Hydrocarbon production catalyst, liquefied petroleum gas production apparatus, and method for producing liquefied petroleum gas

Abstract

The present invention provides a hydrocarbon production catalyst, a liquefied petroleum gas production apparatus, and a method for producing liquefied petroleum gas that can improve the yield of liquefied petroleum gas. [Solution] The hydrocarbon production catalyst comprises a zeolite and an acid-controlling component contained in the zeolite. The zeolite includes a zeolite having a porous structure of an 8-membered oxygen ring, a Si / Al ratio of 50 or less, and an average primary particle diameter of 1000 nm or less. The acid-controlling component contains at least one selected from the group consisting of alkali metals, alkaline earth metals, alkali metal oxides, and alkaline earth metal oxides. Furthermore, the metal content of the acid-controlling component is 0.390 mmol or less per 1 g of zeolite.

Description

[Technical Field]

[0001] This disclosure relates to a hydrocarbon production catalyst, a liquefied petroleum gas production apparatus, and a method for producing liquefied petroleum gas. [Background technology]

[0002] Liquefied petroleum gas (LPG) is widely used as a fuel for both household and commercial purposes because it can be stored and transported in liquid form. According to the Liquefied Petroleum Gas Safety Regulations, such LPG is defined as "a substance mainly composed of hydrocarbons with 3 or 4 carbon atoms," and is generally obtained by compressing and liquefying hydrocarbon gas mainly composed of propane or butane. Furthermore, according to the Enforcement Regulations of the Act on Ensuring the Safety and Fairness of Transactions of Liquefied Petroleum Gas, the LPG widely used as a fuel for household and commercial purposes is classified as "Type I LPG," and has a propane content of 80 mol% or more.

[0003] Traditionally, liquefied petroleum gas (LPG) has been produced using fossil fuel-derived methods, such as separating LPG generated during the petroleum refining process. However, from a zero-emission perspective, there is a need to produce LPG using methods that do not originate from fossil fuels. As such a method for producing LPG, a method has been investigated that uses a raw material containing at least one selected from the group consisting of methanol and dimethyl ether, along with hydrogen. For example, Non-Patent Literature 1 discloses a zeolite (ZSM-5) having an MFI structure as a catalyst for synthesizing LPG from a methanol-containing raw material. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Semi-indirect synthesis of LPG from syngas: Conversion of DME into LPG(Catalysis Today 106 (2005) 247-251) [Overview of the project] [Problems that the invention aims to solve]

[0005] However, catalysts using zeolite (ZSM-5) having an MFI structure as described in Non-Patent Document 1 have the drawback of low LPG yield.

[0006] The object of this disclosure is to provide a zeolite catalyst, a liquefied petroleum gas production apparatus, and a method for producing liquefied petroleum gas that can improve the yield of liquefied petroleum gas. [Means for solving the problem]

[0007] The present disclosure [1] includes a hydrocarbon production catalyst comprising a zeolite and an acid-controlling component contained in the zeolite, wherein the zeolite includes a zeolite having a porous structure of an 8-membered oxygen ring, the Si / Al ratio of the zeolite is 50 or less, the average primary particle diameter of the zeolite is 1000 nm or less, the acid-controlling component includes at least one selected from the group consisting of alkali metals, alkaline earth metals, alkali metal oxides, and alkaline earth metal oxides, and the metal content of the acid-controlling component is 0.390 mmol or less per 1 g of the zeolite.

[0008] This disclosure [2] includes the hydrocarbon production catalyst described in [1] above, wherein the acid control component comprises at least one selected from the group consisting of sodium, potassium, calcium, magnesium, strontium, barium, and oxides thereof.

[0009] This disclosure [3] includes the hydrocarbon production catalyst described in [1] or [2] above, wherein the metal content of the acid control component is 0.078 mmol or more and 0.338 mmol or less per 1 g of zeolite.

[0010] This disclosure [4] includes a hydrocarbon production catalyst according to any one of the above [1] to [3], supported on the zeolite, wherein the acid control component comprises the above-mentioned hydrocarbon production catalyst.

[0011] The present disclosure [5] includes a liquefied petroleum gas production apparatus for producing hydrocarbons having at least 3 and 4 carbon atoms from a raw material comprising at least one selected from the group consisting of methanol and dimethyl ether and hydrogen, the apparatus comprising a hydrocarbon production catalyst according to any one of the above [1] to [4] and a hydrogenation catalyst disposed downstream of the hydrocarbon production catalyst in the flow direction of the raw material.

[0012] The present disclosure [6] includes a method for producing liquefied petroleum gas, comprising a preparation step of preparing a hydrocarbon production catalyst as described in any one of [1] to [4] above, and a reaction step of contacting a raw material comprising at least one selected from the group consisting of methanol and dimethyl ether and hydrogen with the hydrocarbon production catalyst to obtain a reaction product comprising hydrocarbons having at least 3 and 4 carbon atoms.

[0013] This disclosure [7] includes a method for producing liquefied petroleum gas as described in [6] above, wherein the reaction pressure in the reaction step is 0.05 MPa or more and 5.00 MPa or less.

[0014] This disclosure [8] includes a method for producing liquefied petroleum gas according to [6] or [7] above, wherein the reaction product exhibits the highest selectivity for a C3 hydrocarbon.

[0015] The present disclosure [9] includes a method for producing liquefied petroleum gas according to any one of the above [6] to [8], further comprising a second reaction step of contacting the reaction product with a hydrogenation catalyst to obtain a second reaction product. [Effects of the Invention]

[0016] The hydrocarbon production catalyst of this disclosure comprises a zeolite having a porous structure of an 8-membered oxygen ring, and an acid control component contained in the zeolite that includes at least one selected from the group consisting of alkali metals, alkaline earth metals, alkali metal oxides, and alkaline earth metal oxides, wherein the Si / Al ratio of the zeolite is 50 or less, the average primary particle diameter of the zeolite is 1000 nm or less, and the metal content of the acid control component is 0.390 mmol or less per 1 g of zeolite. Therefore, it is possible to improve the conversion rate from a raw material containing at least one selected from the group consisting of methanol and dimethyl ether and hydrogen to a reaction product containing at least C3 and C4 hydrocarbons, and to improve the selectivity of C3 and C4 hydrocarbons in the reaction product. As a result, the yield of liquefied petroleum gas can be improved.

[0017] The liquefied petroleum gas production apparatus of this disclosure is equipped with the hydrocarbon production catalyst described above. Therefore, the conversion rate from a raw material containing at least one selected from the group consisting of methanol and dimethyl ether and hydrogen to a reaction product containing at least three- and four-carbon hydrocarbons can be improved, and the selectivity of three- and four-carbon hydrocarbons in the reaction product can be improved. Furthermore, the liquefied petroleum gas production apparatus of this disclosure is equipped with a hydrogenation catalyst positioned downstream of the hydrocarbon production catalyst in the flow direction of the raw material. Therefore, the proportion of paraffin in the three- and four-carbon hydrocarbons can be improved. As a result, the yield of liquefied petroleum gas can be improved.

[0018] The method for producing liquefied petroleum gas according to the present disclosure includes a preparation step of preparing the above-mentioned hydrocarbon production catalyst, and a reaction step of bringing a raw material into contact with the hydrocarbon production catalyst to obtain a reaction product containing at least hydrocarbons having 3 and 4 carbon atoms. Therefore, the conversion rate from a raw material containing at least one selected from the group consisting of methanol and dimethyl ether and hydrogen to a reaction product containing at least hydrocarbons having 3 and 4 carbon atoms is improved, and in the reaction product, the selectivity of hydrocarbons having 3 and 4 carbon atoms can be improved. As a result, the yield of liquefied petroleum gas can be improved.

Brief Description of Drawings

[0019] [Figure 1] FIG. 1 shows a schematic diagram of an embodiment of a liquefied petroleum gas production apparatus according to the present disclosure. [Figure 2] FIG. 2 shows an image of a scanning electron microscope (SEM image) of the zeolite of Example 1. [Figure 3] FIG. 3 shows an SEM image of the zeolite of Example 3. [Figure 4] FIG. 4 shows an SEM image of the zeolite of Example 10.

Embodiments for Carrying Out the Invention

[0020] 1. Hydrocarbon production catalyst The hydrocarbon production catalyst is a catalyst for producing hydrocarbons. Specifically, the hydrocarbon production catalyst is a catalyst for obtaining a reaction product containing at least hydrocarbons having 3 and 4 carbon atoms from a raw material containing at least one selected from the group consisting of methanol and dimethyl ether and hydrogen.

[0021] The reaction products include hydrocarbons having at least three and four carbon atoms. Examples of hydrocarbons having three and four carbon atoms include paraffins and olefins having three and four carbon atoms. The paraffin with three carbon atoms is propane, and the paraffin with four carbon atoms is butane. The olefin with three carbon atoms is propylene (propene), and the olefin with four carbon atoms is butene.

