SELECTIVE PRODUCTION OF ETHYLENE FROM METHANE

Abstract

Disclosed are processes for producing ethylene. The processes can include contacting a first stream containing methane with an oxidant and oxidizing at least a portion of the methane under conditions suitable to produce a second stream containing carbon monoxide (CO) and hydrogen (H.sub.2), contacting the second stream with a CO hydrogenation catalyst under conditions suitable to produce a third stream containing methanol and ethanol, obtaining a fourth stream containing the ethanol and a fifth stream containing the methanol from the third stream, and contacting the fourth stream with an ethanol dehydration catalyst under conditions suitable to dehydrate at least a portion of the ethanol and produce a products stream containing ethylene.

Claims

1. A process for producing ethylene, the process comprising: (a) contacting a first stream comprising methane with an oxidant and oxidizing at least a portion of the methane under conditions suitable to produce a second stream comprising carbon monoxide (CO) and hydrogen (H.sub.2); (b) contacting the second stream with a CO hydrogenation catalyst under conditions suitable to produce a third stream comprising methanol and ethanol; (c) obtaining a fourth stream comprising the ethanol, and a fifth stream comprising methanol from the third stream; and (d) contacting the fourth stream with an ethanol dehydration catalyst under conditions suitable to dehydrate at least a portion of the ethanol and produce a products stream comprising ethylene.

2. The process of claim 1, wherein the third stream further comprises C2-C7 paraffins and carbon dioxide (CO.sub.2) and the process further comprises: (i) separating the third stream to obtain a first intermediate stream containing the methanol and ethanol and a second intermediate stream containing the C2-C7 paraffins and CO.sub.2; and (ii) separating the first intermediate stream to obtain the fourth stream and the fifth stream.

3. The process of claim 1, wherein the CO hydrogenation catalyst comprises a crystalline cobalt molybdenum catalyst.

4. The process of claim 3, wherein the crystalline cobalt molybdenum catalyst comprises a monoclinic crystalline structure.

5. The process of claim 4, wherein the crystalline cobalt molybdenum catalyst is a monoclinic cobalt molybdenum oxide.

6. The process of claim 5, wherein the monoclinic cobalt molybdenum oxide is Co.sub.xMo.sub.yO.sub.z, wherein x ranges from 0.5 to 1.5, y ranges from 0.5 to 1.5, and z ranges from 3.5 to 4.5.

7. The process of claim 6, wherein the monoclinic cobalt molybdenum oxide comprises α-CoMoO4 and β-CoMoO.sub.4 at a α-CoMO.sub.4 to β-CoMO.sub.4 wt. % ratio 15:85 to 35:65.

8. The process of claim 1, wherein the CO hydrogenation catalyst is reduced and activated prior to contacting with the second stream.

9. The process of claim 1, wherein the oxidant in step (a), is steam, oxygen (O.sub.2), CO.sub.2 or a combination thereof.

10. The process of claim 1, wherein the oxidation of the at least a portion of the methane in the step (a) is catalyzed using a methane oxidation catalyst, wherein the methane oxidation catalyst comprises one or more metals selected from La, Ni, Ru, Rh, Pd, Ir, and Pt, on a support comprising alumina, silica, zirconia, ceria, titania, magnesium oxide, magnesium aluminate or any combination thereof.

11. The process of claim 1, wherein the step (a) methane oxidation conditions comprise a pressure of 0 to 180 bar, GHSV of 5000 to 15000 h.sup.−1 and a temperature of 500 to 1600° C.

12. The process of claim 1, wherein the molar ratio of the H.sub.2 and CO in the second stream is 0.5:1 to 3:1.

13. The process of claim 1, wherein the step (b) contacting conditions comprise a pressure of 25 to 90 bar, GHSV of 1000 to 3000 h.sup.−1, and a temperature of 150 to 450° C.

14. The process of claim 2, wherein the third stream comprises 20 mol. % to 40 mol. % methanol, 20 mol. % to 40 mol. % ethanol, 5 mol. % to 25 mol. % C2-C7 paraffins and 10 mol. % to 20 mol. % CO.sub.2.

