Institute of Wood Technology and Wood Biology (HTB), Hamburg, Germany

Life-Cycle Assessment of the LifeBi BiomassBiomass -To T -Oil (BTO®) Process ToP with ith Combined Heat and Power (CHP) Generation tcbiomass 2009, 16-18 September 2009 Chicago, g , IL,, USA Axel Faix*, Jörg Schweinle****, Stefan Schöll***, Gero Becker*, Dietrich Meier**** *

Albert-Ludwigs-Universität, Faculty of Forest and Environmental Sciences, Institute of Forest Utilisation and Work Science, Freiburg im Breisgau, Germany ** Johann Heinrich von Thünen-Institute (vTI), Institute of Forest Based Sector Economics, Hamburg, Germany *** PYTEC Thermochemische Anlagen GmbH, Lüneburg, Germany **** Johann Heinrich von Thünen-Institute (vTI), Institute of Wood Technology and Wood Biology, Hamburg, Germany

Contents „

A quick look at LCA

„

BTO system description

„

Data bases

„

Effi i Efficiencies i

„

Moisture content, a key issue

„

Environmental impact

„

Conclusions

Institute of Wood Technology and Wood Biology (HTB)

LCA - Basics

„

Definition –

Compilation and evaluation of the inputs, outputs and the potential environmental impacts of a product system throughout ist life cycle

„

Improved transparency

„

G i more insight Gain i i ht iinto t materials t i l and d energy flflows

„

Define hot spots p for improvements p

„

Environmental indicators (impacts)

Institute of Wood Technology and Wood Biology (HTB)

Stages of an LCA LCA framework

DIN EN ISO 14040:2006; 14044:2006

Goall and G d scope definition

Inventory analysis

Interpretation

Impact assessment

Institute of Wood Technology and Wood Biology (HTB)

• Product development and improvement • Strategic planning • Public policy making • Marketing • Other

Elements of the Life Cycle Impact Assessment phase

Selection of impact categories, category indicators and characterization modules

Assignment of LCI results (classification)

C l l ti off category Calculation t iindicator di t results lt ((characterization) h t i ti )

Category indicator results, results LCIA results

Institute of Wood Technology and Wood Biology (HTB)

Nomenclature „

GWP100: Global Warming Potential is a measure of how much a given mass of

greenhouse gas is estimated to contribute to global warming in 100 years. It is a relative scale, which compares the gas in question to that of the same mass of carbon dioxide (whose GWP is by definition 1) 1).

„

ODP: The ozone depletion potential of a chemical compound is the relative amount of degradation to the ozone layer it can cause, with trichlorofluoromethane (R-11 or CFC-11) being fixed at an ODP of 1.0.

„

POCP: Photochemical ozone creation potential is referred to in ethyleneequivalents (C2H4-equ.). It is important to remember that the actual ozone concentration is g y influenced by y the weather and by y the characteristics of the local conditions. strongly

„

EP: Eutrophication is the enrichment of nutrients in a certain place. Eutrophication can be aquatic or terrestrial. Air pollutants, wastewater and fertilization in agriculture all contribute to p The eutrophication p p potential is calculated in p phosphate p equivalents q ((PO4 Eq) q). eutrophication.

„

AP: The acidification potential of soils and waters occurs predominantly through the transformation of air pollutants into acids. The acidification potential is given in sulphur dioxide q ((SO2-Eq.) q ). The acidification ppotential is described as the abilityy of certain equivalents substances to build and release H+ - ions. Certain emissions can also be considered to have an acidification potential, if the given S-, N- and halogen atoms are set in proportion to the molecular mass of the emis-sion. The reference substance is sulphur dioxide.

Institute of Wood Technology and Wood Biology (HTB)

Materials and methods

„

Data from PyTEC y – –

„

Experiments from pilot plant and CHP plant Conservative estimations

Databases – – –

Online „Biobib“ ProBas, HBEFA (German Environmental Agency) Ecoinvent, Switzerland (for supply chains)

„

Software „UMBERTO UMBERTO 5“ 5 (ifu, (ifu Germany)

„

Impact analysis (University Leiden, NL)

Institute of Wood Technology and Wood Biology (HTB)

Scheme of the 6 tpd BTO® pilot plant

Institute of Wood Technology and Wood Biology (HTB)

System description Emissions

Emissions

Fuels

Transportation energy

Reference

Emissions

Emissions

Emissions

• • • •

• • • •

• Condensation • CHP • Oil condit condit. • DeNOx • Additive admixing

Push floor Impurities Drying Conveying

Diesel transport, di t distance 35 kkm Fuels and emissions

Pyrolyzer Char manag manag. Gasifier Gas condit.

Bio-oil transport, distance 120 km Fuels and emissions

Institute of Wood Technology and Wood Biology (HTB)

Emissions

Scheme of the planned 48 tpd BTO® plant in Malliß, construction started in 2008 Storage wood chips y Dryer

T Transformers f

Storage material Gasifier

Storage tanks

Storage char coal Pyrolyser

8 x CHP Pyrolyser Office

Control room

Product recovery y Washroom Institute of Wood Technology and Wood Biology (HTB)

Product treatment

Malliß plant key data

„ „ „ „ „

Throughput Drying energy Production Final moisture Char for energy

48 t/day 1.1 kWhth/kg H20 1200 L/h 12 % 64 %

„

Yields – – –

„

– – – –

Efficiency: Effi i 41 % (Ref. (R f 36 %) Rating with diesel: 450 kWel Rating with bio-oil: 315 kWel Diesel consumption: 0.205 kg/kWhel Bio-oil consumption: 0.506 kg/kWhel

CHP – –

Institute of Wood Technology and Wood Biology (HTB)

70 m% 25 m% 6 m%

Motor –

„

Crude oil: Gas: Char:

Efficiency: 76 % (Ref. 81 %) Exhaust gas cleaning: Adblue®

Supply chains and consumptions

„ „ „ „ „

Forest production Fossil and regenerative energy carriers Additives El t i it Electricity Ammonia

Institute of Wood Technology and Wood Biology (HTB)

„ „ „

Electricity Additives Water

UMBERTO flow model of the BTO® process Fossil fuels Forest production

German energy mix Pyrolyzer

Transport

Technical process

Push floor Impurities Drying removal

Conveyer Char manag.

