Liu, Sen
(2012)
INVESTIGATION OF HOMOGENEOUS-HETEROGENEOUS COUPLING EFFECTS IN THE HIGH TEMPERATURE CATALYTIC OXIDATION REACTIONS OF LIGHT ALKANES IN A NOVEL MICROCHEMICAL REACTOR SYSTEM.
Doctoral Dissertation, University of Pittsburgh.
(Unpublished)
Abstract
Understanding the coupling effects between homogeneous and heterogeneous (HH) chemistry is crucial in the field of high-temperature catalysis. An important example in this area is the catalytic oxidation of light hydrocarbons. Microreactor technology, with its precise control of fluid and temperature fields, improved reactant mixing, and large surface-to-volume ratio, is ideally suited for the study of such reaction systems. Most significantly, the pathways of homogeneous-heterogeneous coupling can be better understood as critical reactor dimensions are reduced into micrometer range, where diffusive flux starts to play an equally important role as convective transport.
Here, we are reporting a novel modular microreactor system based on the use of silicon-based thin-film catalysts, which allows stable operation during thermal cycling up to 800 oC. Precise control and adjustment of the critical dimension, i.e. the height of reaction chamber, offers the ability to steer the relative importance of gas- and catalytic-phase chemistries due to transport of reactants between the gas phase and the catalytic walls. Additionally, a moveable thermocouple and quartz-glass capillary (connected to a mass spectrometer) allow the in-situ measurement of temperature and composition profiles in the reaction chamber. By combining these two capabilities, the system thus provides an efficient and sensitive way to investigate the interplay between gas phase and catalytic chemistries, and to evaluate the catalytic performance of thin-film catalysts. The reactor system was tested using oxidative coupling of methane (OCM) as model reaction. OCM has been studied intensively for many decades and offers a potentially highly efficient path for direct upgrading of methane to higher-value C2 products. The reaction is also well known to include catalytic steps in the generation of methyl radicals (as well as in undesired methane combustion) and homogeneous reaction steps in which methyl radicals are coupled to form the desired C2 products (C2H6 and C2H4). It thus forms an ideal test system for the above described microreactor system.
A La-based thin-film catalyst was deposited onto a silicon chip via dip-coating, characterized, and inserted into the microreactor. The effect of major reactor operating parameters, such as temperature, flow rate, C:O feed ratio, and, most importantly, the surface-to-volume ratio were tested in detailed experimental studies using both reactor outlet and spatially-resolved concentration profiles. The results show a strong decrease of C2 production rates with decreasing microreactor channel height (680 µm to 460 and 330 µm), in agreement with the established OCM reaction mechanism. A 2D FEM-based numeric model was also carried out to provide supports and further insights into OCM system. While the Pt- and Rh-catalyzed oxidative dehydrogenation of ethane (ODH) is currently under investigation as the second model reaction, it is promising that this methodology can be transferred to study several other systems, e.g. hydrogen oxidation and catalytic partial oxidation of methane (CPOM) and propane (CPOP).
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Details
| Item Type: |
University of Pittsburgh ETD
|
| Status: |
Unpublished |
| Creators/Authors: |
|
| ETD Committee: |
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| Date: |
2 February 2012 |
| Date Type: |
Publication |
| Defense Date: |
15 November 2011 |
| Approval Date: |
2 February 2012 |
| Submission Date: |
21 November 2011 |
| Access Restriction: |
3 year -- Restrict access to University of Pittsburgh for a period of 3 years. |
| Number of Pages: |
167 |
| Institution: |
University of Pittsburgh |
| Schools and Programs: |
Swanson School of Engineering > Chemical Engineering |
| Degree: |
PhD - Doctor of Philosophy |
| Thesis Type: |
Doctoral Dissertation |
| Refereed: |
Yes |
| Uncontrolled Keywords: |
high-temperature catalysis
homogeneous-heterogeneous coupling
microchemical reactor |
| Date Deposited: |
02 Feb 2012 15:45 |
| Last Modified: |
15 Nov 2016 13:55 |
| URI: |
http://d-scholarship.pitt.edu/id/eprint/10519 |
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