KR100328677B1 - Catalyst for preparing xylene mixture from benzene toluene and C9 or more aromatic compounds and the preparation method thereof - Google Patents

Abstract

The present invention relates to a catalyst for preparing mixed xylene through disproportionation / transalkylation reaction from benzene, toluene and C9 or more aromatic compounds, and a method for preparing the same. Mordenite or beta (β) type zeolites having a molar ratio of 20 to 200, inorganic binders such as alumina, platinum (Pt) / tin (Sn), platinum / lead (Pb), and platinum It relates to a catalyst consisting of a metal selected from the group consisting of / indium (In) and a method for producing the same. As a result of the disproportionation / transalkylation of benzene, toluene and C9 or more aromatic compounds using the catalyst prepared according to the present invention, the catalyst of the present invention has a higher yield of mixed xylenes compared to the prior art, and the catalyst is deactivated. Speed also has a significant effect.

Description

Catalyst for preparing xylene mixture from benzene, toluene and C9 or more aromatic compounds and preparation method thereof benzene toluene and C9 or more aromatic compounds and the preparation method

The present invention relates to a catalyst for preparing mixed xylene through disproportionation / transalkylation reaction from benzene, toluene and C9 or more aromatic compounds, and a method for preparing the same. Inorganic binders such as mordenite or beta (β) type zeolites, alumina, and platinum (Pt) / tin (Sn), platinum / lead (Pb) and platinum / It relates to a catalyst consisting of one metal selected from the group consisting of indium (In) and a method for producing the same.

Mixed xylene is a very important raw material in the petrochemical industry and is a major source of xylenes such as m-xylene, para-xylene and or-xylene. It is used as a raw material to prepare the basic fractions of pure para-xylene, meta-xylene and ortho-xylene.

Each of the xylene isomers has a similar boiling point, so that it is very difficult to separate specific isomers from mixed xylene by the conventional distillation method, and to separate and produce specific isomers through adsorptive separation, crystallization, and isomerization reaction. This is commonly used. Commercial mixed xylene production methods include a method of separating from mixed xylene-rich oil and a method of synthesis by reaction. The former methods include distillation in the reformed oil produced by naphtha reforming and separation from pyrolysis oil produced as a by-product of naphtha pyrolysis. The latter method involves the disproportionation of toluene and toluene / Transalkylation of C9 aromatic compounds and alkylation of toluene with methanol.

The catalyst prepared according to the present invention is used for the disproportionation reaction of toluene and the transalkylation reaction of toluene / C9 aromatic compound in the commercial mixed xylene production method, and the raw material to be introduced into the catalyst is toluene alone or C9 or more aromatic. When the compound (C9 to C10 aromatic compound) alone can be treated, and can be treated regardless of the ratio of toluene and C9 or more aromatic compound mixed, and when benzene is included in addition to toluene and C9 or more aromatic compound It can also be processed.

Commercially used disproportionation / transalkylation catalysts generally use zeolites such as mordenite and ZSM-5 as base materials, and are used by molding such zeolites or by supporting specific metal components on zeolites. As a conventional disproportionation / transalkylation catalyst, examples of using zeolite as a base material are as follows.

U.S. Patent No. 4,083,886 describes a catalyst for the transalkylation reaction of an alkyl aromatic compound such as toluene, and describes a method for producing a catalyst in which mordenite treated with ammonia water is formed of an inorganic oxide binder. Unlike the present invention, the method does not use a metal having a hydrogenation function and performs a transalkylation reaction only with zeolite itself, so that the transalkylation reaction of toluene alone is not a problem. It is difficult to expect a high level of mixed xylene yield because the dealkylation reaction of the catalyst does not occur smoothly, and the deactivation rate of the catalyst also increases rapidly as the mixing specific gravity of the aromatic compound of C9 or higher increases.

U. S. Patent No. 5,030, 787 describes a transalkylation catalyst using a beta zeolite which attenuates acidity by steam treatment. The above method is expected to reduce side reaction generation and deactivation through acidic weakening, but the method of weakening acidic acid without introducing a metal hydride reduces the reaction activity to reduce the yield of mixed xylene and is not effective in preventing inactivation.

