Catalytic Microwave-Assisted Biomass

Pyrolysis for Distributed Biofuels and

Chemicals Production

Roger Ruan, Ph.D.

Professor and Director

Center for Biorefining and

Department of Biosystems and Bioproducts Engineering
 OUTLINE

• Brief background and introduction – why

microwave-assisted pyrolysis
• Mobile microwave-assisted pyrolysis
system development
• Catalytic microwave assisted pyrolysis
• Non-thermal assisted catalytic reforming
Nature of Current Cellulosic
Biomass Production

• Distributed production
• Transporting bulky biomass from scattering
production sites to a central processing
facility has been a key barrier to biomass
utilization
Cellulosic Ethanol
• 40-50 million gallons/year cellulosic ethanol
plants: cost over $300 million to build, need
over 2,000 tons biomass per day.
• Furthermore, compared with corn ethanol
production, additional processing costs are
needed to convert cellulosic feedstock to
fermentable sugars, which would raise
feedstock-associated costs to as high as 70–
80% of the final product cost, in additional to
other technical and management challenges.
Gasification and Fischer–
Tropsch Liquid Biofuels
• 40-50 million gallons/year liquid fuel plants:
cost about $1 billion to build, need over 3,000-
4,000 tons biomass per day, and expensive to
operate due to catalyst cost and safety issue
related to high pressure and high temperature
of the process, in additional other technical and
management challenges.
Large Scale Processes

• High capital investment

• High operation technicality
• High feedstock transportation and storage
costs
Distributed Biomass Conversion
Systems (DBCS)
-
A “Smaller” Solution
Bale to Barrel DBCS
As fertilizer back to field for biomass production

Power for conversion

One round hay bale
diameter = 5ft
length = 5ft Gas

2,250,000BTU

Conversion

1,500,000BTU

1,000lb, 100ft3 1.2 barrel

10lb/ft3 500lb, 6.7ft3,
7,500,000BTU 75lb/ft3
75,000BTU/ft3 3,750,000BTU
562,500BTU/ft3
Can be implemented on average size farms
or small villages
Distributed Biomass Processing Scheme
Microwave Assisted Pyrolysis (MAP) System

Non-condensable gas

Condenser
Feedstock

Power Microwave Char Bio-oil

Generator Generator
Microwave-Assisted Pyrolysis (MAP) System
Why MAP?
• Microwave heating is uniform and easy to control;
• It does not require high degree of feedstock grinding (e.g., large chunk of wood
logs) and can handle mixed feedstock (e.g., municipal solid wastes);
• The conversion products (pyrolytic gas and bio-oils) are cleaner than those from
gasification and conventional pyrolysis because our process does not have to
use biomass powder and does not require agitation and fluidization;
• The syngas produced has higher heating value since it is not diluted by the
carrying gas for fluidizing the biomass materials;
• Exothermic reactions (chemical reaction that releases energy and microwave
plasma effect) can be maintained through careful control of the process
parameters and therefore MAP is energy efficient; and
• Microwave heating is a mature technology and development of microwave
heating system for biomass pyrolysis is of low cost.
• Scalable, portable, mobile – distributed conversion of biomass
Micorwave Pyrolysis of Aspen
Canola Seed Press Cake
 Mass flux
Heat flux Microwave energy
Mass flux
Heat flux

a. conventional heating approach b. Microwave heating approach

c. Pyrolysis front development with conventional heating d. Pyrolysis front development with microwave heating
Particle size effect in MAP

Note:
Feedstock: Poplar Wood
Microwave Power: 1250 Watt
Municipal Solid Wastes
MSW Pyrolysis Products
Microwave heating characteristics for
different materials:
Power level calibration:
Temperature profile in MAP
Continuous
microwave
assisted
pyrolysis
system
development
Mobile
Microwave
Assisted
Biomass
Pyrolysis
System
Pyrolytic biooil differential yields
Retention time effect in MAP
Feedstock: Corn Stover, Power level:1250 Watt
GC-MS analysis
Biorefining of Biooils and Liquefied Biomass

