Conversion of carbon monoxide, carbon dioxide, or a combination thereof over hybrid catalyst

Abstract

A feedstream comprising hydrogen and a gas selected from carbon monoxide, carbon dioxide, or a combination thereof is converted to a product mixture containing a combination of saturated and unsaturated two carbon atom and three carbon atom hydrocarbons via contact with a mixed catalyst comprising a mixed metal oxide catalyst selected from a copper oxide, copper oxide/zinc oxide, copper oxide/alumina, copper oxide/zinc oxide/alumina catalyst, a zinc oxide/chromium oxide catalyst, or a combination thereof, in admixture with a molecular sieve catalyst having a CHA, AEI, AEL, AFI, BEA, or DDR framework type, or a combination of such molecular sieves. Exemplary molecular sieve catalysts include SAPO-34, SAPO-18, SAPO-5, and Beta. Advantages include reduced production of C1 hydrocarbons, C4 and higher hydrocarbons, or both; long catalyst lifetimes; desirable conversions; and desirable proportions of C2 and C3 paraffins.

Claims

1. A process for preparing C.sub.2 and C.sub.3 hydrocarbons comprising (a) introducing a feedstream into a reactor, the feedstream comprising hydrogen gas and a gas selected from carbon monoxide, carbon dioxide, and combinations thereof, such that the hydrogen gas is present in an amount of from 10 volume percent to 90 volume percent, based on combined volumes of the hydrogen gas and the gas selected from carbon monoxide, carbon dioxide, and combinations thereof; and (b) contacting the feedstream and a mixed catalyst in the reactor, the mixed catalyst comprising as components (1) a mixed metal oxide catalyst selected from a copper oxide catalyst, a copper oxide/zinc oxide catalyst, a copper oxide/alumina catalyst, a copper oxide/zinc oxide/alumina catalyst, a chromium oxide/zinc oxide catalyst, and combinations thereof; and (2) a non-metal-modified molecular sieve catalyst selected from SAPO-34, SSZ-13, SAPO-18, SAPO-5, SAPO-11, Beta-zeolite, ZSM-58, and combinations thereof, such names corresponding to the naming convention of the International Zeolite Association; under reaction conditions sufficient to form a product mixture, the reaction conditions comprising a reactor temperature ranging from 300 degrees Celsius to 440 degrees Celsius; a pressure of at least one bar (100 kilopascals); and a gas hourly space velocity of at least 500 reciprocal hours; the product mixture having, as calculated on a carbon monoxide-free, carbon dioxide-free, and hydrogen-free basis, a combined ethane and propane content that is more than 45 percent by weight; a methane content of less than 15 percent by weight; a combined butane and higher saturated hydrocarbon content of less than 30 percent by weight; and a combined unsaturated hydrocarbon and oxygenate content of less than 10 percent by weight; each weight percentage being based upon total product mixture weight and, when taken together, equaling 100 percent by weight.

2. The process of claim 1 wherein the feedstream comprises carbon in the form of carbon monoxide in an amount greater than 50 mole percent, based on total carbon in the feedstream, such that the volumetric ratio of hydrogen gas to carbon monoxide ranges from 0.1:1 to 10:1; the mixed metal oxide catalyst is a copper oxide/zinc oxide/alumina catalyst; and the molecular sieve catalyst is SAPO-34.

3. The process of claim 1 wherein the feedstream comprises carbon in the form of carbon monoxide in an amount greater than 50 mole percent, based on total carbon in the feedstream, such that the volumetric ratio of hydrogen gas to carbon monoxide ranges from 0.1:1 to 10:1; the mixed metal oxide catalyst is a chromium oxide/zinc oxide catalyst; and the molecular sieve catalyst is SAPO-34.

4. The process of claim 1 wherein the temperature ranges from 350 C. to 440 C.; the pressure is at least 20 bar (2.0 megapascals); and the gas hourly space velocity ranges from 500 reciprocal hours to 12000 reciprocal hours.

5. The process of claim 1 wherein the feedstream comprises carbon in the form of carbon dioxide in an amount greater than 50 mole percent, based on total carbon in the feedstream, such that the volumetric ratio of hydrogen gas to carbon dioxide ranges from 0.1:1 to 10:1; the mixed metal oxide catalyst is a copper oxide/zinc oxide/alumina catalyst; and the molecular sieve catalyst is SAPO-34.

6. The process of claim 1 wherein the feedstream comprises carbon in the form of carbon dioxide in an amount greater than 50 mole percent, based on total carbon in the feedstream, such that the volumetric ratio of hydrogen gas to carbon dioxide ranges from 0.1:1 to 10:1; the mixed metal oxide catalyst is a chromium oxide/zinc oxide catalyst; and the molecular sieve catalyst is SAPO-34.

7. The process of claim 5 wherein the temperature ranges from 300 C. to 400 C.; the pressure is at least 2 bar (0.2 megapascals); and the gas hourly space velocity ranges from 500 reciprocal hours to 22000 reciprocal hours.

8. The process of claim 1 wherein the mixed catalyst has a weight/weight ratio of mixed metal oxide catalyst to molecular sieve ranging from 0.1:1 to 10:1.

9. The process of claim 1 wherein the product mixture has, as calculated on a carbon monoxide-free, carbon dioxide-free, and hydrogen-free basis, a combined ethane and propane content of more than 60 percent by weight; a methane content of less than 10 percent by weight; a combined butane and higher saturated hydrocarbon content of less than 25 percent by weight; and a combined unsaturated hydrocarbon and oxygenate content of less than 5 percent by weight; each weight percentage being based upon total product mixture weight and, when taken together, equaling 100 weight percent.

10. The process of claim 1, wherein the mixed catalyst consists essentially of (1) a mixed metal oxide catalyst selected from a copper oxide catalyst, a copper oxide/zinc oxide catalyst, a copper oxide/alumina catalyst, a copper oxide/zinc oxide/alumina catalyst, a chromium oxide/zinc oxide catalyst, and combinations thereof; and (2) a non-metal-modified molecular sieve catalyst selected from SAPO-34, SSZ-13, SAPO-18, SAPO-5, SAPO-11, Beta-zeolite, ZSM-58, and combinations thereof, such names corresponding to the naming convention of the International Zeolite Association.

Description

EXAMPLE 1

(1) Physically mix 100 microliters (4) of a copper-zinc-aluminum mixed metal oxide catalyst that has a copper (Cu) content of 39 wt %, a zinc (Zn) content of 25 wt %, and an aluminum (Al) content of 10 wt % (HiFUEL R120) and 100 microliters (4) of a silicoaluminophosphate catalyst (SAPO-34) by shaking them together in a bottle. Each of the two catalysts has a particle size before mixing ranging from 40 mesh (0.422 millimeter (mm)) to 80 mesh (0.178 mm).

(2) Activate the physically mixed catalyst using a 90/10 vol %/vol % mix of H.sub.2 and nitrogen (N.sub.2) at a GHSV of 6000 h.sup.1, a temperature of 280 C. and a pressure of 10 bar (1.0 MPa) for a period of three hours (3 hr). Use onset of activation as a reference point for Time-on-Stream (TOS)=0 hour (hr).

(3) Pass a combination of CO and H.sub.2 (H.sub.2:CO ratio of 1) over the activated catalyst at a GHSV of 6000 h.sup.1 while maintaining the pressure at 10 bar (1.0 MPa) and using a screening test protocol varied in H.sub.2:CO ratio and temperature (T) with a dwell time for each stage of 6 hr as follows:

(4) TABLE-US-00001 TABLE 1 Process conditions for CuO/ZnO/Al.sub.2O.sub.3 + SAPO-34 catalyst. H.sub.2:CO Stage ratio (vol/vol) T ( C.) 1 8.5 280 2 1 280 3 8.5 340 4 1 340 5 8.5 400 6 1 400

(5) Data in Table 2 hereinbelow are (a) only for Stages 4 and 6; (b) based on analysis of a sample of gaseous reactor effluent; and (c) determined using a calculation convention wherein selectivity for each product is referenced only to detected products.

(6) TABLE-US-00002 TABLE 2 Results for CuO/ZnO/Al.sub.2O.sub.3 + SAPO-34 catalyst. Calculated Calculated Calculated Calculated Calculated C1 SEL C2 SEL C3 SEL C4 SEL T CONV (mol %) (mol %) (mol %) (mol %) Other* ( C.) (mol %) CO2 CH4 C.sub.2H4 C2H6 C3H6 C3H8 C4H8 C4H10 (mol %) 340 6.0 66 <1 1.5 8.9 5.9 16.6 0 0 <0.1 400 18.3 51 3.8 0 18.4 5.8 20.1 0 0 0.9 *Represents oxygenates and any hydrocarbon that are otherwise below quantification limit (BQL).

