PROMOTED CARBIDE-BASED FISCHER-TROPSCH CATALYST, METHOD FOR ITS PREPARATION AND USES THEREOF

Abstract

A precursor for a Fischer-Tropsch catalyst includes a catalyst support, cobalt or iron on the catalyst support and one or more noble metals on the catalyst support, wherein the cobalt or iron is at least partially in the form of its carbide in the as-prepared catalyst precursor, a method for preparing said precursor and the use of said precursor in a Fischer-Tropsch process.

Claims

1. A method of preparing a Fischer-Tropsch catalyst precursor comprising: depositing a solution or suspension comprising: a) at least one cobalt-containing precursor selected from cobalt benzoylacetonate, cobalt carbonate, cobalt cyanide, cobalt hydroxide, cobalt oxalate, cobalt oxide, cobalt nitrate, cobalt acetate, cobalt acetylacetonate, cobalt carbonyl or a mixture of two or more thereof; b) one or more noble metal precursors; and c) a polar organic compound; onto a catalyst support, wherein the catalyst support comprises silica and the surface of the silica is coated with a non-silicon oxide refractory solid oxide; and calcining the catalyst support onto which the solution or suspension has been deposited in an inert atmosphere.

2. The method of claim 1, further comprising drying the catalyst support onto which the solution or suspension has been deposited before the calcining.

3. The method of claim 1, wherein the solution or suspension contains no water.

4. The method of claim 1, wherein the inert atmosphere contains no oxygen.

5. The method of claim 1, wherein the polar organic compound comprises an organic amine, organic carboxylic acid or salt thereof, an ammonium salt, alcohol, phenoxide, alkoxide, amino acid, compound containing a functional group such as one more hydroxyl, amine, amide, carboxylic acid, ester, aldehyde, ketone, imine or imide groups, a hydroxyamine, trimethylamine, triethylamine, tetramethylamine chloride, tetraethyl amine chloride, or a surfactant.

6. The method of claim 1, wherein the polar organic compound comprises urea.

7. The method of claim 1, wherein the polar organic compound comprises carboxylic acid or salt or ester of the carboxylic acid.

8. The method of claim 1, wherein, during the calcining, the catalyst support reaches a maximum temperature of no more than 1000 C. at atmospheric pressure.

9. The method of claim 1, wherein, during the calcining, the temperature rises at a rate of from 0.0001 to 10 C. per minute.

10. The method of claim 1, wherein the catalyst precursor comprises from 10% to 50% cobalt based on the weight of the metal as a percentage of the total weight of the catalyst precursor.

11. The method of claim 1, wherein the non-silicon oxide refractory solid oxide is zirconia.

12. The method of claim 1, wherein the non-silicon oxide refractory solid oxide is alumina.

13. The method of claim 1, wherein the non-silicon oxide refractory solid oxide is titania.

14. The method of claim 1, wherein the catalyst precursor comprises from 0.01 to 30% of one or more noble metals based on the total weight of all noble metals present as a percentage of the total weight of the catalyst precursor.

15. The method of claim 14, wherein the noble metal is one or more of Pd, Pt, Rh, Ru, Ir, Au, Ag and Os.

16. The method of claim 1, wherein the solution or suspension comprises one or more other metal precursors as promoters or modifiers.

17. The method of claim 16, wherein the catalyst precursor comprises from 0.1 to 10% in total of one or more other metals based on the total weight of all the other metal as a percentage of the total weight of the catalyst precursor.

18. The method of claim 17, wherein the one or more other metals comprises one or more of Zr, Ti, V, Cr, Mn, Ni, Cu, Zn, Nb, Mo, Tc, Cd, Hf, Ta, W, Re, Hg, Tl, and 4f-block lanthanide.

19. The method of claim 1, wherein the catalyst precursor contains from 0.0001 to 10% carbon based on the weight of the carbon, in whatever form, in the catalyst as percentage of the total weight of the catalyst precursor.

