WO2022083566A1 - 用于烯烃歧化反应的催化剂颗粒及其制备方法 - Google Patents

用于烯烃歧化反应的催化剂颗粒及其制备方法 Download PDF

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WO2022083566A1
WO2022083566A1 PCT/CN2021/124570 CN2021124570W WO2022083566A1 WO 2022083566 A1 WO2022083566 A1 WO 2022083566A1 CN 2021124570 W CN2021124570 W CN 2021124570W WO 2022083566 A1 WO2022083566 A1 WO 2022083566A1
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catalyst
disproportionation
active phases
active phase
hours
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PCT/CN2021/124570
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English (en)
French (fr)
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董静
刘苏
王仰东
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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 to EP21881982.9A priority Critical patent/EP4234083A4/en
Priority to KR1020237017176A priority patent/KR20230091981A/ko
Priority to US18/249,649 priority patent/US20230390750A1/en
Priority to JP2023524390A priority patent/JP2023549465A/ja
Publication of WO2022083566A1 publication Critical patent/WO2022083566A1/zh

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    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
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    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
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    • B01J37/04—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/02—Magnesia
    • C01F5/06—Magnesia by thermal decomposition of magnesium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • 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
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    • 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 invention relates to a catalyst particle for olefin disproportionation reaction, a preparation method thereof, and the application of the catalyst particle in the field of olefin disproportionation.
  • Olefin disproportionation technology is one of the effective technical means to adjust product structure. Utilizing the cross-disproportionation of butene and ethylene, the relatively excess butene feedstock with low added value can be converted into high value-added propylene products by adding an appropriate amount of ethylene.
  • Butene disproportionation catalysts mainly include rhenium-based, molybdenum-based and tungsten-based catalysts.
  • US5898091 and US6166279 disclose C 4 , C 5 olefin treatment methods, wherein in the process of olefin disproportionation to propylene, the catalyst used is Re 2 O 7 /Al 2 O 3 , and the reactor is a moving bed.
  • US6358482 discloses a plant for the production of isobutene and propylene from C4 fraction hydrocarbons.
  • the catalyst used in the disproportionation of olefins to propylene adopts dual catalysts, including disproportionation catalysts and isomerization catalysts, wherein the isomerization catalysts usually use alkaline earth metal oxides, and the isomerization catalysts alone have basically no olefin disproportionation effect.
  • the current research shows that the method of loading the two by mixing particles can effectively improve the activity and stability of the low-carbon olefin disproportionation catalyst.
  • the inventors of the present invention have found through research that the migration of the intermediate allyl in the disproportionation reaction in the two types of catalytic active phases has a greater impact on the reaction, and the precise control of the distance between the two types of active phases should be considered in the catalyst design process.
  • the disproportionation catalyst and the isomerization catalyst particles are mixed for the butene disproportionation reaction.
  • the two are combined in disorder, and the active phase distance cannot be accurately controlled, which is unfavorable for the generation and migration of intermediates, and the catalyst efficiency under high space velocity conditions. reduce.
  • simply mixing the two catalyst powders after molding has a relatively low catalytic efficiency.
  • the inventors of the present invention provide a new type of catalyst through research and experimentation, change the inherent mode of particle mixing, and integrate the disproportionation catalyst and the isomerization catalyst into catalyst particles.
  • the integrated catalyst precisely controls the distance between the two active phases, which is not only conducive to the migration of intermediates, but also avoids the fact that the two catalysts are too close to each other and cause the active sites to cover each other and reduce the activity stability, which can improve the catalyst under high space velocity conditions. activity and stability.
  • the isomerization catalyst used is polycrystalline hexagonal flake magnesium oxide, and the morphology and structure can fully expose the active sites of the isomerization catalyst, improve its utilization rate, and help prolong the stability of the catalyst.
  • the present invention provides a new catalyst particle for the disproportionation reaction of olefins and the Its preparation method and application.
  • a “range” disclosed herein is given in the form of lower and upper limits, eg, one or more lower limits and one or more upper limits.
  • a given range can be defined by selecting a lower limit and an upper limit that define the boundaries of the given range. All ranges defined in this manner are inclusive and combinable, ie any lower limit can be combined with any upper limit to form a range.
  • ranges of 60-110 and 80-120 are listed for certain parameters, with the understanding that ranges of 60-120 and 80-110 are also contemplated.
  • the lower limits are listed as 1 and 2 and the upper limits are listed as 3, 4 and 5, the following ranges are contemplated and are within the scope of the present disclosure: 1-3, 1-4, 1 -5, 2-3, 2-4 and 2-5.
  • the "active phase" of a catalyst refers to the structural units that are bound together and remain morphologically stable during storage and reaction.
  • disproportionation catalysts and/or isomerization catalysts are typically used in olefin disproportionation reactions. Therefore, for the purpose of the present invention, in the integrated catalyst of the present invention, the available disproportionation catalyst and isomerization catalyst can be directly used as different active phases. Accordingly, for the purposes of the present invention, the terms “disproportionation catalyst” and “disproportionation active phase” may be used interchangeably as appropriate; and the terms “isomerization catalyst” and “isomerization active phase” may be used interchangeably as appropriate.
  • an "integrated catalyst” includes a plurality of distinct active phases that are integrated together and whose relative positions remain substantially unchanged during the olefin disproportionation reaction; for example, in the described olefin disproportionation reaction During the olefin disproportionation reaction, the relative positional displacement between different active phases is not more than 0.5mm, preferably not more than 0.1mm.
  • the "effective distance" of two adjacent different active phases refers to the average migration distance of the object to be catalyzed between two adjacent different active phases of the catalyst, so as to count the adjacent two different active phases.
  • the distance between the bisectors SA and SB may represent the "effective distance" of the two adjacent two different active phases A and B.
  • its bisector is the cross-section at half its thickness; thus when the active phases A and B are laminated together in the thickness direction in the form of a cuboid, respectively, the "effective distance" of the active phases A and B is equal to half the sum of the thicknesses of the active phases A and B.
  • its bisector is the sphere whose volume is half of the original sphere, that is, the radius is (approximately 0.79R1).
  • the "thickness" of the particles generally refers to the direction perpendicular to the interface S 0 , and the plane direction of the interface S 0 is referred to as the "diameter". to" direction.
  • the direction of the larger scale is called "length".
  • the effective distance occupied by an active phase is the difference between the bisector of the active phase (eg, the bisector S A ) and the interface S 0 between the active phase and another active phase. distance between.
  • One aspect of the present invention provides an integrated catalyst for an olefin disproportionation reaction, wherein the integrated catalyst includes a plurality of different active phases integrated together, and the different active phases are in the process of the olefin disproportionation reaction.
  • the relative position between the two adjacent active phases remains basically unchanged; it is characterized in that the effective distance between the bisectors of two adjacent different active phases is 0.5-5 mm, preferably 1-3 mm.
  • the different active phases are integrated together by a manner selected from the group consisting of: filling the respective active phases in a container with a plurality of chambers; laminating the respective active phases; laminating the respective active phases Active phases are bonded; the active phases are rolled in sequence; the active phases are co-extruded.
  • the ratio of the effective distances occupied by the two different active phases is 1:10-10:1.
  • a plurality of different active phases alternate one or more times in a periodic regular arrangement.
  • periodic regular arrangement means that the arrangement of different active phases exhibits a periodic law.
  • any two adjacent active phases are respectively a disproportionation catalyst and an isomerization catalyst, and the ratio of the effective distance occupied by the adjacent active phases of the disproportionation catalyst and the isomerization catalyst is (1:1 ) to (1:5), preferably (1:2) to (1:3).
  • the relative positional displacement between different active phases during the olefin disproportionation reaction is not more than 0.5 mm, preferably not more than 0.1 mm.
  • the catalyst is in particulate form.
  • the total thickness of the catalyst particles is 2.0mm-8.0mm, preferably 2.5mm-6.0mm; the radial length is 1.8mm-6.0mm, preferably cylindrical.
  • the present invention provides, in an exemplary embodiment, a catalyst particle for olefin disproportionation reaction, the catalyst particle has a multi-layer structure of at least two layers, and any two adjacent layers are respectively a disproportionation catalyst layer and an isomerization catalyst layer.
  • the thickness ratio of the catalyst layer, the adjacent disproportionation catalyst layer and the isomerization catalyst layer is (1:1) to (1:5), preferably (1:2) to (1:3).
  • the catalyst particles have a total thickness of 2.5 mm to 6.0 mm, and a radial length of 1.8 mm to 6.0 mm.
  • the shape of the catalyst particles may be cylindrical, preferably straight cylindrical.
  • the diameter of the cylindrical shape is 1.8mm-6.0mm, and the height is 2.5mm-6.0mm.
  • each layer is a cylindrical shape with an equal bottom surface and a coaxial shape.
  • the catalyst particles have a two-layer structure or a three-layer structure.
  • the two-layer structure is composed of a disproportionation catalyst layer and an isomerization catalyst layer.
  • the three-layer structure is composed of a first disproportionation catalyst layer, an isomerization catalyst layer and a second disproportionation catalyst layer in sequence, or a first isomerization catalyst layer, a disproportionation catalyst layer and a second isomerization catalyst layer.
  • the disproportionation catalyst is a tungsten-based catalyst, preferably, in parts by weight, comprising the following components:
  • the carrier is selected from at least one of SiO 2 and mesoporous molecular sieves.
  • the mesoporous molecular sieve is a silicon-containing mesoporous molecular sieve, selected from at least one of MCM molecular sieve, SBA molecular sieve, HMS molecular sieve, and MSU molecular sieve; more preferably, selected from one of MCM molecular sieve, SBA molecular sieve, HMS molecular sieve, and MSU molecular sieve .
  • the disproportionation catalyst can be prepared by a method commonly used in the art, such as an impregnation method. Generally, after the carrier is impregnated with the supported tungsten source, a process of drying and calcination is required to obtain a disproportionation catalyst. The drying and calcination are carried out using conventional operating conditions, such as drying at 80-120° C. for 1-10 hours, and calcining at 400-600° C. for 2-7 hours.
  • the isomerization catalyst is an alkaline earth metal oxide selected from at least one of calcium oxide, magnesium oxide, strontium oxide and barium oxide; preferably magnesium oxide.
  • the isomerization catalyst magnesium oxide is polycrystalline hexagonal flake magnesium oxide; preferably, the hexagonal side length is 180-600 nm, and the sheet thickness is 8-30 nm.
  • described magnesium oxide preparation method is as follows:
  • step 4 After washing the precipitate obtained in step 3 with water, wash with absolute ethanol, and then dry at 70°C-90°C for 8-12 hours;
  • step 5 calcining the product obtained in step 4, controlling the heating rate to be 5-15°C/min, and calcining at 400°C-520°C for 3-6 hours.
  • the soluble magnesium salt described in step 1) is selected from at least one of magnesium sulfate, magnesium chloride, and magnesium carbonate;
  • the surfactant described in step 2) is selected from at least one molecular surfactant, preferably polyethylene glycol alcohol, at least one of P123;
  • the complexing agent is selected from at least one of ethylenediaminetetraacetic acid and aminotriacetic acid;
  • the precipitating agent in step 3) is selected from at least one of ammonia water and urea, and the concentration 5-30%.
