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(1)

Activities within the framework of team 3 Thermochemical conversion of biomass

Lanny Schmidt Paul Chen Heidi Nygård Arnstein Norheim

NOR W EGI A N UNIVE RSITY OF LIF E SCIENCES

(2)

3/7/2010

Catalytic Autothermal Reforming of Biomass at Millisecond Times

Lanny Schmidt Regents Professor

Department of Chemical Engineering and Materials Science

University of Minnesota

(3)
(4)

3/7/2010

(5)

Millisecond Catalytic Reactor

“Catalytic Fire”

(6)

3/7/2010

Catalytic Partial Oxidation

3 mm

(7)

3/7/2010

Partial Oxidation of Other Fuels

Partial Oxidation of Gases

Partial Oxidation of Non-Volatile Liquids Partial Oxidation of Volatile Liquids

Partial Oxidation of Solids

Methane

Octane Hexadecane

Methanol Ethanol Propanol Ethylene Glycol

Glycerol Ethyl Lactate

Cellulose Starch

Lignin Polyethylene

Glucose (aq)

Soy Oil

(8)

3/7/2010

Fructose

Biomass

Pyrolysis Oils

Synthesis Gas

Monomers Reforming

Upgrading Synthesis

Transportation Fuel

Fermentation Reforming

Glucose, Mannose, Xylose

Ethanol, Butanol DMF

Alkanes

Alcohols, Alkanes, MeOH Furans

Levoglucosan, Glycoaldehyde, Furfural

Major Biomass Process Routes

(9)

Biomass Gasification

alkanes alcohols biomass → H 2 + CO → methanol

syngas dimethyl ether ammonia

hydrogen

The oldest, most versatile, and inexpensive way to make fuels

(10)

3/7/2010

0 20 40 60 80 100

500 600 700 800 900 1000 1100 1200

0.6 0.8 1 1.2

X (%) T ( o C)

C/O

Soybean Oil

T

0 20 40 60 80 100

0.6 0.8 1 1.2

S C

or S H

(%)

C/O H 2

CO

CO 2

C 2 H

4 & C

3 H

6

Fuel

Air Air

Insulation Catalyst

2 cm

Hydrogen and Olefins from Soy Oil

Reactive flash volatilization in <10 milliseconds

No carbon

(11)

Oxidation Products Cold

Drop

Vapor Hot Surface

Hot Catalytic Surface Cold

Drop O 2 O 2

Oxidation Products

(a) (b) (c) Cold

Drop

Hot Porous Catalytic Surface

Reactive Flash Volatilization

(12)

3/7/2010

Solids Feed System

(13)

Catalytic Reforming of Cellulose

H 2 + CO

Catalyst

Air + Biomass

(14)

3/7/2010

t = 0 t = t 1 > 0 t = t 2 > t 1

t < 0 t >> t 2

impact heating volatilization char combustion

Stages of Particle Reaction

(15)

Fast Photography

1000 frames per second 10 μm resolution

foam flat plate

(16)

3/7/2010

Evolution of a Cellulose Particle: Visualization

Impact

0 ms 75 ms 105 ms

123 ms 156 ms 165 ms 171 ms

(17)

Cellulose melts!

Cellulose boils!

(18)

3/7/2010

Reactive flash Volatilization

All reactions occur above 600 o C C 6 H 12 O 6 → CO + H 2

C 6 H 12 O 6 → C s + H 2 O No carbon

Impurities volatile Very fast

Can use catalysts

(19)

Remarks

Distributed energy changes the game

transportation dominates

corporate monopolies difficult build economic ecosystems

Must be sustainable

Infrastructure necessary

distribution system

economics

(20)

3/7/2010

Remarks

The energy future will look very different

whale oil versus light bulb versus solid state lighting horses versus automobiles versus planes

Many solutions required

conservation nuclear energy

New technologies required

New technologies possible

Students hold the key

(21)

