Methods for ethanol conversion and methods for the production of other hydrocarbons.

Abstract

(1) A method for converting ethanol which comprises bringing a mixture feedstock including ethylene and ethanol into contact with a catalyst in an adiabatic reactor to obtain a reaction gas including an olefin having three or more carbon atoms, (2) a method for converting ethanol which comprises bringing a mixture feedstock including methanol and ethanol into contact with a catalyst in an adiabatic reactor to obtain a reaction gas including an olefin having three or more carbon atoms, and (3) a method for converting ethanol which comprises bringing a mixture feedstock including ethanol and ethylene into contact with a catalyst in an adiabatic reactor to obtain a reaction gas including an olefin having three or more carbon atoms, separating the reaction gas by a first distillation tower into a fraction A mainly including hydrocarbons having two to three carbon atoms and a fraction B mainly including hydrocarbons having four to six carbon atoms, and recycling at least some of the fraction A as some of the mixture feedstock to the reaction step.

Description

Methods for converting ethanol and other hydrocarbons

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

[0002] Hydrocarbons such as lower olefins are important core raw materials in the chemical industry, and since 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 a method in which naphtha and olefins are brought into contact 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 a pentasil-type zeolite and a 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 4 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.

[0004] WO2014 / 025021A1WO2015 / 029355A1CN110560155AUS2014 / 0018593A1CN110871107AWO2005 / 56504A1

[0005] The present invention encompasses 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 3 or more carbon atoms. [2] The method for converting ethanol according to [1], wherein the molar ratio of ethylene / 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 / ethanol in the mixed feedstock is 0.20 to 2.0. [4] The method for converting ethanol according to any one of [1] to [3], 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 feedstock 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 / 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 3 or more carbon atoms. [8] The method for converting ethanol according to any one of [1] to [6], wherein the mixed feedstock contains methanol. [9] The method for converting ethanol according to [7] or [8], wherein the molar ratio of methanol / ethanol in the mixed feedstock 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 feedstock is 0.20 to 1.5.

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

[10] , 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 / 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 method for converting ethanol, comprising: contacting a mixed feedstock 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, and recycling at least a portion of the fraction A to the reaction step as part of the mixed feedstock.

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

[14] , comprising: 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, and recycling at least a portion of the fraction A to the reaction step as part of the mixed feedstock.

[17] The method for converting ethanol according to

[15] or

[16] , comprising 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 by a second distillation column, and wherein the recycling comprises recycling at least a portion of the fraction A-1 to obtain the reaction gas and using it as part of the mixed feedstock.

[18] The method for converting ethanol according to any of

[15] to

[17] , wherein the recycling comprises recycling at least a portion of the fraction B to obtain the reaction gas and using it as part of the mixed feedstock.

[19] The method for converting ethanol according to any of

[15] to

[18] , comprising 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.

[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.

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

[20] , comprising: separating the reaction gas into a fraction A mainly containing hydrocarbons having 1 to 3 carbon atoms and a fraction B mainly containing hydrocarbons having 4 to 8 carbon atoms; and separating ethylene and propylene from the fraction A.

[22] The method for converting ethanol according to

[21] , which comprises recycling at least a portion of the fraction B to the reactor and using it as part of the mixed feedstock.

[23] The method for converting ethanol according to

[21] or

[22] , which comprises separating the fraction B into a fraction B1 mainly containing aliphatic hydrocarbons having 4 to 6 carbon atoms and a fraction B2 mainly containing aromatic compounds, and recycling at least a portion of the fraction B1 to the reactor and using it as part of the mixed feedstock.

[24] The method for converting ethanol according to any of

[21] to

[23] , which comprises subjecting the fraction B to steam cracking to obtain a steam cracking product containing ethylene and propylene, and separating the ethylene and propylene from the steam cracking product.

[25] The method for converting ethanol according to any 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 -80K to 80K.

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

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

[32] The method for converting ethanol according to

[31] , wherein the zeolite-containing catalyst contains 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 3 or more carbon atoms.

[36] A method for producing hydrocarbons, comprising: a cracking step of cracking hydrocarbons having 2 or more carbon atoms; and a purification step of purifying the components obtained in the cracking step, wherein the reaction gas obtained by the ethanol conversion method according to any one of [1] to

[34] or a purified fraction thereof is combined in the purification step.

[37] A method for producing monomers, comprising: 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] .

[38] A method for producing olefins, comprising: 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] .

[39] A method for producing propylene, comprising: 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] .

[40] A method for producing ethylene, comprising: an ethylene separation step of separating a fraction mainly containing ethylene from a reaction gas obtained by the method for converting ethanol according to any one of [1] to

[34] .

[41] A method for producing dienes, comprising: a diene separation step of separating a fraction mainly containing dienes from a reaction gas obtained by the method for converting ethanol according to any one of [1] to

[34] .

[42] A method for producing acrylic monomers, comprising: an unsaturated hydrocarbon separation step of separating a fraction mainly containing unsaturated hydrocarbons from a reaction gas obtained by the method for converting ethanol according to any one of [1] to

[34] ; and an acrylic monomer production step of obtaining acrylic monomers from the unsaturated hydrocarbons obtained by the unsaturated hydrocarbon separation step.

[43] A method for producing acrylonitrile, comprising: a propylene separation step of separating a fraction mainly containing propylene from a reaction gas obtained by the method for converting ethanol according to any one of [1] to

[34] ; and an acrylonitrile production step of obtaining acrylonitrile from the propylene obtained by the propylene separation step.

[44] A method for producing styrene, comprising: an ethylene separation step of separating a fraction mainly containing ethylene from a reaction gas obtained by the ethanol conversion method according to any one of [1] to

[34] ; and a styrene production step of obtaining styrene from the ethylene obtained by the ethylene separation step.

[45] A method for producing a polymer, comprising: a step of polymerizing a monomer obtained by the production method according to

[37] .

[46] A method for producing an olefin-based polymer, comprising: a step of polymerizing a polymerizable composition containing an olefin obtained by the production method according to

[38] .

[47] A method for producing a polypropylene-based polymer, comprising: a step of polymerizing a polymerizable composition containing propylene obtained by the production method according to

[39] .

[48] A method for producing a polyethylene-based polymer, comprising: a step of polymerizing a polymerizable composition containing ethylene obtained by the production method according to

[40] .

[49] A method for producing a diene-based polymer, comprising: a step of polymerizing a polymerizable composition containing a diene obtained by the production method according to

[41] .

[50] A method for producing an acrylic monomer-based polymer, comprising: a step of polymerizing a polymerizable composition containing an acrylic monomer obtained by the production method according to

[42] .

[51] A method for producing an acrylonitrile-based polymer, comprising: a step of polymerizing a polymerizable composition containing acrylonitrile obtained by the production method according to

[43] .

[52] A method for producing a styrene-based polymer, comprising: a step of polymerizing a polymerizable composition containing styrene obtained by the production method according to

[44] .

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

[34] .

[54] A method for producing an aromatic monomer, comprising: an aromatic monomer production step of obtaining an aromatic monomer from the aromatic compound obtained by the production method according to

[53] .

[55] A method for producing an aromatic monomer-based polymer, comprising: a step of polymerizing a polymerizable composition containing an aromatic monomer obtained by the production method according to

[53] .

[56] An ethanol conversion apparatus comprising: a reactor that contacts a mixed feedstock containing ethanol and ethylene with a catalyst in an adiabatic reactor to obtain a reaction gas containing olefins having 3 or more carbon atoms; and a first distillation column that separates 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, wherein at least a portion of the fraction A is recycled to the reactor and used as part of the mixed feedstock.

[57] The ethanol conversion apparatus according to

[57] , comprising a second distillation column that separates the fraction A into a fraction A-1 mainly containing hydrocarbons having 2 carbon atoms and a fraction A-2 mainly containing hydrocarbons having 3 carbon atoms, wherein at least a portion of the fraction A-2 is recycled to the reactor and used as part of the mixed feedstock.

[58] The ethanol conversion apparatus according to

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

[0006] FIG. 1 shows a schematic diagram of an embodiment of a fixed-bed, single-stage adiabatic reactor. FIG. 2 shows an embodiment of the flow of the reaction step and separation step. FIG. 3 shows an embodiment of the flow of the reaction step, separation step, and steam cracking step. FIG. 4 shows an embodiment of the flow of the reaction step and separation step. FIG. 5 shows an embodiment of the flow of the reaction step and separation step. FIG. 6 shows an embodiment of the flow of the reaction step and separation step. FIG. 7 shows a schematic diagram of an embodiment of an ethanol and ethylene conversion apparatus. FIG. 8 shows a schematic diagram of an embodiment of an ethanol and ethylene conversion apparatus. FIG. 9 shows a schematic diagram of an embodiment of an ethanol and ethylene conversion apparatus. FIG. 10 shows a schematic diagram of an embodiment of an ethanol and ethylene conversion apparatus. FIG. 11 shows a schematic diagram of an embodiment of an ethanol and ethylene conversion apparatus. FIG. 12 shows a schematic diagram of a conversion apparatus for comparing the effects of the ethanol and ethylene conversion apparatus of this embodiment. FIG. 13 shows a schematic diagram of a conversion apparatus for comparing the effects of the ethanol and ethylene conversion apparatus of this embodiment.

