JP2023177331A - Method for converting alcohol and method for producing hydrocarbon - Google Patents

Abstract

To provide a method for converting alcohol into a target compound with good yield by using an adiabatic reactor and controlling the temperature inside the reaction vessel.SOLUTION: Provided is a method for converting alcohol that comprises contacting a mixed raw material containing methanol and ethanol with an alcohol conversion catalyst in an adiabatic reaction vessel to yield a reaction gas containing an olefin having 3 or more carbon atoms.SELECTED DRAWING: None

Description

The present invention relates to a method for converting alcohol and a method for producing hydrocarbons.

Lower olefins and aromatic compounds are key raw materials in the chemical industry, and demand for propylene in particular is expected to increase, so various production methods have been actively developed and improved. Among these, a method of bringing naphtha or olefins into contact with a catalyst containing zeolite as an active species is known as a general method for producing propylene.

In addition to olefins, the production of chemical products using alcohols such as methanol and ethanol, which are produced from biomass raw materials and waste, has been attracting attention due to the recent rise in environmental conservation awareness. For example, Patent Documents 1 and 2 disclose techniques for converting ethanol to propylene using pentasil-type zeolite and zinc oxide-cerium-supported zeolite, respectively. For example, Patent Document 3 discloses a method for producing propylene from raw materials containing methanol.

International Publication No. 2015/029355 China Application Publication No. 110560155 International Publication No. 2005/56504

When a chemical product manufacturing process is put into practical use, the selection of a reactor and its style is a factor that greatly influences the ease of operation and the size of the environmental impact. Fixed-bed adiabatic reactors do not require heating or cooling of the reactor, and have a less complex structure than reactors such as fluidized beds, making them ideal for reducing the burden on design, construction, and operation. For example, if a fixed bed single-stage adiabatic reactor can be adopted, its advantages will be even greater. However, this reactor also has the disadvantage that it cannot be applied to reaction systems with large endotherms or exotherms.

Patent Documents 1 to 3 disclose technologies for converting each raw material into the desired olefin using a zeolite catalyst, but these technologies cannot be applied to an adiabatic reactor because they generate large amounts of heat and heat. Can not.

Therefore, an object of the present invention is to provide a method for converting alcohol into a target compound with high yield by using an adiabatic reactor and controlling the temperature inside the reactor, and a method for producing hydrocarbons. do.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors discovered that the heat of reaction in a reactor is necessary for converting a raw material mixture of ethanol and methanol into a target compound such as an olefin having 3 or more carbon atoms. It has been found that by controlling the reaction temperature using an adiabatic reactor, alcohol can be converted to the target compound with good yield.
That is, the present invention is as follows.
<1>
A method for converting alcohol, comprising contacting a mixed raw material containing methanol and ethanol with an alcohol conversion catalyst in an adiabatic reactor to obtain a reaction gas containing an olefin having 3 or more carbon atoms.
<2>
The alcohol conversion method according to <1>, wherein the methanol/ethanol molar ratio in the mixed raw material is 0.050 to 2.0.
<3>
The alcohol conversion method according to <1> or <2>, wherein the methanol/ethanol molar ratio in the mixed raw material is 0.20 to 1.5.
<4>
The method for converting alcohol according to any one of <1> to <3>, which comprises separating ethylene and propylene from the reaction gas.
<5>
The alcohol conversion method according to any one of <1> to <4>, wherein the mixed raw material contains an olefin having 4 to 6 carbon atoms.
<6>
The alcohol conversion method according to <5>, wherein the molar ratio of olefin having 4 to 6 carbon atoms/methanol in the mixed raw material is 3.0 or less.
<7>
The alcohol according to any one of <1> to <6>, which comprises recycling at least a part of the reaction gas or a fraction obtained by purifying the reaction gas to the reactor and using it as part of the mixed raw material. Conversion method.
<8>
Separating the reaction gas into a fraction A mainly containing hydrocarbons having 1 to 3 carbon atoms and a fraction B mainly containing hydrocarbons having 4 to 8 carbon atoms, and extracting ethylene from the fraction A. and separating propylene;
The method for converting alcohol according to any one of <1> to <7>, comprising:
<9>
separating the fraction B into a fraction B1 mainly containing aliphatic hydrocarbons having 4 to 6 carbon atoms and a fraction B2 mainly containing aromatic compounds; and at least a part of the fraction B1. recycling it into the reactor and using it as part of the mixed feedstock;
The method for converting alcohol according to <8>, comprising:
<10>
obtaining a steam cracking product containing ethylene and propylene by subjecting said fraction B to steam cracking, and separating ethylene and propylene from said steam cracking product;
The method for converting alcohol according to <8> or <9>, comprising:
<11>
The method for converting alcohol according to any one of <1> to <10>, wherein the reactor is a fixed bed adiabatic reactor.
<12>
The method for converting alcohol according to any one of <1> to <11>, wherein the reactor is a fixed bed single-stage adiabatic reactor.
<13>
The alcohol conversion method according to any one of <1> to <12>, which includes burning coke attached to the alcohol conversion catalyst.
<14>
The alcohol conversion method according to any one of <1> to <13>, wherein the catalyst bed outlet temperature is 450°C to 590°C.
<15>
The alcohol conversion method according to any one of <1> to <14>, wherein the catalyst bed inlet temperature is 450°C to 590°C.
<16>
The alcohol conversion method according to any one of <1> to <15>, wherein the temperature difference between the catalyst bed outlet temperature and the catalyst bed inlet temperature is -70K to 70K.
<17>
The alcohol conversion method according to any one of <1> to <16>, wherein the alcohol conversion catalyst is a zeolite-containing catalyst.
<18>
The method for converting alcohol according to <17>, wherein the zeolite-containing catalyst includes an intermediate pore size zeolite.
<19>
The alcohol conversion method according to <17> or <18>, wherein the zeolite in the zeolite-containing catalyst has a silica/alumina molar ratio of 20 to 2000.
<20>
The method for converting alcohol according to any one of <17> to <19>, wherein the zeolite-containing catalyst contains at least one selected from the group consisting of phosphorus element and silver element.
<21>
The method for converting alcohol according to any one of <1> to <20>, wherein the mixed raw material contains ethylene and the molar ratio of ethylene/ethanol is 0.05 or more.
<22>
The method for converting alcohol according to any one of <1> to <21>, wherein at least one of the methanol and the ethanol is derived from biomass.
<23>
A method for producing hydrocarbons, the method comprising contacting a mixed raw material containing methanol and ethanol with an alcohol conversion catalyst in an adiabatic reactor to obtain a reaction gas containing an olefin having 3 or more carbon atoms.
<24>
A cracking process that decomposes hydrocarbons having two or more carbon atoms;
a purification step of refining the component obtained in the cracking step;
has
A method for producing hydrocarbons, in which the reaction gas obtained by the alcohol conversion method according to any one of <1> to <22> or a purified fraction thereof is combined in the purification step.
<25>
an unsaturated hydrocarbon separation step of separating a fraction mainly containing unsaturated hydrocarbons from the reaction gas obtained by the alcohol conversion method according to any one of <1> to <22>;
A method for producing a monomer, including:
<26>
an olefin separation step of separating a fraction mainly containing olefins from the reaction gas obtained by the alcohol conversion method according to any one of <1> to <22>;
A method for producing an olefin, including.
<27>
a propylene separation step of separating a fraction mainly containing propylene from the reaction gas obtained by the alcohol conversion method according to any one of <1> to <22>;
A method for producing propylene, including:
<28>
an ethylene separation step of separating a fraction mainly containing ethylene from the reaction gas obtained by the alcohol conversion method according to any one of <1> to <22>;
A method for producing ethylene, including:
<29>
a diene separation step of separating a fraction mainly containing diene from the reaction gas obtained by the alcohol conversion method according to any one of <1> to <22>;
A method for producing a diene, including.
<30>
an unsaturated hydrocarbon separation step of separating a fraction mainly containing unsaturated hydrocarbons from the reaction gas obtained by the alcohol conversion method according to any one of <1> to <22>;
an acrylic monomer production step of obtaining an acrylic monomer from the unsaturated hydrocarbon obtained in the unsaturated hydrocarbon separation step;
A method for producing an acrylic monomer, including:
<31>
a propylene separation step of separating a fraction mainly containing propylene from the reaction gas obtained by the alcohol conversion method according to any one of <1> to <22>;
an acrylonitrile production step of obtaining acrylonitrile from the propylene obtained in the propylene separation step;
A method for producing acrylonitrile, including:
<32>
an ethylene separation step of separating a fraction mainly containing ethylene from the reaction gas obtained by the alcohol conversion method according to any one of <1> to <22>;
a styrene production process for producing styrene from the ethylene obtained in the ethylene separation process;
A method for producing styrene, including:
<33>
Polymerizing the monomer obtained by the production method described in <25>,
A method for producing a polymer, including:
<34>
Polymerizing a polymerizable composition containing an olefin obtained by the production method described in <26>,
A method for producing an olefin polymer, including:
<35>
Polymerizing a polymerizable composition containing propylene obtained by the production method described in <27>,
A method for producing a polypropylene polymer, including:
<36>
Polymerizing the ethylene-containing polymerizable composition obtained by the production method according to <28>,
A method for producing a polyethylene polymer, including:
<37>
Polymerizing the diene-containing polymerizable composition obtained by the production method described in <29>,
A method for producing a diene polymer, including:
<38>
Polymerizing a polymerizable composition containing an acrylic monomer obtained by the production method described in <30>,
A method for producing an acrylic monomer-based polymer, comprising:
<39>
Polymerizing a polymerizable composition containing acrylonitrile obtained by the production method described in <31>,
A method for producing an acrylonitrile polymer, including:
<40>
Polymerizing the styrene-containing polymerizable composition obtained by the manufacturing method described in <32>,
A method for producing a styrenic polymer, including:
<41>
Obtaining a reaction gas by the alcohol conversion method according to any one of <1> to <22>;
A method for producing an aromatic compound, the method comprising separating a fraction mainly containing aromatic compounds from the reaction gas.
<42>
an aromatic monomer production step of obtaining an aromatic monomer from the aromatic compound obtained by the production method described in <41>;
A method for producing an aromatic monomer, including:
<43>
Polymerizing a polymerizable composition containing an aromatic monomer obtained by the production method described in <42>,
A method for producing an aromatic monomer-based polymer, comprising:

According to the present invention, it is possible to provide a method for converting alcohol into a target compound with good yield by using an adiabatic reactor and controlling the temperature inside the reactor, and a method for producing hydrocarbons.