Polyester + DGG
Composite Polyester + fibers
Polyester film Composite

Polyurethane foam

Wood Adhesive

Biofuel
Catalytic pyrolysis

Pyrolysis fraction yields (mass% of total biomass input) from runs with different
catalysts and catalyst groups added to the aspen pellets
 Typical Compositions by Nitrates such as (MgNO3)2, Fe(NO3)3

Typical Compositions by Sulfates such as Na2SO4, MgSO4

Typical Compositions by Chlorides such as AlCl3, MgCl2, ZnCl2 and FeCl3

Chlorides help to improve and simplify the composition of bio-oil,

compared with nitrates and sulfates.
 A b u n d a n c e

T I C : C S M - C O N TT RR OO LL .. DD \\ dd aa tt aa .. mm ss

6 0 0 0 0 0 0 Control
4 0 0 0 0 0 0

2 0 0 0 0 0 0

0
3 . 0 0 4 . 0 0 5 . 0 0 6 . 0 0 7 . 0 0 8 . 0 0 9 . 0 0 1 0 . 0 01 1 . 0 01 2 . 0 01 3 . 0 01 4 . 0 01 5 . 0 01 6 . 0 0
T im e - - >
A b u n d a n c e

FF T I C : C S + A lC l3 .. DD \\ dd aa tt aa .. mm ss

6 0 0 0 0 0 0 AlCl3
4 0 0 0 0 0 0

2 0 0 0 0 0 0

0
3 . 0 0 4 . 0 0 5 . 0 0 6 . 0 0 7 . 0 0 8 . 0 0 9 . 0 0 1 0 . 0 01 1 . 0 01 2 . 0 01 3 . 0 01 4 . 0 01 5 . 0 01 6 . 0 0
T im e - - >
A b u n d a n c e

T I C : C S + C o C l2 .. DD \\ dd aa tt aa .. mm ss

6 0 0 0 0 0 0 FF CoCl2
4 0 0 0 0 0 0

2 0 0 0 0 0 0

0
3 . 0 0 4 . 0 0 5 . 0 0 6 . 0 0 7 . 0 0 8 . 0 0 9 . 0 0 1 0 . 0 01 1 . 0 01 2 . 0 01 3 . 0 01 4 . 0 01 5 . 0 01 6 . 0 0
T im e - - >
A b u n d a n c e

T I C : C S + 8 G Z n CC ll 22 .. DD \\ dd aa tt aa .. mm ss

6 0 0 0 0 0 0 ZnCl2
4 0 0 0 0 0 0
FF
2 0 0 0 0 0 0

0
3 . 0 0 4 . 0 0 5 . 0 0 6 . 0 0 7 . 0 0 8 . 0 0 9 . 0 0 1 0 . 0 01 1 . 0 01 2 . 0 01 3 . 0 01 4 . 0 01 5 . 0 01 6 . 0 0
T im e - - >
A b u n d a n c e

T I C : C S + 8 g M g CC ll 22 -- 44 00 00 .. DD \\ dd aa t t aa . . mm ss
FF
6 0 0 0 0 0 0 MgCl2
4 0 0 0 0 0 0

2 0 0 0 0 0 0

0
3 . 0 0 4 . 0 0 5 . 0 0 6 . 0 0 7 . 0 0 8 . 0 0 9 . 0 0 1 0 . 0 01 1 . 0 01 2 . 0 01 3 . 0 01 4 . 0 01 5 . 0 01 6 . 0 0
T im e - - >

Total ion chromatograms from GC-MS analysis of pyrolytic oils from corn stover
when different catalysts were used (8g/100g biomass). FF: furfural.
Microwave Pyrolysis in a Continuous System
Effect of temperature and catalyst on products (Dry basis)
Temperature /oC Catalyst Bio-oil /% Char /% Gas /%
475 - 42.0 35.1 22.9
375 - 39.6 38.9 21.5
325 - 38.5 43.6 17.9
375 Catalyst A2 38.8 41.3 19.9
Sample: Corn cob
Feeding rate: 20Kg/h
Size: <1.2cm No catalyst

Addition of catalyst A2 helps

corn cob pyrolysis to produce 4% Catalyst A2
a chemical-furfural. Furfural
Co-pyrolysis of corn stover and scrap tire
Phase separation!