20. The method of claim 1, further comprising the step of activating the catalyst precursor to provide a catalyst.

Description

EXAMPLE 1

[0094] 10 wt % Co, 1 wt % Zr on SiO.sub.2 Catalyst Precursor

[0095] A shaped SiO.sub.2 support was raised to a temperature of 450 C. at a rate of 2 C./min and was maintained at this temperature for 10 h prior to its impregnation. At room temperature, 10 g Co(NO.sub.3).sub.2.6H.sub.2O was mixed with 3-4 g urea in a small beaker. 0.7 g ZrO(NO.sub.3).sub.2 was dissolved completely with deionised (DI) water (the amount of DI water was determined according to pore volume or H.sub.2O adsorption of the support) in another small beaker. The solution or suspension of ZrO(NO.sub.3).sub.2 was added to the mixture of Co(NO.sub.3).sub.2.6H.sub.2O with urea. A clear solution or suspension of ZrO(NO.sub.3).sub.2, Co(NO.sub.3).sub.2.6H.sub.2O and urea was obtained after warming. The solution or suspension was added to 13 g of the support (SiO.sub.2) by the incipient wetness impregnation method and dried at about 100 C. in an oven for 12 h. The impregnated catalyst support was subjected to temperature-programmed calcination (TPC) in a static air environment as follows: heated to 130 C. at 1 C./min; maintained at this temperature for 3 h; heated to 150 C. at 0.5 C./min; maintained at this temperature for 3 h; heated to 350 C. at 0.5-1 C./min; and maintained at this temperature for 3 h. Shaped 10% Co, 1% Zr on SiO.sub.2 catalyst precursor was obtained.

EXAMPLE 2

[0096] 20 wt % Co, 2 wt % Zr on SiO.sub.a Catalyst Precursor

[0097] This was prepared as in Example 1, except that the 13 g SiO.sub.2 support was replaced by the 10 wt % Co, 1 wt % Zr on SiO.sub.2 catalyst precursor produced in Example 1.

EXAMPLE 3

[0098] 30 wt % Co, 3 wt % Zr on SiO.sub.2 Catalyst Precursor

[0099] This was prepared as in Example 1, except that the 13 g SiO.sub.2 support was replaced by the 20 wt % Co, 2 wt % Zr on SiO.sub.2 catalyst precursor produced in Example 2.

EXAMPLE 4

[0100] 10 wt % Co, 1 wt % Zr on Al.sub.2O.sub.3 Catalyst Precursor

[0101] This was prepared as in Example 1, except that 13 g SiO.sub.2 support was replaced by 13 g of Al.sub.2O.sub.3.

EXAMPLE 5

[0102] 20 wt % Co, 2 wt % Zr on Al.sub.2O.sub.3 Catalyst Precursor

[0103] This was prepared as in Example 4, except that the 13 g of Al.sub.2O.sub.3 support was replaced by the 10 wt % Co, 1 wt % Zr on Al.sub.2O.sub.3 catalyst precursor produced in Example 4.

EXAMPLE 6

[0104] 30 wt % Co, 3 wt % Zr on Al.sub.2O.sub.3 Catalyst Precursor

[0105] This was prepared as in Example 4, except that the 13 g of Al.sub.2O.sub.3 support was replaced by the 20 wt % Co, 2 wt % Zr on Al.sub.2O.sub.3 catalyst precursor produced in Example 5.

EXAMPLE 7

[0106] 30 wt % Co, 3 wt % Zr, 0.5 wt % Ru on SiO.sub.2 Catalyst Precursor

[0107] This was prepared as in Example 3, except that the solution or suspension of ZrO(NO.sub.3).sub.2, Co(NO.sub.3).sub.2 6H.sub.2O and urea was replaced by 6.7 g of 1.5 wt % Ru(NO)(NO.sub.3).sub.3 in 5 ml DI H.sub.2O.

EXAMPLE 8

[0108] 30 wt % Co, 3 wt % Zr, 0.1 wt % Ru on SiO.sub.2 Catalyst Precursor

[0109] This was prepared as in Example 7, except that 6.7 g of 1.5 wt % Ru(NO)(NO.sub.3).sub.3 was replaced by 1.3 g of 1.5 wt % Ru(NO)(NO.sub.3).sub.3.

EXAMPLES 9 and 10

[0110] 30 wt % Co, 3 wt % Zr, 0.5 wt % Ru on Al.sub.2O.sub.3 and 30 wt % Co, 3 wt % Zr, 0.1 wt % Ru on Al.sub.2O.sub.3 Catalyst Precursors

[0111] These were prepared as in Examples 7 and 8, except that the SiO.sub.2 was replaced by Al.sub.2O.sub.3.

