WO2023061256A1 - 硅铝分子筛scm-36、其制造方法和应用 - Google Patents

硅铝分子筛scm-36、其制造方法和应用 Download PDF

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WO2023061256A1
WO2023061256A1 PCT/CN2022/123784 CN2022123784W WO2023061256A1 WO 2023061256 A1 WO2023061256 A1 WO 2023061256A1 CN 2022123784 W CN2022123784 W CN 2022123784W WO 2023061256 A1 WO2023061256 A1 WO 2023061256A1
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molecular sieve
sio
reaction
sample
silica
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PCT/CN2022/123784
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English (en)
French (fr)
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杨为民
王振东
马多征
刘松霖
刘闯
李相呈
袁志庆
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中国石油化工股份有限公司
中国石油化工股份有限公司上海石油化工研究院
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Priority claimed from CN202111184012.0A external-priority patent/CN115959681A/zh
Priority claimed from CN202111233138.2A external-priority patent/CN116003200A/zh
Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司上海石油化工研究院 filed Critical 中国石油化工股份有限公司
Publication of WO2023061256A1 publication Critical patent/WO2023061256A1/zh

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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
    • 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
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
    • 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 present application relates to the technical field of molecular sieves, in particular to a silica-alumina molecular sieve, its manufacturing method and application.
  • molecular sieve materials are widely used in the fields of catalysis, ion exchange, adsorption and separation due to their open structure and large surface area. Subtle differences in the structure of these materials portend differences in the various observable properties used to characterize them, such as their morphology, specific surface area, void size, and the variability of these Significant differences exist in aspects such as catalytic and adsorption properties.
  • the basic framework structure of crystalline microporous zeolite is based on a rigid three-dimensional TO 4 (SiO 4 , AlO 4 , etc.) unit structure; in this structure, TO 4 shares oxygen atoms in a tetrahedral manner, and the charge balance of the framework tetrahedron such as AlO 4 It is maintained by the presence of surface cations such as Na + and H + . It can be seen that the framework properties of zeolite can be changed by cation exchange. At the same time, in the structure of zeolite, there are abundant pore systems with certain pore diameters.
  • pore channels are interlaced to form a three-dimensional network structure, and the skeleton can still exist stably after the water or organic matter in the pore channels is removed (US 4439409).
  • zeolite not only has good catalytic activity and excellent shape selectivity for various organic reactions, but also can achieve good selectivity through modification (US 6162416, US 4954325, US 5362697).
  • XRD X-ray diffraction pattern
  • TS-1 molecular sieve US4410501
  • ZSM-5 molecular sieve US3702886
  • TS-1 molecular sieve Si and Ti
  • ZSM-5 molecular sieve Si and Al
  • framework elements are also the same, but the relative content of framework elements is different, and they belong to different molecular sieves.
  • X zeolite (US2882244) and Y zeolite (US3130007) both have the same XRD spectrum characteristics, and the framework elements are Si and Al, but the relative content of Si and Al is different.
  • the X zeolite Si/Al molar ratio is lower than 1.5 and the Y zeolite Si/Al molar ratio is higher than 1.5.
  • the purpose of this application is to provide a new type of silica-alumina molecular sieve (referred to herein as SCM-36 molecular sieve), its manufacturing method and application.
  • SCM-36 molecular sieve silica-alumina molecular sieve
  • the specific XRD spectrum characteristics of the molecular sieve can be used as adsorbent, catalyst carrier and catalyst When used as a catalyst for the reaction of 2,5-dimethylfuran and/or 2,5-hexanedione to produce p-xylene, it has high p-xylene selectivity and cycle stability.
  • the application provides a silicon-aluminum molecular sieve, the silicon-aluminum ratio of the molecular sieve is n ⁇ 5, and the X-ray diffraction spectrum of the molecular sieve shows the relative intensity of the diffraction peaks as shown in the following table characteristic:
  • the application provides a method for manufacturing silica-alumina molecular sieves, comprising the steps of:
  • the organic structure directing agent (A) is selected from tetramethylammonium compounds; the organic structure directing agent (B) is selected from C6-16 alkylpyridinium compounds, n-octyltrimethylammonium compounds or their combination.
  • a molecular sieve composition comprising the silica-alumina molecular sieve according to the present application and a binder.
  • the application of the silica-alumina molecular sieve or the molecular sieve composition according to the present application as an adsorbent, a catalyst or a catalyst carrier is provided.
  • the application provides a method for preparing p-xylene, comprising: making a raw material containing 2,5-dimethylfuran, 2,5-hexanedione or a combination thereof contain the silica-alumina of the application The step of contacting and reacting with ethylene in the presence of molecular sieve or catalyst composed of it.
  • the molecular sieve of the present application has a novel structure that has not been reported in the prior art, and can be used as an adsorbent, a catalyst carrier or a catalyst.
  • the molecular sieve of the present application when used as a catalyst for the reaction of producing p-xylene from 2,5-dimethylfuran and/or 2,5-hexanedione, it has high p-xylene selectivity and cycle stability.
  • Fig. 1 is the X-ray diffraction (XRD) spectrogram of gained molecular sieve among the embodiment I-1;
  • Fig. 2 is the scanning electron microscope (SEM) image of gained molecular sieve among the embodiment I-1;
  • Fig. 3 is the transmission electron microscope (TEM) image of gained molecular sieve in embodiment I-1;
  • Fig. 4 is the ammonia temperature-programmed desorption (NH 3 -TPD) spectrogram of the molecular sieve obtained in Example I-1;
  • Fig. 5 is the pyridine adsorption infrared (Py-FTIR) spectrogram of molecular sieve obtained in embodiment 1-1;
  • Fig. 6 is the XRD spectrogram of gained molecular sieve among the embodiment 1-2;
  • Fig. 7 is the SEM image of gained molecular sieve among the embodiment 1-3;
  • Fig. 8 is the XRD spectrogram of the sample obtained in comparative example 1-1;
  • Fig. 9 is the XRD spectrogram of the sample obtained in comparative example 1-3;
  • Fig. 10 is the XRD spectrogram of the sample obtained in comparative example 1-4;
  • Fig. 11 is the graph of the conversion rate of 2,5-dimethylfuran and the selectivity of p-xylene under the condition of recycling SCM-36 molecular sieve in Example II-15;
  • Figure 12 is the NH 3 -TPD spectrum of the molecular sieve obtained in Example II-16;
  • Figure 13 is the Py-FTIR spectrum of the molecular sieve obtained in Example II-16.
  • silicon-aluminum ratio or “silicon-aluminum molar ratio” refers to the molar ratio between silicon calculated as SiO2 and aluminum calculated as Al2O3 in the molecular sieve.
  • the so-called “based on oxide” refers to the calculation based on the oxide form of the highest valence state that can exist stably for the corresponding element.
  • the expression “by oxide” means SiO2 for silicon, Al2O3 for aluminum, TiO2 for titanium, B2O3 for boron, Zirconium refers to ZrO2 , tin refers to SnO2 , and iron refers to Fe2O3 .
  • the so-called “synthesized state”, “synthesized form” or “synthesized molecular sieve” refers to the state of the molecular sieve after the synthesis step is completed and before the post-processing step (such as the calcination step) starts.
  • the synthesis state for example, it may be the state presented directly after the synthesis step is completed, and at this time it is generally called a molecular sieve precursor.
  • the molecular sieve may contain water and/or organic matter (in particular organic structure directing agents).
  • the so-called “calcined”, “calcined form” or “calcined molecular sieve” refers to the state of the molecular sieve after calcined.
  • the state after calcination for example, it can be the state presented after the synthesized molecular sieve is calcined to further remove organic matter (especially organic structure directing agent) and water that may exist in its pores.
  • w, m, s, vs, wm, ms and s-vs, etc. represent the diffraction at the corresponding 2 ⁇ angle calculated based on the diffraction peak intensity (in peak height)
  • the relative intensity I/I 0 of the peak relative to the strongest diffraction peak that is, the highest intensity diffraction peak
  • I represents the peak intensity of the corresponding diffraction peak
  • I 0 represents the peak intensity of the strongest diffraction peak
  • w represents weak
  • m represents Medium
  • wm for weak to medium ms for medium to strong
  • s-vs for strong to very strong are well known to those skilled in the art.
  • the structure of molecular sieves is determined by X-ray diffraction pattern after calcination at 550°C for 5 hours, and the X-ray diffraction pattern is determined by X-ray powder diffractometer using Cu-K ⁇ radiation source , Nickel filter.
  • X-ray powder diffractometer using Cu-K ⁇ radiation source , Nickel filter.
  • the sample test use a scanning electron microscope to observe the crystallization of the molecular sieve sample, and confirm that the sample contains only one crystal, that is, the molecular sieve sample is a pure phase. On this basis, perform an XRD test to ensure that there are no diffraction peaks in the XRD spectrum. Interfering peaks from other crystals.
  • the so-called “specific surface area” refers to the total area of a sample per unit mass, including the inner surface area and the outer surface area.
  • Non-porous samples only have an external surface area, such as Portland cement, some clay mineral powders, etc.; porous and porous samples have both external and internal surface areas, such as asbestos fibers, diatomaceous earth, and molecular sieves.
  • the surface area of pores with a pore diameter less than 2 nanometers in porous and porous samples is the internal surface area, and the surface area after deducting the internal surface area is called the external surface area.
  • the external surface area of a sample per unit mass is the external specific surface area.
  • pore volume or "pore volume” refers to the volume of pores per unit mass of molecular sieves.
  • total pore volume refers to the volume of all pores per unit mass of the molecular sieve.
  • micropore volume refers to the volume of all micropores per unit mass of molecular sieves (generally referring to pores with channel diameters less than 2 nanometers).
  • the pore structure parameters of the molecular sieve material such as: total pore volume, micropore volume, total specific surface area and external specific surface area are measured by a physical adsorption instrument (such as the TriStar 3000 physical adsorption instrument of the American Mike Instrument Company).
  • the experimental conditions of nitrogen physical adsorption and desorption are: the measurement temperature is -196°C, the molecular sieve is pretreated in vacuum at 300°C for 10 hours before measurement, and nitrogen is used as the adsorbate.
  • the so-called crystal thickness refers to the use of a transmission electron microscope to observe molecular sieves at a magnification of 100,000 times, randomly select an observation field of view, and calculate the average value of the sum of the thicknesses of all flaky crystals in the observation field of view . This operation was repeated 10 times in total. The average value of the sum of the average values of 10 times was taken as the crystal thickness.
  • the present application provides a silicon-alumina molecular sieve
  • the silicon-alumina ratio of the molecular sieve is n ⁇ 5, preferably n is in the range of 5-80, more preferably n is in the range of 10-65
  • the X-ray diffraction spectrum of described molecular sieve shows the relative intensity characteristics of diffraction peaks as shown in the table below:
  • the X-ray diffraction spectrum of the molecular sieve also shows the relative intensity characteristics of the diffraction peaks shown in any row of the following table:
  • the X-ray diffraction spectrum of the molecular sieve also shows the relative intensity characteristics of the diffraction peaks as shown in any row of the following table:
  • the silica-alumina molecular sieve SCM-36 of the present application has a structure that has never been obtained before in this field.
  • the SCM-36 molecular sieve can exist in an uncalcined state (synthesized state) or in a calcined state.
  • the SCM-36 molecular sieve When present in a synthesized state, the SCM-36 molecular sieve generally has the formula "nSiO 2 ⁇ Al 2 O 3 ⁇ organic structure directing agent ⁇ water" or "nSiO 2 ⁇ Al 2 O 3 ⁇ mMO x ⁇ organic structure directing agent ⁇ Water" shows the schematic chemical composition.
  • the SCM-36 molecular sieve When existing in a calcined state or in a synthesized state, the SCM-36 molecular sieve can also generally have the formula "nSiO 2 ⁇ Al 2 O 3 " or "nSiO 2 ⁇ Al 2 O 3 ⁇ mMO x ” shows the schematic chemical composition, where n represents the silicon-aluminum ratio of the molecular sieve and n ⁇ 5, m represents the molar ratio of silicon to M in the molecular sieve, and the value of m satisfies Calculated by oxides and based on the total amount of Si, Al and element M, the total content of the element M in the molecular sieve is not more than 3 mol%.
  • the molecular sieve has a specific surface area of 300-700 m2 /g, preferably 300-600 m2 /g, more preferably 350-500 m2 /g, for example 360- 480 m 2 /g; the external specific surface area is 50-300 m 2 /g, preferably 80-250 m 2 /g, more preferably 100-220 m 2 /g.
  • the total pore volume of the molecular sieve is 0.20-1.50 cm 3 /g, preferably 0.40-1.20 cm 3 /g, more preferably 0.5-1.0 cm 3 /g;
  • the pore volume is 0.05-0.35 cm3 /g, preferably 0.08-0.30 cm3 /g, more preferably 0.09-0.25 cm3 /g.
  • the crystal shape of the molecular sieve is nanosheet, and the thickness of the crystal is ⁇ 30 nm, preferably 5-25 nm, more preferably 7-20 nm, for example, 10-20 nm.
  • the total acid content of the molecular sieve is 400-1200 ⁇ mol ⁇ g -1 , preferably 500-1000 ⁇ mol ⁇ g -1 , wherein , the weak acid content is ⁇ 40%, preferably 45%-90%, and the weak acid is defined as an acid whose desorption temperature is 100-250°C.
  • the molecular sieve has a Lewis acid/Bronsted acid ratio of 0.1-3.8, preferably 0.4-3.5, as determined by pyridine adsorption infrared spectroscopy.
  • the molecular sieve further comprises at least one element M selected from titanium, boron, zirconium, tin, iron or combinations thereof.
  • the total amount of Si, Al and element M (wherein the amounts of Si, Al and element M are calculated as oxides of SiO 2 , Al 2 O 3 and element M respectively) ) as a benchmark, the total content of the element M in the molecular sieve does not exceed 3mol%.
  • the application provides a method for manufacturing a silica-alumina molecular sieve, comprising the steps of:
  • the organic structure-directing agent (A) is selected from tetramethylammonium compounds; the organic structure-directing agent (B) is selected from C10-16 alkylpyridinium compounds, n-octyltrimethylammonium compounds or their combination.
  • the silicon source (calculated as SiO 2 ), aluminum source (calculated as Al 2 O 3 ), organic structure-directing agent (A), organic structure-directing agent (B), the molar ratio of alkali source and water is 1: (0.01-0.20): (0.05-0.80): (0.05-0.80): (0.05-0.50): (8-80), preferably 1: (0.01- 0.10):(0.08-0.65):(0.08-0.65):(0.08-0.45):(10-70), more preferably 1:(0.02-0.07):(0.10-0.50):(0.10-0.50):( 0.10-0.40): (12-60).
  • the crystallization of step 1) can be carried out in any manner conventionally known in the art, such as making the silicon source, the aluminum source, the organic structure directing agent, alkali
  • the source and water are mixed according to a predetermined ratio, and the obtained mixture is hydrothermally crystallized under crystallization conditions.
  • the crystallization temperature of the crystallization in step 1) is 120-200°C
  • the crystallization time is 1-15 days, preferably the crystallization temperature is 130-190°C
  • the crystallization time is 2- 12 days, more preferably the crystallization temperature is 140-180° C., and the crystallization time is 3-9 days.
  • the molecular sieve can be separated from the obtained product mixture as a product by any conventionally known separation method, thereby obtaining the silica-alumina molecular sieve SCM- 36.
  • the separation means for example, a method of filtering, washing and drying the obtained product mixture can be mentioned.
  • the filtering, washing and drying can be performed in any manner conventionally known in the art.
  • the filtering for example, the resulting product mixture can be suction filtered; as the washing, for example, deionized water can be used for washing; as the drying, for example, the sample can be placed in a commercial drum Dry in an air drying oven.
  • the drying temperature may be 40-150°C, preferably 50-120°C, and the drying time may be 1-30 hours, preferably 2-24 hours. This drying may be performed under normal pressure or under reduced pressure.
  • the molecular sieve obtained in step 1) can also be calcined to remove the organic structure directing agent and possible moisture, etc., thereby obtaining the calcined molecular sieve (also belonging to the SCM of the present application) -36 molecular sieve).
  • the calcination can be carried out in any manner conventionally known in the art, for example, the calcination temperature is generally 300-800°C, preferably 400-650°C, and the calcination time is generally 1-12 hours, preferably 2-10 hours.
  • the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen atmosphere.
  • the silicon source and the aluminum source may be various silicon sources and aluminum sources conventionally used in the manufacture of silica-alumina molecular sieves, which are not strictly limited in the present application.
  • the silicon source is selected from silicic acid, silica gel, silica sol, tetraethyl silicate, water glass or their combination;
  • the aluminum source is selected from aluminum hydroxide, aluminum oxide, aluminate , aluminum salts and aluminum tetraalkoxides or combinations thereof.
  • the alkali source may be various alkali sources conventionally used in the manufacturing process of silica-alumina molecular sieves, and the present application is not strictly limited to this.
