Environment-Enhancing Energy Paradigm -- Integrated ... Cover page Slides.pdfEnvironment-Enhancing...
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Environment-Enhancing Energy Paradigm
-- Integrated Approach for BioEnergy, Water and Carbon
Capture
Yuanhui Zhang, PhD, PE
Innoventor Professor in Engineering
Dept. Agricultural and Biological EngineeringUniversity of Illinois at Urbana-Champaign
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Biocrude oil
Clean water
Multi-cycle nutrient and water reuse
CO2Sun light
Algae production
Hydrothermal liquefaction (HTL)
Wastewater and nutrients from Post HTL to algae
Biomass from algae
to HTL
Liquid
Solids
Biowaste
Environment-Enhancing Energy Road-Map
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Alternative EnergyGenerate electricity and heat:
Generate transportation fuel:
Biofuel
Renewable resourcesConversion
Solar energy Wind farm Geothermal energy Hydroelectric power
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Why Low-Lipid Microalgae?
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(Williams & Laurens, 2010)(Rodolfi et al., 2009)
Energy intensive
(~75% of total)
Harvest
Drying
Oil
Extraction
Transesterification
Current approach: high-lipid microalgae for biodiesel.
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青岛
太湖 滇池
巢湖
The naturally
occurring algal
bloom s are all
Low-lipid, fast –
grow species.Low-lipid
Slow-grow
Lipid Content (%)
Bio
ma
ss
High-lipid
Fast-grow
(Extraction)
High-lipid
Slow-grow
(Pharmceuticals)
High
High
Low
Low Lipid
Fast-grow
(HTL)
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Based on the biogenic hypothesis
All fossil fuels found on earth – petroleum (including oil
shale and tar sand), natural gas and coal, are formed
through processes of ThermoChemical Conversion*
from biomass buried beneath the ground and
subjected to millions of years of high temperature and
pressure.
*ThermoChemical Conversion processes include pyrolysis,
hydrothermasl liquefaction and gasification
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Hydrothermal Liquefaction (HTL)
Mimicking Mother Nature’s millions-of-years
process of turning deceased living matters buried
beneath the ground into petroleum, swine manure and
other bio-waste, have been converted into crude oil in
minutes using hydrothermal liquefaction (HTL)
technology in 10 – 40 minutes.
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Source: Hunt, John. 1996
Petroleum Geochemistry and Geology
HTL
1.8 min
1 billion yr
CHG
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Algae to Biocrude Conversion Efficiency
Initial lipid content and HTL oil conversion efficiency for different
feedstocks. Energy recovery ratio is 3~11 to 1. Note that the HTL
can convert the very low-lipid algae into crude oil – a paradigm
shift from ‘extracting’ to ‘converting’. (Yu et al., 2011)
0%
5%
10%
15%
20%
25%
30%
35%
40%C
hlo
rella
Sp
iru
lina
Ch
lam
ydo
mo
nas
Alg
ae S
WP
Alg
ae G
OM
Dia
tom
Alg
ae U
CS
D
RT
Alg
ae
KE
LP
Re
d A
lgae
Sea
wee
d
Sew
age
slu
dg
e
Sw
ine
man
ure
Pe
rce
nta
ge
(w
t%) Bio-crude oil Yield
Lipid Content
Microalgae Macroalgae Biowastes
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1996 1999 2005 2015201320112007
Hydro-thermal?
He et al., 2000,
2001PFR pilot/commercial
system (12 bbl/d)
Licensed from UIUC
PFR reactor system
(2 gallon/d)
Minarick et al.
