SELECTIVE PRODUCTION OF PROPYLENE AND BUTYLENE FROM METHANE

Abstract

Disclosed are processes for producing propylene and butylene. 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 propanol and butanol, and contacting the third stream with an dehydration catalyst under conditions suitable to dehydrate at least a portion of the propanol and butanol and produce a products stream containing propylene and butylene.

Claims

1. A process for producing propylene and butylene, 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 propanol and butanol; (c) contacting the third stream with a dehydration catalyst under conditions suitable to dehydrate at least a portion of the propanol and butanol and produce a products stream comprising propylene and butylene.

2. The process of claim 1, wherein the third stream further comprises C2-C7 paraffins, methane, and carbon dioxide (CO.sub.2) and at least a portion of the C2-C7 paraffins, methane, and carbon dioxide (CO.sub.2) is separated from the third stream before contacting the third stream with the dehydration catalyst.

3. The process of claim 1, wherein the CO hydrogenation catalyst comprises a cobalt molybdenum containing catalyst having a β-phase crystal structure.

4. The process of claim 3, wherein the cobalt molybdenum containing catalyst includes a cobalt molybdenum oxide having a β-phase crystal structure.

5. The process of claim 4, wherein the CO hydrogenation catalyst comprises a calcined composition comprising: β-Co.sub.xMo.sub.yO.sub.z, wherein x ranges from 0.5 to 2.0, y ranges from 0.5 to 2.0, and z ranges from 3.5 to 4.5.

6. The process of claim 5, wherein the calcined composition is essentially free of beta-molybdenum carbide (β-Mo.sub.2C), an alkaline metal promoter, and an alkaline earth metal promoter.

7. The process of claim 5, wherein the calcined composition comprises β-CoMoO.sub.4.

8. The process of claim 1, wherein the CO hydrogenation catalyst is prepared using a method comprising: (i) preparing a solution comprising a cobalt salt and a molybdenum salt and collecting a precipitate from the solution; (ii) drying the precipitate to give a dried precipitate comprising one or more hydrates of cobalt molybdenum oxide; (iii) optionally pelleting the dried precipitate to produce pellets; and (iv) calcining the dried precipitate or optionally the pellets to generate the CO hydrogenation catalyst, wherein the pellets are optionally not subjected to mechanical deformation subsequent to calcination.

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

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

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

12. The process of claim 1, wherein in step (a) the 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.

13. 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.

14. The process of claim 1, wherein the step (b) contacting conditions comprise a pressure of 50 to 100 bar, GHSV of 1000 to 3000 h.sup.−1, and a temperature of 150 to 450° C.

15. The process of claim 1, wherein in step (b) the CO conversion is 25% to 35%, propanol selectivity is 12% to 25%, and butanol selectivity is 20% to 45%.

16. The process of claim 2, wherein the at least a portion of the C2-C7 paraffins, methane and carbon dioxide (CO.sub.2) is separated from the third stream by distillation.

17. The process of claim 1, wherein the step (c) contacting conditions comprises 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 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 propylene and butylene.

[0023] FIG. 2: is graph depicting CO conversion and product selectivity profile for batch 1 of powdered β-CoMoO.sub.4.

[0024] FIG. 3: is graph depicting CO conversion and product selectivity profile for batch 2 of powdered β-CoMoO.sub.4.

[0025] FIG. 4: is a graph depicting CO conversion and product selectivity profile for α-CoMoO.sub.4 in powdered form.

[0026] FIG. 5: is a graph depicting CO conversion and product selectivity profile for α-CoMoO.sub.4 in pellet form.

[0027] FIG. 6: is a graph depicting CO conversion and product selectivity profile for batch 1 of β-CoMoO.sub.4 in pellet form.

[0028] FIG. 7: is a graph depicting CO conversion and product selectivity profile for batch 2 of β-CoMoO.sub.4 in pellet form.

[0029] FIG. 8: is a graph depicting CO conversion and product selectivity profile for batch 3 of β-CoMoO.sub.4 in pellet form.

