Process for making styrene using mircochannel process technology

• US 7,847,138 B2
• Filed: 03/23/2007
• Issued: 12/07/2010
• Est. Priority Date: 03/23/2006
• Status: Expired due to Fees

• Current Assignee: Velocys Incorporated (Velocys PLC)
• Original Assignee: Velocys Incorporated (Velocys PLC)
• Inventors: Long, Richard Q., Yang, Bin, Tonkovich, Anna Lee, Daly, Francis P., Jarosch, Kai Tod Paul, Marco, Jeffrey, LaPlante, Timothy J., Hickey, Thomas P.
• Primary Examiner(s): DANG, THUAN D
• Application Number:
  US11/690,319
• Publication Number:
  US 20070225532A1
• Time in Patent Office: 1,355 Days
• Field of Search: 585/323, 585/446, 585/440, 585/444, 585/921
• US Class Current: 585/323
• CPC Class Codes: B01F 2101/2204 Mixing chemical components in generals in order to improve chemical treatment or reactions, independently from the specific application
• CPC Class Codes: B01F 25/3142 the conduit having a plurality of openings in the axial direction or in the circumferential direction
• CPC Class Codes: B01F 25/31422 with a plurality of perforations in the axial direction only
• CPC Class Codes: B01F 25/31424 with a plurality of perforations aligned in a row perpendicular to the flow direction
• CPC Class Codes: B01F 25/4317 Profiled elements, e.g. profiled blades, bars, pillars, columns or chevrons
• CPC Class Codes: B01F 25/431971 Mounted on the wall
• CPC Class Codes: B01F 25/433 Mixing tubes wherein the shape of the tube influences the mixing, e.g. mixing tubes with varying cross-section or provided with inwardly extending profiles
• CPC Class Codes: B01F 25/4338 Mixers with a succession of converging-diverging cross-sections, i.e. undulating cross-section
• CPC Class Codes: B01F 33/30 Micromixers
• 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 2219/00804 Plurality of plates
• CPC Class Codes: B01J 2219/0081 Plurality of modules
• CPC Class Codes: B01J 2219/00822 Metal
• CPC Class Codes: B01J 2219/00824 Ceramic
• CPC Class Codes: B01J 2219/00826 Quartz
• CPC Class Codes: B01J 2219/00828 Silicon wafers or plates
• CPC Class Codes: B01J 2219/00831 Glass
• CPC Class Codes: B01J 2219/00833 Plastic
• CPC Class Codes: B01J 2219/00835 Comprising catalytically active material
• CPC Class Codes: B01J 2219/00844 : Comprising porous material
• CPC Class Codes: B01J 2219/0086 : Dimensions of the flow channels
• CPC Class Codes: B01J 2219/00869 : Microreactors placed in parallel, on the same or on different supports
• CPC Class Codes: B01J 2219/00873 : Heat exchange
• CPC Class Codes: B01J 2219/00876 : Insulation elements
• CPC Class Codes: B01J 2219/00878 : Vacuum spaces
• 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 15/073 : Ethylbenzene
• CPC Class Codes: C07C 15/46 : Styrene; Ring-alkylated styrenes
• CPC Class Codes: C07C 2/66 : Catalytic processes
• CPC Class Codes: C07C 2521/02 : Boron or aluminium; Oxides or hydroxides thereof
• CPC Class Codes: C07C 2521/06 : Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
• CPC Class Codes: C07C 2521/08 : Silica
• CPC Class Codes: C07C 2521/10 : Magnesium; Oxides or hydroxides thereof
• CPC Class Codes: C07C 2523/02 : of the alkali- or alkaline earth metals or beryllium
• CPC Class Codes: C07C 2523/04 : Alkali metals
• CPC Class Codes: C07C 2523/10 : of rare earths
• CPC Class Codes: C07C 2523/18 : Arsenic, antimony or bismuth
• CPC Class Codes: C07C 2523/22 : Vanadium
• CPC Class Codes: C07C 2523/26 : Chromium
• CPC Class Codes: C07C 2523/28 : Molybdenum
• CPC Class Codes: C07C 2523/30 : Tungsten
• CPC Class Codes: C07C 2523/42 : Platinum
• CPC Class Codes: C07C 2523/44 : Palladium
• CPC Class Codes: C07C 2523/46 : Ruthenium, rhodium, osmium or iridium
• CPC Class Codes: C07C 2523/745 : Iron
• CPC Class Codes: C07C 2523/847 : Vanadium, niobium or tantalum
• CPC Class Codes: C07C 2523/881 : and iron
• CPC Class Codes: C07C 2523/883 : and nickel
• CPC Class Codes: C07C 2523/888 : Tungsten
• CPC Class Codes: C07C 2527/167 : Phosphates or other compounds comprising the anion (PnO3n+1)(n+2)-
• CPC Class Codes: C07C 5/277 : Catalytic processes
• CPC Class Codes: C07C 5/3332 : with metal oxides or metal sulfides
• CPC Class Codes: C07C 5/48 : with oxygen as an acceptor
• CPC Class Codes: F28D 9/00 : Heat-exchange apparatus having stationary plate-like or laminated conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall F28F3/083, F28F3/086 take precedence
• CPC Class Codes: F28F 13/12 : by creating turbulence, e.g. by stirring, by increasing the force of circulation F28F13/08 takes precedence
• CPC Class Codes: F28F 21/04 : of ceramic; of concrete; of natural stone
• CPC Class Codes: F28F 21/081 : Heat exchange elements made from metals or metal alloys
• CPC Class Codes: F28F 2260/02 : having microchannels
• CPC Class Codes: F28F 2270/00 : Thermal insulation; Thermal decoupling
• CPC Class Codes: F28F 3/048 : in the form of ribs integral with the element or local variations in thickness of the element, e.g. grooves, microchannels
• CPC Class Codes: F28F 3/086 : having one or more openings therein forming tubular heat-exchange passages
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts
• CPC Class Codes: Y02P 20/582 : Recycling of unreacted starting or intermediate materials
• CPC Class Codes: Y10S 585/921 : using recited apparatus structure

