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TRANSCRIPT
Upgrading Hydrothermal Liquefaction
Biocrude Oil from Wet Biowaste into
Transportation Fuel
Wan-Ting (Grace) Chen
Agricultural and Biological Engineering
4
A new paradigm –
Environment-Enhancing Energy
Bio-waste
Liquid
Solids Bio-crude oil
Clean water
Multi-cycle
nutrients &
water reuse
Wastewater
& nutrients
from Post
HTL to
algae
Algae
production
Hydrothermal
liquefaction (HTL)
Biomass
from algae
to HTL
Chen et al., Biorecource Technology 2014, 152, 130-139
0
20
40
60
80
100
120
Nomal/Dry Normal/Wet Low N/Dry Low N/Wet
En
erg
y c
on
sum
pti
on
(MJ/
kg
fu
el
pro
du
ced
)
Oil transesterificationOil ExtractionDryingAlgae culture and harvesting
Algal Biofuel Bottlenecks: Energy Balance
Drying and oil extraction are energy intensive steps
(>75% energy) (Lardon et. al, 2009; Sander & Murthy, 2010 )
5
Harvesting
Dewatering
Oil
Extraction
ConversionCulturing Drying
Wet
Extraction
(adapted from Lardon et. al, 2009)
Biodiesel Energy
Content
Slide Credit: C.T. Kuo, Y. Zhou, L. Schideman, & Y. Zhang (2015)
Hydrothermal
Liquefaction
(HTL)
Pyrolysis Gasification
Comparison of Thermochemical
Conversion (TCC) Technologies
6
Pros:
Wet feedstocks
Similar to crude oil
Higher energy density
Cons:
High
Pressure
Unstable oil
Complex
Slide Credit: C.T. Kuo, Y. Guo, & Y. Zhang (2015)
Research Question:
How much crude oil is consumed
by the U.S. every year and how to
reduce/replace it with renewable
energy?
Proposed Solutions:
Utilizing wet biowaste
Hydrothermal Liquefaction (HTL)
7
Challenge 1
Feedstock -- Would it be feasible to convert mixed-culture algal biomass grown in wastewater into biocrude oil?
– Wet biomass contains 80~98 % moisture content
– Would this bioenergy conversion technique reach a
net positive energy balance?
8
9
Hydrothermal liquefaction (HTL) of mixed-culture
algal biomass from wastewater treatment plants
Gas
Product
Post-HTL
WW
Oil
Product
Solid
Residue
Demonstrated
HTL
Feedstocks
Reactor
Reaction Temp: 260 – 320oC
Reaction Time: 0 – 1.5 hr
Animal Manure
Microalgae
Food waste
Slide Credit: Y. Zhang (2011)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
AW:SW=1:0 AW:SW=3:1 AW:SW=1:1 AW:SW=1:3 AW:SW=0:1
En
erg
y C
on
sum
pti
on
Ra
tio
(-)
Feedstock Combination Ratios (-)
50% heat recovery No heat recovery
HTL Results in a Positive Net Energy Gain
11
ECR <1 Produce
Net Positive Energy
Chen et al., Applied Energy, 128: 209-216, 2014
AW: Wastewater Algae
SW: Swine Manure
output
input
E
E ECR
Produce Enough Biofuel to Replace Fossil Fuel !
Challenge 1
Would it be feasible to convert mixed-culture algal
biomass grown in wastewater into biocrude oil?• Yes. The reaction temperature and time are determined.
• Be able to achieve a net positive energy gain
12
Challenge 2
HTL Biocrude -- How to obtain a large
quantity of biocrude oil for downstream
analysis and upgrading?
– A 1 L batch reactor can only produce 48 g of
biocrude oil (with a 40 wt.% yield)
– Development of high pressure reactor is very
challenging (e.g., feedstock pumping and clogging)
13
Produce Enough Biofuel for the U.S. annual consumption!
Goal 1
Would it be feasible to convert mixed-culture algal
biomass grown in wastewater into biocrude oil?• Yes. The reaction temperature and time is optimized.
• Be able to achieve a net positive energy gain
15
Goal 2
How to obtain a large quantity of biocrude oil
for further analysis and upgrading?• Developed an up-scaled continuous reactor
• Address plugging issues
16
Challenge 3
Upgrading the HTL Biocrude --Since the
composition of the biocrude oil is so
complex, how to properly upgrade it?