EXAMPLE 11

[0112] Co, Zr, Ru on SiO, and Co, Zr, Ru on Al.sub.2O.sub.3 Catalyst Precursors

[0113] These were prepared as in Example 1-6, except that the solution or suspension of ZrO(NO.sub.3).sub.2, Co(NO.sub.3).sub.2.6H.sub.2O and urea was replaced by ZrO(NO.sub.3).sub.2, Co(NO.sub.3).sub.2.6H.sub.2O, Ru(NO)(NO.sub.3).sub.3 and urea.

[0114] During the processes set forth in the Examples, there was very little damage to the catalyst support, even when high loading of metals were achieved following a number of repetitions of the steps.

[0115] The catalyst precursors produced according to Examples 1 to 11 were activated by flowing H.sub.2 at GHSV of 2000H.sup.1 at a heating rate of 1 C./min to 300 C., maintained at 300 C. for 2 hours and then cooled down to 200 C., at which temperature the reaction is started.

[0116] The activated catalysts were used in a Fischer-Tropsch process using the following conditions:

TABLE-US-00002 T: 220 C., P: 17.5 bar, GHSV: 2000H.sup.1, H.sub.2/CO ratio: 2.

[0117] The results of the Fischer-Tropsch processes are shown in the Table below.

TABLE-US-00003 TABLE Catalyst 30%Co3%Zr/SiO.sub.2 30%Co3%Zr0.1%Ru/SiO.sub.2 30%Co3%Zr0.5%Ru/SiO.sub.2 30%Co3%Zr1%Ru/SiO.sub.2 CO conversion 50-60% 68% 83% 84% C.sup.5+ 40-48% 54% 66% 67% productivity

[0118] As can be seen from the results given in the Table above, use of an activated catalyst according to the invention in a Fischer-Tropsch synthesis leads to greater selectivity for hydrocarbons having five or more carbon atoms and enhanced activity.

EXAMPLE 12

[0119] 13 wt % Co, 1.3 wt % Zr on SiO.sub.2 Catalyst Precursor

[0120] A shaped SiO.sub.2 support was raised to a temperature of 450 C. at a rate of 2 C. /min and was maintained at this temperature for 10 h prior to its impregnation. At room temperature, 10 g Co(NO.sub.3).sub.2.6H.sub.2O was mixed with 3-4 g urea in a small beaker. 0.7 g ZrO(NO.sub.3).sub.2 was dissolved completely with deionised (DI) water (the amount of DI water was determined according to pore volume or H.sub.2O adsorption of the support) in another small beaker. The solution or suspension of ZrO(NO.sub.3).sub.2 was added to the mixture of Co(NO.sub.3).sub.2.6H.sub.2O with urea. A clear solution or suspension of ZrO(NO.sub.3).sub.2, Co(NO.sub.3).sub.2.6H.sub.2O and urea was obtained after warming. The solution or suspension was added to 13 g of the support (SiO.sub.2) by the incipient wetness impregnation method and dried at about 100 C. in an oven for 12 h. The impregnated catalyst support was subjected to temperature-programmed calcination (TPC) in a static air environment as follows: heated to 130 C. at 1 C./min; maintained at this temperature for 3 h; heated to 150 C. at 0.5 C./min; maintained at this temperature for 3 h; heated to 350 C. at 0.5-1 C./min; and maintained at this temperature for 3 h. Shaped 13% Co, 1.3% Zr on SiQ.sub.2 catalyst precursor was obtained.

EXAMPLE 13

[0121] 22.7 wt % Co, 2.3 wt % Zr on SiO.sub.2 Catalyst Precursor

[0122] This was prepared as in Example 12, except that 13 g SiO.sub.2 support was replaced by a 13 wt % Co, 1.3 wt % Zr on SiO.sub.2 catalyst precursor of the type produced in Example 12.

EXAMPLE 14

[0123] 30 wt % Co, 3.1 wt % Zr on SiO.sub.2 Catalyst Precursor

[0124] This was prepared as in Example 12, except that 13 g SiQ.sub.2 support was replaced by a 22.7 wt % Co, 2.3 wt % Zr on SiO.sub.2 catalyst precursor of the type produced in Example 13.