[0022] In addition, the reaction product may contain hydrocarbons other than C3 and C4 hydrocarbons. Examples of hydrocarbons other than C3 and C4 hydrocarbons include relatively short-chain hydrocarbons. Examples of relatively short-chain hydrocarbons include C1 and C2 paraffins, C2 olefins, C5-C8 paraffins, and C5-C8 olefins.

[0023] The hydrocarbon production catalyst comprises a zeolite and an acid-controlling component contained in the zeolite. Preferably, it consists of a zeolite and an acid-controlling component contained in the zeolite.

[0024] 1.1. Zeolite Zeolites are crystalline aluminosilicates. Crystalline aluminosilicates consist of crystals with a three-dimensional network structure in which aluminum (Al) and silicon (Si) are used as the skeletal metals (hereinafter referred to as T atoms), and Al and Si are bonded via oxygen (O).

[0025] Zeolites include zeolite-like substances. Zeolite-like substances contain elements other than Al and Si as the T atom. Specifically, examples of zeolite-like substances include silicoaluminophosphate (SAPO) and aluminophosphate (AlPO) containing phosphorus (P).

[0026] The zeolite preferably contains no T atoms other than Al and Si. More preferably, the T atoms consist of Al and Si, and have a three-dimensional network structure in which Al and Si are bonded via O.

[0027] As mentioned above, zeolites are crystalline aluminosilicates, and at least Al and Si are T atoms. In other words, zeolites are silicates in which all T atoms are Si, and some Si 4+ Al 3+ It has been replaced with Al. 3+ is Si 4+ Because of their lower valence, zeolites develop a negative charge. To maintain neutrality, zeolites have cations (countercations) near the Al atoms (within the pores).

[0028] Examples of zeolite countercations include ammonium ions (NH4). + ), and proton (H + ) are some examples.

[0029] Examples of zeolites include proton-type zeolites containing a proton as a countercation, and ammonium-type zeolites containing an ammonium ion as a countercation.

[0030] In this embodiment, the zeolite is a crystalline aluminosilicate particle. Examples of particle shapes include a roughly spherical shape and a roughly hexahedral shape. A roughly hexahedral shape is preferred.

[0031] The particle shape of the zeolite can be confirmed by observation using a scanning electron microscope (SEM). Specifically, in the SEM images shown in Figures 2 and 4, the shape of the zeolite is approximately hexahedral. In the SEM image shown in Figure 3, the shape of the zeolite is approximately spherical.

[0032] Furthermore, zeolites include those with a pore structure of an 8-membered oxygen ring. The value of n (where n is an integer) in zeolites with an n-membered oxygen ring indicates the pore with the largest number of oxygen atoms among those composed of oxygen and skeletal metal that form the zeolite's skeletal structure.

[0033] If the zeolite includes one having a porous structure with an 8-membered oxygen ring, the number of carbon atoms in the hydrocarbons contained in the reaction product can be adjusted to a desired range. As a result, the selectivity of hydrocarbons with 3 and 4 carbon atoms in the reaction product can be improved.

[0034] Furthermore, the zeolite may include zeolites having pore structures other than an 8-membered oxygen ring. Examples of zeolites having other pore structures include zeolites having a 10-membered oxygen ring pore structure and zeolites having a 12-membered oxygen ring pore structure.

[0035] The zeolite preferably contains as its main component a zeolite having a porous structure of an 8-membered oxygen ring.

[0036] To say that a zeolite contains zeolite having an 8-membered oxygen ring pore structure as its main component means that the content of zeolite having an 8-membered oxygen ring pore structure in the total amount of zeolite is 50% by mass or more. Preferably, the content of zeolite having an 8-membered oxygen ring pore structure in the total amount of zeolite is 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 98% by mass or more.

[0037] The zeolite is more preferably composed of a zeolite having a pore structure of an 8-membered oxygen ring. In other words, it is preferable that the zeolite does not contain zeolites having pore structures other than the 8-membered oxygen ring.

[0038] Zeolites having an oxygen 8-membered ring pore structure include, for example, at least one selected from the group consisting of zeolites having a CHA structure and zeolites having an AEI structure.

[0039] If the zeolite includes at least one selected from the group consisting of zeolites having a CHA structure and zeolites having an AEI structure, the number of carbon atoms in the hydrocarbons contained in the reaction product can be adjusted to a desired range. As a result, the selectivity of hydrocarbons with 3 and 4 carbon atoms in the reaction product can be improved.

[0040] Furthermore, the statement that the zeolite includes at least one selected from the group consisting of zeolites having a CHA structure and zeolites having an AEI structure means that either a zeolite having a CHA structure or a zeolite having an AEI structure may be used alone, or a combination of a zeolite having a CHA structure and a zeolite having an AEI structure (physically mixed, as a mixed crystal, or in combination thereof). Alternatively, at least one selected from the group consisting of zeolites having a CHA structure and zeolites having an AEI structure may be used in combination with a zeolite having another skeletal structure (physically mixed, as a mixed crystal, or in combination thereof).

[0041] Examples of zeolites having other skeletal structures include zeolites having one skeletal structure selected from the group consisting of AFX structure, DDR structure, ERI structure, KFI structure, LEV structure, MWF structure, and RHO structure.

[0042] The regular skeletal structure in zeolites is identified by the structural code (hereinafter referred to as "structural code") defined by the Structure Commission of the International Zeolite Association. For example, the CHA structure is identified as the structural code "CHA". The skeletal structure of zeolites can be identified by comparing it with the XRD patterns of each structure described in Collection of simulated XRD powder patterns for zeolites, Fifth revised edition, (2007).

[0043] In this embodiment, "zeolite having a CHA structure" and other "zeolite having a ~ structure" refer to a zeolite having the skeletal structure of the zeolite with the above-mentioned structural code.

[0044] The zeolite preferably contains as a main component at least one selected from the group consisting of zeolites having a CHA structure and zeolites having an AEI structure.

[0045] Furthermore, the statement that the zeolite contains at least one selected from the group consisting of zeolites having a CHA structure and zeolites having an AEI structure as a main component means that the total amount of zeolites having a CHA structure and zeolites having an AEI structure in the total amount of zeolites is 50% by mass or more. The total amount of zeolites having a CHA structure and zeolites having an AEI structure in the total amount of zeolites is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 98% by mass or more.

[0046] The zeolite preferably consists of at least one selected from the group consisting of zeolites having a CHA structure and zeolites having an AEI structure. More preferably, it consists of zeolites having a CHA structure. In other words, it is preferable that the zeolite does not contain zeolites having other skeletal structures.

[0047] The pore size of the zeolite is not particularly limited, and is, for example, 0.1 nm or larger, preferably 0.3 nm or larger, and for example, 3 nm or smaller, preferably 1.0 nm or smaller, and more preferably 0.5 nm or smaller. In zeolites having an oxygen n-membered ring, the pore size of the zeolite tends to increase as n increases (i.e., as the number of oxygen atoms forming the zeolite's skeletal structure increases).

[0048] If the pore size of the zeolite is within the above range, the selectivity of hydrocarbons having 3 and 4 carbon atoms in the reaction product can be improved.

[0049] The pore diameter of a zeolite refers to the crystallographic channel diameter as defined by the International Zeolite Association. If a zeolite contains multiple zeolites with different skeletal structures, the pore diameter of the zeolite is the average pore diameter calculated from the crystallographic channel diameters defined by the International Zeolite Association and the proportion of zeolites with each skeletal structure.

[0050] The average primary particle size of the zeolite is, for example, 10 nm to 1000 nm, preferably 50 nm to 900 nm, more preferably 100 nm to 800 nm, even more preferably 150 nm to 600 nm, and particularly preferably 150 nm to 500 nm.

[0051] The average primary particle diameter of the zeolite is, for example, 10 nm or more, preferably 50 nm or more, more preferably 100 nm or more, and even more preferably 150 nm or more. Alternatively, the average primary particle diameter of the zeolite is 1000 nm or less, preferably 900 nm or less, more preferably 800 nm or less, even more preferably 600 nm or less, and particularly preferably 500 nm or less.

[0052] If the average primary particle size of the zeolite is below the above upper limit, the conversion rate from a raw material containing at least one selected from the group consisting of methanol and dimethyl ether and hydrogen to a reaction product containing at least three- and four-carbon hydrocarbons can be improved, and the selectivity of three- and four-carbon hydrocarbons in the reaction product can be improved.

[0053] In particular, if the average primary particle size of the zeolite is 500 nm or less, a high conversion rate to reaction products can be maintained for a long period of time, and the selectivity of hydrocarbons with 3 and 4 carbon atoms in the reaction products can also be maintained at a high level.

[0054] The average primary particle diameter of the zeolite can be measured, for example, by observation using a scanning electron microscope (SEM), as will be described in detail in the examples below. When the particle shape of the zeolite is approximately spherical, the average primary particle diameter of the zeolite is the length corresponding to the diameter portion of the approximately spherical particle. When the particle shape of the zeolite is approximately hexahedral, the average primary particle diameter of the zeolite is the length corresponding to the average value of the long side and short side (=(long side + short side) / 2) in the SEM image, excluding the depth side of the approximately hexahedral particle. In the examples of this disclosure, the average primary particle diameter of the zeolite is measured by observation using an SEM, but it is not particularly limited and may be measured by observation using a transmission electron microscope (TEM) or the like, as long as it is possible to observe the zeolite particles.

