COBALT CARBIDE-BASED CATALYST FOR DIRECT PREPARATION OF OLEFIN FROM SYNTHESIS GAS, PREPARATION METHOD THEREFOR AND APPLICATION THEREOF

Abstract

A cobalt carbide-based catalyst for direct production of olefin from synthesis gas, a preparation method therefor and application thereof are disclosed. The method for preparing the catalyst comprises the following steps: 1) mixing a cobalt source with water, or mixing a cobalt source, an electron promoter and water to obtain a first solution; and mixing a precipitant with water to obtain a second solution; 2) adding the first solution and the second solution to water, or water and a structure promoter for precipitation, crystallizing, separating, drying and calcination; and 3) reducing a solid obtained in Step 2) in a reducing atmosphere, and then carbonizing in a carbonizing atmosphere. The prepared catalyst has high activity and high selectivity to olefins for direct production of olefins via syngas conversion.

Claims

1. A method for preparing a cobalt carbide-based catalyst for direct production of olefin from synthesis gas, comprising the following steps: 1) mixing a cobalt source with water, or mixing a cobalt source, an electron promoter with water to obtain a first solution; and mixing a precipitant with water to obtain a second solution; 2) adding the first solution and the second solution to water, or water and a structure promoter for precipitation, crystallizing, separating, drying and calcination; and 3) reducing a solid obtained in Step 2) in a reducing atmosphere, and then carbonizing in a carbonizing atmosphere.

2. The preparation method according to claim 1, further comprising adding an alkali metal promoter to the solid obtained in Step 3) by incipient wetness impregnation, then drying, and calcination, or adding an alkali metal promoter to the solid obtained in Step 2) by incipient wetness impregnation, then drying, calcination, and reducing in a reducing atmosphere.

3. The preparation method according to claim 2, wherein the alkali metal promoter includes alkali metal hydroxide and/or alkali metal salt.

4. The preparation method according to claim 2, further comprising one or more of the following: 1) the molar ratio of the cobalt source based on Co to the alkali metal promoter is 1:0.001-0.5; 2) the drying temperature ranges from 60 to 120 C., and the drying time ranges from 4 to 48 hours; and 3) the calcination temperature ranges from 200 to 500 C., and the calcination time ranges from 1 to 24 hours.

5. The preparation method according to claim 1, further comprising one or more of the following: 1) the cobalt source is an organic cobalt source and/or an inorganic cobalt source; 2) the electron promoter is one or more selected from a transition metal salt, an alkaline earth metal salt, and a rare earth metal salt; 3) the precipitant is an alkali and/or a basic salt; and 4) the structure promoter is one or more selected from alumina, silica, titania, zirconia, magnesia and a carbon material.

6. The preparation method according to claim 1, further comprising one or more of the following: 1) in Step 1), the molar ratio of the cobalt source based on Co:electron promoter:water is 1:(0-10):(1-1000); 2) in Step 1), the molar ratio of the precipitant to water is 1:(1-1000); 3) in Step 2), when the first solution and the second solution are added to water, the weight ratio of cobalt:water is 1:(1-1000); 4) in Step 2), when the first solution and the second solution are added to water and the structure promoter, the weight ratio of the structure promoter:cobalt:water is 1:(0.05-1):(1-1000).

7. The preparation method according to claim 1 or 2, further comprising one or more of the following features where 1) in Step 2), the precipitation temperature ranges from 0 to 90 C., and the pH is controlled to 7-12; 2) in Step 2), the crystallization temperature ranges from 0 to 200 C., and the crystallization time ranges from 1 to 72 hours; 3) in Step 2), the drying temperature ranges from 60 to 120 C., and the drying time ranges from 4 to 48 hours; 4) in Step 2), the calcination temperature ranges from 200 to 500 C., and the calcination time ranges from 1 to 24 hours; 5) in Step 3), the reduction conditions comprise a reduction temperature of 100-600 C., a reduction pressure of 0.1-10 MPa, a gas hourly space velocity of 500-100,000 h.sup.1, and a reduction time of 1-24 hours; and 6) in Step 3), the carbonization conditions comprise a carbonization temperature of 100-500 C., a carbonization pressure of 0.1-10 MPa, a gas hourly space velocity of 500-100,000 h.sup.1, and a carbonization time of 1-72 hours.

8. The preparation method according to claim 1, wherein in Step 3), the reducing atmosphere is hydrogen, carbon monoxide, a mixture of hydrogen or carbon monoxide with an inert gas at any ratio.

9. The preparation method according to claim 1, wherein in Step 3), the carbonizing atmosphere is carbon monoxide, or a mixture of carbon monoxide and other gases, where the other gases is hydrogen and/or an inert gas.

10. A cobalt carbide-based catalyst for direct production of olefins from synthesis gas, which is prepared through a method according to claim 1.

11. Use of a cobalt carbide-based catalyst for direct production of olefins from synthesis gas according to claim 10 in the direct production of olefins from syngas, wherein the reaction conditions comprises a reaction temperature of 150-500 C., a reaction pressure of 0.1-10 MPa, a gas hourly space velocity of 500-100,000 h.sup.1, and a molar ratio of H.sub.2 to CO is (1:10)-(10:1).

12. The use of a cobalt carbide-based catalyst for direct production of olefins from synthesis gas according to claim 11, wherein the reaction is carried out in a fixed bed, a slurry bed or a fluidized bed.

