JP5300348B2 - Method for producing alkylated aromatic compound and method for producing phenol - Google Patents

Description

  The present invention relates to a method for producing an alkylated aromatic compound and a method for producing phenol.

  The cumene method for producing phenol using cumene as a starting material is known, but in the cumene method, the produced phenol and an equimolar amount of acetone are always by-produced. By-product acetone has a wide range of uses as a solvent or organic synthesis raw material, but depending on the market trend at that time, acetone may be excessive or the market situation may be bad, which causes the economics of phenol to be produced to decrease It has become. Cumene is usually produced by alkylating benzene with propylene. Propylene is produced by the thermal decomposition of naphtha and is often a bottleneck in cumene production due to the shortage of propylene due to the balance of demand for ethylene and propylene produced at the same time.

  In order to avoid this bottleneck, a method has been proposed in which acetone co-produced at the time of phenol production is hydrogenated to isopropanol, which is further dehydrated to propylene and recycled as a raw material for cumene production or the like (Patent Document 1). reference). However, this method has a problem that two steps, a hydrogenation step and a dehydration step, increase.

Therefore, in order to shorten the process, there has been proposed a method for producing cumene by reacting with benzene by using isopropanol obtained by hydrogenation of acetone as an alkylating agent as it is without dehydration (see Patent Documents 2 to 4). .
Japanese Patent Laid-Open No. 2-174737 JP-A-2-231442 Japanese Patent Laid-Open No. 11-35497 Special table 2003-523985 gazette

  In the method of producing an alkylated aromatic compound using an alcohol as an alkylating agent in the presence of a solid acid catalyst, in addition to a reaction in which the alcohol directly alkylates the aromatic hydrocarbon, an olefin obtained by dehydration of the alcohol The alkylation reaction of aromatic hydrocarbons by means of occurs simultaneously.

  In addition, in the hydrogenation reaction of a ketone, an excess mole of hydrogen is usually fed to the ketone in order to increase the conversion rate. For this reason, there is a possibility that surplus hydrogen resulting from the feeding of an excess mole of hydrogen or hydrogen dissolved in the generated alcohol may also be present in the alkylation step of the aromatic compound with the alcohol.

  Therefore, when an alkylated aromatic compound is produced using the alcohol obtained by the hydrogenation reaction of the ketone as an alkylating agent, the catalyst used for the hydrogenation reaction of the ketone is pulverized by catalyst crushing or the like. The hydrogenated catalyst flows into the alkylation process, hydrogen and the hydrogenation catalyst coexist, and the olefin obtained by dehydration of alcohol may be hydrogenated to generate paraffin as a by-product.

Since this paraffin does not act as an alkylating agent, it does not contribute to the formation of an alkylated aromatic compound, and causes a significant reduction in the productivity of the alkylated aromatic compound.
The disadvantages described above are problems that must be solved when an alkylated aromatic compound is obtained using an alcohol obtained by the hydrogenation reaction of a ketone as an alkylating agent.

  The present invention is a method for producing an alkylated aromatic compound in which a hydrogenation reaction of a ketone is performed in the presence of a metal catalyst, and the resulting alcohol is used as an alkylating agent to react with an aromatic hydrocarbon. It aims at providing the method for manufacturing alkylated aromatic compounds, such as cumene. Moreover, it aims at providing the manufacturing method of the phenol which has the process of obtaining cumene by this method.

  In order to solve the above-mentioned problems, the present inventors have made extensive studies, and as a result, installed a filter between the step of hydrogenating the ketone and the step of alkylating the aromatic compound with alcohol. Thus, it has been found that the metal catalyst acting as a hydrogenation catalyst, hydrogen and olefin can be prevented from coexisting and by-product paraffin can be suppressed.

That is, the method for producing an alkylated aromatic compound and the method for producing phenol according to the present invention relate to the following (1) to (8).
(1) A step of performing a hydrogenation reaction of a ketone in the presence of a metal catalyst containing at least one metal element selected from the group consisting of copper, nickel, cobalt and rhenium to obtain a reaction liquid containing alcohol (step 1) )When,
An alkylated aromatic comprising a step of performing an alkylation reaction of an aromatic compound with an alcohol in the reaction solution in the presence of a solid acid catalyst after passing the reaction solution through a filter (step 2). Compound production method.

