Upgrading of pyrolysis oil for application in standardUpgrading of pyrolysis oil for application in standard refineries

Tcbiomass 2009, September 18, Chicago Kees HogendoornGroup of ThermoChemical Conversion of Biomass (TCCB)University of Twente, The Netherlands

BIOCOUP

Conventional fuels and chemicals

ResidualBiomass

SP1 Primary liquefaction

SP 2 De-oxygenationUT

SP 3 Co-processing in petroleum refinery

Oxygenated products

liquefactionVTT UT

SP 4 Recovery of Chemicals(Phenols Aldehydes Acids) TuE

refinery Shell

p(Phenols, Aldehydes, Acids) TuE

www.biocoup.eu for more info on scope and other SP’s

Goal SP2:Goal SP2:

Development of de-oxygenation technology for pyrolysis oil (derived) liquids

● Catalyst development (BIC), screening (RUG, TKK), support testing (Albemarle)

● Product research (RUG, UT)● Reactor development (UT, BTG)● Process development (BTG, UT)● Analysis feed stock and products (VTT, vTI, RUG)● Oil production and demonstration at PDU scale (BTG, UT)

Upgrading and Technologies

Advantages of pyrolysis oil: low ash content

Left wood; Right pyrolysis oillow ash content

‘high’ energy density (biomass)

Why upgrading: negative sides of pyrolysis oil

Right pyrolysis oilBoth 1 MJ

(Photo BTG)

high acidity/reactivity pyrolysis oiltendency of considerable char formation (blocking, catalyst poisoning)high oxygen and water contentmiscibility problems conventional feedssc b y p ob e s co e o a eeds

Technologies studied in SP2- BIOCOUP

HPTT: High Pressure Thermal Treatment 200-400 oC; 1-20 minutes; 50-200 bar

DCO: Catalytic Decarboxylation = HPTT + catalyst

HDO: Hydrodeoxygenation = DCO + Hydrogen 15 min-4 hours !

HPTT and DCO+ Phase separation: oil, aqueous, gas+ Deoxygenation to ~ 25wt% O (dry oil basis) possible+ Substantial energy densification (up to a factor of 2)

rapid! Increase MwHigh Molecular Mass formed during HPTT

Likely cause: Polymerization of ‘sugars’ in pyrolysis oil

This will complicate hydrodeoxygenation/co-processing

Increase of molecular weight: more so with severity

(minimum)

100 1000 10000

DCO similar to HPTT with respect to decarboxylation and polymerization

HDO results

Increasing severity (T, τ):

• Higher H2 consumption (150-Higher H2 consumption (150800 NL/kg feed)

• Higher deoxygenation (<10-40wt% O in dry remaining)75.0

100.0

ry, w

t.%)

100%

120%

C H O Yield organics

• HDO oil yield ~ 40wt%, decreases with severity

• No (substantial) increase in Mw

50.0

com

posi

tion

(dr

60%

80%

ld (w

t.% o

f oil)

Mw

25.0

Elem

enta

l c

20%

40% Yie

Remaining aqueous0.0

0 100 200 300

Hydrogen consumption (Nm3/t)

0%

Data BTG/RUG (packed bed)

Remaining aqueous phase can be used for chemicals extraction (acids: SP4) or hydrogen production

Data BTG/RUG (packed bed)

HDO process insight

Parallel HDO vs Repolymerization reactions

High Molecular Weight Fragments Char

No catalyst - hydrogen

CharringRe-polymerization

No catalyst and/or hydrogen

Pyrolysis oil

y y g≈ min

H2, catalyst HPTT

Hydrotreating

y y g≈ min (150<T<350oC)

Stable FragmentsHDO oil

and aqueous phase

H2, catalyst≈ min

H2, catalyst≈ min .. hours

HydrodeoxygenationStabilization

Adapted figure from BTG/RUG

≈ min at higher severity

Tested in lab scale refinery units (SP3)Feed back to SP2

KEES.HOGENDOORN@UTWENTE.NL

Bio Fuels By Bio Fuels By Biomass Catalytic Cracking

by Paul O’Connor – KiOR

Biomass BCC Bio-FuelsCCMaking it all happen:

A Creative Network 2006-2009

ITQValencia

RFS targets requires strong RFS targets requires strong technologies

EISA renewable fuel(2007) mandatesBilli llBillion gallons per year

1 17 1821 22

9 11 14 167

2630

Biomass diesel

2824 Advanced biofuel

3336

913 14 15 17

3 4 61 1 2

9 11711 Cellulosic biofuel

Renewable biofuel

2009 2010 2011 2012 2013 2014 20152008 20172016 20192018 2020 2021 2022

• By 2022, at least 16 billion gallons of cellulosic capacity must be added to meet EISA goals