FIG. 1 shows a schematic diagram of one embodiment of a fixed bed single stage adiabatic reactor. FIG. 2 shows one embodiment of the flow of the reaction and separation steps. FIG. 3 shows one embodiment of the flow of reaction steps, separation steps, and steam cracking. FIG. 4 shows one embodiment of the flow of the reaction and separation steps. FIG. 5 shows one embodiment of the flow of the reaction and separation steps. FIG. 6 shows one embodiment of the flow of the reaction and separation steps.

The present invention will be specifically explained below. Note that the present invention is not limited to the following embodiment (this embodiment), and can be implemented with various modifications within the scope of the gist.
In this specification, a numerical range indicated using "~" indicates a range that includes the numerical values written before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described stepwise in this specification, the upper limit or lower limit of the numerical range of one step can be arbitrarily combined with the upper limit or lower limit of the numerical range of another step.

[Alcohol conversion method]
The alcohol conversion method of the present embodiment involves contacting a mixed raw material containing methanol and ethanol with an alcohol conversion catalyst in an adiabatic reactor to obtain a reaction gas containing an olefin having 3 or more carbon atoms (hereinafter referred to as (Also referred to as "reaction process.")
Note that propylene can be obtained by separating from the above-mentioned reaction gas, and aromatic compounds can also be obtained by separating from the above-mentioned reaction gas.

According to this embodiment, by using an adiabatic reactor and controlling the temperature inside the reactor, alcohol can be converted into a target compound with good yield. Further, according to the present embodiment, by using an adiabatic reactor, an environmentally friendly alcohol conversion method with low operational load and high energy efficiency can be implemented. Furthermore, even when an adiabatic reactor is used, alcohol can be converted into the target compound with good yield, and coking deterioration of the catalyst can be suppressed, so it is suitable as an alcohol conversion method.

The present inventor discovered that when attempting to convert alcohol using methanol or ethanol alone as a raw material in an adiabatic reactor, the yield of high value-added compounds such as propylene and aromatic compounds decreases, or coking of the catalyst deteriorates. We found that this process progresses. Note that coking deterioration of the catalyst means that coke adheres to the surface of the catalyst and reduces the activity of the catalyst.

Based on these findings, the present inventors have discovered that alcohol can be converted into a target compound with good yield by bringing a mixed raw material containing methanol and ethanol into contact with an alcohol conversion catalyst packed in an adiabatic reactor. It was also found that coking deterioration can be suppressed.
The reason for this is assumed to be that thermal neutralization was achieved by combining endothermic and exothermic reactions that do not inhibit each other. For example, the conversion reaction from methanol to propylene is an exothermic reaction, and the conversion reaction from ethanol to propylene is an endothermic reaction. In this embodiment, it was discovered that endothermic reactions and exothermic reactions proceed without inhibiting each other in the reactor, and by combining these exothermic and endothermic reactions, the reaction conditions can be adjusted even in an adiabatic reactor. could be easily controlled. However, the factors are not limited to this.

<Raw materials>
The alcohol conversion method of this embodiment uses a mixed raw material containing methanol and ethanol. By using the mixed raw materials, it is possible to use an adiabatic reactor and control the temperature inside the reactor to produce a target compound such as propylene in good yield. At least one of methanol and ethanol is preferably derived from biomass from the viewpoint of being environmentally friendly. Note that biomass refers to organic resources other than fossil resources originating from animals and plants, and biomass-derived refers to compounds manufactured using biomass as a raw material.

In the mixed raw material, the methanol/ethanol molar ratio is preferably 0.050 to 2.0, more preferably 0.20 to 1.5, and preferably 0.30 to 1.5. It is more preferable, and even more preferably from 0.30 to 1.0.

Methanol produced by various methods can be used. For example, those obtained by hydrogenation of carbon monoxide obtained from natural gas or coal, hydrogenation of carbon dioxide, and distillation of wood vinegar can be used. Similarly, ethanol produced by various methods can be used. Among these, it is preferable to use bioethanol or waste-derived ethanol from the viewpoint of excellent environmental friendliness. In the manufacturing process of these methanol and ethanol, water is often produced as a by-product or water coexists in the reactor. Therefore, in the alcohol conversion method of this embodiment, the raw materials methanol and ethanol may contain water.

In the alcohol conversion method of the present embodiment, the mixed raw material may further contain an olefin having 4 to 6 carbon atoms. Like methanol and ethanol, olefins having 4 to 6 carbon atoms can provide target compounds such as propylene by contacting with an alcohol conversion catalyst. Examples of the olefin having 4 to 6 carbon atoms include butene, pentene, and hexene. Note that the term "olefin" mentioned above includes cycloparaffins in addition to linear, branched, and cyclic olefins.

In the mixed raw material, the molar ratio of olefin having 4 to 6 carbon atoms/methanol is preferably 3.0 or less, more preferably 1.0 or less, even more preferably 0.5 or less, It is even more preferably 0.15 to 0.5.

The mixed raw material may further contain ethylene. Ethylene, like methanol and ethanol, can provide target compounds such as propylene by contacting with an alcohol conversion catalyst. In the mixed raw material, the molar ratio of ethylene/ethanol is preferably 0.05 or more, more preferably 0.1 or more, and even more preferably 0.1 to 2.0.

In the alcohol conversion method of the present embodiment, the mixed raw material may further contain an oxygen-containing compound having 1 to 6 carbon atoms other than methanol and ethanol. Similar to methanol and ethanol, oxygen-containing compounds having 1 to 6 carbon atoms can provide target compounds such as propylene by contacting them with a catalyst. Examples of oxygen-containing compounds having 1 to 6 carbon atoms other than methanol and ethanol include propanol, dimethyl ether, and diethyl ether.

In the mixed raw material, the oxygen-containing compound having 1 to 6 carbon atoms/ethanol is preferably 1.0 or less, more preferably 0.5 or less.

Note that methanol, ethanol, ethylene, olefins having 4 to 6 carbon atoms, and oxygen-containing compounds having 1 to 6 carbon atoms other than ethanol are also collectively referred to as "effective raw materials."

The mixed raw material can contain, in addition to the above-mentioned effective raw materials, saturated aliphatic hydrocarbons such as paraffin, and olefins having 7 or more carbon atoms. These saturated aliphatic hydrocarbons, olefins having 7 or more carbon atoms, and oxygen-containing compounds can be converted into target compounds such as propylene by contacting them with a catalyst, similar to methanol and ethanol, but they are less reactive than the effective raw materials mentioned above. low gender.

Further, the mixed raw material can contain the entire amount or a part of the reaction gas containing an olefin having 4 or more carbon atoms obtained from the reaction step and the fraction obtained by refining the reaction gas. In this way, by using a so-called recycling reaction system, it is possible to effectively utilize raw materials.

The mixed raw material may contain an inert gas such as nitrogen in addition to the above-mentioned raw materials that can be converted into propylene by the reaction process. In addition, the mixed raw material may contain hydrogen or methane as a diluent gas, but preferably does not contain hydrogen (does not dilute with hydrogen). Hydrogen is sometimes used to suppress coking deterioration of catalysts, but at the same time hydrogenation reactions of generated propylene etc. occur, which has the negative effect of reducing propylene purity (propylene/(propylene + propane)) [mol/mol]. There is. In the method of this embodiment, even if hydrogen dilution is not performed, the coking deterioration rate of the catalyst is small and stable operation is possible, so it is preferable not to perform hydrogen dilution. However, a small amount of hydrogen supplied to the reactor by recycling a fraction separated from the reaction gas, etc. does not have the same adverse effect as in the hydrogen dilution described above.

The total proportion of methanol, olefin having 4 to 6 carbon atoms, ethanol and ethylene in the mixed raw material is preferably 40% by mass or more, and preferably 50% by mass or more with respect to the total mass flow rate of mixed raw material supply. is more preferable. The total mixed feed mass flow rate refers to the total flow rate of all compounds fed to the reactor, including inert gases.

In the mixed raw material, the total content of methanol and ethanol is preferably 30 to 100% by mass, more preferably 40 to 100% by mass, and even more preferably 50 to 100% by mass, based on the mass of the effective raw material supplied. It is. However, for methanol and ethanol, the mass converted into methylene and ethylene, respectively, is used to calculate the methanol mass, ethanol mass, and effective raw material supply mass. Methylene refers to a CH ₂ group obtained by removing a water molecule from methanol.

