JPH11349511A - Production of (poly)alkylene glycol monoalkyl ether and apparatus therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a (poly)alkylene glycol monoalkyl ether useful as a surfactant or the like efficiently in high purity and yield by reacting an olefin with a (poly)alkylene glycol under finely dispersing mixing under specific conditions. SOLUTION: An olefin such as octene and a (poly)alkylene glycol such as monoethylene glycol at least one of which has been compounded with a solid catalyst of a fine-particle dispersion type in advance are made to react with each other under finely dispersing mixing by passing through a tower-type reactor 1 to produce a (poly)alkylene glycol monoalkyl ether. The tower-type reactor 1 has a liquid-drop fine dispersion means 14 in each of sections which are formed by dividing the inside of the tower into three or more sections in the vertical direction. Further, the liquid-drop dispersion means 14 consists of a horizontally placed perforated plate 142 having a number of holes; and the perforated plates 142 work concurrently as partitions dividing the inside of the tower 11, are fixed on a driving shaft 143 placed along the central shaft of the tower and vibrate vertically by the vertical motion of the driving shaft 143.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method and an apparatus for producing a (poly) alkylene glycol monoalkyl ether. More specifically, the present invention relates to a method and an apparatus for producing a (poly) alkylene glycol monoalkyl ether by reacting an olefin with a (poly) alkylene glycol.

[0002]

2. Description of the Related Art In addition to being used as a solvent, (poly) alkylene glycol monoalkyl ethers are useful as surfactants and intermediates for producing them. In particular, a (poly) alkylene glycol monoalkyl ether obtained from a long-chain olefin having a large number of carbons as a raw material generally has good wettability and solubility and a low pour point, and is extremely useful as a surfactant. Has a function.

[0003] Regarding a method for producing a (poly) alkylene glycol monoalkyl ether by reacting an olefin with a (poly) alkylene glycol in the presence of a solid catalyst, for example, Japanese Patent No. 2703752 discloses that a crystalline metallosilicate is used as a catalyst. Disclosed, this catalyst shows excellent performance.

[0004]

By the way, the olefin and the (poly) alkylene glycol, which are the raw materials for the production of the (poly) alkylene glycol monoalkyl ether, are only slightly soluble in each other, and have a large difference in their densities. Then, two phases are immediately separated. Due to such problems, in the reaction for producing (poly) alkylene glycol monoalkyl ether using olefin and (poly) alkylene glycol as raw materials, the mass transfer rate of the raw materials was low, and the reaction efficiency was poor.

[0005] However, the prior art, as disclosed in the above-mentioned patents, mainly aims at improving only the catalyst, and does not improve the efficient reaction method and reaction apparatus in industrial production. Therefore, an object of the present invention is to
An object of the present invention is to provide a production method and a production apparatus for industrially efficiently producing a (poly) alkylene glycol monoalkyl ether.

[0006]

In order to solve the problem of the two liquid phase system, the present inventor preferably makes one phase into a droplet state and finely disperses and mix it in the other continuous phase. I thought. This droplet formation is obtained, for example, by stirring. However, it has been found that it is difficult for a simple tank-type apparatus to be agitated so as to obtain fine dispersion of droplets when scaled up to a large-scale apparatus. On the other hand, it has also been found that the continuous reactor of the complete mixing tank type generally has lower use efficiency of the reactor than the continuous reactor of the plug flow type.

Therefore, the present inventor has proposed a means for realizing a finely dispersed state of droplets in a continuous phase in order to exhibit an efficiency comparable to that of a plug flow type continuous reactor even though it is a large reactor. The present invention was completed through intensive research and repeated experiments. That is, the method for producing a (poly) alkylene glycol monoalkyl ether according to the present invention comprises reacting an olefin with a (poly) alkylene glycol in a two-liquid phase system in the presence of a solid catalyst to form a (poly) alkylene glycol monoalkyl ether. A method for producing ether, wherein the solid catalyst is a fine particle-dispersed catalyst, and the olefin and the (poly) alkylene glycol are blended in advance with at least one of these two liquids, The inside of the tower is divided into three or more upper and lower sections, and the mixture is finely dispersed and mixed by passing through a tower type reactor having a fine droplet dispersing means in each section, and the reaction is performed.