U. S. Patent No. 5,475, 180 also describes a process for preparing a catalyst in which nickel is supported on mordenite as a catalyst for disproportionation / transalkylation reaction of toluene and a high molecular weight aromatic compound. In the above method, the role of nickel is to facilitate the dealkylation reaction of the aromatic compound having a high molecular weight contained in the reactants as in the present invention and to suppress the deactivation of the catalyst, but the hydrogenation activity of nickel is significantly weaker than that of platinum. Therefore, the rate of deactivation during the reaction is expected to be much faster than the catalyst using platinum with well controlled activity. In addition, the problem of using nickel as a metal hydride is that when a sulfur compound in the reactant is introduced, it is strongly bound to nickel and can greatly reduce the activity of nickel. In general, raw materials introduced into a commercial disproportionation / transalkylation process are introduced after a process of removing sulfur compounds, but sulfur compounds may be introduced due to an accident of an operation, an operation operation error, or the like. In the case of platinum, when the sulfur compound inflows, the activity may temporarily be combined with platinum to decrease the activity, but when the sulfur compound is blocked, the activity is restored because the sulfur compound is desorbed and removed from the platinum again, but in the case of nickel Sulfurized compounds have the disadvantage of use which is impossible to remove during the reaction.

U.S. Patent No. 3,671,602 describes a catalyst for disproportionation / transalkylation reactions of toluene and C9 aromatics, wherein aluminum fluoride and aluminum fluoride, copper (Cu), silver (Ag), gold (Au) Or a method of preparing a catalyst supporting one metal from a metal group such as tungsten (W), molybdenum (Mo), chromium (Cr), arsenic (As), and the like. In the present invention, it is claimed that the deactivation of the catalyst is reduced by suppressing the production of coke through addition of aluminum fluoride. However, when the method for preparing the catalyst is applied, the procedure for preparing the catalyst is complicated, and the reactant When the ratio of C9 aromatic compounds is high, or when C10 or more aromatic compounds are included, it may be ineffective in preventing the catalyst inactive liquor.

U.S. Patent No. 4,723,048 discloses a catalyst for disproportionation / transalkylation of toluene and alkylaromatic compounds, one of the Group VIII metals on the periodic table such as nickel, palladium (Pd), mordenite, Group IB metals such as silver, And a process for preparing a catalyst supporting one metal of Group IVA metals such as tin, lead, germanium (Ge). In the above method, it is described that the performance of the catalyst is improved by using a metal such as nickel or palladium as a metal for hydrogenation and controlling their activity using a group IVA metal. However, metals such as nickel and palladium are used in the present invention. Since the hydrogenation activity is significantly lower than that of platinum, when the content of aromatic compounds of C9 or more in the reactants is increased, it may be difficult to prevent catalyst deactivation, and when sulfur compounds are introduced into the reactants, hydrogenation activity may be drastically lowered and recovery may be difficult. There is a possibility. In addition, when the IVA group metal which can further weaken the hydrogenation activity together with nickel, palladium, there is a possibility that this problem is further exacerbated.

In addition, there are many examples of using zeolite as a base material as a disproportionation / transalkylation catalyst, but using platinum as a metal having a hydrogenation function as in the present invention, and a second metal such as tin, lead or indium to control platinum activity. There is no example of improving the yield of mixed xylenes and deactivation of the catalyst by using.

In order to solve the above problems, the present inventors have repeatedly studied, by supporting platinum / tin, platinum / lead, or platinum / indium on a carrier made of mordenite or zeolite beta and an inorganic binder. It has been found that a superior mixed xylene yield can be obtained compared to the prepared catalyst and that the inert difference of the catalyst can be drastically reduced, and the present invention has been completed based on this finding.

Accordingly, it is an object of the present invention to maintain the yield of mixed xylenes as high as possible during disproportionation / transalkylation of benzene, toluene and C9 aromatic compounds, while suppressing deactivation as much as possible compared to conventional catalysts, thereby improving the catalyst regeneration cycle. It is to provide a disproportionation / transalkylation catalyst which can be extended as much as possible.

Another object of the present invention is to provide a method for preparing the disproportionation / transalkylation catalyst.

The catalyst of the present invention for achieving the above object is 10 to 95% by weight of mordenite or beta zeolite with a molar ratio of silica to alumina adjusted to 20 to 200, gamma alumina, silica, silica alumina, bentonite, kaolin 0.001 to 0.5 parts by weight of platinum, based on the amount of the carrier consisting of 5 to 90% by weight of at least one inorganic binder selected from the group consisting of kaolin, clinoptilolite and montmorillonite One metal selected from the group consisting of tin, lead and lead. The content of the tin and indium contained in the catalyst is 0.01 to 10.0 parts by weight based on the carrier amount of the zeolite and the binder, and the content of lead is 0.01 to 7.0 parts by weight.