  • the weight ratio of the disproportionation catalyst to the isomerization catalyst is (1:1) to (1:12). More preferably, the weight ratio of the disproportionation catalyst to the isomerization catalyst is (1:1) to (1:10).
  • the disproportionation catalyst refers to the disproportionation catalyst derived from all the disproportionation catalyst layers, and the isomerization catalyst refers to the isomerization catalyst derived from all the isomerization catalyst layers.
  • Another aspect of the present invention provides a method for preparing the integrated catalyst of the present invention, comprising:
  • step 1) molding the powders of multiple different active phases in step 1) respectively to form multiple active phases with stable structure;
  • the particle size of the powder is 8-400 meshes.
  • the present invention provides, in an exemplary embodiment, a method for preparing the above catalyst particles, comprising:
  • step 2) molding a kind of powder in step 1) to make catalyst layer A;
  • step 3 using the method of step 3), on the basis of the two-layer catalyst particle shaped body obtained in step 3), combine other catalyst layers;
  • the particle size of the disproportionation catalyst powder in step 1) is 8-50 mesh, and the particle size of the isomerization catalyst powder is 8-50 mesh.
  • step 1) described in step 2) When one kind of powder in step 1) described in step 2) is disproportionation catalyst powder, the other kind of powder in step 3) is isomerization catalyst powder.
  • step 1) described in step 2) can be isomerization catalyst powder, the other kind of powder in step 3) is disproportionation catalyst powder.
  • Step 2) The molding method of the catalyst layer A may adopt a tablet molding process.
  • Step 3) The molding method of the catalyst layer B can adopt a tablet molding process, that is, another powder in step 1) is pressed and molded on a bottom surface of the catalyst layer A to form a combination with the catalyst layer A. the catalyst layer B.
  • step 4) is not performed, the catalyst particle shaped body obtained in step 3) is the catalyst particle shaped body finally obtained.
  • the forming method of the other catalyst layers in step 4) can adopt the tablet forming process, that is, according to the requirement that any two adjacent layers are respectively the disproportionation catalyst layer and the isomerization catalyst layer, the same tablet forming process as in step 3) is used. , forming other catalyst layers combined together to obtain the final catalyst particle shaped body.
  • the tablet forming process is a method well known to those skilled in the art.
  • the shape of the catalyst particles may be a shape commonly used in the art, preferably a cylindrical shape, more preferably a straight cylindrical shape.
  • the catalyst particles are composed of a plurality of catalyst layers in the axial direction.
  • a first binder when the disproportionation catalyst powder is formed, a first binder can be used.
  • the first binder is selected from at least one of silica sol and aluminum sol.
  • a second binder can be used when the isomerization catalyst powder is formed.
  • the second binder is selected from at least one of polyvinyl alcohol, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl cellulose and polyvinylpyrrolidone.
  • the mass ratio of the disproportionation catalyst powder to the first binder is 3:1 to 1:2.
  • the mass ratio of the isomerization catalyst powder and the second binder is 3:1-1:2.
  • the catalyst particle molding body needs to be dried and calcined.
  • the drying conditions described in step 5) are preferably as follows: the drying temperature is 80-110° C., and the drying time is 8-15 hours.
  • the preferred roasting process is as follows: the heating rate is controlled to be 0.5-1.5°C/min in the whole process, firstly, the temperature is raised from room temperature to 280-320°C under an inert atmosphere, the temperature is kept constant for 4-8 hours, and the temperature is continued to be raised to 460-500°C for 4-8 hours.
  • the inert atmosphere can be selected from the atmosphere of at least one gas in nitrogen and inert gas.
  • the oxygen-containing atmosphere can be an air atmosphere.
  • a third aspect of the present invention provides a method for disproportionation of olefins, using a fixed-bed process, wherein the above-mentioned catalyst particles or the catalyst particles prepared according to the above-mentioned shaping method are used.
  • the method for disproportionation of olefins comprises contacting a feedstock containing ethylene and butenes or pentenes with the catalyst particles described above or the catalyst particles prepared according to the molding method described above to obtain a propylene-containing product.
  • the reaction conditions are as follows: the reaction temperature is 200-450° C., the reaction pressure is 0-5 MPa, and the raw material mass space velocity is 1-30 h ⁇ 1 .
  • the reaction temperature is 250-400° C., the reaction pressure is 1-4 MPa, and the raw material weight space velocity is 5-25 h ⁇ 1 .
  • the reaction temperature is 300-350° C., the reaction pressure is 2-3 MPa, and the raw material weight space velocity is 10-20 h ⁇ 1 .
  • the present invention has the following advantages:
  • the present invention by changing the inherent mode of mechanical mixing of the disproportionation catalyst and the isomerization catalyst in the prior art, integrates the disproportionation catalyst and the isomerization catalyst into a single layer into catalyst particles, which is beneficial to the intermediate
  • the migration of the two catalysts can also prevent the two catalysts from being too close to cause the active sites to cover each other, thereby improving the activity and stability of the catalyst.
  • the inventor has further researched and found that the present invention precisely controls the distance between the two types of active centers at the millimeter level by comprehensively controlling the thickness ratio of the adjacent disproportionation catalyst layer and the isomerization catalyst layer, and the mass ratio of the disproportionation catalyst and the isomerization catalyst.
  • the catalyst can have better activity and stability.
  • the present invention overcomes the above-mentioned problem of disconnection between the catalyst layers by controlling the processes of molding materials and calcination, and further improves the activity and stability of the catalyst.
  • 1 is a schematic structural diagram of two-layer catalyst particles (disproportionation catalyst layer and isomerization catalyst layer);
  • FIG. 2 is a schematic structural diagram of three-layer catalyst particles (from top to bottom, the first isomerization catalyst layer, the disproportionation catalyst layer and the second isomerization catalyst layer);
  • 3 is a schematic structural diagram of three-layer catalyst particles (from top to bottom, the first disproportionation catalyst layer, the isomerization catalyst layer and the second disproportionation catalyst layer);
  • Fig. 4 is the SEM, TEM and electron diffraction pattern of magnesium oxide
  • FIG. 5 is a SEM image of magnesium oxide used in Comparative Example 3.
  • FIG. 5 is a SEM image of magnesium oxide used in Comparative Example 3.
  • the particle size of the disproportionation catalyst powder used is 10-20 mesh; the particle size of the used isomerization catalyst powder is 10-20 mesh.
  • the magnesium oxide used in the embodiment of the present invention is polycrystalline hexagonal sheet-shaped mesoporous magnesium oxide; the preparation method is as follows:
  • step 4 After washing the precipitate obtained in step 3 with water, wash with absolute ethanol, and then dry at 80°C for 8h;
  • step 5 calcining the product obtained in step 4, controlling the heating rate to be 10°C/min, and calcining at 500°C for 4 hours.
  • the disproportionation catalyst powder composed of WO 3 /SiO 2 (wherein, the mass content of WO 3 is 15%) and the aluminum sol are mixed and granulated according to the weight ratio of 3:1, and the tablet is made into a diameter*height 1.8mm*3.0mm
  • the thickness ratio of the disproportionation catalyst layer A to the isomerization catalyst layer B is 1:1, and the weight ratio of the disproportionation catalyst to the isomerization catalyst is 1:6.
  • the above catalyst particle shaped body is dried at a drying temperature of 90°C for 10 hours, and then calcined.
  • the calcination process is as follows: the heating rate is controlled to be 0.5°C/min in the whole process, and firstly, the temperature is raised from normal temperature to about 280°C under a nitrogen atmosphere, and the constant temperature is 4h. Continue to heat up to about 460°C for 4 hours, then switch to an air atmosphere, heat up to about 530°C, hold a constant temperature for 4 hours, and then switch to a nitrogen atmosphere again for 4 hours to obtain catalyst particles.
  • the prepared catalyst particles were packed in a ⁇ 25mm fixed-bed reactor, and ethylene and butene were used as raw materials, and the disproportionation reaction was carried out under the conditions that the weight space velocity was 10h -1 , the reaction temperature was 300°C, and the reaction pressure was 3MPa, The results are shown in Table 1.
  • the disproportionation catalyst powder composed of WO 3 /SiO 2 (wherein, the mass content of WO 3 is 5%) and the aluminum sol are mixed and granulated according to the weight ratio of 2:1, and tableted to make a cylindrical catalyst with a size of 6.0mm*1.0mm
  • Layer A Mix barium oxide powder and hydroxymethyl cellulose in a weight ratio of 2:1, press a bottom surface of catalyst layer A and combine cylindrical catalyst layer B to make a 6.0mm*6.0mm cylindrical catalyst Particle shaped body, the effective distance of active phase is 3mm.
  • the thickness ratio of the disproportionation catalyst layer A to the isomerization catalyst layer B is 1:5, and the weight ratio of the disproportionation catalyst to the isomerization catalyst is 1:6.
  • the above catalyst particle shaped body was dried at a drying temperature of 90°C for 10 hours, and then calcined.
  • the calcination process was as follows: the heating rate was controlled to be 1.5°C/min throughout the whole process, and firstly, the temperature was raised from room temperature to about 320°C in a nitrogen atmosphere, and the temperature was kept constant for 8 hours. Continue to heat up to about 500°C for 8 hours, then switch to an air atmosphere, heat up to about 570°C, hold a constant temperature for 8 hours, and then switch to a nitrogen atmosphere again for 8 hours to obtain catalyst particles.
  • the prepared catalyst particles were packed in a ⁇ 25mm fixed-bed reactor, and ethylene and butene were used as raw materials, and the disproportionation reaction was carried out under the conditions that the weight space velocity was 10h -1 , the reaction temperature was 300°C, and the reaction pressure was 3MPa, The results are shown in Table 1.
  • the disproportionation catalyst powder composed of WO 3 /MCM-41 (wherein, the mass content of WO 3 is 10%) and the silica sol are mixed and granulated according to the weight ratio of 1:1, and pressed into a cylindrical shape of 3.0mm*2.0mm.
  • the effective distance of the active phase is 3 mm.
  • the thickness ratio of the disproportionation catalyst layer A to the isomerization catalyst layer B is 1:2, and the weight ratio of the disproportionation catalyst to the isomerization catalyst is 1:6.
  • the above catalyst particle shaped body was dried at a drying temperature of 90°C for 10 hours, and then calcined.
  • the calcination process was as follows: the heating rate was controlled to be 1°C/min throughout the whole process, firstly, the temperature was raised from room temperature to about 300°C under a nitrogen atmosphere, and the temperature was kept constant for 6 hours. Continue to heat up to about 480°C for 6 hours, then switch to an air atmosphere, heat up to about 550°C for 4 hours, and then switch to a nitrogen atmosphere again for 4 hours to obtain catalyst particles.
