Fischer-tropsch catalyst, preparation method and application thereof

Abstract

A micro-spherical iron-based catalyst and a preparation method thereof are disclosed. The catalyst contains a potassium promoter, and at least one transitional metal promoter M which is one or more kinds of metals selected from Cr, Cu, Mn and Zn. It also contains a structure promoter S, which is SiO.sub.2 and/or Al.sub.2O.sub.3, wherein both of SiO.sub.2 and Al.sub.2O.sub.3 are modified by MoO.sub.3, TiO.sub.2 and/or ZrO.sub.2. The weight ratio of components is Fe:M:K:S=100:3-50:1-8:3-50, in which the metal components are calculated based on metal elements, the structure promoter is calculated based on oxides. The catalyst is prepared by co-precipitation method.

Claims

1. A micro-spherical iron-based catalyst for Fischer-Tropsch synthesis in a high temperature slurry bed reactor, the catalyst including Fe element as a main active component, the catalyst comprising: a K promoter, a transitional metal promoter M, and a structure promoter S, wherein the transitional metal promoter M is any combination of two or more kinds of metals selected from the group consisting of Cr, Cu, Mn and Zn; the structure promoter S is selected from the group consisting of SiO2 and Al2O3, wherein the SiO2 and Al2O3 are modified by at least one of MoO3, TiO2 and ZrO2; and the Fe element, K promoter, transitional metal promoter M, and structure promoter S have a respective weight ratio of Fe:M:K:S=100:1-100:6-8:1-80, wherein the Fe element and the transitional metal promoter M are calculated based on metal elements, and the structure promoter S is calculated based on oxides.

2. The iron-based catalyst according to claim 1, wherein the weight ratio of each component is Fe:M:K:S=100:14.5-50:6-8:3-50.

3. The iron-based catalyst according to claim 2, wherein the transitional metal promoter M is any combination of three or four kinds of metals selected from the group consisting of Cr, Cu, Mn, and Zn.

4. The iron-based catalyst according to claim 1, wherein the weight ratio of each component in the structure promoter S is (at least one of MoO3, TiO2 and ZrO2):(at least one of SiO2 and Al2O3)=1-50:100.

5. The iron-based catalyst according to claim 4, wherein the weight ratio of each component in the structure promoter S is (at least one of MoO3, TiO2 and ZrO2):(at least one of SiO2 and Al2O3)=1-30:100.

6. The iron-based catalyst according to claim 5, wherein, in the structure promoter S, two or three kinds of components selected from the group consisting of MoO3, TiO2 and ZrO2 exist simultaneously.

7. A method of preparing the iron-based catalyst of claim 6 comprising: (1) preparing a solution of metal nitrates by using metal Fe, the transition metal promoter M and nitric acid as raw materials; or preparing a mixed solution of metal nitrates by directly dissolving the metal nitrates of the mixed solution; the solution of the metal nitrates is in a total concentration of 5-45 wt %; and adding the structure promoter S into the solution of metal nitrates; (2) co-precipitating the solution of metal nitrates prepared in step (1) to produce a precipitated slurry by using ammonium water in a concentration of 1-25 wt % as a precipitant, wherein the precipitation temperature is 20-95 C.; during the co-precipitation, maintaining a pH value between 6.0-9.5; and aging the precipitated slurry after precipitation, thereby obtaining a final pH value of the precipitated slurry of 5-10; (3) washing and filtering the precipitated slurry prepared in step (2) to obtain a filter cake with a solid content of 5-60 wt %; (4) adding potassium salt as the K promoter and deionized water into the filter cake, pulping to obtain a slurry, and adjusting the pH value of the slurry to 4-10, then emulsifying the slurry to obtain a catalyst slurry with a solid content of 3-50 wt %; (5) molding the catalyst slurry prepared in step (4) by spray-drying the catalyst slurry in a pressurized spray-drying tower, and roasting the molded catalyst to obtain the catalyst; wherein the addition of the structure promoter S in step (1) is changed to be performed in step (4); or respectively adding part of the structure promoter S in steps (1) and (4).

