JPH10168017A - Production of (poly)alkylene glycol mono(higher alkyl) ether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a (poly)alkylene glycol mono(higher alkyl) ether in high reaction rate, high selectivity and high yield by dispersing a long chain olefin phase in a (poly)alkylene glycol phase suspending a crystalline metalosilicate catalyst and mainly forming a continuous phase, and reacting the dispersion. SOLUTION: The objective product is obtained by suspending (B) a crystalline metalosilicate having a BEA structure as a catalyst in (A) a (poly)alkylene glycol, e.g. monoethylene glycol, dispersing (C) an 8-30C olefin having an enhylenically unsaturated bond, e.g. dodecene, in the suspension to form the component A into a continuous phase and reacting the dispersion at 50-250 deg.C under a pressure of a normal pressure to 20kg/cm<2> for 0.1-100hr. The volume ratio of the component C after suspending the catalyst to the component A is 0.01-2, the molar ratio of component A to the component C is 0.05-100, and the concentration of the component B in the component A is 0.1-50wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a (poly) alkylene glycol mono-higher alkyl ether. More specifically, the present invention relates to a method for producing a (poly) alkylene glycol mono-higher alkyl ether by reacting a (poly) alkylene glycol with a long-chain olefin.

[0002]

2. Description of the Related Art As a method for producing a (poly) alkylene glycol mono-higher alkyl ether by reacting a long-chain olefin with a (poly) alkylene glycol, for example, a method using a strongly acidic ion-exchange resin as a catalyst (Japanese Unexamined Patent Publication No. No. 2,959,941), and a method using sulfuric acid, benzenesulfonic acid, or toluenesulfonic acid as a catalyst (Japanese Patent Publication No. 61-57070).

[0003]

However, when these strongly acidic cation exchange resins, sulfuric acid, benzenesulfonic acid and toluenesulfonic acid are used as catalysts, the conversion rate of long-chain olefins is low because the reaction rate is low. And the selectivity from long-chain olefins to (poly) alkylene glycol mono-higher alkyl ethers is low. In particular, the problem is that the reaction rate is significantly reduced as the number of carbon atoms in the long-chain olefin as the raw material increases. was there. Furthermore, since the other raw material (poly) alkylene glycol is a dihydric alcohol, a dehydration-condensation polymerization reaction and a dehydration cyclization reaction of the same occur simultaneously as a side reaction during the reaction, and an addition reaction to a long-chain olefin occurs. There was also a problem that the selectivity of the was very low.

Accordingly, an object of the present invention is to provide a method for producing a (poly) alkylene glycol mono-higher alkyl ether having a high reaction rate, a high selectivity and a high yield.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a crystalline metallosilicate is used as a catalyst in the reaction between a (poly) alkylene glycol and a long-chain olefin. As a result, it has been found that a (poly) alkylene glycol mono-higher alkyl ether can be produced with a high reaction rate, a high selectivity and a high yield.

Further, a (poly) alkylene glycol, a long-chain olefin and the above-mentioned catalyst (crystalline metallosilicate)
As a result of studying a method for efficiently contacting and reacting with and suppressing the deactivation of the catalyst, the (poly) alkylene glycol phase in which the catalyst was suspended was mainly used as the continuous phase, and the long-chain olefin phase was dispersed. It has been found that it is effective to cause the reaction to occur, and the present invention has been completed.

