JPS6022932A - Catalytic composition - Google Patents

Abstract

PURPOSE:To obtain a catalytic compsn. which retards ability for accelerating hydrogenation reaction of benzene ring while maintaining excellent ability for isomerizing xylene by incorporating Pt, Ti, etc. and crystalline aluminosilicate as active components. CONSTITUTION:At least two kinds of metal selected from (a) Pt, and (b) at least one kind selected from Ti, Pb, Cr, Zn, Ga, Ge, Sr, Y, Zr, Mo, Pd, Sn, Ba, Ce, and W, etc., and crystalline aluminosilicate having at least 10 molar ratio of silica/alumina and selected from zeolite ZSM-5, 11, 12, 35, and 38, are incorporated in a catalyst compsn. as active components. As the result, zeolite catalyst contg. Pt having superior isomerizing ability and selective deethylating ability for xylene as well as retarding remarkably ability for accelerating hydrogenating reaction of benzene nucleus, disproportion reaction of xylene, and transalkylation reaction between xylene and ethyl benzene, is obtd.

Description

[Detailed description of the invention]

The present invention is directed to an aromatic hydrocarbon feedstock containing mainly a mixture of xylene isomers which has not reached a thermodynamic equilibrium composition, in particular containing bibenzene, and in which p-xylene is below the thermodynamic equilibrium composition of the mixture of xylene isomers. A method of hydrogenating a xylene isomer mixture present at a concentration of This invention relates to a platinum-containing zeolite catalyst that suppresses side reactions. Industrially, the isomerization of xylenes is an isomerization reaction process of an aromatic hydrocarbon raw material mainly containing a mixture of xylene isomers, and a specific xylene isomer, usually a p- The xylene isolation step and the recycling step of the remaining 91 composition mixture after separation are carried out in an appropriate combination. At that time, the xylene isomer mixture composition in the isomerization reaction product should be as close as possible to the thermodynamic equilibrium composition; decomposition of xylenes (especially hydrogenation of benzene rings);
Suppression of side reactions such as disproportionation reaction increases the efficiency of the isomerization reaction and reduces costs, which has a great impact on industrial value. Many methods for isomerizing xylenes have been proposed in the past, and most of these methods use catalysts containing crystalline aluminosilicate heptaolides. Many proposals have been made regarding the cuff z, which is an important research device. In particular, methods for changing the shape or structure of the zeolite catalyst itself; methods for modifying the zeolite catalyst by subjecting it to physical treatment, such as heat treatment; methods for chemically modifying the zeolite catalyst by adding various components to it; Many studies have been conducted. For example, a method of treating Y-type zeolite with heated steam to improve the activity and stabilization of the catalyst (U.S. Pat. No. 3,887)
630), offretite (offrelite)
), etc., to improve the decomposition activity of ethylbenzene by supporting it (see US t¥fIIf No. 3,848,009). However, among the kiln isomerization catalysts proposed so far, (at 1,000 silene isomerization reaction VC%t) has excellent activity and (b) undesirable side reactions (e.g. nuclear hydrogenation of benzene ring, etc.). Hydrogenolysis, demethylation, especially disproportionation, transalkylation reactions, etc.) are contradictory as catalysts (at, (bl 2
It is almost impossible to find anything that fully satisfies both conditions at the same time. In particular, when isomerizing a mixture of xylene isomers containing ethylbenzene, xylenes') 14 t'f
It is desirable to de-ethylate ethylbenzene in addition to the de-ethylation reaction, and several methods have been proposed for this purpose. For example, the above-mentioned method is described in U.S. Pat. However, in the conventionally proposed method, in addition to the main reactions of xylene isomerization and ethylbenzene deethylation, hydrogenation of the benzene ring is also performed. Xylene cl) Disproportionation + Undesirable side reactions such as transalkylation of xylenes and ethylbenzene occur, and losses of xylenes are inevitable. For example, the three US patents described above disclose a method for isomerizing a dry silene isomer mixture containing ethylbenzene using a 28M series heptaolide modified with a platinum group metal such as nickel or platinum (・However, in the case of a ZSM-It zeolite catalyst modified with nickel (Ni content of 2 weight 1 or more),
Under so-called severe reaction conditions where the conversion rate of ethylbenzene is high, the demethylation reaction of xylene is promoted and xylene loss increases. Therefore, from an industrial perspective, it has been considered advantageous to use ZSM-type zeolite catalysts modified with platinum group metals that undergo less demethylation reactions. However, ZS and M-type zeolites modified with platinum, for example, have excellent isomerization properties of xylenes and the ability to selectively de-ethylate the ethyl group of ethylbenzene. On the other hand, platinum itself has a high urinary temperature activity of the benzene ring, and its hydrogenation reaction occurs more significantly as the temperature decreases from thermodynamic equilibrium, resulting in an increase in the formation of naphthenes. As a result, xylene loss increases, so ZSM-type zeolite catalysts modified with platinum are industrially less than 800% (
It was necessary to use it at high temperatures (427℃) or higher. Furthermore, the temperature required for the isomerization reaction depends on the space velocity, but generally a temperature of about 300 to 320" G is sufficient; higher temperatures do not improve isomerization, but rather cause disproportionation and trans-algyl K promotes undesirable reactions such as oxidation and increases xylene loss. A method has also been proposed in which deethylation is promoted while suppressing xylene loss due to disproportionation, etc. (US Pat. No. 4,152,363).