The method of preparing the catalyst of the present invention for achieving the above another object is a gamma alumina, silica, silica alumina, bentonite, kaolin, clinop, mordenite or beta zeolite having a mole ratio of silica to alumina is adjusted to 20 to 200 A carrier is prepared by mixing at least one inorganic binder selected from the group consisting of tilolite and montmorillonite, impregnated with one metal selected from the group consisting of tin, lead and indium, followed by platinum It consists of.

Another method of preparing the catalyst of the present invention for achieving the above another object is a mordenite or beta zeolite and gamma alumina, silica, silica alumina, bentonite, kaolin, clinof, the mole ratio of silica / alumina is adjusted to 20 to 200 And at least one inorganic binder selected from the group consisting of tilolite and montmorillonite and one metal and platinum selected from the group consisting of tin, lead and indium.

In addition, another method for preparing the catalyst of the present invention for achieving the above another object is to support the platinum by the method of impregnation or ion exchange in the mordenite or beta zeolite whose molar ratio of silica / alumina is adjusted to 20 to 200 Thereafter, a carrier was prepared by mixing at least one inorganic binder selected from the group consisting of gamma alumina, silica, silica alumina, bentonite, kaolin, clinoptilolite and montmorillonite, followed by tin, lead, and indium. Impregnating one metal selected from the group consisting of:

In addition, another method for preparing the catalyst of the present invention for achieving the above another object is a mordenite or beta zeolite and gamma alumina, silica, silica alumina, bentonite, kaolin, the mole ratio of silica / alumina is adjusted to 20 to 200 After preparing a carrier by mixing at least one inorganic binder selected from the group consisting of clinoptilolite and montmorillonite with one metal selected from the group consisting of platinum or tin, lead and indium, Consisting of impregnating a broken metal into the coalescence.

1 is a graph showing the mixed xylene yield according to the reaction time in the catalyst prepared according to the present invention and the catalyst prepared according to a conventional method.

Hereinafter, the present invention will be described in more detail.

As described above, the present invention relates to a catalyst for preparing mixed xylene through disproportionation / transalkylation reaction and a method for preparing the same, and to the disproportionation reaction between toluene, toluene and C9 aromatic compounds on the catalyst prepared by the present invention. Along with the transalkylation reaction, the dealkylation reaction of the C9 or more alkylaromatic compound and the transalkylation reaction between the benzene and the C9 or more aromatic compound occur simultaneously. This dealkylation reaction is an important reaction to produce toluene which is required for disproportionation / transalkylation reactions. In addition, the transalkylation reaction between benzene and C9 or more aromatic compounds is also an important reaction for producing toluene and mixed xylene.

On the other hand, it is very important to rapidly hydrogenate olefins such as ethylene and propylene produced by the dealkylation reaction. If these olefins are not rapidly hydrogenated, they can be realkylated back to aromatics, ultimately reducing the conversion of C9 or more aromatics, and the olefins themselves may cause polymerization or the like to cause catalyst deactivation. Results in promoting production. Therefore, the catalyst described in the present invention must include a metal having a hydrogenation function in addition to the zeolite component such as mordenite or beta.

Unlike the conventional invention, the present invention uses platinum / tin, platinum / lead, or platinum / indium as a gold metal having a hydrogenation function. Thus, by using tin, lead, or indium as the second metal, the hydrogenation function of platinum Has been properly improved and also shows good catalytic performance when the second metal is present in relatively high content, at least three times the platinum content.

The zeolites mordenite and beta used in the present invention are prepared in the form of sodium at the first synthesis, and are easily converted to the mordenite in the hydrogen form by ion exchange with ammonium chloride or ammonium nitrate and then firing. Mordenite and zeolite beta in hydrogen form were used.

As evolved, mordenite having a value between 20 and 200 for the silica / alumina mole ratio of mordenite and zeolite beta according to the present invention was used. At this time, when the molar ratio of silica / alumina is less than 20, there is a problem in that the side reaction increases and the deactivation proceeds a little faster, and when it exceeds 200, the reaction activity is weakened to reduce the yield of mixed xylene. do.

