WO2012036182A1

WO2012036182A1 - Method for manufacturing aromatic hydrocarbon

Info

Publication number: WO2012036182A1
Application number: PCT/JP2011/070925
Authority: WO
Inventors: 柳川　真一朗; 領二伊田; 小林　正英; 泰之岩佐
Original assignee: Ｊｘ日鉱日石エネルギー株式会社
Priority date: 2010-09-14
Filing date: 2011-09-14
Publication date: 2012-03-22
Also published as: JP5485088B2; KR20130108319A; EP2617697B1; JP2012062255A; EP2617697A1; CN103097323B; US20130184506A1; EP2617697A4; CN103097323A

Abstract

Provided is a method for manufacturing an aromatic hydrocarbon comprising: a decomposition reforming reaction step in which a starting material oil having a 10 volume percent distillation temperature of 140°C or higher and a 90 volume percent distillation temperature of 380°C or lower is brought into contact with a catalyst to induce a reaction, and a product containing C₆−C₈ monocyclic aromatic hydrocarbons and a C₉ or greater heavy distillate is obtained, the catalyst containing a crystalline aluminosilicate and being ordinarily used to manufacture monocyclic aromatic hydrocarbons; a separation step for individually separating the C₆−C₈ monocyclic aromatic hydrocarbons and the C₉ or greater heavy distillate from the product obtained in the decomposition reforming step; a refinement recovery step for refining and recovering the C₆−C₈ monocyclic aromatic hydrocarbons separated in the separation step; and a naphthalene recovery step for separating and recovering naphthalenes from the C₉ or greater heavy distillate separated in the separation step.

Description

Process for producing aromatic hydrocarbons

The present invention relates to a method for producing aromatic hydrocarbons.
This application claims priority based on Japanese Patent Application No. 2010-205903 filed in Japan on September 14, 2010, the contents of which are incorporated herein by reference.

Light cycle oil (hereinafter referred to as “LCO”), which is a cracked light oil produced by fluid catalytic cracking (hereinafter referred to as “FCC”), contains a large amount of polycyclic aromatic hydrocarbons and is used as light oil or heavy oil. It was. However, in recent years, high-value-added monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms (eg benzene, toluene, xylene, ethylbenzene, etc.) that can be used as high octane gasoline base materials and petrochemical raw materials from LCO. Obtaining is being considered.
For example, Patent Documents 1 to 3 propose a method for producing monocyclic aromatic hydrocarbons from polycyclic aromatic hydrocarbons contained in a large amount in LCO or the like using a zeolite catalyst.

JP-A-3-2128 JP-A-3-52993 JP-A-3-26791

However, in the methods described in Patent Documents 1 to 3, it cannot be said that the yield of monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms is sufficiently high.
In recent years, further effective utilization of LCO is expected. Specifically, in addition to efficiently producing monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms such as benzene, toluene, xylene, and ethylbenzene, a new process is added to the same process or a part of it. It is expected to be able to produce other chemicals as effective by-products.

The present invention has been made in view of the above circumstances, and an object of the present invention is to produce a monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms in a high yield from a raw material oil containing a polycyclic aromatic hydrocarbon. In addition, another object of the present invention is to provide a method for producing aromatic hydrocarbons, which can produce other chemical products, for example, aromatic hydrocarbons other than the monocyclic aromatic hydrocarbons.

As a result of intensive studies to achieve the above object, the present inventor has obtained the following knowledge.
Since LCO contains a large amount of polycyclic aromatic hydrocarbons, if this is decomposed and reformed, heavy fractions with 9 or more carbon atoms will be included in addition to monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms. Relatively many can be obtained. It has only been studied that this heavy fraction is simply recovered as a light oil / kerosene base material or recycled as a raw material for the monocyclic aromatic hydrocarbon.

Therefore, as a result of detailed analysis of the components of the present inventor in order to effectively use the heavy fraction, it was found that the heavy fraction contains a large amount of naphthalene and alkylnaphthalene. And based on such knowledge, in parallel with the production of the monocyclic aromatic hydrocarbons, the present invention was completed as a result of further studies on the production of naphthalene as a chemical product.

That is, the method for producing an aromatic hydrocarbon of the present invention includes:
A feed oil having a 10% by volume distillation temperature of 140 ° C. or more and a 90% by volume distillation temperature of 380 ° C. or less is brought into contact with and reacted with a catalyst for producing monocyclic aromatic hydrocarbons containing crystalline aluminosilicate. A cracking and reforming reaction step for obtaining a product containing a monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms and a heavy fraction having 9 or more carbon atoms;
A separation step of separating a monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms and a heavy fraction having 9 or more carbon atoms from the product obtained in the cracking and reforming reaction step;
A purification and recovery step of purifying and recovering the monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms separated in the separation step;
A naphthalene recovery step of separating and recovering naphthalenes containing at least naphthalene from the heavy fraction having 9 or more carbon atoms separated in the separation step.

In the method for producing aromatic hydrocarbons, the naphthalene recovery step is preferably a step of separating and recovering methylnaphthalene and / or dimethylnaphthalene and naphthalene.
In addition, the method for producing the aromatic hydrocarbon,
A hydrogenation reaction step of hydrogenating a remaining fraction from which naphthalenes have been separated in the naphthalene recovery step to obtain a hydrogenation reaction product;
And a recycling step for returning the hydrogenation reaction product to the cracking and reforming reaction step.
In the method for producing aromatic hydrocarbons, the means for separating and recovering naphthalene containing naphthalene in the naphthalene recovery step is preferably a means using a distillation apparatus.

In the method for producing aromatic hydrocarbons, it is preferable that the crystalline aluminosilicate is mainly composed of medium pore zeolite and / or large pore zeolite.
In the method for producing aromatic hydrocarbons, the reaction temperature when reacting the raw material oil and the monocyclic aromatic hydrocarbon production catalyst in the cracking and reforming reaction step is 400 ° C. or more and 650 ° C. or less. It is preferable to do.
In the method for producing aromatic hydrocarbons, the reaction pressure when reacting the raw material oil and the monocyclic aromatic hydrocarbon production catalyst in the cracking and reforming reaction step is 0.1 MPaG or more and 1.5 MPaG. The following is preferable.
In the method for producing aromatic hydrocarbons, the contact time for contacting the raw oil and the monocyclic aromatic hydrocarbon production catalyst in the cracking and reforming reaction step is 1 second to 300 seconds. Is preferred.

According to the method for producing an aromatic hydrocarbon of the present invention, a monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms can be produced with a relatively high yield from a raw material oil containing a polycyclic aromatic hydrocarbon, Moreover, naphthalenes containing naphthalene as other chemicals can be produced together.

