1、Designation: E3146 18aStandard Test Method forDetermination of Carbonyls in Pyrolysis Bio-Oils byPotentiometric Titration1This standard is issued under the fixed designation E3146; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, th
2、e year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers the determination of the carbo-nyl content of bio-oils derived from thermochemical d
3、ecom-position of lignocellulosic biomass and their deoxygenatedproducts. This method is used for determination of carbonylsbetween 0.5 and 8 mol/kg.1.2 Review the current and appropriate Safety Data Sheets(SDS) for detailed information concerning toxicity, first aidprocedures, and safety precautions
4、 and proper personal protec-tive equipment.1.3 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.4 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of
5、the user of this standard to establish appro-priate safety, health, and environmental practices and deter-mine the applicability of regulatory limitations prior to use.1.5 This international standard was developed in accor-dance with internationally recognized principles on standard-ization establis
6、hed in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:D664 Test Method for Acid Number of Petroleum Productsby Potentiome
7、tric TitrationD1193 Specification for Reagent WaterD6299 Practice for Applying Statistical Quality Assuranceand Control Charting Techniques to Evaluate AnalyticalMeasurement System Performance2.2 Other StandardsCEN/TR 17103:2017 Petroleum and related products - Fastpyrolysis bio-oils for stationary
8、internal combustion en-gines - quality determination2EN 16900:2017 Fast Pyrolysis bio-oils for industrialboilersRequirement and test methods33. Terminology3.1 Definitions:3.1.1 Bio-Oil, nThe crude liquid product of convertingsolid biomass into a liquid via fast pyrolysis or other thermo-chemical con
9、version process.3.1.2 Carbonyl, nThe chemical functional group consist-ing of a carbon-oxygen double bond, C=O. For this method,this includes all aldehydes and ketones; carboxylic acids,esters, and lactone groups are not measured by this method.3.1.3 fast pyrolysis, nPyrolysis conducted with rapid h
10、eat-ing and short residence time; typically less than 10 seconds.3.1.3.1 Discussion Other definitions for fast pyrolysisstate residence times of typically less than 10 seconds (1),45seconds (CEN standards, EN 16900:2017), and 1 second (2, 3).3.1.4 pyrolysis, nChemical decomposition of organic ma-ter
11、ials by heating in the absence of oxygen.4. Summary of Test Method4.1 A bio-oil sample is dissolved in dimethylsulfoxide(DMSO) and solutions are added containing hydroxylaminehydrochloride (NH2OHHCl) and triethanolamine (TEA). Themixture is sealed, stirred, and heated to 80 C for 2 hours.Carbonyl co
12、mpounds (aldehydes and ketones) react withNH2OHHCl forming the corresponding oxime and liberatingHCl. Liberated HCl is consumed by TEA, which drives thereaction forward. After the reaction, unconsumed TEA istitrated with a standardized HCl titrant to determine the molarconcentration of carbonyls in
13、the sample.1This test method is under the jurisdiction of ASTM Committee E48 onBioenergy and Industrial Chemicals from Biomass and is the direct responsibility ofSubcommittee E48.05 on Biomass Conversion.Current edition approved June 1, 2018. Published January 2018. Originallyapproved in 2018. Last
14、previous edition approved in 2018 as E314618. DOI:10.1520/E314618A.2Available from European Committee for Standardization (CEN), AvenueMarnix 17, B-1000, Brussels, Belgium, http:/www.cen.eu.3Available from British Standards Institution (BSI), 389 Chiswick High Rd.,London W4 4AL, U.K., http:/.Copyrig
15、ht ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of Internationa
16、l Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.15. Significance and Use5.1 While pyrolysis bio-oils are comprised of a large varietyof compounds and chemical functional groups, quantificationof carbonyl groups is especially
17、important. Carbonyls areknown to be responsible for the instability of bio-oil duringboth storage and processing. This method can be used toquantify the total carbonyl content of bio-oils.6. Interferences6.1 The selectivity of the method was tested by using1-butanol, 1-pentanol, tertiary-butanol, 2-
18、propanol, ethylacetate, acetic acid, xylose and glucose as model compounds,representing alcohol, ester, carboxylic acid and carbohydratesin the bio-oil. No interferences were seen for ethyl acetate oracetic acid. Monosaccharides are measured using this method.Addition of alcohols causes interference
