CN100513373C - Production process of 3-alkoxy-1-propanols, and 3-alkoxy-1-propanols obtained by the production process - Google Patents

Abstract

Allyl alcohol is reacted with an alcohol compound in the presence of a catalyst containing at least one element selected from Group III elements, lanthanides, and actinides of the periodic table. A method for efficiently preparing 3-hydroxy-1-propanol using an alcohol as a starting material in a single step is provided.

Description

Process for producing 3-alkoxy-1-propanol and 3-alkoxy-1-propanol obtained by the process

This application claims priority to applications based on US Provisional Application Serial No. 60/543294 (filed February 11, 2004) and US Provisional Application Serial No. 60/543405 (filed February 11, 2004).

technical field

The present invention relates to a method for preparing 3-oxyl-1-propanol, and 3-oxyl-1-propanol and its derivatives prepared by the method. More particularly, it relates to a process for the preparation of 3-alkoxy-1-propanol and its derivatives, which process comprises the use of allyl alcohol as a starting material.

Background technique

3-Alkyloxy-1-propanol has a hydroxyl group in the molecule and can be used as a raw material for various reactions such as esterification, etherification and halogenation, and thus is suitable for use as many useful compounds, especially drugs and An important compound of intermediates of agricultural chemicals, silane coupling agents and raw materials of polyester modifiers. In addition, since 1,3-propanediol, which is a raw material of polytrimethylene terephthalate, which has recently been the subject of major attention when hydrolyzing the alkoxy ether segment, can be derived therefrom, 3-alkoxy-1-propanol is useful compound.

Japanese Unexamined Patent Publication (Kokai) No. 10-306,050 discloses a method comprising hydrogenating 3-alkoxy-1-propanal produced by reacting alcohol with acrolein to prepare 3-alkoxy-1- Propanol method as a method for preparing 3-oxyl-1-propanol.

However, this method has such a problem that 3-alkoxy-1-propanal as an intermediate product and acrolein as a raw material may cause secondary reactions due to excellent reactivity, thereby producing a large amount of by-products, and the production The method requires two steps, thus resulting in a complicated process.

Japanese Unexamined Patent Publication (Kokai) No. 8-113,546 discloses a method for producing 3-alkoxy-1-propanol comprising using an alkali metal alkoxide and a halide. However, this method also has such a problem that the halide and the alkali metal alkoxide used for the reaction must be prepared separately, so the method requires at least two steps, resulting in high cost for industrial production.

Japanese Unexamined Patent Publication (Kokai) No. 13-247,503 discloses a method for producing 3-alkoxy-1-propanol from alcohol and allyl alcohol in a single step as a solution to the problem that many steps are required to prepare the method a method of

This method is an excellent method because 3-alkoxy-1-propanol can be produced in a single step, however it is not suitable for industrial production due to low catalytic activity.

As described above, a method for producing 3-alkoxy-1-propanol in the first step has never been proposed in the field of reactions suitable for industrial production.

The background related to 1,3-propanediol which is one of the derivatives of the above-mentioned 3-alkoxy-1-propanol will now be described.

Low-cost methods have been developed to prepare 1,3-propanediol, a compound with great potential demand for synthetic resin raw materials, especially polyester fiber raw materials, using chemical or biological methods.

As a chemical method for producing 1,3-propanediol, for example, a method for producing 1,3-propanediol is generally known, which comprises: synthesizing 3-hydroxypropionaldehyde (hereinafter abbreviated as "3 -HPA"), followed by a hydrogenation reaction (Japanese Unexamined Patent Publication (Kokai) No. 10-212,253), and a method for producing 1,3-propanediol comprising: 3-HPA was synthesized by acylation reaction, followed by hydrogenation reaction (Kohyo (National Publication of Translation) No. 11-515021).

These conventional methods have a problem that 1,3-propanediol is produced by finally hydrogenating 3-HPA, and thus unreacted 3-HPA may remain in 1,3-propanediol. There are also problems that odor and discoloration occur when polyester is synthesized by using 1,3-propanediol containing a carbonyl compound such as 3-HPA.

Therefore, it is preferred that the resulting product 1,3-propanediol is free of carbonyl compounds such as 3-HPA. Japanese Unexamined Patent Publication (Kokai) No. 6-40,973 and Kohyo (National Publication of Translation) No. 11-509,828 disclose that it is difficult to remove the carbonyl compound by conventional purification methods such as distillation.

In order to obtain 1,3-propanediol having a low content of carbonyl compounds including 3-HPA, Japanese Unexamined Patent Publication (Kokai) No. 6-40,973 discloses a hydrogenation reaction of 3-HPA in two steps and Kohyo (translated version of National Publication) No. 11-509,828 discloses a method for removing carbonyl compounds by reacting with a base. However, according to these two methods, it is difficult to achieve 100% conversion of 3-HPA, and the residual carbonyl compounds must be removed, which would burden the process and thus lead to high production costs.

In order to solve these problems, a chemical method for producing 1,3-propanediol without using 3-HPA as a raw material has been studied. This method includes a method of hydrolyzing 3-oxyl-1-propanol which is an ether alcohol compound.

Japanese Unexamined Patent Publication (Kokai) No. 6-157,378 discloses a method for hydrolyzing 4-oxa-1,7-heptanediol to obtain 1,3-propanediol in the presence of a catalyst such as ion exchange resin or zeolite as a reaction method for producing a diol compound by hydrolyzing an ether alcohol compound such as 3-alkoxy-1-propanol.

However, in this publication, the substrate for hydrolysis is limited to 4-oxa-1,7-heptanediol, and it is not disclosed whether the method is applicable to the ether alcohol compound. This method has a problem that a high temperature of 200° C. or higher is required to efficiently perform the hydrolysis reaction, resulting in high energy costs for industrial production.

Similarly, Japanese Unexamined Patent Publication (Kokai) No. 11-209,318 discloses a method of hydrolyzing ether compounds to obtain alcohols in the presence of an acid catalyst.

However, this method described in this publication has a problem that although a high conversion rate of the ether compound is achieved during the reaction, a large amount of by-products other than alcohol is produced. Due to the low selectivity coefficient, it is also difficult to use this method for industrial purposes. Similar to the above-mentioned method, this method has a problem that a high temperature of 200° C. or higher is required to efficiently perform the hydrolysis reaction, resulting in high cost for industrial production.

European Patent No. 1,201,633 also discloses a method of hydrolyzing ether compounds to obtain alcohols in the presence of an acid catalyst.

However, the method described in this publication also has a problem that a reaction temperature of 250° C. or higher is required in order to achieve a high reaction yield, resulting in high energy costs for industrial production. In this publication, the substrate for hydrolysis is limited to 4-oxa-1,7-heptanediol, and it is not disclosed whether this method is applicable to the ether alcohol compound.

As described above, there has never been proposed a method for efficiently producing the target 1,3-propanediol with low energy by hydrolyzing an ether alcohol compound such as 3-alkoxy-1-propanol.

Patent Document 1: Japanese Unexamined Patent Publication (Kokai) No. 10-306,050

Patent Document 2: Japanese Unexamined Patent Publication (Kokai) No. 13-247,503

Patent Document 3: Japanese Unexamined Patent Publication (Kokai) No. 10-212253

Patent Document 4: Kohyo (National Publication of Translation Version) No. 11-515,021

Patent Document 5: Japanese Unexamined Patent Publication (Kokai) No. 6-40973

Patent Document 6: Kohyo (National Publication of Translation Version) No. 11-509,828

Patent Document 7: Japanese Unexamined Patent Publication (Kokai) No. 6-157,378

Patent Document 8: Japanese Unexamined Patent Publication (Kokai) No. 11-209318

Patent Document 9: European Patent No. 1,201,633

invention disclosure

An object of the present invention is to provide a method for preparing 3-alkoxy-1-propanol and its derivatives, which can solve the above-mentioned problems of the prior art.

Another object of the present invention is to provide a method for efficiently preparing 3-alkoxy-1-propanol and its derivatives in a single step using allyl alcohol as a starting material, and 3-alkane prepared by the method Oxy-1-propanol and its derivatives.

As a result of earnest research, the inventors have found that in the case of producing 3-alkoxy-1-propanol from allyl alcohol and an alcohol compound, 3-alkoxy-1-propanol can be efficiently produced by performing the reaction using a catalyst containing a specific element. -1-propanol, and thus completed the present invention.

The present invention (I) relates to a method for preparing 3-alkoxy-1-propanol, which comprises at least one element containing at least one element selected from group III elements, lanthanides and actinides of the periodic table Allyl alcohol is reacted with an alcohol compound in the presence of a catalyst.

The present invention (II) relates to 3-alkoxy-1-propanol produced by the method for producing 3-alkoxy-1-propanol of the present invention (I).

In addition, the present invention includes the following embodiments:

[1] A method for producing 3-alkoxy-1-propanol, which comprises reacting alkenyl in the presence of a catalyst containing at least one element selected from group III elements, lanthanides, and actinides of the periodic table. Propanol reacts with alcohol compounds.

[2] The method for producing 3-alkoxy-1-propanol according to [1], wherein the catalyst containing at least one element selected from group III elements, lanthanides and actinides of the periodic table is oxide.

[3] The method for producing 3-alkoxy-1-propanol according to [2], wherein the catalyst containing at least one element selected from Group III elements, lanthanides and actinides of the periodic table is selected from From: scandium oxide, yttrium oxide, lanthanum oxide, samarium oxide, ytterbium oxide, neodymium oxide, and lutetium oxide.

[4] The method for producing 3-alkoxy-1-propanol according to [1], wherein the catalyst containing at least one element selected from group III elements, lanthanides and actinides of the periodic table is Alkoxide compounds.

[5] The method for producing 3-alkoxy-1-propanol according to [4], wherein the catalyst containing at least one element selected from the group III elements, lanthanides and actinides of the periodic table is selected from From: scandium trimethoxide, scandium triethoxide, scandium triisopropoxide, yttrium trimethoxide, yttrium triethoxide, yttrium triisopropoxide, ytterbium trimethoxide, ytterbium triethoxide and ytterbium triisopropoxide.

[6] The method for producing 3-alkoxy-1-propanol according to any one of [1] to [5], wherein said group-III element, lanthanoid element, and actinide element selected from the periodic table The catalyst of at least one element is loaded on the carrier.

[7] The method for producing 3-alkoxy-1-propanol according to [6], wherein the carrier is activated carbon or magnesium oxide.

[8] The method for producing 3-alkoxy-1-propanol according to [7], wherein the support has a specific surface area of 1000 m ² /g or more.

[9] The method for producing 3-alkoxy-1-propanol according to any one of [1] to [8], wherein the reaction of allyl alcohol and an alcohol compound is performed by a gas phase method.

[10] The method for producing 3-alkoxy-1-propanol according to any one of [1] to [9], wherein the alcohol compound to be reacted with allyl alcohol is at least one selected from the group consisting of methanol , ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, allyl alcohol, phenol and benzyl alcohol.

