Catalytic Fast Pyrolysis of Ag & Forest

Residues for Aromatic Fuel Additives

Final report

Lin Wei, James Julson

Department of Agricultural & Biosystems Engineering

South Dakota State University

March 2015
 Background
• Funded by DOE through NC Sun Grant Initiative
• Started in Oct. 1st , 2010 and ended up in Sept. 30th, 2014
• The goal is to convert Ag & Forest Residues to Aromatic
Fuel Additives using catalytic fast pyrolysis (CFP)

Specific objectives
• Develop an effective CFP process
• Develop appropriate catalysts for the CFP process
• Preliminarily evaluate technical and economic
feasibility of CFP
 Catalytic fast pyrolysis (CFP )
No air Syngas
Biomass Bio-oil
Catalyst

400 - 600oC Bio-char

Biomass
Sizing and drying Heat

Biomass Breakdown Catalysis Hydrocarbons

 SDSU Proprietary Pyrolysis Reactor
Features
• High heating rate
• No carried gases need
• Atmospheric pressure
• Easy scaling up
• Simple structure with low cost
• Reliable…

Operating conditions:
• Temperature: 450 – 600oC,
• Heating rate: 500 – 1000oC/min
• Processing time: 10 – 30 s
• Pressure: ≈ 1 atm,
• Feeding rate: 1 – 3 kg/h,
• Bio-oil yield rate: 50 – 65 %
Two-step pyrolysis for drop-in fuels

SDSU
Pyrolysis
Forest residues
reactor
SDSU
HDO reactor

Crude
bio-oil
Corn stover

Pyrolysis HDO upgrading

Sawdust Hydrocarbons
(drop in fuel)
Crude bio-oil
Water
 GCMS Analysis of Raw Bio-oil
Abundance

TIC: 1 GUNKYDILUTED.D\ data.ms

n-Hexadecanoic acid
15.195
950000 9.04%

900000
850000
800000
2-Cyclopenten-1-one, 2-methyl-
Crude
bio-oil
750000 13-Octadecenal, (Z)-
3.07%
700000 2.603 9.88%
16.803
650000
600000 3.2472-Furancarboxaldehyde, 5-methyl-
5.13%
550000 Cyclotetradecane
500000 o-Xylene 2-Cyclopenten-1-one, 2,3-dimethyl- 3.03 %
1.60% 1.92% 16.993
450000 2-Cyclopenten-1-one, 2,3-dimethyl-
2.266 1.92% 7.612
7.762 12.743 4-Methyl-dodec-3-en-1-ol
400000 4.133 7.547
7.709 1.02%
7.634
8.799 10.033 13.933
350000 7.504 8.464
7.398
6.493 8.434
8.395 9.942
300000 8.312 9.915 17.194
16.940
3.614 5.585 18.315
250000 3.201 6.568
6.598
7.141 11.296 15.044 16.307
14.633 16.560
2.1982.9273.562 5.043 6.158
5.643
5.365 6.388
4.980
4.616
2.683
200000 2.480 4.8035.443
5.263
4.505 5.313
5.110
4.438
4.202
150000 2.459
3.004 3.890
3.723
3.114 4.087
100000
50000
0
4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
Time-->
 GCMS analysis of upgraded bio-oil
Abundance

