JP6915259B2 - Method for producing propylene and straight-chain butene - Google Patents

Description

The present invention relates to a method for producing propylene and linear butene by contacting at least one raw material selected from methanol and dimethyl ether with a catalyst.

Conventionally, naphtha steam cracking method and reduced pressure light oil have been used as methods for producing olefins such as propylene and linear butene (1-butene, trans-2-butene, cis-2-butene) useful as a raw material for producing butadiene. The flow contact cracking method of naphtha is mainly used. However, in the steam cracking method, ethylene is produced in a large amount, and it is difficult to significantly change the production ratio of the target olefins such as propylene and linear butene. Therefore, it was difficult to respond to changes in the supply-demand balance of each olefin. Further, since the butenes obtained by the steam cracking method contain a large amount of isobutylene, there is a problem that the load of separation / purification becomes large when obtaining linear butene. Further, in recent years, an MTO (methanol to olefin) process using methanol and / or dimethyl ether as a raw material has been known.

The following methods have been proposed as a method for producing a lower olefin using methanol or dimethyl ether as a raw material.
For example, Patent Document 1 discloses a method for producing a lower olefin using a 10-membered ring pore MFI type aluminosilicate as a catalyst.
Further, in Patent Document 2, a catalyst containing CHA-type silicoaluminophosphate (SAPO-34) having 8-membered ring pores as an active ingredient is used to produce a lower olefin containing ethylene and propylene as main components in high yield. The method of manufacturing is disclosed.

Patent Document 3 discloses a method for producing a lower olefin in which the yield of an olefin having 3 or more carbon atoms is increased by using an aluminosilicate having a 12-membered ring pore MSE type structure as a catalyst.
Patent Document 4 discloses a method for producing a lower olefin using an aluminosilicate having an AEI-type structure with 8-membered ring pores having a relatively low silica composition as a catalyst.
On the other hand, Patent Document 5 describes that a lower olefin can be obtained in a high yield by using an aluminosilicate having an AEI type structure having a high silica composition synthesized by adding hydrogen fluoride as a catalyst.

Non-Patent Document 1 describes that a lower olefin can be obtained in a high yield by using a catalyst obtained by steam-treating an aluminosilicate having an AEI type structure.
However, the above-mentioned known methods have various problems, and satisfactory results are not always obtained.
In the method of Patent Document 1, the amount of ethylene and aromatic compounds produced is large, and the total yield of propylene and C4 (butene / butane) components is about 35%, which is practical in terms of production of propylene and linear butene. It's not a thing.

In the method of Patent Document 2, ethylene and propylene are the main products under the condition of a reaction temperature of 350 to 425 ° C. using CHA-type silicoaluminophosphate (SAPO-34) as a catalyst, and ethylene is about the same amount as propylene. Since it is produced (around 40% each), it is not practically usable in terms of co-production of propylene and linear butene.
In the method of Patent Document 3, propylene and butenes are produced under the condition of a reaction temperature of 350 to 400 ° C. using MSE type aluminosilicate (MCM-68) as a catalyst, but the yield of propylene is about 35% and C4. The yield of the components is about 25%, and the total yield of these is about 60%. In addition, there is no description about the ratio of linear butene in the C4 component to be produced, and as a result of additional testing, since about half of isobutene is contained in the C4 component, it can withstand practical use in terms of production of propylene and linear butene. It's not a thing.

In the method of Patent Document _4, the H-type AEI-type aluminosilicate of the SiO 2 / _Al 2 _{O 3} 14.7 as a catalyst, under conditions of a reaction temperature of 400 ° C., but produces propylene and butenes, propylene selectivity The rate is 35%, the C4 (butene / butane) selectivity is 14%, and the total selectivity of these is less than 50%. Further, the ratio of linear butene in the C4 component to be produced is also unknown, and the amount of propane by-produced is large (22%), so that it is not practically usable in terms of production of propylene and linear butene.

In the method of Patent Document 5, the propylene selectivity is 48 under the condition of a reaction temperature of 450 to 540 ° C. using an H-type AEI-type aluminosilicate having _{a Si / Al 2 ratio of 532 synthesized by adding hydrogen fluoride as a catalyst.} It is obtained with a selectivity of ~ 51% and a C4 (butene / butane) selectivity of 17-23%. The proportion of linear butene in the C4 component is unknown. Since the catalyst has a high Si / Al ₂ composition and therefore has few active sites, it is presumed that it is necessary to increase the reaction rate by the reaction under high temperature conditions. Although there is no description about the catalyst life, it has a high ethylene selectivity (27 to 19%) and is not practically usable in terms of producing propylene and linear butene. Furthermore, it aluminosilicates AEI-type structure, with hydrogen fluoride, and are those which are synthesized at a very low amount of water high density conditions _{(H 2 O / Si <5} ), industrial production of the catalyst In that respect, it is not practical.

In Non-Patent Document 1 method, was treated with steam AEI-type aluminosilicate from NH ₄ form states, reaction temperature 400 ° C., the methanol concentration of 10 mole%, it is reacted under the conditions of WHSV1.3Hr ^-1, A propylene selectivity of 48% and a butene selectivity of 20% are obtained, but the ethylene selectivity is as high as 17%, and the catalyst life is so short that the methanol conversion rate decreases to 80% in 520 minutes. Moreover, the ratio of linear butene in the produced butene is unknown. Due to its high ethylene selectivity and short catalyst life, it is not practical in terms of stable production of propylene and linear butene.

On the other hand, as a method for producing ethylene, steam cracking (hereinafter referred to as ethane cracking) using ethane contained in natural gas as a raw material is known. Due to the recent decline in natural gas prices, ethylene production costs for ethane cracking have decreased significantly compared to naphtha steam cracking, and ethylene production by ethane cracking has expanded rapidly. However, unlike naphtha steam cracking, ethane cracking produces almost no hydrocarbons with 3 or more carbon atoms such as propylene, butadiene, butene, etc., so hydrocarbons with 3 or more carbon atoms, especially propylene and butadiene, are deficient. The situation is becoming apparent.
Therefore, there is a demand for a method for stably producing propylene and linear butene in a higher yield and for a longer period of time than ethylene.

U.S. Pat. No. 4,148,835 JP-A-59-084829 Japanese Unexamined Patent Publication No. 2012-92063 U.S. Pat. No. 5,953,370 U.S. Pat. No. 7,08610

ACS Catal. 5, (2015), 6078-6085

The present invention provides a method for efficiently producing propylene and linear butene from at least one raw material selected from methanol and dimethyl ether, particularly for producing linear butene in a high yield and stably for a long period of time. The challenge is to provide.

As a result of diligent studies to solve the above problems, the present inventors are a method for producing propylene and linear butene by contacting at least one raw material selected from methanol and dimethyl ether with a catalyst. The reaction temperature of the step of obtaining a mixture containing propylene and straight-chain butene by contacting the raw material with the catalyst, which contains metallocates satisfying the following (1) to (3) as the active component of the catalyst, is 380. We have found that propylene and straight-chain butene can be efficiently and stably produced for a long period of time when the temperature is below ° C., and have reached the present invention.

(1) Its structure is AEI with a code defined by the International Zeolite Association (IZA).
(2) Contains at least one element M selected from the group consisting of aluminum, gallium, boron, and iron.
(3) The amount ratio of Si contained in the metallosilicate and the M is 5 or more and less than 100 in terms of _{SiO 2} / M ₂ O _{3 molar ratio.} (However, the denominator of the molar ratio represents the total amount of _{Al 2} O ₃ , Ga ₂ O ₃ , B ₂ O ₃ and Fe ₂ O _3).
That is, the gist of the present invention is as follows.

[1] A method for producing propylene and linear butene by contacting at least one raw material selected from methanol and dimethyl ether with a catalyst, which satisfies the following (1) to (3) as active components of the catalyst. A method for producing propylene and linear butene, which comprises a metallosilicate and has a reaction temperature of 380 ° C. or lower in a step of bringing the raw material into contact with the catalyst to obtain a mixture containing propylene and linear butene. ..
(1) Its structure is AEI with a code defined by the International Zeolite Association (IZA).
(2) Contains at least one element M selected from the group consisting of aluminum, gallium, boron, and iron.
(3) The amount ratio of Si contained in the metallosilicate and the M is 5 or more and less than 100 in terms of _{SiO 2} / M ₂ O _{3 molar ratio.} (However, the denominator of the molar ratio represents the total amount of _{Al 2} O ₃ , Ga ₂ O ₃ , B ₂ O ₃ and Fe ₂ O _3).

[2] The method for producing propylene and linear butene according to [1], wherein the total partial pressure of methanol and dimethyl ether is 0.005 MPa or more and 3 MPa or less.
[3] The mass ratio of linear butene to ethylene (linear butene / ethylene) in the step of obtaining the mixture containing propylene and linear butene is 1.5 or more [1] or [2]. ]. The method for producing propylene and linear butene.
[4] Any of [1] to [3], wherein the metallosilicate is treated with at least one selected from the group consisting of steam treatment, heat treatment, acid treatment, and ion exchange. The method for producing propylene and linear butene according to the above.
[5] The method for producing propylene and linear butene according to any one of [1] to [4], wherein the metallosilicate is an aluminosilicate containing at least aluminum.

[6] The method for producing propylene and linear butene according to any one of [1] to [5], wherein the average primary particle size of the metallosilicate is 0.03 μm or more and 5 μm or less. [7] The propylene and direct metal according to any one of [1] to [6], wherein the metallosilicate contains at least one element selected from an alkali metal element and an alkaline earth metal element. Method for producing chain butene.
[8] The propylene and propylene according to [7], wherein the total content of the alkali metal element and the alkaline earth metal element in the metallosilicate is 0.005% by mass or more and 10% by mass or less. A method for producing linear butene.
[9] The method for producing propylene and linear butene according to [7] or [8], which contains at least sodium as the alkali metal element.

[10] The total acid amount obtained from the high-temperature desorption amount of the metallosilicate in the ammonia-temperature desorption spectrum is 0.001 mmol / g or more and 0.80 mmol / g or less [1] to [1] to [ 9] The method for producing propylene and linear butene according to any one of.
[11] The method for producing propylene and linear butene according to any one of [1] to [10], wherein the metallosilicate is silylated.
[12] The total amount of acid determined from the amount of high-temperature desorption in the ammonia temperature desorption spectrum of the catalyst is 0.001 mmol / g or more and 0.80 mmol / g or less [1] to [11]. The method for producing propylene and linear butene according to any one of.

[13] A metallosilicate that satisfies the following (1) to (5).
(1) Its structure is AEI with a code defined by the International Zeolite Association (IZA).
(2) Contains at least one element M selected from the group consisting of aluminum, gallium, boron, and iron.
(3) The amount ratio of Si contained in the metallosilicate and the M is 5 or more and less than 100 in terms of _{SiO 2} / M ₂ O _{3 molar ratio.} (However, the denominator of the molar ratio represents the total amount of _{Al 2} O ₃ , Ga ₂ O ₃ , B ₂ O ₃ and Fe ₂ O _3).
(4) Contains at least one element selected from alkali metal elements and alkaline earth metal elements.
(5) The total amount of acid determined from the amount of high-temperature desorption in the ammonia temperature-temperature desorption spectrum is 0.001 mmol / g or more and 0.80 mmol / g or less.

[14] The metallosilicate according to [13], wherein the total content of the alkali metal element and the alkaline earth metal element is 0.005% by mass or more and 10% by mass or less.
[15] The metallosilicate according to [13] or [14], which contains at least sodium as an alkali metal element.
[16] The metallosilicate according to any one of [13] to [15], wherein the average primary particle size is 0.03 μm or more and 5 μm or less.

[17] A metallosilicate that satisfies the following (1) to (5).
(1) Its structure is AEI with a code defined by the International Zeolite Association (IZA).
(2) Contains at least one element M selected from the group consisting of aluminum, gallium, boron, and iron.
(3) The amount ratio of Si contained in the metallosilicate and the M is 5 or more and less than 100 in terms of _{SiO 2} / M ₂ O _{3 molar ratio.} (However, the denominator of the molar ratio represents the total amount of _{Al 2} O ₃ , Ga ₂ O ₃ , B ₂ O ₃ and Fe ₂ O _3).
(4) The average primary particle size is 0.03 μm or more and 0.60 μm or less.
(5) The total amount of acid determined from the amount of high-temperature desorption in the ammonia temperature-temperature desorption spectrum is 0.001 mmol / g or more and 0.80 mmol / g or less.