  (2) The metal catalyst further includes at least one element selected from the group consisting of Group IIB elements, Group IIIA elements, Group VIB elements and Group VIII elements (excluding nickel and cobalt). The method for producing an alkylated aromatic compound according to (1).

(3) The method for producing an alkylated aromatic compound according to (1) or (2), wherein the solid acid catalyst is zeolite.
(4) The method for producing an alkylated aromatic compound according to (3), wherein the zeolite is a zeolite having a 10-12 membered ring structure.

(5) The method for producing an alkylated aromatic compound according to any one of (1) to (4), wherein the metal catalyst and the solid acid catalyst are packed in separate reactors.
(6) The metal catalyst and the solid acid catalyst are packed in the same reactor,
A catalyst layer made of a metal catalyst is formed on the upstream side, and a catalyst layer made of a solid acid catalyst is formed on the downstream side,
The method for producing an alkylated aromatic compound according to any one of (1) to (4), wherein a filter is present between the catalyst layer comprising a metal catalyst and the catalyst layer comprising a solid acid catalyst. .

(7) The method for producing an alkylated aromatic compound according to any one of (1) to (6), wherein the aromatic compound is benzene and the ketone is acetone.
(8) In the method for producing phenol including the following steps (a) to (e), steps (c) and (d) are carried out according to the method for producing an alkylated aromatic compound described in (7). A method for producing phenol.
Step (a): Step of oxidizing cumene to convert it to cumene hydroperoxide Step (b): Step of acid decomposition of cumene hydroperoxide to obtain phenol and acetone Step (c): obtained in the above step (b) Step (d) for obtaining isopropanol by hydrogenation reaction of acetone: Step (e) for synthesizing cumene by reacting benzene and isopropanol using isopropanol obtained in step (c) above: Step (d) Step of circulating cumene obtained in step (a) to step (a)

  According to the method for producing an alkylated aromatic compound of the present invention, an alkylated aromatic compound such as cumene is converted from a paraffin by-product from an alcohol obtained by hydrogenation of a ketone such as acetone and an aromatic compound such as benzene. It can be obtained by an industrially practical method in which life is suppressed. Moreover, the obtained cumene has no problem in terms of quality compared to cumene obtained from propylene and benzene.

  The method for producing phenol of the present invention reuses the acetone co-produced in the production of phenol without increasing the number of steps of the conventional cumene method by applying the method for producing an alkylated aromatic compound. It becomes possible. Therefore, the method for producing phenol of the present invention can produce phenol significantly and economically in terms of process.

  The method for producing an alkylated aromatic compound of the present invention includes a hydrogenation reaction of a ketone in the presence of a metal catalyst containing at least one metal element selected from the group consisting of copper, nickel, cobalt, and rhenium, and an alcohol. A step of obtaining a reaction solution containing (Step 1), and a step of performing an alkylation reaction of an aromatic compound with an alcohol in the reaction solution in the presence of a solid acid catalyst after passing the reaction solution through a filter (Step 2) ).

  In the method for producing an alkylated aromatic compound of the present invention, the step 1 and the step 2 may be performed in separate reactors or may be performed in one reactor. That is, the metal catalyst and the solid acid catalyst may be charged in separate reactors, or the metal catalyst and the solid acid catalyst may be charged in the same reactor.

  In the present invention, when the metal catalyst and the solid acid catalyst are filled in separate reactors, at least the lower part of the reactor filled with the metal catalyst is filled with the solid acid catalyst. A filter exists in the upper part of the reactor or in a pipe between the reactor filled with the metal catalyst and the reactor filled with the solid acid catalyst, and the filter exists in the two or more locations. May be. When the metal catalyst and the solid acid catalyst are packed in the same reactor, a catalyst layer made of a metal catalyst is formed on the upstream side, and a catalyst layer made of a solid acid catalyst on the downstream side. And a filter exists between the catalyst layer made of a metal catalyst and the catalyst layer made of a solid acid catalyst.

