|Title of Invention||
A KEROSENE COMPOSITION
|Abstract||ABSTRACT 1064/CHENP/2005 A kerosene composition The present invention relates to a kerosene composition comprising 99 to 100 wt% of (i) n-paraffins which have from 7 to 18 carbon atoms and/or (ii) iso-paraffins which have from 7 to 18 carbon atoms along with (iii) cyclo-paraffins, and alkyl derivatives thereof, which have from 9 to 18 carbon atoms, which composition has a smoke point of at least 30 mm.|
The present invention relates to kerosene compositions, particularly for use as heating fuels, which have excellent performance in that, for example, they do not have an unpleasant odor when they are being handled, when they are being Ignited or when they are being extinguished, the combustion exhaust gas is clean and the storage stability is high.
Kerosene is widely used for heating and for cooking purposes. Conventional kerosene, when used for heating purposes, has an oily small when the kerosene is being handled on refueling and this is unpleasant for the user. Furthermore, when used in open-type stoves, such as portable stoves and fan heaters, for example, or when used in a small kitchen oil range for cooking purposes, for example, on lighting and on extinguishing, the combustion is incomplete and there is a disadvantage in that an unpleasant smell is produced by the unbounded hydrocarbons which are produced at this time.
On the other hand, the levels of safety and comfort (low production levels of HOH, hydrocarbon compounds,
CO, SO2, etc. and no accompanying smell], for example, demanded of oil stoves by the user, have also risen year by year. Furthermore, in recent years, problems have arisen with the emergence of kerosene which has been stored over the summer and with the breakdown of oil stoves due to its use, and a demand for improvement in the storage stability of kerosene has also arisen, in view of these circumstances, the kerosene’s which are to be used in oil stoves must satisfactorily fulfill such demands of the user.
A method in which a kerosene vaporizing catalyst is
used/ described in JP'B-59-l$814r a method in which a deodorizing agent is added to the kerosene, described in JP-B-54-32003, and kerosene’s comprising n-paraffin’s and lso-para££ins, dascz-ibed in JP-A-es-ISOaSO/ for example, have been proposed for resolving the problems of the unpleasantness when handling and the unpleasant smell on ignition and on extinguishing, which are observed generally with kerosene’s.
However, with the method in which a kerosene vaporizing catalyst is used, the catalyst deteriorates with the passage of time and so It has been difficult to maintain clean combustion over a prolonged period of tine. Furthermore, the method in which a deodorizing agent is added to kerosene is not very effective because of the problem that the smell is not agreeable to some people, furthermore, although kerosene comprising n-paraffin’s and iso-paeaffins do not have an unpleasant smell when being handled and when being lit and extinguished and with which the exhaust gas is also clean, the production costs are greatly increased and there is therefore the problem that these kerosenes are expensive. Furthermore, kerosenes comprising iso-paraffins and n-paraffins which have 9 or 10 carbon atoms as the main components have a lower density than existing kerosenes and the fuel consultation by volume is Increased, and so, for example, it is likely that the JIS specification |of the Japanese Standards Association) for fuel consumption in an oil stove will not be satisfied. Moreover, the Clash point is reduced and there are also problems with safety.
The present Invention is intended to provide kerosene compositions for which the cost, fuel consumption and flash point axe similar to those of kerosenes in general, and with which, unlike those obtained using conventional-methods, the smell of the
kerosene itself is very slight, there is no unpleasant oily am ell when it ia being handled, with which there is no smell on ignition and extinguishing* which has good combustibility, with which the exhaust gas on combustion is clean, and which also has excellent storage stability.
As a result of thorough research carried out with a view to resolving the problems associated with the aforementioned prior art, it has been found that the aforementioned aims can be realized with kerosenes which contain specified amounts of n-paraffins and/or iso-paraffin, along with cycloparaffins and alkyl derivatives thereof;' which all have specified numbers of carbon atoms, in place of the conventional kerosenes obtained by the distillation of crude oil, and the present invention is based upon this discovery.