  • the alkali source is selected from inorganic bases with alkali metals and/or alkaline earth metals as cations or combinations thereof, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide , or a combination of them.
  • the organic structure-directing agent (A) is selected from tetramethylammonium compounds with (CH 3 ) 4 N + as the cation, such as tetramethylammonium hydroxide, tetramethylammonium organic acid salt and tetramethylammonium Methylammonium inorganic acid salt.
  • the organic structure directing agent (A) is selected from tetramethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide or combinations thereof.
  • the organic structure directing agent (B) is selected from pyridinium compounds with R(C 5 H 5 N) + as the cation, wherein R is C 10-16 alkyl, and C 8 H 17 (CH 3 ) 3 N + is a cationic n-octyltrimethylammonium compound or a combination thereof, such as C 10-16 alkylpyridinium hydroxide, C 10-16 alkylpyridinium organic acid salt, C 10- 16 Alkyl pyridinium inorganic acid salt, n-octyltrimethylammonium hydroxide, n-octyltrimethylammonium organic acid salt and n-octyltrimethylammonium inorganic acid salt.
  • the organic structure directing agent (B) is selected from cetylpyridinium bromide, tetradecylpyridinium bromide, dodecylpyridinium bromide, dedecylpyridinium bromide, chlorine Cetylpyridinium, tetradecylpyridinium chloride, cetylpyridinium hydroxide, n-octyltrimethylammonium chloride, n-octyltrimethylammonium bromide, n-octyltrimethylhydrogen ammonium oxide or combinations thereof.
  • the organic structure-directing agent (B) is selected from the group consisting of cetylpyridinium bromide, tetradecylpyridinium bromide, dodecylpyridinium bromide, cetylpyridinium chloride, decahydryl Hexaalkylpyridine, n-octyltrimethylammonium chloride, n-octyltrimethylammonium bromide, or combinations thereof.
  • the mixture in step 1) further includes at least one source of element M selected from titanium, boron, zirconium, tin and iron.
  • the titanium source is selected from titanium-containing organometallic complexes, titanium tetraalkoxides, titanium dioxide, titanium nitrate or combinations thereof;
  • the boron source is selected from boric acid, borate, borax, diboron trioxide Or their combination;
  • Zirconium source is selected from zirconium-containing organometallic complex, zirconium salt, zirconium hydroxide, zirconium alkoxide, zirconium dioxide or their combination;
  • Tin source is selected from tin-containing organometallic complex, tin salt, dioxide Tin or a combination thereof;
  • the iron source is selected from iron-containing organometallic complexes, ferric nitrate, ferric chloride, iron oxide or a combination thereof.
  • the molar ratio of the silicon source (calculated as SiO 2 ) to the source of the element M (calculated as the corresponding oxide) is 1: (0.002-0.10), preferably 1: (0.005- 0.05).
  • the silica-alumina molecular sieve SCM-36 manufactured according to the method of the present application is provided.
  • the silica-alumina molecular sieve SCM-36 of the present application can be obtained and used in any physical form, such as powder, granule or molded product (such as bar, clover, etc.). These physical forms can be obtained by any means conventionally known in the art and are not particularly limited.
  • the present application provides a molecular sieve composition, comprising the silica-alumina molecular sieve SCM-36 according to the present application or the silica-alumina molecular sieve SCM-36 manufactured according to the method of the present application, and a binder.
  • the silica-alumina molecular sieve SCM-36 of the present application can be used in combination with other materials to obtain a molecular sieve composition.
  • these other materials include active materials and inactive materials.
  • active material for example, synthetic zeolite, natural zeolite or other types of molecular sieves can be mentioned.
  • inactive material generally referred to as binder
  • the application is not strictly limited, for example, conventional Those used in the manufacture of adsorbents or catalysts, including but not limited to clay, clay, silica, silica gel, alumina, etc. or mixtures thereof.
  • One of these other materials may be used alone, or a plurality of them may be used in combination in an arbitrary ratio.
  • usage amount of the other materials it can directly refer to the conventional usage amount in this field, and there is no special limitation.
  • the molecular sieve composition may be in any physical form, such as powder, granule or molding (such as stick, clover, etc.). These physical forms can be obtained by any means conventionally known in the art and are not particularly limited.
  • the application of the silica-alumina molecular sieve SCM-36 or the molecular sieve composition of the present application, or the application of the silica-alumina molecular sieve SCM-36 manufactured according to the method of the present application as an adsorbent, catalyst or catalyst carrier is provided.
  • the SCM-36 molecular sieve or molecular sieve composition of the present application can be used as an adsorbent, for example, to separate at least one component from a mixture of components in the gas or liquid phase. Accordingly, said at least one component may be partially or substantially completely separated from a mixture of components, such as by contacting said mixture with said SCM-36 molecular sieve or said molecular sieve composition, This component is selectively adsorbed.
  • the adsorbent mention may be made, for example, of use for the removal of small amounts of water in organic solvents such as isopropanol, isobutanol, and isobutyl ketone, and for use in the adsorption and removal of small amounts of water in natural gas.
  • SCM-36 molecular sieve or molecular sieve composition of the present application can also be used as a catalyst carrier, catalyst or its catalytically active components directly or after necessary treatment or conversion (such as ion exchange, etc.) conventionally performed on molecular sieves in the art.
  • SCM-36 molecular sieve can be used as a catalyst carrier, such as supporting metal Pd to obtain Pd/SCM-36, which can be used as a Pd catalyst for hydrogenation or dehydrogenation reactions, and SCM-36 is a carrier at this time; it can also be used as Dual-functional catalyst, at this time, SCM-36 is not only the carrier of metal Pd, but also a solid acid catalytic material, providing acid centers.
  • reactants such as hydrocarbons
  • a catalyst comprising the SCM-36 molecular sieve or molecular sieve composition of the present application, thereby obtaining the target product.
  • the predetermined reaction for example: isopropyl Cracking of benzene, conversion of methanol to olefins or aromatics, and reaction of 2,5-dimethylfuran and/or 2,5-hexanedione with ethylene to prepare p-xylene, etc.
  • the present application provides a catalyst, which comprises the silica-alumina molecular sieve SCM-36 or the molecular sieve composition of the present application, or the silica-alumina molecular sieve SCM-36 manufactured according to the method of the present application, or consists of it.
  • the catalyst is suitable for the cracking of cumene, the conversion of methanol into olefins or aromatics, and the use of 2,5-dimethylfuran and/or 2,5-hexanedione as raw materials and Catalyst for the reaction of ethylene to produce p-xylene, etc.
  • the present application provides a method for preparing p-xylene, comprising: making a raw material containing 2,5-dimethylfuran, 2,5-hexanedione or a combination thereof contain the silicon compound of the present application The step of contacting and reacting with ethylene in the presence of aluminum molecular sieve SCM-36 or a catalyst composed of it.
  • the p-xylene preparation method of the present application adopts SCM-36 molecular sieve as catalyst or catalyst active component, and under mild reaction conditions, 2,5-dimethylfuran and/or 2,5-hexanedione can be efficiently converted into For p-xylene, both conversion and product p-xylene selectivity are very high. At the same time, the content of key impurities (such as polyalkylbenzene, 2,5-hexanedione and 2-cyclopentenone) in the obtained product is extremely low, which greatly reduces the energy consumption of separation.
  • the present application adopts SCM-36 molecular sieve as the catalyst, which has high stability, and there is no obvious change in the performance of the catalyst after being recycled for four times.
  • the contact reaction is carried out in the presence of an organic solvent.
  • the type of the organic solvent can be selected in a wide range, and all common organic solvents can be used in this application.
  • the organic solvent is selected from n-hexane, n-heptane, ⁇ -valerolactone, tetrahydrofuran, toluene, cyclohexane or combinations thereof.
  • the amount of the organic solvent can be selected within a wide range, and can be specifically determined according to the reaction requirements.
  • the mass ratio of the organic solvent to the raw material is 8-60: 1, preferably 10-30: 1, which is conducive to improving substrate conversion and product p-xylene selectivity, reducing The content of key impurities in the product.
  • the amount of the catalyst used can be selected within a wide range, and can be specifically determined according to the reaction requirements.
  • the mass ratio of the raw material to the catalyst is 0.6-30: 1, preferably 1.0-10: 1, which is conducive to improving the substrate conversion rate and product p-xylene selectivity and reducing the product content of key impurities.
  • the conditions of the contact reaction can be selected in a wide range, and can be specifically determined according to the reaction requirements.
  • the conditions of the reaction include: the reaction temperature is 160-340°C, preferably 220-270°C; the reaction time can be determined according to the temperature, for example, the reaction time can be 6-64h, preferably 8- 48h, more preferably 18-40h; the reaction pressure is 1-8MPa, preferably 2-4MPa.
  • the reagents and raw materials used are all commercially available products, and the purity is analytically pure.
  • the XRD measurement method of molecular sieve products is: adopt Panalytical X PERPRO type X-ray powder diffractometer, analyze the phase of sample, CuK ⁇ ray source Nickel filter, 2 ⁇ scanning range 2-50°, operating voltage 40KV, current 40mA, scanning rate 10°/min.
  • the Inductively Coupled Plasma Atomic Emission Spectrometer (ICP) model is Varian 725-ES, and the analysis sample is dissolved with hydrofluoric acid to detect the element content of the sample.
  • NH 3 temperature-programmed desorption (NH 3 -TPD) experiment was carried out on a TPD/TPR Altamira AMI-3300 instrument, and the total acid was calculated by fitting the obtained spectra to the peaks.
  • the amount, and the acid corresponding to the desorption temperature of 100-250 ° C is defined as a weak acid, and the proportion of weak acid is calculated from this.
  • the scanning electron microscope images were tested using a Hitachi S-4800II field emission scanning electron microscope from Hitachi, Japan, and the test voltage was 15KV.
  • the transmission electron microscope adopts the G2F30 transmission electron microscope of FEI Company in the Netherlands, the working voltage is 300kV, and the molecular sieve is observed at a magnification of 100,000 times.
  • An observation field of view is randomly selected, and the thickness of all crystals in the observation field of view is measured. This operation is repeated 5 times. The average value of 5 times was taken as the average thickness of the crystal.
  • the obtained calcined product had a specific surface area of 380 m 2 /g, an external specific surface area of 170 m 2 /g, a total pore volume of 0.92 cm 3 /g, and a micropore volume of 0.10 cm 3 /g.
  • the sample is in the form of nanosheets, and the thickness of the crystal is about 15 nanometers.
  • SiO 2 /Al 2 O 3 21.6 (molar ratio) of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP).
  • the ammonia gas temperature-programmed desorption (NH 3 -TPD) spectrogram of the obtained sample is shown in Fig. 4, the total acid content thus obtained was 782 ⁇ mol ⁇ g -1 , and the weak acid content was 63%.
  • the infrared spectrum of pyridine adsorption is shown in Fig. 5, and the Lewis/Bronsted acid ratio was determined to be 2.2.
  • the specific surface area of the obtained calcined product was 392 m 2 /g, the external specific surface area was 166 m 2 /g, the total pore volume was 0.73 cm 3 /g, and the micropore volume was 0.10 cm 3 /g.
  • the sample is in the shape of nanosheets, and the thickness of the crystal is about 12 nanometers.
  • SiO 2 /Al 2 O 3 15.6 (molar ratio) of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP).
  • the ammonia temperature-programmed desorption (NH 3 -TPD) of the obtained sample is similar to that shown in Fig. 4 , the total acid content thus obtained is 827 ⁇ mol ⁇ g -1 , and the weak acid content is 61%.
  • the infrared spectrum of pyridine adsorption is similar to that shown in Figure 5, and the Lewis/Bronsted acid ratio was determined to be 2.5.
  • the obtained calcined product had a specific surface area of 388 m 2 /g, an external specific surface area of 162 m 2 /g, a total pore volume of 0.75 cm 3 /g, and a micropore volume of 0.10 cm 3 /g.
  • the sample is in the shape of nanosheets, and the thickness of the crystal is about 13 nanometers.
  • SiO 2 /Al 2 O 3 26.1 (molar ratio) of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP).
  • ammonia temperature-programmed desorption (NH 3 -TPD) of the obtained sample is similar to that shown in Fig. 4, the total acid content thus obtained is 674 ⁇ mol ⁇ g -1 , and the weak acid content is 68%.
  • the infrared spectrum of pyridine adsorption is similar to that shown in Figure 5, and the ratio of Lewis/Bronsted acid was found to be 1.1.
  • the specific surface area of the obtained calcined product was 377 m 2 /g, the external specific surface area was 158 m 2 /g, the total pore volume was 0.74 cm 3 /g, and the micropore volume was 0.11 cm 3 /g.
  • the sample is in the shape of nanosheets, and the thickness of the crystal is about 11 nanometers.
  • SiO 2 /Al 2 O 3 22.3 (molar ratio) of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP).
  • the ammonia temperature-programmed desorption (NH 3 -TPD) of the obtained sample is similar to that shown in Fig. 4, the total acid content thus obtained is 835 ⁇ mol ⁇ g -1 , and the weak acid content is 64%.
  • the pyridine adsorption infrared spectrum is similar to that shown in Figure 5, and the Lewis/Bronsted acid ratio is 2.8 as measured by analysis.
  • the specific surface area of the obtained calcined product was 372 m 2 /g, the external specific surface area was 149 m 2 /g, the total pore volume was 0.74 cm 3 /g, and the micropore volume was 0.09 cm 3 /g.
  • the sample is in the shape of nanosheets, and the thickness of the crystal is about 12 nanometers.
  • SiO 2 /Al 2 O 3 61.5 (molar ratio) of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP).
  • the ammonia temperature-programmed desorption (NH 3 -TPD) of the obtained sample is similar to that shown in Fig. 4, the total acid content thus obtained is 621 ⁇ mol ⁇ g -1 , and the weak acid content is 56%.
  • the pyridine adsorption infrared spectrum is similar to that shown in Figure 5, and the Lewis/Bronsted acid ratio is 1.0 as measured by analysis.
  • the obtained calcined product had a specific surface area of 362 m 2 /g, an external specific surface area of 149 m 2 /g, a total pore volume of 0.67 cm 3 /g, and a micropore volume of 0.10 cm 3 /g.
  • the sample is in the shape of nanosheets, and the thickness of the crystal is about 12 nanometers.
  • SiO 2 /Al 2 O 3 34.5 (molar ratio) of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP).
  • the ammonia temperature-programmed desorption (NH 3 -TPD) of the obtained sample is similar to that shown in Fig. 4 , the total acid content thus obtained is 643 ⁇ mol ⁇ g -1 , and the weak acid content is 66%.
  • the infrared spectrum of pyridine adsorption is similar to that shown in Figure 5, and the ratio of Lewis/Bronsted acid was found to be 2.1.
  • the specific surface area of the obtained calcined product was 378 m 2 /g, the external specific surface area was 156 m 2 /g, the total pore volume was 0.77 cm 3 /g, and the micropore volume was 0.11 cm 3 /g.
  • the sample is in the shape of nanosheets, and the thickness of the crystal is about 13 nanometers.
  • SiO 2 /Al 2 O 3 21.1 (molar ratio) of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP).
  • the ammonia gas temperature-programmed desorption (NH 3 -TPD) of the obtained sample is similar to that shown in Fig. 4, the total acid content thus obtained is 815 ⁇ mol ⁇ g -1 , and the weak acid content is 68%.
  • the pyridine adsorption infrared spectrum is similar to that shown in Figure 5, and the Lewis/Bronsted acid ratio is 1.7 as measured by analysis.
  • the specific surface area of the obtained calcined product was 394 m 2 /g, the external specific surface area was 171 m 2 /g, the total pore volume was 0.68 cm 3 /g, and the micropore volume was 0.12 cm 3 /g.
  • the sample is in the shape of nanosheets, and the thickness of the crystal is about 12 nanometers.
  • SiO 2 /Al 2 O 3 22.8 (molar ratio) of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP).
  • the ammonia temperature-programmed desorption (NH 3 -TPD) of the obtained sample is similar to that shown in Fig. 4, the total acid content thus obtained is 849 ⁇ mol ⁇ g -1 , and the weak acid content is 59%.
  • the pyridine adsorption infrared spectrum is similar to that shown in Figure 5, and the Lewis/Bronsted acid ratio is 2.3 as measured by analysis.
  • the specific surface area of the obtained calcined product was 372 m 2 /g, the external specific surface area was 144 m 2 /g, the total pore volume was 0.65 cm 3 /g, and the micropore volume was 0.11 cm 3 /g.
  • the sample is in the form of nanosheets, and the thickness of the crystal is about 15 nanometers.
  • SiO 2 /Al 2 O 3 14.5 (molar ratio) of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP).
  • the ammonia temperature-programmed desorption (NH 3 -TPD) of the obtained sample was similar to that shown in Fig. 4, the total acid content thus obtained was 896 ⁇ mol ⁇ g -1 , and the weak acid content was 82%.