[0055] The Si / Al ratio (molar ratio of silicon to aluminum) of the zeolite is, for example, 3 to 50, preferably 3 to 45, more preferably 5 to 40, and even more preferably 8 to 35.

[0056] The Si / Al ratio (molar ratio of silicon to aluminum) of the zeolite is, for example, 3 or more, preferably 5 or more, and more preferably 8 or more. Alternatively, the Si / Al ratio (molar ratio of silicon to aluminum) of the zeolite is 50 or less, preferably 45 or less, more preferably 40 or less, and even more preferably 35 or less.

[0057] If the Si / Al ratio of the zeolite is within the above range, the selectivity of C3 and C4 hydrocarbons in the reaction product can be improved. More specifically, if the Si / Al ratio of the zeolite is below the above upper limit, it is possible to ensure a sufficient number of Al-derived acid sites that act as reaction sites for at least one selected from the group consisting of methanol and dimethyl ether. Furthermore, if the Si / Al ratio of the zeolite is above the above lower limit, the occurrence of side reactions due to an excessive increase in the number of Al-derived acid sites can be suppressed.

[0058] The Si / Al ratio of zeolite can be determined by, for example, X-ray fluorescence spectrometry (XRF) or inductively coupled plasma mass spectrometry (ICP-MS).

[0059] The specific surface area of zeolite is not particularly limited. For example, it is 100 m 2 / g or more, preferably 300 m 2 / g or more. Also, for example, it is 1000 m 2 / g or less, preferably 800 m 2 / g or less.

[0060] The specific surface area of zeolite can be measured by the BET method.

[0061] 1.2. Acid control component The acid control component contains at least one selected from the group consisting of alkali metals, alkaline earth metals, oxides of alkali metals, and oxides of alkaline earth metals.

[0062] In zeolite, the activity as a catalyst can be adjusted by adjusting its acidic properties. To adjust the acidic properties, it is necessary to control the Si / Al ratio. However, depending on the framework structure of zeolite, it is not easy to control the Si / Al ratio, and it is difficult to adjust the acidic properties of zeolite. Therefore, if the acid control component contained in zeolite includes at least one selected from the group consisting of alkali metals, alkaline earth metals, oxides of alkali metals, and oxides of alkaline earth metals, the acidic properties as a hydrocarbon production catalyst can be adjusted without changing the Si / Al ratio of zeolite. As a result, the conversion rate from a raw material containing at least one selected from the group consisting of methanol and dimethyl ether and hydrogen to a reaction product containing at least hydrocarbons having 3 and 4 carbon atoms can be improved, and the selectivity of hydrocarbons having 3 and 4 carbon atoms in the reaction product can be improved.

[0063] Examples of alkali metals include sodium and potassium. Sodium is preferred. Examples of alkaline earth metals include calcium, magnesium, strontium, and barium. Calcium and magnesium are preferred. Calcium is more preferred.

[0064] Examples of alkali metal oxides include sodium oxide and potassium oxide. Sodium oxide is preferred. Examples of alkaline earth metal oxides include calcium oxide, magnesium oxide, strontium oxide, and barium oxide. Calcium oxide and magnesium oxide are preferred. Calcium oxide is more preferred.

[0065] Alkali metals, alkaline earth metals, alkali metal oxides, and alkaline earth metal oxides may be used individually or in combination of two or more. When supporting an acid-controlling component on a zeolite, the zeolite is added to an aqueous solution containing an alkali metal and / or alkaline earth metal salt as the acid-controlling component, and after adsorption, it is calcined in the atmosphere. As a result, the alkali metal and / or alkaline earth metal as the acid-controlling component may become oxides (oxidized). Furthermore, when used as a hydrocarbon production catalyst, some of it may be reduced by hydrogen in the raw material gas, and the alkali metal oxides and / or alkaline earth metal oxides as acid-controlling components may become metallic (reduced).

[0066] The acid control component may include other metals or metal oxides other than alkali metals, alkaline earth metals, alkali metal oxides, and alkaline earth metal oxides. Preferably, the acid control component does not include other metals or metal oxides other than alkali metals, alkaline earth metals, alkali metal oxides, and alkaline earth metal oxides. In other words, preferably, the acid control component consists of at least one selected from the group consisting of alkali metals, alkaline earth metals, alkali metal oxides, and alkaline earth metal oxides.

[0067] The acid-controlling component preferably comprises at least one selected from the group consisting of sodium, potassium, calcium, magnesium, strontium, barium, and their oxides. More preferably, it comprises at least one selected from the group consisting of sodium, potassium, calcium, magnesium, strontium, barium, and their oxides. Even more preferably, it comprises at least one selected from the group consisting of sodium, calcium, magnesium, strontium, barium, and their oxides. Particularly preferably, it comprises at least one selected from the group consisting of calcium, magnesium, calcium oxide, and magnesium oxide. Most preferably, it comprises calcium and / or calcium oxide.

[0068] If the acid control component consists of at least one selected from the group comprising calcium, magnesium, calcium oxide, and magnesium oxide, a high conversion rate to the reaction product can be maintained for a long period of time, and a high selectivity for hydrocarbons having 3 and 4 carbon atoms can also be maintained in the reaction product.

[0069] The acid-controlling component is contained in the zeolite described above. Specifically, the acid-controlling component is supported on the zeolite, and / or alkali metals and / or alkaline earth metals as acid-controlling components are introduced into the zeolite as metal ions by ion exchange. Preferably, the acid-controlling component is supported on the zeolite.

[0070] If the acid control component is supported on a zeolite, the conversion rate from a starting material containing at least one selected from the group consisting of methanol and dimethyl ether and hydrogen to a reaction product containing at least three- and four-carbon hydrocarbons can be further improved, and the selectivity of three- and four-carbon hydrocarbons in the reaction product can be improved.

[0071] In this disclosure, "the acid-controlling component is supported on the zeolite" means that the acid-controlling component is present on the surface of the zeolite by the support method described later.

[0072] Specifically, an acid-controlling component is present on the surface of the zeolite, comprising at least one selected from the group consisting of alkali metals, alkaline earth metals, alkali metal oxides, and alkaline earth metal oxides.

[0073] The acid-controlling component supported on the zeolite may, for example, be supported substantially uniformly across the entire surface of the zeolite, or its distribution on the zeolite surface may differ depending on the method of use of the hydrocarbon production catalyst. Preferably, from the viewpoint of the manufacturability of the hydrocarbon production catalyst, it is supported substantially uniformly across the entire surface of the zeolite.

[0074] Furthermore, in this disclosure, when alkali metals and / or alkaline earth metals as acid control components are introduced into the zeolite as metal ions by ion exchange, it refers to a state in which the metal ions are introduced into the zeolite as countercations by ion exchange as described later.

[0075] As mentioned above, zeolites have countercations near Al (within the pores). Examples of countercations include ammonium ions (NH4). + ), and proton (H + ) are examples, but some or all of these countercations can be exchanged for the metal ions mentioned above.

[0076] The metal ion includes, for example, at least one selected from the group consisting of alkali metal ions and alkaline earth metal ions. Preferably, it consists of at least one selected from the group consisting of alkali metal ions and alkaline earth metal ions.

[0077] Examples of alkali metal ions include sodium ions and potassium ions. Examples of alkaline earth metal ions include calcium ions, magnesium ions, strontium ions, and barium ions. Alkali metal ions and alkaline earth metal ions may be used individually or in combination of two or more types.

[0078] The above-described method of supporting the acid-controlling component on the zeolite and the above-described ion exchange in the zeolite (ion exchange of the zeolite's countercations with metal ions) may be used in combination. Specifically, the acid-controlling component can be supported on a zeolite that has metal ions as countercations. The metal ions and the supported acid-controlling component may be of the same element or of different elements.

[0079] For every gram of zeolite, the content of the acid-controlling metal component is, for example, 0.010 mmol to 0.390 mmol, preferably 0.050 mmol to 0.350 mmol, more preferably 0.078 mmol to 0.338 mmol, even more preferably 0.090 mmol to 0.300 mmol, particularly preferably 0.100 mmol to 0.280 mmol, and most preferably 0.120 mmol to 0.270 mmol.

[0080] For 1 g of zeolite, the content of the acid-controlling metal component is, for example, 0.010 mmol or more, preferably 0.050 mmol or more, more preferably 0.078 mmol or more, even more preferably 0.090 mmol or more, particularly preferably 0.100 mmol or more, and most preferably 0.120 mmol or more. Also, for 1 g of zeolite, the content of the acid-controlling metal component is 0.390 mmol or less, preferably 0.350 mmol or less, more preferably 0.338 mmol or less, even more preferably 0.300 mmol or less, particularly preferably 0.280 mmol or less, and most preferably 0.270 mmol or less.