[11] The method for producing 3-alkoxy-1-propanol according to any one of [1] to [10], wherein the reaction of allyl alcohol and an alcohol compound is performed in the presence of water.

[12] The method for producing 3-alkoxy-1-propanol according to [11], wherein the amount of water present in the reaction system is not less than the The number of moles of elements in the catalyst of at least one element of the actinides and actinides.

[13] The method for producing 3-alkoxy-1-propanol according to any one of [1] to [12], wherein the conversion rate of allyl alcohol is 20% or more.

[14] The method for producing 3-alkoxy-1-propanol according to any one of [1] to [13], wherein the selectivity coefficient of 3-alkoxy-1-propanol is 60% or more .

[15] The method for producing 3-alkoxy-1-propanol according to any one of [1] to [14], wherein the yield of 3-alkoxy-1-propanol is expressed as The catalyst has a metal reaction time per hour of 0.5 or greater; and

[16] 3-alkoxy-1-propanol produced by the method according to any one of [1] to [15].

As a result of further studies on the above-mentioned 3-alkoxy-1-propanol, the present inventors have found that in the case of producing 1,3-propanediol from an ether alcohol compound having a specific structure by 1,3-Propanediol can be produced efficiently by carrying out the reaction using an acid catalyst at a temperature of 200° C., thereby completing the present invention.

That is, the present invention (2-I) relates to a method for producing 1,3-propanediol comprising converting an ether alcohol represented by the general formula (1) at a temperature lower than 200° C. in the presence of at least one acid catalyst Compound hydrolysis:

Formula (1)

(chemical formula 1)

The present invention (2-II) relates to 1,3-propanediol produced by the method of the present invention (2-I).

In addition, the present invention includes the following:

[2-1] A method for producing 1,3-propanediol comprising hydrolyzing an ether alcohol compound represented by the general formula (1) at a temperature lower than 200° C. in the presence of at least one acid catalyst:

Formula (1)

(chemical formula 2)

wherein R represents an aliphatic chain hydrocarbon group, an aliphatic cyclohydrocarbon group or an aryl group having 1 to 10 carbon atoms, provided that R does not have a hydroxyl group.

[2-2] The method for producing 1,3-propanediol according to [2-1], wherein the acid catalyst is an inorganic acid.

[2-3] The method for producing 1,3-propanediol according to [2-1], wherein the acid catalyst is an inorganic solid acid.

[2-4] The method for producing 1,3-propanediol according to [2-1], wherein the acid catalyst is a compound having a sulfonic acid group.

[2-5] The method for producing 1,3-propanediol according to [2-4], wherein the compound having a sulfonic acid group is at least one selected from the group consisting of methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid and sulfonic acid ion exchange resins.

[2-6] The method for producing 1,3-propanediol according to any one of [2-1] to [2-5], wherein the acid catalyst is soluble in the reaction system and the reaction proceeds in a homogeneous state.

[2-7] The method for producing 1,3-propanediol according to any one of [2-1] to [2-5], wherein the acid catalyst is insoluble in the reaction system and the reaction proceeds in a non-uniform state.

[2-8] The method for producing 1,3-propanediol according to any one of [2-1] to [2-7], wherein the At least one compound of ammonium iodide is used as a reaction aid.

[2-9] The method for producing 1,3-propanediol according to any one of [2-1] to [2-8], wherein the substituent R of the ether alcohol compound represented by the general formula (1) is Hydrocarbons having 7 or fewer carbon atoms.

[2-10] The method for producing 1,3-propanediol according to any one of [2-1] to [2-8], wherein the ether alcohol compound represented by the general formula (1) is selected from the following At least one of: 3-methoxy-1-propanol, 3-ethoxy-1-propanol, 3-propoxy-1-propanol, 3-allyloxy-1-propanol and 3- Benzyloxy-1-propanol.

[2-11] The method for producing 1,3-propanediol according to any one of [2-1] to [2-10], wherein the ether alcohol compound represented by the general formula (1) is obtained by making allyl alcohol Prepared by reacting with alcohol compounds.

[2-12] The method for preparing 1,3-propanediol according to any one of [2-1] to [2-11], wherein the hydrolysis reaction is carried out in the presence of water, and the mass of the water does not exceed the 5 times the mass of ether alcohol compound.

[2-13] The method for producing 1,3-propanediol according to any one of [2-1] to [2-12], wherein the conversion rate of 3-alkoxy-1-propanol is 50% or more big.

[2-14] The method for producing 1,3-propanediol according to any one of [2-1] to [2-13], wherein the selectivity coefficient of 1,3-propanediol is 60% or more.

[2-15] 1,3-propanediol produced by the method according to any one of [2-1] to [2-14].

It is obvious that, in the above-mentioned method for producing 1,3-propanediol, when 3-oxyl-1-propanol obtained by the above-mentioned method for producing 3-alkoxy-1-propanol is used as a raw material 1,3-propanediol with a very small carbonyl compound content can be obtained when the ether alcohol compound of the general formula (1), and can be produced at low cost by using the obtained 1,3-propanediol as a raw material for resins such as polyester Resin with less odor and coloration.

Best Mode for Carrying Out the Invention

The present invention will now be described in more detail. In the following description, parts and percentages are by mass unless otherwise specified.

(the present invention (I))

First, the present invention (I) will be described. The present invention (I) relates to a method for preparing 3-alkoxy-1-propanol, which comprises the presence of a catalyst containing at least one element selected from group III elements, lanthanides and actinides of the periodic table Allyl alcohol is reacted with an alcohol compound.

(catalyst)

The catalyst used in the method of (I) of the present invention is characterized in that it contains at least one element selected from the group III elements, lanthanides and actinides of the periodic table. The catalyst may additionally contain any element or compound as long as it does not inhibit the reaction of the allyl alcohol and the alcohol compound.

The catalyst used in the method of the present invention (I) is preferably an oxide, a hydroxide or an alkoxide of an element, particularly preferably an oxide, a hydroxide or an oxide, a hydroxide or alkoxide.

(oxide)

Oxides such as scandium oxide, yttrium oxide, lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide, dysprosium oxide, holmium oxide, erbium oxide, ytterbium oxide, lutetium oxide, actinium oxide, and Thorium oxide was used as a catalyst.

Among these oxides, scandium oxide, yttrium oxide, lanthanum oxide, praseodymium oxide, samarium oxide, gadolinium oxide, dysprosium oxide, holmium oxide, erbium oxide, and ytterbium oxide are preferable, and scandium oxide, yttrium oxide, and ytterbium oxide are more preferable.

(hydroxide)

Hydroxides such as scandium hydroxide, yttrium hydroxide, lanthanum hydroxide, cerium hydroxide, praseodymium hydroxide, neodymium hydroxide, samarium hydroxide, europium hydroxide, gadolinium hydroxide, dysprosium hydroxide, holmium hydroxide, Erbium hydroxide, ytterbium hydroxide, lutetium hydroxide, actinium hydroxide and thorium hydroxide were used as catalysts.

Among these hydroxides, scandium hydroxide, yttrium hydroxide, lanthanum hydroxide, praseodymium hydroxide, samarium hydroxide, gadolinium hydroxide, dysprosium hydroxide, holmium hydroxide, erbium hydroxide, and ytterbium hydroxide are preferred, and more preferred Scandium hydroxide, yttrium hydroxide, and ytterbium hydroxide.

(alcohol salt)

Alkoxides such as scandium trimethoxide, scandium triethoxide, scandium triisopropoxide, yttrium trimethoxide, yttrium triethoxide, yttrium triisopropoxide, lanthanum trimethoxide, lanthanum triethoxide, lanthanum triisopropoxide, praseodymium trimethoxide , praseodymium triethoxide, praseodymium triisopropoxide, samarium trimethoxide, samarium triethoxide, samarium triisopropoxide, gadolinium trimethoxide, gadolinium triethoxide, gadolinium triisopropoxide, dysprosium trimethoxide, dysprosium triethoxide, triisopropylate Dysprosium alcoholate, holmium trimethoxide, holmium triethoxide, holmium triisopropoxide, erbium trimethoxide, erbium triethoxide, erbium triisopropoxide, ytterbium trimethoxide, ytterbium triethoxide, and ytterbium triisopropoxide.

Among these alkoxides, scandium trimethoxide, scandium triethoxide, scandium triisopropoxide, yttrium trimethoxide, yttrium triethoxide, yttrium triisopropoxide, samarium trimethoxide, samarium triethoxide, samarium triisopropoxide, Ytterbium methoxide, ytterbium triethoxide and ytterbium triisopropoxide, more preferably scandium trimethoxide, scandium triethoxide, scandium triisopropoxide, yttrium trimethoxide, yttrium triethoxide and yttrium triisopropoxide.

(form of catalyst)

The form of the catalyst used in the method of (I) of the present invention is not particularly limited, and may be any of a homogeneous form and a heterogeneous form. The catalyst is preferably a heterogeneous catalyst, but may be a homogeneous catalyst, in view of the operation of separating the catalyst after the end of the reaction.

Any homogeneous catalyst can be used as long as it is soluble during the reaction.

The homogeneous catalyst may be used for the reaction in the form of being previously dissolved in a substrate such as allyl alcohol and an alcohol compound, or may be used for the reaction by being supplied simultaneously with the substrate.

Any heterogeneous catalyst can be used as long as it is insoluble during the reaction. For example, a so-called supported catalyst comprising a carrier and a component supported on the carrier containing at least one element selected from group III elements, lanthanides and actinides of the periodic table can also be used.

(supported catalyst)

When the catalyst used in the method of the present invention (I) is a supported catalyst comprising a carrier and a catalyst supported on the carrier, there is no particular limitation on the usable carrier as long as it does not contain Elements, components of at least one element of lanthanides and actinides are reacted, and conventionally known carriers can be used. An important factor required to exhibit catalytic activity is that the support does not react with a component containing at least one element selected from the group III elements, lanthanides and actinides of the periodic table under the conditions under which the catalyst is prepared, and A support that reacts with the components to form a composite oxide after the preparation of the catalyst is finished is not preferred.

(carrier)

As the carrier, activated carbon and magnesium oxide can be used, for example. Activated carbon is preferred in view of the influence on the reaction, the specific surface area during catalyst preparation, or the industrial applicability of the carrier such as strength.

The surface area of the support for the catalyst used in the method of the present invention (I) is preferably 100 to 4000 m ² /g, more preferably 300 to 4000 m ² /g, even more preferably 700 to 4000 m ² /g.

When the component containing at least one element selected from group III elements of the periodic table, lanthanides and actinides as the active species of the catalyst is loaded on the carrier, the amount of the component containing the element is preferably based on the carrier 0.01 to 100% by mass of the total mass. When the amount of the element-containing component is less than 0.01% by mass, sufficient catalytic activity suitable for practical use cannot be obtained due to the low concentration of catalytically active sites, and thus is not preferable. On the other hand, when the amount exceeds 100% by mass, the role of the carrier cannot be exerted, so this is not preferable.