It is a figure for demonstrating one Embodiment of the manufacturing method of the aromatic hydrocarbon of this invention.

Hereafter, the manufacturing method of the aromatic hydrocarbon of this invention is demonstrated in detail.
FIG. 1 is a diagram for explaining an embodiment of the method for producing aromatic hydrocarbons of the present invention. The method for producing aromatic hydrocarbons of this embodiment is a simple method having 6 to 8 carbon atoms from feedstock. This is a method for producing a ring aromatic hydrocarbon and producing naphthalene containing naphthalene.

That is, the method for producing aromatic hydrocarbons of the present embodiment, as shown in FIG.
(A) Production containing raw material oil containing a monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms and a heavy fraction having 9 or more carbon atoms by contacting and reacting with a catalyst for producing monocyclic aromatic hydrocarbons Decomposition reforming reaction step to obtain a product,
(B) a separation step of separating the product produced in the cracking and reforming reaction step into a plurality of fractions;
(C) a hydrogen recovery step for recovering hydrogen by-produced in the cracking and reforming reaction step from the gas component separated in the separation step;
(D) an LPG recovery step for recovering LPG by-produced in the cracking and reforming reaction step from the liquid fraction separated in the separation step;
(E) a purification and recovery step for purifying and recovering the monocyclic aromatic hydrocarbons from the liquid fraction separated in the separation step;
(F) a naphthalene recovery step for separating and recovering naphthalenes containing at least naphthalene from a heavy fraction having 9 or more carbon atoms obtained from the liquid fraction separated in the separation step;
(G) a hydrogen supply step for supplying the hydrogen recovered in the hydrogen recovery step to the hydrogenation reaction step (h) a hydrogenation reaction step for hydrogenating the remaining fraction from which naphthalenes have been separated in the naphthalene recovery step; and (i ) Recycling process to return the hydrogenation reaction product obtained in the hydrogenation reaction process to the cracking and reforming reaction process,
It is preferable to have.
Of the steps (a) to (i), the steps (a), (b), (e), and (f) are essential steps in the invention according to claim 1, The process is an arbitrary process.

Hereinafter, each step will be specifically described.
<Decomposition and reforming reaction process>
In the cracking and reforming reaction step, the feedstock oil is brought into contact with the catalyst for producing monocyclic aromatic hydrocarbons, the saturated hydrocarbon contained in the feedstock oil is used as the hydrogen donor source, and the polycyclic aromatic is obtained by hydrogen transfer reaction from the saturated hydrocarbon. Group hydrocarbons are partially hydrogenated, ring-opened and converted to monocyclic aromatic hydrocarbons. It can also be converted to monocyclic aromatic hydrocarbons by cyclization and dehydrogenation of saturated hydrocarbons obtained in the feedstock or in the cracking process. Furthermore, it is possible to obtain monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms by decomposing monocyclic aromatic hydrocarbons having 9 or more carbon atoms. As a result, a product containing a monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms and a heavy fraction having 9 or more carbon atoms is obtained. This product includes hydrogen, methane, ethane, ethylene, LPG (propane, propylene, butane, butene, etc.), etc. in addition to monocyclic aromatic hydrocarbons and heavy fractions. The heavy fraction contains a large amount of naphthalene, methylnaphthalene, and dimethylnaphthalene. In the present application, these naphthalene, methylnaphthalene, and dimethylnaphthalene are collectively referred to as “naphthalenes”.
In this cracking and reforming reaction step, components such as naphthenobenzenes, paraffins and naphthenes in the feedstock oil can be eliminated by producing monocyclic aromatic hydrocarbons, and polycyclic aromatic hydrocarbons are By cutting the alkyl side chain simultaneously with the conversion to the monocyclic aromatic hydrocarbon, it becomes possible to obtain high-value-added naphthalenes having few side chains such as naphthalene, methylnaphthalene and dimethylnaphthalene. That is, in the present cracking and reforming reaction step, a monocyclic aromatic hydrocarbon can be produced in a high yield, and at the same time, other components having a boiling point close to naphthalenes can be reduced as much as possible. Therefore, by increasing the amount of naphthalene having a short side chain and increasing the content of naphthalene in the cracking and reforming reaction product oil, it is possible to efficiently recover the naphthalene described later.
The cracked light oil and the like listed as the main raw material oil originally contain a lot of naphthalenes, but at the same time contain a lot of other components such as naphthenobenzenes and paraffins. Therefore, the content ratio of naphthalenes relative to the total amount of raw material oil is small, and it is very difficult to separate and purify naphthalenes directly from raw material oil. If naphthalenes are separated and purified directly from the raw oil, an energy intensive process such as crystallization is adopted, which is not preferable.
As described above, the present cracking and reforming reaction step can greatly improve the ratio of recovering useful aromatic hydrocarbons.

(Raw oil)
The feedstock oil used in the present embodiment is an oil having a 10 vol% distillation temperature of 140 ° C or higher and a 90 vol% distillation temperature of 380 ° C or lower. With an oil having a 10% by volume distillation temperature of less than 140 ° C., a monocyclic aromatic hydrocarbon is produced from a light oil, which does not meet the gist of the present embodiment. In addition, when oil having a 90% by volume distillation temperature exceeding 380 ° C. is used, the yield of monocyclic aromatic hydrocarbons is lowered and coke deposition on the catalyst for producing monocyclic aromatic hydrocarbons The amount tends to increase and cause a sharp decrease in catalyst activity.
The 10 vol% distillation temperature of the feedstock oil is preferably 150 ° C or higher, and the 90 vol% distillation temperature of the feedstock oil is preferably 360 ° C or lower. On the other hand, the upper limit of the 10 vol% distillation temperature and the lower limit of the 90 vol% distillation temperature of the feed oil are not particularly limited, but monocyclic aromatic hydrocarbons and naphthalenes having 6 to 8 carbon atoms can be produced efficiently. In this respect, the 10 vol% distillation temperature is preferably 210 ° C or lower, and the 90 vol% distillation temperature is preferably 240 ° C or higher.

The 10 vol% distillation temperature and 90 vol% distillation temperature mentioned here mean values measured in accordance with JIS K2254 “Petroleum products-distillation test method”.
Examples of feedstocks having a 10% by volume distillation temperature of 140 ° C. or higher and a 90% by volume distillation temperature of 380 ° C. or lower include, for example, LCO produced by an FCC unit, LCO hydrorefined oil, hydrocracked diesel oil / heat Other cracked gas oils such as cracked gas oil, coal liquefied oil, heavy oil hydrocracked refined oil, straight-run kerosene, straight-run kerosene, coker kerosene, coker gas oil, and oil sand hydrocracked refined oil can be mentioned.