[0007] The present invention will be described in detail 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, numerical ranges indicated using "to" indicate ranges that include 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] In this specification, the term "target compound" refers to a hydrocarbon such as an olefin or an aromatic compound. 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 the situation, such as demand, but in the ethanol conversion method of this embodiment, it is also possible to obtain propylene, which has three carbon atoms, and aromatic compounds, which have six or more carbon atoms, from ethanol, which has two carbon atoms.

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

[0011] <Method for Conversion of Ethanol—First Embodiment—> The method for converting ethanol according to the first 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 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 the production of chemical products using alcohols such as ethanol produced from biomass feedstocks as raw materials. In particular, because 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 raw materials into target olefins 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 extensive research 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 a 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] (Feedstock) 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, even more 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 target compounds such as propylene when contacted 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 C4-C6 olefins 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 feedstock may further contain an oxygenated compound having 1 to 6 carbon atoms other than ethanol. Similar to ethylene 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 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] 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. 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 feedstock may also contain olefins having 4 or more carbon atoms which 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 feedstock.

[0033] The mixed feedstock may contain an inert gas such as nitrogen in addition to the above-mentioned feedstocks that can be converted into target compounds such as 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)). 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 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 effect that occurs with the hydrogen dilution.

[0034] The total proportion of ethylene, olefins having 4 to 6 carbon atoms, and ethanol in the mixed feedstock is preferably 40 mass% or more, more preferably 50 mass% or more, based on the mass flow rate of the mixed feedstock, which is 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] The total content of olefins having 4 to 6 carbon atoms in the mixed raw material 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, ls. 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 having 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 includes 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 the reactor to the outside. In the production method according to this embodiment, the temperature inside the reactor can be controlled by the heat generation and heat absorption caused 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 temperatures of the mixed feedstock 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] (Conditions for the Reaction Step) In the ethanol conversion method of this embodiment, the reaction temperature may be 300°C or higher. Since the olefins produced 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 accelerated 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 the 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 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 inlet / outlet average reaction temperature is a value (hereinafter simply referred to as "reaction temperature") calculated by measuring the inlet temperature of the catalyst bed and the 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.

[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 hr in terms of the mass-based 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, the WHSV is calculated by converting ethanol into ethylene, as shown in the following formula: From the viewpoint of excellent productivity of target compounds such as propylene and aromatic compounds, the effective raw material supply mass flow rate is preferably 1 kg / hr or more, more preferably 10 kg / hr or more, and even more preferably 1,000 kg / hr or more.

[0049] WHSV (hr －１ ) = mass flow rate of effective raw material supply (kg / hr) / catalyst amount (kg) Mass flow rate of effective raw material supply (kg / hr) = ethylene flow rate (kg / hr) + ethylene-equivalent ethanol flow rate (kg / hr) + C4-C6 olefin flow rate (kg / hr) + C1-C6 oxygen-containing 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)

[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> A 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. An 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." An "intermediate pore size zeolite" has a so-called 10-membered oxygen ring in its crystal structure.

[0052] Examples of intermediate pore size 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 (SiO ２ / Al ２ O ３ The silica / alumina (SiO ) molar ratio of the zeolite contained in the zeolite-containing catalyst 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 the durability of the catalyst, it is more preferably 100 to 1500, even more preferably 300 to 1200, and still more preferably 800 to 1200. ２ / Al ２ O ３ The silica / alumina molar ratio 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 spectrometry or the like.

[0054] The zeolite synthesis method of the present embodiment is not particularly limited, but can be produced by optimizing various conditions of a conventionally known hydrothermal synthesis method for 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, or a method of hydrothermal synthesis in which MFI zeolite is added as a seed slurry in the crystalline stage. Examples of organic structure-directing agents (SDAs) 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 of MFI zeolite as described above, a suitable catalyst can be obtained by appropriately optimizing synthesis conditions such as the raw material charge composition (e.g., the type of raw material and additive (SDA), the amount of additive, pH, silica / alumina molar ratio, medium, cation and anion abundance ratio), synthesis temperature, and synthesis time.

[0055] Specific examples include the synthesis method using a seed slurry described in Japanese Patent No. 5,426,983 and the method exemplified in The Hydrothermal Synthesis of Zeolites (Chemical Reviews, 2003, 103, 663-702).

[0056] Furthermore, 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] The form of phosphorus element includes a polymer of phosphorus (e.g., polyphosphoric acid), an oxide of phosphorus (e.g., P ２ O ５ ), compounds in which phosphorus is added to the aluminum of zeolite, etc. In addition, a plurality of these may be contained. 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 zeolite 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, is 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 having relatively high solubility in water are preferred, and more preferred is at least one selected from the group consisting of ammonium phosphate, diammonium hydrogen phosphate, and ammonium dihydrogen phosphate. 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, it is 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 an atmosphere that is not particularly limited, but in which a mixed gas of air or an inert gas such as nitrogen and steam (water vapor) is circulated, with 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 Having 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. "Reaction gas" refers to a gas composition resulting from reaction of a mixed feedstock with a 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 Step] When a catalyst is used in a reaction for a long period of time, coke may adhere to the catalyst, causing coking degradation. When a catalyst has been degraded by coking, the catalyst can be regenerated by, for example, contacting the catalyst 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 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 can be used to perform a reaction-regeneration switching operation.

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

[0073] [Separation Step] 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 the "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 including reactor 1, distillation column 2, distillation column 3, and distillation column 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. Fraction B and other fractions obtained in the separation step 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 by separating the ethylene and propylene from the steam cracking product, the efficiency of the entire process can be improved. Steam cracking refers to the thermal decomposition of compounds in the fraction with 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 allows the reaction gas to 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. 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 including a reactor 1, a distillation column 2, and a distillation column 8. When recycling fraction B 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, enabling efficient propylene production. 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 Figure 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 a second embodiment will be described.

[0083] <Method for Conversion of Ethanol - Second Embodiment> The method for converting ethanol according to the second embodiment includes 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 (hereinafter also referred to as the "reaction step"). Note that propylene can be obtained by separating the olefins from the reaction gas, and aromatic compounds can also be obtained by separating the olefins from the 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 techniques for converting raw materials into target olefins 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.

[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 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 these findings, the inventors discovered that contacting a mixed feedstock containing methanol and ethanol with a catalyst packed in an adiabatic reactor can efficiently convert the alcohols into the target compound and suppress coking degradation. 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. For example, the conversion reaction from methanol to propylene is an exothermic reaction, and the conversion reaction from ethanol to propylene is an endothermic reaction. In this embodiment, it was discovered that endothermic and exothermic reactions proceed without inhibiting each other within the reactor, 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 behind this are not limited to these.

[0091] (Feedstock) The ethanol conversion method of this embodiment uses a mixed feedstock containing methanol and ethanol. By using this mixed feedstock, it is possible to produce target compounds such as propylene 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 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 feedstock.

[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 produce 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 the olefin having 4 to 6 carbon atoms include butene, pentene, and hexene. In the mixed raw material, the molar ratio of the olefin 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 feedstock 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 feedstock 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 feedstock 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 produce 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] The mixed feedstock can 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. 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 they have lower reactivity than 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 step, 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 (no hydrogen dilution is 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 the hydrogen dilution described above.

[0103] The total proportion of methanol, C4-C6 olefins, 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 in calculating the methanol mass, ethanol mass, and effective raw material supply mass.

[0105] The total content of olefins having 4 to 6 carbon atoms in the mixed raw material 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 is derived from water that has not been 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, ls. 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 having 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 includes 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 the reactor to the outside. In the production method according to this embodiment, the temperature inside the reactor can be controlled by the heat generation and heat absorption caused 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 temperatures of the mixed feedstock 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] (Conditions for the Reaction Step) In the ethanol conversion method of this embodiment, the reaction temperature may be 300°C or higher. Since the olefins produced 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 accelerated 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 the 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 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 inlet / outlet average reaction temperature is a value (hereinafter simply referred to as "reaction temperature") calculated by measuring the inlet temperature of the catalyst bed and the 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.

