JPH10168005A - Production of alcohol by hydration of olefin and catalyst used therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a higher alcohol useful as an intermediate raw material for surfactant at a rapid reaction rate in high selectivity and yield by reacting a long-chain olefin with water in the presence of a BEA type metallosilicate used as a catalyst. SOLUTION: A long-chain olefin (preferably a 8-30C, more preferably 10-20C straight-chain olefin having ethylenic unsaturated bond) is reacted with water in the presence of a BEA type metallosilicate (preferably BEA aluminosilicate having 5-1,500, especially preferably 10-500 atomic ratio of silicon to a metal constituting the metallosilicate and obtained by replacing all or a part of an ion-exchangeable cation of the outside of crystal lattice with H<+> ), preferably in 0.1-200 molar ratio of water to the long chain olefin at 50-250 deg.C at ordinary pressure to 20kg/cm<2> to provide the objective compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing alcohol and a catalyst used therefor. More specifically, the present invention relates to a method for producing a higher alcohol by reacting a long-chain olefin with water and a catalyst used therefor.

[0002]

2. Description of the Related Art Conventionally, a method for producing an alcohol by reacting a light olefin with water has been described with respect to sulfuric acid, phosphoric acid,
Many catalysts such as heteropoly acids, ion exchange resins, and inorganic solid acids have been proposed. For example, Japanese Patent Publication No. 49-3620
No. 3 proposes a method for producing an alcohol by hydrating an olefin using silicotungstic acid as a catalyst. Examples include, in the presence of silicotungstic acid,
A method for producing alcohol by reacting propylene and butene with water is disclosed.

Further, Japanese Patent Application Laid-Open No. 6-1736 proposes a method for producing a higher secondary alcohol by reacting an aqueous solution containing 50% by weight or more of a heteropolyacid as a catalyst with a higher α-olefin. The examples disclose a method for producing a higher secondary alcohol by reacting an aqueous solution of a heteropolyacid of 50% by weight or more with decene.

[0004]

In the above prior art, a heteropolyacid is used as a catalyst, and the hydration reaction of a long-chain olefin is essentially slow in reaction rate. Must be used in a large amount of 50% by weight or more in water, and there is a problem in industrial use.

An object of the present invention is to solve the problems of the above-mentioned conventional method in the hydration reaction of a long-chain olefin having low reactivity, to achieve a high reaction rate, a high selectivity and a high yield. To provide a method for industrially advantageously producing higher alcohols and a catalyst used therefor.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the use of BEA-type metallosilicate as a catalyst has increased the reaction rate between a long-chain olefin and water. The present inventors have found that alcohols can be produced with high selectivity and high yield, and have completed the present invention.

That is, the present invention relates to a method for producing an alcohol by reacting a long-chain olefin with water, wherein the BEA-type metallosilicate is used as a catalyst. Further, the present invention is a catalyst used for producing an alcohol by reacting a long-chain olefin with water, wherein the catalyst contains at least a BEA-type metallosilicate.

In the method for producing an alcohol according to the present invention, the long-chain olefin is preferably at least one selected from the group consisting of olefins having 8 to 30 carbon atoms. Preferably, the BEA-type metallosilicate is a BEA-type aluminosilicate. It is preferable that the BEA-type metallosilicate has an atomic ratio of silicon atoms to metal atoms constituting the metallosilicate of 5 or more and 1500 or less.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION BEA used in the present invention
The type metallosilicate refers to a crystalline metallosilicate having a crystal structure classified according to the IUPAC code named by the International Zeolite Society Structural Committee. Generally, it is also called beta-type metallosilicate or zeolite beta. BE for crystalline metallosilicate
MFI with different crystal structure classification besides type A
Type, MEL type, MTW type, FAU type, MOR type, MTW
Type, LTL type, and the like. Only BEA-type metallosilicates are particularly excellent as catalysts for the reaction of the present invention.

The BEA-type metallosilicate used in the present invention includes BEA-type aluminosilicate and B-type aluminosilicate.
It is a compound in which another metal element is introduced into the crystal lattice in place of the Al atom of the EA-type aluminosilicate. Specific examples of other metal elements include B, Ga, In, Ge, and S.
n, P, As, Sb, Sc, Y, La, Ti, Zr,
V, Cr, Mn, Fe, Co, Ni, Cu, Zn, etc., may be used alone or in a mixture of two or more. BEA in terms of catalytic activity, synthesis and availability
Type aluminosilicate, BEA type ferrosilicate, B
EA-type borosilicate and BEA-type gallosilicate are preferable, and among them, BEA-type aluminosilicate is preferable.

The BEA-type metallosilicate used in the present invention has an atomic ratio of silicon atoms to metal atoms constituting it of 5 to 1500, particularly 10 to 50.
Those having a range of 0 or less are preferred. If the atomic ratio of the silicon atom to the metal atom is too small or too large, the catalytic activity is low, which is not preferable. These BEAs
The metallosilicate has ion-exchangeable cations outside the crystal lattice, and specific examples of these cations include H
⁺ , Li ⁺ , Na ⁺ , Rb ⁺ , Cs ⁺ , Mg ²⁺ , C
a ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , La ³⁺ , R ₄ N
⁺ , R ₄ P ⁺ (R is H or an alkyl group) and the like. Above all, those in which all or part of the cations are substituted with hydrogen ions are suitable as the catalyst of the present invention.

