JP5138307B2 - High performance fuel composition - Google Patents

Description

The present invention relates to a kerosene composition, and more particularly to No. 1 kerosene defined in JIS K2203.
The kerosene composition according to the present invention is suitable for lighting and heating.

  No. 1 kerosene specified in JIS K2203 is mainly used in household heating equipment, has a smoke point of 23 mm or more, and a 95% distillation temperature (T95) of 270 ° C. or less. It is prescribed. Further, the sulfur content is specified to be 0.008% by mass or less from the corrosive viewpoint, and the flash point is specified to be 40 ° C. or higher from the safety viewpoint in handling. Smoke points generally indicate the height of a flame that does not produce smoke when burned with a specified lamp, and fuel with a high smoke point does not produce smoke even as a higher flame. It can be taken as a measure of flammability.

Recent buildings have an excellent heat insulation and airtight structure, and are unhealthy and uncomfortable when using home heating equipment, especially open oil stoves such as core oil stoves and oil fan heaters. From the viewpoint of odor, there is a demand for kerosene with low exhaust gas and good combustibility.
In recent years, GTL (Gas To Liquid) kerosene, which is mainly composed of paraffinic hydrocarbons synthesized from natural gas, is being used as kerosene for household heating equipment due to its extremely good flammability. Due to the extremely high flammability of the heating equipment, there is a problem that the height of the flame is high and it takes time to extinguish the fire when it falls.

  Patent Document 1 states that optimization of the composition and distillation properties of kerosene is effective in solving the above-mentioned problems. “Distillation properties are initial boiling points of 135 to 170 ° C., 50% distillation temperature of 165 to 220 ° C. 70% distillation temperature 170 to 240 ° C., 90% distillation temperature 215 to 265 ° C., 95% distillation temperature 230 to 270 ° C., sulfur content of 10 mass ppm or less, saturation content 75 to 98 volume %, The aromatic content is 2 to 25% by volume, 45 to 95% by volume of the saturated content of 75 to 98% by volume is paraffins, and the isoparaffin ratio in the paraffins is 10% by volume or more. Yes, 1.5% by volume or less of the aromatic content of 2 to 25% by volume is a polycyclic aromatic having two or more rings, and the remainder is a single aromatic, and 70% by volume of the single aromatic The above are alkylbenzenes It discloses a postal oil composition ".

On the other hand, non-patent document 1 compares smoke generation with various pure hydrocarbons (however, a test different from the JIS K2537 smoke point test method), and the smoke emission is generally aromatic hydrocarbon>naphthene≈olefin> paraffin. The naphthene has a tendency to be lower than that of aromatic hydrocarbons, but has a tendency to be higher than that of paraffin. However, the fuming properties differ depending on the number and structure of side chains of individual pure hydrocarbons, for example, 2,2-dimethylbutane (smoke point) which is paraffin rather than cyclohexane (smoke point 7.7 cm) which is naphthene. 6.9 cm) and isooctane (smoke point 6.3 cm) have a lower smoke point. Moreover, it is a measurement with a single component having a relatively low boiling point, and from these results, it is impossible to estimate the smoke point of kerosene, which is a mixture of many hydrocarbons having a higher boiling point.
JP 2006-131710 A A. E. Clarke et al., “Smokeability during combustion of organic materials. Part I (The Tenderness to Smoke of Organics on Burning. Part I)”, Journal Institute of Vortex. . 32, no. 275

  The present invention has been created under such a background, and an object of the present invention is to provide kerosene having high handling safety and good flammability even when used in existing home heating equipment.

  As a result of intensive studies to solve the above problems, the present inventor has adjusted the saturated hydrocarbon content and aromatic hydrocarbon content among the compositions in kerosene, more specifically naphthene content, n-paraffin. The present inventors have found the knowledge that the smoke point representing the combustibility of kerosene is improved and the smoke point range is appropriate (for example, 25 to 35) by adjusting the minute amount and aromatic hydrocarbon content.

