190910_謝子賢_webinar

1. Bioenergy Technology
Hierarchical carbon synthesis by biomass
pyrolysis oil and application in
supercapacitor
GTRI, CPC, Taiwan
Hsieh, Tzu-Hsien
295931@cpc.com.tw
2019/10/17 1

2. Outline
2019/10/17 2
• Biomass Pyrolysis (Carbon precursor)
• Hierarchical carbon process
• Application in supercapacitor

3. Phase-out of fossil fuel vehicles
2019/10/17 3
Country Ban announced Ban commences Scope Selectivity
UK 2017 2040 Gasoline or diesel New vehicle sales
China 2017 2040 Gasoline or diesel New vehicle sales
France 2017 2040 Gasoline or diesel New vehicle sales
India 2017 2030 Gasoline or diesel New vehicle sales
Israel 2018 2030 Gasoline or diesel New vehicle sales
Netherlands 2017 2030 Gasoline or diesel New vehicle sales
Norway 2016 2025 Gasoline or diesel New vehicle sales
Taiwan 2018 2040 Gasoline or diesel New vehicle sales
Denmark 2018 2035 Gasoline or diesel New vehicle sales
Spain 2017 2040 Gasoline or diesel New vehicle sales

4. CPC’s smart green gas station
2019/10/17 4

5. CPC’s smart green gas station
2019/10/17 5

6. CPC’s smart green gas station
2019/10/17 6
Lithium-Titanate Battery
(LTO)
Energy Storage
Vanadium flow battery
Fuel Cell
EMS

7. CPC’s smart green gas station
2019/10/17 7

8. Distributed Generation
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9. Distributed Generation
2019/10/17 9

10. Vanadium Flow Battery Energy Storage
2019/10/17
1
0

11. Energy Management System
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12. Energy Management System
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13. Bioenergy
Thermochemical Process
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14. Thermochemical Conversion
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Thermochemical Conversion
Process G L S
Carbonization 35 30 35
Fast Pyrolysis 13 75 12
Gasification 85 5 10
CO2, CO, H2,
CH4, CxHy
Temperature

15. Thermochemical Process
2019/10/17 15
Fuel
Heat
Pyrolysis
Char Oil
Pyrolysis
oil
Medium E
Gas
Pipeline
Oxygen
Gasifier
Medium E
Gas
Synthetic
fuel
Steam
Steam
Gasifier
Medium E
Gas
Combustio
n
Air
Air
Gasifier
Low E Gas
Power

16. Biomass Pyrolysis
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17. 2019/10/17 17
Biomass Pyrolysis

18. 2019/10/17 18
Process Development
~1kg/s
~1kg/hr

19. BTG Fast pyrolysis
19
Property Unit Value
C
H
N
O (Balance)
wt%
wt%
wt%
wt%
46
7
< 0.01
47
Water content
Ash content
Solids content
Density
wt%
wt%
wt%
kg/m3
25
0.02
0.04
1,170
LHV
LHV
pH
Kinematic
viscosity (40 °C)
MJ/kg
MJ/Ltr
-
cSt
16
19
2.9
13
1. At the AkzoNobel site in Hengelo
2. Complete in end of 2014
3. 20 ML/yr = 12 MCM NG
4. 8,000 Dutch households
5. Saves up to 20,000 tonnes CO2/yr.
6. NTA8080 certificate .

20. Webshop pyrolysis oil samples
20
https://www.btg-btl.com/en/company/services/shop

21. Ensyn
21
Sep 30, 2014
Ensyn and Memorial Hospital
Sign RFO™ Biofuel Supply
Agreement
• 5 year, renewable contract that provides for the delivery
of 300,000 gallons/year of Ensyn’s RFO™ cellulosic biofuel
• Memorial’s boiler has been operating successfully on
100% RFO™ for approximately one month.
• 85% GHG reduction.
July 13, 2016
Ensyn, Arbec and Rémabec
Begin Construction of the
Cote Nord Biocrude Production
Facility in Quebec
• 10.5 million gallon (approximately 40 million litre) per
year biocrude.
• Complete by the end of 2017.
• Ash content: 0.25 w% max。
• Sulfur: 0.1 w% max。
• Specific Gravity @ 20 °C:1.3 kg/L max。
• Net calorific value :15 min MJ/kg。

22. the Côte-Nord Project in Quebec
2017.11
22
http://www.ensyn.com/

23. RTP
23

24. RTP Fuel
24

25. Biomass Pyrolysis
2019/10/17 25
Thermal Chemistry Process
Product G L S
Carbonization 35 30 35
Fast Pyrolysis 13 75 12
Gasification 85 5 10
Residence time and temperature is the key!!
T
Advantage
• Increase biomass energy density (X4)
• Increase value of biomass waste
• Easier Transportation
• Low ash and sulfur content
• Integrate with gasification or FCC
process
Source: Envergent
Feedstock Drying Bio-oil

