JP4324865B2 - Method for producing hydrocarbon fuel oil - Google Patents

Description

The present invention relates to a method for producing a hydrocarbon fuel oil or a base material thereof, particularly a kerosene equivalent fraction, from a paraffinic synthetic raw material produced by the reaction of carbon monoxide and hydrogen, so-called Fischer-Tropsch (FT) synthesis. Is.
More specifically, the present invention is a hydrocarbon fuel oil that is free of sulfur and has good low temperature fluidity, for example, a pour point and cloud point measured according to JIS K2269, or a clogging point measured according to JIS K2288. Or it is related with the manufacturing method of the base material, especially a kerosene oil equivalent fraction.

  Kerosene oil distillate derived from crude oil generally contains sulfur compounds, and when these oils are used as fuel, the sulfur present in the sulfur compounds is converted into low molecular weight sulfur compounds that are released into the atmosphere. Discharged. In addition, in exhaust gas aftertreatment devices that are being introduced in recent years, if a sulfur compound is present in the fuel, the catalyst used may be poisoned. In addition, it is said that aromatics are contained in the kerosene oil distillate derived from crude oil, and these increase the suspended particulate matter (PM) and nitrogen oxides (NOx) in the exhaust gas. Accordingly, it is desirable that the fuel oil has a low sulfur content or aromatic content.

  The product produced by Fischer-Tropsch synthesis (hereinafter also referred to as FT method) using a mixed gas consisting of carbon monoxide and hydrogen contains no sulfur compounds because impurities in the mixed gas are removed. Absent. Moreover, the product by this FT method has normal paraffin as a main component, and hardly contains aromatics.

On the other hand, the product produced by the FT method is composed mainly of normal paraffin and contains a large amount of heavy wax that is solid at room temperature and cannot be used as a liquid fuel. Therefore, for example, when distilled in a cut range equivalent to commercially available light oil derived from crude oil, wax crystals tend to precipitate at low temperatures, and low-temperature fluidity is not very good. In order to improve the low-temperature fluidity as a diesel vehicle fuel, the distillation cut temperature is lowered, the 90% distillation temperature measured according to JIS K2254 is kept low, and the mixing ratio of heavy components is reduced. However, since the heavy component cannot be used, the yield of the light oil fraction is reduced.
Therefore, there is a need for a method for obtaining fuel oil that effectively uses these heavy fractions that cannot be used as kerosene from the product produced by the FT method and that does not impair the low-temperature fluidity.

There has been known a method for obtaining a fuel having a good low temperature fluidity by hydrotreating a product obtained by the FT method to decompose and isomerize the product. For example, in a method for producing a hydrocarbon fuel from a hydrocarbon feedstock obtained from an FT process and comprising a product oil having a boiling point higher than that of the hydrocarbon fuel, the hydrocarbon feedstock is placed in the presence of a liquid. A catalyst comprising a silica-alumina support impregnated with platinum obtained by a process comprising contacting silica-alumina with a platinum salt under acidic conditions, and a hydrocarbon to be contacted at elevated temperature and pressure in the presence of hydrogen A method for producing a fuel, particularly a naphtha or kerosene oil fraction is known (see Patent Document 1). In addition, there is known a method for treating a base oil or the like having good low temperature fluidity by hydroisomerization of a charged raw material produced by the FT method (see Patent Document 2).
JP-A-5-302088 Japanese translation of PCT publication No. 8-511302

  As described above, a method has been proposed so far in which a heavy wax produced by the FT method is hydrotreated, decomposed and isomerized to obtain a fuel having good low-temperature fluidity. However, conventional hydrotreating produces light gases that reduce the yield of valuable distillates. Moreover, although it decomposes | disassembles depending on the kind of catalyst, isomerization does not occur so much and a fuel with favorable low-temperature fluidity cannot be obtained.

