JPH0840947A - Method for reaction in zeolite suspension catalyst system - Google Patents

Abstract

PURPOSE:To continuously carry out the conversion of an aromatic compound with good productivity in a simple process by performing the converting reaction of the aromatic compound in a suspension fluidized bed of zeolite, then separating the zeolite suspension by the precipitation and circulating the resultant concentrated zeolite suspension through the suspension fluidized bed for use. CONSTITUTION:This method for reaction in a zeolite suspension catalyst system is to initially carry out converting reaction of an aromatic compound in a suspension fluidized bed of zeolite, provide a liquid product, then separate the suspension containing the liquid product and zeolite into a liquid reactional product with <=0.3wt.% zeolite content and a concentrated zeolite suspension by the precipitation and subsequently circulate the resultant concentrated zeolite suspension through the suspension fluidized bed in carrying out the converting reaction of the aromatic compound in the liquid phase or a mixed phase of a vapor with the liquid in the presence of the zeolite catalyst (preferably zeolite beta). Furthermore, an interfacial settling method is preferred as the form of the precipitation and the average particle diameter of the zeolite is preferably 0.03-60mum and the slurry concentration is preferably 3-35wt.%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic compound conversion reaction method for producing various polymer raw materials and organic intermediate raw materials.

[0002]

The conversion reaction of aromatic compounds in a liquid phase or a gas-liquid mixed phase using a zeolite catalyst includes alkylation reaction of benzene with olefin, transalkylation reaction of benzene and alkylated benzene, and conversion of alkylated benzene. Many examples such as disproportionation reaction and isomerization reaction of alkylated benzene have been reported.

For example, US Pat. No. 4,169,111,
US Pat. No. 4,185,040, US Pat. No. 4,45
No. 9,426 describes an example of an alkylation reaction of benzene with ethylene in a fixed bed liquid phase reaction system using Y-type zeolite as a catalyst. Japanese Unexamined Patent Publication (Kokai) No. 64-68329 discloses a trans-form of an aromatic compound in a fixed bed liquid phase reaction system using a catalyst containing a zeolite having a silica / alumina ratio of 40 or less, an α value of at least 400 and a control index of 5 to 9. Examples of alkylation are described.

Japanese Unexamined Patent Publication (Kokai) No. 2-96539 discloses that a fixed bed liquid phase reaction system using zeolite as a catalyst has a carbon number of 8 to 16
Examples of alkylation reaction of benzene with olefins are described. JP-A-2-174731 describes an example of benzene alkylation by a fixed bed liquid phase reaction system using modified mordenite as a catalyst.

JP-A-5-49652 describes an example of a benzene alkylation reaction by a moving bed liquid phase reaction system using a zeolite molded body as a catalyst. Japanese Patent Laid-Open No. 3-1
No. 81424 describes a liquid phase alkylation method of aromatic hydrocarbons with olefins using zeolite β as a catalyst. In the description of the reaction mode in the specification of this patent, it is described that a fixed bed reactor or a fluidized bed reactor may be used in the continuous reaction, but all the examples are carried out in the fixed bed reaction mode. However, there is no example of a fluidized bed, and there is no description regarding catalyst separation. .

JP-A-61-161230 describes an example of an alkylation reaction of benzene with an olefin in a reactive distillation system in which a fixed bed of Y-type zeolite is installed in a distillation column. EP 432,814 also describes a liquid-phase alkylation process of aromatic hydrocarbons with olefins, which also uses zeolite β as a catalyst. However, although the examples are carried out in suspension, they are all examples of batch reactions, and no mention is made of catalyst separation.

JP-A-4-187647 describes a liquid phase reaction method in which alkylation and transalkylation of an aromatic compound are carried out in separate reactors, and zeolite is used as a catalyst for either step. All the examples are carried out in a fixed bed reaction format. JP-A-2-28952
No. 4 describes an aromatic hydrocarbon alkylation method using a solid granular acidic catalyst in a slurry state (suspension state). In this method, the slurry is directly supplied to the distillation column to separate the catalyst.

US Pat. No. 5,087,784 describes a method for alkylating an aromatic compound in which a porous filter is provided in a distillation column and a zeolite slurry flowing in the filter is used as a catalyst. The catalyst separation of this method is basically performed by a porous filter. JP-A-5
No. 68869 describes a reaction method using a cross-flow type filter for separating a liquid product obtained from a suspension fluidized bed reactor and a particulate solid catalyst.

[0009]

Among the conventional techniques, the fixed bed reaction system is advantageous in carrying out a continuous reaction in that it requires no catalyst separation. However, since it is necessary to use a molded body as the catalyst, there is a problem that the activity is significantly reduced due to the reduction of the effective surface area of the catalyst. Particularly in the liquid phase reaction, the reaction temperature is relatively low, so that the diffusion rate is slow, and the diffusion in the molding particles has a great influence on the activity. or,
There is also a problem that the decrease in the effective surface area of the catalyst causes a large decrease in activity over time in a continuous reaction. For the above reasons, the conventional fixed bed liquid phase reaction system using zeolite has a problem that an extremely large amount of catalyst is required and, as a result, an extremely large reactor volume is required.