Connection to process Gas mixing Burner

Emissions

Gasifier Gas cond. Condenser

Inputs

CHP

S Supply chains

Oil transp transp. Oil manag.

D NO De-NOx

Institute of Wood Technology and Wood Biology (HTB)

Additives

Supply chains: forest production, fuel, and power

Institute of Wood Technology and Wood Biology (HTB)

Supply chain oil upgrading

Institute of Wood Technology and Wood Biology (HTB)

Exhaust gas components from diesel engine at different bio--oil / additive ratios bio

bio-oil / additive

Unit

80 / 20

91 / 9

100

O2 (0 %O2)

%

97 9.7

13 4 13.4

82 8.2

CO2 (0 %O2)

%

8.3

5.6

9.5

CO (0 %O2)

ppm

1576

956

711

NOx (0 %O2)

ppm

1689

847

1056

Exhaust g gas temp.

°C

268

266

327

Institute of Wood Technology and Wood Biology (HTB)

Emission factors for truck transport (g/kmkg)

pollutants

in town

out of town

Autobahn

weighted mean

0.91% 0 91% empty full load

63.70% 63 70% empty full load

35.40% 35 40% empty full load

100% empty full load

CO2 964.9133 1725.1455 engine fuel 303.9097 543.3529 NO NOx 9 7952 9.7952 15 2302 15.2302 CO 2.5564 4.0446 HC 0.6410 0.8016 NMHC* 0.6256 0.7824 Particulates 0 2912 0.2912 0 4008 0.4008 CH4 0.0154 0.0192 N 2O 0.0084 0.0084 Benzene 0.0107 0.0134 NH3 0 0050 0.0050 0 0050 0.0050 SO2 0.0049 0.0087 Xylene 0.0051 0.0064 Toluene 0.0021 0.0026

607.8923 191.4622 5 7389 5.7389 1.3054 0.2874 0.2805 0 1479 0.1479 0.0069 0.0077 0.0048 0 0050 0.0050 0.0031 0.0023 0.0009

*non-methane non-methane hydrocarbons

Institute of Wood Technology and Wood Biology (HTB)

1079.2810 626.5937 992.7440 339.9310 197.3523 312.6753 9 0890 9.0890 5 2222 5.2222 8 0073 8.0073 1.6999 1.2573 1.3926 0.2926 0.3328 0.3149 0.2856 0.3248 0.3073 0 1705 0.1705 0 1543 0.1543 0 1609 0.1609 0.0070 0.0080 0.0076 0.0077 0.0059 0.0059 0.0049 0.0056 0.0053 0 0050 0.0050 0 0050 0.0050 0 0050 0.0050 0.0054 0.0032 0.0050 0.0023 0.0027 0.0025 0.0009 0.0011 0.0010

617.7522 194.5676 5 5838 5.5838 1.2998 0.3067 0.2999 0 1514 0.1514 0.0074 0.0071 0.0051 0 0050 0.0050 0.0031 0.0025 0.0010

1054.5121 332.1298 8 7619 8.7619 1.6124 0.3051 0.2978 0 1692 0.1692 0.0073 0.0071 0.0051 0 0050 0.0050 0.0053 0.0024 0.0010

Consumption of feestock, rawraw- and ancillary materials, and energy (scaled to 1 MWhel production), excluding supply chain

Material Feedstocks

Mass

Unit

Pine chips Raw and ancillary materials Water Additive A SRC-solvent Additi B Additive Energy

658.42 kg

Diesel fuel Electric power

2.13 2 13 kg 122.86 kWh

Institute of Wood Technology and Wood Biology (HTB)

65.84 36.59 35.45 1 98 1.98

kg kg kg k kg

Consumption of electric power of BTO® process steps (in kWh scaled to 1 MWhel production) excluding supply chains

Process

Consumption

%-Portion

Pyrolysis Condensation

67.6 16.1

55.0 13.1

Gasifier Conditioning of bio-oil D i off wood Drying d Push floor feeder DeNOx

13.4 6.4 49 4.9 3.6 3.3

10.9 5.2 40 4.0 3.0 2.7

3.3 2.7 14 1.4

2.7 2.2 12 1.2

Gas conditioning Separation of impurities C Conveyer Institute of Wood Technology and Wood Biology (HTB)

Emissions (in kg) from transport BTO vs. reference plant (in kg) scaled to 1 MWhel production), excluding supply chains BTO 9.5616343

Diesel 0.5293823

0.0817805 0.0176549

0.0045138 0.0009629

0.0037685 0.0019515 0.0000927 0.0000747 0.0000645 0.0000537

0.0001956 0.0001023 0.0000048 0.0000035 0.0000033 0.0000026

Sulphur dioxide Xylene

0.0000482 0.0000309

0.0000027 0.0000016

Toluene

0 0000123 0.0000123

0 0000006 0.0000006

Total

9.6671667

0.535176

Carbon dioxide, fossil NOx Carbon monoxide, fossil NMVOC Particulates Methane Nitrous oxide Benzene Ammonia

