WO2024070182A1 - エタノールの変換方法、炭化水素の製造方法、プロピレンの製造方法、芳香族化合物の製造方法、及び、エタノールの変換装置 - Google Patents

エタノールの変換方法、炭化水素の製造方法、プロピレンの製造方法、芳香族化合物の製造方法、及び、エタノールの変換装置 Download PDF

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WO2024070182A1
WO2024070182A1 PCT/JP2023/027601 JP2023027601W WO2024070182A1 WO 2024070182 A1 WO2024070182 A1 WO 2024070182A1 JP 2023027601 W JP2023027601 W JP 2023027601W WO 2024070182 A1 WO2024070182 A1 WO 2024070182A1
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ethanol
dehydration
reactor
catalyst
raw material
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English (en)
French (fr)
Japanese (ja)
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鉄平 浦山
隆介 宮崎
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Priority to EP23871425.7A priority Critical patent/EP4596525A1/en
Priority to CN202380068889.4A priority patent/CN119947999A/zh
Priority to KR1020257010197A priority patent/KR20250057863A/ko
Priority to JP2024549794A priority patent/JPWO2024070182A1/ja
Publication of WO2024070182A1 publication Critical patent/WO2024070182A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/001—Processes specially adapted for distillation or rectification of fermented solutions
    • B01D3/002—Processes specially adapted for distillation or rectification of fermented solutions by continuous methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/44—Noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/865—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an ether
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
    • C07C2529/44—Noble metals

Definitions

  • the present invention relates to a method for converting ethanol, a method for producing hydrocarbons, a method for producing propylene, a method for producing aromatic compounds, and an apparatus for converting ethanol.
  • Lower olefins and aromatic compounds are important core raw materials in the chemical industry, and as demand for propylene in particular is expected to increase, various production methods have been actively developed and improved.
  • One commonly known method for producing propylene is to bring naphtha or olefins into contact with a catalyst that uses zeolite as the active species.
  • Patent Document 1 discloses a method for converting olefins or alcohols.
  • Patent Document 2 discloses a pentasil-type zeolite as a catalyst.
  • Patent Document 3 discloses a zinc oxide-cerium supported zeolite as a catalyst.
  • Patent Document 4 shows a method for producing lower olefins using an oxygen-containing compound (oxygenate) and an olefin having 4 or more carbon atoms as raw materials.
  • Patent Document 5 shows a method for producing lower olefins using lower alcohols and naphtha as raw materials.
  • the reaction of converting ethylene to propylene or aromatic compounds after it is produced is an exothermic reaction, and in some cases the temperature inside the reactor increases, resulting in a large amount of by-products such as coke being produced, which reduces the yield of the target compound.
  • Patent Documents 1 to 3 disclose techniques for converting each raw material into the target olefin using a zeolite catalyst, but these techniques involve large endothermic and exothermic generation, making temperature control difficult.
  • 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, in a reaction using ethanol as a raw material, which induces an endothermic reaction, temperature control becomes difficult.
  • the present invention aims to provide an ethanol conversion method that allows easy control of the temperature inside the reactor and efficiently converts ethanol into a target compound, a method for producing hydrocarbons, a method for producing propylene, a method for producing aromatic compounds, and an ethanol conversion device.
  • the inventors have discovered that, when producing olefins having 3 or more carbon atoms from ethanol, a dehydration process in which ethanol is dehydrated and an olefin conversion process are performed, the mixed raw material contains an ether, and the value represented by formula (1) in the mixed raw material is set within a predetermined range, making it easy to control the temperature inside the reactor and enabling ethanol to be converted to the target compound with a high yield.
  • the present invention includes the following embodiments.
  • the mixed raw material contains an ether
  • the following formula (1) (In formula (1), EY is the molar amount of ethylene contained in the mixed raw material, EtOH is the molar amount of ethanol contained in the mixed raw material, and Ether is the molar amount of ether contained in the mixed raw material.) is 0.20 to 4.0.
  • [2] The method for converting ethanol according to [1], wherein the value represented by the formula (1) in the mixed raw material is 0.40 to 3.0.
  • [3] The method for converting ethanol according to [1] or [2], wherein the ether comprises at least one selected from the group consisting of diethyl ether, methyl tertiary butyl ether, and ethyl tertiary butyl ether.
  • [4] The method for converting ethanol according to any one of [1] to [3], wherein the content of ether in the mixed raw material is 20 mass% or less.
  • a method for converting ethanol comprising: [6] The method for converting ethanol according to [5], wherein the conversion rate of ethanol in the dehydrated raw material in the dehydration step is 90 mol % or more.
  • a method for converting ethanol comprising: [8] The method for converting ethanol according to [7], wherein a weight ratio E1/E2 of the ethanol (E1) supplied into the reactor in the dehydration step to the ethanol (E2) supplied into the reactor in the olefin conversion step is 0.10 to 4.0.
  • the method includes a separation step of 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 6 carbon atoms, The method for converting ethanol according to any one of [1] to [14].
  • the mixed raw material contains an ether, In the mixed raw material, the following formula (1): (In formula (1), EY is the molar amount of ethylene contained in the mixed raw material, EtOH is the molar amount of ethanol contained in the mixed raw material, and Ether is the molar amount of ether contained in the mixed raw material.) is 0.20 to 4.0.
  • a method for producing propylene comprising: [23] an aromatic compound separation step of separating a fraction mainly containing aromatic compounds from the reaction gas obtained by the ethanol conversion method according to any one of [1] to [21];
  • a method for producing an aromatic compound comprising: [24] a reactor for dehydrating an ethanol-containing dehydration raw material with a dehydration catalyst to obtain an ethylene-containing dehydration reaction gas; a reactor for contacting a mixed feedstock containing the dehydration reaction gas with an olefin conversion catalyst to obtain a reaction gas containing olefins having 3 or more carbon atoms; 16.
  • An apparatus for converting ethanol comprising: [25] The ethanol conversion apparatus according to [24], further comprising a separation device for 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 6 carbon atoms. [26] an ethanol supply line for introducing ethanol into the reactor for obtaining the reaction gas; a dehydration reaction gas supply line for introducing the dehydration reaction gas into a reactor for obtaining the reaction gas; The ethanol conversion device according to [24] or [25],
  • the present invention provides an ethanol conversion method that allows easy control of the temperature inside the reactor and efficiently converts ethanol into a target compound, a method for producing hydrocarbons, a method for producing propylene, a method for producing aromatic compounds, and an ethanol conversion device.
  • FIG. 1 shows a schematic diagram of one embodiment of an apparatus for converting ethanol.
  • FIG. 2 shows a schematic diagram of one embodiment of a fixed-bed, single-stage adiabatic reactor.
  • FIG. 3 shows a schematic diagram of one embodiment of a single tubular fixed-bed isothermal reactor.
  • FIG. 4 shows a schematic diagram of one embodiment of an apparatus for converting ethanol.
  • FIG. 5 shows a schematic diagram of one embodiment of an apparatus for converting ethanol.
  • FIG. 6 shows a schematic diagram of one embodiment of an apparatus for converting ethanol.
  • the present invention will be described in detail below. Note that the present invention is not limited to the following embodiment (present embodiment), and can be practiced in various modifications within the scope of the gist thereof.
  • the numerical ranges indicated using “to” indicate ranges including the numerical values before and after “to” as the minimum and maximum values, respectively.
  • the upper limit or lower limit of a numerical range of a certain stage can be arbitrarily combined with the upper limit or lower limit of a numerical range of another stage.
  • the ethanol conversion method includes the steps of: a dehydration step of subjecting an ethanol-containing dehydration raw material to a dehydration reaction using a dehydration catalyst in a reactor to obtain an ethylene-containing dehydration reaction gas; an olefin conversion step of contacting the mixed feedstock containing the dehydration reaction gas with an olefin conversion catalyst in a reactor to obtain a reaction gas containing olefins having 3 or more carbon atoms; Including,
  • the mixed raw material contains an ether, In the mixed raw material, the following formula (1): (In formula (1), EY represents the molar flow rate of ethylene contained in the mixed raw material, EtOH represents the molar flow rate of ethanol contained in the mixed raw material, and Ether represents the molar flow rate of ether contained in the mixed raw material) is 0.20 to 4.0.
  • the first term (EY/EtOH) in formula (1) indicates the molar ratio of ethylene and ethanol in the mixed raw material.
  • ethylene, ethanol, and ether are involved in the chemical conversion with a large reaction heat.
  • the content ratio of ethylene and ethanol which are the main raw materials in the olefin conversion process, has a large effect on the temperature change in the reactor. Therefore, by using ethylene, which generates heat as it is converted, as the numerator and ethanol, which generates heat as it is converted, as the denominator, the magnitude of heat generated relative to the endotherm in the olefin conversion process is expressed in the first term.
