WO2019155607A1 - Method for producing light olefin - Google Patents

Method for producing light olefin Download PDF

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Publication number
WO2019155607A1
WO2019155607A1 PCT/JP2018/004616 JP2018004616W WO2019155607A1 WO 2019155607 A1 WO2019155607 A1 WO 2019155607A1 JP 2018004616 W JP2018004616 W JP 2018004616W WO 2019155607 A1 WO2019155607 A1 WO 2019155607A1
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catalyst
ynu
zeolite
methanol
reaction
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PCT/JP2018/004616
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French (fr)
Japanese (ja)
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範立 椿
嘉治 米山
中村　典彦
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Ｔｏｙｏ Ｔｉｒｅ株式会社
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Priority to JP2019570243A priority Critical patent/JPWO2019155607A1/en
Priority to PCT/JP2018/004616 priority patent/WO2019155607A1/en
Publication of WO2019155607A1 publication Critical patent/WO2019155607A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/08—Alkenes with four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • Embodiment of this invention is related with the manufacturing method of a light olefin. More specifically, the present invention relates to a method for producing light olefins such as ethylene, propylene and butene from methanol.
  • zeolite As a catalyst for this reaction, zeolite is used as a solid acid, but catalyst deactivation due to coke formation during the reaction is a problem, and development of a catalyst having a long life is desired.
  • Non-Patent Document 1 discloses a Hi-SAPO-34 catalyst having mesopores as an MTO reaction catalyst.
  • Hi-SAPO-34 catalyst is prepared by co-existing multi-walled carbon nanotubes in the preparation gel of SAPO-34 zeolite catalyst, preparing a mixture of carbon nanotubes and SAPO-34 by hydrothermal synthesis method, and then burning the mixture Is done. Further, a catalyst obtained by impregnating a Hi-SAPO-34 catalyst with Ni or Co is also disclosed. These catalysts are used to convert methanol to light olefins (MTO reaction), and ethylene, propylene, and butene are generated in any catalyst. However, the deactivation of these catalysts is fast and almost no propylene is produced after 200 minutes. In this document, expensive carbon nanotubes are used, and it is required to perform the MTO reaction with a catalyst using a cheaper raw material.
  • MTO reaction light olefins
  • Non-Patent Document 2 discloses the preparation method and structure of YNU-5, which is a novel zeolite, and the catalyst can be used in a method for converting dimethyl ether to light olefin (DTO reaction). It is disclosed.
  • Non-Patent Document 2 describes the use of YNU-5 zeolite as a catalyst for the synthesis of light olefins, but it is used for the DTO reaction using dimethyl ether as a raw material and uses methanol as a raw material. It is not described for use in the MTO reaction. In general, it is considered that the MTO reaction produces much more water as a by-product than the DTO reaction and causes much damage (ie, deactivation) to the catalyst.
  • An object of the present invention is to provide a method capable of producing light olefins from methanol at a high conversion rate over a long period of time.
  • the method for producing a light olefin according to an embodiment of the present invention includes converting methanol into a light olefin in the presence of a catalyst containing YNU-5 zeolite.
  • a light olefin can be synthesized from methanol at a high conversion rate over a long period of time.
  • the graph which shows the XRD analysis result of YNU-5 catalyst in 1st Example Conceptual diagram of the reactor used in the examples Graph showing the methanol conversion rate at a flow rate of 22 mL / min in the first example. Graph showing the methanol conversion rate at a flow rate of 33 mL / min in the first example. The graph which shows the methanol conversion in 2nd Example
  • a catalyst containing YNU-5 zeolite (hereinafter sometimes referred to as YNU-5 catalyst) is used as the solid acid catalyst in the MTO reaction for synthesizing light olefin from methanol. It is characterized by using.
  • YNU-5 zeolite has a crystal structure of 12-membered large pores extending in the x-axis direction, 12-membered large pores extending in the y-axis direction, and a pair of 8-membered small rings extending in the z-axis direction. It is a microporous aluminosilicate zeolite having a three-dimensional pore structure composed of pores and having an independent 8-membered small pore different from the three-dimensional pore structure.
  • the large pores extending in the x-axis direction and the large pores extending in the y-axis direction extend in two dimensions while intersecting the passages of the large pores, and a pair of small pores extending in parallel with each other Connected vertically to the hole passage.
  • an independent 8-membered small pore extends in the z-axis direction to form a one-dimensional passage that is not connected to the three-dimensional pore structure.
  • a light olefin can be synthesized from methanol at a high conversion rate over a long period of time. The reason is not intended to be limited by this, but is considered as follows.
  • Coke which is a cause of deactivation of the conventional zeolite catalyst in the MTO reaction, is considered to be formed due to the high acid strength of the acid sites in the zeolite pore inlet and the pore and the size of the pore diameter. . Therefore, in order to suppress coke formation, it is considered effective to control the acid strength of the zeolite catalyst or to have a large pore diameter that promotes mass transfer. In this regard, YNU-5 zeolite is considered to be able to suppress coke formation mainly by promoting mass transfer due to the size of the pore diameter.
  • YNU-5 zeolite promotes mass transfer in the 12-membered large pores, provides a high surface area reaction field in the 8-membered small pores, and suppresses the production of olefins having 5 or more carbon atoms. It is thought that the reaction is promoted. Therefore, it is considered that coke formation is suppressed and the MTO reaction is promoted to extend the life.
  • the molar ratio Si / Al between Si and Al in the YNU-5 zeolite is not particularly limited, and may be, for example, 5 to 2000 or 8 to 200 from the viewpoint of controlling the acid strength to suppress coke formation. .
  • the BET specific surface area, pore volume and average pore diameter of YNU-5 zeolite are not particularly limited.
  • the BET specific surface area is more preferably 200 to 800 m 2 / g.
  • it is 400 to 500 m 2 / g.
  • the pore volume is preferably 0.1 to 1.0 cm 3 / g, more preferably 0.2 to 0.4 cm 3 / g.
  • the average pore diameter is preferably 0.7 to 2.0 nm, more preferably 0.9 to 1.6 nm.
  • YNU-5 zeolite may carry a metal.
  • the metal is not particularly limited as long as it can enhance the catalytic function of YNU-5 zeolite.
  • metals that is, metal elements include transition metals (for example, Group 8 elements such as Fe, Group 9 elements such as Co, Group 10 elements such as Ni), Group 12 elements such as Zn, La, Ce, and the like. And rare earth elements.
  • transition metals for example, Group 8 elements such as Fe, Group 9 elements such as Co, Group 10 elements such as Ni
  • Group 12 elements such as Zn, La, Ce, and the like.
  • rare earth elements rare earth elements.
  • the form of the supported metal may be a single metal or a compound containing a metal.
  • the metal-containing compound include nitrates, oxides, chlorides, sulfates, and the like, and nitrate hydrates are preferable.
  • the method for supporting the metal is not particularly limited, and for example, it can be supported by a known method such as an impregnation method or an ion exchange method. It may be introduced into the YNU-5 zeolite after calcination, or may be added and introduced during the synthesis of YNU-5 zeolite by hydrothermal synthesis.
  • the amount of the metal element introduced is not particularly limited, and may be, for example, 0.1 to 10% by mass, 1 to 10% by mass, or 3 to 8% by mass with respect to the mass of YNU-5 zeolite.
  • the catalyst other catalysts may be used in combination with the YNU-5 catalyst.
  • the other catalyst include zeolite catalysts such as a SAPO-5 catalyst, a SAPO-18 catalyst, a SAPO-34 catalyst, a DNL-6 catalyst, and an SSZ-13 catalyst.
  • a combination may be used in combination with the YNU-5 catalyst.
  • methanol is converted to light olefin in the presence of YNU-5 catalyst.
  • a raw material containing methanol may be brought into contact with the YNU-5 catalyst.
