use of flue gas from combustion of landfill gas (lfg) as the
TRANSCRIPT
Use of Flue Gas from Combustion of Landfill Gas (LFG) As the Source of CO2 For Algae Biomass
Production with Scenedesmus obliquus: Growth, FAME’s, and Heavy Metals
Joshua S. Wilkenfeld1, Pallab Sarker2, Anne Kapuscinski2
Algae Biomass Summit Orlando Florida 2 October, 2003
1Algae Cultivation Specialist, Contractor 2Environmental Studies Program, Dartmouth College
1
Benemann, 2013
“The concept of C02 utilization and fuel production by microalgae was first proposed over four decades ago…” Benemann & Oswald,1996
2
“The utilization of the flue gas [from incinerated municipal waste] containing 10-13% (v/v) CO2 and 8-10% (v/v) O2 for a photobioreactor …enables [sic] to produce biomass [C. vulgaris], which for contaminants. …cannot be neglected…” Douskova et al., 2008
?!?
3
• “Mercury is the only heavy metal reported in [raw] gaseous emissions from landfills. Measured levels have consistently been low enough to suggest little cause for concern
• …the mean concentration of mercury is between 5 and 10 μg/m3 …theoretically possible that other metals, such as arsenic, could be transformed in a landfill into organic forms volatile enough to escape to the atmosphere
• …combustion of landfill gas will convert organic mercury [and other metals] to inorganic forms.” Aucott, 2006
4
Compare growth (c/ml) and standing-crop production (g/L) of S. obliquus grown with :
• Commercial CO2
• Flue-gas from LFG-fired 300 KW Guascor CHP generator
Test gasses, algae, supernatant, and FG condensate for
Arsenic (As) Cadmium (Cd)
Cobalt (Co) Lead (Pb)
Mercury (Hg) Tin (Sn)
Compare results to and available EPA air and
effluent regulations LFG = Land Fill Gas CHP = Combined Heat & Power 5
Bower 1: , and mix of
Blower 2: Mix of
control mixes
Multiple to check gas mixes using LANDTECH GEM 2000 gas analyzer 6
Starting density: 10.4 x106 c/mL (0.2 g/L afdw)
Daily monitoring/adjusting of gas mixes and flow rates (2% CO2, 0.47 LPM = 1 SCFM)
Daily record of temp, pH, and cell counts
afdw: DOC-0, 3, 6, 10 & 13
FAMEs: DOC-0, 6 & 13
Metals in algae & supernatant: DOC-13
Metals in gases & FG condensate: One time 7
24 Hours After Inoculation 48 Hours After Inoculation
8
• Little control over ambient temp; range was 18.6-26.5 °C
• pH: After stocking, pH in both CO2 treats stayed around 7.5. pH in Air Only climbed steadily to high of 11.0.
• NO3: Was being consumed in all treatments; much less so in Air only (lower c/mL)
• PO4: With Latchat chemistry, seems to disappear in 3-4 days, but unclear if this is limiting.
Min Max Mean AIR+CO2 7.2 8.2 7.5
AIR 8.2 11.0 10.0
AIR+Flue Gas 7.3 8.4 7.6
Min Max Mean AIR+CO2 18.6 26.5 22.9
AIR 18.7 25.9 22.6
AIR+Flue Gas 18.7 25.3 22.4
9
0
50
100
150
200
250
300
0 6 13
NO
3-N
in
mg/
L (p
pm
)
Days of Culture (DOC)
NO3-N FG Condensate BG-11 Media
Starter Culture Air+CO2
Air Air+Flue Gas
0
2
4
6
8
0 6 13
PO
4-P
in
mg/
L (p
pm
)
Days of Culture (DOC)
PO4-P FG Condensate BG-11 MediaStarter Culture Air+CO2Air Air+Flue Gas
0.00
2.00
4.00
6.00
8.00
0 6 13
NO
2-N
in
mg/
L (p
pm
)
Days of Culture (DOC)
NO2-N FG Condensate BG-11 MediaStarter Culture Air+CO2Air Air+Flue Gas
0.0
0.5
1.0
1.5
0 6 13
NH
4-N
in
mg/
L (p
pm
)
Days of Culture (DOC)
