ABR,
(splitfeed anaerobic baffled reactor, SFABR). SFABR
.
,

(Sallis, 2003).

2.5.6. ABR SFABR.

53

 ABR (Hall, 1992):

.
- .

.
,
.
.
ABR :

.
.

.
2.5.3.6
,

, (, 2007):

,
,
2.5.7.

54

2.5.7. .

,

, 2.5.8.

2.5.8. .

,
,
2.5.9.

55

2.5.9. .
2.6
,
,
.


.
:
2.6.1. (Pesta, 2007)

(%)

(% )

C/N

(m3CH4/kg
)

15

77

0.20.4

57

7785

510

0.20.3

> 98

9093

0.690.72

25

79

25

0.50.6

25

86

30

0.30.4

()

56

2022

8790

10

0.60.7

80

95

1427

0.3

95

27

0.50.6

57

3.

3.1
EMS (European Membrane Society),

.

(Electrodialysis),

(Microfiltration,

MF),

(Ultrafiltration, UF), (Nanofiltration, NF)

(Reverse Osmosis, RO) (Judd, S. and Jefferson, B., 2003).

.
3.2
Dead-end
.
3.1.1..
, Crossflow filtration
3.1.1.

3.1.1. (Judd, S., 2003).

58

 Dead-end filtration
. Cross-flow filtration

.
3.1.1
.

3.1.1. ) (complete blocking), )

(standard blocking), ) (intermediate blocking), )
(cake filtration) (Judd, S., 2006).
3.3

3.2.2.
3.2.1.

59

 3.2.1. (Ghosh, 2008).

1-5 atm

2-10 atm

5-50 atm

10-100 atm

(0,02-10 m)

**
(1-20 nm)

(0,01-5 nm)

( <1nm

: .
:
, .

**

3.2.2.
(Prudich et al., 2008)

60


.

, .
3.2.2
.
3.2.2.
(, . 2008, Judd, S., 2006).

MF

UF

RO

()

()

()

(
)

()

(.

)
,

(

)
()

61


. O
:

(flat sheet, FS)

(hollow fibre, HF)

(multi-tubular, MT)

(Capillary tube, CT)

(pleated filter cartridge, FC)

(spiral-wound, SW)

3.2.3. (Judd, S., 2006)

Dead-end ,
TSS

/,
Cross-flow /,

TSS,

/,

3.2.4.
) , ) , )
(Judd, S., 2006).
62

3.4
3.4.1 ()

0,02-10 m.
.
(Dead-end Cross-flow). Dead-end

.

, .. ,
.
3.4.2 ()

1-20 nm .

,
. , cross-flow
,
pH
/. .
, ,
. 3.3.1
.

63

 3.3.1.

(Cheremisinoff, N.P., 2002).
,

.
3.4.3 ()

0,01-5 nm ( ).
.

.
3.4.4 ()
, ,
,
. ,

. 3.3.2 .

64

 3.3.2. (Baker, R.W., 2000)

.
,
(<200)
(<1nm). ,

.
.

, , ..
3.5
(,
., 2008, Prudich, 2008):

(
)

).

(
)

65

( )

( )

(
.
).

(
, -

.

(
,

)

66

4.
4.1

.

,
,
.
4.2 pH
pH , ,
,

pH-

(Hanna

Instruments,

pH

211,

Microprocessor pHmeter) 10-20 ml.

4.3

,
Standard Methods for the examination of water and wastewater.
() .
,
.
103105oC.

() ,
550oC. ,
,
550oC.
.

67

4.4
(Total Alkalinity, TA)
Standard Methods for the Examination of Water and
Wastewater. ,

.

(CO3-2), (HCO3-)
(-).

