advanced biomass to gasoline technology - us … · 2016-05-10 · key innovations in this...

Grant # EE0002991 Exelus 1

Advanced Biomass to Gasoline

Technology

May 24th. 2013 Bio-Oil Technology Area Review

Mitrajit Mukherjee Exelus Inc.

This presentation does not contain any proprietary, confidential, or otherwise restricted information


Outline

Objectives Project Overview Technical Approach Summary of Results Relevance Critical Success Factors Future Work Summary


Goal Statement

Project seeks to develop a low-temperature chemical process to convert cellulosic biomass into a gasoline blend-stock

Key innovations in this technology are Novel biomass deconstruction scheme & Engineered catalysts that convert the de-polymerized

biomass into alcohols as high-octane gasoline additives


FOA Objectives

The objectives of this FOA are to develop: Technologies and processes necessary for abundant

commercial production of bio-fuels at prices competitive with fossil fuels;

High-value bio-based products: to enhance the economic viability of bio-fuels and power; to serve as substitutes for petroleum-based feedstocks and

products; and to enhance the value of co-products produced using the

technologies and processes; and A diversity of economically and environmentally sustainable

domestic sources of renewable biomass for conversion to bio-fuels, bio-energy and bio-based products.


Timeline

Start - September 1, 2010 End - August 31, 2013 Percent complete = 90%

Budget • Total project funding

– DOE share = $1.2 million – Contractor share = $0.4 million

• Funding received so far • DOE = $ 1.0 million • Project Partners = $0.5 million

• ARRA Funding = 0

Partners

Quad Chart

Barriers

1. Glucose Decomposition 2. High H2 Consumption 3. Dilute product concentration

http://www.mustangeng.com/Pages/default.aspx

Exelus Grant # EE0002991 6

Project Overview

Biomass Structure Conventional Processes

Exelus Approach & Targets


Biomass has Complex Structure


Typical Approach


Exelus

Energy

Economics Environment

E3 Constraints

New process technologies must address all three aspects of modern fuel manufacturing:


Process Wish-list

Mild operating conditions Low Temperatures (< 250oC) Modest Pressures (< 40 bar)

Simple processing steps Fixed-bed reactors Conventional unit operations

Inexpensive catalysts Minimize use of precious metal catalysts No hazardous liquid acids

Modest utility requirements No biomass drying step Product concentrations > 20 wt% in water


Integrated Approach Catalyst Reactor

Process

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Exelus Process Overview


Technical Approach

Exelus Approach Technical Targets Major Mile-stones


Biomass-to-Gasoline Process

HOH

HOH

HH HH

OH

OH

Cellulose Crystal

Glucose Oligomers

De-crystalization & De-polymerization

Glucose

Hydrolysis

Deoxygenation & Cracking

Isopropanol

Ethanol

BioGasoline


Finding the Middle Ground

10

100

1000

0 1 10 100 1,000 10,000 100,000

Rea

ctio

n Te

mpe

ratu

re (o

C)

Reaction Time (Sec)

Enzymatic

Reactions

Exelus

Biomass-to-Gasoline (BTG)

Gasification

Pyrolysis

0.1


Innovations

0.00001

0.0001

0.001

0.01

0.1

1

10

100

0.0001 0.001 0.01 0.1 1 10 100 1000

Tim

e S

ca

le (s

ec

)

Length Scale (m)

10-10 10-8 10-6 10-4 10-2 100 102

104

102

100

10-2

10-4

10-6

10-8

Active Sites

Benign acid sites allow selective deconstruction of

cellulose to glucose

Pore Structure

Reactor Configuration

Process Design

Reduces glucose degradation to HMF, polymers, and other

undesired compounds

Uniform operating conditions reduce capital

and operating costs

Allows unrestricted diffusion of oligosaccharide molecules


Overall Chemistry

C6H10O5 + 6 H2 2 C3H8O + 3 H2O

C6H10O5 + 6 H2 3 C2H6O + 2 H2O

Cellulose Monomer

Hydrogen Propanol Water

Cellulose Monomer

Hydrogen Ethanol Water

ΔHf° = -186.5 kJ/mol propanol

ΔHf° = -103.4 kJ/mol ethanol

Propanol

Ethanol


Technical Targets & Barriers

Key Variables Technical Target Associated Barriers

Overall Process Performance (All Reactions Combined) Productivity >150 g biomass converted /

m3 catalyst /sec per reaction Reduced activity in low-cost catalysts Rate of cellulose decomposition

Selectivity >70% Selectivity to alcohols Methanation, reforming & etherification rxns Stability < 1 kg catalyst consumed /

ton alcohols produced Catalyst coking, corrosion under hydrothermal conditions

Catalyst Cost < $100 /kg Precious metal content Capital Requirements

Less than $8000 per barrel-per-day capacity

Separation requirements, reactor volume and configuration, process severity

Total Cost of Production

Less than $2.00 /gal alcohol product

Distillation costs, hydrogen requirement, energy inputs, process selectivity


Experimental Results

Cellulose Deconstruction Oligosaccharide Hydrolysis

Glucose Cracking/De-oxygenation Stability Test


Step 1: Cellulose Deconstruction

Breaking the hydrogen bonds


Types of Biomass Tested

Pine

Sawdust

Paulownia

Plant

Generic

Switchgrass

Switchgrass

EG1101 Switchgrass

EG1102

Exelus


Feedstock Flexibility

90%

92%

94%

96%

98%

100%

0 0.05 0.1 0.15 0.2Biomass Deconstruction Rate (1/hr)