  • the first term alone does not take into account the effect of ether conversion. Since the amount of heat absorbed in the conversion reaction of ether to olefin is greater than that of ethanol, the second term was set with the intention of making a correction to reflect the effect of the amount of heat absorbed by ether on the total reaction heat.
  • the second term in formula (1) is the ratio of ether present among ethylene, ethanol, and ether multiplied by a coefficient. This ratio represents the molar ratio of ether in the mixed raw material, so we assumed that by multiplying this by an appropriate coefficient and subtracting it from the first term, we could appropriately correct the effect of the endothermic reaction due to the conversion of ether to olefins on the reaction heat in the olefin conversion reaction, and we empirically determined the coefficient through experiments.
  • formula (1) shows the value obtained by subtracting the second term, which represents the endothermic effect due to the fact that the mixed raw material contains ether, from the first term, which represents the relative effect of heat generation in the reactor of the olefin conversion process.
  • formula (1) which represents the magnitude of the effect of heat generation and absorption in the mixed raw material, within a specified range, it is possible to adjust the balance between the heat generation and endothermic heat of the reaction in the olefin conversion process.
  • an ethanol conversion method it is possible to provide an ethanol conversion method, a hydrocarbon production method, a propylene production method, an aromatic compound production method, and an ethanol conversion device that can easily control the temperature inside the reactor and convert ethanol into a target compound with high efficiency.
  • the value represented by formula (1) in the mixed raw material can be adjusted to a predetermined range to carry out the olefin conversion process, the balance between the heat generation and endothermic heat of the reaction in the olefin conversion process can be adjusted, temperature fluctuations can be suppressed, the temperature inside the reactor can be easily controlled, and ethanol can be converted into a target compound with high efficiency.
  • the value of formula (1) is preferably 0.4 to 3.0.
  • the reaction temperature balance is likely to be a positive value, and the yield of the target compound is likely to be high.
  • the value of formula (1) is 3.0 or less, it is preferable in that the maximum reaction temperature does not become too high, and the performance degradation due to coke formation can be suppressed.
  • the value of formula (1) is 0.40 to 3.0, preferably 0.50 to 2.5, and more preferably 0.60 to 1.5.
  • the ethanol conversion method includes the following steps: a dehydration step of dehydrating an ethanol-containing raw material in a reactor using 10 parts by mass or more of a dehydration catalyst per 100 parts by mass of ethanol supplied per hour to obtain a dehydration reaction gas containing ethylene; an olefin conversion step of contacting the mixed feedstock containing the dehydration reaction gas with an olefin conversion catalyst in a reactor to obtain a reaction gas containing olefins having 3 or more carbon atoms; including.
  • the second embodiment aims to provide an ethanol conversion method, a hydrocarbon production method, a propylene production method, an aromatic compound production method, and an ethanol conversion device that suppress the amount of diethyl ether produced as a by-product in the dehydration process.
  • the second embodiment described above it is possible to provide an ethanol conversion method, a hydrocarbon production method, a propylene production method, an aromatic compound production method, and an ethanol conversion device, in which the amount of diethyl ether by-produced in the dehydration step is suppressed. It has been found that the by-production of diethyl ether can be suppressed by using a large amount of dehydration catalyst, 10 parts by mass or more per 100 parts by mass of ethanol supplied per hour, in the dehydration step. This diethyl ether exhibits a large endotherm when treated in the olefin conversion step.
  • the by-production of diethyl ether in the dehydration step is suppressed, making it easier to control the temperature in the reactor in the olefin conversion step.
  • the second embodiment by including the above-mentioned dehydration step and olefin conversion step, it is easy to control the temperature inside the reactor, and it is possible to provide an ethanol conversion method, a hydrocarbon production method, a propylene production method, an aromatic compound production method, and an ethanol conversion device, which convert ethanol into a target compound with high efficiency.
  • the conversion rate of ethanol in the dehydrated raw material in the dehydration process is 90 mol % or more.
  • the ethanol conversion method includes the following steps: a dehydration step of subjecting an ethanol-containing dehydration feedstock to a dehydration reaction using a dehydration catalyst in a reactor to a conversion rate of ethanol in the dehydration feedstock of 90 mol % or more, thereby obtaining a dehydration reaction gas containing ethylene; an olefin conversion step of supplying ethanol and the dehydration reaction gas into a reactor and contacting the mixed raw materials with an olefin conversion catalyst in the reactor to obtain a reaction gas containing olefins having 3 or more carbon atoms; including.
  • the third embodiment aims to provide an ethanol conversion method that allows easy control of the temperature inside the reactor in the olefin conversion process, and that converts ethanol into a target compound with high efficiency, a method for producing hydrocarbons, a method for producing propylene, a method for producing aromatic compounds, and an ethanol conversion device.
  • an ethanol conversion method a hydrocarbon production method, a propylene production method, an aromatic compound production method, and an ethanol conversion device, which can easily control the temperature inside the reactor in the olefin conversion step and convert ethanol into a target compound with high efficiency.
  • the amount of ethylene supplied to the olefin conversion step can be stabilized, and by supplying ethanol in the olefin conversion step, the ratio of ethylene to ethanol can be adjusted, temperature fluctuations can be suppressed, and the temperature inside the reactor can be easily controlled.
  • the ratio of ethylene in the dehydration reaction gas is less likely to change even due to changes over time such as catalyst deterioration, and the temperature inside the reactor can be easily controlled.
  • the weight ratio E1/E2 of the ethanol (E1) supplied to the reactor in the dehydration process and the ethanol (E2) supplied to the reactor in the olefin conversion process is preferably 0.10 to 4.0, more preferably 0.30 to 3.50, and even more preferably 0.50 to 3.0. By setting it in this range, it becomes easier to control the temperature inside the reactor.
  • the ethanol supply line 11a is provided with the dehydrated raw material supply line 11b and the ethanol supply line 11c for direct introduction into the olefin conversion process via the control valve V1, and the amount of ethanol introduced into the reactor 1 and the amount of ethanol introduced into the reactor 2 by bypass can be adjusted by the control valve V1.
  • FIG. 1 is a schematic diagram of an ethanol conversion apparatus 100.
  • the ethanol conversion apparatus 100 has a reactor 1 for obtaining a dehydration reaction gas, and a reactor 2 for obtaining a reaction gas.
  • a dehydration reaction material containing ethanol is dehydrated by a dehydration catalyst to obtain a dehydration reaction gas containing ethylene. That is, the dehydration process is carried out in the reactor 1. Details of the reactor will be described later.
  • a mixed material containing the dehydration reaction gas is brought into contact with an olefin conversion catalyst to obtain a reaction gas containing olefins having three or more carbon atoms. That is, the olefin conversion process is carried out in the reactor 2. Details of the reactor will be described later.
  • the ethanol supply line 11a has a dehydration raw material supply line 11b and an ethanol supply line 11c that directly introduces the ethanol into the olefin conversion process via a control valve V1.
  • the control valve V1 adjusts the amount of ethanol introduced into reactor 1 and the amount of ethanol introduced into reactor 2 via a bypass. It is also possible to feed the entire amount of ethanol to the dehydration process without bypassing it.
  • the dehydration reaction gas obtained from the reactor 1 is introduced into the reactor 2 via the dehydration reaction gas supply line 11d. Meanwhile, ethanol is introduced into the reactor 2 from the ethanol supply line 11c. A mixture of the dehydration reaction gas, ether, and ethanol is converted in the reactor 2 as a mixed raw material in the olefin conversion process.
  • the reaction gas generated in the reactor 2 is sent to a purification facility to obtain target compounds such as propylene and aromatic compounds.
  • ether may be introduced into the reactor 2 from the ether supply line 11e. According to the embodiment in which ether is supplied from the ether supply line, ethers other than the ether by-produced from ethanol can be used as a mixed raw material. It is effective in that when there is surplus ether, whether it is biomass or non-biomass, it can be used as a raw material for a reaction to produce olefins with high utility value.
  • a dehydration raw material containing ethanol is dehydrated in a reactor by a dehydration catalyst to obtain a dehydration reaction gas containing ethylene.
  • ethylene is obtained by desorbing H 2 O from ethanol.
  • the raw material introduced into the reactor in the dehydration step is referred to as the "dehydrated raw material.”
  • the dehydration raw material contains ethanol. From the viewpoint of excellent environmental compatibility, it is preferable that the ethanol is derived from biomass. Note that biomass refers to organic resources other than fossil resources originating from animals and plants, and biomass-derived refers to compounds produced using biomass as a raw material.
  • the dehydration raw material may contain hydrocarbons with 4 or more carbon atoms in order to provide excellent variability in the raw material ratio. Hydrocarbons with 4 or more carbon atoms have a lower reactivity than ethanol under the conditions of the dehydration process. Therefore, by containing hydrocarbons with 4 or more carbon atoms, even if heat in the system is absorbed by an endothermic reaction, a drop in temperature can be prevented by the heat held by the hydrocarbons with 4 or more carbon atoms, and the dehydration reaction can proceed efficiently in the reactor.