The apparatus for producing a (poly) alkylene glycol monoalkyl ether according to the present invention comprises reacting an olefin with a (poly) alkylene glycol in a two-liquid phase system in the presence of a solid catalyst. A reactor for use in a method for producing a glycol monoalkyl ether, comprising: a tower-type reactor in which the inside of a tower is divided into three or more vertical sections and each section has fine droplet dispersion means, It is characterized in that the (poly) alkylene glycol is mixed with at least one of these two liquids in advance with the fine particle-dispersed solid catalyst and then passed through the tower reactor.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The olefin used in the present invention is preferably a hydrocarbon having 2 to 40 carbon atoms having an ethylenically unsaturated bond, more preferably a hydrocarbon having 6 to 30 carbon atoms having an ethylenically unsaturated bond. Acyclic hydrocarbons. The (poly) alkylene glycol monoalkyl ether obtained from these acyclic hydrocarbons having 6 to 30 carbon atoms is suitably used as a raw material for a surfactant. Specific examples of the olefin include ethylene, propylene, butene, isobutylene, butadiene, hexene, octene, decene, dodecene, tetradecene, hexadecene, octadecene, eicosene, and the like. These may be used alone or in combination of two or more. Among these, olefins having a large number of carbon atoms, such as octene, decene, dodecene, tetradecene, hexadecene, octadecene, and eicosene, are preferably used. These olefins can be used without particular limitation, even if the position of the unsaturated bond is α-position or inner position, or if both olefins have both α-position and inner position. These olefins having different unsaturated bond positions may be used alone or in combination of two or more.

The (poly) alkylene glycol used in the present invention includes monoethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, monopropylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol and 1,3-propanediol. , 1,
2-butanediol, 2,3-butanediol, 1,4
-Butanediol, 1,6-hexanediol, 1,4
-Cyclohexanemethanediol and the like. These may be used alone or in combination of two or more.

The solid catalyst used in the present invention includes a crystalline metallosilicate, a strongly acidic cation exchange resin, a heteropoly acid, and the like. The crystalline metallosilicate is one of the most preferred solid catalysts for use in the reaction of the present invention. In the present invention, the solid catalyst is used in a fine particle dispersion type. The particle size is not particularly limited as long as a suitable dispersion can be obtained in the raw material system, and is, for example, 1 to 150 μm in terms of volume average particle size.

[0012] Crystalline metallosilicates are ordered, porous materials having a defined crystal structure. That is,
This is a solid substance having a large specific surface area having many regular voids and pores in the structure. Generally, the specific surface area of crystalline metallosilicate is 300 to 2000 cm ² /
It is preferably in the range of g. The crystalline metallosilicate is a crystalline aluminosilicate (generally referred to as zeolite) and a compound in which another metal element is introduced into the crystal lattice instead of the Al atom of the crystalline aluminosilicate. Specific examples of other metal elements include B, Ga, I
n, Ge, Sn, P, As, Sb, Sc, Y, La, T
i, Zr, V, Cr, Mn, Fe, Co, Ni, Cu,
At least one of Zn and the like is given. In terms of catalytic activity and ease of synthesis and availability, crystalline aluminosilicate, crystalline ferrosilicate, crystalline borosilicate,
Crystalline gallosilicate is preferred.

Specific examples of crystalline metallosilicates include IUP named by the International Zeolite Society Structural Committee.
When described using AC codes, MFI (ZSM-5)
MEL (ZSM-11, etc.), BEA (β-type zeolite, etc.), FAU (Y-type zeolite, etc.), MOR (Mo
rdeneite, etc.), MTW (ZSM-12, etc.), LT
L (Linde L etc.). In addition to these, "ZEOLITES, Vol. 1
2, No. 5, 1992 "and" HAND BOOKOF "
MOLECULAR SIEVES, R. Szosta
k, VAN NOSTRAND REINHOLD publishing "and the like.
These may be used alone or in combination of two or more. Among these, MFI or MFI called pentasil type
Those having a structure such as EL or a structure of BEA are preferable from the viewpoint of excellent catalytic activity.