  The type of the filter used in the present invention is not particularly limited as long as it is a filter that does not change in shape or deteriorate due to the reaction temperature range or the raw material, and a filter made of glass fiber, cellulose fiber, or silica fiber is preferably selected. In the present invention, a plurality of filters may be used. When a plurality of filters are used, each filter may be the same material or a different material, and the retained particle diameter may be the same or different. .

  The retained particle size of the filter used in the present invention is not particularly limited, but is preferably retained from the viewpoint of pressure loss during production of the alkylated aromatic compound and capture of fine powder of the metal catalyst used in the hydrogenation reaction of the ketone. A filter having a particle size of 0.1 to 10 μm is used.

In the method for producing an alkylated aromatic compound of the present invention, examples of the aromatic compound include benzene, naphthalene and the like, among which benzene is preferable, and the ketone is
Acetone, methyl ethyl ketone and the like can be mentioned, among which acetone is preferred.

The metal catalyst used in the present invention comprises a metal catalyst containing at least one metal element selected from the group consisting of copper, nickel, cobalt and rhenium. The metal catalyst may be a single element of the metal element itself, a metal oxide such as ReO ₂ , Re ₂ O ₇ , NiO, or CuO, a metal chloride such as ReCl ₃ , NiCl ₂ , or CuCl ₂ , or Ni—Cu. Ni-Cu-C
It may be a cluster metal such as r.

  The metal catalyst may further contain at least one element selected from the group consisting of Group IIB elements, Group IIIA elements, Group VIB elements, and Group VIII elements (excluding nickel and cobalt). .

Specific examples of the element include Zn, Cd, Hg, B, Al, Ga, In, Tl, Cr, Mo, W, Fe, Ru, Os, Rh, Ir, Pd, and Pt.
Among these, when the metal catalyst contains Zn or Al in addition to copper, it is preferable in terms of the effect of extending the catalyst life.

  The metal catalyst containing at least one metal element selected from the group consisting of copper, nickel, cobalt, and rhenium is not particularly limited as long as it can hydrogenate a carbonyl group of a ketone to obtain an alcohol. What is commercially available as a so-called hydrogenation catalyst can be used as it is, and those supported on various carriers are commercially available, and these may be used. For example, a 5% Re carbon catalyst, a 5% Re alumina catalyst, a silica alumina supported nickel catalyst, and those in which the supported amounts of the listed types are changed to 1% or 0.5%, etc. may be mentioned. As the carrier, it is preferable to select at least one of silica, alumina, silica alumina, titania, magnesia, silica magnesia, zirconia, and carbon.

  The shape of the metal component containing at least one metal element selected from the group consisting of copper, nickel, cobalt, and rhenium is not particularly limited, and may be spherical, cylindrical, extruded, or crushed, and the size of the particle. Moreover, it may be selected according to the size of the reactor in the range of 0.01 mm to 100 mm.

  The solid acid catalyst used in the present invention is a catalyst having a function as an acid, and may be anything generally called a solid acid, such as zeolite, silica alumina, alumina, sulfate ion supported zirconia, WO3 supported zirconia, or the like. be able to.

  In particular, zeolite, which is an inorganic crystalline porous compound composed of silicon and aluminum, is a solid acid catalyst suitable for the present invention in terms of heat resistance and selectivity of the target alkylated aromatic compound (cumene). .

  When producing cumene as the alkylated aromatic compound, the zeolite is preferably a zeolite having a 10- to 12-membered ring structure having pores similar to the molecular diameter of cumene, β-type, MCM-22 Is particularly preferred.

  Examples of zeolite having a 12-membered ring structure include Y type, USY type, mordenite type, dealuminated mordenite type, β type, MCM-22 type, MCM-56 type, etc., particularly β type, MCM-22. The mold, MCM-56 type, is a preferred structure.

The composition ratio of silicon and aluminum in these zeolites may be in the range of 2/1 to 200/1, and 5/1 to 100/1 is particularly preferable from the viewpoint of activity and thermal stability. Furthermore, a so-called isomorphously substituted zeolite in which the aluminum atom contained in the zeolite skeleton is substituted with a metal other than aluminum such as Ga, Ti, Fe, Mn, and B can also be used.