That is, according to the process for producing a (poly) alkylene glycol mono-higher alkyl ether of the present invention, a crystalline metallosilicate is used as a catalyst, and the (poly) alkylene glycol phase in which the catalyst is suspended is mainly used as a continuous phase. A long-chain olefin phase is dispersed and reacted. In the above, the volume ratio of the long-chain olefin phase to the (poly) alkylene glycol phase (long-chain olefin phase / (poly) alkylene glycol phase) is 0.01 to 2
It is preferred that Further, the long-chain olefin is preferably at least one selected from the group consisting of olefins having 8 to 30 carbon atoms.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The long-chain olefin used in the present invention is preferably a hydrocarbon having 8 to 30 carbon atoms having an ethylenically unsaturated bond, more preferably a hydrocarbon having 10 to 10 carbon atoms having an ethylenically unsaturated bond. 20 hydrocarbons. Such a long-chain olefin may be a branched olefin, a linear olefin, an acyclic olefin, a cyclic olefin, or a mixture thereof without any particular limitation. However, in consideration of the surfactant application, it is preferable that the acyclic olefin is the main component, and it is further preferable that the linear olefin is the main component. Specific examples include octene, decene, dodecene, tetradecene, hexadecene, octadecene, eicosene, dococene and the like. These long-chain olefins may have an unsaturated bond at the α-position or an inner position,
Alternatively, those having both the α-position and the inner position can be used without particular limitation. Of course, two or more of these long-chain olefins having different unsaturated bond positions can be used in combination. In the reaction process of the present invention, a reaction in which the position of the unsaturated bond of the long-chain olefin is isomerized occurs simultaneously. In general, an inner olefin is more thermodynamically stable than an α-olefin. Therefore, when an α-olefin is used as a raw material, the olefin gradually becomes isomerized into an inner olefin during the reaction. The rate of isomerization varies depending on the reaction temperature and the type and amount of the crystalline metallosilicate used as the catalyst.

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 as a mixture of two or more.

[0010] The crystalline metallosilicate used in the present invention is a regular porous substance having a certain crystal structure. That is, this is a solid substance having a large specific surface area having a number of regular voids and pores in the structure. The crystalline metallosilicate used in the present invention includes crystalline aluminosilicate (generally referred to as zeolite) and crystalline aluminosilicate Al.
A compound in which another metal element is introduced into the crystal lattice instead of an atom. Specific examples of other metal elements include B and G
a, In, Ge, Sn, P, As, Sb, Sc, Y, L
a, Ti, Zr, V, Cr, Mn, Fe, Co, Ni,
Examples thereof include Cu and Zn, which may be used alone or as a mixture of two or more. Crystalline aluminosilicate, crystalline ferrosilicate, crystalline borosilicate, and crystalline gallosilicate are preferred from the viewpoint of catalytic activity and ease of synthesis and availability, and crystalline aluminosilicate is particularly preferred.

As specific examples of the crystalline metallosilicate used in the present invention, MFI (such as ZSM-5) and MEL (ZSM-11) can be described using IUPAC codes named by the International Zeolite Society Structural Committee.
), BEA (β-type zeolite, etc.), FAU (Y-type zeolite, etc.), MOR (Mordenite, etc.), MTW (ZSM
-12) and those having a structure of LTL (such as Linde L). In addition to these, "ZEOLITES,
Vol. 12, No. 5, 1992 "and" HANDBOO "
K OF MOLECULAR SIEVES, R.A. S
Zostak, VAN NOSTRAND REIN
HOLD Publishing ”and the like. These may be used alone or in combination of two or more. Among them, those having a BEA structure are particularly preferable because of their excellent catalytic activity.

The crystalline metallosh used in the present invention
The borrow is the silicon source for the metal atoms that make it up.
The atomic ratio of the child is 5 or more and 1500 or less, particularly 10 or more and 500 or less.
Those having the following ranges are preferred. For the metal atom
The atomic ratio of silicon atoms is too small or too large
Is not preferred because the catalytic activity is low. Their crystallinity
Metallosilicate is an ion-exchangeable click outside the crystal lattice
Has an ON, but as a specific example of these cations,
H⁺, Li⁺, Na⁺, Rb⁺, Cs⁺, Mg²⁺, Ca
²⁺, Sr²⁺, Ba²⁺, Sc³⁺, Y³⁺, La³⁺, R
_FourN⁺, R _FourP⁺(R is H or an alkyl group)
I can do it. Above all, all or part of the cation
Those substituted with hydrogen ions are suitable as the catalyst of the present invention.
is there.