  • Methanol is not particularly limited.
  • methanol produced using natural gas and carbon dioxide as raw materials may be used.
  • saturated hydrocarbons that exist in a gaseous state under MTO reaction conditions such as hexane and heptane, may be added to the above raw materials in order to calculate the conversion rate.
  • the method for bringing methanol into contact with the YNU-5 catalyst is not particularly limited as long as it is a method capable of converting methanol into light olefin in the presence of the YNU-5 catalyst.
  • a gas containing methanol as a gas is included.
  • the stream may be fed to a catalyst bed containing YNU-5 catalyst.
  • the gas flow may be supplied as a mixed gas of an inert gas such as nitrogen or argon and methanol.
  • a YNU-5 catalyst diluted by adding inert inorganic particles (diluent) such as quartz sand to the YNU-5 catalyst may be used as the catalyst bed.
  • the amount of inorganic particles added is not particularly limited, and may be, for example, 2 to 5 times the mass of the YNU-5 catalyst.
  • the reaction temperature of the MTO reaction is not particularly limited as long as it is a temperature at which methanol can be converted into light olefin, and may be, for example, 350 to 450 ° C. or 400 to 450 ° C.
  • the reaction method may be a continuous flow method or a batch method.
  • the gas space velocity (GHSV) is not particularly limited, and may be, for example, 1000 to 2500 mLg cat ⁇ 1 h ⁇ 1 or 1300 to 2000 mLg cat ⁇ 1 h ⁇ 1 per 1 g of YNU-5 catalyst.
  • GHSV gas space velocity
  • limiting in particular as a reaction format Any of a fixed bed type, a moving bed type, and a fluidized bed type may be sufficient.
  • the light olefin produced in this embodiment is an olefin having 2 to 4 carbon atoms (ie, alkene), and at least one olefin selected from the group consisting of ethylene, propylene and butene is produced.
  • the product preferably contains butene.
  • the YNU-5 catalyst is suitable as a method for producing butene because the selectivity of butene in the product is higher than that of the conventional zeolite catalyst.
  • the MTO reaction test was conducted using a fixed bed quartz glass reactor at normal pressure (0.1 MPa).
  • the conceptual diagram of the reaction apparatus is as shown in FIG. 2, and a catalyst bed is provided in the middle of the flow path of a tubular reactor having an inner diameter of 6 mm.
  • the catalyst bed was fixed by packing quartz wool on both sides.
  • a heater for heating the catalyst bed is provided on the outer circumference of the reactor, and a thermocouple thermometer for measuring the internal temperature of the catalyst bed and a reaction temperature control thermocouple for measuring the outer wall temperature of the reactor, It was configured to control the output of the heater.
  • Example 1 a catalyst bed was formed by mixing 1.0 g of H-type YNU-5 zeolite and 3.0 g of quartz sand and mixing them in a reactor. Methanol: hexane is mixed as a reaction gas at a ratio of 90: 1 (molar ratio), 0.005 mL / min of the reaction raw material (liquid mixture) is vaporized at 300 ° C., and then circulated from one end of the reactor into the reactor. I let you.
  • 33 mL / min reaction gas gas space velocity: 1980 mLg cat ⁇ 1 h ⁇ 1 .
  • the reaction was performed by raising the temperature to 400 ° C. in 80 minutes. After the temperature increase was completed, the product was measured online by gas chromatography (“GC-2014” manufactured by Shimadzu Corporation, FID: Porapak Q column) every hour, and the reaction was performed for 7 hours.
  • Example 2 instead of 1.0 g of H-type YNU-5 zeolite, a mixture of 0.4 g of H-type YNU-5 zeolite, 0.3 g of SAPO-5 zeolite and 0.3 g of SAPO-18 zeolite was used. The others were reacted in the same manner as in Example 1.
  • Comparative Example 1 1.0 g of SAPO-5 zeolite was used instead of 1.0 g of H-type YNU-5 zeolite, and the others were reacted in the same manner as in Example 1.
  • Comparative Example 2 1.0 g of SAPO-18 zeolite was used instead of 1.0 g of H-type YNU-5 zeolite, and the others were reacted in the same manner as in Example 1.
  • FIG. 3 shows the methanol conversion rate at a flow rate of 22 mL / min
  • FIG. 4 shows the methanol conversion rate at a flow rate of 33 mL / min. From FIG. 3 and FIG. 4, in all of Examples 1 and 2 and Comparative Examples 1 and 2, the methanol conversion was 80% or more, indicating high catalytic activity. It was also found that even after 7 hours, the methanol conversion rate remained high and the catalyst life was long.
  • Example 1 using YNU-5 catalyst always showed 100% methanol conversion.
  • Comparative Example 1 using the SAPO-5 catalyst the methanol conversion rate was slightly unstable for 2 hours after the start of the reaction, but after that, it became stable and reached 100%.
  • Example 2 In Comparative Example 2 using the SAPO-18 catalyst, although high catalytic activity was exhibited, the methanol conversion was unstable. Further, in Example 2 using the mixture containing YNU-5 zeolite (Mixture), the methanol conversion was stably 100% as in Example 1 (see FIG. 4).
  • the average methanol conversion rate in the 7-hour reaction and the average selectivity of each product in the 7-hour reaction are shown in Table 2 (flow rate 22 mL / min) and Table 3 (flow rate 33 mL / min), respectively. Show. From Tables 2 and 3, in Examples 1 and 2 using YNU-5 catalyst, the average methanol conversion was higher than in Comparative Examples 1 and 2. Further, the methane selectivity at all catalysts is low, had higher light olefins (C 2 H 4, C 3 H 6, C 4 H 8) selectivity. In particular, in Examples 1 and 2, the selectivity for butene was higher than in Comparative Examples 1 and 2, and therefore, it was found that the MTO reaction using YNU-5 catalyst was more effective as a method for producing butene. .
  • the obtained YNU-5Fe catalyst was pretreated at a temperature of 200 ° C. for 2 hours, and the BET specific surface area, pore volume and average pore diameter were measured in the same manner as in Example 1.
  • the specific surface area of the YNU-5Fe catalyst was 295.5 m 2 / g
  • the pore volume was 0.22 cm 3 / g
  • the average pore diameter was 1.51 nm
  • the specific surface area and pore volume were It was lower than the YNU-5 catalyst of the first example.
  • the YNU-5Fe catalyst was subjected to a catalyst performance evaluation test by MTO reaction.
  • the flow rate of nitrogen gas was only 33 mL / min (reaction gas gas space velocity: 1980 mLg cat ⁇ 1 h ⁇ 1 ), and the others were performed in the same manner as in the first example.
  • Example 3 using the YNU-5Fe catalyst the methanol conversion was maintained at almost 100% as in Example 1 using the YNU-5 catalyst not supporting metal. It was found to have a long catalyst life.
  • Table 4 below shows the average methanol conversion in the 7-hour reaction and the average selectivity of each product in the 7-hour reaction.
  • the selectivity for butene was higher than in Example 1 using the YNU-5 catalyst not supporting the metal, so that the metal was supported on the YNU-5 zeolite. By doing so, it turned out that it is more effective as a manufacturing method of butene.
  • light olefins can be synthesized from methanol over a long period of time with high methanol conversion and high olefin selectivity. Therefore, a light olefin useful as an industrial raw material can be efficiently produced from natural gas containing shale gas by an MTO reaction.

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Abstract

A method for producing light olefin according to one embodiment of the present invention converts methanol into light olefin in the presence of a catalyst that contains YNU-5 zeolite. The YNU-5 zeolite may be loaded with a metal. The light olefin includes at least one substance that is selected from the group consisting of ethylene, propylene and butene. According to the present invention, light olefin is able to be produced from methanol with a high conversion rate over a long period of time.

