KR101403517B1 - Method for preparing alpha methyl styrene - Google Patents

Method for preparing alpha methyl styrene Download PDF

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KR101403517B1
KR101403517B1 KR1020100121363A KR20100121363A KR101403517B1 KR 101403517 B1 KR101403517 B1 KR 101403517B1 KR 1020100121363 A KR1020100121363 A KR 1020100121363A KR 20100121363 A KR20100121363 A KR 20100121363A KR 101403517 B1 KR101403517 B1 KR 101403517B1
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cumene hydroperoxide
stream
cumene
cumyl alcohol
hydrogenation reaction
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KR1020100121363A
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KR20120059875A (en
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하승백
유석준
조동현
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주식회사 엘지화학
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Priority to KR1020100121363A priority Critical patent/KR101403517B1/en
Priority to PCT/KR2011/007488 priority patent/WO2012074194A2/en
Priority to CN201180037274.2A priority patent/CN103052611B/en
Priority to JP2013523100A priority patent/JP5635696B2/en
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    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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    • C07—ORGANIC CHEMISTRY
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    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
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    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
    • C07C2527/054—Sulfuric acid or other acids with the formula H2Sn03n+1
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Abstract

The present invention reduces the risk of explosion in the hydrogenation reaction of cumene hydroperoxide with increasing concentration through the selective hydrogenation of cumene hydroperoxide obtained by the oxidation of cumene in the phenol production process under the most stabilized conditions of low concentration and temperature. Which is capable of selectively increasing the amount of alpha methylstyrene and controlling the amount of cumene hydroperoxide by increasing the amount of alpha-methylstyrene to 90% or more to increase the amount of alpha-methylstyrene, To a process for producing methylstyrene.

Description

[0001] The present invention relates to a method for preparing alpha methyl styrene,

The present invention relates to a process for the preparation of alpha methyl styrene for the selective production of alpha methyl styrene.

Alpha-methyl styrene (AMS) has been widely used as an additive in the preparation of certain copolymers and novel polymers such as ABS. In addition, AMS finds its use as an intermediate in the preparation of fine compounds such as unsaturated AMS dimers. These dimers have been used as molecular weight regulators in the preparation of copolymers such as acrylonitrile-butadiene-styrene resins and styrene-butadiene rubbers. The hydrogenation form of the AMS dimer has industrial value as a component in the lubricating composition.

Such AMS is produced as a by-product of the phenol manufacturing process. Generally, phenol and AMS are produced through oxidation and dehydration processes using cumene as a raw material. FIG. 1 is a process diagram schematically showing a conventional process for producing phenol.

Referring to FIG. 1, an existing method is a method in which cumene is oxidized in the presence of oxygen in an oxygen reactor 1 supplied with cumene to produce a stream which is converted into cumene hydroperoxide (CHP) and a small amount of cumyl alcohol (CA) And is conveyed to the reservoir 2, and the CHP-containing stream of about 24% by weight is concentrated to about 82% by weight in the stripper 3. Thereafter, the concentrated CHP and CA-containing streams are fed to a cracking reactor 5 via a reservoir 4 and dehydrated under acid catalysis to produce phenol and acetone from CHP and alpha methyl styrene (AMS) from CA have. However, in the case of the above method, since only 0.035 mol% of CA is produced per 1 mol of CHP in the oxidation process of cumene, the production amount of AMS in the phenol production process is limited by the very small amount of cumyl alcohol produced in the cumene oxidation process.

In order to selectively increase the production amount of AMS, a method of selectively converting a portion of CHP from a stripper to a CA to remove alpha methylstyrene prior to the cleavage reactor have. However, the above method has a low conversion efficiency and low selectivity and thus low process efficiency. Therefore, there is a problem in using the highly concentrated CHP.

In the past, it has been disclosed that the process of converting the hydrogenation process of AMS produced for recycling to an oxidation reactor into cumene, not mainly for the purpose of increasing the AMS, is described (U.S. Patent No. 5,905,178). In addition, the conventional method only attempts to minimize the generation of AMS (U.S. Patent No. 5,530,166), and there is insufficient research to increase the production amount of AMS.

