Process for making unsaturated hydrocarbons using microchannel process technology

• US 7,923,592 B2
• Filed: 02/02/2007
• Issued: 04/12/2011
• Est. Priority Date: 02/02/2007
• Status: Expired due to Fees

• Current Assignee: Velocys Incorporated (Velocys PLC)
• Original Assignee: Velocys Incorporated (Velocys PLC)
• Inventors: Yuschak, Thomas, Simmons, Wayne W., Rankin, Scott, Perry, Steven T., Tonkovich, Anna Lee, LaPlante, Timothy J., Mazanec, Terry, Daymo, Eric, Fitzgerald, Sean Patrick
• Primary Examiner(s): Nguyen; Tam M
• Application Number:
  US11/670,608
• Publication Number:
  US 20080184915A1
• Time in Patent Office: 1,530 Days
• Field of Search: None
• US Class Current: 585/654
• CPC Class Codes: B01J 19/0093 Microreactors, e.g. miniaturised or microfabricated reactors laboratory containers with capillary fluid transport in microfabricated channels or chambers B01L3/5027
• CPC Class Codes: B01J 2219/00783 Laminate assemblies, i.e. the reactor comprising a stack of plates
• CPC Class Codes: B01J 2219/00822 Metal
• CPC Class Codes: B01J 2219/00824 Ceramic
• CPC Class Codes: B01J 2219/00831 Glass
• CPC Class Codes: B01J 2219/00833 Plastic
• CPC Class Codes: B01J 2219/0086 Dimensions of the flow channels
• CPC Class Codes: B01J 2219/00873 Heat exchange
• CPC Class Codes: B01J 2219/00889 Mixing micromixers B01F33/30
• CPC Class Codes: B01J 2219/00891 Feeding or evacuation
• CPC Class Codes: C07C 11/04 Ethylene
• CPC Class Codes: C07C 5/327 Formation of non-aromatic carbon-to-carbon double bonds only
• CPC Class Codes: C07C 5/48 with oxygen as an acceptor
• CPC Class Codes: C10G 45/00 Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
• CPC Class Codes: C10G 47/22 Non-catalytic cracking in the presence of hydrogen
• CPC Class Codes: C10G 9/18 Apparatus

Abstract

The disclosed invention relates to a process for converting a feed composition comprising one or more hydrocarbons to a product comprising one or more unsaturated hydrocarbons, the process comprising: flowing the feed composition and steam in contact with each other in a microchannel reactor at a temperature in the range from about 200° C. to about 1200° C. to convert the feed composition to the product, the process being characterized by the absence of catalyst for converting the one or more hydrocarbons to one or more unsaturated hydrocarbons. Hydrogen and/or oxygen may be combined with the feed composition and steam.

Claims

1. A process for converting a feed composition comprising one or more hydrocarbons to a product comprising one or more unsaturated hydrocarbons, the process comprising:

flowing the feed composition and steam in contact with each other in a microchannel reactor at a temperature in the range from about 200°

C. to about 1200°

C. to convert the feed composition to the product, the process being characterized by the absence of catalyst for converting the one or more hydrocarbons to one or more unsaturated hydrocarbons;

with the proviso that the microchannel reactor optionally further comprises one or more materials that function as a catalyst for a reaction other than the conversion of the one or more hydrocarbons to the one or more unsaturated hydrocarbons, provided such materials do not increase the conversion of the one or more hydrocarbons to the one or more unsaturated hydrocarbons by more than about 10% of what the conversion would be if such materials were not present.

2. The process of claim 1 wherein the process comprises a cracking process wherein one or more C—

C bonds in one or more of the hydrocarbons in the feed composition are ruptured to yield a product comprising one or more hydrocarbons having a lower molecular weight than the one or more hydrocarbons in the feed composition, one or more of the hydrocarbons in the product being the one or more unsaturated hydrocarbons.

3. The process of claim 1 wherein the process comprises a dehydrogenation process wherein one or more C—

H bonds in one or more of the hydrocarbons in the feed composition are ruptured to yield hydrogen and the one or more unsaturated hydrocarbons in the product.

4. The process of claim 1 wherein hydrogen flows in the microchannel reactor in contact with the feed composition and steam.

5. The process of claim 1 wherein oxygen flows in the microchannel reactor in contact with the feed composition and steam.

6. The process of claim 1 wherein hydrogen and oxygen flow in the microchannel reactor in contact with the feed composition and steam.

7. The process of claim 1 wherein the feed composition and steam are mixed with each other prior to entering the microchannel reactor.

