Method for converting ethanol, and method for producing hydrocarbon

Abstract

To provide a method for converting ethanol, and a method for producing hydrocarbon.SOLUTION: Provided are (1) a method for converting ethanol including bringing mixed raw material containing ethylene and ethanol in contact with a catalyst in an adiabatic reactor to obtain reaction gas containing olefin having carbon number 3 or more, (2) a method for converting ethanol including bringing mixed raw material containing methanol and ethanol in contact with a catalyst in an adiabatic reactor to obtain reaction gas containing olefin having carbon number 3 or more, and (3) a method for converting ethanol including bringing a mixed raw material containing ethanol and ethylene in contact with a catalyst in an adiabatic reactor to obtain reaction gas containing olefin having carbon number 3 or more, separating the reaction gas into fraction A which mainly contains hydrocarbon having carbon number 2 to 3 and fraction B which mainly contains hydrocarbon having carbon number 4 to 6 by a first distillation tower, and recycling at least a part of fraction A to the reaction step as a part of the mixed raw material.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a process for the conversion of ethanol and other hydrocarbons. [Background technology]

[0002] Hydrocarbons such as lower olefins are important raw materials in the chemical industry, and because demand for propylene in particular is expected to increase, various production methods have been actively developed and improved. Among these, a commonly known method for producing propylene is to contact naphtha and olefins with a catalyst using zeolite as the active species.

[0003] For example, Patent Document 1 discloses a method for producing propylene from an ethylene feedstock. Patent Documents 2 and 3 disclose technologies for converting ethanol to propylene using pentasil-type zeolite and zinc oxide-cerium-supported zeolite, respectively. For example, Patent Document 4 discloses a method for producing lower olefins using an oxygen-containing compound (oxygenate) and an olefin having four or more carbon atoms as feedstocks, and Patent Document 5 discloses a method for producing lower olefins using a lower alcohol and naphtha as feedstocks. For example, Patent Document 6 discloses a method for producing propylene from a feedstock containing methanol. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] WO2014 / 025021A1 [Patent Document 2] WO2015 / 029355A1 [Patent Document 3] CN110560155A [Patent Document 4] US2014 / 0018593A1 [Patent Document 5] CN110871107A [Patent Document 6] WO2005 / 56504A1 Summary of the Invention

[0005] The present invention includes the following embodiments. [1] A method for converting ethanol, comprising contacting a mixed feedstock containing ethylene and ethanol with a catalyst in an adiabatic reactor to obtain a reaction gas containing olefins having three or more carbon atoms. [2] The method for converting ethanol according to [1], wherein the molar ratio of ethylene to ethanol in the mixed feedstock is 0.20 to 2.5. [3] The method for converting ethanol according to [1] or [2], wherein the molar ratio of ethylene to ethanol in the mixed raw material is 0.20 to 2.0. [4] The method for converting ethanol according to any one of [1] to [3], further comprising separating ethylene and propylene from the reaction gas. [5] The method for converting ethanol according to any one of [1] to [4], wherein the mixed raw material contains olefins having 4 to 6 carbon atoms. [6] The method for converting ethanol according to [5], wherein the molar ratio of olefins having 4 to 6 carbon atoms to ethylene in the mixed feedstock is 3.0 or less. [7] A method for converting ethanol, comprising contacting a mixed feedstock containing methanol and ethanol with a catalyst in an adiabatic reactor to obtain a reaction gas containing olefins having three or more carbon atoms. [8] The method for converting ethanol according to any one of [1] to [6], wherein the mixed raw material contains methanol. [9] The method for converting ethanol according to [7] or [8], wherein the molar ratio of methanol / ethanol in the mixed raw material is 0.050 to 2.0.

[10] The method for converting ethanol according to any one of [7] to [9], wherein the molar ratio of methanol / ethanol in the mixed raw material is 0.20 to 1.5.

[11] The method for converting ethanol according to any one of [7] to

[10] , further comprising separating ethylene and propylene from the reaction gas.

[12] The method for converting ethanol according to any one of [7] to

[11] , wherein the mixed feedstock contains olefins having 4 to 6 carbon atoms.

[13] The method for converting ethanol according to any one of [7] to

[12] , wherein the molar ratio of olefins having 4 to 6 carbon atoms to methanol in the mixed feedstock is 3.0 or less.

[14] The method for converting ethanol according to any one of [7] to

[13] , comprising recycling at least a portion 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.

[15] a mixed raw material containing ethanol and ethylene contacting a catalyst in an adiabatic reactor to obtain a reaction gas containing olefins having 3 or more carbon atoms; Separating the reaction gas into a fraction A mainly containing hydrocarbons having 2 to 3 carbon atoms and a fraction B mainly containing hydrocarbons having 4 to 6 carbon atoms using a first distillation column; Recycling at least a portion of the fraction A to the reaction step as part of the mixed raw material; A method for converting ethanol, comprising:

[16] Separating the reaction gas into a fraction A mainly containing hydrocarbons having 2 to 3 carbon atoms and a fraction B mainly containing hydrocarbons having 4 to 6 carbon atoms using a first distillation column; Recycling at least a portion of the fraction A to the reaction step as part of the mixed raw material; The method for converting ethanol according to any one of [1] to

[14] , comprising:

[17] separating the fraction A into a fraction A-1 containing mainly hydrocarbons having a carbon number of 2 and a fraction A-2 containing mainly hydrocarbons having a carbon number of 3 by a second distillation column; The recycling step includes recycling at least a portion of the fraction A-1 to obtain the reaction gas and using the fraction A-1 as part of the mixed feedstock. The method for converting ethanol according to

[15] or

[16] .

[18] The recycling step includes recycling at least a portion of the fraction B to obtain the reaction gas and using the fraction B as part of the mixed feedstock. The method for converting ethanol according to any one of

[15] to

[17] .

[19] cooling the reaction gas to separate it into a fraction C mainly containing hydrocarbons having a carbon number of 6 or less and a fraction D mainly containing water and hydrocarbon compounds having a carbon number of 7 or more; The method for converting ethanol according to any one of

[15] to

[18] , comprising:

[20] The method for converting ethanol according to any one of

[15] to

[19] , wherein the separation using the first distillation column comprises providing a side cut tray in the first distillation column to obtain an intermediate draw effluent. [twenty one] 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; separating ethylene and propylene from said fraction A; The method for converting ethanol according to any one of [1] to

[20] , comprising: [twenty two]

[21] The method for converting ethanol according to

[21] , further comprising recycling at least a portion of the fraction B to the reactor and using it as part of the mixed feedstock. [twenty three] 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; recycling at least a portion of the fraction B1 to the reactor and using it as part of the mixed feedstock; The method for converting ethanol according to

[21] or

[22] , comprising: [twenty four] Obtaining a steam cracking product containing ethylene and propylene by subjecting the fraction B to steam cracking; separating ethylene and propylene from said steam cracking product; The method for converting ethanol according to any one of

[21] to

[23] , comprising: [twenty five] The method for converting ethanol according to any one of [1] to

[24] , wherein the reactor is a fixed-bed adiabatic reactor.

[26] The method for converting ethanol according to any one of [1] to

[25] , wherein the reactor is a fixed-bed single-stage adiabatic reactor.

[27] The method for converting ethanol according to any one of [1] to

[26] , comprising burning coke adhering to the catalyst.

[28] The method for converting ethanol according to any one of [1] to

[27] , wherein the catalyst bed outlet temperature is 450°C to 590°C.

[29] The method for converting ethanol according to any one of [1] to

[28] , wherein the catalyst bed inlet temperature is 450°C to 590°C.

[30] The method for converting ethanol according to any one of [1] to

[29] , wherein the temperature difference between the catalyst bed outlet temperature and the catalyst bed inlet temperature is −80 K to 80 K.

[31] The method for converting ethanol according to any one of [1] to

[30] , wherein the catalyst is a zeolite-containing catalyst.

[32]

[31] The method for converting ethanol according to

[31] , wherein the zeolite-containing catalyst comprises an intermediate pore size zeolite.

[33] The method for converting ethanol according to

[31] or

[32] , wherein the silica / alumina molar ratio of the zeolite in the zeolite-containing catalyst is 20 to 2000.

[34] The method for converting ethanol according to any one of

[31] to

[33] , wherein the zeolite-containing catalyst contains phosphorus or silver.

[35] A method for producing hydrocarbons, comprising contacting a mixed feedstock containing ethylene and ethanol with a catalyst in an adiabatic reactor to obtain a reaction gas containing olefins having three or more carbon atoms.

[36] a cracking step of decomposing hydrocarbons having two or more carbon atoms; a purification step of purifying the components obtained in the cracking step; and A method for producing hydrocarbons, wherein in the purification step, the reaction gas obtained by the method for converting ethanol according to any one of [1] to

[34] or a purified fraction thereof is combined.

[37] an unsaturated hydrocarbon separation step of separating a fraction mainly containing unsaturated hydrocarbons from the reaction gas obtained by the ethanol conversion method according to any one of [1] to

[34] ; A method for producing a monomer, comprising:

[38] an olefin separation step of separating a fraction mainly containing olefins from the reaction gas obtained by the ethanol conversion method according to any one of [1] to

[34] ; A method for producing an olefin, comprising:

[39] a propylene separation step of separating a fraction mainly containing propylene from the reaction gas obtained by the ethanol conversion method according to any one of [1] to

[34] ; A method for producing propylene, comprising:

[40] an ethylene separation step of separating a fraction mainly containing ethylene from the reaction gas obtained by the ethanol conversion method according to any one of [1] to

[34] ; A method for producing ethylene, comprising:

[41] a diene separation step of separating a fraction mainly containing dienes from the reaction gas obtained by the ethanol conversion method according to any one of [1] to

[34] ; A method for producing a diene, comprising:

[42] an unsaturated hydrocarbon separation step of separating a fraction mainly containing unsaturated hydrocarbons from the reaction gas obtained by the ethanol conversion method according to any one of [1] to

[34] ; 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, comprising:

[43] a propylene separation step of separating a fraction mainly containing propylene from the reaction gas obtained by the ethanol conversion method according to any one of [1] to

[34] ; an acrylonitrile production step of obtaining acrylonitrile from the propylene obtained in the propylene separation step; A method for producing acrylonitrile, comprising:

[44] an ethylene separation step of separating a fraction mainly containing ethylene from the reaction gas obtained by the ethanol conversion method according to any one of [1] to

[34] ; a styrene production step of obtaining styrene from the ethylene obtained in the ethylene separation step; A method for producing styrene, comprising:

[45]

[37] A step of polymerizing the monomer obtained by the production method according to

[37] . A method for producing a polymer, comprising:

[46]

[38] A step of polymerizing a polymerizable composition containing an olefin obtained by the production method according to

[38] . A method for producing an olefin polymer, comprising:

[47]

[39] A step of polymerizing a polymerizable composition containing propylene obtained by the production method according to

[39] . A method for producing a polypropylene-based polymer, comprising:

[48]

[40] A step of polymerizing the polymerizable composition containing ethylene obtained by the production method according to

[40] . A method for producing a polyethylene polymer, comprising:

[49]

[41] A step of polymerizing a polymerizable composition containing a diene obtained by the production method according to

[41] . A method for producing a diene polymer, comprising:

[50]

[42] A step of polymerizing a polymerizable composition containing an acrylic monomer obtained by the production method according to

[42] . A method for producing an acrylic monomer-based polymer, comprising:

[51]

[43] A step of polymerizing a polymerizable composition containing acrylonitrile obtained by the production method according to

[43] . A method for producing an acrylonitrile polymer, comprising:

[52]

[44] A step of polymerizing a polymerizable composition containing styrene obtained by the production method according to

[44] . A method for producing a styrene-based polymer, comprising:

[53] an aromatic compound separation step of separating a fraction mainly containing aromatic compounds from the reaction gas obtained by the ethanol conversion method according to any one of [1] to

[34] ; A method for producing an aromatic compound, comprising:

[54] an aromatic monomer production step of obtaining an aromatic monomer from the aromatic compound obtained by the production method according to

[53] ; A method for producing an aromatic monomer, comprising:

[55]

[53] A step of polymerizing a polymerizable composition containing an aromatic monomer obtained by the production method according to

[53] . A method for producing an aromatic monomer-based polymer, comprising:

[56] a reactor in which a mixed raw material containing ethanol and ethylene is brought into contact with a catalyst in an adiabatic reactor to obtain a reaction gas containing olefins having three or more carbon atoms; a first distillation column for separating the reaction gas into a fraction A mainly containing hydrocarbons having 2 to 3 carbon atoms and a fraction B mainly containing hydrocarbons having 4 to 6 carbon atoms; Equipped with An apparatus for converting ethanol, wherein at least a portion of the fraction A is recycled to the reactor and used as part of the mixed feedstock.

[57] a second distillation column for separating the fraction A into a fraction A-1 mainly containing hydrocarbons having a carbon number of 2 and a fraction A-2 mainly containing hydrocarbons having a carbon number of 3;

[57] The ethanol conversion apparatus according to

[57] , wherein at least a portion of the fraction A-2 is recycled to the reactor and used as part of the mixed feedstock.

[58]

[58] The ethanol conversion apparatus according to

[58] , wherein the first distillation column has a side cut stage for obtaining an intermediate draw effluent. [Brief explanation of the drawings]

[0006] [Figure 1] FIG. 1 shows a schematic diagram of one embodiment of a fixed-bed, single-stage adiabatic reactor. [Figure 2] FIG. 2 shows one embodiment of the reaction and separation process flow. [Figure 3] FIG. 3 shows one embodiment of the reaction process, separation process and steam cracking flows. [Figure 4] FIG. 4 shows one embodiment of the reaction and separation process flow. [Figure 5] FIG. 5 shows one embodiment of the reaction and separation process flow. [Figure 6] FIG. 6 shows one embodiment of the reaction and separation process flow. [Figure 7] FIG. 7 shows a schematic diagram of one embodiment of an apparatus for converting ethanol and ethylene. [Figure 8] FIG. 8 shows a schematic diagram of one embodiment of an apparatus for converting ethanol and ethylene. [Figure 9] FIG. 9 shows a schematic diagram of one embodiment of an apparatus for converting ethanol and ethylene. [Figure 10] FIG. 10 shows a schematic diagram of one embodiment of an apparatus for converting ethanol and ethylene. [Figure 11] FIG. 11 shows a schematic diagram of one embodiment of an apparatus for converting ethanol and ethylene. [Figure 12]FIG. 12 shows a schematic diagram of a conversion device for comparing the effects with those of the ethanol and ethylene conversion device according to this embodiment. [Figure 13] FIG. 13 shows a schematic diagram of a conversion device for comparing the effects with those of the ethanol and ethylene conversion device according to this embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0007] The present invention will be specifically described below. Note that the present invention is not limited to the following embodiments (present embodiments), and can be practiced in various modifications within the scope of the gist thereof.

[0008] In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in this specification, the upper limit or lower limit of a numerical range in one stage can be arbitrarily combined with the upper limit or lower limit of a numerical range in another stage.

[0009] As used herein, the term "target compound" refers to hydrocarbons such as olefins and aromatic compounds. Examples of olefins include ethylene, propylene, butene, and butadiene. Examples of aromatic compounds include benzene, toluene, and xylene. The target compound can be changed as appropriate depending on circumstances such as demand, but in the ethanol conversion method of this embodiment, propylene having a carbon number of 3 and aromatic compounds having a carbon number of 6 or more can also be obtained from ethanol having a carbon number of 2.

[0010] [First embodiment] First, the ethanol conversion method according to the first embodiment will be described.

[0011] <Ethanol Conversion Method - First Embodiment> The ethanol conversion method of the first embodiment includes contacting a mixed raw material containing ethylene and ethanol with a catalyst in an adiabatic reactor to obtain a reaction gas containing olefins having three or more carbon atoms (hereinafter also referred to as the "reaction step").

[0012] In addition to olefins, the recent rise in environmental awareness has led to an increased focus on the production of chemical products using alcohols such as ethanol produced from biomass feedstocks. As ethanol, like ethylene, is a compound with two carbon atoms, there are high hopes for the early development of an efficient method for producing hydrocarbon compounds such as propylene by converting ethanol.

[0013] When commercializing chemical manufacturing processes, the selection of a reactor and its type is a factor that significantly affects ease of operation and the magnitude of the environmental impact. Fixed-bed adiabatic reactors do not require heating or cooling and have a less complicated structure than reactors such as fluidized beds. Therefore, they are ideal reactors with low design, construction, and operation burdens. For example, if a fixed-bed, single-stage adiabatic reactor could be adopted, its advantages would be even greater. However, such reactors have the drawback of being inapplicable to reaction systems with large endothermic or exothermic reactions.

[0014] One effective method for suppressing temperature changes in a reactor due to the influence of reaction heat is to mix multiple compounds and use them as raw materials, causing different reactions that are endothermic and exothermic, thereby offsetting the heat generated and endothermic in the system, i.e., creating a thermal neutralization state. However, when selecting different raw materials that will give a single target product with the aim of thermal neutralization of the reaction system, care must be taken to select the raw materials so as not to inhibit each conversion, and it is necessary to develop a combination that takes into account the properties of the raw materials to be used, so it is difficult to select raw materials by focusing only on the heat of reaction of each elementary reaction.

[0015] Patent Documents 1 to 3 disclose techniques for converting each raw material into the target olefin using a zeolite catalyst, but these techniques cannot be applied to an adiabatic reactor because of the large endothermic and exothermic heat generated by them.

[0016] Patent Documents 4 and 5 disclose thermal neutralization techniques that utilize an exothermic reaction using an oxygen-containing compound such as alcohol as a raw material. However, a reaction using ethanol as a raw material, which induces an endothermic reaction, cannot be carried out in an adiabatic reactor.

[0017] Therefore, an object of the present embodiment is to provide a method for converting ethanol to obtain a target compound with high yield by using an adiabatic reactor and controlling the temperature inside the reactor.

[0018] As a result of intensive studies to achieve the above object, the present inventors have found that by controlling the reaction heat of the entire reaction system for the conversion of ethanol to olefins having 3 or more carbon atoms and the conversion of ethylene to olefins having 3 or more carbon atoms, it is possible to use an adiabatic reactor and control the temperature inside the reactor, thereby converting ethanol to the target compound in a high yield.

[0019] According to this embodiment, an adiabatic reactor is used, and the temperature inside the reactor is controlled to produce target compounds such as propylene with high yield. Furthermore, according to this embodiment, the use of an adiabatic reactor reduces the operational load, and environmentally friendly ethanol conversion with high energy efficiency can be carried out. Furthermore, even when an adiabatic reactor is used, target compounds such as propylene can be produced with high yield and coking deterioration can be suppressed, making this method suitable as an ethanol conversion method.

[0020] As described above, the present inventors have found that when propylene production is attempted using ethylene or ethanol alone as raw materials in an adiabatic reactor, the yield of target compounds such as propylene decreases or the catalyst deteriorates due to coking. Note that the deterioration due to coking refers to the deposition of coke on the catalyst surface, which reduces the activity of the catalyst.

[0021] Based on this finding, the present inventors have found that when a mixed raw material containing ethylene and ethanol is brought into contact with a catalyst packed in an adiabatic reactor, target compounds such as propylene can be produced in good yield, and coking deterioration can be suppressed.

[0022] It is believed that this is due to the fact that thermal neutralization can be achieved by combining an endothermic reaction and an exothermic reaction that do not inhibit each other. The conversion reaction from ethylene to propylene is an exothermic reaction. Furthermore, the conversion reaction from ethanol to propylene, in the presence of a catalyst, is an endothermic reaction consisting of a two-stage reaction: a dehydration reaction from ethanol to ethylene and a conversion reaction from ethylene to propylene. In this embodiment, it was found that the conversion reaction from ethylene to propylene and the conversion reaction from ethanol to propylene proceed without inhibiting each other, and it is believed that by combining these exothermic and endothermic reactions, it was possible to easily control the reaction conditions even in an adiabatic reactor. However, the factors are not limited to this.

[0023] (raw materials) The ethanol conversion method of the present embodiment uses a mixed feedstock containing ethylene and ethanol. By using this mixed feedstock, propylene can be produced with a high yield by using an adiabatic reactor and controlling the temperature inside the reactor.

[0024] In the mixed raw material, the molar ratio of ethylene to ethanol is preferably 0.20 to 2.5, more preferably 0.20 to 2.0, further preferably 0.30 to 1.8, and particularly preferably 0.30 to 1.5.

[0025] Ethylene produced by various methods can be used. For example, ethylene obtained by thermal decomposition of naphtha and / or ethane, direct or oxidative dehydrogenation of ethane, or dehydration of ethanol can be used. Similarly, ethanol produced by various methods can be used. Among these, bioethanol or ethanol derived from waste is preferred from the viewpoint of environmental friendliness. In the production process of these ethylene and ethanol, water is often produced as a by-product or water is often present in the reactor. Therefore, in the ethanol conversion method of this embodiment, the raw materials ethylene and ethanol may contain water.

[0026] In the ethanol conversion method of this embodiment, the mixed feedstock may further contain an olefin having 4 to 6 carbon atoms. Similar to ethylene and ethanol, the olefin having 4 to 6 carbon atoms can give a target compound such as propylene by contacting it with a catalyst. Examples of the olefin having 4 to 6 carbon atoms include butene, pentene, and hexene. In this specification, the term "olefin" includes linear, branched, and cyclic olefins as well as cycloparaffins.

[0027] In the mixed raw material, the molar ratio of olefins having 4 to 6 carbon atoms to ethylene is preferably 3.0 or less, more preferably 1.0 or less, even more preferably 0.5 or less, and even more preferably 0.15 to 0.5.