[0014] The crystalline metallosilicate constitutes it.
The atomic ratio of silicon atoms to metal atoms is 5 or more and 150
Those having a range of 0 or less, especially 10 or more and 500 or less are preferable.
Good. The atomic ratio of silicon atoms to the metal atoms is small
Too large or too large are preferred due to low catalytic activity.
Not good. These crystalline metallosilicates have a crystal lattice
It has an ion-exchangeable cation outside. These katio
H as a specific example⁺, Li⁺, Na⁺, Rb⁺, C
s ⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Sc³⁺,
Y³⁺, La³⁺, R_FourN⁺, R_FourP⁺(R is H or Al
A kill group). Among them, Katio
Of which all or part of the
Preferred as bright catalyst.

[0015] Crystalline metallosilicates are commonly used.
Can be synthesized by a synthetic method such as hydrothermal synthesis.
Wear. Specifically, JP-B-46-10064, US
Japanese Patent No. 3965207, "Journal of
Molecular Catalysis "(Journal of
 Molecular Catalysis) Vol. 31
355-370 (1985).
According to the method, for example, it can be synthesized as follows. Sand
For example, for example, a silica source, a metal source, and tetrapropyl
Quaternary ammonium salts such as ammonium salts
Crystals formed at a temperature of about 100-175 ° C.
Until the solid product is filtered, washed with water and dried.
After drying, firing at 350-600 ° C
Can be achieved. Adjust raw materials and synthesis conditions appropriately.
It is possible to obtain a metallosilicate of a different crystal system depending on
it can. Examples of the silica source include water glass and silica sol.
, Silica gel, alkoxysilane, etc.
Wear. As the metal source, various inorganic or organic
Metal compounds can be used. Those metal compounds
As a preferable example of the compound, a sulfate of a metal [eg, Al_Two(SO
_Four)_Three], Metal nitrates [eg, Fe (NO_Three)_Three],
Alkali metal salts of metal oxides [eg NaAlO _Two]
Any metal salts; metal chlorides [eg TiCl_Four],Money
Genus bromide [eg MgBr_Two] And other metal halides
Substances; metal alkoxides [for example, Ti (OC_TwoH_Five)
_FourAnd the like. The obtained crystalline metallosilicate
If necessary, ion-exchange to the desired cation
Can be. For example, H⁺Type cations are crystalline meta
HCl, NH_FourCl, NH_ThreeAqueous solution such as
And stir the cation species in H⁺Type or NH_Four ⁺Type
And then the solid product is filtered, washed with water, dried
And then calcined at 350-600 ° C.
Can be Part of the cationic species is H⁺Also replaced with
Is H⁺Type of cation
By performing the same operation using an aqueous solution containing
Can be prepared by partially exchanging the target cation type.
it can.

In the present invention, in order to maintain a high catalytic activity, it is important that the average particle size of the crystalline metallosilicate secondary particles is 150 μm or less, preferably 100 μm or less, more preferably 50 μm or less. It is. Further, it is preferable that substantially no particles having a particle size distribution larger than 100 μm are present. “Substantially no particles larger than 100 μm” means that secondary particles 9
0% or more particle diameter is 100 μm or less,
It is preferable that all the secondary particles have a particle size of 100 μm or less. As described above, the main reason for limiting the average particle size of the secondary particles in the present invention is to suppress the rate-limiting diffusion of the reaction material to the catalyst surface, and the average particle size of the secondary particles is about 50 to 100 μm. Occasionally, the diffusion rate of the reaction raw material and the reaction rate become substantially equal. Therefore, if the average particle diameter of the secondary particles is 50 μm or less, the influence of the diffusion rate of the reaction raw material on the reaction rate is almost negligible. For example, when the average particle diameter of the secondary particles is 50 μm and 10 μm, the reaction rate is reduced. There is no big difference. Although the lower limit of the average particle size of the secondary particles is not particularly limited, it is preferably 1 μm or more, more preferably 2 μm or more, for easy recovery. The “average particle size of the crystalline metallosilicate secondary particles” as used herein is a volume average value of the particle size of the aggregate of the crystalline metallosilicate, and is, for example, a laser light scattering particle size distribution analyzer LA manufactured by HORIBA, Ltd.
Water can be measured using -920 as a solvent.

