Catalyst composition and catalytic processes for producing liquid hydrocarbons

Abstract

The invention relates to potassium-promoted, Fe.sup.2+(Fe.sup.3+yAl.sup.3+i-y)2.sup.o4 [0.3<.sub.y0.7] silica-containing extrudates, processes for the preparation of the extrudates with the aid of colloidal silica, and the use of the extrudates to catalyze processes for producing liquid hydrocarbons.

Claims

1. A process for preparing potassium-promoted Fe.sup.2+(Fe.sup.3+.sub.yAl.sup.3+.sub.1-y).sub.2O.sub.4 [0.3y0.7] silica-containing pellets, comprising subjecting colloidal silica to gelation in the presence of Fe.sup.2+(Fe.sup.3+.sub.yAl.sup.3+.sub.1-y).sub.2O.sub.4 spinel particles, converting the gelled material into pellets and adding potassium to said pellets.

2. A process according to claim 1, wherein the colloidal silica used is an aqueous alkali-stabilized colloidal silica comprising amorphous silica with particle size of up to 50 nm.

3. A process according to claim 1, wherein the Fe.sup.2+(Fe.sup.3+.sub.yAl.sup.3+.sub.1-y).sub.2O.sub.4 spinel used is in the form of a powder with particle size of less than 250 m.

4. A process according to claim 1, wherein the potassium-promoted Fe.sup.2+(Fe.sup.3+.sub.yAl.sup.3+.sub.1-y).sub.2O.sub.4 silica-containing pellets are potassium-promoted Fe.sup.2+(Fe.sup.3+.sub.yAl.sup.3+.sub.1-y).sub.2O.sub.4 silica-containing extrudates.

5. A process according to claim 4, comprising: (i) lowering the pH of an aqueous alkali-stabilized colloidal silica; (ii) combining said colloidal silica with Fe.sup.2+(Fe.sup.3+.sub.yAl.sup.3+.sub.1-y).sub.2O.sub.4 spinel particles; (iii) allowing the mixture resulting from step (ii) to transform into a gel; (iv) adjusting the consistency of said gel to obtain an extrudable mass; (v) extruding said mass to form extrudates; (vi) drying the extrudates; (vii) calcining the dried extrudates; (viii) treating the calcined extrudates with an aqueous solution of a potassium salt; (ix) drying the potassium-containing extrudates resulting from step (iii); and (x) calcining the extrudates resulting from step (ix).

6. A process according to claim 5, wherein in step (i) an acid is added to the aqueous alkali-stabilized colloidal silica to lower the pH to the range from 6.5 to 7.5.

Description

IN THE DRAWINGS

(1) FIG. 1 is a scheme of an apparatus suitable for conducting the hydrogenation of CO.sub.2 to form liquid hydrocarbons.

(2) FIG. 2 shows a scheme of an experimental set-up used for conducting the reaction of CO with steam to form liquid hydrocarbons, according to an embodiment of the invention. The same experimental set-up was also used for converting H.sub.2-lean syngas into liquid hydrocarbons, according to another embodiment of the invention.

(3) FIG. 3 is a bar diagram showing the content of paraffins, olefins, aromatics, naphthenes and oxygenates in the liquid product obtained on reacting CO with steam.

(4) FIG. 4 is a bar diagram showing the content of paraffins, olefins, aromatics, naphthenes and oxygenates in the liquid product obtained on reacting CO with steam.

(5) FIG. 5 is a simulated distillation curve of products produced according to Example 8.

(6) FIG. 6 shows a scheme of an experimental set-up used in the dry reforming of methane with CO.sub.2.

(7) FIG. 7 shows a scheme of an apparatus suitable for conducting the reaction of CO with steam to form liquid hydrocarbons, or converting H.sub.2-lean syngas into liquid hydrocarbons.

