Method for producing olefin-containing composition, and catalyst for producing olefin-containing composition

Abstract

Provided is a method for producing an olefin-containing composition, the method comprising a step of decomposing a plastic in the presence of a zeolite to produce an olefin-containing composition containing an olefin having 2 to 5 carbon atoms, and the zeolite is an MFI-type zeolite containing Rb +.

Description

Technical Field

[0001] This invention relates to a method for manufacturing an olefin-containing composition and a catalyst for manufacturing an olefin-containing composition. Background Technology

[0002] In the past, waste plastics were disposed of through landfill, ocean dumping, and incineration. However, securing landfill sites has become increasingly difficult, and ocean dumping has become an environmental problem because plastics cannot decompose. Furthermore, although incineration can be used for thermal energy, the emission of carbon dioxide contributes to global warming.

[0003] Therefore, in recent years, due to increased awareness of environmental issues, the recycling and reuse of waste plastics has become necessary, and related research and development are actively underway. Furthermore, since most plastics are produced from fossil fuels, from the perspective of efficient resource utilization, there is an urgent need to develop recycling methods.

[0004] Among plastic materials, hydrocarbon plastics such as polyethylene (PE), polypropylene (PP), and polystyrene (PS) are widely used in beverage and food containers, packaging materials, molded products, and films due to their excellent heat resistance, weather resistance, mechanical strength, transparency, chemical resistance, and gas barrier properties. Therefore, hydrocarbon plastics constitute a large portion of waste plastic materials. One method of recycling plastic materials is chemical recycling through oil-to-gasification. In this process, waste plastics are converted into low-molecular-weight hydrocarbons through thermal decomposition. However, to improve reactivity and the selectivity of products, many methods using solid catalysts are being researched.

[0005] For example, a method for producing olefins with excellent yields of olefins having 2 to 3 carbon atoms and an excellent ratio of olefins to paraffin in catalytic cracking products having 2 to 3 carbon atoms has been proposed. This method includes a thermal decomposition step of heating a polyolefin plastic to obtain a decomposition product, and a catalytic decomposition step of contacting the decomposition product obtained in the aforementioned thermal decomposition step with an MFI-type zeolite containing 0.10% to 0.30% sodium atoms to obtain a catalytic cracking product containing olefins (see Patent Document 1). Furthermore, as a catalyst with high aromatic yield, a Ga-supported zeolite (HZSM-5 and HZSM-11) catalyst has been proposed, and as a catalyst with high selectivity for lower olefins, a NaHZSM-5 catalyst that undergoes Na ion exchange with HZSM-5 has been proposed (see Non-Patent Document 1).

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: International Publication No. 2021 / 166854

[0009] Non-patent literature

[0010] Non-Patent Literature 1: Yoshio Kamimichi and Yasuharu Kanda, "Hydrogen Transfer-Type Decomposition of Plastic Mixtures Using Zeolite Catalysts", Catalyst, 2023, Vol.65, No.2, pp.114-119 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] However, even when using catalysts disclosed in existing technical literature, the yield of useful components such as propylene cannot adequately meet the requirements relative to byproducts such as paraffin components.

[0013] The object of the present invention is to provide a method for manufacturing an olefin-containing composition with fewer paraffins as a byproduct and excellent yields of olefins having 2 to 5 carbons.

[0014] Methods for solving problems

[0015] An embodiment of the present invention provides a method for manufacturing an olefin-containing composition comprising the step of decomposing plastic in the presence of a zeolite to produce an olefin-containing composition containing an olefin having two to five carbon atoms, wherein the zeolite is Rb-containing. + MFI type zeolite.

[0016] The method for solving the aforementioned problem is as follows. That is,

[0017] <1> A method for manufacturing an olefin-containing composition includes the step of decomposing a plastic in the presence of zeolite to produce an olefin-containing composition containing olefins having 2 to 5 carbon atoms.

[0018] The aforementioned zeolite contains Rb + MFI type zeolite.

[0019] <2> As mentioned above <1> The method for manufacturing the olefin-containing composition, wherein the aforementioned plastic is a polyolefin.

[0020] <3> As mentioned above <1> The method for manufacturing the olefin-containing composition, wherein the aforementioned plastic contains at least one selected from the group consisting of polyethylene, polypropylene, and polystyrene.

[0021] <4> As mentioned above <1> to <3> The method for manufacturing the olefin-containing composition according to any one of the above methods, wherein the temperature at which the aforementioned plastic is decomposed is 300°C or higher and 1,100°C or lower.

[0022] <5> As mentioned above <1> to <4> The method for manufacturing the olefin-containing composition according to any one of the above methods, wherein the aforementioned Rb-containing composition... + The molar ratio of SiO2 to Al2O3 in MFI-type zeolites [SiO2 / Al2O3] is between 10 and 10,000.

[0023] <6> As mentioned above <1> to <5> The method for manufacturing the olefin-containing composition according to any one of the above methods, wherein the aforementioned Rb-containing composition... + The BET specific surface area of ​​MFI type zeolite is 100 m². 2 / g or more 1,000m 2 / g or less.

[0024] <7> As mentioned above <1> to <6> The method for producing the olefin-containing composition according to any one of the following methods further comprises:

[0025] The mixing steps for obtaining a mixture of MFI-type zeolite and a liquid containing a rubidium compound, and

[0026] The aforementioned mixture was calcined in the atmosphere to obtain the aforementioned Rb-containing solution. + The calcination steps of MFI type zeolite.

[0027] <8> As mentioned above <7> The method for manufacturing the olefin-containing composition, wherein, in the aforementioned mixing step,

[0028] When the mass of the aforementioned MFI-type zeolite is set as x (g), the molar ratio of SiO2 to Al2O3 of the aforementioned MFI-type zeolite [SiO2 / Al2O3] is set as y, and the number of moles of the aforementioned rubidium compound is set as z (mmol), 1≤yz / x≤10,000 is satisfied.

[0029] <9> As mentioned above <7> or <8> The method for manufacturing the olefin-containing composition, wherein the aforementioned MFI-type zeolite contains H + MFI type zeolite.

[0030] <10> A catalyst for manufacturing an olefin-containing composition, wherein the catalyst is used to manufacture an olefin-containing composition containing an olefin having 2 to 5 carbon atoms, wherein...

[0031] Contains Rb + MFI type zeolite.

[0032] <11> A type containing Rb + The method of using MFI type zeolite catalysts for the manufacture of olefin-containing compositions containing olefins having 2 to 5 carbon atoms.

[0033] Invention Effects

[0034] According to embodiments of the present invention, a method for manufacturing an olefin-containing composition with fewer paraffins as byproducts and excellent yields of olefins having 2 to 5 carbons can be provided. Attached Figure Description

[0035] Figure 1 This is a functional diagram of the information processing system used in Experiment Example 1.

[0036] Figure 2 for Figure 1 The flowchart for processing machine learning models in the information processing system.

[0037] Figure 3 for Figure 1 The flowchart of the process for predicting candidate zeolites containing metal cations with desired properties in the information processing system. Detailed Implementation

[0038] The present invention will now be described in detail. Furthermore, the embodiments of the present invention are not limited to the following description, and appropriate modifications may be made without departing from the spirit of the invention. In addition, in this specification, the term "~" indicating a numerical range, unless otherwise stated, means that the values ​​described before and after it are included as the lower limit and upper limit values.

[0039] (Method for manufacturing compositions containing olefins)

[0040] A method for manufacturing an olefin-containing composition according to one embodiment of the present invention includes a step of decomposing plastic in the presence of zeolite to manufacture an olefin-containing composition containing olefins having 2 to 5 carbon atoms (hereinafter also referred to as the "decomposition step"), and may further include other steps as needed.

[0041] <Decomposition Steps>

[0042] The aforementioned decomposition step is a step of decomposing plastic in the presence of zeolite to produce an olefin-containing composition containing olefins with 2 to 5 carbon atoms.

[0043] The aforementioned zeolite contains Rb + MFI type zeolite. Therefore, compared with zeolites that do not contain Rb... + Compared to conventional MFI-type zeolites, this composition contains fewer paraffins as byproducts and exhibits excellent yields of olefins with 2 to 5 carbon atoms.

[0044] In the aforementioned decomposition step, the amount of zeolite used relative to the aforementioned plastic is not particularly limited and can be appropriately selected according to the purpose. However, it is preferably 100 parts by mass or less relative to 100 parts by mass of the aforementioned plastic, more preferably 10 parts by mass or more but less than 100 parts by mass, even more preferably 13 parts by mass or more but less than 28 parts by mass, and particularly preferably 15 parts by mass or more but less than 25 parts by mass. If the amount of zeolite used relative to the aforementioned plastic is 10 parts by mass or more but less than 100 parts by mass of the aforementioned plastic, the aforementioned plastic can be appropriately decomposed, and the yield of olefins with 2 to 5 carbon atoms and the O / P ratio of the olefin-containing composition (described later) are good. Furthermore, from the viewpoint of obtaining the effects of the present invention with a smaller amount of zeolite used, it is particularly preferable to set the upper limit of the amount of zeolite used relative to the aforementioned plastic to be 30 parts by mass or less relative to 100 parts by mass of the aforementioned plastic. Therefore, the amount of zeolite used relative to the aforementioned plastic can also be set to 10 parts by mass or more but less than 30 parts by mass.

[0045] <<Compositions Containing Olefins>>

[0046] The aforementioned olefin-containing compositions contain olefins having 2 to 5 carbon atoms, preferably further containing aromatic compounds, and may further contain other components as needed.

[0047] -Alkenes with 2 to 5 carbon atoms-

[0048] As the aforementioned olefin having 2 to 5 carbon atoms, the main component is preferably selected from at least one of the group consisting of olefins and dienes, more preferably from at least one of the group consisting of olefins having 2 to 5 carbon atoms and dienes having 3 to 5 carbon atoms, and even more preferably from olefins having 2 to 5 carbon atoms.

[0049] Examples of olefins with two carbon atoms include ethylene.

[0050] Examples of olefins with three carbon atoms include propylene.

[0051] Examples of 4-carbon olefins mentioned above include 1-butene, cis-2-butene, trans-2-butene, and 2-methylpropene.

[0052] Examples of 5-carbon olefins include, for example, 1-pentene, cis-2-pentene, trans-2-pentene, 2-methyl-1-butene, and 2-methyl-2-butene.

[0053] Furthermore, in this invention, olefins with 2 to 5 carbon atoms are also referred to as "lower olefins".

[0054] The aforementioned lower olefins are raw materials for polyolefins, which can be appropriately used as raw materials in various fields such as plastic bags, cling film, straws, medical equipment, appliance casings, erasers, hoses, tires, pipes, CD cases, food trays, food containers, plastic bottles, and fibers.

[0055] The content of the aforementioned lower olefins in the aforementioned olefin-containing composition is not particularly limited and can be appropriately selected according to the purpose; however, it is preferably 30% by mass or more and 100% by mass or less, more preferably 35% by mass or more and 60% by mass or less.