EXAMPLE 15

[0125] 13 wt % Co, 1.3 wt % Zr on Al.sub.2O.sub.3 Catalyst Precursor

[0126] This was prepared as in Example 12, except that 13 g SiO.sub.2 support was replaced by 13 g of Al.sub.2O.sub.3.

EXAMPLE 16

[0127] 22.7 wt % Co, 2.3 wt % Zr on Al.sub.2O.sub.3 Catalyst Precursor

[0128] This was prepared as in Example 15, except that the 13 g of Al.sub.2O.sub.3 support was replaced by a 13 wt % Co, 1.3 wt % Zr on Al.sub.2O.sub.3 catalyst precursor of the type produced in Example 15.

EXAMPLE 17

[0129] 30 wt % Co, 3.1 wt % Zr on Al.sub.2O.sub.3 Catalyst Precursor

[0130] This was prepared as in Example 15, except that the 13 g of Al.sub.2O.sub.3 support was replaced by a 22.7 wt %Co, 2.3 wt % Zr on Al.sub.2O.sub.3 catalyst precursor of the type produced in Example 16.

EXAMPLE 18

[0131] 30 wt % Co, 3.1 wt % Zr, 0.5 wt % Ru on SiO.sub.2 Catalyst Precursor

[0132] This catalyst was prepared according to Example 14. In the preparation, a specific amount of 30 wt % Co, 3.1 wt % Zr on SiO.sub.2 (oxide form after 350 C. calcination) was impregnated with a mixture of 6.7 g of 1.5 wt % Ru(NO)(NO.sub.3).sub.3 and 5 ml DI H.sub.2O. After impregnation, it was 100 C. in an oven for 12 h. The impregnated catalyst support was subjected to temperature-programmed calcination (TPC) in a static air environment as follows: heated to 130 C. at 1 C./min; maintained at this temperature for 3 h; heated to 150 C. at 0.5 C./min; maintained at this temperature for 3 h; heated to 350 C. at 0.5-1 C./min; and maintained at this temperature for 3 h. A catalyst precursor containing 30 wt % Co, 3.1 wt % Zr, 0.5 wt % Ru on SiO.sub.2 was thus obtained.

EXAMPLE 19

[0133] 30 wt % Co, 3.1 wt % Zr, 0.1 wt % Ru on SiO.sub.2 Catalyst

[0134] This was prepared as in Example 18, except that 6.7 g of 1.5 wt % Ru(NO)(NO.sub.3).sub.3 was replaced by 1.3 g of 1.5 wt % Ru(NO)(NO.sub.3).sub.3.

EXAMPLES 20 and 21

[0135] 30 wt % Co, 3.1 wt % Zr, 0.5 wt % Ru on Al.sub.2O.sub.3 and 30 wt % Co, 3.1 wt % Zr, 0.1 wt % Ru on Al.sub.2O.sub.3 Catalyst Precursors

[0136] These were prepared as in Examples 18 and 19, except that the SiO.sub.2 was replaced by Al.sub.2O.sub.3.

EXAMPLE 22

[0137] 30%Co3.1%Zr1%Ru/SiO.sub.2 Preparation

[0138] This was prepared as in Example 18, except that 6.7 g of 1.5 wt % Ru(NO)(NO.sub.3).sub.3 was replaced by 13 g of 1.5 wt % Ru(NO)(N.sup.O.sub.3).sub.3.

[0139] Co, Zr, Ru on SiO.sub.2 and Co, Zr, Ru on Al.sub.2O.sub.3 Catalyst Precursors

[0140] These were prepared as in Example 12-17, except that the solution or suspension of ZrO(N.sup.O.sub.3).sub.2, Co(NO.sub.3).sub.2.6H.sub.2O and urea was replaced by ZrO(NO.sub.3).sub.2, Co(NO.sub.3).sub.2.6H.sub.2O, Ru(NO)(NO.sub.3).sub.3 and urea.

[0141] During the processes set forth in the Examples, there was very little damage to the catalyst support, even when high loading of metals were achieved following a number of repeats of the steps.