EXAMPLES

Example 1

Preparation of Extrudates Consisting of Spinel Phase [Fe(Fe3+yAl3+1-y)2O4; (y=0.47)] and a Silica Binder Promoted with Potassium

(8) The catalytically active compound was prepared by co-precipitation from an aqueous solution of Fe and Al nitrates, induced by the addition of aqueous ammonium hydroxide solution. 27.0 gram of Al(NO.sub.3).sub.3.9H.sub.2O and 57.9 gram of Fe(NO.sub.3).sub.3.9H.sub.2O were dissolved in 60 cm.sup.3 of distilled water each. The solutions were then mixed together and the pH of the combined solution was adjusted to 8 by adding 250 cm.sup.3 of aqueous NH.sub.4OH solution with concentration of ammonium hydroxide of 5 wt %. The obtained solid was filtered and washed with distilled water and further dried at 110 C. for 24 hours. In the present example the atomic ratio of Fe:Al in the precipitating solution was 2:1. The dried spinel material was grinded using a ball mill to particle size <180 m, and mixed with SiO.sub.2 precursor (Ludox HS-30) at a weight ratio spinel/SiO.sub.2 70/30 (The SiO.sub.2 precursor was brought to pH=7 by few drops of 5M solution of HNO.sub.3 in water before the mixing with the spinel powder). The obtained mixture was left for gelation overnight at room temperature. The obtained gel was formed into pellets by extrusion through a die with openings diameter of 2.5 mm, followed by cutting the extruded wire into extrudates with a length of 15 mm (a single-screw extruder was used). The extrudates were aged in air at room temperature for 24 hours. The aged extrudates were dried in air at 110 C. for 6 hours followed by calcination in air at 350 C. for period of 6 hours. No Fe.sub.2O.sub.3 hematite phase was formed after calcination at 350 C. The calcined extrudates had diameter of 1.6 mm and length of 6-10 mm. An aqueous solution of K.sub.2CO.sub.3 was added by incipient wetness impregnation. The solid was further dried in air at 110 C. for 4 hours followed by calcination in air at 450 C. for period of 3 h. No change in the shape and size of the extrudates was detected at the impregnation step. The material had the following weight ratio of metal components (EDAX):Fe:Al:K=100:24:14.6, surface area 198 m.sup.2/gram, pore volume 0.33 cm.sup.3/gram and average pore diameter 6.7 nm.

Example 2

Preparation of Extrudates Consisting of Spinel Phase [Fe(Fe3+yAl3+1-y)2O4; (y=0.47)] and a Silica Binder Promoted with Potassium

(9) The catalytically active compound was prepared by co-precipitation from an aqueous solution of Fe and Al nitrates, induced by the addition of aqueous ammonium hydroxide solution. 27.0 gram of Al(NO.sub.3).sub.3.9H.sub.2O and 57.9 gram of Fe(NO.sub.3).sub.3.9H.sub.2O were dissolved in 60 cm.sup.3 of distilled water each. The solutions were then mixed together and the pH of the combined solution was adjusted to 8 by adding 250 cm.sup.3 of aqueous NH.sub.4OH solution with concentration of ammonium hydroxide of 5 wt %. The obtained solid was filtered and washed with distilled water and further dried at 110 C. for 24 hours. In the present example the atomic ratio of Fe:Al in the precipitating solution was 2:1. The dried spinel material was grinded using a ball mill to particle size <180 m, and mixed-kneaded with SiO.sub.2 precursor (Ludox HS-30) at a weight ratio spinel/SiO.sub.2 70/30 in a horizontal mixing kneader machine equipped with two Z-type blades, heating mantle and a cover for closing it hermetically (The SiO.sub.2 precursor was brought to pH=7 in a vessel by few drops of 5M solution of HNO.sub.3 in water before addition to kneader; the spinel powder was added to the kneader after addition of SiO.sub.2 precursor with adjusted pH). The obtained mixture was mixed-kneaded in the hermetically closed kneader at temperature of 40 C. for 5 h. The obtained gel was discharged from the kneader and formed into pellets by extrusion through a die with openings diameter of 2.5 mm, followed by cutting the extruded wire into extrudates with a length of 15 mm (a single-screw extruder was used). The extrudates were aged in air at room temperature for 24 hours. The aged extrudates were dried in air at 110 C. for 6 hours followed by calcination in air at 350 C. for period of 6 hours. No Fe.sub.2O.sub.3 hematite phase was formed after calcination at 350 C. The calcined extrudates had diameter of 1.6 mm and length of 6-10 mm. An aqueous solution of K.sub.2CO.sub.3 was added by incipient wetness impregnation. The solid was further dried in air at 110 C. for 4 hours followed by calcination in air at 450 C. for period of 3 h. No change in the shape and size of the extrudates was detected at the impregnation step. The material had the following weight ratio of metal components (EDAX):Fe:Al:K=100:24:14.6, surface area 203 m.sup.2/gram, pore volume 0.31 cm.sup.3/gram and average pore diameter 6.1 nm.

