OLEFIN SELECTIVE FT CATALYST COMPOSITION AND PREPARATION THEREOF

Abstract

The present invention relates to a hydrocarbon synthesis catalyst comprising in its unreduced form a) Fe as catalytically active metal, b) an alkali metal and/or alkaline-earth metal in an alkali metal- and/or alkaline-earth metal-containing promoter, the alkali metal, c) and a further promoter comprising, or consisting of, one or more element(s) selected from the group of boron, germanium, nitrogen, phosphorus, arsenic, antimony, sulphur, selenium and tellurium, to a process for the synthesis of a hydrocarbon synthesis catalyst, to a hydrocarbon synthesis process which is operated in the present of such a catalyst and to the use of such a catalyst in a hydrocarbon synthesis process.

Claims

1-6. (canceled)

7. Process for the preparation of a hydrocarbon synthesis catalyst comprising the following steps: (a) providing a solution of iron or a suspension of a precipitated, non-calcined iron-containing solid in a solvent in which a precursor of a promoter P1 is present, the promoter P1 comprising one or more element(s) selected from the group of boron, germanium, nitrogen, phosphorus, arsenic, antimony, sulphur, selenium and tellurium, (b) removing the solvent from the solution or suspension, and (c) subjecting the product of step (b) to a calcination treatment, wherein the amount of the precursor of promoter P1 is selected so that the one or more element(s) selected from boron, germanium, nitrogen, phosphorus, arsenic, antimony, sulphur, selenium and tellurium is(are) present in an amount of at least 0.02 g/100 g Fe in the catalyst, and a precursor of an alkali metal- and/or alkaline-earth metal containing promoter P2 is added before, after or during any of the steps of the process so that promoter P2 is present in the catalyst.

8. Process according to claim 7, wherein in step (a) a solution of iron in a solvent is provided in which a precursor of a promoter P1 is present, and then a suspension is obtained by forming a precipitate containing iron and the precursor of promoter P1 from the solution before step (b) is carried out.

9. Process according to claim 7 wherein the solvent is an aqueous solvent.

10. Process according to claim 7 wherein the calcination treatment in step (c) is performed at a temperature of 200° C. or more.

11. Process according to claim 7, wherein the product of step (b) has surface area of 50 to 500 m.sup.2/g.

12. Process according to claim 7, wherein the product of step (c) has surface area of 10 to 80 m.sup.2/g.

13. Process according to claim 7, wherein promoter P1 comprises one or more element(s) selected from the group of boron, phosphorus, antimony and sulphur.

14. Process according to claim 7, wherein the amount of the precursor of promoter P2 is selected such that the alkali metal and/or alkaline-earth metal is/are present in an amount of from 0.02 to 1.0 g/100 g Fe in the catalyst.

15. Process according to claim 7, wherein the precursor of promoter P2 is selected from sodium hydroxide, sodium carbonate, sodium oxide, potassium hydroxide, potassium carbonate, potassium oxide, caesium hydroxide, caesium carbonate, caesium oxide or mixtures thereof.

16. (canceled)

17. A hydrocarbon synthesis process which is operated in the presence of a catalyst formed by the process of claim 7, wherein the catalyst is in its reduced form.

18. Process according to claim 17 which is a Fischer-Tropsch process.

19. The process according to claim 17 comprising further processing of an obtained hydrocarbon product.

20. (canceled)

21. A hydrocarbon synthesis process which is operated in the presence of a catalyst comprising: in an unreduced form: a) Fe as catalytically active metal, b) a first promoter comprising an alkali metal and/or an alkaline-earth metal, the alkali metal and/or alkaline-earth metal being present in a combined amount of 0.1 to 1.0 g/100 g Fe, c) a second promoter comprising a metalloid, the metalloid being sulphur, present in an amount of 0.03 to 0.2 g/100 g Fe, d) a surface area of 80 m.sup.2/g or less, and e) a weight ratio of the first promoter to the second promoter of 0.8:1 to 20:1; and in a reduced form further comprising: a chemical bond between the at least one metal of the first promoter and the metalloid of the second promoter, and wherein at least 75 wt. % of the Fe is in the zero oxidation state.