(see issue). However, with this method, it is difficult to maintain the isomerization rate at a high level, and due to the high temperature and high space velocity, the activity of the catalyst is severely degraded.

[1] It has a major industrial drawback: Therefore, the main object of the present invention is to provide platinum-containing 28
While maintaining the excellent xylene isomerization and selective deethylation abilities of the M-based zeolite catalyst, there are drawbacks to this catalyst, such as hydrogenation of habenzene rings, disproportionation of xylene and ethylbenzene. It is an object of the present invention to provide an improved platinum-containing zeolite-based catalyst whose ability to promote the transalkylation reaction of According to the invention, (I) (at platinum) and (b) titanium, zinc, gallium, germanium, strontium, yttrium, zirconium, molybdenum, palladium, tin, barium, cerium, tungsten. , osmium, lead, cadmium, mercury, indium, lanthanum, and beryllium.
M-5, heptaolide ZSM-11, zeolite) ZSM-
12, ze: J-ra () ZSM-35 and heptaolide Z
Nrika/Flumib 0 selected from the group consisting of SM-35
Catalyst compositions are provided that contain as active component a crystalline aluminosilicate in a molar ratio of at least 10. The crystalline aluminosilicate (hereinafter sometimes referred to as zeolite), which is the base of the catalyst of the present invention, has a cation site concentration [hydrogen ions are rich in hydrogen ion precursors such as ammonium ions/ fruit,
and the silica/alumina molar ratio is in the range of 20=200, preferably in the range of 30 to 150, -m preferably 40 to 1
In other words, in the present invention, a silica-containing zeolite with a relatively high content of silica compared to alumina is used as a catalyst base. Many zeolites with a relatively high silica content have been proposed in the past, and high silica-containing zeolites with a silica/alumina molar ratio as high as 2000 are also known. Among zeolites, zeolite has a relatively low silica/alumina ratio, and is therefore characterized by the use of a zeolite with a relatively high silicic acid activity derived from the alumina component.However, in the case of conventional high-silica-containing zeolite catalysts, In order to weaken the acid activity, promote the hydrogenation-fulkylation of furkylbenzenes, especially monofurkylbenzenes, and suppress side reactions such as disproportionation and/or transalkylation, the use of amines, etc. Using a basic substance or treating the zeolite with methyl-4 to destroy some of its acid sites, and shortening the contact time (for example, treating it at a high temperature (e.g., 426.7°C or higher)) Measures such as
However, in the catalyst composition of the present invention, zeolite having a relatively high activity can be used as it is without such treatment. Representative examples of crystalline aluminosilicates as catalyst bases that can be used in the present invention include Mobil Oil Corp.
ZSM-5 <U.S. Patent No. 3702886
No. 3709), ZS-M-11 (U.S. Pat. No. 3709)
No. 979 Specification #), ZSM-12 (U.S. Pat. No. 38
No. 32449 Mei I\llll 4F bath Teru), ZSM-35 (
US Patent No. 4,016,245 F! (see A specification) or ZS
M-3g (see US Pat. No. 4,046,859). These zeolites are generally produced in a form containing an alkali metal in the cation site. In the present invention, by ion-exchanging such zeolite by a conventional method, so-called H
For convenience, it should be understood that in Unknown III, zeolite 1 refers to H-type zeolite unless otherwise specified. In the present invention, it has been found that the most excellent effect is achieved when ZSM-5 type zeolite is used as the catalyst base among the above-mentioned zeolites. According to a preferred embodiment of the present invention, ZSM-5 is used as the base of the catalyst.