That is, the present invention includes the following inventions.
[1] Distillation properties having an initial boiling point of 140 to 180 ° C., a 50% by volume distillation temperature of 170 to 210 ° C., and a 95% by volume distillation temperature of 190 to 270 ° C., and a total aromatic hydrocarbon content of 5 to 5. 20% by volume, 80 to 95% by volume of saturated hydrocarbons, 0 to 10% by volume of naphthenes, 8.16 to 19.16% by volume of decane, undecane and dodecane, based on total aromatic hydrocarbons A fuel composition having a volume ratio of the total content of decane, undecane and dodecane of 0.50 to 1.34 , and a sulfur content of 10 mass ppm or less.
[2] The fuel composition according to [1], wherein the naphthene content is 1 to 5% by volume.
[3] The fuel composition according to [1] or [2], wherein the volume ratio of the naphthene to the total aromatic hydrocarbon is 0.1 or more.
[4 ] The fuel composition according to any one of [1] to [ 3 ], wherein a polycyclic aromatic group having two or more rings is 0 to 0.2% by volume.
[ 5 ] The fuel composition according to any one of [1] to [ 4 ], wherein the smoke point is 25 to 35 mm.

  The kerosene of the present invention has a high smoke point and an appropriate range, so it has good flammability, and even when used in an open-type oil stove, the generation of soot is reduced and uncomfortable during ignition and extinguishing. Odor is also reduced.

<Distillation properties>
The kerosene composition according to the present invention has an initial boiling point of 140 to 180 ° C. Preferably it is 150-180 degreeC, Furthermore, 150-170 degreeC is desirable. If the initial boiling point is less than 140 ° C, the flash point may be lowered, and the flash point of the No. 1 kerosene specified in JIS K2203 may be lower than 40 ° C. If the initial boiling point exceeds 180 ° C, ignitability This is because there is a case where the value decreases.

  The kerosene composition according to the present invention has a 50% distillation temperature of 170 to 210 ° C, preferably 170 to 200 ° C, a 95% distillation temperature of 190 to 270 ° C, preferably 190 to 250 ° C, Is preferably 190 to 230, particularly 190 to 210 ° C. When the 50% distillation temperature is 210 ° C. and the 95% distillation temperature is higher than 270 ° C., it is difficult to ignite and it may take time until the combustion reaches a steady state, and it is formed in a cylindrical shape with a woven cloth or the like. In a core type oil stove that sucks up kerosene with a wick and evaporates and burns it at its tip, unburned matter may remain in the wick, which may cause a combustion failure. In particular, when the upper limit of the 95% distillation temperature is lowered to 230 ° C. and further to 210 ° C. to reduce the weight, the unburned portion remaining in the core is particularly reduced, so that the unburned portion is oxidized and deteriorated. Thus, the possibility of causing poor combustion is further reduced. On the other hand, when the 50% distillation temperature is 170 ° C. and the 95% distillation temperature is lower than 190 ° C., there is a possibility that the combustion is too light to maintain a stable combustion state.

<composition>
The kerosene composition according to the present invention has a total aromatic hydrocarbon content of 5 to 20% by volume, preferably 5 to 15% by volume, a saturated hydrocarbon content of 80 to 95% by volume, preferably 82 to 92% by volume, and more. Preferably it is 83-92 volume%. If the aromatic hydrocarbon content exceeds 20% by volume, the smoke point decreases (increases smoke generation), which is not preferable. When the saturated hydrocarbon content is less than 80% by volume, the smoke point is lowered and the smoking property is increased. If the saturated hydrocarbon content exceeds 95% by volume, the smoke point becomes too high, and the flame detection sensor of the combustion equipment may malfunction.

  The saturated hydrocarbon component includes n-paraffin and naphthene, and the kerosene composition according to the present invention contains 5-30% by volume of n-paraffin and 0-10% by volume of naphthene. The smoke point (combustibility) tends to increase as the amount of n-paraffin increases and decrease as the amount of naphthene and aromatic hydrocarbons increases. The effect of lowering the smoke point is greatest for aromatic hydrocarbons. Therefore, the basic adjustment of the smoke point (combustibility) can be performed by adjusting the ratio of the n-paraffin and the aromatic hydrocarbon content. In order to obtain the smoke point as intended by the present invention, it is important that the volume ratio of n-paraffin (mainly decane, undecane and dodecane) to the aromatic hydrocarbon content is 0.5 or more. It is. The volume ratio is preferably 0.8, more preferably 0.9 or more. If it is less than 0.5, the smoke point is lowered and smoke is generated.

  In a typical embodiment, the fuel composition according to the present invention contains 8 to 20% by volume of n-paraffin, 0 to 5% by volume of naphthene, and 8 to 20% by volume of total aromatic hydrocarbons. To do.

