Method for converting alcohol, zeolite-containing catalyst, method for producing zeolite-containing catalyst, and method for producing hydrocarbon or like

Abstract

A method for converting ethanol, which comprises a reaction step for supplying a raw material mixture containing ethanol to a reactor having a fixed bed filled with a zeolite-containing catalyst and obtaining a reaction gas containing water and an olefin having 3 or more carbon atoms, and wherein: the zeolite contained in the zeolite-containing catalyst has an oxygen ten-membered ring structure; the molar ratio of Na / Al of the zeolite-containing catalyst is 0.0050-0.25, and the amount of acid per unit weight of the zeolite-containing catalyst is 75 [mu] mol / g or less as determined from the amount of ammonia desorption at 100-650 DEG C in an ammonia temperature-rising desorption measurement of the zeolite-containing catalyst.

Description

Technical Field

[0001] The present invention relates to a method for converting ethanol, a zeolite-containing catalyst, a method for producing the 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, the development and improvement of propylene production methods, for which demand is expected to increase, are actively pursued. Among these methods, a common method for producing propylene is to contact naphtha or olefins with a catalyst containing zeolite as the active species.

[0003] In addition to olefins, the production of chemicals such as lower olefins and aromatic compounds using biomass-derived alcohols as raw materials has also attracted attention due to the recent increase in environmental awareness. In particular, ethanol is a compound for which production methods from biomass are already established, leading to the early development of efficient ethanol conversion methods.

[0004] For example, Patent Documents 1 and 2 disclose methods for producing a phosphorus-modified zeolite catalyst that promotes the conversion reaction from ethanol to propylene. Furthermore, Patent Document 3 discloses a method for producing propylene from an ethylene feedstock containing water using a zeolite catalyst.

[0005] Existing patent literature

[0006] Patent Literature

[0007] Patent Document 1: China Patent Gazette No. 107649173A

[0008] Patent Document 2: Japanese Patent No. 6229274

[0009] Patent Document 3: Japanese Patent No. 5116043 Summary of the Invention

[0010] Problems to be solved by the invention

[0011] If ethanol is converted to obtain hydrocarbons such as propylene and aromatic compounds, water is produced as a by-product in an amount equal to the mole of the raw ethanol due to the dehydration reaction of the ethanol. Generally speaking, water (steam) above 400°C causes the structural disintegration of the zeolite catalyst accompanied by dealumination, resulting in a decrease in the catalytic performance of the zeolite. That is, when a raw material containing ethanol is brought into contact with zeolite to convert it into ethanol, the catalyst activity decreases due to the by-product water, and thus, the yield of the target compound decreases as the operating time passes. In particular, when a reactor with a fixed bed is used, the catalyst cannot be exchanged or additionally filled during the reaction, so the degradation of the catalyst is associated with a significant decrease in productivity.

[0012] Patent Documents 1 and 2 each disclose a method for producing a zeolite catalyst for converting an ethanol feedstock into propylene. However, the catalyst activity decreases with the passage of reaction time. Patent Document 3 discloses a method for converting an ethylene feedstock containing water into propylene by contacting it with a zeolite catalyst. However, the propylene selectivity decreases within several hours from the start of the reaction.

[0013] Therefore, an object of the present invention is to provide a method for converting ethanol, a zeolite-containing catalyst, a method for producing a zeolite-containing catalyst, and a method for producing hydrocarbons, etc., which suppress deterioration of catalytic performance due to water vapor and suppress coke accumulation.

[0014] Solutions for solving problems

[0015] The present inventors conducted intensive research to achieve the above-mentioned objectives and found that by using a catalyst containing an oxygen ten-membered ring zeolite exhibiting specific composition and physical properties, the structural collapse of the zeolite and the accumulation of coke on the catalyst due to side reactions can be prevented even in ethanol conversion with the by-production of water, thereby suppressing the decrease in catalyst activity and enabling the production of the target compound with a stable yield.

[0016] That is, the present invention includes the following embodiments.

[0017] <1>

[0018] A method for converting ethanol to ethanol comprises: supplying a mixed raw material containing ethanol to a reactor having a fixed bed filled with a catalyst containing zeolite to obtain a reaction gas containing an olefin having 3 or more carbon atoms and water;

[0019] The zeolite contained in the zeolite-containing catalyst has an oxygen ten-membered ring structure.

[0020] The molar ratio of Na / Al of the zeolite-containing catalyst is 0.0050 to 0.25,

[0021] In ammonia temperature desorption measurement of the zeolite-containing catalyst, the acid amount per unit weight of the zeolite-containing catalyst, determined from the amount of ammonia desorbed at 100 to 650° C., is 75 μmol / g or less.

[0022] <2>

[0023] The ethanol conversion method according to <1>, wherein the acid amount Ac per unit weight of the zeolite-containing catalyst satisfies the following formula (1):

[0024] Ac≤25-60×[Na / Al molar ratio]···(1),

[0025] The unit of the acid amount Ac is μmol / g.

[0026] <3>

[0027] The ethanol conversion method according to <1> or <2>, wherein the acid amount per unit weight of the zeolite-containing catalyst is 0.5 μmol / g or more.

[0028] <4>

[0029] The method for converting ethanol according to any one of <1> to <3>, wherein the acid amount per unit weight of the zeolite, determined from the amount of ammonia desorbed at 100 to 650° C. in ammonia temperature desorption measurement of the zeolite-containing catalyst, is 75 μmol / g or less.

[0030] <5>

[0031] The method for converting ethanol according to any one of <1> to <4>, wherein the content of sodium contained in the zeolite-containing catalyst is 100 ppm by mass or less.

[0032] <6>

[0033] The method for converting ethanol according to any one of <1> to <5>, wherein the Si / Al mass ratio in the zeolite-containing catalyst is 300 to 3000.

[0034] <7>

[0035] The method for converting ethanol according to any one of <1> to <6>, wherein the silica / alumina molar ratio of the zeolite in the zeolite-containing catalyst is 600 to 2000.

[0036] <8>

[0037] The method for converting ethanol 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.

[0038] <9>

[0039] The method for ethanol conversion 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.

[0040] <10>

[0041] The method for converting ethanol 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.

[0042] <11>

[0043] The method for conversion to ethanol according to any one of <1> to <10>, wherein the mixed feedstock contains ethylene.

[0044] <12>

[0045] The method for converting to ethanol according to any one of <1> to <11>, wherein the ethanol content in the mixed raw material is 30% by mass or more relative to the mixed raw material.

[0046] <13>

[0047] The method for converting ethanol according to any one of <1> to <12>, wherein a molar ratio of ethylene to ethanol in the mixed feedstock is 0.20 to 2.50.

[0048] <14>

[0049] The method for converting ethanol according to any one of <1> to <13>, further comprising a regeneration step of contacting the zeolite-containing catalyst supplied to the reaction step with an oxygen-containing gas heated to 400° C. or higher and supplying the catalyst to the reaction step again.

[0050] <15>

[0051] A method for producing propylene, comprising 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 <1> to <14>.

[0052] <16>

[0053] A method for producing aromatic compounds, comprising: an aromatic compound separation step of separating a fraction mainly containing aromatic compounds from a reaction gas obtained by the ethanol conversion method according to any one of <1> to <14>.

[0054] <17>

[0055] A zeolite-containing catalyst, wherein the zeolite contained in the zeolite-containing catalyst has an oxygen ten-membered ring structure,

[0056] The molar ratio of Na / Al of the zeolite-containing catalyst is 0.0050 to 0.25,

[0057] In ammonia temperature desorption measurement of the zeolite-containing catalyst, the acid amount per unit weight of the zeolite-containing catalyst, determined from the amount of ammonia desorbed at 100 to 650° C., is 75 μmol / g or less.

[0058] <18>

[0059] The zeolite-containing catalyst according to <17>, wherein the mass ratio of Si / Al in the zeolite-containing catalyst is 300 to 3000.

[0060] <19>

[0061] The zeolite-containing catalyst according to <17> or <18>, wherein the zeolite-containing catalyst is a catalyst for obtaining an olefin having 3 or more carbon atoms from a mixed feedstock containing ethanol.

[0062] <20>

[0063] 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.

[0064] <21>

[0065] 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.

[0066] <22>

[0067] 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.

[0068] <23>

[0069] A method for producing a zeolite-containing catalyst, wherein:

[0070] The zeolite contained in the zeolite-containing catalyst is a zeolite having an oxygen ten-membered ring structure,

[0071] The molar ratio of Na / Al of the zeolite-containing catalyst is 0.0050 to 0.25,

[0072] In ammonia temperature desorption measurement of the zeolite-containing catalyst, the acid amount per unit weight of the zeolite-containing catalyst, as determined from the amount of ammonia desorbed at 100 to 650° C., is 75 μmol / g or less.

[0073] The method for producing the zeolite-containing catalyst includes a steaming step of contacting the zeolite-containing catalyst with steam at a steaming temperature of 450° C. or higher.

[0074] <24>

[0075] A method for producing hydrocarbons, comprising: supplying a raw material containing ethanol to a reactor having a fixed bed filled with a catalyst containing zeolite to obtain a reaction gas containing an olefin having 3 or more carbon atoms and water;

[0076] The zeolite contained in the zeolite-containing catalyst is a zeolite having an oxygen ten-membered ring structure,

[0077] The molar ratio of Na / Al of the zeolite-containing catalyst is 0.0050 to 0.25,

[0078] In ammonia temperature desorption measurement of the zeolite-containing catalyst, the acid amount per unit weight of the zeolite-containing catalyst, determined from the amount of ammonia desorbed at 100 to 650° C., is 75 μmol / g or less.

[0079] Effects of the Invention

[0080] According to the present invention, there are provided a method for converting ethanol, a zeolite-containing catalyst, a method for producing the zeolite-containing catalyst, and a method for producing hydrocarbons, which suppress deterioration of catalytic performance due to water vapor and coke deposition. BRIEF DESCRIPTION OF THE DRAWINGS

[0081] Figure 1 A schematic diagram showing one embodiment of a fixed-bed single-stage adiabatic reactor.

[0082] Figure 2 A schematic diagram showing one embodiment of an ethanol conversion device.

[0083] Figure 3 A schematic diagram showing one embodiment of an ethanol conversion device.

[0084] Figure 4 The reaction results of Example 1 are shown. DETAILED DESCRIPTION

[0085] The present invention will be described in detail below. However, the present invention is not limited to the following embodiment (present embodiment), and can be implemented with various modifications within the scope of the gist of the invention.

[0086] In this specification, a numerical range expressed using "to" indicates a range including the numerical values described before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in this specification, the upper limit or lower limit of a numerical range in a certain stage can be arbitrarily combined with the upper limit or lower limit of a numerical range in another stage.

[0087] [Conversion method to ethanol]

[0088] The conversion method of ethanol of the present embodiment comprises:

[0089] A reaction step of supplying a mixed raw material containing ethanol to a reactor having a fixed bed filled with a zeolite-containing catalyst to obtain a reaction gas containing an olefin having 3 or more carbon atoms and water,

[0090] The zeolite contained in the above-mentioned zeolite-containing catalyst has an oxygen ten-membered ring structure (also referred to as "ten-membered ring structure" for short).

[0091] The Na / Al molar ratio of the zeolite-containing catalyst is 0.0050 to 0.25.

[0092] In the ammonia temperature desorption measurement of the above-mentioned zeolite-containing catalyst, the acid amount per unit weight of the above-mentioned zeolite-containing catalyst (hereinafter also referred to as "TPD acid amount per unit weight of the catalyst") obtained from the desorption amount at 100-650°C is 75 μmol / g or less.

[0093] According to the present embodiment described above, a method for converting ethanol to 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 can be provided, which suppress the deterioration of catalytic performance caused by water vapor and the accumulation of coke by using the above-mentioned zeolite-containing catalyst. That is, it is believed that by controlling the acidic properties of the zeolite and reducing the affinity of the zeolite with water (water vapor), the catalytic activity of the zeolite can be maintained even under reaction conditions in the coexistence of water vapor, and the activity decline of the zeolite-containing catalyst with the passage of reaction time can be suppressed. Furthermore, it is believed that by controlling the amount of sodium in the zeolite-containing catalyst, the structural collapse of the zeolite and the accumulation of coke on the catalyst due to side reactions can be prevented, and the activity decline of the zeolite-containing catalyst can be suppressed under reaction conditions in the presence of ethanol. In addition, the zeolite-containing catalyst can also suppress the deterioration of the catalytic activity during the catalyst regeneration process accompanied by the generation of water vapor.

