KR101382804B1 - Method for producing propylene - Google Patents

Abstract

Provided is a process for obtaining propylene in high yield from at least one of ethanol and ethylene. In a process for producing propylene by contacting at least one of ethanol and ethylene with a catalyst in a reactor, aluminosilicates having a pore diameter of less than 0.5 nm are used as catalyst. The catalyst is preferably an aluminosilicate having an 8-membered ring or a 9-membered ring, particularly CHA structure. By manufacturing polypropylene which is a general-purpose resin from propylene manufactured using bioethanol which is a plant-derived raw material, environmental load can be reduced.

Description

Process for the production of propylene {METHOD FOR PRODUCING PROPYLENE}

The present invention relates to a process for producing propylene by contacting at least one of ethanol and ethylene in the presence of a catalyst in a reactor.

The invention also relates to a process for producing polypropylene using the produced propylene.

As a method for producing propylene, conventionally, naphtha steam cracking and fluid catalytic cracking of reduced pressure diesel gas have been generally performed. Recently, a metathesis reaction based on ethylene and 2-butene, methanol and / or MTO processes using dimethyl ether as a raw material have also attracted attention (Patent Document 1).

On the other hand, the use of a plant-derived raw material as a polymer with a low environmental load has recently attracted attention, and several polymers have been introduced to the market. Polypropylene, a general-purpose resin, is mainly produced from propylene based on crude oil. If propylene can be produced using a plant-derived raw material (bioethanol), the effect of reducing the environmental load is expected to be very large.

Patent Document 1: U.S. Pat.No.

DISCLOSURE OF INVENTION

Problems to be solved by the invention

Patent Literature 1 discloses that an alcohol having 1 to 4 carbon atoms is used as a raw material, and the raw material is not limited to methanol. However, the alcohol specifically disclosed in the examples is only methanol, and ethanol is used as the raw material. One embodiment is not described.

When the present inventors used ZSM-5, an aluminosilicate generally known as a catalyst for MTO, and SAPO-34, a silica aluminophosphate, as a catalyst, the reaction was carried out using ethanol as a raw material. It has been found to be dehydrated to produce ethylene. And once ethylene was produced, subsequent reaction was very slow and it turned out that the yield of propylene is very low. On the other hand, when methanol is used as a raw material, olefins such as ethylene are generated from methanol, and the produced ethylene and methanol as the raw material can be reacted to efficiently produce propylene, which is verified in Patent Document 1 described above.

As described above, if the propylene can be produced using a plant-derived raw material (bioethanol), the effect of reducing the environmental load is expected to be very large. Conventionally, a method for producing propylene using ethanol as a raw material has been thoroughly studied. There was no desire to establish a method for producing propylene with high yield using ethanol as a raw material.

An object of the present invention is to provide a method for obtaining propylene in high yield from at least one of ethanol and ethylene. The present invention also provides a process for producing polypropylene from propylene produced by this process.

Means for solving the problem

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors discovered that propylene can be manufactured in very high yield from at least one of ethanol and ethylene by using the catalyst which has a specific physical property, and came to this invention. .

That is, the first aspect of the present invention is a method for producing propylene by contacting at least one of ethanol and ethylene with a catalyst in a reactor, wherein the catalyst comprises aluminosilicate having a pore diameter of less than 0.5 nm as a catalytically active component. It contains in the manufacturing method of propylene characterized by the above-mentioned.

A second aspect of the present invention is a method for producing propylene, in the above method, wherein the catalytically active component is an aluminosilicate having an 8-membered ring or a 9-membered ring.

According to a third aspect of the present invention, there is provided a method for producing propylene, in which the aluminosilicate structure is CHA in the above method.

According to a fourth aspect of the present invention, there is provided a method for producing propylene, in which the molar ratio of SiO ₂ / Al ₂ O _{3 in the} aluminosilicate is 5 or more.

A fifth aspect of the present invention is a method for producing propylene, in which the propylene is produced while continuously regenerating the catalyst in a facility equipped with a fluidized bed reactor and a regenerator.

In a sixth aspect of the present invention, in the above method, at least one conversion ratio of ethanol and ethylene (conversion ratio from at least one of ethanol and ethylene to a compound other than ethanol and ethylene) is 20% or more and 80% or less. It is in the manufacturing method of propylene characterized by performing reaction at.