(7) Skilled artisans recognize that conversion of a combination of CO and H.sub.2 may yield a number of unspecified by-products including some that can be deposited on the catalyst bed (e.g., as carbon or as waxes) and, as such, cannot be detected by gas chromatography (GC). A calculation of conversion and selectivity that appears to be more accurate references data to an absolute decrease in amount of CO passing through the reactor (designated herein as absolute carbon conversion and absolute carbon selectivity). Table 3 hereinbelow presents re-calculated results for Stages 3 through 6 of the above screening protocol. The re-calculated results reflect peak assignment corrections based upon use of a reference cylinder of known gas composition (a certified mixture of simple paraffins (lower hydrocarbons (C.sub.1-C.sub.6), with no isomers such as isobutane), olefins (no isomers such as 2-butene), CO, CO.sub.2 and H.sub.2 balanced to 100 vol % by N.sub.2. The re-calculation indicates that the olefins reported in Table 2 are not actually olefins, and thus their values in Table 3 are corrected to zero.

(8) TABLE-US-00003 TABLE 3 Results for CuO/ZnO/Al.sub.2O.sub.3 + SAPO-34 catalyst, re-calculated. C C.sub.1 SEL C.sub.2 SEL C.sub.3 SEL C.sub.4 SEL T H.sub.2:CO CONV (mol %) (mol %) (mol %) (mol %) Other ( C.) ratio (mol %) CO.sub.2 CH.sub.4 C.sub.2H.sub.4 C.sub.2H.sub.6 C.sub.3H.sub.6 C.sub.3H.sub.8 C.sub.4H.sub.8 C.sub.4H.sub.10 (mol %) 340 8.5 28.2 41.4 5.7 0 10.1 0 21.1 0 6.4 13.3 340 1 6.3 30.9 0.3 0 4.1 0 8.5 0 2.9 46.7 400 8.5 46.3 37.5 7.2 0 24.2 0 26.4 0 4.7 0 400 1 18.2 41.8 3.1 0 14.8 0 17.8 0 4.9 17.6

(9) The data in Table 3 demonstrate that the higher temperature shown (400 C.) improves the yield of C.sub.2-C.sub.3 hydrocarbons, by increasing both CO conversion and C.sub.2-C.sub.3 selectivity. The data also demonstrate that, for the conditions shown in this Example 1, an increase in H.sub.2:CO ratio, while maintaining the same temperature, pressure and GHSV, leads to an increase in CO conversion, but with a higher selectivity to CH.sub.4.

EXAMPLE 2

(10) Replicate Example 1, but use four stages rather than six stages, with a H.sub.2:CO ratio of 1, a process pressure of 10 bar (1.0 MPa), a GHSV of 6000 h.sup.1 and a dwell time of 6 hr per stage. Results are recorded in Table 4 hereinbelow.

(11) TABLE-US-00004 TABLE 4 Results for CuO/ZnO/Al.sub.2O.sub.3 + SAPO-34 catalyst. C C.sub.1 SEL C.sub.2 SEL C.sub.3 SEL C.sub.4 SEL T CONV. (mol %) (mol %) (mol %) (mol %) Other Stage ( C.) (mol %) CO.sub.2 CH.sub.4 C.sub.2H.sub.4 C.sub.2H.sub.6 C.sub.3H.sub.6 C.sub.3H.sub.8 C.sub.4H.sub.8 C.sub.4H.sub.10 (mol %) 1 280* 10.7 35.4 0 0 0.8 0 1.4 0 **BQL 62.4 2 340 5.3 45.1 3.7 0 7.3 0 10.1 0 1.1 32.7 3 360 7.3 50.5 3.5 0 19.4 0 23.8 0 2.8 0 4 380 13.8 48.1 1.6 0 22.0 0 25.0 0 3.3 0 *Outside of claimed temperature range. **Below Quantification Limit, an indication that with the GC apparatus used for this Example, a peak value is too small to be quantified.

(12) The data in Table 4 demonstrate that a temperature in excess of 360 C. operates more effectively than a temperature of 360 C. or below to reduce CH.sub.4 (C1 hydrocarbon) formation while improving carbon conversion and selectivity to C2 and C3 products, under the previously defined conditions of this Example 2. A comparison of this data with the data in Table 3 also shows that the overall selectivity to C2 and C3 products is higher at 380 C., 10 bar pressure, and a H.sub.2:CO ratio of 1 than at 400 C., 10 bar (1.0 MPa) pressure, and a H.sub.2:CO ratio of 1.

EXAMPLE 3

(13) Replicate Example 2, but introduce a combination of CO and H.sub.2 to the reactor only after the reactor temperature reaches a temperature of 380 C. Results are reported in Table 5 hereinbelow.

(14) TABLE-US-00005 TABLE 5 Results for CuO/ZnO/Al2O3 + SAPO-34 catalyst at 380 C. C C.sub.1 SEL C.sub.2 SEL C.sub.3 SEL C.sub.4 SEL CONV. (mol %) (mol %) (mol %) (mol %) Other (mol %) CO.sub.2 CH.sub.4 C.sub.2H.sub.4 C.sub.2H.sub.6 C.sub.3H.sub.6 C.sub.3H.sub.8 C.sub.4H.sub.8 C.sub.4H.sub.10 (mol %) 24.3 46.8 0.9 0 17.9 0 27.3 0 6.8 0.3

(15) A comparison of data among Tables 2-5 showing catalytic performance results for the same mixed (hybrid) catalyst tested at pressure=10 bar, GHSV=6000 h.sup.1 and H.sub.2:CO ratio=1 highlights a surprising and important effect on selectivity (less CH.sub.4 and more C.sub.2-C.sub.3 in the product stream) and on activity (higher CO conversion) where the hybrid is prevented from exposure to the reactive feedstream at lower process temperatures (below 360 C.).

EXAMPLE 4

(16) Replicate Example 3, but with the same catalyst being exposed to a combination of CO and H.sub.2 that has a H.sub.2:CO ratio=3, pressure=20 bar (2.0 MPa), reactor temperature of 380 C., with a dwell time of 12 hr. Results are summarized in Table 6 hereinbelow.

(17) TABLE-US-00006 TABLE 6 Results for CuO/ZnO/Al.sub.2O.sub.3 + SAPO-34 catalyst. C C.sub.1 SEL C.sub.2 SEL C.sub.3 SEL C.sub.4 SEL CONV (mol %) (mol %) (mol %) (mol %) Other (mol %) CO.sub.2 CH.sub.4 C.sub.2H.sub.4 C.sub.2H.sub.6 C.sub.3H.sub.6 C.sub.3H.sub.8 C.sub.4H.sub.8 C.sub.4H.sub.10 (mol %) 64 40.7 1.7 0 17.6 0 28.4 0 7.9 3.7

(18) The data in Table 6, in comparison with that in Table 5, demonstrate that process conditions may be varied within the scope of teachings presented herein while still obtaining significant improvement in carbon conversion without appreciable differences in C.sub.1-C.sub.4 selectivities.

EXAMPLE 5

(19) A comparison of use of a CuO/ZnO/Cr.sub.2O.sub.3+SAPO-34 catalyst versus a Cr.sub.2O.sub.3/ZnO+SAPO-34 catalyst is carried out to determine the effect of CuO, as follows:

(20) Mixed metal oxide (MMO) catalyst 5(a): Prepare a mixed metal oxide catalyst from copper nitrate, zinc nitrate and chromium nitrate precursors. Target elemental composition is Cu (10 mol %), Zn (45 mol. %) and chromium (Cr) (45 mol %).

(21) MMO catalyst 5(b): Precursors are zinc nitrate and chromium nitrate. Target elemental composition is 50 mol % each of Zn and Cr.

(22) Start preparation of each catalyst by vigorously mixing solutions of the precursors added in a proportion that targets the desired elemental composition defined hereinabove. Effect co-precipitation at ambient conditions (nominally 25 C. and one (1) atmosphere (atm, 1.01 bar, 98.1 kilopascals (kPa)) pressure by transferring 20 milliliters (mL) volume of mixed precursors to a vial containing 20 mL of ammonium hydroxide (Aldrich, 28-30% NH.sub.3 basis). This results in a rapid co-precipitation of mixed hydroxides. During a follow-up aging stage (16 hr), subject the co-precipitate to constant orbital shaking (500 revolutions per minute (rpm)) and heating (100 C.) to yield a gel-like residue of mixed hydroxides and oxides. Finally, transfer the residue to an oven and calcine it under temperature-programmed conditions (static air, ramp 2 C./min to 550 C., dwell 5 hr at 550 C.). Crush and sieve the calcined residue to a desired particle size (from 40 mesh (0.422 mm) to 80 mesh (0.178 mm)).

