KR101476375B1 - Method for preparing phenol, acetone and alpha methyl styrene - Google Patents

Abstract

The present invention relates to a hydrogenation process of cumene hydroperoxide obtained by oxidation of cumene in a phenol production process and a separation and dehydration process of alpha methyl styrene in cumyl alcohol under the most stabilized condition of low concentration and temperature, In the hydrogenation reaction of oxides, the risk of explosion is lowered and the selectivity is increased to increase the amount of cumyl alcohol, thereby selectively increasing the amount of alpha methyl styrene and controlling the amount of cumene hydroperoxide, And more particularly to a process for preparing alpha methyl styrene.

Description

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

The present invention relates to a process for the production of phenol, acetone and alpha methylstyrene, and more particularly to a process for the production of phenol, acetone and alpha methylstyrene which can selectively produce alphamethylstyrene without reducing the production of phenol .

Alpha-methyl styrene has been used extensively as a specific copolymer such as ABS and as an additive in the production of novel polymers. In addition, alpha methyl styrene has an application as an intermediate for the production of fine compounds such as unsaturated alpha methyl styrene dimers. These dimers have been used as molecular weight control agents in the preparation of copolymers such as acrylynitrile-butadiene-styrene resins and styrene-butadiene rubbers. The hydrogenated form of the alpha methyl styrene dimer has industrial value as a component in the lubricating composition.

Such alpha methyl styrene is generally produced as a by-product of a phenol manufacturing process for producing phenol 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, a cumene is oxidized in the presence of oxygen in an oxygen reactor (1) fed with cumene to convert a cumene hydroperoxide to a small amount of cumyl alcohol by about 24% by weight, ), The stream containing the cumene hydroperoxide of about 24% by weight is concentrated to about 82% by weight in the stripper (3). Thereafter, the concentrated cumene hydroperoxide and cumyl alcohol-containing streams are fed to a cracking reactor 5 via a reservoir 4 and dehydrated under an acid catalyst to produce phenol and acetone from cumene hydroperoxide, Methyl styrene. However, in the case of the above method, only 0.035 moles of cumyl alcohol is produced per 1 mole of cumene hydroperoxide in the oxidation process of cumene, so that the production amount of alpha methyl styrene in the phenol production process is as low as that of cumyl alcohol .

In order to selectively increase the production amount of alpha methyl styrene, a part of cumene hydroperoxide from a stripper was selectively converted into cumyl alcohol prior to the cleavage reactor to obtain alpha methyl styrene . However, the above method has a low conversion efficiency and low selectivity and thus has a poor process efficiency and has a problem in safety due to the use of highly concentrated cumene hydroperoxide.

Also, in the conventional method, a method of converting the hydrogenation process of alpha methyl styrene generated again for recycling to an oxidation reactor into cumene, instead of mainly purifying the above alpha methyl styrene, is disclosed (U.S. Patent No. 5,905,178). Or an attempt to minimize the production of alpha methyl styrene by treating alpha methyl styrene as a byproduct of the phenol manufacturing process (U.S. Patent No. 5,530,166), and studies for increasing the production amount of alpha methyl styrene are insufficient to be.

In order to solve the above-mentioned problems, the present invention provides a process for the hydrogenation of cumene hydroperoxide to cumyl alcohol and the separation of alpha methyl styrene from cumyl alcohol. The process for selectively removing alpha methyl styrene, which is regarded as a by- Phenol, acetone and alpha methyl styrene which can be evaporated.

Accordingly,

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

(b) separating at least a portion of the cumene hydroperoxide stream and hydrogenating it under a noble metal catalyst to produce cumyl alcohol;

(c) dehydrating the reactant containing the cumyl alcohol under an acidic catalyst; And

(d) separately dehydrating the remaining portion of the cumene hydroperoxide stream not subjected to the hydrogenation reaction

Acetone, and alpha methylstyrene.