In addition, if the feedstock oil contains a large amount of polycyclic aromatic hydrocarbons, the yield of monocyclic aromatic hydrocarbons decreases, so the content of polycyclic aromatic hydrocarbons in the feedstock oil (polycyclic aromatic content) ) Is preferably 50% by volume or less, and more preferably 40% by volume or less. However, when it is desired to further increase the yield of naphthalene (or naphthalenes) produced together with monocyclic aromatic hydrocarbons as will be described later, the polycyclic aromatic content in the feedstock oil may be, for example, 50% by volume or more. . However, even in that case, the content of the aromatic hydrocarbon of 3 or more rings is preferably 30% by volume or less, and more preferably 15% by volume or less.
The polycyclic aromatic component mentioned here is measured according to JPI-5S-49 “Petroleum products—Hydrocarbon type test method—High performance liquid chromatograph method” or analyzed by FID gas chromatograph method. It means the sum of the bicyclic aromatic hydrocarbon content (bicyclic aromatic content) and the tricyclic or higher aromatic hydrocarbon content (tricyclic or higher aromatic content). Hereinafter, when the content of polycyclic aromatic hydrocarbon, bicyclic aromatic hydrocarbon, tricyclic or higher aromatic hydrocarbon is indicated by volume%, it is indicated by mass% in JPI-5S-49 method. If it is, it is measured based on the FID gas chromatograph method.

(Reaction format)
Examples of the reaction mode when the raw material oil is brought into contact with and reacted with the catalyst for producing a monocyclic aromatic hydrocarbon include a fixed bed, a moving bed, and a fluidized bed. In this embodiment, since the heavy component is used as a raw material, a fluidized bed that can continuously remove the coke component adhering to the catalyst and can stably perform the reaction is preferable. Particularly preferred is a continuous regenerative fluidized bed in which the catalyst circulates between the reactor and the regenerator, and the reaction-regeneration can be repeated continuously. The feedstock oil in contact with the catalyst for producing monocyclic aromatic hydrocarbons is preferably in a gas phase. Moreover, you may dilute a raw material with gas as needed.

(Catalyst for monocyclic aromatic hydrocarbon production)
The catalyst for monocyclic aromatic hydrocarbon production contains crystalline aluminosilicate.

[Crystalline aluminosilicate]
The crystalline aluminosilicate is preferably a medium pore zeolite and / or a large pore zeolite because the yield of monocyclic aromatic hydrocarbons can be further increased.
The medium pore zeolite is a zeolite having a 10-membered ring skeleton structure. Examples of the medium pore zeolite include AEL type, EUO type, FER type, HEU type, MEL type, MFI type, NES type, and TON type. And zeolite having a WEI type crystal structure. Among these, the MFI type is preferable because the yield of monocyclic aromatic hydrocarbons can be further increased.
The large pore zeolite is a zeolite having a 12-membered ring skeleton structure. Examples of the large pore zeolite include AFI type, ATO type, BEA type, CON type, FAU type, GME type, LTL type, and MOR type. , Zeolites of MTW type and OFF type crystal structures. Among these, the BEA type is preferable because the total yield of monocyclic aromatic hydrocarbons and aliphatic hydrocarbons having 3 to 4 carbon atoms can be further increased.

However, when it is desired to increase the yield of naphthalene (or naphthalenes) produced together with monocyclic aromatic hydrocarbons as described later, it contains a crystalline aluminosilicate other than the above MFI type or BEA type zeolite. A thing may be used.

The crystalline aluminosilicate contains small pore zeolite having a skeleton structure of 10-membered ring or less, and ultra-large pore zeolite having a skeleton structure of 14-membered ring or more, in addition to medium pore zeolite and large pore zeolite. May be.
Here, examples of the small pore zeolite include zeolites having crystal structures of ANA type, CHA type, ERI type, GIS type, KFI type, LTA type, NAT type, PAU type, and YUG type.
Examples of the ultra-large pore zeolite include zeolites having CLO type and VPI type crystal structures.

When the cracking and reforming reaction step is a fixed bed reaction, the content of the crystalline aluminosilicate in the monocyclic aromatic hydrocarbon production catalyst is 100% by mass based on the entire monocyclic aromatic hydrocarbon production catalyst. Is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, and particularly preferably 90 to 100% by mass. If the content of the crystalline aluminosilicate is 60% by mass or more, the yield of monocyclic aromatic hydrocarbons can be sufficiently increased. In addition, the yield of naphthalene can be relatively high.

When the cracking and reforming reaction step is a fluidized bed reaction, the content of crystalline aluminosilicate in the monocyclic aromatic hydrocarbon production catalyst is 100% by mass of the total monocyclic aromatic hydrocarbon production catalyst. Is preferably 20 to 60% by mass, more preferably 30 to 60% by mass, and particularly preferably 35 to 60% by mass. When the content of the crystalline aluminosilicate is 20% by mass or more, the yield of monocyclic aromatic hydrocarbons can be sufficiently increased. In addition, the yield of naphthalene can be relatively high. In addition, when content of crystalline aluminosilicate exceeds 60 mass%, content of the binder which can be mix | blended with a catalyst will decrease and it may become unsuitable for fluid bed use.

[Phosphorus, Boron]
The catalyst for producing monocyclic aromatic hydrocarbons preferably contains phosphorus and / or boron. If the catalyst for producing monocyclic aromatic hydrocarbons contains phosphorus and / or boron, it is possible to prevent the yield of monocyclic aromatic hydrocarbons from decreasing with time, and to suppress the formation of coke on the catalyst surface.

As a method for incorporating phosphorus into the monocyclic aromatic hydrocarbon production catalyst, for example, phosphorus is supported on crystalline aluminosilicate, crystalline aluminogallosilicate, or crystalline aluminodine silicate by an ion exchange method, an impregnation method, or the like. Examples thereof include a method, a method in which a phosphorus compound is contained during zeolite synthesis and a part of the skeleton of the crystalline aluminosilicate is replaced with phosphorus, and a method in which a crystal accelerator containing phosphorus is used during zeolite synthesis. The aqueous solution containing phosphate ions used at that time is not particularly limited, but phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and other water-soluble phosphates can be dissolved in water at an arbitrary concentration. What was prepared can be used preferably.

As a method for incorporating boron into the catalyst for producing monocyclic aromatic hydrocarbons, for example, boron is supported on crystalline aluminosilicate, crystalline aluminogallosilicate, or crystalline aluminodine silicate by an ion exchange method, an impregnation method, or the like. Examples thereof include a method, a method in which a boron compound is contained at the time of zeolite synthesis and a part of the skeleton of the crystalline aluminosilicate is replaced with boron, and a method in which a crystal accelerator containing boron is used at the time of zeolite synthesis.