[0028] In the ethanol conversion method of this embodiment, the mixed raw material may further contain an oxygen-containing compound having 1 to 6 carbon atoms other than ethanol. Similar to ethylene and ethanol, the oxygen-containing compound having 1 to 6 carbon atoms can give a target compound such as propylene by contacting it with a catalyst. Examples of the oxygen-containing compound having 1 to 6 carbon atoms other than ethanol include methanol, propanol, dimethyl ether, and diethyl ether.

[0029] In the mixed raw material, the molar ratio of oxygen-containing compounds having 1 to 6 carbon atoms other than ethanol to ethanol is preferably 1.0 or less, and more preferably 0.5 or less.

[0030] Ethylene, ethanol, 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."

[0031] In addition to the above-mentioned effective raw materials, the mixed feedstock may contain saturated aliphatic hydrocarbons such as paraffin, olefins having 7 or more carbon atoms, and oxygen-containing compounds having 7 or more carbon atoms. When these saturated aliphatic hydrocarbons, olefins having 7 or more carbon atoms, and oxygen-containing compounds having 7 or more carbon atoms are brought into contact with a catalyst in the same way as ethylene and ethanol, they can be converted into target compounds such as propylene through a combination of dehydrogenation and dehydration reactions, but their reactivity is lower than that of the above-mentioned effective raw materials.

[0032] The mixed raw material may also contain olefins having 4 or more carbon atoms that have been separated in whole or in part from a reaction gas containing olefins having 3 or more carbon atoms obtained in the reaction step. In this way, the use of a so-called recycle reaction system makes it possible to effectively utilize the olefin raw material.

[0033] The mixed feedstock may contain inert gases such as nitrogen in addition to the above-mentioned feedstocks that can be converted into target compounds such as propylene by the reaction process. The mixed feedstock may also contain hydrogen or methane as a diluent gas, but it is preferable not to dilute with hydrogen. Hydrogen is sometimes used to suppress catalyst coking degradation, but at the same time, hydrogenation reactions of the produced propylene and other products occur, adversely affecting the propylene purity (propylene / (propylene + propane)). In the method of this embodiment, the rate of catalyst coking degradation is low even without hydrogen dilution, enabling stable operation, so it is preferable not to dilute with hydrogen. However, a small amount of hydrogen supplied to the reactor by recycling the fraction separated from the reaction gas does not have the adverse effects of the hydrogen dilution described above.

[0034] The total proportion of ethylene, olefins having 4 to 6 carbon atoms, and ethanol in the mixed raw material is preferably 40 mass% or more, more preferably 50 mass% or more, based on the mass flow rate of the mixed raw material. The mass flow rate of the mixed raw material refers to the total flow rate of all compounds, including inert components, fed to the reactor.

[0035] The total content of ethylene and ethanol in the mixed raw material is preferably 30 to 100 mass%, more preferably 40 to 100 mass%, and even more preferably 50 to 100 mass%, based on the effective raw material supply mass, provided that the mass of ethanol converted into ethylene is used in calculating the ethanol mass and the effective raw material supply mass.

[0036] In the mixed raw material, the total content of olefins having 4 to 6 carbon atoms is preferably 65 mass % or less, more preferably 10 to 55 mass %, based on the effective raw material supply mass.

[0037] The effective raw material supply mass is the total mass of effective raw materials supplied per unit time. However, for ethanol, the mass converted into ethylene is used for the calculation.

[0038] In the ethanol conversion method of this embodiment, the mixed raw material may contain water. Since the ethylene and ethanol contained in the mixed raw material are produced by various production methods, the mixed raw material may contain "water generated in the production process." Here, "water generated in the production process" refers to water that is generated in the process of producing ethylene and / or ethanol and has not been removed.

[0039] In the ethanol conversion method of this embodiment, steam can be added to the mixed feedstock in addition to the "water generated in the production process." Steam has the effect of suppressing coking degradation by lowering the olefin partial pressure and improving the yield of light olefins. However, steam may promote dealumination of zeolite, so it is preferable not to add steam to the mixed feedstock in addition to the "water generated in the production process."

[0040] (Adiabatic reactor) The ethanol conversion method of this embodiment uses an adiabatic reactor. For details on adiabatic reactors, see Adiabatic Fixed-Bed Reactors (Elsevier, 2014, Ch. 1, P. 4, L. 5-24, ISBN: 978-0-12-801306-9). Examples of adiabatic reactors include fixed-bed adiabatic reactors, moving-bed adiabatic reactors, and fluidized-bed adiabatic reactors. However, a fixed-bed adiabatic reactor is preferred for the method of this embodiment. Among fixed-bed adiabatic reactors, a fixed-bed single-stage adiabatic reactor with only one fixed catalyst bed is more preferred. Because carbonaceous matter (coke) accumulates on the catalyst during the reaction, a multi-column switching type fixed-bed single-stage adiabatic reactor is preferred, as it allows for the combustion and removal of this carbonaceous matter while the reaction continues.

[0041] 1 is a schematic diagram of a fixed-bed, single-stage adiabatic reactor. The fixed-bed, single-stage adiabatic reactor 1 comprises a reaction casing 12 with a heat insulating material 121 provided on the outer periphery, a catalyst bed 13, a reactor inlet 14, and a reactor outlet 15. The reaction casing 12 is provided with the heat insulating material 121 on the outer periphery, thereby preventing heat from escaping from within the reactor to the outside. In the production method according to this embodiment, the temperature within the reactor can be controlled by the heat generated and absorbed by the reaction.

[0042] The catalyst bed 13 is filled with a catalyst, which will be described later. A first sheathed thermocouple 161 is provided in the catalyst bed 13 immediately before it contacts the catalyst bed inlet 131. A second sheathed thermocouple 162 is provided in the catalyst bed 13 immediately after it passes through the catalyst bed outlet 132. These thermocouples measure the temperature of the mixed raw material immediately before it contacts the catalyst bed inlet 131 and the reaction gas immediately after it passes through the catalyst bed outlet 132. The catalyst bed 13 may be of a multi-stage type, but is preferably of a single stage type as shown in FIG. 1.

[0043] In the fixed-bed single-stage adiabatic reactor 1, a mixed raw material is introduced from a reactor inlet 14 and brought into contact with a catalyst bed 13, and a reaction gas is taken out from a reactor outlet 15.

[0044] (Reaction process conditions) In the ethanol conversion method of this embodiment, the reaction temperature may be 300°C or higher. Since the produced olefins are in thermal equilibrium, the reaction temperature is preferably 450°C or higher from the viewpoint of further improving the propylene yield. Furthermore, the reaction temperature is preferably less than 600°C from the viewpoint of suppressing the acceleration of coking deterioration, which is promoted at high temperatures. More specifically, the temperature of the reaction gas at the catalyst bed inlet is preferably 450°C to 590°C, and the temperature of the reaction gas at the catalyst outlet is preferably 450°C to 590°C.

[0045] The temperature difference between the outlet temperature of the catalyst bed and the inlet temperature of the catalyst bed is preferably -80K to 80K, more preferably -60K to 60K.

[0046] The inlet temperature of the catalyst bed is the temperature of the mixed raw material immediately before the raw material fluid comes into contact with the catalyst bed packed in an adiabatic reactor. The outlet temperature of the catalyst bed is the temperature of the reaction gas immediately after it has passed through the catalyst bed. The temperatures of the mixed raw material and reaction gas here refer to the temperatures between 0d and 0.8d in a plane perpendicular to the fluid flow direction, where 0 is the center of the reactor and d is the distance from the center of the reactor to the inner wall surface of the reactor. The average inlet and outlet reaction temperature is calculated by measuring the inlet temperature and outlet temperature of the catalyst bed, as shown in Figure 1, using the formula: [inlet temperature of catalyst bed + outlet temperature of catalyst bed] / 2 (hereinafter simply referred to as "reaction temperature").

[0047] The reaction pressure is preferably 0.01 to 3.0 MPaG, more preferably 0.01 to 1.0 MPaG.

[0048] The feed rate of the effective raw material is preferably 0.1 to 1000 h , in terms of the mass space velocity (WHSV) of the catalyst. -1 and more preferably 0.1 to 500 hours -1 and more preferably 0.5 to 100 hours -1In the ethanol conversion method of this embodiment, WHSV is calculated by converting ethanol into ethylene as shown in the following formula. In addition, the mass flow rate of the effective raw material supply is preferably 1 kg / hr or more, more preferably 10 kg / hr or more, and even more preferably 1,000 kg / hr or more, from the viewpoint of excellent productivity of target compounds such as propylene and aromatic compounds.

[0049] WHSV(hr -1 ) = Effective raw material supply mass flow rate (kg / hr) / Amount of catalyst (kg) Effective raw material supply mass flow rate (kg / hr) = ethylene flow rate (kg / hr) + ethylene-equivalent ethanol flow rate (kg / hr) + olefins flow rate with 4 to 6 carbon atoms (kg / hr) + oxygenated compounds with 1 to 6 carbon atoms other than ethanol flow rate (kg / hr) Ethylene-equivalent ethanol flow rate (kg / hr) = ethanol flow rate (kg / hr) × ethylene molecular weight (g / mol) / ethanol molecular weight (g / mol)

[0050] (catalyst) The catalyst used in the ethanol conversion method of this embodiment is a solid catalyst that exhibits catalytic activity for converting olefins and ethanol into target compounds such as propylene. Zeolite-containing catalysts are preferred as such catalysts because of their excellent thermal durability and propylene selectivity. A common issue in conventional olefin production using zeolites is coking, in which heavy carbonaceous material (coke) accumulates inside the zeolite pores due to reaction with hydrocarbons, deactivating the catalyst. To regenerate the catalyst, it is preferable to burn and remove the coke in an atmosphere containing oxygen molecules. However, this coke combustion causes structural collapse of the zeolite, leading to permanent deterioration of the catalyst that cannot be regenerated. The ethanol conversion method of this embodiment can suppress coke formation, making it easier to maintain activity even when using a zeolite-containing catalyst.

[0051] <Zeolite-containing catalyst> The zeolite-containing catalyst is a catalyst powder or molded body containing zeolite as an active species. In the ethanol conversion method of this embodiment, it is preferable to use a so-called intermediate pore size zeolite having a pore size of 5 to 6 Å as the zeolite in the zeolite-containing catalyst. The intermediate pore size zeolite means "a zeolite whose pore size range is intermediate between the pore size of small pore size zeolites, such as A-type zeolites, and the pore size of large pore size zeolites, such as mordenite, X-type zeolites, and Y-type zeolites." The "intermediate pore size zeolite" has a so-called 10-membered oxygen ring in its crystal structure.

[0052] Examples of intermediate pore diameter zeolites include ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-21, ZSM-23, ZSM-35, and ZSM-38, with ZSM-5-type zeolites such as ZSM-5, ZSM-11, and ZSM-8, and ZSM-38 being preferred. Zeolites similar to ZSM-5 and ZSM-11 described in Stud. Surf. Sci. Catal. 1987, 33, 167-215 can also be used, and among these, MFI-type zeolites are preferred, with ZSM-5 being more preferred, from the viewpoint of excellent catalytic performance (catalytic activity and durability against coking).

[0053] The silica / alumina (SiO2 / Al2O3) molar ratio of the zeolite contained in the zeolite-containing catalyst of this embodiment can be appropriately selected, but from the viewpoint of excellent catalytic activity and propylene selectivity, it is preferably 20 to 2000, and from the viewpoint of improving catalyst durability, it is more preferably 100 to 1500, even more preferably 300 to 1200, and still more preferably 800 to 1200. The silica / alumina (SiO2 / Al2O3) molar ratio of the zeolite contained in the zeolite-containing catalyst may be 20 to 400 or may be 100 to 300. The silica / alumina molar ratio of the zeolite can be measured by a known method, for example, by completely dissolving the zeolite in an alkaline aqueous solution and analyzing the resulting solution by plasma emission spectroscopy or the like.

[0054] The zeolite synthesis method of this embodiment is not particularly limited, but can be produced by optimizing various conditions of a conventionally known hydrothermal synthesis method for MFI zeolite. Generally, methods for efficiently obtaining MFI zeolite by hydrothermal synthesis include hydrothermal synthesis using an appropriate organic structure-directing agent (SDA), hydrothermal synthesis using hydrothermally synthesized MFI zeolite as seed crystals, or hydrothermal synthesis using seed slurry in the crystalline stage. Examples of the organic structure-directing agent (SDA) used here include ammonium salts, urea compounds, amines, and alcohols. It is known that not only organic SDAs 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 for MFI zeolite described above, a suitable catalyst can be obtained by appropriately optimizing synthesis conditions such as the type of raw materials and additives (SDA), the amount of additives, pH, the silica / alumina molar ratio, the medium, the raw material charge composition (e.g., the ratio of cations and anions), the synthesis temperature, and the synthesis time.

[0055] Specific examples include the synthesis method 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).

[0056] In addition, commercially available zeolites can also be used as long as they are MFI zeolites having the above-mentioned specific physical properties and composition.

[0057] The zeolite-containing catalyst in this embodiment preferably contains elemental phosphorus or elemental silver.

[0058] Examples of the form of elemental phosphorus include a phosphorus polymer (e.g., polyphosphoric acid), an oxide of phosphorus (e.g., P2O5), and a compound in which phosphorus is added to aluminum in a zeolite. A combination of these may also be included. When the zeolite contains aluminum, elemental phosphorus has the effect of suppressing dealumination of the zeolite and, in some cases, the effect of improving the propylene yield. In particular, in applications where the catalyst is exposed to a high-temperature steam atmosphere, the properties of the zeolite-containing catalyst are likely to change due to dealumination, so the effect of suppressing dealumination is further improved.

[0059] The content of elemental phosphorus contained in the zeolite-containing catalyst is preferably 0.01 to 2.0 mass % relative to the mass of the entire catalyst, and from the viewpoint of achieving an excellent effect of suppressing dealumination, more preferably 0.05 to 2.0 mass %.

[0060] In this embodiment, the content of phosphorus in the catalyst is a value measured using an X-ray fluorescence analyzer. The content of phosphorus can be measured using a commercially available X-ray fluorescence analyzer under normal conditions in accordance with the instruction manual. For example, when using a Rigaku product under the trade name "RIX3000," the measurement conditions can be P-Kα radiation, a tube voltage of 50 kV, and a tube current of 50 mA.

[0061] In this embodiment, phosphoric acid and / or a phosphate (hereinafter also referred to as a "phosphorus raw material") is used as a raw material for the phosphorus element contained in the zeolite-containing catalyst. Phosphates are more preferred as the phosphorus raw material, and among phosphates, compounds showing a solubility of 1 g or more in 100 g of water at 25°C are more preferred.

[0062] Examples of phosphoric acid include phosphoric acid and pyrophosphoric acid, and examples of phosphates include ammonium phosphate salts such as ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and sodium ammonium hydrogen phosphate, as well as potassium hydrogen phosphate, aluminum hydrogen phosphate, sodium phosphate, and potassium phosphate. Among these, ammonium phosphate salts, which have relatively high solubility in water, are preferred, and at least one 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.

[0063] The silver element may be in the form of, for example, silver ions, which have the effect of improving the hydrothermal resistance of zeolite by controlling the acid sites of the zeolite.

[0064] The content of silver element contained in the zeolite-containing catalyst is preferably 0.01 to 2.0 mass% relative to the mass of the entire catalyst, and from the viewpoint of excellent effect of improving hydrothermal resistance per content, more preferably 0.05 to 2.0 mass%.

[0065] In this embodiment, the silver content in the catalyst is a value measured using an X-ray fluorescence analyzer. The silver content can be measured using a commercially available X-ray fluorescence analyzer under normal conditions in accordance with the instruction manual. For example, when using a Rigaku product under the trade name "RIX3000," the measurement conditions can be P-Kα radiation, a tube voltage of 50 kV, and a tube current of 50 mA.

[0066] In this embodiment, silver nitrate can be used as a source of elemental silver contained in the zeolite-containing catalyst. A zeolite-containing catalyst containing sodium as a counter cation is used, and ion-exchange with silver nitrate and sintered to obtain a zeolite-containing catalyst containing elemental silver. The ion exchange between sodium, the counter cation in the zeolite, and silver nitrate can be performed by immersing the zeolite or the zeolite-containing catalyst in an aqueous solution of silver nitrate, followed by washing with water. In this case, the ion exchange rate can be improved by performing the immersion and washing with water multiple times.

[0067] The zeolite-containing catalyst of this embodiment can be produced by molding a zeolite having the specific physical properties and composition described above, for example, as follows. The molding method is not particularly limited, and a common method can be used. Specific examples include a method of compression molding or extrusion molding of the catalyst components, and a spray-dry molding method that is optimal for a fluidized bed reaction system.

[0068] 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. The mass ratio of zeolite to binder 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 coking, a silica binder is preferred.

[0069] In the ethanol conversion method of this embodiment, a pretreatment step may be performed on the zeolite-containing catalyst prior to contacting the catalyst with the raw material. A preferred pretreatment step is a heat treatment at a temperature of 300°C or higher in the presence of steam. Pretreatment tends to more significantly suppress catalyst degradation and improve selectivity. In the above method, the treatment is preferably performed at a temperature of 300°C or higher and 900°C or lower, in a mixed gas of air or an inert gas such as nitrogen and steam (water vapor), although the atmosphere is not particularly limited, and the treatment is preferably performed under conditions of a water vapor partial pressure of 0.01 atmosphere or higher. The heat treatment temperature is more preferably 400°C or higher and 700°C or lower. Furthermore, this pretreatment step can be performed using a reactor for converting ethanol.

[0070] (Product: Reaction gas containing olefins with 3 or more carbon atoms) In the ethanol conversion method of this embodiment, a reaction gas containing olefins having 3 or more carbon atoms is obtained by contacting a mixed feedstock with a catalyst. The "reaction gas" refers to a gas composition resulting from the reaction of the mixed feedstock with the catalyst. The reaction gas may contain ethylene. The reaction gas may contain hydrogen, 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.

[0071] [Regeneration process] When a catalyst is used in a reaction for a long period of time, coke may adhere to the catalyst, causing coking deterioration. When a catalyst has coked, it can be regenerated by, for example, contacting it with an oxygen-containing gas and burning off the coke on the catalyst at a temperature of 400 to 700°C (hereinafter also referred to as the "regeneration step"). Examples of oxygen-containing gases include air and a mixture of air or oxygen and an inert gas. The oxygen concentration of the oxygen-containing gas is preferably 0.1 to 2.0% by volume. The catalyst may be regenerated by either ex-reactor regeneration, in which the catalyst is withdrawn from the reactor and regenerated outside the reactor, or in-reactor regeneration, in which the catalyst is regenerated within the reactor without being withdrawn from the reactor. Furthermore, by employing a switching reactor, reaction-regeneration switching operation can be performed.

[0072] (Reaction-regeneration switching operation) Reaction-regeneration switching operation is an operation in which a reaction process and a regeneration process are carried out simultaneously using a two-tower or multi-tower switching adiabatic reactor. For example, in the case of a three-tower switching system, two towers are used for the reaction process, and the remaining tower is used for catalyst regeneration. Subsequently, the reaction process in one of the towers used for the reaction process is stopped to perform catalyst regeneration, and the reaction process is carried out in the tower used for catalyst regeneration. This allows catalyst regeneration to be carried out while maintaining the production capacity of the two towers. This type of reaction format is also called the merry-go-round system, and is preferred from the perspective of excellent production efficiency because it does not require stopping the production process for catalyst regeneration.

[0073] [Separation process] The ethanol conversion method of the present embodiment may include separating a target compound such as propylene from the reaction gas (hereinafter also referred to as a "separation step"). The separation step allows ethylene and propylene to be separated from the reaction gas.

[0074] As shown in FIG. 2, the method according to this embodiment can be carried out using an apparatus comprising a reactor 1, distillation columns 2, 3, and 4. The reaction gas obtained in the reaction step carried out in reactor 1 can be separated in distillation column 2 into fraction A, which mainly contains hydrocarbons having 1 to 3 carbon atoms, and fraction B, which mainly contains hydrocarbons having 4 to 8 carbon atoms. Condensed water may be removed from the reaction gas before distillation in distillation column 2 (not shown). Ethylene and propylene are efficiently separated from the reaction gas by separating them from fraction A in distillation columns 3 and 4. 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 various fractions obtained in the separation step, including fraction B, can be recycled as raw materials to the reactor.

[0075] As shown in Figure 3, the method according to this embodiment can be carried out using an apparatus having a reactor 1, a distillation column 2, and a steam cracking apparatus 5. By subjecting fraction B obtained in the separation step to steam cracking, a steam cracking product containing ethylene and propylene is obtained, and the efficiency of the entire process can be improved by separating the ethylene and propylene from the steam cracking product. Steam cracking refers to the thermal decomposition of compounds in the fraction using heated steam.

[0076] As shown in FIG. 4, the method according to this embodiment can be carried out by an apparatus having a reactor 1, a cooling device 6, a distillation column 2, and an oil-water separator 7. A cooling step can be provided in which the reaction gas obtained in the reaction step carried out in the reactor 1 is cooled by the cooling device 6. The cooling step separates the reaction gas 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. 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 fraction D, the aromatic compounds can be efficiently separated from the reaction gas.

[0077] The fraction D recovered in the cooling step is separated in an oil-water separator 7 into a fraction E containing mainly hydrocarbons and a fraction F containing mainly water. The aromatic compounds are efficiently separated from the reaction gas by separating them from fraction E. Separation of the aromatic compounds is carried out by, for example, distillation, extractive distillation, extraction, crystallization, or a combination thereof.

[0078] As shown in FIG. 5, 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. When fraction B is recycled using distillation column 8, it is preferable to separate fraction B1 into fraction B1 containing mainly aliphatic hydrocarbons having 4 to 6 carbon atoms, preferably olefins, and fraction B2 containing mainly aromatic compounds, and recycle at least a portion of fraction B1 to the reactor. By using fraction B1 from which fraction B2 has been removed as a recycled feedstock, aromatic compounds that are not converted to propylene can be removed from the feedstock, allowing propylene to be produced efficiently. In this way, aromatic compounds can also be separated from fraction B as fraction B2. Further separation and purification of aromatic compounds can be carried out by, for example, distillation, extractive distillation, extraction, crystallization, or a combination thereof.