, .
, ,
( 0.1 )
, pH- 4.5.
, mg CaCO3/l, :
= (A/V)*N*50.000
ml , V
ml .
4.5 ()
(Chemical Oxygen Demand,
COD)

:
CnHaObNc + [n + (a/4)-(b/2)-(3/4c)] O2 n CO2 + [(a/2)-(3/2c)] H2 + c NH3
,

. (
2 g Cl-/l) (K2Cr2O7)
141-143 C ( H+).
,
(AgSO4).
(Sawyer and McCarty, 1978):
CnHaOb + c Cr22-7 + 8c H+ n CO2 + [(a+8c)/2] H2O + 2 Cr3+
c = (2/3 )n + (1/6) n (1/3) b.

68

 (
) (Dissolved Chemical Oxygen Demand, DCOD)
600 nm ( Hach
DR/2010), Standard Methods for the Examination of
Water and Wastewater.
,
.
Cr3+,
K2Cr2O7
.

,
.

.
( )
(Total Chemical Oxygen Demand, TCOD)
, Standard Methods for
the Examination of Water and Wastewater.
Cr6+ ( K2Cr2O7 ),
,
(Fe(NH4)2(SO4)2*6H2O) (Sawyer
and McCarty, 1978_a):
6 Fe+2 + Cr2O7-2 +14 H+ 6 Fe+3 + 2 Cr+3 +7 H2O
4.6 Kjeldahl

Standard Methods for the Examination of Water and Wastewater.
(
Na2B4O7) pH 9.5
,
.

4+ 3 + +

69

 ,
70-80% .
(H3BO3) .
methyl blue methyl
red. ,
. ,

.
Kjeldahl

-3 Standard Methods.

-Kjeldahl 50 ml
. :
(H2SO4), (K2SO4) (HgSO4)
(3400C),
(NH4HSO4),
() .
, (Sawyer McCarty ,1978b).
CH3CHNH2COOH + 7H2SO4 3CO2 + 6SO2 + 8H2O + NH4HSO4
,
pH (Na2S2O3
.5H2O ) ,
.
.
0.02 .
4.7
Folin &
Ciocalteu Standard Methods for the Examination of Water and
Wastewater. -
(phenolic hydroxyl groups) .


70

 Folin & Ciocalteu, (

).
( Carry 50, Varian) 760 nm,
. ( )
,
.

.

.
4.8
,
Josefsson (Josefsson, 1983).

L- (H3BO3)
(H2SO4)

20 , ( )

520 nm.

520 nm,
D-.
4.9
( Volatile Fatty Acids, VFAs)
, Varian (CP-3800).
(Hewlett Packard FFAP, 30 m,
0.53 mm 1 m)
,
( ).

), 15 ml .
, (1 ml
+ 30 l H2SO4, 20 % ).

10 l

,
, 175 C.
71

 ( 11
), 105 C,
15 C 165 C, 20

C 235 C 3 .

225 C.
,

, .
4.10

Varian (STAR 3600),
(Poropak Q, 80/100-mesh, 1.83 , 1/8" OD)
(TCD).
1 ml, .

80 C,
180 C,
70 C.
,
, , 1 ml.
4.11
.
,
30 mm, 200mm U.

.
,
.
,
.

72

 4.11.1.
. .
4.12

Soxlet
.

.
103 C. 1,1,2-1,2,2-.

.
4.13
pH, , ,
,
(Water Quality Checker, Horiba U-10,
Horiba Ltd., Kyoto, Japan).

73

4.14

,
Skiadas, I. Lyberatos, G.

,
. .
4.14.1 (PABR)
PABR
,
.
,



. 4.14.1 ,
, D
1,3,6,9 11 .

.
PABR.

74

 4.14.1. ) ) PABR .
PABR
, 15 l. 2 l.
.
PVC (),
.
.

(, ., 1998).
10cm

.
,
.

,
.

35 C .

75

6
4
7

8
9
1

4.14.2. PABR . (1)

, (2) 35C, (3) , (4)
, (5) PABR, (6) , (7)
, (8) , (9)
.