The content of phosphorus and / or boron in the catalyst for monocyclic aromatic hydrocarbon production is preferably 0.1 to 10% by mass relative to the total weight of the catalyst, and the lower limit is 0.5% by mass or more. The upper limit is more preferably 9% by mass or less, and particularly preferably 8% by mass or less. When the content of phosphorus and / or boron with respect to the total weight of the catalyst is 0.1% by mass or more, a decrease in the yield of monocyclic aromatic hydrocarbons over time can be prevented, and by 10% by mass or less. The yield of monocyclic aromatic hydrocarbons can be increased.

[Gallium, zinc]
The catalyst for producing monocyclic aromatic hydrocarbons can contain gallium and / or zinc, if necessary. If gallium and / or zinc is contained, the production rate of monocyclic aromatic hydrocarbons can be increased.
The gallium-containing form in the monocyclic aromatic hydrocarbon production catalyst is one in which gallium is incorporated into the lattice skeleton of crystalline aluminosilicate (crystalline aluminogallosilicate), and gallium is supported on the crystalline aluminosilicate. And those containing both (gallium-supporting crystalline aluminosilicate).

In the catalyst for producing monocyclic aromatic hydrocarbons, the zinc-containing form is one in which zinc is incorporated in the lattice skeleton of crystalline aluminosilicate (crystalline aluminodine silicate), or zinc is supported on crystalline aluminosilicate. One (zinc-supporting crystalline aluminosilicate) and one containing both.
Crystalline aluminogallosilicate and crystalline aluminodine silicate have a structure in which SiO ₄ , AlO ₄ and GaO ₄ / ZnO ₄ structures are present in the skeleton. In addition, crystalline aluminogallosilicate and crystalline aluminodine silicate are, for example, gel crystallization by hydrothermal synthesis, a method of inserting gallium or zinc into the lattice skeleton of crystalline aluminosilicate, or crystalline gallosilicate or crystalline It is obtained by inserting aluminum into the lattice skeleton of zincosilicate.

The gallium-supporting crystalline aluminosilicate is obtained by supporting gallium on a crystalline aluminosilicate by a known method such as an ion exchange method or an impregnation method. The gallium source used in this case is not particularly limited, and examples thereof include gallium salts such as gallium nitrate and gallium chloride, and gallium oxide.
The zinc-supporting crystalline aluminosilicate is obtained by supporting zinc on a crystalline aluminosilicate by a known method such as an ion exchange method or an impregnation method. Although it does not specifically limit as a zinc source used in that case, Zinc salts, such as zinc nitrate and zinc chloride, zinc oxide, etc. are mentioned.

When the catalyst for monocyclic aromatic hydrocarbon production contains gallium and / or zinc, the content of gallium and / or zinc in the catalyst for monocyclic aromatic hydrocarbon production is based on 100% by mass of the entire catalyst. The content is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 1.5% by mass. If the content of gallium and / or zinc is 0.01% by mass or more, the production rate of monocyclic aromatic hydrocarbons can be increased, and if it is 5.0% by mass or less, the monocyclic aromatic hydrocarbons The yield can be higher.

[shape]
The catalyst for monocyclic aromatic hydrocarbon production is, for example, in the form of powder, granules, pellets, etc., depending on the reaction mode. For example, in the case of a fluidized bed, it is in the form of powder, and in the case of a fixed bed, it is in the form of particles or pellets. The average particle size of the catalyst used in the fluidized bed is preferably 30 to 180 μm, more preferably 50 to 100 μm. The bulk density of the catalyst used in the fluidized bed is preferably 0.4 to 1.8 g / cc, more preferably 0.5 to 1.0 g / cc.

The average particle size represents a particle size of 50% by mass in the particle size distribution obtained by classification by sieving, and the bulk density is a value measured by the method of JIS standard R9301-2-3.
When obtaining a granular or pellet-shaped catalyst, if necessary, an inert oxide may be blended into the catalyst as a binder and then molded using various molding machines.
When the catalyst for monocyclic aromatic hydrocarbon production contains an inorganic oxide such as a binder, one containing phosphorus as the binder may be used.

(Reaction temperature)
The reaction temperature when the raw material oil is brought into contact with and reacted with the catalyst for producing a monocyclic aromatic hydrocarbon is not particularly limited, but is preferably 400 to 650 ° C, more preferably 450 to 650 ° C. If reaction temperature is 400 degreeC or more, raw material oil can be made to react easily. If the reaction temperature is 450 ° C. or higher and 650 ° C. or lower, the yield of monocyclic aromatic hydrocarbons can be sufficiently increased, and the yield of naphthalenes can be relatively high.

(Reaction pressure)
About the reaction pressure at the time of making a raw material oil contact and react with the catalyst for monocyclic aromatic hydrocarbon production, it is preferable to set it as 1.5 MPaG or less, and it is more preferable to set it as 1.0 MPaG or less. If the reaction pressure is 1.5 MPaG or less, the by-product of light gas can be suppressed and the pressure resistance of the reactor can be lowered. Moreover, if it is 0.1 MPaG or more and 1.5 MPaG or less, the yield of monocyclic aromatic hydrocarbons can be made sufficiently high, and the yield of naphthalenes can also be made relatively high.

(Contact time)
The contact time between the feedstock and the catalyst for producing monocyclic aromatic hydrocarbons is not particularly limited as long as the desired reaction proceeds substantially. For example, gas passing over the catalyst for producing monocyclic aromatic hydrocarbons The time is preferably 1 to 300 seconds, more preferably a lower limit of 5 seconds and an upper limit of 150 seconds. If the contact time is 1 second or longer, the reaction can be performed reliably, and if the contact time is 300 seconds or shorter, accumulation of carbonaceous matter in the catalyst due to coking or the like can be suppressed. Or the generation amount of the light gas by decomposition | disassembly can be suppressed. Furthermore, the yield of monocyclic aromatic hydrocarbons can be made sufficiently high, and the yield of naphthalenes can be made relatively high.

<Separation process>
In the separation step, the product produced in the cracking and reforming reaction step is separated into a plurality of fractions.
In order to separate into a plurality of fractions, a known distillation apparatus or gas-liquid separation apparatus may be used. As an example of a distillation apparatus, what can distill and isolate | separate a some fraction with a multistage distillation apparatus like a stripper is mentioned. As an example of the gas-liquid separation device, a gas-liquid separation tank, a product introduction pipe for introducing the product into the gas-liquid separation tank, a gas component outflow pipe provided at the upper part of the gas-liquid separation tank, What comprises the liquid component outflow pipe | tube provided in the lower part of the said gas-liquid separation tank is mentioned.