Top phase

Bottom phase

Corn stover : tire = 1:1

Sun Dried Algae
Comparison of fossil oil and bio-oils from MAP of
Chlorella sp. algae and wood

Bio-oils
Properties Chlorella sp. Wooda Fossil oila
Elemental analysis (wt.%)
C 65.40 56.4 83.0-87.0
H 7.84 6.2 10.0-14.0
N 10.28 0.1 0.01-0.7
O 16.48b 37.3 0.05-1.5
HHV (MJ/kg) 30.7c 21 42
Density (kg/L) 0.98d 1.2 0.75-1.0
Viscosity, at 40 oC (Pa s) 0.06 0.04-0.20 2-1000
pH 7-9.5 2.5-3
Elemental composition of algae bio-oil
Algae bio-oil and blend
Hydrothermal pretreatment
• Reduce nitrogen contents in algal feedstock by
hydrolysis of protein; reduce energy inputs
required for algae dewatering and drying.

Algae Slurry Reactor Sand Bath

Continuous Hydrothermal Biomass Pyrolysis System
High Throughput Continuous Catalytic
Hydrothermal Conversion System
 Elemental composition (%)
HHV(MJ/kg)

C H N Ash C retention N retention

Untreated
algae
39.9 5.5 6.2 24.4 16.8

Pretreated
algae
Temperature (°C) Time (min)

10 51.0 7.0 8.3 14.4 81.6 84.9 21.7

20 51.0 7.0 8.0 14.3 83.9 84.5 21.7 Pretreated algae

30 51.1 6.9 7.8 12.4 74.3 73.0 21.7
150
40 50.5 6.9 7.7 14.7 77.7 76.2 21.4 samples had
50

60
51.3

52.0
7.0

7.0
7.7

7.6
14.6

12.8
75.9

77.8
73.1

73.2
21.8

22.1
higher carbon
contents and
10 49.9 6.9 7.0 18.8 64.0 57.8 21.0

20 52.7 7.2 6.7 17.2 60.7 49.5 22.4 enhanced

heating values
30 53.1 7.2 6.5 14.3 56.8 44.9 22.7
175
40 54.8 7.4 6.1 14.0 58.8 42.0 23.6

50

60
54.6

53.7
7.3

7.1
6.0

6.2
14.8

14.0
58.6

56.7
41.1

42.4
23.4

22.9
under all
reaction
10 49.1 6.6 6.6 22.1 55.7 48.3 20.5

20 54.0 7.1 5.7 16.7 49.5 33.5 23.0 conditions and N

200
30

40
51.1

57.5
6.8

7.6
5.8

5.1
19.9

13.6
48.4

44.8
35.1

25.7
21.4

25.1
removal of over
50 56.9 7.6 4.8 13.5 43.8 23.9 24.7
75% at 200
°C−225 °C for
60 54.4 7.2 5.1 12.8 43.4 26.0 23.1

30−60 min.
10 51.1 6.8 6.1 18.8 45.8 34.9 21.4

20 58.2 7.7 5.4 13.9 45.9 27.1 25.6

30 58.7 7.8 4.8 13.6 42.9 22.5 25.9

225
40 63.6 8.3 4.8 12.8 43.8 21.3 29.4

50 63.1 8.1 4.4 12.2 43.3 19.2 28.8

60 67.5 9.1 3.6 13.5 39.6 13.4 32.7

C and N distribution among the Fatty acid retention in pretreated EMC of untreated and pretreated
products of HP under 200 °C, 40 algae.
min condition.

• 75% of N removal was achieved.