4.14.3. PABR
.
4.14.2
,


76

 .

>80m.

2
3
1
4

4.14.4.

1)

2)

3)

, 4) .
,
.
(zirconia), 100 nm, 19 1020 mm , 4
mm 0.24 m2.
1800 l/h m2. 3.44 4.30 m3/h
cross-flow 4 5 m/s . (Transmembrane pressure,
TMP) 1,75 bar.

TMP=

Pin + Pout
- Pp Pin= , Pout= , Pp=
2

.
(Paraskeva et al., 2007).

77

 40 l/h.
20-45 C.
HNO3 1% w/w, NaOH 2% w/w 0.1%
(sodium bisulfite) .

(Hydro Air Research SpA, Merlino (LO), Milan, Italy) :
, 150-300 Dalton ( 1 Dalton = 1.66
*10-24 g), 0.5 27.5 bar, 41.4 bar.

10
4
8
9

3
6

11

4.14.5.

1)

2)

, 3) , 4) , 5)
, 6) , 7) , 8) , 9) ,
10) , 11) .

78

4.14.3

.
(spiral wound), 63.45 mm, 1015 mm
2.5 m2.
50

C,

.
30-40 bar, 30-35 l/h.
(Hydro Air
Research SpA, Merlino (LO), Milan, Italy) :
, <100,
55.2 bar 60 bar.
0.5 w/w P3-Ultrasil 11 (HenkelEcolab, Athens, Greece) 0.1% (sodium bisulfite)
.

3
5
1

6
9
4.14.6. , 1) , 2)

, 3) , 4) , 5)
, 6) , 7) , 8)
, 9)
79

5.

PABR
5.1

.
:

,
.

5.2

, 2007-08 (). . ,
.

1
2
3

5.2.1. 1) decanter, 2)

, 3) .

80

 50 l
.
,
.
(-24 C) .
,
.
5.2.1 11/07-1/08

pH

g/l

g/l

g/l

g/l

g/l

mg/l

mg/l

Kjeldahl

mg/l

g/l

mg/l

5.12 36.98 35.53 121.785 72.250

6.58

28562.52

25995.92

759

10.24

170.94

5.14

139.851 67.920

5.02

18850.75

17352.01

868

11.97

81.45

5.12 39.76 38.26 146.552 71.280

5.83

23546.78

22048.05

714

17.059 116.99

5.12 40.28 38.64 158.867 58.080

4.60

17068.92

15570.19

742

15.696

92.17

5.14 55.04 51.32 172.030 86.640

6.44

26810.69

25311.96

868

16.834

54.54

5.11 36.18 34.76 148.515 63.360

5.07

23213.73

21715.00

728

12.998

75.12

43.6

41.7

, pH,
.
()
55.04 g/l 36.18 g/l.
51.32 g/l
34.76 g/l.
(-)
, 121.785 g/l 172.030 g/l
86.640 g/l.
, .

81


. 1 g/l
(Borja et al., 1996).
90% .
17.059 g/l.
Beccari et al. 0.35 g/l
(Beccari et al., 1999).
Kjeldahl 868 mg/l.
,
.
()
.
5.3

PABR
15 l . 3.75 l.
.

,

.
35

C .

50 l.
7 l (=-24C) .
.

, 1.1
1.3.
,

.

,
82

 .
- ,
.

1:1.
.
.
((NH4)2HPO4)
7 g/L 10 ml/l.
5.3.1.
5.3.1.

(g/l)

CaCl2.2H2O

22.5

NH4Cl

35.9

MgCl2.6H2O

16.2

KCl

117

MnCl2.4H2O

1.8

CoCl2.6H2O

2.7

H3BO3

0.51

CuCl2.2H2O

0.24

Na2MoO4.2H2O

0.23

ZnCl2

0.19

NiCl2.6H2O

0.2

H2WO4

0.01

,

, ,

.
PABR, , 10
g/l.
.