[0094] Furthermore, according to the above embodiment, ethanol can be converted into target compounds such as propylene and aromatic compounds at high yields. Furthermore, according to the above embodiment, the ethylene conversion rate can be kept constant, and ethylene can be stably produced.

[0095] [Reactor]

[0096] In this embodiment, a zeolite-containing catalyst is filled in a reactor having a fixed bed (hereinafter also referred to as a "fixed bed reactor") and a reaction process is carried out. The fixed bed reactor can use a reactor of any type, such as an adiabatic reactor or an isothermal reactor. Among them, from the viewpoint of excellent operability, a fixed bed adiabatic reactor is preferably used. It should be noted that a heating device for heating the raw materials can be provided in front of the reactor as needed.

[0097] (Fixed bed adiabatic reactor)

[0098] For fixed-bed adiabatic reactors, see 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, in which the fixed catalyst bed consists of only a single stage, is more preferred. Because carbon (coke) accumulates on the catalyst during the reaction, a multi-tower, switchable fixed-bed single-stage adiabatic reactor that can combust and remove this carbon while continuing the reaction is preferred.

[0099] Figure 1 This is a schematic diagram of a fixed-bed single-stage adiabatic reactor. The fixed-bed single-stage adiabatic reactor 10a comprises a reaction housing 12 with an outer perimeter provided with thermal insulation 121, a catalyst bed 13, a reactor inlet 14, and a reactor outlet 15. The thermal insulation 121 surrounding the reaction housing 12 prevents heat from escaping to the outside. In the production method of this embodiment, the temperature within the reactor can be controlled by utilizing heat generation and heat absorption generated by the reaction.

[0100] The catalyst bed 13 is filled with the following catalysts. A first armored thermocouple 161 is provided at a position just before contacting the catalyst bed inlet 131 of the catalyst bed 13. A second armored thermocouple 162 is provided at a position just after passing through the catalyst bed outlet 132 of the catalyst bed 3. The temperature of the mixed raw material at the position just before contacting the catalyst bed inlet 131 and the temperature of the reaction gas just after passing through the catalyst bed outlet 132 are measured by these thermocouples. The positions of these thermocouples can be changed as needed. The catalyst bed 13 can also be multi-stage, but is preferably as follows Figure 1 Single-stage type shown.

[0101] In the fixed-bed single-stage adiabatic reactor 10 a , raw materials are introduced from the reactor inlet 14 and brought into contact with the catalyst bed 13 , and reaction gas is withdrawn from the reactor outlet 15 .

[0102] [Zeolite-containing catalyst]

[0103] In the reaction process of the present embodiment, a zeolite-containing catalyst is used. The zeolite-containing catalyst contains zeolite. The zeolite-containing catalyst exhibits catalytic ability to convert ethanol and olefins into target compounds such as propylene. A common problem in the known production of olefins using ethanol as a raw material using zeolite is the degradation of zeolite due to water vapor. It is believed that according to the ethanol conversion method of the present embodiment, the acidic properties of the zeolite-containing catalyst can be controlled, and the affinity of the zeolite-containing catalyst with water (water vapor) can be reduced, thereby making it easier to maintain the yield of the target compound for a long time.

[0104] The zeolite-containing catalyst may be a molded body obtained by molding only zeolite, but is preferably a molded body containing zeolite and a silica binder in terms of excellent pressure resistance.

[0105] In the conversion method of this embodiment, the zeolite has an oxygen ten-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 zeolites are preferred due to their excellent catalytic performance (catalytic activity and durability against coking), and ZSM-5 is more preferred.

[0106] The synthesis method of the zeolite of the embodiment is not particularly limited and can be produced by optimizing various conditions of the hydrothermal synthesis method of MFI zeolite known in the past. Generally speaking, methods for efficiently obtaining MFI zeolite by hydrothermal synthesis include: a method of hydrothermal synthesis using a suitable organic structure directing agent (SDA), a method of hydrothermal synthesis by adding hydrothermally synthesized MFI zeolite as a seed, or a method of hydrothermal synthesis by adding a seed slurry in the crystallization stage. It should be noted that the organic structure directing agent used here includes, for example, ammonium salts, urea compounds, amines, and alcohols. In addition, it is known that not only organic SDAs but also inorganic cations or anions are related to the structure, and zeolite synthesis depends on the complex action of each component. In the hydrothermal synthesis method of MFI zeolite described above, a preferred catalyst can be obtained by appropriately optimizing the synthesis conditions such as the type of raw materials or additives (SDA), the amount of additives, pH value, silica / alumina molar ratio, medium, cations, anions, etc., the raw material input composition, synthesis temperature, synthesis time, etc.

[0107] Specifically, for example, there can be mentioned a method of synthesizing using a seed slurry described in Japanese Patent No. 5426983 or a method exemplified in The Hydrothermal Synthesis of Zeolites (Chemcal Reviews, 2003, 103, 663-702).

[0108] Furthermore, commercially available zeolite may also be used as long as it is MFI zeolite having the above-mentioned specific physical properties and composition.

[0109] (TPD acid amount per unit weight of catalyst)

[0110] The ethanol conversion method of this embodiment uses a zeolite-containing catalyst having an acid content per unit weight of 75 μmol / g or less, as determined from the amount of ammonia desorbed at 100-650°C in ammonia temperature desorption measurements. A catalyst having a TPD acid content within this range can suppress degradation of catalytic performance due to water vapor. Zeolite acid sites contribute to catalytic activity but also function as an autocatalyst, promoting hydrolysis of the zeolite structure. Therefore, in a reactor where the reaction feedstock contains ethanol and high-temperature water vapor coexists, catalysts with excessive acid content tend to experience structural collapse of the zeolite. Therefore, controlling the TPD acid content within a specific range is believed to be related to maintaining the zeolite structure and catalytic function. Furthermore, excessive active sites lead to excessive polymerization reaction and the accumulation of coke on the catalyst surface. Therefore, controlling the acid content to below the upper limit is related to keeping the coke content within an appropriate range. However, the main reason is not limited to this.

[0111] The TPD acid amount per unit weight of the 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, in terms of excellent catalytic activity per unit weight of the catalyst, the TPD acid amount per unit weight of the 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.

[0112] Furthermore, repeated experimental studies have revealed that sodium, which has been conventionally used to adjust the acid content of the catalyst, promotes catalyst degradation in the reaction step of the present embodiment. Therefore, in the ethanol conversion method of the present embodiment, it is preferable to control both the acid content and the sodium content. From the perspective of further improving catalyst durability, the TPD acid content Ac (unit: μmol / g) per unit weight of the catalyst preferably satisfies the following formula (1):

[0113] Ac≤25-60×[molar ratio of Na / Al]···(1).

[0114] The molar ratio of Na / Al is the molar ratio of the amount of sodium to the amount of aluminum contained in the zeolite-containing catalyst.

[0115] Under the conditions of the reaction process of this embodiment, the sodium contained in the zeolite-containing catalyst exhibits a strong alkalinity by coexisting with water or ethanol, thereby promoting the structural disintegration of the zeolite with poor alkalinity resistance and accelerating the degradation of the catalyst. In addition, sodium also exhibits Lewis acidity while exhibiting alkalinity, thus promoting the accumulation of coke on the catalyst. Therefore, in order to stably manufacture the target compound, it is necessary to control the sodium content on the basis of controlling the acid content of the zeolite-containing catalyst. That is, in a zeolite-containing catalyst containing more sodium, only a smaller acid content is allowed, and the relationship that the upper limit of the suitable acid content decreases with the increase of sodium is expressed as formula (1).

[0116] The first term 25 on the right side of formula (1) represents the amount of acid per unit weight of the catalyst suitable for improving the durability of the zeolite structure.

[0117] The second term on the right side of equation (1) represents the effect of sodium on catalyst durability by multiplying the Na / Al molar ratio of the zeolite-containing catalyst by a coefficient of 10. The reason the Na / Al molar ratio of the zeolite-containing catalyst is used as a variable in the second term, rather than the amount of sodium relative to the zeolite-containing catalyst, is that even with the same amount of sodium relative to the zeolite-containing catalyst, a greater amount of acid sites in the zeolite-containing catalyst, i.e., the aluminum content of the catalyst, reduces the adverse effects of sodium. Furthermore, the coefficient of 60 was determined based on examples demonstrating suitable catalytic performance in experimental studies.

[0118] The structural collapse caused by dealumination of zeolite by steam is due to the acidic properties of zeolite, and the reaction process can be carried out while suppressing dealumination by controlling the acidic properties of the zeolite-containing catalyst. However, the main reason is not limited to this.

[0119] In the aforementioned zeolite-containing catalyst, the zeolite-containing catalyst has an acid amount per unit weight of the zeolite (hereinafter referred to as "TPD acid amount per unit weight of the zeolite") determined from the amount of ammonia desorbed at 100 to 650°C in ammonia temperature desorption measurement, preferably 75 μmol / g or less, more preferably 40 μmol / g or less, and even more preferably 30 μmol / g or less, in view of the excellent durability of the zeolite structure. The TPD acid amount per unit weight of the 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.

[0120] The TPD acid amount per unit weight of the catalyst is calculated as follows: based on the desorption spectrum obtained by circulating diluted ammonia gas in a degassed zeolite-containing catalyst and adsorbing ammonia and then heating it, it is calculated using a calibration curve method. It should be noted that the area value of 100°C-650°C of the measured spectrum is used to derive the TPD acid amount. In more detail, according to the method described in the examples. In addition, the TPD acid amount per unit weight of the zeolite-containing catalyst obtained by the above method is calculated by dividing the TPD acid amount per unit weight of the zeolite-containing catalyst by the weight ratio of the zeolite in the zeolite-containing catalyst. Here, the TPD acid amount refers to the acid amount of the zeolite-containing catalyst before use (initial) in the reactor.

[0121] The acid retention rate represented by the following formula in the zeolite-containing catalyst is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more. The upper limit of the acid retention rate is not particularly limited and may be 98% or less.

[0122] Acidity retention rate (%) = Acidity after 6.0 hours of STM treatment (μmol / g) / Acidity after 1.0 hours of STM treatment (μmol / g) × 100

[0123] The acid amount after 6.0 hours of STM treatment refers to the TPD acid amount of the zeolite-containing catalyst after 6 hours of steam treatment, and the acid amount after 1.0 hours of STM treatment refers to the TPD acid amount of the zeolite-containing catalyst after 1 hour of steam treatment.

[0124] It should be noted that the water vapor treatment was carried out as follows: helium was bubbled into water heated to 80°C at a flow rate of 50 mL / min, the temperature was cooled to 75°C using a condenser, and then a zeolite-containing catalyst heated to 650°C was prepared to allow water vapor to contact the zeolite-containing catalyst.

[0125] (Mesopore volume of zeolite-containing catalyst)

[0126] In the ethanol conversion method of this embodiment, a zeolite-containing catalyst having a mesopore volume of 0.15 cc / g or greater, and more preferably 0.20 cc / g or greater, is preferably used from the viewpoint of excellent raw material adsorption characteristics. The mesopore volume can be measured by mercury porosimetry using a mercury intrusion porosimeter.

[0127] (Composition of Zeolite-Containing Catalyst)

[0128] The silica / alumina (SiO2 / Al2O3) molar ratio of the zeolite contained in the zeolite-containing catalyst of this embodiment can be appropriately selected. From the perspective 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 a known method, for example, by completely dissolving the zeolite in an alkaline aqueous solution and analyzing the resulting solution by plasma emission spectrometry or the like.

[0129] The mass ratio of silicon (Si) to aluminum (Al) (Si / Al mass ratio) contained in the zeolite-containing catalyst of the present embodiment can be appropriately selected. From the perspective 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 a known method, for example, by completely dissolving the zeolite-containing catalyst in an alkaline aqueous solution and analyzing the resulting solution by plasma emission spectrometry. By controlling the Si / Al mass ratio of the zeolite-containing catalyst, the affinity of the zeolite-containing catalyst for water is reduced, and the reaction process can be carried out while maintaining catalytic performance even under hydrothermal conditions. However, the main reason is not limited to this. From the perspective of 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, from the perspective of suppressing the deterioration of catalytic performance caused by water vapor, the Si / Al mass ratio is preferably 125 or more, more preferably 300 or more, and even more preferably 500 or more.