The amount is more preferably 0.05 to 50% by mass, and even more preferably 0.1 to 30% by mass.

(preferred combination of supported catalysts)

When the catalyst used in the method of the present invention (I) is a supported catalyst comprising a carrier and a catalyst loaded on the carrier, for example scandia-activated carbon, scandium oxide-magnesia, yttrium oxide-activated carbon, Yttrium oxide - magnesium oxide, lanthanum oxide - activated carbon, lanthanum oxide - magnesium oxide, praseodymium oxide - activated carbon, praseodymium oxide - magnesium oxide, samarium oxide - activated carbon, samarium oxide - magnesium oxide, gadolinium oxide - activated carbon, gadolinium oxide - magnesium oxide, Dysprosium oxide - activated carbon, dysprosium oxide - magnesium oxide, holmium oxide - activated carbon, holmium oxide - magnesium oxide, erbium oxide - activated carbon, erbium oxide - magnesium oxide, ytterbium oxide - activated carbon, ytterbium oxide - magnesium oxide, scandium trimethylate - activated carbon, Scandium trimethoxide-magnesium oxide, scandium trimethoxide-activated carbon, scandium trimethoxide-magnesia, scandium triisopropoxide-activated carbon, scandium triisopropoxide-magnesia, yttrium trimethoxide-activated carbon, yttrium trimethoxide-magnesia, Yttrium triethoxide-activated carbon, yttrium triethoxide-magnesia, yttrium triisopropoxide-activated carbon, yttrium triisopropoxide-magnesia, samarium trimethoxide-activated carbon, samarium trimethoxide-magnesia, samarium triethoxide-activated carbon, three Samarium ethoxide-magnesium oxide, samarium triisopropoxide-activated carbon, samarium triisopropoxide-magnesium oxide, ytterbium trimethoxide-activated carbon, ytterbium trimethoxide-magnesium oxide, ytterbium triethoxide-activated carbon, ytterbium triethoxide-magnesium oxide, three Ytterbium isopropoxide - activated carbon and ytterbium triisopropoxide - magnesium oxide. These catalysts can be used alone or in combination.

When the catalyst used in the method of (I) of the present invention is a heterogeneous catalyst, most preferred is a supported catalyst containing at least one element selected from group III elements, lanthanides and actinides of the periodic table.

(nature of catalyst)

There are no particular restrictions on the nature and size of these catalysts. Specific examples of the nature of the catalyst include powders, solid pulverized products, flakes, spherical molded products, columnar molded products and cylindrical molded products. The size of the catalyst is preferably 1 to 1000 μm in terms of average particle diameter in the case of a suspended bed or a fluidized bed, and approximately 1 to 20 mm in the case of a fixed bed.

In the case of a suspended bed or a fluidized bed, when the average particle diameter of the catalyst is smaller than the above range, it is difficult to separate the catalyst. On the other hand, when the particle diameter is larger than the above range, the reaction cannot be efficiently performed due to the sedimentation of the catalyst. In the case of a fixed bed, when the average particle diameter is smaller than the above range, clogging of the catalyst layer and increase in differential pressure may occur. On the other hand, when the particle diameter is larger than the above range, the surface area of the catalyst per unit area of the reactor decreases, thereby lowering the reaction efficiency, and thus it is not preferable.

When the catalysts used in the method of the present invention (I) are heterogeneous catalysts, those having properties and particle sizes suitable for the reaction form can be selected and used.

The catalyst used in the method of the present invention (I) can be prepared by any conventionally known method for preparing a catalyst.

(preferred method for preparing catalyst)

When the catalyst used in the method of the present invention (I) is a supported catalyst comprising a carrier and a catalyst loaded on the carrier, considering the trade-off between high dispersion of active sites and cost reduction required to prepare the catalyst Capacitively, the catalyst is preferably prepared by a method comprising the following steps.

That is, the catalyst is preferably prepared by a method comprising the following steps (A) and (B).

Step (A):

preparing a solution comprising a compound containing at least one element selected from group III elements, lanthanides, and actinides of the periodic table dissolved in water or an organic solvent, and placing a carrier in the solution, thereby using the solution impregnated carrier

Step (B):

The solid obtained in step (A) is dried and fired to obtain a catalyst for the preparation of 3-alkoxy-1-propanol

The compound containing at least one element selected from group III elements of the periodic table, lanthanides and actinides used in the step (A) is not particularly limited as long as it is soluble in water or an organic solvent, but preferably chlorine compounds, bromides, sulfates, carbonates, nitrates, phosphates, carbonates or alkoxides.

There is no particular limitation on the method of preparing the supported catalyst comprising a carrier and a catalyst supported on the carrier used in the method of the present invention (I), and the catalyst can be prepared by a conventionally known method.

(alcohol compound)

The alcohol compound used for the reaction with allyl alcohol in the presence of a catalyst in the method of the present invention (I) is a compound having one or more hydroxyl groups in the structure. However, the substituent is not limited to the hydroxyl group, and the alcohol compound may have any substituent other than the hydroxyl group.

Specific examples of alcohol compounds useful in the present invention include, but are not limited to, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, allyl alcohol, phenol, benzyl alcohol, ethyl alcohol, Diol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, tri Methylolpropane and Pentaerythritol.

Among these alcohol compounds, methanol, ethanol, n-propanol, allyl alcohol, ethylene glycol and 1,3-propanediol are particularly preferred in view of the industrial value and practicality of the reaction product.

(reactive form)

In the present invention (I), the reaction of the allyl alcohol and the alcohol compound may be performed by bringing the allyl alcohol into contact with the alcohol compound in the presence of the catalyst. The reaction form may be any reaction form of a conventionally known reaction using allyl alcohol, or a continuous batch reaction in a reaction using an alcohol compound, and any of a liquid phase method, a slurry method, and a gas phase method may be used . As the catalyst, any of a homogeneous catalyst and a heterogeneous catalyst can be used as well. There is no particular limitation on the form of the catalyst, and an appropriate form can be selected according to the reaction form.

Specific examples of the reaction format used in the present invention include, but are not limited to, such as a simple stirred tank, a bubble column reactor, and a tubular reactor in the case of a homogeneous catalyst; and, for example, in the case of a heterogeneous catalyst It is a simple stirred tank for a suspended bed, a fluidized bed bubble-cap tower reactor, a fluidized bed tubular reactor, a fixed bed liquid phase circulation tubular reactor, and a fixed bed trickle bed tubular reactor.

(dosage)

The amount of the catalyst used to react allyl alcohol with the alcohol compound in the method for producing 3-alkoxy-1-propanol in the present invention (I) is not particularly limited because it varies depending on the reaction form. When performing a batch reaction, in the case of a homogeneous catalyst, the amount of the catalyst is usually 0.001 to 20% by mass based on the mixed solution of allyl alcohol and an alcohol compound, preferably 0.01 to 10% by mass, more preferably 0.1 ~5% by mass, and in the case of a heterogeneous catalyst, the amount of the catalyst is usually 0.01 to 200% by mass based on the mixed solution of allyl alcohol and alcohol compound, preferably 0.1 to 100% by mass, more preferably 0.5 to 100% by mass 50% by mass.

When the amount of the catalyst is less than the above range, a sufficient reaction rate suitable for practical use cannot be obtained. On the other hand, when the amount of the catalyst exceeds the above range, a reduction in reaction yield and an increase in catalyst cost may be caused by an increase in side reactions. Neither case is preferred.

The amount of allyl alcohol and alcohol compound used in the method of the present invention (I) is not particularly limited. The allyl alcohol and the alcohol compound are generally used such that the ratio of the mass of the alcohol compound to the mass of the allyl alcohol is 0.5-50. When the ratio of the mass of the alcohol compound to the mass of allyl alcohol is less than 0.5, the reaction between allyl alcohols may occur, whereby the target reaction product of allyl alcohol and alcohol compound cannot be easily produced, so it is not preferable . On the other hand, when the ratio of the mass of the alcohol compound to the mass of allyl alcohol exceeds 50, a large amount of unreacted alcohol compound must be removed in the case of isolating the target product, resulting in high cost for industrial production, so it is not preferable . The ratio of the mass of the alcohol compound to the mass of allyl alcohol is preferably 1-30, more preferably 1-10.

(Reaction conditions)

In the method for producing 3-alkoxy-1-propanol in the present invention (I), the reaction pressure in the reaction of allyl alcohol and the alcohol compound is not particularly limited because it depends on the reaction temperature, the kind of the alcohol compound, and the alkene The mixing ratio of propanol to alcohol compound varies. The reaction can be carried out under normal pressure or external pressure. When the reaction is carried out at a temperature above the boiling point of either or both of the allyl alcohol and the alcohol compound, the reaction pressure is determined by the vapor pressure of either or both of them, and an inert gas may be used in addition to the vapor pressure of the substrate The reaction is carried out under applied pressure. Similarly, when the reaction is carried out at a temperature at which no vapor pressure is generated in the allyl alcohol and the alcohol compound, the reaction may be carried out under an applied pressure using an inert gas. In order to allow the reaction to proceed efficiently, it is preferable to react under an applied pressure rather than under normal pressure.

In the method for preparing 3-alkoxy-1-propanol of the present invention (I), the reaction of allyl alcohol and alcohol compound can be carried out at any temperature, as long as the reaction efficiency of the catalyst will not be reduced, the reaction Usually, it carries out at the temperature of 100-350 degreeC, Preferably it is 130-300 degreeC, More preferably, it is 150-250 degreeC. When the temperature is lower than 100° C., a reaction rate suitable for practical use cannot be obtained in the reaction of allyl alcohol and an alcohol compound, and thus this is not preferable. On the other hand, when the temperature exceeds 350° C., an isomerization reaction of allyl alcohol may occur to generate undesired by-products derived from allyl alcohol, and thus this is not preferable.

(presence of water)

In the method for producing 3-alkoxy-1-propanol of the present invention (I), even if water is present in addition to allyl alcohol and the alcohol compound, the reaction of allyl alcohol and the alcohol compound can proceed. There is no particular limitation on the amount of water used. Even if B (the number of moles of water present in the reaction system) and A (the number of moles of at least one element selected from the group III elements of the periodic table, lanthanides and actinides contained in the catalyst, or if present If the ratio (B/A) of the total number of moles of multiple elements) is 1, 5 or greater, or 10 or greater, the reaction of allyl alcohol and the alcohol compound in (I) of the present invention can also be carried out.

The ratio (B/A) is preferably 50 or less, more preferably 5 or less (especially preferably 1 or less). When the ratio (B/A) of the number of moles of water to the number of moles of the above elements exceeds 50, the reaction may not proceed smoothly due to reduced catalytic activity.

(allyl alcohol)

Allyl alcohol used in the method of the present invention (I) can be produced by any method.

