JP2010013365A - Method for producing propylene - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new method for producing propylene. <P>SOLUTION: This method for producing propylene is provided by making ethylene in contact with a catalyst obtained by containing at least one element selected from the group consisting of nickel, titanium, vanadium, chromium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, tantalum, tungsten, rhenium, osmium, iridium and platinum in an irregular mesoporous material, amorphous silica or zeolite. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing propylene. More specifically, the present invention relates to a production method for producing propylene using ethylene or ethylene and n-butene as raw materials.

Conventionally, as a method for selectively producing propylene, for example, a method of producing a mixture of ethylene and n-butene using a molybdenum oxide catalyst or a tungsten oxide catalyst supported on silica is known (Patent Document). 1).
US Pat. No. 4,754,098

  However, when propylene is produced by the conventional production method described above, two types of olefins, ethylene and n-butene, are required as raw materials. Therefore, in the complex where it is difficult to obtain one of the raw materials, it was difficult to synthesize propylene. Furthermore, in this reaction, since water becomes a catalyst poison, it is necessary to highly remove water from the reaction system.

  Under such circumstances, there has been a strong demand for the development of a method for producing propylene from ethylene alone using a new catalyst.

  Then, this invention is made | formed in view of said problem, The objective is to provide the manufacturing method of the novel propylene which manufactures propylene from ethylene.

  Another object is to provide a novel method for producing propylene, which produces propylene from a mixture of ethylene and n-butene.

  In order to solve the above problems, the method for producing propylene according to the present invention includes nickel, titanium, vanadium, chromium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, tantalum, tungsten, rhenium, osmium, iridium and platinum. Propylene is produced by bringing ethylene into contact with a catalyst containing at least one element selected from the group consisting of non-regular mesoporous material, amorphous silica or zeolite.

  ADVANTAGE OF THE INVENTION According to this invention, the novel manufacturing method of propylene which manufactures propylene from ethylene using a novel catalyst can be provided.

(Reaction catalyst)
First, the catalyst used in the present invention will be described.

  The catalyst used in the method for producing propylene according to the present invention (hereinafter also simply referred to as “the method for producing the present invention”) is nickel, titanium, vanadium, chromium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, tantalum, At least one element selected from the group consisting of tungsten, rhenium, osmium, iridium and platinum (hereinafter also referred to as “metal such as titanium”) is contained in a non-regular mesoporous material, amorphous silica or zeolite. It is a catalyst.

  As the support material for the catalyst, non-regular mesoporous material, amorphous silica or zeolite is used.

  In the present specification, the “support material” is a substance for supporting a metal serving as an active site, or a substance for incorporating a metal into the skeleton by isomorphous substitution and holding the metal.

  The non-regular mesoporous material is an inorganic substance having nanopores with no regularity, and the nanopores having an average pore diameter of 1 nm to 10 nm are intended.

  Silica is preferred as the main component of the skeleton constituting the non-regular mesoporous material used as the catalyst support material.

  At least one element selected from the group consisting of nickel, titanium, vanadium, chromium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, tantalum, tungsten, rhenium, osmium, iridium and platinum (hereinafter referred to as “metal such as titanium”) As a method for producing a non-regular mesoporous porous material containing “)” in the skeleton, for example, a conventionally known method can be used. For example, as a method for producing a non-regular mesoporous material containing titanium, a method for producing a titanium-containing silicon oxide disclosed in Japanese Patent Application Laid-Open No. 2000-107605 can be used. Moreover, when manufacturing the non-regular mesoporous porous body containing metals other than titanium, it can manufacture by changing titanium into metals other than titanium in the said manufacturing method.

  After preparing a catalyst by containing a metal such as titanium in a non-regular mesoporous material, the catalyst is preferably subjected to a calcination treatment in the air before the catalyst is used in the reaction. The firing temperature is preferably 300 ° C to 600 ° C, and more preferably 450 ° C to 550 ° C.

  Various methods for preparing amorphous silica are conventionally known. As a method for preparing the amorphous silica used in the present invention, for example, any conventionally known method is adopted. For example, it can be prepared using the method described on pages 161 to 171 of the catalyst manual for each element (4th edition of 1978, Jinshoshokan).

  After preparing a catalyst by containing a metal such as titanium in amorphous silica, the catalyst is preferably subjected to a calcination treatment in the air before the catalyst is used in the reaction. The firing temperature is preferably 300 ° C to 600 ° C, and more preferably 450 ° C to 550 ° C.

  The zeolite used in the present invention is a symbol defined by the International Zeolite Association (IZA), MCM-68, BEA, CFI, FAU, FER, MEI, MEL, MFI, MFS, MOR, MTT, MTW, MWW, NES, It is preferably at least one zeolite selected from the group consisting of zeolites represented by TON and VET. These structures are uniquely determined. These zeolites have a high Si / Al ratio and can be suitably used in the production method of the present invention.

