Catalyst granules for use in olefin disproportionation reactions and method for preparing same

Abstract

An integrated catalyst for use in an olefin disproportionation reaction is disclosed. The integrated catalyst comprises a plurality of different integrated active phases, and the relative positions of the different active phases remain substantially unchanged during the olefin disproportionation reaction. The effective distance between the bisecting planes of two adjacent different active phases is 0.5 to 5 mm, preferably 1 to 3 mm.

Description

Detailed Description of the Invention

[0001] [Technical Field] The present invention relates to catalyst particles for olefin disproportionation reactions, to a process for their preparation, and to the use of catalyst particles in the field of olefin disproportionation.

[0002] 〔background〕 Olefin disproportionation is a process in which C=C double bonds in olefins are broken and recombined under the action of transition metal compound catalysts to give new olefin products.

[0003] Olefin disproportionation is an effective technological means for controlling the structure of products. By utilizing the cross-disproportionation of butylene and ethylene, a relatively large amount of low-value butylene feedstock can be converted into high-value propylene products by adding an appropriate amount of ethylene.

[0004] Catalysts for butylene disproportionation mainly include rhenium-, molybdenum-, and tungsten-based catalysts. US Pat. Nos. 5,898,091 and 6,166,279 disclose a method for treating C4 and C5 olefins, in which the catalyst used is Re2O7 / Al2O3 and the reactor is a moving bed reactor. US Pat. No. 6,358,482 discloses an apparatus for producing isobutylene and propylene from a C4 hydrocarbon fraction. The C4 fraction can be selectively hydrogenated and fractionated to provide 1-butylene and 2-butylene, the separated 1-butylene is converted to 2-butylene by double bond isomerization, and the 2-butylene-rich material is subjected to disproportionation with ethylene to produce propylene, using a disproportionation catalyst of Re2O7 / Al2O3. US6743958 discloses an improved method based on US6358482, in which the separated isobutylene is subjected to skeletal isomerization to produce n-butylene for recycling. WO00014038 introduces a method for preparing propylene by butylene disproportionation, in which the raw butylene is 1-butylene, 2-butylene or a mixture thereof, and the catalyst is WO3 / SiO2 or Cs+ , PO4 3- It is WO3 / SiO2 modified with etc.

[0005] Currently, catalysts for preparing propylene by olefin disproportionation use a dual catalyst, which includes both a disproportionation catalyst and an isomerization catalyst. The isomerization catalyst is typically an alkaline earth metal oxide, and the isomerization catalyst alone has virtually no effect on olefin disproportionation. This study demonstrates that the activity and stability of lower olefin disproportionation catalysts can be effectively improved by mixing both types of catalyst for loading.

[0006] Summary of the Invention The inventors have found that in disproportionation reactions, the transfer of intermediate allyl groups between two catalytically active phases has a significant impact on the reaction, and that precise control of the distance between the two active phases must be considered in catalyst design. In prior art, disproportionation catalyst particles and isomerization catalyst particles are simply mixed and then used for butylene disproportionation reactions. In this case, both catalysts are combined randomly, resulting in the inability to precisely control the distance between the two active phases, resulting in the loss of benefits from intermediate generation and transfer, and reduced catalytic efficiency under high space velocity conditions. On the other hand, catalysts obtained by simply mixing two types of catalyst particles have low catalytic efficiency and may perform poorly due to the two active phases being too close together, resulting in mutual coverage. Therefore, the inventors have conducted research and testing to provide a new catalyst. The new catalyst integrates the disproportionation catalyst and isomerization catalyst into a unified catalyst particle by changing the particle mixing method. The integrated catalyst allows for precise control of the distance between the two active phases, which not only facilitates the transfer of intermediates but also avoids the decline in activity stability caused by mutual coverage of active sites due to the close distance between the two catalysts, thereby improving the activity and stability of the catalyst under high space velocity operating conditions. Meanwhile, the isomerization catalyst used is magnesium oxide in the form of polycrystalline hexagonal flakes, and its morphological structure fully exposes the active sites of the isomerization catalyst, improving the utilization rate of the isomerization catalyst and extending the stability of the catalyst.

[0007] Therefore, aimed at the problem of relatively poor activity and stability of catalysts obtained from mechanically mixing olefin disproportionation catalysts and isomerization catalysts when used in the disproportionation reaction of lower olefins in the prior art, the present invention provides novel catalyst particles for olefin disproportionation reaction and methods for preparing and using the same.

[0008] All publications, patent applications, patents and other references mentioned in this specification are incorporated herein by reference in their entirety.Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this invention belongs.In the event of any discrepancy, this specification, including definitions, shall prevail.

[0009] All ranges contained herein include their endpoints unless otherwise specified. Furthermore, when a range, one or more preferred ranges, or multiple preferred upper and lower limits are given for an amount, concentration, or other value or parameter, it should be understood that all ranges formed from any pair of any upper limit or preferred value with any lower limit or preferred value are specifically disclosed, regardless of whether such pair of values ​​are individually disclosed.

[0010] In the present invention, when a technical solution is given in an open-ended limitation form, such as "comprising" or "including" some enumerated elements, it will be understood by those skilled in the art that an embodiment consisting of or essentially consisting of these elements can obviously be used to implement the technical solution. Therefore, those skilled in the art will understand that the technical solution with the open limitation given in the present invention also encompasses an embodiment consisting of or substantially consisting of the enumerated elements.

[0011] Finally, all percentages, parts, ratios, etc. referred to herein are by weight unless expressly stated otherwise, but where weight is not a basis according to conventional knowledge by those skilled in the art, that basis will be determined according to conventional knowledge by those skilled in the art.

[0012] "Ranges" disclosed herein are given with lower and upper limits, e.g., one or more lower limits and one or more upper limits. A given range can be defined by selecting lower and upper limits that define the boundaries of the given range. All ranges so defined are inclusive and combinable, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60 to 110 and 80 to 120 are recited for a particular parameter, this means that the ranges of 60 to 120 and 80 to 110 are also contemplated. Furthermore, if the recited lower limits are 1 and 2 and the recited upper limits are 3, 4, and 5, then the following ranges are all contemplated: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4, and 2 to 5.

[0013] For the purposes of the present invention, the "active phase" of the catalyst is understood to mean the structural units that are bound together and remain morphologically stable during storage and reaction.

[0014] Those skilled in the art are aware that disproportionation catalysts and / or isomerization catalysts are typically used in olefin disproportionation reactions. Therefore, for purposes of the present invention, commercially available disproportionation catalysts and isomerization catalysts can be directly used as different active phases in the integrated catalyst of the present invention. Therefore, for purposes of the present invention, the terms "disproportionation catalyst" and "disproportionation active phase" can be used interchangeably, if desired, and the terms "isomerization catalyst" and "isomerization active phase" can be used interchangeably, if desired.

[0015] For purposes of the present invention, an "integrated catalyst" comprises a plurality of different active phases integrated together, wherein the relative positions between the different active phases remain substantially unchanged during the olefin disproportionation reaction, e.g., the relative positional displacement, if any, between the different active phases during the olefin disproportionation reaction is 0.5 mm or less, preferably 0.1 mm or less.