According to an embodiment of the present invention, in the step (a), the cumene hydroperoxide stream may be produced at a concentration of 5 to 25% by weight.

According to another embodiment of the present invention, in step (b), 5 to 50% by weight of the cumene hydroperoxide stream may be separated and used for the hydrogenation reaction.

In the production process according to the method of the present invention, the degree of selectivity of the hydrogenation reaction is 95% or more, and the conversion from cumene hydroperoxide to cumyl alcohol may be 95% or more.

Hereinafter, the method for producing phenol, acetone and alpha methyl styrene of the present invention will be described in more detail.

The method for producing phenol, acetone and alpha methylstyrene according to the present invention comprises:

(a) oxidizing cumene to produce a cumene hydroperoxide stream; (b) separating at least a portion of the cumene hydroperoxide stream and hydrogenating it under a noble metal catalyst to produce cumyl alcohol; (c) dehydrating the reactant containing the cumyl alcohol under an acidic catalyst; And (d) separately dehydrating the remaining portion of the cumene hydroperoxide stream not subjected to the hydrogenation reaction.

Generally, in the phenol manufacturing process, a 25% by weight cumene hydroperoxide (CHP) solution prepared through three oxidation reactors is concentrated through a stripper into a 80% by weight CHP solution, and is passed through a decomposition reactor to remove phenol, acetone and alpha And producing methylstyrene.

However, cumene hydroperoxide has an ignition point of 57 to 79 ° C and can explode upon mixing with air. 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. The production process of the present invention provides a process capable of producing cumyl alcohol in a stable state using a low concentration of cumene hydroperoxide.

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.

Further, in the conventional phenol manufacturing process, only about 0.035 moles of cumyl alcohol is produced per 1 mole of cumene hydroperoxide, which limits the production of alpha methyl styrene.

According to the production method of the present invention, the production amount of alpha-methyl styrene can be increased by dehydrating the cumyl alcohol after increasing the production amount of cumyl alcohol through hydrogenation of cumene hydroperoxide to cumyl alcohol. That is, in the prior art, the cumene hydroperoxide stream obtained by the oxidation of cumene is concentrated in a stripper and then dehydrated as it is in the decomposition reactor. On the other hand, according to the production method of the present invention, A part of the obtained cumene hydroperoxide is separated and used in the hydrogenation process, whereby the selectivity of cumene hydroperoxide and the conversion to cumyl alcohol can be improved.

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

In the production method of the present invention, cumene hydroperoxide stream is firstly produced by oxidizing cumene (step (a)).

According to one embodiment of the present invention, a cumene hydroperoxide stream having a concentration of about 5 to about 25 wt% 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 may be carried out under general conditions. For example, the oxidation of cumene can usually be carried out by autoxidation with air-oxygen gas such as air or oxygen-enriched air. The oxidation reaction can also be carried out with or without an additive such as an alkali. Examples of the additives include alkali metal compounds such as sodium hydroxide (NaOH) and potassium hydroxide (KOH), alkaline earth metal compounds, alkaline metal carbonates such as sodium carbonate (Na ₂ CO ₃ ), sodium hydrogen carbonate (NaHCO ₃ ), ammonia, ammonium carbonate Or the like, but the present invention is not limited thereto.

According to one embodiment of the present invention, the oxidation reaction can be carried out at a temperature of from about 50 to about 200 DEG C and atmospheric pressure to about 5 MPa

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. Also, the step (a) may oxidize the cumene-containing stream having a cumene concentration of 80% or more, preferably 99% or more, in the presence of the oxygen-containing stream to form a cumene hydroperoxide-containing stream.

According to one embodiment of the present invention, conventional initiators may be used to promote oxidation of the cumene. Examples of the initiator include, but are not limited to, organic hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide, peroxime free radical initiators, and azo type free radical initiators.

Next, at least a part of the cumene hydroperoxide stream prepared in the step (a) is separated and subjected to a hydrogenation reaction under a noble metal catalyst to produce cumyl alcohol (step (b)).