In the mixed raw material, the total content of olefins having 4 to 6 carbon atoms is preferably 65% by mass or less, more preferably 10 to 55% by mass, based on the mass of the effective raw material supplied.

The effective feed mass of raw materials is the total feed mass of effective raw materials per hour. However, for methanol and ethanol, the mass converted into methylene and ethylene, respectively, is used in the calculation.

In the alcohol conversion method of this embodiment, the mixed raw material may contain water. Since the methanol and ethanol contained in the mixed raw materials are manufactured by various manufacturing methods, they contain "water generated during the manufacturing process." The term "water vapor generated in the manufacturing process" as used herein refers to, for example, moisture generated in the methanol and/or ethanol manufacturing process and derived from moisture that has not been removed.

In the alcohol conversion method of this embodiment, water vapor can be added to the mixed raw material in addition to "water generated in the manufacturing process." Steam has the effect of suppressing coking deterioration by lowering the olefin partial pressure and improving the yield of lower olefins. On the other hand, since water vapor may promote dealumination of zeolite, it is preferable not to include water vapor in the mixed raw material in addition to "water generated in the manufacturing process."

<Adiabatic reactor>
In the alcohol conversion method of this embodiment, an adiabatic reactor is used. Regarding the adiabatic reactor, the description of Adiabatic Fixed-Bed Reactors (Elsevier, 2014, Ch. 1, P. 4, L. 5-24 ISBN: 978-0-12-801306-9) can be referred to. . Examples of the adiabatic reactor include a fixed bed adiabatic reactor, a moving bed adiabatic reactor, and a fluidized bed adiabatic reactor, and a fixed bed adiabatic reactor is preferred for the method of this embodiment. Among the fixed-bed adiabatic reactors, a fixed-bed single-stage adiabatic reactor having only one fixed catalyst bed is more preferable. Since carbonaceous matter (coke) accumulates on the catalyst during the reaction, a single-stage adiabatic fixed-bed reactor with multi-column switching is preferred, which allows combustion and removal of this carbonaceous matter while continuing the reaction.

FIG. 1 is a schematic diagram of a fixed bed single-stage adiabatic reactor. The fixed bed single-stage adiabatic reactor 1 includes a reaction casing 2 provided with a heat insulating material 21 around its outer periphery, a catalyst bed 3, a reactor inlet 4, and a reactor outlet 5. The reaction casing 2 is provided with a heat insulating material 21 on its outer periphery, so that the heat inside the reactor is not released to the outside. In the manufacturing method according to this embodiment, the temperature inside the reactor can be controlled by heat generation and heat absorption due to the reaction.

The catalyst bed 3 is filled with an alcohol conversion catalyst to be described later. A first sheath thermocouple 61 is provided immediately before contacting the catalyst bed inlet 31 of the catalyst bed 3 . A second sheath thermocouple 62 is provided immediately after passing through the catalyst bed outlet 32 of the catalyst bed 3 . These thermocouples measure the temperature of the mixed raw material immediately before contacting the catalyst bed inlet 31 and the temperature of the reaction gas immediately after passing through the catalyst bed outlet 32. Although the catalyst bed 3 may be of a multi-stage type, it is preferably of a single-stage type as shown in FIG.

In the fixed bed single-stage adiabatic reactor 1, a mixed raw material is introduced from the reactor inlet 4, brought into contact with the catalyst bed 3, and a reaction gas is taken out from the reactor outlet 5.

<Reaction conditions>
The inlet temperature of the catalyst bed is the temperature of the mixed raw material immediately before the raw material fluid contacts the catalyst bed filled in the adiabatic reactor. The exit temperature of the catalyst bed is the temperature of the reaction gas immediately after it passes through the catalyst bed. The temperature of the mixed raw materials and reaction gas here means 0d to 0d, where the center of the reactor is 0 and the distance from the center of the reactor to the inner wall of the reactor is d, in a plane perpendicular to the fluid flow direction. It refers to the temperature between 0.8d. As shown in Figure 1, the average input/output reaction temperature is a value calculated by measuring the inlet temperature of the catalyst bed and the outlet temperature of the catalyst bed, and using the calculation formula: [catalyst bed inlet temperature + catalyst bed outlet temperature]/2. (hereinafter also simply referred to as "reaction temperature").

In the alcohol conversion method of this embodiment, the reaction temperature may be 300°C or higher. A thermal equilibrium exists in the produced olefin, and from the viewpoint of achieving an excellent propylene yield, the reaction temperature is preferably 450° C. or higher. Furthermore, from the viewpoint of suppressing the acceleration of coking deterioration promoted at high temperatures, the temperature is preferably lower than 600°C. Specifically, the temperature of the reaction gas at the inlet of the catalyst bed is preferably 450°C to 590°C, and the temperature of the reaction gas at the outlet of the catalyst is preferably 450°C to 590°C.

The temperature difference between the outlet temperature of the catalyst bed and the inlet temperature of the catalyst bed is preferably -70K to 70K, more preferably -60K to 60K.

The reaction pressure is preferably in the range of 0.01 to 3.0 MPaG, more preferably in the range of 0.01 to 1.0 MPaG.

The feed rate of the effective raw material is preferably 0.1 to 1000 hr ⁻¹ , more preferably 0.1 to 500 hr ⁻¹ , and even more preferably 0.5 in terms of the mass-based space velocity (WHSV) of the alcohol conversion catalyst. ~100hr ^-1 . In the alcohol conversion method of the present embodiment, WHSV is calculated after converting ethanol into ethylene as shown in the formula below. In addition, from the viewpoint of excellent productivity of target compounds such as propylene and aromatic compounds, the effective raw material supply mass flow rate is preferably 1 kg/hr or more, more preferably 10 kg/hr or more, and still more preferably 1 t/hr. It is more than hr.

WHSV (hr ⁻¹ ) = Effective raw material supply mass flow rate (kg/hr) / Catalyst amount (kg)
Effective raw material supply mass flow rate (kg/hr) = Methanol flow rate in methylene conversion (kg/hr) + Ethanol flow rate in ethylene conversion (kg/hr) + olefin flow rate with 4 to 6 carbon atoms (kg/hr) + Ethylene flow rate (kg/hr) hr) + flow rate of oxygenated compounds having 1 to 6 carbon atoms other than ethanol (kg/hr)
Methylene conversion methanol flow rate (kg/hr) = methanol flow rate (kg/hr) x 0.438
Ethanol flow rate (kg/hr) = Ethanol flow rate (kg/hr) x 0.609

<Alcohol conversion catalyst>
The alcohol conversion catalyst in the alcohol conversion method of the present embodiment is a solid catalyst that exhibits catalytic ability to convert olefins, methanol, and ethanol into target compounds such as propylene and aromatic compounds. As such a catalyst, a zeolite-containing catalyst is preferable from the viewpoint of the catalyst having excellent thermal durability and propylene selectivity. A common problem in the production of olefins using conventional zeolites is coking deterioration, in which heavy carbon (coke) accumulates and deactivates inside the zeolite pores due to reaction with hydrocarbons. In order to regenerate the catalyst performance, it is necessary to burn and remove the coke in an atmosphere containing oxygen molecules, but as the coke burns, the structure of the zeolite progresses, causing permanent deterioration of the catalyst that cannot be regenerated. Ru. According to the alcohol conversion method of the present embodiment, the production of coke can be suppressed, making it easier to maintain activity even when a zeolite-containing catalyst is used.

(zeolite-containing catalyst)
A zeolite-containing catalyst is a catalyst powder or molded body containing zeolite as an active species. In the alcohol conversion method of the present embodiment, it is preferable to use a so-called intermediate pore diameter zeolite having a pore diameter of 5 to 6 Å as the zeolite in the zeolite-containing catalyst. Intermediate pore size zeolite has a pore size range between the pore size of small pore size zeolite represented by A-type zeolite and the pore size of large pore size zeolite represented by mordenite, X type and Y type zeolite. zeolite found in "Intermediate pore size zeolite" has a so-called 10-membered oxygen ring in its crystal structure.

Examples of intermediate pore size zeolites include ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-21, ZSM-23, ZSM-35, ZSM-38, etc. Among them, ZSM-5 , ZSM-5 type zeolites such as ZSM-11, ZSM-8, and ZSM-38 are preferred. Also, Stud. Surf. Sci. Catal. Zeolites similar to ZSM-5 and ZSM-11 described in 1987, 33, 167-215 can be used, and among these, MFI type zeolite is preferred from the viewpoint of excellent catalytic performance (catalytic activity and durability against coking). Preferably, ZSM-5 is more preferable.

The molar ratio of silica/alumina (SiO ₂ /Al ₂ O ₃ ) in the zeolite contained in the zeolite-containing catalyst of this embodiment can be selected as appropriate, but from the viewpoint of excellent selectivity, it is 20 to 2000, and the From the viewpoint of increasing the durability, the number is more preferably 100 to 1,500, still more preferably 300 to 1,200, and even more preferably 800 to 1,200. The silica/alumina (SiO ₂ /Al ₂ O ₃ ) molar ratio of the zeolite contained in the zeolite-containing catalyst is preferably from 20 to 400, more preferably from 100 to 300, from the viewpoint of catalytic activity. The molar ratio of silica power/alumina of zeolite can be measured by a known method. For example, it can be determined by completely dissolving zeolite in an alkaline aqueous solution and analyzing the resulting solution by plasma emission spectrometry or the like. .