8. The method according to claim 7, wherein the structure promoter S is added by respectively adding part of the structure promoter S in steps (1) and (4), and the weight ratio of Fe to the structure promoter S in the solution of metal nitrates is not less than 100/25 after the addition of the structure promoter S in step (1).

9. The method according to any one of claims 7-8, wherein the raw material of the structure promoter S is silica sol, potash water glass, and/or alumina sol.

10. The method according to any one of claims 7-8, wherein the mixed solution of metal nitrates in step (1) is prepared by metal nitrates.

11. The method according to any one of claims 7-8, wherein, in step (2), the precipitant of ammonia water is in the concentration of 5-20 wt %, and/or the precipitation temperature is 50-90 C.

12. The method according to claim 11, wherein, in step (3), the filter cake obtained by washing and filtering the precipitated slurry contains less than 2.5 wt % ammonium nitrate, and/or the solid content in the filter cake is 15-50 wt %.

13. The method according to claim 12, wherein, the potassium salt in step (4) is at least one member selected from the group consisting of potassium bicarbonate, potassium acetate, organic sylvite and potash water glass; and/or the pH value of the slurry in step (4) is 5.0-9.5; and the solid content in the catalyst slurry is 10-40 wt %.

14. Using the Fe-based catalyst according to any one of claims 1-5 in the Fischer-Tropsch synthesis reaction, wherein the Fischer-Tropsch synthesis reaction is carried out in a slurry bed at a temperature range of 240-280 C.

Description

EXAMPLES

(1) The technical solutions of the present invention will be described in detail according to the following examples which are not intended to limit the protection scope of the present invention in any way.

Example 1

(2) 282.11 kg of iron ingot, 2.78 kg of zinc, 2.78 kg of electrolytic chromium flake, and 2.80 kg of electrolytic copper were weighed and dissolved with nitric acid to prepare a mixed solution of the nitrates with a total concentration of 10.18 wt % for later use. The weight ratio of each component was Fe:Cr:Cu:Zn=100:1.00:1.00:1.01.

(3) 24.0 kg of silica sol, 4.6 kg of alumina sol, 125 g of zirconium nitrate, 86 g of titanium tetrachloride, and 42 g of ammonium molybdate and a small amount of water were weighed, then mixed and well dissolved. The resultant mixed sol was washed with deionized water until the content of Cl.sup. ion could not be detected. The weight ratio of each component in the mixed sol was SiO.sub.2:Al.sub.2O.sub.3:ZrO.sub.2:TiO.sub.2:MoO.sub.3=100:13.33:0.50:0.50:0.50, and the solid content of the mixed sol was 33 wt %.

(4) 25.49 kg of the above mixed sol was taken, then added into the above mixed solution of the nitrates and stirred well, and then heated to 90 C.; a certain amount of ammonia water in a concentration of 5.5 wt % was taken and preheated to 60 C., and then co-precipitated with the above-mentioned mixed solution by continuous coflowing process at a temperature of 90 C. and a pH value of 6.0 under stirring, in which the amount of ammonia water was determined based on the conditions that the solution was completely precipitated and the pH of the slurry was maintained at 6.0; the obtained precipitated slurry was aged for 5 minutes after precipitation and then washed with deionized water until the content of NH.sub.4NO.sub.3 in the slurry was less than 0.1 wt %, and a filter cake was obtained with a solid content of 16.5 wt % after the precipitated being filtered.

(5) Adding a certain amount of deionized water and 8.5 kg of potassium bicarbonate into the above obtained filter cake, then sufficiently pulping to obtain a slurry, and adjusting the pH value of the slurry to 6.5 and the solid content of the slurry to 10.5 wt %; spray-drying the above-prepared slurry materials in a pressurized spray-drying tower with an air inlet temperature of 420 C. and an air outlet temperature of 85 C.; roasting the dried spherical catalyst at 700 C. for 2 hours to obtain the desired catalyst of 772 kg. The weight ratio of each component in the catalyst was Fe:M:K:S=100:3.01:1.20:3.04. This catalyst was designated as A.

