1、Designation: D 7544 09Standard Specification forPyrolysis Liquid Biofuel1This standard is issued under the fixed designation D 7544; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses
2、 indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This specification covers a pyrolysis liquid biofuelproduced from biomass intended for use in industrial burnersequipped to handle these types of fuels. Thi
3、s type of biofuel isnot intended for use in residential heaters, small commercialboilers, engines, or marine applications.NOTE 1For information on the significance of the physical, chemical,and performance properties identified in this specification, see AppendixX1.1.2 This specification is for use
4、in contracts for the purchaseof pyrolysis liquid biofuel and for guidance of consumers ofthis type of fuel.1.3 Nothing in this specification should preclude observanceof national or local regulations, which may be more restrictive.NOTE 2The generation and dissipation of static electricity may create
5、problems in the handling of pyrolysis liquid biofuel. For more informationon the subject, see Guide D 4865.1.4 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.4.1 ExceptionBTU units are included for informationonly in 3.5.1.1.
6、5 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Doc
7、uments2.1 ASTM Standards:2D93 Test Methods for Flash Point by Pensky-MartensClosed Cup TesterD97 Test Method for Pour Point of Petroleum ProductsD 240 Test Method for Heat of Combustion of LiquidHydrocarbon Fuels by Bomb CalorimeterD 396 Specification for Fuel OilsD 445 Test Method for Kinematic Vis
8、cosity of Transparentand Opaque Liquids (and Calculation of Dynamic Viscos-ity)D 482 Test Method for Ash from Petroleum ProductsD 4052 Test Method for Density and Relative Density ofLiquids by Digital Density MeterD 4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD 4177 Practice
9、for Automatic Sampling of Petroleum andPetroleum ProductsD 4294 Test Method for Sulfur in Petroleum and PetroleumProducts by Energy Dispersive X-ray Fluorescence Spec-trometryD 4865 Guide for Generation and Dissipation of StaticElectricity in Petroleum Fuel SystemsD 5854 Practice for Mixing and Hand
10、ling of LiquidSamples of Petroleum and Petroleum ProductsD 6469 Guide for Microbial Contamination in Fuels andFuel SystemsE70 Test Method for pH of Aqueous Solutions With theGlass ElectrodeE 203 Test Method for Water Using Volumetric Karl FischerTitration3. Terminology3.1 Definitions of Terms Specif
11、ic to This Standard:3.2 bulk fuel, nfuel in the storage facility in quantitiesover 190 L.3.3 char, nfine carbonaceous powder that is separatedfrom the vapors of biomass during pyrolysis.3.3.1 DiscussionPyrolysis liquid biofuel contains uni-formly suspended char.3.4 fuel degradation products, nthose
12、materials that areformed in fuel during extended storage or exposure to hightemperatures.3.4.1 DiscussionDuring storage, reactive organic com-pounds in pyrolysis liquid can act together to form largermolecules (fuel degradation products), which can becomeinsoluble or increase the fuel viscosity, or
13、both.1This specification is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.E0 on Burner, Diesel, Non-Aviation Gas Turbine, and Marine Fuels.Current edition approved June 15, 2009. Published August 2009.2For referen
14、ced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West C
15、onshohocken, PA 19428-2959, United States.3.5 industrial burner, ndevice which produces heat forindustrial use through the combustion of liquid fuels.3.5.1 DiscussionIndustrial burners are typically designedfor one of two applications: (1) industrial furnacesintegralcomponents of manufacturing proce
16、sses that provide directheating; for example, in aggregate, cement, lime, or phosphatekilns; coke ovens; or blast, smelting, melting, refining, ordrying ovens and (2) industrial boilerslarge indirect heatingunits which transfer thermal energy to water or other fluids orgases for use in heating in in
17、dustrial settings, power generationand in manufacturing processes. These boilers can be classifiedas utility/large industrial boilers with a heat input greater than105 GJ/h (100 3 106 BTU/h) or small industrial boilers witha heat input of between 10.5 to 105 GJ/h (10 to 100 3106 BTU/h).3.6 long-term
18、 storagestorage of fuel for longer than 3months after it is received by the user.3.7 medium-term storagestorage of fuel for up to 3months after it is received by the user.3.7.1 DiscussionIt is recommended that fuel be consumedwithin 6 months of receipt.3.8 pyrolysis, nchemical decomposition of organ