Abstract

The disclosed invention relates to a process for converting ethylbenzene to styrene, comprising: flowing a feed composition comprising ethylbenzene in at least one process microchannel in contact with at least one catalyst to dehydrogenate the ethylbenzene and form a product comprising styrene; exchanging heat between the process microchannel and at least one heat exchange channel in thermal contact with the process microchannel; and removing product from the process microchannel. Also disclosed is an apparatus comprising a process microchannel, a heat exchange channel, and a heat transfer wall positioned between the process microchannel and heat exchange channel wherein the heat transfer wall comprises a thermal resistance layer.

Claims

1. A process for converting ethylbenzene to styrene, comprising:

flowing a feed composition comprising ethylbenzene in at least one styrene-forming process microchannel in contact with at least one catalyst to dehydrogenate the ethylbenzene and form a product comprising styrene;

exchanging heat between the process microchannel and at least one heat exchange channel in thermal contact with the process microchannel; and

removing product from the process microchannel;

wherein the ethylbenzene is formed by contacting benzene with ethylene in the presence of at least one alkylation catalyst; and

the ethylbenzene is formed in at least one ethylbenzene-forming process microchannel, the styrene-forming process microchannel and the ethylbenzene-forming process microchannel being the same or different.

2. The process of claim 1 wherein the catalyst in the styrene-forming process microchannel comprises at least one dehydrogenation catalyst.

3. The process of claim 1 wherein the feed composition is combined with a fluid comprising oxygen and the catalyst in the styrene-forming process microchannel comprises at least one oxidative dehydrogenation catalyst.

4. The process of claim 1 wherein the ethylene is formed by dehydrogenating ethane in the presence of at least one dehydrogenation catalyst in at least one ethylene-forming process microchannel, the styrene-forming process microchannel and the ethylene-forming process microchannel being the same or different.