(23) Analysis by X-ray fluorescence of catalyst 5(a) gives an elemental oxide composition as follows: CuO 8.9 wt %, ZnO 43.1 wt %, and Cr.sub.2O.sub.3 48.0 wt %, each wt % being based upon combined weight of CuO, ZnO and Cr.sub.2O.sub.3. X-ray fluorescence (XRF) analysis of catalyst 5(b) gives an elemental oxide composition as follows: 51 wt % ZnO and 49 wt % Cr.sub.2O.sub.3 each wt % being based upon combined weight of ZnO and Cr.sub.2O.sub.3.

(24) Physically mix each catalyst independently (5(a) or 5(b)) with SAPO-34 as in Example 1, then activate the physical mix as in Example 1, but change the temperature of the reaction to 400 C. and 450 C., for physical mixtures SAPO-34/5(a) and SAPO-34/5(b), respectively, hereinafter denominated as hybrid catalysts HC-5a and HC-5b, respectively. The onset of the activation stage is herein a reference point for Time-on-Stream (TOS)=0 hours.

(25) Pass a combination of CO and H.sub.2 over the activated catalyst as in Example 1 using a process pressure (P) of 10 bar (1.0 MPa) and a temperature, GHSV and H.sub.2:CO ratio as shown in Table 7a (for HC-5a) and Table 7b (for HC-5b). Tables 8a, 8b, and 8c show CO conversion and selectivity values for the given reactions.

(26) TABLE-US-00007 TABLE 7a Conditions for HC-5a (CuO/ZnO/Cr.sub.2O.sub.3 + SAPO-34 catalyst). H.sub.2:CO Process GHSV Dwell Stage ratio T ( C.) (h.sup.1) time (hr) 1 8.5 400 6000 12 2 1 400 6000 12 3 0.1 400 6000 6 4 8.5 450* 6000 6.22 5 8.5 450* 3000 6 6 1 450* 6000 6 7 1 450* 3000 6 *Outside claimed temperature range.

(27) TABLE-US-00008 TABLE 7b Conditions for HC-5b (Cr.sub.2O.sub.3/ZnO catalyst + SAPO-34 catalyst) Dwell H.sub.2:CO Process GHSV time Stage ratio T ( C.) (hr.sup.1) (hr) 1 8.5 400 6000 6 2 1 400 6000 6 3 0.1 400 6000 6 4 0.1 450* 6000 2.19 *Outside claimed temperature range.

(28) TABLE-US-00009 TABLE 8a Stage 2 (400 C. and H.sub.2:CO ratio = 1) for HC-5a, calculated using same method as in Table 2. Tentative Tentative C.sub.2 Tentative Tentative Tentative C.sub.1 SEL** SEL C.sub.3 SEL C.sub.4 SEL C CONV* (mol %) (mol %) (mol %) (mol %) Other (mol %) CO.sub.2 CH.sub.4 C.sub.2H.sub.4 C.sub.2H.sub.6 C.sub.3H.sub.6 C.sub.3H.sub.8 C.sub.4H.sub.8 C.sub.4H.sub.10 (mol %) 6.3 62.6 9.2 0 8.7 9.0 10.5 <1 0 0 *Conversion **Selectivity

(29) TABLE-US-00010 TABLE 8b HC-5a, corrected calculation using same method as in Table 3. C.sub.1 SEL C.sub.2 SEL C.sub.3 SEL C.sub.4 SEL H.sub.2:CO (mol %) (mol %) (mol %) (mol %) Other T ( C.) ratio C CONV. CO.sub.2 CH.sub.4 C.sub.2H.sub.4 C.sub.2H.sub.6 C.sub.3H.sub.6 C.sub.3H.sub.8 C.sub.4H.sub.8 C.sub.4H.sub.10 (mol %) 400 8.5 14.4 41 19.6 0 4 1.6 9.5 0 0 24.3 400 1 6.8 41 6.1 0.3 5.8 5.8 6.9 0 0.6 26.7 400 0.1 1.2 30.6 0 0 0 4.6 0 0 0 64.8 450* 8.5 22 35.2 33.9 0 10.6 0 7.3 0 0 13.0 450* 8.5 31.1 29.7 31.6 0 4.1 0 4 0 0 30.6 450* 1 8.7 31.4 11.5 0 7.1 1.3 5.7 0 0.8 42.2 450* 1 13.3 25.5 10.1 0 5.4 0 4.1 0 0.6 54.3 *Outside claimed temperature range

(30) TABLE-US-00011 TABLE 8c HC-5b, calculated using same method as in Table 4. C.sub.1 SEL C.sub.2 SEL C.sub.3 SEL C.sub.4 SEL H.sub.2:CO (mol %) (mol %) (mol %) (mol %) Other T ( C.) ratio C CONV. CO.sub.2 CH.sub.4 C.sub.2H.sub.4 C.sub.2H.sub.6 C.sub.3H.sub.6 C.sub.3H.sub.8 C.sub.4H.sub.8 C.sub.4H.sub.10 (mol %) 400 8.5 11.6 39.4 26.6 0 0.1 0.4 4.6 0 0 28.9 400 1 5.8 30.6 6.7 0 5.3 1.5 7.3 0 0 48.6 400 0.1 1.1 16.4 0 0 0 0 1.3 0 0 82.3 450* 0.1 1.4 15.4 0 0 0.1 0 1.2 0 0 83.3 *Outside claimed temperature range.

(31) The data in Tables 8b and 8c demonstrate that the chromium-based mixed metal oxide catalyst (Cr.sub.2O.sub.3/ZnO, HC-5b) gives acceptable results when mixed with SAPO-34 at 400 C. (Table 8c), although its yield of C2 and C3 paraffins is lower than that of the CuO/ZnO/Cr.sub.2O.sub.3 catalyst (HC-5a) under similar conditions (Table 8b). Thus, the inclusion of the CuO in catalyst HC-5a offers a significant benefit.

COMPARATIVE EXAMPLES A and B

(32) Replicate Example 1 with changes to temperature, pressure and GHSV as shown in Tables 9-A and 9-B hereinbelow. Change the amount of HiFUEL R120 and SAPO-34 to 500 L for each catalyst and use a combination of CO and H.sub.2 having a H.sub.2:CO ratio=1. Tables 9-A and 9-B indicate catalyst performance results obtained during two distinct tests, during which conditions are varied as the test proceeds.

(33) In the first test (Table 9-A for Comparative Example A), initiate exposure of the activated catalyst to a combination of CO and H.sub.2 at a temperature of 280 C., pressure of 42 bar (4.2 megapascals (MPa)) and GHSV 7200 h.sup.1. As shown in Table 9-A, this combination of conditions yields a comparatively low conversion with no observed production of hydrocarbons (only CO.sub.2 and oxygenates). In a second step, increase the temperature to 310 C. at the same conditions. In a third step, increase the temperature to 340 C. at the same conditions. In a fourth step, increase the temperature to 370 C. at the same conditions. In a fifth and final step, increase the temperature to 400 C. at the same conditions.

(34) In the second test (Table 9-B for Comparative Example B), start exposure of the activated catalyst to the combination of CO and H.sub.2 at a temperature of 340 C., and the same pressure and GHSV as in the first test. In a second step, decrease the GHSV to 3600 h.sup.1 at the same conditions. In a third step, decrease the pressure to 30 bar (3.0 MPa). In a fourth step, increase the temperature to 360 C. In a fifth step, decrease the pressure to 20 bar (2.0 MPa). In a sixth and final step, increase the temperature to 380 C.

(35) TABLE-US-00012 TABLE 9-A Run C C.sub.1 SEL C.sub.2 SEL C.sub.3 SEL C.sub.4 SEL T time CONV (mol %) (mol %) (mol %) (mol %) Other ( C.) (hr) (mol %) CO.sub.2 CH.sub.4 C.sub.2H.sub.4 C.sub.2H.sub.6 C.sub.3H.sub.6 C.sub.3H.sub.8 C.sub.4H.sub.8 C.sub.4H.sub.10 (mol %) 280* 16 9.3 20.3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 79.7 310 26.2 15.3 29.6 0.6 0.0 1.0 0.0 0.6 0.0 0.0 68.2 340 29.8 16.9 33.7 1.9 0.0 1.7 0.0 1.3 0.0 0.0 61.0 370 34.7 14.1 36.0 4.5 0.0 3.0 0.0 3.3 0.0 0.0 53.2 400 39.8 11.1 43.5 7.3 0.3 12.4 0.0 14.7 0.0 0.0 25.8 *Outside claimed temperature range.

