JP5793922B2 - Heterogeneous liquid phase reaction method - Google Patents

Description

  The present invention relates to a heterogeneous liquid phase reaction method.

Conventionally, a heterogeneous liquid phase reaction method in which liquid phases that do not dissolve each other are reacted is known.
In the heterogeneous liquid phase reaction, the reaction proceeds in a state where the liquid phases form an interface. However, since the contact between both phases is insufficient, it is difficult to obtain a sufficient reaction rate.
Moreover, even if a solid catalyst is used as the catalyst, the reaction field of the heterogeneous liquid phase reaction is liquid-liquid-three-phase, so contact of each phase is likely to be limited, and an industrially sufficient reaction rate is achieved. It was difficult to get.
Therefore, in order to obtain a desired reaction rate, it is necessary to use a large amount of catalyst, which is costly. In addition, since the reaction results greatly depend on the contact state of each phase, it is difficult to stably operate the reaction process.

As a heterogeneous liquid phase reaction method in a reactor filled with a solid catalyst, for example, liquid isobutylene and water are reacted in the presence of a strongly acidic cation exchange resin as a solid catalyst to produce tertiary butyl alcohol. A manufacturing method is known (for example, refer to Patent Documents 1 and 2).
In Patent Document 1, an organic phase (isobutylene) is used as a continuous phase, an aqueous phase is used as a dispersed phase, and water is allowed to flow on the surface of solid catalyst particles packed in a reactor at a linear velocity of 1 m / hr or more. A method of reacting with water is disclosed.
On the other hand, Patent Document 2 discloses a method of reacting isobutylene and water in a state where the composition of the reaction solution includes a region of a specific homogeneous liquid phase and a heterogeneous liquid phase.

JP 54-30104 A JP-A-56-10124

  However, Patent Document 1 does not mention anything about the dispersion state of the aqueous phase in the organic phase. When the aqueous phase is in a large lump, the contact area with the organic phase is reduced, and the reaction rate is reduced. There was a problem that the remarkably decreased. In Patent Document 1, water as a reaction product is continuously supplied to the upper part of the reactor through the disperser, but nothing is said about a specific dispersion method or dispersion state.

  Patent Document 2 does not mention a specific reaction method in the case where the composition of the reaction solution is in the region of a heterogeneous liquid phase. Therefore, even when the reaction is carried out in the composition region disclosed in Patent Document 2, if the composition is in the region of the heterogeneous liquid phase and the heterogeneous liquid phase is not sufficiently dispersed in the reactor, There was a problem that the liquid-liquid-piece contact state was poor, and the reaction rate was significantly reduced.

  The present invention has been made in view of the above circumstances, and provides a heterogeneous liquid phase reaction method in which liquid phases that do not dissolve each other are reacted at a high reaction rate.

  As a result of intensive studies, the present inventors have focused on the fact that the liquid-liquid-solid contact state in the heterogeneous liquid phase reaction is improved and the reaction rate is increased if the liquid dispersion state of the heterogeneous liquid phase is uniform. . The liquid dispersion state of the heterogeneous liquid phase can be controlled by the differential pressure generated before and after the liquid supply means for supplying the reaction liquid to the reactor filled with the solid catalyst, and the reaction liquid is supplied to the reactor with a specific differential pressure. As a result of the supply, the liquid dispersion state was found to be uniform, and the present invention was completed.

That is, the heterogeneous liquid phase reaction method of the present invention is a heterogeneous liquid phase reaction method in which a reaction solution is supplied from a liquid supply unit to a flow reactor filled with a solid catalyst, and liquid phases that do not dissolve each other react with each other. The reaction is a hydration reaction between a hydrophilic phase containing water and a lipophilic phase containing a hydrocarbon containing isobutylene, and a differential pressure generated before and after the liquid supply unit is 0.04 kg / cm ² or more. It is characterized by.
Here, at the same height of the flow reactor, it is preferable to measure the temperature of the solid catalyst in the flow reactor at a plurality of points to manage the liquid dispersion state of the heterogeneous liquid phase during the reaction .

  According to the present invention, it is possible to provide a heterogeneous liquid phase reaction method in which liquid phases that do not dissolve each other are reacted at a high reaction rate.