5. The process of claim 1 wherein the ethylene is formed by reacting ethane with oxygen in the presence of at least one oxidative dehydrogenation catalyst in at least one ethylene-forming process microchannel, the styrene-forming process microchannel and the ethylene-forming process microchannel being the same or different.

6. The process of claim 1 wherein the feed composition further comprises, ethane, oxygen and hydrogen, and the catalyst comprises at least one oxidative dehydrogenation catalyst.

7. The process of claim 6 wherein the product comprises styrene, ethylbenzene, ethylene, and hydrogen.

8. The process of claim 7 wherein the ethylbenzene in the product is recycled to the feed composition.

9. The process of claim 7 wherein the hydrogen in the product is recycled to the feed composition.

10. The process of claim 7 wherein the ethylene in the product is reacted with benzene in the presence of at least one alkylation catalyst to form ethylbenzene, the ethylbenzene being recycled to the feed composition.

11. The process of claim 10 wherein the ethylene is reacted with the benzene in at least one process microchannel containing the alkylation catalyst.

12. The process of claim 3 wherein the feed composition and the oxygen are mixed prior to entering the styrene-forming process microchannel.

13. The process of claim 3 wherein a staged addition feed stream comprising the oxygen flows in a staged addition channel, the staged addition channel being adjacent to the styrene-forming process microchannel, the styrene-forming process microchannel having an entrance for the feed composition, the feed composition entering the styrene-forming process microchannel through the entrance for the feed composition, the staged addition feed stream flowing from the staged addition channel into the styrene-forming process microchannel, the staged addition feed stream entering the styrene-forming process microchannel downstream of the entrance for the feed composition and contacting the feed composition in the styrene-forming process microchannel.

14. The process of claim 1 wherein the feed composition further comprises air and/or steam.

15. The process of claim 3 wherein the feed composition comprises ethylbenzene and oxygen.

16. The process of claim 15 wherein the feed composition further comprises nitrogen.

17. The process of claim 13 wherein the staged addition feed stream comprises air, oxygen or oxygen enriched air.

18. The process of claim 2 wherein the catalyst comprises at least one oxide of iron, chromium, platinum, iridium, rhodium, palladium, or a combination thereof.

19. The process of claim 2 wherein the catalyst comprises iron oxide and one or more of potassium oxide, molybdenum oxide, cerium oxide, and calcium carbonate.

20. The process of claim 3 wherein the catalyst comprises at least one oxide of vanadium, molybdenum, tungsten, or a combination of two or more thereof.

21. The process of claim 3 wherein the catalyst comprises FeVO₄, CrVO₄, NaVO₃, BiVO₄, AIVO₄, CeVO₄, VOPO₄, LaVO₄, SmVO₄, NiMoO₄, MgMoO₄, CaMoO₄, FeMoO₄, Fe₂(MoO₄)₃, MgWO₄, CaWO₄, NiWO₄, FeWO₄, K₂O, MoO₃, SiO₂, TiO₂, or a combination of two or more thereof.

22. The process of claim 1 wherein the catalyst in the styrene-forming process microchannel comprises a graded catalyst.

23. The process of claim 1 wherein the catalyst in the styrene-forming process microchannel is supported on a support, the support comprising a heat conductive material.

24. The process of claim 1 wherein the catalyst in the styrene-forming process microchannel is supported on a support, the support being in the form of a foam, felt, wad, fin, or a combination of two or more thereof.

25. The process of claim 1 wherein the catalyst in the styrene-forming process microchannel is supported on a support, the support comprising a microgrooved support strip with a support strip having a length with a center axis extending along the length, a first surface, a first side edge, a second side edge, a front edge extending from the first side edge to the second side edge, a back edge extending from the first side edge to the second side edge, a plurality of parallel microgrooves in the first surface extending between the first side edge and the second side edge at an angle relative to the center axis.