– High ash content in the mixed-culture algae harvestedfrom wastewater (AW) negatively affect the bio-crude oil quality
– How ash content interacts with volatile components in the feedstock under the HTL processes remains unknown
Pretreat Mixed-culture Algal Biomass from Wastewater
Treatment Plants
Harvest algae
Wash with tap water (1 h) Garbage entrained
with algae
Pulverize
Screen
Ultrasonic Centrifuge Centrifuge
+ Ultrasonic
Test Ash
Content
Scanning Electric
Microscope (SEM)
Thermogravimetric
Analysis (TGA)17
Pretreatment condition Ash content Weight percentage after
centrifugation
Pulverized 27.6 ± 0.07 % N/A
S-2 28.6 ± 1.9 % 100 %
C-1 Upper 32.5 ± 1.2 % 26.4 ± 4.27 %
Middle 18.6 ± 0.8 % 29.0 ± 0.73 %
C-2 Upper 36.7 ± 3.1 % 24.5 ± 2.15 %
Middle 21.8 ± 0.8 % 27.0 ± 0.50 %
C-3 Upper 34.1 ± 3.5 % 24.4 ± 0.18 %
Middle 21.0 ± 0.04 % 33.0 ± 7.35 %
C-4 Upper 34.4 ± 1.7 % 26.7 ± 0.63 %
Middle 19.2 ± 1.9 % 33.5 ± 1.38 %
18
Ash Contents of Pretreated Algae
Reduced by 7-10 wt.%
C1 & C2: Centrifuge at 3000 rpm with 15 min and 25 min, respectively;
C3 & C4: Centrifuge at 3000 rpm with 15 min and 25 min, respectively;
S2: Before Centrifuge.
25.0%
35.0%
45.0%
55.0%
65.0%
75.0%
85.0%
95.0%
105.0%
0 100 200 300 400 500 600 700 800
Wei
ght
Los
s(%
)
Temperate(ºC)
Pulverize
Screen#2
C-1-upper
C-1-middle
Ultrasonic
C-upper+U-0.5h
C-upper+U-1h
C-middle+U-0.5h
C-middle+U-1h
Decomposition Kinetics Analysis of
Pretreated Algal Biomass
Stage.2
Stage.1
Stage.3
19
)1( Xkdt
dX
)exp(RT
EAk a
Sample Pretreatment method Ea (kJ/ mol)
Ea1 Ea2
Algae from a
waste-water
treatment plant
Pulverize 5.60 50.2
S-2 5.63 47.6
C-1-upper 3.92 48.4
C-1-midddle 2.91 47.5
U 5.75 48.0
C+U-1-upper 2.49 37.0
C+U-2-upper 2.23 35.9
C+U-1-middle 2.53 41.1
C+U-2-middle 2.56 40.2
Chlorellaa N/A 6.32 44.4
Apparent Activation Energy (Ea) of Algae
Decreased after Pretreatments of
Centrifugation Plus Ultrasonication
a Adopted from (Gai et al., 2013), which was operated at the same condition under TGA.20
Sample Pretreatment
Method
Ea (kJ/ mol) Biocrude Oil Yields
from HTL (%)b
Higher Heating
Value (MJ/kg)
Ea1 Ea2
Algae from
a waste-
water
treatment
plant
Pulverize 5.60 50.2 30.9 ± 1.87 % 28.2
S-2 5.63 47.6 29.2 ± 3.35% 28.4
C-1-midddle 2.91 47.5 30.6 ± 4.32 % 29.9
U 5.75 48.0 35.4 ± 5.13 % 30.9
C+U-2-middle 2.56 40.2 55.3 ± 1.54 % 32.4
Chlorellaa N/A 6.32 44.4 39.6 ± 0.79 %c 37.8 c
Biocrude Oil Yield of Pretreated Algae
Significantly Improved by 20-25 wt.%
a Adopted from (Gai et al., 2013), which was operated at the same condition under TGA.b HTL processes were conducted with 25 % total solids content of feedstocks at reaction temperature of 300 °C with reaction time of 1 hour c Adopted from (Gai et al., 2014), which was operated at the same condition under HTL.
21
Produce Enough Biofuel for the U.S. annual consumption!
Goal 1
Would it be feasible to convert mixed-culture algal
biomass grown in wastewater into biocrude oil?• Yes. The reaction temperature and time is optimized.