It is a schematic block diagram which shows an example of the reaction apparatus used for this invention. It is the elements on larger scale of the liquid supply means with which the reaction apparatus shown in FIG. 1 is equipped. It is a schematic block diagram which shows the reaction apparatus used by the test example. It is a figure which shows the nozzle attached to the liquid supply part of the reactor shown in FIG. 3, (a) is a side view, (b) is sectional drawing which follows the AA line of (a).

The present invention is a heterogeneous liquid phase reaction method in which liquid phases that do not dissolve each other are reacted.
The heterogeneous liquid phase to which the heterogeneous liquid phase reaction method of the present invention can be applied is not particularly limited, and examples thereof include two liquid phases in which two types of liquids (liquid phases) do not dissolve each other and form an interface. Specifically, a two-liquid phase in which the other liquid phase (dispersed phase) is dispersed in one liquid phase (continuous phase) can be mentioned.
In the present invention, the “liquid dispersion state” means a dispersion state of the other liquid phase (dispersed phase) dispersed in one liquid phase (continuous phase). Further, “does not dissolve in each other” indicates a state in which a liquid-liquid interface is formed by separating an arbitrary composition liquid into two phases.

Examples of the two-liquid phase include a combination of a hydrophilic phase and a lipophilic phase.
The substance that forms the hydrophilic phase is not particularly limited, and examples thereof include water and a mixture of water and a compound having high solubility in water.
Examples of the compound having high solubility in water include alcohols and acids.
Examples of alcohols include methanol, ethanol, butanol and the like. Moreover, you may use polyhydric alcohols, such as ethylene glycol.
Examples of the acids include acetic acid and formic acid.

  On the other hand, the substance forming the lipophilic phase is not particularly limited, and examples thereof include hydrocarbons and aromatic hydrocarbons.

  The heterogeneous liquid phase is particularly preferably a two-liquid phase that is a combination of a hydrophilic phase containing water and a lipophilic phase containing a hydrocarbon containing isobutylene.

The reaction to which the heterogeneous liquid phase reaction method of the present invention can be applied is not particularly limited, but is suitable for hydration reaction, dehydration reaction, hydrolysis reaction, oxidation reaction, esterification reaction, polymerization reaction, and condensation reaction. These reactions may be carried out singly or two or more may be carried out simultaneously.
Among these reactions, the present invention is particularly suitable for a hydration reaction between a hydrophilic phase containing water and a lipophilic phase containing a hydrocarbon containing isobutylene, and economically water of isobutylene at a high reaction rate. The sum reaction can be carried out. The hydrophilic phase and the lipophilic phase may contain tertiary butyl alcohol as a product and other substances.

Hereinafter, the heterogeneous liquid phase reaction method of the present invention will be described in detail with reference to FIG. 1, taking the hydration reaction of isobutylene and water as an example.
FIG. 1 is a schematic configuration diagram showing an example of a reaction apparatus used in the heterogeneous liquid phase reaction method of the present invention. The reaction apparatus 10 in this example includes a flow reactor 11 filled with a solid catalyst and a liquid supply means 12 for supplying a reaction liquid to the flow reactor 11.

The flow reactor 11 is not particularly limited as long as it can be filled with a solid catalyst. For example, a vertical multitubular type, a vertical circular tube type, a horizontal multitubular type, a horizontal circular tube type, or the like can be used. Among these, a vertical tube type is preferable from the viewpoint of ease of manufacture and economical viewpoint.
The specific shape of the vertical tube reactor is not particularly limited.
From the viewpoint of pressure loss that occurs when the reaction solution is passed through the catalyst layer 13 formed by filling the flow type reactor 11 with the solid catalyst, the height and inner diameter of the vertical tube reactor are A smaller ratio (height / inner diameter ratio) is preferable. On the other hand, from the viewpoint of efficiently carrying out mass transfer to the vicinity of the solid catalyst active point, it is preferable that the linear velocity at the time of liquid passing is high, that is, it is preferable that the height / inner diameter ratio is large. Taking both effects into consideration, the height / inner diameter ratio is preferably 0.2 to 3, and more preferably 0.5 to 2.5.