In order to limit the average particle size of the crystalline metallosilicate secondary particles to 150 μm or less in the present invention, a method of removing or pulverizing particles having a large particle size (coarse particles) is simple. . For example, coarse particles are removed or crushed by a general method such as a method of classifying and removing coarse particles, a method of crushing coarse particles with a ball mill-type crusher, an agitator mill-type crusher, a mortar-type crusher, a mortar, or the like. Or you can.

In the present invention, the primary particle size of the crystalline metallosilicate also affects the reaction rate. In order to maintain high reaction activity, the average particle size of the primary particles is preferably 1 μm or less, more preferably 0.1 μm or less. The average particle size of the primary particles can be measured by observing the catalyst surface with an electron microscope. In the present invention, the reaction between the olefin and the (poly) alkylene glycol is as follows:
The reaction can be carried out either in the presence or absence of a solvent. Usable solvents include nitromethane, nitroethane, nitrobenzene, dioxane, ethylene glycol dimethyl ether, sulfolane, benzene, toluene, xylene, hexane, cyclohexane, decane,
Paraffin and the like.

The molar ratio of the olefin as the reaction raw material to the (poly) alkylene glycol is not particularly limited,
The molar ratio of (poly) alkylene glycol to olefin is preferably from 0.05 to 200, more preferably from 0.1 to 5
0 is more preferable, and 0.1 to 10 is further preferable. The reaction temperature is preferably from 50 to 250C, more preferably from 80 to 220C, even more preferably from 100 to 200C. The reaction pressure may be any of reduced pressure, normal pressure or increased pressure, but is preferably in the range of normal pressure to 20 kg / cm ² .

The amount of the catalyst used is not particularly limited, but is preferably from 0.1 to 100% by weight, more preferably from 0.3 to 70% by weight, and more preferably from 0.5 to 100% by weight, based on the starting olefin.
50% by weight is more preferred. The reaction time, that is, the residence time, varies depending on the reaction temperature, the amount of the catalyst, the raw material composition ratio, and the like, but is preferably 0.1 to 100 hours, more preferably 0.3 to 50 hours, and still more preferably 0.5 to 30 hours. After completion of the reaction, the catalyst is separated by a method such as centrifugation or filtration and can be recycled for the next reaction. From the reaction solution from which the catalyst has been separated and removed, the desired (poly) alkylene glycol monoalkyl ether can be recovered by extraction or distillation, and the unreacted raw material can be recycled for the next reaction.

In the present invention, the starting olefin and the (poly) alkylene glycol dissolve each other with only a slight solubility, and the catalyst is contained in the (poly) alkylene glycol phase as the product (poly) alkylene glycol. Monoalkyl ethers often partition into the olefin phase. In the case of such a distribution system, after the reaction is completed, the olefin phase and the (poly) alkylene glycol phase are separated, and the (poly) alkylene glycol phase containing the catalyst is obtained by removing the (poly) alkylene glycol consumed by the reaction. After the replenishment, the mixture is recycled to the next reaction, and a process for recovering the raw material and the desired (poly) alkylene glycol monoalkyl ether from the olefin phase by a separation method such as distillation can be established.

In the present invention, the solid catalyst is a fine particle-dispersed catalyst, and the olefin and the (poly) alkylene are used in a flow-type reactor equipped with a fine droplet dispersing means as exemplified below. The above-mentioned solid catalyst is previously blended with at least one of the glycol and the olefin containing the fine particle-dispersed catalyst and the (poly) alkylene glycol are finely dispersed and mixed by passing through the column reactor. To achieve the intended purpose.
The fixed catalyst may be mixed only with the olefin, mixed only with the (poly) alkylene glycol, or mixed with both the olefin and the (poly) alkylene glycol. However, in consideration of the distribution type as described above, particularly, the solid catalyst is often dispersed in advance only in (poly) alkylene glycol. The particle size of the dispersed phase droplet in the fine droplet dispersion is not particularly limited, but is preferably 20 mm or less and 0.01 mm or more as a volume average particle size. When the droplet diameter of the dispersed phase exceeds 20 mm, the contact interface area between the olefin phase and the (poly) alkylene glycol phase decreases, and the mass transfer rate of the raw materials and products between the phases decreases and the reaction rate decreases, which is not preferable. . Further, the particle diameter of the droplet is 0.0
If it is less than 1 mm, it takes a long time to separate the two phases after completion of the reaction, and an excessive volume separator is required, which is not preferable.

