2005 OBP Bi-Annual Peer Review

TC Platform Analysis Overview

Richard Bain

Thermochemical Platform

November 14-16

Overview

Budget• Nexant – Sulfur Removal

• PNNL – Alcohols Separations

• Princeton – Black Liquor Gasification for fuels

• UOP – Refinery Analysis

Partners

• Provide performance and cost data to Integrated Biorefinery models

• Provide research direction and focus through technoeconomic and environmental evaluation addressing technical barriers

• Set goals/targets

• Measure progress.

Analysis Objective

0

100

200

300

400

500

600

700

800

TC

An

alys

is B

ud

get

(K

$)

FY2004 FY2005 FY2006

Thermo ChemicalR&D

FeedstockR&D

BiochemicalR&D

ProductsR&D

IntegratedBiorefinery

Corn Wet Mill Improvements

Corn Dry Mill Improvements

Agricultural Residue

Processing

Energy Crops

Pulp & Paper Mill

Improvements

Forest Products Mill

Improvements

Corn

Other Grains

Corn StoverWheat StrawRice Straw

Perennial GrassesWoody Crops

Mill WastesWood

Mill WastesWood

Fiber Conversion

DDG Conversion

Biomass & Lignin Gasification

Systems- level demonstration & validation of technologies to

improve corn wet milling facilities using corn grain feedstock by

2008

Systems- level demonstration & validation of technologies to

improve corn dry milling facilities using corn grain feedstock by

2008

Systems- level demonstration & validation of technologies to

utilize agricultural residue feedstocks in existing or new

facilities by 2009

Systems- level demonstration & validation of technologies to

utilize perennial crops in existing or new facilities by 2012

Systems- level demonstration & validation of technologies to improve pulp & paper mill facilities and/ or produce

additional products from wood by 2012

Systems- level demonstration & validation of technologies to improve forest products mill facilities and/ or produce

additional products by 2012

Biomass & Lignin Gasification

Biomass & Lignin Gasification

Biomass & Lignin Gasification

Biomass Pyrolysis

Strategic fit with Pathways

The (Fully) Integrated Biorefinery

An effective integrated biorefinery must include biological and thermochemical conversion

Maximize efficiency of biomass (and land) utilization by producing fuels thermochemically and biologically

Potential Biorefinery Products

Biorefinery Product Target Product Market Comment

Mixed Alcohols Ethanol, existing alcohols marketsEthanol is largest component of mixed alcohol and can enter U.S. ethanol market. Higher alcohols are high-value byproducts.

FT Liquids - Naphtha Motor Gasoline FT naphtha is upgradeable to gasoline blendstock. Co-produced with FT distillate.

FT Liquids – Distillate Distillate Fuel High cetane, sulfur-free diesel blendstock. Co-produced with FT naphtha.

FT Liquids – Waxes WaxesPotential high-value co-product, but wax production in the US is declining. Can crack wax to make more distillate and naphtha.

Renewable Diesel Distillate Fuel Produced by hydrotreating of fatty acids. Also called Green Diesel

Dimethyl Ether (DME) Distillate or LPGBlendable with LPG to 20-25%. Diesel engine use requires fueling infrastructure changes – centrally fueled fleet vehicles are potential near-term market.

Pyrolysis Oil – Naphtha Motor Gasoline Upgrading of lignin fraction

Pyrolysis Oil - Distillate Distillate Upgrading of lignin fraction. Co-produced with naphtha fraction

Methanol MethanolMethanol as chemical intermediate (e.g., for olefins) is most promising market, since fuel use (MTBE) is in decline in U.S.

Hydrogen Hydrogen Market is growing, mainly for use in refineries (captive market)

Ammonia Ammonia Among the largest commodity chemicals

Targets – End Products

Ethanol from Thermochemical Mixed Alcohols

Year

2005 2010 2015 2020

Min

imu

m E

tha

no

l o

r M

A S

ell

ing

Pri

ce

($

/ga

l)

0.00

0.50

1.00

1.50

2.00

2.50

3.00Ethanol w MA at Market - Conversion CostEthanol w MA at Market - Feed CostMixed Alcohols - Conversion CostMixed Alcohols - Feed Cost

Mixed Alcohol (MA) 3% Methanol 73% Ethanol 15% n-propanol 6% n-butanol 3% C5+

Stateof Technology

CostTarget

CostTarget

CostTarget

Eth

ano

l

Mix

ed A

lco

ho

ls

Feed = wood @ $30/BDTValues in 2002$

Feed Processing & Handling

Thermochemical Processing

Clean-Up & Conditioning

Fuels & Chemicals

Heat & Power

Biomass ResiduesDedicated Crops

BiorefineryResidues

Fuels Production

Sensors & Control

Targets – Syngas Intermediate

$0.00

$1.00

$2.00

$3.00

$4.00

$5.00

$6.00

$7.00

$8.00

Today SOT - Currentdesign

Gas clean up &conditioning - Goal

design

Feed handling &drying

Gasification Process integration

Inte

rmed

iate

cle

an,

refo

rmed

syn

gas

pri

ce (

$/M

MB

tu)