  • the prepared catalyst particles were packed in a ⁇ 25mm fixed-bed reactor, and ethylene and butene were used as raw materials, and the disproportionation reaction was carried out under the conditions that the weight space velocity was 10h -1 , the reaction temperature was 300°C, and the reaction pressure was 3MPa, The results are shown in Table 1.
  • the disproportionation catalyst powder with the composition of WO 3 /SBA-15 (wherein, the mass content of WO 3 is 10%) and the silica sol are mixed and granulated according to the weight ratio of 1:2, and pressed into a 4.0mm*1.0mm cylindrical shape.
  • Catalyst layer A Mix magnesium oxide powder and hydroxypropyl cellulose in a weight ratio of 1:2, press a bottom surface of catalyst layer A and combine cylindrical catalyst layer B to make a cylindrical shape of 4.0mm*2.5mm
  • the catalyst particle shaped body has an active phase effective distance of 1.25 mm.
  • the thickness ratio of the disproportionation catalyst layer A to the isomerization catalyst layer B is 1:1.5, and the weight ratio of the disproportionation catalyst to the isomerization catalyst is 1:6.
  • the above catalyst particle shaped body was dried at a drying temperature of 90°C for 10 hours, and then calcined.
  • the calcination process was as follows: the heating rate was controlled to be 1°C/min throughout the whole process, firstly, the temperature was raised from room temperature to about 300°C under a nitrogen atmosphere, and the temperature was kept constant for 6 hours. Continue to heat up to about 480°C for 6 hours, then switch to an air atmosphere, heat up to about 550°C for 4 hours, and then switch to a nitrogen atmosphere again for 4 hours to obtain catalyst particles.
  • the prepared catalyst particles were packed in a ⁇ 25mm fixed-bed reactor, and ethylene and butene were used as raw materials, and the disproportionation reaction was carried out under the conditions that the weight space velocity was 10h -1 , the reaction temperature was 300°C, and the reaction pressure was 3MPa, The results are shown in Table 1.
  • the disproportionation catalyst powder with the composition of WO 3 /MSU (wherein, the mass content of WO 3 is 10%) and the silica sol are mixed and granulated according to the weight ratio of 1:2, and pressed into a 4.0mm*2.0mm cylindrical catalyst layer.
  • the catalyst particle shaped body has an active phase effective distance of 3 mm.
  • the thickness ratio of the disproportionation catalyst layer A to the isomerization catalyst layer B is 1:2, and the weight ratio of the disproportionation catalyst to the isomerization catalyst is 1:6.
  • the above catalyst particle shaped body was dried at a drying temperature of 90°C for 10 hours, and then calcined.
  • the calcination process was as follows: the heating rate was controlled to be 1°C/min throughout the whole process, firstly, the temperature was raised from room temperature to about 300°C under a nitrogen atmosphere, and the temperature was kept constant for 6 hours.
  • the prepared catalyst particles were packed in a ⁇ 25mm fixed-bed reactor, and ethylene and butene were used as raw materials, and the disproportionation reaction was carried out under the conditions that the weight space velocity was 10h -1 , the reaction temperature was 300°C, and the reaction pressure was 3MPa, The results are shown in Table 1.
  • the disproportionation catalyst powder composed of WO 3 /SiO 2 (wherein, the mass content of WO 3 is 10%) and the silica sol are mixed and granulated according to the weight ratio of 1:2, and tableted to make a 3.0mm*1.5mm cylindrical catalyst Layer A:
  • the magnesium oxide powder and hydroxypropyl methylcellulose are mixed and granulated according to the weight ratio of 1:2, and a bottom surface of the catalyst layer A is pressed and combined with the cylindrical catalyst layer B to make a 3.0mm*4.5mm
  • the cylindrical catalyst particle intermediate of 3.0mm*6.0mm is obtained by combining a disproportionation catalyst layer C in the same way, and the effective distance of the active phase is 2.25mm.
  • the thickness ratio of disproportionation catalyst layer A:isomerization catalyst layer B:disproportionation catalyst layer C is 1:2:1, and the weight ratio is 1:2:1.
  • the above catalyst particle shaped body was dried at a drying temperature of 90°C for 10 hours, and then calcined.
  • the calcination process was as follows: the heating rate was controlled to be 1°C/min throughout the whole process, firstly, the temperature was raised from room temperature to about 300°C under a nitrogen atmosphere, and the temperature was kept constant for 6 hours.
  • the catalyst particles are disproportionated by the first disproportionation A catalyst layer 1 (disproportionation catalyst layer A), a first isomerization catalyst layer 2 (isomerization catalyst layer B), and a second disproportionation catalyst layer 3 (disproportionation catalyst layer C) are constituted.
  • the prepared catalyst particles were packed in a ⁇ 25mm fixed-bed reactor, and ethylene and butene were used as raw materials, and the disproportionation reaction was carried out under the conditions that the weight space velocity was 10h -1 , the reaction temperature was 300°C, and the reaction pressure was 3MPa, The results are shown in Table 1.
  • the magnesium oxide powder and hydroxypropyl methylcellulose are mixed and granulated according to the weight ratio of 1:2, and tableted to make a cylindrical catalyst layer A of 3.0mm*2.4mm; the composition is WO 3 /SiO 2 (wherein, The disproportionation catalyst powder with WO 3 mass content of 10%) is mixed with silica sol according to the weight ratio of 1:2, and the catalyst layer B is pressed on the bottom surface of the catalyst layer A to form a cylindrical catalyst with a size of 3.0mm*3.6mm.
  • For the particle intermediate continue to combine a layer of isomerization catalyst layer C in the same way to obtain a cylindrical catalyst particle shaped body of 3.0mm*6.0mm, and the effective distance of the active phase is 1.8mm.
  • the thickness ratio of the isomerization catalyst layer A: the disproportionation catalyst layer B: the isomerization catalyst layer C is 2:1:2, and the weight ratio is 5:1:5.
  • the above catalyst particle shaped body was dried at a drying temperature of 90°C for 10 hours, and then calcined.
  • the calcination process was as follows: the heating rate was controlled to be 1°C/min throughout the whole process, firstly, the temperature was raised from room temperature to about 300°C under a nitrogen atmosphere, and the temperature was kept constant for 6 hours. Continue to heat up to about 480 °C for 6 hours, then switch to an air atmosphere, heat up to about 550 °C, hold a constant temperature for 4 hours, then switch to a nitrogen atmosphere again, and keep a constant temperature for 4 hours to obtain catalyst particles, as shown in Figure 2.
  • the isomerization catalyst layer 2 (isomerization catalyst layer A), the first disproportionation catalyst layer 1 (disproportionation catalyst layer B), and the second isomerization catalyst layer 4 (isomerization catalyst layer C) are constituted.
  • the prepared catalyst particles were packed in a ⁇ 25mm fixed-bed reactor, and ethylene and butene were used as raw materials, and the disproportionation reaction was carried out under the conditions that the weight space velocity was 10h -1 , the reaction temperature was 300°C, and the reaction pressure was 3MPa, The results are shown in Table 1.
  • the disproportionation catalyst powder composed of WO 3 /SiO 2 (wherein, the mass content of WO 3 is 10%) and the silica sol are mixed and granulated according to the weight ratio of 1:2, and pressed into a 4.0mm*2.0mm cylindrical catalyst.
  • Layer A Mix magnesium oxide powder and hydroxypropyl methyl cellulose in a weight ratio of 1:2, press a bottom surface of catalyst layer A to combine catalyst layer B, and make a 4.0mm*6.0mm cylindrical catalyst Particle shaped body, the effective distance of active phase is 3mm.
  • the thickness ratio of the disproportionation catalyst layer A to the isomerization catalyst layer B is 1:2
  • the weight ratio of the disproportionation catalyst to the isomerization catalyst is 1:2.
  • the above catalyst particle shaped body was dried at a drying temperature of 90°C for 10 hours, and then calcined.
  • the calcination process was as follows: the heating rate was controlled to be 1°C/min throughout the whole process, firstly, the temperature was raised from room temperature to about 300°C under a nitrogen atmosphere, and the temperature was kept constant for 6 hours. Continue to heat up to about 480°C for 6 hours, then switch to an air atmosphere, heat up to about 550°C for 4 hours, and then switch to a nitrogen atmosphere again for 4 hours to obtain catalyst particles.
  • the prepared catalyst particles were packed in a ⁇ 25mm fixed-bed reactor, and ethylene and butene were used as raw materials, and the disproportionation reaction was carried out under the conditions that the weight space velocity was 10h -1 , the reaction temperature was 300°C, and the reaction pressure was 3MPa, The results are shown in Table 1.
  • the disproportionation catalyst powder composed of WO 3 SiO 2 (wherein, the mass content of WO 3 is 10%) and the silica sol are mixed and granulated according to the weight ratio of 1:2, and pressed into a 4.0mm*2.5mm cylindrical catalyst layer.
  • the effective distance of the active phase is 2.5 mm.
  • the thickness ratio of the disproportionation catalyst layer A to the isomerization catalyst layer B is 1:1, and the weight ratio of the disproportionation catalyst to the isomerization catalyst is 1:2.
  • the above catalyst particle shaped body was dried at a drying temperature of 90°C for 10 hours, and then calcined.
  • the calcination process was as follows: the heating rate was controlled to be 1°C/min throughout the whole process, and the temperature was first raised from room temperature to about 300°C in a nitrogen atmosphere, and the temperature was kept constant for 6 hours. Continue to heat up to about 480°C for 6 hours, then switch to an air atmosphere, heat up to about 550°C, hold a constant temperature for 4 hours, and then switch to a nitrogen atmosphere again for 4 hours to obtain catalyst particles.
  • the prepared catalyst particles were packed in a ⁇ 25mm fixed-bed reactor, and ethylene and butene were used as raw materials, and the disproportionation reaction was carried out under the conditions that the weight space velocity was 10h -1 , the reaction temperature was 300°C, and the reaction pressure was 3MPa, The results are shown in Table 1.
  • the disproportionation catalyst powder composed of WO 3 /SiO 2 (wherein, the mass content of WO 3 is 10%) and the silica sol are mixed and granulated according to the weight ratio of 1:2, and pressed into a 4.0mm*2.0mm cylindrical catalyst.
  • Layer A Mix magnesium oxide powder and hydroxypropyl methyl cellulose in a weight ratio of 1:2, press a bottom surface of catalyst layer A to combine catalyst layer B, and make a 4.0mm*6.0mm cylindrical catalyst Particle shaped body, the effective distance of active phase is 3mm.
  • the thickness ratio of the disproportionation catalyst layer A to the isomerization catalyst layer B is 1:2
  • the weight ratio of the disproportionation catalyst to the isomerization catalyst is 1:2.
  • the above-mentioned catalyst particle shaped body was dried at a drying temperature of 90°C for 10 hours, and then calcined by a conventional method.
  • the calcination process was as follows: the heating rate was controlled to be 5°C/min in the whole process, and the temperature was raised to about 550°C in a muffle furnace at a constant temperature. After 4 h, catalyst particles were obtained, and it was found that the particles were fractured and could not be used for reaction evaluation.