On the other hand, the method of using the zeolite in a slurry state is advantageous in that it has high activity because the effective surface area of the catalyst is larger than that of the molded body, but separation of the reaction product liquid and the catalyst becomes a problem. In the method of separating zeolite slurry in the prior art, the method of directly supplying the slurry to the distillation tower is that the zeolite and the packing of the distillation tower are clogged with the zeolite or the heat exchange tube surface is covered with the zeolite and transferred. There is a problem that thermal efficiency is reduced.

The method using a porous filter generally has a poor filterability of zeolite, so that when combined with a continuous reaction system, the filtration area of the filter is extremely large and when the filter is continuously used, Problems such as clogging and deterioration of filtration ability occur. Further, a sedimentation separation method is known as a general method for separating a slurry, but in the case of zeolite, the sedimentation separation method is extremely poor in the sedimentation property in a water slurry state at the time of catalyst production and the poor filterability described above. Since it was expected to be difficult, no example of combining a continuous reaction system and a sedimentation separation method has been reported.

As described above, an effective catalyst separation method in a slurry system which uses zeolite as a catalyst and is expected to have high activity and long life has not been known.

[0013]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, when zeolite is mainly used as a slurry in an aromatic compound, the sedimentation is surprisingly good. The present invention has been found out and the present invention has been completed. That is, in the present invention, when a liquid reaction product is obtained by converting an aromatic compound in a liquid phase or a gas-liquid mixed phase in the presence of a zeolite catalyst, (1) a liquid product in a suspension fluidized bed of zeolite (2) A step of separating a zeolite suspension mainly composed of a liquid product into a liquid reaction product having a zeolite content of 0.3% by weight or less and a concentrated zeolite suspension by sedimentation separation ( 3) A continuous reaction method of an aromatic compound, which comprises a step of circulating the concentrated zeolite suspension into a suspension fluidized bed.

According to the present invention, by using zeolite in a slurry, it is possible to achieve high activity and a long life, and it is possible to obtain zeolite by a simple method called settler separation without using a special separation device such as a filter. It can be separated. The rapid sedimentation of the zeolite slurry in the aromatic compound is probably due to the different aggregation states of the zeolite in water and in the aromatic compound. In particular, it is considered that the surface of zeolite particles, which greatly affects the agglomeration state, has a lower crystallinity and is closer to an amorphous state than the inside of the particles, and thus is close to hydrophilic. Therefore, it is considered that, in water, the particles have a good dispersibility due to the stabilization by the coordination of water to the surface of the particles, whereas in the aromatic, the contribution of the stabilization is small, and therefore the particles are likely to aggregate.

Next, the invention will be described in more detail. The aromatic compound in the present invention is a compound having a benzene ring and a naphthalene ring. These compounds may have various substituents, and examples of the substituents include alkyl groups such as methyl group, ethyl group and propyl group, hydroxyl group, carboxyl group, carbonyl group, alkoxy group, nitro group, amino group. , Halogen groups and the like.

Among these, benzene and alkylated benzene having 1 to 4 carbon atoms are preferable, and benzene and ethylated benzene are particularly preferable. Examples of the conversion reaction of the aromatic compound in the present invention include alkylation, disproportionation, transalkylation, isomerization, oxidation, reduction, hydroxylation, carbonylation, nitration, amination and halogenation. Of these, alkylation, disproportionation, transalkylation and isomerization are preferable, and alkylation and transalkylation are particularly preferable.

When the conversion reaction is alkylation, an olefin having 2 to 16 carbon atoms or an alcohol can be used as an alkylating agent, but an olefin having 2 to 4 carbon atoms is preferable, and an olefin having 2 to 4 carbon atoms is particularly preferable. They are ethylene and propylene. In the present invention, the most preferable combination of the starting aromatic compound and its conversion reaction is benzene as the starting aromatic compound and the conversion reaction is a combination of ethylation reaction with ethylene.

The zeolite catalyst in the present invention is a general term for crystalline aluminosilicate having a three-dimensional regular network structure. Generally, in zeolite, Si and Al are cross-bonded in a four-coordinated state via oxygen to form a crystal structure, and in an ideal structure, Al forms an anion site. In order to neutralize the charge of this anion site, H ⁺ or a metal cation is present in the crystal. In recent years, zeolite Si has been used as a zeolite analog.
Alternatively, a crystalline metallosilicate in which a part of Al is replaced by B, Fe, Cr, Ti, Ge, Ga, etc. has been reported, but the zeolite catalyst in the present application also includes these crystalline metallosilicates.

The cation in the zeolite in the present invention can be appropriately selected depending on the conversion reaction. For example, in the case of alkylation, disproportionation, transalkylation, and isomerization reaction, H ⁺ , Group IIA, Group IIIA, IVB on the periodic table
A group metal cation can be selected. In the case of oxidation or reduction reaction, IB group, IIB group, IVA group, IVB group
Group, VB, VIB, VIIB, VIII metal cations can be selected.