(36) TABLE-US-00013 TABLE 9-B Run C C.sub.1 SEL C.sub.2 SEL C.sub.3 SEL C.sub.4 SEL T P time CONV (mol %) (mol %) (mol %) (mol %) Other ( C.) (bar/MPa) (hr) (mol %) CO.sub.2 CH.sub.4 C.sub.2H.sub.4 C.sub.2H.sub.6 C.sub.3H.sub.6 C.sub.3H.sub.8 C.sub.4H.sub.8 C.sub.4H.sub.10 (mol %) 340 42/4.2 12.6 22.2 34.7 1.5 0 2.6 0 3.9 0 1.6 55.7 340 42/4.2 30.9 22.2 36.8 1.8 0 1.3 0 1.3 0 0.7 58.1 340 30/3.0 42.4 13.9 33.1 1.8 0 1.2 0 1.6 0 0 62.3 360 30/3.0 59.3 10.7 36.5 3 0 4.6 0 6.5 0 0 49.4 360 20/2.0 76.2 6.6 43.2 2.5 0 12 0 14.7 0 2.1 25.5 380 20/2.0 87.2 11.6 48.2 1.8 0.7 19.3 3.3 21.8 0 4.7 0.2

(37) The data in Tables 9-A and 9-B show that an initial less preferred reactor temperature has an impact on catalyst performance when the reactor is later brought to some of the more preferred temperature conditions.

EXAMPLE 6

(38) Physically mix a copper-zinc-aluminum mixed metal oxide catalyst, having a copper (Cu) content of 39 wt %, a zinc (Zn) content of 25 wt %, and an aluminum content of 10 wt % (HiFUEL R120), and a silicoaluminophosphate catalyst (SAPO-34) by shaking them together in a bottle. Each of the catalysts has a particle size before mixing within a range of from 40 mesh (0.422 mm) to 80 mesh (0.178 mm). Activate the physically mixed catalyst using a pure hydrogen stream at a flow of 100 milliliters per minute (mL/min), a temperature of 270 C. and a pressure of 10 bar (1.0 MPa) for a period of 6 hr. Pressurize the system with pure N.sub.2 up to the intended operating pressure. Heat up the system to the intended operating temperature while still flowing pure N.sub.2 gas. Switch off the flow of N.sub.2 and start passing the desired feed mix over the activated catalyst.

(39) Tables 10-A1 through 10-F3 demonstrate how variations in a parameter, such as temperature in Tables 10-A1 and 10-A2, affect CO conversion and product selectivity.

(40) TABLE-US-00014 TABLE 10-A1 Temperature screening at a pressure of 20 bar (2.0 MPa), a GHSV of 4000 h.sup.1, a H.sub.2/CO ratio of 3 and a catalyst wt ratio of HiFUEL R120/SAPO-34 of 3 CO C.sub.1 Sel C.sub.2 Sel C.sub.3 Sel C.sub.4 Sel Oxygenates T TOS CONV (mol %) (mol %) (mol %) (mol %) Sel (mol %) Other ( C.) (hr) (mol %) CO.sub.2 CH.sub.4 C.sub.2H.sub.4 C.sub.2H.sub.6 C.sub.3H.sub.6 C.sub.3H.sub.8 C.sub.4H.sub.8 C.sub.4H.sub.10 DME MeOH (mol %) 330* 10 61 43.1 1.8 0 14.2 0.1 25 0 8.2 0.5 0.3 11.0 330* 50 14.5 31.7 3.9 0 1.8 0 1.8 0 1.1 53.8 5.9 0 340* 10 68.5 41.2 1.1 0 14.6 0 26.1 0 8.5 0 0.1 9.4 340* 50 14.3 33.6 5.5 0 3.3 0 4.2 0 1.4 53.2 3.8 5.0 350* 10 66.1 41.2 1.1 0 15.2 0 26.6 0 8.5 0 0.1 7.3 350* 50 13.2 34.7 6.1 0 4.6 0 6.5 0 1.7 43.5 2.9 0 360 10 64.6 42.3 1 0 16.6 0 27.5 0 8.4 0 0.1 4.9 360 50 52.6 42.6 1.1 0 16.1 0 27.8 0 8.1 0.1 0.1 4.0 370 10 59.4 41 1.2 0 16.5 0 26.6 0 8.6 0 0.1 5.0 370 50 50.1 42.9 1.3 0 17 0 28.2 0 8.2 0 0.1 2.3 380 10 50.7 42.6 1.2 0 18.4 0 27.2 0 8 0 0.1 2.5 380 50 36.5 45.1 2 0 18.0 0.1 27.5 0 7.0 0.1 0.2 0 400 10 39.7 40 2.9 0 17.6 0 23.3 0 7.2 0 0 9.0 400 50 30.4 41.7 3.5 0 17.9 0.1 24.2 0 6.5 0 0 8.1 410 10 33.6 41.2 4.2 0 19.5 0 23.3 0 6.7 0 0 5.1 410 50 24 39.3 6.4 0.2 17.5 0.2 20.5 0 4.8 0 0 11.1 430 10 19.1 40 11 0 18.9 0 17.7 0 4.2 0 0.1 8.1 430 50 9.3 41.7 25.4 1.1 21.6 0.4 8.9 0 1.3 0.5 0.2 0.3 *Comparative data

(41) TABLE-US-00015 TABLE 10-A2 (CO.sub.2 free selectivities and CO.sub.2 inclusive selectivities) Temperature screening at a pressure of 20 bar (2.0 MPa), a GHSV of 4000 h1, a H.sub.2/CO ratio of 3 and a catalyst wt ratio of HiFUEL R120/SAPO-34 of 3 CO.sub.2 free selectivities CO.sub.2 inclusive selectivities (wt %) (wt %) T (wt %) (wt %) (wt %) Oxygenates + (wt %) (wt %) (wt %) (wt %) Oxygenates + ( C.) CH.sub.4 C.sub.2H.sub.6 + C.sub.3H.sub.8 C.sub.4H.sub.10 olefins CO.sub.2 CH.sub.4 C.sub.2H.sub.6 + C.sub.3H.sub.8 C.sub.4H.sub.10 olefins 330* 4 77 16 3 72 1 22 4 1 330* 4 4 1 91 46 2 2 1 49 340* 2 81 17 0 71 1 24 5 0 340* 6 7 1 86 49 3 4 1 44 350* 2 81 16 0 70 1 24 5 0 350* 7 12 2 79 52 4 6 1 38 360 2 82 15 0 70 1 25 5 0 360 2 82 15 1 70 1 24 4 0 370 2 81 16 0 70 1 25 5 0 370 3 82 15 0 70 1 25 4 0 380 2 83 14 0 70 1 25 4 0 380 4 82 12 1 71 1 24 4 0 400 6 80 14 0 70 2 24 4 0 400 7 80 12 0 70 2 24 4 0 410 8 79 12 0 69 3 24 4 0 410 14 76 9 1 70 4 23 3 0 430 22 69 8 0 69 7 21 2 0 430 44 49 2 4 67 15 17 1 1 *Comparative data

(42) TABLE-US-00016 TABLE 10-B1 Pressure screening at a temperature of 380 C., a GHSV of 4000 hr.sup.1, a H.sub.2/CO ratio of 3, and a catalyst wt ratio of HiFUEL R120/SAPO-34 of 3 CO C.sub.1 Sel C.sub.2 Sel C.sub.3 Sel C.sub.4 Sel Oxygenates P TOS CONV (mol %) (mol %) (mol %) (mol %) Sel (mol %) Other (bar/kPa) (hr) (mol %) CO.sub.2 CH.sub.4 C.sub.2H.sub.4 C.sub.2H.sub.6 C.sub.3H.sub.6 C.sub.3H.sub.8 C.sub.4H.sub.8 C.sub.4H.sub.10 DME MeOH (mol %) 5/500 10 3.1 28.9 8.5 0 9.2 0 7.8 0 0 0.3 0 45.3 5/500 50 2.3 27 16.2 0 7.9 0 3 0 0 0.4 0 45.4 20/2000 10 50.7 42.6 1.2 0 18.4 0 27.2 0 8 0 0.1 2.2 20/2000 50 36.5 44.6 2 0 18.2 0.1 26.7 0 7.1 0.1 0.2 0 35/3500 10 74 36.9 1.9 0 16.5 0 27.3 0 8.3 0 0.1 9.0 35/3500 50 70.1 38.9 1.8 0 16.5 0 28.7 0 8.3 0 0.1 5.7 50/5000 10 81.4 35.1 2.7 0 16 0 28.7 0 8.6 0 0.2 8.7 50/5000 50 79.4 36.5 2.6 0 15.6 0 29.7 0 8.8 0 0.2 6.6