  Under the circumstances as described above, the present invention hydrotreats heavy wax produced by the FT method, decomposes it at a reduced gasification rate, and increases the isomerization reaction that occurs simultaneously. It is an object to efficiently obtain a liquid fuel that does not contain components and has good low-temperature fluidity.

  As a result of repeated studies to achieve the above object, the inventors of the present invention are platinum group catalysts using a specific support, and under the specific reaction conditions according to the type of the support used, by the FT method. When the generated heavy wax is hydrotreated and decomposed and isomerized, the gasification rate is suppressed, the yield of kerosene oil fractions is high, and the low-temperature fluidity of these fractions is also good. As a result, the present invention has been completed.

That is, the present invention provides the following hydrocarbon fuel oil production method in order to achieve the above object.
(1) A wax containing 70 % by mass or more of normal paraffin having 21 to 100 carbon atoms produced by Fischer-Tropsch synthesis,
A carrier mainly composed of at least one zeolite selected from Y-type zeolite and USY-type zeolite contains at least one platinum group metal in an amount of 0.01 to 10% by mass in terms of metal based on the catalyst. Using the catalyst
The hydrogen partial pressure is 2 to 20 MPa, the temperature is 235 to 320 ° C., the liquid space velocity is 0.1 to 2 h ⁻¹ , and the hydrogen / oil ratio is 100 to 2000 L / L.
With a gasification rate of less than 10% by mass, decomposition and isomerization reaction are performed, and the isoparaffin ratio in the fraction having 9 to 21 carbon atoms is 70% by mass or more.
A method for producing a hydrocarbon fuel oil (hereinafter referred to as “first method” of the present invention).

(2) A wax containing 70 % by mass or more of normal paraffin having 21 to 100 carbon atoms produced by Fischer-Tropsch synthesis,
In a carrier mainly composed of silica-alumina having a silica / alumina mass ratio of 1.5 or more, at least one platinum group metal is contained in an amount of 0.01 to 10% by mass in terms of metal on a catalyst basis. Using the catalyst
The hydrogen partial pressure is 2 to 20 MPa, the temperature is 355 to 390 ° C., the liquid space velocity is 0.1 to 2 h ⁻¹ , and the hydrogen / oil ratio is 100 to 2000 L / L.
With a gasification rate of less than 10% by mass, decomposition and isomerization reaction are performed, and the isoparaffin ratio in the fraction having 9 to 21 carbon atoms is 70% by mass or more.
A method for producing a hydrocarbon fuel oil (hereinafter referred to as “second method” of the present invention).

  According to the present invention, heavy wax produced by the FT method is hydrotreated to decompose at a reduced gasification rate, and simultaneously increase the isomerization reaction. A liquid fuel with good fluidity can be obtained efficiently.

Hereinafter, the present invention will be described in detail.
In the present invention, as described above, the heavy wax produced by the FT method is hydrotreated with a platinum group catalyst using a specific support under specific reaction conditions depending on the type of support used. It is characterized by doing.
The catalyst used in the present invention is a platinum group catalyst in which at least one platinum group metal is contained in a carrier. Examples of the platinum group metal include platinum, palladium, ruthenium, and rhodium, and platinum is particularly preferable. These can be used alone or in combination of two or more. Content of the platinum group metal in the catalyst used by this invention is 0.01-10 mass% in conversion of a metal on a catalyst basis. However, these platinum group metals have different wax decomposition rates depending on the metal species even in the same content, so in order to increase the yield of a desired fraction, the content of each metal species is within the above content range. It is desirable to optimize within. For example, when platinum is used, in order to increase the yield of a kerosene fraction having 9 to 21 carbon atoms, the platinum content in the catalyst is 0.05 to 5 mass in terms of metal on a catalyst basis. % Is preferable, and 0.1 to 1% by mass is more preferable.