Of these cations, preferred are H ⁺ , IIA and IIIA cations, and particularly preferred are H ⁺ and IIIA cations. Particularly in the case of the most preferable benzene alkylation reaction in the present invention, H ⁺ and Al cations are preferable. SiO ₂ / Al ₂ O ₃ constituting the crystal skeleton of the zeolite in the present invention
A ratio of 2 to 1000, preferably 5 to 200, and more preferably 10 to 100 can be used. Further, as described above, a part or all of Al may be replaced with a different element such as B, Fe, Cr, Ti, Ge, Ga.

Examples of such zeolites are A type zeolite, X and Y type faujasite, L type zeolite, mordenite, offretite, erionite, ferrierite, zeolite β, ZSM-4, ZSM-5,
ZSM-8, ZSM-11, ZSM-12, ZSM-2
0, ZSM-35, ZSM-48 and the like. Among them, Y-type zeolite, mordenite, offretite, zeolite β, ZSM-5 and ZSM-11 are preferable, and zeolite β is particularly preferable.

Zeolite β is a product of US Pat. No. 3,308,06
It is a synthetic crystalline aluminosilicate described in Japanese Patent No. Since this zeolite β has the characteristic X-ray diffraction line shown in Table 1, it can be clearly distinguished from other zeolites.

[0023]

[Table 1]

SiO of zeolite β used in the present invention
₂ / Al ₂ O ₃ ratio is in the range of 5 to 100, preferably 1
It is in the range of 0 to 60, and more preferably in the range of 20 to 50. In the present invention, zeolite is used as a catalyst in a suspension fluidized bed type, that is, a slurry system. As a reaction method, a reaction system in which a catalyst and a liquid, and in some cases, a mixture including a gas are mixed by a stirring tank, a gas lift, a circulation pump, or the like and good contact between different phases is used. Of these, the stirred tank type in which the reaction device is simple is preferable.

In the present invention, the sedimentation separation method is used to separate the zeolite from the zeolite suspension mainly composed of the liquid product. The form of this sedimentation separation can be generally divided into bulk sedimentation and interfacial sedimentation. Bulk settling is the usual free settling, where large particles settle first in particles with a size distribution and smaller particles settle later. Therefore, since fine particles remain in the supernatant phase, it takes time to clarify the particles, and the particles settled at the bottom form a layer to gradually consolidate and the boundary surface gradually rises.

On the other hand, when the interfacial sedimentation has cohesive properties in the particles, a plastic structure is formed when the particles become linked to each other as the particle concentration increases, and all the particles trapped in this structure are formed. It is a phenomenon of sedimentation at the same rate. In this case, the supernatant phase becomes transparent from an early period because the fine particles are taken up in the plastic structure and settled,
The supernatant phase and the sedimentation phase form a clear interface and settle.
Also, consolidation of the sedimentation phase is significantly slower than that of bulk sedimentation. (Solid-liquid separation technology: Shirato Monpei, Gihodo Publishing, P98
Reference) Which sedimentation form the zeolite in the present invention takes depends on the type of zeolite, the particle size of the zeolite, the slurry concentration, the type and physical properties of the produced liquid, the temperature, and the like.

For example, bulk sedimentation is often observed when the particle size of zeolite particles is relatively large, for example, 100 μm or more, and the particle size distribution is uniform. In this case, the size of the sedimentation tank is reduced because the sedimentation speed is high, which is preferable. However, if the particles are too large, the activity is significantly decreased with the decrease of the effective surface area of the catalyst, and if the sedimentation is too fast, problems such as clogging due to the accumulation of particles occur, which is not preferable. Usually, the average particle size is 100 to 5
The range of 00 μm is preferable, and 100 to 100 is particularly preferable.
It is in the range of 300 μm.

The average particle size referred to herein is the particle size obtained by dispersing zeolite particles in methanol, dropping the sample on a sample stage, drying it, depositing gold, and observing with a scanning electron microscope. However, the observed particle size is 0.01 to 5 μm.
There are cases where primary particles of a certain degree are dispersed and cases where secondary particles are aggregated to a larger extent. The average particle size referred to here is the primary particle size when dispersed and 2 when aggregated.
Refers to the secondary particle size.

Although various shapes of particles are observed, the particle diameter mentioned here is represented by the diameter of a sphere of equal volume. On the other hand, interfacial sedimentation has the greatest controlling factor on the cohesiveness of zeolite particles, so the type of zeolite, particle size,
It is greatly affected by the concentration. In particular, the particle size greatly affects the cohesiveness of the zeolite particles. The average particle size at which interfacial precipitation of zeolite in the present invention is observed is about 1
This is the case where the thickness is 00 μm or less.

The characteristics of interfacial sedimentation are the high clarity of the supernatant phase and the slow deposition of particles in the sedimentation phase. This is very advantageous in the continuous reaction system like the present invention. This is because the high clarity of the supernatant phase means that the flow of zeolite catalyst from the settling tank (settler) is extremely low, and the slow deposition of particles in the settling phase means that the reactor and concentrated slurry circulation line are This means that the risk of blockage is low.