19、ic mate-rials by heating in the absence of oxygen.3.9 pyrolysis liquid biofuel, nliquid product from thepyrolysis of biomass.3.9.1 DiscussionPyrolysis liquid biofuel is comprised of acomplex mixture of the decomposition products of ligno-cellulosic biomass including highly oxygenated organic com-pou
20、nds. It is produced from the pyrolysis of biomass, followedby the rapid condensation of its vapors.3.10 pyrolysis solids, nsolid particles contained within thepyrolysis liquid biofuel.3.10.1 DiscussionPyrolysis solids is comprised of ash andchar.4. General Requirements4.1 The pyrolysis liquid biofue
21、l specified in this specifica-tion shall remain uniform in medium-term storage and notseparate by gravity into layers.NOTE 3Long-term storage or equipment down time can necessitatecirculation of pyrolysis liquid biofuel in-tank to prevent such separation.The buyer and seller should agree on any requ
22、irements for long-termstorage. If minor separation occurs during medium-term storage, mildagitation or product circulation should reverse such separation.5. Detailed Requirements5.1 The pyrolysis liquid biofuel specified shall conform tothe detailed requirements shown in Table 1.5.2 The properties s
23、elected for limitation are those that arebelieved to be of the greatest significance in obtaining accept-able performance of the burner.6. Sampling6.1 Review all intended test methods prior to sampling tounderstand the importance and effects of sampling technique,proper containers, and special handl
24、ing required for each testmethod. See Table 2.6.2 As indicated in 4.1, during medium-term storage, py-rolysis liquid biofuel shall remain uniform and not separateinto layers. Note, however, that separation may occur duringlong-term storage. Therefore, samples should be well mixedwhen transferring fr
25、om the primary sampling process orcontainer, or both, to another container or analytical apparatus,or both. Sampling from an active circulation loop or a wellmixed or agitated tank is preferred. Refer to Practice D 5854for more guidance on mixing and handling samples.6.3 Sample SizeA minimum of 1 L
26、is recommended.7. Test Methods7.1 The requirements enumerated in this specification shallbe determined in accordance with the following test methods:7.1.1 Gross Heat of CombustionTest Method D 240.7.1.2 Water ContentTest Method E 203.7.1.3 Pyrolysis Solids ContentSee Annex A1.7.1.4 Kinematic Viscosi
27、tyTest Method D 445.7.1.5 DensityTest Method D 4052.7.1.6 SulfurTest Method D 4294.7.1.7 Ash ContentTest Method D 482.7.1.8 pHTest Method E70.7.1.9 Flash PointTest Method D93.7.1.10 Pour PointTest Method D97.8. Keywords8.1 pyrolysis liquid biofuel; bio-oil; pyrolysis oil; pyoil;py-oil; bio-crude-oil
28、; bio-fuel-oil; wood liquids; burner fuel;renewable energy; alternative energy; fuel oils; furnace oilsTABLE 1 Detailed Requirements for Pyrolysis Liquid BiofuelsProperty Test Method Specification UnitsGross Heat of Combustion D 240 15 min MJ/kgWater Content E 203 30 max mass %Pyrolysis Solids Conte
29、nt Annex A1 2.5 max mass %Kinematic Viscosity at 40C D 445A125 max mm2/sDensity at 20C D 4052 1.11.3 kg/dm3Sulfur Content D 4294 0.05 max mass %Ash Content D 482 0.25 max mass %pH E70 Report .Flash Point D93, Procedure B 45 min CPour Point D97 9 max CAWithout filtering.D7544092ANNEX(Mandatory Inform
30、ation)A1. TEST METHOD FOR PYROLYSIS SOLIDS CONTENT IN PYROLYSIS LIQUIDS BY FILTRATION OF SOLIDS INMETHANOLA1.1 ScopeA1.1.1 This test method describes a filtration procedure fordetermining the pyrolysis solids content of pyrolysis liquid. Itis intended for the analysis of pyrolysis liquid with all ra
31、ngesof pyrolysis solids concentrations.3A1.1.2 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.A1.1.3 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility
32、of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. Material SafetyData Sheets are available for reagents and materials. Reviewthem for hazards prior to usage.A1.1.4 For Referenced Documents, see
33、Section 2.A1.1.5 For Terminology, see Section 3.A1.2 Summary of Test MethodA1.2.1 A pyrolysis liquid sample is dissolved in a methanoland dichloromethane solution (1:1), which is then filteredthrough a vacuum filter system. After filtering, the filtrand iswashed with the solvent until the filtrate i
34、s clear. The filter isremoved, dried and weighed. The pyrolysis solids content iscalculated based on the original pyrolysis liquid sample.A1.3 Significance and UseA1.3.1 Pyrolysis liquid can be produced to various charconcentrations. Increasing pyrolysis solids content can affectthe pyrolysis liquid