Example 2

(6) 2000.0 kg of iron nitrate, 213.0 kg of chromium nitrate, 15.8 kg of copper nitrate, and 360.0 kg of 50 wt % manganese nitrate solution were weighed and dissolved in 1500 kg of deionized water to obtain a mixed solution of the nitrates with a total concentration of 37.08 wt % for later use. The weight ratio of each component was Fe:Mn:Cr:Cu=100:20.0:10.0:1.50.

(7) 400.0 kg of silica sol, 5.0 kg of alumina sol, 25.1 kg of zirconium nitrate, 14.25 kg of titanium tetrachloride, 4.15 kg of ammonium molybdate, and an appropriate amount of deionized water were weighed, then mixed and well dissolved. The mixed sol was washed with deionized water until the content of Cl.sup. ion could not be detected. The weight ratio of each component in the mixed sol was SiO.sub.2:Al.sub.2O.sub.3:ZrO.sub.2:TiO.sub.2:MoO.sub.3=100:1.0:6.0:5.0:3.0, and the solid content was 25.07 wt %.

(8) 165.54 kg of the above mixed sol was taken, then added into the above mixed solution of the nitrates and stirred well, and then heated to 50 C.; a certain amount of ammonia water in a concentration of 19.6 wt % was taken and preheated to 20 C., and then co-precipitated with the above mixed solution by continuous coflowing process at a temperature of 50 C. and a pH value of 9.5 under stirring, in which the amount of ammonia water was determined based on the conditions that the solution was completely precipitated and the pH of the slurry was maintained at 9.5; the obtained precipitated slurry was aged for 120 minutes after precipitation and then washed with deionized water until the content of NH.sub.4NO.sub.3 in the slurry was less than 0.5 wt %, and a filter cake with a solid content of 51.2 wt % was obtained after the precipitated slurry being filtered.

(9) Adding a certain amount of deionized water and 55.5 kg of potassium acetate and 384.91 kg of the above obtained mixed sol into the filter cake, then sufficiently pulping to obtain a slurry, and adjusting the pH value of the slurry to 5.2 and the solid content of the slurry to 38.20 wt %; spray-drying the above-prepared slurry materials in a pressurized spray drying tower with an air inlet temperature of 180 C. and an air outlet temperature of 90 C.; roasting the dried spherical catalyst at 550 C. for 4 hours to obtain the desired catalyst of 645 kg. The weight ratio of each component in the catalyst was Fe:M:K:S=100:31.5: 8.0:49.91. This catalyst was designated as B.

Example 3

(10) 2000.0 kg of iron nitrate, 125.8 kg of zinc nitrate, 21.0 kg of copper nitrate, and 684.4 kg of 50 wt % manganese nitrate solution were weighed and dissolved in 8000 kg of deionized water to obtain a mixed solution of the nitrates with a total concentration of 15.10 wt % for later use. The weight ratio of each component was Fe:Mn:Zn:Cu=100:38.0:10.0:2.0.

(11) 175.0 kg of silica sol, 7.31 kg of zirconium nitrate, 0.61 kg of ammonium molybdate, and an appropriate amount of deionized water were weighed, then mixed and well dissolved. The mixed sol was washed with deionized water until the content of Cl.sup. ion could not be detected. The weight ratio of each component in the mixed sol was SiO.sub.2:ZrO.sub.2:MoO.sub.3=100:4.0:1.0, and the solid content was 23.15 wt %.

(12) The above mixed solution of the nitrates was heated to 80 C.; a certain amount of ammonia water in a concentration of 10.0 wt % was taken and preheated to 50 C., and then co-precipitated with the above-mentioned mixed solution of the nitrates by continuous coflowing process at a temperature of 80 C. and a pH value of 8.5 under stirring, in which the amount of ammonia water was determined based on the conditions that the solution was completely precipitated and the pH of the slurry was maintained at 8.5; the obtained precipitated slurry was aged for 10 minutes after precipitation, and then washed with deionized water until the content of NH.sub.4NO.sub.3 in the slurry was less than 0.2 wt %, and a filter cake with a solid content of 38.5 wt % was obtained after the precipitated slurry being filtered.