The zeolites should be mixed with at least one inorganic binder, the inorganic binder being selected from the group consisting of gamma alumina, silica, silica alumina, bentonite, kaolin, clinoptilolite and montmorillonite, among which gamma alumina , Amorphous inorganic oxides of silica and silica alumina are preferred, and gamma alumina and silica are most preferred to exhibit excellent catalytic performance. When combining the inorganic binder with mordenite and zeolite beta, the zeolite is mixed so that the weight ratio is 10 to 95%, and then extruded to form a cylinder. One catalyst grain is about 2 mm in diameter and 5 to length. Mold to 15mm. The catalyst may be molded in a spherical form in addition to the cylindrical form. The mixed carrier of the zeolite and the inorganic binder thus formed has physical properties of an apparent packing density of 0.4 to 0.8 cc / g, an average pore diameter of 50 to 200 A, a pore volume of 0.1 to 1 cc / g, and a specific surface area of 200 to 400 m2 / g. It is desirable to have. At this time, when the content of the zeolite is less than 10% by weight, the reaction activity is weakened to reduce the mixed xylene yield, and when the content exceeds 95% by weight, the mechanical strength of the molded catalyst is weakened occurs. .

In addition, the final catalyst may be prepared by mixing mordenite or zeolite beta with an inorganic binder and then supporting platinum-tin, or platinum-lead, or platinum-indium, and first, the metal component is added to mordenite or zeolite beta. After supporting, the inorganic binder may be mixed and molded. In this way, when the metal is supported before or after molding, the order of introduction of the two supported metals is not significantly different from which metal is introduced first, and two kinds may be introduced at the same time. In addition, the carrier may be molded by mixing the two metals together, or may be molded by mixing one of the two metals during molding and then supporting the remaining metal to prepare a final catalyst.

The platinum is preferably prepared in an amount of 0.001 to 0.5 parts by weight based on the amount of the carrier of the zeolite and the binder. When the weight of platinum is less than 0.001 parts by weight, the dealkylation reaction of the alkyl aromatic compound is weakened to reduce the mixed xylene yield. In addition, the deactivation rate of the catalyst also increases, and if it exceeds 0.5 parts by weight, the function of platinum is so strong that the hydrocracking reaction becomes active, so that the production of hydrogen halides (C1 to C5) having a small molecular weight increases, and also the aromatic ring This results in an increase in naphthene-based compounds by hydrogenation. Platinum introduction may be performed by ion exchange, impregnation, or physical mixing. When introducing platinum by ion exchange, an aqueous solution such as ammonium platinum chloride or dinitro diamino platinum is used as a precursor, and when introducing platinum by impregnation, an aqueous solution of chloroplatinic acid or ammonium platinum chloride may be used as a precursor. In the case of phosphorus mixing, you may use the aqueous solution of all said precursors.

In the reaction of the present invention, tin, which is another important metal component, is preferably introduced in an amount of 0.01 to 10.0 parts by weight based on the amount of carriers of the zeolite and the binder, and when the amount of tin used exceeds 10.0 parts by weight, the method according to the present invention. Too weaken the function of platinum in the water, causing problems such as reduced mixed xylene yield and increased catalyst deactivation, and when the amount used is less than 0.01 parts by weight, it does not adequately control the strong hydrogenation function of platinum, hydrocarbons and naph This results in an increase in the ten-based compound. Tin is preferably introduced by impregnation or mixing, and tin dichloride, tin tetrachloride, tin acetate, tin sulfate and the like can be used as a precursor.

When platinum / lead is introduced into the carrier in addition to platinum / tin, the amount of platinum introduced, the method of introduction and the precursor used are the same as in the case where platinum / tin is introduced. Lead is preferably introduced in an amount of 0.01 to 7.0 parts by weight based on the carrier amount of the zeolite and the binder, and the role of lead is the same as that of tin in the catalyst in which platinum-tin is introduced. The amount of tin used has the same effect on catalyst performance. Lead is preferably introduced by impregnation or mixing, and as a precursor, lead acetate, lead nitrate, lead sulfate and the like can be used.

When platinum / indium is introduced into the carrier, the amount of platinum introduced, the method of introduction, and the precursor used are the same as in the case where platinum / tin is introduced. Indium is preferably introduced in an amount of 0.01 to 10.0 parts by weight based on the amount of the carrier of the zeolite and the binder, and the role of indium is the same as that of tin in the catalyst in which platinum / tin is introduced. The same use of tin has the same effect on catalyst performance. Indium is preferably introduced by a method of incorporation or mixing, and indium chloride, indium acetate, indium nitrate, indium sulfate and the like can be used as a precursor.