Institute of Wood Technology and Wood Biology (HTB)

Emissions (in kg) from power production BTO vs. reference plant (in kg scaled to 1 MWhel production), excluding supply chains BTO Carbon dioxide, fossil Carbon monoxide, fossil Carbon dioxide, 0.8390635171 biogenic NO NOx 0 0069552338 0.0069552338 Carbon monoxide, 0.0045299686 biogenic Dust Nitrous oxide Methane NMVOC Sulphur dioxide Burner Carbon dioxide, biogenic Wood drying Vapour TOTAL

0.000421197 0 000421197 0.000030672 0.000030672

Diesel 0.7433796 0.002099124

0 001614708 0.001614708

0.000419832 0 000419832 0.0000306796 0.0000306796 0.0000306796 0 000773676 0.000773676

0.3673101742 0.9637003332 2.1820417679

Institute of Wood Technology and Wood Biology (HTB)

0.7483789788

Energetic efficiency related to moisture content including all supply chains

60

En nergetic Effficiency in n%

50

el Energy

40

th Energy

30

Total energy efficiency

20

LHV in bio-oil

10 0 -10 10

12

18

23

28

32

36

39

42

45

47

49

51

53

-20 Moisture Content in %

Institute of Wood Technology and Wood Biology (HTB)

55

57

58

60

61

Relationship between moisture content and available external CHP plants 9

120

8 100

Number o of CHP plan nts

7

Number of external CHP plants

6

Available th energy (%)

80

5 60 4 40

3 2

20 1 0

0 12 18 23 28 32 36 39 42 45 47 49 51 53 55 57 58 60

Moisture content in %

Institute of Wood Technology and Wood Biology (HTB)

%

Wood chips transport or biobio-oil transport ?

1 3E-04 1,3E-04 1,1E-04

Wood chips

Energy consumption per MJ of transported energy and km [MJ / MJ*km]

9,0E-05

Bio-oil 7,0E-05 5,0E-05 3 0E-05 3,0E-05 1,0E-05 12 18 23 28 32 36 39 42 45 47 49 51 53 55 57 58 60 61

Moisture content in (%)

Institute of Wood Technology and Wood Biology (HTB)

Influence of additive „A“ portion on environmental impacts

Changes of e C environmenttal impac ct in %

25 20 15 10 5 0

3

4

5

6

7

8

9

10

POCP

0,0

3,3

6,5

9,8

13,1

16,4

19,6

22,9

EP

0,0

2,8

5,6

8,4

11,2

14,1

16,9

19,7

ODP

0,0

2,3

4,5

6,8

9,1

11,3

13,6

15,9

AP

0,0

2,2

4,5

6,7

9,0

11,2

13,5

15,7

GWP

0,0

1,1

2,2

3,4

4,5

5,6

6,7

7,9

Additive "A" fraction in %

Institute of Wood Technology and Wood Biology (HTB)

Influence of Adblue® admixing on environmental impacts

Changes of environmen C ntal impa act in %

12,0 10,0 , 8,0 6,0 4,0 2,0 0,0

3

4

5

6

7

8

9

10

GWP

0,0

1,5

3,0

4,5

6,0

7,5

9,0

10,5

AP

0,0

0,8

1,5

2,3

3,1

3,8

4,6

5,4

EP

0,0

0,5

1,0

1,5

2,0

2,5

3,0

3,5

POCP OC

00 0,0

06 0,6

12 1,2

18 1,8

24 2,4

29 2,9

35 3,5

41 4,1

ODP

0,0

0,0

0,0

0,0

0,0

0,0

0,0

0,0

AdBlueØ-Admixing in %

Institute of Wood Technology and Wood Biology (HTB)

Environmental impact in %

Relative environmental impacts for POWER & HEAT production with the BTO® process vs. the reference system (0 %)

150 100

Reference: diesel CHP

50 0 GWP

EP

AP

POCP

-50 -100 -150 Impact categories according to CML

P Power production d ti

Institute of Wood Technology and Wood Biology (HTB)

H t production Heat d ti

ODP

Conclusion (1)

„

The electrical energy efficiency has to be considered differentiated. Although only renewable resources are used the conversion from wood chips to bio-oil requires energy.

„

The electrical energy consumption is in the range of 20 % after considering the use of primary energies and the intrinsic energy consumptions. Comparable biomass-based systems have similar data.

„

Without considering the primary and intrinsic energies the efficiency increases to approximately 30 %.

„

The thermal energy efficiency is further stressed by the drying of the wood chips to 12 %, as this is a requirement for a good bio-oil bio oil quality. quality

Institute of Wood Technology and Wood Biology (HTB)

Conclusion (2) „

The energy efficiency of the transport processes is only favorable for the BTO® system if the water content of the chips were below b l 25 %. % H Hence, air-drying i d i off th the wood d would ld b be beneficial.

„

Heat production from biomass requires relatively high transportation efforts and costs. The conversion of solid biomass to transportable and storable liquid would be beneficial if the distance between biomass production and energy consumption ti iis llarge enough. h Thi This mustt b be calculated l l t d on a case-by-case basis.

