CATALYST GRANULES USED IN OLEFIN DISPROPORTIONATION REACTION AND PREPARATION METHOD THEREFOR

Abstract

An integrated catalyst can be used in an olefin disproportionation reaction. The integrated catalyst contains a plurality of different integrated active phases. The relative positions among different active phases remain substantially unchanged during the olefin disproportionation reaction. The effective distance between respective bisecting planes of two adjacent different active phases is 0.5-5 mm, preferably 1-3 mm.

Claims

1. An integrated catalyst for olefin disproportionation, wherein the integrated catalyst comprises a plurality of different active phases integrated together, and the relative position between the different active phases is kept substantially unchanged during the olefin disproportionation; characterized in that the effective distance between the respective bisecting surfaces of two adjacent different active phases is 0.5-5 mm, and preferably 1-3 mm.

2. The integrated catalyst according to claim 1, wherein the different active phases are integrated by means selected from the group consisting of: filling each active phase into a container with a plurality of chambers respectively; laminating the respective active phases; bonding the active phases; rolling the active phases in sequence; and coextruding the active phases.

3. The integrated catalyst according to claim 1, wherein the ratio of the effective distances occupied by two different active phases among the distances between the centers of gravity of two adjacent different active phases is 1:10 to 10:1.

4. The integrated catalyst according to claim 1, wherein the plurality of different active phases are alternated one or more times in a periodic regular arrangement.

5. 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 between the effective distances occupied respectively by the adjacent disproportionation catalyst active phase and isomerization catalyst active phase is (1:1) to (1:5), preferably (1:2) to (1:3).

6. The integrated catalyst according to claim 1, wherein the relative position 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.

7. The integrated catalyst according to claim 1, wherein the catalyst is in the form of particles.

8. The integrated catalyst according to claim 7, characterized in that the catalyst particles have a total thickness of from 2.0 mm to 8.0 mm, preferably from 2.5 mm to 6.0 mm; a radial length of 1.8 mm to 6.0 mm, and preferably in a cylindrical shape.

9. The integrated catalyst according to claim 7, characterized in that the catalyst particles are in a multi-layer structure with at least two layers, preferably in a two-layer structure or a three-layer structure.

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

11. The integrated catalyst according to claim 10, characterized in that the support is selected from SiO.sub.2 and mesoporous molecular sieve; preferably, the mesoporous molecular sieve is a silicon-containing mesoporous molecular sieve, preferably selected from the group consisting of an MCM molecular sieve, an SBA molecular sieve, an HMS molecular sieve and an MSU molecular sieve.

12. The integrated catalyst according to claim 1, characterized in that the second active phase of the plurality of different active phases is an isomerization catalyst that is an alkaline earth metal oxide, selected from the group consisting of calcium oxide, magnesium oxide, strontium oxide, and barium oxide, preferably magnesium oxide.

13. The integrated catalyst according to claim 12, characterized in that the second active phase is preferably magnesium oxide in the form of polycrystalline hexagonal flakes; preferably, the hexagon has a side length of 180-600 nm and a thickness of 8-30 nm.

14. A process of preparing magnesium oxide, comprising: 1) preparing a solution of soluble magnesium salt with a concentration of 5-20%, heating to 40-80° C. and stirring to be homogeneous; 2) adding a surfactant and a complexing agent, wherein the molar ratio of the surfactant to 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 precipitator, wherein the molar ratio of the precipitator to magnesium ions is 2:1-5:1; 4) washing the precipitate obtained in the step 3) with water, washing with absolute ethanol, and drying at 70-90° C. for 8-12 h; and 5) calcining the product obtained in the step 4), controlling the heating rate to be 5-15° C./min, and calcining at 400-520° C. for 3-6 h.

15. The process according to claim 14, characterized in that the soluble magnesium salt is selected from magnesium sulfate, magnesium chloride and magnesium carbonate; the surfactant is a molecular surfactant, preferably selected from polyethylene glycol and P123; the complexing agent is selected from ethylenediamine tetraacetic acid and nitrilotriacetic acid; and the precipitator is selected from aqueous ammonia and urea, at a concentration of 5-30%.

16. A process of preparing the integrated catalyst according to claim 1, comprising: 1) respectively providing powders of a plurality of different active phases; 2) respectively molding the powders of the plurality of different active phases from step 1) to form a plurality of active phases with stable structures; and 3) integrating the plurality of active phases together by a means selected from the group consisting of: filling each active phase into a container with a plurality of chambers respectively; laminating the respective active phases; bonding the respective active phases; rolling the active phases in sequence; or co-extruding the active phases; wherein, the effective distance between the respective bisecting surfaces of two adjacent different active phases is controlled to be 0.5-5 mm, and preferably 1-3 mm.