Further, interfacial sedimentation is particularly advantageous in the reaction mode of forced circulation by a stirring tank or a pump. because,
In a stirring tank or a pump circulation, pulverization of zeolite particles occurs over time, and fine powder of 1 μm or less gradually increases. This is because in normal bulk sedimentation, these fine powders no longer settle in the sedimentation tank and flow out, but in interfacial sedimentation, the fine powders are also trapped in the plastic structure and settle.

An interfacial sedimentation method is an advantageous sedimentation method in the reaction type using a stirring tank or pump circulation in the present invention, and for this reason, the average particle diameter of zeolite is preferably 0.01 to
100 μm range, particularly preferably 0.03 to 60 μm
m. The preferred slurry concentration for interfacial sedimentation varies depending on the particle size, but is in the range of approximately 1 to 40% by weight, particularly preferably in the range of 3 to 35% by weight.

The most preferred zeolite in the present invention is zeolite β. In the case of zeolite β, interfacial sedimentation occurs when the average particle size is 0.01 to 100 μm and the slurry concentration is 3 to 30% by weight. However, even with the same particles, normal bulk sedimentation occurs when the slurry concentration is less than 3% by weight. Further, even if the particle and slurry concentrations are the same, when the liquid is water, interfacial sedimentation does not occur, and normal bulk sedimentation occurs.

The content of zeolite in the liquid reaction product which is the supernatant phase of the sedimentation separation in the present invention is 0.3% by weight or less, preferably 0.2% by weight or less, more preferably 0.1% by weight or less. is there. Even with the present invention, a trace amount of zeolite may be mixed in the supernatant phase, but in this case, it may be removed using another separation method.
As a removal method, a usual filtration method, an evaporation separation method, or the like can be used. Also when combined with these separation methods, most of the zeolites have already been separated according to the present invention, so that there is an advantage that the load is very small.

Embodiments of the present invention require a reaction zone and a settling separation zone. In this case, the reaction zone and the sedimentation separation zone may be clearly distinguished in the reactor and the sedimentation tank, or an internal settler may be provided in the reactor to carry out the reaction and the sedimentation separation simultaneously in the reactor. The operating temperature in the present invention includes the temperatures of the reaction zone and the sedimentation separation zone,
The temperature of the reaction zone is not particularly limited as long as the conversion reaction of the aromatic compound proceeds and the liquid phase can be maintained in the reaction system, but is usually 30 to 300 ° C., preferably 50 to 300 ° C.
The temperature is 250 ° C, more preferably 100 to 200 ° C. Further, the temperature of the sedimentation separation zone is not particularly limited as long as the liquid phase can be maintained, but from the viewpoint of the sedimentation rate, a high temperature is advantageous, but if it is too high, an undesired side reaction occurs in the separation zone. 250 ° C, preferably 50-
The temperature is 230 ° C, more preferably 100 to 200 ° C.

The pressure in the present invention is not particularly limited as long as the liquid phase is maintained, but if the pressure in the sedimentation separation zone is lower than that in the reaction zone, bubbles of dissolved gas may be generated to inhibit sedimentation separation. Therefore, it is preferable that both zones have equal pressure. The pressure is usually in the range of 1 to 300 atm, preferably 2 to 200 atm, and more preferably 5 to 100 atm.

[0037]

EXAMPLES The present invention will be described below with reference to examples.

[0038]

Example 1 (1) Preparation of Zeolite β 42 g of NaOH and 60.7 of NaAlO ₂ were added to 1600 g of a 10 wt% aqueous tetraethylammonium hydroxide solution.
g and 1400 g of water were added to obtain a uniform solution. Powdered SiO ₂ (Nipseal NV-3 made by Nippon Silica Industry Co., Ltd.)
705 g was added, and the mixture was charged into a 5-liter autoclave equipped with a stirrer and crystallized at 155 ° C. for 9 days with stirring at 500 rpm.

The product obtained is filtered and washed with water, then 12
It was dried at 0 ° C. for 4 hours and then calcined at 450 ° C. for 5 hours under air flow. Then, after cooling to room temperature, 0.15N
60% by adding 10% by weight slurry to nitric acid aqueous solution
Ion exchange was performed for 2 hours. Then, the slurry was filtered, washed with water, and then dried at 120 ° C. for 5 hours to obtain an H-type. This product was identified as zeolite β by X-ray diffraction analysis of the obtained powder. The SiO ₂ / Al ₂ O ₃ ratio determined by fluorescent X-ray analysis was 25.

FIG. 1 shows a scanning electron micrograph of H-β obtained. From this photograph, it can be seen that this H-β is an extremely fine particle having an average particle diameter of about 0.3 μm. (2) Sedimentation and Separation Experiment H-β prepared in (1) was added to a benzene / ethylbenzene equivalent weight mixture to adjust the slurry concentration to 15% by weight. The slurry was charged into a 1-liter glass autoclave, the gas phase was replaced with nitrogen, and the temperature was raised to 120 ° C. to set the pressure to 8 kg / cm ² .

1 of this slurry was prepared by using a turbine blade (diameter: 30 mm) installed in a glass autoclave.
After stirring at 000 rpm for 5 minutes, the stirring was stopped and the state of zeolite sedimentation was visually observed. The sedimentation condition was interfacial sedimentation, and a clear interface between the supernatant phase and the sedimentation phase was formed, and consolidation of the sedimentation phase was hardly observed in about 10 minutes. The observed interfacial sedimentation velocity was 1.5 mm / s.

