WO2007034556A1

WO2007034556A1 - Method for producing hydrocarbon fuel oil

Info

Publication number: WO2007034556A1
Application number: PCT/JP2005/017522
Authority: WO
Inventors: Hiroaki Hara; Toshio Shimizu; Yutaka Miyata
Original assignee: Japan Oil, Gas And Metals National Corporation; Japan Petroleum Exploration Co., Ltd.; Cosmo Oil Co., Ltd.; Nippon Steel Engineering Corporation; Inpex Corporation
Priority date: 2005-09-22
Filing date: 2005-09-22
Publication date: 2007-03-29
Also published as: EP1927645A1; ZA200700432B; US20080222945A1; EP1927645A4

Abstract

The object of the present invention is to produce a liquid fuel having no sulfur content and exhibiting a good low temperature fluidity with good efficiency by hydrogenating a heavy wax produced by the Fisher-Tropsh (FT) synthesis to decompose the wax while reducing the gasification rate and enhance the isomerization reaction which occurs simultaneously with the decomposition. A method for producing a hydrocarbon fuel oil which comprises subjecting a heavy wax produced by the FT synthesis to a hydrogenation treatment, by the use of a platinum group based catalyst having zeolite or silica-alumina as a carrier, under a specific reaction condition which is selected depending on the type of the carrier, to thereby decompose and isomerize it.

Description

Specification

Method for producing hydrocarbon fuel oil

Technical field

[0001] The present invention relates to a reaction between carbon monoxide and hydrogen, a so-called Fischer's Tropsch (FT) synthesis, a paraffinic synthetic feedstock, a hydrocarbon fuel oil or a base material thereof, particularly a kerosene equivalent fraction. It is related with the method of manufacturing.

More specifically, the present invention is a hydrocarbon fuel that does not contain sulfur and has a good low temperature fluidity, for example, a pour point and cloud point measured according to JIS K2 269, or a clogging point measured according to ¾ JIS K2288. The present invention relates to a method for producing oil or its base material, particularly a kerosene oil equivalent fraction.

Background art

[0002] Kerosene oil distillate derived from crude oil generally contains sulfur compounds, and when these oils are used as fuel, sulfur present in sulfur compounds is converted to low molecular weight sulfur compounds. And discharged into the atmosphere. In addition, in exhaust gas aftertreatment devices that have been introduced in recent years, if a sulfur compound is present in the fuel, the catalyst used may be poisoned. The crude oil-derived kerosene distillate contains aromatics, which are said to increase the amount of suspended particulate matter (PM) and nitrogen oxides (NOx) in the exhaust gas. . Therefore, it is desirable that the fuel oil has a low sulfur content or aromatic content.

[0003] The product produced by Fischer's Tropsch synthesis (hereinafter also referred to as FT method) using a mixed gas composed of carbon monoxide and hydrogen removes impurities in the mixed gas. Compound is not included. In addition, the product obtained by the FT method has normal paraffin as a main component and hardly contains aromatics.

[0004] 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 distilling in the cut range equivalent to commercially available light oil derived from crude oil, low-temperature fluidity is not so good at low temperatures because it precipitates ox crystals. In order to improve low-temperature fluidity and use as a fuel for diesel vehicles, lower the distillation cut temperature and comply with JIS K2254 Therefore, it is possible to reduce the mixing ratio of heavy components by keeping the measured 90% distillation temperature low, etc. This reduces the yield of diesel oil fractions because heavy components cannot be used. Therefore, there is a need for a method for effectively using these heavy and unusable fractions of kerosene from the products produced by the FT method, and obtaining fuel oil that does not impair low-temperature fluidity.

[0005] To date, there has been known a method for obtaining a fuel having good low-temperature fluidity by hydrotreating a product obtained by the FT method to decompose and isomerize the product. For example, in a method of producing a hydrocarbon fuel from a hydrocarbon feedstock that is obtained by the FT method and has a boiling point higher than the boiling range of the hydrocarbon fuel, the hydrocarbon feedstock 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 in the presence of a liquid, and at elevated temperature and pressure in the presence of hydrogen. Production methods for hydrocarbon fuels to be contacted, especially naphtha and kerosene fractions are known!