  The shape of the solid acid catalyst is not particularly limited and may be spherical, cylindrical, extruded, or crushed, and the particle size can be, for example, in the range of 0.01 mm to 100 mm. Select according to the size.

  In practicing the present invention, the method is carried out by a continuous flow method using a solid catalyst. In that case, it can be carried out in any form of a liquid phase, a gas phase, and a gas-liquid mixed phase. A fixed bed reactor is selected as the catalyst filling method, the reaction method may be either gas-liquid co-current or counter flow, and the flow direction may be either downward flow or upward flow.

  A merry-go-round system in which two or three reactors are arranged in parallel to carry out the reaction in the remaining one or two reactors while one reactor is being regenerated in order to maintain cumene production You can take it. Furthermore, when there are three reactors, a method may be used in which the other two reactors are connected in series to reduce fluctuations in production.

  In order to achieve high productivity, the feed rate of the raw material in the present invention is based on the weight of the catalyst in the reactor filled with the metal catalyst for performing Step 1 when Step 1 and Step 2 are performed in separate reactors. The liquid weight based space velocity (WHSV) is usually 100 or less, more preferably 50 or less, and even more preferably 20 or less. The liquid weight based space velocity with respect to the catalyst weight in the reactor filled with the solid acid catalyst for performing step 2 ( WHSV) is usually 50 or less, more preferably 20 or less, and even more preferably 10 or less. When Steps 1 and 2 are performed in a single reactor, the liquid weight reference space velocity (WHSV) relative to the catalyst weight in the reactor is usually 50 or less, more preferably 20 or less, and even more preferably 10 or less. . The liquid weight reference space velocity (WHSV) is usually 1 or more.

In the above range, an alkylated aromatic compound such as cumene can be produced with high yield.
In the present invention, the amount ratio of the metal catalyst to the solid acid catalyst is not particularly limited, but is usually at least one metal element selected from the group consisting of copper, nickel, cobalt and rhenium contained in the metal catalyst. The weight ratio of the weight to the solid acid catalyst (metal element / solid acid catalyst) is usually 0.001 to 10, preferably 0.01 to 2.

  In principle, the aromatic compound used in the present invention may be at least equimolar with the ketone. From the viewpoint of separation and recovery, the aromatic compound is preferably 1 to 15 times mol, preferably 1 to 5 times mol with respect to the ketone. It is more preferable that

Moreover, it is preferable that it is 1-20 times mole with respect to a ketone, and, as for the hydrogen used for this invention, it is more preferable that it is 1-10 times mole with respect to the point of isolation | separation collection | recovery.
When the method for producing an alkylated aromatic compound of the present invention is carried out in a fixed bed reactor, the reaction temperature in the reactor is usually in the range of 100 to 300 ° C, preferably in the range of 120 to 250 ° C. . The reaction pressure is in the range of 0.5 to 10 MPaG, preferably 2 to 5 MPaG.

In addition, as a manufacturing method of the alkylated aromatic compound of this invention, the following two aspects can be illustrated.
A first aspect is the method for producing an alkylated aromatic compound, wherein the hydrogenation reaction of the ketone is performed in the presence of the aromatic compound, and the reaction solution containing the alcohol is a reaction solution containing the alcohol and the aromatic compound. In another aspect, the aromatic compound used in the alkylation reaction of the aromatic compound with the alcohol is an aromatic compound contained in the reaction solution. That is, in the method for producing an alkylated aromatic compound according to the first aspect, in the presence of a metal catalyst containing at least one metal element selected from the group consisting of copper, nickel, cobalt, and rhenium, and an aromatic compound, A step of performing a hydrogenation reaction to obtain a reaction solution containing an alcohol and an aromatic compound (Step 1), and after passing the reaction solution through a filter, the reaction is carried out with the alcohol in the reaction solution in the presence of a solid acid catalyst. And a step of performing an alkylation reaction of the aromatic compound in the liquid (step 2).

  In the first embodiment, the hydrogenation reaction of ketone is performed in the step 1 in the presence of an aromatic compound. That is, in the first embodiment, an aromatic compound, a ketone, and hydrogen are introduced into Step 1.

