KR810001024B1 - Method for producing tert-butyl alcohol - Google Patents

Abstract

Tert-butylalcohol was prepd. by the hydration of isobutene over a strongly acidic cation exchanger catalyst. The catalyst was introduced to a reactor and the isobutene and water were contacted at 50-150oC in a continuous phase. The water descends from the surface of the particles at rate of 1 ml hr with an empty receiver. The reaction mixt. was withdrawn continuously. Pref. the catalyst has surface area 0.2-120 m2/g, porosity>0.03ml/ml, particle size 0.1-5mm, and ion exchange capacity>1 m eq.

Description

Method for preparing tert-butyl alcohol

1 is an outflow schematic illustrating an example of a method according to the invention.

2 is a partially enlarged view showing a state in which isobutylene and catalyst particles are in contact with each other.

The present invention relates to a process for the continuous high yield of tert-butyl alcohol (omitted by TBA) from isobutylene and water using a strongly acidic cation exchange resin as a catalyst.

In particular, the present reaction relates to a method of continuously producing a high yield of TBA without adding an agent such as a reaction aid.

It is known to produce TBA by hydrating isobutylene with sulfuric acid having various concentrations. This method has a high yield of TBA, but produces an isobutylene polymer as a by-product and uses a corrosive sulfuric acid, which does not maintain the device for a long time and consumes sulfuric acid.

It is known to directly hydrate isobutylene using phosphoric acid as a catalyst, but this method requires conditions of high temperature and pressure and is low in yield of TBA.

In addition, many methods for synthesizing TBA by direct hydration with a cation exchange resin catalyst have also been proposed. See, eg, Indusrrial and Engineering Chemistry, Vol. 53, No. 3, PP209-211 discloses a method of continuously hydrating isobutylene using an ion exchange resin catalyst, but the conversion of isobutylene is up to 30%.

In fact, since water and isobutylene form a heterogeneous system, in the presence of the above-described catalyst, it is difficult to simply contact isobutylene with water to effectively achieve the reaction. This fact is clearly described in the specifications of Japanese Patent Publication Nos. 50-32116, 50-126603, 50-137906 and 51-59802. In order to eliminate this drawback, as the reaction aid, an organic acid is added to the reaction system (Japanese Patent Publication Nos. 50-32116 and 50-126603), alcohol is added (Japanese Patent Publication No. 50-137906), or ethyl cellosolve And various methods such as using a polar solvent such as dioxane and using an emulsifier if necessary (Japanese Patent Publication No. 51-59802) have been studied by many technicians until now. However, all these methods of adding reaction aids present a great deal of inconvenience and difficulty in adding a third material, separating and recovering reaction aids, or separating the TBA from the aqueous layer containing the TBA.

Moreover, the method of hydrating isobutylene using the ion-exchange resin of suspension state is well-known (Japanese Patent Publication No. 40-2408). In this method, isobutylene, water and a catalyst are mixed in a reactor, mixed and stirred to form a suspension.

Then, the reaction mixture is separated from the reactor into an aqueous layer and an oil layer, and the aqueous layer containing the catalyst in the suspension is recycled to the reactor. Although this method has its own advantages, there are disadvantages in that it requires stirring to keep the catalyst in a suspended phase, and difficulty in recycling the liquid phase containing the suspended catalyst. In practice, this method is difficult to perform industrially.

In particular, the strong acid cation exchange resin used is used as a catalyst, and the depletion and separation of the catalyst are remarkable because of a large number of microporous materials or cells. According to the present invention, when a reaction is carried out using a catalyst by adding a reaction aid such as an organic acid, alcohol, ethyl cellosolvedioxane surfactant, expansion and deformation of the resin due to the porous group of the reaction aid are remarkable. The life is greatly shortened. Therefore, it is very difficult to carry out this process commercially using strong acid cation exchange resin with high catalytic properties.

