Method for converting ethanol, zeolite-containing catalyst, method for producing a zeolite-containing catalyst, and method for producing hydrocarbons, etc.

Abstract

The method for converting ethanol includes a reaction step for supplying a mixed raw material containing ethanol to a reactor having a fixed bed packed with a zeolite-containing catalyst to obtain a reaction gas containing water and olefins having three or more carbon atoms. The zeolite contained in the zeolite-containing catalyst has an oxygen 10-membered ring structure. The molar ratio of Na / Al in the zeolite-containing catalyst is 0.0050-0.25. The acid amount per weight of the zeolite-containing catalyst, determined from the ammonia desorption amount at 100-650°C in ammonia temperature-programmed desorption measurement of the zeolite-containing catalyst, is 75 μmol / g or less.

Description

Technical Field

[0001] The present invention relates to a method for converting ethanol, a zeolite-containing catalyst, a method for producing a zeolite-containing catalyst, and a method for producing hydrocarbons and the like.

Background Art

[0002] Hydrocarbons such as lower olefins and aromatic compounds are important basic raw materials in the chemical industry. In particular, for propylene, the demand for which is expected to increase, the development and improvement of production methods have been actively carried out. Among them, as a general method for producing propylene, a method of contacting naphtha or olefins with a catalyst having zeolite as an active species is known.

[0003] In addition to olefins, in recent years, due to the increasing awareness of environmental protection, the production of chemical products such as lower olefins and aromatic compounds from biomass-derived alcohols as raw materials has attracted attention. In particular, since ethanol is a compound for which a production method from biomass raw materials has been established, the early development of an efficient method for converting ethanol is expected.

[0004] For example, Patent Documents 1 and 2 disclose a method for producing a phosphorus-modified zeolite catalyst that promotes the conversion reaction of ethanol to propylene. Further, Patent Document 3 shows a method for producing propylene using a zeolite catalyst to produce propylene from an ethylene raw material containing water.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] When ethanol is converted to obtain hydrocarbons such as propylene and aromatic compounds, the dehydration reaction of ethanol produces equimolar water as a by-product. Generally, water (water vapor) at temperatures above 400°C causes structural breakdown of the zeolite catalyst due to dealuminization, reducing the catalytic performance of the zeolite. In other words, when ethanol is converted by contacting a zeolite with a raw material containing ethanol, the catalytic activity decreases due to the by-product water, resulting in a lower yield of the target compound as the operating time progresses. In particular, when using a reactor with a fixed bed, catalyst replacement or additional charging is not possible during the reaction, so catalyst degradation leads to a significant decrease in productivity.

[0007] Patent documents 1 and 2 disclose methods for producing a zeolite catalyst that converts an ethanol raw material to propylene, but they show that the catalytic activity decreases as the reaction time progresses. Patent document 3 discloses a method for converting an ethylene raw material containing water to propylene by contacting it with a zeolite catalyst, but it shows that the propylene selectivity decreases within a few hours from the start of the reaction.

[0008] Therefore, the present invention aims to provide a method for converting ethanol that suppresses the deterioration of catalyst performance due to water vapor and suppresses coke deposition, a zeolite-containing catalyst, a method for producing a zeolite-containing catalyst, and a method for producing hydrocarbons, etc. [Means for solving the problem]

[0009] As a result of diligent research to achieve the above objectives, the present inventors have found that by using a catalyst containing an oxygen 10-membered ring zeolite exhibiting a specific composition and physical properties, structural collapse of the zeolite and coke deposition on the catalyst due to side reactions are prevented even in ethanol conversion accompanied by water byproduct, and the decrease in catalytic activity is suppressed, thereby enabling the production of the target compound in a stable yield. That is, the present invention encompasses the following embodiments.

[0010] <1> The reaction includes a step of supplying a mixed raw material containing ethanol to a reactor having a fixed bed filled with a zeolite-containing catalyst, and obtaining a reaction gas containing an olefin having 3 or more carbon atoms and water. The zeolite contained in the zeolite-containing catalyst has an oxygen 10-membered ring structure, The Na / Al molar ratio of the zeolite-containing catalyst is 0.0050 to 0.25. The acid content per unit weight of the zeolite-containing catalyst, determined from the amount of ammonia desorbed at 100-650°C during ammonia temperature-controlled desorption measurement of the zeolite-containing catalyst, is 75 μmol / g or less. Methods for converting ethanol. <2> The amount of acid (Ac) per unit weight of the zeolite-containing catalyst (unit: μmol / g) is given by the following formula (1): Ac ≤ 25-60 × [Molar ratio of Na / Al] ... (1) Satisfying <1> The method for converting ethanol as described. <3> The acid content per unit weight of the zeolite-containing catalyst is 0.5 μmol / g or more. <1> or <2> The method for converting ethanol as described. <4> In the ammonia desorption measurement of the zeolite-containing catalyst, the amount of acid per unit weight of the zeolite, determined from the amount of ammonia desorbed at 100 to 650°C, is 75 μmol / g or less. <1> ~ <3> The method for converting ethanol described in any of the following. <5> The amount of sodium contained in the zeolite-containing catalyst is 100 ppm by mass or less. <1> ~ <4> The method for converting ethanol described in any of the following. <6> The mass ratio of Si / Al in the zeolite-containing catalyst is 300 to 3000. <1> ~ <5> The method for converting ethanol described in any of the following. <7> The silica / alumina molar ratio of the zeolite in the zeolite-containing catalyst is 600 to 2000. <1> ~ <6> The method for converting ethanol described in any of the following. <8> The ethanol conversion method according to any one of <1> to <7>, wherein the zeolite-containing catalyst contains at least one doping element selected from the group consisting of phosphorus and Group 11 elements. <9> The ethanol conversion method according to <8>, wherein the content of the doping element is 2.0% by mass or less based on the total amount of the zeolite-containing catalyst. <10> The ethanol conversion method according to any one of <1> to <9>, wherein the aluminum content is 0.01% by mass to 1% by mass based on the total amount of the zeolite-containing catalyst. <11> The ethanol conversion method according to any one of <1> to <10>, wherein the mixed raw material contains ethylene. <12> The ethanol conversion method according to any one of <1> to <11>, wherein the ethanol content in the mixed raw material is 30% by mass or more based on the mixed raw material. <13> The ethanol conversion method according to any one of <1> to <12>, wherein the molar ratio of ethylene / ethanol in the mixed raw material is 0.20 to 2.50. <14> The ethanol conversion method according to any one of <1> to <13>, which has a regeneration step of contacting the zeolite-containing catalyst subjected to the reaction step with a gas containing oxygen heated to 400 °C or higher and then subjecting it to the reaction step again. <15> 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 <14>, A method for producing propylene, comprising the above steps. <16> An aromatic compound separation step of separating a fraction mainly containing an aromatic compound from the reaction gas obtained by the ethanol conversion method according to any one of <1> to <14>, A method for producing an aromatic compound, comprising the above steps. <17> A zeolite-containing catalyst, The zeolite contained in the zeolite-containing catalyst has an oxygen 10-membered ring structure, the molar ratio of Na / Al in the zeolite-containing catalyst is 0.0050 to 0.25, the amount of acid per unit weight of the zeolite-containing catalyst, determined from the ammonia desorption amount at 100 to 650 °C in the temperature-programmed ammonia desorption measurement of the zeolite-containing catalyst, is 75 μmol / g or less, a zeolite-containing catalyst. <18> The zeolite-containing catalyst according to <17>, wherein the mass ratio of Si / Al in the zeolite-containing catalyst is 300 to 3000. <19> The zeolite-containing catalyst according to <17> or <18>, wherein the zeolite-containing catalyst is a catalyst for obtaining olefins having 3 or more carbon atoms from a mixed raw material containing ethanol. <20> The zeolite-containing catalyst according to any one of <17> to <19>, wherein the zeolite-containing catalyst contains at least one doping element selected from the group consisting of phosphorus and Group 11 elements. <21> The zeolite-containing catalyst according to <20>, wherein the content of the doping element is 2.0% by mass or less based on the total amount of the zeolite-containing catalyst. <22> The zeolite-containing catalyst according to any one of <17> to <21>, wherein the aluminum content is 0.01% by mass to 1% by mass based on the total amount of the zeolite-containing catalyst. <23> A method for producing a zeolite-containing catalyst, the zeolite contained in the zeolite-containing catalyst is a zeolite having an oxygen 10-membered ring structure, [[ID=!]] the molar ratio of Na / Al in the zeolite-containing catalyst is 0.0050 to 0.25, the amount of acid per unit weight of the zeolite-containing catalyst, determined from the ammonia desorption amount at 100 to 650 °C in the temperature-programmed ammonia desorption measurement of the zeolite-containing catalyst, is 75 μmol / g or less, A method for producing a zeolite-containing catalyst, comprising a steaming step of bringing the zeolite-containing catalyst into contact with water vapor at a steaming temperature of 450°C or higher. <24> The reaction includes a step of supplying a raw material containing ethanol to a reactor having a fixed bed filled with a zeolite-containing catalyst, and obtaining a reaction gas containing an olefin having 3 or more carbon atoms and water. The zeolite contained in the zeolite-containing catalyst is a zeolite having an oxygen 10-membered ring structure. The Na / Al molar ratio of the zeolite-containing catalyst is 0.0050 to 0.25. A method for producing hydrocarbons, wherein the amount of acid per unit weight of the zeolite-containing catalyst, determined from the amount of ammonia desorbed at 100 to 650°C during ammonia temperature-controlled desorption measurement of the zeolite-containing catalyst, is 75 μmol / g or less. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a method for converting ethanol that suppresses the deterioration of catalyst performance due to water vapor and suppresses coke deposition, a zeolite-containing catalyst, a method for producing a zeolite-containing catalyst, and a method for producing hydrocarbons, etc. [Brief explanation of the drawing]

[0012] [Figure 1] Figure 1 shows a schematic diagram of one embodiment of a fixed-bed, single-stage adiabatic reactor. [Figure 2] Figure 2 shows a schematic diagram of one embodiment of an ethanol conversion apparatus. [Figure 3] Figure 3 shows a schematic diagram of one embodiment of an ethanol conversion apparatus. [Figure 4] Figure 4 shows the reaction results of Example 1. [Modes for carrying out the invention]

[0013] The present invention will be described in detail below. However, the present invention is not limited to the following embodiments (this embodiment), and can be implemented with various modifications within the scope of its gist. In this specification, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described stepwise in this specification, the upper or lower limit of a numerical range in one step can be arbitrarily combined with the upper or lower limit of a numerical range in another step.

[0014] [Method for converting ethanol] The method for converting ethanol according to this embodiment is: The reaction includes a step of supplying a mixed raw material containing ethanol to a reactor having a fixed bed filled with a zeolite-containing catalyst, and obtaining a reaction gas containing an olefin having 3 or more carbon atoms and water. The zeolite contained in the zeolite-containing catalyst has an oxygen 10-membered ring structure (also simply called a "10-membered ring structure"), The Na / Al molar ratio of the zeolite-containing catalyst is 0.0050 to 0.25. The amount of acid per unit weight of the zeolite-containing catalyst (hereinafter also referred to as "TPD acid per unit weight of catalyst"), determined from the amount of ammonia desorption measured at 100 to 650°C in the ammonia temperature-controlled desorption measurement of the zeolite-containing catalyst, is 75 μmol / g or less. According to this embodiment, by using the zeolite-containing catalyst described above, it is possible to provide a method for converting ethanol, a zeolite-containing catalyst, a method for producing a zeolite-containing catalyst, a method for producing hydrocarbons, a method for producing propylene, and a method for producing aromatic compounds, which suppress the deterioration of catalytic performance due to water vapor and suppress coke deposition. In other words, by controlling the acidic properties of the zeolite and reducing the affinity between the zeolite and water (water vapor), it is thought that the catalytic activity of the zeolite can be maintained even under reaction conditions in which water vapor is present, and the decrease in activity of the zeolite-containing catalyst as the reaction time progresses can be suppressed. Furthermore, by controlling the amount of sodium in the zeolite-containing catalyst, it is thought that structural collapse of the zeolite and coke deposition on the catalyst due to side reactions can be prevented, and the decrease in activity of the zeolite-containing catalyst can be suppressed even under reaction conditions in which ethanol is present. In addition, the zeolite-containing catalyst can suppress the deterioration of catalytic activity even in a catalyst regeneration process that involves the generation of water vapor.