Accordingly, the present invention provides a method for producing alpha methyl styrene, which is used as an additive for ABS or the like, for the selective production of AMS, which is regarded as a by-product in the phenol manufacturing process, through selective hydrogenation of cumene hydroperoxide to cumyl alcohol I want to.

The present invention also provides a method for producing alpha methyl styrene which can control the amount of cumene hydroperoxide stream injected into the hydrogenation process to control the amount of AMS produced according to market demand.

The present invention also relates to a process for the preparation of alpha methylstyrene which is capable of increasing the yield of AMS ultimately by producing low-concentration hydrogenation of the cumene hydroperoxide stream to eliminate the possibility of ignition of cumene hydroperoxide to produce cumyl alcohol stably .

(A) oxidizing cumene to produce a cumene hydroperoxide stream;

(b) separating at least a portion of the cumene hydroperoxide stream without concentration and selectively hydrogenating the catalyst under a noble metal catalyst to produce cumyl alcohol; And

(c) concentrating the reaction product containing the cumyl alcohol and dehydrating it under an acid catalyst to prepare a product containing alpha methylstyrene

≪ RTI ID = 0.0 > a < / RTI >

In the step (b), the cumene hydroperoxide stream may be used in the hydrogenation reaction at a concentration of 5 to 25% by weight. Further, in the step (b), 5 to 50% by weight of the cumene hydroperoxide stream may be separated and used for the hydrogenation reaction. The cumene hydroperoxide stream further comprises cumyl alcohol.

According to the method of the present invention, the degree of selectivity of the hydrogenation reaction may be 95% or more, and the conversion of cumene hydroperoxide may be 95% or more.

In the step (b), hydrogenation reaction proceeds on a part of the cumene hydroperoxide stream. In the step (c), the reaction product containing the cumyl alcohol further comprises a cumene hydroperoxide stream not subjected to the hydrogenation reaction I can do it. The product comprising alpha methyl styrene in step (c) further comprises phenol and acetone. The reactant containing the cumyl alcohol may be concentrated to a concentration of 80 to 82% by weight and used for the dehydration reaction. The method may further comprise, after step (c), neutralizing and distilling the product comprising alpha methyl styrene to obtain alpha methyl styrene, phenol and acetone.

Hereinafter, a method for producing alpha-styrene according to a specific embodiment of the present invention will be described.

In general phenol process, about 25% by weight of cumene hydroperoxide (CHP) solution prepared through three oxidation reactors is concentrated to 80% by weight CHP solution through a stripper, and produced by phenol, acetone and AMS through a decomposition reactor .

However, cumene hydroperoxide is an explosive substance when mixed with air and has a flash point between 57 and 79 ° C. Furthermore, there is a risk of explosion and fire when in contact with organic materials, acids, bases and metal components. In addition, there is a report that the runway reaction temperature decreases as the concentration of cumene hydroperoxide increases, thereby increasing the risk of explosion (Thermochimica acta, 501, 2010, 65-71). Therefore, there is a need for a method for performing the phenol process in a stable manner without using high concentration cumene hydroperoxide as described above.

Therefore, it is very important to carry out the conversion process of cumene hydroperoxide at the most stabilized condition, that is, at a low concentration of cumene hydroperoxide and at a low temperature.

In addition, in the conventional oxidation process of cumene, only cumene alcohol was produced in an amount of 0.035 mol% based on 1 mol of cumene hydroperoxide, and thus there was a limit to increase the production amount of alpha methyl styrene.

Accordingly, the present invention provides a process capable of producing cumyl alcohol in a stable state using a low concentration of cumene hydroperoxide. The present invention also provides a method for increasing the production of cumyl alcohol through hydrogenation of cumene hydroperoxide to cumyl alcohol, followed by dehydration of cumyl alcohol to ultimately increase production of alpha methyl styrene.