After the metal components having the hydrogenation function as described above are introduced into the catalyst, the drying process is carried out in air, and the temperature is preferably between 60 ° C. and 200 ° C., and the drying time is between 30 minutes and 12 hours. The dried catalyst has to go through a calcination process, it is preferable to bake at a temperature between 300 ° C and 650 ° C in an air or nitrogen atmosphere, and the firing time is preferably between 1 hour and 12 hours.

As mentioned above, when the pair of metal components of platinum / tin, platinum / lead, or platinum / indium is introduced into the mixed carrier of the zeolite and the inorganic binder, the introduction order does not matter, and the two metals Although it may be introduced at the same time, the metals are preferably present in a properly bonded state with each other. In particular, platinum may be combined with tin, lead, or indium, or present at a close distance such that it may affect each other electrically and chemically, rather than being independently present in the catalyst, so that good catalyst performance may be expected.

That is, when platinum is present alone, side reactions as described above may occur due to the high hydrogenation activity of platinum, but when tin, lead, or indium is combined with platinum or is present at a sufficiently close distance, an ensemble effect or a ligand effect, etc. Due to the interaction between the metal components, which can be described as, high hydrogenation activity of platinum is suppressed, it is possible to expect an optimum reduction of mixed xylene yield and deactivation rate.

As a result of the disproportionation / transalkylation of a mixture of benzene, toluene and a C9 or more aromatic compound on the catalyst prepared according to the present invention, a mixed xylene yield of at least 32% by weight was obtained, at which time the aromatic ring loss was 2.0%. Good results down to% were obtained.

Hereinafter, the present invention will be described in more detail with reference to the following Examples, but the scope of the present invention is not limited to the following Examples.

Comparative Example 1

A carrier prepared by molding a hydrogen mordenite having a molar ratio of silica / alumina of 90 to a diameter of 2 mm and a length of 10 mm using gamma alumina as a binder so that the weight ratio of mordenite was 50% was 10 at 150 ° C. After drying for 3 hours, firing was performed at 500 ° C for 3 hours. In order to evaluate the disproportionation / transalkylation reactivity without separately introducing a metal into the support, 2.0 g of the carrier catalyst was charged into a fixed bed reactor, reduced to hydrogen at 400 ° C. for 2 hours, and then used as a catalyst. Thereafter, a raw material consisting of benzene, toluene and C9 or more aromatic compounds was introduced into the reactor to carry out the reaction. Reaction conditions and results are shown in Table 1 and FIG. 1.

Comparative Example 2

A carrier was prepared using zeolite beta in the form of hydrogen having a molar ratio of silica / alumina of 25 as zeolite, and other preparation conditions, treatment conditions, and reaction conditions were the same as those described in Comparative Example 1, and the disproportionation / The transalkylation reaction was carried out and the results are shown in Table 1 and FIG. 1.

Comparative Example 3

After preparing a carrier in the same manner as in Comparative Example 1, the solution was impregnated with 0.02 parts by weight of platinum using an aqueous solution of H2PtCl6, dried at 150 ° C for 10 hours, and calcined at 500 ° C for 3 hours. Manufacture. The disproportionation / transalkylation reaction was carried out under the same reaction conditions as described in Comparative Example 1 using the catalyst thus prepared, and the reaction conditions and results are shown in Table 1.

Example 1

Hydrogen mordenite having a molar ratio of silica / alumina of 90 was formed to have a diameter of 2 mm and a length of 10 mm using gamma alumina as a binder, and the carrier prepared so that the weight ratio of mordenite was 50% was 10 at 150 ° C. After drying for 3 hours, firing was performed at 500 ° C for 3 hours. The aqueous solution of SnCl2 was used to impregnate tin in an amount of 0.j parts by weight based on the amount of the carrier, followed by drying at 150 ° C for 10 hours, and then baking at 500 ° C for 3 hours. The impregnated carrier was again impregnated with 0.05 parts by weight of platinum based on the carrier amount of mordenite and binder by using H 2 PtCl 6 aqueous solution, dried at 150 ° C. for 10 hours, and calcined at 500 ° C. for 3 hours to prepare a catalyst.