(10) In the set of experiments reported in Examples 3 to 5, the hydrogenation of carbon dioxide is illustrated. The extrudate of Example 1 and comparative catalysts were tested for their ability to advance the reaction of carbon dioxide with hydrogen to produce hydrocarbons.

Examples 3 and 4 (Both Comparative)

Carbon Dioxide Hydrogenation in Three Fixed Bed Reactors in Series in the Presence of Binder-Free Pellets and Alumina-Containing Pellets

(11) Two experiments were run, using an experimental set-up consisting of three serially positioned SS fixed bed reactors, as illustrated in WO 2014/111919.

(12) In the experiment corresponding to Example 3, the reaction was carried out in the presence of binder-free granules consisting of the spinel Fe.sup.2+(Fe.sup.3+.sub.0.47Al.sup.3+.sub.0.53).sub.2O.sub.4 which were produced by pressing the powdered catalyst in a press at a force of 10 tons, crushing and sieving the granules yielding a material with pellets size in the range 1.2-1.5 mm. Then, 3 g of these pellets (granules) were equally divided between the three reactors of the experimental set-up.

(13) In the experiment corresponding to Example 4, the catalytically active material was employed in the form of alumina-containing pellets, prepared as described in Example 29 of WO 2014/111919 (consisting of 66.6% Fe.sup.2+(Fe.sup.3+.sub.0.47Al.sup.3+.sub.0.53).sub.2O.sub.4, 24.2% Al.sub.2O.sub.3 and 9.2% K; 3% K was inserted before addition of Al.sub.2O.sub.3, the restafter calcination of Al.sub.2O.sub.3-containing extrudates). Then, 3 g of these pellets were equally divided between the three reactors in the experimental set-up.

(14) In both experiments, all the three reactors were kept at the same temperature (T=300 C.) and total pressure of 10 atm. WHSV of CO.sub.2 was 1 h.sup.1. H.sub.2/CO.sub.2 reactants molar ratio was roughly the same for both experiments (3.4 and 3.3, respectively). The experimental protocol is as described in WO 2014/111919 for the three reactors in series configuration. Measurements and calculations of conversion (X), selectivity (S) and productivity (P) are as explained in WO 2014/111919. The results are tabulated in Table 1.

(15) TABLE-US-00002 TABLE 1 CO.sub.2 C.sub.5+ C.sub.7+ oil WHSV P P Ex. h.sup.1 X.sub.CO2 % S.sub.CH4 % S.sub.CO % S.sub.C2-C4 S % (g/g.sub.cat .Math. h) .Math. 10.sup.2 S % (g/g.sub.cat .Math. h) .Math. 10.sup.2 3 1 59 8 8 23 52 9.1 37 6.5 4 1 61 9 10 29 44 7.9 29 5.2

(16) The results shown in Table 1 indicate the inferior performance of binder-containing pellets (with alumina as a binder) in comparison with that of binder-free pellets.

Examples 5 (Comparative) and 6 (of the Invention)

Carbon Dioxide Hydrogenation in a Single Fixed Bed Reactor in the Presence of Binder-Free Pellets and Silica-Containing Extrudates

(17) Two experiments were run. In each experiment, CO.sub.2 hydrogenation reaction was conducted by passing a mixture of H.sub.2 and CO.sub.2 flows in a tubular reactor (11 mm ID and 210 mm long, 45 mm catalytic phase) heated up to 330 C. at a total pressure of 20 atm. The WHSV and H.sub.2/CO.sub.2 reactants molar ratio were roughly the same in these experiments.

(18) In the experiment corresponding to Example 5, the reaction was carried out in the presence of binder-free granules. These granules were produced by pressing Fe.sup.2+(Fe.sup.3+.sub.0.47Al.sup.3+.sub.0.53).sub.2O.sub.4 powder prepared according to Example 7 of WO 2014/111919 which was impregnated with 3% potassium. The powder was pressed at a force of 10 tons, crushed and sieved to give granules. The so-formed granules were sieved to collect 1.2-1.5 mm large granules.

(19) In the experiment corresponding to Example 6, the performance of silica-containing extrudates was tested. These extrudates were prepared as described in Example 1 above, with the following weight composition: 65.8% Fe.sup.2+(Fe.sup.3+.sub.yAl.sup.3+.sub.1-y).sub.2O.sub.4, 28.2% SiO.sub.2, 6% K.