[0081] If the metal content of the acid-controlling component per 1g of zeolite is within the above range, the conversion rate from a raw material containing at least one selected from the group consisting of methanol and dimethyl ether and hydrogen to a reaction product containing at least three- and four-carbon hydrocarbons can be improved, and the selectivity of three- and four-carbon hydrocarbons in the reaction product can be improved. Furthermore, if the metal content of the acid-controlling component per 1g of zeolite is within the above range, a high conversion rate to the reaction product can be maintained for a long period of time, and a high selectivity of three- and four-carbon hydrocarbons in the reaction product can also be maintained.

[0082] Furthermore, the metal in the acid-controlling component refers to the metal within the acid-controlling component (e.g., alkali metals and alkaline earth metals). Also, if the acid-controlling component contains metal oxides (e.g., oxides of alkali metals and alkaline earth metals), the metal in the acid-controlling component refers to the metal within the metal oxide.

[0083] In hydrocarbon production catalysts, the metal content of the acid control component per 1 ml of Al in the zeolite is, for example, 0.010 ml to 0.400 ml, preferably 0.030 ml to 0.350 ml, more preferably 0.050 ml to 0.320 ml, even more preferably 0.060 ml to 0.300 ml, and particularly preferably 0.070 ml to 0.290 ml.

[0084] In hydrocarbon production catalysts, the metal content of the acid control component per 1 ml of Al in the zeolite is, for example, 0.010 ml or more, preferably 0.030 ml or more, more preferably 0.050 ml or more, even more preferably 0.060 ml or more, particularly preferably 0.070 ml or more, and also, for example, 0.400 ml or less, preferably 0.350 ml or less, more preferably 0.320 ml or less, even more preferably 0.300 ml or less, particularly preferably 0.290 ml or less.

[0085] In a hydrocarbon production catalyst, if the metal content of the acid control component per 1 mol of Al in the zeolite is within the above range, the conversion rate from a raw material containing at least one selected from the group consisting of methanol and dimethyl ether and hydrogen to a reaction product containing at least three- and four-carbon hydrocarbons can be improved, and the selectivity of three- and four-carbon hydrocarbons in the reaction product can be improved. Furthermore, in a hydrocarbon production catalyst, if the metal content of the acid control component per 1 mol of Al in the zeolite is within the above range, a high conversion rate to the reaction product can be maintained for a long period of time, and a high selectivity of three- and four-carbon hydrocarbons in the reaction product can also be maintained.

[0086] 2. Method for producing hydrocarbon catalysts The method for producing the hydrocarbon catalyst described above will now be explained.

[0087] The method for producing a hydrocarbon production catalyst includes a step of preparing a zeolite (zeolite preparation step) and a step of incorporating an acid control component into the zeolite (catalyst formation step).

[0088] 2.1. Zeolite Preparation Process Zeolites are prepared by commonly used hydrothermal synthesis methods.

[0089] In this embodiment, first, an alkali metal source and an organic structure-determining agent are dissolved in water. Next, an aluminum source and a silica source are added to the resulting solution and stirred to prepare a gel-like mixture. If necessary, a seed crystal zeolite may be added along with the aluminum source and silica source. Alternatively, water may be added separately, or an aqueous solution containing the dissolved alkali metal source and / or an aqueous solution containing the dissolved organic structure-determining agent may be used.

[0090] Examples of alkali metal sources include alkali metal hydroxides. Preferably, sodium hydroxide and potassium hydroxide are used. The alkali metal sources may be used alone or in combination of two or more.

[0091] Organic structure-determining agents can promote the crystallization of zeolites having a desired skeletal structure. The organic structure-determining agent is not particularly limited as long as it is a compound that promotes the crystallization of zeolites having a desired skeletal structure. Examples of organic structure-determining agents used in producing zeolites having a CHA structure include N,N,N-trialkyl-1-adamantaneammonium, N,N,N-trialkylbenzylammonium, and 1-adamantylamine. Preferably, N,N,N-trialkyl-1-adamantaneammonium is used. More preferably, N,N,N-trimethyl-1-adamantaneammonium is used. Examples of organic structure-determining agents used in producing zeolites having an AEI structure include 1,1,3,5-tetramethylpiperidinium, 1,1-diethyl-2,6-dimethylpiperidinium, 1,1,2,6-tetramethylpiperidinium, 1-ethyl-1,2,6-trimethylpiperidinium, and 1,1,2-triethylpiperidinium. Preferably, 1,1,3,5-tetramethylpiperidinium is used. The organic structure modifier may be used alone or in combination of two or more.

[0092] The aluminum source is a raw material compound that becomes the aluminum atoms constituting the zeolite. Examples of aluminum sources include aluminum sulfate, aluminum nitrate, pseudoboehmite, aluminum alkoxide, aluminum hydroxide, alumina sol, and sodium aluminate. Aluminum hydroxide is preferred. The aluminum source may be used alone or in combination of two or more.

[0093] The silica source is a raw material compound that becomes the silicon atoms constituting the zeolite. Examples of silica sources include fumed silica, silica sol (colloidal silica), silica gel, silicates such as silicon dioxide and water glass, silicon alkoxides such as tetraethoxyorthosilicate and tetramethoxysilane, and silicon halides. Silica sol (colloidal silica) is preferred. The silica source may be used alone or in combination of two or more types.

[0094] The amounts of aluminum source (solids) and silica source (solids) added are adjusted as appropriate within the range where the desired zeolite parameters (e.g., Si / Al ratio) can be obtained.

[0095] The seed crystal zeolite promotes the crystallization of the desired zeolite. Examples of seed crystal zeolites include those having the same skeletal structure as the desired zeolite. However, the seed crystal zeolite does not necessarily have to have the same skeletal structure as the desired zeolite. Furthermore, the seed crystal zeolite may be used alone or in combination of two or more types.

[0096] The Si / Al ratio of the seed crystal zeolite is not particularly limited and can be adjusted as appropriate within the range in which the desired zeolite can be obtained. For example, the Si / Al ratio of the seed crystal zeolite is 2 to 1000. The average primary particle size of the seed crystal zeolite is also not particularly limited and can be adjusted as appropriate within the range in which the desired zeolite can be obtained. The average primary particle size of the seed crystal zeolite can be adjusted by grinding or other processes. The amount of seed crystal zeolite added is, for example, 1% to 50% by mass relative to the silica source.

[0097] Next, the resulting gel-like mixture is crystallized by hydrothermal synthesis in a heated and pressurized container such as an autoclave.

[0098] The heating temperature is, for example, 100°C to 250°C. The pressure is, for example, 1 MPa to 30 MPa. The heating and pressurizing time is, for example, 1 hour to 120 hours.

[0099] Next, the crystallized product is filtered, washed with water, and dried. Then, it is calcined to obtain powdered zeolite.

[0100] The drying temperature is, for example, 110°C to 170°C. The drying time is 1 hour to 24 hours.

[0101] The firing temperature is, for example, 350°C to 800°C, preferably 450°C to 700°C. The firing time is, for example, 1 hour to 24 hours, preferably 2 hours to 20 hours.

[0102] Furthermore, if an alkali metal source is added during the above preparation process, the resulting zeolite will contain alkali metal ions as countercations (alkali metal type zeolite).

[0103] 2.2.Catalyst formation process In the catalyst formation step, the acid control component is incorporated into the zeolite. Specifically, the catalyst formation step includes a step of supporting the acid control component on the zeolite (supporting step), and / or a step of introducing metal ions (alkali metal ions and / or alkaline earth metal ions) as the acid control component by ion exchange (ion exchange step). Preferably, the catalyst formation step includes a step of supporting the acid control component on the zeolite (supporting step).

[0104] (Supporting process) In the loading process, the acid control component is loaded onto the zeolite. If the zeolite is an alkali metal type zeolite, the alkali metal ions acting as countercations of the alkali metal type zeolite may be ion-exchanged before the metal is loaded.

[0105] Specifically, protons are introduced as countercations to alkali metal zeolites by ion exchange.

[0106] For ion exchange in zeolites, known methods can be used. Specifically, to obtain proton-type zeolite from alkali metal-type zeolite, first, alkali metal-type zeolite powder is added to an aqueous solution of an ammonium salt (for example, an aqueous solution of ammonium nitrate and an aqueous solution of ammonium acetate) to form ammonium-type zeolite. Then, proton-type zeolite is obtained by calcining under air circulation.

[0107] Next, an acid-controlling component is supported on the obtained proton-type zeolite.

[0108] A known method can be used to support the acid-controlling component on the zeolite. Examples of methods for supporting the acid-controlling component on the zeolite include impregnation and kneading. The impregnation method is preferred. In other words, the acid-controlling component is preferably impregnated and supported on the zeolite.