„

All impact categories (except EP) have a positive environmental effect

„

The use of agricultural g based additives has a negative g effect on the eutrophication impact category

Institute of Wood Technology and Wood Biology (HTB)

Envergent Biofuel Technology and Life Cycle Assessment Tom Kalnes UOP LLC, a Honeywell Company Geoff Hopkins, Envergent, a Honeywell Company Mark Reno UOP LLC, a Honeywell Company David Shonnard Michigan Technological University 2009 International Conference TC Biomass Conversion Science September 16 - 18, 2009 Chicago, Illinois © Envergent Technologies 2009

ENV 5233-01

Presentation Overview • Introduction • Envergent Technologies LLC • RTP™ Rapid Thermal Processing • Commercial Applications • Life Cycle Assessments

• Fossil Fuel Substitution • Conversion to Transportation Fuel • Technology Benefits & Summary

ENV 5233-02 © Envergent Technologies 2009

Envergent Technologies LLC – UOP / Ensyn Joint Venture • Formed in October 2008 • Provides pyrolysis oil technology for fuel oil substitution and electricity generation • Channel for UOP R&D program to upgrade pyrolysis oil to transportation fuels

• Leading process technology licensor~$2 billion in sales, 3000 employees • Co-inventor of FCC technology • Modular process unit supplier • Global reach via Honeywell & UOP sales channels

• Over twenty years of commercial fast pyrolysis operating experience • Developers of innovative RTPTM fast pyrolysis process • Eight commercial RTP units designed and operated

Second Generation Renewable Energy Company – Global Reach © Envergent Technologies 2009

ENV 5233-03

Rapid Thermal Processing (RTPTM) Technology Pyrolysis Oil

Solid Biomass

Commercially Proven Patented Technology © Envergent Technologies 2009

ENV 5233-04

RTP Operating History & Commercial Experience • Commercialized in the 1980’s • 8 units designed and operated in the US & Canada • Continuous process with >90% availability Plant

Year Built

Operating Capacity (Metric Tonnes Per Day)

Location

Manitowoc Chemical #1

1989

1

Manitowoc, WI, USA

Manitowoc RTPTM – 1

1993

30

Manitowoc, WI, USA

Rhinelander RTPTM – 1

1995

35

Rhinelander, WI, USA

Rhinelander Chemical #2

1995

2

Rhinelander, WI, USA

Rhinelander RTPTM – 2

2001

45

Rhinelander, WI, USA

Rhinelander Chemical #3

2003

1

Rhinelander, WI, USA

Petroleum Demo # 1

2005

300 barrels per day

Bakersfield, CA, USA

Renfrew RTPTM – 1 (Owned and operated by Ensyn)

2007

100

Renfrew, Ontario, Canada

Note: design basis for wood based plants assumes feedstocks with 6wt% moisture content.

Significant Commercial Experience © Envergent Technologies 2009

ENV 5233-05

RTP Product Yields 400 BDMTPD of Hardwood Whitewood Feed, wt% Hardwood Whitewood

100

Typical Product Yields, wt% Dry Feed Pyrolysis Oil

70

By-Product Vapor

15

Char

15

Yields For Various Feeds Biomass Feedstock Type

Typical Pyrolysis Oil Yield, wt% of Dry Feedstock

Hardwood

70 – 75

Softwood

70 – 80

Hardwood Bark

60 – 65

Softwood Bark

55 – 65

Corn Fiber

65 – 75

Bagasse

70 – 75

Waste Paper

60 – 80

Cellulosic Feedstock Flexible With High Yields of Pyrolysis Oil © Envergent Technologies 2009

ENV 5233-06

RTP Pyrolysis Oil Properties • Pourable and transportable liquid fuel • High oxygenate content • Contains 55-60% the energy content of crude-based fuel oils • As produced, can be corrosive Comparison of Heating Value of Pyrolysis Oil and Typical Fuels

Fuel

MJ / Litre

BTU / US Gallon

Methanol

17.5

62,500

Pyrolysis Oil (Wood)

21.0

75,500

Pyrolysis Oil (Bark)

22.7

81,500

Ethanol

23.5

84,000

Light Fuel Oil / Diesel

38.9

138,500

Suitable for Energy Applications © Envergent Technologies 2009

ENV 5233-07

Pyrolysis Oil to Energy & Fuels Vision Electricity Production

Biomass

Fuel Oil Substitution

Pyrolysis Oil

Fast Pyrolysis

Refinery

P

P

Transport Fuels (Gasoline, Jet, Diesel)

Ag Residue P

P

Phased Commercialization © Envergent Technologies 2009

Commercially Available in 2012

P

P

Available for Sale

Forest Fiber

ENV 5233-08

Pyrolysis Oil Energy Applications

RTP Unit

Fuel Burner

Heat

Gas Turbine

Electricity CHP

Diesel Engine

Optimized UOP Upgrading Technology

Gasification

Syngas

Fischer Tropsch

Green Gasoline, Green Diesel & Green Jet Hydrocracking/ Dewaxing

• Compatible with specialized turbines • Specialized burner tips improve flame/burning • Convert to steam to use existing infrastructure • Use as a blend in diesel engines • Upgradable to hydrocarbon fuels

Multiple Applications for Pyrolysis Oil, a Renewable Fuel Available Today © Envergent Technologies 2009

ENV 5233-09

Delivery & Scope of Supply • Range of modular units offered

• 100-1000 Bone Dry Metric Tonne per • •

Day (BDMTPD) Smaller units can be considered Design adjusted to meet site specific requirements

• Design based on hardwood whitewood

• If alternate feedstock being processed, unit performance to be re-rated

• Broad modular experience in refining, petrochemical and oil & gas industries

Modular Delivery Provides Faster Execution and Higher Reliability © Envergent Technologies 2009