[0056] -Aromatic compounds-

[0057] There are no particular limitations on the aforementioned aromatic compounds, and they can be appropriately selected according to the purpose. However, it is preferred that they contain at least one of the group consisting of three positional isomers selected from benzene, toluene, ethylbenzene, xylene (p-xylene, m-xylene, and o-xylene), styrene, and cumene.

[0058] Furthermore, in this invention, the aforementioned aromatic compounds are also referred to as "useful aromatic compounds".

[0059] The aforementioned useful aromatic resins can be used as raw materials in various fields such as CD cases, food trays, food containers, plastic bottles, and fibers.

[0060] The content of the aforementioned useful aromatic compounds in the aforementioned olefin-containing composition is not particularly limited and can be appropriately selected according to the purpose; however, it is preferably 0% by mass or more and 50% by mass or less, more preferably 0.1% by mass or more and 30% by mass or less, even more preferably 1% by mass or more and 20% by mass or less, and particularly preferably 1% by mass or more and 10% by mass or less.

[0061] Furthermore, in this invention, the aforementioned lower olefins and the aforementioned useful aromatics are collectively referred to as "useful components".

[0062] --O / P ratio--

[0063] In this invention, the paraffin byproduct is minimal, and the yield of olefins with 2 to 5 carbon atoms is excellent. This can be evaluated by calculating the ratio of the total yield (%) of the olefin products with 2 to 5 carbon atoms to the total yield (%) of the paraffin products with 2 to 5 carbon atoms, i.e., the ratio [total yield (%) of the olefin products with 2 to 5 carbon atoms / total yield (%) of the paraffin products with 2 to 5 carbon atoms] (hereinafter also referred to as the "O / P ratio"). In this invention, "paraffin" refers to aliphatic saturated hydrocarbons with 2 to 5 carbon atoms, preferably chain-like aliphatic saturated hydrocarbons with 2 to 5 carbon atoms.

[0064] There are no particular limitations on the aforementioned O / P ratio, which can be appropriately selected according to the purpose; however, it is preferred to be 1.0 or higher, and more preferably 1.5 or higher. The higher the value of the aforementioned O / P ratio, the better. Therefore, although there are no particular limitations on its upper limit, it is preferred to be 50 or lower, and more preferably 20 or lower.

[0065] The molar number of carbon atoms contained in the aforementioned useful components and the aforementioned O / P ratio refer to the olefin-containing composition obtained in the aforementioned decomposition step. Specifically, this refers to the analysis of the tetrahydrofuran (hereinafter also referred to as "THF-soluble products") soluble in the gaseous products and residues using a gas chromatography (GC) apparatus equipped with a flame ionization detector under the following analytical conditions, and the quantification of each component by the ratio of the peak area of ​​each component to the internal standard material using an internal standard method. Furthermore, there are no particular limitations on the aforementioned internal standard material if it is stable under analytical conditions and easily separated from the analyte; for example, at least one selected from the group consisting of cyclopentane and tert-butylbenzene can be used. The GC analysis of the gaseous products and THF-soluble products is performed under the analytical conditions described in the examples.

[0066] Furthermore, when the aforementioned decomposition step is carried out in a closed-system reaction vessel, the aforementioned THF-soluble product is obtained by adding THF to the residue within the reaction vessel. Furthermore, when the aforementioned decomposition step is carried out in a continuous or open-system reaction vessel, since the aforementioned gaseous products and the aforementioned residue are recovered not only within the reaction vessel but also in a trap outside the reaction vessel, the aforementioned THF-soluble product is obtained by adding THF to the residue within the reaction vessel, and by adding THF within the trap and the connection between the reaction vessel and the trap.

[0067] --Yield of useful ingredients--

[0068] The yield of useful components is preferably 35% or more, and more preferably 40% or more.

[0069] The yield of useful components is calculated using the following formula, based on the ratio of the number of moles of carbon atoms in the aforementioned useful components to the number of moles of carbon atoms in the aforementioned plastic.

[0070] Useful component yield (%) = (mass of the aforementioned useful component produced [g] calculated by GC analysis) / (total mass of plastic sample [g]) × 100

[0071] -Other ingredients-

[0072] Other components in the aforementioned olefin-containing compositions may include, for example, the aforementioned zeolite, decomposition products of the aforementioned plastics other than the aforementioned useful components, undecomposed plastics, materials other than plastics contained in the raw materials, or additives.

[0073] The aforementioned other components in the olefin-containing compositions may be appropriately removed by conventional methods during the recycling of the aforementioned useful components.

[0074] The content of the aforementioned other components in the aforementioned olefin-containing composition is not particularly limited, and can be appropriately selected according to the purpose, without impairing the effects of the embodiments of the present invention.

[0075] <<Contains Rb + MFI type zeolite >>

[0076] The skeletal structure of zeolites has been databased by the International Zeolite Association (IZA) and its IUPAC structural codes (hereinafter referred to as "structural codes") have been defined. "MFI" is the aforementioned structural code. The preferred MFI type zeolite is ZSM-5 (Zeolite Socony Mobil-5).

[0077] The crystal system of the aforementioned MFI type zeolite can be analyzed and identified by X-ray diffraction (XRD) under the analytical conditions described in the examples. Furthermore, it can be identified by comparison with either the XRD pattern described in *Collection of simulated XRD powder patterns for zeolites, Fifth revised edition (2007)* or the XRD pattern described in the Zeolite Framework Types section of the IZA Structural Committee website (http: / / www.iza-struture.org / databases / ).

[0078] -Fine pore size-

[0079] The pore size of the aforementioned MFI type zeolites is generally 0.50 nm to 0.60 nm. For example, the HSZ-800 series sold by Tosoh Corporation has a pore size of 0.58 nm as listed in the product catalog.

[0080] The aforementioned contains Rb +The fine pore size of MFI type zeolite can be determined according to ISO 15901-3:2007 "Pore size distribution and porosity of solid materials by mercury porosimetry and gas adsorption - Part 3: Analysis of micropores by gas adsorption".

[0081] -Molar ratio [SiO2 / Al2O3]-

[0082] As mentioned above, containing Rb + The molar ratio of SiO2 to Al2O3 [SiO2 / Al2O3] of the MFI-type zeolite is not particularly limited and can be appropriately selected according to the purpose; however, it is preferably 10 to 10,000 or less, more preferably 20 to 10,000 or less, even more preferably 20 to 5,000 or less, and particularly preferably 500 to 2,000 or less. If the aforementioned molar ratio [SiO2 / Al2O3] is 10 to 10,000 or less, the yield of olefins with 2 to 5 carbon atoms and the O / P ratio of the olefin-containing composition are good.

[0083] The aforementioned molar ratio [SiO2 / Al2O3], for example, allows for the accurate weighing of the aforementioned substances containing Rb. + The MFI type zeolite was completely dissolved in an aqueous solution containing nitric acid and hydrofluoric acid. The Si and Al contents of the diluted sample were determined using an ICP-based spectrophotometer (e.g., PlasmaQuant PQ 9000, Analytick Jena AG). The molar amounts of Si and Al were calculated based on the following formula using the molar amounts of Si and Al derived from the contents.

[0084] The molar ratio [SiO2 / Al2O3] = 2 × (number of moles of Si) / (number of moles of Al)

[0085] -BET specific surface area-

[0086] As mentioned above, containing Rb + The BET specific surface area of ​​MFI-type zeolites is not particularly limited and can be appropriately selected according to the purpose; however, 100 m² is preferred. 2 / g or more 1,000m 2 / g or less, more preferably 100m 2 / g or more 250m 2 / g or less, and more preferably 150m 2 / g or more 250m 2 / g or less, especially preferably 200m 2 / g or more 250m 2 / g or less. If the aforementioned BET specific surface area is 100m²... 2 / g or more 1,000m 2 Below / g, the yield of olefins with 2 to 5 carbon atoms and the O / P ratio of the olefin-containing composition are good. If it is below 100m 2 / g or more 250m 2 For samples with a yield of less than 1 g, the yield of olefins with 2 to 5 carbon atoms and the O / P ratio of olefin-containing compositions are better.

[0087] The aforementioned contains Rb + The BET specific surface area of ​​MFI type zeolites can be determined according to ISO 9277:2010 "Determination of specific surface area of ​​powders (solids) by gas adsorption".

[0088] -Particle Size-

[0089] As mentioned above, containing Rb + MFI type zeolite, using powdered form containing Rb + In the case of MFI type zeolite, there is no particular limitation on its 50% particle diameter D50 (median diameter) (volume average), which can be appropriately selected according to the purpose. However, from the viewpoint of BET specific surface area, operability, etc., it is preferred to be 1 μm or more and 500 μm or less, more preferably 2 μm or more and 350 μm or less, and even more preferably 2 μm or more and 100 μm or less.

[0090] Here, in this invention, "powder" refers to at least one of the following groups: primary particles, aggregates of primary particles (secondary particles), particles formed by granulation of primary particles, and particles formed by granulation of secondary particles.

[0091] The aforementioned contains Rb + The 50% particle size D50 (volume average) of MFI type zeolite refers to the median diameter measured by a laser diffraction particle size distribution measuring device (e.g., the laser diffraction particle size distribution measuring device SALD-7100, manufactured by Shimadzu Corporation).

[0092] The aforementioned contains Rb + The particle shape of MFI type zeolites is not particularly limited; for example, spherical, ellipsoidal, fragmented, flat, and irregular shapes can be used. One type can be used alone, or two or more types can be used together.

[0093] -Contains Rb+ Method for manufacturing MFI type zeolites -

[0094] As mentioned above, containing Rb + The method for manufacturing MFI-type zeolites is not particularly limited, and can be appropriately selected from methods known in the art. The method of the present invention, described later, allows for the production of zeolites without Rb... + MFI type zeolite with Rb + The source is processed to import Rb + In other embodiments, for example, it is also possible to pre-fabricate the material containing Rb. + zeolite.

[0095] --Manufacturing method of MFI type zeolite--

[0096] A representative method for manufacturing MFI-type zeolites includes, for example, a hydrothermal synthesis of a mixture (raw material composition) containing a silica source, an alumina source, and, further, an organic structure-directing agent, a hydroxide-containing compound, a fluoride-containing compound, and water, which may be added as needed. Following the aforementioned hydrothermal synthesis, further solid-liquid separation and washing processes may be performed using conventional methods, such as drying at approximately 50°C to 150°C in the atmosphere. Alternatively, the organic structure-directing agent may be removed by calcination without disintegrating the zeolite framework; in this case, the calcination temperature is preferably 500°C to 600°C.