(20) In both experiments, the reaction products were cooled down to +4 C. and separated in cooled (+4 C.) container. Gas products were analyzed in online Agilent 7890A Series Gas Chromatograph equipped with 7 columns and 5 automatic valves using helium as a carrier gas. Liquid products were separated into aqueous and organic phases. Aqueous phase was analyzed for Total Organic Carbon in Shimadzu TOC-V.sub.CPN Analyzer. The selectivity of all products was calculated on the carbon basis as S.sub.i=[C.sub.i/(C.sub.CO2*X.sub.CO2)]*100%, where C.sub.i amount of carbon (gram) contained in product (i) produced at period of time, C.sub.CO2amount of carbon (gram) contained in CO.sub.2 passed the reactor at the same period of time, X.sub.CO2CO.sub.2 conversion.

(21) The results of the experiments are shown in Table 2. Note the following glossary: C.sub.5+hydrocarbons composed of five or more carbon atoms; C.sub.i(o)an olefin containing i carbon atoms; C.sub.i(p)a paraffin containing i carbon atoms; oxyoxygen-containing products. The capital letters X and S stand for conversion and selectivity, respectively.

(22) TABLE-US-00003 TABLE 2 WHSV Ex. (h) H.sub.2/CO.sub.2 X.sub.CO2 X.sub.H2 S.sub.C5+ S.sub.C1 S.sub.C2 (o) S.sub.CO S.sub.C3-C4 (o) S.sub.C2-C4 (p) S.sub.OXy 5 3.6 2.6 36 41 40 10 6.2 12 19 4.0 8.7 6 4.0 2.4 35 46 43 6.2 6.0 15 17 3.1 9.3

(23) The results indicate that the silica-containing extrudates function better than the binder-free competitors, demonstrating higher selectivity to C.sub.5+ hydrocarbons concurrently with lower selectivity to the lower alkanes and alkenes.

(24) In the set of experiments reported in Examples 7 to 9, the extrudates of Example 1 was tested for its ability to advance the reaction of carbon monoxide with steam to produce hydrocarbons according to the following conditions.

(25) A schematic description of the experimental set-up is shown in FIG. 2. Catalysts activation was done by in-situ reduction in hydrogen at 20 cm.sup.3/min*gram.sub.cat at temperature of 450 C. and atmospheric pressure in reactor (3), for 4 h. H.sub.2 stream supplied for the activation step is also shown (11).

(26) CO reaction with steam was then conducted by passing a mixture of steam and CO streams ((1) and (2), respectively) at a molar ratio 0.35:1 through a tubular reactor (3) (16 mm ID, 250 mm long) packed with 12 gram of the extrudates of Example 1 and heated up to 280 C. at a total pressure of 30 atm. Steam is produced by vaporizing water stream in a vaporizer (10). All gaseous reactants are fed via feed line (13) to the reactor (3).

(27) With the aid of a cooler (4A), the reaction products were cooled down to a temperature T.sub.1 (T.sub.1>100 C.) to form a first mixture consisting of non-condensable and liquid products. The first mixture is separated in a first gas-liquid separator (5A) into a first liquid component and a first gaseous component.

(28) The first liquid component obtained under the experimental conditions consists of organic and aqueous phases. The first liquid is therefore separated in a liquid-liquid separator (6) into organic and aqueous phases, which are collected in vessels(7A) and (8), respectively.

(29) The first gaseous component is cooled down with the aid of a second cooler (4B) to a temperature T.sub.2 (T.sub.2<10 C.), undergoing condensation to form a second mixture consisting of non-condensable materials and liquid products. The second mixture is then separated in a second gas-liquid separator (5B) into a second liquid component and a second gaseous component. The second liquid component, consisting of light organic products, is collected in a vessel (7B). The non-condensable components (9) consist of CO.sub.2, CO, light hydrocarbons and residual H.sub.2 generated by the water gas shift reaction.