Specific examples of the method for producing allyl alcohol include, but are not limited to, a method of isomerizing propylene oxide, a method of hydrolyzing allyl chloride, and producing allyl acetate from propylene and acetic acid and converting the resulting acetic acid Method for the hydrolysis of allyl esters.

The allyl alcohol in the method of the present invention (I) is preferably allyl alcohol obtained by producing allyl acetate from propylene and acetic acid in the above method and hydrolyzing the obtained allyl acetate, because in said Contamination with industrially undesirable impurities such as chlorine compounds used as poisoning materials for reaction catalysts and epoxy compounds capable of producing by-products can be prevented during the reaction with the alcohol compound.

(Conversion rate)

According to the method for preparing 3-alkoxyl-1-propanol of the present invention (I), when preparing 3-methoxyl-1-propanol from allyl alcohol and methanol, under preferred conditions allyl alcohol The conversion is 20% or greater, and under more preferred conditions 40% or greater. As described in the later-mentioned Examples (Table 1), the selectivity coefficient for 3-methoxy-1-propanol is 60% or more under preferred conditions, and 70% under more preferred conditions or greater (especially preferably 75% or greater).

(product yield)

In the present invention, the yield of the target product (3-alkoxy-1-propanol) is preferably 0.5 or more, more preferably 2.0 or more ( Especially preferably 3.0 or greater).

(the present invention (II))

The present invention (II) will now be described. The present invention (II) relates to 3-alkoxy-1-propanol produced by the method for producing 3-alkoxy-1-propanol of the present invention (I).

Since the method for preparing 3-oxyl-1-propanol of the present invention (I) is a method for preparing 3-oxyl-1-propanol by reacting allyl alcohol with an alcohol compound, the product 3 -Alkyloxy-1-propanol is substantially free of carbonyl compounds as impurities. Therefore, when the 3-alkoxy-1-propanol of the present invention (II) is used as a raw material, 1,3-propanediol substantially free of carbonyl compounds as impurities can be produced. When polyester is prepared by using the obtained 1,3-propanediol, coloring and odor caused by the carbonyl compound can be suppressed.

(Confirmation of carbonyl compounds)

The following procedure can confirm whether 3-alkoxy-1-propanol contains the carbonyl compound. 1) Detect known carbonyl compounds by gas chromatography, liquid chromatography and gas chromatography/mass spectrometry 2) Confirm the C=O stretching vibration peak at about 1600-1800 cm ^-1 by IR spectrum 3) Visible light spectrum (ASTM E411- 70) Detecting the condensate solution of carbonyl compound and 2,4-dinitrophenylhydrazine

(the present invention (2-I))

First, the present invention (2-I) will be described. The present invention (2-I) relates to a method for producing 1,3-propanediol comprising hydrolyzing an ether alcohol compound represented by the general formula (1) in the presence of at least one acid catalyst at a temperature lower than 200°C :

Formula (1)

(chemical formula 3)

wherein R represents an aliphatic chain hydrocarbon group, an aliphatic cyclohydrocarbon group or an aryl group having 1 to 10 carbon atoms, provided that R does not have a hydroxyl group.

(catalyst)

The catalyst used in the method of the present invention (2-I) is an acid catalyst. In addition, the catalyst may be Bronsted acid or Lewis acid as long as it does not inhibit the hydrolysis reaction.

The catalyst used in the method of (2-I) of the present invention is preferably an inorganic acid, an inorganic solid acid, or a compound containing a sulfonic acid group.

Inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and boric acid can be used as the catalyst.

Among these inorganic acids, nitric acid, sulfuric acid and phosphoric acid are preferred, and sulfuric acid and phosphoric acid are more preferred.

Inorganic solid acids such as zeolite, Nafion, activated clay and montmorillonite can be used as the catalyst.

Among these inorganic solid acids, zeolite and Nafion are preferred, and zeolite is more preferred.

Compounds containing sulfonic acid groups such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, 2,4,6- Trimethylbenzenesulfonic acid, hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthalenesulfonic acid and sulfonic acid-based ion exchange resins are used as the catalyst.

Among these compounds containing sulfonic acid groups, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid are preferred, p-toluenesulfonic acid and dodecylbenzenesulfonic acid are more preferred acid.

(form of catalyst)

The form of the catalyst used in the method of (2-I) of the present invention is not particularly limited, and may be any of a homogeneous form and a heterogeneous form. The catalyst is preferably a heterogeneous catalyst, but may be a homogeneous catalyst, in view of the operation of separating the catalyst after the end of the reaction.

Any homogeneous catalyst can be used as long as it is soluble during the reaction.

The homogeneous catalyst may be used for the reaction in the form of being previously dissolved in a substrate such as an ether alcohol compound and water, or may be used for the reaction by being supplied simultaneously with the substrate.

Any heterogeneous catalyst can be used as long as it is insoluble during the reaction. For example, a so-called supported catalyst comprising a carrier and components supported on the carrier can also be used.

(supported catalyst)

When the catalyst used in the method of the present invention (2-I) is a supported catalyst comprising a carrier and a catalyst supported on the carrier, there is no particular limitation on the usable carrier as long as it does not react with the acid component , and conventionally known vectors can be used. Specific examples of the support include activated carbon, silica, alumina, silica-alumina, zeolite, titania, zirconia, magnesia and diatomaceous earth. Silica, alumina, and zeolite are preferred in view of influence on the reaction, the specific surface area during catalyst preparation, or the industrial applicability of the support such as strength.

The surface area of the carrier for the catalyst used in the method of the present invention (2-I) is preferably 50 to 4000 m ² /g, more preferably 100 to 2000 m ² /g, even more preferably 200 to 1000 m ² /g.

When an acid component as an active species of the catalyst is supported on the support, the amount of the acid component is preferably 0.01 to 100% by mass based on the total mass of the support. When the amount of the acid component is less than 0.01% by mass, sufficient catalytic activity suitable for practical use cannot be obtained due to the low concentration of catalytically active sites, and thus is not preferable. On the other hand, when the amount exceeds 100% by mass, the effect of the carrier cannot be exerted, so this is not preferable.

The amount is more preferably 0.05 to 50% by mass, and even more preferably 0.1 to 30% by mass.

When the catalyst used in the method of the present invention (2-I) is a supported catalyst comprising a carrier and a catalyst loaded on the carrier, for example, sulfonic acid-terminated surface hydroxyl-modified silica, sulfonic acid Terminated surface hydroxyl modified alumina, phosphoric acid terminated surface hydroxyl modified silica and phosphoric acid terminated surface hydroxyl modified alumina. These catalysts can be used alone or in combination.

When the catalyst used in the method of (2-I) of the present invention is a homogeneous catalyst, an inorganic solid acid catalyst is most preferred.

(nature of catalyst)

There are no particular restrictions on the nature and size of these catalysts. Specific examples of the nature of the catalyst include powders, solid pulverized products, flakes, spherical molded products, columnar molded products and cylindrical molded products. The size of the catalyst is preferably 1 to 1000 μm in terms of average particle diameter in the case of a suspended bed or a fluidized bed, and approximately 1 to 20 mm in the case of a fixed bed.

In the case of a suspended bed or a fluidized bed, when the average particle diameter of the catalyst is smaller than the above range, it is difficult to separate the catalyst. On the other hand, when the particle diameter is larger than the above range, the reaction cannot be efficiently performed due to the sedimentation of the catalyst. In the case of a fixed bed, when the average particle diameter is smaller than the above range, clogging of the catalyst layer and increase in differential pressure may occur. On the other hand, when the particle diameter is larger than the above range, the surface area of the catalyst per unit area of the reactor decreases, thereby lowering the reaction efficiency, and thus it is not preferable.

When the catalysts used in the method of the present invention (2-I) are heterogeneous catalysts, those having properties and particle diameters suitable for the reaction form can be selected and used.

The catalyst used in the method of the present invention (2-I) can be prepared by any conventionally known method for preparing a catalyst.

(preferred method for preparing catalyst)

When the catalyst used in the method of the present invention (2-I) is a supported catalyst comprising a carrier and a catalyst loaded on the carrier, in consideration of preventing active species from being eliminated from the catalyst, preferably by Methods to prepare the catalyst.

That is, it is preferable to prepare the catalyst by a method including the following steps (A) and (B).

Step (A):

adding a compound having a thiol and a trimethoxysilyl group in the structure and a support to an organic solvent and heating them, thereby causing the silanol and trimethoxysilyl to react on the surface of the support

Step (B):

The solid obtained in step (A) is washed and subjected to oxidation treatment in an organic solvent, thereby converting thiol groups into sulfonic acid groups, followed by washing and drying to obtain - Catalyst for propylene glycol.

Of course, the method is not limited to these methods, and the catalyst can be prepared by conventionally known methods.

(ether alcohol compound)

The ether alcohol compound represented by the general formula (1) in the method of the present invention (2-I) is a compound having one hydroxyl group and one ether structure in the structure.

Specific examples of ether alcohol compounds in the present invention include, but are not limited to, 3-methoxy-1-propanol, 3-ethoxy-1-propanol, 3-n-propoxy-1-propanol, 3-isopropoxy-1-propanol, 3-allyloxy-1-propanol, 3-n-butoxy-1-propanol, 3-tert-butoxy-1-propanol, 3- Pentyloxy-1-propanol, 3-hexyloxy-1-propanol, 3-phenoxy-1-propanol and 3-benzyloxy-1-propanol.

Among these ether alcohol compounds, 3-methoxy-1-propanol, 3-allyloxy-1-propanol, and 3-benzyloxy-1-propanol are particularly preferable in view of easiness of carrying out the hydrolysis reaction .

(Hydrolysis reaction)

In the present invention (2-I), the hydrolysis reaction of the ether alcohol compound can be performed by bringing the ether alcohol compound into contact with water in the presence of a catalyst. The reaction form may be any reaction form used in a conventionally known hydrolysis reaction, a continuous batch reaction. As the catalyst, any of a homogeneous catalyst and a heterogeneous catalyst can be used. There is no particular limitation on the form of the catalyst, and an appropriate form can be selected according to the reaction form.

Specific examples of the reaction format used in the present invention include, but are not limited to, such as a simple stirred tank, a bubble column reactor, and a tubular reactor in the case of a homogeneous catalyst; and, for example, in the case of a heterogeneous catalyst It is a simple stirred tank for a suspended bed, a fluidized bed bubble-cap tower reactor, a fluidized bed tubular reactor, a fixed bed liquid phase circulation tubular reactor, and a fixed bed trickle bed tubular reactor.

(dosage)

The amount of the catalyst used for the hydrolysis reaction in the method for producing 1,3-propanediol of the present invention (2-I) is not particularly limited because it varies depending on the reaction form. When performing a batch reaction, in the case of a homogeneous catalyst, the amount of the catalyst is usually 0.01 to 100% by mass based on the mixed solution of the ether alcohol compound and water, preferably 0.1 to 50% by mass, more preferably 1 ~30% by mass, and in the case of heterogeneous catalysts, the amount of the catalyst is usually 0.01-200% by mass based on the mixed solution of ether alcohol compound and water, preferably 0.1-150% by mass, more preferably 1-200% by mass 100% by mass.

