Quantifying rate enhancements for acid catalysis in CO 2 -enriched high-temperature water
dc.contributor.author | Hunter, Shawn E. | en_US |
dc.contributor.author | Savage, Phillip E. | en_US |
dc.date.accessioned | 2008-02-04T19:15:13Z | |
dc.date.available | 2009-02-03T16:28:50Z | en_US |
dc.date.issued | 2008-02 | en_US |
dc.identifier.citation | Hunter, Shawn E.; Savage, Phillip E. (2008). "Quantifying rate enhancements for acid catalysis in CO 2 -enriched high-temperature water." AIChE Journal 54(2): 516-528. <http://hdl.handle.net/2027.42/57897> | en_US |
dc.identifier.issn | 0001-1541 | en_US |
dc.identifier.issn | 1547-5905 | en_US |
dc.identifier.uri | https://hdl.handle.net/2027.42/57897 | |
dc.description.abstract | Thermodynamic calculations revealed that 10 to 100-fold increases in reaction rate are obtainable with added CO 2 (0.1–1 MPa) for an acid-catalyzed reaction in high-temperature liquid water (HTW) that is first order in H + concentration. These calculations suggest that CO 2 is most effective as a rate-enhancing additive in HTW at lower temperatures (150–200°C). When compared with increased temperature as a competitive option for accelerating acid-catalyzed reactions in HTW, CO 2 addition generally carries a lower pressure penalty (and no temperature penalty) for the model acid-catalyzed reaction with activation energies of up to 35 kcal/mol. An experimental survey revealed that CO 2 addition is effective for achieving increased reaction rates for dibenzyl ether hydrolysis in HTW, but that bisphenol A cleavage, methyl benzoate hydrolysis, and o -phthalic acid decarboxylation were not significantly impacted by added CO 2 . This behavior is consistent with previous results for these reactions wherein mineral acid, rather than CO 2 , was added to lower the pH. A summary of experimental results reported for reactions in CO 2 -enriched HTW revealed that product yields of some reactions can be increased by a factor of 23 with added CO 2 . Taken collectively, these results suggest that CO 2 addition may be a practical technique for making HTW more attractive as a reaction medium for acid-catalyzed organic synthesis. © 2007 American Institute of Chemical Engineers AIChE J, 2008 | en_US |
dc.format.extent | 306273 bytes | |
dc.format.extent | 3118 bytes | |
dc.format.mimetype | application/pdf | |
dc.format.mimetype | text/plain | |
dc.publisher | Wiley Subscription Services, Inc., A Wiley Company | en_US |
dc.subject.other | Chemistry | en_US |
dc.subject.other | Chemical Engineering | en_US |
dc.title | Quantifying rate enhancements for acid catalysis in CO 2 -enriched high-temperature water | en_US |
dc.type | Article | en_US |
dc.rights.robots | IndexNoFollow | en_US |
dc.subject.hlbsecondlevel | Chemical Engineering | en_US |
dc.subject.hlbtoplevel | Engineering | en_US |
dc.subject.hlbtoplevel | Science | en_US |
dc.description.peerreviewed | Peer Reviewed | en_US |
dc.contributor.affiliationum | Chemical Engineering Dept., University of Michigan, Ann Arbor, MI 48109 | en_US |
dc.contributor.affiliationum | Chemical Engineering Dept., University of Michigan, Ann Arbor, MI 48109 ; Chemical Engineering Dept., University of Michigan, Ann Arbor, MI 48109 | en_US |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/57897/1/11392_ftp.pdf | |
dc.identifier.doi | http://dx.doi.org/10.1002/aic.11392 | en_US |
dc.identifier.source | AIChE Journal | en_US |
dc.owningcollname | Interdisciplinary and Peer-Reviewed |
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