SRB(Sulfatewebbook.me.go.kr/DLi-File/094/003/005/5549970.pdf · 2015-10-30 · -6 매립장대기질개선을위한SRB억제방안연구 Sulfite(SO3 2-) ③ APS SO 3 2-,Sulfite dissimila-t

SRB(Sulfate

Reducing Bacteria)

2013. 03.

수도권매립지관리공사

.Ⅰ 1

1.1. 1

1.2. 4

.Ⅱ 5

2.1. SRB H2S 5

2.1.1 (SRB) 5

2.1.2 (SRB) 6

2.1.3 (SRB) (MPB) 9

2.1.4 (SRB) 14

2.1.5 H2S 16

2.1.6 H⋅ 2S 20

2.2. (Gypsum) 23

2.2.1 (Gypsum) 23

2.2.2 (Gypsum) SO42-

26

2.2.3 SO42- 31

2.3. 32

2.3.1 H2S 32

2.3.2 34

2.3.3 (Gypsum) SRB(Sulfate reducing Bacteria)

35

2.3.4 39

.Ⅲ 43

3.1. 43

3.1.1 43

3.1.2 45

3.1.3 45

3.2. SO42- 46

3.2.1 46

3.2.2 46

3.2.3 47

3.3. (Batch test) 48

3.3.1 48

3.3.2 49

3.4. (Lysimeter) H2S 52

3.4.1 Lysimeter ⋅ 52

3.4.2 52

3.4.3 Lysimeter 54

3.5. 55

3.6. H2S 56

3.7. 57

3.8. 58

3.8.1 58

3.8.2 58

.Ⅳ 61

4.1. 61

4.1.1 61

4.1.2 61

4.1.3 65

4.2. SO42- 66

4.2.1 66

4.2.2 SO42-

74

4.3. Batch test CH4 H2S 78

4.3.1 CH4 H2S 78

4.3.2 Batch test 88

4.4. (Lysimeter) 92

4.4.1 H2S 92

4.4.2 (Lysimeter) 110

4.5. 114

4.6. H2S 117

4.7. 121

. SRBⅤ 125

5.1. H2S H2S 125

5.1.1 SO42- 125

5.1.2 H2S 126

5.1.3 H2S CH4 128

5.1.4 H2S 130

5.2. ⋅ 131

5.2.1 (Lysimeter) 131

5.2.2 134

5.3. ⋅ 136

5.3.1 136

5.3.2 138

5.4. SRB H2S 141

1-1. 4

2-1. SRB pH 7

2-2. Electron donor Gibbs free energy 8

2-3. COD/SO42- 12

2-4. COD/SO42- 13

2-5. Sulfide Gibbs free energy 15

2-6. H2S 17

2-7. H2S 20

2-8. H2S 21

2-9. H2S 22

2-10. 25

2-11. 1 kg SO42-

27

2-12. SO42- 29

2-13. SO42- 31

2-14. Sulfide mineral 36

2-15. H2S 38

3-1. 44

3-2. 48

3-3. Batch test 50

3-4. 59

4-1. 62

4-2. 64

4-3. 65

4-4. (Digestion) SO42- 74

4-5. (Extraction) (Digestion) SO42- 77

4-6. Batch test (80 ) 89

4-7. Batch test 90

4-8. (k) 91

4-9. Lysimeter 109

4-10. Lysimeter 111

4-11. Lysimeter CH4 112

4-12. Lysimeter H2S 113

4-13. (Digestion) Lysimeter H2S 113

4-14. 118

4-15. H2S 119

4-16. 124

5-1. BOD SO42- 127

5-2. H2S CH4 129

5-3. BOD/SO42- H2S 134

5-4. 137

5-5. 138

5-6. Lysimeter BOD/SO42- 142

5-7. 2 BOD/SO42- 143

5-8. (Lysimeter) 144

5-9. 2011 2 145

1-1. 2

2-1. SRB SO42- 5

2-2. COD/SO42- 11

2-3. NRB SRB H2S 14

2-4. pH Sulfide 16

2-5. SO42- 18

2-6. H2S MPB pH 18

2-7. 24

2-8. SO42- 28

2-9. ZnO H2S 33

2-10. 39

2-11. 40

2-12. Bulking agents( , Moringa oleifera seed) 42

3-1. 46

3-2. Batch test 49

3-3. Batch test 51

3-4. Lysimeter 53

3-5. Lysimeter , 53

3-6. Lysimeter 54

3-7. 55

3-8. (Soil-covering column) 56

3-9. 57

4-1. BOD 66

4-2. COD 67

4-3. SO42- 67

4-4. BOD 68

4-5. COD 69

4-6. SO42- 69

4-7. BOD 70

4-8. COD 71

4-9. SO42- 71

4-10. BOD 72

4-11. COD 73

4-12. SO42- 73

4-13. VS CH4 79

4-14. VS H2S 79

4-15. + VS CH4 80

4-16. + VS H2S 80

4-17. + VS CH4 81

4-18. + VS H2S 81

4-19. VS CH4 82

4-20. VS H2S 82

4-21. VS CH4 83

4-22. VS H2S 83

4-23. VS CH4 84

4-24. VS H2S 84

4-25. VS CH4 85

4-26. VS H2S 85

4-27. + VS CH4 86

4-28. + VS H2S 86

4-29. + VS CH4 87

4-30. + VS H2S 87

4-31. 93

4-32. 93

4-33. 94

4-34. 94

4-35. + 96

4-36. + 96

4-37. + 97

4-38. + 97

4-39. + 98

4-40. + 99

4-41. + 99

4-42. + 100

4-43. 101

4-44. 101

4-45. 102

4-46. 102

4-47. 103

4-48. 103

4-49. 104

4-50. 104

4-51. 105

4-52. 105

4-53. 106

4-54. 106

4-55. 107

4-56. 107

4-57. 108

4-58. 108

4-59. 115

4-60. + 115

4-61. 116

4-62. H2S 118

4-63. H2S Sulfide mineral 119

4-64. H2S 120

4-65. SO42-

121

4-66. 122

4-67. SO42- mass 123

5-1. SO42-

125

5-2. Lysimeter 132

5-3. Lysimeter CH4 132

5-4. Lysimeter H2S 133

5-5. + 135

5-6. 145

수도권매립지관리공사- 1 -

.Ⅰ

1.1.

1990 ,

,

,

(Nimby: Not In My Backyard)

. 1990

, 1991 , , ,

, , ,

.

1992 1

, 1993 , 2000 10 1

2 .

,

2000

. ,

2001 , MBT(Mechanical

Biological Treatment) 2007

20%

56% ( 1-1).

매립장 대기질 개선을 위한 억제방안 연구SRB- 2 -

1-1.

(Gypsum) , (Drywall)

, ,

. Sulfate(SO42-) ,

SO42- SRB(Sulfate Reducing Bacteria)

(H2S) . H2S

, ,

(OSHA) 1%

, H2S . H2S

( ) ,

.

, , ,

,

1,000 ,

(Threshold) 10

.

, .

.


,

. H2S 100~300

ppm 2~15 ,

.


1.2.

H2S SRB

, H2S

1) (H2S) H2S

2) SRB Pilot 3)

, 4)

, H2S

.

1-1.

2012

(H2S)

H2S

� SRB

H2S

� H2S

SRB MPB

� Lab. test

H2S

SRB

Pilot

� Pilot

� H2S

�

� Pilot test

H2S

�

H2S CH4

� ,

�

��

SRB H2S � SRB H2S

�

� SRB

H2S


.Ⅱ

2.1 SRB H2S

2.1.1 (SRB)

(H2S) (SRB: Sulfate Reducing Bacteria)

, Sulfate(SO42-) SRB

2-1

.

2-1. SRB SO42-

SO42- Sulfite (SO3

2-) Sulfid

e(HS-) , 2-1 SO① 42-

. SRB ATP sulfurylase②

ATP , SO⋅ 42- ATP APS(adenosine-5-phosphosul-

fate) SO42- (Einsiedl, 2009).