Although there are no particular limitations on the method for synthesizing the zeolite of this embodiment, it can be produced by optimizing various conditions of the conventionally known hydrothermal synthesis method for MFI type zeolite. In general, as a means to efficiently obtain MFI type zeolite by hydrothermal synthesis, methods include hydrothermal synthesis using ammonium salts, urea compounds, amines, alcohols, etc. as appropriate organic agents (SDA); There is a hydrothermal synthesis method in which hydrothermally synthesized MFI zeolite is added as a seed crystal or as a seed slurry in the crystallization stage. Furthermore, it is known that not only organic SDA but also inorganic cations and anions are involved in the structure, and zeolite synthesis depends on the combined functions of each component. In the hydrothermal synthesis method of MFI type zeolite as described above, raw materials such as the type of raw materials and additives (SDA), the amount of additives, pH, silicate power/alumina molar ratio, medium, abundance ratio of cations and anions, etc. A suitable catalyst can be obtained by appropriately optimizing synthesis conditions such as charging composition, synthesis temperature, and synthesis time.

Specifically, for example, the method of synthesis using a seed slurry described in Japanese Patent No. 5426983 and the method exemplified in The Hydrothermal Synthesis of Zeolites (Chemcal Reviews, 2003, 103, 663-702) are listed. It will be done.

Moreover, commercially available zeolite can also be used as long as it is an MFI zeolite having the above-mentioned specific physical properties and composition.

The zeolite-containing catalyst in this embodiment preferably contains at least one element selected from the group consisting of phosphorus element and silver element from the viewpoint of catalyst durability.

Examples of the form of elemental phosphorus include phosphorus polymers (for example, polyphosphoric acid), phosphorus oxides (for example, P ₂ O ₅ ), and compounds in which phosphorus is added to aluminum of zeolite. Moreover, a plurality of them may be included. When the zeolite contains aluminum, the phosphorus element has the effect of suppressing dealumination of the zeolite and, depending on the case, the effect of improving the propylene yield in the propylene production reaction. In the method according to this embodiment, water is generated in the reactor due to the dehydration reaction of alcohol, and the raw materials methanol and ethanol may contain water, so the inside of the reactor tends to become a high-temperature steam atmosphere, and dealumination Although the properties of the zeolite-containing catalyst are likely to change, the zeolite-containing catalyst containing the phosphorus element suppresses dealumination of the zeolite and increases the durability of the catalyst.

The content of the phosphorus element contained in the zeolite-containing catalyst is preferably 0.01 to 2.0% by mass with respect to the mass of the entire catalyst, and more preferably 0.01 to 2.0% by mass from the viewpoint of being excellent in the effect of suppressing dealumination. 05 to 2.0% by mass.

In this embodiment, the content of elemental phosphorus in the catalyst is a value measured using a fluorescent X-ray analyzer. The content of phosphorus element can be measured using a commercially available fluorescent X-ray analyzer under normal conditions according to the instruction manual. For example, when using Rigaku product name "RIX3000", The measurement conditions can be as follows: P-Kα rays are used, the tube voltage is 50 kV, and the tube current is 50 mA.

In this embodiment, phosphoric acid and/or phosphate (hereinafter also referred to as "phosphorus raw material") is used as a raw material for the phosphorus element contained in the zeolite-containing catalyst. As the phosphorus raw material, phosphates are more preferable, and among phosphates, compounds exhibiting a solubility of 1 g or more in 100 g of water at 25° C. are more preferable.

Examples of phosphoric acid include phosphoric acid and pyrophosphoric acid, and examples of phosphates include ammonium phosphate such as ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and sodium ammonium hydrogen phosphate. salts, potassium hydrogen phosphate, aluminum hydrogen phosphate, sodium phosphate, potassium phosphate, and the like. Among these, ammonium phosphate salts having relatively high solubility in water are preferred, and at least one salt selected from the group consisting of ammonium phosphate, diammonium hydrogen phosphate, and ammonium dihydrogen phosphate is more preferred. These may be used alone or in combination of two or more.

The form of silver element is, for example, silver ion. Silver element has the effect of improving the steaming resistance of zeolite by controlling the acid sites of zeolite. Deterioration of zeolite occurs both during reaction and regeneration, but deterioration tends to occur during regeneration, and this deterioration is said to be caused by its own acid sites. Silver does not reduce the zeolite acid sites during reaction, but tends to reduce the acid sites by moving to the zeolite acid sites during regeneration. Therefore, the zeolite acid sites are used for chemical reactions, have high catalytic activity, and during regeneration, deterioration is suppressed by reducing the acid sites, and the catalyst exhibits high durability.

The content of silver element contained in the zeolite-containing catalyst is preferably 0.01 to 2.0% by mass with respect to the mass of the entire catalyst, and more preferably from the viewpoint of improving hydrothermal resistance per supported amount. It is 0.01 to 1.5% by mass.

In this embodiment, the content of silver element in the catalyst is a value measured using a fluorescent X-ray analyzer. The content of silver element can be measured using a commercially available fluorescent X-ray analyzer under normal conditions according to the instruction manual. For example, when using Rigaku product name "RIX3000", The measurement conditions can be as follows: P-Kα rays are used, the tube voltage is 50 kV, and the tube current is 50 mA.

In this embodiment, silver nitrate is used as a raw material for the silver element contained in the zeolite-containing catalyst. By mixing the zeolite-containing catalyst and silver nitrate, the counter cations of the zeolite are exchanged into silver ions, and a silver element is introduced into the zeolite-containing catalyst.

The zeolite-containing catalyst of this embodiment can be manufactured by using the zeolite having the above-mentioned specific physical properties and composition, for example, by molding it as follows. The molding method is not particularly limited, and a general method can be used. Specifically, a method of compression molding the catalyst component, a method of extrusion molding, and a spray dry molding method that is most suitable for a fluidized bed reaction method can be mentioned.

Moreover, a binder can be used for molding. The binder is not particularly limited, and for example, silica, alumina, and kaolin can be used alone or in combination. Commercially available binders can be used as these binders. The zeolite/binder mass ratio is preferably in the range of 10/90 to 90/10, more preferably in the range of 20/80 to 80/20. From the viewpoint of suppressing caulking, a silica binder is preferred.

In the alcohol conversion method of this embodiment, the zeolite-containing catalyst may be subjected to a pretreatment step prior to contacting the zeolite-containing catalyst with the raw material. A preferred pretreatment step includes a step of heat treatment at a temperature of 300° C. or higher in the presence of water vapor. When pretreatment is performed, the effects of suppressing catalyst deterioration and improving selectivity tend to become more pronounced. In the case of the above method, a mixed gas of steam (water vapor) and an inert gas such as air or nitrogen is passed through the atmosphere at a temperature of 300°C or more and 900°C or less, and the water vapor partial pressure is 0.01. It is preferable to process under conditions of atmospheric pressure or higher. The heat treatment temperature is more preferably 400°C or higher and 700°C or lower. Further, this pretreatment step can be performed using a reactor that converts alcohol.

<Product: Reaction gas containing olefin having 3 or more carbon atoms>
In the alcohol conversion method of the present embodiment, a reaction gas containing an olefin having 3 or more carbon atoms is obtained by bringing a mixed raw material into contact with an alcohol conversion catalyst. The reaction gas may include ethylene. The reaction gas may contain hydrogen, an aliphatic hydrocarbon having 1 to 3 carbon atoms, an aliphatic hydrocarbon having 4 to 8 carbon atoms, an aromatic compound, and a hydrocarbon having 9 or more carbon atoms.
In this specification, aliphatic hydrocarbons having 1 to 3 carbon atoms, aliphatic hydrocarbons having 4 to 8 carbon atoms, aromatic compounds, and hydrocarbons having 9 or more carbon atoms are referred to as target compounds.

<Regeneration process>
If an alcohol conversion catalyst is used for a long-term reaction, coke may adhere to the catalyst and cause coking deterioration. When the catalyst deteriorates due to coking, for example, in air or in a mixed gas consisting of air and/or oxygen and an inert gas, preferably under conditions of an oxygen concentration of 0.1 to 2.0% by volume. By burning off the coke on the catalyst at a temperature of 400 to 700°C, it is possible to regenerate the catalyst that has suffered coking deterioration (hereinafter also referred to as "regeneration step"). The alcohol conversion catalyst can be regenerated using either external regeneration, in which it is extracted from the reactor and regenerated outside the reactor, or in-reactor regeneration, in which it is regenerated within the reactor without being extracted from the reactor. Good too. Furthermore, by employing a switching reactor, reaction-regeneration switching operation can be performed.

<Reaction-regeneration switching operation>
The reaction-regeneration switching operation is an operation in which a reaction step and a regeneration step are performed simultaneously using a two-column or multi-column switching type adiabatic reactor. For example, in the case of a three-column switching system, two columns are used for the reaction process, and at the same time, the remaining one column is used for catalyst regeneration. After that, the reaction process in one of the towers used for the reaction process was stopped and the catalyst was regenerated, and the reaction process was performed in the one tower that was used for catalyst regeneration, thereby maintaining the production capacity of two towers. Catalyst regeneration can be performed at the same time. Such a reaction format is also called a merry-go-round method, and is preferable from the viewpoint of excellent production efficiency since it is not necessary to stop the manufacturing process for catalyst regeneration.