35、 biofuel handling, atomization, and storagestability in a negative manner.A1.4 Apparatus (see Fig. A1.1)A1.4.1 Smooth-tip Forceps.A1.4.2 Beaker, 400 mL.A1.4.3 Glass Stirring Rod.A1.4.4 Oven, explosion-proof, capable of maintaining atemperature of 105 6 3C.A1.4.5 Filtering Flask,1L.A1.4.6 Filter Hold
36、ers, borosilicate glass.A1.4.7 Filter Membrane, binder free glass microfiber, 1 m.A1.4.8 Weighing Dish, aluminum.A1.4.9 Balance, capable of weighing to the nearest 0.0001 g(0.1 mg) with a range of 300 g.A1.4.10 Vacuum.A1.5 Reagents and SolventsA1.5.1 Purity of ReagentsReagent grade chemicals shall b
37、e used in all tests. Unlessotherwise indicated, it is intended that all reagents shallconform to the specifications of the Committee on AnalyticalReagents of the American Chemical Society, where suchspecifications are available.4Other grades may be used, pro-vided it is first ascertained that the re
38、agent is of sufficientlyhigh purity to permit its use without lessening the accuracy ofthe determination. If an industrial grade reagent is used, it shallbe filtered using 0.45 m filter paper prior to use.A1.5.2 Ethanol, reagent grade (WarningFlammable.Toxic. Can be harmful or fatal if ingested or i
39、nhaled. Avoidskin contact.)A1.5.3 Methanol (MeOH), reagent grade (WarningFlammable. Toxic. Can be harmful or fatal if ingested orinhaled. Avoid skin contact.)A1.5.4 Dichloromethane (DCM), reagent grade(WarningFlammable. Toxic. Can be harmful or fatal ifingested or inhaled. Avoid skin contact.)A1.5.5
40、 Filter Paper, 1 m pore size, binder free glassmicrofiber.A1.6 SamplingA1.6.1 Obtain a sample using either Practice D 4057 orD 4177.A1.6.2 Obtain a representative sample of the pyrolysisliquid from a well-mixed container. The sample should be wellmixed to ensure homogeneity.3Oasmaa, A., and Peacocke
41、, C., A Guide To Physical Property Characteriza-tion Of Biomass-Derived Fast Pyrolysis Liquids, VTT Publications 450, VTTEnergy, Technical Research Centre of Finland, ESPOO 2001, www.vtt.fi/inf/pdf/publications/2001/P450.pdf4Reagent Chemicals, American Chemical Society Specifications, AmericanChemic
42、al Society, Washington, DC. For Suggestions on the testing of reagents notlisted by the American Chemical Society, see Annual Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockvi
43、lle,MD.TABLE 2 Typical Sampling Procedures for ContainersType of Container ProcedureStorage tanks that are well-mixed by circulation or agitation Automatic or Manual Pipeline SamplingTank cars, tank trucks, or ship tanks Dipper Sampling or All-Level SamplingD7544093FIG. A1.1 Paper Filtration Apparat
44、usD7544094A1.7 ProcedureA1.7.1 Dry a clean filter membrane for 15 min in adesiccator, place in a labeled aluminum weighing dish, andweigh to the nearest 0.1 mg.A1.7.2 Place a 400 mL beaker on the balance, and tare it.A1.7.3 Vigorously shake the sample by hand for a minimumof 15 s.A1.7.4 Using a disp
45、osable pipette, weigh approximately 15g of pyrolysis liquid sample into the beaker. Record the weightto the nearest 0.1 mg.A1.7.5 Add approximately 100 to 200 mL MeOH-DCMsolution (1:1) into the beaker and stir the mixture vigorously todissolve the pyrolysis liquid in the solvent.A1.7.6 Mount the fil
46、ter on a dry holder and apply a vacuum.Mount and securely clamp the filter funnel to the filter holder.A1.7.7 Use methanol to wash the filter paper to properlyseal the latter to the bottom of the funnel.A1.7.8 Filter the solution through the vacuum filter systemon 1 m filter paper. Quickly but caref
47、ully poor the solutioninto the center of the funnel. Thoroughly wash the beaker withMeOH-DCM solution and return the contents to the funnel.Wash the filtrand with methanol until the filtrate runs clear.A1.7.9 Remove the filter funnel from the filter holder andensure the edges of the filter funnel ar
48、e clean of any pyrolysissolids. If required, rinse any pyrolysis solids on the filter funnelonto the filter paper with methanol, ensuring no pyrolysissolids are lost.A1.7.10 Release the vacuum, and using the smooth-tipforceps transfer the filter membrane and filtrand to its originalweighing dish, an
49、d dry in the oven at 105 6 3C for 30 min.A1.7.11 Remove the weighing dish and filter membrane andcool to room temperature in a dessicator for a minimum of 1 h.A1.7.12 Weigh the filter membrane and weighing dish andrecord the stabilized weight to the nearest 0.1 mg.A1.8 CalculationA1.8.1 Calculate the pyrolysis solids content of the pyroly-sis liquid sample in accordance with Eq A1.1.pyrolysis solids wt %!5PS1PL3 100% (A1.1)pyrolysis solids = pyrolysis solids content, wt%,PS1= pyrolysis solids retained on 1 m filterpaper (g), andPL = py