Key to meeting  mandates:

• If plants are 50 MM gallons/yr capacity, need 320 plants, or average of  about 25 plants/year

• If average development time for plant is 48 months*, need about 100 plants under development at any given time

•Robust technology• Infrastructure ready productproduct

•Scalable process with rapid rollout* Average total time for pioneer process plants, RAND 1984

Source: Energy Independence and Security Act of 2007, RAND, KiOR analysis

Evolution of Biofuels and Technologies

Vegetable Corn Lignocellulose

Evolution of Biofuels and Technologies

VegetableOil

Corn Lignocellulose

PyrolysisDelignification

Gasification

Fermentation

g

Hydrogenolysis Stabilization BCCF‐T Methanol 

MTG  Upgrading

RefiningEthanol

G pg g

Renewable (Biomass based) Fuels

Geo Thermo BCCMillions of Years Minutes Seconds

1methanol

Millions of Years Minutes Seconds

3/4

cellulose

lignocellulosicbiomass

l i ile

BCC:“One pot”

2/4 hemicellulosesethanol DMEmethyl

levulinate

pyrolysis oil

mol

e/m

ol

pLiquefaction

+De-oxygenation2/4

lignin butanol

ethyllevulinate

hydrothermalli f ti

O/C

, De-oxygenation

1/4

methane hydrogen

lignin

crude oildiesel (FT)gasoline

MTBE

antracitecoal

FAMEFAEE

MTHFliquefactionoil

5

0 1 2 3 4

0

H/C [mole/mole]

methane hydrogen

History repeatingHeavy Oil Conversion (WWII) Biomass?y ( )

Fluid Catalytic Cracking:ll d f l l f

Biomass Catalytic Cracking:F ll i f l i li i f• Followed successful commercialization of 

“topping” refineries•Objective: catalytically convert heavy product to gasoline

l d l ’ l

• Following successful commercialization of ethanol and biodiesel

•Objective: catalytically convert cellulosic biomass to crude substituteD l d 2005 2007 l i• Developed in early 1940’s to solve 

pressing national problem (aviation gasoline for WWII)

• Rapidly scaled up (<4yrs from idea to d i ) d hi hl f l

• Developed 2005‐2007 to solve pressing problem (domestic, green source of fuel)

•…In process of scaling up from pilot to demonstration and  first 

production) and highly successful• Platform for continuous improvement for next 50 years

p fcommercial unit

•…Growing world class R&D for continued improvements

leveraging existing technology and leveraging existing technology and infrastructure

BCC reduces technical and scale up risk while reducing market risk and roll outBCC reduces technical and scale up riskby leveraging existing refining and solids handling equipment….

… while reducing market risk and roll out costs by using existing infrastructure to make existing products

Bio Crude

Core equipment based on FCC technology• Robust conversion technology, over 60 years

Biomass feed

High quality oil processed in existing refineries:• Non corrosive miscible withoperating history

• Well known scale up and cost• Solid catalyst handling – minimal retrofit for

biomass feed

• Non-corrosive, miscible with refining process streams

• Easily refined into on-spec gasoline diesel and jet fuel with low sulfur, no heavy metals

SummarySummary

• BCC produces low oxygen content stable oils suitable for refinery processing into liquid transportation fuelsrefinery processing into liquid transportation fuels.

• BCC can convert solid biomass (500-2000tpd) in distributedBCC can convert solid biomass (500 2000tpd) in distributed local units, while the stable oil produced can be upgraded in existing large scale refineries (economy of scale).

• BCC can be scaled and commercialized fast based on existing extensive FCC technology experienceextensive FCC technology experience

• BCC can compete economically with fossil fuels.

• BCC can handle all types of feed stocks (Straws, Algae,…).