o-Xylene
2.298
38.02% Over 80% of Aromatics
TIC: 2LESS GUNKYDILUTED.D\ data.ms

8e+07
(38.02 + 14.85 + 14.46 +4.15 + 4.65 + 5.62 + 2.13+…)
7.5e+07

7e+07

6.5e+07
Upgraded Upgraded
bio-oil bio-oil
6e+07

5.5e+07
p-Xylene
5e+07 14.85%
2.487
4.5e+07

3.580 Benzene, 1,2,3-trimethyl-

4e+07
14.46%
3.5e+07

3e+07

2.5e+07 Ethylbenzene Naphthalene, 1-methyl-

2.201
4.15% 5.62%
2e+07 7.557
Benzene, 1-ethyl-3-methyl-
1.5e+07 4.65%
3.191

4.089
1e+07
6.069
Naphthalene, 2,7-dimethyl-
5.451
3.265 5.589 2.13%
8.970
5000000 4.198
5.663 7.763
3.9184.673
3.397 4.730 7.076
7.145 9.142
9.182 10.178
8.816
3.100 4.330
4.376 5.137 7.002
5.749 6.716
7.208 9.382 10.710 14.595
0
4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
Time-->
 Comparison of bio-oil, drop-in fuel to
Petroleum-derived fuels
Properties of raw bio-oil and upgraded bio-oil and petroleum-derived gasoline and diesel
Properties Raw bio-oil Drop-in fuel Gasoline Diesel
Freezing point, oC ~0 < -15* - 30 -5
pH value 2.8 – 3.2 5.0 – 5.6
Viscosity cSt @ 20 oC 30 – 50 1.20 – 1.88 0.40 – 0.80 1.90 – 4.10
Density, Kg/L 0.98 – 1.06 0.80 – 0.85 0.74 0.83
Heating Value, MJ/kg 16-25 41 – 48 43 42
Carbon Content, % w.t. 25 84.59 – 85.12 85 – 88 87
Hydrogen Content, % w.t. 10 9.90 – 11.26 12 – 15 13
Oxygen Content, % w.t. 39 0.40 – 0.72 0 0
Water Content, % w.t. 40 < 0.2% 0 0

* the lowest temp. we can get in our labs

The HDO upgraded bio-oil is compatible with petroleum hydrocarbons

 Catalyst Development
Active metals
Pt, Pd, Ru, Cu, Mo, Ni, Co, etc.
ZSM-5 Activated Alumina
Supports/carriers carbon oxide
• Activated carbon
• Alumina oxide
• ZSM-5

Steps
• Prepare support materials
• Impregnating precursors to the supports
• Dried and calcined at 350 – 650℃ for 5 – 8 hr
Development of Bifunctional Catalysts
Bifunctional Mo-Cu catalyst samples

Fresh catalyst

Better selectivity and activity to light

hydrocarbon (gasoline ranged),
lower cost, long lifetime, etc.
Used catalyst
 Characterization of Catalysts

Surface and Microstructure Catalysts

Catalysts BET Langmuir Total
Surface area Surface area Pore volume
(m2/g) (m2/g) (cm3/g)
HZSM-5 432.18 517.44 0.37
Mo/HZSM-5 364.33 433.84 0.32
#1 Mo-Cu/HZSM-5 122.77 157.51 0.24
#2 Mo-Cu/HZSM-5 166.45 229.64 0.28
#3 Mo-Cu/HZSM-5 206.45 263.38 0.29
Cu/HZSM-5 372.87 426.06 0.35

The BET surface is calculated from the size and number of the adsorbed gas molecules (N2, Argon, Krypton), which is forming a monolayer on the surface of the catalyst samples at
standard temperature and pressure.
Langmuir surface area is determined by maximum amount of adsorbate adsorbed per gram of adsorbent for forming a monolayer.
 Characterization of Catalysts

Investigate bulk structure

(crystallite structure and size) (d)
using X-ray diffraction (XRD):
(c)
a) Fresh HZSM-5

Intensity (a.u.)
b) HZSM-5 used in CFP at 400 °C
c) HZSM-5 used in CFP at 500 °C
(b)
d) HZSM-5 used in CFP at 600 °C

(a)
There is no significant difference
in the spectra patterns
10 20 30 40 50
2 theta (degree)
 Characterization of Catalysts
Surface active sites (or concentration) of active
intermediates using FTIR
SEM images of Catalysts

Fresh ZSM-5 Used ZSM-5

100nm 100nm

Fresh Zn-ZSM-5 Used Zn-ZSM-5 100nm

100nm
 TEM images of Catalysts

100nm
Fresh ZSM-5 100nm
Used ZSM-5

100nm
Fresh Zn-ZSM-5 100nm Used Zn-ZSM-5
 Different CFP Approaches
In-situ CFP Method

Syngas

Ice bath

Bio-oil

Biomass

Catalyst

Heating furnace Pyrolysis Reactor

• Bio-oil yield and quality improvement depending on

catalyst/biomass (C/B) ratio. Higher C/B, better quality and yield
• Increase hydrocarbon contents
• Higher water content (phase separation )
• High catalyst consumption.
• Difficult to regenerate catalyst
 Ex-situ CFP Method
Ex-situ CFP System
Pyrolysis reactor
Catalytic cracking reactor Biomass
Catalyst

Syngas

Heater
Heater

N2

Coolant

Quality Bio-oil

Condenser

• Better bio-oil yield and quality. Easy to separation biofuels

• Better activity and selectivity
• Low catalyst consumption. Longer lifetime
• Easy to regenerate catalyst
 Ex-Situ CFP of Sawdust
Temperatures, feedstocks, and catalysts used in the test runs