The supernatant phase was sampled 1 minute after the stirring was stopped and the zeolite concentration in the sample was measured.
It was 30 ppm by weight. (3) Stirred tank flow reaction A benzene alkylation reaction with ethylene was carried out using the H-β obtained in (1) as a catalyst using a stirred tank reactor having an internal volume of 2 liters having a settler inside. It was

The structure of the reactor and the settler is shown in FIG.
The separation cross-sectional area of the settler was 31 cm ² , and the volume of the settler portion was 200 cm ³ . Reaction conditions Slurry hold-up: 1400 cm ³ Catalyst amount: 190 g (slurry concentration: 15% by weight) Benzene supply rate: 7.3 liters / hr Oil withdrawal linear velocity in settler: 0.65 mm / s Reaction pressure: 18 kg / cm ² G (Ethylene is supplied through the pressure control valve installed at the inlet of the reactor for the amount of reaction consumption so as to keep the pressure in the system constant.) Ethylene partial pressure is about 9 kg / cm ² ) Reaction temperature: 190 ° C. Stirring: 800 rpm using a self-contained stirring blade (diameter: 40 mm) with a gas inlet in the gas phase of the stirring shaft
It was stirred at.

Result The ethylation rate ε is defined by the following formula. ε: Amount of ethyl groups in benzene ring / amount of raw material benzene (for example, if 50% of benzene becomes diethylbenzene, ε = 0.5 × 2/1 = 1.0) 3 hours and 100 hours after starting the reaction The catalyst concentrations in the spilled oil at the time of are 110 wtppm and 90 ppm, respectively.
It was ppm by weight.

Ε at 3 hours and 100 hours after the start of the reaction,
The selectivity of ethylated benzene (benzenes having an ethyl group) was as follows. Reaction time (hr) 3 100 ε 0.6 0.4 Selectivity (%) 99.7 99.7 Further, the liquid composition (weight ratio) in 3 hours is benzene / ethylbenzene / diethylbenzene / triethylbenzene = 47.
It was / 33/15/5.

In this reaction, about 60 g of catalyst flowed out after 100 hours of reaction, and when the amount of flow-out catalyst was corrected, there was almost no decrease in ε.

[0047]

Example 2 A filter was installed in the oil line flowing out of the reactor of Example 1 and the catalyst collected every 30 hours was returned to the reaction system to carry out a continuous alkylation reaction of benzene with ethylene for 500 hours as follows. I went under the conditions. Reaction conditions Catalyst: H-β 240 g (slurry concentration: 19% by weight) same as in Example 1 Benzene supply rate: 8.0 liter / hr Oil extraction linear velocity in settler: 0.72 mm / s Pressure: 18 kg / cm ² G Temperature: 190 ° C. Stirring: 1000 rpm Results The reaction results at each time are shown below. Reaction time (hr) 3 100 300 500 Catalyst concentration in output oil (ppm by weight) 170 140 140 150 160 ε 0.7 0.68 0.65 0.61 Ethylated benzene selectivity (%) 99.7 99.8 99.8 99.7

[0048]

Example 3 (1) Catalyst The SiO ₂ / Al ₂ O ₃ ratio of H-β manufactured by PQ Corporation was 30 as a result of fluorescence X-ray analysis. This H
A scanning electron micrograph of -β is shown in FIG. It can be seen that it is a mixture of larger and smaller particles than the photograph. The average particle size of this H-β was 30 μm. (2) Sedimentation and Separation Experiment H-β of (1) was added to the same benzene / ethylbenzene mixture as in Example 1 to prepare a 7.9 wt% slurry,
The sedimentation separation situation was observed by the same operation as in (2) of Example 1.

The sedimentation condition was interfacial sedimentation in which the supernatant phase and the sedimentation phase formed a clear interface and sedimented, and the sedimentation velocity at the interface was 1.0 mm / s. Further, the catalyst concentration in the supernatant phase one minute after the stirring was stopped was 800 ppm by weight. (3) Stirring tank flow reaction Using the same reactor as in Example 1, an alkylation reaction of benzene with ethylene was performed under the following conditions.

Reaction conditions Catalyst: 100 g of (1) H-β (slurry concentration: 7.
9 wt%) Benzene supply rate: 2 liters / hr Oil extraction linear velocity in settler: 0.18 mm / s Pressure: 15 kg / cm ² G Temperature: 180 ° C. Stirring: 1000 rpm Results The reaction results at each reaction time are as follows. Show.

Reaction time (hr) 3 50 Catalyst concentration (weight ppm) in spilled oil 800 700 ε 0.4 0.15 Ethylated benzene selectivity (%) 99.8 99.8

[0052]

EXAMPLE 4 (1) catalyst PQ Corporation Ltd. _{H-β (SiO 2 / Al} 2 O 3 =
25) was classified by sedimentation separation in water to obtain H-β having an average particle size of 150 μm. (2) Sedimentation and Separation Experiment H-β of (1) was added to the same benzene / ethylbenzene mixture as in Example 1 to obtain a 21 wt% slurry. Using this, the sedimentation separation situation was observed by the same operation as in (2) of Example 1.