26. CPC Biomass Pyrolysis
2019/10/17 26

27. CPC Biomass Pyrolysis
2019/10/17
Biomass
Heat + N2
Pyrolysis
Char / Oil /
Gas
Air
Air Gasifier
Low E Gas
Steam
Steam
Gasifier
Medium E
Gas
Oxygen
Gasifier
Medium E
Gas
• Solid feeding test
• Process Variable
• Fluidized Bed
• Thermochemical Conversion
27

28. CPC Biomass Pyrolysis
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Research Summary
• Lab Scale Pyrolysis System (3kg/hr)
• Test different feedstock and sand
• Advanced Bio-oil utilization
• Evaluate FCC use
• Test Biomass gasification
Total sawdust use: 795kg
before after

29. Biomass pyrolysis oil (Bio-oil)
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Pyrolysis Temp. 450
Product A B
kg 5.999 3.192
Yield % 61.2733
Char kg 0.637
GHV Cal/g 4175 3848
Viscosity cSt 17.56 5.525
Density g/ml 1.1975 1.0689
Ash wt% 0.594 0.042
N wt% 0.23 0.14
C wt% 41 36
H wt% 10 12
S wt% 0.01 N.D.
O wt% 57 63
Precursor 轉碳率(%)
a.裂解油A1 14.5
b.裂解油A2 16
c. 裂解油B1 8.3
d. 裂解油B2 1.4
e.碳粉 20.5

30. Bio-oil Combustion
302019/10/17

31. Bio-Phenolic Resin
31
4cm X4cm 20cm X20cm
2019/10/17

32. Biomass waste to high-value carbon
2019/10/17 32
Sawdust Bio-oil Carbonization Coating
0.2$/kg 0.5~1$/kg 30~100$/kg

33. Energy storage technology
2019/10/17 33
https://en.wikipedia.org/wiki/
Supercapacitor

34. Motivation
342019/10/17

35. Hierarchical Carbon Process
35
Advantage: No solvent process
2019/10/17

36. Hierarchical Carbon Synthesis by Biomass
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• Hierarchical Carbon Synthesis by
Templated method can application
in supercapacitor, desalination,
waste water treatment, advanced
battery
• Surface area >1000m2/g, 50%
Mesopore, High capacitance(120F/g)
and retention (60%)
https://en.wikipedia.org/wi
ki/Supercapacitor
Patent
Approved

37. Hierarchical Carbon
2019/10/17 37
No. Template
Surface Area
m2/g
Micropore
m2/g
Mesopore
m2/g
I ZnO 1538.2 105.5 1432.7
II ZnO 889 173 715
III CaCO3 844.3 425.96 418.3
IV CaCO3 1326 426 900
ZnO CaCO3

38. D G
Hierarchical Carbon
38
Items Spec.
N 1.2%
C 83%
H 2%
S 0.5%
O 10.1%
Ash 0.9019%
Particle size D90=10.04 um
Micro 426 m2/g
Meso 900 m2/g
BET 1326 m2/g
Pore V 1.22 cm3/g
Pore Size 5.5 nm
• Adjust Meso/Micro pore ratio for coating
• High Capacitance (120F/g) and High retention(>60%)
Commercial
CPC
100mV/s
2019/10/17

39. Supercapacitor Application(0~1.5V)
39
Charge
Discharge
2019/10/17

40. SC process optimization
40
Grinding
Electrode drying Bag Filter
Vacuum packing
Glove box maintain
2019/10/17

41. 20F Supercapacitor
41
塗佈 滾壓製漿
36.5 mm36.5mm
52.0mm
52.0mm
1~20 pieces
32
漿料
太稀
未研
磨&
過篩
(200
mesh)
成功
參數
2019/10/17

42. 172 372 572 772
0.0
0.5
1.0
1.5
2.0
Voltage/V
Time / s
200 cycle
1000 cycle
2000 cycle
3000 cycle
4000 cycle
5000 cycle
No gas swelling23 F 2000 cycle  23 F  5000 cycle 
17 F （74% retention）
Current : 0.25 A
Charge
Voltage
(0.25A)
Retention
(after 5000 C)
1.5 >98%
1.8 74%
2.0 78%
2.0 (0.1A) 70%
20F Supercapacitor
2019/10/17 42

43. 5F / 10V SC module
43
Replace commercial SC
Charge-Discharge test
2019/10/17

44. Future Work
44
1. Enhance carbon properties
2. Enhance SC life cycle
3. Hybrid type capacitor
4. Sodium ion battery application
2019/10/17

45. Thank you for your listening!!
2019/10/17 45