Many methods to eliminate the drawbacks of these methods have been found to continuously produce TBA, which results in the formation of a non-uniform or non-uniform mixture with water in the manner described above on the surface of the strong acid cation exchange resin catalyst particles. The present invention was completed by the discovery that contacting isobutylene with very effective TBA can be obtained.

The present invention provides a method for preparing TBA by reacting isobutylene with water in the presence of a strong acid cation exchange resin catalyst, in particular, filling the catalyst particles in the reactor, and filling the liquid isobutylene in a continuous phase between the catalyst particles. Continuous contact with water at 50 to 150 ° C. and an average linear velocity of 1.0 m / hr. Or more than (empty container basis) relates to a method for continuously producing a TBA characterized in that the surface of the catalyst particles to flow down the water to flow out the reaction product from the reactor continuously. The present invention also provides another method for preparing TBA by reacting isobutylene with water in the presence of a strong acid cation exchange resin catalyst, that is, surface area of 0.2 to 120 m 2 / g, porosity of 0.03 ml / ml or more, exchange capacity of 1.0 meq / g or more and a strong acid cationic exchange resin catalyst having a particle size of 0.1 to 5 mm was dried in the reactor and filled with liquid isobutylene continuously between the catalyst particles to form a liquid isobutylene at 50 to 150 ° C. In continuous contact with an average linear velocity of 1.0 m or more / hr. It relates to a method for continuously producing TBA, characterized in that water is flowed down the surface of the catalyst particles in an empty container, that is, based on a reactor, and the reaction product is continuously discharged from the reactor.

The present invention aims to produce a high TBA yield continuously from water and isobutylene using a strong acid cationic exchange resin as a catalyst. It is also an object of the present invention to continuously obtain a large amount of TBA without adding a third substance which is a reaction accelerator such as, for example, an organic acid, alcohol, ethyl cellosolve, dioxane, and a surfactant.

It is also an object of the present invention to continuously prepare TBA on a commercial scale without the use of sulfuric acid, which is corrosive and harmful.

Isobutylene in the present invention uses a hydrocarbon containing isobutylene, such as isobutylene itself, isobutylene mixture, a mixture of butene and / or butane, and a mixture of isobutylene and other inert hydrocarbons. For industrial purposes, hydrocarbon mixtures of 4 carbon atoms obtained from pyrolysis, catalytic cracking and steam cracking of petroleum are used, in particular hydrocarbon mixtures having carbon dioxide removed. The concentration of isobutylene in this mixture is generally 80% or less and in the range of approximately 20-50%. In particular, the present invention provides a method for effectively synthesizing TBA from isobutylene containing such hydrocarbons.

The strong acid cation exchange resin mentioned in the present invention is a strong acid cation exchange resin, and styrenesulfonic acid resins and phenolsulfonic acid resins are typical examples. The resin obtained by copolymerizing a high unsaturation compound such as styrene and divinyl benzene is sulfonated to obtain a styrene sulfonic acid type resin and introducing sulfonic acid group (-SO ₃ H) into the copolymer to be crosslinked.

The phenol sulfonic acid type resin is a resin obtained by introducing a -SO ₃ H group into a condensation product of phenol and formaldehyde.

According to the present invention, the strong acid ion exchange resin generally uses a particle type having an average particle size of about 0.1 to 10 mm, particularly 0.3 to 2 mm.

Strongly acidic cation exchange resins to which the present invention is used are based on styrene-divinylbenzene copolymers, and the elements exhibiting properties are particularly important in terms of ion exchange capacity, particle size specific gravity, crosslinking degree, surface area and porosity. Strong acid cation exchange resins having a specific surface area, porosity, ion exchange capacity and particle size are very useful as catalysts for synthesizing TBA from isobutylene and water.

The surface area is preferably 0.4 to 100 m 2 / g in the range of 0.2 to 120 m 2 / g. The measurement of the surface area is performed by measuring the surface area of BET using nitrogen using a cation exchange resin dried at 80 ° C. for 6 hours in a vacuum. If the value is 0.2 m 2 / g or less, the rate of the desired hydration reaction is delayed, and when it is larger than 120 m 2 / g, problems arise in the durability of the resin and the strength of the machine. Porosity was achieved using Prac. Natl. Acad, Soci., Vol. 7, P., 115 (1921). It is useful when the value of the resin is 0.03 ml / ml or more, with the range of 0.05 to 1.0 ml / ml being particularly useful.