[0109] Specifically, the acid-controlling component is loaded onto the zeolite using the inducer wetness method, one of the impregnation methods. First, a predetermined amount of zeolite is placed in a round-bottom flask and vacuum-dried for about 1 to 4 hours. After vacuum drying, an aqueous solution of pure water equivalent to the pore capacity of the zeolite is added, in which the above-mentioned acid-controlling component salt is dissolved, and the zeolite and the aqueous solution of the acid-controlling component salt are mixed. At this time, the mixture is shaken until the zeolite and the aqueous solution of the acid-controlling component salt are uniformly mixed and no longer adhere to the flask walls in a wet state. Next, after drying, the mixture is transferred to a crucible or similar container and calcined to obtain zeolite loaded with the acid-controlling component. The calcination temperature and calcination time are adjusted as appropriate within the same range as described in the preparation steps above.

[0110] As described above, a zeolite with an acid-controlling component supported can be obtained.

[0111] (Ion exchange process) In the ion exchange process, metal ions are introduced as countercations to the zeolite, acting as acid control components. If alkali metal ions are desired as countercations, the desired alkali metal-type zeolite can be obtained by selecting the type of alkali metal source used in the preparation process described above.

[0112] The following is an example of introducing alkaline earth metal ions as countercations to proton-type or ammonium-type zeolites by ion exchange.

[0113] First, a predetermined amount of proton-type or ammonium-type zeolite is placed in a round-bottom flask. An aqueous solution of the alkaline earth metal salt mentioned above, dissolved in pure water, is added, and the zeolite and the aqueous solution of the alkaline earth metal salt are mixed. The reaction time is not particularly limited, but it is preferable to be 2 hours or more to promote ion exchange to the desired metal. The reaction temperature is also not particularly limited, but it is preferable to be 80°C or higher to promote ion exchange. Next, the reaction solid is recovered by filtration or centrifugation, dried, transferred to a crucible or the like, and calcined to obtain zeolite into which alkaline earth metal ions have been introduced by ion exchange. The calcination temperature and calcination time are adjusted as appropriate within the same range as described in the preparation step above.

[0114] 3. Liquefied petroleum gas production equipment Next, with reference to Figure 1, the liquefied petroleum gas production apparatus of this disclosure will be described.

[0115] The liquefied petroleum gas production apparatus 10 produces hydrocarbons having at least 3 and 4 carbon atoms from a raw material containing at least one selected from the group consisting of methanol and dimethyl ether, and hydrogen.

[0116] As shown in Figure 1, the liquefied petroleum gas production apparatus 10 comprises the hydrocarbon production catalyst 1 described above and a hydrogenation catalyst 11 positioned downstream of the hydrocarbon production catalyst 1 in the direction of raw material flow. The direction of raw material flow refers to the direction in which the raw material gas, which contains at least one selected from the group consisting of methanol and dimethyl ether and hydrogen, flows.

[0117] The liquefied petroleum gas production apparatus 10 may include one reactor 20 filled with a hydrocarbon production catalyst 1 and a hydrogenation catalyst 11, or it may include a first reactor filled with the hydrocarbon production catalyst 1 and a second reactor located downstream of the first reactor in the direction of raw material flow and filled with the hydrogenation catalyst 11. As shown in Figure 1, the liquefied petroleum gas production apparatus 10 preferably includes one reactor 20 filled with the hydrocarbon production catalyst 1 and the hydrogenation catalyst 11.

[0118] Furthermore, if the liquefied petroleum gas production apparatus 10 includes a single reactor 20 filled with a hydrocarbon production catalyst 1 and a hydrogenation catalyst 11, a spacer 12 such as quartz wool may be provided between the hydrocarbon production catalyst 1 and the hydrogenation catalyst 11 to prevent the catalysts from mixing.

[0119] In the liquefied petroleum gas production apparatus 10, first, a raw material containing at least one selected from the group consisting of methanol and dimethyl ether, and hydrogen is introduced, and these raw materials come into contact with the hydrocarbon production catalyst 1. This produces a reaction product containing hydrocarbons having at least 3 and 4 carbon atoms.

[0120] Next, the resulting reaction product comes into contact with the hydrogenation catalyst 11, which is positioned downstream of the hydrocarbon production catalyst 1 in the flow direction of the raw materials. This produces a second reaction product containing at least three and four carbon atoms.

[0121] Since the liquefied petroleum gas production apparatus 10 is equipped with the hydrocarbon production catalyst 1 described above, it is possible to improve the conversion rate to reaction products containing at least three- and four-carbon hydrocarbons, and furthermore, to improve the selectivity of three- and four-carbon hydrocarbons in the reaction products.

[0122] On the other hand, the hydrocarbons with 3 and 4 carbon atoms in the reaction products produced by hydrocarbon production catalyst 1 include, in addition to propane and butane (paraffins with 3 and 4 carbon atoms), which are the main components of liquefied petroleum gas, propylene and butene (olefins with 3 and 4 carbon atoms), isobutane, and butadiene.

[0123] The hydrogenation catalyst 11 converts olefins into paraffins by adding hydrogen. In other words, the hydrogenation catalyst 11 adds hydrogen to the olefins (olefins with 3 and 4 carbon atoms) in the reaction product, increasing the proportion of paraffins in the hydrocarbons with 3 and 4 carbon atoms.

[0124] If the liquefied petroleum gas production apparatus 10 is equipped with a hydrogenation catalyst 11 positioned downstream of the hydrocarbon production catalyst 1 in the direction of raw material flow, then olefins having 3 and 4 carbon atoms in the reaction product can be hydrogenated, and the proportion of paraffins having 3 and 4 carbon atoms in the hydrocarbons having 3 and 4 carbon atoms in the second reaction product can be increased.

[0125] As a result, the yield of liquefied petroleum gas can be improved.

[0126] As the hydrogenation catalyst 11, for example, a known catalyst capable of converting olefins to paraffins can be used. As an example of the hydrogenation catalyst 11, the active component of the hydrogenation catalyst 11 is supported on a support component of the hydrogenation catalyst 11.

[0127] Examples of the active components of the hydrogenation catalyst 11 include metals such as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, and Re; alloys thereof; oxides of metals such as Cu, Co, Ni, Cr, Zn, Re, Mo, and W; and sulfides of metals such as Co, Re, Mo, and W. Preferably, metals are used, and more preferably, Fe, Ni, Pd, and Pt are used.

[0128] Examples of support components for the hydrogenation catalyst 11 include carbon, silica, alumina, and silica-alumina. Silica is preferred.

[0129] Preferably, the hydrogenation catalyst 11 is one in which Pd is supported on silica.

[0130] 4. Method of producing liquefied petroleum gas A method for producing liquefied petroleum gas comprises a preparation step of preparing the above-mentioned hydrocarbon production catalyst, and a reaction step of contacting a raw material containing at least one selected from the group consisting of methanol and dimethyl ether and hydrogen with the hydrocarbon production catalyst to obtain a reaction product containing hydrocarbons having at least 3 and 4 carbon atoms. The method for producing liquefied petroleum gas further comprises, if necessary, a second reaction step of contacting the reaction product with a hydrogenation catalyst to obtain a second reaction product.

[0131] 3.1. Preparation process In the preparation step, the hydrocarbon production catalyst described above is prepared.

[0132] 3.2. Reaction Process In the reaction step, a starting material containing at least one selected from the group consisting of methanol and dimethyl ether, and hydrogen, is brought into contact with a hydrocarbon production catalyst to obtain a reaction product containing hydrocarbons having at least 3 and 4 carbon atoms.

[0133] The reaction temperature is, for example, 200°C or higher, preferably 300°C or higher, more preferably 330°C or higher, and also, for example, 600°C or lower, preferably 500°C or lower, more preferably 470°C or lower.

[0134] If the reaction temperature is within the above range, the conversion rate from a raw material containing at least one selected from the group consisting of methanol and dimethyl ether and hydrogen to a reaction product containing at least three- and four-carbon hydrocarbons can be improved, and the selectivity of three- and four-carbon hydrocarbons in the reaction product can be improved. In other words, in the method for producing liquefied petroleum gas of this disclosure, even if the reaction step temperature is relatively low (not excessively high), the conversion rate from a raw material containing at least one selected from the group consisting of methanol and dimethyl ether and hydrogen to a reaction product containing at least three- and four-carbon hydrocarbons can be improved, and the selectivity of three- and four-carbon hydrocarbons in the reaction product can be improved.

[0135] The reaction pressure is, for example, 0.05 MPa to 5.00 MPa, preferably 0.10 MPa to 3.00 MPa, more preferably 0.20 MPa to 1.00 MPa, and even more preferably 0.25 MPa to 0.80 MPa.

[0136] The reaction pressure is, for example, 0.05 MPa or higher, preferably 0.10 MPa or higher, more preferably 0.20 MPa or higher, even more preferably 0.25 MPa or higher, and also, for example, 5.00 MPa or lower, preferably 3.00 MPa or lower, more preferably 1.00 MPa or lower, and even more preferably 0.8 MPa or lower.