• 73%-99% of fatty acids retention was obtained, which
means very minor amount of lipids loss during
pretreatment.
• Pretreated algae were more hydrophobic, had much
lower water holding capacity, and were much easier to
be dried and stored with less biological deterioration
GC-MS profiles of bio-oils from
untreated and pretreated algae

raw microalgae pretreated microalgae

The pyrolytic bio-oil from pretreated algae contained less N-

containing compounds and the bio-oil contained mainly long-chain
fatty acids (C14−C18, over 45%) which can be more readily
converted into hydrocarbon fuels in the presence of simple catalysts.
Wastewater
to algae
to biofuels
system
• Acquire Commercially Available
Catalysts

• Acquire Raw Materials for Making

Biorefining Catalysts

• Synthesize Biorefining Catalysts

- Hydrotreating/Hydrocracking Catalysts
- Metathesis Catalysts
Acquire/Catalysts Synthesis

Catalyst Used for Bio-oil Conversion

 Catalysts Synthesis

Zeolite Precursor Synthesis Zeolite Precursor Synthesis

Catalyst Screening Microreactor Setup
Pressurized hydro-processing system
 Catalyst Used for Bio-oil Conversion

Catalyst A Catalyst B Catalyst C Catalyst D

Ni-Ru/ Al2O3(self- Ni-Co/C (self- CBV-400 CBV-780 (Zeolyst
prepared) prepared) (Zeolyst International )
International)
Catalyst E Catalyst F Catalyst G Catalyst H
Ni/Alumina/Silica Al2O3 Zeolite mixed Cu-CBV 400 (
with Al2O3 Self prepared)
 Canola oil with catalysts

Catalyst A
1-Pentene, 2-methyl-

Co-Mo/Al2O3
Benzene

Co-Mo/ZSM-5
Toluene
Hydrotreating Canola oil

Gasoline

Co-Mo/C,600°C, Canola Oil, 0.5 Hr

 HDO of wood derived oil

Aspen biooil

Reaction temperature=400oC

Phenol,2-methyl
p-Xylene
Toluene
Benzene

Phenol

Reaction temperature=500oC

Reaction temperature=600oC
 HDN/HDO of N-O containing compound

Indole
Feedstock

Pyridine
1-Propene, 2-methyl-

trimethyl-
Benzene, 1,3,5-
Reaction temperature=400oC

Reaction temperature=500oC
Benzene

Reaction temperature=600oC
Hydrogenation of algal pyrolytic biooil

Catalyst: W-Mo/Al2O3
At 350 C, 1000 psi, 0.5-2
ml/min
HDO/HDN of algae derived oil

Benzene, 3-ethyl-1,2,4,5-tetramethyl-
Benzene, pentamethyl-
Benzene, 12,3,4-tetramethyl-
Benzene, 1,3,5-trimethyl-
Catalytic upgrading

Top phase

Bottom phase

Catalyst: Ni-Mo/Al2O3
At 350 C, 1000 psi, 0.5-2
ml/min

Co-pyrolysis oil from Corn stover : tire = 1:1

Oleic acid conversion over catalysts
Liquid product yield of Canola oil over various
catalysts
HydroDeOxygenation (HDO) of Model Compounds

(Syn-Biooil and Aspen biooil+SynBiooil Mixture)

HDO of N-O containing compound solution

Ni-Mo/Al2O3
HDN of N-O containing compound
 Heating values (HHV, measured by bomb calorimeter, Cal/g)

High heating value of feedstocks

Oleic acid Lineolic acid Canola oil JP-8 Gasoline
9446.5 9451.1 9310.2 10982.3 10794.6

High heating value of products

A-6 A-7 A-8 A-23 A-27
9651.7 10023.6 9856.5 9554.0 9609.4

Note: The heating value of gasoline from internet, the other were measured in the lab
 Pyrolyzer-GC/MS:
Quick and convenient catalyst
screening method

Biomass (yellow) is pyrolyzed in the quartz tube

and vapors go through the catalysts bed (blue)
and then analyzed by GC/MS.
Microwave Assisted Catalytic Pyrolysis
Direct catalytic pyrolysis of algae
Oleic acid