According to the present invention there Is provided a kerosene composition containing at least 99 wt% of n-parafflns which have from 7 to IS carbon atoms and/or Iso-paraffins which have from 7 to 18 carbon atoms along with cyclo-paratflns, and alkyl derivatives thereof, which have from 9 to 18 carbon atoms. Preferably, at least 99 wt of said n-paraffins and/or iso-paraffins have from 7 to 12 carbon atoms. Preferably, at least 99 wt% of said cyclO'paraffins have from 9 to 12 carbon atoms.
In said kerosene composition according to the present invention the ratio by weight of the n-parafflns and/or Iso-paraffins to the eyelid-paraffins and alkyl derivatives thereof is penetrably from 92:8 to 25:75, more preferably from 85:IS to ^5:45.
Said kerosene composition according to the present invention preferably has a smoke point of at least 30 mn.
The n-paraffins and iso-paraffins which have from 7
to 18 carbon atoms which are used in the present invention can be obtained by taking synthetic gas obtained by partial oxidation, steam reforming from coal, natural gas, for example, and producing long-chain alkyl hydrocarbon polymer oil by means of a fischer-Tropsch reaction and then carrying out hydro cracking and distillation. Furthermore, they can also be obtained in view of production costs by cracking or synthesis, for example, from the various fractions which are obtained in petroleum refining.
If the n-paraffins or iso-paraffins have less than 7 carbon atoms then the boiling point and flash point are too low and this is undesirable, and If the number of carbon atoms exceeds 18 then there are problems with low temperature fluidity, the boiling point is also raised too far and there is an adverse effect on the combustibility, which is undesirable.
Examples of the n-paraffin and iso-parafflns which can be used in the present invention include n-heptane, iso-heptane, n-octane, iso-octano, n-nominee, iso-nonane, n-decane, Iso'decane, n-undecane, iso-undecane, n-dodecane, iso-dodecane, 2-methylheptane, 2r2-dlnethylhexane, 2-methyloctane, 2,2-dimethylheptane, 2-methylnonane, 2,2-dlmethyloctane, 2-methyldecane and 2 -dluiethyl/ionano.
The cyclo-paraffins, and the alkyl derivatives thereof, which have from 9 to 16 carbon atoms and which can be used in the present invention can be obtained by the hydrogenation of the light oil and intermediate oil fractions obtained by the distillation of coal tar, or by separation by distillation from crude oil and hydrogenation of the various distillate fractions.
If the number of carbon atoms of the cyclo-paraffins or alkyl derivatives thereof is leas then 9 then the flash point is too low and this is undesirable, and if
the number of carbon atoms exceeds 1.B then the boiling point is too high and there Is an adverse effect on the combustibility, and this is undesirable.
Examples of the cyclo-parafflns and alkyl derivatives thereof which can be used In the present invention include n-butyl-cyclopentane, n-pentyl-cyclopentane, n-hexyl-cyolopentane, isopropyl-cyclohexane, n-butylcyclohexane, n-pentyl-cyclohexane, n~hexyl-cyclohexane, cis-decahydronaphthalene, trans-decahydronaphthalene, 1-tnethyl- (trans-decahydronaphthalene) and 9-ethyl- [cis-decahydronaphthalene).
The kerosenes of the present Invention must contain at least 99 wt4 of the aforementioned n-parafflns anti/or iso-paraffins along with the cyclo-parafflns and alicyl derivatives thereof. If the content is less than 99 wt*, then aromatic components oleflnlc components, oxygen ‘containing components, nitrogen-containing components and sculpture-containing components are a
Suitably, said n-paraffin’s and/ox iso-paraffins have been obtained by mean of Fischer-Tropsch synthesis.