According to the present invention, propylene and linear butene can be simultaneously produced in high yield using methanol and / or dimethyl ether as raw materials. In particular, linear butene can be stably produced in a high yield and for a long period of time. Further, since the by-product of isobutene can be suppressed and the linear butene can be selectively produced, the load in the step of separating and purifying the linear butene and isobutene can be significantly reduced.

It is a figure which shows the linear butene yield with respect to the elapsed time in Example 1 and Comparative Example 1.

A typical embodiment for carrying out the present invention will be specifically described below, but the present invention is not limited to the following embodiments as long as the gist of the present invention is not exceeded, and the present invention may be implemented in various modifications. Can be done.
The present invention is a method for producing propylene and linear butene by contacting at least one raw material selected from methanol and dimethyl ether with a catalyst, wherein the following (1) to (3) are used as active components of the catalyst. The reaction temperature of the step of contacting the raw material with the catalyst to obtain a mixture containing propylene and linear butene, which contains the metallosilicate to be satisfied, is 380 ° C. or lower.

(1) Its structure is AEI with a code defined by the International Zeolite Association (IZA).
(2) Contains at least one element M selected from the group consisting of aluminum, gallium, boron, and iron.
(3) The amount ratio of Si contained in the metallosilicate and the M is 5 or more and less than 100 in terms of _{SiO 2} / M ₂ O _{3 molar ratio.} (However, the denominator of the molar ratio represents the total amount of _{Al 2} O ₃ , Ga ₂ O ₃ , B ₂ O ₃ and Fe ₂ O _3).
The metallosilicate is hereinafter referred to as "metallosilicate of the present invention".
Hereinafter, the present invention will be described in detail.

1. 1. Catalyst The catalyst used in the present invention contains the following metallocates as active ingredients.
[Metallocate of the present invention]
(Construction)
The metallosilicates of the present invention are usually crystalline. Metallosilicate is a porous crystalline compound that forms open regular micropores (hereinafter, may be simply referred to as "pores"), usually called zeolite, and has a tetrahedral structure. It _{has a structure in which 4} units of TO (T means an element other than oxygen constituting zeolite) share an oxygen atom and are three-dimensionally linked.

The metallosilicate of the present invention has an AEI type structure.
Metallosilicates having an AEI-type structure have three-dimensional pores composed of three types of 3.8 × 3.8 Å 8-membered ring pores. By intersecting the 8-membered ring pores, a wide cavity (cage) exists in the structure. Moreover, when the unit cell (unit cell) of the AEI type structure is represented by an atom having fixed spatial coordinates, its composition is T ₄₈ O _96, which is a monoclinic system.

The framework density of metallosilicates having an AEI-type structure is usually 14.8 T / nm ³ .
The framework density (unit: T / nm ³ ) means the number of atoms T other than oxygen that form the skeleton existing per unit volume (1 nm ^{3) of zeolite, and this value is determined by the structure of zeolite.} It is a thing. The relationship between the framework density and the structure of zeolite is shown in the data collection on zeolite (Atlas of Zeolite Framework Types, Sixth Revised Edition 2007, ELSEVIER) compiled by the Structure Commission of IZA. ..

(Structural component)
In addition to silicon and oxygen, the metallosilicates of the present invention contain at least one element M selected from aluminum, gallium, boron, and iron. The metallosilicate of the present invention contains 70 mol% or more of silicon atoms in T atoms.
If the metallosilicate contains aluminum, gallium, or iron, these atoms are incorporated into the skeleton as T atoms of the metallosilicate to become relatively strong acid points, which serve as active points for the methanol conversion reaction. Therefore, it has excellent catalytic activity. Specific examples thereof include aluminum-containing aluminosilicates, gallium-containing gallosilicates, boron-containing borosilicates, and iron-containing ferricates.

Further, when boron is contained in the metallosilicate, a boron atom is incorporated into the skeleton as a T atom of the metallosilicate, resulting in a relatively weak acid point. Therefore, boron can appropriately adjust the acid properties and the amount of acid of the metallosilicate by coexisting with other constituent elements such as aluminum and gallium that exhibit strong acid properties. Specific examples thereof include boroaluminosilicate containing aluminum and boron, galloaluminosilicate containing gallium and boron, and the like.

It is preferable that the metallosilicate of the present invention contains at least aluminum in terms of promoting the methanol conversion reaction due to its particularly strong acidity and suppressing desorption from the skeleton, so that the catalyst has a long life.
The metallosilicate of the present invention is preferably aluminosilicate, boroaluminosilicate, galosilicate, galoborosilicate, ferricate, more preferably aluminosilicate, boroaluminosilicate, and further. Aluminosilicate is preferred.

Further, the metallosilicate of the present invention may contain other elements in addition to the above-mentioned elements. Examples of other elements include, but are not limited to, zinc (Zn), germanium (Ge), titanium (Ti), zirconium (Zr), tin (Sn) and the like. These constituent elements may be one kind or two or more kinds.
_{SiO 2} / M ₂ O ₃ of the metallosilicate of the present invention (however, the denominator of the molar ratio represents the total amount of _{Al 2} O ₃ , Ga ₂ O ₃ , B ₂ O ₃ and Fe ₂ O _3). Is 5 or more, preferably 10 or more, more preferably 12 or more, still more preferably 15 or more, less than 100, preferably 60 or less, more preferably 40 or less, still more preferably 30 or less. The above ratio is a value obtained on the assumption that _{all Si atoms in the metallosilicate are contained as SiO 2 and} all the M contained in the metallosilicate is contained as M ₂ O _3. When the SiO ₂ / M ₂ O ₃ molar ratio is in the above range, the amount of acid derived from the strong acid point and the weak acid point can be sufficiently obtained, and high methanol adsorption ability, high methanol conversion activity and olefin interconversion activity can be obtained. Further, it is possible to prevent phenomena such as deactivation of the catalyst due to coke adhesion, desorption of T atoms other than silicon from the skeleton, and decrease in acid strength per acid point. _{The SiO 2} / M ₂ O ₃ molar ratio of the metallosilicate of the present invention can usually be measured by ICP elemental analysis or fluorescent X-ray analysis. In the fluorescent X-ray analysis, a calibration curve of the fluorescent X-ray intensity of the analytical element in the standard sample and the atomic concentration of the analytical element is prepared, and the calibration curve is used in the metallocate sample by the fluorescent X-ray analysis method (XRF). The contents of silicon atom, aluminum, gallium, and iron atom can be determined. Since the fluorescent X-ray intensity of the boron element is relatively small, it is preferable to measure the content of the boron atom by ICP elemental analysis.

The phosphorus content contained in the crystals of the metallosilicate of the present invention is not particularly limited, but is preferably small, usually 500 ppm or less, preferably 300 ppm or less, more preferably 100 ppm or less, and most preferably 0 ppm. Is. By setting the phosphorus content in the crystal of the metallosilicate in the above range, a sufficient specific surface area can be obtained, a high intracrystal diffusibility of the hydrocarbon component can be obtained, and the methanol conversion activity can be increased. .. Since side reactions at phosphorus-derived acid points are suppressed, the yields of propylene and linear butene can be improved. The metallosilicate of the present invention may contain a part of phosphorus in the skeleton and / or outside the skeleton of the metallosilicate, but it is preferably contained only outside the skeleton, and more preferably. It is not contained.

(Total acid amount)
The total acid amount of the metallosilicate of the present invention (hereinafter referred to as the total acid amount) is the amount of acid points existing in the crystal pores of the metallosilicate and the amount of the acid point on the outer surface of the crystal of the metallosilicate. It is the sum of (hereinafter referred to as the amount of acid on the outer surface). The total amount of acid is not particularly limited, but is usually 0.001 mmol / g or more, preferably 0.01 mmol / g or more, more preferably 0.03 mmol / g or more, still more preferably 0.05 mmol / g or more. , Particularly preferably 0.07 mmol / g or more. Further, it is usually 1.2 mmol / g or less, preferably 0.80 mmol / g or less, more preferably 0.50 mmol / g or less, still more preferably 0.30 mmol / g or less, and particularly preferably 0.20 mmol / g or less. .. By setting the total amount of acid in the above range, the conversion activity of methanol is ensured, coke formation inside the pores of metallosilicate is suppressed, and the diffusibility in the crystal of the molecule is increased, so that propylene and propylene are used. It is preferable in that it can promote the production of linear butene.

Here, the total acid amount is calculated from the desorption amount of ammonia temperature-programmed desorption _(NH 3 -TPD). Specifically, as a pretreatment, the metallosilicate is dried under vacuum at 500 ° C. for 30 minutes, and then the pretreated metallosilicate is brought into contact with an excess amount of ammonia at 100 ° C. to adsorb ammonia to the metallosilicate. Let me. Excess ammonia is removed from the metallosilicate by vacuum drying it at 100 ° C. (or contacting it with water vapor at 100 ° C.). Next, the metallosilicate on which ammonia is adsorbed is heated at a heating rate of 10 ° C./min in a helium atmosphere, and the amount of ammonia desorbed at 100-600 ° C. is measured by mass spectrometry. The amount of ammonia desorbed per metallocate is taken as the total acid amount. However, the total amount of acid in the present invention is the total area of the waveform having the peak top of 240 ° C. or higher after the TPD profile is waveform-separated by the Gaussian function. This "240 ° C." is an index used only for determining the position of the peak top, and does not mean to obtain the area of the portion of 240 ° C. or higher. As long as the peak top is a waveform of 240 ° C. or higher, the "area of the waveform" is the total area including the portion other than 240 ° C. When there are a plurality of waveforms having peak tops at 240 ° C. or higher, the sum of the areas thereof is used.
The total amount of acid in the present invention does not include the amount of acid derived from a weak acid point having a peak top of less than 240 ° C. This is because it is not easy to distinguish between adsorption derived from a weak acid point and physical adsorption in the TPD profile.

(Amount of acid on the outer surface)
The amount of acid on the outer surface of the crystal of the metallosilicate of the present invention is not particularly limited, but is usually preferably 5% or less, preferably 3% or less, based on the total acid amount of the metallosilicate. Is more preferable, and 0% is most preferable.
If the amount of outer surface acid is too large, the selectivity of propylene or linear butene tends to decrease due to side reactions that occur at the outer surface acid points. It is presumed that this is because the reaction for producing hydrocarbons other than the target substance proceeds at the acid point on the outer surface. Further, it is presumed that the propylene or linear butene produced in the pores of the metallosilicate further reacts at the acid point on the outer surface, which is also one of the causes of the decrease in selectivity.

The value of the amount of acid on the outer surface of the metallosilicate of the present invention can be measured by the method described in International Publication No. 2010/128644 pamphlet.
The method for adjusting the amount of acid on the outer surface of the metallosilicate within the above range is not particularly limited, but usually includes methods such as silylation of the outer surface of the metallosilicate, steam treatment, and heat treatment. Further, a method of binding the binder and the outer surface acid point of the metallosilicate when molding the metallosilicate can be mentioned.

(Weak acid amount)
In the present invention, not only the total acid amount of the metallosilicate, but also the weak acid points derived from aluminum, gallium, boron, and iron contained in the metallosilicate are effective for methanol adsorption, methanol conversion, and olefin interconversion. Acts on. Therefore, as an index of the amount of weak acid derived from the weak acid point, the value obtained by subtracting the total amount of acid (mmol / g) from the total amount (mmol / g) of aluminum, gallium, boron, and iron contained in the metallocate. (Mmol / g), is used. This value is usually 0.10 mmol / g or more, preferably 0.30 mmol / g or more, more preferably 0.50 mmol / g or more, still more preferably 1.0 mmol / g or more, and usually 5.0 mmol / g or less. It is preferably 4.0 mmol / g or less, more preferably 3.0 mmol / g or less, still more preferably 2.0 mmol / g or less. By setting this value in the above range, methanol adsorption and methanol conversion can be promoted, and high catalytic activity can be obtained.
The total amount (mmol / g) of aluminum, gallium, boron, and iron contained in the metallocate is calculated by ICP elemental analysis, XRF analysis, or the like.