13. The preparation method according to claim 2, further comprising one or more of the following: 1) the cobalt source is an organic cobalt source and/or an inorganic cobalt source; 2) the electron promoter is one or more selected from a transition metal salt, an alkaline earth metal salt, and a rare earth metal salt; 3) the precipitant is an alkali and/or a basic salt; and 4) the structure promoter is one or more selected from alumina, silica, titania, zirconia, magnesia and a carbon material.

14. The preparation method according to claim 2, further comprising one or more of the following: 1) in Step 1), the molar ratio of the cobalt source based on Co:electronpromoter:water is 1: (0-10): (1-1000); 2) in Step 1), the molar ratio of the precipitant to water is 1:(1-1000); 3) in Step 2), when the first solution and the second solution are added to water, the weight ratio of cobalt:water is 1:(1-1000); 4) in Step 2), when the first solution and the second solution are added to water and the structure promoter, the weight ratio of the structure promoter:cobalt:water is 1:(0.05-1):(1-1000).

15. The preparation method according to claim 2, further comprising one or more of the following features where 1) in Step 2), the precipitation temperature ranges from 0 to 90 C., and the pH is controlled to 7-12; 2) in Step 2), the crystallization temperature ranges from 0 to 200 C., and the crystallization time ranges from 1 to 72 hours; 3) in Step 2), the drying temperature ranges from 60 to 120 C., and the drying time ranges from 4 to 48 hours; 4) in Step 2), the calcination temperature ranges from 200 to 500 C., and the baking time ranges from 1 to 24 hours; 5) in Step 3), the reduction conditions comprise a reduction temperature of 100-600 C., a reduction pressure of 0.1-10 MPa, a gas hourly space velocity of 500-100,000 h.sup.1, and a reduction time of 1-24 hours; and 6) in Step 3), the carbonization conditions comprises a carbonization temperature of 100-500 C., a carbonization pressure of 0.1-10 MPa, a gas hourly space velocity of 500-100,000 h.sup.1, and a carbonization time of 1-72 hours.

16. The preparation method according to claim 2, wherein in Step 3), the reducing atmosphere is hydrogen, carbon monoxide, a mixture of hydrogen or carbon monoxide with an inert gas at any ratio.

17. The preparation method according to claim 2, wherein in Step 3), the carbonizing atmosphere is carbon monoxide, or a mixture of carbon monoxide and other gases, where the other gases is hydrogen and/or an inert gas.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0055] FIG. 1 describes the X-ray diffraction pattern of a catalyst obtained in Example 1, showing that the active phase is Co.sub.2C.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0056] The technical solutions of the present invention are explained below by way of specific examples. It should be understood that the one or more method steps mentioned in the present invention does not exclude a situation that there are other method steps before or after the combination of steps or other steps may be inserted between these explicitly mentioned steps. It should also be understood that these examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention. Moreover, unless otherwise stated, the numbering of each method step is merely a convenient tool for identifying the each method step, and is not intended to limit the order in which the method steps are arranged, or to limit the scope of the present invention. The change or adjustment made to the relative relationship thereof without substantially change the technical content is also deemed to fall within the scope of the present invention.

[0057] The technical details of the present invention are elaborated by the following examples. It is to be noted that the examples are merely illustrative of the technical features of the present invention and are not intended to limit the present invention.

Example 1

[0058] Cobalt nitrate was fully dissolved in water by stirring at a molar ratio of cobalt nitrate:water=1:25, to obtain a first solution. Sodium carbonate was fully dissolved in water by stirring at a molar ratio of sodium carbonate:water=1:25, to obtain a second solution. A certain amount of deionized water is prepared according to a weight ratio of cobalt:water=1:10. Both the first solution and the second solution were added dropwise to the deionized water at a precipitation temperature of 60 C. and pH controlled to 8. After addition, it was crystallized at a temperature of 60 C. for 2 hours, and centrifuged. The obtained solid product was dried at 80 C. for 12 hours, and the dried solid was calcined at 330 C. for 4 hours. The solid was reduced for 4 hours at 250 C. under a pure H.sub.2 atmosphere of 0.1 MPa at a space velocity of 8000 h.sup.1, and then carbonized for 6 hours at 250 C. under a CO atmosphere of 0.1 MPa at a space velocity of 8000 h.sup.1. FIG. 1 shows an X-ray diffraction pattern. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 240 C., under 0.1 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

Example 2

[0059] Cobalt nitrate and manganese nitrate were fully dissolved in water by stirring at a molar ratio of cobalt nitrate:manganese nitrate:water=1:5:25, to obtain a first solution. Sodium carbonate was fully dissolved in water by stirring at a molar ratio of sodium carbonate:water=1:25, to obtain a second solution. A certain amount of deionized water is prepared according to a weight ratio of cobaltwater=1:100. Both the first solution and the second solution were added dropwise to the deionized water at a precipitation temperature of 30 C. and pH controlled to 8. After addition, it was crystallized at a temperature of 30 C. for 4 hours, and centrifuged. The obtained solid product was dried at 80 C. for 10 hours, and the dried solid was calcined at 330 C. for 3 hours. The solid was reduced for 5 hours at 300 C. under a 10% H.sub.2/Ar atmosphere of 1 MPa at a space velocity of 8000 h.sup.1, and then carbonized for 8 hours at 250 C. under a CO atmosphere of 0.1 MPa at a space velocity of 8000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=10 as a raw gas at 260 C., under 0.1 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