• Be able to achieve a net positive energy gain
22
Goal 2
How to obtain a large quantity of biocrude oil
for further analysis and upgrading?• Developed an up-scaled continuous reactor
• Address plugging issues
How to properly upgrade HTL Biocrude Oil?• Remove excessive amounts of ash contents
• Understand the role of ash content under HTL
Goal 3
23
– The composition of biocrude oil would be different from feedstock to feedstock
– Simple separation methods such as extraction was not able to fractionate biocrude oil into transportation fuel
– Catalytic upgrading of biocrude oil with hydroprocessinghas not been effective to improve the fuel properties
Pretreatment of
Biowaste
Solids
Continuous Hydrothermal
liquefaction (producing 5
gallons biocrude oil /day)
Biocrude
oil
Liquid
Algae
production
Sun light CO2
Clean
water
Phenols
Fatty Acids
Hydrocarbon
s
Nitrogen-doped
Carbonaceous
Material
Aviation
BiofuelBiodiesel Functional MaterialsEngine Test 24
Chen et al., Nature Energy, in preparation
70% of the Distillates of Biocrude Oil
are in the Diesel Range
25
0.0%
10.0%
20.0%
30.0%
40.0%
50.0%
60.0%
70.0%
80.0%
0.0 100.0 200.0 300.0
Wei
gh
t of
Bio
cru
de
( w
t.%
)
Temperature (°C)
Test 1
Test 2
Test 3
Test 4
Test 5
Diesel Range:
200-338 ° C*
*According to ASTM-D7467 and D975
Chen et al., Nature Energy, in preparation
Distillates from FPW-derived Biocrude
Contains Alkanes and Fatty Acids
26Chen et al., Nature Energy, in preparation
A B C D E F G H
10
20
30
40
50
60
70
80
90
100
% o
f Tota
l Rela
tive P
eak A
reas
(%)
Distillate Fractions
Hydrocarbons Cyclic Hydrocarbons Fatty Acids Derivatives
Fatty Nitriles N-Heterocyclic cmpds.
Phenols Amino Acids
27
Acidity of Different FPW-Distillates
Chen et al., Nature Energy, in preparation 27
203.4208.5
137.9
71.3
26.6
8.15 1.68 1.000%
10%
20%
30%
40%
50%
60%
70%
80%
0
50
100
150
200
250
A B C D E F G H
Yie
ld (
wt.
%)
Ac
idit
y (
mg
KO
H/g
s
am
ple
)
Distillation Fraction (-)
Acidity
Distillation Yield
ASTM: 0.3
28
Mild Upgrading
Esterification for FPW (food processing waste)-
derived distillates to reduce their acidity
Neutralization with NaOH for SW (Swine Manure)-derived distillates to reduce gum contents that caused by phenolic compounds
Chen et al., Nature Energy, in preparation
Energy Consumption Ratio and Process Severity
(Ro) of Different Upgrading Approaches
Distillation of HTL biocrude oil is competitive to other available
upgrading strategies, without the consumption of H229Chen et al., Nature Energy, in preparation
0
2
4
6
8
10
12
0.00
0.05
0.10
0.15
0.20
0.25
0.30
Zeolite (425 C)
SCW (400 C)
HDT (400 C)
DL of SW DL of FPW
DL of SP
Lo
g R
o
En
erg
y C
on
su
mp
tio
n R
ati
o
Different Upgrading Strategies (-)
Severity 50% heat recovery No heat recovery
Fuel Spec
Property
Bio-diesel
(B5-20)
Diesel HTL 10 HTL20
Viscosity
(mm2/s)a
3.241f 3.746 3.737 3.050
Acidity
(mgKOH/g)b
<0.3d <0.3d 0.10 0.29
Gross Heat of
Cumbustion
(MJ/kg) c
40-41f 46.0 44.7 44.2
Cetane Number
(min)
40>d 40e 44.2 43.6
Lubricity (µm) <520d <460g-
520e
364 324
Oxidation
Stability (hr)
6 >d N/A 48> 48>
aMeasured by ASTM D445; bMeasured by ASTM D664; cMeasured by bomb
Calorimeter (ASTM D4809);d ASTM D7467;eASTM D975;fLin et al., Fuel, 2012gEngine Manufacture Association recommendation
Fuel Specification of Drop-in Biodiesel Prepared
with Upgraded HTL Distillates meets ASTM
High Cetane
