General BioOil Plus Information

Content What is BioOil Plus? Applications Environmental Choice Program Combustion Testing BioOil Plus Handling Technical Requirements for BioOil Handling

What is BioOil Plus?

BioOil Plus is a blended pyrolysis fuel made from Char and BioOil. BioOil Plus has approximately 20% Char and 80% BioOil. The Char content in BioOil Plus is ground down to approximately eight microns. Because of the char content, BioOil Plus has higher viscosity, higher heating value, and higher specific gravity than BioOil. The higher heating value of BioOil Plus gives it a volumetric transportation cost advantage. (see following tables for properties)

BioOil Plus contains about 25% water. The water component in BioOil Plus is not a separate phase and is important because it lowers the viscosity of the fuel. BioOil is not a hydrocarbon-water mix like Orimulsion. Another feature of BioOil is its propensity to change slowly over time. This is not to be considered an instability because it can take months.

BioOil Plus is a fossil fuel substitute. It pumps well, ignites, and burns readily when atomized.

BioOil Plus has EcoLogo certification, having met stringent environmental criteria for industrial fuels as measured by Environment Canada’s Environmental Choice Program. The EcoLogo signifies that the manufacturing process of the product has been audited by a credible third party, and supported by empirical data on combustion tests conducted by both the company and authorized third parties.

BioOil Plus should be handled in a similar manner as conventional fuels. Direct contact with skin, as well as inhalation of its vapours should be avoided. Although not as readily flammable as conventional fuels, pyrolysis fuels should always be kept away from open flame or other heat sources. For further information, please see the material safety data sheet at the end of this document.

BioOil Plus properties and how they compare with conventional fuels

Table 1: Comparison of fuel properties – wood based pyrolysis fuel

Parameter	Unit	Analytical methods	BioOil Plus	BioOil	Heating oil #2	Heavy fuel oil
High Heating Value	MJ/kg	DIN51900	18-20	16-19	45.5	42.5
High Heating Value	MJ/L	DIN51900	23-25	19-23	39.4	41.7
Flash Point	oC	ASTM D93	50-60	48-55	38	60
Pour Point	oC	ASTM D97	-11	-15	-6	-
Density (15oC)	Kg/liter	ASTM D4052	1.22-1.3	1.2	0.865	0.986
Acidity	pH	pH meter	2-3	2-3	-	-
Solids (char)	wt %	Insolubles in Ethanol	20-23	0.01-0.2	-	-
Moisture	wt%	Karl Fisher	20-25	20-25	-	< 0.5
Ash	wt %	ASTM D482	<1	<0.02	Trace	0.08
Kinematic Viscosity	cSt	ASTM D445	-	-	-	-
20°C	-	-	1500-3700	70	3-6	2000-9000
40°C	-	-	300-500	19	1.8-3.5	500-1000
60°C	-	-	140-250	8	1.4-2.5	100-200
80°C	-	-	70-90	4	1.1-1.8	40-70

Table 2: Ultimate Analysis of different fuels (% by wt)

	BioOil	BioOil Plus	Char	Heating oil #2	Heavy fuel oil
Ash	< 0.02	<1	< 8	< 0.01	0.02-0.08
Carbon	42-47	45-51	75-78	86.4	85.7
Hydrogen	6-8	5-6	3-4	12.7	10.5
Nitrogen	< 0.1	< 0.3	< 0.3	0.006	0.18
Sulfur	< 0.02	< 0.06	-	0.2-0.7	< 2.8
Oxygen (by difference)	46-51	43-49	7-14	0.04	0.38

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BioOil Plus Applications

Paper Mill Firing BioOil in Lime Kiln

BioOil Plus’s potential use as a fossil fuel replacement is well recognized. Customers can include local, regional and national electrical utilities and power producers operating with partial or complete fuel substitution depending on scale and application. The opportunities for industrial applications are too numerous to list but some immediate applications in primary industry are kilns and boilers in pulp and paper, process heat in boilers in sawmills, metallurgy, oil and gas industries, as well as in secondary industries such as greenhouses, and district heating.

Pyrolysis fuels have a very complex chemical composition, containing a multitude of different compounds.  The specialty applications of these compounds in industrial processes and manufacturing are just beginning to be explored.  They represent a potentially very large market for value-added products derived from BioOil. 