[0142] The catalyst precursors produced according to Examples 12 to 22 were activated by flowing H.sub.2 at GHSV of 2000H.sup.1 at a heating rate of 1 C./min to 300 C., maintained at 300 C. for 2 hours and then cooled down to 200 C., at which temperature the reaction is started.

[0143] The activated catalysts were used in a Fischer-Tropsch process using the following conditions:

TABLE-US-00004 T: 220 C., P: 17.5 bar, GHSV: 2000H.sup.1, H.sub.2/CO ratio: 2.

[0144] The results of the Fischer-Tropsch processes are shown in the Table below.

TABLE-US-00005 TABLE Catalyst 30%Co3.1%Zr/SiO.sub.2 30%Co3.1%Zr0.1%Ru/SiO.sub.2 30%Co3.1%Zr0.5%Ru/SiO.sub.2 30%Co3.1%Zr1%Ru/SiO.sub.2 CO conversion 50-60% 68% 83% 84% C.sup.5+ 40-48% 54% 66% 67% productivity

[0145] As can be seen from the results given in the Table above, use of an activated catalyst according to the invention in a Fischer-Tropsch synthesis leads to greater selectivity for hydrocarbons having five or more carbon atoms and enhanced activity.

EXAMPLE 23

[0146] Modification of the silica support with titanium: TiO.sub.2/SiO.sub.2

[0147] At room temperature, 2.75 g of (C.sub.3H.sub.7O).sub.4Ti is mixed with 5.95 g of absolute ethanol in a small beaker: the volume of ethanol is determined according to the pore volume of the support. The solution is added to 9.30 g of silica support (sieved between 200-350 micron) by incipient wetness impregnation method. The impregnated support is dried at 100 C. over a hot plate for 3 hours and subjected to temperature-programmed calcination in a muffle furnace, as follows: the sample is introduced at 100 C. in the furnace, the temperature is maintained at 100 C. for 3 hours, the temperature is raised to 350 C. at

[0148] 2 C./min, the temperature is maintained to 350 C. during 4 hours. A silica titanium modified support is obtained.

EXAMPLE 24

[0149] First Impregnation with Co

[0150] At room temperature, 11.27 g of Co(NO.sub.3).sub.2.6H.sub.2O is mixed with 4.50 g of urea in a small beaker until a pink paste is obtained. 0.77 g of Zr(NO.sub.3).sub.2 is mixed with 5.05 g of deionised water (the amount of water is determined by the pore volume of the support obtained in Example 23) and heated over a hot plate at 100 C. until a clear solution is obtained. The solution of Zr(NO.sub.3).sub.2 is added over the mixture of Co(NO.sub.3).sub.2.6H.sub.2O and urea. The resulting mixture is heated over a hot plate at 100 C. until a clear red solution is obtained. This solution is added to the support synthesized in Example 23 by incipient wetness impregnation method. The impregnated catalyst is dried over a hot plate at 100 C. for 3 hours and subjected to temperature-programmed calcination in a muffle furnace, as follows: the sample is introduced at 100 C. in the furnace, the temperature is maintained at 100 C. for 3 hours, the temperature is raised to 128 C. at 1 C./min., the temperature is maintained to 128 C. for 3 hours, the temperature is raised to 150 C. at 1 C./min., the temperature is maintained to 150 C. for 3 hours, the temperature is raised to 350 C. at 0.5 C./min., the temperature is maintained to 350 C. for 3 hours. A cobalt impregnated catalyst is obtained.

EXAMPLE 25

[0151] Second Impregnation with Co to Obtain 30.0%Co3.0%Zr/5.0%TiO.sub.2/SiO.sub.2

[0152] This is prepared as in Example 24 except that the silica titanium modified support of Example 23 is replaced by the cobalt impregnated catalyst obtained in Example 24.

EXAMPLE 26

[0153] Impregnation with Ru to Obtain 30.0%Co3.0%Zr/5.0%TiO.sub.2/0.2%RuISiO.sub.2

[0154] At room temperature, 2 g of Ru(NO)(NO.sub.3).sub.3 (1.5%Ru in water) is mixed with 4.52 g of water in a small beaker (the amount of water is determined by the pore volume of the catalyst obtained in Example 25). This solution is added to 15 g of the catalyst synthesized in Example 25 by incipient wetness impregnation method. The impregnated support is dried at 100 C. over a hot plate for 3 hours and subjected to temperature-programmed calcination in a muffle furnace, as follows: the sample is introduced at 100 C. in the furnace, the temperature is maintained at 100 C. for 3 hours, the temperature is raised to 350 C. at 2 C./rain, the temperature is maintained to 350 C. for 3 hours.