17. The process of claim 16, characterized in that the particle size of the powders is 8 to 400 mesh.

18. The process according to claim 16 for preparing a multilayer structure of at least two layers, comprising: 1) respectively providing powders of a first active phase and powders of a second active phase; 2) molding one type of the powders obtained from step 1) to prepare a catalyst layer A; 3) combining a catalyst layer B formed by another type of powders in the step 1) on one bottom surface of the catalyst layer A; 4) optionally, using the method of step 3), combining other catalyst layer(s) on the basis of the two-layer catalyst particles compact obtained in step 3); and 5) drying and calcining the finally obtained catalyst particles compact to obtain the catalyst particles.

19. The process according to claim 18, characterized in that a tabletting or rolling process is used for the molding process.

20. The process according to claim 18, characterized in that the first active phase is a disproportionation catalyst, wherein a first adhesive is used during the first active phase powder being molded, and the first adhesive is at least one selected from silica sol and aluminum sol; and/or the second active phase is an isomerization catalyst, wherein a second binder is used during the second active phase powder being molded, and the second binder is at least one selected from polyvinyl alcohol, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl cellulose and polyvinylpyrrolidone.

21. The process according to claim 20, characterized in that the weight ratio of the first active phase powders to the first adhesive is 3:1-1:2; and/or the weight ratio of the second active phase powders to the second adhesive is 3:1-1:2.

22. The process according to claim 18, characterized in that the step 5) is carried out under conditions of: drying at a temperature of 80-110° C. for 8-15 hours; and preferably the calcining process is as follows: controlling the heating rate to be 0.5-1.5° C./min in the whole process, raising the temperature from room temperature to 280-320° C. in an inert atmosphere, keeping the temperature for 4-8 h, raising again the temperature to 460-500° C., keeping temperature for 4-8 h, then shifting the atmosphere to an oxygen-containing atmosphere, raising the temperature to 530-570° C., keeping the temperature for 4-8 h, then shifting the atmosphere to the inert atmosphere again, and keeping the temperature for 4-8 h.

23. Use of the integrated catalyst according to claim 1 for the disproportionation of olefins.

Description

DRAWINGS

[0074] FIG. 1 shows a schematic view of the structure of two-layer catalyst particles (a disproportionation catalyst layer and an isomerization catalyst layer);

[0075] FIG. 2 shows a schematic view of the structure of three-layer catalyst particles (a first isomerization catalyst layer, a disproportionation catalyst layer and a second isomerization catalyst layer from top to bottom);

[0076] FIG. 3 shows a schematic structural view of three-layer catalyst particles (a first disproportionation catalyst layer, an isomerization catalyst layer, and a second disproportionation catalyst layer from top to bottom);

[0077] wherein the reference numerals are as follows:

[0078] 1-a denotes a first disproportionation catalyst layer, 2-a denotes a first isomerization catalyst layer, 3-a denotes a second disproportionation catalyst layer, and 4-a denotes a second isomerization catalyst layer.

[0079] FIG. 4 shows SEM, TEM and electron diffraction photographs of magnesium oxide; and

[0080] FIG. 5 shows an SEM photograph of magnesium oxide used in comparative example 3.

DETAILED DESCRIPTION

[0081] 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.

[0082] In the Examples of the present invention and the Comparative Examples, 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.

[0083] The magnesium oxide used in the Examples of the invention was polycrystalline hexagonal flaky mesoporous magnesium oxide; prepared by: [0084] 1) preparing a solution of soluble magnesium salt with a concentration of 10%, heating to 60° C., and stirring; [0085] 2) adding polyethylene glycol and ethylene diamine tetraacetic acid, wherein the molar ratio of the surfactant to the magnesium ions was 1%, and the molar ratio of the complexing agent to the magnesium ions was 2%; [0086] 3) adding aqueous ammonia as a precipitator, wherein the molar ratio of the precipitator to magnesium ions was 3:1; [0087] 4) washing the precipitate obtained in the step 3 with water, washing with absolute ethanol, and drying at 80° C. for 8 hours; [0088] 5) calcining the product obtained in the step (4), controlling the heating rate to be 10° C./min, and calcining at 500° C. for 4 h.

Example 1

[0089] Disproportionation catalyst powders with a composition of WO.sub.3/SiO.sub.2 (wherein WO.sub.3 was used in an amount of 15 wt %) was mixed with alumina sol at a weight ratio of 3:1 and granulated, tableted into a cylindrical catalyst layer A with diameter*height=1.8 mm*3.0 mm. Calcium oxide powders and polyvinyl alcohol were mixed at a weight ratio of 3:1, from which a cylindrical catalyst layer B was tableted and combined on one bottom surface of the catalyst layer A, to prepare a compact of cylindrical catalyst particles with 1.8 mm*6.0 mm, wherein the effective distance of active phases was 3 mm. The thickness ratio of the disproportionation catalyst layer A to the isomerization catalyst layer B was 1:1, and the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:6.