Small porosity slows down the desired rate of hydration. Resins called gel-types are not within this porosity range. In the present invention, a resin having the above small holes in the structure is preferably used.

The strong acid cation exchange resin used in the present invention has an ion exchange capacity of 1.0 meq / g or more (preferably 2.0 to 6.0 meq), particle size of 0.1 to 5 mm and specific gravity of 1.0 to 1.4. The ion exchange capacity is expressed in mg amount of sulfonic acid group contained in 1 g of dry catalyst particles. When the ion exchange capacity is 1.0 or less, the yield of TBA is reduced.

If the particle size is 0.1mm or less, it cannot be used for the filled holder, and when 5mm or more, the catalytic action of the resin is reduced. The strong acid cation exchange resin of the present invention preferably contains 1 to 15% of divinylbenzene and its properties in the resin structure (crosslinking degree).

The strong acid cation exchange resin having the properties of the present invention is polymerized using a solvent such as tert-amyl alcohol, secondary-butyl alcohol and isooctane, which is suitable for an equivalent and not suitable for a swelling polymer, and copolymerizes styrene and divinylbenzene. The obtained high molecular weight polymer is prepared by sulfonation. The present invention provides a method of continuously producing a high yield of TBA by contacting isobutylene with water using a strong acid cation exchange resin as a catalyst on the surface of the catalyst particles as described above.

The invention can be further illustrated by the accompanying drawings. In FIG. 1, catalyst particles 1 are charged to the reactor and 2 is in a stationary state. The reactor is longitudinally long and there is a wire mesh or perforated plate at the bottom filled with granular catalyst. Reaction zone 3 was filled with catalyst particles in the reactor and filled with liquid isobutylene between the catalyst particles.

Water is continuously charged into the liquid phase through a distributor 6 at the top of the reactor.

The way in which isobutylene and catalyst particles are contacted is clearly indicated in FIG. In FIG. 2, the catalyst particles are labeled with 1 and isobutylene 7 is filled in the continuous phase and the liquid phase. The water labeled 8 flows along the surface of the catalyst particles. It is not necessary for water to run down all the surfaces of the catalyst particles, but the greater the surface area covered in the water, the better. Water flows downward due to gravity and the specific gravity of water is greater than that of isobutylene forming a continuous phase.

When water flows through the catalyst particles, isobutylene penetrates into the water and dissolves, causing water and isobutylene to be in contact with each other at the surface of the catalyst.

When the catalytic reaction is carried out in this way, the yield of TBA is high and little by-product of the isobutylene polymer is produced.

The reason for the superior synthesis effect of TBA is not clear, but the specific contact method on the catalyst particles, the affinity and adsorption conditions of the isobutylene and water on the catalyst surface appear to influence the high yield of TBA.

The isobutylene forming the continuous phase is continuously filled along the number line with the liquid phase, and the reaction mixture contacted as described above flows out through the number 9 line. When isobutylene is charged to form a continuous phase, some of the isobutylene moves down in the reactor.

1 shows the continuous phase isobutylene moving from the top of the reactor to the bottom. Thus, in the present invention, a method of putting isobutylene in the lower part of the reactor and gradually moving upwards to form a continuous phase as a whole and flowing out of the upper part of the reactor (not shown in the drawing) is used.

The contact method according to the present invention is effectively performed in the following manner.

That is, the liquid hydrocarbon (hydrocarbon or inert hydrocarbon containing isobutylene) is first charged to the reactor, isobutylene is supplied through No. 5 line and mon is fed into No. 4 line, and then the temperature is gradually raised to start the reaction. In the initial stage, isobutylene and water were supplied through lines 5 and 4, respectively, but isobutylene was charged into the reactor and water was discharged through line 3 to increase the temperature.