). In addition, a method for treating a feedstock produced by the FT method into a base oil having good low-temperature fluidity by hydroisomerization is known (see Patent Document 2).

Patent Document 1: Japanese Patent Laid-Open No. 5-302088

Patent Document 2: Japanese Patent Publication No. 8-511302

Disclosure of the invention

Problems to be solved by the invention

[0006] As described above, there has been proposed a method for obtaining a fuel having good low-temperature fluidity by hydrotreating heavy wax produced by the FT method and decomposing and isolating it. Has been. However, conventional hydrotreating produces light gases that reduce the yield of valuable distillates. Depending on the type of catalyst, decomposition may occur, but isomerization does not occur so much and fuel with good low temperature fluidity cannot be obtained.

[0007] 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. Thus, it is an object to efficiently obtain a liquid fuel that does not contain sulfur and has good low-temperature fluidity. Means for solving the problem

[0008] 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 under specific reaction conditions according to the type of support used. When the heavy wax produced by the FT method is hydrotreated and decomposed and isomerized, the gasification rate is reduced, and the yield of kerosene oil fractions is high. The present inventors have found that the fluidity is improved and completed the present invention.

That is, the present invention provides the following method for producing hydrocarbon fuel oil in order to achieve the above object.

(1) A wax containing 50% by mass or more of normal paraffin having 7 to 100 carbon atoms produced by Fitzsha 'Tropsch synthesis,

Using a catalyst comprising 0.01 to 10% by mass of at least one platinum group metal on a catalyst basis, in terms of metal, on a support mainly containing zeolite.

Hydrogen partial pressure is 2 ~ 20MPa, temperature is 200 ~ 320 ° C, liquid space velocity is 0.1 ~ 2h Hydrogen Z oil ratio is 100 ~ 2000LZL,

When the gasification rate is less than 10% by mass, decomposition and isomerization are performed, and the isoparaffin ratio in the fraction having 9 to 21 carbon atoms is set to 70% by mass or more.

A method for producing a hydrocarbon fuel oil (hereinafter referred to as the “first method” of the present invention) o

[0010] (2) Fitzia, a wax containing 50% by mass or more of normal paraffin having 7 to 100 carbon atoms produced by Tropsch synthesis,

Using a catalyst comprising 0.01 to 10% by mass of at least one platinum group metal on a catalyst basis, in terms of metal, on a carrier mainly composed of silica alumina,

Hydrogen partial pressure is 2 ~ 20MPa, temperature is 350 ~ 400 ° C, liquid space velocity is 0.1 ~ 2h Hydrogen Z oil ratio is 100 ~ 2000LZL,

The method of manufacturing hydrocarbon fuel oil, characterized in that (hereinafter, referred to as "second process" of the present invention.) ₀ Effect of the Invention

[0011] According to the present invention, a heavy wax produced by the FT method is hydrotreated to produce a gas. By suppressing the decomposition rate and increasing the isomerization reaction that occurs at the same time, it is possible to obtain a liquid fuel efficiently without containing a sulfur content and having good low-temperature fluidity.

Brief Description of Drawings

FIG. 1 is a graph showing the normal paraffin content according to the number of carbon atoms of the raw material wax used in Examples and Comparative Examples.

BEST MODE FOR CARRYING OUT THE INVENTION

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 hydrogenated under a specific reaction condition corresponding to the type of support used with a platinum group catalyst using a specific support. It is characterized in that it is processed.

