Name: temperature-programmed deoxygenation of acetic acid on molybdenum carbide catalysts
Uploaded: 2017-02-07T15:00:00
Description: Watch this Scientific Journal Video about Temperature-programmed Deoxygenation of Acetic Acid on Molybdenum Carbide Catalysts at JoVE.com

This work was supported by the Department of Energy Bioenergy Technologies Office under Contract no. DE-AC36-08-GO28308. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes.

CAUTION: Consult safety data sheets (SDS) for all chemicals used prior to operation. Flammable gases may present explosion hazards if combined with air or oxygen and an ignition source. Hydrogen is an extremely flammable gas. Acids are corrosive, and in the case of skin or eye contact, are irritants and may produce burns. Acetic acid is a flammable liquid and vapor and thus may ignite and/or explode in the presence of open flames, sparks and oxidizing agents, in addition to potentially causing severe skin burns and eye d...

<ol>
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A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Vanadia/Titania+Catalysts+for+Selective+Catalytic+Reduction+(SCR)+of+Nitric-Oxide+by+Ammonia.">Vanadia/Titania Catalysts for Selective Catalytic Reduction (SCR) of Nitric-Oxide by Ammonia.</a> J Catal. 151 (1), 226-240 (1995).</li><li>Clarke, D. B., Bell, A. T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=An+Infrared+Study+of+Methanol+Synthesis+from+CO2+on+Clean+and+Potassium-Promoted+Cu/SiO2.">An Infrared Study of Methanol Synthesis from CO2 on Clean and Potassium-Promoted Cu/SiO2.</a> J Catal. 154 (2), 314-328 (1995).</li><li>Schaidle, J. A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Experimental+and+Computational+Investigation+of+Acetic+Acid+Deoxygenation+over+Oxophilic+Molybdenum+Carbide:+Surface+Chemistry+and+Active+Site+Identity.">Experimental and Computational Investigation of Acetic Acid Deoxygenation over Oxophilic Molybdenum Carbide: Surface Chemistry and Active Site Identity.</a> ACS Catal. 6 (2), 1181-1197 (2016).</li><li>Ruddy, D. A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recent+advances+in+heterogeneous+catalysts+for+bio-oil+upgrading+via+"ex+situ+catalytic+fast+pyrolysis":+catalyst+development+through+the+study+of+model+compounds.">Recent advances in heterogeneous catalysts for bio-oil upgrading via "ex situ catalytic fast pyrolysis": catalyst development through the study of model compounds.</a> Green Chem. 16 (2), 454-490 (2014).</li><li>Dutta, A., Schaidle, J. A., Humbird, D., Baddour, F. G., Sahir, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Conceptual+Process+Design+and+Techno-Economic+Assessment+of+Ex+Situ+Catalytic+Fast+Pyrolysis+of+Biomass:+A+Fixed+Bed+Reactor+Implementation+Scenario+for+Future+Feasibility.">Conceptual Process Design and Techno-Economic Assessment of Ex Situ Catalytic Fast Pyrolysis of Biomass: A Fixed Bed Reactor Implementation Scenario for Future Feasibility.</a> Top. Catal. 59 (1), 2-18 (2016).</li><li>Venkatakrishnan, V. K., Delgass, W. N., Ribeiro, F. 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The TPRxn method is a powerful tool for screening of catalytic materials, providing information about the activity and selectivity of a catalyst as a function of reaction temperature. Other temperature-programmed methods such as TPD, TPO and TPR can provide information on the adsorption strength of reactants, number of adsorption sites, and appropriate catalyst pre-treatment procedures, but do not provide direct catalytic performance data. It is important to note that the TPRxn method detailed in this work does not measu...