To evaluate the disproportionation / transalkylation reactivity of the prepared catalyst. 2.0 g of the catalyst was charged in a fixed bed reactor, reduced to hydrogen at 400 ° C. for 2 hours, and then a reaction was performed by introducing a raw material consisting of benzene, toluene, and C9 or more aromatic compounds.

The reaction results are shown in Table 1, and the mixed xylene yield was much higher than that of the catalysts of Comparative Examples 1 to 4 prepared by a conventional method, and the aromatic loss rate was also higher than that of Comparative Examples 3 to 4. It showed a significant decrease. In addition, as shown in Figure 1, when comparing the change of the mixed xylene according to the reaction time, the reduction rate of the mixed xylene yield is significantly reduced compared to the catalysts of Comparative Examples 1 to 2 significantly in terms of deactivation of the catalyst It was found to be improved.

Example 2

Catalysts were prepared and reacted in the same manner and conditions as described in Example 1, except for using zeolite beta in the hydrogen form with a molar ratio of silica / alumina of 25 instead of mordenite, and the results were shown in Table 1 And shown in FIG. 1.

Reactivity showed similar performance to the catalyst prepared by Example 1.

Example 3

In the process of forming a hydrogen mordenite having a molar ratio of silica / alumina of 90 to gamma alumina as a binder and mixing an aqueous solution of H2PtCl6 and an aqueous solution of SnCl2, the weight ratio of mordenite was 50% in the carrier excluding platinum and tin. . The catalyst is molded so that the platinum is 0.04 parts by weight and the tin is 0.4 parts by weight to have a diameter of 2 mm and a length of 10 mm, followed by drying at 150 ° C. for 10 hours and firing at 500 ° C. for 3 hours. The disproportionation / transalkylation reaction was carried out under the same reaction conditions as described in Example 1 using the catalyst thus prepared, and the reaction conditions and results are shown in Table 1 and FIG. 1. Reactivity showed similar performance to the catalyst prepared by Example 1.

Example 4

Catalysts were prepared and reacted in the same manner and conditions as described in Example 3, except that zeolite beta in the hydrogen form with a molar ratio of silica / alumina of 25 was used instead of mordenite, and the results are shown in Table 1. Indicated.

The reaction performance showed similar performance to the catalyst prepared by Example 1.

TABLE 1

Evaluation result of disproportionation / transalkylation reactivity (Comparative Examples 1-4 and Examples 1-4)

Example 5

In the same method and conditions as described in Example 1, except that the catalyst was prepared so that lead is 0.6 parts by weight based on the carrier amount of mordenite and the binder using an aqueous solution of Pb (NO ₃ ) ₂ instead of an aqueous solution of SnCl ₂ . A catalyst was prepared and the reaction was carried out and the results are shown in Table 2.

Example 6

In the same method and conditions as described in Example 1, except that the catalyst was prepared so that the indium was 0.5 parts by weight based on the mordenite and the binder amount using an aqueous solution of In (NO ₃ ) ₂ instead of an aqueous solution of SnCl ₂ . A catalyst was prepared and the reaction was carried out and the results are shown in Table 2.

Example 7

Example 3 except that the catalyst is prepared so that lead is 0.5 parts by weight based on the carrier amount of mordenite and binder by mixing Pb (NO ₃ ) ₂ aqueous solution with aqueous H ₂ PtCl ₆ instead of aqueous SnCl ₂ solution. The catalyst was prepared and the reaction was carried out in the same methods and conditions as described, and the results are shown in Table 2.

Example 8

An In (NO ₃ ) ₂ aqueous solution was mixed with an aqueous H ₂ PtCl ₆ solution instead of an aqueous SnCl ₂ solution, except that the catalyst was prepared so that indium was 0.4 parts by weight based on the carrier amount of mordenite and the binder. The catalyst was prepared and the reaction was carried out in the same methods and conditions as described, and the results are shown in Table 2.

TABLE 2

Results of Evaluation of Disproportionation / Transalkylation Reactivity (Examples 5 to 8)

Example 9

Hydrogen mordenite having a molar ratio of silica / alumina of 90 was impregnated with platinum using an aqueous solution of H ₂ PtCl ₆ , and mordenite impregnated with platinum was gamma alumina as a binder with a diameter of 2 mm and a length of 10 mm. The carrier was molded so that the weight ratio of mordenite was 50% in the carrier excluding platinum, and the carrier was dried at 150 ° C. for 10 hours, at 500 ° C., for platinum to 0.04 part by weight based on the amount of mordenite and zeolite. Fire for 3 hours. Tin was impregnated in the carrier to 0.4 parts by weight with respect to the carrier amount of mordenite and the binder using SnCl ₂ aqueous solution, and dried at 150 ° C. for 10 hours, and then calcined at 500 ° C. for 3 hours to prepare a catalyst.