(Ion exchange site)
The ion exchange site of the metallosilicate of the present invention is not particularly limited. Usually, proton type (hereinafter, also referred to as H type), partly alkali metals such as sodium (Na), potassium (K) and cesium (Cs); magnesium (Mg), calcium (Ca), strontium (Sr) and Alkaline earth metals such as barium (Ba); metal ions such as. The ion exchange site is preferably proton, sodium, potassium, calcium, more preferably proton, sodium, potassium, still more preferably sodium, potassium, and particularly preferably sodium. Hereinafter, for example, those exchanged with Na ions may be referred to as "Na type". Those ion-exchanged with ammonium (NH ₄ ) are usually treated in the same manner as the proton type because ammonia is eliminated under high temperature under the reaction conditions.

The total content of the alkali metal and the alkaline earth metal in the metallosilicate of the present invention is not particularly limited, but is usually 0.005% by mass or more, preferably 0.01% by mass or more, and more preferably 0. 1% by mass or more, more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, usually 10% by mass or less, preferably 8% by mass or less, more preferably 6% by mass or less, still more preferably 4 It is mass% or less, particularly preferably 2 mass% or less. By setting the total content of the alkali metal and the alkaline earth metal within the above range, the acid amount of the metallosilicate and the cage space volume can be adjusted, so that coke accumulation during the reaction can be suppressed. It is preferable in that respect. It is also preferable in that the thermal / hydrothermal stability is improved and deterioration due to dealumination can be suppressed.

(Containing metal)
In addition to these ion exchange sites, alkali metals such as Na and K; alkaline earth metals such as Mg and Ca; and transition metals such as Cr, Cu, Ni, Fe, Mo, W, Pt, and Re are supported by metals. May be good. Here, the metal support can usually be carried out by an impregnation method such as an equilibrium adsorption method, an evaporation dry drying method, or a pore filling method.
The total amount of the alkali metal and the alkaline earth metal in the metallosilicate of the present invention is preferably in the above range even when it is contained in other than the ion exchange site.

(Average primary particle size)
The average primary particle size of the metallosilicate of the present invention is not particularly limited, but is usually 0.03 μm or more, preferably 0.05 μm or more, more preferably 0.1 μm or more, still more preferably 0.15 μm or more. It is particularly preferably 0.20 μm or more, usually 5 μm or less, preferably 2 μm or less, more preferably 1 μm or less, still more preferably 0.60 μm or less, and particularly preferably 0.40 μm or less. Within the above range, the diffusibility in the zeolite crystal and the catalytic effectiveness coefficient in the catalytic reaction are sufficiently high, the zeolite crystallinity is sufficient, and the hydrothermal stability is high, which is preferable.

The average primary particle size in the present invention corresponds to the particle size of the primary particles. Therefore, it is different from the particle size of the agglomerate measured by a light scattering method or the like. The average particle size is determined by arbitrarily measuring 20 or more particles when observing particles with a scanning electron microscope (hereinafter abbreviated as "SEM") or a transmission electron microscope (hereinafter abbreviated as "TEM"). Then, the particle size of the primary particles is averaged. If the particle is rectangular, measure the long and short sides of the particle (without measuring the depth), calculate the average of the sums (that is, (long side + short side) ÷ 2), and then calculate the particle of that particle. The diameter.

(BET specific surface area)
The BET specific surface area of the metallosilicate of the present invention is not particularly limited, but is usually 300 m ² / g or more, preferably 400 m ² / g or more, more preferably 500 m ² / g or more, and usually 1000 m ^{2 or more.} It is / g or less, preferably 800 m ² / g or less, and more preferably 750 m ² / g or less. Within the above range, there are sufficiently many active sites existing on the inner surface of the pores, and the catalytic activity is increased, which is preferable. The BET specific surface area can be measured by a measuring method according to JIS8830 (method for measuring the specific surface area of powder (solid) by gas adsorption). Nitrogen is used as the adsorbed gas, and the BET specific surface area is determined by the one-point method (relative pressure: p / p0 = 0.30).

(Pore volume)
The pore volume of the metallosilicate of the present invention is not particularly limited, but is usually 0.1 ml / g or more, preferably 0.2 ml / g or more, and usually 3 ml / g or less, preferably 2 ml / g. It is less than or equal to g. Within the above range, there are sufficiently many active sites existing on the inner surface of the pores, and the catalytic activity is increased, which is preferable. The pore volume is preferably a value obtained from the adsorption isotherm of nitrogen obtained by the relative pressure method.

(Production method)
The method for producing the metallosilicate of the present invention is not particularly limited, and for example, it can be produced by a known method such as the method described in US Pat. No. 5,953,370.
The metallosilicate of the present invention can generally be prepared by a hydrothermal synthesis method. For example, at least one selected from an aluminum source, a gallium source, a boron source, and an iron source, a silicon source, an alkaline aqueous solution, etc. are added to water to generate a uniform gel, and a structure defining agent is added to this as necessary. Stir to prepare the raw material gel. The obtained raw material gel is heated in a closed container and reacted under self-pressure to crystallize it. The reaction temperature at this time is not particularly limited, but is usually kept at 100 to 200 ° C. for crystallization. A seed crystal may be added at the time of crystallization as needed, and it is preferable to add the seed crystal in terms of manufacturability because the reaction time can be shortened and the crystal particles can be made into fine particles. Then, after filtering and washing the crystallized solid component, the solid content is dried and subsequently calcined to obtain an alkali (earth) metal type metalloidate. The drying temperature is not limited, but is usually 100 to 200 ° C. The firing temperature is not limited, but is usually 400 to 700 ° C. Then, the H-type metallosilicate can be obtained by ion-exchange with an acidic solution or an ammonium salt solution and calcining.

Further, after hydrothermal synthesis, treatments such as ion exchange, impregnation, and acid treatment may be added to change the composition of the metallosilicate. The ion exchange and impregnation treatment can be performed using an aqueous solution containing at least one element source selected from the group consisting of aluminum, gallium, boron, and iron, and the content of the above elements can be increased. Further, the acid treatment can be carried out using an acidic aqueous solution such as an inorganic acid or an organic acid, and the content of the above elements can be reduced.

A structure-defining agent is usually used for the production of the metallosilicate, and the structure-determining agent described in US Pat. No. 5,953,370 is preferable. Specifically, a cation derived from N, N-dialkylpiperidine, a cation derived from N, N-dialkyl-9-azonia bicyclo [3.3.1] nonane, 2-azonia bicyclo [3.2.1]. Examples include cations derived from octane, cations derived from N, N-dialkyl-2,5-dihydropyrrole and the like.

The two independent alkyl groups, N, N-dialkylpiperidin and N, N-dialkyl-2,5-dihydropyrrole, are not particularly limited as long as they serve as a structure defining agent that contributes to the formation of AEI type structure. , Usually a lower alkyl group, preferably an alkyl group having 4 or less carbon atoms, and more preferably a methyl group or an ethyl group. Further, the alkyl group may be linear or branched, and the two alkyl groups may be bonded to each other to form a ring. When two alkyl groups are bonded to each other to form a ring, the two alkyl groups usually form a methylene chain having 4 to 6 carbon atoms, preferably a methylene chain having 4 carbon atoms.

Further, the piperidine ring of the N, N-dialkylpiperidine may have a substituent. The substituent is usually a lower alkyl group, preferably an alkyl group having 4 or less carbon atoms, and more preferably a methyl group or an ethyl group. The number of substituents may be 2 or more.
Of the above, preferably N, N-dimethyl-3,5-dimethylpiperidium cation, N, N-diethyl-2,6-dimethylpiperidium cation, N, N-dimethyl-9-azonia bicyclo [3.3. 1] Nonane cation and the like.

The cation used as the structure defining agent is accompanied by an anion that does not inhibit the formation of the metallosilicate of the present invention. The anion is not particularly limited, but specifically includes halogen ions such as Cl-, Br-, and I-, hydroxide ions, acetates, sulfates, and carboxylates. Among them, hydroxide ions are particularly preferably used.
Further, as a phosphorus-containing structure-determining agent, a substance such as tetraethylphosphonium hydroxide or tetraethylphosphonium bromide can also be used.

However, the phosphorus compound is preferably a nitrogen-based structure-determining agent because it may generate a harmful substance such as diphosphorus pentoxide when the structure-determining agent is removed from the synthetic metallosilicate by calcination.
As a method for synthesizing AEI-type metallocate, there is a known technique of adding a fluorine source such as hydrofluoric acid instead of an alkaline source, but hydrofluoric acid is a very dangerous acid, let alone. It is not industrially practical to use it during hydrothermal synthesis at high temperatures. Further, the AEI type metallosilicate synthesized by adding hydrofluoric acid is not preferable in the following points for use as a catalyst for producing propylene and linear butene.

(1) The composition is high silica (Si / M ₂ ratio> 100), the number of strong acid points tends to be small, the number of weak acid points tends to be small, and the adsorption activity of methanol and the conversion activity to olefin tend to be low.
(2) The particle size is large, and the effective coefficient of the catalyst tends to be small.
(3) Even if firing is performed to remove the structure-determining agent, fluorine is not removed, the specific surface area and pore volume tend to be small, and the conversion activity to olefin tends to be low.

It is preferable that the metallosilicate having an AEI type structure of the present invention is appropriately subjected to at least one treatment selected from steam treatment, heat treatment, acid treatment and ion exchange after the above-mentioned firing. Of these, at least one treatment selected from steam treatment, heat treatment, and ion exchange is preferably performed, and more preferably, at least one treatment selected from steam treatment and ion exchange is performed, which is even more preferable. Is steam-treated. In addition to these treatments, silylation treatment may be performed before use. It is preferably a combination of at least one treatment selected from steam treatment and ion exchange and a silylation treatment, and more preferably a combination of steam treatment and silylation treatment.
Hereinafter, these processing methods will be described.

<Steam treatment>
The method for treating water vapor of the metallosilicate having the AEI type structure of the present invention is not particularly limited, but it can be brought into contact with a gas containing water vapor as long as the effects of the present invention are not impaired. Specific examples thereof include a method of contacting with water vapor, water vapor diluted with air or an inert gas, a reaction atmosphere containing water vapor together with methanol and / or dimethyl ether, a reaction atmosphere for generating water vapor, and the like. The reaction that produces water vapor is a reaction in which dehydration occurs to generate water vapor, such as the dehydration reaction of methanol and / or dimethyl ether. Although water vapor may partially exist as liquid water depending on the conditions, it is preferable that the entire metallosilicate salt is present in the state of water vapor in order to give a uniform water vapor treatment effect. ..

It is considered that not only the amount of the outer surface acid but also the total amount of the acid is reduced because the heterometal atoms forming the skeleton of the metallosilicate are eliminated from the entire crystal by the steam treatment. This decrease in the total amount of acid suppresses the formation of cork inside the pores of the metallosilicate, and improves the intracrystal diffusivity of the molecule. Therefore, it is presumed that the production of linear butene, which is a molecule larger than propylene, is relatively promoted.

When excessive water vapor treatment is performed, the diffusibility of the molecule in the crystal increases more than necessary, and the amount of hydrocarbon molecules having 5 or more carbon atoms such as pentene and hexene tends to increase.
The steam treatment temperature of the metallosilicate is not particularly limited, but is usually 600 ° C. or higher, preferably 700 ° C. or higher, more preferably 750 ° C. or higher, still more preferably 800 ° C. or higher. Further, it is usually 1000 ° C. or lower, preferably 950 ° C. or lower, more preferably 900 ° C. or lower, and further preferably 850 ° C. or lower. By setting the steam treatment temperature in the above range, heterometal atoms can be efficiently removed from the skeleton in a short treatment time without causing collapse of the skeleton structure, which is preferable.

The steam used for steam treatment can be diluted with air or an inert gas such as helium or nitrogen. The water vapor concentration at that time is not particularly limited, but is usually 5% by volume or more, preferably 20% by volume or more, more preferably 35% by volume, based on the total gas used for steaming the metallocate. % Or more, more preferably 50% by volume or more, usually 100% by volume or less, preferably 90% by volume or less, more preferably 80% by volume or less, still more preferably 70% by volume or less.