[0137] If the reaction pressure is within the above range, the conversion rate from a raw material containing at least one selected from methanol and dimethyl ether and hydrogen to a reaction product containing at least three- and four-carbon hydrocarbons can be improved, and the selectivity of three- and four-carbon hydrocarbons in the reaction product can be improved. In other words, in the method for producing liquefied petroleum gas of this disclosure, even if the pressure of the reaction step is relatively low (not excessively high), the conversion rate from a raw material containing at least one selected from methanol and dimethyl ether and hydrogen to a reaction product containing at least three- and four-carbon hydrocarbons can be improved, and the selectivity of three- and four-carbon hydrocarbons in the reaction product can be improved.

[0138] In a raw material comprising at least one selected from the group consisting of methanol and dimethyl ether and hydrogen, the volume of hydrogen relative to the total volume of methanol and dimethyl ether is not particularly limited, for example, 1 or more, preferably 2 or more, and for example, 8 or less, preferably 5 or less.

[0139] Furthermore, the raw material supply amount is adjusted so that the W / F (mass of hydrocarbon production catalyst (g) / raw material gas flow rate (mol / h)) is, for example, 1.0 g·h / mol or more, preferably 2.0 g·h / mol or more, and for example, 20.0 g·h / mol or less, preferably 10.0 g·h / mol or less.

[0140] The conversion rate of the raw materials (conversion rate of methanol and dimethyl ether) is, for example, 80% or more, preferably 85% or more, more preferably 90% or more, even more preferably 93% or more, and particularly preferably 95% or more.

[0141] In the reaction product, the selectivity (C-mol%) of the C1 hydrocarbon is, for example, 10.0 C-mol% or less, preferably 7.0 C-mol% or less, and more preferably 4.0 C-mol% or less.

[0142] In the reaction product, the selectivity (C-mol%) of the C2 hydrocarbon is, for example, 20.0 C-mol% or less, preferably 18.0 C-mol% or less, more preferably 16.0 C-mol% or less, and even more preferably 13.0 C-mol% or less.

[0143] In the reaction product, the selectivity (C-mol%) of the C3 hydrocarbon is, for example, 30.0 C-mol% or more, preferably 40.0 C-mol% or more, more preferably 45.0 C-mol% or more, and even more preferably 48.0 C-mol% or more.

[0144] The reaction product exhibits the highest selectivity for hydrocarbons with three carbon atoms. Therefore, it is a suitable method for producing liquefied petroleum gas.

[0145] In the reaction product, the selectivity (C-mol%) of the C4 hydrocarbon is, for example, 5.0 C-mol% or more, preferably 10.0 C-mol% or more, and for example, 30.0 C-mol% or less, preferably 25.0 C-mol% or less.

[0146] In the reaction product, the selectivity (C-mol%) of C3 and C4 hydrocarbons is, for example, 65 C-mol% or more, preferably 68 C-mol% or more, and more preferably 70 C-mol% or more. In other words, in the reaction product, C3 and C4 hydrocarbons are the main components (specifically, 50 C-mol% or more).

[0147] In the reaction product, the selectivity (C-mol%) of hydrocarbons having 5 to 8 carbon atoms is, for example, 20 C-mol% or less, preferably 15 C-mol% or less, and more preferably 13 C-mol% or less.

[0148] Note that C-mol refers to the number of carbon-based moles.

[0149] The conversion rates of the raw materials (conversion rates of methanol and dimethyl ether) and the selectivity of hydrocarbons with each carbon number in the reaction product were measured using the method described in the examples below. Furthermore, the conversion rates of the raw materials (conversion rates of methanol and dimethyl ether) and the selectivity of hydrocarbons with each carbon number in the reaction product can be adjusted by the amount of hydrocarbon production catalyst, the amount of raw material gas supplied, and its composition.

[0150] 3.3. Second reaction step In the second reaction step, the reaction product obtained in the above reaction step is brought into contact with a hydrogenation catalyst to obtain a second reaction product.

[0151] The second reaction step may be carried out immediately following the above reaction step, or the reaction product obtained in the above reaction step may be recovered and carried out separately. Preferably, the second reaction step is carried out immediately following the above reaction step.

[0152] The reaction temperature and reaction pressure are adjusted as appropriate, for example, within the ranges described in the reaction steps above.

[0153] In the second reaction product, the proportion (%) of paraffin (propane) among the C3 hydrocarbons is, for example, 70% or more, preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more.

[0154] If the method for producing liquefied petroleum gas includes a second reaction step, the proportion of paraffin (propane) among the C3 hydrocarbons in the second reaction product can be increased as described above.

[0155] Furthermore, if the method for producing liquefied petroleum gas includes a second reaction step, the above reaction step and the second reaction step are steps that occur sequentially when a raw material containing at least one selected from the group consisting of methanol and dimethyl ether and hydrogen is supplied to the above-mentioned liquefied petroleum gas production apparatus 10.

[0156] In other words, if the method for producing liquefied petroleum gas includes a second reaction step, the method for producing liquefied petroleum gas comprises the steps of preparing the liquefied petroleum gas production apparatus 10, supplying a raw material containing at least one selected from the group consisting of methanol and dimethyl ether and hydrogen to the liquefied petroleum gas production apparatus 10 and contacting it with the hydrocarbon production catalyst 1 to obtain a reaction product containing at least three and four hydrocarbons, and contacting the reaction product with the hydrogenation catalyst 11 to obtain a second reaction product.

[0157] 4. Effects The hydrocarbon production catalyst of this disclosure comprises a zeolite having a porous structure of an 8-membered oxygen ring, and an acid control component contained in the zeolite that includes at least one selected from the group consisting of alkali metals, alkaline earth metals, alkali metal oxides, and alkaline earth metal oxides, wherein the Si / Al ratio of the zeolite is 50 or less, the average primary particle diameter of the zeolite is 1000 nm or less, and the metal content of the acid control component is 0.390 mmol or less per gram of zeolite. Therefore, it is possible to improve the conversion rate from a raw material containing at least one selected from the group consisting of methanol and dimethyl ether and hydrogen to a reaction product containing at least C3 and C4 hydrocarbons, and to improve the selectivity of C3 and C4 hydrocarbons in the reaction product. As a result, the yield of liquefied petroleum gas can be improved.

[0158] The liquefied petroleum gas production apparatus 10 of this disclosure includes the hydrocarbon production catalyst 1 described above. Therefore, it is possible to improve the conversion rate from a raw material containing at least one selected from the group consisting of methanol and dimethyl ether and hydrogen to a reaction product containing at least three- and four-carbon hydrocarbons, and to improve the selectivity of three- and four-carbon hydrocarbons in the reaction product. Furthermore, the liquefied petroleum gas production apparatus 10 of this disclosure includes a hydrogenation catalyst 11 positioned downstream of the hydrocarbon production catalyst 1 in the flow direction of the raw material. Therefore, it is possible to improve the proportion of paraffin in the three- and four-carbon hydrocarbons. As a result, the yield of liquefied petroleum gas can be improved.

[0159] The method for producing liquefied petroleum gas according to this disclosure comprises a preparation step of preparing the hydrocarbon production catalyst described above, and a reaction step of contacting a raw material with the hydrocarbon production catalyst to obtain a reaction product containing at least three- and four-carbon hydrocarbons. Therefore, it is possible to improve the conversion rate from a raw material containing at least one selected from the group consisting of methanol and dimethyl ether and hydrogen to a reaction product containing at least three- and four-carbon hydrocarbons, and to improve the selectivity of three- and four-carbon hydrocarbons in the reaction product. As a result, the yield of liquefied petroleum gas can be improved. [Examples]

[0160] Examples and comparative examples are shown below to further explain this disclosure. However, this disclosure is not limited to the examples and comparative examples. Furthermore, specific numerical values ​​such as blending ratios (content), physical properties, and parameters used in the following description may be replaced with the upper limits (numbers defined as "less than or equal to" or "less than") or lower limits (numbers defined as "greater than or equal to" or "greater than") of the corresponding blending ratios (content), physical properties, and parameters described in the "Modes for Carrying Out the Invention" above.

[0161] Example 1 The hydrocarbon production catalyst of Example 1 was prepared according to the following procedure.

[0162] (Zeolite preparation process) 1.5 g of sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in 5.1 g of water, and 15.85 g of an aqueous solution of N,N,N-trimethyl-1-adamantan ammonium hydroxide (25% by mass, manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred. Next, 0.97 g of aluminum hydroxide (manufactured by Aldrich) was added and mixed, and 18.21 g of colloidal silica AS-40 (SiO2: 40% by weight, manufactured by Aldrich) and 1.1 g of diethylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added as silica sources and stirred. Next, seed crystal proton-type zeolite (Si / Al=9, zeolite with CHA structure, manufactured by ACS materials) was added to a concentration of 3% by mass relative to the added SiO2, and the mixture was stirred further to obtain a gel-like mixture. This gel-like mixture was placed in a 50 ml autoclave and hydrothermally synthesized at 160°C for 48 hours while rotating at 20 rpm. After synthesis, the obtained zeolite was filtered, washed with water, and then dried. The dried zeolite was calcined at 550°C for 12 hours under air circulation to obtain a zeolite having a CHA structure containing Na ions as countercations. Next, ion exchange was performed at 80°C for 2 hours using a 1M aqueous solution of ammonium nitrate (prepared using ammonium nitrate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), dried at 110°C, and then calcined at 550°C for 3 hours under air circulation to obtain a proton-type zeolite having a CHA structure.