[0097] While there are no particular limitations on the aforementioned silica source, preferred sources include precipitated silica, colloidal silica, fumed silica, silica gel, sodium silicate (e.g., sodium metasilicate, sodium orthosilicate, sodium silicate 1, sodium silicate 2, sodium silicate 3, sodium silicate 4), alkoxysilanes (e.g., tetraethoxysilane (TEOS) or trimethylethoxysilane (TMEOS)), more preferably tetraethoxysilane (TEOS) or trimethylethoxysilane (TMEOS), and even more preferably tetraethoxysilane (TEOS). One of these sources may be used alone, or two or more may be used in combination.

[0098] While there are no particular limitations on the aforementioned alumina source, aluminum chloride, aluminum nitrate, aluminum sulfate, sodium aluminate, aluminum alkoxide such as aluminum isopropoxide, and aluminum hydroxide such as gibbsite are preferred, with aluminum nitrate being even more preferred. One of these sources may be used alone, or two or more may be used in combination.

[0099] The aforementioned organic structure directing agent is not particularly limited, but tetrapropylammonium compounds such as tetrapropylammonium hydroxide or tetraethylammonium compounds such as tetraethylammonium hydroxide are preferred. The molar ratio of the organic structure directing agent to the silica source is preferably 0.01 to 0.60, more preferably 0.03 to 0.40, and even more preferably 0.05 to 0.35.

[0100] The aforementioned compounds containing hydroxides or fluoride ions are added to promote the crystallization of zeolites. Due to their low cost and ease of handling, compounds containing hydroxides are widely used. There are no particular restrictions on whether a compound containing hydroxides exhibits alkalinity in aqueous solution.

[0101] For example, the aforementioned organic structure directing agent can also function as the aforementioned hydroxide-containing compound, in which case the hydroxide is used as the aforementioned tetrapropylammonium compound or tetraethylammonium compound. If this method is used, alkali metals will not enter the zeolite, and proton-type zeolites can be produced.

[0102] On the other hand, zeolites may also contain alkali metal ions. Alternatively, if it is desired to actively introduce alkali metal ions into the zeolite, in addition to the aforementioned organic structure directing agent, hydroxides of alkali metals or alkaline earth metals may be added, preferably alkali metal hydroxides as the aforementioned hydroxide-containing compounds. Examples of organic structure directing agents used in this case include tetrapropylammonium bromide and tetraethylammonium bromide. Furthermore, examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide.

[0103] As a result of pre-containing Rb + The aforementioned Rb used in the manufacture of MFI type zeolite + The source is not particularly limited; for example, rubidium compounds can be cited. Specifically, rubidium hydroxide can be used as the aforementioned hydroxide, and it can also serve as Rb. + Source. Furthermore, as Rb + Methods for introducing alkali metal ions, such as those involving hydroxides, can also involve adding alkali metal compounds other than hydroxides. However, in such cases, compounds containing hydroxides or fluoride ions are added to promote zeolite crystallization. Furthermore, Rb is used in zeolite manufacturing. + When the source or other alkali metal compounds cause the presence of alkali metal ions, the alkali metal compounds often become excessive. Therefore, after hydrothermal synthesis, water washing is performed to remove the excess alkali metal ions. These Rb + The source is preferably added before hydrothermal synthesis.

[0104] There are no particular restrictions on the water used in the aforementioned hydrothermal synthesis. Examples include industrial water, tap water, distilled water, deionized water, pure water, RO water (reverse osmosis membrane treated water), and ultrapure water. One type of water can be used alone, or two or more types can be used in combination.

[0105] The aforementioned hydrothermal synthesis is typically carried out in a reaction vessel. Any well-known vessel suitable for hydrothermal synthesis can be used, and its type is not particularly limited, as long as it is a closed, pressure-resistant vessel appropriate for hydrothermal synthesis. For example, a closed, heat-resistant, and pressure-resistant vessel such as a high-pressure vessel equipped with a stirring device, heat source, pressure gauge, and safety valve is preferred. Furthermore, zeolite crystallization can also be carried out while the aforementioned mixture is allowed to stand; however, from the viewpoint of improving the uniformity of the obtained zeolite, it is preferable to carry it out while the aforementioned mixture is stirred and mixed.

[0106] The processing temperature (reaction temperature) of the aforementioned hydrothermal synthesis is not particularly limited and can be appropriately selected from the viewpoint of the crystallinity and economy of the obtained zeolite. However, it is preferred to be 100°C or higher and 200°C or lower, more preferably 120°C or higher and 190°C or lower, and even more preferably 150°C or higher and 180°C or lower.

[0107] The processing time (reaction time) for the aforementioned hydrothermal synthesis is not particularly limited if crystallization is possible, and can be appropriately selected from the viewpoint of the crystallinity and economy of the obtained zeolite. However, it is preferred to be 1 hour or more and 20 days or less, more preferably 4 hours or more and 15 days or less, and even more preferably 12 hours or more and 11 days or less.

[0108] Furthermore, there are no particular limitations on the processing pressure for the aforementioned hydrothermal synthesis; the self-generated pressure generated when the mixture is heated to the aforementioned temperature range is sufficient. At this time, inert gases such as nitrogen and argon may also be introduced into the container as needed.

[0109] The aforementioned zeolites sometimes contain ammonium ions (NH4+). + ) or proton (H + Non-metallic cations such as Rb, etc. The aforementioned non-metallic cations and the aforementioned Rb + Source Rb + There are no particular restrictions on the methods used for ion exchange; conventional methods can be used.

[0110] --Rb-containing MFI-type zeolite as raw material + Manufacturing method of MFI type zeolite--

[0111] The present invention contains Rb +The method for manufacturing MFI type zeolite includes a mixing step and a calcination step, preferably further including a stirring step and an evaporation and drying step, and may further include other steps as needed.

[0112] ---Mixing Steps---

[0113] The aforementioned mixing step is a step of obtaining a mixture of MFI-type zeolite (hereinafter also referred to as "raw material zeolite") and a liquid containing rubidium compounds.

[0114] By performing the aforementioned mixing steps, for example, the cations (Rb) contained in the rubidium compound can be mixed. + It is ionicly bonded to the acidic sites of the aforementioned raw material zeolite.

[0115] There are no particular limitations on the aforementioned rubidium compounds, and examples include rubidium hydroxide, rubidium nitrate, rubidium chloride, and rubidium carbonate. One of these can be used alone, or two or more can be used in combination. Among these, rubidium nitrate is preferred due to its excellent solubility.

[0116] The raw material zeolite used in the mixing step can be either acidic or basic. Among these, when using a liquid containing a rubidium compound, acidic zeolite with Brønsted acidic sites is preferred in terms of better cation exchange.

[0117] There are no particular restrictions on the zeolite raw material used in the mixing step; it can be synthesized appropriately or commercially available products can be used.

[0118] There are no particular limitations on the synthesis method of the aforementioned raw material zeolite, and it can be appropriately selected from known methods. For example, a method can be given by adding an aqueous solution of aluminum nitrate to tetraalkoxysilane and hydrolyzing it, then distilling off the resulting alcohol and performing hydrothermal synthesis and calcination.

[0119] While there are no particular limitations on the solvent used in the aforementioned liquid containing rubidium compounds, it is preferable to use a solvent that can dissolve the rubidium compounds and is relatively easy to remove without decomposition during the calcination step described later; a highly polar solvent is more preferred. Examples of such solvents include water, methanol, ethanol, acetonitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and hexamethylphosphotriamide. One of these can be used alone, or two or more can be used in combination. Among these solvents, at least one selected from the group consisting of water, methanol, and ethanol is preferred due to its relatively low boiling point and ease of removal; water, which is of particularly low cost, is particularly preferred.

[0120] The concentration of the rubidium compound in the aforementioned liquid containing the rubidium compound is not particularly limited and can be appropriately selected according to the purpose. However, from the perspective of reducing solvent costs, it is preferable to be 0.01 mol / L to 10 mol / L, more preferably 0.05 mol / L to 2.5 mol / L, and even more preferably 0.05 mol / L to 0.5 mol / L. If the concentration of the aforementioned rubidium compound is 0.01 mol / L to 10 mol / L, a homogeneous mixture of the aforementioned raw material zeolite and the solution in which the rubidium compound is dissolved in the aforementioned solvent can be obtained, which is also cost-effective.

[0121] The amount of rubidium compound used in the aforementioned liquid containing rubidium compound can be determined based on the amount of cation (Rb) in the rubidium compound. + The valence of ) and the cation (Rb) in rubidium compounds + The product of the amounts of the substances is relative to the acidity of the aforementioned raw material zeolite (i.e., the aforementioned raw material zeolite can impart cations (Rb). + The ratio of the amount of rubidium at a given site to the amount of Rb in the rubidium compound contained in the liquid. + The appropriate value is determined by [(valence × mass) / acidity of the raw material zeolite]. Furthermore, when using two or more rubidium compounds, the cation (Rb) in the rubidium compound... + The valence of ) is that of cations (Rb) in two or more rubidium compounds. + The sum of the valences of ) and the cations (Rb) in rubidium compounds. + The amount of substance is the cation (Rb) in two or more rubidium compounds. + The sum of the mass of objects.

[0122] As mentioned above, [the Rb content of the rubidium compound contained in the liquid containing the rubidium compound] + The ratio of (valence number × mass) / acidity of the raw material zeolite is not particularly limited and can be appropriately selected according to the purpose; however, it is preferably 40 to 4,000, more preferably 200 to 600. The aforementioned ratio [Rb in the rubidium compound contained in the liquid containing the rubidium compound] is not particularly limited and can be appropriately selected according to the purpose; however, it is preferably 40 to 4,000, more preferably 200 to 600. + [(valence × mass) / acidity of raw material zeolite] If it is above 40, then the cations (Rb) in rubidium nitrate + This can sufficiently impart cation-attributing potential sites to the aforementioned raw material zeolite. The aforementioned ratio [of Rb in the rubidium compound contained in the liquid containing the rubidium compound] + [(valence number × mass) / acidity of raw material zeolite] If it is below 4,000, it is advantageous in terms of cost.

[0123] The acidity of the above-mentioned starting zeolite can be determined, for example, by a temperature-programmed desorption method (TPD method) using an appropriate base (e.g., ammonia) and measuring the amount of the base adsorbed on the starting zeolite.

[0124] The method of mixing the above-mentioned starting zeolite with a liquid containing a rubidium compound as a mixed liquid is not particularly limited and can be appropriately selected according to the purpose. For example, a method of immersing the above-mentioned starting zeolite in a solution in which a rubidium compound is dissolved in a solvent can be cited.

[0125] The cation contained in the zeolite as the above-mentioned starting material is not particularly limited, but a zeolite of the MFI type containing H + is preferred because the substitution efficiency for Rb + is good.