[0130] The molar ratio of sodium to aluminum (Na / Al molar ratio) contained 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. By setting the Na / Al molar ratio to 0.25 or less, deterioration of catalytic performance due to water vapor can be suppressed, and by setting the Na / Al molar ratio to 0.0050 or more, coke accumulation can be suppressed. In terms of excellent durability against catalyst degradation due to higher temperature water vapor, the Na / Al molar ratio is preferably 0.20 or less, and more preferably 0.15 or less. In terms of further suppressing the formation of coke, the Na / Al molar ratio is preferably 0.0060 or more, and more preferably 0.0070 or more.

[0131] In the synthesis process of zeolite or the molding process of the catalyst, sodium is used as part of the raw material. Therefore, in general, the molar ratio of Na / Al of the zeolite-containing catalyst 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 use acid to wash the zeolite-containing catalyst (hereinafter also referred to as "acid washing") to remove the sodium. The type of acid used in the acid washing is not particularly limited. For example, the molar ratio of Na / Al can be adjusted by washing with an aqueous nitric acid solution. In terms of excellent cleaning efficiency, the acid concentration of the washing liquid used in the acid washing is preferably 0.010 to 10N. In addition, in terms of suppressing the deactivation of zeolite accompanying acid washing, the acid concentration of the washing liquid is more preferably 0.01 to 2.0N, and further preferably 0.05 to 1.5N. Acid washing does not need to be particularly heated or cooled, but from the viewpoint of excellent cleaning efficiency, it is preferably carried out at 10 to 90°C, and more preferably at 20 to 70°C. Acid cleaning is performed, for example, by impregnating the zeolite-containing catalyst with a cleaning solution. For excellent cleaning efficiency, the impregnation time is preferably 0.10 to 10 hours, more preferably 0.50 to 6.0 hours. For ease of waste liquid treatment, the weight of the cleaning solution used for one acid cleaning is preferably 500 parts by mass or less, more preferably 250 parts by mass or less, relative to 10 parts by mass of zeolite. Acid cleaning can be performed multiple times to increase the sodium removal rate, but for ease of waste liquid treatment, it is preferably performed only once during catalyst production.

[0132] Cation exchange is also effective as a method for removing sodium retained in cationic sites. For example, ion exchange treatment using an aqueous silver nitrate solution can be used to reduce the sodium content in the zeolite-containing catalyst, thereby adjusting the Na / Al molar ratio. Furthermore, the sodium content of 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.

[0133] The sodium contained in the zeolite-containing catalyst causes the structural disintegration of the zeolite and the generation of coke by forming alkaline sites under the conditions of water and ethanol, and promotes catalyst degradation. Therefore, in the reaction process of the present embodiment, in order to suppress catalyst degradation, it is desirable to reduce the sodium in the zeolite. Sodium is a component that is easily mixed into during zeolite synthesis or catalyst forming steps and particularly requires management. Therefore, it is believed that by controlling the molar ratio of Na / Al, the generation of alkaline sites in the reaction can be suppressed, and even under the reaction conditions of the coexistence of water vapor, the activity decline of the zeolite-containing catalyst over the reaction time can be suppressed.

[0134] The sodium content in the zeolite-containing catalyst of this embodiment is preferably 1,000 mass ppm or less, more preferably 100 mass ppm or less, and even more preferably 10 mass ppm or less, relative to the total amount of the zeolite-containing catalyst. Furthermore, from the perspective of suppressing the formation of coke associated with side reactions, the sodium content is preferably 100 mass ppm or less. In this embodiment, the sodium content in the zeolite-containing catalyst represents a value measured by XRF analysis.

[0135] (Dopant Elements in Zeolite-Containing Catalysts)

[0136] The zeolite-containing catalyst of this embodiment may contain at least one doping element selected from the group consisting of phosphorus and elements belonging to Group 11 of the periodic table (hereinafter, these elements are collectively referred to as "dopant elements"). Among these, the zeolite-containing catalyst preferably contains phosphorus or silver.

[0137] Examples of phosphorus include phosphorus polymers (e.g., polyphosphoric acid), phosphorus oxides (e.g., P2O5), and compounds in which phosphorus is added to zeolite in the form of aluminum. Furthermore, multiple forms of these may be present. When the zeolite contains aluminum, phosphorus has the effect of suppressing dealumination of the zeolite. In the method of this embodiment, water is generated within the reactor, and the raw material ethanol may also contain water. Therefore, the reactor becomes a high-temperature steam atmosphere that causes dealumination. By incorporating phosphorus into the zeolite-containing catalyst, dealumination of the zeolite can be suppressed, further improving the durability of the catalyst.

[0138] Examples of elements belonging to Group 11 of the Periodic Table include copper, silver, and gold. The inclusion of elements belonging to Group 11 can suppress dealumination of zeolite and improve catalyst durability. Among these elements belonging to Group 11, silver is preferred due to its excellent loading efficiency.

[0139] The content of the doping element contained in the zeolite-containing catalyst may be 2.0 mass % or less, preferably 0.01 to 2.0 mass %, and more preferably 0.05 to 1.0 mass % based on the total amount of the zeolite-containing catalyst from the viewpoint of further suppressing dealumination.

[0140] In this embodiment, the content of the doping element in the zeolite-containing catalyst is a value measured using a fluorescent X-ray analyzer. The phosphorus, copper, silver, or gold content can be measured using a commercially available fluorescent X-ray analyzer under standard conditions according to the operating instructions. For example, when using the "RIX3000" manufactured by Rigaku, the measurement conditions can be set to use P-Kα radiation, a tube voltage of 50 kV, and a tube current of 50 mA.

[0141] In this embodiment, phosphoric acid and / or a phosphate (hereinafter also referred to as a "phosphorus raw material") can be used as a raw material for phosphorus contained in the zeolite-containing catalyst. As the phosphorus raw material, a phosphate is more preferred, and among the phosphates, a compound having a solubility of 1 g or more in 100 g of water at 25°C is more preferred.

[0142] Examples of phosphoric acid include phosphoric acid and pyrophosphoric acid. Examples of phosphates include ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium hydrogen ammonium phosphate, and other ammonium phosphate salts, potassium hydrogen phosphate, aluminum hydrogen phosphate, sodium phosphate, and potassium phosphate. Among these, ammonium phosphate salts having high solubility in water are preferred, and at least one selected from the group consisting of ammonium phosphate, diammonium hydrogen phosphate, and ammonium dihydrogen phosphate is more preferred. These may be used alone or in combination of two or more.

[0143] In the present embodiment, as the raw material of the element belonging to the 11th group of the periodic table contained in the catalyst containing zeolite, metal nitrates such as copper nitrate and silver nitrate can be used. Using a catalyst containing zeolite containing sodium as a counter cation, ion exchange is carried out with metal nitrate, and sintering is carried out, thus obtaining a catalyst containing zeolite containing an element belonging to the 11th group of the periodic table. The ion exchange of the sodium as the counter cation in the zeolite and the metal nitrate can be carried out by impregnating zeolite or the catalyst containing zeolite in an aqueous solution of metal nitrate, and then washing, thereby implementing. At this time, by implementing multiple impregnation and washing, the exchange rate of ions can be improved. In addition, as mentioned above, sodium remaining in the catalyst can cause the degradation resistance of the zeolite to be impaired, so it is preferably used to prepare a catalyst containing zeolite containing an element belonging to the 11th group of the periodic table using a proton-type or ammonium-type zeolite-containing catalyst.

[0144] (Method for Molding Zeolite-Containing Catalyst)

[0145] The zeolite-containing catalyst of this embodiment can be produced by molding a zeolite having the aforementioned specific physical properties and composition, for example, as follows. The molding method is not particularly limited, and conventional methods can be used. Specifically, examples include compression molding or extrusion molding of the catalyst component, and spray drying molding, which is most suitable for fluidized bed reactions.

[0146] In addition, a binder can be used during molding. As a binder, there is no particular limitation, for example, silica, alumina, kaolin can be used alone or in combination. These binders can use commercially available products. The mass ratio of zeolite / binder is preferably in the range of 10 / 90 to 90 / 10, more preferably in the range of 20 / 80 to 80 / 20. In the conversion method of this embodiment, it is required to precisely control the acid sites on the catalyst, so it is preferred that the catalyst does not contain compounds showing acidic properties other than zeolite, but binders such as alumina or kaolin show acidic properties. Therefore, it is preferred to use a binder that does not show acidic properties, wherein, from the viewpoint of excellent coking resistance, it is more preferred to use a silica binder. The total content of zeolite and binder can be 80% to 100% by mass relative to the total amount of the catalyst containing zeolite, or it can be 90% to 100% by mass. 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, based on the total amount of the zeolite-containing catalyst.

[0147] (Pretreatment Step of Zeolite-Containing Catalyst)

[0148] In the ethanol conversion method of the present embodiment, after arbitrary shaping, before the zeolite-containing catalyst is brought into contact with the raw material, a pretreatment process can be performed on the zeolite-containing catalyst. As a preferred pretreatment process, a steaming process in which heat treatment is performed at a temperature of 450°C or above in the presence of water vapor can be cited. If pretreatment is performed, there is a tendency that the effect of suppressing the degradation of the catalyst or improving the selectivity becomes more significant. In the case of the above method, at a temperature of 450°C or above and 900°C or below, the atmosphere is not particularly limited, and it is preferred to circulate a mixed gas of an inert gas such as air or nitrogen and steam (water vapor), and to perform the treatment under conditions of a water vapor partial pressure of 0.01 atmospheres or above. As the heat treatment temperature, a temperature of 500°C or above and 700°C or below is more preferred. In addition, this pretreatment process can be performed using a reactor for converting ethanol and ethylene.

[0149] (Shape of Zeolite-Containing Catalyst)

[0150] In the ethanol conversion method of this embodiment, zeolite-containing catalysts having various shapes, such as cylindrical and toroidal, can be used. From the perspective of ease of handling, cylindrical zeolite-containing catalysts are preferred. Among them, from the perspective of excellent catalyst strength, cylindrical molded bodies having a diameter of 1.6 mm or greater and a length of 0.1 to 10.0 cm are preferably used.

[0151] [Mixed raw materials]

[0152] In the reaction step of this embodiment, a mixed raw material containing ethanol is used. From the perspective of excellent environmental compatibility, ethanol is preferably derived from biomass. It should be noted that biomass refers to organic resources other than fossil resources derived from plants and animals, and the term "derived from biomass" refers to compounds produced using biomass as a raw material.

[0153] From the viewpoint of excellent production efficiency of the target compound, the ethanol content in the mixed raw material is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more.

[0154] In the reaction step of this embodiment, ethanol is first converted to ethylene. Ethanol is more reactive than olefins with four or more carbon atoms. Increasing the ethanol content in the mixed feedstock improves the production efficiency of target light olefins such as propylene and ethylene. Ethanol's high reactivity stems from the ease with which these substrates access the reactive sites of the zeolite. Specifically, ethanol and ethylene, with two carbon atoms, have smaller molecular sizes than olefins with four or more carbon atoms, making them less susceptible to steric hindrance within the pores of the zeolite. Furthermore, ethanol's high reactivity is also due to the presence of heteroatom-containing functional groups in ethanol, which results in a biased electron distribution within the molecule.

[0155] While similar effects can be expected by using more ethylene as the mixed feedstock, it is preferable to increase the ratio of C2 materials in the mixed feedstock with ethanol from the perspective of stable device operation. This is because the process of converting ethylene to the target compound is an exothermic reaction, and if there is excess ethylene, the temperature inside the reactor rises, accelerating the coking of the catalyst.