DETAILED DESCRIPTION OF THE INVENTION

[0030] A discovery has been made that provides a solution to at least some of the problems associated with the production of propylene and butylene. The solution is premised on using C1 hydrocarbon feedstock to produce these olefins. By way of example, CO and H.sub.2 can be produced from methane. The CO can by hydrogenated with the produced (or supplemental) H.sub.2 using a CO hydrogenation catalyst to produce propanol and butanol with high selectivity. The propanol and butanol can be dehydrated to produce propylene and butylene. It was surprisingly found that a cobalt/molybdenum catalyst having a β-phase crystal structure, such as β-CoMoO.sub.4, exhibits improved syngas conversion and propanol and butanol selectivity compared to a cobalt/molybdenum catalyst having a α-phase crystal structure, such as α-CoMoO.sub.4. Conventional catalyst preparation and processing, specifically, post-calcination grinding or pelletization, can induce a phase change of β-CoMoO.sub.4 to α-CoMoO.sub.4. A method has been discovered for the preparation of a cobalt/molybdenum catalyst that maintains a β-phase crystal structure during work-up and processing.

[0031] These and other non-limiting aspects of the present invention are discussed in further detail in the following paragraphs with reference to the figures.

[0032] Referring to FIG. 1, one example of a system and process of the present invention for producing propylene and butylene is described. System 100 can include a methane oxidizing unit 102, a CO hydrogenation unit 104, a separation unit 106, and a dehydration unit 108 (e.g., an alcohol dehydration unit).

[0033] 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 syngas (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: (1) 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; (2) a gas hour space velocity (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 GHSV 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, 11000 h.sup.−1, 12000 h.sup.−1, 13000 h.sup.−1, 14000 h.sup.−1 and 15000 h.sup.−1; and/or (3) 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, or any alloy, oxide, or combination thereof. The support can be alumina, silica, zirconia, ceria, titania, magnesium oxide, magnesium aluminate, or any 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, or K, or any alloy, oxide, or 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.

[0034] 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 propanol, butanol, C2-C7 paraffins, methane and CO.sub.2. The combined selectivity of the propanol and butanol can be 50% to 70% 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%, and 70%. In some particular aspects, the selectivity of the propanol can be 12% to 25% or at least any one of, equal to any one of, or between any two of 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, and 25%. In some particular aspects, the selectivity of the butanol can be 20% to 45% 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%, 40%, 41%, 42%, 43%, 44%, and 45%. In some particular aspects, the selectivity of the C2 to C7 paraffins can be 30% to 45% or at least any one of, equal to any one of, or between any two of 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, and 45%. In some particular aspects, the selectivity of the CO.sub.2 can be 0% to 5% or at least any one of, equal to any one of, or between any two of 0%, 1%, 2%, 3%, 4%, and 5%. In some particular aspects, the selectivity of the methane can be 3% to 10% or at least any one of, equal to any one of, or between any two of 3%, 4%, 5%, 6%, 7%, 8%, 9%, and 10%. 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.−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 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 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 off line 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.

[0035] The CO hydrogenation catalyst can include a cobalt molybdenum catalyst having a β-phase crystal structure. In some aspects, the CO hydrogenation catalyst can comprise a cobalt molybdenum oxide having a β-phase crystal structure. In some aspects, the CO hydrogenation catalyst can comprise a calcined composition comprising: β-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 aspects, the calcined composition can be essentially free of beta-molybdenum carbide (β-Mo.sub.2C), an alkaline metal promoter, and an alkaline earth metal promoter. In some particular aspects, the calcined composition can comprise β-CoMoO.sub.4. In some aspects, the cobalt molybdenum catalyst having a β-phase crystal structure can be prepared using a method including the steps of preparing a solution comprising a cobalt salt and a molybdenum salt and collecting a precipitate from the solution; drying the precipitate to give a dried precipitate comprising one or more hydrates of cobalt molybdenum oxide; optionally pelleting the dried precipitate to produce pellets; and calcining the dried precipitate or optionally the pellets to generate the β-phase catalyst. In some aspects, the pellets are not subjected to mechanical deformation such as grinding subsequent to calcination. The cobalt salt can be cobalt acetate and the molybdenum salt can be ammonium heptamolybdate. In some aspects, the solution contains a binary solvent, preferably ethanol and water, more preferably from 10 to 30% ethanol and from 70 to 90% water, even more preferably 20% ethanol and 80% water, vol:vol. In some aspects, precipitate is dried at a temperature ranging from 70 to 150° C., preferably from 90 to 130° C., more preferably from 100 to 120° C. In some aspects, the precipitate is dried for a period of time ranging from 4 to 8 hours, preferably from 5 to 7 hours. In some embodiments, the pellets are calcined at a temperature ranging from 300 to 700° C., preferably from 400 to 600° C., more preferably from 450 to 550° C. In some aspects, the pellets are calcined for a period of time ranging from 2 to 6 hours, preferably from 3 to 5 hours, more preferably from 2.5 to 3.5 hours. In some aspects, the pellets are calcined under an ambient air environment. Ambient air is defined as atmospheric air present at the calcination unit. In further embodiments, the pellets are calcined under oxygen, nitrogen, helium, or a combination thereof. In other aspects of the invention, however, other CO hydrogenation catalysts can be used.