The catalyst used in the present invention is a platinum group catalyst in which at least one platinum group metal is contained in a support. Examples of the platinum group metal include platinum, noradium, ruthenium, and rhodium, and platinum is particularly preferable. These can be used alone or in combination of two or more. The platinum group metal content in the catalyst used in the present invention is 0.01 to 10% by mass in terms of metal based on the catalyst. However, these platinum group metals have different wax decomposition rates depending on the metal species even if they have the same content, so in order to increase the yield of the desired fraction, the content of each metal species is within the above content range. It is desirable to optimize within. For example, when using platinum, 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 in terms of metal on a catalyst basis. % By mass is preferred. 0.1 to 1% by mass is more preferred.

[0014] In the first method, the platinum group catalyst carrier used in the present invention is a carrier mainly containing zeolite. Examples of zeolites may be natural or synthesized. Forgerite X-type zeolite, faujasite Y-type zeolite (hereinafter referred to as “Y-type zeolite”), chapasite zeolite, mordenite zeolite, zeolite zeolite MCM-type zeolite, ZSM-type zeolite and the like, and among them, vertical zeolite, stabilized zeolite (hereinafter referred to as “USY-type zeolite”) and the like are preferable. Particularly preferred is proton type zeolite. In addition, the atomic ratio Si ZA1 of kaye to aluminum in zeolite is preferably about 1 or more. Furthermore, alkali such as sodium in zeolite is preferred. If the content of the metal ion is large, the catalytic activity is lowered. Therefore, it is usually preferable to adjust the content to about 0.5% by mass or less based on the zeolite.

In the second method, the support is mainly composed of silica alumina. The weight ratio of silica and alumina is not particularly limited, but the weight ratio of silica Z alumina in the carrier is 1 in order to promote the isomerization reaction and obtain a fuel oil having a high isoparaffin ratio and good low temperature fluidity. More than 5 is desirable.

In the present invention, as described later, in the first method and the second method, different reaction conditions are adopted depending on the type of support. However, if the reaction conditions to be adopted are optimized, zeolite and silica-alumina It is also possible to use other carriers than the above.

[0015] As the other carrier, an inorganic oxide, or one or more selected from inorganic crystalline compounds or clay mineral powers can be used.

Examples of inorganic oxides include silica, alumina, polya, magnesia, titer, silica magnesia, silica-zinoleconia, silica-tria, silica monoberia, silica titania, silica-boria, and alumina zirconia. , Alumina-Titania, Alumina-Boria, Alumina-Kina, Titania-Zirconia, Silica-Alumina-Tria, Silica-Alumina-Zircoure, Silica-Alumina-Magnesia, Silica-Magnesia-Zirconia, Alumina, Alumina-Boria, Alumina-- Of these, titania and alumina-zircoa are preferred, and γ-alumina is particularly preferred. In addition, examples of inorganic crystalline compounds or clay minerals include molecular sieves, other inorganic crystalline compounds, and clays such as montmorillonite, kaolin, bentonite, adadaval guide, bauxite, kaolinite, nacrite, and anoxite. Minerals. These can be used alone or in combination of two or more.

[0016] The specific surface area, pore volume, and average pore diameter of the above-mentioned 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 25. The pore volume that is preferably Om ² / g or more is preferably 0.1 to 1. The average pore diameter that is preferably OmL / g is preferably 0.5 to 25 nm.

In addition, in a catalyst using a carrier containing silica, 20% by mass or more of silica is used in order to promote the isomerization reaction and obtain a fuel oil having a high isoparaffin ratio and good low-temperature fluidity. It is preferable that the carrier contains.

[0017] A method of incorporating an active metal such as a platinum-based metal into a support, that is, a method of preparing a 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. Can be mentioned. Drying and firing are performed after the impregnation treatment, but when the number of impregnation treatments is plural, drying and firing may be performed between each impregnation treatment.

Other methods include a spraying method in which a solution in which a metal compound of a platinum-based metal is dissolved in a support 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.

[0018] 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 have excellent hydrogenation activity. In order to obtain a catalyst having a specific surface area of 200 m ² / g or more, a pore volume of 0.1 to 1.2 mLZg, an average pore diameter of 0.5 to 25 nm, and a pore diameter distribution (MPD ± 1.5 nm) 70% or more is preferable.