  The zeolite used in the present invention preferably has a Si / Al ratio of 3 or more, and more preferably has a Si / Al ratio of 5 or more.

  After preparing the catalyst by containing a metal such as titanium in the zeolite, it is preferable to subject the catalyst to a calcination treatment in the air before using the catalyst for the reaction. The firing temperature is preferably 300 ° C to 600 ° C, and more preferably 450 ° C to 550 ° C.

  As described above, the metal elements contained in the non-regular mesoporous material, amorphous silica and zeolite are nickel, titanium, vanadium, chromium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, tantalum, tungsten, It is at least one element selected from the group consisting of rhenium, osmium, iridium and platinum.

  As a method for incorporating a metal such as titanium into the irregularly ordered mesoporous porous material, amorphous silica and zeolite, which are carrier materials, for example, a conventional method may be used. Examples of the method of incorporating a metal such as titanium into the carrier material include a method of incorporating a metal such as titanium into the skeleton of the carrier material simultaneously with the formation of the carrier material. In this case, when preparing the carrier material, a metal such as titanium can be added simultaneously to be incorporated into the skeleton of the carrier material. Another method for incorporating a metal such as titanium into the carrier material is a method in which the carrier material is formed without taking in the metal such as titanium, and after the carrier material is formed, the metal such as titanium is supported on the carrier material. Is mentioned. In this case, after forming the support material, a method for impregnating and supporting, a method for supporting ion exchange, a method for supporting equilibrium adsorption, and a template ion for ion exchange in the presence of a template disclosed in WO 2005/023420 Examples of the exchange method include template ion exchange method.

  The form of the metal used when a metal such as titanium is contained in the irregular mesoporous porous material, amorphous silica, and zeolite, which are support materials, differs depending on the method of inclusion, and can be appropriately selected.

  In the method of adding a metal simultaneously with the formation of the support material to incorporate a metal such as titanium into the skeleton of the support material, it is preferable to use a metal alkoxide, nitrate, chloride, acetate and sulfate. It is more preferable to use

  In the method of supporting a metal such as titanium by the impregnation method, ion exchange method, equilibrium adsorption method or template ion exchange method after forming the skeleton of the support material, the metal nitrate, chloride, acetate and sulfate are added. It is preferable to use it.

  The ratio of the metal such as titanium contained in the support material is 0.1 mass as the mass ratio of the metal element to the support material, regardless of whether the support material is a non-regular mesoporous material, amorphous silica, or zeolite. % To 10% by mass, preferably 0.2% to 5% by mass. When the content ratio of the metal element is 0.1% by mass or more, the active point of the catalyst increases. When the content ratio of the metal element is 10% by mass or less, the ratio at which the metal oxide is aggregated decreases.

(Raw material gas)
The method for producing propylene according to the present invention is a method for producing propylene from ethylene in the presence of the above-described catalyst.

  When impurities such as acetylenes and allenes are contained in ethylene as a raw material, these act as catalyst poisons. Therefore, the yield of propylene decreases. Therefore, the ratio of these impurities in the raw material is preferably 5 ppm or less, more preferably 1 ppm or less.

  Even if an inert component such as ethane coexists in the raw ethylene, there is no problem in the reaction. However, when employing a process for recycling ethylene, it is preferable to use high-purity ethylene. Therefore, in the case of employing the above process, the ratio of the inert component in the raw material is preferably 2% or less, more preferably 1% or less.

  Another method for producing propylene according to the present invention is a method for producing propylene from a mixture of ethylene and n-butene in the presence of the catalyst.

  When a mixture of ethylene and n-butene is used as a raw material, 1-butene, cis-2-butene, and trans-2-butene isomers can be used for the reaction as n-butene. In addition, n-butene contained in the mixture may be only one of the above isomers, or may be a mixture of a plurality of isomers.

  When impurities such as butadiene are contained in the raw material n-butene, these act as catalyst poisons. Therefore, the yield of propylene decreases. Therefore, the ratio of impurities in the raw material containing ethylene and n-butene is preferably 100 ppm or less, more preferably 10 ppm or less.

  Even if an inert component such as n-butane and isobutane coexists in the raw material n-butene, the reaction is not hindered.

  When a mixture of ethylene and n-butene is used as a raw material, the mixing ratio is not particularly limited. If it is a mixture of ethylene and n-butene, it can be made to react by a free ratio.

  When n-butene is not included as a raw material, the concentration of ethylene in the raw material containing ethylene is preferably 20% or more.

  The raw material ethylene or a mixture of ethylene and n-butene is directly introduced into the reactor.

  In the production method of the present invention, moisture can coexist in the raw material gas.