15. The process of claim 2, wherein in step (i) the third stream is separated by distillation using a distillation column and the first intermediate stream is obtained as a bottom distillate product and the second intermediate stream is obtain as a top distillate product.

16. The process of claim 2, wherein in step (ii) first intermediate stream is separated by distillation using a distillation column and the fourth stream is obtain as a bottom distillate product and the fifth stream is obtained as a top distillate product.

17. The process of claim 1, wherein the step (d) contacting conditions comprise a pressure of 0 to 90 bar, GHSV of 1000 to 3000 h.sup.−1 and a temperature of 105 to 450° C.

18. The process of claim 1, wherein the dehydration catalyst in step (d) is an acid type catalyst.

19. The process of claim 18, wherein the acid type catalyst is cesium doped silicotungstic acid supported on alumina.

20. The process of claim 1, wherein the methane in the first stream is obtained from a refinery, petroleum by product, renewable feedstock, or a combination thereof.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0022] FIG. 1: Schematic of an example of the present invention to produce ethylene.

[0023] FIG. 2: Thermal Gravimetric Analysis of crystalline cobalt molybdenum catalyst.

[0024] FIG. 3: X-ray power diffraction of crystalline cobalt molybdenum catalyst.

[0025] FIG. 4: Raman spectrum of crystalline cobalt molybdenum catalyst.

[0026] FIG. 5: CO conversion percentage obtained with cobalt molybdenum catalyst.

DETAILED DESCRIPTION OF THE INVENTION

[0027] A discovery has been made that provides solutions to at least some of the problems associated with the production of ethylene from a methane containing C1 hydrocarbon feedstock. The solution is premised on producing CO and H2 from the C1 hydrocarbon feedstock, hydrogenating the CO with the H2 (or supplemental) using a CO hydrogenation catalyst to produce ethanol with high selectivity, optionally separating the ethanol from the other products produced during CO hydrogenation, and dehydrating the ethanol to produce ethylene.

[0028] These and other non-limiting aspects of the present invention are discussed in further detail in the following paragraphs with reference to the figures.

[0029] Referring to FIG. 1, one example of a system and process of the present invention for producing ethylene is described. System 100 can include a methane oxidizing unit 102, a CO hydrogenation unit 104, a first separation unit 106, a second separation unit 108, and an ethanol dehydration unit 110.

[0030] A first stream 112 containing methane can be fed to the methane oxidizing unit 102. In the methane oxidizing unit 102 the methane can get oxidized by an oxidant to produce CO and H.sub.2. The oxidant can be steam, O.sub.2, CO.sub.2 or any combination thereof. The oxidant can be fed to the methane oxidizing unit 102 as a separate feed 114 or it can be mixed with the first stream 112 and fed to the methane oxidizing unit 102 as a single feed (not shown). The methane oxidation conditions in the methane oxidizing unit 102 can include a pressure of 0 bar to 180 bar, or at least any one of, equal to any one of, or between any two of 0 bar, 15 bar, 30 bar, 45 bar, 60 bar, 75 bar, 90 bar, 105 bar, 120 bar, 135 bar, 150 bar, 165 bar and 180 bar, GHSV of 5000 h.sup.−1 to 15000 h.sup.−1 or at least any one of, equal to any one of, or between any two of 5000 h.sup.−1, 6000 h.sup.−1, 7000 h.sup.−1, 8000 h.sup.−1, 9000 h.sup.−1, 10000 h.sup.−1, 1000 h.sup.−1, 12000 h.sup.−1, 13000 h.sup.−1, 14000 h.sup.−1 and 15000 h.sup.−1 and/or a temperature of 500° C. to 1600° C. or at least any one of, equal to any one of, or between any two of 500° C., 600° C., 700° C., 800° C., 900° C., 1000° C., 1100° C., 1200° C., 1300° C., 1400° C., 1500° C. and 1600° C. In some aspects, the methane oxidizing unit 102 can contain a methane oxidation catalyst (not shown) and the methane oxidation can be catalyzed by the methane oxidation catalyst. In some aspects, the methane oxidizing unit 102 can be a part of a chemical looping system (not shown), and the methane can be oxidized via chemical looping, wherein the oxidant can be provided to the methane by an oxidized methane oxidation catalyst and/or oxygen transfer agent. The methane oxidation catalyst can contain one or more metals on a support. The one or more metals can be one or more of La, Ni, Ru, Rh, Pd, Ir or Pt. The support can be alumina, silica, zirconia, ceria, titania, magnesium oxide, magnesium aluminate or a combination thereof. In some aspects, the methane oxidation catalyst can contain a promoter. In some aspects the promoter can be an alkali metal, and/or an alkaline earth metal. In some aspects the promoter can be Li, Na, K, or a combination thereof Non-limiting examples of methane oxidation catalysts that can be used in the context of the present invention can include LaNiAl.sub.2O.sub.3, LiLaNiAl.sub.2O.sub.3, NaLaNiAl.sub.2O.sub.3, KLaNiAl.sub.2O.sub.3, or a methane oxidation catalyst as described in Khalesi et. al., Ind. Eng. Chem. Res., 2008, 47, 5892-5898.