  In addition, since the aromatic compound is introduced at the time of step 1, in the first embodiment, the metal catalyst and the solid acid catalyst may be charged in the same reactor. In this case, step 1 and step 2 are performed in the same reactor.

  According to a second aspect, in the method for producing an alkylated aromatic compound, the step 1 is performed under a condition in which the aromatic compound is not present or almost absent, and the reaction solution obtained in the step 1 is mixed with the aromatic compound. In this embodiment, step 2 is performed.

  That is, the method for producing an alkylated aromatic compound according to the second aspect includes a hydrogenation reaction of a ketone in the presence of a metal catalyst containing at least one metal element selected from the group consisting of copper, nickel, cobalt, and rhenium. And a step of obtaining a reaction liquid containing alcohol (Step 1), and after passing the reaction liquid through a filter, an alkylation reaction of an aromatic compound is performed with the alcohol in the reaction liquid in the presence of a solid acid catalyst. A step (step 2), wherein the reaction solution and the aromatic compound are mixed before or after passing the reaction solution through the filter.

The method for producing phenol according to the present invention is a method for producing phenol including the following steps (a) to (e), wherein steps (c) and (d) are carried out according to the method for producing an alkylated aromatic compound described above. It is characterized by. In addition, when implementing the manufacturing method of the above-mentioned alkylated aromatic compound as process (c) and (d) of the manufacturing method of a phenol, the said aromatic compound is benzene and a ketone is acetone.
Step (a): Step of oxidizing cumene to convert it to cumene hydroperoxide Step (b): Step of acid decomposition of cumene hydroperoxide to obtain phenol and acetone Step (c): obtained in the above step (b) Step (d) for obtaining isopropanol by hydrogenation reaction of acetone: Step (e) for synthesizing cumene by reacting benzene and isopropanol using isopropanol obtained in step (c) above: Step (d) The step of circulating the cumene obtained in step (a) to the step (a) is the phenolno production method of the present invention. In the steps (a) and (b), phenol is produced from cumene, and acetone as a by-product is produced in step (c) by isopropanol. In step (d), cumene is produced, and in step (e), the cumene obtained in step (d) is processed. Since it circulates as much as (a), it is theoretically unnecessary to introduce acetone from outside the reaction system, which is excellent in terms of cost. In an actual plant, it is difficult to recover 100% of acetone, and at least the reduced amount of acetone is newly introduced into the reaction system.

  In the method for producing phenol of the present invention, there is no problem even if various improved methods are provided.

EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.

[Example 1]
Stainless steel vertical reaction tube with an inner diameter of 38.4 mm and a length of 4800 mm, metal pack from the top of the reaction tube, helipack (Tokyo Special Wire Mesh): 100 g, β-zeolite catalyst (φ1.5 mm pellet form as solid acid catalyst) , Manufactured by Tosoh): 1806g (2895mm), 25 sheets of glass fiber filter paper (Kiriyama Seisakusho, φ40mm, retention particle diameter 0.8μm) as a filter, Cu-Zn catalyst (φ3mm x H3mm cylindrical shape, made by Zude Chemie, element Mass% Cu 32 to 35%, Zn 35 to 40%, Al 6 to 7%, atomic ratio of Zn to Cu 1.0 to 1.2)): 885 g (602 mm), helipak: 100 g were sequentially filled.

After filling, isopropanol: 24L / h was poured from the top of the reactor and the catalyst was washed for 1 hour. After completion of the washing, the catalyst was activated for 3 hours by flowing hydrogen: 630 NL / h in the reactor at 3 MPaG, preheating temperature: 100 ° C.

Benzene: 7.7 L / h, acetone: 0.61 L / h, hydrogen: 348 NL / h were fed into the reactor, the inlet temperature of the layer formed from the metal catalyst was 181 ° C, and the inlet temperature of the layer formed from the zeolite catalyst was Maintained at 175 ° C.
The reaction conditions were set to low cumene selectivity in order to clarify whether propane was produced. The reaction results are shown in Table 1. This shows that cumene selectivity is 34.7%, cumene selectivity is 35.7%, propane selectivity is 1.9%, and propylene selectivity is 41.8%, and propane by-product is suppressed.