No. Reaction conditions sawdust, g catalyst, g

1 Py 500oC only 50 0

2 Py500oC+Cracking400oC 50 20

3 Py500oC+Cracking500oC 50 20

4 Py500oC+Cracking600oC 50 20
Effect of temperature on Ex-situ CFP

100%

90%

80%

70%
syngas
60%

50%

40% bio-oil

30%

20% bio-char
10%

0%
Py 500 only Py500+Cracking400 Py500+Cracking500 Py500+Cracking600

Proportions of syngas, bio-oil, and bio-char produced in sawdust CFP at

different reaction conditions
Ex-situ CFP bio-oil properties
Elemental analysis of oil phase
80.00

60.00

40.00

20.00

0.00
No catalyst 400oC 500oC 600oC

C H N Rest
Oil phase
Elemental analysis of aqueous phase
100.00

aqueous phases 80.00

60.00

40.00

20.00

0.00
No catalyst 400oC 500oC 600oC
C H N Rest
Ex-situ CFP bio-oil properties
Oil phase Aqueous phase
Reaction
Temperature, C
Heating values, MJ/kg Viscosity, cP
No catalyst 29.29 2.02
400 22.37 2.135
500 23.80 2.02
600 22.89 1.99
Density, g/ml pH value
1.15 3.60
3.50
1.10
3.40
1.05 3.30
1.00 3.20
3.10
0.95
3.00
0.90 2.90
No catalyst 400oC 500oC 600oC No catalyst 400oC 500oC 600oC
Aqueous phase Oil phase Aqueous phase Oil phase
 What we have done
• Filed a U.S. patent application for the proprietary
pyrolysis reactors and process.
• Successfully convert corn stover, sawdust,
switchgrass, etc.) to crude bio-oil and upgraded the
bio-oils to drop-in fuel (additives aromatic
hydrocarbons)
• Developed appropriate catalysts for CFP and bio-oil
upgrading processes.
• Designed the second generation CFP system
• Support 3 postdoc and 4 PhD students
• Published 5 journal papers and 12 conference
presentations/papers
Issues need to be addressed
Catalyst system
• Catalyst deactivation
• Coking and alkali metal deposition
• Lifetime
• Catalyst cost, selectivity, and activity
Operation
• Syngas applications (heating, F-T synthesis, etc.)
• Bio-char applications (activated carbon, soil amendment ,)
• Condensation efficiency
Second generation CFP reactors
Project Progress attracted
• Congress senator and
Representative visited the labs
• Made connections with national and
international companies
• Established a start-up company
• Provide education to more students
and public
First generation reactor

New Generation Technologies

• Combine pyrolysis and upgrading
two steps in one continuous process
• Scale up CFP process
• Catalysts screening for
commercialization
• Improve catalyst selectivity and
activity with low costs
Second generation reactor
 Plans for Next
• Publish research results an provide proper
information to the community and public
• Provide more bio-refinery education and
training for the community
• Looking for new funding to move on the
research
• Improve the second generation technologies
for high drop-in fuel yield and quality
• Exploring any collaboration opportunity to
scale up the process for commercialization
 Conclusions
• The CFP system can produce quality bio-
oils that can be upgraded to aromatics or
fuel additives (drop-in fuels).
• Catalyst implementation and reaction
conditions (heating rate, temperature,
pressure, etc.) played critical roles in the
yield and quality of bio-oils and drop-in
fuels.
• It is tech-economic feasible if improve the
CFP system and catalysts.
 Thank you for your attention !
Acknowledgment
Research teams:
Postdoc: Zhongyi Ma, Yang Gao, Chunkai Shi
Graduate students: Wangda Qu, Yinbin Huang, Shouyun Cheng, Zhongwei Liu,
Xianhui Zhao
GCMS analyses helped by Dr. Douglas Raynie, Ms. Shanmugapriya Dharmarajan,
Mr. John Kiratu, and Ms. Changling Qiu in the Chemistry Dept. SDSU

XRD analysis helped by Dr. Qiquan Qiao and Mr. Ashish Dubey. The XRD equipment
is supported by the NSF MRI grant (Award No. 1229577).

TEM analysis helped by Dr. Phil Ahrenkiel.

BET measurement helped by Dr. Zhengrong Gu, Yuhe Cao, Ms. Xiaomin Wang for the

Funding supported by DOE: Award #: DE-FG36-08GO88073