JP4774813B2 - Propylene production method - Google Patents

Description

  The present invention relates to a process for producing propylene from ethylene and methanol and / or dimethyl ether.

  As a method for producing propylene, steam cracking of naphtha and fluid catalytic cracking of vacuum gas oil have been conventionally performed. In recent years, metathesis reaction using ethylene and 2-butene as raw materials and methanol and / or dimethyl ether are used. The MTO process used as a raw material is also attracting attention. On the other hand, a method for producing propylene using ethylene and methanol and / or dimethyl ether as raw materials is also known (Non-Patent Document 1).

Zeolite is effective as a catalyst for producing propylene using ethylene and methanol and / or dimethyl ether as raw materials. However, Non-Patent Document 1 has a problem that the propylene selectivity is low (about 30%).
Proc. 12th Int. Zeolite Conf. (1999) 1057-1064

In Non-Patent Document 1, a zeolite (aluminosilicate) of SiO ₂ / Al ₂ O ₃ = 90 is used as a catalyst, but the present inventors have used a general alumino as used in Non-Patent Document 1. When the reaction was carried out using silicate (SiO ₂ / Al ₂ O ₃ = 50-300), when the space velocity of the reaction raw material was lowered to increase the conversion rate of the reaction, 4 or more carbon atoms other than propylene In addition to these olefins, by-products of paraffin and aromatic compounds increased, and there was a problem that propylene selectivity was not always sufficient. Further, when the space velocity of the reaction raw material is increased, there is a problem that the conversion rate of the reaction decreases.
As described above, in the conventional technology, the selectivity of propylene is insufficient, and it is difficult to achieve both the conversion rate of the reaction raw material and the propylene selectivity. Therefore, an object of the present invention is to provide a method for obtaining propylene from ethylene and methanol and / or dimethyl ether at a higher selectivity than the conventional method.

As a result of intensive studies to solve the above-mentioned problems, the present inventors use a catalyst having a specific range of composition and react ethylene with methanol and / or dimethyl ether at a specific range of substrate concentration. Surprisingly, it has been found that the selectivity of propylene increases as the space velocity decreases, as opposed to conventional catalysts. Based on the above findings, the present inventors have found that propylene can be obtained with high selectivity and efficiency by reacting ethylene with methanol and / or dimethyl ether under reaction conditions in a specific range.
That is, the gist of the present invention is a method for producing propylene by contacting ethylene and methanol and / or dimethyl ether in a reactor in the presence of a catalyst.
As a catalyst, a zeolite selected from MFI type, MWW type, and BEA type having the composition of the following formula (1) is used.
MIxMIIySizOv (1)
(In the formula (1),
MI indicates the Al.
MII represents boron .
x: y: z = 0.0003~ 0.01 : 0.005 ~0.5: 1)
A method for producing propylene , comprising contacting ethylene and methanol and / or dimethyl ether at a reaction temperature of 400 to 600 ° C. and a reaction pressure of 50 kPa to 1 MPa under conditions satisfying the following conditions (A) and (B):
Condition (A): The total concentration of methanol and / or dimethyl ether and ethylene fed to the reactor is 85 mol% or less with respect to all the feed components. Condition (B): The reactor is changed by changing the weight hourly space velocity WHSV in advance . to the number of moles of methanol supplied, relative to the sum of twice the number of moles of dimethyl ether, and the number of moles of methanol at the reactor outlet, when the sum of twice the number of moles of dimethyl ether is 1/20 The total weight space velocity WHSV ₉₅ of methanol and / or dimethyl ether and ethylene was determined, and the weight space velocity WHSV of methanol and / or dimethyl ether in the reactor was 0.85 times or less of WHSV ₉₅ . Exist.

The second gist of the present invention is that, in the production method, the amount of ethylene supplied to the reactor is moles relative to the sum of the number of moles of methanol fed to the reactor and twice the number of moles of dimethyl ether. It exists in the manufacturing method of propylene characterized by being 0.2-10.

  According to the present invention, propylene can be produced with ethylene and methanol and / or dimethyl ether as raw materials at a much higher selectivity than conventional methods.