  The platinum group catalyst carrier used in the present invention is a carrier mainly composed of zeolite in the first method, and a carrier mainly composed of silica-alumina in the second method. In the present invention, as described later, in the first method and the second method, different reaction conditions are adopted depending on the kind of the support. If the reaction conditions to be adopted are optimized, zeolite and silica-alumina It is also possible to use other carriers than the above.

As said other support | carrier, 1 or more types of various types chosen from an inorganic oxide or an inorganic crystalline compound or a clay mineral can be used.
Examples of the inorganic oxide include silica, alumina, boria, magnesia, titania, silica-magnesia, silica-zirconia, silica-tria, silica-beryllia, silica-titania, silica-boria, alumina-zirconia, alumina-titania, Alumina-boria, alumina-chromina, titania-zirconia, silica-alumina-tria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, among others, alumina, alumina-boria, alumina-titania, Alumina-zirconia is preferable, and γ-alumina among alumina is particularly preferable. Examples of the inorganic crystalline compound or clay mineral include molecular sieves, other inorganic crystalline compounds, and clay minerals such as montmorillonite, kaolin, bentonite, Adabalu guide, bauxite, kaolinite, nacrite, and anoxite. These can be used alone or in combination of two or more.

The specific surface area, pore volume, and average pore diameter of the above various carriers are not particularly limited in the present invention, but in order to obtain a catalyst having excellent hydrogenation activity, the specific surface area is 250 m ² / g or more. The pore volume is preferably 0.1 to 1.0 mL / g, and the average pore diameter is preferably 0.5 to 2.5 nm.
Further, in a catalyst using a carrier containing silica, the carrier contains 20% by mass or more of silica in order to promote isomerization reaction and obtain a fuel oil having a high isoparaffin ratio and good low-temperature fluidity. Is preferred. Further, when a silica-alumina carrier is used, the silica / alumina mass ratio in the carrier is desirably 1.5 or more for the same reason.

A method for incorporating an active metal such as a platinum-based metal into the support, that is, a method for preparing the catalyst used in the present invention, can be performed using several known techniques.
As one of the methods, there is an impregnation method in which a solution in which a metal compound of a platinum-based metal is dissolved in a solvent such as water, alcohols, ethers, and ketones is contained in the support by one or more impregnation treatments. It is done. Drying / firing is performed after the impregnation treatment. When the number of impregnation treatments is plural, drying / firing may be performed between the respective impregnation treatments.
Other methods include a spraying method in which a solution in which a metal compound of a platinum-based metal is dissolved in a carrier is sprayed, or a chemical vapor deposition method in which the metal component is chemically deposited.
Still other methods include a kneading method, a coprecipitation method, and an alkoxide method in which a carrier component before molding contains part or all of the metal component of the platinum-based metal for molding.

The physical properties such as the specific surface area and pore volume of the catalyst used in the present invention prepared by various methods as described above are not particularly limited in the present invention, but the catalyst having excellent hydrogenation activity and In order to achieve this, the specific surface area is 200 m ² / g or more, the pore volume is 0.3 to 1.2 mL / g, the average pore diameter is 6 to 12 nm, and the pore diameter distribution (MPD ± 1.5 nm) is 70% or more. Is preferred.

In the present invention, as the reaction conditions for the decomposition and isomerization reactions, the reaction conditions corresponding to the type of catalyst support used are employed in order to achieve the intended purpose. That is, in the first method, decomposition and isomerization are carried out with a hydrogen partial pressure of 2 to 20 MPa, a temperature of 200 to 320 ° C., a liquid space velocity of 0.1 to 2 h ⁻¹ , and a hydrogen / oil ratio of 100 to 2000 L / L. Perform the reaction.
In the second method, the hydrogen partial pressure, the liquid space velocity, and the hydrogen / oil ratio are in the same ranges as in the first method, and the temperature is 350 to 400 ° C.
Furthermore, in the case of a catalyst using a support other than the zeolite and silica-alumina, the hydrogen partial pressure, liquid space velocity, and hydrogen / oil ratio are in the same range as the first method and the second method. However, it is preferable to adopt the optimum range depending on the type of other carrier used, including the temperature.