Catalyst compositions using m-zeolites are provided. In the catalyst composition of the present invention, the above-mentioned silica/
A heptaolide having an alumina molar ratio, (a) platinum (hereinafter sometimes referred to as the six metals (a)); (b) titanium, chromium, Etf' lead, potassium, )
f Lou? nium, stantium, yttrium,'
) luconium, molysdene, palladium, tin. ""U A, SE1J L: 7mu, tungsten,
Osmium, lead, cadmium, mercury, indium. At least one metal selected from the group consisting of lanthanum and beryllium. According to the research conducted by the present inventors, the theophyte catalyst modified only with the above-mentioned metal (i.e., only with platinum) has the ability to isomerize xylenes as described above, but at the same time, the benzene ring It also has a catalytic effect on reactions such as hydrogenation of xylenes and demethylation of xylenes.
・During the isomerization of xylenes, it causes an undesirable side reaction and results in the loss of xylenes.
When iiJ is added to zeolite (-7), Kanahashi (a
) while maintaining the high xylene isomerization U pi when containing only I'l! It was unexpectedly discovered that vc' can effectively suppress It-mediated effects. In addition, in the present invention, the other metal component used for modifying the zeolite (metal) is, among the above-mentioned, particularly soot. It has a large reaction suppression ability and is suitable. Here, "modified with metal (al and (bl)" refers to a state in which metal (a) and (bl) are ion-exchanged to the cation site of zeolite and/or metal (al and (A with bl maintained physically attached on the zeolite surface)
- 1 gold in either or both situations! %(al and (bl
It means containing. Zeolites modified with metals (al and bl) can thus be prepared by generally known methods for modifying zeolites with metals.
The modification with K may be carried out first or at the same time, but the preferred preparation method is gold! 4 (After some denaturation by at, metal (bl
This method performs denaturation by To facilitate understanding, typical methods will be explained in more detail. Industrially useful zeolites generally have their cation sites substituted with ions of alkali metals or alkaline earth metals such as Na, Ca, etc. is exchanged with hydrogen or gamma 7-ium ion. This exchange may be carried out simultaneously with or prior to the modification with the metal (Al).Thus, in one method, if the cation side is an alkali metal or alkaline earth metal ion. One method is to immerse zeolite substituted with metal (at ion) and ammonium ion in an aqueous solution containing cation sites. The metal (ammonium ion type zeolite modified with al) thus obtained is 11 then about 20
By calcining at a temperature of 0 to 600°C, it can be converted to hydrogen ion type zeolite modified with metal (a). The other method is to treat zeolite (K) whose cation sites are substituted with alkali metal or alkaline earth metal ions with an inorganic or organic acid such as hydrochloric acid, sulfuric acid, acetic acid, or oxalic acid to remove most of the cation sites. This is a method in which metal (a) is ion-exchanged or supported using a hydrogen ion carrier. Still another method is to treat zeolite whose cation sites have been replaced with alkali metal or alkaline earth metal ions with an aqueous solution of a water-soluble ammonium compound, and to prepare a zeolite whose cation sites have been mostly replaced with ammonium ions. This is a method in which gold zeolite (Al) is ionic-exchanged or supported, either as it is or after being calcined in advance at a temperature of about 250 to 650°C to form H-type zeolite. In this case, the ammonium ion replacement treatment involves converting the zeolite into water-soluble ammonium compounds such as ammonium chloride and ammonium nitrate.