[0163] (Catalyst formation process) Next, an acid-controlling component (calcium and / or calcium oxide) was supported on the proton-type zeolite having the CHA structure described above by the spontaneous wetness method described above. Specifically, water equivalent to the pore volume of the proton-type zeolite having the CHA structure was prepared, and calcium nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in 1 g of zeolite so that the calcium content was 0.260 mmol / g-zeolite (in the hydrocarbon production catalyst, the calcium content per 1 ml of Al in the zeolite is 0.187 ml / mol-Al). Then, the aqueous calcium nitrate solution was adsorbed onto the proton-type zeolite having the CHA structure. This was dried overnight at 110°C and calcined at 550°C (1°C / min) for 3 hours to obtain the hydrocarbon production catalyst of Example 1 (proton-type zeolite having a CHA structure with calcium and / or calcium oxide supported as an acid-controlling component). In Tables 1 to 3, the elemental symbol for an acid-controlling component (e.g., Ca) indicates calcium and / or calcium oxide (the same applies hereafter). Tables 1 to 3 also show the content of the acid-controlling metal component per 1g of zeolite, and the content of the acid-controlling metal component per 1mol of Al in the zeolite in the hydrocarbon production catalyst (the same applies hereafter).

[0164] Example 2 The hydrocarbon production catalyst for Example 2 was prepared using the same procedure as in Example 1, except that 0.75 g of sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 0.31 g of aluminum hydroxide (manufactured by Aldrich) were used in the zeolite preparation step.

[0165] Example 3 The hydrocarbon production catalyst of Example 3 was prepared using the same procedure as in Example 1, except that a commercially available proton-type zeolite having a CHA structure (Si / Al=9, manufactured by ACS materials) was used as the proton-type zeolite having a CHA structure.

[0166] Example 4 The hydrocarbon production catalyst of Example 4 was prepared using the same procedure as in Example 1, except that calcium nitrate was used in the catalyst formation step so that the calcium content was 0.130 mmol per 1 g of zeolite.

[0167] Example 5 The hydrocarbon production catalyst of Example 5 was prepared using the same procedure as in Example 3, except that calcium nitrate was used in the catalyst formation step so that the calcium content was 0.130 mmol per 1 g of zeolite.

[0168] Example 6 The hydrocarbon production catalyst of Example 6 was prepared using the same procedure as in Example 1, except that magnesium and / or magnesium oxide was supported on it. In the catalyst formation step, magnesium nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used instead of calcium nitrate.

[0169] Example 7 The hydrocarbon production catalyst of Example 8 was prepared using the same procedure as in Example 1, except that sodium and / or sodium oxide was supported on it. In the catalyst formation step, sodium nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used instead of calcium nitrate.

[0170] Example 8 The hydrocarbon production catalyst of Example 6 was prepared using the same procedure as in Example 3, except that strontium and / or strontium oxide was supported on it. In the catalyst formation step, strontium nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used instead of calcium nitrate.

[0171] Example 9 The hydrocarbon production catalyst of Example 7 was prepared using the same procedure as in Example 3, except that barium and / or barium oxide was supported on it. In the catalyst formation step, barium nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used instead of calcium nitrate.

[0172] Example 10 (Zeolite preparation process) 0.72 g of sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in 4.7 g of water, and 9.2 g of aqueous solution of 1,13,5,tetramethylpiperidinium hydroxide (2.08% by mass) was added and stirred. Next, 0.97 g of aluminum hydroxide (manufactured by Aldrich) was added and mixed, and 18.21 g of colloidal silica AS-40 (SiO2: 40% by weight, manufactured by Aldrich) and 1.1 g of diethylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added as silica sources and stirred. Next, seed crystal proton-type Y zeolite (Si / Al=12, zeolite with FAU structure) was added to a concentration of 3% by mass relative to the added SiO2, and further stirred to obtain a gel-like mixture. This gel-like mixture was placed in a 50 ml autoclave and allowed to stand, and hydrothermally synthesized at 160°C for 92 hours. After synthesis, the obtained zeolite was filtered, washed with water, and then dried. The dried zeolite was calcined at 550°C for 12 hours under air circulation to obtain a zeolite having an AEI structure containing Na ions as countercations. Next, ion exchange was performed using a 1M aqueous solution of ammonium nitrate at 70°C for 3.5 hours, followed by drying at 110°C, and then calcined at 550°C for 3 hours under air circulation to obtain a proton-type zeolite having an AEI structure.

[0173] Next, calcium was supported on the proton-type zeolite having the above-described AEI structure using the same procedure as in Example 4 to prepare the hydrocarbon production catalyst of Example 10.

[0174] Comparative Example 1 The hydrocarbon production catalyst for Comparative Example 1 was prepared using the same procedure as in Example 1, except that 0.40 g of sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 0.15 g of aluminum hydroxide (manufactured by Aldrich) were used in the zeolite preparation step.

[0175] Comparative Example 2 The hydrocarbon production catalyst for Comparative Example 2 was prepared using the same procedure as in Example 1, except that a commercially available proton-type zeolite with a CHA structure (Si / Al=13, manufactured by Tosoh Corporation) was used as the proton-type zeolite having a CHA structure.

[0176] Comparative Example 3 The hydrocarbon production catalyst for Comparative Example 3 was prepared using the same procedure as in Example 3, except that calcium nitrate was used in the catalyst formation step so that the calcium content was 0.520 mmol per 1 g of zeolite.

[0177] Comparative Example 4 The hydrocarbon production catalyst of Comparative Example 4 was prepared using the same procedure as in Example 1, except that palladium and / or palladium oxide was supported on it. In the catalyst formation step, palladium nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used instead of calcium nitrate, and the catalyst was calcined at 300°C for 3 hours under air circulation.

[0178] Comparative Example 5 The hydrocarbon production catalyst for Comparative Example 5 was prepared using the same procedure as in Example 4, except that a commercially available proton-type zeolite with an MFI structure (Si / Al=20, manufactured by Tosoh Corporation) was used as the proton-type zeolite having an MFI structure.

[0179] Comparative Example 6 The hydrocarbon production catalyst for Comparative Example 6 was prepared using the same procedure as for Comparative Example 5, except that calcium nitrate was used in the catalyst formation step so that the calcium content was 1.040 mmol per 1 g of zeolite.

[0180] [Zeolite skeletal structure] In each example and comparative example, the zeolite framework structure was identified by drying the zeolite obtained by hydrothermal synthesis and performing XRD analysis. The results are shown in Tables 1 and 2.

[0181] [Average primary particle size of zeolite] In each example and comparative example, the average primary particle size of the zeolite was determined by observing SEM images obtained by a scanning electron microscope (SEM). Specifically, zeolite obtained by hydrothermal synthesis was dried, and photographs (SEM images) of the zeolite particles were taken using a scanning electron microscope (SEM). The particle sizes of 100 arbitrarily selected zeolite particles were measured, and the average value was calculated. The results are shown in Tables 1 and 2. When the shape of the zeolite particle was approximately spherical, the length corresponding to its diameter was measured and this was taken as the particle size of one zeolite particle. When the shape of the zeolite particle was approximately hexahedral, its long side and short side (excluding the depth direction) were measured, and the average value of the long side and short side (= (long side + short side) / 2) was calculated and taken as the particle size of one zeolite particle.

[0182] [Si / Al ratio of zeolite] In each example and comparative example, the Si / Al ratio of the zeolite was measured by drying the zeolite obtained by hydrothermal synthesis and performing XRF analysis. The results are shown in Tables 1 and 2.

[0183] [Hydrogen production] 0.5 g of the hydrocarbon production catalyst for each example and comparative example was gently packed into the reactor. A tubular furnace was placed around the reactor, and the reactor was heated until the catalyst temperature reached 400°C. After reaching the predetermined temperature, the raw material gas (a mixture of hydrogen and methanol; hydrogen volume:methanol volume = 3.2:1) was supplied at a W / F (hydrocarbon production catalyst mass (g) / raw material gas flow rate (mol / h)) of 4.1 g·h / mol. The pressure at the reactor inlet was adjusted to 0.5 MPa. The gas at the reactor outlet was collected 1 hour after the start of the reaction (Time On Stream = 1 Hr), and the collected gas was analyzed using gas chromatography (Agilent GC 8890: detectors FID and TCD). For the TCD column, Porapak Q (80 / 100 mesh, 2m, GL Sciences), MolSieve 5A (60 / 80 mesh, 2m, GL Sciences), and ShinCarbon ST (50 / 80 mesh, 2m, GL Sciences) were used. For the FID column, PoraPLOT Q-HT (25m × 0.32mm × 10um, Agilent) was used. Based on gas chromatography analysis, the methanol conversion rate and the selectivity (C-mol%) of each hydrocarbon (1-8 carbon atoms) in the reaction product were calculated. The selectivity of hydrocarbons with 3 and 4 carbon atoms was also calculated. The conversion rate was calculated based on the following formula. The results are shown in Tables 1 and 2. For Comparative Example 4, the reaction temperature (catalyst temperature in the reactor) was set to 350°C. In the table, C indicates the number of carbon atoms, and C5-C8 is the sum of hydrocarbons with 5-8 carbon atoms.