Example 3

[0060] Cobalt acetate was fully dissolved in water by stirring at a molar ratio of cobalt acetate:water=1:25, to obtain a first solution. Sodium carbonate was fully dissolved in water by stirring at a molar ratio of sodium carbonate:water=1:1000, to obtain a second solution. A certain amount of deionized water is prepared according to a weight ratio of cobalt:water=1:20. Both the first solution and the second solution were added dropwise to the deionized water at a precipitation temperature of 60 C. and pH controlled to 8. After addition, it was crystallized at a temperature of 180 C. for 2 hours, and centrifuged. The obtained solid product was dried at 80 C. for 12 hours, and the dried solid was calcined at 330 C. for 4 hours. The solid was reduced for 4 hours at 250 C. under a pure H.sub.2 atmosphere of 10 MPa at a space velocity of 10000 h.sup.1, and then carbonized for 6 hours at 250 C. under a CO atmosphere of 0.1 MPa at a space velocity of 8000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=0.1 as a raw gas at 240 C., under 0.1 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

Example 4

[0061] Cobalt formate was fully dissolved in water by stirring at a molar ratio of cobalt formate:water=1:50, to obtain a first solution. Sodium carbonate was fully dissolved in water by stirring at a molar ratio of sodium carbonate:water=1:500, to obtain a second solution. A certain amount of deionized water is prepared according to a weight ratio of cobalt:water=1:1000. Both the first solution and the second solution were added dropwise to the deionized water at a precipitation temperature of 60 C. and pH controlled to 8. After addition, it was crystallized at a temperature of 60 C. for 2 hours, and centrifuged. The obtained solid product was dried at 80 C. for 12 hours, and the dried solid was calcined at 330 C. for 4 hours. The solid was reduced for 4 hours at 250 C. under a pure H.sub.2 atmosphere of 0.1 MPa at a space velocity of 8000 h.sup.1, and then carbonized for 6 hours at 250 C. under a CO atmosphere of 10 MPa at a space velocity of 10000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=1:3 as a raw gas at 240 C., under 0.1 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

Example 5

[0062] Cobalt nitrate was fully dissolved in water by stirring at a molar ratio of cobalt nitrate:water=1:25, to obtain a first solution. Potassium hydroxide was fully dissolved in water by stirring at a molar ratio of potassium hydroxide:water=1:1, to obtain a second solution. A certain amount of deionized water is prepared according to a weight ratio of cobalt:water=1:500. Both the first solution and the second solution were added dropwise to the deionized water at a precipitation temperature of 60 C. and pH controlled to 8. After addition, it was crystallized at a temperature of 60 C. for 2 hours, and centrifuged. The obtained solid product was dried at 80 C. for 12 hours, and the dried solid was calcined at 330 C. for 4 hours. The solid was reduced for 4 hours at 250 C. under a pure H.sub.2 atmosphere of 0.1 MPa at a space velocity of 8000 h.sup.1, and then carbonized for 6 hours at 250 C. under a CO atmosphere of 5 MPa at a space velocity of 8000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=3 as a raw gas at 240 C., under 0.1 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

Example 6

[0063] Cobalt nitrate was fully dissolved in water by stirring at a molar ratio of cobalt nitrate:water=1:50 AM, to obtain a first solution. Sodium hydroxide was fully dissolved in water by stirring at a molar ratio of sodium hydroxide:water=1:75, to obtain a second solution. A certain amount of deionized water is prepared according to a weight ratio of cobalt:water=1:50. Both the first solution and the second solution were added dropwise to the deionized water at a precipitation temperature of 60 C. and pH controlled to 8. After addition, it was crystallized at a temperature of 60 C. for 2 hours, and centrifuged. The obtained solid product was dried at 80 C. for 12 hours, and the dried solid was calcined at 330 C. for 5 hours. The solid was reduced for 4 hours at 250 C. under a pure H.sub.2 atmosphere of 5 MPa at a space velocity of 8000 h.sup.1, and then carbonized for 4 hours at 250 C. under a CO atmosphere of 0.1 MPa at a space velocity of 8000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 250 C., under 0.1 MPa, and at a space velocity of 40000 h.sup.1. The experimental results are shown in Table 1.

Example 7

[0064] Cobalt nitrate was fully dissolved in water by stirring at a molar ratio of cobalt nitrate:water=1:50 AM, to obtain a first solution. Ammonium carbonate was fully dissolved in water by stirring at a molar ratio of ammonium carbonate:water=1:100, to obtain a second solution. A certain amount of deionized water is prepared according to a weight ratio of cobalt:water=1:900. Both the first solution and the second solution were added dropwise to deionized water at a precipitation temperature of 80 C. and a pH controlled to 8. After addition, it was crystallized at a temperature of 60 C. for 2 hours, and centrifuged. The obtained solid product was dried at 80 C. for 12 hours, and the dried solid was calcined at 330 C. for 5 hours. The solid was reduced for 4 hours at 250 C. under a pure H.sub.2 atmosphere of 1 MPa at a space velocity of 8000 h.sup.1, and then carbonized for 12 hours at 250 C. under a CO atmosphere of 1 MPa at a space velocity of 8000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 230 C., under 0.1 MPa, and at a space velocity of 500 h.sup.1. The experimental results are shown in Table 1.