  • the pyridine adsorption infrared spectrum is similar to that shown in Figure 5, and the Lewis/Bronsted acid ratio was determined to be 3.0.
  • the specific surface area of the obtained calcined product was 364 m 2 /g, the external specific surface area was 146 m 2 /g, the total pore volume was 0.71 cm 3 /g, and the micropore volume was 0.12 cm 3 /g.
  • the sample is in the form of nanosheets, and the thickness of the crystal is about 18 nanometers.
  • ammonia temperature-programmed desorption (NH 3 -TPD) of the obtained sample is similar to that shown in Fig. 4 , the total acid content thus obtained is 795 ⁇ mol ⁇ g -1 , and the weak acid content is 60%.
  • the infrared spectrum of pyridine adsorption is similar to that shown in Figure 5, and the ratio of Lewis/Bronsted acid was found to be 1.6.
  • the specific surface area of the obtained calcined product was 385 m 2 /g, the external specific surface area was 152 m 2 /g, the total pore volume was 0.63 cm 3 /g, and the micropore volume was 0.09 cm 3 /g.
  • the sample is in the form of nanosheets, and the thickness of the crystal is about 20 nanometers.
  • the ammonia temperature-programmed desorption (NH 3 -TPD) of the obtained sample is similar to that shown in Fig. 4, the total acid content thus obtained is 860 ⁇ mol ⁇ g -1 , and the weak acid content is 74%.
  • the pyridine adsorption infrared spectrum is similar to that shown in Figure 5, and the Lewis/Bronsted acid ratio is 3.2 as measured by analysis.
  • the obtained calcined product had a specific surface area of 373 m 2 /g, an external specific surface area of 148 m 2 /g, a total pore volume of 0.75 cm 3 /g, and a micropore volume of 0.09 cm 3 /g.
  • the sample is in the shape of nanosheets, and the thickness of the crystal is about 16 nanometers.
  • the ammonia temperature-programmed desorption (NH 3 -TPD) of the obtained sample is similar to that shown in Fig. 4, the total acid content thus obtained is 773 ⁇ mol ⁇ g -1 , and the weak acid content is 63%.
  • the pyridine adsorption infrared spectrum is similar to that shown in Figure 5, and the Lewis/Bronsted acid ratio is 2.8 as measured by analysis.
  • the specific surface area of the obtained calcined product was 386 m 2 /g, the external specific surface area was 154 m 2 /g, the total pore volume was 0.73 cm 3 /g, and the micropore volume was 0.10 cm 3 /g.
  • the sample is in the form of nanosheets, and the thickness of the crystal is about 15 nanometers.
  • the ammonia temperature-programmed desorption (NH 3 -TPD) of the obtained sample is similar to that shown in Fig. 4, the total acid content thus obtained is 794 ⁇ mol ⁇ g -1 , and the weak acid content is 66%.
  • the pyridine adsorption infrared spectrum is similar to that shown in Figure 5, and the Lewis/Bronsted acid ratio is 2.4 as measured by analysis.
  • the obtained calcined product had a specific surface area of 383 m 2 /g, an external specific surface area of 155 m 2 /g, a total pore volume of 0.75 cm 3 /g, and a micropore volume of 0.10 cm 3 /g.
  • the sample is in the shape of nanosheets, and the thickness of the crystal is about 17 nanometers.
  • the ammonia gas temperature-programmed desorption (NH 3 -TPD) of the obtained sample is similar to that shown in Fig. 4, the total acid content thus obtained is 787 ⁇ mol ⁇ g -1 , and the weak acid content is 68%.
  • the pyridine adsorption infrared spectrum is similar to that shown in Figure 5, and the Lewis/Bronsted acid ratio is 1.8 as measured by analysis.
  • the specific surface area of the obtained calcined product was 368 m 2 /g, the external specific surface area was 145 m 2 /g, the total pore volume was 0.72 cm 3 /g, and the micropore volume was 0.09 cm 3 /g.
  • the sample is in the shape of nanosheets, and the thickness of the crystal is about 17 nanometers.
  • SiO 2 /Al 2 O 3 22.8 (molar ratio) of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP).
  • the ammonia temperature-programmed desorption (NH 3 -TPD) of the obtained sample was similar to that shown in Fig. 4 , the total acid content thus obtained was 861 ⁇ mol ⁇ g -1 , and the weak acid content was 57%.
  • the infrared spectrum of pyridine adsorption is similar to that shown in Figure 5, and the ratio of Lewis/Bronsted acid was found to be 2.0.
  • the obtained calcined product had a specific surface area of 388 m 2 /g, an external specific surface area of 159 m 2 /g, a total pore volume of 0.71 cm 3 /g, and a micropore volume of 0.10 cm 3 /g.
  • the sample is in the shape of nanosheets, and the thickness of the crystal is about 17 nanometers.
  • SiO 2 /Al 2 O 3 26.1 (molar ratio) of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP).
  • the ammonia temperature-programmed desorption (NH 3 -TPD) of the obtained sample is similar to that shown in Fig. 4, the total acid content thus obtained is 872 ⁇ mol ⁇ g -1 , and the weak acid content is 75%.
  • the pyridine adsorption infrared spectrum is similar to that shown in Figure 5, and the Lewis/Bronsted acid ratio was determined to be 3.0.
  • the obtained calcined product had a specific surface area of 392 m 2 /g, an external specific surface area of 159 m 2 /g, a total pore volume of 0.72 cm 3 /g, and a micropore volume of 0.09 cm 3 /g.
  • the sample is in the form of nanosheets, and the thickness of the crystal is about 15 nanometers.
  • SiO 2 /Al 2 O 3 21.6 (molar ratio) of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP).
  • the ammonia temperature-programmed desorption (NH 3 -TPD) of the obtained sample is similar to that shown in Fig. 4 , the total acid content thus obtained is 908 ⁇ mol ⁇ g- 1 , and the weak acid content is 79%.
  • the pyridine adsorption infrared spectrum is similar to that shown in Figure 5, and the Lewis/Bronsted acid ratio is 3.2 as measured by analysis.
  • the XRD spectrum data of the dried sample is similar to that shown in Figure 8, which is amorphous, not SCM-36 molecular sieve.
  • the molecular sieve synthesized in Example I-5 was ion-exchanged with 0.5 mol/L NH 4 Cl solution (the mass ratio of molecular sieve to ammonium chloride solution was 1:20) at 70° C. for 2 hours, then centrifuged and washed, and ion-exchanged two times. The obtained sample was dried at 100°C for 12 hours and calcined at 550°C for 6 hours to obtain H-type SCM-36 molecular sieve.
  • the reaction conditions are: the reaction temperature is 320°C, the reaction pressure At normal pressure, the weight space velocity of cumene is 2h -1 .
  • the product was analyzed by Shimadzu GC-2014 gas chromatograph. After 1 hour of reaction, the conversion rate of cumene was 25.2%, and the selectivity of benzene in the product was 94.1%.
  • the cumene cracking reaction uses cumene as a raw material, which is cracked into products such as propylene and benzene under the action of a catalyst.
  • Conversion rate % of cumene (molar amount of cumene fed-molar amount of cumene in product)/(molar amount of cumene fed) ⁇ 100%.
  • the selectivity % of benzene (the molar weight of benzene in the product)/(the total molar weight of aromatics in the product) ⁇ 100%;
  • aromatics in the product do not include raw material cumene.
  • the molecular sieve synthesized in Example 1-5 was ion-exchanged with 0.5mol/L NH 4 Cl solution (the mass ratio of molecular sieve to ammonium chloride solution was 1:20) at 70°C for 2 hours, then centrifugally washed, and ion-exchanged
  • the samples obtained after two times were dried at 100°C for 12 hours and calcined at 550°C for 6 hours to obtain H-type SCM-36 molecular sieves.
  • the reaction conditions are as follows: the reaction temperature is 460° C., the reaction pressure is 0.1 MPa, and the weight space velocity of the raw material methanol is 1 h ⁇ 1 .
  • the product was analyzed by a Shimadzu GC-2014 gas chromatograph. After 45 minutes of reaction, the conversion rate of methanol was 99.0%, the selectivity of C2-C4 olefins in the product was 58.6%, and the selectivity of aromatics was 4.2%.
  • the methanol conversion reaction uses methanol as a raw material, which is converted into hydrocarbons such as olefins and aromatics under the action of a catalyst.
  • the conversion rate % of methyl alcohol (the molar weight of feed methanol-the molar weight of methyl alcohol in the product-2 * the molar weight of dimethyl ether in the product)/(the molar weight of feed methanol)*100%;
  • Selectivity % of C2-C4 olefins (2 ⁇ molar amount of C2 olefins in the product+3 ⁇ molar amount of C3 olefins in the product+4 ⁇ molar amount of C4 olefins in the product)/(molar amount of feed methanol-product The molar amount of methanol-2*the molar amount of dimethyl ether in the product)*100%.
  • the selectivity % of aromatics (6 x molar amount of benzene in the product + 7 x molar amount of toluene in the product + 8 x molar amount of xylene in the product) / (molar amount of feed methanol - molar amount of methanol in the product -2 x the molar amount of dimethyl ether in the product) x 100%.
  • reaction product p-xylene is qualitatively analyzed by gas chromatography-mass chromatography (GC-MS), and the substrate 2,5-methylfuran and/or 2,5-hexanediox are analyzed by gas chromatography (GC). Conversion of ketone and yield of reaction product pX.
  • the gas spectrometer is Agilent 7890A of Agilent Corporation of the United States
  • the chromatographic column is a HP-5 non-polar capillary column (30m, 0.53mm)
  • the gas chromatograph is Agilent 7890B
  • the detector is a hydrogen flame ionization detector (FID).
  • the chromatographic column is SE-54 capillary column (30m, 0.53mm).
  • 2,5-dimethylfuran (and/or 2,5-hexanedione) conversion % (2,5-dimethylfuran (and/or 2,5-hexanedione) moles that participated in the reaction amount)/(the molar amount of the reaction substrate 2,5-dimethylfuran (and/or 2,5-hexanedione)) ⁇ 100%.
  • the yield % of product pX (the molar amount of pX produced by the reaction)/(the molar amount of the reaction substrate 2,5-dimethylfuran (and/or 2,5-hexanedione)) ⁇ 100%.
  • the selectivity % of product pX (the molar amount of pX produced by the reaction)/(the molar amount of 2,5-dimethylfuran (and/or 2,5-hexanedione) reacted) ⁇ 100%.
  • the mass ratio of n-heptane to 2,5-dimethylfuran (DMF) was 20
  • the mass ratio of DMF to catalyst was 1
  • the reaction temperature was 240°C
  • the reaction time was 24h.
  • the SCM-36 molecular sieve that 1.0g embodiment I-1 makes, 1.0g DMF and 20g n-heptane are added in the autoclave with stirring, and are filled with 2.0MPa ethylene. Use a temperature-programmed heating mantle to reach the preset temperature and magnetically stir and then stir. After reacting at 240° C. for 24 hours, the gas phase analysis of the reaction liquid calculated that the DMF conversion rate was 86%, the pX selectivity was 94%, and the key impurity polyalkylbenzene selectivity was less than 1%.
  • the mass ratio of n-heptane to DMF is 20
  • the mass ratio of DMF to catalyst is 1
  • the reaction temperature is 240°C
  • the reaction time is 24h.
  • the SCM-36 molecular sieve that 1.0g embodiment 1-2 makes, 1.0g DMF and 20g n-heptane are added in the autoclave with agitation, and are filled with 2.0MPa ethylene. Use a temperature-programmed heating mantle to reach the preset temperature and magnetically stir and then stir. After reacting at 240° C. for 24 hours, the gas phase analysis of the reaction liquid calculated that the DMF conversion rate was 90%, the pX selectivity was 94%, and the key impurity polyalkylbenzene selectivity was less than 1%.
  • Adopt n-heptane as the reaction solvent the mass ratio of n-heptane to DMF is 20, the mass ratio of DMF to catalyst is 1, the reaction temperature is 240°C, and the reaction time is 24h.
  • the SCM-36 molecular sieve that 1.0g embodiment 1-3 makes, 1.0g DMF and 20g n-heptane are added in the autoclave with stirring, and are filled with 2.0MPa ethylene. Use a temperature-programmed heating mantle to reach the preset temperature and magnetically stir and then stir. After reacting at 240° C. for 24 hours, the gas phase analysis of the reaction liquid calculated that the DMF conversion rate was 86%, the pX selectivity was 95%, and the key impurity polyalkylbenzene selectivity was less than 1%.
  • the mass ratio of n-heptane to DMF is 20
  • the mass ratio of DMF to catalyst is 1
  • the reaction temperature is 240°C
  • the reaction time is 24h.
  • the SCM-36 molecular sieve that 1.0g embodiment I-4 makes, 1.0g DMF and 20g n-heptane are added in the autoclave with stirring, and are filled with 2.0MPa ethylene. Use a temperature-programmed heating mantle to reach the preset temperature and magnetically stir and then stir. The reaction was carried out at 240° C. for 24 hours, and the gas phase analysis of the reaction liquid calculated that the DMF conversion rate was 92%, the pX selectivity was 95%, and the key impurity polyalkylbenzene selectivity was less than 1%.
  • n-heptane was used as the reaction solvent
  • the mass ratio of n-heptane to DMF was 20
  • the mass ratio of DMF to catalyst was 1.5
  • the reaction temperature was 250° C.
  • the reaction time was 30 h.
  • Use a temperature-programmed heating mantle to reach the preset temperature and magnetically stir and then stir.
  • the reaction was carried out at 250° C. for 30 h, and the gas phase analysis of the reaction liquid calculated that the DMF conversion rate was 88%, the pX selectivity was 96%, and the key impurity polyalkylbenzene selectivity was less than 1%.
  • n-heptane was used as the reaction solvent
  • the mass ratio of n-heptane to 2,5-hexanedione (HDO) was 20
  • the mass ratio of HDO to catalyst was 1
  • the reaction temperature was 230° C.
  • the reaction time was 20 h.
  • 1.0g of the SCM-36 molecular sieve catalyst prepared in Example I-1, 1g of HDO and 20g of n-heptane were added into a stirred autoclave, and filled with 2.0MPa ethylene. Use a temperature-programmed heating mantle to reach the preset temperature and magnetically stir and then stir. After reacting at 230°C for 20 hours, the gas phase analysis of the reaction liquid calculated that the HDO conversion rate was 86%, the pX selectivity was 95%, and the key impurity polyalkylbenzene selectivity was lower than 1%.
  • n-hexane is used as the reaction solvent
  • the mass ratio of n-hexane to DMF is 30, the mass ratio of DMF to catalyst is 2
  • the reaction temperature is 260° C.
  • the reaction time is 24 hours.
  • the SCM-36 molecular sieve catalyst that 1.0g embodiment I-1 makes, 2.0g DMF and 60g n-hexane are added in the autoclave with agitation, and are filled with 4.0MPa ethylene. Use a temperature-programmed heating mantle to reach the preset temperature and magnetically stir and then stir. After reacting at 260° C. for 24 hours, the gas phase analysis of the reaction liquid calculated that the DMF conversion rate was 83%, the pX selectivity was 94%, and the key impurity polyalkylbenzene selectivity was less than 1%.
  • n-hexane is used as the reaction solvent
  • the mass ratio of n-hexane to DMF is 20
  • the mass ratio of DMF to catalyst is 1.5
  • the reaction temperature is 240° C.
  • the reaction time is 30 h.
  • the SCM-36 molecular sieve catalyst that 1.0g embodiment I-1 makes, 1.5g DMF and 30g n-hexane are added in the autoclave with agitation, and are filled with 2.0MPa ethylene. Use a temperature-programmed heating mantle to reach the preset temperature and magnetically stir and then stir. The reaction was carried out at 240° C. for 30 h, and the gas phase analysis of the reaction liquid calculated that the DMF conversion rate was 88%, the pX selectivity was 93%, and the key impurity polyalkylbenzene selectivity was less than 1%.
  • ⁇ -valerolactone was used as the reaction solvent
  • the mass ratio of ⁇ -valerolactone to HDO was 15
  • the mass ratio of HDO to catalyst was 2
  • the reaction temperature was 270° C.
  • the reaction time was 28 hours.
  • 1.0g of the SCM-36 molecular sieve catalyst prepared in Example I-1, 2g of HDO and 30g of gamma-valerolactone were added into a stirred autoclave, and charged with 3.0MPa ethylene. Use a temperature-programmed heating mantle to reach the preset temperature and magnetically stir and then stir. After reacting at 270° C. for 28 hours, the reaction liquid gas phase analysis calculated that the HDO conversion rate was 89%, the pX selectivity was 95%, and the key impurity polyalkylbenzene selectivity was less than 1%.
  • ⁇ -valerolactone was used as the reaction solvent
  • the mass ratio of ⁇ -valerolactone to DMF was 30, the mass ratio of DMF to catalyst was 3, the reaction temperature was 270° C., and the reaction time was 32 hours.
