JPH0352993A - Production of hydrocarbon rich in btx - Google Patents

Abstract

PURPOSE:To obtain hydrocarbon rich in BTX in high yield with relatively low reaction pressure by adding light hydrocarbon to hydrocarbon containing (polycyclic) aromatic hydrocarbon and reacting in the presence of zeolite- containing catalyst. CONSTITUTION:(B) 1-50wt.% (preferably 1-30wt.%) in total hydrocarbon of 2-8C light hydrocarbon is added to (A) >=9C hydrocarbon containing (i) >=40wt.% aromatic hydrocarbon and (ii) >=3wt.% polycyclic aromatic hydrocarbon and reacted in the presence of catalyst containing zeolite having >=1 CI-value, preferably containing at least one metal element selected from Cu, Ag, Zn, Cd, Ga, Cr, W, Se, Te, Re, Co, Ni, Pd, Ir and Pt to afford the aimed hydrocarbon.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a method for producing BTX-rich hydrocarbons, and more specifically, BTX-rich hydrocarbons containing aromatic hydrocarbons such as polycyclic aromatic components having a carbon number of 9 or more. This article relates to a method for efficiently producing BTX, that is, a hydrocarbon rich in benzene, toluene, and silane, which is useful as a base material for high-octane gasoline and a petrochemical raw material, from hydrocarbons. [Prior Art] In recent years, hydrocarbons containing aromatics such as polycyclic aromatics and having a carbon number of 9 or more, or heavy aromatic-containing hydrocarbons (for example, FCC (fluid catalytic) LCO (light cycle oil), HCO (heavy cycle oil), CLO (talarified oil), coal liquefied oil, oil produced by heavy oil pyrolysis process, oil produced by heavy oil hydrolysis, etc.) Therefore, there is a need for efficient conversion technology to convert BTX-containing hydrocarbons into higher value-added BTX-containing hydrocarbons. However, in the conventional FCC method using, for example, a Y-type zeolite catalyst, conversion of BTX from polycyclic aromatic-containing LCO and the like hardly occurs. Therefore, with the intention of producing high octane gasoline containing BTX from LCO etc., for example,
In the first stage reaction (R.), hydrogenation is carried out using a Ni-Mo catalyst at a hydrogen pressure of 42 kg/cj, and in the second stage reaction (R.'), a Pd-containing Y-type zeolite catalyst is used. A method of carrying out a decomposition reaction using
687), ■N i -W/SiO. - Al
A method of reacting using a TOS catalyst at a hydrogen pressure of 28 to 140 kg/cj (British Patent Specification No. 1,287)
, No. 722) have been proposed. However, method (2) has problems such as the two-stage reaction (R.) method, which is a complicated process, and the addition of high-pressure hydrogen is essential, consuming a large amount of expensive hydrogen. , although the above method (■) is a one-stage reaction method,
It still requires the addition of a large amount of hydrogen and considerable pressurization,
There are problems such as disadvantages in terms of process costs. By the way, the conversion reaction of heavy aromatic-containing hydrocarbons as described above, especially hydrocarbons having 9 or more carbon atoms containing aromatic hydrocarbons such as polycyclic aromatic hydrocarbons, to BTX is an exothermic reaction. Another important issue is how to alleviate the heat of reaction (exothermic heat). On the other hand, using light hydrocarbons with a carbon number of 2 to 8 and relatively heavy hydrocarbons, which have relatively low utility value, as reaction raw materials, BT
As a conventional technique for producing X-containing hydrocarbons, for example, (1) a method using a hydrocarbon having 5 or more carbon atoms containing 15% by weight or less of aromatics as a reaction raw material (Japanese Patent Publication No. 56
-42639 Publication), ■ A method aiming at increasing the octane number of naphtha and lowering the pour point of gas oil by using a mixture of naphtha and gas oil as reaction raw materials (US Patent No. 3,893,906)
No. specification) and (1) a method using a mixture of an olefin having 2 or more carbon atoms and light oil as a reaction raw material (Japanese Patent Application Laid-Open No. 57-14
No. 4791) is known. However, these techniques cannot be said to be a technology for converting heavy aromatic-containing hydrocarbons into BTX-containing high-octane gasoline fractions, and in fact, in the method Furthermore, there are problems such as the large reaction heat (in this case, endothermic heat) and the fact that it is relatively difficult to maintain the reaction temperature. There is no mention of using a fraction with a high hydrogen content as a reaction raw material. In addition, in the method (2) above, general gas oil is used as a source of heavy hydrocarbons, and the aromatic hydrocarbons in the raw materials are mainly generated in connection with the conversion reaction of olefins, and their content is also 1.
It is small, about 5 to 30% by volume, and the heat of reaction (endothermic)
There are also problems, such as the fact that the reduction in In other words, the conventional technology has various problems as described above, and it is difficult to efficiently process hydrocarbons having 9 or more carbon atoms containing aromatic hydrocarbons such as polycyclic aromatic hydrocarbons.< BTX-rich hydrocarbons There is no satisfactory method for converting the reaction to , and the technology to maintain a well-balanced reaction heat remains an unresolved problem. [Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances.