(43) TABLE-US-00017 TABLE 10-B2 (CO.sub.2 free selectivities and CO.sub.2 inclusive selectivities) - Pressure screening at a temperature of 380 C., a GHSV of 4000 h.sup.1, a H.sub.2/CO ratio of 3 and a catalyst wt ratio of HiFUEL R120/SAPO-34 of 3 CO.sub.2 free selectivities CO.sub.2 inclusive selectivities (wt %) (wt %) P (wt %) (wt %) (wt %) Oxygenates + (wt %) (wt %) (wt %) (wt %) Oxygenates + (bar/MPa) CH.sub.4 C.sub.2H.sub.6 + C.sub.3H.sub.8 C.sub.4H.sub.10 olefins CO.sub.2 CH.sub.4 C.sub.2H.sub.6 + C.sub.3H.sub.8 C.sub.4H.sub.10 olefins 5/0.5 34 64 0 2 76 8 15 0 0 5/0.5 60 38 0 2 73 16 10 0 1 20/2.0 2 83 14 0 70 1 25 4 0 20/2.0 4 82 12 1 71 1 24 4 0 35/3.5 4 81 15 0 67 1 27 5 0 35/3.5 4 81 15 0 68 1 26 5 0 50/5.0 5 79 15 1 65 2 28 5 0 50/5.0 5 79 15 1 66 2 27 5 0

(44) TABLE-US-00018 TABLE 10-C1 H.sub.2/CO volumetric feed ratio screening at a temperature of 380 C., a pressure of 50 bar (5.0 MPa), a GHSV of 4000 h.sup.1, a H.sub.2/CO ratio of 3 and a catalyst wt ratio of HiFUEL R120/SAPO-34 of 3 CO C.sub.1 Sel C.sub.2 Sel C.sub.3 Sel C.sub.4 Sel Oxygenates H.sub.2/CO TOS CONV (mol %) (mol %) (mol %) (mol %) Sel (mol %) Other v-ratio (hr) (mol %) CO.sub.2 CH.sub.4 C.sub.2H.sub.4 C.sub.2H.sub.6 C.sub.3H.sub.6 C.sub.3H.sub.8 C.sub.4H.sub.8 C.sub.4H.sub.10 DME MeOH (mol %) 2 10 82.3 38.8 2.1 0 15.4 0 27.6 0 8 0 0.1 8.0 2 50 77.5 40.2 2.2 0 14.6 0 27.1 0 7.9 0 0.1 7.9 3 10 81.4 35.1 2.7 0 16 0 28.7 0 8.6 0 0.2 8.7 3 50 79.4 36.5 2.6 0 15.6 0 29.7 0 8.8 0 0.2 6.6 4 10 80 31.3 3.6 0 16.9 0 30.9 0 9 0 0.1 8.7 4 50 79.5 31.1 3.3 0 16.3 0 31.2 0 8.8 0 0.1 9.2 5 10 79.6 29.3 3.8 0 15.9 0 31.5 0 9.4 0 0.2 8.9 5 50 78 30.7 3.4 0 16.1 0 32.7 0 9.4 0 0.2 7.5 6 10 78.7 26.9 4.7 0 16.4 0 32.1 0 9.5 0 0.2 10.2 6 50 76.9 28.4 4.3 0 16.7 0 33.4 0 9.6 0 0.2 7.4

(45) TABLE-US-00019 TABLE 10-C2 (CO.sub.2 free selectivities and CO.sub.2 inclusive selectivity) - H.sub.2/CO feed ratio screening at a temperature of 380 C., a pressure of 50 bar (5.0 MPa), a GHSV of 4000 h.sup.1, and a catalyst wt ratio of HiFUEL R120/SAPO-34 of 3 CO2 free selectivities CO2 inclusive selectivities (wt %) (wt %) H.sub.2:CO (wt %) (wt %) (wt %) Oxygenates + (wt %) (wt %) (wt %) (wt %) Oxygenates + ratio CH.sub.4 C.sub.2H.sub.6 + C.sub.3H.sub.8 C.sub.4H.sub.10 olefins CO.sub.2 CH.sub.4 C.sub.2H.sub.6 + C.sub.3H.sub.8 C.sub.4H.sub.10 olefins 2 4 81 15 0 68 1 25 5 0 2 5 80 15 0 70 1 24 5 0 3 5 79 15 1 65 2 28 5 0 3 5 79 15 1 66 2 27 5 0 4 6 79 15 0 61 3 31 6 0 4 6 79 14 0 61 2 31 6 0 5 7 77 15 1 59 3 32 6 0 5 6 79 15 1 60 2 32 6 0 6 8 77 15 1 56 4 34 6 0 6 7 78 15 1 57 3 34 6 0

(46) TABLE-US-00020 TABLE 10-D1 Cat weight (wt) ratio HiFUEL R120/SAPO-34(screening at a temperature of 380 C., GHSV of 4000 h1, and a H.sub.2/CO ratio of 3 Cat CO C.sub.1 Sel C.sub.2 Sel C.sub.3 Sel C.sub.4 Sel Oxygenates P wt TOS CONV (mol %) (mol %) (mol %) (mol %) Sel (mol %) Other (bar/MPa) ratio (hr) (mol %) CO.sub.2 CH.sub.4 C.sub.2H.sub.4 C.sub.2H.sub.6 C.sub.3H.sub.6 C.sub.3H.sub.8 C.sub.4H.sub.8 C.sub.4H.sub.10 DME MeOH (mol %) 20/2.0 1 10 43.1 42.5 1.3 0 17.5 0.1 25.8 0 7.8 0 0.1 4.9 20/2.0 1 50 27.2 43 1.9 0 16.4 0.4 25.2 0 6.2 0 0.1 6.8 20/2.0 3 10 50.7 42.6 1.2 0 18.4 0 27.2 0 8 0 0.1 2.5 20/2.0 3 50 36.5 45.1 2 0 18.0 0.1 27.5 0 7.0 0.1 0.2 0 20/2.0 9.1 10 50.3 42.4 1.9 0 17.7 0 27 0 8.3 0 0.1 2.6 20/2.0 9.1 50 37 43.3 2.5 0 17 0 26.7 0 7.4 0 0.2 2.9 20/2.0 27.3 10 31.5 41 6.4 0 14.7 0 22.9 0 6.5 0.2 0.3 8.0 20/2.0 27.3 50 13.9 36.1 18.5 0 8.3 0 10.6 0 2.8 6.7 1.3 15.7 50/5.0 1.2 10 77.9 35.4 3 0 14.9 0 27.5 0 8.2 0 0.2 10.8 50/5.0 1.2 50 69.9 38.1 2.5 0 14.9 0 29 0 8.5 0.1 0.3 6.6 50/5.0 3 10 81.4 35.1 2.7 0 16 0 28.7 0 8.6 0 0.2 8.7 50/5.0 3 50 79.4 36.5 2.6 0 15.6 0 29.7 0 8.8 0 0.2 6.6 50/5.0 9.1 10 81.2 35.5 4 0 15.7 0 29.3 0 8.7 0.2 0.2 6.4 50/5.0 9.1 50 29.8 35.4 18.0 0 5.2 0 4.5 0 1.7 31.4 3.8 0

(47) TABLE-US-00021 TABLE 10-D2 (CO.sub.2 free selectivities and CO.sub.2 inclusive selectivity)- Pressure screening at a temperature of 380 C., GHSV of 4000 h.sup.1, and a H.sub.2/CO ratio of 3 CO.sub.2 free selectivities CO.sub.2 inclusive selectivities Oxygenates + Oxygenates + P CH.sub.4 C.sub.2H.sub.6 + C.sub.3H.sub.8 C.sub.4H.sub.10 olefins CO.sub.2 CH.sub.4 C.sub.2H.sub.6 + C.sub.3H.sub.8 C.sub.4H.sub.10 olefin (bar/MPa) (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) (wt %)s 20/2.0 3 82 15 1 71 1 24 4 0 20/2.0 4 83 12 1 72 1 23 3 0 20/2.0 2 83 14 0 70 1 25 4 0 20/2.0 4 82 12 1 71 1 24 4 0 20/2.0 4 81 15 0 70 1 25 4 0 20/2.0 5 81 13 1 70 1 24 4 0 20/2.0 13 73 12 2 70 4 22 4 1 20/2.0 36 34 5 24 66 12 12 2 8 50/5.0 6 78 15 1 66 2 27 5 0 50/5.0 5 79 15 1 67 2 26 5 0 50/5.0 5 79 15 1 65 2 28 5 0 50/5.0 5 79 15 1 66 2 27 5 0 50/5.0 7 77 15 1 64 3 27 5 0 50/5.0 22 12 2 65 54 10 5 1 30