Temperature programmed reaction (TPRxn) is one of many temperature programmed methods, including desorption (TPD), oxidation (TPO), and reduction (TPR), and proceeds via exposure of a catalyst to a reactant concurrent with or followed by a steady increase in temperature.1,2,3 TPRxn is a transient technique that provides information about catalyst activity and selectivity as a function of reaction temperature.4,5,6 It is also a popular technique: a search of the keywords &#39;temperature programmed reaction&#39; in the literature yields over 1,000 sources citing its use.
TPRxn experiments are typically performed in a microreactor system, equipped with a mass spectrometer (MS) for real-time analysis of the reactor effluent and correlation of performance with temperature. Reactant gases can be introduced using mass flow controllers and liquids can be introduced via a syringe pump or as vapors by bubbling inert gas through a liquid. The catalyst is often pre-treated in situ to form the desired catalytic phase for the reaction. Some systems are equipped with additional analytical equipment, beyond the typical mass spectrometer, to provide quantitative or qualitative information about the catalyst selectivity, surface species present on the catalyst, or reaction mechanism. For example, temperature programmed in situ Fourier Transform Infrared Spectroscopy (FTIR) provides information about the evolution of surface species with varying reaction temperature.7,8 The TPRxn system demonstrated in this work is equipped with a gas chromatogram (GC) in addition to the more typical MS. This GC, equipped with four parallel columns, allows for more accurate quantification of the reaction products, but is limited in analysis frequency by the time it takes the products to elute through the columns. Thus, the combination of MS and GC can be particularly useful for coupling real-time identification with accurate quantification of reactants and products.
Here, we apply the TPRxn methodology to study the deoxygenation of acetic acid on molybdenum carbide catalysts. This is an interesting and important reaction in catalyst research, as acetic acid is a useful analog for the many carboxylic acids present in biomass pyrolysis vapors.9 The high oxygen content in biomass pyrolysis vapors necessitates oxygen removal to produce hydrocarbon fuels,10,11,12 and molybdenum carbide catalysts have shown promising deoxygenation performance for many biomass pyrolysis vapor model compounds, including furfural, 1-propanol, phenolics and acetic acid.9,13,14,15,16 However, the activity and selectivity of molybdenum carbide catalysts in deoxygenation reactions is dependent on the catalyst structure and composition, the reacting species and the reaction conditions.
The data collected from TPRxn of acetic acid shows that molybdenum carbide catalysts are active for deoxygenation reactions above ca. 300 &#176;C, and when combined with catalyst characterization information allows for quantification of the catalyst activity as a function of temperature via the calculation of acetic acid turnover rates. The TPRxn results show that deoxygenation (i.e., C-O bond-breaking) products are favored at temperatures below ca. 400 &#176;C and decarbonylation (i.e., C-C bond-breaking) products are favored at temperatures above ca. 400 &#176;C. Additionally, TPRxn studies illustrate the changes in the activity and selectivity of molybdenum carbide catalysts produced using various synthetic procedures (i.e., the production of different molybdenum carbide catalyst structures and compositions). Still, the value of this information and, more generally, the successful application of TPRxn experimental data toward catalyst design and process optimization is a function of the quality of the data obtained. Careful consideration and knowledge of the potential difficulties and limitations highlighted throughout the TPRxn procedure is paramount.