[0156] From the viewpoint of easiness in changing the composition of the raw materials, the mixed raw material may contain ethylene in addition to ethanol. As ethylene, those produced by various production methods can be used. For example, those obtained by thermal cracking of naphtha and / or ethane, direct or oxidative dehydrogenation of ethane, or dehydration of ethanol can be used. Among them, the mixed raw material preferably contains ethylene and water in the form of a gas obtained by dehydration of ethanol. Since water is produced as a by-product in the process of converting ethanol to ethylene, ethylene usually contains water. From the viewpoint of excellent environmental harmony, it is preferred to use ethylene obtained by dehydrating ethanol derived from biomass. From the viewpoint of excellent ease of reaction control, the molar ratio of ethylene / ethanol in the mixed raw material is preferably 0.20 to 2.50, more preferably 0.40 to 2.0.

[0157] The mixed raw material may also contain hydrocarbons having 4 to 6 carbon atoms. Examples of the 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 them, olefins having 4 to 6 carbon atoms, like ethylene and ethanol, can be brought into contact with a catalyst containing zeolite to obtain target compounds such as propylene. Examples of hydrocarbons having 4 to 6 carbon atoms include butene, pentene, hexene, butane, pentane, and hexane. In the mixed raw material, the molar ratio of olefins having 4 to 6 carbon atoms / ethylene is preferably 3.0 or less, more preferably 1.0 or less, and further preferably 0.14 to 1.0. It should be noted that the term "olefin" mentioned above includes not only linear, branched, and cyclic olefins, but also cycloparaffins.

[0158] In the ethanol conversion method of this embodiment, the mixed feedstock may further contain a C1-6 oxygenate other than ethanol. Similar to ethylene and ethanol, C1-6 oxygenates can provide target compounds such as propylene upon contact with a catalyst. Examples of C1-6 oxygenates other than ethanol include methanol, propanol, dimethyl ether, and diethyl ether. In the mixed feedstock, the molar ratio of C1-6 oxygenate to ethylene is preferably 1.0 or less, and more preferably 0.5 or less.

[0159] In addition, ethylene, ethanol, olefins having 4 to 6 carbon atoms, and oxygen-containing compounds having 1 to 6 carbon atoms other than ethanol are also collectively referred to as "effective raw materials."

[0160] In addition to the above-mentioned effective raw materials, the mixed raw material may also contain saturated aliphatic hydrocarbons such as paraffin, olefins having 7 or more carbon atoms, and oxygen-containing compounds having 7 or more carbon atoms. These saturated aliphatic hydrocarbons, olefins having 7 or more carbon atoms, and oxygen-containing compounds having 7 or more carbon atoms can be converted into the target compound by contact with the conversion catalyst, similar to ethylene and ethanol, but their reactivity is lower than that of the above-mentioned effective raw materials.

[0161] In addition to the above-mentioned raw materials that can be converted into propylene through the reaction process, the mixed raw material may also contain inert gases such as nitrogen. Furthermore, the mixed raw material may contain hydrogen or methane as diluent gases, but preferably, no hydrogen dilution is performed. Hydrogen is sometimes used to suppress coking and degradation of the catalyst, but it also has the adverse effect of causing hydrogenation reactions that produce propylene, etc., and reducing the propylene purity (propylene / (propylene+propane)) [mol / mol]. In the method of this embodiment, even without hydrogen dilution, the rate of coking and degradation of the catalyst is low, allowing stable operation, so it is preferably not performed.

[0162] The total content of ethylene and ethanol in the mixed raw material is preferably 30 to 100 mass%, more preferably 40 to 100 mass%, and even more preferably 50 to 100 mass% relative to the total amount of the effective raw materials. Ethanol is calculated in terms of its mass converted to ethylene.

[0163] The total content of C4-6 olefins in the mixed raw material is preferably 65% by mass or less, more preferably 10 to 55% by mass, based on the total amount of the effective raw materials.

[0164] The mixed raw material may contain diethyl ether, but preferably does not contain diethyl ether. The content of diethyl ether in the active raw material is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0165] In the conversion method of the present embodiment, water may be contained in the mixed raw material. The ethylene and ethanol contained in the raw material are manufactured by various manufacturing methods and therefore contain "water generated in the manufacturing process". The "water generated in the manufacturing process" here refers to moisture generated in the manufacturing process of ethylene and / or ethanol and not removed. In the conversion method of the present embodiment, in addition to the "water generated in the manufacturing process", water may also be contained in the mixed raw material. Water suppresses coking degradation by reducing the olefin partial pressure and has the effect of increasing the yield of lower olefins. On the other hand, from the viewpoint of excellent production efficiency of the target compound per unit flow rate of the raw material, it is preferred that the mixed raw material does not contain water except for the "water generated in the manufacturing process".

[0166] [Reaction conditions]

[0167] From the viewpoint of excellent yield of the target compound, 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.

[0168] It should be noted that when using an adiabatic reactor, the so-called reaction temperature is as follows. The so-called inlet temperature of the catalyst bed refers to the temperature of the raw material at the position before the raw material fluid contacts the catalyst bed filled in the adiabatic reactor. The so-called outlet temperature of the catalyst bed refers to the temperature of the reaction gas at the position just after the reaction gas passes through the catalyst bed. The temperature of the raw material and the reaction gas here refers to the temperature between 0d and 0.8d when the center of the reactor is set to 0 and the distance from the center of the reactor to the inner wall of the reactor is set to d in a plane perpendicular to the flow direction of the fluid. The average inlet and outlet reaction temperatures are as follows: Figure 1The values shown are calculated by measuring the catalyst bed inlet temperature and the catalyst bed outlet temperature using the formula: [catalyst bed inlet temperature + catalyst bed outlet temperature] / 2 (hereinafter 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 catalyst bed outlet temperature and the catalyst bed inlet temperature is preferably -80K to 80K, more preferably -60K to 60K.

[0169] The reaction pressure in the reaction step is preferably 0.01 to 3.0 MPaG, more preferably 0.01 to 1.0 MPaG.

[0170] The supply rate of the effective raw material is preferably 0.1 to 1000 hr in terms of the mass-based space velocity (WHSV) of the zeolite-containing catalyst. -1 , more preferably 0.1 to 100 hr -1 , more preferably 0.5 to 50 hr -1 In the reaction step, WHSV is calculated by converting ethanol into ethylene as shown in the following formula. In addition, from the perspective of excellent productivity of the target compound, the effective raw material supply mass flow rate is preferably 1 kg / hr or more, more preferably 10 kg / hr or more, and even more preferably 1 t / hr or more.

[0171] WHSV(hr -1 ) = effective raw material supply flow rate (kg / hr) / catalyst amount (kg)

[0172] Effective feedstock flow rate (kg / hr) = ethylene flow rate (kg / hr) + ethylene-equivalent ethanol flow rate (kg / hr) + C4-6 olefin flow rate (kg / hr) + C1-6 oxygen-containing compound flow rate other than ethanol (kg / hr)

[0173] Ethylene conversion ethanol flow rate (kg / hr) = ethanol flow rate (kg / hr) × ethylene molecular weight (g / mol) / ethanol molecular weight (g / mol)

[0174] [Regeneration process]

[0175] 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 supplied to the reaction step is contacted with an oxygen-containing gas heated to 400°C or higher and then supplied to the reaction step again. If the zeolite-containing catalyst is used for a long period of time, coke accumulates on the catalyst, causing coking and degradation. The regeneration step allows the coke accumulated on the zeolite-containing catalyst to be burned. Examples of the oxygen-containing gas used in the regeneration step include air, or a mixed gas of air, oxygen, and an inert gas. The oxygen concentration in the contacting gas is preferably 0.1 to 2.0% by volume. The contact temperature with the gas is preferably at least 20°C higher (preferably 30°C higher, more preferably 40°C higher) than the temperature of the reaction step. Specifically, the contact temperature may be 400 to 700°C. In the regeneration step, the zeolite catalyst supplied to the reaction step is used so as to contain water derived from water vapor generated in the reaction step, or the coke is burned to generate water. Therefore, in the regeneration process, the zeolite catalyst is brought into contact with water vapor at a temperature of 400°C or higher, which promotes the structural disintegration of the zeolite. By controlling the TPD acid content of the specific zeolite-containing catalyst as shown in this embodiment, the affinity of the zeolite for water (water vapor) can be reduced, thereby suppressing the degradation of the catalyst activity. It should be noted that either regeneration method can be adopted: external regeneration in which the catalyst is extracted from the reactor and regenerated outside the reactor, or internal regeneration in which the catalyst is regenerated inside the reactor without being extracted from the reactor. In addition, a reaction-regeneration switching operation can also be performed by using a switching reactor.

[0176] (Reaction-regeneration switching operation)

[0177] The so-called reaction-regeneration switching operation refers to the use of a 2-tower or multi-tower switching reactor to simultaneously perform the operation of the reaction process and the regeneration process. For example, in the case of a 3-tower switching system, 2 towers are used in the reaction process, and at the same time, the remaining 1 tower is used in the catalyst regeneration. Afterwards, the reaction process of one of the towers used in the reaction process is stopped to regenerate the catalyst, and the reaction process is carried out in the tower used for catalyst regeneration. This allows the production capacity of the two towers to be maintained while the catalyst is regenerated. This reaction form is also called a carousel method. Since there is no need to stop the manufacturing process for catalyst regeneration, it is preferred from the perspective of excellent production efficiency.

[0178] [Product: Reaction gas containing an olefin having 3 or more carbon atoms]

[0179] In the conversion method of this embodiment, a reaction gas containing olefins having 3 or more carbon atoms is obtained by contacting a feedstock with a zeolite-containing catalyst. The reaction gas may contain ethylene. The reaction gas may contain hydrogen, aliphatic hydrocarbons having 1 to 3 carbon atoms, aliphatic hydrocarbons having 4 to 6 carbon atoms, aromatic compounds, and hydrocarbons having 9 or more carbon atoms.

[0180] In the conversion method of the present 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.

[0181] [Separation process]

[0182] In the conversion method of this embodiment, a separation step is provided to perform various separation operations, thereby efficiently purifying the target compound. Preferably, the step includes separating the reaction gas obtained in the above-described reaction step into a fraction A primarily containing hydrocarbons with 2 to 3 carbon atoms and a fraction B primarily containing hydrocarbons with 4 to 6 carbon atoms using a separation device. This separation into the respective fractions allows for efficient isolation of the target compound. Examples of the separation device used in the separation step include a distillation column, a quench tower, and a decanter.

[0183] Furthermore, the reaction gas obtained in the above reaction step or a fraction separated from the reaction gas (hereinafter also referred to as a "connecting fraction") is introduced into a purification system of an ethylene plant to separate target compounds such as ethylene, propylene, and aromatic compounds.

[0184] like Figure 2 As shown, the method of this embodiment can be implemented using an apparatus comprising a reactor 1 and a first distillation column 2. The reaction gas obtained from the reaction step in reactor 1 is separated in the first distillation column 2 into a fraction A primarily containing hydrocarbons having 1 to 3 carbon atoms, and a fraction B primarily containing hydrocarbons having 4 to 6 carbon atoms. Ethylene is separated from fraction A in a distillation column (not shown), and propylene is further separated in a distillation column (not shown), thereby efficiently separating ethylene and propylene from the reaction gas. Furthermore, although not shown, at least a portion of the reaction gas and / or fraction A can be introduced into a purification system of an ethylene plant, where target compounds such as ethylene and propylene can be separated from the reaction gas.

[0185] like Figure 3As shown, the method of this embodiment can be implemented using an apparatus comprising a reactor 1, a cooler 3, an oil-water separator 4, and a first distillation column 2. The reaction gas obtained from the reaction step in reactor 1 is separated in cooler 3 into a fraction C primarily containing hydrocarbons having 1 to 6 carbon atoms, and a fraction D primarily containing water, hydrocarbons having 7 or more carbon atoms, and aromatic compounds. In fraction D, "primarily containing water, hydrocarbons having 7 or more carbon atoms, and aromatic compounds" means that the combined amount of water, hydrocarbons having 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 a fraction A primarily containing hydrocarbons having 1 to 3 carbon atoms, and a fraction B primarily containing hydrocarbons having 4 to 6 carbon atoms. Fraction D is separated in the oil-water separator 4 into a fraction E primarily containing hydrocarbons having 7 or more carbon atoms and aromatic compounds, and a fraction F primarily containing water. By introducing fraction E into a purification system, aromatic compounds can be efficiently purified. By separating the reaction gas into Fraction A, Fraction B, and Fraction E in this manner, target compounds such as propylene and aromatic compounds can be efficiently purified. At least a portion of Fraction A, Fraction B, and Fraction E can be introduced into a purification system of an ethylene plant, where target compounds such as ethylene, propylene, and aromatic compounds can be separated from the reaction gas.