In addition, after the reaction was completed, the content of metals (Cu, Zn) in the zeolite was analyzed in order to confirm whether or not the Cu-Zn catalyst was mixed into the zeolite catalyst. There are four analysis points, 0, 300, 1000, and 2800 mm from the top of the zeolite layer.

As an analysis method, first, dilute sulfuric acid and hydrofluoric acid were added to zeolite, followed by heat treatment and then incinerated. Next, the incinerated zeolite was melted with potassium hydrogen sulfate, dissolved in dilute nitric acid, fixed in pure water, and then the metal components were quantified by ICP emission spectrometry (apparatus: Varian-Vista-MPX). . The analysis results are shown in Table 2. As a result, almost no Cu-Zn catalyst was mixed into the zeolite catalyst, and the effect of preventing the metal catalyst (Cu-Zn catalyst) from being mixed with the filter was confirmed.

[Comparative Example 1]
A metal catalyst (Cu-Zn catalyst) and a solid acid catalyst (zeolite catalyst) were packed in one reactor in layers, and evaluation was performed without inserting a filter (glass fiber filter paper) between the two catalysts.

In the experimental apparatus and experimental conditions described in Example 1, the catalyst test was performed in the same manner as in Example 1 except that no filter was inserted between the catalysts. The reaction results are shown in Table 1. As a result, cumene selectivity: 30.7%, cumene selectivity: 33.2%, propane selectivity was 57.2%, propylene selectivity: 5.5%, and a large amount of propane was by-produced.

Table 2 shows the results of the metal content analysis of the zeolite catalyst. From this, the metal content was higher in the upper part, and 30-40 ppm of metal was detected in the lowermost part. Thus, it was proved that when the metal catalyst is mixed in the step 2 of performing the alkylation reaction, propane is by-produced and the reaction result is deteriorated.

Claims (8)

A step of hydrogenating a ketone in the presence of a metal catalyst containing at least one metal element selected from the group consisting of copper, nickel, cobalt and rhenium to obtain a reaction solution containing alcohol (step 1);
A step of performing an alkylation reaction of an aromatic compound with an alcohol in the reaction solution in the presence of a solid acid catalyst after the reaction solution is passed through a filter having a retention particle diameter of 0.1 to 10 μm (step 2). And a method for producing an alkylated aromatic compound.   The metal catalyst further comprises at least one element selected from the group consisting of Group IIB elements, Group IIIA elements, Group VIB elements and Group VIII elements (excluding nickel and cobalt). A process for producing the alkylated aromatic compound according to 1.   The method for producing an alkylated aromatic compound according to claim 1 or 2, wherein the solid acid catalyst is zeolite.   The method for producing an alkylated aromatic compound according to claim 3, wherein the zeolite is a zeolite having a 10-12 membered ring structure.   The method for producing an alkylated aromatic compound according to any one of claims 1 to 4, wherein the metal catalyst and the solid acid catalyst are packed in separate reactors. The metal catalyst and the solid acid catalyst are packed in the same reactor,
A catalyst layer made of a metal catalyst is formed on the upstream side, and a catalyst layer made of a solid acid catalyst is formed on the downstream side,
5. A filter having a retained particle diameter of 0.1 to 10 [mu] m exists between a catalyst layer made of a metal catalyst and a catalyst layer made of a solid acid catalyst. A process for producing an alkylated aromatic compound.   The method for producing an alkylated aromatic compound according to any one of claims 1 to 6, wherein the aromatic compound is benzene and the ketone is acetone. A phenol production method comprising the following steps (a) to (e), wherein steps (c) and (d) are carried out according to the method for producing an alkylated aromatic compound according to claim 7. Manufacturing method.
Step (a): Step of oxidizing cumene to convert it to cumene hydroperoxide Step (b): Step of acid decomposition of cumene hydroperoxide to obtain phenol and acetone Step (c): obtained in the above step (b) Step (d) for obtaining isopropanol by hydrogenation reaction of acetone: Step (e) for synthesizing cumene by reacting benzene and isopropanol using isopropanol obtained in step (c) above: Step (d) Step of circulating cumene obtained in step (a) to step (a)