According to a preferred embodiment of this invention, there is provided a process for the preparation of cumene hydroperoxide, comprising: (a) oxidizing cumene to produce cumene hydroperoxide stream; (b) separating at least a portion of the cumene hydroperoxide stream without concentration and selectively hydrogenating the catalyst under a noble metal catalyst to produce cumyl alcohol; And (c) concentrating the reactant containing the cumyl alcohol and dehydrating it under an acid catalyst to produce a product containing alpha methyl styrene.

The method of the present invention can be applied not only to a conventional dehydration reaction in a decomposition reactor after concentrating a cumene hydroperoxide stream obtained by oxidation of cumene in a stripper but also to a cumene obtained after the oxidation reaction in a low concentration state before concentration in a stripper, By separating a portion of the hydroperoxide and using it in the catalytic hydrogenation process, the selectivity and conversion to cumyl alcohol can be improved.

Therefore, the present invention is able to convert cumene hydroperoxide into cumyl alcohol in a region where stability at a low concentration is secured in the production process, and the result is far superior to the conventional one. That is, in the present invention, the stream of cumene hydroperoxide before entering the cleavage reactor via the stripper is not used as a reactant for the hydrogenation reaction, and the stability of the process is secured by using cumene hydroperoxide after the cumene oxidation .

According to the present invention, a cumene hydroperoxide stream having a concentration of 5 to 25% by weight is produced through the process of step (a). In addition, a small amount of cumyl alcohol may be contained in the stream through oxidation of the cumene.

In this case, the oxidizing conditions in the step (a) are not particularly limited and can be carried out under general conditions. For example, oxidation of cumene can usually be performed by autoxidation with air-oxygen gas such as air or oxygen-enriched air. This oxidation reaction can be carried out with or without an additive such as an alkali. The normal oxidation reaction temperature is 50 to 200 캜, and the reaction pressure may be atmospheric pressure to 5 MPa. When the additive is used, an alkali metal compound such as NaOH or KOH; Alkaline earth metal compounds; Alkali metal carbonates such as Na 2 CO 3 and NaHCO 3 ; ammonia; Alkali metal ammonium carbonate salts and the like can be used.

Also, in step (a), the oxidation of cumene can be carried out through a plurality of oxidation reactors, preferably three oxidation reactors, used in conventional phenol processes. The step (a) may also include the step of oxidizing a cumene-containing stream having a cumene concentration of 80% or more, preferably 99% or more, in the presence of an oxygen-containing stream to form a cumene hydroperoxide-containing stream.

Further, ordinary initiators may be used to promote oxidation of the cumene, and organic hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide, peroxime free radical initiators, and azo type free radical initiators, etc., Can be used.

The step (b) is a step of increasing the content of cumyl alcohol by performing a hydrogenation reaction using the cumene hydroperoxide stream obtained in the step (a).

For this, in the step (b), the hydrogenation reaction proceeds on a part of the cumene hydroperoxide stream. In the step (b) of producing the cumyl alcohol, 5 to 50% by weight of the cumene hydroperoxide stream is preferably separated and used in the hydrogenation reaction.

The noble metal catalyst used in the hydrogenation reaction may include at least one selected from the group consisting of gold, silver, platinum, palladium, iridium, ruthenium, rhenium, rhodium and osmium. The noble metal catalyst may further include a carrier selected from the group consisting of alumina, silica, clay, carbon, zirconia, titania, mesoporous molecular sieve, and mixtures thereof.

The noble metal catalyst is preferably used in an amount of 1 to 15 parts by weight based on 100 parts by weight of the cumene hydroperoxide stream. When the amount of the noble metal catalyst is less than 1 part by weight, there is a problem that the conversion rate is lowered. When the amount is more than 15 parts by weight, there is a problem that the selectivity is lowered.