The crystalline metallosilicate used in the present invention can be synthesized by a generally used synthesis method, for example, a hydrothermal synthesis method. To be more specific,
No. 6-10064, U.S. Pat. No. 3,965,207, "Journal of Molecular Catalysis" Vol. 31, 35.
5-370 (1985), Zeolites Vol. 8, P46 (19
1988). These crystalline metallosilicates, for example, a silica source,
A composition comprising a metal source and a quaternary ammonium salt such as a tetraethylammonium salt, a tetrapropylammonium salt, etc., is heated at a temperature of about 100-175 ° C. until crystals form, and then the solid product is filtered. After washing with water and drying, it can be synthesized by firing at 350 to 600 ° C. A metallosilicate having a different crystal system can be obtained by appropriately adjusting the raw materials and the synthesis conditions.

As the silica source, water glass, silica sol, silica gel, alkoxysilane and the like can be used. As the metal source, various inorganic or organic metal compounds can be used. Preferred examples of such metal compounds include metal sulfates [eg, Al ₂ (S
O ₄ ) ₃ ], metal nitrate [eg, Fe (N
O ₃ ) ₃ ], alkali metal salts of metal oxides [eg Na
Metal salts such as AlO ₂ ]; metal chlorides [eg Ti
Metal halides such as Cl ₄ ], metal bromide [eg MgBr ₂ ]; metal alkoxides [eg Ti
(OC ₂ H ₅ ) ₄ ]. The obtained crystalline metallosilicate can be ion-exchanged to a desired cation as required. For example, H ⁺ -type cations are obtained by converting crystalline metallosilicate into HCl, NH ₄ Cl, N
Mix and stir in an aqueous solution such as H ₃ to exchange the cation species for H ⁺ or NH ₄ ⁺ form, then filter the solid product,
After washing with water and drying, it can be prepared by baking at 350 to 600 ° C. A cation other than H ⁺ can be prepared by performing the same operation using an aqueous solution containing the desired cation.

In the present invention, the crystalline metallosilicate is used as a catalyst when a long-chain olefin is reacted with a (poly) alkylene glycol to produce a (poly) alkylene glycol mono-higher alkyl ether. Crystalline metallosilicates of various types may be used, or crystalline metallosilicates of various types may be used in combination. Alternatively, it may be used in combination with a known catalyst such as sulfuric acid, heteropolyacid, benzenesulfonic acid, and ion exchange resin.

In the present invention, the catalyst may be used in any form. However, in order to stably suspend the catalyst in the (poly) alkylene glycol phase, the catalyst is preferably in the form of powder or granules, and in particular, fine particles. Is preferred. In the reaction between the (poly) alkylene glycol and the long-chain olefin in the present invention, the (poly) alkylene glycol phase in which the crystalline metallosilicate is suspended is mainly used as a continuous phase, and the long-chain olefin phase is dispersed and reacted. (Poly) alkylene glycol mono-higher alkyl ether can be efficiently produced.