Description

軽質オレフィンの製造方法Production method of light olefin
　本発明の実施形態は、軽質オレフィンの製造方法に関する。より詳細には、メタノールからエチレン、プロピレン、ブテン等の軽質オレフィンを製造する方法に関するものである。 Embodiment of this invention is related with the manufacturing method of a light olefin. More specifically, the present invention relates to a method for producing light olefins such as ethylene, propylene and butene from methanol.
　従来、軽質オレフィン（低級オレフィンとも称される。）は主にナフサのクラッキングから得られている。近年その需要が高まっているため、石油以外の原料からの軽質オレフィンの合成が求められている。その中で、メタノールから軽質オレフィンへの変換反応（ＭＴＯ反応）が代替製造法として注目されている。天然ガスを原料とするメタノールを利用できるためである。特に近年開発されたシェールガス（天然ガス）は価格が安いことから、低コストで軽質オレフィンの合成が可能になるとして、高い性能を持つＭＴＯ反応触媒の開発が望まれている。 Conventionally, light olefins (also referred to as lower olefins) have been obtained mainly from naphtha cracking. In recent years, since the demand has increased, synthesis of light olefins from raw materials other than petroleum has been demanded. Among them, a conversion reaction from methanol to light olefin (MTO reaction) has attracted attention as an alternative production method. This is because methanol from natural gas can be used. In particular, since shale gas (natural gas) developed in recent years is inexpensive, it is desired to develop an MTO reaction catalyst having high performance, because it enables synthesis of light olefins at low cost.
　この反応の触媒としては、固体酸としてゼオライトが用いられているが、反応中でのコーク生成による触媒失活が問題となっており、長寿命を持つ触媒の開発が望まれている。 As a catalyst for this reaction, zeolite is used as a solid acid, but catalyst deactivation due to coke formation during the reaction is a problem, and development of a catalyst having a long life is desired.
　非特許文献１には、ＭＴＯ反応触媒として、メソ細孔を持つＨｉ－ＳＡＰＯ－３４触媒が開示されている。Ｈｉ－ＳＡＰＯ－３４触媒は、ＳＡＰＯ－３４ゼオライト触媒の調製ゲルに多層膜カーボンナノチューブを共存させ、水熱合成法によりカーボンナノチューブとＳＡＰＯ－３４の混合物を調製した後、混合物を燃焼させることにより調製される。また、Ｈｉ－ＳＡＰＯ－３４触媒にＮｉもしくはＣｏを含浸させた触媒も開示されている。そして、これらの触媒を用いて、メタノールから軽質オレフィンへの変換（ＭＴＯ反応）を行っており、いずれの触媒もエチレン、プロピレン及びブテンが生成している。しかしながら、これらの触媒の失活は早く、２００分後にはプロピレンはほとんど生成していない。また、この文献では、高価なカーボンナノチューブを用いており、より安価な原料を用いた触媒でＭＴＯ反応を行うことが求められる。 Non-Patent Document 1 discloses a Hi-SAPO-34 catalyst having mesopores as an MTO reaction catalyst. Hi-SAPO-34 catalyst is prepared by co-existing multi-walled carbon nanotubes in the preparation gel of SAPO-34 zeolite catalyst, preparing a mixture of carbon nanotubes and SAPO-34 by hydrothermal synthesis method, and then burning the mixture Is done. Further, a catalyst obtained by impregnating a Hi-SAPO-34 catalyst with Ni or Co is also disclosed. These catalysts are used to convert methanol to light olefins (MTO reaction), and ethylene, propylene, and butene are generated in any catalyst. However, the deactivation of these catalysts is fast and almost no propylene is produced after 200 minutes. In this document, expensive carbon nanotubes are used, and it is required to perform the MTO reaction with a catalyst using a cheaper raw material.
　一方、非特許文献２には、新規なゼオライトであるＹＮＵ－５についてその調製法と構造が開示されており、また、この触媒をジメチルエーテルから軽質オレフィンに変換する方法（ＤＴＯ反応）に用いることが開示されている。このように非特許文献２には、ＹＮＵ－５ゼオライトを軽質オレフィンの合成用触媒に用いることが記載されているが、ジメルエーテルを原料とするＤＴＯ反応に用いるものであり、メタノールを原料とするＭＴＯ反応に用いることは記載されていない。一般に、ＭＴＯ反応は、ＤＴＯ反応より遥かに多い水を副生し、触媒に与えられるダメージ（即ち、失活）が多いと考えられている。水によるルイス酸点の被毒、及び、水による脱アルミニウム（ゼオライトの永久失活）などはいずれも深刻な難関である。このように両者は全く別の反応であり、ＤＴＯ反応で使えるゼオライトがＭＴＯ反応に使えないケースが、多くみられるのが実情である。 On the other hand, Non-Patent Document 2 discloses the preparation method and structure of YNU-5, which is a novel zeolite, and the catalyst can be used in a method for converting dimethyl ether to light olefin (DTO reaction). It is disclosed. Thus, Non-Patent Document 2 describes the use of YNU-5 zeolite as a catalyst for the synthesis of light olefins, but it is used for the DTO reaction using dimethyl ether as a raw material and uses methanol as a raw material. It is not described for use in the MTO reaction. In general, it is considered that the MTO reaction produces much more water as a by-product than the DTO reaction and causes much damage (ie, deactivation) to the catalyst. The poisoning of Lewis acid sites with water and dealumination with water (permanent deactivation of zeolite) are all serious difficulties. Thus, the two are completely different reactions, and in reality, there are many cases where zeolite that can be used in the DTO reaction cannot be used in the MTO reaction.
　本発明の実施形態は、メタノールから高い転化率でかつ長時間にわたって軽質オレフィンを製造することができる方法を提供することを目的とする。 An object of the present invention is to provide a method capable of producing light olefins from methanol at a high conversion rate over a long period of time.
　本発明の実施形態に係る軽質オレフィンの製造方法は、ＹＮＵ－５ゼオライトを含む触媒の存在下でメタノールを軽質オレフィンに変換することを含むものである。 The method for producing a light olefin according to an embodiment of the present invention includes converting methanol into a light olefin in the presence of a catalyst containing YNU-5 zeolite.
　本実施形態によれば、メタノールから高い転化率でかつ長時間にわたって軽質オレフィンを合成することができる。 According to this embodiment, a light olefin can be synthesized from methanol at a high conversion rate over a long period of time.
第１実施例におけるＹＮＵ－５触媒のＸＲＤ分析結果を示すグラフThe graph which shows the XRD analysis result of YNU-5 catalyst in 1st Example 実施例で用いた反応装置の概念図Conceptual diagram of the reactor used in the examples 第１実施例の流速２２ｍＬ／ｍｉｎでのメタノール転化率を示すグラフGraph showing the methanol conversion rate at a flow rate of 22 mL / min in the first example. 第１実施例の流速３３ｍＬ／ｍｉｎでのメタノール転化率を示すグラフGraph showing the methanol conversion rate at a flow rate of 33 mL / min in the first example. 第２実施例におけるメタノール転化率を示すグラフThe graph which shows the methanol conversion in 2nd Example
　本実施形態に係る軽質オレフィンの製造方法は、メタノールから軽質オレフィンを合成するＭＴＯ反応において、その固体酸触媒として、ＹＮＵ－５ゼオライトを含む触媒（以下、ＹＮＵ－５触媒ということがある。）を用いることを特徴とする。 In the light olefin production method according to the present embodiment, a catalyst containing YNU-5 zeolite (hereinafter sometimes referred to as YNU-5 catalyst) is used as the solid acid catalyst in the MTO reaction for synthesizing light olefin from methanol. It is characterized by using.