  • the disproportionation catalyst powder composed of WO 3 /SiO 2 (wherein, the mass content of WO 3 is 10%) and the silica sol are mixed and granulated according to the weight ratio of 1:2, and pressed into a 4.0mm*2.0mm cylindrical catalyst.
  • Layer A Mix magnesium oxide powder and hydroxypropyl methyl cellulose in a weight ratio of 1:2, press a bottom surface of catalyst layer A to combine catalyst layer B, and make a 4.0mm*6.0mm cylindrical catalyst Particle shaped body, the effective distance of active phase is 3mm.
  • the thickness ratio of the disproportionation catalyst layer A to the isomerization catalyst layer B is 1:2
  • the weight ratio of the disproportionation catalyst to the isomerization catalyst is 1:2.
  • the above catalyst particle shaped body was dried at a drying temperature of 90°C for 10 hours, and then calcined.
  • the calcination process was as follows: the heating rate was controlled to be 1°C/min throughout the whole process, firstly, the temperature was raised from room temperature to about 300°C under a nitrogen atmosphere, and the temperature was kept constant for 6 hours. Continue to heat up to about 480°C for 6 hours, then switch to an air atmosphere, heat up to about 550°C for 4 hours, and then switch to a nitrogen atmosphere again for 4 hours to obtain catalyst particles.
  • the prepared catalyst particles were packed in a ⁇ 25mm fixed-bed reactor, and ethylene and butene were used as raw materials, and the disproportionation reaction was carried out under the conditions that the weight space velocity was 1 h -1 , the reaction temperature was 200 °C, and the reaction pressure was 5 MPa, The results are shown in Table 1.
  • the disproportionation catalyst powder composed of WO 3 /SiO 2 (wherein, the mass content of WO 3 is 10%) and the silica sol are mixed and granulated according to the weight ratio of 1:2, and pressed into a 4.0mm*2.0mm cylindrical catalyst.
  • Layer A Mix magnesium oxide powder and hydroxypropyl methyl cellulose in a weight ratio of 1:2, press a bottom surface of catalyst layer A to combine catalyst layer B, and make a 4.0mm*6.0mm cylindrical catalyst Particle shaped body, the effective distance of active phase is 3mm.
  • the thickness ratio of the disproportionation catalyst layer A to the isomerization catalyst layer B is 1:2
  • the weight ratio of the disproportionation catalyst to the isomerization catalyst is 1:2.
  • the above catalyst particle shaped body was dried at a drying temperature of 90°C for 10 hours, and then calcined.
  • the calcination process was as follows: the heating rate was controlled to be 1°C/min throughout the whole process, firstly, the temperature was raised from room temperature to about 300°C under a nitrogen atmosphere, and the temperature was kept constant for 6 hours. Continue to heat up to about 480°C for 6 hours, then switch to an air atmosphere, heat up to about 550°C for 4 hours, and then switch to a nitrogen atmosphere again for 4 hours to obtain catalyst particles.
  • the prepared catalyst particles were packed in a ⁇ 25mm fixed-bed reactor, and ethylene and butene were used as raw materials, and the disproportionation reaction was carried out under the conditions that the weight space velocity was 30h -1 , the reaction temperature was 450°C, and the reaction pressure was 0.1MPa. , and the results are shown in Table 1.
  • the disproportionation catalyst powder composed of WO 3 /SiO 2 (wherein, the mass content of WO 3 is 10%) and the silica sol are mixed and granulated according to the weight ratio of 1:2, and pressed into a 4.0mm*5.0mm cylindrical catalyst.
  • Particle A shaped body, the catalyst particle shaped body was dried at a drying temperature of 90°C for 10 hours, and then calcined.
  • the calcination process is as follows: the heating rate is controlled to be 1°C/min throughout the whole process, and firstly, the temperature is increased from room temperature to 300°C under a nitrogen atmosphere.
  • the magnesium oxide powder and hydroxypropyl methylcellulose are mixed and granulated according to the weight ratio of 1:2, and pressed into a 4.0mm*5.0mm cylindrical catalyst particle B molded body.
  • the drying temperature of the catalyst particle molded body is: Dry at 90°C for 10 hours, and then calcinate.
  • the calcination process is as follows: the heating rate is controlled to be 1°C/min throughout the whole process. First, the temperature is raised from room temperature to about 300°C under nitrogen atmosphere, and the temperature is kept constant for 6 hours. , and then switched to an air atmosphere, heated to about 550° C., maintained at a constant temperature for 4 hours, and then switched to a nitrogen atmosphere again, maintained at a constant temperature for 4 hours, to obtain catalyst particles B.
  • the above two catalyst particles were mechanically mixed and packed in a ⁇ 25mm fixed bed reactor, wherein the weight ratio of disproportionation catalyst and isomerization catalyst was 1:6.
  • the disproportionation reaction was carried out under the conditions of a weight space velocity of 10 h -1 , a reaction temperature of 300° C. and a reaction pressure of 3 MPa. The results are shown in Table 1.