Toluene
Xylene

Benzene
Naphthalene

• Aromatic hydrocarbons are the major pyrolysis

products (74% yield) with the use of catalyst A.
• Acetic acid, furfural, N-containing compounds and fatty
acids were converted to aromatics.
NTP-Assisted Catalytic Reforming
• Catalytic reforming has become a useful way
to produce biofuels and other chemicals
• Conventional catalytic reforming usually
requires high temperature and high pressure
• Catalysts can perform well at low
temperature and pressure with assistance of
Non-thermal Plasma (NTP).
NTP Reactor

Energetic electrons, ions, molecules, highly

reactive radicals, etc. generated though
electrical discharge in syngas to help synthesize
liquid fuels and chemicals

Electrode

High Voltage Power Plasma

Electrode
Pulsed Corona Discharge Reactors

Silent discharge reactors

NTP Reactors
NTP Reactors for Catalytic Reforming
 FT-IR

Products

Power Supply
GC-MS

MFC 1

NTP reactor

N2 T

Drier T


MFC 2

Controlled
temperature
H2 Cupper foil (ground)

H2O Quartz tube (dielectric barrier)

MFC 3 Catalysts

Insulation Stainless steel tube (anode)

CO

Cross section of the NTP reactor

Ionizations of Nitrogen and Hydrogen with
NTP-Assisted Catalysis
• N2 → 2N+
• H2 → 2H+
• N+ + H+ → NH+
• NH+ + H+ → NH2+
• NH2+ + H+ → NH3+
Example - Ammonia Production
• 12% + ammonia produced at 150 °C and
atmospheric pressure
• Potential to reach higher concentration with
further optimization of catalysts and
conditions
• Low capital, operation, and maintenance
costs
 4
3.5
Ammonia yield (%) 3
2.5
2
1.5
1
0.5
0
NTP NTP + MgO NTP + Ru /MgO NTP + Cs-Ru
/MgO

NTP Ammonia synthesis different catalysts.

(VN2:VH2=1:3, N2 and H2 total flow rate 60ml/min, voltage 5000V,
frequency 8000Hz.)
FT-IR spectrum of NTP reforming of N2,
CO, H2 and/or H2O vapor.
FT-IR spectroscopy of NTP reforming of CO and H2O vapor.
Summary
• The microwave-assisted catalytic pyrolysis technology has
great potential for large scale demonstration and
commercialization.
• The innovative NTP assisted catalytic reforming processes
show many advantages over conventional high temperature
and high pressures processes
• The pyrolysis time (i.e. retention time) plays an important
role in oil quality and liquid product yield;
• Particle size is not a significant issue in terms of oil quality
(composition) and product yield distribution;
• Co-pyrolysis of solid wastes such as scrap tires/plastics and
biomass is practically feasible;
• With the aid of catalyst, the quality (heating value, O and N
content, etc.) of the pyrolytic oil (bio-oil) can be significantly
improved.
Http:// biorefining.cfans.umn.edu
Acknowledgments:
Related Group Members and Collaborators: B. Polta, J. Willett, A. Sealock, R.
Hemmingsen, R. Larkins, J. Sheehan, P. Chen, M. Min, Y. Chen, W. Zhou, L. Wang,
Yecong Li, Q. Kong, X. Wang, Y. Wan, K. Hennessy, Y. Liu, X. Lin, Yun Li, Y. Cheng,
X. Ma, L. Li, Y. Zhao, S. Deng, Q. Chen, C. Wang, Y. Wang, Z. Du, M. Mohr, X. Lu,
R. Zhu, Z. Wang, A. Olson, B. Martinez, B. Zhang, J. Zhu, B. Hu, P. Wang, L.
Schmidt, D. Kittelson, R. Morey, D. Tiffany, H. Lei, F. Yu, X. Ye, Yebo Li, X. Pan, B.
Zhang, M. Muthukum, W. Gibbons, D. Raynie, P. Heyerdahl, ……
Funding Agencies:

Metropolitan Council
Environmental Services
Q u est io n s?
R. Roger Ruan, Ph.D.

Professor and Director

Center for Biorefining
Department of Bioproducts and Biosystems Engineering
University of Minnesota
1390 Eckles Ave., St. Paul, MN 55113
[email protected]
612-625-1710
Biorefining.cfans.umn.edu