[0031] A second stream 116 containing at least a portion of the CO and H.sub.2 produced from methane oxidation can enter the CO hydrogenation unit 104. The H.sub.2 and CO molar ratio in the second stream can be 0.5:1 to 3:1 or at least any one of, equal to any one of, or between any two of 0.5:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 2:1, 2.5:1, and 3:1. In the CO hydrogenation unit 104 the second stream 116 can be contacted with a CO hydrogenation catalyst (not shown) to hydrogenate the CO with the H.sub.2 and produce methanol, ethanol, C2-C7 paraffins and CO.sub.2. The combined selectivity of the methanol and ethanol can be 50% to 75% or at least any one of, equal to any one of, or between any two of 50 %, 51 %, 52 %, 53 %, 54 %, 55 %, 56 %, 57 %, 58%, 59 %, 60 %, 61%, 62 %, 63%, 64 %, 65 %, 66 %, 67 %, 68 %, 69 %, 70 %, 71%, 72%, 73%, 74%, and 75%. In some particular aspects, the selectivity of the methanol can be 20% to 40% or at least any one of, equal to any one of, or between any two of 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% and 40%. In some particular aspects, the selectivity of the ethanol can be 20% to 40% or at least any one of, equal to any one of, or between any two of 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% and 40%. In some particular aspects, the selectivity of the C2 to C7 paraffins can be 5% to 25% or at least any one of, equal to any one of, or between any two of 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, and 25%. In some particular aspects, the selectivity of the CO.sub.2 can be 10% to 20% or at least any one of, equal to any one of, or between any two of 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, and 20%. In some aspects, the CO conversion can be 20% to 40% or at least any one of, equal to any one of, or between any two of 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% and 40%. The CO hydrogenation conditions can include a pressure 25 bar to 90 bar or at least any one of, equal to any one of, or between any two of 25 bar, 35 bar, 45 bar, 55 bar, 65 bar, 75 bar, 85 bar, and 90 bar, GHSV 1000 h.sup.−1 to 3000 h.sup.−1 or at least any one of, equal to any one of, or between any two of 1000 h.sup.1, 1100 h.sup.−1, 1200 h.sup.−1, 1300 h.sup.−1, 1400 h.sup.−1, 1500 h.sup.−1, 1600 h.sup.−1, 1700 h.sup.−1, 1800 h.sup.−1, 1900 h.sup.−1, 2000 h.sup.−1, 2100 h.sup.−1, 2200 h.sup.−1, 2300 h.sup.−1, 2400 h.sup.−1, 2500 h.sup.−1, 2600 h.sup.−1, 2700 h.sup.−1, 2800 h.sup.−1, 2900 h.sup.−1, and 3000 h.sup.−1 and/or a temperature 150° C. to 450° C. or at least any one of, equal to any one of, or between any two of 150° C., 200° C., 250° C., 300° C., 350° C., 400° C., and 450° C. In some aspects, the CO hydrogenation catalyst can be activated, prior to contacting the catalyst with the second stream 116. In some aspects, the CO hydrogenation catalyst can be contacted with a stream containing H.sub.2 at a temperature 200° C. to 500° C. or at least any one of, equal to any one of, or between any two of 200° C., 250° C., 300° C., 350° C., 400° C., 450° C. and 500° C., at a GHSV 1000 h.sup.−1 to 3000 h.sup.−1 or at least any one of, equal to any one of, or between any two of 1000 h.sup.−1, 1100 h.sup.−1, 1200 h.sup.−1, 1300 h.sup.−1, 1400 h.sup.−1, 1500 h.sup.−1, 1600 h.sup.−1, 1700 h.sup.−1, 1800 h.sup.−1, 1900 h.sup.−1, 2000 h.sup.−1, 2100 h.sup.−1, 2200 h.sup.−, 2300 h.sup.−, 2400 h.sup.−1, 2500 h.sup.−1, 2600 h.sup.−1, 2700 h.sup.−1, 2800 h.sup.−1, 2900 h.sup.−1, and 3000 h.sup.−1, and/or at a pressure 25 bar to 90 bar or at least any one of, equal to any one of, or between any two of 25 bar, 35 bar, 45 bar, 55 bar, 65 bar, 75 bar, 85 bar, and 90 bar for 8 h to 20 h or at least any one of, equal to any one of, or between any two of 8 h, 10 h 12 h, 14 h, 16 h, 18 h and 20 h to reduce and activate the catalyst. In some aspects, the system 100 can include an off-line secondary CO hydrogenation reactor (not shown) in addition to the on-line primary CO hydrogenation reactor 104. The CO hydrogenation catalyst can be activated and/or regenerated in the secondary CO hydrogenation reactor. Activation and/or regeneration of the CO hydrogenation catalyst in the secondary CO hydrogenation reactor can be performed in parallel to the CO hydrogenation in the primary CO hydrogenation reactor 104. Once regeneration/activation of the CO hydrogenation catalyst in the primary CO hydrogenation reactor becomes necessary, the primary CO hydrogenation reactor can be taken offline and the secondary CO hydrogenation reactor with the activated catalyst can be brought on-line and thereby primary become secondary and the secondary becomes primary CO hydrogenation reactor. The parallel activation process can be repeated to ensure continuous operation of the ethylene production process.

