JP2014105246A - Kerosene base material and kerosene composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a kerosene base material having reduced specific odor due to olefin or dienes, and capable of exhibiting good oxidation stability and low temperature fluidity when made as a kerosene composition, and to provide a kerosene composition containing the kerosene base material and having good oxidation stability and low temperature fluidity.SOLUTION: There is provided a kerosene base material manufactured by mixing 100 pts.vol. of heavy naphtha and/or straight-run gas oil and 1 to 50 pts.vol. of pyrolysis oil having specific characteristic obtained by a heat decomposition of naphtha, and having PetroOXY obtained by a hydrogenation treatment of 6 min. or more and the mercaptan concentration of 18 mass ppm or less. There is also provided a kerosene composition having the kerosene base material of 1 vol.% or more and having the flash point of 40°C or higher, the smoke point of 21.0 or more, 90% distillation temperature of 268°C or lower and PetroOXY of 50 min. or more.

Description

  The present invention relates to a kerosene base material and a kerosene composition containing the same.

  As a naphtha pyrolysis fraction, for example, a pyrolysis fraction by-produced from an ethylene production apparatus contains a large amount of olefins and dienes, and is difficult to use as a fuel oil because of its characteristic odor and low oxidation stability. . For this reason, the pyrolysis fraction is passed through the fluid catalytic cracking apparatus to perform the catalytic cracking treatment, but there is a problem that a large amount of coke is generated and the regeneration tower temperature is increased. As another method for removing olefins and dienes, there is a method of hydrogenation. However, in the usual method, since olefins and dienes are polymerized before hydrogenation, special processes and expensive noble metal catalysts are required. There was a problem of high cost.

  Further, when hydrorefining of a pyrolysis fraction is performed using a catalyst in which Mo, Co, Ni, or W is supported on alumina or silica alumina, there is a problem that the catalyst life is remarkably shortened. Therefore, in general, hydrorefining treatment has been performed by mixing pyrolyzed oil with straight-run gas oil to such an extent that the catalytic activity is not significantly deteriorated. However, in this method, the throughput of the pyrolysis fraction is limited, and deterioration of the catalyst activity cannot be avoided sufficiently.

  Therefore, a hydrorefining treatment method in which a pyrolysis fraction and a straight-run gas oil fraction are mixed at a volume ratio of 5:95 to 80:20, and 5-45 vol% catalytic cracking oil is mixed and hydrogenated. Has been proposed (see, for example, Patent Document 1). According to this treatment method, it is said that the amount of pyrolysis oil can be increased, catalyst activity deterioration is suppressed, and deep desulfurization or advanced denitrification treatment is possible.

Japanese Patent Application Laid-Open No. 08-049881

  However, even with the above-described method, there is a problem that a characteristic odor due to olefins and dienes remains, and good oxidation stability and low-temperature fluidity cannot be obtained when a kerosene composition is obtained.

  As described above, the present invention is a kerosene base material that has reduced characteristic odor due to olefins and dienes, and can exhibit good oxidation stability and low-temperature fluidity when used as a kerosene composition. An object of the present invention is to provide a kerosene composition comprising the kerosene base material and having good oxidation stability and low temperature fluidity.

  As a result of intensive studies to solve the above problems, the present inventors have arrived at the following present invention and found that the problems can be solved. That is, the present invention is as follows.

[1] 100 parts by volume of heavy naphtha and / or kerosene are mixed with 1 to 50 parts by volume of pyrolyzed oil having the following properties (1) and (2) obtained from the thermal decomposition of naphtha, and a reaction temperature of 180 A kerosene base material having PetroOXY obtained by hydrogenation at ˜210 ° C. for 6 minutes or more and a mercaptan concentration of 18 mass ppm or less.
(1) The 10% distillation temperature is 40 to 100 ° C, the 50% distillation temperature is 150 to 210 ° C, and the 90% distillation temperature is 240 to 380 ° C.
(2) The density is 0.93 to 0.99 g / cm ³ .
[2] The kerosene base material according to [1], wherein dicyclopentadiene and styrene monomer are not contained in a component obtained by volatilization when heated to 56 ° C.
[3] The hydrogenation treatment is performed using a hydrogenation catalyst in the presence of hydrogen, and the treatment conditions are a hydrogen pressure of 2 to 6 MPa and a liquid space velocity (LHSV) of 0.3 to 1.5 h. ^-1 , The kerosene base material according to [1] or [2], wherein the hydrogen / oil ratio is 250 to 500 Nm ³ / kL.