　ＹＮＵ－５ゼオライトは、その結晶構造として、ｘ軸方向に延びる１２員環の大細孔とｙ軸方向に延びる１２員環の大細孔とｚ軸方向に延びる一対の８員環の小細孔とからなる三次元細孔構造を有するとともに、該三次元細孔構造とは別の独立した８員環の小細孔を持つ、ミクロ多孔性のアルミノシリケートゼオライトである。ｘ軸方向に延びる大細孔とｙ軸方向に延びる大細孔により、大細孔の通路が交差しながら二次元に延びており、互いに平行に並んで延びる一対の小細孔がこの大細孔の通路に垂直に接続されている。また、独立した８員環の小細孔がｚ軸方向に延びており、上記三次元細孔構造とは接続されていない一次元の通路を形成している。ＹＮＵ－５ゼオライトについては、上記非特許文献２にその調製法及び構造が詳細に記載されており、該非特許文献２の内容を参照によりここに取り込む。 YNU-5 zeolite has a crystal structure of 12-membered large pores extending in the x-axis direction, 12-membered large pores extending in the y-axis direction, and a pair of 8-membered small rings extending in the z-axis direction. It is a microporous aluminosilicate zeolite having a three-dimensional pore structure composed of pores and having an independent 8-membered small pore different from the three-dimensional pore structure. The large pores extending in the x-axis direction and the large pores extending in the y-axis direction extend in two dimensions while intersecting the passages of the large pores, and a pair of small pores extending in parallel with each other Connected vertically to the hole passage. In addition, an independent 8-membered small pore extends in the z-axis direction to form a one-dimensional passage that is not connected to the three-dimensional pore structure. The preparation method and structure of YNU-5 zeolite are described in detail in Non-Patent Document 2, and the contents of Non-Patent Document 2 are incorporated herein by reference.
　このような特異な空間構造を持つＹＮＵ－５ゼオライトをＭＴＯ反応の触媒として用いることにより、メタノールから高い転化率でかつ長時間にわたって軽質オレフィンを合成することができる。その理由は、これにより限定されることを意図するものではないが、次のように考えられる。 By using YNU-5 zeolite having such a unique spatial structure as a catalyst for the MTO reaction, a light olefin can be synthesized from methanol at a high conversion rate over a long period of time. The reason is not intended to be limited by this, but is considered as follows.
　ＭＴＯ反応における従来のゼオライト触媒の失活の要因であるコークは、ゼオライト細孔入り口と細孔中における酸点の酸強度の高さと、細孔径の大きさとが要因となり、形成されると考えられる。そのため、コーク形成を抑制するためには、ゼオライト触媒の酸強度を制御したり、物質移動を促進する大きな細孔径を持たせたりすることが有効であると考えられる。この点に関し、ＹＮＵ－５ゼオライトは、主として細孔径の大きさによる物質移動促進によりコーク形成を抑制することができると考えられる。すなわち、ＹＮＵ－５ゼオライトであると、１２員環の大細孔において物質移動が促進されるとともに、８員環の小細孔中において高表面積反応場の提供および炭素数５以上のオレフィン生成抑制により反応が促進されると考えられる。そのため、コーク形成を抑制してＭＴＯ反応を促進し、長寿命化されると考えられる。 Coke, which is a cause of deactivation of the conventional zeolite catalyst in the MTO reaction, is considered to be formed due to the high acid strength of the acid sites in the zeolite pore inlet and the pore and the size of the pore diameter. . Therefore, in order to suppress coke formation, it is considered effective to control the acid strength of the zeolite catalyst or to have a large pore diameter that promotes mass transfer. In this regard, YNU-5 zeolite is considered to be able to suppress coke formation mainly by promoting mass transfer due to the size of the pore diameter. That is, YNU-5 zeolite promotes mass transfer in the 12-membered large pores, provides a high surface area reaction field in the 8-membered small pores, and suppresses the production of olefins having 5 or more carbon atoms. It is thought that the reaction is promoted. Therefore, it is considered that coke formation is suppressed and the MTO reaction is promoted to extend the life.
　ＹＮＵ－５ゼオライトにおけるＳｉとＡｌとのモル比Ｓｉ／Ａｌについては、特に限定されず、例えば、酸強度を制御してコーク形成を抑制する観点から、５～２０００でもよく、８～２００でもよい。 The molar ratio Si / Al between Si and Al in the YNU-5 zeolite is not particularly limited, and may be, for example, 5 to 2000 or 8 to 200 from the viewpoint of controlling the acid strength to suppress coke formation. .
　ＹＮＵ－５ゼオライトのＢＥＴ比表面積、細孔容積及び平均細孔径は特に限定されないが、例えばコーク形成を抑制し転化率を高める観点から、ＢＥＴ比表面積は２００～８００ｍ２／ｇであることがより好ましく、より好ましくは４００～５００ｍ２／ｇである。細孔容積は０．１～１．０ｃｍ３／ｇであることが好ましく、より好ましくは０．２～０．４ｃｍ３／ｇである。平均細孔径は０．７～２．０ｎｍであることが好ましく、より好ましくは０．９～１．６ｎｍである。 The BET specific surface area, pore volume and average pore diameter of YNU-5 zeolite are not particularly limited. For example, from the viewpoint of suppressing coke formation and increasing the conversion rate, the BET specific surface area is more preferably 200 to 800 m 2 / g. Preferably, it is 400 to 500 m 2 / g. The pore volume is preferably 0.1 to 1.0 cm 3 / g, more preferably 0.2 to 0.4 cm 3 / g. The average pore diameter is preferably 0.7 to 2.0 nm, more preferably 0.9 to 1.6 nm.
　ＹＮＵ－５ゼオライトには金属を担持させてもよい。金属としては、ＹＮＵ－５ゼオライトの触媒機能を高めることができるものであれば特に限定されない。金属、即ち金属元素としては、遷移金属（例えば、Ｆｅなどの第８族元素、Ｃｏなどの第９族元素、Ｎｉなどの第１０族元素など）、Ｚｎなどの第１２族元素、Ｌａ、Ｃｅなどの希土類元素などが挙げられる。これらのうち、Ｆｅ、Ｃｏ、Ｎｉ、Ｚｎ、Ｌａ及びＣｅからなる群から選択される少なくとも１種の金属が好ましく、より好ましくはＦｅである。 YNU-5 zeolite may carry a metal. The metal is not particularly limited as long as it can enhance the catalytic function of YNU-5 zeolite. Examples of metals, that is, metal elements include transition metals (for example, Group 8 elements such as Fe, Group 9 elements such as Co, Group 10 elements such as Ni), Group 12 elements such as Zn, La, Ce, and the like. And rare earth elements. Among these, at least one metal selected from the group consisting of Fe, Co, Ni, Zn, La, and Ce is preferable, and Fe is more preferable.
　担持する金属の形態としては、金属単体でもよく、金属を含む化合物でもよい。金属を含む化合物としては、例えば、硝酸塩、酸化物、塩化物、硫酸塩などが挙げられ、好ましくは硝酸塩水和物である。金属を担持する方法は、特に限定されず、例えば、含浸法やイオン交換法などの公知の方法により担持させることができる。焼成後のＹＮＵ－５ゼオライトに対して導入してもよく、水熱合成によるＹＮＵ－５ゼオライトの合成時に添加して導入してもよい。 The form of the supported metal may be a single metal or a compound containing a metal. Examples of the metal-containing compound include nitrates, oxides, chlorides, sulfates, and the like, and nitrate hydrates are preferable. The method for supporting the metal is not particularly limited, and for example, it can be supported by a known method such as an impregnation method or an ion exchange method. It may be introduced into the YNU-5 zeolite after calcination, or may be added and introduced during the synthesis of YNU-5 zeolite by hydrothermal synthesis.