number refers to
low ignition delay
before
combustion
Lower lubricity
than biodiesel
implies to a better
ability to reduce
wear and friction
Superior
oxidation stability
for long-term
storage
30
Chen et al., Nature Energy, in preparation
Fuel Specification and Engine Test of Drop-in
Biodiesel Prepared with Upgraded HTL Distillates
Competitive
power output of
HTL drop-in
fuel to
petroleum
diesel
Lower pollutant
emissions of
CO, CO2, NOx,
and unburned
hydrocarbons
31Chen et al., Nature Energy, in preparation
Engine Testa HTL10 HTL20 Diesel/
Biodiesel
Power Output (kW) 3.68-4.26 3.67-4.24 3.41-4.26
CO emission (ppm) 0.09-0.31 0.07-0.32 0.12-0.34
CO2 emission (ppm) 8.70-10.2 8.06-9.80 8.76-10.5
NOx emission (ppm) 606-1304 551-1456 540-1320
Unburnthydrocarbons
(ppm)
14-26 16-28 14-32
Soot (FSN) 0.01-0.12 0.06-0.13 0.01-0.11
aOperated at 1200-2000 rpm with injection timing of 0-12° BTDC under
medium loading of fuel (20 mg/stroke);b filter smoke number (FSN)
32
HTL 10 and 20 Leads to a Higher Power
Output in Diesel Engine
HTL 10 can achieve a higher power output than regular
diesel at 0-4 CA BTDC and 2000rpm.
HTL 20 can lead to a superior power output to diesel at 4-8
CA BTDC and 1500 rpm.
1.2 1.4 1.6 1.8 2.00
2
4
6
8
10
12
Inje
cti
on
Tim
ing
(C
A B
TD
C)
Enigne Speed (1000*RPM)
0.972
0.986
0.999
1.01
1.03
1.04
1.05
1.07
1.08
Power-HTL10 (%)
1.2 1.4 1.6 1.8 2.00
2
4
6
8
10
12
Inje
cti
on
Tim
ing
(C
A B
TD
C)
Enigne Speed (1000*RPM)
0.955
0.963
0.971
0.980
0.988
0.996
1.00
1.01
1.02
Power-HTL20 (%)
33
HTL 10 and 20 Leads to a lower NOx
emission in Diesel Engine
HTL 10 can achieve a 6% lower NOx emission than diesel
at 1500rpm for all tested crank angle, due to lower EGT.
HTL 20 can lead to a 13% lower NOx emission than diesel
at 1500-2000 rpm for all tested crank angel.
1.2 1.4 1.6 1.8 2.00
2
4
6
8
10
12
Inje
cti
on
Tim
ing
(C
A B
TD
C)
Enigne Speed (1000*RPM)
0.940
0.963
0.986
1.01
1.03
1.05
1.08
1.10
1.12
NOx-HTL10 (%)
1.2 1.4 1.6 1.8 2.00
2
4
6
8
10
12
Inje
cti
on
Tim
ing
(C
A B
TD
C)
Enigne Speed (1000*RPM)
0.870
0.901
0.933
0.964
0.995
1.03
1.06
1.09
1.12
NOx-HTL20 (%)
Produce Enough Biofuel for the U.S. annual consumption!
Goal 1
Would it be feasible to convert mixed-culture algal
biomass grown in wastewater into biocrude oil?• Yes. The reaction temperature and time is optimized.
• Be able to achieve a net positive energy gain
34
Goal 2
How to obtain a large quantity of biocrude oil
for further analysis and upgrading?• Developed an up-scaled continuous reactor
• Address plugging issues
Goal 3
How to properly upgrade HTL Biocrude Oil?• Fractionate Biocrude oil by distillation
• Mildly upgrading HTL distillates (esterification)
• Fuel Spec and Diesel Engine Test is conducted
How to properly upgrade HTL Biocrude Oil?• Remove excessive amounts of ash contents
• Understand the role of ash content under HTL
Relevant Publication List 10. Wan-Ting Chen, Yuanhui Zhang, Timothy Lee, Zhenwei Wu, B.K. Sharma, Chia-Fon Lee, Lance Schideman,
“Renewable Transportation Biofuel Production Converted from Wet Biowaste via Hydrothermal Liquefaction,” Nature Energy, in preparation, Mar, 2017
9. Wan-Ting Chen, Wanyi Qian, Yuanhui Zhang, Zachary Mazur, Karalyn Scheppe, Chih-Ting Kuo, “Hydrothermal Liquefaction of High-Ash Algal Biomass: the Effect of Ash Contents in HTL Reactions,” Algal Research, submitted, Dec 2016.