[4] The kerosene substrate according to any one of [1] to [4] is contained in an amount of 1% by volume or more, a flash point is 40 ° C. or more, a smoke point is 21.0 or more, and a 90% distillation temperature. Is a kerosene composition having a temperature of 268 ° C. or lower and PetroOXY of 50 minutes or longer.

  According to the present invention, a characteristic odor due to olefins and dienes is reduced, and a kerosene base material capable of exhibiting good oxidation stability and low-temperature fluidity when used as a kerosene composition, And a kerosene composition comprising the kerosene base material and having good oxidation stability and low temperature fluidity.

[Kerosene base material]
The kerosene base material of the present invention is a pyrolysis oil having a predetermined property obtained from the thermal decomposition of naphtha (hereinafter referred to as “the pyrolysis oil according to the present invention”) for 100 parts by volume of heavy naphtha and / or kerosene. 1) to 50 parts by volume are mixed and obtained by hydrogenation at a reaction temperature of 180 to 210 ° C.

If the pyrolysis oil according to the present invention is less than 1 part by volume, there is no effect of addition, and if it exceeds 50 parts by volume, a large amount of heat of hydrogenation is generated in the reaction tower used for the hydrotreatment, and there is a risk of thermal runaway. Moreover, there exists a problem that reduction of an odor is inadequate.
The pyrolysis oil according to the present invention is preferably 5 to 40 parts by volume, and more preferably 10 to 30 parts by volume.

The pyrolysis oil according to the present invention has the following properties (1) and (2) as predetermined properties.
(1) The 10% distillation temperature (T10) is 40 to 100 ° C, the 50% distillation temperature (T50) is 150 to 210 ° C, and the 90% distillation temperature (T90) is 240 to 380 ° C.
By having such a distillation property, the hydrogenation treatment can be suitably performed.
The 10% distillation temperature is preferably 45 to 95 ° C, more preferably 50 to 90 ° C. The 50% distillation temperature is preferably 160 to 200 ° C, more preferably 170 to 190 ° C. 90% distillation temperature becomes like this. Preferably it is 240-370 degreeC, More preferably, it is 240-360 degreeC.
If it is in the range of these distillation temperature, content of nitrogen content can be reduced and poisoning to the hydrogenation catalyst by nitrogen content can be suppressed. In addition, it is preferable that the nitrogen content of pyrolysis oil is 50 mass ppm or less, and it is more preferable that it is 30 mass ppm or less. Moreover, each distillation temperature in pyrolysis oil is the distillation temperature of gas chromatography.

(2) The density is 0.93 to 0.99 g / cm ³ . If the density is less than 0.93 g / cm ³ , the calorific value is reduced and the amount of fuel used is increased. On the other hand, if it exceeds 0.99 g / cm ³ , the hydrogenation process becomes difficult (caulking, reduced catalyst activity). Preferably the density is 0.94~0.985g / cm ^3, more preferably 0.945~0.98g / cm ^3, further to be 0.95~0.98g / cm ³ preferable.

  The kerosene base material of the present invention preferably contains no dicyclopentadiene and styrene monomer in the component obtained by volatilization when heated to 56 ° C. Odor-causing substances include cyclopentadiene, dicyclopentadiene, 2,4,4-trimethyl-1-pentene, styrene monomer and 4-vinylcyclohexene. Since pentadiene and styrene monomer remain to the end, the absence of dicyclopentadiene and styrene monomer serves as an index, and the characteristic odor caused by olefins and dienes can be greatly reduced.

Further, the PetroOXY of the kerosene base material of the present invention is 6 minutes or more, preferably 50 minutes or more, and the mercaptan concentration is 18 mass ppm or less, preferably 16 ppm or less.
PetroOXY serves as an index of oxidation stability and is measured by the method described in the examples described later. If PetroOXY is less than 6 minutes, the possibility of oxidative degradation during long-term storage increases.
Further, the mercaptan concentration is also measured by the method described in Examples described later. When the mercaptan concentration exceeds 18 mass ppm, a unique strong odor is felt.
Further, by reducing the mercaptan concentration of the base material, the mercaptan concentration of the product (kerosene) also decreases, and if the product is 5 ppm or less, a unique odor cannot be felt.