The hydrogenation is preferably carried out at a hydrogen flow rate of 1: 1 to 1:10 for 1 to 5 hours, depending on the temperature of 40 to 80 DEG C and the molar ratio to CHP. Also, the hydrogenation reaction can be carried out under conditions of ordinary fluid space velocity.

The hydrogenation reaction may be carried out by adding 1 to 10 moles of hydrogen to 1 mole of cumene hydroperoxide. If the molar number of addition of hydrogen is less than 1 mole, there is a problem that the conversion and selectivity are lowered. If the molar number exceeds 10 moles, an excessive amount of hydrogen must be recycled.

The present invention proceeds with the hydrogenation of cumene hydroperoxide at low concentrations and low temperatures, as in step (b), so that the risk of explosion at the runway reaction temperature of cumene hydroperoxide is reduced and, under the most stabilized conditions, Can be increased. Also, the high concentration of cumene hydroperoxide is converted to cumyl alcohol to increase its content, and the content of alpha methyl styrene can be increased at a later stage. Preferably, the selectivity of the hydrogenation reaction may be at least 90%, more preferably at least 95%. That is, the catalytic hydrogenation of the present invention has a conversion rate of 95% or less, while the conventional catalyst reduction has a conversion of 20 to 35% and a selectivity of 80% to a maximum yield of 40% Or more, a selectivity of 95% or more, and a yield of 90% or more. In addition, in the hydrogenation process, cumene mixed with cumene hydroperoxide can be converted into some cumyl alcohol, and further improvement in yield can be expected.

The step (c) is a step of producing alphamethylstyrene using cumyl alcohol. At this time, in the step (c), the reactant containing the cumyl alcohol may further include a cumene hydroperoxide stream not subjected to the hydrogenation reaction. Therefore, the product containing the alpha methyl styrene may further contain phenol and acetone together with alpha methyl styrene through dehydration reaction of the reactant. Preferably, the phenol and acetone can be produced by a dehydration process after the cumene hydroperoxide stream in the reactant is contacted with the acid catalyst. Alphamethylstyrene is also produced by the dehydration process after the cumyl alcohol in the reactant is contacted with the acid catalyst. In addition, the product may further contain a trace amount of acetophenone, cumene, and a heavy compound.

The reaction product containing the cumyl alcohol is preferably concentrated to a concentration of 80 to 82% by weight and used for dehydration reaction.

In the case of the present invention, before carrying out the step (c) in order to minimize the generation of a heavy compound, if necessary, the residue of the remaining stream except for the cumene hydroperoxide stream used in the hydrogenation reaction of the step (b) The mixture of cumyl alcohol obtained in step b) may be diluted.

In the step (c), the acid catalyst is preferably a liquid or solid acid catalyst. The liquid acid catalyst is hydrochloric acid, sulfuric acid or nitric acid, preferably sulfuric acid. Further, the solid acid catalyst is selected from the group consisting of a Group 4 metal oxide modified by a Group 6 metal oxide, a sulfurized transition metal oxide, a mixed metal oxide of a cerium oxide and a Group 4 metal oxide, and a mixture thereof desirable.

Further, the present invention may further include, after step (c), neutralizing and distilling the product containing the alphamethylstyrene. Through this process, alpha methyl styrene, phenol and acetone can be separated.

The distillation conditions are not particularly limited and can be performed by a conventional method. In the neutralizing step, the kind and content of the neutralizing agent are not particularly limited and can be used under ordinary conditions.

Hereinafter, a method for producing alpha methyl styrene according to a preferred embodiment of the present invention will be described in more detail with reference to the drawings. 2 is a schematic view of a phenol process for producing alpha methyl styrene of the present invention.