22. Catalyst obtainable by the following process steps: (a) providing a precipitation mixture comprising: a precipitated, non-calcined iron-containing solid; an aqueous solvent; and a precursor of a first promoter, the precursor of the first promoter comprising sulphur, (b) removing the solvent from the precipitation mixture, (c) subjecting the product of step (b) to a calcination treatment, the calcined catalyst comprising an amount of sulphur of at least 0.12 g/100 g Fe, and (d) providing a precursor of a second promoter to the calcined catalyst, the second precursor comprising an alkali metal and/or an alkaline-earth metal, the second precursor provided to the calcined catalyst by at least one: adding the second precursor to the precipitation mixture and retaining the metal of the second precursor while removing the solvent from the precipitation mixture; adding the second precursor to the precipitation mixture after the solvent has been removed; and adding the second precursor to the calcined catalyst, wherein the precursor of the second promoter is provided in amount sufficient to provide in the calcined catalyst a ratio of the metal of the second precursor to the combined amount of the metalloid and/or the non-metal of the first precursor of 0.8:1 to 20:1, and (e) reducing the calcined catalyst comprising the precursor of the second promoter, wherein the reduced form of the catalyst comprises a chemical bond between the metal of the second promoter and the sulphur of the first promoter, and wherein at least 75 wt. % of the Fe is in the zero oxidation state.

Description

EXAMPLES

1. Methods

1.1 Surface Area

[0201] Surface Area measurements were done using a Micromeritics Tristar 3000. Samples were degassed under dynamic nitrogen flow at 200° C. for a minimum time of 12 hours. Thereafter 250-300 mg of sample were accurately weighed out and loaded into ⅜ inch tubes onto the instrument. Sample tubes were immersed in a liquid nitrogen bath and evacuated. Leak tests were conducted, where after a total of eight relative pressure points were measured in a range from 0.08 to 0.98. Measured parameters were used by the instrument software to calculate the surface area.

1.2 Particle Size

[0202] The Particle size of the catalyst particles is determined using fine test sieves fitted with stainless steel wire cloth meeting ASTM specification E-11.

1.3 Catalyst Preparation Procedure

[0203] For the reverse precipitation of iron, up to 100 ml 25% (v/v) NH.sub.4OH solution was added drop-wise, whilst stirring with an overhead stirrer, to 400 ml of 1 M aqueous solution of Fe(NO.sub.3).sub.3.Math.9 H.sub.2O (161.6 g) until a pH of 7 at room temperature (25° C.) was reached. Thereafter, Na 2 CO 3 and the selected non-metal precursor, if present, were added in the appropriate amounts to the precipitation mixture. The resultant slurry was then dried in a fan-oven overnight (approximately 16 hours) at 150° C., and then calcined in air at 350° C. for 4 hours. Finally, the catalyst was crushed and screened to a particle size range of 38-150 μm. This was achieved by screening the catalyst over a 38 μm sieve and discarding the <38 μm fraction, followed by screening over a 150 μm sieve and discarding the >150 μm fraction using fine test sieves fitted with stainless steel wire cloth meeting ASTM specification E-11.

1.4 Catalyst Testing Procedure

[0204] 25 mg calcined catalyst was loaded into a micro fixed bed reactor and reduced in situ under hydrogen at 420° C. for 16 hours at 20 bar. Thereafter, synthesis gas was introduced at a flow rate of 13 liters (n) per g catalyst per hour (H.sub.2=57 volume %, CO=14 volume %, CO.sub.2=11 volume %) at 20 bar total pressure and at a temperature of 330° C. Analysis of hydrocarbon products was performed using GC-FID, and permanent gas analysis was done by GC-TCD.

1.5 Selectivity

[0205] All selectivities are expressed as carbon-atom % selectivity and are not normalized. CO.sub.2 formation is excluded in selectivity calculations.

2. Experiments

Comparative Example 1

[0206] Following the general catalyst preparation procedure described above a catalyst with a composition of 0.295 g Na per 100 g Fe was prepared and tested in a micro fixed bed reactor as described in the general catalyst testing procedure above. The synthesis results are summarized in Tables 1, 2, 3 and 4.

Comparative Example No 2

[0207] Following the general catalyst preparation procedure described above, except that Na.sub.2(CO.sub.3) was not added, a catalyst with a composition of 0.05 g S per 100 g Fe was prepared and tested in a micro fixed bed reactor as described in the general catalyst testing procedure above. The synthesis results are summarized in Table 1, 2, 3 and 4

Example 3

[0208] Following the general catalyst preparation procedure described above a catalyst with a composition of 0.591 g Na per 100 g Fe and 0.12 g S per 100 g Fe was prepared and tested in a micro fixed bed reactor as described in the general catalyst testing procedure above. The sulphur precursor used was ammonium sulphate. The synthesis results are summarized in Table 1 and compared to Comparative Examples 1 and 2.