By setting the water vapor concentration in the above range, the T atom can be efficiently removed from the skeleton in a short treatment time, which is preferable.
The pressure of steam treatment (total pressure including diluting gas) is not particularly limited, but is usually 50 kPa (absolute pressure, the same applies hereinafter) or more, preferably 75 kPa or more, more preferably 100 kPa or more, and usually 2 MPa or less. It is preferably 1 MPa or less, more preferably 0.5 MPa or less. By setting the pressure of steam treatment in the above pressure range, the T atom can be efficiently removed from the skeleton in a short time, which is preferable.

The partial pressure of water vapor is not particularly limited, but is usually 0.01 MPa or more (absolute pressure, the same applies hereinafter), preferably 0.03 MPa or more, more preferably 0.05 MPa or more, still more preferably 0.06 MPa or more. It is particularly preferably 0.07 MPa or more, usually 3 MPa or less, preferably 2 MPa or less, more preferably 1 MPa or less, still more preferably 0.2 MPa or less, and particularly preferably 0.1 MPa or less. By setting the partial pressure of water vapor within the above pressure range, the T atom can be efficiently removed from the skeleton in a short time, which is preferable.

The steam treatment time of the metallosilicate is not particularly limited, but is usually 0.1 hours or more, preferably 0.5 hours or more, and more preferably 1 hour or more. There is no upper limit to the treatment time as long as the catalytic activity is not significantly impaired. The treatment time can be appropriately adjusted depending on the steam treatment temperature and the steam concentration.
The steam treatment of the metallosilicate may be carried out in a state where an organic substance is present inside the pores. Since the organic substance is present inside the pores, it is possible to significantly reduce the acid points on the outer surface while preventing an extreme decrease in the acid points inside the pores when a particularly strong steam treatment is performed.

Examples of the organic substance include, but are not limited to, a structure-determining agent used during hydrothermal synthesis of metallosilicates, cork produced by a reaction, and the like. These organic substances can also be removed through a combustion step such as air firing after steam treatment of the metallosilicate after hydrothermal synthesis (hereinafter, may be referred to as a metallosilicate before firing), or air or the like. By treating with steam diluted with the oxygen-containing gas of the above, steam treatment can also be performed while removing organic substances.

It is also possible to physically mix the metallosilicate with a compound containing an alkaline earth metal before subjecting it to steam treatment. By adding an alkaline earth metal, it may be possible to neutralize the strong acid point of the metallosilicate and suppress the formation of cork produced at the strong acid point. Examples of the compound containing an alkaline earth metal include calcium carbonate, calcium hydroxide and magnesium carbonate, and calcium carbonate is preferable.
The amount of the compound containing an alkaline earth metal is not particularly limited, but is usually 0.5% by mass or more, preferably 3% by mass or more, usually 30% by mass or less, preferably 10% by mass, based on the metallosilicate. It is as follows.

<Heat treatment>
The method for heat-treating the metallosilicate having the AEI type structure of the present invention is not particularly limited, but specifically, the metallosilicate is placed in at least one atmosphere selected from air and an inert gas. Examples thereof include a method of high temperature treatment and a method of high temperature treatment in a mixed gas atmosphere containing methanol and / or dimethyl ether.

In the heat treatment of the metallocate, the total amount of acid due to the elimination of heterometal atoms in the skeleton can be reduced as in the case of steam treatment.
The heat treatment temperature is not particularly limited, but is usually 600 ° C. or higher, preferably 700 ° C. or higher.
As described above, it is more preferably 800 ° C. or higher, further preferably 900 ° C. or higher, usually 1200 ° C. or lower, preferably 1100 ° C. or lower, more preferably 1000 ° C. or lower, still more preferably 950 ° C. or lower. By setting the heat treatment temperature in the above range, it is preferable that the T atom can be efficiently removed from the skeleton in a short treatment time without causing the skeleton structure to collapse.

As the gas type used in the heat treatment, helium, nitrogen, air or the like can be used.
Similar to the steam treatment, the heat treatment may be performed in a state where an organic substance is present inside the pores. When an inert gas such as helium or nitrogen is used, the organic substance may be carbonized by heat treatment, but it can be removed by firing with air.

The heat treatment may be performed at the same time as the calcination performed when the metallosilicate is produced, or may be separately performed separately. The heat treatment is performed at a relatively high temperature for the purpose of desorption of the T atom in the skeleton, and is not particularly limited. Specifically, when the above firing and the heat treatment are performed separately, The heat treatment is usually performed at a temperature higher than that of the firing.
The heat treatment time is not particularly limited, but is usually 0.1 hours or more, preferably 0.5 hours or more, and more preferably 1.0 hours or more. Further, there is no upper limit of the treatment time as long as the catalytic activity is not significantly impaired, and the treatment time can be appropriately adjusted depending on the heat treatment temperature.

<Acid treatment>
The method for acid treatment of the metallosilicate having an AEI type structure of the present invention is not particularly limited, and specific examples thereof include a method using an acidic aqueous solution.
The type of acid used in the acidic aqueous solution is not particularly limited, but is not limited to inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid and phosphoric acid, carboxylic acids such as formic acid, acetic acid and propionic acid, oxalic acid, malonic acid and the like. Dicarboxylic acid and the like can be used. Of these, sulfuric acid, nitric acid and hydrochloric acid are preferred.

The acid concentration of the acidic aqueous solution is not particularly limited, but is usually 0.01 M or more, preferably 0.1 M or more, more preferably 1 M or more, usually 10 M or less, and preferably 8 M or less. It is more preferably 6M or less. By setting the acid concentration in the above range, the T atom can be efficiently removed from the skeleton in a short treatment time without causing the collapse of the skeleton structure, which is preferable.

The amount of the acidic aqueous solution with respect to the metallosilicate is not particularly limited, but the total amount of the acidic aqueous solution is usually 3 g or more, preferably 5 g or more, more preferably 10 g or more with respect to 1 g of the metallosilicate. It is usually 100 g or less, preferably 80 g or less, and more preferably 50 g or less. By setting the amount of the acidic aqueous solution in the above range, it is preferable in that sufficient stirring efficiency of the slurry can be obtained and a certain productivity can be ensured.

The temperature of the acid treatment is not particularly limited, but it can be carried out at normal pressure from room temperature to 100 ° C. and in a pressure-resistant container at 100 ° C. or higher, and is usually 40 ° C. or higher, preferably 60 ° C. or higher. , More preferably 80 ° C. or higher, usually 200 ° C. or lower, preferably 180 ° C. or lower, more preferably 160 ° C. or lower. By setting the acid treatment temperature within the above range, heterometal atoms can be efficiently removed from the skeleton in a short time while suppressing the collapse of the skeleton structure.

The treatment time of the acid treatment is not particularly limited and depends on the acid concentration and the reaction temperature, but is usually 0.01 hours or more, preferably 0.1 hours or more, as long as the performance of the catalyst is not impaired. There is no particular upper limit on the processing time. The treatment time can be appropriately adjusted depending on the acid concentration and the reaction temperature.
By adding a silylating agent to the acidic aqueous solution, the acid treatment and the silylation treatment can be performed at the same time. The silylating agent used at that time is the same as the silylating agent.

<Ion exchange>
The counter cation of the metalloid atom of the metalloid is usually an alkali metal such as sodium, an alkaline earth metal, ammonium (NH ₄ ) or a proton (H). These counter cations are ion-exchangeable and can be used by appropriately exchanging metal ions.

The metal to be exchanged is not particularly limited, and examples thereof include alkali metals such as lithium, sodium, potassium, rubidium and cesium, and alkaline earth metals such as magnesium, calcium, strontium and barium. It is preferably sodium, potassium, magnesium and calcium, more preferably sodium, potassium and calcium, and even more preferably sodium and potassium. By ion exchange, the acid amount of metallocate and the cage space volume can be adjusted, which is preferable in that coke accumulation during the reaction can be suppressed. It is also preferable in that the thermal / hydrothermal stability is improved and deterioration due to dealumination can be suppressed.

The method of metal ion exchange is not particularly limited, but can be performed by a known ion exchange method. The cation of the metallosilicate when used in the ion exchange method is not particularly limited, and a sodium type, an ammonium type, or a proton type is usually used.
As the metal source, nitrates, sulfates, acetates, carbonates, chloride salts, bromide salts, iodide salts and the like are usually used, preferably nitrates, sulfates, chloride salts, and more preferably nitrates. Is.

The solvent used is not particularly limited as long as it dissolves the metal source, but water is usually used.
The concentration of the metal source solution is not particularly limited, but is usually 0.1 M or more, preferably 0.5 M or more, more preferably 1 M or more, and the upper limit is usually 10 M or less, preferably 8 M or less. More preferably, it is 6 M or less. It is desirable to adjust the concentration according to the solubility of the metal source.

The temperature at which ion exchange is performed is from room temperature to about the boiling point of the solvent. The treatment time may be any time as long as the ion exchange reaches a sufficient equilibrium, and is usually about 1 to 6 hours. It is also possible to repeat ion exchange multiple times in order to increase the metal exchange rate.
Separation of the metallocate from the suspension treated for a predetermined time is carried out by a usual solid-liquid separation operation, such as filtration or centrifugation.

The atmosphere for drying the metallosilicate after ion exchange is not particularly limited, and is performed, for example, in air, in an inert gas, in vacuum, or the like. The drying temperature is usually from room temperature to about the boiling point of the solvent.
The metallosilicate after ion exchange is used after being appropriately calcined. The firing temperature may be higher than the decomposition temperature of the metal source, and is usually 200 ° C. to 600 ° C., preferably 300 ° C. to 500 ° C. If the calcination temperature is too low, the metal source tends to remain, and if the calcination temperature is too high, the structure of the metallocate is likely to collapse and metal sintering is likely to proceed.

<Cyrilization treatment>
The method for silylating the metallosilicate having an AEI type structure is not particularly limited, and a known method can be appropriately used, specifically, liquid phase silylation, gas phase silylation, or the like. Can be done.
It is considered that the amount of acid on the outer surface of the metallosilicate having an AEI type structure is reduced by the silylation treatment, which usually covers the acid spots on the outer surface and is inactivated. When the amount of acid on the outer surface decreases, side reactions that occur on the outer surface of the metallosilicate are suppressed. Specifically, when the organic compound raw material or the lower olefin generated in the pores of the metallosilicate comes into contact with the acid point on the outer surface of the metallosilicate, the reaction of forming a component other than the target substance is suppressed. It is considered to be effective. Further, in the silylation of the outer surface acid point, since the silyl group is also bonded to the acid point constituting the pores of the metallocate, the pore diameter of the outer surface opening is slightly reduced to the outside of the crystal. It is also considered to have the effect of suppressing molecular diffusion. It is considered that this makes it possible to suppress the formation of hydrocarbons having 5 or more carbon atoms, which are larger molecules, and improve the selectivity of lower olefins.

Hereinafter, the silylation treatment will be specifically described by taking liquid phase silylation as an example.
The silylating agent is not particularly limited, and usually, an agent capable of silylating the outer surface of the metallosilicate and not being able to silylate the inside of the pores of the metallosilicate is used. Specifically, silicones, chlorosilanes, alkoxysilanes, siloxanes, silazanes and the like can be used. Of these, chlorosilanes are usually used for gas phase silylation, and alkoxysilanes are usually used for liquid phase silylation, and more preferable silylating agents are highly reactive and relatively easy to handle. , Alkoxysilanes.

Specific examples of silicones include dimethyl silicone, diethyl silicone, phenyl methyl silicone, methyl hydrogen silicone, ethyl hydrogen silicone, phenyl hydrogen silicone, methyl ethyl silicone, phenyl ethyl silicone, diphenyl silicone, and methyl trifluoropropyl silicone. , Ethyltrifluoropropyl silicone, tetrachlorophenylmethyl silicone, tetrachlorophenylethyl silicone, tetrachlorophenylhydrogen silicone, tetrachlorophenyl silicone, methyl vinyl silicone, ethyl vinyl silicone and the like are used.