  Below, the typical aspect for implementing this invention is demonstrated concretely, However, It is not limited to this.

1. Catalyst The catalyst used in the present invention includes zeolite having a composition represented by the following formula (1). The zeolite in the present invention is a crystalline porous silicate having a Bronsted acid point.
M ^I _x M ^II _y Si _z O _v (1)
In formula (1), M ^I is one or more metal elements selected from Al, Ga, and Fe (III). Of these, Al is preferable.
M ^II is one or more metal elements of Groups 1 to 15 of the periodic table other than Al, Ga, Fe (III), and Si elements. Among them, M ^II is Al, is preferably a metal element of the periodic table group 13 other than Ga, when boron is particularly preferred.
x: y: z: v = 0.0003-0.02: 0.001-0.5: 1: 1-5.
x is 0.0003 to 0.02, preferably 0.0003 to 0.01. If x is too small, the reaction rate decreases, which is not preferable. If x is too large, by-products of paraffin and aromatic compounds increase, which is not preferable.
y is 0.001 or more and 0.5 or less. It is preferable that it is 0.005-0.5. If y is too small, the effect of addition is reduced, and by-products of paraffin and aromatic compounds increase, such being undesirable.
Especially, it is preferable that x is 0.0003-0.01 and y is 0.005-0.5.
v is a number in the range of 1-5.

As a structure of zeolite, for example, expressed by a code defined by International Zeolite Association (IZA), AEI, AET, AEL, AFI, AFO, AFS, AST, ATN, BEA, CAN, CHA, DDR, EMT, ERI, EUO, FAU, FER, LEV, LTL, MAZ, MEL, MFI, MOR, MTT, MTW, MWW, OFF, PAU, RHO, STT, TON, etc. can be used. Among these, those having micropores having a pore diameter of 3 to 9 Å are preferable.
Specifically, AEI, BEA, CHA, FER, MFI, and MWW are preferable.

The catalyst may be used for the reaction as it is, or may be used for the reaction by granulation and molding using a substance or a binder inert to the reaction.
Examples of the substance or binder inert to the reaction include alumina or alumina sol, silica, silica gel, quartz, and a mixture thereof. However, the above-mentioned catalyst composition is a composition of a catalytically active component that does not contain these inactive substances and binders.
The particle size of the catalytically active component varies depending on the conditions during synthesis, but is usually 0.01 to 500 μm.
By using such a zeolite and further performing the reaction under specific conditions, the selectivity for propylene can be improved.
And it becomes possible to suppress remarkably byproduct of paraffins and an aromatic compound, and as a result, it becomes possible to obtain very high propylene selectivity by combining appropriate reaction conditions.

(Catalyst preparation)
The method for producing the zeolite of the present invention is not particularly limited, and can be prepared by a method generally called hydrothermal synthesis. It is also possible to change the composition after the hydrothermal synthesis by modification such as ion exchange, dealumination treatment, impregnation or loading. The zeolite used in the present invention may be prepared by any method as long as it falls within the above composition range when subjected to the reaction.

2. Reaction raw material (ethylene)
The ethylene used as a reaction raw material is not particularly limited. For example, those produced from petroleum feedstock by catalytic cracking or steam cracking, etc., those obtained by performing FT (Fischer-Tropsch) synthesis using hydrogen / CO mixed gas obtained by coal gasification as raw material, ethane Obtained by various known methods such as those obtained by the dehydrogenation method or oxidative dehydrogenation method, those obtained by the metathesis reaction and homologation reaction of propylene, those obtained by the MTO reaction, those obtained by the dehydration reaction of ethanol In this case, a compound in which a compound other than ethylene resulting from each production method is arbitrarily mixed may be used as it is, or purified ethylene may be used.

(Methanol and dimethyl ether)
The origin of production of methanol and dimethyl ether used as raw materials for the reaction is not particularly limited. For example, one obtained by hydrogenation reaction of coal and natural gas, and by-product hydrogen / CO mixed gas in the steel industry, one obtained by reforming reaction of plant-derived alcohols, one obtained by fermentation method And those obtained from organic materials such as recycled plastic and municipal waste. At this time, a state in which compounds other than methanol and dimethyl ether resulting from each production method are arbitrarily mixed may be used as it is, or a purified one may be used.