The object of the present invention is to solve the above problems and to
, FCC circulating oil such as HCO and CLO, coal liquefied oil, heavy oil pyrolysis process raw oil, and heavy oil hydrolysis product oil. The purpose of the present invention is to provide a method for efficiently producing BTX-rich hydrocarbons from hydrocarbons having 9 or more carbon atoms containing a certain amount of hydrocarbons in the group, while alleviating the heat of reaction (exothermic heat) and maintaining its balance. ．． [Means for Solving the Problems] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that carbon atoms containing aromatic hydrocarbons such as polycyclic aromatic hydrocarbons in a specific amount or more When converting a hydrocarbon having a carbon number of 9 or more into a hydrocarbon rich in BTX, a light hydrocarbon having a carbon number of 2 to 8 is added to this in a proportion within a specific range,
It was discovered that a method of bringing this into contact with a catalyst containing a specific zeolite with a CI value of 1 or more and causing a reaction is an excellent method that satisfies the above object, and based on this knowledge, the present invention has been completed. I ended up doing it.

That is, the present invention provides for adding light hydrocarbons having 2 to 8 carbon atoms to hydrocarbons having 9 or more carbon atoms containing 40% by weight or more of aromatic hydrocarbons and 3% or more by weight of polycyclic aromatic hydrocarbons. Production of BTX-rich hydrocarbons, characterized in that the reaction is carried out in the presence of a catalyst containing zeolite, which is added in a proportion of 1 to 50% by weight of the total hydrocarbons and whose CI{l[ is 1 or more. The present invention provides a method.