Key Properties to Accommodate Switching Fuel to BioOil or BioOil Plus

Viscosity	Preheat BioOil Plus to 50° C.  Select air or steam atomized nozzles. Wherever possible, avoid pipe diameters < 1.5” ID in longer runs.
Acidity	Due to corrosivity, avoid carbon steel and use stainless or HDPE in all BioOil Plus wetted surfaces and instrumentation
Lower heating value	Select larger feed pump and preferably consider a positive displacement type for BioOil Plus pumping.
Aging	Avoid sustained heating to > 60° C. Use BioOil Plus within 3 months.
Ignition	Ignition is not a problem – what works with fuel oil generally works with BioOil Plus.  It is necessary to attend to the fuel / combustion air ratio before ignition.

While the properties of BioOil Plus are somewhat different from the fuel type the user may be accustomed to, the modifications required for switching to a pyrolysis fuel are fairly simple and mechanically traditional. Standard inspection and maintenance procedures, as described by the equipment manufacturers, still apply. Dynamotive can provide expertise and consultation on all aspects of its fuel combustion. This includes, for instance, equipment and material suitability, modification requirements or a tailored maintenance, and inspection program for burning BioOil Plus.

Industrial fuel, Cogeneration

Dynamotive’s successful burner tests have created opportunities for early commercial applications of BioOil as a clean burning fuel to replace natural gas, diesel and other liquid fossil fuels in the multi-billion dollar industrial boilers and kiln markets.

Lime Kilns and Lumber Kilns

Field tests showed that BioOil and natural gas were equivalent in thermal performance and product quality. 

Boilers

Pyrolysis fuels are an effective substitute for diesel, heavy fuel oil, light fuel oil or natural gas in essentially any type of boilers where these fuels are fired or contemplated to be fired. These are relatively simple applications requiring basic modifications limited mainly to fuel nozzles and transport systems

Green House Gas credits

Replacing fossil fuel use with BioOil Plus will also generate Green House Gas emissions reduction credits.  These credits could then be traded through domestic trading systems or through the established international mechanisms set out under the Kyoto Protocol.  The quantity and value of these credits will depend on what type of fossil fuel BioOil is displacing and where the credits are traded. 

Synthesis Gas Production/Gasification

Conventional liquid transportation fuels like diesel or gasoline are carbon based. But biomass is the only source of renewable carbon. While hydrogen is touted as the transportation fuel for the long term, it will require a whole new distribution infrastructure and new engines, e.g. fuel cells. Such changes will require decades to implement. It would be far cheaper in the short run to simply replace conventional fuels with equivalent fuels made from biomass derived carbon.

There is, at present, essentially only one known viable way to convert whole biomass to hydrocarbon fuels, namely by gasification and followed by Fischer-Tropsch conversion to liquids – the so-called BTL (biomass-to-liquids) process. Alternative biomass based fuels like ethanol or biodiesel, use only a fraction of the total plant biomass.

Economically practical plants for fuel synthesis will have to be of very large scale (several thousand tons per day of raw biomass required). This implies large costs associated with the transportation of large quantities of biomass; an intrinsically dilute resource. Dynamotive views BioOil as a key intermediate in the conversion of biomass to hydrogen or syngas since the volume reduction associated with the conversion of biomass to BioOil, BioOil Plus, and Char leads to enormous reduction in transportation and storage costs.

BioOil, BioOil Plus, and Char may be a suitable feedstock for the production of medium to high BTU synthesis gas via steam gasification. Successful lab-scale experiments have been performed at the University of Saskatchewan in cooperation with NRCan and CANMET labs. Additional successful gasification tests on BioOil/Char slurry (with 30% of Char content) have been performed by Dynamotive, Future Energy and FZK (research institute based in Germany) in September 2005.

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Environmental Choice Program

This certificate indicates that Dynamotive’s BioOil meets the stringent criteria of Canada’s Environmental Choice Program as a renewable industrial liquid fuel.