[0015] Furthermore, according to this embodiment, ethanol can be converted to target compounds such as propylene and aromatic compounds in good yield. Moreover, according to this embodiment, the ethylene conversion rate can be kept constant, and ethylene can be produced stably.

[0016] [reactor] In this embodiment, the reaction process is carried out by filling a reactor having a fixed bed (hereinafter also referred to as a "fixed-bed reactor") with a zeolite-containing catalyst. The fixed-bed reactor can be of either an adiabatic reactor or an isothermal reactor. Of these, a fixed-bed adiabatic reactor is preferred from the viewpoint of superior operability. If necessary, a heating device for heating the raw materials can be provided in front of the reactor.

[0017] (Fixed-floor insulated reactor) Regarding fixed-bed adiabatic reactors, refer to the description in Adiabatic Fixed-Bed Reactors (Elsevier, 2014, Ch.1, P.4, L.5~24 ISBN:978-0-12-801306-9). Among fixed-bed adiabatic reactors, a single-stage fixed-bed adiabatic reactor with only one fixed catalyst bed is more preferable. As carbonaceous material (coke) accumulates on the catalyst during the reaction, a multi-column switching type single-stage fixed-bed adiabatic reactor that can burn off this carbonaceous material while continuing the reaction is preferable.

[0018] Figure 1 is a schematic diagram of a fixed-bed, single-stage, insulated reactor. The fixed-bed, single-stage, insulated reactor 10a comprises a reaction casing 12 with an insulating material 121 on its outer periphery, a catalyst bed 13, a reactor inlet 14, and a reactor outlet 15. The insulating material 121 on the outer periphery of the reaction casing 12 prevents heat from escaping from inside the reactor to the outside. In the manufacturing method according to this embodiment, the temperature inside the reactor can be controlled by the heat generated and absorbed by the reaction.

[0019] The catalyst bed 13 is filled with a catalyst, which will be described later. A first sheathed thermocouple 161 is placed just before it comes into contact with the catalyst bed inlet 131 of the catalyst bed 13. A second sheathed thermocouple 162 is placed immediately after it passes through the catalyst bed outlet 132 of the catalyst bed 3. These thermocouples measure the temperature of the mixed raw materials just before they come into contact with the catalyst bed inlet 131 and the temperature of the reaction gas immediately after it passes through the catalyst bed outlet 132. The positions of these thermocouples can be changed as needed. The catalyst bed 13 may be a multi-stage type, but it is preferable to have a single-stage type as shown in Figure 1.

[0020] In a fixed-bed, single-stage insulated reactor 10a, raw materials are introduced from the reactor inlet 14, brought into contact with the catalyst bed 13, and the reaction gas is removed from the reactor outlet 15.

[0021] [Zeolite-containing catalyst] The reaction step of this embodiment uses a zeolite-containing catalyst. The zeolite-containing catalyst contains zeolite. The zeolite-containing catalyst exhibits catalytic activity to convert ethanol and olefins into target compounds such as propylene. A common problem in conventional olefin production using zeolite as an ethanol raw material is the degradation of the zeolite due to water vapor. According to the ethanol conversion method of this embodiment, by controlling the acidic properties of the zeolite-containing catalyst and reducing the affinity between the zeolite-containing catalyst and water (water vapor), it is thought that the yield of the target compound can be more easily maintained over a long period of time.

[0022] The zeolite-containing catalyst may be a molded body made solely of zeolite, but a molded body containing both zeolite and a silica binder is preferred due to its superior crush strength.

[0023] In the conversion method of this embodiment, the zeolite has an oxygen 10-membered ring structure. Examples of such zeolites include ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-21, ZSM-23, ZSM-35, and ZSM-38. Among these, MFI type zeolites are preferred from the viewpoint of excellent catalytic performance (catalytic activity and durability against coking), and ZSM-5 is more preferred.

[0024] There are no particular restrictions on the method of synthesizing the zeolite in this embodiment, but it can be produced by optimizing various conditions of conventionally known hydrothermal synthesis methods for MFI-type zeolites. Generally, means of efficiently obtaining MFI-type zeolites by hydrothermal synthesis include methods using appropriate organic structure-regulating agents (SDAs), methods of adding hydrothermally synthesized MFI zeolites as seed crystals for hydrothermal synthesis, and methods of adding them as seed slurry in the crystalline stage for hydrothermal synthesis. Examples of organic structure-regulating agents used here include ammonium salts, urea compounds, amines, and alcohols. It is also known that inorganic cations and anions, not just organic SDAs, are involved in the structure, and zeolite synthesis depends on the combined function of each component. In the hydrothermal synthesis method of MFI-type zeolites described above, a suitable catalyst can be obtained by appropriately optimizing the raw material composition, such as the type of raw materials and additives (SDAs), the amount of additives, pH, silica / alumina molar ratio, medium, and the abundance ratio of cations and anions, as well as synthesis conditions such as synthesis temperature and synthesis time.

[0025] Specifically, examples include the synthesis method using the seed slurry described in Japanese Patent Publication No. 5426983, and the method exemplified in "The Hydrothermal Synthesis of Zeolites" (Chemical Reviews, 2003, 103, 663-702).

[0026] Furthermore, commercially available zeolites can also be used, as long as they possess the specific physical properties and composition described above.

[0027] (TPD acid content per unit weight of catalyst) The ethanol conversion method of this embodiment uses a zeolite-containing catalyst in which the acid content per unit weight of the zeolite-containing catalyst is 75 μmol / g or less, as determined from the amount of ammonia desorbed at 100 to 650°C during ammonia temperature-controlled desorption measurement of the zeolite-containing catalyst. By having a TPD acid content within this range, the catalyst can suppress the deterioration of catalytic performance due to water vapor. Although the acid sites of zeolite contribute to catalytic activity, they also function as autocatalysts that promote hydrolysis of the zeolite structure. Therefore, in a reactor where ethanol is included in the reaction raw materials and high-temperature water vapor is present, catalysts with too much acid tend to undergo structural breakdown of the zeolite. Controlling the TPD acid content within a specific range is considered to lead to the maintenance of the zeolite structure and catalytic function. Furthermore, if there are too many active sites, the polymerization reaction proceeds excessively, and coke tends to accumulate on the catalyst surface. Therefore, controlling the acid content below the upper limit helps to keep the amount of coke within an appropriate range. However, the factors are not limited to these.

[0028] The TPD acid content per unit weight of catalyst is preferably 40 μmol / g or less, more preferably 30 μmol / g or less, and even more preferably 25 μmol / g or less. Furthermore, because of the excellent catalytic activity per unit weight of catalyst, the TPD acid content per unit weight of catalyst is preferably 0.5 μmol / g or more, more preferably 1.5 μmol / g or more, and even more preferably 5.0 μmol / g or more.

[0029] Furthermore, repeated experimental studies revealed that sodium, conventionally used to adjust the acid content of catalysts, accelerates catalyst degradation in the reaction process of this embodiment. Therefore, in the ethanol conversion method of this embodiment, it is preferable to control the amount of sodium in addition to the amount of acid, and from the viewpoint of further improving the durability of the catalyst, the TPD acid content Ac (unit: μmol / g) per unit weight of catalyst is given by the following formula (1): Ac ≤ 25-60 × [Molar ratio of Na / Al] ... (1) It is preferable that the following conditions are met. The molar ratio of Na / Al is the molar ratio of the amount of sodium to aluminum contained in the zeolite-containing catalyst.

[0030] The sodium contained in the zeolite-containing catalyst exhibits strong basicity when present with water or ethanol under the reaction conditions of this embodiment, promoting the structural breakdown of the zeolite, which has poor basicity resistance, and accelerating catalyst degradation. In addition, sodium exhibits Lewis acidity at the same time as basicity, promoting coke deposition on the catalyst. Therefore, in order to stably produce the target compound, it is necessary to control the amount of sodium in addition to controlling the amount of acid in the zeolite-containing catalyst. In other words, in a zeolite-containing catalyst with a high sodium content, only a smaller amount of acid is permissible, and the relationship in which the upper limit of the suitable acid amount decreases with increasing sodium is expressed as equation (1). The first term 25 on the right-hand side of equation (1) represents the amount of acid per unit weight of catalyst that is suitable for achieving excellent durability of the zeolite structure. The second term on the right-hand side of equation (1) represents the effect of sodium on the catalyst's durability, calculated by multiplying the Na / Al molar ratio in the zeolite-containing catalyst by the coefficient 10. The reason the Na / Al molar ratio in the zeolite-containing catalyst is used as the variable in the second term, rather than the amount of sodium in the zeolite-containing catalyst, is that even with the same amount of sodium in the zeolite-containing catalyst, catalysts with a higher amount of acid sites, i.e., a higher aluminum content, can mitigate the adverse effects of sodium. The coefficient 60 was determined from examples that showed favorable catalyst performance in experimental studies.

[0031] The structural breakdown of zeolites due to dealuminization by water vapor is caused by the acidic properties of the zeolite. By controlling the acidic properties of the zeolite-containing catalyst, the reaction process can be carried out while suppressing dealuminization. However, the causes are not limited to this.

[0032] Among the zeolite-containing catalysts described above, the zeolite-containing catalyst exhibits superior durability, and therefore, the amount of acid per unit weight of zeolite (hereinafter referred to as "TPD acid per unit weight of zeolite"), determined from the amount of ammonia desorption at 100-650°C in the ammonia temperature-controlled desorption measurement of the zeolite-containing catalyst, is preferably 75 μmol / g or less, more preferably 40 μmol / g or less, and even more preferably 30 μmol / g or less. The TPD acid per unit weight of zeolite is preferably 0.5 μmol / g or more, more preferably 1.5 μmol / g or more, and even more preferably 5.0 μmol / g or more.

[0033] The amount of TPD acid per unit weight of catalyst can be calculated using a calibration curve method from the desorption spectrum obtained by passing diluted ammonia gas through a degassed zeolite-containing catalyst to adsorb ammonia, and then increasing the temperature. The area value of the spectrum obtained from the measurement between 100°C and 650°C is used to derive the amount of TPD acid. More details are provided in the examples. The amount of TPD acid per unit weight of zeolite is calculated by dividing the amount of TPD acid per unit weight of zeolite-containing catalyst obtained by the above method by the weight ratio of zeolite in the zeolite-containing catalyst. Here, the amount of TPD acid refers to the amount of acid before (initial) use of the zeolite-containing catalyst in the reactor.

[0034] In the zeolite-containing catalyst, the acid content retention rate, represented by the following formula, is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more. The upper limit of the acid content retention rate is not particularly limited, but it may be 98% or less.

[0035] Acid amount maintenance rate (%) = 6.0hr Acid amount after STM treatment (μmol / g) / 1.0hr Acid amount after STM treatment (μmol / g) × 100

[0036] The acid content after 6.0hr STM treatment refers to the TPD acid content of the zeolite-containing catalyst after 6 hours of steam treatment, and the acid content after 1.0hr STM treatment refers to the TPD acid content of the zeolite-containing catalyst after 1 hour of steam treatment.

[0037] The steam treatment is carried out by bubbling helium gas at a flow rate of 50 mL / min into water heated to 80°C, then cooling it to 75°C using a condenser, preparing a zeolite-containing catalyst heated to 650°C, and bringing the steam into contact with the zeolite-containing catalyst.

[0038] (Mesopore volume of zeolite-containing catalyst) In the ethanol conversion method of this embodiment, from the viewpoint of excellent adsorption characteristics of the raw material, it is preferable to use a zeolite-containing catalyst with a mesopore volume of 0.15 cc / g or more, and more preferably 0.20 cc / g or more. The mesopore volume can be measured by the mercury intrusion method using a mercury porosimeter.

[0039] (Composition of zeolite-containing catalyst) The silica / alumina (SiO2 / Al2O3) molar ratio of the zeolite contained in the zeolite-containing catalyst of this embodiment can be appropriately selected, but from the viewpoint of excellent catalyst durability, it is preferably 20 to 3000, more preferably 200 to 2500, and even more preferably 600 to 2000. The silica / alumina molar ratio of the zeolite can be measured by known methods, for example, by completely dissolving the zeolite in an alkaline aqueous solution and analyzing the resulting solution by plasma emission spectroscopy or the like.