In the present invention, the hydrocarbons having 9 or more carbon atoms used as reaction raw materials include aromatic hydrocarbons having 9 or more carbon atoms (monocyclic aromatic hydrocarbons and polycyclic aromatic hydrocarbons having 2 or more rings). It is a hydrocarbon having 9 or more carbon atoms, which contains 40% by weight or more and 3% by weight or more of a polycyclic aromatic hydrocarbon having 2 or more rings. Specific examples of the monocyclic aromatic hydrocarbon having 9 or more carbon atoms include trimethylbenzene, tetramethylbenzene, pentamethylbenzene, hexamethylbenzene, ethylmethylbenzene, diethylbenzene,
Examples include benzene compounds having various hydrocarbon substituents, such as alkylbenzenes such as probylbenzene and butylbenzene, and alkenylbenzenes such as methylvinylbenzene, propenylbenzene and butenylbenzene. These may be contained singly or as a mixture of two or more. In the present invention, the polycyclic aromatic hydrocarbon having two or more rings is an aromatic hydrocarbon having two or more rings having at least one aromatic nucleus, and these may have no substituent. , or any one of them may be used. Examples of the polycyclic aromatic hydrocarbons include substituted naphthalenes, biphenyls, diphenylalkanes, and alkenes having one or more acyclic hydrocarbon groups as substituents such as naphthalene, alkyl, or alkenylnaphthalene. Aromatic system 2 having two phenyl groups or substituted phenyl groups
Benzenes or indenes having as a substituent a hydrocarbon group containing one non-aromatic cyclic hydrocarbon group such as a cyclic hydrocarbon, a cycloalkyl group, or a cycloalkenyl group;
Various two-ring aromatic hydrocarbons, such as two-ring aromatic hydrocarbons containing one benzene nucleus or substituted benzene nucleus and one non-aromatic hydrocarbon ring, such as dihydronaphthalenes and tetrahydronaphthalenes; Anthracene, substituted anthracenes having one or more acyclic hydrocarbon groups as a substituent, phenanthrene, substituted phenanthrenes having one or more acyclic hydrocarbon groups as a substituent, one or two benzene rings or various tricyclic aromatic hydrocarbons such as tricyclic aromatic hydrocarbons having a substituted benzene ring (including fluorene, substituted fluorene, etc.), or tricyclic aromatic hydrocarbons having one naphthalene ring or substituted naphthalene ring. Examples include aromatic hydrocarbons. Among these, polycyclic aromatic hydrocarbons having two or more rings which are usually suitably used in the method of the present invention include naphthalene, alkylnaphthalenes such as methylnaphthalene, dimethylnaphthalene, trimethylnaphthalene, and ethylnaphthalenes, anthracene and methyl Examples include alkyl anthracenes such as anthracene and dimethylanthracene, and alkyl phenanthrenes such as phenanthrene and methylphenanthrene.The polycyclic aromatic hydrocarbons having two or more rings may be contained alone. or two or more types may be contained as a mixture.

In the method of the present invention, the content of the aromatic hydrocarbon having 9 or more carbon atoms in the hydrocarbon having 9 or more carbon atoms used as the reaction raw material is less than 40% by weight, or the aromatic hydrocarbon having 2 or more rings is less than 40% by weight. If the content of ring aromatic hydrocarbons is less than 3% by weight, the reaction will proceed, but the reaction heat will be small, and the effect of adding light hydrocarbons having 2 to 8 carbon atoms (i.e., the effect of adding light hydrocarbons having 2 to 8 carbon atoms) The effect of improving the overall reaction heat balance due to the endothermic component of the reaction) becomes insufficient.
The exothermic reaction for converting the hydrocarbon having 9 or more carbon atoms to the BTX-rich hydrocarbon includes, for example,
Examples include dealkylation reactions of various substituted aromatic hydrocarbons and hydrogenolysis reactions including partial hydrogenation reactions of polycyclic aromatic hydrocarbons.

In the method of the present invention, there are various hydrocarbon oils that can be used as the hydrocarbon having 9 or more carbon atoms, but among them, those that can be normally preferably used include, for example, LCO ,HCO
, FCCWi ring oil such as CLO, coal liquefied oil, heavy oil pyrolysis process raw oil, heavy oil hydrolysis product oil, etc. Two types of these may be mixed as desired, or the ingredients and composition may be appropriately adjusted for use.

Note that the hydrocarbons having 9 or more carbon atoms contain heteroatom-containing hydrocarbons containing sulfur content, oxygen content, nitrogen content, etc., within a range that does not interfere with the purpose of the present invention. It's okay. In the method of the present invention, the carbon number 2 which is added to the carbon number 9 or more hydrocarbon and subjected to reaction.
Examples of light hydrocarbons of ~8 include ethane, propane, n-7'tane, isobutane, n-pentane, isopentane, n-hexane, isohexane, neohexane,
Straight chain or branched paraffinic hydrocarbons such as n-hebutane, isohebutane, n-octane, isooctane, ethylene, propylene, butene, isobutene, bentene,
Linear or branched olefinic hydrocarbons such as isoarξ-lene, hexene, isohexene, heptene, isoheptene, octene, isooctene, etc.; acetylene hydrocarbons such as acetylene, methylacetylene, butyne, pentyne, hexyne, heptyne, octyne; allene; , dienes such as butadiene, pentadiene, hexadiene, hebutadiene, and octadiene, or polyene-based hydrogen hydride, cyclic paraffinic hydrocarbons such as cyclopenkune, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, cyclohebutane, and cyclooctane,
Examples include cyclic olefin hydrocarbons such as cyclobentene, methylcyclobentene, cyclohexene, methylcyclohexene, ethylcyclohexene, vinylcyclohexene, cyclohebutene, and cyclooctene. Incidentally, these can be used alone or in combination of two or more in various proportions. Further, these may contain methane and other impurities, and may contain a small amount of monocyclic aromatic hydrocarbons such as BTX, within a range that does not impede the purpose of the present invention.