Certification Criteria

• To be authorizes to carry the EcoLogo™ the Char-Enriched Renewable Liquid Industrial Liquid Fuel must have the following characteristics;

Water Content	Ash Content	Viscocity at 20°C	Viscocity at 80°C	Heating Value
<25%	<3%	<1,500 centistokes	<90 centistokes	>18MJ/kg

• Written product information shall explicitly state the uses for Char-Enriched Renewable Liquid Industrial Liquid Fuel, do not include electricity turbines and;
• Written product information shall explicitly state the storage requirements for Char-Enriched Renewable Liquid Industrial Liquid Fuel, noting the differences from Regular Renewable Liquid Industrial Liquid Fuel;

Verification

• To verify a claim that a product meets the criterea listed in this document, the ECP will require access, as it is normal practise, to relevant purchasing records, quality control and production records and the right of access to production facilities on an announced basis.
• Compliance with requirement 3(b) shall be attested to by a signed statement of the Chief Executive Officer or the equivalent officer of the licensee. The ECP shall be advised in writing immediately by the licensee of any non-compliance which may occur during the term of the license. On the occurrence of any non-compliance, the license may be suspended or terminated as stipulated in the license agreement.

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BioOil Plus Combustion Testing

Eclipse BioOil Plus Test Showing Flame and Water Vapor

14V- HI BioOil Operating Parameters

• Operational Range = 24.5 to 6.0 MM Btu/hr
• BioOil Nozzle Pressure = 85 PSIG Recommended
• Bio Oil Temperature = 135°F ± 9°F
• Maximum Atomization Air Nozzle Pressure = 100 PSIG
• Air Consumption = 18613 SCFM

BioOil Plus Testing

A test on BioOil Plus fuel was also conducted. The purpose of the test was to confirm suitable operation of the burner and to collect emissions data. The BioOil Plus takes a higher nozzle pressure drop versus BioOil and required significantly more atomization air consumption.

Emissions Data

Low fire ignition and high fire were the primary conditions tested to obtain a baseline for sensitivity of atomization air and oil parameters. Emissions were taken by Airtech during nozzle and feasibility testing at 3MM Btu/hr. The two valid tests were recorded with heating of the oil just prior to the burner and with heating of the entire re-circulation system. Those results are found in Airtech report Di4700609291533.

General

Airtech Environmental Services Inc. (Airtech) was contracted by Eclipse, Inc. (Eclipse) to perform an air emission test program at their facility located in Rockford Illinois. Testing was performed on the burner test stand. The objective of the test program was to determine the emissions of particulate matter (PM), sulfur dioxide (SO2), nitrogen oxides (NOx) and carbon monoxide (CO) from a burner test stand while burning wood-based bio-fuel.

All testing was performed on September 13 and September 14, 2006. Coordinating the field portion of the test program were:

John McCown – Eclipse, Inc.
Jeff Kaput – Airtech Environmental Services Inc.

Parameters

The following specific parameters were determined at the test location:

• Gas velocity
• Gas temperature
• Oxygen concentration
• Carbon dioxide concentration
• Moisture concentration
• Total particulate concentration
• Sulfur dioxide concentration
• Nitrogen concentration
• Carbon monoxide concentration

Summary of Results Table 1 - Summary Results Test Parameter Run 1 Run 2 Run 3 Date 9/13/2006 9/14/2006 9/14/2006 Start Time 17:31 12:18 15:45 End Time 18:31 13:18 16:29         Gas Conditions       Temperature (°F) 954 1,076 1,104 Volumetric Flow Rate (acfm) 2,780 4,310 4,320 Volumetric Flow Rate (scfm) 1,010 1,450 1,430 Volumetric Flow Rate (dscfm) 915 1,260 1,230 Carbon Dioxide (% Dry) 12.4 11.8 11.3 Oxygen (% Dry) 7.70 8.39 8.79 Moisture (%) 9.58 13.3 14.2   Particulate Results Concentration (grains/dscf) 0.458 0.112 0.155 Concentration (grains/dscf @ 7% O2) 0.482 0.125 0.178 Emission Rate (lb/hr) 3.59 1.21 1.64   Sulfur Dioxide       Concentration (ppmd) 0.704 5.77 4.89 Emission Rate (lb/hr) 0.00642 0.0723 0.0597   Nitrogen Oxides Concentration (ppmd) 125 137 131 Emission (lb/hr) 0.823 1.24 1.15   Carbon Monoxide Concentration (ppmc) 127 1.80 5.28 Emission Rate (lb/hr) 0.508 0.00984 0.0283 Run 2 and 3 tested BioOil Run 1 tested BioOil Plus