  • the ethanol that is the dehydrated raw material may contain water.
  • the mass ratio of hydrocarbons having 4 or more carbon atoms to ethanol in the dehydration feedstock is preferably 0.0 to 8.0, more preferably 0.1 to 6.0, even more preferably 0.5 to 5.0, and even more preferably 0.8 to 3.0, from the viewpoint of obtaining ethylene by the dehydration reaction of ethanol while controlling the temperature in the reactor.
  • the dehydrated raw material may contain ether.
  • ether since at least a portion of the ether reacts in the dehydration step, if it is intended that the mixed raw material for the olefin conversion reaction contains ether, from the viewpoint of controlling the ether ratio in the mixed raw material, it is preferable to add the ether after the dehydration step, or to generate the ether from ethanol in the dehydration step, rather than adding it as a raw material for the dehydration step.
  • ethers include dimethyl ether, diethyl ether, methyl tertiary butyl ether, ethyl tertiary butyl ether, tetrahydrofuran, and tetrahydropyran. Among these, methyl tertiary butyl ether and ethyl tertiary butyl ether are preferred from the viewpoint of excellent atom efficiency.
  • the ether is preferably derived from biomass from the viewpoint of excellent environmental compatibility.
  • the ether content in the dehydrated raw material is preferably 20 mass% or less, more preferably 10 mass% or less, and even more preferably 5 mass% or less.
  • the reactor used in the dehydration step may be either an adiabatic reactor or an isothermal reactor.
  • an isothermal reactor from the viewpoint of excellent temperature controllability in the reactor, it is preferable to use an isothermal reactor, and from the viewpoint of excellent operability, it is preferable to use an adiabatic reactor.
  • a heating device for heating the raw material can be provided in front of the reactor.
  • Adiabatic Reactor For the adiabatic reactor, the description in Adiabatic Fixed-Bed Reactors (Elsevier, 2014, Ch. 1, P. 4, L. 5-24 ISBN: 978-0-12-801306-9) can be referred to.
  • the adiabatic reactor include a fixed-bed adiabatic reactor, a moving-bed adiabatic reactor, and a fluidized-bed adiabatic reactor, but a fixed-bed adiabatic reactor is preferred for the method of this embodiment.
  • fixed-bed adiabatic reactors a fixed-bed single-stage adiabatic reactor having only one fixed catalyst bed is more preferred. Since carbonaceous matter (coke) accumulates on the catalyst as the reaction proceeds, a multi-column switching type fixed-bed single-stage adiabatic reactor capable of burning and removing the carbonaceous matter while continuing the reaction is preferred.
  • FIG. 2 is a schematic diagram of a fixed-bed, single-stage adiabatic reactor.
  • the fixed-bed, single-stage adiabatic reactor 10a comprises a reaction casing 12 with insulation 121 on its outer periphery, a catalyst bed 13, a reactor inlet 14, and a reactor outlet 15.
  • the reaction casing 12 is provided with insulation 121 on its outer periphery, so that heat inside the reactor is not released to the outside.
  • the temperature inside the reactor can be controlled by the heat generation and absorption due to the reaction.
  • the catalyst bed 13 is filled with a catalyst, which will be described later.
  • a first sheathed thermocouple 161 is provided immediately before contacting the catalyst bed inlet 131 of the catalyst bed 13.
  • a second sheathed thermocouple 162 is provided immediately after passing through the catalyst bed outlet 132 of the catalyst bed 13.
  • These thermocouples measure the temperature of the mixed raw material immediately before contacting the catalyst bed inlet 131 and the reaction gas immediately after passing through the catalyst bed outlet 132. The positions of these thermocouples can be changed as necessary.
  • the catalyst bed 13 may be of a multi-stage type, but is preferably of a single stage type as shown in FIG. 2.
  • the mixed raw material is introduced through the reactor inlet 14, brought into contact with the catalyst bed 13, and the reaction gas is taken out through the reactor outlet 15.
  • An isothermal reactor is a reactor that has a function of keeping the temperature inside the reactor constant by cooling or heating from the outside.
  • isothermal reactors include fixed-bed isothermal reactors, moving-bed isothermal reactors, and fluidized-bed isothermal reactors, but a fixed-bed isothermal reactor is preferred for the method of this embodiment.
  • fixed-bed isothermal reactors from the viewpoint of excellent controllability of the reaction temperature, a multi-tube fixed-bed isothermal reactor, which has a smaller diameter per reactor than a single-tube fixed-bed isothermal reactor, is more preferred. Since carbonaceous matter (coke) accumulates on the catalyst as the reaction proceeds, a multi-tower switching type fixed-bed isothermal reactor that can burn and remove the carbonaceous matter while continuing the reaction is preferred.
  • FIG 3 is a schematic diagram of a single-tube fixed-bed isothermal reactor.
  • the single-tube fixed-bed isothermal reactor 10b basically has the same configuration as the fixed-bed single-stage adiabatic reactor 10a, so the same reference numerals are used for similar parts and their explanations are omitted.
  • the fixed-bed single-stage isothermal reactor 10b differs from the fixed-bed single-stage adiabatic reactor 1 in that it uses a reaction casing 12b with a heat medium layer 121b on its outer periphery.
  • the reaction casing 12b is heated or cooled by controlling the temperature of the heat medium layer 121b on its outer periphery, and the temperature of the catalyst bed 13 can be kept constant.
  • reaction temperature in the dehydration step is preferably 200 to 600°C, more preferably 250 to 500°C, and even more preferably 270 to 480°C, from the viewpoint of proceeding with the dehydration reaction of ethanol.
  • the reaction temperature is as follows.
  • 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 the reaction gas passes through the catalyst bed.
  • the temperature of the mixed raw material and the reaction gas here refers to the temperature between 0d and 0.8d in a plane perpendicular to the flow direction of the fluid, where the center of the reactor is 0 and the distance from the center of the reactor to the inner wall surface of the reactor is d.
  • the average inlet and outlet reaction temperature is a value (hereinafter simply referred to as the "reaction temperature") calculated by measuring the inlet temperature of the catalyst bed and the outlet temperature of the catalyst bed as shown in Figure 2 and using the formula: [inlet temperature of the catalyst bed + outlet temperature of the catalyst bed]/2.
  • reaction temperature a value calculated by measuring the inlet temperature of the catalyst bed and the outlet temperature of the catalyst bed as shown in Figure 2 and using the formula: [inlet temperature of the catalyst bed + outlet temperature of the catalyst bed]/2.
  • the inlet temperature of the catalyst bed is preferably 350°C to 550°C
  • the outlet temperature of the catalyst bed is preferably 100°C to 450°C.
  • an outlet temperature of 250°C or higher is more preferable from the viewpoint of excellent efficiency of the dehydration reaction.
  • the temperature inside the reactor is considered to be uniform, so the inlet temperature of the catalyst bed is treated as the dehydration temperature.
  • the inlet temperature of the catalyst bed is the temperature of the dehydrated raw material immediately before the raw material fluid comes into contact with the catalyst bed packed in the reactor.
  • the temperature of the dehydrated raw material here refers to a temperature between 0d and 0.8d on a plane perpendicular to the flow direction of the fluid, where the center of the reactor is 0 and the distance from the center of the reactor to the inner wall surface of the reactor is d.
  • the dehydration temperature is preferably 200°C to 450°C. Among these, it is more preferable that the dehydration temperature is 350°C or less from the viewpoint of excellent resistance to deterioration of the heat transfer medium used in the isothermal reactor.
  • the reaction pressure in the dehydration process is preferably 0.01 to 3.0 MPaG, and more preferably 0.01 to 1.0 MPaG.
  • the feed rate of the dehydration raw material is preferably 0.1 to 1000 hr -1 , more preferably 0.1 to 500 hr -1 , even more preferably 0.5 to 100 hr -1 , and even more preferably 0.5 to 10 hr -1 , in terms of the mass space velocity (WHSV ) of the dehydration catalyst.
  • WHSV mass space velocity
  • a WHSV of 10 hr -1 or less is preferable from the viewpoint of suppressing the by-production of diethyl ether in the dehydration step.
  • the WHSV is calculated after converting ethanol into ethylene as shown in the following formula.
  • the mass flow rate of the raw material feed is preferably 1 kg/hr or more, more preferably 10 kg/hr or more, and even more preferably 1 t/hr or more, from the viewpoint of excellent productivity of the target compound.
  • WHSV (hr ⁇ 1 ) ethanol feed rate converted into ethylene (kg/hr)/amount of catalyst (kg)
  • Ethylene-equivalent ethanol flow rate (kg/hr) ethanol flow rate (kg/hr) ⁇ ethylene molecular weight (g/mol)/ethanol molecular weight (g/mol)
  • the dehydration catalyst of this embodiment is a catalyst that exhibits catalytic ability to convert ethanol into ethylene through a dehydration reaction.