[Propylene production method and aromatic compound production method]
Various chemical products can be obtained by separating target compounds from the reaction gas obtained by this embodiment.

The method for producing propylene of this embodiment is as follows:
Obtaining a reaction gas by the alcohol conversion method of the present embodiment (same as the reaction step described above);
separating a fraction mainly containing propylene from the reaction gas;
including.

The method for producing an aromatic compound according to the present embodiment includes:
Obtaining a reaction gas by the alcohol conversion method of the present embodiment (same as the reaction step described above);
The method includes separating a fraction mainly containing aromatic compounds from the reaction gas.

Hereinafter, separation operations including separating a fraction mainly containing propylene from the reaction gas and separating a fraction mainly containing aromatic compounds from the reaction gas will be collectively referred to as the separation process, and will be described below. Explain details.

<Separation process>
In the separation step, the target compound is separated from the reaction gas. Ethylene, propylene, and aromatic compounds can be separated from the reaction gas through the separation step.

The method according to this embodiment can be carried out using an apparatus having a reactor 1, a distillation column 2, a distillation column 3, and a distillation column 4, as shown in FIG. After removing condensed water from the reaction gas obtained in the reaction process performed in the reactor 1, a distillation column 2 separates a fraction A mainly containing hydrocarbons having 1 to 3 carbon atoms and a fraction A containing 4 to 8 carbon atoms. It can be separated into a fraction B containing mainly hydrocarbons. Note that water condensed from the reaction gas may be removed before distillation in the distillation column 2 (not shown). By separating ethylene and propylene from fraction A in distillation column 3 and distillation column 4, ethylene and propylene are efficiently separated from the reaction gas. Alternatively, at least a portion of the reaction gas and/or fraction A may be introduced into a purification system of an ethylene plant, and ethylene and propylene may be separated from the reaction gas in the purification system. The reaction gas and each fraction including fraction B obtained in the separation step can be recycled to the reactor as raw materials.

The method according to this embodiment can be carried out using an apparatus including a reactor 1, a distillation column 2, and a steam cracking apparatus 5, as shown in FIG. By subjecting the fraction B obtained by the separation step to steam cracking, a steam cracking product containing ethylene and propylene is obtained, and the efficiency of the entire process is increased by separating ethylene and propylene from the steam cracking product. be able to. Steam cracking refers to the thermal decomposition of compounds in a fraction with heated steam.

The method according to this embodiment can be carried out using an apparatus including a reactor 1, a cooling device 6, a distillation column 2, and an oil-water separator 7, as shown in FIG. A cooling step may be provided in which the reaction gas obtained in the reaction step performed in the reactor 1 is cooled by the cooling device 6. Through the cooling step, the reaction gas is divided into a fraction C mainly containing aliphatic hydrocarbons having 2 to 6 carbon atoms and a fraction D mainly containing water, aliphatic hydrocarbons having 7 or more carbon atoms, and aromatic compounds. Can be separated. Fraction C is obtained as a gas component in the cooling step, and fraction D is recovered as a liquid component. By separating the aromatic compounds from the fraction D, the aromatic compounds can be efficiently separated from the reaction gas.

The fraction D recovered in the cooling step is separated into a fraction E mainly containing hydrocarbons and a fraction F mainly containing water in the oil-water separator 7. By separating the aromatic compounds from the fraction E, the aromatic compounds can be efficiently separated from the reaction gas. Separation of aromatic compounds is carried out, for example, by distillation, extractive distillation, extraction, crystallization and combinations thereof.

The method according to this embodiment can be carried out using an apparatus having a reactor 1, a distillation column 2, and a distillation column 8, as shown in FIG. When the fraction B is recycled by the distillation column 8, it is separated into a fraction B1 mainly containing aliphatic hydrocarbons having 4 to 6 carbon atoms, preferably olefins, and a fraction B2 mainly containing aromatic compounds. However, it is preferred that at least a portion of fraction B1 is recycled to the reactor. By using fraction B1 from which fraction B2 has been removed as a recycled raw material, aromatic compounds that are not converted into propylene can be removed from the raw material, and propylene can be efficiently produced. In this way, aromatic compounds can also be separated from fraction B as fraction B2. Further separation and purification of aromatic compounds is carried out, for example, by distillation, extractive distillation, extraction, crystallization, and combinations thereof.

Further, the method according to the present embodiment can be carried out using an apparatus having a reactor 1, a distillation column 2, and a distillation column 9, as shown in FIG. The distillation column 9 separates the fraction B into a fraction B3 mainly containing hydrocarbons having 4 to 8 carbon atoms and a fraction B4 mainly containing hydrocarbons having 9 or more carbon atoms. Preferably, a portion is recycled to the reactor. By using fraction B3 from which fraction B4 has been removed as a recycled raw material, heavy components that can promote coking deterioration can be removed from the raw material, and coking deterioration of the catalyst can be suppressed.

"Mainly containing" in various fractions means that the total mass of the components described as "mainly containing" is more than 50% by mass with respect to each fraction.

Note that these separation steps can be carried out by combining various known methods such as distillation and extraction.

[Method for producing hydrocarbons, etc.]
Various chemical products can be obtained by separating target compounds from the reaction gas obtained in the first to third embodiments.
In other words, the method for producing hydrocarbons according to the present embodiment includes contacting a mixed raw material containing methanol and ethanol with a catalyst in an adiabatic reactor to obtain a reaction gas containing an olefin having 3 or more carbon atoms. . The details of the production method are as explained in the above-mentioned alcohol conversion method, and the preferred embodiment thereof is also the same.

Hydrocarbons obtained by this production method include, for example, olefins such as propylene, ethylene, butene, pentene, hexene, and heptene, aliphatic unsaturated hydrocarbons such as dienes such as 1,3-butadiene and isoprene, benzene, and toluene. Examples include aromatic hydrocarbons such as ethane, aliphatic saturated hydrocarbons such as ethane, propane, butane, and pentane. Note that the aromatic hydrocarbon preferably has a boiling point of 500° C. or lower at normal pressure.

By introducing the obtained hydrocarbon into the cracker purification system, the target hydrocarbon compound can be efficiently purified.
The method for producing hydrocarbons according to this embodiment includes:
A cracking process that decomposes hydrocarbons having two or more carbon atoms;
a purification step of refining the component obtained in the cracking step;
has
In the purification step, the reaction gas or purified fraction thereof obtained by the above alcohol conversion method is combined.
With the above configuration, the target hydrocarbon can be obtained from alcohol resources using a conventional cracker. For example, by using bio-derived alcohol as a raw material in an alcohol conversion method, bio-derived hydrocarbons can be produced.

Examples of hydrocarbons having 2 or more carbon atoms include ethylene, propylene, butene, paraffin, and aromatic hydrocarbons. Naphtha may be used as the hydrocarbon having 2 or more carbon atoms.

As the cracker, a pyrolysis furnace used for ethane crackers, naphtha crackers, etc. may be used.

In addition, in the purification process, a purification system used in a conventional ethane cracker or naphtha cracker is used, and for example, distillation may be performed using equipment equipped with a distillation column, a quench column, etc.

The reaction gas obtained by the above-mentioned alcohol conversion method or its purified fraction is combined in the above-mentioned purification step, and the joining location is appropriately selected depending on the components to be combined.

The method for producing a monomer according to this embodiment is as follows:
an unsaturated hydrocarbon separation step of separating a fraction mainly containing unsaturated hydrocarbons from the reaction gas obtained by the above alcohol conversion method;
including.
Examples of unsaturated hydrocarbons include aliphatic unsaturated hydrocarbons such as olefins such as propylene, ethylene, butene, butane, pentene, hexene, and heptene, and dienes such as 1,3-butadiene and isoprene.

The method for producing olefin according to this embodiment includes:
an olefin separation step of separating a fraction mainly containing olefins from the reaction gas obtained by the above-mentioned alcohol conversion method;
including.

The method for producing propylene according to this embodiment includes:
a propylene separation step of separating a fraction mainly containing propylene from the reaction gas obtained by the above alcohol conversion method;
including.

The method for producing ethylene according to this embodiment includes:
an ethylene separation step of separating a fraction mainly containing ethylene from the reaction gas obtained by the above alcohol conversion method;
including.

The diene manufacturing method according to the present embodiment includes:
a diene separation step of separating a fraction mainly containing diene from the reaction gas obtained by the above-mentioned alcohol conversion method;
including.

The method for producing a monomer according to this embodiment may further include a step of converting unsaturated hydrocarbons.

The method for producing an acrylic monomer according to this embodiment includes:
an unsaturated hydrocarbon separation step of separating a fraction mainly containing unsaturated hydrocarbons from the reaction gas obtained by the above alcohol conversion method;
an acrylic monomer production step of obtaining an acrylic monomer from the unsaturated hydrocarbon obtained in the unsaturated hydrocarbon separation step;
including.
The acrylic monomer production process uses a known method of introducing an acrylic monomer from an unsaturated hydrocarbon.

The method for producing acrylonitrile according to the present embodiment includes:
a propylene separation step of separating a fraction mainly containing propylene from the reaction gas obtained by the above-mentioned alcohol conversion method;
an acrylonitrile production step of obtaining acrylonitrile from the propylene obtained in the propylene separation step;
including.
The acrylic monomer production process uses a known method of introducing an acrylic monomer from an unsaturated hydrocarbon.

The method for producing styrene according to this embodiment includes:
an ethylene separation step of separating a fraction mainly containing ethylene from the reaction gas obtained by the above-mentioned alcohol conversion method;
a styrene production process for producing styrene from the ethylene obtained in the ethylene separation process;
including.