  The number of flow reactors 11 is not particularly limited, and may be one or two or more. When two or more flow reactors 11 are used, these may be arranged in parallel or in series, but are preferably arranged in series. If two or more flow reactors 11 are arranged in series, it becomes easy to adjust the temperature between the reactors, and the degree of freedom in operation increases. In particular, in the case of an equilibrium reaction, the ultimate conversion rate is significantly affected by temperature. Therefore, it is preferable to adjust the temperature of the fluid by installing a heat exchanger between the reactors.

The solid catalyst filled in the flow reactor 11 is not particularly limited as long as it contributes to the reaction as a catalyst.
When the hydration reaction of isobutylene and water is performed, the solid catalyst is preferably an acid catalyst, and examples thereof include strongly acidic cation exchange resins, zeolites, and heteropoly acids. Among these, a strong acidic cation exchange resin is preferable from an economical viewpoint. As the strongly acidic cation exchange resin, for example, commercially available products such as “Levacit K2431” and “Levacit K2621” manufactured by LANXESS and “Amberlyst 15J” manufactured by Rohm and Haas can be used.
A catalyst may be used independently and may mix and use two or more types.

  The method for holding the solid catalyst in the flow reactor 11 is not particularly limited, but it is preferable to use a wire mesh-like support (not shown) from the standpoint of ease of production and economics. Examples of the shape of the metal mesh support include a sheet shape, a sheet metal mesh bent, a cylindrical shape, a box shape, and the like. A commercially available product can be used as the wire mesh-like support, and examples thereof include “Johnson Screen” manufactured by Johnson Screens.

The liquid supply means 12 is not particularly limited as long as a liquid (reaction liquid) that forms a heterogeneous liquid phase can be dispersed.
As the liquid supply means 12, for example, a perforated plate, a nozzle, a nozzle provided with a throttling mechanism at the tip, a circular pipe 121 provided with a plurality of liquid supply holes 121b in the body 121a as shown in FIG. 2, the circular pipe For example, two or more 121 pieces may be arranged. Further, “Johnson Screen” manufactured by Johnson Screens Inc. can be used as a commercial product. Among these, from the economical viewpoint and the liquid dispersibility viewpoint, it is preferable to arrange two or more circular pipes 121 each having a plurality of liquid supply holes 121b in the body 121a as shown in FIG.

The method of arranging two or more circular tubes is not particularly limited, but a method of arranging them in parallel, a method of arranging them in a lattice shape, and arranging so that a plurality of circular tubes are orthogonal to a single circular tube. The method etc. are mentioned. Among these, the method of arranging two or more circular pipes in parallel is preferable because of the ease of structure.
The liquid supply means 12 shown in FIG. 1 has a hollow shaft tube 122 connected to a plurality of circular tubes 121 in parallel with each other (connected to the shaft tube 122 so as to be orthogonal). The pair of supply parts 123 are arranged so as to face each other so that the circular pipe 121 of the other supply part 123 fits between the circular pipes 121 of one supply part 123.

Although the shape of the liquid supply hole 121b of the circular pipe 121 shown in FIG. 2 is not particularly limited, a circular shape is preferable from the viewpoint of easy processing.
Also, the size of the liquid supply hole 121b is not particularly limited, but if it is too large, pressure loss during the supply of the reaction liquid is difficult to occur. Specifically, when the shape of the liquid supply hole 121b is circular, the diameter (hole diameter) is preferably 10 mm or less, and more preferably 8 mm or less.

From the viewpoint of liquid dispersibility, the liquid supply holes 121b are preferably disposed in a portion facing the catalyst layer in the flow type reactor, and a plurality of liquid supply holes 121b are preferably disposed in the concentric cross section of the body 121a.
The number of liquid supply holes 121b can be determined according to the cross-sectional area of the flow reactor. From the viewpoint of liquid dispersibility, 10 or more per cross-sectional area (1 m ² ) is preferable, and 20 or more is more preferable. On the other hand, from the viewpoint of ease of processing of the circular pipe 121 and the number of circular pipes, 100 or less per cross-sectional area (1 m ² ) is preferable and 50 or less is more preferable.

  Further, the liquid supply hole 121b may be configured to be movable by an external force. For example, a structure in which one of two overlapping perforated plates can be moved by an external force to change the number of holes and the shape of the holes can be used. By adopting such a structure for the liquid supply hole 121b, it is possible to control the differential pressure generated in the liquid supply means described later without opening the flow reactor during the heterogeneous liquid phase reaction. That is, there is an advantage that the liquid dispersion state can be easily controlled during the reaction.