　金属元素の導入量は、特に限定されず、例えば、ＹＮＵ－５ゼオライトの質量に対して、０．１～１０質量％でもよく、１～１０質量％でもよく、３～８質量％でもよい。 The amount of the metal element introduced is not particularly limited, and may be, for example, 0.1 to 10% by mass, 1 to 10% by mass, or 3 to 8% by mass with respect to the mass of YNU-5 zeolite.
　触媒としては、ＹＮＵ－５触媒とともに、他の触媒を併用してもよい。他の触媒としては、例えば、ＳＡＰＯ－５触媒、ＳＡＰＯ－１８触媒、ＳＡＰＯ－３４触媒、ＤＮＬ－６触媒、ＳＳＺ－１３触媒などのゼオライト触媒が挙げられ、これらはいずれか１種又は２種以上組み合わせて、ＹＮＵ－５触媒と併用してもよい。 As the catalyst, other catalysts may be used in combination with the YNU-5 catalyst. Examples of the other catalyst include zeolite catalysts such as a SAPO-5 catalyst, a SAPO-18 catalyst, a SAPO-34 catalyst, a DNL-6 catalyst, and an SSZ-13 catalyst. A combination may be used in combination with the YNU-5 catalyst.
　本実施形態では、ＹＮＵ－５触媒の存在下でメタノールを軽質オレフィンに変換する。そのためには、メタノールを含む原料をＹＮＵ－５触媒に接触させればよい。 In this embodiment, methanol is converted to light olefin in the presence of YNU-5 catalyst. For this purpose, a raw material containing methanol may be brought into contact with the YNU-5 catalyst.
　メタノールとしては、特に限定するものではないが、例えば天然ガスと二酸化炭素を原料として製造されたメタノールを用いてもよい。これにより、従来の石油由来ナフサを原料として製造される軽質オレフィンの代替製造法になるとともに、二酸化炭素の削減にも繋がる。 Methanol is not particularly limited. For example, methanol produced using natural gas and carbon dioxide as raw materials may be used. As a result, it becomes an alternative production method of light olefins produced using conventional petroleum-derived naphtha as a raw material, and also leads to reduction of carbon dioxide.
　上記原料には、メタノールとともに、その転化率を計算するためにヘキサン、へプタンなどのＭＴＯ反応条件下において気体で存在する飽和炭化水素を加えてもよい。 In addition to methanol, saturated hydrocarbons that exist in a gaseous state under MTO reaction conditions, such as hexane and heptane, may be added to the above raw materials in order to calculate the conversion rate.
　ＹＮＵ－５触媒にメタノールを接触させる方法としては、ＹＮＵ－５触媒の存在下でメタノールを軽質オレフィンに変換できる方法であれば、特に限定されず、例えば、メタノールを気体にして、これを含むガス流を、ＹＮＵ－５触媒を含む触媒床に供給することが挙げられる。 The method for bringing methanol into contact with the YNU-5 catalyst is not particularly limited as long as it is a method capable of converting methanol into light olefin in the presence of the YNU-5 catalyst. For example, a gas containing methanol as a gas is included. The stream may be fed to a catalyst bed containing YNU-5 catalyst.
　その場合、ガス流は、窒素やアルゴンなどの不活性ガスとメタノールとの混合ガスとして供給してもよい。 In that case, the gas flow may be supplied as a mixed gas of an inert gas such as nitrogen or argon and methanol.
　また、触媒床としては、ＹＮＵ－５触媒に石英砂などの不活性な無機粒子（希釈材）を加えることにより、ＹＮＵ－５触媒を希釈したものを用いてもよい。無機粒子の添加量は特に限定されず、例えばＹＮＵ－５触媒の質量の２～５倍の質量でもよい。 Further, as the catalyst bed, a YNU-5 catalyst diluted by adding inert inorganic particles (diluent) such as quartz sand to the YNU-5 catalyst may be used. The amount of inorganic particles added is not particularly limited, and may be, for example, 2 to 5 times the mass of the YNU-5 catalyst.
　ＭＴＯ反応の反応温度（触媒床の温度）は、メタノールを軽質オレフィンに変換できる温度であれば特に限定されず、例えば３５０～４５０℃でもよく、４００～４５０℃でもよい。 The reaction temperature of the MTO reaction (catalyst bed temperature) is not particularly limited as long as it is a temperature at which methanol can be converted into light olefin, and may be, for example, 350 to 450 ° C. or 400 to 450 ° C.
　反応方式としては、連続流通式でも、回分式でもよい。連続流通式の場合、ガス空間速度（ＧＨＳＶ）は特に限定されず、例えば、ＹＮＵ－５触媒１ｇ当たり、１０００～２５００ｍＬｇcat －１ｈ－１でもよく、１３００～２０００ｍＬｇcat －１ｈ－１でもよい。また、反応形式としては、特に制限はなく、固定床式、移動床式、流動床式のいずれでもよい。反応器の形式としても特に制限はなく、例えば管型反応器等を用いることができる。 The reaction method may be a continuous flow method or a batch method. In the case of the continuous flow type, the gas space velocity (GHSV) is not particularly limited, and may be, for example, 1000 to 2500 mLg cat −1 h −1 or 1300 to 2000 mLg cat −1 h −1 per 1 g of YNU-5 catalyst. . Moreover, there is no restriction | limiting in particular as a reaction format, Any of a fixed bed type, a moving bed type, and a fluidized bed type may be sufficient. There is no restriction | limiting in particular also as a form of a reactor, For example, a tubular reactor etc. can be used.
　本実施形態において生成される軽質オレフィンは、炭素数２～４のオレフィン（即ち、アルケン）であり、エチレン、プロピレン及びブテンからなる群から選択される少なくとも１種のオレフィンが生成される。生成物は、好ましくはブテンを含むことである。ＹＮＵ－５触媒であると、従来のゼオライト触媒に比べて、生成物におけるブテンの選択率が高いため、ブテンの製造方法として好適である。 The light olefin produced in this embodiment is an olefin having 2 to 4 carbon atoms (ie, alkene), and at least one olefin selected from the group consisting of ethylene, propylene and butene is produced. The product preferably contains butene. The YNU-5 catalyst is suitable as a method for producing butene because the selectivity of butene in the product is higher than that of the conventional zeolite catalyst.
　以下、実施例を示すが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, examples will be shown, but the present invention is not limited to these examples.
　［１］第１実施例
　［ＹＮＵ－５触媒の調製］
　フッ素樹脂製容器に１．４４ｇのＮａＯＨと２．０２ｇのＫＯＨと３５．２ｇのコロイダルシリカ（Sigma-Aldrich社製「LUDOX SM Colloidal silica」３０質量％水分散体）を入れて溶解させた。次いで、ジメチルジプロピルアンモニウム１５．０ｇを加えて、８０℃で１２時間撹拌した。撹拌後、室温まで冷却し、Ｙ型ゼオライト（東ソー（株）製「ＨＳＺ－３５０ＨＵＡ」、Ｓｉ／Ａｌ＝５．３）５．９８ｇを入れて撹拌してゲル溶液を調製した。ゲル溶液を１６０℃で７日間にわたり水熱合成を行った。水熱合成後、生成物をｐＨが中性になるまで洗浄し、１２０℃で一晩乾燥した後、５５０℃で８時間焼成した。ここで得られたのはＮａ型ＹＮＵ－５ゼオライトであるため、該ゼオライトをＨ型にするため、１．０Ｍ硝酸アンモニウムを用いて８０℃で１２時間イオン交換を行い、ＮＨ４型に転換した。その後、１２０℃で一晩乾燥し、更に５５０℃で６時間焼成して、Ｈ型ＹＮＵ－５ゼオライト（Ｓｉ／Ａｌ＝９）を得た。 [1] First Example [Preparation of YNU-5 catalyst]
In a fluororesin container, 1.44 g of NaOH, 2.02 g of KOH, and 35.2 g of colloidal silica (“LUDOX SM Colloidal silica” 30% by mass aqueous dispersion manufactured by Sigma-Aldrich) were added and dissolved. Next, 15.0 g of dimethyldipropylammonium was added and stirred at 80 ° C. for 12 hours. After stirring, the mixture was cooled to room temperature, and 5.98 g of Y-type zeolite (“HSZ-350HUA” manufactured by Tosoh Corporation, Si / Al = 5.3) was added and stirred to prepare a gel solution. The gel solution was hydrothermally synthesized at 160 ° C. for 7 days. After hydrothermal synthesis, the product was washed until the pH became neutral, dried at 120 ° C. overnight, and then calcined at 550 ° C. for 8 hours. Since Na type YNU-5 zeolite was obtained here, in order to convert the zeolite to H type, ion exchange was performed using 1.0 M ammonium nitrate at 80 ° C. for 12 hours to convert to NH 4 type. Thereafter, it was dried at 120 ° C. overnight and further calcined at 550 ° C. for 6 hours to obtain H-type YNU-5 zeolite (Si / Al = 9).