It is easily carried out by contacting with a 20% by weight solution. Ion exchange of zeolite from metal (al V- and/
Compatibility can be carried out using known methods such as ion exchange or supporting methods of metal (aluminum) with respect to the usual heptaolide. For example, when various zeolites to be treated are desired, The contact treatment may be carried out with a water-soluble or water-insoluble medium containing a dissolved compound of metal (a). Compounds of such metal (at) include halides, oxides, sulfides, oxyacids, and complexes. For example, water-soluble platinum compounds such as H, PtC1, P
Platinum may be supported on zeolite by impregnating heptaolide with an aqueous solution of
Platinum may be ion-exchanged by immersing the zeolite in an aqueous solution of a platinum compound having ion-exchange ability such as (NH,)4C4) and thoroughly washing the zeolite by passing through f. In addition, the above-mentioned modification treatment with the metal (a) is carried out in Step 5 and 1 by pre-heating zeolite at a temperature of 100 to 700°C, preferably 200 to 600°C, in an oxygen atmosphere such as air, or under an oxygen atmosphere such as nitrogen. Heat treatment under an inert gas atmosphere for 1 to 50 hours is also possible and can yield superior catalysts, which is generally preferred. Zeolite modified with metal (a) in this way is
Heat treatment can be, and is preferred, at a temperature of 100 to 700°C, preferably 200 to 600°C, in an oxygen-containing atmosphere such as air, or in an inert gas atmosphere F, such as nitrogen, for about 1 to about 5 hours. The zeolite modified with metal(al) prepared as described above is then modified with metal(bl). Therefore, modification with metal (bl) is not particularly different from the commonly known method for preparing modified zeolaft with metal (makikin). Although various metal compounds mentioned above are exemplified, these are merely examples, and it goes without saying that even compounds not exemplified can be used as long as they are water-soluble or bath medium-soluble compounds. +1) Titanium compounds 1,000 fluorides, chlorides, bromides, iodides, sulfates and nitrates v18i,'/ammonium hexafluorotitanate 9 Ammonium pentafluoroperoxothionate. Ammonium hexachloro1000anate. Diethylammonium Hexachlorothionate, diethylammonium hexaphamo titanate, bis(acetonitrile)tetrafucrotitanium (2) Chromium compound CrC11,, CrSO4, Cr(CH,Coo)IH
,0,CrC1q. Cr<No, ), -9Hρ, Cr(SO4), ,
Cr(Nj(,nXs(hexamine compound, M,Cr,07,(NHn)tc'zc)y(3
) Germanium compound GeCe4. GeC1, GeR4 (R=alkyl)
(4) Molybdenum compound H? M1104, (NH4)aMoaot49MoC
Aa (5) Palladium compound PdCrl,, PdSO4.2H,0,Pd(NO,
hmm,. ['P d (Nl(l)4)C12(6) Tin compound 8nC11,5nC4, Hp(SnCJ6), 5n
R4 (R=alkyl), (NHn)t(SnCJa)
, (CtHs)4N(SnC4)()) Barium compounds Barium fluoride, chloride, perchloride. Bromide, iodide, thousand sulfate, secondary sulfite, sulfate, 4
LA acid salts, phosphates, carbonates. Oxocyanate, metasiligate, acetate, hydroxide, acetate, Ariichi salt (8) Tungsten compound tungstic acid, (NH4), IW, 04・5H
70(9n Osmium compound 0s04 * O!1c14 α1 Lead compound Pb(CM,Coo)t, Pb(NO,)?,
Pb(J4゜PbR4(R=alkyl) Uυ Cadmium compound Cadmium chloride, perchlorate, bromide, iodide, sulfate, nitrate, noanate. Thiocyanate, carbonate,
Acetate. Hydroxide and 匪*V salt, tris(ethylenedi7mine) cadmium nitrate. Dikuoo (ethylenedi7mine) cadmium R4 indium compounds Indium fluoride, chloride, bromide. iodides,) 11 chlorates, nitrates and sulfates. Ammonium hexafluoroindium. Ammonium Aquabentac OC + Indicum 03 Other metal compounds strontium, beryllium, gallium. Yttrium, zirconium, cerium. Zinc, lanthanum and mercury are used in the form of the following compounds. Fluorides, chlorides, bromides, iodides, perchlorides, cyanides, sulfates, nitrates. Nitrite, sulfite, acetate, acetate, formate, charcoal +1? ! Salts, phosphates, thiocinates, thiosulfates, hydroxides. Oxide 9 Various complexes The noble metal-modified zeolite obtained in this way can be prepared in the form of a fine powder or, as required, with K, K,
It can be formed into various desired shapes, such as pellets or tablets. When molding the modified zeolite, the modified zeolite is processed using a synthetic or natural chemical-resistant inorganic oxide, such as silica, alumina, etc., which is usually used as a binder for zeolite catalysts.