  • the disproportionation catalyst powder composed of WO 3 /SiO 2 (wherein, the mass content of WO 3 is 10%) and the silica sol are mixed and granulated according to the weight ratio of 1:2, and the magnesium oxide powder and hydroxypropyl methylcellulose are mixed according to the weight ratio.
  • the weight ratio is 1:2 for mixing and granulation, the disproportionation catalyst powder is mixed with the magnesium oxide powder according to the weight ratio of 1:6, and the tablet is pressed to make a cylindrical catalyst particle molded body of 4.0mm*5.0mm.
  • the above catalyst particle shaped body was dried at a drying temperature of 90°C for 10 hours, and then calcined.
  • the calcination process was as follows: the heating rate was controlled to be 1°C/min throughout the whole process, firstly, the temperature was raised from room temperature to about 300°C under a nitrogen atmosphere, and the temperature was kept constant for 6 hours. Continue to heat up to about 480°C for 6 hours, then switch to an air atmosphere, heat up to about 550°C for 4 hours, and then switch to a nitrogen atmosphere again for 4 hours to obtain catalyst particles.
  • the above catalyst particles were packed in a fixed bed reactor of ⁇ 25 mm.
  • the weight ratio is 1:2 mixed granulation, the disproportionation catalyst powder is mixed with the magnesium oxide powder according to the weight ratio of 1:6, and the tablet is made into a 4.0mm*5.0mm cylindrical catalyst particle molded body, wherein the magnesium oxide used is: Non-flaky magnesium oxide, SEM characterization is shown in Figure 5.
  • the above catalyst particle shaped body was dried at a drying temperature of 90°C for 10 hours, and then calcined.
  • the calcination process was as follows: the heating rate was controlled to be 1°C/min throughout the whole process, firstly, the temperature was raised from room temperature to about 300°C under a nitrogen atmosphere, and the temperature was kept constant for 6 hours. Continue to heat up to about 480°C for 6 hours, then switch to an air atmosphere, heat up to about 550°C for 4 hours, and then switch to a nitrogen atmosphere again for 4 hours to obtain catalyst particles.
  • the above catalyst particles were packed in a fixed bed reactor of ⁇ 25 mm.
  • **1:2:1 in Example 6 is the thickness ratio of disproportionation catalyst layer A, isomerization catalyst layer B, and disproportionation catalyst layer C;
  • Example 7 ***2:1:2 in Example 7 is the thickness ratio of the isomerization catalyst layer A, the disproportionation catalyst layer B, and the isomerization catalyst layer C.

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Abstract

本发明公开了一种用于烯烃歧化反应的整合式催化剂，其中，该整合式催化剂包括整合在一起的多个不同的活性相，且在所述烯烃歧化反应的过程中不同活性相之间的相对位置保持基本不变；其特征在于，相邻的两个不同活性相各自的平分面之间的有效距离为0.5～5mm，优选为1～3mm。

Description

用于烯烃歧化反应的催化剂颗粒及其制备方法 技术领域
本发明涉及一种用于烯烃歧化反应的催化剂颗粒及其制备方法，以及该催化剂颗粒在烯烃歧化领域中的应用。
背景技术
烯烃歧化是通过在过渡金属化合物催化剂的作用下，使烯烃中C＝C双键断裂并重组，以获得新的烯烃产物的过程。
烯烃歧化技术是调节产品结构的有效技术手段之一。利用丁烯与乙烯的交叉歧化作用，可通过加入适量乙烯，将相对过剩的、附加值较低的丁烯原料转化为高附加值丙烯产品。
丁烯歧化催化剂主要有铼基、钼基和钨基催化剂。US5898091和US6166279公开的C 4、C 5烯烃处理方法，其中烯烃歧化制丙烯过程中，所采用的催化剂为Re 2O 7/Al 2O 3，反应器为移动床。US6358482公开了一种用C 4馏分烃生产异丁烯和丙烯的装置。C 4馏分烃经过选择加氢和精馏后分离出异丁烯和1-丁烯以及2-丁烯，分离出来的1-丁烯通过双键异构化生成2-丁烯，富2-丁烯物料与乙烯歧化反应生成丙烯，所用的歧化反应催化剂为Re 2O 7/Al 2O 3。US6743958公开的是US6358482的改进工艺，分离出来的异丁烯经过骨架异构化生成正丁烯循环使用。WO00014038介绍了一种丁烯歧化制丙烯的方法，原料丁烯为1-丁烯、2-丁烯或其混合物，催化剂为WO 3/SiO 2或Cs +、PO 4 3-等改性的WO 3/SiO 2。
目前，烯烃歧化制丙烯所用催化剂采用双元催化剂，包括歧化催化剂及异构化催化剂，其中异构化催化剂通常采用碱土金属氧化物，而且单独的异构化催化剂基本没有烯烃歧化作用。当前研究表明，二者通过颗粒混合进行装填的方法，可以有效提高低碳烯烃歧化催化剂的活性和稳定性。
发明内容
本发明的发明人经研究发现，歧化反应中中间体烯丙基在两类催化活性相的迁移对反应影响较大，催化剂设计过程中要考虑两类活性相 距离的精确控制。现有技术将歧化催化剂和异构化催化剂颗粒混合后用于丁烯歧化反应，二者无序组合，无法精确控制活性相距离，对中间体的生成和迁移不利，高空速工况下催化剂效率降低。而简单的将两种催化剂粉末混合后成型催化效率也比较低，究其原因，两类活性相距离太近互相覆盖导致性能下降。为此，本发明的发明人经研究和试验，提供一种新型催化剂，改变颗粒混合的固有模式，将歧化催化剂和异构化催化剂整合于一体制成催化剂颗粒。该整合式催化剂精确控制两类活性相的距离，既有利于中间体的迁移，又可以避免两种催化剂距离太近致使活性位互相覆盖而导致活性稳定性降低，可以改善高空速工况下催化剂的活性、稳定性。同时，保证所用异构化催化剂为多晶六边形片状氧化镁，该形貌结构可以使得异构化催化剂的活性位点充分暴露，提高其利用率，有利于延长催化剂的稳定性。
针对现有技术中存在的烯烃歧化催化剂和异构化催化剂机械混合用于低碳烯烃歧化反应时，催化剂活性和稳定性差的问题，本发明提供一种新的用于烯烃歧化反应的催化剂颗粒及其制备方法和应用。
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发明所属领域内一般技术人员常理解的相同意思。在有冲突的情况下，包括定义在内，以本说明书为准。
此外，本说明书提到的各种范围均包括它们的端点在内，除非另有明确说明。此外，当对量、浓度或其它值或参数给出范围、一个或多个优选范围或很多优选上限值与优选下限值时，应把它理解为具体公开了由任意对任意范围上限值或优选值与任意范围下限值或优选值所形成的所有范围，不论是否一一公开了这些数值对。
在本发明中，当技术方案以“包含”、“包括”所列举的某些要素等开放式限定的形式给出时，本领域技术人员将理解的是，由这些要素构成、或者基本上由这些要素构成的实施方式显然能够用于实施所述技术方案。因此，本领域技术人员理解的是，本发明中以所述开放式限定给出的技术方案也涵盖由列举要素构成、或者基本上其构成的具体实施方式。
最后，在没有明确指明的情况下，本说明书内所提到的所有百分数、份数、比率等都是以重量为基准的；但是以重量为基准时不符合本领 域技术人员的常规认识时，由本领域技术人员的常规认识来确定其基准。
本文所公开的“范围”以下限和上限的形式，例如一个或多个下限与一个或多个上限的形式给出。给定范围可通过选择一个下限和一个上限来进行限定，选定的下限和上限限定了给定范围的边界。所有以这种方式限定的范围是包含和可组合的，即任何下限可与任何上限组合形成一个范围。例如，针对特定参数列出了60-110和80-120的范围，理解为60-120和80-110的范围也是可预料到的。此外，如果列出的下限为1和2而列出的上限为3，4和5，则下面的范围都是可预计并且属于本发明公开范围之内的：1-3、1-4、1-5、2-3、2-4和2-5。
对于本发明目的，催化剂的“活性相”是指结合在一起，并在储存和反应过程中保持其形态稳定的结构单元。
本领域技术人员已知的是，通常在烯烃歧化反应中使用歧化催化剂和/或异构化催化剂。因此，对于本发明目的，在本发明的整合式催化剂中，可以直接将可用的歧化催化剂和异构化催化剂分别作为不同的活性相使用。相应地，对于本发明目的，术语“歧化催化剂”与“歧化活性相”可以视情况互换使用；而术语“异构化催化剂”与“异构化活性相”可以视情况互换使用。