[0016] For the purposes of the present invention, the "effective distance" of two adjacent active phases is intended to mean the average distance counted between the substances contained in each of the two adjacent active phases for the purpose of quantifying the average travel distance of an object to be catalyzed between the two adjacent active phases of the catalyst. It will be easily understood that for two adjacent distinct active phases A and B, there exists an interface SO of planar or curved shape. Also, within said active phase A, there exists a bisecting surface S in the form of a plane that bisects the mass of active phase A and is parallel to the planar interface SO. A , or a bisecting surface S in the form of a curved surface equidistant from various points on the curved interface S0 A and correspondingly, within the active phase B, there is a bisection surface S B Therefore, the bisecting surface S A and S B The distance between can represent the "effective distance" of two adjacent different active phases A and B. For example, in the case of a uniform cube, its bisecting plane is a cross section of half its thickness, therefore, if active phases A and B are stacked in the thickness direction in the form of a cube, the "effective distance" between active phases A and B is equal to half the sum of the thicknesses of active phases A and B. As another example, in the case of a uniform sphere with radius R1, the bisecting plane is the spherical surface that bisects the volume of the original sphere, i.e., the surface of radius R1.

[0017]

number

[0018] It is a spherical surface with a radius of about 0.79R1.

[0019] Therefore, for the purposes of the present invention, the "thickness" of a catalyst particle generally refers to the direction perpendicular to the interface S0, and the planar direction of the interface S0 is called the "radial" direction, taking into account the shape of the reactor in which the catalyst is loaded, etc. If the interface S0 is not circular or cannot be described as circular, the larger scale direction is called the "length."

[0020] Thus, for purposes of the present invention, the effective distance occupied by an active phase (e.g., active phase A) is the effective distance between the bisection plane of the active phase (e.g., bisection plane S A ) and the interface S0 of the active phase with another active phase.

[0021] In one aspect, the present invention provides an integrated catalyst for olefin disproportionation, wherein the integrated catalyst comprises a plurality of different active phases integrated together, wherein the relative positions between the different active phases are kept substantially unchanged during the olefin disproportionation, and the effective distance between the respective bisecting planes of two adjacent different active phases is 0.5 to 5 mm, preferably 1 to 3 mm.

[0022] In one embodiment, the different active phases are combined by a means selected from the group consisting of: filling each active phase into a multi-chamber container; stacking the active phases; bonding the active phases; rolling the active phases in sequence; and co-extruding the active phases.

[0023] In one embodiment of the present invention, the ratio of the effective distance occupied by two different active phases to the distance between the centers of gravity of two adjacent different active phases is 1:10 to 10:1.

[0024] In one embodiment of the present invention, optionally, a plurality of different active phases are arranged alternately one or more times in a periodic regular arrangement.For the purpose of the present invention, a periodic regular arrangement means that the arrangement of different active phases shows a periodic regularity.For example, for two different active phases A and B, they are arranged in the form of AB, BA, ABA, BAB, ABAB or BABA, while for three different active phases A, B and C, they are arranged in the form of ABC, ABCABC, etc.

[0025] In one embodiment of the present invention, any two adjacent active phases are a disproportionation catalyst and an isomerization catalyst, respectively, and the ratio of the effective distances occupied by the adjacent disproportionation catalyst active phase and the adjacent isomerization catalyst active phase is (1:1) to (1:5), preferably (1:2) to (1:3).

[0026] In one embodiment of the present invention, the relative positional displacement, if any, between the different active phases during the olefin disproportionation reaction is not more than 0.5 mm, preferably not more than 0.1 mm.

[0027] In one embodiment of the present invention, the catalyst is in the form of particles.

[0028] In one embodiment of the present invention, the catalyst particles have a total thickness of 2.0 mm to 8.0 mm, preferably 2.5 mm to 6.0 mm; a radial length of 1.8 mm to 6.0 mm, and preferably a cylindrical shape.

[0029] Therefore, in one exemplary embodiment, the present invention provides a catalyst particle for an olefin disproportionation reaction, the catalyst particle having a multilayer structure of at least two layers, where any two adjacent layers are a disproportionation catalyst layer and an isomerization catalyst layer, respectively, and the thickness ratio between the adjacent disproportionation catalyst layer and the isomerization catalyst layer is (1:1) to (1:5), preferably (1:2) to (1:3).

[0030] In one embodiment of the present invention, 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.

[0031] In one embodiment of the present invention, the catalyst particles may be cylindrical, preferably straight, in shape. The cylinder may have a diameter of 1.8 mm to 6.0 mm and a height of 2.5 mm to 6.0 mm. In a multi-layer structure, each layer is a coaxial cylinder with an equal base area.

[0032] In one embodiment of the present invention, the catalyst particles have a two-layer structure or a three-layer structure. A two-layer structure is composed of a disproportionation catalyst layer and an isomerization catalyst layer. A three-layer structure is composed of a first disproportionation catalyst layer, an isomerization catalyst layer, and a second disproportionation catalyst layer in that order, or a first isomerization catalyst layer, a disproportionation catalyst layer, and a second isomerization catalyst layer in that order.

[0033] In one embodiment of the present invention, the disproportionation catalyst is a tungsten-based catalyst, preferably comprising the following components in parts by weight: (1) 85 to 95 parts of a carrier; and (2) 5 to 15 parts tungsten oxide.

[0034] In one embodiment of the present invention, the support is preferably at least one selected from the group consisting of SiO2 and mesoporous molecular sieves. The mesoporous molecular sieves are silicon-containing mesoporous molecular sieves, and are at least one selected from the group consisting of MCM molecular sieves, SBA molecular sieves, HMS molecular sieves, and MSU molecular sieves; more preferably selected from the group consisting of MCM molecular sieves, SBA molecular sieves, HMS molecular sieves, and MSU molecular sieves.

[0035] In one embodiment of the present invention, the disproportionation catalyst can be prepared by a method commonly used in the art, such as impregnation. Generally, the disproportionation catalyst is obtained by impregnating a support with a supported tungsten source, followed by drying and calcination. The drying and calcination are carried out under conventional operating conditions, such as drying at 80-120°C for 1-10 hours and calcination at 400-600°C for 2-7 hours.

[0036] In one embodiment of the present invention, 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.

[0037] In one embodiment of the present invention, the magnesium oxide as the isomerization catalyst is magnesia in the form of polycrystalline hexagonal flakes; preferably, the hexagons have a side length of 180-600 nm and a thickness of 8-30 nm.

[0038] In one embodiment of the present invention, the magnesium oxide is 1) Prepare a solution of soluble magnesium salt with a concentration of 5-20%, heat it to 40-80°C, and stir it; 2) adding a surfactant and a complexing agent, wherein the molar ratio of the surfactant to the magnesium ions is 0.5-3%, and the molar ratio of the complexing agent to the magnesium ions is 1-8%; 3) adding a precipitating agent, wherein the molar ratio of the precipitating agent to magnesium ions is 2:1 to 5:1; 4) washing the precipitate obtained in step 3 with water, then with absolute ethanol, and drying at 70 to 90°C for 8 to 12 hours; and 5) calcining the product obtained in step (4) by controlling the heating rate to 5-15°C / min and calcining at 400-520°C for 3-6 hours; It is prepared by a method comprising:

[0039] The soluble magnesium salt in step 1) is at least one selected from magnesium sulfate, magnesium chloride, and magnesium carbonate; the surfactant in step 2) is at least one molecular surfactant, preferably at least one of polyethylene glycol and P123; the complexing agent is at least one selected from ethylenediaminetetraacetic acid and nitrilotriacetic acid; and the precipitating agent in step 3) is at least one of aqueous ammonia and urea at a concentration of 5 to 30%.