In the separation step, it is preferable to separate at least the gas component and the liquid fraction, and the liquid fraction may be further separated into a plurality of fractions. As an example of a separation process, there exists a form which isolate | separates into the gas component and liquid fraction which mainly contain C4 or less components (for example, hydrogen, methane, ethane, LPG, etc.). Moreover, there exists a form which isolate | separates into a gas component and liquid fraction containing a C2-C2 component (for example, hydrogen, methane, ethane) as a separation process. In addition, as a separation step, there is a form in which the liquid fraction is further separated into a fraction containing LPG, a monocyclic aromatic hydrocarbon, and a heavy fraction. In addition, as the separation step, the liquid fraction is further separated into LPG (for example, propylene, propane, butene, butane, etc.), a fraction containing monocyclic aromatic hydrocarbons, and a plurality of heavy fractions, etc. Is mentioned. Further, when a fluidized bed is employed as a reaction format in the cracking and reforming reaction step, the mixed catalyst powder and the like may be removed in this step. However, as for the heavy fraction, naphthalenes may be separated separately, or the heavy fraction may be fractionated together without dividing into a plurality of fractions. The boiling range of the fraction containing the monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms is preferably 78 ° C. to 150 ° C., and the boiling range of the heavy fraction containing mainly naphthalenes is 210 ° C. to 270 ° C. It is preferable that

<Purification and recovery process>
In the purification and recovery step, the monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms obtained in the separation step is purified and recovered.
In this purification and recovery step, when the liquid fraction is sufficiently fractionated in the separation step and the monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms is separated into benzene / toluene / xylene, A process of purifying and recovering the slag is employed. In addition, when fractionated as monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms, the monocyclic aromatic hydrocarbons are recovered and then separated into benzene / toluene / xylene. Processes for purification and recovery are adopted.

In the separation step, the liquid fraction is not fractionated well, and when a monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms is recovered, a large amount of fraction other than the monocyclic aromatic hydrocarbon is contained. In this case, this fraction may be separated and supplied to, for example, a hydrogenation reaction step or a naphthalene recovery step described later. In particular, among fractions other than monocyclic aromatic hydrocarbons, a fraction heavier than the monocyclic aromatic hydrocarbon (heavy fraction having 9 or more carbon atoms) is supplied to the naphthalene recovery step. Is preferred. This is because the heavy fraction having 9 or more carbon atoms is mainly composed of polycyclic aromatic hydrocarbons, and particularly contains a large amount of naphthalene or alkylnaphthalene.

<Naphthalene recovery process>
In the naphthalene recovery step, naphthalenes containing at least naphthalene are separated and recovered from the heavy fraction having 9 or more carbon atoms obtained from the liquid fraction separated in the separation step.
In the naphthalene recovery step, when the heavy fraction separated in the separation step is separated into a heavy fraction mainly containing naphthalenes and other heavy fractions, The heavy fraction containing naphthalene is purified, and naphthalene is separated and recovered. Further, in the separation step, when the heavy fraction having 9 or more carbon atoms is fractionated without dividing into a plurality of fractions, fractions containing naphthalenes, specifically naphthalene, methylnaphthalene, dimethyl It is separated into naphthalene containing naphthalene and other fractions, and at least naphthalene containing naphthalene is purified and recovered.
In order to separate the heavy fraction into a plurality of fractions, a known distillation apparatus (distillation tower) such as that used in the separation step may be used.

Through the cracking and reforming reaction step, components having boiling points close to naphthalenes in the cracking and reforming reaction product oil have been greatly reduced. Therefore, in the present naphthalene recovery step, it was used in the separation step. Naphthalene can be separated and purified and recovered with high purity using only such known distillation apparatus. For example, naphthalene can be purified to a purity of about 80 to 98% and recovered. The purity of the recovered naphthalene is determined by the number of components having a boiling point close to naphthalene remaining in the cracking and reforming reaction step, the amount of the components generated, and the performance of the distillation apparatus. When naphthalene is recovered with a purity of 95% or more, it can be handled as a product having commercial value that is generally distributed as crude naphthalene, and the purity is less than 95%, for example, about 80 to 95%. By carrying out a purification treatment later to increase the purity to 95% or more, it becomes possible to obtain crude naphthalene as a chemical product. Further, even a fraction having a purity of 95% or more can be further purified to obtain higher-purity naphthalene. Examples of the purification treatment means in this case include crystallization.

In the naphthalene recovery step, as long as naphthalene can be separated and recovered, naphthalenes other than naphthalene may be collected together as alkyl naphthalene or separately as methyl naphthalene, dimethylnaphthalene, etc., and purified and recovered. In this case, methylnaphthalene and dimethylnaphthalene are purified to a purity of about 80 to 95% and recovered. Then, it refine | purifies to the purity requested | required as a chemical product.

Here, in the naphthalene recovery step, fractions other than the target naphthalene, methylnaphthalene, and dimethylnaphthalene are also obtained. This fraction is sent out of the system and, for example, is subjected to a treatment such as refining as necessary, and then used as a light oil / kerosene base material. Or it is sent to the hydrogenation reaction process mentioned later, and also it is recycled through this process.

In the present embodiment shown in FIG. 1, the naphthalene recovery step is a single step. In the naphthalene recovery process, first, a process for separating and recovering naphthalene from a heavy fraction having 9 or more carbon atoms is provided, and then a process for separating and recovering methylnaphthalene, dimethylnaphthalene, etc. is provided. Separately, naphthalene, methylnaphthalene and dimethylnaphthalene may be fractionated and recovered. Further, the fractions other than these are used as a light oil / kerosene base material as described above, or subjected to recycling to a raw material oil through a hydrogenation reaction step or the like.

<Hydrogenation reaction process>
In this hydrogenation reaction step, a part or all of the remaining fraction from which naphthalenes are separated in the naphthalene recovery step is supplied to the hydrogenation reaction step and hydrogenated. Here, when only naphthalene is separated and recovered in the naphthalene recovery step and alkylnaphthalene such as methylnaphthalene and dimethylnaphthalene is not separated and recovered, these alkylnaphthalenes become the above-mentioned “remaining fractions from which naphthalenes are separated”. The hydrogenation reaction process is started. In addition, you may utilize the remaining fraction which isolate | separated naphthalene which was not supplied to the hydrogenation reaction process as fuel base materials, such as light oil and kerosene.