As for the sedimentation condition, the supernatant phase and the sedimentation phase did not form a clear interface, and the sedimentation phase particles formed a sedimentary phase in a few minutes. This settling is bulk settling, about 90% of all particles are 4 m
Although it had a high sedimentation velocity of m / s or more, fine powder with extremely slow sedimentation was present in the supernatant phase. The catalyst concentration in the supernatant phase 1 minute after the stirring was stopped was 1500 ppm by weight. (3) Stirring tank flow reaction Using H-β of (1) as a catalyst and using a device provided with a filter for collecting the effluent catalyst of Example 2, a continuous alkylation reaction of benzene with ethylene was carried out under the following conditions. I went there. The catalyst collected by the filter was returned to the reactor for reaction every 10 hours.

Reaction conditions Catalyst amount: 270 g (slurry concentration: 21% by weight) Benzene supply rate: 10 liter / hr Oil withdrawal linear velocity from settler: 0.9 mm / s Pressure: 20 kg / cm ² G Temperature: 190 ° C. Stirring: 1000 rpm Results The reaction results at each time are shown below. Reaction time (hr) 3 103 303 Catalyst concentration in output oil (ppm by weight) 1400 1300 1350 ε 0.58 0.55 0.51 Selectivity of ethylated benzene (%) 99.8 99.8 99.8

[0055]

Example 5 (1) Sedimentation Experiment H-β of Example 1 was added to a benzene / ethylbenzene mixture to prepare a 1 wt% slurry. Using this slurry, the sedimentation situation was observed in the same manner as in (2) of Example 1.

Regarding the sedimentation condition, bulk sedimentation was observed without forming a clear interface between the supernatant phase and the sedimentation phase. (2) Continuous flow reaction Using the H-β of (1) as a catalyst, the size of the Settler was changed in the same reactor as in Example 1 to carry out an alkylation reaction of benzene with ethylene. Settler separation cross section: 5 cm ² Settler volume: 32 c
m ³ Reaction condition Catalyst amount: 13 g (slurry concentration: 1 wt%) Benzene supply rate: 0.5 liter / hr Oil withdrawal linear velocity in settler: 0.27 mm / s Pressure: 15 kg / cm ² G Temperature: 185 ° C. Agitation: 1000 rpm Results The reaction results at each reaction time are shown below.

Reaction time (hr) 3 10 Catalyst concentration in output oil (ppm by weight) 1200 1200 ε 0.5 0.35 Ethylated benzene selectivity (%) 99.8 99.8

[0058]

Example 6 (1) Preparation of catalyst 60.7 g of NaAlO ₂ was added to 3150 g of a 10 wt% concentration tetraethylammonium hydroxide aqueous solution to obtain a uniform solution. Powdered SiO ₂ (nip seal) 70
5 g was added and the mixture was charged into a 5 liter autoclave equipped with a stirrer and crystallized at 155 ° C. for 10 days with stirring at 500 rpm.

The obtained product was filtered and washed with water, and then 12
It was dried at 0 ° C. for 4 hours and then calcined at 450 ° C. for 5 hours under air flow. Then, after cooling to room temperature, 0.15N
60% by adding 10% by weight slurry to nitric acid aqueous solution
Ion exchange was performed for 2 hours. Then, the slurry was filtered, washed with water, and then dried at 120 ° C. for 5 hours to obtain an H-type. This product was identified as zeolite β by X-ray diffraction analysis of the obtained powder. The SiO ₂ / Al ₂ O ₃ ratio determined by fluorescent X-ray analysis was 28.

The average particle diameter of the H-β obtained from the scanning electron micrograph was 1.0 μm. (2) Sedimentation and Separation Experiment H-β prepared in (1) was added to a benzene / ethylbenzene mixture to form an 11 wt% slurry. Using this slurry, the sedimentation situation was observed by the same operation as in (2) of Example 1.

The sedimentation condition was interfacial sedimentation in which the supernatant phase and the sedimentation phase formed a clear interface and sedimentation, and the descending speed of the interface was 1.2 mm / s. The catalyst concentration in the supernatant phase was 150 ppm by weight 1 minute after the stirring was stopped. (3) Stirring tank flow reaction Using the H-β obtained in (1) as a catalyst, an alkylation reaction of benzene with ethylene was carried out in a reaction device having a stirring tank and an external settler shown in FIG.

Reactor volume: 2 liter Slurry hold-up: 1500 cm ³ Settler separation cross section: 25 cm ² Settler volume: 200 cm ³ Reaction conditions Catalyst amount: 150 g (slurry concentration: 11 wt%) Benzene feed rate: 2.9 liters / hr Settler oil withdrawal linear velocity: 0.32 mm / s Pressure: 20 kg / cm ² G Temperature: 180 ° C. Stirring: 1000 rpm Results The reaction results at each reaction time are shown below.