[0032] The CO hydrogenation catalyst can be a crystalline cobalt molybdenum catalyst. The crystalline cobalt molybdenum catalyst can include a monoclinic crystalline structure. In some aspects, the monoclinic cobalt molybdenum catalyst can be a monoclinic cobalt molybdenum oxide. In some aspects, the monoclinic cobalt molybdenum oxide can be Co.sub.xMo.sub.yO.sub.z, where x can be 0.5 to 1.5 or at least any one of, equal to any one of, or between any two of 0.5, 0.6, 0.7, 0.8, 0.9. 1, 1.1, 1.2, 1.3, 1.4 and 1.5, y can be 0.5 to 1.5 or at least any one of, equal to any one of, or between any two of 0.5, 0.6, 0.7, 0.8, 0.9. 1, 1.1, 1.2, 1.3, 1.4 and 1.5, and z can balance the valencies of Co and Mo. In certain aspects, z can be 3.5 to 4.5 or at least any one of, equal to any one of, or between any two of 3.5, 3.6, 3.7, 3.8, 3.9. 4, 4.1, 4.2, 4.3, 4.4 and 4.5. In some particular aspects, the monoclinic cobalt molybdenum oxide can include α-CoMoO.sub.4 and β-CoMoO.sub.4 at a α-CoMoO.sub.4 to β-CoMoO.sub.4 wt. % ratio 15:85 to 35:65 or at least any one of, equal to any one of, or between any two 15:85, 16:84, 17:83, 18:82, 19:81, 20:80, 21:79, 22:78, 23:77, 24:76, 25:75, 26:74, 27:73, 28:72, 29:71, 30:70, 31:69, 32:68, 33:67, 34:66 and 35:65. The catalyst can be a bulk or a supported catalyst, preferably a bulk catalyst. In some aspects the catalyst does not contain a support. In some aspects, the catalyst does not contain a cobalt sulfide, a molybdenum sulfide and/or a metal sulfide. In some aspects, the catalyst does not contain an alkali metal. In some aspects, the catalyst does not contain an alkaline earth metal. In some aspects, the crystalline cobalt molybdenum catalyst can have an X-ray power diffraction pattern as substantially depicted in FIG. 3. In other aspects of the invention, however, other CO hydrogenation catalysts can be used.