(13) Adding a certain amount of deionized water, 19.53 kg of potassium carbonate and 238.13 kg of the above obtained mixed sol into the filter cake, then sufficiently pulping to obtain a slurry, and adjusting the pH value of the slurry to 9.2 and the solid content of the slurry to 28.90 wt %; spray-drying the above-prepared slurry materials in a pressurized spray-drying tower with an air inlet temperature of 270 C. and an air outlet temperature of 110 C.; roasting the dried spherical catalyst at 450 C. for 5 hours to obtain the desired catalyst of 628 kg. The weight ratio of each component in the catalyst was Fe:M:K:S=100:50.0:4.0:19.94. This catalyst was designated as C.

Example 4

(14) 2000.0 kg of iron nitrate, 10.65 kg of chromium nitrate, 125.0 kg of zinc nitrate, and 180.0 kg of 50 wt % manganese nitrate solution were weighed and dissolved in 2000 kg of deionized water to obtain a mixed solution of the nitrates with a total concentration of 31.82 wt % for later use. The weight ratio of each component was Fe:Mn:Zn:Cr=100:10.0:10.0:0.5.

(15) 130.0 kg of alumina sol, 3.26 kg of zirconium nitrate, 0.75 kg of titanium tetrachloride, 1.80 kg of ammonium molybdate, and an appropriate amount of deionized water were weighed, then mixed and well dissolved. The mixed sol was washed with deionized water until the content of Cl.sup. ion could not be detected. The weight ratio of each component in the mixed sol was Al.sub.2O.sub.3:ZrO.sub.2:TiO.sub.2:MoO.sub.3=100:3.0:1.0:4.0, and the solid content was 28.70 wt %.

(16) 29.63 kg of the above mixed sol was taken, then added into the above mixed solution of the nitrates and stirred well, and then heated to 70 C.; a certain amount of ammonia water in a concentration of 15.2 wt % was taken and preheated to 40 C., and then co-precipitated with the above mixed solution by continuous coflowing process at a temperature of 70 C. and a pH value of 9.2 under stirring, in which the amount of ammonia water was determined based on the conditions that the solution was completely precipitated and the pH value of the slurry was maintained at 9.2; the obtained precipitated slurry was aged for 90 minutes after precipitation and then washed with deionized water until the content of NH.sub.4NO.sub.3 in the slurry was less than 0.8 wt %, and a filter cake with a solid content of 28.5 wt % was obtained after the precipitated slurry being filtered.

(17) Adding a certain amount of deionized water, 20.85 kg of potassium acetate and 88.88 kg of the above obtained mixed sol into the filter cake, then sufficiently pulping to obtain a slurry, and adjusting the pH of the slurry to 7.3 and the solid content of the slurry to 24.5 wt %; spray-drying the above-prepared slurry materials in a pressurized spray drying tower with an air inlet temperature of 280 C. and an air outlet temperature of 120 C.; roasting the dried spherical catalyst at 350 C. for 7.5 hours to obtain the desired catalyst of 490 kg, and the weight ratio of each component in the catalyst was Fe:M:K:S=100:20.5:3.0:12.30. This catalyst was designated as D.

Example 5

(18) 2000.0 kg of iron nitrate, 21.3 kg of chromium nitrate, 18.9 kg of zinc nitrate, 10.5 kg of copper nitrate, and 72.0 kg of 50 wt % manganese nitrate solution were weighed and dissolved in 3000 kg of deionized water to obtain a mixed solution of the nitrates with a total concentration of 24.72 wt % for later use. The weight ratio of each component was Fe:Mn:Zn:Cr:Cu=100:4.0:1.5:1.0:1.0.

