WO2022085095A1 - 軽質オレフィンの製造方法 - Google Patents

軽質オレフィンの製造方法 Download PDF

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Publication number
WO2022085095A1
WO2022085095A1 PCT/JP2020/039470 JP2020039470W WO2022085095A1 WO 2022085095 A1 WO2022085095 A1 WO 2022085095A1 JP 2020039470 W JP2020039470 W JP 2020039470W WO 2022085095 A1 WO2022085095 A1 WO 2022085095A1
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catalyst
mcm
zeolite
zsm
light olefin
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PCT/JP2020/039470
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English (en)
French (fr)
Japanese (ja)
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嘉治 米山
範立 椿
典彦 中村
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Ｔｏｙｏ Ｔｉｒｅ株式会社
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Priority to JP2022556876A priority Critical patent/JPWO2022085095A1/ja
Priority to PCT/JP2020/039470 priority patent/WO2022085095A1/ja
Publication of WO2022085095A1 publication Critical patent/WO2022085095A1/ja

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    • 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
    • C07C11/06—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
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—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
    • B01J29/04—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
    • 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

  • the embodiment of the present invention relates to a method for producing a light olefin.
  • Patent Document 1 proposes a catalyst containing YNU-5 zeolite, and also proposes a catalyst in which YNU-5 zeolite is impregnated with iron nitrate nine hydrate and calcined to support a metal. ..
  • the method for producing a light olefin according to an embodiment of the present invention is at least one selected from the group consisting of cerium oxide and iron oxide in a zeolite having pores composed of 10-membered oxygen rings and having a channel structure of two or more dimensions. It involves converting methanol to a light olefin in the presence of a catalyst carrying the metal oxide of.
  • the light olefin means a chain hydrocarbon having at least one carbon-carbon double bond and having 5 or less carbon atoms.
  • the zeolite may contain at least one selected from the group consisting of ZSM-5 and MCM-22.
  • the catalyst may include a catalyst in which cerium oxide is carried on the zeolite, and the cerium oxide may contain at least one selected from the group consisting of CeO 2 and Ce 2 O 3 .
  • the catalyst may include a catalyst in which iron oxide is carried on the zeolite, and the iron oxide may contain at least one selected from the group consisting of Fe 2 O 3 , Fe 3 O 4 and FeO.
  • the catalysts are from CeO 2 / ZSM-5, Fe 2 O 3 / ZSM-5, CeO 2 / MCM-22, Fe 2 O 3 / MCM-22 and Fe 3 O 4 / MCM-22. It may contain at least one selected from the group of
  • the molar ratio Si / Al of the silicon element to the aluminum element in the zeolite may be 10 to 400.
  • the amount of the metal oxide supported on the catalyst may be 1 to 20% by mass in terms of metal element.
  • the light olefin may contain at least one selected from the group consisting of propylene and butene.
  • a light olefin can be synthesized from methanol at a high conversion rate.
  • a zeolite having pores composed of 10-membered oxygen rings and having a channel structure of two dimensions or more is used as a solid acid catalyst thereof.
  • a catalyst carrying at least one metal oxide selected from the group consisting of cerium oxide and iron oxide is used.
  • the oxygen 10-membered ring means a ring surrounded by 10 oxygen atoms. Since the number of oxygen on the ring and the number of T atoms (tetrahedral atoms in the skeleton) at the apex of the zeolite skeleton are equal, the oxygen 10-membered ring is a ring surrounded by 10 T atoms.
  • the pores of zeolite include small pores composed of 8-membered oxygen rings, medium pores composed of 10-membered oxygen rings, large pores composed of 12-membered oxygen rings, and ultra-large pores composed of 14-membered oxygen rings or more. There is. In this embodiment, a zeolite having a medium pore composed of a 10-membered ring of oxygen is used.
  • a zeolite having a channel structure of two dimensions or more is used as the zeolite used in this embodiment.
  • the pore structure of zeolite is classified into a one-dimensional channel, a two-dimensional channel in which the channels are two-dimensionally connected, and a three-dimensional channel in which the channels are three-dimensionally connected.
  • two-dimensional or three-dimensional ones are used.
  • Zeolites having pores composed of 10-membered oxygen rings and having a channel structure of two or more dimensions include ZSM-5, MCM-22, Dachiardite, EMM-26, Ferrierite, IM-5, and the like.