If the hydrogen partial pressure is less than 2 MPa, the decomposition activity of the wax is too low, and if it exceeds 20 MPa, expensive equipment that can withstand such a high pressure is required, which is uneconomical. The hydrogen partial pressure is preferably 2 to 10 MPa, and more preferably 2.5 to 8 MPa.
In the case of the first method, if the temperature is less than 200 ° C., the catalytic activity is too low, and if it exceeds 320 ° C., decomposition proceeds too much and the gasification rate increases. In the case of the first method, the temperature is preferably 235 to 320 ° C, more preferably 245 to 315 ° C. In the case of the second method, if the temperature is less than 350 ° C., the catalytic activity is too low, and if it exceeds 400 ° C., the decomposition proceeds too much and the gasification rate increases. In the case of the second method, the temperature is preferably 355 to 390 ° C, more preferably 370 to 380 ° C.
If the liquid hourly space velocity is less than 0.1 h ^-1, the process efficiency is lowered, and when it exceeds 2h ^-1, the catalytic activity is not sufficiently exhibited too short contact time between the catalyst and feedstock. The liquid space velocity is preferably 0.5 to ¹ h ⁻¹ .
When the hydrogen / oil ratio is less than 100 L / L, the decomposition activity of the wax is too low, and when it exceeds 2000 L / L, the hydrogen production cost increases, which is uneconomical. The hydrogen / oil ratio is preferably 200 to 1500 L / L, more preferably 300 to 1200 L / L.

The processing target oil (raw material oil) used in the present invention is a wax containing 50% by mass or more of normal paraffins having 7 to 100 carbon atoms as a main component of normal paraffin, and a liquid product obtained by the FT method ( Synthetic hydrocarbon oil).
As the raw material oil, for example, one obtained in a single lot may be used alone, or a plurality of those obtained in a plurality of lots may be mixed and used. In addition, a catalyst obtained under a certain catalyst and a certain reaction condition may be used alone, or a plurality of catalysts obtained under a different catalyst and different reaction conditions may be used in combination. .

  According to the method for producing hydrocarbon fuel oil of the present invention, a kerosene oil fraction having a high isoparaffin ratio and good low-temperature fluidity can be obtained from the synthetic hydrocarbon oil obtained by FT synthesis as described above. . Commercial kerosene oil fractions are generally fractions containing those having 9 to 25 carbon atoms, but when producing kerosene oil fractions in the present invention, fractions having 9 to 21 carbon atoms ( It is preferable to produce a distillation temperature of about 150 to 350 ° C. from the viewpoint of easy prevention of wax precipitation.

  In the present invention, when 50% by mass or more of normal paraffins having 7 to 100 carbon atoms are included, the raw material oil obtained by the FT method may be used as it is (including those having approximately 5 or more carbon atoms) or distilled. May be used after removing light components. Preferably, light components are removed by distillation, and normal paraffins having a carbon number corresponding to the kerosene fraction in the feedstock, particularly normal paraffins having 20 or less carbon atoms, preferably 30% by mass or less, more preferably 10% by mass. % Or less is desirable. That is, the normal paraffin having 21 or more carbon atoms in the raw material oil is preferably more than 70% by mass, more preferably more than 90% by mass. By removing light components by distillation, normal paraffins with carbon numbers corresponding to kerosene oil fractions or lighter fractions may be gasified to cause an increase in gasification rate, It is preferable in that it can prevent the pour point of the fuel oil obtained without being decomposed and isoparaffinized without being decomposed.