[0040] In one embodiment of the present invention, the weight ratio of the disproportionation catalyst to the isomerization catalyst in the catalyst particles is preferably (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 obtained from all of the disproportionation catalyst layers, and the isomerization catalyst refers to the isomerization catalyst obtained from all of the isomerization catalyst layers.

[0041] In another aspect, the present invention provides a method for preparing an integrated catalyst according to the present invention, the method comprising: 1) Providing a plurality of different active phase powders; 2) molding each of the powders of the different active phases from step 1) to form a plurality of active phases having a stable structure; and 3) Consolidating the multiple active phases together by means selected from the group consisting of: respectively filling each active phase into a container having multiple chambers; stacking each active phase; bonding the respective active phases; rolling the active phases in turn; or co-extruding the active phases, wherein the effective distance between the bisecting planes of each of the two adjacent different active phases is controlled to be 0.5-5 mm, preferably 1-3 mm.

[0042] In one embodiment of the present invention, the particle size of the powder is 8-400 mesh.

[0043] Thus, in one exemplary embodiment, the present invention provides a method for preparing the above-described catalyst particles, the method comprising: 1) preparing a disproportionation catalyst powder and an isomerization catalyst powder respectively; 2) forming one of the powders obtained in step 1) to prepare a catalyst layer A; 3) combining a catalyst layer B formed by another type of powder in step 1) with one bottom surface of the catalyst layer A; 4) Optionally, combining another catalyst layer based on the two-layer catalyst particle compact obtained in step 3 using the method of step 3; and 5) The finally obtained catalyst particle compact is dried and calcined to obtain catalyst particles.

[0044] In step 1), the particle size of the disproportionation catalyst powder is 8-50 mesh, and the particle size of the isomerization catalyst powder is 8-50 mesh.

[0045] When one of the powders obtained from step 1) used in step 2) is a disproportionation catalyst powder, another type of powder in step 3) is an isomerization catalyst powder.When one of the powders obtained from step 1) used in step 2) can be an isomerization catalyst powder, another type of powder in step 3) is a disproportionation catalyst powder.

[0046] The molding method for the catalyst layer A in step 2) may be a tablet molding method.

[0047] The molding method of catalyst layer B in step 3) may be a tablet molding method, i.e., another type of powder from step 1) is tableted onto one bottom surface of catalyst layer A to form catalyst layer B combined with catalyst layer A. If step 4) is not performed, the catalyst particle compact obtained in step 3) is the finally obtained catalyst particle compact.

[0048] The molding method for the other catalyst layers in step 4) may be a tablet molding method, i.e., subject to the requirement that any two adjacent layers are a disproportionation catalyst layer and an isomerization catalyst layer, respectively, the other catalyst layers can be combined and molded together by utilizing the same tablet molding method as in step 3), thereby obtaining the final catalyst particle compact.

[0049] According to the present invention, "optionally" means that the corresponding step is or is not performed.

[0050] The tableting method according to the present invention is well known to those skilled in the art. The shape of the catalyst particles may be any shape conventionally used in the art, preferably a cylindrical shape, more preferably a straight cylindrical shape. The catalyst particles are composed of multiple catalyst layers in the axial direction.

[0051] In one embodiment of the present invention, a first binder may be used during molding of the disproportionation catalyst powder. The first binder is at least one selected from silica sol and aluminum sol. A second binder may be used during molding of the isomerization catalyst powder. The second binder is at least one selected from polyvinyl alcohol, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl cellulose, and polyvinylpyrrolidone.

[0052] In one embodiment of the present invention, the weight ratio of the disproportionation catalyst powder to the first binder is 3:1 to 1:2, and the weight ratio of the isomerization catalyst powder to the second adhesive is 3:1 to 1:2.

[0053] In one embodiment of the present invention, after catalyst particle compacts satisfying the size requirements are obtained, the catalyst particle compacts are subjected to drying and calcination. Step 5) is preferably performed under conditions of drying at a temperature of 80 to 110°C for 8 to 15 hours. A preferred calcination method is as follows: the heating rate is controlled to 0.5 to 1.5°C / min throughout the entire process, the temperature is raised from room temperature to 280 to 320°C in an inert atmosphere, the temperature is maintained for 4 to 8 hours, the temperature is raised again to 460 to 500°C and maintained for 4 to 8 hours, the atmosphere is then changed to an oxygen-containing atmosphere, the temperature is raised to 530 to 570°C and maintained for 4 to 8 hours, the atmosphere is then changed back to an inert atmosphere, and the temperature is maintained for 4 to 8 hours. The inert atmosphere may be at least one selected from nitrogen and an inert gas. The oxygen-containing atmosphere may be air.

[0054] In a third aspect, the present invention provides a method for the disproportionation of olefins using a fixed bed process, in which the catalyst particles described above or obtained according to the molding method described above are used.

[0055] In one embodiment of the present invention, a process for the disproportionation of olefins comprises contacting a feedstock comprising ethylene and butylene or pentylene with catalyst particles described above or catalyst particles prepared according to the shaping process described above to obtain a product comprising propylene.

[0056] In one embodiment of the present invention, the reaction conditions are preferably as follows: a reaction temperature of 200 to 450°C, a reaction pressure of 0 to 5 MPa, and a weight hourly space velocity of the raw material of 1 to 30 h -1 Preferably, the reaction temperature is 250 to 400°C, the reaction pressure is 1 to 4 MPa, and the weight hourly space velocity of the raw material is 5 to 25 h- 1 More preferably, the reaction temperature is 300 to 350°C, the reaction pressure is 2 to 3 MPa, and the weight hourly space velocity of the raw material is 10 to 20 h -1 is.

[0057] Compared with the prior art, the present invention has the following advantages: 1. The present inventors have studied and discovered that by modifying the conventional manner of mechanically mixing the disproportionation catalyst and the isomerization catalyst in the prior art, the disproportionation catalyst and the isomerization catalyst are layered and integrated into catalyst particles, which is not only beneficial to the transfer of intermediates, but also avoids mutual coverage of active sites due to the close distance of the two catalysts, thereby improving the activity and stability of the catalyst.

[0058] 2. The inventors further researched and discovered that by comprehensively controlling the thickness ratio between adjacent disproportionation catalyst layers and isomerization catalyst layers, the weight ratio between the disproportionation catalyst and the isomerization catalyst, etc., and accurately controlling the distance between the two types of active centers to the millimeter level, the catalyst can have better activity and stability.