Referring to Figure 2, the method of the present invention comprises: an oxidation reactor 10 for conducting the oxidation of cumene; A catalyst hydrogenation reactor 30 for using a portion of the cumene hydroperoxide stream obtained after the oxidation in the hydrogenation reaction; A stripper 40 for concentrating the cumyl alcohol obtained by the hydrogenation reaction and the remaining cumene hydroperoxide stream not used for the hydrogenation reaction; A cleavage reactor 60 for conducting a dehydration reaction of the concentrated mixture in the stripper; A neutralization reactor (70) for progressing the neutralization of the product obtained by the dehydration reaction; And a distillation device 80 for separating the product. Also, a receiver (20, 50) may be provided between the oxidation reactor (10) and the stripper (40) and between the stripper (40) and the decomposition reactor (60).

Specifically, the present invention relates to a process for producing cumene hydroperoxide and cumyl alcohol having a low concentration by the oxidation of cumene, preparing a cumyl alcohol by directly hydrogenating at least a part of the cumene hydroperoxide without concentration, The remaining residue of cumene hydroperoxide which has not been reacted with the cumyl alcohol obtained by the hydrogenation reaction is mixed to prepare a reaction product containing cumyl alcohol and dehydration reaction is carried out under an acid catalyst to obtain a product containing increased productivity of alphamethylstyrene Can be obtained. Since phenol and acetone are also included in the product, after the above step, the product is neutralized and distilled to obtain AMS having increased productivity together with phenol and acetone. Therefore, through the selective hydrogenation process of cumene hydroperoxide, the conversion of cumene hydroperoxide to cumyl alcohol can be increased to increase or decrease the amount of cumene hydroperoxide, and finally, the amount of alpha methyl styrene can be increased or decreased.

That is, in the present invention, cumene is supplied to the oxidation reactor (10), and the oxidation reaction of cumene proceeds in the presence of oxygen. Oxidation of the cumene produces a cumene hydroperoxide stream at a concentration of 5 to 25% by weight, which contains cumyl alcohol.

In the present invention, a part of the stream is separated and transferred to the storage unit 20, and then supplied to the hydrogenation reactor 30 to progress the hydrogenation reaction. At this time, the low concentration cumene hydroperoxide stream transferred to the reservoir 20 is fed to the top of the catalytic hydrogenation reactor 30 or bottom-up to produce cumyl alcohol by a hydrogenation reaction. The reaction used in the hydrogenation reaction may be carried out through a CSTR reactor (continuous stirred tank reactor), but not limited thereto, and can be used as long as it is used in ordinary hydrogenation reaction conditions. For example, it is preferable that the hydrogenation reactor is charged with a catalyst and the reaction is carried out by injecting hydrogen and maintaining the internal temperature. In addition, the reactant, the concentrated cumene hydroperoxide stream, can be injected to the top of the reactor using a pressurized pump.

When the hydrogenation reaction is completed, the prepared cumyl alcohol is supplied again to the reservoir 20 and transferred to the stripper 40. In addition, the CHP stream at a concentration of 5 to 25% by weight, which has not yet proceeded to the hydrogenation reaction, is directly conveyed to the stripper 40.

Accordingly, the stripper 40 includes a mixture of the cumyl alcohol obtained by the hydrogenation reaction and the stream containing cumyl alcohol and cumene hydroperoxide not used for the hydrogenation reaction.

Thereafter, in the stripper 40, the mixture is concentrated to a concentration of 80 to 82% by weight, and then is transferred to the decomposition reactor 60 via the reservoir 50.

Subsequently, dehydration is continuously performed on the mixture in the decomposition reactor 60 so that the acid catalyst decomposes cumene hydroperoxide into phenol and acetone, and dehydrates cumyl alcohol with AMS.

The mixture of phenol, acetone and AMS produced in the decomposition reactor 60 is transferred to a neutralization reactor 70, and a neutralizing agent is added thereto to proceed a neutralization reaction.

Finally, the product is transferred to distillation unit 80 and separated by distillation into phenol, acetone and AMS, respectively.

At this time, in the present invention, the condition of the reactor used in each reaction step is not particularly limited, and a well-known conventional reactor in this field can be used. In addition, each reactor can be connected via a separate transfer line. The finally separated phenol, acetone, and AMS can also be collected into a collection reservoir through a separately connected outlet.