Olig

osac

char

ide

Sel

ectiv

ity (%

) Micro-crystalline CelluloseGenetically Modified

Switch-Grass (EG-1102)

Birchwood

Pine

Genetically Modified Switch-Grass (EG-

1101)

Typical rates for industrial reactions


Step 2: Oligosaccharide Hydrolysis

Breaking the b-bonds

Oligosaccharide

Glucose


Step 2: Catalyst Screening Results

0

20

40

60

80

100

A B C D E F G

Olig

osac

char

ide

Conv

ersio

n to

Glu

cose

(%)

ConversionSelectivity

Catalyst Number


Step 3: Cracking and De-oxygenation

Breaking C-C and C-O bonds

Ethanol Iso-Propanol

Glucose

H2 H2

http://upload.wikimedia.org/wikipedia/commons/8/82/Ethanol-2D-skeletal.svg

http://upload.wikimedia.org/wikipedia/commons/0/0d/2-Propanol.svg


Step 3: Catalyst Screening Results

0

20

40

60

80

100

A B C D E

Glu

cose

to A

lcoh

ols

(%)

ConversionSelectivity

Catalyst Number


Integrated Test Unit


Integrated Stability Test Results

0

20

40

60

80

100

0 40 80 120 160 200 240 280 320

time on stream (hrs)

Con

vers

ion

/ Sel

ectiv

ity (%

)

Conversion of biomass

Selectivity to bio-gasoline


Bio-Gasoline Composition

Ethanol35%

Iso & n-Propanol60%

Methanol2%Butanol

3%


Project Relevance

MYPP Mission & Goals Project Relevance

Approach to meeting targets


MYPP Mission & Goals


Project Relevance

BTG

Process80% Yield

1.3 Billion Tons of Biomass per

year

70% Usable for Biofuel

Lignin (burned for fuel), Inorganics, & Water

8.5 Million Barrels of

Gasoline Equivalent

per Day

450 Million Gallons per Year

of Alcohols

BTG

Process80% Yield

1.3 Billion Tons of Biomass per

year

70% Usable for Biofuel

Lignin (burned for fuel), Inorganics, & Water

8.5 Million Barrels of

Gasoline Equivalent

per Day

450 Million Gallons per Year

of Alcohols

Estimated Bio-Gasoline Cost = $2.00/gal


Approach to meeting project targets

Exelus Approach

Advantages Benefits

Liquid Phase Processing

No expensive solvents required “Green” process Ability to use wet biomass

Reduced energy consumption

Feedstock flexibility Heterogeneous

Catalysts No neutralization required No acid migration through process Simple separation of catalyst and process

streams

Low operating costs Low equipment costs

Engineered Catalyst Functionality

Intensifies and simplifies process by eliminating multiple separation steps.

Minimize coke, acid and polymer formation High overall selectivity

Low capital cost High catalyst stability Efficient conversion of

feedstock Novel Process

Chemistry High carbon efficiency and retention of 94%

of input chemical energy Highly efficient

process


Critical Success Factors

RFS Mandates Biomass Logistics

Capital Cost Variable Cost of Production


RFS Mandate


Biomass Logistics

Biomass is a diffuse energy source

Has low energy content per unit mass and unit volume

Is limited in the amount that can be produced per unit land area.

Transporting biomass over large distances is energy-inefficient and economically prohibitive

Feeding solid bio-mass to reactors under pressure is a challenge

0

2000

4000

6000

8000

10000

5 10 15 20

Maximum Transport Distance (miles)

Max

imum

Bio

fuel

Pro

duct

ion

(bar

rels

per

day

)

Operating Window


High Capital Costs


Variable Costs

Biomass34%

Hydrogen38%

Utilities14%

Fixed Costs14%

Total Cost of Production = $530 /MT

Assumes 75% biomass and hydrogen selectivityEstimated Bio-Gasoline Cost = $2.00/gal


Future Work

Techno Economic Evaluation Technology Validation

Developing Consortium Team


Mass Balance

Biomass to Fuels

Process

Biomass 1000 kg/hr

Hydrogen 50 kg/hr

Hydrocarbons 400 kg/hr

Water 400 kg/hr

By-products 250 kg/hr

Carbon Efficiency = 75%


Exelus

Bio-Gasoline Cost of Production

0

1

2

3

50 60 70 80 90 100Biomass Selectivity to Alcohols (%)*

Cos

t of P

rodu

ctio

n ($

/gal

)

$0.45/gal Utility Costs

Hydrogen Selectivity = 100%

50%

$0.45/gal Fixed Costs

*Lignin-free

Cost of Biomass $100/tonCost of Hydrogen $1500/ton


Technology Validation


Develop Consortium

Exelus

Launch

Customer

Catalyst

Manufacturer

Engineering Company


Summary

This project seeks to develop a break-through thermo-chemical process to convert cellulosic biomass into a high-octane gasoline blend-stock

Exelus process replaces conventional high-temperature processes like gasification and pyrolysis with a series of mild, low-temperature reactions achieved using novel catalytic methods

Selective conversion (>90%) of bio-mass to mixed alcohols has been demonstrated at mild conditions using “green” catalysts

Future work will focus on techno-economic evaluation of this new B2G process


Questions

advanced biomass to gasoline technology - us … · 2016-05-10 · key innovations in this...

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