  If n-paraffin exceeds 30% by volume, or if the aromatic hydrocarbon content is less than 5% by volume, the flammability increases excessively and the smoke point value as intended by the present invention may be exceeded. There is. On the other hand, when n-paraffin is less than 5% by volume or the aromatic hydrocarbon content is more than 20% by volume, the flammability is deteriorated, and there is a high possibility that the smoke point is less than the value intended in the present invention. In particular, the aromatic hydrocarbon content is preferably 15% by volume or less.

  In addition, a polycyclic aromatic component having two or more rings tends to lower the smoke point. For this reason, it is preferable that the polycyclic aromatic content of two or more rings is 0.20 vol% or less.

  Naphthene is a component that lowers the smoke point. Conventionally, the smoke point lowering action is the second largest after the aromatic hydrocarbon content, and it is close to the aromatic hydrocarbon content compared to the high smoke point of the paraffin content. Was thought to have. However, the present inventor has examined this time, and it is clear that the naphthene content tends to be closer to the paraffin content than the conventionally thought tendency, or has an intermediate tendency between the aromatic hydrocarbon content and the n-paraffin content. It became. Thereby, in the kerosene composition of the present invention, the naphthene content is in the range of 0 to 10% by volume, and the n-paraffin content and the aromatic hydrocarbon content are also adjusted, so that the smoke point is high and appropriate. Since it is within the range, the combustibility is good, and even when used in an open-type oil stove, the generation of soot is reduced, and the unpleasant odor at the time of ignition and extinguishing is reduced.

  Further, in the future, further reduction of sulfur in kerosene is desired, and even when severer reaction conditions are applied in hydrodesulfurization treatment, the kerosene composition according to the present invention has a naphthene content of 0. -10% by volume, so long as a desired desulfurization rate (sulfur concentration) can be achieved, even if a side reaction occurs in which aromatic hydrocarbons are hydrogenated to produce naphthenes to some extent. In addition, since it is possible to select processing conditions such that the naphthene content falls within the scope of the present invention, there is also an advantage that the selection range (option) of reaction conditions in the hydrodesulfurization processing can be expanded.

  If the ratio of the total aromatic hydrocarbon content and the naphthene content is set so that the volume ratio of the naphthene content to the total aromatic hydrocarbon content is 0.1 or more, the smoke point can be significantly improved.

  The sulfur content is 10 mass ppm or less, preferably 5 mass ppm or less, more preferably 1 mass ppm or less. If the sulfur content exceeds 10 ppm by mass, more sulfur oxide (SOx) is generated when burning in an open stove or the like, which is not preferable.

<Properties>
From the viewpoint of moderate combustibility, the smoke point is preferably in the range of 25 to 35 mm, but the kerosene composition according to the present invention has such a smoke point in one embodiment. When the smoke point is less than 25 mm, soot is easily generated in the core type oil stove. In addition, when the smoke point is 35 mm or more, the flame detection sensor resistance value of some oil small water heaters becomes high, which may cause malfunction. Accordingly, the smoke point is preferably in the range of 25 to 35 mm, more preferably in the range of 27 to 35.

  The kerosene composition according to the present invention usually has a flash point of 40 ° C. or higher. In a typical embodiment, the kerosene composition according to the present invention has a flash point of 40-50 ° C, and in a more typical embodiment, 43-46 ° C.

  Copper plate corrosion is 1 or less. When the copper plate corrosion exceeds 1, the copper plate is discolored. When it is severe, the copper plate is deeply discolored or corroded.

  Saybolt color is +25 or more. When the Saybolt color is less than +25, it may be determined that kerosene is colored and is oxidized and deteriorated.