  • the SCM-36 molecular sieve catalyst that 1.0g embodiment I-1 makes, 3.0g DMF and 90g gamma-valerolactone are added in the autoclave with stirring, and are filled with 4.0MPa ethylene. Use a temperature-programmed heating mantle to reach the preset temperature and magnetically stir and then stir. After reacting at 270° C. for 32 hours, the gas phase analysis of the reaction liquid calculated that the DMF conversion rate was 85%, the pX selectivity was 94%, and the key impurity polyalkylbenzene selectivity was less than 1%.
  • toluene is used as the reaction solvent
  • the mass ratio of toluene to HDO is 22
  • the mass ratio of HDO to catalyst is 1
  • the reaction temperature is 250° C.
  • the reaction time is 18 hours.
  • 1.0g of the SCM-36 molecular sieve catalyst prepared in Example I-1, 1g of HDO and 22g of toluene were added into a stirred autoclave, and charged with 2.0MPa ethylene.
  • Use a temperature-programmed heating mantle to reach the preset temperature and magnetically stir and then stir.
  • the gas phase analysis of the reaction liquid calculated that the HDO conversion rate was 93%, the pX selectivity was 95%, and the key impurity polyalkylbenzene selectivity was less than 1%.
  • toluene is used as the reaction solvent
  • the mass ratio of toluene to HDO is 25
  • the mass ratio of HDO to catalyst is 1.5
  • the reaction temperature is 260° C.
  • the reaction time is 24 hours.
  • the SCM-36 molecular sieve catalyst that 1.0g embodiment I-1 makes, 1.5g HDO and 37.5g toluene are added in the autoclave with stirring, and are filled with 4.0MPa ethylene. Use a temperature-programmed heating mantle to reach the preset temperature and magnetically stir and then stir. The reaction was carried out at 260° C. for 24 hours, and the reaction liquid gas phase analysis calculated that the HDO conversion rate was 90%, the pX selectivity was 95%, and the key impurity polyalkylbenzene selectivity was less than 1%.
  • cyclohexane is used as the reaction solvent
  • the mass ratio of cyclohexane to DMF is 30, the mass ratio of DMF to catalyst is 2
  • the reaction temperature is 250° C.
  • the reaction time is 40 h.
  • the SCM-36 molecular sieve catalyst that 1.0g embodiment I-1 makes, 2.0g DMF and 60g hexanaphthene are added in the autoclave with stirring, and charge into 4.0MPa ethylene. Use a temperature-programmed heating mantle to reach the preset temperature and magnetically stir and then stir. The reaction was carried out at 250° C. for 40 hours, and the gas phase analysis of the reaction liquid calculated that the DMF conversion rate was 86%, the pX selectivity was 96%, and the key impurity polyalkylbenzene selectivity was less than 1%.
  • cyclohexane was used as the reaction solvent
  • the mass ratio of cyclohexane to HDO was 20
  • the mass ratio of HDO to catalyst was 2
  • the reaction temperature was 255° C.
  • the reaction time was 38 hours.
  • 1.0g of the SCM-36 molecular sieve catalyst prepared in Example I-1, 2.0g of HDO and 40.0g of cyclohexane were added into a stirred autoclave, and charged with 4.0MPa ethylene. Use a temperature-programmed heating mantle to reach the preset temperature and magnetically stir and then stir.
  • the reaction was carried out at 255°C for 38 hours, and the gas phase analysis of the reaction liquid calculated that the HDO conversion rate was 87%, the pX selectivity was 95%, and the key impurity polyalkylbenzene selectivity was less than 1%.
  • the mass ratio of n-heptane to DMF is 20
  • the mass ratio of DMF to catalyst is 1
  • the reaction temperature is 240°C
  • the reaction time is 24h.
  • the SCM-36 molecular sieve that 1.0g embodiment I-1 makes, 1.0g DMF and 20g n-heptane are added in the autoclave with stirring, and are filled with 2.0MPa ethylene. Use a temperature-programmed heating mantle to reach the preset temperature and magnetically stir and then stir. The reaction was carried out at 240° C. for 24 hours, and the reaction liquid was analyzed by gas phase to calculate the conversion rate of DMF and the selectivity of pX.
  • the specific surface area of the obtained calcined product was 372 m 2 /g, the external specific surface area was 149 m 2 /g, the total pore volume was 0.74 cm 3 /g, and the micropore volume was 0.09 cm 3 /g.
  • the sample is in the shape of nanosheets, and the thickness of the crystal is about 12 nanometers.
  • SiO 2 /Al 2 O 3 61.5 (molar ratio) of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP).
  • the ammonia gas temperature-programmed desorption (NH 3 -TPD) of the obtained sample is shown in Fig. 12, the total acid content thus obtained is 470 ⁇ mol ⁇ g -1 , and the weak acid content is 47%.
  • the infrared spectrum of pyridine adsorption is shown in Figure 13, and the Lewis/Bronsted acid ratio was determined to be 0.4.
  • n-heptane Using n-heptane as the reaction solvent, add 1.0 g of the above-prepared SCM-36 molecular sieve, 1.0 g of DMF and 20 ml of n-heptane into a stirred autoclave, and fill it with 2.0 MPa ethylene. Use a temperature-programmed heating mantle to reach the preset temperature and magnetically stir and then stir. The reaction was carried out at 240°C for 24 hours, and the gas phase analysis of the reaction liquid calculated that the DMF conversion rate was 93%, the pX selectivity was 90%, and the key impurity polyalkylbenzene selectivity was 3%.
  • n-heptane a reaction solvent
  • 1.0g of the catalyst prepared above, 1.0g of DMF and 20ml of n-heptane were added to a stirred autoclave, and filled with 2.0MPa ethylene.
  • the reaction was carried out at 240° C. for 24 hours, and the gas phase analysis of the reaction liquid calculated that the DMF conversion rate was 67%, and the pX selectivity was 72%.

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Abstract

一种硅铝分子筛SCM-36、其制造方法和应用，分子筛的硅铝比n≥5，并且具有独特的XRD衍射谱图。SCM-36分子筛是一种新型分子筛，可作为吸附剂、催化剂或催化剂载体。

Description

硅铝分子筛SCM-36、其制造方法和应用 技术领域
本申请涉及分子筛的技术领域，具体涉及一种硅铝分子筛、其制造方法和应用。
背景技术
在工业上，分子筛材料因其具有空旷的结构和大的表面积而被广泛用于催化、离子交换、吸附和分离等领域。这些材料结构上的细微差别，预示着用来表征它们的各种可观察性能有差异，如它们的形貌、比表面积、空隙尺寸和这些尺寸的可变性等，同时也意味着它们本身在材料的催化和吸附性能等方面存在重大差异。
结晶微孔沸石的基本骨架结构是基于刚性的三维TO 4(SiO 4，AlO 4等)单元结构；在此结构中TO 4是以四面体方式共享氧原子，骨架四面体如AlO 4的电荷平衡是通过表面阳离子如Na +、H +的存在保持的。由此可见通过阳离子交换方式可以改变沸石的骨架性质。同时，在沸石的结构中存在着丰富的、孔径一定的孔道体系，这些孔道相互交错形成三维网状结构，且孔道中的水或有机物被去除后其骨架仍能稳定存在(US 4439409)。正是基于上述结构，沸石不但对多种有机反应具有良好催化活性、优良的择形性、并通过改性可实现良好的选择性(US 6162416，US 4954325，US 5362697)。
分子筛的特定结构是由X-射线衍射谱图(XRD)确定的，X-射线衍射谱图(XRD)由X-射线粉末衍射仪测定，使用Cu-Kα射线源、镍滤光片。不同的沸石分子筛，其XRD谱图特征不同。已有的分子筛，如A型沸石、Y型沸石、MCM-22分子筛等等均具有各自特点的XRD谱图。
同时，具有相同XRD谱图特征，但骨架元素种类不同，也是不同分子筛。如TS-1分子筛(US4410501)与ZSM-5分子筛(US3702886)，它们二者具有相同的XRD谱图特征，但骨架元素不同。具体来说，TS-1分子筛骨架元素为Si和Ti，具有催化氧化功能，而ZSM-5分子筛骨架元素为Si和Al，具有酸催化功能。
另外，具有相同XRD谱图特征，骨架元素种类也相同，但是骨架 元素的相对含量不同，属于不同分子筛。如X沸石(US2882244)与Y沸石(US3130007)，二者具有相同的XRD谱图特征，骨架元素均为Si和Al，但Si和Al的相对含量不同。具体来说，X沸石Si/Al摩尔比低于1.5，而Y沸石Si/Al摩尔比高于1.5。
发明内容
本申请的目的是提供一种新型的硅铝分子筛(本文中称为SCM-36分子筛)、其制造方法和应用，所述分子筛具体特定的XRD谱图特征，可作为吸附剂、催化剂载体和催化剂使用，并且作为催化剂用于2，5-二甲基呋喃和/或2，5-己二酮制备对二甲苯的反应时具有高对二甲苯选择性和循环稳定性。
为了实现上述目的，一方面，本申请提供了一种硅铝分子筛，所述分子筛的硅铝比n≥5，并且所述分子筛的X射线衍射谱图显示出如下表所示的衍射峰相对强度特性：
2θ(°) 相对强度(I/I 0×100)
8.99-9.59 s
12.48-13.08 s-vs
18.91-19.51 s-vs
23.39-23.99 m
24.00-24.41 m
25.65-26.25 vs
另一方面，本申请提供了一种制造硅铝分子筛的方法，包括如下步骤：
1)使包含硅源、铝源、有机结构导向剂(A)、有机结构导向剂(B)、碱源和水的混合物进行晶化反应，以获得分子筛；和
2)任选地，焙烧步骤1)所得的分子筛；
其中，所述有机结构导向剂(A)选自四甲基铵类化合物；所述有机结构导向剂(B)选自C6-16烷基吡啶鎓化合物、正辛基三甲基铵类化合物或者它们的组合。
另一方面，提供了一种分子筛组合物，包含根据本申请的硅铝分子筛以及粘结剂。
再一方面，提供了根据本申请的硅铝分子筛或者分子筛组合物作为吸附剂、催化剂或者催化剂载体的应用。
又一方面，本申请提供了一种制备对二甲苯的方法，包括：使包含2，5-二甲基呋喃、2，5-己二酮或者它们的组合的原料在包含本申请的硅铝分子筛或由其组成的催化剂存在下、与乙烯接触反应的步骤。
