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Process for making styrene using mircohannel process technology

Inactive Publication Date: 2011-05-12
TONKOVICH ANNA LEE +7
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

This invention, in at least one embodiment, provides the advantage of increasing product yield and energy efficiency by improving heat and mass transfer performance. With this invention it is possible to reduce capital costs by reducing the size of processing equipment and the number of downstream separation units. Catalyst productivity may be enhanced by allowing the catalyst to operate in its peak performance window and by avoiding hot spots. With this invention it is possible to provide cost-effective plant expansion by adding incremental capacity with favorable economics.

Problems solved by technology

This reaction is endothermic and equilibrium limited.
A problem with the process is that it consumes a high level of energy.
As a result, reactant recycles are often needed.
However, the separation of unreacted ethylbenzene from styrene is costly due to the close boiling points of ethylbenzene (136° C.) and styrene (145° C
Thus far this process has not been commercialized.
An increase in the reaction temperature may increase the ethylbenzene conversion, but styrene selectivity tends to decrease significantly due to combustion of styrene and ethylbenzene.
The presence of hot spots in the catalyst bed tends to sinter the catalyst resulting in catalyst deactivation.

Method used

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  • Process for making styrene using mircohannel process technology
  • Process for making styrene using mircohannel process technology
  • Process for making styrene using mircohannel process technology

Examples

Experimental program
Comparison scheme
Effect test

example 1

0.7% K2O-15% MoO3 / SiO2—TiO2 catalyst is prepared by the sol-gel method. 20.0 g tetraethylorthosilicate and 27.29 g titanium isopropoxide are dissolved in 200 ml isopropyl alcohol solution with stirring. In another beaker, 2.93 g ammonium paramolybdate are dissolved in 13.65 g H2O and then 0.30 g 45% KOH solution are added. The aqueous solution is added dropwise to the alcohol solution (1 ml / min). After all of the aqueous solution is added, the resulting gel is stirred for additional 15 min. The gel is dried at 110° C. overnight and calcined at 550° C. for 5 hours. The catalyst is crushed and sieved to 60-100 mesh.

The catalyst (0.4 g) is loaded in a quartz tube reactor having a 0.2 inch O.D. (0.635 cm). The reactor volume is 0.3 ml. A feed gas composition containing 9.9% by volume ethylbenzene, 5% by volume O2 and 85.1% by volume N2 flows into the reactor. The feed gas flow rate is 180 ml / min. The contact time based on reactor volume is 0.1 second. The process operates for 3 hours wi...

example 2

0.7% K2O-18% V2O5 / SiO2—ZrO2 catalyst is prepared by the sol-gel method. 7.05 g vanadium (III) 2,4-pentanedionate are dissolved in 200 ml iso-butanol with stirring at 60° C. After cooling, 19.97 g zirconium n-butoxide are added at room temperature with stirring, followed by 15.0 g n-butoxysilane. In another beaker, 0.19 g 45% KOH solution are mixed with 6.63 g H2O. The aqueous solution is added dropwise to the alcohol solution (1 ml. / min). After all of the aqueous solution is added, the resulting mixture is stirred for an additional 15 min. The gel is then dried at 110° C. overnight and calcined at 550° C. for 5 hours. The catalyst is crushed and sieved to 60-100 mesh.

The catalyst (0.5 g) is loaded in the quartz tube reactor identified in Example 1. The feed gas composition contains 9.9% by volume ethylbenzene, 5% by volume O2 and 85.1% by volume N2. The contact time is 0.1 second. The process operates for 3 hours with no evidence of catalyst deactivation. The process is operated at ...

example 3

Mg0.99MoO3.99 catalyst is prepared by the sol-gel method. 16.00 g molybdenum (VI) oxide bis(2,4-pentanedionate) is dissolved in 200 ml methoxyethanol. 5.56 g magnesium ethoxide are then added with stirring.

Subsequently, 14.13 g 2.5 mol / L NH4OH solution are added dropwise to the mixture. The resulting gel is dried at 110° C. for 5 hours and then calcined at 550° C. for 12 hours. The catalyst is crushed and sieved to 60-100 mesh.

The catalyst (0.3 g) is loaded in the quartz tube reactor identified in Example 1. The feed gas composition contains 9.9% by volume ethylbenzene, 5% by volume O2 and 85.1% by volume N2. The contact time is 0.1 second. The process operates for 4 hours with no evidence of catalyst deactivation. The process is conducted at atmospheric pressure. The products are analyzed by GC. At 500° C., 29% ethylbenzene conversion and 88% styrene selectivity are achieved. The styrene yield is 26%. O2 conversion is 78%.

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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.

Description

TECHNICAL FIELDThis invention relates to a process for making styrene using microchannel process technology.BACKGROUNDStyrene is typically produced commercially by dehydrogenating ethylbenzene in the presence of an iron-based catalyst. This reaction is endothermic and equilibrium limited. The process is usually operated at temperatures between about 600-850° C. and at atmospheric or sub-atmospheric pressure. Steam is often co-fed to the reactor with the ethylbenzene. A problem with the process is that it consumes a high level of energy. The conversion of ethylbenzene is typically below 65% to maintain selectivity to styrene in excess of 95%. As a result, reactant recycles are often needed. However, the separation of unreacted ethylbenzene from styrene is costly due to the close boiling points of ethylbenzene (136° C.) and styrene (145° C.).The use of oxidative dehydrogenation of ethylbenzene has been suggested as a substitute for the dehydrogenation of ethylbenzene. Thus far this pr...

Claims

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Application Information

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IPC IPC(8): C07C5/367B01J19/00C07C5/333
CPCB01F5/0475B01J2219/00878B01F5/0483B01F5/061B01F5/0646B01F5/0655B01F13/0059B01F2005/0621B01F2005/0636B01J19/0093B01J2219/00783B01J2219/00804B01J2219/0081B01J2219/00822B01J2219/00824B01J2219/00826B01J2219/00828B01J2219/00831B01J2219/00833B01J2219/00835B01J2219/00844B01J2219/0086B01J2219/00873B01J2219/00889B01J2219/00891C07C2/66C07C5/3332C07C5/48C07C15/46C07C2521/02C07C2521/06C07C2521/08C07C2523/02C07C2523/04C07C2523/10C07C2523/18C07C2523/22C07C2523/26C07C2523/28C07C2523/30C07C2523/42C07C2523/44C07C2523/46C07C2523/745C07C2523/847C07C2523/881C07C2523/883C07C2523/888C07C2527/167F28D9/00F28F3/048F28F3/086F28F2260/02B01F5/0478Y10S585/921B01J2219/00876C07C15/073C07C11/04Y02P20/582Y02P20/52B01F25/31422B01F25/3142B01F25/31424B01F25/4317B01F25/431971B01F25/4338B01F25/433B01F33/30B01F2101/2204B01J2219/00869C07C5/277C07C2521/10F28F13/12F28F21/04F28F21/081F28F2270/00
Inventor TONKOVICH, ANNA LEEJAROSCH, KAI TOD PAULYANG, BINDALY, FRANCIS P.HICKEY, THOMAS P.MARCO, JEFFREYLAPLANTE, TIMOTHY J.LONG, RICHARD Q.
Owner TONKOVICH ANNA LEE
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