Example 8

[0065] Cobalt nitrate was fully dissolved in water by stirring at a molar ratio of cobalt nitrate:water=1:50 AM, to obtain a first solution. Sodium bicarbonate was fully dissolved in water by stirring at a molar ratio of sodium bicarbonate:water=1:50, to obtain a second solution. A certain amount of deionized water is prepared according to a weight ratio of cobalt:water=1:80. Both the first solution and the second solution were added dropwise to deionized water at a precipitation temperature of 80 C. and pH controlled to 9. After addition, it was crystallized at a temperature of 60 C. for 2 hours, and centrifuged. The obtained solid product was dried at 80 C. for 12 hours, and the dried solid was calcined at 330 C. for 5 hours. The solid was reduced for 4 hours at 250 C. under a pure H.sub.2 atmosphere of 0.1 MPa at a space velocity of 8000 h.sup.1, and then carbonized for 6 hours at 300 C. under a CO atmosphere of 10 MPa at a space velocity of 8000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 250 C., under 0.1 MPa, and at a space velocity of 1000 h.sup.1. The experimental results are shown in Table 1.

Example 9

[0066] Cobalt nitrate and lanthanum nitrate were fully dissolved in water by stirring at a molar ratio of cobalt nitrate:lanthanum nitrate:water=1:0.5:25, to obtain a first solution. Sodium carbonate was fully dissolved in water by stirring at a molar ratio of sodium carbonate:water=1:50, to obtain a second solution. A certain amount of deionized water is prepared according to a weight ratio of cobalt:water=1:10. Both the first solution and the second solution were added dropwise to the deionized water at a precipitation temperature of 20 C. and a pH controlled to 7.5. After addition, it was crystallized at a temperature of 60 C. for 4 hours, and centrifuged. The obtained solid product was dried at 80 C. for 10 hours, and the dried solid was calcined at 330 C. for 3 hours. The solid was reduced for 5 hours at 500 C. under a 10% H.sub.2/Ar atmosphere of 1 MPa at a space velocity of 8000 h.sup.1, and then carbonized for 6 hours at 350 C. under a CO atmosphere of 2 MPa at a space velocity of 8000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 270 C., under 0.1 MPa, and at a space velocity of 100000 h.sup.1. The experimental results are shown in Table 1.

Example 10

[0067] Cobalt nitrate and cerium nitrate were fully dissolved in water by stirring at a molar ratio of cobalt nitrate:cerium nitrate:water=1:0.3:25, to obtain a first solution. Sodium carbonate was fully dissolved in water by stirring at a molar ratio of sodium carbonate:water=1:800, to obtain a second solution. A certain amount of deionized water is prepared according to a weight ratio of cobalt:water=1:110. Both the first solution and the second solution were added dropwise to the deionized water at a precipitation temperature of 30 C. and pH controlled to 8. After addition, it was crystallized at a temperature of 60 C. for 4 hours, and centrifuged. The obtained solid product was dried at 80 C. for 10 hours, and the dried solid was calcined at 330 C. for 4 hours. The solid was reduced for 5 hours at 300 C. under a 10% H.sub.2/Ar atmosphere of 3 MPa at a space velocity of 500 h.sup.1, and then carbonized for 12 hours at 350 C. under a CO atmosphere of 8 MPa at a space velocity of 8000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 260 C., under 10 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

Example 11

[0068] Cobalt nitrate and ammonium meta-vanadate were fully dissolved in water by stirring at a molar ratio of cobalt nitrate:ammonium meta-vanadate:water=1:0.1:1000, to obtain a first solution. Sodium carbonate was fully dissolved in water by stirring at a molar ratio of sodium carbonate:water=1:1000, to obtain a second solution. A certain amount of deionized water is prepared according to a weight ratio of cobaltwater=1:100. Both the first solution and the second solution were added dropwise to the deionized water at a precipitation temperature of 20 C. and pH controlled to 8. After addition, it was crystallized at a temperature of 60 C. for 2 hours, and centrifuged. The obtained solid product was dried at 80 C. for 10 hours, and the dried solid was calcined at 330 C. for 4 hours. The solid was reduced for 1 hour at 300 C. under a 10% H.sub.2/Ar atmosphere of 8 MPa at a space velocity of 8000 h.sup.1 and then carbonized for 12 hours at 300 C. under a CO atmosphere of 0.1 MPa at a space velocity of 8000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 150 C., under 0.1 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

Example 12

[0069] Cobalt nitrate and potassium chromate were fully dissolved in water by stirring at a molar ratio of cobalt nitrate:potassium chromate:water=1:0.3:1, to obtain a first solution. Sodium carbonate was fully dissolved in water by stirring at a molar ratio of sodium carbonate:water=1:50, to obtain a second solution. A certain amount of deionized water is prepared according to a weight ratio of cobalt:water=1:50. Both the first solution and the second solution were added dropwise to the deionized water at a precipitation temperature of 30 C. and pH controlled to 8. After addition, it was crystallized at a temperature of 60 C. for 5 hours, and centrifuged. The obtained solid product was dried at 80 C. for 10 hours, and the dried solid was calcined at 330 C. for 5 hours. The solid was reduced for 24 hours at 100 C. under a 10% H.sub.2/Ar atmosphere of 5 MPa at a space velocity of 8000 h.sup.1, and then carbonized for 6 hours at 400 C. under a CO atmosphere of 7 MPa at a space velocity of 8000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 240 C., under 0.1 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

