ASTM D7544-09

Standard Specification for Pyrolysis Liquid Biofuel

ABSTRACT
This specification details the physical and chemical requirements for pyrolysis liquid biofuels produced from biomass that are intended for use in industrial burners equipped to handle these types of fuels. The type of biofuel covered here is not intended for use in residential heaters, small commercial boilers, engines, or marine applications. It shall remain uniform in medium-term storage and shall not separate into layers due to gravity. Properly sampled test specimens shall undergo test procedures to determine their adherence to the following requirements: gross heat of combustion, water content, pyrolysis solids content, kinematic viscosity, density, sulfur content, ash content, pH, flash point, and pour point.
SCOPE
1.1 This specification covers a pyrolysis liquid biofuel produced from biomass intended for use in industrial burners equipped to handle these types of fuels. This type of biofuel is not intended for use in residential heaters, small commercial boilers, engines, or marine applications.
Note 1—For information on the significance of the physical, chemical, and performance properties identified in this specification, see Appendix X1.
1.2 This specification is for use in contracts for the purchase of pyrolysis liquid biofuel and for guidance of consumers of this type of fuel.
1.3 Nothing in this specification should preclude observance of national or local regulations, which may be more restrictive.
Note 2—The generation and dissipation of static electricity may create problems in the handling of pyrolysis liquid biofuel. For more information on the subject, see Guide D 4865.
1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.4.1 Exception—BTU units are included for information only in 3.5.1.
1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

General Information

• Status: Historical
• Publication Date: 14-Jun-2009
• ICS: 75.160.20 - Liquid fuels
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.E0 - Burner, Diesel and Non-Aviation Gas Turbine Fuels

Relations

• Replaced By: ASTM D7544-10 - Standard Specification for Pyrolysis Liquid Biofuel
• Effective Date: 01-Oct-2010