(30) Gas products (9) were analyzed in online Agilent 7890A Series Gas Chromatograph equipped with 7 columns and 5 automatic valves using helium as a carrier gas. The liquid composition (7A, 7B) was analyzed by Agilent 190915-433 Gas Chromatograph combined with Mass Spectrometer in the range M/Z=33-500, equipped with 5973 mass selective detector, HP-5MS column (30 m, 250 m, i.d. 0.25 m) and helium as a carrier gas. The distillation patterns of the hydrocarbon oil produced were estimated by simulated distillation method based on the maximal boiling points of components in 10 vol % oil fractions. The liquid productivity was calculated based on the weighted amounts of liquid (W.sub.L) collected over a specific period of time on stream: P=W.sub.L/W.sub.cat*t gram/gram catalyst/h, where W.sub.cat is weight of catalyst (gram) loaded into reactor, ttime for collecting W.sub.L (hours). In the tables below, the capital letters X and S stand for conversion and selectivity, respectively. The weight selectivity to CH.sub.4, C.sub.2-C.sub.4 olefins (olefins are abbreviated in the tables below C.sub.2.sup.= and C.sub.3-C.sub.4.sup.=), C.sub.2-C.sub.4 paraffins and C.sub.5+ hydrocarbons was calculated on the carbon basis as S.sub.i=[C.sub.i/C.sub.i*100%, where C.sub.i is the amount of carbon (gram) contained in product (i) produced at period of time, C.sub.i-amount of carbon (gram) contained in all hydrocarbons produced over the same period of time. The selectivity to CO.sub.2, S.sub.CO2=F.sub.CO2/(F.sub.CO,0F.sub.CO), was calculated as the moles of CO.sub.2 produced per moles of CO reacted.

Example 7

Carbon Monoxide Reaction with Steam in a Fixed Bed Reactor in the Presence of Silica-Containing Extrudates

(31) The reaction of carbon monoxide with steam to produce hydrocarbons in a fixed bed reactor packed with the catalyst of Example 1 was carried out according to the general procedure set out above, under the following specific conditions:

(32) WHSV.sub.CO=0.42 h.sup.1, Temperature 280 C., total pressure in the reactor inlet 30 atm, H.sub.2O/CO=0.34 mol/mol. The time on stream was 506 hours. The results are shown in Table 3.

(33) TABLE-US-00004 TABLE 3 x.sub.CO, x.sub.H2O, s.sub.C1 s.sub.C2-C4 s.sub.C2.sup.= s.sub.C3-C4.sup.= s.sub.C5+ S.sub.CO2 H.sub.2/CO % % wt % wt % wt % wt % wt % mole % outlet 83 98 2.6 4.4 2.6 14 76 70 0.5

(34) The composition of the liquid product is shown in FIG. 3 in the form of a bar diagram.

Example 8

Carbon Monoxide (Mixed with Carbon Dioxide) Reaction with Steam in a Fixed Bed Reactor in the Presence of Silica-Containing Extrudates

(35) The reaction of carbon monoxide with steam in the presence of CO.sub.2, to produce hydrocarbons in a fixed bed reactor packed with the catalyst of Example 1 was carried out according to the general procedure set out above, under the following specific conditions:

(36) WHSV.sub.CO=0.42 h.sup.1, Temperature 280 C., total pressure at the reactor inlet 30 atm, H.sub.2O/CO=0.34 mol/mol, CO.sub.2/CO=0.25 mol/mol. The time on stream was 530 hours. The results are shown in Table 4.

(37) TABLE-US-00005 TABLE 4 x.sub.CO, x.sub.H2O, s.sub.C1 s.sub.C2-C4 s.sub.C2.sup.= s.sub.C3-C4.sup.= s.sub.C5+ S.sub.CO2 H.sub.2/CO % % wt % wt % wt % wt % wt % mole % outlet 73 96 0.7 3.8 4.2 15 76 70 0.5

(38) The composition of the liquid product is shown in FIG. 4 in the form of a bar diagram. The simulated distillation curve of products is depicted in FIG. 5.

Example 9

Carbon Monoxide (Mixed with Carbon Dioxide) Reaction with Steam in a Fixed Bed Reactor in the Presence of Silica-Containing Extrudates

(39) The reaction of carbon monoxide with steam in the presence of CO.sub.2, to produce hydrocarbons in a fixed bed reactor packed with the catalyst of Example 1 was carried out according to the general procedure set out above, under the following specific conditions:

(40) WHSV.sub.CO=0.6 h.sup.1, Temperature 300 C., total pressure at the reactor inlet 30 atm, H.sub.2O/CO=0.34 mol/mol, CO.sub.2/CO=0.25 mol/mol. The time on stream was 560 hours. The results are shown in Table 5.