<Analysis method>
The components and properties of the fuel oil composition according to the present application can be evaluated by the following methods.
1) Distillation properties: Atmospheric pressure distillation test of JIS K2254 2) Saturated hydrocarbon content: Petroleum product of JPI-5S-49-97-Hydrocarbon type test method-High performance liquid chromatographic method 3) N-paraffin content: JPI- Petroleum products of 5S-49-97-Hydrocarbon type test method-High performance liquid chromatographic method 4) Naphthene content: described in the next paragraph 5) Aromatic hydrocarbon content (totally aromatic, partially aromatic, bicyclic or more aromatic ): JPI-5S-49-97 Petroleum Products-Hydrocarbon Type Test Method-High Performance Liquid Chromatograph Method 6) Sulfur Content: JIS K2541-6 Sulfur Content Test Method (Ultraviolet Fluorescence Method)
7) Flash point: JIS K2265 (Tag closed flash point test method)
8) Smoke point: JIS K2537 (smoke point test method)
9) Copper plate corrosion: JIS K2513 (copper plate corrosion test method)
10) Saebold color: JIS K2580 (Saebold color test method)

The naphthene content was measured using gas chromatography in which two gas chromatography columns having different polarities were connected in series via a modulator. Detailed conditions are as follows.
GC system: After passing through the primary column, the mass transfer is controlled by the modulator, and then the oil is passed through the secondary column and separated by the difference in polarity. This analyzer system configuration consists of a GC with HP-6890N FID detector manufactured by Agilent Technologies, and an AccuTOF JMS-T100GC time-of-flight mass spectrometer manufactured by JEOL.
Primary column: nonpolar or slightly polar column (for example, PTE-5 manufactured by Supelco, length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm)
Modulator hollow column: length 2m, inner diameter 0.1mm
Secondary column: High polarity column (for example, SpelcoWAX10 manufactured by Supelco, length 2 m, inner diameter 0.25 mm, film thickness 0.25 μm)
Temperature rising condition: 50 ° C. (5 minutes hold) → 280 ° C. (27 minutes hold) Temperature rising rate 10 ° C./min Inlet temperature: 280 ° C.
Injection volume: 0.2 μL
Split ratio: 100: 1
Carrier gas: He, 1.0 mL / min Modulator temperature: The following cold temperature and hot temperature are repeated.
Hot jet gas temperature: 150 ° C. (5 min hold) → 320 ° C. (33 min hold) Temperature rising rate 10 ° C./min Cold jet gas temperature: about −140 ° C.
Modulator frequency: 0.3 seconds hot temperature for 6 seconds, then cold temperature for 5.7 seconds Interface hollow column: 0.5 m length, 0.25 mm inner diameter
FID gas conditions: hydrogen (45 mL / min), air (450 mL / min), make-up helium (25 mL / min, constant)

<Production method>
The method for producing the fuel oil composition of the present invention is not particularly limited. For example, as a raw material oil, a kerosene fraction obtained from an atmospheric distillation apparatus, a catalytic cracking apparatus, a thermal cracking apparatus, or the like, that is, a boiling point is set. It can be obtained by hydrorefining using a fraction distilled in the range of about 140 to 270 ° C. For example, a fraction having a boiling point range of 140 to 280 ° C. flowing out from an atmospheric distillation apparatus is hydrodesulfurized as it is, or a fraction having a boiling point range of 140 to 270 ° C. distilled from a catalytic cracking apparatus or a thermal cracking apparatus is added to this fraction It can be easily obtained by using a mixture of fractions as a raw material.
The hydrodesulfurization is performed using, for example, a catalyst in which an active metal such as Ni, Co, Mo, and W is supported on a porous carrier such as alumina, a reaction temperature of 270 to 350 ° C., a reaction pressure of 2 to 7 MPa, and a liquid space velocity. The fuel composition of the present invention described above is obtained by appropriately selecting the conditions within the range of 0.5 to 6.0 h ⁻¹ and the hydrogen / oil ratio of 130 to 280 Nm ³ / kL. The hydrodesulfurization may be performed under reaction conditions such that the final fuel composition is 10 ppm or less, and monocyclic aromatics and naphthenes may be included in the above range. In particular, it is more preferable that two or more aromatic hydrocarbons are not contained.

  In addition, a fraction rich in normal paraffin, isoparaffin, naphthene, or aromatic hydrocarbon obtained from various purification apparatuses and secondary treatment apparatuses may be used as a base material, and these may be mixed as appropriate.

  The kerosene composition of the present invention may be added to known additives such as an antioxidant, a metal deactivator, a surface ignition preventive, a cleaning dispersant, an anti-icing agent, an auxiliary retardant, an antistatic agent, and a rust inhibitor, as desired. May be added. Although there is no restriction | limiting in particular regarding the kind and addition amount, Usually, it is preferable that it is the range of 1-3000 mass ppm from surfaces, such as a balance of an effect and economical efficiency.