本申请的分子筛具有现有技术中未见报道的新颖的结构，可用作吸附剂、催化剂载体或者催化剂。特别地，本申请的分子筛作为催化剂用于2，5-二甲基呋喃和/或2，5-己二酮制备对二甲苯的反应时具有高对二甲苯选择性和循环稳定性。
附图说明
图1为实施例I-1中所得分子筛的X射线衍射(XRD)谱图；
图2为实施例I-1中所得分子筛的扫描电镜(SEM)图像；
图3为实施例I-1中所得分子筛的透射电镜(TEM)图像；
图4为实施例I-1中所得分子筛的氨气程序升温脱附(NH 3-TPD)谱图；
图5为实施例I-1中所得分子筛的吡啶吸附红外(Py-FTIR)谱图；
图6为实施例I-2中所得分子筛的XRD谱图；
图7为实施例I-3中所得分子筛的SEM图像；
图8为对比例I-1中所得样品的XRD谱图；
图9为对比例I-3中所得样品的XRD谱图；
图10为对比例I-4中所得样品的XRD谱图；
图11为实施例II-15中SCM-36分子筛循环使用条件下2，5-二甲基呋喃转化率和对二甲苯选择性的图；
图12为实施例II-16中所得分子筛的NH 3-TPD谱图；
图13为实施例II-16中所得分子筛的Py-FTIR谱图。
具体实施方式
下面对本申请的具体实施方式进行详细说明，但是需要指出的是，本申请的保护范围并不受这些具体实施方式的限制，而是由附录的权利要求书来确定。
本说明书提到的所有出版物、专利申请、专利和其它参考文献全 都引于此供参考。除非另有定义，本说明书所用的所有技术和科学术语都具有本领域技术人员常规理解的含义。在有冲突的情况下，以本说明书的定义为准。
当本说明书以词头“本领域技术人员公知”、“现有技术”或其类似用语来导出材料、物质、方法、步骤、装置或部件等时，该词头导出的对象涵盖本申请提出时本领域常规使用的那些，但也包括目前还不常用，却将变成本领域公认为适用于类似目的的那些。
在本说明书的上下文中，除了明确说明的内容之外，未提到的任何事宜或事项均直接适用本领域已知的那些而无需进行任何改变。而且，本文描述的任何实施方式均可以与本文描述的一种或多种其他实施方式自由结合，由此而形成的技术方案或技术思想均视为本申请原始公开或原始记载的一部分，而不应被视为是本文未曾披露或预期过的新内容，除非本领域技术人员认为该结合是明显不合理的。
在本说明书的上下文中，所谓“硅铝比”或“硅铝摩尔比”是指分子筛中以SiO 2计的硅和以Al 2O 3计的铝之间的摩尔比例。
在本说明书的上下文中，所谓“以氧化物计”，是指以相应元素的能够稳定存在的最高价态的氧化物形式来计算。例如，表述“以氧化物计”，对于硅是指以SiO 2计，对于铝是指以Al 2O 3计；对于钛是指以TiO 2计，对于硼是指以B 2O 3计，对于锆是指以ZrO 2计，对于锡是指以SnO 2计，对于铁是指以Fe 2O 3计。
在本说明书的上下文中，对于分子筛，在其孔道中的除水及金属离子以外的其他合成该分子筛时填充在孔道中的物质(比如有机结构导向剂分子等)未被脱除之前，称为“前驱体”。
在本说明书的上下文中，所谓“合成态”、“合成态形式”或者“合成态分子筛”，是指所述分子筛在合成步骤结束之后、后处理步骤(如焙烧步骤)开始之前的状态。作为所述合成态，具体举例而言，可以是合成步骤结束之后直接呈现的状态，此时一般称为分子筛前驱体。鉴于此，处于所述合成态时，所述分子筛可能含有水和/或有机物(特别是有机结构导向剂)。
在本说明书的上下文中，所谓“焙烧后”、“焙烧后形式”或者“焙烧后分子筛”，是指所述分子筛在焙烧之后的状态。作为所述焙烧后状态，具体举例而言，可以是将合成态分子筛通过焙烧而进一步 脱除其孔道中可能存在的有机物(特别是有机结构导向剂)和水等之后而呈现的状态。
在本说明书的上下文中，在分子筛的XRD数据中，w、m、s、vs、w-m、m-s和s-vs等代表基于衍射峰强度(以峰高计)计算得到的相应2θ角处的衍射峰相对于最强衍射峰(即强度最大的衍射峰)的相对强度I/I 0，其中I表示相应衍射峰的峰强度而I 0表示最强衍射峰的峰强度，w代表弱，m代表中等，s代表强，vs代表非常强，w-m代表弱到中等，m-s代表中等到强，且s-vs代表强到非常强，这种表示方式是本领域技术人员所熟知的。一般而言，w代表小于20；m代表20-40；s代表40-70；vs代表大于70，w-m代表小于40，m-s代表20-70，而s-vs代表大于40。
在本说明书的上下文中，分子筛的结构是在550℃焙烧5小时后由X-射线衍射谱图确定的，而X-射线衍射谱图由X-射线粉末衍射仪测定，使用Cu-Kα射线源、镍滤光片。样品测试前，采用扫描电子显微镜观察分子筛样品的结晶情况，确认样品中只含有一种晶体，即分子筛样品为纯相，在此基础上再进行XRD测试，确保XRD谱图中的衍射峰中没有其他晶体的干扰峰。
根据本申请，分子筛的XRD衍射谱图中各衍射峰的晶面间距可以基于衍射峰的2θ值通过布拉格公式：λ＝2dsinθ(其中λ为入射波的波长，
Figure PCTCN2022123784-appb-000001
d为晶面间距，θ是入射光与散射平面间的夹角)计算得到。
在本说明书的上下文中，所谓“比表面积”，是指单位质量样品所具有的总面积，包括内表面积和外表面积。非孔性样品只具有外表面积，如硅酸盐水泥、一些粘土矿物粉粒等；有孔和多孔样品具有外表面积和内表面积，如石棉纤维、硅藻土和分子筛等。有孔和多孔样品中孔径小于2纳米的孔的表面积是内表面积，扣除内表面积后的表面积称为外表面积，单位质量样品具有的外表面积即外比表面积。
在本说明书的上下文中，所谓“孔容”或“孔体积”，是指单位质量分子筛所具有的孔的容积。所谓“总孔体积”，是指单位质量分子筛所具有的全部孔的容积。所谓“微孔体积”，是指单位质量分子筛所具有的全部微孔(一般指的是孔道直径小于2纳米的孔)的容积。
在本申请中，分子筛材料的孔结构参数，如：总孔体积、微孔体 积、总比表面积和外比表面积是通过物理吸附仪(如美国麦克仪器公司的TriStar 3000物理吸附仪)测得分子筛的氮气物理吸脱附等温线，再经BET法和t-plot法计算得到，总孔体积取相对压力P/P 0＝0.99对应的孔体积。氮气物理吸脱附实验条件为：测量温度-196℃，测量前将分子筛在300℃真空预处理10小时，以氮气为吸附质。
在本说明书的上下文中，所谓晶体的厚度，指使用透射电子显微镜在10万倍的放大倍率下观测分子筛，随机选取一个观测视野，计算该观测视野中所有片状晶体的厚度之和的平均值。重复该操作共计10次。以10次的平均值之和的平均值作为晶体厚度。
如上所述，在第一方面，本申请提供了一种硅铝分子筛，所述分子筛的硅铝比n≥5，优选n在5-80范围内，进一步优选n在10-65范围内，并且所述分子筛的X射线衍射谱图显示出如下表所示的衍射峰相对强度特性：
2θ(°) 相对强度(I/I 0×100)
8.99-9.59 s
12.48-13.08 s-vs
18.91-19.51 s-vs
23.39-23.99 m
24.00-24.41 m
25.65-26.25 vs
。
在优选的实施方式中，所述分子筛的X射线衍射谱图还显示出如下表任一行所示的衍射峰相对强度特性：
2θ(°) 相对强度(I/I 0×100)
16.50-17.10 w-m
48.33-48.93 w-m
。
在进一步优选的实施方式中，所述分子筛的X射线衍射谱图还显示出如下表任一行所示的衍射峰相对强度特性：
2θ(°) 相对强度(I/I 0×100)
13.65-14.25 w
30.23-30.83 w
36.67-37.27 w
43.05-43.65 w
。
本申请的硅铝分子筛SCM-36具有本领域之前从未获得过的结构。根据本申请，所述SCM-36分子筛可以以未焙烧状态(合成态)存在，也可以以焙烧的状态存在。在以合成态存在时，所述SCM-36分子筛一般具有如式“nSiO 2·Al 2O 3·有机结构导向剂·水”或“nSiO 2·Al 2O 3·mMO x·有机结构导向剂·水”所示的示意性化学组成，在以焙烧状态存在或以合成态存在时，所述SCM-36分子筛一般还可以具有如式“nSiO 2·Al 2O 3”或“nSiO 2·Al 2O 3·mMO x”所示的示意性化学组成，其中n表示所述分子筛的硅铝比且n≥5，m表示所述分子筛中硅元素与M元素的摩尔比，且m的值满足以氧化物计并以Si、Al和元素M的总量为基准，所述分子筛中所述元素M的总含量不超过3mol％。在后者的情况下，已知的是，分子筛中有时会(尤其是在刚合成之后)含有一定量的水分，但本申请认为并没有必要对该水分的量进行测定，因为该水分的存在与否并不会实质上影响该分子筛的XRD谱图。鉴于此，该示意性化学组成实际上代表的是该分子筛的无水化学组成。
在优选的实施方式中，通过BET法测定，所述分子筛的比表面积为300-700米 2/克，优选300-600米 2/克，更优选350-500米 2/克，例如为360-480米 2/克；外比表面积为50-300米 2/克，优选80-250米 2/克，更优选100-220米 2/克。
在优选的实施方式中，所述分子筛的总孔体积为0.20-1.50厘米 3/克，优选0.40-1.20厘米 3/克，更优选0.5-1.0厘米 3/克；通过t-plot法测定的微孔体积为0.05-0.35厘米 3/克，优选0.08-0.30厘米 3/克，更优选0.09-0.25厘米 3/克。
在优选的实施方式中，所述分子筛的晶体形貌为纳米片状，晶体的厚度＜30纳米，优选5-25纳米，更优选7-20纳米，例如为10-20纳米。
在优选的实施方式中，通过NH 3程序升温脱附(NH 3-TPD)方法测定，所述分子筛的总酸量为400-1200μmol·g -1，优选为500-1000μmol·g -1，其中，弱酸含量≥40％，优选为45％-90％，所述弱 酸定义为脱附温度为100-250℃的酸。
在优选的实施方式中，通过吡啶吸附红外光谱法测定，所述分子筛的Lewis酸/Bronsted酸比例为0.1-3.8，优选为0.4-3.5。
在优选的实施方式中，所述分子筛还包含至少一种选自钛、硼、锆、锡、铁或者它们的组合的元素M。
在进一步优选的实施方式中，以氧化物计并以Si、Al和元素M的总量(其中Si、Al和元素M的量分别以SiO 2、Al 2O 3和元素M的氧化物形式计)为基准，所述分子筛中所述元素M的总含量不超过3mol％。
在第二方面，本申请提供了一种制造硅铝分子筛的方法，包括如下步骤：
1)使包含硅源、铝源、有机结构导向剂(A)、有机结构导向剂(B)、碱源和水的混合物进行晶化反应，以获得分子筛；和
2)任选地，焙烧步骤1)所得的分子筛；
其中，所述有机结构导向剂(A)选自四甲基铵类化合物；所述有机结构导向剂(B)选自C10-16烷基吡啶鎓化合物、正辛基三甲基铵类化合物或者它们的组合。
在优选的实施方式中，步骤1)的所述混合物中，所述硅源(以SiO 2计)、铝源(以Al 2O 3计)、有机结构导向剂(A)、有机结构导向剂(B)、碱源和水的摩尔比例为1∶(0.01-0.20)∶(0.05-0.80)∶(0.05-0.80)∶(0.05-0.50)∶(8-80)，优选1∶(0.01-0.10)∶(0.08-0.65)∶(0.08-0.65)∶(0.08-0.45)∶(10-70)，更优选1∶(0.02-0.07)∶(0.10-0.50)∶(0.10-0.50)∶(0.10-0.40)∶(12-60)。
在本申请的方法中，步骤1)的所述晶化可以按照本领域常规已知的任何方式进行，比如可以举出使所述硅源、所述铝源、所述有机结构导向剂、碱源和水按照预定的比例混合，并使所获得的混合物在晶化条件下水热晶化的方法。
在优选的实施方式中，步骤1)的所述晶化的晶化温度为120-200℃，晶化时间为1-15天，优选晶化温度为130-190℃，晶化时间为2-12天，更优选晶化温度为140-180℃，晶化时间为3-9天。
在本申请的方法中，在步骤1)的晶化结束之后，可以通过常规已知的任何分离方式从所获得的产物混合物中分离出分子筛作为产品，由此获得本申请的硅铝分子筛SCM-36。作为所述分离方式，比如可以举出对所述获得的产物混合物进行过滤、洗涤和干燥的方法。在此， 所述过滤、洗涤和干燥可以按照本领域常规已知的任何方式进行。具体举例而言，作为所述过滤，例如可以对所得的产物混合物进行抽滤；作为所述洗涤，例如可以使用去离子水进行洗涤；作为所述干燥，例如可以将样品置于商品化的鼓风干燥箱中进行烘干。干燥温度可以为40-150℃，优选50-120℃，干燥时间可以为1-30小时，优选2-24小时。该干燥可以在常压下进行，也可以在减压下进行。
在本申请的方法中，根据需要，还可以对步骤1)所得的分子筛进行焙烧，以脱除有机结构导向剂和可能存在的水分等，由此获得焙烧后的分子筛(同样属于本申请的SCM-36分子筛)。所述焙烧可以按照本领域常规已知的任何方式进行，比如焙烧温度一般为300-800℃，优选400-650℃，而焙烧时间一般为1-12小时，优选2-10小时。另外，所述焙烧一般在含氧气氛下进行，比如空气或者氧气气氛下。
根据本申请，所述硅源和铝源可以是各种常规用于制造硅铝分子筛的硅源和铝源，本申请对此并没有严格的限制。在优选的实施方式中，所述硅源选自硅酸、硅胶、硅溶胶、硅酸四乙酯、水玻璃或者它们的组合；所述铝源选自氢氧化铝、氧化铝、铝酸盐、铝盐和四烷氧基铝或者它们的组合。
根据本申请，所述碱源可以是各种常规用于硅铝分子筛制造过程的碱源，本申请对此并没有严格的限制。在优选的实施方式中，所述碱源选自以碱金属和/或碱土金属为阳离子的无机碱或者它们的组合，例如可以选自氢氧化钠、氢氧化钾、氢氧化钙、氢氧化锂，或者它们的组合。
根据本申请，所述有机结构导向剂(A)选自以(CH 3) 4N +为阳离子的四甲基铵类化合物，例如四甲基氢氧化铵、四甲基铵有机酸盐和四甲基铵无机酸盐。在优选的实施方式中，所述有机结构导向剂(A)选自四甲基氢氧化铵、四甲基氯化铵、四甲基溴化铵、四甲基碘化铵或者它们的组合。
根据本申请，所述有机结构导向剂(B)选自以R(C 5H 5N) +为阳离子，其中R为C 10-16烷基，的吡啶鎓化合物、以C 8H 17(CH 3) 3N +为阳离子的正辛基三甲基铵类化合物或者它们的组合，例如C 10-16烷基吡啶鎓氢氧化物、C 10-16烷基吡啶鎓有机酸盐、C 10-16烷基吡啶鎓无机酸盐、正辛基三甲基氢氧化铵、正辛基三甲基铵有机酸盐和正辛基三甲基铵无机酸 盐。在优选的实施方式中，所述有机结构导向剂(B)选自溴化十六烷基吡啶、溴化十四烷基吡啶、溴化十二烷基吡啶、溴化十烷基吡啶、氯化十六烷基吡啶、氯化十四烷基吡啶、氢氧化十六烷基吡啶、正辛基三甲基氯化铵、正辛基三甲基溴化铵、正辛基三甲基氢氧化铵或者它们的组合。进一步优选地，所述有机结构导向剂(B)选自溴化十六烷基吡啶、溴化十四烷基吡啶、溴化十二烷基吡啶、氯化十六烷基吡啶、氢氧化十六烷基吡啶、正辛基三甲基氯化铵、正辛基三甲基溴化铵或者它们的组合。
在优选的实施方式中，步骤1)的所述混合物中还包含至少一种元素M源，所述元素M选自钛、硼、锆、锡和铁。
在进一步优选的实施方式中，钛源选自含钛有机金属配合物、四烷氧基钛、二氧化钛、硝酸钛或者它们的组合；硼源选自硼酸、硼酸盐、硼砂、三氧化二硼或者它们的组合；锆源选自含锆有机金属配合物、锆盐、氢氧化锆、醇锆、二氧化锆或者它们的组合；锡源选自含锡有机金属配合物、锡盐、二氧化锡或者它们的组合；铁源选自含铁有机金属配合物、硝酸铁、氯化铁、氧化铁或者它们的组合。
在进一步优选的实施方式中，所述硅源(以SiO 2计)与所述元素M源(以相应的氧化物计)的摩尔比为1∶(0.002-0.10)，优选1∶(0.005-0.05)。
在第三方面，提供了按照本申请的方法制造得到的硅铝分子筛SCM-36。
本申请的硅铝分子筛SCM-36可以任何的物理形式得到和使用，比如粉末状、颗粒状或者模制品状(比如条状、三叶草状等)。可以按照本领域常规已知的任何方式获得这些物理形式，并没有特别的限定。
在第四方面，本申请提供了一种分子筛组合物，包含根据本申请的硅铝分子筛SCM-36或者按照本申请的方法制造得到的硅铝分子筛SCM-36，以及粘结剂。
本申请的硅铝分子筛SCM-36可以与其他材料复合使用，由此获得分子筛组合物。作为这些其他材料，比如可以举出活性材料和非活性材料。作为所述活性材料，比如可以举出合成沸石、天然沸石或者其他类型的分子筛等，作为所述非活性材料(一般称为粘结剂)，本申请并没有严格的限制，例如可以采用常规用于制造吸附剂或催化剂的那些，包括但不限于粘土，白土，氧化硅，硅胶，氧化铝等或其混合物 等。这些其他材料可以单独使用一种，或者以任意的比例组合使用多种。作为所述其他材料的用量，可以直接参照本领域的常规用量，并没有特别的限制。
根据本申请，所述分子筛组合物可以呈现为任何的物理形式，比如粉末状、颗粒状或者模制品状(比如条状、三叶草状等)。可以按照本领域常规已知的任何方式获得这些物理形式，并没有特别的限定。
在第五方面，提供了本申请的硅铝分子筛SCM-36或者分子筛组合物，或者按照本申请的方法制造得到的硅铝分子筛SCM-36作为吸附剂、催化剂或者催化剂载体的应用。
本申请的SCM-36分子筛或分子筛组合物可用作吸附剂，例如用来在气相或液相中从多种组分的混合物中分离出至少一种组分。据此，所述至少一种组分可以部分或基本全部从各种组分的混合物中分离出来，具体方式比如是让所述混合物与所述SCM-36分子筛或所述分子筛组合物相接触，有选择地吸附这一组分。作为所述吸附剂的例子，可以提及例如用于异丙醇，异丁醇和异丁酮等有机溶剂中少量水分的去除，以及用于天然气中少量水分的吸附和脱除。