The monomer obtained by the above production method may be further polymerized.
The method for producing a polymer according to this embodiment includes:
a step of polymerizing the monomer obtained by the above-mentioned monomer production method,
including.
In the step of polymerizing the monomer, the polymerization can be performed using a conventional polymerization method, and the polymerization can be performed using various initiators and polymerization catalysts.

The method for producing an olefin polymer according to this embodiment includes:
a step of polymerizing a polymerizable composition containing an olefin obtained by the above-mentioned olefin production method;
including.
Here, the polymerizable composition may contain an olefin alone as a monomer, or may contain other monomers having unsaturated bonds.

The method for producing a polypropylene polymer according to this embodiment includes:
a step of polymerizing a polymerizable composition containing propylene obtained by the above-mentioned method for producing propylene;
including.
Here, the polymerizable composition may contain propylene alone as a monomer, or may contain other monomers having unsaturated bonds.

The method for producing a polyethylene polymer according to this embodiment includes:
a step of polymerizing a polymerizable composition containing ethylene obtained by the above-mentioned method for producing ethylene;
including.
Here, the polymerizable composition may contain ethylene alone as a monomer, or may contain other monomers having unsaturated bonds.

The method for producing a diene polymer according to the present embodiment includes:
a step of polymerizing a polymerizable composition containing a diene obtained by the above-described method for producing a diene;
including.
Here, the polymerizable composition may contain diene alone as a monomer, or may contain other monomers having unsaturated bonds.

The method for producing an acrylic monomer-based polymer according to this embodiment includes:
a step of polymerizing a polymerizable composition containing an acrylic monomer obtained by the above-described method for producing an acrylic monomer;
including.
Here, the polymerizable composition may contain an acrylic monomer alone as a monomer, or may contain other monomers having unsaturated bonds.

The method for producing an acrylonitrile polymer according to this embodiment includes:
a step of polymerizing a polymerizable composition containing acrylonitrile obtained by the above-mentioned method for producing acrylonitrile;
including.
Here, the polymerizable composition may contain acrylonitrile alone as a monomer, or may contain other monomers having unsaturated bonds.

The method for producing a styrenic polymer according to this embodiment includes:
a step of polymerizing a polymerizable composition containing styrene obtained by the above-mentioned method for producing styrene;
including.
Here, the polymerizable composition may contain styrene alone as a monomer, or may contain other monomers having unsaturated bonds.

Aromatic compounds may be separated from the reaction gas obtained by the above-described ethanol conversion method.
The method for producing an aromatic compound according to the present embodiment includes:
an aromatic compound separation step of separating a fraction mainly containing aromatic compounds from the reaction gas obtained by the above-mentioned ethanol conversion method;
including.
Examples of aromatic hydrocarbons include benzene, toluene, and xylene.

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to the Examples described below.

[Methods for measuring various physical properties]
The methods for measuring various physical properties are as follows.
(Silica/alumina molar ratio of zeolite in zeolite-containing catalyst)
A solution in which zeolite was completely dissolved in a sodium hydroxide solution was prepared. The amounts of Si and Al contained in the solution were measured using an ICP (inductively coupled plasma) emission spectrometer (manufactured by Rigaku, trade name "JY138") using a conventional method, and from the results, the molar ratio of silica/alumina was determined. was derived. The measurement conditions were set as high frequency power: 1 kW, plasma gas: 13 L/min, sheath gas: 0.15 L/min, nebulizer gas: 0.25 L/min, Si measurement wavelength: 251.60 nm, and Al measurement wavelength: 396.152 nm. did.

(Phosphorus element content and silver element content of zeolite-containing catalyst)
The contents of phosphorus element and silver element in the zeolite-containing catalyst were measured by a conventional method using a fluorescent X-ray analyzer (manufactured by Rigaku, trade name "RIX3000").

(Structure type of zeolite)
The structural type of the zeolite in the zeolite-containing catalyst can be determined by measuring the X-ray diffraction pattern of the zeolite using an X-ray analyzer (manufactured by Rigaku, trade name "RINT") and by referring to the diffraction pattern of known zeolites. Identified. The measurement conditions are as follows.
Cu cathode tube voltage: 40kV
Bulb current: 30mA
Scan speed: 1deg/min

[Method for preparing zeolite-containing catalyst]
(Preparation of zeolite-containing catalyst 1)
Clay obtained from 70 parts by mass of proton type ZSM-5 (silica/alumina molar ratio 200), which is an intermediate pore diameter zeolite, and 30 parts by mass of silica (water content adjusted using colloidal silica and fumed silica) was mixed. After kneading, extrusion molding was performed to obtain an extrusion molded body adjusted to a diameter of 1.6 mm and a length of 4 to 6 mm. After drying the obtained molded product at 350° C. for 5 hours, a predetermined amount of diammonium hydrogen phosphate aqueous solution was supported on the obtained dried product to obtain a phosphorus-supported product. The obtained phosphorus-supported product was fired at 600° C. for 5 hours in an air atmosphere using a firing furnace to obtain a fired product. Zeolite-containing catalyst 1 was obtained by filling a reactor with the calcined product and supplying and circulating a steam-nitrogen mixed gas containing 50% by volume of steam under conditions of a pressure of 0.1 MPaG and a temperature of 600° C. for 20 hours. When the content of elemental phosphorus contained in the zeolite-containing catalyst 1 was measured by the above-mentioned method, it was found to be 0.36% by mass.

(Preparation of zeolite-containing catalyst 2)
Clay obtained from 70 parts by mass of proton type ZSM-5 (silica/alumina molar ratio 1162), which is an intermediate pore diameter zeolite, and 30 parts by mass of silica (water content adjusted using colloidal silica and fumed silica) was mixed. After kneading, extrusion molding was performed to obtain an extrusion molded body adjusted to a diameter of 1.6 mm and a length of 4 to 6 mm. The obtained molded body was dried at 350°C for 5 hours and then calcined at 600°C for 5 hours to obtain a zeolite-containing catalyst 2.

(Preparation of zeolite-containing catalyst 3)
Clay obtained from 70 parts by mass of proton type ZSM-5 (silica/alumina molar ratio 1162), which is an intermediate pore diameter zeolite, and 30 parts by mass of silica (water content adjusted using colloidal silica and fumed silica) was mixed. After kneading, extrusion molding was performed to obtain an extrusion molded body adjusted to a diameter of 1.6 mm and a length of 4 to 6 mm. The obtained molded body was dried at 350°C for 5 hours and then calcined at 600°C for 5 hours to obtain a catalyst precursor. The obtained catalyst precursor was stirred in a 0.1N aqueous sodium nitrate solution for 1 hour, filtered and washed, and calcined at 600° C. for 5 hours to obtain a sodium exchanger. The sodium exchanger was stirred in a 0.01N silver nitrate aqueous solution for 1 hour, filtered and washed, and then baked at 600° C. for 5 hours to obtain a silver exchanger. Zeolite-containing catalyst 3 was obtained by supplying and circulating a steam-air mixed gas containing 50% by volume of steam through the silver exchanger under conditions of a pressure of 0.1 MPaG and a temperature of 600° C. for 20 hours. At this time, the content of silver element contained in the zeolite-containing catalyst 3 was 0.16% by mass.

[Alcohol conversion method]
(Reactor)
The following Examples and Comparative Examples were evaluated using a fixed bed single-stage adiabatic reactor 1 shown in FIG.

(material)
The methanol/ethanol molar ratio, the C4-C6 olefin/methanol molar ratio, and the ethylene/ethanol molar ratio in Examples and Comparative Examples were calculated according to the following formulas.
Methanol/ethanol molar ratio (-) = methanol molar flow rate (mol/hr)/ethanol molar flow rate (mol/hr)
Molar ratio of methanol/olefin having 4 to 6 carbon atoms (-) = molar molar flow rate (mol/hr)/flow rate of olefin having 4 to 6 carbon atoms (mol/hr)
Ethylene/ethanol molar ratio (-) = ethylene molar flow rate (mol/hr)/ethanol molar flow rate (mol/hr)

(Temperature measurement)
The temperature at the inlet of the catalyst bed and the temperature at the outlet of the catalyst bed were measured by a thermocouple inserted from outside the reactor. Specifically, as shown in Figure 1, in a plane perpendicular to the fluid flow direction, if the center of the reactor is 0 and the distance from the center of the reactor to the inner wall of the reactor is d, then 0.5 d. The temperature was measured at ~0.6d. Note that the effect of heat radiation due to the insertion of this thermocouple was so small that it could be ignored.