Silica-alumina, kaolin. After mixing with silica-magnesia or the like, it can be molded into a desired shape, and then fired to give a -1 temperature. The responsibility of the modified zeolite as a catalytically active component in such a molded product is generally 1 to 99 liters, based on the weight of the molded product.
ii&%, preferably from 10 to 90% by weight. The thus prepared catalyst consisting of zeolite modified with gold (PA body)
, preferably at a temperature of 250 to 550°C,
This reduction treatment is usually performed after filling the reactor. The content of each of the metals (at) and (bl) in the zeolite modified with the metals (at) and (bl) according to the present invention can be varied depending on the type of metal used, etc.; Based on the weight of the crystalline aluminum non-silicate, it is generally KO, 001 to 2, preferably 0.005 to 1.5% by weight, and preferably 0,01 to 1, σ5. , is advantageously contained in the crystalline aluminosilicate, and the metal (b) is generally 110.01 to 1/10, preferably in terms of the atomic ratio of a1/gold@(bl). is 110.05
It is convenient to use within the range of 115 to 115, more preferably 110.1 to 1/3. The catalyst according to the present invention prepared by K as described above contains the metal (at, usually in the form of a cation and/or oxide), and the metal (at) in the state before reduction of the target to be subjected to a reaction such as isomerization. b) is contained in an oxide or cation form depending on the type of metal, and when reduced during the isomerization reaction, gold j!
+ is converted into an elemental state, an oxide state, a cation state, or a mixture thereof. When the catalyst composition of the present invention is used in the isomerization reaction of quince, the aromatic hydrocarbon raw material mainly contains a mixture of xylene isomers that have not reached thermodynamic equilibrium. As is well known, xylene has three types of isomers: ortho-, meta-, and para-isomers, and when a mixture of these 3f1 isomers in any proportion is subjected to an isomerization reaction, the isomerization reaction It is known that an equilibrium state is reached when the proportion of the German isomer reaches a certain value, and isomerization apparently does not proceed any further. The composition of the xylene isomer mixture in this flat state is called the thermodynamic equilibrium composition J, and this thermodynamic equilibrium composition is slightly different from temperature 9. For example, the composition of the xylene isomer mixture at the temperature listed in The equilibrium composition is as follows: (1') In the case of a mixture of only three isomers of xylene [427°C]; p-xylene 23.47 [ikk Sorry m-xylene 52.1% by weight 0-xylene 24.5 Mk% (II) In the case of a xylene isomer mixture containing ethylbenzene [427°C]; Ethylbenzene 8.3 weight ratio p-xylene 21.5 weight, tqb m-xylene 47.8 weight% 0-xylene 22-4% by weight Therefore, in this example #111 m K, the "xylene isomer mixture that has not reached thermodynamic equilibrium composition" means that the concentration of at least 1811 isomers of the 3fjl isomers of xylene is A mixture of xylene isomers whose concentration deviates from the thermodynamic equilibrium composition. The aromatic hydrocarbon feedstock used as the starting material may consist solely of a xylene isomer mixture, or may consist of a xylene isomer mixture and other aromatic hydrogen ethylbenzene, benzene, toluene, ethyltoluene. , trimethylbenzene, diethylbenzene. A mixture with dicarboxylene, tetramethylbenzene, etc. may also be used. In the latter case, the xylene isomer mixture is
Based on the weight of the aromatic hydrocarbon raw materials, generally 3
It is desirable that the amount is 0, preferably 50 or more. Aromatic hydrocarbon feedstocks that can be used with particular advantage are C8 aromatic hydrocarbon fractions obtained from petroleum glue forming, pyrolysis, hydrocranking, which fractions, in addition to xylene isomer mixtures, are It also contains ethylbenzene with the same carbon X atom and number of molecules. In the present invention, among others, these xylene i-form compound and ethylbenzene are
Very advantageous results are obtained when using a C1 aromatic hydrocarbon fraction which in total accounts for at least 80% by weight, preferably more than 90% by weight, based on the weight of the fraction. The isomerization of the aromatic hydrocarbon raw material described above can be carried out under the per se known xylene isomerization reaction conditions 1., except for the use of the above-mentioned specific catalyst. Therefore, the reaction temperature is generally 250-450°C, preferably 270-400°C, particularly preferably 280-380°C.
and the hydrogen partial pressure is generally within the range of θ
~25 kg/adG, preferably O~20 kg/dG
, particularly preferably 0 to 1zkg/c++! You can freely choose within the range of G. The feed ratio of the aromatic hydrocarbon raw material can vary widely depending on the type of hydrocarbon raw material and/or catalyst used, but is generally about 1 to about 50, preferably 2 to 100, more preferably 3 to 5. It is preferable to supply it at a weight unit hourly space velocity within the range of . In this specification, [-weight unit hourly space velocity] is a value calculated by the following formula, where the weight of one catalyst iJ+I
It means the weight of crystalline aluminum/silicate that is the base of MMI. Also, defulkylation is carried out in the presence of hydrogen. At that time, the hydrogen supply ratio can vary widely depending on the hydrocarbon raw material and/or catalyst class 411 used, etc., but is generally 0.