Work in the Center for Biorefining at UMN

• Processes

– microwave assisted pyrolysis, hydrothermal liquefaction, catalytic reforming

• Equipment

– Batch and continuous, pilot demo

• Feedstock

– Cellulosics, wastes, algae

• Products

• Funding

• Involvements

Goal: Biomass to Liquid Fuels

(22)

3/7/2010

Microwave Assisted Pyrolysis (MAP) System

(23)

Microwave-assisted pyrolysis (MAP)

• Under development at the University of Minnesota in collaboration with UMB

• Unique features

– Particle size is not a critical limiting factor – No agitation and fluidization

– Microwave is a mature technology

(24)

3/7/2010

Effect of power input of microwave oven on products

Optimum Yield

Aspen: Liquid 50%, Solid 25%, Gas 25%

Corn cob: Liquid 47%, Solid 22%, Gas 31%

0 10 20 30 40 50 60 70 80 90 100 110 0

10 20 30 40 50 60 70 80

Pr oduct Yield ( % )

Power Input (%)

Liquid Char Gas

Aspen, 300g

0 10 20 30 40 50 60 70 80 90 100 110 0

10 20 30 40 50 60 70 80

Produc t Yie ld (% )

Power Input (%)

Liquid Solid Gas

Corn cob, 300g

Vary with feedstock and processing conditions

(25)

Major accomplishments

• Process development

– Catalytic pretreatment – Catalytic pyrolysis

– Catalytic reforming

– Improved liquid yield and selectivity

• Continuous pilot scale system

– Design, construction

– Installation and testing

(26)

3/7/2010

Microwave assisted pyrolysis

(27)

Catalytic pretreatment

H 2 SO 4 pretreatment improved selectivity.

No catalyst

4% H 2 SO 4

Furfural

(28)