[0040] The mass ratio of silicon (Si) to aluminum (Al) contained in the zeolite-containing catalyst of this embodiment (Si / Al mass ratio) can be appropriately selected, but from the viewpoint of excellent catalyst durability, it is preferably 125 to 3000, and more preferably 300 to 3000. The Si / Al mass ratio can be measured by known methods, for example, by completely dissolving the zeolite-containing catalyst in an alkaline aqueous solution and analyzing the resulting solution by plasma emission spectroscopy or the like. By controlling the Si / Al mass ratio of the zeolite-containing catalyst, the affinity of the zeolite-containing catalyst for water can be reduced, and the reaction process can be carried out while maintaining catalytic performance even under hydrothermal conditions. However, the factors are not limited to this. For excellent catalytic activity, the Si / Al mass ratio is preferably 3000 or less, more preferably 2500 or less, and even more preferably 2000 or less. In addition, to suppress the deterioration of catalytic performance due to water vapor, the Si / Al mass ratio is preferably 125 or more, more preferably 300 or more, and even more preferably 500 or more.

[0041] The molar ratio of sodium to aluminum (Na / Al molar ratio) in the zeolite-containing catalyst of this embodiment is 0.0050 to 0.25, preferably 0.0050 to 0.20, and more preferably 0.005 to 0.15. A Na / Al molar ratio of 0.25 or less suppresses the deterioration of catalyst performance due to water vapor, and a Na / Al molar ratio of 0.0050 or more suppresses coke deposition. A ratio of 0.20 or less is preferable, and 0.15 or less is more preferable, as it provides superior durability against catalyst deterioration due to higher temperature water vapor. Furthermore, to further suppress coke formation, a Na / Al molar ratio of 0.0060 or more is preferable, and 0.0070 or more is more preferable.

[0042] In the synthesis process of zeolites and the molding process of catalysts, sodium is used as part of the raw materials, so generally, the molar ratio of Na / Al in zeolite-containing catalysts is greater than 0.5. In order to adjust the sodium contained in the zeolite-containing catalyst to the above range, it is effective to remove sodium by washing the zeolite-containing catalyst with an acid (hereinafter also referred to as "acid washing"). The type of acid used for acid washing is not particularly limited, but for example, the molar ratio of Na / Al can be adjusted by washing with an aqueous solution of nitric acid. The acid concentration of the washing solution used for acid washing is preferably 0.010 to 10 N for excellent washing efficiency. Furthermore, in order to suppress the deactivation of zeolites associated with acid washing, the acid concentration of the washing solution is more preferably 0.01 to 2.0 N, and even more preferably 0.05 to 1.5 N. Acid washing does not particularly require heating or cooling, but from the viewpoint of excellent washing efficiency, it is preferably carried out at 10 to 90°C, and more preferably at 20 to 70°C. Acid washing is carried out, for example, by immersing the zeolite-containing catalyst in a washing solution. The immersion time is preferably 0.10 to 10 hours, and more preferably 0.50 to 6.0 hours, for optimal washing efficiency. The weight of the washing solution used for one acid washing is preferably 500 parts by mass or less, and more preferably 250 parts by mass or less, per 10 parts by mass of zeolite, for ease of wastewater treatment. Although the sodium removal rate can be increased by performing acid washing multiple times, it is preferable to perform it only once during catalyst production for ease of wastewater treatment.

[0043] Another effective method for removing sodium retained at cation sites is cation exchange. For example, ion exchange treatment using an aqueous silver nitrate solution can reduce the sodium content in the zeolite-containing catalyst and adjust the Na / Al molar ratio. Alternatively, the sodium content in the zeolite-containing catalyst can be adjusted by acid washing the raw materials used in zeolite synthesis to reduce the sodium content in the raw materials.

[0044] Sodium contained in zeolite-containing catalysts forms base sites under conditions where water or ethanol is present, causing structural breakdown of the zeolite and coke formation, thereby accelerating catalyst degradation. Therefore, in the reaction process of this embodiment, it is desirable to reduce the amount of sodium in the zeolite in order to suppress catalyst degradation. Sodium is a component that is easily introduced during zeolite synthesis and catalyst molding processes, and therefore requires particular control. Accordingly, it is thought that by controlling the molar ratio of Na / Al, the formation of base sites during the reaction can be suppressed, and the decrease in the activity of the zeolite-containing catalyst over time can be suppressed even under reaction conditions where water vapor is present.

[0045] The sodium content in the zeolite-containing catalyst of this embodiment is preferably 1,000 ppm by mass or less, more preferably 100 ppm by mass or less, and even more preferably 10 ppm by mass or less, relative to the total amount of the zeolite-containing catalyst. Furthermore, from the viewpoint of suppressing coke formation associated with side reactions, it is preferable that the sodium content be 100 ppm by mass or less. In this embodiment, the sodium content in the zeolite-containing catalyst is shown as the value measured by XRF analysis.

[0046] (Doped elements in zeolite-containing catalysts) The zeolite-containing catalyst in this embodiment may contain phosphorus and at least one doped element selected from the group consisting of elements belonging to Group 11 of the periodic table (hereinafter, these elements are collectively referred to as "doped elements"). Among these, the zeolite-containing catalyst preferably contains phosphorus or silver.

[0047] Phosphorus can take the form of phosphorus polymers (e.g., polyphosphate), phosphorus oxides (e.g., P2O5), or compounds in which phosphorus is added to the aluminum in the zeolite. Multiple forms of these may also be included. When the zeolite contains aluminum, phosphorus has the effect of suppressing the dealuminization of the zeolite. In the method according to this embodiment, water is generated in the reactor, and the raw material, ethanol, may also contain water, resulting in a high-temperature steam atmosphere in the reactor that causes dealuminization. By including phosphorus in the zeolite-containing catalyst, the dealuminization of the zeolite is suppressed, further improving the durability of the catalyst.

[0048] Elements belonging to Group 11 of the periodic table include copper, silver, and gold. Including elements from Group 11 of the periodic table suppresses the dealuminization of the zeolite, thereby increasing the durability of the catalyst. Among these elements from Group 11 of the periodic table, silver is preferred from the viewpoint of superior loading efficiency.

[0049] The doping element content in the zeolite-containing catalyst may be 2.0% by mass or less relative to the total amount of the zeolite-containing catalyst, preferably 0.01 to 2.0% by mass, and more preferably 0.05 to 1.0% by mass from the viewpoint of further suppressing dealuminization.

[0050] In this embodiment, the content of doped elements in the zeolite-containing catalyst is shown as the 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 according to the instruction manual. For example, when using a Rigaku product, product name "RIX3000", the measurement conditions can be set to use P-Kα rays, tube voltage of 50kV, and tube current of 50mA.

[0051] In this embodiment, phosphoric acid and / or phosphates (hereinafter also referred to as "phosphorus raw material") may be used as the phosphorus raw material contained in the zeolite-containing catalyst. Phosphates are more preferred as the phosphorus raw material, and among phosphates, compounds that exhibit a solubility of 1 g or more in 100 g of water at 25°C are even more preferred.

[0052] Examples of phosphoric acid include phosphoric acid and pyrophosphate, and examples of phosphate salts include ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium ammonium hydrogen phosphate, potassium hydrogen phosphate, aluminum hydrogen phosphate, sodium phosphate, potassium phosphate, etc. Among these, ammonium phosphate salts, which have relatively high solubility in water, are preferred, and more preferably, at least one selected from the group consisting of ammonium phosphate, diammonium hydrogen phosphate, and ammonium dihydrogen phosphate. These may be used individually or in combination of two or more.

[0053] In this embodiment, metal nitrate salts such as copper nitrate and silver nitrate may be used as raw materials for the elements belonging to Group 11 of the periodic table contained in the zeolite-containing catalyst. A zeolite-containing catalyst containing elements belonging to Group 11 of the periodic table can be obtained by ion exchange with a metal nitrate salt using a zeolite-containing catalyst containing sodium as a countercation and then sintering it. Ion exchange between sodium, which is the countercation in the zeolite, and the metal nitrate salt can be carried out by immersing the zeolite or zeolite-containing catalyst in an aqueous solution of the metal nitrate salt and then washing it with water. At this time, the ion exchange rate can be improved by performing the immersion and washing multiple times. Furthermore, since the degradation resistance of the zeolite is impaired if sodium remains in the catalyst as described above, it is preferable to prepare a zeolite-containing catalyst containing elements belonging to Group 11 of the periodic table using a proton-type or ammonium-type zeolite-containing catalyst.

[0054] (Method for forming zeolite-containing catalysts) The zeolite-containing catalyst of this embodiment can be manufactured by molding, for example, the following method using a zeolite having the specific physical properties and composition described above. The molding method is not particularly limited, and general methods can be used. Specifically, methods include compression molding of the catalyst component, extrusion molding, and spray-drying molding, which is optimal for fluidized bed reaction systems.

[0055] Furthermore, a binder can be used for molding. The binder is not particularly limited, and for example, silica, alumina, and kaolin can be used individually 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. In the conversion method of this embodiment, precise control of acid sites on the catalyst is required, so it is preferable that the catalyst does not contain any compounds that exhibit acidic properties other than zeolite, but binders such as alumina and kaolin exhibit acidic properties. Therefore, it is preferable to use a binder that does not exhibit acidic properties, and among these, it is more preferable to use a silica binder from the viewpoint of excellent coking resistance. The total content of zeolite and binder may be 80 to 100% by mass or 90 to 100% by mass relative to the total amount of zeolite-containing catalyst. The aluminum content in the zeolite-containing catalyst is preferably 0.01% to 1% by mass, more preferably 0.03% to 0.5% by mass, and even more preferably 0.05% to 0.1% by mass, relative to the total amount of the zeolite-containing catalyst.

[0056] (Pretreatment step for zeolite-containing catalyst) In the ethanol conversion method of this embodiment, a pretreatment step may be performed on the zeolite-containing catalyst after molding, prior to contacting the zeolite-containing catalyst with the raw materials. A preferred pretreatment step is a steaming step in which the catalyst is heated at a temperature of 450°C or higher in the presence of water vapor. Pretreatment tends to more significantly suppress catalyst degradation and improve selectivity. In the above method, it is preferable to process the catalyst at a temperature of 450°C to 900°C, with the atmosphere not particularly limited, but by circulating 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 atmospheres or higher. A more preferable heating temperature is 500°C to 700°C. Furthermore, this pretreatment step can be carried out using a reactor that converts ethanol and ethylene.

[0057] (Shape of zeolite-containing catalyst) In the ethanol conversion method of this embodiment, zeolite-containing catalysts having various shapes such as cylindrical or ring-shaped can be used, but from the viewpoint of ease of handling, it is preferable to use a cylindrical zeolite-containing catalyst. Among these, from the viewpoint of excellent catalyst strength, it is preferable to use a cylindrical molded body having a diameter of 1.6 mm or more and a length of 0.1 to 10.0 cm.

[0058] [Mixed raw materials] In the reaction process of this embodiment, a mixed raw material containing ethanol is used. From the viewpoint of excellent environmental compatibility, the ethanol is preferably derived from biomass. Biomass refers to organic resources other than fossil resources that originate from plants and animals, and biomass-derived means a compound produced using biomass as a raw material.

[0059] From the viewpoint of achieving excellent production efficiency of the target compound, the ethanol content in the mixed raw materials is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more.

[0060] In the reaction process of this embodiment, ethanol is first converted to ethylene. Ethanol is more reactive than olefins with four or more carbon atoms, and as the ethanol content in the mixed raw materials increases, the production efficiency of the target compounds, such as propylene and ethylene, which are light olefins, improves. The high reactivity of ethanol is due to the ease with which these substrates can access the zeolite reaction active sites; in other words, ethanol and ethylene, which have two carbon atoms, have smaller molecular sizes compared to olefins with four or more carbon atoms, and are less constrained by steric hindrance within the pores of the zeolite. Furthermore, the high reactivity of ethanol is also due to the fact that ethanol has a functional group containing a heteroatom, that is, the electron imbalance within the molecule.

[0061] Similar effects can be expected by using a large amount of ethylene as a mixed raw material, but from the viewpoint of stable operation of the apparatus, it is preferable to increase the proportion of carbon-2 raw materials in the mixed raw material with ethanol. This is because the process of converting ethylene to the target compound is an exothermic reaction, and if ethylene is present in excess, the temperature inside the reactor rises, and catalyst coking is promoted.