Specific examples of the chlorosilanes include tetrachlorosilane, trichlorosilane, trichloromethylsilane, dichlorodimethylsilane, chlorotrimethylsilane, trichloroethylsilane, dichlorodiethylsilane, and chlorotriethylsilane.
Specific examples of the alkoxysilanes include tetramethoxysilane, tetraethoxysilane, etc .; quaternary alkoxysilane, trimethoxymethylsilane, trimethoxyethylsilane, triethoxymethylsilane, triethoxyethylsilane, etc.; Alkoxysilane, dimethoxydimethylsilane, dimethoxydiethylsilane, diethoxydimethylsilane, diethoxydiethylsilane, etc .; secondary alkoxysilane, methoxytrimethylsilane, methoxytriethylsilane, ethoxytrimethylsilane, ethoxytriethylsilane, etc .; primary alkoxysilane Is used. It is preferably a secondary or higher alkoxysilane, more preferably a tertiary or higher alkoxysilane, and even more preferably a quaternary alkoxysilane.

Specific examples of the siloxanes include hexamethyldisiloxane, hexaethyldisiloxane, pentamethyldisiloxane, tetramethyldisiloxane, and the like, with hexamethyldisiloxane being preferred.
Specific examples of the silazanes include hexamethyldisilazane, dipropyltetramethyldisilazane, diphenyltetramethyldisilazane, tetraphenyldimethyldisilazane and the like, and hexamethyldisilazane is preferable.

The amount of the silylating agent with respect to the metallosilicate is not particularly limited, but is usually 0.001 mol or more, preferably 0.01 mol or more, and more preferably 0, based on 1 mol of the metallosilicate. .1 mol or more. Further, it is usually 5 mol or less, preferably 3 mol or less, and more preferably 1 mol or less. By setting the amount of the silylating agent in the above range, the silylation coating of the outer surface acid spots proceeds efficiently, and the decrease in catalytic activity due to the excessive silylation coating can be suppressed, which is preferable. The amount of the silylating agent is represented by the number of moles of Si atoms contained in the silylating agent, and in the case of a silylating agent having a plurality of Si atoms in the molecule, the total number of moles of the Si atoms is silyl. It will be treated as the number of moles of the agent.

When liquid phase silylation is performed, a solvent can be used, and the solvent is not particularly limited, but hydrocarbons such as hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, benzene, toluene, and xylene. And water can be used. When liquid phase silylation is performed with an aqueous solvent, an acidic aqueous solution to which an acid such as sulfuric acid or nitric acid is added can be used in order to promote the silylation reaction.

When liquid phase silylation is carried out, the concentration of the silylating agent in the solution for which the liquid phase silylation reaction is carried out is not particularly limited, but is usually 0.01% by mass or more, preferably 0.5% by mass or more. As mentioned above, it is more preferably 1% by mass or more. Further, it is usually 80% by mass or less, preferably 60% by mass or less, and more preferably 40% by mass or less. By setting the concentration of the silylating agent in the above range, condensation between the silylating agents can be suppressed and the silylation rate can be maintained, which is preferable.

The amount of the solvent with respect to the metallosilicate when performing liquid phase silylation is not particularly limited, but is usually 1 g or more, preferably 3 g or more, more preferably 5 g or more with respect to 1 g of the metallosilicate. Is. Further, it is usually 100 g or less, preferably 80 g or less, and more preferably 50 g or less. By setting the amount of the solvent in the above range, it is preferable in that sufficient stirring efficiency of the slurry can be obtained and a certain productivity can be ensured.

When liquid phase silylation is performed, a specific range of water may be added to the metallosilicate to be subjected to the silylation treatment. The water content of the metallosilicate may be adjusted to a specific range by artificially supplying water even if the metallosilicate originally contains the water. Usually, as the metallosilicate of the present invention, one obtained by hydrothermal synthesis is calcined, and if necessary, it is converted into an ammonium type and then calcined to be converted into a proton type. Therefore, it is usually assumed that the water content of the metallosilicate before the silylation treatment is very small, and the metallosilicate may be subjected to the silylation treatment as it is, or the water content of the metallosilicate is set to a specific water content. May be used after adjusting the water content (hereinafter, may be referred to as humidity control treatment).

The water content is not particularly limited, but the weight of water contained in the metallosilicate is represented by mass% with respect to the weight of the dry metallosilicate, and is usually 30% by mass or less, preferably 25% by mass or less. The lower limit is 0% by mass in a completely dry state. By setting the water content in the above range, the silylated coating of the outer surface acid spots proceeds efficiently, and pore clogging due to excessive silylation can be prevented, which is preferable.

The humidity control treatment method is not particularly limited as long as it can be adjusted to a predetermined water content. For example, a method of leaving the metallosilicate in the air having an appropriate relative humidity, the metallosilicate is allowed to coexist in a closed container (desiccanter, etc.) together with a saturated aqueous solution of water or an inorganic salt, and left in a saturated steam atmosphere. A method of circulating a gas having an appropriate water vapor pressure through the metallosilicate. In the above method, in order to perform more uniform humidity control, the humidity control treatment may be performed while mixing or stirring the metallosilicate.

The temperature at which the silylation treatment is performed is appropriately adjusted depending on the type of silylating agent and solvent used, and is not particularly limited, but is usually 20 ° C. or higher, preferably 40 ° C. or higher, and more preferably 60 ° C. or higher. .. Further, it is usually 140 ° C. or lower, preferably 120 ° C. or lower, and more preferably 100 ° C. or lower. By setting the silylation treatment temperature within the above range, the discharge of water in the metallosilicate pores is suppressed, so that the silylation coating of the outer surface acid point proceeds efficiently and the silylation rate is increased. It is preferable because it can be maintained.

The time required to raise the temperature from the addition of the silylating agent to the silylation temperature is not particularly limited, and the silylating agent may be added at the silylation temperature, but it is usually 0.01 hour. As described above, it is preferably 0.05 hours or more, more preferably 0.1 hours or more, and there is no particular upper limit on the time required for raising the temperature. When the silylation temperature is high, by setting the time required for raising the temperature within the above range, the discharge of water from the pores of the metallocate is suppressed, so that the silylating agent in the solution is hydrolyzed and It is preferable in that the polymerization reaction is suppressed and the silylation of the metallosilicate proceeds efficiently.

The treatment time for silylation depends on the reaction temperature, but is usually 0.1 hours or more, preferably 0.5 hours or more, more preferably 1 hour or more, and the treatment time is as long as the performance of the catalyst is not impaired. There is no particular upper limit. By setting the treatment time within the above range, the silylation coating of the outer surface acid point of the metallosilicate proceeds, and the amount of the outer surface acid is sufficiently reduced, which is preferable.

[Other active ingredients]
The catalyst of the present invention may contain an active ingredient other than the metallosilicate of the present invention as long as the effect of the present invention is not impaired. Examples of other active ingredients include aluminophosphates such as silicoaluminophosphate. The content of the aluminophosphate contained in the catalyst of the present invention is usually 20% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 0% by mass. The content of the metallosilicate contained in the catalyst of the present invention is usually 80% by mass or more, preferably 90% by mass or more, and more preferably 100% by mass. Since silicoaluminophosphate has low stability under high temperature conditions and water vapor conditions, it is preferable that the content of metallosilicate is high. Other active ingredients may be contained in the metallosilicate of the present invention in the form of mixed crystals, but usually, each active ingredient is synthesized and then mixed.

[Catalyst molding]
The above-mentioned metallosilicate of the catalytically active ingredient may be used as it is as a catalyst in the reaction, or may be mixed with a substance or a binder inactive in the reaction to form a catalyst, which may be used in the reaction.
Examples of the substance or binder inert to the reaction include alumina or alumina sol, silica, silica sol, quartz, and a mixture thereof.

[Amount of acid in catalyst]
The total acid amount and the outer surface acid amount of the catalyst can be measured by the same method as the total acid amount and the outer surface acid amount of the metallosilicate described above. The total acid content of the catalyst is not particularly limited, but is usually 0.001 mmol / g or more, preferably 0.01 mmol / g or more, more preferably 0.03 mmol / g or more, still more preferably 0.05 mmol / g or more. It is g or more, particularly preferably 0.07 mmol / g or more. Further, it is usually 1.2 mmol / g or less, preferably 0.80 mmol / g or less, more preferably 0.50 mmol / g or less, still more preferably 0.30 mmol / g or less, and particularly preferably 0.20 mmol / g or less. .. By setting the total amount of acid in the catalyst within the above range, the conversion activity of methanol is ensured, the coke formation inside the pores of the metallosilicate is suppressed, and the formation of propylene and linear butene can be promoted. It is preferable in that respect.

The amount of acid on the outer surface of the catalyst is not particularly limited, but is usually preferably 5% or less, more preferably 3% or less, and 0%, based on the total acid amount of the catalyst. The one is the most preferable. If the amount of outer surface acid is too large, the selectivity of propylene or linear butene tends to decrease due to side reactions that occur at the outer surface acid points.
When a mixture of a metallosilicate and a substance or binder inert to the reaction is used as a catalyst, silica having no acid point is used to adjust the total acid amount and the outer surface acid amount of the catalyst within the above ranges. Or silica sol or the like is preferably used as a binder.

When a binder having an acid point such as alumina is used, in the method for measuring the total acid amount and the outer surface acid amount of the catalyst, the total value including the acid amount of the metallocate and the acid amount of the binder is used. Be measured. In that case, the amount of acid derived from the binder can be obtained by another method, and the value can be subtracted from the amount of acid of the catalyst to obtain the amount of acid of only the metallocate salt that does not contain the amount of acid derived from the binder. The acid amount of the binder is determined by determining the acid amount of the metallocate from the peak intensity of the 4-coordinated Al derived from the acid point of the metallosilicate in ^{27 Al-NMR, and the acid amount of the catalyst obtained by the ammonia heating desorption method.} It is calculated by subtracting the value from.

[Particle size]
The particle size of the catalyst varies depending on the synthesis conditions of the metallocate and the granulation / molding conditions, but the average particle size is usually 0.01 μm to 500 μm, preferably 0.1 to 100 μm. If the particle size of the catalyst is too large, the effective coefficient of the catalyst tends to decrease, and if it is too small, the handleability becomes poor. This average particle size can be determined by SEM observation or the like.

2. Method for producing propylene and linear butene (methanol, dimethyl ether)
The origin of production of methanol and dimethyl ether, which are the raw materials of the present invention, is not particularly limited. For example, those obtained by the hydrogenation reaction of coal and natural gas, and CO / hydrogen mixed gas derived from by-products in the iron manufacturing industry, those obtained by the modification reaction of plant-derived alcohols, and those obtained by the fermentation method. , Recycled plastics, those obtained from organic substances such as municipal waste, etc. At this time, a compound in which compounds other than methanol and dimethyl ether resulting from each production method are arbitrarily mixed may be used as they are, or a purified compound may be used.
As the reaction raw material, only methanol may be used, only dimethyl ether may be used, or a mixture of these may be used. When methanol and dimethyl ether are mixed and used, there is no limitation on the mixing ratio.

(Reactor)
The reaction mode in the present invention is not particularly limited as long as the methanol and / or dimethyl ether feedstock is in the gas phase in the reaction region, but a fixed bed reactor, a moving bed reactor or a fluidized bed reactor is selected. When propylene and straight-chain butene are co-produced, the selectivity of propylene and straight-chain butene tends to fluctuate as the conversion rate fluctuates. , Fluidized bed reactors are preferred.

Further, it may be carried out in any form of batch type, semi-continuous type or continuous type, but it is preferably carried out in a continuous type, and the method may be a method using a single reactor, or in series or in parallel. A method using a plurality of arranged reactors may also be used.
When the fluidized bed reactor is filled with the above-mentioned catalyst, particles that are inert to the reaction, such as quartz sand, alumina, silica, and silica-alumina, are mixed with the catalyst in order to keep the temperature distribution of the catalyst layer small. And fill it. In this case, the amount of granules that are inert to the reaction, such as quartz sand, is not particularly limited. The granular material preferably has a particle size similar to that of the catalyst from the viewpoint of uniform mixing with the catalyst.
Further, the reaction substrate (reaction raw material) may be divided and supplied to the reactor for the purpose of dispersing the heat generated by the reaction.

(Substrate concentration)
The total concentration (substrate concentration) of methanol and dimethyl ether in all the feed components supplied to the reactor is not particularly limited, but the sum of methanol and dimethyl ether is usually 5 mol% or more, preferably 10 mol, in the total feed components. % Or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, particularly preferably 50 mol% or more, usually 95 mol% or less, preferably 90 mol% or less, more preferably 70 mol% or less. be. By setting the substrate concentration in the above range, the production of aromatic compounds and paraffins can be suppressed, and the yields of propylene and linear butene can be improved. Further, since the reaction rate can be maintained, the amount of catalyst can be suppressed, and the size of the reactor can also be suppressed.
Therefore, it is preferable to dilute the reaction substrate with the diluent described below, if necessary, so as to obtain such a preferable substrate concentration.