When the amount of the catalyst is less than the above range, a sufficient reaction rate suitable for practical use cannot be obtained. On the other hand, when the amount of the catalyst exceeds the above range, a reduction in reaction yield and an increase in catalyst cost may be caused by an increase in side reactions. Neither case is preferred.

(presence of water)

In the method of the present invention (2-I), the amounts of the ether alcohol compound and water are not particularly limited. In general, they can be used so that the ratio (B/A) of the mass (B) of water to the mass (A) of the ether compound is 0.1-50. When the ratio of the mass of water to the mass of the ether compound is less than 0.1, the hydrolysis reaction cannot proceed smoothly and the target 1,3-propanediol cannot be easily produced, so this is not preferable. On the other hand, when the ratio of the mass of water to the mass of ether compound exceeds 50, a large amount of water must be removed in the case of isolating the target product, resulting in high cost for industrial production, and thus it is not preferable. The ratio is preferably 0.5-30, more preferably 1-20. In view of reducing the cost of producing 1,3-propanediol, the ratio of the mass of water to the mass of ether compound is preferably 5 or less (more preferably 3 or less).

(Reaction conditions)

In the method for producing 1,3-propanediol in the present invention (2-I), the reaction pressure in the hydrolysis reaction of the ether alcohol compound is not particularly limited because it varies depending on the reaction temperature and the mixing ratio of the ether alcohol compound and water . The reaction can be carried out under normal pressure or external pressure. When the reaction is carried out at a temperature higher than the boiling point of one or both of the ether alcohol compound and water, the reaction pressure is determined by the vapor pressure of either or both of them, and an inert gas can be used in addition to the vapor pressure of the substrate. The reaction was carried out under applied pressure. Similarly, when the reaction is carried out at a temperature at which the ether alcohol compound and water cannot generate vapor pressure, the reaction can be carried out under an applied pressure using an inert gas. In order to allow the reaction to proceed efficiently, it is preferable to react under an applied pressure rather than under normal pressure.

In the method for preparing 1,3-propanediol of the present invention (2-I), the reaction of the ether alcohol compound and water can be carried out at any temperature, as long as the reaction efficiency of the catalyst is not reduced, and the reaction is usually between 50 200°C, preferably 80 to 190°C, more preferably 100 to 180°C. When the temperature is lower than 50° C., a reaction rate suitable for practical use cannot be obtained in the reaction of the ether alcohol compound and water, and thus this is not preferable. On the other hand, when the temperature exceeds 200°C, the isomerization reaction of the alcohol compound produced by the hydrolysis reaction together with 1,3-propanediol may occur, thereby generating undesirable by-products, which will combine with 1,3-propanediol - The propylene glycol reaction would form secondary by-products, thereby reducing the selectivity coefficient for 1,3-propanediol, so this is not preferred.

(reaction accelerator)

In the method for producing 1,3-propanediol of the present invention (2-I), the reaction rate can be significantly increased by adding a reaction accelerator in addition to the catalyst in the reaction of the ether alcohol compound and water. The reaction accelerator is not particularly limited, and is preferably iodide or bromide. Examples of preferable reaction accelerators include sodium iodide, potassium iodide, tetraethylammonium iodide, tetrabutylammonium iodide, hydrogen iodide, sodium bromide and potassium bromide. The amount of the reaction accelerator is usually 0.01 to 100% by mass, preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, based on the mixed solution of the ether alcohol compound and water.

When the amount of the reaction accelerator is less than that of the mixed solution of the ether alcohol compound and water, sufficient accelerating action suitable for practical use cannot be exerted. On the other hand, when the amount of the reaction accelerator is larger than that of the mixed solution of the ether alcohol compound and water, corrosion of the reaction device and increased cost for removing the reaction accelerator after use may occur. Therefore, these two cases are not preferred.

(Method for preparing ether alcohol compound)

The ether alcohol compound used in the method of the present invention (2-I) can be produced by any method.

Specific examples of methods for producing 3-alkoxy-1-propanol in ether alcohol compounds include, but are not limited to, a method of adding an alcohol compound to acrolein and hydrolyzing the mixture, Process for reacting hydrocarbyl halides with 1,3-propanediol in the presence of sodium oxide, process for reacting 3-halogen-1-propanol with alcohol compounds in the presence of metallic sodium or sodium hydroxide, and in the presence of specific catalysts A method of reacting allyl alcohol with an alcohol compound in the presence.

In the method of the present invention (2-I), the ether alcohol compound is preferably 3-alkoxy-1-propanol obtained by reacting allyl alcohol with an alcohol compound in the presence of a specific catalyst, because in the reaction Contamination with industrially undesirable impurities such as chlorine compounds used as poisoning materials for reaction catalysts and carbonyl compounds capable of producing by-products is prevented in the meantime.

According to the method for preparing 1,3-propanediol of the present invention (2-I), when 1,3-propanediol is prepared by hydrolyzing 3-methoxy-1-propanol, under preferred conditions, 3-methoxypropanediol The conversion of oxy-1-propanol is 50% or greater, and under more preferred conditions is 70% or greater. Under preferred conditions, the selectivity coefficient of 1,3-propanediol is 60% or greater, and under more preferred conditions is 70% or greater (especially preferably 75% or greater).

(the present invention (2-II))

The present invention (2-II) will now be described. The present invention (2-II) relates to 1,3-propanediol produced by the method for producing 1,3-propanediol of the present invention (2-I).

Since the method for preparing 1,3-propanediol of the present invention (2-1) is a method of hydrolyzing 3-alkoxy-1-propanol prepared by reacting allyl alcohol with an alcohol compound, the product 1, 3-Propanediol does not substantially contain carbonyl compounds as impurities. Therefore, when polyester is produced by using 1,3-propanediol obtained by means of the present invention (2-II), coloration and odor caused by the carbonyl compound can be suppressed.

Example

The present invention will be described in more detail by the following Examples and Comparative Examples, but the present invention is not limited thereto.

Each reaction in the Examples was analyzed by gas chromatography (hereinafter abbreviated as "GC") under the following conditions.

Conditions for GC analysis

GC-17A (manufactured by Shimadzu Corporation)

Column: TC-FFAP 0.25mmφ x 30m (manufactured by GL Science Co.)

Carrier: He1ml/min

Split ratio: 1/30

Detector: FID

Column temperature: 40°C (10min)→10°C/min-→200°C (40min)

Injection temperature: 200°C

Injection volume: 0.2μl

Example 1

(Preparation of activated carbon _- supported _La2O3 catalyst)

1.48 g of lanthanum nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a beaker and dissolved in 5.00 g of deionized water to obtain an aqueous solution (1). 5.00 g of activated carbon (manufactured by Mitsubishi Chemical Corporation, Diahope 008B, specific surface area: 1200 m ² /g) was added to the beaker in which the aqueous solution (1) was prepared so that the content of lanthanum oxide was 10% by mass based on the activated carbon, thereby making Activated carbon adsorbs the entire amount of aqueous solution (1).

The activated carbon adsorbing the aqueous solution (1) was dried at 110° C. for 2 hours in the presence of air. The activated carbon was then oxidized at 400° C. for 2 hours in the presence of air to obtain an activated carbon-supported lanthanum oxide catalyst.

Example 2

1.00 g of the activated carbon-supported lanthanum oxide catalyst prepared in Example 1, 30.00 g of methanol and 5.00 g of allyl alcohol were charged into a stainless steel autoclave equipped with a stirrer (produced by Taiatsu Techno Corporation) having an inner volume of 120 ml, The device is then assembled. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while stirring at 800 rpm, and then allowed to react at 200° C. for 6 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 1 described below. GC showed no detection of peaks attributed to carbonyl compounds such as 3-methoxy-1-propanal and 3-allyloxy-1-propanal (in this example these carbonyl compounds exhibited 10 ppm or more small GC detection limit).

Example 3

(Preparation of activated carbon-supported Pr ₆ O ₁₁ catalyst)

1.44 g of praseodymium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a beaker and dissolved in 4.00 g of deionized water to obtain an aqueous solution (2). 5.00 g of activated carbon (manufactured by Mitsubishi Chemical Corporation, Diahope 008B, specific surface area: 1200 m ² /g) was added to the beaker in which the aqueous solution (2) was prepared so that the content of praseodymium oxide was 10% by mass based on the activated carbon, thereby making Activated carbon adsorbs the entire amount of aqueous solution (2).

The activated carbon adsorbing the aqueous solution (2) was dried at 110° C. for 2 hours in the presence of air. The activated carbon was then oxidized at 400° C. for 2 hours in the presence of air to obtain an activated carbon-supported praseodymium oxide catalyst.

Example 4

In a stainless steel autoclave equipped with a stirrer (manufactured by Taiatsu Techno Corporation) having an internal volume of 120 ml, 1.00 g of the activated carbon-supported praseodymium oxide catalyst prepared in Example 3, 30.00 g of methanol and 5.00 g of allyl alcohol were charged, The device is then assembled. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while stirring at 800 rpm, and then allowed to react at 200° C. for 3 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 1 described below. GC showed no detectable peaks attributed to carbonyl compounds such as 3-methoxy-1-propanal and 3-allyloxy-1-propanal (in this example these carbonyl compounds exhibited 10 ppm or more small GC detection limit).

Example 5

(Preparation of activated carbon _- supported _Sm2O3 catalyst)

1.42 g of samarium nitrate hexahydrate (produced by Wako Pure Chemical Industries, Ltd.) was placed in a beaker and dissolved in 4.00 g of deionized water to obtain an aqueous solution (3). 5.00 g of activated carbon (manufactured by Mitsubishi Chemical Corporation, Diahope 008B, specific surface area: 1200 m ² /g) was added to the beaker in which the aqueous solution (3) was prepared so that the content of samarium oxide was 10% by mass based on the activated carbon, thereby making Activated carbon adsorbs the entire amount of aqueous solution (3).

The activated carbon adsorbing the aqueous solution (3) was dried at 110° C. for 2 hours in the presence of air. The activated carbon was then oxidized at 400° C. in the presence of air for 2 hours to obtain an activated carbon-supported samarium oxide catalyst.

Example 6

In a stainless steel autoclave equipped with a stirrer (manufactured by Taiatsu Techno Corporation) having an internal volume of 120 ml, 1.00 g of the activated carbon-supported samarium oxide catalyst prepared in Example 5, 30.00 g of methanol and 5.00 g of allyl alcohol were charged, The device is then assembled. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while stirring at 800 rpm, and then allowed to react at 200° C. for 6 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 1 described below. GC showed no detection of peaks attributed to carbonyl compounds such as 3-methoxy-1-propanal and 3-allyloxy-1-propanal (in this example these carbonyl compounds exhibited 10 ppm or more small GC detection limit).