83


.
,
() 17.5 1.1-1.7
g/l/d.
,
XAO ,
17.5 .
2.9-4 g/l/d.
,
.
, ,
, ,
.

PABR ,
.

30 l .
(4 C).
,
. 5.3.1
.

84

 5.3.1.

. .
PABR ,

. 5.3.2

.

85

 5.3.2.

.
.
5.4
PABR

270
. 5.4.1.
5.4.1.

()
-
(g/l)

#1

#2

#3

#4

#5

#6

17.5

17.5

17.5

8.75

3.75

20-30

50-70

10-25

20-30

20-30

20-30

1.1-1.7

2.9-4

0.6-1.4

2.3-3.4

4-6

5.6-8

(g/l/d)

86


PABR.
5.4.1 #1

. 17.5
60 .

8,0

(mg CaCO3/l)

#1

7,5
7,0

pH

6,5
6,0
5,5
5,0
4,5
4,0

14000

#1

12000

10000

8000

6000

4000

2000

0
0

30

60

90

120

150

180

210

240

270

30

60

()

90

120

150

180

210

()

()

()

5.4.1. ) pH , )

5.4.1, #1 pH 7.71.

. pH
7.13. pH 5.35.
5.4.1
.
13000 mg CaCO3/l 4.7-4.8 g CaCO3/l .
.

87

240

270

70

(g/l)

60
50
40
30
20
10

80

#1

4,5

70
80

4,0
60
3,5
50

3,0

40

2,5
2,0

30

30

60

90

120

150

180

210

240

270

60

40

1,5
20
20

1,0
10

0,5

0,0

100

30

60

()

()

90

120

150

180

210

240

()

()

5.4.2. )

, )
(#1).

5.4.2, #1 ,
20-30 g/l. ,
4-6 g/l. 80-90%
.
, 0.55-0.75
l/l/d.
.
- .
54-69 %.

88

270

(g/l)

#1

,
,

5,0

% CH4

(l/l/d)

80

,
5000

E,

#1

4500

#1

(g/l)

4000

(mg/l)

3500
3000
2500
2000
1500
1000

5
4
3
2
1

500
0

0
0

30

60

90

120

150

180

210

240

270

()

()

30

60

90

120

150

180

210

()

()

5.4.3. )

, )
(#1).

(Ahring, K.B., 1995).
,
( 5.4.3, #1).

.
1.49-2.62 g/l (
5.4.3, #1).
1 g/l.

89

240

270

(g/l)

30

#1

20

10

0
0

30

60

90

12 0

150

1 80

2 10

24 0

2 70

( )

5.4.4.

.
PABR
,
.
5.3 g/l. 80-95 %
.
( 5 g/l), PABR,

(Stamatelatou et al., 2008).
5.4.2 #2

,
. 17,5
56 . 77
.
.

90

(g/l)

30

#1

#2

20

10

0
0

30

60

90

120

150

180

210

240

270

()

5.4.5.

.
,
.
,

.

,
#1

#2

(mg CaCO3/l)

8,0
7,5
7,0

pH

6,5
6,0
5,5
5,0
4,5
4,0

14000

#1

#2

12000

10000

8000

6000

4000

2000

30

60

90

120

150

180

210

240

270

30

()

()

60

90

120

150

180

210

()

()

5.4.6. ) pH , )

91

240

270

 5.4.6, #2 pH
. 60-68 pH
(pH~7.13). 68 77 , pH
.

. 77
,
. pH
7 7.14. , pH
5.98.
( 5.4.6, #2)
4.5-5.2
g CaCO3/l. ,
pH
.

5000

#1

80

,
#2

70

4500
4000

60

(g/l)

3500

(mg/l)

#1

#2

3000
2500
2000
1500

50
40
30
20

1000

10

500

0
0

30

60

90

120

150

180

210

240

270

()

()

30

60

90

120

150

180

210

240

()

()

5.4.7. )

, )
.
,
- .