In the present invention, a mixture consisting of at least a hydrocarbon fraction having 9 or more carbon atoms of the specific composition and one or more of the above light hydrocarbons having 2 to 8 carbon atoms is used as a reaction raw material. supplied to a reaction system carried out in the presence of the catalyst,
The reaction produces BTX-rich hydrocarbons. The proportion of the light hydrocarbons having 2 to 8 carbon atoms used at this time is 1% by weight when the total hydrocarbons (sometimes abbreviated as HC) supplied to the reaction system are 100% by weight.
~50% by weight, preferably 1-301! ! t%
Set within the range. When this proportion is less than 1% by weight, as described above, the effect of reducing the calorific value of the exothermic reaction accompanying the conversion of the hydrocarbon having 9 or more carbon atoms of the specific composition, that is, the effect of maintaining heat balance, cannot be sufficiently obtained. Moreover, the generation of active hydrogen decreases, making it impossible to supply sufficient hydrogen for hydrogenolysis, making it impossible to achieve the object of the present invention. On the other hand, if the proportion exceeds 50% by weight, endothermic reactions become dominant, resulting in a large thermal imbalance during the reaction, making it impossible to achieve the purpose of the present invention. In addition, there is no particular restriction on the order or method of mixing the precepts in the above reaction. The various hydrocarbons and mixtures thereof are mixed appropriately to the predetermined ratio, or those that already have the composition as the mixed raw material are directly subjected to the reaction. In the method of the present invention, the reaction can be carried out in the presence of hydrogen (H2) or in its absence. Hydrogen (
The ratio of Hd), expressed as a molar ratio to the total hydrocarbons (HC) to be supplied, is preferably within the range of O≦(tit/HC)≦1. If this proportion exceeds 1% by weight, excessive hydrogenolysis tends to occur, lower paraffins are produced, and the yield of BTX may decrease. Further, the reaction can be carried out in the presence of other gas components such as inert gas such as nitrogen gas, argon, and helium, or steam, within a range that does not interfere with the purpose of the present invention.

In the method of the present invention, a reaction obtained by mixing one or more of the above-mentioned specific group of hydrocarbons having 9 or more carbon atoms and the above-mentioned light hydrocarbons having 2 to 8 carbon atoms in the above-mentioned specific ratio. The raw material or a mixed raw material containing hydrogen therein is treated with the catalyst (
That is, the catalyst is brought into contact with a catalyst containing zeolite having a CI value of 1 or more to produce a BTX-rich hydrocarbon.