(Reaction evaluation)
In accordance with the following Examples and Comparative Examples, reactions were carried out such that the average reaction temperature at input and output was 540°C. A portion of the reactor outlet gas was sampled every 3 hours from the start of the reaction and introduced into a gas chromatograph (TCD, FID detector) to analyze the reaction gas composition. The reaction was stopped 48 hours after the start of the reaction. The average value of the GC analysis results from the start of the reaction to the end of the reaction was calculated. In addition, the average reaction temperature of input and output was calculated according to the following formula, and was expressed as "reaction temperature" in the table.
Average reaction temperature in and out (℃) = [Catalyst bed inlet temperature (℃) + catalyst bed outlet temperature (℃)] / 2

(Coke yield)
In the following Examples and Comparative Examples, after the reaction was stopped, nitrogen was supplied to the reactor to purge the hydrocarbons and the catalyst bed was maintained at 500°C. Next, air/nitrogen with an oxygen concentration of 2% by volume was circulated to burn off the coke on the catalyst. At this time, the reactor outlet gas is periodically sampled, the regeneration gas is analyzed using a gas chromatograph, the concentration of CO ₂ and CO is measured, and the amount of carbon attached to the catalyst is determined from this value. , this was taken as the amount of coke. The method of regeneration gas analysis using a gas chromatograph is described below (gas chromatograph analysis conditions). Hereinafter, coke yields in Examples and Comparative Examples were determined according to the following formula.
Coke yield (mass ppm) = coke amount/[effective raw material supply mass flow rate (kg/hr) x reaction time (hr)]
Effective raw material supply mass flow rate (kg/hr) = ethylene flow rate (kg/hr) + ethylene equivalent ethanol flow rate (kg/hr) + methylene equivalent methanol flow rate + olefin flow rate with 4 to 6 carbon atoms (kg/hr)
Ethanol flow rate (kg/hr) = Ethanol flow rate (kg/hr) x 0.609
Methylene conversion methanol flow rate (kg/hr) = methanol flow rate (kg/hr) x 0.438

(Gas chromatograph analysis conditions)
≪Regeneration gas analysis≫
Equipment: Shimadzu GC-8A
Column: Use the following column (1) and column (2) connected in parallel.
Column (1) SUS column (inner diameter 3 mm, length 3 m) packed with 80-100 mesh molecular sieve 5A (manufactured by Wako Pure Chemical Industries)
Column (2) 80 to 100 mesh Porapac-Q manufactured by WATERS ASSOCIATES (inner diameter 3 mm, length 2 m) and SUS resistance column (inner diameter 3 mm, length 1 m) directly connected Column temperature: 70°C
Carrier gas (helium) flow rate: 60mL/min

≪Reactive gas analysis≫
Equipment: Shimadzu GC-2030
Column: Custom capillary column SPB-1 manufactured by SUPELCO, USA (inner diameter 0.25 mm, length 60 m, film thickness 3.0 μm)
Sample gas amount: 1mL (sampling line kept at 200℃ to 300℃)
Temperature raising program: Hold at 40°C for 12 minutes, then heat up to 200°C at 5°C/min, then hold at 200°C for 22 minutes.
Split ratio: 200:1
Carrier gas (nitrogen) flow rate: 120 mL/min FID detector: Air supply pressure 50 kPa (approx. 500 mL/min), hydrogen supply pressure 60 kPa (approx. 50 mL/min)
Measurement method: A TCD detector and an FID detector are connected in series, and composition analysis is performed based on the data detected by the TCD detector for hydrogen and the data detected by the FID detector for oxygenated substances such as hydrocarbons and ethanol. The propylene concentration, benzene concentration, toluene concentration, and C8 aromatic hydrocarbon concentration in the reaction gas were determined using the calibration curve method, and the propylene mass and aromatic mass per hour produced by the reaction were determined. Note that the mass of aromatic compounds produced by the reaction per hour is the total mass of benzene, toluene, and aromatic hydrocarbons having 8 carbon atoms produced by the reaction per hour.
The propylene yield and aromatic yield were calculated using the following formula.
Propylene yield (mass%) = mass of propylene produced by reaction per hour (kg/hr)/effective raw material supply mass flow rate (kg/hr)
Aromatic yield (mass%) = aromatic mass per hour produced by reaction (kg/hr)/effective raw material supply mass flow rate (kg/hr)
Effective raw material supply mass flow rate (kg/hr) = Ethylene flow rate (kg/hr) + ethylene equivalent ethanol flow rate (kg/hr) + methylene equivalent methanol flow rate (kg/hr) + olefin flow rate with 4 to 6 carbon atoms (kg/hr) hr) + flow rate of oxygen-containing compounds having 1 to 6 carbon atoms other than methanol and ethanol (kg/hr)
Ethanol flow rate (kg/hr) = Ethanol flow rate (kg/hr) x 0.609
Methylene conversion methanol flow rate (kg/hr) = methanol flow rate (kg/hr) x 0.438

[Example 1]
A mixed raw material gas of methanol and ethanol with a methanol/ethanol molar ratio of 0.22 was heated and supplied to a reactor filled with zeolite-containing catalyst 1 so that WHSV = 3.8, and a reaction was performed. . At this time, the inlet temperature of the catalyst bed was 563°C, the outlet temperature was 518°C, and the average reaction temperature of input and output was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 19.5% by mass, and the aromatic yield was 7.8% by mass. Further, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 277 mass ppm. Details of the reaction results and reaction conditions are shown in Table 1.

[Example 2]
A mixed raw material gas of methanol and ethanol with a methanol/ethanol molar ratio of 0.50 was heated and supplied to a reactor filled with zeolite-containing catalyst 1 so that WHSV = 3.8, and a reaction was performed. . At this time, the inlet temperature of the catalyst bed was 536°C, the outlet temperature was 544°C, and the average reaction temperature of input and output was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 20.1% by mass, and the aromatic yield was 7.5% by mass. Further, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 270 mass ppm. Details of the reaction results and reaction conditions are shown in Table 1.

[Example 3]
A mixed raw material gas of methanol and ethanol with a methanol/ethanol molar ratio of 0.86 was heated and supplied to a reactor filled with zeolite-containing catalyst 1 so that WHSV = 3.8, and a reaction was performed. . At this time, the inlet temperature of the catalyst bed was 511°C, the outlet temperature was 569°C, and the average reaction temperature of input and output was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 19.3% by mass, and the aromatic yield was 8.8% by mass. Further, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 357 mass ppm. Details of the reaction results and reaction conditions are shown in Table 1.

[Comparative example 1]
The reaction was carried out in the same manner as in Example 1, except that methanol was not included, only ethanol raw material gas was used, and the catalyst bed inlet temperature was adjusted to 588°C. At this time, the outlet temperature of the catalyst bed was 492°C, and the average input and output reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 18.3%, and the aromatic yield was 1.2% by mass. Further, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 483 mass ppm. The reaction results are shown in Table 1 along with the reaction conditions.

[Comparative example 2]
The reaction was carried out in the same manner as in Example 1, except that ethanol was not included, only methanol raw material gas was used, and the catalyst bed inlet temperature was 450°C. Then, the temperature at the outlet of the catalyst bed exceeded 650° C. and continued to rise, so from the viewpoint of safety, the reaction was stopped after one hour had passed. This comparative example shows that it is difficult to efficiently carry out a reaction that generates intense heat in an adiabatic reactor.

From the results of Examples 1 to 3 and Comparative Examples 1 to 2, using a mixed raw material with a methanol/ethanol molar ratio within a specific range achieves both high propylene yield and aromatic yield and suppression of coke deposition on the catalyst. It turns out it can be done.

[Example 4]
Mainly methanol/ethanol with a molar ratio of 0.35 and a molar ratio of olefin with 4 to 6 carbon atoms/methanol with 0.97, ethanol, and hydrocarbons with 4 to 8 carbon atoms in the composition ratio shown in Table 2. A mixed raw material gas of hydrocarbons containing 4 or more carbon atoms was heated and supplied to a reactor filled with zeolite-containing catalyst 1 so that WHSV=4.9, and a reaction was carried out. At this time, the inlet temperature of the catalyst bed was 566°C, the outlet temperature was 514°C, and the average reaction temperature of input and output was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 18.9% by mass, and the aromatic yield was 8.3% by mass. Further, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 315 mass ppm. Details of the reaction results and reaction conditions are shown in Table 3. In this example, the aromatic yield is calculated from the difference between the aromatic concentration in the raw material and the aromatic concentration in the reaction gas.

[Example 5]
Example except that a mixed raw material gas with a methanol/ethanol molar ratio of 0.50 and a C4-C6 olefin/methanol molar ratio of 0.49 was used, and the inlet temperature of the catalyst bed was adjusted to 558°C. The reaction was carried out in the same manner as in 4. At this time, the outlet temperature of the catalyst bed was 522°C, and the average input and output reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 19.5% by mass, and the aromatic yield was 7.8% by mass. Further, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 297 mass ppm. The reaction results are shown in Table 3 together with the reaction conditions.

[Example 6]
Example except that a mixed raw material gas with a methanol/ethanol molar ratio of 0.86 and a C4-C6 olefin/methanol molar ratio of 0.32 was used, and the inlet temperature of the catalyst bed was adjusted to 526°C. The reaction was carried out in the same manner as in 4. At this time, the outlet temperature of the catalyst bed was 558°C, and the average input and output reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 19.9% by mass, and the aromatic yield was 7.6% by mass. Further, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 270 mass ppm. The reaction results are shown in Table 3 together with the reaction conditions.

[Example 7]
Example except that a mixed raw material gas with a methanol/ethanol molar ratio of 1.33 and a C4-C6 olefin/methanol molar ratio of 0.24 was used, and the inlet temperature of the catalyst bed was adjusted to 526°C. The reaction was carried out in the same manner as in 4. At this time, the outlet temperature of the catalyst bed was 554°C, and the average input and output reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 19.5% by mass, and the aromatic yield was 7.6% by mass. Further, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 266 mass ppm. The reaction results are shown in Table 3 together with the reaction conditions.