[0059] 3. Because the physical properties of the powders used in disproportionation catalysts and isomerization catalysts are significantly different, the contact interface between the disproportionation catalyst and isomerization catalyst is prone to faulting during the preparation process. The present invention overcomes the faulting problem between the catalyst layers by controlling the material molding method and calcination, thereby further improving the activity and stability of the catalyst.

[0060] 〔drawing〕 Figure 1 shows a schematic diagram of the structure of a two-layer catalyst particle (disproportionation catalyst layer and isomerization catalyst layer); FIG. 2 shows a schematic diagram of the structure of a three-layer catalyst particle (from top to bottom: a first isomerization catalyst layer, a disproportionation catalyst layer, and a second isomerization catalyst layer); FIG. 3 shows a schematic structural diagram of a three-layer catalyst particle (from top to bottom: a first disproportionation catalyst layer, an isomerization catalyst layer, and a second disproportionation catalyst layer).

[0061] Here, the reference numerals are as follows: 1 indicates the first disproportionation catalyst layer, 2 indicates the first isomerization catalyst layer, 3 indicates the second disproportionation catalyst layer, and 4 indicates the second isomerization catalyst layer.

[0062] Figure 4 shows SEM, TEM, and electron diffraction images of magnesium oxide; FIG. 5 shows an SEM photograph of the magnesium oxide used in Comparative Example 3.

[0063] Detailed Description The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.

[0064] In the examples and comparative examples of the present invention, the disproportionation catalyst powder used had a particle size of 10-20 mesh, and the isomerization catalyst powder used had a particle size of 10-20 mesh.

[0065] The magnesium oxide used in the present examples was polycrystalline hexagonal flaky mesoporous magnesium oxide prepared by: 1) Prepare a soluble magnesium salt solution with a concentration of 10%, heat it to 60°C and stir it; 2) adding polyethylene glycol and ethylenediaminetetraacetic acid, where the molar ratio of surfactant to magnesium ions was 1% and the molar ratio of complexing agent to magnesium ions was 2%; 3) adding ammonia water as a precipitant, where the molar ratio of the precipitant to magnesium ions was 3:1; 4) Washing the precipitate obtained in step 3 with water, then with absolute ethanol, and drying at 80°C for 8 hours; 5) Calcining the product obtained in step (4), controlling the heating rate at 10°C / min, and calcining at 500°C for 4 hours.

[0066] Example 1 A disproportionation catalyst powder having a composition of WO3 / SiO2 (WO3 was used in an amount of 15 wt%) was mixed with alumina sol in a weight ratio of 3:1, granulated, and compressed into a cylindrical catalyst layer A measuring 1.8 mm in diameter x 3.0 mm in height. Calcium oxide powder and polyvinyl alcohol were mixed in a weight ratio of 3:1, from which a cylindrical catalyst layer B was compressed and attached to one bottom surface of catalyst layer A to prepare a cylindrical catalyst particle compact measuring 1.8 mm x 6.0 mm. The effective distance of the active phase was 3 mm. The thickness ratio of disproportionation catalyst layer A to isomerization catalyst layer B was 1:1, and the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:6.

[0067] The catalyst particle compact was dried at a drying temperature of 90°C for 10 hours and then calcined. The calcination method was as follows: the heating rate was controlled at 0.5°C / min throughout the entire process, the temperature was raised from room temperature to 280°C in a nitrogen atmosphere, the temperature was maintained for 4 hours, the temperature was again raised to 460°C and maintained for 4 hours, the atmosphere was then changed to air, the temperature was raised to 530°C and maintained for 4 hours, the atmosphere was then changed back to nitrogen, and the temperature was maintained for 4 hours to obtain catalyst particles.

[0068] The prepared catalyst particles were loaded into a Φ25 mm fixed-bed reactor and the weight space velocity was 10 h- 1The reaction was carried out under the conditions of a reaction temperature of 300°C and a reaction pressure of 3 MPa, using ethylene and butylene as the raw materials for disproportionation. The results are shown in Table 1.

[0069] Example 2 A disproportionation catalyst powder having a composition of WO3 / SiO2 (WO3 was used in an amount of 5 wt%) was mixed with alumina sol in a weight ratio of 2:1, granulated, and compressed into a 6.0 mm x 1.0 mm cylindrical catalyst layer A. Barium oxide powder and hydroxymethylcellulose were mixed in a weight ratio of 2:1, from which a cylindrical catalyst layer B was compressed and attached to one bottom surface of catalyst layer A to prepare a 6.0 mm x 6.0 mm cylindrical catalyst particle compact. Here, the effective distance of the active phase was 3 mm. The thickness ratio of disproportionation catalyst layer A to isomerization catalyst layer B was 1:5, and the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:6.

[0070] The catalyst particle compact was dried at a drying temperature of 90°C for 10 hours and then calcined. The calcination method was as follows: the heating rate was controlled at 1.5°C / min throughout the entire process, the temperature was raised from room temperature to 320°C in a nitrogen atmosphere, the temperature was maintained for 8 hours, the temperature was again raised to 500°C and maintained for 8 hours, the atmosphere was then changed to air, the temperature was raised to 570°C and maintained for 8 hours, the atmosphere was then changed back to nitrogen, and the temperature was maintained for 8 hours to obtain catalyst particles.

[0071] The prepared catalyst particles were loaded into a Φ25 mm fixed-bed reactor and the weight space velocity was 10 h- 1 The reaction was carried out under the conditions of a reaction temperature of 300°C and a reaction pressure of 3 MPa, using ethylene and butylene as the raw materials for disproportionation. The results are shown in Table 1.

[0072] Example 3 A disproportionation catalyst powder having a composition of WO3 / MCM-41 (WO3 was used in an amount of 10 wt%) was mixed with silica sol in a 1:1 weight ratio, granulated, and compressed into a 3.0 mm x 2.0 mm cylindrical catalyst layer A. Strontium oxide powder and polyvinylpyrrolidone were mixed in a 1:1 weight ratio, from which a cylindrical catalyst layer B was compressed and attached to one bottom surface of catalyst layer A to prepare a 3.0 mm x 6.0 mm cylindrical catalyst particle compact. In this case, the effective distance of the active phase was 3 mm. The thickness ratio of disproportionation catalyst layer A to isomerization catalyst layer B was 1:2, and the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:6.

[0073] The catalyst particle compact was dried at a drying temperature of 90°C for 10 hours and then calcined. The calcination method was as follows: the heating rate was controlled at 1°C / min throughout the entire process, the temperature was raised from room temperature to 300°C in a nitrogen atmosphere, the temperature was maintained for 6 hours, the temperature was again raised to 480°C and maintained for 6 hours, the atmosphere was then changed to air, the temperature was raised to 550°C and maintained for 4 hours, the atmosphere was then changed back to nitrogen, and the temperature was maintained for 4 hours to obtain catalyst particles.

[0074] The prepared catalyst particles were loaded into a Φ25 mm fixed-bed reactor and the weight space velocity was 10 h- 1 The reaction was carried out under the conditions of a reaction temperature of 300°C and a reaction pressure of 3 MPa, using ethylene and butylene as the raw materials for disproportionation. The results are shown in Table 1.

