EP2083061A1 - Leichtölzusammensetzung - Google Patents

Leichtölzusammensetzung Download PDF

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Publication number
EP2083061A1
EP2083061A1 EP07829322A EP07829322A EP2083061A1 EP 2083061 A1 EP2083061 A1 EP 2083061A1 EP 07829322 A EP07829322 A EP 07829322A EP 07829322 A EP07829322 A EP 07829322A EP 2083061 A1 EP2083061 A1 EP 2083061A1
Authority
EP
European Patent Office
Prior art keywords
nylon
light oil
test sample
paraffin
isoparaffin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07829322A
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English (en)
French (fr)
Other versions
EP2083061A4 (de
Inventor
Hitoshi Hayashi
Tadao Ogawa
Eiichi Sudo
Ayako Ohshima
Keiko Fukumoto
Atsushi Murase
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyota Motor Corp
Original Assignee
Toyota Motor Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyota Motor Corp filed Critical Toyota Motor Corp
Publication of EP2083061A1 publication Critical patent/EP2083061A1/de
Publication of EP2083061A4 publication Critical patent/EP2083061A4/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon

Definitions

  • the present invention relates to a light oil composition, and in particular to a GTL (Gas to Liquid) light oil composition.
  • GTL Gas to Liquid
  • GTL light oil is a synthetic oil fraction with a boiling point within the range of that of light oil obtained by: conversion of natural gas and heavy oil into a water gas; synthesis thereof using a Fischer-Tropsch reaction (FT synthesis); fractionating off the highly volatile components of this synthetic oil; and carrying out hydrocracking and isomerization as required.
  • FT synthesis Fischer-Tropsch reaction
  • objective of the present invention is to address the above issue. Namely, objective of the present invention is to provide a light oil composition that does not cause deterioration in Nylon-based materials.
  • the present invention is a light oil composition containing paraffin(s) at a concentration of 97% by mass or greater, with isoparaffin(s) having 14 or fewer carbon atoms at a concentration of 10% by mass or less of the above paraffin(s).
  • a light oil composition that does not cause deterioration in Nylon-based materials can be provided.
  • the present invention is a light oil composition, and in particular, a GTL light oil or a light oil composition containing a GTL light oil, wherein paraffin(s) are contained at a concentration of 97% by mass or greater, and isoparaffin(s) having 14 or fewer carbon atoms are contained in the above paraffin(s) at a concentration of 10% by mass or less. If the concentration of isoparaffin(s) is less than 97% by mass, then it ceases to be called a clean fuel due to the PM discharge properties and the like. If bio light oil were to be permitted, then deterioration of the fuel itself and deterioration of other materials becomes a problem.
  • Nylon materials used in fuel systems oxidize, and become low molecular weight molecules by being depolymerized or reduce the extension thereof, leading to deterioration in Nylon-based materials.
  • the presence of isoparaffins lowers the cetane number of GTL light oils (lowers the too high cetane number of normal paraffins), and also exhibits the effect of lowering the viscosity. Consequently, a highly branched isoparaffin having 15 or more carbon atoms is preferably added if the viscosity of the light oil of the present invention becomes too high, thereby adjusting the viscosity. There is no particular limitation to the amount contained of the highly branched isoparaffin having 15 or more carbon atoms as long as the resultant has the desired viscosity and cetane number.
  • the light oil of the present invention can, for example, be manufactured as described below. Namely, manufacture is by hydrocracking paraffin obtained by FT reaction (Fischer-Tropsch reaction) over a solid acid catalyst to obtain an isoparaffin. This isoparaffin is next analyzed by gas chromatography and the concentration of isoparaffin(s) having 14 or fewer carbon atoms is investigated. An addition amount is decided in consideration of the gas chromatography-analyzed concentration of isoparaffin(s) having 14 or fewer carbon atoms (such that the isoparaffin concentration is 10% by mass or less after mixing) and the above isoparaffin is then mixed with the paraffin obtained by FT reaction.
  • FT reaction Fischer-Tropsch reaction
  • the light oil of the present invention such as above has the following advantages.
  • Test Sample - A was prepared to include a greater amount of low molecular weight paraffin in comparison to Test Sample - B, and this composition was confirmed using a GC method.
  • Test Sample - A and Test Sample - B were derived using a gas chromatography method (mounted to a thermal conductivity detector) with a 3 meter long column packed with molecular sieve 13X. The results are shown in FIG. 1 . It is clear from FIG. 1 that the dissolved oxygen amount of Test Sample - A is greater in comparison to that of Test Sample - B. This is thought to be because the Test Sample - A contains a greater amount of low molecular weight isoparaffin than Test Sample - B.
  • the dissolved oxygen amount was measured for normal paraffins and isoparaffins (2-methyl paraffin) having 8 to 12 carbon atoms. The results are shown in FIG. 2 .