[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 hr in terms of the mass-based 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, the WHSV is calculated by converting ethanol into ethylene, as shown in the following formula: From the viewpoint of excellent productivity of target compounds such as propylene and aromatic compounds, the effective raw material supply mass flow rate is preferably 1 kg / hr or more, more preferably 10 kg / hr or more, and even more preferably 1 t / hr or more.

[0118] WHSV (hr －１ ) = mass flow rate of effective raw material supplied (kg / hr) / catalyst amount (kg) Mass flow rate of effective raw material supplied (kg / hr) = methylene-equivalent methanol flow rate (kg / hr) + ethylene-equivalent ethanol flow rate (kg / hr) + C4-C6 olefin flow rate (kg / hr) + ethylene flow rate (kg / hr) + flow rate of oxygenated compounds having C1-C6 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> A 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. An 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." An "intermediate pore size zeolite" has a so-called 10-membered oxygen ring in its crystal structure.

[0121] Examples of intermediate pore size 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 (SiO ２ / Al ２ O ３ The silica / alumina (SiO ) molar ratio of the zeolite contained in the zeolite-containing catalyst 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. ２ / Al ２ O ３ The silica / alumina molar ratio 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 spectrometry or the like.

[0123] The zeolite synthesis method of the present embodiment is not particularly limited, but can be produced by optimizing various conditions of a conventionally known hydrothermal synthesis method for 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, or a method of hydrothermal synthesis in which MFI zeolite is added as a 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 of MFI zeolite as described above, a suitable catalyst can be obtained by appropriately optimizing synthesis conditions such as the raw material charge composition (e.g., the type of raw material and additive (SDA), the amount of additive, pH, silica / alumina molar ratio, medium, cation and anion abundance ratio), synthesis temperature, and synthesis time.

[0124] Specific examples include the synthesis method using a seed slurry described in Japanese Patent No. 5,426,983 and the method exemplified in The Hydrothermal Synthesis of Zeolites (Chemical Reviews, 2003, 103, 663-702).

[0125] Furthermore, 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] The form of phosphorus element includes a polymer of phosphorus (e.g., polyphosphoric acid), an oxide of phosphorus (e.g., P ２ O ５ ), compounds in which phosphorus is added to aluminum in zeolite, etc. Furthermore, a plurality of these may be contained. 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 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 makes it easy for the reactor to become a high-temperature steam atmosphere, and the properties of the zeolite-containing catalyst are easily changed by dealumination. However, when the zeolite-containing catalyst contains elemental phosphorus, the effect of suppressing dealumination of the zeolite is further improved.

[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, is 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 having relatively high solubility in water are preferred, and more preferred is at least one selected from the group consisting of ammonium phosphate, diammonium hydrogen phosphate, and ammonium dihydrogen phosphate. 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, it is 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 an atmosphere that is not particularly limited, but in which a mixed gas of air or an inert gas such as nitrogen and steam (water vapor) is circulated, with 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 Having 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. "Reaction gas" refers to the gas composition after reaction by contacting a mixed feedstock with a 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 Step] When a catalyst is used in a reaction for a long period of time, coke may adhere to the catalyst, causing coking degradation. When a catalyst has been degraded by coking, the catalyst can be regenerated by, for example, contacting the catalyst 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 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 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 step and a regeneration step are carried out simultaneously using a two-tower or multi-tower switching type adiabatic reactor. For example, in the case of a three-tower switching type, two towers are used for the reaction step, and at the same time, the remaining tower is used for catalyst regeneration. Thereafter, the reaction step in one of the towers used for the reaction step is stopped to perform catalyst regeneration, and the reaction step is carried out in the one tower used for catalyst regeneration, thereby enabling catalyst regeneration while maintaining the production capacity of the two towers. This type of reaction format is also called a merry-go-round system, and is preferred from the viewpoint of excellent production efficiency because it does not require stopping the production process for catalyst regeneration.

[0142] [Separation Step] In the separation step, the target compound is 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 including reactor 1, distillation column 2, distillation column 3, and distillation column 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. Fraction B and other fractions obtained in the separation step 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 by separating the ethylene and propylene from the steam cracking product, the efficiency of the entire process can be improved. Steam cracking refers to the thermal decomposition of compounds in the fraction with 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 allows the reaction gas to 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. 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 including a reactor 1, a distillation column 2, and a distillation column 8. When recycling fraction B 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, enabling efficient propylene production. 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 Figure 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 various fractions 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 following steps: contacting a mixed feedstock containing ethanol and ethylene 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 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 (hereinafter also referred to as the "first separation step"); and recycling at least a portion of the fraction A as part of the mixed feedstock to the reaction step (hereinafter also referred to as the "recycle step"). According to this embodiment, a method for efficiently converting ethanol into a target compound can be provided by using an adiabatic reactor and controlling the temperature within the reactor. Propylene can be obtained by separating propylene from the reaction gas, and aromatic compounds can also be obtained by separating propylene from the 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 raw materials into target olefins using a zeolite catalyst, but these techniques cannot be applied to an adiabatic reactor because of the large endothermic and exothermic reactions. 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, but 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 into target compounds in good 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 Step> In the reaction step according to this embodiment, 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. 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 into target compounds with high yields, and coking deterioration 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 assumed 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 involving a two-stage reaction consisting of 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] (Feedstock) In the ethanol conversion method of this embodiment, a mixed feedstock containing ethylene and ethanol is used. By using this mixed feedstock, it is possible to produce target compounds such as propylene 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 compounds produced using biomass as a feedstock.

[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 target compounds such as propylene when brought into contact 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.

[0170] In the mixed raw material, the molar ratio of C4-6 olefins 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 feedstock may further contain an oxygenated compound having 1 to 6 carbon atoms other than ethanol. Similar to ethylene 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 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 feedstock is preferably 40 mass% or more, more preferably 50 mass% or more, based on the mass flow rate of the mixed feedstock, which is 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] The total content of olefins having 4 to 6 carbon atoms in the mixed raw material 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, pp. 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 having 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 includes 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 the reactor to the outside. In the production method according to this embodiment, the temperature inside the reactor can be controlled by the heat generation and heat absorption caused 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 temperatures of the mixed feedstock 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] (Conditions for the Reaction Step) In the ethanol conversion method of this embodiment, the reaction temperature may be 300°C or higher. Since the olefins produced 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 accelerated 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 the 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 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 inlet / outlet average reaction temperature is a value (hereinafter simply referred to as "reaction temperature") calculated by measuring the inlet temperature of the catalyst bed and the 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.

[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 hr in terms of the mass-based 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, the WHSV is calculated by converting ethanol into ethylene as shown in the following formula: From the viewpoint of excellent productivity of the target compound, the effective raw material supply mass flow rate 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 ) = mass flow rate of effective raw material supply (kg / hr) / amount of catalyst (kg) Mass flow rate of effective raw material supply (kg / hr) = ethylene flow rate (kg / hr) + ethylene-equivalent ethanol mass flow rate (kg / hr) + flow rate of olefins with 4 to 6 carbon atoms (kg / hr) + flow rate of oxygenated compounds with 1 to 6 carbon atoms other than ethanol (kg / hr) Ethylene-equivalent ethanol flow rate (kg / hr) = ethanol flow rate (kg / hr) × molecular weight of ethylene (g / mol) / molecular weight of ethanol (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, deactivating the catalyst. 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> A 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. An 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." An "intermediate pore size zeolite" has a so-called 10-membered oxygen ring in its crystal structure.

[0193] Examples of intermediate pore size 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 (SiO ２ / Al ２ O ３ The silica / alumina (SiO ) molar ratio of the zeolite contained in the zeolite-containing catalyst 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. ２ / Al ２ O ３The silica / alumina molar ratio 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 spectrometry or the like.

[0195] The zeolite synthesis method of the present embodiment is not particularly limited, but can be produced by optimizing various conditions of a conventionally known hydrothermal synthesis method for 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, or a method of hydrothermal synthesis in which MFI zeolite is added as a seed slurry in the crystalline stage. Examples of organic structure-directing agents (SDAs) 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 of MFI zeolite as described above, a suitable catalyst can be obtained by appropriately optimizing synthesis conditions such as the raw material charge composition, including the types of raw materials and additives (SDA), the amount of additive, pH, silica / alumina molar ratio, 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. 5,426,983 and the method exemplified in The Hydrothermal Synthesis of Zeolites (Chemical Reviews, 2003, 103, 663-702).