[0062] The mixed raw materials may include ethylene in addition to ethanol, from the viewpoint of easy modification of the raw material composition. Various types of ethylene produced by different 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. Among these, it is preferable that the mixed raw materials contain ethylene and water, such as the gas obtained by the dehydration of ethanol. Since water is produced as a by-product in the process of converting ethanol to ethylene, ethylene generally contains water. From the viewpoint of excellent environmental compatibility, it is preferable to use ethylene obtained by dehydrating biomass-derived ethanol. In the mixed raw materials, the molar ratio of ethylene / ethanol is preferably 0.20 to 2.50, and more preferably 0.40 to 2.0, from the viewpoint of excellent ease of reaction control.

[0063] The mixed raw materials may further contain hydrocarbons having 4 to 6 carbon atoms. Examples of hydrocarbons having 4 to 6 carbon atoms include olefins having 4 to 6 carbon atoms and saturated hydrocarbons having 4 to 6 carbon atoms. Among these, olefins having 4 to 6 carbon atoms, like ethylene and ethanol, can yield target compounds such as propylene when contacted with a zeolite-containing catalyst. Examples of hydrocarbons having 4 to 6 carbon atoms include butene, pentene, hexene, butane, pentane, and hexane. In the mixed raw materials, the molar ratio of olefins having 4 to 6 carbon atoms to ethylene is preferably 3.0 or less, more preferably 1.0 or less, and even more preferably 0.14 to 1.0. The term "olefin" above includes cycloparaffins in addition to linear, branched, and cyclic olefins.

[0064] In the ethanol conversion method of this embodiment, the mixed raw materials may further contain oxygen-containing compounds having 1 to 6 carbon atoms other than ethanol. Similar to ethylene and ethanol, oxygen-containing compounds having 1 to 6 carbon atoms can be brought into contact with a catalyst to yield target compounds such as propylene. Examples of oxygen-containing compounds having 1 to 6 carbon atoms other than ethanol include methanol, propanol, dimethyl ether, and diethyl ether. In the mixed raw materials, the molar ratio of oxygen-containing compounds having 1 to 6 carbon atoms to ethylene is preferably 1.0 or less, and more preferably 0.5 or less.

[0065] Furthermore, ethylene, ethanol, olefins with 4 to 6 carbon atoms, and oxygen-containing compounds with 1 to 6 carbon atoms other than ethanol are collectively referred to as "effective raw materials."

[0066] The mixed raw materials may also contain saturated aliphatic hydrocarbons such as paraffin, olefins with 7 or more carbon atoms, and oxygen-containing compounds with 7 or more carbon atoms, in addition to the above-mentioned effective raw materials. These saturated aliphatic hydrocarbons, olefins with 7 or more carbon atoms, and oxygen-containing compounds with 7 or more carbon atoms can be converted into the target compound by contact with a conversion catalyst, similar to ethylene and ethanol, but they are less reactive than the above-mentioned effective raw materials.

[0067] In addition to the above-mentioned raw materials that can be converted to propylene by the reaction process, the mixed raw materials may also contain inert gases such as nitrogen. Furthermore, the mixed raw materials may contain hydrogen or methane as diluent gases, but hydrogen dilution is preferable. Although hydrogen is sometimes used to suppress the deterioration of catalyst coking, it simultaneously causes hydrogenation reactions of the generated propylene, etc., which has the adverse effect of lowering the propylene purity (propylene / (propylene + propane)) [mol / mol]. In the method of this embodiment, even without hydrogen dilution, the rate of catalyst coking deterioration is small and stable operation is possible, so it is preferable not to perform hydrogen dilution.

[0068] The total content of ethylene and ethanol in the mixed raw materials 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 total amount of active raw materials. However, the amount of ethanol used in the calculation is calculated based on its equivalent mass as ethylene.

[0069] In the mixed raw materials, the total content of olefins having 4 to 6 carbon atoms is preferably 65% ​​by mass or less, and more preferably 10 to 55% by mass, relative to the total amount of effective raw materials.

[0070] The mixed raw materials may contain diethyl ether, but it is preferable that they do not contain diethyl ether. The diethyl ether content in the active raw materials is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0071] In the conversion method of this embodiment, water can be included in the mixed raw materials. Since the ethylene and ethanol contained in the raw materials are produced by various manufacturing methods, they contain "water generated during the manufacturing process." Here, "water generated during the manufacturing process" refers to water that is generated during the manufacturing process of ethylene and / or ethanol and has not been removed. In the conversion method of this embodiment, water can be added to the mixed raw materials in addition to the "water generated during the manufacturing process." Water has the effect of suppressing coking deterioration by lowering the partial pressure of olefins and improving the yield of lower olefins. On the other hand, from the viewpoint of having excellent production efficiency of the target compound per raw material flow rate, it is preferable not to include water in the mixed raw materials in addition to the "water generated during the manufacturing process."

[0072] [Reaction conditions] The reaction temperature in the reaction step is preferably 400 to 600°C, more preferably 450 to 580°C, and even more preferably 480 to 550°C, from the viewpoint of obtaining an excellent yield of the target compound.

[0073] When using an adiabatic reactor, the reaction temperature is as follows: The catalyst bed inlet temperature is the temperature of the raw materials just before the raw material fluid comes into contact with the catalyst bed packed in the adiabatic reactor. The catalyst bed outlet temperature is the temperature of the reaction gas immediately after it passes through the catalyst bed. The temperatures of the raw materials and reaction gas referred to here are temperatures between 0d and 0.8d, where the center of the reactor is defined as 0 and the distance from the center of the reactor to the inner wall of the reactor is d, in a plane perpendicular to the direction of fluid flow. The average inlet and outlet reaction temperature is calculated by measuring the catalyst bed inlet temperature and catalyst bed outlet temperature, as shown in Figure 1, and using the formula: [catalyst bed inlet temperature + catalyst bed outlet temperature] / 2 (hereinafter also simply referred to as "reaction temperature"). When using an adiabatic reactor, the catalyst bed inlet temperature is preferably 480°C to 550°C, and the catalyst bed outlet temperature is preferably 480°C to 550°C. The temperature difference between the outlet temperature of the catalyst bed and the inlet temperature of the catalyst bed is preferably -80K to 80K, and more preferably -60K to 60K.

[0074] The reaction pressure in the reaction process is preferably 0.01 to 3.0 MPaG, and more preferably 0.01 to 1.0 MPaG.

[0075] The supply rate of the active raw material is preferably 0.1 to 1000 hours, based on the space velocity (WHSV) of the zeolite-containing catalyst on a mass basis. -1 More preferably 0.1 to 100 hours -1 More preferably 0.5 to 50 hours -1 In the reaction process, WHSV is calculated by converting ethanol to ethylene, as shown in the formula below. Furthermore, the mass flow rate of the active raw material 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.

[0076] WHSV(hr -1 ) = Effective raw material supply flow rate (kg / hr) / Catalyst amount (kg)

[0077] Effective raw material flow rate (kg / hr) = Ethylene flow rate (kg / hr) + Ethylene-equivalent ethanol flow rate (kg / hr) + Olefin flow rate (4-6 carbon atoms) (kg / hr) + Oxygen-containing compound flow rate (1-6 carbon atoms) other than ethanol (kg / hr)

[0078] Ethylene-equivalent ethanol flow rate (kg / hr) = Ethanol flow rate (kg / hr) × Ethylene molecular weight (g / mol) / Ethanol molecular weight (g / mol)

[0079] [Regeneration process] The ethanol conversion method of this embodiment may include a regeneration step (hereinafter also referred to as the "regeneration step") in which the zeolite-containing catalyst used in the reaction step is brought into contact with an oxygen-containing gas heated to 400°C or higher, and then used again in the reaction step. When the zeolite-containing catalyst is used in the reaction for a long period of time, coke accumulates on the catalyst, causing coking deterioration. The regeneration step allows the coke accumulated on the zeolite-containing catalyst to be burned off. Examples of oxygen-containing gas used in the regeneration step include air, or a mixture of air or oxygen and an inert gas. The oxygen concentration in the gas to be brought into contact is preferably 0.1 to 2.0 by volume. The contact temperature with the gas is preferably 20°C higher (preferably 30°C higher, more preferably 40°C higher) or higher than the temperature of the reaction step. Specifically, the contact temperature may be 400 to 700°C. In the regeneration step, by using the zeolite catalyst used in the reaction step, water derived from water vapor generated in the reaction step is included, and water is also generated by burning the coke. Therefore, in the regeneration process, the zeolite catalyst comes into contact with water vapor under temperature conditions of 400°C or higher, which promotes structural breakdown of the zeolite. However, as shown in this embodiment, by controlling the amount of TPD acid in a specific zeolite-containing catalyst, the affinity between the zeolite and water (water vapor) can be reduced, thereby suppressing the deterioration of catalytic activity. Either external regeneration, in which the catalyst is removed from the reactor and regenerated outside the reactor, or internal regeneration, in which the catalyst is not removed from the reactor and regenerated inside the reactor, may be employed. Furthermore, by employing a switchable reactor, reaction-regeneration switching operation can also be performed.

[0080] (Reaction-Regeneration switching operation) Reaction-regeneration switching operation is an operating method that uses a two-column or multi-column switching reactor to simultaneously carry out the reaction process and the regeneration process. For example, in the case of a three-column switching reactor, two columns are used for the reaction process, while the remaining column is used for catalyst regeneration. Subsequently, the reaction process in one of the columns that was used for the reaction process is stopped to perform catalyst regeneration, and the reaction process is then carried out in the column that was used for catalyst regeneration. This allows for catalyst regeneration while maintaining the production capacity of two columns. This type of reaction is also called the merry-go-round method, and it is preferable from the standpoint of superior production efficiency because it does not require stopping the manufacturing process for catalyst regeneration.

[0081] [Product: Reaction gas containing olefins with 3 or more carbon atoms] In the conversion method of this embodiment, a reaction gas containing an olefin having 3 or more carbon atoms is obtained by contacting the raw material with a zeolite-containing catalyst. The reaction gas may also contain ethylene. The reaction gas may also 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 the conversion method of this embodiment, 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.

[0082] [Separation process] In the conversion method according to this embodiment, the target compound can be efficiently purified by providing a separation step and performing various separation operations. In particular, it is preferable to include a step of separating the reaction gas obtained in the above-mentioned reaction step into fraction A mainly containing hydrocarbons having 2 to 3 carbon atoms and fraction B mainly containing hydrocarbons having 4 to 6 carbon atoms using a separation apparatus. By separating into each fraction in this way, the target compound can be efficiently separated. Examples of separation apparatus used in the separation step are a distillation column, a quench column, and a decanter.

[0083] Alternatively, the reaction gas obtained in the above-described reaction step, or the fraction separated from the reaction gas (hereinafter also referred to as the "connecting fraction"), may be introduced into the purification system of an ethylene plant to separate target compounds such as ethylene, propylene, and aromatic compounds.

[0084] The method according to this embodiment may be carried out using an apparatus having a reactor 1 and a first distillation column 2, as shown in Figure 2. The reaction gas obtained from the reaction step carried out in reactor 1 is separated in the first distillation column 2 into fraction A mainly containing hydrocarbons having 1 to 3 carbon atoms and fraction B mainly containing hydrocarbons having 4 to 6 carbon atoms. Ethylene and propylene are efficiently separated from the reaction gas by separating ethylene from fraction A in a distillation column (not shown) and further separating propylene in a distillation column (not shown). Alternatively, although not shown, the reaction gas and / or at least a portion of fraction A may be introduced into the 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.

[0085] The method according to this embodiment can be carried out using an apparatus having a reactor 1, a cooler 3, an oil-water separator 4, and a first distillation column 2, as shown in Figure 3. The reaction gas obtained from the reaction process carried out in reactor 1 is separated in cooler 3 into fraction C mainly containing hydrocarbons with 1 to 6 carbon atoms and fraction D mainly containing water, hydrocarbons with 7 or more carbon atoms, and aromatic compounds. In fraction D, "mainly containing water, hydrocarbons with 7 or more carbon atoms, and aromatic compounds" means that the total amount of water, hydrocarbons with 7 or more carbon atoms, and aromatic compounds exceeds 50% by mass of the total amount of fraction D. Fraction C is separated in the first distillation column 2 into fraction A mainly containing hydrocarbons with 1 to 3 carbon atoms and fraction B mainly containing hydrocarbons with 4 to 6 carbon atoms. Fraction D is separated in oil-water separator 4 into fraction E mainly containing hydrocarbons with 7 or more carbon atoms and aromatic compounds, and fraction F mainly containing water. By introducing fraction E into the purification system, the purification of aromatic compounds can be carried out efficiently. In this way, by separating the reaction gas into fractions A, B, and E, the target compounds such as propylene and aromatic compounds can be efficiently purified. At least a portion of fractions A, B, and E 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.