92

270

 77
.
,
1.5 g/l 150 mg/l.
,
3.7 g/l, 1 g/l.

,
,

5,0

#1

80

#2

4,5

70

50
40

2,0

30

60

40

1,5
20
1,0

20

0,0
0

30

60

90

120

150

180

210

240

()

()

0
270

5
4
3
2
1

10

0,5

(g/l)

60
3,5

(g/l)

80

2,5

#2

#1

4,0

3,0

E,

100

% CH4

(l/l/d)

0
0

30

60

90

120

150

180

210

()

()

5.4.8. )

, )

-
( 5.4.8, #2).
,
.


( 5.4.8, #2),
.
(

93

240

270

 , .)
, ,
(Fedorak, M.P. and Hrudey, E.S., 1984).
(2.62
g/l), (3.17
g/l). 5.5 g/l. Fedorak, M.P. and
Hrudey, E.S. ,
2 g/l, (Fedorak, M.P.
and Hrudey, E.S., 1984).
5.4.3 #3

PABR,
. 2/3
( 5.4.2)
1:1
.
117 130 ,
.
5.4.2.

pH

7.22

(g/l)

23.4

(g/l)

15.6

. 17.5
48 .

94


#3

#2

(mg CaCO3/l)

#1

7,5

7,0

pH

6,5
6,0
5,5
5,0
4,5

14000

#1

#2

#3

12000

10000

8,0

8000

6000

4000

2000

4,0
0

30

60

90

120

150

180

()

210

240

270

30

60

90

120

150

180

210

240

()

()

()

5.4.9. ) pH , )

(#1, #2, #3).

pH
.
#1 3.1 g CaCO3/l.

.

95

270

#1

4,5

80

100

80

#3

#2

#1

,
#2

#3

70

70
80

4,0

2,0

30

40

1,5
20
1,0

(g/l)

40

60

(g/l)

2,5

50

% CH4

3,0

60

60
3,5

(l/l/d)

,
,

5,0

50
40
30
20

20
10

0,5
0,0
0

30

60

90

120

150

180

210

240

0
270

()

()

10
0

0
0

30

60

90

120

150

180

210

()

()

5.4.10. )

, )
(#1, #2, #3).
( 5.4.10, #3),
.
.
(60-70%)

.
,
80-90% - ( 5.4.10, #3).

96

240

270

,
5000

#1

#2

4500

#2

#1

#3

3000
2500
2000
1500
1000

3500

(g/l)

4000

4
3
2
1

500

0
0

30

60

90

120

150

180

210

240

270

30

60

90

120

150

180

210

()

()

()

()

5.4.11. )

, )
(#1, #2, #3).
1 g/l
.( 5.4.11, #3).
.

.

( 5.4.11, #3)

.
,

30

#1

#2

20

#3

(g/l)

(mg/l)

E,

#3

10

0
0

30

60

90

120

150

180

210

240

270

()

5.4.12.

(#1, #2, #3).

97

240

270

 ,
( 5.4.12).
5.4.4 #4

,
, , 8.75.
2.3-3.4 g/l/d.

178 232.

#3

#2

#4

7,5

7,0

pH

6,5
6,0
5,5
5,0
4,5
4,0

14000

#1

#2

#4

#3

12000

10000

#1

(mg CaCO3/l)

8,0

8000

6000

4000

2000

0
0

30

60

90

120

150

180

()

()

210

240

270

30

60

90

120

150

180

210

()

()

5.3.13. ) pH , )

(#1, #2, #3, #4).

17.5 8.75
, pH
6.7 ( 5.4.13, #4).
3.4 g CaCO3/l,

pH . (NaHCO3)
3 g/l ( 183, 187) 1 g/l ( 191),
PABR,

98

240

270

, 4 g CaCO3/l ( 5.4.13, #4). pH

7 .