[0197] Furthermore, 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] The form of phosphorus element includes a polymer of phosphorus (e.g., polyphosphoric acid), an oxide of phosphorus (e.g., P ２ O ５ ), compounds in which phosphorus is added to the aluminum of zeolite, etc. Furthermore, a plurality of these may be contained. When the zeolite contains aluminum, phosphorus has the effect of suppressing dealumination of the zeolite and, in some cases, the effect of improving the propylene yield in the propylene production reaction. In the method according to this embodiment, water is generated in the reactor, and the raw material ethanol may also contain water, so the reactor is likely to become a high-temperature steam atmosphere that causes dealumination. Dealuminization causes the activity of the zeolite-containing catalyst to deteriorate due to structural collapse, but the inclusion of 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, is 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 having relatively high solubility in water are preferred, and more preferred is at least one selected from the group consisting of ammonium phosphate, diammonium hydrogen phosphate, and ammonium dihydrogen phosphate. 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, it is 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 compression molding or extrusion molding of the catalyst components, and spray-dry molding, which is optimal for fluidized bed reaction systems. A binder can also 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, and more preferably in the range of 20 / 80 to 80 / 20. Among these, a silica binder is preferably used 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 an atmosphere that is not particularly limited, but in which a mixed gas of air or an inert gas such as nitrogen and steam (water vapor) is circulated, with 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. This pretreatment step can be performed using a reactor for converting ethanol and ethylene.

[0210] [Regeneration Step] 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 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 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 step and a regeneration step are carried out simultaneously using a two-tower or multi-tower switching type adiabatic reactor. For example, in the case of a three-tower switching type, two towers are used for the reaction step, and at the same time, the remaining tower is used for catalyst regeneration. Thereafter, the reaction step in one of the towers used for the reaction step is stopped to perform catalyst regeneration, and the reaction step is carried out in the one tower used for catalyst regeneration, thereby enabling catalyst regeneration while maintaining the production capacity of the two towers. This type of reaction format is also called a merry-go-round system, and is preferred from the viewpoint of excellent production efficiency because it does not require stopping the production process for catalyst regeneration.

[0212] [Product: Reaction Gas Containing Olefins Having 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. "Reaction gas" refers to the 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, the 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 Step and Recycling Step> 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 also simply referred to as “reactor 1”) and a first distillation column 2. The reaction gas obtained in 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. 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 having 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 by separating the ethylene and propylene from the steam cracking product, the efficiency of the entire process can be improved. 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 using an apparatus including 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 performed 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. 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 the coolant are circulated through a space separated by a wall to perform heat exchange through the wall. Fraction C recovered 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. At least a portion of fraction A may be recycled to reactor 1 as part of the mixed feedstock. In addition, at least a portion of fraction B may be recycled to reactor 1 as part of the mixed feedstock. Fraction D recovered in the cooling step is separated in oil-water separator 7 into fraction E containing mainly hydrocarbons and fraction F containing mainly water. By separating aromatic compounds from fraction E, the aromatic compounds are efficiently separated from the reaction gas. Separation of 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 for efficient production of propylene.

[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 compounds from the side cut stage, separation efficiency can be improved. By providing the distillation column with a side cut stage for withdrawing 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 for Producing Hydrocarbons, etc.] Various chemical products can be obtained by separating 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 three or more carbon atoms. Details of this production method are as described above for 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 cracker's purification system, the target hydrocarbon compounds can be efficiently purified. The hydrocarbon production method according to this embodiment includes: a cracking step for cracking hydrocarbons having two or more carbon atoms; and a purification step for purifying the components obtained in the cracking step. In the purification step, the reaction gas or its purified fraction obtained by the above-described ethanol conversion method is combined. With the above configuration, the target hydrocarbons can be obtained from ethanol resources using a conventional cracker. For example, bio-derived hydrocarbons can be produced by using bioethanol as a raw material in the ethanol conversion method.

[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 an unsaturated hydrocarbon separation step of separating a fraction mainly containing unsaturated hydrocarbons from the reaction gas obtained by the above-described ethanol conversion method. 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 an olefin separation step of separating a fraction mainly containing olefins from the reaction gas obtained by the above-described ethanol conversion method.

[0231] The propylene production method according to this embodiment includes a propylene separation step of separating a fraction mainly containing propylene from the reaction gas obtained by the above-described ethanol conversion method.

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

[0233] The diene production method according to this embodiment includes a diene separation step of separating a fraction mainly containing dienes from the reaction gas obtained by the above-described ethanol conversion method.

[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: an unsaturated hydrocarbon separation step of separating a fraction mainly containing unsaturated hydrocarbons from the reaction gas obtained by the above-described ethanol conversion method; and an acrylic monomer production step of obtaining an acrylic monomer from the unsaturated hydrocarbons obtained by the unsaturated hydrocarbon separation step. In the acrylic monomer production step, a known method for introducing an acrylic monomer from an unsaturated hydrocarbon is used.

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

[0237] The method for producing styrene according to this embodiment includes an ethylene separation step of separating a fraction mainly containing ethylene from the reaction gas obtained by the above-described method for converting ethanol, and a styrene production step of obtaining styrene from the ethylene obtained by the ethylene separation step.

[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 step of polymerizing the monomer obtained by the above-mentioned method for producing a monomer. The step of polymerizing the monomer can be carried out using 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 the present embodiment includes a step of polymerizing a polymerizable composition containing an olefin obtained by the above-described method for producing an olefin. Here, the polymerizable composition may contain an olefin alone as a monomer, or may contain another monomer having an unsaturated bond.

[0240] The method for producing a polypropylene-based polymer according to the present embodiment includes a step of polymerizing a polymerizable composition containing propylene obtained by the above-described method for producing propylene. Here, the polymerizable composition may contain propylene alone as a monomer, or may contain other monomers having an unsaturated bond.

[0241] The method for producing a polyethylene polymer according to the present embodiment includes a step of polymerizing a polymerizable composition containing ethylene obtained by the above-described method for producing ethylene. Here, the polymerizable composition may contain ethylene alone as a monomer, or may contain another monomer having an unsaturated bond.

[0242] The method for producing a diene polymer according to the present embodiment includes a step of polymerizing a polymerizable composition containing a diene obtained by the above-described method for producing a diene. The polymerizable composition may contain only a diene as a monomer, or may contain another monomer having an unsaturated bond.

[0243] The method for producing an acrylic monomer-based polymer according to this embodiment includes a step of polymerizing a polymerizable composition containing an acrylic monomer obtained by the above-described method for producing an acrylic monomer. Here, the polymerizable composition may contain only the acrylic monomer as the monomer, or may contain another monomer having an unsaturated bond.

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

[0245] The method for producing a styrene-based polymer according to the present embodiment includes a step of polymerizing a polymerizable composition containing styrene obtained by the above-described method for producing styrene. Here, the polymerizable composition may contain styrene alone as a monomer, or may contain other monomers having an unsaturated bond.

[0246] Aromatic compounds may be separated from the reaction gas obtained by the above-described ethanol conversion method. The method for producing an aromatic compound according to this embodiment includes an aromatic compound separation step of separating a fraction mainly containing aromatic compounds from the reaction gas obtained by the above-described ethanol conversion method. Examples of aromatic hydrocarbons include benzene, toluene, and xylene.

[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) Silica / Alumina Molar Ratio of Zeolite in Zeolite-Containing Catalyst Zeolite was completely dissolved in a sodium hydroxide solution to prepare a solution. The amounts of Si and Al contained in the solution were measured using an ICP (inductively coupled plasma) emission spectrometer (manufactured by Rigaku, trade name "JY138") in a standard manner, and the silica / alumina molar ratio was derived from the results. The measurement conditions were set as follows: 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 Catalyst The phosphorus and silver contents 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) Structural Type of Zeolite The structural type of 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, trade name "RINT") and referring to the diffraction patterns of known zeolites. The measurement conditions were as follows: Cu cathode, tube voltage: 40 kV, tube current: 30 mA, scan speed: 1 deg / 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 diameter 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 adjusted to a diameter of 1.6 mm and a length of 4 to 6 mm. A predetermined amount of diammonium hydrogen phosphate aqueous solution was loaded onto the obtained molded body to obtain a phosphorus-loaded product. The obtained 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 a pressure of 0.1 MPa and a temperature of 600°C, thereby obtaining Zeolite-Containing Catalyst 1. The phosphorus content in 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), which is a medium pore diameter zeolite, and 30 parts by mass of silica (the moisture content was adjusted using colloidal silica and fumed silica) was kneaded and then extrusion-molded to obtain an extruded molded body adjusted to 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) 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 adjusted to a diameter of 2.1 mm and a length of 4 to 6 mm. A predetermined amount of diammonium hydrogen phosphate aqueous solution was supported on the obtained molded body to obtain a phosphorus-supported product. The obtained phosphorus-supported 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 water vapor was supplied and circulated for 24 hours under conditions of a pressure of 0.1 MPa and a temperature of 600°C, to obtain Zeolite-Containing Catalyst 3. At this time, the phosphorus content in the zeolite-containing catalyst was 0.032% by mass.