By the way, CI value is an index indicating whether the pores of zeolite have the necessary characteristics to control the entry of molecules with a cross section larger than n-baraffin, that is, a control index, and the CI value that gives the definition of this CI value is The method for measuring the value follows that described in US Pat. No. 4,016,218. Specifically, when a mixture of equal weights of n-hexane and 3-methylbentane is passed over a zeolite at 90-510° C. and atmospheric pressure, there is no change in each of the two hydrocarbons. Measure what's left. In the method of the present invention, various known zeolites can be used as the zeolite having a CI value of 1 or more to be used as the catalyst or its component, and specific examples include ZSM-5. , ZSM-8, ZSM
ZSM-5 type zeolite such as -11, ZSM-23, Z
Examples include SM-35, clinoptilolite, and TMA offretite. Among these, ZSM
ZSM-5 type zeolites such as ZSM-5, ZSM-8, and ZSM-11 are preferred. In the method of the present invention, even if zeolite is used as a catalyst or its component, if a zeolite with a CI value of 1 or more is not used, the yield of BTX will decrease and the purpose of the present invention may not be achieved. Can not. The catalyst used in the method for producing BTX-rich hydrocarbons of the present invention contains at least one zeolite having the CI value of 1 or more, but this catalyst also contains a metal having hydrogenation-dehydrogenation ability. Those containing active ingredients are preferably used. As the metal element that becomes this metal component,
For example, Cu, Ag, Zn, CdSGa, Cr, W, S
Mention may be made of e, Te, Re, Co, Ni, Pd, Ir and PL. Note that these metal elements can be used alone or in combination of two or more. These metal components include, for example, metals, carbonates, sulfates,
It is added in various forms such as nitrates, oxides, sulfides, and chlorides. Preferably, it is used as an oxide or sulfide by processing such as burning. In determining the catalyst or its components used in the method of the present invention,
The various metal bottoms can be used in various combinations with the zeolite. These various metals are, for example, structural components of the zeolite (e.g., ion-exchangeable cations, substituent atoms in the framework, or these metals are used during catalyst preparation, pretreatment, reaction, regeneration, etc.). The zeolite may contain the zeolite as a solvent in various forms resulting from denaturation due to treatment such as time, or the zeolite containing one or more of the metal components, the zeolite not containing these, or a mixture thereof. It may be contained in the form of being supported on a carrier consisting of, for example, by an ion exchange method or an impregnation method, or it may be contained in the form of a physical mixture with those zeolites, and it may be contained in any form. In the method of the present invention, as the zeolite used as a component of the catalyst, galloaluminosilicate and its modified zeolite can be particularly preferably used among the various ones mentioned above. In the modified zeolite, the Ga state may be an ionic state, a lattice disubstituted atom state, an oxide state, or a mixed state thereof.