[0086] In each fraction, "mainly contains" means that the total mass of the components listed as "mainly contains" exceeds 50% by mass for each fraction. These separation processes can be carried out by combining various known methods such as distillation and extraction.

[0087] As described above, various hydrocarbons can be obtained by the ethanol conversion method of this embodiment. In other words, the ethanol conversion method of this embodiment is, from another perspective, a method for producing hydrocarbons. The hydrocarbon may be either a saturated hydrocarbon or an unsaturated hydrocarbon. Examples of unsaturated hydrocarbons include olefins and aromatic hydrocarbon compounds.

[0088] [Methods for producing hydrocarbons, etc.] Various chemical products can be obtained by separating the target compound from the reaction gas obtained by this embodiment. In other words, the hydrocarbon production method according to this embodiment involves contacting a mixed raw material containing ethylene and ethanol with a catalyst in an adiabatic reactor to obtain a reaction gas containing an olefin having 3 or more carbon atoms. The details of this production method are as described above in the ethanol conversion method, and the preferred embodiments are similar.

[0089] Examples of hydrocarbons obtained by this manufacturing method include aliphatic unsaturated hydrocarbons such as olefins like propylene, ethylene, butene, pentene, hexene, and heptene, dienes like 1,3-butadiene and isoprene, aromatic hydrocarbons like benzene and toluene, and aliphatic saturated hydrocarbons like ethane, propane, butane, and pentane. It is preferable that the aromatic hydrocarbons have a boiling point of 500°C or lower at atmospheric pressure.

[0090] By introducing the obtained hydrocarbons into the cracker's purification system, the target hydrocarbon compounds can be efficiently purified. The hydrocarbon manufacturing method according to this embodiment is A cracking process that breaks down hydrocarbons with 2 or more carbon atoms, A purification step for purifying the components obtained in the cracking step, It has, In the purification step described above, the reaction gas obtained by the ethanol conversion method described above, or its purified fraction, is added. With the above configuration, it is possible to obtain the desired hydrocarbon from ethanol resources using conventional crackers. For example, by using bioethanol as a raw material in the ethanol conversion method, bio-derived hydrocarbons can be produced.

[0091] Examples of hydrocarbons having two or more carbon atoms include ethylene, propylene, butene, paraffin, and aromatic hydrocarbons. Naphtha may also be used as a hydrocarbon having two or more carbon atoms.

[0092] For the cracker, a pyrolysis furnace used for ethane crackers, naphtha crackers, etc., may be used.

[0093] In the refining process, a refining system used in conventional ethane crackers or naphtha crackers may be used, and distillation may be carried out using equipment equipped with, for example, a distillation column and a quench column.

[0094] The reaction gas obtained by the ethanol conversion method described above, or its purified fraction, is combined in the purification process described above, but the confluence point is appropriately selected depending on the components to be combined.

[0095] The method for producing monomers according to this embodiment is: An unsaturated hydrocarbon separation step is performed to separate a fraction mainly containing unsaturated hydrocarbons from the reaction gas obtained by the ethanol conversion method described above. Includes. Examples of unsaturated hydrocarbons include aliphatic unsaturated hydrocarbons such as olefins like propylene, ethylene, butene, butane, pentene, hexene, and heptene, and dienes like 1,3-butadiene and isoprene.

[0096] The method for producing olefins according to this embodiment is: An olefin separation step is performed to separate a fraction mainly containing olefins from the reaction gas obtained by the ethanol conversion method described above. Includes.

[0097] The method for producing propylene according to this embodiment is: A propylene separation step is performed to separate a fraction mainly containing propylene from the reaction gas obtained by the ethanol conversion method described above. Includes.

[0098] The method for producing ethylene according to this embodiment is: An ethylene separation step is performed to separate a fraction mainly containing ethylene from the reaction gas obtained by the ethanol conversion method described above. Includes.

[0099] The method for producing the diene according to this embodiment is: A diene separation step is performed to separate a fraction mainly containing dienes from the reaction gas obtained by the ethanol conversion method described above. Includes.

[0100] The monomer production method according to this embodiment may further include a step of converting unsaturated hydrocarbons.

[0101] The method for producing acrylic monomer according to this embodiment is: An unsaturated hydrocarbon separation step is performed to separate a fraction mainly containing unsaturated hydrocarbons from the reaction gas obtained by the ethanol conversion method described above, An acrylic monomer production step for obtaining acrylic monomers from unsaturated hydrocarbons obtained by the unsaturated hydrocarbon separation step, Includes. The acrylic monomer production process employs known methods for introducing acrylic monomers from unsaturated hydrocarbons.

[0102] The method for producing acrylonitrile according to this embodiment is: A propylene separation step is performed to separate a fraction mainly containing propylene from the reaction gas obtained by the ethanol conversion method described above, An acrylonitrile manufacturing process for obtaining acrylonitrile from propylene obtained in the propylene separation process, Includes. The acrylic monomer production process employs known methods for introducing acrylic monomers from unsaturated hydrocarbons.

[0103] The method for producing styrene according to this embodiment is: An ethylene separation step is performed to separate a fraction mainly containing ethylene from the reaction gas obtained by the ethanol conversion method described above, A styrene production process for obtaining styrene from ethylene obtained in the ethylene separation step, Includes.

[0104] The monomers obtained by the above-described manufacturing method may be further polymerized. The method for producing the polymer according to this embodiment is: A step of polymerizing the monomer obtained by the above-described monomer manufacturing method, Includes. The process of polymerizing monomers can be carried out using conventional polymerization methods, and polymerization can be performed using various initiators and polymerization catalysts.

[0105] The method for producing the olefin polymer according to this embodiment is: A step of polymerizing a polymerizable composition containing an olefin obtained by the above-described method for producing olefins, Includes. The polymerizable composition may consist of an olefin alone as the monomer, or it may contain other monomers having unsaturated bonds.

[0106] The method for producing the polypropylene polymer according to this embodiment is: A step of polymerizing a polymerizable composition containing propylene obtained by the above-described method for producing propylene, Includes. The polymerizable composition may consist of propylene alone as the monomer, or it may contain other monomers having unsaturated bonds.

[0107] The method for producing polyethylene polymers according to this embodiment is: A step of polymerizing a polymerizable composition containing ethylene obtained by the above-described method for producing ethylene, Includes. The polymerizable composition may consist of ethylene alone as the monomer, or it may contain other monomers having unsaturated bonds.

[0108] The method for producing the diene polymer according to this embodiment is: A step of polymerizing a polymerizable composition containing the diene obtained by the above-described method for producing the diene, Includes. The polymerizable composition may consist of a diene alone as the monomer, or it may contain other monomers having unsaturated bonds.

[0109] The method for producing the acrylic monomer-based polymer according to this embodiment is: A step of polymerizing a polymerizable composition containing an acrylic monomer obtained by the above-described method for producing acrylic monomers, Includes. The polymerizable composition may consist of acrylic monomers alone, or it may contain other monomers having unsaturated bonds.

[0110] The method for producing the acrylonitrile polymer according to this embodiment is as follows: A step of polymerizing a polymerizable composition containing acrylonitrile obtained by the above-described method for producing acrylonitrile, Includes. The polymerizable composition may consist of acrylonitrile alone as the monomer, or it may contain other monomers having unsaturated bonds.

[0111] The method for producing a styrene-based polymer according to this embodiment is: A step of polymerizing a polymerizable composition containing styrene obtained by the above-described method for producing styrene, Includes. The polymerizable composition may consist of styrene alone as the monomer, or it may contain other monomers having unsaturated bonds.

[0112] Aromatic compounds may be separated from the reaction gas obtained by the ethanol conversion method described above. The method for producing an aromatic compound according to this embodiment is: A fraction mainly containing aromatic compounds is separated from the reaction gas obtained by the ethanol conversion method described above in an aromatic compound separation step. Includes. Examples of aromatic hydrocarbons include benzene, toluene, and xylene. [Examples]

[0113] The embodiment will be described in more detail below with reference to examples, but this embodiment is not limited to the following examples.

[0114] [Method for measuring catalyst properties] The various physical properties of the catalyst were measured as shown below.

[0115] (1) Molar ratio of silica / alumina in zeolite A solution was prepared by completely dissolving zeolite in a sodium hydroxide solution. The amounts of Si and Al contained in this solution were measured using a conventional method with an ICP (inductively coupled plasma) emission spectrometer (Rigaku, product name "JY138"), 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.

[0116] (2) Al content and Si content in the zeolite-containing catalyst A solution was prepared by completely dissolving the zeolite-containing catalyst in a sodium hydroxide solution, and the amount of aluminum (Al) in the zeolite-containing catalyst was measured and derived using the same method as in (1).

[0117] (3) Content of doped elements in zeolite-containing catalysts The doped element content in the zeolite-containing catalyst was measured using a conventional method with an X-ray fluorescence analyzer (Rigaku, product name "RIX3000").

[0118] (4) Zeolite structural types 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 (Bruker, product name "D8 Advance") and referring to the diffraction patterns of known zeolites. The measurement conditions were as follows. Cu cathode Tube voltage: 40kV Bulb current: 40mA Scan speed: 6 degrees / minute

[0119] (5) Amount of TPD acid per unit weight of zeolite-containing catalyst, and amount of TPD acid per unit weight of zeolite The TPD acid content of the zeolite-containing catalyst, "the acid content determined from the amount of ammonia desorbed at 100-650°C in ammonia temperature-controlled desorption measurement," was measured using the BELCAT II temperature-controlled desorption spectrometer by the following method. As a pretreatment, 1.0 g of the catalyst sample was heated to 650°C in He gas and then cooled to 100°C. Next, with the catalyst sample heated to 100°C, 5 vol% ammonia gas diluted with helium gas was passed through it to adsorb ammonia onto the catalyst sample. Then, with the catalyst sample heated to 100°C, helium gas containing saturated water vapor at 80°C was passed through it to remove the ammonia physically adsorbed onto the catalyst. After passing helium gas at 50 mL / min and holding at 100°C for 90 minutes, the amount of ammonia desorbed was measured by heating from 100°C to 850°C at a heating rate of 5°C / min. A mass spectrum with m / z=16 was used to detect the desorbed ammonia. From the mass spectrum obtained from the measurement, the area value from the point where heating from 100°C to 850°C started to the point where 650°C was reached was calculated, and the amount of TPD acid per unit weight of zeolite-containing catalyst was calculated using the calibration curve method. Furthermore, the amount of TPD acid per unit weight of zeolite was calculated from the weight ratio of TPD acid per unit weight of zeolite to the amount of TPD acid per unit weight of the obtained zeolite-containing catalyst. (Acid amount maintenance rate) In this example, the acid retention rate was calculated by steam treatment (STM treatment) of a zeolite-containing catalyst and observing the acid content over time. The steam treatment used to calculate the acid retention rate was carried out by bubbling helium gas at a flow rate of 50 mL / min into water heated to 80°C, cooling it to 75°C using a condenser, and then bringing it into contact with the zeolite-containing catalyst heated to 650°C. The acid content retention rate, which indicates the degradation resistance of zeolite-containing catalysts under hydrothermal conditions, was calculated using the following formula. Acid amount maintenance rate (%) = 6.0hr Acid amount after STM treatment (μmol / g) / 1.0hr Acid amount after STM treatment (μmol / g) × 100

[0120] (6) Mesopore volume of zeolite-containing catalyst The mesopore volume of the zeolite-containing catalyst was measured using a mercury intrusion porosimeter (Autopore 9500, MicroMeritics) by the following method. First, as a pretreatment, the zeolite-containing catalyst was coarsely ground and then sieved to adjust the particle size. After drying the sample after particle size adjustment, 0.5 g of the sample was introduced into a measurement cell, filled with mercury, and pressurized. The mesopore volume was calculated from the amount of mercury that penetrated.