Since a part of the cumene hydroperoxide stream separated in the step (b) is converted to cumyl alcohol, and the continuous dehydration reaction produces alpha methyl styrene, the proportion of the cumene hydroperoxide stream used in the hydrogenation reaction is required The production amount of alpha methyl styrene can be controlled. According to one embodiment of the present invention, some, preferably about 5 to about 50 weight percent of the cumene hydroperoxide stream may be separated and used in the hydrogenation reaction.

Also, according to one embodiment of the present invention, the cumene hydroperoxide stream may be subjected to a hydrogenation reaction by separating at least a portion thereof without concentration.

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. According to an embodiment of the present invention, the noble metal catalyst may be a Pd / C catalyst containing carbon as a carrier.

According to one embodiment of the present invention, the noble metal catalyst may be used in an amount of about 0.5 to about 15 parts by weight based on 100 parts by weight of the cumene hydroperoxide stream. When the amount of the noble metal catalyst is 0.5 to 15 parts by weight, high conversion and selectivity can be exhibited.

The hydrogenation reaction may be conducted at a temperature of about 40 to about 80 캜 for about 0.2 to about 7 hours. Also, the hydrogenation reaction can be carried out under conditions of ordinary fluid space velocity.

The hydrogenation reaction may be performed by adding about 1 to about 10 moles of hydrogen per 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, which may lead to economical problems.

According to the production method of the present invention, since the process of hydrogenating cumene hydroperoxide is carried out under mild conditions, the risk of explosion at the runway reaction temperature of cumene hydroperoxide is reduced to increase the conversion to cumyl alcohol under the maximally stabilized condition . In addition, high concentrations of cumene hydroperoxide can be converted to cumyl alcohol, which can increase the content of alpha methyl styrene in subsequent steps.

In the production process of the present invention, the selectivity of the hydrogenation reaction may be 95% or more. The catalytic hydrogenation process of the present invention has a catalytic hydrogenation rate of about 3%, while the conventional catalyst reduction method has a conversion of 20% to 35% and a selectivity of 80% to a maximum yield of 40% A conversion rate of not less than 80%, a selectivity of not less than 95% and a yield of not less than 80% When cumyl alcohol is obtained and the reaction time is increased, cumyl alcohol can be obtained with a conversion of 95% 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.

Next, the reaction product containing the cumyl alcohol is dehydrated (step (c)) under an acidic catalyst, and the remaining part of the cumene hydroperoxide stream not subjected to the hydrogenation reaction is separately dehydrated (step (d)). .

The step (c) is a step of obtaining alpha methyl styrene by dehydration reaction of cumyl alcohol. The step (d) is a step of obtaining phenol and acetone by dehydration reaction of cumene hydroperoxide.

In the production process of the present invention, the dehydration reaction of the cumyl alcohol converted by the hydrogenation reaction and the dehydration reaction of the cumene hydroperoxide not subjected to the hydrogenation reaction are respectively carried out in separate physically separated decomposition reactors. Therefore, in the prior art, the process for producing phenol and acetone and the process for producing cumyl alcohol were performed in the same space (decomposition reactor). In contrast, in the production process of the present invention, the step of producing alphamethylstyrene from cumyl alcohol, The process of producing phenol and acetone from hydroperoxide is distinguished and separated in a separate decomposition reactor.

Accordingly, the detailed process conditions of the dehydration process for producing phenol and acetone and the dehydration process for producing alpha methylstyrene can be optimized and set differently, thereby increasing the production amount of phenol and alpha methyl styrene. For example, the reaction conditions such as temperature, pressure, reaction time, type of catalyst, and amount of catalyst in steps (c) and (d) can be independently set.

In the step (c), the acid catalyst may be 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.

The acid catalyst used in the dehydration reaction of cumyl alcohol may be used in an amount of about 0.01 to about 10 parts by weight based on 100 parts by weight of the cumyl alcohol.

