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, comprising a plurality of different active phases integrated together, and the relative position between two of the plurality of different active phases is kept substantially unchanged during the olefin disproportionation, wherein an effective distance between the respective bisecting surfaces of two adjacent active phases is 0.5-5 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, 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 arrangement.

5. The integrated catalyst according to claim 1, wherein, for two adjacent active phases, one active phase is a disproportionation catalyst and the other active phase is an isomerization catalyst, and a 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).

6. The integrated catalyst according to claim 1, wherein a displacement of the relative position between the two of the plurality of active phases during the olefin disproportionation reaction is 0 to 0.5 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, wherein the catalyst particles have a total thickness of from 2.0 mm to 8.0 mm, and a radial length of 1.8 mm to 6.0 mm.

9. The integrated catalyst according to claim 7, wherein the catalyst particles are in a multi-layer structure having at least two layers.

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

11. The integrated catalyst according to claim 10, wherein the support is SiO.sub.2 or a mesoporous molecular sieve.

12. The integrated catalyst according to claim 1, wherein the second active phase of the plurality of 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.

13. The integrated catalyst according to claim 12, wherein the second active phase is-preferably magnesium oxide in the form of polycrystalline hexagonal flakes.

14. The integrated catalyst according to claim 13, wherein the magnesium oxide in the form of polycrystalline hexagonal flakes is prepared according to a method 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 3-6h.

15. The integrated catalyst according to claim 14, 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 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) providing powders of the plurality of different active phases; 2) molding the powders of the plurality of different active phases from step 1) to form a plurality of active phases; and 3) integrating the plurality of active phases together by filling each of the plurality of active phases into a container having a plurality of chambers respectively; laminating the plurality of active phases; bonding the plurality of active phases; rolling the plurality of active phases in sequence; or co-extruding the plurality of active phases.

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

18. The process according to claim 16, comprising: 1) providing a first powder of a first active phase and a second powder of a second active phase; 2) molding the first powder to prepare a catalyst layer A; 3) combining a catalyst layer B formed by the second powders on a bottom surface of the catalyst layer A to form a compact; 4) optionally, combining other catalyst layer(s) on the compact obtained in step 3); and 5) drying and calcining the compact having two or more layers to obtain the integrated catalyst.

19. The process according to claim 18, wherein the molding step is by tabletting or rolling.

20. The process according to claim 18, wherein the first active phase is a disproportionation catalyst comprising the first powder and a first binder, and the first binder is at least one selected from silica sol and aluminum sol; and/or the second active phase is an isomerization catalyst comprising the second powder and a second binder, 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, wherein a weight ratio of the first powder to the first binder is 3:1-1:2; and/or a weight ratio of the second powder to the second binder is 3:1-1:2.

22. The process according to claim 18, wherein the drying in step 5) is carried out under conditions of: drying at a temperature of 80-110C. for 8-15 hours; and the calcining in step 5) is as follows: controlling the heating rate to be 0.5-1.5C./min in the whole process, raising the temperature from room temperature to 280-320C. in an inert atmosphere, keeping the temperature for 4-8 h, raising again the temperature to 460-500C., keeping temperature for 4-8 h, then shifting the atmosphere to an oxygen-containing atmosphere, raising the temperature to 530-570C., 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. A method for disproportionation of olefins, comprising contact the olefins with the integrated catalyst according to claim 1.

24. The integrated catalyst according to claim 11, wherein the mesoporous molecular sieve is selected from the group consisting of an MCM molecular sieve, an SBA molecular sieve, an HMS molecular sieve, and an MSU molecular sieve.

25. The integrated catalyst according to claim 12, wherein the isomerization catalyst is magnesium oxide.

26. The integrated catalyst according to claim 15, wherein the surfactant is polyethylene glycol or P123.

Description

DRAWINGS

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

(2) 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);

(3) 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); wherein the reference numerals are as follows: 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.

(4) FIG. 4 shows SEM, TEM and electron diffraction photographs of magnesium oxide; and

(5) FIG. 5 shows an SEM photograph of magnesium oxide used in comparative example 3.

DETAILED DESCRIPTION

(6) 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.

(7) 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.

(8) The magnesium oxide used in the Examples of the invention was polycrystalline hexagonal flaky mesoporous magnesium oxide; prepared by: 1) preparing a solution of soluble magnesium salt with a concentration of 10%, heating to 60 C., and stirring; 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%; 3) adding aqueous ammonia as a precipitator, wherein the molar ratio of the precipitator to magnesium ions was 3:1; 4) washing the precipitate obtained in the step 3 with water, washing with absolute ethanol, and drying at 80 C. for 8 hours; 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

(9) 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.

(10) 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.

(11) The catalyst particles prepared were loaded in a fixed bed reactor of 25 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

(12) 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.

(13) 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.

(14) The catalyst particles prepared were loaded in a fixed bed reactor of 25 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

(15) 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.

(16) 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.

(17) The catalyst particles prepared were loaded in a fixed bed reactor of 25 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

(18) 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.

(19) 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.

(20) The catalyst particles prepared were loaded in a fixed bed reactor of 25 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

(21) 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.

(22) 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).

(23) The catalyst particles prepared were loaded in a fixed bed reactor of 25 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

(24) 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.

(25) 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).

(26) The catalyst particles prepared were loaded in a fixed bed reactor of 25 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

(27) 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.

(28) 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).

(29) The catalyst particles prepared were loaded in a fixed bed reactor of 25 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

(30) 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.

(31) 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.

(32) The catalyst particles prepared were loaded in a fixed bed reactor of 25 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

(33) 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.

(34) 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.

(35) The catalyst particles prepared were loaded in a fixed bed reactor of 25 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

(36) 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.

(37) 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

(38) 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.

(39) 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.

(40) The catalyst particles prepared were loaded in a fixed bed reactor of 25 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

(41) 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.

(42) 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.

(43) The catalyst particles prepared were loaded in a fixed bed reactor of 25 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

(44) 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.

(45) 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.

(46) The two types of catalyst particles above were mechanically loaded in a fixed bed reactor of 25 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

(47) 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.

(48) 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 25 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

(49) 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.

(50) 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 25 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.

(51) 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.

(52) 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.