In the present invention, the long-chain olefin and the (poly) alkylene glycol, which are the raw materials, dissolve each other only in a small amount to form two phases. Then, the (poly) alkylene glycol mono-higher alkyl ether, which is a reaction product, is mainly distributed to the long-chain olefin phase. The crystalline metallosilicate as a catalyst is contained in the (poly) alkylene glycol phase. Therefore, in order for the reaction to proceed efficiently, it is necessary to efficiently mix and contact the long-chain olefin, the (poly) alkylene glycol, and the crystalline metallosilicate as a catalyst. In the present invention, by suspending the crystalline metallosilicate in the (poly) alkylene glycol, the contact efficiency between the catalyst and the raw material can be increased and the reaction can proceed efficiently. In addition, by using the (poly) alkylene glycol phase as the continuous phase and the long-chain olefin phase as the dispersed phase, the mixing efficiency of the two liquid phases can be improved, the reaction speed can be improved, and the reactivity and operating efficiency of the apparatus can be improved. Is improved. For example, when performing a batch reaction under stirring using a tank-type reactor, when the (poly) alkylene glycol phase is a continuous phase, a uniform mixing state can be formed with lower stirring power, and the upper and lower mixing efficiency can be improved. Therefore, it is preferable. Further, for example, when a flow-type reaction is performed using a continuous tank reactor, one of the liquid phases can be prevented from flowing by bypass, and the volume ratio of the two liquid phases to be continuously charged and the volume ratio of the two liquid phases in the reactor can be reduced. This is preferable because the volume ratio of the liquid phase can be kept substantially the same. Further, the (poly) alkylene glycol phase in which the crystalline metallosilicate is suspended is mainly used as a continuous phase, and a long-chain olefin phase is dispersed and reacted, so that a decrease in the activity of the catalyst is preferably suppressed. When the long-chain olefin phase is used as the continuous phase, the mixing efficiency of the two liquid phases is reduced, and the activity of the catalyst is liable to decrease.

The volume ratio of the long-chain olefin phase in which the crystalline metallosilicate is suspended to the (poly) alkylene glycol phase (long-chain olefin phase / (poly) alkylene glycol phase) in the present invention is in the range of 0.01 to 2. , More preferably in the range of 0.05 to 1.5. If the volume ratio is less than 0.01, the (poly) alkylene glycol phase becomes too large, which undesirably reduces productivity. On the other hand, if the volume ratio exceeds 2, the long-chain olefin phase becomes too large, and the (poly) alkylene glycol phase cannot be made a continuous phase, which is not preferable.

In the present invention, the concentration of the crystalline metallosilicate used as the catalyst suspended in the (poly) alkylene glycol phase is not particularly limited, but may be 0.1 to 50% by weight in the (poly) alkylene glycol phase. Preferably, more preferably 0.2 to 30% by weight
Range. The reaction between the long-chain olefin and the (poly) alkylene glycol in the present invention is carried out in the presence of a solvent.
Alternatively, it can be performed in the absence of any of them. As the solvent, a solvent such as nitromethane, nitroethane, nitrobenzene, dioxane, ethylene glycol dimethyl ether, sulfolane, benzene, toluene, xylene, hexane, cyclohexane, decane, and paraffin can be used.

The long-chain olefin and (poly) in the present invention
The reaction with the alkylene glycol can be carried out by a generally used method such as a batch reaction, a flow reaction and the like, and is not particularly limited. As described above, the ratio between the long-chain olefin and the (poly) alkylene glycol, which are the raw materials for the reaction, is preferably such that the volume ratio between the long-chain olefin phase and the (poly) alkylene glycol phase is in the range of 0.01 to 2, Further, the molar ratio of the (poly) alkylene glycol to the long-chain olefin is preferably 0.05 to 10
0, more preferably in the range of 0.1 to 50. The reaction temperature is preferably from 50 to 250 ° C, more preferably 100 to 250 ° C.
To 200 ° C., and 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 .

When a batch reactor is used, a (poly) alkylene glycol having a crystalline metallosilicate of the present invention suspended therein and a long-chain olefin are charged into the reactor, and the (poly) alkylene glycol phase is mainly used as a continuous phase. By reacting at a predetermined temperature and a predetermined pressure while mixing a long-chain olefin phase as a dispersed phase, a (poly) alkylene glycol mono-higher alkyl ether as a product can be produced. In order to make the (poly) alkylene glycol phase a continuous phase, the shape of the reactor and the stirrer, the installation position of the stirring blade, the volume ratio of the (poly) alkylene glycol to the long-chain olefin, the order of the feed, and the like are adjusted. , (Poly) alkylene glycol phase can be obtained as a continuous phase. For example, when using a tank-type reactor equipped with a stirrer, first, a catalyst and a (poly) alkylene glycol are charged and stirred to form a (poly) alkylene glycol phase in which the catalyst is suspended, and a long-chain olefin is added thereto. There is a method of feeding a predetermined amount.