(19) 200.0 kg of silica sol, 25.0 kg of alumina sol, 20.9 g of zirconium nitrate, 14.27 kg of titanium tetrachloride, 6.92 kg of ammonium molybdate, and an appropriate amount of deionized water were weighed, then mixed and well dissolved. The mixed sol was washed with deionized water until the content of Cl.sup. ion could not be detected. The weight ratio of each component in the mixed sol was SiO.sub.2:Al.sub.2O.sub.3:ZrO.sub.2:TiO.sub.2:MoO.sub.3=100:10.0:10.0:10.0:10.0, and the solid content was 15.49 wt %.

(20) 54.23 kg of the above mixed sol was taken and added into the above mixed solution of the nitrates and stirred well, and then heated to 60 C.; a certain amount of ammonia water in a concentration of 12.5 wt % was taken and preheated to 40 C., and co-precipitated with the above-mentioned mixed solution by continuous coflowing process at a temperature of 60 C. and a pH value of 7.3, in which the amount of ammonia water was determined based on the conditions that the solution was completely precipitated and the pH value was maintained at 7.3; the obtained precipitated slurry was aged for 15 minutes after precipitation, then washed with deionized water until the content of NH.sub.4NO.sub.3 in the slurry was less than 0.6 wt %, and a filter cake with a solid content of 39.8 wt % was obtained after the precipitated slurry being filtered.

(21) Adding a certain amount of deionized water, 42.5 kg of potassium bicarbonate and 488.1 kg of the above obtained mixed sol into the filter cake, then sufficiently pulping to obtain a slurry, and adjusting the pH of the slurry to 8.6 and the solid content of the slurry to 32.3 wt %; spray-drying the above-prepared slurry materials in a pressurized spray-drying tower with an air inlet temperature of 260 C. and an air outlet temperature of 100 C.; roasting the dried spherical catalyst at 500 C. for 6 hours to obtain the desired catalyst of 493 kg, and the weight ratio of each component in the catalyst was Fe:M:K:S=100:7.5:6.0:30.4. This catalyst was designated as E.

Example 6

(22) 2000.0 kg of iron nitrate, 10.65 kg of chromium nitrate, 6.3 kg of zinc nitrate, and 36.0 kg of 50 wt % manganese nitrate solution were weighed and dissolved in 1500 kg of deionized water to obtain a mixed solution of the nitrates with a total concentration of 34.50 wt % for later use. The weight ratio of each components was Fe:Mn:Zn:Cr=100:2.0:0.5:0.5.

(23) 370.0 kg of silica sol, 3.85 kg of zirconium nitrate, 2.65 kg of titanium tetrachloride, and an appropriate amount of deionized water were weighed, then mixed and well dissolved. The mixed sol was washed with deionized water until the content of Cl.sup. ion could not be detected. The weight ratio of each component in the mixed sol was SiO.sub.2:ZrO.sub.2:TiO.sub.2=100:1.0:1.0, and the solid content was 35.12 wt %.

(24) 161.19 kg of the above mixed sol was weighed, then added into the mixed solution of the nitrates and stirred well, and then heated to 75 C.; a certain amount of ammonia water in a concentration of 17.2 wt % was taken and preheated to 45 C., and then co-precipitated with the above-mentioned mixed solution by continuous coflowing process at a temperature of 75 C. and a pH value of 6.5 under stirring, in which the amount of ammonia water was determined based on the conditions that the solution was completely precipitated and the pH value of the slurry was maintained at 6.5; the obtained precipitated slurry was aged for 100 minutes, then washed with deionized water until the content of NH.sub.4NO.sub.3 in the slurry was less than 0.5 wt % and a filter cake with a solid content of 43.0 wt % was obtained after the precipitated slurry being washed.

(25) Adding a certain amount of deionized water, 34.2 kg of potassium carbonate and 161.19 kg of the above obtained mixed sol into the filter cake, then sufficiently pulping to obtain a slurry, and adjusting the pH value of the slurry to 8.8 and the solid content of the slurry to 21.9 wt %; spray-drying the above-prepared slurry materials in a pressurized spray-drying tower with an air inlet temperature of 320 C. and an air outlet temperature of 145 C.; roasting the dried spherical catalyst at 650 C. for 3 hours to obtain the desired catalyst of 508 kg and the weight ratio of each component in the catalyst was Fe:M:K:S=100:3.0:7.0:40.95. This catalyst was designated as F.

