RTI International is a trade name of Research Triangle Institute. www.rti.org

Catalytic Biomass

Pyrolysis Technology

Development for

Advanced Biofuels

David C. Dayton

Director of Biofuels

Energy Technology Division

RTI International

September 5, 2013

RTI International

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into practice

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organizations

>3,700 staff working in over 75 countries

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Sciences

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RTI Energy Technologies

Biomass and Biofuels

Shale Gas

Syngas Carbon Capture

Industrial Water

• Developing advanced process technologies

for energy applications

• Partnering with leaders in energy

Advanced Biofuels Technology

Development Approach

Objective: Demonstrate an advanced biofuels technology that integrates a catalytic biomass

pyrolysis step and a hydroprocessing step to produce infrastructure compatible biofuels.

> Design and operate fully integrated processes capable of

reaching steady state and generating long term, continuous

data sufficient to validate the process for scale-up.

> Demonstrate the upgrading step(s) in a continuous,

integrated process

> Estimate the cost of the final hydrocarbon product stream

that meet advanced biofuels specifications

Scale-Up and

Commercialization Process Development

Catalytic Pyrolysis

Process

Biomass

Bio-crude

Oxygen Rejection

Catalyst Synthesis

Catalyst Characterization

BET, TPR, Surface Analysis

Model Compound Testing

Bench-scale Catalytic Pyrolysis

Identify key parameters for

reactor design

Deoxygenation

Regeneration

Coke yields/Energy efficiency

Oxidation and reduction rates

Real Biomass Testing

Yields

Gas

Bio-crude

Char/Coke

Hydrogen demand

Bio-crude Analysis and Quality

Process Modeling

Heat and Material Balances

Reactor Design

Catalyst Development

Advanced Biofuels

Technology Proof-of-Concept

Catalytic Biomass

PyrolysisHydroprocessing

Feedstocks

Woody biomass

Energy Grasses

Corn Stover

Advanced

Biofuels

Gasoline,

Diesel, Jet Fuel

Proof of Concept

(1" dia fluidized bed)

RTI (ARPA-E)

Bench-scale

(1 TPD)

RTI (BETO)

Proof of Concept

(1-L upgrading)

P66 (ARPA-E)

Bench-scale

(250-mL integrated)

Haldor Topsøe (BETO)

The technical goals are to:

1) Develop a catalyst to achieve high degree of deoxygenation

• Model compound screening

• Lab-scale testing with biomass

2) Maximize biofuels yields and energy recovery

3) Determine technical feasibility of bio-crude upgrading

4) Develop preliminary techno-economics

Catalyst Development

Screened catalysts for

deoxygenation activity to

control bio-crude properties

and maximize carbon efficiency

Automated microreactor with model compounds

• Programmed reaction sequence for unattended operation

• Rapid screening to evaluate deoxygenation activity with model compounds

• Quantitative real-time product analysis

• Measure regeneration products for coke yield

Bench-top fluidized bed reactor for catalytic biomass pyrolysis

• Correlate deoxygenation activity with bio-crude oxygen content

• On-line gas analysis

• Liquid and solid product collection and analysis

• > 95% mass closure for bio-crude yield and energy recovery

• Over 100+ trials of catalytic fast pyrolysis in the bench-top fluidized bed reactor

Model Compound Results

Real-time, online MS analysis

• Products correlated with specific

ions (m/z)

• Products quantified by calibration

and integration under curve

• Provides time resolved product

composition

• Measure both reaction and

regeneration

Guaiacol flow rate adjusted for 90% or less conversion to

evaluate time-dependent deoxygenation activity

Catalytic Biomass Pyrolysis

Proof-of-Concept

1”-diameter Fluid Bed Reactor System

Bio-crude Properties Baseline RTI-A9

TAN (mg KOH/g bio-crude)

105 25

KF water Content (wt%) 27 10

Kinematic Viscosity at 40°C (cSt)

53.2 56

Revaporization Efficiency at 350°C 48% 82%

Baseline RTI-A9

Solids (wt%) 14.3 19.8

Gas (wt%) 11.6 23.9

Water (wt%) 18.4 28.7

Bio-crude, dry (wt%) 49.4 24.8

Bio-crude Composition (wt%)

C 56.6 72.8

H 5.8 7.2

O 37.7 19.9

Gas composition (vol%)

H2 1.5 7.7

CO 25.4 37.1

CO2 42.1 32.6

CH4 3.5 10.6

C2+ 27.4 12.0

Bio-crude Production in a 2”

