pyne -- glasgow wp 2h biorefinery tony bridgwater and doug elliott september 20, 2006

PyNe -- Glasgow PyNe -- Glasgow PyNe -- Glasgow PyNe -- Glasgow

WP 2H Biorefinery

Tony Bridgwater and Doug ElliottSeptember 20, 2006

2

Presentation OrganizationPresentation OrganizationPresentation OrganizationPresentation Organization

Biorefinery basics

Biorefinery concepts

TEA for Biorefineries

3

An Example of a Current BiorefineryAn Example of a Current BiorefineryAn Example of a Current BiorefineryAn Example of a Current Biorefinery

Corn Wet Mill

starch corn oilcorn gluten

mealcorn gluten

feed

food & industrial starches

hydrolysis

glucose

fuelethanol

High fructosecorn syrup

sorbitol

• foodstuffs• pharma.

polyols isosorbide

hydrogenation

Othersweeteners

citric acid lysine

xanthan gumsitaconic acid

& other fermentation

products

industrial oils

lactic acid

PLApolymers

•resins & plasticsapplications

•polyesters•surfactants•pharmaceuticals

deicerssolventscoatings

glycerolfood oilsfeed oils

Corn Wet Mill

starch corn oilcorn gluten

mealcorn gluten

feed

food & industrial starches

hydrolysis

glucose

fuelethanol

fermentation

sorbitol

• foodstuffs• pharma.

polyols isosorbide

hydrogenation

citric acid lysine

xanthan gumsitaconic acid

& other fermentation

products

industrial oils

lactic acid

PLApolymers

•resins & plasticsapplications

•polyesters•surfactants•pharmaceuticals

deicerssolventscoatings

glycerolfood oilsfeed oils

T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005

4

Current Ethanol ProcessCurrent Ethanol ProcessCurrent Ethanol ProcessCurrent Ethanol Process

Corn Dry Grind Liquefaction Scarification

FermentationPrimary

DistillationDistillationRectifier

MolecularSieves

Centrifuge

Triple EffectEvaporator

DDGDryer

DDGAnimal Feed Ethanol

Solids

50%EtOH

95%EtOH

100%EtOH

Liquids

Water Recycle

Solids


5

Strategies for Creating Additional ValueStrategies for Creating Additional ValueStrategies for Creating Additional ValueStrategies for Creating Additional Value

Modify dry mills to include a quick steeping process that allows germ recoveryAdd an intermediate filtration process to recovery non-starch derived sugars (hemicellulose)Develop new fermentations for utilization of five carbon sugars (itaconic acid, succinic acid, etc)Develop new chemistry to produce value added products from hemi-cellulose (sugar alcohols, polyols)Include an energy component-pyrolyze “DDG or modified DDG” to produce bio-oil


6

The Holistic Ethanol FacilityThe Holistic Ethanol FacilityThe Holistic Ethanol FacilityThe Holistic Ethanol Facility

Corn Quick Steep Scarification

Filtration Fermentation EthanolRecovery

MolecularSieves

“Fiber” HydrolysisNew DDG

Animal FeedEthanol

StarchEtOH 95%

EtOH100%EtOH

GermSeparation

Fermentation

CatalyticConversions

Pyrolysis

Fuel/PowerEG, PG

Glycerol, Etc

ItaconicSuccinic, Etc

Oil


7

Possible Future BiorefineryPossible Future BiorefineryPossible Future BiorefineryPossible Future Biorefinery

Lignocellulosic Biomass

Hydrolysis Fermentation

UpgradingPyrolysis

Ethanol FuelDistillation

Products

Products

lignin

sugars

bio-oilAdditionalBiomass

Motor Fuel

D.J. Stevens, PyNe, 2005

Heat, electricity

8

The Potential Role of PyrolysisThe Potential Role of PyrolysisThe Potential Role of PyrolysisThe Potential Role of Pyrolysis

Part of a Petroleum Refinery Biomass first would be converted to bio-oil, possibly at

distributed locations at small scale Bio-oil can be partially upgraded by catalytic

hydrotreatment at larger scale in proximity of a petroleum refinery

Upgraded bio-oil then would be co-fed with petroleum feedstocks through a catalytic process to produce conventional refinery product slate

The global petroleum industry is showing more interest From the Department of Energy perspective, this is a

medium-term approach

9

Pyrolysis/Petroleum BiorefineryPyrolysis/Petroleum BiorefineryPyrolysis/Petroleum BiorefineryPyrolysis/Petroleum Biorefinery