[0186] In various fractions, "mainly contains" means that the total mass of the components described as "mainly contains" exceeds 50% by mass of each fraction. Note that these separation steps can be carried out by combining various known methods such as distillation and extraction.

[0187] As described above, various hydrocarbons are obtained by the ethanol conversion method of this embodiment. That is, the ethanol conversion method of this embodiment is, from another perspective, a method for producing hydrocarbons. The hydrocarbons may be either saturated hydrocarbons or unsaturated hydrocarbons. Examples of unsaturated hydrocarbons include olefins and aromatic hydrocarbon compounds.

[0188] [Method for producing hydrocarbons, etc.]

[0189] By separating target compounds from the reaction gas obtained according to this embodiment, various chemicals can be obtained.

[0190] Specifically, the hydrocarbon production method of this embodiment includes contacting a mixed feedstock containing ethylene and ethanol with a catalyst in an adiabatic reactor to produce a reaction gas containing olefins having 3 or more carbon atoms. The details of this production method are as described in the aforementioned ethanol conversion method, and preferred embodiments thereof are also the same.

[0191] Examples of hydrocarbons obtained by this production method include olefins such as propylene, ethylene, butene, pentene, hexene, and heptene; aliphatic unsaturated hydrocarbons such as dienes such as 1,3-butadiene and isoprene; aromatic hydrocarbons such as benzene and toluene; and aliphatic saturated hydrocarbons such as ethane, propane, butane, and pentane. The aromatic hydrocarbons preferably have a boiling point of 500° C. or less at normal pressure.

[0192] By introducing the obtained hydrocarbons into a purification system of a cracking unit, target hydrocarbon compounds can be purified efficiently.

[0193] The method for producing hydrocarbons according to this embodiment has the following features:

[0194] A cracking step to decompose hydrocarbons with a carbon number of 2 or more, and

[0195] A purification step of purifying the components obtained in the above cracking step,

[0196] In the purification step, the reaction gas obtained by the ethanol conversion method or the purified fraction thereof is combined.

[0197] The above configuration allows the use of conventional cracking units to obtain target hydrocarbons from ethanol resources. For example, by using bioethanol as a raw material in an ethanol conversion process, bio-derived hydrocarbons can be produced.

[0198] Examples of hydrocarbons having 2 or more carbon atoms include ethylene, propylene, butene, paraffin, and aromatic hydrocarbons. Naphtha can be used as the hydrocarbon having 2 or more carbon atoms.

[0199] As the cracking device, a pyrolysis furnace used in an ethane cracking device, a naphtha cracking device, etc. can be used.

[0200] In the purification step, a purification system used in a conventional ethane cracker or naphtha cracker is used, and distillation can be performed using equipment including, for example, a distillation column, a quenching column, and the like.

[0201] The reaction gas obtained by the above-mentioned ethanol conversion method or its purified fraction merges in the above-mentioned purification step, and the merging position is appropriately selected according to the merged components.

[0202] The method for producing a monomer of this embodiment includes:

[0203] The unsaturated hydrocarbon separation step is to separate a fraction mainly containing unsaturated hydrocarbons from the reaction gas obtained by the above-mentioned ethanol conversion method.

[0204] Examples of the unsaturated hydrocarbons include aliphatic unsaturated hydrocarbons such as olefins such as propylene, ethylene, butene, butane, pentene, hexene, and heptene, and dienes such as 1,3-butadiene and isoprene.

[0205] The method for producing olefins according to this embodiment includes:

[0206] An olefin separation step is performed to separate a fraction mainly containing olefins from the reaction gas obtained by the above-mentioned ethanol conversion method.

[0207] The method for producing propylene according to this embodiment includes:

[0208] A propylene separation step is performed to separate a fraction mainly containing propylene from the reaction gas obtained by the above-mentioned ethanol conversion method.

[0209] The method for producing ethylene of the present embodiment includes:

[0210] An ethylene separation step is performed to separate a fraction mainly containing ethylene from the reaction gas obtained by the above-mentioned ethanol conversion method.

[0211] The method for producing diene of this embodiment includes:

[0212] A diene separation step is performed to separate a fraction mainly containing dienes from the reaction gas obtained by the ethanol conversion method.

[0213] The method for producing a monomer according to the present embodiment may further include a step of converting an unsaturated hydrocarbon.

[0214] The method for producing an acrylic acid-based monomer according to this embodiment includes:

[0215] an unsaturated hydrocarbon separation step of separating a fraction mainly containing unsaturated hydrocarbons from the reaction gas obtained by the above-mentioned ethanol conversion method, and

[0216] An acrylic acid monomer production step of obtaining an acrylic acid monomer from the unsaturated hydrocarbon obtained in the unsaturated hydrocarbon separation step.

[0217] The acrylic monomer production step uses a known method of introducing an acrylic monomer from an unsaturated hydrocarbon.

[0218] The method for producing acrylonitrile of the present embodiment includes:

[0219] a propylene separation step of separating a fraction mainly containing propylene from the reaction gas obtained by the above-mentioned ethanol conversion method, and

[0220] An acrylonitrile production step of obtaining acrylonitrile from the propylene obtained in the above-mentioned propylene separation step.

[0221] The acrylic monomer production step uses a known method of introducing an acrylic monomer from an unsaturated hydrocarbon.

[0222] The method for producing styrene in this embodiment includes:

[0223] an ethylene separation step of separating a fraction mainly containing ethylene from the reaction gas obtained by the above-mentioned ethanol conversion method, and

[0224] A styrene production step of obtaining styrene from the ethylene obtained in the above-mentioned ethylene separation step.

[0225] The monomer obtained by the above-mentioned production method may be further polymerized.

[0226] The method for producing a polymer according to this embodiment includes:

[0227] A step of polymerizing the monomer obtained by the above-mentioned monomer production method.

[0228] The step of polymerizing the monomers can be carried out by using conventional polymerization methods, and various initiators and polymerization catalysts can be used.

[0229] The method for producing an olefin-based polymer according to this embodiment includes:

[0230] A step of polymerizing a polymerizable composition containing an olefin obtained by the above-mentioned method for producing an olefin.

[0231] The polymerizable composition may contain an olefin alone as a monomer or may contain other monomers having an unsaturated bond.

[0232] The method for producing a polypropylene-based polymer according to this embodiment includes:

[0233] A step of polymerizing a polymerizable composition containing propylene obtained by the above-mentioned method for producing propylene.

[0234] The polymerizable composition may contain propylene alone as a monomer or may contain other monomers having an unsaturated bond.

[0235] The method for producing a polyethylene polymer according to this embodiment includes:

[0236] A step of polymerizing a polymerizable composition containing ethylene obtained by the above-mentioned method for producing ethylene.

[0237] The polymerizable composition may contain ethylene alone as a monomer or may contain other monomers having an unsaturated bond.

[0238] The method for producing a diene polymer according to this embodiment includes:

[0239] A step of polymerizing a polymerizable composition containing a diene obtained by the above-mentioned method for producing a diene.

[0240] The polymerizable composition may contain a diene alone as a monomer or may contain other monomers having an unsaturated bond.

[0241] The method for producing an acrylic monomer polymer according to the present embodiment includes:

[0242] A step of polymerizing a polymerizable composition containing an acrylic monomer obtained by the above-mentioned method for producing an acrylic monomer.

[0243] The polymerizable composition may contain an acrylic monomer alone as a monomer, or may contain other monomers having an unsaturated bond.

[0244] The method for producing an acrylonitrile-based polymer according to the present embodiment includes:

[0245] A step of polymerizing a polymerizable composition containing acrylonitrile obtained by the above-mentioned method for producing acrylonitrile.

[0246] The polymerizable composition may contain acrylonitrile alone as a monomer or may contain other monomers having an unsaturated bond.

[0247] The method for producing a styrene-based polymer according to this embodiment includes:

[0248] A step of polymerizing a polymerizable composition containing styrene obtained by the above-mentioned method for producing styrene.

[0249] The polymerizable composition may contain styrene alone as a monomer or may contain other monomers having an unsaturated bond.

[0250] Aromatic compounds can be separated from the reaction gas obtained by the above-mentioned ethanol conversion process.

[0251] The method for producing an aromatic compound of this embodiment includes:

[0252] An aromatic compound separation step is performed to separate a fraction mainly containing aromatic compounds from the reaction gas obtained by the ethanol conversion method.

[0253] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene.

[0254] Example

[0255] Hereinafter, the present embodiment will be described in more detail with reference to examples, but the present embodiment is not limited to the following examples.

[0256] [Methods for measuring catalyst properties]

[0257] Various physical properties of the catalyst were measured as follows.

[0258] (1) Molar ratio of silica to alumina in zeolite

[0259] 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 using an ICP (inductively coupled plasma) emission spectrometer (Rigaku, trade name "JY138"). The silica / alumina molar ratio was derived from the results. The measurement conditions were: high-frequency power: 1 kW, plasma gas: 13 L / min, sheath gas: 0.15 L / min, nebulizer gas: 0.25 L / min, Si measurement wavelength: 251.60 nm, Al measurement wavelength: 396.152 nm.

[0260] (2) Al content and Si content in zeolite-containing catalyst

[0261] A solution obtained by completely dissolving zeolite in a sodium hydroxide solution was prepared, and the amount of aluminum (Al) in the zeolite-containing catalyst was measured and derived in the same manner as in (1).

[0262] (3) Content of doping elements in zeolite-containing catalysts

[0263] The content of the doping element in the zeolite-containing catalyst was measured by a conventional method using a fluorescent X-ray analyzer (manufactured by Rigaku, trade name "RIX3000").

[0264] (4) Zeolite structure type

[0265] The structural type of the zeolite in the zeolite-containing catalyst was identified by measuring the X-ray diffraction pattern of the zeolite using an X-ray analyzer (manufactured by Bruker, trade name "D8 Advance"), and referring to the diffraction patterns of known zeolites. The measurement conditions were as follows.

[0266] Cu cathode

[0267] Tube voltage: 40kV

[0268] Tube current: 40mA

[0269] Scanning speed: 6 degrees per minute

[0270] (5) TPD acid amount per unit weight of the zeolite-containing catalyst and TPD acid amount per unit weight of the zeolite

[0271] The TPD acid amount of the zeolite-containing catalyst (the acid amount determined from the amount of ammonia desorbed at 100 to 650° C. in ammonia temperature desorption measurement) was measured by the following method using a temperature desorption spectrometer BELCAT II.

[0272] As a pretreatment, a 1.0 g catalyst sample was heated to 650°C in He gas and then cooled to 100°C. Next, while the catalyst sample was heated to 100°C, 5 vol% ammonia gas diluted with helium was passed through the sample to allow ammonia to adsorb onto the catalyst. After the catalyst sample was heated to 100°C, 80°C helium gas containing saturated water vapor was passed through the sample to remove the ammonia physically adsorbed onto the catalyst. Helium gas was passed through at 50 mL / min, and after maintaining the temperature at 100°C for 90 minutes, the temperature was increased from 100°C to 850°C at a rate of 5°C / min to measure the amount of ammonia desorbed. A mass spectrum with m / z = 16 was used to detect the desorbed ammonia. The area value from the point where the temperature was increased from 100°C to 850°C to the point where the temperature reached 650°C was calculated from the measured mass spectrum. The TPD acid content per unit weight of the zeolite-containing catalyst was calculated using a calibration curve method. The TPD acid amount per unit weight of the zeolite was calculated from the weight ratio of the TPD acid amount per unit weight of the obtained zeolite-containing catalyst to the zeolite.

[0273] (Acidity maintenance rate)

[0274] In this example, a zeolite-containing catalyst was subjected to steam treatment (STM treatment), and the acid content was observed over time to calculate the acid content maintenance rate. The steam treatment for calculating the acid content maintenance rate was performed by bubbling helium at a flow rate of 50 mL / min through water heated to 80°C. After cooling to 75°C using a condenser, the water was brought into contact with the zeolite-containing catalyst heated to 650°C.

[0275] The acidity maintenance rate at which the zeolite-containing catalyst exhibits resistance to degradation under hydrothermal conditions is calculated by the following formula.