The present invention promotes the hydrogenation reaction of cumene hydroperoxide obtained by the oxidation of cumene under the most stabilized conditions of low concentration and low temperature to produce cumyl alcohol in a more stable state without the danger of explosion of cumene hydroperoxide. In addition, the present invention relates to a process for the conversion of cumene hydroperoxide into cumyl alcohol at a high selectivity through a hydrogenation process, thereby increasing the yield of AMS in the phenol plant and controlling the amount of cumene hydroperoxide stream injected into the hydrogenation process, Can be controlled according to market demand.

FIG. 1 is a process diagram schematically showing a conventional process for producing phenol.
2 is a schematic view of a phenol process for producing alpha methyl styrene of the present invention.

Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through a specific embodiment of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

[Examples 1 and 2]

Alpha methyl styrene was prepared according to the process diagram shown in Fig.

First, in the phenol process, the oxidation of cumene was carried out using an oxidizing agent under the following conditions using three oxidation reactors to prepare a stream containing cumene hydroperoxide (CHP) at a concentration of 25 wt%.

(1) Conditions for introducing the first oxidizer

(CHP 0.4% + cumene 99.6%) 1 ml / min, 02: 100 ml / min, pressure: 3 bar, reaction temperature: 100 ° C

(2) Conditions for introducing a second oxidizer

(CHP 8.42% + cumene 91.58%) 1 ml / min, 02: 100 ml / min, pressure: 3 bar, reaction temperature: 96 ° C

(3) Conditions for introducing a third oxidizer

(CHP 16.27% + cumene 83.73%) 1 ml / min, 02: 100 ml / min, pressure: 3 bar, reaction temperature: 94 ° C

At this time, the concentration of the CHP stream was changed from 8.4 to 24% by weight through three oxidation reactors as shown in Table 1 below.

Then, 25 wt% of the low-concentration stream was separated and transferred to the storage unit 20, and then supplied to the catalytic hydrogenation reactor 30.

The hydrogenation reactor was filled with Pd / C as a catalyst and hydrogen was injected to maintain the internal temperature. In addition, a cumene hydroperoxide stream having a concentration of 25 wt%, which is a reactant, was injected into the reactor top-down using a pressure pump. The hydrogenation reaction was carried out under the conditions of 150 g of cumene hydroperoxide (CHP) at a concentration of 25 wt%, 1 g of 1 wt% Pd / C, and a hydrogen flow rate of 150 cc / min. In addition, the molar ratio of the cumene hydroperoxide stream to the hydrogen charged was maintained at 1: 8. The hydrogenation reaction time was 7 hours and 3 hours, respectively, and thus Examples 1 and 2 were used. As a result, the final product of cumene hydroperoxide (CHP) conversion rate of 99.97%, CA increase rate of 960.5% and CA concentration of 25% was obtained.

After completion of the reaction, the conversion of cumene hydroperoxide to cumyl alcohol was analyzed by liquid chromatography, and the results are shown in Table 2.

When the hydrogenation reaction is completed, the prepared cumyl alcohol is supplied to the storage device 20 and transferred to the stripper 40. Accordingly, the stripper 40 is filled with a mixture of the cumyl alcohol obtained by the hydrogenation reaction and the stream containing cumyl alcohol and cumene hydroperoxide not used for the hydrogenation reaction.

Thereafter, the mixture was concentrated in the stripper 40, transferred to the decomposition reactor 60 via the reservoir 50, and the remainder was immediately transferred to the decomposition reactor.

Then, the acid catalyst was added to the decomposition reactor 60 to continuously dehydrate the mixture to decompose cumene hydroperoxide into phenol and acetone and dehydrate cumyl alcohol with AMS.

At this time, 100 g of the feed (CHP 72 wt%, CA 8 wt%, cumene 20 wt%) and 1 g of H 2 SO 4 were added to the cleavage condition to carry out the reaction. Also, the reaction temperature was maintained at 65 캜 to convert CH to less than 1%, and then the temperature was increased to 110 캜 to convert CA to AMS.