The reaction time varies depending on the reaction temperature, the amount of the catalyst, the composition ratio of the raw materials and the like, but is in the range of 0.1 to 100 hours, preferably 0.5 to 30 hours. After the reaction, the two liquid phases are separated into liquid and liquid, and the target substance is obtained from the long-chain olefin phase (poly)
The alkylene glycol mono-higher alkyl ether can be recovered by extraction or distillation, and the unreacted raw materials can be recycled for the next reaction. The (poly) alkylene glycol phase in which the catalyst is suspended can be recycled to the next reaction after replenishing the (poly) alkylene glycol consumed by the reaction.

When a flow reactor is used, it can be carried out in any of a moving bed system and a stirred bed system. The reaction may be carried out using either a continuous tank reactor or a tubular reactor, and the continuous tank reactor may have one stage or two or more stages. The reaction conditions vary depending on the raw material composition, the catalyst concentration, the reaction temperature and the like, but the liquid hourly space velocity (LHSV), that is, the value obtained by dividing the volume flow rate of the flowing raw material by the volume of the reactor, is 0.01 to 50 hr ^-1. ,
In particular, it is preferably in the range of 0.1 to 20 hr ^-1 .
After completion of the reaction, the desired (poly) alkylene glycol mono-higher alkyl ether can be recovered by the same operation as in the batch reaction.

(Poly) obtained by the production method of the present invention
Alkylene glycol mono-higher alkyl ethers are suitable as raw materials for surfactants.

[0025]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. However, this embodiment is one aspect of the present invention, and the present invention is not limited to this. In the examples, the yield (mol%) of monoethylene glycol monododecyl ether was calculated according to the following equation.

Yield (mol%) of monoethylene glycol monododecyl ether = (mol number of monoethylene glycol monododecyl ether produced / mol number of dodecene supplied) × 100 <Preparation of catalyst> BEA type zeolite manufactured by PQ (Product name:
VALFOR CP 811BL-25) was treated with 15 ml of 0.1N hydrochloric acid per gram at 40 ° C. for 3 hours to remove a part of Al in the zeolite, and then washed with distilled water.
Washing was performed. Next, the product was dried at 120 ° C. overnight and calcined in air at 400 ° C. for 3 hours to obtain a catalyst (1).

When the composition of the obtained catalyst (1) was analyzed by fluorescent X-ray, the atomic ratio of Si to Al was 23. This catalyst (1) has a BEA type and its X
The results of the line diffraction analysis were as shown in Table 1.

[0028]

[Table 1]