此外，本申请的SCM-36分子筛或分子筛组合物还可直接或者经过本领域常规针对分子筛进行的必要处理或转化(比如离子交换等)之后用作催化剂载体、催化剂或其催化活性组分。例如，SCM-36分子筛可以用作催化剂载体，比如负载金属Pd，得到Pd/SCM-36，其可以作为Pd催化剂用于加氢或脱氢反应，此时SCM-36是载体；也可以用作双功能催化剂，此时SCM-36既是金属Pd的载体，也是固体酸催化材料，提供酸中心。此外，可以使反应物(比如烃类)在包含本申请的SCM-36分子筛或分子筛组合物的催化剂存在下进行预定反应，由此获得目标产物，作为所述预定反应可以提及例如：异丙苯裂解、甲醇转化生成烯烃或芳烃的反应、以及以2，5-二甲基呋喃和/或2，5-己二酮为原料与乙烯反应制备对二甲苯的反应等。
在第六方面，本申请提供了一种催化剂，其包含本申请的硅铝分子筛SCM-36或者分子筛组合物，或者按照本申请的方法制造得到的硅铝分子筛SCM-36，或者由其组成。
在优选的实施方式中，所述催化剂为适用于异丙苯裂解、甲醇转化生成烯烃或芳烃的反应、以及以2，5-二甲基呋喃和/或2，5-己二酮为 原料与乙烯反应制备对二甲苯的反应等的催化剂。
在第七方面，本申请提供了一种制备对二甲苯的方法，包括：使包含2，5-二甲基呋喃、2，5-己二酮或者它们的组合的原料在包含本申请的硅铝分子筛SCM-36或由其组成的催化剂存在下，与乙烯接触反应的步骤。
本申请的对二甲苯制备方法采用SCM-36分子筛为催化剂或催化剂活性组分，在温和反应条件下，2，5-二甲基呋喃和/或2，5-己二酮能够高效地转化为对二甲苯，转化率和产物对二甲苯选择性均非常高。同时，所得产物中关键杂质(例如多烷基苯，2，5-己二酮和2-环戊烯酮)含量极低，大大减少了分离能耗。此外，本申请通过采用SCM-36分子筛为催化剂，具有很高的稳定性，循环使用四次未见催化剂性能有明显变化。
在优选的实施方式中，在有机溶剂存在下进行所述接触反应，所述有机溶剂种类可在较宽范围内进行选择，常用有机溶剂均可以用于本申请。优选地，所述有机溶剂选自正己烷、正庚烷、γ-戊内酯、四氢呋喃、甲苯、环己烷或者它们的组合。所述有机溶剂的用量可在较宽范围内进行选择，具体可以依据反应需求确定。在一种优选的实施方式中，所述有机溶剂与原料的质量比为8-60∶1，优选为10-30∶1，这样有利于提高底物转化率和产物对二甲苯选择性，降低产物中关键杂质含量。
在本申请的方法中，所述催化剂的用量可在较宽范围内进行选择，具体可以依据反应需求确定。在一种优选的实施方式中，所述原料与催化剂的质量比为0.6-30∶1，优选为1.0-10∶1，这样有利于提高底物转化率和产物对二甲苯选择性，降低产物中关键杂质含量。
在本申请的方法中，所述接触反应的条件可在较宽范围内进行选择，具体可以依据反应需求确定。在优选的实施方式中，所述反应的条件包括：反应温度为160-340℃，优选为220-270℃；反应时间可以依据温度进行确定，例如反应时间可以为6-64h，优选为8-48h，更优选18-40h；反应压力为1-8MPa，优选为2-4MPa。
实施例
下面通过实施例进一步详细地说明本申请的技术方案，但本申请 的保护范围并不限于这些实施例。
以下实施例和对比例中，如无明确说明，所用试剂和原料均为市售产品，纯度为分析纯。
以下实施例和对比例中未注明具体条件的实验方法，按照常规方式和条件，或按照商品说明书选择。
以下实施例和对比例中，分子筛产品的XRD测量方法是：采用Panalytical X PERPRO型X-射线粉末衍射仪，分析样品的物相，CuKα射线源
Figure PCTCN2022123784-appb-000002
镍滤光片，2θ扫描范围2-50°，操作电压40KV，电流40mA，扫描速率10°/min。
以下实施例和对比例中，电感耦合等离子体原子发射光谱仪(ICP)型号为Varian 725-ES，将分析样品用氢氟酸溶解检测得到样品的元素含量。
以下实施例和对比例中，NH 3程序升温脱附(NH 3-TPD)实验在TPD/TPR Altamira AMI-3300型仪器上进行，并通过对所得谱图进行拟合分峰，计算得到总酸量，并将脱附温度为100-250℃对应的酸定义为弱酸，由此计算得到弱酸所占比例。
以下实施例和对比例中，扫描电子显微镜图的测试采用日本日立公司Hitachi S-4800II型场发射扫描电镜，测试电压为15KV。透射电子显微镜采用荷兰FEI公司G2F30透射电子显微镜，工作电压300kV，在10万倍的放大倍率下观测分子筛，随机选取一个观测视野，测量该观测视野中所有晶体的厚度，重复该操作5次，以5次的平均值作为晶体的平均厚度。
以下实施例和对比例中，Py-FTIR图的测试采用Thermo Nicolet 5700FT-IR光谱仪。
实施例I-1
将24.73克去离子水、6.89克氢氧化钠溶液(含NaOH 10重量％)、5.35克有机结构导向剂(A)四甲基氢氧化铵(含TMAOH 25重量％)、3.05克有机结构导向剂(B)正辛基三甲基氯化铵、1.234克偏铝酸钠(含Al 2O 340.5重量％，Na 2O 30.6重量％)、14.72克硅溶胶(含SiO 240重量％)混合均匀，制得混合物，反应物的物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.05
四甲基氢氧化铵(A)/SiO 2＝0.15
正辛基三甲基氯化铵(B)/SiO 2＝0.15
NaOH/SiO 2＝0.30
H 2O/SiO 2＝25；
混合均匀后，装入不锈钢反应釜中，在160℃下晶化6天。晶化结束后过滤、洗涤，在110℃烘箱中干燥12小时，在550℃空气中焙烧6小时得分子筛。
干燥样品的XRD谱图数据如表I-1和图1所示，样品的SEM图如图2所示，TEM图如图3所示。
表I-1实施例I-1所得分子筛的XRD谱图数据
Figure PCTCN2022123784-appb-000003
所得焙烧产品的比表面积为380米 2/克，外比表面积为170米 2/克，总孔体积0.92厘米 3/克，微孔体积为0.10厘米 3/克。样品为纳米片状形貌，晶体的厚度约为15纳米。
采用电感耦合等离子体原子发射光谱(ICP)测得焙烧样品的SiO 2/Al 2O 3＝21.6(摩尔比)。
所得样品的氨气程序升温脱附(NH 3-TPD)谱图如图4所示，由此得到的总酸量为782μmol·g -1，弱酸含量为63％。吡啶吸附红外谱图如图5所示，分析测得Lewis/Bronsted酸比例为2.2。
实施例I-2
参照实施例I-1进行试验，只是所用反应物和物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.067
四甲基氢氧化铵(A)/SiO 2＝0.15
正辛基三甲基氯化铵(B)/SiO 2＝0.20
NaOH/SiO 2＝0.30
H 2O/SiO 2＝20；
混合均匀后，装入不锈钢反应釜中，在160℃下晶化5天。晶化结束后过滤、洗涤，在100℃烘箱中干燥16小时，在550℃空气中焙烧8小时得分子筛。
干燥样品的XRD谱图数据如表I-2和图6所示，样品的SEM图与图2所示类似；
表I-2实施例I-2所得分子筛的XRD谱图数据
Figure PCTCN2022123784-appb-000004
所得焙烧产品的比表面积为392米 2/克，外比表面积为166米 2/克，总孔体积0.73厘米 3/克，微孔体积为0.10厘米 3/克。样品为纳米片状形貌，晶体的厚度约为12纳米。
采用电感耦合等离子体原子发射光谱(ICP)测得焙烧样品的SiO 2/Al 2O 3＝15.6(摩尔比)。
所得样品的氨气程序升温脱附(NH 3-TPD)与图4所示相类似，由此得到的总酸量为827μmol·g -1，弱酸含量为61％。吡啶吸附红外谱图与图5所示类似，分析测得Lewis/Bronsted酸比例为2.5。
实施例I-3
参照实施例I-1进行试验，只是所用反应物和物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.04
四甲基氯化铵(A)/SiO 2＝0.20
正辛基三甲基氯化铵(B)/SiO 2＝0.15
NaOH/SiO 2＝0.25
H 2O/SiO 2＝35；
混合均匀后，装入不锈钢反应釜中，在155℃下晶化7天。晶化结束后过滤、洗涤，在80℃烘箱中干燥16小时，在500℃空气中焙烧10小时得分子筛。
干燥样品的XRD谱图数据如表I-3所示，样品的SEM图如图7所示。
表I-3实施例I-3所得分子筛的XRD谱图数据
Figure PCTCN2022123784-appb-000005
所得焙烧产品的比表面积为388米 2/克，外比表面积为162米 2/ 克，总孔体积0.75厘米 3/克，微孔体积为0.10厘米 3/克。样品为纳米片状形貌，晶体的厚度约为13纳米。
采用电感耦合等离子体原子发射光谱(ICP)测得焙烧样品的SiO 2/Al 2O 3＝26.1(摩尔比)。
所得样品的氨气程序升温脱附(NH 3-TPD)与图4所示相类似，由此得到的总酸量为674μmol·g -1，弱酸含量为68％。吡啶吸附红外谱图与图5所示类似，分析测得Lewis/Bronsted酸比例为1.1。
实施例I-4
参照实施例I-1进行试验，只是所用反应物和物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.045
四甲基氢氧化铵(A)/SiO 2＝0.25
正辛基三甲基氯化铵(B)/SiO 2＝0.15
NaOH/SiO 2＝0.20
H 2O/SiO 2＝45；
混合均匀后，装入不锈钢反应釜中，在165℃下晶化4天。晶化结束后过滤、洗涤，在60℃烘箱中干燥24小时，在600℃空气中焙烧4小时得分子筛。
干燥样品的XRD谱图数据如表I-4所示，样品的SEM图与图2所示类似。
表I-4实施例I-4所得分子筛的XRD谱图数据
Figure PCTCN2022123784-appb-000006
Figure PCTCN2022123784-appb-000007
所得焙烧产品的比表面积为377米 2/克，外比表面积为158米 2/克，总孔体积0.74厘米 3/克，微孔体积为0.11厘米 3/克。样品为纳米片状形貌，晶体的厚度约为11纳米。
采用电感耦合等离子体原子发射光谱(ICP)测得焙烧样品的SiO 2/Al 2O 3＝22.3(摩尔比)。
所得样品的氨气程序升温脱附(NH 3-TPD)与图4所示类似，由此得到的总酸量为835μmol·g -1，弱酸含量为64％。吡啶吸附红外谱图与图5所示类似，分析测得Lewis/Bronsted酸比例为2.8。
实施例I-5
参照实施例I-1进行试验，只是所用反应物和物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.017
四甲基氢氧化铵(A)/SiO 2＝0.20
正辛基三甲基氯化铵(B)/SiO 2＝0.25
NaOH/SiO 2＝0.20
H 2O/SiO 2＝30；
混合均匀后，装入不锈钢反应釜中，在155℃下晶化8天。晶化结束后过滤、洗涤，在120℃烘箱中干燥6小时，在550℃空气中焙烧8小时得分子筛。
干燥样品的XRD谱图数据如表I-5所示，样品的SEM图与图2所示类似。
表I-5实施例I-5所得分子筛的XRD谱图数据
Figure PCTCN2022123784-appb-000008
Figure PCTCN2022123784-appb-000009
所得焙烧产品的比表面积为372米 2/克，外比表面积为149米 2/克，总孔体积0.74厘米 3/克，微孔体积为0.09厘米 3/克。样品为纳米片状形貌，晶体的厚度约为12纳米。
采用电感耦合等离子体原子发射光谱(ICP)测得焙烧样品的SiO 2/Al 2O 3＝61.5(摩尔比)。
所得样品的氨气程序升温脱附(NH 3-TPD)与图4所示相类似，由此得到的总酸量为621μmol·g -1，弱酸含量为56％。吡啶吸附红外谱图与图5所示类似，分析测得Lewis/Bronsted酸比例为1.0。
实施例I-6
参照实施例I-1进行试验，只是所用反应物和物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.03
四甲基碘化铵(A)/SiO 2＝0.20
正辛基三甲基氯化铵(B)/SiO 2＝0.20
NaOH/SiO 2＝0.25
H 2O/SiO 2＝35；
混合均匀后，装入不锈钢反应釜中，在170℃下晶化5天。晶化结束后过滤、洗涤，在100℃烘箱中干燥12小时，在500℃空气中焙烧10小时得分子筛。
干燥样品的XRD谱图数据如表I-6所示，样品的SEM图与图2所示类似。
表I-6实施例I-6所得分子筛的XRD谱图数据
Figure PCTCN2022123784-appb-000010
Figure PCTCN2022123784-appb-000011
所得焙烧产品的比表面积为362米 2/克，外比表面积为149米 2/克，总孔体积0.67厘米 3/克，微孔体积为0.10厘米 3/克。样品为纳米片状形貌，晶体的厚度约为12纳米。
采用电感耦合等离子体原子发射光谱(ICP)测得焙烧样品的SiO 2/Al 2O 3＝34.5(摩尔比)。
所得样品的氨气程序升温脱附(NH 3-TPD)与图4所示相类似，由此得到的总酸量为643μmol·g -1，弱酸含量为66％。吡啶吸附红外谱图与图5所示类似，分析测得Lewis/Bronsted酸比例为2.1。
实施例I-7
参照实施例I-1进行试验，只是所用反应物和物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.05
四甲基氢氧化铵(A)/SiO 2＝0.15
溴化十四烷基吡啶(B)/SiO 2＝0.15
NaOH/SiO 2＝0.30
H 2O/SiO 2＝35；
混合均匀后，装入不锈钢反应釜中，在160℃下晶化7天。晶化结束后过滤、洗涤，在110℃烘箱中干燥6小时，在550℃空气中焙烧6小时得分子筛。
干燥样品的XRD谱图数据如表I-7所示，样品的SEM图与图2所示类似。
表I-7实施例I-7所得分子筛的XRD谱图数据
Figure PCTCN2022123784-appb-000012
Figure PCTCN2022123784-appb-000013
所得焙烧产品的比表面积为378米 2/克，外比表面积为156米 2/克，总孔体积0.77厘米 3/克，微孔体积为0.11厘米 3/克。样品为纳米片状形貌，晶体的厚度约为13纳米。
采用电感耦合等离子体原子发射光谱(ICP)测得焙烧样品的SiO 2/Al 2O 3＝21.1(摩尔比)。
所得样品的氨气程序升温脱附(NH 3-TPD)与图4所示相类似，由此得到的总酸量为815μmol·g -1，弱酸含量为68％。吡啶吸附红外谱图与图5所示类似，分析测得Lewis/Bronsted酸比例为1.7。
实施例I-8
参照实施例I-1进行试验，只是采用溴化十六烷基吡啶为有机结构导向剂(B)，反应物的物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.045
四甲基氢氧化铵(A)/SiO 2＝0.15
溴化十六烷基吡啶(B)/SiO 2＝0.20
NaOH/SiO 2＝0.25
H 2O/SiO 2＝30；
混合均匀后，装入不锈钢反应釜中，在160℃下晶化6天。晶化结束后过滤、洗涤，在90℃烘箱中干燥12小时，在550℃空气中焙 烧6小时得分子筛。
干燥样品的XRD谱图数据如表I-8所示，样品的SEM图与图2所示类似。
表I-8实施例I-8所得分子筛的XRD谱图数据
Figure PCTCN2022123784-appb-000014
所得焙烧产品的比表面积为394米 2/克，外比表面积为171米 2/克，总孔体积0.68厘米 3/克，微孔体积为0.12厘米 3/克。样品为纳米片状形貌，晶体的厚度约为12纳米。
采用电感耦合等离子体原子发射光谱(ICP)测得焙烧样品的SiO 2/Al 2O 3＝22.8(摩尔比)。
所得样品的氨气程序升温脱附(NH 3-TPD)与图4所示相类似，由此得到的总酸量为849μmol·g -1，弱酸含量为59％。吡啶吸附红外谱图与图5所示类似，分析测得Lewis/Bronsted酸比例为2.3。
实施例I-9
参照实施例I-8进行试验，只是所用反应物和物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.068
四甲基氢氧化铵(A)/SiO 2＝0.20
溴化十六烷基吡啶(B)/SiO 2＝0.15
NaOH/SiO 2＝0.30
H 2O/SiO 2＝40；
混合均匀后，装入不锈钢反应釜中，在160℃下晶化6天。晶化结束后过滤、洗涤，在80℃烘箱中干燥16小时，在550℃空气中焙烧6小时得分子筛。
干燥样品的XRD谱图数据如表I-9所示，样品的SEM图与图2所示类似。
表I-9实施例I-9所得分子筛的XRD谱图数据
Figure PCTCN2022123784-appb-000015
所得焙烧产品的比表面积为372米 2/克，外比表面积为144米 2/克，总孔体积0.65厘米 3/克，微孔体积为0.11厘米 3/克。样品为纳米片状形貌，晶体的厚度约为15纳米。
采用电感耦合等离子体原子发射光谱(ICP)测得焙烧样品的SiO 2/Al 2O 3＝14.5(摩尔比)。
所得样品的氨气程序升温脱附(NH 3-TPD)与图4所示相类似，由此得到的总酸量为896μmol·g -1，弱酸含量为82％。吡啶吸附红外谱图与图5所示类似，分析测得Lewis/Bronsted酸比例为3.0。
实施例I-10
参照实施例I-1进行试验，只是所用反应物和物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.05
TiO 2/SiO 2＝0.01
四甲基氢氧化铵(A)/SiO 2＝0.15
正辛基三甲基氯化铵(B)/SiO 2＝0.20
NaOH/SiO 2＝0.25
H 2O/SiO 2＝35；