,
5000

#1

#2

E,

#4

#3

4500

#2

#1

#4

#3

3000
2500
2000
1500
1000

(mg/l)

3500

(g/l)

4000

4
3
2
1

500
0

0
0

30

60

90

120

150

180

210

240

270

30

()

()

60

90

120

150

180

210

()

()

5.4.14. )

, )
(#1, #2, #3, #4).
pH
( 5.4.14, #4).
.

. 2 ,
pH
6.8. pH
, ,
,
.
.
#1, #3
3 g/l ( 5.4.14, #4).

99

240

270

#1

80

#4

#3

#2

4,5

100

80

70

#1

,
#2

#3

#4

70
80

2,5

50
40

2,0

30

% CH4

3,0

60

40

1,5
20
20

1,0
10

0,5
0,0
0

30

60

90

120

150

180

210

240

0
270

()

60

(g/l)

3,5

(g/l)

60

4,0

50
40
30
20
10

0
0

30

60

90

120

150

180

210

()

()

()

5.4.15. )

, )
(#1, #2, #3, #4).

( 5.4.15, #4). (25%) #3, CO2
NaHCO3.
- 20-30 g/l
80% ( 5.4.15, #4).

30

#1

#2

20

#3

#4

(g/l)

(l/l/d)

,
,

5,0

10

0
0

30

60

90

120

150

180

210

240

270

()

5.4.16.

(#1, #2, #3, #4).

100

240

270

 #1, #3 10 g/l
( 5.3.16, #4).
5.4.5 #5

232
249. 5 4-6 g/l/d,
.
.
.

#4 #5

#3

#2

7,5

7,0

pH

6,5
6,0
5,5
5,0
4,5
4,0

14000

#1

#2

#4 #5

#3

12000

10000

#1

(mg CaCO3/l)

8,0

8000

6000

4000

2000

0
0

30

60

90

120

150

180

()

()

210

240

270

30

60

90

120

150

180

210

()

()

5.4.17. ) pH , )

(#1, #2, #3, #4, #5).

pH 7
6.76 ( 5.4.17, #5). (NaHCO3)
3 g/l 234 ( 5.4.17, #5). pH
6.71. 237
NaHCO3 10
g/l.
, 2 g/l NaHCO3 PABR. pH
238 7.02.
101

240

270

 pH ,
239 NaHCO3 5 g/l.
NaHCO3
4-5.8 g CaCO3/l ( 5.4.17, #5).

,
5000

#1

#2

80

4500

,
#2

#3

#4 #5

70

4000

3000
2500
2000
1500

(g/l)

60

3500

(mg/l)

#1

#4 #5

#3

50
40
30
20

1000

10

500

0
0

30

60

90

120

150

180

210

240

270

30

60

()

()

90

120

150

180

210

()

()

5.4.18. )

, )
(#1, #2, #3, #4, #5).
pH ( 5.4.18,
#5). 1 g/l 900 mg/l.
234-237, 1 g/l
. 238 ,
200 mg/l.
. 234 239
200 mg/l 900 mg/l.
.
,
150 mg/l.
,
- ( 5.4.18, #5).

102

240

270

, .

,
,

5,0

#1

100

80

#4 #5

#3

#2

4,5

E,

70

#2

#1

#4 #5

#3

2,5

40

2,0

% CH4

3,0

50

30

60

40

1,5
20
20

1,0

0,0
0

30

60

90

120

150

180

210

240

0
270

0
30

60

90

120

150

180

210

()

#2

#4 #5

#3

20

()

()

#1

()

30

10

0,5

3,5

(g/l)

60

(g/l)

80

4,0

(g/l)

(l/l/d)

60-80% - .

10

0
0

30

60

90

120

150

180

210

240

270

()

()
5.4.19. )

, )
, )
(#1, #2, #3, #4, #5).
2.4-3.2
l/l/d 59-70% ( 5.4.19, #5).