  As shown in FIG. 1, the distance from the liquid supply hole (not shown) provided in the circular tube 121 constituting the liquid supply means 12 to the upper surface (uppermost portion) 13a of the catalyst layer 13 is preferably 3 m or less, and 2 m or less. Is more preferable. If the distance is too long, the liquid dispersion state of the reaction liquid (two liquid phases) may decrease before reaching the catalyst layer 13. On the other hand, if the distance is too short, there is a problem that the catalyst floats due to the reaction liquid supplied from the liquid supply hole. The distance from the liquid supply hole to the upper surface 13a of the catalyst layer 13 is preferably 0.1 m or more, and more preferably 0.2 m or more.

  A throttle mechanism (not shown) may be further provided inside the liquid supply means 12. The diaphragm mechanism is not particularly limited, but an orifice plate is preferable. The diaphragm mechanism may be installed alone or in a plurality of stages, but it is preferable to install a plurality of stages. If the throttle mechanism is installed in a plurality of stages, a differential pressure at the time of supplying the reaction liquid described later can be generated in a plurality of stages, the liquid dispersion state can be further improved, and further improvement in the reaction rate can be expected.

In the heterogeneous liquid phase reaction method of the present invention using such a reactor 10, the differential pressure generated in the liquid supply means 12 when the reaction liquid is supplied to the flow reactor 11 is 0.04 kg / cm ² (gauge). Pressure, the same shall apply hereinafter).
Here, “the differential pressure generated in the liquid supply means” means the differential pressure generated before and after the liquid supply means, the differential pressure generated in the pipe or valve in the liquid supply means, the differential pressure generated in the liquid supply hole, This is the differential pressure generated by the throttle mechanism.

If the differential pressure is 0.04 kg / cm ² or more, the liquid dispersion state of the heterogeneous liquid phase (reaction liquid) becomes uniform and good, and the contact between the solid catalyst in the flow reactor 11 and the heterogeneous liquid phase is improved. Well done and increases the reaction rate. Differential pressure is preferably 0.1 kg / cm ² or more, 0.2 kg / cm ² or more is more preferable.
The higher the differential pressure, the better the liquid dispersion state. However, if the pressure is too high, the reactor 10 is required to have high pressure resistance performance, or a high-pump liquid supply pump is required, and the cost tends to increase. It is in. Therefore, from an economic point of view, the differential pressure is preferably 5 kg / cm ² or less, 2 kg / cm ² or less being more preferred.

The method for adjusting the differential pressure generated in the liquid supply means 12 to a desired value is not particularly limited. For example, the flow rate of the reaction liquid is adjusted, or the liquid is adjusted to have an appropriate size with respect to the flow rate of the reaction liquid. For example, the diameter of the supply hole may be determined, or the liquid supply hole may be moved by an external force to adjust the diameter of the liquid supply hole.
When determining the appropriate hole diameter of the liquid supply hole with respect to the flow rate, a small-scale model experiment that can confirm the differential pressure and the liquid dispersion state is performed in advance to clarify the relationship between the flow rate and the generated differential pressure with respect to the hole diameter. It is preferable to keep it.

  In order to manage the differential pressure generated during the supply of the reaction liquid, it is preferable to install a pressure gauge (not shown) inside the flow reactor 11 and upstream of the liquid supply means 12. The type of pressure gauge is not particularly limited.

The particle size of the dispersed phase droplets in the reaction liquid (heterogeneous liquid phase) supplied to the flow reactor 11 is not particularly limited, but is preferably 2 mm or less, and more preferably 1 mm or less. More preferably, the particle diameter is smaller than the particle diameter of the solid catalyst packed in the flow reactor 11. If the particle size of the droplets of the dispersed phase is larger than the particle size of the solid catalyst, the contact between the liquid and the solid becomes insufficient, and the function of the catalyst may not be sufficiently exhibited, thereby reducing the reaction rate.
The droplets in the dispersed phase can be controlled by adjusting the differential pressure generated in the liquid supply means 12. Specifically, when the differential pressure is increased, the droplets in the dispersed phase tend to become smaller.