FIG. 1 shows an embodiment of a tower reactor used in the present invention. The tower reactor 1 includes liquid separation units 12 a and 12 b at the upper and lower ends in a tower 11, and a reaction unit 13 is provided between the liquid separation units 12 a and 12 b. A large number of droplet fine dispersion means 14 are provided in the reaction section 13.
... are installed. The droplet fine dispersion means 14 comprises a perforated plate 142. The perforated plate 142 has a large number of holes 141.
Are arranged horizontally in the tower 11. The perforated plate 142 also serves as a partition that partitions the inside of the tower 11 up and down, and the drive shaft 1 arranged along the tower center axis.
43, and vibrates up and down by the vertical movement of the drive shaft 143. This vertical movement is preferably performed at a stroke of 5 to 100 mm and a cycle of 50 to 600 times / min. The outer peripheral edge of the perforated plate 142 hardly creates a gap between itself and the inner peripheral surface of the tower 11 to such an extent that the above-mentioned vibration is not hindered. As a result, the dispersed phase existing between the upper and lower porous plates 142, 142 is formed into droplets while passing through the holes 141 of the porous plate 142, and is finely dispersed and mixed uniformly in the continuous phase. Since the droplet formation is always performed in the entire reaction section 13, the olefin and the (poly) alkylene glycol always keep suitably in contact during the reaction. In FIG. 1A, both raw materials come into contact in parallel, and the product comes out from the lower end of the column. In FIG. 1B, both raw materials come into contact in countercurrent, and the product comes out from the upper end of the column. It has become.

In the tower type reactor 1 shown in FIG. 2, the droplet fine dispersion means 24 is composed of a horizontally arranged rotary disk 241 and donut-shaped grids 242, 242 horizontally arranged above and below the rotary disk 241. The grid 242 also serves as a partition that partitions the inside of the tower 11 up and down. The rotary disks 241 are attached to a drive shaft 243 arranged along the center axis of the tower, and rotate at a high speed by the rotation of the drive shaft 243. The liquid to be the dispersed phase is
Droplets are formed by high-speed rotation of the rotary disk 241.
The donut-shaped grid 242 is a rotary disc 24
Between 1 and shearing force on the dispersed phase. The liquid dispersed phase is finely dispersed in the continuous phase and reacts. In FIG. 2, 12a,
12b is a liquid separation section at the upper and lower ends of the column, and 13 is a reaction section. In this example, the olefin and the (poly) alkylene glycol come into contact in parallel, and the product exits from the bottom of the column. You can do it.

In the tower type reactor 1 shown in FIG. 3, the droplet fine dispersion means 34 comprises a stirring blade 341 and donut-shaped grids 342, 342 horizontally arranged above and below the stirring blade.
The grid 342 also serves as a partition that partitions the inside of the tower 11 up and down. The stirring blades 341 are attached to a drive shaft 343 arranged along the center axis of the tower.
The high-speed rotation is achieved by the rotation of 43. The liquid to be the dispersed phase is formed into droplets by the high-speed rotation of the stirring blade 341. The donut-shaped grid 342 applies a shear force to the dispersed phase with the stirring blade 341. The liquid dispersed phase is finely dispersed in the continuous phase and reacts. In FIG. 3, 12a, 12b
Is a liquid separation section at the upper and lower ends of the column, and 13 is a reaction section. Also in this example, the olefin and the (poly) alkylene glycol come into contact in parallel, and the product comes out from the bottom of the tower. You can do it. When a stirring blade as shown in FIG. 3 is used, a baffle plate (baffle plate) generally installed in a tank reactor can be installed in each section in the tower 11 to further enhance the dispersion effect. . As the stirring blade, for example, a paddle blade, a turbine blade, an inclined turbine blade, a propeller blade, an anchor type blade, a faudler blade, a max blend blade, and the like can be used.