3. Reaction (1) Reaction method (reaction form)
In the present invention, the reaction between ethylene and methanol and / or dimethyl ether is a gas phase reaction. Although there is no restriction | limiting in particular in the form of a reactor, Usually, a continuous type fixed bed reactor and a fluidized bed reactor are selected.
Further, the reaction substrate may be divided and supplied for the purpose of dispersing heat generated by the reaction.
The catalyst of the present invention has less coking than the conventional catalyst and the rate of catalyst deterioration is slow, but when performing continuous operation for one year or longer, it is necessary to regenerate the catalyst during operation.
When selecting a fixed bed reactor, it is desirable to install at least two reactors and operate while switching between reaction and regeneration.
On the other hand, when selecting a fluidized bed reactor, it is preferable to carry out the reaction while continuously feeding the catalyst to the regeneration tank and continuously returning the catalyst regenerated in the regeneration tank to the reactor.

(Supply concentration ratio of ethylene and methanol and / or dimethyl ether)
The amount of ethylene supplied to the reactor is usually 0.2 or more, preferably 0.5 or more in terms of a molar ratio based on the total number of moles of methanol supplied to the reactor and twice the number of moles of dimethyl ether. More preferably, it is 0.8 or more, and is usually 10 or less, preferably 5 or less, more preferably 3 or less.
If it is too low, the amount of ethylene consumed by the reaction tends to decrease. If it is too high, the amount of unreacted ethylene increases, and the production cost including the separation operation tends to increase.
When ethylene and methanol and / or dimethyl ether are supplied to the reactor, they may be supplied separately or after a part or all of them are mixed in advance.

(Substrate concentration)
The sum of the concentrations of ethylene, methanol, and dimethyl ether in the gas fed to the reactor is 85 mol% or less in all the feed components. More preferably, it is 5 mol% or more and 85 mol% or less. When the substrate concentration is too high, the production of aromatic compounds and paraffins becomes remarkable, and the selectivity for propylene decreases as the space velocity decreases. If the substrate concentration is too low, the reaction rate becomes slow, so a large amount of catalyst is required, and the reactor tends to be too large.

(Diluent)
In the reactor, in addition to ethylene and methanol and / or dimethyl ether, helium, argon, nitrogen, carbon monoxide, carbon dioxide, hydrogen, water, paraffins, hydrocarbons such as methane, aromatic compounds, In addition, a gas inert to the reaction, such as a mixture thereof, can be present, and among these, water (water vapor) is preferably present together.
Impurities contained in the reaction raw material may be used as a diluent, or a separately prepared diluent may be mixed with the reaction raw material. The diluent may be mixed with the reaction raw material before entering the reactor, or may be supplied to the reactor separately from the reaction raw material.

(2) Reaction conditions (space velocity)
The space velocity mentioned here is the weight space velocity per catalyst weight, and the catalyst weight is the weight of the inert component used for granulation / molding and the catalytically active component containing no binder.
The total number of moles of methanol fed to the reactor and twice the number of moles of dimethyl ether is 1/20 (below, When the total weight space velocity of methanol and / or dimethyl ether and ethylene at the time of methanol conversion 95% is WHSV ₉₅ , the weight space velocity WHSV in the actual reaction is less than 0.85 times WHSV _95. The reaction is performed under the following conditions. More preferably, it is 0.05 times or more and 0.85 times or less of WHSV ₉₅ .
If the space velocity is too high, sufficient propylene selectivity cannot be obtained. On the other hand, if the space velocity is too low, the amount of catalyst necessary to obtain a certain production amount increases, and the reactor tends to be too large.

(Reaction temperature)
The reaction temperature is usually about 300 ° C. or higher, preferably 400 ° C. or higher, more preferably 450 ° C. or higher, and the upper limit is 700 ° C. or lower, preferably 600 ° C. or lower. If the reaction temperature is too low, the reaction rate tends to be low, a large amount of unreacted raw material tends to remain, and the propylene selectivity tends to decrease. On the other hand, when the reaction temperature is too high, the selectivity for propylene tends to decrease remarkably.