  • the dehydration catalyst is preferably a solid acid catalyst.
  • Such catalysts include zeolite-containing catalysts, heteropolyacid catalysts, and alumina catalysts.
  • alumina catalysts include SynDol catalysts. Among these, zeolite-containing catalysts are preferred from the viewpoint of excellent thermal durability of the catalyst.
  • the zeolite-containing catalyst is a catalyst powder or molded body containing zeolite as an active species. In the conversion method of this embodiment, it is preferable to use a so-called medium pore size zeolite having a pore size of 5 to 6 ⁇ as the zeolite in the zeolite-containing catalyst.
  • the medium pore size zeolite means "a zeolite whose pore size range is intermediate between the pore size of a small pore size zeolite represented by A-type zeolite and the pore size of a large pore size zeolite represented by mordenite, X-type, and Y-type zeolite.”
  • the "medium pore size zeolite” has a so-called 10-membered oxygen ring in its crystal structure.
  • intermediate pore size zeolites examples include ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-21, ZSM-23, ZSM-35, and ZSM-38, among which MFI type zeolites are preferred, with ZSM-5 being more 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).
  • the silica/alumina (SiO 2 /Al 2 O 3 ) molar ratio of the zeolite contained in the zeolite-containing catalyst of this embodiment can be appropriately selected, but from the viewpoint of excellent catalytic activity and propylene selectivity, it is preferably 20 to 2000, more preferably 40 to 1800, and even more preferably 150 to 1500.
  • the silica/alumina molar ratio of the zeolite can be measured by a known method, and for example, it can be determined by completely dissolving the zeolite in an alkaline aqueous solution and analyzing the resulting solution by plasma emission spectrometry or the like.
  • the synthesis method of the zeolite of this embodiment can be produced by optimizing various conditions of the conventionally known hydrothermal synthesis method of MFI type zeolite.
  • a means for efficiently obtaining MFI type zeolite by hydrothermal synthesis there is a method of hydrothermal synthesis using ammonium salts, urea compounds, amines, alcohols, etc. as an appropriate organic template (SDA), or a method of hydrothermal synthesis by adding hydrothermally synthesized MFI zeolite as seed crystals or as seed slurry in the crystallization stage.
  • SDA organic template
  • a suitable catalyst can be obtained by appropriately optimizing synthesis conditions such as the type of raw material and additive (SDA), the amount of additive, pH, silica/alumina molar ratio, raw material charge composition such as the medium, cation and anion abundance ratio, synthesis temperature, synthesis time, etc.
  • zeolites can be used as long as they are MFI zeolites that have the specific physical properties and composition described above.
  • the zeolite-containing catalyst in this embodiment preferably contains at least one element selected from the group consisting of phosphorus and elements belonging to Group 11 of the periodic table (hereinafter, these elements are collectively referred to as doping element).
  • the zeolite-containing catalyst used as the dehydration catalyst preferably contains phosphorus.
  • Examples of the form of phosphorus include a phosphorus polymer (e.g., polyphosphoric acid), an oxide of phosphorus (e.g., P 2 O 5 ), and a compound in which phosphorus is added to aluminum of zeolite. A plurality of these may be included.
  • phosphorus has the effect of suppressing dealumination of the zeolite.
  • water is generated in the reactor, and the raw material ethanol may contain water, so that the reactor is likely to become a high-temperature steam atmosphere that causes dealumination.
  • Dealuminization causes activity deterioration due to structural collapse of the zeolite-containing catalyst, but when the zeolite-containing catalyst contains phosphorus, dealumination of the zeolite is suppressed, and the durability of the catalyst is improved.
  • Elements belonging to Group 11 of the periodic table include copper, silver, and gold. By including an element belonging to Group 11 of the periodic table, dealumination of the zeolite is suppressed, and the durability of the catalyst is increased. Among these elements belonging to Group 11 of the periodic table, silver is preferred from the viewpoint of excellent support efficiency.
  • the content of the doping element in the zeolite-containing catalyst is preferably 0.01 to 2.0 mass% based on the total mass of the catalyst, and more preferably 0.05 to 2.0 mass% from the viewpoint of excellent effect in suppressing dealumination.
  • the content of the doping element in the zeolite-containing catalyst is a value measured using an X-ray fluorescence analyzer.
  • the content of phosphorus, copper, silver, or gold can be measured using a commercially available X-ray fluorescence analyzer under normal conditions in accordance with the instruction manual.
  • the measurement conditions can be P-K ⁇ radiation, a tube voltage of 50 kV, and a tube current of 50 mA.
  • phosphoric acid and/or phosphate (hereinafter also referred to as "phosphorus raw material”) is used as the raw material for phosphorus contained in the zeolite-containing catalyst.
  • Phosphate is more preferable as the phosphorus raw material, and among phosphates, a compound that has a solubility of 1 g or more in 100 g of water at 25°C is more preferable.
  • Examples of phosphoric acid include phosphoric acid and pyrophosphoric acid
  • examples of phosphate salts 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.
  • ammonium phosphate salts which have a relatively high solubility in water, are preferred, and at least one selected from the group consisting of ammonium phosphate, diammonium hydrogen phosphate, and ammonium dihydrogen phosphate are more preferred. These may be used alone or in combination of two or more.
  • a metal nitrate such as copper nitrate or silver nitrate may be used as a raw material for the element belonging to Group 11 of the periodic table contained in the zeolite-containing catalyst.
  • a zeolite-containing catalyst containing sodium as a counter cation is used to perform ion exchange with the metal nitrate, followed by sintering, to obtain a zeolite-containing catalyst containing an element belonging to Group 11 of the periodic table.
  • the zeolite-containing catalyst of the present embodiment can be produced by molding the zeolite having the above-mentioned specific physical properties and composition, for example, as follows.
  • the molding method is not particularly limited, and a general method can be used. Specifically, the catalyst components are compressed and molded, extruded, or spray-dried, which is optimal for a fluidized bed reaction system, can be used.
  • 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/binder is preferably in the range of 10/90 to 90/10, more preferably in the range of 20/80 to 80/20. Among these, it is preferable to use a silica binder from the viewpoint of excellent caulking resistance.
  • 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 step of heat treatment at a temperature of 300°C or higher in the presence of water vapor. Pretreatment tends to have a more pronounced effect of suppressing catalyst deterioration and improving selectivity.
  • the temperature is 300°C or higher and 900°C or lower, and although there are no particular limitations on the atmosphere, it is preferable to circulate a mixed gas of air or an inert gas such as nitrogen and steam (water vapor) under conditions of a water vapor partial pressure of 0.01 atmosphere or higher.
  • a temperature of 400°C or higher and 700°C or lower is more preferable as the heat treatment temperature.
  • this pretreatment step can be performed using a reactor for converting ethanol and ethylene.
  • a dehydration reaction gas containing ethylene is obtained.
  • the ethylene content in the dehydration reaction gas is preferably 20 to 80 mass %, more preferably 25 to 70 mass %, and further preferably 25 to 60 mass %.
  • the water content in the dehydration reaction gas is preferably 20 to 80 mass%, more preferably 25 to 70 mass%, and even more preferably 25 to 60 mass%.
  • the dehydration reaction gas may contain ether.
  • the content of ether is preferably 40 mass% or less, more preferably 30 mass% or less, and even more preferably 20 mass% or less.
  • the dehydration reaction gas may contain diethyl ether, but preferably does not contain diethyl ether.
  • the content of diethyl ether in the dehydration reaction gas is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass or less.
  • the dehydration reaction gas may contain a hydrocarbon having a carbon number of 4 or more. By containing a hydrocarbon having a carbon number of 4 or more, it becomes easier to adjust the reaction temperature in the dehydration step.
  • the content of hydrocarbons having 4 or more carbon atoms in the dehydration reaction gas is preferably 10 to 60 mass %, more preferably 20 to 55 mass %, and even more preferably 30 to 50 mass %.
  • the conversion rate of ethanol in the dehydration process is preferably 80 mol% or more, more preferably 85 mol% or more, and even more preferably 90 mol% or more.
  • a mixed raw material containing a dehydration reaction gas is contacted with an olefin conversion catalyst in a reactor to obtain a reaction gas containing an olefin having a carbon number of 3 or more.
  • the component ratio in the mixed raw material can be adjusted, making it easier to control the temperature in the reactor.
  • the mixed raw material used in the olefin conversion process in this embodiment preferably contains ether, and the value represented by formula (1) is preferably 0.20 to 4.0.
  • the value represented by formula (1) is preferably 0.20 to 4.0.
  • Ethanol and ether are accompanied by endothermic heat in the process of being converted to olefins having 3 or more carbon atoms in the olefin conversion process.