[Comparative example 3]
The reaction was carried out in the same manner as in Example 2, except that ethanol was not used, methanol and an olefin having 4 to 6 carbon atoms were used as raw material gases, and the inlet temperature of the catalyst bed was adjusted to 441°C. At this time, the outlet temperature of the catalyst bed was 639°C, and the average input and output reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 14.8% by mass, and the aromatic yield was 11.3% by mass. Further, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 684 mass ppm. The reaction results are shown in Table 3 together with the reaction conditions.

[Example 8]
Using a mixed raw material gas with a methanol/ethanol molar ratio of 0.40, a C4-C6 olefin/methanol molar ratio of 0.24, and an ethylene/ethanol molar ratio of 0.13, The reaction was carried out in the same manner as in Example 4 except that the temperature was adjusted to 555°C. At this time, the outlet temperature of the catalyst bed was 525°C, and the average input and output reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 19.5% by mass, and the aromatic yield was 7.4% by mass. Further, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 251 mass ppm. The reaction results are shown in Table 4 together with the reaction conditions.

[Example 9]
Using a mixed raw material gas with a methanol/ethanol molar ratio of 0.46, an olefin methanol/carbon number ratio of 0.20, and an ethylene/ethanol molar ratio of 0.31, the inlet of the catalyst bed was used. The reaction was carried out in the same manner as in Example 4 except that the temperature was adjusted to 544°C. At this time, the outlet temperature of the catalyst bed was 536°C, and the average reaction temperature of input and output was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 19.8% by mass, and the aromatic yield was 7.7% by mass. Further, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 280 mass ppm. The reaction results are shown in Table 4 together with the reaction conditions.

[Example 10]
The reaction was carried out in the same manner as in Example 1, except that a mixed raw material gas with a methanol/ethanol molar ratio of 0.078 and an ethylene/ethanol molar ratio of 0.26 was used, and the inlet temperature of the catalyst bed was adjusted to 546°C. went. At this time, the outlet temperature of the catalyst bed was 534°C, and the average reaction temperature of input and output was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 19.8% by mass, and the aromatic yield was 7.7% by mass. Further, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 291 mass ppm. The reaction results are shown in Table 4 together with the reaction conditions.

[Example 11, 12]
The reaction was carried out in the same manner as in Example 1, except that the catalyst was changed from zeolite-containing catalyst 1 to zeolite-containing catalyst 2 and zeolite-containing catalyst 3, and the amount of catalyst was changed. Table 5 shows the reaction results and reaction conditions.

Claims (43)

A method for converting alcohol, comprising contacting a mixed raw material containing methanol and ethanol with an alcohol conversion catalyst in an adiabatic reactor to obtain a reaction gas containing an olefin having 3 or more carbon atoms. The method for converting alcohol according to claim 1, wherein the methanol/ethanol molar ratio in the mixed raw material is 0.050 to 2.0. The method for converting alcohol according to claim 1, wherein the methanol/ethanol molar ratio in the mixed raw material is 0.20 to 1.5. The method of converting alcohol according to claim 1, comprising separating ethylene and propylene from the reaction gas. The method for converting alcohol according to claim 1, wherein the mixed raw material contains an olefin having 4 to 6 carbon atoms. The method for converting alcohol according to claim 5, wherein the molar ratio of olefin having 4 to 6 carbon atoms/methanol in the mixed raw material is 3.0 or less. The method for converting alcohol according to claim 1, comprising recycling at least a part of the reaction gas or a fraction obtained by purifying the reaction gas to the reactor and using it as a part of the mixed raw material. Separating the reaction gas into a fraction A mainly containing hydrocarbons having 1 to 3 carbon atoms and a fraction B mainly containing hydrocarbons having 4 to 8 carbon atoms, and extracting ethylene from the fraction A. and separating propylene;
The method for converting alcohol according to claim 1, comprising: separating the fraction B into a fraction B1 mainly containing aliphatic hydrocarbons having 4 to 6 carbon atoms and a fraction B2 mainly containing aromatic compounds; and at least a part of the fraction B1. recycling it into the reactor and using it as part of the mixed feedstock;
The method for converting alcohol according to claim 8, comprising: obtaining a steam cracking product containing ethylene and propylene by subjecting said fraction B to steam cracking, and separating ethylene and propylene from said steam cracking product;
The method for converting alcohol according to claim 8, comprising: The method for converting alcohol according to claim 1, wherein the reactor is a fixed bed adiabatic reactor. The method for converting alcohol according to claim 1, wherein the reactor is a fixed bed single stage adiabatic reactor. The method for converting alcohol according to claim 1, comprising burning coke adhering to the alcohol conversion catalyst. The method for converting alcohol according to claim 1, wherein the catalyst bed outlet temperature is between 450°C and 590°C. The method for converting alcohol according to claim 1, wherein the catalyst bed inlet temperature is between 450°C and 590°C. The method for converting alcohol according to claim 1, wherein the temperature difference between the catalyst bed outlet temperature and the catalyst bed inlet temperature is -70K to 70K. The method for converting alcohol according to claim 1, wherein the alcohol conversion catalyst is a zeolite-containing catalyst. 18. The method of converting alcohol according to claim 17, wherein the zeolite-containing catalyst comprises an intermediate pore size zeolite. The method for converting alcohol according to claim 17, wherein the silica/alumina molar ratio of the zeolite in the zeolite-containing catalyst is from 20 to 2000. The method for converting alcohol according to claim 17, wherein the zeolite-containing catalyst contains at least one selected from the group consisting of phosphorus element and silver element. The method for converting alcohol according to claim 1, wherein the mixed raw material contains ethylene and the molar ratio of ethylene/ethanol is 0.05 or more. The method for converting alcohol according to claim 1, wherein at least one of the methanol and the ethanol is derived from biomass. A method for producing hydrocarbons, the method comprising contacting a mixed raw material containing methanol and ethanol with an alcohol conversion catalyst in an adiabatic reactor to obtain a reaction gas containing an olefin having 3 or more carbon atoms. A cracking process that decomposes hydrocarbons having two or more carbon atoms;
a purification step of refining the component obtained in the cracking step;
has
A method for producing hydrocarbons, wherein in the purification step, a reaction gas obtained by the alcohol conversion method according to any one of claims 1 to 22 or a purified fraction thereof is combined. an unsaturated hydrocarbon separation step of separating a fraction mainly containing unsaturated hydrocarbons from the reaction gas obtained by the alcohol conversion method according to any one of claims 1 to 22;
A method for producing a monomer, including: an olefin separation step of separating a fraction mainly containing olefins from the reaction gas obtained by the alcohol conversion method according to any one of claims 1 to 22;
A method for producing an olefin, including. a propylene separation step of separating a fraction mainly containing propylene from the reaction gas obtained by the alcohol conversion method according to any one of claims 1 to 22;
A method for producing propylene, including: an ethylene separation step of separating a fraction mainly containing ethylene from the reaction gas obtained by the alcohol conversion method according to any one of claims 1 to 22;
A method for producing ethylene, including: a diene separation step of separating a fraction mainly containing diene from the reaction gas obtained by the alcohol conversion method according to any one of claims 1 to 22;
A method for producing a diene, including. an unsaturated hydrocarbon separation step of separating a fraction mainly containing unsaturated hydrocarbons from the reaction gas obtained by the alcohol conversion method according to any one of claims 1 to 22;
an acrylic monomer production step of obtaining an acrylic monomer from the unsaturated hydrocarbon obtained in the unsaturated hydrocarbon separation step;
A method for producing an acrylic monomer, including: a propylene separation step of separating a fraction mainly containing propylene from the reaction gas obtained by the alcohol conversion method according to any one of claims 1 to 22;
an acrylonitrile production step of obtaining acrylonitrile from the propylene obtained in the propylene separation step;
A method for producing acrylonitrile, including: an ethylene separation step of separating a fraction mainly containing ethylene from the reaction gas obtained by the alcohol conversion method according to any one of claims 1 to 22;
a styrene production process for producing styrene from the ethylene obtained in the ethylene separation process;
A method for producing styrene, including: Polymerizing the monomer obtained by the production method according to claim 25,
A method for producing a polymer, including: Polymerizing a polymerizable composition containing an olefin obtained by the production method according to claim 26,
A method for producing an olefin polymer, including: Polymerizing a polymerizable composition containing propylene obtained by the production method according to claim 27,
A method for producing a polypropylene polymer, including: Polymerizing the ethylene-containing polymerizable composition obtained by the production method according to claim 28,
A method for producing a polyethylene polymer, including: Polymerizing a diene-containing polymerizable composition obtained by the production method according to claim 29,
A method for producing a diene polymer, including: Polymerizing a polymerizable composition containing an acrylic monomer obtained by the production method according to claim 30,
A method for producing an acrylic monomer-based polymer, comprising: Polymerizing a polymerizable composition containing acrylonitrile obtained by the production method according to claim 31,
A method for producing an acrylonitrile polymer, including: Polymerizing a polymerizable composition containing styrene obtained by the production method according to claim 32,
A method for producing a styrenic polymer, including: Obtaining a reaction gas by the method for converting alcohol according to any one of claims 1 to 22;
A method for producing an aromatic compound, the method comprising separating a fraction mainly containing aromatic compounds from the reaction gas. An aromatic monomer production step of obtaining an aromatic monomer from an aromatic compound obtained by the production method according to claim 41,
A method for producing an aromatic monomer, including: Polymerizing a polymerizable composition containing an aromatic monomer obtained by the production method according to claim 42,
A method for producing an aromatic monomer-based polymer, comprising:

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