[0276] Acidity retention rate (%) = Acidity after 6.0 hours of STM treatment (μmol / g) / Acidity after 1.0 hours of STM treatment (μmol / g) × 100

[0277] (6) Mesopore volume of zeolite-containing catalyst

[0278] The mesopore volume of the zeolite-containing catalyst was measured by the following method using a mercury intrusion porosimeter (AutoPore 9500, manufactured by MicroMeritics).

[0279] First, as a pretreatment, the zeolite-containing catalyst was coarsely pulverized and sieved to adjust the particle size. After drying the adjusted sample, 0.5 g of the sample was introduced into a measurement cell, filled with mercury, and pressurized. The mesopore volume was calculated based on the mercury intrusion amount.

[0280] (7) Sodium content in zeolite-containing catalyst

[0281] The sodium content in the zeolite-containing catalyst was measured by a conventional method using a fluorescent X-ray analyzer (manufactured by Rigaku, trade name "RIX3000") (hereinafter also referred to as "XRF analysis").

[0282] (Na / Al molar ratio)

[0283] The molar ratio of Na / Al was calculated from the following formula.

[0284] Molar ratio of Na / Al in the zeolite-containing catalyst = [content of sodium (mass %) ÷ atomic weight of sodium] ÷ [(content of aluminum (mass %) / atomic weight of aluminum)]

[0285] (8) Strength of zeolite-containing catalysts

[0286] The strength of the zeolite-containing catalyst was calculated using a digital hardness tester (manufactured by Fujiwara Seisakusho, trade name "KHT-40"). Catalyst samples were dried at 120°C for at least 3 hours, and the compressive strength (unit: N) in the diametrical direction was measured using a hardness tester equipped with a 3 mm diameter indenter. Thirty points of the sample were measured, and the value (unit: N / mm) obtained by dividing the average by 3 was determined as the strength of the zeolite-containing catalyst.

[0287] (9) Coke quantity

[0288] The coke content was calculated as follows. The zeolite-containing catalyst after the reaction was crushed and the weight loss rate was measured in the temperature range of 500°C to 700°C using a thermogravimetric differential thermal analyzer. The value obtained by dividing the weight loss rate by the mass of the effective raw material supplied (unit: mass ppm) was defined as the coke content.

[0289] Effective raw material supply mass (kg) = effective raw material supply mass flow rate (kg / hr) × time from the start to the end of the reaction (hr)

[0290] [Analysis conditions of thermogravimetric differential thermal analyzer]

[0291] Device: Rigaku TG-DTA8122

[0292] Sample container: Pt pot (φ5mm×2.5mmh)

[0293] Reference sample: α-alumina

[0294] Atmosphere: Air (500cc / min)

[0295] Temperature: (1) from room temperature to 120°C at 20°C / min

[0296] (2) Maintain at 120°C for 10 minutes

[0297] (3) Raise the temperature from 120°C to 900°C at 10°C / min

[0298] [Conversion method to ethanol]

[0299] (reactor)

[0300] The following examples and comparative examples use Figure 1 The fixed-bed single-stage adiabatic reactor 1 shown was evaluated.

[0301] (Temperature measurement)

[0302] The temperature of the catalyst bed inlet and the temperature of the catalyst bed outlet were measured by thermocouples inserted from the outside of the reactor. Figure 1 As shown, in a plane perpendicular to the fluid flow direction, with the center of the reactor at 0 and the distance from the center to the reactor inner wall at d, the temperature is measured at 0.5d to 0.6d. It should be noted that the effect of heat generation caused by the insertion of this thermocouple is negligible. Furthermore, if necessary, the thermocouple can be moved in the direction of fluid flow to measure the lowest temperature within the reactor.

[0303] (raw material)

[0304] The following examples utilize a feedstock containing ethanol. The feedstock may also contain ethylene, 1-butene, or water in addition to ethanol. The molar ratio of ethylene / ethanol and the molar ratio of the C4-6 olefin / ethylene in the feedstock are calculated using the following formulas.

[0305] Ethylene / ethanol molar ratio (-) = ethylene molar flow rate (mol / hr) / ethanol molar flow rate (mol / hr)

[0306] Molar ratio of olefins with 4 to 6 carbon atoms / ethylene (-) = Flow rate of olefins with 4 to 6 carbon atoms (mol / hr) / Molar flow rate of ethylene (mol / hr)

[0307] (Reaction Evaluation of Reaction Process)

[0308] According to the following examples and comparative examples, the reaction was carried out in such a way 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), 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 stop of the reaction was calculated. It should be noted that the average inlet and outlet reaction temperature was calculated according to the following formula.

[0309] Average inlet and outlet reaction temperature (°C) = [catalyst bed inlet temperature (°C) + catalyst bed outlet temperature (°C)] / 2

[0310] [Gas chromatography analysis conditions]

[0311] (Reaction Gas Analysis)

[0312] Device: GC-2030 manufactured by Shimadzu Corporation

[0313] Column: Special capillary column SPB-1 manufactured by SUPELCO, USA

[0314] (Inner diameter 0.25mm, length 60m, film thickness 3.0μm)

[0315] Sample gas volume: 1mL (sampling pipe insulation is 200℃~300℃)

[0316] Temperature program: maintain at 40°C for 12 minutes, then increase the temperature to 200°C at a rate of 5°C / min, and maintain at 200°C for 22 minutes.

[0317] Split ratio: 200 to 1

[0318] Carrier gas (nitrogen) flow rate: 120mL / min

[0319] FID detector: Air supply pressure 50 kPa (approximately 500 mL / min), hydrogen supply pressure 60 kPa (approximately 50 mL / min)

[0320] Measurement method: Connect a TCD detector and an FID detector in series. Perform composition analysis based on the data detected by the TCD detector for hydrogen and based on the data detected by the FID detector for oxygen-containing substances such as hydrocarbons and ethanol. Use a calibration curve method to determine the concentration of each component in the reaction gas and the mass generated by the reaction per unit time.

[0321] (Ethylene yield)

[0322] The ethylene yield represents the selectivity for ethylene in the reaction step and is calculated by the following formula.

[0323] Ethylene yield (mass %) = mass of ethylene generated per unit time in the reaction step (kg / hr) / effective raw material supply mass flow rate (kg / hr) × 100

[0324] (Ethylene conversion rate)

[0325] The raw materials of this embodiment do not necessarily contain ethylene. However, ethylene is produced in the reaction step of this embodiment, and ethylene is the smallest olefin. Therefore, the ethylene conversion rate, derived from the mass of ethylene per unit time in the reaction gas, is used as an indicator for evaluating catalyst activity. The ethylene conversion rate is calculated using the following formula.

[0326] Ethylene conversion (mass %) = (effective raw material supply mass flow rate (kg / hr) - ethylene mass per unit time in the reaction gas (kg / hr)) / effective raw material supply mass flow rate (kg / hr) × 100

[0327] Effective feedstock mass flow rate (kg / hr) = ethylene flow rate (kg / hr) + ethylene-equivalent ethanol flow rate (kg / hr) + C4-6 olefin flow rate (kg / hr) + C1-6 oxygenate flow rate (kg / hr)

[0328] Ethylene conversion ethanol flow rate (kg / hr) = ethanol flow rate (kg / hr) × ethylene molecular weight (g / mol) / ethanol molecular weight (g / mol)

[0329] (Propylene yield)

[0330] The propylene yield represents the selectivity for propylene in the reaction step and is calculated by the following formula.

[0331] Propylene yield (mass %) = mass of propylene generated per unit time in the reaction step (kg / hr) / effective raw material supply mass flow rate (kg / hr) × 100

[0332] (Aromatic yield)

[0333] The aromatic yield represents the selectivity for aromatic compounds in the reaction step and is calculated by the following formula.

[0334] Aromatic yield (mass %) = Aromatic mass generated per unit time in the reaction step (kg / hr) / Effective raw material supply mass flow rate (kg / hr) × 100

[0335] Effective feedstock mass flow rate (kg / hr) = ethylene flow rate (kg / hr) + ethylene-equivalent ethanol flow rate (kg / hr) + C4-6 olefin flow rate (kg / hr) + C1-6 oxygenate flow rate (kg / hr)

[0336] Ethylene conversion ethanol flow rate (kg / hr) = ethanol flow rate (kg / hr) × ethylene molecular weight (g / mol) / ethanol molecular weight (g / mol)

[0337] (Yield maintenance rate)

[0338] In Examples 1 to 6 and Comparative Example 1, a 48-hour reaction was regarded as one cycle, and the maintenance rate of the ethylene conversion rate after 24 hours, the maintenance rate of the ethylene conversion rate after 48 hours, the maintenance rate of the propylene yield after 24 hours, the maintenance rate of the propylene yield after 48 hours, the maintenance rate of the aromatic yield after 24 hours, and the maintenance rate of the aromatic yield after 48 hours were calculated by the following formulae.

[0339] In Examples 7 to 14 and Comparative Examples 3 to 5, the catalyst was further regenerated after the first cycle to remove the accumulated coke, and a second cycle was carried out under the same conditions. Thus, the maintenance rate of the ethylene conversion rate after regeneration, the maintenance rate of the propylene yield after regeneration, and the maintenance rate of the aromatic yield after regeneration were calculated by the following formulas.

[0340] Maintenance rate of ethylene conversion after 24 hours (mass %) = ethylene conversion at 24 hours from the start of the first cycle of reaction (mass %) / ethylene conversion at 3 hours from the start of the first cycle of reaction (mass %) × 100

[0341] Maintenance rate of ethylene conversion after 48 hours (mass %) = ethylene conversion at 48 hours from the start of the first cycle of reaction (mass %) / ethylene conversion at 3 hours from the start of the first cycle of reaction (mass %) × 100

[0342] Maintenance rate of ethylene conversion after regeneration (mass %) = ethylene conversion at the time of 3 hours from the start of the reaction of the second cycle (mass %) / ethylene conversion at the time of 3 hours from the start of the reaction of the first cycle (mass %) × 100

[0343] Maintenance rate of propylene yield after 24 hours (mass %) = propylene yield (mass %) at the time of 24 hours from the start of the reaction of the first cycle / propylene yield (mass %) at the time of 3 hours from the start of the reaction of the first cycle × 100

[0344] Maintenance rate of propylene yield after 48 hours (mass %) = propylene yield (mass %) at the time of 48 hours from the start of the reaction of the first cycle / propylene yield (mass %) at the time of 3 hours from the start of the reaction of the first cycle × 100

[0345] Maintenance rate of propylene yield after regeneration (mass %) = propylene yield (mass %) at the time of 3 hours from the start of the reaction of the second cycle / propylene yield (mass %) at the time of 3 hours from the start of the reaction of the first cycle × 100

[0346] Maintenance rate of aromatic yield after 24 hours (mass %) = aromatic yield (mass %) at 24 hours from the start of the first cycle of reaction / aromatic yield (mass %) at 3 hours from the start of the first cycle of reaction × 100

[0347] Maintenance rate of aromatic yield after 48 hours (mass %) = aromatic yield (mass %) at 48 hours from the start of the first cycle of reaction / aromatic yield (mass %) at 3 hours from the start of the first cycle of reaction × 100

[0348] Maintenance rate of aromatic yield after regeneration (mass %) = aromatic yield (mass %) at the time of 3 hours from the start of the reaction of the second cycle / aromatic yield (mass %) at the time of 3 hours from the start of the reaction of the first cycle × 100

[0349] [Production Example 1: Preparation of Zeolite-Containing Catalyst 1]

[0350] Clay obtained from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 980), a medium-pore-diameter zeolite, was kneaded with 89 parts by mass of a colloidal silica solution equivalent to 30 parts by mass of silica (33.8% by mass of silica, 28 ppm by mass of sodium relative to the total amount of the colloidal silica solution). The mixture was then extruded to obtain an extruded body having a diameter of 2.1 mm and a length of 4 to 6 mm. The resulting body was calcined at 600°C for 5 hours to obtain zeolite-containing catalyst 1. The sodium content of the zeolite-containing catalyst at this point was 55 ppm by mass.