Specifically, the remaining fraction from which naphthalenes have been separated in the naphthalene recovery step and hydrogen are supplied to a hydrogenation reactor, and a hydrogenation catalyst is used to contain many of the remaining fractions from which naphthalenes have been separated. At least a part of the ring aromatic hydrocarbon is hydrotreated.
Although it does not specifically limit about polycyclic aromatic hydrocarbon, It is preferable to hydrogenate until an aromatic ring becomes one or less on average. If the hydrogenation is carried out until the average number of aromatic rings is 1 or less, it can be easily converted into monocyclic aromatic hydrocarbons when returned to the cracking and reforming reaction step.

In particular, in order to further improve the yield of monocyclic aromatic hydrocarbons, the polycyclic aromatic hydrocarbon content in the hydrogenation reaction product obtained in the hydrogenation reaction step is preferably 20% by mass or less. It is preferable to make it 10 mass% or less. The polycyclic aromatic hydrocarbon content in the hydrogenation reaction product is preferably less than the polycyclic aromatic hydrocarbon content of the feedstock, and decreases as the amount of hydrogenation catalyst increases and the reaction pressure increases. be able to.
However, it is not necessary to hydrotreat all the polycyclic aromatic hydrocarbons until they become saturated hydrocarbons. Excessive hydrogenation tends to increase hydrogen consumption and heat generation.

If priority is given to improving the yield of naphthalene (naphthalenes) over improving the yield of monocyclic aromatic hydrocarbons, the polycyclic aromatic hydrocarbons in the hydrogenation reaction product obtained in the hydrogenation reaction step The content is preferably 20% by mass or more.
In the present embodiment, it is possible to use hydrogen as a by-product in the cracking and reforming reaction step. That is, hydrogen is recovered from the gas component obtained in the separation step in a hydrogen recovery step described later, and the recovered hydrogen is supplied to the hydrogenation reaction step in the hydrogen supply step.

As the reaction format in the hydrogenation reaction step, a fixed bed is preferably employed.
As the hydrogenation catalyst, a known hydrogenation catalyst (for example, nickel catalyst, palladium catalyst, nickel-molybdenum catalyst, cobalt-molybdenum catalyst, nickel-cobalt-molybdenum catalyst, nickel-tungsten catalyst, etc.) should be used. Can do.
The reaction temperature varies depending on the hydrogenation catalyst used, but is usually in the range of 100 to 450 ° C., more preferably 200 to 400 ° C., and further preferably 250 to 380 ° C.

The reaction pressure varies depending on the hydrogenation catalyst and raw materials used, but is preferably in the range of 0.7 MPa to 13 MPa, more preferably 1 MPa to 10 MPa, and particularly preferably 1 MPa to 7 MPa. If the reaction pressure is 13 MPa or less, a hydrogenation reactor having a low withstand pressure can be used, and the equipment cost can be reduced.
On the other hand, the reaction pressure is preferably 0.7 MPa or more from the viewpoint of the yield of the hydrogenation reaction.
Hydrogen consumption is preferably not more than ^{^{3000scfb (506Nm 3 / m 3)}} , more preferably less ^{^{2500scfb (422Nm 3 / m 3)}} , more preferably not more than 1500scfb (253Nm ^³ / ^m ³⁾ .
On the other hand, the hydrogen consumption is preferably 300 scfb (50 Nm ³ / m ³ ) or more from the viewpoint of the yield of the hydrogenation reaction.
The liquid hourly space velocity (LHSV) is preferably set to below 0.1 h ^-1 or ^{20h -1,} and more preferably to 0.2 h ^-1 or ^{10h -1} or less. When LHSV is 20 h ⁻¹ or less, polycyclic aromatic hydrocarbons can be sufficiently hydrogenated at a lower hydrogenation reaction pressure. On the other hand, by setting 0.1 ^-1 or more, it is possible to avoid an increase in size of the hydrogenation reactor.

<Hydrogen recovery process>
In the hydrogen recovery step, hydrogen is recovered from the gas component obtained in the separation step.
The method for recovering hydrogen is not particularly limited as long as hydrogen contained in the gas component obtained in the separation step and other gas can be separated. For example, the pressure fluctuation adsorption method (PSA method), the cryogenic separation method, Examples thereof include a membrane separation method.
Usually, the amount of hydrogen recovered in the hydrogen recovery step is larger than the amount necessary for hydrogenating the heavy fraction or the light oil / kerosene fraction.

<Hydrogen supply process>
In the hydrogen supply step, the hydrogen obtained in the hydrogen recovery step is supplied to the hydrogenation reactor in the hydrogenation reaction step. The amount of hydrogen supplied at that time is adjusted according to the amount of the remaining fraction that is supplied to the hydrogenation reaction step and from which naphthalenes have been separated in the naphthalene recovery step. If necessary, the hydrogen pressure is adjusted.
By providing a hydrogen supply step as in this embodiment, the remaining fraction obtained by separating naphthalenes in the naphthalene recovery step can be hydrogenated using hydrogen by-produced in the cracking and reforming reaction step. The efficiency of the apparatus can be improved.

<Recycling process>
In the recycling process, the hydrogenation reaction product is mixed with the raw material oil and returned to the cracking and reforming reaction process. The hydrogenation reaction product is obtained by reacting the remaining fraction after separation of naphthalenes in the naphthalene recovery step in the hydrogenation reaction step.
By returning such a hydrogenation reaction product to the cracking and reforming reaction step, it is possible to obtain monocyclic aromatic hydrocarbons and naphthalenes from the heavy fractions (except naphthalenes) that were by-products as raw materials. it can. Therefore, the amount of by-products can be reduced, and the production amount of monocyclic aromatic hydrocarbons and naphthalenes can be increased. Moreover, since saturated hydrocarbons are also produced by hydrogenation, the hydrogen transfer reaction in the cracking and reforming reaction step can be promoted. From these, it is possible to improve the overall yield of monocyclic aromatic hydrocarbons relative to the amount of feedstock supplied, and also improve the yield of naphthalenes.
If the remaining fraction from which naphthalene was separated in the naphthalene recovery step without being hydrotreated is returned to the cracking reforming reaction step as it is, the reactivity of the polycyclic aromatic hydrocarbon is low, Almost no improvement in the yield of aromatic hydrocarbons can be expected. However, it is possible to improve the yield of naphthalenes.

<LPG recovery process>
In the LPG recovery step, LPG produced as a by-product in the cracking and reforming reaction step is recovered from the liquid fraction separated in the separation step.
In this LPG recovery step, liquid fractions having 3 and 4 carbon atoms, that is, propylene, propane, butene and butane are purified and recovered as LPG. In the method for producing aromatic hydrocarbons of the present embodiment, the cracked reforming reaction product oil contains more olefins such as propylene and butene, unlike products such as hydrocracking in a normal petroleum refining process. Therefore, olefins can be recovered by hydrogenation or rectification as necessary.

