Distributed Bio-Oil Reforming - Energy.gov...Process Upsets Long Duration Runs Demonstrate Distributed Hydrogen Production from Bio-Oil for $3.6/gge Safety Analysis Review and Analysis

Distributed Bio-Oil Reforming

R. Evans, S. Czernik, R. French, M. RatcliffNational Renewable Energy Laboratory

J. Marda, A. M. DeanColorado School of Mines

Bio-Derived Liquids Distributed Reforming Working Group Meeting

HFC&IT Program Baltimore, MD

October 24, 2006

1

GasificationPartial oxidation

CH1.46O.67 + 0.16 O2 → CO + 0.73 H2 Biomass Syngas

Water-Gas ShiftCO + H2O CO2 + H2

CH1.46O.67 + 0.16 O2 +H2O →CO2 + 1.73 H2

Biomass Hydrogen (14.3% yield)

Practical yields 10%2

Pyrolysis

Thermal decomposition occurring in the absence of oxygen

Is always the first step in combustion and gasification processes

Known as a technology for producing charcoal and chemicals for thousands years

3

4

Biomass

Lignin: 15%–25% Complex aromatic structure

Hemicellulose: 23%–32%

sugars

abundant sugar in the biosphere

Cellulose: 38%–50% Most abundant form of carbon

Polymer of glucose

Polymer of 5- and 6-carbon

Xylose is the second most

in biosphere

Biomass Pyrolysis ProductsLiquid Char Gas

FAST PYROLYSIS 75% 12% 13% •moderate temperature •short residence time

CARBONIZATION 30% 35% 35% •low temperature •long residence time

GASIFICATION .1 - 5% 10% 85% •high temperature •Short to long residence time

5

Fast Pyrolysis

• Fast pyrolysis is a thermal process that rapidly heats biomass to a carefully controlled temperature (~500°C), then very quickly cools the volatile products (<2 sec) formed in the reactor

• Offers the unique advantage of producing a liquid that can be stored and transported

• Has been developed in many reactor configurations; at present is at early stage of development (100 t/day commercial plant)

6

Bubbling Fluid Bed Pyrolysis

GAS

7

BIOMASS

BIO-OIL CHAR

For reactor or export

Gas recycle

For fluidization or export

Fluid Bed

Reactor

Fast Pyrolysis

CH1.46O0.67 → 0.71CH1.98O0.76 + 0.21CH0.1O0.15 + 0.08CH0.44O1.23

Biomass Bio-oil Char Gas 75% 13% 12%

Catalytic Steam Reforming of Bio-oil

CH1.98O0.76 + 1.24 H2O ⎯→ CO2 + 2.23 H2

Bio-oil Steam Hydrogen

Biomass 13.0% yield H2 Practical yield 10%

8

9

Fast Pyrolysis Bio-oil Bio-oil is water miscible and is comprised

of many oxygenated organic chemicals. • Dark brown mobile liquid, • Combustible, • Not miscible with hydrocarbons, • Heating value ~ 17 MJ/kg, • Density ~ 1.2 kg/l, • Acid, pH ~ 2.5, • •

time

Pungent odour, “Ages” - viscosity increases with

Approach

PYROLYSIS Bio-oilBiomass Methanol

VOLATILIZATION

10

REFORMING

H2

Show that bio-oil and blends with methanol can be fed without excessive coking and develop a process to meet HFC&IT cost and performance objectives.

O2 Low Temperature Oxidative Cracking

SHIFT

CO2SEPARATION

H2O

Thermal Severity

O HO CH2 C H OH

OH

Primary TertiarySecondary

Biomass H2O CO CO2

Char

“Carbon”