In the heterogeneous liquid phase reaction method of the present invention, it is preferable to measure a plurality of temperatures of the solid catalyst in the flow reactor 11 at the same height of the flow reactor 11.
Many commonly known chemical reactions involve heat transfer. In particular, in a heterogeneous liquid phase reaction, the progress of the reaction varies significantly depending not only on the liquid dispersion state but also on the supply state of the reaction liquid to the catalyst layer 13, and therefore a temperature difference is likely to occur.

When the liquid dispersion state of the heterogeneous liquid phase is good, the reaction tends to be performed uniformly in the radial direction of the flow reactor 11, and the temperature difference of the solid catalyst measured at a plurality of points tends to be small. On the other hand, when the liquid dispersion state is poor, the reaction is difficult to be performed uniformly in the radial direction, and thus the temperature difference of the solid catalyst tends to increase.
Accordingly, it is possible to determine the liquid dispersion state and the uniform supply state of the reaction liquid to the catalyst layer 13 by using the temperature difference of the solid catalyst as an index. Therefore, by measuring the temperature of the solid catalyst at the same height at a plurality of points. The liquid dispersion state can be managed, and the progress of the reaction can be easily known.

The position at which the temperature of the solid catalyst in the flow reactor 11 is measured is not particularly limited as long as it is the same height, but a position as far as possible from the liquid supply means 12 is preferable. At a position away from the liquid supply means 12, the reaction liquid tends to drift more easily and uniform supply to the catalyst layer 13 tends to be difficult. From the measurement result at this position to the catalyst layer 13 in the entire reactor. It is preferable to estimate the uniform supply state and manage the liquid dispersion state.
The number of measurement points at the same height is preferably 2 or more, more preferably 4 or more.
The position of the measurement point in the radial direction of the flow reactor 11 is not particularly limited, and a plurality of measurement points may be arranged on the circumference of the same radial position, or the measurement points are arranged at different radial positions. May be. From the viewpoint of evaluating liquid dispersibility in more detail, it is preferable to arrange measurement points at different radial positions.

As long as the heterogeneous liquid phase reaction is economically implemented, the temperature difference of the solid catalyst measured at multiple points at the same height is not particularly limited, but the liquid dispersion state is better as the temperature difference is smaller. Is preferably 5 ° C. or lower, more preferably 3 ° C. or lower.
The temperature difference of the solid catalyst can be controlled by adjusting the differential pressure generated in the liquid supply means 12. For example, in order to reduce the temperature difference, the differential pressure generated in the liquid supply unit 12 may be increased. However, as the differential pressure is increased, the cost tends to increase.

Note that, as the inner diameter of the flow reactor 11 increases, it becomes difficult to form an ideal extrusion flow of the reaction solution, and the temperature distribution of the solid catalyst in the radial direction tends to occur.
However, in the case of the heterogeneous liquid phase reaction method of the present invention, the liquid dispersion state can be satisfactorily maintained by defining the differential pressure generated by the liquid supply means. Since the distribution hardly occurs and an ideal extruded flow of the reaction liquid can be formed, a high reaction rate can be obtained. Such an effect of the present invention is more easily obtained as the inner diameter of the reactor is larger, and the present invention is particularly suitable when a reactor having an inner diameter of 1 m or more is used.

Further, as described above, the heterogeneous liquid phase reaction method of the present invention is suitable for various reactions such as a hydration reaction and a dehydration reaction, and is particularly suitable for a hydration reaction of isobutylene and water.
As isobutylene used as a raw material, isobutylene may be used alone, or a liquefied gas composed of a hydrocarbon containing isobutylene (isobutylene-containing hydrocarbon) may be used. Examples of the isobutylene-containing hydrocarbon include hydrocarbon mixtures having 4 carbon atoms such as butenes containing isobutylene (such as 1-butene and 2-butene) and butanes (such as n-butane and isobutane). These isobutylene-containing hydrocarbons are obtained as a by-product when naphtha is pyrolyzed in the presence of water vapor to obtain ethylene, a by-product when catalytic decomposition of heavy oil is catalyzed, preferably obtained by removing butadiene from these. It is done.