Reaction time (hr) 3 50 Catalyst concentration (weight ppm) in spilled oil 100 95 ε 0.8 0.7 Ethylated benzene selectivity (%) 99.4 99.4

[0064]

Example 7 (1) Sedimentation Separation Experiment HY type zeolite (SiO ₂ / Al ₂ O ₃ ratio: 6.0)
Average particle size: 100 μm) was added to the benzene / ethylbenzene mixture to give a 16 wt% slurry. Using this slurry, the sedimentation condition was observed by the same operation as in Example 1 (2).

Regarding the sedimentation condition, the clear phase and the sedimentation phase did not form a clear interface, and the sedimentation phase formed a sedimentary phase in a few minutes. 90% of all particles had a sedimentation velocity of 3 mm / s or more. In addition, the catalyst concentration in the supernatant phase was 2500 after 1 minute from stopping the stirring.
It was ppm by weight. (2) Stirring tank flow reaction Using the reactor with the internal settler used in Example 1,
The benzene alkylation reaction with ethylene was performed under the following conditions.

Reaction conditions Catalyst amount: 200 g (slurry concentration: 16% by weight) Benzene supply rate: 7 liter / hr Oil withdrawal linear velocity in settler: 0.63 mm / s Pressure: 12 kg / cm ² G Temperature: 175 ° C. Stirring : 1000 rpm Results The reaction results at each time are shown below.

Reaction time (hr) 3 10 Catalyst concentration in output oil (ppm by weight) 2000 1800 ε 0.15 0.07 Ethylated benzene selectivity (%) 99.0 99.0

[0068]

Example 8 (1) Sedimentation and Separation Experiment H-β of Example 1 was added to a benzene / cumene equal weight mixture to prepare a 20 wt% slurry. This slurry was charged into a 1 liter glass autoclave, the gas phase was replaced with nitrogen, and the temperature was raised to 120 ° C. to a pressure of 8 k.
It was set to g / cm ² .

1 of this slurry was prepared by using a turbine blade (diameter: 30 mm) installed in a glass autoclave.
After stirring at 000 rpm for 5 minutes, the stirring was stopped and the state of zeolite sedimentation was visually observed. The sedimentation condition was interfacial sedimentation, and the supernatant phase and the sedimentation phase formed a clear interface, and consolidation of the sedimentation phase was hardly observed in about 10 minutes. The observed interfacial sedimentation velocity was 1.6 mm / s. The zeolite concentration in the supernatant phase 1 minute after the stirring was stopped was 110 ppm by weight. (2) Stirred tank flow reaction In the stirred tank reactor having a settler inside the reactor of (3) of Example 1, benzene was alkylated with propylene using the above catalyst.

Reaction conditions Slurry hold-up: 1400 cm ³ Catalyst amount: 252 g (slurry concentration: 20% by weight) Benzene supply rate: 7.0 liters / hr Liquid propylene supply rate: 2.5 liters / hr Oil extraction line in settler Speed: 0.63 mm / s Reaction pressure: 13 kg / cm ² G Reaction temperature: 160 ° C. Stirring: 1000 rpm Results The reaction results at each reaction time are shown below.

Reaction time (hr) 3 100 Catalyst concentration (weight ppm) in spilled oil 100 95 Propylation rate 0.5 0.35 Propylation benzene selectivity (%) 99.8 99.8

[0072]

Example 9 Using the same HY type zeolite as in Example 7, a transalkylation reaction of benzene and diethylbenzene was carried out in the same reaction apparatus as in (3) of Example 1. Reaction conditions Catalyst amount: 200 g (slurry concentration: 16% by weight) Raw material composition: benzene / diethylbenzene equivalent weight mixture Raw material liquid supply rate: 1 liter / hr Reaction pressure: 20 kg / cm ² G (nitrogen pressure) Reaction temperature: 200 ° C. Results The reaction results at each time are shown below.

Reaction time (hr) 3 50 Catalyst concentration in oil spill (ppm by weight) 1000 900 Liquid composition (weight ratio) Benzen / Ethylbenzene / Diethylbenzene / Other 35.5 / 38/25 / 1.5 38/31/30/1

[0074]

Example 10 Using H-β of Example 1 as a catalyst, a transalkylation reaction of benzene and diisopropylbenzene was carried out in the same reaction apparatus as in (3) of Example 1. Reaction conditions Catalyst amount: 150 g (slurry concentration: 12% by weight) Raw material composition: benzene / diisopropylbenzene equivalent weight mixture Raw material liquid supply rate: 1 liter / hr Reaction pressure: 20 kg / cm ² G (nitrogen pressure) Reaction temperature: 160 ° C. Results The results at each reaction time are shown below.

Reaction time (hr) 3 100 Catalyst concentration in spilled oil (ppm by weight) 80 70 Liquid composition (weight ratio) Benzen / Cumen / Diisoprohydrobenzen 40/30/30 41/28/31

[0076]

Example 11 (1) Sedimentation Separation Experiment H-ZSM-5 (SiO ₂ / Al ₂ O ₃ ratio: 30, average particle size: 1.5 μm) was added to meta-xylene to prepare a 20 wt% slurry. . This slurry was placed in a glass autoclave and a sedimentation separation experiment was conducted in the same manner as in (2) of Example 1. As for the sedimentation condition, interfacial sedimentation was observed.
The sedimentation velocity at the interface was 0.5 mm / s, and the catalyst concentration in the supernatant phase 1 minute after the stirring was stopped was 200 wtpp.
It was m. (2) Stirring tank flow reaction An isomerization reaction of xylenes was performed using the above catalyst in the same reaction apparatus as in (3) of Example 1.