A seventh aspect of the present invention is a method for producing propylene, wherein in the above method, at least part of ethylene contained in the reactor outlet gas is recycled to the reactor.

An eighth aspect of the present invention is a method for producing polypropylene, wherein polypropylene is produced using propylene produced by the method for producing propylene as a raw material.

Effects of the Invention

According to the present invention, propylene can be produced in high yield from at least one of ethanol and ethylene.

Therefore, according to the present invention, the environmental load can be reduced by producing polypropylene, which is a general-purpose resin, from propylene produced using bioethanol, which is a plant-derived raw material.

Carrying out the invention  Best form for

EMBODIMENT OF THE INVENTION Although the typical aspect for implementing this invention is demonstrated concretely below, this invention is not limited to the following aspect, unless the summary is exceeded.

[catalyst]

<Catalyst active ingredient>

First, the catalyst used by this invention is demonstrated.

The catalyst used in the present invention is an aluminosilicate having a pore diameter of less than 0.5 nm as the catalytically active component. The pore diameter here refers to a crystallographic free diameter of the channels defined by the International Zeolite Association (IZA) and is described in ATLAS OF ZEOLITE FRAMEWORKTYPES FIFTH RIVISED EDITION 2001 (ELSEVIER). And when the pore diameter is less than 0.5 nm, when the shape of a pore (channel) is a round shape, it means that the diameter is less than 0.5 nm, but when a pore shape is elliptical, it means that a short diameter is less than 0.5 nm.

If the pore diameter of the aluminosilicate is 0.5 nm or more, there arises a problem that the by-products (butene, pentene, etc.) other than propylene will increase, and it is impossible to produce propylene in high yield from at least one of ethanol and ethylene. The details of the mechanism of the production of propylene in high yield from at least one of ethanol and ethylene by using aluminosilicates with pore diameters of less than 0.5 nm are not clear, but due to the expression of strong scattering points It is considered that ethanol and ethylene can be activated and that propylene can be selectively produced by a small pore diameter. In other words, as long as the pores are smaller than 0.5 nm in diameter, propylene as the target product can come out of the pores, but it is estimated that butene and pentene as by-products remain in the pores because the molecules are too large. It is thought that such a mechanism improves the selectivity of propylene.

Moreover, there is no restriction | limiting in particular about the minimum of the pore diameter of an aluminosilicate.

As a structure of such aluminosilicate, it is preferable to contain an 8-membered ring or a 9-membered ring normally, and it is more preferable that it consists only of an 8-membered ring.

Aluminosilicates composed of only 8-membered rings are represented by codes prescribed by the International Zeolite Association (IZA), for example, AFX, CAS, CHA, DDR, ERI, ESV, GIS, GOO, ITE, JBW, KFI, LEV, LTA, MER, MON, MTF, PAU, PHI, RHO, RTE, RTH and the like. Aluminosilicates having these structures can be synthesized based on known information. For example, US4544538A discloses a method for synthesizing aluminosilicates having a CHA structure (the crystallographic channel diameter determined by IZA is 0.38 nm). .

Especially, the aluminosilicate whose framework density is 18.0T / nm <^3> or less is preferable, More preferably, AFX, CHA, DDR, ERI, LEV, RHO can be illustrated. Most preferably CHA.

The framework density (unit: T / nm ³ ) herein means the number of T atoms (atoms other than oxygen among the atoms constituting the skeleton of the zeolite) per unit volume (1 nm ³ ) of the zeolite, and this The value is determined by the structure of the zeolite.

The molar ratio of SiO ₂ / Al ₂ O ₃ of the aluminosilicate as the catalytically active component is preferably 5 or more, more preferably 10 or more. If the SiO ₂ / Al ₂ O ₃ molar ratio is too low, it is not preferable because the durability of the catalyst is lowered. The upper limit of the molar ratio of SiO ₂ / Al ₂ O ₃ is usually 1000 or less. If the molar ratio of SiO ₂ / Al ₂ O ₃ is too high, it is not preferable because the catalytic activity is lowered. The molar ratio can be obtained by conventional methods such as fluorescence X-rays and chemical analysis.

The said catalytically active component may be used for reaction as it is as a catalyst, may be granulated and shape | molded using the substance and binder which are inert to reaction, or may be mixed and used for reaction. Examples of the substance or binder inert to the reaction include alumina or alumina sol, silica, silica gel, quartz, and mixtures thereof.