Sulfite(SO32-) APS SO③ 3

2- , Sulfite dissimila-t

ory sulfite reductse(DSR) Sulfide(HS-) H2S (⑥

). , Trithionate(S2O62-) Thiosulfate(S2O3

2-) , HS-

H2S ( ).④ ⑤

2.1.2 (SRB)

SRB SO42- , ,

SRB . SRB

100 , SRB

(MPB) .

SRB Desulfovibrio

, , Ethanol, Pyruvate, Lactate

Group . Bergey's manual SRB

4 Group .

SRB 15~45 , 30~40℃ ℃

, 2-1 15 60℃ ℃

(Rabus , 2006, Sven Aerts, 2009). pH 5.5~9

, .


2-1. SRB pH

Genus Optimum temperature [ ]℃ Optimum pH

Desulfofrigus 10 7.0-7.5

Desulfofaba 7

Desulfotalea 10 7.5-7.6

Desulfovibrio 30-38 7.5

Desulfobacter 28-32 6.2-8.5

Desulfotomaculum 30-38 & 50-65a

Thermodesulfovibrio 65

Thermodesulfobacterium 65-70

Thermodesulfohabdus 60

Desulfacinum 60

Archaeoglobus 82-83 6.5-7.0

a : 45~75℃

(1999) SO42- ( )

(Electron donor) , Monocarboxylic acids

Formate, Acetate, Propionate, Butyrate, Lactate, Pyruvate, Dicarboxylic

acids (Malate, Fumarate, Succinate), Alcohols(Methanol, Ethanol, 1-propanol,

2-propanol, 1-butanol, Glycerol) ( 2-2).

SRB ,

. SRB

(Electron acceptor)

. SRB (Fermentative bac-

teria) .


2-2. Electron donor Gibbs free energy

G°△

Hydrogen 4H2 + SO22- 4H⟶ 2O + S

2- -123.98

Acetate CH3COO- + SO4

2- H⟶ 2O + CO2 + HCO3- + S2- -12.41

Formate 4HCOO- + SO42- 4HCO⟶ 3

- + S2- -182.67

Pyruvate 4CH3COCOO- + SO4

2- 4CH⟶ 3COO- + 4CO2 + S

2- -331.06

Lactate 2CH3CHOHCOO- + SO4

2- 2CH⟶ 3COO- + 2CO2 + 2HCO3

- + S2- -140.45

Malate 2(OOCCH2CHOHCOO)2 + SO42- 2CH⟶ 3COO

- + 2CO2 + 2HCO3- + S2- -180.99

Fumarate 2(OOCCH2CHOHCOO)2 + SO42- + 2H2O 2CH⟶ 3COO

- + 2CO2 + 2HCO3- + S2- -190.19

Succinate 4(OOCCH2CHOHCOO)2 + 3SO42- 4CH⟶ 3COO

- + 4CO2 + 4HCO3- + 3S2- -150.48

Propionate, Butyrate, Higher fatty acids Phenyl-substituted

organic acids . SRB

,

SRB, ,

.

SRB Lactate

Ethanol .

SRB .

SRB .

Acetate ,

Acetate (CO2)

.


2.1.3 (SRB) (MPB)

MPB SRB

, (1) ~ (4)

H2S .

SRB .

4H2 + SO42-+ H

+HS→

-+ 3H2O G°= -157 kJ (1)∆

CH3COO-+ SO4

2-HS→

-+ HCO3

-G°= -47 kJ∆ (2)

MPB .

4H2 + HCO3- + H+ CH→ 4 + 3H2O G°=-136 kJ∆ (3)

CH3COO- + H2O CH→ 4 + HCO3

- G°=-31 kJ∆ (4)

COD/SO○ 42-

SRB MPB

- COD/SO42-

0.67 COD/SO42- SRB MPB

SRB

MPB .

- SRB MPB COD/SO42- 1 2

, . McCartney (1993) COD/SO42-

3.7 Lactate

, SO42- COD/SO4

2- 1.6 , SRB

Acetate . Propionate/SO42- 2.2 ,

Acetate MPB , SO42- SRB

.


(Electron flow)○

- Iss (1986) SRB MPB

(Electron flow) .

COD MPB SRB COD

,

.

- By the SRB

Sulfate reduction : 4H2 + H++ SO4

2-HS→

-+ 4H2O (5)

CH3COO-+ SO4

2-HS→

-+ 2HCO3

-(6)

H2S COD

H2S + 2O2 H→ 2SO4 (7)

, SO42- 1 mol = 2 mol COD = 64 g COD

SRB = S × 64 g = A g

- By the MPB

Methane production : 4H2 + HCO3- + H+ CH→ 4 + 3H2O (8)

CH3COO- + H2O CH→ 4 + HCO3

- (9)

CH4 COD

CH4 + 2O2 CO→ 2 + 2H2O (10)

, CH4 1 mol = 2 mol COD = 64 g COD

MPB = CH4 × 64 g = B g

,


Percent electron flow by SRB = [A/(A+B)] x 100

Percent electron flow by MPB = [B/(A+B)] x 100

2-2. COD/SO42-

2-2 COD/SO42-

SRB MPB

COD/SO42- SRB MPB . SRB

MPB COD/SO42- 6.7 .

Acetate/Ethanol 5 g COD/L 0.5 g COD/L

10 , MPB 89% 66%

.

MPB Acetate Ethanol

SRB . Butyl acid

COD/SO42- MPB SRB COD/SO4

2- ,

COD/SO42- MPB

.

2-3 COD/SO42- SRB MPB

. COD/SO42- 36.5~91.53% , COD/SO4

2-


. COD/SO42- SO4

2-

SRB MPB

.

, COD/SO42-

2 . COD 7.15%

SRB

.

2-3. COD/SO42-

COD/SO42-

ratio

%

SO42--S

reduced

Composition of biogas

% COD

removed

Methane

produciton

rate

(L of CH4/g

of COD

removed)

% Electron

flow

% CH4 % CO2 % H2S SRB MPB

Control

2.0

3.3

5.0

6.7

10.0

20.0

85.62

35.50

52.12

73.84

88.02

90.94

91.53

68.99

4.12

12.47

21.05

47.83

65.67

66.54

3.34

2.90

3.08

3.47

3.07

3.20

3.97

0

2.55

1.36

1.09

0.82

0.15

0.07

69.37

7.15

10.26

30.13

65.66

68.30

69.04

0.36

0

0.08

0.13

0.24

0.31

0.33

0.02

100

96.23

83.77

50.76

33.74

19.32

99.98

0

3.77

16.23

49.24

66.26

80.68

(2003) COD/SO42-

SRB MPB MPN , 30

35 incubator COD/SO℃ 42-

MPB SRB .


2-4 SRB MPB

, COD/SO42- SRB , COD/SO4

2-

MPB . , Acetate

SRB 1.2×102~2.3×10

12, 2.3×10

3~4.9×10

13

, MPB Acetate 1.7×101~3.3×10

7, 2.1×10

2~3.5×10

10

.

COD/SO42- 6.7 MPB SRB , COD/SO4

2-

2 MPB . SRB SO42-

H2S ..

2-4. COD/SO42-

COD/SO42-

ratio

SRB (MPN/mL) MPB (MPN/mL)SRB:MPB

ratioH2-utilizingAcetate-

utilizingH2-utilizing

Acetate-

utilizing

Control 1.2 × 102 2.3 × 103 3.3 × 107 3.5 × 1010 0.1 : 99.9

20.0 2.2 × 107 2.5 × 105 2.5 × 107 5.5 × 108 3.7 : 96.3

10.0 3.4 × 107 5.6 × 107 3.6 × 107 4.9 × 108 14.6 : 85.4

6.7 4.7 × 107 4.8 × 107 2.5 × 107 5.1 × 108 49.6 : 50.4

5.0 5.6 × 107 7.9 × 108 2.1 × 107 3.9 × 108 67.3 : 32.7

3.3 2.9 × 108

5.5 × 1011

1.7 × 103

2.1 × 105

99.9 : 0.1

2.0 3.3 × 1012

4.9 × 1012

- - 100 : 0


2.1.4 (SRB)

SRB MPB

, NRB(Nitrate reducing bacteria)

. SRB In-situ Nitrate

SRB .