Example 13

[0070] Cobalt nitrate and lanthanum nitrate were fully dissolved in water by stirring at a molar ratio of cobalt nitrate:lanthanum nitrate:water=1:10:100, to obtain a first solution. Sodium carbonate was fully dissolved in water by stirring at a molar ratio of sodium carbonate:water=1:50 AM, to obtain a second solution. A certain amount of deionized water is prepared according to a weight ratio of cobaltwater=1:100. Both the first solution and the second solution were added dropwise to the deionized water at a precipitation temperature of 15 C. and a pH controlled to 7.5. After addition, it was crystallized at a temperature of 70 C. for 6 hours, and centrifuged. The obtained solid product was dried at 80 C. for 10 hours, and the dried solid was calcined at 300 C. for 5 hours. The solid was reduced for 5 hours at 600 C. under a H.sub.2 atmosphere of 0.1 MPa at a space velocity of 8000 h.sup.1, and then carbonized for 6 hours at 250 C. under a 10% CO/He atmosphere of 7 MPa at a space velocity of 8000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 500 C., under 0.1 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

Example 14

[0071] Cobalt nitrate and magnesium chloride were fully dissolved in water by stirring at a molar ratio of cobalt nitrate:magnesium chloride:water=1:0.2:100, to obtain a first solution. Sodium carbonate was fully dissolved in water by stirring at a molar ratio of sodium carbonate:water=1:50, to obtain a second solution. A certain amount of deionized water is prepared according to a weight ratio of cobalt:water=1:80. Both the first solution and the second solution were added dropwise to the deionized water at a precipitation temperature of 25 C. and pH controlled to 9. After addition, it was crystallized at a temperature of 70 C. for 6 hours, and centrifuged. The obtained solid product was dried at 80 C. for 10 hours, and the dried solid was calcined at 300 C. for 5 hours. The solid was reduced for 5 hours at 300 C. under a H.sub.2 atmosphere of 10 MPa at a space velocity of 8000 h.sup.1, and then carbonized for 72 hours at 300 C. under a 10% CO/He atmosphere of 0.1 MPa at a space velocity of 500 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 260 C., under 0.1 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

Example 15

[0072] 1) Cobalt acetate and cerium nitrate were fully dissolved in water by stirring at a molar ratio of cobalt acetate:cerium nitrate:water=1:5:50, to obtain a first solution. Ammonium carbonate was fully dissolved in water by stirring at a molar ratio of ammonium carbonate:water=1:100, to obtain a second solution. 2) Zirconia was stirred uniformly in water according to a weight ratio of zirconia:cobalt:water=1:0.05:10. Both the first solution and the second solution obtained in Step 1) were added dropwise to the solution obtained in Step 2) at a precipitation temperature of 90 C. and pH controlled to 9. After addition, it was crystallized at a temperature of 150 C. for 72 hours, and filtered or centrifuged. The obtained solid product was dried at 80 C. for 48 hours, and then calcined at 500 C. for 4 hours. The solid was reduced for 5 hours at 300 C. under a pure H.sub.2 atmosphere of 10 MPa at a space velocity of 4000 h.sup.1, and then carbonized for 12 hours at 250 C. under a 10% CO/He atmosphere of 10 MPa at a space velocity of 8000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 270 C., under 0.1 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

Example 16

[0073] 1) Cobalt chloride and lanthanum nitrate were fully dissolved in water by stirring at a molar ratio of cobalt chloride:lanthanum nitrate:water=1:2:100, to obtain a first solution. Potassium carbonate was fully dissolved in water by stirring at a molar ratio of potassium carbonate:water=1:50, to obtain a second solution. 2) Activated carbon was stirred uniformly in water according to a weight ratio of carbon:cobaltwater=1:0.3:1000. Both the first solution and the second solution obtained in Step 1) were added dropwise to the solution obtained in Step 2) at a precipitation temperature of 50 C. and a pH controlled to 7.5. After addition, it was crystallized at a temperature of 100 C. for 10 hours, and centrifuged. The obtained solid product was dried at 120 C. for 48 hours, and the dried solid was calcined at 300 C. for 4 hours. The solid was reduced for 5 hours at 300 C. under a 10% H.sub.2/Ar atmosphere of 6 MPa at a space velocity of 8000 h.sup.1, and then carbonized for 1 hour at 100 C. under a 10% CO/He atmosphere of 0.1 MPa at a space velocity of 2000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 240 C., under 0.1 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

Example 17

[0074] 1) Cobalt nitrate and magnesium nitrate were fully dissolved in water by stirring at a molar ratio of cobalt nitrate:magnesium nitrate:water=1:1:50, to obtain a first solution. Ammonium carbonate was fully dissolved in water by stirring at a molar ratio of ammonium carbonate:water=1:100, to obtain a second solution. 2) Silica was stirred uniformly in water according to a weight ratio of silica:cobalt:water=1:1:1. Both the first solution and the second solution obtained in Step 1) were added dropwise to the solution obtained in Step 2) at a precipitation temperature of 0 C. and pH controlled to 7. After addition, it was crystallized at a temperature of 120 C. for 12 hours, and filtered or centrifuged. The obtained solid product was dried at 80 C. for 24 hours, and then calcined at 400 C. for 6 hours. The solid was reduced for 12 hours at 400 C. under a pure H.sub.2 atmosphere of 2 MPa at a space velocity of 2000 h.sup.1, and then carbonized for 6 hours at 500 C. under a 10% CO/He atmosphere of 2 MPa at a space velocity of 2000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 300 C., under 0.1 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

