1. Fast Pyrolysis of Oilseed Byproduct Feedstocks North Central Regional Sun Grant Center Annual Meeting March 18, 2015
Gregory Michna, Ph.D.
Assistant Professor
Mechanical Engineering Dept.
South Dakota State University
Stephen Gent, Ph.D.
Assistant Professor
Mechanical Engineering Dept.
South Dakota State University
Graduate Student Contributors: W. Sonnek, J. Harris, B. Lawburgh, J. Lawburgh
Undergraduate Student Contributor: Z. Parks

2. Pathways for Nonfood Oilseeds
MEAL
Beef
Oilseed
Renewable Plastics
Dairy
Protein Supplement
(low concentration)
Lubricants
Swine
Renewable Diesel
Aquaculture
Renewable Jet Fuel

3. Where we fit in… OIL MEAL Fast Pyrolysis Upgrade Bio-Oil via of Meal
Beef
Oilseed
Renewable Plastics
Dairy
Protein Supplement
(low concentration)
Lubricants
Swine
Renewable Diesel
Aquaculture
Renewable Jet Fuel
Fast
Pyrolysis
of Meal
Upgrade
Bio-Oil via
Hydrotreatment
Bio-Oil

4. Project Scope
Characterize the properties of meals from Ethiopian mustard (Brassica carinata) and camelina (Camelina sativa) as feedstocks for fast pyrolysis
Produce bio-oils via fast pyrolysis from these meals and characterize bio-oil properties
Investigate use of catalysts and hydrogenation for upgrading

5. Biofuels Laboratory Equipment Fast Pyrolysis Fluidized Bed Reactor
Fast Pyrolysis Auger Reactor
Analytical Equipment
Gas chromatograph mass spectrometers, CHNS-O elemental analyzer, calorimeters, rheometer, viscometer, volumetric Karl Fischer titrator, volumetric potentiometric titrator
Capabilities
Produce bio-oil from cellulosic feedstocks
Analyze bio-oil properties: elemental analysis, energy content, etc.

6. Thermochemical Processes
Pyrolysis: Reaction at Temps of °C in absence of oxygen
Fast Pyrolysis: Heating rate of C/s; resident time on order of seconds
Energy &
Water Vapor
GASIFICATION
PYROLYSIS
TORREFACTION
FEEDSTOCK
COMBUSTION
Gas
(Bio-gas)
Liquids (Bio-oils)
Solids
(Bio-char)
Waste Heat

7. Fluidized Bed Reactor

8. Carinata (Brassica carinata)
Supplier: Agrisoma Biosciences, Ltd., Saskatchewan, Canada
Hexane extracted oils
Fine, nearly powder consistency

9. Camelina (Camelina sativa)
Supplier: Willamette Biomass, Rickreall, OR
Cold-press extracted oils

10. Project Progress
Calorimetry and physical properties of meals feedstock completed
as received and dried
unground and ground
Production of bio-oils from both meals using fluidized bed and auger reactors
Analysis of bio-oils
Yield
Energy content
Water content
TAN
Viscosity
Aging Effects

11. Feedstock Characterization

12. Feedstock Characterization (2)
Species
Form
Calorific Value (kJ/kg)
Carinata
Undried Meal
17,700
Dried Meal
19,500
Camelina
21,300
22,700
Results of digital microscope tests to determine particle size ranges.
Oilseed Meal
Form
Bulk Density
(kg/m3)
Average Particle
Size (mm)
Carinata
Unground, Undried
670
0.726
Unground, Dried
650
0.921
Ground, Undried
730
0.543
Ground, Dried
760
0.207
Camelina
530
1.380
510
0.890
560
0.563
550
0.520

13. Fast Pyrolysis Parametric Study
Independent Variables
Set Values
Reactor Temperature (°C)
400, 450, 500, 550, 600
Condenser Temperature (°C)
20, 40
Zeolite Catalyst Present
550°C Reactor,
40°C Condenser
Feedstock Type
Carinata Meal,
Camelina Meal

14. Bio-Oil Analysis Dependent Variables Measured Properties Bio-Oil Yield
Digital scale measurement of bio-oil from set quantity of feedstock
Bio-Oil Energy Content
Bomb calorimeter energy content
Bio-Oil Water Content
Karl Fischer measurement of water content
Bio-Oil TAN
Titrator measurement of mg KOH/g oil
Bio-Oil Viscosity
Rheometer measurement of dynamic viscosity (Pa-s)

15. Summary of Results of Bio-Oil from Carinata Meal
Ranges of energy content, yield, water content, TAN, and dynamic viscosity of bio-oils from carinata meal.
NOTE: Two consistencies of bio-oil were collected: 1) a lower viscosity bio-oil (LVBO) from condenser 1, and 2) a higher viscosity bio-oil (HVBO) from the rest of the condensers
Property
Value Range
Bio-Oil Yield
12-20% (LVBO)
4-22% (HVBO)
Bio-Oil Energy Content
7,600-8,600 kJ/kg (LVBO)
26,900-30,030 kJ/kg (HVBO)
Bio-Oil Water Content
56-63% (LVBO)
% (HVBO)
Bio-Oil TAN
(LVBO)
mg KOH/g (HVBO)
Bio-Oil Viscosity
Pa-s (LVBO)
Pa-s (HVBO)