Nitrate SRB 2-3 , NR-SOB(Sulfide

oxidizing bacteria) hNRB(Heterotrophic nitrate reducing bacteria)

. NR-SOB H2S SO42- , hNRB

SRB SRB (Hubert , 2006).

2-3. NRB SRB H2S

SRB Sulfide NR-SOB Nitrate ( DNRA(Dissimilat-

ory nitrate/nitrite reduction to ammonium) SO42- , Lactate

hNRB SRB Acetate CO2 .

NRB Sulfide SRB .(

2-5).


2-5. Sulfide Gibbs free energy

ReactionG°∆ ′

(kJ/reaction)

Aerobic

HS- + 0.5O2 S→ 0 + OH- -209.3

HS- + 2O2 SO→ 42- + H+ -796.4

Anoxic(denitrification)

HS- + 0.4NO3- + 1.4H+ S→ 0 + 0.2N2 + 1.2H2O -196.3

HS- + 0.67NO2- + 1.67H+ S→ 0 + 0.33N2 + 1.33H2O -240.3

HS- + 1.6NO3- + 0.6H+ SO→ 4

2- + 0.8N2 + 0.8H2O -744.3

HS- + 2.67NO2- + 1.67H+ SO→ 42- + 1.33N2 + 1.33H2O -920.4

Anoxic(DNRA)

HS- + 0.25NO3- + 1.5H+ S→ 0 + 0.25NH4

+ + 0.75H2O -122.4

HS- + 0.25NO2- + 1.67H+ S→ 0 + 0.33NH4

+ + 0.67H2O -119.4

HS- + NO3- + H+ + H2O SO→ 4

2- + NH4+ -447.5

HS- + 1.33NO2- + 1.67H+ + 1.33H2O SO→ 4

2- + 1.33NH4+ -436.7


2-4. pH Sulfide

2.1.5 H2S

H2S . 2-4 pH 7 H2S HS-

Sulfide , H2S

. H2S

pKa 18 7 .℃

pH 6~8 H2S pH

.

H2S H2S , H2S

H2S . 2-6

(Lange handbook of chemistry, 1979), H2S

.


2-6. H2S

Temp( )℃ H2S(mg/L)

15 4410

20 3850

25 3380

30 2980

35 2650

40 2360

45 2100

50 1880

60 1480

SRB , SRB MPB

. SRB MPB

.

SO42-

SO42- 2,200~10,000 mg/L , 50%

. Sulfite Sulfate Sulfide

. 2-5 Sulfite

Sulfite 150~200 mg/L 50% (

, 2001).


2-5. SO42-

pH 6.4~7.2 H2S .

70~78% MPB H2S 200~250 mg/L 50%

pH 7.8~8.0 H2S

( 2-6).

2-6. H2S MPB pH


, , ,

, , ,

.

.

SRB H2S

,

H2S . 11

H2S , (SO2)

(Cooper, 2008).

2H2S (g) + 3O2 (g) 2SO→ 2 (g) + 2H2O (11)

SO2 (g) + H2O (g) H→ 2SO4 (aq) (12)

SO2 12

(H2SO4) pH 5.6 .

.⋅


2.1.6 H⋅ 2S

H2S (2001) ‘

CDM ’ 12 H2S

2-7 , 35 2,650℃

mg/L , 200 ppm

.

, H2S

.

Lee (2006) (Florida)

7 H2S 2-8

, Marion 12,000 ppm .

2-7. H2S

H2S(ppm)

42.7

28.5

124.9

31.0

101.5

103.5

153.7

22.3

195.1

85.4

55.7

90.1

86.2


2-8. H2S

Landfill minimum Maximum

Pasco 3 ppb 470 ppm

Citrus 3 ppb 920 ppm

Marion 0.013 ppm 12,000 ppm

Volusia 3 ppb 7000 ppm

Alachua 3 ppb 49 ppm

Columbia 3 ppb 3300 ppm

Highlands 3 ppb 11,000 ppm

Kuniholm(2007) H2S

2-9 .

58% Site 1

5 H2S 9,500 ppm

. Site 2 15%

H2S 1,000 ppm , Site 4

H2S 800 ppm

.

, , ,

,

H2S . ,

SO42-

H2S .


2-9. H2S

Landfill

Site

Total Waste C&D Screenig Plain C&D 5th year H2S

(1000TPY) (1000TPY) (%) (1000TPY) (%) (ppm)

1 306 76 25 102 33 9500

2 264 35 13 3000

3 1200 91 9 80 6 1000

4 285 61 21 800

5 100 110 100 3000


2.2 (Gypsum)

2.2.1 (Gypsum)

Sulfate(SO42-) ,

(CaSO4 2H⋅ 2O) ⋅

, 3~5%

.

( ) , ,

.

1824 (J. Aspdin)

,

,

.

(2006 ) 9

. 1990 1.5

.

1998 1994

51,635 2005 47,197 53,134 .

. , 1,45

0℃

(Gypsum) 3~5% ( 2-7).


2-7.

(Calcite)

, . (2010)

(Monocarbonat

e) , (Ettringite)

( 2-10).

SO42- .


2-10.

Solid phase(g)

Calcite/Gypsum(wt%/wt %)

0/0 5/0 0/5 2.5/2.5

C-S-H 65.4 65.4 65.4 65.4

Ettringite 0.000173 10.9 18.8 16.9

Hemicarbonate 5.49 0 0 0

Monocarbonate 10.1 22.5 12.9 19.8

AFm 5.52 0 3.32 0

Partlandite 26.7 27.1 27.1 27.1

Goethite 3.11 3.11 3.111 3.11

Calcite 0 3.31 0 1.29


2.2.2 (Gypsum) SO42-

.

SO42- .

13 .

1 kg 0.256~0.543 ton/m3

. - ,

, 1.5 ton/m3

3~5% .

(CaSO4·2H2O) SO42-

2-11 , 1 kg 3,614~12,776 mg/kg

SO42-

.

1 kg × (A/1.5) × B × 96/136= X mg (13)

A : (ton/m3)

B : (%)

X : 1 kg Sulfate


2-11. 1 kg SO42-

: ( )

· 1 kg : 0.543 ton/m3,

, 2009

· : 1.5 ton/m3, , ,

2008

· : 5%,

· SO42- : 96(SO4

2-)/136(CaSO4·2H2O)

1 kg = 1 kg ×(0.543/1.5)‣

1 kg = 18,100 mg/kg‣

1 kg SO‣ 42- = 12,776 mg/kg

.

3~5%

, SO42-

21,176~35,294 mg/kg .

KS F 3504

3% . 2.3 kg/m3 ,

297,689 mg/kg SO42- ( 2-8).

SO42-

.

9%

. 1% 3,000 mg/kg

SO42- .


2-8. SO42-

‘ (Gypsum) SRB(Sulfate reducing bacteria) ’

79% ,

, 29%

26% .

SO42-

EPA method TCLP Digestion (EPA method 3050B )

,

285~2,274 mg/kg , TCLP 447~5,458 mg/kg

, .

Digestion 2,157~32,060 mg/kg

.


SO42- ( 2-12) ,

SO42- 8 mm 90~15,420 mg/k

g , 45 mm 60~5,340 mg/kg (Trankl

er , 1996). (Wahlstrom , 2000)

Column test Batch test SO42- 4

mm 181~1,300 mg/kg, 20 mm 2,700 mg/kg

. TCLP SO42-

.

2-12. SO42-

Sulfate

Demolition waste

(Trankler , 1996)

1L 100 g

(<10mm),

24

<8mm : 90~15,420 mg/kg

<45mm : 60~5,340 mg/kg

Demolition waste

(Wahlstrom , 2000)

: =10:1

Column test, Batch test

( pH 12.5) 64

concrete, bricks

<4mm : 181~1,300 mg/kg

<20mm : 2,700 mg/kg

C&D debris

Rock/Concrete 15.4%

Gypsum 1.2%

C&D soil 72.6%

(Jang , 2001)

TCLP 17,840~31,700 mg/kg

SPLP Mulfiple

extraction leaching test

(66 hr)

8,400~51,00 mg/kg


SO42-

. SO42- SO4

2-

Digestion SO42-

.

