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
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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)
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Stages of an LCA LCA framework
DIN EN ISO 14040:2006; 14044:2006
Goall and G d scope definition
Inventory analysis
Interpretation
Impact assessment
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• 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
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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.
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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)
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Scheme of the 6 tpd BTO® pilot plant
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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
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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 – –
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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
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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
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Additives
Supply chains: forest production, fuel, and power
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Supply chain oil upgrading
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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
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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
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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
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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
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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
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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 %
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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 %
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%
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 (%)
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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 %
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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 %
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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
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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
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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
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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
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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
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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
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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
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‘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 .
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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
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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
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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.
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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
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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
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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
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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
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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
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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