  • ITQ-13, ITQ-34, GAGEO-CJ63, ZSM-11, NU-87, OSB-2, IPC-4, SSZ-58, SSZ-74, Terranovaite, TNU-9, IM-18 may be used alone or in combination of two or more.
  • ZSM-5 is a zeolite having medium pores composed of a 10-membered oxygen ring and having a three-dimensional channel structure.
  • MCM-22 is a zeolite having medium pores composed of a 10-membered oxygen ring and having a two-dimensional channel structure.
  • the molar ratio Si / Al of the silicon element to the aluminum element in the zeolite is not particularly limited, and may be, for example, 10 to 400 or 20 to 200. In one embodiment, the molar ratio Si / Al in ZSM-5 may be, for example, 40-300, 80-250, or 100-200. In one embodiment, the molar ratio Si / Al in MCM-22 may be, for example, 10-60, 20-40, or 25-35.
  • a catalyst in which at least one metal oxide selected from the group consisting of cerium oxide and iron oxide is supported on the zeolite is used. This makes it possible to synthesize a light olefin from methanol with a high conversion rate, and in particular, to increase the selectivity of butene.
  • the method for supporting the metal oxide is not particularly limited, and the metal oxide can be supported by a known method such as an impregnation method or an ion exchange method.
  • cerium oxide examples include cerium oxide (IV) (CeO 2 ) and cerium oxide (III) (Ce 2 O 3 ), which may be used alone or in combination. Since Ce 2 O 3 is easily oxidized and becomes CeO 2 by oxidation, the supported cerium oxide is preferably CeO 2 .
  • CeO 2 is a metal oxide showing basicity, and due to its atomic size, it does not enter the pores of zeolite and can deactivate only the acid spots on the outer surface, so that it can be deactivated on the outer surface of zeolite. Reactions without shape selectivity can be suppressed.
  • iron oxide examples include iron oxide (III) (Fe 2 O 3 ), iron oxide (II, III) (Fe 3 O 4 ), and iron oxide (II) (FeO). You may use more than seeds together.
  • iron oxide III
  • iron oxide II
  • III iron oxide
  • II iron oxide
  • the presence of iron on the inner surface of the zeolite pores has the effect of reducing the pore diameter of the zeolite.
  • the iron deactivates the acid point of the zeolite, so that the reaction without shape selectivity on the outer surface of the zeolite can be suppressed.
  • the iron present in the skeleton needs to be trivalent as it replaces trivalent aluminum.
  • a change in the acid strength of the zeolite appears, which can be more favorable for olefin formation than trivalent aluminum.
  • the iron oxide to be carried is preferably Fe 2 O 3 and / or Fe 3 O 4 .
  • the method for supporting the above three types of iron oxide is not particularly limited.
  • a metal species when supported on zeolite and calcined in an air atmosphere, it becomes Fe 2 O 3 , and when calcined in a nitrogen atmosphere, it becomes Fe 2 O 3. Is obtained as Fe 3 O 4 .
  • the amount of the metal oxide supported on the catalyst is not particularly limited, and may be, for example, 1 to 20% by mass, 2 to 15% by mass, or 3 to 10% by mass in terms of metal element.
  • the supported amount is the ratio of the mass of the supported metal element contained in the catalyst when the total mass of the catalyst is 100% by mass.
  • the amount of the metal oxide carried is measured by EDX (energy dispersive X-ray spectroscopy).
  • Preferred specific examples of the catalyst include at least one selected from the group consisting of the following (1) to (5).
  • another catalyst may be used in combination with the catalyst in which cerium oxide and / or iron oxide is supported on the above-mentioned specific zeolite.
  • the other catalyst can be used without particular limitation as long as the effect of the present embodiment is not impaired, and examples thereof include other zeolite catalysts and metal oxide catalysts.
  • methanol is converted to a light olefin in the presence of the above catalyst.
  • a raw material containing methanol may be brought into contact with the catalyst.
  • the methanol is not particularly limited, but for example, methanol produced from natural gas and carbon dioxide as raw materials may be used. This will be an alternative production method for light olefins produced from conventional petroleum-derived naphtha as a raw material, and will also lead to a reduction in carbon dioxide.
  • Saturated hydrocarbons existing in gas under MTO reaction conditions such as hexane and heptane may be added to the above raw materials together with methanol in order to calculate the conversion rate.
  • the method for bringing methanol into contact with the catalyst is not particularly limited as long as it is a method capable of converting methanol into a light olefin in the presence of the catalyst. Supplying to the catalyst bed can be mentioned.