In the step (d), the remainder of the cumene hydroperoxide stream not subjected to the hydrogenation reaction may also undergo a dehydration reaction under the catalyst. The catalyst may be an acidic catalyst and may be the same or different acidic catalyst than the acidic catalyst used in the dehydration reaction of cumyl alcohol in step (c).

When the dehydration reaction is carried out for the remaining part of the cumene hydroperoxide stream under an acidic catalyst, it is preferable to undergo a neutralization reaction.

According to an embodiment of the present invention, the remainder of the cumene hydroperoxide stream not subjected to the hydrogenation reaction may be concentrated to conduct a dehydration reaction.

Separating the dehydration reaction of cumyl alcohol with cumene hydroperoxide in this way has the advantage of increasing the yield of methylstyrene without reducing the yield of the main products phenol and acetone. Further, when the cumene hydroperoxide and the cumyl alcohol coexist in a single reactor in the dehydration reaction, there is an additional advantage that by-products can be prevented from being produced according to the reaction therebetween. For example, when performing the dehydration reaction separately, the content of impurities may be less than 7 wt%, preferably less than 5 wt%, based on the total amount of phenol, acetone and alpha methyl styrene.

After the steps (c) and (d), the product of the dehydration reaction may be further subjected to neutralization and then combined to purify a product containing the phenol, acetone, and alpha methylstyrene, followed by separation by distillation. Through this process, alpha methyl styrene, phenol, and acetone can be separated, respectively.

The purification step can be used under normal conditions. The distillation conditions are not particularly limited and can be performed by a conventional method.

Hereinafter, a method for producing phenol, acetone and alpha methylstyrene according to a preferred embodiment of the present invention will be described in detail with reference to the drawings.

2 is a schematic view illustrating a process for producing phenol, acetone, and alpha methyl styrene according to an embodiment of the present invention.

Referring to FIG. 2, the method of the present invention comprises: an oxidation reactor 100 for conducting oxidation of cumene; A catalyst hydrogenation reactor 300 for using a portion of the cumene hydroperoxide stream obtained after the oxidation in the hydrogenation reaction; A stripper 400 for concentrating the remaining cumene hydroperoxide stream not used for the hydrogenation reaction; A first cleavage reactor 320 for conducting the dehydration reaction of the cumyl alcohol obtained by the hydrogenation reaction; A second cleavage reactor 600 for conducting a dehydration reaction of the remaining cumene hydroperoxide stream not used in the hydrogenation reaction in the stripper; A neutralization unit 700 for progressing the neutralization of the product obtained from the second decomposition reactor 600; And a separation device 800 for separating the products. A receiver 200 or 500 may further be provided between the oxidation reactor 100 and the stripper 400 or between the stripper 400 and the second decomposition reactor 600. Also, a reservoir 310 may be further provided between the hydrogenation reactor 300 and the first decomposition reactor 320.

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, and then dehydrating And the remainder of cumene hydroperoxide not used in the hydrogenation reaction is separately dehydrated to obtain a product containing phenol, acetone and alpha methylstyrene with increased productivity.

That is, the step of producing phenol and acetone from cumene hydroperoxide by dehydration and the step of producing alpha methylstyrene by dehydration from cumyl alcohol are carried out separately. After this step, phenol, acetone and alpha methyl styrene Are obtained by mixing, purifying and separating the products of the main products, phenol and acetone. In addition, since the decomposition reaction proceeds independently in the state where the cumyl alcohol and the cumene hydroperoxide are spatially separated, the byproducts due to the reaction do not occur, and the content of the total impurities is also lowered.

More specifically, referring to FIG. 2, first, cumene is supplied to the oxidation reactor 100, and the oxidation reaction of cumene proceeds in the presence of oxygen. According to an embodiment of the present invention, although not shown in the drawing, the oxidation reactor 100 may include a plurality of oxidation reactors in a stepwise manner. For example, the oxidation reaction can be carried out in three stages in three oxidation reactors. Oxidation of the cumene produces a cumene hydroperoxide stream at a concentration of 5 to 25% by weight.