[0121] (7) Sodium content in zeolite-containing catalyst The sodium content in the zeolite-containing catalyst was measured by a conventional method using an X-ray fluorescence analyzer (Rigaku, product name "RIX3000") (hereinafter also simply referred to as "XRF analysis").

[0122] (Molar ratio of Na / Al) The molar ratio of Na / Al was calculated using the following formula. The molar ratio of Na / Al in a zeolite-containing catalyst = [Sodium content (mass%) ÷ Atomic weight of sodium] ÷ [(Aluminum content (mass%) / Atomic weight of aluminum)]

[0123] (8) Strength of zeolite-containing catalyst The strength of the zeolite-containing catalyst was calculated using a digital hardness tester (Fujiwara Seisakusho Co., Ltd., product name "KHT-40"). Catalyst samples were prepared by drying them at 120°C for more than 3 hours, and the diametrical crushing strength was obtained using a hardness tester fitted with a 3 mm diameter indenter (unit: N). Thirty samples were measured, and the value obtained by dividing the average value by 3 (unit: N / mm) was defined as the strength of the zeolite-containing catalyst.

[0124] (9) Coke amount The amount of coke was calculated using the following method: The zeolite-containing catalyst after the reaction was crushed, and the weight loss rate in the temperature range of 500°C to 700°C was measured using a thermogravimetric differential thermal analyzer. The value obtained by dividing the weight loss rate by the effective raw material supply mass (unit: mass ppm) was defined as the amount of coke. Effective raw material supply mass (kg) = Effective raw material supply mass flow rate (kg / hr) × Time from start to end of reaction (hr) [Analysis conditions for thermogravimetric differential thermal analysis equipment] Device: Rigaku TG-DTA8122 Sample container: Pt pan (φ5mm × 2.5mmh) Reference sample: α-alumina Atmosphere: Air (500cc / min) Temperature: (1) Increase temperature from room temperature to 120°C at a rate of 20°C / min. (2) Hold at 120°C for 10 minutes (3) Increase the temperature from 120°C to 900°C at a rate of 10°C / min.

[0125] [Method for converting ethanol] (reactor) The following examples and comparative examples were evaluated using the fixed-bed, single-stage, insulated reactor 1 shown in Figure 1.

[0126] (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, with the reactor center set to 0 and the distance from the reactor center to the reactor inner wall being d, the temperature was measured between 0.5d and 0.6d. The effect of heat dissipation due to the insertion of these thermocouples is negligibly small. In addition, the thermocouples were moved in the direction of fluid flow as needed to measure the lowest temperature inside the reactor.

[0127] (raw materials) In the following examples, the process was carried out using a raw material containing ethanol. In addition to ethanol, the raw material may also contain ethylene, 1-butene, and water. The molar ratio of ethylene / ethanol and the molar ratio of olefins with 4 to 6 carbon atoms / ethylene in the raw material were calculated using the following formulas.

[0128] Ethylene / ethanol molar ratio (-) = Molar flow rate of ethylene (mol / hr) / Molar flow rate of ethanol (mol / hr)

[0129] The molar ratio of olefins with 4-6 carbon atoms to ethylene (-) = flow rate of olefins with 4-6 carbon atoms (mol / hr) / molar flow rate of ethylene (mol / hr) (Evaluation of reaction processes)

[0130] The reaction was carried out according to the following examples and comparative examples, so that the average inlet and outlet reaction temperature was 530°C or 500°C. A portion of the reactor outlet gas was sampled every 3 hours from the start of the reaction and introduced into a gas chromatograph (TCD (Thermal Conductivity Detector) and FID (Flame Ionization Detector) 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 stoppage was calculated. The average inlet and outlet reaction temperature was calculated according to the following formula. Average inlet / outlet reaction temperature (°C) = [Catalyst bed inlet temperature (°C) + Catalyst bed outlet temperature (°C)] / 2

[0131] [Analytical conditions for gas chromatography] (Reaction gas analysis) Equipment: Shimadzu GC-2030 Column: Custom capillary column SPB-1 manufactured by SUPELCO, USA (inner diameter 0.25 mm, length 60 m, film thickness 3.0 μm) Sample gas volume: 1 mL (Sampling line should be kept warm at 200°C to 300°C) Temperature increase program: The temperature was maintained at 40°C for 12 minutes, then increased at a rate of 5°C / min to 200°C, and then maintained at 200°C for 22 minutes. Split ratio: 200:1 Carrier gas (nitrogen) flow rate: 120 mL / min FID detector: Air supply pressure 50kPa (approx. 500mL / min), hydrogen supply pressure 60kPa (approx. 50mL / min) Measurement method: A TCD detector and an FID detector were connected in series. Composition analysis was performed based on the data detected by the TCD detector for hydrogen and the data detected by the FID detector for oxygen-containing substances such as hydrocarbons and ethanol. The concentration of each component in the reaction gas was determined using a calibration curve method, and the mass produced per unit time by the reaction was calculated.

[0132] (Ethylene yield) The ethylene yield represents the selectivity for ethylene in the reaction process and was calculated using the following formula. Ethylene yield (mass%) = Mass of ethylene produced per hour in the reaction process (kg / hr) / Mass flow rate of available raw materials (kg / hr) × 100

[0133] (Ethylene conversion rate) Although the raw materials in this embodiment do not necessarily contain ethylene, ethylene is produced in the reaction process of this embodiment, and since ethylene is the smallest olefin, the ethylene conversion rate, derived from the mass of ethylene per unit time in the reaction gas, was adopted as an indicator to evaluate catalytic activity. The ethylene conversion rate was calculated using the following formula. Ethylene conversion rate (mass%) = (Effective raw material supply mass flow rate (kg / hr) - Ethylene mass per hour in reaction gas (kg / hr)) / Effective raw material supply mass flow rate (kg / hr) × 100

[0134] Effective raw material supply mass flow rate (kg / hr) = Ethylene flow rate (kg / hr) + Ethylene-equivalent ethanol flow rate (kg / hr) + Olefin flow rate (4-6 carbon atoms) (kg / hr) + Oxygen-containing compound flow rate (1-6 carbon atoms) (kg / hr)

[0135] Ethylene-equivalent ethanol flow rate (kg / hr) = Ethanol flow rate (kg / hr) × Ethylene molecular weight (g / mol) / Ethanol molecular weight (g / mol)

[0136] (Propylene yield) The propylene yield represents the selectivity for propylene in the reaction process and was calculated using the following formula.

[0137] Propylene yield (mass%) = Mass of propylene produced per hour in the reaction process (kg / hr) / Mass flow rate of available raw materials (kg / hr) × 100

[0138] (Aromatic yield) The aromatic yield represents the selectivity for aromatic compounds in the reaction process and was calculated using the following formula.

[0139] Aromatic yield (mass%) = Mass of aromatic compounds produced per hour in the reaction process (kg / hr) / Mass flow rate of available raw materials (kg / hr) × 100

[0140] Effective raw material supply mass flow rate (kg / hr) = Ethylene flow rate (kg / hr) + Ethylene-equivalent ethanol flow rate (kg / hr) + Olefin flow rate (4-6 carbon atoms) (kg / hr) + Oxygen-containing compound flow rate (1-6 carbon atoms) (kg / hr)

[0141] Ethylene-equivalent ethanol flow rate (kg / hr) = Ethanol flow rate (kg / hr) × Ethylene molecular weight (g / mol) / Ethanol molecular weight (g / mol)

[0142] (Yield maintenance rate) In Examples 1-6 and Comparative Example 1, a 48-hour reaction cycle was defined as one cycle, and the retention rates of the ethylene conversion rate after 24 hours, the ethylene conversion rate after 48 hours, the propylene yield after 24 hours, the propylene yield after 48 hours, the aromatic yield after 24 hours, and the aromatic yield after 48 hours were calculated using the following formulas.

[0143] In Examples 7-14 and Comparative Examples 3-5, the accumulated coke was removed by regenerating the catalyst after the first cycle, and the second cycle was performed under the same conditions. The retention rates of the ethylene conversion rate, propylene yield, and aromatic yield after regeneration were then calculated using the following formulas.

[0144] Maintenance rate of ethylene conversion rate after 24 hours (mass%) = Ethylene conversion rate at 24 hours after the start of the first cycle (mass%) / Ethylene conversion rate at 3 hours after the start of the first cycle (mass%) × 100

[0145] Maintenance rate of ethylene conversion rate after 48 hours (mass%) = Ethylene conversion rate at 48 hours after the start of the first cycle (mass%) / Ethylene conversion rate at 3 hours after the start of the first cycle (mass%) × 100

[0146] Maintenance rate of ethylene conversion rate after regeneration (mass%) = Ethylene conversion rate at 3 hours after the start of the second cycle (mass%) / Ethylene conversion rate at 3 hours after the start of the first cycle (mass%) × 100

[0147] Maintenance percentage of propylene yield after 24 hours (mass%) = Propylene yield at 24 hours after the start of the first cycle (mass%) / Propylene yield at 3 hours after the start of the first cycle (mass%) × 100

[0148] Maintenance rate of propylene yield after 48 hours (mass%) = Propylene yield at 48 hours after the start of the first cycle (mass%) / Propylene yield at 3 hours after the start of the first cycle (mass%) × 100

[0149] Maintenance rate of propylene yield after regeneration (mass%) = Propylene yield at 3 hours after the start of the second cycle (mass%) / Propylene yield at 3 hours after the start of the first cycle (mass%) × 100

[0150] Maintenance percentage of aromatic yield after 24 hours (mass%) = Aromatic yield at 24 hours after the start of the first cycle (mass%) / Aromatic yield at 3 hours after the start of the first cycle (mass%) × 100

[0151] The retention rate of aromatic yield after 48 hours (mass%) = Aromatic yield at 48 hours after the start of the first cycle (mass%) / Aromatic yield at 3 hours after the start of the first cycle (mass%) × 100

[0152] Maintenance rate of aromatic yield after regeneration (mass%) = Aromatic yield at 3 hours after the start of the second cycle (mass%) / Aromatic yield at 3 hours after the start of the first cycle (mass%) × 100

[0153] [Production Example 1: Preparation of Zeolite-Containing Catalyst 1] Clay was obtained by kneading clay from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 980), an intermediate pore size zeolite, and 89 parts by mass of colloidal silica solution equivalent to 30 parts by mass of silica (33.8% by mass of silica, sodium content of 28 ppm by mass relative to the total amount of colloidal silica solution). After kneading, extrusion molding was performed to obtain extruded bodies adjusted to a diameter of 2.1 mm and a length of 4-6 mm. The obtained bodies were fired at 600°C for 5 hours to obtain zeolite-containing catalyst 1. At this time, the sodium element content in the zeolite-containing catalyst was 55 ppm by mass.

[0154] [Production Example 2: Preparation of Zeolite-Containing Catalyst 2] Clay obtained from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 980), an intermediate pore size zeolite, and 89 parts by mass of colloidal silica (33.8% by mass of silica, sodium content of 28 ppm by mass relative to the total volume of colloidal silica liquid), equivalent to 30 parts by mass of silica, was kneaded and then extruded to obtain extruded molded bodies with a diameter of 2.1 mm and a length of 4-6 mm. The obtained molded bodies were calcined at 600°C for 5 hours to obtain a catalyst precursor. The obtained catalyst precursor was stirred in a 0.1N sodium nitrate aqueous solution for 1 hour, then filtered and washed, and calcined at 600°C for 5 hours to obtain a sodium exchanger. The sodium exchanger was stirred in a 0.01N silver nitrate aqueous solution for 1 hour, and the process of filtration and washing was repeated three times, and then calcined at 600°C for 5 hours to obtain a silver exchanger. Zeolite-containing catalyst 2 was obtained by supplying and circulating a water vapor-air mixture gas containing 80% by volume of water vapor to a silver exchanger under conditions of a pressure of 0.1 MPa and a temperature of 600°C for 24 hours. At this time, the silver element content in the zeolite-containing catalyst was 0.16 mass%, and the sodium element content was 46 mass ppm.