Distributed Lignocellulosic

Biomass

Upgrading and Refining with Petroleum

Fast Pyrolysis

Products

Motor Fuel

bio-oil transport

10

10

Overall Biorefining Concept

Primary fractionation

and liquefaction

Biomass residues

Co-processing in conventional

petroleum refineryDe-oxygenation

Hydrocarbon-rich fraction

Lignin-rich fraction

ConversionDerivatives of hemicelluloses and celluloses

Conventional fuels and chemicals

Oxygenated products

Energy production

Process residues

(blending)

Yrjö Solantausta, 14.3.2006, VTT

11


Stand-alone facilities Small size makes economics of fuel production difficult May be more appropriate for heat and power

applications High-value specialty chemicals may provide the

economic driver Unlikely to gain strong support from Department of

Energy in the U.S. because of current focus on petroleum displacement, but Department of Agriculture is interested

12

Concept of a BiorefineryConcept of a BiorefineryConcept of a BiorefineryConcept of a Biorefinery

D. Radlein, Fast Pyrolysis Handbook, 1999

Pyrolyzer

Fuel Gas

Char Converter

Bio-oil

Ash Activatedcarbon

Biomass Anhydrosugars

Hydrolysis & Fermentation

Reaction

Reaction

Reaction

Separation

Separation

Catalytic Reforming

NH3

lime

alcohol

water

Ethanol

Slow Release Fertilizers(N, Ca, Zn, Fe ...)

Noxolene™(NOx reduction)

BioLime™(NOx/SOx reduction)

Fuel EnhancersFlavor ChemicalsChemicalsFlavors

Adhesives

Diesel/boiler FuelSpecialty

Synthesis GasHydrogen

Biomass Refinery ConceptD. Meier

Biomass

Fractionation

FibersCellulose

HemicelluloseLignin

direct use

•in situ treatment•post treatment

direct use

PHENOLS

alcoholswater (NCW, steam)

14

Biomass Refinery ConceptBiomass Refinery ConceptD. MeierD. Meier

Biomass Refinery ConceptBiomass Refinery ConceptD. MeierD. Meier

Biomass

Fractionation

FibersCellulose

HemicelluloseLignin

direct use

•in situ treatment•post treatment

direct use

PHENOLS

alcoholswater (NCW, steam)

15

BIOREFINERY CONCEPT

Fast pyrolysis

Wet fuelsMixed fuels

Woody biomass

waste wood, Acacia bark, agro-biomasses, constr. wood

ExtractivesSolvent

extraction Biodiesel

Aqueous phaseSteam

reformationH2 for fuel cells

Lignin phase Alcohol addition, solids removal

Fuel oils,Diesel fuels

Hydrolysis, fermentation

Bio-ethanol for fuel cells

Thermal cracking/Catalytic

hydrotreatment

Char Process energy

Steam activation

Activated carbon

Optional hydrolysis

Lignans

Anja Oasmaa, 2005, VTT

Forschungszentrum Karlsruhe in der Helmholtz-Gemeinschaft

ITC-CPV HEFW

FW

fast pyrolysis

biomass preparation

liquid fuel synthesis

rail transport from many pyrolysis plants

to large, central plant for syngas generation and use

entrained flow gasification

gas cleaning

electricity generation

Different biomass and carbon feedstocks

bio-oil/char -slurry

lignocellulosic biomass:wood, straw, hay ....fossil

fuel:

other biomass:

coal ...starch, oil ...

pulverised coalcoal/water slurry

organic waste:paper, plastics, dung ...

synthesis products:synfuel, chemicals, H2

electricity

low Theat

O2

CO2

specialchemicals

17

SummarySummarySummarySummary

Numerous opportunities involving: incorporation into sugar biorefinery incorporation into a petroleum refinery stand-alone with chemical, fuel, and power production incorporation into a gasification and synthesis plant

Pyrolysis demonstration will lead to biorefineryProduct separation and recovery is a major hurdleFinding the right niche is key


Progress in BiorefineryCase studies

Max Lauer and Doug ElliottSeptember 20, 2006

19


Part of a sugars-based biorefinery based on residue pyrolysis for fuel and, perhaps, products

Part of a Petroleum Refinery with distributed production and centralized processing

Stand-alone facilities with distributed production and centralized processing and refining or true stand-alone with or without fractionation and product processing

Incorporation into a gasification and chemical/fuel synthesis plant

20

TEA of Pyrolysis BiorefineryTEA of Pyrolysis BiorefineryTEA of Pyrolysis BiorefineryTEA of Pyrolysis Biorefinery

What process concept (or concepts?) Single concept in depth, or Comparison of several concepts

Technical or Technoeconomic Detailed mass and energy balance only, or M&E balance to allow capital & operating cost estimate

What methods?

What level of detail?