26. The process of claim 25 wherein the support strip further comprises a plurality of parallel microgrooves extending between the front edge of the support strip and the first side edge of the support strip, and a plurality of parallel microgrooves extending between the back edge of the support strip and the second side edge of the support strip.

27. The process of claim 25 wherein the support strip is made of a thermally conductive material.

28. The process of claim 1 wherein the styrene-forming process microchannel exchanges heat with a heat exchange fluid flowing in the heat exchange channel.

29. The process of claim 28 wherein the heat exchange fluid undergoes a phase change as it flows in the heat exchange channel.

30. The process of claim 1 wherein the heat flux between the heat exchange channel and the styrene-forming process microchannel is in the range from about 0.01 to about 250 watts per square centimeter of surface area of the process microchannel.

31. The process of claim 1 wherein an endothermic process is conducted in the heat exchange channel.

32. The process of claim 1 wherein an exothermic process is conducted in the heat exchange channel.

33. The process of claim 1 wherein the process is conducted in a microchannel reactor comprising a plurality of the styrene-forming process microchannels and a plurality of the heat exchange channels.

34. The process of claim 33 wherein the microchannel reactor further comprises at least one header providing for the flow of the reactant composition into the process microchannels and at least one footer providing for the flow of product out of the process microchannels.

35. The process of claim 33 wherein the microchannel reactor further comprises a preheat section for heating the feed composition prior to flowing the feed composition in the styrene-forming process microchannels and a cool down section for cooling product flowing out of the styrene-forming process microchannels.

36. The process of claim 35 wherein the product flows from the cool down section to a styrene knockout drum where the product is cooled.

37. The process of claim 35 wherein the microchannel reactor comprises a microchannel reactor core containing the process microchannels and heat exchange channels, the microchannel reactor core and the cool down section being in thermal contact with the preheat section.

38. The process of claim 37 wherein the microchannel reactor core and the cool down section are adjacent to the preheat section.

39. The process of claim 1 wherein the gas hourly space velocity for the flow of the feed composition in the at least one styrene-forming process microchannel is at least about 1000 normal liters of feed per hour per liter of volume within the process microchannel.

40. The process of claim 1 wherein the catalyst in the styrene-forming process microchannel is supported on a support, the support having a length with a center axis extending along the length, a first surface, a first side edge, a second side edge, a front edge extending from the first side edge to the second side edge, a back edge extending from the first side edge to the second side edge, and a plurality of parallel microgrooves in the first surface aligned at an angle of about 90°

C. relative to the center axis.

41. The process of claim 1 wherein the catalyst in the styrene-forming process microchannel is supported on a support, the support having a length with a center axis extending along the length, a first surface, a first side edge, a second side edge, a front edge extending from the first side edge to the second side edge, a back edge extending from the first side edge to the second side edge, and a plurality of parallel microgrooves in the first surface aligned parallel to the center axis.

42. The process of claim 1 wherein the catalyst in the styrene-forming process microchannel is supported by a composite support structure, comprising:

at least one first support strip comprising a first surface, a second surface, a length with a center axis extending along the length, a front edge, a back edge, a first side edge, a second side edge, the front edge and the back edge extending from the first side edge and to the second side edge, and a plurality of parallel microgrooves in the first surface;

at least one second support strip comprising a first surface, a second surface, a length with a center axis extending along the length, a front edge, a back edge, a first side edge, a second side edge, the front edge and the back edge extending from the first side edge to the second side edge, and a plurality of parallel microgrooves in the first surface;

the first support strip being adjacent to the second support strip with the second surface of the first support strip contacting the first surface of the second support strip;

the microgrooves penetrating through the support strips sufficiently to permit fluid to flow through the support strips from one support strip to another;

microgrooves in the first surface of the first support strip intersecting microgrooves in the first surface of the second support strip to provide through holes extending through the first support strip and through the second support strip.

43. The process of claim 1 wherein a heat transfer wall is positioned between the styrene-forming process microchannel and the heat exchange channel, the heat transfer wall comprising at least one thermal resistance layer.