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D7544 – 09
Standard Specification for
Pyrolysis Liquid Biofuel
This standard is issued under the fixed designation D7544; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope D240 Test Method for Heat of Combustion of Liquid
Hydrocarbon Fuels by Bomb Calorimeter
1.1 This specification covers a pyrolysis liquid biofuel
D396 Specification for Fuel Oils
produced from biomass intended for use in industrial burners
D445 Test Method for Kinematic Viscosity of Transparent
equipped to handle these types of fuels. This type of biofuel is
and Opaque Liquids (and Calculation of Dynamic Viscos-
not intended for use in residential heaters, small commercial
ity)
boilers, engines, or marine applications.
D482 Test Method for Ash from Petroleum Products
NOTE 1—For information on the significance of the physical, chemical,
D4052 Test Method for Density and Relative Density of
and performance properties identified in this specification, see Appendix
Liquids by Digital Density Meter
X1.
D4057 Practice for Manual Sampling of Petroleum and
1.2 This specificationisforuseincontractsforthe purchase
Petroleum Products
of pyrolysis liquid biofuel and for guidance of consumers of
D4177 Practice for Automatic Sampling of Petroleum and
this type of fuel.
Petroleum Products
1.3 Nothinginthisspecificationshouldprecludeobservance
D4294 Test Method for Sulfur in Petroleum and Petroleum
of national or local regulations, which may be more restrictive.
Products by Energy Dispersive X-ray Fluorescence Spec-
trometry
NOTE 2—The generation and dissipation of static electricity may create
problemsinthehandlingofpyrolysisliquidbiofuel.Formoreinformation D4865 Guide for Generation and Dissipation of Static
on the subject, see Guide D4865.
Electricity in Petroleum Fuel Systems
D5854 PracticeforMixingandHandlingofLiquidSamples
1.4 The values stated in SI units are to be regarded as
of Petroleum and Petroleum Products
standard. No other units of measurement are included in this
D6469 Guide for Microbial Contamination in Fuels and
standard.
Fuel Systems
1.4.1 Exception—BTU units are included for information
E70 Test Method for pH of Aqueous Solutions With the
only in 3.5.1.
Glass Electrode
1.5 This standard does not purport to address all of the
E203 Test Method forWater UsingVolumetric Karl Fischer
safety concerns, if any, associated with its use. It is the
Titration
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
3. Terminology
bility of regulatory limitations prior to use.
3.1 Definitions of Terms Specific to This Standard:
2. Referenced Documents 3.2 bulk fuel, n—fuel in the storage facility in quantities
over 190 L.
2.1 ASTM Standards:
3.3 char, n—fine carbonaceous powder that is separated
D93 Test Methods for Flash Point by Pensky-Martens
from the vapors of biomass during pyrolysis.
Closed Cup Tester
3.3.1 Discussion—Pyrolysis liquid biofuel contains uni-
D97 Test Method for Pour Point of Petroleum Products
formly suspended char.
3.4 fuel degradation products, n—those materials that are
This specification is under the jurisdiction of ASTM Committee D02 on
formed in fuel during extended storage or exposure to high
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
temperatures.
D02.E0 on Burner, Diesel, Non-Aviation Gas Turbine, and Marine Fuels.
3.4.1 Discussion—During storage, reactive organic com-
Current edition approved June 15, 2009. PublishedAugust 2009. DOI: 10.1520/
D7544-09.
pounds in pyrolysis liquid can act together to form larger
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
molecules (fuel degradation products), which can become
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
insoluble or increase the fuel viscosity, or both.
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D7544 – 09
TABLE 1 Detailed Requirements for Pyrolysis Liquid Biofuels
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 %
A 2
Kinematic Viscosity at 40°C D445 125 max mm /s
Density at 20°C D4052 1.1–1.3 kg/dm
Sulfur Content D4294 0.05 max mass %
Ash Content D482 0.25 max mass %
pH E70 Report .
Flash Point D93, Procedure B 45 min °C
Pour Point D97 –9 max °C
A
Without filtering.
3.5 industrial burner, n—device which produces heat for 5. Detailed Requirements
industrial use through the combustion of liquid fuels.
5.1 The pyrolysis liquid biofuel specified shall conform to
3.5.1 Discussion—Industrial burners are typically designed
the detailed requirements shown in Table 1.
for one of two applications: (1) industrial furnaces—integral
5.2 The properties selected for limitation are those that are