  • the dissolved oxygen concentration at room temperature is shown on the vertical axis of FIG. 2 (in a similar manner to FIG. 1 ). It can be seen from FIG. 2 that (1) isoparaffin contains a greater amount of oxygen than normal paraffin, and (2) for the same type of paraffin, the smaller the number of carbon atoms the more oxygen is contained.
  • Nylon-66 (referred to below simply as Nylon) was immersed in Test Sample - A and in Test Sample - B, respectively. After immersion for 500 hours the surface layer was removed from each Nylon and heated to 250 °C in Helium, and any gas generated was analyzed by gas chromatographic/ mass spectroscopic methods. The results thereof are shown in FIG. 3 .
  • Nylon that had been immersed in Test Sample - A contained more low molecular weight paraffin than Nylon that had been immersed in Test Sample - B.
  • the paraffin that had permeated into the Nylon had a higher proportion of isoparaffin than the original Test Sample.
  • FIG. 4A Samples extracted from the surface of each of the Nylons above were analyzed using Matrix Assisted Laser Desorption Ionisation Mass Spectrometry (MALDI-MS).
  • MALDI-MS Matrix Assisted Laser Desorption Ionisation Mass Spectrometry
  • FIG. 4D Nylon subjected to oxidizing treatment
  • FIG. 4E Nylon subjected to hydrolysis treatment
  • FIG. 4B the mass spectrograph of Nylon that has been immersed in Test Sample - A substantially matches the mass spectrograph of Nylon that has been force-oxidized in the atmosphere. Namely it is seen that Nylon that has been immersed in Test Sample - A is oxidized.
  • FIG 4B is Nylon that has been immersed in Test Sample - B
  • FIG. 4C is Nylon that has been immersed in Test Sample - A.
  • the cut faces of the Nylon that has been immersed in Test Sample - A and of the Nylon that has been immersed in Test Sample - B were analyzed with infrared spectroscopic imaging. The results are shown in FIG. 6 .
  • the relative intensity of the absorption for carbonyl groups generated by oxidation (1710 cm -1 ) to the absorption for amide bonds of Nylon main chains (1650 cm -1 ) is shown on the vertical axis. It can be seen from FIG. 6 that the Nylon that has been immersed in the GTL light oil Test Sample - A is oxidized to a depth of 400 ⁇ m from the surface. It can be seen from the results that there is a high probability that the Nylon that has been immersed in the GTL light oil of Test Sample - A has deteriorated as in the manner of the following (1) to (6).
  • a model fuel was prepared of the compositions shown in Table 1 below, from reagents of normal paraffin having 7 to 13 carbon atoms, isoparaffin having 7 to 12 carbon atoms (2-methyl paraffin) and an isomer of heptane (7 carbon atoms).
  • n-C7 to n-C13 indicates normal heptane, normal octane, normal nonane, normal decane, normal undecane, normal dodecane, and normal tridecane
  • 2-Me-C6 to 2-Me-C11 indicates 2-methylhexane, 2-methylheptane, 2-methyloctane, 2-methylnonane, 2-methyldecane, and 2-mathylundecane
  • n-C7 to n-C13 and 2-Me-C6 to 2-Me-C11 indicates a mixture of both of the above.
  • ⁇ indicates that 2 ml of normal hexadecane has been added, as an internal standard.
  • Nylon was immersed in these model fuels, the model fuels were analyzed before and after immersion using gas chromatographic/ mass spectrographic methods, and the Nylons were analyzed before and after immersion using thermal desorption - gas chromatographic/mass spectrographic methods.
  • the analysis results of using gas chromatographic/ mass spectrographic methods on the model fuels before and after immersion are shown in FIG 7 .
  • Model fuels (light oils) A to E were produced of Component A and Component B as below, in blends as shown in Table 2.
  • the paraffin concentration in the model fuels was 97% by mass or more in all cases.
  • Component A mixture of equal amounts of normal paraffins having 8, 10, 12, and 14 carbon atoms.
  • Component B mixture of isoparaffins having 8 and 9 carbon atoms (2-methylheptane: 3-methylheptane : 2-methyloctane, at 4:3:3 (volume ratio)).
  • Nylon-66 was formed according to JISK7162 (ISO3167) and manufactured into test pieces.
  • model fuel 250ml was placed in a 300ml volume pressure container (internal diameter: 45mm, internal height: 235mm), 3 test pieces were immersed therein and heated to 120 °C for 475 hours. Before immersion the test pieces were dried for 4 hours at 100 °C in a vacuum.
  • Tensile testing was carried out on the test pieces after immersion using a tension testing device (made by Shimadzu: AG-10kNC) in accordance with ISO527 (the extension velocity was set at 50mm/min).
  • the test pieces were stored in a desiccator from after immersion up until just before tensile testing.
  • Table 2 shows values of the average extensions measured at breakage of the three test pieces.
  • FIG. 9 A plot of the results of Table 2 is shown in FIG. 9 . It can be seen from FIG 9 that the extension of the Nylon test pieces falls off rapidly when the concentration of isoparaffin exceeds 10% by mass.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
EP07829322A 2006-10-06 2007-10-05 Leichtölzusammensetzung Withdrawn EP2083061A4 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006275311A JP2008094879A (ja) 2006-10-06 2006-10-06 軽油組成物
PCT/JP2007/069584 WO2008044641A1 (fr) 2006-10-06 2007-10-05 Composition d'huile légère