[0033] A third stream 118 containing at least a portion of the ethanol, methanol, C2-C7 paraffins, and CO.sub.2 obtained from CO hydrogenation can enter the first separation unit 106. In some aspects, the third stream can contain at least any one of, equal to any one of, or between any two of 20 mol. %, 21 mol. %, 22 mol. %, 23 mol. %, 24 mol. %, 25 mol. %, 26 mol. %, 27 mol. %, 28 mol. %, 29 mol. %, 30 mol. %, 31 mol. %, 32 mol. %, 33 mol. %, 34 mol. %, 35 mol. %, 36 mol. %, 37 mol. %, 38 mol. %, 39 mol. % and 40 mol. % methanol; at least any one of, equal to any one of, or between any two of 20 mol. %, 21 mol. %, 22 mol. %, 23 mol.

[0034] %, 24 mol. %, 25 mol. %, 26 mol. %, 27 mol. %, 28 mol. %, 29 mol. %, 30 mol. %, 31 mol. %, 32 mol. %, 33 mol. %, 34 mol. %, 35 mol. %, 36 mol. %, 37 mol. %, 38 mol. %, 39 mol. % and 40 mol. % ethanol; at least any one of, equal to any one of, or between any two of 5 mol. %, 6 mol. %, 7 mol. %, 8 mol. %, 9 mol. %, 10 mol. %, 11 mol. %, 12 mol. %, 13 mol. %, 14 mol. %, 15 mol. %, 16 mol. %, 17 mol. %, 18 mol. %, 19 mol. %, 20 mol. %, 21 mol. %, 22 mol. %, 23 mol. %, 24 mol. %, and 25 mol. % C2-C7 paraffins and at least any one of, equal to any one of, or between any two of 10 mol. %, 11 mol. %, 12 mol. %, 13 mol. %, 14 mol. %, 15 mol. %, 16 mol. %, 17 mol. %, 18 mol. %, 19 mol. %, and 20 mol. % CO2.

[0035] In the first separation unit 106 the third stream 118 can be separated to obtain a first intermediate stream 120 containing the ethanol and methanol and a second intermediate stream 122 containing the C2-C7 paraffins and CO.sub.2. The separation of the third stream 118 in the first separation unit 106 can be obtained by any suitable methods known in the art e.g., distillation, fractionation, pressure swing adsorption, and the like. In some aspects, the first separation unit 106 can contain a distillation column and the first intermediate stream 120 can be obtained as a bottom distillate product and the second intermediate stream 122 can be obtained as a top distillate product. In some aspects, column operating conditions can include a pressure 0 bar to 5 bar or at least any one of, equal to any one of, or between any two of 0 bar, 1 bar, 2 bar, 3 bar, 4 bar and 5 bar and/or a temperature 25° C. to 35° C. or at least any one of, equal to any one of, or between any two of 25° C., 26° C., 27° C., 28° C., 29° C., 30° C., 31° C., 32° C., 33° C., 34° C. and 35° C.

[0036] The first intermediate stream 120 can enter the second separation unit 108. In the second separation unit 108 the first intermediate stream 120 can be separated to obtain a fourth stream 124 containing the ethanol and a fifth stream 126 containing the methanol. The separation of the first intermediate stream 120 in the second separation unit 108 can be obtained by any suitable methods known in the art e.g., distillation, fractionation, pressure swing adsorption, and the like. In some aspects, the second separation unit 108 can contain a distillation column and the fourth stream 124 can be obtained as a bottom distillate product and the fifth stream 126 can be obtained as a top distillate product. In some aspects, column operating conditions can include a pressure 0 bar to 5 bar or at least any one of, equal to any one of, or between any two of 0 bar, 1 bar, 2 bar, 3 bar, 4 bar and 5 bar and/or a temperature 25° C. to 35° C. or at least any one of, equal to any one of, or between any two of 25° C., 26° C., 27° C., 28° C., 29° C., 30° C., 31° C., 32° C., 33° C., 34° C. and 35° C.