混合均匀后，装入不锈钢反应釜中，在160℃下晶化7天。晶化结束后过滤、洗涤，在100℃烘箱中干燥10小时，在550℃氧气中焙烧6小时得分子筛。
干燥样品的XRD谱图数据如表I-10所示，样品的SEM图与图2所示类似。
表I-10实施例I-10所得分子筛的XRD谱图数据
Figure PCTCN2022123784-appb-000016
所得焙烧产品的比表面积为364米 2/克，外比表面积为146米 2/克，总孔体积0.71厘米 3/克，微孔体积为0.12厘米 3/克。样品为纳米片状形貌，晶体的厚度约为18纳米。
采用电感耦合等离子体原子发射光谱(ICP)测得焙烧样品的SiO 2/Al 2O 3＝21.2(摩尔比)，SiO 2/TiO 2＝106.2(摩尔比)。
所得样品的氨气程序升温脱附(NH 3-TPD)与图4所示相类似，由此得到的总酸量为795μmol·g -1，弱酸含量为60％。吡啶吸附红外谱图与图5所示类似，分析测得Lewis/Bronsted酸比例为1.6。
实施例I-11
参照实施例I-1进行试验，只是所用反应物和物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.065
B 2O 3/SiO 2＝0.012
四甲基氢氧化铵(A)/SiO 2＝0.20
正辛基三甲基氯化铵(B)/SiO 2＝0.15
NaOH/SiO 2＝0.30
H 2O/SiO 2＝40；
混合均匀后，装入不锈钢反应釜中，在155℃下晶化7天。晶化结束后过滤、洗涤，在80℃烘箱中干燥8小时，在550℃空气中焙烧6小时得分子筛。
干燥样品的XRD谱图数据如表I-11所示，样品的SEM图与图2所示类似；
表I-11实施例I-11所得分子筛的XRD谱图数据
Figure PCTCN2022123784-appb-000017
所得焙烧产品的比表面积为385米 2/克，外比表面积为152米 2/克，总孔体积0.63厘米 3/克，微孔体积为0.09厘米 3/克。样品为纳米片状形貌，晶体的厚度约为20纳米。
采用电感耦合等离子体原子发射光谱(ICP)测得焙烧样品的SiO 2/Al 2O 3＝15.9(摩尔比)，SiO 2/B 2O 3＝96.3(摩尔比)。
所得样品的氨气程序升温脱附(NH 3-TPD)与图4所示相类似，由此得到的总酸量为860μmol·g -1，弱酸含量为74％。吡啶吸附红外谱图与图5所示类似，分析测得Lewis/Bronsted酸比例为3.2。
实施例I-12
参照实施例I-7进行试验，只是所用反应物和物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.035
ZrO 2/SiO 2＝0.008
四甲基氢氧化铵(A)/SiO 2＝0.20
溴化十二烷基吡啶(B)/SiO 2＝0.20
NaOH/SiO 2＝0.25
H 2O/SiO 2＝30；
混合均匀后，装入不锈钢反应釜中，在165℃下晶化6天。晶化结束后过滤、洗涤，在110℃烘箱中干燥12小时，在550℃空气中焙烧5小时得分子筛。
干燥样品的XRD谱图数据如表I-12所示，样品的SEM图与图2所示类似；
表I-12实施例I-12所得分子筛的XRD谱图数据
Figure PCTCN2022123784-appb-000018
Figure PCTCN2022123784-appb-000019
所得焙烧产品的比表面积为373米 2/克，外比表面积为148米 2/克，总孔体积0.75厘米 3/克，微孔体积为0.09厘米 3/克。样品为纳米片状形貌，晶体的厚度约为16纳米。
采用电感耦合等离子体原子发射光谱(ICP)测得焙烧样品的SiO 2/Al 2O 3＝30.6(摩尔比)，SiO 2/ZrO 2＝131.2(摩尔比)。
所得样品的氨气程序升温脱附(NH 3-TPD)与图4所示相类似，由此得到的总酸量为773μmol·g -1，弱酸含量为63％。吡啶吸附红外谱图与图5所示类似，分析测得Lewis/Bronsted酸比例为2.8。
实施例I-13
参照实施例I-1进行试验，只是所用反应物和物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.05
SnO 2/SiO 2＝0.008
四甲基溴化铵(A)/SiO 2＝0.15
正辛基三甲基溴化铵(B)/SiO 2＝0.20
NaOH/SiO 2＝0.30
H 2O/SiO 2＝25；
混合均匀后，装入不锈钢反应釜中，在160℃下晶化7天。晶化结束后过滤、洗涤，在110℃烘箱中干燥12小时，在550℃空气中焙烧6小时得分子筛。
干燥样品的XRD谱图数据如表I-13所示，样品的SEM图与图2所示类似；
表I-13实施例I-13所得分子筛的XRD谱图数据
Figure PCTCN2022123784-appb-000020
Figure PCTCN2022123784-appb-000021
所得焙烧产品的比表面积为386米 2/克，外比表面积为154米 2/克，总孔体积0.73厘米 3/克，微孔体积为0.10厘米 3/克。样品为纳米片状形貌，晶体的厚度约为15纳米。
采用电感耦合等离子体原子发射光谱(ICP)测得焙烧样品的SiO 2/Al 2O 3＝21.5(摩尔比)，SiO 2/SnO 2＝126.4(摩尔比)。
所得样品的氨气程序升温脱附(NH 3-TPD)与图4所示相类似，由此得到的总酸量为794μmol·g -1，弱酸含量为66％。吡啶吸附红外谱图与图5所示类似，分析测得Lewis/Bronsted酸比例为2.4。
实施例I-14
参照实施例I-8进行试验，只是所用反应物和物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.04
Fe 2O 3/SiO 2＝0.005
四甲基氯化铵(A)/SiO 2＝0.15
氢氧化十六烷基吡啶(B)/SiO 2＝0.25
NaOH/SiO 2＝0.20
H 2O/SiO 2＝30；
混合均匀后，装入不锈钢反应釜中，在165℃下晶化7天。晶化结束后过滤、洗涤，在110℃烘箱中干燥12小时，在550℃空气中焙烧6小时得分子筛。
干燥样品的XRD谱图数据如表I-14所示，样品的SEM图与图2所示类似；
表I-14实施例I-14所得分子筛的XRD谱图数据
Figure PCTCN2022123784-appb-000022
Figure PCTCN2022123784-appb-000023
所得焙烧产品的比表面积为383米 2/克，外比表面积为155米 2/克，总孔体积0.75厘米 3/克，微孔体积为0.10厘米 3/克。样品为纳米片状形貌，晶体的厚度约为17纳米。
采用电感耦合等离子体原子发射光谱(ICP)测得焙烧样品的SiO 2/Al 2O 3＝26.5(摩尔比)，SiO 2/Fe 2O 3＝188.4(摩尔比)。
所得样品的氨气程序升温脱附(NH 3-TPD)与图4所示相类似，由此得到的总酸量为787μmol·g -1，弱酸含量为68％。吡啶吸附红外谱图与图5所示类似，分析测得Lewis/Bronsted酸比例为1.8。
实施例I-15
参照实施例I-1进行试验，只是所用反应物和物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.045
四甲基氢氧化铵(A)/SiO 2＝0.45
溴化十二烷基吡啶(B)/SiO 2＝0.20
NaOH/SiO 2＝0.25
H 2O/SiO 2＝25；
混合均匀后，装入不锈钢反应釜中，在160℃下晶化6天。晶化结束后过滤、洗涤，在110℃烘箱中干燥12小时，在550℃空气中焙烧6小时得分子筛。
干燥样品的XRD谱图数据如表I-15所示，样品的SEM图与图2所示类似；
表I-15实施例I-15所得分子筛的XRD谱图数据
Figure PCTCN2022123784-appb-000024
所得焙烧产品的比表面积为368米 2/克，外比表面积为145米 2/克，总孔体积0.72厘米 3/克，微孔体积为0.09厘米 3/克。样品为纳米片状形貌，晶体的厚度约为17纳米。
采用电感耦合等离子体原子发射光谱(ICP)测得焙烧样品的SiO 2/Al 2O 3＝22.8(摩尔比)。
所得样品的氨气程序升温脱附(NH 3-TPD)与图4所示相类似，由此得到的总酸量为861μmol·g -1，弱酸含量为57％。吡啶吸附红外谱图与图5所示类似，分析测得Lewis/Bronsted酸比例为2.0。
实施例I-16
参照实施例I-7进行试验，只是所用反应物和物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.040
四甲基氯化铵(A)/SiO 2＝0.15
溴化十二烷基吡啶(B)/SiO 2＝0.45
NaOH/SiO 2＝0.15
H 2O/SiO 2＝30；
混合均匀后，装入不锈钢反应釜中，在160℃下晶化8天。晶化 结束后过滤、洗涤，在110℃烘箱中干燥12小时，在550℃空气中焙烧6小时得分子筛。
干燥样品的XRD谱图数据如表I-16所示，样品的SEM图与图2所示类似；
表I-16实施例I-16所得分子筛的XRD谱图数据
Figure PCTCN2022123784-appb-000025
所得焙烧产品的比表面积为388米 2/克，外比表面积为159米 2/克，总孔体积0.71厘米 3/克，微孔体积为0.10厘米 3/克。样品为纳米片状形貌，晶体的厚度约为17纳米。
采用电感耦合等离子体原子发射光谱(ICP)测得焙烧样品的SiO 2/Al 2O 3＝26.1(摩尔比)。
所得样品的氨气程序升温脱附(NH 3-TPD)与图4所示相类似，由此得到的总酸量为872μmol·g -1，弱酸含量为75％。吡啶吸附红外谱图与图5所示类似，分析测得Lewis/Bronsted酸比例为3.0。
实施例I-17
参照实施例I-1进行试验，只是所用反应物和物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.05
四甲基氢氧化铵(A)/SiO 2＝0.20
氯化十六烷基吡啶(B)/SiO 2＝0.25
NaOH/SiO 2＝0.15
H 2O/SiO 2＝20；
混合均匀后，装入不锈钢反应釜中，在160℃下晶化7天。晶化结束后过滤、洗涤，在110℃烘箱中干燥12小时，在550℃空气中焙烧6小时得分子筛。
干燥样品的XRD谱图数据如表I-17所示，样品的SEM图与图2所示类似；
表I-17实施例I-17所得分子筛的XRD谱图数据
Figure PCTCN2022123784-appb-000026
所得焙烧产品的比表面积为392米 2/克，外比表面积为159米 2/克，总孔体积0.72厘米 3/克，微孔体积为0.09厘米 3/克。样品为纳米片状形貌，晶体的厚度约为15纳米。
采用电感耦合等离子体原子发射光谱(ICP)测得焙烧样品的SiO 2/Al 2O 3＝21.6(摩尔比)。
所得样品的氨气程序升温脱附(NH 3-TPD)与图4所示相类似，由此得到的总酸量为908μmol·g- 1，弱酸含量为79％。吡啶吸附红外谱图与图5所示类似，分析测得Lewis/Bronsted酸比例为3.2。
对比例I-1
参照实施例I-1进行试验，只是所用反应物和物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.22
四甲基氢氧化铵(A)/SiO 2＝0.15
正辛基三甲基氯化铵(B)/SiO 2＝0.15
NaOH/SiO 2＝0.30
H 2O/SiO 2＝25；
混合均匀后，装入不锈钢反应釜中，在160℃下晶化6天。晶化结束后过滤、洗涤，在110℃烘箱中干燥12小时，在550℃空气中焙烧6小时得样品。
干燥样品的XRD谱图数据如图8所示，为无定形物，不为SCM-36分子筛。
对比例I-2
参照实施例I-1进行试验，只是所用反应物和物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.05
四甲基氢氧化铵(A)/SiO 2＝0.15
正辛基三甲基氯化铵(B)/SiO 2＝0.15
NaOH/SiO 2＝0.55
H 2O/SiO 2＝25；
混合均匀后，装入不锈钢反应釜中，在160℃下晶化6天。晶化结束后过滤、洗涤，在110℃烘箱中干燥12小时，在550℃空气中焙烧6小时得样品。
干燥样品的XRD谱图数据与图8所示类似，为无定形物，不为SCM-36分子筛。
对比例I-3
参照实施例I-1进行试验，只是使用辛胺为有机结构导向剂(B)，所用反应物和物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.05
四甲基氢氧化铵(A)/SiO 2＝0.15
辛胺(B)/SiO 2＝0.15
NaOH/SiO 2＝0.30
H 2O/SiO 2＝25；
混合均匀后，装入不锈钢反应釜中，在160℃下晶化6天。晶化结束后过滤、洗涤，在110℃烘箱中干燥12小时，在550℃空气中焙烧6小时得样品。
干燥样品的XRD谱图数据如图9所示，为MOR和其他结构分子筛的混合物，不为SCM-36分子筛。
对比例I-4
参照实施例I-1进行试验，只是仅使用四甲基氢氧化铵为有机结构导向剂，所用反应物和物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.05
四甲基氢氧化铵/SiO 2＝0.15
NaOH/SiO 2＝0.30
H 2O/SiO 2＝25；
混合均匀后，装入不锈钢反应釜中，在160℃下晶化6天。晶化结束后过滤、洗涤，在110℃烘箱中干燥12小时，在550℃空气中焙烧6小时得样品。
干燥样品的XRD谱图数据如图10所示，为SOD和其他结构分子筛的混合物，不为SCM-36分子筛。
实施例I-18
将实施例I-5合成的分子筛与0.5mol/L的NH 4Cl溶液(分子筛与氯化铵溶液的质量比1∶20)在70℃下进行离子交换2小时，然后离心洗涤，离子交换两次后得到的样品在100℃下干燥12小时，在550℃下焙烧6小时，得到H型SCM-36分子筛。
取上述焙烧后的H型SCM-36分子筛粉末样品，破碎后筛取20-40目的粒度部分放入固定床反应器，进行异丙苯裂解反应，反应条件为：反应温度为320℃、反应压力为常压、异丙苯重量空速2h -1。采用岛津GC-2014气相色谱仪分析产物，反应1小时后异丙苯的转化率为25.2％，产物中苯的选择性94.1％。
在该实施例中，所述异丙苯裂解反应是以异丙苯为原料，在催化剂作用下裂解为丙烯和苯等产物。
异丙苯的转化率％＝(进料异丙苯的摩尔量-产物中异丙苯的摩尔量)/(进料异丙苯的摩尔量)×100％。
苯的选择性％＝(产物中苯的摩尔量)/(产物中芳烃的总摩尔量)×100％；
其中产物中芳烃不包括原料异丙苯。
实施例I-19
将实施例I-5合成的分子筛与0.5mol/L的NH 4Cl溶液(分子筛与氯化铵溶液的质量比为1∶20)在70℃下进行离子交换2小时，然后离心洗涤，离子交换两次后得到的样品在100℃下干燥12小时，在550℃下焙烧6小时得到H型SCM-36分子筛。
取上述焙烧后的H型SCM-36分子筛粉末样品，破碎后筛取20-40目的粒度部分放入固定床反应器，进行甲醇转化反应。反应条件为：反应温度为460℃、反应压力为0.1MPa、原料甲醇重量空速为1h -1。采用岛津GC-2014气相色谱仪分析产物，反应45分钟后甲醇的转化率为99.0％，产物中C2-C4烯烃的选择性58.6％，芳烃的选择性4.2％。
在该实施例中，所述甲醇转化反应是以甲醇为原料，在催化剂作用下转化为烯烃和芳烃等碳氢化合物。
甲醇的转化率％＝(进料甲醇的摩尔量-产物中甲醇的摩尔量-2×产物中二甲醚的摩尔量)/(进料甲醇的摩尔量)×100％；
C2-C4烯烃的选择性％＝(2×产物中C2烯烃的摩尔量+3×产物中C3烯烃的摩尔量+4×产物中C4烯烃的摩尔量)/(进料甲醇的摩尔量-产物中甲醇的摩尔量-2×产物中二甲醚的摩尔量)×100％。
芳烃的选择性％＝(6×产物中苯的摩尔量+7×产物中甲苯的摩尔量+8×产物中二甲苯的摩尔量)/(进料甲醇的摩尔量-产物中甲醇的摩尔量-2×产物中二甲醚的摩尔量)×100％。
以下实施例和对比例中，反应产物对二甲苯用气质联用(GC-MS)分析定性，用气相色谱(GC)分析底物2，5-甲基呋喃和/或2，5-己二酮的转化率和反应产物pX的收率。气质联用仪为美国安捷伦公司的Agilent 7890A，色谱柱为HP-5非极性毛细管柱(30m，0.53mm)，气相色谱仪为Agilent 7890B，检测器为氢焰离子化检测器(FID)，色谱柱为SE-54毛细管柱(30m，0.53mm)。
以下实施例和对比例中，2，5-二甲基呋喃(或2，5-己二酮)转化率公式为：
2，5-二甲基呋喃(和/或2，5-己二酮)的转化率％＝(参加反应的2，5-二甲基呋喃(和/或2，5-己二酮)摩尔量)/(反应底物2，5-二甲基呋喃(和/或2，5-己二酮)的摩尔量)×100％。
本申请中，产物对二甲苯(pX)收率计算公式为：
产物pX的收率％＝(反应生成的pX摩尔量)/(反应底物2，5-二甲基呋喃(和/或2，5-己二酮)的摩尔量)×100％。
本申请中，产物对二甲苯选择性计算公式为：
产物pX的选择性％＝(反应生成的pX摩尔量)/(反应的2，5-二甲基呋喃(和/或2，5-己二酮)摩尔量)×100％。
实施例II-1
采用正庚烷为反应溶剂，正庚烷与2，5-二甲基呋喃(DMF)质量比为20，DMF与催化剂质量比为1，反应温度为240℃，反应时间为24h。将1.0g实施例I-1制得的SCM-36分子筛、1.0g DMF和20g正庚烷加入带搅拌的高压反应釜中，并充入2.0MPa乙烯。采用程序升温加热套升至预设温度，并采用磁力搅拌然后搅拌。在240℃条件下反应24h，将反应液气相分析计算DMF转化率为86％，pX选择性为94％，关键杂质多烷基苯选择性低于1％。