Reaction conditions Catalyst amount: 252 g (slurry concentration: 20% by weight) Raw material composition (weight ratio): Ethylbenzene / Metaxylene / Orthoxylene = 1
6/61/23 Raw material liquid supply rate: 3 liters / hr Reaction pressure: 30 kg / cm ² G (nitrogen pressure) Reaction temperature: 280 ° C. Stirring: 1000 rpm Results Results at each reaction time are shown below.

Reaction time (hr) 3 100 Catalyst concentration in oil spill (wt ppm) 80 70 Para-xylene concentration in xylene (wt%) 23 20

[0079]

COMPARATIVE EXAMPLE 1 H-β of Example 1 was compression molded for 9 to 20 minutes.
A molded body of mesh was obtained. Using this molded body as a catalyst, an alkylation reaction of benzene with ethylene was carried out in a fixed-bed liquid ring upflow reaction mode. Reaction conditions Reactor: Inner diameter 10.5 mm, length 500 mm, stainless steel reaction tube with heat medium jacket Catalyst amount: 2.5 g Benzene supply rate: 0.13 liters / hr Ethylene gas supply rate: 13.14 normal liters /
hr Reaction pressure: 20 kg / cm ² G (liquid sealing pressure) Heat medium temperature: 170 ° C. Maximum catalyst layer temperature: 190 ° C. Results Epsilon at the 6th hour after the start of the reaction was 0.038, and ethylated benzene selectivity was 99.3. %Met. The productivity when all ethylbenzene is ethylbenzene is 2.15g.
-Ethylbenzene / g-cat / hr. On the other hand, the productivity of Example 1 was 25.4 g-ethylbenzene / g-c.
Since it is at / hr, it can be seen that the productivity of the slurry system of the present application is high.

[0080]

EFFECTS OF THE INVENTION By the combination of the highly active slurry system of the present invention and the simple process of sedimentation, the conversion reaction of aromatic compounds can be continuously carried out with high productivity. This is extremely advantageous for industrial implementation.

[Brief description of drawings]

FIG. 1 is a scanning electron micrograph of the H-β particle structure obtained in (1) of Example 1.

FIG. 2 is a schematic diagram of a reaction device used in the stirring tank flow reaction of (3) of Example 1.

FIG. 3 is a scanning electron micrograph of the H-β particle structure in (3) of Example 3.

FIG. 4 is a schematic view of a reaction device used in the stirring tank flow reaction of (3) of Example 6.

Claims (16)

[Claims] 1. When a liquid reaction product is obtained by converting an aromatic compound in a liquid phase or a gas-liquid mixed phase in the presence of a zeolite catalyst, (1) a liquid product in a suspension fluidized bed of zeolite. (2) A step of separating a zeolite suspension mainly composed of a liquid product into a liquid reaction product having a zeolite content of 0.3% by weight or less and a concentrated zeolite suspension by sedimentation separation ( 3) A continuous reaction method of an aromatic compound, which comprises a step of circulating the concentrated zeolite suspension into a suspension fluidized bed. 2. A process according to claim 1, characterized in that the sedimentation separation from the zeolite suspension is a bulk sedimentation separation. 3. The method according to claim 1, wherein the sedimentation separation from the zeolite suspension is an interfacial sedimentation separation. 4. The method according to claim 1, wherein the zeolite is zeolite β. 5. The zeolite has an average particle size of 100 to 50.
The zeolite β having a diameter of 0 μm.
The method described in. 6. The zeolite has an average particle size of 0.01 to 1
The method according to claim 3, wherein the zeolite β is 00 μm, and the zeolite concentration in the suspension is in the range of 3 to 30% by weight. 7. The method according to claim 1, wherein the aromatic compound is benzene and / or an alkylated benzene having an alkyl group having 1 to 4 carbon atoms. 8. The method according to claim 1, wherein the conversion reaction of the aromatic compound is an alkylation reaction. 9. The method according to claim 8, wherein the alkylating agent is an olefin having 2 to 4 carbon atoms. 10. The method of claim 8 wherein the alkylating agent is ethylene. 11. The method according to claim 8, wherein the alkylation reaction of the aromatic compound is an ethylation reaction of benzene with ethylene. 12. The method according to claim 8, wherein the zeolite is zeolite β. 13. The method according to claim 8, wherein the sedimentation separation is an interfacial sedimentation separation. 14. The method according to claim 1, wherein the conversion reaction of the aromatic compound is a transalkylation reaction. 15. The method according to claim 14, wherein the aromatic compound is benzene and an alkylated benzene having an alkyl group having 1 to 4 carbon atoms. 16. The method of claim 15, wherein the alkylated benzene is ethylated benzene.