(48) TABLE-US-00022 TABLE 10-E1 GHSV screening at a temperature of 380 C., a pressure of 50 bar (5.0 MPa), a H.sub.2/CO ratio of 3 and a catalyst wt ratio of HiFUEL R120/SAPO-34 of 3 CO C.sub.1 Sel C.sub.2 Sel C.sub.3 Sel C.sub.4 Sel Oxygenates GHSV TOS CONV (mol %) (mol %) (mol %) (mol %) Sel (mol %) Other (h.sup.1) (hr) (mol %) CO.sub.2 CH.sub.4 C.sub.2H.sub.4 C.sub.2H.sub.6 C.sub.3H.sub.6 C.sub.3H.sub.8 C.sub.4H.sub.8 C.sub.4H.sub.10 DME MeOH (mol %) 4000 10 81.4 35.1 2.7 0 16 0 28.7 0 8.6 0 0.2 8.7 4000 50 79.4 36.5 2.6 0 15.6 0 29.7 0 8.8 0 0.2 6.8 10000 10 70.4 36.1 2.5 0 14.6 0.1 26.9 0 8 0.1 0.3 11.5 10000 50 36.5 40.5 3.9 0 12.6 0 23.4 0 6.6 4.4 2.6 6.0 13400 10 46.7 39.2 2.8 0 13.9 0 26.1 0 7.6 0.4 1.2 8.8 13400 50 13.1 34.4 11.9 0 6.9 0.3 8.9 0 2.3 26.9 8.4

(49) TABLE-US-00023 TABLE 10-E2 CO.sub.2 free selectivities and CO.sub.2 inclusive selectivity) - GHSV screening at a temperature of 380 C., a pressure of 50 bar (5000 kPa), a H.sub.2/CO ratio of 3 and a catalyst wt ratio of HiFUEL R120/SAPO-34 of 3 CO.sub.2 free selectivities CO.sub.2 inclusive selectivities (wt %) (wt %) GHSV (wt %) (wt %) (wt %) Oxygenates + (wt %) (wt %) (wt %) (wt %) Oxygenates + (h.sup.1) CH.sub.4 C.sub.2H.sub.6 + C.sub.3H.sub.8 C.sub.4H.sub.10 olefins CO.sub.2 CH.sub.4 C.sub.2H.sub.6 + C.sub.3H.sub.8 C.sub.4H.sub.10 olefins 4000 5 79 15 1 65 2 28 5 0 4000 5 79 15 1 66 2 27 5 0 10000 5 78 15 2 67 2 26 5 1 10000 7 61 11 21 67 2 20 4 7 13400 6 74 14 6 68 2 23 4 2 13,400 14 17 3 66 53 7 8 1 31

(50) TABLE-US-00024 TABLE 10-F1 CO.sub.2 co-feed screening at a temperature of 380 C., a pressure of 40 bar (4.0 MPa), a H.sub.2/CO volume ratio of 3, a GHSV of 3,800 h1, and a catalyst wt ratio of HiFUEL R120/SAPO-34 of 3 CO.sub.2 CO C.sub.1 Sel C.sub.2 Sel C.sub.3 Sel C.sub.4 Sel Oxygenates Sel in feed TOS CONV (mol %) (mol %) (mol %) (mol %) (mol %) (mol %) (mol %) (mol %) (mol %) (mol %) Other (vol %) (hr) (mol %) CO.sub.2 CH.sub.4 C.sub.2H.sub.4 C.sub.2H.sub.6 C.sub.3H.sub.6 C.sub.3H.sub.8 C.sub.4H.sub.8 C.sub.4H.sub.10 DME MeOH (mol %) 0 0 71.7 42.9 2.3 0 14.2 0 26.4 0 7.3 0 0.1 6.8 10 0 58.2 27 2 0 18.4 0 33.1 0 9.8 0 0.2 9.5 20 0 46 13.6 2 0 22.2 0 38.4 0 11.7 0 0.2 11.9

(51) TABLE-US-00025 TABLE 10-F2 (CO.sub.2 free selectivities and CO.sub.2 inclusive selectivity)- CO.sub.2 co-feed screening at a temperature of 380 C., a pressure of 40 bar (4000 kPa), a H.sub.2/CO volume ratio of 3, a GHSV of 3,800 hr1 and a catalyst wt ratio of HiFUEL R120/SAPO-34 of 3 CO.sub.2 free selectivities CO.sub.2 inclusive selectivities (wt %) (wt %) CO.sub.2 (wt-%) (wt-%) (wt-%) Oxygenates + (wt %) (wt %) (wt %) (wt %) Oxygenates + in feed (vol %) CH.sub.4 C.sub.2H.sub.6 + C.sub.3H.sub.8 C.sub.4H.sub.10 olefins CO.sub.2 CH.sub.4 C.sub.2H.sub.6 + C.sub.3H.sub.8 C.sub.4H.sub.10 olefins 0 5 80 14 0 72 1 23 4 0 10 3 81 15 1 56 2 36 7 0 20 3 81 15 1 35 2 53 10 0

(52) The data presented in Tables 10-A through 10-F demonstrate first, that in certain embodiments the invention may lead to production of a combination of saturated and unsaturated two carbon atom and three carbon atom hydrocarbons selected from ethane, ethylene, propane and propylene. Operating outside the parameters of the present invention may lead to production of oxygenates at temperatures below 350 C. at long TOS (see Table 10-A1 comparative data). Second, an increase in pressure within the ranges shown in the Examples leads to an increase in CO conversion. For example, Table 10-B shows that, at 20 bar (2.0 MPa) and higher, there is more than ten times the conversion that occurs at 5 bar (0.5 MPa), while at higher pressure, such as 35 bar (3.5 MPa), catalyst performance improves with TOS. Third, a certain minimum H.sub.2:CO ratio is desirable for long term performance, with higher H.sub.2:CO ratios tending to favor a reduction in CO.sub.2 selectivity as shown in Table 10-C, where better catalyst stability is observed with a H.sub.2:CO ratio of 3 or higher. Table 10-D also shows that, at a catalyst ratio (HiFUEL R120/SAPO-34) of 3 or less, better catalyst stability and productivity are observed. Fourth, within certain limits, higher GHSV rates may lead to faster catalyst deactivation than lower GHSV rates. For example, Table 10-E shows that, at a GHSV below 10000 h.sup.1, the catalyst performance is observed to be more stable than at higher GHSV. Fifth, use of a CO.sub.2 co-feed may lead to a reduction in net CO.sub.2 selectivity, as shown in Table 4-F1, where net CO.sub.2 selectivity drops from 42.9% to 13.6% when the amount of CO.sub.2 in the feedstream increases from 0 volume percent (vol %) to 20 vol %.

EXAMPLE 7

(53) Physically mix 1 gram (g) of a copper-zinc-aluminum mixed metal oxide catalyst, having a copper (Cu) content of 39 wt %, a zinc (Zn) content of 25 wt %, and an aluminum content of 10 wt % (HiFUEL R120), with 0.33 gram of a silicoaluminophosphate catalyst (SAPO-34) by shaking them together in a bottle. Each of the catalysts has a particle size before mixing within a range of from 40 mesh (0.422 mm) to 80 mesh (0.178 mm). Activate the physically mixed catalyst using a pure hydrogen stream at a flow of 100 milliliters per minute (mL/min), a temperature of 270 C. and a pressure of 10 bar (1.0 MPa) for a period of 6 hours. Pressurize the system with pure nitrogen (N.sub.2) up to 40 bar (4.0 MPa). Heat up the system to 400 C. while still flowing pure nitrogen. Pass 22.5 mL/min CO.sub.2, 67.5 mL/min H.sub.2 and 10 mL/min N.sub.2 over the activated catalyst. Hold the temperature for 24 hours. Next, reduce the temperature by 25 C. and hold again for 24 hr. Repeat until a temperature of 300 C. is obtained. The results are recorded in Table 11.