(Reaction pressure)
The reaction pressure is usually 2 MPa (absolute pressure, the same applies hereinafter) or less. Preferably it is 1 MPa or less, More preferably, it is 0.7 MPa or less. The lower limit is not particularly limited, but is usually 1 kPa or more, preferably 50 kPa or more. When the reaction pressure is too high, the production of paraffins and aromatic compounds increases, and the propylene selectivity tends to decrease. If the reaction pressure is too low, the reaction rate tends to be slow.

(3) Reaction product As the gas at the outlet of the reactor, a mixed gas containing propylene as a reaction product, unreacted raw materials, by-products and a diluent is obtained.
The propylene concentration in the mixed gas is usually 5 to 95%.
The unreacted raw material is usually ethylene. Depending on the reaction conditions, methanol and / or dimethyl ether are included, but it is preferable to carry out the reaction under such reaction conditions that the conversion of methanol and / or dimethyl ether is 100%. Thereby, separation of the reaction product and the unreacted raw material becomes easy.
By-products include olefins having 4 or more carbon atoms, paraffins, aromatic compounds and water.

(4) Product Separation Method These gases are introduced into a known separation / purification facility, and may be collected, purified, recycled, and discharged according to their components.
Unreacted ethylene is recycled by mixing with the reaction raw materials or by feeding directly to the reactor. In addition, among the by-products, components inactive to the reaction can be used as a diluent.

Specific examples of the present invention are shown in the following examples. However, the present invention is not limited to this example.
[Catalyst preparation]
Preparation Example 1
26.6 g of tetra-n-propylammonium bromide (TPABr), 12.4 g of boric acid and 4.8 g of sodium hydroxide are dissolved successively in 280 g of water, and then 75 g of colloidal silica (SiO ₂ 40%, Al about 0.06%) A mixed solution with 35 g of water was slowly added and sufficiently stirred to obtain an aqueous gel. Next, this gel was charged into a 1000 ml autoclave, and hydrothermal synthesis was performed while stirring at 300 rpm for 72 hours at 170 ° C. under an autogenous pressure. The product was subjected to pressure filtration to separate solid components, sufficiently washed with water, and then dried at 100 ° C. for 24 hours. The dried catalyst was calcined at 550 ° C for 6 hours under air flow to obtain Na-type boroaluminosilicate.

2.0 g of Na-type boroaluminosilicate was suspended in 40 cc of 1M ammonium nitrate aqueous solution and stirred at 80 ° C. for 2 hours. The liquid after the treatment was separated from solid components by suction filtration, sufficiently washed with water, then suspended again in 40 cc of 1M aqueous ammonium nitrate solution and stirred at 80 ° C. for 2 hours. After the treatment, the solid component was separated by suction filtration, sufficiently washed with water, and then dried at 100 ° C. for 24 hours. The dried catalyst was calcined at 500 ° C. for 4 hours under air flow to obtain an H-type boroaluminosilicate (catalyst A). When the composition of the catalyst was quantified by chemical analysis, it was SiO ₂ / Al ₂ O ₃ = 727 (molar ratio) and SiO ₂ / B ₂ O ₃ = 82 (molar ratio) (in formula (1), x = 0.0028). , Y = 0.024). XRD confirmed that the zeolite structure was MFI type.

Preparation Example 2
In the same manner as in Preparation Example 1 except that the amount of sodium hydroxide added in Preparation Example 1 was changed to 5.1 g, and 0.62 g of aluminum nitrate nonahydrate was added together with 12.4 g of boric acid (H-type boroaluminosilicate ( Catalyst B) was obtained. When the composition of the catalyst was quantified by chemical analysis, it was SiO ₂ / Al ₂ O ₃ = 324 (molar ratio) and SiO ₂ / B ₂ O ₃ = 94 (molar ratio) (in formula (1), x = 0.0062). , Y = 0.021). XRD confirmed that the zeolite structure was MFI type.