Fluidized Bed Reactor

• 14-kg of white oak converted

• 1.5-L bio-crude produced

• 345 reaction/regeneration cycles

• Total biomass/catalyst contact time of 87

hours time on stream

• Average mass balance: 90%

• Average bio-crude oxygen content: 19.5 wt%

Goal: To produce 1-L of bio-crude intermediate for 100 hour hydrotreating test and

evaluate long-term catalyst stability (material balance and bio-crude oxygen content)

during repeated catalytic biomass pyrolysis and regeneration cycles

Bio-crude Upgrading -

Hydroprocessing

Hydroprocessing reactions:

• Decarbonylation

• Decarboxylation

• Hydrodeoxygenation (HDO)

Competing reactions:

CO2 + H2 ↔ CO + H2O

CO + 3H2 → CH4 + H2O

Proof-of-Principle (2-stage Upgrading)

• Bio-crude can be upgraded to

hydrocarbons

• Product is mainly in gasoline range

• Product is rich in cyclic alkanes and

monoaromatics

Simulated Distillation Results

Advanced Biofuels

Technology Scale-up

The technical goals are to:

1) Optimize the catalytic biomass pyrolysis process to achieve high

degree of deoxygenation, while maximizing the bio-crude yield

2) Improve bio-crude thermal stability

3) Evaluate the impact of bio-crude quality in the hydroprocessing step

4) Minimize hydrogen demand of the integrated process

5) Maximize biofuels yields

Catalytic Biomass

PyrolysisHydroprocessing

Feedstocks

Woody biomass

Energy Grasses

Corn Stover

Advanced

Biofuels

Gasoline,

Diesel, Jet Fuel

Proof of Concept

(1" dia fluidized bed)

RTI (ARPA-E)

Bench-scale

(1 TPD)

RTI (BETO)

Proof of Concept

(1-L upgrading)

P66 (ARPA-E)

Bench-scale

(250-mL integrated)

Haldor Topsøe (BETO)

Process Development

1 TPD Catalytic Biomass Pyrolysis Unit

Objectives: • Demonstrate RTI’s catalytic biomass pyrolysis

process at pilot-scale with a biomass feed rate

of 100 lb/hr • Bio-crude with less than 20 wt% oxygen

• At least 50% energy recovery

• Mass closure at least 90%

• Understand the effect of operating parameters

on product yields and quality – Pyrolysis temperature (350-500 ºC)

– Residence time (0.5-1.0 s)

– Regenerator temperature (500-700 ºC)

– Catalyst circulation rate

– Type of biomass

Design based on single-loop transport reactor system • Catalyst undergoes continuous reaction and regeneration

• System can be operated autothermally with heat of

regeneration (and char combustion) carried over by the

catalyst to the reaction zone

Design Basis and System

Overview

Process Sub-systems

Biomass Feeder • Bulk bag discharge system

• Double lock hopper – T.R. Miles

design

Reactor System • Transport reactor

• Make-up catalyst storage

• Quench system for pyrolysis

products recovery

– Spray column

– Separation vessel

– Heat exchanger

Product Collection and Storage

Regenerator Off-gas Cooler

Thermal Oxidizer and Vent

Design

Basis Range

Pyrolysis temperature, ˚C 500 350-500

Regeneration temperature, ˚C 700 500-700

System pressure, psia 20 20-30

Biomass feed rate, lb/hr 100 25-110

Residence time, s 0.5 0.4-1.2

Biomass Feed System

Feedstock Preparation

Biomass received in super sacks (0.5” top

size, ~10% moisture, 15-30 lb/ft3 bulk density)

Bulk bag discharger for loading the feeder

hopper

Biomass Feeder (T.R. Miles Design)

Double lock hopper design to purge and

pressurize feed

Design feed rate: 100 lb/hr based on

volumetric flow rate

Bottom bin capacity above level switch: 1.8 ft3

Cycle time every 15-30 minutes

Cooling water jacket surrounding the feeder

screw

Transport Reactor

Reactor

• Biomass and catalyst are fluidized with N2 in the

mixing zone

• Biomass and regenerated catalyst fed just above

gas distributor

• Reactor cyclone separates coked catalyst, char,

ash and unconverted biomass from pyrolysis

vapors and permanent gases

Regenerator

• Char and coke oxidize in the regenerator

• Water or diesel can be added to the regenerator

to control the bed temperature

• Ash and catalyst fines entrain out of the

regenerator at the operating gas velocity

• Make-up catalyst is added when solids level in

the regenerator drops below a certain level

Regenerator

Cyclone

Reactor

Cyclone 1

Regen

Off-gas

Catalyst, Ash

and Char

Riser2" x 169"

Mixing Zone6" x 41"

Loop Seal

Regenerator Air

169"

41"

36"

RegeneratorBottom: 18" x 76"

Top: 24" x 120"

Biomass

48"

76"

Fluidization N2

66"