Example 7

(26) 2000.0 kg of iron nitrate, 106.4 kg of chromium nitrate, 18.9 kg of zinc nitrate, and 144.0 kg of 50 wt % manganese nitrate solution were weighed and dissolved in 4000 kg of deionized water to obtain a mixed solution of the nitrates with a total concentration of 21.45 wt % for later use, and the weight ratio of each components was Fe:Mn:Zn:Cr=100:8.0:1.5:5.0.

(27) 120.0 kg of silica sol, 150.0 kg of alumina sol, 1.88 kg of zirconium nitrate, 1.71 kg of titanium tetrachloride, 0.83 kg of ammonium molybdate, and an appropriate amount of deionized water were weighed, then mixed and well dissolved. The mixed sol was washed with deionized water until the content of Cl.sup. ion could not be detected. The weight ratio of each component in the mixed sol was SiO.sub.2:Al.sub.2O.sub.3:ZrO.sub.2:TiO.sub.2:MoO.sub.3=100:100:1.5:2.0:2.0 and the solid content was 27.87 wt %.

(28) The above mixed solution of the nitrates was heated to 85 C.; a certain amount of ammonia water in a concentration of 11.3 wt % was taken and preheated to 45 C., and then co-precipitated with the above-mentioned mixed solution by continuous coflowing process at a temperature of 80 C. and a pH value of 7.9 under stirring; The obtained slurry was aged for 35 minutes after precipitation, and then was washed with deionized water until the content of NH.sub.4NO.sub.3 in the slurry was less than 0.35 wt % and a filter cake with a solid content of 21.3 wt % was obtained after the precipitated slurry being filtered.

(29) Adding a certain amount of deionized water, 24.45 kg of potassium carbonate and 265.44 kg of the above obtained mixed sol into the filter cake; then sufficiently pulping to obtain a slurry, and adjusting the pH value of the slurry to 9.4 and the solid content of the slurry to 16.3 wt %; spray-drying the above-prepared slurry materials in a pressurized spray-drying tower with an air inlet temperature of 380 C. and an air outlet temperature of 130 C.; roasting the dried spherical catalyst at 600 C. for 5 hours to obtain the desired catalyst of 510 kg and the weight ratio of each component in the catalyst was Fe:M:K:S=100:14.5:5.0:26.8. This catalyst was designated as G.

(30) The following Table 1 lists the composition and physical properties of the prepared catalysts described in the examples 1-7.

(31) TABLE-US-00001 TABLE 1 Catalyst labels Preparation conditions A B C D E F G Dispersed SiO.sub.2 100 100 100 100 100 100 and solidified Al.sub.2O.sub.3 13.33 1.00 100.00 10.00 100 sol ZrO.sub.2 0.50 6.00 4.00 3.00 10.00 1.00 1.50 composition TiO.sub.2 0.50 5.00 1.01 10.00 1.00 2.00 MoO.sub.3 0.51 3.00 1.01 4.00 10.00 2.00 Catalyst Fe 100 100 100 100 100 100 100 composition Mn 19.99 38.00 9.99 4.00 2.00 8.00 (weight Cr 1.00 10.01 0.50 1.00 0.50 5.00 ratio) Zn 1.00 10.00 9.94 1.50 0.50 1.50 Cu 1.01 1.50 2.00 1.00 K 1.20 8.00 4.00 3.00 6.00 7.00 5.00 Precipitating and the mixed sol 3.04 15.01 3.08 3.04 20.48 Molding and the mixed sol 34.90 19.94 9.23 27.35 20.48 26.76 Catalyst Concentration of salt 10.18 37.08 15.10 31.82 24.72 34.50 21.45 composition solution (wt %) Concentration of ammonia 5.5 19.60 10.00 15.20 12.50 17.20 11.30 water (wt %) Temperature of salt solution ( C.) 90 50 80 70 60 75 85 Temperature of ammonia 60 20 50 40 40 45 45 water ( C.) Preparation temperature ( C.) 90 50 80 70 60 75 80 Preparation pH value 6.0 9.5 8.5 9.2 7.3 6.5 7.9 Aging time (min) 5 120 10 90 15 100 35 Molding pH value of the slurry 6.5 5.2 9.2 7.3 8.6 8.8 9.4 and Solid content of the slurry (wt %) 10.50 38.20 28.90 24.50 32.30 21.90 16.30 roasting Air inlet temperature ( C.) 420 180 270 280 260 320 380 Air outlet temperature ( C.) 85 90 110 120 100 145 130 Roasting temperature ( C.) 700 550 450 350 500 650 600 Roasting time (h) 2 4 5 7.5 6 3 5 Structure BET specific surface area (m.sup.2/g) 108 320 230 165 180 307 132 properties and Pore volume (cm.sup.3/g) 0.29 0.57 0.40 0.35 0.38 0.53 0.33 particle size Percentage of 30-180 m 93% 97% 98% 95% 96% 96% 94%