BioOil Plus Flame John Stanley, Eclipse and Gholam Yavari, Dynamotive

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BioOil Handling

Storage stability

BioOil Plus is very stable.  However, with time and when left undisturbed (usually months) it will slowly begin to separate into a heavier component (lignin components) that  will form a thick bottom layer, several inches thick, and is viscous like honey.  This bottom layer shows no distinct line of separation from the bulk but rather a gradual transition, unlike oil and water separation for example.   Also, a 0.5”-2” thick floating layer may also form at the top.  With vigorous stirring, however, both these layers will mix back into the BioOil Plus, particularly if helped by the addition of 5% alcohol and/or by heating to 40° – 60°C   It should be noted that these processes will accelerate if the BioOil Plus is exposed to higher temperatures and thus extended exposure to > 60° C should be avoided.

In the bottom “lignin fragment” layer, the water content can reduce to 15% while the density remains 1.2 kg/litre and the high heating value increases to 18-22 MJ/kg.

Under ideal conditions BioOil Plus should be used within three months to avoid separation.

Storage and Transport Temperature

With a pour point of -11° C, BioOil Plus can be stored below freezing but it will become very viscous and very difficult to pump or transport (see pyrolysis fuels viscosities in Table 2).   The recommended storage is continuous agitation, insulated, and heated to at least 10° C with ability to heat it (electrically or with steam) to +40° C.  As mentioned before, heating BioOil to 60°C or higher will promote internal reactions and polymerization that can be significant if left at elevated temperatures for prolonged periods.  Another consequence of over heating will be the reduction / elimination of certain extractives and commercially viable products. The temperature required for handling and combustion of BioOil Plus is recommend to be ~10 °C higher than that of BioOil due to its higher viscosity.

BioOil Plus Sampling Procedures from Tanks or Containers

In order to take a representative sample of BioOil Plus it should be thoroughly mixed beforehand.

Technical Requirements for BioOil Handling

Material of container for shipment & storage

All BioOil wetted surfaces should be in Stainless 304, 316, HDPE, EPDM, PVC or Teflon because of BioOil’s acidity (pH of 2.2 - 3.0).

Temperature

During storage and transportation BioOil should be kept above 15 OC to maintain good fluidity, but should not be stored at temperatures higher than 40 OC for long to avoid polymerization.

Mixing

During storage BioOil should be agitated or circulated to maintain good homogeneity.

Pumping

For pumping large quantities of BioOil(more than 10 tons), all piping must be generous and not less than 3" on suction (keep as short as possible with generous NPSH) and 2" diameter on discharge-use reinforced PVC hose if practical. 

Pressure

BioOil does not exert pressures at temperature much different from water. Carriers designed to handle diesel fuels or equal will suffice for BioOil.

Cleaning BioOil out of tanker

Cleaning is best done with denatured ethanol. It will depend on end user requirements of the BioOil but it may be possible to add the collected wash spill to the BioOil, in particular if the end use is as a fuel. Do not wash with water as it will cause separation. Ethanol is preferable to methanol. Carrier is advised to carry a small amount of denatured ethanol with him to clean tools and valves.

Cleaning of spills in water

Contrary to oil spills, BioOil being heavier, in water it will quickly sink to the bottom where much of it will dissolve with time (up to 65%),  because parts of it are water-soluble (J.Blin, G. Volle, P. Girard, “Biodegradability of Fast Pyrolysis Oil”, CIRAD Forestry Department, International Research Centre for Agricultural and Development, France).

BioOil is a natural product and therefore a spill is believed not to cause nearly the catastrophic damage of fossil oil. However, work is ongoing to determine its exact effect on marine life (C. Peacocke, “Transport, Handling and Storage of Fast Pyrolysis Liquids”, Conversion and Resource Evaluation Ltd., Ireland). Since BioOil has a density greater than 1, marine transport may have to follow similar regulations as higher density chemicals.

Initial report of toxicology tests by CIRAD, France on EU funded project advises that BioOil (defined as hydrolyzed wood) is not explosive and non-toxic, further testing is ongoing.