　［ＳＡＰＯ－５触媒の調製］
　フッ素樹脂製容器にイオン交換水２１．６９ｇ、アルミニウムイソプロポキシド１０．４５ｇ、フュームドシリカ（Sigma-Aldrich製「0.007μｍ」）０．３ｇおよびリン酸５．７８ｇを入れ撹拌後、トリエチルアミン２．５４ｇを添加し６時間撹拌しゲル溶液を調製した。ゲル溶液を２００℃で４８時間にわたり水熱合成を行った。水熱合成後、生成物をｐＨが中性になるまで洗浄し、１２０℃で一晩乾燥後、６００℃で１０時間焼成して、ＳＡＰＯ－５ゼオライトを得た。 [Preparation of SAPO-5 catalyst]
In a fluororesin container, 21.69 g of ion-exchanged water, 10.45 g of aluminum isopropoxide, 0.3 g of fumed silica (“0.007 μm” manufactured by Sigma-Aldrich) and 5.78 g of phosphoric acid were added and stirred. 54 g was added and stirred for 6 hours to prepare a gel solution. The gel solution was hydrothermally synthesized at 200 ° C. for 48 hours. After hydrothermal synthesis, the product was washed until the pH became neutral, dried at 120 ° C. overnight, and calcined at 600 ° C. for 10 hours to obtain a SAPO-5 zeolite.
　［ＳＡＰＯ－１８触媒の調製］
　フッ素樹脂製容器にイオン交換水７．４ｍＬとアルミニウムイソプロポキシド４．８４ｇを入れ、さらにリン酸１．４ｇとイオン交換水１．４ｇを入れて撹拌した。次に、コロイダルシリカ（Sigma-Aldrich製「LUDOX SM Colloidal silica」３０質量％水分散体）０．５ｇをイオン交換水１．１ｇで懸濁させた溶液とＮ，Ｎ－ジイソプロピルエチルアミン３．３ｇを加え撹拌しゲル溶液を調製した。ゲル溶液を１６０℃で７日間にわたり水熱合成を行った。水熱合成後、生成物をｐＨが中性になるまで洗浄し、１２０℃で一晩乾燥後、５５０℃で６時間焼成して、ＳＡＰＯ－１８ゼオライトを得た。 [Preparation of SAPO-18 catalyst]
In a fluororesin container, 7.4 mL of ion exchange water and 4.84 g of aluminum isopropoxide were added, and 1.4 g of phosphoric acid and 1.4 g of ion exchange water were further added and stirred. Next, a solution obtained by suspending 0.5 g of colloidal silica (“LUDOX SM Colloidal silica” 30 mass% aqueous dispersion manufactured by Sigma-Aldrich) in 1.1 g of ion-exchanged water and 3.3 g of N, N-diisopropylethylamine were added. The mixture was stirred and a gel solution was prepared. The gel solution was hydrothermally synthesized at 160 ° C. for 7 days. After hydrothermal synthesis, the product was washed until the pH became neutral, dried at 120 ° C. overnight, and calcined at 550 ° C. for 6 hours to obtain SAPO-18 zeolite.
　［結晶構造の解析］
　上記で調製したＹＮＵ－５触媒について、Ｘ線回折（ＸＲＤ）法（ＣｕＫα　４０ｋＶ，２０ｍＡ，２°～８０°)を用いて結晶構造の解析を行った。 [Analysis of crystal structure]
The crystal structure of the YNU-5 catalyst prepared above was analyzed using an X-ray diffraction (XRD) method (CuKα 40 kV, 20 mA, 2 ° to 80 °).
　結果は図１に示す通りであり、非特許文献２に記載されたＹＮＵ－５のＸＲＤ結果と同様の特有のピークが見られたため、調製した触媒はＹＮＵ－５ゼオライトであることがわかる。なお、図示しないが、ＳＡＰＯ－１８触媒及びＳＡＰＯ－５触媒についても、ＸＲＤ法を用いた結晶構造解析により、それぞれ標準チャートと同様の特有のピークを持ち、触媒の調製に成功したことを確認した。 The results are as shown in FIG. 1, and since a unique peak similar to the XRD result of YNU-5 described in Non-Patent Document 2 was observed, it can be seen that the prepared catalyst was YNU-5 zeolite. Although not shown in the figure, the SAPO-18 catalyst and the SAPO-5 catalyst each had a specific peak similar to that of the standard chart by the crystal structure analysis using the XRD method, and it was confirmed that the catalyst was successfully prepared. .
　［比表面積、細孔容積及び細孔直径の測定］
　上記で調製したＹＮＵ－５触媒、ＳＡＰＯ－１８触媒及びＳＡＰＯ－５触媒についてそれぞれ、温度２００℃で２時間前処理した後、ＢＥＴ比表面積、細孔容積及び平均細孔径を測定した。これらの測定は、カンタクローム社「Ｎｏｖａ２２００ｅ」自動吸着装置のセルに触媒を入れ、機械にセットし、測定を開始することにより行った（測定点数７９ｐｏｉｎｔ）。 [Measurement of specific surface area, pore volume and pore diameter]
Each of the YNU-5 catalyst, SAPO-18 catalyst, and SAPO-5 catalyst prepared above was pretreated at a temperature of 200 ° C. for 2 hours, and then the BET specific surface area, pore volume and average pore diameter were measured. These measurements were carried out by placing the catalyst in the cell of Cantachrome's “Nova 2200e” automatic adsorption device, setting it in the machine, and starting the measurement (number of measurement points 79 points).
　結果は、下記表１に示す通りであり、いずれの触媒も比表面積が高く、また平均細孔径が１ｎｍ以上と大きな細孔径を持っており、コーク形成の抑制が期待できるものであった。 The results are as shown in Table 1 below, and all of the catalysts have a high specific surface area and a large pore diameter of 1 nm or more, and the suppression of coke formation can be expected.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　［ＭＴＯ反応］
　上記で調製したＹＮＵ－５触媒、ＳＡＰＯ－１８触媒及びＳＡＰＯ－５触媒について、ＭＴＯ反応による触媒性能評価試験を行った。 [MTO reaction]
The YNU-5 catalyst, the SAPO-18 catalyst, and the SAPO-5 catalyst prepared above were subjected to a catalyst performance evaluation test by MTO reaction.