对于本发明目的，“整合式催化剂”包括整合在一起的多个不同的活性相，且在所述烯烃歧化反应的过程中不同活性相之间的相对位置保持基本不变；例如，在所述烯烃歧化反应的过程中，不同活性相之间的相对位置位移不超过0.5mm，优选不超过0.1mm。
对于本发明目的，相邻的两个不同活性相的“有效距离”是指为量化待催化的对象在催化剂的相邻的两个不同活性相之间的平均迁移距离，从而统计所述相邻的两个不同活性相各自所含物质的平均间距。容易理解的是，对于两个相邻的两个不同活性相A和B，存在一个为平面或曲面的界面S 0。同样容易理解的是，在所述活性相A内部，存在一个平分活性相A的质量、并且与平面界面S 0平行的平面形式的平分面S A或者与曲面S 0界面上的各个点距离均相等的曲面形式的平分面 S A；以及相应地，在所述活性相B内部，存在一个平分面S B。由此，所述平分面S A与S B之间的距离可以代表所述两个相邻的两个不同活性相A和B的“有效距离”。例如，对于均匀的长方体，其平分面为其厚度一半处的横截面；因而当活性相A和B分别以长方体的形式在厚度方向上层压在一起时，活性相A与B的“有效距离”等于活性相A和B的厚度之和的一半。再如，对于半径为R1的均匀的球体，其平分面是使其体积为原球体一半处的球面，即半径为
Figure PCTCN2021124570-appb-000001
(大约0.79R1)处的球面。
由此，对于本发明目的，考虑到装在催化剂的反应器的形状等因素，颗粒的“厚度”一般是指与所述界面S 0垂直的方向，而界面S 0所在平面方向称为“径向”方向。当所述界面S 0并非圆形或不能以圆形来描述时，则较大尺度的方向称为“长度”。
相应地，对于本发明目的，某活性相(例如活性相A)占据的有效距离则为该活性相的平分面(例如平分面S A)与该活性相与另一活性相的界面S 0之间的距离。
本发明一方面提供了一种用于烯烃歧化反应的整合式催化剂，其中，该整合式催化剂包括整合在一起的多个不同的活性相，且在所述烯烃歧化反应的过程中不同活性相之间的相对位置保持基本不变；其特征在于，相邻的两个不同活性相各自的平分面之间的有效距离为0.5～5mm，优选为1～3mm。
在本发明的一种实施方式中，所述不同活性相通过选自以下的方式整合在一起：将各个活性相分别装填在具有多个腔室的容器中；将各个活性相层压；将各个活性相粘结；将各个活性相按顺序滚球；将各个活性相共挤出。
在本发明的一种实施方式中，相邻的两个所述不同活性相的重心之间的距离中，两个不同活性相各自占据的有效距离之比为1:10-10:1。
在本发明的一种实施方式中，可选地，多个不同活性相交替一次或多次的周期性规则排列。对于本发明的目的，周期性规则排列是指不 同活性相的排列呈现周期性的规律。例如，对于两个不同活性相A和B，其排列为AB、BA、ABA、BAB、ABAB或BABA等形式；而对于例如三个不同活性相A、B和C，其排列为例如ABC、ABCABC等形式。
在本发明的一种实施方式中，任意相邻两个活性相分别为歧化催化剂和异构化催化剂，相邻的歧化催化剂和异构化催化剂活性相各自占据的有效距离比例为(1:1)～(1:5)，优选为(1:2)～(1:3)。
在本发明的一种实施方式中，在所述烯烃歧化反应的过程中不同活性相之间的相对位置位移不超过0.5mm，优选不超过0.1mm。
在本发明的一种实施方式中，该催化剂呈颗粒形式。
在本发明的一种实施方式中，所述的催化剂颗粒的总厚度为2.0mm～8.0mm，优选2.5mm～6.0mm；径向长度为1.8mm～6.0mm，优选地为圆柱形。
由此，本发明在一个例示实施方式中提供了一种用于烯烃歧化反应的催化剂颗粒，该催化剂颗粒呈至少两层的多层结构，任意相邻两层分别为歧化催化剂层和异构化催化剂层，相邻的歧化催化剂层和异构化催化剂层的厚度比例为(1:1)～(1:5)，优选为(1:2)～(1:3)。
在本发明的一种实施方式中，所述的催化剂颗粒的总厚度为2.5mm～6.0mm，径向长度为1.8mm～6.0mm。
在本发明的一种实施方式中，所述的催化剂颗粒的形状可以为圆柱形，优选为直圆柱形。所述圆柱形的直径为1.8mm～6.0mm，高度为2.5mm～6.0mm。所述多层结构中，每层均为等底面同轴的圆柱形。
在本发明的一种实施方式中，所述的催化剂颗粒为两层结构或三层结构。其中两层结构为歧化催化剂层和异构化催化剂层构成。三层结构依次为第一歧化催化剂层、异构化催化剂层和第二歧化催化剂层构成，或者为第一异构化催化剂层、歧化催化剂层和第二异构化催化剂层构成。
在本发明的一种实施方式中，所述的歧化催化剂为钨基催化剂，优选地，以重量份数计，包括以下组分：
(1)85～95份的载体，
(2)5～15份的氧化钨。
在本发明的一种实施方式中，优选的，载体选自SiO 2和介孔分子筛中的至少一种。介孔分子筛为含硅介孔分子筛，选自MCM分子筛、SBA分子筛、HMS分子筛、MSU分子筛中的至少一种；更优选的，选自MCM分子筛、SBA分子筛、HMS分子筛、MSU分子筛中的一种。
在本发明的一种实施方式中，所述歧化催化剂可采用本领域常用方法制备，比如浸渍法。一般在载体浸渍负载钨源后需要干燥和焙烧过程，得到歧化催化剂。所述干燥和焙烧采用常规的操作条件进行，比如在80～120℃干燥1～10h，在400～600℃焙烧2～7h。
在本发明的一种实施方式中，所述的异构化催化剂为碱土金属氧化物，选自氧化钙、氧化镁、氧化锶和氧化钡中的至少一种；优选为氧化镁。
在本发明的一种实施方式中，所述的异构化催化剂氧化镁为多晶六边形片状氧化镁；优选地，六边形边长为180-600nm，片厚为8-30nm。
在本发明的一种实施方式中，所述的氧化镁制备方法如下：
1)制备浓度为5-20％的可溶性镁盐溶液，升温至40℃-80℃进行搅拌；
2)加入表面活性剂及络合剂，其中表面活性剂与镁离子摩尔比例为0.5％-3％，络合剂与镁离子的摩尔比为1-8％；
3)加入沉淀剂，沉淀剂与镁离子的摩尔比为2:1-5:1；
4)将步骤3所得沉淀物水洗之后，用无水乙醇洗涤，之后在70℃-90℃干燥8-12h；
5)将步骤4所得物焙烧，控制升温速率为5～15℃/min，400℃-520℃焙烧3-6h。
步骤1)中所述的可溶性镁盐选自硫酸镁、氯化镁、碳酸镁中的至少一种；步骤2)中所述表面活性剂选自分子型表面活性剂至少一种，优选为聚乙二醇，P123中的至少一种；所述络合剂选自乙二胺四乙酸、氨基三乙酸的至少一种；步骤3)中所述沉淀剂选自氨水、尿素中的至少一种，浓度为5-30％。
在本发明的一种实施方式中，优选的，催化剂颗粒中，歧化催化剂与异构化催化剂的重量比例为(1:1)～(1:12)。更优选的，歧化催化剂与异构化催化剂的重量比例为(1:1)～(1:10)。其中歧化催化剂是指源于所 有歧化催化剂层的歧化催化剂，异构化催化剂是指源于所有异构化催化剂层的异构化催化剂。
本发明另一方面提供了制备如本发明所述的整合式催化剂的方法，包括：
1)分别提供多个不同的活性相的粉料；
2)对步骤1)中的多个不同的活性相的粉料分别进行成型，形成结构稳定的多个活性相；
3)将不同活性相的多个活性相通过选自以下的方式整合在一起：将各个活性相分别装填在具有多个腔室的容器中；将各个活性相层压；将各个活性相粘结；将各个活性相按顺序滚球；将各个活性相共挤出；其中，控制相邻的两个不同活性相各自的平分面之间的有效距离为0.5～5mm，优选为1～3mm。
在本发明的一种实施方式中，所述粉料的粒径为8～400目。
由此，本发明在一个例示实施方式中提供了一种上述催化剂颗粒的制备方法，包括：
1)分别准备歧化催化剂粉料和异构化催化剂粉料；
2)将步骤1)中的一种粉料成型，制成催化剂层A；
3)在催化剂层A的一底面上结合由步骤1)中的另一种粉料成型的催化剂层B；
4)任选地，利用步骤3)的方法，在步骤3)所得两层催化剂颗粒成型体基础上，结合其他催化剂层；
5)将最终所得的催化剂颗粒成型体进行干燥和焙烧，得到催化剂颗粒。
步骤1)中所述歧化催化剂粉料的粒径为8～50目，异构化催化剂粉料的粒径为8～50目。
当步骤2)所述的步骤1)中的一种粉料为歧化催化剂粉料时，步骤3)中的另一种粉料为异构化催化剂粉料。步骤2)所述的步骤1)中的一种粉料可以为异构化催化剂粉料时，步骤3)中的另一种粉料为歧化催化剂粉料。
步骤2)所述催化剂层A的成型方法可以采用压片成型工艺。
步骤3)所述催化剂层B的成型方法可以采用压片成型工艺，即将步骤1)中的另一种粉料在催化剂层A的一底面上进行压片成型，形 成与催化剂层A结合在一起的催化剂层B。当不进行步骤4)时，步骤3)所得的催化剂颗粒成型体，即为最终所得的催化剂颗粒成型体。
步骤4)所述其他催化剂层的成型方法可以采用压片成型工艺，即根据任意相邻两层分别为歧化催化剂层和异构化催化剂层的要求，利用与步骤3)相同的压片成型工艺，形成结合在一起的其他催化剂层，得到最终所得的催化剂颗粒成型体。
根据本发明，“任选地”是指进行或不进行该步骤。
根据本发明，压片成型工艺为本领域技术人员所熟知的方法。所述催化剂颗粒的形状可以为本领域中常规使用的形状，优选为圆柱形，进一步优选为直圆柱形。所述催化剂颗粒沿轴向由多个催化剂层构成。
在本发明的一种实施方式中，歧化催化剂粉料成型时，可以采用第一粘合剂。所述第一粘合剂选自硅溶胶和铝溶胶中的至少一种。异构化催化剂粉料成型，可以采用第二粘合剂。所述第二粘合剂选自聚乙烯醇、羟甲基纤维素、羟丙基甲基纤维素、羟丙基纤维素和聚乙烯吡咯烷酮中的至少一种。
在本发明的一种实施方式中，所述歧化催化剂粉料和第一粘合剂的质量比为3:1～1:2。所述异构化催化剂粉料和第二粘合剂的质量比为3:1～1:2。
在本发明的一种实施方式中，在得到符合尺寸要求的催化剂颗粒成型后，需要对催化剂颗粒成型体进行干燥处理和焙烧处理。步骤5)所述的干燥条件优选如下：干燥温度为80～110℃，干燥时间为8～15小时。优选的焙烧过程如下：全程控制升温速率为0.5～1.5℃/min，首先在惰性气氛下由常温升至280～320℃，恒温4～8h，继续升温至460～500℃，恒温4～8h，之后切换成含氧气氛，升温至530～570℃，恒温4～8h，之后再次切换成惰性气氛，恒温4～8h。所述的惰性气氛可以选自氮气、惰性气体中至少一种气体的气氛。所述的含氧气氛可以为空气气氛。
本发明第三方面提供了一种烯烃歧化的方法，采用固定床工艺，其中采用上述的催化剂颗粒或根据上述成型方法制得的催化剂颗粒。
在本发明的一种实施方式中，烯烃歧化的方法包括使含乙烯和丁烯或者戊烯的原料与上述的催化剂颗粒或根据上述成型方法制得的催化剂颗粒接触，得到含丙烯的产物。
在本发明的一种实施方式中，优选的，反应条件如下：反应温度为200～450℃，反应压力为0～5MPa，原料质量空速为1～30h -1。优选地，反应温度为250～400℃，反应压力为1～4MPa，原料重量空速为5～25h -1。进一步优选地，反应温度为300～350℃，反应压力为2～3MPa，原料重量空速为10～20h -1。
与现有技术相比，本发明具有如下优点：
1、发明人研究发现，本发明通过改变现有技术中歧化催化剂和异构化催化剂机械混合的固有模式，将歧化催化剂和异构化催化剂分层集于一体制成催化剂颗粒，既有利于中间体的迁移，又可以避免两种催化剂距离太近致使活性位互相覆盖，提高了催化剂的活性和稳定性。
2、发明人进一步研究发现，本发明通过综合控制相邻歧化催化剂层和异构化催化剂层的厚度比、歧化催化剂和异构化催化剂质量比等，精确控制两类活性中心距离在毫米级，可以使催化剂具有更好的活性和稳定性。
3、由于歧化催化剂与异构化催化剂所用粉料物性差异较大，在制备过程中二者接触界面容易发生断层现象。本发明通过控制成型物料和焙烧等过程克服了上述各催化剂层之间断层的问题，而且还进一步提高了催化剂的活性和稳定性。
附图说明
图1为两层催化剂颗粒(歧化催化剂层和异构化催化剂层)结构示意图；
图2为三层催化剂颗粒(由上到下依次为第一异构化催化剂层、歧化催化剂层与第二异构化催化剂层)结构示意图；
图3为三层催化剂颗粒(由上到下依次为第一歧化催化剂层、异构化催化剂层与第二歧化催化剂层)结构示意图；
其中，附图标记说明如下：
1-第一歧化催化剂层，2-第一异构化催化剂层，3-第二歧化催化剂层，4-第二异构化催化剂层。
图4为氧化镁的SEM、TEM及电子衍射图；
图5为对比例3中所用氧化镁的SEM图。