In addition, the composition of the above-mentioned catalytically active component is a composition only of the catalytically active component which does not contain a substance, a binder, etc. which are inert to this reaction. In addition, when the catalyst which concerns on this invention contains a substance, binder, etc. which are inert to this reaction, the catalyst active component mentioned above and the substance, binder, etc. which are inert to this reaction are called a catalyst, and are inert to this reaction. When it does not contain a substance, a binder, etc., it is called a catalyst only by a catalytically active component.

Although the particle diameter of a catalyst changes with the conditions at the time of synthesis, it is 0.01 micrometer-500 micrometers normally as an average particle diameter. If the particle size of the catalyst is too large, the surface area showing the catalytic activity is small, and if the particle size is too small, the handleability is poor, which is not preferable in either case. This average particle diameter can be calculated | required by SEM observation etc.

<Method for Preparing Catalyst>

The preparation method of the catalyst used by this invention is not specifically limited, It is possible to prepare by the well-known method generally called hydrothermal synthesis. In addition, after hydrothermal synthesis, the composition can be changed by modification such as ion exchange, dealumination treatment, impregnation, or supporting.

The catalyst used in the present invention may be one having the above-described physical properties and, furthermore, a composition when provided to the reaction, or may be prepared by any method.

[Feedstock]

Next, ethanol, ethylene, etc. which are used as reaction raw materials in this invention are demonstrated.

Ethanol

It does not specifically limit as ethanol used for the raw material of reaction. For example, those obtained by various known methods, such as those produced by hydration of ethylene, those produced from synthesis gas, and those produced by fermentation using polysaccharides derived from plants as raw materials, may be arbitrarily used. At this time, the compound (especially water) resulting from each manufacturing method may be used as it is, and the refined ethanol may be used as it is.

<Ethylene>

It does not specifically limit as ethylene used for the raw material of reaction. For example, those produced by catalytic cracking or steam cracking from petroleum feedstocks, obtained by performing FT (Fischer Tropsch) synthesis using a hydrogen / CO mixed gas obtained by gasification of coal as a raw material, dehydrogenation of ethane. Obtained by a variety of known methods, such as those obtained by the method or by the oxidative dehydrogenation method, those obtained by the metathesis reaction and homologation reaction of propylene, those obtained by the MTO reaction, and those obtained by the dehydration reaction of ethanol. Can be used arbitrarily, and the thing of the state in which the compound other than ethylene which originates in each manufacturing method was arbitrarily mixed may be used as it is, and purified ethylene may be used.

In addition, when producing propylene by the method of this invention, you may recycle and use the ethylene contained in reactor outlet gas.

<Other raw materials>

In the present invention, in addition to the ethanol and ethylene, an olefin having 4 or more carbon atoms may be present in the reaction raw material. Although it does not specifically limit as C4 or more olefin, For example, when manufacturing propylene by the method of this invention, you may recycle and use the olefin contained in reactor outlet gas. Since some of the olefins having 4 or more carbon atoms are converted to propylene, the olefin in the reactor outlet gas can be recycled in this way to improve the consistent yield of propylene.

In addition, oxygen compounds other than ethanol may be present. As oxygen compound other than ethanol, methanol and dimethyl ether are mentioned, for example.

[Reaction Operation Conditions]

The operation and conditions of the propylene production reaction of the present invention using the catalyst and the reaction raw material described above will be described below.

(1) reaction method

(Reactor)

Although there is no restriction | limiting in particular in the form of the reactor used, Usually, a continuous fixed bed reactor or a fluidized bed reactor is selected. Preferably it is a fluidized bed reactor.

In addition, when filling the above-mentioned catalyst in the fluidized bed reactor, in order to suppress the temperature distribution of the catalyst layer small, granular materials inert to the reaction of quartz sand, alumina, silica, silica-alumina, and the like may be mixed with the catalyst and filled. . In this case, the amount of the granular material inert to the reaction of quartz sand or the like is not particularly limited. Moreover, it is preferable that this granular material is the particle size of the grade similar to a catalyst from a uniform mixing property with a catalyst.

The reaction substrate (reaction raw material) may be dividedly supplied to the reactor in order to disperse the exothermic heat accompanying the reaction.