Example 18

[0075] 1) Cobalt acetate was fully dissolved in water by stirring at a molar ratio of cobalt acetate:water=1:25, to obtain a first solution. Potassium hydroxide was fully dissolved in water by stirring at a molar ratio of potassium hydroxide:water=1:25, to obtain a second solution. 2) Titania was stirred uniformly in water according to a weight ratio of titania:cobalt:water=1:0.4:800. Both the first solution and the second solution obtained in Step 1) were added dropwise to the solution obtained in Step 2) at a precipitation temperature of 90 C. and pH controlled to 10. After addition, it was crystallized at a temperature of 80 C. for 72 hours, and centrifuged. The obtained solid product was dried at 60 C. for 48 hours, and the dried solid was calcined at 330 C. for 12 hours. The solid was reduced for 8 hours at 400 C. under a 10% H.sub.2/Ar atmosphere of 0.1 MPa at a space velocity of 8000 h.sup.1, and then carbonized for 6 hours at 250 C. under a 10% CO/He atmosphere of 2 MPa at a space velocity of 100,000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 200 C., under 0.1 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

Example 19

[0076] 1) Cobalt nitrate was fully dissolved in water by stirring at a molar ratio of cobalt nitrate:water=1:35, to obtain a first solution. Potassium carbonate was fully dissolved in water by stirring at a molar ratio of potassium carbonate:water=1:25, to obtain a second solution. 2) Alumina was stirred uniformly in water according to a weight ratio of alumina:cobalt:water=1:0.8:1000. Both the first solution and the second solution obtained in Step 1) were added dropwise to the solution obtained in Step 2) at a precipitation temperature of 90 C. and pH controlled to 9. After addition, it was crystallized at a temperature of 80 C. for 72 hours, and centrifuged. The obtained solid product was dried at 80 C. for 48 hours, and the dried solid was calcined at 330 C. for 12 hours. The solid was reduced for 8 hours at 400 C. under a 10% CO/Ar atmosphere of 0.1 MPa at a space velocity of 8000 h.sup.1, and then carbonized for 18 hours at 320 C. under a 10% CO/He atmosphere of 5 MPa at a space velocity of 8000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 200 C., under 0.1 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

Example 20

[0077] 1) Cobalt nitrate was fully dissolved in water by stirring at a molar ratio of cobalt nitrate:water=1:40, to obtain a first solution. Potassium carbonate was fully dissolved in water by stirring at a molar ratio of potassium carbonate:water=1:30, to obtain a second solution. 2) Alumina was stirred uniformly in water according to a weight ratio of alumina:cobalt:water=1:1:500. Both the first solution and the second solution obtained in Step 1) were added dropwise to the solution obtained in Step 2) at a precipitation temperature of 90 C. and a pH controlled to 9. After addition, it was crystallized at a temperature of 80 C. for 72 hours, and centrifuged. The obtained solid product was dried at 80 C. for 48 hours, and the dried solid was calcined at 330 C. for 12 hours. The solid was reduced for 8 hours at 400 C. under a 10% CO/Ar atmosphere of 0.1 MPa at a space velocity of 8000 h.sup.1, and then carbonized for 24 hours at 300 C. under a 10% CO/He atmosphere of 10 MPa at a space velocity of 8000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 200 C., under 0.1 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

Example 21

[0078] Cobalt nitrate and manganese nitrate were fully dissolved in water by stirring at a molar ratio of cobalt nitrate:manganese nitrate:water=1:0.5:25, to obtain a first solution. Sodium carbonate was fully dissolved in water by stirring at a molar ratio of sodium carbonate:water=1:25, to obtain a second solution. Both the first solution and the second solution were added dropwise to deionized water at a precipitation temperature of 30 C. and pH controlled to 8 according to a weight ratio of cobalt:water=1:800. After addition, it was crystallized at a temperature of 60 C. for 4 hours, and centrifuged. The obtained solid product was dried at 80 C. for 10 hours, and the dried solid was calcined at 330 C. for 3 hours. The solid was reduced for 5 hours at 300 C. under a 10% H.sub.2/Ar atmosphere of 7 MPa at a space velocity of 8000 h.sup.1, and then carbonized for 48 hours at 150 C. under a 10% CO/He atmosphere of 4 MPa at a space velocity of 2000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 230 C., under 1 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

Example 22

[0079] Cobalt nitrate and manganese nitrate were fully dissolved in water by stirring at a molar ratio of cobalt nitrate:manganese nitrate:water=1:0.5:25, to obtain a first solution. Sodium carbonate was fully dissolved in water by stirring at a molar ratio of sodium carbonate:water=1:25, to obtain a second solution. Both the first solution and the second solution were added dropwise to deionized water at a precipitation temperature of 30 C. and a pH controlled to 8 according to a weight ratio of cobaltwater=1:150. After addition, it was crystallized at a temperature of 60 C. for 4 hours, and centrifuged. The obtained solid product was dried at 80 C. for 10 hours, and the dried solid was calcined at 330 C. for 3 hours. The solid was reduced for 5 hours at 300 C. under a H.sub.2 atmosphere of 6 MPa at a space velocity of 8000 h.sup.1, and then carbonized for 24 hours at 400 C. under a 10% CO/He atmosphere of 0.1 MPa at a space velocity of 20,000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 240 C., under 0.5 MPa, and at a space velocity of 4000 h.sup.1. The experimental results are shown in Table 1.