The kerosene compositions of the present invention ccMtiprislng the compositions indicated above have the properties (IJ to (4) indicated below, and in particular they have a high smoke point and excellent combustibility. As the smoke point is raised and the coiabuatiblllty la reproved, the /row ignition to complete combustion is shortened and complete combustion is promoted in the steady combustion state. Consequently there is no unpleasant smell or soot on ignition and the exhaust gas on Ignition and during steady state combustion is also clean.
(1) Distillation IBP (Initial Boiling Point) is above ISO'C, and preferably above 155'C, and the 95% distillation temperature is less than 270"C.
(2) Flash point is at least 40*'C.
(3) Sculpture content is not more than 10 pub.
(4) Smoke point is at least 30 mm [corporations with smoke points of at least 35 nm, and even of 40 mm can also be obtained.]
The present invention will now be described by way of example with reference to the accompanying drawings, in which:-
Figure 1 shows the change in the Saybolt value in an oxidation stability teat; and
Figure 2 shows the change in the amount of peroxide in an oxidation stability test. Example I
An n-paraffin/iso-paraffin mixed oil of the composition shown in Table 1 was obtained by production with the SHDS (Shell Middle Distillate Synthesis) process, in which natural gas la partially oxidized,
heavy paraffins are synthesized by is means of Fischer-Tropes synthesis, and naphtha, kerosene and light oil fractions are obtained by hydro cracking of the
Next. 92 parts by weight of the mixed oil and 8 parts by weight of decalin (decahydronaphthalenc) were mixed together and an n-paraffln/iso-paraffin/decalin mixed kerosene was obtained.
Moreover, the concentrations of the iso-paraffins in Table 1 indicate the concentrations of all of the branched hydrocarbons which have the same carbon number since it is difficult to determine the isomers with different structures. For example iso-octane includes all isomers such as 2-methylheptane, 2,2-dliriethylhexane and the like. Example 2
Seventy parts by weight of the n-paraffin/iso-paraffin mixed oil obtained in Example 1 and 30 parts by weight of decalin were mixed and an n-paraffin/iso-paraffin/decal mixed kerosene was obtained. Example 3
Twenty five parts by weight of the n-paraffin/iso-paraffin mixed oil obtained in Example 1
and 75 parts by weight Q£ decalin were mixed and an n-paraffin/isQ-paraffln/decalln mixed kerosene was obtained.
The properties o£ the kerosene mixtures of Examples 1 to a obtained in the way outlined above, kerosene of the composition shown in Table I produced by the SHDS process (Comparative Example 1) and JIS No.l kerosene which ia generally sold (Comparative Example 2) axe shown In Table 2.
As in clear from Table Z, the properties of the kerosene compositions of the present invention showed a smoke point much higher than that of Comparative Example 2, superior burning properties and a smaller sulphur fraction. EMrthexnoreF they had a higher ignition point (flash point] than that of Comparative Example 1, and the JIS specification was satisfied.
The test5 indicated below were carried out using the kerosene of Spangles 1 to 3 and Comparative Examples, 1 and 2. Stove Burning Teat
Combustion performance tests were carried out using a .wick top to bottom type stove and a petroleum fan heater. The Cue! consumptions for maximum burning and the CO/CO2 ratio of the exhaust gas were measured in
accordance with the test methods laid down in JIS S 2019 and JIS S 2031 in the case of the wick top to bottom type stove and in accordance with JIS S 2036 and JIS S 3031 in the case of the petroleum fan heater. The results obtained are shown in Table 3.
As 1B clear from Table 3, the kerosene compositions of the present invention had a lower CO/CO2 and a much lower SO2 content in the exhaust gas when compared with the Icerosene of Comparative Example 2, and they provided a cleaner exhaust gas. Furthermore, the kerosene of Comparative Example 1 was such that the difference between the Indicated and measured fuel consumption (L/h) per stove capacity did not satisfy the JIS specification of within ±10>, while the kerosene compositions of the present Invention did satisfy this JIS specification. Odors Function Teat
Twenty function teats were carried out using a wick top to bottom type stove and a petroleum fan heater, when ignited and when extinguished. The results are shown in Table 4.