TABLE-US-00001 TABLE 1 Comparative Comparative Example 3* Example 1† Example 2† 0.591 g Na/ 0.295 g Na/100 0.05 g S/100 g 0.12 g S/100 g g Fe Fe Fe CO + H.sub.2 54% 43% 41% conversion CO + CO.sub.2 50% 38% 40% conversion CH.sub.4 selectivity  9% 38%  9% C.sub.2-C.sub.4 selectivity 24% 50% 52% C.sub.2-C.sub.8 selectivity 52% 55% 76% C.sub.5+ selectivity 58%  8% 34% % olefins in 80% 12% 75% C.sub.2-C.sub.4 fractions % alcohols in 12%  4% 15% C.sub.2-C.sub.4 fractions Surface area 32.8 m.sup.2/g 30.9 m.sup.2/g 31.7 m.sup.2/g (unreduced catalyst) †estimated mass balance: 95%; *estimated mass balance: 97%

Example 4

[0209] Following the general catalyst preparation procedure described above a catalyst with a composition of 0.31 g Na per 100 g Fe and 0.08 g P per 100 g Fe was prepared and tested in a micro fixed bed reactor as described in the general catalyst testing procedure above. The phosphorous precursor used was ammonium phosphate dibasic. The synthesis results are summarized in Table 2 and compared to Comparative Examples 1 and 2.

TABLE-US-00002 TABLE 2 Comparative Comparative Example 1† Example 2† Example 4* 0.295 g Na/100 0.05 g S/100 g 0.31 g Na/0.08 g Fe Fe g P/100 g Fe CO + H.sub.2 54% 43% 44% conversion CO + CO.sub.2 50% 38% 41% conversion CH.sub.4 selectivity 9% 38% 10% C.sub.2-C.sub.4 selectivity 24% 50% 37% C.sub.2-C.sub.8 selectivity 52% 55% 62% C.sub.5+ selectivity 58%  8% 45% % olefins in 80% 12% 80% C.sub.2-C.sub.4 fractions % alcohols in 12%  4%  8% C.sub.2-C.sub.4 fractions †estimated mass balance: 95%; *estimated mass balance: 93%

Example 5

[0210] Following the general catalyst preparation procedure described above a catalyst with a composition of 0.369 g Na per 100 g Fe and 0.05 g B per 100 g Fe was prepared and tested in a micro fixed bed reactor as described in the general catalyst testing procedure methodology above. The boron precursor used was ammonium biborate tetrahydrate. The synthesis results are summarized in Table 3 and compared to Comparative Examples 1 and 2.

TABLE-US-00003 TABLE 3 Comparative Comparative Example 1† Example 2† Example 5* 0.295 g Na/100 0.05 g S/100 g 0.369 g Na/0.05 g Fe Fe g B/100 g Fe CO + H.sub.2 54% 43% 47% conversion CO + CO.sub.2 50% 38% 43% conversion CH.sub.4 selectivity  9% 38%  9% C.sub.2-C.sub.4 selectivity 24% 50% 37% C.sub.2-C.sub.8 selectivity 52% 55% 67% C.sub.5+ selectivity 58%  8% 49% % olefins in 80% 12% 82% C.sub.2-C.sub.4 fractions % alcohols in 12%  4%  6% C.sub.2-C.sub.4 fractions †estimated mass balance: 95%; *estimated mass balance: 95%

Example 6

[0211] Following the general catalyst preparation procedure described above a catalyst with a composition of 0.591 g Na per 100 g Fe and 0.1 g Sb per 100 g Fe was prepared and tested in a micro fixed bed reactor as described in the general catalyst testing methodology above. The antimony precursor used was antimony acetate. The synthesis results are summarized in Table 4 and compared to Comparative Examples 1 and 2.