The catalyst used in the present invention can be used in the form of powder, granules, spheres, pellets, honeycombs, and any other shape, and the shape and structure are not particularly limited, but the shape according to the type of the reactor. Is preferably selected. When the reactor is a fixed bed, a molded product is generally used. Further, when the catalyst is molded and used, a binder such as an organic or inorganic compound, a binder, or the like may be used as long as the effects of the present invention are not impaired.

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—hydrogen / oil ratio of 100 to 2000 L / L. Perform the reaction.

In the second method, the hydrogen partial pressure, liquid space velocity, and hydrogen Z oil ratio are The temperature is 350 to 400 ° C.

Furthermore, in the case of a catalyst using a support other than the above zeolite and silica alumina, the hydrogen partial pressure, the liquid space velocity, and the hydrogen Z oil ratio are within the same ranges as in the first method and the second method. However, it is preferable to adopt the optimum range depending on the type of other carriers used, including the temperature.

[0020] 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, a high-cost facility that can withstand such a high pressure is required, which is uneconomical. Hydrogen partial pressure is 2 to: LOMPa is preferred. 2.5 to 8 MPa is more preferable.

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, the 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 lower 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 from 355 to 390. C, more preferably 370-380. C.

If the liquid hourly space velocity is less than 0.1 lh ¹ , the processing efficiency decreases. If it exceeds 2 h- ¹ , the contact time between the catalyst and the raw material oil becomes too short, and the catalytic activity is not fully exhibited. The liquid space velocity is preferably 0.5 to lh ¹ .

If the hydrogen Z oil ratio is less than 100LZL, the cracking activity of the wax is too low, and if it exceeds 200 OLZL, the hydrogen production cost increases, which is uneconomical. The hydrogen Z oil ratio is preferably 200 to 1500 LZL, more preferably 300 to 1200 LZL.

[0021] The oil to be treated (raw oil) used in the present invention is a wax containing 50% by mass or more of normal paraffins having 7 to more carbon atoms as a main component, and obtained by the FT method. Liquid product (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. Further, 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. .

[0022] According to the method for producing a hydrocarbon fuel oil of the present invention, it was obtained by the FT synthesis as described above. A kerosene oil fraction having a high isoparaffin ratio and good low-temperature fluidity can be obtained from synthetic hydrocarbon oil. Commercial kerosene oil fractions are generally those containing 9-25 carbon atoms, but when producing kerosene oil fractions according to the present invention, fractions having 9-21 carbon atoms ( It is preferable to produce a distillation temperature of about 150 to 350 ° C. in terms of easy prevention of wax precipitation.

[0023] In the present invention, when 50% by mass or more of normal paraffin having 7 to C: LOO is 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). However, it may be used after removing light components by distillation. 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, it is desirable that the normal paraffin having 21 or more carbon atoms in the feedstock 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. This is preferable in that it can be prevented from increasing the pour point of the fuel oil obtained without being decomposed and isoparaffinized without being decomposed.

[0024] Further, if 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 likely to cause clogging in 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. In addition, if the raw material oil containing a large amount of paraffins with more than 100 carbon atoms is to be decomposed, it is necessary to use more severe decomposition conditions, which increases the cost of thermal energy. Furthermore, under such severe conditions, decomposed components that are difficult to control decomposition may not be retained in the kerosene oil fraction, but may be excessively decomposed into lighter fractions. Therefore, it is desirable for paraffins with more than 100 carbon atoms in the feedstock oil to be below the lower limit of detection (less than about 0.1% by mass) by gas chromatography or the like.

[0025] Furthermore, in the conventional hydrotreatment, if the heavy wax produced by the FT method as the raw material oil contains an oxygen-containing compound, the catalyst is poisoned. In the present invention, there is no problem even if the raw material oil contains an oxygen-containing compound. In the present invention, the oxygen-containing compound is added to the feedstock You may contain 0.01 mass% or more by mass ratio.