The BEA-type metallosilicate used in the present invention can be synthesized by a generally used synthesis method, for example, a hydrothermal synthesis method. Specifically, ZEOL
ITES, Vol. 8, P46 (1988) and the like. These BEA-type metallosilicates include, for example, a silica source, a metal source,
A composition comprising a quaternary ammonium salt, such as a tetraethylammonium salt, is heated at a temperature of about 100-150 ° C. until crystals form, after which the solid product is filtered, washed with water, dried and then dried at 350-600 ° C. Can be synthesized by firing. Various BEA-type metallosilicates 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. Preferable examples of such metal compounds include metal salts such as metal sulfates, metal nitrates and metal alkali metal salts; metal halides such as metal chlorides and metal bromides; metal oxides; Examples include organometallic compounds such as alkoxides. The obtained BEA-type metallosilicate can be ion-exchanged to a target cation as required. For example, the H ⁺ type cation is prepared by mixing and stirring a BEA type crystalline metallosilicate in an aqueous solution of HCl, NH ₄ Cl, NH _3, etc., exchanging the cation species to H ⁺ type or NH ₄ ⁺ type, and then solid The product can be prepared by filtering, washing with water, drying and calcining 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 BEA-type metallosilicate is used as a catalyst for reacting a long-chain olefin with water, but may be used alone, or may be used as another catalyst such as sulfuric acid, phosphoric acid, heteropolyacid, or the like. A known catalyst such as an ion exchange resin may be used in combination. 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 a molded article is used, alumina, silica, titania, or the like can be used as a carrier or a binder.

The long-chain olefin used in the alcohol production process of 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 can be used without particular limitation, even when the position of the unsaturated bond is α-position, at the inner position, or at both the α-position and the inner position. Of course, two of these long-chain olefins having different unsaturated bond positions
More than one species may be used in combination. In the reaction process of the present invention, a reaction in which the position of the unsaturated bond of the olefin is isomerized occurs simultaneously. Generally, the inner olefin is more thermodynamically stable than the α-olefin,
When an olefin is used, the olefin gradually isomerizes to an inner olefin during the reaction. The rate of isomerization varies depending on the reaction temperature and the type and amount of BEA-type metallosilicate used as a catalyst. The higher alcohol produced by the alcohol production method of the present invention is industrially useful as an intermediate raw material for a surfactant, particularly when an acyclic olefin having 8 to 30 carbon atoms is used as the raw material.

In the present invention, the reaction for producing an alcohol by reacting a long-chain olefin with water can be carried out either in the presence or absence of a solvent.
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 reaction between the long-chain olefin and water in the present invention can be carried out by a commonly used method such as a batch reaction or a flow reaction, and is not particularly limited. The molar ratio of the long-chain olefin, which is a raw material for the reaction, to water is not particularly limited, but the molar ratio of water to the long-chain olefin is preferably 0.1 to 200, more preferably 0.5 to 200.
50 are used. 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.
A range of 20 kg / cm 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 the desired alcohol. The amount of the catalyst used is not particularly limited, but is 0.1 to 100 with respect to the long-chain olefin as a raw material.
% By weight, more preferably from 0.5 to
50% by weight are used. The reaction time varies depending on the reaction temperature, the amount of the catalyst, the composition ratio of the raw materials, and the like.
Hours, preferably in the range of 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. From the reaction solution from which the catalyst has been separated and removed, the target alcohol can be recovered by extraction or distillation, and the unreacted raw material can be recycled for the next reaction. Usually, the long-chain olefin as the raw material and water dissolve only in a small amount to each other, the BEA-type metallosilicate as the catalyst is mainly contained in the aqueous phase, and the alcohol as the product is mainly contained in the olefin phase.
Therefore, in the method of the present invention, after the reaction is completed, the aqueous phase and the olefin phase are separated, the aqueous phase containing the catalyst is replenished with the water consumed by the reaction, then recycled to the next reaction, and the olefin phase is distilled. And the like, a process for recovering the starting olefin and the target alcohol can be established.

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 target alcohol can be recovered by the same operation as in the batch reaction.

When a higher alcohol is produced according to the present invention, the higher alcohol may undergo an addition reaction with an olefin or the higher alcohols may be dehydrated and condensed to form an ether as a by-product. The ether by-produced here is
It can be used as a raw material for lubricants, plasticizers, waxes and the like.

[0021]

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. Yield of alcohol (mol%) = (mol number of generated alcohol / mol number of supplied olefin) × 100 <Preparation of catalyst> Example 1 (catalyst (1)) 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 (1) was obtained by calcining at 3 ° C. for 3 hours.