Preparation Example 3
An H-type aluminosilicate (catalyst C) was obtained in the same manner as in Preparation Example 2, except that boric acid was not added in Preparation Example 2. When the composition of the catalyst was quantified by chemical analysis, it was SiO ₂ / Al ₂ O ₃ = 323 (molar ratio) (x = 0.0062, y = 0 in formula (1)). XRD confirmed that the zeolite structure was MFI type.

Preparation Example 4
2.4 g of sodium hydroxide was dissolved in 51 g of water, 21 g of hexamethyleneimine was added with stirring, and 0.12 g of sodium aluminate (70%) was further added. To the transparent solution, 12.4 g of boric acid was added and stirred for 30 minutes, and 9.0 g of fumed silica was added and sufficiently stirred to obtain an aqueous gel. Next, this gel was charged into a 200 ml autoclave, and hydrothermal synthesis was performed while stirring at 300 rpm at 175 ° C. for 7 days under an autogenous pressure. The treatment after synthesis was carried out in the same manner as in Preparation Example 1 to obtain an H-type boroaluminosilicate (catalyst D). When the composition of the catalyst was quantified by chemical analysis, it was SiO ₂ / Al ₂ O ₃ = 311 (molar ratio) and SiO ₂ / B ₂ O ₃ = 109 (molar ratio) (in formula (1), x = 0.0064). , Y = 0.018). XRD confirmed that the zeolite structure was MWW type.

Preparation Example 5
35% tetra-n-ethylammonium hydroxide (TEAOH) 37.0 g, boric acid 0.33 g, sodium hydroxide 0.2 g and water 12 g were added sequentially, and 12 g of colloidal silica (SiO ₂ 40%, Al approx. 0.06%) was stirred. Slowly added and stirred well for 2 hours to obtain an aqueous gel. Next, the gel was stirred at 100 ° C. for 3 hours to evaporate water. 12 g of the solid with reduced water content was charged into a 100 ml autoclave, and hydrothermal synthesis was performed at 175 ° C. for 72 hours under an autogenous pressure. The product was sufficiently washed with water and then dried at 100 ° C. for 24 hours. The operation after drying was performed in the same manner as in Preparation Example 1 to obtain an H-type boroaluminosilicate (catalyst E). When the composition of the catalyst was quantified by chemical analysis, it was SiO ₂ / Al ₂ O ₃ = 671 (molar ratio) and SiO ₂ / B ₂ O ₃ = 128 (molar ratio) (in formula (1), x = 0.0030). , Y = 0.016). XRD confirmed that the zeolite structure was the BEA type.

[reaction]
Example 1
(Measurement of WHSV ₉₅ ): Comparative Example 1
A normal pressure fixed bed flow reactor was used for the reaction, and a quartz reaction tube having an inner diameter of 6 mm was filled with a mixture of 0.1 g of catalyst and 0.4 g of quartz sand as a diluent. Catalyst A produced in Preparation Example 1 was used as the catalyst, and ethylene, methanol, water and nitrogen were supplied to the reactor through an evaporator. 70 minutes after the start of the reaction, the product was analyzed by gas chromatography.
As a result of obtaining WHSV ₉₅ (weight space velocity of total of ethylene and methanol when methanol conversion becomes 95%) by changing WHSV, it was 26 Hr ⁻¹ .
Table 1 shows reaction conditions and reaction results.

Example 1
The reaction was performed in the same manner as in Comparative Example 1 except that WHSV / WHSV ₉₅ was changed to 0.71.
The reaction conditions and reaction results are shown in Table 1.
Example 2
The reaction was conducted in the same manner as in Comparative Example 1 except that WHSV / WHSV ₉₅ was changed to 0.09.
The reaction conditions and reaction results are shown in Table 1.