具体实施方式
以下通过实施例对本发明进行详细说明，但本发明的保护范围并不限于下述说明。
本发明实施例和对比例中，所用歧化催化剂粉末的粒度为10-20目；所用异构化催化剂粉末的粒度为10-20目。
本发明实施例中所用氧化镁均为多晶六边形片状介孔氧化镁；制备方法如下：
1)制备浓度为10％的可溶性镁盐溶液，升温至60℃进行搅拌；
2)加入聚乙二醇及乙二胺四乙酸，其中表面活性剂与镁离子摩尔比例为1％，络合剂与镁离子的摩尔比为2％；
3)加入沉淀剂氨水，沉淀剂与镁离子的摩尔比为3:1；
4)将步骤3所得沉淀物水洗之后，用无水乙醇洗涤，之后在80℃干燥8h；
5)将步骤4所得物焙烧，控制升温速率为10℃/min，500℃焙烧4h。
实施例1
将组成为WO 3/SiO 2(其中，WO 3质量含量为15％)的歧化催化剂粉末与铝溶胶按照重量比为3:1混合造粒，压片制作成直径*高度＝1.8mm*3.0mm的圆柱状催化剂层A；将氧化钙粉末与聚乙烯醇按照重量比为3:1混合，在催化剂层A的一底面上压片结合圆柱状催化剂层B，制作成1.8mm*6.0mm的圆柱状催化剂颗粒成型体，活性相有效距离为3mm。其中歧化催化剂层A与异构化催化剂层B的厚度比为1:1，歧化催化剂与异构化催化剂的重量比例为1:6。
上述催化剂颗粒成型体在干燥温度为90℃下干燥10小时，然后进行焙烧，焙烧过程如下：全程控制升温速率为0.5℃/min，首先在氮气气氛下由常温升至280℃左右，恒温4h，继续升温至460℃左右，恒温4h，之后切换成空气气氛，升温至530℃左右，恒温4h，之后再次切换成氮气气氛，恒温4h，得到催化剂颗粒。
将制得的催化剂颗粒装填在Φ25mm的固定床反应器中，以乙烯和丁烯为原料，在重量空速为10h -1，反应温度为300℃，反应压力为3MPa的条件下进行歧化反应，结果见列表1。
实施例2
将组成为WO 3/SiO 2(其中，WO 3质量含量为5％)的歧化催化剂粉末与铝溶胶按照重量比为2:1混合造粒，压片制作成6.0mm*1.0mm的圆柱状催化剂层A；将氧化钡粉末与羟甲基纤维素按照重量比为2:1混合，在催化剂层A的一底面上压片结合圆柱状催化剂层B，制作成6.0mm*6.0mm的圆柱状催化剂颗粒成型体，活性相有效距离为3mm。其中歧化催化剂层A与异构化催化剂层B的厚度比为1:5，歧化催化剂与异构化催化剂的重量比例为1:6。
上述催化剂颗粒成型体在干燥温度为90℃下干燥10小时，然后进行焙烧，焙烧过程如下：全程控制升温速率为1.5℃/min，首先在氮气气氛下由常温升至320℃左右，恒温8h，继续升温至500℃左右，恒温8h，之后切换成空气气氛，升温至570℃左右，恒温8h，之后再次切换成氮气气氛，恒温8h，得到催化剂颗粒。
将制得的催化剂颗粒装填在Φ25mm的固定床反应器中，以乙烯和丁烯为原料，在重量空速为10h -1，反应温度为300℃，反应压力为3MPa的条件下进行歧化反应，结果见列表1。
实施例3
将组成为WO 3/MCM-41(其中，WO 3质量含量为10％)的歧化催化剂粉末与硅溶胶按照重量比为1:1混合造粒，压片制作成3.0mm*2.0mm的圆柱状催化剂层A；将氧化锶粉末与聚乙烯吡咯烷酮按照重量比为1:1混合，在催化剂层A的一底面上压片结合圆柱状催化剂层B，制作成3.0mm*6.0mm的圆柱状催化剂颗粒成型体，活性相有效距离为3mm。其中歧化催化剂层A与异构化催化剂层B的厚度比为1:2，歧化催化剂与异构化催化剂的重量比例为1:6。
上述催化剂颗粒成型体在干燥温度为90℃下干燥10小时，然后进行焙烧，焙烧过程如下：全程控制升温速率为1℃/min，首先在氮气气氛下由常温升至300℃左右，恒温6h，继续升温至480℃左右，恒温6h，之后切换成空气气氛，升温至550℃左右，恒温4h，之后再次切换成氮气气氛，恒温4h，得到催化剂颗粒。
将制得的催化剂颗粒装填在Φ25mm的固定床反应器中，以乙烯和丁烯为原料，在重量空速为10h -1，反应温度为300℃，反应压力为3MPa的条件下进行歧化反应，结果见列表1。
实施例4
将组成为WO 3/SBA-15(其中，WO 3质量含量为10％)的歧化催化剂粉末与硅溶胶按照重量比为1:2混合造粒，压片制作成4.0mm*1.0mm的圆柱状催化剂层A；将氧化镁粉末与羟丙基纤维素按照重量比为1:2混合，在催化剂层A的一底面上压片结合圆柱状催化剂层B，制作成4.0mm*2.5mm的圆柱状催化剂颗粒成型体，活性相有效距离为1.25mm。其中歧化催化剂层A与异构化催化剂层B的厚度比为1:1.5，歧化催化剂与异构化催化剂的重量比例为1:6。
上述催化剂颗粒成型体在干燥温度为90℃下干燥10小时，然后进行焙烧，焙烧过程如下：全程控制升温速率为1℃/min，首先在氮气气氛下由常温升至300℃左右，恒温6h，继续升温至480℃左右，恒温6h，之后切换成空气气氛，升温至550℃左右，恒温4h，之后再次切换成氮气气氛，恒温4h，得到催化剂颗粒。
将制得的催化剂颗粒装填在Φ25mm的固定床反应器中，以乙烯和丁烯为原料，在重量空速为10h -1，反应温度为300℃，反应压力为3MPa的条件下进行歧化反应，结果见列表1。
实施例5
将组成为WO 3/MSU(其中，WO 3质量含量为10％)的歧化催化剂粉末与硅溶胶按照重量比为1:2混合造粒，压片制作成4.0mm*2.0mm的圆柱状催化剂层A；将氧化镁粉末与羟丙基甲基纤维素按照重量比为1:2混合，在催化剂层A的一底面上压片结合圆柱状催化剂层B，制作成4.0mm*6.0mm的圆柱状催化剂颗粒成型体，活性相有效距离为3mm。其中歧化催化剂层A与异构化催化剂层B的厚度比为1:2，歧化催化剂与异构化催化剂的重量比例为1:6。
上述催化剂颗粒成型体在干燥温度为90℃下干燥10小时，然后进行焙烧，焙烧过程如下：全程控制升温速率为1℃/min，首先在氮气气氛下由常温升至300℃左右，恒温6h，继续升温至480℃左右，恒温 6h，之后切换成空气气氛，升温至550℃左右，恒温4h，之后再次切换成氮气气氛，恒温4h，得到催化剂颗粒，如图1，由第一歧化催化剂层1(歧化催化剂层A)和第一异构化催化剂层2(异构化催化剂层B)构成。
将制得的催化剂颗粒装填在Φ25mm的固定床反应器中，以乙烯和丁烯为原料，在重量空速为10h -1，反应温度为300℃，反应压力为3MPa的条件下进行歧化反应，结果见列表1。
实施例6
将组成为WO 3/SiO 2(其中，WO 3质量含量为10％)的歧化催化剂粉末与硅溶胶按照重量比为1:2混合造粒，压片制作成3.0mm*1.5mm的圆柱状催化剂层A；将氧化镁粉末与羟丙基甲基纤维素按照重量比为1:2混合造粒，在催化剂层A的一底面上压片结合圆柱状催化剂层B，制作成3.0mm*4.5mm的圆柱状催化剂颗粒中间体，同样的办法继续结合一层歧化催化剂层C，得到3.0mm*6.0mm的圆柱状催化剂颗粒成型体，活性相有效距离为2.25mm。其中歧化催化剂层A：异构化催化剂层B：歧化催化剂层C的厚度比为1:2:1，其重量比例为1:2:1。
上述催化剂颗粒成型体在干燥温度为90℃下干燥10小时，然后进行焙烧，焙烧过程如下：全程控制升温速率为1℃/min，首先在氮气气氛下由常温升至300℃左右，恒温6h，继续升温至480℃左右，恒温6h，之后切换成空气气氛，升温至550℃左右，恒温4h，之后再次切换成氮气气氛，恒温4h，得到催化剂颗粒，如图3，该催化剂颗粒由第一歧化催化剂层1(歧化催化剂层A)、第一异构化催化剂层2(异构化催化剂层B)和第二歧化催化剂层3(歧化催化剂层C)构成。
将制得的催化剂颗粒装填在Φ25mm的固定床反应器中，以乙烯和丁烯为原料，在重量空速为10h -1，反应温度为300℃，反应压力为3MPa的条件下进行歧化反应，结果见列表1。
实施例7
将氧化镁粉末与羟丙基甲基纤维素按照重量比为1:2混合造粒，压片制作成3.0mm*2.4mm的圆柱状催化剂层A；将组成为WO 3/SiO 2(其中，WO 3质量含量为10％)的歧化催化剂粉末与硅溶胶按照重量比为 1:2混合，在催化剂层A的一底面上压片结合催化剂层B，制作成3.0mm*3.6mm的圆柱状催化剂颗粒中间体，同样的办法继续结合一层异构化催化剂层C，得到3.0mm*6.0mm的圆柱状催化剂颗粒成型体，活性相有效距离为1.8mm。其中异构化催化剂层A：歧化催化剂层B：异构化催化剂层C厚度比为2:1:2，其重量比例为5:1:5。
上述催化剂颗粒成型体在干燥温度为90℃下干燥10小时，然后进行焙烧，焙烧过程如下：全程控制升温速率为1℃/min，首先在氮气气氛下由常温升至300℃左右，恒温6h，继续升温至480℃左右，恒温6h，之后切换成空气气氛，升温至550℃左右，恒温4h，之后再次切换成氮气气氛，恒温4h，得到催化剂颗粒，如图2，该催化剂颗粒由第一异构化催化剂层2(异构化催化剂层A)、第一歧化催化剂层1(歧化催化剂层B)和第二异构化催化剂层4(异构化催化剂层C)构成。
将制得的催化剂颗粒装填在Φ25mm的固定床反应器中，以乙烯和丁烯为原料，在重量空速为10h -1，反应温度为300℃，反应压力为3MPa的条件下进行歧化反应，结果见列表1。
实施例8
将组成为WO 3/SiO 2(其中，WO 3质量含量为10％)的歧化催化剂粉末与硅溶胶按照重量比为1:2混合造粒，压片制作成4.0mm*2.0mm的圆柱状催化剂层A；将氧化镁粉末与羟丙基甲基纤维素按照重量比为1:2混合，在催化剂层A的一底面上压片结合催化剂层B，制作成4.0mm*6.0mm的圆柱状催化剂颗粒成型体，活性相有效距离为3mm。其中歧化催化剂层A与异构化催化剂层B的厚度比为1:2，歧化催化剂与异构化催化剂的重量比例为1:2。
上述催化剂颗粒成型体在干燥温度为90℃下干燥10小时，然后进行焙烧，焙烧过程如下：全程控制升温速率为1℃/min，首先在氮气气氛下由常温升至300℃左右，恒温6h，继续升温至480℃左右，恒温6h，之后切换成空气气氛，升温至550℃左右，恒温4h，之后再次切换成氮气气氛，恒温4h，得到催化剂颗粒。
将制得的催化剂颗粒装填在Φ25mm的固定床反应器中，以乙烯和丁烯为原料，在重量空速为10h -1，反应温度为300℃，反应压力为3MPa的条件下进行歧化反应，结果见列表1。
实施例9
将组成为WO 3SiO 2(其中，WO 3质量含量为10％)的歧化催化剂粉末与硅溶胶按照重量比为1:2混合造粒，压片制作成4.0mm*2.5mm的圆柱状催化剂层A；将氧化镁粉末与羟丙基甲基纤维素按照重量比为1:2混合，在催化剂层A的一底面上压片结合催化剂层B，制作成4.0mm*5.0mm的圆柱状催化剂颗粒成型体，活性相有效距离为2.5mm。其中歧化催化剂层A与异构化催化剂层B的厚度比为1:1，歧化催化剂与异构化催化剂的重量比例为1:2。
上述催化剂颗粒成型体在干燥温度为90℃下干燥10小时，然后进行焙烧，焙烧过程如下：全程控制升温速率为1℃/min，首先在氮气气氛下由常温升至300℃左右，恒温6h，继续升温至480℃左右，恒温6h，之后切换成空气气氛，升温至550℃左右，恒温4h，之后再次切换成氮气气氛，恒温4h，得到催化剂颗粒。
将制得的催化剂颗粒装填在Φ25mm的固定床反应器中，以乙烯和丁烯为原料，在重量空速为10h -1，反应温度为300℃，反应压力为3MPa的条件下进行歧化反应，结果见列表1。
实施例10
将组成为WO 3/SiO 2(其中，WO 3质量含量为10％)的歧化催化剂粉末与硅溶胶按照重量比为1:2混合造粒，压片制作成4.0mm*2.0mm的圆柱状催化剂层A；将氧化镁粉末与羟丙基甲基纤维素按照重量比为1:2混合，在催化剂层A的一底面上压片结合催化剂层B，制作成4.0mm*6.0mm的圆柱状催化剂颗粒成型体，活性相有效距离为3mm。其中歧化催化剂层A与异构化催化剂层B的厚度比为1:2，歧化催化剂与异构化催化剂的重量比例为1:2。
上述催化剂颗粒成型体在干燥温度为90℃下干燥10小时，然后采用常规方法焙烧，焙烧过程如下：全程控制升温速率为5℃/min，在马弗炉中由常温升至550℃左右，恒温4h，得到催化剂颗粒，发现颗粒断层破碎，无法用于反应评价。
实施例11
