JPH10167991A - Production of long-chain olefin and (poly)alkylene glycol mono-higher alkyl ether and catalyst used therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To industrially and advantageously produce a long-chain olefin at a high reactional rate in high selectivity and high yield by carrying out the eliminating reaction of a higher alcohol by using a crystalline metallosilicate as a catalyst. SOLUTION: The eliminating reaction of a higher alcohol is carried out by using a crystalline metallosilicate such as a BEA type metallosilicate as a catalyst to afford a long-chain olefin. The eliminating reaction of an alkylene or a polyalkylene glycol mono-higher alkyl ether is similarly conducted to provide the long-chain olefin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a process for producing a long-chain olefin and a (poly) alkylene glycol mono-higher alkyl ether, and a catalyst used therefor. More specifically, a method for producing a long-chain olefin by elimination reaction of higher alcohol, a method for producing a long-chain olefin by elimination reaction of (poly) alkylene glycol mono-higher alkyl ether, and (poly) alkylene glycol di-higher alkyl ether A process for producing a (poly) alkylene glycol mono-higher alkyl ether by an elimination reaction of the compound and a catalyst used therefor.

[0002]

2. Description of the Related Art It is generally known that an inorganic acid such as sulfuric acid is used as a catalyst when an alcohol, particularly a secondary or tertiary alcohol is dehydrated to synthesize an olefin. It is not industrially satisfactory, such as difficulty in separating the catalyst, low selectivity and low yield. It is not known to produce olefins or monoalkyl ethers from ethers, particularly (poly) alkylene glycol di-higher alkyl ethers and (poly) alkylene glycol mono-higher alkyl ethers.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to industrially advantageously use a higher alcohol, a (poly) alkylene glycol mono-higher alkyl ether and ( An object of the present invention is to provide a method for producing a long-chain olefin and a (poly) alkylene glycol mono-higher alkyl ether by an elimination reaction of a (poly) alkylene glycol di-higher alkyl ether, and a catalyst used therefor.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the use of a crystalline metallosilicate as a catalyst makes it possible to reduce the reaction rate of the elimination reaction of a higher alcohol. A long-chain olefin can be produced quickly, with high selectivity and high yield, and a long-chain olefin can be produced with a high reaction rate and high selectivity and high yield in the elimination reaction of (poly) alkylene glycol mono-higher alkyl ether. , The rate of elimination reaction of (poly) alkylene glycol di-higher alkyl ether is high, high selectivity,
They have found that a (poly) alkylene glycol mono-higher alkyl ether can be produced in high yield, and have completed the present invention.

That is, the present invention provides a method for producing a long-chain olefin by elimination reaction of a higher alcohol,
A method for producing a long-chain olefin, comprising using a crystalline metallosilicate as a catalyst. The present invention also relates to a method for producing a long-chain olefin by an elimination reaction of a (poly) alkylene glycol mono-higher alkyl ether, comprising using a crystalline metallosilicate as a catalyst. It is.

The present invention also relates to a process for producing a (poly) alkylene glycol mono-higher alkyl ether by an elimination reaction of the (poly) alkylene glycol di-higher alkyl ether, wherein a crystalline metallosilicate is used as a catalyst. A method for producing a (poly) alkylene glycol mono-higher alkyl ether, which is a feature. In these production methods, the crystalline metallosilicate is B
It is preferably an EA type metallosilicate.

Further, the present invention is a catalyst used for producing a long-chain olefin by a elimination reaction of a higher alcohol, which is characterized by containing at least a crystalline metallosilicate. Also, the present invention
A catalyst used for producing a long-chain olefin by elimination reaction of a (poly) alkylene glycol mono-higher alkyl ether, characterized in that the catalyst contains at least a crystalline metallosilicate.