TCLP 31,

700 mg/kg, Multiple extraction leaching test 51,000 mg/kg

, .

,

.


2.2.3 SO42-

SO

42- 2-13 , COD/SO4

2- SO4

2-, SRB MPB

.

BOD BOD/SO42- 2

, SRB

, H2S .

,

SO42-

,

.

2-13. SO42-

COD BOD SO42- COD/SO4

2- BOD/SO42-

762 377 608 1.25 0.62

845 417 1,452 0.58 0.29

1,695 697 25,025 0.07 0.03


2.3

2.3.1 H2S

AWCI(1992) SRB H2S

7 .

- : H2S SO42-

.

- : SRB

.

- SO42-

: SO42-

SO42-

H2S .

- SRB : SRB

.

- SRB : Desulfovibrio Desulfotomaculum SRB

H2S .

- pH : SRB pH 7~8 . pH 5 pH 9

.

- : SRB 30~38 45℃ ℃

.

7 SRB .

H2S

.

NREL(1998) LFG .

H2S ZnO(Zinc oxide) , H2S

50 ppb , Sulfide mineral ZnS H2S

. H2S 3% 45 ppb .


2-9. ZnO H2S

H2S (Ferric oxide) Sulfa treat

1,000 ppb . ,

(140 , 60 ) .℉ ℃

LFG

H2S .

MDEP(2007) Massachusetts Landfills

, (C&D) (Gypsum)

, 3:1 coal ash

wood ash .

.


2.3.2

1980

,

.

1995

. 2~3

, 1996

.

, ,

,

, ‘ (Gypsum)

SRB(Sulfate Reducing Bacteria) ’ .

SRB SO42-

, SRB .


2.3.3 (Gypsum) SRB(Sulfate reducing Bacteria)

2000 SO42-

H2S , .

SO42- ,

.

SRB SO42-

.

SO42-

SO42- SRB

.

SO42- , SO4

2- SRB

MPB CH4

.

, (pH)

pH

, .

SRB H2S

.

H2S NH3

. pH 7, 35℃

, NH3 pH 8 10 . pH 8

NH3

, (MPB) pH .


SRB H2S

Sulfide mineral(MeS) (

2-14), MeS ( , , , )

(TCE, Hexachloroe-thane, nitrobenzene ) 14

.

→↓ (14)

2-14. Sulfide mineral

Metal

Discrete compound that may be present

oxidizing reducing condition

Cd CdCO3 CdS

Cu Cu2(OH)2CO3 CuS

Fe Fe2O3 x(H⋅ 2O) FeS, FeS2

Hg HgO HgS

Mn MnO2 x(H⋅ 2O) MnS, MnCO3

Ni Ni(OH)2 NiCO⋅ 3 NiS

Pb 2PbCO3 Pb(OH)⋅ 2 PbCO⋅ 3 PbS

Zn ZnCO3, ZnSiO3 ZnS


Sulfide mineral(MeS) H2S

. (Coal ash)

.

H2S

,

.

H2S ,

(pH) pH

. pH SRB

pH .

SRB SO42- (NO3

-) (El

e-ctron acceptor) . NaNO

3, Fe(NO3)2, Ca(NO3)2 H2S ,

H2S ( 2-15).


2-15. H2S

(W/W)

Sulfide

(mg/L)(%) ( /kgS)

References

FeCl2 and

FeCl32.5:1

Plant scale,

75,000m3/d6.4 97 10.0

Padival .

(1995)

FeCl3 1.5:1Lab scale,

3.00L3.8 100 5.0

Nielsen .

(2005)

NaNO3 6.7:1Lab scale,

0.05L54.0 100 18.0

Jenneman

. (1986)


1.37L35.0 65 0.6

Okabe .

(2003a)


1.00L10.2 100 3.7

Okabe .

(2003b)

NutrioxTMe 2.50:1Plant scale,

15,000m3/d70.0 95-100 8.9

Einarsen

. (2000)

NutrioxTMe 0.36:1Plant scale,

50,000m3/d70.0 68-95 0.9

Lomass .

(2005)

Ca(NO3)2 1.92:1Plant scale,

2000m3/d2.6 100 6.5

Gomez .

(2005)

, H2S

SO42- H2S

.⋅


2.3.4

.

. ‘

’

.

2-10.

, ,

, .

2-10 2 50~25%

.

( - ), ( - )無有

, ,


.

2-11

, .

( ) ( ) ( )

2-11.

,① ② ③

Dia-genesis( ) , bulking agents④

, ⑤

ripening process

.

○

,

, , , ,

. (KS)

,

.

, ,

.

, ·

.


○

, , pH C, H, O, N,

S, P , ․

.

,

, ․

.

,

(Cation exchange capacity, CEC) .

(Bioavailability) · , ,

pH, , , .

Diagenesis○

Microwave

humification .

Biopolymer materials

· (Condensation)

Fulvic acid, Humic acid, Humin humification .

bulking agents○

2-12 bulking agents

15

. ,

, .

유기물토사 →

열개량토 (15)


( , ,

, )

Moringa Oleifera Seed

( , )

2-12 Bulking agents( , Moringa Oleifera Seed)


.Ⅲ

3.1.

3.1.1

, H2S

. (CaSO4 2H⋅ 2O)

( ), ( )

SRB , 2012 10

, ,

. 2009~2011 ,

, , ,

.

, , , , ,⋅

. , , ,

, , ⋅

.

, ,

, , , ( ,

), , ( ) SO42-

H2S

, 3-1 7

.


3-1.

, , ,

+,

+,

, , , ,

, ,

,

( )


3.1.2

7 (2011.01)

, , . -

(ES 06303.1) 105~110 4℃

(%) .

, - (ES 06301.1)

(25%) 600±25 3℃

(%) .

, , ,

TS(Total solid) ,

VS(Volatile solid) .

3.1.3

(EA) (900 )℃

, , , , ,

. Batch test Lysimeter Pilot test

.


3.2. SO42-

3.2.1

(2011.01) . 100 g

pH 5.8~6.3 (mL) :

= 1:10(W:V) 2,000 mL .

, 200 , 4~5 ㎝

6 1.0 ㎛

.

3.2.2

(Multi-extraction) ‘ ) ’

, 3-1 53 ㎛

,

.

1.0 ㎛

. 6

.

3-1.


3.2.3

EPA method 3050B (Digestion)

. 1 g 1:1 HNO3 10 mL

95±5 10~15 .℃

HNO3 5 mL 95±5 30℃

. HNO3 HNO3

5 mL .

2 mL 30% H2O2 3 mL ,

. H2O2 1 mL

( , H2O2 10 mL

).

95±5 5 mL .℃

HCl 10 mL 95±5 15 20~25 Membrane℃ ㎛

filter 100 mL Digestion

.


3.3. (Batch test)

3.3.1

(Batch test) BMP(Biochemical methane

potential) , 3-2

Bhattacharya (1996)

. 120 15℃

.

.

3-2.

(g/L)

NH4Cl 1.2

MgCl2 0.5

KCl 0.4

(NH4)2HPO4 0.08

FeCl2 4H⋅ 2O 0.04

CaCl2 2H⋅ 2O 0.025

(NaPO3)6 0.01

CoCl2 6H⋅ 2O 0.0025

KI 0.0025

MnCl2 6H⋅ 2O 0.0005

NH4VO3 0.0005

ZnCl2 0.0005

H3PO3 0.0005

NiCl2 6H⋅ 2O 0.0005

NaHCO3 3.0


3.3.2

(serum-bottle, 630 mL)

(300 mL)

(30 mL)

( 10%)

(2g VS/L)

pH ,

(N2) (Purging)

NaHCO3(1.2 g/L)

(N2) (Purging)

(35 )℃

3-2. Batch test

Owens (1979) , 630 mL serum

bottle(Duran Gem) 30 mL( 10%) 300 mL

bottle , 2g VS/L 3-3 .

pH 1N NaOH 1N HCl pH 7.0 ,

pH

(NaHCO3) 1.2 g/L . , 35℃

(Incubator) ( 3-3).