BioOil data sheet for tanker shipment

TDG information

UN Number: UN1993
TDG Shipping Name: Flammable Liquid N.O.S. (lignin Solution)
TDG Classification: Class 3, Packing Group III

Cleaning agents

To clean BioOil from equipment, denatured ethanol (recommended) and methanol are both good cleaning agents for BioOil. Obtain their MSDS information and observe that they have their own dangers (poisonous and flammable).

Shipment of BioOil

BioOil Tanker

Note:

1. BioOil made from bark usually contains some wax (floating on top) and needs to be heated15 °C more than wax free BioOil.
2. Heated container truck may be needed in cold weather to transport BioOil but is not an absolute requirement.
3. To empty Whitewood BioOil from the truck, a temperature above 15/20 °C is recommended and for Whitewood/bark BioOil >30 °C is required.

BioOil Material Safety Data Sheet

Section I Hazardous Ingredients

Ingredients	CAS Registry Number	Concentration (%-weight/weight)
Acetic acid	64-19-7	from 1 to 5 %
Acetone	67-64-1	from 1 to 5 %
Formaldehyde	50-00-0	from 1 to 5 %
Formic acid	64-18-6	from 1 to 5 %
Glyoxal	107-22-2	from 1 to 5 %

Section II Preparation Information

Prepared on July 18, 2006

by:

Corporate Headquarters

Angus Corporate Centre
1700 West 75th Avenue
Suite 230
Vancouver BC V6P 6G2
Canada

T: (604) 267-6000

T: 1-877-863-2268

F: (604) 267-6005

info@dynamotive.com

Dynamotive USA, Inc.	First Resources Corporation	Dynamotive Latinoamericana
1650 Tysons Boulevard Suite 1550 McLean, VA 22102 U.S.A.	6520 Salish Drive Vancouver, BC V6N 2C7 Canada	Av. Quintana 585, 6º piso (C1129ABB) Buenos Aires Argentina
T: (703) 336-8450	T: (604) 267-6040	T: (54 11) 4802 2220
F: (703) 336-8462	F: (604) 267-6005	F: (54 11) 4802 1211

 

Section III Product Information

Manufacturer:

Emergency Phone Numbers:

Corporate Headquarters Angus Corporate Centre 1700 West 75th Avenue Suite 230 Vancouver BC V6P 6G2 Canada T: (604) 267-6000 T: 1-877-863-2268 F: (604) 267-6005 info@dynamotive.com Dynamotive USA, Inc. First Resources Corporation Dynamotive Latinoamericana 1650 Tysons Boulevard Suite 1550 McLean, VA 22102 U.S.A.  6520 Salish Drive Vancouver, BC V6N 2C7 Canada   Av. Quintana 585, 6º piso (C1129ABB) Buenos Aires Argentina T: (703) 336-8450 T: (604) 267-6040 T: (54 11) 4802 2220 F: (703) 336-8462 F: (604) 267-6005 F: (54 11) 4802 1211

Dynamotive (604) 267-6000 CANUTEC (24 hours) (613) 996-6666

Product Name:	BioOil
Synonyms:	Pyrolysis oil, biomass pyrolysis oil
UN number:	UN1993
TDG Shipping Name:	Flammable Liquid N.O.S. (lignin solution)
TDG Classification:	Class 3, Packing Group III
Use:	Applications as a liquid fuel or raw material for industrial processes

Section IV Physical Data

Physical State:	Liquid
Appearance:	Dark brown liquid
Odour:	Smoky odour
Odour Threshold:	Not applicable
Vapour Pressure:	~5 kPa at 38 °C
Vapour Density:	Not available
Evaporation Rate:	Not available
Boiling Point:	Not available
Freezing Point:	Not available
pH:	~2.2
Specific gravity:	~1.2 / ASTM D4052
Pour point:	-21 °C to -33 °C / ASTM D97
Coefficient of Water/Oil Distribution:	Not available

Section V Fire or Explosion Hazard

Conditions of flammability:	WHMIS Class B, Division 3. Combustible liquid. Flammable at extremely high temperatures.  BioOil consists of about 25% water.  When BioOil is distilled to 250 °C, the collected distillate is about 35% of original weight.
Extinguishing media:	Water, foam, carbon dioxide, dry chemical. Fire fighters should wear self-contained breathing apparatus.
Flash point/method:	48 - 55 °C / ASTM D93
UEL:	Not available
LEL:	Not available
Auto-ignition temperature:	~500°C
Hazardous Combustion Products:	COx
Explosion Data	Sensitivity to mechanical impact: no Sensitivity to static discharge:       no

Section VI Reactivity Data 

Conditions of Instability:	Normally stable
Incompatibilities:	Oxidizers
Conditions of Reactivity:	High temperatures may generate highly flammable volatile organics.
Hazardous Decomposition Products:	Carbon monoxide, acetone, formaldehyde and other volatile organics.