Example 23

[0080] Cobalt nitrate and manganese nitrate were fully dissolved in water by stirring at a molar ratio of cobalt nitrate:manganese nitrate:water=1:0.5:25, to obtain a first solution. Sodium carbonate was fully dissolved in water by stirring at a molar ratio of sodium carbonate:water=1:25, to obtain a second solution. Both the first solution and the second solution were added dropwise to deionized water at a precipitation temperature of 30 C. and pH controlled to 8 according to a weight ratio of cobaltwater=1:250. After addition, it was crystallized at a temperature of 60 C. for 4 hours, and centrifuged. The obtained solid product was dried at 80 C. for 10 hours, and the dried solid was calcined at 330 C. for 3 hours. The solid was reduced for 5 hours at 300 C. under a H.sub.2 atmosphere of 0.1 MPa at a space velocity of 8000 h.sup.1, and then carbonized for 12 hours at 350 C. under a 10% CO/Ar atmosphere of 0.5 MPa at a space velocity of 8000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 240 C., under 0.5 MPa, and at a space velocity of 4000 h.sup.1. The experimental results are shown in Table 1.

Example 24

[0081] Cobalt nitrate and manganese nitrate were fully dissolved in water by stirring at a molar ratio of cobalt nitrate:manganese nitrate:water=1:0.5:25, to obtain a first solution. Sodium carbonate was fully dissolved in water by stirring at a molar ratio of sodium carbonate:water=1:25, to obtain a second solution. Both the first solution and the second solution were added dropwise to deionized water at a precipitation temperature of 30 C. and pH controlled to 8 according to a weight ratio of cobalt:water=1:500. After addition, it was crystallized at a temperature of 60 C. for 4 hours, and centrifuged. The obtained solid product was dried at 80 C. for 10 hours, and the dried solid was calcined at 330 C. for 3 hours. The calcined solid was subject to incipient wetness impregnation at a molar ratio of cobalt source:sodium hydroxide=1:0.001 and dried at 60 C. for 24 hours. Then, the dried solid was calcined for 3 hours at 400 C. under 0.7 MPa. The solid was reduced for 5 hours at 300 C. under a H.sub.2 atmosphere of 0.2 MPa at a space velocity of 8000 h.sup.1, and then carbonized for 6 hours at 200 C. under a 10% CO/Ar atmosphere at a space velocity of 8000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 240 C., under 1 MPa, and at a space velocity of 4000 h.sup.1. The experimental results are shown in Table 1.

Example 25

[0082] 1) Cobalt acetate and magnesium nitrate were fully dissolved in water by stirring at a molar ratio of cobalt nitrate:magnesium nitrate:water=1:1:10, to obtain a first solution. Ammonium carbonate was fully dissolved in water by stirring at a molar ratio of ammonium carbonate:water=1:200, to obtain a second solution. 2) Zirconia was stirred uniformly in water according to a weight ratio of zirconia:cobalt:water=1:0.2:10. Both the first solution and the second solution obtained in Step 1) were added dropwise to the solution obtained in Step 2) at a precipitation temperature of 90 C. and pH controlled to 9. After addition, it was crystallized at a temperature of 100 C. for 12 hours, and filtered or centrifuged. The obtained solid product was dried at 120 C. for 4 hours, and then calcined at 400 C. for 5 hours. The solid was reduced for 5 hours at 300 C. under a pure H.sub.2 atmosphere of 0.1 MPa at a space velocity of 4000 h.sup.1, and then carbonized for 48 hours at 150 C. under a 10% CO/N.sub.2 atmosphere of 0.9 MPa at a space velocity of 8000 h.sup.1. The carbonized solid was subjected to incipient wetness impregnation at a molar ratio of cobalt source:sodium carbonate=1:0.5, dried at 80 C. for 24 hours, and then calcined at 400 C. for 3 hours. The reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 270 C., under 0.1 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

Example 26

[0083] 1) Cobalt nitrate was fully dissolved in water by stirring at a molar ratio of cobalt nitrate:water=1:60, to obtain a first solution. Potassium carbonate was fully dissolved in water by stirring at a molar ratio of potassium carbonate:water=1:100, to obtain a second solution. 2) Alumina was stirred uniformly in water according to a weight ratio of alumina:cobalt:water=1:0.4:100. Both the first solution and the second solution obtained in Step 1) were added dropwise to the solution obtained in Step 2) at a precipitation temperature of 90 C. and a pH controlled to 8. After addition, it was crystallized at a temperature of 80 C. for 72 hours, and centrifuged. The obtained solid product was dried at 80 C. for 48 hours, and the dried solid was calcined at 330 C. for 12 hours. The calcined solid was subject to incipient wetness impregnation at a molar ratio of cobalt source:lithium hydroxide=1:0.01 and dried at 100 C. for 12 hours. Then, the dried solid was calcined for 6 hours at 300 C. The solid was reduced for 8 hours at 400 C. under a 10% CO/Ar atmosphere of 0.8 MPa at a space velocity of 5000 h.sup.1 and then carbonized for 18 hours at 300 C. under a 10% CO/He atmosphere of 0.1 MPa at a space velocity of 10,000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 300 C., under 0.1 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