EXAMPLE 27

[0155] Third Impregnation with Co to Obtain 37.5%Co2.7%Zr/4.5%TiO.sub.2/SiO.sub.2

[0156] At room temperature, 9.0 g of Co(NO.sub.3).sub.2.6H.sub.2O is mixed with 3.6 g of urea in a small beaker until a pink paste is obtained. 4.52 g of deionised water (the amount of water is determined by the pore volume of the catalyst synthesized in Example 25) is heated over a hot plate at 100 C. for 10 min. The hot water is added over the mixture of Co(NO.sub.3).sub.2.6H.sub.2O and urea. The resulting mixture is heated over a hot plate at 100 C. until a clear red solution is obtained. This solution is added to 15 g of the catalyst synthesized in Example 25 by incipient wetness impregnation method. The impregnated catalyst is dried over a hot plate at 100 C. for 3 hours and subjected to temperature-programmed calcination in a muffle furnace, as follows: the sample is introduced at 100 C. in the furnace, the temperature is maintained at 100 C. for 3 hours, the temperature is raised to 128 C. at 1 C./min., the temperature is maintained to 128 C. for 3 hours, the temperature is raised to 150 C. at 1 C./min., the temperature is maintained to 150 C. for 3 hours, the temperature is raised to 350 C. at 0.5 C./min., the temperature is maintained to 350 C. for 3 hours. A cobalt impregnated catalyst is obtained.

EXAMPLE 28

[0157] Impregnation with Ru to Obtain 37.5%Co2.7%Zr/4.5%TiO.sub.2/0.2%Ru/SiO.sub.2

[0158] This is prepared as in Example 26 except that the cobalt impregnated catalyst obtained in Example 25 is replaced by 15 g of the cobalt impregnated catalyst obtained in Example 27.

EXAMPLE 29

[0159] Fourth Impregnation with Co to Obtain 44.4%Co2.4%Zr/4.0%TiO.sub.2/SiO.sub.2

[0160] This is prepared as in Example 27 except that the cobalt impregnated catalyst obtained in Example 25 is replaced by 14.5 g of the cobalt impregnated catalyst obtained in Example 27.

EXAMPLE 30

[0161] Impregnation with Ru to Obtain 44.4%Co2.4%Zr/4.0%TiO.sub.2/0.2%Ru/SiO.sub.2

[0162] This is prepared as in Example 26 except that the cobalt impregnated catalyst obtained in Example 25 is replaced by 15 g of the cobalt impregnated catalyst obtained in Example 29.

EXAMPLE 31

[0163] Fifth Impregnation with Co to Obtain 50.9%Co2.1%Zr/3.5%TiO.sub.2/SiO.sub.2

[0164] This is prepared as in Example 27 except that the cobalt impregnated catalyst obtained in Example 25 is replaced by 13.7 g of the cobalt impregnated catalyst obtained in Example 29.

EXAMPLE 32

[0165] Impregnation with Ru to Obtain 50.8%Co2.1%Zr/3.5%TiO.sub.2/0.2%Ru/SiO.sub.2

[0166] This is prepared as in Example 26 except that the cobalt impregnated catalyst obtained in Example 25 is replaced by 15 g of the cobalt impregnated catalyst obtained in Example 31.

[0167] Catalytic Results

[0168] The catalyst precursors produced according to Examples 25, 27, 28 and 29 were activated in flowing hydrogen at GHSV of 6,000 H.sup.1 at the heating rate of 1K/min. to 400 C., and kept for 2 hours, cooled down to 190 C. The activated catalysts were used in 10 the Fischer-Tropsch reaction with the following operating conditions: P=21 bar, GHSV=6,050 H.

[0169] Effect of Cobalt Loading

[0170] T=200 C.