[0026] In the method for producing a hydrocarbon fuel oil of the present invention, the gasification rate can be reduced to less than 10%, preferably less than 5% by suppressing the content of light normal paraffin as described above.

[0027] 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, but this low-temperature fluidity is good. As a preferred kerosene fraction, it is desirable that the isoparaffin ratio is 70% by mass or more. A isoparaffin ratio of 70% by mass or more is desirable in order to satisfy the JIS standard for diesel oil. In other words, 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 specified). When used as fuel for diesel engines, the pour point is preferably + 5 ° C or lower even in warm regions, more preferably 7.5 ° C or lower.

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 substrate having better low temperature fluidity. can do. The base material with excellent low-temperature fluidity at that time may be a light hydrocarbon or a substance 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. So, because of excessive PM and NOx increase

I want to do it.

[0028] 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-mentioned feedstock is introduced into this reactor, and the above-mentioned water What is necessary is just to process on a raw material processing condition. Most commonly, the catalyst is maintained as a fixed bed so that feedstock passes down the fixed bed.

For implementation on a commercial scale, a single reactor can be used, or two or more reactors in series can be used. The reaction is performed in multiple stages using two or more reactors. By carrying out the above reaction conditions under mild reaction conditions, the overall yield of the desired kerosene oil fraction can be improved.

In addition, 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 catalysts can be divided and packed in each layer, 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.

[0029] Furthermore, a separation device may be provided on the downstream side of the reactor, and the heavy component may 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 the hydrocracking apparatus to disappear and then hydrocracked again.

Furthermore, 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.

Example

Hereinafter, the ability to explain the present invention more specifically with reference to examples and comparative examples The present invention is not limited to the following examples.

[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, and wax 1 shown in Table 2 and FIG. As a result, the hydrogenation reaction was performed at a reaction temperature of 360 ° C., and the activity was evaluated. Table 4 shows the evaluation results.

Here, activity evaluation was performed as follows. That is, the raw material wax was supplied downward to the cylindrical fixed bed flow type reaction apparatus upright. The reactor was 12 mm in inner diameter (3 mm thick) and packed with 18 mL of catalyst. Prior to the reaction evaluation, a pretreatment reduction was performed at 300 ° C. for 2 hours using a heater provided in the reactor under hydrogen flow. The hydrogen flow rate at that time is 150 mLZmin, and the hydrogen partial pressure is 3. OMPa. For the reaction, set the heater to set the reaction temperature, the pressure adjustment valve to set the reaction pressure, Each of the hydrogen / oil ratios was controlled by a roller. Downstream of the fixed bed flow reactor

Two stages of product recovery traps are provided, the first stage is heated to 200 ° C, the second stage is cooled with ice water, and the heavy and light fractions are collected respectively. .

[0032] The gasification rate, kerosene oil yield, and isoparaffin ratio in kerosene oil in Table 4 are defined as follows.

The gasification rate was determined by the mass% of the recovered product with respect to the mass of the raw material charged in the activity evaluation.

The kerosene oil yield was determined by first analyzing the product recovered in the activity evaluation with a gas chromatograph to determine the total mass% of substances having 9 to 21 carbon atoms. After that, the 100 mass% force was also defined by multiplying the mass% excluding the gasification rate by the total mass% of substances having 9 to 21 carbon atoms.

Isoparaffins ratio in kerosene and gas oil are, when formed into a 100 wt% material having a carbon number of 9 to 21 in a gas chromatograph was defined by the mass ^_0/0 isoparaffins therein.

[0033] [Table 1]

[0034] [Table 2]

[0035] [Table 3] s o ^ ¾ "a ^ ¥ () w state s pdjlodo plρΙl ε" to "Eseedno: ηυ :. ,

(Example 2)

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

[0037] (Example 3)

A platinum group catalyst containing 0.5% by mass of platinum in metal conversion on a catalyst basis on a USY-type zeolite 1 carrier shown in Table 3 under the conditions shown in Table 1 and the wax 1 shown in Table 2 and FIG. As a raw material, the hydrogenation reaction was carried out at a reaction temperature of 230 ° C, and the activity was evaluated. Table 4 shows the evaluation results.