Example 7

( _Preparation of activated carbon-supported _Gd2O3 catalyst)

1.37 g of gadolinium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a beaker and dissolved in 4.00 g of deionized water to obtain an aqueous solution (4). 5.00 g of activated carbon (manufactured by Mitsubishi Chemical Corporation, Diahope 008B, specific surface area: 1200 m ² /g) was added to the beaker in which the aqueous solution (4) was prepared so that the content of gadolinium oxide was 10% by mass based on the activated carbon, thereby making Activated carbon adsorbs the entire amount of aqueous solution (4).

The activated carbon adsorbing the aqueous solution (4) was dried at 110° C. for 2 hours in the presence of air. The activated carbon was then oxidized at 400° C. for 2 hours in the presence of air to obtain an activated carbon-supported gadolinia catalyst.

Example 8

Into a stainless steel autoclave equipped with a stirrer (manufactured by Taiatsu Techno Corporation) having an inner volume of 120 ml, 1.00 g of the gadolinium oxide catalyst supported on activated carbon prepared in Example 7, 30.00 g of methanol and 5.00 g of allyl alcohol were charged, The device is then assembled. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while stirring at 800 rpm, and then allowed to react at 200° C. for 3 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 1 described below. GC showed no detection of peaks attributed to carbonyl compounds such as 3-methoxy-1-propanal and 3-allyloxy-1-propanal (in this example these carbonyl compounds exhibited 10 ppm or more small GC detection limit).

Example 9

(Preparation of activated carbon _- supported _Dy2O3 catalyst)

1.39 g of dysprosium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a beaker and dissolved in 4.00 g of deionized water to obtain an aqueous solution (5). 5.00 g of activated carbon (manufactured by Mitsubishi Chemical Corporation, Diahope 008B, specific surface area: 1200 m ² /g) was added to the beaker in which the aqueous solution (5) was prepared so that the content of dysprosium oxide was 10% by mass based on the activated carbon, thereby making Activated carbon adsorbs the entire amount of aqueous solution (5).

The activated carbon adsorbing the aqueous solution (5) was dried at 110° C. for 2 hours in the presence of air. The activated carbon was then oxidized at 400° C. for 2 hours in the presence of air to obtain an activated carbon-supported dysprosium oxide catalyst.

Example 10

1.00 g of the activated carbon-supported dysprosium oxide catalyst prepared in Example 9, 30.00 g of methanol and 5.00 g of allyl alcohol were charged in a stainless steel autoclave equipped with a stirrer (produced by Taiatsu Techno Corporation) having an inner volume of 120 ml, The device is then assembled. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while stirring at 800 rpm, and then allowed to react at 200° C. for 3 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 1 described below. GC showed no detection of peaks attributed to carbonyl compounds such as 3-methoxy-1-propanal and 3-allyloxy-1-propanal (in this example these carbonyl compounds exhibited 10 ppm or more small GC detection limit).

Example 11

(Preparation of activated carbon-supported Ho ₂ O ₃ catalyst)

1.36 g of holmium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a beaker and dissolved in 4.00 g of deionized water to obtain an aqueous solution (6). 4.00 g of activated carbon (manufactured by Mitsubishi Chemical Corporation, Diahope 008B, specific surface area: 1200 m ² /g) was added to the beaker in which the aqueous solution (6) was prepared so that the content of holmium oxide was 10% by mass based on the activated carbon, thereby making Activated carbon adsorbs the entire amount of aqueous solution (6).

The activated carbon adsorbing the aqueous solution (6) was dried at 110° C. for 2 hours in the presence of air. The activated carbon was then oxidized at 400° C. for 2 hours in the presence of air to obtain an activated carbon-supported holmium oxide catalyst.

Example 12

1.00 g of the activated carbon-supported holmium oxide catalyst prepared in Example 11, 30.00 g of methanol and 5.00 g of allyl alcohol were charged into a stainless steel autoclave equipped with a stirrer (manufactured by Taiatsu Techno Corporation) having an inner volume of 120 ml, The device is then assembled. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while stirring at 800 rpm, and then allowed to react at 200° C. for 3 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 1 described below. GC showed no detection of peaks attributed to carbonyl compounds such as 3-methoxy-1-propanal and 3-allyloxy-1-propanal (in this example these carbonyl compounds exhibited 10 ppm or more small GC detection limit).

Example 13

(Preparation of activated carbon _- supported _Er2O3 catalyst)

1.37 g of erbium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a beaker and dissolved in 4.00 g of deionized water to obtain an aqueous solution (7). 5.00 g of activated carbon (manufactured by Mitsubishi Chemical Corporation, Diahope 008B, specific surface area: 1200 m ² /g) was added to the beaker in which the aqueous solution (7) was prepared so that the content of erbium oxide was 10% by mass based on the activated carbon, thereby making Activated carbon adsorbs the entire amount of aqueous solution (7).

The activated carbon adsorbing the aqueous solution (7) was dried at 110° C. for 2 hours in the presence of air. The activated carbon was then oxidized at 400° C. in the presence of air for 2 hours to obtain an activated carbon-supported erbium oxide catalyst.

Example 14

1.00 g of the activated carbon-supported erbium oxide catalyst prepared in Example 13, 30.00 g of methanol and 5.00 g of allyl alcohol were charged into a stainless steel autoclave equipped with a stirrer (manufactured by Taiatsu Techno Corporation) having an inner volume of 120 ml, The device is then assembled. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while stirring at 800 rpm, and then allowed to react at 200° C. for 3 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 1 described below. GC showed no detection of peaks attributed to carbonyl compounds such as 3-methoxy-1-propanal and 3-allyloxy-1-propanal (in this example these carbonyl compounds exhibited 10 ppm or more small GC detection limit).

Example 15

(Preparation of activated carbon-supported Yb ₂ O ₃ catalyst)

1.22 g of ytterbium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a beaker and dissolved in 4.00 g of deionized water to obtain an aqueous solution (8). 5.00 g of activated carbon (manufactured by Mitsubishi Chemical Corporation, Diahope 008B, specific surface area: 1200 m ² /g) was added to the beaker in which the aqueous solution (8) was prepared so that the content of ytterbium oxide was 10% by mass based on the activated carbon, thereby making Activated carbon adsorbs the entire amount of aqueous solution (8).

The activated carbon adsorbing the aqueous solution (8) was dried at 110° C. for 2 hours in the presence of air. The activated carbon was then oxidized at 400° C. for 2 hours in the presence of air to obtain an activated carbon-supported ytterbium oxide catalyst.

Example 16

Into a stainless steel autoclave equipped with a stirrer (manufactured by Taiatsu Techno Corporation) having an inner volume of 120 ml, 1.00 g of the activated carbon-supported ytterbium oxide catalyst prepared in Example 15, 30.00 g of methanol and 5.00 g of allyl alcohol were charged, The device is then assembled. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while stirring at 800 rpm, and then allowed to react at 200° C. for 6 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 1 described below. GC showed no detection of peaks attributed to carbonyl compounds such as 3-methoxy-1-propanal and 3-allyloxy-1-propanal (in this example these carbonyl compounds exhibited 10 ppm or more small GC detection limit).

Example 17

(Preparation of activated carbon-supported Y ₂ O ₃ catalyst)

1.88 g of yttrium nitrate hexahydrate (manufactured by Kanto Kagaku) was placed in a beaker and dissolved in 4.00 g of deionized water to obtain an aqueous solution (9). 5.00 g of activated carbon (manufactured by Mitsubishi Chemical Corporation, Diahope 008B, specific surface area: 1200 m ² /g) was added to the beaker in which the aqueous solution (9) was prepared so that the content of yttrium oxide was 10% by mass based on the activated carbon, thereby making the activated carbon The entire amount of aqueous solution (4) is adsorbed.

The activated carbon adsorbing the aqueous solution (9) was dried at 110° C. for 2 hours in the presence of air. The activated carbon was then oxidized at 400° C. for 2 hours in the presence of air to obtain an activated carbon-supported yttrium oxide catalyst.

Example 18

1.00 g of the activated carbon-supported yttrium oxide catalyst prepared in Example 17, 30.00 g of methanol and 5.00 g of allyl alcohol were charged into a stainless steel autoclave equipped with a stirrer (manufactured by Taiatsu Techno Corporation) having an inner volume of 120 ml, The device is then assembled. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while stirring at 800 rpm, and then allowed to react at 200° C. for 6 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 1 described below. GC showed no detection of peaks attributed to carbonyl compounds such as 3-methoxy-1-propanal and 3-allyloxy-1-propanal (in this example these carbonyl compounds exhibited 10 ppm or more small GC detection limit).

Example 19

(Preparation of activated carbon-supported Y ₂ O ₃ catalyst)

1.86 g of yttrium nitrate hexahydrate (manufactured by Kanto Kagaku) was placed in a beaker and dissolved in 4.00 g of deionized water to obtain an aqueous solution (10). 5.00 g of activated carbon (manufactured by TSURUMICOAL Co., LTD., HC-20CS, specific surface area: 1855 m ² /g) was added to the beaker in which the aqueous solution (10) was prepared so that the content of yttrium oxide was 10% by mass based on the activated carbon, This allows the activated carbon to adsorb the entire amount of the aqueous solution (10).

The activated carbon adsorbing the aqueous solution (10) was dried at 110° C. for 2 hours in the presence of air. The activated carbon was then oxidized at 400° C. for 2 hours in the presence of air to obtain an activated carbon-supported yttrium oxide catalyst.

Example 20

1.00 g of the activated carbon-supported yttrium oxide catalyst prepared in Example 19, 30.00 g of methanol and 5.00 g of allyl alcohol were charged into a stainless steel autoclave equipped with a stirrer (manufactured by Taiatsu Techno Corporation) having an inner volume of 120 ml, The device is then assembled. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while stirring at 800 rpm, and then allowed to react at 200° C. for 5 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 1 described below. GC showed no detection of peaks attributed to carbonyl compounds such as 3-methoxy-1-propanal and 3-allyloxy-1-propanal (in this example these carbonyl compounds exhibited 10 ppm or more small GC detection limit).

Example 21

(Preparation of activated carbon-supported Y ₂ O ₃ catalyst)

1.86 g of yttrium nitrate hexahydrate (manufactured by Kanto Kagaku) was placed in a beaker and dissolved in 4.00 g of deionized water to obtain an aqueous solution (11). 5.00 g of activated carbon (manufactured by TSURUMICOAL Co., LTD., HC-20CS, specific surface area: 1855 m ² /g) previously fired at 110° C. for 2 hours was added to the beaker in which the aqueous solution (11) was prepared so that the yttrium oxide The content of is 10% by mass based on the activated carbon, so that the activated carbon absorbs the entire amount of the aqueous solution (11).

The activated carbon adsorbing the aqueous solution (11) was dried at 110° C. for 2 hours in the presence of air. The activated carbon was then oxidized at 400° C. for 2 hours in the presence of air to obtain an activated carbon-supported yttrium oxide catalyst.