Galloaluminosilicate does not necessarily contain all the G
a is not in a 4-coordinated state incorporated into its lattice, but in a 6-coordinated state.
It is thought that there is a coordinating gallium oxide. In addition, by subjecting galloaluminosilicate to a modification treatment such as high temperature firing or steam treatment, Ga
can be dropped from the lattice to form 6-coordinated Ga,
Zeolites can be used to provide more favorable catalytic properties such as activity. The shape of the catalyst used in the method of the present invention is not particularly limited, and it can be molded into various shapes as desired. A binder may be used as appropriate during this precept. Any binder can be used as long as it does not interfere with the purpose of the present invention, and specific examples include alumina, silica, silica/alumina, and various clay minerals. be able to. Further, the catalyst may contain other additive components within a range that does not interfere with the purpose of the present invention. The method for preparing the catalyst used in the method of the present invention is not particularly limited, and can be prepared by applying various methods such as known methods. For example, compounds containing the various metal components described above may be used in the various zeolites to prepare them by an ion exchange method, an impregnation method, a physical mixing method, or the like. It is also possible to use a method of containing various metal compounds. Furthermore, the various metal components may be added before or after binding with the binder. After the binder is impregnated or kneaded with a metal component compound, this may be mixed with zeolite. Catalysts in various shapes prepared in this way can be used as catalysts in the method of the present invention as they are, but they are usually subjected to air calcination as appropriate, and further subjected to various activation treatments and modification treatments as desired. It is preferable to perform pre-treatment such as treatment before use. Examples of this modification treatment include the above-mentioned steam treatment, acid treatment, and other deal-aluminum treatments, and activation treatments include, for example, heat treatment in an inert gas or under vacuum exhaust, etc. dehydration treatment using hydrogen gas, or reduction treatment using reducing gases such as hydrogen gas. Through these activation treatments and modification treatments, the catalytic activity can be further improved, and the catalytic properties can also be adjusted as appropriate depending on the composition, properties, etc. of the reaction raw materials used. In the method of the present invention, the reaction can be carried out using various reaction methods and various reaction apparatuses suitable therefor, for example, it can be carried out using any of fixed bed, moving bed, fluidized bed, etc. It is usually preferable to use a fluidized bed. In particular, a system in which a device consisting of a fluidized bed reactor and a fluidized bed regenerator is used to perform both reaction and catalyst regeneration in a fluidized bed system and circulate the catalyst between the reactor and the catalyst regenerator, that is, a reaction-regeneration catalyst circulation fluidized bed. It is preferable to use the method. Fluidized beds allow sufficient mixing and stirring of catalyst particles, and a relatively uniform temperature distribution can be obtained even when the heat of reaction is large. In addition, the catalyst can be easily supplied and discharged and can be carried out continuously during the reaction, and the reaction-catalyst regeneration can be carried out in a short cycle. Therefore, even if the catalyst is severely degraded, the initially highly active regenerated catalyst can be used for the reaction at all times, and a highly active state can be maintained. In addition, when using the reaction-regenerated catalyst circulation fluidized bed method, by using the light hydrocarbon having 2 to 8 carbon atoms as the reaction raw material component in the predetermined ratio, the catalyst is improved compared to the case where it is not added. Since the amount of coke produced in the regenerator can be reduced, and the heat of combustion of this coke in the regenerator can be suppressed within an appropriate range, the temperature of the regenerator can be adjusted much more easily. In the method of the present invention, the reaction usually includes
It is appropriate to carry out the reaction temperature within the range of 350 to 700'C, the reaction pressure within the range of 0 to 10Scg/dG, and the space velocity (WHSV) within the range of 0.1 to 15hr-'. be. For example, if the reaction is carried out using a fixed bed method, the above reaction conditions can be used. When using a fluidized bed method, the reaction temperature (reactor temperature) is usually
The temperature is 350 to 700°C, preferably 450 to 600°C, the reaction pressure is usually 0 to 10 kg/dG, preferably 0 to 5 kg/cjG, and the space velocity (W
HSV) is in the range of 0.1-15 br-', while the temperature of the catalyst regenerator is usually in the range of 400 to soo'c, preferably 500 to 750 °C, and the catalyst regeneration pressure is usually in the range of O ~10kg/cjG, preferably 0-5kg
It is appropriate to set it within the range of /cjG. If the reaction temperature is too high, undesirable decomposition reactions will occur, resulting in a decrease in the yield of BTX and the deterioration or destruction of the catalyst. On the other hand, if the reaction temperature is too low, sufficient reaction rate may not be achieved. Sometimes I can't. In addition, if the catalyst regeneration temperature is too high, the catalyst may be easily destroyed, which may be disadvantageous in terms of energy costs and balance. On the other hand, if the catalyst regeneration temperature is too low, catalyst regeneration may be insufficient. .