The cocurrent and countercurrent in the tower reactor as shown in FIGS. 1, 2 and 3 will be described in detail. When the olefin is a dispersed phase and the (poly) alkylene glycol is a continuous phase, the specific gravity of the olefin is generally lower than that of the (poly) alkylene glycol.
The two materials come into contact with each other in a countercurrent flow with the alkylene glycol as the downflow or in a parallel flow with the (poly) alkyleneglycol as the ascending flow. When the (poly) alkylene glycol is a dispersed phase and the olefin is a continuous phase, the (poly) alkylene glycol generally has a higher specific gravity than the olefin, so that only a downflow is possible. The two materials come into contact in countercurrent with the olefin ascending. Which of the olefin and the (poly) alkylene glycol is the dispersed phase depends on the physical properties of the raw materials, products and catalysts, the volume ratio or flow ratio of the olefin phase and the (poly) alkylene glycol phase, the temperature, the stirring / dispersing means, and the partition. It is determined by the structure and the like. The product (poly) alkylene glycol monoalkyl ether is generally distributed to the olefin phase, so that the outlet of the product and the outlet of the olefin are the same.

In the tower type reactor 1 shown in FIG. 4, the fine droplet dispersion means 44 comprises a perforated plate 441 and a baffle plate 442. Perforated plate 4
41 have a number of fine holes 443... And are arranged horizontally in the tower 11. The perforated plate 441 has its outer edge in contact with the inner peripheral surface of the tower 11 and also serves as a partition for partitioning the inside of the tower 11 up and down. The location 444 is a continuous phase flow passage. In order to regulate this liquid flow, a baffle plate 442 (a) hangs from the edge of the notch 444. In this embodiment, another baffle 442 (b) is provided to reverse the liquid flow in one compartment. Thus, the baffle plate 442 creates a liquid flow in the space between the upper and lower perforated plates 441, 441 in the tower 11. The liquid to be the dispersed phase is the pores 443 of the perforated plate 441.
To form droplets. Dispersed phase is perforated plate 441
Are generated due to the specific gravity difference between the dispersed phase and the continuous phase. Usually, the olefin is introduced from the lower end of the column 11 because the specific gravity of the olefin is smaller than that of the (poly) alkylene glycol. In the tower reactor 1 shown in FIG. 9A, the baffle plate 442 (a) is also hung down at the edge of the lacking portion 444 of the lowermost perforated plate 441, so that it is introduced into the liquid separation portion 12b at the lower end of the column. The olefin is blocked by the lowermost baffle plate 442 (a) and cannot pass through the missing portion 444. As a result, the olefin passes through the pores 443... Of the lowermost perforated plate 441 due to its buoyancy and is turned into droplets. Thereafter, it passes through the upper perforated plates 441... One after another while ascending in the tower 11, and undergoes further droplet formation and maintenance of the droplet state. The black dots in the figure represent this droplet. The (poly) alkylene glycol moves to the lower section through the notch 444, and its flow is reversed at the baffle plate 442 (b) and then to the next notch 444. In (b) of the figure, there is no hanging baffle plate 442 (a) in the missing portion 444 of the lowermost perforated plate 441, and the lower baffle plate 441 protrudes upward.
42 (c) is provided. Liquid separation unit 12a at the top of the tower
Is blocked by the baffle plate 442 (a) provided on the uppermost perforated plate 441, and cannot pass through the missing portion 444. as a result,
The (poly) alkylene glycol passes through the pores 443... Of the uppermost perforated plate 441 due to its gravity and is converted into droplets. Thereafter, while descending in the tower 11, the lower perforated plate 4
41, and undergoes further droplet formation and maintenance of the droplet state. The black dots in the figure represent this droplet. The olefins pass through the cutouts 444 to the upper compartment, where the flow is directed to a fourth baffle 442 located above each cutout 444.
After being inverted at (d), inverted again at the second baffle plate 442 (b), and again inverted at the hanging baffle plate 442 (a), it goes to the next missing part 444. In FIG. 4, 13
Is a reaction part.