Example 8

(32) Using the catalysts prepared in the examples 1-7, the F-T synthesis reaction was performed in the slurry bed reactor under such catalyst reduction conditions and F-T synthesis reaction conditions as follows. The catalytic parameters of the performance of these F-T reactions are listed in Table 2.

(33) Catalyst Reduction Conditions:

(34) The catalysts were reduced for 5-48 hours by using syngas as a reduction atmosphere at a temperature of 230-350 C. and a pressure of 0.1-4.0 MPa. The space velocity used was 500-10000 h.sup.1.

(35) F-T Synthesis Reaction Conditions in Slurry Bed Reactor:

(36) The F-T reaction was performed in syngas with H.sub.2/CO ratio of 0.7-3.0 at a temperature of 250-300 C. and a pressure of 1.0-5.0 MPa. The space velocity of the fresh air was 8000 to 20000 h.sup.1.

(37) The data in Table 2 demonstrate a high F-T synthesis reactivity of the catalysts according to the present invention for the F-T synthesis in a high temperature slurry bed reactor even at a high space velocity. The CO conversion was above 80% and the target hydrocarbon selectivity (C.sub.2.sub.=C.sub.4.sub.=+C.sub.5.sub.+) maintain 90 wt % or higher, while CH.sub.4 selectivity was less than 4.0%. Particularly, C.sub.5.sub.+ selectivity and yield are very high. Therefore, the catalysts according to the present invention are especially suitable for the high temperature slurry bed reactor to produce the products such as gasoline, diesel and wax from syngas.

(38) TABLE-US-00002 TABLE 2 Catalytic performance of the catalysts according to the present invention F-T synthesis Catalyst labels reactivity A B C D E F G Reaction 260 255 290 270 280 275 290 temperature CO conversion (%) 92.1 82.5 88.1 83.2 91.5 83.5 88.6 Hydrocarbon selectivity (wt %) CH.sub.4 2.9 2.3 3.2 4.0 2.7 3.6 3.5 C.sub.2~C.sub.4 6.3 8.2 7.0 7.9 7.6 5.2 6.3 C.sub.5.sup.+ 90.8 89.5 89.8 88.1 89.7 91.2 90.2 C.sub.2.sup.=~C.sub.4.sup.= + C.sub.5.sup.+ 94.3 94.1 92.8 91.9 94.0 94.4 93.2 (wt %) C.sub.2.sup.=~C.sub.4.sup.=/C.sub.2~C.sub.4 (%) 55.2 56.2 43.2 47.5 56.8 62.1 47.9 CO.sub.2 selectivity 14.3 18.8 16.4 18.2 15.7 21.2 15.4 (mol %) Yield (C.sub.5.sup.+ g/g-cat./h) 0.96 0.97 1.03 1.00 1.04 1.36 1.06

(39) It is understood that the present invention has been described in combination of the detailed description, the foregoing description is intended to illustrate but not to limit the scope of the invention. It is obvious to the skilled in the art that various modifications and improvements can be made within the scope of the present invention without departing from the spirit of the present invention. All these modifications and improvements are within the scope of the present invention.