[0037] The fourth stream 124 can enter the ethanol dehydration unit 110. In the ethanol dehydration unit 110 the fourth stream 124 can be contacted with an ethanol dehydration catalyst (not shown) under conditions suitable to dehydrate at least a portion of the ethanol and produce a products stream 128 containing ethylene. The products stream 128 can contain 90 wt. % to 100 wt. % or at least any one of, equal to any one of, or between any two of 90 wt. %, 91 wt. %, 92 wt. %, 93 wt. %, 94 wt. %, 95 wt. %, 96 wt. %, 97 wt. %, 98 wt. %, 99 wt. % and 100 wt. % ethylene. The ethanol dehydration conditions can include a pressure 0 bar to 90 bar or at least any one of, equal to any one of, or between any two of 0 bar, 10 bar, 20 bar, 30 bar, 40 bar, 50 bar, 60 bar, 70 bar, 80 bar, and 90 bar, GHSV 1000 h.sup.−1 to 3000 h.sup.−1 or at least any one of, equal to any one of, or between any two of 1000 h.sup.−1, 1500 h.sup.−1, 2000 h.sup.−1, 2500 h.sup.−1 and 3000 h.sup.−1 and/or a temperature 105° C. to 450° C. or at least any one of, equal to any one of, or between any two of 105° C., 150° C., 200° C., 250° C., 300° C., 350° C., 400° C., and 450° C. The ethanol dehydration catalysts can be an acid type catalyst. In some aspects, the acid type catalyst can be cesium doped silicotungstic acid supported on alumina. Non-limiting examples of ethanol dehydration catalysts that can be used in the context of the present invention include one or more of CeSiW.sub.12O.sub.40, RbSiW.sub.12O.sub.40, CePMo.sub.12O.sub.40, RbH.sub.3PMo.sub.12O.sub.40, or a dehydration catalyst as described in Haider et al., Journal of Catalysis 286 (2012) 206-213.

[0038] In FIG. 1, the reactors, units and/or zones can include one or more heating and/or cooling devices (e.g., insulation, electrical heaters, jacketed heat exchangers in the wall) and/or controllers (e.g., computers, flow valves, automated values, inlets, outlets, etc.) that can be used to control the reaction temperature and pressure of the reaction mixture. While only one unit or zone is shown, it should be understood that multiple reactors or zones can be housed in one unit or a plurality of reactors housed in one heat transfer unit. In some aspects, the reactors can be a fixed bed reactor, moving bed reactors, trickle-bed reactor, rotating bed reactor, slurry reactors or fluidized bed reactor.

[0039] Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the above disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

EXAMPLES

[0040] As part of the disclosure of the present invention, specific examples are included below. The examples are for illustrative purposes only and are not intended to limit the invention. Those of ordinary skill in the art will readily recognize parameters that can be changed or modified to yield essentially the same results.

Example 1

Crystalline Cobalt Molybdenum Catalyst Preparation and Activity Evaluation

[0041] Catalyst preparation. Catalysts were prepared via co-precipitation method. Separate solutions of cobalt acetate (12.45 g, 100 ml d.H.sub.2O) and ammonium heptamolybdate (8.45 g, 100 ml d.H.sub.2O) were heated to 65° C. to dissolve the salts. While under stirring and the molybdenum solution heated at 65° C., the cobalt solution was added dropwise using a separating funnel and aged for 2 h. The solution was then filtered without washing and the dark purple precipitate was dried in an oven (110° C.) for 6 h. The catalyst precursor was calcined (500° C., static air, 10° C./min, 4 h) resulting in the cobalt molybdenum catalyst.