[0090] The catalyst particles compact was dried at a drying temperature of 90° C. for 10 hours and then calcined, where the calcination process was as follows: controlling the heating rate to be 0.5° C./min in the whole process, raising the temperature from room temperature to 280° C. in a nitrogen atmosphere, keeping the temperature for 4 h, raising again the temperature to 460° C., keeping temperature for 4 h, then shifting the atmosphere to an air atmosphere, raising the temperature to 530° C., keeping the temperature for 4 h, then shifting the atmosphere to the nitrogen atmosphere again, and keeping the temperature for 4 h, to obtain the catalyst particles.

[0091] The catalyst particles prepared were loaded in a fixed bed reactor of Φ25 mm, and ethylene and butylene were used as feedstocks for disproportionation under the conditions of a weight space velocity of 10 h.sup.−1, a reaction temperature of 300° C., and a reaction pressure of 3 MPa, and the results were shown in Table 1.

Example 2

[0092] Disproportionation catalyst powders with a composition of WO.sub.3/SiO.sub.2 (wherein WO.sub.3 was used in an amount of 5 wt %) was mixed with alumina sol at a weight ratio of 2:1 and granulated, tableted into a cylindrical catalyst layer A with 6.0 mm*1.0 mm. Barium oxide powders and hydroxymethyl cellulose were mixed at a weight ratio of 2:1, from which a cylindrical catalyst layer B was tableted and combined on one bottom surface of the catalyst layer A, to prepare a compact of cylindrical catalyst particles with 6.0 mm*6.0 mm, wherein the effective distance of active phases was 3 mm. The thickness ratio of the disproportionation catalyst layer A to the isomerization catalyst layer B was 1:5, and the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:6.

[0093] The catalyst particles compact was dried at a drying temperature of 90° C. for 10 hours and then calcined, where the calcination process was as follows: controlling the heating rate to be 1.5° C./min in the whole process, raising the temperature from room temperature to 320° C. in a nitrogen atmosphere, keeping the temperature for 8 h, raising again the temperature to 500° C., keeping temperature for 8 h, then shifting the atmosphere to an air atmosphere, raising the temperature to 570° C., keeping the temperature for 8 h, then shifting the atmosphere to the nitrogen atmosphere again, and keeping the temperature for 8 h, to obtain the catalyst particles.

[0094] The catalyst particles prepared were loaded in a fixed bed reactor of Φ25 mm, and ethylene and butylene were used as feedstocks for disproportionation under the conditions of a weight space velocity of 10 h.sup.−1, a reaction temperature of 300° C., and a reaction pressure of 3 MPa, and the results were shown in Table 1.

Example 3

[0095] Disproportionation catalyst powders with a composition of WO.sub.3/MCM-41 (wherein WO.sub.3 was used in an amount of 10 wt %) was mixed with silica sol at a weight ratio of 1:1 and granulated, tableted into a cylindrical catalyst layer A with 3.0 mm*2.0 mm. Strontium oxide powders and polyvinylpyrrolidone were mixed at a weight ratio of 1:1, from which a cylindrical catalyst layer B was tableted and combined on one bottom surface of the catalyst layer A, to prepare a compact of cylindrical catalyst particles with 3.0 mm*6.0 mm, wherein the effective distance of active phases was 3 mm. The thickness ratio of the disproportionation catalyst layer A to the isomerization catalyst layer B was 1:2, and the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:6.

[0096] The catalyst particles compact was dried at a drying temperature of 90° C. for 10 hours and then calcined, where the calcination process was as follows: controlling the heating rate to be 1° C./min in the whole process, raising the temperature from room temperature to 300° C. in a nitrogen atmosphere, keeping the temperature for 6 h, raising again the temperature to 480° C., keeping temperature for 6 h, then shifting the atmosphere to an air atmosphere, raising the temperature to 550° C., keeping the temperature for 4 h, then shifting the atmosphere to the nitrogen atmosphere again, and keeping the temperature for 4 h, to obtain catalyst particles.

[0097] The catalyst particles prepared were loaded in a fixed bed reactor of Φ25 mm, and ethylene and butylene were used as feedstocks for disproportionation under the conditions of a weight space velocity of 10 h.sup.−1, a reaction temperature of 300° C., and a reaction pressure of 3 MPa, and the results were shown in Table 1.