After the pyrolysis oil according to the present invention is mixed with heavy naphtha and / or kerosene, hydrogenation is performed at a reaction temperature of 180 to 210 ° C. to obtain the kerosene base material of the present invention. By this hydrogenation treatment, malodorous substances such as styrene and dienes are hydrogenated to hydrogenate alkylbenzenes and monoolefins with relatively little odor.
In a normal kerosene hydrotreating apparatus, the reaction temperature is 300 ° C. or higher. Therefore, when the pyrolysis oil is blended, olefins and dienes are polymerized at sites exceeding 210 ° C., resulting in heat exchangers, heating furnaces, reaction towers. In such cases, dirt and pressure loss increase, and it may be difficult to continue operation.
Detailed conditions (preferred conditions) for the hydrogenation treatment will be described later.

Here, as the heavy naphtha, the 10% distillation temperature in the Angler distillation is 120 ° C. or higher in consideration of the flash point, preferably 140 ° C. or higher, and the 90% distillation temperature is 240 in consideration of the presence of the resin content. Those having a temperature of ℃ or less, preferably 220 ℃ or less are suitably used. In consideration of use as a heavy oil composition, the 90% distillation temperature is preferably 160 ° C. or higher. For example, light naphtha mainly composed of fractions having 5 and 6 carbon atoms and heavy naphtha which is a bottom fraction obtained by distilling and separating heavy naphtha composed mainly of fractions having 7 and 8 carbon atoms from imported naphtha. .
As a naphtha raw material for obtaining heavy naphtha, naphtha generally called full-range naphtha can be mentioned. Since imported naphtha contains heavy components having 9 or 10 carbon atoms, heavy naphtha obtained after separating light naphtha or heavy naphtha is particularly preferably used.

  Kerosene is not particularly limited, and general kerosene can be used, but kerosene also has a 10% distillation temperature (T10) in the Engler distillation of 120 ° C. or higher, preferably considering the flash point. In consideration of the presence of the resin component, 140 ° C. or higher and a 90% distillation temperature (T90) of 240 ° C. or lower, preferably 220 ° C. or lower are preferably used. For example, a straight-run kerosene fraction or a cracked kerosene fraction is applicable.

  As properties of heavy naphtha and kerosene, the nitrogen content is preferably 20 mass ppm or less, more preferably 10 mass ppm or less, in order to suppress poisoning of the hydrogenation catalyst, and 5 mass ppm or less. More preferably, it is most preferably 3 ppm by mass or less. Moreover, it is preferable that a density is 0.76-0.80 g / ml.

  Various additives can be mixed in the kerosene base of the present invention as long as the effects of the present invention are not impaired. For example, antioxidants, low-temperature flow improvers and the like can be mentioned.

  The kerosene substrate of the present invention as described above is prepared by mixing 1 to 50 parts by volume of the pyrolysis oil according to the present invention with 100 parts by volume of the above-described heavy naphtha and / or kerosene, and a reaction temperature of 180 to 210 ° C. It is manufactured through a hydrogenation process at

  As the pyrolysis oil according to the present invention, a pyrolysis fraction by-produced from an ethylene production apparatus can be applied. The pyrolysis oil having the predetermined properties described above can be obtained by controlling the pyrolysis conditions and distillation conditions. In order to effectively use by-products from other petrochemical production apparatuses, the by-products can be used as part of the pyrolysis oil as long as the effects of the present invention are not impaired. For example, the slop etc. byproduced from a styrene monomer apparatus are mentioned.

  The mixing method of the heavy naphtha and / or kerosene and the pyrolysis oil according to the present invention is not particularly limited, and examples thereof include stirring and mixing in a tank, mixing using a static mixer in a pipe, and the like.

  The hydrogenation treatment is performed using a hydrogenation catalyst in the presence of hydrogen. As a hydrogenation catalyst, P may be contained in an existing molybdenum-based hydrogenation catalyst (CoMo or NiMo). A support of an alumina type is preferably used.