[0008] The present invention also relates to a catalyst used for producing a (poly) alkylene glycol mono-higher alkyl ether by an elimination reaction of the (poly) alkylene glycol di-higher alkyl ether, wherein at least a crystalline metallosilicate is used. It is a catalyst characterized by containing.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The crystalline metallosilicate used in the present invention is a regular porous material 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 is a crystalline aluminosilicate (generally referred to as zeolite) and a compound in which another metal element is introduced into the crystal lattice in place of the Al atom of the crystalline aluminosilicate. Specific examples of other metal elements include B, Ga, In, Ge, Sn, P, As, Sb, and S.
c, Y, La, Ti, Zr, V, Cr, Mn, Fe, C
o, Ni, Cu, Zn, etc., 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 (ZSM-5, etc.) 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 preferred because of their excellent catalytic activity.

The crystalline metallocene 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 for each elimination reaction, but a single crystalline metallosilicate may be used, or various crystalline crystalline metallosilicates may be used. They 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, such as a powder, a granule, or a molded article having a specific shape. When using a molded body, alumina or silica as a carrier or a binder,
Titania or the like can also be used. As the higher alcohol used in the elimination reaction of the higher alcohol of the present invention, secondary or tertiary is preferred because primary is less reactive. As the higher alkyl group of the higher alcohol,
It is preferably a hydrocarbon group having 8 to 30 carbon atoms, more preferably a higher alkyl group comprising a hydrocarbon group having 10 to 20 carbon atoms. Further, when the obtained long-chain olefin is used for a surfactant, a linear higher secondary alkyl group is preferred. Specific examples of the higher alcohol include various isomers of decanol (such as 2-6-decanol), various isomers of undecanol (such as 2-6-undecanol),
Various isomers of dodecanol (such as 2-7-dodecanol), various isomers of tridecanol (such as 2-7-tridecanol), various isomers of tetradecanol, various isomers of pentadecanol, and various isomers of hexadecanol , Various isomers of heptadecanol, various isomers of octadecanol, various isomers of nonadecanol, various isomers of eicosanol, and the like. These higher alcohols may be used alone or in combination of two or more.

As the higher alkyl group of the (poly) alkylene glycol mono-higher alkyl ether used in the elimination reaction of the (poly) alkylene glycol mono-higher alkyl ether of the present invention, the primary is lower in reactivity, so Tertiary is preferred. Furthermore, the carbon number 8
It is preferably a hydrocarbon group having from 30 to 30, more preferably a higher alkyl group comprising a hydrocarbon group having from 10 to 20 carbon atoms. Further, when the obtained long-chain olefin is used for a surfactant, a linear higher secondary alkyl group is preferred. As the (poly) alkylene glycol residue of the (poly) alkylene glycol mono-higher alkyl ether, monoethylene glycol, diethylene glycol,
Triethylene glycol, polyethylene glycol, monopropylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol,
1,3-propanediol, 1,2-butanediol,
2,3-butanediol, 1,4-butanediol,
Residues such as 1,6-hexanediol and 1,4-cyclohexanemethanediol are exemplified. These (poly) alkylene glycol mono-higher alkyl ethers may be used alone or in combination of two or more.

In the present invention, when the higher alcohol is eliminated, a long-chain olefin and water are produced. Further, in the present invention, when the (poly) alkylene glycol mono-higher alkyl ether is subjected to an elimination reaction, a long-chain olefin and a (poly) alkylene glycol are produced. A reaction in which the position of the unsaturated bond of the long-chain olefin formed in the reaction process of the present invention isomerizes occurs simultaneously. Generally, the inner olefin is more thermodynamically stable with respect to the α-olefin. Therefore, even when an α-olefin such as 1-dodecene is directly produced from a higher alcohol, the type of the raw material alcohol and the type of the catalyst The temperature varies depending on the reaction temperature, reaction time, etc., but gradually isomerizes into a mixture having a distribution at the position of the unsaturated bond. Further, even when an inner olefin having an unsaturated bond at the center of an alkyl chain such as 6-dodecene is directly produced from a higher alcohol, the inner olefin varies depending on the type of the starting alcohol, the type of the catalyst, the reaction temperature, the reaction time, and the like. However, the position of the unsaturated bond gradually widens from the center and isomerizes into a mixture having a distribution at the position of the unsaturated bond.