[0079] Furthermore, the method according to this embodiment can be carried out by an apparatus having a reactor 1, a distillation column 2, and a distillation column 9, as shown in Fig. 6. It is preferable that the distillation column 9 separates fraction B into fraction B3 containing mainly hydrocarbons having 4 to 8 carbon atoms and fraction B4 containing mainly hydrocarbons having 9 or more carbon atoms, and at least a portion of fraction B3 is recycled to the reactor. By using fraction B3 from which fraction B4 has been removed as a recycled feedstock, heavy components that may promote coking degradation can be removed from the feedstock, and coking degradation of the catalyst can be suppressed.

[0080] The phrase "mainly comprises" in various fractions means that the total mass of the components described as "mainly comprises" exceeds 50 mass% of the total mass of the fraction.

[0081] These separation steps can be carried out by combining various known methods such as distillation and extraction.

[0082] [Second embodiment] Next, an ethanol conversion method according to the second embodiment will be described.

[0083] <Ethanol Conversion Method - Second Embodiment> The ethanol conversion method of the second embodiment includes contacting a mixed raw material containing methanol and ethanol with a catalyst in an adiabatic reactor to obtain a reaction gas containing olefins having three or more carbon atoms (hereinafter also referred to as the "reaction step"). Propylene can be obtained by separating the above-mentioned reaction gas, and aromatic compounds can also be obtained by separating the above-mentioned reaction gas.

[0084] Conventionally, when commercializing chemical production processes, the selection of a reactor and its type has a significant impact on ease of operation and the magnitude of environmental impact. Fixed-bed adiabatic reactors do not require heating or cooling and have a less complicated structure than reactors such as fluidized beds. Therefore, they are ideal reactors with low design, construction, and operation burdens. For example, if a fixed-bed, single-stage adiabatic reactor could be adopted, its advantages would be even greater. However, such reactors have the drawback of being inapplicable to reaction systems with large endothermic or exothermic reactions.

[0085] Patent Documents 2, 3, and 6 disclose technologies for converting raw materials into the target olefins using a zeolite catalyst, but these technologies cannot be applied to adiabatic reactors because of the large endothermic and exothermic heat generated by them.

[0086] Therefore, an object of the present embodiment is to provide a method for converting alcohol into a target compound in a high yield by using an adiabatic reactor and controlling the temperature inside the reactor, a method for producing propylene, and a method for producing an aromatic compound.

[0087] As a result of intensive research to achieve the above object, the present inventors have found that by controlling the reaction heat in a reactor for converting a raw material mixture of ethanol and methanol into a target compound such as an olefin having 3 or more carbon atoms, an adiabatic reactor can be used and the reaction temperature can be controlled, thereby enabling alcohol to be converted into the target compound in a high yield.

[0088] According to this embodiment, an adiabatic reactor is used, and the temperature inside the reactor is controlled, thereby enabling the alcohol to be converted into the target compound with high yield. Furthermore, according to this embodiment, the use of an adiabatic reactor reduces the operational load, and an environmentally friendly alcohol conversion method with high energy efficiency can be implemented. Furthermore, even when an adiabatic reactor is used, the alcohol can be converted into the target compound with high yield, and coking degradation of the catalyst can be suppressed, making this method suitable as an ethanol conversion method.

[0089] The present inventors have discovered that when methanol or ethanol alone are used as raw materials to convert alcohols in an adiabatic reactor, the yield of high-value-added compounds such as propylene and aromatic compounds decreases, or catalyst coking deterioration occurs. Note that catalyst coking deterioration refers to the deposition of coke on the catalyst surface, reducing the catalytic activity.

[0090] Based on this finding, the present inventors have found that when a mixed raw material containing methanol and ethanol is brought into contact with a catalyst packed in an adiabatic reactor, the alcohols can be converted into target compounds with high yield, and coking deterioration can be suppressed. This is presumably due to the fact that thermal neutralization can be achieved by combining an endothermic reaction and an exothermic reaction 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 the endothermic reaction and the exothermic reaction proceed in the reactor without inhibiting each other, and by combining these exothermic and endothermic reactions, it was possible to easily control the reaction conditions even in an adiabatic reactor. However, the factors are not limited to this.

[0091] (raw materials) The ethanol conversion method of this embodiment uses a mixed raw material containing methanol and ethanol. By using this mixed raw material, an adiabatic reactor can be used and the temperature inside the reactor can be controlled to produce target compounds such as propylene with high yield. From the viewpoint of excellent environmental friendliness, it is preferable that at least one of methanol and ethanol is derived from biomass. Note that biomass refers to organic resources other than fossil resources originating from plants and animals, and biomass-derived refers to compounds produced using biomass as a raw material.

[0092] In the mixed raw material, the molar ratio of methanol / ethanol is preferably 0.050 to 2.0, more preferably 0.20 to 1.5, even more preferably 0.30 to 1.5, and even more preferably 0.30 to 1.0.

[0093] Methanol produced by various methods can be used. For example, methanol obtained by hydrogenating carbon monoxide or carbon dioxide obtained from natural gas or coal, or by distilling wood vinegar can be used. Similarly, ethanol produced by various methods can be used. Among these, bioethanol or ethanol derived from waste is preferred from the viewpoint of environmental friendliness. In the production process of these methanol and ethanol, water is often produced as a by-product or water is often present in the reactor. Therefore, in the ethanol conversion method of this embodiment, the raw materials, methanol and ethanol, may contain water.

[0094] In the ethanol conversion method of this embodiment, the mixed feedstock may further contain an olefin having 4 to 6 carbon atoms. Similar to methanol and ethanol, the olefin having 4 to 6 carbon atoms can give target compounds such as propylene by contacting it with a catalyst. Note that the term "olefin" above includes linear, branched, and cyclic olefins as well as cycloparaffins.

[0095] Examples of olefins having 4 to 6 carbon atoms include butene, pentene, and hexene. In the mixed raw material, the molar ratio of olefins having 4 to 6 carbon atoms to methanol is preferably 3.0 or less, more preferably 1.0 or less, even more preferably 0.5 or less, and even more preferably 0.15 to 0.5.

[0096] The mixed raw material may further contain ethylene. Similar to methanol and ethanol, ethylene can produce target compounds such as propylene by contacting it with a catalyst. The molar ratio of ethylene / ethanol in the mixed raw material is preferably 0.05 or more, more preferably 0.1 or more, and even more preferably 0.1 to 2.0.

[0097] In the ethanol conversion method of this embodiment, the mixed raw material may further contain an oxygenated compound having 1 to 6 carbon atoms other than methanol and ethanol. Similar to methanol and ethanol, the oxygenated compound having 1 to 6 carbon atoms can give a target compound such as propylene by contacting it with a catalyst. Examples of the oxygenated compound having 1 to 6 carbon atoms other than methanol and ethanol include propanol, dimethyl ether, and diethyl ether.

[0098] In the mixed raw material, the molar ratio of oxygen-containing compounds having 1 to 6 carbon atoms other than methanol and ethanol to ethanol is preferably 1.0 or less, and more preferably 0.5 or less.

[0099] Ethylene, ethanol, 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."

[0100] In addition to the above-mentioned effective raw materials, the mixed feedstock can contain saturated aliphatic hydrocarbons such as paraffin, olefins having 7 or more carbon atoms, and oxygen-containing compounds having 7 or more carbon atoms. These saturated aliphatic hydrocarbons, olefins having 7 or more carbon atoms, and oxygen-containing compounds having 7 or more carbon atoms can be converted into target compounds such as propylene by contacting them with a catalyst, similar to methanol and ethanol, but their reactivity is lower than that of the above-mentioned effective raw materials.

[0101] The mixed raw material may contain all or part of the reaction gas containing olefins having 4 or more carbon atoms obtained in the reaction step and the fraction obtained by purifying the reaction gas. In this way, by using a so-called recycle reaction system, it is possible to effectively utilize the raw material.

[0102] In addition to the above-mentioned raw materials that can be converted into target compounds such as propylene by the reaction process, the mixed feedstock may also contain an inert gas such as nitrogen. The mixed feedstock may also contain hydrogen or methane as a diluent gas, but it is preferable that the mixed feedstock does not contain hydrogen (i.e., hydrogen dilution is not performed). Hydrogen is sometimes used to suppress catalyst coking deterioration, but at the same time, hydrogenation reactions of the produced propylene and the like occur, which has the adverse effect of reducing the propylene purity (propylene / (propylene + propane)) [mol / mol]. In the method of this embodiment, the rate of catalyst coking deterioration is low even without hydrogen dilution, 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 the fraction separated from the reaction gas does not have the adverse effect that occurs with hydrogen dilution.

[0103] The total proportion of methanol, olefins having 4 to 6 carbon atoms, ethanol, and ethylene in the mixed raw material is preferably 40 mass% or more, more preferably 50 mass% or more, based on the total mass flow rate of the mixed raw material. The total mass flow rate of the mixed raw material refers to the total flow rate of all compounds, including inert gas, supplied to the reactor.

[0104] The total content of methanol and ethanol in the mixed raw material 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 effective raw material supply mass, provided that the masses of methanol and ethanol converted into methylene and ethylene, respectively, are used to calculate the methanol mass, ethanol mass, and effective raw material supply mass.

[0105] In the mixed raw material, the total content of olefins having 4 to 6 carbon atoms is preferably 65 mass % or less, more preferably 10 to 55 mass %, based on the effective raw material supply mass.

[0106] The mass of effective raw materials supplied is the total mass of effective raw materials supplied per unit time, except that for methanol and ethanol, the mass converted into methylene and ethylene, respectively, is used for calculation.

[0107] In the ethanol conversion method of this embodiment, the mixed raw material may contain water. Since the methanol and ethanol contained in the mixed raw material are produced by various production methods, the mixed raw material contains "water generated in the production process." Here, "water generated in the production process" refers to, for example, water that is generated during the production process of methanol and / or ethanol and that is not removed.

[0108] In the ethanol conversion method of this embodiment, the mixed feedstock may contain steam in addition to "water generated in the production process." Steam has the effect of suppressing coking deterioration by lowering the olefin partial pressure and improving the yield of light olefins. On the other hand, steam may promote dealumination of zeolite, so it is preferable not to include steam in the mixed feedstock in addition to "water generated in the production process."

[0109] (Adiabatic reactor) The ethanol conversion method of this embodiment uses an adiabatic reactor. For details on adiabatic reactors, see Adiabatic Fixed-Bed Reactors (Elsevier, 2014, Ch. 1, P. 4, L. 5-24, ISBN: 978-0-12-801306-9). Examples of adiabatic reactors include fixed-bed adiabatic reactors, moving-bed adiabatic reactors, and fluidized-bed adiabatic reactors. However, a fixed-bed adiabatic reactor is preferred for the method of this embodiment. Among fixed-bed adiabatic reactors, a fixed-bed single-stage adiabatic reactor with only one fixed catalyst bed is more preferred. Because carbonaceous matter (coke) accumulates on the catalyst during the reaction, a multi-column switching type fixed-bed single-stage adiabatic reactor is preferred, as it allows for the combustion and removal of this carbonaceous matter while the reaction continues.

[0110] 1 is a schematic diagram of a fixed-bed, single-stage adiabatic reactor. The fixed-bed, single-stage adiabatic reactor 1 comprises a reaction casing 12 with a heat insulating material 121 provided on the outer periphery, a catalyst bed 13, a reactor inlet 14, and a reactor outlet 15. The reaction casing 12 is provided with the heat insulating material 121 on the outer periphery, thereby preventing heat from escaping from within the reactor to the outside. In the production method according to this embodiment, the temperature within the reactor can be controlled by the heat generated and absorbed by the reaction.

[0111] The catalyst bed 13 is filled with a catalyst, which will be described later. A first sheathed thermocouple 161 is provided in the catalyst bed 13 immediately before it contacts the catalyst bed inlet 131. A second sheathed thermocouple 162 is provided in the catalyst bed 13 immediately after it passes through the catalyst bed outlet 132. These thermocouples measure the temperature of the mixed raw material immediately before it contacts the catalyst bed inlet 131 and the reaction gas immediately after it passes through the catalyst bed outlet 132. The catalyst bed 13 may be of a multi-stage type, but is preferably of a single stage type as shown in FIG. 1.

[0112] In the fixed-bed single-stage adiabatic reactor 1, a mixed raw material is introduced from a reactor inlet 14 and brought into contact with a catalyst bed 13, and a reaction gas is taken out from a reactor outlet 15.

[0113] (Reaction process conditions) In the ethanol conversion method of this embodiment, the reaction temperature may be 300°C or higher. Since the produced olefins are in thermal equilibrium, the reaction temperature is preferably 450°C or higher from the viewpoint of further improving the propylene yield. Furthermore, the reaction temperature is preferably less than 600°C from the viewpoint of suppressing the acceleration of coking deterioration, which is promoted at high temperatures. More specifically, the temperature of the reaction gas at the catalyst bed inlet is preferably 450°C to 590°C, and the temperature of the reaction gas at the catalyst outlet is preferably 450°C to 590°C.

[0114] 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.

[0115] The inlet temperature of the catalyst bed is the temperature of the mixed raw material immediately before the raw material fluid comes into contact with the catalyst bed packed in an adiabatic reactor. The outlet temperature of the catalyst bed is the temperature of the reaction gas immediately after it has passed through the catalyst bed. The temperatures of the mixed raw material and reaction gas here refer to the temperatures between 0d and 0.8d in a plane perpendicular to the fluid flow direction, where 0 is the center of the reactor and d is the distance from the center of the reactor to the inner wall surface of the reactor. The average inlet and outlet reaction temperature is calculated by measuring the inlet temperature and outlet temperature of the catalyst bed, as shown in Figure 1, using the formula: [inlet temperature of catalyst bed + outlet temperature of catalyst bed] / 2 (hereinafter simply referred to as "reaction temperature").

[0116] 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.

[0117] The feed rate of the effective raw material is preferably 0.1 to 1000 h , in terms of the mass space velocity (WHSV) of the catalyst. -1 and more preferably 0.1 to 500 hours -1 and more preferably 0.5 to 100 hours -1In the ethanol conversion method of this embodiment, ethanol is converted into ethylene and then WHSV is calculated as shown in the following formula. From the viewpoint of excellent productivity of target compounds such as propylene and aromatic compounds, the mass flow rate of the effective raw material supply is preferably 1 kg / hr or more, more preferably 10 kg / hr or more, and even more preferably 1 t / hr or more.

[0118] WHSV(hr -1 ) = Effective raw material supply mass flow rate (kg / hr) / Amount of catalyst (kg) Effective raw material supply mass flow rate (kg / hr) = methylene-equivalent methanol flow rate (kg / hr) + ethylene-equivalent ethanol flow rate (kg / hr) + carbon number 4-6 olefin flow rate (kg / hr) + ethylene flow rate (kg / hr) + carbon number 1-6 oxygenated compound flow rate other than ethanol (kg / hr) Methylene-equivalent methanol flow rate (kg / hr) = methanol flow rate (kg / hr) x 0.438 Ethylene-equivalent ethanol flow rate (kg / hr) = ethanol flow rate (kg / hr) x 0.609

[0119] (catalyst) The catalyst used in the ethanol conversion method of this embodiment is a solid catalyst that exhibits catalytic activity for converting olefins, methanol, and ethanol into target compounds such as propylene and aromatic compounds. Zeolite-containing catalysts are preferred as such catalysts because of their excellent thermal durability and propylene selectivity. A common issue in conventional olefin production using zeolites is coking, in which heavy carbonaceous material (coke) accumulates inside the zeolite pores due to reaction with hydrocarbons, deactivating the catalyst. To regenerate the catalyst, the coke must be burned and removed in an atmosphere containing molecular oxygen. However, this coke combustion causes structural collapse of the zeolite, leading to permanent deterioration of the catalyst, which cannot be regenerated. The ethanol conversion method of this embodiment can suppress coke formation, making it easier to maintain activity even when using a zeolite-containing catalyst.

[0120] <Zeolite-containing catalyst> The zeolite-containing catalyst is a catalyst powder or molded body containing zeolite as an active species. In the ethanol conversion method of this embodiment, it is preferable to use a so-called intermediate pore size zeolite having a pore size of 5 to 6 Å as the zeolite in the zeolite-containing catalyst. The intermediate pore size zeolite means "a zeolite whose pore size range is intermediate between the pore size of small pore size zeolites, such as A-type zeolites, and the pore size of large pore size zeolites, such as mordenite, X-type zeolites, and Y-type zeolites." The "intermediate pore size zeolite" has a so-called 10-membered oxygen ring in its crystal structure.

[0121] Examples of intermediate pore diameter zeolites include ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-21, ZSM-23, ZSM-35, and ZSM-38, with ZSM-5-type zeolites such as ZSM-5, ZSM-11, and ZSM-8, and ZSM-38 being preferred. Zeolites similar to ZSM-5 and ZSM-11 described in Stud. Surf. Sci. Catal. 1987, 33, 167-215 can also be used, and among these, MFI-type zeolites are preferred, with ZSM-5 being more preferred, from the viewpoint of excellent catalytic performance (catalytic activity and durability against coking).

[0122] The silica / alumina (SiO2 / Al2O3) molar ratio of the zeolite contained in the zeolite-containing catalyst of this embodiment can be appropriately selected, but from the viewpoint of excellent catalytic activity and selectivity, it is preferably 20 to 2000, and from the viewpoint of improving the durability of the catalyst, it is more preferably 100 to 1500, even more preferably 300 to 1200, and even more preferably 800 to 1200. The silica / alumina (SiO2 / Al2O3) molar ratio of the zeolite contained in the zeolite-containing catalyst may be 20 to 400 or may be 100 to 300. The silica / alumina molar ratio of the zeolite can be measured by a known method, for example, by completely dissolving the zeolite in an alkaline aqueous solution and analyzing the resulting solution by plasma emission spectroscopy or the like.

[0123] The method for synthesizing the zeolite of this embodiment is not particularly limited, but can be produced by optimizing various conditions of a conventionally known method for hydrothermal synthesis of MFI zeolite. Generally, means for efficiently obtaining MFI zeolite by hydrothermal synthesis include a method of hydrothermal synthesis using an appropriate organic structure-directing agent (SDA), a method of hydrothermal synthesis in which hydrothermally synthesized MFI zeolite is added as seed crystals, and a method of hydrothermal synthesis in which seed slurry in the crystallization stage is added. Examples of the organic structure-directing agent (SDA) used here include ammonium salts, urea compounds, amines, and alcohols. It is known that not only organic SDAs 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 for MFI zeolites described above, a suitable catalyst can be obtained by optimizing the synthesis conditions, such as the type of raw materials and additives (SDAs), the amount of additives, pH, silica / alumina molar ratio, medium, and the ratio of cations and anions in the raw material feed composition, synthesis temperature, and synthesis time.

[0124] Specific examples include the synthesis method 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).

[0125] In addition, commercially available zeolites can also be used as long as they are MFI zeolites having the above-mentioned specific physical properties and composition.

[0126] The zeolite-containing catalyst in this embodiment preferably contains elemental phosphorus or elemental silver.

[0127] Examples of the form of elemental phosphorus include a phosphorus polymer (e.g., polyphosphoric acid), an oxide of phosphorus (e.g., PO), and a compound in which phosphorus is added to aluminum in a zeolite. A combination of these may also be included. When the zeolite contains aluminum, elemental phosphorus has the effect of suppressing dealumination of the zeolite and, in some cases, of improving the propylene yield in the propylene production reaction. In the method according to this embodiment, water is generated in the reactor by the dehydration reaction of alcohol, and the raw materials, methanol and ethanol, may contain water. This tends to create a high-temperature steam atmosphere in the reactor, and dealumination can easily change the properties of the zeolite-containing catalyst. However, the inclusion of elemental phosphorus in the zeolite-containing catalyst further improves the effect of suppressing dealumination of the zeolite.

[0128] The content of elemental phosphorus contained in the zeolite-containing catalyst is preferably 0.01 to 2.0 mass % relative to the mass of the entire catalyst, and from the viewpoint of achieving an excellent effect of suppressing dealumination, more preferably 0.05 to 2.0 mass %.

[0129] In this embodiment, the content of phosphorus in the catalyst is a value measured using an X-ray fluorescence analyzer. The content of phosphorus can be measured using a commercially available X-ray fluorescence analyzer under normal conditions in accordance with the instruction manual. For example, when using a Rigaku product under the trade name "RIX3000," the measurement conditions can be P-Kα radiation, a tube voltage of 50 kV, and a tube current of 50 mA.

[0130] In this embodiment, phosphoric acid and / or a phosphate (hereinafter also referred to as a "phosphorus raw material") is used as a raw material for the phosphorus element contained in the zeolite-containing catalyst. Phosphates are more preferred as the phosphorus raw material, and among phosphates, compounds showing a solubility of 1 g or more in 100 g of water at 25°C are more preferred.

[0131] Examples of phosphoric acid include phosphoric acid and pyrophosphoric acid, and examples of phosphates include ammonium phosphate salts such as ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and sodium ammonium hydrogen phosphate, as well as potassium hydrogen phosphate, aluminum hydrogen phosphate, sodium phosphate, and potassium phosphate. Among these, ammonium phosphate salts, which have relatively high solubility in water, are preferred, and at least one 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.

[0132] The silver element may be in the form of, for example, silver ions, which have the effect of improving the hydrothermal resistance of zeolite by controlling the acid sites of the zeolite.