(Reaction conditions)
In the method for producing propylene according to the present invention, the reaction mode is not particularly limited, and various reaction modes such as a fluidized bed reaction mode, a fixed bed reaction mode, and a fixed bed flow reaction mode can be used. Among them, the fixed bed flow reaction method is preferably used from the viewpoint that the equipment cost is low.

  The reaction temperature in the production method of the present invention is preferably 200 ° C to 600 ° C, more preferably 300 ° C to 500 ° C. When the reaction temperature is 200 ° C. or higher, there is an advantage that the reaction rate and the reaction activity are high. In addition, when the reaction temperature is 600 ° C. or lower, there is an advantage of preventing deterioration of the activity of the catalyst.

  The reaction pressure in the production method of the present invention can be appropriately selected from a wide range from normal pressure to high pressure, but is preferably in the range from normal pressure to 3.0 MPa. If it is 3.0 MPa or less, equipment costs can be suppressed.

  In the production method of the present invention, the supply amount of the raw material gas to the catalyst is W / F converted to 25 ° C. and 1 atta when the catalyst mass is expressed as W (g) and the gas supply amount is expressed as F (l / min). As described above, it is preferable that the reaction is performed within the range of W / F = 1 to W / F = 500. If W / F is 1 or more, there is an advantage that the conversion of ethylene and n-butene proceeds sufficiently. Moreover, if W / F is 500 or less, an undesirable side reaction can be suppressed and the selectivity of propylene can be increased.

  As described above, according to the present invention, ethylene alone or a mixture of ethylene and n-butene can be used as a raw material. The raw material can be appropriately determined depending on the location of the complex. For example, in a complex centering on a naphtha cracking furnace, both ethylene and n-butene are available, and therefore either ethylene alone or a mixture of ethylene and n-butene can be used as a raw material. For example, it is difficult to obtain n-butene in a complex centered on an ethane cracking furnace. In this case, propylene may be produced using ethylene alone as a raw material. According to the present invention, propylene can be produced from ethylene alone. Therefore, even in regions where n-butene is difficult to obtain as a raw material, propylene can be produced according to the present invention, which is advantageous.

(Tungsten oxide catalyst contact process)
In the production method of the present invention, a raw material gas which is ethylene or a mixture of ethylene and n-butene is converted into a catalyst containing a metal such as titanium in an irregular mesoporous porous material, amorphous silica or zeolite (hereinafter, You may make it contact with a tungsten oxide catalyst, after making it contact with "the 1st catalyst"). In this case, even if the conversion rate of ethylene when the raw material gas is brought into contact with the first catalyst is low, the conversion rate of ethylene is improved by contacting with the tungsten oxide catalyst thereafter. As a result, the yield of propylene can be improved. In addition, generation of by-products such as hexene can be suppressed.

  The tungsten oxide catalyst may be any catalyst that causes a metathesis reaction, and any catalyst can be employed. For example, the catalyst described in Patent Document 1 can be used. Preferably, a tungsten oxide catalyst supported on silica is used.

  The reaction conditions when the gas after contacting with the first catalyst is brought into contact with the tungsten oxide catalyst for reaction are the same as those in the first catalyst for any of the reaction temperature, reaction pressure, gas supply amount and reaction mode. The explanation can be applied mutatis mutandis.

  In the method for producing propylene according to the present invention, when a step of contacting with tungsten oxide is included, it is preferable that ethylene as a raw material does not contain impurities such as acetylenes and allenes. Similarly, the water content in the raw material is preferably 5 ppm or less.

  The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims, and embodiments obtained by appropriately combining the respective technical means disclosed are also included in the present invention. Included in the technical scope. Moreover, all the literatures described in this specification are used as reference.

  According to the production method of the present invention, propylene can be produced only from ethylene. Since the demand for propylene-based petrochemical products is increasing, the production method according to the present invention is very useful in the petrochemical industry.

Claims (6)

  A mesoporous porous material in which at least one element selected from the group consisting of nickel, titanium, vanadium, chromium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, tantalum, tungsten, rhenium, osmium, iridium and platinum is an irregular mesoporous material, A method for producing propylene, wherein ethylene is brought into contact with a catalyst contained in amorphous silica or zeolite.   The method for producing propylene according to claim 1, wherein a mixture obtained by mixing n-butene with ethylene is brought into contact with the catalyst.   The method for producing propylene according to claim 1, wherein the ethylene concentration in the raw material containing ethylene is 20% or more.   The zeolite is selected from the group consisting of zeolites represented by the symbols MCM-68, BEA, CFI, FAU, FER, MEI, MEL, MFI, MFS, MOR, MTT, MTW, MWW, NES, TON and VET The manufacturing method according to claim 1, wherein the manufacturing method is at least one.   5. The production method according to claim 1, wherein a content of the element in the catalyst is 0.1% by mass to 10% by mass.   6. The method according to claim 1, wherein the non-regular mesoporous material has an average pore diameter of 1 nm to 10 nm.