8. Peng Zhang, Yuanhui Zhang, Wan-Ting Chen, Lance Schideman, B.K. Sharma, “ Hydrothermal Liquefaction of Diatom Skeletonema costatum and the Effect of Frustules on Biocrude Oil Production,” International Journal of Agricultural and Biological Engineering, accepted, Dec, 2016
7. Wan-Ting Chen, Liyin Tang, Wanyi Qian, Karalyn Scheppe, Ken Nair, Zhenwei Wu, Chao Gai, Peng Zhang, YuanhuiZhang, “Extract Nitrogen-Containing Compounds in Biocrude Oil Converted from Wet Biowaste via Hydrothermal Liquefaction,” ACS Sustainable Chemistry & Engineering, 4 (4): 2182-2190, 2016.
6. Chao Gai, Yuanhui Zhang, Wan-Ting Chen, Peng Zhang, Yuping Dong, “An Investigation of Reaction Pathways of Hydrothermal Liquefaction Using Chlorella pyrenoidosa and Spirulina platensis,” Energy Conversion & Management, 96:330-339, 2015.
5. Giovana Tommaso, Wan-Ting Chen, Peng Li, Lance Schideman, Yuanhui Zhang, “Chemical Characterization and Anaerobic Biodegradability of Aqueous Products Generated from Hydrothermal Liquefaction of Mixed-Culture Algae from Wastewater Treatment System,” Bioresource Technology, 178:139-146, 2015.
4. Wan-Ting Chen, Junchao Ma, Yuanhui Zhang, Gai Chao, Wanyi Qian, “Physical Pretreatments of Wastewater Algae to Reduce Ash Content and Improve Thermal Decomposition Characteristics,” Bioresource Technology, 169: 816-820, 2014.
3. Wan-Ting Chen, Yuanhui Zhang, Jixiang Zhang, Lance Schideman, Guo Yu, Peng Zhang, Mitchell Minarick, “Co-liquefaction of Swine Manure and Mixed-culture Algal Biomass from a Wastewater Treatment System to Produce Bio-crude Oil,” Applied Energy, 128: 209-216, 2014.
2. Wan-Ting Chen, Yuanhui Zhang, Jixiang Zhang, Peng Zhang, Guo Yu, Lance Schideman, Mitchell Minarick, “Hydrothermal Liquefaction of Mixed-culture Algal Biomass from Wastewater Treatment System into Bio-crude Oil,” Bioresource Technology, 152: 130-139, 2014.
1. Jixiang Zhang, Wan-Ting Chen, Peng Zhang, Yuanhui Zhang, Zhongyang Luo, “Hydrothermal Liquefaction of Chlorella pyrenoidosa in Sub- and Supercritical Ethanol with Heterogeneous Catalysts,” Bioresource Technology, 133: 389-397, 2013.
36
Produce Enough Biofuel for the U.S. annual consumption!
Would it be feasible to convert mixed-culture algal biomass
grown in wastewater into biocrude oil?• Yes. The reaction temperature and time is optimized.
• Be able to achieve a net positive energy gain
37
How to obtain a large quantity of biocrude oil for
further analysis and upgrading?• Developed an up-scaled continuous reactor
• Address plugging issues
How to properly upgrade HTL Biocrude Oil?• Fractionate Biocrude oil by distillation
• Mildly upgrading HTL distillates (esterification)
• Fuel Spec and Diesel Engine Test is conducted
How to properly upgrade HTL Biocrude Oil?• Remove excessive amounts of ash contents
• Understand the role of ash content under HTL
Q&A
Learn more at:
[email protected]://Sites.google.com/view/gracechen
Thank you
38
Acknowledgments• All the members in Prof. Yuanhui Zhang’s Group
• T. Lee, K. Nithyanandan and Prof. Chia-Fon Lee
• K.C. Tsao and Prof. Hong Yang in Dept. of CHBE
• Dr. Lance Schideman & Dr. B.K. Sharma in ISTC
• Prof. Alan Hansen in Dept. of ABE (Fuel Spec Test)
• Dave and Tom Burtons in Snapshot Energy LLC
• Dedicated Support from my family and Dr. Mei-Hsiu Lai
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