  Although the isobutylene density | concentration in isobutylene containing hydrocarbon is not specifically limited, 5-95 mass% is preferable and 10-90 mass% is more preferable. When the isobutylene concentration is extremely low, it is difficult to obtain an industrially required reaction rate, and when the isobutylene concentration is high, it is difficult to obtain industrially.

On the other hand, although it does not specifically limit as water used as a raw material, Deionized water, distilled water, etc. are preferable and deionized water is more preferable. Impurities in water may adversely affect catalyst deactivation and product quality, and are preferably removed as much as possible.
The amount of water in the hydration reaction of isobutylene and water is not particularly limited, but the molar ratio of water to 1 gram mole of isobutylene in the raw material (reaction solution) is preferably 0.1 to 50, 0.5 ~ 30 is more preferred. If the water molar ratio is too small, isobutylene dimers and trimers are likely to be formed, and if the water molar ratio is too large, the reaction rate of the hydration reaction tends to be low.

In the hydration reaction of isobutylene and water, an organic solvent and other additives may be contained in the reaction solution as necessary.
Moreover, although the temperature in a hydration reaction is not specifically limited, 25-100 degreeC is preferable and 45-80 degreeC is more preferable. If the temperature is too low, it is difficult to obtain a sufficient hydration reaction rate, and if the temperature is too high, dimerization, trimerization and other impurities of the raw isobutylene tend to be easily generated.

Moreover, the pressure in the hydration reaction is not particularly limited, but a pressure sufficient to liquefy isobutylene or isobutylene-containing hydrocarbon gas is preferable. Specifically, ² to 20 kg / cm ² is preferable, and 4 to 16 kg / cm ² is more preferable.
In order to maintain the pressure during the hydration reaction, an inert gas that does not participate in the hydration reaction may be introduced into the flow reactor 11. Examples of the inert gas include nitrogen and argon, but are not particularly limited.

  After the heterogeneous liquid phase reaction, a purification step may be provided as necessary. For example, in the hydration reaction of isobutylene and water, a mixture of isobutylene, water, and tertiary butyl alcohol obtained by the reaction can be purified by any method such as distillation, membrane separation, and decantation. Of these, distillation is preferred from an economical viewpoint.

As described above, when two or more flow reactors 11 are used, the composition of the reaction liquid (non-uniform liquid phase) in each reactor may be the same in all of the reactor groups, Each of the reactor groups may be different, or only a part of the reactor group may be a heterogeneous liquid phase.
Further, the flow direction to the flow reactor 11 is not particularly limited, but a downward flow is preferable from the viewpoint that the solid catalyst is easily held in the flow reactor 11. In the case of upward flow, it is sufficient to provide a space portion or a metal net for preventing outflow in order to prevent the solid catalyst particles from flowing out of the flow type reactor 11, but in this case, the cost tends to increase.

According to the heterogeneous liquid phase reaction method of the present invention described above, the liquid dispersion state of the heterogeneous liquid phase reaction can be made uniform by regulating the differential pressure generated in the liquid supply means, and the reaction rate is increased. be able to. Therefore, the amount of catalyst used can be reduced, which is economical.
In particular, if the temperature of the solid catalyst is measured at multiple points at the same height of the flow reactor, the liquid dispersion state can be managed, so it is easy to improve or change the liquid dispersion state by adjusting the differential pressure generated in the liquid supply means. Thus, the reaction rate can be increased more easily.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

[Test example]
Hereinafter, test examples will be described. In addition, the following test examples 1-4 were implemented in order to confirm a liquid dispersion state.
As a model substance of a heterogeneous liquid phase, 50 L of deionized water and 100 L of n-hexane (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) were used, and the test was performed using the reaction apparatus 20 shown in FIG.
The reactor 20 shown in FIG. 3 includes an acrylic square water tank (depth: 100 mm, width: 1040 mm, height: 2300 mm, internal volume: 240 L) 21 and a liquid suction port 21 a provided at the bottom of the water tank 21. And a water supply circulation unit for extracting a part of the water phase from the liquid supply unit 22 installed in the upper part of the water tank 21 and the liquid suction port 21a and re-supplying the extracted water phase from the liquid supply part 22 to the water tank 21. A pump 23 and a pressure gauge 24 installed upstream of the liquid supply unit 22 are provided. A flow meter 25 is installed between the water phase circulation pump 23 and the liquid supply unit 22.
The liquid outlet 22a of the liquid supply section 22 is a T-shaped nozzle having an inner diameter of 34 mm and a length of 76 mm, as shown in FIGS. 4A and 4B, with both ends closed. 22b is attached. The nozzle 22b is provided with four liquid supply holes 22c having an inner diameter of 5 mm at a position of 38 mm in the length direction, two in the horizontal direction and two in the downward 45 ° direction. The nozzle 22b is immersed in the upper phase (n-hexane phase) generated by the two-phase separation, and the horizontal liquid supply hole 22c is located at a height of 200 mm below the upper liquid surface of the n-hexane phase. Was installed.