Publications (2)

Publication Number Publication Date
EP2083061A1 true EP2083061A1 (de) 2009-07-29
EP2083061A4 EP2083061A4 (de) 2013-03-20

Family

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EP07829322A Withdrawn EP2083061A4 (de) 2006-10-06 2007-10-05 Leichtölzusammensetzung

Country Status (4)

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US (1) US20100012551A1 (de)
EP (1) EP2083061A4 (de)
JP (1) JP2008094879A (de)
WO (1) WO2008044641A1 (de)

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US10540729B1 (en) 2015-12-30 2020-01-21 Wells Fargo Bank, N.A. Mobile wallets with packaged travel services
US10853783B1 (en) 2015-12-30 2020-12-01 Wells Fargo Bank, N.A. Processing online transactions with an intermediary system
US10902405B1 (en) 2016-05-11 2021-01-26 Wells Fargo Bank, N.A. Transient mobile wallets
US11080685B1 (en) 2017-06-12 2021-08-03 Weils Fargo Bank, N.A. Direct payment authorization path

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997004038A1 (en) * 1995-07-24 1997-02-06 Union Oil Company Of California Non-toxic, inexpensive synthetic drilling fluid
WO2000020535A1 (en) * 1998-10-05 2000-04-13 Sasol Technology (Pty) Ltd Process for producing middle distillates and middle distillates produced by that process

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5814109A (en) * 1997-02-07 1998-09-29 Exxon Research And Engineering Company Diesel additive for improving cetane, lubricity, and stability
JPH11217575A (ja) * 1997-11-07 1999-08-10 Toyota Central Res & Dev Lab Inc パティキュレート低減用軽油
US7217852B1 (en) * 1998-10-05 2007-05-15 Sasol Technology (Pty) Ltd. Process for producing middle distillates and middle distillates produced by that process
EP1835011A1 (de) * 1998-10-05 2007-09-19 Sasol Technology (Pty) Ltd Biologisch abbaubare Mitteldestillate und ihre Herstellung
ES2275445B1 (es) * 2003-04-11 2008-06-01 Sasol Technology (Pty) Ltd Combustible diesel con bajo contenido de azufre y combustible para turbinas de aviacion.
US8053614B2 (en) * 2005-12-12 2011-11-08 Neste Oil Oyj Base oil
US20070142242A1 (en) * 2005-12-15 2007-06-21 Gleeson James W Lubricant oil compositions containing GTL base stock(s) and/or base oil(s) and having improved resistance to the loss of viscosity and weight and a method for improving the resistance to loss of viscosity and weight of GTL base stock(s) and/or base oil(s) lubricant oil formulations
AU2007232024B2 (en) * 2006-03-30 2011-10-06 Nippon Oil Corporation Light oil composition
US20070232503A1 (en) * 2006-03-31 2007-10-04 Haigh Heather M Soot control for diesel engine lubricants
EP2423295A3 (de) * 2006-03-31 2012-08-01 Nippon Oil Corporation Leichtölzusammensetzungen
JP5393372B2 (ja) * 2008-09-25 2014-01-22 昭和シェル石油株式会社 パラフィン主体の燃料電池システム用炭化水素燃料油

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997004038A1 (en) * 1995-07-24 1997-02-06 Union Oil Company Of California Non-toxic, inexpensive synthetic drilling fluid
WO2000020535A1 (en) * 1998-10-05 2000-04-13 Sasol Technology (Pty) Ltd Process for producing middle distillates and middle distillates produced by that process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2008044641A1 *

Also Published As

Publication number Publication date
EP2083061A4 (de) 2013-03-20
US20100012551A1 (en) 2010-01-21
WO2008044641A1 (fr) 2008-04-17
JP2008094879A (ja) 2008-04-24

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