[0255] (Preparation of Zeolite-Containing Catalyst 4) 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 adjusted to a diameter of 2.1 mm and a length of 4 to 6 mm. The obtained molded body was calcined at 600 ° C. for 5 hours to obtain a catalyst precursor. The obtained catalyst precursor was stirred in a 0.1 N aqueous sodium nitrate solution for 1 hour, filtered and 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, and the filtration and washing process was repeated three times, followed by calcination at 600 ° C. for 5 hours to obtain a silver-exchanged body. Zeolite-containing catalyst 2 was obtained by supplying and circulating a steam-air mixed gas containing 80% by volume of steam to the silver-exchanged body for 24 hours under conditions of a pressure of 0.1 MPa and a temperature of 600 ° C. 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), which is a medium pore diameter zeolite, and 30 parts by mass of silica (the moisture content was adjusted using colloidal silica and fumed silica) was kneaded and then extrusion-molded to obtain an extruded molded body adjusted to 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) 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 adjusted to a diameter of 1.6 mm and a length of 4 to 6 mm. A predetermined amount of diammonium hydrogen phosphate aqueous solution was loaded onto the obtained molded body to obtain a phosphorus-loaded product. The obtained 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 a pressure of 0.1 MPa and a temperature of 600°C, to obtain Zeolite-Containing Catalyst 5. At this time, the phosphorus content of the zeolite-containing catalyst was 0.085% by mass.

[0258] [Examples 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] [Method for Conversion of 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 olefins 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] Molar ratio of ethylene / C4-C6 olefin (-)=Ethylene molar flow rate (mol / hr) / C4-C6 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 was set to 0, and the distance from the center of the reactor to the inner wall surface of the reactor was set to d, and the temperatures were 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 (°C) = [catalyst bed inlet temperature (°C) + catalyst bed outlet temperature (°C)] / 2

[0266] (Coke Yield) In the following Examples and Comparative Examples, after the reaction was stopped, nitrogen was supplied to the reactor to purge 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. ２ The CO concentration was measured, and the amount of carbon adhering to the catalyst was calculated from this value, which was taken as the amount of coke. The method for analyzing the regeneration gas using a gas chromatograph is described below (Gas Chromatography Analysis Conditions). The coke yield in the following examples and comparative examples 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) + C4-C6 olefin flow rate (kg / hr) + C1-C6 oxygen-containing compound flow rate (kg / hr) other than ethanol

[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) [Regenerated gas analysis] Apparatus: Shimadzu GC-8A Column: The following columns (1) and (2) connected in parallel were used: Column (1): SUS column (internal 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, Inc., USA, directly connected to a SUS resistance column (internal diameter 3 mm, length 1 m) Column temperature: 70°C Carrier gas (helium) flow rate: 60 mL / min

[0271] [Reaction gas analysis] Apparatus: GC-2030 manufactured by Shimadzu Corporation Column: Custom capillary column SPB-1 manufactured by SUPELCO, USA (inner diameter 0.25 mm, length 60 m, film thickness 3.0 μm) Sample gas amount: 1 mL (sampling line kept at 200°C to 300°C) Heating program: Maintain at 40°C for 12 minutes, then heat to 200°C at 5°C / min, and then 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 (approximately 500 mL / min), hydrogen supply pressure 60 kPa (approximately 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 concentration of the target compound in the reaction gas was determined using the calibration curve method, and the mass per hour produced by the reaction was determined. 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) + C4-C6 olefin flow rate (kg / hr) + C1-C6 oxygen-containing compound flow rate (kg / hr) other than ethanol

[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 supplied to a reactor packed with a zeolite-containing catalyst so that the 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 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 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. The average propylene yield from the start of the reaction to the end of the reaction 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 are shown in Table 1 together with the reaction conditions.

[0278] Comparative Example 2 A reaction was carried out in the same manner as in Example 1, except that no ethanol was used and only ethylene feed gas was used, and the catalyst bed inlet temperature was set to 450° C. However, since the temperature at the catalyst bed outlet exceeded 650° C. and continued to rise, the reaction was stopped after 1 hour from a safety standpoint. 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] 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, respectively. The inlet / outlet temperature difference and reaction results for each are shown in Table 1.

[0280]

[0281] The results of Example 1 and Comparative Examples 1 and 2 show 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 in the composition shown in Table 2, and steam was heated and supplied to a reactor packed with a zeolite-containing catalyst so as to achieve a WHSV of 4.9, and a 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 A 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 ppm by mass. The reaction results are shown in Table 3, along with the reaction conditions.

[0284] Example 9 A 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 ppm by mass. The reaction results are shown in Table 3, along with the reaction conditions.

[0285] Example 10 A 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 are shown in Table 3, along with the reaction conditions.

[0286] Example 11 A 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 ppm by mass. 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]

[0290]

[0291] [Examples 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] [Method for Conversion of 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 C4-6 olefin / methanol, and the molar ratio of ethylene / ethanol in the examples and comparative examples were calculated according to the following formulas: Molar ratio of methanol / ethanol (-) = molar flow rate of methanol (mol / hr) / molar flow rate of ethanol (mol / hr) Molar ratio of methanol / C4-6 olefin (-) = molar flow rate of methanol (mol / hr) / molar flow rate of C4-6 olefin (mol / hr) Molar ratio of ethylene / ethanol (-) = molar flow rate of ethylene (mol / hr) / molar flow rate of ethanol (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 was set to 0, and the distance from the center of the reactor to the inner wall surface of the reactor was set to d, and the temperatures were 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) Reactions were carried out according to the following Examples and Comparative Examples 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 and outlet reaction temperature (°C) = [catalyst bed inlet temperature (°C) + catalyst bed outlet temperature (°C)] / 2

[0296] (Coke Yield) In the following Examples and Comparative Examples, after the reaction was stopped, nitrogen was supplied to the reactor to purge 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. ２ , the CO concentration was measured, and the amount of carbon adhering to the catalyst was calculated from this value, which was taken as the amount of coke. The method for analyzing regeneration gas using a gas chromatograph is described below (Gas Chromatography Analysis Conditions). Hereinafter, the coke yield in the Examples and Comparative Examples 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 + C4-6 olefin flow rate (kg / hr) + flow rate of oxygenated compounds having C1-6 other than methanol and ethanol (kg / hr) Ethylene-equivalent ethanol flow rate (kg / hr) = ethanol flow rate (kg / hr) × 0.609 Methylene-equivalent methanol flow rate (kg / hr) = methanol flow rate (kg / hr) × 0.438

[0297] (Gas chromatograph analysis conditions) <Regenerated gas analysis> Apparatus: Shimadzu GC-8A Column: The following columns (1) and (2) connected in parallel were used: Column (1): SUS column (internal 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, Inc., USA, directly connected to a SUS resistance column (internal diameter 3 mm, length 1 m) Column temperature: 70°C Carrier gas (helium) flow rate: 60 mL / min

[0298] <<Reaction Gas Analysis>> Apparatus: GC-2030 manufactured by Shimadzu Corporation Column: Custom capillary column SPB-1 manufactured by SUPELCO, USA (inner diameter 0.25 mm, length 60 m, film thickness 3.0 μm) Sample gas amount: 1 mL (sampling line kept at 200°C to 300°C) Heating program: Hold at 40°C for 12 minutes, then heat to 200°C at 5°C / min, and hold at 200°C for 22 minutes. Split ratio: 200:1 Carrier gas (nitrogen) flow rate: 120 mL / min FID detector: air supply pressure 50 kPa (approximately 500 mL / min), hydrogen supply pressure 60 kPa (approximately 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 propylene concentration, benzene concentration, toluene concentration, and carbon number 8 aromatic hydrocarbon concentration in the reaction gas were determined using a calibration curve method, and the propylene mass and aromatic mass per hour produced by the reaction were determined. The aromatic mass per hour produced by the reaction is the total mass of benzene, toluene, and carbon number 8 aromatic hydrocarbons produced per hour by the reaction. The propylene yield and aromatic yield were calculated using 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) Aromatics yield (mass %) = mass of aromatics 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) + C4-C6 olefin flow rate (kg / hr) + C1-C6 oxygen-containing compounds flow rate (kg / hr) other than methanol and ethanol 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 the WHSV was 3.8, and the reaction was carried out. At this time, 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 aromatics yield was 7.8 mass%. In addition, 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 supplied to a reactor packed with a zeolite-containing catalyst so that the WHSV was 3.8, and the reaction was carried out. At this time, 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 aromatics yield was 7.5 mass%. In addition, 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 supplied to a reactor packed with a zeolite-containing catalyst so that the WHSV was 3.8, and the reaction was carried out. At this time, 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 aromatics yield was 8.8 mass%. In addition, 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 an ethanol feedstock gas 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 / 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. In addition, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 483 ppm by mass. The reaction results are shown in Table 4 together with the reaction conditions.