3/7/2010

3.00 4.00 5.00 6.00 7.00 8.00 9.0010.0011.0012.0013.0014.0015.0016.00 0

2000000 4000000 6000000

T ime-->

Abundanc e

T IC: CS M-CONT ROL.D\ data.ms

3.00 4.00 5.00 6.00 7.00 8.00 9.0010.0011.0012.0013.0014.0015.0016.00 0

2000000 4000000 6000000

T ime-->

Abundanc e

T IC: CS+AlCl3.D\ data.ms

3.00 4.00 5.00 6.00 7.00 8.00 9.0010.0011.0012.0013.0014.0015.0016.00 0

2000000 4000000 6000000

T ime-->

Abundanc e

T IC: CS+CoCl2.D\ data.ms

3.00 4.00 5.00 6.00 7.00 8.00 9.0010.0011.0012.0013.0014.0015.0016.00 0

2000000 4000000 6000000

T ime-->

Abundanc e

T IC: CS+8G Z nCl2.D\ data.ms

3.00 4.00 5.00 6.00 7.00 8.00 9.0010.0011.0012.0013.0014.0015.0016.00 0

2000000 4000000 6000000

T ime-->

Abundanc e

T IC: CS+8g MgCl2-400.D\ data.ms

Control

AlCl 3

CoCl 2

ZnCl 2

MgCl 2 FF

FF

FF

FF

3.00 4.00 5.00 6.00 7.00 8.00 9.0010.0011.0012.0013.0014.0015.0016.00 0

2000000 4000000 6000000

T ime-->

Abundanc e

T IC: CS M-CONT ROL.D\ data.ms

3.00 4.00 5.00 6.00 7.00 8.00 9.0010.0011.0012.0013.0014.0015.0016.00 0

2000000 4000000 6000000

T ime-->

Abundanc e

T IC: CS+AlCl3.D\ data.ms

3.00 4.00 5.00 6.00 7.00 8.00 9.0010.0011.0012.0013.0014.0015.0016.00 0

2000000 4000000 6000000

T ime-->

Abundanc e

T IC: CS+CoCl2.D\ data.ms

3.00 4.00 5.00 6.00 7.00 8.00 9.0010.0011.0012.0013.0014.0015.0016.00 0

2000000 4000000 6000000

T ime-->

Abundanc e

T IC: CS+8G Z nCl2.D\ data.ms

3.00 4.00 5.00 6.00 7.00 8.00 9.0010.0011.0012.0013.0014.0015.0016.00 0

2000000 4000000 6000000

T ime-->

Abundanc e

T IC: CS+8g MgCl2-400.D\ data.ms

Control

AlCl 3

CoCl 2

ZnCl 2

MgCl 2 FF

FF

FF

FF

Total ion chromatograms from GC-MS analysis of pyrolytic oils from corn stover

when different catalysts were used (8g/100g biomass). FF: furfural.

(29)

Left to right: (1) light oil #2; (2) Light oil #1;

(3) Heavy oil

Heavy and Light Oil Fractions

Heavy and Light Oil Fractions

(30)

3/7/2010

Blends of light oil (L) with gasoline (G)

Left to right : (1) 1/5(L/G); (2) 2/5; (3) 3/5;

4) 4/5; (5) 5/5; (6) gasoline; (7) light oil.

Blend of Light Oil and Gasoline

Blend of Light Oil and Gasoline

(31)

Continuous Hydrothermal Biomass Pyrolysis System

(32)

3/7/2010

Continuous hydrothermal system –

straightened out and lengthened – attached

to Mercur pump with black tubing at left.

(33)

Direct Conversion of Algal Biomass into

Biofuels

Algae slurry was pumping into the reactor

Algal biofuel product coming

out the reactor

(34)

3/7/2010

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).

(35)

NTP Reactors for Catalytic Reforming

(36)

3/7/2010

Biomass

CO 2 CO

H 2 O

H 2 O

CH 4 , NH 3 , other hydrocarbons N 2

Air Photosynthesis

Gasification

NTP Assisted Catalysis

O 2

An NTP assisted catalysis based “green

chemistry” pathway for chemical synthesis.

(37)

Funding

• IREE/IOE UMN

• DOE/USDA Biomass R&D program

• DOT Sun grant

• LCCMR (MN State legislature)

(38)

3/7/2010

Involvements

• PhD and MS students: >7, 2 exchange students from Norway

• Postdocs: >10

• Visiting scholars: >5

• Faculty and staff

(39)

Future collaborations

• Communication/exchange mechanisms

• Funding mechanisms

– Special funding opportunities – Joint proposals/publications

• Area of potential collaborations

– Catalysts for conversion and reforming/upgrading

– Fractionation/purification

(40)

Departm en t of M athematic al Sciences and Tech nology

NOR W EGI A N UNIVE RSITY OF LIF E SCIENCES

www.umb.no

Departm en t of M athematic al Sciences and Tech nology

40

Pyrolysis of biomass in molten salts

Heidi S. Nygård PhD-student

Norwegian University of Life Sciences –

Department of Mathematical Sciences and Technology

(41)

Departm en t of M athematic al Sciences and Tech nology

NOR W EGI A N UNIVE RSITY OF LIF E SCIENCES

www.umb.no

Molten salts

Molten salts (fused salts) are salts that are heated above the temperature where they melt into liquids

– Halides (NaCl, ZnCl 2 )

– Carbonates (K 2 CO 3 , Na 2 CO 3 )

Characteristiscs of molten salts

– Very good heat transfer characteristics (heat capacities) – Very high thermal stability

– Can function as solvents

– Some molten salts have chemical catalytic properties

Departm en t of M athematic al Sciences and Tech nology

41

(42)

Departm en t of M athematic al Sciences and Tech nology

NOR W EGI A N UNIVE RSITY OF LIF E SCIENCES

www.umb.no

Molten salt technology

Solar power towers

– Molten salts are used as heat transfer medium

Fuel cells

– Molten salts work as the electrolyte

Metal industry

– Molten salts are used for production and purifying of metals

Pyrolysis

Departm en t of M athematic al Sciences and Tech nology

42

(43)