Example 2: Example in which the total concentration of ethylene and methanol was 90 mol% with respect to Example 1 (measurement of WHSV ₉₅ ): Comparative Example 2
The reaction was performed in the same manner as in Comparative Example 1 except that the total concentration of ethylene and methanol was 90 mol%. As a result of obtaining WHSV ₉₅ by changing WHSV, it was 38 Hr ⁻¹ .
The reaction conditions and reaction results are shown in Table 1.
Comparative Example 3
The reaction was conducted in the same manner as in Comparative Example 2 except that WHSV / WHSV ₉₅ was changed to 0.68.
The reaction conditions and reaction results are shown in Table 1.
Comparative Example 4
The reaction was conducted in the same manner as in Comparative Example 2 except that WHSV / WHSV ₉₅ was changed to 0.09.
The reaction conditions and reaction results are shown in Table 1.

Example 3: Example in which the composition of the catalyst was changed from Example 1 and a catalyst outside the scope of the present invention was used (measurement of WHSV ₉₅ ): Comparative Example 5
The reaction was performed in the same manner as in Comparative Example 1 except that the catalyst used was changed to Catalyst C produced in Preparation Example 3. As a result of obtaining WHSV ₉₅ by changing WHSV, it was 38 Hr ⁻¹ .
The reaction conditions and reaction results are shown in Table 1.
Comparative Example 6
The reaction was performed in the same manner as in Comparative Example 5 except that WHSV / WHSV ₉₅ was changed to 0.68.
The reaction conditions and reaction results are shown in Table 1.
Comparative Example 7
The reaction was conducted in the same manner as in Comparative Example 5 except that WHSV / WHSV ₉₅ was changed to 0.09.
The reaction conditions and reaction results are shown in Table 1.
In the following table, MeOH means methanol, ETY means ethylene, and PPY means propylene.

In Table 1, when Examples 1 and 2 of Example 1 are compared with Comparative Example 1, it can be seen that the selectivity for propylene is high within the range of condition (B) (WHSV / WHSV ₉₅ is 0.85 or less).
On the other hand, in Example 2 that does not satisfy the condition (A) (the total concentration of methanol and / or dimethyl ether and ethylene supplied to the reactor is 0.85 mol% or less with respect to the total supply components), the condition (B) Within the range, propylene selectivity is low. That is, if the condition (A) is not satisfied, the selectivity of propylene is low even within the range of the condition (B), and both the conditions (A) and (B) must be satisfied in order to increase the selectivity of propylene. I understand that there is.
In Example 3 where the catalyst does not have M ^II (one or more metal elements of Groups 1 to 15 of the periodic table other than Al, Ga, Fe (III), Si), the conditions are the same as in Example 2. Even within the range of (B), the selectivity of propylene is reduced. That is, it can be seen that the M ^II component is necessary to increase the selectivity of propylene even if both the conditions (A) and (B) are satisfied.

Example 4: Example in which the total concentration of methanol and ethylene was changed from Example 1 (measurement of WHSV ₉₅ ): Comparative Example 8
The reaction was performed in the same manner as in Example 1 except that the total concentration of methanol and ethylene was changed to 13 mol%. As a result of obtaining WHSV ₉₅ by changing WHSV, it was 7.5 Hr ⁻¹ .
The reaction conditions and reaction results are shown in Table 2.

Example 3
The reaction was conducted in the same manner as in Comparative Example 8 except that WHSV / WHSV ₉₅ was changed to 0.68.
The reaction conditions and reaction results are shown in Table 2.
Example 4
The reaction was conducted in the same manner as in Comparative Example 8 except that WHSV / WHSV ₉₅ was changed to 0.09.
The reaction conditions and reaction results are shown in Table 2.

Example 5: Example in which the composition of the catalyst was changed with respect to Example 1 (measurement of WHSV ₉₅ ): Comparative Example 9
The reaction was performed in the same manner as in Example 1 except that the catalyst used was changed to the catalyst B produced in Preparation Example 2. As a result of obtaining WHSV ₉₅ by changing WHSV, it was 29 Hr ⁻¹ .
The reaction conditions and reaction results are shown in Table 2.
Example 5
The reaction was conducted in the same manner as in Comparative Example 9 except that WHSV / WHSV ₉₅ was changed to 0.66.
The reaction conditions and reaction results are shown in Table 2.
Example 6
The reaction was conducted in the same manner as in Comparative Example 9 except that WHSV / WHSV ₉₅ was changed to 0.10.
The reaction conditions and reaction results are shown in Table 2.