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	<tbody>
		<tr height="57">
			<td height="57" style="height:58px;width:215px;">glacial acetic acid</td>
			<td style="width:179px;">Cole-Parmer</td>
			<td style="width:148px;">EW-88401-62</td>
			<td style="width:401px;">alternate supplier acceptable if ACS purity grade. See caution statement in protocol for safety information</td>
		</tr>
		<tr height="57">
			<td height="57" style="height:58px;width:215px;">UHP H&#8322;</td>
			<td style="width:179px;">Airgas</td>
			<td style="width:148px;">HY R300</td>
			<td>alternate supplier acceptable if &#62;99.99% purity</td>
		</tr>
		<tr height="57">
			<td height="57" style="height:58px;width:215px;">UHP He</td>
			<td style="width:179px;">Airgas</td>
			<td style="width:148px;">HE R300SS</td>
			<td>alternate supplier acceptable if &#62;99.99% purity</td>
		</tr>
		<tr height="57">
			<td height="57" style="height:58px;width:215px;">UHP Ar</td>
			<td style="width:179px;">Arigas</td>
			<td style="width:148px;">AR R200</td>
			<td>alternate supplier acceptable if &#62;99.99% purity</td>
		</tr>
		<tr height="57">
			<td height="57" style="height:58px;width:215px;">acetone</td>
			<td style="width:179px;">VWR International</td>
			<td style="width:148px;">BDH1101-4LP</td>
			<td>alternate supplier acceptable if &#62;99.5% purity</td>
		</tr>
		<tr height="57">
			<td height="57" style="height:58px;width:215px;">quartz chips</td>
			<td style="width:179px;">Powder Technology Inc.</td>
			<td style="width:148px;">Crushed Quartz</td>
			<td style="width:401px;">sieved 180-300 &#181;m, calcined in air at 500 &#176;C overnight</td>
		</tr>
		<tr height="56">
			<td height="56" style="height:56px;width:215px;">mass spectrometer - turbo vacuum pump</td>
			<td style="width:179px;">Pfeiffer Vacuum</td>
			<td style="width:148px;">TSU 071</td>
			<td style="width:401px;">mass spectrometer is controlled with LabVIEW 2010 software package (National Instruments)</td>
		</tr>
		<tr height="56">
			<td height="56" style="height:56px;width:215px;">mass spectrometer - turbo vacuum pump</td>
			<td style="width:179px;">Stanford Research Systems</td>
			<td style="width:148px;">RGA100</td>
			<td style="width:401px;"></td>
		</tr>
		<tr height="126">
			<td height="126" style="height:126px;width:215px;">micro gas chromatograph</td>
			<td style="width:179px;">Agilent</td>
			<td style="width:148px;">CP740388</td>
			<td style="width:401px;">490 Micro GC; 4-channel system 
			Channel 1: 494001360 Molseive 10m, heated backflush 
			Channel 2: 494001460 PPU 10m, heated backflush 
			Channel 3: 490040 AL2O3/KCL 10+0.2m, heated backflush SPECIAL 
			Channel 4: 492005750 5CB 15m, heated</td>
		</tr>
		<tr height="56">
			<td height="56" style="height:56px;width:215px;">GC software</td>
			<td style="width:179px;">Aglient</td>
			<td style="width:148px;">OpenLAB CDS EZChrom Edition</td>
			<td style="width:401px;"></td>
		</tr>
		<tr height="57">
			<td height="57" style="height:58px;width:215px;">clean gas filters</td>
			<td style="width:179px;">Agilent</td>
			<td style="width:148px;">CP17974</td>
			<td>for use on GC carrier gases (He, Ar)</td>
		</tr>
		<tr height="57">
			<td height="57" style="height:58px;width:215px;">quartz &#34;U-tube&#34; reactor</td>
			<td style="width:179px;">n/a</td>
			<td style="width:148px;"></td>
			<td>hand blown glass, custom built to order</td>
		</tr>
		<tr height="57">
			<td height="57" style="height:58px;width:215px;">bubbler</td>
			<td style="width:179px;">n/a</td>
			<td style="width:148px;"></td>
			<td>custom built to order</td>
		</tr>
		<tr height="57">
			<td height="57" style="height:58px;width:215px;">ceramic furnace</td>
			<td style="width:179px;">Watlow</td>
			<td style="width:148px;">discontinued</td>
			<td>Similar furnace part #: VC401J12A-B000R</td>
		</tr>
		<tr height="57">
			<td height="57" style="height:58px;width:215px;">heat tape controller</td>
			<td style="width:179px;">n/a</td>
			<td style="width:148px;"></td>
			<td>custom built with Watlow EZ-zone parts</td>
		</tr>
		<tr height="57">
			<td height="57" style="height:58px;width:215px;">heat tape</td>
			<td style="width:179px;">Omega</td>
			<td style="width:148px;">FGH051-060</td>
			<td style="width:401px;">alternate supplier for extreme temperature heat tape acceptable</td>
		</tr>
		<tr height="57">
			<td height="57" style="height:58px;width:215px;">heat tape insulation</td>
			<td style="width:179px;">JEGS</td>
			<td style="width:148px;">710-80809</td>
			<td>alternate supplier acceptable</td>
		</tr>
		<tr height="57">
			<td height="57" style="height:58px;width:215px;">thermocouple</td>
			<td style="width:179px;">Omega</td>
			<td style="width:148px;">e.g., KMQSS-062U-18</td>
			<td>K-type thermocouples; alternate sizes may be required</td>
		</tr>
		<tr height="57">
			<td height="57" style="height:58px;width:215px;">thermocouple o-ring</td>
			<td style="width:179px;">Swagelok</td>
			<td style="width:148px;">VT-7-OR-001-1/2</td>
			<td>perfluoroelastomer(fluorocarbon FKM) o-ring</td>
		</tr>
		<tr height="57">
			<td height="57" style="height:58px;width:215px;">2 &#181;m solids filter, VCR gasket</td>
			<td style="width:179px;">Swagelok</td>
			<td style="width:148px;">SS-4-VCR-2-2M</td>
			<td></td>
		</tr>
		<tr height="57">
			<td height="57" style="height:58px;width:215px;">1 &#181;m orifice, VCR gasket</td>
			<td style="width:179px;">Lenox Laser</td>
			<td style="width:148px;">SS-4-VCR-2</td>
			<td>for mass spectrometer orifice</td>
		</tr>
		<tr height="93">
			<td height="93" style="height:94px;width:215px;">316/316L stainless steel tubing and fittings</td>
			<td style="width:179px;">Swagelok</td>
			<td style="width:148px;">Varies</td>
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temperature-programmed deoxygenation of acetic acid on molybdenum carbide catalysts