3-3. Batch test

(g)

0.15

0.48

0.64

+

0.14

0.45

0.59

0.46

+

0.15

0.46

0.61

0.32

0.89

0.09

0.28

0.37

0.33

0.29

18.94

5.16

+0.79

0.69

+0.82

0.50


20 gauge needle (Syringe)

(Manometer) , (TCD)

(CH4), (CO2) , 1~5 mL (N2)

500 mL , (PFPD) H2S

.

3-3. Batch test


3.4. (Lysimeter) H2S

3.4.1 Lysimeter ⋅

100 L Lysimeter

SUS(Stainless use steel) , ,

.

,

.

,⋅

.

. ,

,

( 3-4).

3.4.2

SiO2 90% 5~10 mm 20~30 mm

.

,

3 ,

100 L . 20 mm ,

.

,

. 2 ,

, (N2) 20 (Purging)

( 3-5).


3-4. Lysimeter

3-5. Lysimeter ,


3.4.3 Lysimeter

30±3℃

, 40±3%

( 3-6).

(LFG)

, 2 L

(Tedlar gas sampling bag) .

(LFG) (H2S), (CH4), (CO2)

, (Sulfate; SO42-), (Sulfide; S2-),

(BOD5), (CODcr), (T-N), (T-P)

(pH) .

3-6. Lysimeter


3.5.

2012 8 21 ~ 11 2 ( 2 , 7 )

, 2011 12 1 6

,

. 2 3D , + ,

500 m3(10×10×5 m) 1,500 m

33

, H2S, CH4 CO2

. (50 cm), (50

cm) , 6~7 150

cm .

3-7.


3.6. H2S

(Soil-covering column) 15 cm

, (Acrylic) 70 cm, 20 cm ,

15 cm .

15 cm ,

50 mm . 6,000 ppm 1.60

kg/L, 3,500 ppm 1.63 kg/L 1,000 ppm 1.59 kg/L .

H2S 2011 H2S 6,000 ppm

3,500 ppm 1,000 ppm .

60 L (m2) 1,910

L/hr/m2 . H2S ,

( 3-8).

3-8. (Soil-covering column)


3.7.

,

. , (Silt) (Clay)

.

, ,

, . ,

.

(2005.09) 4 1

. ,

. , ,

3~4 , 105 ( 3-9)℃

.

3-9.


3.8.

3.8.1

Sensoronic (OSR-1000)

. CH4 CO2 0~100% , H2S 0~5,000 ppm ,

(Syringe)

. Shiagawa(Japan) (W-NK-5A)

.

Agilent Technologies(USA) GC chromatography 7890A(TCD

detector) CH4 CO2 , H2S

Varian(USA) GC chromatography CP-3800(PFPD detector)

.

3.8.2

3-4

, pH, BOD5, CODcr Standard Methods(21st edition 2005)

, SO42-, Total-sulfide(H2S, HS

-, S2-), T-N, T-P Hach

DR5000 Spectrophotometer . BOD5, CODcr

BOD, COD .


3-4.

pH

BOD5

CODCr (Closed Reflux Method)

T-N

T-P

SO42-

Total-sulfide



.Ⅳ

4.1.

4.1.1

2012 10 2009~2011

, .

.

, , , , SO42-

, .

( , , ) , ,

, , .

,

.

.

7 , + ,

+ , , ,

( ) 4-1 , .

,

. H2S

.

.


4-1.

a)

12%, 38%, 20%, b) 30%

+72%, c) 28%

+79%, d) 21%

e) 11%, 44%, 23%,

1%, 4%,

55%, 24%, 21%

, 100%

( ) 100%

a) 2012 10 2009~2011 ,

b) , , , ,

c)

d)

e) ( , , )


4.1.2

, ,

, , . VS

, .

70% (TS) , +

68.67% ,

86.30% . ,

44.17% + 78.29%

. , 50%

.

67.47% ,

50% 45.68% .

3.17%, 11.63% .

+ +

34.63%, 36.49% , 38.20%

( 4-2).


4-2.

(%)(%) (%) (%)

92.12 7.88 45.68 46.44

+68.67 31.33 34.63 34.04

+78.29 21.71 36.49 41.80

74.25 25.76 67.47 6.77

70.21 29.79 38.20 32.01

99.98 0.02 3.17 96.82

( )86.92 13.08 11.63 75.29

2※


4.1.3

(EA) (900 )℃

, (N), (C), (H),

(S), (O) . 4-3 , 2012

10 2009~2011 ( 4-3).

4-3. (%, )

C H O N S

3.24 0.45 36.01 0.20 0.00

7.23 1.42 42.42 0.67 5.15

47.27 5.53 38.97 2.88 0.25

26.77 3.36 39.93 1.72 2.08

32.25 4.67 23.32 5.15 0.41

23.93 2.27 13.59 2.35 1.41

57.17 8.42 21.78 0.41 0.00

+28.31 3.73 35.28 2.68 1.62

+26.17 3.13 34.40 1.85 1.94

35.22 4.85 32.09 2.12 1.23

2※


4.2. SO42-

4.2.1

, + +

4-1 4-2 . + +

,

+ + 140 BOD

9,414 mg/kg 5,639 mg/kg

.

Sulfate(SO42-) ,

, SO42- ( 4-3). ,

, . , COD

6,151 mg/kg BOD COD

.

4-1. BOD


4-2. COD

4-3. SO42-


(Gypsum) ( ) 140

4-4, 4-5 . ,

, BOD 226 mg/kg, COD 436 mg/kg

. ,

BOD 1,140 mg/kg, COD 6,843 mg/kg . 38%

.

SO42- 6 730 mg/kg , 140

1,910 mg/kg ,

. 3 20,153 mg/kg

SO42- , ,

. (6 )

10 SO42- . 140 25,233

mg/kg SO42-

( 4-6).

4-4. BOD


4-5. COD

4-6. SO42-


4-7 4-8 .

BOD COD

, , . ,

. 140 BOD

25,667 mg/kg, 23,343 mg/kg .

4-9 SO42- ,

. 140 SO42- 1,450 mg/kg

, 1,690 mg/kg

. 10% , ,

.

4-7. BOD


4-8. COD

4-9. SO42-


4-10 4-11

. BOD COD

,

, 140 20% BOD .

BOD 56,149

mg/kg .

1,090 mg/kg SO42-

, 140 3,000

mg/kg SO42- . SO4

2-

(Gypsum) ( 4-12).

4-10. BOD


4-11. COD

4-12. SO42-


4.2.2 SO42-

) SO42-

(Digestion) ,

, Sulfate(SO42-) SO4

2-

, 4-4 .

SO42- ( ) 58,381

mg/kg , 8,038 mg/kg

. SRB H2S

.

4-4. (Digestion) SO42-

3 .※

a : ‘ SRB ’

b :

c :

Sulfate(mg/kg)

a 8,038±3,060

a 58,381±5,198

c 699±173

b 17,661

4,564±1,884

1,253±106

3,305±345

+ b 13,067

+ b 14,646

** 11,072


) SO42-

H2S

SO42- .

(Extraction)

SO42- , (Digestion)

SO42- . SRB

SO42- H2S . ,

SO42-

, H2S

.

SO42- 4-5 ,

6 .

. ,

, 140

. SO42-

, SRB SO42-

( 4-5).

6 SO42- , 140

SO42- 2.2 . 43%

. 140 SO42- 1,910 mg/kg

, 24%

.

SO42- .


6 160 mg/kg

SO42- , 4,564 mg/kg

. 140 SO42-

1,450 mg/kg 1,253 mg/kg ,

,

. 6 140 SO42-

, SO42- 3,305 mg/kg

3 SO42- .


4-5. (Extraction) (Digestion) SO42-

( : mg/kg)

Extraction

Digestion

6 hr 140 day

570 6,200 17,661

+550 3,120 13,067

+540 3,560 14,646

160 1,090 4,564

440 3,000 11,072

730 1,910 8,038

( )11,733 25,233 58,381

210 1,450 1,253

290 1,690 3,305


4.3. Batch test CH4 H2S

4.3.1 CH4 H2S

Batch test , (Headspace)

16 , 35 0 , 1℃ ℃

, 35 42.2 mmHg℃

( 17). , VS

.