　ＭＴＯ反応試験は、常圧（０．１ＭＰａ）において、固定床石英ガラス反応器を用いて行った。反応装置の概念図は図２に示す通りであり、内径６ｍｍの管状の反応器の流路の途中に触媒床を設けた。触媒床はその両側に石英ウールを詰めて固定した。反応器の外周には触媒床を加熱するためのヒータを設け、触媒床の内部温度を測定する温度測定用熱電対温度計と、反応器の外壁温度を測定する反応温度コントロール用熱電対により、ヒータの出力を制御するように構成した。 The MTO reaction test was conducted using a fixed bed quartz glass reactor at normal pressure (0.1 MPa). The conceptual diagram of the reaction apparatus is as shown in FIG. 2, and a catalyst bed is provided in the middle of the flow path of a tubular reactor having an inner diameter of 6 mm. The catalyst bed was fixed by packing quartz wool on both sides. A heater for heating the catalyst bed is provided on the outer circumference of the reactor, and a thermocouple thermometer for measuring the internal temperature of the catalyst bed and a reaction temperature control thermocouple for measuring the outer wall temperature of the reactor, It was configured to control the output of the heater.
　実施例１では、Ｈ型ＹＮＵ－５ゼオライト１．０ｇと石英砂３．０ｇを混ぜ合わせて反応器内に入れることにより触媒床を形成した。反応ガスとしてメタノール：ヘキサンを９０：１（モル比）の割合で混合し、該反応原料（液体混合物）０．００５ｍＬ／ｍｉｎを３００℃で気化させて、反応器の一端から反応器内に流通させた。その際、窒素ガスを２２ｍＬ／ｍｉｎ（反応ガスのガス空間速度：１３２０ｍＬｇcat －１ｈ－１）又は３３ｍＬ／ｍｉｎ（反応ガスのガス空間速度：１９８０ｍＬｇcat －１ｈ－１）で流通させた。反応は４００℃まで８０分で昇温させて行った。昇温が完了した後、１時間ごとにガスクロマトグラフィー（（株）島津製作所製「ＧＣ－２０１４」、ＦＩＤ：Ｐｏｒａｐａｋ　Ｑカラム)によりオンラインで生成物を測定し、７時間反応を行った。 In Example 1, a catalyst bed was formed by mixing 1.0 g of H-type YNU-5 zeolite and 3.0 g of quartz sand and mixing them in a reactor. Methanol: hexane is mixed as a reaction gas at a ratio of 90: 1 (molar ratio), 0.005 mL / min of the reaction raw material (liquid mixture) is vaporized at 300 ° C., and then circulated from one end of the reactor into the reactor. I let you. At that time, nitrogen gas was circulated at 22 mL / min (reaction gas gas space velocity: 1320 mLg cat −1 h −1 ) or 33 mL / min (reaction gas gas space velocity: 1980 mLg cat −1 h −1 ). The reaction was performed by raising the temperature to 400 ° C. in 80 minutes. After the temperature increase was completed, the product was measured online by gas chromatography (“GC-2014” manufactured by Shimadzu Corporation, FID: Porapak Q column) every hour, and the reaction was performed for 7 hours.
　ガスクロマトグラフィーによる測定により、メタノール転化率を求めるとともに、各生成物の選択率を求めた。算出式は以下の通りである。 Measured by gas chromatography, the methanol conversion was determined and the selectivity of each product was determined. The calculation formula is as follows.
Figure JPOXMLDOC01-appb-M000002
Figure JPOXMLDOC01-appb-M000002
　実施例２では、Ｈ型ＹＮＵ－５ゼオライト１．０ｇの代わりに、Ｈ型ＹＮＵ－５ゼオライト０．４ｇとＳＡＰＯ－５ゼオライト０．３ｇとＳＡＰＯ－１８ゼオライト０．３ｇを混合したものを用い、その他は実施例１と同様にして反応を行った。 In Example 2, instead of 1.0 g of H-type YNU-5 zeolite, a mixture of 0.4 g of H-type YNU-5 zeolite, 0.3 g of SAPO-5 zeolite and 0.3 g of SAPO-18 zeolite was used. The others were reacted in the same manner as in Example 1.
　比較例１では、Ｈ型ＹＮＵ－５ゼオライト１．０ｇの代わりに、ＳＡＰＯ－５ゼオライト１．０ｇを用い、その他は実施例１と同様にして反応を行った。 In Comparative Example 1, 1.0 g of SAPO-5 zeolite was used instead of 1.0 g of H-type YNU-5 zeolite, and the others were reacted in the same manner as in Example 1.
　比較例２では、Ｈ型ＹＮＵ－５ゼオライト１．０ｇの代わりに、ＳＡＰＯ－１８ゼオライト１．０ｇを用い、その他は実施例１と同様にして反応を行った。 In Comparative Example 2, 1.0 g of SAPO-18 zeolite was used instead of 1.0 g of H-type YNU-5 zeolite, and the others were reacted in the same manner as in Example 1.
　図３に流速２２ｍＬ／ｍｉｎでのメタノール転化率を、図４に流速３３ｍＬ／ｍｉｎでのメタノール転化率をそれぞれ示す。図３及び図４より、実施例１，２及び比較例１，２のいずれについても、メタノール転化率８０％以上であり、高い触媒活性を示した。また、７時間経過後でも高いメタノール転化率のままであり、長い触媒寿命を持つことが分かった。ＹＮＵ－５触媒を用いた実施例１では、常に１００％のメタノール転化率を示した。ＳＡＰＯ－５触媒を用いた比較例１では、反応開始してから２時間はメタノール転化率がやや不安定であったが、その後は安定し１００％となった。ＳＡＰＯ－１８触媒を用いた比較例２では、高い触媒活性を示したものの、メタノール転化率が不安定であった。また、ＹＮＵ－５ゼオライトを含む混合物（Mixture）を用いた実施例２では、実施例１と同様、メタノール転化率が安定して１００％を示した（図４参照）。 3 shows the methanol conversion rate at a flow rate of 22 mL / min, and FIG. 4 shows the methanol conversion rate at a flow rate of 33 mL / min. From FIG. 3 and FIG. 4, in all of Examples 1 and 2 and Comparative Examples 1 and 2, the methanol conversion was 80% or more, indicating high catalytic activity. It was also found that even after 7 hours, the methanol conversion rate remained high and the catalyst life was long. Example 1 using YNU-5 catalyst always showed 100% methanol conversion. In Comparative Example 1 using the SAPO-5 catalyst, the methanol conversion rate was slightly unstable for 2 hours after the start of the reaction, but after that, it became stable and reached 100%. In Comparative Example 2 using the SAPO-18 catalyst, although high catalytic activity was exhibited, the methanol conversion was unstable. Further, in Example 2 using the mixture containing YNU-5 zeolite (Mixture), the methanol conversion was stably 100% as in Example 1 (see FIG. 4).
　また、７時間の反応における平均のメタノール転化率と、７時間の反応での各生成物の選択率の平均を、下記表２（流速２２ｍＬ／ｍｉｎ）及び表３（流速３３ｍＬ／ｍｉｎ）にそれぞれ示す。表２及び表３より、ＹＮＵ－５触媒を用いた実施例１及び２では、比較例１及び２に対して、平均メタノール転化率が高かった。また、全ての触媒でメタン選択率は低く、軽質オレフィン（Ｃ２Ｈ４、Ｃ３Ｈ６、Ｃ４Ｈ８）の選択率が高かった。特に、実施例１及び２では、比較例１及び２に対して、ブテンの選択率が高く、そのため、ＹＮＵ－５触媒を用いたＭＴＯ反応はブテンの製造方法としてより有効であることが分かった。 In addition, the average methanol conversion rate in the 7-hour reaction and the average selectivity of each product in the 7-hour reaction are shown in Table 2 (flow rate 22 mL / min) and Table 3 (flow rate 33 mL / min), respectively. Show. From Tables 2 and 3, in Examples 1 and 2 using YNU-5 catalyst, the average methanol conversion was higher than in Comparative Examples 1 and 2. Further, the methane selectivity at all catalysts is low, had higher light olefins (C 2 H 4, C 3 H 6, C 4 H 8) selectivity. In particular, in Examples 1 and 2, the selectivity for butene was higher than in Comparative Examples 1 and 2, and therefore, it was found that the MTO reaction using YNU-5 catalyst was more effective as a method for producing butene. .