(54) The catalyst is loaded only once, prior to Run 1, for Runs 1-5, and no reloading is done. All conditions of pressure, W/F and H.sub.2:CO.sub.2 ratios are consistent for these runs, with only the temperature changed. New catalyst is loaded for each of Runs 6-14, and pressure, W/F, H.sub.2:CO.sub.2 ratio, or MMO/SAPO-34 weight ratios are changed as shown in Table 12. This Example 6 shows that, despite the changes in parameters, a product mixture falling within the definition of claim 1 can be obtained, although the exact amounts of C1, C2 and C3 products are somewhat altered. Runs 9, 10 and 14 in Table 11 provide examples of optimized reaction conditions resulting in higher production of C2 and C3 paraffins.

(55) TABLE-US-00026 TABLE 11 Screening data from Example 7 for CuO/ZnO/Al.sub.2O.sub.3 + SAPO-34 catalyst and CO.sub.2 + H.sub.2 feed with varying temperatures, pressures, H.sub.2/CO.sub.2 ratios, W/F, and MMO/SAPO ratios. W/F MMO CO and CO2 free, carbon based selectivities (g- cat/- H2 CO2 COx Meth- T P H.sub.2:CO.sub.2 cat * h/- SAPO CONV CONV CONV ane C2 C2 Run C. (bar) ratio mol) (wt/wt) (%) (%) (%) (%) (%) (%) 1 400 40 3 5.5 3.0 14.5 37 1.6 22 30 0 2 375 40 3 5.5 3.0 16.5 33.8 5.3 6 26 0 3 350 40 3 5.5 3.0 17.8 30.7 7.9 5 22 0 4 325 40 3 5.5 3.0 14.3 27.3 3.7 7 12 0 5 300 40 3 5.5 3.0 11.1 23.4 2.9 0 0 0 6 350 28 3 5.5 3.0 11.7 30.5 1.6 7 25 0 7 350 2 3 5.5 3.0 10.4 28.7 0 0 0 0 8 350 40 1 5.5 3.0 21.5 18.7 1.5 4 25 0 9 350 40 10 5.5 3.0 11.5 51.5 24.7 7 22 0 10 350 40 3 19.6 3.0 11.7 51.2 24.4 7 22 0 11 350 40 3 1 3.0 13.5 30.5 1.3 0 16 0 12 350 40 3 5.5 10 14.8 29.6 4.4 5 23 0 13 350 40 3 5.5 0.1 16.8 29.9 6.7 4 22 0 14 350 40 10 19.6 3.0 12.9 53.1 29.4 11 21 0 C2 + C3 CO and CO2 free, carbon based selectivities paraffin C1 C3 C3 C4 C4 C5 C5 MeOH DME yield yield Run (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) 1 35 0 9 0 0 0 3 1 1.0 0.4 2 47 0 14 0 4 0 2 1 3.8 0.3 3 48 0 15 0 6 0 2 1 5.6 0.4 4 27 0 8 0 0 0 19 27 1.4 0.3 5 1 0 0 0 0 0 57 42 0.0 0.0 6 51 0 0 0 0 0 10 4 1.2 0.1 7 0 0 3 0 0 0 0 0 0.0 0.0 8 48 0 0 0 4 0 3 2 1.1 0.1 9 49 0 14 0 5 0 1 1 17.6 1.8 10 49 0 14 0 5 0 1 1 17.3 1.7 11 34 0 15 0 1 0 19 20 0.7 0.0 12 46 0 10 0 5 0 4 3 3.0 0.2 13 55 0 14 0 3 0 1 0 5.1 0.3 14 45 0 15 0 5 0 1 1 19.4 3.2 The extent of reaction is calculated as COx conversion, where the reaction of CO.sub.2 into CO does not contribute to the conversion calculation.

(56) TABLE-US-00027 TABLE 12 Screening data from Example 7 reported as wt % of outlet, excluding CO, CO.sub.2 and H.sub.2. Wt % of outlet, excluding CO, CO.sub.2 and H2 Meth- ane C2 C2 C3 C3 C4 C4 C5 C5 MeOH DME Run (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) 1 22.9 28.9 0.0 32.8 0.0 8.1 0.0 0.0 0.0 6.0 1.4 2 6.3 25.6 0.0 45.4 0.0 13.6 0.0 3.8 0.0 4.2 1.1 3 5.0 22.0 0.0 46.6 0.0 14.2 0.0 5.5 0.0 5.7 2.1 4 5.7 9.1 0.0 19.1 0.0 5.6 0.0 0.0 0.0 29.5 30.9 5 0.0 0.0 0.0 0.6 0.0 0.0 0.0 0.0 0.0 65.4 34.0 6 6.6 22.2 0.0 44.2 0.0 2.6 0.0 0.0 0.0 18.9 5.4 7 4.4 24.7 0.0 46.2 0.0 12.9 0.0 3.9 0.0 5.5 2.4 8 7.6 22.4 0.0 47.7 0.0 13.8 0.0 4.9 0.0 2.2 1.6 9 7.4 21.9 0.0 47.7 0.0 14.5 0.0 4.8 0.0 2.1 1.5 10 0.0 12.2 0.0 25.4 0.0 7.4 0.0 0.7 0.0 30.9 23.4 11 5.1 21.4 0.0 42.6 0.0 13.0 0.0 4.6 0.0 8.5 4.9 12 4.4 21.7 0.0 53.6 0.0 15.0 0.0 3.0 0.0 2.2 0.0 13 12.0 21.5 0.0 45.0 0.0 12.9 0.0 4.9 0.0 2.2 1.6 14 37.5 39.3 0.0 20.2 0.0 3.0 0.0 0.0 0.0 0.0 0.0 As noted in Table 11, the extent of reaction is calculated as COx conversion, where the reaction of CO.sub.2 into CO does not contribute to the conversion calculation.

COMPARATIVE EXAMPLE C

(57) Two embodiments of the inventive catalyst system are tested against a catalyst system as described in Park, Y.-K.; Park, K.-C.; Ihm, S.-K., Hydrocarbon synthesis through CO.sub.2 hydrogenation over CuZnOZrO.sub.2/zeolite hybrid catalysts, Catalysis Today 44 (1998) 165-173, hereinafter Park, in a hydrogenation of CO.sub.2. Two separate mixed catalyst beds made up of the components for each catalyst, as shown in Table 13, are prepared, wherein the weight ratio of the mixed metal oxide to the zeolite component is 1:1. A mixed flow of hydrogen and carbon dioxide, in a H.sub.2:CO.sub.2 volumetric ratio of 3:1, is flowed through each catalyst bed at a pressure of 28 bar (2.8 MPa); a temperature of 400 C.; and a catalyst g per flow rate of 20 g-cat.Math.h/mol. Products produced and weight percentages thereof, based upon 100 weight percent, are shown in Table 13.

(58) TABLE-US-00028 TABLE 13 CO.sub.2 hydrogenation over hybrid catalysts, Park data only. Hybrid Catalyst CuZnOZrO.sub.2 + CuZnOZrO.sub.2 + H-ZSM-5* SAPO-34* CO.sub.2 conversion (%) 38.4 33.9 Yield (%): HC 2.7 12.2 CO 34.7 20.5 MeOH 1.0 1.2 DME 0.0 0.0 HC selectivity (wt %) C.sub.1 17.5 2.1 C.sub.2 75.4 34.2 C.sub.3 5.5 53.1 C.sub.4 1.2 9.6 C.sub.5 0.4 0.8 C.sub.6.sup.+ 0.0 0.2 C.sub.2.sup.+ yield 2.2 11.9 *Park catalyst
Table 13 shows that, for the Park process, yield of C.sub.2 and C.sub.3 hydrocarbons is 10.7 wt % ((34.2+53.1)/100.Math.12.2 wt %=10.7 wt %), and yield of CH.sub.4 is 0.3 wt % (2.1/100.Math.12.2 wt %=0.3 wt %).

(59) The Park data is then employed to compare the inventive catalyst system with the Park catalyst system, under the conditions employed in Park, including temperature (400 C.), pressure (28 bar, 2.8 MPa), weight catalyst per flow rate (W/F) of 20 g-cat*h/mol, H.sub.2:CO.sub.2 volumetric ratio of 3, and a mixed metal oxide catalyst to molecular sieve catalyst ratio of 1:1 on a weight/weight basis. Results are shown in Table 14.

(60) TABLE-US-00029 TABLE 14 Comparison of yields using Park and Example catalysts under Park conditions. C1 C2 + C3 hydrocarbon hydrocarbon Hybrid catalyst yield yield CuZnOZrO.sub.2 + SAPO-34* 10.7 0.3 CuO/ZnO/Al.sub.2O.sub.3 + SAPO-34** 0.8 0.5 Cr.sub.2O.sub.3/ZnO + SAPO-34** 5.4 5.4 *Park catalyst **Example catalyst.