Research in this area results in the largest syngas cost reduction

$4.75 $5.25 $7.25 $3.93 $4.05

Plant size = 2,000 BD tonne/day

• DOE program targets based on intermediate syngas price to track progress toward reducing technical barriers

Decrease in syngas price due to increased yields, decreased capital costs, & efficiency gains

(2025)(2010)

Fractional Conversion at 875oCModel N1D1

Time, Hours

0 1 2 3 4 5

Fra

cti

on

al C

on

ve

rsio

n

0.0

0.2

0.4

0.6

0.8

1.0

Benzene

Ethane

Methane

Naphthalene

Total Tar & Toluene

Targets – Tied with Research

$0.00

$1.00

$2.00

$3.00

$4.00

$5.00

$6.00

$7.00

$8.00

Current Design Goal Design

Inte

rmed

iate

cle

an,

refo

rmed

syn

gas

pri

ce (

$/M

MB

tu)

Current

Goal

Results from NREL’s PDU tar reformer

• Goal case yield is increased & capital cost is less

Potential Impact of Reformer Efficiency on Syngas Price

Attaining research goals = reduction in syngas price

Ethanol via bioconversion

Corn Stover 2,000 dMT/day

Ethanol198,400 gpd

Lignin-rich Residue

600 dMT/day

Steam & Power

Gas-FiredCHP Plant

SyngasProduction

Synthesis

Chemical Alcohols 11,800 gpd n-Propanol

9,100 gpd n-Butanol11,800 gpd Amyl/Hex Alcohols

Biomass Residues/Pyrolysis Oils1,205 dMT/day

SyngasEthanol

98,000 gpd

Ethanol296,400 gpd

Products from sugars will be made in both the stand-alone sugars biorefinery and in this Advanced Ethanol Biorefinery.

Sugars Based Biorefinery

FY05 Tasks

• State of syngas technology/update

• Equipment design and costs – design & cost detail for gas clean up, air separation unit, and modular systems (work with Nexant)

• Potential of ethanol from mixed alcohols (gasification of biomass and subsequent conversion to ethanol from mixed alcohols)

• Effect of oxygen purity on direct gasification (examine different oxygen purities then compare indirectly-heated LP gasification to directly heated HP gasification)

• Energy densification of distributed biomass (energy requirements and cost of delivering pyrolysis oil and biomass in various forms)

• Cost-benefit assessment of biorefineries making fuels from black liquor – Princeton University/Navigant/IPST-Georgia Tech/ Politecnico di Milano

• Opportunities for Bio-renewables in petroleum refineries – UOP/NREL/PNNL

Equipment Design & Costs Task

Gas Cleanup Design and Cost Estimates• Detailed design and costs for low pressure & high pressure gas

clean up & conditioning designs

cyclonessyngas

ScrubberTar reformer

Syngas cooling

Water

To treatment

LO-CATSulfur

Amine

CO2

Syngas compression

ZnO bed

For LP case

O2 Purity & Direct versus Indirect Gasification Task

Parameter Indirect BCL Direct GTI

Pressure Low pressure (25 psia) High pressure (350-450 psia)

Feeding system Feed screw conveyor Pressurized lock hoppers with feed screw conveyor

Syngas compression Additional compression needed No additional compression

Heat supply -two vessels (gasifier/combustor) with a circulating medium-air for combustion

-one vessel-oxygen blown thus ASU is needed

Raw syngas quality/properties

-more tar-more char-more CO-lower H2:CO ratio-higher heating value

-more CO2

-higher H2:CO ratio-lower heating value but higher gasifier efficiency because mass flow of dry gas is higher

Operating cost - lower - same

Capital cost - lower - 25% higher

Biofuel product yield - same - 3% higher

Energy Densification Task

• total delivered cost on an energy equivalent basis ($/GJ) for transport distances of 0 – 200 miles for:- wood chip delivery with drying at end use site - delivery of dried wood chips- delivery of pelletized wood- delivery of corn stover cubes- delivery of pyrolysis oil