[0075] Example 4 A disproportionation catalyst powder having a composition of WO3 / SBA-15 (WO3 was used in an amount of 10 wt%) was mixed with silica sol in a weight ratio of 1:2, granulated, and compressed into a 4.0 mm x 1.0 mm cylindrical catalyst layer A. Magnesium oxide powder and hydroxypropyl cellulose were mixed in a weight ratio of 1:2, from which a cylindrical catalyst layer B was compressed and attached to one bottom surface of catalyst layer A to prepare a 4.0 mm x 2.5 mm cylindrical catalyst particle compact. In this case, the effective distance of the active phase was 1.25 mm. The thickness ratio of disproportionation catalyst layer A to isomerization catalyst layer B was 1:1.5, and the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:6.

[0076] The catalyst particle compact was dried at a drying temperature of 90°C for 10 hours and then calcined. The calcination method was as follows: the heating rate was controlled at 1°C / min throughout the entire process, the temperature was raised from room temperature to 300°C in a nitrogen atmosphere, the temperature was maintained for 6 hours, the temperature was again raised to 480°C and maintained for 6 hours, the atmosphere was then changed to air, the temperature was raised to 550°C and maintained for 4 hours, the atmosphere was then changed back to nitrogen, and the temperature was maintained for 4 hours to obtain catalyst particles.

[0077] The prepared catalyst particles were loaded into a Φ25 mm fixed-bed reactor and the weight space velocity was 10 h- 1 The reaction was carried out under the conditions of a reaction temperature of 300°C and a reaction pressure of 3 MPa, using ethylene and butylene as the raw materials for disproportionation. The results are shown in Table 1.

[0078] Example 5 A disproportionation catalyst powder having a composition of WO3 / MSU (WO3 was used in an amount of 10 wt%) was mixed with silica sol in a weight ratio of 1:2, granulated, and compressed into a 4.0 mm x 2.0 mm cylindrical catalyst layer A. Magnesium oxide powder and hydroxypropyl methylcellulose were mixed in a weight ratio of 1:2, from which a cylindrical catalyst layer B was compressed and attached to one bottom surface of catalyst layer A to prepare a 4.0 mm x 6.0 mm cylindrical catalyst particle compact. In this case, the effective distance of the active phase was 3 mm. The thickness ratio of disproportionation catalyst layer A to isomerization catalyst layer B was 1:2, and the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:6.

[0079] The catalyst particle compact was dried at a drying temperature of 90°C for 10 hours and then calcined. The calcination method was as follows: the heating rate was controlled at 1°C / min throughout the entire process, and the temperature was raised from room temperature to 300°C in a nitrogen atmosphere, maintained at that temperature for 6 hours, raised again to 480°C and maintained at that temperature for 6 hours, then the atmosphere was changed to air, the temperature was raised to 550°C and maintained at that temperature for 4 hours, and then the atmosphere was changed back to nitrogen and maintained at that temperature for 4 hours to obtain catalyst particles. As shown in Figure 1, the catalyst particle compact was composed of a first disproportionation catalyst layer 1 (disproportionation catalyst layer A) and a first isomerization catalyst layer 2 (isomerization catalyst layer B).

[0080] The prepared catalyst particles were loaded into a Φ25 mm fixed-bed reactor and the weight space velocity was 10 h- 1 The reaction was carried out under the conditions of a reaction temperature of 300°C and a reaction pressure of 3 MPa, using ethylene and butylene as the raw materials for disproportionation. The results are shown in Table 1.

[0081] Example 6 A disproportionation catalyst powder having a WO / SiO composition (WO was used in an amount of 10 wt%) was mixed with silica sol in a weight ratio of 1:2, granulated, and compressed into a 3.0 mm x 1.5 mm cylindrical catalyst layer A. Magnesium oxide powder and hydroxypropyl methylcellulose were mixed in a weight ratio of 1:2, granulated, and compressed into a cylindrical catalyst layer B. The resulting mixture was attached to one bottom surface of catalyst layer A to prepare a 3.0 mm x 4.5 mm cylindrical catalyst particle intermediate. Subsequently, a disproportionation catalyst layer C was further attached by the same method to obtain a 3.0 mm x 6.0 mm cylindrical catalyst particle compact. Here, the effective distance of the active phase was 2.25 mm. The thickness ratio of disproportionation catalyst layer A:isomerization catalyst layer B:disproportionation catalyst layer C was 1:2:1, and the weight ratio was 1:2:1.

[0082] The catalyst particle compact was dried at a drying temperature of 90°C for 10 hours and then calcined. The calcination method was as follows: the heating rate was controlled at 1°C / min throughout the entire process, and the temperature was raised from room temperature to 300°C in a nitrogen atmosphere, maintained at that temperature for 6 hours, raised again to 480°C and maintained at that temperature for 6 hours, then the atmosphere was changed to air, the temperature was raised to 550°C and maintained at that temperature for 4 hours, and then the atmosphere was changed back to nitrogen and maintained at that temperature for 4 hours to obtain catalyst particles. As shown in Figure 3, the catalyst particle compact was composed of a first disproportionation 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).

[0083] The prepared catalyst particles were loaded into a Φ25 mm fixed-bed reactor and the weight space velocity was 10 h- 1 The reaction was carried out under the conditions of a reaction temperature of 300°C and a reaction pressure of 3 MPa, using ethylene and butylene as the raw materials for disproportionation. The results are shown in Table 1.

[0084] Example 7 Magnesium oxide powder and hydroxypropyl methylcellulose were mixed in a 1:2 weight ratio, granulated, and compressed into tablets to prepare a 3.0 mm x 2.4 mm cylindrical catalyst layer. A disproportionation catalyst powder (WO3 / SiO2) (WO3 was used in an amount of 10 wt%) was mixed with silica sol in a 1:2 weight ratio, from which cylindrical catalyst layer B was compressed and attached to one bottom surface of catalyst layer A to prepare a 3.0 mm x 3.6 mm cylindrical catalyst particle intermediate. Subsequently, disproportionation catalyst layer C was further attached by the same method to obtain a 3.0 mm x 6.0 mm cylindrical catalyst particle compact. The effective distance of the active phase was 1.8 mm. The thickness ratio of disproportionation catalyst layer A:isomerization catalyst layer B:disproportionation catalyst layer C was 2:1:2, and the weight ratio was 5:1:5.

[0085] The catalyst particle compact was dried at a drying temperature of 90°C for 10 hours and then calcined. The calcination method was as follows: the heating rate was controlled at 1°C / min throughout the entire process, and the temperature was raised from room temperature to 300°C in a nitrogen atmosphere, maintained at that temperature for 6 hours, then raised again to 480°C and maintained at that temperature for 6 hours. The atmosphere was then changed to air, the temperature was raised to 550°C, and maintained at that temperature for 4 hours. The atmosphere was then changed back to nitrogen, and the temperature was maintained for 4 hours to obtain catalyst particles. As shown in Figure 2, the catalyst particle compact was composed of a first isomerization catalyst layer 2 (isomerization catalyst layer A), a first disproportionation catalyst layer 1 (disproportionation catalyst layer B), and a second isomerization catalyst layer 4 (isomerization catalyst layer C).