EXAMPLE 8

(61) A mixed catalyst comprising CuO/ZnO/Al.sub.2O.sub.3 is employed in a reaction to show the alteration in yields, and improvement in C.sub.2 and C.sub.3 yield, attributable to use of conditions including a temperature of 350 C., a pressure of 40 bar (4 MPa), a weight to flow ratio (W/F) of 19.6 g-cat*h/mol, a H.sub.2:CO.sub.2 ratio of 10:1, and a mixed metal oxide catalyst to weight/weight ratio of 3:1. Results are shown in Table 15.

(62) TABLE-US-00030 TABLE 15 Hydrocarbon yields at given conditions. C1 C2 + C3 hydrocarbon hydrocarbon Hybrid catalyst yield yield CuO/ZnO/Al.sub.2O.sub.3 + SAPO-34** 19.4 3.2 **Example catalyst

(63) This Example 8 shows that the example catalyst under the given claimed process conditions shows better performance than the Park catalyst under Park's conditions.

EXAMPLE 9

(64) A Cr.sub.2O.sub.3/ZnO catalyst is prepared as follows:

(65) A 0.14 molar (M) cation solution is prepared via addition of appropriate quantities (targeting a Cr to Zn molar ratio of 0.4:1) of Cr(NO.sub.3).sub.39H.sub.2O and Zn(NO.sub.3).sub.2.3H.sub.2O to distilled water (H.sub.2O). In addition, a 0.5 M solution of (NH.sub.4).sub.2CO.sub.3 is prepared as a precipitating agent. The cation (Cr.sub.3.sup.+/Zn.sub.2.sup.+) and anion ((CO.sub.3).sub.2) solutions are simultaneously added dropwise to a stirred beaker of distilled H.sub.2O maintained at 7.0<=pH<=7.5 and T=338+/5 K. Co-precipitated materials are filtered, washed repeatedly with distilled water, dried in static air at 383 K, and subsequently calcined at 873 K for 2 hr.

(66) The prepared Cr.sub.2O.sub.3/ZnO catalyst is then physically mixed with a silicoaluminophosphate catalyst (SAPO-34) by taking appropriate amounts to reach the weight ratio as indicated in Table 16 hereinbelow and shaking them together in a bottle. Each of the catalysts has a particle size before mixing within a range of from 40 mesh (0.422 mm) to 80 mesh (0.178 mm). Pressurize the system with pure N.sub.2 up to the value as indicated in Table 15. Heat up the system to the value as indicated in Table 16 while still flowing pure N.sub.2. Switch off the flow of nitrogen and start passing a certain amount of CO, H.sub.2 and He over the catalyst to reach the feed ratio and GHSV as indicated in the table. The results are shown in Table 16.

(67) TABLE-US-00031 TABLE 16 Screening of Cr.sub.2O.sub.3/ZnO + SAPO-34 catalyst at varying pressures, cat ratios, and GHSVs. Wt % of outlet, excluding CO, CO.sub.2 and H.sub.2 P Cat H.sub.2:CO CO Meth- T (bar/ ratio GHSV ratio TOS CONV ane C2 C2 ( C.) MPa) (wt/wt) (h.sup.1) (v/v) (hr) (mol %) (wt %) (wt %) (wt %) 400 50/5.0 2 2000 3 10 67.0 12.5 11.7 1.6 400 50/5.0 2 2000 3 50 63.6 14.4 13.5 0.0 400 70/7.0 2 1000 3 10 81.6 13.9 23.6 0.0 400 70/7.0 2 1000 3 50 78.7 14.7 22.0 0.0 400 50/5.0 1 1000 3 10 74.2 14.8 27.0 0.0 400 50/5.0 1 1000 3 50 71.1 10.6 23.1 0.0 Wt % of outlet, excluding CO, CO.sub.2 T C3 C3 C4 C4 C5 C5 MeOH DME ( C.) (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) 400 57.3 1.6 12.9 0.0 2.4 0.0 0.0 0.0 400 57.6 1.6 11.4 0.0 1.6 0.0 0.0 0.0 400 48.5 1.1 10.6 0.0 1.5 0.0 0.0 0.8 400 49.5 1.0 10.3 0.0 1.7 0.0 0.0 0.8 400 45.3 0.6 10.0 0.0 1.0 0.0 0.0 1.3 400 52.2 0.7 11.3 0.0 1.0 0.0 0.0 1.0

EXAMPLE 10

(68) Replicate Example 6, but change the catalyst type in a first run to a mixture CuO/ZnO/Al.sub.2O.sub.3 and a combination of molecular sieve catalysts comprised of 75 wt % SAPO-5 and 25 wt % of SAPO-34.

(69) In a second run, change the catalyst type to a mixture of CuO/ZnO/Al.sub.2O.sub.3 and SAPO-18.

(70) For a third run, physically mix 50 microliters (4) of a CuO/ZnO/Al.sub.2O.sub.3 mixed metal oxide catalyst that has a Cu content of 39 wt %, a Zn content of 25 wt %, and an Al content of 10 wt % (HiFUEL R120) with 150 L of a H-Beta zeolite (ZEOCAT PB/H, SiO.sub.2/Al.sub.2O.sub.3 ratio=24, available from Zeochem AG, Switzerland) by shaking them together in a bottle.

(71) Each of the catalysts has a particle size before mixing ranging from 40 mesh (0.422 mm) to 80 mesh (0.178 mm). For the first and second run, activate the physically mixed catalyst according to Example 6. For the third run, activate the physically mixed catalyst using a mix of H.sub.2 and He at a 90:10 vol %/vol % ratio, at a GHSV of 2400 h.sup.1, a temperature of 300 C. and a pressure of 3 bar (0.3 MPa) for a period of 6 hr.

(72) Pass a mixture of H.sub.2 and CO, volumetric ratio H.sub.2:CO=3, over each activated catalyst under the conditions shown in Table 17. Table 18 illustrates the corresponding wt % of outlet, excluding CO.sub.2, CO and H.sub.2, for each of the three catalyst runs.

(73) TABLE-US-00032 TABLE 17 Comparison of different molecular sieve catalysts in conversion of CO. MMO/- P H2:CO zeollite Carbon based selectivities (bar-/ ratio GHSV ratio T CO CH4 C2H4 C2H6 Catalyst MPa) (v/v) (hr1) (wt/wt) ( C.) CONV (%) (%) (%) CuO/ZnO/- 50/5.0 3 4000 3 380 79.2 2.5 0.0 15.0 Al2O3 + (75 wt % SAPO-5 + 25 wt % SAPO-34) CuO/ZnO/- 50/5.0 3 4000 3 400 69.0 4.9 0.0 14.9 Al2O3 + SAPO-18 CuO/ZnO/- 30/3.0 3 1950 0.6 385 70.5 6.2 0.0 14.4 Al2O3 + Beta Carbon based selectivities C3H6 C3H8 C4H8 C4H10 C5H10 C5H12 Catalyst (%) (%) (%) (%) (%) (%) MeOH DME CO.sub.2 CuO/ZnO/- 0.0 29.9 0.0 8.8 0.0 2.8 0.1 3.6 37.3 Al2O3 + (75 wt % SAPO-5 + 25 wt % SAPO-34) CuO/ZnO/- 0.0 33.2 0.0 7.6 0.0 1.6 0.1 0.0 37.8 Al2O3 + SAPO-18 CuO/ZnO/- 0.0 24.5 0.0 6.1 0.0 0.9 0.0 0.0 47.9 Al2O3 + Beta

(74) TABLE-US-00033 TABLE 18 Wt % of outlet corresponding to use of different molecular sieve catalysts. Wt % of outlet, excluding CO.sub.2, CO and H.sub.2 CH4 C2H4 C2H6 C3H6 C3H8 C4H8 C4H10 C5H10 C5H12 MeOH DME Catalyst (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) CuO/ZnO/Al2O3 + (75 wt % SAPO-5 + 4.2 0.0 23.5 0.0 45.8 0.0 13.4 0.0 4.3 0.4 8.6 25 wt % SAPO-34 CuO/ZnO/Al2O3 + SAPO-18 8.5 0.0 24.2 0.0 52.7 0.0 11.9 0.0 2.4 0.4 0.0 CuO/ZnO/Al2O3 + Beta 12.9 0.0 27.8 0.0 46.3 0.0 11.4 0.0 1.7 0.0 0.0