[0042] Catalyst Characterization. Catalyst characterization results are shown in FIG. 2-4. Thermogravimetric analysis (TGA) was used to assess the decomposition of the cobalt molybdate precursor to the final state catalyst (FIG. 2). TGA shows a weight loss from 300° C. to 400° C. showing the acetate evolving to CO2 shown by the negative peak (exothermic). This confirms the calcination at 500° C. would result in decomposition of the acetates and nitrates. X-ray powder diffraction (FIG. 3) shows reflections corresponding to monoclinic CoMoO.sub.4 with α-CoMoP.sub.4 and β-CoMoO.sub.4 at a wt. % ratio 25:75. The peak at 11.7°, which is the main reflection of molybdenum trioxide is also observed suggesting phase separation as 1:1 Co:Mo ratio was used. The excess can also be seen in the Raman spectrum 819 cm.sup.−1 (FIG. 4).

[0043] Catalyst activity and selectivity evaluation. The catalysts were evaluated for the activity and selectivity calculations along with short term as well as long studies of the catalyst stabilities. Prior to activity measurement, the catalysts were subjected to activation procedure, by reducing the catalyst with a H.sub.2 (H.sub.2, 100 ml/min, 350° C., 1° C./min, 16 h). Catalytic evaluation was carried out in high throughput fixed bed flow reactor setup housed in temperature-controlled system fitted with regulators to maintain pressure during the reaction. The products of the reactions were analyzed through online GC analysis. The evaluation was carried out under the following conditions unless otherwise mentioned elsewhere; 47.5% H.sub.2/47.5% CO/5% N.sub.2, 75 Bar, 300° C., 1° C./min, 48 h stabilization, 100 ml/min, 50% SiC mix.

[0044] The mass balance of the reactions is calculated to be 95±5%. Dehydration of alcohols produced can be carried out at a temperature above their boiling points and in the presence of and acid type catalyst for example cesium doped silicotungstic acid supported on alumina.

[0045] The results of catalyst testing are illustrated in FIG. 5 and Table 1. Duplicate sets of data show that the catalyst testing is reproducible. The catalyst is stable under reaction conditions, after a stabilization time of 48 h, with CO conversion at 24-30% (FIG. 5, Table 1). The catalyst produces substantial amount of MeOH and EtOH (ca. 60 mol. %) with small amount of propanol and butanol (ca. 10 mol. %) (Table 1).

TABLE-US-00001 TABLE 1 Product selectivity profile obtained from CO hydrogenation with the crystalline cobalt molybdenum catalyst. Conversion/Selectivity (mole %) TOS [h.sup.−1] Methanol Ethanol Propanol Butanol C.sub.2-C.sub.7 CH.sub.4 CO.sub.2 Conversion 0 25 25 8 7 19 0 15 30 2 33 28 7 6 10 0 16 30 4 25 25 9 8 19 0 14 30 5 32 30 8 7 10 0 13 30 6 30 34 8 7 8 0 13 30 7 30 28 9 9 10 0 14 30 8 29 29 9 8 10 0 15 30 10 31 30 9 9 9 0 12 30 11 28 31 6 6 18 0 11 30 12 33 26 8 7 11 0 15 30 13 30 30 7 7 10 0 16 30 14 30 29 8 7 15 0 11 30 16 29 35 7 7 10 0 12 30 17 34 30 6 5 10 0 15 30 18 28 27 6 6 20 0 13 30 19 30 29 10 9 10 0 12 30 20 28 35 7 7 8 0 15 30 22 30 27 4 4 20 0 15 30 23 28 27 8 7 13 0 17 30 24 30 29 8 8 10 0 15 30 25 29 33 3 3 18 0 14 30 26 33 30 5 4 12 0 16 30 28 30 29 7 7 10 0 17 30