19、s, but it is dependenton chain length. The reason is as yet undetermined but may berelated to solvent properties of the alcohol rather than reactionwith NH2OHHCl or TEA. Tests with primary, secondary andtertiary butanol have shown the same effect.7. Apparatus7.1 Analytical balance, accurate to 0.000
20、1 g.7.2 Micro Reaction Vial, borosilicate glass, cone shapedinside with at least 5 mL capacity and PTFE lined caps. SeeFig. 1.7.3 Triangular Magnetic Stirring Bar, PTFE lined andsuitable size for use with micro reaction vessels.7.4 Dry Block Heater with Magnetic Stirrer, capable ofmaintaining a temp
21、erature of 80 C, for use with micro reactionvials. See Fig. 2.7.4.1 A hot water bath with flat circular magnetic stirrer isalso acceptable.7.5 Potentiometric TitratorAutomatic titration systemscapable of adding fixed increments of titrant at fixed timeintervals (monotonic) or variable titrant increm
22、ents with elec-trode stability between increment additions (dynamic) withendpoint seeking capabilities as prescribed in the method. Atthe very least, the automatic titration system shall meet theperformance and specification requirements as warranted bythe manufacturer.7.5.1 Amonotonic or dynamic mo
23、de of titrant addition shallbe used. During the titration, the speed and volume of theaddition may vary depending on the rate of change of thesystem. The recommended minimum volume increment is0.05 mL, and the recommended maximum volume incrementis 0.1 mL. A signal drift of 10 mV/min and endpoint re
24、cogni-tion set to last is recommended to ensure endpoint detection.When using a monotonic titrant addition, the waiting timebetween increment additions shall be sufficient to allow formixing and a stable electrode response. Wait at least 10 sbetween additions.7.6 Buret, capable of delivering titrant
25、 in 0.02 mL or largerincrements. The buret tip shall deliver titrant directly into thetitration vessel (immersed about 25 mm in liquid) withoutexposure to the surrounding air.7.7 Titration Stand, suitable for supporting the electrode,stirrer and buret.7.8 Sensing Electrode, standard pH, suitable for
26、 non-aqueous titrations.7.9 Reference ElectrodeSilver/Silver Chloride (Ag/AgCl)Reference Electrode, filled with 1M-3M LiCl in ethanol.7.10 Combination pH ElectrodesSensing electrodes mayhave the Ag/AgCl reference electrode built into the sameelectrode body, which offers the convenience of working wi
27、thand maintaining only one electrode. A combination pH elec-trode designed for non-aqueous titrations of organic solvents isneeded for titration of ethanol and ethanol blends. The combi-nation pH electrode shall have a sleeve junction on thereference compartment and shall use an inert ethanolelectro
28、lyte, 1 to 3 mol/L (M) LiCl in ethanol. Combination pHelectrodes shall have the same or better response than a dualelectrode system. They shall have a movable sleeve for easyrinsing and addition of electrolyte.7.11 Titration Beaker, borosilicate glass or plastic beaker ofsuitable size for the titrat
29、ion.7.12 Variable-Speed Mechanical Stirrer, a suitable type,equipped with either magnetic stirrer and stirring bars orpropeller-type stirring paddle. The rate of stirring shall beFIG. 1 Micro Reaction Vial with PTFE Lined Cap and TriangularMagnetic Stirring BarFIG. 2 Dry Block HeaterE3146 18a2suffic
30、ient to produce vigorous agitation without spattering andwithout stirring air into the solution.7.12.1 If an electrical stirring apparatus is used, it shall beelectrically correct and grounded so that connecting or discon-necting the power to the motor will not produce a permanentchange in the instr
31、ument reading during the course of thetitration.8. Reagents and Materials8.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the commit-tee on Analytical Reagents of the American C
32、hemical Society,where such specifications are available.5Other grades may beused provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.8.1.1 Commercially available solutions may be used inplace of laborato
33、ry preparations provided the solutions havebeen certified as being equivalent.8.1.2 Alternate volumes of the solutions may be prepared,provided the final solution concentration is equivalent.8.2 Purity of WaterUnless otherwise indicated, referenceto water shall be understood to mean reagent water th
34、at meetsthe requirements of either Type I, II, or III of SpecificationD1193.8.3 Ethanol, reagent grade (WarningFlammable andtoxic).NOTE 1Do not use ethanol containing 2-butanone or other ketonedenaturant as this will interfere with this method.8.4 Lithium Chloride, LiCl.8.5 Lithium Chloride Electrol