NH4-N BG-11 Media Starter CultureAir+CO2 AirAir+Flue Gas
• Cell Density (c/ml) & Biomass (mg/ml): No significant difference between flue gas or CO2
(p>0.05), but both are significantly greater than air (p<0.05)
• Productivity (g/L/d)
• Starter Culture:
DOC = 37 Approx. 35% evap. c/ml = 210-million Afdw = 4,399 mg/L
0
20
40
60
80
100
0 1 2 3 4 5 6 7 8 9 10 11 12 13
c/m
l x 1
0 6
Days of Culture (DOC)
Air+CO2 MeanAir MeanAir+FG Mean
0
500
1,000
1,500
2,000
2,500
0 3 6 10 13
afd
w (
mg
/L)
Days of Culture (DOC)
a
a
b
a a
b
10
Air & CO2 0.141
Air 0.084
Air + FG 0.163
a a b
a a b
• Six of 17 FA’s = 91% of total FA’s at start
• By end, major FE’s have dropped to around 80% in treatments with CO2 or FG
• Biggest changes: Increase in Palmitoleic (16-1) and Oleic (18:1n9, and a 50% drop in ALA (18:3n3) and)
Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry by Chemical Analysis and Instrumentation Laboratory, NMSU
Fatty Acid
DOC-0 DOC-6 DOC-13
Starter Culture
Air + CO2
Air Air + FG Air + CO2
Air Air + FG Air + CO2
Air Air + FG
Myristic 14:0 0.46 0.56 0.65 0.55 0.36 0.46 0.34 0.49 0.45 0.43
Myristoleic 14:1 0.63 0.55 0.68 0.59 0.59 0.45 0.62 0.65 0.49 0.63
Pentadecanoic 15:0 0.27 0.32 0.34 0.29 0.34 0.14 0.29 0.53 0.14 0.33
Pentadecenoic 15:1 0.22 0.27 0.32 0.22 0.34 0.18 0.39 0.37 0.24 0.31
Palmitic 16:0 22.59 22.71 25.78 22.69 24.32 21.77 23.21 29.20 22.81 25.88
Palmitelaidic 16:1 0.71 0.98 1.09 0.91 3.26 1.52 3.10 3.69 1.50 2.94
Palmitoleic 16:1 0.76 0.96 1.16 0.91 7.24 0.45 5.84 9.22 0.30 5.12
Hexadecadienoic 16:2 0.69 0.75 0.77 0.78 1.49 0.69 1.49 1.33 0.89 1.88
Heptadecanoic 17:0 0.21 0.24 0.26 0.22 0.44 0.19 0.35 0.54 0.24 0.45
Hexadecatrienoic 16:3 1.74 1.51 1.51 1.56 0.41 0.74 0.40 1.19 1.03 0.93
Hexadecatetraenoic 16:4 9.03 8.69 7.73 9.15 10.31 11.79 11.23 6.11 11.09 6.50
Stearic 18:0 0.79 0.87 0.83 0.88 1.19 0.84 1.09 2.54 1.01 1.92
Oleic 18:1n9 9.64 10.22 11.03 10.08 14.81 15.41 13.99 17.50 14.43 18.01
Linoleic (LA) 18:2n6 9.18 8.84 8.54 8.89 11.55 7.12 12.02 9.85 8.24 14.28
Gamma-Linolenic (GLA) 18:3n6 1.44 1.34 1.31 1.42 1.02 0.61 1.06 1.23 0.84 1.60
Alpha-Linolenic (ALA) 18:3n3 33.40 33.24 30.99 33.26 19.09 31.71 20.79 13.17 30.94 15.76
Octadecatetraenoic 18:4 8.26 7.96 7.01 7.60 3.25 5.92 3.82 2.39 5.37 3.04
Total %: Six Major Fatty Acids 92.09 91.66 91.08 91.66 83.33 93.72 85.05 78.22 92.87 83.46
Total %: 11 Minor Fatty Acids 7.91 8.34 8.92 8.34 16.67 6.28 14.95 21.78 7.13 16.54
11
• %FAME/Unit wt not significantly different (P>0.05)
• Slight decline of % FAME by DOC-13
• Yield of FAME/L is significantly different (P<0.05)
• % FAME and mg/L on DOC-0 are greater for starter (Time and evap = high c/ml and mg/L)
20
84
127
20
58
101
21
107
180
0
20
40
60
80
100
120
140
160
180
200
0 6 13
8-Mar-13 14-Mar-13 21-Mar-13
Tota
l FA
ME
(mg
/L)
Day of Culture (DOC) and Date
Starter Culture Air+CO2 Air Air+Flue Gas514
a
Day of Culture (DOC)
0
2
4
6
8
10
12
0 6 13
8-Mar-13 14-Mar-13 21-Mar-13
% F
AM
E (m
g/1
00m
g d
w) Starter Culture Air+CO2 Air Air+Flue Gas
Day of Culture (DOC)
DOC-37
12
a a
b
ab b
13
Metal
Analyte
PQL
(µg)
Projected
Emission
from
Combustion
of Nat.Gas
Permitted
Air
Discharge
Levels2
Landfill
Gas Main
Supply
Line
Flue Gas
Main
Supply
Line
Air+CO2
Inlet
Air+CO2
Exhaust
Air+FG
Inlet
Air+FG
Exhaust