  In addition, when the raw material oil contains a large amount of paraffin having more than 100 carbon atoms, the melting point of the raw material oil becomes high, so that it is easy to cause clogging with a pump or a line for supplying the raw material. In order to prevent this blockage, it is necessary to heat to a higher temperature, but the cost increases. Moreover, since it is necessary to use more severe decomposition conditions when attempting to decompose a raw material oil containing a large amount of paraffins having more than 100 carbon atoms, the cost of thermal energy increases. Furthermore, under such severe conditions, it is difficult to control the decomposition, and the decomposed components may not be limited to the kerosene oil fraction but may be excessively decomposed into a lighter fraction. Therefore, it is desirable that the paraffin having more than 100 carbon atoms in the feedstock oil is below the lower limit of detection (less than about 0.1% by mass) by gas chromatography or the like.

  Furthermore, in the conventional hydrotreatment, the catalyst is poisoned if the heavy wax produced by the FT method, which is the raw material oil, contains oxygenated compounds, so the oxygenated compounds are removed from the raw material in advance. In the present invention, there is no problem even if the raw material oil contains an oxygen-containing compound. In the present invention, the raw material oil may contain an oxygen-containing compound in an oxygen mass ratio on an anhydrous basis of 0.01% by mass or more.

  In the method for producing hydrocarbon fuel oil of the present invention, the gasification rate can be reduced to less than 10%, preferably less than 5% by suppressing the inclusion of light normal paraffin as described above.

As described above, according to the method for producing hydrocarbon fuel oil of the present invention, a kerosene fraction having a high isoparaffin ratio and good low temperature fluidity can be obtained. The fraction preferably has an isoparaffin ratio of 70% by mass or more. An isoparaffin ratio of 70% by mass or more is desirable for satisfying the JIS standard for light oil. That is, in order to use as light oil in Japan, it is necessary to satisfy the pour point and clogging point specified in JIS K2204. For example, No. 2 diesel oil used in a wide area has a pour point of -7.5 ° C or less and a clogging point of -5 ° C or less. The pour point is defined as + 5 ° C. or less (the clogging point is not defined). When used as a fuel for a diesel engine, the pour point is preferably + 5 ° C. or lower, more preferably −7.5 ° C. or lower, even in a warm region.
However, in the present invention, even when the isoparaffin ratio is less than 70% by mass and the pour point is higher than the desired pour point, the pour point is adjusted to the desired pour point by mixing with a base material having better low temperature fluidity. can do. In this case, the base material having excellent low-temperature fluidity may be a light hydrocarbon or a material containing a large amount of aromatics, but when mixing light hydrocarbons, the kinematic viscosity should not be too low. It is desirable. In addition, when mixing materials containing a large amount of aromatics, it is generally said that a substrate containing a large amount of aromatics increases suspended particulate matter (PM) and nitrogen oxides (NOx) in the exhaust gas of diesel vehicles. Therefore, it is desirable not to cause an excessive increase in PM or NOx.

When the present invention is carried out on a commercial scale, the catalyst is used in a suitable reactor as a fixed bed, moving bed or fluidized bed, the above feed oil is introduced into this reactor, and the above hydrotreatment conditions are used. Can be processed. Most commonly, the catalyst is maintained as a fixed bed so that the feedstock passes down the fixed bed.
In practice on a commercial scale, a single reactor may be used, or two or more reactors in series may be used. By performing the reaction in multiple stages using two or more reactors, and performing the reaction conditions in each stage under mild reaction conditions, the overall yield of the desired kerosene fraction can be improved.
When a single reactor is used, the reaction can be carried out by charging two or more different catalysts in the reactor. At this time, the catalyst can be divided into two or more layers in the reactor, and different layers can be filled with different catalysts, or the catalyst can be mixed and packed in one layer. Furthermore, when using two or more reactors in succession, different catalysts can be used for each reactor.

Furthermore, a separation device can be provided on the downstream side of the reactor, and the heavy component can be guided upstream of the reactor to perform the hydrocracking process again. For example, the hydrotreated product can be separated in a rectification column, and the heavy unconverted material can be guided to a hydrocracking apparatus for disappearance to be hydrocracked again.
Further, when recovering the hydrotreated product, at least a part of the hydrocracked raw material is separated and treated in a single operation to produce hydrogen, and the hydrogen is at least partially used as a product. Can also be recovered.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to a following example.