components of manufacturing processes that provide direct
believed to be of the greatest significance in obtaining accept-
heating; for example, in aggregate, cement, lime, or phosphate
able performance of the burner.
kilns; coke ovens; or blast, smelting, melting, refining, or
drying ovens and (2) industrial boilers—large indirect heating
6. Sampling
units which transfer thermal energy to water or other fluids or
gases for use in heating in industrial settings, power generation
6.1 Review all intended test methods prior to sampling to
andinmanufacturingprocesses.Theseboilerscanbeclassified
understand the importance and effects of sampling technique,
as utility/large industrial boilers with a heat input greater than
proper containers, and special handling required for each test
105 GJ/h (100 3 106 BTU/h) or small industrial boilers with
method. See Table 2.
a heat input of between 10.5 to 105 GJ/h (10 to 100 3
6.2 As indicated in 4.1, during medium-term storage, py-
106 BTU/h).
rolysis liquid biofuel shall remain uniform and not separate
3.6 long-term storage—storage of fuel for longer than 3
into layers. Note, however, that separation may occur during
months after it is received by the user.
long-term storage. Therefore, samples should be well mixed
3.7 medium-term storage—storage of fuel for up to 3
when transferring from the primary sampling process or
months after it is received by the user.
container, or both, to another container or analytical apparatus,
3.7.1 Discussion—Itisrecommendedthatfuelbeconsumed
or both. Sampling from an active circulation loop or a well
within 6 months of receipt. mixedoragitatedtankispreferred.RefertoPracticeD5854for
more guidance on mixing and handling samples.
3.8 pyrolysis, n—chemical decomposition of organic mate-
rials by heating in the absence of oxygen.
6.3 Sample Size—A minimum of 1 L is recommended.
3.9 pyrolysis liquid biofuel, n—liquid product from the
pyrolysis of biomass. 7. Test Methods
3.9.1 Discussion—Pyrolysisliquidbiofueliscomprisedofa
7.1 The requirements enumerated in this specification shall
complex mixture of the decomposition products of ligno-
be determined in accordance with the following test methods:
cellulosic biomass including highly oxygenated organic com-
7.1.1 Gross Heat of Combustion—Test Method D240.
pounds. It is produced from the pyrolysis of biomass, followed
7.1.2 Water Content—Test Method E203.
by the rapid condensation of its vapors.
7.1.3 Pyrolysis Solids Content—See Annex A1.
3.10 pyrolysissolids,n—solidparticlescontainedwithinthe
pyrolysis liquid biofuel. 7.1.4 Kinematic Viscosity—Test Method D445.
3.10.1 Discussion—Pyrolysissolidsiscomprisedofashand
7.1.5 Density—Test Method D4052.
char.
7.1.6 Sulfur—Test Method D4294.
7.1.7 Ash Content—Test Method D482.
4. General Requirements
7.1.8 pH—Test Method E70.
4.1 The pyrolysis liquid biofuel specified in this specifica-
7.1.9 Flash Point—Test Method D93.
tion shall remain uniform in medium-term storage and not
7.1.10 Pour Point—Test Method D97.
separate by gravity into layers.
NOTE 3—Long-term storage or equipment down time can necessitate 8. Keywords
circulation of pyrolysis liquid biofuel in-tank to prevent such separation.
8.1 pyrolysis liquid biofuel; bio-oil; pyrolysis oil; pyoil;
The buyer and seller should agree on any requirements for long-term
py-oil; bio-crude-oil; bio-fuel-oil; wood liquids; burner fuel;
storage. If minor separation occurs during medium-term storage, mild
agitation or product circulation should reverse such separation. renewable energy; alternative energy; fuel oils; furnace oils
D7544 – 09
TABLE 2 Typical Sampling Procedures for Containers
Type of Container Procedure
Storage tanks that are well-mixed by circulation or agitation Automatic or Manual Pipeline Sampling
Tank cars, tank trucks, or ship tanks Dipper Sampling or All-Level Sampling
ANNEX
(Mandatory Information)
A1. TEST METHOD FOR PYROLYSIS SOLIDS CONTENT IN PYROLYSIS LIQUIDS BY FILTRATION OF SOLIDS IN
METHANOL
A1.1 Scope A1.4.6 Filter Holders, borosilicate glass.
A1.4.7 Filter Membrane,binderfreeglassmicrofiber,1µm.
A1.1.1 This test method describes a filtration procedure for
A1.4.8 Weighing Dish, aluminum.
determining the pyrolysis solids content of pyrolysis liquid. It
A1.4.9 Balance,capableofweighingtothenearest0.0001 g
is intended for the analysis of pyrolysis liquid with all ranges
(0.1 mg) with a range of 300 g.
of pyrolysis solids concentrations.
A1.4.10 Vacuum.
A1.1.2 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this
standard.
A1.5 Reagents and Solvents