[0133] The content of silver element contained in the zeolite-containing catalyst is preferably 0.01 to 2.0 mass% relative to the mass of the entire catalyst, and from the viewpoint of excellent effect of improving hydrothermal resistance per content, more preferably 0.05 to 2.0 mass%.

[0134] In this embodiment, the silver content in the catalyst is a value measured using an X-ray fluorescence analyzer. The silver content can be measured using a commercially available X-ray fluorescence analyzer under normal conditions in accordance with the instruction manual. For example, when using a Rigaku product under the trade name "RIX3000," the measurement conditions can be P-Kα radiation, a tube voltage of 50 kV, and a tube current of 50 mA.

[0135] In this embodiment, silver nitrate can be used as a source of elemental silver contained in the zeolite-containing catalyst. A zeolite-containing catalyst containing sodium as a counter cation is used, and ion-exchange with silver nitrate and sintered to obtain a zeolite-containing catalyst containing elemental silver. The ion exchange between sodium, the counter cation in the zeolite, and silver nitrate can be performed by immersing the zeolite or the zeolite-containing catalyst in an aqueous solution of silver nitrate, followed by washing with water. In this case, the ion exchange rate can be improved by performing the immersion and washing with water multiple times.

[0136] The zeolite-containing catalyst of this embodiment can be produced by molding a zeolite having the specific physical properties and composition described above, for example, as follows. The molding method is not particularly limited, and a common method can be used. Specific examples include a method of compression molding or extrusion molding of the catalyst components, and a spray-dry molding method that is optimal for a fluidized bed reaction system.

[0137] 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. The mass ratio of zeolite to binder 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 coking, a silica binder is preferred.

[0138] In the ethanol conversion method of this embodiment, a pretreatment step may be performed on the zeolite-containing catalyst prior to contacting the catalyst with the raw material. A preferred pretreatment step is a heat treatment at a temperature of 300°C or higher in the presence of steam. Pretreatment tends to more significantly suppress catalyst degradation and improve selectivity. In the above method, the treatment is preferably performed at a temperature of 300°C or higher and 900°C or lower, in a mixed gas of air or an inert gas such as nitrogen and steam (water vapor), although the atmosphere is not particularly limited, and the treatment is preferably performed under conditions of a water vapor partial pressure of 0.01 atmosphere or higher. The heat treatment temperature is more preferably 400°C or higher and 700°C or lower. Furthermore, this pretreatment step can be performed using a reactor for converting alcohol.

[0139] (Product: Reaction gas containing olefins with 3 or more carbon atoms) In the ethanol conversion method of this embodiment, a reaction gas containing olefins having 3 or more carbon atoms is obtained by contacting a mixed feedstock with a catalyst. The "reaction gas" refers to a gas composition resulting from the reaction of the mixed feedstock with the catalyst. The reaction gas may contain ethylene. The reaction gas may contain hydrogen, 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. 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.

[0140] [Regeneration process] When a catalyst is used in a reaction for a long period of time, coke may adhere to the catalyst, causing coking deterioration. When a catalyst has coked, it can be regenerated by, for example, contacting it with an oxygen-containing gas at a temperature of 400 to 700°C to burn off the coke on the catalyst (hereinafter also referred to as the "regeneration step"). Examples of the oxygen-containing gas include air and a mixture of air or oxygen and an inert gas. The oxygen concentration of the oxygen-containing gas is preferably 0.1 to 2.0% by volume. The catalyst may be regenerated by either an out-of-reactor regeneration method in which the catalyst is withdrawn from the reactor and regenerated outside the reactor, or an in-reactor regeneration method in which the catalyst is regenerated within the reactor without being withdrawn from the reactor. Furthermore, a switching reactor can be used to perform a reaction-regeneration switching operation.

[0141] (Reaction-regeneration switching operation) Reaction-regeneration switching operation is an operation in which a reaction process and a regeneration process are carried out simultaneously using a two-tower or multi-tower switching adiabatic reactor. For example, in the case of a three-tower switching system, two towers are used for the reaction process, and the remaining tower is used for catalyst regeneration. Subsequently, the reaction process in one of the towers used for the reaction process is stopped to perform catalyst regeneration, and the reaction process is carried out in the tower used for catalyst regeneration. This allows catalyst regeneration to be carried out while maintaining the production capacity of the two towers. This type of reaction format is also called the merry-go-round system, and is preferred from the perspective of excellent production efficiency because it does not require stopping the production process for catalyst regeneration.

[0142] [Separation process] In the separation step, the target compounds are separated from the reaction gas, and ethylene, propylene, and aromatic compounds can be separated from the reaction gas by the separation step.

[0143] As shown in FIG. 2, the method according to this embodiment can be carried out using an apparatus comprising a reactor 1, distillation columns 2, 3, and 4. The reaction gas obtained in the reaction step carried out in reactor 1 can be separated in distillation column 2 into fraction A, which mainly contains hydrocarbons having 1 to 3 carbon atoms, and fraction B, which mainly contains hydrocarbons having 4 to 8 carbon atoms. Condensed water may be removed from the reaction gas before distillation in distillation column 2 (not shown). Ethylene and propylene are efficiently separated from the reaction gas by separating them from fraction A in distillation columns 3 and 4. 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 various fractions obtained in the separation step, including fraction B, can be recycled as raw materials to the reactor.

[0144] As shown in Figure 3, the method according to this embodiment can be carried out using an apparatus having a reactor 1, a distillation column 2, and a steam cracking apparatus 5. By subjecting fraction B obtained in the separation step to steam cracking, a steam cracking product containing ethylene and propylene is obtained, and the efficiency of the entire process can be improved by separating the ethylene and propylene from the steam cracking product. Steam cracking refers to the thermal decomposition of compounds in the fraction using heated steam.

[0145] As shown in FIG. 4, the method according to this embodiment can be carried out by an apparatus having a reactor 1, a cooling device 6, a distillation column 2, and an oil-water separator 7. A cooling step can be provided in which the reaction gas obtained in the reaction step carried out in the reactor 1 is cooled by the cooling device 6. The cooling step separates the reaction gas 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. 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 fraction D, the aromatic compounds can be efficiently separated from the reaction gas.

[0146] The fraction D recovered in the cooling step is separated in an oil-water separator 7 into a fraction E containing mainly hydrocarbons and a fraction F containing mainly water. The aromatic compounds are efficiently separated from the reaction gas by separating them from fraction E. Separation of the aromatic compounds is carried out by, for example, distillation, extractive distillation, extraction, crystallization, or a combination thereof.

[0147] As shown in FIG. 5, 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. When fraction B is recycled using distillation column 8, it is preferable to separate fraction B1 into fraction B1 containing mainly aliphatic hydrocarbons having 4 to 6 carbon atoms, preferably olefins, and fraction B2 containing mainly aromatic compounds, and recycle at least a portion of fraction B1 to the reactor. By using fraction B1 from which fraction B2 has been removed as a recycled feedstock, aromatic compounds that are not converted to propylene can be removed from the feedstock, allowing propylene to be produced efficiently. In this way, aromatic compounds can also be separated from fraction B as fraction B2. Further separation and purification of aromatic compounds can be carried out by, for example, distillation, extractive distillation, extraction, crystallization, or a combination thereof.

[0148] Furthermore, the method according to this embodiment can be carried out by an apparatus having a reactor 1, a distillation column 2, and a distillation column 9, as shown in Fig. 6. It is preferable that the distillation column 9 separates fraction B into fraction B3 containing mainly hydrocarbons having 4 to 8 carbon atoms and fraction B4 containing mainly hydrocarbons having 9 or more carbon atoms, and at least a portion of fraction B3 is recycled to the reactor. By using fraction B3 from which fraction B4 has been removed as a recycled feedstock, heavy components that may promote coking degradation can be removed from the feedstock, and coking degradation of the catalyst can be suppressed.

[0149] The phrase "mainly comprises" in each fraction means that the total mass of the components described as "mainly comprises" exceeds 50 mass% of each fraction.

[0150] These separation steps can be carried out by combining various known methods such as distillation and extraction.

[0151] [Third embodiment] Next, an ethanol conversion method according to a third embodiment will be described.

[0152] <Ethanol Conversion Method -Third Embodiment-> The ethanol conversion method according to this embodiment includes the steps of: A mixed feedstock containing ethanol and ethylene is brought into contact with a conversion catalyst in an adiabatic reactor to obtain a reaction gas containing olefins having 3 or more carbon atoms (hereinafter also referred to as the "reaction step"); separating the reaction gas into a fraction A mainly containing hydrocarbons having 2 to 3 carbon atoms and a fraction B mainly containing hydrocarbons having 4 to 6 carbon atoms using a first distillation column (hereinafter also referred to as the "first separation step"); recycling at least a portion of the fraction A to the reaction step as a part of the mixed raw material (hereinafter also referred to as the "recycle step"); Includes. According to the present embodiment described above, it is possible to provide a method for converting ethanol into a target compound with high yield by using an adiabatic reactor and controlling the temperature inside the reactor. Propylene can be obtained by separating the above-mentioned reaction gas, and aromatic compounds can also be obtained by separating the above-mentioned reaction gas.

[0153] Conventionally, when commercializing chemical manufacturing processes, the selection of a reactor and its reaction mode has a significant impact on ease of operation and the magnitude of environmental impact. Adiabatic reactors have a simple configuration that does not require heating or cooling of the reactor, making them ideal reactors with low design, construction, and operational burdens. For example, if a fixed-bed, single-stage adiabatic reactor could be adopted, its advantages would be even greater. However, adiabatic reactors have challenges with temperature control in reaction systems with large endothermic or exothermic reactions.

[0154] Patent Documents 1 to 3 disclose techniques for converting each raw material into the target olefin using a zeolite catalyst, but these techniques cannot be applied to an adiabatic reactor because of the large endothermic and exothermic heat generated by them. Patent Documents 4 and 5 disclose thermal neutralization techniques that utilize an exothermic reaction using an oxygen-containing compound such as alcohol as a raw material. However, a reaction using ethanol as a raw material, which induces an endothermic reaction, cannot be carried out in an adiabatic reactor.

[0155] When a mixed feedstock containing ethanol and ethylene is converted using a catalyst, compounds other than the target compounds are contained in the reaction gas. By effectively utilizing these compounds as feedstock, we will investigate a method for efficiently converting ethanol and ethylene to the target compounds while solving the above-mentioned problem of temperature control in the reactor.

[0156] Therefore, an object of the present invention is to provide a method for converting ethanol, which uses an adiabatic reactor and controls the temperature inside the reactor to convert ethanol and ethylene into target compounds with high efficiency, a method for producing propylene, a method for producing aromatic compounds, and an apparatus for converting ethanol and ethylene.

[0157] As a result of intensive research to achieve the above object, the present inventors have found that by subjecting the reaction gas obtained by the conversion of ethanol and ethylene to a separation step and then recycling it to a reaction step, it becomes possible to control the reaction heat for the conversion of ethanol and ethylene to olefins having 3 or more carbon atoms, etc., and that ethanol and ethylene can be converted to target compounds in high yields by using an adiabatic reactor and controlling the temperature inside the reactor.

[0158] According to the present embodiment, it is possible to provide a method for converting ethanol into a target compound with high efficiency by using an adiabatic reactor and controlling the temperature inside the reactor, a method for producing propylene, a method for producing an aromatic compound, and an apparatus for converting ethanol and ethylene.

[0159] <Reaction process> In the reaction step according to this embodiment, a mixed feedstock containing ethanol and ethylene is contacted with a catalyst in an adiabatic reactor to obtain a reaction gas containing olefins having three or more carbon atoms. Furthermore, according to this embodiment, the use of an adiabatic reactor reduces the operational load and enables an environmentally friendly conversion method with high energy efficiency to be implemented. Furthermore, even when an adiabatic reactor is used, the recycling step described below allows ethanol and ethylene to be converted to the target compounds with high yields, and coking degradation of the catalyst can be suppressed, making this method suitable as an ethanol conversion method.

[0160] The present inventors have found that when propylene is produced in an adiabatic reactor using ethylene or ethanol alone as raw materials, the propylene yield decreases or the catalyst deteriorates due to coking. The term "catalyst deterioration due to coke deposition on the catalyst surface reduces the activity of the catalyst."

[0161] Based on this finding, the present inventors have found that when a mixed raw material containing ethylene and ethanol is brought into contact with a catalyst packed in an adiabatic reactor, propylene can be produced in a high yield and coking deterioration can be suppressed.

[0162] It is believed that this is due to the fact that thermal neutralization can be achieved by combining an endothermic reaction and an exothermic reaction that do not inhibit each other. The conversion reaction from ethylene to propylene is an exothermic reaction. Furthermore, the conversion reaction from ethanol to propylene, in the presence of a catalyst, is an endothermic reaction consisting of a two-stage reaction: a dehydration reaction from ethanol to ethylene and a conversion reaction from ethylene to propylene. In this embodiment, it was found that the conversion reaction from ethylene to propylene and the conversion reaction from ethanol to propylene proceed without inhibiting each other, and it is believed that the combination of these exothermic and endothermic reactions made it possible to control the reaction conditions even in an adiabatic reactor. However, the factors are not limited to this.

[0163] (raw materials) In the ethanol conversion method of this embodiment, a mixed raw material containing ethylene and ethanol is used. By using this mixed raw material, a target compound such as propylene can be produced with high yield by using an adiabatic reactor and controlling the temperature inside the reactor. From the viewpoint of excellent environmental friendliness, it is preferable that the ethanol is derived from biomass. Note that biomass refers to organic resources other than fossil resources originating from plants and animals, and biomass-derived refers to a compound produced using biomass as a raw material.

[0164] The ethylene contained in the mixed raw material is supplied by recycling a part or all of the ethylene contained in the fraction separated from the reaction gas as the raw material. In this way, by using a so-called recycle reaction system, it is possible to effectively utilize the raw material.

[0165] From the viewpoint of excellent variability of the raw material ratio, the mixed feedstock may further contain "additional ethylene" in addition to the ethylene contained in the fraction separated from the reaction gas. The "additional ethylene" may be produced by various methods. For example, it may be obtained by thermal cracking of naphtha and / or ethane, direct or oxidative dehydrogenation of ethane, or dehydration of ethanol.

[0166] In the production process of ethylene and ethanol, water is often produced as a by-product or water is often present in the reactor. Therefore, in the conversion method of the present embodiment, the raw materials ethylene and ethanol may contain water.

[0167] In terms of controlling the temperature in the reactor and converting ethanol into the target compound in a high yield, the molar ratio of ethylene / ethanol in the mixed raw material is preferably 0.20 to 2.5, more preferably 0.20 to 2.0, even more preferably 0.30 to 1.5, and particularly preferably 0.30 to 1.0.

[0168] In the ethanol conversion method of this embodiment, the mixed raw material may further contain methanol. Methanol produced by various methods can be used. For example, methanol obtained by hydrogenation of carbon monoxide or carbon dioxide obtained from natural gas or coal, or by distillation of wood vinegar can be used.

[0169] In the ethanol conversion method of this embodiment, the mixed feedstock may further contain an olefin having 4 to 6 carbon atoms. Similar to ethylene and ethanol, the olefin having 4 to 6 carbon atoms can give a target compound such as propylene by contacting it with a catalyst. Examples of the olefin having 4 to 6 carbon atoms include butene, pentene, and hexene. In the present specification, the term "olefin" includes linear, branched, and cyclic olefins as well as cycloparaffins.

[0170] In the mixed raw material, the molar ratio of olefins having 4 to 6 carbon atoms to ethylene is preferably 3.0 or less, more preferably 1.0 or less, even more preferably 0.5 or less, and even more preferably 0.15 to 0.5.

[0171] In the ethanol conversion method of this embodiment, the mixed raw material may further contain an oxygen-containing compound having 1 to 6 carbon atoms other than ethanol. Similar to ethylene and ethanol, the oxygen-containing compound having 1 to 6 carbon atoms can give a target compound such as propylene by contacting it with a catalyst. Examples of the oxygen-containing compound having 1 to 6 carbon atoms other than ethanol include methanol, propanol, dimethyl ether, and diethyl ether.

[0172] In the mixed raw material, the molar ratio of oxygen-containing compounds having 1 to 6 carbon atoms other than ethanol to ethanol is preferably 1.0 or less, and more preferably 0.5 or less.

[0173] Ethylene, ethanol, 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."

[0174] The mixed feedstock may contain, in addition to the above-mentioned effective raw materials, saturated aliphatic hydrocarbons such as paraffin, olefins having 7 or more carbon atoms, and oxygen-containing compounds having 7 or more carbon atoms. Like ethylene and ethanol, saturated aliphatic hydrocarbons, olefins having 7 or more carbon atoms, and oxygen-containing compounds having 7 or more carbon atoms can be converted into target compounds by contacting them with a catalyst, but they have lower reactivity than the above-mentioned effective raw materials.

[0175] The mixed feedstock may contain an inert gas such as nitrogen in addition to the above-mentioned feedstocks that can be converted to propylene by the reaction step. The mixed feedstock may also contain hydrogen or methane as a diluent gas, but it is preferable not to dilute with hydrogen. Hydrogen is sometimes used to suppress catalyst coking deterioration, but at the same time, hydrogenation reactions of the produced propylene and the like occur, which has the adverse effect of reducing the propylene purity (propylene / (propylene + propane)) [mol / mol]. In the method of this embodiment, it is preferable not to dilute with hydrogen because the rate of catalyst coking deterioration is low and stable operation is possible even when hydrogen dilution is not performed.

[0176] The total proportion of ethylene, olefins having 4 to 6 carbon atoms, and ethanol in the mixed raw material is preferably 40 mass% or more, more preferably 50 mass% or more, based on the mass flow rate of the mixed raw material. The mass flow rate of the mixed raw material refers to the total flow rate of all compounds, including inert components, fed to the reactor.

[0177] The total content of ethylene and ethanol in the mixed raw material is preferably 30 to 100 mass%, more preferably 40 to 100 mass%, and even more preferably 50 to 100 mass%, based on the effective raw material supply mass, provided that the mass of ethanol converted into ethylene is used in calculating the ethanol mass and the effective raw material supply mass.

[0178] In the mixed raw material, the total content of olefins having 4 to 6 carbon atoms is preferably 65 mass % or less, more preferably 10 to 55 mass %, based on the effective raw material supply mass.

[0179] In the ethanol conversion method of this embodiment, the mixed raw material may contain water. Since the ethylene and ethanol contained in the mixed raw material are produced by various production methods, the mixed raw material may contain "water generated in the production process." Here, "water generated in the production process" refers to water that is generated in the process of producing ethylene and / or ethanol and has not been removed.

[0180] In the ethanol conversion method of this embodiment, the mixed feedstock may contain steam in addition to "water generated in the production process." Steam has the effect of suppressing coking deterioration by lowering the olefin partial pressure and improving the yield of light olefins. On the other hand, steam may promote dealumination of zeolite, so it is preferable that the mixed feedstock does not contain steam in addition to "water generated in the production process."

[0181] (Adiabatic reactor) The ethanol conversion method of this embodiment is characterized by the use of an adiabatic reactor. For details on adiabatic reactors, see Adiabatic Fixed-Bed Reactors (Elsevier, 2014, Ch. 1, P. 4, L. 5-24, ISBN: 978-0-12-801306-9). Examples of adiabatic reactors include fixed-bed adiabatic reactors, moving-bed adiabatic reactors, and fluidized-bed adiabatic reactors. However, a fixed-bed adiabatic reactor is preferred for the method of this embodiment. Among fixed-bed adiabatic reactors, a fixed-bed single-stage adiabatic reactor with only one fixed catalyst bed is more preferred. Because carbonaceous matter (coke) accumulates on the catalyst during the reaction, a multi-column switching type fixed-bed single-stage adiabatic reactor is preferred, as it allows for the combustion and removal of this carbonaceous matter while the reaction continues.

[0182] 1 is a schematic diagram of a fixed-bed, single-stage adiabatic reactor. The fixed-bed, single-stage adiabatic reactor 1 comprises a reaction casing 12 with a heat insulating material 121 provided on the outer periphery, a catalyst bed 13, a reactor inlet 14, and a reactor outlet 15. The reaction casing 12 is provided with the heat insulating material 121 on the outer periphery, thereby preventing heat from escaping from within the reactor to the outside. In the production method according to this embodiment, the temperature within the reactor can be controlled by the heat generated and absorbed by the reaction.

[0183] The catalyst bed 13 is filled with a catalyst, which will be described later. A first sheathed thermocouple 161 is provided in the catalyst bed 13 immediately before it contacts the catalyst bed inlet 131. A second sheathed thermocouple 162 is provided in the catalyst bed 13 immediately after it passes through the catalyst bed outlet 132. These thermocouples measure the temperature of the mixed raw material immediately before it contacts the catalyst bed inlet 131 and the reaction gas immediately after it passes through the catalyst bed outlet 132. The catalyst bed 13 may be of a multi-stage type, but is preferably of a single stage type as shown in FIG. 1.

[0184] In the fixed-bed single-stage adiabatic reactor 1, a mixed raw material is introduced from a reactor inlet 14 and brought into contact with a catalyst bed 13, and a reaction gas is taken out from a reactor outlet 15.

[0185] (Reaction process conditions) In the ethanol conversion method of this embodiment, the reaction temperature may be 300°C or higher. Since the produced olefins are in thermal equilibrium, the reaction temperature is preferably 450°C or higher from the viewpoint of further improving the propylene yield. Furthermore, the reaction temperature is preferably less than 600°C from the viewpoint of suppressing the acceleration of coking deterioration, which is promoted at high temperatures. More specifically, the temperature of the reaction gas at the catalyst bed inlet is preferably 450°C to 590°C, and the temperature of the reaction gas at the catalyst outlet is preferably 450°C to 590°C.

[0186] The temperature difference between the outlet temperature of the catalyst bed and the inlet temperature of the catalyst bed is preferably -80K to 80K, more preferably -60K to 60K.