[0126] When using a zeolite of the MFI type containing H + as the starting material for the zeolite of the MFI type containing Rb + , the acidity of the zeolite of the MFI type containing H + is not particularly limited and can be appropriately selected according to the purpose. However, it is preferably 0.01 mmol / g or more and 2.5 mmol / g or less, more preferably 0.01 mmol / g or more and 2.0 mmol / g or less, and still more preferably 0.01 mmol / g or more and 0.1 mmol / g or less. If the acidity of the zeolite of the MFI type containing H + is 0.01 mmol / g or more and 2.5 mmol / g or less, a zeolite of the MFI type containing Rb + with good yields of olefins having 2 to 5 carbon atoms and a good O / P ratio of the olefin-containing composition can be obtained.

[0127] The acidity of the zeolite of the MFI type containing H + can be measured by an ammonia temperature-programmed desorption method (hereinafter, also simply referred to as "TPD").

[0128] In the above-mentioned mixing step, when the mass of the zeolite of the MFI type is set to x (g), the molar ratio of SiO2 to Al2O3 in the zeolite of the MFI type [SiO2 / Al2O3] is set to y, and the molar number of the above-mentioned rubidium compound is set to z (mmol), the range after dividing the value obtained by multiplying y by z by x (the range of yz / x (mmol / g)) is not particularly limited and can be appropriately selected according to the purpose. However, it is preferably 1 ≤ yz / x ≤ 10,000, more preferably 2,000 ≤ yz / x ≤ 8,000, and still more preferably 4,000 < yz / x ≤ 6,000. By satisfying 1 ≤ yz / x ≤ 10,000, the zeolite of the MFI type containing Rb +The resulting improvement in the O / P ratio of the olefin-containing composition is advantageous in terms of the time, labor, and raw material costs involved in preparing the zeolite.

[0129] ---Stirring Steps---

[0130] The aforementioned stirring step involves stirring the mixture of the aforementioned raw material zeolite and the aforementioned liquid containing rubidium compounds to produce the zeolite after solution treatment.

[0131] There are no particular restrictions on the method of stirring the aforementioned mixture; any known method may be used.

[0132] The stirring time of the aforementioned mixture is not particularly limited and can be appropriately determined based on the concentration of the rubidium compound contained in the liquid containing the rubidium compound. However, at room temperature under atmospheric conditions, it is preferably 0.5 hours to 48 hours, more preferably 1 hour to 24 hours, and even more preferably 6 hours to 15 hours. If the stirring time is 0.5 hours or more, the cations contained in the rubidium compound can be sufficiently incorporated into the raw material zeolite. Furthermore, if the stirring time is 48 hours or less, contamination caused by substances contained in the air or uneven cation incorporation caused by changes in the concentration of the mixture can be prevented.

[0133] The zeolite obtained after solution treatment by the aforementioned stirring step is preferably filtered and washed by, for example, natural filtration or suction filtration. Washing of the solution-treated zeolite can be further performed, for example, by passing the solvent used in the solution in which the rubidium compound is dissolved through the solution-treated zeolite after filtration.

[0134] ---Evaporation and Drying Steps---

[0135] The aforementioned evaporation and drying step involves directly evaporating and drying the zeolite after solution treatment without filtering out the residue. By including the aforementioned evaporation and drying step, cation exchange can be further facilitated.

[0136] The aforementioned evaporation and drying method is not particularly limited and can be appropriately selected according to the type of solvent contained in the aforementioned mixture. When the solvent is water, for example, a method of allowing the mixture to stand at room temperature under atmospheric conditions for an appropriate time can be cited. In this case, the standing time is not particularly limited, as long as the solvent can be removed; however, 2 to 14 days is preferred, more preferably 3 to 12 days, and even more preferably 4 to 6 days.

[0137] The aforementioned evaporation and drying step can also be performed using an oven set at a temperature above room temperature and below the solvent's boiling point, a temperature that will not cause the solvent to boil over, under atmospheric conditions for an appropriate duration. Using this method, the time required to complete the evaporation and drying process can be shortened. The heating time in the aforementioned oven can be adjusted appropriately according to the heating temperature. For example, when the solvent is water, it can be carried out at approximately 80°C for 5 to 10 hours, or at approximately 50°C for 40 to 60 hours.

[0138] Furthermore, in order to remove excess rubidium compounds that may precipitate on the surface of the zeolite obtained by evaporation and drying after solution treatment, it is preferable to perform a calcination step after washing with a solvent used in the preparation of the rubidium compound solution.

[0139] ---Firing Steps---

[0140] The aforementioned firing step refers to firing the zeolite obtained after the aforementioned mixing step, the aforementioned stirring step, or the aforementioned evaporation and drying step.

[0141] When using acidic zeolite as the aforementioned raw material zeolite, the calcination step removes protons and nitrate ions from rubidium compounds that remain on the acidic sites of the raw material zeolite even after the aforementioned mixing and stirring steps, which are then volatilized as water and nitrogen dioxide, thereby further promoting cation donation. Furthermore, almost all solvent remaining even after the filtration and evaporation drying steps can be removed.

[0142] There are no particular restrictions on the firing conditions and temperature of the zeolite after solution treatment in the aforementioned firing steps. Preferably, it is fired at 300°C to 600°C in an atmospheric atmosphere, and more preferably at 450°C to 550°C in an atmospheric atmosphere.

[0143] Furthermore, there is no particular limitation on the firing time of the zeolite after solution treatment in the aforementioned firing step, which is preferably 1 hour to 20 hours, and more preferably 6 hours to 15 hours.

[0144] In addition, the aforementioned Rb + The pore size of MFI-type zeolites can be controlled by varying the conditions of the aforementioned mixing and stirring steps. A smaller BET specific surface area presumably results in a smaller pore size in the produced zeolite. This is achieved by adjusting the valence of the cations selected from the rubidium compounds contained in the solution relative to the cations (Rb) in the rubidium compounds. + The product of the amounts of rubidium and rubidium is relative to the amount of rubidium in the raw material zeolite that can confer cation sites (the acidity of the raw material zeolite). [Rb in the rubidium compound contained in the liquid] +Zeolites with different BET specific surface areas can be manufactured by varying at least one of the following conditions: [(valence number × mass) / acidity of raw material zeolite], the concentration of rubidium compound in the solution in which the rubidium compound is dissolved in the solvent, and the stirring time of the mixture.

[0145] <<Plastics>>

[0146] There are no particular restrictions on the aforementioned plastics, and they can be appropriately selected according to the purpose. However, from the viewpoint of reducing environmental impact, it is preferable to contain waste plastics, more preferably to contain polyolefins, and even more preferably to contain at least one of polyethylene (PE), polypropylene (PP), and polystyrene (PS), which are widely used in containers, packaging materials, molded articles, films, etc. for beverages and food.

[0147] In addition to the plastics mentioned above, the aforementioned plastics may also include other plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polycarbonate (PC), polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, polyamide, polyurethane, acrylonitrile-butadiene-styrene copolymer, and polymethyl methacrylate.

[0148] When the aforementioned plastic is waste plastic, the preferred composition ratio is 20% to 40% by mass of PE, 20% to 40% by mass of PP, and 10% to 30% by mass of PS.

[0149] There is no particular limitation on the content of the aforementioned other plastics in the aforementioned plastics, and they can be appropriately selected according to the type of waste plastics, etc. However, from the viewpoint of the yield of olefins with 2 to 5 carbons and the O / P ratio of the composition containing olefins, it is preferable to be 50% by mass or less of the total mass of the aforementioned plastics, more preferably 45% by mass or less, and even more preferably 40% by mass or less.

[0150] The aforementioned plastic may also be a plastic composition that further includes materials or additives other than plastic. Examples of materials other than plastic, in the case of a waste plastic composition, include, for example, paper and metal.

[0151] There are no particular restrictions on the content of materials or additives other than the aforementioned plastics in the aforementioned plastic composition.

[0152] From the perspective of good decomposition efficiency, the aforementioned decomposition steps are preferably performed by heating.

[0153] There are no particular restrictions on the reactor used for the aforementioned decomposition steps; it can be appropriately selected according to the purpose. For example, batch reactors, fixed-bed reactors, and fluidized-bed reactors can be mentioned.

[0154] The temperature at which the aforementioned decomposition step is performed (hereinafter also referred to as the "decomposition temperature") is not particularly limited and can be appropriately selected according to the purpose; however, it is preferably 300°C to 1,100°C, and more preferably 300°C to 600°C. If the aforementioned decomposition temperature is 300°C to 1,100°C, the aforementioned zeolite is easily activated, and the yield of olefins with 2 to 5 carbon atoms and the O / P ratio of the olefin-containing composition are good.

[0155] The time for decomposition at the aforementioned decomposition temperature (hereinafter also referred to as "decomposition time") is not particularly limited and can be appropriately selected depending on the reaction system, etc. For example, when the aforementioned decomposition is carried out using a closed batch reactor, the aforementioned decomposition time is preferably 1 hour to 20 hours, more preferably 5 hours to 10 hours. If the aforementioned decomposition time is 1 hour or more, the aforementioned plastic can be properly decomposed, and the yield of olefins with 2 to 5 carbons and the O / P ratio of the olefin-containing composition are good. Furthermore, the aforementioned decomposition time of 20 hours or less is more efficient.

[0156] There are no particular restrictions on the atmosphere in which the aforementioned decomposition is carried out; it can be appropriately selected according to the purpose, but it is preferred to carry it out in the presence of an inert gas.

[0157] There are no particular restrictions on the inert gases mentioned above, and they can be selected appropriately according to the purpose. For example, nitrogen and argon can be used. One of these can be used alone, or two or more can be used together.

[0158] To ensure the complete fluidization of the aforementioned plastics, a portion of the plastics may also be vaporized during the aforementioned decomposition step. Furthermore, in the case of industrial waste, relatively homogeneous waste plastic materials composed of specific plastic components and with a molecular weight distribution within a certain range can be obtained. In such cases, it is preferable to set the processing conditions of the decomposition step according to the type and molecular weight of the plastic components constituting the waste plastic material. Additionally, when separating inorganic substances from waste plastic materials that are considered general waste, laboratory-scale separation equipment can be used; however, industrial-scale implementation is also possible, for example, in various plants such as oil refineries.

[0159] <Other Steps>

[0160] The other steps in the aforementioned method for manufacturing the olefin-containing composition are not particularly limited and can be appropriately selected according to the purpose. Examples include the aforementioned pretreatment step for the plastic and the recovery step of volatile components obtained in the aforementioned decomposition step. Furthermore, the method may also include the aforementioned manufacturing process for the aforementioned Rb-containing composition. + The mixing, stirring, and firing steps of MFI type zeolite.

[0161] <<Pre-processing steps>>

[0162] The aforementioned pretreatment step involves pretreating the plastic before it undergoes the aforementioned decomposition step. By making the plastic easier to decompose in the aforementioned pretreatment step, the plastic can be decomposed more efficiently.

[0163] Examples of the aforementioned pretreatments include, for instance, the aforementioned plastic pulverization process, the aforementioned plastic pulverization (slicing) process, and the aforementioned plastic melting process.