(41) TABLE-US-00006 TABLE 5 x.sub.CO, x.sub.H2O, s.sub.C1 s.sub.C2-C4 s.sub.C2.sup.= s.sub.C3-C4.sup.= s.sub.C5+ S.sub.CO2 H.sub.2/CO % % wt % wt % wt % wt % wt % mole % outlet 85 96 3.4 4.7 4.2 23 65 70 0.6

(42) The experiments reported in Examples 10 to 13 relate to the conversion H.sub.2-lean syngas into hydrocarbons. First, Example 10 shows the generation of H.sub.2-lean syngas by dry reforming of natural gas with carbon dioxide with the aid of Ni-containing catalyst (the synthesis of the Ni-containing catalyst is shown in Preparation 1 below). Then, in Examples 11 to 13, the extrudates of Example 1 and 2 according to the invention and comparative extrudates are tested for their ability to advance the conversion of H.sub.2-lean syngas into hydrocarbons.

Example 10

Dry Reforming: Carbon Dioxide Reaction with Methane in a Fixed Bed Reactor

(43) A schematic description of the experimental set-up is shown in FIG. 6. The catalytic performance of the dry reforming (DR) catalyst (Ni-haxaaluminateBaNiAl.sub.11O.sub.19- of Preparation 1) was measured in stainless steel (0.95 cm I.D.) fixed bed reactor (21) with a central tube (0.31 cm O.D.) equipped with a movable thermocouple for measuring the axial temperature profile. The reactor is heated at the wall by a high temperature electrical heater. The reactor was packed with powder catalyst diluted with SiC powder of ring shape catalyst. Each gaseous reactant flows from cylinders (22) and its rate is controlled by an electronic mass flow controller (FC) (Brooks Co.). Feed and effluent streams were analyzed with an Agilent 7890A GC (GC) equipped with FID and TCD detectors and IR analyzer. Water was condensed (23) from the products gas stream using a cold trap (24) at the outlet of the reactor.

(44) The BaNiAl.sub.11O.sub.19- catalyst of Preparation 1 was used to promote the reaction of methane with carbon dioxide, to produce H.sub.2-lean syngas. 0.2 g of the catalyst of Preparation 1 in powdered form (106-150 m) diluted with 0.2 g SiO.sub.2 was loaded into the reactor. A gas mixture containing CH.sub.4 and CO.sub.2 was fed to the reactor. The catalyst was reduced at 900 C. for 1 h in a 60% H.sub.2-40% N.sub.2 mixture flow.

(45) The dry reforming of methane was conducted with the catalyst described in Preparation 1 at atmospheric pressure and 870 C. The feed was composed of 66 mol % CO.sub.2 and 34 mol % CH.sub.4. Running at 15 NL/g catalyst/h yielded 99% and 66% conversion of methane and CO.sub.2 respectively with H.sub.2/CO=0.6 in the product.

Examples 11 and 12 (of the Invention) and 13 (Comparative)

Carbon Monoxide Reaction with Hydrogen in a Fixed Bed Reactor

(46) A schematic description of the experimental set-up is shown in FIG. 2. Catalysts activation was done by in-situ reduction in hydrogen at 20 cm.sup.3/min*gram.sub.cat at temperature of 450 C. and atmospheric pressure in reactor (3), for 4 h.

(47) CO was contacted with H.sub.2 and optionally with steam by passing a mixture of CO, H.sub.2 and optionally H.sub.2O streams (indicated by numerals (2), (11) and (1), respectively) through a tubular reactor (3) (16 mm ID, 250 mm long) packed with 12 gram of the extrudates of the invention and heated up to 280 C. at a total pressure of 30 atm. Steam is produced by vaporizing water stream in a vaporizer (10). All gaseous reactants are fed via line (13) to the reactor (3).

(48) With the aid of a cooler (4A), the reaction products were cooled down to a temperature T.sub.1 (T.sub.1>100 C.) to form a first mixture consisting of non-condensable and liquid products. The first mixture is separated in a first gas-liquid separator (5A) into a first liquid component and a first gaseous component.

(49) The first liquid component obtained under the experimental conditions consists of organic and aqueous phases. The first liquid is therefore separated in a liquid-liquid separator (6) into organic and aqueous phases, which are collected in vessels (7A) and (8), respectively.