When selecting a fluidized bed reactor, it is preferable to install a regenerator of the catalyst to the reactor, to continuously send the catalyst extracted from the reactor to the regenerator, and to carry out the reaction while continuously returning the regenerated catalyst to the reactor. .

Here, as a regenerator of a catalyst, what is regenerated by treating the catalyst introduce | transduced from a reactor by nitrogen gas, water vapor, etc. containing oxygen is mentioned.

(Substrate concentration)

Although there is no restriction | limiting in particular about the density | concentration (namely, substrate concentration) of at least 1 of ethanol and ethylene in the total feed component supplied to a reactor, 90 mol% or less is preferable in the total feed component of the sum total of ethanol and ethylene. More preferably, they are 5 mol% or more and 70 mol% or less. When the substrate concentration is too high, the production of aromatic compounds and paraffins becomes remarkable, and the yield of propylene tends to decrease. If the substrate concentration is too low, a large amount of catalyst is required because the reaction rate is delayed, and the reactor tends to be too large.

Therefore, it is preferable to dilute at least one of ethanol and ethylene with the diluents described below as needed in such a substrate concentration.

(diluent)

In the reactor, in addition to at least one of ethanol and ethylene, gases inert to the reaction, such as helium, argon, nitrogen, carbon monoxide, carbon dioxide, hydrocarbons such as hydrogen, water, paraffins, methane, aromatic compounds, and mixtures thereof, Although it can exist, it is preferable that water (water vapor) coexists among these.

As such a diluent, the impurity contained in the reaction raw material may be used as it is, or the diluent prepared separately may be mixed with the reaction raw material and used.

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.

(2) reaction conditions

(Space speed)

The space velocity herein refers to a flow rate of at least one of ethanol and ethylene which are reaction raw materials per weight of the catalyst (catalyst active component), where the weight of the catalyst is a catalyst that does not contain an inert component or binder used for assembling and forming the catalyst. The weight of the active ingredient. The flow rate is a flow rate (weight / hour) of at least one sum of ethanol and ethylene (that is, the sum when using ethanol and ethylene).

The space velocity is preferably between 0.01hr ^-1 to 500hr ^-1, and is even more preferably between 0.1hr ^-1 to 100hr ^-1. If the space velocity is too high, it is not preferable because the ethylene in the reactor outlet gas increases and the propylene yield decreases. In addition, when the space velocity is too low, undesirable by-products such as paraffins are generated, which is not preferable because the propylene yield is lowered.

(Reaction temperature)

As a minimum of reaction temperature, it is about 200 degreeC or more normally, Preferably it is 300 degreeC or more, and as an upper limit of reaction temperature, it is 700 degrees C or less normally, Preferably it is 600 degrees C or less. If the reaction temperature is too low, the reaction rate is low, there is a tendency for many unreacted raw materials to remain, and the yield of propylene also decreases. On the other hand, when reaction temperature is too high, the yield of propylene will fall remarkably.

(Reaction pressure)

The upper limit of the reaction pressure is usually 2 MPa (absolute pressure, the same below), preferably 1 MPa or less, and more preferably 0.7 MPa or less. In addition, the minimum of reaction pressure is although it does not restrict | limit especially, Usually, it is 1 kPa or more, Preferably it is 50 kPa or more. When the reaction pressure is too high, the amount of undesirable by-products such as paraffins increases, and the yield of propylene tends to decrease. If the reaction pressure is too low, the reaction rate tends to be delayed.

(Telephone rate)

In the present invention, the reaction is preferably carried out under the condition that the conversion ratio of at least one of ethanol and ethylene (the conversion of at least one of ethanol and ethylene to a compound other than ethanol and ethylene) is 20% or more and 80% or less. .

When this conversion rate is less than 20%, since unreacted ethanol or ethylene is large and propylene yield is low, it is unpreferable. On the other hand, when it exceeds 80%, undesirable by-products, such as paraffins, increase, and since propylene yield falls, it is unpreferable. The conversion rate is more preferably 20% or more and 70% or less.

When reacting in a fluidized bed reactor, it is possible to operate at a desirable conversion rate by adjusting the residence time of the catalyst in the reactor and the residence time in the regenerator.

(3) reaction products

As the reactor outlet gas (reactor effluent), a mixed gas containing propylene, ethylene, by-products and diluents as reaction products is obtained. The propylene concentration in the mixed gas is usually 1 to 95% by weight, preferably 2 to 80% by weight.