Thereafter, the present invention separates a portion of the cumene hydroperoxide stream and, via a reservoir 200, And is supplied to the hydrogenation reactor 300 to advance the hydrogenation reaction. The low concentration cumene hydroperoxide stream delivered to the reservoir 200 can be fed to the top-down or bottom-up of the hydrogenation reactor 300 to produce cumyl alcohol by hydrogenation. 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 300 is filled with a catalyst and the reaction is carried out by injecting hydrogen and maintaining the internal temperature. According to an embodiment of the present invention, the hydrogenation reactor 300 may be charged with a Pd / C catalyst to perform the reaction. In addition, the reactant, the concentrated cumene hydroperoxide stream, can be injected to the top of the reactor using a pressurized pump. The cumene hydroperoxide is converted to cumyl alcohol by the hydrogenation reaction.

When the hydrogenation reaction is completed, the prepared cumyl alcohol is supplied to the first decomposition reactor 320 through the storage unit 310 again. Dehydration reaction proceeds to the alpha methylstyrene in the first decomposition reactor 320. The dehydration reaction can be carried out using an acidic catalyst.

The product comprising alpha methylene produced in the first cracking reactor 320 is combined with the product comprising phenol and acetone through the second cracking reactor 600 and the neutralizer 700 described below.

The remaining stream of cumene hydroperoxide, which has not undergone the hydrogenation reaction, is directly conveyed to the stripper 400. Accordingly, the stripper 400 includes cumene hydroperoxide not used for the hydrogenation reaction. The stripper 400 may also contain a small amount of cumyl alcohol obtained by oxidation of cumene.

Then, the cumene hydroperoxide is decomposed into phenol and acetone by performing a dehydration reaction on the cumene hydroperoxide in the second decomposition reactor (600). The dehydration reaction in the second decomposition reactor 600 may be performed under an acidic catalyst. Reaction conditions such as temperature, pressure, reaction time, type of catalyst, amount of catalyst, etc. in the first decomposition reactor 320 and the second decomposition reactor 600 can be independently set.

The product containing phenol and acetone produced in the second decomposition reactor 600 is transferred to the neutralization apparatus 700 to perform the neutralization process.

Next, the product containing the phenol and acetone, which has been subjected to the neutralization process, and the product containing the alpha methyl styrene produced in the first decomposition reactor 320 are transferred to the separation device 800. In the separation device 800, it is separated into phenol, acetone and alpha methyl styrene through purification and distillation, respectively. Finally, the finally separated phenol, acetone and alpha methyl styrene can be collected into a collection reservoir through a separately connected outlet.

As described above, according to the production method of the present invention, the step of producing phenol and acetone from cumene hydroperoxide and the step of producing alpha methyl styrene from cumyl alcohol are separately performed, By mixing, purifying and separating the products, it is possible to obtain alphamethylstyrene which is simultaneously increased in productivity without decreasing the yield of the main products phenol and acetone. In addition, since the cumyl alcohol and cumene hydroperoxide are spatially separated and the process proceeds, there is no possibility that by-products due to these reactions will occur, the total impurity content is lowered and the subsequent purification process can be simplified, .

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, according to the production method of the present invention, the step of producing alpha methylstyrene from cumyl alcohol and the step of producing phenol and acetone from cumene hydroperoxide are carried out separately, whereby impurities are reduced and the yield of phenol and acetone The production of alpha methyl styrene can be increased without reducing the amount of alpha methyl styrene.

1 is a process diagram schematically showing a conventional process for producing phenol.
FIG. 2 is a process diagram briefly showing a process for producing phenol, acetone, and alpha methyl styrene according to an embodiment 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.

Example  One

Phenol, acetone and alpha methyl styrene were 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 25% by weight through three oxidation reactors.

Among the low concentration streams 25% by weight was separated and fed to the hydrogen storage reactor 300 after being transferred to the reservoir 200.