[0086] The prepared catalyst particles were loaded into a Φ25 mm fixed-bed reactor and the weight space velocity was 10 h- 1 The reaction was carried out under the conditions of a reaction temperature of 300°C and a reaction pressure of 3 MPa, using ethylene and butylene as the raw materials for disproportionation. The results are shown in Table 1.

[0087] Example 8 A disproportionation catalyst powder having a composition of WO3 / SiO2 (WO3 was used in an amount of 10 wt%) was mixed with silica sol in a weight ratio of 1:2, granulated, and compressed into a 4.0 mm x 2.0 mm cylindrical catalyst layer A. Magnesium oxide powder and hydroxypropyl methylcellulose were mixed in a weight ratio of 1:2, from which a cylindrical catalyst layer B was compressed and attached to one bottom surface of catalyst layer A to prepare a 4.0 mm x 6.0 mm cylindrical catalyst particle compact. Here, the effective distance of the active phase was 3 mm. The thickness ratio of disproportionation catalyst layer A to isomerization catalyst layer B was 1:2, and the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:2.

[0088] The catalyst particle compact was dried at a drying temperature of 90°C for 10 hours and then calcined. The calcination method was as follows: the heating rate was controlled at 1°C / min throughout the entire process, the temperature was raised from room temperature to 300°C in a nitrogen atmosphere, the temperature was maintained for 6 hours, the temperature was again raised to 480°C and maintained for 6 hours, the atmosphere was then changed to air, the temperature was raised to 550°C and maintained for 4 hours, the atmosphere was then changed back to nitrogen, and the temperature was maintained for 4 hours to obtain catalyst particles.

[0089] The prepared catalyst particles were loaded into a Φ25 mm fixed-bed reactor and the weight space velocity was 10 h- 1 The reaction was carried out under the conditions of a reaction temperature of 300°C and a reaction pressure of 3 MPa, using ethylene and butylene as the raw materials for disproportionation. The results are shown in Table 1.

[0090] Example 9 A disproportionation catalyst powder having a composition of WO3 / SiO2 (WO3 was used in an amount of 10 wt%) was mixed with silica sol in a weight ratio of 1:2, granulated, and compressed into a 4.0 mm x 2.5 mm cylindrical catalyst layer A. Magnesium oxide powder and hydroxypropyl methylcellulose were mixed in a weight ratio of 1:2, from which a cylindrical catalyst layer B was compressed and attached to one bottom surface of catalyst layer A to prepare a 4.0 mm x 5.0 mm cylindrical catalyst particle compact. In this case, the effective distance of the active phase was 2.5 mm. The thickness ratio of disproportionation catalyst layer A to isomerization catalyst layer B was 1:1, and the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:2.

[0091] The catalyst particle compact was dried at a drying temperature of 90°C for 10 hours and then calcined. The calcination method was as follows: the heating rate was controlled at 1°C / min throughout the entire process, the temperature was raised from room temperature to 300°C in a nitrogen atmosphere, the temperature was maintained for 6 hours, the temperature was again raised to 480°C and maintained for 6 hours, the atmosphere was then changed to air, the temperature was raised to 550°C and maintained for 4 hours, the atmosphere was then changed back to nitrogen, and the temperature was maintained for 4 hours to obtain catalyst particles.

[0092] The prepared catalyst particles were loaded into a Φ25 mm fixed-bed reactor and the weight space velocity was 10 h-1 The reaction was carried out under the conditions of a reaction temperature of 300°C and a reaction pressure of 3 MPa, using ethylene and butylene as the raw materials for disproportionation. The results are shown in Table 1.

[0093] Example 10 A disproportionation catalyst powder having a composition of WO3 / SiO2 (WO3 was used in an amount of 10 wt%) was mixed with silica sol in a weight ratio of 1:2, granulated, and compressed into a 4.0 mm x 2.0 mm cylindrical catalyst layer A. Magnesium oxide powder and hydroxypropyl methylcellulose were mixed in a weight ratio of 1:2, from which a cylindrical catalyst layer B was compressed and attached to one bottom surface of catalyst layer A to prepare a 4.0 mm x 6.0 mm cylindrical catalyst particle compact. Here, the effective distance of the active phase was 3 mm. The thickness ratio of disproportionation catalyst layer A to isomerization catalyst layer B was 1:2, and the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:2.

[0094] The catalyst particle compacts were dried at 90°C for 10 hours, and then calcined in a muffle furnace from room temperature to 550°C, maintaining the temperature for 4 hours, using a conventional method. The particles were found to be fractured in the fault zone, making them unusable for reaction evaluation.

[0095] Example 11 A disproportionation catalyst powder having a composition of WO3 / SiO2 (WO3 was used in an amount of 10 wt%) was mixed with silica sol in a weight ratio of 1:2, granulated, and compressed into a 4.0 mm x 2.0 mm cylindrical catalyst layer A. Magnesium oxide powder and hydroxypropyl methylcellulose were mixed in a weight ratio of 1:2, from which a cylindrical catalyst layer B was compressed and attached to one bottom surface of catalyst layer A to prepare a 4.0 mm x 6.0 mm cylindrical catalyst particle compact. Here, the effective distance of the active phase was 3 mm. The thickness ratio of disproportionation catalyst layer A to isomerization catalyst layer B was 1:2, and the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:2.

[0096] The catalyst particle compact was dried at a drying temperature of 90°C for 10 hours and then calcined. The calcination method was as follows: the heating rate was controlled at 1°C / min throughout the entire process, the temperature was raised from room temperature to 300°C in a nitrogen atmosphere, the temperature was maintained for 6 hours, the temperature was again raised to 480°C and maintained for 6 hours, the atmosphere was then changed to air, the temperature was raised to 550°C and maintained for 4 hours, the atmosphere was then changed back to nitrogen, and the temperature was maintained for 4 hours to obtain catalyst particles.

[0097] The prepared catalyst particles were loaded into a Φ25 mm fixed-bed reactor and the weight space velocity was 1 h- 1 The reaction was carried out under the conditions of a reaction temperature of 200°C and a reaction pressure of 5 MPa, using ethylene and butylene as the raw materials for disproportionation. The results are shown in Table 1.

[0098] Example 12 A disproportionation catalyst powder having a composition of WO3 / SiO2 (WO3 was used in an amount of 10 wt%) was mixed with silica sol in a weight ratio of 1:2, granulated, and compressed into a 4.0 mm x 2.0 mm cylindrical catalyst layer A. Magnesium oxide powder and hydroxypropyl methylcellulose were mixed in a weight ratio of 1:2, from which a cylindrical catalyst layer B was compressed and attached to one bottom surface of catalyst layer A to prepare a 4.0 mm x 6.0 mm cylindrical catalyst particle compact. Here, the effective distance of the active phase was 3 mm. The thickness ratio of disproportionation catalyst layer A to isomerization catalyst layer B was 1:2, and the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:2.

[0099] The catalyst particle compact was dried at a drying temperature of 90°C for 10 hours and then calcined. The calcination method was as follows: the heating rate was controlled at 1°C / min throughout the entire process, the temperature was raised from room temperature to 300°C in a nitrogen atmosphere, the temperature was maintained for 6 hours, the temperature was again raised to 480°C and maintained for 6 hours, the atmosphere was then changed to air, the temperature was raised to 550°C and maintained for 4 hours, the atmosphere was then changed back to nitrogen, and the temperature was maintained for 4 hours to obtain catalyst particles.