Using this reactor 20, the test was carried out as follows.
After placing the model substance in the water tank 21 and allowing it to stand, a part of the water phase generated by the two-phase separation is extracted from the liquid suction port 21a provided in the lower part of the water tank 21 with the water phase circulation pump 23, and the water tank 21 It was resupplied to the water tank 21 from the liquid supply part 22 installed in the upper part.
In addition, the lid was not provided in the upper part of the water tank 21, but the inside of the water tank 21 was made into atmospheric pressure. The gauge pressure measured by the pressure gauge 24 provided upstream of the liquid supply unit 22 was regarded as a pressure loss generated in the liquid supply unit 22.

In this test, the liquid in a non-uniform state is not directly supplied from the liquid supply unit 22 to the water tank 21, but only the aqueous phase is supplied from the liquid supply unit 22 to the n-hexane phase existing in the water tank 21. It is known that the dispersion of the liquid greatly depends on the viscosity and surface tension of the liquid in addition to the differential pressure generated in the liquid supply unit 22. Since water has a high viscosity and surface tension, the liquid dispersion state is worse than when a liquid in a non-uniform state containing an n-hexane phase having a low viscosity and surface tension is supplied. Specifically, the particle size obtained after dispersion tends to increase.
However, in the case of actually supplying a liquid in a non-uniform state, the ratio between the continuous phase and the dispersed phase is not always constant, and the state becomes unstable with variations. Therefore, the superiority and inferiority of the liquid dispersion state should be compared in the state of the aqueous phase supply in which the liquid dispersion state is estimated to be the worst. This condition is one of the most severely evaluated conditions for the liquid dispersion state. When applied to a heterogeneous liquid phase system that does not contain substances with higher viscosity and surface tension than water, the liquid dispersion state is definitely good. Is obtained.
In the combination of a hydrophilic phase (water phase) containing water and a lipophilic phase (isobutylene phase) containing a hydrocarbon containing isobutylene, which is an example of a heterogeneous liquid phase suitable for the present invention, isobutylene is: Usually a gas at atmospheric pressure. Therefore, in order to carry out the test in the visualization state as in the test example, it is necessary to pressurize to a pressure at which isobutylene liquefies, and a large pressure-resistant transparent container is required, which is very difficult. Therefore, this test was carried out with a combination of deionized water (aqueous phase) and n-hexane (n-hexane phase) as a model substance of a heterogeneous liquid phase.

[Test Example 1]
The flow rate of the water phase was adjusted by the water phase circulation pump 23 so that the pressure loss generated in the liquid supply unit 22 was 0.04 kg / cm ^2, and the water was supplied again to the water tank 21.
As a result, in the n-hexane phase 230 mm downward from the liquid outlet 22 a of the liquid supply unit 22, the water phase has a diameter of 1 mm or less and a visible mist in the range of 300 mm from the center of the width of the water tank 21. There were many, and it was the favorable liquid dispersion state.

[Test Example 2]
The flow rate of the water phase was adjusted by the water phase circulation pump 23 so that the pressure loss generated in the liquid supply unit 22 was 0.1 kg / cm ^2, and the water was supplied again to the water tank 21.
As a result, in the n-hexane phase 240 mm downward from the liquid outlet 22 a of the liquid supply unit 22, the water phase is all in the range of 350 mm from the center of the lateral width of the water tank 21, and the water phase is all visually 1 mm in diameter. There was a good liquid dispersion state.