[0038] (Example 4)

The activity was evaluated in the same manner as in Example 3 except that the reaction temperature was 240 ° C. Table 4 shows the evaluation results.

[Example 5]

The activity was evaluated in the same manner as in Example 3 except that the reaction temperature was 250 ° C. Table 4 shows the evaluation results.

[0040] (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 and wax 1 shown in Table 2 and FIG. 1 under the conditions shown in Table 1. The raw material was subjected to a hydrotreating reaction at a reaction temperature of 300 ° C, and the activity was evaluated. Table 4 shows the evaluation results.

[Example 7]

The activity was evaluated in the same manner as in Example 6 except that the reaction temperature was 310 ° C. Table 4 shows the evaluation results.

[0042] (Example 8)

A platinum group catalyst containing 0.5% by mass of platinum in metal conversion, based on the catalyst, on the USY-type zeolite 2 carrier shown in Table 3, with a liquid space velocity of 1. O hydrogen Z oil ratio of 500 LZL Except for the above, under the conditions shown in Table 1, the hydrotreating reaction was carried out at a reaction temperature of 220 ° C. using wax 1 shown in Table 2 and FIG. Table 4 shows the evaluation results.

[0043] (Comparative Example 1)

The activity was evaluated in the same manner as in Example 1 except that the reaction temperature was 350 ° C. Table 4 shows the evaluation results. [0044] (Comparative Example 2)

The activity was evaluated in the same manner as in Example 1 except that the reaction temperature was 400 ° C. Table 4 shows the evaluation results.

[0045] (Comparative Example 3)

The activity was evaluated in the same manner as in Example 1 except that the reaction temperature was 410 ° C. Table 4 shows the evaluation results.

[Comparative Example 4]

The activity was evaluated in the same manner as in Example 3 except that the reaction temperature was 260 ° C. Table 4 shows the evaluation results.

[0047] (Comparative Example 5)

The activity was evaluated in the same manner as in Example 6 except that the reaction temperature was 280 ° C. Table 4 shows the evaluation results.

[0048] (Comparative Example 6)

The activity was evaluated in the same manner as in Example 6 except that the reaction temperature was 320 ° C. Table 4 shows the evaluation results.

[0049] (Comparative Example 7)

A platinum group catalyst containing 0.5% by mass of platinum in metal conversion, based on the catalyst, on the USY-type zeolite 2 carrier shown in Table 3, with a liquid space velocity of 1. O hydrogen Z oil ratio of 500 LZL Except for the above, the hydrotreating reaction was carried out at the reaction temperature of 240 ° C using the wax 1 shown in Table 2 and FIG. Table 4 shows the evaluation results.

[0050] (Comparative Example 8)

Activity evaluation was performed in the same manner as in Example 8 except that the raw material was wax 2 shown in Table 2 and FIG. Table 4 shows the evaluation results.

As shown in Table 2, wax-2 has a higher gasification rate than that of Example 8 and has a carbon number of 9 to 21 because normal paraffins having 21 or less carbon atoms exceed 30% by mass. The normal paraffin that remained undecomposed remains in the kerosene fraction, resulting in a low isoparaffin ratio.

[0051] (Comparative Example 9) The activity was evaluated in the same manner as in Comparative Example 8 except that the reaction temperature was 230 ° C. Table 4 shows the evaluation results.

Since wax 1-2 was used as the raw material, raising the gas temperature by 10 ° C from Comparative Example 8 further increased the gasification rate, and the isoparaffin ratio in the kerosene oil having 9 to 21 carbon atoms was low.