TABLE-US-00004 TABLE 4 Comparative Comparative Example 6* Example 1† Example 2† 0.591 g Na/ 0.295 g Na/ 0.05 g S/100 g 0.1 g Sb/100 g 100 g Fe Fe Fe* CO + H.sub.2 54% 43% 41% conversion CO + CO.sub.2 50% 38% 39% conversion CH.sub.4 selectivity  9% 38%  7% C.sub.2-C.sub.4 selectivity 24% 50% 38% C.sub.2-C.sub.8 selectivity 52% 55% 67% C.sub.5+ selectivity 58%  8% 49% % olefins in 80% 12% 73% C.sub.2-C.sub.4 fractions % alcohols in 12%  4% 14% C.sub.2-C.sub.4 fractions †estimated mass balance: 95%; *estimated mass balance: 94%

Example 7

[0212] Following the general catalyst preparation procedure described above a catalyst with a composition of 0.29 g Na per 100 g Fe and 0.05 g S per 100 g Fe was prepared and tested in a micro fixed bed reactor as described in the general catalyst testing methodology above. The sulphur precursor used was ammonium sulphate. The synthesis results are summarized in Table 5 and compared to Example 3.

TABLE-US-00005 TABLE 5 Example 7 Example 3 0.29 g Na/0.05 g 0.59 g Na/0.12 g S/100 g Fe S/100 g Fe CO + H.sub.2 conversion 48% 41% CO + CO.sub.2 conversion 46% 40% CH.sub.4 selectivity  9%  9% C.sub.2-C.sub.4 selectivity 47% 52% C.sub.2-C.sub.8 selectivity 74% 76% C.sub.5+ selectivity 40% 34% % olefins in C.sub.2-C.sub.4 74% 75% fractions % alcohols in C.sub.2-C.sub.4 15% 15% fractions Surface area (unreduced 29.4 m.sup.2/g 31.7 m.sup.2/g catalyst)

Example 8

[0213] The procedure for Example 7 was repeated except this time the reactor synthesis temperature was lowered from 330° C. to 300° C. The synthesis results are summarized in Table 6 and compared to Example 7.

TABLE-US-00006 TABLE 6 Example 8 Example 7 0.29 g Na/0.05 g 0.29 g Na/0.05 g S/100 g Fe S/100 g Fe CO + H.sub.2 conversion 34% 48% CO + CO.sub.2 conversion 30% 46% CH.sub.4 selectivity  8%  9% C.sub.2-C.sub.4 selectivity 45% 47% C.sub.2-C.sub.8 selectivity 66% 74% C.sub.5+ selectivity 40% 40% % olefins in C.sub.2-C.sub.4 76% 74% fractions % alcohols in C.sub.2-C.sub.4 11% 15% fractions Surface area 29.4 m.sup.2/g 29.4 m.sup.2/g (unreduced catalyst)

Example 9

[0214] The procedure for Example 7 was repeated except this time the reactor synthesis temperature was raised from 330° C. to 360° C. The synthesis results are summarized in Table 7 and compared to Example 7.

TABLE-US-00007 TABLE 7 Example 9 Example 7 0.29 g Na/0.05 g 0.29 g Na/0.05 g S/100 g Fe S/100 g Fe CO + H.sub.2 conversion 52% 48% CO + CO.sub.2 conversion 47% 46% CH.sub.4 selectivity 10%  9% C.sub.2-C.sub.4 selectivity 43% 47% C.sub.2-C.sub.8 selectivity 64% 74% C.sub.5+ selectivity 34% 40% % olefins in C.sub.2-C.sub.4 80% 74% fractions % alcohols in C.sub.2-C.sub.4  8% 15% fractions Surface area 29.4 m.sup.2/g 29.4 m.sup.2/g (unreduced catalyst)

Example 10

[0215] The procedure for Example 7 was repeated except for the total reactor pressure which was raised from 20 bar to 40 bar while the synthesis temperature was raised from 330 to 360° C. The synthesis results are summarized in Table 8.

TABLE-US-00008 TABLE 8 Example 10 0.29 g Na/0.05 g S/100 g Fe CO + H.sub.2 conversion 59% CO + CO.sub.2 conversion 54% CH.sub.4 selectivity 13% C.sub.2-C.sub.4 selectivity 45% C.sub.2-C.sub.8 selectivity 64% C.sub.5+ selectivity 29% % olefins in C.sub.2-C.sub.4 72% fractions % alcohols in C.sub.2-C.sub.4 10% fractions Surface area 29.4 m.sup.2/g (unreduced catalyst)

Example 11

[0216] Following the general catalyst preparation procedure described above a catalyst with a composition of 0.8 g K per 100 g Fe and 0.2 g S per 100 g Fe was prepared and tested in a micro fixed bed reactor as described in the general catalyst testing procedure described above. In this case the synthesis temperature was raised to 360° C. and the total reactor pressure was increased to 40 bar. The synthesis results are summarized in Table 9 and compared to Example 10 which was tested under identical conditions.