As conditions for the hydrogenation treatment, the hydrogen pressure is preferably 2 to 6 MPa, and more preferably 3 to 4 MPa. By setting the hydrogen pressure to 2 to 6 MPa, coking can be prevented and the life of the catalyst can be extended.
The higher the hydrogen pressure (= total pressure (pressure of the high-pressure separator at the outlet of the reaction tower) x hydrogen concentration in the supplied hydrogen gas), the easier the hydrogenation, but at the same time, more heat is generated by the hydrogenation. Inconveniences such as excessive control becomes difficult and equipment costs increase, and therefore, it is preferable to set the above-mentioned range in consideration of costs.

Reaction temperature is 180-210 degreeC, and it is more preferable to set it as 190-200 degreeC. By suppressing the progress of the polymerization reaction by setting the reaction temperature to 180 to 210 ° C., it becomes possible to operate safely and stably, and the odor can be improved. The odor can be reduced by setting the reaction temperature to 180 ° C. or higher, thereby reducing the specific odor caused by the olefins and dienes described above, and by hydrodesulfurization by setting the reaction temperature to 210 ° C. or lower. Odor due to mercaptans produced by reacting sulfur compounds again can be reduced.
The reaction temperature when the reactor is a tubular reactor (reaction tower) refers to a temperature defined by the catalyst weight average temperature.
Further, it is preferable that the liquid hourly space velocity (LHSV) 0.3～1.5H ^-1, more preferably, to 0.5～1.0H ^-1, and 0.75～1.0H ^-1 More preferably. By setting the liquid space velocity to 0.3 to 1.5 h ⁻¹ , the odor-causing substance can be selectively hydrogenated.
Furthermore, the hydrogen / oil ratio is preferably in the 250 to 500 nm ³ / kL, and more preferably in the 300 to 500 nm ³ / kL. By setting the hydrogen / oil ratio to 250 to 500 Nm ³ / kL, hydrogen necessary for the reaction can be supplied and deterioration of the catalyst can be suppressed. In addition, the oil of hydrogen / oil ratio is based on the pump liquid supply (kL: kiloliter).

[Kerose oil composition]
The kerosene composition of the present invention contains 1% by volume or more of the above-described kerosene substrate of the present invention, has a flash point of 40 ° C. or higher, a smoke point of 21.0 or higher, and a 90% distillation temperature of 268 ° C. It is as follows.

    When the content of the kerosene base material of the present invention is less than 1% by volume, the addition amount is small and the effect is small. The kerosene base material of the present invention is preferably 1 to 50% by volume, more preferably 1 to 25% by volume, further preferably 1 to 20% by volume, and 5 to 20% by volume. Is particularly preferred.

  When the cetane index of the kerosene composition of the present invention is less than 35, combustibility is deteriorated. Further, if the flash point is less than 60 ° C., it is not preferable in terms of handling safety. Furthermore, if the clogging point is higher than −6 ° C., there is a high possibility that the filter at a low temperature is clogged. Moreover, when a pour point is higher than -20 degreeC, possibility that it will solidify in a line at low temperature becomes high.

  The cetane index is preferably 35 or more, and more preferably 40 or more. The flash point is preferably 60 ° C. or higher, and more preferably 62 ° C. or higher. The clogging point is preferably −6 ° C. or lower, and more preferably −9 ° C. or lower. The pour point is preferably −20 ° C. or lower, more preferably −22.5 ° C. or lower.

  The cetane index can be set to 35 or more by adjusting the hydrogenation conditions, specifically, the hydrogen pressure, the hydrogen / oil ratio, the reaction temperature, and controlling the density and distillation properties. The flash point can be adjusted to 60 ° C. or higher by adjusting the distillation conditions. Regarding the clogging point and the pour point, the pyrolysis oil has few linear paraffins that worsen the clogging point. Therefore, by adjusting the blend amount, it can be made -6 ° C or lower and -20 ° C or lower, respectively. .