The number of sections in the reactor is at least 3 sections, preferably at least 5 sections. However, as the number of sections increases, the cost of equipment increases. As shown in FIG. 4, when the droplet fine dispersion means does not move and the mixing with the next section is small, 10
50 to 50, as shown in FIGS. 1 to 3, when there is a movement in the droplet fine dispersion means and considerable mixing with the next compartment occurs.
There are 200 sections.

[0029]

EXAMPLES Hereinafter, specific examples of the present invention will be described together with comparative examples, but the scope of the present invention is not limited to these examples. In the examples, the product yield (mol%) was calculated according to the following formula. Yield of monoethylene glycol monododecyl ether (Y-EMD) = (moles of monoethylene glycol monododecyl ether produced / moles of dodecene supplied) × 100 -Example 1- The size of the liquid separation part at the end is inner diameter 5
0 mm, height 150 mm, reaction section size 25.4 mm inside diameter,
It is 3050mm in height (1585ml in internal volume),
This reaction part is divided into 60 sections (61 sections) with 61 perforated plates.
0 mm) was used. The perforated plate has four holes with a diameter of 8 mm. The outer periphery of the reactor is covered with a jacket, and a heating medium circulates in the jacket to heat the reactor.

As the starting olefin, 1-dodecene (O
L) Ethylene glycol (MEG) was used as the starting alkylene glycol. Further, as a catalyst, BEA type zeolite (Si /
Al = 12) was used and suspended at 10% by weight in the raw material MEG using a volume average particle diameter of 8 μm. The reaction conditions are
Reaction temperature: 143 ° C., OL flow rate: 13.20 ml / min, MEG flow rate including catalyst: 75.00 ml / min, vertical vibration stroke: 25 mm, number of vibrations: 400 times / min. OL is supplied from the bottom, and MEG including the catalyst is supplied from the top. Countercurrent contact.

At this time, the yield (Y-EMD) was 14.3.
Met. -Examples 2 to 7-The reaction was carried out in the same manner as in Example 1 except that the reaction conditions were changed as shown in Table 1. In Examples 6 and 7, since the isomerization was advanced and a raw material having a small α-olefin fraction was used, the equilibrium conversion was smaller than that in the case of using only α-olefin (Examples 1 to 5). Therefore, the yield is small. In the co-current contact, OL, M
EG was also supplied from above.

The yield (Y-EMD) of each example was as shown in Table 1.

[0033]

[Table 1]

Comparative Example A continuous tank type reactor with an internal volume of 2 liters and equipped with a stirrer was used. The kind and composition of the raw material and the catalyst were the same as in Example 1.
The reaction conditions were as follows: reaction temperature 145 ° C., OL flow rate 4.16 ml /
Min, MEG flow rate including catalyst 39.4 ml / min, stirring speed 6
00 times / minute. The liquid level inside the reactor was controlled to 1 liter by liquid level control. The state of separation of the two liquids at the liquid outlet is controlled, and OL / OL of the reaction liquid staying in the reactor is controlled.
The MEG volume ratio including the catalyst was about 8/2. The reaction conditions of this comparative example are almost comparable to those of Example 5.

The yield (Y-EMD) at this time was 15.6.
Met. From these results, the yield of Example 5 (Y-EM
D) is inferior to 23.1. -Reference Example-A batch tank reactor having an internal volume of 2 liters was used. The kind and composition of the raw material and the catalyst were the same as in Example 1. The reaction conditions were as follows: reaction temperature 145 ° C., reaction time 3 hours, OL amount 800
ml, MEG (containing 10% by weight of catalyst) amount: 200 ml, and stirring speed: 600 times / min. The reaction conditions of this reference example are almost comparable to those of Example 5.

At this time, the yield (Y-EMD) was 23.5.
Met. The yield (Y-EMD) of Example 5 is 23.1, which is almost equal to the yield of this reference example. From these results, it can be seen that, in the present invention, a yield comparable to that of a batch system is obtained while being a continuous system.

[0037]

According to the present invention, a (poly) alkylene glycol monoalkyl ether can be industrially advantageously produced in high yield.

[Brief description of the drawings]

FIG. 1 shows a perforated plate reactor used in the present invention, wherein (a)
1 is a cross-sectional view of a co-current contact type reactor, (b) is a cross-sectional view of a counter-current contact type reactor, and (c) is a partial perspective view of a droplet dispersion means.