The disproportionation / transalkylation reaction was carried out under the same reaction conditions as described in Example 1 using the catalyst thus prepared, and the reaction conditions and results are shown in Table 3.

Example 10

In the same method and conditions as described in Example 9 except that the catalyst was prepared so that lead was 0.5 parts by weight based on the carrier amount of mordenite and the binder using an aqueous solution of Pb (NO ₃ ) ₂ instead of an aqueous solution of SnCl ₂ . A catalyst was prepared and the reaction was carried out and the results are shown in Table 3.

Example 11

In the same method and conditions as described in Example 9 except that the catalyst was prepared such that indium was 0.4 parts by weight based on the carrier amount of mordenite and the binder using an aqueous solution of In (NO ₃ ) ₂ instead of an aqueous solution of SnCl ₂ . A catalyst was prepared and the reaction was carried out and the results are shown in Table 3.

Example 12

Catalysts were prepared and subjected to the reaction in the same manner and conditions as described in Example 9, except that zeolite beta in a hydrogen form having a molar ratio of silica / alumina of 25 was used instead of mordenite, and the results are shown in Table 3. Indicated.

TABLE 3

Disproportionation / transalkylation reactivity evaluation results (Examples 9-12)

Example 13

Hydrogen mordenite having a molar ratio of silica / alumina of 90 was mixed with gamma alumina as a binder to form an aqueous solution of SnCl ₂ , whereby the weight ratio of mordenite was 50% and tin A catalyst is prepared by forming 0.4 parts by weight of the carrier of the mordenite and the binder so as to have a diameter of 2 mm and a length of 10 mm, drying at 150 ° C for 10 hours, and calcining at 500 ° C for 3 hours. The prepared carrier was again impregnated with 0.02 parts by weight of platinum based on the amount of mordenite and binder using aqueous solution of H ₂ PtCl ₆ , dried at 150 ° C. for 10 hours, and calcined at 500 ° C. for 3 hours to prepare a catalyst. . The disproportionation / transalkylation reaction was carried out under the same reaction conditions as described in Example 1 using the catalyst thus prepared, and the reaction results are shown in Table 4.

Example 14

The catalyst described in Example 13 was prepared by mixing Pb (NO ₃ ) ₂ aqueous solution instead of SnC1 ₂ aqueous solution in the carrier molding process so that the catalyst was prepared to be 0.5 parts by weight based on the amount of lead-mordenite and binder. The catalyst was prepared and the reaction was carried out in the same method and conditions, and the results are shown in Table 4.

Example 15

By mixing the aqueous solution of In (NO ₃ ) ₂ instead of the aqueous solution of SnCl _{2 in the} process of forming the carrier, the catalyst was prepared in the same manner as described in Example 13 except that the catalyst was prepared so that indium was 0.4 parts by weight based on the amount of the mordenite and the binder. The catalyst was prepared and the reaction was carried out in the same method and conditions, and the results are shown in Table 4.

Example 16

Catalysts were prepared and reacted in the same manner and conditions as described in Example 13, except that zeolite beta in the hydrogen form with a molar ratio of silica / alumina of 25 was used instead of mordenite, and the results are shown in Table 4. Indicated.

TABLE 4

Results of Evaluation of Disproportionation / Transalkylation Reactivity (Examples 13 to 16)

In the results of the above examples, the catalysts prepared by the methods of Examples 5 to 16 also showed similar reaction performances compared to the catalysts prepared by the method of Example 1.

As described above, the catalyst of the present invention can significantly increase the mixed xylene yield in the disproportionation / transalkylation reaction of benzene, toluene and C9 or more aromatic compounds, greatly reduce the aromatic loss rate, and also in terms of deactivation of the catalyst. It is a significant improvement and can be used as a very useful catalyst in industry.