As the kerosene component to which the kerosene base material of the present invention is added in the kerosene composition of the present invention, it is preferable to use kerosene that complies with the provisions of JIS K 2203 No. 1 or No. 2.
Further, as the above kerosene, straight-run kerosene (or desulfurized kerosene) obtained from an atmospheric distillation apparatus, straight-run light diesel oil (or desulfurized light diesel oil), straight-run heavy diesel oil (or desulfurized heavy diesel oil) ) As a main component, a light cycle oil obtained from a fluid catalytic cracking device and / or a residue fluid catalytic cracking device, a hydrogenated vacuum gas oil obtained by hydrogenating a vacuum gas oil obtained from a vacuum distillation device, Mix hydrocracked light oil obtained from hydrocracking equipment, direct degasified light oil obtained from direct heavy oil desulfurization equipment, etc., and further mix atmospheric residual oil for directing residual carbon, direct dehydrated residual oil, vacuum residual oil, etc. In other words, it is possible to use a product manufactured so that the residual carbon content of 10% residual oil exceeds 0.2% by weight.

  Various additives can be mixed in the kerosene composition of the present invention as long as the effects of the present invention are not impaired. Examples thereof include cetane number improvers, antioxidants, stabilizers, dispersants, fluidity improvers, metal deactivators, microbial disinfectants, auxiliary agents, antistatic agents, discriminating agents and the like.

Each substrate used in this example is as follows.
[Base material]
(1) Heavy naphtha The properties of heavy naphtha used are shown in Table 1 below.

(2) Pyrolysis oil The properties of the pyrolysis oil used are shown in Table 2 below.

(3) Kerosene Properties of the kerosene used are shown in Table 3 below.

[Measurement and evaluation method]
Various measurement / evaluation methods in this example are as follows.
(1) Density Measured according to JIS K 2249.

(2) Distillation property (i) Gas chromatography distillation property It measured based on JISK2254.
(Ii) Engler distillation properties Measured according to JIS K 2254.
(3) Mercaptan Concentration and Sulfur Content Mercaptan Concentration: JIS K 2276 Mercaptan Sulfur Content Analysis Test Method Sulfur Content: JIS K 2541-4 “Radiation Excitation Method” (in the case of 10 wtppm or more)
JIS K 2541-7 “wavelength dispersive X-ray fluorescence method” (when less than 10wtppm)

(4) Measurement of concentration of dicyclopentadiene and styrene monomer The concentration of dicyclopentadiene in the component obtained by volatilization when heated to 56 ° C was measured as follows. The concentration of styrene monomer was also measured in the same manner. Here, when the area% of gas chromatography measured for dicyclopentadiene and styrene monomer was less than 0.1%, it was regarded as having no odor component. There was a case of 0.1 or more.

First, 0.03 g of a sample was collected in a vial bottle size of 20 ml, placed in an oven and heated at 56 ° C. for 0.1 minute, and a volatilized component was collected. Then, GC-MS analysis was performed using 1 ml of the sample of the volatilized component.
GC condition: inlet 240 ° C
Column DB-1 (length 30m, diameter 0.32mm)
Oven temperature 40 ° C (5min) → 240 ° C (10min)
Temperature increase rate is 10 ° C / min
MS conditions: Scan Mode (m / z 29-400)

(5) Sensory test The sensory test was performed according to the three-point preference method. When it felt that there was a peculiar strong smell, it was set as x when there was a little peculiar smell, and when there was no peculiar smell.

(6) Smoke point Measured according to JIS K2537.
(7) Flash point Measured according to JIS K 2265.

(8) Oxidation stability The oxidation stability of the kerosene base material and kerosene composition was measured by the PetroOXY test "Ministry of Economy, Trade and Industry Notification No. 72 (method determined by the Minister of Economy, Trade and Industry as a method for measuring oxidation stability in diesel oil)" Expressed by induction period. The induction period is the time from when a predetermined amount of oxygen is sealed in 5 ml of the sample and raised to 140 ° C. until the initial pressure is reduced by 10%.
(9) Bromine number It measured based on JISK2605.
(10) Nitrogen content Measured according to JIS K 2609.