16. Results: Carinata Meal Yield
Measured mass fractions of the bio-oil and char products created from carinata meal
Measured Yield (Mass Fraction)
Product
LVBO
HVBO
Char
Condenser (°C)
Reactor (°C) 20 40
400
0.12 --
0.04
0.68
450
0.19
0.10
0.13
0.48
500
0.22
0.11
0.20
0.47
0.35
550
0.21
0.18
0.31
0.42
600
0.32
500 CAT
0.51
Higher reactor temperature reduced char yield and increased bio-oil yields

17. Results: Carinata Bio-Oil Water Content
Measured water content of the high viscosity and low viscosity bio-oils on the days in which they were produced
Water Content (% H2O)
Product
HVBO
LVBO
Condenser (°C)
Reactor (°C) 20 40
400
17.2 --
450
12.6
12.0
62.5
61.3
500
13.1
12.2
60.0
60.1
550
13.9
12.7
59.0
600
11.7
14.5
60.9
56.9
500 CAT
12.5
62.0
Higher reactor temperature and low condenser temperature minimized water content in HVBO

18. Results: Carinata Bio-Oil Calorific Values
Measured energy content (kJ/kg) of the high viscosity bio-oils for the different pyrolysis conditions and comparison of aging
Day 1 7 14 28
Condenser (°C)
Reactor (°C) 20 40
400
25,080 --
450
27,800
28,216
30,037
29,317
30,057
28,838
29,253
29,272
500
27,328
27,155
27,974
26,886
28,657
27,281
28,978
27,944
550
27,558
27,375
27,979
27,321
29,015
27,786
29,437
27,791
600
27,904
26,786
28,789
27,515
29,332
27,176
29,364
27,317
500 CAT
27,651
27,584
28,607
28,701
Overall, energy value of HVBO was between 27,000 and 30,000 kJ/kg.
Energy contents with aging are constant for first month.

19. Results: Carinata Bio-Oil TAN
Measured total acid numbers (TAN in mg KOH/g oil)) of the high viscosity bio-oils for the different pyrolysis conditions and the effects of aging
Day 1 7 14 28
Condenser
(°C)
Condenser (°C)
Reactor (°C) 20 40
400
64.8 --
450
20.2
18.7
17.6
22.0
18.9
21.5
19.2
19.0
500
15.8
24.6
19.3
13.7
24.2
18.0
26.2
550
14.2
24.5
17.1
20.5
19.1
22.8
600
17.2
14.5
18.5
19.9
14.3
20.7
16.9
18.1
500 CAT
18.6
13.4
15.7
Overall, TAN values of HVBO are consistent and relatively stable over one month. Long-term tests are ongoing.

20. Results: Carinata Bio-Oil Viscosity
Measured dynamic viscosity (Pa-s) of the high viscosity bio-oils for the different pyrolysis conditions and how the bio-oils compare with aging
Day 1 7 14 28
Condenser (°C)
Reactor (°C) 20 40
400
0.49 --
450
0.34
0.86
0.63
1.27
0.50
1.67
0.93
1.94
500
0.36
0.94
0.84
1.50
1.10
3.63
2.30
3.53
550
0.89
2.10
1.57
2.51
3.60
3.10
600
0.48
1.45
1.02
0.98
1.13
1.06
1.58
1.30
500 CAT
0.72
1.42
1.84
3.12
Overall, viscosity of HVBO increases with aging (2-3 times over 1 month period). Long-term tests are ongoing.

21. Preliminary Results of Bio-Oil from Camelina Meal
Ranges of energy content, yield, water content, TAN, and dynamic viscosity of bio-oils from camelina meal.
Property
Value Range
Bio-Oil Yield
30-46%
g from 1.5 kg feedstock
Bio-Oil Energy Content
28,200-29,000 kJ/kg
Bio-Oil Water Content %
Bio-Oil TAN
mg KOH/g
Bio-Oil Viscosity
Pa-s

22. Ongoing and Future Work
Continue investigation of camelina meal for bio-oil production
Continue in situ upgrading of bio-oils with zeolite catalysts
Investigate hydrotreatment of bio-oils

23. Dissemination
Sonnek, W., Michna, G., and Gent, S. (2015). Investigation of Fast Pyrolysis of Brassica Carinata in an Auger Type Reactor. Proceedings of the ASME Power & Energy Conference, PowerEnergy , June 28-July 3, San Diego, CA (accepted for publication)
Harris, J., Lawburgh, B., Lawburgh, B., Michna, G., and Gent, S. (2014). Properties of Brassica Carinata and Camelina Sativa Meals and Fast Pyrolysis Derived Bio-Oils. Proceedings of the ASME th Energy Sustainability Conference, ESFuelCell , June 30-July 2, Boston, MA. (published)

24. Mechanical Engineering Department
Special Thanks to:
South Dakota
Oilseed Initiative
Mechanical Engineering Department
This study was supported by the US Department of Transportation, Office of the Secretary, Grant No. DTOS59-07-G

25. Thank you
Stephen Gent, PhD Gregory Michna, PhD