From the test-tube to the test-engine: Assessing the suitability of prospective liquid biofuel compounds

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1 From the test-tube to the test-engine: Assessing the suitability of prospective liquid biofuel compounds Falk Harnisch*, Ingo Blei, Tatiane Regina dos Santos, Maria Möller, Peter Nilges, Peter Eilts & Uwe Schröder Table SI -1: Raw data of Figure 2 Substances Auto ignition temperature/ C [1-6] Cetane Number / [-][1, 7] Hydrocarbons Dodecane n-tridecane n-pentadecane n-hexadecane heptadecane n-heptane n-nonane n-decane n-octane n-tetradecane n-hexane tetradecene nonene undecene Undecane hexadecene cyclohexane bicyclohexyl n-butylcyclohexane octene octadecene trans-decalin methylcyclohexane heptene hexene n-pentane cyclooctane methylpentane ,3-dimethylpentane ,4-dimethylpentane n-butylnaphthalene ,2-dimethylbutane sec-butylbenzene ,4,4-trimethyl-1-pentene

2 ethyl benzene ,3-diethylbenzene Isohexadecane ,2-diphenylethane diphenylmethane ,3-dimethylbenzene Methylnaphthalene biphenyl alcohols 1-octadecanol hexadecanol tetradecanol decanol octanol ethyl-1-hexanol heptanol dodecanol nonanol undecanol hexanol pentanol butanol propanol sec-butanol iso-butanol Ethanol Methanol tert-butanol acids and ester oleic acid decanoic acid Ethoxyethyl acetate ethyl levulinate Dimethyl carbonate diethyl dipentyl ethoxyethyl dibutyl Diethylene glycol dimethyl Triethylene glycol dimethyl [8] 1.2-dimethoxyethane dipropylene glycol monomethyl Dipropylene glycol monomethyl triethylene glycol monomethyl tetraoxaundecane

3 butylal dimethyl dimethoxymethane butoxyethanol Dioxolane tripropylene glycol monomethyl methoxyethanol methoxy-2 propanol furanics 2-Methyltetrahydrofuran methylfuran aldehydes and ketones octanal octanone heptanone Table SI-2: Raw data of Figure 3 Substance H f / kj mol -1 [9, 10] Cetane Number / [-] [1, 11] hydrocarbons heptadecane n-hexadecane n-pentadecane n-tetradecane n-tridecane Dodecane Undecane n-decane hexadecene n-nonane bicyclohexyl n-butylcyclohexane ,3,5-trimethylcyclohexane n-octane ,4-dimethylpentane ,3-dimethylpentane n-heptane ,2-dimethylbutane trans-decalin methylpentane n-hexane methylcyclohexane n-pentane cyclohexane ,4,4-trimethyl-1-pentene octene heptene

4 1-hexene sec-butylbenzene ,3-dimethylbenzene ethyl benzene Methylnaphthalene diphenylmethane ,2-diphenylethane biphenyl s Diethylene glycol dimethyl butylal dipentyl methoxyethanol dimethoxymethane dimethoxyethane dibutyl Dioxolane diethyl dimethyl alcohols 1-hexadecanol tetradecanol dodecanol decanol nonanol ethyl-1-hexanol octanol heptanol hexanol tert-butanol pentanol sec-butanol iso-butanol butanol propanol ethanol methanol acids and ester tristearin tripalmitin triolein trilaurin diethyl adipate isobutyl stearate dibutyl maleate butyl stearate propyl stearate methyl arachidate decyl caprate

5 butyl palmitate ethyl stearate octadecyl acetate isopropyl palmitate methyl stearate ethyl palmitate hexadecyl acetate methyl palmitate butyl oleate ethyl myristate propyl laurate methyl myristate ethyl oleate ethyl laurate acetic acid. dodecyl ester isopropyl decanoate oleic acid propyl decanoate octyl valerate methyl oleate ethyl levulinate methyl laurate butyl octanoate ethyl decanoate decyl acetate Ethoxyethyl acetate decanoic acid methyl decanoate ethyl octanoate Dimethyl carbonate linoleic acid. ethyl ester methyl octanoate butyl butanoate linoleic acid methyl heptanoate methyl linoleate methyl caproate linolenic acid linolenic acid. methyl ester methyl sorbate Diethylene glycol dimethyl Butylal dipentyl methoxyethanol dimethoxymethane dimethoxyethane dibutyl Dioxolane