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. Example 2 (Catalyst (2)) The following two solutions A and B were prepared. Solution A water glass (JIS No. 3) 55.6 g distilled water 69.3 g solution B anhydrous aluminum sulfate 1.61 g concentrated sulfuric acid 4.62 g tetrapropylammonium bromide 6.95 g sodium chloride 16.4 g distilled water 94.6 g 500 ml beaker while stirring solution B The solution A was dropped into the solution B to obtain a mixed gel. The resulting mixed gel was charged into an autoclave, the space was replaced with nitrogen, and the mixture was heated at 120 ° C. for 72 hours with stirring.
The temperature was raised to 0 ° C., and the mixture was further heated for 5 hours.

After cooling to room temperature, the resulting solid was taken out together with the solution, and the supernatant was removed by decantation. The obtained solid was washed with distilled water to remove ammonium salts, and then washed. The solid after washing was dried at 130 ° C. overnight, and then calcined at 550 ° C. in the air to obtain a Na ⁺ type crystalline aluminosilicate.
Further, this product was ion-exchanged to an NH ⁴⁺ type using an aqueous ammonium chloride solution. 80 ° C after ion exchange
By washing with water until chlorine is no longer observed in the above, drying at 130 ° C. overnight, and baking in air at 400 ° C. for 2 hours,
Catalyst (2) was obtained.

The obtained catalyst (2) was treated with a fluorescent X-ray (XR
The composition analysis in F) revealed that the atomic ratio of Si to Al was 26. The specific surface area was 390 m ² / g. This catalyst (2) is of MFI type (ZSM-5),
Table 2 shows the results of the X-ray diffraction analysis. <Production of alcohol> Example 3 119.0 g (0.708 mol) of 1-dodecene, 65.8 g (3.66 mol) of distilled water, and 5.0 g of the catalyst (1) were charged into a 500 ml stainless steel autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the autoclave was closed at normal pressure, and the temperature was raised to 150 ° C. while stirring at 600 rpm. Four hours after the temperature was raised, a part of the reaction solution in the autoclave was sampled, and the olefin phase was analyzed using a gas chromatograph. The olefin phase contained the produced alcohol, and the yield was 2.50%. When the reaction was continued for further 10 hours, the yield of alcohol was 3.95%. No by-products were found in the reaction solution other than the starting material and the product alcohol. Example 4 30.0 g (0.179 mol) of 1-dodecene, 3.2 g (0.178 mol) of distilled water, 1,4-dioxane 11
0.0g and 1.26 g of catalyst (1) were
It was charged in a 0 ml autoclave. Next, after replacing the inside of the autoclave with nitrogen, the autoclave was closed at normal pressure, and 600 r.
The temperature was raised to 150 ° C. while stirring at pm. After the temperature was raised, a part of the reaction solution in the autoclave was sampled at predetermined time intervals and analyzed using a gas chromatograph. The reaction solution contained the produced alcohol, and the yield was 5.62%. When the reaction was continued for further 9 hours, the alcohol yield was 8.21%. No by-products were found in the reaction solution other than the starting material and the product alcohol. Comparative Example 1 119.0 g (0.708 mol) of 1 -dodecene, 65.8 g (3.66 mol) of distilled water, and 5.0 g of catalyst (2) were charged in a 500 ml stainless steel autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the autoclave was closed at normal pressure, and the temperature was raised to 150 ° C. while stirring at 600 rpm. A part of the reaction solution 4 hours after the temperature was raised was sampled, and the olefin phase was analyzed using a gas chromatograph. The olefin phase contained the alcohol formed, but the yield was only 0.18%. Comparative Example 2 10.0 g (0.595 mol) of 1-dodecene, 53.6 g (2.98 mol) of distilled water, and 10.0 g of phosphomolybdic acid (produced by Nippon Inorganic Chemical Industry Co., Ltd.) as a catalyst were made of glass. It was charged in a 1000 ml autoclave. Then
After the inside of the autoclave was replaced with nitrogen, the autoclave was closed at normal pressure, and the temperature was raised to 155 ° C. while stirring at 600 rpm. After the temperature was raised, the reaction was carried out for 4 hours, but no production of alcohol was confirmed. The temperature was further raised to 185 ° C., and the reaction was carried out for 4 hours.
%Met.

[0025]

[Table 1]

[0026]

[Table 2]

[0027]

According to the present invention, by using a BEA-type metallosilicate as a catalyst, a higher alcohol can be produced with a high reaction rate between a long-chain olefin and water, a high selectivity and a high yield.

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

Claims (5)

[Claims] 1. A method for producing an alcohol by reacting a long-chain olefin with water, wherein a BEA-type metallosilicate is used as a catalyst. 2. The method for producing an alcohol 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. 3. The method for producing an alcohol according to claim 1, wherein the BEA type metallosilicate is a BEA type aluminosilicate. 4. The method for producing an alcohol according to claim 1, wherein the BEA-type metallosilicate has an atomic ratio of silicon atoms to metal atoms constituting the metallosilicate of 5 or more and 1500 or less. 5. A catalyst used for producing an alcohol by reacting a long-chain olefin with water, wherein the catalyst contains at least a BEA-type metallosilicate.