TABLE-US-00009 TABLE 9 Example 11 Example 10 0.8 g K/0.2 g 0.29 g Na/0.05 g S/100 g Fe S/100 g Fe CO + H.sub.2 conversion 12% 59% CO + CO.sub.2 conversion 14% 54% CH.sub.4 selectivity 12% 13% C.sub.2-C.sub.4 selectivity 50% 45% C.sub.2-C.sub.8 selectivity 66% 64% C.sub.5+ selectivity 33% 29% % olefins in C.sub.2-C.sub.4 74% 72% fractions % alcohols in C.sub.2-C.sub.4 10% 10% fractions
3.1 Catalyst Preparation Procedure A (inventive Example 1A)

[0217] For the reverse precipitation of iron, up to 100 ml 25% (v/v) NH.sub.4OH solution was added drop-wise, whilst stirring with an overhead stirrer, to 400 ml of 1 M aqueous solution of Fe(NO.sub.3).sub.3.Math.9H.sub.2O (161.6 g) containing the appropriate amount of the selected non-metal precursor of promoter P1 until a pH of 7 at room temperature (25° C.) was reached. Thereafter, Na 2 CO 3 was added in the appropriate amounts to the precipitation mixture. The resultant slurry was then dried in a fan-oven overnight (approximately 16 hours) at 150° C., and then calcined in air at 350° C. for 4 hours. Finally, the catalyst was crushed and screened to a particle size range of 38-150 μm. This was achieved by screening the catalyst over a 38 μm sieve and discarding the <38 μm fraction, followed by screening over a 150 μm sieve and discarding the >150 μm fraction using fine test sieves fitted with stainless steel wire cloth meeting ASTM specification E-11.

3.2 Catalyst Preparation Procedure B (Example 2A)

[0218] For the reverse precipitation of iron, up to 100 ml 25% (v/v) NH.sub.4OH solution was added drop-wise, whilst stirring with an overhead stirrer, to 400 ml of 1 M aqueous solution of Fe(NO.sub.3).sub.3.Math.9H.sub.2O (161.6 g) until a pH of 7 at room temperature (25° C.) was reached. Thereafter, Na 2 CO 3 was added in the appropriate amounts to the precipitation mixture. The resultant slurry was then dried in a fan-oven overnight (approximately 16 hours) at 150° C., and then calcined in air at 350° C. for 4 hours. The catalyst was then crushed and screened to a particle size range of 38-150 μm using fine test sieves fitted with stainless steel wire cloth meeting ASTM specification E-11. Thereafter the iron oxide particles were suspended in a water mixture containing the appropriate amount of the selected non-metal precursor of promoter P1 and agitated for approximately 30 minutes. The resultant slurry was then dried in a fan-oven overnight (approximately 16 hours) at 150° C., and again calcined in air at 350° C. for 4 hours.

3.3 Catalyst Preparation Procedure C (comparative Example 3A)

[0219] For the reverse precipitation of iron, up to 100 ml 25% (v/v) NH.sub.4OH solution was added drop-wise, whilst stirring with an overhead stirrer, to 400 ml of 1 M aqueous solution of Fe(NO.sub.3).sub.3.Math.9H.sub.2O (161.6 g) until a pH of 7 at room temperature (25° C.) was reached. Thereafter, Na 2 CO 3 was added in the appropriate amounts to the precipitation mixture. The resultant slurry was then dried in a fan-oven overnight (approximately 16 hours) at 150° C., and then calcined in air at 350° C. for 4 hours. Finally, the catalyst was crushed and screened to a particle size range of 38-150 μm using fine test sieves fitted with stainless steel wire cloth meeting ASTM specification E-11.

3.4 Catalyst Preparation Procedure D using spray drying (example 6A)

[0220] Iron nitrate salt [Fe(NO.sub.3).sub.3.Math.9H.sub.2O] was dissolved in water to a concentration of 200 g Fe/litre. The solution was promoted with 0.4 g Na/100 g Fe by using Sodium carbonate (Na 2 CO 3) and with 0.11 g S/100 g Fe by using ammonium sulphate. This solution was spray dried on a Niro Production Minor spray dryer with an inlet temperature of 390° C. and outlet temperature of 140° C. A TX2.5 Unijet hollow cone spray nozzle tip was used to atomize the feed solution. At a pressure of 15 bar, the feed rate was approximately 19.8 litres/hour. A Hydra-cell G-13 positive displacement diaphragm feed pump was used to feed the high-pressure nozzle. The catalyst was calcined at 350° C. for 4 hours.