[0187] The inlet temperature of the catalyst bed is the temperature of the mixed raw material immediately before the raw material fluid comes into contact with the catalyst bed packed in an adiabatic reactor. The outlet temperature of the catalyst bed is the temperature of the reaction gas immediately after it has passed through the catalyst bed. The temperatures of the mixed raw material and reaction gas here refer to the temperatures between 0d and 0.8d in a plane perpendicular to the fluid flow direction, where 0 is the center of the reactor and d is the distance from the center of the reactor to the inner wall surface of the reactor. The average inlet and outlet reaction temperature is calculated by measuring the inlet temperature and outlet temperature of the catalyst bed, as shown in Figure 1, using the formula: [inlet temperature of catalyst bed + outlet temperature of catalyst bed] / 2 (hereinafter simply referred to as "reaction temperature").

[0188] 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.

[0189] The feed rate of the effective raw material is preferably 0.1 to 1000 h , in terms of the mass space velocity (WHSV) of the catalyst. -1 and more preferably 0.1 to 500 hours -1 and more preferably 0.5 to 100 hours -1 In the ethanol conversion method of this embodiment, ethanol is converted into ethylene and then the WHSV is calculated as shown in the following formula. From the viewpoint of excellent productivity of the target compound, the mass flow rate of the effective raw material supply is preferably 1 kg / hr or more, more preferably 10 kg / hr or more, and even more preferably 1 t / hr or more.

[0190] WHSV(hr -1 ) = Effective raw material supply mass flow rate (kg / hr) / Amount of catalyst (kg) Effective raw material supply mass flow rate (kg / hr) = ethylene flow rate (kg / hr) + ethylene-equivalent ethanol mass flow rate (kg / hr) + carbon number 4-6 olefin flow rate (kg / hr) + carbon number 1-6 oxygenated compound flow rate other than ethanol (kg / hr) Ethylene-equivalent ethanol flow rate (kg / hr) = ethanol flow rate (kg / hr) × ethylene molecular weight (g / mol) / ethanol molecular weight (g / mol)

[0191] (catalyst) The catalyst used in the ethanol conversion method of this embodiment is a solid catalyst that exhibits catalytic activity for converting olefins and ethanol into target compounds such as propylene. Zeolite-containing catalysts are preferred as such catalysts because of their excellent thermal durability. A common issue in conventional olefin production using zeolites is coking, in which heavy carbonaceous material (coke) accumulates inside the zeolite pores due to reaction with hydrocarbons, resulting in deactivation. To regenerate the catalyst, the coke must be burned and removed in an atmosphere containing oxygen molecules. However, this coke combustion causes structural collapse of the zeolite, leading to permanent deterioration of the catalyst that cannot be regenerated. The ethanol conversion method of this embodiment can suppress coke formation, making it easier to maintain activity even when using a zeolite-containing catalyst.

[0192] <Zeolite-containing catalyst> The zeolite-containing catalyst is a catalyst powder or molded body containing zeolite as an active species. In the ethanol conversion method of this embodiment, it is preferable to use a so-called intermediate pore size zeolite having a pore size of 5 to 6 Å as the zeolite in the zeolite-containing catalyst. The intermediate pore size zeolite means "a zeolite whose pore size range is intermediate between the pore size of small pore size zeolites, such as A-type zeolites, and the pore size of large pore size zeolites, such as mordenite, X-type zeolites, and Y-type zeolites." The "intermediate pore size zeolite" has a so-called 10-membered oxygen ring in its crystal structure.

[0193] Examples of intermediate pore diameter zeolites include ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-21, ZSM-23, ZSM-35, and ZSM-38, with ZSM-5-type zeolites such as ZSM-5, ZSM-11, and ZSM-8, and ZSM-38 being preferred. Zeolites similar to ZSM-5 and ZSM-11 described in Stud. Surf. Sci. Catal. 1987, 33, 167-215 can also be used, and among these, MFI-type zeolites are preferred, with ZSM-5 being more preferred, from the viewpoint of excellent catalytic performance (catalytic activity and durability against coking).

[0194] The silica / alumina (SiO2 / Al2O3) molar ratio of the zeolite contained in the zeolite-containing catalyst of this embodiment can be appropriately selected, but from the viewpoint of excellent catalytic activity and selectivity, it is preferably 20 to 2000, and from the viewpoint of improving the durability of the catalyst, it is more preferably 200 to 1500, even more preferably 300 to 1200, and still more preferably 800 to 1200. The silica / alumina (SiO2 / Al2O3) molar ratio of the zeolite contained in the zeolite-containing catalyst may be 20 to 1200 or 150 to 1000. The silica / alumina molar ratio of the zeolite can be measured by a known method, for example, by completely dissolving the zeolite in an alkaline aqueous solution and analyzing the resulting solution by plasma emission spectroscopy or the like.

[0195] The zeolite synthesis method of this embodiment is not particularly limited, but can be produced by optimizing various conditions of a conventionally known hydrothermal synthesis method for MFI zeolite. Generally, methods for efficiently obtaining MFI zeolite by hydrothermal synthesis include hydrothermal synthesis using an appropriate organic structure-directing agent (SDA), hydrothermal synthesis using hydrothermally synthesized MFI zeolite as seed crystals, or hydrothermal synthesis using seed slurry in the crystalline stage. Examples of the organic structure-directing agent (SDA) used here include ammonium salts, urea compounds, amines, and alcohols. It is known that not only organic SDAs 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 for MFI zeolite described above, a suitable catalyst can be obtained by appropriately optimizing synthesis conditions such as the type of raw materials and additives (SDA), the amount of additives, pH, silica / alumina molar ratio, raw material charge composition (e.g., medium, cation and anion abundance ratio), synthesis temperature, and synthesis time.

[0196] Specific examples include the synthesis method 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).

[0197] In addition, commercially available zeolites can also be used as long as they are MFI zeolites having the above-mentioned specific physical properties and composition.

[0198] The zeolite-containing catalyst in this embodiment preferably contains elemental phosphorus or elemental silver.

[0199] Examples of the form of elemental phosphorus include a phosphorus polymer (e.g., polyphosphoric acid), an oxide of phosphorus (e.g., PO), and a compound in which phosphorus is added to aluminum in a zeolite. A combination of these may also be included. When the zeolite contains aluminum, elemental phosphorus has the effect of suppressing dealumination of the zeolite and, in some cases, improving the propylene yield in the propylene production reaction. In the method according to this embodiment, water is generated in the reactor, and the raw material ethanol may also contain water, so the reactor is prone to a high-temperature steam atmosphere that causes dealumination. Dealuminization causes the structural collapse of the zeolite-containing catalyst, resulting in a deterioration in activity. However, the inclusion of elemental phosphorus in the zeolite-containing catalyst further improves the effect of suppressing dealumination of the zeolite.

[0200] The content of elemental phosphorus contained in the zeolite-containing catalyst is preferably 0.01 to 2.0 mass % relative to the mass of the entire catalyst, and from the viewpoint of achieving an excellent effect of suppressing dealumination, more preferably 0.05 to 2.0 mass %.

[0201] In this embodiment, the content of phosphorus in the catalyst is a value measured using an X-ray fluorescence analyzer. The content of phosphorus can be measured using a commercially available X-ray fluorescence analyzer under normal conditions in accordance with the instruction manual. For example, when using a Rigaku product under the trade name "RIX3000," the measurement conditions can be P-Kα radiation, a tube voltage of 50 kV, and a tube current of 50 mA.

[0202] In this embodiment, phosphoric acid and / or a phosphate (hereinafter also referred to as a "phosphorus raw material") is used as a raw material for the phosphorus element contained in the zeolite-containing catalyst. Phosphates are more preferred as the phosphorus raw material, and among phosphates, compounds showing a solubility of 1 g or more in 100 g of water at 25°C are more preferred.

[0203] Examples of phosphoric acid include phosphoric acid and pyrophosphoric acid, and examples of phosphates include ammonium phosphate salts such as ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and sodium ammonium hydrogen phosphate, as well as potassium hydrogen phosphate, aluminum hydrogen phosphate, sodium phosphate, and potassium phosphate. Among these, ammonium phosphate salts, which have relatively high solubility in water, are preferred, and at least one 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.

[0204] The silver element may be in the form of, for example, silver ions, which have the effect of improving the hydrothermal resistance of zeolite by controlling the acid sites of the zeolite.

[0205] The content of silver element contained in the zeolite-containing catalyst is preferably 0.01 to 2.0 mass% relative to the mass of the entire catalyst, and from the viewpoint of excellent effect of improving hydrothermal resistance per content, more preferably 0.05 to 2.0 mass%.

[0206] In this embodiment, the silver content in the catalyst is a value measured using an X-ray fluorescence analyzer. The silver content can be measured using a commercially available X-ray fluorescence analyzer under normal conditions in accordance with the instruction manual. For example, when using a Rigaku product under the trade name "RIX3000," the measurement conditions can be P-Kα radiation, a tube voltage of 50 kV, and a tube current of 50 mA.

[0207] In this embodiment, silver nitrate can be used as a source of elemental silver contained in the zeolite-containing catalyst. A zeolite-containing catalyst containing sodium as a counter cation is used, and ion-exchange with silver nitrate and sintered to obtain a zeolite-containing catalyst containing elemental silver. The ion exchange between sodium, the counter cation in the zeolite, and silver nitrate can be performed by immersing the zeolite or the zeolite-containing catalyst in an aqueous solution of silver nitrate, followed by washing with water. In this case, the ion exchange rate can be improved by performing the immersion and washing with water multiple times.

[0208] The zeolite-containing catalyst of this embodiment can be produced by molding a zeolite having the specific physical properties and composition described above, for example, as follows. The molding method is not particularly limited, and a common method can be used. Specific examples include a method of compression molding or extrusion molding of the catalyst components, and a spray-dry molding method that is optimal for a fluidized bed reaction system. 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 for these binders. The mass ratio of zeolite to binder is preferably in the range of 10 / 90 to 90 / 10, and more preferably in the range of 20 / 80 to 80 / 20. Among these, it is preferable to use a silica binder from the viewpoint of excellent coking resistance.

[0209] In the ethanol conversion method of this embodiment, a pretreatment step may be performed on the zeolite-containing catalyst prior to contacting the catalyst with the raw material. A preferred pretreatment step is a heat treatment at a temperature of 300°C or higher in the presence of steam. Pretreatment tends to more significantly suppress catalyst degradation and improve selectivity. In the above method, the treatment is preferably performed at a temperature of 300°C or higher and 900°C or lower, in a mixed gas of air or an inert gas such as nitrogen and steam (water vapor), although the atmosphere is not particularly limited, under conditions of a water vapor partial pressure of 0.01 atmosphere or higher. The heat treatment temperature is more preferably 400°C or higher and 700°C or lower. Furthermore, this pretreatment step can be performed using a reactor for converting ethanol and ethylene.

[0210] [Regeneration process] The ethanol conversion method of this embodiment may include a regeneration step (hereinafter also referred to as the "regeneration step") in which coke adhering to the catalyst is burned. When a catalyst is used in a reaction for a long period of time, coke may adhere to the catalyst, causing coking degradation. When the catalyst has been degraded by coking, the degraded catalyst can be regenerated by, for example, contacting the catalyst with an oxygen-containing gas at a temperature of 400 to 700°C to burn off the coke on the catalyst. Examples of the oxygen-containing gas include air and a mixture of air or oxygen and an inert gas. The oxygen concentration of the oxygen-containing gas is preferably 0.1 to 2.0% by volume. The catalyst may be regenerated using either an ex-reactor regeneration method in which the catalyst is withdrawn from the reactor and regenerated outside the reactor, or an in-reactor regeneration method in which the catalyst is regenerated within the reactor without being withdrawn from the reactor. Furthermore, a switching reactor may be used to perform a reaction-regeneration switching operation.

[0211] (Reaction-regeneration switching operation) Reaction-regeneration switching operation is an operation in which a reaction process and a regeneration process are carried out simultaneously using a two-tower or multi-tower switching adiabatic reactor. For example, in the case of a three-tower switching system, two towers are used for the reaction process, and the remaining tower is used for catalyst regeneration. Subsequently, the reaction process in one of the towers used for the reaction process is stopped to perform catalyst regeneration, and the reaction process is carried out in the tower used for catalyst regeneration. This allows catalyst regeneration to be carried out while maintaining the production capacity of the two towers. This type of reaction format is also called the merry-go-round system, and is preferred from the perspective of excellent production efficiency because it does not require stopping the production process for catalyst regeneration.

[0212] [Product: Reaction gas containing olefins with 3 or more carbon atoms] In the ethanol conversion method of this embodiment, a reaction gas containing olefins having 3 or more carbon atoms is obtained by contacting a mixed feedstock with a catalyst. The "reaction gas" refers to a gas composition resulting from the reaction of the mixed feedstock with the catalyst. The reaction gas may contain ethylene. The reaction gas may contain hydrogen, aliphatic hydrocarbons having 1 to 3 carbon atoms, aliphatic hydrocarbons having 4 to 6 carbon atoms, aromatic compounds, and hydrocarbons having 9 or more carbon atoms. In this specification, aliphatic hydrocarbons having 1 to 3 carbon atoms, aliphatic hydrocarbons having 4 to 6 carbon atoms, aromatic compounds, and hydrocarbons having 9 or more carbon atoms are referred to as target compounds.

[0213] <Separation process and recycling process> In the separation step according to this embodiment, the reaction gas obtained in the reaction step described above is separated into a fraction A containing mainly hydrocarbons having 2 to 3 carbon atoms and a fraction B containing mainly hydrocarbons having 4 to 6 carbon atoms using a first distillation column.

[0214] In the recycling step, at least a part of the fraction A is recycled to the reaction step as part of the mixed raw material.

[0215] Recycling refers to the process of subjecting all or part of the fraction obtained by subjecting the reaction gas to the separation process to the reaction process again as a raw material. The fraction recycled in this case is called the recycled fraction. By subjecting the recycled fraction to the reaction process, carbon components derived from ethanol, etc. can be efficiently converted into target compounds.

[0216] As shown in FIG. 7, the method according to this embodiment may be carried out using an apparatus including a fixed-bed, single-stage adiabatic reactor 1 (hereinafter simply referred to as "reactor 1") and a first distillation column 2. The reaction gas obtained by the reaction step performed in reactor 1 is separated in first distillation column 2 into fraction A, which mainly contains hydrocarbons having 1 to 3 carbon atoms, and fraction B, which mainly contains hydrocarbons having 4 to 6 carbon atoms. Ethylene is separated from fraction A in a distillation column (not shown), and propylene is further separated in a distillation column (not shown), thereby efficiently separating ethylene and propylene from the reaction gas. Furthermore, although not shown, at least a portion of the reaction gas and / or fraction A may be introduced into a purification system of an ethylene plant, and target compounds such as ethylene and propylene may be separated from the reaction gas in the purification system. At least a portion of fraction A is recycled to the reactor as a raw material. Fraction B may also be recycled to reactor 1 as a raw material.

[0217] As shown in Figure 8, the method according to this embodiment can be carried out using an apparatus including a reactor 1, a first distillation column 2, and a steam cracking apparatus 5. By subjecting fraction B obtained in the separation step to steam cracking, a steam cracking product containing ethylene and propylene is obtained, and the efficiency of the entire process can be improved by separating the ethylene and propylene from the steam cracking product. Steam cracking refers to the thermal decomposition of compounds in the fraction using heated steam.

[0218] As shown in FIG. 9, the method according to this embodiment can be carried out by an apparatus having a reactor 1, a cooling device 6, a first distillation column 2, and an oil-water separator 7. By providing a cooling step in which the reaction gas obtained in the reaction step carried out in the reactor 1 is cooled by the cooling device 6, the reaction gas can be separated 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. Fraction C is obtained as a gas component in the cooling step, and fraction D is recovered as a liquid component. The cooling device can be a direct heat exchanger in which the reaction gas and a coolant are brought into direct contact with each other to perform heat exchange, or an indirect (partition wall) heat exchanger in which the reaction gas and a coolant are circulated through a space separated by a wall to perform heat exchange through the wall. The fraction C recovered in the cooling step is separated in the first distillation column 2 into a fraction A containing mainly hydrocarbons having 1 to 3 carbon atoms and a fraction B containing mainly hydrocarbons having 4 to 6 carbon atoms. At least a portion of the fraction A may be recycled to the reactor 1 as part of the mixed feedstock. In addition, at least a portion of the fraction B may be recycled to the reactor 1 as part of the mixed feedstock. The fraction D recovered in the cooling step is separated in an oil-water separator 7 into a fraction E containing mainly hydrocarbons and a fraction F containing mainly water. The aromatic compounds are efficiently separated from the reaction gas by separating them from fraction E. Separation of the aromatic compounds is carried out by, for example, distillation, extractive distillation, extraction, crystallization, or a combination thereof.

[0219] As shown in FIG. 10, the method according to this embodiment can be carried out using an apparatus including a reactor 1, a cooling device 6, a first distillation column 2, and a second distillation column 8. By providing a cooling step in which the reaction gas obtained in the reaction step carried out in the reactor 1 is cooled using the cooling device 6, the reaction gas can be separated 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. Fraction C is obtained as a gas component in the cooling step, and fraction D is recovered as a liquid component. Separation of aromatic compounds from the reaction gas is efficiently achieved by separating aromatic compounds from fraction D recovered in the cooling step. Separation of aromatic compounds can be carried out, for example, by distillation, extractive distillation, extraction, crystallization, or a combination thereof. Fraction C obtained in the cooling step is separated in the first distillation column 2 into a fraction A mainly containing hydrocarbons having 1 to 3 carbon atoms and a fraction B mainly containing hydrocarbons having 4 to 6 carbon atoms. Furthermore, by supplying fraction A to second distillation column 8, fraction A is separated into fraction A-1 containing mainly hydrocarbons with a carbon number of 2 and fraction A-2 containing mainly hydrocarbons with a carbon number of 3. By using fraction A-1 as a recycled feedstock, the propylene concentration in the mixed feedstock is reduced, allowing propylene to be produced efficiently.

[0220] As shown in Figure 11, the distillation column of the method according to this embodiment may be provided with a side cut stage. By obtaining an intermediate draw fraction containing the target compound from the side cut stage, separation efficiency can be improved. By providing the distillation column with a side cut stage that draws fraction E, which mainly contains hydrocarbons with a carbon number of 3, from the intermediate portion of the first distillation column 2, the propylene recovery yield can be improved.

[0221] The term "mainly comprises" in various fractions means that the total mass of the components described as "mainly comprises" exceeds 50 mass% of each fraction. These separation steps can be carried out by combining various known methods such as distillation and extraction.

[0222] [Method of producing hydrocarbons, etc.] Various chemical products can be obtained by separating the target compounds from the reaction gas obtained by the first to third embodiments. That is, the method for producing hydrocarbons according to this embodiment includes contacting a mixed feedstock containing ethylene and ethanol with a catalyst in an adiabatic reactor to obtain a reaction gas containing olefins having a carbon number of 3 or more. Details of the production method are as described above in the ethanol conversion method, and preferred embodiments thereof are also the same.

[0223] Examples of hydrocarbons obtainable by this production method include aliphatic unsaturated hydrocarbons such as olefins such as propylene, ethylene, butene, pentene, hexene, and heptene, dienes such as 1,3-butadiene and isoprene, aromatic hydrocarbons such as benzene and toluene, and aliphatic saturated hydrocarbons such as ethane, propane, butane, and pentane. The aromatic hydrocarbons preferably have a boiling point of 500° C. or lower at normal pressure.

[0224] By introducing the obtained hydrocarbons into the refining system of the cracker, the target hydrocarbon compounds can be efficiently refined. The method for producing hydrocarbons according to this embodiment includes the steps of: a cracking step of decomposing hydrocarbons having two or more carbon atoms; a purification step of purifying the components obtained in the cracking step; and In the purification step, the reaction gas obtained by the above-mentioned method for converting ethanol or a purified fraction thereof is combined. With the above configuration, it is possible to obtain target hydrocarbons from ethanol resources using a conventional cracker. For example, by using bioethanol as a raw material in an ethanol conversion method, it is possible to produce bio-derived hydrocarbons.

[0225] Examples of hydrocarbons having two or more carbon atoms include ethylene, propylene, butene, paraffin, and aromatic hydrocarbons. Naphtha may also be used as the hydrocarbon having two or more carbon atoms.

[0226] As the cracker, a thermal cracking furnace used in an ethane cracker, naphtha cracker, etc. may be used.

[0227] In the purification step, a purification system used in a conventional ethane cracker or naphtha cracker may be used, and distillation may be carried out using equipment equipped with, for example, a distillation column, a quench column, etc.

[0228] The reaction gas or purified fraction thereof obtained by the above-mentioned method for converting ethanol is joined in the above-mentioned purification step, and the joining point is appropriately selected depending on the components to be joined.

[0229] The method for producing a monomer according to this embodiment includes the steps of: an unsaturated hydrocarbon separation step of separating a fraction mainly containing unsaturated hydrocarbons from the reaction gas obtained by the above-mentioned ethanol conversion method; Includes. 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.

[0230] The olefin production method according to this embodiment includes the steps of: an olefin separation step of separating a fraction mainly containing olefins from the reaction gas obtained by the above-mentioned ethanol conversion method; Includes.

[0231] The method for producing propylene according to this embodiment is as follows: a propylene separation step of separating a fraction mainly containing propylene from the reaction gas obtained by the above-mentioned ethanol conversion method; Includes.

[0232] The ethylene production method according to this embodiment includes the steps of: an ethylene separation step of separating a fraction mainly containing ethylene from the reaction gas obtained by the above-mentioned ethanol conversion method; Includes.