Example 4

[0098] Disproportionation catalyst powders with a composition of WO.sub.3/SBA-15 (wherein WO.sub.3 was used in an amount of 10 wt %) was mixed with silica sol at a weight ratio of 1:2 and granulated, tableted into a cylindrical catalyst layer A with 4.0 mm*1.0 mm. Magnesium oxide powders and hydroxypropyl cellulose were mixed at a weight ratio of 1:2, from which a cylindrical catalyst layer B was tableted and combined on one bottom surface of the catalyst layer A, to prepare a compact of cylindrical catalyst particles with 4.0 mm*2.5 mm, wherein the effective distance of active phases was 1.25 mm. The thickness ratio of the disproportionation catalyst layer A to the isomerization catalyst layer B was 1:1.5, and the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:6.

[0099] The catalyst particles compact was dried at a drying temperature of 90° C. for 10 hours and then calcined, where the calcination process was as follows: controlling the heating rate to be 1° C./min in the whole process, raising the temperature from room temperature to 300° C. in a nitrogen atmosphere, keeping the temperature for 6 h, raising again the temperature to 480° C., keeping temperature for 6 h, then shifting the atmosphere to an air atmosphere, raising the temperature to 550° C., keeping the temperature for 4 h, then shifting the atmosphere to the nitrogen atmosphere again, and keeping the temperature for 4 h, to obtain catalyst particles.

[0100] The catalyst particles prepared were loaded in a fixed bed reactor of Φ25 mm, and ethylene and butylene were used as feedstocks for disproportionation under the conditions of a weight space velocity of 10 h.sup.−1, a reaction temperature of 300° C., and a reaction pressure of 3 MPa, and the results were shown in Table 1.

Example 5

[0101] Disproportionation catalyst powders with a composition of WO.sub.3/MSU (wherein WO.sub.3 was used in an amount of 10 wt %) was mixed with silica sol at a weight ratio of 1:2 and granulated, tableted into a cylindrical catalyst layer A with 4.0 mm*2.0 mm. Magnesium oxide powders and hydroxypropyl methylcellulose were mixed at a weight ratio of 1:2, from which a cylindrical catalyst layer B was tableted and combined on one bottom surface of the catalyst layer A, to prepare a compact of cylindrical catalyst particles with 4.0 mm*6.0 mm, wherein the effective distance of active phases was 3 mm. The thickness ratio of the disproportionation catalyst layer A to the isomerization catalyst layer B was 1:2, and the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:6.

[0102] The catalyst particles compact was dried at a drying temperature of 90° C. for 10 hours and then calcined, where the calcination process was as follows: controlling the heating rate to be 1° C./min in the whole process, raising the temperature from room temperature to 300° C. in a nitrogen atmosphere, keeping the temperature for 6 h, raising again the temperature to 480° C., keeping temperature for 6 h, then shifting the atmosphere to an air atmosphere, raising the temperature to 550° C., keeping the temperature for 4 h, then shifting the atmosphere to the nitrogen atmosphere again, and keeping the temperature for 4 h, to obtain catalyst particles, which, as shown in FIG. 1, was composed by a first disproportionation catalyst layer 1 (disproportionation catalyst layer A) and a first isomerization catalyst layer 2 (isomerization catalyst layer B).

[0103] The catalyst particles prepared were loaded in a fixed bed reactor of Φ25 mm, and ethylene and butylene were used as feedstocks for disproportionation under the conditions of a weight space velocity of 10 h.sup.−1, a reaction temperature of 300° C., and a reaction pressure of 3 MPa, and the results were shown in Table 1.

Example 6

[0104] Disproportionation catalyst powders with a composition of WO.sub.3/SiO.sub.2 (wherein WO.sub.3 was used in an amount of 10 wt %) was mixed with silica sol at a weight ratio of 1:2 and granulated, tableted into a cylindrical catalyst layer A with 3.0 mm*1.5 mm. Magnesium oxide powders and hydroxypropyl methylcellulose were mixed at a weight ratio of 1:2 and granulated, from which a cylindrical catalyst layer B was tableted and combined on one bottom surface of the catalyst layer A, to prepare an intermediate of cylindrical catalyst particles with 3.0 mm*4.5 mm, followed by further combining a disproportionation catalyst layer C with the same means, to obtain cylindrical catalyst particles compact with 3.0 mm*6.0 mm, wherein the effective distance of active phases was 2.25 mm. The thickness ratio of disproportionation catalyst layer A:isomerization catalyst layer B:disproportionation catalyst layer C was 1:2:1, at a weight ratio of 1:2:1.