[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. Therefore, 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.

[0304]

[0305] From the results of Examples B1 to B3 and Comparative Examples B1 and B2, it was found that by using a mixed feedstock with a specific range of methanol / ethanol molar ratio, it is 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 having 4 or more carbon atoms, mainly containing hydrocarbons having 4 to 8 carbon atoms, with a methanol / ethanol molar ratio of 0.35 and a C4-6 olefin / methanol molar ratio of 0.97, and having the composition shown in Table 5, was heated and supplied to a reactor packed with a zeolite-containing catalyst so as to achieve a WHSV of 4.9, and the reaction was carried out. At this time, the inlet temperature of the catalyst bed was 566°C, the outlet temperature was 514°C, and the average 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%. 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 6. In this example, the aromatics yield was calculated from the difference between the aromatics concentration in the feedstock and the aromatics concentration in the reaction gas.

[0307] [Example B5] 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 reaction was carried out in the same manner as in Example B4, except that 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% by mass, and the aromatics yield was 7.8% by mass. In addition, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 297 ppm by mass. The reaction results are shown in Table 6 together with the reaction conditions.

[0308] [Example B6] 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 reaction was carried out in the same manner as in Example B4, except that 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% ​​by mass, and the average aromatics yield was 7.6% by mass. In addition, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 270 ppm by mass. The reaction results are shown in Table 6 together with the reaction conditions.

[0309] [Example B7] 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 reaction was carried out in the same manner as in Example B4, except that 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% by mass, and the aromatics yield was 7.6% by mass. In addition, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 266 ppm by mass. The reaction results are shown in Table 6 together 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 / 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 average 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]

[0312]

[0313] [Example B8] 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 reaction was carried out in the same manner as in Example B4, except that the inlet temperature of the catalyst bed was adjusted to 555°C. At this time, 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. In addition, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 251 ppm by mass. The reaction results are shown in Table 7 together with the reaction conditions.

[0314] [Example B9] 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 reaction was carried out in the same manner as in Example B4, except that the inlet temperature of the catalyst bed was adjusted to 544°C. At this time, 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. In addition, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 280 ppm by mass. The reaction results are shown in Table 7 together with the reaction conditions.

[0315] [Example B10] 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 reaction was carried out in the same manner as in Example B1, except that the inlet temperature of the catalyst bed was adjusted to 546°C. At this time, 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. In addition, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 291 ppm by mass. The reaction results are shown in Table 7 together with the reaction conditions.

[0316]

[0317] [Examples 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] [Method for Conversion of 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 C4-6 olefin / ethylene in the examples and comparative examples are calculated by the following formulas: Molar ratio of ethylene / ethanol (-) = Molar flow rate of ethylene (mol / hr) / Molar flow rate of ethanol (mol / hr) Molar ratio of C4-6 olefin / ethylene (-) = Molar flow rate of C4-6 olefin (mol / hr) / Molar flow rate of ethylene (mol / hr)

[0320] (Temperature Measurement) The temperatures at the catalyst bed inlet and catalyst bed 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 negligibly small.

[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 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 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 and outlet reaction temperature (°C) = [catalyst bed inlet temperature (°C) + catalyst bed outlet temperature (°C)] / 2

[0322] (Coke Yield) In the following Examples and Comparative Examples, after the reaction is stopped, nitrogen is supplied to the reactor to purge 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. ２ The CO concentration is measured, and the amount of carbon adhering to the catalyst is calculated from this value, which is taken as the amount of coke. 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) + C4-C6 olefin flow rate (kg / hr) + C1-C6 oxygen-containing compound flow rate (kg / hr) other than ethanol

[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) Apparatus: Shimadzu GC-8A Column: The following columns (1) and (2) connected in parallel were used: Column (1): SUS column (internal diameter 3 mm, length 3 m) packed with 80-100 mesh molecular sieve 5A (Fujifilm Wako Pure Chemical Industries, Ltd.) Column (2): 80-100 mesh Porapac-Q (internal diameter 3 mm, length 2 m) manufactured by Waters Associates, Inc. (USA) directly connected to a SUS resistance column (internal diameter 3 mm, length 1 m) Column temperature: 70°C Carrier gas (helium) flow rate: 60 mL / min

[0327] (Reaction Gas Analysis) Apparatus: GC-2030 manufactured by Shimadzu Corporation Column: Custom capillary column SPB-1 manufactured by SUPELCO, USA (inner diameter 0.25 mm, length 60 m, film thickness 3.0 μm) Sample gas amount: 1 mL (sampling line kept at 200°C to 300°C) Heating program: Maintain at 40°C for 12 minutes, then heat to 200°C at 5°C / min, and then 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 (approximately 500 mL / min), hydrogen supply pressure 60 kPa (approximately 50 mL / min) Measurement method: The TCD detector and 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, and the calibration curve method was used to determine the concentration of the target compound in the reaction gas, and the mass per hour produced by the reaction.

[0328] (Propylene Yield) 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 the 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) + C4-C6 olefin flow rate (kg / hr) + C1-C6 oxygen-containing compound flow rate (kg / hr) other than ethanol

[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 by the following formula. The recovery yield of each component represents the discharge amount of each component relative to the raw material introduced into the reactor. The discharge amount is the mass per hour of each component discharged to the outside of the system after the separation process. Propylene recovery yield (mass%) = propylene discharge rate (kg / hr) / mixed raw material feed mass flow rate (kg / hr) Aromatic compound recovery yield (mass%) = aromatic compound discharge rate (kg / hr) / mixed raw material feed 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 the WHSV was 3.8, and the reaction was carried out. The catalyst bed inlet temperature 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. This Reference Example demonstrated that by controlling the molar ratio of ethylene to ethanol, ethylene and ethanol could be converted to target compounds 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) having 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 as to achieve a WHSV of 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 ppm by mass.

[0334] Example C1: The effectiveness of the ethanol conversion method according to this embodiment was verified using the apparatus shown in FIG. 9 . A 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, where it was separated into fraction C, primarily containing hydrocarbons with a carbon number of 6 or less, and fraction D, primarily containing water and hydrocarbons with a carbon number of 7 or more. Fraction C was passed through first distillation column 2, where it was separated into fraction A, primarily containing hydrocarbons with a carbon number of 3 or less, and fraction B, primarily containing hydrocarbons with a carbon number of 4 or more. These fractions were used as feedstocks such that the recycle ratio of fraction A was 0.60 and the recycle ratio of fraction B was 0.90. Based on the results of Reference Examples 1 and 2 described above, the propylene yield and other data for steady-state operation of the above process are shown in Table 8. The feedstock introduced into reactor 1 had an ethylene / ethanol molar ratio of 0.40 and a C4-6 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 was supplied to the reactor at a WHSV of 3.8. The catalyst bed inlet temperature was 553°C, resulting in an outlet temperature of 527°C and an average inlet / outlet reaction temperature of 540°C. The average propylene yield from the start of the reaction to the end of the reaction was 22.1% by mass, and the coke yield of the zeolite-containing catalyst after 48 hours of operation was 251 ppm by mass. The propylene recovery yield at the outlet of the separation step was 5.4% by mass, and the aromatic compound recovery yield was 12.3% by mass.