[0351] [Production Example 2: Preparation of Zeolite-Containing Catalyst 2]

[0352] Clay obtained from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio of 980), a medium-pore-diameter zeolite, and 89 parts by mass of colloidal silica (33.8% by mass of silica, 28 ppm by mass of sodium relative to the total amount of the colloidal silica liquid) was mixed and kneaded, and then extruded to obtain an extruded body adjusted to a diameter of 2.1 mm and a length of 4 to 6 mm. The obtained body was 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 0.01N silver nitrate aqueous solution for 1 hour, filtered and washed, and this process was repeated three times. The silver exchanger was calcined at 600°C for 5 hours to obtain a silver exchanger. A steam-air mixture containing 80% by volume of water vapor was supplied and flowed through the silver exchanger at a pressure of 0.1 MPa and a temperature of 600°C for 24 hours to obtain zeolite-containing catalyst 2. At this time, the silver content of the zeolite-containing catalyst was 0.16% by mass, and the sodium content was 46% by mass.

[0353] [Production Example 3: Preparation Method of Zeolite-Containing Catalyst 3]

[0354] Clay obtained from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio of 980), a medium-pore-diameter zeolite, was mixed with 89 parts by mass of colloidal silica (33.8% by mass of silica, 28% by mass ppm of sodium relative to the total amount of the colloidal silica solution) equivalent to 30 parts by mass of silica. The mixture was then extruded to obtain an extruded body adjusted to a diameter of 2.1 mm and a length of 4 to 6 mm. A predetermined amount of aqueous diammonium hydrogen phosphate solution was loaded onto the resulting body to obtain a phosphorus-supported product. The resulting phosphorus-supported product was calcined at 600°C for 5 hours in an air atmosphere. The calcined product was then filled into a reactor and a steam-nitrogen mixture containing 80% by volume of water vapor was supplied and circulated at a pressure of 0.1 MPa and a temperature of 600°C for 24 hours to obtain zeolite-containing catalyst 3. At this point, the phosphorus content of the zeolite-containing catalyst was 0.032% by mass, and the sodium content was 76% by mass.

[0355] [Production Example 4: Preparation of Zeolite-Containing Catalyst 4]

[0356] Clay obtained from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 2:12), a medium-pore-diameter zeolite, was mixed with 89 parts by mass of colloidal silica (33.8% silica, 28 ppm sodium content relative to the total amount of the colloidal silica solution) equivalent to 30 parts by mass of silica. The mixture was then extruded to obtain an extruded body adjusted to a diameter of 1.6 mm and a length of 4-6 mm. A predetermined amount of aqueous diammonium hydrogen phosphate solution was loaded onto the resulting body to obtain a phosphorus-supported product. The resulting phosphorus-supported product was calcined at 600°C for 5 hours in an air atmosphere. The calcined product was filled into a reactor and a steam-nitrogen mixture containing 80% water vapor was supplied and circulated at a pressure of 0.1 MPa and a temperature of 600°C for 24 hours to obtain zeolite-containing catalyst 4. At this point, the phosphorus content of the zeolite-containing catalyst was 0.14% by mass, and the sodium content was 253 ppm by mass.

[0357] [Production Example 5: Preparation of Zeolite-Containing Catalyst 5]

[0358] Clay obtained from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 302), a zeolite with an intermediate pore size, was mixed with 89 parts by mass of colloidal silica (33.8% silica, 28 ppm sodium content relative to the total amount of the colloidal silica solution) equivalent to 30 parts by mass of silica. The mixture was then extruded to obtain an extruded body adjusted to a diameter of 1.6 mm and a length of 4 to 6 mm. The resulting body was supported with a predetermined amount of aqueous diammonium hydrogen phosphate solution to obtain a phosphorus-supported product. The resulting phosphorus-supported product was calcined at 600°C for 5 hours in an air atmosphere. The calcined product was filled into a reactor, and a steam-nitrogen mixture containing 80% water vapor was supplied and circulated at a pressure of 0.1 MPa and a temperature of 600°C for 24 hours to obtain zeolite-containing catalyst 5. At this point, the phosphorus content of the zeolite-containing catalyst was 0.085% by mass, and the sodium content was 98 ppm by mass.

[0359] [Production Example 6: Preparation of Zeolite-Containing Catalyst 6]

[0360] Clay obtained from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio of 150), a medium-pore-diameter zeolite, was kneaded with 89 parts by mass of colloidal silica (33.8% by mass of silica, 28 ppm by mass of sodium relative to the total amount of the colloidal silica solution) and then extruded to obtain an extruded body having a diameter of 1.6 mm and a length of 4 to 6 mm. The obtained body was dried at 350°C for 5 hours and then calcined at 600°C for 5 hours to obtain zeolite-containing catalyst 6. The sodium content of the zeolite-containing catalyst was 141 ppm by mass.

[0361] [Production Example 7: Preparation of Zeolite-Containing Catalyst 7]

[0362] 80 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 850), a zeolite with an intermediate pore size, was mixed with 59 parts by mass of colloidal silica (33.8% by mass of silica, 28% by mass ppm of sodium relative to the total amount of the colloidal silica solution) and then extruded to obtain an extruded body adjusted to a diameter of 2.6 mm and a length of 4 to 6 mm. The obtained body was calcined at 600°C for 5 hours to obtain a catalyst precursor. The obtained catalyst precursor was stirred in a 0.01N aqueous silver nitrate solution for 1 hour, filtered and washed, and this process was repeated three times. The catalyst was then calcined at 600°C for 5 hours to obtain zeolite-containing catalyst 7. At this time, the silver content of the zeolite-containing catalyst was 0.2339% by mass, and the sodium content was 10% by mass.

[0363] [Production Example 8: Preparation of Zeolite-Containing Catalyst 8]

[0364] A steam-air mixed gas containing 80% by volume of water vapor was supplied and flowed through the zeolite-containing catalyst 7 under the conditions of a pressure of 0.1 MPa and a temperature of 600° C. for 24 hours, thereby obtaining a zeolite-containing catalyst 8 .

[0365] [Production Example 9: Preparation of Zeolite-Containing Catalyst 9]

[0366] Clay obtained from 80 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio of 850), a medium-pore-diameter zeolite, was mixed with 59 parts by mass of colloidal silica (33.8% by mass of silica, 28% by mass ppm of sodium relative to the total amount of the colloidal silica solution) equivalent to 20 parts by mass of silica. The mixture was then extruded to obtain an extruded body having a diameter of 2.6 mm and a length of 4 to 6 mm. The resulting body was calcined at 600°C for 5 hours to obtain a catalyst precursor. The resulting body was stirred in a 0.002N aqueous silver nitrate solution for 1 hour, then filtered and washed. This process was repeated three times, followed by calcination at 600°C for 5 hours to obtain zeolite-containing catalyst 9. At this time, the silver content of the zeolite-containing catalyst was 0.1360% by mass, and the sodium content was 14% by mass.

[0367] [Production Example 10: Preparation of Zeolite-Containing Catalyst 10]

[0368] A steam-air mixed gas containing 80% by volume of water vapor was supplied and flowed through the zeolite-containing catalyst 9 under the conditions of a pressure of 0.1 MPa and a temperature of 600° C. for 24 hours, thereby obtaining a zeolite-containing catalyst 10 .

[0369] [Production Example 11: Preparation of Zeolite-Containing Catalyst 11]

[0370] 80 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 850), a medium-pore-diameter zeolite, was mixed with 59 parts by mass of colloidal silica (33.8% by mass of silica, 28 ppm by mass of sodium relative to the total amount of the colloidal silica solution) and then extruded to obtain an extruded body adjusted to a diameter of 2.6 mm and a length of 4 to 6 mm. The obtained body was 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 0.01N silver nitrate aqueous solution for 1 hour, filtered and washed, and this process was repeated three times. The silver exchanger was calcined at 600°C for 5 hours to obtain a silver exchanger. A steam-air mixture containing 80% by volume of water vapor was supplied and flowed through the silver exchanger at a pressure of 0.1 MPa and a temperature of 600°C for 24 hours to obtain a zeolite-containing catalyst 11. At this time, the silver content of the zeolite-containing catalyst was 0.2641% by mass, and the sodium content was 38 ppm by mass.

[0371] [Production Example 12: Preparation of Zeolite-Containing Catalyst 12]

[0372] Clay obtained from 80 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 850), a zeolite with an intermediate pore size, was kneaded with 59 parts by mass of colloidal silica (33.8% by mass of silica, 28% by mass ppm of sodium relative to the total amount of the colloidal silica solution) and then extruded to obtain an extruded body adjusted to a diameter of 2.6 mm and a length of 4 to 6 mm. The obtained body was calcined at 600°C for 5 hours, stirred in a 0.001N aqueous silver nitrate solution for 1 hour, and then filtered and washed. This process was repeated three times, and the body was further calcined at 600°C for 5 hours to obtain zeolite-containing catalyst 12. At this time, the silver content of the zeolite-containing catalyst was 0.1899% by mass, and the sodium content was 61% by mass.

[0373] [Production Example 13: Preparation of Zeolite-Containing Catalyst 13]

[0374] Clay obtained from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio of 980), a medium-pore-diameter zeolite, and 89 parts by mass of colloidal silica (33.8% by mass of silica, 28 ppm by mass of sodium relative to the total amount of the colloidal silica solution) were kneaded and extruded to obtain an extruded body having a diameter of 2.1 mm and a length of 4 to 6 mm. The obtained body was calcined at 600°C for 5 hours, impregnated with 100 parts by mass of 0.1N nitric acid relative to 10 parts by mass of the body at room temperature for 1 hour, and then washed with water to obtain zeolite-containing catalyst 13. The sodium content of the zeolite-containing catalyst at this time was 18 ppm by mass.

[0375] [Production Example 14: Preparation of Zeolite-Containing Catalyst 14]

[0376] 80 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 850), a medium-pore-diameter zeolite, was mixed with 59 parts by mass of colloidal silica (33.8% by mass of silica, 28 ppm by mass of sodium relative to the total amount of the colloidal silica solution) equivalent to 20 parts by mass of silica. The mixture was then extruded to obtain an extruded body having a diameter of 2.6 mm and a length of 4 to 6 mm. The resulting body was calcined at 600°C for 5 hours, immersed in 100 parts by mass of 0.1N nitric acid relative to 10 parts by mass of the body at room temperature for 1 hour, and then washed with water to obtain a catalyst precursor. The resulting precursor was filled into a reactor, and a steam-nitrogen mixture containing 80% by volume of water vapor was supplied and circulated at a pressure of 0.1 MPa and a temperature of 600°C for 48 hours to obtain zeolite-containing catalyst 14. At this point, the sodium content in the zeolite-containing catalyst was 21 ppm by mass.

[0377] [Production Example 15: Preparation of Zeolite-Containing Catalyst 15]

[0378] 80 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 850), a medium-pore-diameter zeolite, was mixed with 59 parts by mass of colloidal silica (33.8% by mass of silica, 28 ppm by mass of sodium relative to the total amount of the colloidal silica solution) equivalent to 20 parts by mass of silica. The mixture was then extruded to obtain an extruded body having a diameter of 2.6 mm and a length of 4 to 6 mm. The resulting body was calcined at 600°C for 5 hours, immersed in 100 parts by mass of 0.1N nitric acid relative to 10 parts by mass of the body at room temperature for 1 hour, and then washed with water to obtain a catalyst precursor. A predetermined amount of diammonium hydrogen phosphate aqueous solution was loaded onto the resulting precursor to obtain a phosphorus-supported product. The resulting 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 content in the zeolite-containing catalyst was 0.1687 mass ppm, and the sodium content was 18 mass ppm.

[0379] [Production Example 16: Preparation of Zeolite-Containing Catalyst 16]

[0380] 80 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 850), a medium-pore-diameter zeolite, was mixed with 59 parts by mass of colloidal silica (33.8% by mass of silica, 28 ppm by mass of sodium relative to the total amount of the colloidal silica solution) and then extruded to obtain an extruded body adjusted to a diameter of 2.6 mm and a length of 4 to 6 mm. The obtained body was calcined at 600°C for 5 hours, immersed in 100 parts by mass of 0.1N nitric acid relative to 10 parts by mass of the body at room temperature for 1 hour, and then washed with water to obtain a catalyst precursor. 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 content in the zeolite-containing catalyst was 0.0371% by mass, and the sodium content was 7 ppm by mass.