Departm en t of M athematic al Sciences and Tech nology

NOR W EGI A N UNIVE RSITY OF LIF E SCIENCES

www.umb.no

Molten salt pyrolysis

Biomass is heated in the absence of oxygen

Departm en t of M athematic al Sciences and Tech nology

43

Gas Liquid Solid

CO 2 , CH 4 , CO, H 2 -Fuel gas

-Synthesis gas to

produce other organic materials like methanol

Bio-oil

-Refine to fuel -Synthesize other valuable chemicals

Char and ashes

-Refine to active carbon

-Metallurgical industry

(44)

Departm en t of M athematic al Sciences and Tech nology

NOR W EGI A N UNIVE RSITY OF LIF E SCIENCES

www.umb.no

Molten salt pyrolysis

The role of the molten salt

– Heat transfer medium – Fluid reacting bed – Catalyst

Departm en t of M athematic al Sciences and Tech nology

44

(Jiang et al., 2009)

(45)

Departm en t of M athematic al Sciences and Tech nology

NOR W EGI A N UNIVE RSITY OF LIF E SCIENCES

www.umb.no

Molten salt pyrolysis

The composition of the products depends on

– feedstock – temperature – heating rate – reaction time – type of salt

Gases are favored by high temperatures and liquids are favored by low temperatures and high heating rates (flash-pyrolysis)

Chlorides (e.g. ZnCl 2 ) give single-ring aromatic

compounds (liquids) and carbonates (e.g. K 2 CO 3 or Na 2 CO 3 ) give gases

Departm en t of M athematic al Sciences and Tech nology

45

(46)

Departm en t of M athematic al Sciences and Tech nology

NOR W EGI A N UNIVE RSITY OF LIF E SCIENCES

www.umb.no

Advantages of molten salt pyrolysis

Higher heating rates

(Yashunishi and Tada, 1985)

Higher concentrations of H 2 in the gaseous fraction

(Tada and Yasunishi, 1987, Ça ğ lar and Demirba ş , 2002)

Higher yields of phenolic compounds in the liquid fraction

(Sada et al., 1992)

Retaining of noxius contaminants

(Hammond and Mudge, 1975)

Chlorine containing plastics are completely dechlorinated – no HCl produced

(Menzel et al., 1973, Bertolini and Fontaine, 1987, Chambers et al., 1984)

Hybridization with solar energy

(Adinberg et al., 2004)

Departm en t of M athematic al Sciences and Tech nology

46

(47)

Departm en t of M athematic al Sciences and Tech nology

NOR W EGI A N UNIVE RSITY OF LIF E SCIENCES

www.umb.no

Objectives

Experiments

– Produce bio-oils from different feedstocks (difficult convertible biomass like lignin) – Moderate temperatures (around 500 o C)

– Test different kinds of salts and salt mixtures

Explore product possiblities

– Characterize products (FTIR, GC)

Build up a laboratory molten salt reactor

Departm en t of M athematic al Sciences and Tech nology

47

(48)

UMB-UMN workshop 2009

Institute for Energy Technology

• Independent foundation established in 1948

• 550 employees (Kjeller and Halden)

• Turnover: MNOK 500 (US$ 80 mill)

• Contract Research

• Internationally oriented

• Energy research lab JEEP II research reactor, Kjeller

(49)

UMB-UMN workshop 2009

Energy, Environmental Technology and Physics

• Main activity areas

• Energy efficiency

• New renewables; solar, wind

• Hydrogen technology: production, storage, system analysis

• Basic research in physics

• Pollution and climate technology; CO 2 -management

• Geochemistry; stable isotopes

• Waste management; low and intermediate radioactive waste

• 90 employees

• Turnover: MNOK 80 (US$ 13 mill)

(50)

UMB-UMN workshop 2009

Outline

• Hydrogen activities

• Pyrolysis

(51)

UMB-UMN workshop 2009

Carbon capture and hydrogen production

(52)