Temperature programmed reaction (TPRxn) is a simple yet powerful tool for screening solid catalyst performance at a variety of conditions. A TPRxn system includes a reactor, furnace, gas and vapor sources, flow control, instrumentation to quantify reaction products (e.g., gas chromatograph), and instrumentation to monitor the reaction in real time (e.g., mass spectrometer). Here, we apply the TPRxn methodology to study molybdenum carbide catalysts for the deoxygenation of acetic acid, an important reaction among many in the upgrading/stabilization of biomass pyrolysis vapors. TPRxn is used to evaluate catalyst activity and selectivity and to test hypothetical reaction pathways (e.g., decarbonylation, ketonization, and hydrogenation). The results of the TPRxn study of acetic acid deoxygenation show that molybdenum carbide is an active catalyst for this reaction at temperatures above ca. 300 &#176;C and that the reaction favors deoxygenation (i.e., C-O bond-breaking) products at temperatures below ca. 400 &#176;C and decarbonylation (i.e., C-C bond-breaking) products at temperatures above ca. 400 &#176;C.

The online MS provides the capability to analyze the gas composition at the reactor outlet in real-time. The online MS is not coupled with any device to separate products prior to analysis, and thus species identification is challenging when differentiating between compounds with overlapping mass fragmentation patterns. As shown in Table 2, many of the common products from acetic acid TPRxn experiments are characterized by multiple common m/z signals. Deconvolution of the...

Watch this Scientific Journal Video about Temperature-programmed Deoxygenation of Acetic Acid on Molybdenum Carbide Catalysts at JoVE.com

Temperature-programmed Deoxygenation of Acetic Acid on Molybdenum Carbide Catalysts

Presented here is a protocol for the operation of a micro-scale temperature-programmed reactor for evaluating the catalytic performance of molybdenum carbide during acetic acid deoxygenation.

Temperature programmed reaction (TPRxn) is a simple yet powerful tool for screening solid catalyst performance at a variety of conditions. A TPRxn system ...

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