6 diethyl dimethyl furanics 2-Methyltetrahydrofuran methylfuran Aldehydes and ketones 3-octanone heptanone octanal Table SI-3: Raw data of Figure 4 substances H LHV / kj g - 1 H LHV (Dulong) / kj g -1 H LHV (Boie) / kj g -1 hydrocarbons 1-Methylnaphthalene cyclooctane diphenylmethane Benzol Tetralin Toluol ,3-dimethylbenzene ethyl benzene ,3-diethylbenzene sec-butylbenzene trans-decalin bicyclohexyl methylcyclohexane n-butylcyclohexane cyclohexane hexadecene heptadecane n-hexadecane n-pentadecane ,4,4-trimethyl-1-pentene n-tetradecane n-tridecane octene Dodecane Undecane ,2,5-trimethylhexane octene n-decane heptene n-nonane

7 1-hexene n-octane ,4-dimethylpentane ,3-dimethylpentane n-heptane ,2-dimethylbutane methylpentane n-hexane n-pentane alcohols Glycerol Ethylene glycol methanol ethanol propanol tert-butanol sec-butanol iso-butanol butanol pentanol hexanol heptanol ethyl-1-hexanol octanol nonanol decanol undecanol dodecanol tetradecanol acids and ester methyl formate methyl acetate Diethyl malonate Trimethyl orthoformate Diethyl carbonate Ethyl acetoacetate ethyl acetate methyl caproate butyl butanoate methyl heptanoate methyl octanoate decanoic acid ethyl octanoate methyl decanoate ethyl decanoate

8 methyl laurate ethyl laurate methyl myristate ethyl myristate methyl linoleate methyl oleate Diethylene glycol Dioxolane Triethylene glycol methoxyethanol Diethylene glycol monomethyl dimethoxymethane Diethylene glycol dimethyl dimethoxyethane dimethyl Diethoxymethane Acetal butylal diethyl Isopropyl methyl Methyl propyl TAME tert-butyl isopropyl dibutyl furanics Furfural Tetrahydrofurfuryl alcohol Furan ,3-Dihydrofuran THF aldehydes and ketones Ethanal g-valerolactone Cyclohexanone octanone Table SI-4: Raw data of Figure 5 substances Lst H LHV / kj g -1 [9, 12, 13] *1 hydrocarbons Naphthalin biphenyl Methylnaphthalene

9 diphenylmethane Benzol ,2-diphenylethane ,6-dimethylnaphthalene Toluol n-butylnaphthalene Tetralin cyclooctane ethyl benzene ,3-dimethylbenzene ,3-diethylbenzene sec-butylbenzene n-hexylbenzene n-octylbenzene n-nonylbenzene n-dodecylbenzene n-tetradecylbenzene trans-decalin ,9-decadiene bicyclohexyl cyclohexane methylcyclohexane ,3,5-trimethylcyclohexane n-butylcyclohexane hexene heptene octene ,4,4-trimethyl-1-pentene octene nonene undecene tetradecene hexadecene octadecene methylheptadecane heptadecane n-hexadecane Isohexadecane n-pentadecane n-tetradecane n-tridecane butylnonane Dodecane ,2,4,6,6-pentamethylheptane Undecane

10 n-decane ,2-dimethyloctane n-nonane ,2,5-trimethylhexane n-octane n-heptane ,3-dimethylpentane ,4-dimethylpentane n-hexane ,2-dimethylbutane methylpentane n-pentane alcohols Glycerol Ethylene glycol Formalglycerol methanol ethanol propanol butanol iso-butanol sec-butanol tert-butanol pentanol hexanol heptanol octanol ethyl-1-hexanol octanol nonanol decanol undecanol dodecanol palmitoleyl alcohol tetradecanol oleyl alcohol hexadecanol octadecanol acids and ester Dimethyl carbonate Trimethyl orthoformate methyl acetate Diethyl malonate Diethyl carbonate Diethyl maleate

11 Ethyl acetoacetate diethyl succinate Ethoxyethyl acetate ethyl acetate Propylene glycol monomethyl acetate ethyl levulinate diethyl adipate dibutyl maleate methyl sorbate methyl caproate butyl butanoate methyl heptanoate methyl octanoate decanoic acid ethyl octanoate methyl decanoate butyl octanoate ethyl decanoate trilaurin methyl laurate isopropyl decanoate propyl decanoate octyl valerate acetic acid. dodecyl ester ethyl laurate linolenic acid methyl myristate propyl laurate linolenic acid. methyl ester linoleic acid ethyl myristate tripalmitin methyl linoleate oleic acid triolein methyl palmitate linoleic acid. ethyl ester methyl oleate hexadecyl acetate ethyl palmitate tristearin ethyl oleate methyl stearate isopropyl palmitate