(50) The first gaseous component is cooled down with the aid of a second cooler (4B) to a temperature T.sub.2 (T.sub.2<10 C.), undergoing condensation to form a second mixture consisting of non-condensable materials and liquid products. The second mixture is then separated in a second gas-liquid separator (5B) into a second liquid component and a second gaseous component. The second liquid component, consisting of light organic products, is collected in a vessel (7B). The non-condensable components (9) consist of CO.sub.2, CO, light hydrocarbons and residual H.sub.2 generated by the water gas shift reaction.

(51) Products were analyzed as described in the previous set of Examples. In the tables below, the capital letters X and S stand for conversion and selectivity, respectively. The weight selectivity to CH.sub.4, C.sub.2-C.sub.4 olefins (olefins are abbreviated in the tables below C.sub.2.sup.= and C.sub.3-C.sub.4.sup.=), C.sub.2-C.sub.4 paraffins and C.sub.5+ hydrocarbons was calculated on the carbon basis as S.sub.i=[C.sub.i/C.sub.i*100%, where C.sub.i is the amount of carbon (gram) contained in product (i) produced at period of time, C.sub.iamount of carbon (gram) contained in all hydrocarbons produced over the same period of time. The selectivity to CO.sub.2, S.sub.CO2=F.sub.CO2/(F.sub.CO,0F.sub.CO), was calculated as the moles of CO.sub.2 produced per moles of CO reacted.

(52) In Example 11, the reaction of carbon monoxide with hydrogen to produce hydrocarbons was run in the experimental set-up described above, using the extrudate of Example 1, under the following specific conditions:

(53) WHSV.sub.CO=0.67 h.sup.1, temperature 280 C., total pressure at the reactor inlet 30 atm, H.sub.2/CO=0.25 mol/mol, H.sub.2O/CO=0.23 mol/mol. The time on stream was 280 hours. The results are shown in Table 7.

(54) TABLE-US-00007 TABLE 7 x.sub.CO, x.sub.H2O, s.sub.C1 s.sub.C2-C4 s.sub.C2.sup.= s.sub.C3-C4.sup.= s.sub.C5+ S.sub.CO2 H.sub.2/CO % % wt % wt % wt % wt % wt % mole % outlet 80 96 5.8 6.6 2.9 15 69 60 0.6

(55) In Example 12, the reaction of carbon monoxide with hydrogen to produce hydrocarbons was run in the experimental set-up described above, using the extrudates of Example 2, under the following specific conditions:

(56) WHSV.sub.CO=0.91 h.sup.1, Temperature 280 C., total pressure in the reactor inlet 30 atm, H.sub.2/CO=0.7 mol/mol. The results are shown in Table 8 (TOS indicates time on stream).

(57) TABLE-US-00008 TABLE 8 s.sub.C1 s.sub.C2-C4 s.sub.C2.sup.= s.sub.C3-C4.sup.= s.sub.C5+ S.sub.CO2 H.sub.2/CO TOS h x.sub.CO, % x.sub.H2, % wt % wt % wt % wt % wt % mole % outlet 170 91 80 6.2 6.1 3.4 13.3 70 48 1.6 290 90 79 6.3 6.5 3.2 13.0 70 48 1.4

(58) In Example 13, a comparative catalyst prepared as described in Preparation 2 was tested for its ability to advance the reaction of carbon monoxide with hydrogen to produce hydrocarbons. The catalyst was synthesized according to the procedure of D. B. Bukur et. al [Ind. & Eng. Chem. Res. 1989, 28, 1130], formed into silica-containing extrudates by the method of the invention and then tested under to the following conditions:

(59) WHSV.sub.CO=0.66 h.sup.1, Temperature 280 C., total pressure in the reactor inlet 30 atm, H.sub.2/CO=0.7 mol/mol. The results are shown in Table 9 (TOS indicates time on stream).

(60) TABLE-US-00009 TABLE 9 s.sub.C1 s.sub.C2-C4 s.sub.C2.sup.= s.sub.C3-C4.sup.= s.sub.C5+ S.sub.CO2 H.sub.2/CO TOS h x.sub.CO, % x.sub.H2, % wt % wt % wt % wt % wt % mole % outlet 138 83 74 6.7 5.6 3.4 12.1 72 48 1.1 208 79 79 6.8 5.7 3.5 12.2 71 48 1.0

(61) It is seen from the results set forth in Tables 8 and 9 that the extrudates of the invention have better performance than the prior art catalyst, achieving superior CO conversion over a prolonged period of time under higher WHSV.