[0100] The obtained fine particles were loaded into a Φ25 mm fixed bed reactor and subjected to a weight hourly space velocity of 30 h- 1The reaction was carried out under the conditions of a reaction temperature of 450°C and a reaction pressure of 0.1 MPa, using ethylene glycol and butylene as raw materials for disproportionation. The results are shown in Table 1.

[0101] Comparative Example 1 A disproportionation catalyst powder having a composition of WO3 / SiO2 (WO3 was used in an amount of 10 wt%) was mixed with silica sol in a weight ratio of 1:2, granulated, and compressed into 4.0 mm x 5.0 mm cylindrical catalyst particle A compacts. The catalyst particle compacts were dried at a drying temperature of 90°C for 10 hours and then calcined. The calcination method was as follows: the heating rate was controlled at 1°C / min throughout the entire process, and the temperature was raised from room temperature to 300°C in a nitrogen atmosphere, maintained at this temperature for 6 hours, then raised to 480°C and maintained at this temperature for 6 hours, then the atmosphere was changed to air, the temperature was raised to 550°C and maintained at this temperature for 4 hours, and then the atmosphere was changed back to nitrogen and maintained at this temperature for 4 hours to obtain catalyst particle A.

[0102] Magnesium oxide powder and hydroxypropyl methylcellulose were mixed in a weight ratio of 1:2, granulated, and tableted to prepare a 4.0 mm x 5.0 mm catalyst particle B molded body. The catalyst particle molded body was dried at a drying temperature of 90°C for 10 hours and then calcined. The calcination method was as follows: the heating rate was controlled at 1°C / min throughout the entire process, and the temperature was raised from room temperature to 300°C in a nitrogen atmosphere, maintained at that temperature for 6 hours, raised again to 480°C and maintained at that temperature for 6 hours, then the atmosphere was changed to air, the temperature was raised to 550°C and maintained at that temperature for 4 hours, and then the atmosphere was changed back to nitrogen and maintained at that temperature for 4 hours, thereby obtaining catalyst particle B.

[0103] The above two types of catalyst particles were mechanically loaded into a Φ25mm fixed-bed reactor. The weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:6. The weight space velocity was 10 h- 1 The reaction was carried out under the conditions of a reaction temperature of 300°C and a reaction pressure of 3 MPa, using ethylene and butylene as the raw materials for disproportionation. The results are shown in Table 1.

[0104] Comparative Example 2 A disproportionation catalyst powder having a composition of WO / SiO (WO was used in an amount of 10 wt%) was mixed with silica sol in a weight ratio of 1:2 and granulated, magnesium oxide powder and hydroxypropyl methylcellulose were mixed in a weight ratio of 1:2 and granulated, and the disproportionation catalyst powder was mixed with magnesium oxide powder in a weight ratio of 1:6 and compressed into tablets to prepare a catalyst particle B molded body of 4.0 mm x 5.0 mm.

[0105] The catalyst particle compact was dried at a drying temperature of 90°C for 10 hours and then calcined. The calcination method was as follows: the heating rate was controlled at 1°C / min throughout the entire process, the temperature was raised from room temperature to 300°C in a nitrogen atmosphere, the temperature was maintained for 6 hours, the temperature was again raised to 480°C and maintained for 6 hours, the atmosphere was then changed to air, the temperature was raised to 550°C and maintained for 4 hours, the atmosphere was then changed back to nitrogen, and the temperature was maintained for 4 hours to obtain catalyst particles. The above catalyst fine particles were loaded into a Φ25mm fixed-bed reactor and calcined at a weight hourly space velocity of 10 h- 1 The reaction was carried out under the conditions of a reaction temperature of 300°C and a reaction pressure of 3 MPa, using ethylene and butylene as the raw materials for disproportionation. The results are shown in Table 1.

[0106] Comparative Example 3 A disproportionation catalyst powder having a composition of WO3 / SiO2 (WO3 was used in an amount of 10 wt%) was mixed with silica sol in a weight ratio of 1:2 and granulated, magnesium oxide powder and hydroxypropyl methylcellulose were mixed in a weight ratio of 1:2 and granulated, and the disproportionation catalyst powder was mixed with magnesium oxide powder in a weight ratio of 1:6 and compressed into tablets to prepare a 4.0 mm x 5.0 mm catalyst particle B molded body. The magnesium oxide used here was non-flake magnesium oxide, and its SEM characteristics are shown in Figure 5.

[0107] The catalyst particle compact was dried at a drying temperature of 90°C for 10 hours and then calcined. The calcination method was as follows: the heating rate was controlled at 1°C / min throughout the entire process, the temperature was raised from room temperature to 300°C in a nitrogen atmosphere, the temperature was maintained for 6 hours, the temperature was again raised to 480°C and maintained for 6 hours, the atmosphere was then changed to air, the temperature was raised to 550°C and maintained for 4 hours, the atmosphere was then changed back to nitrogen, and the temperature was maintained for 4 hours to obtain catalyst particles. The above catalyst fine particles were loaded into a Φ25mm fixed-bed reactor and calcined at a weight hourly space velocity of 10 h- 1 The reaction was carried out under the conditions of a reaction temperature of 300°C and a reaction pressure of 3 MPa, using ethylene and butylene as the raw materials for disproportionation. The results are shown in Table 1.

[0108] [Table 1] JPEG0007765468000003.jpg107169

[0109] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical idea of ​​the present invention, many simple modifications can be made to the technical solutions of the present invention, including various technical features that can be combined in any other suitable manner. These simple modifications and combinations should also be considered as the disclosure of the present invention, and all are included in the scope of the present invention. [Brief explanation of the drawings]

[0110] [Figure 1] FIG. 1 shows a schematic diagram of the structure of a two-layer catalyst particle (disproportionation catalyst layer and isomerization catalyst layer). [Figure 2] FIG. 2 shows a schematic diagram of the structure of a three-layer catalyst particle (from top to bottom: a first isomerization catalyst layer, a disproportionation catalyst layer, and a second isomerization catalyst layer). [Figure 3] FIG. 3 shows a schematic structural diagram of a three-layer catalyst particle (from top to bottom: a first disproportionation catalyst layer, an isomerization catalyst layer, and a second disproportionation catalyst layer). [Figure 4]FIG. 4 shows SEM, TEM, and electron diffraction images of magnesium oxide. [Figure 5] FIG. 5 shows an SEM photograph of the magnesium oxide used in Comparative Example 3.

Claims

1. 1. An integrated catalyst for olefin disproportionation, comprising: a plurality of different active phases integrated together, wherein the relative positions between the different active phases are kept unchanged during the olefin disproportionation; and the effective distance between the respective bisecting planes of two adjacent different active phases is 0.5 to 5 mm.

2. The integrated catalyst described in claim 1, characterized in that the effective distance between the respective bisecting planes of the two adjacent different active phases is 1 to 3 mm.