Depending on the reaction conditions, ethanol is contained in this mixed gas, but it is preferable to carry out the reaction under reaction conditions in which no ethanol is contained in the reactor outlet gas. This facilitates separation of the reaction product and the unreacted raw material.

Ethylene is usually contained in this mixed gas, and it is preferable to recycle at least one part of the ethylene in this mixed gas to a reactor and reuse it as a reaction raw material.

Moreover, as a by-product, C4 or more olefins, paraffins, an aromatic compound, and water are mentioned.

(4) separation of product

The mixed gas containing propylene, ethylene, by-products and diluents, which are reaction products, as a reactor outlet gas product, is introduced into a known separation and purification facility, and the recovery, purification, recycling and discharge treatment are performed according to the respective components. Just do it.

It is preferable to recycle part or all of components other than propylene (olefin, paraffin, etc.), especially ethylene, by mixing with the reaction raw material or supplying directly to a reactor after the said separation and purification. In addition, in in-products, the component inactive to reaction can be reused as a diluent.

[Production of Polypropylene]

The manufacturing method of the polypropylene of this invention is a method of manufacturing polypropylene using the propylene manufactured by the manufacturing method of the propylene of this invention mentioned above.

The manufacturing method of this polypropylene is not specifically limited, What is necessary is just to polymerize propylene in presence of the catalyst for propylene polymerization in accordance with a conventional method.

Although an Example is given to the following and this invention is demonstrated to it further more concretely, this invention is not limited to a following example at all.

&Lt; Example 1 >

Proton type aluminosilicate having CHA structure, SiO ₂ / Al ₂ O ₃ = 36 (molar ratio) was used as a catalyst, and propylene was produced according to the present invention using ethanol as a raw material. This aluminosilicate is 0.38 nm in both pore diameter and short diameter.

The reaction was filled with a mixture of 100 mg of the catalyst and 400 mg of quartz yarn in a quartz reaction tube having an inner diameter of 6 mm using a atmospheric pressure fixed bed flow reactor. Ethanol and nitrogen were supplied to the reactor through an evaporator so that the space velocity of ethanol was 0.3hr ^{- 1} , and 10 volume% ethanol and 90 volume% nitrogen, and reaction was performed at 400 degreeC and 0.1 Mpa. 3.5 hours after the start of the reaction, the product was analyzed by gas chromatography.

Table 1 shows the reaction results.

In addition, since ethanol dehydrates immediately to become ethylene when it enters the reactor, the conversion rate is calculated as ((moles of ethanol supplied-moles of ethylene at the outlet of the reactor) / moles of ethanol supplied). . In addition, the selectivity of each product was calculated as carbon mol% of the component except ethylene in the reactor outlet gas, and the propylene yield was calculated as the product of ethanol-ethylene conversion and propylene selectivity.

As shown in Table 1, the conversion rate was 51.6% and the propylene selectivity was 81.3%, all very high, and the result was 41.9% as the propylene yield. Therefore, in the present embodiment, it can be seen that when ethylene in the reactor outlet gas is recycled, 80% or more is possible in the consistent yield of propylene.

<Example 2>

The reaction was carried out under the same catalyst and reaction conditions as in Example 1 except that the space velocity of ethanol was changed to 0.6 hr ⁻¹ , the ethanol concentration was 30 vol%, and the nitrogen was 70 vol%. The product was analyzed by gas chromatography 4.5 hours after the start of the reaction.

Table 2 shows the reaction results.

As shown in Table 2, the conversion rate was 65.1% and the propylene selectivity was 63.0%, all very high, and a result of 41.1% was obtained as the propylene yield.

&Lt; Example 3 >

The same catalyst and reaction conditions as those of Example 1 were used except that ethanol as a raw material was changed to ethylene, ethylene concentration was 30 vol%, nitrogen concentration was 70 vol%, and ethylene space velocity was changed to 0.4 hr ⁻¹ . The reaction was carried out. The product was analyzed by gas chromatography 3.3 hours after the start of the reaction. Table 2 shows the reaction results.

As shown in Table 2, the conversion rate was 73.7% and the propylene selectivity was 54.6%, all very high, and a result of 40.3% was obtained as the propylene yield.

