srb(sulfatewebbook.me.go.kr/dli-file/094/003/005/5549970.pdf · 2015-10-30 · -6...
TRANSCRIPT
.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
.
, .
.
매립장 대기질 개선을 위한 억제방안 연구SRB- 4 -
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
수도권매립지관리공사- 5 -
.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).
매립장 대기질 개선을 위한 억제방안 연구SRB- 6 -
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
, .
수도권매립지관리공사- 7 -
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) .
매립장 대기질 개선을 위한 억제방안 연구SRB- 8 -
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)
.
수도권매립지관리공사- 9 -
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
.
매립장 대기질 개선을 위한 억제방안 연구SRB- 10 -
(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
,
수도권매립지관리공사- 11 -
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-
매립장 대기질 개선을 위한 억제방안 연구SRB- 12 -
. 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 .
수도권매립지관리공사- 13 -
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
매립장 대기질 개선을 위한 억제방안 연구SRB- 14 -
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).
수도권매립지관리공사- 15 -
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
매립장 대기질 개선을 위한 억제방안 연구SRB- 16 -
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
.
수도권매립지관리공사- 17 -
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).
매립장 대기질 개선을 위한 억제방안 연구SRB- 18 -
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
수도권매립지관리공사- 19 -
, , ,
, , ,
.
.
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 .
.⋅
매립장 대기질 개선을 위한 억제방안 연구SRB- 20 -
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
수도권매립지관리공사- 21 -
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 .
매립장 대기질 개선을 위한 억제방안 연구SRB- 22 -
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
수도권매립지관리공사- 23 -
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).
매립장 대기질 개선을 위한 억제방안 연구SRB- 24 -
2-7.
(Calcite)
, . (2010)
(Monocarbonat
e) , (Ettringite)
( 2-10).
SO42- .
수도권매립지관리공사- 25 -
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
매립장 대기질 개선을 위한 억제방안 연구SRB- 26 -
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
수도권매립지관리공사- 27 -
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- .
매립장 대기질 개선을 위한 억제방안 연구SRB- 28 -
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
.
수도권매립지관리공사- 29 -
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
매립장 대기질 개선을 위한 억제방안 연구SRB- 30 -
SO42-
. SO42- SO4
2-
Digestion SO42-
.
TCLP 31,
700 mg/kg, Multiple extraction leaching test 51,000 mg/kg
, .
,
.
수도권매립지관리공사- 31 -
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
매립장 대기질 개선을 위한 억제방안 연구SRB- 32 -
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 .
수도권매립지관리공사- 33 -
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 .
.
매립장 대기질 개선을 위한 억제방안 연구SRB- 34 -
2.3.2
1980
,
.
1995
. 2~3
, 1996
.
, ,
,
, ‘ (Gypsum)
SRB(Sulfate Reducing Bacteria) ’ .
SRB SO42-
, SRB .
수도권매립지관리공사- 35 -
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 .
매립장 대기질 개선을 위한 억제방안 연구SRB- 36 -
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
수도권매립지관리공사- 37 -
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).
매립장 대기질 개선을 위한 억제방안 연구SRB- 38 -
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)
NaNO3 0.18:1Lab scale,
1.37L35.0 65 0.6
Okabe .
(2003a)
NaNO3 1.37:1Lab scale,
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
.⋅
매립장 대기질 개선을 위한 억제방안 연구SRB- 40 -
.
2-11
, .
( ) ( ) ( )
2-11.
,① ② ③
Dia-genesis( ) , bulking agents④
, ⑤
ripening process
.
○
,
, , , ,
. (KS)
,
.
, ,
.
, ·
.
수도권매립지관리공사- 41 -
○
, , 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)
매립장 대기질 개선을 위한 억제방안 연구SRB- 42 -
( , ,
, )
Moringa Oleifera Seed
( , )
2-12 Bulking agents( , Moringa Oleifera Seed)
수도권매립지관리공사- 43 -
.Ⅲ
3.1.
3.1.1
, H2S
. (CaSO4 2H⋅ 2O)
( ), ( )
SRB , 2012 10
, ,
. 2009~2011 ,
, , ,
.
, , , , ,⋅
. , , ,
, , ⋅
.
, ,
, , , ( ,
), , ( ) SO42-
H2S
, 3-1 7
.
수도권매립지관리공사- 45 -
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
.
매립장 대기질 개선을 위한 억제방안 연구SRB- 46 -
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.
수도권매립지관리공사- 47 -
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
.
매립장 대기질 개선을 위한 억제방안 연구SRB- 48 -
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
수도권매립지관리공사- 49 -
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).
매립장 대기질 개선을 위한 억제방안 연구SRB- 50 -
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
수도권매립지관리공사- 51 -
20 gauge needle (Syringe)
(Manometer) , (TCD)
(CH4), (CO2) , 1~5 mL (N2)
500 mL , (PFPD) H2S
.
3-3. Batch test
매립장 대기질 개선을 위한 억제방안 연구SRB- 52 -
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).
매립장 대기질 개선을 위한 억제방안 연구SRB- 54 -
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
수도권매립지관리공사- 55 -
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.
매립장 대기질 개선을 위한 억제방안 연구SRB- 56 -
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)
수도권매립지관리공사- 57 -
3.7.
,
. , (Silt) (Clay)
.
, ,
, . ,
.
(2005.09) 4 1
. ,
. , ,
3~4 , 105 ( 3-9)℃
.
3-9.
매립장 대기질 개선을 위한 억제방안 연구SRB- 58 -
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 .
수도권매립지관리공사- 61 -
.Ⅳ
4.1.