  • the gas flow may be supplied as a mixed gas of an inert gas such as nitrogen or argon and methanol.
  • a catalyst bed may be used in which the catalyst is diluted by adding inert inorganic particles (diluting material) such as quartz sand to the catalyst.
  • inert inorganic particles such as quartz sand
  • the amount of the inorganic particles added is not particularly limited, and may be, for example, 2 to 5 times the mass of the catalyst.
  • the reaction temperature (temperature of the catalyst bed) of the MTO reaction is not particularly limited as long as it can convert methanol into a light olefin, and may be, for example, 350 to 450 ° C. or 400 to 450 ° C.
  • the reaction method may be a continuous distribution 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 the catalyst.
  • the reaction type is not particularly limited, and may be a fixed bed type, a moving bed type, or a fluidized bed type.
  • the type of the reactor is not particularly limited, and for example, a tubular reactor or the like can be used.
  • the light olefin produced in the present embodiment is preferably an olefin having 2 to 4 carbon atoms, and more preferably contains at least one selected from the group consisting of propylene and butene, and more preferably. It is to include butene.
  • the catalyst according to the present embodiment 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.
  • ion-exchanged water 21.672 g of tetrapropylammonium hydroxide 10% by mass aqueous solution (TPAOH), 8.182 g of ethanol 99.5% (EtOH), and aluminum nitrate nineahydrate are placed in a TFF container. 0.111 g was added and stirred. 9.74 g of tetraethyl orthosilicate (TEOS) as a silica source was slowly added to the stirring solution, and the mixture was stirred for 4 hours. After that, it was confirmed that the precursor solution was a uniform sol solution, and hydrothermal synthesis was carried out while stirring at 180 ° C. for 24 hours at 4 rpm.
  • TEOS tetraethyl orthosilicate
  • Metal support amount The amount of metal supported on the catalyst was calculated from the measurement results by elemental analysis by EDX.
  • the MTO reaction test was carried out at normal pressure (0.1 MPa) using a fixed-bed quartz glass reactor.
  • the conceptual diagram of the reactor is as shown in FIG. 6, and a catalyst bed is provided in the middle of the flow path of the tubular reactor having an inner diameter of 6 mm.
  • the catalyst bed was fixed by filling both sides with quartz wool.
  • a heater for heating the catalyst bed is provided on the outer periphery of the reactor, and a thermocouple thermometer for temperature measurement that measures the internal temperature of the catalyst bed and a thermocouple for reaction temperature control that measures the outer wall temperature of the reactor are used. It was configured to control the output of the heater.
  • the catalyst bed was formed by mixing 1.0 g of catalyst and 3.0 g of quartz sand and putting them in a reactor.
  • As the reaction gas methanol: n-hexane is mixed at a ratio of 90: 1 (molar ratio), and the reaction raw material (liquid mixture) is vaporized at 300 ° C. and circulated from one end of the reactor into the reactor. rice field.
  • the reaction was carried out by raising the temperature to 400 ° C. in 80 minutes.
  • the methanol conversion rate was determined by measurement by gas chromatography, and the selectivity of each product was determined.
  • the calculation formula is as follows.
  • Example 1 As the catalyst, a CeO 2 / ZSM-5 catalyst was used in Example 1, and a ZSM-5 catalyst was used in Comparative Example 1.
  • the average methanol conversion rate in the 6-hour reaction and the average selectivity of each product in the 6-hour reaction are shown in Table 1 below. From Table 1, in Example 1 using the CeO 2 / ZSM-5 catalyst, the selectivity of butene is higher than that in Comparative Example 1 using the ZSM-5 catalyst which has a high methanol conversion rate and does not support cerium oxide. was significantly higher.
  • Example 2 a 3% Fe 2 O 3 / ZSM-5 catalyst was used in Example 2
  • a 5% Fe 2 O 3 / ZSM-5 catalyst was used in Example 3
  • ZSM-5 was used in Comparative Example 2.
  • a catalyst was used.
  • the amount of catalyst was 0.5 g, and the conversion rate of methanol and the selectivity of each product were determined in the same manner as in the first embodiment.
  • Example 4 a 5% CeO 2 / MCM-22 catalyst was used in Example 4
  • a 10% CeO 2 / MCM-22 catalyst was used in Example 5
  • An MCM-22 catalyst was used
  • a 5% Fe 2 O 3 / MCM-22 catalyst was used in Example 7
  • a 3% Fe 3 O 4 / MCM-22 catalyst was used in Example 8
  • MCM-22 was used in Comparative Example 3.
  • the conversion rate of methanol and the selectivity of each product were determined in the same manner as in the first embodiment.