Bio-Oil H2, CO, CO2, H2O, C2H4,+

Olefins… Furans, Phenols, BTX, Ketenes,

H2O H2 CH4 CO CO2 PAH

11

Schematic of Pyrolysis Reactor & NREL’s MBMS Sampling System

Products and

Collisions Q1 Q2 Q3

Argon Collision

Transients Three Stage Free-Jet

{P+} +} e-

EI Source

He

He

Tpy

T1 T3 T4 T5

He

T2

Turbomolecular Pump

Turbomolecular Pump

Turbomolecular Pump

Molecular Beam Source Triple Quadrupole Mass Analyzer

{D

Detector

Molecular Gas Drag Pump

12

Rel

ativ

e In

tens

ity

Lignin Pyrolysis 675 ms @ 500 oC

208 CH2 CH CH OH CH3

210180 MeO OMe OMe OHOH

m/z 210 m/z 138 138 168

124 272 302 332234 358

388 418

0 50 100 150 200 250 300 350 400 450

m/z 13

14

Lignin Pyrolysis Score Plot

-3

0

3

-4 -2 0 2

500 550 600 625 650 675 700 725 750 775 800

12

Lignin Resolved Component Spectra

8

4

0

50 100 150 200 250 300 350 400

168

358

332 302

272 220

234

210

194

180

151

Primary

2.4

268 214

200

190 176

298 242 226

164 150

138

124

Secondary

3.2

2.4

1.6

1.6

0.8

0.8

0 0

50 100 150 200 250 300 350 400 50 100 150 200 250 300 350 400

120

66

78

94

158 170

206

264

104

128

142

184

232 248

Tertiary

15

-LN

(Cp/

Cp0

)4

3

2

1

0

Lignin Empirical Kinetic Model

500 C

550 C

600 C

0 0.2 0.4 0.6 0.8

Residence time, S 16

17O0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

C

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

650 oC

550 oC

P = 1 atm

CarbonDeposition

No CarbonDeposition

12 3

4 5 6 78

910111213

14

15161718

19

2021

2223

Equilibrium Modeling Results

1 = Bio-Oil composition, which liesin the region where carbon will form at 650 C

2-8 = O2 addition points9-13 = H2O addition

14-23 = both O2 and H2O

Goal is to identify the thermodynamic and kinetic domains for deposit free operation

18

oC

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

5

0 0.75 1

Dife

rent

ial S

igna

l, %

of t

otal

0

25

50

75

100

Inte

grat

ed S

igna

l,% o

f tot

al

46 mg

51 mg

54 mg

Average Residue = 6% Bio-Oil Film Volatilization – 400

0.25 0.5

Time, Min.