．． Suitably, the proportion is within the range of 1 to 15, preferably 1 to 10. When the above-described catalyst composition of the present invention is used for the isomerization of hemorrhoids, it achieves a number of superior advantages over conventional similar techniques, as described below. 19 [It is extremely dog-like to contribute to the industry.] The advantages of the present invention are as follows. (1) Since the xylene demethylation reaction is suppressed, xylene loss is greatly reduced and the xylene isomerization yield is improved. (11) Since it becomes possible to operate under hydrogen pressure, the efficiency of xylene production equipment can be greatly increased. (till It becomes possible to suppress coke formation on the catalyst, and the equipment operating rate will be improved to a minimum. The present invention will be further explained below with reference to Examples. Example 1 (Al H-Z SM -5(j) Preparation U.S. Patent 39
Zeolite ZSM=5 was synthesized according to the method disclosed in No. 65207. During the synthesis, n-) rib abylamine and n-propylbromite were added as organic sources. The compound was identified as ZSM-5 from the X-ray diffraction pattern. The obtained ZSM-5 was filtered once and thoroughly washed with water, then dried for 8 hours at 200°C in an air dryer, then for 16 hours at 200°C, and further dried in an α-air Matsufuru furnace with sudden air flow at F450°C. ] Baked for 6 hours. Then 250g of ammonium chloride aqueous solution 1.54
Ion exchange was performed at 80°C for 24 hours. This operation was repeated two more times. After that, it was thoroughly washed with water and dried for 8 hours at 100°C in an air dryer, then dried at 200°C for 16 hours.
H+ type ZSM-5 was obtained by baking for 16 hours. The sodium content of this is c+, o5 weight t, s
The silica/aluminum molar ratio was 92. (b) Pt/28M-50) Preparation-1 CPt(NHs)4)C4o, 173 was dissolved in water at 90 eC, and H-form ZSM-53og obtained by the method of (al) above was added thereto. After immersing this at 50℃ for 8 hours while shaking occasionally, it was treated with δ-j and thoroughly washed with water at room temperature.Next, it was soaked in an air dryer IP100℃ for 8 hours, then at 200℃ for 16 hours. After drying and further calcining for 8 hours at 450° C. with air flow in an electric Matsufuru furnace, pt/ZSM-5 was obtained.The catalyst contained 0.24% platinum based on the total weight. (hereinafter referred to as catalyst A) fc) Preparation of Pt/28M-s-2 H-ZSM-s 2z, oiVc 35% 7 ammonia water 1
20ai! Total 120ai! While optically stirring with a glass rod, (Pt(NHs)4)C4o, +13y was added 2.
A solution of 5 thiammonia dissolved in 6 omes of aqueous solution was added dropwise using a pipette. After stirring for 5 hours at room temperature using a magnetic cooler, the electric conductivity of the f liquid was 15.
Washed with deionized water until μU/am. After drying at 100° C. and 200° C.K. for 4 hours each, it was fired in an electric Matsufuru furnace in an air atmosphere for 4 hours. The platinum-containing test was 0.28 heavy weight [Catalyst B]. Catalysts C to H were prepared using the same procedure, and their platinum contents were as shown in Table 1. (di various metal supported Pt-ZSM-5) ilJ table-
1-1 Weigh out the metal salts of each compound shown in 1-1 in a suitable solvent (deionized water unless specified in %) so that the metal atomic ratio is constant as shown in Table 1 based on the total amount of supported white. Pt-ZSM-s prepared by the above-mentioned method was added to the solution, and the mixture was evaporated to dryness to impregnate the metal salt. then 10
After drying at 0°C and 200°C, it was fired in an electric Matsufuru furnace at 450°C in an air atmosphere to obtain various metal-supported P.
t-ZSM-5 powder was prepared. As a specific example, an example of indium-supported Pt-ZSM-s is shown here:
To the solution dissolved in oml, add the solvent E3,9, 7
After heating for 4 hours with occasional shaking in a 0'''C thermostatic water bath, water was exchanged at 45°C in a hot water bath using an A-Clee Evaporator, then at 100°C and 200°C.