In the present invention, the (poly) alkylene glycol di-higher alkyl ether used in the elimination reaction of the (poly) alkylene glycol di-higher alkyl ether includes a higher alkyl group similar to the aforementioned (poly) alkylene glycol mono-higher alkyl ether. And those having a (poly) alkylene glycol residue can be used. In the present invention, when the (poly) alkylene glycol di-higher alkyl ether is eliminated, a (poly) alkylene glycol mono-higher alkyl ether and a long-chain olefin are produced. Further, when the (poly) alkylene glycol di-higher alkyl ether is reacted in the presence of the (poly) alkylene glycol, two molecules of the (poly) alkylene glycol mono-higher alkyl ether may be formed.

The higher alcohol of the present invention, (poly)
The elimination reaction of the alkylene glycol mono-higher alkyl ether and the (poly) alkylene glycol di-higher alkyl ether can be carried out either in the presence or absence of a solvent. As the solvent, a solvent such as water, alcohol, nitromethane, nitroethane, nitrobenzene, dioxane, ethylene glycol dimethyl ether, sulfolane, benzene, toluene, xylene, hexane, cyclohexane, decane, and paraffin can be used. Specific examples of alcohol include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, decyl alcohol, dodecyl alcohol, monoethylene glycol, diethylene glycol, triethylene glycol, (poly) Ethylene glycol, monoethylene glycol monomethyl ether, monoethylene glycol monoethyl ether, monoethylene glycol monoalkyl ether, propylene glycol, dipropylene glycol, tripropylene glycol, (poly) propylene glycol, 1,3-propanediol, 1,4 -Butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, etc. It can gel.
These may be used alone or as a mixture.

In the present invention, the higher alcohol, (poly)
The elimination reaction of the alkylene glycol mono-higher alkyl ether and the (poly) alkylene glycol di-higher alkyl ether can be carried out by a commonly used method such as a batch reaction or a flow reaction, and is not particularly limited. The reaction temperature is preferably from 50 to 250 ° C., more preferably from 100 to 200 ° C., and the reaction pressure may be any of reduced pressure, normal pressure or increased pressure, but normal pressure to 20 kg / c.
A range of m ² is preferred.

When a batch reactor is used, the catalyst and the raw material of the present invention are charged into the reactor, and the mixture is stirred at a predetermined temperature and a predetermined pressure to obtain a mixture containing a product. The amount of the catalyst used is not particularly limited, but may be from 0.1 to 100% by weight based on the raw material higher alcohol, (poly) alkylene glycol mono-higher alkyl ether or (poly) alkylene glycol di-higher alkyl ether. Preferably, more preferably 0.5 to 50
% By weight is used. The reaction time depends on the reaction temperature, amount of catalyst,
Although it depends on the raw material composition ratio and the like, it is in the range of 0.1 to 100 hours, preferably 0.5 to 30 hours. After the reaction, the catalyst is separated by a method such as centrifugation, filtration, and drying, and can be recycled for the next reaction. The product, long-chain olefin or (poly) alkylene glycol mono-higher alkyl ether, can be recovered from the reaction solution from which the catalyst has been separated and removed by extraction or distillation, and unreacted raw materials can be recycled for the next reaction. Can be.

When a flow reactor is used, it can be carried out in any of a fluidized bed system, a moving bed system, a fixed bed system and a stirred tank system. 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 long-chain olefin or (poly) alkylene glycol mono-higher alkyl ether can be recovered by the same operation as in the batch reaction.

In the elimination reaction, the elimination product (a long-chain olefin or water in the case of elimination of a higher alcohol, or a long-chain olefin or water in the case of elimination of a (poly) alkylene glycol mono-higher alkyl ether). In the case of elimination of (poly) alkylene glycol or (poly) alkylene glycol di-higher alkyl ether, a long-chain olefin or (poly) alkylene glycol or (poly) alkylene glycol mono-higher alkyl ether)
Is extracted outside the reaction system, whereby the equilibrium is biased toward the product side, and the yield can be increased.