44. The process of claim 13 wherein a reaction zone is positioned within the styrene-forming process microchannel, the staged addition feed stream contacting the feed composition in the reaction zone.

45. The process of claim 13 wherein a mixing zone and a reaction zone are positioned within the styrene-forming process microchannel, the mixing zone being upstream of the reaction zone, the staged addition feed stream contacting the feed composition in the mixing zone.

46. The process of claim 13 wherein a mixing zone and a reaction zone are positioned within the styrene-forming process microchannel, the mixing zone being upstream of the reaction zone, part of the staged addition feed stream contacting the feed composition in the mixing zone, and part of the staged addition feed stream contacting the feed composition in the reaction zone.

47. The process of claim 1 wherein the styrene-forming process microchannel has an internal dimension of width or height of up to about 10 mm.

48. The process of claim 1 wherein the styrene-forming process microchannel has an internal dimension of width or height of up to about 2 mm.

49. The process of claim 1 wherein the styrene-forming process microchannel 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 a polymer and fiberglass;

quartz;

silicon;

or a combination of two or more thereof.

50. The process of claim 13 wherein the staged addition channel has an internal dimension of width or height of up to about 10 mm.

51. The process of claim 13 wherein the staged addition channel has an internal dimension of width or height of up to about 2 mm.

52. The process of claim 13 wherein the staged addition 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 a polymer and fiberglass;

quartz;

silicon;

or a combination of two or more thereof.

53. The process of claim 1 wherein the heat exchange channel is adjacent to the process microchannel.

54. The process of claim 1 wherein the heat exchange channel is in thermal contact with the process microchannel.

55. The process of claim 1 wherein the heat exchange channel comprises a microchannel.

56. The process of claim 1 wherein the heat exchange channel has an internal dimension of width or height of up to about 10 mm.

57. The process of claim 1 wherein the heat exchange channel has an internal dimension of width or height of up to about 2 mm.

58. The process of claim 1 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.

59. The process of claim 13 wherein the styrene-forming process microchannel and the staged addition channel have a common wall, the common wall having a plurality of openings extending along at least part of the length of the process microchannel, the staged addition feed stream flowing through the openings in the common wall.

60. The process of claim 13 wherein the styrene-forming process microchannel and the staged addition microchannel have a common wall with an apertured section in the common wall, the staged addition feed stream flowing from the staged addition channel through the apertured section into the process microchannel.

61. The process of claim 60 wherein the apertured section comprises a relatively thin sheet overlying a relatively thick sheet or plate, the relatively thin sheet containing an array of relatively small apertures, and the relatively thick sheet or plate containing an array of relatively large apertures, at least some of the relatively small apertures being aligned with the relatively large apertures.

62. The process of claim 60 wherein the apertured section comprises apertures that are partially filled with a coating material.

63. The process of claim 60 wherein the apertured section is made from a porous material.

64. The process of claim 60 wherein the apertured section is made from a porous material that is heat treated.

65. The process of claim 60 wherein the apertured section is made from a porous material, the porous material being metallic, nonmetallic, oxidized, and/or coated with nickel or alumina.

66. The process of claim 60 wherein the apertured section is made from a porous material, the surface of the porous material being treated by filling the pores on the surface with a liquid filler, solidifying the filler, grinding or polishing the surface, and removing the filler.

67. The process of claim 3 wherein the catalyst comprises V₂O₅, MoO₃, WO₃, or a combination of two or more thereof.

68. The process of claim 3 wherein the catalyst comprises at least one vanadate, molybdate, tungstate, or a combination of two or more thereof.

69. The process of claim 1 wherein the catalyst in the styrene-forming process microchannel is in the form of particulate solids.

70. The process of claim 1 wherein the catalyst in the styrene-forming process microchannel is washcoated on interior walls of the process microchannel or grown on interior walls of the process microchannel from solution.

71. The process of claim 1 wherein the catalyst in the styrene-forming process microchannel comprises a support, an optional buffer layer overlying the support, an interfacial layer overlying the optional buffer layer or the support, and a catalyst material dispersed or deposited on the interfacial layer.