The mixture of phenol, acetone, and AMS produced in the decomposition reactor 60 was transferred to the neutralization reactor 70, and a neutralization agent was added thereto to proceed the neutralization reaction. After neutralization, the product was transferred to a distillation reactor (80) and separated by distillation into phenol, AMS and acetone, respectively.

According to the above reaction, the conversion of CHP to phenol was 99.36%, the conversion of CHP to acetone was 98.30%, and that of CA to AMS was 82.45%.

Oxidation reactor Stripper Decomposition reactor A B C 1st 2nd 1st 2nd CHP concentration
(weight%) 8.4 16.3 24 24 → 50 50 → 82 82 → 1 1 → 1 or less week)
A: First oxidizer
B: Second oxidizer
C: Third oxidizer
CHP: cumene hydroperoxide
CA: Cumyl alcohol

In Table 1, it is shown that most of the CHP in the 1 st decomposition reactor is decomposed into phenol and acetone, and the concentration is reduced from 82 wt% to 1 wt%. In the 2 nd decomposition reactor, 1 wt% Lt; / RTI >

[Comparative Examples 1 and 2]

150 g of cumene hydroperoxide having a concentration of 25% by weight and 1 g of Co / Al / PO 4 (Co: 7 wt%, Al: 25 wt%, P: 3 wt% . The reaction time was 7 hours and 3 hours, respectively, and Comparative Examples 1 and 2 were used. Other conditions were carried out in the same manner as in Example 1 to prepare AMS. The conversion of cumene hydroperoxide and the increase rate of cumyl alcohol are shown in Table 2.

[Comparative Examples 3 to 4]

50 g of cumene hydroperoxide having a concentration of 80% by weight, which had been concentrated through the oxidation reaction of cumene and a stripper, was diluted in 100 g of acetone and the cumene alcohol was prepared by a reduction reaction using the catalyst shown in Table 2 without conducting the hydrogenation reaction. The conversion of cumene hydroperoxide and the increase rate of cumyl alcohol are shown in Table 2.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Catalyst component Pd / C Pd / C Co / Al / PO 4 Co / Al / PO 4 Co / Al / PO 4 Co / ZrO The amount of catalyst (g) One One One One One One Hydrogen
(cc / min) 150 150 0 0 0 0 CHP (g) 150 150 150 150 50 50 Solvent (g) 0 0 0 0 100 100 The reaction liquid (g) 150 150 150 150 150 150 CHP concentration (wt%) 25 25 25 25 27 27 Temperature (℃) 65 65 65 65 57 57 Reaction time (hr) 7 3 7 3 3 3 CHP Conversion Rate (%) 99.97 46.2 3.8 2.3 23.1 35.1 CA growth rate (%) 960.5 479.6 57.5 39 225.2 321.9

From the results shown in Table 2, Examples 1 and 2 of the present invention show that the use of 25 wt% CHP solution through an oxidation reactor as a feed for the hydrogenation reaction makes cumene hydroperoxide (CHP ), And the yield of cumyl alcohol was increased. Also, in the production of phenol, acetone and alpha methylstyrene through dehydration using cumyl alcohol, the production amount of AMS was increased to about 100 to 1200% in Comparative Example 1-4 in the case of Example 1-2 of the present invention.

[Experimental Example]

After the addition of CHP was completed during the hydrogenation process in Example 1, the composition of the reactant solution was analyzed over time. According to this composition analysis, CHP conversion rate and CA increase rate in the catalytic hydrogenation process were measured by the following method, and the results are shown in Table 3.