12 octadecyl acetate decyl caprate butyl palmitate ethyl stearate butyl oleate methyl arachidate propyl stearate butyl stearate isobutyl stearate Diethylene glycol methoxy(methoxymethoxy)methane Dioxolane Triethylene glycol dimethoxymethane methoxyethanol Diethylene glycol monomethyl triethylene glycol monomethyl tetraoxaundecane Tetraethylene glycol dimethyl Triethylene glycol dimethyl (2-Ethoxyethoxy)ethanol Diethylene glycol dimethyl dimethoxyethane methoxy-2 propanol dipropylene glycol monomethyl Dipropylene glycol monomethyl dimethyl tripropylene glycol monomethyl Diethoxymethane ethoxyethyl butoxyethanol Acetal butoxy-2-propanol diethoxybutane dimethoxyhexane diethyl Methyl propyl Isopropyl methyl butylal TAME tert-butyl isopropyl ethylhexylal dibutyl dipentyl

13 furanics 5-HMF Furfural Furaldehyde (ethoxymethyl)-2-furfural Methylfurfural Furfuryl methyl Tetrahydrofurfuryl alcohol (diethoxymethyl)furan Furan furfuryl ethyl Methyl tetrahydrofurfuryl ,3-Dihydrofuran methylfuran THF Dimethylfuran Methyltetrahydrofuran aldehydes and ketones 3-Furaldehyde Ethanal Hydroxy-2-butanone Cyclohexanone heptanone octanal octanone *1: value derived according to [13] from H f [9] and the heat of vaporization[12]. Table SI-5: Raw data of Figure 6 Substances Lst H LHV (from H LHV (experimentally)[10]) / MJ m -3 hydrocarbons 1-Methylnaphthalene diphenylmethane Benzol Toluol Tetralin cyclooctane ,3-dimethylbenzene ethyl benzene ,3-diethylbenzene sec-butylbenzene trans-decalin bicyclohexyl methylcyclohexane

14 n-butylcyclohexane cyclohexane hexadecene ,4,4-trimethyl-1-pentene octene octene heptene hexene heptadecane n-hexadecane n-pentadecane n-tetradecane n-tridecane Dodecane Undecane n-decane ,2,5-trimethylhexane n-nonane n-octane ,4-dimethylpentane ,3-dimethylpentane n-heptane ,2-dimethylbutane methylpentane n-hexane n-pentane alcohols Glycerol Ethylene glycol methanol ethanol propanol tert-butanol sec-butanol iso-butanol butanol pentanol hexanol heptanol ethyl-1-hexanol octanol nonanol decanol undecanol dodecanol

15 1-tetradecanol acids and ester methyl formate Trimethyl orthoformate methyl acetate Diethyl malonate Diethyl carbonate Ethyl acetoacetate ethyl acetate methyl caproate butyl butanoate methyl heptanoate methyl octanoate decanoic acid ethyl octanoate methyl decanoate ethyl decanoate methyl laurate ethyl laurate methyl myristate ethyl myristate methyl linoleate methyl oleate s Diethylene glycol Dioxolane Triethylene glycol Furfural methoxyethanol dimethoxymethane Diethylene glycol monomethyl Diethylene glycol dimethyl dimethoxyethane Tetrahydrofurfuryl alcohol dimethyl Furan Diethoxymethane ,3-Dihydrofuran Acetal THF diethyl Isopropyl methyl Methyl propyl butylal

16 TAME tert-butyl isopropyl dibutyl furanics Furfural Tetrahydrofurfuryl alcohol Furan ,3-Dihydrofuran THF aldeyhdes and ketones Furfural Ethanal g-valerolactone Cyclohexanone octanone Table SI-6: Raw data of Figure 7 Substances C/H ratio CO 2 /H LHV g MJ -1 [9, 12] *1 hydrocarbons n-pentane n-hexane ,2-dimethylbutane methylpentane n-heptane ,3-dimethylpentane ,4-dimethylpentane n-octane n-nonane ,2,5-trimethylhexane n-decane ,2-dimethyloctane Undecane Dodecane ,2,4,6,6-pentamethylheptane n-tridecane butylnonane n-tetradecane n-pentadecane n-hexadecane Isohexadecane heptadecane

17 9-methylheptadecane cyclohexane methylcyclohexane ,3,5-trimethylcyclohexane n-butylcyclohexane hexene heptene octene ,4,4-trimethyl-1-pentene octene nonene undecene tetradecene hexadecene octadecene bicyclohexyl trans-decalin ,9-decadiene n-tetradecylbenzene n-dodecylbenzene n-nonylbenzene n-octylbenzene n-hexylbenzene ,3-diethylbenzene sec-butylbenzene cyclooctane ethyl benzene ,3-dimethylbenzene Tetralin Toluol n-butylnaphthalene Benzol ,2-diphenylethane ,6-dimethylnaphthalene diphenylmethane Methylnaphthalene biphenyl Naphthalin alcohols 1.3-Formalglycerol ethanol propanol butanol iso-butanol sec-butanol