[Test Example 3]
The flow rate of the water phase was adjusted by the water phase circulation pump 23 so that the pressure loss generated in the liquid supply unit 22 was 0.01 kg / cm ^2, and the water tank 21 was re-supplied.
As a result, in the n-hexane phase 200 mm downward from the liquid outlet 22 a of the liquid supply unit 22, most of the aqueous phase exceeds 1 mm in diameter in the range of 200 mm from the center of the width of the water tank 21. The liquid dispersion state was bad.

[Test Example 4]
The flow rate of the water phase was adjusted by the water phase circulation pump 23 so that the pressure loss generated in the liquid supply unit 22 was 0.25 kg / cm ^2, and the water tank 21 was supplied again.
As a result, in the n-hexane phase that is 340 mm downward from the liquid outlet 22 a of the liquid supply unit 22, and within the range of 520 mm from the center of the lateral width of the water tank 21, all the water phases are 1 mm or less in diameter and are visually mist-like. There was a good liquid dispersion state.

[Example 1]
The hydration reaction of isobutylene and water was performed using the reaction apparatus 10 shown in FIG. In the circular pipe 121 (see FIG. 2) constituting the reaction apparatus 10, the number of the liquid supply holes 121 ^b with respect to the unit cross-sectional area of the flow reactor 11 is 37 / m ^2, which is the radius of the flow reactor 11. The hole diameter of the liquid supply hole 121b when the length is 1 is 0.0022.
A vertical cylindrical reactor is used as the flow reactor 11, and the reactor is filled with a strong acidic cation exchange resin (Rum & Haas, “Amberlyst 15J”) as a solid catalyst to form a catalyst layer 13. I let you.
Further, as a reaction liquid, a two-liquid phase (non-uniformity) composed of 66% by mass of isobutylene-containing hydrocarbons having the composition shown in Table 1, 3.4% by mass of deionized water, and 30.6% by mass of tertiary butyl alcohol. (Liquid phase, gauge pressure 0.9 megapascal).

Using the reaction apparatus 10 shown in FIG. 1, the reaction liquid was supplied to the flow reactor 11 while adjusting the flow rate so that the differential pressure generated before and after the liquid supply means 12 was 0.1 kg / cm ² . The liquid flow direction was downward.
The temperature of the solid catalyst in the flow reactor 11 was measured. The results are shown in Table 2. In Table 2, the “position in the height direction” refers to the position of the temperature measurement point in the height direction. The height (position) of the liquid supply means 12 is the starting point, and the lower surface of the catalyst layer 13 ( The length from the start point to the end point when the height (position) of the lowermost part 13b is the end point is 1, and the length is expressed as a ratio of the length from the liquid supply means 12 to each measurement point with respect to this length. The “radial position” means the position of the temperature measurement point in the radial direction of the cross-sectional circle of the flow reactor 11, and the center of this cross-sectional circle is the starting point and the outer periphery is the end point. The length (radius) from the start point to the end point was set to 1, and the ratio from the center of the circle to each measurement point with respect to this radius was expressed as a ratio.

  As is apparent from Table 2, the measurement points 3A, 3B, 3C, 3D, 3E, and 3F (A to C and D to F are axially symmetric positions) measured at the same height of the flow reactor 11 are used. The maximum temperature difference was 1.42 ° C., and under the conditions of this example, the reaction proceeded almost uniformly in the radial direction of the reactor, indicating that the liquid dispersion state of the heterogeneous liquid phase was good.

DESCRIPTION OF SYMBOLS 10 Reactor 11 Flow type reactor 12 Liquid supply means 13 Catalyst layer

Claims (2)

In a heterogeneous liquid phase reaction method in which a reaction liquid is supplied from a liquid supply unit to a flow-type reactor filled with a solid catalyst, and liquid phases that do not dissolve each other react with each other.
The reaction is a hydration reaction between a hydrophilic phase containing water and a lipophilic phase containing a hydrocarbon containing isobutylene,
A heterogeneous liquid phase reaction method in which a differential pressure generated before and after the liquid supply unit is 0.04 kg / cm ² or more.   The non-uniformity according to claim 1, wherein the temperature of the solid catalyst in the flow reactor is measured at a plurality of points at the same height of the flow reactor to manage the liquid dispersion state of the heterogeneous liquid phase during the reaction. Homogeneous liquid phase reaction method.

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