The cation exchange resin used in the present invention is preferably used after sufficiently wetting with water from the beginning. When wetted with water, the cation exchange resin is immersed in a large amount of water having a temperature of 0 ° to 100 ° C for 1 minute to 24 hours.

The use of a cation exchange resin sufficiently moistened with water in the present invention inhibits the production of secondary reaction products, in particular isobutylene polymers and significantly reduces the degradation of the activity of the catalyst. In the case of using a cation exchange resin sufficiently wetted with water in advance, a method in which the dried resin is filled into the reactor, filled with water to come into contact with the resin, followed by draining the water and filling the reactor with isobutylene in the above-described manner is preferably performed.

In the present invention, the reaction temperature is in the range of 50 ° to 150 ° C and preferably 60 ° to 100 ° C. When the reaction temperature is lower than 50 ℃ reaction rate is slowed down and TBA is not produced effectively. On the contrary, if it is 150 degreeC or more, by-products, such as an isobutylene dimer, an isobutylene trimer, and a secondary-butyl alcohol, are produced | generated abundantly and the quality of a catalyst will fall significantly.

According to the present reaction, there is no particular limitation on the reaction pressure, and the pressure is such that hydrocarbon and water containing isobutylene or isobutylene can form a liquid phase at the reaction temperature. 2 to 50 kg / cm 2. G pressure is easy and 5 to 40 kg / cm 2. G is preferred.

In this reaction, water has an average linear velocity of 1.0 m / hr or more based on the empty reactor, preferably 1.0 to 30 m / hr, and particularly preferably 1.5 to 20 m / hr.

In order to maintain the linear velocity of the water, in addition to continuously filling the above-mentioned amount of water, the unreacted water flowing out of the reactor is recycled and supplied. When the average linear velocity is 1.0 m / hr or less, the rate at which isobutylene is converted to TBA decreases and undesirable copolymerization of butene is likely to be promoted.

Isobutylene is filled with an average linear velocity of 0.2 to 50 m / hr based on the empty reactor, and preferably 1.0 m / hr or more (Examples 1 to 30 m / hr).

The supply amount of water and isobutene indicated by the LHSV compared to the catalyst is from 0.1 to 5.0hr ^-1, respectively, 0.2 to 4hr ^-1 are preferred, and most preferred from 0.3 to 1.5hr ^-1.

When a cation exchange resin having a linear velocity of water based on an empty container of 1.0 m / hr or more, for example, 0.1 to 30 m / hr and having properties outside the range described in the present invention as a catalyst, the contact action of the hydration reaction is A large amount of catalyst is required to lower and obtain a satisfactory contact action, resulting in an overall lengthwise reactor. These facts make it difficult for water to flow along the surface of the catalyst particles, and more water flows along the tube walls, making production of shell and tubular reactors effective in reducing TBA production and removing heat of reaction.

In the case of using the catalyst according to the present invention and not using a special method of contacting the reactant with the catalyst particles according to the present invention, the contact reaction between water and isobutylene on the catalyst surface is difficult to proceed constantly, whereas the catalyst High side activity tends to cause undesirable side reactions.

In addition, when the catalytic reaction is carried out while stirring, for example, using a special catalyst of the present reaction under the conditions of the suspension, catalyst depletion and separation are caused.

The reaction mixture subjected to the contact reaction as described above flows out along line 9 to separate the TBA and recover by a conventional method. In this case, the reaction mixture along line 9 is recycled to the reactor via line 13. In this way, in order to make the contact reaction more effective when recycling, the temperature is controlled in the reactor and a constant reaction is performed.

In the present invention, the contact reaction is carried out in several steps. In this case, as shown in FIG. 1, in the first step, the reaction mixture discharged from Reactor 2 through Line 9 is introduced into Precipitator 10 to separate the hydrocarbon phase and the water phase. As in the first stage, the hydrocarbon phase is sent through the 5 'line to the 2' reactor and the aqueous phase is discharged from the lower part of the settler 10 to transfer to a separation and recovery device (not shown) such as a kind or azeotropic distillation unit. TBA is recovered. In step 2, water is fed from the top of reactor 2 'through line 4' and branch 6 '. In the two-stage reactor, the reaction is the same as the contact reaction in the one-stage reactor.