[0233] The method for producing a diene according to this embodiment includes the steps of: a diene separation step of separating a fraction mainly containing dienes from the reaction gas obtained by the above-mentioned ethanol conversion method; Includes.

[0234] The method for producing a monomer according to this embodiment may further include a step of converting the unsaturated hydrocarbon.

[0235] The method for producing an acrylic monomer according to this embodiment includes the steps of: an unsaturated hydrocarbon separation step of separating a fraction mainly containing unsaturated hydrocarbons from the reaction gas obtained by the above-mentioned ethanol conversion method; an acrylic monomer production step of obtaining an acrylic monomer from the unsaturated hydrocarbon obtained in the unsaturated hydrocarbon separation step; Includes. The acrylic monomer production process employs a known method of introducing an acrylic monomer from an unsaturated hydrocarbon.

[0236] The method for producing acrylonitrile according to this embodiment is as follows: a propylene separation step of separating a fraction mainly containing propylene from the reaction gas obtained by the above-mentioned ethanol conversion method; an acrylonitrile production step of obtaining acrylonitrile from the propylene obtained in the propylene separation step; Includes. The acrylic monomer production process employs a known method of introducing an acrylic monomer from an unsaturated hydrocarbon.

[0237] The method for producing styrene according to this embodiment is an ethylene separation step of separating a fraction mainly containing ethylene from the reaction gas obtained by the above-mentioned ethanol conversion method; a styrene production step of obtaining styrene from the ethylene obtained in the ethylene separation step; Includes.

[0238] The monomer obtained by the above-mentioned production method may be further polymerized. The method for producing a polymer according to this embodiment includes the steps of: a step of polymerizing the monomer obtained by the above-mentioned method for producing a monomer; Includes. The step of polymerizing the monomer can be carried out by a conventional polymerization method, and various initiators and polymerization catalysts can be used for the polymerization.

[0239] The method for producing an olefin polymer according to this embodiment includes the steps of: a step of polymerizing a polymerizable composition containing an olefin obtained by the above-mentioned method for producing an olefin; Includes. The polymerizable composition may contain only an olefin as a monomer, or may contain other monomers having unsaturated bonds.

[0240] The method for producing a polypropylene-based polymer according to this embodiment includes the steps of: a step of polymerizing a polymerizable composition containing propylene obtained by the above-mentioned method for producing propylene; Includes. The polymerizable composition may contain only propylene as a monomer, or may contain other monomers having unsaturated bonds.

[0241] The method for producing a polyethylene polymer according to this embodiment includes the steps of: a step of polymerizing a polymerizable composition containing ethylene obtained by the above-mentioned method for producing ethylene; Includes. The polymerizable composition may contain ethylene alone as a monomer, or may contain other monomers having unsaturated bonds.

[0242] The method for producing a diene polymer according to this embodiment includes the steps of: a step of polymerizing a polymerizable composition containing a diene obtained by the above-mentioned method for producing a diene; Includes. The polymerizable composition may contain only a diene as a monomer, or may contain other monomers having unsaturated bonds.

[0243] The method for producing an acrylic monomer-based polymer according to this embodiment includes the steps of: a step of polymerizing a polymerizable composition containing the acrylic monomer obtained by the above-mentioned method for producing an acrylic monomer; Includes. The polymerizable composition may contain only an acrylic monomer as the monomer, or may contain other monomers having unsaturated bonds.

[0244] The method for producing an acrylonitrile polymer according to this embodiment includes the steps of: a step of polymerizing a polymerizable composition containing acrylonitrile obtained by the above-mentioned method for producing acrylonitrile; Includes. The polymerizable composition may contain acrylonitrile alone as the monomer, or may contain other monomers having unsaturated bonds.

[0245] The method for producing a styrene-based polymer according to this embodiment includes the steps of: a step of polymerizing a polymerizable composition containing styrene obtained by the above-mentioned method for producing styrene; Includes. The polymerizable composition may contain styrene alone as a monomer, or may contain other monomers having unsaturated bonds.

[0246] Aromatic compounds may be separated from the reaction gas obtained by the above-mentioned ethanol conversion process. The method for producing an aromatic compound according to this embodiment includes the steps of: 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; Includes. Examples of aromatic hydrocarbons include benzene, toluene, and xylene. [Example]

[0247] The present invention will be described in more detail below by showing examples, but the present invention is not limited to the examples described below.

[0248] [Methods for measuring various physical properties] The methods for measuring various physical properties are as follows.

[0249] (1) The silica / alumina molar ratio of the zeolite in the zeolite-containing catalyst Zeolite was completely dissolved in sodium hydroxide solution to prepare a solution. The amounts of Si and Al contained in the solution were measured using an inductively coupled plasma (ICP) emission spectrometer (Rigaku, product name "JY138") according to standard methods, and the silica / alumina molar ratio was calculated from the results. The measurement conditions were: 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, Al measurement wavelength: 396.152 nm.

[0250] (2) Phosphorus and silver contents of zeolite-containing catalysts The contents of phosphorus and silver in the zeolite-containing catalyst were measured by a conventional method using an X-ray fluorescence analyzer (manufactured by Rigaku, trade name "RIX3000").

[0251] (3) Zeolite structural type The structural type of the zeolite in the zeolite-containing catalyst was identified by measuring the X-ray diffraction pattern of the zeolite using an X-ray analyzer (manufactured by Rigaku, product name "RINT") and referring to the diffraction patterns of known zeolites. The measurement conditions were as follows: Cu cathode Tube voltage: 40kV Bulb current: 30mA Scan speed: 1deg / min

[0252] [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), a medium pore size zeolite, and 30 parts by mass of silica (water content adjusted using colloidal silica and fumed silica) was kneaded and extruded to obtain extruded bodies with a diameter of 1.6 mm and a length of 4-6 mm. A predetermined amount of diammonium hydrogen phosphate aqueous solution was loaded onto the resulting body to obtain a phosphorus-loaded product. The resulting phosphorus-loaded product was calcined in an air atmosphere at 600°C for 5 hours using a calcination furnace. The calcined product was loaded into a reactor, and a steam-nitrogen mixed gas containing 80% by volume of steam was supplied and circulated for 24 hours under conditions of 0.1 MPa pressure and 600°C, yielding zeolite-containing catalyst 1. The phosphorus content of the zeolite-containing catalyst was measured and found to be 0.36% by mass.

[0253] (Preparation of Zeolite-Containing Catalyst 2) A clay obtained from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 980), a medium pore size zeolite, and 30 parts by mass of silica (water content adjusted using colloidal silica and fumed silica) was kneaded and then extrusion-molded to obtain an extruded molded body with a diameter of 2.1 mm and a length of 4 to 6 mm. The obtained molded body was calcined for 5 hours to obtain zeolite-containing catalyst 2.

[0254] (Preparation of Zeolite-Containing Catalyst 3) A clay obtained from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 980), a medium pore size zeolite, and 30 parts by mass of silica (water content adjusted using colloidal silica and fumed silica) was kneaded and extruded to obtain an extruded molded product with a diameter of 2.1 mm and a length of 4-6 mm. A predetermined amount of diammonium hydrogen phosphate aqueous solution was loaded onto the resulting molded product to obtain a phosphorus-loaded product. The resulting phosphorus-loaded product was calcined at 600°C for 5 hours in an air atmosphere. The calcined product was loaded into a reactor, and a steam-nitrogen mixed gas containing 80% by volume of steam was supplied and circulated for 24 hours under conditions of 0.1 MPa pressure and 600°C, to obtain zeolite-containing catalyst 3. The phosphorus content of the zeolite-containing catalyst was 0.032% by mass.

[0255] (Preparation of Zeolite-Containing Catalyst 4) A clay obtained from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 980), a medium pore size zeolite, and 30 parts by mass of silica (water content adjusted using colloidal silica and fumed silica) was kneaded and extruded to obtain an extruded molded body with a diameter of 2.1 mm and a length of 4–6 mm. The resulting molded body was calcined at 600°C for 5 hours to obtain a catalyst precursor. The resulting catalyst precursor was stirred in a 0.1 N aqueous sodium nitrate solution for 1 hour, filtered, washed, and calcined at 600°C for 5 hours to obtain a sodium-exchanged body. The sodium-exchanged body was stirred in a 0.01 N aqueous silver nitrate solution for 1 hour, filtered, and washed three times, and then calcined at 600°C for 5 hours to obtain a silver-exchanged body. A steam-air mixture containing 80% by volume of steam was supplied to and circulated through the silver-exchanged body at a pressure of 0.1 MPa and a temperature of 600°C for 24 hours to obtain zeolite-containing catalyst 2. At this time, the content of elemental silver contained in the zeolite-containing catalyst was 0.16% by mass.

[0256] (Preparation of Zeolite-Containing Catalyst 5) A clay obtained from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 302), a medium pore size zeolite, and 30 parts by mass of silica (water content adjusted using colloidal silica and fumed silica) was kneaded and then extrusion-molded to obtain an extruded molded body with a diameter of 1.6 mm and a length of 4 to 6 mm. The obtained molded body was calcined in an air atmosphere at 600°C for 5 hours to obtain zeolite-containing catalyst 5.

[0257] (Preparation of Zeolite-Containing Catalyst 6) A clay obtained from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 302), a medium pore size zeolite, and 30 parts by mass of silica (water content adjusted using colloidal silica and fumed silica) was kneaded and extruded to obtain extruded bodies with a diameter of 1.6 mm and lengths of 4 to 6 mm. A predetermined amount of aqueous diammonium hydrogen phosphate solution was loaded onto the resulting body to obtain a phosphorus-loaded product. The resulting phosphorus-loaded product was calcined at 600°C for 5 hours in an air atmosphere. The calcined product was loaded into a reactor, and a steam-nitrogen mixed gas containing 80% by volume of steam was supplied and circulated for 24 hours under conditions of 0.1 MPa pressure and 600°C, yielding Zeolite-Containing Catalyst 5. The phosphorus content of the zeolite-containing catalyst was 0.085% by mass.

[0258] [Example of the first embodiment] The present invention will be explained in more detail below by showing examples of the first embodiment, but the present invention is not limited to the examples described below.

[0259] [How to convert ethanol] (Reaction Apparatus) In the following examples and comparative examples, evaluations were carried out using a fixed-bed single-stage adiabatic reactor 1 shown in FIG.

[0260] (raw materials) The molar ratio of ethylene / ethanol and the molar ratio of olefin having 4 to 6 carbon atoms / ethylene in the examples and comparative examples were calculated according to the following formulas.

[0261] Ethylene / ethanol molar ratio (-) = ethylene molar flow rate (mol / hr) / ethanol molar flow rate (mol / hr)

[0262] Ethylene / C4-6 olefin molar ratio (-) = Ethylene molar flow rate (mol / hr) / C4-6 olefin flow rate (mol / hr)

[0263] (temperature measurement) The temperatures at the catalyst bed inlet and outlet were measured using thermocouples inserted from outside the reactor. Specifically, as shown in Figure 1, in a plane perpendicular to the fluid flow direction, the center of the reactor is defined as 0, and the distance from the center of the reactor to the inner wall surface of the reactor is defined as d. The temperature was measured at 0.5d to 0.6d. The effect of heat radiation due to the insertion of these thermocouples was negligibly small.

[0264] (Reaction evaluation) According to the following examples and comparative examples, reactions were carried out so that the average inlet and outlet reaction temperature was 540°C. A portion of the gas at the reactor outlet was sampled every 3 hours from the start of the reaction and introduced into a gas chromatograph (hereinafter simply referred to as "GC", 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. The average inlet and outlet reaction temperature was calculated according to the following formula and is represented as "reaction temperature" in the tables.

[0265] Average inlet / outlet reaction temperature (℃) = [catalyst bed inlet temperature (℃) + catalyst bed outlet temperature (℃)] / 2

[0266] (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. Then, air / nitrogen with an oxygen concentration of 2% by volume was passed through to burn off the coke on the catalyst. During this process, the gas at the reactor outlet was periodically sampled as regeneration gas, and the regeneration gas was analyzed using a gas chromatograph to measure the concentrations of CO and CO. From these values, the amount of carbon adhering to the catalyst was calculated, and this was taken as the coke amount. The method for analyzing the regeneration gas using a gas chromatograph is described below (Gas Chromatography Analysis Conditions). In the following examples and comparative examples, the coke yield was calculated according to the following formula:

[0267] Coke yield (mass ppm) = coke amount / [effective raw material supply mass flow rate (kg / hr) × reaction time (hr)]

[0268] Effective raw material supply mass flow rate (kg / hr) = ethylene flow rate (kg / hr) + ethylene-equivalent ethanol flow rate (kg / hr) + olefins flow rate with 4 to 6 carbon atoms (kg / hr) + oxygenated compounds with 1 to 6 carbon atoms other than ethanol flow rate (kg / hr)

[0269] Ethylene-equivalent ethanol flow rate (kg / hr) = ethanol flow rate (kg / hr) × ethylene molecular weight (g / mol) / ethanol molecular weight (g / mol)

[0270] (Gas chromatograph analysis conditions) [Regeneration gas analysis] Equipment: Shimadzu GC-8A Column: The following columns (1) and (2) connected in parallel are used. 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, Ltd.) Column (2) 80-100 mesh Porapac-Q (internal diameter 3 mm, length 2 m) manufactured by Waters Associates, USA, and a SUS resistance column (internal diameter 3 mm, length 1 m) directly connected Column temperature: 70℃ Carrier gas (helium) flow rate: 60 mL / min

[0271] [Reaction gas analysis] Equipment: Shimadzu GC-2030 Column: Custom capillary column SPB-1 (inner diameter 0.25 mm, length 60 m, film thickness 3.0 μm) manufactured by SUPELCO, USA Sample gas volume: 1 mL (sampling line is kept at 200°C to 300°C) Temperature program: maintain at 40°C for 12 minutes, then increase temperature to 200°C at 5°C / min, and maintain 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 were connected in series, and composition analysis was performed based on data detected by the TCD detector for hydrogen and data detected by the FID detector for oxygen-containing compounds such as hydrocarbons and ethanol. The calibration curve method was used to determine the concentration of the target compound in the reaction gas, and the mass per unit time produced by the reaction was calculated. The yield was calculated using the following formula.

[0272] Propylene yield (%) = mass of propylene produced by reaction per hour (kg / hr) / effective raw material supply mass flow rate (kg / hr)

[0273] Aromatic yield (%) = mass of aromatic compounds produced by reaction per hour (kg / hr) / effective raw material supply mass flow rate (kg / hr)

[0274] Effective raw material supply mass flow rate (kg / hr) = ethylene flow rate (kg / hr) + ethylene-equivalent ethanol flow rate (kg / hr) + olefins flow rate with 4 to 6 carbon atoms (kg / hr) + oxygenated compounds with 1 to 6 carbon atoms other than ethanol flow rate (kg / hr)

[0275] Ethylene-equivalent ethanol flow rate (kg / hr) = ethanol flow rate (kg / hr) × ethylene molecular weight (g / mol) / ethanol molecular weight (g / mol)

[0276] [Example 1] A mixed feed gas of ethylene, ethanol, and steam with an ethylene / ethanol molar ratio of 0.37 was heated and fed to a reactor packed with a zeolite-containing catalyst so that WHSV was 3.8, and the reaction was carried out. The inlet temperature of the catalyst bed was 539°C, the outlet temperature was 542°C, and the average inlet / outlet reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 23.2% by mass, and the average aromatics yield was 2.7% by mass. Furthermore, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 270 ppm by mass. The reaction results and details of the reaction conditions are shown in Table 1.

[0277] [Comparative Example 1] The reaction was carried out in the same manner as in Example 1, except that only ethanol feedstock gas, without ethylene or steam, was used and the catalyst bed inlet temperature was adjusted to 588°C. At this time, the catalyst bed outlet temperature was 492°C, and the average inlet and outlet reaction temperature was 540°C. From the start of the reaction to the end of the reaction, the average propylene yield was 19.3%, and the average aromatics yield was 1.5% by mass. In addition, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 507 ppm by mass. The reaction results, along with the reaction conditions, are shown in Table 1.

[0278] Comparative Example 2 The reaction was carried out in the same manner as in Example 1, except that no ethanol was added and only ethylene feed gas was used, and the catalyst bed inlet temperature was set to 450°C. However, the temperature at the catalyst bed outlet exceeded 650°C and continued to rise, so for safety reasons the reaction was stopped after 1 hour had elapsed. This comparative example demonstrates that it is difficult to efficiently carry out a reaction that generates a great deal of heat in an adiabatic reactor.

[0279] [Examples 2 to 6] The reactions were carried out in the same manner as in Example 1, except that zeolite-containing catalyst 2, zeolite-containing catalyst 3, zeolite-containing catalyst 4, zeolite-containing catalyst 5, and zeolite-containing catalyst 6 were used. The inlet / outlet temperature difference and reaction results for each catalyst are shown in Table 1.

[0280] [Table 1]

[0281] The results of Example 1 and Comparative Examples 1 and 2 reveal that by using a mixed feedstock with an ethylene / ethanol molar ratio within a specific range, it is possible to achieve both a high propylene yield and suppress coke deposition on the catalyst.

[0282] [Example 7] A mixed feed gas of ethylene (with an ethylene / ethanol molar ratio of 0.25 and a C4-6 olefin / ethylene molar ratio of 0.7), ethanol, hydrocarbons with 4 or more carbon atoms, mainly containing hydrocarbons with 4 to 8 carbon atoms, and steam, with the composition shown in Table 2, was heated and fed to a reactor packed with a zeolite-containing catalyst so that the WHSV was 4.9, and the reaction was carried out. The inlet temperature of the catalyst bed was 568°C, the outlet temperature was 512°C, and the average inlet / outlet reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 22.5 mass%, and the average aromatics yield was 3.0 mass%. Furthermore, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 315 mass ppm. The reaction results and details of the reaction conditions are shown in Table 3.

[0283] [Example 8] The reaction was carried out in the same manner as in Example 7, except that a mixed feed gas having an ethylene / ethanol molar ratio of 0.82 and a C4-6 olefin / ethylene molar ratio of 0.3 was used, and the inlet temperature of the catalyst bed was adjusted to 539°C. At this time, the outlet temperature of the catalyst bed was 541°C, and the average inlet / outlet reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 23.7 mass%, and the average aromatics yield was 2.6 mass%. In addition, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 273 mass ppm. The reaction results are shown in Table 3, along with the reaction conditions.

[0284] [Example 9] The reaction was carried out in the same manner as in Example 7, except that a mixed feed gas having an ethylene / ethanol molar ratio of 1.5 and a C4-6 olefin / ethylene molar ratio of 0.2 was used, and the inlet temperature of the catalyst bed was adjusted to 522°C. At this time, the outlet temperature of the catalyst bed was 558°C, and the average inlet / outlet reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 23.2 mass%, and the average aromatics yield was 2.8 mass%. In addition, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 277 mass ppm. The reaction results are shown in Table 3, along with the reaction conditions.

[0285] [Example 10] The reaction was carried out in the same manner as in Example 7, except that a mixed feed gas having an ethylene / ethanol molar ratio of 2.3 and a C4-6 olefin / ethylene molar ratio of 0.2 was used, and the inlet temperature of the catalyst bed was adjusted to 511°C. At this time, the outlet temperature of the catalyst bed was 569°C, and the average inlet / outlet reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 22.7 mass%, and the average aromatics yield was 2.4 mass%. In addition, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 318 mass ppm. The reaction results, along with the reaction conditions, are shown in Table 3.

[0286] [Example 11] The reaction was carried out in the same manner as in Example 7, except that a mixed feed gas having an ethylene / ethanol molar ratio of 0.25 and a C4-6 olefin / ethylene molar ratio of 2.00 was used, and the inlet temperature of the catalyst bed was adjusted to 572°C. The outlet temperature of the catalyst bed was 508°C, and the average inlet / outlet reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 20.4% by mass, and the average aromatics yield was 3.9% by mass. Furthermore, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 320 ppm by mass. The reaction results, along with the reaction conditions, are shown in Table 3.

[0287] Comparative Example 3 The reaction was carried out in the same manner as in Example 7, except that ethylene was not used, and ethanol and an olefin having 4 to 6 carbon atoms were used as the feed gas, and the inlet temperature of the catalyst bed was adjusted to 590°C. At this time, the outlet temperature of the catalyst bed was 490°C, and the average inlet and outlet reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 17.6 mass%, and the average aromatics yield was 1.4 mass%. In addition, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 507 mass ppm. The reaction results are shown in Table 3 together with the reaction conditions.

[0288] Comparative Example 4 The reaction was carried out in the same manner as in Example 7, except that ethanol was not used, a mixed feed gas having a C4-6 olefin / ethylene molar ratio of 0.1 was used, and the catalyst bed inlet temperature was adjusted to 477°C. At this time, the catalyst bed outlet temperature was 603°C, and the average inlet / outlet reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 16.5 mass%, and the average aromatics yield was 1.2 mass%. In addition, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 565 mass ppm. The reaction results are shown in Table 3 together with the reaction conditions.

[0289] [Table 2]

[0290] [Table 3]

[0291] [Example of the second embodiment] The present invention will be explained in more detail below by showing examples of the second embodiment, but the present invention is not limited to the examples described below.

[0292] [How to convert ethanol] (Reaction Apparatus) In the following examples and comparative examples, evaluations were carried out using a fixed-bed single-stage adiabatic reactor 1 shown in FIG.

[0293] (raw materials) The molar ratio of methanol / ethanol, the molar ratio of olefin having 4 to 6 carbon atoms / methanol, and the molar ratio of ethylene / ethanol in the 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) Methanol / C4-C6 olefin molar ratio (-) = Methanol molar flow rate (mol / hr) / C4-C6 olefin flow rate (mol / hr) Ethylene / ethanol molar ratio (-) = ethylene molar flow rate (mol / hr) / ethanol molar flow rate (mol / hr)

[0294] (temperature measurement) The temperatures at the catalyst bed inlet and outlet were measured using thermocouples inserted from outside the reactor. Specifically, as shown in Figure 1, in a plane perpendicular to the fluid flow direction, the center of the reactor is defined as 0, and the distance from the center of the reactor to the inner wall surface of the reactor is defined as d. The temperature was measured at 0.5d to 0.6d. The effect of heat radiation due to the insertion of these thermocouples was negligibly small.