8. The process of claim 1 wherein the feed composition and steam are mixed with each other in the microchannel reactor.

9. The process of claim 1 wherein part of the steam is mixed with the feed composition prior to entering the microchannel reactor and part of the steam is mixed with the feed composition in the microchannel reactor.

10. The process of claim 1 wherein the microchannel reactor comprises at least one process microchannel, the at least one process microchannel having a feed entrance for permitting the feed composition to enter the at least one process microchannel and at least one staged addition entrance for permitting the steam to enter the at least one process microchannel, the at least one staged addition entrance being downstream of the feed entrance.

11. The process of claim 1 wherein the process is conducted in a microchannel reactor comprises a plurality of process microchannels and at least one header for distributing the feed composition and the steam to the process microchannels, the process further comprising mixing the feed composition and the steam in the header, the resulting mixture of feed composition and steam flowing from the header into the process microchannels.

12. The process of claim 1 wherein the microchannel reactor comprises at least one process microchannel, the feed composition and steam contacting surface features in the at least one process microchannel, the contacting of the surface features with the feed composition and steam imparting a disruptive flow to the feed composition and steam.

13. The process of claim 12 wherein the surface features are oriented at oblique angles relative to the direction of the bulk flow of the feed composition in the at least one process microchannel.

14. The process of claim 12 wherein the surface features comprise two or more layers stacked on top of each other and/or intertwined in one or more three-dimensional patterns.

15. The process of claim 12 wherein the surface features are in the form of circles, oblongs, squares, rectangles, checks, chevrons, wavy shapes, or combinations thereof.

16. The process of claim 12 wherein the surface features comprise sub-features where the major walls of the surface features further contain smaller surface features in the form of notches, waves, indents, holes, burrs, checks, scallops, or combinations thereof.

17. The process of claim 12 wherein the surface features comprise a plurality of interconnected oblique angles.

18. The process of claim 1 wherein the microchannel reactor comprises at least one process microchannel, the at least one process microchannel having an internal dimension of width or height of up to about 10 mm.

19. The process of claim 1 wherein the microchannel reactor comprises at least one process microchannel, the at least one process microchannel being made of a material comprising:

steel;

monel;

inconel;

aluminum;

titanium;

nickel;

copper;

brass;

an alloy of any of the foregoing metals;

a polymer;

ceramics;

glass;

a composite comprising a polymer and fiberglass;

quartz;

silicon;

or a combination of two or more thereof.

20. The process of claim 1 wherein the microchannel reactor comprises at least one process microchannel, the at least one process microchannel having a length in the range up to about 10 meters.

21. The process of claim 1 wherein the microchannel reactor comprises at least one process microchannel, the at least one process microchannel being heated by a heat source.

22. The process of claim 21 wherein the heat source comprises at least one heat exchange channel.

23. The process of claim 22 wherein the heat exchange channel comprises a microchannel.

24. The process of claim 22 wherein the heat exchange channel is made of a material comprising:

steel;

monel;

inconel;

aluminum;

titanium;

nickel;

copper;

brass;

an alloy of any of the foregoing metals;

a polymer;

ceramics;

glass;

a composite comprising polymer and fiberglass;

quartz;

silicon;

or a combination of two or more thereof.

25. The process of claim 22 wherein a heat exchange fluid is in the heat exchange channel.

26. The process of claim 25 wherein the heat exchange fluid undergoes a phase change in the heat exchange channel.

27. The process of claim 22 wherein an exothermic process is conducted in the heat exchange channel.

28. The process of claim 22 wherein a combustion reaction is conducted in the heat exchange channel.

29. The process of claim 22 wherein the bulk flow direction for the feed composition in the process microchannel is in a first direction, and a heat exchange fluid flows in the heat exchange channel in a second direction, the second direction being cross current relative to the first direction.

30. The process of claim 22 wherein the bulk flow direction for the feed composition in the process microchannel is in a first direction, and a heat exchange fluid flows in the heat exchange channel in a second direction, the second direction being cocurrent or counter current relative to the first direction.

31. The process of claim 22 wherein a heat exchange fluid is in the heat exchange channel, the heat exchange fluid comprising one or more of steam, carbon monoxide, carbon dioxide, gaseous nitrogen, inert gas, gaseous hydrocarbon, liquid hydrocarbon, or a mixture of two or more thereof.