Therefore, the formed reaction product flows out along the 9 'line and is introduced into the precipitator 10'. The reaction mixture in precipitator 10 'is divided into a hydrocarbon phase and an aqueous phase. The separated hydrocarbon phase flows out through line 12, and the water phase flows out through line 11 'to separate and recover TBA in the same manner.

To illustrate the reaction more clearly, some examples are given below.

Example 1

In a cylindrical reactor having a diameter of 10 cm and a volume of 15.7 liters, a strong acid cation exchange resin (effective diameter of 0.45 to 0.6 mm, ion exchange capacity of 3.5 meq / g) is charged with a catalyst. Catalytic resin is obtained by sulfonating a resin prepared by copolymerizing styrene and divinylbenzene (divinylbenzene content 12%) and soaking with water sufficiently before adding. Hydrocarbons containing water and liquid isobutylene are continuously charged to the reactor with a piston pump. As a hydrocarbon containing liquid isobutylene, one obtained by extracting butadiene from a fraction obtained by steam cracking petroleum naphtha is used. The composition is as follows.

Before starting the reaction, the reactor is cooled to 5 ° C. and hydrocarbons containing liquid isobutylene are charged to the reactor to form a continuous phase. Hydrocarbons containing water and isobutylene are initially added to the reactor at the top of the reactor, gradually increasing at a rate of 0.5 l / hr to 16 l / hr. The linear velocity of water based on the reactor at this time is 2 m / hr.

Water flows down along the surface of the catalyst particles. The temperature of the reactor is initially 5 ° C. and gradually rises to 90 ° C. Continued pressure maintains the standard pressure at 30 kg / cm 2 while continuously discharging the liquid volume and balancing with the feed volume.

The hydration reaction is carried out in a non-uniform state under the above conditions. The obtained result is as follows.

As is clear from the results, the conversion rate of isobutylene to TBA is about 50% and the generation of by-products is very small.

Example 2

In a cylindrical reactor having a diameter of 7 cm and a volume of 4.2 L, the same strong acid cation exchange resin as in Example 1 (divinylbenzene content of 2%, effective diameter of 0.4 to 0.6 mm, ion exchange capacity of 3.3 meq / g) Put into catalyst.

Initially, the ion exchange resin is sufficiently moistened with pure water at the reaction temperature in the reactor. A hydrocarbon containing liquid isobutylene is fed and water is flowed to form a continuous phase of the hydrocarbon containing isobutylene in the reactor. The hydrocarbon containing liquid isobutylene used at this time is obtained by catalytic decomposition of gas oil, and the composition is as follows.

In the above-described state, the hydrocarbon and water containing the liquid isobutylene are charged in a reactor kept at 90 ° C., a speed of 5 L / hr, and a pressure of 20 kg / cm 2 .G. At this time, the linear velocity of water based on the empty container is 1.3 m / hr, and water flows down the surface with catalyst particles. The pressure of the system continuously flows out the amount of liquid compatible with the supply amount and maintains it at 20 kg / cm 2 .G. The reaction product obtained is as follows.

As is clear from the results, the conversion of isobutylene to TBA is 51%, and only a very small amount of by-products are produced.