19

Bio-Oil Film Volatilization MBMS Bio-Oil Spectrum

Toil = 300 oC Tvc = 300 oC no O2

31

272

164

137

60

43

18

0

1

2

3

4

5

0 125 150 175 225 250 300

m/z

% o

f Tot

al Io

n Si

gnal

HC

O

CH2HO

CH3

OH O

O

HO

25 50 75 100 200 275

OMe

20

Bio-Oil Film Volatilization Cracking 0.5 s @ 650 C

Toil = 400 oC Tvc = 650 oC no O2

124 136

110

28

31

60

43

18

0

1

2

3

4

5

6

7

0 125 150 200 225 250 300

m/z

% o

f Tot

al Io

n Si

gnal

OH

OH

OH

CH3

25 50 75 100 175 275

CHO

110

21

Bio-Oil Film Volatilization Oxidative Cracking 0.5 s @ 650 C

44

60

18

0

5

10

15

20

25

0 125 150 175 200 225 250 300

m/z

% o

f Tot

al Io

n Si

gnal

T = 400 oC Tvc = 650 oC 2

256240226212

198 162

144

122

110

0.00

0.10

0.20

0.30

0.40

0.50

0.60

100 150 175 225 250 275

H2O

CO

CO2

25 50 75 100 275

oil with O

125 200 300

22

Ultrasonic Nozzle

• fine mist at 0.3g/min

• steady liquidfeed at low rates

Generating a

Enables

23

yringe Pump

l

r

Power Supply

Gas

MBMS

Furnace

Bed

Temperature Read-Out

Gas

Dual S

Bio-Oi

Wate

MFM Ultrasonic Nozzle

Catalyst

MFM

24

Ultrasonic NebulizerOxidative Cracking 0.5 s @ 650 C

0.0E+00

5.0E+07

1.0E+08

1.5E+08

2.0E+08

2.5E+08

3.0E+08

3.5E+08

0 2 4 6 8 10 12 14

Time, min

Abu

ndan

ce

18324428

0.0E+00

1.0E+08

2.0E+08

3.0E+08

4.0E+08

10 10.5 11 11.5 120.0E+00

1.0E+07

2.0E+07

3.0E+07

4.0E+07

28

44

1878

32

% Residual Carbon: 7.7%

% o

f Tot

al S

igna

l

Ultrasonic NebulizerThermal Cracking 0.5 s @ 650 C

6

5

4

3

2

1

0

15013677

11094 60

43

18

OH

CH3

OH

OH

OH

CH3 C

O

H

HC

O

CH2HO

31 = 13.4% 32 = 8.8%

CHO

0 20 40 60 80 100 120 140 160 180 200

m/z 25

40

Ultrasonic Nebulizer

% o

f Tot

al S

igna

l

Oxidative Cracking 0.5 s @ 650 C 28 CO

78

94 128

178

0

1

2

3

4

75 125

0.5

1.5

2.5

3.5

175

35

30

25

20 H2O

1815

10

5

0

CO2

44

MeOH OH31 78

94 128 178

0 20 40 60 80 100 120 140 160 180 200

m/z

26

Carbon ConversionOxidative Cracking 0.5 s @ 650 C

Equil. CO Equil. CO2

0

20

40

60

80

Car

bon

Con

vers

ion,

%

/

/

l

CO-Bio-Oil/MeOH

CO-MeOH

CO2-Bio-Oil/MeOH

CO2-MeOH

CO-Bio-Oil MeOH/H2O

CO2-Bio-Oil/MeOH/H2O

CO-Bio-Oil/MeOH (H2O)*

*H2O not inc uded in O/C

0.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9 2.1 2.3

O/C Mole Ratio

27

Carbon ConversionOxidative Cracking 0.5 s @ 500-650oC

0

10

20

30

40

50

60

70

80 C

O Y

ield

%

500 525 550 575 600 650

0.0 0.5 1.0 1.5 2.0

O/C

28

29

Methanol

Bio-Oil

Oxidative Cracking - Methanol vs Bio-Oil

30

Process Comparison0

C 44.2 H O 47.1 47.4

H/C O/C 0.8

1500 i 11.9 11.9 i

525 525 236 232

0 246 ith O2

) O/C( 0.5

/407 430

800 600

M 6 5 l 372 l 0 130

0 130 632

Fluid Bed Staged Bio-Oil Organics % 80 78

MeOH % 10 water,wt% 20 18

45 7.9 8.4

2.1 2.3 0.8

H2 production rate, kg/day 1500 H2 Y eld, wt%

Conversion eff ciency,% 70 70 Bio-Oil Feed Rate, kg/hr Feed C feed rate, kg/hr

O2 feed rate, kg/hr Ratios wH/C(H2Ofree 1.5 1.7

H2Ofree) 1.3 Starting H2O/C 0.30 0.27

H2O C after Oxcrack 0.30 0.75 Water addition, Kg/hr 1668

Catalyst load, kg 1734 Temperature, C

Reactor diameter, M 1.03 0.31 Reactor height,

Catalyst reactor vo ume, L 5029 Cracking reactor vo ume, L

Vaporizer, L Total reactor volume, L 5029

Project Timeline

31

Task Name

Bio-Oil Volatilization Processing Options Modification and Characterization Injector Development Coking Studies Go / No Go on Bio-Oil performance

Oxidative Cracking Proof of Concept Reduce Catalyst Loading by 50% Partial Oxidation Database Modeling and Optimization Jon Marda Thesis

Catalytic Auto-Thermal Reforming Catalyst Development

Integrated Separation Concept Evaluation Membrane Support Integrated Laboratory System Experiment Go / No Go on Conceptual Design

Systems Engineering Oxygen, Steam and Heat Integration Engineering Design and Construction Prototype System Developed Heat and Mass Balances Process Upsets Long Duration Runs Demonstrate Distributed Hydrogen Production from Bio-Oil for $3.6/gge

Safety Analysis Review and Analysis of Pressure, O2, H2 Systems Integration

5/31

6/30

5/30

6/1

6/30

12/3

2005 2006 2007 2008 2009 2010 2011

Summary

Relevance Near Term Renewable Feedstock for Distributed Reforming

Approach Bio-Oil Processed at Low Temp Homogeneous and Catalytic Auto-Thermal Reforming

Accomplishments Progress in Volatilization and Oxidative Cracking

Collaborations •Colorado School of Mines •Chevron

Future Work •Catalysis Integration in FY07 by working with DOE funded team

32

Technical Challenges

• Bio-Oil Volatilization – Management of residue

• Oxidative Homogeneous Cracking – High Reactivity but Unexpected Aromatics

• Catalyst System Design and Performance• Carbon Deposit Removal and Catalyst

Regeneration Management • Process Energy Integration • Integrated Hydrogen Separation

33

Complementary Projects

• Chevron Bio-oil Feedstock Effects – Bio-oils produced from a variety of feedstocks– Performance in staged auto-thermal reforming– Determine effect of major and trace constituents

• USDA/DOE Bioenergy Initiative – ISU, Cargill, NREL, ORNL, Eprida, USDA ARS – Corn Stover Pyrolysis for H2, NH3, Bio-carbon

based soil amendments– NREL: Bio-oil characterization and reforming

• DOE Biomass Program – Bio-oil Stabilization and Derivatization

34