18 tert-butanol pentanol hexanol heptanol octanol ethyl-1-hexanol octanol nonanol decanol undecanol dodecanol tetradecanol hexadecanol octadecanol palmitoleyl alcohol oleyl alcohol acids and ester Trimethyl orthoformate methyl acetate Diethyl carbonate Diethyl malonate Ethoxyethyl acetate ethyl acetate Propylene glycol monomethyl acetate diethyl succinate Ethyl acetoacetate ethyl levulinate diethyl adipate Diethyl maleate methyl caproate butyl butanoate methyl heptanoate methyl octanoate decanoic acid dibutyl maleate ethyl octanoate methyl decanoate butyl octanoate ethyl decanoate methyl laurate isopropyl decanoate propyl decanoate octyl valerate acetic acid. dodecyl ester

19 ethyl laurate methyl myristate propyl laurate ethyl myristate methyl palmitate hexadecyl acetate ethyl palmitate trilaurin methyl stearate isopropyl palmitate octadecyl acetate decyl caprate butyl palmitate ethyl stearate methyl arachidate propyl stearate butyl stearate isobutyl stearate tripalmitin tristearin oleic acid methyl oleate ethyl oleate butyl oleate triolein methyl sorbate linoleic acid methyl linoleate linoleic acid. ethyl ester Diethylene glycol methoxy(methoxymethoxy)methane dimethoxymethane methoxyethanol Triethylene glycol dimethyl Dioxolane Diethylene glycol monomethyl triethylene glycol monomethyl tetraoxaundecane dimethoxyethane methoxy-2 propanol (2-Ethoxyethoxy)ethanol Diethylene glycol dimethyl Triethylene glycol dimethyl

20 Tetraethylene glycol dimethyl dipropylene glycol monomethyl Dipropylene glycol monomethyl Diethoxymethane tripropylene glycol monomethyl ethoxyethyl butoxyethanol Acetal diethyl Methyl propyl Isopropyl methyl butoxy-2-propanol diethoxybutane dimethoxyhexane butylal TAME tert-butyl isopropyl dibutyl dipentyl ethylhexylal furanics Tetrahydrofurfuryl alcohol Methyl tetrahydrofurfuryl THF Methyltetrahydrofuran (diethoxymethyl)furan HMF Furfuryl methyl furfuryl ethyl ,3-Dihydrofuran (ethoxymethyl)-2-furfural Dimethylfuran methylfuran Methylfurfural Furfural Furan Furaldehyde aldehydes and ketones Ethanal Hydroxy-2-butanone heptanone octanal octanone Cyclohexanone Furaldehyde

21 *1: value derived from H f [9] and the heat of vaporization[12]. Table SI-7a: Raw data of Figure 8, own measurements Institute of Internal Combustion Engines, TU Braunschweig. temperature [ C] evaporated Fisher- Swedish class 1 volume [%] US diesel Tropschdiesel diesel B10 B100 kerosine Table SI-7b: Raw data of Figure 8 derived from[10]. pure substances boiling point [ C] n-hexadecane 287 References 1. Song, C., C.H. His, and I. Mochida, Chemistry of diesel fuels. 2000, New York: Taylor Francis. 2. The Chemical Database. 2012, The University of Akron. 3. Yanowitz, J.C., E.; McCormick, R. L., Utilization of Renewable Oxygenates as Gasoline Blending Components Center for Transportation Technologies and Systems Colorado. 4. Andrea Bertola, K.B., Oxygenated Fuels for Particulate Emissions Reduction in Heavy-Duty DI- Diesel Engines with Common-Rail Fuel Injection, S.T. Paper, Editor ChemicalLAND Arcoumanis, C., et al., The potential of di-methyl (DME) as an alternative fuel for compression-ignition engines: A review. Fuel, (7): p Mani Natarajan, E.A.F., David W. Naegeli,Tom Asmus, Wendy Clark, John Garbak, A. Manuel, D. González, Eleanor Liney, Wiliam Piel, James P. Wallace Oxygenates for Advanced Petroleum-Based Diesel Fuels: Part 1. Screening and Selection Methodology for the Oxygenates, in Interim Draft Report. 2001, Southwest Research Institute. 8. Boot, M., et al., Cyclic Oxygenates: A New Class of Second-Generation Biofuels for Diesel Engines Energy & Fuels, (4): p

22 9. National Institute of Standards and Technology (NIST) Lide, D.R., Handbook of Chemistry and Physics. 81st edition ed. 2000: CRC Press. 11. Mollenhauer, K.T., Helmut Handbuch Dieselmotoren. 3. ed. 2007, Berlin Heidelberg New York: Springer. 12. Joback, K.G., A Unified Approach to Physical Property Estimation Using Multivariative Statistical Techniques, in Massachusetts Institute of Technology, Dept. of Chemical Engineering,. 1984, Massachusetts Institute of Technology: Cambridge, MA. p DIN resp. ASTM D 240. Testing of solid and liquid fuels - Determination of gross calorific value by the bomb calorimeter and calculation of net calorific value - Part 1: Principles, apparatus, methods