[Equation 1]

CHP conversion (%) = (CHP feed (wt%) - CHP product (wt%)) / (CHP feed (wt%))

&Quot; (2) "

CA growth rate (%) = (CA product (wt%) - CA feed (wt%)) / (CA feed (wt%))

Time (h) Sample (g) supply One 2 3 4 5 6 7 CHP 0.202 0.181 0.145 0.109 0.072 0.029 0 0 CA 0.023 0.063 0.097 0.131 0.170 0.207 0.235 0.240 Cumen 0.797 0.781 0.785 0.781 0.796 0.780 0.779 0.787 AP 0.004 0.004 0.004 0.005 0.005 0.005 0.005 0.005 AMS 0 0.001 0.001 0.001 0.001 0.001 0.001 0.001 phenol 0 0 0 0 0 0 0 0 Acetone 0 0 0 0 0 0 0 0 DCP 0 0 0 0 0 0 0 0 CHP Conversion Rate (%) 10.59 28.12 46.18 64.31 85.43 99.97 99.97 CA growth rate (%) 178.52 330.68 479.58 649.85 816.72 937.64 960.50

1, 10: oxidation reactor
2, 4, 20, 50: the receiver,
30: catalytic hydrogenation reactor
3, 40: stripper
5, 60: a cleavage reactor
6, 70: Neutralizer reactor
7, 80: distillation device

Claims (16)

(a) oxidizing cumene to produce a cumene hydroperoxide stream;
(b) separating at least a portion of the stream without concentration of the cumene hydroperoxide stream and subjecting it to hydrogenation under a noble metal catalyst to produce cumyl alcohol; And
(c) concentrating the reactant comprising the cumyl alcohol and dehydrating it under an acid catalyst to produce a product comprising alpha methyl styrene,
In the step (b), the cumene hydroperoxide stream is used in a hydrogenation reaction at a concentration of 5 to 25% by weight. delete The method of claim 1, wherein in step (b), 5 to 50% by weight of the cumene hydroperoxide stream is separated and used for the hydrogenation reaction to divide some of the total flow. The method of claim 1, wherein the noble metal catalyst comprises at least one selected from the group consisting of gold, silver, platinum, palladium, iridium, ruthenium, rhenium, rhodium and osmium. 5. The process of claim 4, wherein the noble metal catalyst is selected from the group consisting of alpha methyl styrene < RTI ID = 0.0 > (A) < / RTI > further comprising a carrier selected from the group consisting of alumina, silica, clay, carbon, zirconia, titania, mesoporous molecular sieves, ≪ / RTI > The method of claim 1, wherein the noble metal catalyst is used in an amount of 1 to 15 parts by weight based on 100 parts by weight of the cumene hydroperoxide stream. The process according to claim 1, wherein the hydrogenation reaction is carried out at a hydrogen flow rate of 1: 1 to 1:10 according to a molar ratio of cumene hydroperoxide (CHP) to a temperature of 40 to 80 DEG C for 1 to 5 hours. Gt; The method of claim 1, wherein the selectivity of the hydrogenation reaction is 95% or more. The method of claim 1, wherein the conversion of cumene hydroperoxide is at least 95%. The method of claim 1, wherein the cumene hydroperoxide stream further comprises cumyl alcohol. The method of claim 1, wherein the acid catalyst is a liquid or solid acid catalyst. 12. The method of claim 11, wherein the liquid acid catalyst is hydrochloric acid, sulfuric acid, or nitric acid, the Group 4 metal oxide modified by a Group 6 metal oxide, the sulfurized transition metal oxide, And a mixture thereof. ≪ RTI ID = 0.0 > 21. < / RTI > The method according to claim 1, wherein in step (b), a hydrogenation reaction proceeds on a part of the cumene hydroperoxide stream, and in the step (c), the reactant containing the cumyl alcohol is reacted with cumene hydroperoxide ≪ / RTI > further comprising an oxide stream. The method of claim 1, wherein the product comprising alpha methyl styrene in step (c) further comprises phenol and acetone. The method according to claim 1, wherein the reactant containing the cumyl alcohol is concentrated to a concentration of 80 to 82% by weight and used for dehydration reaction. 2. The method of claim 1, wherein the method further comprises, after step (c), neutralizing and distilling the product comprising alpha methyl styrene.
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