Example 1
A platinum group catalyst containing 0.5% by mass of platinum in terms of metal on a silica-alumina support shown in Table 3 on a catalyst basis under the conditions shown in Table 1 and Wax-1 shown in Table 2 and FIG. As a raw material, a hydrogenation reaction was carried out at a reaction temperature of 360 ° C. to evaluate the activity. The evaluation results are shown in Table 4.
Here, activity evaluation was performed as follows. That is, the raw material wax was supplied downward from the top to a cylindrical fixed bed flow type reaction apparatus upright. The reactor had an inner diameter of 12 mm (thickness of 3 mm) and was filled with 18 mL of catalyst. Prior to the reaction evaluation, pretreatment reduction was performed at 300 ° C. for 2 hours using a heater provided in the reaction apparatus under hydrogen flow. In this case, the hydrogen flow rate is 150 mL / min, and the hydrogen partial pressure is 3.0 MPa. The reaction was carried out by controlling the reaction temperature with a heater setting, the reaction pressure with a pressure regulating valve, and the hydrogen / oil ratio with a mass flow controller. Downstream of the fixed bed flow type reactor, two stages of traps for reaction product recovery are provided, the first stage is heated to 200 ° C., the second stage is cooled with ice water, Heavy and light fractions were collected.

The gasification rate, kerosene yield, and isoparaffin ratio in kerosene in Table 4 are defined as follows.
The gasification rate was defined as the mass% of the recovered product relative to the mass of the raw material charged in the activity evaluation.
The kerosene oil yield was determined by first analyzing the product recovered by activity evaluation with a gas chromatograph and determining the total mass% of the substance having 9 to 21 carbon atoms. After that, the mass% obtained by removing the gasification rate from 100% by mass was multiplied by the total mass% of the substance having 9 to 21 carbon atoms.
The isoparaffin ratio in kerosene oil was defined as the mass% of isoparaffin in the substance having a carbon number of 9 to 21 as 100 mass% in the gas chromatograph.

(Example 2)
The activity was evaluated in the same manner as in Example 1 except that the reaction temperature was 375 ° C. The evaluation results are shown in Table 4.

( Reference Example 3)
A platinum group catalyst containing 0.5% by mass of platinum in metal conversion on the basis of catalyst on the USY-type zeolite 1 carrier shown in Table 3 under the conditions shown in Table 1 and the waxes shown in Table 2 and FIG. Using 1 as a raw material, a hydrogenation reaction was carried out at a reaction temperature of 230 ° C., and activity evaluation was performed. The evaluation results are shown in Table 4.

(Example 4)
The activity was evaluated in the same manner as in Reference Example 3 except that the reaction temperature was 240 ° C. The evaluation results are shown in Table 4.

(Example 5)
The activity was evaluated in the same manner as in Reference Example 3 except that the reaction temperature was 250 ° C. The evaluation results are shown in Table 4.

(Example 6)
A platinum group catalyst containing 0.5% by mass of platinum in terms of metal on a catalyst basis on the Y-type zeolite carrier shown in Table 3 under the conditions shown in Table 1 and wax-1 shown in Table 2 and FIG. As a raw material, the hydrogenation reaction was carried out at a reaction temperature of 300 ° C., and the activity was evaluated. The evaluation results are shown in Table 4.

(Example 7)
The activity was evaluated in the same manner as in Example 6 except that the reaction temperature was 310 ° C. The evaluation results are shown in Table 4.

( Reference Example 8)
A platinum group catalyst containing 0.5% by mass of platinum in metal conversion on a catalyst basis with respect to the USY-type zeolite 2 carrier shown in Table 3, the liquid space velocity is 1.0 h ⁻¹ , and the hydrogen / oil ratio is Except for setting it to 500 L / L, under the conditions of Table 1, using the wax-1 shown in Table 2 and FIG. 1 as a raw material, a hydrogenation reaction was carried out at a reaction temperature of 220 ° C. to evaluate the activity. The evaluation results are shown in Table 4.