21

Biorefinery Concepts to be EvaluatedBiorefinery Concepts to be EvaluatedBiorefinery Concepts to be EvaluatedBiorefinery Concepts to be Evaluated

The following institutions agreed to provide the relevant information for the concepts listed below, and these would form the basis of an evaluation exercise. USDA - compare pyrolysis to combustion in ethanol plants IWC – pre-separation concept and pyrolyse products (lignin), maximise by-products and chemicals from the process, particularly phenolsFZK – bio-slurry gasification + synthesis PNNL - Distributed pyrolysis to central refinery for upgrading and integrationBTG – direct gasification of bio-oil in existing gasifier + synthesisAston – Speciality chemicals and fuelsRodim – Chemicals and animal pharmaceuticals and fertiliserJR - Pyrolysis + CHP stand-aloneECN – comparison with biomass gasification routes

22

Biorefinery Concepts to be EvaluatedBiorefinery Concepts to be EvaluatedBiorefinery Concepts to be EvaluatedBiorefinery Concepts to be EvaluatedChemicals as primary product

IWC – pre-separation concept and pyrolyse products (lignin), maximise by-products and chemicals from the process, particularly phenolsAston – Speciality chemicals and fuelsRodim – Chemicals and animal pharmaceuticals and fertiliser

Fuels as primary productFZK – bio-slurry gasification + synthesis BTG – direct gasification of bio-oil in existing gasifier + synthesisECN – comparison with biomass gasification routesPNNL - Distributed pyrolysis to central refinery for upgrading and integrationUSDA - compare pyrolysis to combustion in ethanol plants JR - Pyrolysis + CHP stand-alone

TemplateBlock flowsheet starting with biomass input – maybe as bio-oil, using all

products in some way and minimising waste productionOutline mass balance through „blocks“Capital costsProduct costs

23

Biorefinery Concepts to be EvaluatedBiorefinery Concepts to be EvaluatedBiorefinery Concepts to be EvaluatedBiorefinery Concepts to be EvaluatedChemicals as primary product1. Speciality chemicals and/or separation of biomass

componentsTransport fuels as primary product2. Bio-oil for transport fuels via gasification and FT and/or

methanol 3. Bio-oil (hydro) de-oxygenation for transport fuels Reference case4. Power and heatProcessa. Template for specifications and bio-oil costsb. Block flowsheet starting with biomass (industrial sawmill

waste ISW) input, using all products in some way and minimising waste production, to give end products

c. Outline mass balance through „blocks“. Size d. Capital costse. Product costsHow and when?Small working groups, Email, Draft (a) & (b) & (c) by end 2006 to

DCESmall meetings if needed(d) & (e) TBD but NOT after next TNet meetingGroup meeting 2007FT 20,000bbl/d=3000t/dBiomass 2,000t/d = 660,000t/y

AU, IWC, UN, USDA

ECN, FZK, BTG, VUT,

PNNL, VTT, UT, AU, CF

JR, NTNU, UF, USDA

@ JRDefine ISW @ JR

24

Biorefinery Concepts to be EvaluatedBiorefinery Concepts to be EvaluatedBiorefinery Concepts to be EvaluatedBiorefinery Concepts to be Evaluated

FACTSFT single train 20,000bbl/d = 3000t/d diesel = ca 12,000t/d biomassUSA Biomass 2,000t/d = 660,000t/yEU Biomass 300 t/d = 100,000 t/yChoren planning 1,000,000 t/y for gasification + FT

SIZE OF BIOMASS PROCESSING PLANTS for considerationSmall = 200 t/d input dry biomassLarge = 2000 t/d input dry biomass = 400 MWth input = 160 MWe

SIZE OF intermediate fuel products dependent of biomass input, e.g. partially refined product to refinery

SIZE OF FT12,000 bbl/d output diesel productionUpgraded bio-oil hydrotreater = 6000 bbl/d diesel = 800 t/d diesel


Round Robin on Lignin Pyrolysis

Dietrich Meier and Doug ElliottSeptember 20, 2006

26

Round RobinRound RobinRound RobinRound Robin

Participants Which laboratories? list of potential participants at Lille

Feedstock requirements What kind? many potential sources How much? depends on the laboratory method

Time line Acquire feedstock Distribute feedstock Perform tests Collect data Submit report

27

Potential Round Robin ParticipantsPotential Round Robin ParticipantsPotential Round Robin ParticipantsPotential Round Robin Participants

Laboratory ProcessAston University Fluid bed, TGA, Py-GCMSForschungszentrum Karlsruhe (FZK) Fluid bed, screw feedECN Fluid bedUniversity of Napoli BatchUniversity of Twente Fluid bedUSDA-Eastern Regional Research Center Fluid bed, TGABFH-Institute for Wood Chemistry Fluid bed, EFNational Renewable Energy Lab (NREL) Fluid bed