Section VII Toxicological Properties

Route of Entry:
* Skin contact:    * Skin absorption:    * Eye contact:	May irritate No information available Eyes are sensitive to BioOil with probable corneal damage resulting from exposure.  Refer to section IX for first aid measures
* Inhalation:    * Ingestion:	Irritating and can be harmful to respiratory tract Irritating and can be harmful to gastro-intestinal tract
LC50:	Not available
LD50:	> 2000 mg/kg body weight (oral, rat)
Exposure limits:	Not established
Effects of Acute Exposure:	Coughing or mild breathing difficulties may result.
Effects of Chronic Exposure:	No information available
Irritancy:	No experimental information available
Sensitizing capability:	No information available
Carcinogenicity:	No information available
Reproductive toxicity:	No information available
Teratogenicity:	No information available
Mutagenicity	Mutagenic tests:
	Ames test (Salmonella typhimurium): positive Bone marrow micronucleus test by oral route gavage in mice: negative Micronucleus test in L5178 TK mouse lymphoma cells: light mutagenic activity
Toxicologically Synergistic Products:	No information available

Section VIII Preventive Measures

Engineering Controls:	Engineering control measures to reduce hazardous exposures are preferred. Methods include mechanical ventilation (dilution and local exhaust), control of personnel exposure, control of process conditions and process modification. Administrative controls and personal protective equipment may also be required.
Personal protective equipment:
* Gloves:    * Respiratory protection:    * Eye protection:    * Clothing:	Neoprene, latex or equivalent Fume hood or NIOSH/MSHA approved organic vapour respirator as appropriate Chemical safety goggles Plastic apron, sleeves and boots as appropriate
Storage Requirements:	Store in suitable labeled acid-proof steel or plastics such as PETE, PP, HDPE containers. Keep containers tightly closed when not in use and when empty. Protect from damage. Store in a cool, dry, well ventilated area, out of direct sunlight. Store away from oxidants.
Handling Procedures and Equipment:	Follow routine safe handling procedures.
Leak or Spill Cleanup:	Before dealing with spills take necessary protective measures, inform others to keep at a safe distance and shut off all possible sources of ignition. Mix with absorbent such as floor dry, transfer carefully to container and arrange removal by disposal company. Wash site of spill thoroughly with water.
Disposal:	Follow all federal, provincial and local regulations for disposal. Use only licensed disposal and waste hauling companies. Disposal of small amounts of spilled material may be handled as described under “Leak or Spill Cleanup”. Large spills must be dealt with separately and must be handled by qualified disposal companies.
Special Shipping Information:	Follow all TDG regulations and see classification in Section III.

Section IX First Aid Measures

Skin:	Flush the contact area with lukewarm running water for at least 15 minutes. Remove contaminated clothing, taking care not to spread the chemical. If contamination is extensive, remove the clothing under running water. Discard or decontaminate clothing before use. Unless contact has been slight, seek medical attention. Seek medical attention if irritation persists.
Eye:	Flush the contaminated eye(s) for at least 15 minutes with lukewarm running water, holding the eyelids open. Take care not to rinse contaminated water into the non-affected eye. Always seek medical attention for accidents involving the eyes.
Inhalation:	Take proper precautions to ensure your own safety before attempting rescue. Remove source of contamination or move victim to fresh air. If breathing has stopped, trained personnel should begin artificial respiration, or if the heart has stopped, cardiopulmonary resuscitation (CPR) immediately. Seek medical attention.
Ingestion:	Never give anything by mouth if victim is rapidly losing consciousness, or is unconscious or convulsing. Rinse mouth thoroughly with water. Do not induce vomiting. Have victim drink 200 to 400 mL of water to dilute. If breathing has stopped, trained personnel should begin artificial respiration, or if the heart has stopped, cardiopulmonary resuscitation (CPR) immediately.

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