  • ethylene is accompanied by heat in the process of being converted to olefins having 3 or more carbon atoms in the olefin conversion process.
  • ether since ether has a larger endothermic amount than ethanol, it is expressed as a separate term from the molar ratio of ethylene/ethanol in the above formula and is multiplied by "10". In this way, it is assumed that thermal neutralization can be achieved by combining endothermic and exothermic reactions that do not inhibit each other. In other words, in this embodiment, it was found that the conversion reaction from ethylene to propylene and the conversion reaction from ethanol and ether to propylene proceed without inhibiting each other's reactions, and it is believed that the reaction temperature can be controlled by combining these exothermic and endothermic reactions. However, the factors are not limited to this.
  • the value represented by formula (1) is preferably 0.40 to 3.0, more preferably 0.50 to 2.5, and even more preferably 0.6 to 1.5.
  • Ether is the molar amount of ether contained in the mixed raw material.
  • ethers having 10 or less carbon atoms are preferred, ethers having 8 or less carbon atoms are more preferred, and ethers having 6 or less carbon atoms are even more preferred.
  • the ether contains one ether group.
  • ethers examples include dimethyl ether, diethyl ether, methyl tertiary butyl ether, ethyl tertiary butyl ether, tetrahydrofuran, and tetrahydropyran.
  • the ether in formula (1) may be diethyl ether, methyl tertiary butyl ether, and ethyl tertiary butyl ether.
  • the molar ratio of ethylene/(ethanol + 2 ⁇ diethyl ether) in the mixed raw material used in the olefin conversion process (hereinafter also simply referred to as the "mixed raw material composition ratio”) may be 0.20 to 4.0.
  • the mixed raw material composition ratio is in this range, the balance between the endothermic reaction and the exothermic reaction in the reactor is good, and it becomes easier to control the temperature in the reactor.
  • ethylene generates heat in the process of being converted to olefins having 3 or more carbon atoms in the olefin conversion process.
  • diethyl ether is multiplied by "2" in the above formula because it is accompanied by an endothermic reaction of 2 atoms in the olefin conversion process.
  • ethylene generates heat in the process of being converted to olefins having 3 or more carbon atoms in the olefin conversion process. In this way, it is assumed that thermal neutralization can be achieved by combining endothermic and exothermic reactions that do not inhibit each other.
  • the inventors first investigated the control of reaction heat in an ethanol conversion method that includes a dehydration step in which a dehydration feedstock containing ethanol is dehydrated in a reactor with a dehydration catalyst to obtain a dehydration reaction gas containing ethylene, and an olefin conversion step in which a mixed feedstock containing the dehydration reaction gas is contacted with an olefin conversion catalyst in a reactor to obtain a reaction gas containing olefins having 3 or more carbon atoms.
  • the inventors found that by setting the molar ratio of ethylene/(ethanol + 2 x diethyl ether) in the mixed feedstock to 0.20 to 4.0, temperature fluctuations can be suppressed, the temperature in the reactor can be easily controlled, and ethanol tends to be converted to the target compound with a high yield.
  • the dehydrated raw material containing ethanol is dehydrated in a dehydration process to produce ethylene, and the raw material containing this ethylene is then used in the olefin conversion process.
  • the researchers discovered that it is possible to adjust the balance between the heat generated and the heat absorbed by the reaction in the olefin conversion process.
  • the molar ratio of ethylene/(ethanol + 2x diethyl ether) is preferably 0.20 to 4.0, more preferably 0.30 to 3.5, and even more preferably 0.5 to 3.0, from the viewpoint of facilitating temperature control in the reactor.
  • the weight ratio E1/E2 of the ethanol (E1) supplied to the reactor in the dehydration process and the ethanol (E2) supplied to the reactor in the olefin conversion process is preferably 0.10 to 4.0, more preferably 0.30 to 3.50, and even more preferably 0.50 to 3.0. By setting it in this range, it is possible to more easily control the temperature inside the reactor.
  • a mixed raw material containing a dehydration reaction gas is used.
  • the mixed raw material may be mixed with ethanol in addition to the dehydration reaction gas.
  • the ethanol is derived from biomass.
  • biomass refers to organic resources other than fossil resources originating from animals and plants
  • biomass-derived refers to a compound produced using biomass as a raw material.
  • the ethylene contained in the mixed raw material is preferably the ethylene contained in the dehydration reaction gas. Since water is a by-product in the process of converting ethanol to ethylene, the dehydration reaction gas generally contains water.
  • the mixed raw material may further contain "additional ethylene” in addition to the ethylene contained in the dehydration reaction gas, from the viewpoint of excellent variability in the raw material ratio.
  • the "additional ethylene” may be produced by various methods. For example, it may be obtained by thermal decomposition of naphtha and/or ethane, direct or oxidative dehydrogenation of ethane, or dehydration of ethanol.
  • the mixed raw material may contain ether.
  • the content is set so that the value of formula (1) satisfies 0.20 to 4.0.
  • ethers from the viewpoint of excellent reactivity in the olefin conversion reaction, ethers having a carbon number of 10 or less are preferable, ethers having a carbon number of 8 or less are more preferable, and ethers having a carbon number of 6 or less are even more preferable.
  • the ether contains one ether group.
  • ethers examples include dimethyl ether, diethyl ether, methyl tertiary butyl ether, ethyl tertiary butyl ether, tetrahydrofuran, and tetrahydropyran.
  • methyl tertiary butyl ether and ethyl tertiary butyl ether are preferable from the viewpoint of excellent atom efficiency.
  • the ether is preferably derived from biomass from the viewpoint of excellent environmental compatibility. As described above, it is preferable that the ether contains at least one selected from the group consisting of diethyl ether, methyl tertiary butyl ether, and ethyl tertiary butyl ether.
  • the mixed feedstock may further contain a hydrocarbon having 4 to 6 carbon atoms.
  • the hydrocarbon having 4 to 6 carbon atoms include olefins having 4 to 6 carbon atoms and saturated hydrocarbons having 4 to 6 carbon atoms.
  • the olefins having 4 to 6 carbon atoms can give the target compound such as propylene by contacting them with a conversion catalyst, similar to ethylene and ethanol.
  • the hydrocarbons having 4 to 6 carbon atoms include butene, pentene, hexene, butane, pentane, and hexane.
  • the molar ratio of the olefins having 4 to 6 carbon atoms to ethylene is preferably 3.0 or less, more preferably 1.0 or less, and even more preferably 0.14 to 1.0.
  • olefin above includes linear, branched, and cyclic olefins as well as cycloparaffins.
  • the mixed feedstock can also contain hydrocarbons with 7 or more carbon atoms, and oxygen-containing compounds other than ethanol, such as methanol, propanol, dimethyl ether, and diethyl ether.
  • hydrocarbons with 7 or more carbon atoms and oxygen-containing compounds can be brought into contact with a conversion catalyst to give the target compound.
  • the mixed raw material may contain inert dilution gases such as nitrogen, hydrogen, and methane, in addition to the organic matter defined above that can be converted to propylene by the olefin conversion process, but it is preferable not to dilute with hydrogen.
  • Hydrogen is sometimes used to suppress coking deterioration of the catalyst, but at the same time, hydrogenation reactions of the produced propylene and the like occur, which has the adverse effect of lowering the propylene purity (propylene/(propylene + propane)) [mol/mol].
  • the rate of coking deterioration of the catalyst is low even when hydrogen dilution is not performed, and stable operation is possible, so it is preferable not to dilute with hydrogen.
  • the total content of ethylene and ethanol in the mixed raw material is preferably 30 to 100 mass% relative to the total amount of the conversion raw material, more preferably 40 to 100 mass%, and even more preferably 50 to 100 mass%.
  • the mass converted into ethylene is used in the calculation.
  • the total content of ethylene and ethanol is in the range of 50 mass% or more, it becomes easier to control the reaction heat by satisfying the value of formula (1) in the olefin conversion reaction process.
  • the content of ether in the mixed raw material is preferably 20 mass% or less, more preferably 10 mass% or less, and even more preferably 5 mass% or less.
  • the content of ether in the mixed raw material may be 0.01 mass% or more, 0.05 mass% or more, or 0.2 mass% or more. When the content of ether is in the range of 20 mass% or less, it becomes easier to control the reaction heat by satisfying the value of formula (1) in the olefin conversion reaction process.
  • the total content of olefins having 4 to 6 carbon atoms in the mixed raw material is preferably 65 mass% or less, and more preferably 10 to 55 mass%.
  • the mixed feed may contain diethyl ether.
  • the content of diethyl ether in the mixed raw material is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.
  • the content of diethyl ether in the mixed raw material may be 0.01% by mass or more, 0.05% by mass or more, or 0.2% by mass or more.
  • the mixed raw material may contain an olefin having 4 to 6 carbon atoms in order to facilitate the temperature in the reactor.