[0105] The catalyst particles compact was dried at a drying temperature of 90° C. for 10 hours and then calcined, where the calcination process was as follows: controlling the heating rate to be 1° C./min in the whole process, raising the temperature from room temperature to 300° C. in a nitrogen atmosphere, keeping the temperature for 6 h, raising again the temperature to 480° C., keeping temperature for 6 h, then shifting the atmosphere to an air atmosphere, raising the temperature to 550° C., keeping the temperature for 4 h, then shifting the atmosphere to the nitrogen atmosphere again, and keeping the temperature for 4 h, to obtain catalyst particles, which, as shown in FIG. 3, was composed by 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).

[0106] The catalyst particles prepared were loaded in a fixed bed reactor of Φ25 mm, and ethylene and butylene were used as feedstocks for disproportionation under the conditions of a weight space velocity of 10 h.sup.−1, a reaction temperature of 300° C., and a reaction pressure of 3 MPa, and the results were shown in Table 1.

Example 7

[0107] Magnesium oxide powders and hydroxypropyl methylcellulose were mixed at a weight ratio of 1:2 and granulated, and tableted to prepare a cylindrical catalyst layer with 3.0 mm*2.4 mm. Disproportionation catalyst powders having a composition of WO.sub.3/SiO.sub.2 (wherein WO.sub.3 was used in an amount of 10 wt %) was mixed with silica sol at a weight ratio of 1:2, from which a cylindrical catalyst layer B was tableted and combined on one bottom surface of the catalyst layer A, to prepare an intermediate of cylindrical catalyst particles with 3.0 mm*3.6 mm, followed by further combining an isomerization catalyst layer C with the same means, to obtain cylindrical catalyst particles compact with 3.0 mm*6.0 mm, wherein the effective distance of active phases was 1.8 mm. The thickness ratio of isomerization catalyst layer A:disproportionation catalyst layer B:isomerization catalyst layer C was 2:1:2, at a weight ratio of 5:1:5.

[0108] The catalyst particles compact was dried at a drying temperature of 90° C. for 10 hours and then calcined, where the calcination process was as follows: controlling the heating rate to be 1° C./min in the whole process, raising the temperature from room temperature to 300° C. in a nitrogen atmosphere, keeping the temperature for 6 h, raising again the temperature to 480° C., keeping temperature for 6 h, then shifting the atmosphere to an air atmosphere, raising the temperature to 550° C., keeping the temperature for 4 h, then shifting the atmosphere to the nitrogen atmosphere again, and keeping the temperature for 4 h, to obtain catalyst particles, which, as shown in FIG. 2, was composed by 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).

[0109] The catalyst particles prepared were loaded in a fixed bed reactor of Φ25 mm, and ethylene and butylene were used as feedstocks for disproportionation under the conditions of a weight space velocity of 10 h.sup.−1, a reaction temperature of 300° C., and a reaction pressure of 3 MPa, and the results were shown in Table 1.

Example 8

[0110] Disproportionation catalyst powders with a composition of WO.sub.3/SiO.sub.2 (wherein WO.sub.3 was used in an amount of 10 wt %) was mixed with silica sol at a weight ratio of 1:2 and granulated, tableted into a cylindrical catalyst layer A with 4.0 mm*2.0 mm. Magnesium oxide powders and hydroxypropyl methylcellulose were mixed at a weight ratio of 1:2, from which a cylindrical catalyst layer B was tableted and combined on one bottom surface of the catalyst layer A, to prepare a compact of cylindrical catalyst particles with 4.0 mm*6.0 mm, wherein the effective distance of active phases was 3 mm. The thickness ratio of the disproportionation catalyst layer A to the isomerization catalyst layer B was 1:2, and the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:2.

[0111] The catalyst particles compact was dried at a drying temperature of 90° C. for 10 hours and then calcined, where the calcination process was as follows: controlling the heating rate to be 1° C./min in the whole process, raising the temperature from room temperature to 300° C. in a nitrogen atmosphere, keeping the temperature for 6 h, raising again the temperature to 480° C., keeping temperature for 6 h, then shifting the atmosphere to an air atmosphere, raising the temperature to 550° C., keeping the temperature for 4 h, then shifting the atmosphere to the nitrogen atmosphere again, and keeping the temperature for 4 h, to obtain catalyst particles.

[0112] The catalyst particles prepared were loaded in a fixed bed reactor of Φ25 mm, and ethylene and butylene were used as feedstocks for disproportionation under the conditions of a weight space velocity of 10 h.sup.−1, a reaction temperature of 300° C., and a reaction pressure of 3 MPa, and the results were shown in Table 1.