[0164] The aforementioned melt treatment of the plastic is preferably carried out in the absence of zeolite at a temperature below 300°C.

[0165] There are no particular limitations on the shredded form of the aforementioned plastics; it can be appropriately selected according to the purpose, for example, powder or fragments.

[0166] There are no particular limitations on the method for obtaining the aforementioned plastic pulverized material; any method known in the prior art may be appropriately selected. For example, a method of pulverizing the aforementioned plastic by means of a pulverizer to obtain powder or fragments may be cited.

[0167] Furthermore, there are no particular limitations on the method for granulating (slicing) the aforementioned pulverized material. Appropriate methods can be selected from those known in the past. For example, a method can be given where the aforementioned pulverized material is melted and extruded, and then sliced ​​by cutting the linear melt extrusion.

[0168] The aforementioned plastic can also be supplied to the aforementioned decomposition step in a molten state. There are no particular limitations on the method of melting the aforementioned plastic, and appropriate methods known in the art can be selected, for example, a method of continuously supplying the plastic to the aforementioned decomposition step using a melt extruder.

[0169] <<Volatile Component Recovery Steps>>

[0170] The aforementioned volatile component recovery step is a step of recovering the volatile components obtained in the aforementioned decomposition step.

[0171] The advantage of including the aforementioned volatile component recovery step is that, when volatile components are generated in the aforementioned decomposition step, they can be recovered or removed according to their usefulness. For example, if the aforementioned plastic contains polystyrene, the styrene monomer generated in the aforementioned decomposition step can be vaporized and recovered. The recovered styrene monomer is advantageous from the viewpoint that it can be reused in the manufacture of polystyrene. Furthermore, when the aforementioned plastic material contains chlorine-containing plastics such as polyvinyl chloride and polyvinylidene chloride, it is preferable to vaporize and remove the hydrogen chloride generated when heating the chlorine-containing plastic in the aforementioned decomposition step. In addition to the aforementioned decomposition step, hydrogen chloride can also be preheated at a low temperature to vaporize it before being supplied to the aforementioned decomposition step. The heating temperature at this low temperature is preferably 100°C or higher and less than 300°C. Therefore, after the aforementioned plastic is fluidized, the chlorine content of the fluidized olefin-containing composition can be reduced.

[0172] There are no particular restrictions on the methods for recovering the aforementioned volatile components; any previously known methods may be appropriately selected.

[0173] The above method for manufacturing olefin-containing compositions yields a raw material suitable for chemical recovery that has low paraffin content as a byproduct and excellent yields of olefins with 2 to 5 carbon atoms.

[0174] (Catalyst for manufacturing compositions containing olefins)

[0175] The catalyst for manufacturing an olefin-containing composition according to one embodiment of the present invention is a catalyst for manufacturing an olefin-containing composition containing olefins having 2 to 5 carbon atoms, wherein it contains Rb + MFI type zeolite, and may further contain other components as needed.

[0176] Raw materials for compositions containing olefins include plastics.

[0177] <Contains Rb> + MFI type zeolite >

[0178] The aforementioned contains Rb + The MFI type zeolite is as described in the aforementioned item (method for manufacturing compositions containing olefins).

[0179] In the catalyst for manufacturing the aforementioned olefin-containing composition, the aforementioned Rb-containing... + The content of MFI-type zeolite is not particularly limited within a range that does not impair the effects of this embodiment, and can be appropriately selected according to the purpose. The catalyst for manufacturing the aforementioned olefin-containing composition can also be the aforementioned Rb-containing catalyst. + The MFI type zeolite itself (i.e., the aforementioned Rb-containing zeolite) + The content of MFI type zeolite is 100% by mass.

[0180] <Other Ingredients>

[0181] There are no particular limitations on the other components mentioned above in the catalyst for manufacturing the aforementioned olefin-containing composition. Examples include pH adjusters, preservatives and mildew inhibitors, binding additives (adhesives), and granulation aids.

[0182] The content of the other components in the catalyst for manufacturing the aforementioned olefin-containing composition is not particularly limited to the extent that it does not impair the effects of the embodiments of the present invention, and can be appropriately selected according to the purpose.

[0183] The catalyst used in the manufacture of the aforementioned olefin-containing composition is a catalyst, that is, a catalyst used in the manufacture of the aforementioned Rb-containing composition. + The manufacture of olefin-containing compositions containing olefins of the MFI type zeolite having 2 to 5 carbon atoms. Therefore, in the process of manufacturing olefin-containing compositions containing olefins having 2 to 5 carbon atoms, a zeolite containing Rb is used. + The method of using MFI-type zeolite catalysts is also included within the scope of this invention.

[0184] Example

[0185] The following examples, including test examples, reference manufacturing examples, manufacturing examples, comparative manufacturing examples, embodiments, and comparative examples, are provided to specifically illustrate the implementation of the present invention. However, the implementation of the present invention is not limited to these test examples, reference manufacturing examples, manufacturing examples, comparative manufacturing examples, embodiments, and comparative examples. Furthermore, unless otherwise specified, "%" in the following description represents "mass %".

[0186] (Experimental Example 1: Prediction Experiment)

[0187] An information processing system was constructed using parameters of zeolite, metal cations, and ion-exchange anions as explanatory variables and the reaction yield of organic compounds as an object variable. This system was used to predict the relationship between the yield of useful components obtained from the decomposition of plastics and the O / P ratio when using zeolite containing metal cations as a catalyst.

[0188] Specifically, using Figure 1 The information processing system 1 shown has the functions described, and is based on... Figure 2 The steps shown are used to process the machine learning model, and... Figure 3 The steps shown are used to predict the relationship between the yield of useful components obtained from the decomposition of plastics and the O / P ratio when using zeolites containing metal cations as catalysts.

[0189] Information processing system 1 includes a design support device 10, a learning device 11, and a user terminal 12. The user terminal 12 is an information processing terminal operated by an operator. The design support device 10 is an information processing device that supports the more efficient design of PCs, etc., containing zeolites with desired metal cations. The design support device 10 is an apparatus that generates a comprehensive combination of parameters for zeolites, metal cations, and ion-exchange anions, and uses a learned machine learning model to predict the reaction yield of organic compounds corresponding to the comprehensive combination, and outputs candidate zeolites containing metal cations with desired properties. The learning device 11 is an apparatus that enables the machine learning model to learn the correspondence between information on zeolite parameters, metal cation parameters, and ion-exchange anion parameters and the reaction yield of organic compounds.

[0190] Figure 2 In step S10, the learning dataset acquisition unit 52 of the learning device 11 acquires a learning dataset for learning the machine learning model. The learning dataset represents the correspondence between the parameters of zeolite, the parameters of metal cations, and the parameters of ion-exchange anions and the reaction yield of organic compounds.

[0191] Next, through Figure 2 The processing in step S12 shown converts the learning dataset into parameters representing zeolite (item "Crystallization System"), metal cations (items "Cation Type", "Cation Ion Crystallization Radius", "Cation Electronegativity", and "Cation Charge"), and ion-exchange anions (item "Ion-exchange Anion: NO3-"). - "and "ion exchange anion: OH - A learning dataset showing the correspondence between the reaction yields of organic compounds (items "ethylene yield", "propylene yield", "total yield of 4-carbon and 5-carbon olefins", "useful aromatic yield", and "O / P ratio") and the reaction yields of organic compounds.

[0192] then, Figure 2 In step S14 shown, the learning unit 54 uses the learning dataset after parameter conversion as a basis to enable the machine learning model to learn the correspondence between the parameters of zeolite, the parameters of metal cations and ion-exchange anions and the reaction yield of organic compounds.

[0193] Next, information processing system 1 uses Figure 3 The steps shown are used to predict candidates for zeolites containing metal cations that can provide good yields of useful components and O / P ratios.

[0194] In step S20, the design support device 10 obtains the machine learning model that has been learned by the learning device 11.

[0195] In step S22, the exploration range receiving unit 26 receives the input of the exploration range of the zeolite containing metal cations.

[0196] In step S24, the parameter generation unit 28 receives the input of the zeolite containing metal cations in step S22 and generates a comprehensive combination of the parameters of the zeolite, the parameters of the metal cations, and the parameters of the ion-exchange anions.

[0197] In step S26, the parameter generation unit 28 uses a specific parameter table to comprehensively combine the parameters of the zeolite, metal cations, and ion-exchange anions generated in step S24, and performs parameter conversion for items that must be converted into parameters. Furthermore, the BET specific surface area and the molar ratio [SiO2 / Al2O3] of the zeolite cannot be determined solely by the zeolite framework, so these values ​​must be input separately.

[0198] In step S28, the prediction unit 30 inputs a comprehensive combination of the parameters of the zeolite generated by the parameter generation unit 28, the parameters of the metal cations, and the parameters of the ion-exchange anions into the learned machine learning model, thereby predicting the reaction yield of the organic compound (items "ethylene yield", "propylene yield", "total yield of 4-carbon olefins and 5-carbon olefins", "useful aromatic yield", and "O / P ratio").

[0199] In step S30, the candidate output unit 32 counts the reaction yields of organic compounds corresponding to the comprehensive combinations predicted by the prediction unit 30, and sorts them from high to low yield in each item.

[0200] In step S32, the candidate output unit 32 outputs data on candidate zeolites containing metal cations based on the reaction yield of organic compounds corresponding to the comprehensive combination predicted by the prediction unit 30.

[0201] Based on the results of the predictive experiments conducted using the information processing system 1 described above, the zeolite that yields good useful component yield and O / P ratio is predicted to be of the MFI crystal type with Rb as the cation. + 、Sr 2+ and Cs + .

[0202] Based on the aforementioned predictions, more detailed predictions were made regarding the crystallization system, cation and anion combinations of zeolites as recorded in Table 1 below. The results are shown in Table 1 below.

[0203] Table 1

[0204]

[0205] (Refer to manufacturing example 1)

[0206] <Synthesis steps of zeolite A>

[0207] In a 200 mL three-necked flask equipped with a stirrer, condenser, and dropping funnel, 55 g (0.26 mol) of tetraethoxysilane was weighed. Separately, an aqueous solution of aluminum nitrate (0.132 g) in 10 g of pure water was prepared. While stirring the tetraethoxysilane in the three-necked flask at room temperature (20 °C ± 5 °C), the entire volume of the aluminum nitrate aqueous solution was added and mixed to prepare a mixture. Next, while stirring the mixture at room temperature, 85.06 g (0.085 mol) of a 1 mol / L tetrapropylammonium hydroxide aqueous solution was added dropwise through the dropping funnel over 1 hour. Then, the reactor was heated in an oil bath at 100 °C and stirred for 1 hour to hydrolyze the tetraethoxysilane. Next, the condenser of the three-necked flask was replaced with a distillation apparatus, and the reactor was heated in an oil bath at 130 °C to remove the ethanol generated during the hydrolysis by distillation over 1.5 hours. During the ethanol distillation process, 5 mL of pure water was added twice, resulting in a final mixture of approximately 70 mL. All the obtained mixture was placed in an autoclave equipped with a Teflon (registered trademark) inner cylinder and subjected to hydrothermal synthesis at 180°C for 11 days. After cooling to room temperature, the mixture was centrifuged for solid-liquid separation. Pure water was added to the obtained solid, and the washing process via centrifugation was repeated twice. The obtained solid was dried at 80°C for 1 day. The dried solid was then calcined in air at 550°C for 6 hours to decompose and remove organic matter, yielding MFI-type zeolite (hereinafter also referred to as "zeolite a").