In the hydrogenation reactor 300, Pd / C was filled as a catalyst, hydrogen was injected, and the internal temperature was maintained at 65 ° C to conduct the reaction. A cumene hydroperoxide stream with a 25 wt% concentration of reactant was also injected at the bottom of the reactor using a pressure pump. The hydrogenation reaction was carried out under the conditions of 150 g of cumene hydroperoxide having a concentration of 25 wt%, 1 g of a Pd / C catalyst, 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 3 hours.

After the completion of the hydrogenation reaction, the prepared cumyl alcohol was supplied to the first decomposition reactor 320 through the storage unit 310. The first decomposition reactor 320 was dehydrated with alpha methylstyrene using sulfuric acid (H ₂ SO ₄ ) as an acid catalyst. At this time, 2.6 wt% of sulfuric acid was used as the weight of the cumyl alcohol supplied to the first decomposition reactor 320, and the reaction temperature was maintained at 100 DEG C until the cumyl alcohol concentration was less than 2%.

On the other hand, the remaining 75% stream of cumene hydroperoxide not transferred to the hydrogenation reactor 300 was concentrated to 82% through the stripper 400.

The concentrated cumene hydroperoxide was transferred from the stripper 400 to the second decomposition reactor 600.

The acid catalyst was added to the second decomposition reactor 600 to decompose cumene hydroperoxide into phenol and acetone. At this time, 0.04% by weight of sulfuric acid (H ₂ SO ₄ ) was added to the reactant to be fed into the second decomposition reactor to proceed the reaction. Further, the reaction temperature was maintained at 60 DEG C so that the concentration of cumene hydroperoxide was 1% ≪ / RTI >

The phenol and acetone produced in the second decomposition reactor 600 are combined with the alpha methylstyrene produced in the first decomposition reactor 320 through the neutralization unit 700 and transferred to the separation unit 800. The phenol, Acetone, and alpha methyl styrene.

Comparative Example  One

The oxidation of cumene with an oxidizing agent using an oxidizing reactor was carried out to prepare a stream containing cumene hydroperoxide having a concentration of 25% by weight.

150 g of cumene hydroperoxide having a concentration of 25% by weight and 1 g of Co / Al / PO ₄ (Co: 7% by weight, Al: 25% by weight, P: 3% To prepare cumyl alcohol. The reaction time was 3 hours.

Upon completion of the reduction reaction, the mixture containing the prepared cumyl alcohol and cumene hydroperoxide not used for the reduction reaction was transferred to the decomposition reactor.

The mixture is continuously dehydrated by adding sulfuric acid (H ₂ SO ₄ ) as an acidic catalyst to the decomposition reactor to decompose the cumene hydroperoxide into phenol and acetone, dehydrate the cumyl alcohol with alpha methylstyrene Respectively. At this time, 0.04% by weight of sulfuric acid was added to 150 g of the mixture in the decomposition reactor to proceed the reaction. The reaction temperature was maintained at 65 占 폚.

Other conditions were carried out in the same manner as in Example 1 to prepare phenol, acetone and alpha methyl styrene.

Comparative Example  2 to 3

50 g of cumene hydroperoxide having a concentration of 80% by weight through concentration of cumene and a stripper was diluted with 100 g of acetone to a concentration of 27% by weight. Then, 1 g of Co / Al / PO ₄ And Co / ZrO ₂ catalyst were used to produce cumyl alcohol. The reaction time was 3 hours.

Upon completion of the reduction reaction, the reaction product was transferred to the decomposition reactor to proceed the decomposition reaction.

Other conditions were the same as in Comparative Example 1 to prepare phenol, acetone and alpha methyl styrene.

The experimental conditions of Example 1 and Comparative Examples 1 to 3 are summarized in Table 1 below.