[0335] Example C2 The effectiveness of the ethanol conversion method according to this embodiment was verified using the apparatus shown in FIG. 10 . A raw material was supplied to a 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 contained hydrocarbons with a carbon number of 6 or less, and fraction D, which mainly contained water and hydrocarbons with a carbon number of 7 or more. Fraction C was passed through a first distillation column 2 to separate fraction A, which mainly contained hydrocarbons with a carbon number of 3 or less, and fraction B, which mainly contained hydrocarbons with a carbon number of 4 or more. The resulting fraction A was passed through a second distillation column 8 to separate fraction A-1, which mainly contained hydrocarbons with a carbon number of 2 or less, and fraction A-2, which mainly contained hydrocarbons with a carbon number of 3. These fractions were used as raw materials so that the recycle ratio of fraction A-1 was 0.72, and the recycle ratio of fraction B was 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 0.36. The composition of 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 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 recovery yield of propylene obtained at the outlet of the separation step is 15.5 mass%, and the recovery yield of aromatic compounds 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 effectiveness of the conversion method according to this embodiment was verified using the apparatus shown in FIG. 11 . A raw material was supplied to reactor 1, which was packed with a zeolite-containing catalyst 1, to obtain a reaction gas. The resulting reaction gas was passed through cooling device 6 to separate fraction C, which mainly contained hydrocarbons with a carbon number of 6 or less, and fraction D, which mainly contained 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 contained hydrocarbons with a carbon number of less than 3, fraction B, which mainly contained hydrocarbons with a carbon number of 4 or more, and fraction E, which mainly contained hydrocarbons with a carbon number of 3. These fractions were used as raw materials so that the recycle ratio of fraction A was 0.78 and the recycle ratio of fraction B was 0.90. Based on the results of Reference Examples 1 and 2 described above, the propylene yield and other data for steady-state operation of the above process are shown in Table 8. The raw material introduced into reactor 1 had an ethylene / ethanol molar ratio of 0.40 and a C4-6 olefin / ethylene molar ratio of 0.39. 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 feed rate of the feedstock 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 recovery yield of propylene obtained at the outlet of the separation step is 12.1 mass%, and the recovery yield of aromatic compounds is 12.0 mass%. A comparison of Example C1 and Example C3 shows that the propylene recovery yield is improved by providing a side cut stage in the distillation column 2, which extracts fraction E mainly containing hydrocarbons with a carbon number of 3 from the middle of the first distillation column 2.

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

[0338] [Comparative Example C2] The effect of the conversion method using the apparatus having the reactor 1 shown in FIG. 13 was verified. The raw material was supplied to the reactor 1 filled with the zeolite-containing catalyst 1 to obtain a reaction gas. A mixed raw material with the same composition as the raw material was obtained by mixing with ethanol so that the reaction gas recycle ratio was 0.65. The raw material introduced into the reactor 1 had an ethylene / ethanol molar ratio of 0.40 and a C4-C6 olefin / ethylene molar ratio of 0.15. The feed rate of the raw material to the reactor 1 was WHSV = 3.8, the inlet temperature of the catalyst bed was 537°C, the outlet temperature was 543°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 23.6% by mass. Furthermore, the coke yield of the zeolite-containing catalyst after 48 hours of operation was 310 ppm by mass. The recovery yield of propylene obtained at the outlet of the separation step was 2.8 mass%, and the recovery yield of aromatic compounds was 7.4 mass%. Comparison of Example C1, Comparative Example C1, and Comparative Example C2 shows that the recovery yield of propylene is improved by providing a distillation step and a cooling step when recycling the reaction gas.

[0339]

[0340]

[0341] Example C4 The procedure was the same as in Example C2, except for changing the composition of the raw material introduced into reactor 1. These fractions were used as raw materials so that the recycle ratio of fraction A-1 was 0.42 and the recycle ratio of fraction B was 0.90. 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 had an ethylene / ethanol molar ratio of 0.20 and a C4-C6 olefin / ethylene molar ratio of 0.61. The composition of 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 was WHSV = 3.8, the inlet temperature of the catalyst bed was 563°C, the outlet temperature was 517°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 22.1 mass%, and the coke yield of the zeolite-containing catalyst after 48 hours of operation was 256 mass ppm. The recovery yield of propylene obtained at the outlet of the separation step was 13.8 mass%, and the recovery yield of aromatic compounds was 12.5 mass%.

[0342] Example C5 The same procedure as in Example C2 was repeated except for changing the composition of the raw material introduced into reactor 1. These fractions were used as raw materials so that the recycle ratio of fraction A-1 was 0.94 and the recycle ratio of fraction B was 0.90. 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 had an ethylene / ethanol molar ratio of 0.60 and a C4-C6 olefin / ethylene molar ratio of 0.27. The composition of 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 was WHSV = 3.8, the inlet temperature of the catalyst bed was 534°C, the outlet temperature was 546°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 23.8% by mass, and the coke yield of the zeolite-containing catalyst after 48 hours of operation was 220 ppm by mass. The recovery yield of propylene obtained at the outlet of the separation step was 17.1% by mass, and the recovery yield of aromatic compounds was 15.5% by 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 cooling device 6 to separate fraction C containing mainly hydrocarbons with a carbon number of 6 or less and fraction D containing mainly water and hydrocarbons with a carbon number of 7 or more. Fraction C was fed to first distillation column 2 to separate it into fraction A containing mainly hydrocarbons with a carbon number of 3 or less and fraction B containing mainly hydrocarbons with a carbon number of 4 or more. The obtained fraction A was fed to second distillation column 8 to separate it into fraction A-1 containing mainly hydrocarbons with a carbon number of 2 or less and fraction A-2 containing mainly 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 in 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 of Example C2 and Example C6 shows that recycling fraction B, which mainly contains hydrocarbons with a carbon number of 4 or more, improves the recovery yield of aromatic compounds.

[0344] Example C7: The effect 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 zeolite-containing catalyst 1 to obtain a reaction gas. The resulting reaction gas was passed through cooling device 6 to separate fraction C, which mainly contained hydrocarbons with a carbon number of 6 or less, and fraction D, which mainly contained 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 contained hydrocarbons with a carbon number of 3 or less, and fraction B, which mainly contained hydrocarbons with a carbon number of 4 or more. The resulting fraction A was passed through second distillation column 8 to separate fraction A-1, which mainly contained hydrocarbons with a carbon number of 2 or less, and fraction A-2, which mainly contained hydrocarbons with a carbon number of 3. These fractions were used as feedstocks so that the recycle ratio of fraction A-1 was 0.28 and the recycle ratio of fraction B was 0.90. 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. The feedstock introduced into reactor 1 had an ethylene / ethanol molar ratio of 0.80 and a C4-C6 olefin / ethylene molar ratio of 0.23. Table 9 shows the composition of components recycled from fraction B contained in the feedstock (mainly hydrocarbons with 4 or more carbon atoms). The feedstock feed rate to reactor 1 was WHSV = 3.8, the catalyst bed inlet temperature was 520°C, the outlet temperature was 560°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 24.5 mass%, and the coke yield of the zeolite-containing catalyst after 48 hours of operation was 321 mass ppm. The propylene recovery yield at the outlet of the separation step was 14.8 mass%, and the aromatic compound recovery yield was 13.4 mass%.

[0345]

[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.

[0347] 1: adiabatic reactor, 12: reaction casing, 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

DEPCT671. Method for ethanol conversion, comprising: exposure of a feedstock mixture containing ethylene and ethanol to a catalyst in an adiabatic reactor to obtain a reaction gas containing olefins with 3 or more carbon atoms.

2. Method for ethanol conversion according to claim 1, where the molar ratio of ethylene / ethanol in the feedstock mixture is 0.20 to 2.

5.

3. Method for ethanol conversion according to claim 1, where the molar ratio of... The ethylene / ethanol ratio in the raw material mixture is 0.20 to 2.

04. The method for ethanol conversion under claim 1, which includes: separation of ethylene and propylene from reaction gases.

5. The method for ethanol conversion under claim 1, where the raw material mixture contains olefins with 4 to 6 carbon atoms.

6. The method for ethanol conversion under claim 5, where the molar ratio of olefins with 4 to 6 carbon atoms / ethylene in the raw material mixture is 3.0 or less. 7.Methods for ethanol conversion, comprising: exposure of a feedstock mixture containing methanol and ethanol to a catalyst in an adiabatic reactor to obtain a reaction gas consisting of olefins with 3 or more carbon atoms.

8. Methods for ethanol conversion according to claim 7, where the molar ratio of methanol / ethanol in the feedstock mixture is 0.050 to 2.

09. Methods for ethanol conversion according to claim 7, where the molar ratio of methanol / ethanol...

10. The method for ethanol conversion under claim 7, which includes: separation of ethylene and propylene from reaction gases.

11. The method for ethanol conversion under claim 7, where the raw material mixture contains olefins with 4 to 6 carbon atoms.

12. The method for ethanol conversion under claim 7, where the molar ratio of olefins with 4 to 6 carbon atoms / methanol in the raw material mixture is 3.0 or less. 13.The method for ethanol transformation under claim 7, which includes: recycling at least a portion of the reaction gas or fractions obtained by reaction gas separation to the reactor for use as part of the feedstock mixture.