(Diluent)
In the reactor, in addition to methanol and / or dimethyl ether, hydrocarbons such as helium, argon, nitrogen, carbon monoxide, carbon dioxide, hydrogen, water, paraffins, methane, aromatic compounds, and them. A gas inert to the reaction can be present, such as a mixture of helium, nitrogen, and water (steam), which are preferable because of good separation.
As such a diluent, impurities contained in the reaction raw material may be used as they are, or a separately prepared diluent may be mixed with the reaction raw material and used.
Further, the diluent may be mixed with the reaction raw material before being put into the reactor, or may be supplied to the reactor separately from the reaction raw material.

(Weight space speed)
The weight space velocity referred to here is the flow rate of methanol and / or dimethyl ether which is a reaction raw material per weight of the catalyst (catalyst active ingredient), and the weight of the catalyst is not used for granulation / molding of the catalyst. It is the weight of the catalytically active ingredient that does not contain the active ingredient or binder. The flow rate is the total flow rate (weight / hour) of methanol and / or dimethyl ether.

The weight space velocity is not particularly limited, but is usually 0.01 Hr ^-1 or more, preferably 0.1 Hr ^-1 or more, more preferably 0.3 Hr ^-1 or more, still more preferably 0.5 Hr ^-1 or more. It is usually 50 Hr ^-1 or less, preferably 20 Hr ^-1 or less, more preferably 10 Hr ^-1 or less, still more preferably 5.0 Hr ^-1 or less. By setting the weight space velocity in the above range, the proportion of unreacted methanol and / or dimethyl ether in the reactor outlet gas can be reduced, and by-products such as aromatic compounds and paraffins can be reduced. Therefore, it is preferable in that the yields of propylene and linear butene can be improved. Further, it is preferable because the amount of catalyst required to obtain a constant production amount can be suppressed and the size of the reactor can be suppressed.

(Reaction temperature)
The reaction temperature is not particularly limited as long as it is a temperature at which methanol and / or dimethyl ether contacts the catalyst to produce propylene and linear butene, but is usually 250 ° C.
Above, preferably 280 ° C. or higher, more preferably 310 ° C. or higher, still more preferably 330 ° C. or higher, particularly preferably 350 ° C. or higher, 380 ° C. or lower, preferably 375 ° C. or lower, more preferably 370 ° C. or lower, still more preferable. Is 365 ° C. or lower, particularly preferably 360 ° C. or lower. By setting the reaction temperature within the above range, the production of ethylene, aromatic compounds and paraffins can be suppressed, so that the yields of propylene and linear butene, particularly the yield of linear butene, can be improved. In addition, since the conversion activity of methanol and / or dimethyl ether can be maintained at a high level, it can be produced with a high yield of propylene and linear butene over a long period of time. Further, since dealumination from the zeolite skeleton is suppressed, it is preferable in that the catalyst life can be maintained. The reaction temperature here refers to the temperature at the outlet of the catalyst layer.

(Reaction pressure)
The reaction pressure is not particularly limited, but is usually 0.01 MPa (absolute pressure, the same applies hereinafter) or more, preferably 0.05 MPa or more, more preferably 0.1 MPa or more, still more preferably 0.2 MPa or more. It is usually 5 MPa or less, preferably 1 MPa or less, more preferably 0.7 MPa or less, still more preferably 0.5 MPa or less. By setting the reaction pressure within the above range, the formation of by-products such as aromatic compounds and paraffins can be suppressed, and the yields of propylene and linear butene can be improved. The reaction rate can also be maintained.

(Partial pressure of raw materials)
The total partial pressure of methanol and dimethyl ether is not particularly limited, but is usually 0.005 MPa or more (absolute pressure, the same applies hereinafter), preferably 0.01 MPa or more, more preferably 0.03 MPa or more, still more preferably 0. It is 0.05 MPa or more, particularly preferably 0.07 MPa or more, usually 3 MPa or less, preferably 1 MPa or less, more preferably 0.5 MPa or less, still more preferably 0.3 MPa or less, and particularly preferably 0.1 MPa or less. By setting the partial pressure of the raw material within the above range, the formation of by-products such as aromatic compounds and paraffins can be suppressed, and the yields of propylene and linear butene can be improved. The reaction rate can also be maintained.

(Conversion rate)
In the present invention, the conversion rate of methanol and / or dimethyl ether is not particularly limited, but the conversion rate is usually 90% or more, preferably 95% or more, more preferably 99% or more, still more preferably 99.5%. The above is usually 100% or less. According to the present invention, by adjusting the conversion ratio so as to be within the above range, it is possible to suppress the by-product of aromatic compounds and paraffins and the accumulation of cork in the pores, and it is possible to suppress the accumulation of cork in the pores of propylene and linear butene. The yield can be improved and it can be produced with a high linear butene / propylene ratio. Also, the efficiency of separation of methanol and / or dimethyl ether from the product can be increased.

Usually, the accumulation of cork progresses with the lapse of the reaction time, and the conversion rate of methanol and / or dimethyl ether tends to decrease. Therefore, the catalyst reacted for a certain period of time needs to be subjected to the regeneration treatment. The method of operating within the above conversion rate range is not particularly limited.
For example, when the reaction is carried out in a fixed bed reactor, a plurality of reactors are provided in parallel, and when the conversion rate drops from the above preferable range, the contact between the catalyst and the reaction raw material is stopped, and the reaction is stopped. The catalyst is used in the regeneration process. In the fixed bed reactor, the reaction time and the regeneration time are appropriately adjusted, that is, the time for switching between the reaction step and the regeneration step in the operation is appropriately adjusted, so that the reactor is continuously operated at the above-mentioned preferable range of conversion rate. be able to.

When the reaction is carried out in a fluidized bed reactor, a catalyst regenerator is attached to the reactor, the catalyst extracted from the reactor is continuously sent to the regenerator, and the catalyst regenerated in the regenerator is used. It is preferable to carry out the reaction while continuously returning to the reactor. By appropriately adjusting the residence time of the catalyst in the reactor and the residence time in the regenerator, continuous operation can be performed with the conversion rate in the above-mentioned preferable range.
Catalysts with reduced conversion of methanol and / or dimethyl ether can be regenerated using various known catalyst regeneration methods.
The regeneration method is not particularly limited, but specifically, for example, it can be regenerated using air, nitrogen, steam, hydrogen, etc., and it is preferable to regenerate using air, hydrogen, or the like.

(Coke)
Conversion of methanol and / or dimethyl ether causes some of it to accumulate as cork on the inner / outer surfaces of the crystal. The amount of cork is not particularly limited as long as it is an amount in which methanol and / or dimethyl ether is converted to produce propylene and linear butene, but is usually 0.1% by mass or more with respect to metallosilicate. It is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, further preferably 2.0% by mass or more, and usually 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass. % Or less, more preferably 8.0% by mass or less. By adjusting the amount of cork so as to be within the above range, it is possible to suppress by-products of ethylene and paraffin while maintaining the conversion activity of methanol and / or dimethyl ether, and improve the yield of propylene and linear butene. Can be made to. The amount of cork here can be determined by, for example, thermogravimetric analysis (TG). Specifically, the metallosilicate in which cork has accumulated due to the conversion reaction of methanol and / or dimethyl ether is heated to 550 ° C. at a heating rate of 10 ° C./min under the flow of an inert gas such as helium (50 cc / min). By holding for 30 minutes, adsorbed water and lightly boiling hydrocarbon components are removed. Subsequently, it is switched to air flow (50 cc / min), heated from 550 ° C. to 600 ° C. at a heating rate of 10 ° C./min, and held for 60 minutes. The weight loss due to oxidative combustion in the temperature range of 550 ° C. or higher at this time is defined as the amount of cork.

(Reaction product)
As the reactor outlet gas (reactor effluent), a mixed gas containing reaction products such as lower olefins such as ethylene, propylene and linear butene, by-products and diluents can be obtained. The concentration of propylene and linear butene in the mixed gas is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, and usually 95% by mass or less, preferably 90% by mass or less.

Depending on the reaction conditions, methanol and / or dimethyl ether is contained in the reaction product as an unreacted raw material, but it is preferable to carry out the reaction under reaction conditions such that the conversion rate of methanol and / or dimethyl ether is 100%. As a result, the reaction product and the unreacted raw material are easily separated, preferably unnecessary. By-products include ethylene, olefins having 4 or more carbon atoms, paraffins, aromatic compounds and water. In the present invention, components other than propylene and linear butene may be separated and recovered, if desired. In particular, when the market price of ethylene is high and the demand is high, it is desirable to separate and recover ethylene together with propylene and straight-chain butene. The residue obtained by separating and recovering the desired component contains light paraffin, ethylene, C5 or higher olefin, aromatic compound, steam and the like. At least a part of this residue can be mixed with a part of the above-mentioned raw material gas and used as a so-called recycled gas.

In the present invention, the total yield of propylene and linear butene is not particularly limited, but is usually 50% or more, preferably 60% or more, more preferably 70%, still more preferably 80% or more. The upper limit is not particularly limited, but is usually 100%. When the total yield of propylene and linear butene is within the above range, the yield of the target product at the outlet of the reactor is sufficient, and the raw material cost and the load of separation / purification can be reduced. preferable.

In the present invention, the yield of linear butene is not particularly limited, but is usually 20% or more, preferably 25% or more, more preferably 30%, still more preferably 35% or more, and the upper limit is particularly limited. However, it is usually 90% or less, preferably 70% or less, more preferably 50% or less, still more preferably 40% or less. When the yield of the linear butene is in the above range, the yield of the target product at the outlet of the reactor becomes sufficient, and the raw material cost and the load of separation / purification can be reduced, which is preferable. As a reaction condition, the yield of linear butene can be increased by lowering the reaction temperature.

In the present invention, the total mass ratio of propylene and linear butene to ethylene (hereinafter, (propylene + linear butene) / ethylene) is not particularly limited, but is usually 1.0 or more, preferably 3. It is 0 or more, more preferably 6.0 or more, still more preferably 9.0 or more, and the upper limit is not particularly limited, but is usually 30 or less, preferably 20, more preferably 15 or less. As a reaction condition, the (propylene + linear butene) / ethylene ratio can be improved by lowering the reaction temperature.

In the present invention, the mass ratio of linear butene to ethylene (hereinafter, linear butene / ethylene) is not particularly limited, but is usually 1.0 or more, preferably 1.5 or more, and more preferably 2. It is 0 or more, more preferably 3.0 or more, particularly preferably 4.0 or more, and the upper limit is not particularly limited, but is usually 10 or less, preferably 8.0 or less, more preferably 7.0 or less, particularly preferably 7.0 or less. It is 6.0 or less. As a reaction condition, the linear butene / ethylene ratio can be improved by lowering the reaction temperature.

In the present invention, the mass ratio of linear butene to propylene (hereinafter, linear butene / propylene) is not particularly limited, but is usually 0.1 or more, preferably 0.2 or more, and more preferably 0. It is 4 or more, and the upper limit is not particularly limited, but is usually 2.0 or less, preferably 1.5 or less, and more preferably 1.0 or less. As a reaction condition, the linear butene / propylene ratio can be improved by lowering the reaction temperature.

In the present invention, the ratio of linear butene to total butene (hereinafter, linear butene / total butene) is not particularly limited, but is usually 60% or more, preferably 80% or more, more preferably 90%. The above is the most preferable, and it is 100%. When the linear butene / total butene ratio is within the above range, the yield of the target linear butene is sufficient, and the load in the separation / purification step of the linear butene can be reduced. Is preferable.