  • the molar ratio of olefins having 4 to 6 carbon atoms to ethylene in the mixed feedstock is preferably 3.5 or less, more preferably 3.0 or less, even more preferably 1.0 or less, and even more preferably 0.14 to 1.0.
  • olefin as mentioned above includes linear, branched and cyclic olefins as well as cycloparaffins.
  • water vapor can be included in the mixed raw material.
  • the ethylene and ethanol contained in the mixed raw material are produced by various production methods, and therefore contain "water vapor generated during the production process.”
  • water vapor generated during the production process refers to moisture that is generated during the production process of ethylene and/or ethanol and has not been removed.
  • steam can be added to the mixed raw material in addition to the "steam generated during the production process.”
  • Steam has the effect of suppressing coking deterioration by lowering the olefin partial pressure and improving the yield of low olefins.
  • steam may promote dealumination of zeolite, so it is preferable not to add steam to the mixed raw material in addition to the "steam generated during the production process.”
  • the reactor used in the olefin conversion step may be either an adiabatic reactor or an isothermal reactor.
  • an isothermal reactor from the viewpoint of excellent temperature controllability in the reactor, it is preferable to use an isothermal reactor, and from the viewpoint of excellent operability, it is preferable to use an adiabatic reactor.
  • the adiabatic reactor and the isothermal reactor are as described above.
  • the reaction temperature in the olefin conversion step is preferably 300 to 600° C., more preferably 400 to 590° C., and even more preferably 450 to 550° C., from the viewpoint of obtaining an excellent propylene yield.
  • the reaction temperature is preferably 400° C. or higher, from the viewpoint of suppressing the acceleration of coking deterioration promoted at high temperatures.
  • the reaction temperature in the adiabatic reactor is defined as the same as in the dehydration step.
  • the temperature difference between the catalyst bed outlet temperature and the catalyst bed inlet temperature is preferably -80K to 80K, more preferably -60K to 60K.
  • the reaction pressure is preferably 0.01 to 3.0 MPaG, more preferably 0.01 to 1.0 MPaG.
  • the feed rate of the mixed raw material is preferably 0.1 to 1000 hr -1 , more preferably 0.1 to 500 hr -1 , and even more preferably 0.5 to 100 hr -1 , in terms of the mass space velocity (WHSV) of the olefin conversion catalyst.
  • the WHSV is calculated by converting ethanol into ethylene as shown in the following formula.
  • the mass flow rate of the raw material feed is preferably 1 kg/hr or more, more preferably 10 kg/hr or more, and even more preferably 1 t/hr or more.
  • WHSV(hr ⁇ 1 ) olefin supply flow rate(kg/hr)/catalyst amount(kg)
  • Olefin supply flow rate (kg/hr) Ethylene flow rate (kg/hr)+Ethylene converted ethanol flow rate (kg/hr)+Olefin converted ether flow rate (kg/hr)+C4-6
  • Ethylene-equivalent ethanol flow rate (kg/hr) ethanol flow rate (kg/hr) ⁇ ethylene molecular weight (g/mol)/ethanol molecular weight (g/mol)
  • Olefin conversion ether flow rate (kg/hr) ether flow rate (kg/hr) ⁇ (ether molecular weight (g/mol) ⁇ water molecular weight (g/mol))/ether molecular weight (g/mol)
  • the olefin conversion catalyst is a catalyst that exhibits catalytic ability to convert olefins and ethanol into target compounds such as propylene.
  • the olefin conversion catalyst is preferably a solid acid catalyst.
  • a zeolite-containing catalyst is preferable from the viewpoint of excellent thermal durability of the catalyst.
  • the zeolite-containing catalyst is as described above for the dehydration catalyst.
  • a common problem in conventional olefin production using zeolite is coking deterioration, in which heavy carbonaceous matter (coke) accumulates inside the zeolite pores due to reaction with hydrocarbons and deactivates the zeolite.
  • the zeolite-containing catalyst in the olefin conversion process has a silica/alumina molar ratio of the zeolite in the zeolite-containing catalyst of preferably 20 to 2000, more preferably 40 to 1800, and even more preferably 150 to 1500, from the viewpoint of excellent catalytic activity and propylene selectivity.
  • the zeolite-containing catalyst preferably contains at least one element selected from the group consisting of phosphorus and elements belonging to Group 11 of the periodic table.
  • the zeolite-containing catalyst used as the dehydration catalyst preferably contains phosphorus or silver.
  • the ethanol conversion method of this embodiment may include a regeneration step (hereinafter also referred to as the "regeneration step") of burning the coke attached to the catalyst.
  • a regeneration step hereinafter also referred to as the "regeneration step” of burning the coke attached to the catalyst.
  • the catalyst When the catalyst is used in a reaction for a long period of time, coke may adhere to the catalyst, causing coking deterioration.
  • the catalyst When the catalyst has been degraded by coking, the catalyst can be regenerated by burning and removing the coke on the catalyst at a temperature of 400 to 700°C, for example, in air or a mixed gas of air and/or oxygen and an inert gas, preferably under conditions of an oxygen concentration of 0.1 to 2.0% by volume.
  • Either of the regeneration methods may be adopted: out-of-reactor regeneration, in which the catalyst is extracted from the reactor and regenerated outside the reactor, or in-reactor regeneration, in which the catalyst is not extracted from the reactor and regenerated inside the reactor.
  • a switching type reactor may be used to perform reaction-regeneration switching operation.
  • reaction-regeneration switching operation is an operation in which a reaction step and a regeneration step are performed simultaneously using a two-tower or multi-tower switching reactor.
  • a reaction step and a regeneration step are performed simultaneously using a two-tower or multi-tower switching reactor.
  • two towers are used for the reaction step, and at the same time, the remaining one tower is used for catalyst regeneration.
  • the reaction step of one of the towers used for the reaction step is stopped to perform catalyst regeneration, and the reaction step is performed in the one tower used for catalyst regeneration, thereby making it possible to perform catalyst regeneration while maintaining the production capacity of two towers.
  • This type of reaction format is also called a merry-go-round method, and is preferable from the viewpoint of excellent production efficiency because there is no need to stop the production process for catalyst regeneration.
  • a reaction gas containing olefins having 3 or more carbon atoms is obtained by contacting a mixed feedstock with a conversion 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.
  • target compounds 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.
  • the purification of the target compound can be efficiently carried out by providing a separation step.
  • the separation step the reaction gas obtained in the above-mentioned reaction step is separated 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 by a separation device.
  • the separation device used in the separation step is, for example, a distillation column.
  • the separation step may be omitted, and the reaction gas obtained in the above-mentioned reaction step may be introduced into a purification system of an ethylene plant, and the target compounds such as ethylene, propylene, and aromatic compounds may be separated from the reaction gas in the purification system.
  • the method according to this embodiment may be carried out by an apparatus having a reactor 1, a reactor 2, and a first distillation column 3, as shown in FIG. 4.
  • the reaction gas obtained by the olefin conversion process carried out in the reactor 2 is separated in the first distillation column 3 into a fraction A mainly containing hydrocarbons with 1 to 3 carbon atoms and a fraction B mainly containing hydrocarbons with 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.
  • 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.
  • the method according to this embodiment can be carried out by an apparatus having a reactor 1, a reactor 2, a first distillation column 3, a second distillation column 4, a third distillation column 5, a fourth distillation column 6, and a fifth distillation column 7, as shown in FIG. 5.
  • the reaction gas obtained by the olefin conversion process carried out in the reactor 2 is separated in the first distillation column 3 into a fraction A mainly containing hydrocarbons with a carbon number of 1 to 3 and a fraction B mainly containing hydrocarbons with a carbon number of 4 to 6.
  • the fraction A is separated in the second distillation column 4 into a fraction C mainly containing hydrocarbons with a carbon number of 1 and a fraction D mainly containing hydrocarbons with a carbon number of 2 to 3.
  • the fraction D is separated in the third distillation column 5 into a fraction E mainly containing hydrocarbons with a carbon number of 2 and a fraction F mainly containing hydrocarbons with a carbon number of 3.
  • the fraction E is separated in the fourth distillation column 6 into a fraction G mainly containing ethylene and a fraction H mainly containing ethane.
  • Fraction F is separated into fraction I, which mainly contains propylene, and fraction J, which mainly contains propane.
  • the target compound can also be obtained by the same method after separating fraction A into a fraction mainly containing hydrocarbons with 1 to 2 carbon atoms and a fraction mainly containing hydrocarbons with 3 carbon atoms.
  • the method according to this embodiment can be carried out by an apparatus having a reactor 1, a reactor 2, a cooler 8, an oil-water separator 9, and a first distillation tower 3, as shown in FIG. 6.
  • the reaction gas obtained by the olefin conversion process carried out in the reactor 2 is separated in the cooler 8 into a fraction K mainly containing hydrocarbons with a carbon number of 1 to 6, and a fraction L mainly containing water, hydrocarbons with a carbon number of 7 or more, and aromatic compounds.