72. The process of claim 1 wherein the catalyst in the styrene-forming process microchannel is supported by a support, the support being made of a material comprising one or more of silica gel, foamed copper, sintered stainless steel fiber, steel wool, alumina, poly(methyl methacrylate), polysulfonate, poly(tetrafluoroethylene), iron, nickel sponge, nylon, polyvinylidene difluoride, polypropylene, polyethylene, polyethylene ethylketone, polyvinyl alcohol, polyvinyl acetate, polyacrylate, polymethylmethacrylate, polystyrene, polyphenylene sulfide, polysulfone, polybutylene, or a combination of two or more thereof.

73. The process of claim 1 wherein the catalyst in the styrene-forming process microchannel is supported on a support, the support comprising an alloy comprising Ni, Cr and Fe, or an alloy comprising Fe, Cr, Al and Y.

74. The process of claim 1 wherein the catalyst in the styrene-forming process microchannel is supported on a support having a flow-by configuration, a flow-through configuration, a honeycomb structure or a serpentine configuration.

75. The process of claim 1 wherein the catalyst in the styrene-forming process microchannel is supported on a support having a flow-by configuration with an adjacent gap, a foam configuration with an adjacent gap, a fin structure with gaps, a washcoat on a substrate, or a gauze configuration with a gap for flow.

76. The process of claim 1 wherein the catalyst in the styrene-forming process microchannel is supported on a support, the support comprising a fin assembly comprising at least one fin.

77. The process of claim 76 wherein the fin assembly comprises a plurality of parallel spaced fins.

78. The process of claim 76 wherein the fin has an exterior surface and a porous material overlies at least part of the exterior surface of the fin, the catalyst being supported by the porous material.

79. The process of claim 78 wherein the porous material comprises a coating, fibers, foam or felt.

80. The process of claim 76 wherein the fin has an exterior surface and a plurality fibers or protrusions extend from at least part of the exterior surface of the fin, the catalyst being supported by the protrusions.

81. The process of claim 76 wherein the fin has an exterior surface and the catalyst is:

washcoated on at least part of the exterior surface of the fin;

grown on at least part of the exterior surface of the fin from solution;

or deposited on at least part of the exterior surface of the fin using vapor deposition.

82. The process of claim 76 wherein the fin assembly comprises a plurality of parallel spaced fins, at least one of the fins having a length that is different than the length of the other fins.

83. The process of claim 76 wherein the fin assembly comprises a plurality of parallel spaced fins, at least one of the fins having a height that is different than the height of the other fins.

84. The process of claim 76 wherein the fin has a cross section having the shape of a square, a rectangle, or a trapezoid.

85. The process of claim 76 wherein the fin is made of a material comprising:

steel;

aluminum;

titanium;

iron;

nickel;

platinum;

rhodium;

copper;

chromium;

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.

86. The process of claim 76 wherein the fin is made of an alloy comprising Ni, Cr and Fe, or an alloy comprising Fe, Cr, Al and Y.

87. The process of claim 76 wherein the fin is made of an Al₂O₃ forming material or a Cr₂O₃ forming material.

88. The process of claim 25 wherein the support strip further comprises a plurality of parallel microgrooves extending between the front edge of the support strip and the second side edge of the support strip.

89. The process of claim 25 wherein the support strip further comprises a plurality of parallel microgrooves extending between the back edge of the support strip and the first side edge of the support strip.

90. The process strip of claim 25 wherein the support strip further comprises a plurality of parallel microgrooves extending between the front edge of the support strip and the first side edge of the support strip.

91. The process of claim 25 wherein the support strip further comprises a plurality of parallel microgrooves extending between the back edge of the support strip and the second side edge of the support strip.

92. The process of claim 25 wherein the support strip further comprises a plurality of parallel microgrooves extending between the front edge of the support strip and the second side edge of the support strip, and a plurality of parallel microgrooves extending between the back edge of the support strip and the first side edge of the support strip.