(Comparative Example 1)
The activity was evaluated in the same manner as in Example 1 except that the reaction temperature was 350 ° C. The evaluation results are shown in Table 4.

(Comparative Example 2)
The activity was evaluated in the same manner as in Example 1 except that the reaction temperature was 400 ° C. The evaluation results are shown in Table 4.

(Comparative Example 3)
The activity was evaluated in the same manner as in Example 1 except that the reaction temperature was 410 ° C. The evaluation results are shown in Table 4.

(Comparative Example 4)
The activity was evaluated in the same manner as in Reference Example 3 except that the reaction temperature was 260 ° C. The evaluation results are shown in Table 4.

(Comparative Example 5)
The activity was evaluated in the same manner as in Example 6 except that the reaction temperature was 280 ° C. The evaluation results are shown in Table 4.

(Comparative Example 6)
The activity was evaluated in the same manner as in Example 6 except that the reaction temperature was 320 ° C. The evaluation results are shown in Table 4.

(Comparative Example 7)
A platinum group catalyst containing 0.5% by mass of platinum in metal conversion on a catalyst basis with respect to the USY-type zeolite 2 carrier shown in Table 3, the liquid space velocity is 1.0 h ⁻¹ , and the hydrogen / oil ratio is Except for setting it to 500 L / L, under the conditions of Table 1, using the wax-1 shown in Table 2 and FIG. The evaluation results are shown in Table 4.

(Comparative Example 8)
Activity evaluation was performed in the same manner as in Reference Example 8 except that the raw material was wax-2 shown in Table 2 and FIG. The evaluation results are shown in Table 4.
As can be seen in Table 2, since the normal paraffin having 21 or less carbon atoms exceeds 30% by mass, the wax-2 has a higher gasification rate than that of Reference Example 8, and has 9 to 21 carbon atoms. Since the normal paraffin that was not decomposed remained in the kerosene fraction, the isoparaffin ratio was lowered.

(Comparative Example 9)
The activity was evaluated in the same manner as in Comparative Example 8 except that the reaction temperature was 230 ° C. The evaluation results are shown in Table 4.
Since wax-2 was used as a raw material, the gasification rate was further increased by raising the temperature by 10 ° C. from Comparative Example 8, and the isoparaffin ratio in the kerosene oil having 9 to 21 carbon atoms was low.

(Comparative Example 10)
A platinum group catalyst containing 0.5% by mass of platinum in metal conversion on the basis of catalyst on the USY-type zeolite 2 carrier shown in Table 3 under the conditions shown in Table 1 and the waxes shown in Table 2 and FIG. 2 was used as a raw material, and a hydrogenation reaction was carried out at a reaction temperature of 210 ° C. to evaluate the activity. The evaluation results are shown in Table 4.
Although the gasification rate was the same as that of Comparative Example 8, it was less than 10% by mass, but since wax-2 was used as a raw material, the isoparaffin ratio in kerosene oil was low.

Example 9
The oil produced in Example 5 was distilled at a cut range of 225 ° C. to 250 ° C. to evaluate low temperature fluidity. This evaluation of low-temperature fluidity is an evaluation of the fraction obtained by distilling the oil to be evaluated in a device in accordance with the crude oil distillation method shown in ASTM-D2892 within a predetermined temperature range cut range. . The evaluation results are shown in Table 5.
Here, the isoparaffin ratio was defined by mass% of isoparaffin in the substance having a carbon number of 9 to 21 as 100 mass% in the gas chromatograph. The cloud point and pour point were measured according to JIS K2269. Furthermore, Table 5 also shows the 10% distillation temperature and 90% distillation temperature measured by the distillation test method shown in JIS K2254 of the fraction obtained by distillation in the cut range of the predetermined temperature range.