[0381] [Production Example 17: Preparation of Zeolite-Containing Catalyst 17]

[0382] 80 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio 850), a medium-pore-diameter zeolite, was mixed with 59 parts by mass of colloidal silica (33.8% by mass of silica, 28 ppm by mass of sodium relative to the total amount of the colloidal silica solution) and then extruded to obtain an extruded body adjusted to a diameter of 2.6 mm and a length of 4 to 6 mm. The obtained body was 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 content of silver element contained in the zeolite-containing catalyst was 0.1291 mass %, and the content of sodium element was 339 mass ppm.

[0383] [Production Example 18: Preparation of Zeolite-Containing Catalyst 18]

[0384] Clay obtained from 70 parts by mass of proton-type ZSM-5 (silica / alumina molar ratio of 980), a medium-pore-diameter zeolite, was kneaded with 89 parts by mass of a colloidal silica solution equivalent to 30 parts by mass of silica (33.8% by mass of silica, 28 ppm by mass of sodium relative to the total amount of the colloidal silica solution). The mixture was then extruded to obtain an extruded body having a diameter of 2.1 mm and a length of 4 to 6 mm. The resulting body was calcined at 600°C for 5 hours to obtain zeolite-containing catalyst 18. At this point, the sodium content of the zeolite-containing catalyst was 156 ppm by mass.

[0385] [Example 1]

[0386] (Evaluation of Catalyst Properties)

[0387] The initial TPD acid content of the zeolite-containing catalyst 1 was 10.7 μmol / g, and the acid content maintenance rate was 78.1%. The physical properties of the catalyst obtained by characterization are shown in Table 1.

[0388] (Reaction process)

[0389] 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 filled with a 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 a reaction process was carried out for 48 hours. The propylene yield was 18.4% by mass and the aromatic yield was 3.5% by mass at the time of 3 hours from the start of the reaction. The maintenance rate of the propylene yield at the time of 48 hours was 91.7%, and the maintenance rate of the aromatic yield was 60.2%. The reaction results are shown in Tables 1 and Figure 4 .

[0390] [Example 2]

[0391] (Regeneration process)

[0392] With the zeolite-containing catalyst 1 used in the reaction step in Example 1 filled in the reactor, the circulating gas was switched from the raw material to a nitrogen-diluted gas, and a regeneration step was performed under the conditions of the following steps 1 to 5. The regenerated zeolite-containing catalyst 1 (regenerated catalyst) was reused in the reaction step.

[0393] Step 1) Temperature 480°C, oxygen concentration 1%, 1 hour

[0394] Step 2) Temperature 520°C, oxygen concentration 1%, 3 hours

[0395] Step 3) Temperature 550°C, oxygen concentration 1%, 3 hours

[0396] Step 4) Temperature 550°C, oxygen concentration 5%, 1 hour

[0397] Step 5) Temperature 580°C, oxygen concentration 5%, 2 hours

[0398] (Reaction process: 2nd cycle)

[0399] The reaction process was carried out in the same manner as in Example 1 except that the regenerated catalyst was used. The propylene yield maintenance rate at the time of 48 hours was 91.8%, and the aromatic yield maintenance rate was 63.1%. The reaction results are shown in FIG. Figure 4 .

[0400] (Reaction process: 3rd cycle)

[0401] After the second cycle of the reaction process, the regeneration process was carried out in the same manner as above, and the third cycle of the reaction process was carried out. After 48 hours, the propylene yield was maintained at 92.4%, and the aromatic yield was maintained at 57.1%. The reaction results are shown in FIG. Figure 4 .

[0402] [Example 3]

[0403] The reaction 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 propylene yield retention rate was 93.6%, and the aromatic yield retention rate was 61.4%. The physical properties of the catalyst obtained by characterization and the reaction results are shown in Table 1.

[0404] [Example 4]

[0405] The reaction 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 propylene yield retention rate was 92.1%, and the aromatic yield retention rate was 61.2%. The physical properties of the catalyst obtained by characterization and the reaction results are shown in Table 1.

[0406] [Example 5]

[0407] The reaction 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 propylene yield retention rate was 79.4%, and the aromatic yield retention rate was 50.1%. The physical properties of the catalyst obtained by characterization and the reaction results are shown in Table 1.

[0408] [Example 6]

[0409] The reaction 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 maintenance rate was 73.1%. After 48 hours, the propylene yield maintenance rate was 78.1%, and the aromatic yield maintenance rate was 52.1%. The physical properties of the catalyst obtained by characterization and the reaction results are shown in Table 1.

[0410] [Comparative Example 1]

[0411] The reaction 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 maintenance rate was 44.8%. Three hours after 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 propylene yield maintenance rate was 54.7%, and the aromatic yield maintenance rate was 42.9%. The physical properties of the catalyst obtained by characterization and the reaction results are shown in Table 1.

[0412] From the comparison between the examples and the comparative examples, it can be seen that the acidity maintenance rate of the zeolite-containing catalysts showing an initial TPD acidity of more than a certain amount significantly decreases. In addition, for the zeolite-containing catalysts with a low acidity maintenance rate, it can be seen that the average yield of the target compound decreases and cannot be maintained.

[0413] [Comparative Example 2]

[0414] Zeolite-containing catalyst 6 used in Comparative Example 1 was subjected to a regeneration step in the same manner as in Example 2. When the reaction step was repeated using the resulting regenerated catalyst, the propylene yield was 12.2% by mass and the aromatic yield was 1.1% by mass at 3 hours from the start of the reaction, significantly lower than those in Comparative Example 1.

[0415] [Table 1]

[0416] Table 1

[0417]

[0418] [Example 7]

[0419] (Evaluation of Catalyst Properties)

[0420] Table 2 shows the physical properties of the zeolite-containing catalyst 7 obtained by characterization.

[0421] (Reaction Evaluation)

[0422] A mixed feedstock 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 filled with a 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 for a 48-hour reaction step. Three hours after the start of the reaction, the ethylene yield was 22.6% by mass (ethylene conversion was 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 was 73.5% by mass), the propylene yield was 21.3% by mass, and the aromatic yield was 6.3% by mass.

[0423] Then, the zeolite-containing catalyst 7 used for the 48-hour reaction evaluation was extracted from the reactor and calcined at 580°C for 3 hours under air circulation to regenerate the catalyst. Using the regenerated catalyst obtained, the reaction evaluation was carried out under the same conditions as the above-mentioned reaction evaluation. The ethylene yield at the time point of 3 hours from the start of the reaction was 30.2% by mass (ethylene conversion was 69.8% by mass), the propylene yield was 21.3% by mass, and the aromatic yield was 5.2% by mass. The maintenance rate of each yield is shown in Table 2.

[0424] [Examples 8 to 16, Comparative Examples 3 to 5]

[0425] The physical property evaluation and reaction evaluation of each catalyst were carried out in the same manner as in Example 7, except that the catalysts listed in Table 2 were used.

[0426] Comparing Comparative Example 3 with Examples, it is found that when the TPD acid content of the zeolite is high, the ethylene conversion rate and the propylene yield 24 hours after the start of the reaction cannot be maintained, and the product composition fluctuates greatly.

[0427] Comparing Comparative Examples 4 and 5 with the Examples, it can be seen that when the sodium content of the zeolite-containing catalyst is high or the Na / Al molar ratio is large, the ethylene conversion rate and the propylene yield 24 hours after the start of the reaction, and the ethylene conversion rate and the propylene yield after regeneration cannot be maintained, and a large amount of coke is generated.

[0428] [Table 2]

[0429]

[0430] Description of Reference Numerals

[0431] 1: Reactor

[0432] 2: 1st distillation tower

[0433] 3: Cooler

[0434] 4: Oil-water separator

Claims

1. A method for converting ethanol, comprising: A reaction step of supplying a mixed raw material containing ethanol to a reactor having a fixed bed filled with a zeolite-containing catalyst to obtain 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 ten-membered ring structure. The molar ratio of Na / Al of the zeolite-containing catalyst is 0.0050 to 0.25, In ammonia temperature desorption measurement of the zeolite-containing catalyst, the acid amount per unit weight of the zeolite-containing catalyst, determined from the amount of ammonia desorbed at 100 to 650° C., is 75 μmol / g or less.

2. The ethanol conversion method according to claim 1, wherein: The acid amount Ac per unit weight of the zeolite-containing catalyst satisfies the following formula (1): Ac≤25-60×[Na / Al molar ratio]···(1), The unit of the acid amount Ac is μmol / g.

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

4. The ethanol conversion method according to claim 1, wherein: In ammonia temperature desorption measurement of the zeolite-containing catalyst, the acid amount per unit weight of the zeolite, determined from the amount of ammonia desorbed at 100 to 650° C., is 75 μmol / g or less.

5. The ethanol conversion method according to claim 1, wherein: The sodium content in the zeolite-containing catalyst is 100 ppm by mass or less.

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

7. The ethanol conversion method according to claim 1, wherein: The silica / alumina molar ratio of the zeolite in the zeolite-containing catalyst is 600 to 2000.

8. The ethanol conversion method 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.

9. The ethanol conversion method according to claim 8, wherein: The content of the doping element is 2.0 mass % or less relative to the total amount of the zeolite-containing catalyst.

10. The ethanol conversion method according to claim 1, 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 claim 1, wherein: The mixed feed contains ethylene.

12. The ethanol conversion method according to claim 1, wherein: The ethanol content in the mixed raw material is 30% by mass or more relative to the mixed raw material.

13. The ethanol conversion method according to claim 1, wherein: The molar ratio of ethylene to ethanol in the mixed raw material is 0.20 to 2.

50. The ethanol conversion method according to claim 1, comprising a regeneration step of bringing the zeolite-containing catalyst supplied to the reaction step into contact with an oxygen-containing gas heated to 400°C or higher and supplying the catalyst to the reaction step again.

15. A method for producing propylene, comprising: A propylene separation step for separating a fraction mainly containing propylene from the reaction gas obtained by the ethanol conversion method according to any one of claims 1 to 14.

16. A method for producing an aromatic compound, comprising: An aromatic compound separation step of separating a fraction mainly containing aromatic compounds from the reaction gas obtained by the ethanol conversion method according to any one of claims 1 to 14.

17. A zeolite-containing catalyst, wherein: The zeolite contained in the zeolite-containing catalyst has an oxygen ten-membered ring structure. The molar ratio of Na / Al of the zeolite-containing catalyst is 0.0050 to 0.25, In ammonia temperature desorption measurement of the zeolite-containing catalyst, the acid amount per unit weight of the zeolite-containing catalyst, determined from the amount of ammonia desorbed at 100 to 650° C., is 75 μmol / g or less.

18. The zeolite-containing catalyst according to claim 17, wherein The mass ratio of Si / Al in the zeolite-containing catalyst is 300 to 3000.

19. The zeolite-containing catalyst according to claim 17, wherein The zeolite-containing catalyst is a catalyst for obtaining olefins having 3 or more carbon atoms from a mixed feedstock containing ethanol.

20. The zeolite-containing catalyst according to claim 17, 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 claim 20, wherein The content of the doping element is 2.0 mass % or less relative to the total amount of the zeolite-containing catalyst.

22. The zeolite-containing catalyst according to claim 17, 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, wherein: The zeolite contained in the zeolite-containing catalyst is a zeolite having an oxygen ten-membered ring structure, The molar ratio of Na / Al of the zeolite-containing catalyst is 0.0050 to 0.25, In ammonia temperature desorption measurement of the zeolite-containing catalyst, the acid amount per unit weight of the zeolite-containing catalyst, as determined from the amount of ammonia desorbed at 100 to 650° C., is 75 μmol / g or less. The method for producing the zeolite-containing catalyst includes a steaming step of contacting the zeolite-containing catalyst with steam at a steaming temperature of 450° C. or higher.

24. A method for producing hydrocarbons, comprising: A reaction step of supplying a raw material containing ethanol to a reactor having a fixed bed filled with a zeolite-containing catalyst to obtain 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 ten-membered ring structure, The molar ratio of Na / Al of the zeolite-containing catalyst is 0.0050 to 0.25, In ammonia temperature desorption measurement of the zeolite-containing catalyst, the acid amount per unit weight of the zeolite-containing catalyst, determined from the amount of ammonia desorbed at 100 to 650° C., is 75 μmol / g or less.

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