35、ytePrepare a 1M3M solu-tion of lithium chloride (LiCl) in ethanol.8.6 Commercial Aqueous pH 4 and pH 7 Buffer SolutionsThese solutions shall be replaced at regular intervals consistentwith their stability or when contamination is suspected. Infor-mation relating to their stability is provided by the
36、 manufac-turer.8.7 Hydroxylamine hydrochloride (NH2OHHCl), 99%purity.8.8 Hydroxylamine hydrochloride solution (Solution A)Add 7.7 g of hydroxylamine hydrochloride and 50 mL of waterto a 250 mL volumetric flask. Swirl until all solids aredissolved, then dilute up to the mark with ethanol.8.9 Sodium C
37、arbonate (primary standard, Na2CO3), 99%purity.8.10 Triethanolamine (TEA), 99% purity.8.11 Triethanolamine solution (Solution B)Add 17.4 mLof triethanolamine to a 250 mL volumetric flask, then dilute upto the mark with ethanol.8.12 Hydrochloric acid (HCl), concentrated (WarningToxic and corrosive).8
38、.13 Hydrochloric acid solutionPrepare 0.1N solution byadding 10 ml concentrated HCl and 1 L water.8.14 4-(Benzyloxy)benzaldehyde (4-BBA), 99% purity.9. Sampling, Test Specimens, and Test Units9.1 Make sure the oil sample is at room temperature prior towithdrawing an aliquot for analysis. Bio-oil sho
39、uld be thor-oughly homogenized to obtain a representative sample. Mix byshaking vigorously for at least 1 minute, and visually inspectthe sample to ensure it is homogenous. Some bio-oils mayrequire longer shaking times.9.2 Exposure to oxygen and heat should be minimized toprevent sample degradation
40、prior to analysis.10. Preparation of Apparatus10.1 Prepare the titrator in accordance with the manufactur-ers instructions. Any visible air bubbles in the buret tip shallbe eliminated prior to titration since this can lead to errors.10.2 Preparation of ElectrodesWhen the combination pHelectrode cont
41、ains Ag/AgCl reference with an electrolyte,which is not 1 to 3 mol/L (M) LiCl in ethanol, the electrolyteshall be replaced. Drain the electrolyte from the electrode(vacuum suction), wash away all the salt (if present) with waterand then rinse with ethanol. Rinse several times with LiClelectrolyte so
42、lution. Finally, replace the sleeve and fill theelectrode with the LiCl electrolyte to the filling hole. Whenrefitting the sleeve, ensure that there will be a free flow ofelectrolyte into the system.10.3 Maintenance and Storage of Electrodes:10.3.1 Follow the manufacturers instructions for storagean
43、d use of the electrode.10.3.2 Prior to each titration, soak the prepared electrode inwater for at least 2 min. Rinse the electrode with waterimmediately prior to use. The glass membrane needs to berehydrated after titration of non-aqueous solutions.10.3.3 When not in use, immerse the lower half of t
44、hecombination electrode in LiCl electrolyte. Do not allow elec-trodes to remain immersed in a titrated sample solution for anylonger than it is necessary. While the electrodes are notextremely fragile, handle them carefully at all times.11. Calibration and Standardization11.1 Calibration of Electrod
45、e:11.1.1 Verify that the electrode is filled with 1 to 3 mol/L(M) LiCl in ethanol solution (see 10.2).11.1.2 Prepare the two buffer solutions, pH 7.0 and pH 4.0by placing approximately 50 mL of each solution in individualbeakers.11.1.3 Calibrate the electrode using the two buffer solutionsaccording
46、to the manufacturers instructions. Immerse theelectrode in each buffer solution, adjust the stirring speed sothat adequate mixing occurs without forming a vortex and waitfor the instrument reading. When the reading is complete, rinsethe electrode in high purity water, wipe gently and repeat the5Reag
47、ent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia an
48、dNational Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.E3146 18a3measurements with the other buffer solution. Record the pHvalue with an accuracy of 0.01 and the temperature with anaccuracy of 0.1 C. The measured pH values should be within60.05 pH units of the buffers certifi
49、ed value.11.1.3.1 Verify that the calibration slope is between 0.95and 1.02. An ideal pH glass electrode has a slope of 1.00(100 % of the Nernst slope) and an electrode zero point of0 mV for pH 7 at 25 C. In practice, the electrode zero pointpotential shall be within 615 mV (corresponding to pH 6.75 to7.25) and the slope shall be 0.95 (56.2 mV per pH at 25 C).The electrode zero point and the electrode slope may change asa result of the aging of the glass membrane or contamination ofthe diaphragm. If the electrode slope fal