Cumene hydroperoxide -> cumyl alcohol Cumyl alcohol -> alpha methyl styrene catalyst Hydrogen
(cc / min) CHP concentration
(weight%) catalyst Whether the dehydration process is separated Example 1 Pd / C 150 25 Sulfuric acid detach Comparative Example 1 Co / Al / PO ₄ 0 25 Sulfuric acid Non-separation Comparative Example 2 Co / Al / PO ₄ 0 27 Sulfuric acid Non-separation Comparative Example 3 Co / ZrO ₂ 0 27 Sulfuric acid Non-separation

Experimental Example  One

The conversion of cumene hydroperoxide (CHP) and the selectivity and yield of cumyl alcohol (CA) in Example 1 and Comparative Examples 1 to 3 were calculated according to the following equations (1) to (3)

[Equation 1]

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

&Quot; (2) "

CA selectivity (%) = (CA product (mol%)) / (CHP feed (mol%) - CHP product (mol%

&Quot; (3) "

CA yield (%) = CHP conversion (%) * CA selectivity (%)

CHP Conversion Rate (%) CA
Selectivity (%) CA
yield(%) Example 1 84.52 98.33 83.11 Comparative Example 1 2.28 74.07 1.69 Comparative Example 2 23.1 83 19.17 Comparative Example 3 35.1 83 29.13

From the results shown in Table 2, Example 1 of the present invention shows that the conversion of cumene hydroperoxide (CHP) and the selectivity of cumyl alcohol (CA) are carried out by performing a hydrogenation reaction using Pd / C as a catalyst As a catalyst, Co / Al / PO₄ And Co / ZrO₂Using It was remarkably superior to Comparative Examples 1 to 3 in which the reduction reaction proceeded, and the production of cumyl alcohol was remarkably increased.

Measurement of Conversion Rate, Selectivity and Yield by Dewatering Process Separation

In order to compare the yields of phenol, acetone and alpha methylstyrene with respect to the case of separating the dehydration process of alpha methylstyrene from cumyl alcohol and the dehydration process together with the cumene hydroperoxide stream, the following experiment was conducted Respectively.

Experimental Example  2

The dehydration process was carried out for 7 hours at a temperature of 60 DEG C under 0.06 g of sulfuric acid catalyst per 150 g of 25% by weight cumene hydroperoxide.

Experimental Example  3

112.5 g of 25% by weight cumene hydroperoxide and 37.5 g of 30% by weight of cumyl alcohol were subjected to a dehydration process at a temperature of 80 ° C for 7 hours under 0.06 g of sulfuric acid catalyst.

Experimental Example  4

75 g of 25% by weight cumene hydroperoxide and 75 g of 30% by weight cumyl alcohol were subjected to a dehydration process at a temperature of 80 ° C for 7 hours under 0.06 g of sulfuric acid catalyst.

Experimental Example  5

The dehydration process was conducted for 7 hours at a temperature of 80 DEG C under 0.06 g of sulfuric acid catalyst with respect to 150 g of 30 wt% cumyl alcohol.

The reaction conditions of Experimental Examples 2 to 5 are summarized in Table 3 below.

Cumene hydroperoxide
(g) Cumyl alcohol
(g) Sulfuric acid (g) Reaction temperature
(° C) Reaction time
(hr) Experimental Example 2 150 0 0.06 60 7 Experimental Example 3 112.5 37.5 0.06 80 7 Experimental Example 4 75 75 0.06 80 7 Experimental Example 5 0 150 0.06 80 7

In Experimental Example 2, the dehydration reaction was carried out only on cumene hydroperoxide, and the reaction temperature was lowered to 60 ° C due to the high reactivity of cumene hydroperoxide.

The conversion, selectivity and yield of phenol, acetone and alpha methylstyrene for Experimental Examples 2 to 5 are shown in Table 4 below.