  • the fraction L "mainly containing water, hydrocarbons with a carbon number of 7 or more, and aromatic compounds” means that the total amount of water, hydrocarbons with a carbon number of 7 or more, and aromatic compounds is more than 50 mass% of the total amount of the fraction L.
  • the fraction K is separated into a fraction A mainly containing hydrocarbons with a carbon number of 1 to 3, and a fraction B mainly containing hydrocarbons with a carbon number of 4 to 6.
  • the fraction L is separated into a fraction M mainly containing hydrocarbons with a carbon number of 7 or more and aromatic compounds, and a fraction N mainly containing water.
  • the purification of aromatic compounds can be carried out efficiently.
  • the purification of target compounds such as propylene and aromatic compounds can be carried out efficiently.
  • At least a portion of fraction A, fraction B, and fraction M may be introduced into the purification system of an ethylene plant, and the target compounds such as ethylene, propylene, and aromatic compounds may be separated from the reaction gas in the purification system.
  • mainly contains in various fractions means that the total mass of the components described as “mainly contains” is more than 50% by mass for each fraction.
  • the ethanol conversion method of this embodiment is a method for producing hydrocarbons.
  • the hydrocarbons may be either saturated or unsaturated hydrocarbons.
  • unsaturated hydrocarbons include olefins and aromatic hydrocarbon compounds.
  • the propylene production method of the present embodiment includes a propylene separation step of separating a fraction mainly containing propylene from the reaction gas obtained by the ethanol conversion method of the present embodiment.
  • a known propylene purification method such as distillation can be used as the propylene separation step.
  • the propylene separation step can be performed using equipment associated with an ethylene plant by connecting a part or the whole of the reaction gas to a purification system of the ethylene plant.
  • the method for producing aromatic compounds according to the present embodiment includes an aromatic compound separation step of separating a fraction mainly containing aromatic compounds from the reaction gas obtained by the ethanol conversion method according to the present embodiment.
  • a known aromatic compound purification method such as distillation can be used as the aromatic compound separation step.
  • the propylene separation step can be carried out using equipment associated with the ethylene plant by connecting a part or the whole of the reaction gas to a purification system of the ethylene plant.
  • thermocouple The temperature at the catalyst bed inlet and the temperature at the catalyst bed outlet were measured by a thermocouple inserted from outside the reactor. Specifically, as shown in Figures 2 and 3, 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. Note that the effect of heat radiation due to the insertion of this thermocouple was negligibly small. In addition, the thermocouple was moved in the fluid flow direction as necessary to measure the minimum temperature in the reactor.
  • reaction evaluation of dehydration process Reactions were carried out according to the following examples and comparative examples. A portion of the reactor outlet gas was sampled every 3 hours from the start of the reaction, and introduced into a gas chromatograph (TCD and 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. When an adiabatic reactor was used, the catalyst bed inlet temperature and catalyst bed outlet temperature were both recorded, and when an isothermal reactor was used, the catalyst bed inlet temperature was recorded as the reaction temperature.
  • TCD and FID detector gas chromatograph
  • the dehydration reaction gas was mixed with the bypass feed, ether, and hydrocarbons having 4 or more carbon atoms as required to prepare a mixed feed.
  • the value of formula (1) was calculated from EY, the molar flow rate of ethylene contained in the mixed feedstock, EtOH, the molar flow rate of ethanol contained in the mixed feedstock, and Ether, the molar flow rate of ether contained in the mixed feedstock.
  • the molar ratio of ethylene/(ethanol+2 ⁇ diethyl ether) and the molar ratio of olefins having 4 to 6 carbon atoms/ethylene in the mixed feed gas were calculated by the following formulas.
  • Molar ratio (-) of ethylene/(ethanol+2 ⁇ diethyl ether) molar flow rate of ethylene (mol/hr)/(molar flow rate of ethanol (mol/hr)+2 ⁇ molar flow rate of diethyl ether (mol/hr))
  • Molar ratio of C4-6 olefin/ethylene (-) flow rate of C4-6 olefin (mol/hr)/mol flow rate of ethylene (mol/hr)
  • Coke yield (wtppm) coke amount / [olefin feed rate (kg/hr) x reaction time (hr)]
  • Olefin supply flow rate (kg/hr) Ethylene flow rate (kg/hr)+Ethylene converted ethanol flow rate (kg/hr)+Olefin converted ether flow rate (kg/hr)+C4-6 olefin flow rate (kg/hr)
  • Ethylene-equivalent ethanol flow rate (kg/hr) ethanol flow rate (kg/hr) ⁇ ethylene molecular weight (g/mol)/ethanol molecular weight (g/mol)
  • Olefin conversion ether flow rate (kg/hr) ether flow rate (kg/hr) ⁇ (ether molecular weight (g/mol) ⁇ water molecular weight (g/mol))/ether molecular weight (g/mol)
  • Ethanol conversion rate and diethyl ether by-product rate The ethanol conversion rate represents the amount of ethanol converted in the dehydration process, and the diethyl ether by-product rate represents the conversion rate of ethanol to diethyl ether.
  • Ethanol conversion rate (mol%) (1-amount of ethanol contained in dehydration reaction gas (kg/hr)/flow rate of ethanol supplied to the dehydration step (kg/hr)) ⁇ 100
  • Diethyl ether by-production rate (mol %) (2 ⁇ amount of diethyl ether by-product (kmol/hr)/flow rate of ethanol supplied to the dehydration step (kmol/hr)) ⁇ 100
  • Propylene yield represents the selectivity to propylene in the olefin conversion process and was calculated by the following formula.
  • Propylene yield (mass%) mass of propylene produced per hour in the olefin conversion process (kg/hr) / olefin supply flow rate (kg/hr)
  • Olefin supply flow rate (kg/hr) Ethylene flow rate (kg/hr)+Ethylene converted ethanol flow rate (kg/hr)+Olefin converted ether flow rate (kg/hr)+C4-6 olefin flow rate (kg/hr)
  • Ethylene-equivalent ethanol flow rate (kg/hr) ethanol flow rate (kg/hr) ⁇ ethylene molecular weight (g/mol)/ethanol molecular weight (g/mol)
  • Olefin conversion ether flow rate (kg/hr) ether flow rate (kg/hr) ⁇ (ether molecular weight (g/mol) ⁇ water molecular weight (g
  • Olefin supply flow rate (kg/hr) Ethylene flow rate (kg/hr)+Ethylene converted ethanol flow rate (kg/hr)+Olefin converted ether flow rate (kg/hr)+C4-6 olefin flow rate (kg/hr)
  • Olefin conversion ether flow rate (kg/hr) ether flow rate (kg/hr) ⁇ (ether molecular weight (g/mol) ⁇ water molecular weight (g/mol))/ether molecular
  • the obtained phosphorus-supported product was fired at 600 ° C. for 5 hours in an air atmosphere.
  • the fired product was filled in a reactor, and a steam-nitrogen mixed gas containing 80% by volume of steam was supplied and circulated under conditions of a pressure of 0.1 MPaG and a temperature of 600 ° C. for 24 hours to obtain a zeolite-containing catalyst 4.
  • the content of phosphorus element contained in the zeolite-containing catalyst was 0.18% by mass.
  • the obtained catalyst precursor was stirred in a 0.1 N aqueous sodium nitrate solution for 1 hour, filtered and washed, and baked at 600 ° C. for 5 hours to obtain a sodium exchanger.
  • the sodium exchanger was stirred in a 0.01 N aqueous silver nitrate solution for 1 hour, and the filtering and washing operations were repeated three times, and the silver exchanger was obtained by baking at 600 ° C. for 5 hours.
  • a steam-air mixed gas containing 80% by volume of steam was supplied to the silver exchanger under conditions of a pressure of 0.1 MPaG and a temperature of 600 ° C. for 24 hours, and a zeolite-containing catalyst 5 was obtained. At this time, the content of silver element contained in the zeolite-containing catalyst was 0.16% by mass.
  • the obtained phosphorus-supported product was fired at 600 ° C. for 5 hours in an air atmosphere.
  • the fired product was filled in a reactor, and a steam-nitrogen mixed gas containing 80% by volume of steam was supplied and circulated under conditions of a pressure of 0.1 MPaG and a temperature of 600 ° C. for 24 hours to obtain a zeolite-containing catalyst 6.
  • the content of phosphorus element contained in the zeolite-containing catalyst was 0.05% by mass.
  • Example 1 (Dehydration process) Of the total amount of 10.50 kg/hr of 93.3 mass% ethanol used in Example 1, 6.21 kg/hr (ethanol 5.80 kg/hr + water 0.41 kg/hr) was used as a dehydration feedstock to be fed to the dehydration step, and 4.29 kg/hr (ethanol 4.00 kg/hr + water 0.29 kg/hr) was used as a bypass feedstock to be directly fed to the olefin conversion step.