FIGS. 2A and 2B show a rotary disk type tower reactor used in the present invention, wherein FIG. 2A is an overall sectional view, and FIG. 2B is a partial perspective view of a droplet dispersing means.

FIG. 3 is a sectional view showing a stirring blade type reactor used in the present invention.

FIG. 4 shows a perforated plate-baffled plate type reactor used in the present invention, wherein (a) is a cross-sectional view of a reactor for forming olefin droplets,
(B) is a cross-sectional view of a reactor for forming (poly) alkylene glycol droplets, and (c) is a partial perspective view of droplet dispersing means.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 tower reactor 11 tower 12a liquid separation section at top of tower 12b liquid separation section at bottom of column 13 reaction section 14 droplet dispersion means 142 perforated plate 143 drive shaft 24 droplet dispersion means 241 rotary disk 242 donut-shaped grid 243 drive shaft 34 Droplet Dispersing Means 341 Stirring Blade 342 Donut Shape Grid 343 Drive Shaft 44 Droplet Dispersing Means 441 Perforated Plate 442 Baffle Plate

Continued on the front page (72) Inventor Yukio Sumino 14-1 Chidoricho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Nippon Shokubai Co., Ltd.

Claims (6)

[Claims] 1. A method for producing a (poly) alkylene glycol monoalkyl ether by reacting an olefin and a (poly) alkylene glycol in a two-liquid phase system in the presence of a solid catalyst, wherein the solid catalyst is dispersed in fine particles. Type catalyst, wherein the olefin and the (poly) alkylene glycol are blended in advance with the solid catalyst in at least one of these two liquids, and the inside of the tower is divided into three or more vertical sections. A method of producing a (poly) alkylene glycol monoalkyl ether, wherein the mixture is finely dispersed and mixed by passing through a tower type reactor having a droplet fine dispersion means therein. 2. A reactor for use in a method for producing a (poly) alkylene glycol monoalkyl ether by reacting an olefin and a (poly) alkylene glycol in a two-liquid phase system in the presence of a solid catalyst, comprising: Is divided into three or more upper and lower sections, and a tower type reactor having fine droplet dispersing means in each section is provided, and the olefin and the (poly) alkylene glycol are dispersed in at least one of these two liquids in advance. An apparatus for producing a (poly) alkylene glycol monoalkyl ether, wherein the solid catalyst of the type is mixed and passed through the tower reactor. 3. The droplet fine dispersion means comprises a horizontally arranged perforated plate having a large number of holes, and the perforated plate also serves as a partition for partitioning the inside of the tower, and is arranged along the center axis of the tower. The apparatus for producing a (poly) alkylene glycol monoalkyl ether according to claim 2, wherein the apparatus is attached to a drive shaft arranged in a vertical direction and vibrates up and down by the vertical movement of the drive shaft. 4. The fine droplet dispersing means comprises a rotary disk arranged horizontally and a donut-shaped grid arranged horizontally above and below the rotary disk, and the grid also serves as a partition for dividing the inside of the tower. 3. The production of the (poly) alkylene glycol monoalkyl ether according to claim 2, wherein the rotary disk is attached to a drive shaft arranged along the center axis of the tower, and is rotated at a high speed by rotation of the drive shaft. apparatus. 5. The droplet fine dispersing means comprises a stirring blade and a donut-shaped grid horizontally arranged above and below the stirring blade, the grid also serving as a partition for partitioning the inside of the tower, and the stirring blade is used as a tower. The apparatus for producing a (poly) alkylene glycol monoalkyl ether according to claim 2, wherein the apparatus is attached to a drive shaft arranged along the central axis and rotates at a high speed by rotation of the drive shaft. 6. The droplet fine dispersion means comprises a horizontally arranged perforated plate having a large number of pores, and a baffle plate for forming a liquid flow in a space in a tower sandwiched between upper and lower perforated plates. The apparatus for producing a (poly) alkylene glycol monoalkyl ether according to claim 2, wherein the perforated plate also serves as a partition for partitioning the inside of the tower.