Example 27

[0084] 1) Cobalt nitrate was fully dissolved in water by stirring at a molar ratio of cobalt nitrate:water=1:500, to obtain a first solution. Potassium carbonate was fully dissolved in water by stirring at a molar ratio of potassium carbonate:water=1:100, to obtain a second solution. 2) Alumina was stirred uniformly in water according to a weight ratio of alumina:cobalt:water=1:0.1:100. Both the first solution and the second solution obtained in Step 1) were added dropwise to the solution obtained in Step 2) at a precipitation temperature of 90 C. and a pH controlled to 8. After addition, it was crystallized at a temperature of 0 C. for 1 hour, and centrifuged. The obtained solid product was dried at 100 C. for 48 hours, and the dried solid was calcined at 200 C. for 24 hours. The calcined solid was subject to incipient wetness impregnation at a molar ratio of cobalt source:lithium hydroxide=1:0.1 and dried at 100 C. for 12 hours. Then, the dried solid was calcined for 6 hours at 300 C. The solid was reduced for 8 hours at 400 C. under a 10% CO/Ar atmosphere of 0.8 MPa at a space velocity of 5000 h.sup.1, and then carbonized for 18 hours at 300 C. under a 10% CO/He atmosphere of 0.1 MPa at a space velocity of 10,000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 300 C., under 0.1 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

Example 28

[0085] 1) Cobalt nitrate was fully dissolved in water by stirring at a molar ratio of cobalt nitrate:water=1:40 AM, to obtain a first solution. Potassium carbonate was fully dissolved in water by stirring at a molar ratio of potassium carbonate:water=1:30, to obtain a second solution. 2) Alumina was stirred uniformly in water according to a weight ratio of alumina:cobalt:water=1:0.5:500. Both the first solution and the second solution obtained in Step 1) were added dropwise to the solution obtained in Step 2) at a precipitation temperature of 90 C. and pH controlled to 9. After addition, it was crystallized at a temperature of 200 C. for 48 hours, and centrifuged. The obtained solid product was dried at 80 C. for 48 hours, and the dried solid was calcined at 330 C. for 1 hour. The solid was reduced for 8 hours at 400 C. under a 10% CO/Ar atmosphere of 0.1 MPa at a space velocity of 8000 h.sup.1, and then carbonized for 24 hours at 300 C. under a 10% CO/He atmosphere of 10 MPa at a space velocity of 8000 h.sup.1. Reaction was carried out with syngas of H.sub.2/CO=2 as a raw gas at 200 C., under 0.1 MPa, and at a space velocity of 2000 h.sup.1. The experimental results are shown in Table 1.

TABLE-US-00001 TABLE 1 Catalytic results in the presence of catalysts in the examples Selectivity Selectivity to to methane olefins CO among among Olefin product Ex- conversion hydro- hydro- distribution (C %) pamle rate carbons carbons C.sub.2 C.sub.3 C.sub.4 C.sub.5+ No (C %) (C %) (C %) olefin olefin olefin olefins 1 8 15 76 13 55 16 16 2 58 6 81 28 22 23 27 3 5 16 69 18 57 23 2 4 10 18 74 16 38 24 22 5 3 20 72 22 29 28 21 6 7 18 68 18 35 25 22 7 12 15 81 13 38 26 23 8 20 10 67 18 36 26 20 9 32 23 73 15 42 25 18 10 28 21 78 19 35 25 21 11 22 19 79 22 40 20 18 12 35 30 80 31 32 21 16 13 27 25 83 43 21 19 17 14 45 19 72 28 43 18 11 15 38 11 75 17 39 23 21 16 32 12 81 21 36 23 20 17 12 19 65 30 35 18 17 18 29 20 82 30 41 16 13 19 33 21 79 21 35 23 21 20 18 19 59 16 35 28 21 21 52 4 86 21 42 19 18 22 45 8 79 15 37 24 24 23 38 12 84 18 37 26 19 24 42 16 76 23 41 26 10 25 23 23 82 23 51 18 8 26 61 43 32 50 31 11 8 27 20 31 60 32 25 28 15 28 30 15 80 22 35 24 19

[0086] As shown in Table 1, the present catalyst can be effectively used in the direct production of olefins from syngas, and has high catalytic activity, high selectivity to olefins and low selectivity to methane.

[0087] While preferred embodiments of the present invention have been described above, the present invention is not limited thereto in any way. It should be appreciated that some improvements and variations can be made by those skilled in the art without departing from the technical principles of the present invention, which are also contemplated to be within the scope of the present invention. Equivalent changes, modifications, and evolutions can be made by those skilled in the art based on the disclosure herein without departing from the spirit and scope of the present invention, which constitute equivalent embodiments of the present invention. Moreover, any equivalent changes, modifications, and evolutions made to the embodiments according to the technical essence of the present invention are still within the scope of the present invention.