Example 22

1.00 g of the activated carbon-supported yttrium oxide catalyst prepared in Example 21, 30.00 g of methanol and 5.00 g of allyl alcohol were charged into a stainless steel autoclave equipped with a stirrer (manufactured by Taiatsu Techno Corporation) having an inner volume of 120 ml, The device is then assembled. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while stirring at 800 rpm, and then allowed to react at 200° C. for 5 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 1 described below. GC showed no detection of peaks attributed to carbonyl compounds such as 3-methoxy-1-propanal and 3-allyloxy-1-propanal (in this example these carbonyl compounds exhibited 10 ppm or more small GC detection limit).

Example 23

Into a stainless steel autoclave equipped with a stirrer (manufactured by Taiatsu Techno Corporation) having an inner volume of 120 ml, 1.00 g of the activated carbon-supported yttrium oxide catalyst prepared in Example 17, 30.00 g of methanol, 4.50 g of allyl alcohol and 0.50 g deionized water, then assemble the device. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while stirring at 800 rpm, and then allowed to react at 200° C. for 6 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 1 described below. GC showed no detection of peaks attributed to carbonyl compounds such as 3-methoxy-1-propanal and 3-allyloxy-1-propanal (in this example these carbonyl compounds exhibited 10 ppm or more small GC detection limit).

Example 24

(Preparation of activated carbon-supported Sc ₂ O ₃ catalyst)

2.30 g of scandium nitrate trihydrate (manufactured by AVOCADO Co.) was placed in a beaker and dissolved in 4.00 g of deionized water to obtain an aqueous solution (12). 5.00 g of activated carbon (produced by Mitsubishi Chemical Corporation, Diahope 008B, specific surface area: 1200 m ² /g) was added to the beaker in which the aqueous solution (12) was prepared so that the content of scandium oxide was 10% by mass based on the activated carbon, thereby making the activated carbon The entire amount of aqueous solution (12) is adsorbed.

The activated carbon adsorbing the aqueous solution (12) was dried at 110° C. for 2 hours in the presence of air. The activated carbon was then oxidized at 400° C. for 2 hours in the presence of air to obtain an activated carbon-supported scandium oxide catalyst.

Example 25

1.00 g of the activated carbon-supported scandium oxide catalyst prepared in Example 24, 30.00 g of methanol and 5.00 g of allyl alcohol were charged into a stainless steel autoclave equipped with a stirrer (manufactured by Taiatsu Techno Corporation) having an inner volume of 120 ml, The device is then assembled. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while stirring at 800 rpm, and then allowed to react at 200° C. for 3 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 1 described below. GC showed no detection of peaks attributed to carbonyl compounds such as 3-methoxy-1-propanal and 3-allyloxy-1-propanal (in this example these carbonyl compounds exhibited 10 ppm or more small GC detection limit).

Example 26

1.00 g of the activated carbon-supported scandium oxide catalyst prepared in Example 24, 30.00 g of methanol, 4.50 g of allyl alcohol and 0.50 g deionized water, then assemble the device. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while stirring at 800 rpm, and then allowed to react at 200° C. for 6 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 1 described below. GC showed no detection of peaks attributed to carbonyl compounds such as 3-methoxy-1-propanal and 3-allyloxy-1-propanal (in this example these carbonyl compounds exhibited 10 ppm or more small GC detection limit).

Example 27

In a stainless steel autoclave (manufactured by Taiatsu Techno Corporation) having an internal volume of 30 ml including a stirrer, 0.20 g of the activated carbon-supported yttrium oxide catalyst prepared in Example 17 and 5.00 g of allyl alcohol were charged, and then the apparatus was assembled . After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred with a magnetic stirrer, and then allowed to react at 200° C. for 5 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 1 described below. GC showed no detection of peaks attributed to carbonyl compounds such as 3-methoxy-1-propanal and 3-allyloxy-1-propanal (in this example these carbonyl compounds exhibited 10 ppm or more small GC detection limit).

Example 28

In a stainless steel autoclave (manufactured by Taiatsu Techno Corporation) having an internal volume of 30 ml including a stirrer, 0.20 g of the activated carbon-supported scandium oxide catalyst prepared in Example 24 and 5.00 g of allyl alcohol were charged, and then the device was assembled . After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred with a magnetic stirrer, and then allowed to react at 200° C. for 5 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 1 described below. GC showed no detection of peaks attributed to carbonyl compounds such as 3-methoxy-1-propanal and 3-allyloxy-1-propanal (in this example these carbonyl compounds exhibited 10 ppm or more small GC detection limit).

Comparative example 1

1.00 g of a magnesium oxide catalyst (manufactured by Wako Pure Chemical Industries, Ltd., 0.01 μm), 30.00 g of methanol, and 5.00 g of allyl propylene were fed into a stainless steel autoclave (manufactured by Taiatsu Techno Corporation) having an inner volume of 120 ml equipped with a stirrer Alcohol, then assemble the device. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while stirring with a magnetic stirrer, and then allowed to react at 200° C. for 6 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 1 described below.

Comparative example 2

3.54 g of magnesium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a beaker and dissolved in 4.00 g of deionized water to obtain an aqueous solution (13). 5.00 g of activated carbon (manufactured by Mitsubishi Chemical Corporation, Diahope 008B, specific surface area: 1200 m ² /g) was added to the beaker in which the aqueous solution (13) was prepared so that the content of magnesium oxide was 10% by mass based on the activated carbon, thereby making Activated carbon adsorbs the entire amount of aqueous solution (13).

The activated carbon adsorbing the aqueous solution (13) was dried at 110° C. for 2 hours in the presence of air. The activated carbon was then oxidized at 400° C. for 2 hours in the presence of air to obtain an activated carbon-supported magnesium oxide catalyst.

1.00 g of this catalyst, 30.00 g of methanol, and 5.00 g of allyl alcohol were fed into a stainless steel autoclave equipped with a stirrer (manufactured by Taiatsu Techno Corporation) having an inner volume of 120 ml, and the apparatus was assembled. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred at 800 rpm with a magnetic stirrer, and then allowed to react at 200° C. for 6 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 1 described below.

Comparative example 3

1.00 g of a magnesium oxide catalyst (produced by Wako Pure Chemical Industries, Ltd., 0.01 μm), 30.00 g of methanol, 4.50 g of allyl propylene were charged in a stainless steel autoclave (produced by Taiatsu Techno Corporation) with an inner volume of 120 ml equipped with a stirrer Alcohol and 0.50 g deionized water, then assemble the device. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred at 800 rpm with a magnetic stirrer, and then allowed to react at 200° C. for 6 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 1 below.

Example 2-1

0.10 g of sulfuric acid, 6.00 g of deionized water and 0.30 g of 3-methoxy-1-propane were fed into a stainless steel autoclave (manufactured by Taiatsu Techno Corporation in a Teflon pestle) having an inner volume of 30 ml including a stirrer Alcohol, then assemble the device. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred with a magnetic stirrer, and then allowed to react at 190° C. for 10 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 2-1 described below.

GC showed no detectable peaks attributable to carbonyl compounds such as 3-methoxy-1-propanal and 3-hydroxy-1-propanal (in this example, these carbonyl compounds exhibited 10 ppm or less GC detection limit).

Example 2-2

0.10 g of sulfuric acid, 6.00 g of deionized water and 1.20 g of 3-methoxy-1-propane were fed into a stainless steel autoclave (manufactured by Taiatsu Techno Corporation in a Teflon pestle) having an inner volume of 30 ml including a stirrer Alcohol, then assemble the device. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred with a magnetic stirrer, and then allowed to react at 190° C. for 10 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 2-1 described below.

GC showed no detectable peaks attributable to carbonyl compounds such as 3-methoxy-1-propanal and 3-hydroxy-1-propanal (in this example, these carbonyl compounds exhibited 10 ppm or less GC detection limit).

Example 2-3

0.30 g of methanesulfonic acid, 6.00 g of deionized water and 0.30 g of 3-methoxy-1 -propanol, and then assemble the device. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred with a magnetic stirrer, and then allowed to react at 190° C. for 5 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 2-1 described below.

GC showed no detectable peaks attributable to carbonyl compounds such as 3-methoxy-1-propanal and 3-hydroxy-1-propanal (in this example, these carbonyl compounds exhibited 10 ppm or less GC detection limit).

Example 2-4

0.30 g of p-toluenesulfonic acid, 6.00 g of deionized water and 0.30 g of 3-methoxy -1-propanol, and then assemble the device. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred with a magnetic stirrer, and then allowed to react at 180° C. for 10 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 2-1 described below.

GC showed no detectable peaks attributable to carbonyl compounds such as 3-methoxy-1-propanal and 3-hydroxy-1-propanal (in this example, these carbonyl compounds exhibited 10 ppm or less GC detection limit).

Example 2-5

0.30 g of p-toluenesulfonic acid, 6.00 g of deionized water and 1.20 g of 3-methoxy -1-propanol, and then assemble the device. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred with a magnetic stirrer, and then allowed to react at 190° C. for 10 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 2-1 described below.

GC showed no detectable peaks attributable to carbonyl compounds such as 3-methoxy-1-propanal and 3-hydroxy-1-propanal (in this example, these carbonyl compounds exhibited 10 ppm or less GC detection limit).

Example 2-6

0.30 g of dodecylbenzenesulfonic acid, 6.00 g of deionized water, and 0.60 g of 3-formaldehyde were charged in a stainless steel autoclave (manufactured by Taiatsu Techno Corporation, in a Teflon pestle) having an inner volume of 30 ml including a stirrer. Oxy-1-propanol, and then assemble the device. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred with a magnetic stirrer, and then allowed to react at 190° C. for 10 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 2-1 described below.

GC showed no detectable peaks attributable to carbonyl compounds such as 3-methoxy-1-propanal and 3-hydroxy-1-propanal (in this example, these carbonyl compounds exhibited 10 ppm or less GC detection limit).

Example 2-7

0.30 g of dodecylbenzenesulfonic acid, 6.00 g of deionized water, and 1.20 g of 3-formaldehyde were charged into a stainless steel autoclave (manufactured by Taiatsu Techno Corporation, in a Teflon pestle) having an inner volume of 30 ml including a stirrer. Oxy-1-propanol, and then assemble the device. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred with a magnetic stirrer, and then allowed to react at 190° C. for 10 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 2-1 described below.

GC showed no detectable peaks attributable to carbonyl compounds such as 3-methoxy-1-propanal and 3-hydroxy-1-propanal (in this example, these carbonyl compounds exhibited 10 ppm or less GC detection limit).

Example 2-8

0.10 g of sulfuric acid, 0.03 g of potassium iodide, 5.00 g of deionized water, and 1.00 g of 3-methoxy -1-propanol, and then assemble the device. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred with a magnetic stirrer, and then allowed to react at 180° C. for 6 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 2-1 described below.

GC showed no detectable peaks attributable to carbonyl compounds such as 3-methoxy-1-propanal and 3-hydroxy-1-propanal (in this example, these carbonyl compounds exhibited 10 ppm or less GC detection limit).

Example 2-9

0.10 g of sulfuric acid, 0.40 g of tetrabutylammonium iodide, 5.00 g of deionized water and 1.00 g of 3-methoxy-1-propanol, and then assemble the device. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred with a magnetic stirrer, and then allowed to react at 180° C. for 6 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 2-1 described below.

GC showed no detectable peaks attributable to carbonyl compounds such as 3-methoxy-1-propanal and 3-hydroxy-1-propanal (in this example, these carbonyl compounds exhibited 10 ppm or less GC detection limit).

Example 2-10

1.42 g of hydroiodic acid, 5.00 g of deionized water and 1.00 g of 3-methoxy-1 -propanol, and then assemble the device. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred with a magnetic stirrer, and then allowed to react at 120° C. for 5 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 2-1 described below.

GC showed no detectable peaks attributable to carbonyl compounds such as 3-methoxy-1-propanal and 3-hydroxy-1-propanal (in this example, these carbonyl compounds exhibited 10 ppm or less GC detection limit).

Example 2-11

0.10 g of sulfuric acid, 0.13 g of potassium bromide, 5.00 g of deionized water, and 1.00 g of 3-formazol were fed into a stainless steel autoclave (produced by Taiatsu Techno Corporation, in a Teflon pestle) having an inner volume of 30 ml including a stirrer. Oxy-1-propanol, and then assemble the device. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred with a magnetic stirrer, and then allowed to react at 180° C. for 5 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 2-1 described below.

GC showed no detectable peaks attributable to carbonyl compounds such as 3-methoxy-1-propanal and 3-hydroxy-1-propanal (in this example, these carbonyl compounds exhibited 10 ppm or less GC detection limit).

Example 2-12

0.10 g of sulfuric acid, 0.18 g of potassium bromide, 3.00 g of deionized water, and 1.00 g of 3-formazol were fed into a stainless steel autoclave (manufactured by Taiatsu Techno Corporation, in a Teflon pestle) having an inner volume of 30 ml including a stirrer. Oxy-1-propanol, and then assemble the device. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred with a magnetic stirrer, and then allowed to react at 150° C. for 5 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 2-1 described below.

GC showed no detectable peaks attributable to carbonyl compounds such as 3-methoxy-1-propanal and 3-hydroxy-1-propanal (in this example, these carbonyl compounds exhibited 10 ppm or less GC detection limit).

Example 2-13

0.06 g of sulfuric acid, 3.90 g of deionized water and 1.30 g of 3-allyloxy-1- propanol, and then assemble the device. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred with a magnetic stirrer, and then allowed to react at 180° C. for 3 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 2-1 described below.

GC showed no detection of peaks attributed to carbonyl compounds such as acrolein, 3-allyloxy-1-propanal, and 3-hydroxy-1-propanal (in this example, these carbonyl compounds exhibited 10 ppm or smaller GC detection limit).

Example 2-14

Into a stainless steel autoclave (produced by Taiatsu Techno Corporation, in a Teflon pestle) having an internal volume of 30 ml including a stirrer, 0.50 g of β-type zeolite (produced by Zeolist Co., Si/Al=75), 3.90 g of Ionized water and 1.30 g of 3-allyloxy-1-propanol, and the device was assembled. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred with a magnetic stirrer, and then allowed to react at 180° C. for 3 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 2-1 described below.

GC showed no detection of peaks attributed to carbonyl compounds such as acrolein, 3-allyloxy-1-propanal, and 3-hydroxy-1-propanal (in this example, these carbonyl compounds exhibited 10 ppm or smaller GC detection limit).

Example 2-15

0.50 g of H-ZSM-5 (Si/Al=25), 3.90 g of deionized water and 1.30 g of 3-allyloxy-1-propanol, and the device was assembled. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred with a magnetic stirrer, and then allowed to react at 180° C. for 1 hour.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 2-1 described below.

GC showed no detection of peaks attributed to carbonyl compounds such as acrolein, 3-allyloxy-1-propanal, and 3-hydroxy-1-propanal (in this example, these carbonyl compounds exhibited 10 ppm or smaller GC detection limit).

Comparative example 2-1

0.10 g of sulfuric acid, 5.00 g of deionized water and 1.00 g of 3-methoxy-1-propane were fed into a stainless steel autoclave (manufactured by Taiatsu Techno Corporation in a Teflon pestle) having an inner volume of 30 ml including a stirrer Alcohol, then assemble the device. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while stirring with a magnetic stirrer, and then allowed to react at 220° C. for 10 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 2-1 described below.

GC showed no detection of peaks attributed to carbonyl compounds such as acrolein, 3-allyloxy-1-propanal, and 3-hydroxy-1-propanal (in this example, these carbonyl compounds exhibited 10 ppm or smaller GC detection limit), but produced 1,3-dimethoxypropane.

Comparative example 2-2

0.10 g of sulfuric acid, 6.50 g of deionized water and 1.30 g of 3-allyloxy-1- propanol, and then assemble the device. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred with a magnetic stirrer, and then allowed to react at 220° C. for 5 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 2-1 described below.

GC showed no detection of peaks attributed to carbonyl compounds such as acrolein, 3-allyloxy-1-propanal, and 3-hydroxy-1-propanal (in this example, these carbonyl compounds exhibited 10 ppm or smaller GC detection limit), but yielded diallyl ether and 1,3-diallyloxypropane.

Comparative example 2-3

0.10 g of sulfuric acid, 5.00 g of deionized water and 1.00 g of 4-oxa-1,7- Heptanediol, and then assemble the device. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred with a magnetic stirrer, and then allowed to react at 180° C. for 5 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 2-1 described below.

GC showed no detection of peaks attributed to carbonyl compounds such as acrolein, 3-allyloxy-1-propanal, and 3-hydroxy-1-propanal (in this example, these carbonyl compounds exhibited 10 ppm or smaller GC detection limit).

Comparative example 2-4

0.50 g of H-ZSM-5 (Si/Al=25), 5.00 g of deionized water and 1.00 g of 4-oxa-1,7-heptanediol, and the device was assembled. After closing the vessel, the air in the autoclave was replaced with nitrogen by repeating pressurization of the autoclave with nitrogen to 1.0 MPa (gauge pressure) and depressurization to 0.0 MPa (gauge pressure) 5 times. The contents were heated while being stirred with a magnetic stirrer, and then allowed to react at 180° C. for 5 hours.

After the reaction was complete, the vessel was cooled to room temperature and depressurized. After opening the reactor, the supernatant was sampled and analyzed by GC.

The results calculated from the GC chromatogram are shown in Table 2-1 described below.

GC showed no detection of peaks attributed to carbonyl compounds such as acrolein, 3-allyloxy-1-propanal, and 3-hydroxy-1-propanal (in this example, these carbonyl compounds exhibited 10 ppm or smaller GC detection limit).

Industrial Applicability

As described above, according to the method for producing 3-oxyl-1-propanol of the present invention, 3-oxyl-1-propanol having a very small content of carbonyl impurities can be efficiently produced.

Therefore, the 3-oxyl-1-propanol obtained by the method for 3-oxyl-1-propanol of the present invention is compared with the 3-oxyl-1-propanol obtained by the conventional method It has high purity and can produce 1,3-propanediol substantially free of carbonyl compounds as impurities by using 3-alkoxy-1-propanol as a raw material.

According to the method for preparing 1,3-propanediol of the present invention, 1,3-propanediol having a very small content of carbonyl impurities can be efficiently produced.

Also, 1,3-propanediol obtained by the method for producing 1,3-propanediol of the present invention has a high purity compared with 1,3-propanediol obtained by a conventional method, and it is apparent that by converting the obtained 1,3-propanediol - Propylene glycol is used as a raw material for resins such as polyester to produce less odorous and colored resins at low cost.

Claims (10)

1. one kind prepares 1, the method for ammediol, and it comprises:

In the presence of the catalyzer of at least a element that contains the scandium, yttrium, lanthanon and the actinide elements that are selected from periodictable, vinyl carbinol and alkylol cpd are reacted, obtain 3--oxyl-1-propyl alcohol thus, the wherein said catalyzer that contains at least a element of the scandium, yttrium, lanthanon and the actinide elements that are selected from periodictable be oxide compound and wherein will be with the alkylol cpd of vinyl carbinol reaction be selected from following at least a: methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, vinyl carbinol; With

Be lower than under 200 ℃ the temperature in the presence of at least a acid catalyst 3--oxyl-1-propyl alcohol hydrolysis.

2. method for preparing 3--oxyl-1-propyl alcohol, its catalyzer that is included at least a element that contains the scandium, yttrium, lanthanon and the actinide elements that are selected from periodictable exists down with vinyl carbinol and alkylol cpd reaction, the wherein said catalyzer that contains at least a element of the scandium, yttrium, lanthanon and the actinide elements that are selected from periodictable be oxide compound and wherein will be with the alkylol cpd of vinyl carbinol reaction be selected from following at least a: methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, vinyl carbinol.

3. according to the method for preparing 3--oxyl-1-propyl alcohol of claim 2, the wherein said catalyzer that contains at least a element of the scandium, yttrium, lanthanon and the actinide elements that are selected from periodictable is selected from: Scium trioxide, yttrium oxide, lanthanum trioxide, Samarium trioxide, ytterbium oxide, Neodymium trioxide and lutecium oxide.

4. according to the method for preparing 3--oxyl-1-propyl alcohol of claim 2, the catalyst loading of the wherein said at least a element that contains the scandium, yttrium, lanthanon and the actinide elements that are selected from periodictable is on carrier.

5. according to the method for preparing 3--oxyl-1-propyl alcohol of claim 4, wherein said carrier is gac or magnesium oxide.

6. according to the method for preparing 3--oxyl-1-propyl alcohol of claim 5, the specific surface area of wherein said carrier is 100 to 4000m ²/ g.

7. according to the method for preparing 3--oxyl-1-propyl alcohol of claim 2, the reaction of wherein said vinyl carbinol and alkylol cpd is undertaken by vapor phase process.

8. according to the method for preparing 3--oxyl-1-propyl alcohol of claim 2, carry out under the existence that is reflected at water of wherein said vinyl carbinol and alkylol cpd.

9. the method for preparing 3--oxyl-1-propyl alcohol according to Claim 8, the amount that wherein is present in the water in the described reaction system are no less than the mole number of element in the catalyzer of the described at least a element that contains the scandium, yttrium, lanthanon and the actinide elements that are selected from periodictable.

10. according to the method for preparing 3--oxyl-1-propyl alcohol of claim 2, wherein the productive rate of 3--oxyl-1-propyl alcohol in every 1mmol as the metal of catalyzer reaction times 0.5 or bigger per hour.