ENV 5233-10

LCA Study Overview
Conducted to ISO 14040 standards
LCA software employed SimaPro 7.1 Cumulative Energy Demand & IPCC GWP 100a methodologies
Functional unit for comparison = 1 MJ of fuel energy
System boundaries: Raw material extraction (cultivation) through fuel production to fuel combustion (WTW for transportation fuel comparisons)
Primary Focus: Emission of GHGs
Several fuels considered
Conventional fossil fuels
Biofuels from logging residues
Biofuels from short rotation forestry (SRF) LCA study team included: Jiqing Fan, Ph.D. Candidate Matthew Alward, Undergraduate Researcher Jordan Klinger, Undergraduate Researcher Adam Sadevandi, Undergraduate Researcher ENV 5233-11 © Envergent Technologies 2009

Life Cycle Pathway Diagrams Petroleum Gasoline

PyGasoline from Short Rotation Forestry (SRF) Crops

PyGasoline from Logging Residue

Seed Fertilizer Fuel Chemicals

Wood Logging

Extraction of Crude Oil Logging Residue

SRF Farming

Logging Residue Collection Transport of Crude Oil

SRF Transport

Logging Residue Transport PyOil Production

PyOil Production

Hydrogen

PyOil Refining

Consumer Use

PyOil Conversion Process PyGasoline

Hydrogen

PyOil

PyDiesel

PyOil Conversion Process

PyGasoline

PyDiesel

Consumer Use

Consumer Use ENV 5233-12

© Envergent Technologies 2009

Feedstock Cultivation and Harvesting GHG Emissions Logging

Willow

Poplar

Biomass Yield 0.62

odt/ha/yr

11.95

13.50

GHG kg CO2-eq/kg dry Biomass

0.027

GHG Contribution by Process

SRF Crops

0.035

0.044

Logging Residue 0.03 kg CO2 eq/kg Biomass

Residue

0.025 0.02

Total of all Processes Combustion of Diesel Diesel, Low-sulphur Building Machinery

0.015 0.01 0.005 0

GHG Contribution by Process

GHG Contribution by Process

Willow 0.03 0.025 0.02 0.015 0.01 0.005 0.000

Total of all Processes N2O Emissions from N Fertilizer Use CO2 Emissions from Diesel Combustion Ammonium Sulfate, as N, at Regional Storehouse/RER S Diesel, Low-sulphur, at Regional storage/RER S CO2 from Heavy Fuel Oil Combustion Others

Hybrid/Poplar kg CO2 eq/kg Biomass

kg CO2 eq/kg Biomass

0.035

0.050 0.045 0.040 0.035 0.030 0.025 0.020

Total of all Processes Ammonium Nitrate CO2 Emissions from Diesel Combustion N2O Emissions from N Fertilizer Use Single Superphosphate, as P205 Diesel, Low-sulfur Other

0.015 0.010 0.005 0.000 ENV 5233-13

© Envergent Technologies 2009

Pyrolysis Oil Production LCA PyOil Logging Residue

PyOil Willow

PyOil Poplar

Cultivation and Harvesting

2.2

2.6

3.6

Transportation

9.9

1.2

1.2

Pyrolysis

8.6

8.6

8.6

Total

20.7

12.4

13.4

gCO2 eq /MJ

18

2.0

g-CO2 eq/MJ

14 12

1.8 1.6 1.4 1.2

10

1.0

8

0.8

6

0.6

4

0.4

2

0.2

0

0.0 Carbon Dioxide, Fossil

Dinitrogen Monoxide

Carbon Dioxide

Methane, Fossil

g-CO2 eq/MJ

PyOil from Logging Residue PyOil from Poplar PyOil from Willow

16

Other ENV 5233-14

© Envergent Technologies 2009

Pyrolysis Oil vs. Fossil Fuel LCA Comparison of GHG Emissions Cradle to Delivered Energy 120

Energy Extraction GHG Emissions

gCO2 eq/MJ

100 80

Pyrolysis Oil Production foot print similar to other energy alternatives Assumed biomass transport distances

60


200 km for logging residues
25 km for short rotation forest crops

40 20 0 Petroleum Crude Oil

Hard Coal

Natural Canadian PyOil PyOil from Gas Oil Sands from Crude Oil Logging Willow Residues

PyOil from Poplar

Comparison of GHG Emissions Cradle to Delivered Energy, and Burned 120

Life Cycle GHG Emissions

gCO2 eq/MJ

100 80

through combustion

60 40

Pyrolysis Oil Life Cycle foot print Greener than other alternatives
70-88% lower GHG emissions
SOx emissions similar to Natural Gas

20 0 Petroleum Fuel Oil © Envergent Technologies 2009

Hard Coal

Natural Gas

PyOil from Logging Residues

PyOil from Willow

PyOil from Poplar

ENV 5233-15

Conversion to Transportation Fuel Preliminary LCA of Integrated Bio-Refinery (IBR) Complex Spent Air Air Water

H2 Generation Unit

Wastewater Steam

Fuel Utilities Biomass

Rapid Thermal Processing Unit

Pyrolysis Oil Conversion Unit

Gasoline Kerosene Diesel

(Py)Gasoline is Primary Product ENV 5233-17 © Envergent Technologies 2009

Basis: Bench Scale Production* 100

Mixed Wood Corn Stover Poplar

80 wt%

Several Biomass Feeds Processed • Mixed Wood • Corn Stover • Poplar

60 40 20 0 C, wt%

H, wt%

N, wt%

60 Mixed Wood Corn Stover

50 40 30 20 10

t% ,w na te

w ic ,

xy ge

m at A ro

he ne ht

N ap

t%

t% ,w

t% w in , le f

O

ffi n

,w

t% -P ar a

Is o

ffi n Pa ra

* UOP experience in commercial hydroprocessing process scale-up and design

t%

0 ,w

Quality similar to Petroleum Fuel • 99.5+% Hydrocarbon • LHV ~43 MJ/kg • 70% Naphthenes & Aromatics • High Octane Value