As described above, in the method for producing aromatic hydrocarbons of the present embodiment, monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms in a relatively high yield from the raw material oil containing polycyclic aromatic hydrocarbons. In addition, naphthalenes containing naphthalene as other chemicals and olefins such as propylene, propane, butene and butane can be produced together.

In particular, naphthalene is conventionally produced by a crystallization method in which coal tar distillate is cooled and crystallized, but the crystallization method requires a complicated process, and thus the production cost is high. There are challenges.
In contrast, the method for producing aromatic hydrocarbons of the present embodiment adds a naphthalene recovery step and, if necessary, a naphthalene separation and recovery step to the process for producing monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms. This makes it possible to obtain naphthalene having a relatively high purity. Therefore, the production cost of naphthalene (or naphthalenes), when subtracting the amount of monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms, is significantly lower than the conventional method by crystallization, and therefore naphthalene ( Or naphthalenes) can be provided at low cost.

"Other embodiments"
It should be noted that the present invention is not limited to the above embodiment, and various modifications can be made without departing from the gist of the present invention.
For example, in the method shown in FIG. 1, a hydrogenation reaction step for hydrogenating part of the liquid components separated in the separation step is provided between the separation step and the purification and recovery step. The hydrogenation reaction product obtained in the step may be distilled to purify and recover the monocyclic aromatic hydrocarbon.
Alternatively, a part of the heavy fraction separated in the separation step may be supplied to the hydrogenation reaction step without going through the naphthalene recovery step, and hydrogenated to return to the cracking reforming reaction step.
Further, in these methods and the method shown in FIG. 1, the hydrogen used in the hydrogenation reaction step is replaced with the one produced as a by-product in the cracking and reforming reaction step, using hydrogen obtained by a known hydrogen production method. Alternatively, hydrogen produced as a by-product in other catalytic cracking methods may be used.

Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to these examples.

[Catalyst preparation example for monocyclic aromatic hydrocarbon production]
Preparation of catalyst comprising Ga and phosphorus-supported crystalline aluminosilicate:
Sodium oxalate (J sodium silicate No. 3, SiO ₂ : 28-30% by mass, Na: 9-10% by mass, balance water, manufactured by Nippon Chemical Industry Co., Ltd.): 1706.1 g and water: 2227.5 g Solution (A), Al ₂ (SO ₄ ) ₃ · 14 to 18H ₂ O (special reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.): 64.2 g, tetrapropylammonium bromide: 369.2 g, H ₂ SO ₄ (97% by mass): 152.1 g, NaCl: 326.6 g and water: 2975.7 g, respectively, were prepared (B).
Next, the solution (B) was gradually added to the solution (A) while stirring the solution (A) at room temperature.
The resulting mixture was vigorously stirred with a mixer for 15 minutes to break up the gel into a milky homogeneous fine state.
Next, this mixture was put into a stainless steel autoclave, and a crystallization operation was performed under self-pressure under the conditions of a temperature of 165 ° C., a time of 72 hours, and a stirring speed of 100 rpm. After completion of the crystallization operation, the product was filtered to recover the solid product, and washing and filtration were repeated 5 times using about 5 liters of deionized water. The solid substance obtained by filtration was dried at 120 ° C., and further calcined at 550 ° C. for 3 hours under air flow.
As a result of X-ray diffraction analysis (model name: Rigaku RINT-2500V), the obtained fired product was confirmed to have an MFI structure. The fluorescent X-ray analysis (model name: Rigaku ZSX101e) _by, SiO 2 / _Al 2 _{O 3} ratio (molar ratio) was 64.8. Moreover, the aluminum element contained in the lattice skeleton calculated from this result was 1.32% by mass.
Subsequently, 30 mass% ammonium nitrate aqueous solution was added in the ratio of 5 mL per 1 g of obtained baked products, and it heated and stirred at 100 degreeC for 2 hours, Then, it filtered and washed with water. This operation was repeated 4 times, followed by drying at 120 ° C. for 3 hours to obtain an ammonium type crystalline aluminosilicate.
Thereafter, baking was performed at 780 ° C. for 3 hours to obtain a proton-type crystalline aluminosilicate.
Next, 120 g of the obtained proton-type crystalline aluminosilicate was impregnated with 120 g of an aqueous gallium nitrate solution so that 0.4% by mass (a value obtained by setting the total mass of the crystalline aluminosilicate to 100% by mass) was supported, Dry at 120 ° C. Then, it baked at 780 degreeC under air circulation for 3 hours, and obtained the gallium carrying | support crystalline aluminosilicate.
Next, 30 g of the obtained gallium-supporting crystalline aluminosilicate was charged with 30 g of diammonium hydrogenphosphate aqueous solution so that 0.7% by mass of phosphorus (a value obtained by setting the total mass of the crystalline aluminosilicate to 100% by mass) was supported. Impregnation and drying at 120 ° C. Then, it baked at 780 degreeC under air circulation for 3 hours, and obtained the catalyst A containing crystalline aluminosilicate, gallium, and phosphorus.
In the case of producing monocyclic aromatic hydrocarbons in a fluidized bed reaction mode, catalyst A is added to crystalline aluminosilicate, gallium and phosphorus, and a silica binder (silica binder content is 60% relative to the total mass of the catalyst). % By mass).

Example 1
LCO (10% by volume distillation temperature 224.5 ° C., 90% by volume distillation temperature 349.5 ° C.) shown in Table 1 which is a raw material oil, reaction temperature: 550 ° C., reaction pressure: 0.1 MPaG, contact time Under a condition of 30 seconds, 60% by mass of the silica binder was added to the catalyst A (MFI type zeolite carrying 0.4% by mass of gallium and 0.7% by mass of phosphorus with respect to the total mass of the catalyst in a fluidized bed reactor. To produce a monocyclic aromatic hydrocarbon.
When the obtained reaction product oil was analyzed by FID gas chromatography, the amount of impurities between durene (boiling point: 196 ° C.) and naphthalene (boiling point: 218 ° C.) was 1.9% by mass with respect to naphthalene 100. It was. The amount of impurities between naphthalene and 2-methylnaphthalene (boiling point: 241 ° C.) is 0.6% by mass with respect to naphthalene 100, and 0.4% by mass with respect to methyl naphthalene 100. It was found that there were very few components having boiling points close to each other.
Subsequently, the obtained reaction product oil is subjected to a gas fraction, a fraction containing monocyclic aromatic hydrocarbons (benzene, toluene, xylene), a heavy fraction having 9 or more carbon atoms (heavy fraction) in a rectifying column. Fraction fraction 1).
The heavy fraction 1 was further distilled in a rectification column, and fractionated into a fraction mainly composed of naphthalene (boiling point 218 ° C.) and a fraction other than naphthalene (heavy fraction 2).
The yield of monocyclic aromatic hydrocarbons (benzene, toluene, crude xylene (xylene containing a small amount of ethylbenzene, etc.)) obtained by fractional distillation was 30% by mass, and the yield of naphthalene fraction was 7% by mass. . The naphthalene purity in the naphthalene fraction was 96% by mass.