The conversion rate is a value calculated by the following formula.
Methanol conversion rate (%) = [[reactor inlet methanol (mol / Hr) -reactor outlet methanol (mol / Hr)] / reactor inlet methanol (mol / Hr)] × 100
Dimethyl ether conversion rate (%) = [[Reactor inlet dimethyl ether (mol / Hr) -Reactor outlet dimethyl ether (mol / Hr) -Reactor outlet methanol (mol / Hr) / 2] / Reactor inlet dimethyl ether (mol / Hr) )] × 100
The selectivity in the present specification is a value calculated by each of the following formulas. In each of the following formulas, the "derived carbon flow rate (mol / Hr)" of hydrocarbons such as ethylene, propylene, butene, C5 +, paraffin and aromatic compounds means the molar flow rate of carbon atoms constituting each hydrocarbon. do. When dimethyl ether is used as the raw material, the total carbon molar flow rate of dimethyl ether and methanol is used for the carbon molar flow rate derived from the reactor outlet raw material of the following formula.

Paraffin is the total of paraffin having 1 to 4 carbon atoms, aromatic compound is the total of benzene, toluene and xylene, and C5 + is the total of hydrocarbons having 5 or more carbon atoms excluding the aromatic compound.
Ethylene selectivity (%) = [reactor outlet ethylene-derived carbon molar flow rate (mol / Hr) / [reactor outlet total carbon molar flow rate (mol / Hr) -reactor outlet methanol-derived carbon molar flow rate (mol / Hr)) ]] × 100
-Propine selectivity (%) = [reactor outlet propylene-derived carbon molar flow rate (mol / Hr) / [reactor outlet total carbon molar flow rate (mol / Hr) -reactor outlet methanol-derived carbon molar flow rate (mol / Hr)) ]] × 100
Butene selectivity (%) = [reactor outlet butene-derived carbon molar flow rate (mol / Hr) / [reactor outlet total carbon molar flow rate (mol / Hr) -reactor outlet methanol-derived carbon molar flow rate (mol / Hr)) ]] × 100
C5 + selectivity (%) = [reactor outlet C5 + derived carbon molar flow rate (mol / Hr) / [reactor outlet total carbon molar flow rate (mol / Hr) -reactor outlet methanol derived carbon molar flow rate (mol / Hr)) ]] × 100
Paraffin selectivity (%) = [reactor outlet paraffin-derived carbon molar flow rate (mol / Hr) / [reactor outlet total carbon molar flow rate (mol / Hr) -reactor outlet methanol-derived carbon molar flow rate (mol / Hr)) ]] × 100
Aromatic compound selectivity (%) = [reactor outlet aromatic compound-derived carbon molar flow rate (mol / Hr) / [reactor outlet total carbon molar flow rate (mol / Hr) -reactor outlet methanol-derived carbon molar flow rate (mol / Hr) mol / Hr)]] × 100
Dimethyl ether selectivity (%) = [reactor outlet dimethyl ether-derived carbon molar flow rate (mol / Hr) / [reactor outlet total carbon molar flow rate (mol / Hr) -reactor outlet methanol-derived carbon molar flow rate (mol / Hr)) ]] × 100 (However, it is used only when methanol is used as the raw material)
The ratio of each isomer in butenes is calculated by the following formulas.

1-Butene ratio (%) = [Reactor outlet 1-Butene-derived carbon molar flow rate (mol / Hr) / Reactor outlet butene-derived carbon molar flow rate (mol / Hr)] × 100
-Trans-2-butene ratio (%) = [reactor outlet trans-2-butene-derived carbon molar flow rate (mol / Hr) / reactor outlet butene-derived carbon molar flow rate (mol / Hr)] × 100
-Cis-2-butene ratio (%) = [reactor outlet cis-2-butene-derived carbon molar flow rate (mol / Hr) / reactor outlet butene-derived carbon molar flow rate (mol / Hr)] × 100
Isobutene ratio (%) = [reactor outlet isobutylene-derived carbon molar flow rate (mol / Hr) / reactor outlet butene-derived carbon molar flow rate (mol / Hr)] × 100
The yield in the present specification is determined by the product of the raw material conversion rate and the selectivity of each produced component. Specifically, the propylene yield and the linear butene yield are represented by the following formulas, respectively. Will be done. The linear butene selectivity here is represented by the product of the butene selectivity and the sum of the ratios of 1-butene, trans-2-butene and cis-2-butene in the butenes.

-Propene yield (%) = raw material conversion rate (%) x propylene selectivity (%) / 100
-Linear butene yield (%) = raw material conversion rate (%) x linear butene selectivity (%) / 100
-Linear butene selectivity (%) = butene selectivity (%) x [1-butene ratio + trans-2-butene ratio + cis-2-butene ratio (%)] / 100

(Separation of products)
The mixed gas containing the reaction products propylene and linear butene, unreacted raw materials, by-products and diluent as the reactor outlet gas is introduced into a known separation / purification facility, and depending on the respective components. It may be collected, refined, recycled, and discharged.

One embodiment of this separation / purification method includes a step of cooling / compressing the gas at the outlet of the reactor to remove most of the condensed water, and a hydrocarbon fluid containing a part of water after removing the water. Is dried with a molecular sieve or the like, and then a method including a step of purifying each olefin and paraffin by distillation is applied. In the above method, the compressed hydrocarbon fluid may be supplied to one distillation column, but a multi-stage compressor is installed to roughly separate easily condensing hydrocarbons and hard-to-condensate hydrocarbons, and separate them. It may be supplied to the distillation column of the above and distilled.
Ingredients other than propylene and linear butene (olefins, paraffins, etc.), in particular some or all of hydrocarbons having 5 or more carbon atoms, are separated and purified and then mixed with the reaction raw materials or directly supplied to the reactor. You may recycle it by doing so. In addition, among the by-products, the components that are inert to the reaction can be reused as a diluent.

(Use of propylene)
Propylene obtained by the production method of the present invention can be produced by polymerizing it. The method for polymerizing propylene is not particularly limited, but the propylene obtained by the present invention can be directly introduced into a polymerization reactor as a raw material monomer and used. In addition to polypropylene, the propylene obtained by the present invention can also be used as a raw material for propylene derivatives through various reactions described later. For example, acrylonitrile can be produced by ammonia oxidation, acrolein, acrylic acid and acrylic acid ester can be produced by selective oxidation, normal butyl alcohol can be produced by oxo reaction, and propylene oxide and propylene glycol can be produced by selective oxidation. Further, propylene can produce acetone by a Wacker reaction, and further, methyl isobutyl ketone can be produced from the obtained acetone. Further, from acetone, methyl methacrylate can be produced via acetone cyanide hydrin. In addition, propylene can produce isopropyl alcohol by a hydration reaction. Further, propylene can produce phenol, bisphenol A, or polycarbonate resin from cumene, which is obtained by reacting with benzene.

(Use of linear butene)
Butene obtained by the production method of the present invention can produce butadiene by dehydrogenation. Further, butadiene can produce polybutadiene (BR) by homopolymerization, styrene butadiene rubber (SBR) by polymerization with styrene, acrylonitrile-styrene-butadiene resin (ABS resin) by polymerization of acrylonitrile and styrene, and the like. The linear butene can also be used as a raw material for other butene derivatives. For example, straight-chain butene can produce methyl ethyl ketone by a subsequent dehydrogenation reaction via sec-butyl alcohol by an indirect hydration method. As 1-butene, polybutene-1 can be produced by polymerization, amyl alcohol and the like can be produced by oxo reaction.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
In the following preparation examples, the X-ray diffraction (XRD) pattern of the zeolite crystals obtained by synthesis was obtained using X'Pert Pro MPD manufactured by PANalytical. The X-ray source is CuKα (X-ray output: 40 kV, 30 mA) and the read width is 0.016 °.

The Si and Al compositions of the synthesized zeolite were measured by fluorescent X-ray analysis. For the measurement, Rayny EDX-700 manufactured by Shimadzu Corporation was used. Further, for Na analysis, after HF decomposition treatment, treatment with acid, constant volume, and then quantification was performed by an atomic absorption spectrometer (AAS). SpectorAA-220 manufactured by Agilent Technologies was used as the AAS.
As for the shape of the zeolite particles, a scanning electron microscope (S-4100) manufactured by Hitachi High-Tech was used to observe the conductively treated sample at an acceleration voltage of 15 kV.
The total acid content of the metallocate was measured by NH _3- TPD. For the measurement, AGS7000 manufactured by Canon Anerva Co., Ltd. was used, and the measurement was performed as follows. 50 mg of the metallosilicate of the sample was weighed in a Pt boat, set in a quartz tube, and dried under vacuum at 500 ° C. for 30 minutes as a pretreatment. Then, it was brought into contact with an excess amount of ammonia at 100 ° C. for 15 minutes to adsorb ammonia on the metallosilicate. Subsequently, the mixture was vacuum-dried at 100 ° C. to remove excess ammonia, thereby obtaining a metallocate salt on which ammonia was adsorbed. Next, the metallosilicate on which ammonia was adsorbed was heated at a heating rate of 10 ° C./min in a helium atmosphere, and the amount of ammonia desorbed at 100-600 ° C. was measured by mass spectrometry. The obtained TPD profile was waveform-separated by a Gaussian function, and the total acid amount per mass of metallocate was calculated from the total area of the waveform having a peak top of 240 ° C. or higher.

(Preparation Example 1)
123 g of 1 M aqueous sodium hydroxide solution and 32.9 g of N, N-dimethyl-3,5-dimethylpiperidium hydroxide aqueous solution (21.8% by mass) were dissolved in 8.2 g of water in this order, and Y-type zeolite CBV720 ( 14.4 g of SiO ₂ / Al ₂ O ₃ ratio 30, manufactured by ZEOLYST) was added, and the mixture was stirred for 30 minutes. Further, 14.8 g of colloidal silica SI-30 (SiO ₂ 30% by mass, Na 0.3% by mass, manufactured by JGC Catalysts and Chemicals Co., Ltd.) was added to prepare a gel-like reaction solution (hereinafter, may be referred to as a raw material gel). Stirred for hours. The raw material gel was placed in a 1000 ml autoclave and subjected to a hydrothermal synthesis reaction at 135 ° C. for 7 days while stirring at 150 rpm under self-pressure. The obtained product was filtered, washed with water, and then dried at 100 ° C.
From the XRD pattern of the product, it was confirmed that the obtained product was an aluminosilicate having an AEI type structure. From the fluorescent X-ray analysis, the SiO ₂ / Al ₂ O ₃ ratio was 17. Moreover, the average primary particle diameter was about 800 nm from the scanning electron microscope.
The aluminosilicate obtained by hydrothermal synthesis (aluminosilicate before calcination) was calcined at 580 ° C. for 6 hours under air flow to obtain a Na-type aluminosilicate. As a result of elemental analysis, the content of sodium in the aluminosilicate was 1.0% by mass.
Water vapor was obtained by treating 1.0 g of the obtained aluminosilicate having an AEI type structure at 800 ° C. under normal pressure under 50% water vapor (steam / air = 50/50 (volume / volume)) for 5 hours. A treated Na-type AEI-type structure aluminosilicate was obtained. There was no change in the Si and Al contents of the entire crystal due to the steam treatment, and the SiO ₂ / Al ₂ O ₃ ratio was 17. As a result of elemental analysis, the content of sodium in the aluminosilicate was 1.0% by mass. All acid content of the aluminosilicate _is from NH 3 -TPD, was 0.08 mmol / g. (Catalyst 1)

(Preparation Example 2)
1.60 g of sodium hydroxide and 205 g of N, N-dimethyl-3,5-dimethylpiperidium hydroxide aqueous solution (21.8% by weight) were dissolved in 56.6 g of water in this order, and Y-type zeolite CBV720 (SiO _{2) was dissolved.} / Al ₂ O ₃ ratio 30, manufactured by ZEOLYST) 51.2 g was added and stirred for 2 hours. Further CHA-type zeolite which corresponds to 5% by weight relative to the weight of silica _(SiO 2 / _Al 2 _{O 3} ratio of 25, average particle diameter 200 nm, not including the organic structure-directing agent) was added 2.40g as a seed crystal, stirred The mixture was obtained by The mixture was placed in a 1000 ml autoclave and subjected to a hydrothermal synthesis reaction at 160 ° C. for 7 days while rotating at 150 rpm under self-pressure. The obtained product was filtered, washed with water, and dried at 100 ° C. to obtain 41.0 g of a white powder.
From the XRD pattern of the product, it was confirmed that the obtained product was an aluminosilicate having an AEI type structure. From the fluorescent X-ray analysis, the SiO ₂ / Al ₂ O ₃ ratio was 22. Further, from the scanning electron microscope, the average primary particle size was about 100 to 200 nm. The aluminosilicate (aluminosilicate before calcination) obtained by hydrothermal synthesis was calcined at 580 ° C. for 6 hours under air flow to obtain a Na-type aluminosilicate (aluminosilicate (A)).
1.0 g of the obtained aluminosilicate (A) having an AEI type structure is treated at 800 ° C. under normal pressure under 50% water vapor (water vapor / air = 50/50 (volume / volume)) flow for 5 hours. To obtain an aluminosilicate having a Na-type AEI-type structure of fine particles treated with steam. There was no change in the Si and Al contents of the entire crystal by steam treatment, and the SiO ₂ / Al ₂ O ₃ ratio was 22. As a result of elemental analysis, the Na concentration in the zeolite was 1.0% by weight. (Catalyst 2)