实施例II-2
采用正庚烷为反应溶剂，正庚烷与DMF质量比为20，DMF与催化剂质量比为1，反应温度为240℃，反应时间为24h。将1.0g实施例I-2制得的SCM-36分子筛、1.0g DMF和20g正庚烷加入带搅拌的高压反应釜中，并充入2.0MPa乙烯。采用程序升温加热套升至预设温度，并采用磁力搅拌然后搅拌。在240℃条件下反应24h，将反应液气相分析计算DMF转化率为90％，pX选择性为94％，关键杂质多烷基苯选择性低于1％。
实施例II-3
采用正庚烷为反应溶剂，正庚烷与DMF质量比为20，DMF与催 化剂质量比为1，反应温度为240℃，反应时间为24h。将1.0g实施例I-3制得的SCM-36分子筛、1.0g DMF和20g正庚烷加入带搅拌的高压反应釜中，并充入2.0MPa乙烯。采用程序升温加热套升至预设温度，并采用磁力搅拌然后搅拌。在240℃条件下反应24h，将反应液气相分析计算DMF转化率为86％，pX选择性为95％，关键杂质多烷基苯选择性低于1％。
实施例II-4
采用正庚烷为反应溶剂，正庚烷与DMF质量比为20，DMF与催化剂质量比为1，反应温度为240℃，反应时间为24h。将1.0g实施例I-4制得的SCM-36分子筛、1.0g DMF和20g正庚烷加入带搅拌的高压反应釜中，并充入2.0MPa乙烯。采用程序升温加热套升至预设温度，并采用磁力搅拌然后搅拌。在240℃条件下反应24h，将反应液气相分析计算DMF转化率为92％，pX选择性为95％，关键杂质多烷基苯选择性低于1％。
实施例II-5
本实施例采用正庚烷为反应溶剂，正庚烷与DMF质量比为20，DMF与催化剂质量比为1.5，反应温度为250℃，反应时间为30h。将1.0g实施例I-1制得的SCM-36分子筛催化剂、1.5gDMF和30g正庚烷加入带搅拌的高压反应釜中，并充入3.0MPa乙烯。采用程序升温加热套升至预设温度，并采用磁力搅拌然后搅拌。在250℃条件下反应30h，将反应液气相分析计算DMF转化率为88％，pX选择性为96％，关键杂质多烷基苯选择性低于1％。
实施例II-6
本实施例采用正庚烷为反应溶剂，正庚烷与2，5-己二酮(HDO)质量比为20，HDO与催化剂质量比为1，反应温度为230℃，反应时间为20h。将1.0g实施例I-1制得的SCM-36分子筛催化剂、1g HDO和20g正庚烷加入带搅拌的高压反应釜中，并充入2.0MPa乙烯。采用程序升温加热套升至预设温度，并采用磁力搅拌然后搅拌。在230℃条件下反应20h，将反应液气相分析计算HDO转化率为86％，pX选 择性为95％，关键杂质多烷基苯选择性低于1％。
实施例II-7
本实施例采用正己烷为反应溶剂，正己烷与DMF质量比为30，DMF与催化剂质量比为2，反应温度为260℃，反应时间为24h。将1.0g实施例I-1制得的SCM-36分子筛催化剂、2.0g DMF和60g正己烷加入带搅拌的高压反应釜中，并充入4.0MPa乙烯。采用程序升温加热套升至预设温度，并采用磁力搅拌然后搅拌。在260℃条件下反应24h，将反应液气相分析计算DMF转化率为83％，pX选择性为94％，关键杂质多烷基苯选择性低于1％。
实施例II-8
本实施例采用正己烷为反应溶剂，正己烷与DMF质量比为20，DMF与催化剂质量比为1.5，反应温度为240℃，反应时间为30h。将1.0g实施例I-1制得的SCM-36分子筛催化剂、1.5g DMF和30g正己烷加入带搅拌的高压反应釜中，并充入2.0MPa乙烯。采用程序升温加热套升至预设温度，并采用磁力搅拌然后搅拌。在240℃条件下反应30h，将反应液气相分析计算DMF转化率为88％，pX选择性为93％，关键杂质多烷基苯选择性低于1％。
实施例II-9
本实施例采用γ-戊内酯为反应溶剂，γ-戊内酯与HDO质量比为15，HDO与催化剂质量比为2，反应温度为270℃，反应时间为28h。将1.0g实施例I-1制得的SCM-36分子筛催化剂、2g HDO和30gγ-戊内酯加入带搅拌的高压反应釜中，并充入3.0MPa乙烯。采用程序升温加热套升至预设温度，并采用磁力搅拌然后搅拌。在270℃条件下反应28h，将反应液气相分析计算HDO转化率为89％，pX选择性为95％，关键杂质多烷基苯选择性低于1％。
实施例II-10
本实施例采用γ-戊内酯为反应溶剂，γ-戊内酯与DMF质量比为30，DMF与催化剂质量比为3，反应温度为270℃，反应时间为32h。将 1.0g实施例I-1制得的SCM-36分子筛催化剂、3.0g DMF和90gγ-戊内酯加入带搅拌的高压反应釜中，并充入4.0MPa乙烯。采用程序升温加热套升至预设温度，并采用磁力搅拌然后搅拌。在270℃条件下反应32h，将反应液气相分析计算DMF转化率为85％，pX选择性为94％，关键杂质多烷基苯选择性低于1％。
实施例II-11
本实施例采用甲苯为反应溶剂，甲苯与HDO质量比为22，HDO与催化剂质量比为1，反应温度为250℃，反应时间为18h。将1.0g实施例I-1制得的SCM-36分子筛催化剂、1g HDO和22g甲苯加入带搅拌的高压反应釜中，并充入2.0MPa乙烯。采用程序升温加热套升至预设温度，并采用磁力搅拌然后搅拌。在250℃条件下反应18h，将反应液气相分析计算HDO转化率为93％，pX选择性为95％，关键杂质多烷基苯选择性低于1％。
实施例II-12
本实施例采用甲苯为反应溶剂，甲苯与HDO质量比为25，HDO与催化剂质量比为1.5，反应温度为260℃，反应时间为24h。将1.0g实施例I-1制得的SCM-36分子筛催化剂、1.5g HDO和37.5g甲苯加入带搅拌的高压反应釜中，并充入4.0MPa乙烯。采用程序升温加热套升至预设温度，并采用磁力搅拌然后搅拌。在260℃条件下反应24h，将反应液气相分析计算HDO转化率为90％，pX选择性为95％，关键杂质多烷基苯选择性低于1％。
实施例II-13
本实施例采用环己烷为反应溶剂，环己烷与DMF质量比为30，DMF与催化剂质量比为2，反应温度为250℃，反应时间为40h。将1.0g实施例I-1制得的SCM-36分子筛催化剂、2.0g DMF和60g环己烷加入带搅拌的高压反应釜中，并充入4.0MPa乙烯。采用程序升温加热套升至预设温度，并采用磁力搅拌然后搅拌。在250℃条件下反应40h，将反应液气相分析计算DMF转化率为86％，pX选择性为96％，关键杂质多烷基苯选择性低于1％。
实施例II-14
本实施例采用环己烷为反应溶剂，环己烷与HDO质量比为20，HDO与催化剂质量比为2，反应温度为255℃，反应时间为38h。将1.0g实施例I-1制得的SCM-36分子筛催化剂、2.0g HDO和40.0g环己烷加入带搅拌的高压反应釜中，并充入4.0MPa乙烯。采用程序升温加热套升至预设温度，并采用磁力搅拌然后搅拌。在255℃条件下反应38h，将反应液气相分析计算HDO转化率为87％，pX选择性为95％，关键杂质多烷基苯选择性低于1％。
为更直观地描述上述实施例II-1至II-14的反应条件和结果，将各项参数及结果列于表II-1中。
Figure PCTCN2022123784-appb-000027
Figure PCTCN2022123784-appb-000028
实施例II-15
采用正庚烷为反应溶剂，正庚烷与DMF质量比为20，DMF与催化剂质量比为1，反应温度为240℃，反应时间为24h。将1.0g实施例I-1制得的SCM-36分子筛、1.0g DMF和20g正庚烷加入带搅拌的高压反应釜中，并充入2.0MPa乙烯。采用程序升温加热套升至预设温度，并采用磁力搅拌然后搅拌。在240℃条件下反应24h，将反应液气相分析计算DMF转化率和pX选择性。将使用后的的催化剂经洗涤后烘干后投入下一个反应，共循环4次反应，结果如图11所示。结果显示，4次反应后DMF转化率保持在82％以上，pX选择性保持在92％，且关键杂质多烷基苯选择性低于1％，说明SCM-36分子筛具有良好的循环稳定性。
实施例II-16
1)SCM-36分子筛的制造
参照实施例I-1进行试验，只是所用反应物和物料配比(摩尔比)为：
Al 2O 3/SiO 2＝0.017
四甲基氢氧化铵(A)/SiO 2＝0.20
正辛基三甲基氯化铵(B)/SiO 2＝0.25
NaOH/SiO 2＝0.20
H 2O/SiO 2＝30；
混合均匀后，装入不锈钢反应釜中，在155℃下晶化8天。晶化结束后过滤、洗涤，在120℃烘箱中干燥6小时，在550℃空气中焙烧8小时得分子筛。
干燥样品的XRD谱图数据如表II-2所示，样品的SEM图与图2所示类似。
表II-2实施例II-16所得分子筛的XRD谱图数据
Figure PCTCN2022123784-appb-000029
Figure PCTCN2022123784-appb-000030
所得焙烧产品的比表面积为372米 2/克，外比表面积为149米 2/克，总孔体积0.74厘米 3/克，微孔体积为0.09厘米 3/克。样品为纳米片状形貌，晶体的厚度约为12纳米。采用电感耦合等离子体原子发射光谱(ICP)测得焙烧样品的SiO 2/Al 2O 3＝61.5(摩尔比)。
所得样品的氨气程序升温脱附(NH 3-TPD)如图12所示，由此得到的总酸量为470μmol·g -1，弱酸含量为47％。吡啶吸附红外谱图如图13所示，分析测得Lewis/Bronsted酸比例为0.4。
2)对二甲苯的制备
采用正庚烷为反应溶剂，将1.0g上述制得的SCM-36分子筛、1.0g DMF和20ml正庚烷加入带搅拌的高压反应釜中，并充入2.0MPa乙烯。采用程序升温加热套升至预设温度，并采用磁力搅拌然后搅拌。在240℃条件下反应24h，将反应液气相分析计算DMF转化率为93％，pX选择性为90％，关键杂质多烷基苯选择性为3％。
对比例II-1
根据文献(Microporous and Mesoporous Materials，2018，263，11-20)报道制造AlPO-17分子筛，按照1 P 2O 5∶0.9 Al 2O 3∶1 CHA(环己胺)：50H 2O将磷酸、异丙醇铝、环己胺和去离子水混合均匀成凝胶，然后在190℃温度下水热晶化120h，经洗涤、干燥，在空气条件下，550℃焙烧5h制得到所述AlPO-17分子筛。样品的总酸量为262μmol·g -1，其中弱酸含量为93％，Lewis酸/Bronsted酸比例为4.2。
采用正庚烷为反应溶剂，将1.0g上述制得的催化剂、1.0g DMF 和20ml正庚烷加入带搅拌的高压反应釜中，并充入2.0MPa乙烯。采用程序升温加热套升至预设温度，并采用磁力搅拌然后搅拌。在240℃条件下反应24h，将反应液气相分析计算DMF转化率为67％，pX选择性为72％。
以上详细描述了本申请的优选实施方式，但是，本申请并不限于上述实施方式中的具体细节，在本申请的技术构思范围内，可以对本申请的技术方案进行多种简单变型，这些简单变型均属于本申请的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本申请对各种可能的组合方式不再另行说明。
此外，本申请的各种不同的实施方式之间也可以进行任意组合，只要其不违背本申请的思想，其同样应当视为本申请所公开的内容。

Claims (17)

  1. 一种硅铝分子筛，所述分子筛的硅铝比n≥5，优选n在5-80范围内，进一步优选n在10-65范围内，并且所述分子筛的X射线衍射谱图显示出如下表所示的衍射峰相对强度特性：
    2θ(°) 相对强度(I/I 0×100) 8.99-9.59 s 12.48-13.08 s-vs 18.91-19.51 s-vs 23.39-23.99 m 24.00-24.41 m 25.65-26.25 vs
    。
  2. 根据权利要求1所述的硅铝分子筛，其中所述分子筛的X射线衍射谱图还显示出如下表任一行所示的衍射峰相对强度特性：
    2θ(°) 相对强度(I/I 0×100) 16.50-17.10 w-m 48.33-48.93 w-m
    。
  3. 根据权利要求2所述的硅铝分子筛，其中所述分子筛的X射线衍射谱图还显示出如下表任一行所示的衍射峰相对强度特性：
    2θ(°) 相对强度(I/I 0×100) 13.65-14.25 w 30.23-30.83 w 36.67-37.27 w 43.05-43.65 w
    。
  4. 根据权利要求1-3中任一项所述的硅铝分子筛，具有以下特征中的至少一个：
    比表面积为300-700米 2/克，优选300-600米 2/克，更优选350-500米 2/克；
    外比表面积为50-300米 2/克，优选80-250米 2/克，更优选100-220米 2/克；
    总孔体积为0.20-1.50厘米 3/克，优选0.40-1.20厘米 3/克，更优选0.5-1.0厘米 3/克；
    微孔体积为0.05-0.35厘米 3/克，优选0.08-0.30厘米 3/克，更优选0.09-0.25厘米 3/克；
    总酸量为400-1200μmol·g -1，优选为500-1000μmol·g -1，其中，弱酸含量≥40％，优选为45％-90％；
    Lewis酸/Bronsted酸比例为0.1-3.8，优选为0.4-3.5。
  5. 根据权利要求1-4中任一项所述的硅铝分子筛，其中所述分子筛的晶体形貌为纳米片状，晶体的厚度＜30纳米，优选5-25纳米，更优选7-20纳米。
  6. 根据权利要求1-5中任一所述的硅铝分子筛，其中所述分子筛还包含至少一种选自钛、硼、锆、锡和铁的元素M；
    优选地，以氧化物计并以Si、Al和元素M的总量为基准，所述分子筛中所述元素M的总含量不超过3mol％。
  7. 制造权利要求1-6中任一项所述的硅铝分子筛的方法，包括如下步骤：
    1)使包含硅源、铝源、有机结构导向剂(A)、有机结构导向剂(B)、碱源和水的混合物进行晶化反应，以获得分子筛；和
    2)任选地，焙烧步骤1)所得的分子筛；
    其中，所述有机结构导向剂(A)选自四甲基铵类化合物；所述有机结构导向剂(B)选自C6-16烷基吡啶鎓化合物、正辛基三甲基铵类化合物或者它们的组合。
  8. 根据权利要求7所述的方法，其中步骤1)所述的混合物中，所述硅源(以SiO 2计)、铝源(以Al 2O 3计)、有机结构导向剂(A)、有机结构导向剂(B)、碱源和水的摩尔比例为1∶(0.01-0.20)∶(0.05-0.80)∶(0.05-0.80)∶(0.05-0.50)∶(8-80)，优选1∶(0.01-0.10)∶(0.08-0.65)∶(0.08-0.65)∶(0.08-0.45)∶(10-70)，更优选1∶(0.02-0.07)∶(0.10-0.50)∶(0.10-0.50)∶(0.10-0.40)∶(12-60)。
  9. 根据权利要求7或8所述的方法，其中步骤1)的晶化温度为120-200℃，优选130-190℃，更优选140-180℃；晶化时间为1-15天， 优选2-12天，更优选3-9天。
  10. 根据权利要求7-9中任一项所述的方法，其中所述有机结构导向剂(A)选自四甲基氢氧化铵、四甲基氯化铵、四甲基溴化铵、四甲基碘化铵或者它们的组合；和/或
    所述有机结构导向剂(B)选自溴化十六烷基吡啶、溴化十四烷基吡啶、溴化十二烷基吡啶、溴化十烷基吡啶、氯化十六烷基吡啶、氯化十四烷基吡啶、氢氧化十六烷基吡啶、正辛基三甲基氯化铵、正辛基三甲基溴化铵、正辛基三甲基氢氧化铵或者它们的组合；优选选自溴化十六烷基吡啶、溴化十四烷基吡啶、溴化十二烷基吡啶、氯化十六烷基吡啶、氢氧化十六烷基吡啶、正辛基三甲基氯化铵、正辛基三甲基溴化铵或者它们的组合。
  11. 根据权利要求7-10中任一项所述的方法，其中所述硅源选自硅酸、硅胶、硅溶胶、硅酸四乙酯、水玻璃或者它们的组合；
    所述铝源选自氢氧化铝、氧化铝、铝酸盐、铝盐、四烷氧基铝或者它们的组合；和/或
    所述碱源选自以碱金属为阳离子的无机碱、以碱土金属为阳离子的无机碱或者它们的组合。
  12. 根据权利要求7-11中任一所述的方法，其中步骤1)所述的混合物中还包括元素M源，所述元素M选自钛、硼、锆、锡、铁或者它们的组合；
    优选地，以氧化物计，所述硅源与所述元素M源的摩尔比为1∶(0.002-0.10)，优选1∶(0.005-0.05)。
  13. 一种分子筛组合物，包含根据权利要求1-6中任一项所述的硅铝分子筛，以及粘结剂。
  14. 权利要求1-6中任一项所述的硅铝分子筛或者权利要求13所述的分子筛组合物作为吸附剂、催化剂或者催化剂载体的应用。
  15. 一种制备对二甲苯的方法，包括：使包含2，5-二甲基呋喃、2，5-己二酮或者它们的组合的原料在包含权利要求1-6中任一项所述的硅铝分子筛或由其组成的催化剂存在下，与乙烯接触反应的步骤。
  16. 根据权利要求15所述的方法，具有以下特征中的至少一个：
    所述反应在有机溶剂存在下进行，所述有机溶剂选自正己烷、正庚烷、γ-戊内酯、四氢呋喃、甲苯、环己烷，或者它们的组合；
    所述原料与催化剂的质量比为0.6-30∶1，优选为1.0-10∶1；和
    所述有机溶剂与原料的质量比为8-60∶1，优选为10-30∶1。
  17. 根据权利要求15或16所述的方法，所述反应的条件包括：
    反应温度为160-340℃，优选为220-270℃；
    反应时间为6-64h，优选为8-48h；和
    反应压力为1-8MPa，优选为2-4MPa。
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