In the manner described above, the hydrocarbon having 9 or more carbon atoms can be converted into BTX (benzene, toluene, xylene) with a high yield. In addition, the number of carbon atoms added is 2 to 8.
Light hydrocarbons can also be efficiently converted to BTX at the same time. The reaction product obtained in this way contains a large amount of BTX, but it usually contains BTX such as naphthalene.
Ring aromatic hydrocarbons, hydrogen and light hydrocarbons (carbon number l~
It also contains about 5 paraffins and olefins). The reaction product containing a high concentration of BTX obtained in this way is separated into gas components such as light hydrocarbons and hydrogen gas and heavy hydrocarbon fractions by conventional separation means such as gas-liquid separation and distillation. By appropriately separating and removing BTX, etc., it is possible to recover BTX-rich hydrocarbons (high octane gasoline fraction, etc.) in a desired fraction range. At this time, the aromatic hydrocarbons that escaped to the gas side due to gas-liquid separation etc. can be recovered, for example, by countercurrent contact treatment with heavy aromatic hydrocarbons. The liquid after gas-liquid separation is usually separated by distillation, but the bottom liquid of the distillation column (hydrocarbons heavier than the boiling point of gasoline) can be recycled to the reactor and used effectively if desired. In addition, if the catalyst that flows out of the reactor along with the reaction raw materials is deposited at the bottom of the gas-liquid separator or distillation column, it can be returned to the reactor together with the cycle oil as described above. Furthermore, hydrocarbon gases lighter than gasoline fractions (usually hydrocarbons having about 1 to 5 carbon atoms) and hydrogen gas can be recycled to the reactor as needed, and
It is also possible to further improve the conversion rate of aromatic hydrocarbons. The BTX-rich hydrocarbon obtained as described above can be efficiently produced. The BTX-rich hydrocarbon obtained as described above can be suitably used as a mixed liquid as it is, or by adjusting the composition as appropriate, for example, as a base material for high octane gasoline, or It is also possible to appropriately separate useful components such as monocyclic aromatic hydrocarbons such as benzene, toluene, and xylene, and use them as petrochemical raw materials and high-quality solvents. [Example] Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Preparation Example of Catalyst A solution consisting of 7.6 g of aluminum nitrate, 6.9 g of gallium nitrate, 26.4 g of tetrapyrammonium bromide, 15.0 g of acid (97%), and 250 ad of water was prepared as A.
Liquid, water glass (SIO128.4%, Na.0 9.5
%) 214g, water 212af! A solution consisting of 80 g of sodium chloride and 122 d of water was used as solution C, and they were mixed into solutions A and B @ solution C while being gradually added dropwise at the same time. The pH of this reaction mixture was adjusted to PH with sulfuric acid.
9. After adjusting the temperature to 5, the mixture was kept in a tX autoclave under autogenous pressure at 170°C for 20 hours with stirring at 300 rpm. After cooling, the solid was filtered, thoroughly washed with excess pure water, and dried at 120'C overnight to obtain a galloaluminosilicate zeolite having a ZSM-5 + JI structure. Next, this was heated in an air stream at 540°C for 3 hours at an IN NH. NO, water at 80℃ for 2 hours
After ion exchange, filtration, washing with water, drying at 120'C,
After incineration at 540''C in an air stream, ion exchange with IN NH.NO. water was performed again, filtered, washed with water, and dried at 120'C, followed by 3 hours at 720'C.
Fired in an air stream. The element strength of this galloaluminosilicate is S i Oz: A 12oz: G
a gos (molar ratio) = 80:I:0.7, and its CI value was 8.1. This galloaluminosilicate and alumina binder were mixed to obtain a binder content of 35%.
wt%, granulated with a spray dryer, and heated to 600°C.
It was burned for 3 hours and used as a catalyst. In addition, as a control, a granulated product containing 100% alumina binder was separately prepared. Example 1 and Comparative Example 1 Using the catalyst prepared in the above catalyst preparation example, a reaction was carried out under the following conditions using a fluidized bed catalyst circulation regeneration reactor with a reactor/regenerator each having a catalyst amount of 200 cc. did. In Comparative Example 1, the raw material oil was ■LCOIOOwt%,
Example! In this case, ■ LCO/DLN = 75/25wt% was used, and the total supply amount was kept constant at 100 g/h. The general properties of LCO and DLN used are shown in Tables 1 and 2.

The circulation amount of the catalyst is 0 when the feedstock oil is ■. It was set at 1 ks/hr. Regarding the reaction temperature, the regeneration tower temperature was set to 6
Assuming that the temperature was constant at 50°C, the reactor heater output was adjusted so that the temperature was 530°C when feedstock oil (①) was used. When using feedstock oil (■), the reaction temperature was set at 530°C by adjusting the catalyst circulation rate without changing the reactor heater output. The pressure of the entire system is 0.
7 kg/cj G.