After drying in an electric dryer for 4 hours in an air atmosphere of 1.5 hours, the catalyst was calcined for 4 hours in an air atmosphere of 450 C. IL to obtain catalyst E-2. Table 1 Example 2 The powdered catalyst AIA-2VC obtained in Example 1 was mixed with alumina gel for chromatograph (3OO Metsuyu) at a weight ratio of 1
．． /1 was added, thoroughly mixed, and molded into a size of 10 to 20 meshes. The obtained molded product was fired in an electric Matsufuru furnace at 1.450° C. in an air atmosphere for 8 hours, and then filled into a pressurized fixed bed reactor. Thereafter, reduction treatment was performed at 400° C. for 2 hours in a hydrogen stream, and subsequently, xylene isomerization reaction was performed using mixed xylene having the composition shown in Table 2. The reaction conditions were: reaction temperature: 350°C, Ti unit hourly space velocity (WH8V): s, ollr-” (based on zeolite weight), hydrogen/aromatic hydrocarbon (molar ratio): 3/1.
．． Pressure is 120 psia and 5 feet after starting
The tact composition at 0 hours was as shown in Table 2. From these results, a second metal species (b) was added to Pt/ZSM-s.
When tin is added as PX, which shows the strength of isomerization activity
The equilibrium concentration of platinum is not lowered at all, and the deethylation rate, which is unique to platinum, is maintained at a high level. As a result of greatly suppressing the chemical activity, the industrially important xylene loss rate is significantly improved. NA: NON AROMATIC8 Mainly paraffins and naphthenes Deethylation rate (@= × 100 Demethylation roughness = Phase due to moles of toluene and C, naphthene generated - Sole number of C9 aromatics generated The abbreviations are respectively (PX) F: Concentration of balakin 1-' in the 3-isomer of chircin in the feed liquid (weight J1%) (PXJP nib a
Variant xylene concentration (weight) in xylene 3 isomer in tact liquid (PXJE: Variant xylene equilibrium concentration (weight %) of xylene isomer L41 at reaction temperature (EB), : Fee Fl HJ 3m degree (Car 11
%) (EB), EB concentration in nib a tact liquid (weight ratio) (X) F: Concentration of xylene 344 isomer in feed liquid (**%) (X),: Xylene 3 isomer in product liquid concentration,(
Example 3 Powdered catalysts H-5, D-4, E, E obtained in Example 1
-2, F-+ was molded, calcined, and reduced in exactly the same manner as catalysts A and A-2 described in Example 2, and the xylene isomerization reaction was carried out using the same reaction apparatus and raw material 1 reaction conditions. . The reaction characteristic values at 70 o'clock after the foot start were as shown in Table 31C. Note that the definition of the reaction characteristic value is the same as in Example 2. As in Example 2, B a * I n + T i
It is clear that the addition of cd'lf (1) does not suppress the isomerization activity and the deethylation activity of pt (2) suppresses the hydrogenation activity of benzene rings and the demethylation activity of xylenes. Table 3 Example 4 In this example, the same catalysts A, A-2, B-5, D-4°E, E-2 and F-4 as described in Example 2 and Example 3 were used.