(Preparation Example 3)
1.0 g of aluminosilicate (A) of Preparation Example 2 was ion-exchanged twice at 80 ° C. for 1 hour with a 1 M aqueous ammonium nitrate solution, dried at 100 ° C., and then calcined at 500 ° C. for 6 hours under air flow. , H-type aluminosilicate was obtained. 1 g of the obtained aluminosilicate having an AEI type structure is steam-treated by treating it at 750 ° C. under normal pressure under 50% steam (steam / air = 50/50 (volume / volume)) for 5 hours. An H-type AEI-type aluminosilicate was obtained. There was no change in the Si and Al contents of the entire crystal by steam treatment, and the SiO ₂ / Al ₂ O ₃ ratio was 22. (Catalyst 3)

(Preparation Example 4)
1.0 g of the aluminosilicate (A) of Preparation Example 2 was ion-exchanged once with a 5 M aqueous calcium nitrate solution at 80 ° C. for 5 hours, dried at 100 ° C., and then the obtained aluminosilicate having an AEI type structure was obtained. Was treated at 900 ° C. under normal pressure under air flow for 6 hours to obtain a heat-treated Ca, Na-type aluminosilicate having an AEI-type structure. There was no change in the Si and Al contents of the entire crystal by steam treatment, and the SiO ₂ / Al ₂ O ₃ ratio was 22. (Catalyst 4)

(Examples 1 and 2)
Using catalysts 1 and 2, a synthetic reaction of propylene and straight-chain butene was carried out using methanol as a raw material. For the reaction, a normal pressure fixed bed flow reactor was used, and a quartz reaction tube having an inner diameter of 6 mm was filled with a mixture of 200 mg of the catalyst and 300 mg of quartz sand. Methanol and nitrogen were supplied to the reactor at a weight space velocity of 0.50 Hr- ¹ and 50% by volume of methanol and 50% by volume of nitrogen, and propylene and nitrogen at 350 ° C. and 0.1 MPa (absolute pressure). A straight-chain butene synthesis reaction was carried out, and the reactor outlet gas was analyzed by gas chromatography. The reaction results are shown in Table 1.

(Comparative Example 1)
Using the catalyst 1, methanol and nitrogen were supplied to the reactor so that the weight space velocity of methanol was 1.3 Hr- ¹ , and the methanol was 10% by volume and the nitrogen was 90% by volume. The same operation as in Examples 1 and 2 was carried out except for the absolute pressure), and the synthesis reaction of propylene and linear butene was carried out. The reaction results are shown in Table 1.

Example 1 uses _{an aluminosilicate (catalyst 1) having an AEI type structure having a SiO 2} / Al ₂ O ₃ molar ratio of 17, an average primary particle size of about 800 nm, and a total acid content of 0.08 mmol / g as a catalyst at 350 ° C. This is an example of a reaction in which propylene and linear butene were synthesized by contacting with methanol under the conditions of a methanol concentration of 50% by volume, a partial pressure of methanol of 0.05 MPa (absolute pressure), and a weight space velocity of 0.50 Hr- ^1. The propylene yield after 1.83 hours from the start of the reaction was 34.2%, and the linear butene yield was 29.0%. After 4.17 hours from the start of the reaction, the propylene yield was 46.0% and the linear butene yield was 27.5%, and high yields of both propylene and linear butene were maintained.
In Example 2, _{an aluminosilicate (catalyst 2) having an AEI type structure having a SiO 2} / Al ₂ O ₃ molar ratio of 22 and an average primary particle size of 100 to 200 nm was used as a catalyst at 350 ° C. and a methanol concentration of 50% by volume. This is an example of a reaction in which propylene and linear butene are synthesized by contacting with methanol under the conditions of methanol partial pressure of 0.05 MPa (absolute pressure) and weight space velocity of 0.50 Hr- ^1. The propylene yield after 1.83 hours from the start of the reaction was 37.6%, and the linear butene yield was 34.2%. After 4.17 hours from the start of the reaction, the propylene yield was 45.2% and the linear butene yield was 31.1%, and high yields of both propylene and linear butene were maintained.
On the other hand, in Comparative Example, propylene was brought into contact with methanol under the conditions of 400 ° C., methanol concentration 10% by volume, methanol partial pressure 0.01 MPa (absolute pressure), and weight space velocity 1.3 Hr- ^{1 using catalyst 1.} This is an example of a reaction in which straight-chain butene is synthesized. The propylene yield after 1.92 hours from the start of the reaction was 48.6%, and the linear butene yield was 22.3%. However, 4.25 hours after the start of the reaction, the propylene yield decreased to 41.7% and the linear butene yield decreased to 19.1.
As can be seen from Examples 1 and 2, by carrying out the reaction at a low temperature such as 350 ° C., high yields of propylene and linear butene were achieved, and the decrease in activity due to coke accumulation was suppressed, and the activity was reduced for a long time. It can be stably synthesized in a high yield.

(Example 3)
Using the catalyst 2, the same operation as in Example 2 was carried out except that the reaction temperature was 335 ° C., and the synthesis reaction of propylene and linear butene was carried out. The reaction results are shown in Table 2.

(Example 4)
Using the catalyst 2, the same operation as in Example 2 was carried out except that the reaction temperature was 365 ° C., and the synthesis reaction of propylene and linear butene was carried out. The reaction results are shown in Table 2.

(Example 5)
Using the catalyst 2, the same operation as in Example 2 was carried out except that the reaction temperature was set to 380 ° C., and the synthesis reaction of propylene and linear butene was carried out. The reaction results are shown in Table 2.

(Example 6)
The same operation as in Example 2 was carried out except that methanol and nitrogen were supplied to the reactor so as to be 30% by volume of methanol and 70% by volume of nitrogen using the catalyst 2, and the synthesis reaction of propylene and linear butene was carried out. carried out. The reaction results are shown in Table 3.

(Example 7)
The same operation as in Example 2 was carried out except that methanol and nitrogen were supplied to the reactor so as to be 75% by volume of methanol and 25% by volume of nitrogen using the catalyst 2, and the synthesis reaction of propylene and linear butene was carried out. carried out. The reaction results are shown in Table 3.

(Example 8)
The same operation as in Example 1 was carried out except that the catalyst 3 was used, and a synthetic reaction of propylene and linear butene was carried out. The reaction results are shown in Table 3.

(Example 9)
The same operation as in Example 1 was carried out except that the catalyst 4 was used, and a synthetic reaction of propylene and linear butene was carried out. The reaction results are shown in Table 3.

In Examples 3, 4, and 5, using an aluminosilicate having an AEI type structure (catalyst 2) as a catalyst, the methanol concentration is 50% by volume, the methanol partial pressure is 0.05 MPa (absolute pressure), and the weight space velocity is 0. This is an example of a reaction in which propylene and linear butene were synthesized by contacting with methanol at a reaction temperature of 335 ° C., 365 ° C., and 380 ° C. under the condition of 50 Hr- ^1. At a reaction temperature of 380 ° C. or lower, the propylene yield was 44.6 to 47.5% and the linear butene selectivity was 26.0% to 29.8% even after 4.17 hours from the start of the reaction. High yields were maintained for both butene.

In Examples 6 and 7, the methanol concentration was 30% by volume (methanol partial pressure 0 ^{) under the conditions of 350 ° C. and a weight space velocity of 0.50 Hr-1 using} an aluminosilicate (catalyst 2) having an AEI type structure as a catalyst. This is an example of a reaction in which propylene and linear butene were synthesized by contacting with methanol at .03 MPa (absolute pressure)) and 75% by volume (0.075 MPa (absolute pressure)). In a wide methanol concentration region, 4.17 hours after the start of the reaction, the yield of linear butene is 30% or more, and propylene and linear butene can be produced in good yield.

In Examples 8 and 9, a catalyst obtained by steam-treating H-type AEI-type aluminosilicate (catalyst 3) and a catalyst heat-treated after calcium ion exchange (catalyst 4) were used as catalysts at 350 ° C. and methanol, respectively. This is an example of a reaction in which propylene and linear butene are synthesized by contacting with methanol under the conditions of a concentration of 50% by volume, a partial pressure of methanol of 0.05 MPa (absolute pressure), and a weight space velocity of 0.50 Hr- ^1. With either catalyst, propylene and linear butene can be produced in good yield.

According to the production method of the present invention, propylene and linear butene can be simultaneously produced from methanol and / or dimethyl ether in high yield. Further, since the by-product of isobutene can be suppressed and the linear butene can be selectively produced, the load of separating and purifying the linear butene from the butenes can be significantly reduced.

Claims (12)

A method for producing propylene and linear butene by contacting at least one raw material selected from methanol and dimethyl ether with a catalyst, wherein the active ingredient of the catalyst is a metallosilicate that satisfies the following (1) to (3). A method for producing propylene and linear butene, which comprises, and the reaction temperature of the step of bringing the raw material into contact with the catalyst to obtain a mixture containing propylene and linear butene is 250 ° C. or higher and 380 ° C. or lower. ..
(1) Its structure is AEI with a code defined by the International Zeolite Association (IZA).
(2) Contains at least one element M selected from the group consisting of aluminum, gallium, boron, and iron.
(3) The amount ratio of Si contained in the metallosilicate and the M is 5 or more and less than 100 in terms of _{SiO 2} / M ₂ O _{3 molar ratio.} (However, the denominator of the molar ratio represents the total amount of _{Al 2} O ₃ , Ga ₂ O ₃ , B ₂ O ₃ and Fe ₂ O _3). The method for producing propylene and linear butene according to claim 1, wherein the total partial pressure of methanol and dimethyl ether is 0.005 MPa or more and 3 MPa or less. The propylene according to claim 1 or 2, wherein the mass ratio of linear butene to ethylene (linear butene / ethylene) in the step of obtaining the mixture containing propylene and linear butene is 1.5 or more. And a method for producing linear butene. The invention according to any one of claims 1 to 3, wherein the metallosilicate is treated with at least one selected from the group consisting of steam treatment, heat treatment, acid treatment, and ion exchange. A method for producing propylene and linear butene. The method for producing propylene and linear butene according to any one of claims 1 to 4, wherein the metallosilicate is an aluminosilicate containing at least aluminum. The method for producing propylene and linear butene according to any one of claims 1 to 5, wherein the average primary particle size of the metallosilicate is 0.03 μm or more and 5 μm or less. The propylene and linear butene according to any one of claims 1 to 6, wherein the metallosilicate contains at least one element selected from an alkali metal element and an alkaline earth metal element. Production method. The propylene and linear butene according to claim 7, wherein the total content of the alkali metal element and the alkaline earth metal element in the metallosilicate is 0.005% by mass or more and 10% by mass or less. Manufacturing method. The method for producing propylene and linear butene according to claim 7 or 8, wherein the alkali metal element contains at least sodium. Any of claims 1 to 9, wherein the total acid amount obtained from the high-temperature desorption amount of the metallosilicate in the ammonia-temperature desorption spectrum is 0.001 mmol / g or more and 0.80 mmol / g or less. The method for producing propylene and linear butene according to item 1. The method for producing propylene and linear butene according to any one of claims 1 to 10, wherein the metallosilicate is silylated. Any one of claims 1 to 11, wherein the total acid amount obtained from the high-temperature desorption amount in the ammonia temperature desorption spectrum of the catalyst is 0.001 mmol / g or more and 0.80 mmol / g or less. The method for producing propylene and linear butene according to.

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