3.5 Catalyst Testing Procedure

[0221] 5 g calcined catalyst was loaded into a berty type gradientless micro fixed bed reactor and reduced in situ under hydrogen at 420° C. for 16 hours at bar. Thereafter, synthesis gas was introduced at a flow rate of 13 liters (n) per g catalyst per hour (H.sub.2=57 volume %, CO=14 volume %, CO.sub.2=11 volume %) at 20 bar total pressure and at a temperature of 330° C. Analysis of hydrocarbon products was performed using GC-FID, and permanent gas analysis was done by GC-TCD.

3.6 Selectivity

[0222] All selectivities are expressed as carbon-atom % selectivity and are not normalized. CO.sub.2 formation is excluded in selectivity calculations.

4. Experiments

Inventive Example 1A

[0223] Following the general catalyst preparation procedure A described in item 3.1 above, a catalyst with a composition of 0.419 g Na per 100 g Fe and 0.112 g S per 100 g Fe was prepared and tested in a Berty type gradientless micro reactor as described in the general catalyst testing methodology (item 3.5) above. The sulphur precursor used was ammonium sulphate. The synthesis results are summarized in Table 10.

Example 2A

[0224] Following the general catalyst preparation procedure B described in item 3.2 above a catalyst with a composition of 0.419 g Na per 100 g Fe and 0.112 g S per 100 g Fe was prepared and tested in a Berty type gradientless micro reactor as described in the general catalyst testing methodology (item 3.5) above. The sulphur precursor used was ammonium sulphate. The synthesis results are summarized in Table 10.

Comparative Example 3A

[0225] Following the general catalyst preparation procedure C described in item 3.3 above a catalyst with a composition of 0.295 g Na per 100 g Fe was prepared and tested in a Berty type gradientless microreactor as described in the general catalyst testing procedure (item 3.5) above. The synthesis results are summarized in Table 10.

TABLE-US-00010 TABLE 10 Example Example Comparative 1A† 2A* Example 3A† Na 0.419 g 0.419 g 0.295 g S 0.112 g 0.112 g — Fe   100 g   100 g   100 g CO + H.sub.2 conversion 33.5% 39.8% 46% CO + CO.sub.2 conversion 33.9% 38.3% 44% CH.sub.4 selectivity 10.8% 14.1% 10% C.sub.2-C.sub.4 selectivity 59.3% 58.2% 34% C.sub.2-C.sub.8 selectivity 76.4% 78.6% 60% C.sub.5+ selectivity 22.3% 24.5% 46% olefins in C.sub.2-C.sub.4 fraction 61.6% 63.7% 70% alcohols in C.sub.2-C.sub.4 22.1% 15.8% 13% fraction paraffins in C.sub.2-C.sub.4  9.7% 14.3% 17% fraction Surface area (unreduced 27 m.sup.2/g 15 m.sup.2/g 32.8 m.sup.2/g catalyst) †Estimated mass balance: 95%; *Estimated mass balance: 97%

Example 4A

[0226] Following the general catalyst preparation procedure D described in item 3.4 above a catalyst with a composition of 0.52 g Na per 100 g Fe and 0.1 g S per 100 g Fe was prepared and tested in a Berty type gradientless micro reactor as described in the general catalyst testing procedure (item 3.5) above. The synthesis results are summarized in Table 11.

TABLE-US-00011 TABLE 11 Example 4A 0.52 g Na/0.1 g S/100 g Fe CO + H.sub.2 conversion 36.6% CO + CO.sub.2 conversion 41.8% CH.sub.4 selectivity 12.2% C.sub.2-C.sub.4 selectivity 59.0% C.sub.2-C.sub.8 selectivity 80.4% C.sub.5+ selectivity 28.6% % olefins in C.sub.2-C.sub.4 fraction 53.0% % alcohols in C.sub.2-C.sub.4 fraction 37.0% % paraffins in C.sub.2-C.sub.4 fraction  5.3%

Discussion of the Results in Tables 1 to 11:

[0227] Surprisingly, when comparing the synthesis performance of the catalyst of Comparative Example 1 with the catalysts promoted by a series of non-metals in combination with alkali metal, it will be noted that the methane selectivity remained relatively constant while a dramatic increase in selectivity for light hydrocarbons (C.sub.2-C.sub.4 hydrocarbon fraction) was observed.