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　［２］第２実施例
　第１実施例で調製したＨ型ＹＮＵ－５ゼオライト（Ｓｉ／Ａｌ＝９）に、鉄担持量が５質量％となるように、硝酸鉄（ＩＩＩ）九水和物を含浸し、一晩乾燥させた後、５５０℃で６時間焼成を行って、鉄を５質量％担持させたＹＮＵ－５ゼオライト（ＹＮＵ－５Ｆｅ）を得た。 [2] Second Example Iron (III) nitrate nonahydrate so that the amount of iron supported on the H-type YNU-5 zeolite (Si / Al = 9) prepared in the first example is 5% by mass. And dried overnight, and calcined at 550 ° C. for 6 hours to obtain YNU-5 zeolite (YNU-5Fe) supporting 5% by mass of iron.
　得られたＹＮＵ－５Ｆｅ触媒について、第１実施例と同様に、温度２００℃で２時間前処理した後、ＢＥＴ比表面積、細孔容積及び平均細孔径を測定した。その結果、ＹＮＵ－５Ｆｅ触媒の比表面積は２９５．５ｍ２／ｇであり、細孔容積は０．２２ｃｍ３／ｇであり、平均細孔径は１．５１ｎｍであり、比表面積と細孔容積が第１実施例のＹＮＵ－５触媒よりも低下した。 The obtained YNU-5Fe catalyst was pretreated at a temperature of 200 ° C. for 2 hours, and the BET specific surface area, pore volume and average pore diameter were measured in the same manner as in Example 1. As a result, the specific surface area of the YNU-5Fe catalyst was 295.5 m 2 / g, the pore volume was 0.22 cm 3 / g, the average pore diameter was 1.51 nm, and the specific surface area and pore volume were It was lower than the YNU-5 catalyst of the first example.
　また、ＹＮＵ－５Ｆｅ触媒について、ＭＴＯ反応による触媒性能評価試験を行った。窒素ガスの流速を３３ｍＬ／ｍｉｎ（反応ガスのガス空間速度：１９８０ｍＬｇcat －１ｈ－１）のみとし、その他は第１実施例と同様に行った。 Further, the YNU-5Fe catalyst was subjected to a catalyst performance evaluation test by MTO reaction. The flow rate of nitrogen gas was only 33 mL / min (reaction gas gas space velocity: 1980 mLg cat −1 h −1 ), and the others were performed in the same manner as in the first example.
　図５に示されるように、ＹＮＵ－５Ｆｅ触媒を用いた実施例３では、金属を担持していないＹＮＵ－５触媒を用いた上記実施例１と同様、メタノール転化率がほぼ１００％で維持されており、長い触媒寿命を持つことが分かった。 As shown in FIG. 5, in Example 3 using the YNU-5Fe catalyst, the methanol conversion was maintained at almost 100% as in Example 1 using the YNU-5 catalyst not supporting metal. It was found to have a long catalyst life.
　７時間の反応における平均のメタノール転化率と、７時間の反応での各生成物の選択率の平均を、下記表４に示す。ＹＮＵ－５Ｆｅ触媒を用いた実施例３では、金属を担持していないＹＮＵ－５触媒を用いた上記実施例１に比べて、ブテンの選択率が高く、そのため、ＹＮＵ－５ゼオライトに金属を担持することにより、ブテンの製造方法としてより有効であることが分かった。 Table 4 below shows the average methanol conversion in the 7-hour reaction and the average selectivity of each product in the 7-hour reaction. In Example 3 using the YNU-5Fe catalyst, the selectivity for butene was higher than in Example 1 using the YNU-5 catalyst not supporting the metal, so that the metal was supported on the YNU-5 zeolite. By doing so, it turned out that it is more effective as a manufacturing method of butene.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　以上のように、本実施形態であると、メタノールから、高いメタノール転化率かつ高いオレフィン選択率で、長時間にわたって軽質オレフィンを合成することができる。そのため、シェールガスを含む天然ガスからＭＴＯ反応により工業原料として有用な軽質オレフィンを効率良く製造することができる。 As described above, in the present embodiment, light olefins can be synthesized from methanol over a long period of time with high methanol conversion and high olefin selectivity. Therefore, a light olefin useful as an industrial raw material can be efficiently produced from natural gas containing shale gas by an MTO reaction.
　以上、本発明のいくつかの実施形態を説明したが、これら実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これら実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。これら実施形態やその省略、置き換え、変更などは、発明の範囲や要旨に含まれると同様に、特許請求の範囲に記載された発明とその均等の範囲に含まれるものである。 Although several embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the spirit of the invention. These embodiments and their omissions, replacements, changes, and the like are included in the inventions described in the claims and their equivalents as well as included in the scope and gist of the invention.

Claims (4)

  1. 　ＹＮＵ－５ゼオライトを含む触媒の存在下でメタノールを軽質オレフィンに変換することを含む、軽質オレフィンの製造方法。 A process for producing light olefins, comprising converting methanol to light olefins in the presence of a catalyst containing YNU-5 zeolite.
  2. 　前記ＹＮＵ－５ゼオライトが金属を担持したものである、請求項１に記載の軽質オレフィンの製造方法。 The method for producing a light olefin according to claim 1, wherein the YNU-5 zeolite carries a metal.
  3. 　前記軽質オレフィンが、エチレン、プロピレン及びブテンからなる群から選択される少なくとも１種である、請求項１又は２に記載の軽質オレフィンの製造方法。 The method for producing a light olefin according to claim 1 or 2, wherein the light olefin is at least one selected from the group consisting of ethylene, propylene and butene.
  4. 　前記軽質オレフィンがブテンを含む、請求項１～３のいずれか１項に記載の軽質オレフィンの製造方法。 The method for producing a light olefin according to any one of claims 1 to 3, wherein the light olefin contains butene.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022085096A1 (en) * 2020-10-20 2022-04-28
WO2022165354A1 (en) * 2021-02-01 2022-08-04 Basf Corporation Ynu-5 zeolite, methods of preparation, and methods of use thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004074411A1 (en) * 2003-02-18 2004-09-02 Japan Gas Synthesize, Ltd. Method for producing liquefied petroleum gas
JP2013245163A (en) * 2012-05-23 2013-12-09 Tokyo Institute Of Technology Method for producing propylene
US20170166493A1 (en) * 2015-12-11 2017-06-15 Uop Llc Sapo catalyst for a high pressure mto process

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008080238A (en) * 2006-09-27 2008-04-10 Jgc Corp Regeneration method of mfi structure zeolite catalyst
JP5646279B2 (en) * 2010-10-28 2014-12-24 国立大学法人横浜国立大学 Production method of light olefin

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004074411A1 (en) * 2003-02-18 2004-09-02 Japan Gas Synthesize, Ltd. Method for producing liquefied petroleum gas
JP2013245163A (en) * 2012-05-23 2013-12-09 Tokyo Institute Of Technology Method for producing propylene
US20170166493A1 (en) * 2015-12-11 2017-06-15 Uop Llc Sapo catalyst for a high pressure mto process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NAKAZAWA, N. ET AL.: "A microporous aluminosilicate with 12-, 12-, and 8-ring pores and isolated 8- ring channels", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, pages 7989 - 7997, XP055501405, doi:10.1021/jacs.7b03308 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022085096A1 (en) * 2020-10-20 2022-04-28
JP7407966B2 (en) 2020-10-20 2024-01-04 Ｔｏｙｏ Ｔｉｒｅ株式会社 Method for producing light olefins
WO2022165354A1 (en) * 2021-02-01 2022-08-04 Basf Corporation Ynu-5 zeolite, methods of preparation, and methods of use thereof

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