3. 2. The integrated catalyst of claim 1, wherein the different active phases are integrated by a means selected from the group consisting of: filling each active phase into a container having multiple chambers; stacking the respective active phases; bonding the active phases; rolling the active phases one after the other; and co-extruding the active phases.

4. 2. The integral catalyst according to claim 1, wherein the ratio of the effective distance occupied by two different active phases to the distance between the centers of gravity of two adjacent different active phases is 1:10 to 10:

1.

5. 10. The integral catalyst of claim 1, wherein the plurality of different active phases are arranged one or more times alternating in a periodic regular arrangement.

6. 2. The integrated catalyst according to claim 1, wherein any two adjacent active phases are a disproportionation catalyst and an isomerization catalyst, respectively, and the ratio of the effective distances occupied by the adjacent disproportionation catalyst active phases and the isomerization catalyst active phases, respectively, is from (1:1) to (1:5).

7. The integrated catalyst described in claim 1, characterized in that the ratio of the effective distances occupied by the adjacent disproportionation catalyst active phase and isomerization catalyst active phase, respectively, is (1:2) to (1:3).

8. The integrated catalyst of claim 1 , wherein the integrated catalyst is in the form of particles.

9. 9. The integrated catalyst according to claim 8, wherein the particles of the integrated catalyst have a total thickness of 2.0 mm to 8.0 mm; and a radial length of 1.8 mm to 6.0 mm.

10. The integrated catalyst of claim 9, wherein the particles of the integrated catalyst have a cylindrical shape.

11. The integrated catalyst according to claim 8, wherein the particles of the integrated catalyst have a multi-layer structure of at least two layers.

12. The integrated catalyst described in Claim 8, characterized in that the particles of the integrated catalyst have a two-layer structure or a three-layer structure.

13. a first active phase in the plurality of different active phases is a disproportionation catalyst; 2. The integrated catalyst of claim 1, characterized in that it comprises the following components in parts by weight: (1) 85 to 95 parts of a carrier; and (2) 5 to 15 parts tungsten oxide.

14. The support is SiO ２ and mesoporous molecular sieves.

15. The integrated catalyst described in Claim 14, characterized in that the mesoporous molecular sieve is a silicon-containing mesoporous molecular sieve.

16. The integrated catalyst described in Claim 15, characterized in that the mesoporous molecular sieve is selected from the group consisting of MCM molecular sieve, SBA molecular sieve, HMS molecular sieve and MSU molecular sieve.

17. 2. The integrated catalyst of claim 1, wherein the second active phase of the plurality of distinct active phases is an alkaline earth metal oxide selected from the group consisting of calcium oxide, magnesium oxide, strontium oxide, and barium oxide.

18. The integrated catalyst of claim 17, wherein the alkaline earth metal oxide is magnesium oxide.

19. 18. The integral catalyst of claim 17, wherein the second active phase is magnesium oxide in the form of polycrystalline hexagonal flakes.

20. The integrated catalyst described in claim 19, characterized in that the hexagons of the polycrystalline hexagonal flakes have a side length of 180 to 600 nm and a thickness of 8 to 30 nm.

21. 1) Providing a plurality of different active phase powders; 2) molding the powders of the different active phases from step 1) to form a stable structure of the active phases; and 3) integrating the multiple active phases together by means selected from the group consisting of: respectively filling each active phase into a container having multiple chambers; stacking the respective active phases; bonding the respective active phases; rolling the active phases in sequence; or co-extruding the active phases; and controlling the effective distance between the bisecting planes of each of the two adjacent different active phases to be the effective distance in the integrated catalyst of any one of claims 1 to 20. A method for preparing the integrated catalyst of any one of claims 1 to 20, comprising:

22. 22. The method of claim 21, wherein the powder has a particle size of 8 to 400 mesh.

23. 22. A method according to claim 21 for preparing a multilayer structure of at least two layers, comprising: 1) providing a first active phase powder and a second active phase powder, respectively; 2) forming one of the powders obtained from step 1) to prepare a catalyst layer A; 3) combining a catalyst layer B formed by another type of powder in step 1) with one bottom surface of the catalyst layer A; 4) Optionally, combining another catalyst layer based on the two-layer catalyst particle compact obtained in step 3) using the method of step 3); and 5) drying and calcining the finally obtained catalyst particle compact to obtain catalyst particles; A method comprising:

24. 24. The method according to claim 23, characterized in that a tableting or rolling method is used for the molding method.

25. 25. The method according to claim 23 or 24, characterized in that the first active phase is a disproportionation catalyst, a first adhesive is used during molding of the first active phase powder, the first adhesive being at least one selected from silica sol and aluminum sol; and / or the second active phase is an isomerization catalyst, a second binder is used during molding of the second active phase powder, the second binder being at least one selected from polyvinyl alcohol, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl cellulose and polyvinylpyrrolidone.

26. 26. The method of claim 25, wherein the weight ratio of the first active phase powder to the first adhesive is between 3:1 and 1:2; and / or the weight ratio of the second active phase powder to the second binder is between 3:1 and 1:

2.

27. The method of claim 23, wherein the step 5) is carried out under conditions of drying at a temperature of 80-110°C for 8-15 hours; the calcination is as follows: controlling the heating rate at 0.5-1.5°C / min in the whole process, raising the temperature from room temperature to 280-320°C in an inert atmosphere, maintaining the temperature for 4-8 hours, raising the temperature again to 460-500°C and maintaining the temperature for 4-8 hours, then changing the atmosphere to an oxygen-containing atmosphere, raising the temperature to 530-570°C and maintaining the temperature for 4-8 hours, then changing the atmosphere back to an inert atmosphere, and maintaining the temperature for 4-8 hours.

28. A method for preparing the integrated catalyst of claim 21, comprising: The integrated catalyst is the integrated catalyst of claim 19, Magnesium oxide is prepared by a method comprising the following steps 1) to 5): 1) Prepare a solution of soluble magnesium salt with a concentration of 5-20%, heat it to 40-80°C, and stir to homogenize it; 2) adding a surfactant and a complexing agent, wherein the molar ratio of the surfactant to the magnesium ions of the magnesium salt is 0.5-3%, and the molar ratio of the complexing agent to the magnesium ions of the magnesium salt is 1-8%; 3) adding a precipitating agent, wherein the molar ratio of the precipitating agent to magnesium ions is 2:1 to 5:1; 4) Washing the precipitate obtained in step 3) with water, washing with absolute ethanol, and drying at 70-90°C for 8-12 hours; and 5) Calcining the product obtained in step 4) by controlling the heating rate at 5 to 15°C / min at 400 to 520°C for 3 to 6 hours; method.

29. The method of claim 28, wherein the soluble magnesium salt is selected from magnesium sulfate, magnesium chloride, and magnesium carbonate; the surfactant is a molecular surfactant; the complexing agent is selected from ethylenediaminetetraacetic acid and nitrilotriacetic acid; and the precipitating agent is selected from aqueous ammonia and urea at a concentration of 5 to 30%.

30. The method of claim 29, wherein the surfactant is selected from polyethylene glycol and P123.

31. Use of the integrated catalyst according to any one of claims 1 to 20 for the disproportionation of olefins.

Images