.

℃ (16)

, C1 : (%)

C0 : (%)

V1 : Syringe (mL)

V0 : Serum bottle Headspace (mL)

℃

×

(17

, STP : 0 , 1atm℃

CH4 12.59~23.43 mL/g VS

, 18.01 mL/g VS ( 4-13). H2S 0.061~0.082 mL/g VS

, 0.07 mL/g VS CH4

( 4-14).

SRB 30 SRB

.


4-13. VS CH4

4-14. VS H2S


+ Batch test 4-15, 4-16 ,

CH4 63.21~96.06 mL/g VS , 79.63

mL/g VS . H2S 0.065~0.085 mL/g VS ,

0.075 mL/g VS CH4 , H2S

.

4-15. + VS CH4

4-16. + VS H2S


+ Batch test 4-17, 4-18 ,

CH4 47.80~57.67 mL/g VS , 52.73

mL/g VS . H2S 0.056~0.060 mL/g VS ,

0.058 mL/g VS CH4 , H2S

.

4-17. + VS CH4

4-18. + VS H2S


4-19, 4-20 , CH4

166.11~167.58 mL/g VS , 166.85 mL/g VS

. H2S 0.040~0.071 mL/g VS , 0.055 mL/g

VS .

CH4 .

4-19. VS CH4

4-20. VS H2S


4-21, 4-22 , CH4 H2S

. ,

.

4-21. VS CH4

4-22. VS H2S


4-23, 4-24 ,

. CH4 7.27~5.99 mL/g VS

, 6.63 mL/g VS . H2S 0.017~0.030 mL/g VS

, 0.024 mL/g VS . (Multi-extarction)

, .

4-23. VS CH4

4-24. VS H2S


4-25, 4-26 ,

, CH4 244.54~286.58 mL/g VS

, 265.56 mL/g VS . H2S 0.032~0.033 mL/g VS

, 0.032 mL/g VS . 70

.

4-25. VS CH4

4-26. VS H2S


Batch test

, + 4-27, 4-28 ,

. CH4

286.49~326.22 mL/g VS , 306.36 mL/g VS .

H2S 0.029~0.030 mL/g VS , 0.030 mL/g VS

. CH4 , H2S

.

4-27. + VS CH4

4-28. + VS H2S


+ 4-29, 4-30 . CH4

260.06~273.93 mL/g VS , 266.99 mL/g VS

. H2S 0.031~0.034 mL/g VS , 0.032 mL/g VS

, CH4 , H2S

SO42- .

4-29. + VS CH4

4-30. + VS H2S


4.3.2 Batch test

Batch test 18~20 1 ,

(Linear)

. (K)

, 4-6 .

- 1 , 18 .

(18)

- S= t (g VS/L), k= (day-1)

(19)

- M= t (mL/g VS), Y=

, S0=

- t=0 , S0 2 20

.

(20)

- S0Y= M0(mL/g VS), k= (day-1)


4-6. Batch test (80 )

CH4

(mL/g VS)

H2S

(mL/g VS)

18.013 0.071

+ 79.632 0.075

+ 52.732 0.058

265.560 0.032

166.848 0.055

0.000 0.000

6.628 0.024

+ 306.358 0.030

+ 266.992 0.032

Batch test CH4 H2S 80 4-6

, CH4 ,

,

.

. 52.732~79.632 mL/g VS CH4 ,

CH4 . H2S

,

+ 0.075 mL/g VS 0.071 mL/g VS

.


4-7. Batch test

CH4K (day

-1)

H2SK (day

-1)

0.2685 0.1037

+ 0.4153 0.0661

+ 0.3202 0.0658

0.0788 0.2847

0.4147 0.1111

0.0000 0.0000

0.7484 0.5907

+ 0.1853 0.4915

+ 0.1113 0.3826

, (1997)

(K) 0.03~0.12 day-1 . 0.08

day-1 (K) , 265.560 mL/g VS

CH4 ( 4-7). (2004)

. CH4

(K) ,

, (K) . Owens (1993)

369 mL/g VS CH4 0.14 day-1 (K)

, .


4-8. (k)

CH4

(mL CH4/g VS) k(day-1)

(1997)*

( ) 269 0.08

315 0.10

234 0.12

127 0.03

262 0.06

82 0.03

(2004)*

( ) 258.5 0.08

( ) 264.6 0.07

153.8 0.08

97.9 0.06

Owens (1993)

369 0.14

278 0.06

( ) 84 0.08

( ) 100 0.07

203 0.12

349 0.1

343 0.12

334 0.14

318 0.09

341 0.08

*


4.4. (Lysimeter)

4.4.1 H2S

pilot ,

(Lysimeter)

30 ±3 , 0 , 1atm℃ ℃

, 21 .

(kg) , (%)

(L/day) .

℃±×

×

(21)

- , STP : 0 , 1atm℃

Lysimeter 4-31~34 .

,

. LFG 164 0.4 L/kg ,

CH4 15 mL/kg, H2S 9 mL/kg .

LFG CH4 3.4%, H2S 2.0% .

, pH 7~8 , 27 BOD SO42-

.


4-31.

4-32.


4-33.

4-34.


+ Lysimeter 4-35~38 .

(LFG) ,

164 5 L/kg , CH4 50

40% H2S

. CH4 Lysimeter

.

. 80 H2S CH4

. 80 H2S 26%

, CH4 10% . ,

SRB H2S

.

, Plaza (2006)

H2S

H2S 150,000 ppm .

H2S CH4 H2S CH4

, 0.51, 1.65 L/kg .

SO42- SRB . ,

H2S , CH4

, .

113 Total-sulfide SO42-

, BOD .


4-35. +

4-36. +


4-37. +

4-38. +


+ Lysimeter +

, 4-39~42 . CH4

, 40

, 130 H2S CH4 17% .

H2S CH4

, SRB H2S CH4

.

,

H2S .

4-39. +


4-40. +

3-41. +


4-42. +


Lysimeter 4-43~46 ,

(LFG) 83.28 L/kg

. CH4 58%

. H2S

1,200 ppm 100 100 ppm

. BOD 30 ,

, Total-sulfide SO42- .

4-43.

4-44.


4-45.

4-46.


Lysimeter 4-47~50 .

, 20

. H2S CH4 H2S

CH4 (LFG)

.

SO42- SRB .

4-47.

3-48.


4-49.

4-50.


Lysimeter 4-51~54 , 164

, pH 11.3 .

, pH ,

SRB MPB .

4-51.

4-52.


4-53.

4-54.


Lysimeter 4-55~56 .

, SO42-

.

4-55.

4-56.


4-57.

4-58.


4-9. Lysimeter

LFG (mL/kg) CH4 (mL/kg) H2S (mL/kg) CH4/LFG (%) H2S/LFG (%)

446 15 9 3.4 2.0

+5,400 1,646 514 30.5 9.5

+2,825 1,097 109 38.8 3.9

83,278 42,807 20 51.4 0.0

5,764 3,188 68 55.3 1.2

40 (0.4) 0 1.0 0.0

31 (0.4) 0 1.3 0.0

164 Lysimeter

4-9 , LFG CH4 H2S

. CH4/LFG 3.4%, H2S/LFG 2.0%

, H2S +

CH4/LFG 30.5%, H2S/LFG 9.5% , H2S

. 2

CH4/LFG 55.3%, H2S/LFG 1.2% .

H2S ,

.


4.4.2 (Lysimeter)

C, H, O, N, S (Buswell’s equa-

tion) 22 (Tchobanoglous

, 1993 Owen , 1979), (Lysimeter)

. (Digestion)

SO42- pH SRB Acetate 23

, 24 SO42- 1g H2S Lysimeter

H2S .