O, wt%

O

Liquid Product is a HC mixture of • Gasoline • Kerosene • Diesel

ENV 5233-18 © Envergent Technologies 2009

PyGasoline GHG Emissions by Life Cycle Stage 100 Fuel Combustion Fuel Transportation Fuel Production Transportation of Feedstocks Feedstock Production, RMA Feedstock Chemicals

90

g CO2 eq./MJ

80 70 60 50 40 30 20 10 0 Petroleum Diesel

PyGasoline: Logging Residue

PyGasoline: Poplar

PyGasoline: Willow

Energy Allocation for Co-products © Envergent Technologies 2009

Petroleum Gasoline

ENV 5233-19

PyGasoline GHG Emissions by GHG-Type 100 90

N2O CH4 CO2

g CO2 eq./MJ

80 70 60 50 40 30 20 10 0 Petroleum Diesel

PyGasoline: Logging Residue

PyGasoline: Poplar

PyGasoline: Willow

Energy Allocation for Co-products © Envergent Technologies 2009

Petroleum Gasoline

ENV 5233-20

68-77% Lower GHG emissions Relative to Petroleum Gasoline Summary of Life Cycle GHG emissions in gCO2-eq/MJ PyGasoline Logging Residue

PyGasoline Poplar

PyGasoline Willow

Petroleum Gasoline

Feedstock Chemicals

0

2.1

0.6

0.0

Feedstock Production

2.1

1.9

1.8

6.9

Feedstock Transportation

9.3

1.2

1.2

1.3

Fuel Production

17.0

17.0

17.0

9.3

Fuel Transportation

0.6

0.6

0.6

1.1

0

0

0

72.6

Total

29.0

22.8

21.2

91.2

Savings (%)

68.3

75.0

76.8

Fuel Combustion

Energy Allocation for Co-products © Envergent Technologies 2009

ENV 5233-21

RTP Technology Benefits Economics

• Economic solution • • •

for renewable energy Competitive relative to fossil fuels Leverages existing assets Provides alternate revenue stream

Technical

• Proven application • Feedstock flexibility • Minimal net utilities • Storable product allows decoupling from end user

Environment & Social

• Reduction of greenhouse • • • •

gases and emissions Waste disposal Minimum environmental Impact Agriculture development Employment

Energy Security

• Energy diversification • Reduction of fossil energy requirements

Pyrolysis to Energy Now – Transport Fuels in 2012 © Envergent Technologies 2009

ENV 5233-22

RTP Summary • Commercially proven technology: 8 units designed and operated • Reliable operation with 90+% on-line availability • Designed to maximize pyrolysis oil yield, 70-75 wt% based on hardwood whitewood feed • Cost competitive with fossil fuel oil • Engineering and modular delivery by world-renowned industry leader • Technology for upgrading to transportation fuels expected to be available in 2012

ENV 5233-23 © Envergent Technologies 2009

Questions

ENV 5233-24 © Envergent Technologies 2009

Quality Control in Pyrolysis Oil Production and Use Anja Oasmaa, Technical Research Centre of Finland (VTT), Finland Douglas C. Elliott, Pacific Northwest National Laboratory (PNNL), USA Stefan Müller, Ensyn Corporation, Canada

2

CONTENT Physico-chemical properties of pyrolysis oil t Quality control in pyrolysis oil production and use t Fuel oil specifications for pyrolysis oil t Legislative aspects, REACH in EU t Summary t

3

BIOMASS PYROLYSIS OIL - A COMPLEX MIXTURE OF COMPOUNDS

Microsoft PowerPoint Presentation

Microsoft PowerPoint Presentation

Microsoft PowerPoint Presentation Microsoft PowerPoint Presentation

4 –6 wt-% carboxylic acids 15 –20 wt-% aldehydes, ketones, furans, pyrans, monomeric phenols, etc. 25 –35 wt-% carbohydrates, ‘sugars’ 20 –30 wt-% water

Microsoft PowerPoint Presentation

Microsoft PowerPoint Presentation

20 –25 wt-% pyrolytic lignin, extractives, solids, polymerisation products

Change in composition in ageing Microsoft Slowering the ageing by stabilizationPowerPoint Presentation

4

ACIDS IN BIOMASS PYROLYSIS OILS O

H

H

C

O C C

H

COMPOSITION 2 - 6 wt-% acetic acid < 2 wt-% formic acid < 1 wt-% glycolic acid < 1 wt-% propionic acid < 1 wt-% lactic acid

O

ANALYSIS Amount by Capillary Electro Phoresis (CE) Acidity as Total Acid Number (TAN) or pH

H

H

H O

5

ALDEHYDES AND KETONES IN BIOMASS PYROLYSIS OILS COMPOSITION 5 –10 wt-% 2 –3 wt-% < 5 wt-% 3 –4 wt-% 2 –5 wt-%

hydroxyacetaldehyde hydroxypropanone other aldehydes and ketones furans, pyrans monomeric phenols

ANALYSIS Total amount by solvent fractionation Compound identification by GC-MSD

6

‘SUGARS’IN BIOMASS PYROLYSIS OILS COMPOSITION 3 –6 wt-% levoglucosan < 1 wt-% cellobiosane, cellotriosane 20 –30 wt-% anhydrosugar oligomers ANALYSIS Amount by solvent extraction or BRIX* Compounds by HPLC or GC-MSD with derivatisation

Radlein in PyNe Newsletter 1997 issue 4

* Oasmaa, Anja; Kuoppala, Eeva. Solvent fractionation method with BRIX for rapid characterisation of wood fast pyrolysis liquids. Energy and fuels, 2008, 22 (6), pp 4245 –4248 .