[0155] [Manufacturing Example 3: Method for preparing zeolite-containing catalyst 3] Clay was obtained by kneading clay made from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 980), an intermediate pore size zeolite, and 89 parts by mass of colloidal silica (33.8% by mass of silica, sodium content of 28 ppm by mass relative to the total amount of colloidal silica liquid), which corresponds to 30 parts by mass of silica. After kneading, extrusion molding was performed to obtain extruded molded bodies adjusted to a diameter of 2.1 mm and a length of 4-6 mm. A predetermined amount of diammonium hydrogen phosphate aqueous solution was supported on the obtained molded bodies to obtain phosphorus-supported products. The obtained phosphorus-supported products were calcined at 600°C for 5 hours in an air atmosphere. The calcined products were filled into a reactor, and a water vapor-nitrogen mixed gas containing 80% by volume of water vapor was supplied and circulated under conditions of a pressure of 0.1 MPa and a temperature of 600°C for 24 hours to obtain zeolite-containing catalyst 3. At this time, the phosphorus element content in the zeolite-containing catalyst was 0.032% by mass, and the sodium element content was 76 ppm by mass.

[0156] [Production Example 4: Preparation of Zeolite-Containing Catalyst 4] Clay was obtained by kneading clay made from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 212), an intermediate pore size zeolite, and 89 parts by mass of colloidal silica (33.8% by mass of silica, sodium content of 28 ppm by mass relative to the total amount of colloidal silica liquid), which corresponds to 30 parts by mass of silica. After kneading, extrusion molding was performed to obtain extruded molded bodies adjusted to a diameter of 1.6 mm and a length of 4-6 mm. A predetermined amount of diammonium hydrogen phosphate aqueous solution was supported on the obtained molded bodies to obtain phosphorus-supported products. The obtained phosphorus-supported products were calcined at 600°C for 5 hours in an air atmosphere. The calcined products were filled into a reactor, and a water vapor-nitrogen mixed gas containing 80% by volume of water vapor was supplied and circulated under conditions of a pressure of 0.1 MPa and a temperature of 600°C for 24 hours to obtain zeolite-containing catalyst 4. At this time, the phosphorus element content in the zeolite-containing catalyst was 0.14% by mass, and the sodium element content was 253 ppm by mass.

[0157] [Production Example 5: Preparation of Zeolite-Containing Catalyst 5] Clay was obtained by kneading clay made from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 302), a zeolite with an intermediate pore size, and 89 parts by mass of colloidal silica (33.8% by mass of silica, sodium content of 28 ppm by mass relative to the total amount of colloidal silica liquid), which corresponds to 30 parts by mass of silica. After kneading, extrusion molding was performed to obtain extruded bodies adjusted to a diameter of 1.6 mm and a length of 4-6 mm. A predetermined amount of diammonium hydrogen phosphate aqueous solution was supported on the obtained bodies to obtain phosphorus-supported products. The obtained phosphorus-supported products were calcined at 600°C for 5 hours in an air atmosphere. The calcined products were filled into a reactor, and a water vapor-nitrogen mixed gas containing 80% by volume of water vapor was supplied and circulated under conditions of a pressure of 0.1 MPa and a temperature of 600°C for 24 hours to obtain zeolite-containing catalyst 5. At this time, the phosphorus element content in the zeolite-containing catalyst was 0.085% by mass, and the sodium element content was 98 ppm by mass.

[0158] [Production Example 6: Preparation of Zeolite-Containing Catalyst 6] Clay was obtained by kneading clay made from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 150), an intermediate pore size zeolite, and 89 parts by mass of colloidal silica (33.8% by mass of silica, sodium content of 28 ppm by mass relative to the total amount of colloidal silica liquid), equivalent to 30 parts by mass of silica. After kneading, extrusion molding was performed to obtain extruded bodies adjusted to a diameter of 1.6 mm and a length of 4-6 mm. The obtained bodies were dried at 350°C for 5 hours and then calcined at 600°C for 5 hours to obtain zeolite-containing catalyst 6. At this time, the sodium element content in the zeolite-containing catalyst was 141 ppm by mass.

[0159] [Production Example 7: Preparation of Zeolite-Containing Catalyst 7] Clay was obtained by kneading clay made from 80 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 850), a zeolite with an intermediate pore size, and 59 parts by mass of colloidal silica (33.8% by mass of silica, sodium content of 28 ppm by mass relative to the total volume of colloidal silica liquid), which corresponds to 20 parts by mass of silica. After kneading, extrusion molding was performed to obtain extruded bodies adjusted to a diameter of 2.6 mm and a length of 4-6 mm. The obtained bodies were calcined at 600°C for 5 hours to obtain a catalyst precursor. The obtained catalyst precursor was stirred in a 0.01 N silver nitrate aqueous solution for 1 hour, and the process of filtration and washing was repeated three times, followed by calcination at 600°C for 5 hours to obtain zeolite-containing catalyst 7. At this time, the silver element content in the zeolite-containing catalyst was 0.2339% by mass, and the sodium element content was 10 ppm by mass.

[0160] [Production Example 8: Preparation of Zeolite-Containing Catalyst 8] A zeolite-containing catalyst 8 was obtained by supplying and circulating a water vapor-air mixture gas containing 80% by volume of water vapor to a zeolite-containing catalyst 7 under conditions of a pressure of 0.1 MPa and a temperature of 600°C for 24 hours.

[0161] [Production Example 9: Preparation of Zeolite-Containing Catalyst 9] Clay was obtained by kneading clay made from 80 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 850), a zeolite with an intermediate pore size, and 59 parts by mass of colloidal silica (33.8% by mass of silica, sodium content of 28 ppm by mass relative to the total volume of colloidal silica liquid), which corresponds to 20 parts by mass of silica. After kneading, extrusion molding was performed to obtain extruded bodies adjusted to a diameter of 2.6 mm and a length of 4-6 mm. The obtained bodies were calcined at 600°C for 5 hours to obtain a catalyst precursor. The obtained bodies were stirred in a 0.002N silver nitrate aqueous solution for 1 hour, and the process of filtration and washing was repeated three times, followed by calcination at 600°C for 5 hours to obtain zeolite-containing catalyst 9. At this time, the silver element content in the zeolite-containing catalyst was 0.1360% by mass, and the sodium element content was 14 ppm by mass.

[0162] [Manufacturing Example 10: Preparation of Zeolite-Containing Catalyst 10] A zeolite-containing catalyst 10 was obtained by supplying and circulating a water vapor-air mixture gas containing 80% by volume of water vapor to a zeolite-containing catalyst 9 under conditions of a pressure of 0.1 MPa and a temperature of 600°C for 24 hours.

[0163] [Production Example 11: Preparation of Zeolite-Containing Catalyst 11] Clay obtained from 80 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 850), an intermediate pore size zeolite, and 59 parts by mass of colloidal silica (33.8% by mass of silica, sodium content of 28 ppm by mass relative to the total volume of colloidal silica liquid), equivalent to 20 parts by mass of silica, was kneaded and then extruded to obtain extruded molded bodies with a diameter of 2.6 mm and a length of 4-6 mm. The obtained molded bodies were calcined at 600°C for 5 hours to obtain a catalyst precursor. The obtained catalyst precursor was stirred in a 0.1N sodium nitrate aqueous solution for 1 hour, then filtered and washed, and calcined at 600°C for 5 hours to obtain a sodium exchanger. The sodium exchanger was stirred in a 0.01N silver nitrate aqueous solution for 1 hour, and the process of filtration and washing was repeated three times, and then calcined at 600°C for 5 hours to obtain a silver exchanger. A zeolite-containing catalyst 11 was obtained by supplying and circulating a water vapor-air mixture gas containing 80% by volume of water vapor to a silver exchanger under conditions of a pressure of 0.1 MPa and a temperature of 600°C for 24 hours. At this time, the silver element content in the zeolite-containing catalyst was 0.2641% by mass, and the sodium element content was 38 ppm by mass.

[0164] [Production Example 12: Preparation of Zeolite-Containing Catalyst 12] Clay was obtained by kneading clay made from 80 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 850), an intermediate pore size zeolite, and 59 parts by mass of colloidal silica (33.8% by mass of silica, sodium content of 28 ppm by mass relative to the total amount of colloidal silica liquid), which corresponds to 20 parts by mass of silica. After extrusion molding was performed, extruded molded bodies were obtained with a diameter of 2.6 mm and a length of 4-6 mm. The obtained molded bodies were fired at 600°C for 5 hours, stirred in a 0.001N silver nitrate aqueous solution for 1 hour, and then filtered and washed. This process was repeated three times, and the bodies were fired again at 600°C for 5 hours to obtain zeolite-containing catalyst 12. At this time, the silver element content in the zeolite-containing catalyst was 0.1899% by mass, and the sodium element content was 61 ppm by mass.

[0165] [Production Example 13: Preparation of Zeolite-Containing Catalyst 13] Clay was obtained by kneading clay made from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 980), an intermediate pore size zeolite, and 89 parts by mass of colloidal silica (33.8% by mass of silica, sodium content of 28 ppm by mass relative to the total amount of colloidal silica liquid), and then extruded to obtain extruded bodies with a diameter of 2.1 mm and a length of 4-6 mm. The obtained bodies were fired at 600°C for 5 hours, and then immersed in 100 parts by mass of 0.1N nitric acid per 10 parts by mass of the bodies for 1 hour at room temperature, followed by washing with water to obtain zeolite-containing catalyst 13. At this time, the sodium content in the zeolite-containing catalyst was 18 ppm by mass.

[0166] [Production Example 14: Preparation of Zeolite-Containing Catalyst 14] Clay was obtained by kneading clay made from 80 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 850), an intermediate pore size zeolite, and 59 parts by mass of colloidal silica (33.8% by mass of silica, sodium content of 28 ppm by mass relative to the total volume of colloidal silica liquid), equivalent to 20 parts by mass of silica. After extrusion molding was performed, extruded bodies were obtained with a diameter of 2.6 mm and a length of 4-6 mm. The obtained bodies were fired at 600°C for 5 hours, and a catalyst precursor was obtained by immersing 100 parts by mass of 0.1N nitric acid per 10 parts by mass of the bodies in 0.1N nitric acid for 1 hour at room temperature, followed by washing with water. The obtained precursor was packed into 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 MPa and a temperature of 600°C for 48 hours to obtain zeolite-containing catalyst 14. At this time, the sodium content in the zeolite-containing catalyst was 21 ppm by mass.

[0167] [Manufacturing Example 15: Preparation of Zeolite-Containing Catalyst 15] Clay was obtained by kneading clay made from 80 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 850), a zeolite with an intermediate pore size, and 59 parts by mass of colloidal silica (33.8% by mass of silica, sodium content of 28 ppm by mass relative to the total amount of colloidal silica liquid), which corresponds to 20 parts by mass of silica. After extrusion molding was performed, extruded bodies were obtained that were adjusted to a diameter of 2.6 mm and a length of 4-6 mm. The obtained bodies were calcined at 600°C for 5 hours, and a catalyst precursor was obtained by immersing 100 parts by mass of 0.1N nitric acid per 10 parts by mass of the bodies at room temperature for 1 hour, followed by washing with water. A predetermined amount of diammonium hydrogen phosphate aqueous solution was supported on the obtained precursor to obtain a phosphorus-supported product. The obtained phosphorus-supported product was calcined at 600°C for 5 hours in an air atmosphere to obtain zeolite-containing catalyst 15. At this time, the phosphorus element content in the zeolite-containing catalyst was 0.1687% by mass, and the sodium element content was 18 ppm by mass.

[0168] [Production Example 16: Preparation of Zeolite-Containing Catalyst 16] Clay was obtained by kneading clay made from 80 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 850), a zeolite with an intermediate pore size, and 59 parts by mass of colloidal silica (33.8% by mass of silica, sodium content of 28 ppm by mass relative to the total amount of colloidal silica liquid), which corresponds to 20 parts by mass of silica. After extrusion molding was performed, extruded bodies were obtained that were adjusted to a diameter of 2.6 mm and a length of 4-6 mm. The obtained bodies were calcined at 600°C for 5 hours, and a catalyst precursor was obtained by immersing 100 parts by mass of 0.1N nitric acid per 10 parts by mass of the bodies at room temperature for 1 hour, followed by washing with water. A predetermined amount of diammonium hydrogen phosphate aqueous solution was supported on the obtained precursor to obtain a phosphorus-supported product. The obtained phosphorus-supported product was calcined at 600°C for 5 hours in an air atmosphere to obtain zeolite-containing catalyst 16. At this time, the phosphorus element content in the zeolite-containing catalyst was 0.0371% by mass, and the sodium element content was 7 ppm by mass.