4.1.1
2012 10 2009~2011
, .
.
, , , , SO42-
, .
( , , ) , ,
, , .
,
.
.
7 , + ,
+ , , ,
( ) 4-1 , .
,
. H2S
.
.
매립장 대기질 개선을 위한 억제방안 연구SRB- 62 -
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) ( , , )
수도권매립지관리공사- 63 -
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).
매립장 대기질 개선을 위한 억제방안 연구SRB- 64 -
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※
수도권매립지관리공사- 65 -
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※
매립장 대기질 개선을 위한 억제방안 연구SRB- 66 -
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
매립장 대기질 개선을 위한 억제방안 연구SRB- 68 -
(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
매립장 대기질 개선을 위한 억제방안 연구SRB- 70 -
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
매립장 대기질 개선을 위한 억제방안 연구SRB- 72 -
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
매립장 대기질 개선을 위한 억제방안 연구SRB- 74 -
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
수도권매립지관리공사- 75 -
) 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- .
매립장 대기질 개선을 위한 억제방안 연구SRB- 76 -
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- .
수도권매립지관리공사- 77 -
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
매립장 대기질 개선을 위한 억제방안 연구SRB- 78 -
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
.
매립장 대기질 개선을 위한 억제방안 연구SRB- 80 -
+ 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
수도권매립지관리공사- 81 -
+ 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
매립장 대기질 개선을 위한 억제방안 연구SRB- 82 -
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
매립장 대기질 개선을 위한 억제방안 연구SRB- 84 -
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
수도권매립지관리공사- 85 -
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
매립장 대기질 개선을 위한 억제방안 연구SRB- 86 -
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
수도권매립지관리공사- 87 -
+ 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
매립장 대기질 개선을 위한 억제방안 연구SRB- 88 -
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)
수도권매립지관리공사- 89 -
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
.
매립장 대기질 개선을 위한 억제방안 연구SRB- 90 -
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)
, .
수도권매립지관리공사- 91 -
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
*
매립장 대기질 개선을 위한 억제방안 연구SRB- 92 -
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-
.
수도권매립지관리공사- 95 -
+ 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 .
매립장 대기질 개선을 위한 억제방안 연구SRB- 98 -
+ Lysimeter +
, 4-39~42 . CH4
, 40
, 130 H2S CH4 17% .
H2S CH4
, SRB H2S CH4
.
,
H2S .
4-39. +
수도권매립지관리공사- 101 -
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.
수도권매립지관리공사- 109 -
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 ,
.
매립장 대기질 개선을 위한 억제방안 연구SRB- 110 -
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)
수도권매립지관리공사- 111 -
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
매립장 대기질 개선을 위한 억제방안 연구SRB- 112 -
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
.
수도권매립지관리공사- 113 -
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
매립장 대기질 개선을 위한 억제방안 연구SRB- 114 -
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 ,
.
수도권매립지관리공사- 117 -
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 .
매립장 대기질 개선을 위한 억제방안 연구SRB- 118 -
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) .
수도권매립지관리공사- 119 -
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
매립장 대기질 개선을 위한 억제방안 연구SRB- 120 -
Xu (2012) H2S
, Serum bottle
Fine concrete, CaCO3, Ca(OH)2 Xu (2010)
, H2S 5 90%
.
( 4-64).
4-64. H2S
수도권매립지관리공사- 121 -
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-
매립장 대기질 개선을 위한 억제방안 연구SRB- 122 -
4-66.
4-67 SO42-
, SO42- (%) .
106 µm 65% SO42-
, 55% 10% , SO42-
. 106 µm SO42-
,
. , 38 µm 5% SO42-
25% 20% .
수도권매립지관리공사- 123 -
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-
.
매립장 대기질 개선을 위한 억제방안 연구SRB- 124 -
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
수도권매립지관리공사- 125 -
. 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-
매립장 대기질 개선을 위한 억제방안 연구SRB- 126 -
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)
수도권매립지관리공사- 127 -
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
매립장 대기질 개선을 위한 억제방안 연구SRB- 128 -
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 .
수도권매립지관리공사- 129 -
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
매립장 대기질 개선을 위한 억제방안 연구SRB- 130 -
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
.
수도권매립지관리공사- 131 -
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).
매립장 대기질 개선을 위한 억제방안 연구SRB- 134 -
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 -
수도권매립지관리공사- 135 -
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 .
매립장 대기질 개선을 위한 억제방안 연구SRB- 136 -
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
, .
수도권매립지관리공사- 137 -
100 mm ,
5% , ,
50% .
5-4.
, 2 , 1
2 , 1
100 mm ,
5% ,
⋅
, 4 , 3,⋅
,
, 5 2, 2
3
50% ,
⋅
매립장 대기질 개선을 위한 억제방안 연구SRB- 138 -
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
* :
수도권매립지관리공사- 139 -
. ‘
5 ’ ,
,
, , ,
( ) .
(pH) (
5-5).
(S) H2S
, (S) , ,
, , , ,
. .
, (Ca)
, ,
. ,
Ca
,
( ) .
‘ , 4 2 , 1, ∙ ∙
’
, , 2 3 · · · ·
, .
,
. ,
.
, .
매립장 대기질 개선을 위한 억제방안 연구SRB- 140 -
( ), ( ),
( 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)
수도권매립지관리공사- 141 -
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
.
매립장 대기질 개선을 위한 억제방안 연구SRB- 142 -
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 .
수도권매립지관리공사- 143 -
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 .
매립장 대기질 개선을 위한 억제방안 연구SRB- 144 -
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-
, .
수도권매립지관리공사- 145 -
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.
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