7

WATER-INSOLUBLES IN BIOMASS PYROLYSIS OILS 15 - 20 wt-% pyrolytic lignin < 1 wt-% solids

1 –5 wt-% extractives CH3 - (CH 2)n - CO 2H HOCH2 - (CH 2)n - CO2H

n = 10-30 n = 10-28

COOH

Polymerisation products in aged liquids

8

CHANGE OF COMPOSITION IN AGEING Storage at room temperature 50

Decrease in aldehydes and ketones

Amount, wt % of d.m.

45 40

‘Sugars’

Decrease in ‘sugars’

35

Increase in water-insolubles

30 25

Increase in water Water insolubles

20

Methods to stabilize the oil

15

Aldehydes, ketones, etc.

10 5

Diebold, J. A Review of the Chemical and Physical Mechanisms of the Storage Stability of Fast Pyrolysis Bio-Oils. http://www.nrel.gov/docs/fy00osti/27613.pdf

0 0

1

2

3

4

5

6

7

8

9

10 11 12

Storage time, months Data has been produced by following changes of several softwood and hardwood pyrolysis liquid at room temperature. Ref. Oasmaa, Anja. 2003. Fuel oil quality properties of wood-based pyrolysis liquids. Academic dissertation. Jyväskylä. Department of Chemistry, University of Jyväskylä. 32 p. + app. 251 p.. Research Report Series, Report 99. Doctoral thesis

9

VARIATIONS IN PHYSICAL PROPERTIES

Acidic, pH 2-3 Heating value 14 - 19 MJ/kg (LHV)

Microsoft PowerPoint Presentation

Viscosity between that of light and heavy fuel oils High ignition temperature Density 1.15 - 1.2 kg/l

Norms and standards for fast pyrolysis liquids 1. Round robin test. Oasmaa, Anja; Meier, Dietrich. Journal of Analytical and Applied Pyrolysis., vol. 73 (2005) 2, s. 323 - 334.

10

CHALLENGES FOR QUALITY CONTROL FEEDSTOCK PROCESSING

PYROLYSIS

LIQUID END-USE

BIOMASS

GAS, LIQUID, CHAR

FUEL OIL

Moisture follow-up Fuel analyses

On-line monitoring of gas, water and solids

Specifications

Microsoft PowerPoint Presentation

Microsoft PowerPoint Presentation

Microsoft PowerPoint Presentation

11

Sartorius MA 45 Moisture Analyzer

Microsoft PowerPoint Presentation

PRESENT STANDARDS Moisture DIN 51718 Ash DIN 51719 Volatiles DIN 51720 CHN ASTM D 5373 Sulphur ASTM D 4239 Heating value DIN 51900

NEW STANDARDS CEN/TS 14774 CEN/TS 14775 CEN/TS 15148 CEN/TS 15104 CEN/TS 15289 CEN/TS 14918

CEN/TC 335 developing standards for solid biomass processing and analyses

http://www.biomassenergycentre.org.uk/portal/page?_pageid=77,19836&_dad=portal&_schema=PORTAL

12

13

QUALITY CONTROL –ON-LINE METHODS

t

t

t

t

Water using volumetric Karl-Fischer titration (ADI 2040 with sample dilution) Change in particle concentration using particle counters or high-speed cameras Acidity by TAN and pH may be followed on-line (ADI 2016) Control samples by fixed intervals for laboratory measurements, correlation curves

14

CHARACTERISATION OF FAST PYROLYSIS OILS t t t t

Water extraction -> Water insolubles Fast BRIX methods from aqueous phase -> ’ Sugars’ TAN of aqueous phase, use of correlation curve -> Acids Simple but accurate field test meters available for BRIX sugars Volatile acids

100 90

Aldehydes, ketones

80 Brix

70 60

Ether-insolubles

50 40

Water

30 WIS

20 10

LMM lignin + extractives + pol.product HMM lignin + pol.products

B

-1 2

B

-f re m sh B on -1 th 2 s m -5 on °C B t hs -2 +2 4 ho 2 °C ur s at 80 °C

A

A

-1 2

A

-f re m sh on -1 th 2 s m -5 on °C A t h -2 s +2 4 ho 2 °C ur s at 80 °C

0

Follow up of main changes in chemical composition during oil production or storage Oasmaa, Anja; Kuoppala, Eeva. Solvent fractionation method with BRIX for rapid characterisation of wood fast pyrolysis liquids. Energy and fuels, 2008, 22 (6), pp 4245 –4248.

15

FUEL OIL QUALITY HAS TO BE ENSURED*

t

Water –

t

Solids –

t

Water distribution, microscopy

Acidity –

t

Insolubles in methanol-dichloromethane

Homogeneity –

t

Karl-Fischer titration ASTM E203

TAN, acids by CE, pH

Stability – –

Fixed temperature and time Test is affected by numerous variables and the whole procedure should be standardized and a reference sample included

*VTT Publication 450, http://www.vtt.fi/inf/pdf/publications/2001/P450.pdf Updated version under work, to be published on http://www.vtt.fi/

16

FUEL OIL USE - SPECIFICATIONS ARE NEEDED Detailed requirements for Fast pyrolysis liquid Biofuels in ASTM D7544 burner fuel standard Property