<Example 4>

Embodiment, as a catalyst, except that as an aluminosilicate of the proton type having a LEV structure, a _{SiO 2 / Al 2 O 3 =} 30 ( mole ratio), a pore, the minor axis as the catalyst having a pore of 0.36㎚, 0.48㎚ major axis, The reaction was carried out under the same reaction conditions as in Example 3. The product was analyzed by gas chromatography 1.0 hour after the start of the reaction.

Table 2 shows the reaction results.

As shown in Table 2, the conversion ratio was 71.2% and the propylene selectivity was 57.4%, all very high, and the result was 40.9% as the propylene yield.

&Lt; Comparative Example 1 &

As a catalyst, a proton type aluminosilicate (H-ZSM5) having an MFI structure, SiO ₂ / Al ₂ O ₃ = 311 (molar ratio), pores having a short diameter of 0.51 nm and a long diameter of 0.55 nm, and a short diameter of 0.53 nm as pores The reaction was carried out under the same reaction conditions as those in Example 1 except that those having pores having a long diameter of 0.56 nm were used. The product was analyzed by gas chromatography 2.0 hours after the start of the reaction. Table 1 shows the reaction results.

As can be seen from Table 1, the conversion was 34.4%, the propylene selectivity 32.2%, the propylene yield 11.1%, and a sufficient yield was not obtained.

&Lt; Comparative Example 2 &

As the catalyst, the reaction was carried out under the same reaction conditions as those in Example 1 except that proton type silicoaluminophosphate (SAPO-34) having a CHA structure synthesized according to US Patent 4440871 was used. The product was analyzed by gas chromatography 3.3 hours after the start of the reaction. Table 1 shows the reaction results. Moreover, this silicoaluminophosphate has a pore of 0.38 nm in both short diameter and long diameter.

As can be seen from Table 1, the conversion ratio was 5.7%, the propylene selectivity 88.5%, the propylene yield 5.0%, and a sufficient yield was not obtained.

&Lt; Comparative Example 3 &

As a catalyst, a proton type aluminosilicate having a FAU structure, SiO ₂ / Al ₂ O ₃ The reaction was carried out under the same reaction conditions as those in Example 3, except that those having a pore diameter of 0.74 nm were used for both = 7 (molar ratio), short diameter, and long diameter. The product was analyzed by gas chromatography 5.7 hours after the start of the reaction. Table 2 shows the reaction results.

As can be seen from Table 2, the conversion rate was 14.6%, the propylene selectivity was 10.5%, the propylene yield was 1.5%, and a sufficient yield was not obtained.

Although this invention was detailed also demonstrated with reference to the specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention.

This application is based on the JP Patent application (Japanese Patent Application No. 2006-094538) of an application on March 30, 2006, The content is taken in here as a reference.

The present invention provides a process for obtaining propylene in high yield from at least one of ethanol and ethylene, and a process for producing polypropylene from propylene produced by this process. The present invention can reduce the environmental load by producing polypropylene, which is a general-purpose resin, from propylene produced using bioethanol, which is a plant-derived raw material.

Claims (8)

A process for producing propylene by contacting at least one of ethanol and ethylene with a catalyst in a reactor, wherein the catalyst comprises aluminosilicates having a pore diameter of less than 0.5 nm and having 8 or 9 membered rings as catalytically active components. It is contained as a manufacturing method of propylene. The method according to claim 1, A process for producing propylene in which the structure of the aluminosilicate is chebazite (CHA). The method according to claim 1, The method of the aluminosilicate of the SiO ₂ / Al ₂ O ₃ molar ratio is less than 5 1000 polypropylene. 4. The method according to any one of claims 1 to 3, A fluidized bed reactor is used as the reactor, and a catalyst regenerator is provided for the reactor, and the catalyst extracted from the reactor is continuously sent to the regenerator, and the catalyst regenerated in the regenerator is continuously returned to the reactor. The manufacturing method which manufactures a propylene while retarding. 4. The method according to any one of claims 1 to 3, In the above production method, propylene is reacted under the condition that the conversion ratio of at least one of ethanol and ethylene (the conversion of at least one of ethanol and ethylene to a compound other than ethanol and ethylene) is 20% or more and 80% or less. Manufacturing method. 4. The method according to any one of claims 1 to 3, And at least part of ethylene contained in the reactor outlet gas of the reactor is recycled to the reactor. delete delete