Preparation 1

Catalyst for Use in Dry Reforming

(62) Ni-substituted hexaaluminate catalyst with the general formula BaNi.sub.xAl.sub.11-xO.sub.19- was prepared by co-precipitation from a solution of the corresponding metal nitrate salts by addition of ammonium carbonate at pH=7.5-8.0. Metal nitrates were dissolved separately in deionized water at 60 C. The clear solutions of metal nitrates (with the exception of aluminum nitrate) were then mixed together, followed by adjusting the pH value to 1 with the aid of nitric acid, before adding the aluminum nitrate solution into the metal nitrate mixture. The resulting solution was then poured at 60 C. with vigorous stirring into an aqueous solution containing a large excess of (NH.sub.4).sub.2CO.sub.3 to form the hexaaluminate precursor precipitate. During the precipitation, a large amount of CO.sub.2 was released while the pH value of the solution was maintained between 7.5 and 8.0. The resulting slurry was aged with continuous stirring at 60 C. for 3 h followed by filtration and washing with deionized water. The obtained cake was then dried at 110 C. in air overnight. The powder was further calcined at 500 C. for 2 h, followed by calcination at 1300 C. and 1400 C. for 3-5 h.

(63) The resulting powder was crushed and sieved to collect the fraction smaller than 160 m. XRD analysis yielded the following phases: Ba.sub.0.69Ni.sub.0.48Al.sub.6.36O.sub.1195%, -Al.sub.2O.sub.35%. The BET surface area is 12 cm.sup.2/g.

Preparation 2

Comparative Extrudate for Converting H2-Lean Syngas into Hydrocarbons Based on Ind. & Eng. Chem. Res. 1989, 28, 1130

(64) The preparation of CuFe-oxide powder component of extrudates was conducted according to procedure published by D. B. Bukur et. al [Ind. & Eng. Chem. Res. 1989, 28, 1130]. The solid was precipitated at pH=6 by reaction between Cu(NO.sub.3).sub.2.2.5H.sub.2O (0.22 g), Fe(NO.sub.3).sub.2.9H.sub.2O (144.7 g) in 596.7 cm.sup.3 water with 409 cm.sup.3 of 2.7 M aqueous ammonia solution at 82 C. After washing of precipitate with 3 L water and separation by filtration, the material was evacuated at 50 C. for 48 h and then at 120 C. for 18 h. A portion of this dried material was impregnated with aqueous solution of KHCO.sub.3, dried in vacuum at 120 C. for 16 h and calcined in air at 300 C. for 5 h yielding a material with composition 100Fe/3Cu/0.2K (atomic composition determined by EDAX analysis). Its surface area was 152 m.sup.2/g, pore volume 0.38 cm.sup.3/g and according to XRD analysis it contained only one crystalline phase-Fe.sub.2O.sub.3in full agreement with the results presented by D. B. Bukur for this material [Catal. Today, 1995, 24, 111].

(65) Another portion of the dried material, prepared as described above (15.3 g) was ground using a ball mill to particle size 25-180 m, and mixed with 21.9 g of SiO.sub.2 precursor Ludox HS-30 (The SiO.sub.2 precursor was brought to pH=7 by few drops of 5M solution of HNO.sub.3 in water before the mixing with the dried K/CuFe-oxide catalyst powder). The obtained gel was formed into pellets by extrusion through a die with openings diameter of 1.8 mm, followed by cutting the extruded wire in pellets with the length of 15 mm. The extrudates were aged in air at room temperature for 24 hours. The aged extrudates were dried in air at 110 C. for 6 hours followed by calcination in air at 300 C. for period of 3 hours. The calcined extrudates had diameter of 1.6 mm and length of 6-10 mm. An aqueous solution of KHCO.sub.3 was added by incipient wetness impregnation at amount yielding 4 wt. % K in extrudates. The solid was further dried in air at 110 C. for 8 hours followed by calcination in air at 300 C. for period of 6 h. No change in the shape and size of the pellets was detected at the impregnation step. The material had following weight ratio of metal components (EDAX): Fe:Cu:K=100:3:5.7, surface area 203 m.sup.2/gram, pore volume 0.43 cm.sup.3/gram and average pore diameter 8.5 nm.