32. The process of claim 21 wherein the heat source comprises an electric heating element and/or resistance heater.

33. The process of claim 21 wherein the at least one process microchannel has at least one heat transfer wall, the heat flux between the heat source and the at least one process microchannel being in the range from about 0.01 to about 500 watts per square centimeter of surface area of the heat transfer wall.

34. The process of claim 1 wherein the microchannel reactor comprises at least one process microchannel, the at least one process microchannel being in thermal contact with a plurality of heat exchange zones, the temperature in each heat exchange zone being different.

35. The process of claim 1 wherein the microchannel reactor comprises at least one process microchannel, the product being quenched in the at least one process microchannel.

36. The process of claim 1 wherein the product flows out of the microchannel reactor and is quenched.

37. The process of claim 1 wherein the feed composition is preheated and the product is quenched, the product being quenched transferring heat to the feed composition being preheated.

38. The process of claim 1 wherein the microchannel reactor comprises at least one process microchannel, the feed composition being preheated in the at least one process microchannel and the product being quenched in the at least one process microchannel, the product being quenched transferring heat to the feed composition being preheated.

39. The process of claim 1 wherein the feed composition comprises one or more saturated hydrocarbon compounds, one or more unsaturated hydrocarbon compounds, one or more hydrocarbyl substituted aromatic compounds, or a mixture of two or more thereof.

40. The process of claim 1 wherein the feed composition comprises one or more alkanes of 2 to about 25 carbon atoms.

41. The process of claim 1 wherein the feed composition comprises mineral oil, synthetic oil, atmospheric gas oil, straight run gas oil, vacuum gas oil, demetallized oil, deasphalted vacuum residue, coker distillate, cat cracker distillate, shale oil, tar sand oil, coal liquid, or a mixture of two or more thereof.

42. The process of claim 1 wherein the steam is at a temperature in the range from about 100°

C. to about 1100°

C. at the entrance to the microchannel reactor.

43. The process of claim 4 wherein the hydrogen is derived from a steam reforming process, partial oxidation process, autothermal reforming process, carbon dioxide reforming process, coal gassification process, or a combination of two or more thereof.

44. The process of claim 5 wherein the oxygen is from a source of oxygen which comprises air, oxygen enriched air, a nitrogen oxide, carbon dioxide, carbon monoxide, a peroxide, a gaseous mixture comprising oxygen and at least one inert gas and/or a diluent gas, or a mixture of two or more thereof.

45. The process of claim 1 wherein the pressure in the microchannel reactor is in the range from about 1 to about 100 atmospheres.

46. The process of claim 1 wherein the Q-factor for the microchannel reactor is less than about 50%.

47. The process of claim 1 wherein the microchannel reactor comprises at least one process microchannel and fluid is flowing in the at least one process microchannel, the superficial velocity for fluid flowing in the at least one process microchannel being at least about 0.01 m/s.

48. The process of claim 1 wherein the product comprises one or more unsaturated aliphatic compounds.

49. The process of claim 1 wherein the product comprises one or more hydrocarbylene substituted aromatic compounds.

50. The process of claim 1 wherein the product comprises ethylene, propylene, butene, isobutene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-dodecene, styrene, or a mixture of two or more thereof.

51. The process of claim 1 wherein the product comprises a middle distillate boiling in the range from about 125°

C. to about 375°

C. at atmospheric pressure.

52. The process of claim 1 wherein the product comprises a C₅ to about 205°

C. end point distillate fraction.

53. The process of claim 1 wherein the product comprises diesel fuel, jet fuel, kerosene, gasoline, naphtha, or a mixture of two or more thereof.

55. The process of claim 1 wherein the microchannel reactor comprises one or more interior surfaces wherein one or more passivation layers are on one or more of the interior surfaces.

56. The process of claim 1 wherein the contact time is in the range from about 1 to about 100 ms.

57. The process of claim 1 wherein reactants and product flow through the microchannel reactor, the reactants and product flowing through the microchannel reactor at a rate of at least about 5 standard liters per minute.

54. A process for converting a feed composition comprising ethane to a product comprising ethylene, the process comprising:

flowing the feed composition and steam in contact with each other in a microchannel reactor at a temperature in the range from about 700°

C. to about 1100°

C. to convert the feed composition to the product, the process being characterized by the absence of catalyst for converting ethane to ethylene;

with the proviso that the microchannel reactor optionally further comprises one or more materials that function as a catalyst for a reaction other than the conversion of ethane to ethylene, provided such materials do not increase the conversion of ethane to ethylene by more than about 10% of what the conversion would be if such materials were not present.