CSTR system
(1 gallon/d)
Ochemia et al., 2005,
CSTR Commercial
system (160 bbl/d)
Licensed from UIUC
CSTR Pilot system
(10 bbl/d)
Licensed from UIUC
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HTL Feedstock and Biocrude
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Food- Slaughter- Swine MWWprocessing house manure Algae
Feedstook Properties:
Ash Content (dry based) 1.5 8.38 16.3 47.5
Lipid content 52.3 23.8 20.3 1.7
C 60.7 59.5 41.1 27.9
H 8.49 8.77 5.42 3.01
N 3.33 5.44 3.36 3.9
O 27.5 26.3 50.1 65.2
Biocrude oil yield (% dw TS) 62.4 72.1 39 46.8**
High Heating Value (MJ/kg) 40.6 36.5 38.8 32.5
C 75.4 69.7 76.6 59.4
H 12 11.1 10.3 7.79
N 1.79 2.32 3.76 2.5
O 10.8 16.8 9.4 30.3
Energy Recovery (%)* 91.2 96.7 83.8 84.2**
* ER not include 5-10% HTL process energy; ** For volatile solids
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Distillation of HTL Biocrude
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Fuel specification analysis and engine test of BD10-20
Fuel Spec Property Upgraded BD-10
(FPW)
Upgraded BD-20
(FPW)
Diesel
Viscosity @20 °C (mm2/s)a 3.737 3.050i 3.746
Acidity (mg KOH/g)b 0.08-0.23 0.26-0.33 0.3 e
Existent Gum (mg/100ml)f 0.17 wt.% 0.21 wt.% 0.21 wt.%
Net Heat of Combustion (MJ/kg)e 44.7 44.2 46.1
Cetane Number (min) f 44.2 43.6 40> e
Lubricity (μm) f 364 324 <520 e
Oxidation Stability (hrs) f 48> 48> 6> e
Engine Test
Power Generated (ft-lb) 7.4 -13.5 6.0-13.7 7.3-13.5
EGT (°C) h 326.3- 569.6 303.7-554.1 334.9 -574.4
Thermal Efficiencies j TBAi TBAi TBAi
CO emission (ppm) 0.04-1.82 0.05-1.66 0.05-2.12
CO2 emission (ppm) 7.06-11.4 6.22-11.7 7.12-11.6
NOx emission (ppm) 606-1576 551-1456 540-1549
Unburnt hydrocarbons (ppm) 14-26 18-29 14-32
Particulate matter emission (Soot) TBD TBD TBDaMeasured by Cannon-Fenske Viscometer (ASTM D7566-14a); bMeasured by ASTM D664; cMeasured by ASTM D93; d According to ASTM D7566-14a;e ASTM D7467-13; f Modified ASTM D381, heat the sample in the furnace from room temperature to 240 °C for 30 minutes; g Not applied; h Exhaust Gas
Temperature; Through the cooperation with Prof. Chia-Fon Lee; i To be analyzed; j check the reference papers on Biomass & Bioenergy
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Synergy of Algae and Wastewater Treatment
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National Algal Biofuels Technology Roadmap:
(DOE, 2010, pg. 83)
“Inevitably, wastewater treatment and recycling must be
incorporated with algae biofuel production.” WHY?
“Nutrient recycling would be needed since wastewater
flows in the United States are insufficient to support
large-scale algae production on the basis of a single use
of nutrients.”
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Nitrogen Balance of the HTL Process
As temperature increased, more nitrogen was recovered by aqueous product.
NR of bio-crude oil increased mainly due to the increase of its yield.
About 75% of nitrogen remained in the aqueous phase after HTL.
Chlorella Chlorella
Yu et al., 2011
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Destruction of Bio-active Compounds and
Antibiotic Resistance Gene via HTL Process
14 C-BPA/Estradiol
+ Swine Manure
Flofernicol
Certiofur
Estrone
HTL Treatment
Temperature:250 – 300oC
Reaction Time: 15, 30, 60 min HPLC Analysis
Liquid Scintillation
Counter
BPA Estradiol
Distribution of 14C from BPA and Estradiol in the HTL final products (3000C, 60 min RT)
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Destruction of Bisphenol A
a) 3000C-60 min
b) 3000C-45 min
c) 3000C-15 min
60 min 45 min 15 min0
20
40
60
80
100
Feedstock
% C
14 in
pos
t HT
L w
aste
wat
er
Figure 3: Percentage of 14C in HTL
wastewater.