[0184] Conversion rate (%) = (Methanol supplied (moles) - Methanol remaining after reaction (moles)) / Methanol supplied (moles) × 100

[0185] Furthermore, from one hour after the start of the reaction, gas was recovered at the reactor outlet every hour, and the recovered gas was analyzed using gas chromatography (Agilent GC 8890: detectors FID and TCD) under the same conditions as above. The time T1 (h) during which the conversion rate was maintained at 80% or higher in the hydrocarbon production catalyst, and the total amount of carbon-3 and carbon-4 hydrocarbons recovered per 1 g of zeolite from the start of the reaction to T1 (g / g-zeolite) were calculated. The results are shown in Tables 1 and 2. Specifically, the time T1 during which the conversion rate was maintained at 80% or higher was calculated by plotting the conversion rate every hour, drawing a straight line connecting the point at which the conversion rate fell below 80% with the point one hour prior, and using the equation of that line. Comparative Examples 4-6 were not measured.

[0186] Apparatus Example 1 The liquefied petroleum gas production apparatus of Apparatus Example 1 was prepared according to the following procedure.

[0187] (Preparation of hydrogenation catalyst) Palladium was supported on a silica (CARiACT Q-30, manufactured by Fuji Silicia Chemical Co., Ltd.) carrier by the inducer wetness method. Specifically, water equivalent to the pore volume of the silica was prepared, and palladium nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in it so that the palladium content was 0.047 mmol per gram of silica. The aqueous solution of palladium nitrate was then adsorbed onto the silica carrier. This was dried overnight at 110°C and calcined at 300°C (1°C / min) for 3 hours to obtain a hydrogenation catalyst in which palladium was supported on silica.

[0188] (Preparation of liquefied petroleum gas production equipment) 0.5 g of the hydrogenation catalyst mentioned above, quartz wool, and 0.5 g of the hydrocarbon production catalyst from Example 1 were sequentially packed into the reactor. In other words, in the reactor, the hydrocarbon production catalyst, quartz wool, and hydrogenation catalyst were stacked sequentially from the reactor inlet to the reactor outlet. In this way, the liquefied petroleum gas production apparatus of Apparatus Example 1 was prepared.

[0189] Apparatus Example 2 Except for using the hydrocarbon production catalyst of Example 4 as the hydrocarbon production catalyst, the liquefied petroleum gas production apparatus of Apparatus Example 2 was prepared using the same procedure as in Apparatus Example 1.

[0190] Apparatus Comparative Example 1 Except for the preparation of the liquefied petroleum gas production apparatus as described below, the liquefied petroleum gas production apparatus for Comparative Example 1 was prepared using the same procedure as in Apparatus Example 1.

[0191] (Preparation of liquefied petroleum gas production equipment) A catalyst mixture was obtained by mixing 0.5 g of the same hydrogenation catalyst as in Apparatus Example 1 with 0.5 g of the hydrocarbon production catalyst from Comparative Example 2. Then, quartz wool and the catalyst mixture were sequentially packed into the reactor. In other words, in the reactor, the catalyst mixture and quartz wool were layered sequentially from the reactor inlet to the reactor outlet.

[0192] [Hydrogen production] In each apparatus example and comparative example 1, a tubular furnace was placed around the reactor, and the reactor was heated until the catalyst temperature reached 400°C. After reaching the predetermined temperature, the raw material gas (a mixture of hydrogen and methanol; hydrogen volume: methanol volume = 3.2:1) was supplied so that the W / F (hydrocarbon production catalyst mass (g) / raw material gas flow rate (mol / h)) was 4.1 g·h / mol. The pressure at the reactor inlet was adjusted to 0.5 MPa. The gas at the reactor outlet was collected 1 hour after the start of the reaction (Time On Stream = 1 Hr), and the collected gas was analyzed using the above gas chromatography (Agilent "GC 8890": detectors FID and TCD). Based on the gas chromatography analysis, the methanol conversion rate and the selectivity (C-mol%) of each hydrocarbon (C1-C8) in the second reaction product were calculated. The selectivity of C3 and C4 hydrocarbons was also calculated. The conversion rate was calculated based on the following formula. The results are shown in Table 3. For comparative example 1 of the apparatus, the reaction temperature (catalyst temperature in the reactor) was set to 350°C.

[0193] Conversion rate (%) = (Methanol supplied (moles) - Methanol remaining after reaction (moles)) / Methanol supplied (moles) × 100

[0194] Table 3 shows the respective percentages (%) of olefins and paraffins in hydrocarbons with 3 carbon atoms.

[0195] Table 3 includes Example 1 for reference.

[0196] [Table 1]

[0197] [Table 2]

[0198] [Table 3]

[0199] (Consideration) Referring to Table 1, the conversion rate in Examples 1 to 10 was 90% or higher (specifically, 93% or higher). On the other hand, referring to Table 2, the conversion rate in Comparative Example 5 was 79%, and in Comparative Example 6, it was 63%. In other words, it can be seen that in Examples 1 to 10, the conversion rate from a starting material containing methanol and hydrogen to a reaction product containing at least three and four hydrocarbons was improved.

[0200] Furthermore, referring to Table 1, in Examples 1 to 10, the combined selectivity of C3 and C4 hydrocarbons in the reaction product is 70 C-mol% or more (specifically, 70.9 C-mol% or more). On the other hand, referring to Table 2, in Comparative Examples 1 to 6, the combined selectivity of C3 and C4 hydrocarbons in the reaction product is less than 70 C-mol%. In other words, it can be seen that in Examples 1 to 10, the selectivity of C3 and C4 hydrocarbons in the reaction product was improved.

[0201] Furthermore, referring to Table 3, in apparatus examples 1 and 2, the selectivity for C3 and C4 hydrocarbons in the second reaction product is higher compared to apparatus comparative example 1. And, compared to example 1 (reference), it can be seen that the proportion of paraffin in the C3 hydrocarbon has been improved. [Explanation of Symbols]

[0202] 1. Hydrocarbon manufacturing catalyst 10. Liquefied Petroleum Gas Production Equipment 11 Hydrogenation catalyst 12 Spacers 20 Reactors

Claims

1. The system comprises a zeolite and an acid-controlling component contained in the zeolite, The zeolite includes a zeolite having a porous structure of an 8-membered oxygen ring. The Si / Al ratio of the zeolite is 50 or less. The average primary particle size of the zeolite is 1000 nm or less. The acid control component comprises at least one selected from the group consisting of alkali metals, alkaline earth metals, alkali metal oxides, and alkaline earth metal oxides. A hydrocarbon production catalyst wherein the content of the metal in the acid-controlling component is 0.390 mmol or less per 1 g of the zeolite.

2. The hydrocarbon production catalyst according to claim 1, wherein the acid control component comprises at least one selected from the group consisting of sodium, potassium, calcium, magnesium, strontium, barium, and oxides thereof.

3. The hydrocarbon production catalyst according to claim 1, wherein the content of the metal in the acid control component is 0.078 mmol or more and 0.338 mmol or less per 1 g of the zeolite.

4. The hydrocarbon production catalyst according to claim 1, wherein the acid-controlling component is supported on the zeolite.

5. A liquefied petroleum gas production apparatus that produces hydrocarbons having at least 3 and 4 carbon atoms from a raw material comprising at least one selected from the group consisting of methanol and dimethyl ether and hydrogen, A hydrocarbon production catalyst according to any one of claims 1 to 4, A hydrogenation catalyst is provided for the hydrocarbon production catalyst, which is positioned downstream of the raw material in the flow direction. A liquefied petroleum gas production apparatus equipped with [a specific feature].

6. A preparation step for preparing a hydrocarbon production catalyst according to any one of claims 1 to 4, A reaction step of contacting a raw material containing at least one selected from the group consisting of methanol and dimethyl ether and hydrogen with the hydrocarbon production catalyst to obtain a reaction product containing at least three and four hydrocarbons. A method for producing liquefied petroleum gas, comprising the following:

7. The method for producing liquefied petroleum gas according to claim 6, wherein the reaction pressure in the reaction step is 0.05 MPa or more and 5.00 MPa or less.

8. The method for producing liquefied petroleum gas according to claim 6, wherein the selectivity for hydrocarbons having 3 carbon atoms is highest in the reaction product.

9. The method for producing liquefied petroleum gas according to claim 6, further comprising a second reaction step of contacting the reaction product with a hydrogenation catalyst to obtain a second reaction product.

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