-

→

(22)

-Acetate H2S

(23)

-1 g SO42-

H2S

×

× (24)


164 Lysimeter (LFG)

4-10 , 6.49% ,

1% . CH4

7.95% , + 2.06%, 1.68%

+ 1.52% . 60

0.04% CH4 ,

. ,

.

4-10. Lysimeter

Lysimeter(L)

Lysimeter(L) (%)

42,516 31 0.07

+ 41,418 345 0.83

+ 37,469 177 0.47

6,812 442 6.49

47,110 339 0.72

19,497 4 0.02

35,229 3 0.01


4-11. Lysimeter CH4

Lysimeter CH4(L)

Lysimeter CH4(L)

CH4(%)

2,388 1 0.04

+ 5,106 105 2.06

+ 4,526 69 1.52

2,859 212 7.95

11,157 174 1.68

0 0 0.00

0 0 0.00

H2S (Digestion)

SO42-

H2S . H2S

( ) 10,529 L , Lysimeter

. H2S

+ 1.42% . +

, , .

(S) ( 4-12).

H2S

, + H2S 32.84% .

SO42- 2 L H2S ,

164 0.1 L . (LFG), CH4 H2S

, SRB

CH4 (inhibition) ,

(LFG) . Lysimeter

.


4-12. Lysimeter H2S

Lysimeter H2S(L)

Lysimeter H2S(L)

H2S(%)

3,281 0.60 0.02

+ 2,311 32.84 1.42

+ 2,660 6.81 0.26

0 0.11 0.00

1,625 4.03 0.25

0 0.00 0.00

10,529 0.00 0.00

4-13. (Digestion) Lysimeter H2S

Lysimeter H2S(L)

Lysimeter H2S(L)

H2S(%)

133 0.60 0.35

+ 90 32.84 28.89

+123 6.81 4.37

2 0.11 0.00

70 4.03 4.66

91 0.00 0.00

549 0.00 0.00


4.5.

(1~5 ) ( 4-59)

SRB H2S 8 , 10

40,000 ppm . +

( 4-60) CH4 10%

, H2S 9 50,000 ppm .

( 4-61) SO42-

40,000 ppm H2S . Lysimeter CH4 H2S

50% CH4 ,

1,200 ppm H2S .

9 ,

, 11

(Crack) ,

. 1 5 10% , 8

50% CH4 , Lysimeter

MPB .

,

11 ,

.


4-59.

4-60. +


4-61.


4.6. H2S

H2S 4-62

. 6,000 ppm 32 hr, 3,500 ppm 138 hr

1,000 ppm 332 hr .

H2S , (linear equation)

. 4-14

, H2S .

1,000 ppm 286 hr , 83 hr . 6,000

ppm 29 hr, 4 hr ,

. H2S

Sulfide mineral H2S H2S

.

(

2010~2011, 2012) 2011

4.27 L/m2/hr

, , 2012

0.42 L/m2/hr 2011 10%

.

1,910 L/m2/hr 2

3 1.91 L/m2/hr 1,000

. 2 1,000 ppm 10

, 3,500 ppm 3 , 6,000 ppm 0.5 ( 6 )

H2S

. , 15 cm ,

50 cm

. ,

H2S 6,000 ppm 1 .


4-14.

주입 농도 미 출기간(hr) 파과점(hr) R2

1,000 ppm 83 286 0.9898

3,500 ppm 24 122 0.9820

6,000 ppm 4 29 0.9611

4-62. H2S

H2S

(linear) 25

(Thomas model) (Thomas, 1948). 4-15

, H2S 0.406~0.325 L/hr/g

,

.

ln

(25)

- Ce (ppm) , C0 (ppm) k Thomas (L/hr/g), q0

H2S (g/kg), M (kg), V (L), Q

(L/hr) .


4-15. H2S

주입 농도도상수 KTH

(L/hr/g)

흡착량 q0

(g/kg)R2

1,000 ppm 0.325 0.325 0.961

3,500 ppm 0.297 0.736 0.924

6,000 ppm 0.406 2.956 0.965

4-63. H2S Sulfide mineral


Xu (2012) H2S

, Serum bottle

Fine concrete, CaCO3, Ca(OH)2 Xu (2010)

, H2S 5 90%

.

( 4-64).

4-64. H2S


4.7.

( ) 4-65 (Mulfi-extraction)

(Digestion) SO42-

, 2011 11%

. SO42- .

4-66 (Sand) 1 mm ~ 75 µm

83.9% , 71.8% ,

(Silt) (Clay) 6.4% 24.0% .

,

.

4-65. SO42-


4-66.

4-67 SO42-

, SO42- (%) .

106 µm 65% SO42-

, 55% 10% , SO42-

. 106 µm SO42-

,

. , 38 µm 5% SO42-

25% 20% .


4-67. SO42- mass

SO42- ,

. (2005) 10-3

cm/sec, 52%, (pH) 9.9, 90 mg/kg, 2,000

mg/kg, 27.7 cmol/kg ,⋅

4-16 (1999) , ‘ ’

‘ ’ . ,

, . ,

.

106 µm

. SO42-

. 106 µm

, SO42- 93% .

91%

. 106 µm

20% , SO42- 31% . SO4

2-

.


4-16.

m3/m3 0.6 0.5~0.5 0.4~0.5 0.4

cm/sec 10-3 10-4~10-3 10-5~10-4 10-5

6.0~6.55.5~6.0

6.5~7.0

4.5~5.5

7.0~8.0

4.5

8.0

dS/m 0.2 0.2~1.0 1.0~1.5 1.5

cmol/kg 20 6~20 6

mg/kg 200 100~200 100

cmol/kg 3.0 0.6~3.0 0.6

cmol/kg 5.0 2.5~5.0 2.5

% 5.0 3.0~5.0 3.0


. SRBⅤ

5.1. H2S H2S

5.1.1 SO42-

(H2S) Sulfate(SO42-)

, 140 (Multi-extraction) (Digestion)

5-1 . 6

SO42- .

SO42- 5.8%

SO42-

,

SO42- .

SO42- , SO4

2- 4,564 mg/kg .

(CaSO4 2H⋅ 2O) SO42-

, SO42-

.

5-1. SO42-


5.1.2 H2S

(SRB) (MPB) pH, , , ,

, , , (Sulfate), , , ⋅

. SRB MPB (Acetate)

, . Bhattacharya (1996)

Acetate SRB H2S 26 ,

SO42- H2S .

Acetate SO42-

, H2S . 5-1

(BOD) SO42- H2S , SO4

2-

SO42-

. 6

4% SO42- , 140 ,

SO42- 31% H2S ,

.

H2S

, , SRB

. ,

SO42- .

-SRB reaction

(26)


5-1. BOD SO42-

6hr 140day *

BOD

(mg/kg)

Sulfate

(mg/kg)

Sulfate

(%)

BOD

(mg/kg)

Sulfate

(mg/kg)

Sulfate

(%)

22 570 4 1,732 6,200 31

+3,855 550 100 9,414 3,120 100

+1,325 540 100 4,980 3,560 100

18,816 160 100 197,223 1,090 100

6,900 440 100 56,149 3,000 100

* 140


5.1.3 H2S CH4

H2S CH4 Batch test ,

1 , (K)

( , 1998).

H2S CH4 , SRB SO42-

SO42- .

5-2 Batch test H2S CH4 (K) VS

. CH4 (K)

0.269 0.079 , 18.013 mL/g VS

, 265.560 mL/g VS .

(K) .

CH4 265.560 mL/g VS,

306.358 mL/g VS, 266.992 mL/g VS

, .

,

MPB .

CH4

.

H2S

. SO42- ,

SO42-

. SO42- H2S

.

Batch test BMP

CH4 ,

H2S .


5-2. H2S CH4

CH4

K(day-1)

H2S

K(day-1)

CH4

(mL/g VS)

H2S

(mL/g VS)

0.269 0.104 18.013 0.071

+0.415 0.066 79.632 0.075

+0.320 0.066 52.732 0.058

0.079 0.285 265.560 0.032

0.415 0.111 166.848 0.055

0.000 0.000 0.000 0.000

0.748 0.591 6.628 0.024

+0.185 0.492 306.358 0.030

+0.111 0.383 266.992 0.032


5.1.4 H2S

(LFG)

, (CO2), CH4, H2S

H2S 99.9% (

, 2011).