Cumene hydroperoxide
-> phenol Cumene hydroperoxide
-> acetone Cumyl alcohol
-> alpha methyl styrene Conversion Rate
(%) Selectivity
(%) yield
(%) Conversion Rate
(%) Selectivity
(%) yield
(%) Conversion Rate
(%) Selectivity
(%) yield
(%) Experimental Example 2 100.0 91.4 91.4 100.0 83.3 83.3 - - - Experimental Example 3 65.9 38.6 25.5 65.9 33.1 21.8 87.8 30.7 27.0 Experimental Example 4 66.4 19.5 12.9 66.4 21.3 14.1 69.5 52.5 36.5 Experimental Example 5 - - - - - - 42.9 97.3 41.8

Referring to Table 4, in Experimental Examples 2 and 5, phenol, acetone and alpha methylstyrene showed higher conversion, selectivity, and yield than Experiments 3 and 4, respectively.

Therefore, when the dehydration process for producing phenol and acetone from cumene hydroperoxide and the dehydration process for producing alpha methylstyrene from cumyl alcohol are separately conducted, when the dehydration process is simultaneously performed for cumene hydroperoxide and cumyl alcohol It can be seen that alpha methyl styrene can be produced at a high yield without lowering the yield of phenol and acetone.

1, 100: oxidation reactor
2, 4, 200, 310, 500: reservoir
3, 400: Stripper
5: decomposition reactor
6, 700: neutralizing device
7, 800: Separation device
300: hydrogenation reactor
320: First decomposition reactor
600: Second decomposition reactor

Claims (13)

(a) oxidizing cumene to produce a cumene hydroperoxide stream;
(b) separating at least a portion of the cumene hydroperoxide stream and hydrogenating it under a noble metal catalyst to produce cumyl alcohol;
(c) dehydrating the reactant containing the cumyl alcohol under an acidic catalyst; And
(d) separately dehydrating the remaining portion of the cumene hydroperoxide stream not subjected to the hydrogenation reaction;
≪ / RTI > wherein the phenol, acetone,
The method according to claim 1, wherein in the step (d), the remaining part of the cumene hydroperoxide stream not subjected to the hydrogenation reaction is dehydrated under an acidic catalyst.
The catalyst according to 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. Gt;
The method of claim 1, wherein the noble metal catalyst further comprises a carrier selected from the group consisting of alumina, silica, clay, carbon, zirconia, titania, mesoporous molecular sieve, ≪ / RTI > wherein the phenol, acetone, and alpha methylstyrene are prepared.
The method of claim 1, wherein the noble metal catalyst is used in an amount of 0.5 to 15 parts by weight based on 100 parts by weight of the cumene hydroperoxide stream.
2. The process of claim 1, wherein in step (a), the cumene hydroperoxide stream produces a cumene hydroperoxide stream at a concentration of from 5 to 25% by weight.
The process for producing phenol, acetone and alpha methylstyrene according to claim 1, wherein 5 to 50% by weight of the cumene hydroperoxide stream is separated and used in the hydrogenation reaction in the step (b).
The process according to claim 1, wherein the hydrogenation reaction is carried out at a hydrogen flow rate of 1: 1 to 1:10 for 0.2 to 7 hours, depending on the temperature and the molar ratio of cumene hydroperoxide to 40 to 80 ° C. And alpha methyl styrene.
2. The process of claim 1, wherein the cumene hydroperoxide stream further comprises cumyl alcohol.
The process for producing phenol, acetone and alpha methylstyrene according to claim 1 or 2, wherein the acid catalyst is a liquid or solid acid catalyst.
The method of claim 10, wherein the liquid acid catalyst is hydrochloric acid, sulfuric acid, or nitric acid, the solid acid catalyst is a Group 4 metal oxide modified with a Group 6 metal oxide, a sulfurated transition metal oxide, a cerium oxide and a Group 4 metal oxide Mixed metal oxides, and mixtures thereof. ≪ RTI ID = 0.0 > 8. < / RTI >
The method of claim 1, wherein in step (b), the cumene hydroperoxide stream is at least partially separated without concentration.
The method according to claim 1, wherein the cumene hydroperoxide stream is concentrated and dehydrated in step (d).

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