UMB-UMN workshop 2009

CH 4 (g) + H 2 O (g) → CO (g) + 3H 2 (g)

CO (g) + H 2 O (g) → CO 2 (g) + H 2 (g)

Sorption enhanced steam methane reforming

H 2 -production in one single step

• Steam methane reforming :

• Water gas shift :

CaO (s) + CO 2 (g) → CaCO 3 (s)

CaO (s) + CH 4 (g) + 2H 2 O (g) → CaCO 3 (s) + 4H 2 (g) ΔH 550°C =13.4 KJ/mol

• Carbonation :

• Overall :

(53)

UMB-UMN workshop 2009

Sorption enhanced steam methane reforming

Process description

Regenerator Natural Gas

Steam Reformer with Integrated

CO2-capture H2-Purification

(PSA)

High purity H2 CO2 ready for storage

Spent sorbent

Regen. sorbent

Tail gas

Air

Indirect heat exchange Reformate, 95%+ H2 (dry basis)

Exhaust gas

Steam

CO2-separation

Condensate

Bu rn e r

Regenerator Natural Gas

Steam Reformer with Integrated

CO2-capture H2-Purification

(PSA)

High purity H2 CO2 ready for storage

Spent sorbent

Regen. sorbent

Tail gas

Air

Indirect heat exchange Reformate, 95%+ H2 (dry basis)

Exhaust gas

Steam

CO2-separation

Condensate

Bu rn e r

(54)

UMB-UMN workshop 2009

• Co- production of

electricity and hydrogen with integrated CO 2 -

capture

• Electricity from high temperature solid oxide fuel cells (SOFC)

• Hydrogen production by sorption enhanced steam methane reforming

• High total energy efficiency

www.zegpower.com

Co-production of hydrogen and power

The Zero Emission Gas power concept (ZEG)

(55)

UMB-UMN workshop 2009

Multi-cycle test of the SE-SMR process in lab fixed bed reactor (50-100 cycles)

Test of the novel sorbent in the SE-SMR process

Dolomite

Decrease of the H 2 production time reduced by a factor 3 after 25 runs

Stable production time

evidenced for 66 runs so far…

Synthetic Ca-based sorbent

(56)

UMB-UMN workshop 2009

ZEG-lab demo

2 kW, H 2 -production

1 kW, SOFC stack module

(57)

UMB-UMN workshop 2009

200 kW H 2 pilot plant

2.5 kW laboratory demonstration

2009

2005 2015

2002 2001

Time frame for the ZEG-technology

30 kW H 2 pilot

plant

(58)

UMB-UMN workshop 2009

ZEG POWER

ZEG POWER - -

K K å å rst rst ø ø

(59)

UMB-UMN workshop 2009

Pyrolysis of waste/biomass

• History: Microwave pyrolysis of biomass and waste

• Recent: Renewed interest in microwave assisted pyrolysis of biomass

• Participation in expert panel IEA Task 27: Hydrogen production from biomass

• Main focus: Construction of small-scale laboratory

reactors

(60)

UMB-UMN workshop 2009

Pyrolysis of waste/biomass

• Timeline:

• Batch-reactor (MWTGA) to be finished in October

• Fluidised bed reactor to be finished 2010

• Cooperation

• Norwegian University of Life Sciences: pyrolysis, biogas, system design

• Tel-Tek (Telemark Technological Research & Development Centre): biogas, system design, techno-economic analyses

• Joint project proposal: PYROGAS – Biorefinery for integrated thermochemical and biochemical

conversion of biomass

(61)

UMB-UMN workshop 2009

Collaboration possibilities

• Conversion of biomass:

• Catalytic gasification

• Catalytic pyrolysis

• Microwave pyrolysis

• Sorption enhanced gasification

• Molten salt pyrolysis

• Product upgrading

• Catalytic reforming

• Separation/upgrading of bio-oils

NOR W EGI A N UNIVE RSITY OF LIF E SCIENCES

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