  • 6.21 kg/hr ethanol 5.80 kg/hr + water 0.41 kg/hr
  • 4.29 kg/hr ethanol 4.00 kg/hr + water 0.29 kg/hr
  • the above 6.21 kg/hr of ethanol and 3.70 kg/hr of hydrocarbons having 4 or more carbon atoms shown in Table 1 were fed to a fixed-bed single-stage adiabatic reactor filled with a zeolite-containing catalyst 1 (silica/alumina molar ratio: 40, alumina binder) so that the WHSV was 3.0 and the pressure was 0.20 MPaG to carry out the dehydration step.
  • the inlet temperature of the catalyst bed in the fixed-bed single-stage adiabatic reactor was 480°C, and the outlet temperature of the catalyst bed was 285°C.
  • the concentrations of each component in the resulting dehydration reaction gas are shown in Table 2.
  • the dehydration reaction gas obtained in the dehydration step and the bypass feedstock were mixed to prepare a mixed feedstock.
  • the molar ratio of ethylene/(ethanol + 2 ⁇ diethyl ether) in the mixed feedstock was 1.06, the value of formula (1) was 0.96, and the molar ratio of olefins having 4 to 6 carbon atoms/ethylene was 0.26.
  • the mixed raw material was supplied to a fixed-bed single-stage adiabatic reactor filled with a zeolite-containing catalyst 2 (silica/alumina molar ratio: 1000, silica binder) so that the WHSV was 2.0 and the pressure was 0.15 MPaG, and an olefin conversion process was carried out.
  • the inlet temperature of the catalyst bed in the fixed-bed single-stage adiabatic reactor 24 hours after the start of the reaction was 534 ° C.
  • the outlet temperature of the catalyst bed was 546 ° C.
  • the inlet/outlet temperature difference was 12 K.
  • the average propylene yield from the start of the reaction to the end of the reaction was 20.8 mass%, the average aromatic yield was 2.3 mass%, and the coke yield of the zeolite-containing catalyst 2 after 48 hours of operation was 238 wtppm.
  • the reaction results and details of the reaction conditions are shown in Table 3.
  • Examples 2 to 4 The reaction was carried out in the same manner as in Example 1, except that the dehydration catalyst, the feed rate of the dehydration raw material, and the feed rate of the bypass raw material in the dehydration step were changed as shown in Table 2, and the olefin conversion catalyst and various conditions in the olefin conversion step were changed as shown in Table 3. The results are shown in Tables 2 and 3. As in Examples 1 to 4, by supplying a hydrocarbon having a carbon number of 4 or more to the dehydration step, it was possible to mitigate the temperature drop in the reactor even in an adiabatic reactor.
  • Examples 5 to 6 The reaction was carried out in the same manner as in Example 1, except that a single-tube fixed-bed isothermal reactor was used in the dehydration step, the dehydration catalyst, the feed rate of the dehydration raw material, and the feed rate of the bypass raw material were changed as shown in Table 2, and the olefin conversion catalyst and various conditions in the olefin conversion step were changed as shown in Table 3. The results are shown in Tables 2 and 3. In addition, since the temperature change inside the isothermal reactor is small, the catalyst bed inlet temperature is regarded as the reaction temperature, and the minimum temperature inside the reactor is also shown in Table 2.
  • the value of formula (1) is 3.0 or less, so that the temperature rise in the olefin conversion process can be suppressed and the coke yield can be kept low.
  • the value of formula (1) is kept low, so that the amount of coke adhering to the catalyst during the reaction can be suppressed and the catalytic performance during the reaction can be maintained.
  • Example 7 to 8 The reaction was carried out in the same manner as in Example 5, except that the dehydration catalyst, the feed rate of the dehydration raw material, and the feed rate of the bypass raw material in the dehydration step were changed as shown in Table 4, and the olefin conversion catalyst and various conditions in the olefin conversion step were changed as shown in Table 5. The results are shown in Tables 4 and 5.
  • Example 9 The reaction was carried out in the same manner as in Example 1, except that the dehydration catalyst, the feed rate of the dehydration raw material, and the feed rate of the bypass raw material in the dehydration step were changed as shown in Table 4, and the olefin conversion catalyst and various conditions in the olefin conversion step were changed as shown in Table 5. The results are shown in Tables 4 and 5.
  • water was supplied in addition to 93.3 mass % ethanol as the dehydration raw material. By adding water, it was possible to mitigate the temperature drop in the reactor even in an adiabatic reactor.
  • Comparative Example 1 (Dehydration process)
  • a total amount of 10.50 kg/hr of 93.3 mass% ethanol was used as the dehydration raw material to be subjected to the dehydration step.
  • the dehydration raw material was supplied to a fixed-bed single-stage isothermal reactor filled with a zeolite-containing catalyst 1 (silica/alumina molar ratio: 40, alumina binder) so that the WHSV was 4.0 and the pressure was 0.20 MPaG, and the dehydration step was carried out under a constant condition of 350°C.
  • the concentrations of each component in the obtained dehydration reaction gas are shown in Table 4. At this time, the ethanol conversion rate was 98.2 mol%.
  • the dehydration reaction gas obtained in the dehydration step was used as a mixed raw material as it is in the olefin conversion step.
  • the mixed raw material was supplied to a fixed-bed single-stage adiabatic reactor packed with a zeolite-containing catalyst 2 (silica/alumina molar ratio: 1000, silica binder) so that the WHSV was 3.0 and the pressure was 0.15 MPaG, and an olefin conversion process was carried out.
  • the inlet temperature of the catalyst bed was 419°C
  • the outlet temperature of the catalyst bed was 661°C
  • the inlet/outlet temperature difference was 242K.
  • the catalytic activity significantly decreased with the passage of reaction time, and the propylene yield at 24 hours was 6.3 mass% and the aromatics yield was 0.5 mass%, so the reaction was stopped.
  • Comparative Example 2 In Comparative Example 2, the dehydration step was not provided, and the entire amount of ethanol was directly subjected to the olefin conversion step. 93.3 mass% ethanol was supplied to a fixed-bed single-stage adiabatic reactor filled with a zeolite-containing catalyst 2 (silica/alumina molar ratio: 1000, silica binder) so that the WHSV was 3.0 and the pressure was 0.15 MPaG, and the olefin conversion step was carried out. At this time, the inlet temperature of the catalyst bed was 592 ° C., the outlet temperature of the catalyst bed was 488 ° C., and the inlet/outlet temperature difference was 104 K.
  • zeolite-containing catalyst 2 siliconca/alumina molar ratio: 1000, silica binder
  • the average propylene yield from the start of the reaction to the end of the reaction was 11.4 mass%, the average aromatic yield was 0.9 mass%, and the coke yield of the zeolite-containing catalyst 2 after the end of 48 h operation was 379 wtppm.
  • the reaction results and details of the reaction conditions are shown in Table 5. Comparison between the working example and comparative example 2 reveals that when ethanol is directly supplied to the olefin conversion process without providing a dehydration process, the temperature inside the adiabatic reactor cannot be controlled due to the endothermic reaction, the reactor outlet temperature drops, and catalyst deterioration is accelerated, resulting in a decrease in the yield of the target compound.
  • Example 10 was carried out in the same manner as in Example 1, except that in addition to the dehydration reaction gas and the bypass feedstock, ethyl tertiary butyl ether (0.50 kg/hr) was used as a mixed feedstock.
  • the reaction results and details of the reaction conditions are shown in Table 6.
  • the catalyst loading was increased so that the WHSV was the same as in Example 1.
  • Example 11 was carried out in the same manner as in Example 1, except that in addition to the dehydration reaction gas and the bypass feedstock, methyl tertiary butyl ether (0.50 kg/hr) was used as a mixed feedstock.
  • the reaction results and details of the reaction conditions are shown in Table 6.
  • the catalyst loading was increased so that the WHSV was the same as in Example 1.
  • Example 12 was carried out in the same manner as in Example 6, except that in addition to the dehydration reaction gas and the bypass feedstock, methyl tertiary butyl ether (4.0 kg/hr) was used as a mixed feedstock. The reaction results and details of the reaction conditions are shown in Table 6. The catalyst loading was increased so that the WHSV was the same as in Example 6.
  • Comparative Example 3 In Comparative Example 3, the same procedure as in Example 1 was carried out except that methyl tert-butyl ether (4.0 kg/hr) was used as a mixed raw material in addition to the dehydration reaction gas and the bypass raw material. The reaction temperature in the reactor dropped rapidly, and the temperature at the catalyst bed inlet was not stabilized, so the reaction was stopped. In addition, unreacted ethanol and methyl tert-butyl ether were detected at the reactor outlet. Comparison between the examples and Comparative Example 3 reveals that the temperature control in the adiabatic reactor becomes easy by setting the value represented by formula (1) in the olefin conversion process within a predetermined range.

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