(Example 2)
LCO (10 vol% distillation temperature 224.5 ° C, 90 vol% distillation temperature 349.5 ° C) shown in Table 1 as a raw material oil was reacted at 550 ° C, reaction pressure: 0.3 MPaG, and contact time 18 The monocyclic aromatic hydrocarbon is produced by contacting and reacting with catalyst A (MFI type zeolite carrying 0.4% by mass of gallium and 0.7% by mass of phosphorus) in a fixed bed reactor under the conditions of seconds. It was.
When the obtained reaction product oil was analyzed by FID gas chromatography, the amount of impurities between durene (boiling point: 196 ° C.) and naphthalene (boiling point: 218 ° C.) was 2.4% by mass with respect to naphthalene 100. It was. The amount of impurities between naphthalene and 2-methylnaphthalene (boiling point: 241 ° C.) is 1.6% by mass with respect to naphthalene 100, 0.9% by mass with respect to methyl naphthalene 100, and naphthalene. It was found that there were very few components having boiling points close to each other.
Next, the obtained reaction product oil is fractionated in a fractionation tower into a gas fraction, a fraction containing monocyclic aromatic hydrocarbons (benzene, toluene, crude xylene), and a heavy fraction having 9 or more carbon atoms. did.
The heavy fraction having 9 or more carbon atoms was further distilled in a rectifying column, and fractionated into a fraction mainly composed of naphthalene (boiling point 218 ° C.) and a fraction other than naphthalene.
The yield of monocyclic aromatic hydrocarbons (benzene, toluene, crude xylene) obtained by fractional distillation was 37% by mass, and the yield of naphthalene fraction was 9% by mass. The naphthalene purity in the naphthalene fraction was 95% by mass.

(Example 3)
A fraction other than naphthalene obtained in Example 1 (heavy fraction 2: polycyclic aromatic hydrocarbon content 95% by mass or more) was used with a commercially available nickel-molybdenum catalyst, reaction temperature 350 ° C., reaction pressure The hydrogenation reaction was performed under the condition of 5 MPaG. The obtained hydrogenation reaction product contains 69% by mass of a hydrocarbon compound having one aromatic ring and 28% by mass of a compound having two or more aromatic rings (polycyclic aromatic hydrocarbon). In comparison, the polycyclic aromatic hydrocarbon content was significantly reduced.
Next, a raw material oil obtained by recycling the hydrogenation reaction product in an amount of 0.4 mass times with respect to LCO to LCO shown in Table 1 was reacted at a reaction temperature of 550 ° C., a reaction pressure of 0.3 MPaG, and a contact time of 30 seconds. In the fluidized bed reactor, catalyst A (60% by mass of silica binder in MFI type zeolite carrying 0.4% by mass of gallium and 0.7% by mass of phosphorus with respect to the total mass of the catalyst) To produce a monocyclic aromatic hydrocarbon.
The yield of the obtained monocyclic aromatic hydrocarbon (benzene, toluene, crude xylene) was 36% by mass, and the monocyclic aromatic hydrocarbon was compared with Example 1 in which the hydrogenation reaction product was not recycled. The yield was improved.

From the results of Examples 1 to 3, monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms composed of benzene, toluene, and crude xylene can be obtained with high yield based on the method for producing aromatic hydrocarbons according to the present invention. At the same time, it was found that high-purity (90% by mass or more) naphthalene can also be produced.

According to the method for producing aromatic hydrocarbons of the present invention, not only monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms but also naphthalene are contained using oil containing polycyclic aromatic hydrocarbons such as LCO. Naphthalenes can be produced together.

Claims

A method for producing an aromatic hydrocarbon, comprising:
A feed oil having a 10% by volume distillation temperature of 140 ° C. or more and a 90% by volume distillation temperature of 380 ° C. or less is brought into contact with and reacted with a catalyst for producing monocyclic aromatic hydrocarbons containing crystalline aluminosilicate. A cracking and reforming reaction step for obtaining a product containing a monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms and a heavy fraction having 9 or more carbon atoms;
A separation step of separating a monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms and a heavy fraction having 9 or more carbon atoms from the product obtained in the cracking and reforming reaction step;
A purification and recovery step of purifying and recovering the monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms separated in the separation step;
A naphthalene recovery step of separating and recovering naphthalene containing at least naphthalene from the heavy fraction having 9 or more carbon atoms separated in the separation step.
The method for producing an aromatic hydrocarbon according to claim 1, wherein the naphthalene recovery step is a step of separating and recovering methylnaphthalene and / or dimethylnaphthalene and naphthalene.
A method for producing an aromatic hydrocarbon according to claim 1 or 2, further comprising:
A hydrogenation reaction step of hydrogenating a remaining fraction from which naphthalenes have been separated in the naphthalene recovery step to obtain a hydrogenation reaction product;
A recycling step of returning the hydrogenation reaction product to the cracking and reforming reaction step.
The method for producing an aromatic hydrocarbon according to any one of claims 1 to 3, wherein the means for separating and recovering naphthalene containing naphthalene in the naphthalene recovery step is a means using a distillation apparatus.
The method for producing an aromatic hydrocarbon according to any one of claims 1 to 4, wherein the crystalline aluminosilicate is mainly composed of medium pore zeolite and / or large pore zeolite.
The reaction temperature at the time of reacting the raw material oil and the monocyclic aromatic hydrocarbon production catalyst in the cracking and reforming reaction step is set to 400 ° C or more and 650 ° C or less. The manufacturing method of aromatic hydrocarbon of description.
7. The reaction pressure when the raw material oil and the monocyclic aromatic hydrocarbon production catalyst are reacted in the cracking and reforming reaction step is 0.1 MPaG or more and 1.5 MPaG or less. A method for producing an aromatic hydrocarbon according to Item.
The contact time in which the raw material oil and the monocyclic aromatic hydrocarbon production catalyst are contacted in the cracking and reforming reaction step is 1 second or more and 300 seconds or less. A method for producing aromatic hydrocarbons.