Test Method

Specification

Units

Gross Heat of Combustion

D240

15 min

MJ/kg

Water Content

E203

30 max

mass %

Pyrolysis Solids Content

Annex A1

2.5 max

mass %

Kinematic Viscosity at 40 oC

D445A

125 max

mm2/s

Density at 20 oC

D4052

1.1 –1.3

kg/dm3

Sulfur Content

D4294

0.05 max

mass %

Ash Content

D482

0.25 max

mass %

pH

E70-07

Report

Flash Point

D93 Procedure B

45 min

oC

Pour Point

D97

- 9 max

oC

A without

filtering

A1 - VTT Publication 450, http://www.vtt.fi/inf/pdf/publications/2001/P450.pdf, Updated version under work

17

HEALTH AND SAFETY - A NEW CHEMICALS REGULATION SYSTEM IN EU

t

t

t

REACH requires that chemical substances have to be registered to the European Chemicals Agency (ECHA)

Microsoft PowerPoint Presentation

Within the EU Biotox project toxicological, ecotoxicological, and physico-chemical data was created for fast pyrolysis liquids under CAS number 94114-43-9 Tasks to be done:

Microsoft PowerPoint Presentation

– –

–

Formation of SIEF (discussion forum), choose of lead registrant Create the missing data: some changes to MSDS, preparation of a chemical safety report Registration* – before 30 Nov 2010 if yearly production 1000 tonnes pyrolysis liquid – before 31 May 2013 if yearly production 100 - 1000 tonnes pyrolysis liquid

* PPORD notification may also be applied if a new product under piloting –gives 5 year time for registration

18

http://echa.europa.eu/home_en.asp

19

http://www.pyne.co.uk/?_id=29

20

SUMMARY t

t

t

Standardisation of biomass pyrolysis oil as a fuel is going on – Fuel oil specifications under ASTM – Health and safety issues under REACH in EU Analytical methods need validification – Test methods for ASTM standard – On-line methods for quality control in pyrolysis oil production and use The work will continue in IEA Pyrolysis project 2010 - 2012

Center for Sustainable Environmental Technologies

What Does it Mean to Characterize Bio-oil? Robert C. Brown, Marge Rover, Ming Li, Najeeb Kuzhiyi, Patrick Johnston, Sam Jones Iowa State University TC Biomass Conference Chicago, IL September 16-18, 2009

Center for Sustainable Environmental Technologies

Bio-Oil •

Complex mixture of hundreds of compounds present at relatively small concentrations depending upon the feedstock, pyrolysis conditions, and bio-oil collection system – Carbohydrates, phenols, furans, low molecular weight compounds (organic acids, alcohols, etc.)

•

Bio-oil is prone to phase separation, chemical condensation and polymerization

Pine 12%

Wheatstraw 8%

18% 13%

44% 19%

57%

Low molecular weight

29%

Furans

Phenols

Carbohydrates

GC-MS analysis of Bio-oil from Fluid bed pyrolyzer, ISU (2008)

Center for Sustainable Environmental Technologies

Bio-Oil Arises from Both Vapors and Aerosols Mechanisms of Fast Pyrolysis (Observed at very high heating rates) (dT/dt)→∞ H+

Biomass M+

Molten Biomass T ~ 430oC

Oligomers H+ M+ Monomers/ Isomers

M+ : Catalyzed by Alkaline Cations H+ : Catalyzed by Acids TM+ : Catalyzed by Zero Valent Transition Metals

Thermomechanical Ejection Vaporization

Low Mol.Wt Species

Aerosols High MW Species

Gases/Vapors

CO + H2

Reforming TM+

Synthesis Gas

Ring-opened Chains

Volatile Products

Radlein, D.; in Fast Pyrolysis of Biomass: Handbook Volume 1,A.V. Bridgwater, Ed. (1999) 164-188.

Center for Sustainable Environmental Technologies

What is Important to Measure? Physical Properties • Percent solids • Percent moisture • Viscosity • pH • Total acid number • Higher heating value • Water insoluble fraction • Proximate analysis

Chemical Composition • Ultimate Analysis – CHNOS analyzer

• Volatile compounds – GC/MS, GC/FID

• Non-volatile compounds – HPLC, IC

• Carbohydrate profile – High Performance Anion Exchange Chromatography (HPAEC) Pulsed Amperometric Detection (PAD)

• Lignin oligomers MW – GPC

• Alkali and alkaline earth metals – AA, IC

Center for Sustainable Environmental Technologies

Different Approaches to Bio-Oil Analysis

Bio-Oil

GC-MS Analysis

Volatile (mostly low molecular weight) Non-Volatile (mostly high molecular weight)

Water Soluble (mostly carbohydrate-derived) Phase separation prior to analysis

Water Insoluble (mostly lignin-derived)

Center for Sustainable Environmental Technologies

Bio-Oil Analysis Water 20%

Volatile fraction (as measured by GC-MS)

25% 15%

40%

Non-volatile (as measured by HPLC) Water insoluble (as measured by precipitation test) Water soluble compounds are partitioned between volatile and non-volatile fractions Source: Meier (1999)

Center for Sustainable Environmental Technologies

Recovery of Bio-oil as Fractions* Red Oak

Char

Fraction 1

Fraction 1 Yield (wt % bio-oil) 21.02 Moisture (wt %) 4.1 Water Insoluble (wt %) 51.0 Solids (wt %) 1.7 Total Acid Number (mg KOH/gm) 31.2 Higher Heating Value (MJ/kg) 24.4 Major Chemicals anhydrosugars

Fraction 2

Fraction 3

Fraction 4

Fraction 5

Fraction 2

Fraction 3

Fraction 4

Fraction 5

30.59

5.73

8.72

33.94

3.7

7.3

9.9

61.3

50.5

10.7

6.5