In the present invention, the elimination reaction of the (poly) alkylene glycol mono-higher alkyl ether and the (poly)
The elimination reaction of the alkylene glycol di-higher alkyl ether may be carried out independently of each other, or may be carried out continuously. When the reaction is performed continuously, a long-chain olefin may be produced at a stroke without taking out a (poly) alkylene glycol mono-higher alkyl ether from the (poly) alkylene glycol di-higher alkyl ether as a raw material. The (poly) alkylene glycol mono-higher alkyl ether obtained by the elimination reaction of the higher alkyl ether may be once taken out and then used for producing a long-chain olefin.
In both the elimination reaction of the (poly) alkylene glycol di-higher alkyl ether and the elimination reaction of the (poly) alkylene glycol mono-higher alkyl ether, it is desirable to use a crystalline metallosilicate as a catalyst. A crystalline metallosilicate can also be used as a catalyst in only one of the elimination reaction of the higher alkyl ether and the elimination reaction of the (poly) alkylene glycol mono higher alkyl ether.

According to the process for producing a long-chain olefin and a (poly) alkylene glycol mono-higher alkyl ether of the present invention, a useful product as a surfactant raw material can be obtained.

[0026]

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 of the product was calculated according to the following formula. <Production of long-chain olefin by elimination reaction of higher alcohol> Yield of dodecene (mol%) = (mol number of generated dodecene / mol number of supplied 2-dodecanol) × 100 <(poly) alkylene glycol di-higher Formation of (poly) alkylene glycol mono-higher alkyl ether by elimination reaction of alkyl ether and formation of long-chain olefin by elimination reaction of (poly) alkylene glycol mono-higher alkyl ether> Residual amount of monoethylene glycol didodecyl ether (mol %) = (Number of moles of monoethylene glycol didodecyl ether remaining / number of moles of monoethylene glycol dododecyl ether supplied) × 100 Yield (mol%) of monoethylene glycol monododecyl ether = (monoethylene glycol produced) Monododecylue Number of moles of ter / (number of moles of monoethylene glycol didodecyl ether supplied × 2) × 100 Yield of dodecene (mol%) = (number of moles of generated dodecene / (number of moles of supplied monoethylene glycol didodecyl ether) (Mol number x 2)) x 100 <Preparation of catalyst> Example 1 (catalyst (1)) BEA type zeolite manufactured by PQ (trade name: VALFOR)
CP 811BL-25) was used as catalyst (1). The atomic ratio of Si to Al in the catalyst (1) was 12.5,
The specific surface area was 750 m ² / g. Example 2 (Catalyst (2)) BEA-type zeolite manufactured by PQ (trade name: VALFOR)
CP 811BL-25) in 15 ml of 0.
After treating with 1N hydrochloric acid at 40 ° C. for 3 hours to remove a part of Al in the zeolite, it was washed with distilled water and washed.
The product is then dried overnight at 120 ° C.
The catalyst (2) was obtained by calcining at 3 ° C. for 3 hours.

When the composition of the obtained catalyst (2) was analyzed by fluorescent X-ray, the atomic ratio of Si to Al was 23. The catalyst (2) retained the BEA type, and the result of X-ray diffraction analysis thereof was as shown in Table 1.

[0028]

[Table 1]