Detection of BPA and its breakdown products before and after HTL treatment at 300oC
and three different reaction times: a) 60 min, b) 45 min, and c) 15 min. (Pham et al.,
2013)
300 C
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Left: DNA concentration pre- and post HTL treatment;
Right: Agarose gel of plasmid DNA extracts from pure E. Coli
culture before HTL treatment (Well 1) and after various HTL
treatments (Well 2-7) versus size standards (Well 8).
0 15 30 45 60 750.1
1
10
100
1000
E.Coli-250oC
E.Coli-300oC
Swine manure+E.Coli-250oC
DN
A c
oncentr
ation (
ng/m
L)
Retention time (min)
Destruction of Plasmid DNA via HTL Treatment
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Aq
ueo
us
Solids
Gases
Bio
cru
de
→Ⅰ: 3, 2+4(2-, 3-)
→Ⅱ: 4(6)+(5, 2)
→Ⅲ: 3(1, 2)
Ⅰ
Ⅱ
Ⅲ
HTL Pathway Analysis (Outputs Distribution)
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Pathway Analysis -- Effect of FS Composition
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STELLA Widely used in biological, ecological, and environmental sciences
(Hannon and Ruth 1999, Ouyang 2008)
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Model Construction
1 2 3 4 5
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Evaluate process improvements
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Dilute Liquid
Concentrated
Biosolids
Hydrothermal
Liquefaction
Algal-
bacterial
Cultivation
Waste
PretreatmentHarvested Biomass
PHWW
Biocrude Oil
Residue
CO2
Waste
Stream
Q 1000
TSS 210
C 132
N 40
Q 999TSS 63
C 75N 37
Q 0.7
TSS 147
C 57
N 4
Q 9.0
C 226
N 121
CO2 C 31
TSS 942
C 472
N 147
Q 1008TSS 20
C 38N 9
Oil 990
C 657
N 23
Residue 379
C 123
N 7
Improved Scenario:
10 Times Biosolids Amplification
Treated
Wastewater
C 314
Solids 210C 132
C 686
Solids 1959
C 992
= 10_________+
TSS 147
1 2 3 4 5Zhou, 2014
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The combination system diagram
Raw
materials
Biogas Membrane
The condensed effluent was used
for water soluble fertilizer
The diluted
Microalgae
cultivation
N, P absorption and
wastewater treatment
Biocrude
oil
production
Microalgae used as co-
digestion to produce CH4
Fig. The diagram of anaerobic digestion and microalgae
cultivation
CO2
E2-Energy Demonstration Unit on Campus
Pilot HTL Reactor (2 ton/day Biocrude Capacity)
Feedstock Supply System
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Clean water
Multi-cycle nutrient and water reuse
CO2Sun light
Hydrothermal liquefaction (HTL)
Wastewater and nutrients from Post HTL to algae
Biomass from algae
to HTL
Liquid
Solids
Manure
Q = 1000
TSS = 4.0C = 3.6
N = 0.725
Carbon capture
C = 9.1 ton
Biomass = 37.9C captured = 18.9
N recycled = 2.61
Biocrude
= 14.5 ton
A Case Study: 1,000 t/d Wastewater Treatment Plant(Equivalent to a 6,000 hog farm based on TSS, N&C)
Let’s think big … E2-Energy Potential
Collected per year:
54 Billion m3 wastewater
200 million tons
nutrient-rich solids
http://news.cnet.com/i/bto/20080620/Seambio
tic_Ponds_540x354.jpg
0.6~1.2 Billion tons
Biocrude equivalent!
US consumed
1.1 billion tons of
crude oil in 2013
Hydrothermal liquefaction (HTL)
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Thank you