For IK, a pen-sen hydrogenation reaction was carried out using an atmospheric fixed bed flow reactor. The reaction conditions are reaction temperature: 200
'C, Weight unit time space velocity (WH8V): s
, o (zeolite heavy duty standard), hydrogen/pensene-1/
1 (molar ratio). The pressure is normal pressure and ft is 99.98 wt% benzene. Table 4 shows the Hensen conversion force starting at 2:00 after the feed started. In addition, Figure-1 shows the amount of liquid non-aromatics (more than 99 wt% of C6+ naphthenes) produced by hydrogenation of benzene under the reaction conditions of atmospheric pressure 1 and Examples-2 and -
3. Pressure 1: Hydrogenation products of xylenes (Cn
(naphthenes), and an IE correlation is observed between the two. That is, the metal that suppresses the formation of naphthenes during the xylene isomerization reaction under pressure (BL suppresses the hydrogenation of pentene under normal pressure conditions. Table 4 Example 5 Example) Among the catalysts, the catalyst described in ff-5 was molded and calcined in the same manner as described in Example 2, using an atmospheric fixed bed flow reactor, and using the same benzene under the reaction conditions F described in Example 4. The results are shown in $-5.As is clear from Table-5, the hydrogenation activity of the benzene ring was improved by the addition of the metals listed in Table-5 (bl), and from the relationship shown in Figure-1, the xylene isomerization reaction It is clear that 06+ naphthenes in the product are reduced and xylene loss is suppressed. Table 5 Example 6 A xylene isomerization reaction was carried out under normal pressure using the catalyst used in Example 5. Calcination of the catalyst and The reduction treatment was as described in Example 5.The reaction conditions were as follows: Catalysts B and B-1 were used as reaction source W 3so
'C, WH3V6, except for catalysts B and B-1, the reaction temperature is 350'' (:,, WH8Vs, and the following reaction conditions are the same for all the catalysts listed in Table 5. That is, the pressure is The hydrogen/hydrocarbon molar ratio was 1/1, and the feedstock was the same as in Example 2.The reaction characteristic values at 20:00 after the start of feeding are as shown in Table 6, and the definition of the characteristic values. is the same as that described in Example 2. As is clear from Table 6, the platinum-ZSM-5 catalyst
When the metal described in 6 (BL) is added, (1) the xylene isomerization property is almost maintained. (2) the gB deethylation activity unique to platinum is not impaired. (3) platinum's individual coconut It is clear that the demethylation activity of metals (BL) as described in Table 6 (Table 5 and Voice 1) is suppressed. By adding tl'a,
/V7 isomerization reaction L61c was used as a catalyst for xylene (the loss rate was improved to +jJ). -+. 1 (-2 for chromatography)
00 mesh) in a weight ratio of ]/1 JIJ, thoroughly mixed, and molded into 9-length molds with a size of 10 to 20 mesh σ). Each of the molded products obtained is +1 in ZL! '＋
After baking at 11℃ for 8 hours,
Ll. 'CIf, reduction treatment was performed for 2 hours. After 12 days, a benzene hydrogenation reaction was carried out using the same method and conditions as described in Example 5. Pensen envelopment rate at 2 o'clock opening after feed start +t'! Shown in Autumn-7-+1
11th c-;h. Furthermore, continued (・teJ MeiM[i(ri1
A. Shiren 54 using the same method and Shiba case lζ described in 6.
Perform sexualization reaction

[7. 51t41i4 after starting feet
First reaction lr! As shown in Table 8, there were 17 shifts for the first shift. Note that the definition of the reaction 11' property value is the same as that described in Example 2. From the table it is clear that power is 011 < , Sn/
Does benzene hydrogen occur if the Pt atomic ratio is too small? archaic σ)
It can be seen that the inhibitory effect is insufficient, and conversely, when the amount of water exceeds 1q, the tetrasexualization activity and the amount of chlorbenzene decomposition are also increased. Table 7 Table 8 Example 8 Catalysts i, J, K, and L listed in Table 1 prepared by the method of Example 1 (bl) by changing only the platinum concentration were molded and calcined in the same manner as described in Example 2. After that, the hydrogenation mass of benzene was measured under the same conditions as described above. Table 9 shows the results of the isomerization reaction of xylenes at normal pressure F using the same reaction conditions and feed materials as in Example 6. If the subactivation of benzene ring water occurs, the platinum concentration reaches 0.3%, and only the demethylation activity increases with the addition of platinum (1 degree). Table 9 Example 9 The catalyst described in Example 8 was packed into a pressurized fixed bed flow reactor at a reaction temperature of 380°C and a hydrogen/'hydrocarbon molar ratio of 3/1.
All 1. The isomerization reaction of xylenes was carried out using the feedstock 9 (feed material) described in Example 2 by changing the WH8V at 4 kg/iG, and after the start of the reaction,
0. From Table 10, wHsv is thick (if the loss is ``4''
Although S decreases, the equilibrium attainment rate of PX, which is most important for the xylenes conversion, decreases. Table 10

Claims (1)

[Claims] (T) (al platinum and (bl titanium, rim, zinc,
Gallium, germanium, strontium, yttrium, zirconium, molybdenum, palladium, tin, barium, cerium, tungsten, osmium, lead, cadmium, mercury. At least two metals selected from the group consisting of indium, lanthanum, and beryllium, and (II) Zeolite ZSM-5, Part 5 A) Z
SM-1l, Zeolite ZSM-12, Zeolite Z
A catalyst composition containing as an active ingredient a crystalline aluminosilica selected from the group consisting of SM-35 and zeolite zSM-38 and having a silica/alumina molar ratio of at least IO.