A1.1.3 This standard does not purport to address all of the
A1.5.1 Purity of Reagents
safety concerns, if any, associated with its use. It is the
Reagent grade chemicals shall be used in all tests. Unless
responsibility of the user of this standard to establish appro-
otherwise indicated, it is intended that all reagents shall
priate safety and health practices and determine the applica-
conform to the specifications of the Committee on Analytical
bility of regulatory limitations prior to use. Material Safety
Reagents of the American Chemical Society, where such
Data Sheets are available for reagents and materials. Review
specifications are available. Other grades may be used, pro-
them for hazards prior to usage.
vided it is first ascertained that the reagent is of sufficiently
A1.1.4 For Referenced Documents, see Section 2.
high purity to permit its use without lessening the accuracy of
A1.1.5 For Terminology, see Section 3.
the determination. If an industrial grade reagent is used, it shall
be filtered using 0.45 µm filter paper prior to use.
A1.2 Summary of Test Method
A1.5.2 Ethanol, reagent grade (Warning—Flammable.
A1.2.1 Apyrolysis liquid sample is dissolved in a methanol
Toxic. Can be harmful or fatal if ingested or inhaled. Avoid
and dichloromethane solution (1:1), which is then filtered
skin contact.)
through a vacuum filter system. After filtering, the filtrand is
A1.5.3 Methanol (MeOH), reagent grade (Warning—
washed with the solvent until the filtrate is clear. The filter is
Flammable. Toxic. Can be harmful or fatal if ingested or
removed, dried and weighed. The pyrolysis solids content is
inhaled. Avoid skin contact.)
calculated based on the original pyrolysis liquid sample.
A1.5.4 Dichloromethane (DCM), reagent grade
(Warning—Flammable. Toxic. Can be harmful or fatal if
A1.3 Significance and Use
ingested or inhaled. Avoid skin contact.)
A1.3.1 Pyrolysis liquid can be produced to various char
A1.5.5 Filter Paper, 1 µm pore size, binder free glass
concentrations. Increasing pyrolysis solids content can affect
microfiber.
the pyrolysis liquid biofuel handling, atomization, and storage
stability in a negative manner.
A1.6 Sampling
A1.4 Apparatus (see Fig. A1.1) A1.6.1 Obtain a sample using either Practice D4057 or
D4177.
A1.4.1 Smooth-tip Forceps.
A1.6.2 Obtain a representative sample of the pyrolysis
A1.4.2 Beaker, 400 mL.
liquid from a well-mixed container.The sample should be well
A1.4.3 Glass Stirring Rod.
mixed to ensure homogeneity.
A1.4.4 Oven, explosion-proof, capable of maintaining a
temperature of 105 6 3°C.
A1.4.5 Filtering Flask,1L.
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
Oasmaa, A., and Peacocke, C., A Guide To Physical Property Characteriza- listed by the American Chemical Society, see Annual Standards for Laboratory
tion Of Biomass-Derived Fast Pyrolysis Liquids, VTT Publications 450, VTT Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Energy, Technical Research Centre of Finland, ESPOO 2001, www.vtt.fi/inf/pdf/ and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
publications/2001/P450.pdf MD.
D7544 – 09
FIG. A1.1 Paper Filtration Apparatus
D7544 – 09
A1.7 Procedure A1.8 Calculation
A1.8.1 Calculate the pyrolysis solids content of the pyroly-
A1.7.1 Dry a clean filter membrane for 15 min in a
sis liquid sample in accordance with Eq A1.1.
desiccator, place in a labeled aluminum weighing dish, and
weigh to the nearest 0.1 mg. PS
pyrolysis solids ~wt %!5 3 100% (A1.1)
PL
A1.7.2 Place a 400 mL beaker on the balance, and tare it.
A1.7.3 Vigorouslyshakethesamplebyhandforaminimum
of 15 s.
pyrolysis solids = pyrolysis solids content, wt%,
A1.7.4 Using a disposable pipette, weigh approximately 15 PS = pyrolysis solids retained on 1 µm filter
g of pyrolysis liquid sample into the beaker. Record the weight paper (g), and
PL = pyrolysis liquid sample taken for analy-
to the nearest 0.1 mg.
sis (g).
A1.7.5 Add approximately 100 to 200 mL MeOH-DCM
solution (1:1) into the beaker and stir the mixture vigorously to
A1.9 Report
dissolve the pyrolysis liquid in the solvent.
A1.9.1 Report the pyrolysis oil solids content to two sig-
A1.7.6 Mountthefilteronadryholderandapplyavacuum.
nificant figures.
Mount and securely clamp the filter funnel to the filter holder.
A1.10 Precision and Bias
A1.7.7 Use methanol to wash the filter paper to properly
A1.10.1 This interim precision statement represents repli-
seal the latter to the bottom of the funnel.
cateanalysesperformedintwolaboratoriesovertensuccessive
A1.7.8 Filter the solution through the vacuum filter system
days by the same analyst on the same day on the sam
...