93. The process strip of claim 25 wherein the microgrooves are oriented toward the front edge and the first side edge at an angle with the center axis of more than about 0°

and less than about 90°

.

94. The process of claim 25 wherein the microgrooves are oriented toward the front edge and the first side edge at an angle with the center axis in the range from about 50°

to about 80°

.

95. The process of claim 25 wherein the microgrooves are oriented toward the front edge and the first side edge at an angle with the center axis of more than 90°

and less than about 180°

.

96. The process strip of claim 25 wherein the microgrooves are oriented toward the front edge and the first side edge at an angle with the center axis in the range from about 100°

to about 150°

.

97. The process of claim 25 wherein the front edge and the back edge are sufficiently closed to block the flow of fluid through the front edge and the back edge.

98. The process of claim 25 wherein the front edge and the back edge are sufficiently open to permit the flow of fluid through front edge and the back edge.

99. The process of claim 25 wherein the first side edge and the second side edge are sufficiently open to permit the flow of fluid through the first side edge and the second side edge.

100. The process of claim 25 wherein the first side edge and the second side edge are sufficiently closed to block the flow of fluid through the first side edge and the second side edge.

101. The process of claim 25 wherein the support strip has a thickness in the range from about 1 to about 1000 microns.

102. The process of claim 25 wherein the microgrooves have a depth in the range from about 0.1 to about 1000 microns.

103. The process of claim 25 wherein the microgrooves have widths in the range from about 0.1 to about 1000 microns.

104. The process of claim 25 wherein the spacing between the microgrooves is in the range up to about 1000 microns.

105. The process of claim 25 wherein the microgrooves have cross sections in the shape of a square, rectangle, vee, semi-circle, dovetail and/or trapezoid.

106. The process of claim 27 wherein the thermally conductive material comprises metal, silicon carbide, graphite, or a combination of two or more thereof.

107. The process of claim 27 wherein the thermally conductive material comprises stainless steel or an alloy comprising iron, chromium, aluminum and yttrium.

108. The process of claim 25 wherein the catalyst comprises particulates positioned in the microgrooves.

109. The process of claim 1 wherein the catalyst in the styrene-forming process microchannel is supported by a composite support structure, comprising:

at least one first support strip comprising a first surface, a second surface, a length with a center axis extending along the length, a front edge, a back edge, a first side edge, a second side edge, the front edge and the back edge extending from the first side edge and to the second side edge, a plurality of parallel microgrooves in the first surface extending from the front edge to the second side edge, and a plurality of parallel microgrooves in the first surface extending from first side edge to the back edge;

at least one second support strip comprising a first surface, a second surface, a length with a center axis extending along the length, a front edge, a back edge, a first side edge, a second side edge, the front edge and the back edge extending from the first side edge to the second side edge, a plurality of parallel microgrooves in the first surface extending from the front edge to the first side edge, and a plurality of parallel microgrooves in the first surface extending from second side edge to the back edge;

the first support strip being adjacent to the second support strip with the second surface of the first support strip contacting the first surface of the second support strip;

the front and back edges of each of the support strips being open to permit fluid to flow through the front and back edges;

the side edges of each of the support strips being closed to prevent fluid from flowing through the side edges;

each of the microgrooves penetrating through the support strips sufficiently to permit fluid to flow through the support strips from one support strip to another;

the microgrooves in the first surface of the first support strip being oriented toward the front edge and the first side edge of the first support strip and forming an angle with the center axis of more than about 0° and

less than 90°

; and

the microgrooves in the first surface of the second support strip being oriented toward the front edge and the first side edge of the second support strip and forming an angle with the center axis of more than 90° and

less than about 180°

.

110. The process of claim 109 wherein the support structure further comprises end plates to prevent the flow of fluid out of the sides of the support structure.

111. The process of claim 109 wherein the support structure comprises a plurality of the first support strips and a plurality of the second support strips, the first and second support strips being stacked one above the other or positioned side by side one another in alternating sequence.