[0295] (Reaction evaluation) According to the following examples and comparative examples, reactions were carried out so that the average inlet and outlet reaction temperature was 540°C. A portion of the gas at the reactor outlet 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. The average inlet and outlet reaction temperature was calculated according to the following formula and is represented as "reaction temperature" in the tables. Average inlet / outlet reaction temperature (℃) = [catalyst bed inlet temperature (℃) + catalyst bed outlet temperature (℃)] / 2

[0296] (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. Then, air / nitrogen with an oxygen concentration of 2% by volume was passed through to burn off the coke on the catalyst. During this process, the reactor outlet gas was periodically sampled, and the regeneration gas was analyzed using a gas chromatograph to measure the concentrations of CO and CO. From these values, the amount of carbon adhering to the catalyst was calculated, and this was taken as the coke amount. The method for analyzing the regeneration gas using a gas chromatograph is described below (Gas Chromatography Analysis Conditions). In the following examples and comparative examples, the coke yield was calculated according to the following formula: Coke yield (mass ppm) = coke amount / [effective raw material supply mass flow rate (kg / hr) × 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 + carbon number 4-6 olefin flow rate (kg / hr) + flow rate of oxygenated compounds with carbon numbers 1-6 other than methanol and ethanol (kg / hr) Ethylene-equivalent ethanol flow rate (kg / hr) = ethanol flow rate (kg / hr) x 0.609 Methylene-equivalent methanol flow rate (kg / hr) = methanol flow rate (kg / hr) x 0.438

[0297] (Gas chromatograph analysis conditions) <Regeneration gas analysis> Equipment: Shimadzu GC-8A Column: The following columns (1) and (2) connected in parallel are used. 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, Ltd.) Column (2) 80-100 mesh Porapac-Q (internal diameter 3 mm, length 2 m) manufactured by Waters Associates, USA, and a SUS resistance column (internal diameter 3 mm, length 1 m) directly connected Column temperature: 70℃ Carrier gas (helium) flow rate: 60 mL / min

[0298] <Reaction gas analysis> Equipment: Shimadzu GC-2030 Column: Custom capillary column SPB-1 (inner diameter 0.25 mm, length 60 m, film thickness 3.0 μm) manufactured by SUPELCO, USA Sample gas volume: 1 mL (sampling line is kept at 200°C to 300°C) Temperature program: maintain at 40°C for 12 minutes, then increase temperature to 200°C at 5°C / min, and maintain 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 were connected in series, and composition analysis was performed based on data detected by the TCD detector for hydrogen and data detected by the FID detector for oxygenated substances such as hydrocarbons and ethanol. The calibration curve method was used to determine the propylene concentration, benzene concentration, toluene concentration, and aromatic hydrocarbon concentration with a carbon number of 8 in the reaction gas, and the mass of propylene and aromatic hydrocarbons per hour produced by the reaction were calculated. The mass of aromatics per hour produced by the reaction is the total mass of benzene, toluene, and aromatic hydrocarbons with a carbon number of 8 produced by the reaction per hour. The propylene yield and aromatics yield were calculated by the following formulas. 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%) = mass of aromatic produced by reaction per hour (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) + carbon number 4-6 olefin flow rate (kg / hr) + carbon number 1-6 oxygenated compound flow rate other than methanol and ethanol (kg / hr) Ethylene-equivalent ethanol flow rate (kg / hr) = ethanol flow rate (kg / hr) x 0.609 Methylene-equivalent methanol flow rate (kg / hr) = methanol flow rate (kg / hr) x 0.438

[0299] [Example B1] A mixed feed gas of methanol and ethanol with a methanol / ethanol molar ratio of 0.22 was heated and supplied to a reactor packed with zeolite-containing catalyst 1 so that WHSV was 3.8, and the reaction was carried out. The inlet temperature of the catalyst bed was 563°C, the outlet temperature was 518°C, and the average inlet / outlet reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 19.5 mass%, and the average aromatics yield was 7.8 mass%. Furthermore, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 277 mass ppm. The reaction results and details of the reaction conditions are shown in Table 4.

[0300] [Example B2] A mixed feed gas of methanol and ethanol with a methanol / ethanol molar ratio of 0.50 was heated and fed to a reactor packed with a zeolite-containing catalyst so that WHSV was 3.8, and the reaction was carried out. The inlet temperature of the catalyst bed was 536°C, the outlet temperature was 544°C, and the average inlet / outlet reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 20.1 mass%, and the average aromatics yield was 7.5 mass%. Furthermore, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 270 mass ppm. The reaction results and details of the reaction conditions are shown in Table 4.

[0301] [Example B3] A mixed feed gas of methanol and ethanol with a methanol / ethanol molar ratio of 0.86 was heated and fed to a reactor packed with a zeolite-containing catalyst so that WHSV was 3.8, and the reaction was carried out. The inlet temperature of the catalyst bed was 511°C, the outlet temperature was 569°C, and the average inlet / outlet reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 19.3 mass%, and the average aromatics yield was 8.8 mass%. Furthermore, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 357 mass ppm. The reaction results and details of the reaction conditions are shown in Table 4.

[0302] [Comparative Example B1] The reaction was carried out in the same manner as in Example B1, except that no methanol was added and only ethanol feed gas was used, and the catalyst bed inlet temperature was adjusted to 588°C. The catalyst bed outlet temperature was 492°C, and the average inlet / outlet 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 average aromatics yield was 1.2% by mass. Furthermore, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 483 ppm by mass. The reaction results, along with the reaction conditions, are shown in Table 4.

[0303] [Comparative example B2] A reaction was carried out in the same manner as in Example B1, except that no ethanol was used and only methanol was used as the feed gas, and the catalyst bed inlet temperature was set to 450°C. However, the temperature at the catalyst bed outlet exceeded 650°C and continued to rise, so for safety reasons, the reaction was stopped after 1 hour. This comparative example demonstrates that it is difficult to efficiently carry out a highly exothermic reaction in an adiabatic reactor.

[0304] [Table 4]

[0305] The results of Examples B1 to B3 and Comparative Examples B1 and B2 show that using a mixed feedstock with a specific range of methanol / ethanol molar ratio makes it possible to achieve both high propylene yield and aromatics yield while suppressing coke deposition on the catalyst.

[0306] [Example B4] A mixed feed gas of methanol, ethanol, and hydrocarbons with 4 or more carbon atoms, mainly containing hydrocarbons with 4 to 8 carbon atoms and having a methanol / ethanol molar ratio of 0.35 and a C4-6 olefin / methanol molar ratio of 0.97, with the composition shown in Table 5, was heated and supplied to a reactor packed with a zeolite-containing catalyst so that the WHSV was 4.9, and the reaction was carried out. The inlet temperature of the catalyst bed was 566°C, the outlet temperature was 514°C, and the average inlet / outlet reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 18.9 mass%, and the aromatics yield was 8.3 mass%. The coke yield of the zeolite-containing catalyst after 48 hours of operation was 315 mass ppm. Table 6 shows the reaction results and details of the reaction conditions. In this example, the aromatics yield was calculated from the difference between the aromatics concentration in the feed and the aromatics concentration in the reaction gas.

[0307] [Example B5] A reaction was carried out in the same manner as in Example B4, except that a mixed feed gas having a methanol / ethanol molar ratio of 0.50 and a C4-6 olefin / methanol molar ratio of 0.49 was used, and the inlet temperature of the catalyst bed was adjusted to 558°C. At this time, the outlet temperature of the catalyst bed was 522°C, and the average inlet / outlet reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 19.5 mass%, and the aromatics yield was 7.8 mass%. In addition, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 297 mass ppm. The reaction results are shown in Table 6, along with the reaction conditions.

[0308] [Example B6] A reaction was carried out in the same manner as in Example B4, except that a mixed feed gas having a methanol / ethanol molar ratio of 0.86 and a C4-6 olefin / methanol molar ratio of 0.32 was used, and the inlet temperature of the catalyst bed was adjusted to 541°C. At this time, the outlet temperature of the catalyst bed was 539°C, and the average inlet / outlet reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 19.9 mass%, and the aromatics yield was 7.6 mass%. In addition, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 270 mass ppm. The reaction results are shown in Table 6, along with the reaction conditions.

[0309] [Example B7] A reaction was carried out in the same manner as in Example B4, except that a mixed feed gas having a methanol / ethanol molar ratio of 1.33 and a C4-6 olefin / methanol molar ratio of 0.24 was used, and the inlet temperature of the catalyst bed was adjusted to 526°C. At this time, the outlet temperature of the catalyst bed was 554°C, and the average inlet / outlet reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 19.5 mass%, and the aromatics yield was 7.6 mass%. In addition, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 266 mass ppm. The reaction results are shown in Table 6, along with the reaction conditions.

[0310] [Comparative Example B3] The reaction was carried out in the same manner as in Example B2, except that ethanol was not used, and methanol and an olefin having 4 to 6 carbon atoms were used as the feed gas, 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 inlet and outlet 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 aromatics yield was 11.3% by mass. In addition, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 684 ppm by mass. The reaction results are shown in Table 6 together with the reaction conditions.

[0311] [Table 5]

[0312] [Table 6]

[0313] [Example B8] A reaction was carried out in the same manner as in Example B4, except that a mixed feed gas having a methanol / ethanol molar ratio of 0.40, a C4-6 olefin / methanol molar ratio of 0.24, and an ethylene / ethanol molar ratio of 0.13 was used, and the inlet temperature of the catalyst bed was adjusted to 555°C. The outlet temperature of the catalyst bed was 525°C, and the average inlet / outlet 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 aromatics yield was 7.4% by mass. Furthermore, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 251 ppm by mass. The reaction results, along with the reaction conditions, are shown in Table 7.

[0314] [Example B9] A reaction was carried out in the same manner as in Example B4, except that a mixed feed gas having a methanol / ethanol molar ratio of 0.46, a C4-6 olefin / methanol molar ratio of 0.20, and an ethylene / ethanol molar ratio of 0.31 was used, and the inlet temperature of the catalyst bed was adjusted to 544°C. The outlet temperature of the catalyst bed was 536°C, and the average inlet / outlet reaction temperature 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 aromatics yield was 7.7% by mass. Furthermore, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 280 ppm by mass. The reaction results, along with the reaction conditions, are shown in Table 7.

[0315] [Example B10] A reaction was carried out in the same manner as in Example B1, except that a mixed feed gas having 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. The outlet temperature of the catalyst bed was 534°C, and the average inlet / outlet reaction temperature 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 average aromatics yield was 7.7% by mass. Furthermore, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 291 ppm by mass. The reaction results, along with the reaction conditions, are shown in Table 7.

[0316] [Table 7]

[0317] [Example of the third embodiment] The present invention will be explained in more detail below by showing examples of the third embodiment, but the present invention is not limited to the examples described below.

[0318] [How to convert ethanol] (Reaction Apparatus) In the following examples and comparative examples, evaluations are carried out using a fixed-bed single-stage adiabatic reactor 1 shown in FIG.

[0319] (raw materials) The molar ratio of ethylene / ethanol and the molar ratio of olefin having 4 to 6 carbon atoms / ethylene in the examples and comparative examples are calculated by the following formulas. Ethylene / ethanol molar ratio (-) = ethylene molar flow rate (mol / hr) / ethanol molar flow rate (mol / hr) Molar ratio of olefins with 4 to 6 carbon atoms / ethylene (-) = flow rate of olefins with 4 to 6 carbon atoms (mol / hr) / mol flow rate of ethylene (mol / hr)

[0320] (temperature measurement) The temperatures at the catalyst bed inlet and outlet are measured using thermocouples inserted from outside the reactor. Specifically, as shown in Figure 1, in a plane perpendicular to the fluid flow direction, the center of the reactor is set to 0, and the distance from the center of the reactor to the inner wall surface of the reactor is set to d, and the temperature is measured at 0.5d to 0.6d. Note that the effect of heat radiation due to the insertion of these thermocouples is negligible.

[0321] (Reaction evaluation) According to the following examples and comparative examples, the reaction is carried out so that the average inlet and outlet reaction temperature is 540°C. A portion of the gas at the reactor outlet is 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 is 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 is calculated. The average inlet and outlet reaction temperature is calculated according to the following formula and is referred to as "reaction temperature" in the tables. Average inlet / outlet reaction temperature (℃) = [catalyst bed inlet temperature (℃) + catalyst bed outlet temperature (℃)] / 2

[0322] (Coke yield) In the following examples and comparative examples, after the reaction has stopped, nitrogen is supplied to the reactor to purge the hydrocarbons, and the catalyst bed is maintained at 500°C. Then, air / nitrogen with an oxygen concentration of 2% by volume is passed through to burn off the coke on the catalyst. During this process, the reactor outlet gas is periodically sampled, and the regeneration gas is analyzed using a gas chromatograph to measure the CO2 and CO concentrations. From these values, the amount of carbon adhering to the catalyst is calculated, and this is taken as the coke amount. The method for analyzing the regeneration gas using a gas chromatograph is described below (Gas Chromatography Analysis Conditions). Hereinafter, the coke yield in the examples and comparative examples is calculated according to the following formula:

[0323] Coke yield (mass ppm) = coke amount / [effective raw material supply mass flow rate (kg / hr) × reaction time (hr)]

[0324] Effective raw material supply mass flow rate (kg / hr) = ethylene flow rate (kg / hr) + ethylene-equivalent ethanol flow rate (kg / hr) + olefins flow rate with 4 to 6 carbon atoms (kg / hr) + oxygenated compounds with 1 to 6 carbon atoms other than ethanol flow rate (kg / hr)

[0325] Ethylene-equivalent ethanol flow rate (kg / hr) = ethanol flow rate (kg / hr) × ethylene molecular weight (g / mol) / ethanol molecular weight (g / mol)

[0326] [Gas chromatograph analysis conditions] (Regeneration gas analysis) Equipment: Shimadzu GC-8A Column: The following columns (1) and (2) connected in parallel are used. Column (1): A stainless steel column (inner diameter 3 mm, length 3 m) packed with 80-100 mesh molecular sieve 5A (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). Column (2) 80-100 mesh Porapac-Q (internal diameter 3 mm, length 2 m) manufactured by Waters Associates, USA, and a SUS resistance column (internal diameter 3 mm, length 1 m) directly connected Column temperature: 70℃ Carrier gas (helium) flow rate: 60 mL / min

[0327] (Reaction gas analysis) Equipment: Shimadzu GC-2030 Column: Custom capillary column SPB-1 (inner diameter 0.25 mm, length 60 m, film thickness 3.0 μm) manufactured by SUPELCO, USA Sample gas volume: 1 mL (sampling line is kept at 200°C to 300°C) Temperature program: maintain at 40°C for 12 minutes, then increase temperature to 200°C at 5°C / min, and maintain 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 data detected by the TCD detector for hydrogen and data detected by the FID detector for oxygen-containing substances such as hydrocarbons and ethanol. The calibration curve method is used to determine the concentration of the target compound in the reaction gas, and the mass per unit time produced by the reaction is calculated.

[0328] (Propylene yield) The propylene yield represents the selectivity to propylene in the reaction and is calculated by 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)

[0329] Effective raw material supply mass flow rate (kg / hr) = ethylene flow rate (kg / hr) + ethylene-equivalent ethanol flow rate (kg / hr) + olefins flow rate with 4 to 6 carbon atoms (kg / hr) + oxygenated compounds with 1 to 6 carbon atoms other than ethanol flow rate (kg / hr)

[0330] Ethylene-equivalent ethanol flow rate (kg / hr) = ethanol flow rate (kg / hr) × ethylene molecular weight (g / mol) / ethanol molecular weight (g / mol)

[0331] (recovery yield) The recovery yield of propylene and aromatic compounds is calculated using the following formula. The recovery yield of each component represents the amount of each component discharged relative to the raw material introduced into the reactor. The discharged amount is the mass of each component discharged per unit time outside the system after the separation process. Propylene recovery yield (mass%) = Propylene discharge (kg / hr) / Mixed raw material supply mass flow rate (kg / hr) Aromatic compound recovery yield (mass%) = Aromatic compound discharge amount (kg / hr) / Mixed feedstock supply mass flow rate (kg / hr)

[0332] [Reference example 1] A mixed feed gas (ethylene 1.0 kg / hr, ethanol 4.6 kg / hr, steam 0.7 kg / hr) with an ethylene / ethanol molar ratio of 0.37 was heated and supplied to a reactor packed with zeolite-containing catalyst 1 so that WHSV was 3.8, and the reaction was carried out. The inlet temperature of the catalyst bed was 539°C, the outlet temperature was 542°C, the average inlet / outlet reaction temperature was 540°C, and the average propylene yield from the start of the reaction to the end of the reaction was 23.2 mass%, and the average aromatics yield was 2.7 mass%. Furthermore, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 270 mass ppm. From this Reference Example, it was found that by controlling the molar ratio of ethylene to ethanol, ethylene and ethanol can be converted into the target compound while controlling the reaction temperature.

[0333] [Reference example 2] A mixed feed gas (ethylene 1.7 kg / hr, ethanol 3.4 kg / hr, C4-C6 olefins 1.1 kg / hr, and steam 1.1 kg / hr) with an ethylene / ethanol molar ratio of 0.82 and an ethylene / C4-C6 olefin molar ratio of 0.3 was heated and supplied to a reactor packed with zeolite-containing catalyst 1 so that WHSV was 4.9, and the reaction was carried out. The inlet temperature of the catalyst bed was 539°C, the outlet temperature was 541°C, and the average inlet / outlet reaction temperature was 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 22.5 mass%, and the average aromatics yield was 13.1 mass%. Furthermore, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 273 mass ppm.

[0334] [Example C1] The effectiveness of the ethanol conversion method according to this embodiment is verified using the apparatus shown in FIG. 9. A raw material is supplied to a reactor 1 packed with a zeolite-containing catalyst 1 to obtain a reaction gas. The resulting reaction gas is passed through a cooling device 6 to separate fraction C, which contains primarily hydrocarbons with a carbon number of 6 or less, and fraction D, which contains primarily water and hydrocarbons with a carbon number of 7 or more. Fraction C is passed through a first distillation column 2 to separate fraction A, which contains primarily hydrocarbons with a carbon number of 3 or less, and fraction B, which contains primarily hydrocarbons with a carbon number of 4 or more. These fractions are used as raw materials so that the recycle ratio of fraction A is 0.60 and the recycle ratio of fraction B is 0.90. Based on the results of Reference Examples 1 and 2 described above, the propylene yield and other data for the steady-state operation of the above process are shown in Table 8. The feedstock introduced into reactor 1 has an ethylene / ethanol molar ratio of 0.40 and a C4-C6 olefin / ethylene molar ratio of 0.43. The composition of components (mainly hydrocarbons with a carbon number of 4 or more) recycled from fraction B contained in the feedstock is shown in Table 9. The feedstock feed rate to the reactor is WHSV = 3.8, the catalyst bed inlet temperature is 553°C, the outlet temperature is 527°C, and the average inlet / outlet reaction temperature is 540°C. The average propylene yield from the start of the reaction to the end of the reaction is 22.1 mass%, and the coke yield of the zeolite-containing catalyst after 48 hours of operation is 251 mass ppm. The propylene recovery yield obtained at the outlet of the separation step is 5.4 mass%, and the aromatic compound recovery yield is 12.3 mass%.

[0335] [Example C2] The effectiveness of the ethanol conversion method according to this embodiment is verified using the apparatus shown in FIG. 10. A raw material is supplied to a reactor 1 packed with a zeolite-containing catalyst 1 to obtain a reaction gas. The resulting reaction gas is passed through a cooling device 6 to separate fraction C, which contains primarily hydrocarbons with a carbon number of 6 or less, and fraction D, which contains primarily water and hydrocarbons with a carbon number of 7 or more. Fraction C is passed through a first distillation column 2 to separate fraction A, which contains primarily hydrocarbons with a carbon number of 3 or less, and fraction B, which contains primarily hydrocarbons with a carbon number of 4 or more. The resulting fraction A is passed through a second distillation column 8 to separate fraction A-1, which contains primarily hydrocarbons with a carbon number of 2 or less, and fraction A-2, which contains primarily hydrocarbons with a carbon number of 3. These fractions are used as raw materials so that the recycle ratio of fraction A-1 is 0.72, and the recycle ratio of fraction B is 0.90. Based on the results of Reference Examples 1 and 2 described above, the propylene yield and other data for the steady-state operation of the above process are shown in Table 8. The raw material introduced into reactor 1 has an ethylene / ethanol molar ratio of 0.40 and a C4-C6 olefin / ethylene molar ratio of 0.36. The composition of components (mainly hydrocarbons with a carbon number of 4 or more) recycled from fraction B contained in the raw material is shown in Table 9. The feed rate of the raw material to reactor 1 is WHSV = 3.8, the inlet temperature of the catalyst bed is 547 °C, the outlet temperature is 533 °C, and the average inlet / outlet reaction temperature is 540 °C. The average propylene yield from the start of the reaction to the end of the reaction is 23.5 mass%, and the coke yield of the zeolite-containing catalyst after 48 hours of operation is 235 mass ppm. The propylene recovery yield obtained at the outlet of the separation step is 15.5 mass%, and the aromatic compound recovery yield is 14.0 mass%. A comparison between Example C1 and Example C2 shows that the propylene recovery yield is improved by providing a distillation column for separating fraction A-1, which mainly contains hydrocarbons having a carbon number of 2 or less, from fraction A-2, which mainly contains hydrocarbons having a carbon number of 3.