Example 9

[0113] Disproportionation catalyst powders with a composition of WO.sub.3/SiO.sub.2 (wherein WO.sub.3 was used in an amount of 10 wt %) was mixed with silica sol at a weight ratio of 1:2 and granulated, tableted into a cylindrical catalyst layer A with 4.0 mm*2.5 mm. Magnesium oxide powders and hydroxypropyl methylcellulose were mixed at a weight ratio of 1:2, from which a cylindrical catalyst layer B was tableted and combined on one bottom surface of the catalyst layer A, to prepare a compact of cylindrical catalyst particles with 4.0 mm*wherein the effective distance of active phases was 2.5 mm. The thickness ratio of the disproportionation catalyst layer A to the isomerization catalyst layer B was 1:1, and the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:2.

[0114] The catalyst particles compact was dried at a drying temperature of 90° C. for 10 hours and then calcined, where the calcination process was as follows: controlling the heating rate to be 1° C./min in the whole process, raising the temperature from room temperature to 300° C. in a nitrogen atmosphere, keeping the temperature for 6 h, raising again the temperature to 480° C., keeping temperature for 6 h, then shifting the atmosphere to an air atmosphere, raising the temperature to 550° C., keeping the temperature for 4 h, then shifting the atmosphere to the nitrogen atmosphere again, and keeping the temperature for 4 h, to obtain catalyst particles.

[0115] The catalyst particles prepared were loaded in a fixed bed reactor of Φ25 mm, and ethylene and butylene were used as feedstocks for disproportionation under the conditions of a weight space velocity of 10 h.sup.−1, a reaction temperature of 300° C., and a reaction pressure of 3 MPa, and the results were shown in Table 1.

Example 10

[0116] Disproportionation catalyst powders with a composition of WO.sub.3/SiO.sub.2 (wherein WO.sub.3 was used in an amount of 10 wt %) was mixed with silica sol at a weight ratio of 1:2 and granulated, tableted into a cylindrical catalyst layer A with 4.0 mm*2.0 mm. Magnesium oxide powders and hydroxypropyl methylcellulose were mixed at a weight ratio of 1:2, from which a cylindrical catalyst layer B was tableted and combined on one bottom surface of the catalyst layer A, to prepare a compact of cylindrical catalyst particles with 4.0 mm*6.0 mm, wherein the effective distance of active phases was 3 mm. The thickness ratio of the disproportionation catalyst layer A to the isomerization catalyst layer B was 1:2, and the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:2.

[0117] The catalyst particles compact was dried at a drying temperature of 90° C. for 10 hours, and then calcined by a conventional process by: controlling the heating rate to be 5° C./min in the whole process, raising the temperature from room temperature to 550° C. in a muffle furnace, keeping the temperature for 4 h, to obtain catalyst particles, which particles were found to be broken in a fault and could not be used for reaction evaluation.

Example 11

[0118] Disproportionation catalyst powders with a composition of WO.sub.3/SiO.sub.2 (wherein WO.sub.3 was used in an amount of 10 wt %) was mixed with silica sol at a weight ratio of 1:2 and granulated, tableted into a cylindrical catalyst layer A with 4.0 mm*2.0 mm. Magnesium oxide powders and hydroxypropyl methylcellulose were mixed at a weight ratio of 1:2, from which a cylindrical catalyst layer B was tableted and combined on one bottom surface of the catalyst layer A, to prepare a compact of cylindrical catalyst particles with 4.0 mm*6.0 mm, wherein the effective distance of active phases was 3 mm. The thickness ratio of the disproportionation catalyst layer A to the isomerization catalyst layer B was 1:2, and the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:2.

[0119] The catalyst particles compact was dried at a drying temperature of 90° C. for 10 hours and then calcined, where the calcination process was as follows: controlling the heating rate to be 1° C./min in the whole process, raising the temperature from room temperature to 300° C. in a nitrogen atmosphere, keeping the temperature for 6 h, raising again the temperature to 480° C., keeping temperature for 6 h, then shifting the atmosphere to an air atmosphere, raising the temperature to 550° C., keeping the temperature for 4 h, then shifting the atmosphere to the nitrogen atmosphere again, and keeping the temperature for 4 h, to obtain catalyst particles.

[0120] The catalyst particles prepared were loaded in a fixed bed reactor of Φ25 mm, and ethylene and butylene were used as feedstocks for disproportionation under the conditions of a weight space velocity of 1 h.sup.−1, a reaction temperature of 200° C., and a reaction pressure of 5 MPa, and the results were shown in Table 1.

Example 12

[0121] Disproportionation catalyst powders with a composition of WO.sub.3/SiO.sub.2 (wherein WO.sub.3 was used in an amount of 10 wt %) was mixed with silica sol at a weight ratio of 1:2 and granulated, tableted into a cylindrical catalyst layer A with 4.0 mm*2.0 mm. Magnesium oxide powders and hydroxypropyl methylcellulose were mixed at a weight ratio of 1:2, from which a cylindrical catalyst layer B was tableted and combined on one bottom surface of the catalyst layer A, to prepare a compact of cylindrical catalyst particles with 4.0 mm*6.0 mm, wherein the effective distance of active phases was 3 mm. The thickness ratio of the disproportionation catalyst layer A to the isomerization catalyst layer B was 1:2, and the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:2.