[0208] (Manufacturing Example 1)

[0209] <Processing Steps>

[0210] 1.5 g (mass) (10.20 mmol) of rubidium nitrate (RbNO3, purity: 95.0% or higher, manufactured by Kanto Chemical Co., Ltd.) was dissolved completely in pure water to prepare a 0.20 mol / L rubidium nitrate aqueous solution. In a glass container, 5 g of zeolite a obtained in Reference Manufacturing Example 1 was mixed with the entire volume of the aforementioned rubidium nitrate aqueous solution, and the mixture was stirred at room temperature under atmospheric atmosphere for 12 hours to obtain the reactant.

[0211] <Firing Steps>

[0212] Following the aforementioned processing steps, the reactants were left to stand at room temperature under atmospheric conditions for 5 days to obtain a solidified product after evaporation and drying. The obtained solidified product was washed with water and transferred to a magnetic crucible, and then calcined in an electric furnace set at 500°C under atmospheric conditions for 8 hours to obtain the solid catalyst of Manufacturing Example 1.

[0213] (Manufacturing Example 2)

[0214] Except for the step in Manufacturing Example 1 where 1.5 g (mass) (10.20 mmol) of rubidium nitrate (RbNO3, purity: 95.0% or higher, manufactured by Kanto Chemical Co., Ltd.) was added to pure water and completely dissolved to prepare a 0.20 mol / L rubidium nitrate aqueous solution, the step of preparing a 0.28 mol / L sodium nitrate aqueous solution was changed to adding 2.0 g (mass) (13.90 mmol) of rubidium nitrate (RbNO3, purity: 95.0% or higher, manufactured by Kanto Chemical Co., Ltd.) to pure water and completely dissolved to prepare a 0.28 mol / L sodium nitrate aqueous solution. The zeolite treatment and calcination steps were performed in the same way as in Manufacturing Example 1 to obtain the solid catalyst of Manufacturing Example 2.

[0215] (Manufacturing Example 3)

[0216] Except for the step in Manufacturing Example 1 where the step of adding pure water to 1.5 g (mass) (10.20 mmol) of rubidium nitrate (RbNO3, purity: 95.0% or higher, manufactured by Kanto Chemical Co., Ltd.) to prepare a 0.20 mol / L rubidium nitrate aqueous solution and completely dissolving it, the step of adding pure water to 2.7 g (mass) (18.60 mmol) of rubidium nitrate (RbNO3, purity: 95.0% or higher, manufactured by Kanto Chemical Co., Ltd.) to completely dissolve it and prepare a 0.37 mol / L sodium nitrate aqueous solution was carried out using the same method as in Manufacturing Example 1 for the zeolite treatment and calcination steps, to obtain the solid catalyst of Manufacturing Example 3.

[0217] (Comparative Manufacturing Example 1)

[0218] Except for changing the processing steps of Manufacturing Example 1 as described below, the zeolite synthesis and calcination steps were carried out in the same way as in Manufacturing Example 1 to obtain the solid catalyst of Comparative Manufacturing Example 1.

[0219] <Processing Steps>

[0220] 0.84 g (by weight) (9.88 mmol) of sodium nitrate (NaNO3, manufactured by Fujifilm and Kojun Chemical Co., Ltd.) was dissolved completely in pure water to prepare a 0.20 mol / L sodium nitrate aqueous solution. In a glass container, 5 g of zeolite a obtained in Reference Manufacturing Example 1 was mixed with the entire volume of the aforementioned sodium nitrate aqueous solution, and the mixture was stirred at room temperature under atmospheric pressure for 12 hours to obtain the reactant.

[0221] (Comparative Manufacturing Example 2)

[0222] Except for changing the processing steps of Manufacturing Example 1 as described below, the zeolite synthesis and calcination steps were carried out in the same way as in Manufacturing Example 1 to obtain the solid catalyst of Comparative Manufacturing Example 2.

[0223] <Processing Steps>

[0224] 1.0 g (9.89 mmol) of potassium nitrate (KNO3, manufactured by Fujifilm and Kojun Chemical Co., Ltd.) was dissolved completely in pure water to prepare a 0.20 mol / L potassium nitrate aqueous solution. In a glass container, 5 g of zeolite a obtained in Reference Manufacturing Example 1 was mixed with the entire volume of the aforementioned potassium nitrate aqueous solution, and the mixture was stirred at room temperature under atmospheric pressure for 12 hours to obtain the reactant.

[0225] (Comparative Manufacturing Example 3)

[0226] Except for changing the processing steps of Manufacturing Example 1 as described below, the zeolite synthesis and calcination steps were carried out in the same way as in Manufacturing Example 1 to obtain the solid catalyst of Comparative Manufacturing Example 3.

[0227] <Processing Steps>

[0228] 1.9 g (9.75 mmol) of cesium nitrate (CsNO3, manufactured by Fujifilm and Kojun Chemical Co., Ltd.) was dissolved completely in purified water to prepare a 0.20 mol / L cesium nitrate aqueous solution. In a glass container, 5 g of zeolite a obtained in Reference Manufacturing Example 1 was mixed with the entire volume of the aforementioned cesium nitrate aqueous solution, and the mixture was stirred at room temperature under atmospheric pressure for 12 hours to obtain the reactant.

[0229] (Comparative Manufacturing Example 4)

[0230] Except for changing the processing steps of Manufacturing Example 1 as described below, the zeolite synthesis and calcination steps were carried out in the same way as in Manufacturing Example 1 to obtain the solid catalyst of Comparative Manufacturing Example 4.

[0231] <Processing Steps>

[0232] 1.0 g (4.70 mmol) of strontium nitrate (Sr(NO3)2, manufactured by Fujifilm and Koujun Chemical Co., Ltd.) was dissolved completely in purified water to prepare a 0.09 mol / L strontium nitrate aqueous solution. In a glass container, 5 g of zeolite a obtained in Reference Manufacturing Example 1 was mixed with the entire volume of the aforementioned strontium nitrate aqueous solution, and the mixture was stirred at room temperature under atmospheric pressure for 12 hours to obtain the reactant.

[0233] (Comparative Manufacturing Example 5)

[0234] <Synthesis Steps of Titanium Silicate>

[0235] 107 g (0.514 mol) of tetraethoxysilane and 4.9 g of tetra(n-butoxy)titanium were weighed into a 500 mL three-necked flask equipped with a stirrer, condenser, and dropping funnel. Then, under ice-cooled conditions, 168.1 g (0.168 mol) of a 1 mol / L tetrapropylammonium hydroxide aqueous solution was added dropwise over 1.5 hours with stirring. The reactor was then heated in an oil bath at 100 °C and stirred for 1 hour to hydrolyze the tetraethoxysilane. Next, the condenser of the three-necked flask was replaced with a distillation apparatus, and the reactor was heated in an oil bath at 130 °C to remove the ethanol generated from the hydrolysis by distillation over 1.5 hours. During the ethanol distillation process, 5 mL of pure water was added twice, ultimately yielding approximately 70 mL of mixed slurry. All the obtained slurry mixtures were placed in an autoclave equipped with a Teflon (registered trademark) inner cylinder and subjected to hydrothermal synthesis at 180°C for 6 days. After cooling to room temperature, the slurry was centrifuged to separate the solid and liquid. Pure water was added to the obtained solid and stirred, and the washing process by centrifugation was repeated twice. The obtained solid was dried at 80°C for 1 day. The dried solid was then calcined in the atmosphere at 550°C for 6 hours to decompose and remove organic matter, yielding titanosilicon (hereinafter also referred to as "TS-1"). This TS-1 was used as the solid catalyst for Comparative Manufacturing Example 5.

[0236] (Comparative Manufacturing Example 6)

[0237] Except for changing the processing steps of Manufacturing Example 1 as described below, the zeolite synthesis and calcination steps were carried out in the same way as in Manufacturing Example 1 to obtain the solid catalyst of Comparative Manufacturing Example 6.

[0238] <Processing Steps>

[0239] 0.92 g (6.24 mmol) of rubidium nitrate (RbNO3, manufactured by Kanto Chemical Co., Ltd.) was dissolved completely in pure water to prepare a 0.12 mol / L rubidium nitrate aqueous solution. In a glass container, 5 g of FAU-type zeolite (high-silica zeolite HSZ-300, 350HUA type, manufactured by Tosoh Co., Ltd., molar ratio [SiO2 / Al2O3]:10) (hereinafter also referred to as "zeolite b") was mixed with the entire volume of the aforementioned rubidium nitrate aqueous solution. The mixture was stirred at room temperature under atmospheric atmosphere for 12 hours to obtain the reactant.

[0240] (Comparative Manufacturing Example 7)

[0241] Except for changing the process in Comparative Manufacturing Example 1, where 0.84 g (mass) (9.88 mmol) of sodium nitrate was dissolved in pure water to prepare a 0.2 mol / L sodium nitrate aqueous solution, to 0.61 g (mass) (7.20 mmol) of sodium nitrate was dissolved in pure water to prepare a 0.14 mol / L sodium nitrate aqueous solution, and changing zeolite a obtained in Comparative Manufacturing Example 1 to commercially available MFI type zeolite (high-silica zeolite HSZ-800, 840HOA type, manufactured by Tosoh Corporation, molar ratio [SiO2 / Al2O3]: 40) (hereinafter also referred to as "zeolite c"), the zeolite processing and calcination steps were performed in the same manner as in Comparative Manufacturing Example 1 to obtain the solid catalyst of Comparative Manufacturing Example 7.

[0242] (Comparative Manufacturing Example 8)

[0243] Except for Comparative Manufacturing Example 7, where 0.61 g (mass) (7.20 mmol) of sodium nitrate was dissolved in pure water to prepare a 0.14 mol / L sodium nitrate aqueous solution, and 0.40 g (mass) (10.00 mmol) of sodium hydroxide (NaOH, manufactured by Fujifilm and Kojun Chemical Co., Ltd.) was dissolved in pure water to prepare a 0.20 mol / L sodium hydroxide aqueous solution, the zeolite treatment and calcination steps were performed in the same manner as in Comparative Manufacturing Example 1 to obtain the solid catalyst of Comparative Manufacturing Example 8.