Progress in Bio‐oil Upgrading atMi i i i St t U i itMississippi State University

Philip SteelePhilip Steele

Professor and SERC 

Bio‐oil Thrust LeaderBio‐oil Thrust Leader

Sustainable Energy Research Center

Mississippi State UniversityMississippi State University

MSU proprietary HDO catalyst produces a high‐quality hydrocarbon mix:quality hydrocarbon mix:

Hydrogen

Removal of oxygen

Hydro‐CO H OHydrogen +HT catalyst

Water

Hydro‐carbons

‐ CO2 + H2O

HDO bio‐oil

Water

Bio‐oil

Current HDO bio‐oil quality: 

Paraffins&

PNA's11%

iso-paraffins

36%

Aromatics17%

Napthenes 100 % U d d

p36% Upgraded 

HDO

Properties of HDO bio‐oil vs diesel:

P t HDO bi ilProperty HDO bio-oil

Water content (wt%) 0

Acid value (mg KOH/g) ~0 13Acid value (mg KOH/g) ~0.13

HHV (MJ/kg) 45.5

Oxygen (%) <0.1

FTIR spectra comparison of jet fuel, gasoline and HDO bio‐oil: 

180Raw Bio oil HDO Diesel Gasoline

120

140

160

ce

80

100

120

nsm

itta

nc

40

60

% t

ran

0

20

1000125015001750200022502500275030003250350037504000

5

1000125015001750200022502500275030003250350037504000

wavenumber cm-1

Simulated distillation of jet fuel, gasoline and HDO bio oil:and HDO bio‐oil:

700

500

600

e (F

)

Jet fuel Gasoline HDO bio-oil

200

300

400

Tem

pera

tur

0

100

200T

00 10 20 30 40 50 60 70 80 90 100

Distilled (%)

6

Mild Hydrotreating of Pyrolysis OilMild Hydrotreating of Pyrolysis Oil

Robert M. BaldwinPrincipal Scientist and Group

ManagerThermochemical Process R&D and

Bi fi A l iBiorefinery Analysis

tctcbiomassbiomass20092009

NREL is a national laboratory of the U.S. Department of Energy Office of Energy Efficiency and Renewable Energy operated by Midwest Research Institute • Battelle

Yesterday’s Panel Discussions

Q: Role of R&D community in developing andQ: Role of R&D community in developing and accelerating commercial deployment of pyrolysis oil?

p oil as a commodit• py-oil as a commodity• quickest path to commercial acceptance: take

advantage of existing fossil fuel infrastructure• engage refining industry in R&D activities

National Renewable Energy Laboratory Innovation for Our Energy Future

Integration with Refining Infrastructure

Bio-Crude from Biomass PyrolysisIntegration with Existing Refining Infrastructure

P l iBio-Crude Fuels

andBiRefining

Pyrolysis andChemicalsBiomass Infrastructure

Improve oil quality-Stabilize oil by partial

di- Improve oil qualityby catalysis- Produce bio-oils with lowash (hot-gas filtration)

upgrading- Reduce oxygen content and acidity-Build molecular structure

National Renewable Energy Laboratory Innovation for Our Energy Future

Effect of Economies of Scale

40

45

25

30

35

Cos

t ($/

bbl)

0 2% O

10

15

20

Upg

radi

ng C 0.2% O

7% O

0

5

1000 10000 100000 1000000

U

C it (bbl/D)

7% O

Capacity (bbl/D)2000 MTDDry Wood

$4-6/bbl total upgrading costs for conventional refining

Source: Global Energy Management Inst. (GEMI), U Houston, 2009

Biofuels: Refinery Integration Strategies

National Renewable Energy Laboratory Innovation for Our Energy Future

Global Energy Management Institute Study

NREL/GEMI Study

“Alternate Value Chains for the Manufacture, Upgrading and Transport of Pyrolysis Oil to

Conventional Petroleum Refineries”Conventional Petroleum Refineries

National Renewable Energy Laboratory Innovation for Our Energy Future

Primary Conclusions: Cost Drivers

• Improved oxygen removal during pyrolysis (CFP)p yg g py y ( )• Partial upgrading• Improved HDO catalysts (selective oxygen

removal)• Multi-stage HT with interstage aromatics removal

Use of aqueous phase reforming for manufacture• Use of aqueous phase reforming for manufacture of H2

Combined effect on upgrading costs:$47/bbl → $14/bbl

Value Chains: GEMI

Lowest cost case:1) Centralized pyrolysis facility located near

refinery with XS H22) Upgrading to ~7 % oxygen3) Blend 7/1 (v/v) with low-TAN crude (<0.2)

• Gives feed of TAN = 2 oxygen = 0 9 wt%• Gives feed of TAN = 2, oxygen = 0.9 wt%4) Co-process with crude oil in refinery

• Requires “armored” metallurgy in refinery• Cost may be partially offset by low sulfur content of

pyrolysis oil

National Renewable Energy Laboratory Innovation for Our Energy Future