As is clear from Table 4, the kerosene compositions ol the present invention were such that the keroaenea themselves had less odour than th« kerosene of Comparative Example 2, and they also had less odour when they were lit and when they were extinguished. Oxidation Stability Teat
The Saybolt colour and the amount of peroxide were determined as measures of the deterioration which had occurred after a fixed period of time with carbon-arc irradiation at 40'C In a weathermeter (manufactured by the Suga Testing Machine Co.] as the test apparatus. The results are shown in Figures 1 and 2.
It is clear from figures 1 and 2 that the kerosene composition of the present invention was much less liable to deteriorate than the kerosene of Comparative Example 2 and had excellent storage stability.
By means of the present invention it is possible to provide a kerosene ccsnposition for which the cost, fuel consumption and ignition point are the sane as those of a general kerosene, with which the odour of the kerosene itself is very slight so that there is no unpleasant oily smell when it la being handled, which has good burning properties and provides a clean exhaust gas when it is burned, and which has excellent storage properties, which has not been obtained with conventional methods.
1. A kerosene composition comprising 99 to 100 wt% of (i) n-paraffins which have from 7 to 18 carbon atoms and/or (ii) iso-paraffins which have from 7 to 18 carbon atoms along with (iii) cyclo-paraffms, and alkyl derivatives thereof, which have from 9 to 18 carbon atoms, which composition has asmoke point of at least 30 mm,
2. The kerosene composition as claimed in claim 1, wherein 99 to 100 wt% of said n-paraffins and iso-paraffins have from 7 to 12 carbon atoms.
3. The kerosene composition as claimed in claim 1 or 2, wherein 99 to 100 wt% of said cyclo-paraffms have from 9 to 12 carbon atoms.
4. The kerosene composition as claimed in claim 1, 2 or 3, wherein the ratio by weight of the n-paraffms and/or iso-paraffins to the cyclo-paraffms and alkyl derivatives thereofis 92:8 to 25:75.
5. The kerosene composition as claimed in claim 4, wherein said ratio is from 85:15 to
6. The kerosene composition as claimed in any one of the preceding claims wherein
the n-paraffms and iso-paraffins are selected from n-heptane, iso-heptane, n-octane,
iso-octane, n-nonane, iso-nonane, n-decane, iso-decane, n-undecane, iso-midecane, n-
dodecane, iso-dodecane, 2-methylheptane, 2, 2-dimethylhexane, 2-methyIoctane, 2,2-
dimethylheptane, 2-methyhionane, 2,2-dimethyloctane, 2-methyldecane and 2-
7. The kerosene composition as claimed in any one of the precedmg ciauns wnerem the cyclo-paraffins are selected from n-butyl-cyclopentane, n-pentyl-cyclopentane, n-hexyl-cyclopentane, isopropyl-cyclohexane, n-butyl-cyclohexane, n-pentyl-cyclohexane, n-hexyl-cyclohexane, cis-decahydronaphthalene, trans-decahydronaphthalene, l-methyl-(trans-decahydronaphthalene) and 9-ethyl-(cis-decahydronaphthalene).
8. The kerosene composition as claimed in claim 7, wherein the cyclo-paraffins are selected from cis- and trans-decahydronaphthalene.
9. The kerosene composition as claimed in any one of the preceding claims wherein
the n-paraffins and iso-paraffins have been obtained by means of Fischer-Tropsch
|Indian Patent Application Number||1064/CHENP/2005|
|PG Journal Number||23/2008|
|Date of Filing||30-May-2005|
|Name of Patentee||SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V|
|PCT International Classification Number||C10 L 01/04|
|PCT International Application Number||PCT/EP2003/050935|
|PCT International Filing date||2003-12-03|