[0244] <Determination of Acidity of Solid Catalysts (Zeolites)>

[0245] In the manufacture of solid catalysts in Manufacturing Examples 1 to 3 and Comparative Manufacturing Examples 1 to 4 and 6 to 8, the acidity of the MFI type zeolite (zeolite a), FAU type zeolite (zeolite b), and MFI type zeolite (zeolite c) used as raw materials in Reference Manufacturing Example 1 (hereinafter, these are collectively referred to as "raw material zeolites") was analyzed by ammonia temperature desorption (TPD) under the following determination conditions.

[0246] [Acidity Measurement Conditions]

[0247] • Device: BEL-CAT-BASIC (Made by Microtrac-BEL Co., Ltd.)

[0248] • Detector: BEL-Mass quadrupole mass analyzer (manufactured by Microtrac-BEL Co., Ltd.)

[0249] • Specimen type measured: NH3 (m / z=16)

[0250] • Preprocessing conditions: Perform preprocessing according to the conditions listed in Table 1 below, in the order of 1 to 9 as described in Table 2 below.

[0251] • Heating conditions: Increase the temperature from 100℃ to 600℃ at a rate of 10℃ / min, and hold at 600℃ for 30 minutes. The He gas flow rate during heating is set to 30 mL / min.

[0252] Table 2

[0253]

[0254] The acidity of MFI type zeolite (zeolite a) is 0.037 mmol / g, the acidity of FAU type zeolite (zeolite b) is 1.0 mmol / g, and the acidity of MFI type zeolite (zeolite c) is 0.86 mmol / g.

[0255] [Evaluation of the physical properties of zeolites]

[0256] The crystal system, BET specific surface area, molar ratio [SiO2 / Al2O3], and salt concentration in aqueous solution of the zeolites obtained in Reference Manufacturing Examples 1, Manufacturing Examples 1-3, and Comparative Manufacturing Examples 1-8 were analyzed using the following methods. Furthermore, the ratio [valence × mass of cations in the salt-containing aqueous solution / acidity of the raw material zeolite] of the zeolites obtained in Reference Manufacturing Examples 1, Manufacturing Examples 1-3, and Comparative Manufacturing Examples 1-8 was calculated using the following methods. The results are shown in Tables 3-1 and 3-2 below.

[0257] Furthermore, in Tables 3-1 and 3-2 below, the ionic crystal radii of the zeolites containing ions obtained in Reference Manufacturing Example 1, Manufacturing Examples 1-3, and Comparative Manufacturing Examples 1-4 and 6-8 represent the values ​​of the crystal radii determined by RD Shannon and CT Prewitt et al., and the electronegativity of the cation element represents the value of Pauling's electronegativity.

[0258] Analysis of the Crystalline System of Zeolites

[0259] The crystal systems of the zeolites obtained in Manufacturing Examples 1, 1-3 and Comparative Manufacturing Examples 1-8 were analyzed by X-ray diffraction (XRD) under the following measurement conditions.

[0260] [X-ray diffraction measurement conditions]

[0261] • Device: X'Pert Pro MPD (made by Pnalytical)

[0262] X-ray source: CuKα rays

[0263] • Circulation X-ray side filter: 10mm brass shield

[0264] • Detector-side filter: Ni filter

[0265] • Incident side slit: Sollerslit 0.04 rad ASS 1 / 8°

[0266] • Detector-side slit: ASS 5.0mm, Sollerslit 0.04rad

[0267] • Detector: PIXel1D

[0268] • Measurement method: Reflectance method

[0269] • Operating area (measurement range): 2θ = 5°~120°

[0270] • Step width: 0.006565°

[0271] Counting time: 78.795 seconds / step

[0272] <Determination of BET specific surface area of ​​zeolites>

[0273] The BET specific surface area of ​​each zeolite obtained in manufacturing examples 1, 1-3 and comparative manufacturing examples 1-8 was determined according to ISO 9277:2010 "Determination of specific surface area of ​​powders (solids) by gas adsorption".

[0274] Specifically, using nitrogen molecules as probes, the specific surface area is measured at liquid nitrogen temperature using a specific surface area measuring device (BELSORP MAX II, manufactured by Microtrac-BEL Co., Ltd.) according to ISO 9277:2010, and analyzed by the BET method to determine the specific surface area.

[0275] <Calculation of the molar ratio [SiO2 / Al2O3] of solid catalysts (zeolites)>

[0276] Accurately weigh each solid catalyst obtained in Reference Manufacturing Example 1, Manufacturing Examples 1-3, and Comparative Manufacturing Examples 1-8, using nitric acid (manufactured by Kanto Chemical Co., Ltd., EL nitric acid 1.38 for electronic industry, purity 60.0%-61.0%) and hydrofluoric acid (manufactured by Kanto Chemical Co., Ltd., Ultrapure reagent). TM The sample was prepared by completely dissolving an aqueous solution (-100°C, purity 46.0%–51.0%) in water to a fixed volume. The contents of Si and Al were determined using an ICP-based spectrophotometer (PlasmaQuant PQ 9000, Analytick Jena AG). The molar ratio [SiO2 / Al2O3] was calculated based on the molar numbers of Si and Al obtained from the content, using the following formula.

[0277] The molar ratio [SiO2 / Al2O3] = 2 × (number of moles of Si) / (number of moles of Al)

[0278] <Determination of Salt Concentration in Aqueous Solutions>

[0279] The salt concentration in each aqueous solution used in the processing steps of manufacturing examples 1 to 3, and comparative manufacturing examples 1 to 4 and 6 to 8, was determined by molar calculation, assuming no change in liquid volume due to mixing.

[0280] <Calculated by [the ratio of the valence (mass) of the cations in the salt contained in the aqueous solution to the acidity of the raw zeolite]>

[0281] The acidity of the raw material zeolite used in the manufacture of the solid catalysts in Manufacturing Examples 1-3, and Comparative Manufacturing Examples 1-4 and 6-8, corresponds to the amount of material that the raw material zeolite can impart cation sites to. Furthermore, the cations (Rb) in the various salts (rubidium nitrate, sodium nitrate, potassium nitrate, cesium nitrate, or sodium hydroxide) contained in the rubidium nitrate aqueous solution prepared in Manufacturing Examples 1-3 and Comparative Manufacturing Example 6, the sodium nitrate aqueous solution prepared in Comparative Manufacturing Examples 1 and 7, the potassium nitrate aqueous solution prepared in Comparative Manufacturing Example 2, the cesium nitrate solution prepared in Comparative Manufacturing Example 3, the strontium nitrate aqueous solution prepared in Comparative Manufacturing Example 4, and the sodium hydroxide aqueous solution prepared in Comparative Manufacturing Example 8 (hereinafter, these are collectively referred to as "salt-containing aqueous solutions") were determined. + Na + K + Cs + 、or Sr 2+ The product of the valence of the cation and the amount of substance of the cation in the salt contained in the aqueous solution is calculated. Next, the ratio of the valence (mass) of the cation in the salt contained in the aqueous solution to the acidity of the raw zeolite is calculated [valence (mass) of the cation in the salt contained in the aqueous solution / acidity of the raw zeolite]. The results are shown in Tables 3-1 and 3-2 below.

[0282] Table 3-1

[0283]

[0284] Table 3-2

[0285]

[0286] (Example 1)

[0287] The solid catalyst obtained in Manufacturing Example 1 (hereinafter also referred to as "Rb") + In the presence of "replace MFI type zeolite", the decomposition of mixed plastics is carried out by the method shown below.

[0288] A mixture of 0.3 g of polyethylene (manufactured by Sigma-Aldrich, number average molecular weight 1,700, weight average molecular weight 4,000), 0.3 g of polypropylene (manufactured by Sigma-Aldrich, number average molecular weight 5,000, weight average molecular weight 12,000), 0.3 g of polystyrene (manufactured by Sigma-Aldrich, weight average molecular weight 35,000), and 0.2 g of the solid catalyst of Preparation Example 1 was placed in a quartz inner cylinder. The inner cylinder was then sealed together with nitrogen gas at atmospheric pressure in a high-temperature and high-pressure reaction vessel (Type 4790, SUS-316, 100 mL capacity, manufactured by Parr), and heated to an internal temperature of 450°C for 8 hours. After cooling, the gaseous products were recovered, and 10 mL of tetrahydrofuran (THF) (manufactured by Kanto Chemical Co., Ltd., a reagent for high-performance liquid chromatography, without stabilizer) was added to the residue. The mixture was thoroughly mixed at room temperature, and the solid components were separated by filtration and washed twice with a small amount of THF. Thus, a THF-soluble product (THF-soluble product) was extracted from the combined THF solution containing the filtrate and washings.

[0289] (Example 2)

[0290] Except that the solid catalyst of Manufacturing Example 1 in Example 1 was changed to the solid catalyst of Manufacturing Example 2 (hereinafter also referred to as "Na") + Except for those replacing MFI-type zeolite, the gaseous products and THF-soluble products were extracted using the same method as in Example 1.

[0291] (Example 3)

[0292] Except that the solid catalyst of Manufacturing Example 1 in Example 1 was changed to the solid catalyst of Manufacturing Example 3 (hereinafter also referred to as "Na") + Except for those replacing MFI-type zeolite, all other gaseous products and THF-soluble products were extracted using the same method as in Example 1.

[0293] (Comparative Example 1)

[0294] Except that the solid catalyst of manufacturing example 1 in Example 1 was changed to the solid catalyst of comparative manufacturing example 1 (hereinafter also referred to as "Na") + Except for those replacing MFI-type zeolite, all other gaseous products and THF-soluble products were extracted using the same method as in Example 1.

[0295] (Comparative Example 2)

[0296] Except that the solid catalyst of Manufacturing Example 1 in Example 1 was changed to Comparative Manufacturing Example 2 (hereinafter also referred to as "K"), +Except for the solid catalyst (which replaces MFI-type zeolite), the gaseous products and THF-soluble products were extracted using the same method as in Example 1.

[0297] (Comparative Example 3)

[0298] Except that the solid catalyst of manufacturing example 1 in Example 1 was changed to the solid catalyst of comparative manufacturing example 3 (hereinafter also referred to as "Cs") + Except for those replacing MFI-type zeolite, all other gaseous products and THF-soluble products were extracted using the same method as in Example 1.

[0299] (Comparative Example 4)

[0300] Except that the solid catalyst of manufacturing example 1 in Example 1 was changed to the solid catalyst of comparative manufacturing example 4 (hereinafter also referred to as "Sr") 2+ Except for those replacing MFI-type zeolite, all other gaseous products and THF-soluble products were extracted using the same method as in Example 1.

[0301] (Comparative Example 5)

[0302] Except for changing the solid catalyst of Manufacturing Example 1 in Example 1 to the solid catalyst (TS-1) of Comparative Manufacturing Example 5, the gaseous products and THF soluble products were extracted by the same method as in Example 1.