[0046] In the context of the present invention, at least the following 20 embodiments are described. Embodiment 1 is a process for producing ethylene. The process includes: a) contacting a first stream containing methane with an oxidant and oxidizing at least a portion of the methane under conditions suitable to produce a second stream containing carbon monoxide (CO) and hydrogen (H.sub.2); (b) contacting the second stream with a CO hydrogenation catalyst under conditions suitable to produce a third stream containing methanol and ethanol; (c) obtaining a fourth stream containing the ethanol, and a fifth stream containing methanol from the third stream; and (d) contacting the fourth stream with an ethanol dehydration catalyst under conditions suitable to dehydrate at least a portion of the ethanol and produce a products stream containing ethylene. Embodiment 2 is the process of embodiment 1, wherein the third stream further contains C2-C7 paraffins and carbon dioxide (CO.sub.2) and the process further includes: (i) separating the third stream to obtain a first intermediate stream containing the methanol and ethanol and a second intermediate stream containing the C2-C7 paraffins and CO.sub.2, and (ii) separating the first intermediate stream to obtain the fourth stream and the fifth stream. Embodiment 3 is the process of either of embodiments 1 or 2, wherein the CO hydrogenation catalyst contains a crystalline cobalt molybdenum catalyst. Embodiment 4 is the process of embodiment 3, wherein the crystalline cobalt molybdenum catalyst contains a monoclinic crystalline structure. Embodiment 5 is the process of embodiment 4, wherein the crystalline cobalt molybdenum catalyst is a monoclinic cobalt molybdenum oxide. Embodiment 6 is the process of embodiment 5, wherein the monoclinic cobalt molybdenum oxide is Co.sub.xMo.sub.yO.sub.z, wherein x ranges from 0.5 to 1.5, y ranges from 0.5 to 1.5, and z ranges from 3.5 to 4.5. Embodiment 7 is the process of embodiment 6, wherein the monoclinic cobalt molybdenum oxide contains α-CoMoO4 and β-CoMoO.sub.4 at a α-CoMoO.sub.4 to β-CoMoO.sub.4 wt. % ratio 15:85 to 35:65. Embodiment 8 is the process of any one of embodiments 1 to 7, wherein the CO hydrogenation catalyst is reduced and activated prior to contacting with the second stream. Embodiment 9 is the process of any one of embodiments 1 to 8, wherein the oxidant in step (a), is steam, oxygen (O.sub.2), CO.sub.2 or a combination thereof. Embodiment 10 is the process of any one of embodiments 1 to 9, wherein the oxidation of the at least a portion of the methane in the step (a) is catalyzed using a methane oxidation catalyst, wherein the methane oxidation catalyst contains one or more metals selected from La, Ni, Ru, Rh, Pd, Ir, and Pt, on a support containing alumina, silica, zirconia, ceria, titania, magnesium oxide, magnesium aluminate or any combination thereof. Embodiment 11 is the process of any one of embodiments 1 to 10, wherein the step (a) methane oxidation conditions include a pressure of 0 to 180 bar, GHSV of 5000 to 15000 and a temperature of 500 to 1600° C. Embodiment 12 is the process of any one of embodiments 1 to 11, wherein the molar ratio of the H.sub.2 and CO in the second stream is 0.5:1 to 3:1. Embodiment 13 is the process of any one of embodiments 1 to 12, wherein the step (b) contacting conditions include a pressure of 25 to 90 bar, GHSV of 1000 to 3000 and a temperature of 150 to 450° C. Embodiment 14 is the process of any one of embodiments 2 to 13, wherein the third stream contains 20 mol. % to 40 mol. % methanol, 20 mol. % to 40 mol. % ethanol, 5 mol. % to 25 mol. % C2-C7 paraffins and 10 mol. % to 20 mol. % CO2. Embodiment 15 is the process of any one of embodiments 2 to 14, wherein in step (i) the third stream is separated by distillation using a distillation column and the first intermediate stream is obtained as a bottom distillate product and the second intermediate stream is obtain as a top distillate product. Embodiment 16 is the process of any one of embodiments 2 to 15, wherein in step (ii) first intermediate stream is separated by distillation using a distillation column and the fourth stream is obtain as a bottom distillate product and the fifth stream is obtained as a top distillate product. Embodiment 17 is the process of any one of embodiments 1 to 13, wherein the step (d) contacting conditions include a pressure of 0 to 90 bar, GHSV of 1000 to 3000 h.sup.−1 and a temperature of 105 to 450° C. Embodiment 18 is the process of any one of embodiments 1 to 17, wherein the dehydration catalyst in step (d) is an acid type catalyst. Embodiment 19 is the process of embodiment 18, wherein the acid type catalyst is cesium doped silicotungstic acid supported on alumina. Embodiment 20 is the process of any one of embodiments 1 to 19, wherein the methane in the first stream is obtained from a refinery, petroleum by product, renewable feedstock, or a combination thereof