. H2S 2 1,000

1,000 ppm 10 ,

3,500 ppm 3 , 6,000 ppm 0.5 ( 6 ) ,

(50 cm)

6,000 ppm 1 ,

H2S .

H2S 0.325~2.956 g/kg

.

H2S

(K+), (Mg2+), (Ca2+), (Mn2+), (Fe2+), (Cu2+),

(Zn2+), (Na+) H2S Sulfide mineral

(Xu, 2010), Sulfide

mineral . , H2S

H2S

, Sulfide

.


5.2. ⋅

5.2.1 (Lysimeter)

Lysimeter H2S , 164

. (LFG)

40 ,

, 164 442.21 L ( 5-2). CH4

227.30 L , H2S 0.11 L CH4 H2S

. , 60

(LFG) 31.40 L, CH4 1.07 L,

H2S 0.60 L . 80

CH4 , ( 5-3).

60 CH4

LFG , H2S , LFG

. H2S 32.84 L

, H2S 6.81 L

. H2S

,

SO42- SRB

H2S . ,

. SO42-

,

H2S ( 5-4).


5-2. Lysimeter

5-3. Lysimeter CH4


5-4. Lysimeter H2S


5.2.2

SO42- Iss (1986) SRB MPB

. SO42-

COD Acetate, Lactate

. COD

BOD . SRB MPB

/SO42- 6.7 MPB

, SRB .

(Lysimeter) , +

BOD/SO42- SRB

, CH4 .

41.79, 80.09 , +

BOD/SO42- MPB , H2S

. BOD/SO42- SRB

MPB , BOD/SO42-

,

CH4 .

5-3. BOD/SO42- H2S

BOD/SO42- H2S (L)

0.51 ±0.36 0.60

+41.79 ±38.25 32.84

+2.09 ±2.48 6.81

80.09 ±58.08 0.11

3.51 ±1.30 4.03

0.81 ±0.61 -

0.09 ±0.04 -


5-5. +

5-5 + SO42-

Total-sulfide

CH4, H2S BOD/SO42-

MPB

SRB , CH4

. , 27 SO42-

61 H2S

9.24% , 23.89% Total-Sulfide SO42-

. H2S /SO42-

SO42- Sulfide .


5.3. ⋅

5.3.1

SO42-

( ) , Sulfate 140 (Multi-extraction)

1,910 mg/kg, (Digestion) 8,038 mg/kg .

(Multi-extraction) 25,233 mg/kg, (Digestion)

58,381 mg/kg SO42- .

⋅

, H2S . 5

mm 8%, 72%, 3%, 21%

( ) .

.

5-4 ‘

, 2 , 1, ’

, ’

2 1 ’ , 100mm ,

5% , ,

.

, ‘

4 3 ’ ,ㆍ

,

. ’ , 5 2,

, 2 3 ’

50% ,ㆍ ㆍ

, .


100 mm ,

5% , ,

50% .

5-4.

, 2 , 1

2 , 1

100 mm ,

5% ,

⋅

, 4 , 3,⋅

,

, 5 2, 2

3

50% ,

⋅


5.3.2

2004~2005 ‘

‘ ( )

.

, , ,

,

,

pH 6.5 .

5-5.

m3/m3 0.6 0.5~0.5 0.4~0.5 0.4

cm/sec 10-3 10-4~10-3 10-5~10-4 10-5

6.0~6.55.5~6.0

6.5~7.0

4.5~5.5

7.0~8.0

4.5

8.0

dS/m 0.2 0.2~1.0 1.0~1.5 1.5

cmol/kg 20 6~20 6

mg/kg 200 100~200 100

cmol/kg 3.0 0.6~3.0 0.6

cmol/kg 5.0 2.5~5.0 2.5

% 5.0 3.0~5.0 3.0

* :


. ‘

5 ’ ,

,

, , ,

( ) .

(pH) (

5-5).

(S) H2S

, (S) , ,

, , , ,

. .

, (Ca)

, ,

. ,

Ca

,

( ) .

‘ , 4 2 , 1, ∙ ∙

’

, , 2 3 · · · ·

, .

,

. ,

.

, .


( ), ( ),

( 30% ), ( )

, ,

, ( ), , ( ,

) .

( · · · · )

, .

1 (2000)

( ) (1 ) ,

,

2010

.

,

CO2 27 CO2 ,

pH 8.5~10 ( , 2010). (2013)

CO2

10.6% CO2 .

, SO42- ,

SRB SO42- , CaO Sulfide

mineral( 28) H2S , CO2

.

SO42- , pH

10-7 cm/sec .

.

CaO+ H2O + CO2 CaCO→ 3 + H2O (27)

CaO+ H2O + H2S CaS(Sulfide mineral) + 2H→ 2O (28)


5.4. SRB H2S

(Gypsum) H2S

(CDM)

CH4 .

H2S , CH4

. Sulfide mineral

( 등 과Xu , 2011) ( 등Xu , 2010), SRB

H2S .

,

. H2S

.

H2S

. SO42- ,

( ) 5.8% SO42-

(Digestion)

, Batch test CH4 H2S .

(Lysimeter) Pilot test

.

, H2S H2S

. , 70%

2 , H2S

5 .

,

pH 8

.


5-6. Lysimeter BOD/SO42-

DayBOD(mg/kg)

SO42-

(mg/kg)BOD/SO4

2- CH4(mL/day)

H2S(mL/day)

0 151 7 21.53 0 0

12 2,120 460 4.61 7,296 0

27 2,080 400 5.20 4,849 0

61 2,150 600 3.58 1,024 25

87 1,320 1,000 1.32 223 57

113 1,368 680 2.01 64 33

133 1,758 400 4.39 98 58

166 1,634 470 3.48 49 33

1) 2 2009~2011

2)

3)

2 2009~2011

(Lysimeter) 5-7 , 61

BOD/SO42- 3.58 , CH4 1,024 mL/day, H2S

25 mL/day . BOD/SO42-

, 2

Lysimeter BOD/SO42- 5 CH4

. 5-8 2001 2011 BOD/SO42-

2005 11.37 , 2007 1 .

Lysimeter CH4 ,

H2S .


5-7. 2 BOD/SO42-

BOD(mg/kg)

SO42-

(mg/kg)BOD/SO4

2-

2001 20,195 380 53.17

2002 12,151 167 72.62

2003 4,058 58 69.75

2004 3,871 61 63.90

2005 1,561 137 11.37

2006 1,122 261 4.29

2007 207 334 0.62

2008 141 362 0.39

2009 108 326 0.33

2010 145 216 0.67

2011 173 212 0.82

- 2 2001~2011

164 Lysimeter

, 5-8 . 3

CH4 3,188 mL/kg, H2S 68 mL/kg

9 mL/kg H2S CH4 15 mL/kg .

H2S 20 mL/kg , CH4 42,807 mL/kg .


5-8. (Lysimeter)

LFG (mL/kg) CH4 (mL/kg) H2S (mL/kg)

446 15 9

+5,400 1,646 514

+2,825 1,097 109

83,278 42,807 20

5,764 3,188 68

40 (0.4) 0

31 (0.4) 0

- Lysimeter 164

5-6 RDF

. , H2S kg 68

mL 9 mL, 20 mL .

, 5-9 2011

H2S 89.3% .

. ⋅

, .

SRB

SO42-

, .


5-9. 2011 2

(ton) 4,334,283 765,142 1,789,547

H2S ( m3) 295 15 16

CH4 ( m3) 13,818 32,753 25

- 164 Lysimeter Kg

H2S

, , ( )

,

. SO42-

, SRB H2S . ,

SO42-

CH4

CH4 (50~60%V/V) 2011

, 2.4

CH4 . UNFCCC

CER(Certified Emission Redution) 39.4 CO2

(CDM) IPCC (BAU

15~30%) , .

5-6.

매립장 대기질 개선을 위한 억제방안 연구SRB



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SRB(Sulfate Reducing

Bacteria)

2013. 03


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