Example 3 <Elimination Reaction of Higher Alcohol> 2-Dodecanol
4 g (0.36 mol) and 2.5 g of catalyst (1) were charged into a 200-ml glass reactor equipped with a thermometer, a cooling pipe and a stirrer, and the inside of the reactor was replaced with nitrogen. Held. Then, while stirring at 600 rpm, 1
The temperature was raised to 50 ° C. and maintained at the same temperature. After the reaction for 2 hours, a part of the reaction solution was sampled and analyzed by gas chromatography. The yield of dodecene was 98.5 mol%. Example 4 <Production of (poly) alkylene glycol di-higher alkyl ether> 840.0 g (5 mol) of 1-dodecene, 930.0 g (15 mol) of monoethylene glycol, catalyst
(2) 103.3 g was charged into a glass-made 2000 ml reactor equipped with a thermometer, a cooling pipe and a stirrer, and 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 135 ° C. while stirring at 500 rpm, and the temperature was maintained for 20 hours. After 20 hours, the reaction solution was cooled and the olefin phase was separated. As a result of analysis by gas chromatography, the olefin phase contained 276 g of monoethylene glycol monododecyl ether and 199 g of monoethylene glycol didodecyl ether.
This olefin phase is decompressed and a distillation column (height 500 m)
m, inner diameter 20 mm, filled with stainless steel Dickson packing of 1.5 mmφ as a filler).
The resulting solution was transferred to a ml flask, and vacuum distillation was performed to separate and collect dodecene, monoethylene glycol monododecyl ether, and monoethylene glycol didodecyl ether contained in the olefin phase. The vapor pressure of monoethylene glycol didodecyl ether was 193 ° C. and 1 mmHg. The yield of the obtained monoethylene glycol didodecyl ether was 150 g, and the purity calculated from the area ratio of the gas chromatograph was 93.5%. <Elimination reaction of (poly) alkylene glycol di-higher alkyl ether> 85.1 g (0.2 mol) of monoethylene glycol didodecyl ether obtained above, 62.0 g (1 mol) of monoethylene glycol, catalyst (2 ) 7.
1 g of glass 2 equipped with thermometer, cooling tube and stirrer
The reactor was charged into a 00 ml reactor, the atmosphere in the reactor was replaced with nitrogen, and the reactor was maintained at a normal pressure in a nitrogen atmosphere. Then, 600 rpm
The temperature was raised to 150 ° C. while stirring at m and maintained at the same temperature. After the start of the reaction, a part of the reaction solution was sampled with time and analyzed by gas chromatography. Table 2 shows the results. It can be seen that monoethylene glycol didodecyl ether reacts to produce monoethylene glycol monododecyl ether and olefin, and that monoethylene glycol monododecyl ether is once accumulated and then decomposed into olefin.

[0030]

[Table 2]

[0031]

According to the present invention, by using a crystalline metallosilicate as a catalyst, a higher alcohol,
The reaction rate of the elimination reaction of the (poly) alkylene glycol mono-higher alkyl ether and the (poly) alkylene glycol di-higher alkyl ether is high, and the selectivity is high.
Long chain olefins and (poly) alkylene glycol mono-higher alkyl ethers can be produced in high yield.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07C 43/10 C07C 43/10 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Yukio Sumino Kawasaki, Kawasaki City, Kanagawa Prefecture 14-1 Chidoricho, Ward Inside Nippon Shokubai Co., Ltd.

Claims (9)

[Claims] 1. A method for producing a long-chain olefin by a elimination reaction of a higher alcohol, which comprises using a crystalline metallosilicate as a catalyst. 2. The method for producing a long-chain olefin according to claim 1, wherein the crystalline metallosilicate is a BEA-type metallosilicate. 3. A method for producing a long-chain olefin by an elimination reaction of a (poly) alkylene glycol mono-higher alkyl ether, wherein a crystalline metallosilicate is used as a catalyst. 4. The method for producing a long-chain olefin according to claim 3, wherein the crystalline metallosilicate is a BEA-type metallosilicate. 5. A method for producing a (poly) alkylene glycol mono-higher alkyl ether by an elimination reaction of the (poly) alkylene glycol di-higher alkyl ether, characterized in that a crystalline metallosilicate is used as a catalyst. Method for producing poly) alkylene glycol mono-higher alkyl ether. 6. The method for producing a (poly) alkylene glycol mono-higher alkyl ether according to claim 5, wherein the crystalline metallosilicate is a BEA-type metallosilicate. 7. A catalyst used for producing a long-chain olefin by a elimination reaction of a higher alcohol, which comprises at least a crystalline metallosilicate. 8. A catalyst used for producing a long-chain olefin by an elimination reaction of a (poly) alkylene glycol mono-higher alkyl ether, wherein the catalyst contains at least a crystalline metallosilicate. . 9. A catalyst used for producing a (poly) alkylene glycol mono-higher alkyl ether by an elimination reaction of the (poly) alkylene glycol di-higher alkyl ether, comprising at least a crystalline metallosilicate. A catalyst comprising: