JP2010105974A - Method for producing olefin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an olefin in a high yield using a mixture of an alcohol and an aldehyde as the raw material. <P>SOLUTION: The raw material containing the mixture of an alcohol and an aldehyde is brought into contact with a catalyst having a regular mesoporous material as its main component at a temperature of 150°C or higher and 600°C or lower, preferably 250°C or higher and 500°C or lower. The mixing ratio (partial pressure ratio) of the alcohol and the aldehyde in the raw material to be brought into contact with the catalyst having a regular mesoporous material as its main component is (alcohol/aldehyde)=0.1 to 10. Thereby ethylene, propylene and butene are produced in high yields. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an olefin production method for producing an olefin using a mixture of an alcohol and an aldehyde as a raw material.

Conventionally, use of biomass-derived ethyl alcohol as a fuel has been attracting attention in order to suppress carbon dioxide emission. In addition to using biomass-derived ethyl alcohol as a fuel, it is also possible to switch from petrochemical industry to biomass complex, for example, by using it as an alternative raw material for petroleum. It is conceivable that further effective utilization can be obtained as a raw material.
Processes and catalysts for converting ethyl alcohol to lower olefins or other hydrocarbons are known. For example, a method of converting ethyl alcohol into an olefin, paraffin, or aromatic compound using a proton-type zeolite typified by H-ZSM-5 as a catalyst is known (for example, Patent Document 1 and Non-Patent Document 1 to Non-Patent Document 1). (See Patent Document 3). Moreover, the catalyst which has a regular mesoporous body as a main component as a new catalyst is also reported (patent document 2).

The thing of patent document 1 introduce | transduces ethyl alcohol vapor | steam on the catalyst which carry | supported aluminum or nickel in calcium phosphate, and produces | generates ethylene, acetaldehyde, butadiene, butanol, and diethyl ether at 623K-823K.
Non-patent literature 1 to non-patent literature 3 are prepared by introducing ethyl alcohol onto an acid catalyst, which is a proton type zeolite represented by H-ZSM-5, at various temperatures such as ethylene, propylene, and butene at 573K or higher. This produces hydrocarbons.

JP-A-11-217343 WO 2007/083684 A1 C.W.Ingram, R.J.Lancashire, Catal.Lett., 31, 395 (1995). A.K.Talukdar, K.G.Bhattacharyya, S.Sivasankar, Appl.Catal.A, 148,357 (1997). A.T.Aguayo, A.G.Gayubo, A.M.Tarrio, A. Atutxa, J. Bilbao, J. Chem. Tech. Biothech., 77, 211 (2002).

  However, in the conventional ones as described in Patent Document 1 and Non-Patent Document 1 to Non-Patent Document 3, for example, when ethylene is to be obtained with high selectivity, the reaction can be performed in a very short contact time, There is a possibility that special condition setting such as reducing the number of times is required. In addition, the strong acid-catalyst characteristics of zeolite cause oligomerization, carbon-carbon bond breakage, catalyst skeleton isomerization, etc., so it is necessary to utilize the shape selectivity of zeolite, and the types of raw alcohol and olefins to be produced May be restricted. As a catalyst for overcoming these problems, a regular mesoporous catalyst, which is a non-acidic catalyst, is reported in Patent Document 2 described above, but its activity is not sufficient. Thus, the conventional method may cause various inconveniences.

  In view of these points, the object of the present invention is to provide an olefin production method for producing an olefin in a high yield using a mixture of an alcohol and an aldehyde as a raw material.

The olefin production method of the present invention is characterized in that a raw material containing a mixture of an alcohol and an aldehyde is brought into contact with a catalyst mainly composed of a regular mesoporous material at 150 ° C. or more and 600 ° C. or less.
In the present invention, ethylene, propylene and butene are obtained in high yield.
In addition, for example, a desired olefin can be produced continuously and at a high yield with a simple structure in which a layer filled with a catalyst through which the raw material can flow is provided in the raw material flow path.
Here, when the temperature of the reaction for bringing the vaporized raw material and the catalyst into contact with each other is lower than 150 ° C., the reaction rate is lowered and olefin cannot be produced with a high yield. On the other hand, when the temperature of the reaction is higher than 600 ° C., for example, the catalytic activity is reduced due to the generation of coke, and it becomes impossible to produce olefin in high yield. By this, a raw material and a catalyst are made to contact at 150 to 600 degreeC. In particular, the contact is preferably performed at 250 ° C. or more and 500 ° C. or less.
Note that water may be mixed in the raw material.

And in this invention, it is the manufacturing method of the olefin of Claim 1, Comprising: It is preferable that the frame | skeleton which comprises the said regular mesoporous body is set as the structure whose main component is a silica.
This makes it possible to easily obtain a regular mesoporous material having good physical properties with good support of nickel, aluminum, manganese, iron or copper.

Moreover, in this invention, it is a manufacturing method of the olefin of Claim 1 or Claim 2, Comprising: It is preferable that the said regular mesoporous body is set as the structure whose opening diameter is 1.4 nm or more and 10 nm or less.
This makes it easy to produce the desired olefin in a higher yield.
Here, if the opening diameter of the regular mesoporous material is smaller than 1.4 nm, the diffusibility of the reaction molecules and the generated molecules may be lowered, and the reaction efficiency may be lowered. On the other hand, when the opening diameter of the regular mesoporous material is larger than 10 nm, it is difficult to obtain the effect of pores, and there is a possibility that a high yield cannot be obtained. For this reason, it is preferable to set the opening diameter of the regular mesoporous material to 1.4 nm or more and 10 nm or less.

Furthermore, in this invention, it is a manufacturing method of the olefin as described in any one of Claim 1- Claim 3, Comprising: The said catalyst is nickel, aluminum, manganese, iron in the said regular mesoporous body, And one or more selected from the group consisting of copper are preferably supported.
This gives a higher yield with the desired olefin.

Moreover, in this invention, it is a manufacturing method of the olefin as described in any one of Claim 1- Claim 4, Comprising: The alcohol and the aldehyde contained in the said raw material are each derived from biomass, The said raw material Is preferably brought into contact with the catalyst at 150 ° C. or higher and 600 ° C. or lower.
In this invention, agricultural and forestry products such as plants and biomass that fix carbon dioxide in the atmosphere as carbon content and biomass can be used as raw materials. Since carbon dioxide in the atmosphere does not increase on the net, it can be effectively used as a substitute for petroleum, It is beneficial from the viewpoint of environment and resources, such as suppression of carbon emission and effective use of biomass.

Furthermore, in this invention, it is a manufacturing method of the olefin of Claim 5, Comprising: It is preferable that the said alcohol is ethyl alcohol derived from biomass.
In this invention, since bioethyl alcohol can be produced in large quantities, the use of bioethyl alcohol as a biomass-derived alcohol raw material is more beneficial from the viewpoint of effective use of the environment and resources.

Moreover, in this invention, it is a manufacturing method of the olefin as described in any one of Claim 1-6, Comprising: The said alcohol and aldehyde made to contact with the catalyst which has the said regular mesoporous body as a main component It is preferable that the mixing ratio (partial pressure ratio) of both in the raw material containing the mixture of (alcohol / aldehyde) = 0.1-10.
In this invention, since the mixing ratio of alcohol and aldehyde is specified, the yield of olefins can be improved and the yields of various olefins produced can be controlled.
On the other hand, when the mixing ratio is less than 0.1 or exceeds 10, the olefin yield may be reduced.

Hereinafter, an embodiment according to the method for producing olefin of the present invention will be described.
In the present embodiment, the structure for producing olefin using ethyl alcohol as alcohol and acetaldehyde as aldehyde as raw materials will be described. However, propyl alcohol having 3 carbons, propionaldehyde, acrolein, butyl alcohol having 4 carbons, Butyraldehyde, crotonaldehyde, or the like may be used as a raw material.
Moreover, as alcohol and aldehyde used as a raw material, various alcohols and aldehydes may be mixed, or water may be mixed. Furthermore, the raw material may be supplied directly to a fixed bed type gas flow reactor or supplied by appropriately diluting with an inert gas such as nitrogen, helium, argon, carbon dioxide, that is, mixed with an inert gas. Good. Furthermore, the aldehyde may be obtained by using alcohol as a starting material, passing through a dehydrogenation catalyst and converted to an aldehyde.
In addition to the above, the aldehyde may be formaldehyde, paraaldehyde, propiolaldehyde, valeraldehyde, capronaldehyde, heptone aldehyde.
The aforementioned alcohol and aldehyde are preferably derived from biomass. The aldehyde is preferably one obtained by dehydrogenating alcohol, one obtained by oxidation, or one obtained by fermentation reaction of sugar.

(Composition of catalyst)
The catalyst used for the production of olefin in the present embodiment is a regular mesoporous material.
This regular mesoporous material is an inorganic or inorganic-organic composite solid material having regular nanopores. As the catalyst, for example, alumina powder particles may be mixed.

Silica is preferred as the main component of the skeleton constituting the regular mesoporous material.
Here, the method for synthesizing the regular mesoporous material is not particularly limited. For example, a method of synthesizing a silica precursor as a raw material using a quaternary ammonium salt having a higher alkyl group having 8 or more carbon atoms as a template. Etc. can be exemplified.
And as a kind of silica precursor, for example, amorphous silica such as colloidal silica, silica gel, fumed silica, alkali silicate such as sodium silicate and potassium silicate, alkoxide such as tetramethyl orthosilicate, tetraethyl orthosilicate, They can be used alone or in combination. The type of template is not particularly limited, but the general formula CH ₃ (CH ₂ ) _n N (CH ₃ ) ₃ .X (n is an integer of 7 to 21, X is a halogen ion or a hydroxide ion) A halogen or alkyltrimethylammonium cationic surfactant represented by is preferred. Specific examples include n-octyltrimethylammonium bromide, n-decyltrimethylammonium bromide, n-dodecyltrimethylammonium bromide, n-tetradecyltrimethylammonium bromide, n-octadecyltrimethylammonium bromide and the like.
In addition, silica has a structure in which regular nanopores are easily obtained, physical properties such as strength are good, and stable support of nickel, aluminum, manganese, iron, or copper is easily obtained. It is preferable to use it.

Furthermore, as the regular mesoporous material, it is preferable to use one having an opening diameter of 1.4 nm to 10 nm, for example.
Here, when the opening diameter of the regular mesoporous material is smaller than 1.4 nm, for example, the diffusibility of the reaction molecules and the generated molecules may be lowered, and the reaction efficiency may be lowered. On the other hand, when the opening diameter of the regular mesoporous material is larger than 10 nm, it is difficult to obtain, for example, the effect of pores, that is, good support of nickel, aluminum, manganese, iron or copper, which are active components, and a high yield is obtained. There is a risk of being lost. Accordingly, it is preferable to set the opening diameter of the regular mesoporous material to 1.4 nm or more and 10 nm or less in terms of production with a high yield of olefin.

As the catalyst, a regular mesoporous material carrying one or more metals selected from the group of nickel, aluminum, manganese, iron, and copper may be used.
Here, the method for supporting the metal on the regular mesoporous material is not particularly limited, and for example, an impregnation method, a vapor deposition method, a supported complex decomposition method, and the like can be used. In particular, a template ion exchange method in which metal ions and template ions are exchanged in an aqueous solvent without firing and removing the template stored in the pores obtained by synthesizing the regular mesoporous material is preferable in terms of manufacturability. . Further, template ion exchange can use a method in which a regular mesoporous material having a template occluded in pores is brought into contact with a metal inorganic acid salt or organic acid salt aqueous solution.
The amount of the metal (Me) supported on the regular mesoporous material is, for example, an atomic ratio Si / Me of 5 or more and 500 or less, based on silica (Si) constituting the skeleton of the regular mesoporous material. It is preferably 15 or more and 100 or less. Here, when the atomic ratio Si / Me is smaller than 5, the ratio of Me increases, it becomes difficult to suppress the formation of metal oxide particles having low catalytic activity, and the catalytic activity may be lowered. On the other hand, when the atomic ratio Si / Me is larger than 500, the ratio of Me decreases, and sufficient support of the metal cannot be obtained, and the catalytic activity may be lowered. Accordingly, the metal loading is preferably set so that the atomic ratio Si / Me is 5 or more and 500 or less, particularly 15 or more and 100 or less.
In addition, the regular mesoporous material on which a metal is supported by template ion exchange is preferably subjected to a heat treatment in an atmosphere in which oxygen exists in order to remove the remaining template by firing. Here, the temperature of heat processing is 200 degreeC or more and 800 degrees C or less, for example, Preferably they are 300 degreeC or more and 600 degrees C or less. And when the temperature of heat processing becomes lower than 200 degreeC, there exists a possibility that time may be required for baking of a template. On the other hand, when the temperature of the heat treatment is higher than 800 ° C., the silica constituting the pore walls may be collapsed. Thus, the temperature of the heat treatment of the regular mesoporous material carrying a metal is preferably set to 200 ° C. or higher and 800 ° C. or lower, preferably 300 ° C. or higher and 600 ° C. or lower.

(Olefin production method)
In the olefin production method of the present invention, a raw material containing a mixture of the above-mentioned alcohol and aldehyde is brought into contact with the above-mentioned catalyst to produce or produce an olefin.
Here, the olefin production apparatus is not particularly limited. For example, a fixed bed gas phase flow reaction apparatus which is a reactor filled with the above-described catalyst and having a catalyst layer inside and capable of circulating raw materials. Can be used.
Further, the raw material may be directly supplied to the fixed bed gas phase flow reactor, or may be appropriately diluted with an inert gas such as nitrogen, helium, argon, carbon dioxide, etc., that is, the inert gas may be mixed. .

And as reaction temperature, it is preferable that they are 150 degreeC or more and 600 degrees C or less. Here, when the reaction temperature is lower than 150 ° C., sufficient catalytic activity cannot be obtained, the reaction rate is lowered, and the production efficiency of olefin may be lowered. On the other hand, if the reaction rate is higher than 600 ° C., for example, coke may be generated, which may cause deterioration of catalytic activity. Accordingly, the reaction temperature is preferably set to 150 ° C. or more and 600 ° C. or less, more preferably 250 ° C. or more and 500 ° C. or less.
The reaction pressure of the raw material gas can be appropriately set within a wide range from normal pressure to high pressure. From the viewpoint of manufacturability and apparatus configuration, it is preferable to set the pressure from normal pressure to about 1.0 MPa.

The contact time between the raw material and the catalyst is, for example, 0.001 (g-catalyst · second) / (mL-raw material gas) or more and 10 (g-catalyst · second) / (mL-) when the raw material is reacted in the gas phase. Raw material gas) or less, particularly preferably 0.01 (g-catalyst · second) / (mL-raw material gas) or more and 10 (g-catalyst · second) / (mL-raw material gas) or less.
Here, when the contact time with the catalyst is shorter than 0.001 (g-catalyst · second) / (mL-raw gas), the improvement of the conversion of the raw olefin cannot be expected, and the desired olefin is obtained in a high yield. There is a risk that it cannot be manufactured. On the other hand, if the contact time with the catalyst is longer than 10 (g-catalyst · second) / (mL-source gas), side reactions such as polymerization may occur, and the desired olefin may not be obtained in a high yield. is there. Thus, the contact time between the source gas and the catalyst is 0.001 (g-catalyst · second) / (mL-source gas) to 10 (g-catalyst · second) / (mL-source gas), particularly It is preferable to set it to 0.01 (g-catalyst · second) / (mL-source gas) or more and 10 (g-catalyst · second) / (mL-source gas) or less.

Moreover, when water is contained as the source gas, the amount of water supply in the source gas is preferably 20 vol% or less.
Here, when the amount of water supply in the raw material gas exceeds 20 vol%, the conversion rate of the raw material is lowered, and there is a possibility that olefin cannot be obtained in a high yield. Accordingly, the water supply amount in the raw material gas is preferably set to 20 vol% or less, and preferably 10 vol% or less.

(Effect of embodiment)
As described above, in the above embodiment, a catalyst containing a regular mesoporous material as a main component is contacted with a raw material containing a mixture of alcohol and aldehyde at 150 ° C. or more and 600 ° C. or less, preferably 250 ° C. or more and 500 ° C. I am letting.
For this reason, ethylene, propylene, and butene are obtained with a high yield.
Further, for example, a desired olefin can be produced continuously and at a high yield with a simple structure in which a layer filled with a catalyst through which a raw material can flow is provided in the flow path of the raw material.

In the above embodiment, as the regular mesoporous material constituting the catalyst, the main component of the skeleton is silica.
For this reason, a regular mesoporous material having good physical properties with good support of nickel, aluminum, manganese, iron or copper can be easily obtained.

  Moreover, in the said embodiment, what was prepared with an aperture diameter of 1.4 nm or more and 10 nm or less is used as a regular mesoporous body.

Furthermore, in the said embodiment, the catalyst which carry | supported 1 type (s) or 2 or more types chosen from the group of nickel, aluminum, manganese, iron, and copper is used for a regular mesoporous body.
For this reason, higher yields are obtained with the desired olefins.

And in the said embodiment, the raw material containing the mixture of ethyl alcohol and acetaldehyde derived from biomass is made to contact with a catalyst at 150 to 600 degreeC, Preferably it is 250 to 500 degreeC, and the olefin is produced | generated.
For this reason, it is beneficial from the viewpoint of environment and resources, such as suppression of carbon dioxide emission and effective use of biomass. In addition, bioethyl alcohol can be produced in large quantities, and using bioethyl alcohol as a biomass-derived alcohol raw material is more beneficial from the viewpoint of effective use of the environment and resources.

Moreover, in the said embodiment, the mixing ratio (partial pressure ratio) of both in the raw material containing the alcohol and aldehyde contacted with the catalyst which has a regular mesoporous body as a main component is (alcohol / aldehyde) = 0.1-0.1. 10.
For this reason, since the mixing ratio of alcohol and aldehyde is specified, it is possible to improve the yield of olefins and to control the yields of various olefins produced.

In the above embodiment, bioethyl alcohol is used as the raw material ethyl alcohol, and the raw material acetaldehyde is obtained by dehydrogenation of bioethyl alcohol.
For this reason, since ethyl alcohol and acetaldehyde are each derived from biomass, the biomass can be effectively used, which is further beneficial from the viewpoint of environment and resources. The raw material aldehyde can be easily obtained by dehydrogenation of alcohol.

[Modification of Embodiment]
The aspect described above shows one aspect of the present invention, and the present invention is not limited to the above-described embodiment, and within the scope of achieving the objects and effects of the present invention. Needless to say, the modifications and improvements are included in the contents of the present invention. In addition, the specific structure and shape in carrying out the present invention may be used as other structures and shapes within the scope of achieving the object and effect of the present invention.

That is, the production apparatus for carrying out the olefin production method of the present invention is not limited to the above-described fixed bed gas phase flow reaction apparatus. For example, any configuration in which the raw material is brought into contact with the catalyst, such as bringing the raw material gas into contact with the catalyst as a fluidized bed, can be applied. Furthermore, as a catalyst, it can utilize with various forms, such as a granular material and a lump, what is called a honeycomb structure.
Further, the composition is not limited to the silica mesoporous material, and any composition may be applied as long as it is a regular mesoporous material such as a material in which the main component of the skeleton includes other inorganic materials such as alumina. .
The catalyst is not limited to a structure using a regular mesoporous material alone, and as described above, one or more selected from the group of nickel, aluminum, manganese, iron, and copper are supported. May be used.

The physical properties of the regular mesoporous material, and the physical properties of the catalyst such as one or more supported amounts selected from the group of nickel, aluminum, manganese, iron, and copper supported on the regular mesoporous material are as described above. The conditions are not limited to those described above, and can be set as appropriate depending on the processing efficiency, the apparatus configuration, and the like.
Furthermore, the raw material is not limited to ethyl alcohol or acetaldehyde as long as it corresponds to the product olefin, and may further contain water, other alcohols, aldehyde, or the like.
Further, the reaction treatment conditions, which are the contact conditions of the raw material gas vaporized with the catalyst, are not limited to the above-mentioned conditions. If the reaction temperature is 150 ° C. or more and 600 ° C. or less, the treatment efficiency and the equipment configuration It can be set as appropriate.

  In addition, the specific structure and shape in the implementation of the present invention may be other structures as long as the object of the present invention can be achieved.

  Next, the manufacturing method of the olefin of this invention is demonstrated concretely by an Example. The present invention is not limited to the following examples.

[Comparative Example 1 and Example 1]
(Preparation of catalyst)
First, preparation of the catalyst will be described. Snowtex 20 (colloidal silica) manufactured by Nissan Chemical Industries, Ltd. was used as the silica source, and dodecyltrimethylammonium bromide (manufactured by Tokyo Chemical Industry) as the surfactant. All experimental tools were made of Teflon.
First, 641.4 g of ion-exchanged water was mixed with 225.0 g of a surfactant and stirred vigorously. Snowtex 20 (306.7 g) and an aqueous sodium hydroxide solution (NaOH 11.7 g + H ₂ O 125.6 g) were alternately added dropwise thereto. After dropping the entire amount, the mixed solution was stirred at 313K for 2 hours. The final pH of the mixed solution was 11.6. This mixed solution was hydrothermally treated at 413 K in an autoclave for 48 hours under standing conditions. The obtained white product was filtered, washed with 2 L of ion exchange water, and then dried overnight at 353 K in a dryer. The obtained product (MCM-41as-syn) was mixed in ion-exchanged water slightly acidified with hydrochloric acid and stirred (the H ₂ O: MCM-41as-syn weight ratio at this time was 30: 1). Hydrochloric acid was slowly added to this solution to adjust the pH to 6-7. After the pH was stabilized, it was allowed to stand at 353 K for 20 hours. After this treatment, it was filtered, washed with 500 mL of ion exchange water, and dried overnight in a dryer.
Further, the obtained white powder was pulverized in a mortar, spread thinly on a magnetic dish, and fired in air at 873 K for 6 hours.
This was designated as MCM-41 and used for the reaction.

(Reaction of ethyl alcohol and acetaldehyde)
The reaction of ethyl alcohol and acetaldehyde was carried out using MCM-41 as a catalyst. Quartz wool is packed at the bottom of a heat-resistant glass reactor having an inner diameter of 10 mm, and 0.2 g of catalyst is packed thereon. Prior to the reaction, 50 mL / min of nitrogen gas was circulated at 673 K for 2 hours as a catalyst pretreatment. Thereafter, the temperature of the catalyst layer is kept at 673 K, and under conditions of GHSV = 1000 h ⁻¹ under a nitrogen stream, each raw material partial pressure is about 6%, only ethyl alcohol, with a mixed gas of ethyl alcohol and acetaldehyde. Reaction was performed.
The obtained results are shown in Tables 1 and 2.

In Tables 1 and 2, EtOH represents ethyl alcohol, AA represents acetaldehyde, C1 represents methane, C2 = represents ethylene, C3 = represents propylene, and C4 = represents butene (1-butene + 2-butene). In addition, since the yield when supplying ethyl alcohol and acetaldehyde (Example 1) was calculated on the basis of the amount of supplied ethyl alcohol, it exceeded 100%.
According to Tables 1 and 2, in Example 1, since both were mixed and supplied, the olefin yield increased compared with the case where ethyl alcohol was reacted alone (Comparative Example 1), and C2 = It can be seen that more valuable C3 =, C4 = components can be taken. This is an effect that cannot be predicted from the conventional technique of Comparative Example 1.
[Comparative Example 2 and Example 2]

(Preparation of Ni-MCM-41)
Next, preparation of Ni-MCM-41 (catalyst) used in Comparative Example 2 and Example 2 will be described. 100 mL of ion-exchanged water was added to 10.0 g of unfired MCM-41, and the mixture was stirred and suspended. Moreover, 10.0 g of nickel nitrate hexahydrate (special grade of Wako Pure Chemical Industries) was dissolved in 100 mL of ion exchange water.
While stirring the unfired MCM-41 suspension vigorously, the Ni ion aqueous solution was slowly added using a pasteur, and the mixture was stirred at room temperature for 1 hour. After stirring, the mixture was allowed to stand in a 353K water bath for 20 hours. Thereafter, the mixture was filtered, dispersed in about 1 L of ion exchange water, stirred for 5 minutes, filtered, and dried overnight at 353 K to obtain unfired Ni-MCM-41. This unfired Ni-MCM-41 was thinly spread on a magnetic dish, heated to 773 K, and then fired in air for 6 hours to obtain Ni-MCM-41. The Ni / MCM-41 had an Si / Ni atomic ratio of 20.

(Reaction of ethyl alcohol and acetaldehyde)
The reaction was carried out using Ni-MCM-41 as a catalyst. The reaction method is the same as in Comparative Example 1 and Example 1.
The obtained results are shown in Tables 3 and 4.

In Example 2 of Table 4, since the calculation was based on the amount of supplied ethyl alcohol, the yield exceeded 100%.
From Tables 3 and 4, in Example 2, since both were mixed and supplied, the olefin yield increased and C2 =, C4 = components compared to the case where ethyl alcohol was reacted alone (Comparative Example 2). It can be seen that more can be taken. This is an effect that cannot be predicted from the technique of the conventional comparative example 2.

  INDUSTRIAL APPLICATION This invention can be utilized for the method of manufacturing an olefin from alcohol and an aldehyde as a raw material.

Claims (7)

A method for producing an olefin, comprising bringing a raw material containing a mixture of an alcohol and an aldehyde into contact with a catalyst mainly composed of a regular mesoporous material at a temperature of 150 ° C to 600 ° C. A method for producing an olefin according to claim 1,
The skeleton constituting the regular mesoporous material is mainly composed of silica. A method for producing an olefin according to claim 1 or 2, wherein
The regular mesoporous material has an opening diameter of 1.4 nm or more and 10 nm or less. It is a manufacturing method of the olefin according to any one of claims 1 to 3,
The said catalyst is what the 1 or 2 types chosen from the group of nickel, aluminum, manganese, iron, and copper were carry | supported by the said regular mesoporous body. The manufacturing method of the olefin characterized by the above-mentioned. It is a manufacturing method of the olefin according to any one of claims 1 to 4,
The alcohol and aldehyde contained in the raw material are each derived from biomass,
The said raw material is made to contact with the said catalyst at 150 to 600 degreeC. The manufacturing method of the olefin characterized by the above-mentioned. A method for producing an olefin according to claim 5,
The method for producing olefin, wherein the alcohol is biomass-derived ethyl alcohol. It is a manufacturing method of the olefin according to any one of claims 1 to 6,
The mixing ratio (partial pressure ratio) of both in the raw material containing the mixture of the alcohol and the aldehyde brought into contact with the catalyst mainly composed of the regular mesoporous material is (alcohol / aldehyde) = 0.1-10. An olefin production method characterized by the above.