[0036] A third stream before separation 118 containing at least a portion of the propanol, butanol, C2-C7 paraffins, methane, and CO.sub.2 obtained from CO hydrogenation unit 104 can enter the separation unit 106. In some aspects, the stream 118 can contain at least any one of, equal to any one of, or between any two of 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. %, propanol; 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. %, 40 mol. %, 41 mol. %, 42 mol. %, 43 mol. %, 44 mol. %, and 45 mol. %, butanol; at least any one of, equal to any one of, or between any two of 30 mol. %, 31 mol. %, 32 mol. %, 33 mol. %, 34 mol. %, 35 mol. %, 36 mol. %, 37 mol. %, 38 mol. %, 39 mol. %, 40 mol. %, 41 mol. %, 42 mol. %, 43 mol. %, 44 mol. %, and 45 mol. % C2-C7 paraffins, at least any one of, equal to any one of, or between any two of 3 mol. %, 4 mol. %, 5 mol. %, 6 mol. %, 7 mol. %, 8 mol. %, 9 mol. %, and 10 mol. % methane, and at least any one of, equal to any one of, or between any two of 0 mol. %, 1 mol. %, 2 mol. %, 3 mol. %, 4 mol. %, and 5 mol. % CO.sub.2. In the separation unit 106, the C2-C7 paraffins, methane, and CO.sub.2 can be separated from propanol and butanol. The third stream after separation 120 containing the propanol and butanol can enter the dehydration unit 108 from the separation unit 106 and a stream 122 containing the C2-C7 paraffins, methane, and CO.sub.2 can exit the separation unit 106. The separation of the C2-C7 paraffins, methane, and CO.sub.2 from the third stream in the 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 separation unit 106 can contain a distillation column and the stream 120 can be obtained as a bottom distillate product and the 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. In some aspects, at least a portion of methane from stream 122 can be recycled to the methane oxidizing unit 102 (not shown).

[0037] The stream 120 can enter the dehydration unit 108. In the dehydration unit 108 the stream 120 can be contacted with an alcohol dehydration catalyst (not shown) under conditions suitable to dehydrate at least a portion of the propanol and butanol and produce a products stream 124 containing propylene and butylene. The dehydration conditions can include: (1) 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; (2) a GHSV 1000 h.sup.−1 to 3000 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 (3) 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 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 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

Catalyst Preparation

Example 1A: β-CoMo Powder Preparation

[0041] Separate solutions (each in 100 ml of a binary solvent; 80% H.sub.2O, 20% EtOH) of cobalt acetate (12.45 g) and ammonium heptamolybdate (8.45 g) were heated to 65° C. to dissolve the salts. The molybdenum solution was heated at 65° C. while stirring, and the cobalt solution was added dropwise using a separatory funnel. The combined solution was 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 dried catalyst precursor was ground to a powder then calcined (500° C., static air, 10° C./min heating rate, 4 h). The powder was sieved through 180 micron sieve before testing. The purple color was maintained after calcination. The calcined catalyst (6 ml volume comprising 3 ml catalyst and 3 ml SiC) was then reduced in situ (16 h, H.sub.2, 50 ml/min, 350° C., 1° C. min.sup.−1). Two batches, batch 1 (B1) and batch 2 (B2) were than tested to asses reproducibility.