  From Table 2, Example 4 in which the total concentration of methanol and / or dimethyl ether and ethylene fed to the reactor within the range of the condition (A) was reduced with respect to Example 1, and the catalyst within the scope of the present invention. Also in Example 5 in which the components were changed, it was found that the selectivity for propylene was high within the range of the requirement (B) as in Example 1.

Example 6: Example in which the catalyst was changed from Example 4 (measurement of WHSV ₉₅ ): Comparative Example 10
The reaction was performed in the same manner as in Example 3, except that the catalyst used was changed to the catalyst D produced in Preparation Example 4. As a result of obtaining WHSV ₉₅ by changing WHSV, it was 2.3 Hr ⁻¹ .
Table 3 shows reaction conditions and reaction results in WHSV ₉₅ (WHSV / WHSV ₉₅ = 1).
Example 7
The reaction was performed in the same manner as in Comparative Example 10 except that WHSV / WHSV ₉₅ was changed to 0.70. The reaction conditions and reaction results are shown in Table 3.
Example 8
The reaction was conducted in the same manner as in Comparative Example 10 except that WHSV / WHSV ₉₅ was changed to 0.09. The reaction conditions and reaction results are shown in Table 3.

Example 7: Example in which the catalyst was changed from Example 4 (measurement of WHSV ₉₅ ): Comparative Example 11
The reaction was carried out in the same manner as in Example 3, except that the catalyst used was changed to the catalyst E produced in Preparation Example 5. As a result of obtaining WHSV ₉₅ by changing WHSV, it was 1.4 Hr ⁻¹ .
Table 3 shows reaction conditions and reaction results in WHSV ₉₅ (WHSV / WHSV ₉₅ = 1).
Example 9
The reaction was conducted in the same manner as in Comparative Example 11 except that WHSV / WHSV ₉₅ was changed to 0.67. The reaction conditions and reaction results are shown in Table 3.
Example 10
The reaction was conducted in the same manner as in Comparative Example 11 except that WHSV / WHSV ₉₅ was changed to 0.09. The reaction conditions and reaction results are shown in Table 3.

  From Table 3, it can be seen that also in Example 6 and Example 7 in which the catalyst component was changed within the scope of the present invention with respect to Example 4, the propylene selectivity was high within the range of the conditions (A) and (B). .

Claims (2)

In a process for producing propylene by contacting ethylene and methanol and / or dimethyl ether in a reactor in the presence of a catalyst,
As a catalyst, a zeolite selected from MFI type, MWW type, and BEA type having the composition of the following formula (1) is used.
MIxMIIySizOv (1)
(In the formula (1),
MI indicates the Al.
MII represents boron .
x: y: z = 0.0003~ 0.01 : 0.005 ~0.5: 1)
A method for producing propylene , comprising contacting ethylene and methanol and / or dimethyl ether at a reaction temperature of 400 to 600 ° C. and a reaction pressure of 50 kPa to 1 MPa under conditions satisfying the following conditions (A) and (B):
Condition (A): The total concentration of methanol and / or dimethyl ether and ethylene fed to the reactor is 85 mol% or less with respect to all the feed components. Condition (B): The reactor is changed by changing the weight hourly space velocity WHSV in advance . to the number of moles of methanol supplied, relative to the sum of twice the number of moles of dimethyl ether, and the number of moles of methanol at the reactor outlet, when the sum of twice the number of moles of dimethyl ether is 1/20 The total weight space velocity WHSV ₉₅ of methanol and / or dimethyl ether and ethylene was determined, and the weight space velocity WHSV of methanol and / or dimethyl ether in the reactor was 0.85 times or less than the WHSV ₉₅ . The amount of ethylene supplied to the reactor, and the number of moles of methanol fed to the reactor, and wherein the relative sum of twice the number of moles of dimethyl ether is 0.2 to 10 molar ratio The method for producing propylene according to claim 1 .