[0122] The catalyst particles compact was dried at a drying temperature of 90° C. for 10 hours and then calcined, where the calcination process was as follows: controlling the heating rate to be 1° C./min in the whole process, raising the temperature from room temperature to 300° C. in a nitrogen atmosphere, keeping the temperature for 6 h, raising again the temperature to 480° C., keeping temperature for 6 h, then shifting the atmosphere to an air atmosphere, raising the temperature to 550° C., keeping the temperature for 4 h, then shifting the atmosphere to the nitrogen atmosphere again, and keeping the temperature for 4 h, to obtain catalyst particles.

[0123] The catalyst particles prepared were loaded in a fixed bed reactor of Φ25 mm, and ethylene and butylene were used as feedstocks for disproportionation under the conditions of a weight space velocity of 30 h.sup.−1, a reaction temperature of 450° C., and a reaction pressure of 0.1 MPa, and the results were shown in Table 1.

Comparative Example 1

[0124] Disproportionation catalyst powders with a composition of WO.sub.3/SiO.sub.2 (wherein WO.sub.3 was used in an amount of 10 wt %) was mixed with silica sol at a weight ratio of 1:2 and granulated, tableted into a cylindrical catalyst particles A compact with 4.0 mm*5.0 mm. The catalyst particles compact was dried at a drying temperature of 90° C. for 10 hours and then calcined, where the calcination process was as follows: controlling the heating rate to be 1° C./min in the whole process, raising the temperature from room temperature to 300° C. in a nitrogen atmosphere, keeping the temperature for 6 h, raising again the temperature to 480° C., keeping temperature for 6 h, then shifting the atmosphere to an air atmosphere, raising the temperature to 550° C., keeping the temperature for 4 h, then shifting the atmosphere to the nitrogen atmosphere again, and keeping the temperature for 4 h, to obtain catalyst particles A.

[0125] Magnesium oxide powders and hydroxypropyl methylcellulose were mixed at a weight ratio of 1:2 and granulated, and tableted to prepare a catalyst particles B compact with 4.0 mm*5.0 mm. The catalyst particles compact was dried at a drying temperature of for 10 hours and then calcined, where the calcination process was as follows: controlling the heating rate to be 1° C./min in the whole process, raising the temperature from room temperature to 300° C. in a nitrogen atmosphere, keeping the temperature for 6 h, raising again the temperature to 480° C., keeping temperature for 6 h, then shifting the atmosphere to an air atmosphere, raising the temperature to 550° C., keeping the temperature for 4 h, then shifting the atmosphere to the nitrogen atmosphere again, and keeping the temperature for 4 h, to obtain catalyst particles B.

[0126] The two types of catalyst particles above were mechanically loaded in a fixed bed reactor of Φ25 mm, where the weight ratio of the disproportionation catalyst to the isomerization catalyst was 1:6. Ethylene and butylene were used as feedstocks for disproportionation under the conditions of a weight space velocity of 10 h.sup.−1, a reaction temperature of 300° C., and a reaction pressure of 3 MPa, and the results were shown in Table 1.

Comparative Example 2

[0127] Disproportionation catalyst powders with a composition of WO.sub.3/SiO.sub.2 (wherein WO.sub.3 was used in an amount of 10 wt %) was mixed with silica sol at a weight ratio of 1:2 and granulated, magnesium oxide powders and hydroxypropyl methylcellulose were mixed at a weight ratio of 1:2 and granulated, the disproportionation catalyst powders was mixed with the magnesium oxide powders at a weight ratio of 1:6, and tableted to prepare a catalyst particles B compact with 4.0 mm*5.0 mm.

[0128] The catalyst particles compact was dried at a drying temperature of 90° C. for 10 hours and then calcined, where the calcination process was as follows: controlling the heating rate to be 1° C./min in the whole process, raising the temperature from room temperature to 300° C. in a nitrogen atmosphere, keeping the temperature for 6 h, raising again the temperature to 480° C., keeping temperature for 6 h, then shifting the atmosphere to an air atmosphere, raising the temperature to 550° C., keeping the temperature for 4 h, then shifting the atmosphere to the nitrogen atmosphere again, and keeping the temperature for 4 h, to obtain catalyst particles. The catalyst particles above were loaded in a fixed bed reactor of Φ25 mm, and ethylene and butylene were used as feedstocks for disproportionation under the conditions of a weight space velocity of 10 h.sup.−1, a reaction temperature of 300° C., and a reaction pressure of 3 MPa, and the results were shown in Table 1.