Example 3

A sulfonic acid type cation exchange resin (ion exchange capacity of 2.9 meq / g) and a particle size of 0.35 to 1.2 mm prepared by sulfonating a styrene-divinylbenzene copolymer into a shell and tubular reactor having an inner volume of 15 m 3 is added as a catalyst. In the same manner as in Example 1, a continuous phase of a hydrocarbon containing liquid isobutylene is formed. The hydrocarbon containing isobutylene as a raw material is a hydrocarbon mixture obtained by extracting butanediene from a hydrocarbon mixture having 4 carbon atoms obtained by steam cracking naphtha, and the content of isobutylene is 46.4% by weight. While controlling the temperature of the reaction zone with cold water, hydrocarbon and water containing liquid isobutylene are continuously added at the top of the reactor. The feed rate is maintained at 8 ㎥ / hr, respectively, and the reaction temperature is adjusted to cold water to 90 ℃. The linear velocity of water, based on the empty container at rest, is 10.8 m / hr and the water flows down the surface of the catalyst particles. The pressure of the reactor is maintained at 20 kg / cm 2 .G while balancing the amount of hydrocarbon containing water and isobutylene while continuously flowing the liquid amount.

The reaction mixture obtained by carrying out the reaction under the above conditions is analyzed. The result is as follows:

As is clear from the results, the conversion rate of isobutylene to TBA is 60.8% and minor by-products are produced.

Example 4

The reaction is carried out in the same manner as in Example 3, the reaction mixture is introduced into the precipitator in a liquid phase, and divided into a hydrocarbon phase and an aqueous phase. The outflow rate from the first reactor of unreacted isobutylene containing hydrocarbons containing isobutylene is 5.74 m 3 / hr and the isobutylene content of the hydrocarbon is 25.3% by weight.

The hydrocarbon containing this isobutylene is fed continuously with freshly fed water at the top of the second reactor. The feed rate of water is 5 m3 / hr and the linear velocity based on the empty container is 6.75 m / hr.

The second reactor was also of the same type as the reactor used in Example 3. The reaction temperature of the second reactor is maintained at 85 ℃, the pressure is adjusted to 20kg / ㎠G.

In this state, the amount of reaction product obtained from the second reactor and the total amount obtained in the first and second are as follows:

Comparative Example 1

The same strong acid cation exchange resin as used in Example 1 is placed in a cylindrical reactor having a diameter of 10 cm and a volume of 4.2 liters. Pure water initially supplied to the reactor is sufficiently moistened with an ion exchange resin and a hydrocarbon containing liquid isobutylene is introduced into the reactor to form a continuous phase of hydrocarbon containing isobutylene. The hydrocarbon containing liquid isobutylene used at this time is the same as that obtained by extracting butadiene from what was obtained by steam cracking naphtha. The composition is the same as in Example 1.

In this state, hydrocarbon and water containing liquid isobutylene forming a continuous phase are charged at the top of the reactor at a rate of 2 l / hr. In this case, the reactor maintains a linear velocity of water at 0.25 m / hr based on 90 ° C., 20 kg / cm 2 G and the empty container. After stopping the reaction for 6 hours after the start of the reaction, the linear velocity of water is so small that the product of isobutylene polymer is as follows.

As is clear from the results, the production rate of TBA is 28% and a large amount of side reaction products are produced.

Comparative Example 2

The same strong acid cation exchange resin as used in Example 1 is placed in a cylindrical reactor having a diameter of 10 cm and a volume of 4.2 liters. Butadiene was extracted from the fraction obtained by steam cracking naphtha, and hydrocarbons and vapors containing the same isobutylene as used in Example 1 were continuously supplied to the reactor at 100 ° C. under atmospheric pressure. The rate of adding hydrocarbon containing isobutylene is 800 l / hr (GHSV, 190 / hr) and the steam is charged at 1000 l / hr (GHSV, 240 / hr). The amount of TBA produced is small and the production rate is as follows.

As is apparent from the above results, when both isobutylene and water react in the vapor state, the production rate of TBA is less than 1% and many by-products are produced.

Example 5

A strong acid cation exchange resin (surface area 54.1 m 2 / g: porosity 0.36 ml / ml: ion exchange capacity 3.8 meq / g: exchange rate of 13.1%, particle size 0.2 to 1.5 mm) was put in a cylindrical reactor having a diameter of 15 cm and a volume of 38 l. Put into catalyst. Catalytic resin is obtained by sulfonating a resin produced by copolymerizing styrene and divinylbenzene and sufficiently wetted with water before adding. Before starting the reaction, the reactor is cooled to 5 ° C. and a hydrocarbon containing liquid isobutylene is charged to the reactor to form a continuous phase of this hydrocarbon. Hydrocarbons containing isobutylene are prepared by extracting and removing butadiene from a hydrocarbon group having 4 carbon atoms obtained by steam cracking petroleum naphtha. The composition is as follows.