Pacific Northwest National Lab (PNNL) Analytical, TGA, Fluid bedVTT-Technical Research Centre of Finland Py-GC-AEDCIRAD-Forêt AnalyticalInstitut Français du Pétrole (IFP) TGA, Analytical,

28

Potential Round Robin ParticipantsPotential Round Robin ParticipantsPotential Round Robin ParticipantsPotential Round Robin Participants

Lab Process

Aston Fluid bed (150, 300, 1000g/h), TGA (10mg), Py-GCMS (0.1mg)FZK Fluid bed, screw feed (10000g/h)ECN Fluid bed (Napoli Batch, fluid bed (10g?)Twente Fluid bed (1000g/h)USDA Fluid bed (1000g/h), TGA

BFH Fluid bed (150, 5000g/h), PyGC (0.1mg), microbatch (20mg)NREL Fluid bed (10000g/h)PNNL Analytical, TGA (10mg), Fluid bed (100g/h)VTT Py-GC-AED (0.1mg)CIRAD Analytical, fluid bed (1000g/h)IFP TGA (10mg), Analytical,

29

Potential Lignin Sources for Potential Lignin Sources for Round Robin Round Robin

Potential Lignin Sources for Potential Lignin Sources for Round Robin Round Robin

MeadWestvaco Indulin AT – precipitated Kraft lignin (softwood)

Lignol (Alcell) Organosolve lignin Variable biomass source potential

IOGEN EtOH residue (straw lignocellulosic)

International Lignin InstituteOthers Sigma Aldrich (sulfur-free) Borregard (kraft lignin or lignosulfonates, both with sulfur) STFI (Swedish pulp & paper institute), kraft lignin

30

Lignin SourceLignin SourceLignin SourceLignin Source

MeadWestvaco www.meadwestvaco.com pulping lignin products several grades

sulfonated Kraft lignins – REAX and KRAFTSPERSE sulfonated sulfite lignin – POLYFON unsulfonated Kraft lignin – Indulin

- AT: 5% moisture, 6.5 pH (15% aq) 3% ash, 97% lignin - C: 5% moisture, 10.2 pH (15% aq)

commercial products, readily available in most quantities

31


Lignol (Alcell process) – Bridgwater/Elliott organosolve hardwood lignin Michael Rushton, Vancouver, BC, Canada kilogram quantities available signed agreement by each researcher

no third party distribution no publication without permission – source attributed no chemical analysis without permission – data shared inform Lignol of patenting efforts involving Lignol lignin joint ownership of jointly developed IP mutual confidentiality recipient pays cost of shipping, duties, etc.

many potential biomass types in the future

32


Iogen – Elliott ligno-cellulosic EtOH residue Ron R. Paradis, VP EtOH and Byproduct Marketing not responsive

33


ENEA-Trisaia -- Chiaramonti steam explosion, alkali extracted, acid precipitated Dr. Braccio and Dr. Zimbardi 1 kg lignin available for round robin tests

they would ship the lignin they would like to know some details like what kind of

tests and who would carry them out

34


Abengoa – Prins biorefinery residue Viorel Duma, Chesterfield, MO, USA a few hundred kilos available at a time start up this winter 30% dry solids (could be treated (?) to reduce moisture

for pyrolysis) lignin content of 60%, balance fiber and ash less interesting alternative -- dry purified lignin product

35


Aldrich Chemical www.sigma-aldrich.com Several grades, commercially available

low sulfonate, alkali $0.30-0.40/g hydrolytic $1.20-1.60/g organosolve $0.60-1.00/g

100s of gram quantities

36


Lignoboost -- Meier/Elliott pulping residue lignin Per Tomani, STFI-Packforsk AB, Stockholm sulfur content depends on method, but typically 1-3% several hundred kilos of product available

they need to know more of purpose of testing

37


Swedish Energy Agency – Bridgwater organosolve enzyme acid

38

Other Potential Lignin Sources Other Potential Lignin Sources for Round Robin for Round Robin

Other Potential Lignin Sources Other Potential Lignin Sources for Round Robin for Round Robin

Lignin without sulfur Baltic hydrolysis ILI Genencor enzyme hydrolysis lignin Mondi

Sulfur containing lignin Kraft lignin (Borregard?)

pyne -- glasgow wp 2h biorefinery tony bridgwater and doug elliott september 20, 2006

Documents

biorefineries slide

electricity slide

current biorefinery

succinic acid

small scale biooil

acs mtg

catalytic process

petroleum refinery biomass