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PCT/JP2020/039470 2020-10-20 2020-10-20 軽質オレフィンの製造方法 WO2022085095A1 (ja)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK202330116A1 (en) * 2023-07-05 2025-03-12 Topsoe As Process and plant for conversion of alcohols to hydrocarbons

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002510660A (ja) * 1998-04-06 2002-04-09 モービル・オイル・コーポレーション メタノールを炭化水素に転化するための触媒及び方法
CN101234353A (zh) * 2006-12-25 2008-08-06 汉能科技有限公司 一种甲醇制丙烯用催化剂及其制备方法和应用方法
CN101279281A (zh) * 2007-04-04 2008-10-08 中国石油化工股份有限公司 甲醇转化制丙烯的高稳定性分子筛催化剂及其制备方法
US20090326299A1 (en) * 2006-08-08 2009-12-31 Sud-Chemie Ag Use of a Catalyst Based on Zeolites in the Conversion of Oxygenates to Lower Olefins, and Associated Method
JP2014508632A (ja) * 2010-11-02 2014-04-10 サウディ ベーシック インダストリーズ コーポレイション Ｚｓｍ−５系触媒を使用した軽質オレフィンの製造方法
JP2017507773A (ja) * 2013-12-20 2017-03-23 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 含酸素化合物をオレフィンに変換するための触媒および方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002510660A (ja) * 1998-04-06 2002-04-09 モービル・オイル・コーポレーション メタノールを炭化水素に転化するための触媒及び方法
US20090326299A1 (en) * 2006-08-08 2009-12-31 Sud-Chemie Ag Use of a Catalyst Based on Zeolites in the Conversion of Oxygenates to Lower Olefins, and Associated Method
CN101234353A (zh) * 2006-12-25 2008-08-06 汉能科技有限公司 一种甲醇制丙烯用催化剂及其制备方法和应用方法
CN101279281A (zh) * 2007-04-04 2008-10-08 中国石油化工股份有限公司 甲醇转化制丙烯的高稳定性分子筛催化剂及其制备方法
JP2014508632A (ja) * 2010-11-02 2014-04-10 サウディ ベーシック インダストリーズ コーポレイション Ｚｓｍ−５系触媒を使用した軽質オレフィンの製造方法
JP2017507773A (ja) * 2013-12-20 2017-03-23 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 含酸素化合物をオレフィンに変換するための触媒および方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK202330116A1 (en) * 2023-07-05 2025-03-12 Topsoe As Process and plant for conversion of alcohols to hydrocarbons

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