[0303] (Comparative Example 6)

[0304] Except for replacing the solid catalyst of Manufacturing Example 1 in Example 1 with the solid catalyst of Reference Manufacturing Example 1 (hereinafter also referred to as "unsubstituted MFI type zeolite"), the gaseous products and THF soluble products were extracted by the same method as in Example 1.

[0305] (Comparative Example 7)

[0306] Except that the solid catalyst of manufacturing example 1 in Example 1 was changed to the solid catalyst of comparative manufacturing example 6 (hereinafter also referred to as "Rb") + Except for FAU-type zeolite, all other gaseous products and THF-soluble products were extracted using the same method as in Example 1.

[0307] [Evaluation of the biodegradability of plastics]

[0308] To the gas products recovered in Examples 1 to 3 and Comparative Examples 1 to 7, 38 mg of cyclopentane (manufactured by Tokyo Chemical Industry Co., Ltd., reagent, purity: 98.0% or more) was added as an internal standard substance to prepare samples for analysis. In addition, 0.12 g of tert-butylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd., reagent, purity: 98.0% or more) was added to the THF-soluble products recovered in Example 1 and Comparative Examples 1 to 7 as an internal standard substance to prepare samples for analysis.

[0309] For these samples for analysis, a gas chromatography (GC) apparatus equipped with a flame ionization detector was used to perform analysis under the following analysis conditions, and each component was quantified based on the ratio of the peak area of each component to the internal standard substance. The results are shown in Tables 4-1 and 4-2 below.

[0310] <<GC Analysis Conditions for Gas Products>>

[0311] · Apparatus: Nexis GC-2030 (manufactured by Shimadzu Corporation)

[0312] · Column: Rt-Alumina BOND (diameter: 0.32 mm, length: 30 m, manufactured by Restek Corporation)

[0313] · Carrier gas type: Ar

[0314] · Carrier gas flow rate: 360 mL / min

[0315] · Injection temperature: 200 °C

[0316] · Sample injection volume: 1 mL

[0317] · Split ratio: 1 / 200

[0318] · Column temperature: The temperature increase process was set in the order of 120 °C (9 minutes) → temperature increase (10 °C / minute) → 200 °C (30 minutes).

[0319] · Detector: Flame ionization detector (FID)

[0320] · Detector temperature: 200 °C

[0321] <<GC Analysis Conditions for THF-Soluble Products>>

[0322] · Apparatus: Nexis GC-2030 (manufactured by Shimadzu Corporation)

[0323] · Column: DB-1 (diameter: 0.25 mm, length: 30 m, manufactured by Agilent Technology)

[0324] • Carrier gas type: He

[0325] • Carrier gas flow rate: 97 mL / min

[0326] • Injection temperature: 350℃

[0327] • Sample injection volume: 1 μL

[0328] • Flow split ratio: 1 / 50

[0329] • Column temperature: Set the heating process in the following order: 35℃ (10 minutes) → heating up (5℃ / minute) → 350℃ (10 minutes).

[0330] • Detector: Flame Ionization Detector (FID)

[0331] • Detector temperature: 350℃

[0332] Furthermore, in Tables 4-1 and 4-2 below, "4-carbon olefins" refers to 1-butene, cis-2-butene, trans-2-butene, and 2-methylpropene. "5-carbon olefins" refers to 1-pentene, cis-2-pentene, trans-2-pentene, 2-methyl-1-butene, and 2-methyl-2-butene. "Useful aromatics" refers to benzene, toluene, ethylbenzene, the three positional isomers of xylene (p-xylene, m-xylene, and o-xylene), styrene, and cumene. "Lower olefins" refers to olefins with 2 to 5 carbon atoms. "Useful components" refers to lower olefins and useful aromatics. Additionally, "O / P ratio" represents the ratio of "total yield (%) of 2- to 5-carbon olefin products / total yield (%) of 2- to 5-carbon paraffin products."

[0333] Table 4-1

[0334]

[0335] Table 4-2

[0336]

[0337] Based on the results in Tables 1, 4-1, and 4-2, among the cations predicted to perform well in the prediction model, those containing Rb... + The MFI-type zeolite yielded the best useful component yield and O / P ratio. Furthermore, its useful component yield and O / P ratio were higher than those predicted by the predictive model.

[0338] (Experimental Example 2: The effect of the molar ratio [SiO2 / Al2O3] of solid catalyst)

[0339] In addition to the solid catalyst (Na) from Comparative Example 1 of Comparative Preparation Example 1, +The MFI-type zeolite was replaced with the solid catalyst of Comparative Manufacturing Example 7 (hereinafter also referred to as "Na"). + Except for those replacing MFI-type zeolites, all gaseous products and THF-soluble products were extracted using the same method as in Comparative Example 1.

[0340] For the obtained gaseous products and THF-soluble products, the same method as used in evaluating the plastic decomposability in Examples 1 and Comparative Examples 1-7 was employed to quantify each component by the ratio of its peak area to that of the internal standard substance. The results compared with Comparative Example 1 are shown in Table 5 below.

[0341] Table 5

[0342]

[0343] (Experimental Example 3: The effect of nitrate aqueous solution in the treatment step)

[0344] In addition to the solid catalyst (Na) from Comparative Example 1 of Comparative Preparation Example 1, + The MFI-type zeolite was replaced with the solid catalyst of Comparative Manufacturing Example 8 (hereinafter also referred to as "Na"). + Except for those replacing MFI-type zeolites, all gaseous products and THF-soluble products were extracted using the same method as in Comparative Example 1.

[0345] For the obtained gaseous products and THF-soluble products, the same method as used in evaluating the plastic decomposability in Examples 1 and Comparative Examples 1-7 was employed to quantify each component by the ratio of its peak area to that of the internal standard substance. The results compared with Comparative Example 1 are shown in Table 6 below.

[0346] Table 6

[0347]

[0348] (Comparative Example 8)

[0349] Except for replacing the solid catalyst in Manufacturing Example 1 with the solid catalyst (zeolite a) in Reference Manufacturing Example 1, the gaseous products and THF soluble products were extracted using the same method as in Example 1.

[0350] (Example 4)

[0351] Except for changing the addition of 0.2g of the solid catalyst from Manufacturing Example 1 to 0.3g of polyethylene, 0.3g of polypropylene and 0.3g of polystyrene in Example 1 to 0.135g of the solid catalyst from Manufacturing Example 1 to 0.3g of polyethylene, 3g of polypropylene and 0.3g of polystyrene, the gaseous products and THF-soluble products were extracted using the same method as in Example 1.

[0352] (Example 5)

[0353] Except for changing the addition of 0.2g of the solid catalyst from Manufacturing Example 1 to 0.3g of polyethylene, 0.3g of polypropylene and 0.3g of polystyrene in Example 1 to 0.225g of the solid catalyst from Manufacturing Example 1 to 0.3g of polyethylene, 3g of polypropylene and 0.3g of polystyrene, the gaseous products and THF-soluble products were extracted using the same method as in Example 1.

[0354] [Evaluation of the biodegradability of plastics]

[0355] The analytical samples of the gaseous products and THF-soluble products recovered in Comparative Examples 8, 4, and 5 were prepared using the same method as for evaluating the plasticity of Examples 1-3 and Comparative Examples 1-7. Analysis was performed using a gas chromatography (GC) apparatus equipped with a flame ionization detector under the aforementioned analytical conditions. Each component was quantified by the ratio of its peak area to that of an internal standard. The results are shown in Table 7 below. Furthermore, the results of Example 1 are also recorded in Table 7 below.

[0356] Furthermore, in Table 7 below, the “amount added [phr]” for solid catalyst indicates the number of parts by mass of solid catalyst added when the total mass of polyethylene, polypropylene and polystyrene (0.9 g) is taken as 100 parts by mass.

[0357] Table 7

[0358]

[0359] As described above, the present invention has been explained based on specific embodiments, manufacturing examples, and examples. However, these embodiments, manufacturing examples, and examples are merely illustrative and the present invention is not limited to them. The above embodiments can be implemented in various other ways, and various combinations, omissions, substitutions, additions, and modifications can be made without departing from the spirit of the invention. These embodiments and their variations are all included in the scope and spirit of the invention, as well as within the scope of the invention as described in the claims and their equivalents.

[0360] This international application claims priority based on Japanese Patent Application No. 2023-131007, filed on August 10, 2023, the contents of which are incorporated herein by reference.

[0361] Symbol Explanation

[0362] 1: Information Processing System

[0363] 10: Design support device

[0364] 11: Learning Device

[0365] 12: User Terminal

[0366] 28: Parameter Generation Department

[0367] 30: Forecasting Department

[0368] 32: Candidate Output Section

[0369] 52: Learning to obtain parts using datasets

[0370] 54: Study Department

Claims

1. A method for manufacturing an olefin-containing composition, comprising the step of decomposing a plastic in the presence of zeolite to produce an olefin-containing composition containing an olefin having 2 to 5 carbon atoms, and The zeolite contains Rb. + MFI type zeolite.

2. The method for manufacturing the olefin-containing composition as described in claim 1, wherein, The plastic is a polyolefin.

3. The method for manufacturing the olefin-containing composition as described in claim 1, wherein, The plastic contains at least one selected from the group consisting of polyethylene, polypropylene, and polystyrene.

4. The method for manufacturing the olefin-containing composition as described in claim 1 or 2, wherein, The temperature at which the plastic is decomposed is between 300°C and 1,100°C.

5. The method for manufacturing an olefin-containing composition as described in claim 1 or 2, wherein, The containing Rb + The molar ratio of SiO2 to Al2O3 in MFI-type zeolites, i.e., SiO2 / Al2O3, is between 10 and 10,000.

6. The method for manufacturing an olefin-containing composition as described in claim 1 or 2, wherein, The containing Rb + The BET specific surface area of ​​MFI type zeolite is 100 m². 2 / g or more 1,000m 2 / g or less.

7. The method for manufacturing the olefin-containing composition as described in claim 1, further comprising: The mixing steps for obtaining a mixture of MFI-type zeolite and a liquid containing a rubidium compound, and The mixture was calcined in the atmosphere to obtain the Rb-containing solution. + The calcination steps of MFI type zeolite.

8. The method for manufacturing the olefin-containing composition as described in claim 7, wherein, In the mixing step, When the mass of the MFI-type zeolite is set as x (g), the molar ratio of SiO2 to Al2O3 of the MFI-type zeolite, i.e. SiO2 / Al2O3, is set as y, and the number of moles of the rubidium compound is set as z (mmol), 1≤yz / x≤10,000 is satisfied.

9. The method for manufacturing the olefin-containing composition as described in claim 7, wherein, The MFI type zeolite contains H + MFI type zeolite.

10. A catalyst for manufacturing an olefin-containing composition, characterized in that, A catalyst for the manufacture of olefin-containing compositions containing olefins having 2 to 5 carbon atoms. It contains Rb + MFI type zeolite.

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