Arsenic 0.0100 0.0032 0.0500 < 0.0100 < 0.0100 < 0.0100 < 0.0100 < 0.0100 < 0.0100
Beryllium 0.0010 0.0002 0.3600 < 0.0010 < 0.0010 < 0.0010 < 0.0010 < 0.0010 < 0.0010
Cadmium 0.0010 0.0176 0.04-0.05 < 0.0010 < 0.0010 < 0.0010 < 0.0010 < 0.0010 < 0.0010
Chromium 0.0100 0.0224 0.4650 < 0.0100 < 0.0100 < 0.0100 < 0.0100 < 0.0100 < 0.0100
Copper 0.0100 0.0136 0.5-1.0 < 0.0100 < 0.0100 < 0.0100 < 0.0100 < 0.0100 < 0.0100
Lead 0.0200 0.0080 0.02-0.5 < 0.0200 < 0.0200 < 0.0200 < 0.0200 < 0.0200 < 0.0200
Nickel 0.0100 0.0336 0.4440 < 0.0100 < 0.0100 < 0.0100 < 0.0100 < 0.0100 < 0.0100
MERCURY 0.0005 0.0042 0.05-0.08 0.0016 0.0013 0.0021 ND 0.0013 0.0019
Zinc 0.0100 0.4640 1.0000 0.0161 0.0324 0.0177 0.0323 0.0168 0.0163
1 PQL = Practical Quantitation Limits 2 http://www.epa.gov/ttnchie1/ap42/ch01/final/c01s04.pdf 2 Rao, 199?, Montgomery County Department of Public Works and Transportation,Division of Solid Waste Services * Adirondack Environmental Services (gas analysis, NIMAM): Metals, (ICP-AES); Mercury: Atomic Absorption
• Most of the metals are below detection limits
1 BDL = Below Detection Limits; Analysis by ICP-MS (Inductively coupled plasma mass spectrometry) 2 Pollution Prevention and Abatement Handbook WORLD BANK GROUP,Effective July 1998
Metal Arsenic
(As)
Cadmium
(Cd)
Chromium
(Cr)
Lead
(Pb)
Mercury
(Hg)
Tin
(Sn)
Air+CO2 BDL1 BDL 0.0899 BDL BDL 0.0013
Air BDL BDL 0.2271 BDL BDL 0.0018
Air+FG BDL BDL 0.2054 BDL BDL 0.0218
BG-11 Medium BDL BDL BDL 0.0010 BDL 0.0001
FG Condensate 0.0027 0.0053 0.0053 2.2532 BDL 0.0027
Regulations For
Effluent2 0.1 0.1 0.5 0.1 0.01 2.0
Sample Specific
Definition Limit
(SSDL)
0.00004 0.00003 0.00060 0.00001 0.00050 0.00004
14
Metal Arsenic
(As)
Cadmium
(Cd)
Chromium
(Cr)
Lead
(Pb)
Mercury
(Hg)
Tin
(Sn)
Air+CO2 BDL1 BDL 0.0214 0.0062 BDL 0.0899
Air ?!? BDL BDL 0.0382 0.0292 BDL 0.2271
Air+FG BDL BDL 0.0174 0.0104 BDL 0.2054
Douskova et al., 2009 0.2-1 0.05-1 ND 0.1-1.5 0.1-1 ND
Strictest Food
Regulations2 0.10 0.05 1.00 0.02 0.50 50.00
Sample Specific
Definition Limit
(SSDL)
0.0198 0.0149 0.2975 ? 0.0050 0.2479 0.0198
1BDL = Below Detection Limits; Analysis by Dartmouth College Earth Sciences Program using ICP-MS (Inductively coupled plasma mass spectrometry)
2 International Standards: Codex Alimentarius Standard 193-1995, and Hong Kong CAP 132V e b5 2 EC Commission Regulation No 1881.2006
15
Scenedesmus obliquus grown with either
than
with air alone
With a and a flow rate of 0.26 LPM/L of
culture (0.56 SCFM/L of culture; v:v), at a
level of 7.5-7
,
well above what is permissible in effluent (0.1 ppm) or in food
(0.02 ppm)
16
DOC-37
Vermnot Sustainable Jobs Fund: For funding CHE’s VSJF Algae Biofuel Grant
DE-FG36-08GO88182 (VBI-FY09, VBI-FY10); Special thanks to Ellen Kahler and Netaka White
U.S. Department of Energy: For providing funds to VSJF
Carbon Harvest Energy, LTD: They had a dream…
Dartmouth College, Environmental Studies Program: Dr. Anne Kapuscinski (Chair) Dr. Pallab Sarker (Senior Research Associate) and Paul Zietz (Environmental Measurements Lab Manager) for funding from Kapuscinski's Sherman Fairchild Professorship in Sustainability Science, access to lab facilities, library and their support throughout the research.
Senator Patrick Lehey: For his interest in and support of sustainability in Vermont
17