<Production of (poly) alkylene glycol mono-higher alkyl ether> 252 g of 1-dodecene (1.
5 mol), 279 g (4.5 mol) of monoethylene glycol, 10.6 g of catalyst (1) (molar ratio of dodecene / monoethylene glycol = 1/3, weight of catalyst to dodecene = 4.2% by weight) A 1000 ml glass reactor equipped with a meter, a condenser and a stirrer was charged, the inside of the reactor was replaced with nitrogen, and then kept in a nitrogen atmosphere at normal pressure. Next, the temperature was raised to 150 ° C. while stirring at 500 rpm, and maintained at the same temperature. At this time, the catalyst was suspended in the monoethylene glycol phase, the monoethylene glycol phase mainly formed a continuous phase, and the two liquids were well mixed and stirred with the dodecene phase as the dispersed phase. The volume ratio of the dodecene phase to the monoethylene glycol phase at 150 ° C. (volume of the dodecene phase / volume of the monoethylene glycol phase) was 1.4. The reaction solution was sampled 1.5 hours and 3 hours after the start of the reaction, and the monoethylene glycol monododecyl ether contained in the dodecene phase was measured using a gas chromatograph. The results are shown in Table 2. After reacting for 3 hours, the mixture was cooled, stopped stirring, and allowed to stand. After separating and removing the upper layer of the dodecene phase from the reactor, 28.0 g of monoethylene glycol (corresponding to monoethylene glycol consumed in the reaction) and 252 g of 1-dodecene were added to the monoethylene glycol phase containing the catalyst remaining in the reactor. And add
The same reaction as the first reaction was performed and analyzed by the same method. The results are shown in Table 2. Comparative Example 1 In Example 2, the amount of the raw material and the amount of catalyst charged in the reactor were
1-dodecene 336 g (2 mol), monoethylene glycol 124 g (2 mol), catalyst (1) 14.1 g (molar ratio of dodecene / monoethylene glycol = 1/1, weight of catalyst to dodecene = 4.2% by weight) The first reaction was carried out in the same manner as in Example 2 except that the above was used. The catalyst was suspended in the monoethylene glycol phase, with the dodecene phase mainly forming the continuous phase and the monoethylene glycol phase being the dispersed phase. There was a transparent dodecene phase at the top of the reaction solution, and the mixed state of the two solutions was heterogeneous. 1
The volume ratio of the dodecene phase to the monoethylene glycol phase at 50 ° C. (volume of the dodecene phase / volume of the monoethylene glycol phase) was 4.0. Start the reaction 1.5
After a lapse of 3 hours, the reaction solution was sampled, and the monoethylene glycol monododecyl ether contained in the dodecene phase was measured using a gas chromatograph. The results are shown in Table 2. After reacting for 3 hours, the mixture was cooled, stopped stirring, and allowed to stand. After separating and removing the upper layer of the dodecene phase from the reactor, 36.0 g of monoethylene glycol (equivalent to the monoethylene glycol consumed in the reaction) and 336 g of 1-dodecene were added to the monoethylene glycol phase containing the catalyst remaining in the reactor. Was added, the same reaction as in the first reaction was performed, and analysis was performed by the same method. The results are shown in Table 2.

[0030]

[Table 2]

[0031]

According to the present invention, by using a crystalline metallosilicate as a catalyst, a (poly) alkylene glycol mono-higher alkyl ether can be produced with a high reaction rate, a high selectivity and a high yield. Further, by suspending the crystalline metallosilicate in the (poly) alkylene glycol, the contact efficiency between the catalyst and the raw material can be increased, and the reaction can proceed efficiently. Furthermore, by using the (poly) alkylene glycol phase as the continuous phase and the long-chain olefin phase as the dispersed phase, the mixing efficiency of the two liquid phases is improved, the reaction rate is improved, and the reactivity and the operation efficiency of the apparatus are improved. improves. Further, the (poly) alkylene glycol phase in which the crystalline metallosilicate is suspended is mainly used as a continuous phase, and a long-chain olefin phase is dispersed and reacted, whereby a decrease in the activity of the catalyst can be suppressed.

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

Claims (3)

[Claims] 1. A method for producing a (poly) alkylene glycol mono-higher alkyl ether by reacting a (poly) alkylene glycol with a long-chain olefin, comprising using a crystalline metallosilicate as a catalyst and suspending the catalyst. A method for producing a (poly) alkylene glycol mono-higher alkyl ether, characterized in that the (poly) alkylene glycol phase thus obtained is mainly used as a continuous phase, and a long-chain olefin phase is dispersed and reacted. 2. The volume ratio of the long chain olefin phase to the (poly) alkylene glycol phase (long chain olefin phase / (poly) alkylene glycol phase) is 0.01 to 2.
The method for producing the (poly) alkylene glycol mono-higher alkyl ether described in the above. 3. The method for producing a (poly) alkylene glycol mono-higher alkyl ether according to claim 1, wherein the long-chain olefin is at least one selected from the group consisting of olefins having 8 to 30 carbon atoms.