Small Distributed Systems100 ton per day

Wood Chips

Truck Delivery

Pyrolysis Unit

Truck Delivery

Pelletizing Plant

Truck Delivery

Wood Chipping

Truck Delivery

Dryer Facility

At Forest/Field Harvesting Site

At End-Use Facility

On Delivery Truck

Wood Chips

Wood Pellets

Pyrolysis Oil

Raw Biomass

Dryer Facility

Dryer Facility

Corn Stover Cubing

Truck Delivery

Corn Stover CubesField-Dried

Corn Stover Bales

Wood Chips

Truck Delivery

Pyrolysis Unit

Truck Delivery

Pelletizing Plant

Truck Delivery

Wood Chipping

Truck Delivery

Dryer Facility

At Forest/Field Harvesting Site

At End-Use Facility

On Delivery Truck

Wood Chips

Wood Pellets

Pyrolysis Oil

Raw Biomass

Dryer Facility

Dryer Facility

Corn Stover Cubing

Truck Delivery

Corn Stover CubesField-Dried

Corn Stover Bales

LargePyrolysis

Plant

$0.00

$2.00

$4.00

$6.00

$8.00

$10.00

$12.00

$14.00

0 50 100 150 200 250

Delivery Distance (mi)

Del

iver

y C

ost

($/

GJ(

LH

V),

dry

)

Wood Chip Delivery, Drying at Pad Pellet Delivery

Pyrolysis Oil Delivery Wood Chip Delivery, Drying at Conversion Facility

Central Pyrolysis: Dry Chips Central Pyrolysis: Wet Chips

Pyrolysis Oil

Dry Wood

Forest Biorefinery Analysis

ObjectiveComplete a detailed design and cost-benefit assessment of biorefineries making synthetic fuels from

black liquor (BL) and wood residues at U.S. Kraft pulp mills; reference mill case-study approach; assess potential energy and environmental impacts for the industry and the country.

Activities to date• Screened and prioritized biorefinery products for detailed analysis. • Developed modeling tools for process design/simulation, mill-integration analysis, financial analysis,

and cost-benefit evaluation.• Heat and mass balances developed for two fuel products (F-T liquids and DME), ongoing for third

product (mixed alcohols), and planned (pending additional funding) for fourth product (methanol as a chemical intermediate).

• Scoping analysis ongoing for low-temperature BLG to identify most promising mill integration and biorefinery products.

• Financial/environmental cost-benefit spreadsheet model under development.• Initial discussions with engineering company for capital cost estimates.

Analytical Team Eric Larson – Princeton University Ryan Katofsky – Navigant Consulting Stefano Consonni – Politecnico di Milano Kristiina Lisa – IPST/Georgia Tech Jim Frederick – IPST/Georgia Tech

Opportunities for Bio-renewables in Petroleum Refineries

• Evaluate the economics for use of Biorenewables in Oil Refineries ( Based on $40/bbl crude)

• Uncover attractive near and long term Opportunities for Biorenewables in Oil Refineries

- Proof of Principle Experiments to Confirm Ideas

Goal

Activities

• Production of Renewable (green) Diesel• Upgrading of Pyrolysis Oils

•Separation into Lignin and Aqueous Fractions•Upgrading of Lignin Fraction

Team

UOP/NREL/PNNL

Renewable Diesel

Stand Alone Skid Mounted Unit

Oil or grease

DHTDiesel

H2

Green Diesel

Diesel

12-16% water,C02

80-100Cetane Number

Feed

<10

83-89

2-5

1.5-3.8

100

ppm S

% diesel

% Lt HC

Products

% H2

% Oil or Grease

12-16% water,C02

80-100Cetane Number

Feed

<10

83-89

2-5

1.5-3.8

100

ppm S

% diesel

% Lt HC

Products

% H2

% Oil or Grease

.78.883Density g/ml

0 to -10+10 % change in NOx emission

265-320340-355Distillation 10-90% pt

<10ppm<10ppmSulfur content

4438Heating Value (lower) MJ/kg

011%O

-5 to -30-5 Cloud Point C

80-9050Cetane

Green dieselBiodiesel (FAME)

.78.883Density g/ml

0 to -10+10 % change in NOx emission

265-320340-355Distillation 10-90% pt

<10ppm<10ppmSulfur content

4438Heating Value (lower) MJ/kg

011%O

-5 to -30-5 Cloud Point C

80-9050Cetane

Green dieselBiodiesel (FAME)

H2

FY05 Milestones

Milestone type

Task / Milestone DescriptionCompletion

Date

D Biomass syngas to product design report 1/31/05

D Energy densification of distributed biomass 4/15/05

DEffect of oxygen purity on direct-fired gasification & comparison to indirect gasification

9/30/05

EPotential of thermochemical ethanol from mixed alcohols

10/31/05

J

Complete a technical and economic evaluation to validate the cost of syngas from biomass suitable for producing a fuel product.

3/31/056/30/059/30/05

Future Work - FY06

• State of syngas technology/update

• Dry or CO2 reforming versus steam reforming – potential economic & environmental benefits

• Sugars/Thermochemical Integrated Biorefinery (cost shared with strategic analysis)

• Cost-benefit assessment of biorefineries making fuels from black liquor

Lignocellulosic Biomass

Fermentation

Catalysis

Syngas Production

Sugar Production

Ethanol

Products:propanol, butanol

other alcohols

Lignin-rich Residues

Low Quality Residues

CHP DistillationCO2