103

240

270

 2.1-2.5 g/l
1.3-1.8 g/l ( 5.4.19, #5).

#1, #3, #4 10 g/l( 5.4.19, #5).
5.4.6 #6

249 263 . 3.75

5.6-8 g/l/d.
,

#1

#2

#3

#4 #5

#6

7,5

7,0

pH

6,5
6,0
5,5
5,0
4,5
4,0

14000

#1

#2

#4 #5

#3

#6

12000

10000

8,0

(mg CaCO3/l)

. .

8000

6000

4000

2000

0
0

30

60

90

120

150

180

210

240

270

()

()

30

60

90

120

150

180

210

()

()

5.4.20. ) pH , )

(#1, #2, #3, #4, #5, #6).

pH .
, pH
.
pH
pH 6.95 .
.
5.1 g CaCO3/l 3.8 g CaCO3/l

104

240

270

. ( 5.4.20,

#1

#4 #5 #6

#3

#2

4,5

80

100

80
70

80

2,0

30

40

1,5
20

(g/l)

40

60

(g/l)

50

% CH4

2,5

#3

#4 #5

#6

60

60

3,0

,
#2

70

4,0
3,5

#1

,
,

5,0

(l/l/d)

#6).

50
40
30
20

20

1,0
10

0,5
0,0
0

30

60

90

120

150

180

210

240

0
270

()

10
0

0
0

30

60

90

120

150

180

210

()

()

()

5.4.21. )

, )
(#1, #2, #3, #4, #5, #6).

2.7-4.2 l/l/d
57-64%.
-
. -
, 60-80%.

105

240

270

,
5000

#1

#2

#4 #5

#3

E,

#6

4500

#2

#1

#4 #5

#3

#6

3000
2500
2000
1500
1000

(mg/l)

3500

(g/l)

4000

4
3
2
1

500
0

0
0

30

60

90

120

150

180

210

240

270

30

60

()

90

120

150

180

210

()

()

()

5.4.22. )

, )
(#1, #2, #3, #4, #5, #6).

1 g/l ( 5.4.22, #6).
,

.

3.3 g/l ( 5.4.22, #6).
.
1.9-2.1 g/l
1.4-1.7 g/l.

106

240

270

,
#1

#2

20

#4 #5 #6

#3

(g/l)

30

10

0
0

30

60

90

120

150

180

210

240

270

()

5.4.23.

(#1, #2, #3, #4, #5, #6).

6-9 g/l 9097 % .
10 g/l PABR .
5.5

PABR
.
,
.
.

5.5.1. PABR.

107


, ,
30.
,
.
5.5.1.
5.5.1.
PABR

(TMP) bar

1.75-2

1.75-2

30

30

10-12

8-10

25-30*

20-25

58.7

54.4

45

38

59

51.5

36.5

31

(Qp) L/h

() C

* , Qp
(<10).

5.5.1

.
80 m.
.

.
92.9 72.2 g/L 5.08 g/L.
11.5 mS/cm 0.66%.
108

 (>999 NTU)
.
30.16% 14.8% .
56 NTU. .
.
1 g/L.
. pH
5 5.8 . (0.13
mS/cm), 0%, (6 NTU) (0.1 g/L)

.

.
,
.
,

.
PABR

. pH PABR
7 .
,
. 3

. PABR
.
7.5 6.24 g/L
1.28 g/L.
(844 NTU). 14.8 mS/cm
0.82%.
,
.
PABR,
109

 .
,

(: 0.1 g/L, : 0.01 g/L, : 2 NTU) .

, PABR
.

()

()

5.5.2. ) , )

30 bar.
.

110

6.
,
,
,

.

, .
PABR 1:1
.
80%,
3.75 . 17.5 ,
90%.
.

(>5g/L).
17.5 3.75 ,
.
pH
,
. ,
.

. 10-20 % , .

.
60%
.

PABR
.
6.1.

111

 6.1. .

,
,

, .

112


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