Comparative Example 3

[0129] Disproportionation catalyst powders with a composition of WO.sub.3/SiO.sub.2 (wherein WO.sub.3 was used in an amount of 10 wt %) was mixed with silica sol at a weight ratio of 1:2 and granulated, magnesium oxide powders and hydroxypropyl methylcellulose were mixed at a weight ratio of 1:2 and granulated, the disproportionation catalyst powders was mixed with the magnesium oxide powders at a weight ratio of 1:6, and tableted to prepare a catalyst particles B compact with 4.0 mm*5.0 mm, wherein the magnesium oxide used was a non-flaky magnesium oxide, for which the SEM characterization was shown in FIG. 5.

[0130] The catalyst particles compact was dried at a drying temperature of 90° C. for 10 hours and then calcined, where the calcination process was as follows: controlling the heating rate to be 1° C./min in the whole process, raising the temperature from room temperature to 300° C. in a nitrogen atmosphere, keeping the temperature for 6 h, raising again the temperature to 480° C., keeping temperature for 6 h, then shifting the atmosphere to an air atmosphere, raising the temperature to 550° C., keeping the temperature for 4 h, then shifting the atmosphere to the nitrogen atmosphere again, and keeping the temperature for 4 h, to obtain catalyst particles. The catalyst particles above were loaded in a fixed bed reactor of Φ25 mm, and ethylene and butylene were used as feedstocks for disproportionation under the conditions of a weight space velocity of 10 h.sup.−1, a reaction temperature of 300° C., and a reaction pressure of 3 MPa, and the results were shown in Table 1.

TABLE-US-00001 TABLE 1 thickness ratio of the disproportionation catalyst layer to Disproportionation Isomerization the isomerization Conversion catalyst + binder catalyst + binder catalyst layer (%) Stability Ex. 1 SiO.sub.2/85 + CaO + polyvinyl 1:1 57.2 750 WO.sub.3/15 + alcohol alumina sol Ex. 2 SiO.sub.2/95 + BaO + polyvinyl 1:5 57.0 751 WO.sub.3/5 + alcohol alumina sol Ex. 3 MCM-41/90 + SrO + 1:2 56.5 753 WO.sub.3/10 + polyvinylpyrrolidone silica sol Ex. 4 SBA-15/90 + MgO +   1:1.5 61.3 805 WO.sub.3/10 + hydroxypropyl silica sol cellulose Ex. 5 MSU/90 + MgO + 1:2 62.1 814 WO.sub.3/10 + hydroxypropyl silica sol methylcellulose Ex. 6 SiO.sub.2/90 + MgO + 1:2:1**  70.4 820 WO.sub.3/10 + hydroxypropyl silica sol methylcellulose Ex. 7 SiO.sub.2/90 + MgO + 2:1:2*** 71.0 822 WO.sub.3/10 + hydroxypropyl silica sol methylcellulose Ex. 8 SiO.sub.2/90 + MgO + 1:2 69.8 815 WO.sub.3/10 + hydroxypropyl silica sol methylcellulose Ex. 9 SiO.sub.2/90 + MgO + 1:1 60.3 641 WO.sub.3/10 + hydroxypropyl silica sol methylcellulose Ex. 10 SiO.sub.2/90 + MgO + 1:2 — — WO.sub.3/10 + hydroxypropyl silica sol methylcellulose Ex. 11 SiO.sub.2/90 + MgO + 1:2 67.5 805 WO.sub.3/10 + hydroxypropyl silica sol methylcellulose Ex. 12 SiO.sub.2/90 + MgO + 1:2 68.1 781 WO.sub.3/10 + hydroxypropyl silica sol methylcellulose C.E. 1 SiO.sub.2/90 + MgO + — 52.1 630 WO.sub.3/10 + hydroxypropyl silica sol methylcellulose C.E. 2 SiO.sub.2/90 + WO.sub.3/10 + silica sol + MgO + — 59.1 628 hydroxypropyl methylcellulose C.E. 3 SiO.sub.2/90 + MgO + 1:2 47.3 421 WO.sub.3/10 + hydroxypropyl silica sol methylcellulose Note: *stability referred to the duration under stable operation with catalyst conversion greater than 60%; **The ratio of 1:2:1 in Example 6 referred to the thickness ratio of the disproportionation catalyst layer A, the isomerization catalyst layer B, and the disproportionation catalyst layer C; ***The ratio of 2:1: 2 in Example 7 referred to the thickness ratio of the isomerization catalyst layer A, the disproportionation catalyst layer B, and the isomerization catalyst layer C.

[0131] The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.