[0169] [Production Example 17: Preparation of Zeolite-Containing Catalyst 17] Clay was obtained by kneading clay made from 80 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 850), a zeolite with an intermediate pore size, and 59 parts by mass of colloidal silica (33.8% by mass of silica, sodium content of 28 ppm by mass relative to the total volume of colloidal silica liquid), which corresponds to 20 parts by mass of silica. After kneading, extrusion molding was performed to obtain extruded bodies adjusted to a diameter of 2.6 mm and a length of 4-6 mm. The obtained bodies were calcined at 600°C for 5 hours to obtain a catalyst precursor. The obtained catalyst precursor was stirred in a 0.1N sodium nitrate aqueous solution for 1 hour, filtered and washed, and calcined at 600°C for 5 hours to obtain a sodium exchanger. The sodium exchanger was stirred in a 0.002N silver nitrate aqueous solution for 1 hour, filtered and washed, and calcined at 600°C for 5 hours to obtain zeolite-containing catalyst 17. At this time, the silver element content in the zeolite-containing catalyst was 0.1291% by mass, and the sodium element content was 339 ppm by mass.

[0170] [Production Example 18: Preparation of Zeolite-Containing Catalyst 18] Clay was obtained by kneading clay made from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 980), an intermediate pore size zeolite, and 89 parts by mass of colloidal silica (33.8% by mass of silica, sodium content of 28 ppm by mass relative to the total volume of colloidal silica liquid), and then extruded to obtain extruded bodies with a diameter of 2.1 mm and a length of 4-6 mm. The obtained bodies were fired at 600°C for 5 hours to obtain zeolite-containing catalyst 18. At this time, the sodium content in the zeolite-containing catalyst was 156 ppm by mass.

[0171] [Example 1] (Evaluation of catalyst properties) The initial TPD acid content of zeolite-containing catalyst 1 was 10.7 μmol / g, and the acid content retention rate was 78.1%. The physical properties of the catalyst obtained through characterization are shown in Table 1. (Reaction process) A mixed raw material containing 19.2% by mass of ethylene, 48.1% by mass of ethanol, 18.1% by mass of water, and 14.6% by mass of 1-butene was supplied to a reactor packed with zeolite-containing catalyst 1 at a WHSV of 2.2, a pressure of 0.15 MPaG, and a catalyst bed inlet temperature of 530°C, and the reaction process was carried out for 48 hours. After 3 hours from the start of the reaction, the propylene yield was 18.4% by mass and the aromatic yield was 3.5% by mass. After 48 hours, the retention rate of the propylene yield was 91.7% and the retention rate of the aromatic yield was 60.2%. The reaction results are shown in Table 1 and Figure 4.

[0172] [Example 2] (Regeneration process) With the zeolite-containing catalyst 1 used in the reaction step in Example 1 still packed in the reactor, the flow gas was switched from the raw material to nitrogen diluent gas, and the regeneration process was carried out under the conditions of steps 1 to 5 below. The regenerated zeolite-containing catalyst 1 (regenerated catalyst) was used again in the reaction step. Procedure 1) Temperature 480°C, oxygen concentration 1%, 1 hour Step 2) Temperature 520°C, oxygen concentration 1%, 3 hours Step 3) Temperature 550°C, oxygen concentration 1%, 3 hours Step 4) Temperature 550°C, oxygen concentration 5%, 1 hour Step 5) Temperature 580°C, oxygen concentration 5%, 2 hours (Reaction process: Cycle 2) The reaction process was carried out in the same manner as in Example 1, except that a regenerated catalyst was used. After 48 hours, the retention rate of the propylene yield was 91.8%, and the retention rate of the aromatic yield was 63.1%. The reaction results are shown in Figure 4. (Reaction process: 3rd cycle) After carrying out the second reaction cycle, a regeneration process was performed using the same procedure as described above, followed by the third reaction cycle. After 48 hours, the retention rate of the propylene yield was 92.4%, and the retention rate of the aromatic yield was 57.1%. The reaction results are shown in Figure 4.

[0173] [Example 3] The procedure was carried out in the same manner as in Example 1, except that zeolite-containing catalyst 2 was used. The initial TPD acid content of zeolite-containing catalyst 2 was 10.3 μmol / g, and the acid content retention rate was 93.5%. After 48 hours, the retention rate of propylene yield was 93.6%, and the retention rate of aromatic yield was 61.4%. The physical properties of the catalysts obtained by characterization and the reaction results are shown in Table 1.

[0174] [Example 4] The procedure was carried out in the same manner as in Example 1, except that zeolite-containing catalyst 3 was used. The initial TPD acid content of zeolite-containing catalyst 3 was 11.3 μmol / g, and the acid content retention rate was 81.5%. After 48 hours, the retention rate of propylene yield was 92.1%, and the retention rate of aromatic yield was 61.2%. The physical properties of the catalysts obtained by characterization and the reaction results are shown in Table 1.

[0175] [Example 5] The procedure was carried out in the same manner as in Example 1, except that zeolite-containing catalyst 4 was used. The initial TPD acid content of zeolite-containing catalyst 4 was 40.9 μmol / g, and the acid content retention rate was 73.1%. After 48 hours, the retention rate of propylene yield was 79.4%, and the retention rate of aromatic yield was 50.1%. The physical properties of the catalysts obtained by characterization and the reaction results are shown in Table 1.

[0176] [Example 6] The procedure was carried out in the same manner as in Example 1, except that zeolite-containing catalyst 5 was used. The initial TPD acid content of zeolite-containing catalyst 5 was 32.1 mol / g, and the acid content retention rate was 73.1%. After 48 hours, the retention rate of propylene yield was 78.1%, and the retention rate of aromatic yield was 52.1%. The physical properties of the catalysts obtained by characterization and the reaction results are shown in Table 1.

[0177] [Comparative Example 1] The procedure was carried out in the same manner as in Example 1, except that zeolite-containing catalyst 6 was used. The initial TPD acid content of zeolite-containing catalyst 6 was 86.2 μmol / g, and the acid content retention rate was 44.8%. After 3 hours from the start of the reaction, the propylene yield was 18.2% by mass and the aromatic yield was 3.1% by mass. After 48 hours, the retention rate of the propylene yield was 54.7% and the retention rate of the aromatic yield was 42.9%. The physical properties of the catalysts obtained by characterization and the reaction results are shown in Table 1.

[0178] A comparison of the examples and comparative examples revealed that zeolite-containing catalysts exhibiting an initial TPD acid content above a certain level showed a significant decrease in acid content retention. Furthermore, zeolite-containing catalysts with low acid content retention rates showed a decrease in the average yield of the target compound, making maintenance impossible.

[0179] [Comparative Example 2] The zeolite-containing catalyst 6 used in Comparative Example 1 was subjected to the regeneration process in the same manner as in Example 2. When the reaction process was carried out again using the obtained regenerated catalyst, the propylene yield after 3 hours from the start of the reaction was 12.2% by mass and the aromatic yield was 1.1% by mass, which were significantly lower than those in Comparative Example 1.

[0180] [Table 1]

[0181] [Example 7] (Evaluation of catalyst properties) The physical properties of the zeolite-containing catalyst 7 obtained through characterization are shown in Table 2. (Response evaluation) A mixed raw material containing 28.1% by mass of ethylene, 57.1% by mass of ethanol, and 14.8% by mass of water was supplied to a reactor packed with zeolite-containing catalyst 7 at a WHSV of 2.2, a pressure of 0.15 MPaG, and an average catalyst bed temperature of 500°C, and the reaction process was carried out for 48 hours. After 3 hours from the start of the reaction, the ethylene yield was 22.6% by mass (ethylene conversion rate 77.4% by mass), the propylene yield was 21.5% by mass, and the aromatic yield was 7.9% by mass. After 24 hours, the ethylene yield was 26.5% by mass (ethylene conversion rate 73.5% by mass), the propylene yield was 21.3% by mass, and the aromatic yield was 6.3% by mass. Next, the zeolite-containing catalyst 7 used in the 48-hour reaction evaluation was removed from the reactor and regenerated by calcining at 580°C for 3 hours under air circulation. The regenerated catalyst was then used to conduct a reaction evaluation under the same conditions as described above. Three hours after the start of the reaction, the ethylene yield was 30.2% by mass (ethylene conversion rate 69.8% by mass), the propylene yield was 21.3% by mass, and the aromatic yield was 5.2% by mass. The retention rates of each yield are shown in Table 2.

[0182] [Examples 8-16, Comparative Examples 3-5] The physical properties and reaction evaluations of each catalyst were carried out in the same manner as in Example 7, except that the catalysts listed in Table 2 were used. The results are shown in Table 2. Comparing Comparative Example 3 with the Example, it was found that when the amount of TPD acid in the zeolite is high, the ethylene conversion rate and the propylene yield after 24 hours from the start of the reaction cannot be maintained, and the product composition fluctuates significantly. Comparing Comparative Examples 4 and 5 with the Examples, it was found that when the sodium element content of the zeolite-containing catalyst was high, or when the Na / Al molar ratio was high, the ethylene conversion rate 24 hours after the start of the reaction, the propylene yield 24 hours after the start of the reaction, the ethylene conversion rate after regeneration, and the propylene yield after regeneration could not be maintained, and the amount of coke produced was also high.

[0183] [Table 2] [Explanation of Symbols]

[0184] 1…Reactor, 2…First distillation column, 3…Cooler, 4…Oil-water separator

Claims

1. The reaction includes a step of supplying a mixed raw material containing more than 30% by mass of ethanol to a reactor having a fixed bed filled with a zeolite-containing catalyst, and obtaining a reaction gas containing an olefin having 3 or more carbon atoms and water. The zeolite contained in the zeolite-containing catalyst has an oxygen 10-membered ring structure, The Na / Al molar ratio of the zeolite-containing catalyst is 0.0050 to 0.

25. The amount of acid per unit weight of the zeolite-containing catalyst, determined from the amount of ammonia desorbed at 100 to 650°C in the ammonia temperature-controlled desorption measurement of the zeolite-containing catalyst, is 75 μmol / g or less. The sodium content in the zeolite-containing catalyst is 100 ppm by mass or less. The amount of acid Ac (unit: μmol / g) per unit weight of the zeolite-containing catalyst is given by the following formula (1): Ac ≤ 25 - 60 × [Molar ratio of Na / Al] ... (1) A method for converting ethanol that satisfies the following conditions.

2. The method for converting ethanol according to claim 1, wherein the amount of acid per unit weight of the zeolite-containing catalyst is 0.5 μmol / g or more.

3. The method for converting ethanol according to claim 1, wherein the Si / Al mass ratio in the zeolite-containing catalyst is 300 to 3000.

4. The method for converting ethanol according to claim 1, wherein the silica / alumina molar ratio of the zeolite in the zeolite-containing catalyst is 850 to 2000.

5. The method for converting ethanol according to claim 1, wherein the zeolite-containing catalyst contains at least one doping element selected from the group consisting of phosphorus and group 11 elements.

6. The method for converting ethanol according to claim 5, wherein the content of the doping element is 2.0% by mass or less relative to the total amount of the zeolite-containing catalyst.

7. The method for converting ethanol according to claim 1, wherein the aluminum content is 0.01% by mass to 1% by mass relative to the total amount of the zeolite-containing catalyst.

8. The method for converting ethanol according to claim 1, wherein the mixed raw materials contain ethylene.

9. The method for converting ethanol according to claim 1, wherein the ethanol content in the mixed raw materials is 30% by mass or more relative to the mixed raw materials.

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

50.

11. The method for converting ethanol according to claim 1, further comprising a regeneration step of contacting the zeolite-containing catalyst subjected to the above reaction step with an oxygen-containing gas heated to 400°C or higher, and subjecting it to the above reaction step again.

12. A propylene separation step of separating a fraction mainly containing propylene from a reaction gas obtained by the ethanol conversion method according to any one of claims 1 to 11, A method for producing propylene, including the method described above.

13. A fraction mainly containing aromatic compounds is separated from the reaction gas obtained by the ethanol conversion method according to any one of claims 1 to 11. A method for producing aromatic compounds, including

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