In addition, the amount of powder circulation was measured in this fluidized bed reactor in a state where no heat of reaction was transferred. For this purpose, 100% alumina binder granulated product/raw oil ■ was used, the reactor heater output was made the same as the adjusted value above, and the circulation amount of the powder was adjusted so that the reaction temperature was 530"C. As a result, the circulation The amount was 0.45 kg/hr. The products obtained in the reactions of Comparative Example 1 and Example 1 (0.45 kg/hr)
5 hours later) was analyzed using a gas chromatograph.
The results are shown in Table 3. The circulation rate results in Table 3 show that Comparative Example 1 is an exothermic reaction. This reaction is based on dealkylation of aromatic hydrocarbons and partial hydrogenolysis of polycyclic aromatics. On the other hand, in Example 1 in which D L N was added, unlike Comparative Example 1, heat generation was sufficiently suppressed (rather close to endothermic heat generation), indicating that heat balance control can be easily performed by controlling the amount added. Table 2 Raw Materials DLNMi Formation DMB: Dimethylbutane MP: Methylpentane MCP: Methylcyclopentane [Effects of the Invention] According to the present invention, hydrocarbons having a carbon number of 9 or more in a specific group have a carbon number of 9 or more. Since 2 to 8 light hydrocarbons are added in proportions within a specific range and the reaction is carried out in the presence of a specific catalyst, the following effects can be achieved. (1) Use The excess heat generated by the conversion of the hydrocarbon fraction with 9 or more carbon atoms can be successfully offset by the heat absorbed by the reaction of light hydrocarbons with 2 to 8 carbon atoms, significantly improving the balance of reaction heat. (2) Since the hydrogen generated by the reaction involving dehydrogenation of light hydrocarbons having 2 to 8 carbon atoms can be effectively used, the amount of hydrogen to be supplied and its pressure can be significantly reduced. ( 3) BTX-rich hydrocarbons can be obtained in high yield in the one-stage reaction (R8) even at relatively low reaction pressure.As described above, according to the present invention, aromatic compounds such as polycyclic aromatic Raw material hydrocarbon components, including hydrocarbons with 9 or more carbon atoms containing a specific amount or more of group hydrocarbons, can be converted to BTX in high yield, and hydrocarbons rich in BTX can be efficiently produced. It is possible to provide a method for producing BTX-rich hydrocarbons that is extremely advantageous in practice.

Claims (1)

[Scope of Claims] 1. Hydrocarbons having 9 or more carbon atoms containing 40% by weight or more of aromatic hydrocarbons and 3% or more by weight of polycyclic aromatic hydrocarbons, and light hydrocarbons having 2 to 8 carbon atoms. is added in a proportion of 1 to 50% by weight of the total hydrocarbon, and the mixture is reacted in the presence of a catalyst containing zeolite having a CI value of 1 or more. Method. 2. The method for producing BTX-rich hydrocarbons according to claim 1, wherein the addition ratio of light hydrocarbons having 2 to 8 carbon atoms is 1 to 30% by weight of the total hydrocarbons. 3. The catalyst is Cu, Ag, Zn, Cd, Ga, Cr, W
, Se, Te, Re, Co, Ni, Pd, Ir and Pt
The method for producing a BTX-rich hydrocarbon according to claim 1 or 2, wherein the BTX-rich hydrocarbon contains one or more metal elements selected from the following. 4. The molar ratio (H_2/HC) of hydrogen (H_2) and total hydrocarbons (HC) supplied to the reaction system is 0 or more and 1
BT according to claim 1, 2 or 3, which is carried out within the following range:
A method for producing an X-rich hydrocarbon. 5. The method for producing BTX-rich hydrocarbons according to any one of claims 1 to 4, wherein the reaction is carried out using an apparatus consisting of a fluidized bed reactor and a fluidized bed regenerator. 6. Hydrocarbons with a hydrocarbon number of 9 or more are FCC (fluid catalytic cracking) circulating oil, coal liquefied oil,
The method for producing BTX-rich hydrocarbons according to any one of claims 1 to 5, wherein the BTX-rich hydrocarbon is a heavy oil pyrolysis process product oil or a heavy oil hydrolysis product oil.