Claims (7)

10 to 95% by weight of mordenite or beta zeolite and gamma alumina, silica, silica alumina, bentonite, kaolin, clinoptilolite and montmorillonite with a molar ratio of silica / alumina adjusted in the range of 20 to 200 At least one inorganic binder selected from the group consisting of 5 to 90% by weight of a hydrogenated metal in the mixed carrier, which is selected from the group consisting of 0.001 to 0.5 parts by weight of platinum, tin, indium and lead based on the amount of the carrier of the mixed carrier. A catalyst for producing mixed xylenes from benzene, toluene and C9 or higher aromatic compounds, characterized by the introduction of metals. According to claim 1, wherein the content of the tin is 0.01 to 10.0 parts by weight, the content of lead is 0.01 to 7.0 parts by weight, and the content of indium is 0.01 to 10.0 parts by weight relative to the carrier amount of the mixed carrier. A catalyst for producing mixed xylenes from benzene, toluene and C9 or more aromatic compounds. The catalyst for preparing mixed xylenes from benzene, toluene and C9 or higher aromatic compounds according to claim 1, wherein the inorganic binder is gamma alumina. a) 10 to 95% by weight of mordenite or beta zeolite with a molar ratio of silica / alumina in the range of 20 to 200, and gamma alumina, silica, silica alumina, bentonite, kaolin, clinoptilolite and montmo Mixing and molding 5 to 90% by weight of at least one inorganic binder selected from the group consisting of lilonite; And b) sequentially or simultaneously introducing one or more metals and platinum selected from the group consisting of tin, lead and indium into the mixed carrier comprising the zeolite and the inorganic binder; To include, the content of platinum is 0.001 to 0.5 parts by weight, the content of tin is 0.01 to 10.0 parts by weight, the content of lead is 0.01 to 7.0 parts by weight, and the content of indium relative to the amount of the carrier of the mixed carrier 0.01 to 10.0 parts by weight of the method for producing a catalyst for producing mixed xylenes from benzene, toluene and C9 or more aromatic compounds. 10 to 95% by weight mordenite or beta zeolite with a molar ratio of silica / alumina in the range of 20 to 200, and gamma alumina, silica, silica alumina, bentonite, kaolin, clinoptilolite and montmorillonite 5 to 90% by weight of at least one inorganic binder selected from the group consisting of platinum, and tin, indium and lead is prepared by introducing at least one metal selected from the group consisting of lead and made of the zeolite and inorganic binder The content of platinum is 0.001 to 0.5 parts by weight, the content of tin is 0.01 to 10.0 parts by weight, the content of lead is 0.01 to 7.0 parts by weight, and the content of indium is 0.01 to 10.0 parts by weight based on the amount of the carrier of the mixed carrier. A process for producing a catalyst for producing mixed xylenes from benzene, toluene and C9 or more aromatic compounds. a) introducing platinum into a mordenite or beta zeolite having a molar ratio of silica / alumina in the range of 20-200; b) platinum is introduced by mixing and molding at least one inorganic binder selected from the group consisting of gamma alumina, silica, silica alumina, bentonite, kaolin, clinoptilolite, and montmorillonite with zeolite introduced with platinum. Preparing a mixed carrier; c) introducing one metal selected from the group consisting of tin, lead and indium into the mixed carrier into which platinum is introduced; Wherein the mixed carrier comprises 10 to 95% by weight of zeolite and 5 to 90% by weight of an inorganic binder, and the content of platinum is 0.001 to 0.5 parts by weight based on the amount of the carrier of the mixed carrier. Is 0.01 to 10.0 parts by weight of lead, 0.01 to 7.0 parts by weight of lead, and indium content of 0.01 to 10.0 parts by weight for producing mixed xylenes from aromatic compounds of benzene, toluene and C9 or more Method for preparing a catalyst. a) 10 to 95% by weight of mordenite or beta zeolite with a molar ratio of silica / alumina in the range of 20 to 200 and gamma alumina, silica, silica alumina, bentonite, kaolin, clinoptilolite and montmorillon Introducing 5 to 90% by weight of at least one inorganic binder selected from the group consisting of nitrate and introducing one metal of platinum and one metal selected from the group consisting of tin, lead and indium; And b) introducing the remaining metal not introduced in step a) into the mixed carrier comprising the zeolite and the inorganic binder; To include, the content of platinum is 0.001 to 0.5 parts by weight, the content of tin is 0.01 to 10.0 parts by weight, the content of lead is 0.01 to 7.0 parts by weight, and the content of indium relative to the amount of the carrier of the mixed carrier 0.01-10.0 weight part of this, The manufacturing method of the catalyst for manufacturing mixed xylene from benzene, toluene, and C9 or more aromatic compound.