Hydrocarbons containing water and liquid isobutylene are continuously introduced into the reactor with a piston pump at the top of the reactor. Hydrocarbons containing water and isobutylene are initially added at 0.5 l / hr and gradually increased to 26 L / hr. The linear velocity of water based on the empty container is 1.5 m / hr and the water flows down the surface of the catalyst date. The reaction temperature of the reactor gradually increases from 5 ° to 92 ° C. In order to maintain the pressure of the system to 30kg / ㎠ to continue to supply the liquid amount from the bottom of the reactor while maintaining the balance.

Under such conditions, the hydration reaction is carried out in a non-uniform state. The obtained result is as follows.

As is evident from the results, the conversion of isobutylene to TBA is 57.4% and very little byproducts are produced.

Example 6

Strong acid cation exchange resin prepared by sulfonating styrene-divinylbenzene weight in a shell and tubular reactor with an inner surface of 15m3 (surface area of 3.4㎡ / g, porosity 0.11ml / ml: ion exchange capacity 3.6meq / g: particle size) 0.2 to 1.5 mm) as a catalyst. In the same manner as in Example 5, a continuous phase of hydrocarbon containing isobutylene in the liquid phase is formed in the reactor. Hydrocarbons containing isobutylene as a raw material are obtained by extracting butadiene from hydrocarbons having 4 carbon atoms by steam cracking naphtha, and isobutylene content is 46.4%. Water and isobutylene are charged continuously to the reactor from the top of the reactor while controlling the temperature of the reaction zone with cold water. Each feed rate is finally maintained at 7.2 m3 / hr. The reaction temperature is adjusted to water to 91 캜. The linear velocity of water at standstill relative to the empty container is 9.7 m / hr and the water flows along the surface of the catalyst particles. The reaction pressure is maintained at 20 kg / cm 2 G by continuously flowing out the liquid amount corresponding to the amount of hydrocarbons containing water and isobutylene continuously supplied. The reaction is carried out under the above conditions. The result obtained by analyzing the resulting reaction mixture is as follows.

In the results, the conversion rate of isobutylene to TBA is 67.0 and the by-products are produced in trace amounts.

Example 7

After the reaction is carried out according to the method described in Example 6, the reaction mixture is introduced into the precipitator in the liquid phase to separate the hydrocarbon phase and the main phase. The outflow rate from the first reactor of the hydrocarbon containing isobutylene including unreacted isobutylene was 5.31 m 3 / hr and the fraction of isobutylene was 17.3% by weight. Hydrocarbons containing isobutylene, along with freshly fed water, are continuously fed in the top of the second column. The amount of water supplied is 5.3 m3 / hr and the linear velocity based on the empty container is 7.16 m / hr. The second reactor is of the same type as the reactor used in Example 6. A continuous phase of hydrocarbon containing isobutylene has already been formed in the second reactor and the temperature and pressure of the second reactor are controlled at 85 ° C. and 20 kg / cm 2, respectively.

Under the above conditions, the amount of reaction product obtained from the second reactor and the total amount of reaction product obtained from the first and second reactors are as follows.

Claims (1)

In a method of preparing tert-butyl alcohol by reacting water with liquid isobutylene in the presence of a strongly acidic cation exchange resin as a catalyst, the catalyst particles are charged to a reactor and the liquid isobutylene is continuously separated between the catalyst particles. Continuous contact with water at 50 to 150 ° C. under conditions filled with water and with an average linear velocity of 1.0 m / hr or more (reactor based) allowing water to flow along the surface of the catalyst particles to continuously discharge the reaction mixture from the reactor. Characterized in that continuously preparing tert-butyl alcohol.

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