[0336] [Example C3] The effect of the conversion method according to this embodiment is verified using the apparatus shown in FIG. 11. The raw material is supplied to a reactor 1 packed with a zeolite-containing catalyst 1 to obtain a reaction gas. The obtained reaction gas is passed through a cooling device 6 to separate fraction C, which mainly contains hydrocarbons with a carbon number of 6 or less, and fraction D, which mainly contains water and hydrocarbons with a carbon number of 7 or more. Fraction C is passed through a first distillation column 2 to separate fraction A, which mainly contains hydrocarbons with a carbon number of less than 3, fraction B, which mainly contains hydrocarbons with a carbon number of 4 or more, and fraction E, which mainly contains hydrocarbons with a carbon number of 3. These fractions are used as raw materials so that the recycle ratio of fraction A is 0.78 and the recycle ratio of fraction B is 0.90. Based on the results of Reference Examples 1 and 2 described above, the propylene yield and other data for the above process during steady-state operation are shown in Table 8. The raw material introduced into reactor 1 has an ethylene / ethanol molar ratio of 0.40 and a C4-C6 olefin / ethylene molar ratio of 0.39. The composition of the components (mainly hydrocarbons with 4 or more carbon atoms) recycled from fraction B contained in the raw material is shown in Table 9. The feed rate of the raw material to reactor 1 is WHSV = 3.8, the inlet temperature of the catalyst bed is 549 °C, the outlet temperature is 531 °C, and the average inlet / outlet reaction temperature is 540 °C. The average propylene yield from the start of the reaction to the end of the reaction is 23.8 mass%, and the coke yield of the zeolite-containing catalyst after 48 hours of operation is 240 mass ppm. The propylene recovery yield obtained at the outlet of the separation step is 12.1 mass%, and the aromatic compound recovery yield is 12.0 mass%. A comparison between Example C1 and Example C3 shows that the propylene recovery yield can be improved by providing a side cut stage in the distillation column 2, which extracts fraction E, which mainly contains hydrocarbons with a carbon number of 3, from the middle of the first distillation column 2.

[0337] [Comparative Example C1] The effect of the conversion method was verified using an apparatus having a reactor 1 and a cooling device 6, as shown in Figure 12. The raw material is supplied to the reactor 1, which is filled with a zeolite-containing catalyst 1, to obtain a reaction gas. The obtained reaction gas is passed through the cooling device 6 to separate it into a fraction C, which mainly contains hydrocarbons with a carbon number of 6 or less, and a fraction D, which mainly contains water and hydrocarbons with a carbon number of 7 or more. These fractions are used as raw materials so that the recycle ratio of fraction C is 0.67. Table 8 shows the propylene yield and other data for the above process when operated at a steady state. The raw material introduced into reactor 1 has an ethylene / ethanol molar ratio of 0.40 and a C4-6 olefin / ethylene molar ratio of 0.29. The feed rate of the raw material to reactor 1 is WHSV = 3.8, the inlet temperature of the catalyst bed is 534°C, the outlet temperature is 546°C, and the average inlet / outlet reaction temperature is 540°C. The average propylene yield from the start of the reaction to the end of the reaction is 23.0 mass%, and the coke yield of the zeolite-containing catalyst after 48 hours of operation is 255 mass ppm. The recovery yield of propylene obtained at the outlet of the separation step is 4.4 mass%, and the recovery yield of aromatic compounds is 12.1 mass%. Comparison between Example C1 and Comparative Example C1 reveals that the recovery yield of propylene can be improved by providing a distillation step when recycling the reaction gas.

[0338] [Comparative Example C2] The effect of the conversion method was verified using an apparatus having a reactor 1 shown in Figure 13. The raw material was supplied to the reactor 1 filled with a zeolite-containing catalyst 1 to obtain a reaction gas. By mixing with ethanol so that the reaction gas recycle ratio was 0.65, a mixed raw material with the same composition as the raw material was obtained. The raw material introduced into reactor 1 has an ethylene / ethanol molar ratio of 0.40 and a C4-6 olefin / ethylene molar ratio of 0.15. The feed rate of the raw material to reactor 1 is WHSV = 3.8. The inlet temperature of the catalyst bed is 537°C, the outlet temperature is 543°C, and the average inlet / outlet reaction temperature is 540°C. The average propylene yield from the start of the reaction to the end of the reaction is 23.6 mass%. The coke yield of the zeolite-containing catalyst after 48 hours of operation is 310 mass ppm. The recovery yield of propylene obtained at the outlet of the separation step is 2.8 mass%, and the recovery yield of aromatic compounds is 7.4 mass%. Comparison of Example C1, Comparative Example C1 and Comparative Example C2 reveals that the recovery yield of propylene is improved by providing a distillation step and a cooling step when recycling the reaction gas.

[0339] [Table 8]

[0340] [Table 9]

[0341] [Example C4] The procedure of Example C2 was repeated except for changing the composition of the raw materials introduced into the reactor 1. These fractions were used as raw materials so that the recycle ratio of the fraction A-1 was 0.42 and the recycle ratio of the fraction B was 0.90, and based on the results of Reference Examples 1 and 2 described above, the propylene yield and other data for steady-state operation are shown in Table 10. The raw material introduced into reactor 1 has an ethylene / ethanol molar ratio of 0.20 and a C4-6 olefin / ethylene molar ratio of 0.61. The composition of components (mainly hydrocarbons with a carbon number of 4 or more) recycled from fraction B contained in the raw material is shown in Table 9. The feed rate of the raw material to reactor 1 is WHSV = 3.8, the inlet temperature of the catalyst bed is 563 °C, the outlet temperature is 517 °C, and the average inlet / outlet reaction temperature is 540 °C. The average propylene yield from the start of the reaction to the end of the reaction is 22.1 mass%, and the coke yield of the zeolite-containing catalyst after 48 hours of operation is 256 mass ppm. The propylene recovery yield obtained at the outlet of the separation step is 13.8 mass%, and the aromatic compound recovery yield is 12.5 mass%.

[0342] [Example C5] The procedure of Example C2 was repeated except for changing the composition of the raw materials introduced into the reactor 1. These fractions were used as raw materials so that the recycle ratio of the fraction A-1 was 0.94 and the recycle ratio of the fraction B was 0.90, and based on the results of Reference Examples 1 and 2 described above, the propylene yield and other data for steady operation are shown in Table 10. The raw material introduced into reactor 1 has an ethylene / ethanol molar ratio of 0.60 and a C4-6 olefin / ethylene molar ratio of 0.27. The composition of components (mainly hydrocarbons with a carbon number of 4 or more) recycled from fraction B contained in the raw material is shown in Table 9. The feed rate of the raw material to reactor 1 is WHSV = 3.8, the inlet temperature of the catalyst bed is 534 °C, the outlet temperature is 546 °C, and the average inlet / outlet reaction temperature is 540 °C. The average propylene yield from the start of the reaction to the end of the reaction is 23.8 mass%, and the coke yield of the zeolite-containing catalyst after 48 hours of operation is 220 mass ppm. The propylene recovery yield obtained at the outlet of the separation step is 17.1 mass%, and the aromatic compound recovery yield is 15.5 mass%.

[0343] [Example C6] The procedure was the same as in Example C4, except that fraction B was not recycled. The raw material was supplied to reactor 1 packed with zeolite-containing catalyst 1 to obtain a reaction gas. The obtained reaction gas was fed to a cooling device 6 to separate fraction C, which mainly contains hydrocarbons with a carbon number of 6 or less, and fraction D, which mainly contains water and hydrocarbons with a carbon number of 7 or more. Fraction C was fed to first distillation column 2 to separate fraction A, which mainly contains hydrocarbons with a carbon number of 3 or less, and fraction B, which mainly contains hydrocarbons with a carbon number of 4 or more. The obtained fraction A was fed to second distillation column 8 to separate fraction A-1, which mainly contains hydrocarbons with a carbon number of 2 or less, and fraction A-2, which mainly contains hydrocarbons with a carbon number of 3. Fraction A-1 was used as a raw material so that the recycle ratio of fraction A-1 was 0.41. Table 10 shows the propylene yield and other data for the above process during steady-state operation based on the results of Reference Examples 1 and 2 described above. The raw material introduced into reactor 1 has an ethylene / ethanol molar ratio of 0.20. The feed rate of the raw material to reactor 1 is WHSV = 3.8, the inlet temperature of the catalyst bed is 563°C, the outlet temperature is 517°C, and the average inlet / outlet reaction temperature is 540°C. The average propylene yield from the start of the reaction to the end of the reaction is 24.5 mass%, and the coke yield of the zeolite-containing catalyst after 48 hours of operation is 210 mass ppm. The recovery yield of propylene obtained at the outlet of the separation step is 18.5 mass%, and the recovery yield of aromatic compounds is 1.7 mass%. A comparison between Example C2 and Example C6 shows that recycling fraction B, which mainly contains hydrocarbons having 4 or more carbon atoms, improves the recovery yield of aromatic compounds.

[0344] [Example C7] The effectiveness of the conversion method according to this embodiment was verified using the apparatus shown in FIG. 10 when external ethylene was introduced as a feedstock. In this example, in addition to the ethylene contained in fraction A-1, additional ethylene was added externally to the feedstock. The feedstock was supplied to reactor 1 packed with a zeolite-containing catalyst 1 to obtain a reaction gas. The resulting reaction gas was passed through a cooling device 6 to separate fraction C, which mainly contains hydrocarbons with a carbon number of 6 or less, and fraction D, which mainly contains water and hydrocarbons with a carbon number of 7 or more. Fraction C was passed through first distillation column 2 to separate fraction A, which mainly contains hydrocarbons with a carbon number of 3 or less, and fraction B, which mainly contains hydrocarbons with a carbon number of 4 or more. Fraction A was passed through second distillation column 8 to separate fraction A-1, which mainly contains hydrocarbons with a carbon number of 2 or less, and fraction A-2, which mainly contains hydrocarbons with a carbon number of 3. These fractions were used as feedstocks so that the recycle ratios of fraction A-1 and fraction B were 0.28 and 0.90, respectively. Table 10 shows the propylene yield and other data for the above process in steady state operation based on the results of Reference Examples 1 and 2 described above. The feedstock introduced into reactor 1 has an ethylene / ethanol molar ratio of 0.80 and a C4-6 olefin / ethylene molar ratio of 0.23. The composition of components recycled from fraction B contained in the feedstock (mainly hydrocarbons with a carbon number of 4 or more) is shown in Table 9. The feedstock feed rate to reactor 1 is WHSV = 3.8, the catalyst bed inlet temperature is 520 °C, the outlet temperature is 560 °C, and the average inlet / outlet reaction temperature is 540 °C. The average propylene yield from the start of the reaction to the end of the reaction is 24.5 mass%, and the coke yield of the zeolite-containing catalyst after 48 hours of operation is 321 mass ppm. The propylene recovery yield obtained at the outlet of the separation step is 14.8 mass%, and the aromatic compound recovery yield is 13.4 mass%.

[0345] [Table 10] [Industrial Applicability]

[0346] According to the present invention, a method for converting ethanol into a target compound with high yield by using an adiabatic reactor and controlling the temperature inside the reactor can be provided. Since the target compound, such as propylene or an aromatic compound, can be used for synthesizing chemical products, the present invention has industrial applicability. [Explanation of symbols]

[0347] 1: adiabatic reactor, 12: reaction box, 121: heat insulating material, 13: catalyst bed, 131: catalyst bed inlet, 132: catalyst bed outlet, 14: reactor inlet, 15: reactor outlet, 161: first sheathed thermocouple, 162: second sheathed thermocouple, 2, 3, 4, 8: distillation column, 5: steam cracking device, 6: cooling device, 7: oil-water separator

Claims

1. A method for converting ethanol, comprising contacting a mixed feedstock containing ethylene and ethanol with a catalyst in an adiabatic reactor to obtain a reaction gas containing olefins having 3 or more carbon atoms.

2. 2. The method for converting ethanol according to claim 1, wherein the ethylene / ethanol molar ratio in the mixed feedstock is 0.20 to 2.

5.

3. 2. The method for converting ethanol according to claim 1, wherein the ethylene / ethanol molar ratio in the mixed feedstock is 0.20 to 2.

0.

4. 10. The method for converting ethanol according to claim 1, further comprising separating ethylene and propylene from the reaction gas.

5. 2. The method for converting ethanol according to claim 1, wherein the mixed feedstock contains olefins having 4 to 6 carbon atoms.

6. 6. The method for converting ethanol according to claim 5, wherein the molar ratio of C4-C6 olefins to ethylene in the mixed feedstock is 3.0 or less.

7. A method for converting ethanol, comprising contacting a mixed feedstock containing methanol and ethanol with a catalyst in an adiabatic reactor to obtain a reaction gas containing olefins having three or more carbon atoms.

8. 8. The method for converting ethanol according to claim 7, wherein the molar ratio of methanol / ethanol in the mixed feedstock is 0.050 to 2.

0.

9. 8. The method for converting ethanol according to claim 7, wherein the molar ratio of methanol / ethanol in the mixed feedstock is 0.20 to 1.

5.

10. 8. The method for converting ethanol according to claim 7, further comprising separating ethylene and propylene from the reaction gas.

11. The method for converting ethanol according to claim 7, wherein the mixed feedstock contains olefins having 4 to 6 carbon atoms.

12. 8. The method for converting ethanol according to claim 7, wherein the molar ratio of C4-C6 olefins to methanol in the mixed feedstock is 3.0 or less.

13. 8. The method for converting ethanol according to claim 7, further comprising recycling at least a portion of the reaction gas or a fraction obtained by purifying the reaction gas to the reactor and using it as part of the mixed feedstock.

14. contacting a mixed raw material containing ethanol and ethylene with a catalyst in an adiabatic reactor to obtain a reaction gas containing olefins having 3 or more carbon atoms; separating the reaction gas into a fraction A mainly containing hydrocarbons having 2 to 3 carbon atoms and a fraction B mainly containing hydrocarbons having 4 to 6 carbon atoms using a first distillation column; Recycle at least a portion of the fraction A to the reaction step as part of the mixed raw material; A method for converting ethanol, comprising:

15. separating the fraction A into a fraction A-1 containing mainly hydrocarbons having a carbon number of 2 and a fraction A-2 containing mainly hydrocarbons having a carbon number of 3 by a second distillation column; The recycling step includes recycling at least a portion of the fraction A-1 to obtain the reaction gas and using the fraction A-1 as part of the mixed feedstock.

15. The method for converting ethanol according to claim 14.

16. The recycling step includes recycling at least a portion of the fraction B to obtain the reaction gas and using the fraction B as part of the mixed feedstock.

15. The method for converting ethanol according to claim 14.

17. cooling the reaction gas to separate it into a fraction C mainly containing hydrocarbons having a carbon number of 6 or less and a fraction D mainly containing water and hydrocarbon compounds having a carbon number of 7 or more; 15. The method for converting ethanol according to claim 14, comprising:

18. 15. The method of claim 14, wherein separating by a first distillation column comprises providing a side cut stage on the first distillation column to obtain an intermediate draw effluent.

19. 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; separating ethylene and propylene from said fraction A; 2. The method for converting ethanol according to claim 1, comprising:

20. 20. The method for converting ethanol according to claim 19, comprising recycling at least a portion of said fraction B to said reactor and using it as part of said mixed feedstock.

21. 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; recycling at least a portion of the fraction B1 to the reactor and using it as part of the mixed feedstock; 20. The method for converting ethanol according to claim 19, comprising:

22. Obtaining a steam cracking product containing ethylene and propylene by subjecting the fraction B to steam cracking; separating ethylene and propylene from said steam cracking product; 20. The method for converting ethanol according to claim 19, comprising:

23. 2. The method for converting ethanol according to claim 1, wherein the reactor is a fixed-bed adiabatic reactor.

24. 2. The method for converting ethanol according to claim 1, wherein the reactor is a fixed-bed, single-stage adiabatic reactor.

25. 10. The method of claim 1, further comprising burning coke adhering to the catalyst.

26. 2. The process for converting ethanol according to claim 1, wherein the catalyst bed outlet temperature is 450°C to 590°C.

27. 2. The process for converting ethanol according to claim 1, wherein the catalyst bed inlet temperature is 450°C to 590°C.

28. 2. The method for converting ethanol according to claim 1, wherein the temperature difference between the catalyst bed outlet temperature and the catalyst bed inlet temperature is −80K to 80K.

29. 2. The method for converting ethanol according to claim 1, wherein the catalyst is a zeolite-containing catalyst.

30. 30. The process for converting ethanol according to claim 29, wherein the zeolite-containing catalyst comprises an intermediate pore size zeolite.

31. 30. The process for converting ethanol according to claim 29, wherein the silica / alumina molar ratio of the zeolite in the zeolite-containing catalyst is 20-2000.

32. 30. The method for converting ethanol according to claim 29, wherein the zeolite-containing catalyst comprises elemental phosphorus or elemental silver.

33. A method for producing hydrocarbons, comprising contacting a mixed feedstock containing ethylene and ethanol with a catalyst in an adiabatic reactor to obtain a reaction gas containing olefins having three or more carbon atoms.

34. a cracking step of cracking hydrocarbons having two or more carbon atoms; a purification step of purifying the components obtained in the cracking step; and A method for producing hydrocarbons, wherein in the purification step, the reaction gas obtained by the method for converting ethanol according to any one of claims 1 to 32 or a purified fraction thereof is combined.

35. an unsaturated hydrocarbon separation step of separating a fraction mainly containing unsaturated hydrocarbons from the reaction gas obtained by the ethanol conversion method according to any one of claims 1 to 32; A method for producing a monomer, comprising:

36. an olefin separation step of separating a fraction mainly containing olefins from the reaction gas obtained by the ethanol conversion method according to any one of claims 1 to 32; A method for producing an olefin, comprising:

37. A propylene separation step of separating a fraction mainly containing propylene from the reaction gas obtained by the ethanol conversion method according to any one of claims 1 to 32; A method for producing propylene, comprising:

38. an ethylene separation step of separating a fraction mainly containing ethylene from the reaction gas obtained by the ethanol conversion method according to any one of claims 1 to 32; A method for producing ethylene, comprising:

39. a diene separation step of separating a fraction mainly containing dienes from the reaction gas obtained by the ethanol conversion method according to any one of claims 1 to 32; A method for producing a diene, comprising:

40. an unsaturated hydrocarbon separation step of separating a fraction mainly containing unsaturated hydrocarbons from the reaction gas obtained by the ethanol conversion method according to any one of claims 1 to 32; 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, comprising:

41. a propylene separation step of separating a fraction mainly containing propylene from the reaction gas obtained by the ethanol conversion method according to any one of claims 1 to 32; an acrylonitrile production step of obtaining acrylonitrile from the propylene obtained in the propylene separation step; A method for producing acrylonitrile, comprising:

42. an ethylene separation step of separating a fraction mainly containing ethylene from the reaction gas obtained by the ethanol conversion method according to any one of claims 1 to 32; a styrene production step of obtaining styrene from the ethylene obtained in the ethylene separation step; A method for producing styrene, comprising:

43. Polymerizing the monomer obtained by the process according to claim 35; A method for producing a polymer, comprising:

44. A step of polymerizing the polymerizable composition containing the olefin obtained by the production method according to claim 36; A method for producing an olefin polymer, comprising:

45. A step of polymerizing a polymerizable composition containing propylene obtained by the production method according to claim 37; A method for producing a polypropylene-based polymer, comprising:

46. A step of polymerizing the polymerizable composition containing ethylene obtained by the production method according to claim 38; A method for producing a polyethylene polymer, comprising:

47. A step of polymerizing a polymerizable composition containing a diene obtained by the production method according to claim 39; A method for producing a diene polymer, comprising:

48. A step of polymerizing a polymerizable composition containing an acrylic monomer obtained by the production method according to claim 40; A method for producing an acrylic monomer-based polymer, comprising:

49. A step of polymerizing a polymerizable composition containing acrylonitrile obtained by the production method according to claim 41; A method for producing an acrylonitrile polymer, comprising:

50. A step of polymerizing the styrene-containing polymerizable composition obtained by the production method according to claim 42; A method for producing a styrene-based polymer, comprising:

51. an aromatic compound separation step of separating a fraction mainly containing aromatic compounds from the reaction gas obtained by the ethanol conversion method according to any one of claims 1 to 32; A method for producing an aromatic compound, comprising:

52. an aromatic monomer production step of obtaining an aromatic monomer from the aromatic compound obtained by the production method according to claim 51; A method for producing an aromatic monomer, comprising:

53. A step of polymerizing a polymerizable composition containing an aromatic monomer obtained by the production method according to claim 52; A method for producing an aromatic monomer-based polymer, comprising:

54. a reactor in which a mixed raw material containing ethanol and ethylene is brought into contact with a catalyst in an adiabatic reactor to obtain a reaction gas containing olefins having 3 or more carbon atoms; a first distillation column for separating the reaction gas into a fraction A mainly containing hydrocarbons having 2 to 3 carbon atoms and a fraction B mainly containing hydrocarbons having 4 to 6 carbon atoms; Equipped with An apparatus for converting ethanol, wherein at least a portion of the fraction A is recycled to the reactor and used as part of the mixed feedstock.

55. a second distillation column that separates the fraction A into a fraction A-1 that mainly contains hydrocarbons having a carbon number of 2 and a fraction A-2 that mainly contains hydrocarbons having a carbon number of 3; 55. The ethanol conversion apparatus according to claim 54, wherein at least a portion of the fraction A-2 is recycled to the reactor and used as part of the mixed feedstock.

56. 56. The ethanol conversion apparatus of claim 55, wherein the first distillation column has a sidecut stage for obtaining an intermediate draw effluent.

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