PROCESS FOR MAKING STYRENE USING MIRCOHANNEL PROCESS TECHNOLOGY

• US 20070225532A1
• Filed: 03/23/2007
• Published: 09/27/2007
• Est. Priority Date: 03/23/2006
• Status: Active Grant

• Current Assignee: Velocys Incorporated (Velocys PLC)
• Original Assignee: Velocys Incorporated (Velocys PLC)
• Inventors: Yang, Bin, Marco, Jeffrey, Daly, Francis, Tonkovich, Anna, Hickey, Thomas, Paul Jarosch, Kai
• Granted Patent: US 7,847,138 B2
• Time in Patent Office: Days
• US Class Current: 585/444
• 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 25/431 Straight mixing tubes with baffles or obstructions that do not cause substantial pressure drop; Baffles therefor
• 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 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.

2. The process of claim 1 wherein the catalyst 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 comprises at least one oxidative dehydrogenation catalyst.

4. The process of claim 1 wherein the ethylbenzene is formed by contacting benzene with ethylene in the presence of at least one alkylation catalyst.

5. The process of claim 4 wherein the ethylbenzene is formed in at least one process microchannel.

6. The process of claim 4 wherein the ethylene is formed by dehydrogenating ethane in the presence of at least one dehydrogenation catalyst in at least one process microchannel.

7. The process of claim 4 wherein the ethylene is formed by reacting ethane with oxygen in the presence of at least one oxidative dehydrogenation catalyst in at least one process microchannel.

8. 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.

9. The process of claim 8 wherein the product comprises styrene, ethylbenzene, ethylene, and hydrogen.

10. The process of claim 9 wherein the ethylbenzene in the product is recycled to the feed composition.

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

12. The process of claim 9 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.

13. The process of claim 12 wherein the ethylene is reacted with the benzene in at least one process microchannel containing the alkylation catalyst.

14. The process of claim 3 wherein the feed composition and the oxygen are mixed prior to entering the process microchannel.

15. 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 process microchannel, the process microchannel having an entrance for the feed composition, the feed composition entering the process microchannel through the entrance for the feed composition, the staged addition feed stream flowing from the staged addition channel into the process microchannel, the staged addition feed stream entering the process microchannel downstream of the entrance for the feed composition and contacting the feed composition in the process microchannel.

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

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

21. The process of claim 20 wherein the feed composition further comprises nitrogen.

22. The process of claim 15 wherein the staged addition feed stream comprises air, oxygen or oxygen enriched air.

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

44. 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.

45. 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.

48. The process of claim 3 wherein the catalyst comprises FeVO₄, CrVO₄, NaVO₃, BiVO₄, AlVO₄, 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.

49. The process of claim 1 wherein the catalyst comprises a graded catalyst.

54. The process of claim 1 wherein the catalyst is supported on a support, the support comprising a heat conductive material.

57. The process of claim 1 wherein the catalyst 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.

71. The process of claim 1 wherein the catalyst 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.

77. The process of claim 71 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.

91. The process of claim 71 wherein the support strip is made of a thermally conductive material.

98. The process of claim 1 wherein the process microchannel exchanges heat with a heat exchange fluid flowing in the heat exchange channel.

99. The process of claim 98 wherein the heat exchange fluid undergoes a phase change as it flows in the heat exchange channel.

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

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

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

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

110. The process of claim 109 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.

111. The process of claim 109 wherein the microchannel reactor further comprises a preheat section for heating the feed composition prior to flowing the feed composition in the process microchannels and a cool down section for cooling product flowing out of the process microchannels.

112. The process of claim 111 wherein the product flows from the cool down section to a styrene knockout drum where the product is cooled.

113. The process of claim 111 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.

114. The process of claim 113 wherein the microchannel reactor core and the cool down section are adjacent to the preheat section.

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

134. The process of claim 1 wherein the catalyst 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.

135. The process of claim 1 wherein the catalyst 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.

137. The process of claim 1 wherein the catalyst 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.

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

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149. An apparatus, comprising:

a process microchannel;

a heat exchange channel; and

a heat transfer wall positioned between the process microchannel and the heat exchange channel, the heat transfer wall comprising at least one thermal resistance layer.

168. A microchannel reactor comprising the apparatus of claim 149.

169. An apparatus, comprising:

a plurality of the microchannel reactors of claim 168 positioned in a vessel, each microchannel reactor comprises a plurality of process microchannels, a plurality of heat exchange channels, and optionally a plurality of staged addition channels,

the vessel being equipped with a manifold for flowing a feed to the process microchannels, a manifold for flowing product from the process microchannels, a manifold for flowing heat exchange fluid to the heat exchange channels, optionally a manifold for flowing oxygen or a source of oxygen to the staged addition channels, and a manifold for flowing heat exchange fluid from the heat exchange channels.

170. The apparatus of claim 169 wherein each microchannel reactor comprises from about 1 to about 50,000 process microchannels, and the vessel comprises from 1 to about 1000 microchannel reactors.

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