Example 1B: α-CoMoO.SUB.4 .Powder and Pellet Preparation

[0042] Separate solutions (each in 100 ml of a binary solvent; 80% H.sub.2O, 20% EtOH) of cobalt acetate (12.45 g) and ammonium heptamolybdate (8.45 g) were heated to 65° C. to dissolve the salts. The molybdenum solution was heated at 65° C. while stirring, and the cobalt solution was added dropwise using a separatory funnel. The combined solution was 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 dried catalyst precursor was ground to a powder then calcined (500° C., static air, 10° C./min, 4 h). The calcined powder was then grinded. Post-calcination grinding induced a phase change from β-CoMoO.sub.4 (purple) to α-CoMoO.sub.4 (green). The color and phase change were observed before loading the green α-CoMoO.sub.4 into the reactor. An in situ pre-reduction H.sub.2 step was performed before syngas testing. The power obtained with post-calcination grinding was then pelleted (10 ton pressure). The pellets were sieved through 200-425 micron sieve before testing.

Example 1C: β-CoMo Pellet Preparation

[0043] In order to confirm that the catalyst prepared in Example 1 is stable in pelleted form and does not change phase upon pelleting, a pelleted version of the Example 1 catalyst (Example 3) was prepared. After preparing the Example 1 catalyst powder described above, the powder was then pelleted (10 ton pressure) then calcined (500° C., static air, 10° C./min, 4 h) to give the final stable pelleted β-CoMoO.sub.4 catalyst. Preparing the catalyst pellets before calcination (when catalyst exists as hydrated form of the β-CoMoO.sub.4) ensured that the catalyst remained in the β-form. The pellets were sieved through 200-425 micron sieve before testing.

Example 2

Catalyst Activity/Selectivity Evaluation

[0044] The catalysts produced in Examples 1A-C were evaluated for the activity and selectivity, as well as short- and long-term stabilities. Prior to activity measurement, all of the catalysts were subjected to a reductive activation procedure (H.sub.2, 100 ml/min, 350° C., 1° C./min, 16 h). Catalyst evaluation was carried out in a high-throughput, fixed-bed flow reactor setup housed in temperature-controlled system fitted with regulators to maintain pressure during reactions. The products of the reactions were analyzed through online GC analysis. The evaluation was carried out under the following conditions unless otherwise indicated: 75 bar, 300° C., 1° C./min, 48 h stabilization, 100 ml/min, 50% SiC mix. The mass balances of the reactions were calculated to be 95±5%.

[0045] Catalyst testing results are depicted in FIGS. 2-8. FIGS. 2-3 provide results for two catalyst batches prepared in powder form without pelleting, i.e., the β-phase. Cumulative selectivity towards C.sub.3-C.sub.4 alcohols was in the range of 50-60%, with approximately 30% conversion.

[0046] When the catalyst is pelleted/ground post-calcination, the product distribution changes, with methane, methanol, and other hydrocarbons observed as major products (FIGS. 4-5). The distinct product distribution was attributed to the α-CoMoO.sub.4 phase, which was green in color. The results demonstrate that the β-phase catalyst is vastly superior for the production of C.sub.3-C.sub.4 alcohols.

[0047] In order to make the catalyst industrially applicable, robust catalytic material must be produced that will endure the harsh conditions provided by fixed bed reactor setups. This goal was achieved by pelleting the catalyst before calcination (in hydrated form). The catalyst (Example 1C) was purple in color and successfully retained the β-CoMoO.sub.4 phase. The results were examined for three batches (FIGS. 6-8). When β-CoMoO.sub.4 was pelleted before calcination, it retained high selectivity for C.sub.3-C.sub.4 alcohols. Cumulative selectivity towards C.sub.3-C.sub.4 alcohols was in the range of 50-60%, however, butanol selectivity was higher for β-pellets (Example 1C, FIGS. 6-8) than for β-powders (Example 1A, FIGS. 2-3). Syngas conversion for β-pellets and β-powders was similar, with conversion amounts at approximately 30%.