TABLE-US-00006 CO.sub.2 sel. CH.sub.4 sel. C.sub.5.sup.+ prod. Catalyst CO conv. (%) C.sub.5.sup.+ sel. (%) (%) (%) (%) Ex. 25 25 89 0.00 5.1 22 Ex. 27 40 86 0.09 7.4 35 Ex. 29 54 81 0.33 11 43

[0171] The CO conversion and the C.sub.5.sup.+ productivity increase with the Co loading. The selectivity in CH.sub.4 and CO.sub.2 increases at the expense of the selectivity in C.sub.5.sup.+.

[0172] Effect of Addition of Ruthenium

[0173] T=220 C.

TABLE-US-00007 CO conv. CO.sub.2 sel. CH.sub.4 sel. C.sub.5.sup.+ prod. Catalyst (%) C.sub.5.sup.+ sel. (%) (%) (%) (%) Ex. 27 68 85 0.4 8.7 58 Ex. 28 81 80 0.9 13 64

[0174] The CO conversion and the C.sub.5.sup.+ productivity increase with the addition of ruthenium. The selectivity in CH.sub.4 and CO.sub.2 increases at the expense of the selectivity in C.sub.5.sup.+.

[0175] The catalyst precursor produced according to Example 31 was activated in flowing hydrogen at GHSV of 8,000 H.sup.1 at the heating rate of 1 C. /min. to 400 C., and kept for 2 hours, cooled down to 160 C. The activated catalyst was used in the Fischer-Tropsch reaction with the following operating conditions: P=20 bar.

[0176] Effect of GHSV

[0177] T=199 C.

TABLE-US-00008 CO conv. CO.sub.2 sel. CH.sub.4 sel. C.sub.5.sup.+ prod. GHSV (H.sup.1) (%) C.sub.5.sup.+ sel. (%) (%) (%) (%) 5,000 82 86 0.43 7.2 70 14,150 38 84 0.00 7.7 32

[0178] The CO conversion and the C.sub.5.sup.+ productivity are divided by around 2 with the increase in GHSV (H.sup.1) from 5,000 to 14,150. The selectivities don't change with the GHSV.

[0179] Effect of Temperature

[0180] GHSV=5,000 H.sup.1

TABLE-US-00009 CO conv. CO.sub.2 sel. CH.sub.4 sel. C.sub.5.sup.+ prod. Temp. ( C.) (%) C.sub.5.sup.+ sel. (%) (%) (%) (%) 173 28 87 0.02 4.0 25 180 39 86 0.17 4.7 33 191 66 87 0.02 5.7 58 199 82 86 0.43 7.2 70

[0181] The CO conversion and the C.sub.5.sup.+ productivity increase with the increase in temperature. The C.sub.5.sup.+ selectivity is constant. The selectivities in CO.sub.2 and CH.sub.4 increase with the temperature.

[0182] The catalyst precursor produced according to Example 29 was activated in flowing hydrogen at GHSV of 8,000 H.sup.1 at the heating rate of 1 C./min. to 400 C., and kept for 2 hours, cooled down to 160 C. The activated catalysts were used in the Fischer-Tropsch reaction with the following operating conditions: T=206 C., P=20 bar, GHSV=8,688 H.sup.1.

[0183] Effect of Time on Stream

TABLE-US-00010 Time on CO conv. CO.sub.2 sel. CH.sub.4 sel. C.sub.5.sup.+ prod. stream (Hrs) (%) C.sub.5.sup.+ sel. (%) (%) (%) (%) 46 66.60 82.95 0.24 9.91 55.24 70 65.55 83.36 0.24 9.70 54.64 94 64.60 83.22 0.22 9.51 53.76 119 62.99 82.88 0.16 9.57 52.21 143 62.57 82.82 0.18 9.45 51.82

[0184] The CO conversion and the C.sub.5.sup.+ productivity decrease with the time on stream: the decrease of the conversion is around 1% per day. The C.sub.5.sup.+, CO.sub.2 and CH.sub.4 selectivities are constant.

[0185] The catalyst synthesized in the presence of urea show robust performance over a wide range of GHSV, temperature, time on stream. The increase in Co loading and the addition of ruthenium increase the conversion without decreasing greatly the C.sub.5.sup.+ selectivity. The addition of titanium also improves the selectivity in C.sub.5.sup.+. These catalysts are suitable for application of the Fischer-Tropsch reaction at high GHSV (H.sup.1) and low temperature.