[Examples 1 to 6 and Comparative Example 1]
Under the conditions shown in the following Table 4-1 and Table 4-2 and the following conditions, various base materials were mixed and hydrogenated to prepare a kerosene base material.
The hydrotreating uses a high-pressure fixed-bed flow reactor, and the catalyst is a cobalt oil-based commercial diesel oil desulfurization system that has been used for 2 years so that the sulfur content of the desulfurized diesel oil is 10 mass ppm or less in a diesel oil deep desulfurization unit. The catalyst (used catalyst) was washed with commercially available kerosene and then air-dried in air, and filled with 60 ml.
The raw material oil was circulated in a down flow type introduced from the upper stage of the reaction tube together with hydrogen gas having a purity of 100% to evaluate the reaction.
Although the used catalyst used was sulfided, there was a possibility that it was oxidized with air, so a treatment corresponding to presulfidation was performed. The reaction pressure (hydrogen pressure) was adjusted at the reactor outlet. The hydrogen / raw oil ratio was adjusted by the feed rate at the hydrogenation reactor inlet.
As pretreatment, DMDS (dimethyl disulfide) was added and the sulfur concentration was adjusted to 2.0% by mass. A presulfurized oil based on a Middle East gas oil with a density of 0.844 g / cm ³ was circulated together with hydrogen gas, After first treating at 110 ° C. for 4 hours, the temperature was raised to 360 ° C. over 10 hours, and sulfiding treatment was performed at 360 ° C. for 4 hours. Thereafter, the raw material oil was switched to heavy naphtha, and the oil was passed at a temperature of 360 ° C. for 4 hours. After washing and removing heavy components considered to be contained in the catalyst, the temperature was lowered to a predetermined temperature.
The produced oil was recovered up to 2 L from 400 cc by adjusting the recovery time. Nitrogen gas was passed through the produced oil collected in a predetermined amount in the system container at 60 NL / h for 0.5 hour to remove hydrogen sulfide contained in the produced oil. Since the pyrolysis oil and the diluted oil such as heavy naphtha change in quality at room temperature, they were stored in a cool box at a temperature of 0 ° C.
Various measurements and evaluations were performed on the produced kerosene base material. The results are shown in the following Table 4-1 and Table 4-2, and the following Table 5-1 and Table 5-2.

  When pyrolysis oil B was 75% by volume (Comparative Example 2), coking occurred due to olefin polymerization and the like at a reaction temperature of 220 ° C. At this time, an exothermic reaction was observed, coking occurred near the reactor inlet, and clogging occurred. For this reason, the product oil was not obtained and could not be evaluated.

[Examples 8 to 13 and Comparative Examples 4 and 5]
As shown in Table 6-1 and Table 6-2 below, various base materials were mixed to prepare a kerosene composition. Various measurements and evaluations were performed on the produced kerosene composition. The results are shown in Tables 6-1 and 6-2 below.

Claims (4)

1 to 50 parts by volume of pyrolysis oil having the following properties (1) and (2) obtained from pyrolysis of naphtha is mixed with 100 parts by volume of heavy naphtha and / or kerosene, and the reaction temperature is 180 to 210 ° C. A kerosene base material having a PetroOXY (oxidation stability) of 6 minutes or more and a mercaptan concentration of 18 mass ppm or less obtained by hydrotreating at a temperature of 5%.
(1) The 10% distillation temperature is 40 to 100 ° C, the 50% distillation temperature is 150 to 210 ° C, and the 90% distillation temperature is 240 to 380 ° C.
(2) The density is 0.93 to 0.99 g / cm ³ .   The kerosene base material according to claim 1, wherein dicyclopentadiene and a styrene monomer are not contained in a component obtained by volatilization when heated to 56 ° C. The hydrogenation treatment is a treatment performed using a hydrogenation catalyst in the presence of hydrogen. The treatment conditions are a hydrogen pressure of 2 to 6 MPa, a reaction temperature of 180 to 230 ° C., and a liquid space velocity (LHSV) of 0.3. The kerosene base material according to claim ¹ , which has a hydrogen / oil ratio of 250 to 500 Nm ³ / kL.   The kerosene base material according to any one of claims 1 to 3 is contained at 1% by volume or more, a flash point is 40 ° C or higher, a smoke point is 21.0 or higher, and a 90% distillation temperature is 268 ° C or lower. A kerosene composition having PetroOXY (oxidation stability) of 50 minutes or more.