(Example 10)
The low temperature fluidity was evaluated in the same manner as in Example 9 except that the cut range of distillation was 250 ° C to 275 ° C. The evaluation results are shown in Table 5.

Example 11
The low temperature fluidity was evaluated in the same manner as in Example 9 except that the cut range of distillation was 275 ° C to 300 ° C. The evaluation results are shown in Table 5.

Example 12
The low temperature fluidity was evaluated in the same manner as in Example 9 except that the distillation cut range was 300 ° C. to 325 ° C. The evaluation results are shown in Table 5.

(Example 13)
The low temperature fluidity was evaluated in the same manner as in Example 9 except that the cut range of distillation was 325 ° C to 350 ° C. The evaluation results are shown in Table 5.

(Comparative Example 11)
In the FT method, a naphtha fraction, a kerosene fraction, and a light oil fraction are simultaneously generated in addition to the wax. These light fractions produced simultaneously with wax-1 shown in Table 2 and FIG. 1 are hydrotreated using a catalyst in which nickel is supported on diatomaceous earth to remove olefins and oxygen-containing compounds, and 225 ° C. Distillation was performed at a cut range of ˜250 ° C. to evaluate low temperature fluidity. The evaluation results are shown in Table 5.

(Comparative Example 12)
The low-temperature fluidity was evaluated in the same manner as in Comparative Example 11 except that the distillation cut range was 250 ° C. to 275 ° C. The evaluation results are shown in Table 5.

(Comparative Example 13)
The low-temperature fluidity was evaluated in the same manner as in Comparative Example 11 except that the distillation cut range was 275 ° C to 300 ° C. The evaluation results are shown in Table 5.

(Comparative Example 14)
The low-temperature fluidity was evaluated in the same manner as in Comparative Example 11 except that the distillation cut range was 300 ° C. to 325 ° C. The evaluation results are shown in Table 5.

(Comparative Example 15)
The low temperature fluidity was evaluated in the same manner as in Comparative Example 11 except that the distillation cut range was 325 ° C to 350 ° C. The evaluation results are shown in Table 5.

It is a graph which shows the normal paraffin content rate according to carbon number of the raw material wax used by the Example and the comparative example.

Claims (2)

A wax containing 70 % by mass or more of normal paraffin having 21 to 100 carbon atoms produced by Fischer-Tropsch synthesis,
A carrier mainly composed of at least one zeolite selected from Y-type zeolite and USY-type zeolite contains at least one platinum group metal in an amount of 0.01 to 10% by mass in terms of metal based on the catalyst. Using the catalyst
The hydrogen partial pressure is 2 to 20 MPa, the temperature is 235 to 320 ° C., the liquid space velocity is 0.1 to 2 h ⁻¹ , and the hydrogen / oil ratio is 100 to 2000 L / L.
With a gasification rate of less than 10% by mass, decomposition and isomerization reaction are performed, and the isoparaffin ratio in the fraction having 9 to 21 carbon atoms is 70% by mass or more.
A method for producing a hydrocarbon fuel oil. A wax containing 70 % by mass or more of normal paraffin having 21 to 100 carbon atoms produced by Fischer-Tropsch synthesis,
In a carrier mainly composed of silica-alumina having a silica / alumina mass ratio of 1.5 or more, at least one platinum group metal is contained in an amount of 0.01 to 10% by mass in terms of metal on a catalyst basis. Using the catalyst
The hydrogen partial pressure is 2 to 20 MPa, the temperature is 355 to 390 ° C., the liquid space velocity is 0.1 to 2 h ⁻¹ , and the hydrogen / oil ratio is 100 to 2000 L / L.
With a gasification rate of less than 10% by mass, decomposition and isomerization reaction are performed, and the isoparaffin ratio in the fraction having 9 to 21 carbon atoms is 70% by mass or more.
A method for producing a hydrocarbon fuel oil.

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