14. The method for ethanol transformation, which includes: contact of the feedstock mixture containing ethanol and ethylene with a catalyst in an adiabatic reactor to obtain a reaction gas consisting of olefins with 3 or more carbon atoms; separation of the reaction gas into fractions A, mainly composed of hydrocarbons with 2 to 3 carbon atoms, and fractions B, mainly composed of hydrocarbons with 4 to 6 carbon atoms, by a first distillation column; and recycling at least a portion of fraction A as part of the feedstock mixture to the reaction step.15.The method for the conversion of ethanol under claim 14, which includes the following additional components:

16. The separation of fraction A into fraction A-1, primarily composed of hydrocarbons with 2 carbon atoms, and fraction A-2, primarily composed of hydrocarbons with 3 carbon atoms, by a second distillation column, where recycling includes the recycling of at least part of fraction A-1 to obtain reactive gas for use as part of the feedstock mixture.

17. The method for the conversion of ethanol under claim 14, where recycling includes the recycling of at least part of fraction B to exposure for use as part of the feedstock mixture.

18. The method for the conversion of ethanol under claim 14, which includes the following additional components:

19. The separation of the reactive gas, by cooling, into fraction C, primarily composed of hydrocarbons with 6 carbon atoms or fewer, and fraction D, primarily composed of water and hydrocarbon compounds with 7 carbon atoms or more.The method for ethanol conversion under claim 14, in which separation by the first distillation column is included with the acquisition of an overflow which is discharged in the middle by the preparation of a side cut-off layer in the first distillation column.

19. The method for ethanol conversion under claim 1, which is further included with: the separation of the reaction gas into fraction A, mainly composed of hydrocarbons with 1 to 3 carbon atoms, and fraction B, mainly composed of hydrocarbons with 4 to 8 carbon atoms; and the separation of ethylene and propylene from fraction A.

20. The method for ethanol conversion under claim 19, which is further included with: the recycling of at least a portion of fraction B to the reactor for use as part of the feedstock mixture.21.The method for ethanol conversion under claim 19, which includes: the separation of fraction B into fraction B1, primarily composed of aliphatic hydrocarbons with 4 to 6 carbon atoms, and fraction B2, primarily composed of aromatic compounds; and the recycling of at least a portion of fraction B1 to a reactor for use as part of the feedstock mixture.

22. The method for ethanol conversion under claim 19, which includes: the introduction of fraction B into steam cracking to obtain the product.

22. Steam cracking of ethylene and propylene; and separation of ethylene and propylene from the steam cracking products.

23. Method for ethanol transformation according to claim 1, where the reactor is an adiabatic fixed-bed reactor.

24. Method for ethanol transformation according to claim 1, where the reactor is a single-stage adiabatic fixed-bed reactor.

25. Method for ethanol transformation according to claim 1, which includes the additional: combustion of coke deposited on the catalyst. 26.

27. Method for ethanol conversion according to claim 1, where the outlet temperature of the catalyst bed is 450°C to 590°C.

28. Method for ethanol conversion according to claim 1, where the inlet temperature of the catalyst bed is 450°C to 590°C.

29. Method for ethanol conversion according to claim 1, where the temperature difference between the outlet temperature of the catalyst bed and the inlet temperature of the catalyst bed is -80K to 80K.

30. Method for ethanol conversion according to claim 29, where the zeolite-containing catalyst consists of medium-pore-sized zeolites.

31. Method for ethanol conversion according to claim 29, where the molar ratio of silica / alumina of the zeolites in the zeolite-containing catalyst is 20 to 2000.

32. Method for ethanol conversion according to claim 29, where the zeolite-containing catalyst consists of phosphorus or silver. 33.Methods for the production of hydrocarbons, comprising: contact of a mixture of raw materials containing ethylene and ethanol with a catalyst in an adiabatic reactor to obtain a reaction gas consisting of olefins with 3 or more carbon atoms.

34. Methods for the production of hydrocarbons, comprising: the cracking step of hydrocarbons with 2 or more carbon atoms; and the purification step of the purification of the component obtained in the cracking step, in which, in the purification step, the reaction gas obtained by one of the methods for ethanol conversion under Reputations 1 to 32 or its purified fraction is combined with that component.

35. Methods for the production of monomers, comprising: the separation step of unsaturated hydrocarbons, comprising the separation of a fraction mainly consisting of unsaturated hydrocarbons from the reaction gas obtained by one of the methods for ethanol conversion under Reputations 1 to 32.36.Methods for the production of olefins, comprising: an olefin separation procedure for the separation of olefin-based fractions from reaction gases, which is obtained by any of the ethanol conversion methods in Claims 1 to 3237. Methods for the production of propylene, comprising: a propylene separation procedure for the separation of propylene-based fractions from reaction gases, which is obtained by any of the ethanol conversion methods in Claims 1 to 3238. Methods for the production of ethylene, comprising: an ethylene separation procedure for the separation of ethylene-based fractions from reaction gases, which is obtained by any of the ethanol conversion methods in Claims 1 to 3239. Methods for the production of diene, comprising: a diene separation procedure for the separation of diene-based fractions from reaction gases, which is obtained by any of the ethanol conversion methods in Claims 1 to 3240.Methods for the production of acrylic monomer, comprising: the separation procedure of unsaturated hydrocarbon fractions primarily composed of unsaturated hydrocarbons from reaction gases, which are obtained by any of the ethanol conversion methods in Reputations 1 to 32; and the acrylic monomer production procedure for the acquisition of acrylic monomer from unsaturated hydrocarbons obtained by the separation procedure of unsaturated hydrocarbons.

41. Methods for the production of acrylonitrile, comprising: the separation procedure of propylene fractions primarily composed of propylene from reaction gases, which are obtained by any of the ethanol conversion methods in Reputations 1 to 32; and the acrylonitrile production procedure for the acquisition of acrylonitrile from propylene obtained by the propylene separation procedure.42.Methods for the production of styrene, comprising: the ethylene separation procedure of the fraction primarily composed of ethylene from reaction gases, which is obtained by any of the ethanol conversion methods in claims 1 to 32; and the styrene production procedure of the acquisition of styrene from ethylene, which is obtained by the ethylene separation procedure 43. Methods for the production of polymers, comprising: the polymerization procedure of monomers, which is obtained by the methods in claim 35 44. Methods for the production of olefin-based polymers, comprising: the polymerization procedure of polymerizable olefin-based components, which is obtained by the methods in claim 36 45. Methods for the production of polypropylene-based polymers, comprising: the polymerization procedure of polymerizable propylene-based components, which is obtained by the methods in claim 37 46.Methods for the production of polyethylene-based polymers, comprising: the polymerization procedure of polymerizes polymerizeable components containing ethylene obtained by the method specified in Patent 3847. Methods for the production of diene-based polymers, comprising: the polymerization procedure of polymerizes polymerizeable components containing diene obtained by the method specified in Patent 3948. Methods for the production of acrylic monomer-based polymers, comprising: the polymerization procedure of polymerizes polymerizeable components containing acrylic monomer obtained by the method specified in Patent 4049. Methods for the production of acrylonitrile-based polymers, comprising: the polymerization procedure of polymerizes polymerizeable components containing acrylonitrile obtained by the method specified in Patent 4150.Methods for the production of styrene-based polymers, comprising: a procedure for polymerizing polymerizable compounds containing styrene, which are obtained by the method specified in Patent 4251. Methods for the production of aromatic compounds, comprising: a procedure for separating aromatic compounds, comprising: a fractionation primarily composed of aromatic compounds from reaction gases, which are obtained by any of the ethanol conversion methods specified in Patents 1 to 3252. Methods for the production of aromatic monomers, comprising: a procedure for the production of aromatic monomers, comprising: an aromatic monomer production procedure, comprising: the acquisition of aromatic monomers from aromatic compounds, which are obtained by the method specified in Patent 5153. Methods for the production of polymers based on aromatic monomers, comprising: a procedure for polymerizing polymerizable compounds containing aromatic monomers, which are obtained by the method specified in Patent 5254.The ethanol conversion apparatus, comprising: a reactor which contacts the feedstock mixture of ethanol and ethylene with a catalyst in an adiabatic reactor to obtain a reaction gas consisting of olefins with 3 or more carbon atoms; and a first distillation column which separates the reaction gas into fraction A, primarily composed of hydrocarbons with 2 to 3 carbon atoms, and fraction B, primarily composed of hydrocarbons with 4 to 6 carbon atoms, in which at least a portion of fraction A is recycled to the reactor to be used as part of the feedstock mixture.

55. The ethanol conversion apparatus pursuant to claim 54, comprising additionally: a second distillation column which separates fraction A into fraction A-1, primarily composed of hydrocarbons with 2 carbon atoms, and fraction A-2, primarily composed of hydrocarbons with 3 carbon atoms, in which at least a portion of fraction A-2 is recycled to the reactor to be used as part of the feedstock mixture.56.The equipment for the ethanol conversion under claim 55, in which the first distillation column has a side-cut-off layer for obtaining an overflow which is discharged mid-stream;

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