  The kerosene composition according to the present invention is not particularly limited, but is particularly suitable for use as a fuel for household heating appliances, particularly open-type oil stoves such as core-type oil stoves and oil fan heaters.

  EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not limited at all by these examples.

In preparing the light oil composition, each base material used is shown below.
Substrate A (n-C11): undecane fraction obtained from a normal paraffin production apparatus (undecane content 99% by mass or more)
Substrate B (n-C12): dodecane fraction obtained from normal paraffin production apparatus (dodecane content of 99% by mass or more)
Substrate C (Isopara): Isoparaffinic solvent obtained by purifying a polymer of butene and butylene fractions (boiling range: 160 ° C. to 195 ° C.)
Substrate D (naphthene): A fraction obtained by subjecting a straight kerosene fraction to a nuclear hydrogenation treatment of aromatic nuclei and precision distillation (boiling range: 150 ° C. to 200 ° C.)
Substrate E (single ring aroma): fraction obtained by precision distillation of a reformed oil obtained by reforming a straight-run naphtha fraction (boiling range: 150 ° C. to 180 ° C.)

  Table 1 shows the properties of the kerosene compositions used as examples and comparative examples. For each of these kerosene, the smoke point was measured by JIS K2537 (smoke point test method), and the results are also shown in Table 1.

  Comparative Example 1 is an example in which the saturated hydrocarbon content is slightly smaller than the specified range, the total aromatic hydrocarbon content is slightly higher than the specified range, and the smoke point is 24.0 mm. In Example 2, where the saturated hydrocarbon content was the same and the normal paraffin content was increased by about 10% by volume based on Comparative Example 1, the smoke point increased to 25.0 mm. In Example 4, the aromatic hydrocarbon content was reduced by 5% by volume based on Comparative Example 1, the naphthene content was increased, the smoke point was increased, and the smoke point was increased to 26.5 mm. In Example 1, the aromatic hydrocarbon content was reduced by 5% by volume from Example 2, the naphthene content was increased, the smoke point was further increased, and the smoke point was increased to 29.0 mm. In Example 3, the aromatic hydrocarbon content was reduced by 10% by volume based on Comparative Example 1, the naphthene content was increased, and the smoke point was increased to 32.0 mm.

  In Comparative Example 2, the ratio of the n-paraffin content to the total aromatic hydrocarbon content is slightly smaller than the specified range, and the smoke point is 23.0 mm. In Example 6, in which the saturated hydrocarbon content was the same and the normal paraffin content was increased by about 10% by volume based on Comparative Example 2, the smoke point increased to 25.0 mm. In Example 8, the aromatic hydrocarbon content was reduced by 5% by volume based on Comparative Example 2, the naphthene content was increased, the smoke point was increased, and the smoke point was increased to 25.5 mm. In Example 5, the aromatic hydrocarbon content was reduced by 5% by volume from Example 6, the naphthene content was increased, the smoke point was further increased, and the smoke point was increased to 28.0 mm. In Example 7, the aromatic hydrocarbon content was reduced by 10% by volume based on Comparative Example 2, the naphthene content was increased, and the smoke point was increased to 31.5 mm.

Claims (5)

It has a distillation property with an initial boiling point of 140 to 180 ° C, a 50% by volume distillation temperature of 170 to 210 ° C, a 95% by volume distillation temperature of 190 to 270 ° C, and a total aromatic hydrocarbon content of 5 to 20% by volume. 80 to 95% by volume of saturated hydrocarbon, 0 to 10% by volume of naphthene, 8.16 to 19.16% by volume of decane, undecane and dodecane , decane and undecane based on total aromatic hydrocarbons And the fuel composition whose volume ratio of the total content of dodecane is 0.50 or more and 1.34 or less , and whose sulfur content is 10 mass ppm or less.   The fuel composition according to claim 1, wherein the naphthene content is 1 to 5% by volume.   The fuel composition according to claim 1 or 2, wherein the volume ratio of the naphthene to the total aromatic hydrocarbon is 0.1 or more. The fuel composition according to any one of claims 1 to 3 , wherein a polycyclic aromatic content of two or more rings is 0 to 0.2% by volume. The fuel composition according to any one of claims 1 to 4 , wherein the smoke point is 25 to 35 mm.