[0052] (Comparative Example 10)

A platinum group catalyst containing 0.5% by mass of platinum in metal conversion on a catalyst basis on the USY-type zeolite 2 support shown in Table 3 under the conditions shown in Table 1 and the wax 2 shown in Table 2 and FIG. As a raw material, the hydrogenation reaction was carried out at a reaction temperature of 210 ° C, and the activity was evaluated. Table 4 shows the evaluation results.

Although the gasification rate was the same as in Comparative Example 8 and less than 10% by mass, the ratio of isoparaffin in kerosene oil was low because wax 2 was used as a raw material.

[0053] [Table 4]

Gasification rate in lantern oil fraction Lamp Yield in oil

Isoparaffin ratio Mass ¾ Poor ¾

Example 1 4.2 50.3 71.5 Example 2 5.3 80.3 85.8 Example 3 0.0 28.1 72.8 Example 4 1.5 41.9 87.2 Example 5 2.0 72.8 98.4 Example 6 2 4 57.0 89.8 Example 7 6.0 47.6 96 7 Example 8 7.8 35.8 74.4 Comparative Example 1 2 6 33.3 59.2 Comparative Example 2 1 1.2 54.2 94.1 Comparative Example 3 23.2 38.5 94.6 Comparative Example 4 10.3 38.4 97.4 Comparative Example 5 0.8 22.6 65.0 Comparative Example 6 43.0 40.8 90.0 Comparative Example 7 14.6 17.1 77.4 Comparative Example 8 9.2 43.8 56.5 Comparative Example 9 13.1 38.0 62.4 Comparative Example 10 9.2 50.0 68.7 (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 low-temperature fluidity evaluation is based on the fraction obtained by distilling the oil to be evaluated in the cut range of the specified temperature range using an apparatus conforming to the crude oil distillation method shown in ASTM-D2892. It is a thing. The evaluation results are shown in Table 5.

Here, isoparaffins ratio, when formed into a 100 wt% material having a carbon number of 9 to 21 in a gas chromatograph was defined by the mass ^_0/0 isoparaffins therein. The cloud point and the flow point were measured according to JIS K2269. Table 5 also shows the 10% distillation temperature and 90% distillation temperature measured by the distillation test method shown in JIS K2254 for 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 distillation cut range was 250 ° C to 275 ° C. Table 5 shows the evaluation results.

[Example 11]

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

[0057] (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. Table 5 shows the evaluation results.

[Example 13]

Low-temperature fluidity was evaluated in the same manner as in Example 9 except that the distillation cut range was 325 ° C to 350 ° C. Table 5 shows the evaluation results.

[0059] (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. The light fractions produced simultaneously with wax-1 shown in Table 2 and Fig. 1 are hydrotreated with a catalyst with nickel supported on diatomaceous earth to remove olefins and oxygenated compounds, Distillation was performed at a cut range of 225 ° C to 250 ° C to evaluate low-temperature fluidity. Table 5 shows the evaluation results.

[0060] (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. Table 5 shows the evaluation results.

[0061] (Comparative Example 13)

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

[0062] (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. Table 5 shows the evaluation results.

[0063] (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. Table 5 shows the evaluation results.

[0064] [Table 5]

[0065] The power of the present invention in detail using specific embodiments It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application (Japanese Patent Application No. 2004-090424) filed on March 25, 2004, which is incorporated by reference in its entirety.

Industrial applicability

[0066] According to the present invention, the heavy wax produced by the FT method is hydrotreated to decompose at a low gasification rate, and at the same time increase the isomerization reaction that occurs, thereby containing a sulfur content. First, the low temperature fluidity is good, and liquid fuel can be obtained efficiently.

Claims

The scope of the claims

[1] Fuitsusha one 'carbon atoms produced by Tropsch synthesis 7: a wax containing normal para Fi down 50 mass ^_0/0 above LOO,

A method for producing a hydrocarbon fuel oil.

[2] Fuitsusha carbon atoms produced by one-Tropsch synthesis. 7 to: L00 of normal para Fi down the wax containing 50 mass ^_0/0 or more,

A method for producing a hydrocarbon fuel oil.