[0048] It is evident from the data provided herein that the β-CoMoO.sub.4 provides higher selectivity towards propanol and butanol, whereas α-CoMoO.sub.4 catalyst produces more methanol and CO.sub.2. Upon further extending the process to dehydration, metal doped heteropoly acids like silicotungstic acid doped with cesium supported on alumina or silica may be used to produce propylene and butylene in high yields.

[0049] In the context of the present invention at least the following 20 embodiments are described. Embodiment 1 is a process for producing propylene and butylene. 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 propanol and butanol; and (c) contacting the third stream with a dehydration catalyst under conditions suitable to dehydrate at least a portion of the propanol and butanol and produce a products stream containing propylene and butylene. Embodiment 2 is the process of embodiment 1, wherein the third stream further contains C2-C7 paraffins, methane, and carbon dioxide (CO.sub.2) and at least a portion of the C2-C7 paraffins, methane, and carbon dioxide (CO.sub.2) is separated from the third stream before contacting the third stream with the dehydration catalyst. Embodiment 3 is the process of either of embodiments 1 or 2, wherein the CO hydrogenation catalyst includes a cobalt molybdenum containing catalyst having a β-phase crystal structure. Embodiment 4 is the process of embodiment 3, wherein the cobalt molybdenum containing catalyst includes a cobalt molybdenum oxide having a β-phase crystal structure. Embodiment 5 is the process of embodiment 4, wherein the CO hydrogenation catalyst includes a calcined composition containing: β-Co.sub.xMo.sub.yO.sub.z, wherein x ranges from 0.5 to 2.0, y ranges from 0.5 to 2.0, and z ranges from 3.5 to 4.5. Embodiment 6 is the process of embodiment 5, wherein the calcined composition is essentially free of beta-molybdenum carbide (β-Mo.sub.2C), an alkaline metal promoter, and an alkaline earth metal promoter. Embodiment 7 is the process of either of embodiments 5 or 6, wherein the calcined composition contains β-CoMoO.sub.4. Embodiment 8 is the process of any one of embodiments 1 to 7, wherein the CO hydrogenation catalyst is prepared using a method including preparing a solution containing a cobalt salt and a molybdenum salt and collecting a precipitate from the solution and drying the precipitate to give a dried precipitate containing one or more hydrates of cobalt molybdenum oxide. The method further includes optionally pelleting the dried precipitate to produce pellets, and calcining the dried precipitate or optionally the pellets to generate the CO hydrogenation catalyst, wherein the pellets are optionally not subjected to mechanical deformation subsequent to calcination. Embodiment 9 is the process of any one of embodiments 1 to 8, wherein the CO hydrogenation catalyst is reduced and activated prior to contacting with the second stream. Embodiment 10 is the process of any one of embodiments 1 to 9, wherein the oxidant is steam, oxygen (O.sub.2), CO.sub.2, or a combination thereof. Embodiment 11 is the process of any one of embodiments 1 to 10, wherein the oxidation of the at least a portion of the methane is catalyzed using a methane oxidation catalyst, wherein the methane oxidation catalyst contains one or more metals of La, Ni, Ru, Rh, Pd, Ir, or Pt, on a support containing alumina, silica, zirconia, ceria, titania, magnesium oxide, or magnesium aluminate, or any combination thereof. Embodiment 12 is the process of any one of embodiments 1 to 11, wherein in step (a) the 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 13 is the process of any one of embodiments 1 to 12, wherein the molar ratio of the H.sub.2 and CO in the second stream is 0.5:1 to 3:1. Embodiment 14 is the process of any one of embodiments 1 to 13, wherein the step (b) contacting conditions include a pressure of 50 to 100 bar, GHSV of 1000 to 3000 and a temperature of 150 to 450° C. Embodiment 15 is the process of any one of embodiments 1 to 14, wherein in step (b) the CO conversion is 25% to 35%, propanol selectivity is 12% to 25%, and butanol selectivity is 20% to 45%. Embodiment 16 is the process of any one of embodiments 2 to 15, wherein the at least a portion of the C2-C7 paraffins, methane and carbon dioxide (CO.sub.2) is separated from the third stream by distillation. Embodiment 17 is the process of any one of embodiments 1 to 16, wherein the step (c) contacting conditions includes a pressure of 0 to 90 bar, GHSV of 1000 to 3000 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 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