Fuel

Water

Riser Reactor and Regenerator

Riser Reactor

Regenerator

Regenerator

Distributor

RTI’s Energy Technology

Development Facility

RTI’s 1 TPD Catalytic Biomass

Pyrolysis Unit

Front View Back View

Biomass

Conveyer

Screw

Biomass

Feeder

Regenerator

Reactor

Product Storage Tanks

Gas/Liquid

Separator

Chiller Controls

Cabinet

1 TPD Shakedown

• Biomass feeder calibrated with 2 mm loblolly pine sawdust – up to 200 lbs/hr

• FCC Catalyst used for cold flow and hot flow testing to verify solids

circulation rates - ~1000 lbs/hr

• Biomass feeding with diesel and water injection in regenerator

• First bio-oil produced on August 9, 2013

• Pyrolysis catalyst loaded August 12, 2013 – solids circulated at ~1000-2000

lbs/hr

• First bio-crude produced August 21, 2013 (analyses pending)

• Process optimization in progress

Loblolly Pine Sawdust

Liquids

Aqueous Organics

Solids

(Ash and Catalyst Fines)

Process Development

Hydroprocessing Unit

Hydro

treater

Hydro

cracker Fractionator

Separator

Diesel

Naphtha

Gas

Recycle

Recycle Heavy Ends

H2Bio-crude

Design Basis: Hydroprocessing reactor with a high-

pressure separator (HPS) followed by a low-pressure

stabilizer (LPS) for removal of gases and other non-

condensed light hydrocarbons

• Reactor volume - 250 ml

• Catalyst volume - 20 to 60 ml of catalyst

• Liquid hourly space velocity - 0.5 to 1.0

• Flow rates - 10 to 60 ml/h

Key process variables to determine

• H2 consumption

• product yields

• catalyst performance

• reactant gas composition

• CO, CO2, and CH4 content in the hydroprocessing

reactor

• heat balance Conceptual Process Flow Diagram for Bio-crude

Hydroprocessing (Recycle streams to be validated)

Critical Success Factors

Catalytic fast pyrolysis – Demonstrate 1-TPD operation for bio-crude

production

– Validate catalyst durability and properties

– Demonstrate bio-crude yield and quality

– Bio-crude production at scale relevant for integrated hydroprocessing demonstration

– 3 high impact feedstocks (wood, corn stover, switchgrass)

Bio-crude upgrading – Impact of bio-crude properties

– Establish process conditions (T, P, pH2)

– Optimize hydroprocessing catalyst

performance; product yield and quality

– Over 1000 h operation

– Catalyst lifetime (regeneration)

– Develop hydroprocessing model

Techno-economic evaluation – Cost per gallon of upgraded bio-crude

– Cost per gallon of finished fuel

– Hydrogen demand

Catalytic Pyrolysis

Process

Biomass

Bio-crude

Oxygen Rejection

Catalyst

Development

Process

Development

Scale-up and

Commercialization

Acknowledgments

DOE/EERE/BETO

• Melissa Klembara

ARPA-E

• Mark Hartney

• Karma Sawyer

• Daniel Matuszak

Archer Daniels Midland

• Todd Werpy • Tom Binder • Ahmad Hilaly • Gustavo Dassori

Phillips66 • Kristi Fjare • Ron Brown • Liang Zhang • Sam Jones

Haldor Topsøe • Kim Knudsen • Glen Hytoft • Jostein Gabrielsen

RTI Contributors

• David C. Dayton (PI) • John Carpenter • Matt von Holle • Jonathan Peters • Gary Howe • Martin Lee • Atish Kataria • Josh Hlebak • Tim Bellamy

Your Invited….

Advanced Biofuels Technology Open House

• Who’s invited – Advanced biofuels technology

researchers and developers from industry,

academia, and government

• Where - RTI’s Main Campus in Research

Triangle Park, NC

• When – Q4 2013 or Q1 2014

• E-mail me (ddayton@rti.org) or drop your

contact information at one of our posters to

be added to the list of invitees

Technology Development Timeline

RTI Internal

R&D Funds

2009 – 2011

DOE/EERE ($1.875MM)

Catalytic Deoxygenation of Biomass Pyrolysis Vapors to

Improve Bio-Oil Stability 2010 – 2013

DOE/ARPA-E ($4MM)

Catalytic Bio-crude Production in a Novel, Short-Contact Time Reactor

2012 – 2015

DOE/EERE ($5MM)

Catalytic Upgrading of Thermochemical Intermediates to Hydrocarbons

2008 2009 2010 2011 2012 2013 2014 2015 2016

Proof-of-Principle

Experiments

Capability Development

Catalyst Development

and Testing

1 TPD Process Development

Design and Engineering

Catalyst Scale-up

RTI Facility

Design and Construction

1 TPD System Delivery

1 TPD System

Fabrication

Installation and Commissioning

Bio-crude Upgrading

Proof-of-Principle

Process Operation

and Optimization

Bio-crude Upgrading

Process Development

Process Scale-up

and Demonstration