将组成为WO 3/SiO 2(其中，WO 3质量含量为10％)的歧化催化剂粉末与硅溶胶按照重量比为1:2混合造粒，压片制作成4.0mm*2.0mm的圆柱状催化剂层A；将氧化镁粉末与羟丙基甲基纤维素按照重量比为1:2混合，在催化剂层A的一底面上压片结合催化剂层B，制作成4.0mm*6.0mm的圆柱状催化剂颗粒成型体，活性相有效距离为3mm。其中歧化催化剂层A与异构化催化剂层B的厚度比为1:2，歧化催化剂与异构化催化剂的重量比例为1:2。
上述催化剂颗粒成型体在干燥温度为90℃下干燥10小时，然后进行焙烧，焙烧过程如下：全程控制升温速率为1℃/min，首先在氮气气氛下由常温升至300℃左右，恒温6h，继续升温至480℃左右，恒温6h，之后切换成空气气氛，升温至550℃左右，恒温4h，之后再次切换成氮气气氛，恒温4h，得到催化剂颗粒。
将制得的催化剂颗粒装填在Φ25mm的固定床反应器中，以乙烯和丁烯为原料，在重量空速为1h -1，反应温度为200℃，反应压力为5MPa的条件下进行歧化反应，结果见列表1。
实施例12
将组成为WO 3/SiO 2(其中，WO 3质量含量为10％)的歧化催化剂粉末与硅溶胶按照重量比为1:2混合造粒，压片制作成4.0mm*2.0mm的圆柱状催化剂层A；将氧化镁粉末与羟丙基甲基纤维素按照重量比为1:2混合，在催化剂层A的一底面上压片结合催化剂层B，制作成4.0mm*6.0mm的圆柱状催化剂颗粒成型体，活性相有效距离为3mm。其中歧化催化剂层A与异构化催化剂层B的厚度比为1:2，歧化催化剂与异构化催化剂的重量比例为1:2。
上述催化剂颗粒成型体在干燥温度为90℃下干燥10小时，然后进行焙烧，焙烧过程如下：全程控制升温速率为1℃/min，首先在氮气气氛下由常温升至300℃左右，恒温6h，继续升温至480℃左右，恒温6h，之后切换成空气气氛，升温至550℃左右，恒温4h，之后再次切换成氮气气氛，恒温4h，得到催化剂颗粒。
将制得的催化剂颗粒装填在Φ25mm的固定床反应器中，以乙烯和丁烯为原料，在重量空速为30h -1，反应温度为450℃，反应压力为0.1MPa的条件下进行歧化反应，结果见列表1。
对比例1
将组成为WO 3/SiO 2(其中，WO 3质量含量为10％)的歧化催化剂粉末与硅溶胶按照重量比为1:2混合造粒，压片制作成4.0mm*5.0mm的圆柱状催化剂颗粒A成型体，上述催化剂颗粒成型体在干燥温度为90℃下干燥10小时，然后进行焙烧，焙烧过程如下：全程控制升温速率为1℃/min，首先在氮气气氛下由常温升至300℃左右，恒温6h，继续升温至480℃左右，恒温6h，之后切换成空气气氛，升温至550℃左右，恒温4h，之后再次切换成氮气气氛，恒温4h，得到催化剂颗粒A。
将氧化镁粉末与羟丙基甲基纤维素按照重量比为1:2混合造粒，压片制作成4.0mm*5.0mm的圆柱状催化剂颗粒B成型体，上述催化剂颗粒成型体在干燥温度为90℃下干燥10小时，然后进行焙烧，焙烧过程如下：全程控制升温速率为1℃/min，首先在氮气气氛下由常温升至300℃左右，恒温6h，继续升温至480℃左右，恒温6h，之后切换成空气气氛，升温至550℃左右，恒温4h，之后再次切换成氮气气氛，恒温4h，得到催化剂颗粒B。
将上述两种催化剂颗粒机械混合装填在Φ25mm的固定床反应器中，其中歧化催化剂与异构化催化剂重量比例为1:6。以乙烯和丁烯为原料，在重量空速为10h -1，反应温度为300℃，反应压力为3MPa的条件下进行歧化反应，结果见列表1。
对比例2
将组成为WO 3/SiO 2(其中，WO 3质量含量为10％)的歧化催化剂粉末与硅溶胶按照重量比为1:2混合造粒，将氧化镁粉末与羟丙基甲基纤维素按照重量比为1:2混合造粒，将歧化催化剂粉末与将氧化镁粉末按照重量比为1:6混合，压片制作成4.0mm*5.0mm的圆柱状催化剂颗粒成型体。
上述催化剂颗粒成型体在干燥温度为90℃下干燥10小时，然后进行焙烧，焙烧过程如下：全程控制升温速率为1℃/min，首先在氮气气氛下由常温升至300℃左右，恒温6h，继续升温至480℃左右，恒温6h，之后切换成空气气氛，升温至550℃左右，恒温4h，之后再次切换成氮气气氛，恒温4h，得到催化剂颗粒。将上述催化剂颗粒装填在 Φ25mm的固定床反应器中。以乙烯和丁烯为原料，在重量空速为10h -1，反应温度为300℃，反应压力为3MPa的条件下进行歧化反应，结果见列表1。
对比例3
将组成为WO 3/SiO 2(其中，WO 3质量含量为10％)的歧化催化剂粉末与硅溶胶按照重量比为1:2混合造粒，将氧化镁粉末与羟丙基甲基纤维素按照重量比为1:2混合造粒，将歧化催化剂粉末与将氧化镁粉末按照重量比为1:6混合，压片制作成4.0mm*5.0mm的圆柱状催化剂颗粒成型体，其中所用氧化镁为非片状氧化镁，SEM表征见图5。
上述催化剂颗粒成型体在干燥温度为90℃下干燥10小时，然后进行焙烧，焙烧过程如下：全程控制升温速率为1℃/min，首先在氮气气氛下由常温升至300℃左右，恒温6h，继续升温至480℃左右，恒温6h，之后切换成空气气氛，升温至550℃左右，恒温4h，之后再次切换成氮气气氛，恒温4h，得到催化剂颗粒。将上述催化剂颗粒装填在Φ25mm的固定床反应器中。以乙烯和丁烯为原料，在重量空速为10h -1，反应温度为300℃，反应压力为3MPa的条件下进行歧化反应，结果见列表1。
表1
Figure PCTCN2021124570-appb-000002
注：*稳定性是指催化剂转化率在60％以上的稳定运行时间；
**实施例6中的1:2:1为歧化催化剂层A、异构化催化剂层B、歧化催化剂层C的厚度比；
***实施例7中的2:1:2为异构化催化剂层A、歧化催化剂层B、异构化催化剂层C的厚度比。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单 变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (23)

  1. 一种用于烯烃歧化反应的整合式催化剂，其中，该整合式催化剂包括整合在一起的多个不同的活性相，且在所述烯烃歧化反应的过程中不同活性相之间的相对位置保持基本不变；其特征在于，相邻的两个不同活性相各自的平分面之间的有效距离为0.5～5mm，优选为1～3mm。
  2. 按照权利要求1所述的整合式催化剂，其中所述不同活性相通过选自以下的方式整合在一起：将各个活性相分别装填在具有多个腔室的容器中；将各个活性相层压；将各个活性相粘结；将各个活性相按顺序滚球；将各个活性相共挤出。
  3. 按照权利要求1所述的整合式催化剂，其中相邻的两个所述不同活性相的重心之间的距离中，两个不同活性相各自占据的有效距离之比为1:10-10:1。
  4. 按照权利要求1所述的整合式催化剂，其中多个不同活性相交替一次或多次的周期性规则排列。
  5. 按照权利要求1所述的整合式催化剂，其中任意相邻两个活性相分别为歧化催化剂和异构化催化剂，相邻的歧化催化剂和异构化催化剂活性相各自占据的有效距离比例为(1:1)～(1:5)，优选为(1:2)～(1:3)。
  6. 按照权利要求1所述的整合式催化剂，其中在所述烯烃歧化反应的过程中不同活性相之间的相对位置位移不超过0.5mm，优选不超过0.1mm。
  7. 按照权利要求1所述的整合式催化剂，其中，该催化剂呈颗粒形式。
  8. 按照权利要求7所述的整合式催化剂，其特征在于：所述的催化剂颗粒的总厚度为2.0mm～8.0mm，优选2.5mm～6.0mm；径向长度为1.8mm～6.0mm，优选地为圆柱形。
  9. 按照权利要求7所述的整合式催化剂，其特征在于：所述的催化剂颗粒为至少两层的多层结构，优选两层结构或三层结构。
  10. 按照权利要求1所述的整合式催化剂，其特征在于：所述多个不同的活性相中的第一活性相为歧化催化剂，以重量份数计，包括以下组分：
    (1)85～95份的载体，
    (2)5～15份的氧化钨。
  11. 按照权利要求10所述的整合式催化剂，其特征在于：所用的载体选自SiO 2和介孔分子筛；优选地，所述介孔分子筛为含硅介孔分子筛，优选选自MCM分子筛、SBA分子筛、HMS分子筛和MSU分子筛中。
  12. 按照权利要求1所述的整合式催化剂，其特征在于：所述多个不同的活性相中的第二活性相为异构化催化剂，其为碱土金属氧化物，选自氧化钙、氧化镁、氧化锶和氧化钡中，优选为氧化镁。
  13. 按照权利要求12所述的整合式催化剂，其特征在于：所述的第二活性相优选为多晶六边形片状氧化镁；优选地，六边形边长为180-600nm，片厚为8-30nm。
  14. 制备氧化镁的方法，包括：
    1)制备浓度为5-20％的可溶性镁盐溶液，升温至40℃-80℃，搅拌直至均匀；
    2)加入表面活性剂及络合剂，其中表面活性剂相对于所述镁盐的镁离子的摩尔比例为0.5％-3％，络合剂相对于所述镁盐的镁离子的摩尔比例为1-8％；
    3)加入沉淀剂，沉淀剂与镁离子的摩尔比为2:1-5:1；
    4)将步骤3)所得沉淀物水洗，然后用无水乙醇洗涤，之后在70℃-90℃干燥8-12h；
    5)将步骤4)所得物焙烧，控制升温速率为5～15℃/min，在400℃-520℃焙烧3-6h。
  15. 按照权利要求14所述的方法，其特征在于：所述可溶性镁盐选自硫酸镁、氯化镁和碳酸镁；所述表面活性剂选自分子型表面活性剂，优选选自聚乙二醇和P123；所述络合剂选自乙二胺四乙酸和氨基三乙酸；所述沉淀剂选自氨水和尿素中，浓度为5-30％。
  16. 制备权利要求1-13任一所述的整合式催化剂的方法，包括：
    1)分别提供多个不同的活性相的粉料；
    2)对步骤1)中的多个不同的活性相的粉料分别进行成型，形成结构稳定的多个活性相；
    3)将不同活性相的多个活性相通过选自以下的方式整合在一起：将各个活性相分别装填在具有多个腔室的容器中；将各个活性相层压；将各个活性相粘结；将各个活性相按顺序滚球；将各个活性相共挤出；其中，控制相邻的两个不同活性相各自的平分面之间的有效距离为0.5～5mm，优选为1～3mm。
  17. 按照权利要求16所述的制备方法，其特征在于：
    所述粉料的粒径为8～400目。
  18. 按照权利要求16所述的方法，其用于制备至少两层的多层结构，包括：
    1)分别提供第一活性相的粉料和第二活性相的粉料；
    2)将步骤1)中的一种粉料成型，制成催化剂层A；
    3)在催化剂层A的一个底面上结合由步骤1)中的另一种粉料成型的催化剂层B；
    4)任选地，利用步骤3)的方法，在步骤3)所得两层催化剂颗粒成型体基础上，结合其他催化剂层；
    5)将催化剂颗粒成型体进行干燥和焙烧，得到催化剂颗粒。
  19. 按照权利要求18所述的方法，其特征在于：
    所述成型方法采用压片或滚球成型工艺。
  20. 按照权利要求18或19所述的方法，其特征在于：第一活性相为歧化催化剂，其中第一活性相粉料成型时，采用第一粘合剂，所述第一粘合剂选自硅溶胶和铝溶胶中的至少一种；和/或，第二活性相为异构化催化剂，其中第二活性相粉料成型时，采用第二粘合剂，所述第二粘合剂选自聚乙烯醇、羟甲基纤维素、羟丙基甲基纤维素、羟丙基纤维素和聚乙烯吡咯烷酮中的至少一种。
  21. 按照权利要求20所述的方法，其特征在于：所述第一活性相粉料和第一粘合剂的质量比为3:1～1:2；和/或，所述第二活性相粉料和第二粘合剂的质量比为3:1～1:2。
  22. 按照权利要求18所述的方法，其特征在于：步骤5)所述的干燥条件如下：干燥温度为80～110℃，干燥时间为8～15小时；优选的焙烧过程如下：全程控制升温速率为0.5～1.5℃/min，首先在惰性气 氛下由常温升至280～320℃，恒温4～8h，继续升温至460～500℃，恒温4～8h，之后切换成含氧气氛，升温至530～570℃，恒温4～8h，之后再次切换成惰性气氛，恒温4～8h。
  23. 权利要求1-13任一所述的整合式催化剂的用于烯烃歧化反应的用途。
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