112. The process of claim 31 wherein the endothermic process comprises a steam reforming reaction or a dehydrogenation reaction.

113. The process of claim 32 wherein the exothermic process comprises a water-gas shift reaction, methanol synthesis reaction or ammonia synthesis reaction.

114. The process of claim 1 wherein fluid flows in the styrene-forming process microchannel 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.

115. The process of claim 1 wherein fluid flows in the styrene-forming process microchannel 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.

116. The process of claim 1 wherein a heat exchange fluid flows in the heat exchange channel, the heat exchange fluid comprising the feed composition or the product.

117. The process of claim 1 wherein a heat exchange fluid flows in the heat exchange channel, the heat exchange fluid comprising one or more of air, steam, liquid water, carbon monoxide, carbon dioxide, gaseous nitrogen, liquid nitrogen, inert gas, gaseous hydrocarbon, oil and/or liquid hydrocarbon.

118. The process of claim 1 wherein the conversion of ethylbenzene is at least about 25% per cycle.

119. The process of claim 1 wherein the conversion of ethylbenzene is at least about 70% per cycle.

120. The process of claim 1 wherein the selectivity to styrene is at least about 50% per cycle.

121. The process of claim 1 wherein the selectivity to styrene is at least about 80% per cycle.

122. The process of claim 1 wherein the selectivity to styrene is at least about 90% per cycle.

123. The process of claim 1 wherein the catalyst in the styrene-forming process microchannel is supported by a composite support structure, comprising:

at least one first support strip comprising a first surface, a second surface, a length with a center axis extending along the length, a front edge, a back edge, a first side edge, a second side edge, the front edge and the back edge extending from the first side edge and to the second side edge, a plurality of parallel microgrooves in the first surface aligned at an angle of about 90°

with the center axis; and

at least one second support strip comprising a first surface, a second surface, a length with a center axis extending along the length, a front edge, a back edge, a first side edge, a second side edge, the front edge and the back edge extending from the first side edge to the second side edge, a plurality of parallel microgrooves in the first surface aligned parallel with the center axis;

the first support strip being adjacent to the second support strip with the second surface of the first support strip contacting the first surface of the second support strip;

the microgrooves penetrating through the support strips sufficiently to permit fluid to flow through the support strips from one support strip to another support strip.

124. The process of claim 123 wherein the through holes are of sufficient dimension to permit reactants and/or product to flow from the first surface of the first support strip to the first surface of the second support strip and/or from the first surface of the second support strip to the first surface of the first support strip.

125. The process of claim 123 wherein the first support strip and the second support strip are made of thermally conductive materials and the contacting between the second surface of the first support strip and the first surface of the second support strip is sufficient to permit heat to be conducted between the first support strip and the second support strip.

126. The process of claim 43 wherein the thermal resistance layer is positioned on the heat transfer wall and/or embedded within the heat transfer wall.

127. The process of claim 43 wherein the thermal resistance layer comprises a vacuum, a gaseous material, a liquid and/or a solid material.

128. The process of claim 43 wherein the thermal resistance layer comprises a solid material which contains void spaces, openings and/or through holes.

129. The process of claim 43 wherein the thermal resistance layer comprises one or more strips or shims which contain void spaces, openings and/or through holes.

130. The process of claim 43 wherein the thermal resistance layer comprises one or more strips or shims with grooves formed in the strip.

131. The process of claim 43 wherein the thermal resistance layer comprises one or more strips or shims, each of the shims having a first surface and a second surface, and grooves formed in the first surface and/or second surface.

132. The process of claim 43 wherein the thermal resistance layer comprises one or more sub-assemblies, each sub-assembly comprising two or more shims stacked one above another with one or more void spaces positioned between the shims.

133. The process of claim 43 wherein the heat transfer wall and/or thermal resistance layer comprise one or more sub-assemblies, each sub-assembly comprising two or more shims stacked one above another with one or more void spaces positioned between the shims.